NEW

P RAC T CA L
C HEM ST RY
Fu n d a m e nt on] pr i n c i p l e s
A ppl i e d t o M o d e r n Li fe

NEW T ON HENR Y BLAC K

JA M ES BR YA NT C ON A N T

A ut h o rized b y t h e D ep art ment of Ed uc at io n

'

for us e i n the s ch ool s of A lb er t a

”

T OR ONT O : T H E M A C M I LLA N C O M P A NY OF
C A N A DA L I M I T E D A T S T M A R T I N S H O US E
’
, .
 C OP YR I G H T . 1 93 7

T HE M A C M I L L AN C OM P AN Y OF C AN A D A LI M I T ED

A ll r ig h t s reser v ed no p art o f t h i s b o o k may b e

rep ro d uc e d i n any fo rm w it h o ut p erm is s io n i n wri t ing
fro m t h e p ub lis h er ex c ep t b y a revi ewer wh o wis h es
,

t o q uo t e b r ief p as s ag es i n c o nnec t io n wi t h a re vi e w
wri t t en for i nc l us i o n in mag az ine o r news p ap er .

P R INT E D m C A N A DA
 P R EFA C E
’
IN th is textboo k we h ave tried t o arous e t h e pupil s interest
in c h emistry by app eal ing t o h is l o ve of t h e dramatic and b y
ul ating h is c uriosity c onc erning t h e nature of t h e com mon
+

stim

th ings in h is environment With th is in mind we h ave sug

.

gest ed many c lassroom experim ents t o b e d one by t h e t each er

on t h e lec ture t abl e and h ave c all ed attent io n t o num erous

appl ic ations of c h emistry in t h e pup il s everyd ay life We

’
.

have h oped in th ese ways t o make his study of t h e subj ec t

a v ital and prac tic al o ne On t h e oth er h and we h ave not
.
,

lost sight of t h e real o bj ec t of suc h a c ourse t h e mastery of

t h e fund ament al princ ip les and fac ts of c h emistry as t h e sc ience
of t h e c h anges i n m atter.

It i s unquestionably true th at t h e c onst ituenc y of our m o dern

h igh sc h ob l h as l n recent years expand ed and th at t h e maj ority

of t h e stud ent s wh o use th is b o o k will not continue th eir s tud ies

in any h igh er instit ution We h ave th erefore worked o ver t h e

.

t ext most c arefully t o insure simplicity of style t o make ex ,

planations c onvi ncing and t o inc l ud e only th ose facts laws ,

, ,

and th eories th at any well informed person to d ay need s t o know

-
.

T h e material is we b el ieve up t o d at e
, , We h ave enric h ed t h e
.

treatment by exc eeding t h e fac tual requirements of t h e C ollege

Entrance Examinat ion B o ard .

Our d iscussion of mo d ern th eories on t h e structure of matter

h as b eenfput in as simpl e a fo rmas is possibl e with suc h h ighly
tec hnical material and we h ave l imited ourselves t o wh at is
,

necessary for an und erst and ing of fund am ent al princ ipl es .

I n th is c onnection it is well for c h em istry t each ers t o remember

th at t h e ingenious electron diagrams of t h e atom wh ic h are
now so m uc h in vogue really d o not expl ain valenc e or any other
7
vi P R EFA C E

ch emical facts T h ey merel y set up o ne f asc inating pic t ure

.
,

wh ic h even t o d ay t h e invest igators in at o mic physic s are

repl ac ing by som eth ing m uc h l ess d efinit e and more math e
mat ical .

One of t h e d ifficult t as ks h emistry t each er is th at of of any

'

s o p l anning h is c ours e as t o m eet t h e d ifferen t interests need s , ,

and c ap acities of h is p upil s M any teach ers h ave found it .

h el pful t o d ivid e t h e year s wo rk into bloc ks or units A lth ough ’

”

.
,

we b elieve th at every t eac h er mus t work out h is own sy st em

of unit s t o fit his o wn situat ion we h ave ventured t o suggest ,

o ne p ossibl e d ivisio n of t h e subj ec t m atter int o w ork units -

.

Furth er suggestions on th is subj ec t will b e f ound in th e T eac h

'

er s M anual
’
.

We h ave arranged t h e mat erial on met als with a View t o

em ph as iz ing t h e general processes of met all urgy and t h e real
uses of t h e met als in mo d ern l ife W e h ave c onsistentl y .

avoid ed an enc y c l op ed ic c o mp iling of more or l ess useful

information ab out th eir extrac tion prop erties us es and , , ,

com pound s :
T h e ques t i ons and p ro b l ems at t h e end s of t h e c h ap ter s
h ave b een d ivide d int o th r ee g r oups w h ich ar e c l ear l y i nd i .
,

c at e d T h e fi r s t g r o up is mad e up of r at h er eas y b as i c
.

q u e s t i ons o n t h e t ext t h e se c o nd c o nt ai ns m or e ad v anc ed ,

ques t i ons and t h e th ir d numer i c al ques t i ons

, ,
.

W e h ave b een g r eatl y as sist ed in t h e w or k on th is b ook b y

many teac h er s in various sec tions of t h e c ountr y wh o h ave ,
-

mad e val ua bl e s ug g esti ons b as ed on th eir c l ass roomex per ienc e .

We w ould es pec iall y mention with g r atef ul ack nowl edg ment
t h e f oll ow ing : M r Fr ank B r id ges M r F r ank H B r oome .
,
. .
,

M r G F C l ukey M r J ames F C onway M r R ic h ar d O

. . .
, . .
,
. .

D ummer M r S S E nd sl ow M r E A rth ur E r ik s on P r o f
,
. . .
,
. .
,
.

J O Fr ank M r E K G ifi en M is s H attie D F H aub M r

'

.
. .
, . . .
,
. .
,

J oh n H H ill M r J C H ow ar d M iss G ret c hen Kauf man

.
, . . .
, ,

M r W alt er M c C r ory M r H ar o ld C M ar tin M r R ud ol p h

.
, . .
, .

M ey er M r E d win P et ers on M r M E P os t M r C W R ead

, .
,
. . .
,
. . .
,
P R EFA C E Vii

M r W F R oec k er M r L W S altz M r J L S l oanaker

. . .
, . . .
, . . .
,

M r R ay mond S T ob ey
. . .

T h e auth ors are muc h ind ebt ed t o D r G us t av us J E ssel en

. .

for val uabl e h el p , al s o t o M r A ug ust us K l oc k for c r it ic ally

.

rea d ing t h e p r oo f s h eet s and for pr ep ar ing new quest ions

and p r obl ems Dr D unc an P M ac D oug all h as b een g ood
. . .

eno ug h t o r ead t h e p r oo f s h eet s and t o m ak e us eful s ugg es

t ions B oth t h e manus c r ipt and t h e p r oo f sh eet s h ave b een
.

r ead cr it i c ll y b y m
a y w i f e w h o h as a dd e d m uc h t o t h
,
e c l ea r

nes s and s imp l ic ity of t h e sty l e T h e r es p onsib il ity f or any .

err or s th a t may appear in th is b ook rest s entirel y on t h e

s eni or auth or .

W e h ave mad e an effort t o s ec ur e l ine d r awing s th at would

c l ar i f y d iffic ult p r oces ses and h al f t ones th at w ould il l um
,
in
at e and g ive r eal ity t o t h e c h emic al ind us t r ies d isc us s ed in
t h e b ook I n th is we h ave b een g r eatl y as si st ed by g ener ous
.

f r iend s and coll eag ues t o wh om w e ar e g r atef ul , .

W e ar e muc h ind ebted t o t h e r es ear ch l ab or at or ies of many

l ar g e ind ust r ial c onc er ns f or t h e r el iable d at a and pert inent
ill ust r ations w h ic h th ey h ave fur nis h ed us .

N H B
. . .

N OTE . T h e d irec t ions for t h e ex peri ment s t o b e p erformed b y the s t ud ent s

are print ed in a sep arat e v olu me ent it l ed : NE W L AB ORATOR Y EXPE RIME NTS IN
PR ACTICAL C HEMISTRY .
 T A B LE OF C ON T E NTS

H ISTORICA L I NTROD U CTION . FIE L D OF C HEMIST R Y

C HEMICA L AND P H Y SICA L C HANGES
EL EMENTS AND C OM P O U NDS
OXY GEN C OM B U STION AND OZ ONE
, ,

H Y DROGEN AND I T S U SES

W ATER AND I T S C OM P OSITION H Y DROGEN P ERO XIDE
.

R E VIEW QU ESTIONS ON C HA P TERS I VI -

D A LTON S T HEOR Y OF A TOMS AND M O L EC U L ES

’

SY M B O L S FORM UL AS AND VA LEN c E

, ,

C HEMICA L EQUATIONS AND C OM P U TATIONS

R E VIEW QU ESTIONS ON C HA P TERS VI I I X -

S ODI U M C H L ORIDE AND H Y DRO X IDE

C H L ORINE AD H Y DROGEN C H L ORIDE
A CIDS B ASES AND S A LT S
, ,

I ONS AND EL ECTRONS

A TOMIC S TR U CT U RE AND VA LEN c E

R E VI EW QU EST IONS ON C HA P TERS X X I V -

S ULFU R AND T H E S U LFIDES

OX IDES O F S ULFU R AND THE A CIDS
C AR B ON A N D I T S T W O OXIDES
M O L EC ULAR AND A T OMIC W EIGHTS
G ENERA L R E VIEW QU ESTIONS ON C HA P TERS I XV I I I -

N ITROGEN AND A TMO S P HERIC G ASE S

A MMONIA AND A MMONI U M C OM P O U NDS

N ITRIC A CID AND FI X AT ION O F N ITROGEN

'

R E V IEW QU ESTIONS ON C HA P TERS X I X XX I -

XX I I . N Ew P ERIODIC LA W
I: T A B LE OF C ONT !

A P P EN DI X

P h y s ic al P r inc ip l es 1 n r eg ar d t o G as es
List of B ooks f o r F ur t h er S t ud y
I nd us t r ial C h ar t
S ol ub ilit y of W at er
S ol i d s i n
S ol ub il it y of G as es in W at er
P r es s ur e of W at er Vapor
D ens it ies of I mp o r t ant G ases
S ome C ommo n S ub s t anc es , C h emi c al N ames ,
F or mul as
S c al e of H ar d nes s

I N DEX
 P R A C T I C A L C H EM I ST R Y

C HA P T ER I

H I S T O R I CA L INTR O DUC T I O N . FIELD OF CHEM I STR Y

C h emist ry in ev ery d ay life b eginnings of ch emist ry in ancient

t imes c h em ist ry in t h e M idd le A ges t h e renaissance o f ch em
is t ry b eginnings of scient ific ch emis t ry c h emist ry in t h e eigh t
eent h cent ury .

C h emist ry and mod ern life d rugs , d y es , met als and al loy s ,
glass , t h e s oil and fert ilizers pure foo d s and d rinks
, .

Ed ucat ional v al ue of ch emis t ry , s cient ific met h od ; experiment s

and t h eories .

1 . C h emist ry v yd ay lif e
in e er t h e c ountl ess
.
“
A mong
artic l es entering into y our d ail y life are many th at all t h e
money in t h e world could not b uy a few sh ort y ears ago T h ey .

sim pl y d id not exis t M ost of th ese things are of humbl e

.

origin built up fro m m

, aterial s th at are often unattrac tive in
t h e raw state giving t o t h e c asual o b serv er l it tl e h int of t h e
,

wond rous ric h es th ey contain Lowly pro duc ts of t h e farm

.
,

t h e mine t h e forest
, even of air and wat er are transform ed
b y t h e magic wand of c h emist ry into things of th rill ing b eauty
and marvel ous util ity .

Stic ky ill smell ing coal t ar is now mad e t o yield gorgeous

,
-

c ol ors d el ic ious fl avors ex o tic perfum

, es and h eal ing m
, ed ic ines ; ,

t h e fuz z fro m c otton seed s is c onverted into ex quisite t oil et

ware gl eaming fi nish es l uxurious fab rics d urabl e uph ol stery
, , , ,

and powerful d y namite ; grimy mineral s are c h anged i nto

d el icate d ecorations for ch im aware l i estone and c oal find
-
m
th eir way into synth etic rubb er and p ine stumps produce
"
2 H I S T OR I C A L I NT R OD U C T I ON . FIEL D OF C HEM I S T R Y

ca mph or air and wat er are used as raw material s in making

fertiliz ers expl osives motor fuel s antifreez e and
, , , , smell ing

salts A nd c h emical wond ers far fro m c easing h ave j ust

.
, ,

b egun .

T h ese statements were mad e in 1 919 by t h e l ate Dr A rth ur .

D Littl e th en P resid ent of t h e A merican I nstitute of C h emical

.
,

Engineers and th ey are j ust as true t o d ay

,
I n fac t t h e .
,

progress mad e in t h e l ast fifteen y ears points t o t h e tremend o us

p ossibil ities th at t h e future h old s in store for t h e nation th at
und erstand s it s c h emistry and appl ies it intel ligentl y .

2 . B eginni ngs h emis t ry in anc ient t imes A lth ough

of c .

t h e sc ienc e o f c h emistry as we k now it tod ay is only a l ittl e -

more th an a hund red y ears old it s b eginnings d ate b ack

"
,

sev eral th ousand years I n fac t th ere is no d oubt th at

.
,

t h e p eopl e of ancient
G reec e, R ome, and
esp ec iall y Egyp t h ad

a goo d d eal of prac

‘

tical knowl edge ab out

cert ain m et al s , suc h

as gold and silver

( Fig . T h ey h ad
l earned h ow t o ex
Fig I Egy pt ian gold smit h s in t h e age of pyra id m
. .

b uil d ing
trac t c opp er, t in, iron,
mercury
.

l ead , and
from t h e ores T h eir d oc tors knew h ow t o prepare c ertain
.

medicines from pl ant and animal material s as well as from ,

mineral s T h ey dy ed th eir textil es with vegetabl e d y es T h ey

. .

were ac quaint ed with t h e pro c ess of ferment ation and t h e c h ange

of wine int o v inegar T h e manufacture o f p o tt ery and gl ass
.

h ad b een d evel op ed t o a fine art B ut th ese were c rafts or .

“
trad es and t h e peopl e und erstoo d l ittl e ab out t h e whys and
,

wh erefores of th ese process es .

T o t h e anc ient G reeks must b e given t h e c red it for h aving

h inted at some of t h e found ations o f our id eas ab out t h e
,
T H E R ENA I S S A NC E OF C HEM I S T R Y

t
s ruc ture o f matter T h al es o f M il etus a ph il osoph er wh o
.
,

lived ab out 600 B C too k it for granted th at water was t h e b asic

. .
,

el em ent Oth er G reek ph il osoph ers th ought th at all kind s of

matter could b e mad e fromair and fire b y suit abl e transforma
t io ns .L A —
ater rist ot l e ( 384 32 2 assumed th at th ere were
four primary el ements fire , wat er , air , and eart h M oreover .
,

it was th ought th at all obj ec t s in t h e world c ould so meh ow b e

_

mad e b y fusing small indivisibl e particl es togeth er Here we

,
.

h ave t h e b eginnings of t h e atomic th eory of our d ay .

3 . The ch e mist ry of t h e M id d l e A ges For several h und red .

years no _ p rogress was mad e t o ward t esting out t h e truth or

fal sity of th ese anc ient th eories I nd eed it was not consid ered .
,

necessary t o d o so M oreo ver all t h e efforts of t h e l earned

.
,

men of th is period were directed toward c h anging t h e c h eap

( b ase) metal s into t h e val uabl e (nobl e) metal s T h is ph ase
‘

o f c h em istry is known as al ch emy A lth ough t h e al c h emists .

fail ed t o reach th eir goal th ey d id d isc over a h ost of fac ts useful

,

in l ater c h emistry T h e city of A l exand ria was t h e c ent er

.

o f th is ac tivity and in t h e eighth c entury t h e A rab s s eem t o

,

h ave c arried th eir stud ies in th is fi eld furth er th an t h e rest of

t h e world Fro m th eir universities th es e t eac h ings spread
.

t o t h e Euro pean c o untries I tal y Franc e G ermany and , , ,

Engl and T h at is wh y certain c h emic al terms suc h as al c oh ol

.
,

and alkali h ave an A rab ic or1g1n

, .

A t ab out th is time t h e th eory of t h e struc ture of matter

und erwent a d rastic c h ange A ccording t o t h e new hyp oth esis
m
.
,

th ere were now th ought t o b e only three el e ent s mercury ,

s alt and sulfur

, M y stic sy mb ol s for th ese were ad opt ed
. B ut .

th en again for c enturies l ittl e advance was reall y mad e Si nc e

all t h e c h emists were still b usy l oo king for so me sub stanc e
t h e ph il o s oph er s st one whic h would c h ange met al s l ike
’

l ead and c opper into gold and silver Neverth el ess t h e end .

o f t h e prac tice of al c h em y ( Fig 2 and 3) was I n sight . .

4 . Th e renais s anc e o f ch e mist ry . It was a Swiss ch emist ,

P arac el sus ( 1 4 93 wh o b roke away from t h e ol d time -

T HE B EGI NNING S or SC IENT I FI C C HEM I S T R Y 5

c h em istry and burned up as usel ess t he b o o ks o f his forerunners .

T his scientifi c pioneer said th at t h e c h ief aim of c h emistry

was not t h e searc h for t h e ph il osoph er s stone or for an el ixir
’

that would ind efinitely prol ong life b ut t h e preparation and ,

study of d rugs for h eal ing t h e Sic k He waged unceasing war .

upon med icine as it was th en prac ticed and insisted th at .

c h em istry must b e studied by everyone p l anning t o b e a d octor .

Whil e his great c ontribution was a practice of med icine b ased

o n reason instead of o n superstition,h e really th ereby c l eared

t h e way for a study of c h em

ist ry al so b ased on reason .

One of h is greatest foll owers

was vanH elmont ( 1 577 1 644 ) -

T his early c hemist Spent most

“
o f h is l ife in h is l ab orat ory

j ust outsid e of Brussel s pur ,

suing c h em ic al investigations
and writing scient ifi c b oo ks .

H e was prob ably t h e first t o

d istinguish b etween air h y
”

d rogen c arbon d ioxid e and

, ,

marsh gas I n fact h e add ed

“
.
,

t h e word gas t o t h e ch em i
c al v oc ab ulary .

5. Th e b eginnings of s cien
t ific ch e mist W T h e rapid
Fig R OB ER T B O YL E ( 1 6 2 7 One
growt h Of l earnl ng I n Europ e
.

o f t h e firs t t o r ealize t h e d iff erence b et we en

111 t h e second h alf of t h e sev en el ement s and c om pound s S t ud i ed t h e

.

effect of pt es s ut e on vol um es o f gas es

t eent h century b rought an
.

imp ortant ch ange in c h emistry I t h ad b een, up t o now, t h e

.

tool of t h e d o ctors and of t h e craftsmen in metallurgy I t

-

now b ecame what we call a pure science, wh ic h means that

it aims t o increase our knowl edge ab out nature irrespective
of t h e prac tical use t o wh ic h we m ay put our find ings R ob ert
.

B oyl e ( Fig 4 ) is som

. etim es c all ed t h e found er of scientifi c
6 H I S T OR I C A L I NT R OD U C T I ON . FI EL D OF C H EM I S T R Y

c h emistry His great b ook was T he S cep tical Chymis t first

.
,

publ ish ed in L ond on in 1 661 Here h e sh owed th at th ere was

.

no reason for limiting t h e num b er of el ements t o four as t h e ,

G reek ph il osoph ers h ad d one or t o three as d id t h e l at er

, ,

al c h em ists T h e c h emist h e said sh ould regard as el em

.
, ent s all
,

th ose sub stanc es wh ic h h e h ad not y et b een abl e t o spl it up into

t wo or more c onstituent s .

T his is so muc h like our own p oint o f V iew th at we find

it h ard t o real iz e h ow revol utionary it must h av e seemed t o
B oy l e s fell ow c h emists H e was a c ont emp orary o f S ir I saac
’
.

Newt on b ut h is work d id not receive t h e immed iate s upport

,

wh ic h was ac cord ed t o th at of Newt on H owev er h e set up .

,

t h e meth o d of stud y th at h as b een f oll owed ev er since in

c h em istry I t was B oyl e t oo wh o s tressed t h e value of ind uc
.
, ,

tive reasoning ; th at is of starting with experimental fac ts

,

and with ac curate o b servatio ns and d rawing c o ncl usions from

th em

6 C h emist ry d uring t h e eigh t eent h c ent ury

. T h e c h emists .

now mad e rapid strid es forward , p artl y b ec ause of th eir in

creased s kill and partl y o n acc o unt o f t h e im prov ements in
t h e means o f c ommunication T h ese enabl ed scientist s t o k eep
.

th emselves informed in regard t o t h e work of oth ers in d ifferent

“
part s of t h e world I n t h e succeed ing c h apters we Sh all study
.

th is d evel opment of c h emistry in t h e work of Black ( 172 8

wh o investigated t h e c o mposition of l imestone and
quic kl ime ; P ries t l ey ( 1 733 wh o isol ated t h e ac tiv e
p art of t h e air ( oxy gen) b y h eating t h e red c alx ( oxid e) of
mercury ; C avendish ( 1731 wh o is b est known on
account o f h is c areful work on gases no tabl y h is meth o d of ,

id entifyi ng gases by ac c urate measurement o f th eir p roperties ,

and h is d isc overy o f t h e comp osition of water and of nitri c

acid ; S ch eel e ( 1 74 2 a poor Swed ish apoth ec ary b ut a
b rilliant experimenter wh o d isc overed chl orine oxygen am
, , ,

monia and hydrogen chlorid e as well as numerous organic

,

i
ac d s ; Lavoisier ( 174 3 17— wh o b y t h e use of t h e b al ance set
8 HI S T OR I C A L INT R ODUC T ION . FIELD OF C HEM I S T R Y

in t h e manufacture of incand escent lamps and of t h e\ so call ed -

special st eel s .

T h e c h emist h as greatly improved t h e m anufac ture of gl ass .

We now h ave special kind s of gl ass th at stand great h eat and

t h erefore are useful in t h e l ab oratory and t h e kitc h en T h us .

we have P yrex glass ( Fig .

which is very strong and d oes

not easily crac k wh en sud
d enly h eated or cool ed .

I n agriculture, c h e istry m
h as perh aps rend ered it s
greatest servic e, for t h e c h em
ist h as l earned wh at sort of
pl ant foo d is required by d if
ferent c rops a nd what must
th erefore b e supplied by fer
t ilizers ( Fig Wh en t h e .

na tural supply of sodium ni

trate, found in C h il e, seemed
limited and l ikely t o b e ex
h aust ed in a few y ears, t h e
c h em ist mirac ul ously suc
ceed ed in m anufac turing th is
fertilizer out of t h e el ements
in t h e air .

A n extremely important
task of t h e c h emist to d ay is
Fig 5 C offee pot , mad e o f P yrex gl as s ,
. .

h eat ed b y an el ec t ric s t ove

o v er o ur foo d sup
t o watch
Water and mi lk must
.

pb ss .

c onst antly b e te sted for im p ur it ies and a d u lt erat io n of foo d

p rev ent ed b y t h e c h emist s t irel ess

’
a nd ex per t Vigil anc e .

8 . val ue of ch emist ry Find ing o ut new th ings

Ed ucat io nal .

ab out t h e world around us is in itself o ne o f t h e nobl est pur

suit s B ut quite apart fromt h e importance t o t h e community
.

o f t h e C h emist s d isc ov eries th ere is an add itional v al ue in

’

,
ED UCA T I ONA L VA L UE OF C HEM I S T R Y 9

st u dying t h e subj ect Namely we get a start in ac qui ri ng t h e

.
,

sc ien tific way of thinking th at c h emist ry represents T h is re .

q u ires t h e h ab it o f fac ing real ity quit e unprej ud iced by an y

earl ier conc eptions and th at is of incal cul abl e val ue
,
M oreover .
,

t h e enthusiasm th at carries us al ong t o face d iffi culties in a

straightforw ard fashion and t h e h ab itual urge t o l o ok for t h e

C ourt es y of t h e A m A gri cult ural C h emi cal 0 0

. .

Fig 6 . . P ot at o crop in M aine, grown wit h t h e h el p b f fert iliz ers

mistakes th at are b ound tot th em at onc e

o cc ur and t o c orrec

are a well recognized part of t h e scientifi c spirit

f
I n sh ort t h e .
,

scientifi c m mo re e éSs
“

eth o d of study ing

esta blish ed if we seriously und ertake t o study c hemistry A ccu

m
.

rate ob s rvation and d epend ence on ex perim n t a h ?)

e e re e

guid ing pTin aples .

T h e watchword is not What d oes t h e b oo k say ab out th is

or th at , b ut
” “‘
,

Let s t ry t o find out for ourselves

’
T h en .
”
10 H I S T OR I C A L I NT R OD UCT I ON . FI EL D OF C H EM I S T R Y

t he t in t h e p ro c es s o f fi nd ing o ut are alway s t h es e

s ep s We .

c o ll e o ur fac t s b y c aref ull y o b s erv ing wh at is h appening

ct .

We group th em and t ry t o interpret th em in t h e l ight of other

fac ts th at we al ready know T h en we set up a th eory, or
.

pic ture, o f wh at th ey mean wh ic h will expl ain t h e newl y dis

Fig 7
.
‘

. A hi gh -
sch ool ch e mical l ab orat ory .

co vered fac ts A nd fi nall y we test out our th eory by getting

.
,

more d ata of a simil ar kind and co mparing th em with t h e

facts th a t we got th rough t h e earl ier experiments Wh en our .

th eory d oes not quite fit t h e facts we must mo d ify it and at t h e

,

sam e time v erify t h e f ac t s by gett ing more d at a We cannot .

,

o f c ourse h op e t o l earn everyth ing in th is exp erim

,
ental way .

I t would t ake t oo much time B ut a satisfyi ng gl impse of

.

t h e way a sc ien tist works and t h e ac quisition of h is h ab it

of m ind and way o f th inking c an unquestionabl y b e got by
s tudying th is fasc inating subj ec t in t h e l ab orat ory ( Fig .
SUM M A R Y OF C H A P T ER I 1

SUM M A R Y OF CHA P T ER I

T h e EA R L Y H I S T O R Y OF C H EM I S T R Y may b e d ivid ed t h us

(0 ) A nc ient perio d up t o C h ris t ian era . Egypt ians , G reeks , and

m
R o ans l earned h ow t o w ork in s ev eral mmon met al s
co ,

such as c opper, t in, iron, l ead , and mercury , as well as in t h e

rarer gol d and s ilv er . T h ey al s o l earned h ow t o us e v ege

t ab l e d y es . P making b ecame a fine art

o t t ery and gl as s .

( b ) Early al ch emis t s up t o 1 500 A D spent much t ime and l ab or .

ph er s s t one wh ich woul d enab l e t h emt o

s e eking t h e ph il o s o
’
,

ch ange b as e m et al s int o nob l e met al s .

(0 ) L at er al ch emist s up t o 1 6 50 w ere s eeking t h e el ixir of l ife and

w ere preparing and t es t ing new s ub s t anc es for med ic al us e .

(d ) S cient ific ch emis t ry b egan wit h R ob ert B oyl e ( 1 6 2 7

C H EM I S T R Y A ND M O DER N LIFE . A mong t h e val uab l e sub

s t anc e s wh ich w e
‘

ow e to th e ch e mist s are ‘

(a) D y es s ynt h es is of ind igo

( b ) D rugs c o c aine and N ovoc ain

(c) M et al s and all oy s m m and magnesium

al u inu
magnal ium
tungst en and mol yb d énum
spec ial s t eel s

(d ) G l ass P yrex
A gricul t ural ch e mi s t ry includ es s oil anal ysis and preparat ion of

fert il iz ers .

C it y , s t at e , and fed eral gov ern ment s h av e d epart ment s for t es t ing
fo o d s and d rinks .

ED U C A T IO NA L VA LUE OF C H EM I S T R Y main purpo s e

. The
of th e st ud y of c h e mist ry in s ch o o l i s t o t each t h e s cient ific met h od ;
t h at is , t h e app eal t o eXperi ment . T h e s econd aim is t o ac quire a
mat ion ab out t h e preparat ion propert ies
_

b ody of infor , , and uses of

cert ain ch emical s wh ich are ess ent ial t o our mo d ern l ife .

QUES T I ONS
1 . N ame fiv e met als known t o t h e ancient s .

2 . Wh at element s were d is covered d uring t h e p eriod of al ch e my ?

12 H I S T OR I CA L INT R OD U C T I ON . FIEL D OF C H EM I S T R Y

met als
~

3 . T h e al ch emist s d ist inguish ed b et ween

,
b ase and nob l e
met als . Expl ain .

4 . N ame five art icles in y our h ome which could not h ave b een in t h e
h ome of an al ch emis t .

5 . W h o ad d ed t h e word gas t o t h e vocab ul ary

. of ch e mist ry ?
6 . W h o first clearly d efined an elem ent ?
7 . N ame five men wh o figured prominent ly in t h e d evelopment of

ch e mist ry d uring t h e eigh t eent h c ent ury .

8 Name s ev eral s pec ial kind s of gl ass used in modern life

“T h
. .

9 . J us t ify t h e s t at e ment : e common man t o d ay lives b ett er t h an

a king d id h und red y ears ago
”
one .

10 . Wh at h ab it s of t h ough t and act ion ch aract eriz e the s cient ific way
of t h inking ?

11 . W h at mean b y i nductive reasoning?

d o we
12 . W h at d y e formerly ob t ained from pl ant s is now mad e ch emically ?
al c h emis t s failed t o find t h e ph il osoph er s s t one and t h e elixir
’
13 . T he
of l ife D id t h ey d is cov er any t hing of v alue ?
“
.

14 . W h ich are th e more useful , t h e ba se met als or t h e nob le

me t als ? T O wh ich
’

cl ass do es t h e most useful of all met al s b el o ng ?

15 . N ame t wo d rugs useful t o t h e d ent ist and t h e ph y sician wh ic h

, ,

are mad e b y manufact uring ch emist

t he .

16 . Wh en an al ch emist cut h is finger , did h e appl y ( a) M ercuroch rome ;

(b ) t inct ure of iod ine ; ( c ) Unguent ine ?
“
1 7 D o t h e el ement s mercury salt and sulfur of t h e M iddle A ges seem
“
.
, ,

t o y ou an improv ement o n t h e element s earth air fire and water of t h e

”
, , ,

ancient Greeks ? Expl ain .

18 . L ook
t h e pic t ure (Fig 2 ) o f an al ch e is t in h is l ab orat ory
,
at . m .

( )
a W h a t p iec es o f a pp ara t u s d o y ou r eco gniz e ?
( b ) H ow did h e d o h is
h eat ing ? ( )
0 H o w d id h e b l ow h is fi re ? d
( ) D id h e h av e el ec t ric c urrent ?

G ? l
( )
e as (f) G ass t ub ing
?

19 . N ame sev eral exa mples of t h e use o f ch e mis t ry in mod ern l ife wh ich
y ou h ave found fro m y our read ing out sid e of t h is t ext b ook .

20 . W hich of t h e met als d is covered b y mod ern ch emic al met h o ds are

used in ( a) t h e airpl ane ; ( b ) a st rat osph ere gond ol a; ( c) t h e incand es cent
m
la p ?
 C HA P TER I I

P HYSI CA L A ND CHEM I CA L CHA NC ES

P h y sic al s t at es of mat t er ph y sical c h anges familiar exa m

ples c h arac t erist ics .

C h emical ch anges exa mples wh at h appens ch a

ract eris

t ics . P ropert ies of mat erials . L aw of C onservat ion of M at t er .

9 . T h ree s t at es of matt er
Everyone kno ws th at wh en .

water is c o ol ed sufficientl y , it turns into ice and th at wh en it

Is b oil ed , it b ec omes s t eam I f we study ice, water, and stea ,
. m
we find th at all h ave exac tl y t h e same c omposition T h ese .

three s olid , liquid , and gas are known as t h e t h ree ph ysical

st at es of m at t er M any o th er sub stances b esid es water can
.

b e studied in all three states if t h e conditions are j ust right .

T ake sulfur, or brim

stone, for exam pl e It .

is ordinarily a y el Vap or
l ow solid B ut wh en
.

h eated , it melts and b e

qui d
com es a viscous l iquid ,

and by still furth er h eat m um

l ng it m
b e c o es a gas Fig 8 S olid l iquid and vapor st at es of sul fur
. .
, , .

( Fig . Even air, t h e

most common gas, c an b e cooled and liquefied , and when still
furth er cool ed it turns into a sol id So we see th at t h e ch ange
, .

in physical state of th ese sub stances inv olves no c h ange in th eir

‘

c om position I t is merely a result of h eating or coo ling

. .

10 . P h ysic al c h anges . T h ese

h anges in state will al so c

work b ac kward or as we say th ey are reversibl e T hus b y

, , , .
,

taking away h eat we freez e water int o ic e and by add ing h eat ,

We melt t h e ic e into wat er I n t h e same way if we cool t h e

.
,

13
14 P H YS I C A L A ND C HEM I C A L C HA N GES

su lfur vapor (gas) we get liquid sulfur and if we c ool t h e molten

, ,

sulfur we get t h e s ol id f orm of sulfur

, Suc h c h anges of st ate .

are physic al c h anges Oth ers are th ese : I f we p ass an el ec tric

.

c urrent th rough a pl atinum wire it b ecom es wh it e h ot ; b ut ,

on c ool ing it returns t o it s original state

, A gain if we mag .
,

net iz e a piece of h ard ened steel ( such as a knitting needl e) ,

it will attrac t iron tac ks ; b ut if we d rop it on t h e fl o or a few

times it b ec omes d emagnetiz ed We h ave not c h anged it s
,
.

c om p o sition b ut we h ave c h anged it s p hy sic al p roperties

m
.
,

A lth ough th ese p hysic al c h anges are very i portant th ey are ,

much less spectacul ar th an t h e c h emical ch anges Which we

are ab out t o stud y .

11 . Famil iar ch e mic al

Everyone knows th at c h anges .

wh en woo d b urns, a great d eal of h eat is produced and t h e

original woo d entirely d isapp ears, ex c ept for a few partic l es

o f ash es T h is is suc h a common h ap

’

p ening
th at we d o not generall y stop
’

t o think wh at it means A pparently .

s om e sort of c h ange h as t aken p l ace

d uring t h e b urning for we can now no ,

l onger find any of t h e original woo d .

A no th er c h ange al mo st as striking , ,

o c c urs if we l et a piece o f iro n suc h as ,

yg n a rail lie for some time ex posed t o t h e

x e ,

weath er We find th at it first b ecomes .

Fig 9
. P h ot ofl ash l am
.
p coated and th en c rum
. bl es t o a mass of
brown powd er wh ic h we c all rust I n .

th ese c ases suc h well known sub stanc es as woo d and iron h ave
-

disappeared b efore our very ey es T h ese are exampl es of wh at .

we c all c h emic al c h anges

m
T h e d ec ay ing of woo d t h e souring
.
,

of m ilk t h e putrefac tion of meat are l ikewise c om on ex ampl es

,

of c h em ic al c h ange Still o th ers are t h e expl osion of gasol ine

.

in an aut omobil e cy l ind er t h e sudd en b urning of t h e al uminum

,
,

foil in a ph ot oflash l amp ( Fig and t h e b ursting of a h igh

.

expl osive sh ell I n all th ese c ases c ertain material s disappear

.
16 P HY S IC A L A ND C HEMI C A L C H A NC ES

at o nce appe ars and a cl oud of wh it e solid p art icles float s ofi A gain we find .

neit h er our original s ulfur nor o ur original z inc , b ut only a new wh it e sub

s t ance which is known as z inc sulfide .

In every ch e mi cal more materi als disappear and

ch ange one or

one or more new sub stances are formed Since in a c h emic al .

c h ange new sub st ances are f ormed fro m o l d and since o ne

el em ent c anno t usuall y b e c h anged d irec tl y int o ano th er it is ,

evi d ent th at a c h em ic al c h ang e is merely a rearrangement of

t h e el ements into a new comb ination .

We find th at in a chemi cal change heat i s usually produced and

li gh t is often emi tted .

13 . H o w we rec o gniz e mat erial s . We notice th at ash es

are d ifferent fro m woo d We ob serve th at t h e brown s olid .

formed b y d issolving nail s in nitric acid is different frommetallic

iron I n d oing this we are unconscious l y taking advantage o f
.

our ev eryd ay kn o wl ed ge o f wh at s uc h c o mmon materials as

wo o d and iro n are reall y l ike No one would h ave any d iffi
’

c ulty in d istinguish ing b et ween a stic k of wo o d and a b ar o f

“

iron ev en if t h e stic k were p ainted bl ac k

, Woo d will read ily .

fl oat on water iron will not A magnet will attrac t a piece

,
.
"

of iron b ut not a piece o f woo d Woo d easily c atch es fire .

,

wh ereas iron will not b urn Suc h c h arac teristic fac ts ab out .

a given material are c all ed it s propert ies We c an recogniz e .

and id entify any particul ar material b y knowing a numb er

o f th ese prop erties
‘

For exampl e wh at are t h e properties of water ? We all

,

know th at water wh en pure is an o d orl ess tastel ess liquid

, , ,

and th at it is usually c ol orl ess ex cept in very th ic k l ayers T h en ,

.

it is bl uish green Water freez es at 32 Fah renh eit ( or 0

-
.
° °

C entigrad e) and b oil s at 2 12 Fah renh eit (or 100 C entigrad e) ° °

und er standard pressure ( 760 I mpure wat er usually

b oil s at a h igh er temperature and freez es at a l ower t em
’

p e r

ature P erh aps it s most imp ortant p hysic al property is it s

.

d ens it y If we weigh in grams a c ertain v ol ume of water

.
,

expressed in cub ic c entim et ers at 4 C we find th at one cubic °

.
, ,
C HA R A C T ER I S T I C S OF A C HEM I CA L C HA NGE 17

cen timeter of water weigh s exac tly one gram If we weigh a .

known volume of mercury ( quic ksilver) we find th at one ,

c ubic centim eter of m erc ury weigh s gram s I n general .

,

th en we may say th at the density of any substance is the weight

m
,

of a uni t v olum e Since in t h e c h e ic al l ab oratory we generally

.

ex pr ess weight in gram s and v o l um e in c ub ic c entim eters we ,

may also say th at t h e d ensity of any sub stance is t h e weight in

grams of one c ub ic Centimeter of th at sub stanc e For exampl e, .

t h e d ensity of alum inumis grams p er cub ic c entim eter and ,

of l ead is gr ams p er c u b ic c ent im e t er Lik e wise t h e .

,

melting point of aluminum is and of l ead is 32 7 C

°
.

T hus we see th at c ertain p roperties of material s can b e ac

c urat ely d eterm ined and expressed b y numb ers .

14 . C h arac t eris t ic s of a ch e mical c h ange . Let us t ake so me

fi y powd ered sul fur and
ne l ‘
so me iron filings ,
*
W e not ice t h at t h e sulfur is
‘

y ell ow and rel at ively l igh t . I t will d iss ol ve in

a l iquid c alled c arb on b isulfid e T h e iron is a .

h eavy gray s olid , insolub le in c arb on b is ulfid e

and readily at t ract ed b y a agnet mL et us ix . m
t h ese t wo m at erials t oget h er in s uch prop ort ions
t h at t h ere is ab out t wice as m
uch sulfur (b y
v ol u me) as iron . We pl ace t h e mixt ure in a t est
t ub e and h eat it in a flame (Fig I n a few
mm nt
.

o e s a gl ow s preads all t h rough t h e c o nt ent s

of t he t ub e . T h is gl ow c ont inues for a t i e even m
aft er t he flame is removed . Ev id ent ly somet h ing
h as h appened in t h e t ub e wh ich h as prod uced
h eat and l igh t I f we b reak t h e t es t t ub e and
.

exam ine t h e s olid , we S h all see t h at it is a h ard

“
Fig 12 H eat ing iron and
b l ack mass I f we grind it up int o small b it s , we
. .

. g ul f .

Sh all find t h at none f it has the

o prop erti es ei ther

of sulfur or o f iron . T h at is , none of it is S ol ub l e in c arb on b isulfid e, and

none of it is at t ract ed b y a magnet .

I n th is xperiment t h e t wo substances iron and sulfur h ave

e , ,

d isappeared and a new Sub stanc e wh ich is c all ed iron sulfid e , ,

h as b een formed We are abl e t o rec ogniz e th ese fac ts by c are

.

T h e weigh t o f iron s h o ul d b e ab o ut o ne and t h ree fourt h s t imes t h e weigh t -

o f s ul fur .
18 P H Y S I C A L A ND C HEM IC A L C HA NC ES

fully noting t h e properties of t he origina l material s and t h e

properties of t he final prod uct .

15 . A not h er c h arac t eris t ic A v ery of a ch e mical c h ange .

important examp l e of c h emical c h ange is t h e burning of coal .

T h ere is no d oubt th at this is a c h emical c h ange for t h e fol

l owing reasons : ( a) new sub stanc es are f ormed , namel y ,
“

t h e gases wh ic h go up t h e c himney as well as t h e ash es and

c linkers ; ( b ) h eat is pro d uc ed ( c) it would b e impossibl e .

t o get t h e c oal b ac k fro m t h e prod uc ts ; and fi nall y , ( a

t) t h e
resid ue weigh s l ess th an t h e c o al wh ic h is b urned B ut we .

must examine furth er into this apparent ch ange in weight

d uring a c hemical c h ange D oes this mean th at some of t h e .

coa l h as b een d estroyed ? What ab out t h e weight of t h e gases

whic h go up t he
c h im ney ? T his p ar
t ic ul ar experiment is
S i l ver d iffic ult t o c arry out
30 mm ” f
°
with great p recision ,

so we sh all d evise an

exp erim ent in wh ic h

t h e Ch emic al c h ange
t ak e s p l ac e i n a
tightly c l o sed vessel .

16 . T h ere is no
c h ange int o t al weigh t
in a c h e mic al ch ange .

W e may s el ec t any t wo
Fig 1 3. A ch e mical ch ange, b ut t h ere is no c h ange in
anc e s w h 1 ch
.

s ub s t ac t
th e t ot al w eigh t .

quickl y on each o t h er

wh en b rough t t o get h er mple suppose we

. For exa c c o f c om
, put ab out 2 5 .

mon salt s ol ut ion int o a conic al fl ask and pour int o a S h ort t est t ub e some
-

s il v er nit rat e solut io n W e pl ace t h e t ub e in t h e fl ask as sh own in figure

. ,

13 c arefull y cl os e it and d et ermine it s weigh t

, ,
T h en we t il t t h e fl ask s o .

as t o mix t h e t wo cl ear liquid s and we pro d uce a wh it is h s olid s ub s t ance

, ,

S il ver ch l orid e T h e ch emic al ch ange c auses some rise in t emperat ure

.
.

A ft er t h e fl ask h as c ooled we again weigh it and find t h at its wei ght is

,

unchanged .
S UM M A R Y OF C HA P T ER II

l arge
A numb er xperiments h ave b een performed
:
o f suc h e

With great precI SI On Th ese h ave sh ow n th at in every chem

. i cal
change th e total weigh t of all th e sub stances form
,
ed is exact ly equal

to the t otal wei gh t of all the subs tances whi ch ent ered i nto the change .

T his is known as t h e LA W OF C ONSER VA T I ON OF M A TTER and

c an b e c oncisel y st at ed as foll ows :

M att er *
can neit h er be creat ed nor d est royed .

A law in scienc e is Simp l y a st at e ent o f So me general fac t m

wh ic h h as b een proved t o b e true b y a l arge numb er of exp eri
ments It is a d escription of t h e way certai n material s al way s
.

beh ave und er certain cond itions .

S UM M A R Y OF C HA P T ER II

C H EM I S T R Y d eal s wit h t h e co mpo sit ion of mat erial s and wit h th e

ch anges may und ergo
wh ich t h ey .

T H E P R O P ER T IES of a mat erial are t h e ch arac t eri s t i c s b y wh ich

w e id ent ify it , suc h as it s c o l or, h ard ness , t as t e , d ensit y, s ol ub il it y ,
melt ing po int , and it s ch e mic al b eh avior .

T h e T H R EE P H Y S I C A L S T A T ES of mat t er are s o l id ,
liquid , and
gas . Th e s t at e in Wh ich any sub st anc e is found d epend s on t h e nat ure

of th e s ub s t ance it s elf and on it s t emperat ure .

The ch ief feat ure s of aC H EM ICA L CH A N GE a re

1 . N ew sub s t anc es are for med .

2 . H eat and ligh t are oft en pro duc ed .

3 . U sually met imes impo s sib l e t o get t h e

it is d ifficul t and so

gain from t h e pro d uc t

o riginal s ub s t anc e s b ack a .

I n a P H Y S I CA L C H A N GE no new sub s t anc e 1 s forme d U sually .

1

it is quit e e as y to rev ers e th e c h ange and b ring t h e

'

sub st anc e b ack t o

it s o riginal s t at e .

LA W OF C O N S ER VA T IO N OF M A TT ER g
’

: T h e t ot al w ei h t of all
t h e sub s t anc e s for me d in ach emical ch ange I s exact ly equal t o t h e t ot al '

weigh t of al l t h e s ub s t anc es wh ich ent ered int o t h e ch ange .

M at t er is t h e general na me for any t h ing wh ich h as weigh t and wh ich o c cupies

s p ac e .
20 P H Y S I C A L A ND C HEM I C A L C H A NGES

QUES T I ONS
1 . Sh ow h ow wat er can be mad e t o assu me t h e t h ree ph y s ical st at es of

mat t er
2 St at e carefully j ust wh at is meant b y a ph y sical c h ange G ive
‘
. .

five exam ples not ment ioned in t h e t ext .

3 . f five import ant

M ake alist O propert ies us ed in id ent ify ing sub s t ances .

4 . I f y ou h ad a mixt ure o f s ugar and s a

nd , h ow c oul d y ou recover each

pure and d ry ?

5 . W h at p ropert ies wo ul d y o u m
ake use of in d ist inguish ing b et ween
( a) c o pper W ire and iro n wire, ( b ) woo d and iron, ( 0 ) al u inu and s il ver, m m
(d ) powd ered s ugar and flour , and ( )
e wat er and gas o l ine ?

6 . H ow c an y ou sep arat e powd ered sul fur from powd ered y ellow
gl ass ?
7 . N ame some propert y wh ich is common t o all mat erials .

8 . N ame five examples of ch emical ch ange, not ment ioned in t h e t ext ,

wit h wh ich y ou are famil iar .

I f we p ound iron, it b ecomes h ot

9 . . H ave we prod uced a ch emical
ch ange ? Give y our reasons .

mat
-

10 . I f we s c rat ch a ch a b ox, W e pro d uce b ot h h eat and ligh t

on .

Has a ch emical ch ange t aken pl ace ? G ive y our reas ons .

C an all mat erials be made t o assu me t h e t hree ph y sical s t at es ?

Expl ain .

12 . P ol ish ed magnesium and pol ish ed pl at inu l ook alike m Giv en a .

one -
inch c ub e of each of t h ese met al s , h ow coul d y ou id ent ify each wit h out

inj uring eit h er of t he m?

13 S t at e wh et h er t h e foll owing operat ions c onnect ed wit h a meal are
.

ch emic al or ph y s ic al c h anges and give y our reasons in each case : ( a) ro ast ,

ing t h e l eg of l amb ; m
( b ) war ing t h e soup ; (0 ) digest ing t h e meal ;
(d ) d issolving t h e sugar in a cup of coffee ; ( e) s moking a c igaret t e .

14 . W h en ca mph or is pl aced in clot hing, it grad ually d is appears . Is

t his an except ion t o t h e l aw o f c ons erv at io n o f mat t er ? Expl ain .

15 C opy and supply t h e missing word s : A l aw in science is simply a

.

st at ement of s om e genera l which h as b een proved b y a l arge

numb er of I t is a d escript ion of t h e way cert ain mat erials always
under cert ain
 C HA P T ER II I

ELEM ENT S A ND C O M P O UND S

C h emicals sub s t anc es and mixt u

mpounds ele res co

ment s compounds made from element s compounds h ave a

d efinit e c ompos it ion mixt ures and compound s compared
sep arat ion of m ixt ures o c currence o f t h e el ement s met als ,

alloy s and nonmet als

, numb er and import ance of c ompound s .

Wh at are ch emic al s ? T h e material s wh ich we use in

'

17
“
.

t h e ch em c h emical s
”
ical l ab orat ory are ordinaril y c all ed .

I n fac t any sub stance which is used in t h e l ab oratory even if

, ,

S ome common ch emical s such as sul furic , h y d rochl oric, and nit ric
acid s ; ammonium h y d roxid e ; met al l ic z inc and c o pper ; so d ium h y d roxid e ;
et h er ; copper s ulfat e ; merc ury .

it is al so used in t h e h ome or fac tory, i s a ch emic al ( Fig .

T hus, gold , sugar water, salt t in z inc and sulfur in t h e

, , , ,

ch em ic al l ab oratory are c h emic al s wh il e sugar, s alt , and

,

water int h e kit ch en b ecome foo d s'

I n our study we sh all
.

meet with a great many sub stances which are now known
21
22 ELEM ENT S A ND C OM P O UND S

merely as c h emicals b ut wh ic h may

l ater prove t o b e d irec tly
'

or ind irec tl y v al uabl e t o m an T o bring ord er into t h e vast

.

numb er o f material s th at t h e c h emis t uses and t o simplify th eir

study we m ,
us t firs t l earn t o c l assify th em .

S ub s t ances and mix t ures

18 . W h en we exa ine granite . m
and ordinary c oncrete, we find th at eac h of th emis mad e up of
a numb er of d ifferent sub s tances I n granite we find three .

minerals feld spar and mica Wh en t h e roc k is

quartz , , .

crush ed th ese th ree m

, ineral s fall apart Ordinary c oncrete is .

mad e by mixing togeth er cement sand and crush ed stone , , .

I f we examine t h e mixture o f iron and sulfur whic h we used

in t h e l ast c h ap ter we c an rec ogniz e in it partic l es of sulfur
,

and partic l es of iron On t h e oth er h and if we examine a

.
,

mass of iron filings we find th at every partic l e of iron is like

,

ev ery o th er p artic l e of iron and seem s t o h av e ex ac tly t h e

sam e properties A materi al every p art of which is like every

.

oth er p art i s s aid t o b e h om I t is c all ed by t h e c h emist

“
ogeneous .

a s ub stanc e A material whic h is c omp osed of t wo or more

‘

sub st anc es m erely put t ogeth er is c all ed a m ixt ure G ranite .

is th erefore a mixture and not a sub stance Sulfur and iron .

are sub stances wh ic h we c an easily stir togeth er t o formvarious

mixtures .

Since a sub stance is a h omogeneous material all parts of it ,

will h aVe exac tly t h e same properties Every samp l e of t h e .

sub st ance will b e found t o b e ex ac tl y l ike every o th er sam pl e .

On t h e oth er h and t h e prop erties of a mixture will d ep end on

,

t h e amounts of t h e d ifferent mat erial s th at co mp ose it For .

ex am pl e a mixture of 10 parts o f iron and 1 part of sulfur

,

is gray wh il e a mixture o f 10 parts Of sulfur and 1 p art of iron

,

is al most pure y ell ow .

SO we find th at a mi xture contains two or more sep arate ingredi

ents, or components which keep their own properties unchanged
,
.

1 9 C h emic al c o mpound s
. P rob ably t h e most imp ortant
.

as well as t h e mo st familiar sub stance is water Yet strange .

,

as it may seem ev en pure water i s not a simp l e sub stanc e We

,
.
24 EL EM ENT S A ND C OM P OUND S

so o n thep owd er b ec o es d ark

red m
I f we ins ert int o t h e t ub e a s pl int er
. of

wood wit h a gl owing s p ark on t h e end , t h e sp ark at once b urs t s int o a fl me .

T his ind icat es t h at some gas , not air, is b eing pro d uced On again examining .

t h e t ub e, we no t ic e t h at a p art o r all o f t h e red p owd er h as d is appeared and

t h at lit t l e d rops o f mer cury ( quicks il v er ) are s t icking t o t h e s id es o f t h e
t ub e. T h is forms a s ort of mirror on the c oo l er p art of t h e t ub e . If t h e
h eat ing is c o nt inued l ong eno ugh , all t h e red p ow d er ev ent ually d is appears .

I t h as b een c onv ert ed int o t w o pro d uc t s m erc ury , t h e s il v ery l iquid wh ich

is us ed in t h ermomet ers , and a gas w h ic h is c all ed o xygen .

By means
h eat we h ave thus transformed t h e sub stanc e
of ,

red ox id e of m ercury int o t wo o th er sub s tances m

, ercury and ,

o xy gen A ny subs tance whi ch can b e decomp osed i nto tw

. o or

more other subs tances is mical co mpound

call ed a ch e
'

. Hence
water and red o xid e o f merc ury are c om pound s .

21 . The d efinit io n of tinue our

an el e ment . I f we c on

ex p erim ent with t h e mercury and t ry t o p ro d uc e still o th er

sub stances b y h eating it o r b y b reaking it up in s o m e o th er

way we d o no t suc c eed

, Simil arly h y d rogen and oxygen
.
,

h ave never b een b ro ken d own into oth er sub stances We .

c all th o s e substances whi ch h ave not b een d ecom p osed into sim
pler subs tances el ement s Sc ientists now b el ieve th at th ere are
.

o nl y 92 el em ent s of wh ic h 90 h av e b een d is co vered (l ist facing

,

bac k From th ese all c h emic al c o mp ound s are mad e .

I t is very remarkabl e t o find th at wat er is c o mposed of

“

t wo gases o ne o f whic h b urns and t h e oth er makes things

,

burn muc h faster th an d oes air I t al so seems strange th at .

red m erc ury ox id e is c om p o sed of a h eavy silvery l iquid and a

col orl ess gas We conc lud e that t h e properties Of a c ompo und
.

are in no way l ike t h e prop erties o f t h e el ements o f wh ic h it

is made .

I t was prob abl y R o b ert B oy l e wh o first c l earl y d efined an

el em ent .
“
I n1 6 6 1 h e wrote th at t h e el ements are t h e prac tical
limits of c h emic al analysis or are sub stances inc ap abl e of ,

d ecompo sition b y any means wi th which we are at present

ac quainted
”
.

*T wo o t h ers h ave rec ent l y b een re p o rt ed b ut s t ill await c o nfir mat io n .

C O M P OUN D S H A VE A DEFI NI T E C OM P OS I TI ON 25

22 . C o mpo und s mad e from el e ment s . We S h all no w make

a
”

co mpound from t wo el ements . T h is is t h e re ers e o f

v the
pro cess j ust d iscussed .

W e pl ace a small quant it y of iod ine I n a

‘

mort ar and add a lit t le mercury T h e t wo sub .

s t ances at firs t rem ain sid e b y Sid e unch anged .

B ut wh en we rub t h e mixt ure v igorousl y wit h a

pest le ( Fig . a red sub s t anc e, quit e unl ike
eit h er t h e mercury or t h e iod ine, is for med .

T h is is a new sub s t anc e, a co mpo und c all ed

mercury io did e .

We m
are all fa iliar wit h t h e met al , c opp er,
Fig S y nt h es i s of mer
. I 7.

wh ich h as a ch aract erist ic red d ish b rown co l or, -

c ury i o d i d e .

and wit h s ul fur, wh ich is a b rit t le, y ell ow el e

ment I f we put some co pper ch ips and p owd ered sulfur int o a small flask
.

(Fig 18 ) and h eat it , t h e mixt ure b egins t o gl ow T h e t wo el ement s unit e,

. .

at t h e s ame t ime pro d ucing h eat and l igh t I f we b reak t h e fl ask, we find a
.

b l ack, b rit t l e mass wh ic h resemb l es neit h er c o p per nor sulfur T he copp er

‘

and sulfur have uni ted to form a comp ound c opper s ulfid e ,
.

C ommon salt is a Compound composed of t wo el ements

sod ium , a b right , silv ery , so ft m et al , and c hl orine, a greenish

y ell o w, poisonous gas Sugar is a c o mp o und of c arb o n

.

an el ement with whic h we are famil iar

in t h e form of c h arcoal and t wo
gases : hy drogen, whic h b urns vigor
ousl y , and ox y gen, wh ic h m akes th ings
burn furiousl y I n every c ase we find .

t h e same surprising d ifference b etween

t h e prop erties of a co pound and t h e m
properties of t h e el ement s of wh ic h it
is co mp osed .

23 . C o mpo und s h ave a d efinit e

co mpo sit ion
C h emic al c h anges are
.

oft en c all ed reacti ons We sh all find .

it convenient t o represent th em in a
s h ortened for mthu , s :

Fig . 1 8. S ynt h e sis of copper mercury oxid e mercury o xygen

sul fid e ( 2 17) (20 1)
.
( 16 )
26 ELEM ENT S A ND C OM P OUND S

I n t his word equation, t h e arrow ( w k ) is read yield ( s ) , and t h e plus sign ;

is read and T h e numb ers in p arent h esis ind i c at e t h e proport ions b y

.

weigh t T h us , 2 1 7 grams of mercury o xid e y iel d 20 1 gra s of mercury

. m .

and 1 6 gra ms of oxy gen .

Whatever quantity o f mercury xid e is d ecomposed experi

o ,

ments — , or
sh ow th at ggt p er c ent of t h e wei ght used is l eft
,

as merc ury , and 1 6

2 1 7
or p er cent of t h e weight is oxygen
, .

We may t t he
represen union of copper and sulfur t o form
c opper (cupric ) sulfid e thus
c o pp er su lfur c opper su lfid e
( 6 4) ( 32 ) ( 96 )

T h is means t h at 64 p art s b y weigh t of c oppe r unit e wit h 32 part s of

.

sul fur t o form 96 p art s of copper sulfid e .

I n oth er word s, copper sulfid e is mad e up of g% , or per

cent , copp er and ge ,
or p er cent, sulfur .

Very c are ful h ow th at every compound has a

e xperiments s

defini te comp osi ti on by weight T h e wh ol e science of c h emistry.

is b ased on th is fundamental fact I t is known as t h e LA W OF .

DEFI NI T E C OMP OSI T I ON .

M ixt ures mpound s

"

24 . c o nt ras t ed wit h co T he c h ief d iffer

.

ence mpound and

b etween a co a mixture is this, th at a c om
p ound h as a d efinit e com position wh il e in a mixt ure t h e com
’

ponent p arts may b e in any prop ortion Water starch sugar .

, , ,

and salt are ex ampl es of c ompound s eac h of wh ic h h as o ne ,

d efinite c omposition Fl our b aking powd er and t h e soil

.
, ,

are exampl es of mixtures eac h o f whic h may vary in t h e ,

amounts of t h e material s th at comp ose it .

We must al so rememb er anoth er d ifference b etween a mix

ture h as th at of iron and sulfur and a c om
suc p ound l ike
'

, ,

iron sulfid e I n t h e mixture we can recogniz e t h e p roperties

.

of b oth iron and sulfur and we find th at t h e m aterial is not

,

h omogeneous I n t h e compound iron sulfid e wh ic h we ,

find t o b e h omogeneous we h av e a set of properties entirely

,

different from th ose of eith er iron or sulfur .

A B UN D A N CE OF TH E ELEM ENT S 27

25 S eparat ion of mixt ures

. . A mixture can often b e easily
separat ed int o it s ingred ient s . For ex ampl e, iron
attracted from t h e away
sulfur with a m agnet T he .

sulfur c an b e d issolved away

fromt h e iron in carb on d isnl

fid e l eaving t h e iron b ehind
,

( Fig . No suc h Simpl e

treatment as this will sepa
rate t h e c ompound iron su17
fid e into iron and sulfur As .

a rul e we c an d ec ompose a
,

c om pound into it s el ements

o nly by som
,

e suc h d rastic

meth od as h eating it t o a
very high temperature or S o l ut

passing an el ec tric current

through it . Fig
. 19 . S eparat ing ironpowd er fro ms ulfur
mixt ure of iron and
'

In t h e in S °l ut i°n b y fil t rat ion

Sulfur t h e p artic l es are merel y l y ing sid e by de

si In t h e
h em
, .

com pound t h e el ements are h eld t ogeth er

, ic al c om
in c

bination . T he resu lt is th at we h ave a sub stance entirely

d ifferent fromeith er of t h e origi
nal t wo el ements .

26 . A b und ance of the el e

ment s A lth ough 90 el ements

.

are known, o nly ab out 2 5 of

th ese are at all common or im
portant I nd eed , t h e aec om
.

p anying d iagram ( Fig 20 ) sh ows .

th at ab out 97 per c ent of t h e

’
earth s crust , incl uding t h e
atmosph ere, is c omposed of only
A b und ance of el ement s in t h e
eight el em
Fig 20
ent s
. .

crus t , incl uding t h e at m

’
eart h s
.
os

ph ere .
M ost of t h e el ements in t h e
28 ELEM ENT S A ND C OM P OUNDS

in c omb ination with oth er el ements ; th at

’
ear th s crus t occur

is, as comp ound s . Oc casionally some are found uncombined ,

or , as it is som eti m ,es c all ed in t h e free, or nat ive , s t at e C op .

per, sulfur, and gold are exampl es .

For many purp oses it is conv enient t o c l assify t h e el ements

as met al s and no nmet al s Every o ne is famil iar with t h e
.

c h arac t eris tic prop erties o f m et al s T h ey h ave l uster and .

c o nd uc t el ec tric ity and h eat M any are common sub stanc es,
.

like iron, aluminum, silver, gold , c opper, l ead , z inc A l l oys .

are c o mmonly mad e b y melting t ogeth er c ert ain metal s .

T hus, b rass is an all o y o f c o pper and z inc Wh at fraction of .

eac h m etal is t aken d epend s up o n t h e use t o wh ic h it is t o b e

p ut . I n re c en t y ears t h e u s e o f all o ys in engi neeri ng p roj ec t s

h as assumed enormous imp ortance T h e all oys of iron ( steel s )
.

are superior t o it in strength and are not t oo expensive Wh en .

th ese all oys are t oo h eavy for a given purp ose, all oys of alu
minum are used ; and wh ere all oys which resist rusting are
"

required , all o y s of C opper or st ainl ess st eel are u sed .

T h e nonmetal s are more varied in th eir properties, some

b eing gases ( oxygen, hydrogen, nitrogen) whil e others are
sol id s (sulfur and c arb on) .

T h e numb er of el ements I n t h e h uman b ody is small , and

more than h alf of th ese are present in very inconsiderable
amounts T h e el ements wh ic h are generall y th ought of as
.

b eing essential t o living pl ants and animal s are o xygen, carb on,
hydrogen, nitrogen, c a l c ium, ph osph orus, potassium, iron,
and magnesium T h e c h emical c h anges whic h take pl ace in
_

l iving organisms are, h owever very c ompl ex , and perh aps ,

so m e o f t h e o th er el em ent s wh ic h o c c ur in sm all er quantities

are equall y essential

Numb er and import anc e of c o mpound s

27 . A s mi ght b e .

imagined , t h e numb er of c ompound s th at c an b e pro d uced

by combining t h e ninety Odd el ements I n d ifferent ways is
-

very l arge M ore th an h alf a mill ion are known and new
.
,

o nes are b eing p repared and stud ied ev ery d ay Fortunatel y

S UM M A R Y OF C HA P T ER II I 29

for us, ly rel atively few of th ese c ompound s are of importance

on .

Therefore t h e study of chemistry is not SO c ol ossal a task as

it might oth erwise b e M oreover as we S hall see t he c om
.
, ,

pound s c an b e divid ed into c l asses and within th ese c l asses ,

they are muc h alike I f we know well even a c omparatively

.

sm all numb er Of c om pound s we sh all h ave a firmgrasp on t h e ,

fund amental s of t h e science .

S UMM A R Y OF C HA P T ER III

A S UB ST A NC E is h omogeneous , t h at is , al l part s are alike and sh ow

m
t h e s a e prop ert ies .

A N ELE M ENT i s a sub s t anc e wh ich h as no t b een s eparat e d int o

mpl er
si s ub s t anc es d uring a ch e mic al react i on ment s may b e
. El e
d ivide d int o met al s and nonmet al s . A n A LL O Y is a mixt ure of t wo or
’

more met al s .

A COM P O UND is a s ub st ance wh ich c an b e d ec o mp o s ed by

ch e mic al means int o t wo or more simpl er sub st ances .

LA W OF D EFIN IT E COM P O S IT IO N : mpound

'

Ev ery co h as a
d efinit e co mposit ion b y weigh t .

C OM P OUND S M I XT UR E S

D efinit e co mpos it ion . C omponent s in any proport ion

m
.
_

I n preparat ion, h eat or ligh t e it In preparat ion, generall y no evi

t e d or ab so rb e d . d enc e o f ligh t o r h eat
m m
.

C an b e d ec o po s ed onl y b y C an o ft en b e s eparat e d b y e
ch e m
ic al m
eans . ch anic al means
m
.

P ro d uct o f c h e ic al react ion . S ub st anc e s no t h el d t oget h er b y

ch em ic al forc e .

QUES T I ONS A ND P R OB LEM S

1 . N ame t wo compound s wh ich cont ain oxy gen .

2 . H ow woul d y ou prove t h at wat er is a c ompound ?

3 . Wh at t wo element s make up ab out t h ree fo urt h s
-
of t he eart h s crust ?
’

P . W h at element h av e wat er and red oxid eof mercury in com mon?

5Gol d is found in a free
. s tate, mercury is found in a combined state.
Wh at d oes t his mean?
 30 EL EM ENT S A ND C OM P OUND S

6 . W rit e o ut a cl ear definit ion of t h e foll owing t er ms as used in ch e m

ist ry : ( a) ment
ele , (b ) co mpound .

L is t
all t h e d ifferences y ou c an t hink of b et ween t h e met al cop per

and t h e m
non et al sulfur .

8 . W h at is t h e d ist inct ion b et ween an alloy and a mixture ?

9 . W h at t h ree t h ings are ch aract eris t ic o f ev ery ch e mical ch ange ?

Selec t from t h e t erms in col umn A t h e

10 . one ( or ones ) which most
accurat ely d efines each of t h e word s in list B

A B
Element
C ompound
M ixt ure
Sub st ance

11 C an y ou t ell from t h e appearance

. of a co mpound wh at el ement s
are present in it ?
12 . H ow c o ul d y o u prov e t h at s ugar c ont ains the ment c arb on?
el e

13 D oes t h e fact t h at a sub s t ance d oes no t d ecompose wh en h eat ed

'

prov e t h at it is an el e ment ?
14 . If aluminum Is more ab und ant t h an iron, gi ve me
so reason wh y
iron is c h eaper .

15 . W h ich el ement was d iscov ered b y an A merican?

~
16 . W h y must t h e
ment s b e revised from t ime t o t ime ?
l ist of el e

1 7, C rit iciz e in t h e l igh t of mo d ern ch emis t ry t h e sel ec t ion b y t h e

‘

Greeks o f earth as one of t h e four el ement s .

18 H ow is t h e mod ern d efinit ion of an el ement d ifferent from t h at st at ed

.

b y R ob ert B oy l e ?

C areful experIment s Sh ow t h at 7 grams of iron u it e wit h 4 grams

19 . n
H OW many grams of iron sulfid e will b e prod uced ?
'

of sulfur .

S t at e t h e l aw wh ich is appl ied in P rob l em19

“
20 . .

r “
21 . W h at weigh t of sul fur will b e need ed t o co mb ine wit h gra ms of

I ron I n ord er t o make grams o f iro n sulfid e ?

22 . Wh at is t h e percent age of iron in iron sul fid e ? Of sulfur in iron
s ulfid e ?

N
23 . St at e t h e l aw illust rat ed in P rob lem2 2 .
 2 OXY GEN . C OM B US T ION . OZ ONE

it b urned more b rilliantly than in air I n t h e l ab orat ory it .

*

is now more convenient t o h eat a c ompound c all ed pot assium

c hl orat e T his is a sub stanc e .

used in med icine and in mak

ing matc h es and fireworks .

I t is muc h c h eaper th an t h e
o xid e o f m erc ury and gives ,

wh en h eat ed , a far l arger pro

portion of oxygen P otassium .

c hl orate is awhite cry stalline

so l id a c om p ound Of t h e th ree
,

el em ent s p ot assI um c hl orine , ,

and oxygen Wh en it is .

h eated t o t h e right tempera

ture ( 360 it melts
°
As
"

t h e t em perature rises still

h igh er bubbl es of oxygen ap
,

p ear l eaving b ehind anoth er

,

c om pound of pot assium and

’

c hl o r ine c all ed po t as s ium

Fig 2 1 J E P P E L EY ( 1 733
OS H RI ST ,

We canexpress this
. .

A n Engl ish ch emis t and cl ergyman wh o ch l orid e .

is usuall y regard e d as t h e d is c overer of

c h ange in t h e foll owing way
oxygen.

potassiu mc hlorat e p otassiu mc hl orid e xygen

m]
o
p o t ass ium
c h l o ri ne [ ris
p

ox y g en

m
I f we carefully h eat s ome pot assiu ch lorat e in a t est t ub e unt il it j ust
m el t s and t h rust a gl owing spl int int o t h e t est t ub e, we find t h at no oxy gen

is b eing ev olved W e now d rop a lit t l e b l ack p owd er c alled manganes e

.

d ioxid e int o t h e t ub e and t est it again for oxygen I n spit e of t h e fact .

th at t h e t ub e h as b een sl owl y d own, oxy gen is now prod uced

c ool ing .

T he manganese d ioxid e is not ch anged in t h is process .

A material whic h thus c h anges t h e speed of a c h emical

ac tion with out b eing itself permanent ly altered is c all ed a

cat alyt ic agent or a c at alyst .

A t ab out t h e sa me t ime
a Swe d ish apo t h ec ary , S c h eel e, al s o prepared oxy gen
m
b y t h is s a e met h o d , b ut t h e resul t s were no t m
ad e p ub lic unt il a few y ears l at er .

T T h e cent igrad e sc al e ( C ) is co
. mmo nl y used in c h e is t ry m
S ee A p pend ix . .
SOM E EXP ER IM ENT S WI TH OXY GEN 3

We shall see a ataly i

th t c s s m
pl ays an i portant rol e in c h e m
ist ry .B y means of it c h em m ical processes ay b e h astened ,
and this results in red ucing t h e c ost of operating many ind us
tries .

T h e oxygen Of commerce is now usually mad e from l iquid ,

air, whic h will b e d escrib ed in section 2 51 .

30 . S o me xperiment s wit h oxygen In ord er t o study t h e

e .

properties of oxyg en we sh all need t o h av e it in consid erabl e

,

quant it y S i nc e
.

oxyge n is now a
c om mercial article,
we can b uy it c om
presse d in St eel C Yl P o t as si um c h lo rat e
i nd er s W e c an
.
and
M anganes e d i oxi d e
d r aw I t o ut as
need ed by means of
Oxy g en P neumat i c
a red uction valv e .

W e may , h owev er,

c onv enient ly make it
b y mixing 4 part s b y
weigh t of po t assium
ch l orat e wit h 1 p art of
Fig 2 2 P reparation of oxygen in th e l ab orat ory
manganese d ioxid e and
. . .

pl acing t his in a t h in gl ass fl ask arranged wit h a d elivery t ub e ( Fig

-
.

T h e gas is coll ect ed in wide mout h ed b ot t l es

-
T h ese h ave b een previousl y
.

filled wit h w at er and invert ed in t h e pneumat ic t rough W h en t h e fl ask is .

gent l y h eat ed , t h e oxy gen es capes t h rough t h e t ub e and b ub b l es up t h rough

t h e wat er int o t h e b ot t l es T h e fl ame under t h e fl ask must b e removed
.

from t ime t o t ime in ord er t h at t h e gas may not b e pro duced t oo rapidl y .

Ot h erwise it will b urst t h e flask .

We shall first ,
vince ourselves that we h ave oxygen
of all c on

by appl yi ng t h e same test as b efore We thrus t a

gl owing spl in t of woo d into a b ottl e of t h e gas T h e fac t th at .

t h e spl int b ursts int o flame is used a s a t es t for oxygen sinc e

th ere is only one other gas (nitrous oxid e) wh ic h b eh aves

sim il arly ; I n general we i dentify a substance by m
, eans of its

di stincti ve behavi or property , whi ch i s called

‘

or a t es t .
34 OXY GEN . C OM BU ST I ON . OZ ONE

We Sh all now wat ch h ow v arious sub stances

?

b eh ave when
t h ey are h eated and th rust into oxygen .

C h arcoal : We wrap a piece of c o pper wire around a small b it of char

c oal , h eat it , and t h en pl unge it int o a b ot t l e

y g en
o f oxy gen ( Fig . I t b urst s int o a b ril
liant gl ow .

S ulfur : We
pl ace a b it of sulfur in an
iron s poon ( d eflagrat ing spoon) and ignit e it
Gar b o”
b y h ol d ing it for a o ent in a fl a e mm
It m .

b urns wit h a p al e b lue fl ame, b ut wh en put

int o oxy gen, it b urns wit h a v ery b rilliant
purple ligh t .

Fig 23 ° B urning ch arcoal in I ron: I t is p ossib l e t o b urn Iron I n oxy gen

o xyg ne '

if we use iron rib b on, such p i c tur e w i r e

as a wat ch spring, oriron wire, such as a st rand of
b raid ed pict ure wire . Firs t we c oat t h e end wit h sulfur .

We t h en ignit e t h e sulfur and s us pend t h e wire in a b ot t le

of oxy gen . T h e sulfur c ont inues t o b urn, pro d ucing av ery
int ense h eat , wh ich is sufli cient t o ignit e t h e iron A s t h e .

iro n b urns , it send s off a sh ower of b rilliant sp arks (Fig .

( I t is well t o c over t h e b ot t om o f t h e b ot t le wit h a

l ay er of s and )

m
.

P h o sph o rus : T h is is asoft , y ell ow sub st ance wh ich ay

t ake fire even at ord inary tem perat ures . For t h is reason
it is alway s kept under wat er wh en s t ored ( Fig A .

sm all b it pl aced in a d eflagrat ing s poon and ignit ed will

b urst int o fl ame wh en pl aced in oxy gen T h e fl ame is so
“
B urning
.

‘
i1m
Fg 2 4
m°xygen
vigoro us and t h e l igh t int ense t h at o ne cannot l ook
’

so

at it wit h co mfort . T h e whit e

c l oud swhich appear are t h e
pro d uct o f t h e ch e mical reac~

t ion .

Wat "
31C h aract eri s t i c s o f
.

o xygen From suc h ex

.

m
p eri ent s as th ese, we see
th at it s m
o st no tic eabl e
Fig . 2 5
. P h os ph orus must b e kept und er wat er .

harac teristic is this : sub

c

stances which burn in air will burn i n oxygen more rapidly and
wi th greater bri lliancy I t is a col orl ess gas and is so S l ightly
.

sol ubl e in wat er th at we h av e no d iffi culty in c oll ec ting it over

 '

P R OP ER T I ES OF OXY GEN 35

water When t h e gas is pure, it h as neith er smell nor taste

. .

It is Slightly h eavier th an air .

T h ose c h aracteristics of a substanc e whic h d esc rib e it s

b eh avior are Often call ed it s c h emical propert ies T h e mere .

name of a partic ul ar material t ell s us nothing I t is only .

wh en we know it s properties th at we are truly ac quainted

with it .

P R OP ER T I ES OF OXYGEN

P HYSI CAL C HEM ICAL

C olorless D oes not b urn
Od orl ess S upport s co mb ust ion
T ast el ess M at erials b urn more read il y and
Sligh t l y h eavier t h an air more v igorously in oxy gen t h an
Very Sl igh t l y sol ub le in wat er in air
H as b een l iquefied and s olid ified M od erat ely act ive at ord inary tem
perat ures

32 .W h at is r
“b u ning
? We h ave j ust seen th at various
”

sub stanc es b urn m ore rapidl y in oxy gen th an in t h e air We .

may th erefore reasonably conclud e th at oxygen plays an .

important part in t h e proc ess of b urning or c ombustion T his ,

.

I s suc h an im portant c h emical c h ange th at it will repay us t o

exam ine t h e proc ess with consid erabl e c are We might d o .

well t o rec all in this c onnec tion some of t h e early experiments .

C h emis t s of t h e sevent eent h cent ury formed t h e phl ogist on t h eory t o

expl ain wh at h appens wh en t h ings b urn B riefly it was t h is A ll c om
“
. .

b us t ib l e t h ings , t h ey s aid cont ain a fire s t uff, ph l ogist on, wh ich is l ost
”
-

in t h e air as fl ame wh en t h ey b urn A sh es ( c alx) are l eft b eh ind

. N ow sub .

st ances , l ike c arb o n, wh ich wh en b urned y ield l it t l e ash , cons ist al m ost

ent irel y of ph l o gis t o n and t h erefore , ac cord ing t o t h is t h eory , b urn readily .

P riest l ey in t h e eigh t eent h cent ury , s aid t h at ord inary air must c ont ain
,

phl ogis t on b ecaus e b urning t hings are c ons t ant ly giv ing it off M oreov er, .

ord inary air h e t h eoriz ed , if d epriv ed O

, f t h is phl ogist on, would b e ab l e t o
t ake up more ph l ogist on t h an b efore and so woul d all ow t h ings t o b urn
in it b et t er t h an b efore C onsequent ly , reco gniz ing t h at oxy gen was s ome
.

h ow co nnect ed wit h b urning, h e c alled it dep h logi sti cated air I t remained .

for L avois ier, a French man t o wh omh e t ol d his expl anat ion, t o make proper
use of P riest ley s d is covery of oxy gen and t o s et t h e worl d righ t on t h e
’

nat ure of c omb ust ion T h is was a very great d is covery

. .
36 O XY GEN . C OM B US T ION . OZ ONE

L a
voisier s
’
xperiment
e on co mb ust ion . Lavoisier
2 6) was a famous Frenc h c h emist wh o lived ab out 1 60
years ago He is so metimes
’

c all ed t h e fath er of mod ern

c h em istry b ec ause h e dis
c ov ered t h e correc t ex pl ana

t ion of t h e p roc ess Of b urning .

H e put some mercury in a ret ort

( Fig . t h e neck of wh ich ex
t end ed int o aja r st anding in a l arger

d is h of mercury A ft er h eat ing t h e

.

mercury wit h a ch arco al fire n early

t o it s b oiling point for t welve d ay s ,

h e d is cov ered t h at t h e air inclosed
wi thin the retort and j ar h ad lost o ne
fifth of i ts volume W h enh e examined
.

t h e air t h at was l eft , h e found t h at a

l igh t ed s plint not o nl y woul d not b urn
in it b ut was ext in guish ed T h e ma .

t erial in air wh ich enab l es asub s t ance

t o b urn h ad ev id ent ly b eenremov ed .

H e found s omb red powd er o n t h e

Fig 2 6
. . A N TOIN E LAUR EN T LAV OISI E R surface of t h e m ercury in t h e ret ort
A French ch emist t h e real
.

( 1 74 3 ,
T his h ad all t h e propert ies Of t h e red
found er of mo d ern ch em i st ry Est ab
m
.

li sh ed t h e t h eory of comb ust ion .

o xid e o f e r cu ry wh ich P riest l ey
h ad used for preparing oxy gen .

L av oisier now placed t h is red powder in a suit ab l e app arat us , h eat ed it

st rongly , and coll ect ed t h e gas ev ol ved .He ob t ained an amount of gas
wh ich exact ly correspond ed wit h t h e
sh rinkage und ergone b y t h e incl osed

air . I n t h is gas sub st ances b urned wit h

great v igor .T h ere was now no d oub t
t h at one fift h of t h e air was composed
-

o f t h is gas . L avoisier called it oxygen .

He now mixed t h e rest of t h e air left in

t h e first experiment wit h enough oxy gen
t o b ring it b ack t o it s original v ol ume .

T h is pro d uced agas h aving all t h e prop

ert ies of o rdinary air . T h us h e proved
t h at t h e oxy gen of t h e air is t h e only Fig . 2 7 . Lavoisier s apparat us for stud y
’

gas used up in t h e pro cess of b urning .

ing c omb us t ion .
P R ODU C T S FOR M ED BY B UR NING 7

34 .W h at is oxid at ion We call t h e reaction Of a sub stance

with oxygen oxid at ion Wh en it takes p l ace so rapidly th at

.

heat and light are prod uc ed we call t h e ch ange burning or

‘

, ,

c om b us t io n A famil iar exampl e of oxid ation is t h e b urning

.

o f c oal woo d gas or Oil

,
Here t h e o xidation takes pl ac e so
, ,
.

rapidly th at we h ave c om bustion .

T h ere are many c ases of o xid ation in whic h t h e c h ange

goes on so sl owl y th at no apparent h eat or l ight is pro duced .

One of t h e b est ex ampl es of this is t h e rus ting of iron W h en .

I ron is l eft in c o ntac t with t h e air it S l o wly turns into iron ,

o xid e or as it is com monly c alled rust T h e rusting of

”
.
, , ,

iron is thus exac tl y like t h e burning of wood ex c ept th at in ,

t h e case of Iron t h e c hange t akes pl ac e so Slo wly th at no h eat

effec t is apparent T h e process is h astened by t h e presenc e
.

of wat er .

35 . P ro d uc t s for med b y b urning, or co mb us t ion . B ut if

burning 1s a c h emical reac tion b etween Oxy gen and t h e sub
wh at ab out t h e c omp ound s formed by t h e
“
st ances b urned ,

c h ange What h as h appened

t o th em? A Candl e d isap
pears al most c ompl etel y wh en
it burns I n this c ase t h e
.

products of th e combusti on are

gases l ike oxygen itself and
are invisibl e T h ey are water
.

vapor and agas call ed c arb on

d ioxid e We c an c oll ec t and
.

weigh th em .

We arrange a c and l e o n a b al
Fig
. 2 8 . m
T h e pro d uct s for ed b y b urning a
ance pan A and sus pend ab ove it c andl e w eigh m
ore t h an t h e c andl e
m
.

at ub e fill ed wit h s od iu h y d roxid e .

T h is s ub s t ance ab sorb s b ot h wat er vapor and c arb on d ioxid e W e are now .

ab l e t o weigh b ot h t h e c and le and t h e pro d uc t s of comb ust ion ( Fig .

W e c arefully b al ance t h e s cal es b y put t ing suit ab l e weigh t s on p an B We .

t h en l igh t t h e c and le and not ice t h at , as t h e co mb ust ion pro ceed s , pan A
m
b eco es heavi er al t h ough t h e candle is v isib ly dis appearing T h e sub st ances .
 8 OXY GEN . C OM B U ST ION . o NE

n
prod uced b y t h e b urning are heavier t h a t h e c andl e wh ich is b urned T his .

m
is b ecause t h ey cont ain t h e el e ent oxy gen t aken fro t h e air, in ad d it ionm
t o t h e el e ment s alread y present in t h e c and le .

xperiment sh ows th at if we weigh the p roducts of com

T his e

busti on we always find them to b e h e avi e r than th e substance

burned A noth er exp eriment whic h ill ustrates t h e same im
.

portant p oint is as fo ll ows

We m
pl ac e s o e iro n powd er in a crucib le and c areful ly c ount erpois e

it on ab al ance wit h t h e aid of weigh t s o r s al l S h o t m W e remove t h e crucib le

'

from t h e p an and h eat it wit h a fl ame T he ass b egins t o gl ow

. T h ism .

sh ows t h at a c h emic al ch ange is t aking pl ac e W e c ont inue t h e h eat ing

.

for ab out fiv e minut es and t h en c ool and exa ine t h e mat erial m T he .

cruc ib l e is found t o c o nt ain a new b l ackish s olid resemb l ing iro n rus t . W h en
the is now pl aced on t he b al ance p an, we find t h at it h as gained
crucib l e

a great deal in weigh t A gain t h e increase in wei gh t is d ue t o t h e oxy gen

.

from t h e air T h is h as c omb ined wit h t h e iron t o form a new compound

.

c o nt aining t h e t wo ment s iron and

el e oxy gen .

T h esexperiments S h ow th at wh en a sub stance b urns in air

e ,

new c omp ound s are formed b y t h e c ombination o f t h e c o mbusti

b le material s with t h e ox y gen T h ese new c omp ound s weigh
.

more than t h e original material b ec ause th ey c ontain oxygen in

add itio n t o th e c o mb ustibl e sub stanc es
'

I n t h e c ase of iron t h e .

prod uc t is c all ed iron o xid e We c an represent t h e c h ange as

.

foll ows
iro n o xy gen iro n o xid e

A n oxide is a comp ound of an element and oxygen Wh en sub .

stances b urn inair or oxy gen, o xid es are al ways f ormed .

36 . xid at ion
S pee d D ifferent sub stances o xid iz e at
of o . .

very different sp eed s A lth ough c ombustibl e material s c om

.

b ine w ith oxy gen at all temperatures y et in every case t h e ,

sp eed is inc reased b y raising t h e t em p erature I n fac t experi .

,

ence s h ows th at i n every ch em ical change raising the temp erature

hastens the process S ome sub st ances l ike p h osph orus o xidiz e
.
, ,

so rapidly at t em p eratures o nl y sl ightly h igh er th an normal ,

or ro om t em perature th at th ey take fire on merely b eing exposed

,

t o t h e air T his is well ill ustrated b y t h e foll o wing exp eriment

. .
40 OXYGEN . C OM B U S T I ON . OZ ONE

tend t o expand with great vigor th at gives t h e force of t h e

ex pl osion B ecause terrifi c expl osio ns h ave o ccurred in fl o ur
.

mills and other factories many mod ern mill s are now equipped
,

with d ust remo ving apparatus and with d evic es for preventing
-

t he sparks d ue t o static el ec tricity .

39 Kind l ing point

. T h e oth er extreme of speed in com
.

b ust ion is represented by iron I n ord er t o c ause this sub .

st ance t o b urn rapidly it is necessary fi rst t o get it int o a

,

finely d ivid ed c ondition th en t o raise it t o a h igh temperature

, ,

and finally t o pl ace it inpure o xygen We d id t h is in a previous

.
'

experim ent 30 ) wh en we coat ed a b undl e of iron wires with

sulfur and b rought th emt o t h e proper tem perature by t h e h eat
ev olved t h rough t h e rapid co m b ustion of t h e sulfur in pure
oxygen .Und er th ese c onditions t h e iron itself finally caught
fire and b urned .

We are all familiar with t h e fac t th at c oal can b e mad e t o

burn only by first b uilding a wood fire and th at t h e wood ,

must in turn b e ignited by paper which itself is lighted with ,

a matc h I n th is series t h e b urning of eac h mat eri al raises

“
.

t h e temp erature of t h e next until it in turn finally c at c h es

fire .
and b urns T h e t emperature at whic h a partic ul ar
.

material will c atch fire in air is sometimes call ed it s kindling

p oi n t. B ut t h e t em p e rat u r e i s o nly on e o f t h e c on d itions
whic h pro d uce comb ust ion Finely p owd ered iron will start
.

burning at a l ower temperature th an will an iron wire b ec ause

it ex poses rel ativel y more surfac e t o t h e air B esi d es t h e
.

physical cond ition o f t h e s o lid t h e pressure of t h e surround ing

,
.

air and t h e presenc e or ab senc e o f a c atalytic agent

'

2 9) al so
determine t h e temperature at wh ic h it will start t o b urn I n .

ot h er word s th ere are several c onditions w hic h affect t h e

,

kindling point .

One may b urn a l ittl e gasoline in an open dish with out

d anger b ut a mixture of gasoline vapor and air may burn so
q u ic kly th a t a n ex p l o sio n o c c u r s T h er ef ore. i t i s ver y i m p or

t ant not to use such li quids as gasoli ne near an open flam e s uch ,

D o not t ry t h is experiment .
EXT I NGU I SHI NG FIR E I

as the pi lot li ght in the ki tchen gas range, for th ey evaporate

‘

rapidly an m m
d t h e vapor with air for s a ixture th at will expl od e .

40 . Ext inguis hing fire . When .

we wish t o put out a fire,
we usuall y pour on water t o c ool t h e b urning material b el ow

Fig 3 0
. . A n oxygen t ent for a pneumonia pat ient .
( S ee page

it s kindl ing point T his succeed s as a rul e if we h ave enough

.

water at h and A ll methods of extinguishing fire dep end ei th er

.

upon cooling the combusti ble m ateri al or upon keepi ng out the
air so that oxygen is no longer availab le for the oxi d ati on T he .

air may s ometimes b e exc l ud ed b y t h e use of a bl anket

,

Wh en .

we use water, we combine t h e t wo advantages, alth ough water

42 OXY GEN . C OM B U S T I ON . OZ ONE

acts h iefly by cool ing t h e burning material Sand and gravel

c .
,

whic h are used t o extinguish c ert ain kind s of fires suc h as !

burning gasol ine simply smoth er t h e fire b y excluding t h e

,

air .
So call ed c h emic al fire extinguish ers as we sh all see
-

in C h apter X VI I c o mb ine t h e c ooling effect o f a l iquid with

,

t h e smo th ering effec t of a

h eavy nonc ombustibl e gas .

T his h angs l ike a c l oud o ver

t h e b urning mat erial and .

exc l ud es t h e air A third .

meth o d of ch ecking t h e c ourse

of a fire is t o rem o ve fromit s

p ath t h e c omb ustibl e mate

r ial T h us b uil d ings are
.
,

so m etim es dynam ited in ord er

t o remove material that is
easil y ignit ed from t h e p ath

o f a conflagrat ion .

Us es b f o xygen P h y
41 . .

sicians som etim es ad minister

o xygen t o p atient s wh o are

suffering from pneum

““
Fig 3 1
. A n oxygen h el met used b y avi
. onia or
at h igh al t it ud es
suffo c ation ( Fig I t is
‘

al so used inst ead of air wh en intense h eat is required , as in

t h e ac etyl ene t orc h and in t h e oxyhyd rogen bl owpip e for weld
ing metal s I t is commonly empl oyed in b urning out t h e c arb on
.

fromautomobil e c yl ind ers Oxygen in tanks is used t o restore

.

t h e supply in t h e atmosph ere of sub marine b oats and in tunnel

ing I t h as b een found th at t h e aviators wh o ascend t o h igh
.

altitud es wh ere t h e air is rarefi ed get only h alf t h e normal

amount of oxy gen and so b ec o me d opey
” “
A n equipment .

h as th erefore b een d evised t o supply t h e need ed oxygen from

a t ank through a c onnec t ing tub e t o a face mask c overing t h e
mouth and nose ( Fig . A ll military airpl anes flying at
an altitude of o ver feet are now equippe d for t he
A NOT H ER FOR M OF OXY GEN 43

use of artifi cial o xygen Simil ar apparatus is empl oyed in

.

fight ing mi ne fires and in rescuing m iners trapped b y poiso nous

gas es .

42 . Oz one, anot h er form of o xygen Wh en el ec tric sparks . .

pass through air or oxygen, a peculiar o d or is noticed T his is .

found mof oxygen call ed o z one

t o b e d ue t o a for .

Oz one Is one and one h alf times as h eavy as ord inary oxygen
-

and disso lves more easily in water A t ordinary t emperatures .

it is a muc h more rapid oxidiz ing agent Since it oxidiz es many .

c om pound s found in pl ants and animal s it is a bl eac h ing agent ,

.

I n several l arge Europ ean cities it h as b een used t o disinfec t

'

t h e water supply I t h as b een suggested as a means of puri fy ing

.

t h e ai r in h ouses
0 3+ 02
a nd l arge h all s , b ut
h as not given very
s ucces s f ul r es ult s .

It is h owever a
, ,

d eo d ori z er .

T he app arat us
Fig 3 2 A pparat us for convert ing oxygen int o o z one
sh own in figure 32
. . .

T erminal s A and B are connect ed t o an ind uc t io n coil

makes ozone b ut
.

onl y ab out 7 p er cent of a given quantity o f o x y gen c an b e con

verted into oz one I t s formation from oxy gen involves an ab ;

.

sorp tion of el ec tric al energy ; and c onversel y w h en it passes ,

b ac k into oxy gen it gives out energy in t h e formof h eat T his

, .

action may b e expressed thus

o xygen energy qr : ozone

D ifferent forms of t h e same el ement whic h differ in t h e amount

of energy th ey c o ntain are c all ed all ot ro ic form s, and t h e
p
unstabl e form (in this c ase t h e o z one) t end s t o p ass into t h e
more stabl e form(oxy gen) with t h e evolution of energy Oth er .

el ements suc h as p h osph orus sulfur and c arb on wh ic h oc cur

, , , ,

in all ot r op ic for ms w ill b e st ud ied in l at er c h apt er s ( XV

,

and XVI I )
44 OXY GEN . C OM B U S T I ON . OZ ONE

S UM MA R Y or CHA P TER Iv

O XYGEN CA N BE P R EP A R ED B Y

(a) h eat ing red oxid e of mercury

(h ist oric)
(b ) h eat ing pot assium ch l orat e (l ab ora t ory )

(c) evapo rat ing liquid air ( c om mercial )

A CA T A LYS T i s a sub s t anc e whi ch c h ange s t h e speed of a ch emical
reac t ion b ut wh ich is not it s el f permanent ly al t ere d in t h e proc ess .

For exampl e , t h e ad d it ion o f mangane s e d ioxid e t o pot as sium ch l orat e

makes t h e oxygen c ome off at a l ow er t emperat ure and of cours e much
fast er at t h e s ame t emperat ure .

O XYGEN is a c ol orl es s od orl es s gas s omewh at h eavier t h an air

, .

I t c omb ine s wit h nearl y all ot h er el ement s .

O XY GEN I S U S ED C O M M ER C IA LLY for t h e pro d uct ion o f h eat

and ligh t , in t h e mel t ing, cut t ing, and w el d ing o f met al s , and in
b reat h ing apparat us us ed b y aviat ors and in mines and t h e s i ck

roo m .

O XID A T IO N is t h e proc es s of comb ihing a sub s t anc e wit h

‘

oxygen .

A N O XI DE is a c ompound of oxygen and ano t h er el ement . Oxi d es

are for med wh en an el ement b urns in oxygen or ai r .

C O M B U S T IO N i s a c h emic al ac t ion in wh ich h eat and l igh t are

ro d uced
p .

O R D INA R Y B UR NI N G i s a rapid oxid at ion wh ich i s ac c ompanied

b y h e at and l igh t .

A N EXP L O S IO N i s d ue t o t h e v ery rapid co mb us t ion of c ert ain

mixt ures of gas es mb ust ib l e dust and

or o f c o a gas .

T HE KIND L IN G P OINT o f a mat erial is t h e l ow es t t e mperat ure

at wh ich it t akes fire a d b urns n .

SP O NT A NEO US C O M BU S T IO N o c cur s wh en mat erial is rais ed

t o it s kind ling point b y t h e h eat pro d uced in it t h rough a s l ow oxid at ion

wh ich s t art s at ord inary te mperat ures .

T H E S P EED of all ch emi c al ch anges is increas ed b y raising th e

te mperat ure .

El ement s somet imes o ccur in t wo or more for ms (A LL O TR O P IC

FO R M S ) wh ich d iff er in t h eir propert i e s b ecaus e of a d ifierence in t h e
amount o f energy t h ey c ont ain.
QUEST IONS 5

O Z O NE is an al l otropic for mof oxygen produced b y t h e act ion of a

s il ent el ect ric d is ch arge . I t i s uns t ab l e and is a powerful oxid izing
agent . I t is us ed in some pl ac es fo r purifying t h e wat er suppl y .

QUES T I ON S
a N ame t h ree
i met als wh ich d o not oxid ize .

p H ow can y ou prevent a met al fromrus t ing ?

o
y W h en met al s t arnish or rus t d o t h ey c h ange in weigh t ?

“
mW hy Is oxy gen somet imes called a support er of comb ust ion” ?
,

W h en a mat ch is l igh t ed wh y d oes it s ent ire l engt h not c at ch

, fire
at once ?

6 . Expl ain wh y wood in t h e for m of sh avings b urns more rapidly t h an

t h e same woo d in t h e form of a l og .

7 Na .me t h ree sub st anc es wh ose kind ling point s are lower t h an t h at
of c o al W h at use is mad e o f t h ese in st art ing a coal fire ?
.

8 N ame t h ree c o nd it io ns wh ich affec t t h e kind ling p oint of a s ub st ance

. .

9 C an t h e prod uct ion of l igh t o c cur wit h out c omb us t ion?

.

10 . Why d oes c o al p acked c l os ely in poorly v ent il at ed b unkers oft en

t ake fire ?
fire wh en t h ey h ave
,

11 . Wh y do rags s o aked wit h linseed oil oft en c at ch

b een t h rown in a h eap in a cl os et ?

12 . W h at is t h e safe way t o d is pose of greasy cl ot h s ?

13 . I f y our cl ot h ing c augh t o n fire, h ow would y ou put it out ?

14 . . W hy d o es wat er ext inguish a fire ?

15 . Wh y d o firemen and miners use oxy gen h elmet s ?

16 . For wh at purpose d o aut omob ile s h ops frequent ly use oxy gen?

17 . W h at med ic al use h as oxy gen?

18 . W h y are t h eater curt ains made of asb est os ?
19 . W h y is oz one a more act iv e oxid iz ing agent t h an oxy gen?
20 . W h en we wish t o prepare oxy gen in quant it y in t h e l ab orat ory ,

wh y d o we not h eat mercuric oxid e ydid ?

as P riest l e

21 . Wh y d oes a go od draft make a fire b urn more rapidly ?

22 . W h at formo f life d epend s on t h e sligh t sol ub il it y of oxy gen in wat er ?
23 . H ow coul d y ou prove experi ment ally t h at p art of t h e air d is appears
in t h e rust ing o f iro n?

24 . Wh at use o f o xy gen is m ad e in s t rat osph ere as censio ns ? W y

h ?
 C HA P TER V

HYDR O G EN A ND IT S USES

Occurrence purificat ion preparat ion fro m wat er and acids

d ispl acement simple repl ace entm s eries experi ment s to
illust rat e it s propert ies ch em ic al b eh av ior reducing act ion
uses D iffus ion
. T h e kinet ic molecul ar t h eory
.
-
.

43 . Wh ere h yd rogen is fo und . We have j ust stud ied one of

th e l
ee ments in water oxygen . I n th is
h apter we sh all d eal
c

w ith h
t e o th e r el em e n t — hy
drogen T his el ement is al so
.

a gas b ut unl ike oxygen it , ,

d oes not occur t o any extent in

a free state in nature Small .

amounts of it are found in so .

c all ed natural gas T h is is an .

inflamma bl e mixture of gases

whic h c omes out of t h e ground
in c ertain parts of t h e world .

A b out h alf of t h e gas c on

s um ed in N orth A mer i c a
fo r h eat and l ig ht is nat ur al
g as W ater g as al s o used for
.
,

h eating and ill uminating pur

p oses c on t ain s,a b o ut 38 p e r

cent hyd rogen A nd finall y .

,

hydrogen is al so present in
Fig 33 H ENR Y C A VE N DISH ( 1 73 1
c om bination with oth er el e
. .

A n English man of weal t h wh o l ived as a

e t o ch em
m ent s in pl ant s and anim
recl us e and d evot ed h is t im ical al s ,

including t h e h uman b o dy
and ph y sic al invest igat ions .

It was in 1766 th at H enry C avend ish ( Fig 33) establ ish ed .

t h e fac t th at hyd rogen is an el ement A l ittl e l ater h e proved

.

46
48 H Y D R OGEN A ND I T S U SES

so d ium is d ropped water, and t h e ac tion b egins at o nce

on

( Fi g . T h e m et al is v ery l ight and runs h issing ab out o n

t h e surface o f t h e water A s t h e ac tion o ften end s with a
.

sl ight expl osion, a gl ass pl at e sh ould b e p l aced o ver t h e b eaker

t o prot ec t t h e eyes I f we wish t o coll ec t t h e hyd rogen which

.

is evolved b y t h e ac tion o f
t h e so d ium on t h e water, we
proc eed as foll ows :
d r og en

W e wrap a fresh l y piece of

-
cut

s o d iu m in t in foil and punct ure t h e

foil in s everal pl aces . I f we d rop
t his int o a d ish of wat er, b ub b l es
of h y d rogen ris e and may be c ol

l ect ed in an inv ert ed cy l ind er filled

wit h wat er (Fig .

I f p o tassium is used in
st ead o f so d ium , t h e ac t ion
is more viol ent and so much
h eat is produced th at t h e h y
d rogen is set on fire Wh en .

S od ium and wat er prod uce

Fig 35 . .

c al c ium is used t h e metal

h y d rogen
sm ks t o t h e b ottom of t h e
.

vessel so th at a b ottl e fill ed with water can easily b e inverted

o v er t h e m et al t o co ll ec t t h e gas as it is form ed I n each o f
.

th ese cases the metal sets free only one half of the hydrogen in the
-

water .I t c ombines with t h e remaining h alf and with all of

th e oxygen t o form t h e c ompound known as t h e h yd roxid e of
t h e given metal .T h e c h emical reaction of s odium and water
may b e expressed thus
d ium
m]
so water hyd rogen so d iumhyd roxid e
[ gr
oxy gen

T h e sodium hyd roxid e and potassium hyd roxid e readily d is

solve in water B ut most of t h e c al cium h y d roxid e remains
.

und issolved and may b e seen suspend ed in t h e water .

B EHA VI OR OF M ET A L S WI T H A C ID S 9

46 . B eh avior wit h acid s

of T h e most convenient
met al s .

way t o prepare hydrogen in t h e l ab oratory is b y t h e ac tion of

certain m etal s on ac id s A cid s are compound s whic h contain
.

hy drogen T h ey h ave al so certain o th er peculiar properties,

.

b ut we sh all no t consid er th ese until a l ater c h ap ter T he

“
.

c om monest acid is sulfu ric ( oil o f I t is a h eavy

l iquid and mix es with water in all proportions T h e 96— per cent .

pu re l iq uid is know n as c o nc ent r at e d sulfuric ac id T h e d ilute .

acid m
ay b e p rep ared b y sl o wl y p ouring so e c o nc entrated m
sulfuric ac id int o four or fiv e ti m
es t h e sa e v ol u e o f wat er m m .

D il ute sulfuric acid ac ts vigor

o usly with c o m mercial granu
l ated zinc pro ducing h y d rogen
,

I f t h e z inc and t h e ac id are

pure, t h e action is very sl o w .

d
T h is ac t on c an b e h astened
b y add ing a l ittl e c opp er sul
fate sol ution t o t h e acid .

T h e z inc is pl aced in ab ot t le fit t ed
wit h a t wo h ol e s t o p per ( Fig
A “
“
-
.

d
A l ong t h ist l e t ub e reach es t o t he
b o t t om of t h e b ot t l e . T h rough it Fig 36 M aking h y d mgen in t h e
l ab orat ory
t h e ac id is poured int o t h e b o t t l e
‘

I t als o act s as a s afet y t ub e T he o t h er t ub e c arries t h e h y d rogen int o

mat i
.

a pneu c u
t ro gh , wh ere it may be c oll ec t ed in b o t t l es .

T he reac tion w hich takes pl ac e in this c ase may be repre

sen et d as foll ows :

z inc su lfuric acid hy drogen zinc su lfate
h y d ro gen z inc
s ul fur
o x y gen [ s ul fur
o x y g en ]
T h e o th er pro d uc t of t h e reaction, z inc sulfate, is a wh ite
sol id wh ic h d isso lv es in water I t c an b e obtained if t h e
.

liquid l eft in t he b ottl e is evaporated We see h ere t h at t h e .

el em ent zinc h as t ak en t h e p l ac e o f t h e hyd rogen in t h e sulfuri c

acid and th at t h e h y d rogen h as b ec ome a free el ement T his .

is a new kind o f ch emical c hange We c all it d i spl ac ement

. .
so HYDR O G EN A ND I T S USES

Here an elem ent disp laces one of the elem ents fro a com pound, m
s etti ng i t free, and uni tes wi th th e rest of th e consti tuents of th e

co mp ound .

I nstead of z inc , we might

h ave taken o th er metals mag
nesium al uminum or iron
, t o prepare hyd rogen in this way
, .

Oth er acid s such as d ilute hyd roc hl oric acid could h ave b een
, ,

used instead of sulfuric .

47 . S impl e r epl ace ment In t h e preparation of

s eries .

hydrogen we h ave seen th at a m etal , suc h as z inc , repl aces

hyd rogen in an acid One naturally won .

d ers wh eth er any metal will repl ace t h e

hydrogen of any acid , and wh eth er it will
repl ace any o th er el em ent from a com

pound .I n o th er word s, is th is a typ ical

reac tion? In l o o king for t h e answer t o
th is question, we sh all find it useful t o
s tudy t h e m etal s in t h e adj oining t abl e .

Experiment sh ows th at t h e metal s

ab ove hyd rogen will repl ac e it from d il ute
hyd ro c h l ori c and
sulfuric ac id s and ,

no metal b elow h y
d rogen will repl ac e
it from th ese d il ut e ac id s A l so we .
,

shall see th at th ese m et al s are arranged

in t h e ord er of th eir ac tivity p o tassium

m
,

ost ac tive and gold l east ac tive In .

s eni or c o ur s es y ou m
d r og en
ay st ud y th is .

ar r ang ement of t h e met al s mor e full y .

48 . Experi ment s wit h h y drogen We need .

a st eady st ream of h y d ro gen for many experi

men
ts T h e Kipp generat or (Fig 37) is a piece . Fig 3 7
. . Kipp generat or for
making h y d mgen
.

of app arat us t h at will s upply t h is fo r us I t is .

so arranged t h at it alway s c ont ains a s mall amount of h y d rogen in t h e

mid dle b ulb . W h en t his is d rawn on by o pening the st op co ck, fresh
acid aut omat ic ally rises from t h e l ower b ulb and act s on t he z inc which is
EXP E R IM EN TS WI T H H YDROG EN 51

also in t h e mid dle T h is act io n replenish es t h e s upply of gas

b ulb . If t oo .

much gas is generat ed , t h e acid is forced away fromt h e z inc and t h e act ion
s t o ps
. I n t h is way a st eady s t reamof gas is prod uced ?
“
Firs t we sh all t ake a wid e mout h ed b ot t le filled wit h h y
-

d rogen and apply a flame t o it s mout h If t h e h y d rogen is .

mixed wit h air, a sligh t pop result s B ut if it is free from

.
-

air, it b urns quiet ly .

I f we lift up anot h er b ot t le of h y d rogen, h ol d it mout h

d own, and insert a l igh t ed t aper (Fig we find t h at t h e .

h y d rogen will b urn around t h e mout h of t h e b ot t le b ut t h at

‘

t h e t aper is ext inguish ed On b eing wit h d rawn from t h e

.

b ot t l e, t h e t aper is again ligh t ed as it passes t h rough t h e

b urning h y d ro gen T h is st riking experiment may b e re
.

peat ed several t imes unt il t h e h y d rogen is b urned up It .

sh ows t h at sub s tances wi ll not b urn i n h yd rogen .

T o sh ow h ow very ligh t h y d rogen is, we at t ach a common

cl ay pipe t o a h y d rogen generat or and d ip t h e b owl in
'

so apsud s .W e may t h us fill soap b ub b les wit h t h e gas

-

Wh en t ossed from t h e pipe, each b ub b l e rapidly rises in

t h e air .

A not h er ment illust rat es t his same point Suspend an

s t riking experi .

invert ed b eaker fromone armof a b al ance and t h en p our h yd rogen up i nto i t

(Fig . T h e b eaker
rises .

We s h all next mix

equal v ol u mes of air
and h y d rogen b y lift
ing ab ot t le wh en only
h alf full of h y d rogen
out of t h e p neu at ic m
t rough so t h at air t akes
t h e pl ace of t h e wat er .

W h en fl ame i s
a
b rough t near such a ,

mixt ure of gases , t h ere

Fig 39
. . P ouring h y d rogen up int o t h e b eaker makes it
is a l oud expl os io n.

appear l igh t er .
W h en we h ave h y
d rogen unmixed wit h
air, we may
at t ach t o t h e generat or a clay pipe st e -
m t o serve as a jet and may
. m
ligh t t h e h y d rogen T h e fl a e is very h ot b ut gives very lit t l e l igh t . I t is
m
al ost wit h out color, b eing onl y sligh t ly b luish .

H y drogen is a co mmerc ial art ic le and c an be ob t ained co mpressed in s t eel

t anks .
52 H YD R OGEN A ND I T S U SES

—
In order t h e pro d uct o f b urning h y d rogen in air, we at t ach
to s t udy

a d ry ing t ub e ( Fig 4 0 ) filled wit h c al c iu

. m
c hl orid e b et ween t h e jet and t h e

generat or . m
W h en all t h e air h as b een expelled fro t h e apparat us , t h e h y
drogen b urns wit h a small fl ame . If we h ol d a c ol d , d ry b ell jar o ver t he
fla me as sh own in figure
40 , wat er v ap or is s oon

s een c ond ens ing o n t he

jar , and aft er a sh ort

ti me d rops of wat er run

Fl ame d own t h e s id es .

d r o g en
49 P h ysic al prop
.

ert ies of h yd rogen .

S uc h ex p eriment s
S h ow Som e of t h e

c h arac t eris t i c s o f

h y d r o g en L i k e .

ox y gen it is a c ol or
Fig 4 0 B urning d ry h yd ro gen t o for mwat er
d orl ess gas l ess
. . .

, o

wh en p ure I t 1s one sixteenth as h eavy as o xygen b eing in

'

-
.
,

fac t t h e lightest of all known sub stances Since it is so light .

a gas it esc apes very rapidl y th rough small op enings

, T his .

is t h e reaso n wh y a small rubb er b all oon fill ed with h y d rogen

c o ll ap ses more quic kl y th an a simil ar b all o on fill ed with ill u
minat ing gas Hydrogen dissolves very slightly in water, even
.

l ess th an oxygen .

Hyd rogen can b e l iquefied by compression provid ed it is ,

first suffi ciently cool ed Liquid hydrogen is al so col orl ess

. .

Wh en all owed t o evaporate rapidly it freezes t o a c ol orl ess , .

sol id

50 . C h emical b eh avior of h yd rogen . We h ave seen th at

hyd rogen b urns in t h e air and th at t h e product is water , t he
familiar compound of hydrogen and oxygen
hydrogen oxygen water

A lth ough hydrogen itself t akes fire easily, y et i t is not a

supp orter of combusti on, th at is, sub stanc es will not b urn in
R ED U C I NG A C T ION 3

it At d inary temperatures hyd rogen d oes not read ily unite

“
. or ,

with oth er el ements ; i e it is not an ac tive el ement . .B ut

,
.

und er certain c ond itions it d oes c o mbine with many o f t h e

el em e n t s For ex amp
. l e if a mixt ure o f hyd rogen a n d c hl
,
o rine

is exposed t o t h e sunl ight t h e t wo gases will c omb ine with ,

expl osive viol enc e t o f orm hydrogen chl oride Und er t h e right .

c onditions hyd rogen c om ,

bines with nitrogen t o formammonia .

With sulfur it c ombines t o form hydrogen sulfide t h e o d or of ,

whic h is t h e ch arac teristic smell of ro tten eggs I f a mixture .

C a viol ent
°
o f h y d rogen and oxygen is h eated t o ab out 8 00 .
,

expl o sion o ccurs and water is form ed .

Let us make a mixt ure of t wo p art s b y v ol u e of h y d rogen and one ofm

oxy gen 1 9) and p ass it int o soapy wat er so t h at a frot h of b ub b les filled
wit h t h e mixt ure is for med . We first remove the generator T h en we set t h e
.

frot h fire, us ing a l ong gas ligh t ing

on -
t aper T h e mixt ure expl od es wit h a
.

report l ike t h e S h ot of a gun .

h y drogen and oxy gen combine with great viol ence

A lth ough .

at a comparatively high temperature y et th ese t wo gases c an ,

b e left togeth er at room temperature for a very l ong time and

no thing will h app en B ut if we ad d t o th em certain metal s
.
,

suc h as finely d ivid ed p l atinum c h em ic al reaction sets in

m
.
,

S o etimes t h e p latinum b eco mes so warm th at it gl ows from

t h e h eat prod uced b y t h e c omb ination T h e pl atinum itself .

d oes not ch ange it merely ac ts as a c at al y s t We may think

,
.

o f a catal y st as ac ting l ike t h e oil wh ic h is appl ied t o a mac h ine

as a l ub ric ant We grease t h e b earings t o make t h e wh eel s go
.

around more easily We ad d a c atalyst t o make a c h emical

.

c h ange take pl ac e at a l ower t em perature .

51 . R Hydrogen will not only c omb ine

ed ucing act io n .

with oxygen when h eated , b ut it will al so remove oxygen from

many compounds , suc h as c opper o xid e .

C opper is a b l ack solid consist ing of t h e t wo element s copper and

oxid e

oxy gen I t can b e formed b y h eat ing copper in t h e air

. T his o xid at ion .

goes on slowly , b ut grad ually al l t h e c o pper is ch anged int o t h e oxid e

,
We .

sh all now rem ove t h e oxy gen again fromt h e copper oxide .
54 HY D R OGEN A ND I T S USES

T he a
pparat u s sh own in figure 4 1 is so arranged t h at d ry h y d rogen may
b e p assed o ver h ot co pper oxid e . T h e oxid e is pl aced in t h e gl ass
t ub e and h eat ed wit h a b urner unt il it is almos t red h o t H y d rogen is.

t h en passed over it W at er forms and c ond enses in t h e t ub e M et allic

. .

c o pp er is l eft in t h e t ub e .

I t c an b e rec ognized b y
it s red d is h col or and
met allic l ust er W h y .

C OW " Omd e
Dr y i ng
must t h e h y drogen b e
d ry ?

‘
Wh en hydrogen .

co mb ines with t h e
xygen of a c om
o

p ound and t hus re

moves t h e o xygen ,
Fig 4 1 R ed ucing copper oxid e ( b lac k) t o met allic
. .
we say th at t h e sub
copper (red ) .

s t ance h as b een re

d uc ed R ed uc tion is therefore essentially the rem

. oval of oxygen .

During this pro cess t h e hy drogen c omb ined with t h e oxygen

and form ed wat er T h is c h ange c an b e expressed thus
.

c opp er o xid e hyd rogen water c opper

h y drogen
[ [
co p p er
oxy gen oxy gen

T h e c o mb ining of a sub stance with oxygen h as al ready 34 )

b een d efined as oxid at ion T h erefore t h e hy drogen h as b een
.

o xi diz ed in th is exp erim ent , wh il e t h e c opper oxid e h as b een

reduced R ed uc t ion i s always accom

.
p ani ed by oxid ation For .

if one sub stance is b eing red uced , so me o th er sub stanc e must

b e und ergoing o xid ation B esid es hydrogen, th ere are oth er
.

sub stanc es, suc h as c arb on, wh ic h act as red ucing agent s We
“ “
.

s h all l ater see th at t h e t erm red uction

”
s oxid ation and are
o ften giv en a som ewh at wid er m eaning .

52 Uses of h yd rogen Hydrogen h as a few practical

. .

applications B ecause it is t h e lightest known gas, it h as

.

l ong b een used t o fill b all oons and dirigibl e airsh ips B ut on .

account of t h e d anger o f expl osio ns it h as in l at e years b een

56 HYDR OG EN A ND I T S U SES

mixture of t h e gases . T his means

th at t h e hyd rogen gas in ,

Spit e of it s l ightness h as m o ved d ownward and th at t h e ox y gen

, .

which is nearly 1 6 times as h eavy as h yd rogen h as moved up ,

ward A ll gases h ave th is extraordinary power of motion

. .

T h is pro cess by whic h t h e gases b ec ome uniformly intermingl ed

is c all ed d iffus ion T h e rates at wh ic h different gases d iffuse
.

into a p articul ar gas suc h as air , ,

d epend upon th eir d ensities T h e .

lighter t h e gas t h e faster it mix es ,

with oth er gases Hy d rogen h as .

t h e greatest speed of d iffusio n of all

gases I t mixes with air 4 times as
.

rapidly as oxygen .

B ecaus e of it s col or, we can easily wat ch

t h e d iffus ion of such a v apor as b romine
t h rough t h e air W e p our a l it t le liquid
.

b romine int o a cy lind er T h e red liquid

.

quickly ev aporat es and t h e v apor d iffus es

up t h rough t h e wh ol e cy l ind er ( Fig 4 3) .

even t h ough it is 5 t im es as h eavy as air .

54 . T h e kinet ic -
mol ec ul ar t h eory
xpl ains d iffus ion I t is now gen
e .

eral ly supp osed th at all sub st ances

D iffusi on of b romi ne
Fi g 4 3
. .

vapor upward ar e m a d e up o f exc eed mgl y mi nute

p articl es c all ed mol ecul es ; al so
,

th at all t h e mol ec ul es o f a given sub stance are al ike I n sol id s

‘

and l iquid s th ese mol ecul es are fairly cl ose togeth er B ut in .

gases th ey are wid ely sc attered with muc h vacant sp ace b e

,

tween th em T h en t oo it is supposed th at t h e littl e particl es

.
, ,

of a gas are fl y ing ab o ut in all d irec tions with great sp eed and

th at th ey are traveling in straight lines ex c ept wh en th ey h it ,

one ano th er or t h e wall s of t h e c ont aining v essel and b ou nce

o ff . T h e mol ecul es o f a gas seemt o h ave no inh erent t end ency
t o stay in one pl ace T h is expl ains wh y gases d iffuse so quic kl y
.

and fill t h e wh ol e containing vessel as we saw in t h e prec ed ing

,

paragraph We express t h e fact th at t h e mol ecul es of all gases

.
NEWEY DI S C OVE RED FOR M S OF HYDR OG EN 57

un ed r o rd in ary c o nd it ion s ar e s uppos ed t o b e in rapid m o tio n

by saying th at th ey possess kinet ic energy .

A ll l aws o f gases ( see A ppend ix ) c an b e expl ained by th is

so c -
a ll ed ki net i c m o l e-
c u l ar t h eo ry F or inst an
. ce it accounts ,

for gas pressures since t h e bl ows wh ic h t h e mol ecul es o f a gas

strike against t h e surround ing wall s t end t o push out th ese

wall s A cc ording t o th is th eory t oo t h e expansion of a gas

. , ,

wh en h eated is d ue t o
t he m ore rapid m ov e

ment of it s mol ecul es .

T his results in greater

p re ss u r e si
,
nc e e ac h
mol ecul e hi t s h ard er
as it reb ound s over ,

co mes t he opposi ng

pressure, and thus al

l ows t h e gas t o expand .

A goo d ex a pl e m of

this is t h e ac tion of

t h e gas exp l o d ed in
t h e c yl ind er of an
auto mobil e engine .

55 . N ewly dis cov

ered forms of hy
d ro gen In 1 92 9 Fig 4 4
. . H A R OLD C UR EY ( 1 8 93
. A war d ed
t h e N ob el priz e in c h em
.

ist ry in 1 934 for hi s d is

B onhoeffer sh owed ex c o very of d eut erium

p e r i me nt al l y t h at
.

th ere are t wo kind s of h y d rogen with different physical prop

ert ies I n ordinary h y d rogen, at room t emperature, th ere are
.

three parts of one ( ort h o h yd rogen) and one part o f t h e o th er

-

( para h y d rogen) T h ese sub stances are more fully d iscussed in

-
.

advanced b oo ks on t h e mod ern th eories of t h e structure of t h e

mol ecul e .

M ore , inrecen
1 9tly
32 ,
th ree A meric an c h emist s , Urey
( Fig 44 ) and M urphy of C ol umbia University, and Brickwedd e
.
58 H YDR OGEN A ND I T S U SES

of t h e U S B ureau of Stand ard s , s h owed th at th ere is a for

. . m
of hyd rogen m uc h l ike ord inary h y d ro gen b ut twice as h eavy .

T h is h as b een call ed d eut eriu S till more rec ently ano th erm.

formof hydrogen was discovered wh ic h is th ree times as h eavy

as ord inary h y d rogen T h ese are c all ed isot opes o f hy d rogen
.
,

and we sh all d isc uss th emfurth er in C h apter X VIII .

S UM M A R Y OF C HA P T ER V

H YDR O G EN M A Y B E P R EP A R ED b y
( a) react ion b et ween wat er and a met al
( 17) d ispl ac e ment met al (l ab orat ory met h od )
from an acid b y a

( c) el ec t rol y s i s of wat er ( c ommerc ial met h o d )

H YD R O GEN i s a colorl ess , od orl ess gas . I t i s t h e l igh t est known

gas and d iffus es mo re rapid ly t h an any o th er gas .

H YD R O GEN B U R NS in oxygen or air, for ming w at er . I t is a

powerful red uc in
g agent . Wh en a sub st anc e is red uced b y h y d rogen,
t h e h y d rogen in t urn i s oxid iz ed . R ed uc t ion is al way s acc ompani ed
by oxid at on i .

U S ES OF H YD R O GEN : For fil l ing b al l oons and d irigib l es , for t h e

h yd rogenat ion of oil s , for t h e oxyh y d rogen flame us ed t o pro d uc e
int ens e h eat , for t h e preparat ion o f synt h et ic ammonia; al so (m ixed
wit h ot h er gas es ) as a fuel .

—
T H E K INET I C M OLEC UL A R T H EO R Y of gas es as su mes
( 1) t h at a gas is a vacant spac e wit h
w
exc e ed ingl y minut e part icl es
s c at t ered t h rough out , and (2) t h at t h e s e part icl es (mol ecul es ) und er
o rd inary co ndit ions are flying ab o ut in al l d ire c t ions wit h great sp eed .

NEW LY D I S C O VER ED FOR M S of h y d rogen incl ud e d eut eri um,

t wic e as h eavy as ord inary h y d rogen, and anot h er t h ree t i mes as h eavy .

QUEST I ONS
fi
i
- D escrib e t wo different way s of preparing h y dro gen fro mwat er .

W h at el e ment is present in all acid s ?

t H ow woul d y ou t est h y drogen t o

C omp are h y d rogen and o xy gen as regard s ( a)
(c ) d ensit y ; (d ) sol ub ilit y in wat er ; ( e) comb ust ib ilit y
see if it were c ont a

.
inm
at ed w
c ol or
it h

;
air ?

(b ) Od or ;
QUEST I ONS 59

5 . Wh en C avendish dis covered h y drogen, h e called it inflammab l e

air . Wh y ?
6 . Is it necess ary t o use a pneumat ic t rough i n collect ing h y d rogen?
7 . M ent ion four import ant uses of h y d ro gen .

8 . W h at
prop ert y h as h y d rogen wh ich akes it a d angero us s ub st ancem
wit h wh ich t o infl at e b alloons ? How d oes t h e Unit ed S t at es G overn ent m
meet t h is prob le m?
9 . Wh y d o we not fill b all oons wit h oxy gen?

10 . W h at
t wo propert ies o f h y d ro gen are il lus t rat ed wh en a ligh t ed t aper
is t h rus t up in t o an inv ert ed b o t t l e of h y d ro gen?

11 . H ow woul d y ou arrange a b ot t le of h y d rogen t o keep it ov ernigh t ?

12 . In t he experi ment of b urning h y d rogen t o form wat er, wh y is it
necess ary t o d ry t h e h y d rogen?
13 Expl ain h ow t h e t hist l e t ub e in t h e h y d rogen generat or act s as a
.

safet y t ub e.
14 . Why ‘

is oxy gen pass ed t h rough t h e inner t ub e Of t h e oxy h y d rogen

b l owpipe rat h er t h an t h e o ut er?

15 . W oul d h y d rogen l eak t h rough a s mall h ole in a b alloon more quickly
or more slowly t h an air ? W y
h ?

16 . W h en zinc wit h h y d ro chl oric acid , b ub b l es of h y d rogen ris e

reac t s

fromt h e z inc H ow c an t h is b e t rue if z inc is an element ?

m
.

17 . Will a d efinit e weigh t of iron d ecompose an unli it ed we

igh t of

st ea m?
18 . D o we ev er h ave red uct ion wit h out oxid at ion?

19 D o we h ave oxid at l on wit h out red uct ion?

‘

. ever -

20 . B y wh at ch e mical t es t c oul d y ou d ist inguish powd ered c upric oxid e

from powd ered ch arco al ?

21 . C oul d pure h y d rogen b e used in a B unsen b urner inst ead of ill umi
nat ing gas ?
22 . W o ul d pure h y drogen furnish a s at isfact ory illuminat ing gas ?
Expl ain .

23 H ow is it t h at gas b urns quiet ly in t h e b urner o f t h e gas st ove b ut

.

expl od es wit h v iol ence if ignit ed aft er it es capes in any quant it y int o t h e

roo m?
24 . R ememb er h ow v iol ent l y so d iu m act s on wat er Y our b o d y
cont ains s o dium c h ances t h erefore
’
ab out an o unce of D on t y ou t ake
.

every me y o u go in swimming ? Expl ain

ti .

2 5 N ame t h e t h ree t y pes of ch emical react ions wh ich

. h ave b een st udied
t h us far and d es crib e b riefly an exam pl e of each .
 CHA P TER VI

WA TER A ND I T S C OM P OSI TI ON .

H YDR O G EN P ER OXI DE

Oc currence and import ance ph y sical propert ies ch ange of

s t at e sol vent
power of wat er m
i purit ies in wat er purifica
t ion of d rinking wat er .

m m
C h e ic al co posit ion of wat er el ect rol y s is sy nt h esis by
v ol um G ay Luss ac L aw Vol umes sy nt h esis b y weigh t
’
e -
s of

percent age co mposit ion . H eavy wat er .

H y d rogen peroxid e c ompos it io n, pro pert ies, and uses .

LA W OF M U L T I P L E P R OP OR T I ONS .

O c c urrenc e and import anc e Water is t h e most familiar

mt
56 . .

and t h e most i por ant of all c h e ic al c o mvers mpound s . It co

ab out five I t is c ontained in

sev enth s of t h e earth s surface
"

’
-
.

va rying am ount s in m any of t h e c ommonest obj ec t s The .

soil und er nO rm al cond itions c ontains water wh ic h as we , ,

all kn ow is necessary for t h e growth of p l ant s ( Fig

,
T he .

pl ants th emselves contain l arge quantities of it I n fac t most .

,

Of t h e v eget abl es used for foo d are at l east th ree quarters -

water C ertain of th em such as cucumb ers and tomat oes

.
, ,

c ont ain as m uc h as 95 p er c ent M ilk is ab out 87 p er c ent

.

water T h e h uman b o dy c onsists of ab out 70 p er c ent water

.
,

wh ich is d erived from our foo d and d rink T h e presence of .

water vapor in t h e atmosphere it s formation into rain and ,

s now und er v arying c ond itions and t h e im portant p art it pl ay s

,

in c l imat ic c h anges are famil iar t o ev eryone B ec ause water is .

so im p o rt an t in t h e grow th o f p l ant s and an l m al s and in t h e

pro d uc tion of c l imatic c h anges it is not t oo muc h t o say th at

,

l ife with out it is impossibl e .

57 . P h ys ic al propert ies . P ure wat er is an od orl ess l iquid .

In sm all quantities it is c ol orl ess , b ut l arge masses Sh ow a

60
P H Y S I C A L P R OP ER T IES 61

d istinctl y greenish bl ue c ol or Wh en sufficiently c ool ed it

-
.
,

b ec omes a c ol orl ess sol id known as ice Wh en h eated it b oil s .

,

and c h anges rapidl y into water vap or or as it is usually , ,

c all ed st eam P ure wat er freez es at 0 C ( 32 F ) and b oil s

° °
. . .
,

at 100 C ( 2 1 2 F ) und er stand ard pressure ( 760

° °
. .

Sinc e no oth er sub stanc e h as precisely th ese freez ing and b oiling
points th ese temp eratures serve as a means of id entifying wat er
, .

Fig 4 5
. . W at er is neces sary for t h e growt h of pl ant s Not e t h e fruit
. orch ard

growing in a d es ert b y m eans of irrigat ion .

Water is SOd istributed th at it h as b een used in

universall y
d etermining scientific s tand ard s suc h as t h e fixed p oints ,

(freezing and b oil ing points ) on t h e temperature sc al e I n t h e .

metric sy stemof weights so generally used in ch emical lab ora

,

tories t h e gram is t h e weight of a cubic c entimeter of pure

,

wat er at 4 C ( 39 T his t emperature is c h osen b ec ause

° °
.

wat er is most d ense at 4 C °

T h e d ensit y of any substance i s
.

th e wei gh t of a uni t volum e of that subs tance One cubic c enti .

meter (cc or ml or . l iter) is taken as t h e unit vo l ume of

.

s o l id s and l iquid s B ut in t h e c ase of gases t h e l iter ( 1 000 cc )

.
,
.

und er c ertain stand ard cond itions (760 mm and 0 C ) is taken

°
. .
62 WA T ER A ND I T S C OM P OSI T I ON

as t h e unit
»

vol ume T hus t h e d ensity of water is 1 gramper

.

m
,

c ub ic centim
“

eter t h e d ensity of copp er is, gra s per cubic /

c entim et er and of m erc ury is

, grams p er c ub ic centimeter .

T h e d ensity Of air is grams p er liter of oxygen ,

grams p er liter and of hyd rogen , grams ( or m ore precisely , ,

grams) per l iter .

58C h anges of s t at e in s ub st anc e s

. Wh en liquid water .

freez es into ice or b oils off as steam, we say th at it h as c h anged

it s state T h e transformation fromone t o anoth er is a purely
.

p hy sic al c h ang e T h is means , we rem

. emb er, th at d uring t h e
c h ange t h e composition of t h e substance is not altered
T h e temperature at whic h t h e c h ange fromone state t o ano th er -

takes pl ace is a very important physical property of t h e sub

st ance For inst anc e t h e t emperature at wh ic h water freez es
.
,

t o ic e is t aken as 0 on t h e c entigrad e th ermometer and is

°

marked 32 on t h e Fahrenheit scal e T h e temperature at

°
.

wh ic h sol id ic e melts t o water is al so ,

0 C Liquid water is al ways passing

°
.

t o some extent into t h e gaseous state .

T his is t h e process c all ed evaporation

and is famil iar t o everyone as t h e way
in wh ic h wet c l o th es sl owly d ry .

Since water vapor is a gas it is in ,

visibl e T h e wh ite c l oud s wh ic h are .

c all ed st eamare no t gaseou s wat er at

all b ut c onsist of very fine d rops of

water formed by t h e vap or as it sud
d enly c ool s and returns t o t h e l iquid
c ond ition .

Fig 4 6 Cl oud of s t eam, A , a ” W e may sh ow t h at gaseous wat er, or live

m
. .
”
d isappears wh en h eat ed , B .
s t ea , is inv isib le b y t h e following experi
ment . W e pl ace a lit t le wat er in a l arge
flask prov id ed wit h a o ne h ole st o pper and b ent t ub e ( Fig 4 6 A ) and h eat it
“
-
. .

'
W h en t h e wat er b oils rapid ly , a cl oud of st eam es capes from t h e t ub e
”
.

A nd y et we see t h at t h e fl ask is clear alt h ough evid ent ly full of st eam I f

.
. .

we now h ol d und er t h e jet of st eamanot h er B unsen b urner (Fig 4 6 B ) , t h e .

 4 WA TER A ND I T S C OM P OS I T I ON

t h e amount of salt wh ic h we are d issolving in a given quantity

of wat er , we reac h a point at wh ic h t h e wat er will d isso lv e no

more salt Such a sol ution is said t o b e s at urat ed Just h ow

. .

much lid is required t o make a saturated sol ution d epend s

so

o n t h e nature of t h e so l id and t h e t em p erature of t h e water .

We may prepare water so lutions of sugar copp er sulfate and , ,

saltp et er in t h e same way B ut if we t ry t o disso lve parafli n

.

wax in water we find th at i t d oes not go into s ol ution H ow

, .

ever if we use gasol ine inst ead o f wat er as t h e s o lvent , th en

, ,

we find th at wax d iss o lves b ut salt and Sugar d o no t In .

general we c all t h e sub stance whic h d o es t h e d isso lving t h e

,

solvent and t h e sub st anc e wh ic h is d isso lved t h e s ol ut e T hus .

,

so l ution so lvent so l ute

Usuall y t h e sol id b ut it may b e a liquid For
l ute is a so ,
.

instance glycerin and al c o h ol are l iquid s whic h readil y mix with

,

water Even a gas may b e dissolved in wat er

. T hus so d a .
,

wat er is water in wh ic h c arb o n dioxid e gas h as b een d issolved

Wh en th ere 1s onl y a l ittl e of t h e s ol ute in sol ution we c all it a ,

d il ut e s ol ut io n Wh en th ere is a c onsid erabl e quantity of sol ute

.

l n so l ution we c al l it a c o nc ent r at ed sol ut io n

,
.

61 . S ol ve nt C h emic ally pure water is

po wer Of wat er .

never met with in every d ay l ife and very seld om even in t h e

l ab oratory T h e reason for th is is th at water is an ex c ell ent
.

I n fac t , it is so metimes c all ed t h e universal s o lvent

“
so lv ent .
,

not b eca use it will d isso lve l arge amounts of all th ings b ut
“

b ec ause it will d issolve so me of al most every sub stanc e A .

water sol ution of a sub stance is o ften c all ed an aqueo us sol u

t ion . T h e foo d th at all p l ant s and animal s need is b rought t o
t h e cell s in sol ution, wat er ac ting as t h e c arrier .

62 . Nat ural wat er is impure . Sea water, for exampl e, h as a

l arge amount of c ommon salt and small er a mo unts of many
o th er sub s t ances d issolv ed in it Water obtained from cer
.

tain well s and springs c ontains o nly a l ittl e d issolved material .

B ut t h e purest formof natural water is rain water A nd even . .

P UR IFI CA T I ON OF WA T ER

this c ontains d ust from t h e air and dissolved gases B esid es .

t h e im purities d issolved in it natural water usually h as a great

d eal of material mec h anic ally suspend ed in it
,
“ M uddy .

water for instance c arries al o ng sol id p art icl es whic h are

”
, ,

not in sol ution T his material generally consists o f very fine

.

bits of soil .

Still ano th er sort of impurity c omes from t h e p l ant l ife in

t h e soil and from s ewage I t is c all ed organic matter
. P art .

of it diss o lv es and p art rem ains suspend ed

i n t h e wat er T his is apt t o b e a d an
.

gerons kind of im purity for l iving on it are

,

bacteria ( Fig many of wh ich c ause

.

disease For exampl e typh oid fever is

.
,

often c aught b y d rinking water int o wh ic h

t h e typ h oid b ac teria h ave found th eir way

from persons suffering with t h e disease
Bec ause wat er mad e impure by sewage is Fig B ad e ( g
magmfied ) somet mes
.

rf at l y ' “
very d angerous towns and c 1t 1es m
i

ust b e
” W e“
, f o und i n d r i nk i ng

extrem el y c areful t o get th eir supp ly from

uncontaminated sourc es If th is is impossibl e th ey h ave t o

.
,

purify carefully all t h e water wh ich is used .

63 . P urific at io n of wat er . Water may

be purified in four
ways . Only t h e first pro duces really pure water; T h e o th er
meth od s simply take out of t h e water or kill in it some of t h e
material s whic h make it unfit t o drink .

( ) D is t ill at io n T h e nonvol atil e impurities dissolved and

1 .

suspend ed in t h e wat er c an b e rem o v ed b y a proc ess c all ed di s t il

l at ion T h e water is b oil ed in a vess el whic h is so arranged th at

.

t h e st eamp asses through a c o ld tub e wh ere it turns into a liquid

again ( Fig . T his c h ange of water v apor ( steam) t o l iquid
wat er is c all ed cond ens at io n T h e apparatus in whic h it takes
.

p l ac e is c all ed a c o nd ens er T h e wat er wh ic h drops from t h e

.

end of t h e c ond enser is p ure, for t h e im purities are l eft b ehind

in t h e vessel in whic h t h e water was b oil ed Di st ill ed wat er , .

as it is c all ed , is used in t h e l ab oratory wh en we m ust h ave

66 WA T ER A ND I T S C OM P OSIT I ON

ab sol utely pure water for our experi ents I t is so eti es m . m m

used for d rinking purposes, b ut it h as a peculiar flat ”
taste -

b ecause it contains no d issolved air or solid atter Th is m .

m
unnatural taste c an b e partly re oved by bubbling air through
t h e water . A mall quantity of t h e
s

air dissolves and makes t h e water

more palatabl e .

(2 ) Fil t rat io n T h e suspend ed

.
,

or undisso lv ed , material in water

c an b e filt ered out T his is d one on
.

a l arge sc al e in cities wh ere t h e only

supply of wat er c o m es from m uddy
riv ers or sim il ar sourc es T h e water .

is all owed t o p ass sl owly th rough

M t“
b ed s of gravel and sand ( Fig .

T h e susp end ed material is c aught

b etween t h e small partic l es of t h e
sand and h eld b ac k B ut t h e water
.

whic h c o mes out o f t h e b o ttom of

t h e filter b ed still contains all t h e
dissolved impurities alth ough it is ,

i
Fg 4 . .8 C on d e nsin g t h e s t ea m f re e fr o m su s p e nd e d m att er .

from b oil ing wat er makes pure Water whic h con

W at e”
(3) B o il ing .

tains h armful bac teria may b e mad e

fit t o d ri nk by b oiling it for a sh ort wh il e T h is so c all ed .
-

pro cess of purific ation d oes no t really remove any o f t h e im

p u r it ies. I t m e re ly k ill s t h e b a c t er ia wh ic h c ause d isease .

T h ese minute forms Of pl ant l ife canno t live at t h e t empera

ture of b oil ing water Wh en th ey are d ead th ey c an of
.
, ,

c ourse, no l o nger c ause d isease . T h is meth o d o f treating water

is very effec tive from t h e stand point of h ealth B ut it is
'

g e n e r ally t O o e x p e n siv e t o b e us e d e x ce p t o n a s m a ll s c a l e in
special em ergencies .

( )
4 C h e m ic a l t r e a t m e n t of d rin k in g w at er T h e b
. a c t e ri a
may b e d estroyed by meth od s oth er than b oiling A number .

of c h em ical sub stances wh en add ed t o wat er in very small

DEC OM P OS IT I ON OF WA T ER 67

amounts kill b acteria C hl orine and hypochl orous acid

t he .

material s B ut we sh all wait with this meth od

”

are t wo such .

of purl fy ing water until we h av e s tud ied th ese sub st anc es .

I t is a meth o d th at is rapidly b ec oming very important A .

v r l ik e it i s t h e way in wh ic h nat ural running wat er

p ro cess e y
will in time purify itself T h e oxygen of t h e air d isso lves in
.

Fig 49
. . B ed s of s and und er co nc ret e roof wh ic h are us ed for fil t ering wat er .

t h e water and h emically acts on t h e b acteria d estroying

c ,

th em T his is a sl ow proc ess b ut an artificial form of it h as

.
,

b een used t o some extent for purify ing city water T h e water .

is sprayed into t h e air in fount ains thus all owing as muc h ,

Opportunity as p ossibl e for t h e ai r t o ac t c h em

_

i c ally upon it .

C OM P OSI T I ON OF WA T ER
64 . D ec o mpo sit ion of wat er . d iscussion of ch emic al
I n our
compound s we saw 1 9) th at wat er could b e d ecomposed or
“torn a art b an ”
el ec tric c urrent and th a t t h e result was
,

p , .
y
68 WA TER A ND I T S C OM P OS IT I ON

hyd rogen and oxygen T h ese we c all ed t h e constituent ele .

ments of water and t h e metho d was call ed t h e el ect rolysis of

,

water T his c h emic al c h ange we pic tured t h us :

.

water hyd rogen o xygen

We re memb er
th at we got a vo lume of hyd rogen which
, t oo ,
was d oubl e th at of t h e oxygen N ow knowing t h e d ensities .
,

of h y d rogen and o xy gen we m ight c o mpute t h e wei ghts of ,

th ese gases and so get t h e c o mposition of water in perc entages .

FOR EX A MP LE , suppose we h av e 2 l it ers

“
of h y d rogen and 1 lit er of oxyge n.

T h en we h av e 2 X or grams of h y d ro gen and gra ms of

oxy gen in or gra ms of w at er . T h at is , wat er is

or ab o ut 11 per cent h y d rogen and or ab out 8 9 per cent o xy gen .

65 . S ynt h es is of wat er b y vol ume I nstead o f an anal y sis ,.

or tearing apart , o f wat er in ord er t o find o ut o f W h at it is

*

co mposed , we c an c o mb ine t wo vo lumes

h y d rogen and
of o ne v o l ume o f o x y gen and
20 cc . Hyd g n ro e

o b serve th at wat er is pro d uc ed T his pro c

“
10 cc, O yg n
x e .

ess is c all ed synt h es is wh ic h means put ,

ting togeth er .

T he exp eri ment mb ining t h e t wo

o f co gases is
usually c arried on in a eud iomet er ( Fig . T h is
is a grad uat ed gl ass t ub e wit h t wo p l at inum wires <
fused t h rough t h e gl ass near t h e cl os ed end
’

r c ur y T h ere .

is a s p ark gap of 2 or 3 mm b et ween t h e end s of t h e .

wires . First t h e cl os ed t ub e is ent irely filled wit h

mercury T h en a mixt ure of one v olume of oxy gen
.

u
and t wo v ol mes o f h y d ro gen is prep ared b y elec t rol
0

F’g ‘ A eud mmet er y sis T h is is l ed int o t h e t ub e unt il it is ab out

m
.

gfiaggjxgfif
ffi mixed
‘ ‘y
E
r ‘

A n elect ric
t h ree fourt h s fu l
l of t hegas es
-
.

e
s p ark from an i nd uct l on corl c aus es t h e gas es t o
co mb ine . At o nc e we see a fl as h or flame in t h e gases , t he mercury sud d enl y

fall s , and t h en t h e mercury rises unt il it reach es t h e t op of t h e t ub e . T h is

s h ows t h at al l gas h as d is appeared . T h e wat er formed h as cond ens ed to a
sl igh t d ew .

I f t h e t ub e is surro und ed b y a wid er o ne t h rough wh ich m

a y l al coh ol
-
GAY -
LU S S A C S LA W OF VOLUM ES
’
9

vapor passes ( Fig t h e co nd ens at io n of t h e s t ea

.
pro d uced is pre m
vent ed I n t h is c ase it is found t h at when all t h e gases are
. ,
easured at m
t h e same t emperat ure ( ab out 130 C ) °
. and at t h e sa me pressure , a s h rinkage
of one— thi rd h as occurred ( C are must .

St eam
b e t aken t o ad j ust t h e mercury in t h e
apparat us so t h at t h e t o p of t h e mer
cury in t h e cl osed t ub e, b ot h b efore
and aft er t h e ch ange, is at t h e me
sa
H y d r o g en
mer
i

h eigh t as t h e free surface of the

cury in t h e o pen t ub e .
)
E ud i ornet er '

T his xperiment sh ows th ate

t h e vo l ume o f t h e steamis j ust

equal t o t h e v o l um e of t h e h y

d rogen In oth er word s .

,

2 v ol 1 v ol 2 v ol
‘

. . .

hy dro o xygen s eat m

gen

66 . G ay Luss ac
-
’
s Law o f Vo l
u mes . I t is astonishing .
th at
the volumes of h y drogen and
oxy gen wh ic h w ill c ombine and
form water sh ould h aVe this
sim pl e and ex ac t ratio t o eac h
oth er nam el y,2 to 1 Oth er ,
.

A s t eam jacket e d eud iomet er

gases b esid es hyd rogen and oxy Fig 51
. .
-

for comb ining h y d ro gen and o xy gen

gen have b een c areful ly s tud ied int o st eam
in t h e same way , and t h e fol
.

l owing very interesting fac t h as b een found : the vo l umes of

gas es us ed and p roduced in any chem i cal reac t io n can always
b e represented by the rati o of s mall wh o l e numb ers T his s o .

ca e ll d Law of Volumes was d iscovered by G ay -

Lussao ( Fig 52 ) .

in 180 8 .

*A my l_
-
al co h ol v ap or is b et t er t h an s t ea min t h e jacket .
 0 WA T ER A ND I T S C OM P OS I T I ON

67 . C omposit io nof wat er b y

weigh t We h ave
. found out

l ative volumes
t h e re of t h e t wo
gases th at c o pose wat er m . We
sh all now d et er ine th eir m la
re

tive weights We c an d o
. this
b y taking advantage of t h e
reac tion b etween hyd rogenand

c opp er oxid e I n this experi

.

ment we weigh t h e water ob

t ained by red ucing a known
weight of c opp er oxid e ; i e , . .

b y removing from it t h e oxy

gen . T h e l o ss in weight of
_

t h e copper oxid e gives us t h e

weight of t h e oxygen used .

T h e difference b etween t h e
weight of t h e water formed
Fi g 52 JOS E P H L o urs G A Y LU S S A C
-

d h e W el gh t of t h e oxygen
. .

( 77
1 8 A Fre nc h c h emi s t an d a n t
ph y s icis t famous for h is res earch es on giv es us t h e weight Of t h e
co m b i ni ng vol umes of gas es

m
hydrogen T h e apparatus i s
.

essentially t h e sa e as th at al ready s h own figure 41 T h e .

c opp er o xid e is red uced

in tub e A in figure 53 .

T h e water is c oll ec t ed and

weigh ed in a U— tub e 1?
c ontaining ad rying agent ,
r D y

suc h as c al cium c hl orid e .

e C
T his meth o d of d et er
O id
mining t h e c omposition
x e

o f wat er was fi rst used in

1 8 2 0 by B erz el ius . In
more recent years t h e
A merican c h emist M orl ey
( Fl g ' “ sl ng a m et h o d
Fig 53 A pparat us for finding t h e rel at ive
muc h 11ke th at already
. .

weigh t s of h y drogen and oxygen in wat er .

72 H YDR OGEN P ER OXI DE

wh ic h esc apes fro m t h e ac id ul ated water at t h e c ath o d e (nega =

tiv e po l e) is of t wo kind s h eavy and light T h e l ighter form

, .

es c apes in l arger quantities at fi rst , and t h e h eavier f orm c om es

o ff l at er I f this h eavy h yd rogen, c all ed d eut erium

. is
burned in oxygen, t h e water pro d uc ed h as a greater d ensity
th an ordinary pure water It is th erefore call ed h eavy wat er .

( a l s o d eut e r iu m o x id e) M or eov er, th is h eavy wat er d oes not

.

b oil at 1 00 C or freez e at 0 C
0
.
°
I t is apparently p oisonous t o .

p l ants if und il uted with ord inary wat er A t first h eavy water
m
.

“
was mere1y a ch emical curio sity B ut so uc h interest in it s .

properties h as b een aroused th at it c an now b e b ought in b oth

A merica and Europe for experimental researc h , eith er in a pure
st ate or m ix ed with various pro portions of ordinary wat er *
.

T h at nearly 2 00 artic l es were p ubl ish ed d uring 1 934 ab out

h eavy h y drogen and it s c ompoun d s is evid ence of t h e striking
nature of th is d isc o very .

HYDR OG EN P ER OXI DE

70 . C o mpo sit io n . T h ere is a second c omp ound of hyd rogen

and o xygen wh ich cont ains twice as m uc h oxy gen c omb ined
with t h e sa me
weight of hyd rogen as d oes wat er We h ave .

j ust seen t h at water is c omposed of 1 p art of h y drogen and

'

fl
. .

7 9 4 parts of oxy gen by weight B ut hyd rogen p erox id e is

'

c om d f 1 a t f hyd n and 2 X 7 94 a t f
‘

p o se o p r o ro ge , or p r s o .

o xy gen by weight T he p refix p er means th at this c ompound

.

c o nt ains m ore o xygen th an t h e usual h y d rogen o xid e (wat er) .

71 . P reparat io n and C ommerc ially hyd rogen

pro pert i es .

p ero x id e is mad e b y t h e ac tio n o f col d dilu t e sulfuric ac id o n

t h e c ompound b ariump eroxid e T h e l atter is a wh ite p owd er,

.

an o xid e o f b arium, muc h l ike c al c ium T h is ac tion may b e .

e xpressed as foll ows

b ariumperoxid e sul furic acid b ariumsulfat e h y d rogen p eroxid e
b arium b ari um h y d rogen
[ ]
h y d rog en
oxy g en ] sul fur
oxy gen
sul fur
o xy g en
ox y gen

* “
Wh erever h y d rogen is ment ioned in t h is b oo k, ord inary h y dro gen is meant ,

and t h e s a me ap plies t o wat er .

LA W OF M UL T I P LE P R OP OR T I ONS 73

T heb arium sulfate is a wh ite insolubl e sol id wh ich c an b e

, ,

rem oved by filtration T h e aqueous filtrate o f h y d rogen p erox

.

id e is th en concentrat ed b y evap oratio n und er red uc ed pressure .

Hy drogen p eroxid e can b e prepared as an ab sol utel y p ure

sub stance I t is a c ol orl ess sirupy l iquid
.
,
But it is diffi cult .

t o obtain b ec ause it so easil y d ecomposes into water and

oxygen :
hyd rogen perox1d e water o xygen

For medicinal purposes it is used in d il ute water l utions A

so .

3 p er
-
cent sol ution is c o mm
only so ld under t h e na me of h ydrogen
peroxid e Sinc e it sl owl y gives o ff oxy gen,
. b ottl es c ontaining
t h e sol utio n often h ave th eir corks wired in Since t h e c o m .

mercial hy drogen peroxid e solution y ields 10 times it s vol ume

of ox y gen, it is sometim es c all ed a 10 v ol ume so l ution T his
”
-
.

means th at each c ubic centimeter of t h e hy drogen peroxid e

sol ution will furnis h 1 0 c ub ic c entimet ers o f ox ygen gas A 30 = .

per c ent solution is now commerciall y ava il abl e for c h emical uses .

72 . I t s read iness in giv

Us es . ing o ff oxy gen makes h y drogen
peroxid e, l ike o z one, a strong oxi dizing agent T his is t h e
”

reason wh y it c an b e used for bl eac h ing silk, woo l , h air, feat h

ers , ivory , et c I t is al so used in medic ine as an antisep tic
.

and c l eansin g agent , alth ough it s ac tion as a germic id e h as

b een so mewhat
verestimated However b ec ause of t h e me
o .
,

c h anic al ac tion of t h e free ox ygen wh ic h it gives off it d o es ,

serve t o c l eanse an o p en w ound and t o rem o v e any foreign

material It is especially valuabl e for expelling pus and for

,

loosening d ried bl oo d y b and ages .

73 . Law of M ult ipl e P roport ions

I t h as b een found. 70 )
th at hy drogen and o xy gen unite in t h e ratio of appro ximatel y
1 t o 8 t o formwater and in t h e ratio o f 1 t o 1 6 t o formhy drogen
perox ide We no tic e th at t h e weights of oxygen wh ic h unite
.

wi t h one part of h y d rogen are in t h e ratio o f 1 t o 2 T he .

c ase of wa ter and h y d rogen p eroxid e is not p ecul iar We sh all .

l ater sh ow th at c arb on unites with oxygen t o form carb on

monoxid e, in which t h e ratio of t h e weigh t of carb on t o th at ‘
74 WA T ER A ND I T S C OM P OS I T I ON . HYDR OGEN P ER OXI DE

of o xygen is as 1 t o B ut th ere is anoth er oxid e of car

b on c all ed carb on d ioxid e in wh ich t h e ratio of t h e weight of
, ,

carb on t o th at o f t h e oxygen is as 1 t o I t will b e seen

at once th at is exa c tly t wic e T h is simpl e rel ation
sh ip is in dicated by t h e names mon(one) oxid e and d i (t wo) oxid e .

Wh enever th ere are t wo or more c ompound s containing t h e

sam e el em ents t h e weight s of t h e one el em
, ent wh ich are c om

b ined with a fixed weight of t h e o th er al ways b ear a simpl e »

rel ationsh ip t o eac h o th er ; suc h a s 2 t o 1 o r 3 t o 1 or 3 t o 2 , , .

T his generalization is known as t h e LA W OF M ULTI P LE P R O

P OR TI ONS I t was first stated in 1 8 04 by Joh n D alt on I t
. .

may b e c onveniently expressed in somewh at different language

as fo ll ows : When any two elem ents A and B com bine to form
more than one compound the weights of B which unite wi th a ,

fi xed weight of A are in the ratio of small whole numbers .

T his l aw t ogeth er with t h e Law o f D efinite C omposition is

, ,

fund amental in t h e study of c h emistry I n t h e next ch apter we . .

sh all see h ow D alton ex pl ained th ese sim

fl

pl e general iz ations b y
means of a th eory which h as mad e t h e science of ch emistry
'

possibl e .

S UM M A R Y OF C HA P T ER v1

WA T ER is one of t h e mos t important and ab und ant compounds .

W at er exist s in t h ree s tat es : s olid (ic e) , l iquid , and gas eous

( st eam) One
°
C
°
. I t freez es at 0 C . and b oil s at 1 00 . cub ic cent i

met er of wat er at C w eigh s 1 gram

4
°
. .

W at er Is an excell ent s o l vent for many sub st anc es ; resul ting

s ol ut ions are c all ed aqueous s olut ions .

NA T U R A L W A T ER S mpu
ar e i re ; t h ey cont ain d issolv ed and
suspend ed mat erial and s omet imes b ac t eria .

P U R E WA T ER c an be prepared by d is t illation. S uspend ed

mat erial may b e remov ed b y filtration D is eas e b act eriamay b e kill ed .

b y b oil ing or b y add ing s mall amount s of c ert ain ch emic al s

, .

T H E C OM P OS IT I ON of w at er c an be s h own b y analys is and b y

synt h es is . T wo vol u mes of h y d rogen unit e wit h 1 vol ume of oxygen
t o for m2 vol umes of st eam .
QUEST I ONS A ND PR OBLEM S 75

L WO
A F G A Y—LU S S A C mes of gases us ed and produced
: T h e volu
in a ch emical react ion can alway s b erepres ent ed b y t h e rat io of small
wh ol e numb ers .

C OM P OS IT I ON OF WA T ER BY WEI G H T : 1 part b y weigh t of

h yd rogenand part s b y w eigh t of oxygen . .

H YD R OG EN P ER OXIDE i s compos e d of 1 part b y weigh t of

h y d rogen and 2 X or part s b y w eigh t o f oxygen I t is a .

st rong oxid iz i
n
g agent and i s us e d for b l each ing and as an ant is ept ic .

LA W OF M ULT IP LE P R OP OR T I ONS : Wh en any t wo el e ent s m

A and B co mb ine t o formmore t h an one compound , t h e w eigh t s of B
wh ich unit e wit h a fixed weigh t of A are in t h e rat io of s mall wh ol e
m
nu b ers .

QUEST I ONS A ND P R OB LEM S

1 H ow can y ou prove t h at a cert ain col orless l iquid is wat er ?

“l ment
.

2 T h e Greeks
. c all ed wat er an e e .
”
Wh o firs t proved it t o
be a compound ?
3 . W h at pro pert ies o f wat er ake it m s at isfact ory for ( a) put t ing out

fires ? (b) Use in a h ot wat er b ot t le ?

-

4 . H ow coul d y ou d e monst rat e t h at live st eam is c ol orl ess ?

5 . N ame t wo common solvent s ot h er t h an wat er .

6 . H ow woul d y ou d est roy b act eria in wat er ?

7 . C an wat er b e purified b y freez ing ?
8 . How c ould a st ea mship in mid -
ocean Ob t ain a supply of drinking
Wfl fl ?
9 . Wh y is rain wat er t h e purest formof nat ural wat er ?
10 . W h at d o we mean b y pure wat er in referring t o nat ural wat ers ?
11 . C ompare a pure nat ural wat er wit h pure d ist ill ed wat er . ,

12 . Wh at kind of wat er d oes a ch emis t use in making up solut ions ?

13 . W h y d o we need t o d rink wat er ?
14 . W oul d it b e healt h ful t o drink dist ill ed wat er for a l ong t i m e?

15 H ow
. c oul d y ou sh ow by experi ment t h at h y drogen p eroxid e is
unst ab l e
a
:

16H ow woul d y ou proceed t o d et ermme t h e t ot al amount

. of solid s

present in a s ampl e of wat er ?

17 H ow d oes t h e import ance of wat er c ompare wit h t h at
. of ot h er
liquid s ? G ive reasons for y our answer .
76 WA TER A ND I T S C OM P OS I T I ON . H YDR OGEN P ER OXI DE

S olution i s essenti al to life

18 . . H ow d id t h e severe d rough t in o ur

c ent ral pl ains s t at es in t h e s ummer “

-
Of 1 934 t each t h e ab ov e p rinciple ?

D is t inguish b et ween t h e el ec t ric s p ark t h at ignit es t h e mixt ure

19 . of

h y d rogen and oxy gen and t h e fl ash of t h e expl osion t h at follows .

20 . D efend t h e st at ement : A man is t welve p ounds of ash es and eigh t

wat er
”
b ucket s of
'

21 G iv e t wo analy t ic al way s
. of sh owing t he mposit ion of wat er
co and
t wo way s involv ing s y nt h es is .

22 . Wh at makes h eavy wat er h eavier t h an ord inary wat er ?

23 . H ow is h eavy wat er ob t ained from ordinary wat er ?
2 4 : H ow d o t h e propert ies o f h eavy wat er co mpare wit h t h ose of ordinary
wat er
25 . H ow coul d y ou make ch emically pure wat er more palat ab le ?
>l<

One h undred lit ers of h y d rogen

26 . are b urned . C al culat e t h e
weigh t and t h e v olume ( in c c ) of t h e liquid w at er formed. .

27 h y drogen and 2 0 cc o f o xy gen are mixed in a st eam

W h en 2 0 cc . of .

j acket ed eud iomet er and ignit ed , ( a) wh at v olume of s t eam is formed ?

( b ) Wh at gas rem w m
a ins in ex c es s and h o uc h ?

C al cul at e t h e weigh t of h y d rogen which will unit e wit h 50 0

28 . cc . of

oxy gen and l eav e no free oxy gen .

29 . W h en 2 0 cc . of h y d rogen and 8 cc . o f o xy gen are pl aced in a eud i

o met er
and ignit ed , wh at Vol u me of s t ea m is form ed ? W h at gas re ains m
in excess and h ow uc h ? m
C opy and suppl y t h e missing word s : A mixt ure of 10 0 c c Of h y d rogen
30 . .

and 50 cc of oxy gen wh en expl o d ed prod uces

. c c Of s t eam, all vol um es .

b eing measured at 20 0 C and s t and ard pres sure

°
. .

T OP I C S FOR FU R T H ER S T UDY

D rinking wat er . W h at is t he source of wat er supply ? Wh at

y our
met h od s purific at io n are us ed ?
of M ake a t rip t o y our l o c al wat er w orks .

C an y ou t ell fro m
t h e appearance o f wat er wh et h er it is s afe t o d rink it ?

m
( C he i stry in I ndustry , Vol .

I mport anc e of wat er t o life W h at part d oes wat er pl ay in ch anges in

.

clim at e ? I s t h e prosperit y o f a c ount ry affec t ed b y t h e rainfall ? Wh at

h as b een d o ne in recent y ears t o s upply wat er t o arid regions ? H ow d o
y ou ac count for t h e presence of so much d is solv ed mat erial in t h e s ea, and
i l
so l t t e in riv ers , p
o nd s , and mos t l akes ?
( S cience R emaking the World ) .
R EVI EW QUES T I ONS 77

R EVIEW QUES T I ONS ON C HA P T ER S I~ VI

'

D ist inguish b et ween ( a) a mat erial and a sub st ance ; ( b ) an el ement

m
1 .

and a c o pound ; ( 0 ) a mixt ure and a compound W ould a ch emist ever .

c al l a mat erial a s ub st ance ?

2 D efine and giv e an exampl e of : ( a) oxid e ; ( b ) s pont aneous

. co m
b ust ion ; (c) al l ot ropic forms ; (d ) red uct ion ; ( e) c at aly s t .

3 . Writ e a c areful st at e ment of four fund ament al l aws wh ich we h ave

s t ud ied t h us far .

4 . D escrib e a l ab orat ory experi ment t o ill ust rat e each

‘

of t h ese l aws .

5 . C onserv at ion of M at t er applies t o t h e ch emical

S h ow h ow t h e L aw of

ch ange inv olved in b urning c oal in a s t ov e .

“
6 . N ame t h e t h ree t y pes mic al react ion wh ich h ave b een st udied
of ch e

t h us far and d es crib e b riefly an example of each .

7 C l assify t h e fol lowing as eit h er ph y sical or ch emical ch anges : ( a) t h e

.

b urning wood ; ( b ) t h e ev aporat ion Of gasoline ; (c ) t h e d issolving o f

of

sugar in wat er ; ( d ) t h e s ouring o f milk ; ( e) t h e melt ing of b ut t er ; (f) t h e

d ec ay of food ; (g) t h e expl osion of d y namit e .

8 . W h at t h ree t hings are c h aract erist ic of ev ery ch e mical ch ange ?

9 . N ame t h e pro d uct s formed wh en t h e foll owing el ement s are b urned

I n an : ( a) c arb on ; ( b ) h y d rogen ; (c) s ulfur ; (d ) c opper .

10 I s t h ere a d ifferenc e in t h e prod uct s formed wh en a s ub st ance b urns

.

in air and wh en it b urns in oxy gen?

11 . Wh at A merl can I nvent ed t h e oxy h y drogen t orch ?

12 C omp are h y d rogen peroxid e and

. o z one b y point ing o ut t he re

semb l ances and d ifferences .

13 .
(a) H ow d oes t h e weigh t of iron sul fid e
wit h t h at of t h e co mp are
iron and sulfur from wh ich it was formed ? ( b ) H ow d oes t h e int ernal
ch emic al energy of t h e iron sulfid e c ompare wit h t h at of t h e iron and sul fur
fromwh ich it was formed ?

14 . I s it c orrec t to s ay t h at t h e co mb ined weigh t of t he c arb on dioxid e

and wat er v apor formed b y t h e b urning o f a p araffin c and le is equal - t o t he
weigh t of t he c and l e b urned ? I f not , c orrect t h e s t at ement . N ame and
s t at e t h e l aw wh ich y our c orrect ed s t at e ment ill us t rat es .

15 P iles of fine c oal in st orage b ins oft en t ake fire b y s p ont aneous c om
.

b ust ion P owd ered c oal d us t s us pend ed in air oft en expl o d es wit h great
.

v iol ence wh en ignit ed b y a s p ark Expl ain t h e d ifferences b et ween t h e

.

s po nt aneous c om b us t ion and t h e expl os io n I s spont aneous comb ust ion .

o rd inarily ac c omp ani e d b y an exp l o s io n?

 78 WA T ER A ND I T S C OM P OSI T I ON . H YDR OGEN P ER OXI DE

16 . B eakers of mercury , wat er, al coh ol , and et h er are b oiling .

( D on t
’

try this .
) ( a) How d o t h eir v apor pressures co mpare ? ( 6) H ow in gen
eral d o t h eir t e m peratures c o pam
re ? 0) h at ( W is t h e vapor pressure of

each ?

17 . d is cov ered oxy gen? W h o found out wh at it s funct ion is in

Wh o
t h e process of b urning ? A nd h ow ? L av oisi er originally used 50 cub ic
inch es of air in h is experi ent m
H OW many cub ic inch es d id t h e air l ose
.

d uring t h e 1 2 d ay s t h e mercury was h eat ed ? W h at appeared meant ime

o n t h e s urface o f t h e m erc ury in t h e r et ort ? W h en t h is red sub st ance
was l at er h eat ed , h ow many c ub ic
‘

inch es of gas were given off A nd wh at

gas ?
famous 1 2 d ay experiment (s ee Fig 2 7) h e not iced
L av oisier s ’
18 . In -
.

at th e end of t en d ay s t h at t h e mercury lev el ceased t o rise in t h e b ell jar

and no furt h er red powd er formed on t h e mercury B ut h e c ont inued .

h eat ing for t wo d ay s more nev ert h eless W hy ? .

19 C avend ish d iscov er

. ed h y d rogen in 1 76 6 I n 178 1 h e b urned
.

h y d rogen in air and ob t ained a c onsid erab l e quant it y of liquid wat er ,

s uffic ient t o id ent ify it as s uch B ut h e failed t o und erst and t h e meaning
.

of his work W yh .
? W h o m a d e c l ear it s s ignific ance ?

C omp are th e element s of t h e Greeks wit h t h e ch emical el ement s

”
20 .

of t h e t ime o f L av oisier H ow d o y ou account for t h e d ifference b et ween

.

t h e point of v iew of t h e Greeks and t h at of L av ois ier ? W h o was t h e first

t o d efine a ch emical element ? Wh en?
‘

21 . Wh atme of h y drogen would weigh as much as

v ol u l it ers of
oxy gen? ( A ssume st and ard co nd it ions of t emperat ure and pressure ) .

22 M orley found in one of h is experiment s t h at

.
grams of h y d rogen
c omb ined wit h grams of oxygen C omput e t h e rat io in wh ich t h e
.

h y drogen and oxy gen unit e.

80 D A L T ON S T HEOR Y OF A T OM S A ND M OL EC UL ES
’

A law may b e d efi ned as a general s tatement b ased o n exp eri

mental facts I t is a convenient meth od o f summarizing t h e
.

results o f a l arge num b er of investigatio ns A goo d exampl e .

is B oy l e s l aw : t h e v o l ume o f a given mass of gas varies in

’

v ersely as t h e pressure up on it , if t h e t em perature 1s c onstant

(A ppend ix ) A t h eory, on t h e oth er h and , i s a sort of sci entifi c
.

guess , or hyp oth esi s , whi ch we m ake i n order t o exp lain th e facts .

We must not supp ose th at a scientifi c th eory is a wild guess ;

it is rath er a reaso nabl e exp l anatio n b ased on all t h e knowl ed ge
we h ave ab out t h e subj ec t I f t h e hyp oth esis fit s all t h e fac ts ,
.

it is c o nsid ered a satisfac tory th eory so l o ng as no new fac ts

are d isco vered whic h d isagree with it B ut if fresh fac ts are
.

found whic h w ill no t h armoniz e with t h eth eory, it must eith er

b e revised or entirely given up and anew o ne propo sed A .

th eory al ways starts with c ertain suppositions wh ich we c an .

not test exp erimentally B eginning with th ese assumptions ,

.

we reason t h at s o and so must b e true T h e more c l o sel y th ese

"

c o nc l usions fit t h e known fac t s, t h e m o re l ik el ih o o d th ere is

that t h e th eory is correc t W e c anno t, h owever, say th at t h e

.

th eory is pro ved , b ut merely t h at it is probabl y true A go o d .

exam pl e is t h e kinetic mo l ecul ar th eory , whic h , among o th er

-
,

things, expl ains t h e b eh avior o f gases wh en subj ec ted t o vary ing

pressure (A pp end ix ) A noth er is D alton s th eory of at oms
’
. .

76 W h at is D al t on s t h eory of at oms ? T h e early G reek

.
’

p h il oso p h er s ( ab o u t 3 00 B C ) b e l
. iev ed. th at all matterwas com
p os e d o i v e ry m in ut e p arti c l es w h ic h c ou ld no t b e furth er
s ubdivid ed . Th ese final b its of matter th ey c all ed at oms .

T h e anc ient thinkers however h ad suc h a meager knowl edge

, ,

of natural sci ence th at th ey c ould no t m ake use of th is th eory

t o ex pl ain natural ph enomena .

Joh n D alt on an English sch ool mast er ( Fig

,
in 1 80 8 put
.

forward a th eory very like th at of t h e G reeks b ut much more

far reac hing
-
I t expl ained for instance very simply t h e Laws
.
, ,

of D efi nit e C om position and M ultipl e P roportions Like t h e .

G reeks h e assumed th at all matter was c omposed o f v ery

,
A T OM I C WEI GH T S OF T H E ELEM ENT S 81

minute particl es whic h h e al so c all ed at oms

,
But asid e from .

m
this funda ental supposition, h is views were quite different
“
fromt h ose of t h e early ph il osoph ers His scientifi c guess is
”
.

g en era lly kno w n as t h e at om ic th eo ry a nd h as b een ad op t ed

t o expl ain t h e fac ts ab out c h emical c om pound s I t may th ere .

fore j ustly b e said t o b e t h e

most useful th eory in mod ern
c h em istry .

I n h is th eory D alton sup

p os ed t h e fo ll o win g to b e
true
( 1 ) M at t er is made up of small
part icl es c all ed at oms .

(2 ) A ll t h e at oms of a gl ven ele

ment are exact ly alike in size and
*
weigh t , b ut differ in t h ese respect s
from t h e at oms of every ot h er ele
ment .

( 3) A t oms c an unit e wit h ot h er

at o ms and h ol d t h e mby a force

c all ed c h e mical afli nit y I t is t h is .

union of at oms wh ich prod uces

C h em ical compound s °
Fig 55 O NJ H D A LT O N ( 1 76 6
(4 ) A t oms c annot b e l l ded
. .

, A n Engl is h s ch ool mas t er and c h emis t ,

and t h erefore onl y wh ole at oms wh o announc ed t h e l aw of comb ining
weigh t s and gave us t h e at omic t h eory
unit e wit h one anot h er .
.

77 . A t omic weigh t s of th e el ement s . A n atom h as so me

times b een d efined mallest ment which can
‘

as th e s p art of an ele
take part i n a ch e i cal m reacti on . B ut since ato ms are so very
sm all , we sh all not atte mpt t o use th eir ac tual weights alth ough ,

th eseare now known with great p recision . Instead we sh all

use t h e weights
relati ve ms o f t h e singl e at o of t h e el ement s .

T h e oxygen atomis taken as t h e stand ard b ecause it co mbines

with so many el ement s It s value is fix ed as 1 6
. . On th is
b asis t h e h y drogen atomis slightly more th an 1 Th e
ato m ic weigh t of an element i s the wei gh t of i ts atom as comp ared
wi th the wei gh t of one atomof oxy gen t aken as
A s t o n and o t h ers h ave recent l y proved t h at t h is is not al way s t rue
 z DA L T ON S T H EOR
’
Y OF A T OM S A ND M OL EC UL ES

T h e numb ers wh ich are now acc epted b y c h emists as repre

senting t h e atom ic weights of t h e el ement s are given in t h e
,

tab l e in t h e b ac k of this b ook I t will save time if we b ec ome

.

familiar with t h e approximate atomic weights of some of t h e

c om moner elements In this tabl e we see th at t h e atomic
. .

weight of c arb on is 1 2 and of oxygen is 1 6 T h erefore, in .

c arb on m onox id e we sh ould expec t 1 2 part s b y weight o f c ar

.

b on t o unite with 1 6 part s by weight of oxygen I n oth er .

word s, t h e ratio of c arb on t o oxygen would b e as 1

T his exac tly c orrespond s t o t h e results of t h e c h emic al analysis
of c arb on m onoxid e A ctually, t h e numb ers in t h e tabl e are
.

d erived from t h e rel ative c ombining weights of t h e el ements

in c ompound s ( C hap X VI I I ) T h ese Weights are d etermined
. .

by a very precise analysis of t h e compound s T h erefore t h e

m
.

tabl e of ato ic weights represents certain c h emic al facts in

regard t o t h e el em ents wh ic h are quit e ind epend ent o f any

th eory .

78 M ol ecul es of s ub st anc es
. We h av e already seen in .

Ch apter V th at a gas is assumed t o b e c omposed of a vast

numb er of tiny partic l es c all ed mmon
ol ecul esmIn . most co

gases suc h eac h m

as o xygen, nitrogen, and hyd rogen,
ol ecul e

is mad e up of t wo atom
,

s h eld t ogeth er in c h em ical combina

tion In t h e c ase of a compound such as c arb on monoxid e t h e
.
,

c arb on and o xygen at om s are j oined t ogeth er in groups T h ese .

groups of ato ms are mol ecul es A great num b er of such mol e

.

c ul es m ake up t h e gas wh ic h we rec ogniz e as c arb on monoxid e .

I n c ertain el ementary gases suc h as oxygen hyd rogen and

, , ,

nitrogen t h e mo l ecul e is c o mpo sed o f t wo at oms o f t h e sam

, e

el em ent I n a c ompound t h e mol ecul e is c omposed of t wo or

.

more atoms of difierent el ements For exampl e a mol ecule of .

,

water is c ompo sed of an at om of oxygen and t wo atoms of

hyd rogen T o form some id ea of t h e supposed siz e of th ese
.

mol ecules drink a gl ass of water (ab out 1 60 cc ) and realiz e

,
.

that you h ave swall owed X 10 mol ecul es of water T h ere

24 *
.

“
1 0 m an e s 1 foll o wed b y 24 z eros .
HOW I T H EL P S US T O UNDER ST A ND T H E FA C T S 3

are a few h elium and mercury vap or wh ere

c ases, suc h as ,

t h e mol ecul e of t h e gas consists of a singl e atom T h ese gases .

are said t o h ave m onat om ic molecul es .

From this discussion it is cl ear th at t h e small est p articl e of

a comp ound must c ontain at l eas t t wo atoms since a c om ,

pound c annot c onsist of l ess th an t wo el ements and th ere c an

no t b e l ess th an one atom of eac h of t h e el ements in t h e
c om pou nd W e m ay. su m u p wh at w e h av e l earned ab o ut
atoms and mol ecul es in t h e foll owing d efinitions
1 A n atom is the sm
. allest particle of an element whi ch can

take p art i n a chemi cal reacti on .

2 A molecule is the s mallest particle of an elem

. ent or co m
p ound which can normally lead a separate existence .

79 M ol ecul es in ph ysic al and c h emical ch anges

. Wh en a .

gas, such as ai r i s l iquefi ed we think of t h e mol ecul es as c om

, ,

ing l
c oser togeth er in t h e spac e th ey occupy A nd again wh en .
,

l iquid air is froz en we imagine t h e mol ecul es as c oming still

,

cl oser t ogeth er B ut in all th ree of th ese states of matter we

.

al so think of t h e mol ecul es as vib rating M oreover we l oo k .

,

upon t h e t emperature of a b o dy as ind ic ating t h e rapid ity

with whic h t h e mol ecul es are vibrating T hese changes whi ch
‘

afiect the m olecule as a wh ole we call phys ical ch anges

“
.

If h owever we disturb t h e c omposition o f t h e sub stanc e

, ,

by breaking th rough t h e force whic h united t h e atoms we ,

ro duce a c h em ic al ch ange For ex amp l e wh en we d ecom

p .
,

pose water and so obtain hyd rogen and oxygen whic h are
b oth entirely different in th eir properties from t h e original
water th at is a c h emic al c h ange
'

80 H ow D al t on s t h eory h el ps us t o und erst and experi

.
’

ment al fact s Firs t , as t o t h e fact th at c ompound s always

.

h ave a definite c omposition A ccord ing t o D alton s th eory, a

’
.

c omp ound is t h e result of a union of atom s of d ifferent el e

ments For exampl e, in carbon monoxid e each atom of car

.

b on h as c ombined with one atomof oxy gen t o forma mol ecul e

of carb on m onoxid e Since all t h e ox y gen atoms h ave exactly
.
84 DA L T ON S T HEOR Y OF A T OM S A ND M OL EC UL ES
’

t he me weigh t and t h e carb on atoms al so have each a fixed

sa

weight each mol ecul e of c arb on mo noxid e will h ave t h e same

,

p ercentage c omposition as every o th er mol ecul e A nd since .

any sampl e of carb on monoxid e is an aggregation of l ike mol e

c ul es t h e p ercent age co m
, position of t h e samp le is b ound t o b e
t h e same as th at of one mol ecul e T h e Law of D efinite C om
.

p osition states this in general term s .

S econd , as t o t h e Law of M ultipl e P roportions

One c ould .

easil y imagine th at a c arb on atommight unite with t wo at oms

of o xy gen instead of only one A n entirely different c om
.

p o u n d w o u ld re su lt I n .eac h m o l ec ul e th ere would b e one

c arb on at om and two o xygen at om s th at is th ere would b e

,

twice as muc h oxy gen c ombined with c arb on as in t h e first

c ase . C arb On d ioxid e is in fac t j ust such a sub stance
, , It .

cont ains twic e as m uc h oxygen as carb on monoxid e In t h e .

carb on d iox id e m o l ecul e th erefore we imagine th a t every

at omof carb onis united with t wo atoms of oxy gen
, ,

Finally , as t o t h e Law of C onservation of M att er We sup .

p o s e th at in a c h em ic al c h an ge t h e at om s are red istrib ut ed ,

b ut th at none are pro duced or d estroyed T h e sum o f t h e

.

atoms of t h e sub stances wh ic h take p art in a c h emic al reac tion

must equal t h e sum of t h e atoms in t h e products since none
are l o st in t h e c h ange T his simply means th at matter is
.

in d estructibl e .

81 Val ue of th e a If t h e atomic th eory is

t omic t h eory
“
. .

merely a scientific guess ab out particles which are so small

”

t h at w e c anno t see th em, wh y study t h e th eory at al l ? N ow

it is an interesting fac t th at , alth ough this h yp o th esis is more
th an a hundred years old , it h as never b een repl aced b y a
b etter one C h emists generally agree th at it d oes expl ain sat
.

isfac t orily t h e fac ts regarding c h emical c omb ination, and th at

it h as d one more th an any oth er th eory t o advanc e t h e physi
c al sc ienc es M oreo ver, in recent y ears an ab und ance of new
.

exp erim ent al evid enc e h as b een found , wh ic h we c annot h ere

d escrib e in d etail since it invo lves consid erabl e math ematical

C OM M ER C IA L USE OF A T OM I C H YDR OGEN 85

phy sic s T h e a t
. o mic th eory h as b een so s trength ened and

extend ed by all this wo rk th at scientists h ave c om e t o b elieve

in t h e existenc e of atoms and mo l ecul es with as muc h c ertainty

as i s p o ssibl e ab out things
whic h we c anno t see by d irec t
ob servation .

82 C o mmercial
. us e of

t omic
a h yd rogen . As we
s h ould expect ordinary h y ,

d rogen gas is in t h e form of

mo lecul es Dr Irving Lang . .

muir (Fig 56) h as rec ently .

discovered h owever that , ,

part Of t h e hyd rogen mol e

,

c ul es m ay b e b roken d own
( d issoc iat e d ) in t o h y d rog en C u t y G n al E l t i C o r es e er ec r c o .

at QmS
Fig 56 I R VI N G L A N G M UIR ( 1 88 1
T h l S I S d one by
. .

S e c ond A meric an t o r eceive N ob el pri e

'
z

a in t h e a s th ro u h t h e in c h emi s t ry H e is s h own read ing a

p s s g g g .

vac uum gauge

extraordinarily high t em pera
'

tures of t h e el ectric are T his breaking d own of t h e ol ecul es

. m
into atoms ab sorb s tremend ous amounts o f energy which are ,

s et free again wh en t h e hyd rogen at om s recom bine t o formh y

drogen mol ecul es
hyd rogen ml
o ecu es l energ y hyd rogen atoms
P rac tic al use h as b een mad e o f this so call ed atomic hydrogen -

t o pro duce an intensely h o t flame A streamOf hyd rogen gas .

is bl own over an el ec tric

arc , wh ere t h e dissoc iation
takes pl ace ( Fig A .

sh ort d istanc e from t h e

arc , t h e atoms c ombine

again and formmol ec ul es,
prod ucing at that sp ot a
L ever v ery h ig h t emp erat ure
A t omic h yd ro gen t orch ( b t 4 000 SLI Ch a
0
Fig 57 . . a ou .
86 DA L T ON S T HEOR Y OF A T OM S A ND M OL EC UL ES
’

fl ame of atomic hyd rogen is used in weld ing m etal s ( Fig .

B ecause of t h e reducing ac tion of a tomic hyd rogen th is new ,

type of wel ding is particul arly useful for any filmof metallic
'

o xid e whic h m ight form and so hind er t h e welding proc ess is

red uc ed t o t h e metal .

C ourt es y G eneral E l ectric C o

.

Fig 58
. . W el ding a st eel t ank b y means of at o mic h y d rogen .

S U M M A R Y OF C HA P T ER VI I

T H E A T OM I C S T R UC T UR E of mat t er w as first s ugges t ed by

earl y G re ek ph il o s oph ers .
Joh n D al t on in 18 08 us ed it as a b as is for
a t h eory wh ich expl ained th e L aws of D efinit e and M ul t ipl e P ropor
t io ns .

D A LT ON S T H EOR Y as sume s t h e fol l owing

’

( 1 ) A ll mat t er is compo s ed of at oms .

( 2 ) A ll at oms of a giv en el ement are al ike .

( 3) A t oms c an unit e wit h and h old ot h er at omsab y reason of a

forc e c all ed ch e mical affinit y .
88 D A L T ON S T H EOR Y OF A T OM S A ND M OL EC UL ES
’

11 . Wh at l aw of c h e mist ry was pred ict ed b y D al t on b y means of h is

at omic t h eory and was l at er proved b y him t o b e t rue ? S t at e it .

12 I s it p ossib le t o h av e
. -
( a) an at o m of a compound ; (b) a molecule
o f an el em ent ?

13H ow d oes t h e composit ion of a molecule

. of oxy gen d iffer from t h at
of a mol ecul e o f an oxid e ?

14 . W h at d ifference is t h ere b et ween wh at h appens t o molecules of

water wh en it is v aporized and wh en it und ergoes elect roly sis ?

15 . Wh at t h eory ac count s for t h e effect of temperat ure and pressure
upon t h e mes of gases ?
v o lu

16 H ow d oes t h e at omic t h eory expl ain t h e l a

. w of ( a) d efinit e com
posit io n ; ( b ) mul t ipl e proport io ns ; ( c) conserv at io n of mat t er ?
1 7 C opy and sup ply t h e missing word s : I n h is at omic t h eory D al t on
.

mad e t h e foll owing assump t ions : M at t er is mad e up of small p art icl es

c all ed A l l t h e at oms of a giv en are exact ly al ike in s iz e and
b ut d iffer in t h ese res pec t s from t h e at oms of ev ery el em ent .

A t oms c an unit e wit h ot h er and h ol d t h em b y a force c alle d

'

it is t h is o f at oms wh ich pro duces c h em i c al A t oms

c annot b e and t h erefore o nly at oms unit e wit h one anot h er .

a a a
t

18 . In t he hist ory of ch emis try oxygen was mad e t h e s t and ard

early

of at om ic weigh t s b ut was giv en t h e v alue of W h at woul d b e t h e

at omic weigh t o f h y d rogen in s uch a sy st em? W h at reasons can y ou see
for t h e p e ent at mi we g t
r s o c i h o f 1 6 for o xygen?

19 Sulfur dioxid e is 50 per cent sulfur and 50 per cent oxy gen Sul fur
. .

t rio xid e is 4 0 per c ent sul fur and 60 per cent oxy gen S h ow h ow t h ese .

fact s illust rat e t h e L aw of M ul t iple P roport ions .

20 . T h ere are t wo oxid es o f c arb on : one c o nt ains per cent oxy gen
and t h e oth er per cent . Sh ow t h at t h ese fact s illust rat e t h e Law of
M ul t ipl e P roport ions .
 C HA P T ER VII I

SYM BOLS , FOR M ULA S , A ND VA LENCE

Signs of al ch e mist s sy mb ols and for mul as used t o d ay writ ‘

ing formul as v al ence graph ic al repres ent at io n t ab le of

v al ences v ariab l e v al ence na ing m co mpounds .

83 . S igns used b y t h e al ch emis t s T h e origin of some of .

signs used in al ch em
_

t he y goes b ac k t o t h e ancient G reeks,

.

Wh o got th e m from t h e Egyptians . Oth ers evi d ently h ave

a Hind u origin .

T h e sun, moon , and t h e fiv e known pl anets were represented

in astrol ogy by s ymb ol s . B ecause t h e al c h emists fancied

G old Silver Iron C opper Lead T in M ercury

65
T

S un M oon M ars Venus S at urn Jupit er M erc ury

(9 3 a Q t
B
) 31+
5
Fig 59
. . Th e s igns of t h e al ch e mist s ( ab ove) and t h e sy mb ol s of t h e ast rol ogers
( b el ow) .

c ertain resembl ances b etween th ese h eavenly b o dies and t h e

metals th ey ad opted t h e astrol ogers sy mb ol s ( Fig
,
T hus
’
.

th ey gave t o gold and silver t h e signs used for t h e sun and

moon M ars t h e war god was connected in th eir mind s
.
, ,

with iron and th at metal th erefore received t h e sy mb ol of

,

shield and spear C opper was represented by t h e mirror of

.

Venus ; l ead by t h e scyth e of Saturn ; t in by t h e th rone of

, ,

Jupiter ; and mercury by Hermes s serp ent staff ,

’
.

89
 o SYM B OL S ,
FOR M ULA S , A ND VA L ENC E

C h emic al symb ol s us ed t o d ay C h e ists h av e fo und it

. m
co nvenient t o represent t h e vario us el em ents by t h e sy m b ols
wh ic h are given in t h e tabl e on t h e b ac k c o ver T h ese were .

first used b y t h e Swedish c h e ist, B erzelius ( Fig m A .

s ymb ol is usually t h e first l etter c apitalized of t h e name of

, ,

t h e el ement Exampl es are C for c arb on H for hyd rogen O for

.
, ,

o x y gen and S for sulfur

,
I n many c ases wh ere t wo or more
.
,

el em ent s have t h e same initial

l etter anoth er l etter th at is ,

pro minent in t h e name is

add ed b ut no t capital iz ed , .

Such are C I for c hl ori ne B r ,

for b romine Si for silicon

magn
, ,

and M g for m In
esiu .

o th er c ases , such as t h e met al s

known t o t h e ancients t h e ,

sym b ol is taken fromt h e Latin

name T h us C u stand s for
.

copp er ( cup rum ) Fe for iron ,

( ferrum) A g for silver (argon

,

tam) and A u for go ld ( aarum

, )
I t will b e well t o l earn t h e
sym b ol s o f t h e c ommon ele
s
ment s as we study th em .

Fig 60 JO H A N N B E R Z EL I U S
JA C OB
ymb ol
. .

( 1 779 T h e mos t d is t inguis h ed 85 . Wh at d o es a s

c h em
m od e
is t of h is d ay
m s ymb ol s
I nt ro d uc ed t h e
.
.

meanp . T h ese sy mb ol s are

not used only as sh orth and
signs for t h e el ements Eac h o ne al so stand s for an atomof t h e
.

el em ent For exampl e, t h e symb ol 0 stand s for one atom of

.

oxy gen, and t h e sy m b ol s H , N , Na, Fe represent one atom of

.

hyd rogen, nitrogen, so dium, and iron, respec tively M ore .

ex ac tly, th en, th ey are atom ic symbols and not only abb revia
tions of t h e names of t h e el ements .

We h ave al so seen th at every atom has a perfectly d efinit e

weigh t T h erefore t h e symb ol means not only t h e el e ent
. m
92 S Y M B OL S , FOR M ULA S , A ND VA L ENC E

of hydrogen wh ich consists of 2 atoms j oined togeth er On .

t h e o th er h and 2 H means 2 atoms of hyd rogen not j oined

,

togeth er ; and 2 H 2 means 2 molecul es of hydrogen eac h ,

consisting of 2 atom s j oined t ogeth er .

When we wish t o indicate more than one mol ecul e of any

sub s tance we p l ace l arge num eral s b efore t h e form
, ul a T h us .
,

2 0 2 means t wo mo l ec ul es of o xygen and 5 H 20 means five ,

mol ecules of water .

W h at fac t s d o we l earn from a formul a? I t is very

'

87 .

important that we und erstand t h e full meaning of a formul a .

For exampl e t h e formul a for sulfuri c ac1d is H 2 8 0 4 whic h

, ,

means :
(1) o nemolecul e of sulfuric acid ,

(2 ) c omposed of t wo at oms of h y d rogen , o ne at o m of sulfur , and four

at o ms of oxy gen ;
( 3) 2p art s b y weigh t o f h y d ro gen, 32 part s b y weigh t of s ul fur, and
4 X 1 6 , o r 6 4 p art s b y weigh t of o xy gen ;
(4 ) 2 82 64 , or 98 part s b y weigh t o f sulfuric a
c id .

In c h emistry we sh all o ften use t h e t ermgramformul a weigh t

of a c om pound , b y whic h we mean t h e numb er o f grams ex
pressed by t h e formul a T hus , t h e gram formul a weight of .

sulfuric acid is 98 gram s .

QUES T I ONS
1 . C an we h ave t h e formul a of an el e ment ? T he sy mb ol of a co m
ound ?
p
2 . W h at is t h e d is t inct ion b et ween a sy mb ol and a for mul a? I llus t rat e
each .
x

3 . G ive t h e mb ol of each of t h e following element s : sod ium sulfur

sy , ,

S i lic o n, manganese magnes ium mercury pot assium ph osph orus lead
, , , , , ,

and iron .

4N ame t h e element s wh ich correspond t o t h e foll owing symb ols

.

A g S n W N i A u C u A R a A s and A l
, , , , , , , , , .

5 Expl ain t h e d eriv at ion of t h e foll owing sy m

. b ol s : N a K A g A u , , , ,

and Fe .

6 . W h at is t h e d ifference b et ween Oz and 2 O

VA LENC E HEL P S US T O W R I T E C H EM I C A L FOR M UL A S 93

7 . Expl ain t h e meaning of t h e numb er t o t h e left of mula

a for , such as
2 K C l Oa .

8 St at e t h e fact s
. expressed b y t h e formul as : C uSO4 ; 3 N aC l ; 2 H 20 ;
P 4 ; and B a( OH ) 2 .

9 . Expl ain t h e use of a parent h esis in a formul a; for exampl e, C a3 ( P O4 ) 2 .

10 St at e t h e meaning of each figure and l et t er in t h e foll owing formul as

'

2 H 28 0 4 ; 1 0 H zo ; (N H 4 ) 2 8 0 4 ; F6 2 ( S O4 ) 3 ; c r2 0 7 .

88 : Val enc e h el ps us t o writ e

“
ch e mic al formul as . In o ur

study of c ompound s we sh all notice th at t h e various el ements

differ greatly from one anoth er in t h e numb er of h y d rogen
at oms with which th ey will c ombine T h is fac t is illustrated .

in t h e foll o wing c ompound s

HCl
h y d rog en c hl orid e wat er

th er word s an atom of chl orine will c omb ine with b ut

“
In o ,

one h y d rogen at o m an atom of o xy gen with two an ato m

“

, ,

o f nitrogen with three and an at om of c arb on with four

, We .

ca ll this property of an el ement it s val enc e T h e valence of an .

elem ent i s that num b er of atoms of hy drogen wi th whi ch one atom

of th e elem ent will com bine T h erefore t h e val enc e of c hl orine
.
,

is one of oxygen t wo of nitrogen three and of c arb on fo ur

, , , .

T h ere are h owever some el ements whic h will not c o mbine

, ,

with h y drogen alth ough t h ey d o comb ine with oth er el ements .

Since we c anno t measure t h e valenc e of such el ements direc tl y ,

we shall have t o d o it ind irect ly T hus l ead will not c o mbine

'

.
,

with h y drogen b ut will co mb ine with o xygen One atom of

_

l ea d unites With one atom of oxy gen and one atom of oxygen ,

unites with t wo at oms of hyd rogen T h erefore we assume that .

if l ead and hyd rogen did c ombine one atom of l ead would ,

unite with t wo at oms of h y d rogen T h erefore we say th at .

t h e val enc e of l ead is two A gain gold will not combine with
.
,

hy d rogen b ut will c omb ine with chl orine so th at one at om of

gold unites with three at oms of c hl orine B ut one atom of .

c hl orine unit es with one at om of hyd rogen T h erefore we say .

th at t h e val enc e o f gold is three .

94 SY M B OL S , FOR M UL A S , A ND VA L ENC E

We h ave al ready th at t h e atomisc h emically indivisibl e

seen .

I t foll ows th en th at the valence of an elem ent m ust always be a

whole numb er .

H o w we may pict ure val ences

89 . T h e val ences of ele .

ments d o not tell us anything about t h e reasons wh y certain

el ement s unit e and c ertain o th ers d o not T h ey merely t ell .

us t h e numb er o f h yd rogen ato ms with whic h el ements c an

co mbine Furth ermore, we d o not know in wh at way t h e
.

el ement s are ac tuall y j oined t o one anoth er B ut our rul es .

o f val ence d o t ell us h ow many ato ms will b e united in a given

c om pound We can make a pic ture of this by supposing that
.

eac h at o m h as a c ert ain num

.
b er of b ond s , or h oo ks, which
ena bl e it t o j oin with some o th er atom or atoms We are .
.

quite certain of c ourse th at t h e ac tual way in whic h atoms

, ,

are l inked is d ifferent from th at represent ed in figure 6 1 .

B ut we may use this meth o d in ord er t o visualiz e t h e con

c ep t ion o f val ence .

Wat er

A mmoni a M ar s h G as

Fig 6 1
. . D iagramrepres ent ing t h e val ence of at oms b y b ond s .

T h e accomp any ing diagrams ( Fig 6 1 ) represent such an imaginary

.

linkage of t h e at oms in h y d rogen chl orid e, wat er, ammonia, and marsh
gas . I t is ob vious t h at if cert ain el ement s unit e wit h one at omof h y d rogen,
t h ey must h av e only one b ond , or h ook ; t h eir v al ence is one Simil arly , .

ment s which
el e co mb ine wit h t wo , t h ree, and four at o ms of h y d rogen h ave
t wo, t h ree, and four b ond s resp ec t iv ely . If an el ement l ike z inc wh ich ,

h as a val ence of t wo , unit es wit h wh i ch h as a v al ence of one it

chl orine, ,

will require t wo ch l orine at oms t o l ink up wit h t h e t wo b ond s of a single

z inc at om T he
. formul a will t h erefore b e a l z .

In a l at er c h ap t er ( XIV) we sh all d iscuss, in an el ementary

way , t h e el ec tron th eory of t h e structure of t h e atomand th en
 6 S YM B OL S , FOR M ULA S , A ND VA L ENC E

o f reac tions Such groups of el ements act very much like

.

a S ingl e el ement and are c alled radical s R ad ical s h ave .

val ences j ust as el ements d o El ements or groups which .

h ave t h e val ence of one are call ed unival ent ; if th ey h ave a

val enc e of t wo b ival ent , et c
, .

91 Variab l e val ence

. I t will b e seen in t h e val ence tabl e
.

th at certain el ements h ave more th an One val ence Suc h .

fac ts complicate t h e general rul es of v al ence A l most all

,

el em ents form a certain num b er of compound s in whic h th ey

h ave an unusual val ence For exampl e, t he val ence of carb on
.

is al most with out excep tion four, as in carb on d io xid e ( 0 0 2 )

( oxygen is bival ent, and th ere are t wo oxygen atoms ) B ut .

in c arb on monoxid e ( C O) t h e val enc e is t wo Suc h exceptions .

are rare and must simply b e l earned as th ey o c cur .

A few el ements, l ike iron, form two series of c ompound s, in

whic h t h e el ement h as d ifferent val enc es For examp l e, we
m
.

h ave a numb er of c o pound s of iron c all ed ferrous c ompound s,

'

in whic h iron h as a val ence of t wo Ot h ers are c all ed ferric

.

com p ound s , in wh ic h iron h as a val ence of t h ree Suc h el e .

ments are said t o h ave a variabl e val ence .

92 H o w we use val ence in writ ing formul as

. Let us now .

see h ow we c an app l y t h e inform ation in t h e val ence tabl e t o

t h e writing of formul as A t this p oint we sh all discuss only
.

t wo ca ses :

1 Wh en t wo el ement s ( or radic al s) whic h h ave t h e same

.

val enc e un it e t o form a compound , th ey will c ombine at om

for atom, as sh own in t h e foll owing exampl es Note th at .

val enc es are indicated by t h e and Signs pl ac ed ab ov e

and t o t h eright of t he s ymb ol s

Hydrogen chl oride H Cl
+ Iron ( ferrous) sulfid s e Fe+ + ‘

S odiumchl orid e Na C l
+ ‘

m
A l u inumph osph ate A 1H + P O4
C opper oxid e Cu O
+ + Sli i n a i
bd e Si+ * H C
-

c o c r

2 . Wh en t wo l ments (or radic al s) which h ave different

ee

val enc es unite t o forma compound th ey will combine so th at

,
.
H OW T O L EAR N T HE VA LENCES OF T HE EL EM ENT S

the total valences f one element equal the t otal valences of the
o

For exampl e water is H 2 O

“
other
+
Since t h e val ence of
'

.
,

hydrogen is one and th at of oxygen is t wo we must take 2 atoms

-

of hyd rogen as ind icated by t h e sub script 2 writt en aft er t h e H .

—
A gain al uminum c hl orid e is
, 3 b ec ause al uminum h as
a val enc e of three and c hl ori ne a val ence of o ne C arb on .

“
dioxid e is C H H Of f B ecause c arb on h as aval ence of four and
' ' '

oxy gen of t wo we m ust h ave 2 atoms of oxygen for eac h atom

,

of c arb on A l uminumoxid e is A 12
.
H + 03 Sinc e t h e val ence
of al um inumis three and of oxygen t wo and since t h e small est ,

numb er which is d ivisibl e b y 3 and 2 is 6 we must have t wo ,

atoms of al uminum t o make it s to tal val ence S IX and th ree ,

atoms of oxygen or A 12 0 3 ,
.

In writing formulas of mol ecul es mad e up o f t wo atoms

or rad ic al s of unequal val enc e we Sh all find t h e foll owing ,

R ULE FOR VA LENCE h elpful

Valence x numb er of atoms (or radical s) in t h e case of one
el em ent ( or radic al ) equals valence X num ber of atoms ( or
radical s) in t h e c ase of t h e o th er .

93
. H o w t o l earn t h e I t will save
val enc es of th e el e ment s .

time t o l earn at once t h e tabl e of val ences of t h e common

el em ents and radical s T h en, t o o, it is very imp ortant t o
.

learn the valence of each element or radical as we study i t, and

always to use i t in wri ting form ulas We S h all al so find it good .

prac tic e t o ch ec k up every formul a th at we write in ord er t o

make sure that t h e total val enc es of t h e t wo halves of t h e
'

c om pound b al ance T hus, if we write zinc nitrate Z nN Oa

.

and th en mark t h e val ences iwe see a t once th at

t h e c orrec t formul a must b e Zn( NO I t will often h el p if we
c an re memb er t h e formul a of at l east one simpl e c ompound
of eac h el em ent For exampl e Suppose we want t h e val enc e
.
,

of m erc ury P erh ap s we rec all th at t h e formul a of t h e red

'

o xid e o f m ercury is HgO T h en if we know th at t h e val ence.

,

of oxygen is t wo t h e v al ence of m ercury in this c om

, pound
must also b e t wo .
 8 S YM B OL S , FOR M ULA S , A ND VA L ENCE

94 H ow we name mpound s
wh ic h is A mpound ’

. co . co

mad e up of t wo el ements or of an el ement and a radic al is

call ed a b ina ry c o m pound For th ese compound s t h e suffix
.

-
id e is used ; for exampl e, z inc oxid e, Z nO l ead sulfid e, P b s
ammoniumsulfid e, ( N H 4) 2 8 .

T h e c ompound s whic h are ad e up of three el ements one of m

which is oxy gen usual ly end with at e or it e T h e it e c om - -
.
-

pound h as l ess oxygen than t h e c orresp ond ing at e c omp ound -

.

Exampl es are so dium sulfate, Naa8 0 4, and so dium sulfit e,

N3 2 8 0 3 .

T h e endings ous and ic are used for c o mp o und s in wh ic h

- -

t h e metal h as t wo val enc es ous for t h e l o wer val ence and -

-
ic for t h e h igh er val enc e“ Exampl es are ferrous c hl orid e,
FeC l z, and ferri c c hl ori d e, FeC l 3 .

T h e prefixes mono, di ( or bi ) , tri , tetra, and p ent ind ic ate one, t wo ,

th ree, four, and fiv e atoms of t h e el ement T hus, c arb on mon .

o xid e, C C ; c arb on d io xid e, C Oz p h osp h orus trio xid e, P 2 0 3 ;

c arb on t etrac hl orid e 0 0 14 ; and p h osp h orus p ent oxid e, P 2 0 5
, .

95 . T ro ub l es wit h val enc e . T o t h e b egi nner it d oubtl ess

seems a hard task t o l earn t h e val enc es of t h e c ommon el ements
and t o use th emcorrec tly in writing t h e formul as of c omp ound s
_
.

B ut after a l ittl e prac t ice it will b ec ome easy alth ough h e ,

must always b eware of c ertain pitfall s I t is for instanc e .

, ,

en ire t possibl e t o write, ac c ord ing t o t h e rul es of val enc e,

ly
m m
t h e for ul as o f c o p ound s w hic h h app en not t o exist For .

m
exa pl e, th ere is no o xid e o f a oniu a l th ough it s for ul a mm m m
b e written On t h e o th er h and , we sh all l ater c ome up on
'

c an .

c om p o un d s wh ic h d o no t seem t o fit t h e rul es S uc h are .

c al cium c arb id e, C aC z ; magnetite, Feg0 4 ; and ac etyl ene,

C aH I n sh ort, we must not forget th at fo rmul as really
represent ex peri m ental fac ts ab out real sub st anc es .

QUE S T I ONS
1 . Writ e t h e for mula for each of t h e followin ? g ( a) c al c iu m oxide
( b) z inc oxid e ; (c ) mercuric oxide ; (d ) ammonium h y droxid e ; ( e) al umi
numh y droxide .
 0b S YM B OL S , FOR M ULA S , A ND VA LENC E

7 . Name t h e following oxid es of iron : FeO and Fe2 0 3.

8 . W rit e t h e na mes of t he
in t h e first group (a) , and co mpound s list ed
writ e t h e formul as of t h e compound s lis t ed in t h e second group ( b ) ( a) C d S ;
H 3P O4 ; C OC l z ; P 50 14 ; W o g ; s ( b ) A lumi .

num sulfid e ; t in (s t annic ) c hl orid e ; z irc oniu m oxid e ; ch ro mium sulfat e

ferric nit rat e .

9 . Writ e mul as of t h e following compounds :

t h e for (a) magnesium
nit rid e ; (b ) c al cium oxid e ; (0 ) aluminum fluorid e ; ( d) so d ium s ul fat e ;

and (e) mercuric oxide .

10 . A ssuming t h at c arb o n and S ilicon are t et rav alent writ e t h e formul as ,

for ( a) silicon d ioxid e (s and ) ; ( b ) carb o n t et rach l orid e

( c) S ilicon c arb id e ( carb orund um) (d ) cal cium c arb id e ; (e) S ilicon fluorid e .

1 1 N ame each of t h e following compound s : ( a) t h e pot assium s al t of

.

t ungst ic acid ; ( b ) t h e so d ium s al t of ch lorpl at inic ac id ; ( c) t h e po t ass ium

s al t of t ell urous ac id ; (d ) a c om po und of cal cium and sel enium o nl y
“
.

12 . G iv en t h e v al ence o f B as t wo , d erive t h e prob ab le v alenc es of A ,

C , and D from t h e m
foll owing for ul as : A 2 3 3 ; B 2 0 ; B sD z W h at Woul d .

b e t h e formul a of a compound of A w it h C ? Of C wit h D ?

13 C opy t h e foll owing t ab le and fill
. in t h e b l ank s p aces wit h t h e
formul as of t h e c ompound s as ind icat ed .

H
iggg
x '

NI T R A I
'‘
ES S UL A F TE S
(N ( SOC
( OH )
‘

S od ium, N a +
N aC l N a2 0 N aoH N aN o , Na so z i N aar o i

P ot assium, K +

A mmonium, H
( N 4) +

C al cium, Ca + +

L ead , Pb + +

M agnesium M g ,
+ +

Z inc , Z n+ +

I ron ( ferrous ) Fe,

+ +

I ron (ferric ) ,

A luminum A l i ' “
+
r
,

T in, Sn+
 C HA P T ER IX

CHEM ICAL EQUA T I ONS A ND C OM P UTA TI ONS

Uses of mic al
ch e equat ions h ow t o writ e equat ions five
st eps wh at an equat ion d oes not S h ow review equat ions of

react ions s t ud ied .

Four t y pes of react ions .

I mp ort ance of comput at ions formul aweigh t s of c ompound s

percent age c omp osit ion weigh t rel at ions in equat ions prob
lems inv olvi ng weigh t only S ignific ant figures fiv e st eps .

96 .W h y d o es t h e c h emis t writ e equat ions ? T h e prl ncipal

use whic h t h e c h emist makes of sy mb o l s and formul as is in
writing in a sh ortened and p rec is e form a l arge amount o f .

information ab out c h emi c al c h anges or reac tions Sinc e mat ,

.

t er is ind estruc tibl e (Law of C onservation of M atter) h e re pro ,

s ents th ese ch anges or r eacti ons as equati o ns

,
T h ere is t h e
,
.

sam e am o unt o f eac h el em ent aft er t h e c h ange as b efore We .

h ave already written a few word equations ; we sh all now -

transl ate t h ern int o formulas

'

t .

97 . H o w t o writ e tantly b ear in

equat io ns . We must c ons

mind that c h emical equations are b ased on facts which h ave ,

b een found out through exp eri ments T h ey represent c h emi .

c al reac tions or ch anges wh ic h ac tuall y o cc ur

.

, ,
A S it is quit e .

impossibl e t o rememb er all t h e equations y ou will need we ,

S hall t ry in this c h apt er t o sh ow y ou t h e m ech ani cal process

of writing equations so th at y ou m ay work th em out for y our

self ; We sh all take for illustration th ose reac tions which y ou
h ave al ready studied In this work it is well t o rememb er
.

th at a chemical equati on is either all right or all wrong. .

T h e symb ol s and formul as o f al l t h e materi als undergoing

change are pl ac ed on t h e left ; th ose of t h e new p roducts result

1ng fro mt h e c h ange on t h e ri ght ; t h e arrow m

,
eans form s o r gi ves ;

101
 02 C HEM I C A L EQUA T I ONS A ND C OM P U T A T I ONS

For xampl e t h e union of iron and

e ,
su lfur t o form iron sulfid e
is expressed thus
Fe S FeS
‘

T h e b urning of magnes1ummoxy gen m

i ht at fi
g rs t b e expressed
thus
Mg 0 2 M gO
B ut this t wrong b ecause we h ave two atoms of oxy
equa ion is

en on t h e l eft and only one at om on t h e right sid e T h i

g s .

would indicate th at some o f t h e o xy gen h ad b een l ost T he

'

“
.

very word equation means th at th ere must b e j ust as many

”

atoms of eac h el ement after t h e c h ange ( on t h e right ) as

.
“
b efore (on t h e l eft ) W e c an b al ance t h e equation as it is ”
,

c all ed th us
,

2 Mg 02 2 M gO

T hat is, every atom on t h e l e ft h and sid e 1s accounted for on

-

t h e right h and sid e o f t h e equation

-
.

I n d ec omp osing p ot assium c hl orate b y h eat , we might write

t h e equation at first th us

and th en b al ance it th us

Froma study of t h e ab ove it wil l b e seen th at th ese equations

are not al gebraic T h ey represent c h emic al reac tio ns which
.

actually take pl ace .

B efore we c an write an equation we must knOW '

( 1) that the reaction takes p lace

(2 ) what subs tances enter i nto the reaction
( 3) what th e products are and
(4 ) th eform ulas of all th e substances i nvolved .

98 . S ummary of t h e nec e s s ary s t eps . I n making a ch emical

equa ion
t th ere are five step s :
( 1 ) Write on the left t h e formul a of
. eac h b tanc e taking
su s

part in t h e reac tion .

1 04 C H EM I C A L EQUA T I ONS A ND C OM P U T A T I ONS

T he t ells not hing ab out t h e ph y sic al st at es of t h e s ub st ances

equat ion

concerned ; t h at is , wh et h er t h ey are s olid s , liquid s , or ga s es A gain, t h e .

equat ion d oes no t t ell h ow l ong t h e act ion t akes al t h ough t h is fact is of great

econo m m
ic i p ort ance .

I n general , t h e material s whic h are present b ut whic h und ergo

no c h ange are not represented in t h e equation Suc h are t h e .

water used as a s olvent and t h e various c atalysts Finally, .

we d o not as a rul e t ry t o S h ow t h e amount of h eat wh ic h is

,

e o v lved in t h e c h emical reac tion . For xampl e

e ,

C + Oz
sh ows th at carb on unites with o xygen t o formc arb on d ioxid e .

B ut it d oes not tell us h ow much heat i s produced a piec e of ,

information whic h is most important for t h e industrial c h emist .

10 1 . Fa iliarm r eac t io ns in equat ion form . We sh all now

write t h e c h emic al equations for t h e reactions wh ic h we h av e
s tud ied up t o th is p oint , and wh ic h we h av e h ith ert o sum

mariz ed in W d
or s W se h al l dc well to m
!
. aster th orough ly all
.

th ese equati ons .

When water is el ectrolyz ed , it is d ec omposed into free hydro

gen and oxygen T h e equation for this is
.

2 H 20 —* 2 H2 + 0 2

We h ave t o t ake t wo molecules of wat er in ord er t o provid e one molecule

of oxy gen wh ich consist s of t wo at om
, s T h e formul a for free oxy gen is 0 2
. .

Wh en mercury o xid e is h eated , o xygen and mercury resu lt .

T h e equation is
2 HgO 2 Hg 0 2

A gain, we t ake t wo mol ecules of mercury oxid e s o t h at we may h ave

enough oxy gen at om s t o form a mol ecul e T h e mercury formed is a liquid ;
.

and we h ave reason t o b elieve t h at t h e at oms in met als are oft en not unit ed
in mol ecules H ence we represent t h em as in t h is c ase : 2 H g not H go,
.

t wo singl e at o ms mercury
of . We also t h ink t h at a molecule of mercury
is composed of one at om .

102 . Four t ypes of reac t io ns 1

( ) D irec t co
. b ina t io n, o r s y n m
t h es is . m
A noth er typ e o f c h e ic al reac tion, wh ic h is t h e reverse
of S i mpl e d ecomposition is I n th is t yp e we tart
'

, synt h esis . s
FOUR T YP ES OF R EA C TI ONS 05 ’

with t wo or more sub stanc es and b uild up a compound T he .

foll owing equations are t h e synth eses involving o xygen wh ich

we have th us far consid ered

2 H2 + 02 —
+ 2 H 0
—
2

C + Oz > C OZ
2 C + 02 -
2 CO

P + 50 2
—* 2 P 20 5

T h ese equat ions repr ent t he ch anges wh ich t ook pl ace wh en mercury ,
h y d rogen, c arb on, and h orus were h eat ed in cont act wit h pure oxy gen
or air . T t h e b urning of c arb on in an ins ufficient s upply

of oxy gen xid e ; and t h en t h e b urning of c arb on

mo noxid e t o c ar
( 2 ) Simpl e d ec T his typ e of c h emical c h ange
involv es onl y one breaks d own b y a c h emic al
reac tion int o t wo or m ore sim pl er sub stanc es Suc h a reac tion .

is c all ed a s impl e d ecompo sit ion T h e d ec ompo sition o f water

.

i nto h y d rogen and o xygen is an ex am pl e of this type of c h em

ical reac tion T h e d ec omp o sition b y h eat o f mercuric oxid e
.

and of po tassiumc hl orate are al s o exampl es

2 HgO -
2 Hg + 0 2
2 KC l Os —> 2 KCI + 3 0 2
T h e d ec omposition o f hy d rogen p eroxid e is anoth er exampl e ‘

2 H zo z “3 9 “2 H 20 ‘

i 0
‘

( ) S im
3 pl e repl ace ment , or s ub s titution . T he meth od s Of
prepari ng hyd rogen ( exc ep t t h e electroly sis of water) are ‘

m
exa pl es of a typ e o f c h emic al reac tion c all ed repl ac ement .

In this type of reac tion one el ement takes t h e pl ac e o f so me

.

o th er el ement or el ement s in a c om p ound .

T h us , wh en z inc or magnesium act s on h y d roch l oric ac id or sul furic

acid , t h e met al repl aces t h e h y d ro gen :

Z I] 2 H O] ZH C l z H2
zn mo 4 znso t H2
Mg 2 H0 ] NI n H2
106 C H EM I C A L EQUA T I ONS A ND C OM P U T A T I ONS

W hen st eam is passed ov er h ot iron, t h e iron repl aces t h e h y d rogen of

t h e wat er, form ing t h e m

agnet ic oxid e of iron ( Feg0 4)

3 F€ + 4 H 20 4 Fe 30 4 + 4 H2
N OTE rm
T h e fo ul a of t h e iron oxid e pro d uced in t h is equat ion is t h e
resul t of experi ment and c oul d not h ave b een predict ed b y any v al ence rules .

W h en met allic sod iu m or c al ciu m 1S pl ac ed in wat er, t h e met al repl ac es

h alf of t h e h y d rogen of t h e wat er and forms s od iu m h y d roxid e ( N aoH ) or

c al ciumh y d roxid e

2 Na + 2 H 20 -
2 NaOH H2
Ca 2 H 20 C a( OH ) 2 H2
N OTE . In o rd er t o b e ab l e t o t h e h y d ro gen in t h e
rep res ent mol ecul ar s t at e

( H 2) , We must prefix t h e c oefll c ient 2 in s ev eral p l ac es

‘
.

Wh en o ne e e l ment of a co mpound
l aces anoth er t h e rep ,

numb er of atoms of t h e el ements co ncerned must b e suc h th at

t h e sumof t h e val enc es of t h e repl ac ing el ement must equal t h e
sumof t h e val ences of t h e el em ent repl ac ed T hus wh en z inc .
,

repl aces h y d rogen in h y d roc hl ori c ac id eac h at om of z inc re ,

pl ac es t wo atoms of hyd rogen S inc e t h e val ence of z inc is t wo

,

and t h e val ence of hyd rogen o ne :

Zn 2 HCl a lz Hz l
Wh en aluminumreacts with h y d roc hloric acid , th ree atoms of
hydrogen appear for ev ery at omof al um inum, smce t h e val enc e
of t h e m
“

etal is th ree

2 Al 6 HClf
2 A lCl 3 3 Hz l
Since t h e hy drogen is a gas t h at p asses off, We usually add aft er t h e H z t h e
upw ard p oirit ing arrow 1
-
.

T his use of t h e rul es of v al ence will b e found h el pful in writing

repl acem ent reac tio ns .

(4 ) D oub l e replacement , or d ecompos ition P rob ably t h e .

c om monest ty pe of ch emic al reaction is th at in which t wo com

pound s interac t and pro d uc e t wo o th er c o mpound s T his is .

som etim es c all ed d oub l e d ecom p o s it io n b e c a us e e ac h c o m

p ou n d a pp a rently b reak s u p i nt o t w o p ar t s , ea c h o f which
unites with a d ifferent p art o f t h e oth er c ompound .
108 C H EM I C A L EQUA T I ONS A ND C OM P U T A TI ONS

13 W h en iron is b urned in oxy gen t h e prod uc t is t h e magnet ic oxid e

.
,

of iron ( Fego 4 ) W rit e t h e equat ion

. .

14 ( a) W h en c arb on d ioxid e is b ub b l ed t h rough limewat er

.

c arb o nic ac id ( H 2 0 0 3) is form ed W rit e t h e equat ion ( b ) T h e c arb onic

. .

acid t h en react s wit h t h e c al c iu mh y d roxid e t o for mc al ciumcar

b o nat e ( C aC Oa) and wat er . W rit e t h is equat io n .

15 . B al ance t h e foll owing equat ions

( a) A g oo Ag 0 2

( )
C C
l 02 " “
CO
(d ) Na 02 N azo z
( e) N azo z H 20 N aOH 0 2

16 . Why in b al ancing an equat io n may y ou increas e t h e nu b er of m

mol ecules used or pro d uced b ut may nev er c h ange t he s ub s crip t numerals

of any c orrec t form ul a?

17 . B al ance t h e equat io n in each c as e

( o) f H 20 2 H 20 0 2

b
( ) K i 02
““
K 20 2
( c) P 0 12 P Cls
(d ) A I 11 2 50 4 A 12 ( S O4 ) 3 H2
( e) H as A s 0 13 H Cl A ss
18 . W rit e t h e na me of each s ub st ance und er t h e for mul as used in t h e
j us t
‘

equat ions giv en .

19 . Writ e t h e b al anced equat ions for t h e ch e mical reac t ion inv olved in
( a) P riest ley s d is cov ery of oxy gen
’
.

( b ) L av oisier s cl assic experiment wit h mercury and air ( t h is react ion is

’

reversib l e) .

(c) C avend ish s d is covery of h y drogen (iron and acid )

’
.

(d ) M orley s met h o d of d et ermining t h e composit ion of wat er

’
.

( e) B erz elius met h o d of d et ermining t h e composit ion of wat er

’
.

20 . W rit e
a b al anced equat io n ( using for ul as t h rough out ) for t h e m
reac t io n t aking pl ace in ( a) t h e o z o ne generat or ; ( b ) t h e oxy h y d rogen b l ow

pi pe ; ( ) 0 t h e at o mic h y d rogen b l owt orch

-
.

C HEM I C A L C A LC U LA T I ONS

1 03 . I mport anc e t o ind us t ry

h emic al c al c ul at ions T o of c .

t h e ind ustrial c h emist t h e c h emic al equation is of t h e greatest

importanc e B y means of it h e cal cul ates j ust h ow muc h ma
.

t erial h e need s for a given reac tion ( Fig 6 2 ) and h ow l arge .

an amount of pro d uc t h e may h ope t o get I n ac tual practice .

,
I MP OR T A NC E T O I NDU S T R Y 109

h owever h e very seld om gets t h e full amount of t h e pro duct

,

as c al cul ated from t h e equation T h erefore h e c omp utes t h e ”

efficiency of h is industrial pro cess i e wh at frac tion t he ac tual , . .

,

yield is of t h e th eoretical yield as c omputed from t h e c h emic al

equation T h ese c omputations are all b ased on t h e c h emic al
.

equations of t h e reac tions

and require onl y t h e simpl est

arith metic al work T h ey c an .

b e c l assified into several

typical c ases .

Type 1 .
Mol ecular weigh t
O
_
f a mp o
cou n d f ro m i t s

m l A f rm ul a
f o r u a . o repre

s en ts not onl y t h e name of t h e

co mp d b ut also t h e weight
oun

of a m ol ecul e referred t o t h e

oxygen at omas 1 6 T o c om .

pute t h e mol ecul ar weight of

a co mpound fromIt s form ul a Fig 6 2 W eigh ing is an es s ent ial part of
m
. .

c r ub b er m
,
d uS t ry
.

We h av e onl y t o ad d t h e
'

B ut since t h e atomic
i

weights of all t h e at oms in t h e mol ecul e .

weights are o nly relat iv e weights t h e mol ecul ar weight must b e

‘

rel ativ e al so .

FOR EX A MP LE , t he molecul ar weigh t of cal cium c arb onat e ( C aC Oa) is

40 12 (16 X or 1 00 . A gain, t h e mol ecul ar weigh t of c opper
sul fat e ( C uSO4) is 32 (16 X or

A NOTHER LE Find t h e mol ecul ar weigh t

E XA M P of gy psu m ( C asO4
ml
.

2 H 20 ) N ow gy psumis cry st allized c al cium sulfat e

.
, and each o ecul e of

c al cium sul fat e c arries al ong t wo mol ecul es o f wat er . T h is s o c all ed

-
water
of hyd ration or of cry st alliz at ion is c h emic ally unit ed wit h t h e c al cium Sul

fat e, as is indic at ed b y t h e d ot in t h e formul a, wh ich means in t h is pl ace

p lus . T h e mol ecul ar weigh t t h en of C aS O4 2 H 20 is 4 0 32 ( 16 X 4 )
or 1 72

P erh ap s a b etter termfor mol ecul ar weight is formul a weight

because it more accurately d escrib es wh at it actually is .

Type 2 P erc entage co pos itio n of a co pound fro

. its m m m
formula If t h e c h e ist knows t h e for ul a of a c o pound
. m m m
1 10 C HEM I C A L EQUA T I ONS A ND C OM P U TA TI ONS

and h as a tabl e mic weights h e can easily work

of ato , o ut t he
p erc ent age of eac h el em ent pres ent in t h e c o mpound .

FOR h e wish es t o find t h e percent age comp osit ion of c al cium

E X A MP LE ,

c arb onat e ( C aC 0 3) T h e at omic weigh t Of cal cium is 4 0 , of c arb on is 12 ,

.

and of oxy gen is 1 6 ; 40 12 ( 1 6 X 3) makes t h e formul a weigh t 1 00 .

T h erefore t h e c al cium c arb onat e cont ains —4—

0
or 4 0 er cent c al ciu 1 0 0 , p . m ,

prob l em
4 8
l
i g % , 12 per cent c arb on, and 1 5 3 , or 4 8 per
or
4
c ent ox gen
y . T h is
is esp ecially easy b ec aus e t h e for ul a weigh t is m equal t o 1 00 .

A NOT HER E XA M P LE . Find t he percent age c o p osit io m

n of p ot assiu m
c h l orat e ( K C lo g) . T h e at omic m
weigh t of pot assiu is 39, of ch l orine
and of o xy gen 16 . T h en t h e formul a weigh t is 39 ( 16 X or

T h erefore p ot assium ch l orat e cont ains

or p ot assiu m
,

or chl orine, and

or oxy gen

C HECK T ot al is
.

S T I LL A NOT H ER E X A MP LE . H ow much met allic

b e got froma copper c an

t on (2 000 lb s ) of crys t alliz ed copp er sul fat e ?

. Given t h e formul a of c opp er
sul fat e c ry st al s as C uS Oa 5 H 2 0 T h e formul a weigh t of t h is comp ound
.

is 32 (16 X 4) 4 or 4

T h e p ercent age of co pper is or p er cent , and t h e

weigh t of copp er in a t on of c opper s ulfat e cry st al s is X 2 0 00 , or 490 lb s .

I n general , t o find t h e p ercentage c o mp osition of a c o m

pound from it s formul a, first c al cul ate t h e fo rmula weight,
th en d ivid e t h e at oml c weight of eac h el ement by th is formula
weight , and express t h e quotient as a d ecimal Keep th ree .

T h e first t wo d ecimal s express t h e

.

S ignifi c ant figures

percentage .

Type 3 P ro b l ems.invo l ving weigh t o nly FOR EXA MP LE, .

wh at weight of iron will b e j ust enough t o unite with 1 0 gra s m

of su lfur to formiron sulfid e (Fes)
If more t h an o ne at o m of any e lement appears in t h e formul a, use t h e weigh t
of all t h e at o ms of t h e el ement in t h e mo lec ule .
11 2 C H EM I c A L EQUA T I ONS A ND C OM P U T A T I ONS

104 . met h o d of at t ack We know th at 32 grams

A no t h er .

o f s ulfur y ield 8 8 g ram s o f iro n s ulfid e ( FeS ) wh en pro perly

‘

co m b ined with s uffi cient iron T h en 1 gra m of sulfur would

. .

yield — — of 88 grams of iron sulfid e and 1 0 grams of sulfur would

1
3 2 ,

32
T h e arithmetical c o mputation amounts t o t h e same as th at
given ab ove, b ut t h e meth o d of reasoni ng 1s p erh aps more d irec t .

10 5 Quant it at ive meaning of equat ions A s we h ave seen

. .
,

an equation wh en properly b al anc ed gives us a goo d d eal

of val uabl e inform ation I t tell s us wh at sub stances reac t
.

and Wh at t h e pro d uc ts are I t l ikewise gives us t h e numb er

.

of m o l ecul es of eac h sub st anc e inv olved A nd fi nally by using .

,

the form
'

ula weigh ts we learn th e relati ve wei ghts of the difierent

,

subs tances in th e equati on .

FOR E XA MP LE , in t h e equat ion for preparing oxy gen b y h eat ing p ot assium
ch l orat e, we may com put e t h e rel at ive Weigh t s of p o t as s iumc hl orat e, p ot as

siumchl orid e , and oxy gen t h us :

2 K 0 10 3 2 KCl 3 Oz
(2 X (2 X ( 3 X 32 )
2 45 1 49 96

u
T h e form l a weigh t o f each mol ecul e may b e found b y adding t h e at omic
weigh t s of t h e el ement s inv olved
formul a w t K C 10 3
. of 39 ( 1 6 X 3)
formul a wt o f K C l . 39
formula wt of Oz . 2 X 16 32

Sinc e th ere are t wo mol ecules of potassium chl orate and of

p o t assium c hl orid e in t h e equation, w e m ultiply th eir f ormul a
weights b y t wo A nd as th ere are th ree mol ecul es of oxygen,
.

we multiply it s formul a weight by th ree .

We can now read this equation as foll ows : parts by

wei ght of p otassiumchlorate gi ve p arts by wei ght of potassium
chlori de and 96 p arts by wei gh t of oxygen .

1 06 . T h e atomic weight s th at are t o b e

S ignific ant figures .

used in so lving t h e probl ems given in this b oo k are t h e approxi

FIVE S T EP S I N S OLVI N G WEI GH T P R OB LEM S 1 13

mat e values in t h e table on t h e b ac k cover T hese are not t h e .

most accurate values which h ave b een d etermined b ut th ey ,

are l
c ose enoug h for practical purposes It is only in very .

accurate c h emic al work th at we use t h e most precise val ues

th at h ave b een obtained I t will b e seen th at th ese numb ers
'

h ave not more th an three figures in th em; t h e fourth fifth or , ,

sixth figure counting from t h e l eft h as b een round ed o ff For .

exampl e t h e precise atomic weight of b arium is

,
We
c all th is 1 37 I n t h e s ame way in c arrying out arithmetic al
.
,

pro c esses we sh ould exp ress the answer i n th e nearest t h ree fi gures .

Since we h ave used atomic weights th at h ave not more t han

,

three figures in th em t h e fourth fifth and sixth figures in a

, , ,

possibl e answer will h ave no signifi c ance We therefore say .

th at t h e probl ems in th is b ook sh ould b e c arried t o b ut three

si gnifi cant fi gures Z eros wh ic h occur b efore a set of numb ers
.
,

as for exampl e in are no t consid ered as signifi cant

figures ; t h e three signifi c ant figures h ere are 6 7 and 2 , ,
.

1 07. Five s t eps ving weigh t prob l ems Experienc e

in s ol .

h as sh own th at it is quic ker and th at th ere is l ess c h anc e for

error I f we pro c eed in t h e s o l ution o f c h em ic al p ro bl ems in a
sy stem atic way T h e fo ll owing st ep s are suggest ed
.

( 1 ) Write t h e c ompl ete equation for t h e reac tion in question .

( 2 ) Write t h e formul a weight under t h e formul a of each

sub stanc e involv ed in t h e probl em .

( 3) Write above t h e formul a of t h e sub stanc e t h e ac tual

weight whic h is given P l ace a t ( g or lb s ) ab ov e t h e form
. . ul a .

of t h e sub s t ance t h e weight o f wh ic h we wish t o find .

(4 ) M ake an equation of t wo frac tions One sh ould b e t h e .

ac tual weight o ver t h e formul a weight o f t h e sub stanc e given ,

and t h e oth er h as t h e x over t h e f orm ul a weight of t h e sub

stance required T he actual weights are th e numerators and
.

the form ula wei ghts the denom inators .

( 5) Solve th is equation and d ecid e wh eth er t h e answer is

reasonabl e by m aking a rough c al cul ation as t o wh at t h e answer
sh ould b e .
114 C H EM I C A L EQUA T I ONS A ND C OM P U TA T I ONS

A n ill ust rat ive pro b l e

10 8 . How many grams of pot as m .

siumc hl orate are nec essary t o p repare 1 0 grams of oxygen

Let us pro ceed ac cording t o our fiv e steps

(1 ) Writ e t h e complet e equat ion .

2 K C l Oa 2 KC1 + 3 Oz

( 2 ) Underwrrt e t h e formul a weigh t s .

2 K C l Oa 2 KC1 + 30 2

(2 X ( 3 X 32 )
2 45 96

( 3) Writ e in t h e act ual weigh t s .

10 g .

2 K C l Oa 2 KCl 3 Oz
’

(2 X ( 3 X 32 )
245 96

(4 ) M ake t h e fract ional equat ion.

x 10
245 96

( 5) S olve . 96 x 10 X 24 5
10 24 5 !

9 6
gra ms . A nswer .

CHECK .S ince 24 5 is ab out 2 ; t imes 96, we s h o ul d expec t t h e answer

to b e ab out 2 5 g
‘

QUESTI ONS A ND P R OB LEM S

C al cul at e t h e percent age of nit rogen in ammo niumnit rat e (NH 4N0 3) .

T h e formul a for cry s t alliz ed b arium c h l orid e is B aC l a 2 H 2 0 , which

ind icat es t h at t h ere are t wo mol ecul es of wat er unit ed wit h each mol ecule -

of t h e anh y d ro us b arium ch l orid e C al cul at e t h e p ercent age of wat er of

.

h rat io n in c ry s t allized b arium c h l orid e .

3 . Find t h e weigh t of wat er of h y drat ion ( cry st alliz at ion) in 1 00 ms

gra
of Gl aub er
’
s s al t (N a2 8 0 4 1 0 H aO) K .

4 . ne t on ( 2 00 0 lb s ) of b lue
Given o . v it riol ( C uSO4 5 H 20 ) . H ow
much ( po unds ) is wat er of cry st alliz at ion?
5 . C al cul at e t h e percent age c ompos it ion of t h e foll owing c ompound s
( a) c om mon sal t (N aC l ) ; ( b ) sal t pet er ( K N Oa) ; ( 6 ) c arb on dioxid e
(d ) iron oxid e ( Feg0 4) ; ( e) marb le ( C aC o g) .

6 . A ssume t h at t h e formul a of h emogl ob in, t h e red col oring mat t er of

t he b l ood , is C 758 H 1203N 1958 3Fe C al cul at e t h e percent age o f iro n in it
. .

D oes y our answer ind icat e t h at t h e iron is unimport ant ? Expl ain .
1 16 C HEM I C A L EQUA T I ONS A ND C OM P U T A T I ONS

P R OB LEM S

H ow much pot assiu m ch lorat e must b e us ed t o generat e 4 grams

of oxy gen?

2 . H ow much mercuric
“
oxid e must b e used t o generat e 4 grams of

x
o ygen ?

3 . H ow many gra ms of mercury wil l b e formed in P rob l em2 ?

4 . W hat
weigh t of h y d ro gen will b e pro d uced b y t h e act ion of gra ms
of z inc wit h h y d ro ch l oric acid ? W it h sul furic acid ?
C al cul at e t h e wel gh t of ph os ph orus p ent oxid e ( P 2 0 5) t h at will b e
formed b y b urning grams of ph osph orus .

6 . H ow many grams of h y drogen will b e prod uced b y p assing s t eam

grams o f iro n unt il all t h e iron is c onvert ed int o t h e magnet ic
’

o v er 1 00
e o f iro n ( Fe gOr)
y
ox

7 Fort y grams of co pper oxid e ( C uO) are red uced t o met allic c op per
.
,

b y h eat ing in a s t ream of d ry h y d rogen C omp ut e ( a) t h e weigh t of h y d ro

.

gen required ; ( b ) t h e weigh t of copper formed ; and ( c) t h e weigh t o f wat er

formed .

J8 If 1 0 ms of cry s t all iz ed m carb onat e

.
gra s o diu (sal so d a) are c areful ly
h eat ed , t h e d eh y d rat ed so d iumc arb onat e ( N agC o a) wh ich is l eft weighs
o nl y grams C omput e t h e numb er of
. mol ecul es of wat er of c ry st all i

z at io n .

9 . T h e formul a for al um is K 2A 12 ( S O4) 4 2 4 H eO . Co mp ut e t h e p er

cent age of wat er of h y d rat io n ( cry st alliz at ion) in al um .

10 . C al cul at e t h e per cent age o f oxygen in t h e ab ov e al u m .

T OP I C FOR FU R T HER ST UDY

P ract ical mical c al cul at ions Suppose
-

ch e . cu
. h y drogen
ft . of

are required for some ob serv at ion b all oons W h at is . t h e cos t of t h e raw
mat erials if t h e gas is mad e from ( a) z inc and acid ? b
( ) I ro n and ac id ?

Wh at woul d b e t h e ch eapest ac id t o us e ? W h ich of t h ese met h od s would

seem t o b e t h e m ore ec o no mic al ?
T h ere are ot h er import ant it ems of expens e b esid es raw mat erial s , and
a final answer t o t h e c os t of manufact uring
h y d rogen coul d b e giv en only
if t h ese o t h er expenses were known W h at met h od s were empl oy ed in
.

preparing h y d ro gen for t h e b alloons used in t h e W orl d W ar ? ( M arket

ri es o f m a t ial wil l b fo und in t ad e ioi rn als s uch as Chem ical and i

p
r
c er s e .

M etallurgical Engineer i ng ?
R EVI EW QUES TI ONS 17

R EVIEW QUES T I ONS ON C HA P T ER S VI I —I X

1 D efine and give an example of ( a) v alence ; ( b )

.
.
o xid at i on; (c ) red ue

t ion ; (d ) formul a weigh t ; ( e) d oub l e repl ac ement .

2 . A mical equat ion d epend s on a fund ament al l aw of ch emis t ry

ch e

and a fund ament al t h eory W h at are t h ey ? St at e each of t h em

. .

3 W rit e t h e names of t h e c omp ound s l is t ed in t h e firs t group ( a) and

'

Writ e t h e formul as of t h ose gi v en in t h e second group ( b ) ( a) 8 118 ; H P O ; 2 3 4

TI 0 ; c
2 I ; H s ; C a(N 0 )
3 . A lP O ( b ) T in chl orid e t h allium ni
3 2 r. ,

t rat e ch romiumoxid e c al ciumph osph at e al uminum s ul fid e

, , , .

4 . W rit e a b al anced equat io n for each of t h e fol lowing

(using reac t io ns

formul as t h rough out ) : ( a) t h e d ecomp osit ion of s odium ch l orat e (b y

h eat ing) ; ( b ) t h e union of copper and sul fur (b y h eat ing) ; ( c ) t h e act ion
of s ulfuric acid o n m agnesium; ( d ) t h e act ion o f silver nit rat e and pot ass ium
ch l orid e (in s ol ut ion) ; (e) t h e act ion of b arium chloride and so d ium p h os
ph at e (in solut ion) .

5 . W h ic h t y pe o f ch e mical react ion is represent ed by each o f t he equa

tions in quest ion 4 ?

6 . W h at is t h e d ifference b et ween 2 O, 0 2, and 0 3 ?

7 . P ut int o word s all t h e informat ion wh ich is c o nv ey ed b y t h e equat ion

2 H2 0 2 H 20
'

8 . W hich of t h e foll owing are weight l aws and wh ich are volu e l aws ? m
( a) D efinit e C om p o s it io n b
; ( ) L aw o f G a —
y L uss ac ; ( 0 ) M ul t ipl e P rop or
t ions ; ( d ) C onserv at ion of M at t er ?
9 S t at e and illus t rat e each of t h e foll owing l aws : ( a) C ons erv at ion of
.

M at t er ; ( b ) D efinit e C omposit ion ; ( 0 ) M ul t ipl e P ropor t ions ; (d ) C om

b ining G as Volumes . Wh o first st at ed each of t h e ab ove l aws a
nd at
ab out wh at d at e ? I

10 S t at e in y our
. own words t h e four assumpt ions wh ich D al t on mad e
l n h is h yp ot h esis .

11 . H y d ro gen pro d uces v ery h igh t emperat ures b ot h in t h e at omi c

fl ame of t h e arc wel d ing t orch and in t h e fl ame of t h e oxy h y d ro gen b l ow

pipe . Expl ain .

Writ e b al anced for t h e foll owing react ions : ( a) sod ium

equat ions

on wat er ; ( b ) preparat io n of h y d ro gen p eroxid e ; ( c ) p ass ing nit ro gen over

h ot magnesium; ( d ) c arb on dioxid e and wat er ; ( e) oxy h y d ro gen t orch .

13 S h ow h ow t h e L aw of C ons erv at ion of M at t er applies t o t h e ch emical

.

ch ange inv ol v ed in b urning co al in a st ove .

14 I n wh at forms is energy rel eased wh en a mixt ure of h y drogen and

.

oxy gen is expl o d ed ? I n wh at form was t his rel eased energy prior t o t h e
expl osion? A pply t h e L aw of C onservat ion of Energy t o t h is reac t ion .
1 18 C HEM I C A L EQUA T I ONS A ND C OM P U TA T I ONS

1 5 From wh at is ob serv ed t o h appen wh en iro n and s ulfur unit e , is t h e

.

int ernal c h emic al energy o f t h e iro n sulfid e formed great er or less t h an t h at

h i i l i lf ?
of t e o r g na ro n and su u r

=
l< l=
>

16 . C al cul at e t h e percent age of nit rogen in cupric mmonia

a nit rat e

17 C o pper and
. o xy gen unit e t o formt wo mpounds h aving t h e foll ow
co

. ing c ompos it io ns
I
C o pper
Oxy gen
Sh ow t h at we h ave h ere a c ase mul t iple proport ions
of .

18 I n prep aring oxy gen,

. a mixt ure of 1 0 grams of pot assium ch lorat e
and 5 grams of manganese dioxid e is h eat ed in a l arge P y rex t es t t ub e .

( a) C omput e t h e v ol ume o f o xygen ev ol v ed ( b ) W h at c om .

pound s re m aine d in t h e t es t t ub e ? W h at is t
.
h e w eigh t o f each ?

1 9 H ow many grams of magnesium will b e required t o d ispl ace all t h e

.

h y d ro gen from dil ut e s ul furic acid cont aining 196 grams of pure 11 8 0 ? 2 4

H ow many grams of z inc woul d b e required ? H ow many of al uminum?

2 0 C al cul at e t h e per cent age c ompos it ion of t h e foll owing compound s
.

( a) ammoniumsul fat e ( b ) cane sugar ( 0 H 0 ) (6 ) c al c ium

°

12 22 11 r

ph os ph at e (d ) ca mph or ( e) naph t h alene ( C i cHs) .

1 20 S ODI UM C H L OR I DE A ND H YDR OXI DE

York state furnish es a purer grad e lt T h e United States of sa .

pro d uces more salt th an any o th er nation Salt forms t h e .

greater part of t h e d issolved mat erial in sea wat er and in cer

tain inl and l akes l ike G reat Salt Lake and t h e D ead S ea Salt
, .

for c ommercial purposes is o btained eith er by mining ro c k

salt or by ev aporating sea wat er o r t h e b rine in t h e salt well s

l ocated near salt d eposits I n cert ain pl aces as on some of

'
.
,

t h e sh ores of San Francisc o B ay ( Fig t h e sea water is run .

F ro mA cme P . dc A . P h ot o.

Fi g 6 3 . . Large quant it ies of s al t are coll ect ed from S an Francis c o B ay .

into sh all ow b a sins and evap orated by t h e h eat of t h e sun In .

oth er pl ac es , as in R ussia, t h e wat er is froz en o ut of t h e s olu

tion B ut usually t h e solution is evaporated b y h eat und er

.

red uc ed pressure T h e pure salt crystalliz es out firs t and if

.
,

necessary , can b e c oll ec ted and recry stall iz ed for furth er

purifi c ation .

When salt is t o b e used for ind ustrial purposes, it is gener

ally taken as m
ined and simply crush ed t o a uniform siz e .

For coo king purpos es and for t h e t abl e it must b e purified and
groun d ystalline powd er I t is generally c ontami
t o a fine cr .
.

nat ed with a small quant ity o f c al c ium and magnesium c hl o

'

rid es wh ic h read il y ab sorb m

,
o is ture fro m t h e air and c aus e

t h e salt t o stic k t ogeth er in l umps C h emically pure salt

'

,
.
,
EL EC T R OL Y T I C C ELL FOR DEC OM P OSI N G SA L T 12 1

fro m wh ic h th ese impurities h ave b een removed , d oes not

ab sorb water fromt h e air .

111 . El ec t rolys is of a s al t sol ut io n . h ave j ust sai d

th at lt (so dium c hl orid e) is
sa

c om p o s ed o f t h e el em en ts so
d iumand c hl orine Now wh en Hy d g n
. C hl n ro e ori e

an e l e c t r i c c ur r ent p as s es
th rough a c onc entrated solu
tion o f sodium c hl orid e c hl o ,

ri ne gas is pro duc ed at t he

anod e (positive t erminal ) and
h y drogen at t h e cath o d e (nega
tive terminal ) ( Fig P rob .

ably so d iumis at first l ib erated

at t h e c ath o d e B ut we saw .

th at this el ement rapidly P f at d D i ap h agm er or e r

reac ts with wat er A s a result Fig 6 4 D iagram of t h e el ect rol ys is of

,
,
. .

ht we
h y d rogen is evolved and a sub
’

stance c all ed so d ium hyd roxid e is l eft in s ol utio n T h ese .

c h anges c an b e represented by t h e foll owing equations

2 NaC l 2 Na 0 12 1 (el ec trolysis )

s o d ium m
\
sodiu c h l ori ne
c h l o rid e

2 Na 2 H 20 2 NaOH H 2 1 (at ‘
ca th od e)
s od ium wat er s o d ium h y d rogen
h y d roxid e

This el ectrolytic meth o d is one of t h e com ercial m mth d

e o s

of making sodiumhydroxid e , c hl orine, and hyd rogen

*
.

1 12 . C o mmercial el ect rol yt ic c ell for d ec ompo sing s al t .

T h ere are several t y pes of apparat us Figure 6 5 sh ows t h e principl e o f

.

o ne o f m
t he ,
.
t h e Vorce c y lind ric al cell T h e graph it e ro d s d ip int o t h e
.

b rine and ac t as anod es t er minal ) . T he c at h o d e t er minal ) c o ns is t s

ofa perforat ed s t eel d iaph rag m T h is is l ined wit h c ompressed asb est os
.
,

which prev ent s t h e ch l orine fro m m1x1ng wit h t h e so dium h y droxid e solu
t ion . A c oncent rat ed sol ut ion of s al t is fed in near t h e p os it ive el ec t rod e .

Sinc e h y d rogen is mad e incid ent all y , it is c alled a b y prod uct

-
.
 12 2 S ODI UM C H L OR IDE A ND H YDR OXI DE

m
T h e Sod iu h y droxid e sol ut ion, wh ich is formed near t h e o t h er elect ro d e,
is c ont inually d rawn off T h e s olut io n o f s o d ium h y d roxid e is t h en ev apo
.

rat ed at a h igh t emperat ure and l eav es sod ium h y d roxid e in a mol t en c o n
d it ion T h is can b e cast int o any d esired S h ape
. T h e c h l orine gas es c apes .

t h rough an o ut let
pipe in t h e d o e m
t A s b es t os T op near t h e anod e, and
the h y d rogen gas
passes o ut t h rough an

o pening in t h e c as ing

out sid e the c at h od e .

Large quanti
ties of so d iu hy m
d roxid e, or caustic
d a are mad e b y so ,

t h e el ec trol y sis of
a c o nc ent rat ed
s ol utionof so d ium

c h orid e so m
l I n e .

fac tories suc h as ,

p ap er mill s b o th ,
Fig 6 5 Vert ical s ect ion of Vorc e c ell
bl eac h i ng p o w
. . .

d er wh ic h furnish es c hl orine and c austic so d a are empl oy ed

, , .

Hence immediate use c an b e mad e of all t h e p ro duc t s of this

el ec tro l y sis of so d ium c hl o id e
‘

ex cept t h e h y d rogen T h
r .
, e .

c hl orine pro d uc ed at t h e ano d e is passed d irec tl y int o c al cium

“
hyd roxid e t o form b l eac h T h ere is a l arge and increasing
.
”

use of l iquefied chl orine (in cyl ind ers) for bl eaching purposes .

QUES T I ONS
1 . N ame s1x uses o f co mmon s alt .

2 W h at are t h e ch ief s ourc es o f co mmon salt ?

mw
.

3 . Na e t o s t at es in which t h ere are not ab le d eposit s of c o mmon

s al t .

4 . H ow d oes t h e o cean h appen t o b e sal t y ?

5 I n A fric a nat ives h ave exch anged gol d for sal t ; in for
. mer t imes cakes

of s al t served as m oney Expl ain . .

1 24 O
S ODI UM C H L R I DE A ND H Y DR OXI DE

Sodium is a soft, Silvery metal whic h can b e easily worked

in t h e fingers I t is so quic kl y ac ted on by moist air th at it s
.

b ri gh t l uster is seen only o n a freshly cut surface B ecause .

sod iumis suc h an ac tive m etal , it is k ept i air tight t in c ans n -

.

I n t h e l ab oratory wh ere we
h ave o nly small quantities t o
d eal with , it is kept und er
kerosene .

1 14 . Di scovery of so d iu m
b y D avy . T h e metal so d ium ,

wh ic h is really a l ab oratory
c urio sity, was fi rst prep ared

in 1 8 0 7 b y Sir Humphry
D avy ( Fig His appara
.

t us c onsisted simply of a
pl atinum crucibl e co nnec ted
t o t h e p o sitive p ol e o f a
b attery and a pl atinumwire
‘

connec t ed with t h e negativ e

t erminal of t h e b att ery .

C austic so d a was first melted

Fig 66 S mH UM P HR Y D A VY ( 1 778
. .
in t h e cru c ibl e and th en el ec
B y means oi an el ect ric b att ery h e is o
, t rol y z ed and spl it into oxygen
He m
fif p t
fied zs
d
g g
fi fia ff fifis g m
"

.
a t t h e a n o d e a nd so d iu an d
hyd rogen at t h e c ath o d e; I n
this process small d rops o f metallic so diumrise t o t h e surface
,

of t h e m elted so d ium hyd roxid e and t ake fire on c om ing in

c ont ac t with t h e air .

M etall ic so d iumis still prepared by t h e same meth od ex cept

th at t h e apparatus is b uilt much l arger and out of l ess exp ensive
material s A nd t h e current is now furnish ed by an el ectric
.

generator instead o f a b att ery .

11 5 . M et al l ic so d iu m and po t as s iu m . M etall ic sod ium h as

l ong b een prep ared by t h e l
e ec ro t lysis of fused so dium h y

d roxid e .
H OW S ODI UM H YDR OXI DE M A Y B E M A DE 12 5

I n t h e iron app arat us sh own in figure 67 A t h e mol t en sodiumh y d roxid e

c ond uct s t he current j ust as a solut ion of t he sub s t ance d oes . Oxy gen is
lib erat ed at one el ect rod e and t h e met allic s od iu m and h y d rogen at t h e
ot h er Since in t h e
.

fus ed h y d roxid e t h e 026

met allic sodiumfind s
neit h er wat er nor air
d r i c al
wit h which t o react ,

it c an b e ob t ained in Ves s el
t h e free s t at e . I t is
ligh t er t h ant h e fused
h y d roxid e, fl oat s t o
t h e t op in a mol t en
~

cond it ion, and is

— G as
l ad led off from t ime
to meti . M et allic
p ot as sium is mad e
in exact ly t h e s ame

S o d i um c an
C ell for maki ng met allic s od ium
now b e mad e by
Fig 6 7 A . . .

th e el ectrol y sis of fused so d iumc hl orid e wh ic h c ontains c a l cium

c hl orid e and b ariu m chlorid e t o l ower t h e melting point .

B oth metallic potassiumand metall ic so diu mare very active

sub st ances and c an b e kept o nly if out of contac t with t he air .

T hey are usually preserved und er some suc h

l iquid as kerosene ( Fig 6 7 B ) Wh en freshly . .

c ut ,b oth metal s are silv er white and very s oft .

T h ey combine with most o f t h e no nmetall ic

el em ent s suc h as oxygen and c hl orine with
, ,
K er osene
great energy T h e reac tion with water h as
.

already b een d iscussed In t h e c ase

of p otassium t h e reac tion is so viol ent th at

Fig 6 7 B
. M et allic
. t h e h y d rogen takes fire wh en t h e po tassium
so d iu m
in k eros ene .

acts on water .

1 16 . mh yd roxid e may b e mad e in t h e l ab orat ory

H ow s o d iu .

Wh en we made hy drogen we saw th at so d iumreac ts so

vigorously with water that it c an b e add ed only in small
 26 S ODI U M C H L OR I DE A ND H YD R OXI DE

piec es, one at a t i me . T his must b e b orne in mind in making

m hy d roxid e
so d iu .

T h e metal so d iumrepl ac es o ne hyd rogen at omper mol ecul e

of water and l eaves in sol ution s o d ium h y d rox id e T h is is .

expressed in t h e equation
2 Na + 2 HOH
2 N3 0 H + H2 l
Wh en t h e sol ution i s ev apo

t d a white s olid
ra e , , so d ium
hydroxid e is l eft , .

1 17 . P ropert ies and us es

o f s o d iu m h yd roxid e
T his .

sub st ance, as we saw, is a

w hi t e, b rittl e s o l id Fo r .

l ab oratory purposes it is or
m
u (l eft ) d inarily Sol d in sl end er stic ks
m
Fig 6 8
. . S odi h y d roxid e in sticks '

and mpel l et s y h t ) ’

or p ell et s ( Fig b ut for

.

industrial uses as a so l id mass iniron drums

r

I t rapidly ab sorb s .

Water and c arb on d ioxid e from t h e air I t is extremely solubl e .

in water I t s so l utions are used wh enever a b ase is need ed in

.

t h e l ab oratory .

C o ncentrated sol utions of so d ium hyd roxid e and t h e mois

tened s ol id itself are very corro
siv e h ence t h e name c austic sod a .

It will quic kly d isint egrat e most

vegetabl e and animal material .

In t h e h ouseh old , it is val uabl e

for cleamng purp oses b ecause it
reac ts with and d issolves grease .

I t is ld in t in c ans und er t h e
so

name of ly e ( Fig S o d ium.

hyd roxid e is an enormously im

”
Fig 6 9 C op c ent rat ed l y e i s .

;
mai nly sod i umh yd roxi d e
o

portant raw mat erl al i n t h e

.

industries It is used for instanc e in t h e manufac ture of h ard

.
, ,

soaps and of paper and co tt on goo d s in t h e refining of p etrol eum , ,

128 S ODI UM C H L OR I DE A ND H YD R OXI DE

QUES T I ONS A ND P R OB LEM S

1 . W h o d is covered met allic s od ium?

2 . W h at ot h er d is co veries d id h e make ?
3 . M et allic s o d iumwas dis covered in 1 807 . Wh y was it not d is covered
earlier ?

4 . H ow sh ouldmet allic sodiumb e kept in t h e l ab orat ory ?

5 . H ow may so d iumh y droxid e b e prepared in t h e l ab orat ory ? W rit e
t he equat io n for t he reac t io n .

6 . N ame several import ant uses Of s od iu mh y droxid e .

7 W h at is t h e principal ingred iento f a c an o f h o us eh ol d ly e ?

'

8 . W h y sh oul d a c an Of l y e alway s b e kept near t h e kit ch en s ink ?

9 . W h at personal d anger at t ends t h e use of l y e in t h e h ome ?
10 . W h at is t h e c omp os it io n o f l
( ) y ; ( )
a e b c au s t i c so d a; ( )
0 ro ck s al t ?

3 >l<

11 . W h y is met allic so d ium not found free in nature ?

12 . W h y sh ould so d ium b e c onsid ered a met al ?
13 . W h at ch anges o c cur in a piece of met allic so d iumwh ich is l eft

m
)
’
p osed t o t h e air? ( D o n t t ry it ) .

H ow b e kept from caking ?

ay t ab l e s al t
”
14
mat
.

1 5 G enerally t h e ch eapest c ompound is used as t h e

. . raw erial

t h e manufact ure Of an el ement I s t h is s o wit h s o d ium?

.

>l< >l<

16 . How many p ound s of m

et al lic s o d iu c an b e m Ob t ained b y t h e el ec

t rol y s is of o ne t on Of m m
el t ed so d iu h y d roxid e ?
1 7 H ow many grams o f so d ium h y d roxid e will b e required for t h e
.

re
p p arat io n o f 1 1 5 gram s o f met all ic s o d ium?

18 H ow m
. any grams of s od ium h y d roxid e c an b e mad e b y h eat ing
2 12 grams of s o d ium carb onat e (N a 0 0 ) wit h sl aked lime ( c al cium
2 3

h y d roxid e)
 C HA P TER XI

CHLOR I NE A ND HYDR OG EN CHLOR IDE

D is c overy of c hl orine l ab orat ory prep arat ion ph y sic al

propert ies ch e mical b eh avior mmercial
co prep arat ion and
uses .

C hl orine
wat er and h y p ochl orous acid h y p ochl orit es
b leaching p owd er nascent oxy gen ant isept ic act ion .

P rep arat ion Of h y d rogen chl orid e propert ies h y d rochl oric
acid it s uses c hl orid es t est for chl orid es A naly sis and sy n
.

t h esis Of h y d rogen ch l orid e .

1 19 . D is covery A lth ough t h e Swed ish apot h e

of c h l orine .

c ary S c h eel e mad e c hl orine in 1774 in t h e same way th at it is

now usuall y prepared in t h e l ab oratory , it was Sir Humph ry
D avy wh o gave it it s name Later M ic h ael Farad ay l iquefied
.

it b y c ool ing and compression T h e great maj ority of p eopl e,

.

h owever first h eard Of chl orine in 1 91 5 wh en t h e G ermans

,

mad e a surprise attac k on t h e A llies with this extremely irrit at

i ng and poisonous gas ( Fig R ec ently c hl orine h as found
.

extensiv e use as an agent for steriliz ing germinfect ed water -

for l arge cities and so making it fit t o drink .

12 0 Lab orat ory preparat ion Of ch l orine

. I n t h e preced ing .

c h apt er we d escrib ed a c o m
mercial meth od of anufacturing m
me
c h l or B ut in t h e l ab oratory it is prepared from con
.

c ent rat ed h y d roc hl oric ac id wh ic h is treated with an oxid iz ing

agent T his oxidiz es t h e h y droc hl oric aci d , c h anging t h e

.

h y drogen t o water and pro ducing c hl orine M anganese .

dioxid e ( M I1 0 2 ) is c ommonly used as t h e oxidizing agent .

I n this c ase t h e manganese unites with h alf t h e chl orine Of t h e

hydrochl oric acid T h e rest of t h e chl orine is evolved as a
.

gas wh en t h e mixture is warmed T h e experiment sh ould b e .

12 9
130 C HL OR I NE A ND HY DR OG EN C HLOR I DE

per orf med

ly und er a well ventil ated h oo d
on -
. T h e foll ow m
g
reaction sh ould b e memoriz ed

4 HC 1 M nOz M nC lz 2 H2 0 C 12 1
h yd ro c h l oric manganese manganese wat er c h l orine
ac i d l d 0 c h l o ri d e

It will b e not ed th at one of t he produc ts is a gas ( lorine)

h
c .

T h is is indicated by t h e arrow pointing up .

C ourt esy of F rederi ck G K eyes

. .

Fig 70. Ch l orine gas c om

. ing from t h e front line t rench es and carried b y t h e
-

wind t oward t h e enemy s lines

’
. W h at one s ees is t h e cond ens ed moist ure .

A n airplane pict ure mad e d uring t h e W orl d W ar .

Instead Of using hyd roc hl oric acid with t h e manganese d i

oxid e, it is p ossibl e t o t ake for our purpose a mixture of sodium
c hl orid e and sulfuric acid , wh ic h pro d uc es hyd ro chl oric acid .

Since c hl orine is mod erat ely sol ubl e in water, t h e gas is col
lect ed by t h e d ispl ac ement of air, as sh own in figure 7 1 .

12 1 I mport ant propert ies

. C hl orine is a greenish y ell ow
.
-

gas with a very irritating Od or I t is extremely poisonous

. ,
 C H L OR I NE A ND H Y DR OGEN C H L OR I DE

123 . Us es of ch l orine T h is gas is mad e in enormous

.

quantities ( Fig 73) for use in t h e manufacture of oth er c hem

.

ic al s
.
(See I ndustrial C h art, A ppendix ) For instance, sulfur .

dichl orid e, c arb on tetrachl orid e, and c hl oroformare al l c hl orine

c om p o un d s B ut it
. is al so us ed in t h e manufac ture Of bl eac h
ing and disinfec ting agents, suc h as d il ute so lutions o f hy po
c hl orous acid o r it s salt s T h e c h arac teristic o d or Of c hl orine
.

C ourt esy of W est vaco C h l ori ne P rod uct s C orp .

Fig 73. . S everal h und red orc e c ell s us ed t o prepare ch l orine fromb rine
V .

S od iumh y droxid e i s a b y pro d uct

-
.

can o ften b e d etec ted in l aundries and c l oth es c l eaning

-
es tab
lish ment s .

1 24 . Ch l orine wat er and hypo ch l oro us acid C hl orine is .

s om ewh at s o l ubl e in wat er o ne v ol um e of water und er o rd inary

,

cond itions d issol ving ab o ut th ree v ol um es of t h e gas T he .

s ol utio n wh ic h h as t h e c ol or and sm
, ell o f t h e gas is c all ed ,

ch l orine wat er I f it is pl ac ed in t h e sunl ight it gradually

.
,

d ecomposes and oxygen is set free T h us .

,

2 Clz + 2 H zO -
4 HC 1 + Oz l
HYP OCH L OR I T ES 3
I

When c hl orine water is mad e , it is supposed th at at first h y

d roc hloric acid and anoth er ac id , c all ed hyp och lorous acid
( H C l O) , are formed :
C 12 H 20 HCl HC lO

T his l atter sub stance i s unstabl e and breaks d own easily ,

tting
se

free oxygen :
2 H C lO -
2 HC1 + 0 2 1
I ndustrially it is a very val uabl e su s b tance b ecause Of it s
oxi d iz ing p ower .

T he sl ow d ec omp osit ion

h y p ochl orous acid wit h t h e format ion of
Of

free oxy gen c an b e sh own b y filling a t ub e wit h chl orine wat er and allOW e

ing it t o st and in t h e sunligh t A gas wh ich we

'

c an prov e t o b e oxy gen coll ect s in t h e t op Of t h e

t ub e ( Fig .

T he oxidiz ing act ion of c h l orine

be wat er c an

d emons t rat ed b y t reat ing a s ol ut ion of s ul fur di

oxid e wit h chl orine wat er T h e sul furous acid
.

s olut ion b efore such t reat m ent will not giv e a

precipit at e wit h b arium chl orid e in t h e pres ence

of h y d ro chl oric acid B ut aft er it h as b een oxi
.

diz ed wit h t h e chl orine wat er, a h eavy Wh it e pre

cipit at e is form ed , s h owing t h e presence of s ulfuric

acid

Cl z H 20 H 2 80 3 H zS O4 2 H CI

A s ol ut ion of h y d rogen sulfid e in wat er forms

a precipit at e Of s ul fur on b eing t reat ed wit h chl o

rine wat er, indic at ing t h at t h e oxid at ion h as t aken

pl ace :

m a C h l o ri ne vat e r
'

F g 74
12 5 H y po c h l o ri t e s T h es e fl
. .

ecom
co
posed b y sun gh t
. .

from h y poch lo
,

pound s c an b e prepared
rous acid , b ut th ey are more co nveniently prod uced by o th er
meth o ds .

S odium h y p o chl orit e ( NaC l O) is formed wh en

“
chl orine is run int o a
cold di lute sol ut ion Of sod iumh y d roxid e

0 12 2 NaoH NaCl O NaCl H 20

164 C H L OR I NE A ND HYDR OG EN C H L OR I DE

Wh at really h appens in t h is case is t h at t h e s od ium h y d roxid e react s wit h

b ot h t h e h y p och l orous acid and t h e h y d rochl oric acid formed b y t h e re
act ion oi chl orine and wat er S od ium h y p ochl orit e c an als o b e prep ared
.

b y el ect roly z ing a s olut ion of sod ium chl orid e in a single narrow c ell wit h
out a diaph ragm C h l orine is lib erat ed at one p ole, and sodiumh y d roxid e is
.

formed at t h e ot h er T h e t wo s ub st ances come in c ont act and form s od ium

.

h yp ochl orit e .I n b ot h t h es e met h o d s for t h e prep arat ion of so d ium h y p o

chl orit e we not ice t h at a d ilut e s ol ut ion Of t h e h y p ochl orit e is form ed wh ich

c ont ains c ons id erab l e s odium ch l orid e B ut t h e pres ence Of t h is l at t er

.

s ub s t anc e d oes not int erfere wit h t h e useful ness of t h e h y p och l orit e .

T he h ypochl orit es are unstabl e sub stanc es On account of .

this instabil ity th ey are al way s prepared and used in c ol d

d il ute sol utions On b eing warmed or o n l ong standing th ey
.
,

oxid iz e th em selv es int o c o mpo und s c ontaining more oxygen ,

So dium hyp oc hl orite s ol ution for exampl e

'

c all ed c h l orat es .
, ,

on h eating giv es so diumc hl orid e and s od iumc h l orat e ( NaC 10 3)

3 NaC l O 2 NaC l NaC 10 3

s o d ium s o dium di um
‘

so
h yp o c h l orit e c hl o ri d e c h l o r at e

P otassium c hl orate we h av e al ready used ; it is mad e b y the

action of c hl orine o n warmpo tassium hyd roxid e .

'

12 6 . B l each ing po wd er b tance is T h is su s

mad e by t h e o n sl aked l im
ac tion of c hl orine e I t is a wh ite .

p o w d er wh ic h is rath er u n s t abl e and s mell s s t ro ng ly o f hyp o

c hl o rous acid P ure c al cium hyp oc hl orite h as t h e formul a

.

C a(OC l ) 2 .B l eac hing powd er ac ts v ery muc h l ike a mixed

sa l t of c al cium c hl orid e and c al cium hypoc hl orite and h as ,

0 C]
t h e formul a C a < or C aC l ( OC l )
r

C a( OH ) z C 12 Ca <C l H ao

B l eac hing powd er, or c h l orid e Of lim serv es as a c om

”
e,

mercial sourc e of hypochl orous acid since lime is cheap (See .

I ndustrial C h art, A ppendix ) .

136 C H L OR I NE A ND H YDR OGEN C H L OR I DE

(2 ) sod iu mh y po chlorit e , prepared b y elec t rol y sis or fro m ch lorine gas and
an alkali, is used ; ( 3) a suspensi on of b leaching powd er in wat er i s used
m
.

T his l at t er et h od may be e mpl oy ed in t h e h o useh ol d . Fab rics must b e

t h oroughly wash ed aft er b eing b l eac h ed in ord er to move
re t he ch emicals,

which woul d ot h erwise sl owl y rot t he cl ot h .

Hypochl orous acid is ly displ ac ed fromit s salts by oth er

easi

acid s Wh en a h y poc hl orite is treated with d il ute acid a

.
,

sol ution of hypo chl orous acid result s wh ic h c an th en ac t as a ,

bl eac hing agent In t h e c ommercial use of t h e hypochl orites

'

.
,

th is is accomplish ed as d escrib ed ab ove b y treating t h e ma

, ,

t eri al t o b e bl eac h ed first with t h e h y p ochl orit e and th en with

“
d il ute acid Wh en b l eaching powd er is used in t h e h ouse
.
”

h old t h e acid required is sl owly supplied by carb on dioxid e in

,
'

t h e air T h e equations are :

.

C aC l (OC l ) C0 2 H 20 C aC 0 3 H C lO HC l
H C lO HCl [ 0 ]used up in t h e bl eaching .

12 8 . Disinfect ing and ant isept ic act ion Diseases are c aused .

and co mm unicated by c ertain m

inute p l ants call ed b ac t eria .

T h ese microorganisms are generall y present wh ere th ere is

much waste animal or vegetabl e atter m
H ypoc hl orit es .

rea dily oxidiz e suc h organic material and d estroy t h e b acteria

“
.

For this reason c hl orid e Of l ime h as l ong b een used in t h e

”

h ouseh old as a d isinfectant M ore rec ently a so lution of .

so d ium hypoc hl orit e (prepared b y t h e el ectrolysis of salt

sol ution) h as com e into use for wash ing t h e fl oors and wall s

I n h ospit al s and sic kroom s .

Hypo chl orous acid h as b een found t o b e val uabl e as an

ant isept ic agent in surgery B ut b ec ause Of t h e extreme .

sensitiveness of h um an fl esh it must b e empl oyed only in ,

very dil ute solutions and und er certain special conditions .

’
D akin s solut ion, wh ic h h as b een used with t h e greatest
succ ess in d ressing wound s is essentially a sol ution of so dium ,

hypo chl orite c on taining from

, to per c ent of this
sub stance T h e so l ution mus t b e mad e in suc h a way th at
.

it is practically n eutral If it were eith er alkal ine or acid it

.
,
DI SI NFEC T I NG A ND A NT I SEP T I C A C T I ON
.
3?

would b e t oo in an o pen wound

c orrosi ev Furth ermore, it .

is used most advantageously wh en t h e patient can b e so pl aced

that a stream of t h e solution continuously passes into t h e
wound and wash es it
out .

T he bacteria wh ic h
are present in d ri nking
water can readil y b e
d estroy ed b y h y poch lo
rous a cid T his is usu
.

ally d o ne b y adding
a small amoun t of a
hypochl orite sol ution ,

or by running a sm all
s tream of c hl orine gas

fromsteel c y lind ers c on

taining l iquefied c hl o
rine int o t h e wat er Sll p Fig 76 D iagram ill ust rating h ow wat er i s puri
. .

fied b y I nt ro d ucmg ch l ori ne I nt o t h e wat er mams

ply ( Fig 76) A b out
.

one part o f hypoc hl orous acid in a m ill ion parts Of wat er will
c om pl etel y purify all except t h e most poll uted suppl ies T his .

metho d Of purification h as b een ad opted by many cities and

towns .

QUEST I ONS
1 . W h en and b y wh om was ch l orine d is covered ?
2 D raw a d iagramsh owmg t h e way t h e d el ivery t ub e ent ers t h e b ot t l e
.

wh en y ou collect chl orine in t h e l ab orat ory b y d ispl acement Of air .

3 . Giv e t wo reaso ns for c ol lec t ing c hl o rine b y d ispl acement Of air .

4 . Wh en and b y wh omwas c hlorine first l iquefied ?

5 . W h y was chl orine t h e first gas t o b e liquefied ?
6 . Is ch l orine an act ive
_
or inact ive element ? Expl ain .

7 . Giv e t wo inst ances wh en ch l orine pro d uces comb ust ion .

8 . Why is t h e commercial met h o d Of making ch l orine not used in t h e

lab orat ory ?

9 . W h at are t h e t wo larges t modern uses O f liquid ch l orine?

 38 C H L OR I NE A ND H Y D R OGEN C H L OR I DE

10 . H ow is liquid ch l orine st ored and t ransport ed ?

11 . H ow d oes ch l orine act as a b l eaching agent ?

I n t h e l ab orat ory preparat ion of ch l orine wh at is t h e purp ose for

12 .

wh ich each Of t h e t wo sub st ances is used ?

13 . S ch eel e prep ared chl orine for t h e first t ime b y h eat ing a mixt ure of
manganese d ioxid e and h y d ro ch l oric acid . H e t h ough t ch l orine w as an
oxid e, and so it was regard ed for fort y y ears . C an y ou see wh y ? Expl ain .

14 . Wh en a cy lind er of h y d rogen 1s pl aced ab ov e one c o nt aining chl orine,

t h e t wo gases will mix sl owly and aft er a t i me b ecome a unifor m mixt ure .

Expl ain t his fact .

15 . G ive t wo mples t o
exa ill ust rat e t h e s t ro ng affinit y of ch l orine for
h y d rogen, free or c omb ined .

m
er
i( )
l6
;
.

c
Writ e equat ions
ant i mony ;
for t h e union of ch l orine wit h
( d ) iron ; (e) p h osph orus .
( a) so diu , (b ) c op

17 . Wh en s al t ,
s ul furic acid , and manganese dioxid e are used t o prepare
ch l orine, wh at is t h e purpose o f each ?

I f y ou el ect rol y ze commo n s al t sol ut io n in t h e Vorce cell primarily t o

18 .
-

ob t ain s o d iumh y d roxid e, t h en c hl orine is t h e b y pro d uct ; b ut if yo u c arry -

out t h e pro ces s b ec ause y ou want ch l orine, t h en so d ium h y d roxid e is t h e

b y pro d uct
-
. Expl ain .

19 . W h en a l igh t ed p araffin c andle is l owered int o a b o t t le of ch l orine,

the c andl e c o nt inues to m
b urn wit h a p eculiar red d ish fl a e, giv ing Ofi c l oud s
Of b l ack smoke A ssuming t h at t h e av erage formul a Of p araffin is C 27H 56
.

( )
a w rit e t h e equat io n for t h is reac t io n b
( ) W h a t is t h e b l ack s mo
. k e ?

( 0 ) H ow c oul d y ou d et ec t t h e presence in t h e b ot t le of t h e ot h er pro d uct

Of t he reac t ion?

20 . H ow many m
gra s of c hl orine c an b e ad e fro m m 34 8 grams Of man
ganes e d ioxid e and an ex cess o f h y d ro ch l oric acid ?

21 . s G overnm
D uring t h e W orl d W ar t h e U nit ed S t at e ent was m aking
100 t ons o f c hl orine every 2 4 h ours at t h e Ed gewoo d A rsenal , M ary l and .

H ow many t ons o f pure s al t were used ev ery 2 4 h ours ? A ssume t h at t h e

el ec t roly sis was 1 00 per c ent effic ient .

HYDR OC HLOR I C A C I D

12 9 . A ct io n of sulfuric ac id on co mmon s al t . We h ave

al ready 46) worked with sulfuric ac id ( H 2 S0 4) . D oubtl ess it
1 40 C H L OR I NE A ND H YDR O GEN C H L OR I DE

solid which is call ed sodium sulfate (NagSO4 ) T his . reac tion

proceed s in t wo stages whic h c an b e expressed th us :

NaC l H 28 0 4 NaHS O4 HCl l ( 1)

NaC l N3 HS O4 N3 2 S O4 H O]1 (2 )
Sulfuric acid is used b ecause it b oils at a c omp arat ively h igh t emperat ure
(338 while h y d rogen c h l orid e is a gas at room t emp erat ures
°
T he .

s econd s t age c annot b e c arried out on a smal l

sc al e in t h e l ab orat ory b ec ause it requires a

t emperat ure at wh ich g l ass b egins t o s oft en .

131 . xperiment wit h h yd rogen

An e

c h l orid e T h e extreme solubil it y of

.

this gas in water may b e strikingly

sh own in t h e foll owing exp eriment .

W e fill a d ry flask wit h t h e gas and

insert in
it a t wo h ole rub b er st opper I n one h ole is a
“d ropper ” c ont aining wat er I n t h e ot h er
-
.

t h ere is insert ed a st raigh t gl ass t ub e h aving a

sm all Opening on t h e insid e end T h e appa .

rat us is set up as sh own in figure 78 We now .

pinch t h e rub b er b ulb , expell ing a few d rops of

wat er int o t h e fl ask T his wat er d issolv es so
.

much of t h e gas t h at t h e wat er in t h e jar b el ow

is forced b y at mosph eric pressure t o b eh ave l ike
a fount ain .

this great sol ubil ity of hyd rogen

I t is
c hl orid e in water whic h c auses t h
Experime nt t o sh ow
e
Fig 7 8
c h arac t eri sti c fumi ng of t h e gas I n m
. .

ext reme s ol ub ilit y Of h y d ro 0 1st

gen
air T h e moisture Of t h e air d issolves
.

t h e gas and th en forms small d ropl ets of t h e sol ution hyd ro ,

c hl oric ac id T h ese remain suspend ed in t h e air l ike wh it e fog

. .

132 . P ropert ies . Hydrogen c hl orid e is alcol orl ess gas, ab out
one fourth h eavier th an air It h as a very irritating sh arp
-
.
,

Od or I t is extremely sol ubl e in water : one cub ic centimeter

.
“
of wat er d issolv es no l ess th an 4 50 c ub ic cenim et ers Of t h e

H yd hl id will b
t d w ill n t
1 5 C n n t n an
°
gas at roge c .or e o ur o

support c om b ustion T h e dry gas reacts only very sl owly

.
H YDR OC H L OR I C A C I D 41

with most metal s at room temperature It will react with .

s om e at a high t em p erat ure T h e h y d rogen Of t h e c o mpo und .

is set free as h y d rogen gas and t h e c hl orine c ombines with ,

t h e metal (simpl e repl acement ) .

It react s wit h and t h e prod uc t is

z inc z inc c h l orid e (ZIl Cl z) , a wh it e
solid . T he equat ion for t h e react ion is :

znc n
'

zn Z H Cl H2 1
z inc h y d ro g en z inc h y d rogen
c h l o ri d e c h l o ri d e

T h e ab ove react ion ,

is v ery much like t h at b et ween st eam and iron t o give
h y d rogen and iron oxid e . T he equat ion for t h is reac t ion is

iro n iro n h y d rogen

oxi d e

133 Hyd roch l oric ac id

. T h e so l ution o f h y dro gen c hl orid e
.

in water is known as h yd roch l oric ac id I t s pro perties are quit e .

different from th ose of t h e d ry gas and t h e t wo sub stances

‘

sh ould not b e c o nfused S o l utions o f t h e gas in water c on

.

taining as muc h as 4 0 p er cent by weight of t h e gas c an b e

prep ared A so lution c ontaining more th an 30 p er c ent Of
.

t h e gas is c all ed concent rat ed h yd ro ch l oric acid C ommerciall y

“
.

it is known as muriatic ac id Wh en this is d iluted with 3 or . ,

4 times it s vol ume of water we h av e d il ut e h y droc hl oric acid ,

-

A concentrated sol ution of t h e pure gas in d istill ed wat er i s

“ c h emic ally pu re
”
( C P ) hy d rochl oric acid T his is a c ol orl ess
. . .

liquid with a d ensity of ab out gram s p er cub ic c entim et er .

Hy d roc hl oric acid is a v ery ac tive sub stance W e have .

alread y used it for preparing h y d rogen I t reac ts

vigorously with Z i nc prod ucing z inc c hl orid e I n fac t with
, .
,

all t h e c ommon metal s exc ep t mercury silver cop p er a , nd , , ,

l ead h y drochl oric acid pro d uces a met all ic c hl orid e and hydro
,

gen . T h e equation for t h e reac tion with Z i nc i s :

Zn 2 H Cl l Cl z H2 ?
z inc h y d roc hl oric z inc h y d rogen
ac id c h l orid e

T h is react ion is exact ly the sa me t h e d ry h y d roge

as t h at of mchl oride ,

except t h at it t akes pl ac e v ery rapid l y and at roo t e perat ure m m .

14 2 C H L OR I NE A ND H Y DR OG EN C H L OR I DE

134H y d rochl oric acid is a t ypical acid

. Since this is a .

very common and useful acid in t h e l ab oratory , we may well

sum mariz e it s characteristic properties T hey are also found .

in all th er acid s
o .

1 D il ute h y d roc hl oric aci d h as a s our taste

. .

2 I t turns bl ue l i t mus red and turns a pinkish ph enol

.

phth al ein sol ution c ol orl ess .

3 M any c ommon metal s suc h as zi nc i ron,and magnesium

.
, , ,

repl ace and set free t h e hy d rogen and formt h e c hl ori d es .

4 W h en hy droc hl oric acid is mixed with

.

s o d iumh y d ro xid e sol utio n a neutral sol ution ,

o f c om mon salt in water is formed .

135 . Uses Of h yd roch l oric a

cid . Very
s mallquantities Of hydroc hl oric acid are
m
al way s found in t h e sto ac h since it is nec es
y in t h e d igestive proc ess I t is pro duc ed
sar .

in t h e b o dy fromt h e salt th at is t aken with

food .

C oncen trated hyd roc hl oric acid is manu

Fig 79
. Large b ott l e
.

ans “
fac t ured in consid erabl e quantities for use in
‘

t h e ind ustries and in l ab oratories I t is gen .

eral ly sh ipped in l arge gl ass c arb o ys ( Fig 79) pac k ed in woo d en .

b oxes I t is al so used b y tinmen an

. d p l umb ers for c l eaning
metal surfaces which are t o b e sold ered .

1 36 . C h l orid es . Wh en hl orine
an l
e e ment unites With c ,

t h e c omp ound wh ic h result s is c all ed a ch lorid e A l l t h e salts .

formed by neutral iz ing a b ase with hyd rochl ori c acid are c all ed
c hl orid es irrespec tive Of t h e b ase empl oy ed
, Wh enever a .

metal such as zinc reac ts with h y drochl oric acid t h e metallic

, , ,

c hl orid e (as z inc c hl orid e) is mad e Sometimes a c hl orid e i s

m
.

for ed by c ombining an el ement d irec tly with c hl orine For .

instance antimony and c hl orine will form such a c ombination

,

A ll the mmon chlorides

co easi ly
dissolve in water, except those
f s il ver
o ( A gC l) l ead ( P bC l z) , and merc ury (HgC l )
,
.
144 C H L OR I NE A ND H YDR OGEN C H L OR I DE

l ab oratory Now we s hall analy ze t h e c ompound and sh ow

.

experim entally th at h y d rogen c hl orid e is c o mposed o f h y d rogen

and c hl orine Our meth o d will b e t h e same as th at used in
.

t h e analy sis of water We c all ed

it el ec trolysis .

C oncent rat ed h y d roch l oric acid is pl aced in t h e ap

p arat us ( Fig and an elect ric current is p ass ed
.

t h rough t h e s ol ut ion W e find t h at h y d rogen is pro

.

d uc ed at t h e negat ive c arb on el ect rod e and ch l o

rine at t h e p osit iv e c arb on . A t firs t t h e gas es

c oll ect at unequal rat es b ecaus e t h e ch l orine d iss olves
in t h e s ol ut ion B ut aft er a t ime t h e l iquid b ec omes
.

s at urat ed . T h en b ot h gases , t h e h y d rogen and t h e

c h l orine, c oll ect in t h e t ub es in equal v ol u mes .

In xperiment we Obtain from t h e

this e

aqueous sol ution Of hyd rogen c hl orid e equal

vol umes of hyd rogen and chl orine .

1 39 . S ynt hesis of h yd ro gen c h l orid e . We

c an al so , as in t h e water re c ase of

verse t h eexp eriment and build up (synthesize)

Fig 8 1
. . El ect rol y si s of hy drogen ch lori de by combining equal volum es
h yd m h l of ic acid of hy drogen and C hlorine .

First we prep are a mixt ure of equal v olumes Of hyd rogen and chl orine
b y el ect roly sis A small b ot t l e is now filled wit h conc ent rat ed h y droch l oric
.

acid nearly t o t h e neck A n el ect ric current is s ent t h rough t h e solut ion
.

for ab out 1 5 minut es W e t h en c onnect t h e exit t ub e wit h a st out gl ass

.

t ub e ( Fi g 82 ) which h as a s t op cock at each end

. We all ow t h e gases , .

h y d rogen and ch l orine, t o pass t h rough t h e st raigh t t ub e and t h en t o b ub b l e

t h rough a sod ium h y d roxid e s ol ut ion in ord er t h at t h e excess of h y d rogen
ch l orid e may b e ab s orb ed .

T h e wh ol e apparat us h as
b een covered wit h a d ark
0 10 t h t o prev ent a pre a m Fig 8 2 . . T ub e for synt h esis of h y drogen ch l orid e .

t ure expl osi on d ue t o t h e

sunl igh t I t is b est t o l et t h e gases pass t h rough t h e app arat us for at least
.

1 5 minut es more, t h en t o cl ose b ot h co cks and t o st op t h e current .

T h is mixt ure of equal v olumes of h y d rogen and chl orine may b e expl od ed
b y an el ect ric s park if t h e t ub e is p rovid ed wit h pl at inum wires Or it .
S YNT H ES I S OF H YDR O GEN C H L OR I DE 14 5

may b e expl oded st ill more easily b y exp osure t o d irect sunligh t or t o a
magnesium fl ash ligh t C A UT I ON ! . T h e gases expl od e inst ant ly , b ut t h ere
is no noise, only a lit t le c lick wit h a fl ash Of ligh t in t h e t ub e .

T o s h ow t h e v olume of h y d rogen c h l orid e gas formed , we ay pl ace m

one end of t h e t ub e und er s om e m ercury in a d ish a d open t h e s t op c ock n
at t h at end Since t h e mercury d oes not rise in t h e t ub e and no b ub b les
.

of gas esc ap e, the volu e of th e h ydrogen m ch lorid e i s just equal mof

to the su
m
the volu es of hydrogen and ch lorine .

If we now Op en one end of t h e t ub e b eneat h at er, we not ice t h at t h e w

wat er is sucked up int o t h e t ub e wit h a rush On t es t ing t h e wat er in t h e
.

t ub e, we find t h at it is h y d ro c hl oric acid .

C ooli ng Wat er

Fig 8 3
. . Commercial synt h es is o f h ydro chl oric acid .

T h ese xperi ments sh ow th at one volume of hydrogen combines

e

wi th one volum e of chl orine t o form t wo volum es of h ydrogen

chlori de gas .

1 vol . h yd rogen 1 vol . c h l orine 2 vol . h yd rogen c h l orid e

T h is is a very interesting ill ustration of G ay Lussac ’

s Law of
m
-

Vol u es
 46 C H L OR I NE A ND H YDR OGEN C H L OR I DE

C o mmerc ial synt h esi s Of h yd roch l oric acid

14 0 . R ecently .

hyd rochl oric ac id h as b een mad e on a l arge scal e by t h e d irec t

union Of hyd ro gen and c hl orine T h ese gases may b e Obtained .

as b y pro duc ts in t h e
-
anufac ture of c austic so d am
m
T h e gases c o bine in an acid resisting burner in a sil ica bric k
- -

chamb er (Fig . T h e pro duc t , hyd rogen chl orid e, is d is

so lved in a spray Of water t o form a sol ution of hyd roc hl oric

acid .

SUM M A R Y OF C HA P TER II I

C H L OR INE i s prepared
1 ( I nd us t ri al l y ) b y el ect rolysis
. mch l orid e
o f s o d iu .

2 .
(I n th e l ab orat ory) b y oxi d at ion o f h y d roch l oric acid wit h
manganes e d ioxid e .

P H YS I CA L P R OP ER T IES
1 . G reenish y el l ow , poisonous gas
-

2 . C h aract eris t ic pungent s el l m

3 . S omewh at s ol ub l e in wat er for , ming chl orine wat er
4 . M uch h eavier t h an air
5Easily liquefied
.

C H EM I C A L P R OP ER T IES
1 . W ill not b urn
mb us t ion of some sub st anc es
1

2 . W ill s upport c o , s uch as h y d rogen

and h y d ro carb ons
3 . W ill co mb ine wit h met al s t o formt h e ch l orid es
4 . W il l b l each wh en moi s t b ec aus e of t h e forma t ion Of h ypo
ch l orous ac id , wh ich i s an oxid izing agent
5 . Unit es wit h an equal v ol u m e o f h y d rogen in b righ t sunl igh t or

by S park t o for mh y d rogen ch l orid e

U S ES OR C H L OR I NE
1 . B l eac h ing Of c o t t on and woo d pulp
2 . P urificat ion of wat er
3 . A nt is ept ic and d is infec t ant
4 . M anufact ure Of c o mpound s c ont aining c h l orine

C H L OR I NE W A T ER c ont ains d i ssol ve d c h l orine and h y d ro ch l oric

and h ypo c h l orous ac id s .
1 48 C H L OR I NE A ND HYDR OGEN
- i
C H L OR I DE

5 St art ing wit h co

. mmon salt , h ow woul d y o u prepare ( a) c hl orine and
h y d ro gen ch lorid e ?
6 . W rit e t h e equat ions for preparing c o pper c hl orid e in four way s .

7 . H ow can y ou prove a col orl ess liquid t o b e d ilut e h y d ro ch l oric acid ?

8 . Hy d roch l oric acid may b e prep ared c ommerc ially b y s y nt h es is .

Wh y made in t h e
is it not l ab orat ory b y t h is met h o d ?
9 . N ame four met al s wh ich y ou wo ul d n
ot use t o l ib erat e h y d ro gen

fromh y d roch l oric ac id . Giv e y o ur reaso ns i n each c ase .

10 . W rit e t h e equat ions for t h e act io n o f h y dro chl oric acid upon ( a) z inc ;
( b ) al uminum; (0 ) magnesium; ( d ) sl aked lime ; and (e) c aus t ic s o d a .

l
><

11 . H ow c an we d is t inguis h h y d rogen ch l orid e from h y dro ch l oric acid ?

12 I f y ou h eat
. co ncent rat ed h y d roc h l oric acid , wh at p asses Off ? Give
y our reas ons .

13 . H ow woul d y ou prov e t h at a givensol ut ion cont ained a chl orid e ?

W hy d oes a t inman us e muriat ic acid met als ?
'

14 . in s old ering
15 . Wh y is h y d ro ch l oric ac id not s h ipp ed in t in c ans ?
16 . Wh y d oes an Open b ot t le Of c oncent rat ed h y d roch l oric acid fume
in t h e air and fume more st rongly if t h e b reat h is b l own across it s mout h ?
‘
’

17 . Wh at ch emical l aw is il lus t rat ed in t h e sy nt h es is of h y d rogen c h l o

rid e ? W h at o t h er exp eri ment h av e we h ad wh ich illus t rat es t h e s ame l aw ?
18 C ompare t h e d ensit ies of ( a) oxy gen and c hlorine ;
.
( b ) h y d rogen
and h y d ro gen ch lorid e ; ( 0 ) ch l orine and h y d rogen c h l orid e .

19 . H ow c oul d m
y ou d et er ine wh et h er a b ot t l e marked h y d rochl oric
acid cont ained d ilut e or concent rat ed acid ?
20 Giv e t h e reason for t h e use
. Of each sub s t ance e mploy ed in making
h y d rogen ch l orid e in t h e l ab orat ory .

21 . C al cul at e t h e percent age co mposit ion of h y drogen ch l oride .

22 C omput e t h e weigh t Of s ul furic acid wh ich woul d b e need ed for a

.

c ompl et e react ion wit h 2 34 grams Of s od ium ch l orid e .

23 . H ow many m
gra s of s o d iu m
chl orid e are need ed t o y iel d , wit h con

c ent rat ed sul furic mac id , 14 6 gra s Of h y d rogen chlorid e ?

24 Find t h e numb er of grams of h y d ro gen ch l orid e generat ed b y t h e

.

c om plet e react ion Of 4 9 grams Of sulfuric acid on an excess of s o d iumch l orid e .

2 5 If t h e gas in ques t ion 2 4 is d iss olved in wat er making a 30 per cent

.
,

sol ut ion wh os e d ensit y is grams per cub ic c ent imet er h ow many cub ic ,

cent im et ers Of h y d rochl oric acid will b e pro d uced ?

 C HA P T ER XI I

A CID S , BA SES , A ND SALT S

A cid s in general b ases in general neut ral iz at ion oi b ase and '

acid naming acid s , b ases , and s al t s neut ral iz at ion arid analy
sis mol ar and normal solut ions of a b ase and acid .

14 1 . A c id s in general I n C hapter XI we h ad a go o d
.

d eal t o say ab out h y d oc hl oric acid I t is b ut o ne examp l e of

r .

a large c l ass o f sub sta nces known as acid s A ll of th em c on .

tain h y drogen In a dil ute water sol ution t h e hyd rogen c an

.
,

b e set free b y certain metal s T h e c h emic al ac tion is a c ase

.

of repl ac em ent b ec ause t h e h y d rogen Of t h e ac id is repl aced

by t h e metal Some o th er sub stances l ike sugar al s o c ontain

.
, ,
[

h y d rogen b ut since it c annot b e rep l aced b y metal s th ey are

, ,

not acid s Water soluti ons of all acids have a p eculiar sour
.

t aste and all turn a certain natural dy e called li tm

, us from b lue , ,

t o red Some o f t h e c ommoner ac id s b esid es h y d roc hl oric

.
,

and sulfuric are nit ric (wh ic h is us ed in t h e manufac ture of

,

nitrogly c eri n and nitroc ell ul os e) ac et ic ( whic h giv es vinegar

,

it s sour taste) c itric (wh ich is one Of t h e acid s present in

,

l emons and oranges) t art aric ( found in grapes) malic ( found

, ,

in app l es ) and l act ic (in so ur milk )

, .

A no th er c h arac teris tic of acid s is th eir rapid reac tion with

c ertain c om pound s known as b ases whic h we sh all now d escrib e, .

142 . B as es in general . We have

th at wh en seen 4 5)
so dium hydrogen and a compound c all ed
reac ts with wat er,

so dium h y d roxid e (NaOH ) are form ed T his c ompound is a .

white sol id whic h dissolv es in water It is a ty pical b ase

‘

. .

Wh en sold in t in c ans; it is l ab el ed LYE so da l y e or caustic

_

, ,

so d a and is used as a powerful c l eanin agent b ecause it dis

g
14 9
1 50 A C I D S , B A S ES , A ND SA L T S

s ol ves kitch en or bath room pl umbing b e

Wh en t he
"

grease .

c om es c l ogged a s trong sol ution o f ly e is poured d own t h e

,

pipes I t is estimat ed th at ab out

. tons o f so dium
hydroxid e are manufactured every year in t h e United States .

I t is used in many ch emical ind ust ries such as t h e making of

'

h ard soap .

T h e sol ubl e b ases so d ium hydroxid e (NaOH) and p otassium

hyd roxid e ( KOH) are c all ed alkalies T h ey are strong b ases
“
. .

P otassium hyd roxid e is c o mmonly sold as p o tas h p otash

”
,

ly e OI c austic p otash ‘
Oth er b ases are c al cium h y d roxid e
“
‘

.
,

which is sl aked l ime or l imewater ; magnesium

”

hyd roxid e or
“ milk of magnesia ; and ammo ”

nium hyd roxid e ( NH 4 OH ) o r ammo nia water (spirits of

”
,

h artsh orn) Water soluti ons of b ases h ave as we h ave al ready

.
,

said a peculi ar bi tt er or causti c t aSte and a sm

'

, ooth soap y feeling , .

T h ey change red litmus to b l ue wh ic h is t h e reverse of t h e ,

c h ange c aused b y ac id s T h ey all cont ain o xy gen and hy dro .

gen a c om , bination o f atoms c alled t h e hydroxyl group ( OH ) .

143 N eut ral iz at io n Of b as e and acid

. Wh en sol utions of .

a b ase and of an acid are b rought t ogeth er in j ust t h e right

prop ortions t h e c h arac t eristic p ro perties of eac h d isapp ear
, .

I t is evid ent th at th ere h as b een a c h emic al c h ange T he .

b ase and t h e acid are said t o neutraliz e eac h o th er, and t h e

process is c all ed neut ralizat ion T o d etermine j ust wh en t h e .

right am ount of ac id h as b een used t o neutral iz e a giv en am ount

'

o f ba se, we use l itm us or s ome o th er ind ic at or l ike ph enol

*

phth al ein .

If we all ow 10 cub ic cent imet ers Oi h y dro ch l oric acid t o run fromab uret t e
“
.

( Fig 84 ) int o ab eaker and ad d a d rop or t wo Of l it mus , t h e solut ion b ecomes

.

b righ t red A d ilut e solut io n o f s o d iumh y d roxid e is now ad d ed l it t le b y l it t l e

.

fromt h e ot h er b uret t e, and t h e sol ut ion is st irred W h en a cert ain amount .

of t h e b ase h as run in, t h e c ol or of t he sol ut io n sud d enly t urns b lue . T his

sh ows t h at s l igh t ly t oo much b ase h as b een ad d ed . A few d rops of ac id

A n ind ic at or is a sub st anc e wh ic h sh o ws o ne c ol or in an ac id and anot h er in a

b ase sol ut io n .
1 52 A C I DS , B A SES , A ND S A L T S

pound s, for a v ery

. l ight c hange in t h e name of one of th ese
s

m it into t h e name of a c ompound of quite

,

will o ften transfor

different properties For exampl e mercuric c hl ori d e ( HgC l z) is
.
,

corrosive subl im ate whic h is e xt remely poisonous ; b ut mercu

,

rous c hl o rid e ( HgC l ) is c al o m el wh ic h is a c o m mon medicine

, .

I n naming b as es we simp l y prefix t h e name o f t h e met al t o

t h e word
“h y d roxid e
,

T hus we h ave s o d ium h y d roxid e

.

( NaoH ) c al ciumhyd roxid e ( C a(OH )

, and al um inumh y d rox
id e (A l ( oH )
I n naming ac id s we mus t distinguish b etween an acid c on
,

sis ting o f t wo el ement s (a binary aci d ) and an ac id c o nsisting

of th ree el em ents ( a t ernary acid ) I n t h eb inary acid we h av e

.

b ut one el ement b esid es t h e h y drogen h ere we prefix h y d ro ,

t o t h e name o f t h e sec ond el ement and add t h e termination ic -

.

T h us we h ave h y d roc hl oric acid ( H C l ) and h y d rosulfuric acid

T h e l arge maj ority of ternary acid s c o ntain o xygen
as t h e third el ement I t o ften h appens th at t h e s ame th ree
m
.

el e ents fo rm m ore th an o ne ac id T h e most famil iar one is .

named from t h e c ha rac t eri stic el em ent and end s in t h e suffi x

ic ; whil e t h e o ne with l ess oxy gen h as a simil ar name b ut t h e
"

end ing is t h e s uffix ous T hus we h ave s ulfuric ac id ( H 2 S O4 )

-
.

and sulfurous acid ( H 2 8 0 3) al so nitric acid ( H N O3) and

nitrous ac id ( H NOz) .

I n naming a sal t we h av e t o consid er v ery c arefully t h e acid

,

from whic h it h as b een d erived If t h e acid is binary, th en .

t h e salt is named after it s t wo c o nstituent el ements with t h e

end ing -
id e T h us we h av e so d ium c hl orid e ( NaC l ) z inc
.
,

c hl orid e ( Z fl C l z) and copp er sulfid e ( C uS )

,
I f t h e ac id is .

ternary and it s name end s in ic th en t h e name of t h e salt end s

-

in at e ; b ut if t h e ternary a
-
c id end s in Ous th en t h e nam e of -

t h e salt end s in it e -
T his will b e mad e c l ear in t h e t abl e on
.

t h e next p age .

With acid s l ike sulfuri c and sulfurous th at h ave t wo repl ace

abl e hyd rogen ato ms we c an h ave salts in wh ich only one o f t h e
,

hyd rogen atoms is repl ac ed b y a metal Suc h salts are so me .

tim es c al led aci d s alts and t h e prefix b i is em

, pl oy ed in nam ing
 A P P L I CA T I ON OF NEUT R A L I Z A T I ON T O A NA L YSI S 53

th em T hus sodium bisulfate ( NaHSO4 ) so dium b isulfit e

.
, ,

m m
(

( N aH S o a) s o d iu b ic
,
arb o nat e ( NaH C Oa) are ex a p l es .

NA ME OF A CD
I FOR M U LA NA ME OF SA L T F OR MUL A

H Cl S od ium chl orid e

H gS O4 C op per sul fat e
H 2S0 3 P o t assium sulfit e
H QS Z inc sul fid e
H N0 3 P ot assium nit rat e
H N0 2 S od iumnit rit e

146 . A pplic at io n Of neut raliz at io n t o anal y s is . We c an

easi l y find o ut h ow much

b ase or an acid a solution c on
of a
tains b y appl y ing wh at we h ave j ust l earned ab out neutral
l
iz at ion Sup pose for instanc e th at we know t h e co ncentra
.
, ,

tion of a b a sic so l utio n ; th at is t h e num b er of grams of so d ium,

h y droxid e in a l iter of t h e so l ution W e c an quic kly d etermine .

t h e numb er of grams of acid in t h e s ol ution wh ic h neutral iz es

t h e b asic sol ution b y me rel y m easuring t h e v o l umes o f t h e

sol utions I f we recall wh at we l earned in sec tion 105 we sh all

.
,

know from t h e fo ll owing equation th at 4 0 grams of so d ium

hydroxid e will reac t with grams of h y d roge n c hl orid e

NaOH HC l NaC l H 20
40 g . 36 5 g
.
, .

T h erefore, if we h ave a l iter Of so dium hy droxid e so l ution c on

taining 40 grams o f so dium h y droxid e and a l iter o f acid so l u
tion c ontaining grams of h y d rogen c hl orid e and mi x th ese
so l utio ns , th ere will b e no ex cess o f ac id or b as e Obviou sl y it .

is not necessary t o use al l o f b o th sol utio ns t o Obt ain a neutral

reac tion We h ave onl y t o take equal volumes of b oth (for
.

exampl e 10 cub ic c entimeters of t h e ac id s ol ution and 1 0 c ubic

,

centim et ers of t h e b asic s ol ution and th es e will neutral iz e each ,

o th er. Wh en 1 000 cubic centimeters Of a sol ution contains t h e

formul a weight of a c ompound in grams it is c all ed a molar ,

sol utio n .

Let us suppose th at We st art with amol ar sol ution of so dium

hydroxid e and wish t o d etermine t h e c oncentration of an un
 54 A C I D S , BA SES , A ND SA L T S

known hyd rochl oric acid sol ution Usi ng b urettes and an .

ind ic ator we d etermine h ow much oftt h e mol ar so diumh y d rox

,

id e is required t o neutral iz e t h e given amo unt Of t h e ac id

/

sol ution I f 2 5 cub ic c entimeters of so d ium h y droxid e neu

.

t raliz es 2 5 cub ic c entimeters of t h e acid sol ution of c ourse t h e ,

h y d ro c hl oric acid is of t h e same c oncentration as t h e b ase ; th at

is it is al so mo l ar
,
I f o nly . c ub ic c ent imet ers o f so dium

hyd roxid e is required t o neutral iz e 2 5 c ub ic c entimeters of t h e

acid t h e h y d roc hl oric ac id mus t b e muc h l ess c onc entrated th an
,

t h e b ase in fact o nly o ne tenth mol ar

, ,
If 50 cub ic c entimeters
-
.

of s o d iumh y d ro xid e is required for 2 5 c ub ic c entim eters Of ac id ,

we sh ould co nc l ud e th at th ere are twic e as many mol ecul es of

acid in t h e giv en s ol utio n as o f b ase ; th at is th at t h e ac id is 2 ,

mol ar T hus we see th at the volumes of basic and acid soluti ons
.

requi red for neutrali zati on vary invers ely as th e concentrati on of

th e soluti ons T h is pro cess o f d etermining t h e conc entration

.

Of an unknown acid or b as e is c al l ed tit rat ion .

1 47 . N ormal A s l o ng as our acid and b ase are

s o l ut io n.

l ike h y droc hl oric acid and s odium hy d roxid e, we sh all h ave no

d iffic ulty in using t h e i d ea of a mol ar solution B ut with some .

acid s , l ike sulfuric acid ( H gS O4 ) , o ne mol ec ul e of ac id neutral

iz es 2 mol ec ul es of b ase :
Z NR OH H 28 0 4 Nas 4 2 H 20
s o d i um s ul fur ic m
s o d iu wat er
h y d rox i d e ac i d s ul p h at e

T hus , 10 c ub ic centimeters of amol ar so l ution o f sulfuric acid

requires 2 tim es 1 0 , or 20 c ubic c entim eters Of a m o l ar solution

of so d ium h y d roxid e for neutral iz ation It is convenient t o .

h ave acid and b asic sol utions so th at equal volumes will neu
t raliz e eac h o th er T h is c an b e d one if we use normal s olut ions
. .

A normal aci d soluti on contai ns 1 gram of rep laceab le hydrogen

p er li t er of th e s oluti on (not t h e s olvent ) A normal base s olu .

ti on contains 1 7 gram s of th e hydroxy l ( OH ) group p er li ter of th e

s oluti on .I t will b e s een th at in t h e c ase Of an acid with one

repl ac eabl e hyd rogen at o m p er m ol ecul e and o f a b ase with

one hyd ro xyl group , a norm al s ol ution is t h e same thing as a

1 56 A C I D S , BA SES , A ND S A L T S

QUEST I ONS
? N ame four ch aract eris t ics Of acid s
mN ame
.

s ix mul a for each

ac id s and writ e t h e for .

N ame s ix fo o d s wh ich y ou t hink may c ont ain acids

r
-

g .

n
i N ame t h ree b ases used in t h e h ome .

n
e W h at is meant b y an alkal ine react ion ”

p H ow d oes a b ase d iffer fro m an ac id ?

7 . W h at compound is alway s formed in t h e neut raliz at ion of a b ase
and an acid ?
8 N ame and cl assify t h e foll owing as acids , b ases or salts : H 2 S
.
,

Z II ( OH ) 2 ; H C 2 H 30 2 ; N aN 0 2 ; B aC l z ; H 2 8 0 3 ; N H 4OK ; A 1(N 0 3) 3 ;
H 3P O4 ; K N Os .

9 . G iv e t h e names Of t h e foll owing s al t s : Z nC O B aS ;

KN O K 28 0 3.

10 . C ompl et e and b al ance t h e foll owing equat ions , and und erwrit e t h e
names of the v arious s ub st ances :

(a) K OH H Cl
(b) N aOH ,
m o.
(c ) N ao H HN0 3
(d ) N aOH H .P o .
(e) KOH H zc o .
l
><

11 . W h at is t h e essent ial d ifference b et ween oxid es and h y d roxid es ?

12 . I s t h ere any d iffere
nce b et ween an alkali, an h y d roxid e, and a b ase ?

13 I f an ac id get s int o y our ey e, wh at sh oul d y ou d o ab out it ?

“
.

14 . Wh y is limewat e r somet imes ad d ed t o t h e b ot t l e-

fed
”
b ab y
’
s milk ?
15 . I f ab as e accid ent ally get s int o y o ur ey e, wh at sh oul d y o u d o ab out it ?

16 . P hrase t h ree quest ions t h e answer t o wh ich will b e sodiu mhydroxide .

17 . H ow may ch emic ally pure (C P )

. . co mmon sal t b e prep ared in t h e
l ab orat ory ?
18 . H ow woul d y ou t es t s oil for ac id it y ? Wh at sh o ul d y o u d o if y ou
find it ac idic ?
19Giv en several whit e s ol id s , h ow
. c oul d y ou proceed t o sh ow wh et h er
t h ey are acids , b ases , or s al t s ?
Gl ass s t oppers in b ot t l es of
20 . s o d iu m h y d roxide Oft en st ick as if
c ement ed int o t h e b o t t l e: Expl ain .

21 .D efine and give an example of ( a) an ac id s al t ; ( b ) a b inary sal t

(6 ) t it rat io n; ( d ) a t ernary ac id ; (e) a normal b as ic s o lut io n .

 C HA P T ER X I II

I ONS A ND ELEC TR ONS

Elect roly t es and nonelect roly t es ioniz at ion elect roly sis .

T h e elect ron st ruct ure of sal t s ions and at oms .

Elect ron t h eory of el ect roly sis , acid s and b ases neut raliz at ion .

I onic react ions react ions which go t o com pl et ion sub

st ances ins olub le in wat er h eat s of format ion and st ab ilit y .

1 48 . Up t o t h e year 1 883 wh en A rrh e

A t h eory is need ed .

nius put forth h is th eory of ions, Ch emists h ad no c ompre

h ensiv e th eory with which t o expl ain t h e vast numb er Of fac ts
that th ey h ad coll ected ab out t h e b eh avior of acid s, b ases and
~

salt s in Wat er sol ution T h e foll owing are some Of t h e more

.

i mportant of th ese
1 . Water wh en pure d oes not all ow e ec rici
l t ty t o pass
th rough it .

2 Solid so dium c hl orid e wh en d ry is al so a nonconduc tor

.

Of el ectri city .

3 A sol ution mad e o f th ese t wo noncond uc tors is an exc el

.

l ent conductor Of el ectricity .

14 9 . S ol ut ions as So lutions of d iffer

el e ct ric al cond uc ors t .

ent sub st anc es in water v ary greatly in th eir p ower t o cond uc t

an el ec tri c c urrent . m
So e sol utions will not cond uc t t h e c ur
rent at all ; o th ers c ond uc t it v ery readily Let us t ry t o .

und erstand t h e reason for this difference .

We may st ud y t he c ond uct ing power Of solut ions, rough ly , wit h appa
rat us so mewh at
like t h at sh own in figure 85 T h e t wo .
pl at inum wires
are connect ed wit h t h e el ect ric circuit T h e l a p? which is on on
. m
e Of t h e

wires s erves as resist ance t o c ont rol t h e current , and also as an ind icat or
Of t h e current When it gl ows b righ t ly , t h e sol ut ion is a good conduct or
. .

157
 58 I ONS A ND EL EC T R ONS

Let us use t h is app arat us t o t est dist illed wat er and t h en s ol ut ions of
sugar, com mon salt , h y droch l oric acid , sod ium hy d roxid e, acet ic acid ,

ammonium h y d roxid e, and al coh ol W e find t h at t h e l amp d oes no t ligh t

.

wh en pure wat er or a solut ion Of

sugar or al coh ol is used B ut t h e .

solut ions Of s al t , sul furic acid , and

s od iumh y d roxid e c ause t h e l am p

t o b urn b righ t ly , wh ile t h e s ol u
t ions of acet ic acid and am monium
h y d roxid egive only ad ul l red gl ow
t o t h e fil ament .

Fig 8 5 A T es t ing c ond uc t ivit y Of s ol ut ions

b een notic ed
It may hav e

th at in th ose s olutions wh ich

. . .

conduc t t h e el ec tric c urrent b ubbl es o f gas rose fromt h e el ec

tro d es This indicated th at a c h emic al c h ange wa

. s going on .

S olutions Of acid s b ases and s alts are c all ed el ect rolyt es b ec ause
, ,

t h ey c ond uc t el ec tricity P ure wat er a nd s ol utions l ik e th ose

.

o f sugar and al co h o l are c all ed nonel ec t roly t es A ch emical .

change always accom pani es the passage of electrici ty through an

electroly te I n th is respec t
.

th ese c onductors d iffer

frommetall ic c onduc tors

m
.

S al t
1 50 . Ot h er pec uliari ” m,
t ie s Of el ect r ol y t es SO r ad i c al
‘

A M
lutions Of acid s b ases , , and
H y d w ge”
salt s are p ec ul iar in sev

eral o th er resp ec ts b esid es

th at of b eing el ectrol y tes .

M et al
For exampl e it is found ,
r ad i c al

th at one grammol ecul e Of -

Fig 8 B
. . D iagram of movement of ions in an

wh en d issolved in a l iter
Of wat er l owers t h e freez ing point from 0 C to 18 6 C ,
° °
. .

and raises t h e b oil ing point from100 C t o C I f one

°
. .

grammol ecul e Of sod ium c hl orid e or nitric acid is d issolved

-

in a l iter o f water, t h e freezing p oint will b e l owered and t h e

'

b oil ing point raised ; b ut the efiect will be considerably greater

1 60 I ONS A ND ELEC T R ONS

T h ese h arged p articl es or ions must not b e confused with

c , ,

atom s T h ey are atom

. s carrying an electri c ch arge B ut this .

el ectri c ch arge com p letely modifi es th e nature of the p article .

P articl es of so d iumcould not b e fl oating around in an aqueous

sol ution for so d iumis a v ery ac tive m
, et al wh ic h would im me
d iat ely reac t with t h e wat er T h e so dium io n is h owever
.
, ,

quite d ifferent and does no t reac t with t h e water .

Fig 8 7
. . M ich ael Farad ay at work in h is l ab orat ory .

1 52 . El ect rolysis . Let us now app ly th is th eory in d

or er

to xpl aintwo facts ab out el ectrolytes ; namely th at th ey con

e ,

duct el ec tricity and th at th ey are at t h e same time decomposed

(broken up ) by t h e c urrent We sh all suppose th at we h ave
.

som e hyd rochl oric acid in a b eaker with t wo el ec tro d es d ip

ping into t h e sol ution as sh own in figure 8 8 , A cc ord ing t o .

our th eory t h e sol ution contains b esid es t h e wat er (wh ic h is

, ,

o nly v ery Sl ightly ioniz ed

) hyd rogen c hl orid e ( H C l ) mol ecul es
, ,
T HE I ONI ZA T IO N T HEOR Y OF ELECT R OLYS I S 16 1

hyd rogen ions hl orine ions all flying around

and c

among t h e water mol ecules Wh en t h e el ectro d es are con

.
_

nec t ed t o some source of el ec tricity such as a generator G ,

or a st orage b att ery one el ec tro d e ,

b ec omes positively c h arged and

C h d at o

is c all ed t h e anod e whil e t h e oth er ,

el ec tro d e b ec omes negativ el y

c harged and is c all ed t h e c at h od e .

1 53 . Th e ioniz at ion t h eory of .

el ect rol y s is . Wh en t he
positive
io ns ( H ) c ome w 9 1?
6 11 a
+ in contac t with 7 27 .
)

t he negatively c h arged pol e ( t h e Fig 8 8 D iagram illust rating t h e . .

el ect rol y s is o f h y d ro ch l oric ac id

c at h o d e) , t h e c h arge on t h e ions is
.

neutraliz ed and t h e result is ord inary hy d rogen at o ms B ut , .

as we h all l earn l ater

s at oms o f free h y d rogen unite
in pairs t o formmol ecul es ( H 2 ) and so we notic e b ubbl es of ,

gas . T h e hy drogen escapes into t h e air A t t h e same time t h e .

-

negative io ns ( C l ) are d isc h arged at t h e ano d e and c hl orine is

‘

set free ( at firs t l argel y d iss o lved in t h e h y d roc hl oric acid ) .

T h e disch arge of t h e ions at t h e t wo el ec tro d es removes th ese

ions from t h e sol ution T o t ake t h e p l ac e of t h e ions thus
.

rem ov ed oth er ions m

, igrate t oward th eir prop er el ec tro d es .

T hus wh en t h e circuit is c l osed t h e ions mo ve and actually

, ,

c arry el ec tricity with th em Nonel ect roly t es d o not c onduc t

.

el ectricity b ec ause th ey h ave no ions .

W e t h us find t h at t h e t h eory of
ions gives us a v ery sat isfact ory account
of t h e el ect roly sis of an aqueous sol ut ion, s uch as d il ut e h y d rochl oric acid
(
.

Somet imes t h e process is compl ic at ed b y t h e fact t h at t h e at oms wh ich are

freed at t h e el ect rod es react wit h t h e wat er as fast as t h ey are formed .

T his is t h e c as e wit h sodium h y d roxid e T h e s od ium at oms which are

.

formed at t h e n egat iv e el ect rod e im mediat ely react , forming more s odium _

h y d roxid e and h y d rogen T h e h y d roxy l ions , wh en t h e ch arge is removed ,

.

immediat ely b reak d own int o w at er and oxy gen

_

T h us t h e gases wh ich .

are prod uced at t h e t wo el ect rod es are h y d rogen and oxy gen, and s odium
h y d roxid e is c ont inuously regenerat ed T h e equat ions are .

at t h e negative el ect rod e at t h e p osi tive el ect rod e

2 Na + 2 H 20 -
2 N aOH + . H21 4 OH
162 I O NS A ND ELEC T R ONS

1 54 . Th e el ec t ron . Wh en t h e io nic th eo ry was first pro a

posed , l ittl e was known ab out t h e nature of el ec tricity, and

v ery l ittl e was said ab out t h e nature of t h e el ec tric al c h arges
on t h e ions . I t was necessary t o assume, of c ourse, th at
th ere mus t always b e an equal numb er of p ositive and nega
t ive c h arges b ecause a so l u
tion is el ectrically neutral
th at is, it is neith er positively
nor negatively c h arged Re
.

cent d ev el opm ents in p hys

ics h ave given us a c l earer

id ea ab out t h e nature of el ec
t ricit y .

We now know that t h e el ec

t ron is t h e sm allest quanti ty of
negative electri ci ty whi ch can
b e transferred from one atom
t o another . T h e el ectron h as
a mass ab out th at of
t h e lightest atom ( t h e hyd ro .

gen atom) .El ec trons may

C ourt esy Of R A M utikan
. . .
exis t by th em selves b ut are
Fig . R OB ER T A N D R EW S M ILL I K A N usually associated W ith mat
( 1 868 A n A merican ph ys icis t wh o
received t e N o b l
h e P i
r e z in h
p y s i c s in t er . SU C h t S I C I S t S a s S ir
1 92 3. M ad e preci s e experiment s o n t h e
J 1 T h om s o n a n d R o b er t
N ow s t ud ying c os m
.

el ect ron i c ray s

A M illikan ( Fig 89) h ave
.

. .

sh own us h ow it is p ossibl e t o obt ain stream s of fast m oving

-

el ec trons, and ind eed h ow t o m easure th eir m ass and th eir

164 I O NS A ND EL EC T R O NS

tive el ectricity ; t h e chl orine i on is negatively ch arged b ecause

t h e atomh as gained this negative el ectricity T h e total num .

b er of t h e positive and negative ions is t h e same in a crystal

of com mon salt T h e solid is th erefore el ectrically neutral
. .

1 57 El ect ron t h eory of el ect rolys is

. T h e proc ess of el ec .

t roly sis is somewh at easier t o und erstand now th at we know

more about t h e nature of el ectricity A current of el ec ”
.
“
t ricit y is a stream of el ec trons fl owing al ong a c ond uc tor The .

t wo l d es ( Fig 88 ) are thus path s by wh ic h el ectrons

e ec ro t .

may enter or l eave t h e solution A t t h e negative electro d e

.

(cath o d e) t h e positive hyd rogen ion may ac quire an el ectron

,

and thus b ec ome t h e neutral h y drogen at om A t t h e positive .

el ec tro d e ( ano d e) t h e negative c hl orine ion may d eliver it s

,

extra el ec tron and b ecom e t h e neutral c hl orine at om We may .

l o ok up on t h e process of el ectrolysis as t h e removal of el ectrons

from t h e negative ions and t h e addition of el ectrons t o t h e
positive ions of a c ompound T h e ions must b e free t o move
.

t o t h e el ectro d es and thus we use eith er t h e fused salt or a

, .

sol ut ion .

1 58 . We cannow more c learly understand

A cid s and b as es .

t h e essential c h aracteristics of acid s and b ases Wh en an acid

’

l ike hyd rochl oric acid d issolves in water, it produc es an hy d ro

ge n ion ( H ) and some negative ion in this c ase t h e c hl orine
+
,

ion A l l acid s give hyd rogen ions and we may th us d efine

'

.
,

acid s as substances which dissolve i n water and form hydrogen

‘

i ons .

A ll b ases tain t h e hyd roxyl group On d issolving in

c on .

water th ey dissociate into a positive ion usually a metal and , ,

t h e negative h y d ro xy l ion We can d efine b ases as sub

s tances whi ch di ssolve i n wat er wi th the p roducti on of th e hydroxy l

i on A ll t h e c h arac teristic s of acid s are really p ecul iarities of

.

t h e hyd rogen ion and t h e c h arac t eristics of bases are d ue t o t h e

,

hydroxyl ion In t h e c ase of d ib asic acid s suc h as sulfuric

.
,

acid t wo h y d rogen ions per mol ecul e are pro d uced ; and in t h e
,
NEU T R A LI Z A T I ON 16 5

b ases such as c al ci umhydroxid e

c ase of , , t whydo xyl ions per
ro

molecule are produced :

H 28 0 4 2 H+ $0 4
"

C a( OH ) 2 ~
C a+ + 2 OH

R ecent ly t h e ioniz at ion t h eory h as b een modified in order t o t ake int o

account t h e nat ure of t h e s olvent T h us in wat er solut ion an acid forms
.

a h y d rat ed h y d rogen ion ( H 2 0 H +

, or
wh ich h as b een c all ed oxonium
ion . I n t h e s ame way , a b as e may b e consid ered as a sub s t ance wh ich t end s
t o asso c iat e pro t ons T h us an acid may b e consid ered ap rotond onor
and a b ase a p roton acceptor I n t h is b ook, h owev er, we sh all not ad opt t h is
.

us age s ince it d oes not seem t o h el p us t o und ers t and t h e simpler ch emical
react ions .

Neut ralizat ion We h ave s een

1 59. .144 ) th at wh en an
acid and a b ase are b rought t ogeth er water and a salt are ,

formed I n terms of t h e ionic th eory this means th at t h e

. ,

hyd rogen i on of t h e ac1d and t h e hydroxyl ion of t h e b ase unite

t o formwater
“
H +
OH H 20
T his reaction t akes pl ace b ecause only a very s all numb er of m
mol ecul es of water are dissociated A mol ecul e of water sh ows .

very littl e tendency t o d issociate into a hydrogen ion and a

hydroxy l ion Wh en we neutral iz e hydrochl oric acid with
. .

so dium hyd roxid e th ere are th us form, ed und isso ciat ed water

mol ecul es T h e sodium ions and t h e chlorine ions are not

.

affected ; th ey s till move around freely in t h e sol ution

Na OH H Cl Na
"

+ + +
Cl H 20
T h e sol ution, h owever is el ec tric ally neutral since t h e numb er
,

of p ositiv e c h arges equal s th at of t h e negative c h arges We .

now h ave exactly t h e same cond ition at h and as if we h ad started

with so d ium c hl orid e and h ad dissolved it in water A s we .

evap orat e t h e sol ution it b ec om es m ore concentrat ed

, A nd as .

soon as t h e so lution b ec om es saturated t h e ions b egin t o j oin ,

t ogeth er and t h e sol id crystall ine so d iumc hl orid e sep arates

, .

1 60 . I onic reac t ion R eac tions in water solutions are

s .

c h arac teriz ed by t h e fact th at nearly all of th em occur al most

166 I ONS A ND ELEC T R ONS

instantly T h e reason for this is th at th ese reactions take

’

pl ac e b etween ions For exampl e, an acid neutral iz es a b ase

‘

so rapidly th at we canno t m easure t h e speed In general , we .

c an th ink of al l reac tions wh ic h take pl ace in d il ute sol utions

of acid s , b ases , and salt s as b eing b etween ions We can often .

write such reactions by forming equations in whic h t h e ions

are sh own T h e neutraliz ation re
.

ac tion h as already b een wri tten in

this way .

T h e repl acement of t h e hydrogen

o f an acid by a m et al is really t h e

transfer of t h e el ectron from a me

t allic atom t o an hydrogen ion .

T h e metall ic atomis th ereby turned

into a metallic ion, and free hydro
gen is l ib erated Such a reaction .

c an b e represented thus
Zn 2 H +
HA
T h e negative ion of t h e acid need
w
not b e sh o n in such an equation
.

b ecause it is not involved in t h e

reac tion .

Whenwe mix asolutionof sodium

m “ potassium nitrate,
Fig gr
. . P ouring h y d roch l oric acid c hl orid e and
d! carb mat e pr d uces
ai
p n th in h a en T h e various l ons
o g pp s .

merely move a round freely in t h e

so l ution . B ut wh en we make a mixture of sod ium c hl orid e

and si lver nitrate (A gNOa) we at once get a white pre
,

c ipit at e (A g C l ) T his is b ecause t h e silver ions and c hl orine

.

ions c omb ine t o formt h e insol ubl e solid silv er c hl orid e (A gC l )

, .

In this way more and more silver ions and c hl orid e ions u nite ,

and more and more silver c hl orid e is precipitat ed until eith er ,

t h e c hl orid e ions or silver ions are exh austed T h e reaction .

goes t o c ompl etion :

“
Ag
+
Cl A gC l l
1 68 I ONS A ND ELECT R ONS

hyd roxide If t h e conductivity of t h e solution is ind icated b y

.

t h e ammeter read ing ( Fig it will b e found th at wh en neu

.

t ralizat ion is com pl ete t h e cond ue ,

t ivit y is reduced prac tically t o z ero

We may represent t h e reaction
wh ich occurs as foll ows
“ “
Ba + +
2 OH 2H S0 4
B aSO4 l 2 H2 ( )
T he milliammeter
ind icates z ero
wh en enough sulfuric acid h as b een
add ed t o precipitate al l t h e B a+ + ions
a mmet er as B asO4 I f an exc ess of acid is
.

add ed , t h e c ond uctivity of t h e sol u

tion increases again .

16 2 . S ub s t anc es ins ol ub l e inwat er .

Fig 93 T h e conductivit y of a I n or d er t o us e t h e f oregoing p rinci

“
s ol ut ion d epend s on t h e c on
mat h " °f m s pl es , w
e sh all need t o know wh at

sub s tances are inso l ubl e i n water, or

sol ubl e only with d iffi culty L at er o n yo u w ill c ons i d er t h e

.

c ase of gases We sh all now state some rul es for t h e sol ubility
.

of so lid s which it will b e well t o re memb er .

G ENER AL R ULES FOR SOLU B I LITY

1 . A ll sodiu m , potassi u
, m , and a mmonium c ompound s are
olub le i n wa er: t
2 .A ll ni trates, chlorates, and acet at es are s olub le in water .

3 A ll ct ri des are soluble, ex cep t th os e of silver, mercury

.

( mercurous) , and l ead (l ead sl ightly s ol ubl e)

‘

4 A ll s ulfates are solu

.

c al c ium ( c al c iums l ightly

5 A ll carb onates are insolub le, ex cept th ose of

.

p o t a ss ium , a nd a m m o nium .

6 A ll oxi des and hy droxi des are i nsoluble, ex cept th ose of

.

ammonium, so d ium, p ot assium, and b arium( cal ciumhyd roxid e .

s l ightly so lubl e) .
H EAT S OF FORMATI ON A ND S TAB I L IT Y 5 9

16 3 . H eat s mat ion and st ab ilit y We h ave seen

of for .

59) that h eat c an b e measured in t erms of c al ories Now

'

.
,

wh en 23 grams of sodiumc omb ine with 35 5 grams of c hl orine .

t o form gram s of s od ium c hl orid e it c an b e sh own th at , .

ab out 97, 800 c a o ries of

l T his quantity O
h eat f
are set free .

h eat is c all ed t h e h eat of format ion of s odium c hl orid e I n .

ge nera l , we m ay s ay th at t h e n um b er of calor i es of h eat abs orb ed

or lib erated during the form ati on of a gramform ula wei ght of a -

com pound fromi ts elem ents is cal led th e h eat of form

l

~
ati on .

H EA T S OF FOR MA TI ON OF A . FE W C OMP OUNDS

C OM P OU N D H . F . IN C A L OR IE S
~
C O M P OU N D H . F . IN C A L OR I E S

I t will b e ob served in t h e ab o v e tabl e th t in Some c ases a

t h e h eat of formation is negative, as ind icated by t h e mi nus
T his means th at h eat is ab sorb ed in t h e b uild ing up of
-

m
sign
"

t he co p ound . th at th ose compound s

I t is al so t o b e not ed
with m
high h eats of for ation are very stabl e and are easily

formed b y direc t c ombination On t h e o th er hand t h e c om .

,

p ound s with l ow val ues are uns tabl e and th ose with negat ive ,

values may b e so unstabl e as t o b e expl osive Wh en hydrogen .

and c hl orine reac t t o f orm h y d rogen c hl orid e muc h h eat is ,

liberated T his type of reac tion is c all ed an exoth ermic reaction

. .

“
B ut wh en hydrogen and iod ine unite h eat is ab sorb ed ; th at is , ,

heat must b e supplied c ontinuously t o make t h e reaction go on

m
.

Suc h a reac tion is call ed an endother ic reactio n .

We must rememb er that t h e h eat of formation is only one

of t h e fac tors whic h h av e t o b e consid ered in pred ictin Wh at
g
will happen in a given case .
1 70 I ONS A ND EL EC T R ONS

SUMM A R Y OF CHA P T ER XI II

A QUEOUS S OLU T I ON S of cert ain co mpound s will c ond uct an

el ec t ric c urrent . S uch co mp ound s are c al l ed el ect rolyt es ; s ol ut ions

of o t h er s ub t anc es d o not cond uct t h e c urrent . T h es e are c al l ed

nonel ect roly t es . A c id s , b as es , and s al t s are el ec t rol y t es .

mes
'

T H E I ON I C T H EOR Y assu t h at in s ol ut ions of el ect roly t es

mol ec ul es
‘

the are d is s oc iat ed int o c h arged part icl es c all ed ions .

EL EC T R O LY S I S involv es t h e d isch arge of th e po s it iv e and nega

mical ch ange
'

t iv e io ns at t h eir r espec t iv e el ect ro d es wit h resul t ing ch e .

T H E EL EC T R ON i s a t iny part icl e (or unit ch arge ) of negat iv e

el ec t ric it y . T h e mas s of an el ec t ron i s a
b out 17 1
3
3 t h at of one h y d ro

gen at o m .

S A LT C R Y S T A L S h ave b e en found t o b e
'

mad e up of ions h el d
t oget h er b y el ect ric al at t ract ion .

A T OM S OF EL EM ENT S minut e nucleus ch arged pos itively

c ont ain a

and around t h i s nuc l eus a s uffic ient numb er of negative el ec t rons t o

make t h e wh ol e at omneut ral .

I ONS are at oms ( or groups of at oms ) wh ich h ave gained or l os t

el ec t rons .

A C I D S are sub st anc es wh ich dissolve in wat er and form h yd rogen

ions .

B A S ES are sub s t ances wh ich d iss olv e in wat er and form hyd roxyl
ions .

I ONIZ A T I ON o f c ert ain acid s and b as es i s co mplet e only in d ilut e

s olutio ns . A c id s and b as es wh ich are only s ligh tly ioniz ed are s aid

to b eweak .

NEUT R A LIZ A T I ON merel y involv es t h e c omb inat ion of ah y drogen

ion and a h y d roxyl ion t o formwat er .

I ON I C R EA C T I ON S will t ake pl ac e onl y if t h e int erac t ion of t wo

o
opp s it el y ions pro d uc es an insolub l e
c h arged s ub s tanc e ( s ol i d or

gas ) Or a s l igh tly ioniz ed s ub s tanc e .

H EA T OF FOR M A T I ON i s t h e numb er of c al ori es of h eat ab sorb e d

or l ib erat e d d uring t h e for mat ion of a gra mformul a weigh t
-
of a,

co mpound fromit s el e ment s .

1 72 I ONS A ND ELEC T R ONS

21St at e in each of t h e following c ases wh et h er or no t a react ion w1ll

.

t ake pl ace and t h e reason for t h e reac t ion or t h e fail ure t o react Writ e .

an io nic equat ion for each reac t ion : ( a) wh en magnesi um 1s pl aced in

h y d rochl oric acid ; ( b ) wh en pot assiumnit rat e and s o diumsulfat e s olut ions
are mixed ; ( c) wh en lead nit rat e and p ot ass iumsul fat e solut ions are mixed .

22 . W rit e an io nic a
equt ion t o S h o w wh at h appens ( a) wh en s olut ions of
so d ium chlorid e and po t ass ium nit rat e are mixed ; ( b ) wh en s ol ut ions of
so d ium c h l orid e and s ilver nit rat e are mixed . Expl ain t h e d ifference in
,

res ul t .

23 . W rit e one equat ion for a react ion wh ich m

goes t o co pl et ion b ecaus e of
( a) the a gas ; ( b ) t h e for
es c ape o f m at ion of an insolub l e s ol id ; (c) t h e
form at ion of a sl igh t ly ioniz ed pro d uct .

24 . Writ e t h e io nic equat ion for t h e t est for a sul fat e . I f one wish es t o
precipit at e all t h e b ariu m from a solut ion ,
‘

wh y d oes h e ad d an excess of

sulfuric acid ?

25C opy and c omplet e : A st rong acid 1s one which

. t o l arge d egree
and t h erefore pro d uces a l arge c oncent rat ion of ions A b ase is .

o ne wh ic h d is s o ciat es t o a l arge d egree and h ence pro d uces a l arge c oneen

W eak acid s and b ases d issociat e t o av ery

,

t rat ion of ions . d egree .

T OP I C S FOR FUR T H ER S T U DY

S ir H umph ry D avy and h is b ril liant pupil M ich ael Farad ay Wh ich man .

did m
ore for t h e ad v ancement o f c h emist ry , D av y or Farad ay ?
( M oore s
’

H ist ory of C h emistry and T h orpe s Essays in H i storical Ch e istry )

’
m .

El ect rons and h ow we us e t h em d is cov ered t h e el ect ron? Wh at

Who
'

generat es t h e st ream o f el ect ro ns in a rad io v a c uu m t ub e ?

( C al dwell and
-

Sl oss on s S cience R emaking the World , and R ussell s A B C of A tom

’
s )
’
.
 C HA P T ER XIV

S TR UCTUR E OF T HE A T OM . VA LENCE

I mport ance of at omic st ruct ure el ect ron t h eory Of t h e at om

nucl eus el ect rons S h el ls nucl eus , prot ons , and neut rons .

Elect ron t h eory of v al ence met als and nonmet als P ol ar and .

nonp ol ar c ompound s C h emic al union in t erms of elect ron t h eory

. .

1 64 W h y s t udy t h e s t ruct ure of t h e at om? T h ere are

.

many problems which t h e ch emist h opes t o solve by studying

t h e structure of t h e atom One is t h e p robl em of v al ence
m
. .

For instanc e what is th ere ab ou

, t t h e so diumatomth at akes
it repl ac e one h y drogen atom? Or c al cium th at makes it ,

repl ace t wo or al um, inum,th at it repl ac es three Wh y is t h e

iron atomsometimes equival ent t o t wo and s ometimes t o three
hydrogen atoms Wh at is t h e essential difference b etween t h e
atomof a metal and t h e atom of a nonmetal ? Wh y are some
atoms suc h as c hl orine SO much more ac tiv e th an oth ers
, , ,

suc h as neon? T h ese are some of t h e fund amental pro bl ems

of c h em istry whic h t h e el ectron th eory of matter h as attempted
t o so lve We sh all b egin by restating this th eory very Simply
. .

165 The el e ct ron t h eor y of t h e at om Up t o 1 8 97 c h emists

m
. .

acc ep ted t h e th eory th at t h e atom was t h e ulti ate const it u

ent o f m atter and was ind ivisibl e I t was Sir J J T h omson
“
. . .

( Fig 94 ) of t h e C avendish Lab oratory in C amb ridge Engl and

.
, ,

wh o upset t his c h erish ed b el ief He estab l ish ed some new

.

and important th eories as foll ows : t h e el ec t ron is an atom of

_

negative el ec tricity ; all atoms contain th ese el ec trons ; and

all el ec trons are t h e same no m atter wh ence th ey c om e T he .

A merican ph y sic ist f R ob ert A M illikan, mad e t h e next great

.

strid e and m easured with extrem e precision t h e m ass and ch arge

of t h e el ec tron H e found th at t h e el ec tron is T 48 5 3 as h eavy
.

173
 74 S T R U C T UR E OF T HE A T O M . VA LENC E

m
as t h e l ightest ato , hyd rogen, and th at t h e a ount of el ec tric m
m
c h arge is t h e sa e as th at carried on t h e unival ent ion .

T h e nucl ear at om
“
1 66 . T h e next st ep was t aken l n ab out
.

191 3 wh en Lord R ut h erford ( Fig 95) S h owed th at th ere was a

.

positive nucl eus in t h e atom

which neutral iz ed t h e nega
tive el ec trons T his h e d is .

co vered by b omb arding atoms

of nitrogen s o d ium al u
‘

, ,

minum and oth er el ements

,

with fast moving c h arged -

h elium atoms t o b reak th em

up . I n eac h c ase h e o btained
p ositively c h arged atoms o f
hydrogen T h erefore h e con
.

c l ud ed th at one or m ore of

th ese p ositi vely charged ato ms

of hydrogen whi ch h e , called

pro tons , must b e p resent in

the nucleus f
o all atom s .

From th is
tarting point s ,

various scientists for ex

SR ampl e t h e D anish p hysicist
) !if ’ y , ,

mag
x
C
1
i L
.

y y ea rs h eacl o f ave nc i sh ab b ra N iel s B Oh r h a v e b uilt 1113 a

t ory in C am
n
b rid ge U iversit y . N ob el very compreh ensive y et sim ,
pnz e 1n ph y s 1c s E st ab h sh ed t h e el ect ron
.

pl e th eory Of t h e struc ture Of

.

t h e atom I t is essentially as foll ows

. A ll atoms can b e c on
.
-

sid ered t o b e m ad e of el ec trons (negative c harges ) and protons

(positively c h arged ) Since all atoms are el ec tric ally neutral
.
,

th ere must b e t h e s ame numb er of el ectrons as of protons in

ev ery atom .B ut t h e atoms of t h e 92 d iverse el ements d iffer
fromone anoth er in t h e numb er and arrangement of th eir el ec
trons and protons In oth er word s t h e atomof any one el ement
.
,

is d ifferent from th at o f every oth er el ement b ecause of t h e

,

numb er and arrangement of it s el ectrons and protons P rac .

 76 S T R U C T U R E OF T HE A T OM . VA L ENC E

T h us t h e h el iumat omh as 2 el ectrons , t h e c arb on at omh as

2 el ec trons in t h e fi rst sh ell and 4 el ec trons in t h e sec ond .

T h e so dium atom h as 2 el ec trons in t h e first S h ell , 8 el ec tro ns

in t h e s econd S h ell , and 1 el ec tron in t h e th ird S h ell T he .

c hl orine atom h as 2 el ec trons in t h e first s h ell , 8 in t h e second ,

_

and 7 in t h e th ird , m aking 1 7 el ectrons l n all Since this .

S o d i um C hlo r i ne
C ar b on
H eli um

Fig 9 7
. . D iagram of h elium, carb on, s o diu m and
, chl orine at oms .

arrange ment Of t h e d ifficult t o represent

l t
e ec rons 1n sp ace 1s

on p ap er l n th ree d im ensions it is c us t om ary t o represent t h e

,

S h ell s as c onc entric rings ab out t h e nuc leus .

W h at ab out t h e s t ruc t ure of t h e nucl eus A ll th is ques

tion of t h e struc ture of t h e atomis still t h e subj ect of very active
inv estigation among b oth ph ysicists and c h emists Y et th ere .

are c ert ain c onc eptions whic h seem t o b e fairly well estab
lish ed. First all t h e prot ons of an atom are in t h e nuc l eus
, (
.

S econd t h e weight of t h e at om d epend s mainly on t h e weight

,

of t h e nu c l eus T hird t o h ave a neutral atom we must h ave

.
, ,

as many prot ons in t h e nuc l eus as we h ave el ect rons outsid e .

Fourth t o ac count for t h e ac tual known atomic weights o f

, ,

t h e atoms we must h ave so me extra prot ons in t h e nuc l eus

,

b esid es th ose required t o neutral iz e t h e el ectrons Henc e we .

h av e add ed anoth er conc eption t o t h e el ectron th eory ; namely ,

t h e neutron Now these neutrons wh ic h h av e only recently

.
,

b een d iscovered are assumed to b e very close combinations of

,

prot ons and electrons Each neutron consists of a prot on

.

el ectron p air of v ery sm all Siz e mill ions of times sm all er th an

,

t h e normal hyd rogen atom I n s h ort the nucleus of any atom .

,

is thought to consist only of p rotons and neutrons For exampl e .

,
EL EC T R ON T HEOR Y OF VA LENC E 1 77

t h e nucl eus di um atom c ontains 1 1 protons and 1 2

of t he so

neutrons wh ich accounts for it s at omic weight 2 3 ( Fig

, .

T h at is t h e at omic wel gh t is approximately equal t o t h e sum

,

o f t h e protons and neutrons in t h e nu c l eus of t h e at om .

C h l or i ne
C ar b on

Fig 9 8
. . Diagram of nucl ei of t h e h eliu m, c arb o n, m
s o diu , and c h l o rine at o ms .

169 . El ect ron t h eory val enc e It is well t o remind

of .

o urselves again and again th at t h e val ue of any th eory l ies in

it s applications D oes it work ? Let uS t ry for exampl e t o

.
, ,

ex pl ain val enc e in t erm s of th is el ec tron picture of t h e at om -

.

We have seen th at we may convenientl y represent t h e el ec

trons as arranged in concentric Sh ell s ab out t h e nucl eus ; T h e
“
more recent view of t h e el ect ronl c satellites is th at th ese ”

el em ent ary partic l es of el ec tric ity are not conc entrat ed at

p o in t s b ut a re d is p o s e d in t h e fo rm o f a ch arge c l ou d B ut -
.

sin c e th is is im pos sibl e t o represent graphic ally we S h all use ,

t h e o ld er mo d el .

We h av e represented t h e sod iumatomas Sh own in figure 97 ,

in wh ic h t h e nucl eus h as 1 1 units o f p ositive el ectricity ( pro

tons ) a nd t h e 1 1 el ec trons are arranged in rings o f 2 8 and 1 , ,

el ectron I t will b e ob serv ed th at t h e s odium atom h as one

.

el ec tron in t h e outerm ost ring Wh en it l oses this outer el ec

.

tron t h e atomof sod ium b ecomes positively ch arged with one

,

unit o f el ectricity and th erefore h as a val ence of o ne T h at is .

,

t e o d iumion is Na
h s + A gain take t h e el ement c hl orine
.
,
It s .

atomis represented in figure 97 in whic h t h e nucl eus is c h arged

“

with 1 7 units o f p ositiv e el ectricity T his requires 1 7 el ec .

trons which are supposed t o b e arranged as foll ows : 2 el ec trons

,

in t h e insid e sh ell 8 el ec trons in t h e next sh ell and 7 el ec trons

, ,

in t h e outer sh ell I t will b e ob serv ed th at in th is c ase t h e

.
1 78 S T R U C T U R E OF T HE A T OM . VA LENC E

t
ou er s h ell need s one more el ectron t o compl ete it Wh en t h e .

c hl orine atomb orrows an el ec tron it is negativ ely c h arged with

,

one unit of el ec tricity T h erefore we say th at t h e val enc e of

.

c hl orine is one and represent t h e c hl orine ionas C l

“
.

In short it is t h e el ec trons in t h e outermost

,

sh ell of t h e at om wh ic h d et erm ine it s val enc e .

T he v alence of an elem ent i s th e num ber of electrons

which i ts atommust gai n or lose i n order to com plet e
i ts outermost shell .

For exampl e, th ere are so me el ements, l ike

neon, whose outer S h ell is c o pl ete, as s h own in m
figure 99 Neon will neith er gain nor l ose el ec trons Suc h an
. .

el ement h as a v al ence of z ero and is th erefore c h emically inert .

1 70 . M et al s and non mal et s accord ing t o t h e el ec t ron t h eory .

I t is an exp erimental fac t th at th o se el ements whic h we ordi

naril y cl ass as metal s , suc h as silver, copper, and gold , are
goo d cond uc t ors of h eat and el ec tric ity and th at t h e non etal s , m
such as s ulfur, are p oor c o nd uc tors and th erefore goo d insul a

tors Sinc e t h e physicist th inks of an el ectric current as a

‘

flow of el ectrons we must ima , gine th at th ere are in t h e m et al s

so m e l oose o r l oo sely b ound el ec trons whic h

P t a i um
wh en set in motion constitut e t h e el ectric
o ss

c urrent Wh en we examine t h e el ectron

.

pic ture of t h e metal s we find th at int h e out er

,

S h ell th ere are a few el ec tro ns ( 1 2 or 3) , ,

whic h app arentl y t h e atom c an quite easily

l ose T hus in t h e atomof sod iumor pot as
.
,

sium th ere is only one el ec tron in t h e out er

,

F‘g D i agram Of
s h ell ( Fig T his el ec tron is so l oosely
pc t ass mm at om
held t o t h e rest of t h e atom th at even a
.

'

b eam of l ight will knoc k it l oose T his is t h e principl e of t h e

.

op eration of t h e p h o t oel ec tric cell I n a copper wire whic h is

.

c arrying an el ect ric c urrent we may well suppose th at t h e

,

el ec t rons in t h e out erm ost S h ell of t h e copp er ato m s pl ay an

important part in t h e process of cond uction I n t h e tungst en .

’

180 STR U C T UR E OF T H E A T OM . VA L ENCE

T he co mmonest
lvent for suc h compound s is water But
so .

c ertain salt s d issolv e in oth er l iquid s suc h as al co h ol and t h e , ,

resulting s ol utions ar e al so el ec trolytes A S we h ave seen in . .

t h e preceding sec tions this b eh avior of salts fi nd s an ex pl ana

,

tion in terms of t h e el ectron th eory C ompound s wh ich read

ily c onduc t an el ectri c current eith er in t h e liquid (molten)
‘

c ond ition or in so l ution ap pear t o b e m ad e up of ions Such .

com pound s are o ften c all ed polar c ompound s M ost Simpl e .

s alts are in this c l ass Sugar gly cerol (glycerin) fats al c oh ol

.
, , , ,

and o th er sub stances whic h d o not cond uc t by th emselv es or

in sol ution are often c all ed nonpol ar I n t h e cl ass with t h e .

nonpol ar c ompou nd s we must put t h e hyd rogen mol ecul e ( H

'

'

t h e o xygen mol ecul e c arb on d io xid e ( C 0 2 ) and a great ,

many oth er Simpl e and important substances .

B et ween t h e t wo ext remes of a p ol ar compound ( like salt ) and a nonpol ar

com pound (like sugar) lie a numb er of sub st anc es ab out wh ich it is more d iffi
cul t t o d ecid e . For exa mple , alt h ough a wat er s olut ion of h y d rogen ch l orid e
( h y d roch l oric acid ) is a
n el ect roly t e l iquid h y d rogen ch l orid e is not
, . I nd eed ,
solut ions of h y d rogen chl orid e in many so lvent s o t h er t h an wat er are nonelec
t roly t es . P ure c oncent rat ed sul furic acid is a nonelect roly t e, wh ile a wat er
sol ut ion of it is an excellent cond uct or of elect ricit y I n wat er . s olut ions

t h ese sub st anc es m ust b e ionized ; in t h e pure st at e t h ey b eh ave more like

nonpol ar co mpounds .

1 72 Val ence in pol ar c ompound s

. A cc ord ing t o our .

p re se nt id eas c o nc erning t h e s truc ture of p olar com p ounds, t h e -

c ryst all ine s o l id is an ord erly arrangem ent of p osit ive and neg

at ive ions of suc h numb er th at t h e wh o l e is el ectric ally neutral .

M et all ic at oms f orm p osi ti ve ions b y l osing one or more el ec /

trons N onmet al lic at oms (l ike c hl orine) or groups of non

.

metall ic atoms S0 4 ) b ecome negative ions by ac quiring

el ec trons A s we h ave already s een th e num b er of
'

el ectrons gained or lost b y each atom (or group of atom

’

s ) in

b ecom ing an i on i s th e val ence of t h e io n T h e val ence of .

so me commoni ons is given in t h e table on t h e next page .

T hus wh en s o d ium an
,
d c hl orine c ombine t o form sod ium
c hl ori d e t h e so d ium at om l oses o ne el ec tro n and t h e c hl orin
,
e

at om gains one ( NaC l ) Wh en metallic c alcium and chl orine

.
C H EM I C A L UNI ON A C C OR DI N G T O ELEC T R ON T H EOR Y 18 1

reac ,
t h owever each c al c iumato m gives up t woel ec tro ns and
,

b ec omes t h e d oubl y ch arged c al cium ion t o take th ese t wo

.

el ec trons requires t wo c hl orine at o m s T h e c o mpound is th ere .

fore c al cium c hl orid e C aC l g W h en metallic z inc dissolves in

,
.

sulfuric acid t h e z inc ion is form ed b y t h e l oss of t wo el ec tro ns ;

"
,

th ese are transferred t o two hyd rogen ions which b ecome h y d ro ,

ge n a t o m s O n.ev a p o rat ing t h e s ol ut io n ea c h d o ubly c h a rged ,

p o s it iv e z mc io n d ra w s t o it o n e d ou bl y c h a rg ed sulfa t e io n .

T h e sol id is z inc sulfate ZnS O4 ,

.

VA L ENCE OF S OM E C OMM ON I ONS

P OS I T E
IV I ON S N E T E
GA IV IO N S

Univ al ent B iv al ent T riv al ent U niv alent B 1v al ent T rivalent

It is very useful in writing formul as of salts t o rememb er t h e

val enc e of t h e ions I f one th en rec all s th at every c ompound
.

must b e electrically neutral it is easy t o see h ow many atoms ,

must b e c ombined For exampl e sinc e t h e sulfate ion is

.
,

d oubl y ch arged negativel y t wo singl e p ositive ions must b e ,

-

associated with it in so d ium sulfate for t h e al geb raic sum of ,

t h e total c h arges must b e z ero if an el ec tricall y neutral mol e

c ul e is t o result
-

Simil arly cal cium sulfat e must b e C aSO4

.
,

m m
I

+ t
S O sulfat e A l 2 ( S O4 ) 3 ( 2 A l O
“
( C a ; and al u i nu + + 3 S 4

any oth er combination would give an exces s of p ositive or

negativ e el ec tric ity .

1 73 C h emic al unio n ac c ord ing t o t h e el ect ro n th eory

. .

Wh en c h l orine c omes in c ontact with so d ium, t h e so diumatom

gives it s Singl e outer el ectron t o t h e c hl orine atom T hus t h e .
 Fig . I oz . El ectron d iagram for t h e union of Sod iumand ch l orine.

whic h h old s t h e t wo el ements togeth er T his pro cess of S hift .

-e

ing or sharing el ectrons in t h e outer S h ell s until a stabl e c on

dition is formed is typical of t h e polar c ompound s , .

T h ere are very many comp ound s suc h as t h e nonpo l ar com ,

pound s , in whic h t h e atoms d o not seem t o unit e in this way

to formmol ecul es For exampl e let us take t h e oxygen mol e
.
,

cu l e 0 2 T his d oes not seem t o b e a c ase of shift ing el ect rons

.

fromone atomt o t h e o th er b ut rath er of

Oxy g n ml ul
,
e 0 o ec e, 2
s h aring a pair of el ec tro ns T his process .

is often call ed c oval ent linkage P erh aps

’

it will b e c l earer in t h e d iagram( Fig

t where i will b s n th t h oxy n
l
. , .

t e ee a t e ge
ato m h as six el ec trons in it s o uter sh ell
El ect ron d iagram and need s t wo m ore el ec trons t o form
we“ “
Fig 1 0 3
. .

maew k
t h e mo st stabl e stat e
°f t h e
T h e t wo oxygen
‘

at oms are brought so c l ose togeth er th at t wo pairs of el ec trons

“

are S h ared T h is gives eac h nuc l eus an o c tet in it s outer sh ell

. .

SUM M A R Y OF C HA P TER XI V
1 . A N A T OM c onsi s t s of a s mall , d ens e N U C L EU S , posit iv ely
ch arged , in wh ich al mos t t h e wh ol e of t h e mas s of t h e at om is con
c ent rat ed , s urround e d b y EL EC T R ON S in co mparat ivel y mpty
e

S pac e .

2 . T h e P OS IT I VE C H A R G E on t h e nucl eus i s equal t o t h e nu mb er

of negat ive el ect rons . m as a wh ol e
T h e at o , , is el ect ric al l y neut ral .
184 S T R U C T U R E OF T HE A T OM . VA LENC E

QUES T I ONS
Name t h ree wh o mad e earl y import ant cont rib ut ions t o
‘

1 . scient ist s

our knowled ge ab out t h e s t ruc t ure of t h e at om W h at , b riefly , d id each

.

cont rib ut e ?

2 . H ow must t h e nu b er m of el ec t ro ns in an at om c o mpare wit h t h e

nirmb er of it s prot ons ? Wh y ?
3 . W h at d et ermines t h e weigh t of an at o m?
4 . Of wh at d oes t h e nucl eus of an at o m co nsist ?
5 . H ow d o el ec t ro ns and prot ons d iffer in ( a) ch arge ; ( b ) weigh t
(0 ) loc at ion in t h e at o m?
d oes t h e weigh t mpare wit h
'

6 . H ow of a prot o n co t h at of a neut ron?

7 . D efine each of t h e foll owing : electron, p roton, neutron .

8 . H ow many el ec t ro ns c o ns t it ut e ( a) t h e first co mplet e sh el l ; (b ) t h e

mm
seco nd ; ( )c t h e t hird ?
I n wh a mplet e out er sh ells ?
‘

9 . t t wo general way s d o at o s for co

10 . Wh at in t h e s t ruct ure of an at o m d et ermines it s v al ence ?

11 . N ame t h ree el ement s t h at l end el ec t ro ns easil y and t h ree t h at b or
row t he meagerl y
m
.

12 . N ame four el e ment s wit h co pl et ed out er S h ell s . W h at is t h e

out s t and ing c h aract eris t ic o f t h ese el e m ent s ?

13 . By means of the el ec t ro nt h eory exp l ain wh at is meant b y a p osi

t ively ch arged b ody A negat ivel y c h arged b o dy
”

. .

14 H ow d oes t h e t h eory of at o mic s t ruc t ure ex pl ain c h e

‘

mic al union?
“
.

15 . H ow d o prot ons and neut rons d iffer ( a) in ch arge ; ( b ) in c om osi p

”
t ion ?

16 . Us ing t h e el e ment lit h ium as an exa mpl e , S h ow h ow t h e s t ruc t ure

of an at o m resemb l es a sol ar s y s t e m , in accord ance wit h t h e B oh r t h eory -

17 . W h at is t rue of m
t h e nu b er e
of el ct rons in t h e out er most S h ell s of

v ery act iv e el ement s ?

18 C hl orine and pot ass ium b ot h h ave a v al ence of
. one . Y et o ne is a
pronounc ed nonmet al wh ile t h e o t h er is an ac t iv e met al . E xpl ain in t erms
o f t h e t h eory o f at omic s t ruc t ure .

19 . W h at is t h e v al ence o f argon? H ow d oes t h is expl ain it s ch e mical

inert ness ?
20 . Expl ain in t erms of elec t rons t h e flow of el ect ric current in a met allic
wire .

21 C omp are t h e flow o f t h e el ect ric

. current t h ro ugh a v acuu m t ub e
wit h t h at t h rough a co pper wire .
R EVIEW QUES T I ONS ON CHA P T ER S X XI V — 85

22 M ake d iagr ams t o S h ow t h e s t ruc t ure of t h e at omof ( a) fluorine

.

( b ) neon ; ( c) oxy gen ; ( d ) h elium; and (e) s od ium in accord ance wit h t h e ,

B oh r t h eory .

23 . mo f at omic st ruct ure diagrams t o sh ow

M ake an equat ion in t h e for -

wh at h appens wh en sod iumcomb ines wit h ch l orine t o make common sal t .

2 4 C opy and c ompl et e : T h e v al ence of an el ement is t h e num

. b er of
which it s at ommus t or in ord er t o compl et e it s sh el l .

2 5 C opy and supply t h e miss mg word s : A ll t h e prot ons of an at omare

m
.

in it s T h e weigh t of th e at om d epend s o n t h e nu b er of it s and

To m
h av e a neut ral at o , we mus t h ave as many in t h e nucl eus
as we h av e out sid e . A ll t h e neut rons of an at o m are in it s

R EVI EW QUEST I ONS ON C HA P TER S X XI V -

1 . D es crib e t wo met h o ds ofmaking so diumh y droxide .

2 . D efine el ect ron, prot on, neut ron v al ence pol ar c omp ound
, , .

3 . W rit e t h e equat ion for t h e react io n o f ch l orine wit h : ( a) wat er ;

( b ) h y d ro gen ; (c ) ant i mony ; (d ) co p p er ; ( e) ph os p h orus .

4 I n t h e preparat ion
. of t h e foll owing gas es , h ow is each c oll ect ed
( a) oxy gen ; ( b ) h y d ro gen ; (d ) h y dro gen ch l orid e ? W hy ?
5 . Writ e the equat io ns for t h e foll owing reac t io ns : (a) t h e act ion of

so d iu m on wat er ; ( 6) c al ciu m ch l orid e o n s o d iu m c arb onat e ; (0 ) m

s o d iu

h y droxid e and sul furic ac id .

6 , C ompare ch l orine and oxy gen as regard s ( a) act ivit y at ord inary

te mperat ures ; ( b ) d ensit y ; ( c) col or ; ( d) sol ub ilit y ; .

( e) affinit y for
h yd ro gen .

7 . W rit e t h e equat ions for t h e foll owing react ions : (a) the manufact ure
of h y d rogen c hl orid e ; (b ) t h e making o f ch l orine from a wat er sol ut ion Of

h y d ro gen chl orid e ; (c ) t h e act ion o f sil ver nit rat e on a wat er
, sol ut io n of

h y d rogen chl orid e .

8 . Given a c ol orl ess liquid t

suspec ed of b eing h y d ro ch l oric acid , h ow
coul d y ou prove b y ch e ical t est s m t h at it is h y d ro chl oric acid ?
9 W h at rel at ion d oes ioniz at ion b ear t o
. el ec t rol y sis ? C an t h ere b e
ioniz at ionwit h out elec t roly sis ? C an t h ere b e elec t roly s is wit h out ionizat ion?
10 . Writ e an ionic
equat ion for eac h of t h e fol lowing react ions
Z inc d ilut e sul furic acid
B arium ch l orid e S ilv er nit rat e

A l uminum h y d ro ch l oric ac id
P ot assiumh y d roxid e dilute s ulfuric acid
C al cium h y d roxid e nit ric acid
St at e in each case wh y t h e react ion goes t o prac t ic al c ompl et ion .
1 86 S T R U C T UR E OF T H E A T OM . VA LENC E

11 . W rit e a p aragraph d es c rib i ng an elec t roly sis o f so e sub s t ance in m

wh ic h t h e m
foll owing t er s are c orrec t l y used ; elec t rol y t e ; ano d e ; c at h o d e ;
pos it ive ion ; el ec t rol y s is el ec t ro d e negat iv e io n ; el ec t ron
‘

; ; .

12 I n ac c ord ance wit h t h e t h eory of at omic st ruc t ure, ( a) must t h e

.

t ot al pr ot o ns equ al t h e t o t al el ec t ro ns ?
( b ) W h ere are all t h e elect rons ?
mical “propert ies ment ?
( c) W h at giv es t h e ch e t o t he el e

13 From t h e p oint o f
. V iew o f t h e t h eory of at omic s t ruct ure, wh at
d et ermines ( a) t h e v al ence ment ? ( b ) T h e weigh t of t h e at om o f
of an el e
t h e element ? (c) W h et h er t h e el ement wil l b e a met al or a nonmet al ?
W h at is t h e d ifference of meaning in t h e t erm mol ecul e in t h e c ase
of ( a) a p ol ar c om pound like commo n s al t and ( b ) anonp ol ar c om pound like
,

carb o n d ioxid e ?
15 From t h e po int of V 1ew o f numb er of mol ecul es , wh at is t rue of equal
.

v ol umes of al l s ol ut io ns o f equal mol ar c o nc ent rat io n? W h at is t rue, as

regard s neut ral iz ing p ower, o f equal v ol um es o f all ac id or b asi c s ol ut ions of

equal normalit y ?
16 W h en y ou el ect roly ze a s olut io n o f s o d iumsulfat e for t en minut es in
a U t ub e and
-
mix t h e c o nt ent s , t he so l ut io n is neut ral ; b ut wh en y ou t h us
elec t ro l y z e a s ol ut io n o f s o d iu m c h l orid e for t en m
inut es and m
ix t h e c on
t ent s , t h e s ol ut ion is b asic . Expl ain .

17 .
( a) W h at is t h e d ifference b et ween a h y d rogen mol ecul e,
ess ent ial

a h y d ro gen at o m , and a h y d rogen io n? ( b ) W h at useful d evice t ransforms

h y d rogen mol ecul es int o h y d ro gen at oms ? Giv e t h e equat ion (d ) I n .

wh at t wo way s c an y ou t ransform h yd rogen io ns int o h y d rogen at oms ( and

ult imat el y int o h y d ro gen mol ecules) ? ( e) Give an equat ion t o illust rat e
each m et h o d .

18 If a solut ion c ont aini ng 4 0 grams of so dium h y d roxid e is mixed wit h

.

a sol ut ion c ont aining 4 0 grams of h y d rogen ch l orid e and t h e resul t ing liquid
is ev ap orat ed t o d ry ness , (a) wh at will b e t h e resid ue ? ( b ) W h at will b e
it s weigh t ?
19 . The c oncent rat ed h y d ro ch l orl c acid of t h e l ab orat ory h as a specific
grav it y of and co nt ains 38 per cent pure HCl . C al cul at e ( a) it s nor
m al it y ; ( b ) it s m ol ar c o nc ent rat io n .

20 . Wh at v ol ume of mol ar b ariumh y droxid e s ol ut ion would neut ral

iz e t h e h y d rochl oric acid pro d uced b y d issolving l it ers of h y d rogen
ch lorid e gas in wa e
t r ?
 88 S U L F UR A ND T HE S UL FI DES

A m i an
er c h emist Herman Frasch after t en years of investi
c , ,

gat ion worked out a most ingenious and succ essful meth o d of
getting out this sulfur T h e pro c ess i s essentiall y this A. .

h ol e is d rill ed d own t o t h e b ottomof t h e sul fur b ed Into this .

h ol e is l owered a six inc h iron pipe wh ich contains t wo small er

-

ppi e s o n
, e w i th in t h e o th er ( F ro ntispiece) Water h eated un .

d er pressure ( 100 l b s /in ) t o a temperature well ab ove it s

2
. .

b oiling point ( 170 C ) is forced d own through t h e six inch

°
.
-

pipe I t melts t h e sulfur and turns t h e und erground d eposit

.

into a subterranean l ake o f mo lten sulfur C ompressed h ot air

‘

(a b out 500 lb s in ) is now forced d own th rough t h e small est

’

2
. .

pipe and forms a froth with t h e mo lten sulfur and h ot water .

T h e pressure o f t h e h ot wat er and compressed air forc es this

froth up th rough t h e middl e pipe wh enc e it disc h arges into a ,

wood en vat whic h measures ab out 1 50 by 2 50 feet and is 60

feet high I n this way great quantities of sulfur c an b e melted
.

and bl o wn t o t h e surface I t is very pure ( o ver p er c ent ) . .

A fter it h as s ol idified t h e h uge bl oc ks are bro ken up l oad ed , ,

directly into cars and shipped t o various points for use with out
,

furth er purification Sometimes a singl e bl oc k contains more .

th an one hundred and forty th ousand tons of sulfur .

1 76 . P ropert ies ofbrittl e s ulfur Sulfur is a pal e yell ow,

.
-

sol id and is ab out twice sol ubl e as h eavy as water I t is not .

ln w at er and h as no marked taste or o d or W h en h eated it .

,

melts at 114 C t o a straw c ol ored liquid A s t h e temperature

°

m
-
. .

uses t h e l iquid b ec omes d arker an

, d more and ore viscous .

A t ab out 2 35 C it is al mo st bl ac k and t oo thic k t o run out of

°
.

t h e vessel T h en it grows th inner again on furth er h eating

.

and b oil s at 4 4 5 C A s a sol id it is a very goo d insul ator

°
.

of h eat and el ectricity .

177 . T h ree variet ies fur Let us d issol ve some ordinary roll
of s ul .

sul fur in a small quant it y of t h e infl ammab le liquid known as c arb on b isul
fid e ( 0 8 2 ) and t h en p our t h e s ol ut ion int o a cry st al liz ing dish . We find
t h at t h e s ol vent sl owly evap orat es and l eaves t h e s ul fur in t h e sh ape of

sm all cry s t als .

T HR EE VA R IETIES OF S ULFUR 189

If this experiment is carried out o n a l arger sc al e and with

cert ain precaut io ns crystal s th at are m
, ore p erfec tly sh aped will

b e formed l ike t h e ones sh own in figure 104

,
T h es e gener .

ally have 8 sid es (o ctah edral )

and b el ong t o t h e rh o mbic
system Hence th is variety
.

is called rh o mb ic s ulfur .

T h e free sulfur found in

natur e is r h o mb ic R oll sul .

fur and flowers of sulfur are

largely c omposed of very
m
s all crystal s of th is sort .

A not h er cry st alline variet y can Fig 1 0 4 R h omb ic s ul fur cry stal s
b e ob t ained b y firs t melt ing s ome
. . .
_

sul fur and t h en allowing it t o cool sl owly T h is can b e convenient ly d one

. ,

in aporcel ain ev ap orat ing d is h A s t h e melt ed sul fur b egins t o sol idify , at h in
.

crus t form s over t h e su rface T wo h oles are t h en b roken t h rough and t h e

.

liquid sul fur und erneat h is p oured out a t one

h ole A l oose mass of need lelike cry st als
.

(Fig . 1 05) is found t o fill t h e int erior of t he

crucib l e .

T he cr s y tal s which grow in liquid

su lfur are of t he
pris monoclinic , or

m at ic , variety T h ey are l ong, trans

.

parent , pal e yell ow needl es, al ost

-
m
tangul ar in cross section and
rec

b evel ed at t h e points Sulfur can b e .

kept in this form ind efinitely pro ,

vid ed t h e tem erature is ab ove 96 C

°

Fig ms M aking sul fur p .

and b el ow i t s melt mg pomt

. .

cryst al s . B ut .

wh en it is all owed t o cool it sl owly ,

b ecomes opaque T his is b ecause it ch anges into particl es of

.

rh om bic sulfur .

We sh all now h eat a quant it y of ordinary roll sulfur in a small fl ask unt il
it is almost b oiling We t h en pour t h e h ot sulfur in a t h in st ream int o a
.

b eaker of c old wat er, as sh own in figure 1 06 I t is c onvenient t o pl ace a

.
 90 S UL FU R A ND T H E S UL FI DES

funnel in t h e b eaker and pour t h e st ream of sulfur around it . T h en we

may easily lift out t h e funnel and t h e s olidified sulfur wit h it . I t is no
l onger b rit t l e b ut s eems almos t l ike a gum .

d ough like pro d uc t obtained by sudd enly c hilling t h e

T he -

molten sulfur in cold water is c alled pl ast ic sulfur Since it .

h as no crystalline form it is al so c all ed ,

amorph o us sulfur T his variety is .

unstabl e as is s h own by t h e fact th at,

in t h e c ourse of y ears it c h anges into

t h e rh ombic form T h e crystalline .

forms of sulfur are sol ubl e in c arb on

b isulfld e T h e amorph ous forms are .

no t .

T h ere are a numb er of oth er forms

in whic h el ementary sulfur can exist,
b ut we s hall not discuss th em h ere .

178 . A ll ot ropic forms . T h e differ

variet ies of an el emen
Making plast ic s ul fur
Fig 1 0 6.
ent t suc h as
. .

we h ave j ust d escrib ed for s ulfur are c all ed all o t ropic forms
m
, .

It us t not b e th ought h owever that t h e sulfur ato m itself is

, ,

d ifferent in th ese variations T h e d ifferences i n formmay b e

.

d ue t o t h e numb er of a toms whic h are combined in t h e sulfur "

mol ecule A t any rate t h e different varieties of sulfur differ

.
“
,

in t h e amount of energy whic h th ey contain T his is perh aps .

d ue t o t h e arrangement of th eir el ec t rons and protons In t h e

'

c ase of sulfur we d o no t y et know j ust h o w m

, any at oms
th ere are in t h e mol ecul e of eac h of t h e different varieties B ut
we d o know th at sulfur at om
.

s h av e a t end enc y t o form l arge

mol ecules s ince gaseous sulfur h as a mol ecul e of eight atoms .

Oth er el ements t o o like o xy gen p h osph orus and c arb on

, , , ,

h ave allotropic forms In t h e c ase of t h e all otropy of oxy gen

.
,

it h as b een found that t h e difference is d ue t o t h e fac t t h at

o ne form h as t wo at om s t o the m ol ecul e ( 0 2 ) whil e t h e o th er

form ( oz one) h as three atoms ( 0 3) and c ontains more energy

th an t h e ordinary formof oxygen .
192 S U L F UR
"
A ND r m: S ULFI DES
add iti on of me
so ac et ic aci d . I t is th en ll d
ca e c aout ch ouc

and is tially a compound of hydrogen and carb on It is

essen .

soft and el astic b ut unsuit abl e for most purposes b ec a use it

very grad ually oxidiz es in t h e air and forms a brittle sub
stanc e T h e caoutch ouc is th erefore mixed with 10 per cent
.

of sul fur and certain

metallic c ompounds
and th en h eated out ,

of c ont act with t he ,

air t o ab out 1 50 C
°
.
,

T h is trea tment makes

it stiffer more el as ,

t ic and m uc h more ,

durable T h e process .

i s c al l e d v ul c ani z
ing and pro duces t h e
c om merc ial art ic l e
knownas rubb er (Fig .

H ard rub b er, also

ll d v ul canite isca e ,

o bt ained wh en c aout

c h ouc is m ixed with

from30 t o 50 per c ent
of sulfur and t h en

h eated t o a tempera
Fig 1 0 8
. Vul canizing an aut omob il e inner t ub e
.

ture ab out 30 d egrees

.

high er th an th at applied 1n making t h e soft vul caniz ed rubb er .

Hard rubb er is used in t h e manufac ture of such articl es as

buttons and fountain pens I t is al so a val uabl e insul ating
.

material for el ectrical machinery .

It h as rec entl y b een found p ossibl e t o prepare an art ificial

rub b er ( Fig 1 09) wh ic h is al m
. o st id entic al with t h e natural

variety T h e synth esis starts with cal cium c arbid e which is

.
-

mad e from c oal and limestone T his carbide 1s used t o make

.

acetyl ene ( C 2H 2 ) gas whic h in turn is polym

, eri zed i a, t he . .
R ECL A I MI NG R UB BER 193

j oined with oth er ac ety l ene mol ec ul es

molecule
]

ac etyl ene is
by t h e aid of a catal y st F inall y th is material ( mon
. oviny lacet
,

yl ene) is treated with hydrochl oric acid and forms c hl oroprene

( C 4 HsCl ) W h en f
.reshly p repa red c hl oro prene is a th in c l ea
,
r ,

liquid b ut it is unstabl e and spontaneously ch anges t o a pl astic

,

sol id wh ic h is s old und er t h e trad e nam

,
e D uP rene I t is said ,
.

t o b e muc h more resistant t o t h e action of solvent s and oth er

Fig . 1 0 9. A rt ific ial rub b er (D uP rene ) in h os e pipe

c h emical s than ordinary vul caniz ed rubb er I t still cannot .

c om p ete in pric e with natural rubb er T h e result is th at l arge .

rubb er m anufac turers are d epend ent on extensive rub b er pl ant a

t ions in tropical countries in ord er t o m aintain t h e supply of
avail abl e rubb er .

1 81 R ming
ecl ai M uc h of t he bb er in out
ol d ru
"

. rub b er.

worn aut omob ile tires bec an T his is d one by

th em into sm and h eating th ese in steam
O

gr1nd1ng all pieces

194 SULF UR A ND T HE S UL FI DES

j ac keted c y l ind ers ( d evu

l caniz ers ) with a c austic so d a so l utio n -

t o d estroy t h e co tto n fib er A fter t h e mixture h as coo ked for

.

ab out 20 h ours und er a steam pressure o f 1 2 5 p ound s p er

“
m
s quare inc h it is wash ed and d ried T h e raw sh o dd y now
”
.
,

goes t o a series of stea h eated roll s whic h remo ve vari ous

-

impurities A b out 70 p er cent of t h e ori ginal materi al comes

.

out a s recl aim ed rubb er and is suit abl e for use again .

S U LFI DES

1 82 O cc urrence of h yd rogen Sul fid e. T his is t h e gas

.

m
H 2 8 ) whic h we smell wh en a mal matter Containing sulfur
d ec ay s B ad eggs are a familiar exampl e I t is also found in
. .

sol ution m certain sulfur springs and o ccurs in v ol c anic gases .

1 83Lab orat ory prepa

. rat io n of h y d r ogen s ul fid e Wh e h y . n
m
drogen is sl owly passed over elted Sulfur, t h e t wo c o bine m
t o for m
hyd rogen sulfid e A fter .

l
on y a few minutes , a trace of t he
gas d etec ted b y means of a
c an b e

stri p of paper m ois t ened with l ead

acetate ( P b ( C 2 H 30 2 ) 2 ) sol ution .

T h e p ap er turns d ark b ecause of

t h e formation of l ead sulfid e ( P b S ) ,

whic h is bl ac k .

T h e usual meth od of preparing

hydrogen sulfid e in t h e l ab oratory
is by t h e ac tion of d il ut e hy d ro
chl oric or sulfuri c acid o n iron

sulfid e ( FeS )

FeS 2 H O] FeC l z s i
Fig . 110 . H y d ro gen sul fid e generat or
for l ab orat ory us e
.
When only a s mall mount
a of

t h e gas is need ed , t h e apparatus

sh own 1n figure 1 10 is c o nv enient T h is is a l arge test tub e
.

c ontaining a few l um p s o f iro n sulfid e and d il ut e h y d ro c hl o ric

acid T h e gas is l ed o ff through t h e b ent gl ass tub e

. . B ut .
 96 S UL FUR A ND T HE S UL FI DES

matter T h e air in sewers frequently contains enough hyd ro

.

gen sulfid e t o cause fa tal accid ents It s poisonous action is .

d ue t o t h e fac t th at it takes away t h e oxy gen from t h e red

c orpusc l es of t h e bl oo d I n c ertain oil field s in T exas hy d rogen
.

sulfid e is present and especially d angerous b ec ause t h e m en

b ecome so accustomed t o it s od or that th ey cease t o notic e it .

In t h e h ouseh old t h e hyd rogen sulfid e in coal gas c an usually

b e d etec ted b y t h e smell , b y it s effec t on pl ants, and h y th e .

bl ac kening of silverware .

18 6 W h at are weak acid s and b as es ? Water sol utions of

.

many acids are poorer conductors of electricity than a solution

‘

o f hyd rog n c hl orid e o r so d ium c hl ori d e of t h e same mo l ec ul ar

e
conc entratio n Suc h acid s al so attac k z inc and oth er metal s
.

muc h l ess rapidly In many way s th ey b ehave as if only a

.

sm all proportion of t h e d isso lved mo l ecul es h ad p ro duced

hy drogen ions “ T h ey are for th ese reasons call ed weak ac id s .

A c cording t o t h e ionic th eory th eir sol utions c ontain many

,

und issociated mol ecul es and o nly a small frac tion of t h e t otal
,

mol ecules are dissociated We may write t h e equations repre

.

senting th is reversibl e process :

I

First stage H zs H+ HS
'

“
S econd stage HS z H+ S
‘

m
I n t h e same way , so e b ases, fer exampl e, ammonium
hy droxid e, are only slightly d issociated and are said t o b e
weak b ases I t must b e rememb ered mcomparing t h e strength
.

o f d ifferent acid s and b ases th at we are c om paring t h e relati ve

d egree of dissociation in dilute sol utions In ord er t o c ompare .

t h e properties of t h e d il ute sol utions of t wo acid s, we must

take sol utionsof t h e same mol ar conc entration so th at th ere will
b e t h e same numb er of mol ecul es in a given vol ume of eac h
so l ution I n suc h equimo l ecul ar sol utions, t h e strength of t h e
.

acid s will vary direc tl y with t h e numb er of hyd rogen ions .

Hydroc hl ori c and nitri c acid s are strong acids T h ey are .

com p l et ely d iss o c iat ed in d il ut e s o l ut ions Su lfuric ac id is.al so

a strong ac id A cetic and sulfurous acid s are weak acid s ;

.
H YDR OGEN S UL FI DE I N T HE L A B OR A T OR Y 1 97

hydrogen sulfid e and carb onic acid s are exceedingly weak acid s .

Sodiu m potassium and calcium hy droxid es are strong b ases

, , .

A mmonium h y droxid e is a weak b ase c hiefly b ec ause a l arge

"

portio n o f t h e d is so lv ed ammonia is present as N H 3 in sol ution

187 . Because
T h e us e of hyd rogen s ul fid e in t h e l ab orat ory .

of it s ac tion on m etall ic so l utions , h y d rogen sulfid e is m uc h

n
Used i n a aly tic al ch emistry T h e metallic sulfid es which are .

formed h ave suc h c h aracteristic c ol ors th at th ey furnish a

c onvenient t est for t h e pres enc e o f t h e m
.

etal s .

A s an illus t rat ion l et us experiment wit h t h ree aqueous solut ions

,

( 1 ) D issolve a l it t l e l ead acet at e in s ome wat er in a t es t

t ub e.
(2 ) D issol v e a b it of wh it e arsenic (A s 2 0 3) in a few d ro ps of h y dro
ch l oric acid and t h en add wat er ( 3) D issol ve a s mal l quant it y of an ant imony
.

sal t (t art ar em et ic ) in wat er N ow p ass a few b ub b l es of h y d rogen s ulfide

.

t h rough each s olut io n in t urn I n t h e firs t t es t t ub e we get a b lack precipi

.

t at e ( P b S ) , in t h e sec ond a yellow precipit at e (A s zs a) , and in t h e t h ird an

orange precipit at e

T hus we see th at c ertain metallic sirlfid es whic h are insol ubl e

in water or in dilute acid s c an b e prepared b y passing hydrogen
sulfid e int o an aqueous sol ution o f t h e metall ic salt .

m
Let us now experi ent wit h s al t s olut ions s o e of wh ich give an acid reac m
t ion wit h lit mus W e prep are d ilut e s ol ut ions of c opper sulfat e
.

iron s ulfat e pot ass iumsulfat e ( K 2 8 0 4 ) , and p ass afew b ub b les

of h y d rogen s ul fid e int o /
each . We get a b l ack precip it at e in t h e co p per
and no precipit at e in t h e
s ol ut ion o t h er t wo . If we now add a few d rops of
amm onia w at er t o t h es e t wo so l ut ions , we get a b l ck prec ipit at e in t h e a
iron sol ut ion b ut again not h ing in t h e pot assiu solut io n m .

In this experi ment we note th at copper sulfid e ( CuS) c an b e .

precipitated in an acid So l ution iron sulfid e ( FeS ) in an alka ,

line sol ution and th at potassium sulfid e is precipitated in

,

neith er acid nor alkaline sol utions T his furnish es a means of .

s eparating c opp er iron and p otassium

,
T h e foll owing equa
, .
‘

t i on will h el
p us t o und erst and this reaction :
I

0 11 8 0 4 H ZS CUS l H 28 0 4
198 S UL FU R A ND T HE S UL FI DES

In t h e case of iron sulfate we h ave wh at is c all ed a reversib l e

react ion which is indicated by t h e d oubl e arrow
FeS O4 s ; L
;
FeS 11 2 8 0 4

T h e iron sulfid e is ac ted upon b y t h e dil ute sulfuri c acid , which

is formed in t h e reac tion B ut by adding ammonia we neu
“
.

t raliz e this acid and thus all ow t h e iro n sulfid e t o form T his .

reaction will proc eed one way or t h e o th er according t o s l ight

c h anges in c onditions .

Some metal s, l ike silver and l ead , reac t d irectly with hydro
gen sulfid e t o form t h e metallic sulfid e T h e tarnishing of .

silver in t h e h ouseh old is prob abl y d ue t o , t h e h y d rogen sulfid e

wh ich c omes from sl ight l eaks in

'

gas pipes and fromt h e burning of

c oal I ll uminating gas is sup
.

C S z Vap o r
p osed t o b e free fro mth is gas, b ut
t o C o nd ens er
it usually contains a trac e o f it .

1 88 . C arb on ( C8 2 ) b i s ul fid e .

We h ave already seen 1 77) that

this is a val uabl e s olvent for it ,

dissolves sulfur rubb er and o th er , ,

sub st anc es th at are not sol ubl e in

I t is manufactured from
“
wat er .

c arb on and sulfur :

3

C 4 2 S 0 82 c al
G as C ar b o n
E l ec t r o d es S ulfur th at Wh en gram
T his means
Fur ac e for making carb on atom
Fig 1 1 2
. .

n
b i s ul fid e
ic weights are used in th is
reac tion c al ories of h eat
'

must b e supplied C arb on b isulfid e is call ed an endothermic

.

com pound . In fact t h e reac tion requires a very high t emp era
,

ture which is usually obtained commercially in an el ectric fur

,

nac e ( Fig . T h e main part is fill ed with c oke and t h e ,

sulfur is add ed th rough t h e h oppers T h e el ectric terminal s .

are near t h e bo ttom T h e h eat generated vaporiz es t h e sulfur

. .

T his unite s with t h e h ot c arb on t o fo rm c arb on b isulfid e .

20 0 S UL FU R A ND T HE S UL FI DES

T h e wat er sol ut io n i s c all ed h y d ro sul furic ac id ; it is a w eak acid

,

and for ms s ulfi d e s wit h mos t m

et allic s ol ut ions U s ed in ch e ical . m
analys is t o s eparat e met al s .

QUEs rroNs A ND R OB L EM S
'
P

1 . N ame t h ree pl aces wh ere l arge d eposit s of free sul fur o ccur .

2 . N ame t h ree compound s of sul fur found ab und ant l y in nat ure .

3 Expl ain wit h t h e aid

. of a l ab el ed d iagra m t he essent ial fact s of

t he Fras ch pro cess .

4 . M ent ion t h ree uses of t h e el ement sulfur .

D escrib e h ow y ou woul d pro c eed in t h e l ab orat ory t o prove t h at a

5 .

giv en y ell ow p owd er is sul fur .

6: W h at pro pert ies h av e t h e all ot ropic forms of s ulfur in common?

7 . C omp are s ulfur and oxy gen in s ev eral res pec t s .

8 . D efine all ot ropy and ment ion t he ment s

el e t h us far s t ud ied t h at
exis t in all o t ropic forms .

I n wh at t wo d ifferent w ay s
9 . c an o ne get well d efined -
c ry s t al s of a
sub s t ance ? I llus t rat e wit h sul fur .

10 . M ake a list of t h e ph y sic al pro pert ies of h y d ro gen sulfid e .

h y drogen sul fid e l n wat er is a weak acid Expl ain

'

11 . A sol ut ion of . .

W t
h a is it s name ?

12 S ilv er t arnish es and wh it el ead p aint b l ackensfv ery rapid l y in cit y

‘

air . Expl ain .

13 . W h at is t h e s o c all ed
-
sulfur wat er as found at S h aron S prings or

R ich field S prings , N ew Y ork ?

W rit e t h e na mes and fo r mulas oh fiv e met allic s ulfid es and of t he
c o respond ing oxid es
r .

1
43
15 . Writ e for t h e foll owing react ions : ( a) l ead nit rat e
the equat ions

(P b (N 0 3) 2 ) and h y d ro gen sulfid e ; ( b ) silv er nit rat e (A gN Oa) and h y drogen

( c) z inc chl orid e ( a l z) and so d ium sulfid e ; ( d ) co pper ch l oride
'

sul fid e ;

( 0 11 0 12 ) and h y d rogen sulfid e ; (e) ant imony ch l orid e ( Sh C l a) and h y drogen

sul fid e .

>l<

16 . T h e v ast d eposit s of sul fur in T exas are l ocat ed onl y ab out 1 000 feet
und er t h e ground W y is
h . it n o t mined as c o al is mined ?

17On wh at propert y
. o f sulfur d oes t h e succ essful o perat ion of the
Fras ch process d epend ?
18 . N ame t h e all ot ro pic forms o f sul fur Wh ich of t h e cry st alline forms
.

more int ernal ch emical Wh ich of t h ese is t h e more

'

c o nt ains t he energy ?

unst ab le at roomt em p erat ure ?

T OP IC S FOR FUR T HER S T U DY 20 1

Given as raw mat erials sulfur, h y d rochl oric acid , and iron, h ow
/f9
’

( .

coul d y o u pro ceed t o prep are h y d rogen sulfid e ?

20 . H ow woul d you rec ogniz e a s ul fid e in t h e l ab orat ory ?

21 . Writ e t h e equat ions for making silv er sulfid e in t h ree d ifferent way s .

22 . W h en h y drogen sulfid e is passed int o z inc sulfat e so l ut io n, t he reac

t ion is rev ers ib l e. H ow woul d y ou make it c ompl et e ?

23 . If an aqueous s ol ut io n of h y d ro gen sulfid e is all owed t o st and for
so me t ime in ab ot t le , s ul fur is d eposit ed . Expl ain .

>l< >l<

24 H ow man
ms 0 h drogensulfid e can b e ob t ained from1 00 grams
ra
yy
.

of non sul fid e ? w ? g
2 5 H ow many grams of non s ulfid e are need ed t o give w
. it h dilut e sul
“
furic acid roos ters of h y d ro gen s ulfid e und er s t and ard c o ndit io ns ? 2 5 ?!
7
v

T OP I C S FOR FU R T H ER S T U DY

R ub b er . Wh en was rub b er first used ? W h y h as it b ec ome so import ant

d uring t h e l as t t went y y ears ? H ow c an rub b er b e mad e sy nt h et ically ?
Wh at is t h e d ifference b et ween pl ant at io n and nat iv e rub b er ? Wh at is
_

t h e difference b et ween sy nt h et ic rub b er and pl ant at ion rub b er ?

( Slosso n 5
’

C reative C h emi s try, T il d en s C h emi cal Di scovery and I nventi on, C hemi stry in
’

I ndus try , Vol .

“
T h e S t ory of H ow was sulfur ext ract ed in Sicily ? For c ent uries
S ulfur.

Sicily and I t aly c ont rol led t h e sulfur market W h at ch anged t h e sit uat ion in
.

ab out 1 904 ? N ame six maj or indust ries using sulfur as a raw mat erial in t h e
ord er of t h eir rel at iv e magnit ud e as c onsumers (S ulp hur, A n E ssenti al to I n
. .

dus try and A gri cul ture, T exas G ulf S ul ph ur C o .

, 75 E 4 5t h St
. .
, New York ) .
 C HA P T ER XVI

OXIDES OF S ULFUR A ND T HEIR A C ID S

S ulfur d ioxid e prep arat io n and propert ies . Sulfurous acid

it s uses s ul fit es and b isul fit es .

S ulfur t rioxid e preparat ion and prop ert ies M anufact ure . of

sul furic ac id pro pert ies o f c oncent rat ed and d il ut e sul fat es

t es t for 8 0 4 io n
.

A c id and b asic anh y d rides .

189 . u
s lfuric ac id , afund ament al ch emical In 1 843 t h e .

great G erman c h emist Liebig wrot e th at t h e c o mm

, ercial pros
,

perit y o f a country c o uld b e fairly j ud ged b y t h e amount of

sul furic ac id it c o nsum ed T h at is With out d oubt as true
.

to d ay as it was nearl y a century :ago I t is estimated th at in t h e .

United States al one t h e val ue o f t h e sulfuric acid pro duc ed l n

o ne year is ab out 75 m ill io n d o ll ars Suc h quantities are need ed .

b ecause it is t h e h eavy c h emical whic h enters in one way or

ano th er into t h e manufac ture of nearl y everything we use .

Sinc e very l ittl e 1s stored it is manufac tured as need ed

m , T he .

arket for th is acid may th erefore b e consid ered as a b aro m

et er o f t h e econom ic prosp erity o f our country Sinc e t h e .

principal s ub stance required in it s manufac ture is s ulfur d io x

id e we sh all b egin with that c ompound
,
.

S U LFU R DI OXI DE A ND S ULFUR WSA CID

1 90 . P reparat io n fur d ioxid e Sulfur as we know
of s ul .
,

b urns in t h e air and forms an o xid e known as sulfu r

dioxid e T his gas h as a c h o king effec t familiarl y c all ed

“t h e s mell o f burning sulfur T h e equation is as foll ows :
.
”

S + 0 2

Ind ustrially t h e sulfur is b urned in a rotating drum A n .

o th er meth o d of prepari ng it consist s in h eating strongl y , or

2 02
 04 OXI DES OF S UL FU R A ND T HEI R A C I DS

Sulfurous ac id is so unstabl e a c o mp ound th at it is impos

s ibl e t o separat e it fro mt h e wa ter in wh ic h it is d issolved In .

fact , t h e main reason wh y we b el ieve th at it exists is th at t h e

s alts o f t h e ac id c an b e p repared T hus , wh en t h e ac id so lu .

tion is neutraliz ed by so d ium hydro xid e and evaporated it ,

gives a sub st anc e wh ic h c orresp o nd s t o t h e fo rmul a Na2 8 0 3 .

T h is would indic at e t h e fo ll owing equat ion

2 NaoH H 28 0 3 N3 2 SO3 2 H 20
s o d iu
m
h y d ro x 1
d e
s ul furous
amd
s o diu
s ul fit e
m
‘
"
wat er

Sulfurous ac id d oes not keep b ut s l owl y ab sorb s o xygen from

t h e air and c h anges into sulfuric ac id T h is c h ange is expressed .

by t h e equation
2 11 2 8 0 3 0 2 2 H 28 0 4
sul furo us o xy g en s ulf ric
u
ac i d ac i d

On account of t he rea diness with wh ic h it c omb ines with t h e

o xy gen from o th er c ompound s sulfurous ac id is a p owerful
,

red uc ing agent

FOR E X A MP LE , p ot assiu mpermanganat e

a very good oxidiz ( K M nO4) is
‘

ing agent W e d issolve a c ry s t al i n wat er and get a d eep v iol et sol ut ion
.
-
.

W e now p our t h is c ol ored liquid int o so e sulfurous acid s olut ion T h e m .

resul t is t h at t h e c ol or is i nstantly re mov ed b ec ause t h e sulfurous acid h as

t aken so me of t he oxy gen from t h e permanganat e l eaving p ot ass iumand ,

manganese sulfat es , c ol orl es s c o mpound s , in sol ut ion .

1 93 Us es of s ulfur d ioxi de
. T h e moist gas (th at is , sul .

“
furous ac id ) is used t o bl eac h p ap er pul p straw, silk , and wo ol
‘

.
,

T h ese are mat erial s wh ic h sh o uld not b e bleac h ed with c hl orine

,

sm ee 1t c aus es th em t o b ec o m e h ard and b rittl e T h e bl eac h .

ing effec t d isapp ears aft er at ime, h owever, and th erefore mat e
rial s bl eac h ed b y sulfur d iox id e yell ow with age ”
,

Sulfur
“ .

d ioxid e reduc es t h e c o l oring matt er, i e , rob s it of oxygen, and . .

c h anges it t o a c o l orl ess c omp ound B ut t h e air may c ause t h e .

c o l or t o return b ec aus e of re o xid at ion -

.

T his propert y c an b e sh own b y pl acing a numb er of moist col ored flowers

near b urning s ul fur and t h en c overing t h e wh ol e wit h a glass b ell jar
( Fig . A ft er a sh ort t ime t h e fl owers b ecome wh it e .
 1
S ULFI ES A ND BI S UL FIT ES
' '
20 5

Suc h foo ds as dried fruit s and c anned c orn a d c h erries are n

s om et im es bl eac h ed with sulfurous ac id T h e ac id also h as .

ant iseptic prop ert ies and will prevent t h e ferment ation o f sugar,
,

n
sweet c id er , a d preserves of vario us kind s It s use as a
‘

foo d preservative is , h owever, questionabl e .

T h at it is d ec id edly inj urious t o p l ant l ife

is evid ent from t h e bl ight ed v eget at ion in
t h e vic inity of smelt ers and c h emic al works
wh ere th is gas is all owed t o esc ape
“
.

Sulfur d ioxid e is often us ed in ic el ess

B ur ni ng
refrigerat ors T h e gas is l iquefied by a
.

motor driven c ompressor and th en is al

-

lowed t o exp and and evap orate T h ese Fig 1 1 4 B l e ac h i ng . . .

W it h s ulfur
p r o c es ses o f ex p ans io n and ev ap orat io n
325; 2
ab sorb h eat and keep t h e refrigerator c o ld .

B ut b y far t h e mo st imp ort ant use of s ulfur d ioxid e is in t h e

manufacture of sulfuric acid .

Wh en
“

1 94 . S ul fit es and b is ul fit es lfurous ac id is neu

. su

t raliz ed b y a b ase t h e salt pro duced is c all ed a s ulfit e

,
If an .

exc ess of s ulfur d io xid e is p ass ed int o t h e s ol ut ion of a b ase

—
,

t h e ac id s ulfit e or b is ul fit e (NaI i8 0 3) is formed

,
T h us , .

NaOH H 28 0 3 NaH8 0 3 H20

so d iu m s ul furous sod iu m wat er
h y d ro x 1d e ac id b is ul fit e

In t h e ac id sulfit es, or b isulfit es , th ere is one hydrogen at om

wh ic h h as not b een repl ac ed I n t h e sulfit es , o n t h e oth er
.

h and , all t h e hydrogen at oms h ave b een repl aced T h e ac id .

s alt m ay b e mad e by treat ing t h e ac id with only h alf enough

b ase t o neutral iz e it , or by add ing an excess of ac id t o t h e
normal lt sa .

A c ids l ike c arb onic ac id ( H 2 C O3) h y d rosulfuric ac id ( s ) , ,

sulfurous ac id and sulfuric ac id ( H 2 8 0 4 ) h ave two

rep l aceabl e hyd rogen at om s in eac h m o l ec ul e T h ey are th ere .

fore c all ed d ib as ic acid s Hy d roc hloric ac id and nitric ac id

( H N0 3) eac h h ave b ut one rep l ac eable h y d rogen atomper m
.

ol e
2 06 OXI DES OF S UL FU R A ND T H EI R A CI DS

l
cu e and so are monob asic acid s . P hosph oric ac id (H 3P O4 )
is a t rib as ic ac id .

1 95 Us es of s ul fit e s and b is ulfit es Wh en c alciumh y drox

'

. .

id e, or s l aked l ime is treat ed with an excess of sul

m
furous acid by p ersist ently p assing sulfur d iox id e th rough t h e
s o l utio n, t h e p ro d uc t is c al c iu b isulfit e T he
reac tion is as fo llows
C a( OH ) 2 2 H2 8 0 3 C a(HS Og) 2 2 H 20
m
c al c iu s ul furo us m
c al c iu wat er
h y dr ox id e acid b i sulfit e

In making h eaper varieties of p ap er woo d is c ut into

t he c ,

with a s o l ut ion of c al c ium b isulfit e

”
c h ips and c oo k ed T h is
”

d isso lves out t h e glue l ike substance (l ignin) of t h e woo d leav

"

ing t h e pure cellul os e wh ic h is t h e mat erial d esired for making

,

p ap er .

So d iumsulfit e ( N3 2 8 0 3) is oft en mixed with a wh ite cryst al

l ine sub stance oxal ic ac id , and used for bleac h ing straw h ats
,
[
.

N0 action t akes p l ac e wh ile th es e sub stances are d ry , b ut wh en

wat er 1s add ed , b oth sub st ances d isso lv e and t h e ions react .

SULFUR T R I OXI DE A ND S ULFUR I C A C I D

1 96 . I mport anc e of Sulfuric ac id h as b een

s ulfuric acid .

d es crib ed as t h e ki ng of ch emi cals b ec aus e th ere is s c arcely an

industry in wh ic h it is not d irec tly or ind irec tly used Wh y is .

it so extensivel y used ? For wh at is it used ? H ow is it man

ufact ured fromsulfur ?

B ut b efore w e answer th ese questions , we sh all h ave t o

investigat e sulfur trio xid e s ince it forms an important st ep in
t h e manufac ture of sulfuric ac id .

1 97 P reparat ion I t is p ossibl e t o make

of s ul fur t rioxid e
'

. .

sulfur d iox id e wh en h eat ed c om b ine t o a slight ext ent with

o xygen t o form sulfur trio x id e B ut th is react ion is
exceed ingl y s l ow T h ey c an, h owever, b e mad e t o comb ine
.

rapidly by m eans of t h e same c at alyst th at was used for t h e

 08 OXI DE S o r SUL FUR A ND T H EI R A C I DS

t rio xid e is th rown int o wat er it d issolves with t h e evolution of

,

much h eat
80 3 + 11 2 0 H 28 0 4

H ow s ulfuric acid is mad e A t t h e present t ime th ere .

are t wo meth o d s of manufacture, c alled t h e c ont act pro cess

and t h e c h amb er pro cess I n b oth processes t h e firs t st ep is
.

t h e same, namely , burning sulfur or ro asting a metall ic sulfid e

t o get sulfur d iox id e T h e c h ief d iffic ulty c o mes in t h e next
.

st ep wh ere sulfur d iox id e is c h anged int o sulfur t riox id e T h is .

is o verc ome by using a c at alys t , and h ere is wh ere t h e princ ipal

Wat er C onc H 2 8 0 4
.

D r y i ng H eat er C o nt ac t A b s or p t i o n
B ur ner T o w er T o w er T o w er

Fig
. 1 1 6. D iagramof c ont act proces s for making sul furic acid .

difference b etween t h e t wo proc esses lies I n t h e c ont act proc .

ess t h e c at alyst is vanad iu m oxid e or platinum kept at a defi

nit e t emperature I n t h e c h amb er process t h e c h emic al c hanges
.

are very c ompl ic at ed : t h e sulfur d iox id e is c h anged t o sulfuric

ac id by t h e us e of Steam o x id es of nitrogen an , d air T he , .

"

apparatus is so arranged th at t h e ox id es of nitrogen c annot

escape b ut are used o v er and ov er again .

I n t h e cont act pro c ess ( Fig 116 ) t h e c at aly t ic agent is v anad ium oxid e
.

or, as in our experim ent finel y d iv id ed pl at inum W h en prepared .

c om mercially , t h e mixt ure of sulfur d ioxid e and air is carefully freed from
d ust and ot h er impurit ies Unless t h ese are removed from t h e gases , t h e
.

pl at inum so o n l oses it s c at aly t ic p ower T h e t emperat ure must al so b e

.

c arefully regul at ed a nd kept at 4 00 C ( Fig I f it falls b el ow t h at

°
. .

point , t h e reac t ion is t oo sl ow ; and if it rises ab ov e it , t h e rev erse react ion

set s in . Finall y , t h e sulfur t rioxid e is ab s orb ed in c oncent rat ed sul furic
H OW S UL FUR I C A C I D I S M A DE 209

ac id (inst ead ofin wat er) b ecause it h as a great t end ency t o pass t h rough
t h e l at t er in t h e formof a mist , or fog, wh ich c anno t b e caugh t ( Fig
,
.

T he res ul t ing fuming

acid is c all ed

s ulfuric ac i d o ol eum T his is

”
r .

essent iall y as ol ut ion of sulfur t rioxid e

in conc ent rat ed s ulfuric ac id W h en .

fuming sul furic acid is d il ut ed wit h

wat er, t h e sul fur t rioxid e comb ines
wit h t h e wat er and prod uces sulfuric
acid .

I n t h e ch amb er pro c es s ( Fig 1 19) .

t h e oxid es of nit rogen are us ed as t h e

c at aly t ic agent T h e sulfur d ioxid e
.

is oxid iz ed t o sulfur t rioxid e b y t h e aid

of nit rogen d ioxid e ( N O2 ) , a b rown
gas .T h e l at t er sub s t anc e (N O2 ) is
red uced t o nit ric o xid e (N 0 ) B ut
t h is l n t urn t akes oxy gen fro mt h e air C ourt esy C h e mi cal C onst ruct i on C orp
mt h e
.

t o for high er oxid e of nit rogen

Fig . 1 1 7 . C ont act t ower .

again . T h us t he nit ric o xid e, by

b eing alt ernat ely oxidized b y t h e air and red uced b y t h e s ulfur d ioxid e,
act s as a c arrier of oxy g en T h e reac t ion is c arried out in l arge l ead ch am
.

b ers T o aid in t hi s pro cess , as well as t o furnish t h e necess ary w at er t o c on

.

v ert sul fur t rioxid e int o sul furic acid ,

mis b l ownint o t h e l ead ch amb ers
s t ea .

I n p rac t ice t h e gases from t h e

,

s ul fur or py rit e b urners p ass t h rough a

t ower ( Gl ov er) , wh ich serves t o c ool
t h e gas es and t o c h arge t h e wit h m
o xid es o f nit ro gen. Fro t h e l as t of m
t he s eries of c h a mb ers t h e gases p ass
t h rough ano t h er t ower L
( G ay uss ac ) ,
-

in wh ich t h e oxid es of nit rogen are

ab sorb ed in concent rat ed sulfuric acid .

T h is ac id is t h en pumped t o t h e t op
o f t h e firs t t ower , wh ere it is d il ut ed

and gives up t h e oxid es of nit ro gen

'

T h e acid wh ich col l ect s int h e ch a m

b ers is ab out 60 per cent pure h y
o nl y

d ro gen s ul fat e ( H 2 S O4 ) T h e ch a b er
. m
pro cess is t h e ol d er m
et h o d and is

m
C ourt esy C h e i cal C onst ruct i on C orp . s t ill us ed ex t ens iv el y fo r aking t h em
Fig . 1 1 8. A b s orpt ion t owérs . less co ncent rat ed grad es of sulfuric
210 OXI DES OF S UL FU R A ND T HEI R A C I DS

acid For p rod ucing c oncent rat ed s ul furic acid , t h e co nt act process is
.

superior T h e ad v ant age of t h e cont act pro cess o ver t h e c h amb er pro cess
.

d epend s upon t h e fact t h at a v ery pure acid o f any st rengt h c an be mad e

d irect ly wit h out an expensive process of concent rat ion .

L ead Ch a

G l over

G ay M ss ac
-

T o wer

Fig . 1 1 9. m
D iagramof t h e ch a b er pro cess for making sulfuric acid .

2 00 . P ropert ies of c onc ent rat ed

.
Sulf uri c
P ure sulfuric aci d .

ac id is a c o l orl ess , o ily l iquid ab out twic e as h eavy as water .

C omm erc ially it is known as oil of vit riol b ec ause it was for
merly mad e b y d istill ing ferrous sulfate cry stals , wh ic h h ave
l ong been known as green vi tri ol ( FeSO4 7 E ZO) I t b o il s at 0
.

a h igh t emp erature (338 I t is an exceed ingly c orrosive

°

sub st ance and if spill ed o n t h e S kin pro d uc es b ad b urns It .

mixes with water in all prop ortions , evolving al arge amount of

.

h eat Sinc e t h e c onc entrated ac id h as a great attraction for

.

wat er, it is used for d ry ing many gases .

C l osely c onnect ed with th is avid ity for wat er is t h e d eh y d rat

ing act ion o f t h e ac id I t will remove h y d ro gen and o xy gen
.

in t h e f orm of wat er from many sub stances wh ic h c ontain

th os e elements for exampl e , , sugar

T o sh ow t h e act ion of sulfuric acid on p aper, wh ich is l argely cellulose

( C sH mOs) , we writ e wit h a gl ass rod and s ome d il ut e sul furic ac id upo n
wh it e p aper W e d ry t h e p aper c areful ly b y h ol d ing it at s ome d ist anc e
.

ab ove t h e B unsen fl a e m
W h ere t h ere is writ ing t h e p aper t urns b l ack and
. ,

c h arred ( Fig 1 2 0 ) b ec aus e t h e d il ut e acid b ecom

. es co ncent rat ed t h rough

t h e evaporat ion of t h e wat er .

2 12 OXI DES OF S UL FUR A ND T H EI R A C I DS

2 02 . Dil ut e G reat c are must b e t aken in d i

s ulfuric acid .

luting sulfuric ac id b ec ause a l argeamount o f h eat is generated .

It seems pro b abl e th at t h e sulfuric ac id , or more properly

i

“
h yd rogen s ulfat e , transfers hyd ro gen ions GP ) t o t h e wat er, -

thus pro ducing an h y drated hydrogen ion (sometimes c alled

o x oniumio n, H 30 ) and an ac id sulf at e ion
+
We p our
th e concentrated aci d i n a sm all stream int o t h e wat er, not t h e
wat er int o t h e ac id It reac t s with suc h met al s as z inc , iron,
.

and aluminum, forming free hyd rogen and t h e sulfates of t h e

metal It can b e neutraliz ed with b ases , forming salts D ilute
. .

sulfuric ac id h as no att rac t ion for wat er , is not an o xid iz ing

agent , and o bviously c anno t b e used for suc h p urp os es as p re

paring hyd ro gen c hl orid e I n all th ese respec ts it d iffers fro m
.
-

t h e conc entrated ac id T h is d istinc t ion S h ould b e c arefully

.

noted .

20 3 . S ul fat es . T h e salts of s u
lfuric acid wh ic h c ontain no
hydrogen are c all ed S ulfat es T h e salts wh ic h still h ave one .

at o m of hydrogen per mol ec ul e are c all ed b is ul fat es o r ac id

s ul fat es . m
T h e sulfates o f any metal s arevery imp ort ant and
are in c o mmon use T hus plas t er of P aris is p artl y h y drat ed
.
,

c al c ium sulfat e
_

( (C aSO4) 2 Hzo) Eps o m s al t is h y d rat ed ?

magnesium sulfate (M gSO4 7 H zO) T h ey are for t h e most .

part cryst alline so lid s wh ic h are s ol ubl e in wat er T h e sulfates .

of b arium strontium and l ead are i nsolub l e;

, , sulfat es of S ilver

and c al ciumare only mo d erat ely sol ubl e .

“
T h e t es t for a s ul fat e , th at is for t h e ion S 0 4 , is t h e add i ,

tion of a s oluble b ariums alt (suc h as t h e c hl orid e) t o t h e s o lu

tl on l n question If a wh it e prec ipitat e is formed wh ic h is in
.

so l ubl e in hyd roc hl oric ac id a sulfat e is present ,

133 0 12 Na2 8 0 4 c 133 8 0 4 i ““

i 2 NaCl
b arium sodiu m b arium s od 1 um
c h l ori d e s ulfat e s ulfat e c h lo nd e

20 4 . furic acid C oncentrat ed sulfuric ac id is

Us es of s ul .

us ed as a d ry ing agent b oth in t h e l ab orat ory and in t h e ind us

tries In enormous quant ities it ent ers int o t h e manufac ture
.
A CI D A ND BA SI C A NH YDR I DES 2 13

of dyes and into t h e pro d uc tio n of a nu b er of organic s ub m

stanc es wh ic h s ery e as exp l osives B ecause of it s h igh b oil ing
.

o int it is us ed in t h e l ab o rat o ry for t h e prep arat io n o f o th er

p ,

ac id s from th eir salts T h e d ilut e ac id is used in st orage

'

batteries and in elec tropl ating ; al so in c leaning t h e surfac es

of m any met als Large amounts are c o nsumed in t h e fert iliz er
.

ind ustries It is now o ne of t h e c h eap est of c h emic al s (ab out

.

$10 a t on) On account of it s varied and ext ensive uses

.
,

sulfuri c aci d m ay b e considered as one of the foundati on stones

of m od ern i ndustry ( See Industrial C h art A ppendix )
.
,
.

205 . A cid and b as1c anh y d rid e s . T h e t wo o xid es of lfur

su

( 8 0 2 and 8 0 3) react w ith wat er t o p ro d uc e sulfuro us and sulfuric

ac id respec tively A n o xid e wh ic h c o mb ines with water t o form
.

an ac id is oft en c all ed an ac id anh y d rid e A noth er exampl e is .

c arb on d io xid e wh ic h reac t s with wat er t o f orm c arb onic ac id

,

(H 2 C 0 3) C arb onic acid l ike sulfurous ac id is unst abl e and

.
, ,

on h eating go e s b ac k int o t h e anh y d rid e T h e reaction is .

th erefore reversible
H 20 j C Oz fi
“
H 2 C O3

A noth er ac id anh y drid e is t h e wh it e o xide o bt ained b y burn

ing ph osph orus in air T h is c ombines with h ot wat er t o form
.

ph osph oric acid , wh ic h l ike sulfuric ac id is st abl e and d oes not

easily revert t o t h e anh y d rid e

P 20 5
“
j 3 H 20
"

2 H 3P O4

T he o xides of no nmet al s are ac id anh y d rid es

xides of . T he o

t h e met al s , on t h e o th er h and unit e with wat er t o formb ases , .

For exampl e cal ciumoxid e reac ts with water t o form c al cium

,

h y droxide :
C aO E 20 C a(OH) 2

T h isd ifferenc e in t h e beh avior of t h e o xid es of t h e nonmetal s

and metal s is often ind ic at ed b y c all ing t h e former acid ic oxid es
and t h e l atter b as ic oxid es
[
.
 I4 OXI DES OF S UL FUR A ND T H EI R A C I DS

SUM M A R Y OF C HA P TER XVI

S ULFUR D IO XID E I S P REP A R ED b y

( 1 ) b urning s ul fur or b y roast ing s ulfid es

( 2 ) t h e act ion of h y d roch l oric acid on b is ulfit es
S ULFUR D I OXID E is a c ol orl es s , ch oking gas wh ich is more t h an
t wic e as h eavy as air . I t is v ery s ol ub l e in wat er .

m
I t is us e d as a ger ic id e , a pre s erv at iv e , and a b l each ing agent .

I t is al s o us e d in c ert ain ic el es s refrigerat ors Its ain us e is in . m ,

th e manufacture of t h e acid s of s ul fur .

S UL FU R OU S A CI D is t h e wat er s ol ut ion of s ulfur d ioxid e and is

unst ab l e . I t is a red ucing agent . I t h as b l each ing and ant is ept ic

propert ie s . I t for ms t wo
.
c l ass es of s al t s , s ul fit es and b isulfit es .

A n acid wh ich h as t wo repl ac eab l e h y d rogen at oms per mol ecul e is

c all ed d ib as i c .

S ULFUR T R I O XID E is for med b y t h e uni on of s ulfur d ioxid e and

o xygen wit h t h e aid of a h eat ed c at al y s t . I t unit es wit h w at er t o fo r m
sulfuric aci d .

S UL FUR I C A C ID IS M A NUFA C T U R ED by ( 1) th e contact

O

proc es s , in W h ich t h e s ul fur d io xi d e is o xi d ize d wit h t h e help of a

c at aly st , and (2 ) t h e ch a b er m proc ess , in wh ich th e o xi d at ion is
b rough t ab out b y t h e us e of t h e oxi d es of nit rogen .

C ONC ENT R A T ED S U L FU R I C A C ID h as a s trong at t ract ion for

w at er W h en h ot , it is an oxidiz ing agent W h enh eat ed , it will d riv e
. .

out ot h er aci d s from t h eir s al t s b e c aus e of it s h igh b oiling point .

D I LU T E SUL FU R I C A C I D r eac t s w it h many met al s , forming

h y drogen . I t fo r ms t wo c l as s es of s al t s s ulfat es and b isulfat es .

A ll s ulfat e s are s ol ub l e exc ept t h os e of b arium, s t ront iu m and , l ead ;

sulfat es of silver and c al ciu mare onl y mod erat el y s ol ub l e .

S UL FUR I C A C ID I S U S ED in nearl y all ind us t rie s .

T H E O XI D ES OF T H E NON M ETA L S , s uch as 8 0 2, $0 3, 00 2,

P 20 5, react wit h wat er and foim acid s '

. T h ey are c all ed acid an
h yd rid es or acidic oxid es

T H E O XID ES OF T H E M ETA L S , like C aO , react wit h wat er t o

for mb as es . T h ey are c al l ed b as ic oxid es .
2 16 OXI DES OF S UL FU R A ND T HEI R A C I D S

20S t raw h at s and newspapers t urn y ell ow

. o n l o ng exposure to s unligh t .

Expl ain .

21 . Expl ain h ow s ul furous acid ( H zS Oa) act s as a red ucing agent and
s ul furic acid ( H ZS O4 ) as an o xid iz ing agent .

22 S h ow h ow t h e preparat ion of s ul fur dioxid e from t h e act io n of h ot

.

co ncent rat ed s ulfuric ac id o n co p per ill us t rat es t h e oxidiz ing ac t io n of c o n

cent rat ed sulfuric ac id .

23 C ommercial s ulfuric acid is not generall y

. c ol orl ess . H o w d o y ou
ac count for t h e col or ?
24 H ow coul d y o u d et ermine wh et h er t h e s ul furic acid in a b o t t le were
.

c oncent rat ed or d il ut e ?

25 . A b eaker co nt aining c oncent rat ed s ulfuric cid is s omet imes pl aced a

ins id e t h e c ase o f a c h emic al b al ance W h y ? A ft er it h as s t ood for some
.

time , we not ic e t h at t h e lev el of t h e l iquid in t h e b eaker h as risen . Wh y ?

>l<

26 . C omput e t h e percent age co mp osit i on o f sulfuric acid .

27H ow rnany kil ograms of sul furic acid ( d ensit y

.
‘

g . m
c .and 96 per
3

cent pure) c an b e mad e b y roas t ing 1 0 0 kil o grams of z inc s ulfid e wh ich is

6 0 per cent ur ?
p e

28 . n
H ow ma y grams of s ulfur d ioxide c an b e mad e b y ro ast ing (b urning)
60 grams of iron py rit e ( FeS ? )
29 . H ow much s ul fur will b e required t o prep are a t o n ( 2 00 0 l b s )
. of

sul furic acid c o nt aining 4 per c ent o f wat er ?

’

weigh t of b arium sul fat e (B asO4 ) is precipit at ed wh en a

7
30 . W h at
sol ut io n co nt aining 2 6 grams o f anh y d rous b arium c t rid e is t reat ed wit h

s ufficient sul furic acid ?

T OP I C FOR FU R T H ER S T U DY

C at aly sis in ind us t ry W h at woul d appear t o b e t h e ad v ant age of t h e

.

co nt act pro cess ov er t h e ch am b er process for pro d uc ing sulfuric acid ? W h y

h as it not ent irel y s upers ed ed t h e ch amb er process ? W h at o t h er manu
fact urmg
'

Op erat io ns us e W h at are s ome of t h e s ub st ances used

c at al y s t s ?

as c at al y st s ? ( D uncan s
’
Chemis try of C om merce C hemistry in I ndustry
, ,

Vol .
 C HA P T ER XV I I

CA R B ON A ND IT S T W O O XIDES

C arb on and it s al l ot ropic forms : d iamond , graph it e, c h arcoal ,

and c oal c h emic al b eh av ior of c arb on S t ruc t ure of c arb on .

at o m
.

C arb on d ioxid e — pro d uc t ion b y b urning and d ecay — o ccur

.

rence in air — t es t — us ed b y pl ant s P reparat io n b y act io n of

.

ac id s on c arb onat es exp eriment s propert ies liquid and

solid mmercial uses
co .

C arb on monoxid e pro d uced b y c o al fire , by red uct ion, m

fro
formic ac id prop ert ies and uses
C om
.

pos it ion of t h e d ioxid e and monoxid e .

20 6 . A ll ot ropic for ms of tainly requires

c arb on . It c er

consid erabl e im agination t o b el iev e th at c h arc o al graph it e and

m
, ,

d iamond are onl y d ifferent forms of one and t h e sa eelement .

B ut d espit e th eir wid ely d ifferent physic al prop erties th ey are ,

all el ementary c arb o n We may prove th is experimentally

.

by Sh owing th at eac h of th em will burn in o xygen and evo lve

c arb on d iox id e as t h e s o l e pro d uc t A s in t h e c ase of sulfur
.
,

we h ave h ere t wo crystall ine forms d iamond and graph it e , as ,

well as c ertain amorph o us , or no ncry st all ine f orms suc h as , ,

c h arco al and l am p blac k I t is p ossibl e t o c h ange th ese f orms

.

into o ne anoth er C h arc oal c an b e c onverted int o graph it e by

.

h eating it t o a very h igh temperature out of c ontac t with air .

I t is even possibl e t o make very small d iamonds artifi cially .

2 07 D iamond s
I n c ert ain l o c al ities o f South A fric a,
’

. .

South A meric a, and t h e East I nd ies d iamo nd s are found in

_

gravel d eposits I n th eir nativ e st at e th ey are not at all like

.

t h e gems wh ic h t h e name suggests T h ey generally l oo k .

like ord inary rough stones , h ardly transparent , and with l ittle
2 17
2 18 C A R B ON A ND I T S T W O OXI DES

y tal s T o make th em into gems

being
'
appearanc e of cr s .

( Fig . th ey are ground or c ut in s uc h a way th at th ey

, ,

will reflec t l ight fro manumb er of d if

“
ferent faces ; th at is th ey sparkle ,
”

in t h e l ight .

D iamond is t h e h ard est sub stance

known I t c an b e cut and polish ed .

D iamond s rough o nly by oth er d iam ond s or by d iamo nd

and °“
Fig 1 2 1
. .
,

So me d iamonds are bro wn

t
p owd er
'

ish and even blac k ; th ese are used for c utt ing gl ass and for
giving a c utting ed ge t o d rills and roc k b orers -
.

20 8 . G raph it e A nother for

. of cryst alline m
c arb on is

graph it e . A lth ough it occurs abund antly in nature, it is now

al so m
anufactured on a l arge sc a e l fromh ard c oal . Hard coal

Fig . 122 . R es is t anc e furnac e for making graph it e .

is a formof impure c arb on wh ic h p asses int o graph ite wh en it

is subj ec ted t o a very h igh t emperature out of contac t with
t h e air T h is h igh t emperature is pro d uced in a so c all ed
.
-

el ect ric res is t ance furnac e . A powerful e ec ric c urren

l t t p asses
22 0 C A R B ON A ND I T S T W O OXI DES

c h arcoal th ese were all owed t o esc ape b ut in a mo dern p l ant

, ,

(Fig 12 3) th ey are c ond ensed and used

. C oke is st ill anoth er .

c om mon substance wh ic h is essentially amorph ous c arbon

-

It is formed from c oal in exac tly t h e same Way th at c h arcoal

is mad e fro m woo d B oth c o ke and c h arco al are used as fuel s
.

and as red uc ing agents in met

allurgic al op erations .

T h e reduct ion O f c opper oxid e wit h

C uo + c c arb on will ill ust rat e t h is us e We .

h eat a mixt ure of b l ack c opper oxid e

and ch ar c o al in a h ard gl ass t est t ub e
-

( Fig 124 ) and l ead

. t h e gas ev olved
int o m
li ewat er T h e wh it e precipi
.

t at e S h ows c arb on d ioxid e M et allic

.

c o pper is l eft in t h e t ub e

Z C uO + C —
> 2 Cu

We Shall mention only a few

ther forms of amorp h ous
of t h e o

m
_

c arb on La pb l ack is mad e by .

Fig 1 2 4
. R ed uc t ion o f copper o x—
. id e b urning certainoils in a l imited
W i t h c arb on
s upp ly of an and c o ll ec t i ng t h e
.

soot C arb onb l ack is similarly prep ared b y burning natural

.

gas .B oth are impure c arb on Large quant ities are used in
.

t h emanufac ture of print er s ink p aint and aut omob ile tires
’
.
, ,

T h e c h arco al wh ic h i s mad e by h eating b ones with out ac cess of

air is c all ed animal c h arco al o r b oneb l ac k, and is ext ensively
used in d ec ol oriz ing s o l ut ions ; for examp le in t h e refining o f ,

sugar T h us we s ee th at c oke c h arc o al and b onebl ac k are

.
, ,

pro d uc ed by t h e d estructive d ist ill ation of c o al wo o d and b ones , ,

respect iv ely .

2 10 . C oal . T he variety of amorph ous

most important
c arb o n is ord inary c o al T h e c oal we burn t o d ay was onc e
.

living vegetation T h is h as l ong b een buried und er b ed s of

.

’
sand as t h e result of certain geol o gic al c h anges in t h e earth s

c rust and h as b een subj ec ted t o p ressure and fairly h igh

,
C H EM I CA L B EH A VI OR OF CA R B ON 2 21

temperatures I n c onsequence t h e vegetable material h as

.
,

und ergone a p artial d eco m p o s it io n y ield ing am orph ous c arb on

,

as t h e main pro d uc t
'

A nt h rac it e c oal ( h ard c oal ) is ab out

.

90 per cent c arb on nearl y all of wh ic h is in t h e unc ombined

,

st at e B it umino us c o al (soft c o al ) co ntains s omewh at l ess

.

c arb on ; a consid erabl e p a rt of it is c o m bined with h y drogen ,

ox ygen nitrogen and sulfur

, ,
C oal is us ed d irectly as a fuel
.

and al so for t h e manufac ture of co ke .

T h e p l ant for t h e pro d uct ion of c oal gas ( Fig 1 2 5) c onsists .

essent ially of t h e f o ll owing part s iron r et ort s , or o vens inwh ic h ,

C ond ens er

P ur ifier G as H old er

C oal T ar and
A mmoni acal L i quor

Fig . 12 5
. Diagra mof a pl ant for making coal gas and it s b y prod uct s
-
.

t h e soft coa l is h eated aseries of t o wers and s crub b ers th rough

wh ic h t h e gases pass in ord er t o remo ve h eavy, tarry material
(c oal t ar) , ammonia gas, and h y drogen sulfid e ; a gas h ol d er t o .

c oll ec t t h e purified c o al gas T h e coke is l eft in t h e ret orts

. .

C oal t ar and ammonia, as well as t h e co al gas and t h e co ke, are

of great c om merc ial value (Fig .

2 11 . C h emical None of t h e forms

b eh avior of c arb o n .

of c arb on reac t with b ases or d il ut e ac id s T h ey d o not d is .

s o lve in ord inary so lv ent s alth ough m elt ed i ro n d oes d issolve

,

c arb on t o a certain ext ent A t ord inary t emperatures all .

forms of carbon are very inert A t h igh temperatures how

‘

“
.
,

ever th ey all b urn fo rm

, ing c arb on dio xid e or in a l imited
, , ,

supp l y of ox y gen c arb on m o no x id e

, A l so at h igh t empera .

tures c arb on acts as a reduc ing agent and thus removes oxygen
222 C A R B ON A ND I T S T WO OXI DES

C ourt esy T h e K opp ers C onst ruct i on C o .

Fig
. 12 6 . B y prod uc t
-
c oke oven
-

pl ant .

fromt h e oxid es of many met als T h is is essentially t h e process

.

of pro d uc ing m et al s from th eir o res .

2 1 2 S t riI ct ure of t h e c arb on at om T h e el ectron picture of

. .
-

t h e c arb on at om ( Fig 1 2 7) S h ows a nuc l eus with a p ositive

'

c h arge of 6 pro t ons surround ed b y 6 el ec trons

,
T wo el ectrons .

are in t h e inner sh ell and 4 are in t h e next S h ell .

Ca b n
C onsequently we S h ould exp ec t t h e c arb on atom
r o

eith er t o l ose 4 el ec tro ns and ac t l ike am et al or t o ,

gain4 elec trons and act l ike ano nmet al I nsh ort .
,

we S h ould S ay th at t h e val enc e of c arb on is p lus 4

or m inus 4 d epend ing on t h e el ement with which
,

it reac ts Suc h an el ement wh ich may b eh ave

.

of carb onat om l ike a m et al or a nonm et al is c all ed am p h ot eric

*

.
2 24 C A R B ON A ND I T S T W O OXI DES

cen t in crowd ed rooms It also boeurs in natural waters and

.

in t h e so il I n certain v ol canic l oc al ities it esc ap es fromfissures

.

in t h e earth s crust For exampl e near Napl es th ere is a c ave

’
.
,

in wh ic h t h e air at t h e b ott o mcont ains so l arge a proport ion of

c arb on d iox id e th at a d og would b e o ver

c om e I n Yello wstone P ark th ere is a vall ey

.

wh ere animal s h ave d ied b ec aus e th ey h ave

b een suffocated in c arbon d ioxid e T h is gas .

o cc urs in cert ain m ines and is c all ed b y t h e

‘

“
miners c h o ke d amp I t is oft en found in
”

“
.

t h e b ott omof ol d well s ,c isterns and c l ean ,

outs for sewer pip es I t is not p erceptibl e

”
.
,

and h enc e many peopl e h ave l os t th eir l ives

b ec ause of it T h is d anger may b e avoid ed
.

b y t esting with a l ight ed l antern If t h e .

flame is extinguish ed th ere is insufficient ,

o xygen for l ife .

2 15 . T est s fOr ’
c arb on ,
d ioxid e . We c an
easily prov e th at c arbo n d io xid e is present in
t h e breath b y a S i pl e exp eri ent By m m .

m m
,

eans of a gl ass t ub e we bl ow through so e

l l imewater I n a l arge test tub e as

c ear

“““
,

Fig 1 2 9 Bl owing S h own in fi gure 1 2 9 We notic e th at at

m gh mewmr
. . .

first t h e breath bubbles pro duc e prac tic all y

'

no c h ange B ut as soo n as t h e breath c omes fro m farth er

.

with in t h e lungs t h e c l ear l iquid turns milky T his S h ows

,
.

T h e producti on of m
'

t h e presenc e of c arb o n d io xid e ilkiness .

in limewat er is a ch aracteris ti c of carb on di oxide .

C a( OH ) 2 C O2 030 0 3 1 H 2O
l imewat er p rec ip it at e

C a( OH ) z H 20 0 3 C aC0 3 2 H 20
T o Sh ow t h at c arb on d ioxid e is prod uced wh en any c arb on c ompound is
b urned in t h e air, we set fire t o a piec e o f p aper and d ro p it wh il e b urning
To make limewat er pl ac e a h andful of p o wd ere d sl ake d l i e in a b ig b o t t le and
,
m
fill it wit h wat er . C o rk it and s h ake it for a minut e T h en l eav e t h e ixt ure t o
. m
s et t l e o vernigh t and in t h e morning p o ur off t h e c lear sol ut io n for use .
P R EP A R A T I ON OF P UR E C A R B ON DI OXI DE 225

int o a d ry b ot t le We t h en pour in a lit t le limewat er, cover t he b ot t l e wit h

.

a glass plat e, and sh ake it up .

W e may also h old a d ry b ot t l e invert ed over a c and le flame and S h ow t h e

n e o f c arb on d ioxid e in t h e pro d uc t s of c omb ust ion b y means of l ime
pre se c

wat er .

2 16 . P l ant s need A t first th ought it would

c arb on d ioxid e .

seem th at t h e c on st ant pro duc tio n of suc h vast am ounts of

carb on d ioxid e as we h av e d escrib ed m ust fill t h e atmosph ere

with t h e gas T h e fac t is , h owever, th at wh en pure air in
.

t h e country is anal y z ed , it is never found t o c ontain more

th an three or four h undredth s o f
.

one p er c ent o f it T h is is b e.
Oxy g en
c ause m ost pl an t s r ev e rse t h e

p i '
o cess w h ic h t ak es p l a ce in an i
mal s T h ey ab sorb carb on dioxid e
.

from t h e air and give off oxy gen .

During d ayl igh t all green p l ants

c onv ert t h e c arb on d ioxid e and

Water into aformof sugar and into

"

s tarch
6 C Oz + 5 H2 0 6 0 2 I + C sH10 0 5
eaves
st arc h

T h e l ib erat ion of oxy gen from pl ant s

c an easil y b e sh own W e pl ace fresh
.

green l eav es in ajar und er wat er s at urat ed

Fig 1 30
. . P l ant s ab s orb carb on
wit h c arb on d ioxid e, as in figure 1 30 , and d ioxi d e and s et free oxygen .

t h en set t h e jar in t h e s unligh t . B ub b l es

of gas appear on t h e l eav es , grow l arger, d et ach t h e selves , and rise t o t h e
-
m
t op .T his gas m
ay b e coll ec t ed in a t est t ub e and t es t ed wit h a gl owing
S pl int er of woo d
’

I t i s oxygen
. .

We Sh all in anoth er c h apter (XI X) th at t h e small amount

see

of c arb on d ioxid e in t h e air varies v ery l ittl e I t is of t h e .

greatest S ignifi c ance b ec ause of t h e intimate rel ation it b ears

t o t h e life of all pl ants and animal s .

2 17 . P reparat ion p ur e of
c ar b on d ioxid e in t h e l ab orat ory .

I t is possibl e t o prepare pure c arb on d ioxid e by burning c arb on

2 26 C A R B ON A ND I T S T wo OXI DES

in xygen B ut it is d i ffic ult t o separate t h e gas from t h e

o .

unused o xygen I n t h e l ab o rat ory it is usually prepared b y

.

t h e ac tio n o f an acid on marbl e M arbl e is a c h emic al c om .

pound call ed c al c iumcarb onate and is mad e up of t h e el ements

c al cium c arb on and oxygen
, ,

C aC Os 2 H0 1 C aC l Z
-

H 20 0 3
marb l e
H 20 0 3 H 20 "

i 00
“
2 1
Wh en dilute acid l ike h y d rochl oric ac id is brought into
a
cont ac t with a c arb onat e a vigorous effervesc enc e , or b l ib b ling
, ,

takes pl ac e T h is c ontinues until eith er t h e marbl e or t h e

.

fervesc ence somewh at resembl es b oil ing

'

acid is all used up Ef .

,

ex cep t th at t h e vap or wh ic h rises in b oiling is

al way s t h e same sub stance as t h e l iquid from

whic h it c omes
“

To c oll ect m
t h e gas ev ol ved in t h is ch e ic al ac t io n, w e
may use m
t h e s a e app arat us as in p reparing h y d ro gen
”

(Fig . m
P iec es of arb l e are pl aced in t h e b ot t l e, and
dilut e h y d ro ch l oricacid is p oured in t h rough t h e t h is t l e
t ub e T h e ac t ion s t art s at o née, and t h e gas may b e
.

col l ec t ed as usual in b ot t l es int h e p neu mat i c t rough .

2 18 . Experi ment s wit h c arb on d ioxid e . To

s tudy t h e prop erties of th is gas we may perform ,

t h e fo ll owing ex p eriments :

(1) L igh t ed t apers are pl aced I n a j ar oft h e gas ( Fig

Fig 1 3 1
. .C arb on
d ioxid e put s out
does this S how
T h e lo
w m
er fl a e 1s at o nce put o ut . Wh at p roperty

c and l e fl ame ( 2 ) W e d ip a st irring ro d int o s ome limewat er and

t h en wit h d raw it s o t h at a cl ear d ro p h angs from it s end
,

I f t his is l owered int o a b ot t l e of t h e gas , it immed iat ely b ecomes cl oud ed ,

or m ilky , in appearance T his i s a t es t for carb on di oxi de
. .

( )
3 W e m ay l o w e r a s h ort p iece o f l ig h t e d c and l e int o a wid e mo ut h ed -

b eaker and t h en pour t h e gas fromo ne of t h e b ot t l es o v er t h e c and l e T he .

c and l e goes out . What d oes this sh ow ab out the relative d ensi ti es o f this gas
and air ?
Let
“
US col or s o me w at er wit h a few d rops of t h e d y e s ol ut ion known
as l it mus . We let gas fro m t h e generat or b ub b l e t h rough it for a few
228 C A R B ON A ND I T S T W O OXI DES

m
precipitate for ed wh en l i ewater and carb on d ioxid e m t is
reac

c al ciu m
c arb onat e I t is exac tly t h e sa e c h e ic al c o m m mpound
“
.

as or dinary marbl e , and is ll

ca e d p rec ipit at ed ch alk .
”

220 . Liquid and s ol id c arb o n d iox id e B y app ly ing sufli

.

c ien pressure t o c arb on d io xid e

t gas at ord inary t emperatures
it can b e cond ensed t o a l iquid . T h is l iquid is an artic l e of
mmerce and is put on t h e
co

market in strong steel tanks

,

Wh en t h e l iquid b on d iox c ar

id e runs from suc h a t ank ,

part o f it evaporates quic kly

and remo ves S O muc h h eat
th at t h e rest is froz en t o a
snow l ike sol id
-
.

A t ank of c arb on d ioxid e is t ilt ed

on it s s id e as I n figure 1 34 A .

s t out c anv as b ag is t ied around t h e

out l et , and t h e v al v e is o pened wid e

m
.

A ft er afew inut es t h e b ag is found

Fig:1 34 M aking d ry ice
.
”
.

t o ob nt ain a s now l ike sol id T his -

.

sol id h as very fas cinat ing pro p ert ies I t quickl y d is appears wh en l eft b y
.

it sel f, for it rapid ly ch anges int o gas A p ort ion of it pl aced on wat er v ery
.

soon ev aporat es ; b ut in s o d oing, it rem oves h eat fromt h e wat er and freez es

t h e l at t er .

I f t h e solid is put in a b eaker and mixed wit h et h er, t h e mixt ure will
freez e a t est t ub e of merc ury T h e et h er serves t o c arry t h e h eat quickly
.

fromt h e t est t ub e t o t h e sol id .

C A U TI ON I n h and ling t h e solid c arb on d ioxid e, one mus t av oid pressing

.

it against t h e flesh , ot h erwise it c auses a frost b it e which feels v ery much

_

like a b urn .

Sol id c ar on b d ioxid e enabl es us easi ly to reac h a tempera

ture as l ow as it is sometimes used
78
°
C . AS “
d y i r ce
”

for refrigeration purp oses, suc h as in S h ipping fish and d is

tributing ice cream I t h as t wo advantages over ord inary ice
.

it is muc h cold er and d oes not melt into a l iquid I t c h anges .

t o an I nsul ating d ry gas whic h surround s t h e material t o b e

refrigerat ed H ence t h e name
. .
C OM M ER C I A L USES OF CA R B ON DI OXI DE 22 9

22 1 C ommercial us es C arb on d ioxid e h as a numb er of

”

. .

familiar uses We h ave already mentioned th at it is used for

.

t h e preparation of c arb onat ed b everages like ginger ale The

‘

s o d a wat er o f t h e d rug store, wh ic h was originall y prepared

b y mixing b aking so d a I n solution with s o me fruit acid , i s now

mad e by connecting a tank of carb on dioxid e gas with a supply
of water in suc h a way th at a so l ution of c arb on d iox id e I ssues

Fig . 1 35. Carb on d ioxid e fire ext ingui sh er.

wh en t h e fauc et is opened One typ e of fire ext inguish er

.

( F ig
. 1 35 ) d ep end s o n c arb o n d io xi d e for it s effec t iv enes s T h e .

b ody of t h e container is fill ed with t h e water solution of a

c arb onat e, generally so d ium b ic arb onat e ( b aking so d a) A .

sm all b ottl e at t h e t op contains sulfuric acid When t h e .

ext ingiI iS h er is turned upsid e d own, t h e acid com es int o cont ac t

with t h e c arb onate and pro duc es c arb on dioxid e T h e gas .

thus produced forc es t h e liquid out through t h e h ose and

al so comes out itself Sinc e carb on d ioxid e is h eavy and
.

noninflammab l e it settl es d own up on t h e fl ames, partially

,

sh utting out t h e oxygen o f t h e air I t th us h el p s t h e wat er

.
230 C A R B ON A ND I T S TWO OXI DES

t o put
. out Such extinguish ers are very effec tive
t h e fire .

b ut somewhat h eavy t o handl e .

I n many el ectrical p ower pl ants, a group o f steel tanks

con taining liquid c arb on d ioxid e is so arranged th at t h e gas
would b e automatically Set free in case of fire Small steel .

b o ttl es c ontaining t h e same l iquid are very useful in extinguish

“
.

ing oil or gasoline fires ab out an automob il e ( Fig .

C ourt esy W alter t d e dc C o

.

Fig
. 1 36 . Liquid carb on d ioxi d e in s t eel b ot t l e us ed t o put out an aut omob il e fire .

2 22 . C arb on d ioxid e foa m . One d ifficulty wit h t h e c ar b on

dioxide extinguish er is th at t h e gas d iffuses rapidly T h ere .

fore a meth o d h as b een d evised by wh ich t h e c arb on d ioxid e

gas is c onfined in tough d urabl e b ubbl es of foam or froth
,
.

T h ese fl o at on b urning oil or stic k t o a b urning surface It .

is known as t h e fo amit e meth o d and h as pro ved especially

effec tiv e in fighting oil fi res and al so any oth er fires th at h av e

not gained muc h h eadway T h e carb on d ioxid e is generated

.

by t h e ac tion b etween solutions of so diumbicarb onate (b aking

so d a) and al um inum sulfate ( al um) T h e foamite is obtained
.

from l ic orice root and is mixed with t h e sod ium b icarb onate
“
so l ution I t s purpose is t o prevent t h e escape of t h e gas
. .
 32 C A R B ON A ND I T S T W O OXI DES

d ioxid e . B ut this gas o n passing th rough t h e upper l ay er o f

gl owing co al , wh ere t h e supply o f air is som ewh at c ut Off, 1s

red uced t o c arb on monoxid e A t t h e t op of th is l ay er of coal ,

.

W h ere ab und ance of air c a

n
find access, t h e c arb on mon
o x id e again b urns t o c arb on

d ioxid e with t h e well known -

blue fl ame C arb on mon . .

oxid e p ro d uc ed in th is way

is c ommonl y c all ed co al
“
gas and is famil iar t o every
3’

one wh o h as used anth racite

( h ard ) coal .

“
h es
2 24 . Lab orat ory met h od of
Fig. 1 38 . Format ion Of t h e oxid es Of carb on
in a coal fire
preparat ion . We c a
np repare
m
.

carb on onox1d e I n t h e l ab

t y by p assing c arb on d ioxid e th rough a tub e containing

ora or

c h arcoal T h e c h arcoal must b e heat ed red h ot and t h e gas

.
, ,

as it fl ows o ut must b e passed through a so l ution Of c austic

,

so d a . T his is d one in ord er th at any of t h e c arb on dioxid e

wh ic h rema ins und ec omposed may b e ab sorb ed T h e gas th at .

is l eft is c arb on monoxid e I t .

may b e c oll ected over water

in t h e usual way .

An met h od is t o t reat
eas ier

formic ac id wit h warmc oncent rat ed

s ul furic ac id . T h e l at t er c auses

t h e d eco mpo s it io n Of t h e formic ac id

int o wat er and c arb o n monoxid e .

T h e apparat us may b e set up as in

figure 1 39 .

H C OOH H 2 80 4
formic acid Fig 1 39 . Lab orat ory preparat ion of car
‘
.

H 2 S0 4 H zo CO 1 b on monoxid e .

T h e sulfuric acid is used t o assist in t h e react ion b y unit ing wit h t h e wat er
formed .
C A R B ON M ONOXI DE A DEA DL Y P OIS ON 2 33

225 . P ropert ies Of c arb on monoxid e . C arb on monoxid e ,

l ike c arb on dioxid e 1s a c ol orl ess gas I t is nearl y o d orl ess

,
.
,

j ust a littl e l ighter th an air and very sligh tl solub l e ,

I t is one of t h e gases wh ic h it l iquefy I t s most .

s triking c h em ic al property is t h e fac t th at it burns in air or

oxygen wi th a b lue flam e form i ng carb on di oxi de ,
I t al so ac ts .

as a red ucing agent and will remove t h e oxygen fro mmetall ic

o x id es s uc h as c op p er o x i d e o r ir o n o x id e
, C ommerc iall y -

thi s g as i s us ed in a bl ast f ur nac e t o r ed uc e t h e or es of

i r on.

Fig
. 1 40 . R ed ucing copper oxid e wit h carb on monoxid e .

T h e red ucing act ionof c arb on monoxid e may b e v ery wel l sh own b y t h e
foll owing experiment T h e gas is prepared in fl ask A ( Fig
. B ot t le B .

c ont ains a lit t l e wat er t o wash t h e gas T h e h ard gl ass t ub e C h ol d s t h e

.
-

b l ack c opper oxid e, wh ich is h eat ed T h e met all ic oxid e is red uced b y t h e
.

gas t o reddish met all ic c o pper, and t h e c arb o n mo noxid e is oxid ized t o c ar
b on d ioxid e T h e presence o f t h is l at t er gas is sh own b y t h e milkiness pro
.

d uced in t h e l imewat er in b ot t le D A ny of t h e unch anged c arb on

’

.
_

monoxid e wh ich p asses t h rough is coll ect ed over wat er in E and t h en

got t en rid of b y b urning
’

The resu lts of this experiment c an b e b riefly stated thus

C uO CO Cu 002

226 . C arb on monoxid e a d ead ly porson Less th an h alf Of

one p er c ent this of gas in t h e air c auses a severe h ead ac h e,
and l arge amounts m m ay c ause d eath within a few inut es,
Every winter th ere are c ases o f men wh o are poisoned wh il e
W orking ab out an auto mob il e in a small c l osed garage T he .
 C A R B ON A ND I T S T WO OXI DES -

ex haust gases of the gasoline engine always contain some carbon

monoxide T h e d oors of a small garage sh ould therefore
.
, ,

never b e cl osed whil e t h e automob il e engine is running Some .

times t h e gas escapes into t h e room from a c oal stove wh en

th e d raft is not properly regul ated C ases of sickness and even
.

o f d eath h av e result ed from th is cause I lluminating gas .

,

especially th at kno wn as water gas contains c arb on m onoxid e, ,

Gamer

Fi g 14 1 A . G as -
mas k as w o r n i n Fig . 141 B . m
Diagra sh owing t h e c on
mi l i t ary O p e r at i o ns . nect ions of gas ask m .

wh ich is particul arly d angerous since it is itself practically

Od orl ess and c annot b e rec ogniz ed in t h e air Fortunately .

ill uminating gas generall y c ontains some oth er sub stance

whic h h as a pronounced smell and thus gives warning of t h e
presence of t h e p oisonous m ateri al In m ine expl osions carb on
.

monoxid e is always formed Since bird s are very sensitive t o

.

it , t h e rescuers Often c arry canaries with th em t o warn th em

Of th eir own d anger I n recent y ears a s pecial mas k ( Fig 14 1 )
“
. . .

c ont aining a l ayer o f h opcal ite ( a mixture Of t h e oxid es of

”
2 36 C A R B ON A ND I T S T WO OXI DES

u
c a ses a sort of internal su o c a ion
ff t whic h resu s lt in sic kness
and so metimes d eath .

S U M M A R Y OF C HA P T ER XVI I
CA R B ON h as t h ree al l ot ropic forms : d iamond , graph it e, and
c h arc o al .

C arb on is inac t iv e at ord inary te mperat ures b ut at h igh t emperat ures

unit es wit h met al s and nonmet al s . B ut it d o es no t reac t wit h eit h er

acid s ( exc ept h ot H N Oa or h o t H zS O4 ) or b as e s . I t i s an import ant

red uc ing agent .

C A R B ON D I O XI D E is formed wh en c arb on or c arb on c o mpound s

b urn or d ec ay .

It c an b e prepared
(1) b y b urning c h arc o al in air or oxygen

(2 ) b y t h e ac t ion Of ac i d s on c arb onat es

I t s propert ies : a c ol orl ess gas , sl igh t l y s ol ub l e in w at er, and

s uffo c at ing b ut not pois onous I t i s ab but . ti mes as h eavy as air .

Liquefies easily . Evaporat ing t h e l iquid prgo d uc es s ol id c arb on

d io xid e .
T ES T : D o es not b urn ; prod uces a milkines s zn limewat er;
comb ine s wit h wat er t o form c arb onic acid wh ich react s wit h b as es ,
.

U S ED in making c arb onat ed b everages ; in c ert ain t ypes Of fire

ext inguish ers ; in i c e m d ry ice ”
ac h ines ; and as .

C A R B ON M ON O XI DE i s forme d
( 1 ) wh en c arb on or carb on c ompound s b urn in a l imit ed supply
of air

(2 ) b y th e red uct ion of t h e d ioxi d e

warm c onc entrat ed m
'

( 3) b y ac t ion Of s ul furi c ac id on for i c acid

I t s properties : a c ol orl es s gas and prac t ic all y Od orl e ss , sl igh t ly

l igh t er t h an air, and ins ol ub l e in wat er Very pois onous . . B urns

me forming t h e d ioxid e A ct s as a reducing agent
wit h a b l ue fl a ,
.
,

t aking oxygen fromh ot met allic oxid es s uch as c opper and ironoxi d es ,
.

QUES T I ONS A ND P R OB LEM S

I
. . . N ame t h e amorph ous forms of c arb on .

W h y may misund erst ood wh en h e speaks of a ”

2 . o ne be l ead pencil
QUES T I ONS A ND P R OB LEM S

3 . W h at
~ propert ies Of graph it e make it useful ( a) as a paint ; ( b ) as a
l ub ricant ; ( c) as a st ove polish ?
4 . Wh at most useful is t h e form of c arb on? Expl ain . W h at is t h e
most exp ensiv e form of c arb on?

5 C arb on d ioxid e exis t s in t h e air t o t h e ext ent o f only four part s in

.

t en t h ous and D oes t h at mean t h at it is unimport ant ?

. Expl ain .

H ow is t h e quant it y
6 . of c arb on d ioxid e in t h e at mosph ere kept
rly c onst ant ?
nea
7M ake a list of t h e uses of carb on d ioxid e and
. st at e in each c ase the
propert y ( or propert ies ) on which t h e use d epend s .

8U pon wh at t h ree propert ies

. of carb o n dioxid e d oes it s use in fire
ext inguish ers d ep end ?

9 . W h en the s t opper is re moved from a b ot t l e of mineral wat er, it

ef
fervesces . How c ould y ou prov e t h e b ub b l es t o b e c arb o n d ioxid e ?
10 Wh en c arb on d ioxid e is passed over h ot
.
p owd ered z inc , zinc oxid e

is formed W h at is t h e ot h er prod uct ?

md
.

1 1 W h en al coh ol b urns c arb o n d ioxid e is

.
, for e . W h at d oes t h is
s h ow ab out t h e mposit ion of al coh ol ?
co

12 . C arb o n monoxid e kill s more t h an 30 0 0 peo ple y early in t his c ount ry .

Expl ain h ow . W h at c an b e d o ne t o prevent t h is ?

13 M ake a l ist Of t h e uses of c arb on monoxid e and
. s t at e in each c ase

t h e propert y ( or propert ies ) on wh ich each use d epend s .

14 . T wo sa mples of ill uminat ing gas cont ain 6 per cent and 33 per cent
‘

of carb on monoxid e respect ivel y W hic h.is t h e more p o is o no us ? Why ?

15 . W h en h ard coal is add ed t o a coal fire, a b l ue flame flickers over t he
surface of t h e fire . Expl ain .

16 . H ow woul d y ou t est for a c arb onat e ?

A men s
A nkh — mb
l

W h en King
'

was was
c h arco al
’
17 . T ut -
to o pened ,

found wh ich was put t h ere t h ree t h ous and y ears ago . W h at pro pert y o f
c arb o n is s h o wn b y t h is ?

18 . C o py and s upply the T h e t h ree allot ropic forms

missing words : of

c arb o n T h ey h av e d ifferent ph y sical

'

are and
b ut all y iel d wh en b urned in s ufficient oxy gen .

19 . W h at is t h e funct ion of t he el ect ric current in t h e furnace for t h e

pro d uct ion o f ra
g p hit e ?

20 . W h en graph it e is mad e in t h e el ec t ric fur nace, h igh ly impure co al

is co nvert ed int o 100 per cent pure graph it e . W h at b ecomes of t h e mineral
mpurit ies
1 Of t h e co al in t h e process ?
2 38 C A R B ON A ND I T S T WO OXI DES

B y wh at ch emical t est coul d y ou d ist inguish powd ered manganese

'

21 .
.

d ioxide fromp w
o d ered c h arco al ?

22D oes t h e fact t h at an acid prod uces effervescence wh en add ed t o a

.

mat erial prove t h e presence of c arb on d ioxid e ?

23 . W h at ef
fec t woul d d oub ling t h e pressure h av e up on t h e s ol ub ilit y
Of c arb o n d ioxid e in wat er ?
24 . H ow c an y ou d ist inguish efferves c ence fromb oiling ?
25 . W h en a d ish of cl ear l imewat er is ex p os ed t o t h e air for me t ime
so ,

a t h in wh it e c rust forms On t he s urfac e o f t he l iquid . Expl ain .

26 On wh at propert y
. o f c arb o n d ioxid e d oes it s ext ens iv e use I n refrig
erat io n d epend ?

27C ont rast in t ab ul ar form t h e propert ies

. a
nd us es o f c arb o n d ioxid e
and c arb o n monoxid e .

28 . B y wh at mic al
ch e t est could y ou d ist inguish c arb o n mo noxid e from
h y d rogen?
29 T he s O c all ed wat er gas is mainly a mixt ure o f h y d rogen and c ar
'

-
.

b on mo noxid e . W h y is wat er gas b et t er for h eat ing t h an for ill uminat ing
ur o s es ?
p p
30 . N ame t wo import ant red ucing agent s wh ich we h ave s t ud ied t h us

7k >k

31 . How many gra s of c al c iu m c arb onat e m

us t b e us ed t o prod uce m
88 grams o f c arb o n d ioxid e b y it s act io n wit h an ex cess o f h y d ro ch l oric acid ?

32 . H ow many grams o f c arb o n will b e required to red uce 4 0 gra ms of

c o pp er oxid e t o met all ic co pper ?

33 . W h at v ol u me of c arb on d ioxid e will b e formed b y b urning

12 0 kilograms o f c oke c ont aining 80 per cent c arb o n?
'

34 H ow many t ons of oxy gen are

. required t o b urn co mplet ely o ne t on
of c oal which is 90 per cent c arb on?

T OP I C S FOR FUR T H ER S T U DY

H eat ing apparat us in t h e h ome I nv es t igat e y our kit ch en s t ov e

. D raw s

a d iagram o f it , and ind ic at e wh at c h emic al reac t ions t ake pl ace at each

’ ‘

p o int .H ow is y o ur h o us e h e at ed ? M ake a sket ch o f t h e sy s t em I s .

t h ere any d anger t h at c arb o n mo noxid e will es cape int o t h e rooms ? Wh at

migh t h appen if t h e l ining o f t h e fire b ox in a h ot air furnace were d efect iv e ? -

A d miral B yrd s experienc e wit h c arb on monoxid e

’
. W h at pro d uced t h e
gas ? H o w d id h e d et ec t it ? W h at was h is d anger ?
( N ational Geographi c
M agazine Oct , .
 40 M OLEC UL A R A ND A T OM I C WEI GH T S

given mass o fgas varies di rectly as the absolute t e p erature if m

the press ure m
re ai ns th e s a e m
T h is is c all ed t h e LA W OF
.

’
C HA R LES r .

I n C h apter VI we l earned from t h e v olumetric s ynth esis

Of s ea t mthat
2 vol . h y d rogen 1 v ol . oxygen 2 vol . m
st ea

I n C h ap ter XI we h av e seen th at
1 vol . h y d rogen 1 vol . ch l orine 2 v ol . h y drogen ch l orid e

A ful stud y Of t h e proc ess o f making a monia gas by t h e

c are m
d irec t union of hyd rogen and nitrogen gives th ese results :
3 v ol . h y d rogen 1 v ol .
nit rogen 2 v ol . mmonia
a

T h ese e xperimental facts all illustrat e t h e LA W OF G A Y

LUS SA C :

T h e volumes of gases used and p roduced in a chem ical change can

always b e represented by th e rati o of small whole numbers .

229 v o gad r o s e x p l anat l o n

. A ’
.

T h es e striking c ases of uniformity in

t h e b eh avior of gases were exp l ained
in 1 8 1 1 b y t h e famous I tal ian A vo ,

gadro ( Fig as foll ows

. H e as .

su med th at equal volumes of all gases

under the s ame conditi ons of t emp era
ture and pressure contain equal nu m
bers of molecules I n o th er wo rd s , 1

“ “
.

Fig . 1 43 A M E D E O A VO G A D R O cub ic c enti met er Of hyd rogen h as

j ust as many mol ecul es as 1 cubic

.

7 76 1 3 5 P r ° fe S S °f ° f
-

ph y sics at T urin, I t al y
met er of o xygen n1t rogen, hl o
.

c ent l ,
c

r1ne, hyd rogen c hl orid e or any o th er gas provi d ed , ,

t he con

dit ions of temp erature and p ressure are t h e same .

A b s ol ut e t emp erat ure cent igrad e t em perat ure

T A t t h is p oint so me t each ers will wis h t o review t h e gas l aws as out l ined in t h e
A p pend ix .
T H E H YDR O GEN M OLEC ULE H A S T W O A T OM S 241

T h is famous hy poth esis was not generally accept ed by

c h em ists until anoth er I tal ian professor, C annizzaro ( Fig .

expl ained it s great useful ness

in 1858 (t wo years after A v o

g a d ro d ied ) I t is n
.o w c o n
fund amental
_

sid ered one oft h e

princ ip es l of c h em istry .

230 .Co nc l us i o ns d rawn

fro mt his principl e We must.

no tic e at o nc e th at th is d o es
no t state t h e actual num
b er Of mol ecul es in a c ubic
“

centim et er of a gas f B ut i t

d oes gi ve us a simp le method

'

of com p aring the wei ghts of the

molecules of gases by co mpar
ing the densiti es (of th e gas es ;
th at is, th eir weights per unit
S T A N I S LA O C A N N I Z Z A R O ( 1 8 2 6 —
Vol ume We Fi g 1 44 .
4

. can b est S h ow .

P rofes s or of ch emist ry at A l es
t h lS in a tabl e s and ria in nort h ern I t al y .

D EN T
SI Y R EL T E
A IV W E I G H TS
( G r ams p er l it er) OF M OL EC LE
U S

H y d rogen
Oxy gen
N it rogen
H y d rogen c hl orid e

In this tabl e we h ave used only t h e approximate val ues for

d ensities M oreover we h ave taken h y d rogen as t h e b asis of
.
,

c om p arison d ivid ing each d ensity b y I t will ac cord ingly

m
,

b e seen th at t h e th ird colu n gives us t h e rel ativ e weights o f

t h e mo l ecul es referred t o t h e h y d rogen mol ecul e as a stand ard
]

T h e h yd ro ge nmol ec ul e h as A noth er very

t wo at o ms .

interesting concl usion th at we d raw fromA vogad ro s principl e

’
 M OL EC ULA R A ND A T OM I C WEI GH T S

is th at molecule of hydrogen has at least t wo atoms Let

every .

us see wh y this is so Our ex periment in t h e synth esis of hy dro

.

gen ch l orid e 1 39) s h owed that

1 vol . h y drogen 1 vol . ch l orine 2 vol . h y d rogen c hl orid e

A ccording t o A vogad ro we mus t assume th at we h ave t h e

m
sa e num b er of mo l ecul es o f h y d rogen as of c hl orine and twi ce
th at numb er Of mol ecul es of h y drogen chl orid e Suppose we .

h ave a million mol ecules of hy d rogen T h en we must h ave a .

mill ion mol ecules of c hlorine and two million mo lecul es Of

hydrogen c hl orid e Eac h one o f th ese olecul es of hyd rogen
. m
c hl orid e m ust contain at l east one atom Of hy d rogen T h ere .

fore we h ave in all two milli on at o ms of hydrogen c oming from

one m i lli on mol ecul es Of hyd rogen T h is exper1ment indic ates
'

th at eac h mol ec ul e of h yd rogen c o nt ains at l eas t 2 at o ms Of

h yd rogen ( H 2 )

It may
h el p us t o pict ure t h is rel at ion ii we d raw squares t o represent t he
al volumes ( Fig 145)
d
equ .

H y d ro g en C h l ori ne H y d ro g en c h l o rid e

Fig . 1 4 5. D iagramt o sh ow t h e union of equal vol u mes of h y drogen and ch l orine .

B y a simil ar c ourse o f reas oning it foll o ws th at t h e c hl orine

mol ecul e al so tains at l east t wo atoms
con .

We represent th ese facts b y t h e foll owing . equa ion t

T his means t h at o ne molecul e of h y drogen, c o nt aining 2 at o ms , pl us o ne

molecule o f c hl orine, co nt aining 2 at o ms

mol ecul es of h y d rogen
, gives 2
ch l orid e, eac h c o nt aining o ne at om o f h y d ro gen and o ne at om Of chl orine .

N OT E . It s h oul d be re memb ered t h at any even nu b er m m

igh t b e used ins t ead
of t wo . B ut since t h ere is no reac t io n in wh ic h t h e h y d ro gen m
o l ec ule app ears t o

b e d ivid ed int o more t h an t wo p art s , we d ec id e t h at t h ere mus t b e only t wo at o ms

in t h e mol ec ul e .
244 M OL EC UL A R A ND A T OM I C WEI GH T S

W h en 50 cub ic c ent i met ers of h y d rogen b urn in c h l orine, h ow many

c ub ic c ent i met ers of h y d ro gen chl orid e are pro d uc ed ?
3 . W h en acet y l ene b urns co mpl et ely , t he ch e mic al ac t ion is expressed

b y t h e foll owing equat io n

2 0 2H 2 + 50 2

( a) W h en 2 0 lit ers of ac et y l ene gas are b urned h ow many l it ers of oxy gen ,

are required ? b
( ) H o w m a n y l it ers o f c arb o n d io xid e ar e p ro d uced ?

4 . Ath igh t emperat ures , it is p ossib l e t o form nit ric oxid e (N O)

v ery

b y direc t c omb inat ion of nit rogen and oxy gen ac c ord ing t o t h e foll owing
equat io n : N2 02 2 NO H ow many c ub ic feet of air will b e
.

need ed t o pro d uce 1 0 c ub ic feet of nit ric oxid e? (A ssume air to b e o ne

fift h oxy gen ) .

5 . W h en al coh ol
a m
por is c o plet ely b urned in oxy gen, it
v
“
pro d uces c arb o n d ioxl d e and wat er v apo r accord ing t o t h e foll owing equa
t ion : Os o H 302 2 C0 2 3 H 20 .
( a) H ow many lit ers of

o xy gen will be required t o b urn 2 0 l it ers of al c oh ol v apor ? ( b ) H ow many

l it ers o f c arb o n d ioxid e wil l b e pro d uced in t h is pro cess ?

2 33 . S t and ard of mol ecul ar w gigh t s . We have j ust seen

mol ecul e
xygen contains t wo atoms We
'

th at the of o

m
.

rem e b er 77) th at c h emist s h av e agreed t o t ake as th eir

s tand ar d for at om ic weigh t t h e atomic weight Of oxygen ,

I t foll ows th en th at th e molecular weigh t of oxygen

this is the standard of molecular wei ghts
l

is exactly .

We rec all al so 10 3) th at if we know t h e formul a of a gaseous

sub st ance we can at once com
, pute i ts molecular wei ght by adding
th e wei ghts of i ts atom s For examp l e t h e formul a for hy d ro
.
,

gen c hl orid e is H C l T h erefo re it s mol ec ul ar weight is

.

or T h e formul a for acetyl ene is C 2 H 2 and it s ,

mol ecul ar weight is 2 X + 2 or

2 34 G ram mo l e c ul ar vol ume

.
-
T h e c h emist Oft en h as .

oc c asion t o use as m
any grams of a gas as th ere are units in
it s m
o l ecul ar weight He th erefore c all s th is weight t h e
.

g r a m mo l-
e c ul ar , or m ol ar , weigh t T h us , 32 gra s is t h e . m
gra mmo lecul ar or molar weight of oxygen
-

, ,
.

Wh at vo lume d oes 32 grams of o xygen o ccup y under standard

.

c ond itions ? Sinc e one l it er of o xygen weigh s appro ximately

GR A M —M OLEC UL A R VOLU M E 245

3
8
gra ms ( Fig it fol lows th at it takes , or
1 3
.

liters of oxygen und er stand ard c ond itions t o weigh 32 grams .

I f w d iv id t h amm l c ul ar weight o f any gas by it s d ensity

m
e e egr o e -
,

we al way s get approxi ately

liters T hus.

2 grams of H 2 o ccupy liters

44 grams of C 0 2 o ccupy
liters
gra ms of HC l o c c up y
l iters
17 grams Of NH 3 oc cup y 22 4
’

liters
T h erefore we conc lud e th at the -

grammolecular
-
wei ght of any
a occupi es a volum e of
g s _
.

li ters (N
Of a
T his gaseous volume of
El g '

l iters ( Fig 14 7) is one of great

.

importance t o t h e c h emist in t h e l ab oratory, for it furmsh es

h im with a quic k means of c al cul ating t h e ol ecul ar weight m
Of any s ub st ance wh ic h c an b e weigh ed in t h e gaseous stat e .

A ll h e h as t o d o is t o compute fromt h e weight of a given volume

Fig . G ram mol ec ular weigh t

-
of any gas o ccupies l it ers .

und er tand ard conditions wh at

s l iters woul d weigh in
gra m s .T h erefore we a g ain conc l ud e th a t th e we
.i gh t i n grams

of li ters of any gas ( at 0 C and 760 m m pressure) is equal

°
. .

to the m olecular weight of the gas .

2 46 M OLEC ULA R A ND A T OM I C WEI GH S
”

FOR EX A MP LE, carb on dioxid e weigh s approxi at ely gra s per lit er m m .

T h erefore lit ers w ould weigh X o r ab out 4 4

grams T h e .

molecular weigh t Of carb on dioxid e is , t hen, app roximat ely 4 4 .

A gain, nit rogen weigh s m

gra s per lit er T h erefore . l it ers
would weigh X or ab out 2 8 gra s T hem m
ol ecul ar weigh t of
.

nit rogen is, t h en, approximat ely 2 8 .

QUEST I ONS
1 . Wh at is t h e weigh t Of 2 0 lit ers Of c arb on d ioxid e ?
2I f a lit er o f mars h gas und er st and ard
. c ond it io ns weigh s gra ms ,

wh at is t h e molecular weigh t of marsh gas ?

3 . T h e d ens it y Of a cert ain h y d ro c arb o n in t h e gas eous s t at e is
gra ms per l it er und er st and ard c o nd it io ns W h at is it s molecular
.

weigh t ?
4G iven t h e formul a of carb on monoxid e as C O,
. co mput e it s d ens it y
( grams per lit er) und er st and ard cond it ions .

5 . If the molecul ar weigh t of nit rous oxid e is 4 4 , wh at is t h e approxi

mat e d ensit y (grams p er l it er ) o f t h e gas ?

6 From t he t ab le of d ens it ies Of gases given in t h e A ppendix comput e

.
,

t h e molecul ar weigh t Of t h e foll owing gases : ( a) ac et y lene ; ( b ) ammonia;

(0 ) carb on monoxid e ; ( d ) h y d rogen sulfid e ; and (e) sul fur d ioxid e .

7 T h e d ensit y o f h elium is
. 8 grams per lit er und er s t and ard con
d it ions and it s at omic weigh t is
, H ow many at oms d oes a h elium
molecul e cont ain?
8 . C al cul at e t h e weigh t of a l it er of each Of t h e following
gases : ( a) ammo nia (NH 3) ; (b ) sul fur d ioxid e ( c) pro p ane ( C sH s) .

A rrange t h e foll owing gas es in t h e

9 . ord er of increas ing d ensit y
C O ; NH SO C H 4 ; C12 ; C 0 2 ; 0 2 .

10 . Find t h e molecul ar weigh t Ofa gas of wh ich 1 50 CO at 1 8 .

°
C and
.

7 52 mm weigh .
grams .
( See A ppend ix for gas l aws ) .

2 35 . P rob l ems involving w eigh t and vol u me . Some prob

l ems invo lve both t h e weights of solid or l iquid sub stanc es
and t h e vol umes of gases used or pro d uced in a c h emical reac
t ion .T h es e c an easily b e s o lv ed by means O f t h e gram ~

molecul ar volume .

FOR E X A MP LE . H ow many lit ers Of carb on d ioxid e und er st and ard con
d it ions c an b e ob t ained from2 kil ograms Of marb le b y t h e act ion of h y d ro
c hl oric acid ?
2 48 M OL EC UL A R A ND A T OM I C WEI GH T S

P R OB LEM S

H ow many rm
ga s of pure l i mest one ( C aC Os) wo ul d b e need ed t o
generat e 1 0 lit ers Of c arb o nd ioxid e ?
2 . Wh at
weigh t of z inc will b e need ed t o generat e 10 0 l it ers of h y d rogen
( meas ured at 0 C , 7 60 m m ) if d il
°
ut e s.ul furi c ac id is us
. ed ?

y
3 . W h at weigh t o f z inc will b e need ed t o generat e t h e s ame me of
v ol u

h y d ro gen if d ilut e h y d ro ch l oric acid is used ?

4 . W h at v olu me of h y d ro gen (measured und er s t and ard co nd it io ns )
c oul d be Ob t ained b y t h e el ec t rol y t ic d ec omposit io n Of 1 5 grams of w at er ?
5 . W h at volu me of h y d rogen (measured und er s t and ard c o nd it ions ) is
need ed t o red uce 1 0 0 gra ms o f c opp er o x id e ( C uO) ?

6 . woul d l ib erat e t h e great er v ol ume Of h y d rogen from h y d ro

W h ich
chl oric ac id , 1 0 gram s o f z inc or 1 0 gra s o f m agnes ium? H ow much more ? m ’

7 . Und er s t and ard c o nd it ions

h y d ro gen were p ro d uced l it ers of -

b y a h y d rogen generat or co nt aining h y d ro ch l oric ac id and an ex cess of

z inc T h ere is no o t h er v is ib l e pro d uct of t h e reac t ion
. W h y ? W h at .

ot h er sub s t ance is pro d uced at t h e s am e t ime,

an d w h at is it s w eigh t ?

/
l S . W h at weigh t of pure carb on will h ave t o b _
e b urned t o pro d uce
44 8 .
,
cc . i
o f c arb o n d ioxid e und er s t an ard c o r
d d it io ns ?

/9 W h at v olu me o f c arb o n dioxid e (measured und er s t and ard c o ndi

y .

t ions ) w o ul d b e giv en Off fro 1 kil o gra m m of s o dium b ic arb o nat e in a fire
e x t inguis h er ? T h e equat ion is

2 N3 H C Oa H 28 0 4 2 00 2 T 2 H 20 N a2 8 0 4

10 . W h at weigh t of z inc is required make 1 0 lit ers

to of h y drogen at
15
°
C . and 74 5 mm . by repl ace ment from s ulfuric acid ? ( See A ppend ix
for gas l aws .
)

A T OM I C WEI G H T S
2 37 . Wh y at o mic weigh t s are import ant . We h ave already
seen th at c h emic al formul as h ave a quantitative mean
1 03)
ing in c h emic al equatio ns wh ic h is of t h e utmost imp ortanc e
in industrial proc esses T h e precise d etermination Of t h e .

atomic weights Of t h e el ements is in fac t t h e b asis Of all of o ur

quantitative c h emical anal y sis B ut thus far we h ave sh own .

no experiment al evid ence t o expl ain wh y a mol ecul e of wat er

T h is sec t io n o f t he c h ap t er is a b it mo re d iffi c ul t and may b e p o s t p o ned unt il
A TOM I C WEI GH T S A ND C OM BI NI N G WEI GH T S 9

is t d b y H 2 0 a mol ecul e of sulfuric ac id b y H 28 0 4

represen e , ,

and a mo l ecul e o f ac etylene gas by C 2 H 2 We sh all now

"

t oml c weights Of t h e el ements are d et er

d iscus s firs t h ow t h e a
,

mined b y experiment and second h ow th ese atomic weights

are used t o find t h e form ul a of a c o pound
, ,

m
2 38 . Atomi
weigh t s b y d irec t c o mparl s on A noth er of t h e
c .

many important results of A vogadro s principl e is th at it

’

gives us a d irec t meth o d of cal cul ating t h e rel ative weights

”

o f t h e ato ms ; th at is, t h e at o mic weigh t s We have seen that

,
.

t h e oxygen mol ec ul e is appro ximatel y 1 6 times as h eavy as t h e

‘

h y drogen mol ecul e, and we have al so seen th at t h e oxy gen and

h y drogen mol ecul es eac h h ave 2 atoms T h erefore we c an .

say th at t h e o xygen at o m is ab out 1 6 tim

-

es as h eavy as t h e
_

hydrogen atom Sinc e t h e atomic weight of o xygen is taken

.

as 1 6 and is our stand ard t h e atomic weight Of hyd rogen ,

is
I n t h e same way we c an c ompute t h e atomic weight of
nitrogen as 14 and Of c hl orine as We first d etermine t h e
mol ecul ar weight b y getting t h e weight of l iters T h en, .

knowing th at eac h of th ese mol ecul es contains 2 atoms we ,

take h alf t h e mo l ecul ar weight thus d etermined and this ,

gives us t h e a tomic weight Unfortunatel y we can app ly .

«

this meth o d onl y t o th ose el ements th at we can obtain in t h e

gaseous c ond ition .

2 39 . A t omic weigh t s and co mb ining w eigh t s . If we analyze

hy drogen c hl orid e we sh all find th at , grams o f c hl orine
are united with grams o f hyd rogen T h e c h emist c all s .

th is numb er t h e co mb ining weigh t or equival ent weigh t

Of c hl orine T he comb ining, or equivalent weigh t of an ele
.
,

ment is the weight of that element whi ch combines wi th or replaces

_

gram s of h y drogen I t will b e seen at once th at this

‘

c om bining weight is equal t o t h e atomic weight of ch l orine ,

wh ich we h ave al ready d etermined by comparing t h e d ensities

Of t h e el ement ary gases c hl orine and hyd rogen I nd eed this .
,

c om b ining weight must b e it s atomic weight b ecause a mol ecul e ,

2 50 M OLEC ULA R A ND AT OM I C WEI GH T S

of h y d rogen c hl orid e ( 11 0 1) con sis t s o f b ut o ne at omo f hyd rogen

co m b ined with o ne ato m of ch l orine T his meth o d is much

.

more precise than that of comparing densities .

Unfortunately t h e c omb ining weights of some el ements are

not equal t o th eir atomic weights If we analyz e wat er
.
(

we find th at parts by weight of hy d rogen unite with

8 parts by weight of oxygen T h erefore t h e c omb ining weight
.

o f ox ygen is 8 or one half i ts at om

,
-
ic w eight T his is b ecause
.

o ne atom of oxygen ( 1 6 ) unites with t wo at o m s of hyd rogen

t o formwat er I t h as b een found in general th at th e

.
, ,

atom ic wei gh t of an element is equal to i ts combining weight or

som em ultip le of i t I n t h e case of o xy gen this multipl e is 2
.
?
.

We sh all presently see that th is multipl e is t h e val ence of t h e

el em ent .

Let us take t h e c ase o f an el ement wh ich d oes not c omb ine

with hydrogen b ut whic h repl aces it Suc h an el ement is
.

so d ium I t s c ombining weight may b e d etermined as foll ows

. .

If we put metall ic so d ium in wat er hy drogen and so d ium ,

hydroxid e are formed Wh en th is exp eriment is d one quanti

.

ta t iv ely we find th at
, grams of so d iumrepl ace grams
Of hyd rogen T h erefore t h e c omb ining weight of sod iumis
.

240 H o w t o d et ermine t h e c omb ining weigh t Here t h e

m
. .

ques tio n might easily arise, H ow c an we d ete rmine t h e c o

a
b 1n1ng weight of n el ement which d oes no t c omb ine with or
rep l ac e h y d rogen ? I f we analyz e bl ac k copper oxid e, we find
th at grams of c opp er are c o mb ined with grams of
o xygen T h at is, t h e c ombining weight of oxy gen
.
grams)
is united with grams o f c opper Henc e we feel sure th at
.

if copper and hyd rogen d id unite, grams Of c opper would

co m b ine with g r am s o f hyd ro gen T h e c o.mb inin g w eight
Of c opper is th erefore

I n general , wh en an element d oes not unite with or replace

hydrogen, we can determ ine i ts combining ( or reacting) weight by
finding the weight of i t which will uni te with the known combi ning
wei gh t of another element .
2 52 M OLEC ULA R A ND A T OM I C WEI GH T S

t wo A gain, t h e
. co mb inl ng weight of alu inu m m is it s
atomic weight is and it s val enc e is th ree . In oth er word s,

A to mic weigh t co mb ining weigh t X val enc e

A nd , on t h eoth er
h and al l th at we need to know in ord er t o
,

get t h e atomic weight o f an el ement wh en we h ave it s com

”

bining weight; is it s val ence .

2 43 . D ul ong and P et it sh emists

’
Law . T h ese t wo Frenc h c

d iscovered th at t h e atomic weight of a sol id el ement multipl ied

‘

by it s specifi c h eat generally equal s ab out

A t omic weigh t X s pecific h eat (approximately )
T his is o nl y a very rough rul e, b ut we c an get an approximate
a
v lue for t h e atomic weight b y dividing b y t h e sp ecific
h eat T h en, if we d ivid e this rough val ue for t h e atomic weight
m
.

by t h e exact c omb ining weight we sh all Obtain t h e approxi ate ,

val ence B ut we know th at t h e val enc e is a whole numb er

. .

H ence we take t h e nearest wh ol e numb er as t h e true val enc e

_

Finall y we multipl y t h e ex ac t c omb ining weight by t h e true

,

val ence and th e pro duc t is t h e at oml c wel gh t

‘

.
,

2 44 . El e ment s as mixt u r es . I s ot opes . We h ave assumed

through out this d iscussion th at all t h e atoms of an el ement
are alike B ut th is is no l onger th ought t o b e t h e c ase
. .

M any el ement s according t o our present th eory are c omposed

'

y ,

of sev eral d ifferent kind s Of at o m s wh ic h d iffer h owev er o nl y , ,

in th eir rel ativ e mass Our atomic weight s of th ese el ements

.

are th erefo re averages T h e d ifferent varieties of a given

.

el em ent are c all ed i so t opes T h ese is oto p es are id entic al in

.

all c h emic al reac tio ns and for prac tic al purposes t h e el ement
,

b eh aves as th ough it were h omogeneous .

T h e evi d enc e f or t h e ex is t enc e Of i so t op es fi r s t c ame

fr om a st ud y Of r ad ioact ive s ub st ance s L ate r an E ng l i s h .

T he s pec ific h eat of a s ub st ance is e qual t o t h e nu mb er o f c al ories need ed t o

raise t h e t e mperat ure of 1 m
gra Of it 1 d egree cent igrad e A c al orie is t h e a . mount
of h eat nee d ed t o r ais e m
t h e t e p erat ure of 1 gra o f wat er 1
°
m
C .
EL EM ENT S A S M I XT UR ES . I S OT OP ES 2 53

physic ist A s t on Fi
( g
,
inv ent ed a me th
. o d o f c o mp aring t h e

masses of ind ividual atoms thus d isc overing Isotopes of many

,

com mon elements For example chl orine with an atomic

.
,

Fig
. I 49 . FR A N C I S WI LLIA M A S T O N at work wit h h is mass spect ro graph in t h e
C avend ish Lab orat ory .

weight of .
was f ound t o b e a mixture Of t wo isotopes of
at o mic weights 35 and 37 T h e fo ll owing t abl e gives a sh ort
list of elements and th eir isot op es , acc ord ing t o A ston

M I N I M U M NU M E T M C WE T O
A O I I GH F
EL EMENT A T OM C
I W EI G H T ISO
B
T OP E
R
T PE
ISO O S O DE
IN R R
I NTEN T
OF S
OF SI Y

It will b e noted th at t h e atomic weight s of t h e ind ivid ual

iso topes are wh ol e num b ers in this tabl e .
2 54 M OL EC UL A R A ND A T OM I C W EI GH T S

I n fact , P rout , as early as 18 1 5, s uggest ed t h at all t h e ch e mic al element s

were mad e up groups of h y d rogen at oms only
Of A t present we t hink of .

t h e at o ms Of al l t h e el ement s as c omposed o f el ect ro ns , pro t ons , and neut rons .

S ince t h e weigh t of t h e elect ron is s o small t h at we c an negl ect it in t h is

c al cul at io n, t h e weigh t of t h e at o mmust b e d ue t o pro t o ns and neut rons .

B ut t h e prot on is t h e nucl eus Of t h e h y d ro gen at om, and t h e neut ron weigh s

t h e s ame as t h e h y d ro gen at o m T h erefore we h av e . co me b ack t o me
so

t h ing like P rout t h eory

’
very s .

245 . D et ermining t h e formul a of a c ompo und

T o find t h e .

prec ise value Of at omic weights require s v ery great t ec h nic al

s kill and pat ienc e For most of us th e i m

.
portant thi ng i s t o learn .

t o use atomi c weights

‘

One very imp ort ant use Weights is in find ing t h e of at o mic
formula of a compound Let us illustrate th is by d etermining .

t h e f ormul as of wat er sulfuric ac id and ac etyl ene , , .

W at er We find t h at it s p erc entage c omp ositio n is as fol

.

l ows : hydrogen p er c ent and o xygen p er c ent .

B y exp eriment we als o find th at it s mol ec ular weight is approxi

mately 18 T h en t h e solution is as folloWs :
.

P erc ent age A t omic A t o mic

co m
p os i t io n weigh t rat i o

H y d rogen 1
Oxy gen 16

D ivid ing t h e perc entages (b y weI gh t ) by t h e at omic weights

gives as quotients numb ers wh ic h represent t h e relat ive numb er
Of eac h kind of at o m If we assume th at th ere is one ato mof
.

o xygen in t h e m o l ec ul e, th en th ere m ust b e 2 ato ms Of hyd rogen .

I n oth er words , d ivid e t h e s everal quotient s in col umn three by

t h e small est o ne of th em T h at is . 2 T h ere
,
.

fore t h e simpl est formul afor water is H 2 0 T h is gives a molec .

ular weight of 2 1 6, or 18 , wh ic h c orrespond s with t h e experi

mental value given .

S ulfuric A cid G iven t h e p erc entage composit ion : hydrogen

.

p er c ent , su lf u r p e r ce nt , and o x y gen p er c ent ;

P ercent age A t omic A t omic

c om p o s i t io n weigh t rat io

1
32
16
 2 56 M OL E C ULA R A ND A T O M I C WEI GH T S

7 . T h e analy sis of a s ub st ance s h owed c arb on 8 0 per cent and h y d rogen

2 0 per cent T he . molecular weigh t was found t o b e 30 . W h at was it s
m
for ul a?

/8 . A
gas w as fo und b y analy sis t o h ave t h e following co p osit ion m
c arb o n 7 per c ent ; h y d ro gen per cent ; and nit rogen 1 7 5 per cent
‘

. . .

Its m ol ecul ar weigh t was found t o b e Find t h e for ul a o f t h is m

c om o und .

9 . A l it er of a cert ain gas weigh s gra ms under s t and ard c o nd it ions .

It c o nsis t s o f
7 5 p er cent c arb on and 2 5 p er c ent h y d rogen . C al cul at e it s
m ol cul ar weigh t and it s form ul a .

10 A c ert ain c o mpound is found t o c o nt ain c arb o n 92 3 per cent and

.

h y d rogen 7 7 per cent , and

.
grams o f it s v ap or is found t o o c cupy
314 cub ic cent imet ers und er s t and ard c ondit ions . W h at is it s formul a?

VII . T h e analy s is mmonia gas sh ows t h at it is

of a per cent nit rogen
and t h at t h e remaind er is h y d rogen C omp ut e t h e. co mb ining weigh t of
nit ro gen .

12 T o d et ermine t h e mol ecul ar weigh t of t h e compound used in Ques

.

t ion 3, an experiment was performed wh ich s h owed t h at 0 2 50 grams of t h e

‘

sub s t ance gav e cub ic c ent im et ers o f gas when coll ect ed o v er wat er at
‘

: C and 74 0 mm C al cul at e t h e g
A 20 ram mol ecul ar weigh t
.
-
of t h e sub s t ance,
and rev ise y our answer in Ques t ion 3 accordingly .

13 . Experiment s h ows t h at 500 cub ic c en timet ers t h e v apor of a cer

of

t ain co mpound weigh grams . T he co m pound c o nt ains 72 p er cent

c arb o n, 1 2 per cent h y d ro gen, and 16 per cent o xy gen D et er ine it s
. m
formul a .

14 . T he co mpound used in Ques t io n 4 was h eat ed t o 150

°
C .
, and it
was found t h at 1 8 5 cub ic c ent imet ers of t h e gas formed weigh ed grams .

( a) W at wa t g m m ( b ) W h at is t h e formul a of t h e
'

h i a l ul ar w i h t ?
s s r o ec e g -

co mpound ?

S U M M A R Y OF CHA P T ER XVII I

U NIFOR M B EH A VI OR OF A LL G A S ES

T h evol ume of a giv en mas s of gas vari es invers ely as t h e pressure

if t h e t emperat ure mains t h e s ame (B oyl e s Law)
re
’
.

T h e vol ume of a giv en mas s o f gas varies direct l y as t h e ab sol ut e

t emp e r a t ure if t h e pr e s s ure rem a i ns t h e s ame ( Law o f C h arles ) .

A b s ol ut e t emperat ure c ent igrad e t em perat ure

S U M M A R Y or C HA P TER XVI I I 257

Th e vol u mes of gas es us ed and produc ed in a ch emic al react ion c an

al ways b e repre s ent ed b y t h e rat io of s mall wh ol e numb ers (Law of
G ay -
Lus s ac ) .

A VO G A DR O S P R IN C IP
’
LE :
Equal vol u es m of al l gas es und er
th e me cond it ions of t em
sa a
perat ure nd pressure cont ain equal num
b ers of mol ecul es .

A s a cons equence of t h i s principl e w e c oncl ud e mol ecul es

t h at of

h y d rogen, o xygen, nit rogen, and c h l o rine h av e t wo at oms each .

R ELA T I VE VOLU M E S OF R EA CT I N G G A S ES are repres ent ed

b y t h ecoeffici ent s of t h eir mol ecul es in an equat ion .

M OLEC UL A R W EI G H T of a s ub s t anc e i s t h e numb er wh ich

expres s es t h e w eigh t of it s mol ecul e co mpared wit h t h e oxygen

mol ecul e as 32 . M ol ecul ar w eigh t is equal t o t h e su m of t h e w eigh t s

of it s at oms .

GR A M -
M OL EC UL A R WEI G H T of any gas o ccupi es a v ol u me of

l it ers und er s t and ard co nd it io ns .

“
M OL A R W EI G HT w eigh t in grams of l it ers of a gas und er
s t and ard cond it ions .

A T OM I C WEI G H T of an ment is a numb er wh ich express es

el e .

th e rel at iv e h eaviness of it s at om A t omic w eigh t of o xygen ( 1 6 ) is

.

t aken as t h e s t and ard .

C OM B I NI N G , OR E QU IVA L ENT , WEI G H T of an el e ment is t h e

weigh t of t h at el e ment in grams wh ich c omb ines wit h or r epl ac es 1

gra mm
( ore exac t l y grams ) of h y d rogen .

A T OM I C WEI G H T is eit h er equal to or a mult ipl e of t h e comb ining

weigh t .

A T OM I C W EI G H T comb ining w eigh t X val enc e .

A T OM I C WEI G H T X S P E C I FI C H EA T (approximat el y) .

I S OT OP ES are forms of me el ement wh ich

th e sa d iffer sligh t ly in
mic weigh t
at o b ut are al ike in ch emic al b eh avior .

TO FI ND T HE FOR M UL A FR OM P ER C ENTA G E C OM
“

P O S IT I ON : D iv id e t h e perc ent age o f e ach el ement b y it s at omic \

weigh t ; t h e quot i ent s wil l b e t h e rel at iv e nu b er of each kind of at om m .

Us e mol ecul ar w eigh t t o find wh at mult ipl e of t h e simpl est formul a t o

us e .
2 58 . M OL EC ULA R A ND A T OM I C WEI GHT S

QUES T I ONS
1 . D efine t h e t erms (a) molecular wei ght and
mic weight (b ) ato .

2 Wh y d o we not express t h e weigh t s of at oms as s o many grams ?

.

3 S t at e precisely wh at is meant b y s ay ing t h at t h e at omic weigh t of

.

chl orine is and it s molecul ar weigh t is 71

‘

4 W h at is t h e d ist inct ion b et ween at omic weigh t s and c omb ining

.

weigh t s ?
5 . I n wh at c ases is t h e at omic weigh t equal mol ec ul ar weigh t ?
t o t he
6 . W h at is t h e d is t inct ion b et ween at omic weigh t s and mol ecul ar
weigh t s ?
7 . I n wh at c ases is t h e at omic weigh t equal t o t he mb iningweigh t ?
co

8 S omet imes t h e co mb ining weigh t is referred t o as t h e equiv al ent

“
.

weigh t Expl ain t h e signifi canc e of equiv alent

”
. in t h is use .

9 . Why was t h e oxy gen at o mch osen as t h e st and ard for at omic weigh t s
ins t ead of t h e h y d ro gen at o m?
10 . Why sh oul d t h e t ab l e of precise at o m1o wei ght s need t o b e revised

from t ime t o t ime ?

m
Q

11 . Wh y was it so d ifficul t for ch e is t s t o find t h e isot o pes of wh ich

such el e ment s as mad e up ?
c h l orine are

1 2 T h e t ext s ay s t h at
.
“at omic weigh t c om b i ni ng wei gh t X v al ence .

Expl ain wh y t h is is t rue using al uminumas y o ur example

, .

1 3 W h y c an a ch emist d et ermine t h e c omb ining weigh t of an element

.

wit h more precis io n t h an t h e mol ecul ar weigh t o f a gas ?

S h ow h ow A v o gad ro principle furnis h es t h e b asis for t h e d et er
’
14 . s

minat ion (a) of m m

ol ec ul ar weigh t s and ( b ) of at o ic weigh t s
'

1 5 I t is an experiment al fact t h at 8 grams of oxy gen c omb ines wit h

.

grams o f h y d ro gen ; 2 3 grams o f s o d ium d is pl aces t h e s ame weigh t

"

of h y d ro gen ; and 2 0 gram s o f c al c iumd is pl ac es t h e s ame weigh t o f h y d ro gen .

( a) W h at d o t h ese numb ers represent for each of t h e el ement s ? ( b ) W h at

rel at ion d o t h ey b ear t o t h e at om ic weigh t s of t h ese element s ?

T OP I C FOR FU R T H ER S T U DY

T h e preci s e d et erminat ion of at omic weigh t s T he o d ern et h od s of

. m m
m
at o ic weigh t d et erminat ion inv olve m
any experi ent al prec aut ions ; t h e m
m m
fund a ent al ch e ical fact s are, h owever, v ery si ple C onsul t t h e work m .

of M orley on h y d ro gen and oxy gen ( Smit h sonian C ont rib ut ions No 98 0 ) , .

and R ich ard s ( C arnegie P ub lic at ion N o

"

o n c h lorine and sil v er , .

260 M OLEC UL A R A ND A T OM I C WEI GH T S

H ow c oul d y ou sep arat e amorph ous

17 . s ulf ru from rh omb ic sulfur if
b ot h were in a p owd er t o get h er ?
’

18 . W h at is t h e d ifferenc e b et ween an uns t ab le acid and a weak acid ?

C arb onic acid is b o t h uns t ab l e and weak Expl ain . .

P riest ley d is c ov ered oxy gen in 1774

19 . H ow d id h e accomplish t h is ? .

D id h e und e t
rs an d t h e m ean ing o f h is w ork ? Expl ain .

20 .From t h e point o f v iew o f t h e el ect ron t h eory of mat t er , wh at is

t he d ist inct ion b et ween metals and nonmetals ?
A nimals d ie in an at mos p h ere b o t h of c arb o d ioxid e and
21 . n r
c a b on

mo no xid e I s t h e c au
.s e o f d eat h t h e s ame in each c ase ? Expl ain .

22 . Writ e equat io ns to repres ent t h e for mat ion of sul fur d ioxid e from
( a) sul fur ( b ) sulfuric ac id ; (0 ) iro n pyr it es ; ( d ) a s ulfit e
‘

; .

W h at is formed wh en c arb o n d ioxid e is p assed t h rough t h e

‘

23 . s ol ut io n

of a b ase ? Giv e t h e equat io ns .

24 . B y wh at mical
ch e t es t s co ul d y ou id ent ify ( a) m sulfid e ;
s od iu

msulfit e ;
u m
_

(b) s od i and (0 ) so diu s ulfat e ?

25 . W rit e t he equat io n for t h e ac t ion .

o f s ulfur1 o ac id on s od iu m b icar
b onat e . From t h ese equat io ns d ecid e wh y t h e b ic arb o nat e rat h er t h an t h e
c arb onat e is used in t h e c arb o n d io xid e fire ext inguish er .

26 . W rit e t he equat io n fo r t h e reac t ion of h ot co nnt

ce rat ed sul furic

acid ( a) copper ; ( b ) sil ver ; (0 ) c arb on

on .

2 7 M ake a l is t of all o f t h e foll o wing agent s wh ich we h ave st ud ied t h us

.

far : ( a) b l each ing agent s ; ( b ) oxid iz ing agent s ; (0 ) red ucing agent s .

28 . Expl ain in t erms of t h e t h eory of at o mic st ruct ure ( a) wh at h appens

wh en so diu m comb ines wit h fl uorine ; ( b ) wh y the ml o ecul es o f h el ium,
neo n, and argon are monat omic .

( a) B oy l e s L aw was discov ered as early as 1 6 60 ; ( b ) t h e L aw of

’
29 .

C onserv at ion of M at t er ab out 1786 ; ( c ) t h e L aw of C onservat ion of Energy

as l at e as 1 8 4 2 . Expl ain t h e signific ance of t h ese d at es .

30 C l assify t h e compound s S O N aH S O4 , H B r, P h o , C a( OH ) 2 , P 2 0 5,
.

H 3P O4 , N H 4OH , M n0 2 , C 0 2 , und er t h e fo ll owing h ead ings : ( a) acid s ;

( b ) b ases ; ( 0 ) normal s al t s ; ( d ) acid s al t s ; ( e) acid anh y d rid es ; (f) oxid es .

C arb o n disul fid e is b urned in air s o t h at one lit er of carb o n d ioxid e

31 .

is formed H ow many l it ers of s ulfur d ioxid e are prod uced ?

.

32 If t wo lit ers
. of h y d ro gen s ulfid e are b urned wit h an ab und ance of
air , h ow many lit ers of sul fur d ioxid e will b e formed ? W h at l aw is applied
h ere ?
GENER A L R EVI EW QUES T I ONS 261
I

t/
33 . Wh at weigh t of po t assiu m chl orat e will b e required for t h e prepa
rat ion of l it ers o f oxy gen

W h at me
”

34 . vo l u of d ry h y d rogen will b e required to red uce

a
m oxid e ( C uO) t o m
I

160 gr s o f c upric et allic c opper ?

A rrange t h e gases h av ing t h e foll owing formul as in t h e ord er

35 . of

d ecreasing d ensit y : ( a) N H 3 ; ( b ) C O ; ( 0 ) OH 4 ; ( d ) H e ; and ( 6 ) N O .

36 . One l it er of argon und er s t and ard c o ndit io ns weigh s gra ms .

It s at omic weigh t is H ow many at oms d oes an argon mol ecul e

c o nt ain

37 . Givent h at lit ers ofair weigh s ab o ut 2 9 gra s m . From t h e

formul a o f h y d ro gen s ul fid e co mput e it s m
ol ec ul ar weigh t and compare it s
d ensit y wit h t h at o f air
38 . H alf a lit er of a cert ain gaseous co mpound weigh s gra s m .

T he co mpound is s h own by analy sis t o c ont ain p er c ent c arb on,

per c ent h y d ro gen, and per cent c hl orine . C al cul at e it s molecul ar

weigh t and it s for ul a m .

Experiment sh ows t h at 2 50 cc . of a gas weigh s ms

gra .

T h is gas cont ains p er cent c arb o n and per c ent oxy gen . D et ermine
it s t rue formul a .

40 . Wh at weigh t o f sul fur Will b e required t o prepare b y t h e c o nt act

pro cess one lit er o f c oncent rat ed s ulfuric acid (specific gravit y c on »

t aining 96 per c ent of HZS O4 ?

 C HAP TER XI X

NITR OG EN A ND T HE A T M OSP HER E

I mport ance of nit ro gen prep arat ion from ai r and b y d ecom
“

p os it io n o f c om p o und s — propert ies A ir, a mixt ure

.
‘

liquefac
c om mercial uses of nit rogen
_

t ion .

R are gases in air us e of h elium St rat osp h ere C omposit ion

“
. .

of air rol e o f c arb o n d ioxid e in nat ure impurit ies in b ad air ”

fresh air and air cond it ioning .

24 6 . I mport anc e of nit rogen . We h ave learned (C h apter

IV) th at ab out one fift h -
of t h e air is o xygen Wh at ab out t h e
.

rem aind er ? Nearly all of t h e rema1n1ng gas is nitrogen T h is .

el em ent , com b ined with oth er elements, is al so found t o a

limited extent in cert ain min eral d ep osit s , suc h as s altp et er .

Nitrogen comp ounds are essenti al to life T h ey are present in .

all l iving matt er and in all t h epro ducts of t he d ecay of l iving

matter M oreover, a valuable part of our foo d is protein ma
.

t erial , wh ic h cont ains a l arge p ercent age of c h emic ally c om

b ined nitrogen So ils and fert iliz ers serve as foo d for p lants
.

very largely in prop ort ion t o t h e amount of nitrogen wh ic h

they c ontain M o d ern expl osives, suc h as gunc otton, nitro
.

glyc erin, and dynamit e, are unst abl e nitrogen comp ound s .

Suc h nitrogen c ompounds as ammonia and nitric ac id pl ay a

“

very im portant rol e in t h e ind ustries of a nat ion I n fac t , t h e .

c om pound s of nitrogen are so import ant th at we must c onsid er

th em in separate c h apters (XX and XXI ) We sh all th ere .

fore c onfine our attention for t h e present t o t h e element itself

and t o t h e air .

2 47 . Lavoisier, we rememb er
M aking nit rogen from air .

found th at air c ontains oxygen and removed it by

c ausing it t o com bine with mercury However, we c an remove .

t h e oxygen m uc h more quic kly by burning ph osph orus .

2 64 NI T R OG EN A ND T H E A T M OSP HER E

. T he c h ief sourc e of nitrogen for co mmerc ial p urposes is

liquid T h is liquid is all owed t o
a ir . evap orat e, and s inc e

t h e nitrogen is more vo l at il e (th at is , b o ils at a lo wer temper

ature) th ano xygen, it p asses off more rapidly, l eaving pract i
ca lly pure o xy gen beh ind . B oth pro ducts , t h e o xygen and
t h e nitrogen, are co mmercially valuable .

249 . P h y sic al and

propert ies ch e mical
Nitrogen is l ike .

o xyg en and hyd rogen in h av ing neith er c o l or, t ast e, nor o d or .

B ut ? in oth er resp ec ts it is very d ifferent For inst ance, it .

d oes b urn and d oes not support combustion In fact

not .
,

t h e only c h arac t eristic wh ic h c an b e easily s h own is this th at

-

it d oes not read ily ent er int o c h emic al reac t ions I t d oes . .
,

h owever unite alth ough s l owly with c ertain oth er elements

, , ,

pro vid ed th ese are h eat ed t o t h e prop er t emperature For .

ex am p le it c o mbines with red h ot magnesium forming a

-

, ,

c om p ound of magnesium and nitrogen c all ed magnesium

ni t ri d e :
3 Mg N2 M g 3N 2

A nd wh en magnesiumnitrid e is act ed upon by wat er, ammonia

is iset free :

A more direct meth o d

h owever involves t h e use of a suitable
m
, , ,

Nitrogen th en c o b ines with hydrogen at a mo d er

g
c at alyst .

at ely h igh temperature t o form ammonia gas :

N2 + 3 H2
“

When electric ks are passed th rough a mixture of nitrogen

sp ar

and o xygen, t h e nitro gen will unit e with oxygen t o formoxid es '

of nit rogen
N2 0 2 2 NO

A lth ough th ese l ast t wo t ions t ake plac e only with diffi
reac

c ulty y et th ey h ave recently b eco me of great significance

,

because th ey enabl e us t o transform t h e free nitrogen of t h e

air int o co m pound s of nitrogen C o mpo unds of nitrogen are .
HOW LI QUI D A I R I s M A DE 2 65

essen t o p lant l ife, and th eir preparation fro

tial t h e nitro m
gen of t h e air is a m
o d ern c he ic al probl e m
of enor ous m m
m
i portance .

2 50 W h y we t h ink air is a mix t ure We have already d is

. .

cussed 1 8 ) t h e d ifference b etween a mixture and a c h emic al

c om u n d a n d a a d t t at th at t h xy n and nit gen
’

p o re re y o s e e o g e ro

of t h e air are not c h em ic ally c o mb ined A ir is only a mixture

.

of th ese t wo gas es and very sm all amounts of certain oth ers .

T h ere are a numb er of piec es of evid enc e wh ic h c l early S h ow

th at air is a mixture and not a chemical compound :
( 1 ) I n t h e first pl ace, pure nit rogen and oxy gen c an b e m
ixed t oget h er
t o form an “ art ific ial air
”
m
wh ich is al os t id ent ic al wit h ordinary air

“
.

T h ere is no h eat ev olv ed or ot h er s ign o f a ch emic al react ion ;present wh en

t h ese gases are mixed T h e proport ions of t h e gas es in t h is art ificial air
”
.

may b e varied v ery considerab ly wit h out appreciab ly affect ing t h e ch emical
propert ies of t h e pro d uc t I f t h e oxy gen and nit rogen were ch emic ally
.

c om b ined , t h ere wou

fl

l d b e a d efin it e prOp ort ion in wh ich t h ey woul d unit e .

(2 ) I n t h e seco nd plac e, wat er will d issol ve air I f we fexpel t h is air

_
.

from wat er b y b oiling and t h en analy z e it we find t h at it cont ains nearly

,

t wice as much oxy gen as t h e original air Oxy gen is more s olub l e in wat er
.

t h an nit rogen, and t h erefore rel at ivel y more of it dissol v es I f t h e oxy gen
.

and nit rogen were comb ined , t h e d is solv ed gas woul d h ave t h e s ame c om
posit ion as t h e air
( 3) Finally we c an separat e air int o it s comp onent s b y a purely ph y sical
,

process .T h is is d one b y liquefy ing t h e air and t h en c areful ly b oiling off

t h e more v ol at ile nit rogen I f air were a compound , it would all b oil at
. .

t h e s ame t emperat ure .

2 51 H o w liquid air is mad e

. T h ere is a d efinite temp era
.

ture bel ow wh ic h a gas must b e c ooled b efore it will turn int o

a liquid even und er pressure T h is is known as t h e crit ical
.

t emperat ure and is different for d ifferent gases I n t h e c ase .

of b oth oxygen and nitrogen, t h e c rit ic al t em perature is so

low th at it is impossibl e t o l iquefy th ese gases at ord inary
temp eratures h owever muc h we may compress th em T o .

liquefy air we must cool i t to a very low temp erature as well as

,

subject i t to a hi gh preésure T h is is d o ne on a l arge scal e in an

.

apparatus wh ic h is arranged as in figure 1 51 .

2 66 NI T R OG EN A ND T H E A T M OS P H ER E

T h e d iagram sh ows onl y t h e essent ial part s of t h e app arat us T h e air .

is compressed b y a pump P T h e h eat prod uced b y t h e compression is

.

rem oved b y p ass ing t he air t h rough c ool ing coils T h e compressed air,
.

aft er p assing t h rough t h e c oil D , is mad e t o exp and rapid ly b y allowing it

t o issue froma very small jet
J int o an exp ansion cy lind er
kept at a l ower pressure As .

t h e air p asses t h rough t his jet

and expand s , it ab sorb s a
great d eal of h eat When .

a gas i s com pressed i t gives

out h eat, and wh en a gas ex

p an ds i t ab sorb s heat T h is .

h eat is removed from t h e gas ,

w h ich is und er pressure, b y
c ausing t h e expand ed gas t o

flow b ack over t h e out sid e

o f t h e h igh pressure c oil D -

t h rough t h e c y lind er T he .

c gl d exp and ed a r ret urns t o

Fig I 5I D iagram of t h e e ss ent ial part s of a r
e pum 18 t h en c om
. .

mach ne or making liquid air

i f t h.
p P and
pressed again T h is pro c ess
‘

is repeat ed again and again T h e gas is finally c ool ed so low b y it s own

.

c ont inued exp ansion t h at it l iquefies I t is now coll ect ed in vessel R , from
. .

wh ich it c an b e d rawn off as need ed .

We have j ust seen th at like many oth er gases , ,ai r i s liquefi ed

by the combined efiect of p ressure and low t em p erature Liquid
.

air is essent ially only a mixture of l iquid nitrogen ( b oiling p oint ,

and l iquid o xygen (b oiling p oint ,
m
It is co mercially p ossibl e t o s eparate t h e more vol atile '

nitrogen from t h e oxygen I n th is way o xygen is manu

.

fact ured for industrial use and is c ompressed int o st eel t anks .

Nitrogen is also prepared co mmerc ially ( Fig 152 ) by t h e same .

proc ess .

2 52 Experiment s wit h liquid air

. Liquid air is now an .

artic le of co mm
erce wh ic h c an b e purc h ased in any p l ac es m .

I f poured int o an ordinary gl ass v essel , h owever, it quic kly

ab sorb s enoug h h eat th rough t h e gl ass t o c ause it t o b oil
T h is is al so t he t emperat ure at wh ic h t h e gas b ec o mes a l iquid .
2 68 NI T R OG EN A ND T H E A T M OSP HER E

im mersed in l iquid an and then dropped on t h e floor, it breaks

into many pieces, a s if mad e of gl ass I n t h e same way , a
‘

rubb er tub e wh ic h c onducts l iquid air soon b ecom es so b rittl e

th at it breaks t o pieces Fl owers and grass are froz en solid by

.

immersion in l iquid air and are very brittl e wh enremoved If a .

burning stic k is plunged int o l iquid air, it keeps on b urnmg A .

flame of hydrogen or c oal gas d ipped und er t h e surfac e of liquid

ai r goe s on b urning, and t h e Wat er wh ic h is f orm ed freez es .

2 53S o me us es of nit ro gen Nitrogen gas is used t o fill

. .

cert ain kind s of el ec tric l ight b ulb s On ac c ount of it s inert

-
.

ness it d o es not all ow t h e wh it e h ot filament in t h e l a p t o -

m
xid iz e Wh en mercurial th ermometers are t o b e used at t em
,

o .

peratures from300 t o 500 C t h e spac e ab ove t h e mercury in

° °
'

.
,

t h e stem is fill ed with nitro gen und er pressure In th is way .

t h e merc ury i s prevent ed from b o iling even at t emp eratures

‘

ab ove; it s normal b oil ing p o int ( 357 Free nitrogen is

°

also U sed in enormo us quantit ies in t h e manufac ture of nitric

acid ammonia and cert ain nitrogenous fert il iz ers
, ,

QUES T I ONS
1 . W h y is nit rogen import ant t o life ?
2 . W yw
h ill an anim al d ie if kep t in an at mos p h ere o f pure nit ro gen?

W h y are t h ere s o few nit rogen com

p ound s a mong t h e minerals ?
4 S t at e t h ree way s in wh ich
. oxygen can

be remov ed from air .

5 . D es crib e an for d et ermin

experi ment
i ng t h e percent age of oxy gen in t h e air .

6 B y wh at ch emic al t est coul d y ou dis

.

t inguish nit rogen fro mc arb on d ioxid e ?

7 . Wh y d o we not put a t igh t st opper

I n a b ot t l e c ont aining l iquid air ?

8 . I f a t eaket t le c ont aining liquid air is

Fig .
54
1 Liquid air in t h e t ea
.

ket t l e b oil s on a cake of ice .

pl aced on a c ake of ice, t h e l iquid b oils
vigoro usl y ( Fig . Expl ain .

9 . Writ e for t h e foll owing react ions : ( a) nit rogen c omb ining
equat ions

wit h magnesium; ( b ) wh it e ph os ph orus b urning t h e oxy gen out of t h e air ;

( 0 ) c arb on d ioxide pro d ucing a whit e precipit at e wit h limewat er .
R A R E GA S ES I N T HE A T M OSP HER E 2 69

10 C an y ou see any reason wh y t h e fl ame o f t h e oxy h y d rogen t orch is

.

b et t er t h an t h at of t h e b l as t l amp which uses illuminat ing gas and air ?

Expl ain (See C h apt er V )
. .

2 54 gas e s in t h e at osph ere

. R are Five el e ents m . m
m
argon, neon, h eliu , kryp ton, and xenon e o ccur in t h e air
in very s all quantities m
A r gon, wh ich is t h e ost abundant
. m
of th ese oc curs t o t h e ex
,

tent of only of 1 p er

c ent b y vo l um e T h e o ther .

four togeth er make up l ess

th an per c ent of t h e
air . A rgon was first d iscov
er ed in 1 8 94 b y S ir Will iam

R amsay (Fig 1 55) and Lord .

R ayl eigh T h ey removed all

.

t h e oxygen and nitrogenfrom -

air by c h em ical meth od s a ,

very long and ted ious proc ess .

It h as since b een found p os

sib l e t o prep are argon m ore

c onveniently by t h e liquefac

tion of air T h e oth er four .

rare el em ent s are present in

m
suc h m inut e a mount s th at
m
t h e s ep arat or . an
was a mat t er Of very l ong
d s t u d y ss) S
:
it ri
c overed t h e rare gas es in t h e air
«
a an a u .

and painst aking researc h

T h ese five el em
.

ent s are all rem arkably inert sub stanc es .

I t h as not y et b een p rac ticabl e t o make th ement er int o c h emi

c al reac tions exc ep t in a few ext raord inary c ases B ec ause of .

it s inert h ess argon is often used in pl ac e of nitrogen in ord inary

,

fgas filled electric l amps B oth nitrogen and argon are used
‘ ”
-
.

t o prevent t h e bl ac kening of t h e b ulb wh ic h is d ue t o t h e

evaporation of t h e tungst en from t h e fil am ent T h ese inert .

gases enabl e t h e fil ament t o b e used at a h igh er t em perature .

T h is means a wh iter l ight and greater effic ienc y .

2 70 NI T R OGEN A ND T HE A T M OSP HER E

T h e neon l a p, so m m
uch used for d ispl ay purposes , cons ist s Of a glass
t ub e provid ed , wit h suit ab le t erminals at each end T h e air is pu ped .
m
o ut and a lit t l e neon gas ad m it t ed W h en such a t ub e is connect ed t o so e
.
m
source of high pot ent ial ( ab out vol t s ) such as an ind uct ion coil t h e
,

elec t ric current pass ing t h rough t h e gas c aus es it t o gl ow wit h a ver
y b ril
liant and d ist inct ive orange red ligh t -
To m
ake a b l ue t ub e, a ixt ure of
.
m
neon and argon gases wit h mercury vapor is used T o get a green ligh t ,
.

t h e t ub e filled wit h t h e same mixt ure as for b l ue, b ut amb er or uranium

is

gl ass is used inst ead of clear glass T h e neon t ub e is very econo ical t o
. m
operat e .

2 55 . Uses of h el ium Sinc e 1 918 h elium, anoth er of th ese

.

rare gases, h as come t o b e a sub stance of practic al im t

'

p or ance .

Next t o hydrogen it is t h e light est known gas , b eing ab out

Fig . 1 56 . Nomigid d irigib l e fill ed wit h h el ium .

o ne se en
-
v th as h eavy as am It is noninflammab l e and th ere
fore an id eal gas for fill ing b all oons and d irigibl es (Fig 156 ) .

s ince a num b er of very serious acc id ents h ave occurred in t h e

p as t b e c a u s e t h e hyd ro ge n in th e m c aug ht fi re U n d er t h e .

g re a t s t re s s o f t h e W o rld W ar t h e pro d u c t,
io n o f h e l iu m for

aeronautical purp oses was acc om p l ish ed o n a l arg e s c a l e a nd ,

t h e use of th is gas b ec ame of great im p ort ance in t h e d evel op

ment of balloons and light er th an air airsh ips C ertain natural
- -
.

g a s e s w h ic h is s u e fro m t h e gro un d in T ex as c o nt a in as m u c h a s

1 per c ent of h el ium B y a process of l iquefact ion h el ium

. , ,
 2 72 NI T R OGEN A ND T H E A T M OS P H ER E

by his d aring b alloo n asc ent t o a h eight of ab out t en miles .

‘

A t th is p o int t h e pressure of t h e air was o nl y inch es as ,

c ompared with 30 inc h es at t h e earth s surface He and h is

’
.

c om p anion were l ift ed in a c l osed ,

metallic sph eric al c ab in and lived

,

for s ix h ours al oft in th is very

restric t ed sp ac e with th eir inst ru

ments and a supply of c ompressed

o xygen ( Fig l 58 ) What were .
x
.

th ey try ing t o find out ?

T h e t erm st rat o sph ere is used
t o d enot e t h e wh ol e sh ell of at
mosph ere outsid e t h e l ower t ropo
sph ere; wh ic h is fro m Sev en t o t en

miles th ic k B y means of sound .

ing b all oons we h ave rec entl y d is

covered th at t h e t em p erature of t h e
at m osp h ere d rop s p r ett y regul arly

as we asc end unt il we reac h t h e

‘

strat osph ere wh ere it is more ,

or l ess c onst ant ab out 50 F

°
.
,

Sc ientists wanted t o get s ome real

d ata on t h e t emperatures in t h e
upp er atmosp h ere A noth er very .

alluring subj ect of investigat io n

is th at of t h e c osmic ray s at v a
rions alt itud es B ut l ac k of sp ac e .

forb ids our go ing into th is field of

modern physics .

2 57 . C o mpo s it io n of th e air .

A l c h emists and c h emists h ad b een

stud y in g t h e atmosp h ere for ab out
2 0 00 years b efore it s comp osition
Sampl es of air
Fig 1 58 B all oon for inve s t igat ing
was d isc o vered
. .

t h e s t rat os ph ere W h y t h e ch ange

.

fromt h e open c ountry all h ave t h e

.

in sh ape
T HE R OLE OF C A R B ON DI OXI DE I N T HE A I R 2 73

same composition we find except for t h e amount of water vapor

, ,

in them Suc h a samp l e of d ry air is c omposed as fo llows :

.

100 vo lumes of air c ontain

Nit rogen
Oxy gen
A rgon

m
C arb o n d ioxid e
H eliu , neo n, kry pt o n, xeno n

In ci ties and in p oorl y vent il at ed p lac es , t h e mposition

co

of t h e air m
ay b e very d ifferent T h ere is always . more or less
so lid matter dust soot germs et c ,
float ing ab out in it , , . .

Howeve r th ese d ifferenc es are insignific ant wh en compared

,

with t h e l arge bulk of air wh ic h surrounds t h e earth T h is .

great o c ean of gas is c o nst ant ly b eing stirred by t h e wind s and

‘

air currents T h at is t h e reason wh y it s co mp osition if exam

.
,

ined in t h e op enc ount ry is always c onst ant as we h ave said , , .

2 58 . The rol e of c arb o n d io xid e in t h e air. On e xamining

t he co mp onents of air j us t l isted , we not ic e th at t h e amount
of c ar b on d ioxid e is very small ind eed Neverth eless it p lays .

a most imp ort ant ro l e as we sh all s ee , .

T h is gas 1s p ouri ng in to t h e atmosp h ere fromevery c h imney

and smokest ack ; it is b eing pro duc ed wh erever c arb on co m
p ound s burn or d ecay ; and it is b eing exh al ed b y every l iving
organism
_

Ont h e oth er h and all green p lants ab sorb c arb on

.
,

d ioxid e from t h e air In t h e l eaves it unit es with t h e water

.

wh ic h h as b een ab sorb ed from t h e soil by t h e roots T he .

pro duc t s of th is wond erful s ynth esis are st arc h and sugar
(whic h are c omp ounds of c arbon h y drogen and oxy gen) and
o xygen w
, ,

h ic h is set free We h ave seen 2 16 ) t h e bubbl es of

, . .

o xygen rising from p l ant s wh ic h were gro wing und er wa ter .

T h e c h emical c h ange wh ic h c o nv erts inorganic material

(carb on d ioxid e and wat er) into l iving matter can take p lace
only i n th e sunli gh t and is b rought ab out b y t h e aid of t h e green
,

c o l oring m aterial (c hl oro p h y ll ) in t h e l eaves T h is process is .

c all ed ph ot o synt h es is .
2 74 NIT R OGEN A ND T HE A T M OSP H ER E

T h is brief d escription of t h e import ant use th at pl ants make

of th is gas sh ows at o nc e th at anim als and p lants are com l
p e
ments of each oth er as regards t h e supp ly of oxygen and c arbon
d ioxid e in t h e air T o sum .

up th is c y c l e : p l ants remove
c arb on d ioxid e from t h e air

and c onvert it int o com

p ound s wh ic h in turn b ec ome
,

food for animals ; animals

c onsum e th is foo d m uc h as ,

a en in b u rn gas o l ine
g s g es

vapor and exh al e c arb on d i

,

o xid e (Fig
w

A ni mals
2 59 . I mpurit ies in t h e air

Fig 1 59 Carb on d ioxid e c ycl e

affec t ing h u man c omfort We .

m
. . .

are all fa iliar with t h e s o

ca ell d b ad air wh ic h is found in o vercro wd ed , p o orl y venti
lated rooms A nd we h ave all suffered t h e d iscomfort wh ic h
“
.

th is b ad air produces It was formerly th ought that t h e

.

c h ief fac t or in air wh ic h infl uenc ed h um an c omfort was c arb on

d ioxid e T h is view was h eld b ec ause t h e c arb on d ioxid e con
.

t ent is always h igh in c rowd ed stuffy rooms and t h e oxygen ,

c o nt ent l ower th an norm al B ut th is b elief h as b een sh own t o

.

b e erroneous I t is true th at h ealthful air must c ont ain a

.

c ert ain m inimum of o xy gen and th at o ne c an suffo c at e in an

atmo sph ere cont aining t oo muc h c arb o n d ioxid e Yet t h e .

amount of c arb o n d ioxid e whic h is found in even t h e worst

ventil ated rooms is far b el ow th is amount T h e chi ef factors .

whi ch really determ ine whether or not air is p leasant t o b reath e are
( 1 ) moist ure , (2 ) t emperat ure , (3) d us t , (4 ) minut e amo unt s of
co mpl ex co mpound s exh al ed by men and ani mal s .

T h e first t wo fact ors are closely ass ociat ed T h e h uman b od y is normally

.

at a co ns t ant t emperat ure of 98 6 F ( 37 N ow t h is t emperat ure is

° °
.

regul at ed b y t h e ev ap orat io n o f wat er fro m t h e s urface o f t h e b o d y If t he .

s urround ing at m os p h ere is p art ic ul arly mo ist , ev aporat io n pro ceed s wit h

d ifficul ty , and t h e regulat ion of t h e b ody t emperat ure is corres pond ingly
 76 NIT R OGEN A ND T HE A T M OSP H ER E

t o t he t op of t h e roo m T
h erefore it is b ett er t o open a wind ow
.

b oth at the top t o let t he warmupper air out and als o at the b ot
t omt o ad mit t h e fresh air Of course th is d Oes not mean th at
.
,

one sh ould sl eep in a strong d raft I n many p l aces it is feasible .

t o sl eep out of d oors on a sl eeping porc h and so t o secure

- -

perfect ventil ation .

u
1 4 Rec irc lat ed air intake
i
.

i 5 Flt ers ( 2 )
.

1 6 Blo wer fan

.

1 7 Evapo rat o r
.

1 6 Drl p dram
n n u in n
.

6 Co de sers ( 2) 1 9 S ct o la e
n n i
.

7 Co de ser fan 20 q uId l n e

8 n
Rec eiver ta k 21 H in
ea t g coa l
in n
. .

9 Stra er 2 2 St eami let

Hi u n
.

10 gh and lo w press re 2 3 St eamd rai

u nu
.

1 ° Belt drive swn c hes and g ages 2 4 Ple mc ham b er

n H in
.

Drive shaft
g therm
2 °
11 Sta db y starter swntc h 25 eat o stat

n u in
. .

3 ' Speed 12 Sta db y p l g m 26 Co o l g therm ostat

u
-
. .

4 0 $ and receptacle 2 7 A n d cts

Co m in u
.

5 '
p ressor 13 . Fresh air take 2 8 A i r o t let
.

C ourt esy of P ul l man C orp .

Fig . 1 60 . A ir -
cond it ioned P ull man car . No t e t h at t h e mot ive power c omes fromt h e
axl e Of t h e wh e el .

In t years we h ave seen steady progress mad e in th e

recen
'

d evelopment of equipment t o supply prop erly condit ioned air

not o nly in l arge aud it oriums c l assrooms and fac t ories b ut , , ,

al so in railro ad trains (Fig 1 6 0 ) and in privat e h omes . T h is .

equip m ent c l eans t h e air of d ust keeps t h e t em perature c om ,

fort ab le (ab out 6 8 h o ld s t h e h umid ity at t h e right p oint

°

(ab out 50 p er c ent ) and keeps t h e air in motion Such a con

,
.

d ition is cond uc ive t o efficiency as well as good h ealth .

S UM M A R Y 277

S UMM A R Y OF C HA P T ER XI X

EL EM ENT A R Y NIT R O G E N forms ab o ut fo ur -

fifth s of th e air .

Nit rogen compound s are es sent ial

. t o l ife and i mport ant ind ust rial ly .

P R EP A R ED fro s m th e air b y b urni ng out th e o xygen wit h ph os

ph orus ( or wit h red -
h ot c opper ); t h is is suffi c i ent l y pure for mos t
purpo s es Co . mmercial nit rogen is prepared fro m liquid air b y
evaporat ion .

P UR E N IT R OG EN is prepared b y h eat ing ammonium nit rit e

(sod ium nit rit e and ammonium c h l orid e) , wh ich gives wat er and
nit rogen .

P R OP ER T IES : nit rogen i s an inert s ub s t anc e . I t is a c ol orl ess ,

o d orl ess , t as t el ess gas ; d o es not b urn ; d o es not support
l
co mb us t ion
or respirat ion ; no t poisonous I t d o es not easil y unit e direc t l y
'

is .

wit h ot h er el ement s A t h igh t emperat ures it c omb ines wit h a few

.

met al s such m agnesium, and al s o wit h o xygen and h y d rogen

'

as .

A IR I S A M I XT U R E , NOT A C OM P OU ND . I t is e s s ent iall y

co mpos ed of nit rogen, oxygen, and argon, wit h v arying amount s of

wat er vapo r, c arb on d ioxid e , and d us t .

A I R C A N BE L I QU EFI ED and s eparat e d int o it s co mponent s by

al l owing t h e more vol at il e nit rogen t o b oil Off firs t .

A R G ON o c cur sin air t o t h e ext ent of nearl y o ne per c ent by vol u me .

T h ere are t rac es of four ot h er rar e gas es , wh i ch c annot b e mad e t o

co mb in e wit h an
y ot h er el ement s . A rgo n i s us ed in gas fil l ed
-

el ect ric l amps .

NEON is us ed in l uminous t ub es b ec aus e t h e orange re d -

l igh t is
v ery penet rat ing and ec ono mical t o operat e .

H EL I U M i s gas es ; it c an b e mad e co
one of th e rare ercial l y b y mm
liquefying c e rt ain nat ural gas e s I t is noninfla ab l e and is one
. mm
s ev ent h as h eavy as ai r U s ed in airsh ips . .

C A R B ON D I OXI DE i s int ro d uc ed int o t h e air b y comb ust ion and

respirat ion I t i s removed b y green pl ant s , wh ich get all t h eir carb on
.

fromt h e c arb on dioxid e in t h e air and pro duc e oxygen T h is b al anc e .

of pl ant and anim al l ife keeps t h e amount s of oxygen and c arb on

d ioxid e in t h e air c onst ant .
2 78 NI T R OGEN A ND T H E A T M OS P HER E

T H E C H IEF FA C T OR S in t h e air wh ich affec t H U M A N C OM FOR T

are ( 1) moistur e mperat ure (3)
, (2) te , d us t , (4) mal l amount s of
s

impurit ies giv en off b y t h e h uman b o d y T O get . as muc h fre sh air as

po ssib l e one s h oul d w ork, pl ay , and s l e ep o ut of d o ors - -

.

A IR C OND I T I ONI N G E QUI P M ENT is d esigned t o

-
c ont rol t h es e
four fact ors in t h e air .

QUES T I ONS
N ame t h e fiv e rare gases of t h e air
“air condit io ning
.

W h at is meant by
”
?
Of wh at use is t h e c arb on—dioxid e in t h e air ?
W h at is t h e approximat e co mposit io n O
f air b y v ol u me ?
N ame four gases wh ich are present in appreciab l e quant it ies

6 . N ame fiv e gases wh ich are present as mere t races in t h e air .

7 . D ist inguish b et ween t h e t ro pos ph ere and t h e s t rat os p h ere .

G iv e t h e name of t h e dis c ov erer and t h e d at es of dis c ov ery of each

‘

8 . .

of t he el ement s found in t h e air .

9 . Why was t h e dis c o v ery of t h e rare gases Of t h e air so lo ng d el ay ed ?

10 . Why d oes t h e c arb o n d ioxid e not form a l ay er at t h e b ot t om of a
roo m?

11 . H ow may o ne 1ncrease t he hu midit y of t h e air in a ro o m?

12 . T o wh at are t h e inj urious or dis agreeab l e effect s of t h e air d ue ?
13 . B y wh at ch e mic al t est c oul d y ou d ist inguish i
n t rogen from argo n?

I f air h as a d efinit e mposit ion m

'

14 wh y is it not c o ns id ered a
’

. co ,
co

und ?
p o

15 . W h at are t h e pri n
cip al j
ob ec t io ns t o d ust in t h e ai r we b reat h e ?
16 . Wh at co mponent s of t h e air are alway s present b ut v ary in amount ?

17 . D es crib e a way of get t ing good vent il at ion in a sleeping room .

18 . H ow woul d y ou prove t h at ordinary t ap w at er cont ains dissolved

air ?
19 . Wh y d o no t green pl ant s pro d uce as much oxy gen a t nigh t as d uri g n
t h e d ay ?
20 . Wh at rel ief d oes an elect ric fan in a roomoffer on a h o t d ay
? Ex
pl ain .

21 . H ow woul d y o u prepare a sample Of a

ir so as t o b e fre e fromwat er
vapor and carb on d ioxid e ?
 C HA P T ER XX

A M M ONIA A ND A M M ONIUM
‘

C OM P OUNDS .

E QUILIBR IUM

H ouseh ol d ammo nia mposit ion and formfl a preparat ion

co

propert ies refrigerat io n ammonium h y d roxid e and am

moniumsal t s commercial uses manufact ure of ammonia from
co al and sy nt h et icall y from el em ent s .

Fixat ion of nit ro gen rev ersib l e react io ns kinet ic equilib rium
Effect o f t emperat ure and o t h er co ndit ions
‘

effec t o f c at al y s t s .

o n t h e rat e of a reac t io n L aw of M ol ecul ar oncent rat io n

.

C .

Am mnia famil iar b ottl e

‘

261 in th e h o us eh ol d T he
m
. o .

wh ic h h old s t h e pungent c l eaning fluid c om only used in t h e

l

h ouseh old is lab eled ammonia or more accurately ammonia , ,

T h e name ammonia fi prop erly b el ongs t o t h e gas

’
wat er .

wh ic h c auses it s pecul iarly stinging smell T h is gas is extremely .

s o lubl e in wat er and is th erefore usually s o ld in wat er s o l ut ion .

It owes it s c l eaning qual ities t o t h e fac t th at t h e s ol ut ion is a

base th at is c ontains t h e OH Ion Since b oth ammonia
“
.
, ,

gas and wat er are v ol at il e it was formerly c all ed t h e vo l atile

,
”
alkali .

2 62 . C o mpo sit io n of a mmonia Wh en . we h eat ammonia

wat er, we get a gas wh ic h we c an S h ow is c omp osed of nitrogen
and hyd ro gen T o p rov e first th at ammonia c ont ains nitro gen
.
,

we lead t h e d ried gas through a tub e cont aining h O t copper

ox id e .We find th at t h e c opper oxid e is reduced t o metall ic
c opper wat er is f orm
, ed and a gas c o mes fro m t h e d el ivery
,

t ub e wh ic h is c l earl y nit ro gen

3 C u0 + 2 NH 3
2 80
P R EP A R A T I ON OF A MM ONIA I N T H E L A B OR A T OR Y 281

We d efinitely pro ve th at hydrogen is a c onstitue t o f

c an n
ammonia by passing t h e gas through a tube containing h eated
magnesium . A gas is set

free wh ich is hyd rogen

3 Mg + 2 NH 3
-
M g3N 2 + 3 H2 1
T o d et ermine t h e formula for
ammonia, we h av e only t o d et er
mine t h e d ensit y of t h e gas Since
mm nia w igh
.

one lit er of a o e s ab out

gra
, ms
t h e gra ol ecul ar mm
-

weigh t ( t h at is , t h e weigh t of
lit ers ) is gra s T h is corre m .

Fig 1 61 M aking d rY ammonia gas

mul a N H
. .

s po nd s t o a for s
.

2 63 . P reparat io n o f a mmonia in t h e l ab orat ory . We c an

v
c on enien tl y prepare t h e pure gas b y h eating a wat er so lution
of a onia Wh en t h emm . s ol ut io n

is b oiled t h e d issolved gas is

,

expell ed b ec ause it is m uc h less

s olubl e in h ot wat er th an in c o ld .

If we wish t o free t h e gas of wat er

vapor we arrange t h e apparatus
,

(Fig 16 1 ) s o th at t h e ammonia
.

passes up through a d rying t o wer

fill ed with pieces of s o d a l ime
( NaOH and C aO) Bec ause of it s
.

extrem e s o l ub il ity in wat er t he ,

gas is c o llect ed in a b ottl e h el d ,

mouth d own from wh ic h it d is

,

pl ac es t h e air .

A not h er c onv enient way oi preparing

h e gas is b y h eat ing a m xt ure of am
Fig 1 6 2 M aking am monia t i
mo ni um c h l o rid e , o r s al ammo niac
. . .

(N H 4C I) , and sl aked l ime in a l arge t est t ub e, as sh own i n fig

ure 162 T h e react ion is as fol lows
.
28 2 A M M ONIA A ND A M M ONI UM C OM P OUNDS

2 64 . mmonia A sid e
P ropert ies of a .

fromit s pungent o d o r t h e most strik ,

ing c h arac terist ic o f ammo nia is it s

extrem e s ol ub il ity I t is even more .

s o l ubl e m wat er th an hydrogen c hl o

d
ri e .

T he rapid it y wit h which mmonia gas

a is
ab s orb ed b y wat er may
b y t h e fol
be sh o w n

m
l owing experi ent A l arge flask is ent irel y
.

fill ed wit h ammonia, and a s t o p per is insert ed

t h ro ugh wh ich runs a lo ng t ub e and
“
a d rop
cont aining wat er
”
per T h e l ower end of t h e
.

t ub e dips int o a b eaker wh ich c o nt ains a red

m
lit us sol ut ion (sligh t ly acid ) B y pinch ing
-
.

t he b er b ulb , a l it t l e wat er iS forced int o

rub
'

t h e fl ask T h ereupo n t h e c o nt ent s of t h e

.

b eaker at once rush up int o t h e fl ask ( Fig .

and t h e red s olution b eco mes blue . Why ?

As ight b e supposed from it s mo m

lecul ar weight 1 7, ammonia is ab out
fl

A mmonia i s ah
“ “
Fig 1 6 3
wed readil y b y m
. .

e”
/

one h alf as h eavy as air liters of

-

air weigh ab out 2 9 grams ) T h at it is easily l iquefied was first

.

sh own by Farad ay ; at
Wat er f or c ond ens er
ord inary t em peratures
apressure of only ab out
m
9 at o s p h er es ( 132
p ound s p er square inc h )
is need ed .

Liquid a mmoma is
Fro m
l l
c o or ess b oil s at
. It Go l d s t or age

335 C and freezes

°
.

t o a c o l orl ess cryst al

line so lid at 78 C
°
.

C old s t or age

2 65 . L i q ui d a m
monia and I eft 1gera“
'

C omp r essor B ri ne t ank B ri ne p ump

t ion .
q md ammoma Fig . 1 64 . D iagra mof an ice making mach ine
-
.
 84 A M M ONI A A ND A M M ONI UM C OM P OUNDS

means m
a pu p th rough coils of pipe pl aced in t h e roo
of m .

It returns t o t h e t anks c ont aining t h e a onia c oi s for rec oo l

l mm -f

ing . T h e t emperature of a roo m can thus b e kep t very low,

and m eat and oth er

food placed in it c an ,

b e preserved for a
l ong time, since at
th is low temperature
( 2 5 F ) t h e process
°
.

of d ecay prac tic ally

c eases .

In many ties t h e
ci

t
en ire ice supply is

pro d uc ed in p l ants
“

using t h e ammonia
process j ust tlined ou .

Eikewise c o ld st orage -

p l ant s w h i c h ar e
cool ed by am monia
r e f r i g er at i o n ma

c h ines are l o c ated in

c onvenient p l aces for

C ourt es y B i rd sey e F rost ed F oods .

Fig . 1 66 . M ach ine for making frost ed food s .

” t h e h and h ng Of fQOd
p r o d uc t s i n l ar g e
quantities . T hus , t oo , many h otel s , m apart ent h ouses , and
c lub s h ave small ammonia refrigeratio n p l ants
-
.

Fro st ed food s h ave recent ly b een made av ailab l e at many pl aces T h ese .

are prepared b y wh at is known com mercially as quick freezing One way ”

.

of d oing t h is is t o pl ace t h e fo od t h at is t o b e froz en, such as m eat , fish , fruit ,

or veget ab l es , b et ween m et al pl at es T h en t h ese pl at es are c ooled b y t h e

.

d irect expansion of ammonia so as t o give a t emperat ure of ab out

\
°
25 F .

Wh en t h e food is in p ackages 2 inch es t h ick, it t akes ab out 90 minut es t o

freez e it complet ely B ut if such food s as fish fillet s or st eaks are unpack
.

aged , t h ey freez e in 5 t o 1 0 minut es I n Operat ion, t h e b ot t ompl at e is raised

.

b y a h y d raulic pist on unt il it picks up t h e next pl at e wit h it s l oad , and so

o n unt il all t h e pl at es h ave b een raised and t h e prod uct s are in c ont act on

b ot h s id es wit h t h e refrigerat ed pl at es ( Fig .

A M M ONI UM SA L T S

2 66 . A mmonium h ydroxide in
. Wh en ammonia dissolves
water we find th at we h ave not merely a solution of t h e gas in
,

water b ut a new compound wh ic h h as b asic propert ies It .

turns red l itmus blue ; it feels soapy and slippery t o t h e touch ;

it neutraliz es ac ids for ing salts , m
T h erefore it appears a s .

th ough a part of t h e gas must c ombine c h emically with water .

T h is i s indic ated l n t h e equation

NH 3 H gO $ 2 NH 4OH

T h e pro d uc t of t h e reac tion is c all ed ammonium h yd roxid e .

Wh en th is so lution is h eat ed , t h e c ompound d ec omposes into

ammonia and wat er T herefore t h e equat ion is written t o
.

represent a reversibl e reac tion .

A saturated so lution of ammonium hyd roxid e is lighter th an

wat er (spec ific gravity and at room t emp erature it
c ont ains ab out 36 p er cent by w eight of N H 3 A mmo nium .

hydroxide i s c onsidered a w eak b as e b ecaus e only ab out 1 per

cent of it s m o l ec ul es are d issociat ed Neverth eless it s use as .

a c l eaning agent d ep end s on

it s b asic properties , wh ic h
en abl e it t o d iss olve grease
and so remove d irt .

2 67 . A mmo ni um s al t s .

A mmonia and hyd rogen

c hl orid e co mbine at ord i
nary temp eratures t o pro
d uce awh ite c rystalline solid
c all ed ammonium c hl oride
( NH 4C 1) Fig . 1 6 7. H y d ro gen ch l orid e unit es wit h
NH 3 HQ] NH 4C l ammonia .

T his react ion can b e sh own b y using t wo reagent b ot t l es , one wit h a con
cent rat ed sol ut ion of ammoniaand t h e o t h er wit h concent rat ed hy drochloric
_

acid . Wh en t h e st oppers of t h e t wo b ot t les are b rough t near each ot h er,

awhit e cloud of mmoniumchloride part icles appears (Fig
a . T h e gases ,
ammonia and h y d rogen ch l orid e escape from t h eir aqueous
, solut ions and
cause t h is reac t ion t o t ake pl ace .
 A M M ONIA A ND A M M ONI U M C OM P OUNDS

Wh en ammoniumhydroxid e isneutral iz ed with hyd roc hl oric

acid and t h e solut ion is evaporat ed t o d ryness , a wh it e solid
result s T h is is identical with th at pro duc ed by t h e union
.

of gaseous am monia and hydrogen chlorid e It is, of course, .

a mmoniumchl orid e , or s al a mmoniac :

A lth ough t h e ammonium rad ic al (NH 4 ) h as never b een ob

t ained in a free st at e, y et we h av e many ammonium salts In
m
.

all of th ese c o mpound s th is gr oup of at o s NH 4 ac ts very m uc h

like a univalent metal , suc h as pot assiumor so d ium .

D o not c onfuse ammonia and ammonium A monia is . m

t h e gas N B 3 ammonium is t h e rad ic al NH 4 , wh ic h is f ound
'

onl y in c om pound s .

When ammonium c hlorid e is h eated , it sublimes ; th at is ,

it turns direc tly from sol id t o vap or T h e vapor read ily con.

d enses t o a so lid , or a sub limate

‘J

Wh en ammonium salts are h eat ed in a d ry tub e, th ey are

d ecomp osed : M ost of th em give ammonia and an acid For .

example :
NH 4 C l N H 3 i H G]“ "

It will b e noticed th at in th is c as e b oth pro d uc ts are vo l atil e

.
.

B ut wh en th es e pro duc t s are c o o led , th ey reunit e t o f ormt h e

s o lid am monium c hl orid e Here again we h ave a case of a
.

reversibl e reac tion .

If we wish t o l ib erat e ammo nia fromit s salts, we h ave merely

t o h eat any ammonium comp ound with an alkal i (suc h as
sl aked l im e or so d ium hyd roxid e) in ord er t o neut raliz e t h e

acid We th en get t h e unmistakabl e o d or of free ammonia

. .

T h is c an b e used as a t es t for ammonium s al t s .

Uses of ammo nia We saw th at l iquefi ed ammonia

2 68 . .

is used in ice making and in c onnec tion with c old storage, b eing
-

s h ipped in strong s teel c yl ind ers Large amounts of it ent er .

into t h e new meth od of preparing nitric acid The

aqueous sol ution, aqua ammo nia, is a c l eaning agent in t h e
h ome and in t h e industries A mmonium sulfate .
288 A M M ONIA A ND A M M ONI UM C OM P OUND S

by c oo l ing t h e gas b efore it s passage t o t h e next member of

t h e series .

T h e nitrogen and hydrogen are usually prepared fromwater

gas . Water gas is essentiall y a mixture of nitrogen hyd rogen , ,

Wat er und er
2 00 A t m . P r es sur e

D r i er

°
500 C .

C at al y s t

I nt er c h ang er

p r es s or f or S olut i o n
c i r c ul at i ng t h e G as
A t 2 00

Fig: 1 68 . D iagram o
f t h e H ab er proc es s for making ammonia b y s ynt h esis .

and b on monoxid e mad e b y t h e ac tion of steam on h ot c ar

c ar

b on ( c o ke) T o remove t h e c arb o n mo noxid e t h e gas is mix ed

.
,

with steamand p assed over a h eated c at alyst whic h c auses t h e ,

c arb on m onox id e t o reac t with t h e wat er as foll ows

CO H 20 00 2 l H2
“"

The resu lting n

gas c ontai s nitrogen ( originally present in t h e
air) , hyd rogen, and c arb on dio xid e T h e l atter c o p ound ay . m m
be m
re ov ed by treating t h e h ighl y c o pressed gas with water m .

2 71 v
. R e ers ib l e reac t io ns .
*
T h e prep aration o f ammonia
fromt h e el ements is ano th er exam pl e o f a reversi b le reacti on:

N2 + 3 H2 $ 2 NH 3

T he res t of t h is c h ap t er may b e p os t p o ne d if it s ee ms ad v is ab l e .
KI NET I C E QUI LI B R I UM 289

We have al ready met with a numb er of suc h reac tio ns T h ey .

will work b ac kward s wh en t h e cond itio ns are c h anged T he

‘ ”

m
.

formatio n of carb onic acid 2 18 ) and o f ammo niu hyd roxid e

266 ) in water sol utio n are t wo exampl es o f reversibl e reao
tions T h e d isso ciation of ammonium ch l orid e vapor
. 2 6 7)
is al so an exampl e .

2 72 . Kinet ic e quilib riull th at wh en a mixture

m We. rec a

of h y d rogen and nitrogen was kep t at 500 und er pressure

°

in contac t with finel y divid ed iro n a small amount and only

,

a sm all amo unt of ammonia was pro duc ed I f we were

t o start with pure ammonia at t h e same temperature and
pressure and in t h e s ame apparatus we s h ould find th at al m
, os t

al l o f it would b e d ecomposed int o nitrogen and h y d rogen ,

b ut a small amount of ammoni a would remai n unchanged T h us .

t h e final s tate of affairs in our c l o sed app aratus would b e t h e

sam e wh eth erwe s tarted with nitrogen and hyd rogen or with
p u re a m m o n ia W yh is. th is s o ?

Suppos e we c ould anal y z e t h e mixture in our cl osed reac tion

b ox continuousl y fro mt h e mo ment of mixing We sh ould find
.

th at wh en we started w ith nitrogen and hyd rogen t h e amount ,

o f am monia increased rapidly at first ; th en t h e increase was

sl ower and fi nall y t h e reac tion apparently st o pp ed wh en only a
,

few p er cent o f ammonia was formed No matt er h ow l ong we

.

waited we sh ould get no more I t is evid ent th at ei ther t h e

, .

reac tion h as really st opped or else a b al anc ed s tat e of affairs is

at h and T h ere seems t o b e no reaso n for t h e first po ssibl e

.

exp l anation Wh y sh ould t h e reac tion go t o a certain point

.

and th en t h e mo l ec ul es c ease interacting ?

“
I t is v ery h ard
t o imagine suc h a cond itio n or t o expl ain wh y t h e ammonia
mol ecul es sh ould stop d ecomposing at precisely t h e same
p oint .

B ut an entirely satisfac tory expl anation of th is puz z l ing

situation is at h and if we giv e up t h e id ea of t h e s topping of

c h em ic al ac tion and imagine rath er th at b oth t h e formation

and t h e d eco mp o sition o f ammonia are proc eeding at t h e
290 A MM O I A N A ND A M M ONI U M C O M P O UNDS

same time th at the two reacti ons are going on at the same
and
sp eed T h is state o f affairs is c all ed a kinet ic equilib rium
. .

From t h e point of view of t h e reacting mol ec ul es it is not a

s tate of res t T h e c o mpositio n o f t h e mixture ( c all ed t h e
m
.

equil ib rium ixture) is c onstant b ec au se we exam ine only

t h e sum t otal o f mol ecul es and no t t h e ind ivid ual mol ecul es ,

wh ic h are continually c o mb ining t o formammoniaand spl itting

up again .

2 73, Efiect o f c at al y st s . Nitrogen and hyd rogen will stand

at 50 0 with out forming ammonia, and ammonia may b e kep t
°

at t h e same tem p erature with out d ec o m p osing B oth sy stems .

are, h o we ver, met as t ab l e (un b al anced ) F or if we intro d uce .

t h e right c atal y st , small frac tions of t h e el ements soon c omb ine ;

or if we s tart wit h am mo ma, all b ut a small fraction of it
d ecomposes T h e c atal y st increases t h e sp eed of b oth reao
.

tions, whic h in it s ab senc e are so s l ow as t o b e imperceptibl e .

I n a sh ort time a b al anced stat e o f affairs ( equilib rium) is

reac h ed A catalyst decreases the ti me requi red for a reacti on
.

mi xture t o come to equili brium, but i t does not change the composi
ti on of t he equilib riumm i xture .

2 74 . Th e eff ec t of mposition of an
te mperat ure . The co

equil ib rium m ixture is usuall y d ifferent at d ifferent tempera

tures I n t h e c ase of ammonia t h e l ower t h e temperature t h e
.
,

h igh er t h e yield With oth er reac tions t h e reverse may b e true

. .

I n view of t h e effec t of t emperature on t h e ammonia equilib

rium one m, ay well ask Wh y Op erate at suc h a h igh t emp er
,

at ure as T h e answer is t o b e found b y rememb ering

th at t h e equilibrium state is not reach ed instantaneously b ut
th at i t takes time B oth t h e formation and d ecomposition
:

o f am monia proceed at a measurabl e speed T h ese rates

“
.

d epend on t h e conc entration of t h e sub stances t h e tempera ,

ture and t h e presenc e or ab senc e of catalysts With a given

,
.

c atalyst t h e h igh er t h e tem

,
m
p erature t h e sooner will equilib riu
b e attained I f an ammonia manufac turer h ad t o wait a y ear
.

for t h e maximum amount of ammonia t o b e formed h e c oul d ,

2 92 A M M ONI A A ND A M M ONI UM C OM P OU NDS

so metimes abl e t o d o th is in t h e c ase of reversibl e reactions by

increasing t h e concentration o f t h e reac ting sub stanc es or by
d ecreasing t h e c oncentration of t h e pro ducts A math ematic al .

statem ent of t h e rel ation of t h e c oncentrations of t h e sub

st anc es in an equil ib riumm ixture is sometimes c all ed t h e Law

of M ass A c tio n A d etail ed consid eration o f th is imp ort ant
.

principl e is b eyond t h e s cop e Of an el ementary c ourse b ut o ne ,

or t wo ex am pl es of it s use may b e mentioned .

I f we b oil an ammonium hyd roxid e s o l ution the

ammonia gas esc ap es and more ammon iumhyd roxid e d ec om
poses into water and ammonia Eventually al l t h e ammonium
.

hyd roxid e will h ave b een transformed into water and ammonia
gas wh ic h h as b oil ed out of t h e so lution T h e s am
, e is true .

fo r c arb onic acid so l utio ns Oth er exampl es of t h e L aw o f

.

M ol ecul ar C onc entration wh ic h is al so c all ed t h e Law o f M ass

,

A c tion h ave b een c onsid ered in C h ap ter X I I I d ealing with

, ,

ionic reac tions .

SUM M A R Y OF C HA P T ER XX

A M M ONIA ( NH 3) is a c o l o rl es s gas wit h a pungent Od or, ab out

h alf as h eavy as air and exc eed i gl y n s ol ub l e in wat er . I t is e asil y

liquefied at ord inary t emperat ures .

I n nature a mmonia is forme d b y t h e put refac t ion Of animal and

v eget ab l e mat t er . I n t h e l ab orato ry it i s us uall y prepared b y h eat ing
ammonia w at er or a mixt ure of ammonium ch l orid e and c al cium
h y d roxi d e Commercially ammonia i s prepared as a b y pro d uc t in
.
-

t h e d est ruc t iv e dis t ill at ion of c o al , and sy nt h et ic al l y b y t h e H ab er

process , in wh ic h nit rogen and h y d rogen mb ine

co d irec t l y .

C H EM I CA L BEH A VI OR mmonia red uces copper oxid e t o c opper

: a ,

forming w at er and nit rogen ; a mmonia react s wit h h ot ma g n e s iu m ,

pr o d uc ing m agn e s ium n it ri d e and h y d rogen ; am m on i a c om b i nes

w it h h y d rogen ch l orid e t o form ammonium ch l orid e .

A M M ON I A I N W A T ER S OLUT I ON i s b as ic and cont ains th e

NH 4 and OH rad ic al s of a mmonium h y d roxid e .

A M M ONI U M S A L T S are prepared g amm

b y neut ralizin onium

h yd roxid e wit h acid s .

QUES T I ONS 293

A M M ONIA I S U S ED for refrigerat ion purpos e s , as a c l eaning

agent (in wat er sol ut ion ), and as a s ourc e of a oniu mmco m m
pound s ,
and for t h e manufact ure of nit ric ac id .

T H E FI XA T I ON OF NIT R O G EN
/
means t h e proc es s of manu
mpound s
'

fact uring nit rogen co o ut of t h e free nit rogen Of t h e air .

R EVER S IB LE R EA CT I ONS co me to a c o nd it ion of equil ib riu m ,

in wh ich t h e t wo oppos it e r eac t ions proc e ed at t h e sa me rat e and th e

perc ent age mpo si t ion of t h e mixt ure r emains c onst ant
co .

A C A T A LY S T d ecreas es t h e t ime required for a reac t ion mixt ure

t o c omet o equil ib rium .

A R I S E I N T EM P ER A T U R E incr eas e s t h e sp eed of a ch emic al

reac t ion . I ncr easing t h e conc ent rat ion of t h e reac t ing sub s t anc es al s o
increas es t h e rat e Of a reac t ion .

T H E LA W OF M OL EC UL A R C ON C ENT R A T I O N s t at e s t h at b y
increasing t h e c onc e n
t rat ion of one of th e reac t ing s ub s t anc e s or by
d ecreasing t h e c onc ent rat ion Of one of t h e pro d uc t s , a react ion may go
more nearly t o ‘

co mpl et ion in a given d irect ion .

QUES T I ONS
1 D escrib e t h e l ab orat ory prep arat ionof ammonia (t wo way s )
. . W rit e
t he equat io ns .

2 . D escrib e a sy nt het ic pro cess of making ammoni a c ommercial ly .

3 . W h y are c a t aly s t s s o c o mmonly used in c ommercial ch emical

o ss ?
p r ce es

4 . W h at is t h e difference b et ween ammonia and ammonium

5 . H ow woul d y ou d ry ammo nia?
6 . W h at woul d b e t h e act ion of d ry ammomaon d ry lit mus p aper ? Why
7 . W h en wat er is ad d ed t o magnesium nit rid e ( M g aN z) , t h e pungent
o d or of a mmonia is not iced W rit e t h e equat ion
. .

8 C ompar t h e manner Of c oll ect ion o f ammonia wit h t h at of t he

.

e
h y d rogen chl orid e st ud ied in a previous c h apt er .

W h at pro pert y of a gas is s h own b y t h e fount ain experi ment as

d o ne wit h amm o nia?

10 . D es crib e t h e essent ial part s of amod ern ice making mach ine
-
.

11 H ow d oes t h e h ouseh ol d
. el ec t ric refrigerat or c o mp are wit h a com
mercial refrigerat ion pl ant ?
12 . Wh y not use nit rogen inst ead ofmmoniain arefrigerat ing maghine ?
a
13 . H ow wo ul d y ou prov e t h at ammonium h y d roxid e is a b ase ?
2 94 A M M ONIA A ND A M M ONI UM C OM P OUNDS

14 . How would y ou t est a s alt for t h e pres ence of t h e ammoniumrad ical ?

,

15 . Sh ow und er wh at c ond it ions t h e following react ion 1s reversib le

NH 3 H 20 N H 4OH
‘

16 . W h at is meant b y a reversib le react io n? Give four exa mples from

t h is c h apt er .

17 W h en t h e s t opper froma b ot t le Of concent rat ed a mmo n

iumh y d rox
id e is h el d near one from a b ot t l e of c oncent rat ed h y d ro ch l oric acid , wh it e
“smoke forms
,

Expl ain
”
. .

18 Writ e t h e equat ion in ionic formfor t h e neut ral izat ion of ammonium
.

h y d roxid e ( a) b y sul furic acid ; ( b ) b y nit ric acid ; (0 ) b y h y d ro chl oric acid .

19 H ow c an we prov e experiment all y t h at ( a) a mmonia cont ains nit ro

)

gen ; (b ) a mmonia cont ains h y d rogen?

W hy is it not c orrec t to c all an aqueous sol ut ion of a mmonia
a mmoniumh y d rat e ”
or
“
liquid amm
”
onia ?
=
l<

21 . H o useh ol d ammonia (N H 4OH ) is so met imes c all ed t he v ol at il e

alkali . Why ? u

22 . H ow d oes liquid ammonia differ

f m
ro aqua ammo nia?
23 I s liquid ammo nia a b ase ? s i
I l quid h yd g
ro e n c h l orid e an ac id ?

m
.

H ow is ammonia us ed in t h e anufac t ure of art ific ial ice ?

m
24 .

25 . N a e sev eral mmonia used in refrigerat ion

s ub s t ances o t h er t h an a
pl an t s W .h at ro
p p
’

er t y d o all o f t h e sub s t an c es h av e in c o mmo n?

26 W h at is t h e effect o f apply ing h eat t o ( a) ammonium h y droxid e ;

.

b
( ) a m mo niu m nit rit e ; ( )
c am m o n iu m c h l orid e ?

2 7 W h y is t h e fixation of nitrogen s uch an import ant ch emic al pro c ess ?

.

2 8 W h at is meant b y kinet ic equilib rium?

.

29 S t at e t h e L aw of M olecul ar C oncent rat ion and s h ow h ow it s appl ic a

.

t ion t o t h e H ab er pro cess mad e t h at pro cess more efficient and s uc c essful .

30 S pec ify t h e fol l owing fact s regard ing t h e H ab er pro c ess : ( a) reagent s
.

used ; ( b ) t emperat ure maint ained ; ( 0 ) pressure used ; ( d ) c at aly st ; ( e) per

c ent y iel d W h at ch anges were mad e in t h e improved H ab er pro c ess ?
.

T OP I C FOR FUR T H ER S T UDY

I c el es s I f possib le, v isit a col d s t orage wareh ouse or an

refrigerat io n. -

art ificial ice pl ant

-
W h at is t h e princip al expense ent ail ed in t his et h o d
. m
o f refrigerat io n? I nv est igat e t h e h o useh old refrigerat or M easure t h e .

t emperat ure in a h ouseh ol d refrigerat or wit h a t h ermomet er W h at is t h e .

temperat ure in a c ol d s t orage

-

pl ant ? I n an ice -
c rea m freez er ? On wh at
principle d o t h e iceless refrigerat ors D iscoveri es and
’
o perat e ? ( C ressy s

m
,

I nventions, C he i stry i n I ndustry , Vol .

2 96 N I T R I C A C I D A ND T H E FI XA T I ON OF NI T R O GEN

A no th er simil ar c o m pound , c all ed C h il e s al t pet er ( NaNOa) ,

is fo und in great d ep osits in C h il e and P eru T h is raw C h il e

“
.

c ontains from 1 7 t o 50 p er c ent o f so d ium

”
saltp et er, c al ic h e,

nitrate .

A s l ong ago as t h e ninth century men knew h ow t o make

nit ric ac id ( H NOs) from s altp eter T h ey foll owed a meth o d
“
.

sim il ar t o our o wn and c all ed t h e acid aqua fortis

”
(strong
water) b ecause of it s great c h emical activity .

2 79 . Th e manufact ure of nit ric ac id . It is generally pre

pared by a pro cess very l ike th at used in making hyd ro c hl oric
Smo kes t ac k
m
acid ; na el y , b y
ow es ” t h e action of con
flm
lfuric c ent rat ed su
"

ac id on a nitrat e .

S od ium nitrat e ,

as t h e c h eap est
and most abun _

d ant of t h e ni
trates is mixed ,

Fig 1 6 9 Diagram of a c ommercial met h od of making

. .
W ith c oncentrat ed
nit ric ac id .

sulfuric ac id and

h eated in a ret ort I n t h e lab oratory we t ake a tubul at ed

.

gl ass ret ort fo r th is purpos e b ut in t h e c o mmerc ial m

,
anu
f acture of nitric acid an iron ret ort is used ( Fig T he .

nitric ac id 1s muc h more v o l atile th an t h e sulfuric ac id Hence .

it d ist ill s o ff and is c o nd ensed in a suit abl e apparatus T he .

sub st ance l eft in t h e ret ort is so d ium b isulfat e :

N3 NO3 H 28 0 4 NaHSO4 HNO3 I

In recent years consid erable nitric ac id h as b een manufac

t ured by t h e o x id at ion of ammonia T h e pro cess was succ ess .

fully intro duced by t h e G erman ch emist, Wilh el m Ostwald .

T h is is d one by h eating a mixture of ammonia and air with

so m e c at alyst suc h as p l atinum:

NH 3 2 0 2 HNO3 H 20
P H YS I C A L A ND C H EM I C A L P R OP ER T I ES 297

T h e proc ess works at a rel atively low t emperature and th ere

fore requires very little energy ( Fig . T h e ammonia for
th is purpose is usually synth etic and t h e nitric ac id
pr o d uc ed is c onv ert ed int o nit rat es

T ub ul ar H eat
t er c h ang er

t inu m
G auz e C at al y s t

Fig . 1 70 . Diagra mof Ost wald s syst emof oxid izing ammonia
’
.

2 80 . P h ys ical and ch e mi cal propert ie s . P ure nitric acid

is a c ol orl essi liquid wh ic h b oils at 8 6 C I t fumes stro ngly
’
°
.

wh en x e d t o moist air I t is m1sc ib le with water in all

p os e
‘
.

proportions ; t h e c onc entrat ed form wh ic h we b uy cont ains

ab out 6 8 p er c ent of t h e ac id t h e rest b eing wat er Suc h a
,
.

mixture h as a d ensity of grams p er c ub ic c entimet er and

,

b oils at 12 0 C I t is h ighly c orrosive a few drops on t h e

°
.
, (

s kin c au sing a b a d burn Nitric ac id read ily d issoc iat es in

.

w t l i n i n H and N 0 3 io ns It is one of t h e three

’

a
‘

+
er s o ut o t o .

com mon strong acids Even t h e d ilute acid will turn t h e c loth
.

ing and skin y ellow .

Nitric ac id c an very easily b e d ecomp osed into water ,

nitrogen d ioxid e ( N0 2 ) and o xygen T h is d ecomposition

, .

takes pl ac e wh en t h e ac id is merely exposed for a l ong time

t o sunl ight For th is reason t h e nitric ac id in t h e l ab orat ory
.

oft en h as a y ell owish green co or

l W h en t h e ac id is h eat ed
-
.

strongly t h e d eco m
, p osit ion is very rapid :

4 H NO3

Nitrogen dioxid e is a red brown gas wh ic h d issolves in water -

.

Wh en it d issolves innitric acid , it giv es t h e latter ayell ow col or .

298 NI T R I C A C I D A ND T H E FI XA T I ON or NI T R OGEN

T he ll d fuming nit ric acid

so ca e
-
lt if
resu s

much of this oxid e is dissolved .

We may sh ow mposit ion of nit r1c ac1d

t h e d ec o
b y arranging a cl ay pipe s o t h at t h e st em d ips
b eneat h t h e wat er,
as in figure 1 7 1 .

Oxygen W h en t h e st em is
red h ot , afew d rops
of concent rat ed ni
t ric acid are po ured
int o t h e b owl As .

t h e acid runs d own

t h e s t e m, i t i s
d ec o mp o sed i nt o
wat er, o xy gen, and
ni t r o ge n d i o x id e
D ec ompos it ion of nitri c ac id b y h eat ing
.

Fig . 1 71 . .

T h is l at t er gas d is
so lves in wat er, and t h us only oxy gen is collect ed . T h e red b rown c ol or
-

wh ich is ch aract erist ic of nit rogen dioxid e c an easily b e seen wh en t h e b ub b les

first appear in t h e wat er .

281 Oxid iz ing act ion

. Since nitric acid easily d ec om
.

n
po ses a d gives off o xygen it is a go o d o xid izing agent
,
T he .

equation wh ic h represent s t h e

dec omposition of ord inary

d ilut e nitric acid wh en it acts
as an o xid izing agent is as
fO llows :

2 H N0 3

H zo 2 NO

We 1ndicat e t h e fact th at t he
o xygen is taken up by some

“
oth er sub st anc e and is not

I tself se free by wr1t 1ng t h e

sym
t
b ol l n brac kets
Fig
. 1 72 . Oxid at ion of carb on b y nit ric
. acid .

T h e oxid iz ing act ion of nit ric acid c an b e s h o wn b y gent l y h eat i g a n

sm all quant it y o f s awd us t and put t ing t wo o r t h ree d ro ps of c oncent rat ed
nit ric acid on t h e ch arred mass T h is experiment is b es t c arried out in a
.
300 NI T R I C A C I D A ND T HE FI XA T I ON OF NI T R OGEN

Besid es d issol ving all met als exc ept go ld and platinum, 11:
d issolves anumb er of metall ic oxid es, suc h as copper oxid e,
forming t h e c orrespond ing nitra
te and water :
0 11 0 2 HN 0 3 C U (NO3) 2 H 20
Nitric ac id acts o n suc h sa s lt as t h e c ar ona es , b t wh ic h give
a vo l at il e pro d uc t with t h e ac id

C aC0 3 2 H N0 3 C a(N0 3) 2 11 2 0 C0 2 1
Nitrates c anno t b e prepared by prec1pit at ion b ec ause t h e
ni trates f all metals are solub le
o i n water T h erefore we often
.

us e t h e nitrat e Of a met al wh en we wish t o work with a water

sol ution c ontaining a salt of th at met al .

In general nitrates are unstab le com p ound s W h en a nitrate .

is h eat ed it generall y d ecomp oses int o t h e met all ic o xid e

U

, ,

nitrogen dio xid e and oxygen : ,

2 C u( N 0 3) 2 2 C uO 4 N0 2 0 2

B ut in t h e case of so diumand p o t assiumnitrat es , t h e prod uct s

are oxygen and a nit rit e

2 N aN0 3 2 NaN0 2 0 2

T es t for nit rat es . We may eas ily rec o gniz e

a nit rat e b y adding coneen
t rat ed sulfuric acid and t h en h eat ing wit h c opper T h e it ric acid wh ich . n
m
is for ed act s o n t h e co pper, and
b rown vapors app ear .

M inut e amount s of t he NO
s o, radic al may
b e d et ect ed b y ad d
in g a sol ut io n o f ferro us sul fat e
(FeS O4 ) t o t h e solut ion wh ich is
t o b e t es t ed T h en c oncent rat ed .

Fig 1 73 T es t ing for a nit rat e in s ol ut ion

sul furic ac id is sl owl y p oured in
. . .

s o as t o forin a l ay er b el ow t h e m ixed solut ions T h e appearance of a d ark

.

b rownring (Fig 1 73) just ab ove the h eavi er sulfuric acid i ndicates the p resence
.

of th e N 0 3 radi cal T h e composit ion of t his d ark col ored compound is not
.
-

definit ely known b ut may b e d ue t o t h e ion T h e t est , h owever, .

is v ery d el ic at e, and it requires some skill in manipul at ion .

2 85 . I mport ant uses . Nitric acid

xtensively en ers t very e

into t h e p rep arat ion of a numb er of organic compound s wh ich

QUES T I ONS 01

are used xpl osives and as intermediat e sub stances in

as e

t h e preparation of dyes I t is also em pl oyed as a c leaning

.

agent an d for d isso lving certain met al s suc h as t h e silver in ,

t h e manufact ure of ph ot ograph ic film s T h e nitrates are very .

largely used as fert il iz ers ( See I ndustrial C h art A ppend ix )

/

.
, .

QUES T I ONS
1 . Wh y are t h e d eposit s of C h ile s al t pet er so v al uab le ?

2 . Wh y is t he U nit ed S t at es no l o nger d epend ent on o t h er count ries

for it s fixed nit ro gen (nit rogen compound s ) ?

3 . Why is
h eat ing necess ary in t h e l ab orat ory prep arat ion of nit ric
acid b ut not in t h re ar at io n o f c arb o n d io xid e ?
e p p

4 . M ent ion t h ree import ant pro pert ies of nit ric acid .

5 . L ist t he more import ant uses of nit ric acid .

6 . W hich acid is t he b es t s ol v ent for met als ? W h y ?

7 . N ame t h ree met als wh ich d iss ol ve in nit ric acid b ut d o not d issolv e
in h y d ro ch l oric acid :
8 . W h at is aqua regia?

9 . W h at are t h e s al t s of nit ric acid c all ed ?

10 . W h at are t h e more 1mport ant ch e mical propert ies of t h e nit rat es ?

11 . W h at is t h e rule for t h e s ol ub ilit y of nit rat es ?

12 . W rit e t he equat io n for t h e prod uct ion of nit ric acid b y t h e cat aly t ic
oxid at io n o f ammo nia .

13 . D es crib e th e b rown ring t est for nit rat es

-

(t h e nit rat e io n t es t ) .

W h at o t h er t es t c an b e used t o id ent ify nit rat es ?

14 . H ow may nit ric acid b e ob t ained fro m a mixt ure Of mmonia and
a
air ?

15 . Why is h y drogen no t ev ol v ed wh en z inc is ad d ed t o nit ric acid ?

16 . A l t h o ugh s o diumnit rat e is easily s ol ub l e in wat er, ext ens iv e d epos it s

of it exis t o n t h e wes t c o as t o f C h ile . Expl ai n .

17 . Wh y is s o d iumnit rat e rat h er t h an pot assiumnit rat e used in making

nit ric acid ?

18 C oncent rat ed nit ric acid cont ains ab out 30 per cent of wat er, and
.

co ncent rat ed sulfuric acid a b out 6 per cent of wat er Expl ain wh y t h ere .

is s o much w at er in c oncent rat ed nit ric acid .

302 NI T R IC A C I D A ND T HE FI XA T I ON OF NI T R O G EN

19 A cert ain weigh t of co pper is d issolved in nit ric ac id

. W ould more .

or l ess nit ric acid b e required if it were in di lute sol ut io n t h an if it were in ,

concentrated sol ut ion? Expl ain wh y T h e equat ion for t h e react ion of
.

copper on concent rated nit ric acid m ay b e writ t en t h us : C u 4 H N0 3

C u( N Oa) 2 2 N0 2 2 H20 H ow would t h e weigh t of copper nit rat e
.

formed in t e t h w o c ase s c o mp are ? H ow c oul d y ou recov er t h e co pper

nit rat e in pure cry s t alline form from t h e sol ut ion left b y t h e react ion?
20 . H ow d o we ac c ount for t h e y ell owish c ol or of t he c onc ent rat ed nit ric
acid wh ich h as s t oo d for so me t ime on t h e sh elf in t h e l ab orat ory ? H ow
c an t h e c ol or be re mo ved ?
21 . Wh y d issol ve gold and pl at inum wh ereas neit h er
will aqua regia

conc ent rat ed h y d ro ch l oric nor co ncent rat ed nit ric will ?

22 . Expl ain h ow t h e c h l orid e is formed wh engol d or pl at inu md issolves

in aqua regia .

23 . W rit e t he ch e mical equat ions for t h e ch a hges pro d uced wh en t h e

following nit rat es are h eat ed : (a) C a(N 0 3) 2 ; ( b ) C u(N 0 3) 2 ; (c) KN Os ;
( d ) N H 4N0 3 ; ( e) H N Os

OXI DES or NI T R OG EN
286 . Ox id es Five o xid es of nitrogenare known ;
of nit ro gen .

onl y th ree of th ese are im p ortant T h ey are nitrous oxid e

‘

(N nitric o xid e ( NO) , and nitrogen d ioxid e ( N0 2 ) Nitro .

gen trioxid e ( N 2 0 3) and nitrogen p entoxid e ( N zOs) are unstabl e

'

sub stanc es of no esp ec ial im p ortanc e .

Nit ric
xid e ( N O) Nitric oxid e i s most read ily pre
‘

287 . o .

'

pared b y t h e ac tion of d il ute nit ric acid upon c o pper T he .

equat ion fo r th is reac tion h as al read y b een d isc ussed

T h e apparatus is t h e same as th at used t o generat e hyd rogen .

T h e gas i s col orl ess and al mo st insol ubl e I n water .

T h e most important prop erty o f nitric o xid e 1s it s ab il ity t o

unite with oxygen ev en at ord inary t emperatures t o form a
, ,

red b rown gas nitrogen d ioxid e ( N O2 )

-

2 88 Nit ro gen d iox id e ( N

. T his gas, wh ic h we Just
s aw, is form ed wh en nitric o x id e c omes into c ontac t with oxy

gen h as a very unpl easant o d or and is p oisonous wh en inh al ed

,
.
30 4 NI T R I C A C I D A ND T H E FI XA T I ON o r N I T R O GEN

c o nsc ious of
pain Since it so eti es pro d uc es a
. m m kind of

hy steria, it h as b een na ed l augh ing gas m

I t c an b e c onvenientl y p repared b y h eating a mmonium
nitrate . T h is d ecomposes into water and nitrous o xid e :
NH 4NO3 2 H 2O N 20 l
T h e apparat us may be up as sh own in figure 1 7 5
set T h e h eat ust
. m
be care fully regulated or an exp losi on m
ay occur T h e nit rat e firs t mel t s
.

and t h en b egins t o efferv es ce as it d eco poses m

One of t h e pro d uct s is
.

m
st ea , wh ich is co nd ensed in t h e c at ch b ot t l e ; t h e o t h er , nit rous o xid e, is

c oll ec t ed over warm wat er in wh ic h it is b ut

, sligh t ly s ol ub l e .

Fig . 1 75 . M aki ng nit rous oxid e in t h e l ab orat ory .

Nitrous xid e is a col orl ess gas with a sl ightly sweet taste
o .

I t supports c omb ustion al most as well as o xygen Unlike .

o xygen h owever it d oes not unit e with nitric o x id e t o form

, ,

t h e b rown d ioxid e I t will not support t h e c omb ustion of

.

sulfur unl ess it is burning v igorously Nitrous o xid e is easil y .

l iquefi ed and in this form is sold in steel cy l ind ers Wh en it .

is used in minor Operations it is custo mary t o mix it with

‘

o xygen in ord er not t o d epriv e t h e p at ient entirely of oxygen .

EXP L OSI VES , OLD A N D NEW 30 5

FI XA T I ON OF N IT R OG EN
*

2 90 . T h e d irec t a mmonia proces s . T h is is tod ay t h e most

important p roc ess We h ave al read y . disc ussed t h e d irec t
sy nth esis o f ammoni a from
t h e el ement s i
Th s ’
t ffifféfifg;
’

He z
ammonia may b e c onverted
int o ammonium salts and S h ee t

used as fertil iz ers ,

or into
urea wh ic h is
a val uabl e sp ec ial fertil iz er .

Sy nth etic a mmonia c an b e R efr ac t o r

D i ni ng
o x idiz ed t o nitricacid 2 79)
and thus th is pro cess l ead
eventuall y t o n itrates .

m
'

291 . C yana id e proces s .

T h ere is anoth er ammonia

proc ess b ut it direct Fig 1 76 D iagramof a furnac e for making
IS no t SO . . .

c al c um W anamd e
C al cium c arbid e
1
( C ac z)
whic h 1s used t o generate ac ety l ene will c omb in e with nitrogen ,

wh en h eated (Fig forming carb on and a c ompound c all ed

.

c al ciumc yanam id e ( C EI C N 2 )

0 30 2 N2 C aC N 2 C
c al c i u m mm
c al c
c arb l d e c y anamlde

Wh en this co mp ound ( C aC N ) is treated with steam und er

z

pressure, it d ec omposes forming c al cium c arb onate and am

,

m onia
C aC N g 3 H 2O 0 30 0 3 2 NH g l

292 Expl o s ive s , A n expl osion is a very rap id

Old and new
'

. .

c h em ical ac tion in whic h a l arge vol ume of h ot gases is pro

d uced from liquid or sol id mat erial s c all ed expl o s ive s T he .

more rapid t h e action and t h e greater t h e quantity of gases

“

prod uced t h e more viol ent is t h e expl o sion Ol d fash io ned -

.

b l ac k po wd er is a mixture o f c h arco al sulfur, and potassium ,

T h is s ec t io n o f t he c h ap t er may well b e o mit t ed in a Sh ort c o urse in c h emis t ry .

306 NIT R I C A C I D A ND T HE FI XA T I ON OF NI T R OGEN

nitrat e . On b eing ignited it b urns sudd enly with t h e evol utio n

°

of a l arge volume Of gases If this action o ccurs in a confined .

space suc h as a gun b arrel a st rong ex pansiv e force is exerted

‘

, , .

M o d ern expl osiv es are c arb on compound s wh ic h c ontain

nitro gen and oxy gen T h ey are formed b y t h e ac tion of nitric
.

acid o n a numb er of d ifferent sub stanc es T h ey all h av e t h e .

pro perty of d ec omp osing quic kly wh en th ey are ignited or ,

when anoth er expl osive is set off very nea r th em T his l att er .

proc ess is c alled d et o nati o n Wh en t h ey dec ompose they pro .

'

duce a n enormous volum e of gases at a high tem p erature T h ese .

gases ex ert a terrific pressure wh ic h d o es t h e work required ,

b

o f an exp l osive .

T h e expl osivewhic h forms t h e b asis of t h e s mokel es s p o wd er

used in guns o f all cal ib ers is mad e by t h e ac tion of nitric acid
o n cotton C otton is a c omp ound of c arb on h y d rogen and
. .
, ,

o xygen c all ed cell ul ose and t h e action of t h e nitric acid c o n

‘

, ,

verts it into a c ompound call ed nit rocell ul o s e T h e nitro

m
.

cell ul ose is turned into a j ellyl ike ass by c ertain so lvents .

T his is pressed out into sh ort ro d s o r strips and d ried I t burns .

in t h e b arrel of a gun wh en ignited by t h e prl mmg c harge and ,

t h e gases pro duc ed push out t h e pro j ec til e T rinit ro t ol uene .

and picric ac id are t h e expl osives used in h igh expl o -

siv e s h ell s in mines and in d epth c h arges

, ,
T h ey are pro .

d im ed by t h e a c t ion of nitric ac id o n t ol uene and c arb o l ic ac id

resp ec tiv ely T hese l atter sub stances are prepared from c o al
.

t ar . T rinitrotol uene and picric acid can b e set o ff

only b y fi rst expl o d ing in th em a m ore sensitive exp l osiv e (a

d etonator) T h ey expl o d e sudd enly and with muc h viol enc e

.
,

c ausing great d am age High expl osives d etonate al most one

.

h und red times as rapidly as bl ac k gunpowd er .

Nit roglyc erin is mad e by t h e ac tion of nitric acid on glycerol

I t is a v ery sensitive expl o sive and is seld om
used unmixed When it is soaked up in sawd ust or some oth er
.

porous material and mixed with sod ium nitrat e d ynamit e is ,

pro d uced D ynamite is t oo v iol ent and sensitive an expl o sive

.

t o b e put in guns or sh ell s I t is empl oyed for bl asting o ~f r

.
,
 ‘

30 8 NI T R I C A C I D A ND T H E FI XA T I ON o r NI T R OGEN

nitro gen c o mpo und s wh ic h o c c ur naturally are c all ed prot eins .

T hey are c o mp os ed of c arb on, nitro gen, oxygen, and h y d rogen .

T h e pl ant is abl e t o b uild th em up fro m t h e water, c arb on d i

'

oxid e, and t h e inorganic nit rat es th at it fi nd s in t h e s oil T he .

pro t el n 1n anim al s is o bt ained ent irely fromt h e p l ant s or oth er

animals wh ic h th ey con
sum e . T h e wast e pro d
uct s of p l ant and animal
life c ontain t h e nitrogen
of t h e original prot ein
c om bined in a number
of different c o m pound s .

T h es e are easily act ed

up on by b act eria in t h e
s oil and c h anged into
"

ammonium c omp ound s .

T he mmonium
a co m
p ound s in
turn are o xi
Fig 1 78
. Nit rogen c y cl e
. .
d iz ed by oth er b acteria
'

t o nitrates wh ic h c an b e
,

taken up b y t h e p lants (Fig . Nitrogen th us makes a

cycl e th rough p l ant and anim al l ife and t h e soil .

2 94 .Nit ro gen c o mpo und s as fert iliz ers Unfortunately

.

th ere are t wo factors at work upsetting th is cycl e I n t h e .

first p lace, th ere are certain b ac teria th at c onvert s ome of

t h e nitrat es of t h e s oil int o free nitrogen, wh ic h i s thus l ost .

I n t h e sec ond plac e, inmo d ern c ivil iz at ion t h e waste pro duc t s
of p l ant and anim al l ife no l o nger find th eir way b ac k t o t h e
s o il . Large quant it ies of th em are f orever wast ed by b eing
d umped into rivers and t h e s ea For th ese reasons nitrogen
.

must b e continually suppl ied t o t h e soil in some formin wh ich

t h e p l ant s c an use it . If t h e waste pro d uc t s of l ife, suc h as
manure, are available, th ey make an excellent fertilizer ; b ut
t h e supp l y is very l imit ed .

T h e art ificial fertilizers prepared by t h e c h emist consist of

NI T R OGEN C OM P OUND S A s FER T IL I Z ER S 309

a mmonium c o mpounds and t h e nitrat es . Nitric ac id may b e

pro duced by t h e d irec t oxid ation o f nitrogen converted into ,

c al c ium nitrat e and u sed d irec tly as a fert ilizer In some .

l ocalities calc iumc yanamide can b e used d irectly as a nitrogen

fertilizer T h e ammonia prepared fromit or prepared by t h e
.
,

d irect synth etic process can b e used ,

as ammonium salts ; or it may b e

o xid iz ed t o nit ric ac id and used as

nitrat es Thi s prob lem of ob tai ning

.

availab le ni trogen for p lants from th e

atmosph ere i s one whi ch wi ll h ave i n
creasi ngly great econom i c im p ortance
,

in th e y ears to come .

So me plant s h ave th emselves t h e

power of c onvert ing t h e nitro gen of
t h e air into useful c ompound s T h is .

is brought ab out by c ert ain b acteria

found in t h e tub ercles ou t h e roots of Fig 1 79 Noriul es c ont aining
'

. .

mt mgen fi mg b act em
leguminous p lants , suc h as p eas and
0

'
'

c l o ver ( Fig I t is now p ossibl e t o b uy th ese b ac teria and

.

t o inocul at e b eans and simil ar pl ants W ith themb ef ore p lanting .

T h is insures t h e growt h of t h e b act eria ont h e ro ots of t h e p lant

»

and consequently t h e d irec t pro duc tion of a nitrogen fert iliz er

by t h e pl ant itself .

S U MM A R Y OF C H A P T ER XXI
NIT R I C A C ID I S M A D E b y h eat ing conc ent rat ed s
u l furic acid and
so d iu m nit rat e and b y t h e c at al y t ic o xid at ion of a mmonia It . is a
c ol orl es s l iqui d wh ich m
ixes wit h w at er . T h e commercial con

c entrat ed ac id c ont ains 32 per c ent of w at er .

NITR I C A C I D i s eas il y d ec o m
po s ed , for ming Oxid es of nit rogen
and oxy gen I t is a powerful o xid izing a
.
gent A ixt ure of nitric . m
and h y d roch l oric acid is aqua regia; t h is furnish es nasc ent ch l orine .

U NLI KE M OS T A C ID S nit ric acid very s el d o m prod uces free

h yd rogen wit h met al s Oxid es of nit rogen are usually t h e prod uct s ;
.

in s ome c as es ammonia may b e formed .

310 NI T R I C A C I D A ND T HE FI XA T I ON OF NI T R OGEN

NIT RA T ES M A Y B E P R EP A R ED b y t h e act ion o f nit ric acid on

( 1) met al s , exc ept gol d and pl at inum

(2 ) oxid es and h yd roxid es
( 3) s al t s giving vol at il e pro d uct s
NIT R I C A CI D I S U S ED in t h e preparat ion Of expl osives , fert ilizers ,
and d y es . Of t h e nit rat es , t ho s e of s o d iu m and pot as siu m are
th e most import ant . S o d ium nit rit e is mad e b y h eat ing s o d iu m
nit rat e .

NIT R I C O XI DE ( N O) is prepar ed b y t h e ? act ion of d il ut e nit ric

acid on c opper In c ont act wit h oxygen, it pro d uc es nit rogen d io xid e
.

(N which is a r ed b rown gas , poi s onous ; and S ol ub l e in wat er

-
.

Nitrogen d ioxid e on c o ol ing d oub l es it s mol e cul es and pas s es int o

n
it rogen t et ro xid e ( N 2 0 4 ) .

NIT R OU S OXI DE ( N 2 0 ) is mad e b y h eat ing ammonium nit rat e .

It s upport s co mb ust ion

I t pro d uc es anaes t h esia
. .

T H E FI XA T I ON OF N I T R O G EN means t h e proc e s s Of manu

fact uring nit rogen c ompound s out of th e free nit rogen of t h e air .

T H E C OM MER C IA L P R O C ES SES for t h e fix at ion of nit rogen

namid e pro c e s s es
incl ud e t h e dir ec t ammonia and t h e cy a .

.
NIT R I C A CID i s us ed in t h e manufact ure of al l explos ives .

S mo kel es s po wd er i s nit ro cel l ul o s e and is mad e from cot t on . The

b urs t ing ch arge in s h ell s , mine s , et c , i s t rinit ro to l uene . or

picric acid Dy namit e is nit rogl y c erin ab s orb e d in so me p orous

mat
.

erial and mixed wit h s o d iu mnit rat e .

NIT R A T ES ar e ess ent ial t o pl ant growt h . Nit rogen goes t h rough
a cy cl e I n a mmal and pl ant l ife and t h e s oil T h is c y cl e is ups et b y
.

s everal fact ors . Fo r t h is reas on nit rat es m

us t b e appli ed t o t h e l and
as fertilizers .

QUES T I ONS A ND P R OB LEM S

1D es crib e t h e prep arat ion and pro pert ies of nit rous oxid e
. .

2 H ow woul d y ou d ist inguish in t h e l ab orat ory b et ween

. oxygen and
nitrous oxide
3 . diss ol ved in dilut e nit ric acid , wh at b ecomes Of it ?
Wh en copper is
Wh at gas is evolved ? How coul d we S h ow wh at b ecomes of t h e copper ?
4 . W h ich is t h e most st ab l e of t he oxides of nit r ge
o n?
312 NI T R I C A C I D A ND T HE FI XA T I ON o r NI T R O G EN

.
T OP I C S FOR . FU R T H ER S T U DY

T h e fixat ion nit rogen in t h e Unit e d S t at es

'

of . W h at met h o ds of fixing
nit rogen are c ommercially possib l e t o d ay ? Wh at met h od s h ave b een used
on a l arge s c ale in t h is c o unt ry ? Wh y is t h e manufact ure of nit rogen
compound s from t h e air of nat ional im ( Sl osson s C reative p o rt ance ? ’

Chem i stry D unc an s C hem istry of C om merce U S D ep t of C ommerce

’
. . .
, ,

B ulletin N o 52 Ut iliz at io n o f A t mosph eric N it rogen Find l ay s C hemistry

’
.
,

in the S ervice of M ankind and C hemi stry in A griculture ) .

W h y are nit ric and s ulfuric ac id s co nsid ered t he prime

‘

Expl os ives .

essent ial s for t h e m anufac t ure of explos ives ? W h at ot h er mat erials are
need ed for war t ime -
expl os ives ? For co mmercial expl osiv es ? W h at is t h e
difference in ac t io n b et ween smokel ess p ow d er, mercuric fulminat e ,

and d y namit e ? H ow is each mad e ? W h at explosives are used in mining

and agric ul t ure ?
( M art in s M odern Chemistry, T ild en s C he ical D iscovery
’ ’
m
and I nvention and C he istry i n I ndustry , Vol m .

R EVIEW QUE S T I ONS ON C H A P T ER S XI X XXI -

1 . Wh at is wrong wit h each of t h e following : (a) H eO ; ( b ) A l

(c) N 0 3N H 4 ; (d ) ( C a) 2 C l ; ( e) N a2 ( C O) 3 ? R ewrit e each c orrect ly -
.

2 . W h at are aqua a mmonia ,

aqua forti s, aqua regi a, and aqua p ura?

3 . N ame t h ree fac t ors wh ich affect t h e speed of react io ns :

W h y d oes ammo nium

4 . h y d roxid e feel s o apy and sl ipp ery t o t he
t u h ? W h y from t h e p oint o f V iew o f t h e io niz at io n t h eory , d oes h ous e
“
o c ,

amm nia

m
h ol d
”
o act as a cleaning agent ?

C ompare t h e
5 et h o d o f prep aring nit rous oxid e wit h t h at of pre

paring ch emic ally pure nit rogen

.

W rit e und er each t h e equat ion for t h e .

react ion invol v ed and no t e t h e s imil arit y .

S uppose t h e l ab els h av e
6 . co me off t h e b o t t les of nit ric acid , h y dro
c hloric ac id , and s ulfuri c ac id . H ow woul d y o u proceed t o get t h e d at a
b y which t h e l ab els coul d be repl aced co rrec t ly ?

7 . N itrogen and ch lorine pl ay a d oub l e rol e in h uman eco no my : t h ey

are b ot h p reservers and d es troy ers of life . Expl ain wh at is meant b y t h is
s t at e ent m
(A ft er Sl osso n )
. .

8 . M ent ion four gases which are sol d commercially in met al cy lind ers
mpressed m commercial use is eac g p
h u ?
i n co or l iquefied for T o wh at . as t
Wh ich of t h e gases wo ul d b e in l iquefied
.
fo rm and wh ich wo ul d b e merely
co mpressed ? Wh y ?
H ow c o ul d y ou pro ve experiment ally t h at t h e act io n of
9 . very d il ut e
i
nt c ac d on zi
ri i n c p ro d uc es ammo nia?
R EVI EW QUES T I O NS ON C HAP TE RS —
xxx x xx 13

10 St art ing wit h t h e raw mat erials air and wat er, t h e elect ric current ,
.

and all t h e ot h er necessary ac cessories and app arat us , d es crib e and expl ain
t h e st eps Of t h e proced ure b y which y ou cou l d finally ob t ain ammonium
nit rat e .

11 S t art ing wit h t h e el ement s nit ro gen, h y d rogen, s ulfur, and oxy gen,
'

sh o w b y wh at ch emic al st eps y ou can prepare ammonium s ul fat e G ive .

equat ions .

12 . W h en sod iu m nit rat e is h eat ed , wh at s olid pro d uc t

v igo rously

remains ? B y wh at ch emical t es t could y ou dis t inguish it from t h e original

nit rat e ? Writ e t h e equat ions .

13 . N ame t wo acid s wh ich are st ro ng oxid iz ing

agent s . m
C o pare t h eir
propert ies ( a) wh en in d ilut e s ol ut io n and ( b ) wh en in c o ncent rat ed sol ut io n .

14 . Wh at would b e t h e ac t io n Of d ry ammo nia on d ry l it mus p per ? a

H ow c an ammonia, as ord inaril y prep ared b e mad e , d ry ? C ould y ou d ry
it b y passing it over c al cium ch l orid e or b y b ub b ling it t h rough c oncent rat ed
s ul furic ac id as is d o ne in t h e c ase o f s o m any gases ? Expl ain Wh at .

c h arac t eris t ic of each of t h ese l at t er s ub s t ances is ut il iz ed in t h eir use in

d ry ing gases ?
15 .
( a) W hy are a m
m ni
o a, ch l or ine , and h y d rogen chl orid e c oll ec t ed

b y air d is pl acement rat h er t h an ov er w at er ? ( b ) H ow and wh y d oes t h e

m
c oll ec t io n o f am o nia b y air d is pl ac ement d iffer from t h at used for ch l orine

and h y d rogen ch l orid e ? (0 ) M ake si mple sket c h es to ill ust rat e each of

t h ese l at t er c ases .

16 . W h at is a good met h od of preparing nit rat es ? I llus t rat e wit h an

equat ion for t h e prep ar at io n of z inc , nit rat e .

17 H ow muc h ammo nium nit rat e

. must b e h eat ed t o y iel d 8 8 grams of

nit rous oxid e ?

A mmonium s ulfat e und er t h e name of S ul fat e Of A mmo nia,
“
18 .
, s ol d

is a v al uab l e fert iliz er W h at t es t would y ou use t o d et ermin

. e wh et h er a

c ert ain wh it e solid is t h is sub st anc e ? W h at percent age of nit ro gen d oes it
c o nt ain?

19 . me of d ry nit ric oxide

W h at vol u will b e evolved b y t h e
act ion of 38 4 grams of co pper wit h an exces s of d ilut ed nit ric acid ?
2 0 Wh at volume of ammonia
. will b e generat ed b y t h e act ion
of 1 07 gram s of a
(
mmonium ch l orid e react ing wit h an excess of cal cium
h y d roxid e ?
 C HA P T ER X X II

T HE NEW P ER I ODI C LA W

Families of ment s
el e propert ies and at o mic weigh t s old

and new period ic l aw at omic numb ers perio d ic cl assificat ion .

A t omic numb ers and v al ence

‘

met als and non et als elect rons m

and at o ms el ect rons and v al ence .

2 95 . m
Fa il ie s of el e ment s . We sh all presently find th at
so me of t h e el ements c an very c onveniently b e grouped into
famil ies acc ord ing t o simil arit y in c h emic al properties Fluor .

ine c hl or ine b r omine and i o d i ne f o r m s uc h a f amil y

, , ,

of c l osel y rel at ed el ement s S imil ar l y l ith ium s o d ium

.
, , ,

p ot as s ium r ub id ium and c aes i um mak e up t h e f amil y

, ,

k now n as t h e alk al i metal s A nd th er e ar e oth er g r oup s

[

as w ell S uc h ar r angeme nt s ar e v er y c onv enient in

.

s yst em at iz ing t h e c h emic al fac ts ab out el ements s ince it is

p ossibl e t o make cert ain general st at ements ab out all t h e
members of t h e same family For example th e alkali metals .
,

all react wi th water th eir h ydroxi des are solub le and formstrong
,

b ases their i ons h ave a valence of one and almost all th e alkali
‘

, ,

salts of com mon acids are soluble in water .

2 96 P ropert ie s of el ement s and t h eir at o mic weigh t s

. NOW .

t h e exist ence of fam i l ies of rel at ed el ement s p oint s t o t h e

ex ist ence of som e fund am ent al law in regard t o t h e c h emic al
properties of t h e el ements T h e R ussian M end el ej eff ( Fig 1 8 0 )
. .

was t h e first ch emist t o sh ow c l early h ow t h e el ements might b e

arranged acc ord ing t o a d efi nit e syst em .

If we p l ac e all t h e element s in t h e ord er of th eir atomic

Weights (omitting h y drogen) we sh all find th at t h e eighth a
,
nd
s ixteenth el em ent s are fl uorine and c hl orine respec t ively t wo ,

sub st anc es wh ic h resem bl e eac h oth er very c l osel y T h is kind .

of rel at ionsh ip c an easily b e stud ied int h e firSt sixt een el em ent s .

314
 T HE NEW P ER I ODI C LA W

2 98 Value of t h e Ol d period ic t ab l e
. I n spit e of t h e exc ep .

t1ons , t h e p erio d ic law as stated b y M end el ej eff is a very great

sc ientific general ization Not only d id it bring into o ne orderly
.

s c h eme al m ost all known c h em ic al ph en om ena, b ut al so it eu

abled M end elej eff t o m ake several b old pred ic tions wh ic h were
sub sequently c o nfirm ed by exp erim ents I nprop osing t h e t able, .

t h e R ussian c h emist was obl iged t o leave s everal bl anks in ord er

t o put t h e known el ement s of similar propert ies in t h e same
group T h ese bl anks h e b elieved represented und iscovered
.

el em ents On t h e b asis of t h e p osit ion of th ese b lanks h e was

.

abl e t o pred ic t with great ac curac y not o nly t h e exist enc e of

these elements b ut th eir physic al and c h emical prop ert ies as
well . H is prediction was verified in three instances T he .

fo llowing tabl e sh ows one of th ese He proph esied t h e proper .

ties Oi wh at h e c alled eka aluminum, wh ich , wh en it was finally

-

d iscovered , was c al l ed gallium T h ere is h ardly a sc ientific .

pred ict ion in hi story th at is mor e st artling th an th is

PRO PE T E
R I S OF G A LLI U M
'

PR E D CTE D
I FOU ND

sligh t l y oxid ized at

red h eat
A ct ion on wat er d ec omp oses at red d ec omp os es at h igh
h eat te mperat ures

2 99 .
perio d ic l aw A young Engl ish man M os el ey
T h e new
”
.
,

( Fig
. in 1 91 2 l aid t h e b asis of a new p erio d ic law wh ic h ,

unl ike t h e Old o ne h as no excep t ions , M oseley was investi .

gating X ray s th ose v ibrations of very sh ort wave le ngth

'

w h ic h ar e s o muc h more p enet r ating th an o r d i nar y l ig ht r ay s .

Event uall y h e d iscover ed a meth od of s p read ing o ut X r ay s

f
int o a spec trum wh ic h was of course invisibl e b ut could b e
, , ,

p h ot ograph ed His apparatus was c all ed an X ray sp ectro

.
-

s c op e . He used it for investigating t h e nature of t h e X rays

318 T HE NEW P ER I ODI C LA W

e mitted by various el ements wh en th ey are b o bard ed by m

el ec trons in an X ray t ub e Just so B unsen many years
-
.
,

befo re stud ied with a real spec trosc ope t h e visible l ight of
t he
“ ,

so d ium fl ame T h e X ray spec tra Of various meta

.
-
ls ,

wh ic h M oseley used as ant i

c ath o d es in h is X ray tub e -

( Fig h ad s h arp l ines of

.

d efinite wave l engt h j ust as ,

t h e v isibl e l igh t fro m many

h eat ed element ary v ap ors ,

h ave d efinit e l ines as sh own ,

c l ear l y i n a s p ec t r um c h ar t .

T h e numb er of l ines in
t h e X r ay s p ec t r a is l ess -

th an is usuall y found in t h e .

c as e of v is ibl e sp ec tra M os e .

ley now mad e t h e very imp or

tant d isc overy th at t h e wave
length of t h e lines d ec reased
regul arly as h e sub stitut ed

one el em ent for t h e next one

h l gh er at o m
Of l c wel gh t H e
Fig 1 8 1 H EN R Y G J M O S E L EY ( 1 88 7
'
-
. . . .

A n Engl ish ph y si cis t wh o d et er c ould th us arrange t h e el e

mined t h e X ray spect ra of met al s
-
.

ments in suc h an order th at

t h e p airs Of l ines in t h e sp ec trum of eac h app eared t o h ave
been progressively and regularly sh ifted in t h e d irec tions of
d ecreasing wave l ength as one p assed from one el ement t o
anoth er of higher ato mic weight ( Fig .

T hi s arrangement of th e elements on th e b asis of their X ray -

sp ectra i s found to b e exact ly li ke th e old seri es b ased o n at om ic

weight s , excep t th at now t h e p airs of irregular el ements are no
longer reversed b ut fall int o th eir proper p l ac es T h is arrange .

ment of t h e elements turns out t o b e in t h e order of t h e atomic

numb ers Of t h e el ement s T h erefore we c an revise our ol d
.

law as fo ll ows : T h e ch emical prop erti es of th e elements are a

p eri odi c functi on of th eir atom i c num b ers U nl ik e t h e Ol d .
 20 T HE NEW P ER I ODI C LA W

m
It will b e seen th at t h e el e ents fall int o nine general vertic al
groups , t h e first of wh ic h is c all ed t h e zero group and t h e l ast
t h e eighth group T h e th ird h orizont al row s t arts with argon
.

and end s with th ree el ements , iron, c ob alt , and nic kel , wh ic h
are p l ac ed in t h e eighth group T h e fourth row h as no element
.

in t h e zero group and

is Obvious ly somewh at
d ifferent from t h e pre
V1ous ro ws : it ends with
t h é element bromine
’

T h e th ird and f ourth

rows of th is t abl e t aken

t ogeth er are c alled a

l ong perio d ; t h e first
and sec ond rows are
c all ed s h ort per io d s .

A gain t h e fifth and

,

sixth rows and t h e

s e v e nt h and e i g h t h

make l ong period s It .

I nc reasi ng Wave L eng t h will b e notic ed th at a

Fig 1 8 3 X ray s pect ra and at omic numb ers l ong p eri od h as i n th e .

middle of i t three elements

-
. . .

which are put t ogeth er in the eighth group ; th is seems t o t ake

t h e p l ace of t h e empty spac e in t h e z ero group T h e middl e .

p ortions of t h e l o ng perio d s h ave b een inc l osed by a h eav y l ine,

and t h e el ements print ed in it al ics Suc h el ements forma sub
.

group oi eac h main group and are more nearly relat ed t o one
anoth er th an t o t h e oth er numb ers T hus , in t h e fi rst group
.

t h e alkali metal s formone family, and c opper, silver, and go ld

,

a d ifferent b ut rel at ed family

'

. m
30 1 A t o ic numb ers m
T h e nu b er corresponding t o t h e
.

p o s it io n of t h e el e ent inmth is new s eries , if we t ak e hyd ro gen

as one, is c alled t h e atom ic numb er Of t h e el ement We h ave .

already seen 1 66 ) th at t h e atom of an el ement c o nsis s of

t a
T H E P OS I T I ON O F T H E M ET A L S 21

posi tively c harged nucleus surround ed by o ne o r more h ega u

t ively c h arged elect rons From experim . ent s with alp h a p ar

t ic les emitt ed from rad ium it c an b e sh own th at t h e atom

, ic
num b er measures the p bsi tive charge on th e nucleus and therefore
must also give the number of electrons around the nucleus
,

T h e ato mic numb er is th us a more rel iabl e c riterion of t h e

c h em ic al properties of an el ement th an t h e ato mic weight .

T h e ato mic weight of an el ement is t h e average of t h e weights

of a m ixture of isot op es with due allowance for relat ive abun
,

d ance Var ious pr ob ab le ex p l anations o f th is ar e l eft for

.

mor e s enior s tudy .

302 . Val enc e as ind ic at ed in t h e t ab l e T h e first imp ortant

.

fact t o b e noted ab out t h e p erio d ic t abl e is th at all th e el ements

which occur in a group h ave the same val ence T h e el ements in
.

t h e z ero group will not c o mb ine and may b e c ons id ered as h av

ing a z ero valenc y .

It will furth er b e s een th at as we proceed fro m l eft t o right

al ong any p eri o d , t h e valence of t h e el ement inc reases regularly
(based on t h e oxid es) T h ese regul arities are very striking
. .

When we remember that th is c lassific ation of t h e el ements is

b ased s olely on t h e p osition wh ic h th ey o ccupy in t h e series by
virt ue of t h eir at omic numbers , it is even more extraord inary
i
.

T h e student Would d o well t o familiariz e h imself with t h e p osi

m
tion of t h e com on elements in t h e t able .

30 3 . T h e po sit ion of t h e no nmet al s I n t h e first t wo p erio d s

.

(wh ic h are s h ort p erio d s ) , t h e memb ers of group s VI and VI I

are active nonmetal s t h e el ements o f group s I and I I are very
active met als In t h e lo ng perio ds t h e three middl e elements
.
, ,

wh ic h fall in group VI I I are all metal s of a rath er inac tive s ort ;

,

at t h e b eginning of t h e p erio d are ac tive met al s and at t h e end ,

of t h e period is an ac tive nonm

. et al suc h as brom ine
,
.

304 . T h e posit ion of t h e et al s m

T h e v ery ac tive alkal i
.

m et al s are t ogeth er in group I T h e sub group of met al s b el ong

m
ing t o t h e iddl e of t h e l ong perio d (c opp er, s ilver, and gold )
m m m
h ave t h e sa e valence in any co pound s as t h e alkali etals m .
32 2 T H E NEW P ER I ODI C LA W

But th ey are muc h l ess ac t ive, and th eir hyd ro xid es are weak
bases It is interesting th at t h e elements wh ich h ave variable
.

valenc y and wh ic h formc o lo red io ns occ ur in t h e middl e of t h e

long perio d s ; for examp l e, iron and c opper .

I n general , we may s um up by s aying th at i n the p eri odic

system , th e most acti ve metals are i n group I , th e most acti ve non

metals in group VI I C ertain rath er i nactive metals li e in the

.

middle of the long p eriods .

T h e essent ial c h arac t eristic of a met al l ike s odium is it s

ac tivity and t h e f ormatio n of a p os it iv é ion T h is is some .

times call ed an extreme elec trop ositive c h aract er T h e essen .

tial c h aracteristic of a nonmetal like fluorine is it s ac tivity and

t h e formation of a negat ive io n T h is is somet imes c alled
.

an extreme electronegative c h arac t er With th ese d efinitions

.

in mind , we s ee th at t h e most el ectrop ositive el ements are in

group I and t h e mo st elec tro negative el ement s in group VII .
.

I n b etween th ose extremes lie el ement s wh ic h represent t h e

m any grad at ions b etween th ese t wo opp osit e c h aract eristics .

30 5 . Th enic pic t ure of t h e t ab l e Wh at is t h e funda

el ect ro .

mental reason for M osel ey s law ? H ow can we explain t h e

’

p erio d ic v ariations i n valenc y and o th er c h emic al p rop erties ?

I nd eed h ow c an we pic ture v al enc y itself ? T h ese and simil ar
,

questions h ave b een al ready d isc ussed ( C h ap XI V) and we .

,

are now in a position t o give a fairl y sat is fac tory ex pl anation

o f so m e of t h e many c h emic al ph eno mena whic h are inc lud ed
in t h e perio dic cl assifi c ation M uc h still remai ns i n d oubt
.
,

h owever and t h e present expl anation must b e regard ed as a

,

working hypoth esis and not a scientifi c general iz ation .

30 6 . El ect ro ns and A s at is fac tory expl anation of

val enc e .

t h e val ence Of p olar comp ounds of t h e first twenty el ements h as

b een d evel oped from t h e el ec tronic pic ture of t h e atom T h e .

arrangement of t h e el ec trons in t h e rare gases is supp osed t o

b e such th at in h el ium t wo el ec trons are in t h e outer sh ell , in
neon this group o f t wo el ec trons is surround ed by a group of
eigh t , and argon h as still ano th er sh ell of eight Such arrange .
 24 T HE NEW P ER I ODI C LA W

fluorine atom compl et es it s group of eight and b ecomes t h e

negat ive fluorine i on T h e l ithium atom h aving l ost it s one
.
,

extra el ec tron b ecom es t h e positively c h arged l ithium ion

,

( Fig . I n t h e nonp olar comp ound s we h ave t h e mol ecul e ,

mad e by t h e union of t h e atoms and in this process one or more

,

pairs of el ectrons are sh ared by t h e t wo atom s of t h e mol ecul e .

Li

Fig
. 1 85 . mof t h e union of lit hiumand fluorine
El ect ron d iagra .

307 . El ect ro ns and t h e pro pert ies of t h e at o T h e reason m

.

for t h e m
perio d ic ity in c h e ical prop erti es i s ni c el y accounted
for by th ese mod ern
theories concerning t h e structure of
t h e at om T h e transitio n from one el ement t o t h e next of
.

high er atomic numb er invo lves t h e increase of t h e positive

c h arge on t h e nuc l eus by one and t h e num ber of val ence el ec
trons by one T hus fromh el iumt o fluorine we pass regularl y
.
,

from an el ement With no outer electrons t o one with seven .

T h e next transition t o neon makes t h e total o ut er el ectrons J

eight whic h is a stabl e grouping and we again h ave a rare gas

, , .

T h e series from neon t o chl orine progresses in t h e same w ay .

A nd t h e el ements with t h e same numb er of outer el ec trons fall

und er one anoth er in t h e same group and th erefore h ave t h e
sam e val ence I t sh oul d b e noted particul arly th at among t h e
.

first twenty el ements t h e metal s are th ose el ements which h ave

few val ence el ec trons th at th ey may l ose T h e nonmetal s on .
,

t h e o th er h and are th ose el em , ent s with m any val ence el ec

trons whic h acquire furth er el ectrons t o compl ete t h e octet
( Fig 1 84
.

If t h e at om of an el ement h as four el ectrons in t h e outer

sh ell as is t h e c ase with t h e carb on at om th en we sh ould ex pec t
, ,

i t t o l end or b orrow four electrons t o com plet e t h e outer shell .

S uch an el em ent is said t o b e am pho teri c .

QUEST I ONS 32 5

SUM M A R Y OF C HA P T ER XXI I

A LL T H E EL EM ENT S C A N B E A R R A N G ED in t h e o ld t ab l e
'

n
acc ord i g t o t h eir at o ic weigh t s m . T h e propert i es of t h e el ement s
are a perio dic func t ion of t h eir at o mic weigh t s, wit h t h ree exc ept ions .

A NEW P ER I OD I C S Y S T EM arranges t h e el e ment s on t h e b as is

of t h eir X—
ray s pect ra, mi cal propert ies of t h e el ement s
and t h e ch e

are a perio dic func t ion of t h eir at omic numb ers T h e numb er c or .

respond ing t o t h e po s it ion of t h e el em ent in t h is new s eri es if h y d rogen ,

is one 1 s c all ed it s at o mic numb er

,
.

T H E NEW P ER I OD I C S Y S T E M cl as sifies t h e el ement s int o ni ne

r oup s A ll t h e el em e nt s in a gro up h av e t h e s ame val enc e T h e
g . .

most act ive met al lic el ement s are in group I t h e most act ive non ,

met al lic el ement s in group VII .

A C C OR D I N G T O T H E E LEC TR ON T H EOR Y an at om i s c om

pos e d of a t iny nucl eus s u rround ed b y el e c t rons T h e negat ive .

ch arge of th e l ec t ro ns is
e exa ct ly
b al anc ed b y t h e pos it ive ch arge on
t h e nucl eus . The ato mic numb er Of an el ement i s numeri c all y equal
mb er of el ect ron met allic ment s
_

t o t h e nu s . Th e v al enc e of th e el e is
t h e nu mb er of el ect rons t h ey may l os e in b ecoming posit ive ions and ,

t h e v al enc e o f no nmet al s i s t h e numb er of el ect rons t h ey need t o

com pl et e a groupof eigh t ( an oc t et ) .

QUES T I ONS
1 . D escrib e t h ree way s in wh ich ch e mist s h ave made use of t h e periodic
sy s t e m.

C al cium, st ront ium, and b arium b el o ng t o t h e alkaline eart h family

'

«
2 .
-
.

I n wh at ch emic al way d o t h ey b eh av e al ike ?

.
D raw d iagram s sh owing

t h eir at omic s t ruc t ure and see wh y t h is is so .

3 . Wit h t h e aid of p erio d t wo of t h e p erio d ic cl assificat ion, sh ow h ow

t h e propert ies of the m
el e ent s Of a perio d v ary grad ual ly fro left t o righ t m .

4 W h at nat ural pro cesses migh t b e call ed perio d ic ?

“
.

5 . Wh at d oes t h e ph rase p mean?

erio d ic funct ion
”

I n wh at t h ree cases are element s arranged more nat urally in M osel ey

’
6 . s

t ab l e t h an in M end elej eff s ?

’

S t at e b ot h t h e ol d period ic l aw and t h e new period ic l aw

7 . . Wh en and
b y wh omwas each d is c overed ?
32 6 T HE NEW P ER I ODI C LA W

8 . M ake an at omic st ruct ure diagram for t h e elem ent wh ose at o m ic

m
nu b er is 2 0 . met al or
I s it a a no m
n et al ? P red ict s ome of it s propert ies .

9 T h e exact at omic weigh t of l it hium is

. W h at is it s approxi
mat e at om w g
i c e i h t ? I t s at omic numb er is 3 W h at is it s ( a) valence .

( b ) ch emc
i al ac t iv it y ? I s it a me t al or a no nmet al ?

10 S ome writ ers call t h e at oms of met al s lenders and t h e at om

. s Of non

met als borrowers Expl ain . .

11 . W h at ment al b asis for t h e atomic number of an element ?

is t h e exp eri

12 Expl ain h ow Group 0 (t h e inert gases ) fit s Jnto t h e period ic sy st em

. .

1 3 H ow d oes t h e el ect ron t h eory s h ow t h at l it h ium so d ium and pot es

.
, ,

s iumb el o ng t o t h e s am e c h e m ic al f a mil y
?

14 From t h e n ew period ic t ab l e woul d y ou pred ict t h at rub id ium and

.
,

c hl or ine s h o ul d form a s t a b l e com p o und ? Oxy gen and chl orine ?

15 M ent ion s ev eral respec t s m wh ich oxy gen and sul fur resemb l e each
.

o t h er ch em ic ally M ake at omic st ruct ure diagrams and w it h t h eir aid

.
-

expl ain wh y .

16 . H ow d oes t h e t h eory Of at o mic st ruct ure expl ain isot opes ?

17 . W h at v acant pl aces main in t h e
re periodic t ab l e ? W h at propert ies
sh oul d t h ese el e ment s possess ?
18 H ow d o y ou ac count for t h e fact t h at t h e at omic weigh t s
. of cert ain

el ement s are wh ol e numb ers and ot h ers are not ?

19 St at e t h e numb er and locati on of prot o ns , neut rons , and
. el ec t rons in
th e el ement p ot ass iu m
( at omic numb er 19, at omic weigh t
20 .R ut h erford b omb ard ed nit ro gen wit h al ph a p art icles and lib erat ed
posit ively ch arged p art icles of h y d ro gen m
C o pare t his wit h t h e ques t Of
.

t h e al c h emist s .

21 C h l orine and argon and pot ass iumc ome in succession in t h e period ic
.

t ab le Y et one is an act iv e nonmet al t h e next is a compl et ely inact ive

. ,

el em ent , wh il e t h e l as t is s t ro ngl y met all ic Expl ain in t erms of t h e elec

.

t ron t h eory wh at h appens wh en pot assiumcomb ines wit h ch l orine t o form

pot assiumch l orid e .
32 8 A P P ENDI X

m
gas t o at osph eri c pressure To measure t h e pressure of t h e
.

m
at osph ere, we read t h e b aro et er m T h e mercurial b aromet er
.

(Fig 32 6 ) c onsist s Of a colu n of

. m mercury wh ic h just bal ances
t h e pressure o f t h e atmosph ere
_

Usually t h e .

instrument c onsists of a st out gl ass tub e ab out

a met er l ong c l o sed at o ne end
, T h is h as b een
.

c om pl et ely fill ed with mercury and th en in

verted so th at t h e o p en end proj ec ts into a cup
voir Of merc ury m
(
or reser . A t sea l evel t h e er
c ury in t h e tub e sinks t o a l ev el ab out 7 6 0

millimeters ab ove t h e mercury surface in t h e

c up . T h e spac e ab o v e t h e mercury in t h e tub e
is empty exc ept for a minut e quantity of mer
c ury vap or
,

.
“
T o read t h e b arometer means
”

s im ply t o measure ac c urately t h e h eight of t h e

mercury column ab o ve t h e surfac e Of t h e liquid
in t h e reservo ir Suc h a b aro met er ind ic at es
.

t h e variat io ns in at mosph eric pressure fro m

"

d ay t o d ay d ue t o fluc tuat ions l n t h e at mosph ere

it self I t al s o ind ic at es ch anges Of pressure d ue
.
/

t o c hanges in t h e el evat io n o f t h e Ob server .

The vol u me of a gas wit h pre ssure

c h anges .

T h is was fi rst inv estigat ed in t h e c ase of air

by R ob ert B oy le ( 162 6 T h e results of
h is experiment s s h owed th at if we st art with
a given v ol ume of air subj ec t ed t o a cert ain
p ressure an d th en d o ub le t h e p ressure , t h e

Fig 3 2 6 M ercu
vol ume of air will b e
d uc ed t o o ne h are lf ( Fig -
.

If t h e pressure is mad e th ree t imes as

. .

rial b aro m et er .

great t h e vo l ume of t h e air will b e reduced t o

,

o ne th ird prov id ed t h e t em
-

, p e rat ure of t h e air is k ep t co n st ant .

T h is was found t o b e a general p rincipl e wh ic h appl ies t o all

g ase s I t is k no wn as B OY L E S L A W a n d m a
’
y b e s t at e d as

fOllows : T he volume of a given wei ght of a gas at constant t em

.

p erature vari es i nversely as th e pressure .

A P P ENDIX 32 9

T h is may al so b e e xpressed i n symb ols th us ,

V1 P2
V2 P 1

P 1 V1 Ps ( R ememb er !)
wh ere V1 and P 1 d enot e t h e v olume and pressure of
weight of gas at some t emp erature, and V2 t h e v o lume
d ifferent pressure P 2 b ut at t h e s ame t em
perat ure .

FOR EX A M P LE , supp ose a cert ain weigh t of oxygen

h as av ol ume of 12 00 cc measured at 7 4 0 mm W h at. .

will b e t h e v ol ume und er s t and ard p res sure ( 76 0 mm) .

if t h e t em p er a t ure remain s c ons t ant ?

’
A ccord ing t o B oy l e s L aw
'
P 1 V1 P 2 V2

Sub st it ut ing t h e v al ues gi v en in t h e prob l e m we

,

h av e
7 60 V1 740 X 12 00
74 0 X 1 2 00
1 16 9 cc
76 0

I t will s erv e as a us eful c h eck on t h is r esul t to

not e t h at t h e gas und er s t and ard pressure will b e
sub j ect ed t o a great er pressure t h an b efore, and
accord ingly it s v ol u me will b e less .

I n sol vi ng such pr ob l ems in ch em

m
N OT E . ist ry ,

it will s ave uch t ime t o us e a four pl ace l ogarit h mic -

t ab l e or , b et t er s t ill , a slid e rul e . G enerally it is

sufficient l y ac c urat e t o get t h ree s ignific ant figures B ’
oy l e s
32 7 .

1 0 6 ) in t h e answer . apparat us .

P R OB L EM S

1A given weigh t
. of h y d rogen o c cupies 1 00 cc . at 780mm pressure
. .

Wh at v ol ume woul d it o c cupy at 390 mm pressure ?

. A ssume no ch ange in
temperat ure .

A given weigh t o f gas oc cupies 8 00 c c at 0 C and 38 cm pressure

°
2 . . . . .

H ow many cub ic c ent imet ers w oul d t h e s ame weigh t of gas o ccupy und er
ard co nd it io ns Of t emperat ure and pressure ?

Giv en 500 c c of argon und er a pressure Of 78 0 mm and at a t em

. .

perat ure of 2 0 C A t wh at pres sure wo ul d t h e v ol ume of t h is s ame argon

°

m
.

b e 2 50 c c ( t e perat ure remaining const ant ) ?

.
330 A P P ENDI X

4 . A cert ain weigh t of nit rogen

lit er under st and ard cono c cupies one a

dit ions of t emperat ure and pressure H ow many cub ic c ent imet ers woul d
.

it occupy at 78 0 mm pressure and 0 C

°
. .

5 . I f 10 0 cc . measured at 1 5 C and 570 mm pressure

of o xy gen were
°
. .
,

wh at woul d b e t h e v ol ume at 76 0 mm and at t h e s ame t emperat ure ? .

6 A gas und er a pressure of 6 0 cm and at 2 0 C h as a v ol ume Of

°
. . .

6 30 c c W h at will b e i t s v ol ume und er a pressure of 8 0 cm and at a t em

. .

of C ?
°
perat ure 20 .

A . Oxy gen is s ol d in st eel cy l ind ers und er a pressure Of 1 50 pound s p er

s quare inch . A s t h e gas is used , t h e press ure ro ps W h en it h as d ropped
d .

t o 30 p ound s , mains ?
wh at frac t io nal part of t h e o riginal gas re

8 A cert ain mass of ch l orine o ccupies 1 1 5 c c at 700 mm pressure

.

. . . .

W h at v olume will t h e gas oc cupy at 300 mm pressure if t h e t emperat ure is .

c onst ant ?

9 . S ome air , o c cupy ing 24 5 cc .

,a pressure of 1 at osph ere
is at m
( 76 0 If it is let int o an ev ac uat ed fl ask o f 2 lit ers c ap ac it y , wh at
will b e t h e pressure in t h e flask ?
10 . T h ree lit ers of h y d rogen, measured at 70 cm pres
.

sure, h av e t o b e compressed int o a fl ask of 2 1 00 cc . c apac it y .

W h at increase Of pressure will b e required ?

Th e vol ume wit h t h e t emper

of a gas c h anges

We all know th at nearly everything ex

-

at ure .

pand s when heated ” For exampl e, t h e merc ury

"

or al coh o l in a th erm om et er exp and s and s o

rises in t h e st em wh en warm ed B ut p erh aps .

we are not famil iar with t h e fac t th at gases wh en

warmed expand muc h more th an l iquids ; thus ,
air expand s ab out nine times as muc h as wat er .

%
Even more remarkabl e h owever, is t h e fac t th at ,

all gases expand at nearly t h e same rat e .

Fig 3 2 8
, T ub e
,
It is easy t o measure in a rough way t h e
c o nt aining d ry
amount wh ic h gases expand ( Fig If in .

air and a el l et
of m erc uf
y t h
,
e e xperi ment we h ad b eg un w 1t h a v o l um e of
air of 2 73 c c at 0 C .and h ad cool ed t h e gas
° “
.

from0 C t o 1 C , t h e vol ume would h ave b een red uc ed t o

° °
. .

and if we h ad c ool ed it t o 10 C t h e v olume of t h e

°
2 72 cc .

air would h ave b ec ome 263 cc If th en, t h e air continued t o

.
,
332 A P P ENDI X

wh ere V; and V2 represent t h e vo lumes of a cert ain quantity

of gas at t h e s am e pressure b ut at d ifferent ab so lut e t em p er
atures , T I and T 2 If A is t h e t emp erature o n t h e c entigrad e
.

scal e wh en t h e v o l um e is V1 , th en T I 2 73 tl ; s imil arl y ,

T2 2 73 l2 .

FOR E X A MP LE , supp ose we h av e a quant it y of gas wh ich measures 32 0 c c .

wh en t h e t emperat ure is 15 C W h at v olume will t his oc cupy at 0 C ,
° °
. .

p rov i d ed t h e p ress ure is ke p t cons t ant ?

First ch ange t h e c ent igrad e t emperat ures gi ven i n t h e prob l em t o ab so

lut e t emperat ures b y adding 2 73 and t h en sub st it ut e in t h e equat ion for t h e
L aw of C h arles
V1 2 73
32 0 2 73 15
32 0 X 2 73
30 3 cc.
2 88

N OTE I n s ol ving such prob l ems t h e s t ud ent would d o wel l t o c ompare

.

his resul t wit h t h e original v ol umet o s ee wh et h er it is reasonab l e If t he .

t emperat ure of a gas measured in t h e l ab orat ory is 2 0 C , t h en t h e gas

°
.

und er s t and ard c ond it io ns w oul d c o nt rac t ab out 7 per c ent .

P R OB LEM S

I n t h es t at ement o f b ot h B oy l e s L aw and t h e L aw of C h arl es t h ere

’
1
“
.

appears t h e ph rase a given wei gh t o f gas

”
I s t h is an es sent ial p art of t h e
. 1

s t at em et
n ? W h a t d o es it mean in t e rm s o f m o l ec ul es ?

2 One h und red

. c ub ic cent i met ers of air are at 0
°
C . T h e t emperat ure
is faised t o 546 C
°
. W h at is t h e new v ol u me of t h e gas ?
3 . I f we assume no ch ange in pressure, wh at ch ange in v ol u me woul d
C were c ool ed t o 0 C ?
° °
o c c ur if 2 l it ers of gas at 2 0 0 . .

4 . W h at volume woul d 1 60 c c o f oxy gen measured . at 2 7

°
C . o c cupy

C if we assume t h at t h e pressure remains fixed ?

°
at 0 .
k

5 A g1v en weigh t of gas o c c upies 1 0 0

. cc . wh en measured at 2 7 C .

A t wh at t emperat ure woul d t h e s ame weigh t of gas o c cupy 2 00 cc .

(press ure
rem
?
aining c o ns t ant )
6A giv en weigh t of gas o c c upies 2 50 cc at
. . 23
°
C . and 7 60 mm .

W h at is t h e v olume o f t h e s ame weigh t

_

of gas und er
“

pressure . s t and ard

c o nd it io ns

A cert ain quant it y Of h y d ro gen gas o ccupies 1 000 c c at 2 0 C and

°
7 . . .

760 mm .
pressure T o wh at c ent igrad e t e perat ure
. m
us t t h is h y d ro gen m
be c o ol ed in ord er t h at it s vol u me may b e 500 cc .
( pressure re maining
c o ns t ant )
A P P ENDI X 333

8 . S ome oxy gen o c cupies 39 cc . at 17 C

°
. C orrect it s me t o st and
v ol u

ard t e mperat ure .

9 . me of a s ample of argon at 91 C is 1 8 cc T h e t empera

T he v ol u
“
.
°
. .

t ure is l owered t o 0 C C omput e t h e final v olume of t h e argon

°
.
.

1 0 I f 7 8 c c of neon are at 0 C wh at rise in t emperat ure is need ed t o

°
.
. .
,

make t h e gas o c cupy 2 34 c c ? .

T h e gas e quat io n I n prac tic e t h e c h e ist usually h as t o

. m
m ake c orrec tio ns fo r b oth t h e pressure and t h e t e p erature in m
m
red uc ing h is v o l u e o f gas t o s t and ard c o nd it ions It will .

th erefore b e h elpful to co mbine t h e Laws of B oyle and C h arl es

int o one equation
P 1 V1 P 2 V2

It will dily b e seen th at th is equation reduc es t o equation I

rea ,

yl w w h T T d th t if P P h at i n
’
( B o e s La ) en 1 2 a n a 1 2 t e equ o , ,

bec omes V1 /T 1 Vz/T 2 wh ic h is anoth er f orm of equa ,

tion I I ( C h arl es Law) Equation I I I is c al led t h e gas equa

’
.

*
t ion .

FOR E X A MP LE , supp ose we wish t o find t h e me of a cert ain quant it y

v ol u

gas und er s t and ard c on t h at is at 0 C and 7 60 mm pressure

°
of dit ions , ,
. .
,

wh en it is knownt o oc cupy 12 00 c c at 1 5 C and und er apressure of 74 0 mm

°
. . .
!

Sub st it ut ing in equat ion I I I , we h av e

74 0 x 1 2 0 0 760 x V2
2 7s + 15 2 73 + 0
74 0 x 1 2 00 x 2 73
wh ence 1100
7 60 x 2 8 8

C orrect ion for pres s ure vapor Wh en a gas is col of wat er .

lect ed o v er wat er and t h e l evel o f t h e water is t h e s ame with in

and with o ut t h e measuri ng v e ssel t h e inc l osed ga s is und er ,

atmo sph eric pressure B ut t o s o me extent wat er h as evap o

~

rat ed int o t h e v essel and a p art of t h e v o lum

,
e inc l osed is d ue t o

t h e wat er vap or and not t o t h e gas T h is wat er vap or exert s .

a cert ain pressure d epend ing on t h e tem , p erature A s t he .

T h ere are cert ain d eviat ions fro mt h ese gas l aws t h e d iscussion of wh ich is b e
y o nd t h e sco pe o f t h is b oo k Onl y id eal gases fol l o w t h e l aws as d is cus sed a
. b ove .
334 A P P ENDI X

temperature rises t h e pressur e of water vapor increases steadily

, ,

as sh own in t h e tabl e in this A ppend ix .

T h e pressure insid e a b ottle of gas c o llect ed o ver water is t h e

p re ssu re of t h e gas p lus t h e p ressure o f t h e w a ter vap or and is ,

equal t o th at outsid e wh ic h is s im ply atmosph eric pressur e

, .

Wh at we want h owever is merely t h e pressure exerted by t h e

, ,

gas c oll ect ed We c annot easily remove t h e water vapor We

. .

c an h owever d o wh at am
, ,
ounts t o t h e sam e th ing We subtract .

the p ressure of thewater vapor (aqueous tension) expressed i nm i lli ,

meters of mercury from the b arometric pressure and t h e result

, ,

is t h e pressure of t h e dry gas or t h e c orrect ed pres s ure , T h is .

we use in our c alc ul ation .

N OTE A
t ab l e in t h is A ppendix gives t h e pressures d ue t o wat er
. v ap or
at various t emperat ures .

FOR E XA MP LE , sup p ose a gas m

easured 30 0 cc over wat er wh en t h e
.

b aromet er read 740 mm . m

and t h e t e perat ure was 2 5 C
°
Wh at woul d b e .

it s v ol ume und er st and ard c ondit ions ?

From t h e t ab l e for aqueous t ension, w e see t h at t h e pressure of wat er

v ap or at 2 5 C is 24 m
°
. m ; t h erefore t h e correct ed pressure is 74 0 —2 4, or
.

71 6 mm .

Sub st it ut ing in t h e gas equat ion, we h ave

7 1 6 X 300 760 X V2
2 98 2 73
7 16 2—73
wh ence X X 300 2 59 cc
767) 3
.

2 98

C orrect io n for d ifferenc e in l evel . We h ave med

assu that
t h e gases were c oll ect ed o ver erc ury water in b ottles , and m or

th at t h e level of t h e l iquid was t h e same outsid e and insid e t h e

tub e Occasionally it is impossibl e t o arrange t h e apparatus
.

in th is way , and th en we must make a correction for t h e d iffer

enc e in l evel When t h e l evel of t h e liquid inside t h e tub e is
.

lower th an th at outsid e (Fig 32 5 C ) , th en t h e pressure is .

greater th an atm osph eric ; and wh en t h e insid e l evel is h igh er

( Fig 32 5 B ) , th ent h e pressure is l ess than atmosph eric If t h e

. .

liquid is mercury, t h e d ifference in levels is add ed t o or sub

tracted from t h e h eight of t h e barometer Since water i .
s
336 A P P ENDI X

LI ST OF BOOKS FOR FUR T HER ST U DY

N OTE T his li st of b ooks h as b een very carefully s elected and we think many
.

schools will wi sh to acqui re all of them .

T h os e b ooks wh ich are v ery d esirab l e and wh ich sh oul d b e ac quired as soon as
p ossib le are marked
T h os e b o oks wh ic h are ind ispensab l e and wh ich s h oul d b e in ev ery s c h ool

lib rary are marked

A R R HENI U S , SVA NTE , C h em istry i n M odern Li fe .

D Van N os t rand
. C o , N Y 1 92 5 . . .

*
B OYD , T A , G asoline, Wh at E veryone S hould K now ab out I t
. . .

Fred erick A St okes C o , N Y , 1 92 9

. . . . .

BOYD, T A , R esearch T h e P ath Fi nder of S ci ence and I ndustry

—
. . .

D A ppl et on C ent ury C o , N Y , 1 92 5

. . . . .

*
B R A G G , S I R W I LL I A M , T he Uni verse of L i ght .

T h e M acmill an C o , N Y , 1 933 . . . .

C A VEN C R A NS T ON, S ymb ols and Formula

A ND e i n Che istry m .

B l ackie S on, L ond on, 1 92 8 .

**
C HA M BER LA I N, J S , C h emi stry i n A gri culture
. . .

T h e C h emic al Found at i on, I nc , N Y , 1 92 6 . . . .

**
C ONA NT , JA MES B The Chemistry of Organic
.
, Comp ounds .

T he M acmil l an C o N Y 1 933 .
, . .
, .

C UR I E , M M E M A R IE , P i erre Curi e
. .

T h e M acmill an C o , N Y , 1 92 3 . . . .

D E M I NG , H C , I n the R ealmof C arbon

. . .

J oh n W il ey S ons, N Y , 1 930 . . .

DU NCA N , R K , Ch emistry of Commerce

. . .

H arper B rot h ers , N Y , 1 907 . . .

FA B R E , JEA N H ENR I , T he Wond er B ook of C hemistry .

T h e C ent ury C o .
, 1 930 .

FA R A DA Y , M I C HA E L , T he C hemi cal H is tory o f a C andle .

R epub lish ed b y E P D ut t on C c , N Y , 1 933

. . . . . .

FI NDLA Y , A LE X A NDER , Th e S p i ri t of Chemi stry .

L ongmans , Green C o , N Y , 1 930 . . . .

*
FI S K , D OR OT H Y , Exp loring the Upp er A t mosphere .

Oxford Univ ersit y P res s 1934 . .

R om
WI LL I A M ance of Ch em , istry .

T h e C ent ury C o , N Y , 1 92 7 . . . .

H OLME S , H A R R Y N , Out of the T est T ub e . .

R ay L ong and R ich ard R S mit h , N Y . . .

, 1 934 .

*
H OLMYA R D, E J M akers of C hem
. i stry .

T h e C l arend on P ress , Oxford , 1931 .

A P P ENDI X 337

**
H OWE, H E , Chemistry in I ndustry , 2 volu es
. . m .

T h e C h emical Found at ion, I nc , N Y 1 92 5 . . .

H OWE , H E , C hem istry in the World s Work

’
. . .

D Van N ost rand C og, N Y , 1 92 6

. . . .

H OW E A ND T UR NER , C hem i stry and the H ome .

C h arles S crib ner 3 S ons , N Y 192 7

’
. . .

JA FFE B ER NA R D, C ruci b les, th e L ives and A chievements of theGreat C hem v

i sts .

Simon and Sch ust er, N Y , 1 930 . . .

JOHNS ON, B ER TR A ND L , N itrogen and I ts Comp ounds . .

U S B ureau of M ines C ircul ar N o 6 38 5

. . . .
( Supt . of D oc .
)
KENDA LL , JA MES , A t H ome among th e A toms .

T h e C ent ury C o .
, N Y . .
,
1 92 9 .

LA NG DON -
D A VI ES , J OH NS ON, I nsi de th e A tom .

H arper B rot h ers , N Y .

L ITTLE A D T he H andwriting on the Wall;

, . .
,

L it t le B rown ,

L OWR Y T M H istorical I ntroduction to C hemistry

, . .

M acmillan C o L ond on 1 92 6 .
, , .

M A R T I N GEOFFR E Y T riump hs and Wonders of M odern Chemistry

, , .

D Van N ost rand C o , N Y , 1 911

. . . . .

M C P HER S ON A ND H ENDER S ON, A C ourse i n General Che i stry m .

Fourt h Ed .
, Ginn and C o .
, B ost on, 1 933 .

M OOR E F J H is tory of Chemi s try

* “
. .
,

M c G raw—
H ill B ook C o N Y 1931 .
, . .
,
.

P HI LIP J C T he R omance of M odern Ch em

, . istry
.
, .

J .Lippincot t C o N Y 1 912
B . .
, . .
, .

R OGER S A LLE N I ndustri al C hem

, istry ,
.

D Van N ost rand

. Co .
, N Y . .
, 1 92 5 .

**
SL OSS ON EDWI N E C reati ve C h em
, i stry .
, .

T h e C ent ury C c , N Y , 191 9 . . . .

SM I T H , E F , Chem istry i n A meri ca

. . .

D A ppl et on
. Co .
, N Y . .
, 1 91 4 .

SP R I NG , L W
, N on T echni cal C hats on I ron and S teel
. .
-
.

Fred erick A St okes C o N Y 1 91 7 . .

, . .
, .

*
STI EG LI TZ , C hem JU L I U S
istry i n M edi cine , .

T h e C hemic al Found at ion, I nc , N Y , 1 92 8 . . . .

*
T H OR P A ND L EWI S , Out li nes of I ndustri al Chem istry .

T h e M acmill an C o , N Y , 1 916 . . . .

T HOR P E, T E , Essays on H istori cal Chem . istry . .

T h e M acmill an C o , N Y , 1 92 3 . . . .
34 0 A P P ENDI X

P R ES SU R E OF WA T ER VA P OR , OR A QUEOU S TENSI ON

( I n mi llimeters of mercury)

T EMP E TU E
RA R PR E SS UR E T EM PE TU E
RA R PR E
SS UR E T EMP E T E
R A UR P R E S SUR E

mm . mm . mm .

D ENSI T I ES OF I M P OR T A NT GA S ES

( A pp roximate wei ght of 1 under standard

A c et y l ene ( O2H 2 )
A ir
A mmonia ( N H 3)
C arb on d ioxid e ( 0 0 2 )
C arb on monoxid e ( C O)
C hl orine ( C l z)
H elium ( H e)
H y d rogen ( H 2 )
H y d rogen chl orid e ( C l ) H
H y d rogen sulfid e ( H gS )
M et h ane ( OH 4 )
N it ric oxid e ( N O)
Nit rogen ( N 2 )
Nit rous oxid e ( N 20 )
Oxy gen ( 0 2 )
S ulfur dioxid e ( 8 0 2)
A P P ENDI X 41

S OM E C OMM ON S U B S T A NC ES

CO MMO N NA ME CH EM C
I AL NA M E FOR MU LA

A lum P ot assium, aluminum K 28 0 4 A 12 ( S O4) 3

sul fat e

A mmonia wat er A mmoniumh y d roxid e N H 4 OH

A qua regia H y d roch l oric and nit ric 3 H0 1 H NOs
acid s
B aking sod a Sodium h y d rogen c ar NaH C Os
b onat e
B l ue vit riol C op per s ul fat e C uS O4 5 H 20
B orax S od iumt et rab orat e N agB 4 O7 1 0 H 2 0
C al omel M ercurous chl orid e H gC l
C aust ic p ot ash P ot assium h y d roxid e K OH
C aus t ic sod a S od ium h y d roxid e N aoH
C h alk ( precipit at e ) d . C al cium c arb onat e C aC Os
C h arc oal . C arb on
C orrosiv e s ub limat e M erc uric ch l orid e
i

C ream of t art ar P ot assiumh y d rogen

t art rat e
E ps om s alt s M agnesiumsul fat e M gS O4 7 H 2 0
Grain al coh ol E t h y l al coh ol C s OH
Gypsum C al cium s ul fat e 0 3 8 0 4 2 H 20
“
H y po
”
S odium t h ios ul fat e N a28 2 0 3 5 H 20
Lime ( quicklime)
.

C al cium o xid e C aO
Limest one C al cium c arb onat e C aC Oa
Limewat er S olut ion of c al cium C ! ( OH ) 2
h y d roxid e
C al cium c arb onat e C3 0 0 3
N aph t h al ene C 1 0H 8
Sul furic acid H 2S O4
C al cium sul fat e ( C aS O4 ) 2 H 20
C al cium c arb onat e and C aC Oa
linseed oil
Sil ic on d ioxid e 8 10 2
M ercury He
L ead t et raoxid e P b 30 4
A mmonium ch l orid e NH 4C I
S odium c arb onat e N a2 0 0 3 1 0 H 20
Sod ium h y d rogen car N aH C Os
b onat e
Sucrose
S od ium ch l orid e
A cet ic acid , dilut e
S od ium c arb onat e
 A P P ENDI X

HA R DNESS OF S U B S T A NC ES

We may co mpare t h e h ard ness of t wo mat erials b y rub b ing mt oget h er ;

t he
the onewh ich is h ard er s crat ch es or ind ent s t h e ot h er A scale of h ard ness
. .

h as long b een in use wh ich ext end s from1 t o 1 0 T h e h and b ooks in ch emist ry
.

and ph y sics give t h e foll owing t ab l e

M OHS S C A LE H A R DNESS
’
OF

MI NE RA LS HA R D NE SS MI NE RA LS HA R D NES S

I t will b e useful t o memb er t h at

re a sub st a
nce, . such as gy psu m c an be
s c rat c h ed wit h t h e fingernail and t h at ap at it e ( 5) is a lit t le h ard t o scrat c h

wit h a knife .

S P EC I FI C G R A VI T Y , OR R EL A T I VE DENS I T Y
“
T h e st and ard sub st ance is pure wat er t aken at 4 G
T h e d ensit y of a
°
.

sub st ance c om p ared wit h t h at of wat er is c all ed it s specific gravit y For .

exam ple, t h e specific gravit y of sul fur is 2 , wh ich means t h at sulfur is 2 t imes
as d ense as wat er Since t h e d ensit y of wat er is 1 gramper cub ic cent imet er ,
.

it is evid ent t h at the d ens i ty of any sub st ance i n the metri c s ystem (g cc ) . .

is numerical ly equal to i ts sp ecific gravi ty .

344 I N D EX

( N umb ers refer t o p ages .

)
C ar b o n d i o xi d e ( C o nt i nued ) Co mm o n s al t , 1 1 9
2 2 5 ; p ro d uc t io n o f, 2 2 3 ; p ro p e rt i e s o f , C o mp o u nd s , c h e mic al 2 2 ; d e finit e c o m
p o si t i o n o f, 2 5 ; d e finit i o n o f, 2 4 ; fo r mul a
,

2 2 7 ; t es t fo r , 2 2 4
b
C ar o n m o no xi d e , in c o al fire , 2 3 1 ; and o f, 2 54 ; vs mixt ures , 2 9 ; mo l ec ul ar
b
d io x id e , c o mp o si t io n o f, 2 3 1 ; l a o rat o r y w eig h t o f, 10 9 ; naming 9 8 ; num er and b
.

met h o d o f p rep arat io n 2 32 ; a p o iso n, i mp or t anc e o f, 2 8 ; p e rc ent ag e c o mp o s i

,

2 3 3 ; p ro p ert ies o f, 2 33 ; as a r ed uc i ng t io n o f, 1 0 9 p ro d uc t io n o f, fro m e l e

age nt , 2 3 3 m ent s 2 5
m
,

C ar b o nat e d w at er , 2 2 7 Co p ut at i o ns , 1 0 8
C ar b o ni c ac i d gas , 2 2 7 C o nc e nt r at i o n, e fiec t o f, 2 9 2 ; l aw o f 2 9 1 ,

C at al y s t , 3 2 , 53 ; e fiec t o f, 2 90 C o nd e ns er , 6 5
C at al y t i c age nt , 32 C o ns er vat i o n o f m
at t er , l aw o f 19 8 4 , ,

C at h o d e , 1 58 C o nt ac t p r o c e s s ( s ul f ur i c ac i d ) , 2 0 8
C aus t i c s o d a, 1 2 6 C o r r ec t i o n f o r w at er vap o r , 333
C ave nd i s h , H e nr y , 6 ; ( p o rt rait ) , 4 6 C o val e nt l i n age , 18 2 k
C e nt i gr ad e s c al e , 6 2 C r i t i c al t e m
p er at ur e , 2 6 5
Cha mb er p r o c e s s ( s ul f ur i c ac i d ) , 2 0 9 C r y s t al s t r uc t ur e o f s al t s , 1 6 3
C h an ge , c h e mi c al , 1 3 , 8 3 ; c h arac t eris t i c s C r y s t al s , o f s ul fur , 1 8 9
o i , l 7 ; d e finit io n o f, 1 6 ; d i s p l ac e ment 4 9 , C ur r e nt o f e l ec t r i c i t y , 1 6 4
fami l i ar , 1 4 ; w h at h ap p e ns i n, 1 5 ; t y p e s m
,

C y ana i d e p r o c e s s ( ni t r o ge n) , 30 5
o f, 1 0 4 ; w ei g h t unc h ang e d i n, 18 C y ani d e p r o c e s s ( go l d ) , 30 5
C h an ge , p h y s i c al , 1 3 C y c l e o f c ar b o n and o xy ge n, 2 73
C h an ge s o f s t at e o f m at t er , 6 2
k
D a i n s s o l ut i o n, 1 36
’

C h ar c o al , ani mal , 2 2 0 , w o o d , 2 1 9
D al o n, J o h n at o mic t h e o r y
C h ar l es , l aw o f , 2 4 0
k z g ,

C h ec i ng up ans w er s , 1 1 1
m m
D av y , S i r H u p h r y ( p o rt rait ) 1 2 4
'

C h e i c al c al c ul at i o n s , C al c ul a m b
p o s i t i o n, d o u l e 1 0 6 ; s i mp l e 10 5
,
s ee
D ec o
t i o ns , c h e m i c al
D e fini t e c o m
p o s i t i o n , l aw o f 2 6
, ,

Che m i c al c h ange , s ee C h ange c h e m

i c al D e h y d r at i ng ac t i o n o f s ul fur i c ac i d , 2 1 0
,

m m m
.

Che i c al c o p o und s , s ee C o p o und s D e ns i t y , d e fini t io n o f, 1 6 , 6 1 ; o f a g as h o w

C h e mi c al e q u at i o n , s ee E q u at i o n ,
.

t o c o mp ut e , 3 2 7 ; o f i mp o rt ant
,

c h e mi c al
g as es

m
C h e i c al fir e e xt i n gui s h er s , 4 2
( t ab l e) , 3 4 0 ; vs s p ec i fic g rav it y , 3 4 2
.

D es t r uc t i ve d i s t i l l at i o n, 2 1 9
C h e rni c al fo r m ul a, s ee Fo r m ul a, c h e im D e ut er i um ( h eav y h y d ro g en) , 58
c al
m m D e w ar fl as , 2 6 7 k
Che
m
i c al f o r ul as , 9 1
m
D i a o nd , 2 1 7
Che
m
C h e i c al
i c al p r o p er t i e s , 35
r e ac t i o ns , s ee R e ac t i o ns ,
b
D i as i c ac i d s , 2 0 5
D i ff us i o n, 55
ch e m i c al D i rec t c o
‘

mb i nat i o n , 1 0 4
Che m i c al s , 2 1
D i r i gi b l e ( h el ium) , 2 70
m
C h e i c al s y mb ol , 89 D i s i nfe c t i n g ac t i o n, 1 36
Che m i c al u ni o n, e l e c t ro n t h eo r y o f, 18 1 D i s p l ac e me nt , 4 9
m
C h e i s t r y , agric ul t ural , 8 ; ap p lie d and D i s t i l l at i o n, d e s t ruc t iv e 2 19 ; o f w at er 6 5
p ur e , 8 ; b e g i nning s o f, 2 ; d e finit io n o f D o u l e d e c o mp o s i t i o n, 1 0 6
b
, ,

“
,

19 ; ed uc at io na l v al ue o f, 8 ; i n 18 t h ”
Dr y i c e, 2 28
c ent ur y , 6 i n e v er y d ay l i fe , 1 ; i n i n
“
°

’
D ul o ng and P t i t s L aw , 2 52
d ust r y , 7 ; i n M i d d l e A g e s , 3 ; i n mo d er n
e
”
D u P r e ne , 19 3
l ife , 7 ; re nai ssanc e o f, 3 ; s c ient ific , b e D y es , 7
ginni ng s o f, 5 D y nami t e , 30 6
C h i l e s al t p e t e r , 2 9 6
C h l o r at e s , 1 3 4 Effer ve s c e nc e , 2 2 6
C h l o r i d e , h o w fo r med , 1 4 2 ; o f l i me , 1 34 ; El ec t r o l y s i s , 1 6 0 e l ec t ro n t h eo ry o f, 16 4 ;
,

t es t fo r, 1 4 3 i o nic t h eo ry o f 1 6 0 ; o f s al t so l ut io n
,

C h l o r i ne , c h e mic al ac t i v it y o f 1 3 1 ; p o is o n
,
1 2 1 ; o f w at e r 2 3 ,

g as , 130 ; p rep arat io n o f, 1 2 9 , 1 3 2 ; p ro El e c t r o l y t e s , 1 58

p e r t ies o f, 130 ; us e s o f, 1 32 ; w at er , 1 32 El ec t r o n , 1 6 2 ; w it h in t h e at o m, 17 5, 3 2 4 ;
C i t r i c ac i d , 1 4 9 t h eo ry o f at o m, 1 7 3 , o f c h e mic al unio n
b 1 8 1 , o f el e c t r o l y s is , 1 6 4 , o f met al s , 1 78 ,
,

C o al , 2 2 0 ; ant h rac it e , 2 2 1 ; it umino us ,

2 2 1 ; g as , 2 2 1 ; t ar , 2 2 1 o f no nm e t al s , 1 78 , o f v al enc e , 17 7

C o ke , 2 2 0 , 2 2 2 m
El e c t r o n d i agr a s , 1 7 5 1 76 , 1 77 , 1 78 ,
mb
,

Co i ni ng w e i gh t , 2 50 and at o mic 179 , 18 2 , 2 2 2 , 2 2 3 , 3 2 3 , 3 2 4

'

w eig h t , met h o d o f d et er mi ning , 2 4 9 El ec t r o ns and v al e nc e , 32 2

Co m b us t i o n, d e finit io n o f, 2 7 ; L
av o is ier s
’
El e m b
ent s , a und anc e o f, 2 7 amp h o t er ic ,
'

e x p e ri me nt o n, 36 ; p r o d uc t s o f, 37 ; 2 2 2 ; d e finit io n o f, 2 4 ; l i s t o f, fac ing

s p o nt aneo us 3 9 B ac kC o v e r ; i n h uman o d y 2 8 ; i m b
mm m k b k
.
,

Co o n el e e nt s , B ac C o v er p o rt ant ( t a l e) B ac C o v e r ; i n nat i v e
mm k
,

Co o n uni t s , B ac C o v er s t at e, 2 8 ; o c c urrenc e o f, 2 7
I N D EX 34 5

( N umb ers r efer t o p ages .

)
El i xi r o f l i fe , 5 ex p e ri ment s
w it h , 50 w h ere fo und 4 6 ,
mo l e c ul e, 2 4 1 ; ne w l y d isc o v ered fo r ms
, ,

End p o i nt , 1 51
q
E uat i o n, c h emic al , 1 0 1 ; g as , 333 ; h o w o f, 57 ; p rep ar at io n o f, i n l a o r at o ry , 4 9 b
fro m w at er , 4 7 p r o p e rt ies o f 52 ; p uri fi
,

to w r it e , 1 0 2 ; ne c ess ary s t e p s , 1 0 2 ;
q uant it at iv e , meaning o f, 1 1i2 ; w h at it
,

c at io n o f, 4 7 ; t e s t fo r , 2 3 ; us es o f, 54
d o es no t s h o w 10 3 ; w o rd , 2 6 H y d r o ge nat i o n, 55
q b m k H y d r o ge n c h l o r i d e , 1 4 0 c o mp o s it io n o f
,

E ui l i ri u , inet i c , 2 8 9
q
, ,

E ui v al e nt w ei gh t , 2 4 9 1 4 5 ; p re p arat io n o f, 1 39 ; p ro p er t ie s o f,
E ud i o m e t er , 6 8 1 4 0 ; s y nt h e s i s o f 1 4 4 t e s t fo r , 1 4 3 ,
°

Evap o r at i o n, 6 2 H y d r o ge n p e r o xi d e , 7 2
Ex p l o s i o n, 39 H y d r o ge n s ul fid e , o c c urrenc e o f, 1 9 4 ; a
Ex t i ngui s h i ng fir e , 4 1 p o is o n, 1 9 5 ; p re p ar at i o n o f, 19 4 ; p ro ~
p e rt ie s o f , 19 5 ; us e o f, 1 9 7
H y d r o s ul f ur i c ac i d , 1 9 5
Fac t s and t h e o r i e s , 79
F ar ad ay , M i c h ae l ( p o rt rait ) , 1 6 0
H y d r o xi d e , s o d i um, 4 8
F er t i l i z e r s , 3 0 8
H y d r o xy l gr o up , 1 50
H y p o c h l o r i t e s , 1 33
Fil t r at i o n o f w at er , 2 7 , 6 6
Fi r e e xt i ngui s h e r s , 2 2 9
H y p o c h l o r o us ac i d , 1 3 2 as l eac h i ng b
ag ent 1 35 as d is infe c t i ng ag e nt , 1 36 ;
°

Fi r e e x t i ng ui s h i n g, 4 1 ,

o x id iz i ng ac t io n o f, 1 33
Fi xat i o n o f n i t r o ge n, 2 9 5, 30 5
m
F o a i t e , 2 30
Fo r m ul a, c h e mi c al , 9 1 ; d et er mining , 2 54 I c e , art ific ial , 2 8 3 ;
m
d ry 228
i nat i ng gas , c o al g as , 2 2 1
,

mo l ec ul ar , 1 0 3 ; p erc ent ag e c o mp o s it io n
,
I ll u
fro m, 1 0 9 ; W ei g h t 1 0 9 ; w rit ing , 9 6 I n d i c at o r , 1 50
I nd us t r i al c h ar t , 338
,

Fr as c h p r o c e s s f o r s ul f ur , 1 8 8
Fr o s t e d f o o d s , 2 8 4 I nt er nat i o nal at o ic w e i g t s ( t a l e ) m h b
k
,

m
F u i ng, nit ric ac id , 2 98 ; s ulfuric ac id , fac ing B ac C o v er
I o ni c r e ac t i o ns , 1 6 5
.

2 09
F ur nac e , el ec t ric , res is t anc e , 2 18 I o ni c t h eo r y , o f ac id s and as es 16 4 ; o f b ,

ne ut r aliz at i o n 1 6 5 ,

I o ni z at i o n, 1 59 ; t h eo ry 1 6 1
m
G al l i u , p r ed ic t io n c o nc e rning 3 1 7 , I o ns , 1 57 ; o f ac id s and as e s , 1 6 4 ; and
,

b
G as , d e ns it y o f 3 2 7 ; earl i es t us e o f 5 ; at o ms , 16 3 ; ne ut rali z at io n o f 16 5 ;
q p o i s o n 1 2 9 ; v o l ume o f,
, ,
,
e uat i o n 3 3 3 ;
v al e nc e o f 1 8 1
c h ang e s w it h t e mp erat ur e 3 30
, ,
,

I s o t o p e s , 2 52
C as e s , d i ff us io n o f 55 ; i mp o r t ant d en
,

k
, ,

s i t ies of 34 0 ; i net ic t h e o ry o f, 56
, , K i nd l i ng p o i nt , 4 0
r ar e
b
,
2 63; s t and ar d c o nd it io ns
q unifo r m
32 7 , , q
K i ne t i c e ui l i r i u m, 2 8 9 b
so l u i l i t y o f i n l i ui d s 339 ;
, ity , K i ne t i c mo l ec ul ar t h e o r y , 56
-

o f 2 39
, K i p p ge ner at o r , 50
G as o l i ne , 4 0
m
G as v o l u e s , c o rr ec t io n o f 3 33
’

L a t i a i d 14 9
L L c c c
,

L amp b l a k 2 2 0
,
G ay -
u s s ac , J o s e p h o ui s ( p o rt rait ) 70
G ay L u s s ac s l aw o f v o l ume s , 6 9
, c
L angmui I i ng ( p t ait ) 8 5
’ ,

“
-

r, rv or r
L at 19 1
,
G l as s , P y re x 8
”

m at o mi c We i gh t , 9 1
ex,
,

G ra -

G r am mo l ec ul ar v o l ume , 2 4 4
L a i i A nt i n L au nt 6
v o s er , o e re , , 35 , (por
t r ait ) 36
-

G r am mo l ec ul ar w e i g h t , 2 4 4 m m
,

e nt o n c o b us t i o n ,
’
L av i s i er s e x p er i
-

G r ap h i t e , 2 1 8
G r avi me t r i c s y nt h es i s o f w at er , 7 1
3 g
L aw , B o y l e s 2 39 o f C h ar l es 2 4 0 ; o f c o n
’

D ul o n
,

c e nt rat io n o r mas s ac t io n 2 9 1 ;
, ,

g
H a er p r o c e s s ( ammo ni a) 2 8 7
b
,

and P et i t s c o nse r v at io n o f
’
2 52 ; of
H ar d ne s s o f mi ne r al s , 34 2 mat t er, 19 8 4 ; o f d e finit e c o mp o si t io n
, ,

H e at , o f fo r mat io n 1 6 9 ; o f fusio n
, ,

63; 2 6 7 4 8 4 ; d e finit io n o f 1 9 G ay
L uss ac s 6 9 ; o f mas s ac t io n, 2 9 2 ; o f
, , , , , ,
’
s p ec i fic 6 3 , o f v ap o riz at io n, 6 3
mo lec ul ar c o nc e nt rat io n, 2 9 1 ; p erio d ic
, ,

H e avy w at e r , 7 1
H el i u m, us e s , 2 7 0 ( ne w ) 3 14 ; p er i o d ic ( o ld ) 315; of
m m mul t ip l e p ro p o rt io ns 7 3 8 4
, ,

Ho o ge ne o us at e r i al , 2 2
Lqi ui d ai r , 33 , 2 6 5 ; e x p eri me nt s wit h ; 2 6 6 ;
,

H o p c al i t e, 2 34
H o us e h o l d a mm
o ni a, 2 8 0 o x y g e n mad e fr o m, 33, 2 6 6
m
H u i d it y , 2 75 L i t mu s , 1 50
H y d r o c h l o r i c ac i d , 138 ; c o mmerc ial s y n L i t t l e , D r A r t h ur D . 2
t h e s is o f, 1 4 6 , c o nc e nt r at e d , 14 1 ; a L y e, 1 2 6
t y p i c al ac id 14 2 ; us e s o f, 1 4 2
H y d r o ge n , 4 6 ; at o m, s t and ard 8 1 ; at o mic , M agnal i um 7
,

b
,

8 5 ; c h e mi c al fo r c o m
,

e h av i o r o f, 52 ; M al i c ac i d 1 4 9 ,

merc iai p urp o ses , h o w p re p ar ed , 55 , \ _

M as s ac t i o n l aw , o f, 2 92
a m I N D EX

( N umb ers r efer t o p ag es .

)
M as s s p ec t r o gr ap h , 2 53 O r gani c m
at t er , 6 5
M at er i al s , h o w r ec o g niz ed 1 6 O s mo s i s , 3 79
O s t w al d , W i l h el m, 2 96
,

M at t er c o ns e rv at io n o f 1 9 ; s t at es o f 1 3
, , ,

M e l t i n g p o i nt 6 3 O xi d at i o n, 54 ; d efinit io n o f, 37 ; s p e ed o f, 3 8
D i mi t r i I vano vi t c h ( p o r
,

e nd e l e j e fi , O xi d e , d e finit io n o f 3 8 ,

t rait ) 3 1 5
,
O xi d e s , 3 1 ; ac id ic 2 1 3 ; b asic , 2 1 3
,

M er c ur y , red o x id e o f 36 O x i d i z i ng age nt , 2 1 1
b
,

M e t al s , 2 8 ; e l ec t ro n t h eo ry o f 178 ; and , O x y ge n , 3 1 ; b e h av io r o f s u s t anc es h e at e d

no nme t al s , 2 8 in 34 ; c h ar ac t e ris t ic s of 3 4 ; e x p e ri
k b ment s wit h 33 ; h el me t 4 2 ; i mp o r
, ,

M i l l i an , R o er t A nd r e w ( p o rt rait ) , 1 6 2
M i xt ur e , vs c o mp o und , 2 6 , 2 9 ; d e finit io n
, ,

t anc e o f, 3 1 ; nas c e nt 1 35 ; p re p ar a
t io n o f, c o mmerc ial , 3 3 , h is t o ric al 3 1
.
,

o f, 2 2 ; s e p ar at io n o f, 2 7
b
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M o i s t ur e , i n ai r , 2 7 5 l a o rat o ry 3 2 ; t e s t fo r 3 3 ; us es o f 4 2
m
, , ,

M o l ar s o l u t i o n, 1 53 O xy h y d r o ge n fl a e , 55
M o l ar w e i gh t , 2 4 4 O z o ne , 4 3
m
M o l ec ul ar f o r ul as , 9 1
M o l ec ul ar w e i gh t s , s t and ard o f, 2 4 4 P ar ac e l s us , 3
m
M o l e c ul ar and at o i c w e i gh t s , 2 39 P er nt age c o m
p o s i t i o n fr o fo r ul a,m m
M o l ec ul e s , 8 2 ; d e fini t io n o f, 8 2 , o f g as e s , l gg
56 o f h y d r o g en, 2 4 1
°
P e r i o d i c c l as s i fic at i o n, 3 19 ; c h art , 3 1 6
M o l y b d e nu , 7 m P er i o d i c l aw , ne w , 3 1 4 ; o l d , 3 1 5
M o no b as i c ac i d s , 2 0 6 P er i o d i c t ab l e , 3 1 6 ; v al ue and us e o f, 3 1 7
M o r l e y , E W ( p o r t r ait ) , 7 1
. . P er o xi d e s , 7 2
M o s e l e y , H e nr y G J ( p o rt rai t ) 3 1 8
.
-
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P h e no l , 4 4 9
M ul t i p l e p r o p o r t i o ns , l aw o f , 7 3 ’
P hi l o s o p h er 8 s t o ne , 3
M ur i at i c ac i d , 1 4 1 P h l o gi s t o n t h e o r y , 3 5
P h o t o s y nt h e s i s , 2 7 3
N ami ng c o mp o und s , 98 P h y s i c al c h an ge ,
N as c e nt o x y ge n , 1 35 P i c c ar d , A u gu s t e , 2 7 1
N as c e nt s t at e , 2 99 P i c r i c ac i d , 30 6
N eo n l amp , 2 7 0 Plu mb ago , 2 19
N e ut r al i z at i o n , o f as e and b ac id 1 50 ; i n P o i s o n g as , 1 30
P o l ar and no np o l ar c o mp o und s , 1 79
,

anal y s i s , 1 53 ; i o ni c t h eo ry o f, 1 6 5
m
i

, met all i c , 1
N e ut r o n , 1 7 6 P o t as s i u 24
N e w t o n , S i r I s aac , 6 P o t as s i u m c h l o r at e , 3 2
N i t er , 2 9 5 P o t as s i u m c h l o r i d e , 32
N i t r at e s , 2 9 9 ; t es t fo r , 30 0 P o t as s i u m h y d r o xi d e , 1 2 7
N i t r i c ac i d , 2 9 6 ; ac t i o n w it h et al s , 2 9 9 m P r ec i p i t at a, 1 6 7
m
fu i ng , 2 98 ; o x id i z ing ac t i o n o f, 2 98 P r ec i p i t at e d c h al , 2 28 k
p rep ar at io n o f, 2 96 ; p ro p ert ie s o f , 2 9 7 ; P r e s s ur e , c h ang e s v o l ume o f g as , 3 2 8 ,
us e s o f, 30 0 s t and ard c o nd it i o n o f 32 7
Ni t r i c o xi d e , 30 2 P r i e s t l e y , J o s e p h , 6 , 3 1 ; ( p o rt rait ) 3 2
b m
,

N i t r i t e , 30 0 P ro l e s , s o l v ing , 1 1 3 ; i nv o l v ing v o l ume s

N i t r o c e l l ul o s e , 30 6 o f g as e s , 2 4 3 ; i nv o l v ing w e i g h t o nl y , 1 1 0 ;
N i t r o g e n , 2 6 2 , and b
ac t e r i a, 30 9 , c o m i nv o l v i ng w e igh t and v o l ume , 2 4 6
p o und s as fe r t i li z er s , 3 0 8 , c y c le, 30 8 , P r o p e r t i e s , 1 6 , 1 9 , 35
fix at io n o f, 2 8 7 , 2 9 5, 3 0 5 ; H a er p ro c e s s , b P r o t e i ns , 3 0 8
m
2 8 7 ; i p o rt anc e o f, 2 6 2 ; o x i d e s o f, 30 2 ; P r o ut , 2 5 4
p r e p ar at i o n o f, i r o ni air , 2 6 2 ; p ro p e rt i es P ul l man c ar ( air c o nd it io ning ) , 2 76
o f, 2 6 4 ; p ure, p re p arat io n o f, 2 6 3 ; us e s
o f, 2 6 8 Q ual i t at i ve e xp er i me nt 7 1
Q uant i t at i v e e x p e r i me nt 7 1
,

N i t r o ge n d i o xi d e, 30 2
Q uant i t at i v e me ani ng o f e uat i o ns , 1 1 2 q
,

N i t r o gl y c e r i n, 3 0 6
N i t r o u s o xi d e , 3 0 3
N o d ul e s ( ni t ro g e n fix ing ) , 30 9 R ad i c al s , 96
N o n e l ec t r o l y t es , 1 58 R m
a s ay , S ir W i l l i a m
( p o rt rait ) , 2 6 9
m
N o n e t al s , and t h e p erio d ic s y s t e , 32 1 m R ar e g as es ,
N o np o l ar c o mp o u nd s , 1 79 R ay l e i gh , L
o rd , 2 69

“ m
N or al s o l ut i o n , 1 54 R e ac t i o ns , c h e mic al , 2 5 ; w h ic h g o t o c o m
N o v o c ai n, p l et i o n 1 57 ; i o ni c , 1 6 5 ; r e p l ac e ment 50
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7
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N uc l e us , o f at o , 1 7 4 ; s t r uc t ur e o f, 17 6 re v er s i l e , 2 1 3 , 2 8 5, 2 8 8 ; s p eed o f, 2 9 1 ,
t y p e s o l , l o4
O c t et , 3 2 3 R e cl o xi d e o f m
erc ur y , d ec o mp o s it io n o f,
O i l , o f v it rio l , 4 9 zz3
Oi l d ag, 2 1 9 R e d uc t i o n , 54
Ol e um, 2 0 9 R e f e r e nc e oo b k
s , 336 , 3 3 7
O r gani c c h e mi s t r y , 2 2 3 R q
efri ger at i o n , wi t h l i uid ammo nia, 2 8 2