C H E MIC A L RE A C T IO NS

A ND T H E IR EQU A T IO NS

A G uid e
for Stude nts
a “ R f mice
of
a e-

Che mistry
B ook

ING O W D . . H AC K H , PH C . .
, A B
. .

P RO F E SSO R OF B I O CH E MI ST RY . COL L E G E OF P H Y SICIA NS

A N D SU RG E ONS O F SA N F RA N ClSCO ,

P H I L A D E L P H IA

B L A K IST O N S SO N CO
’
P . .

1 0 1 2 W A L N U T S T RE E T
 I
5 1 1A u "1
3
I

]
x -

COP YRI G HT ,
1 9 2 1 , B Y P . B L A K I ST O N
’
S SON 8: Co.

T H E MA P L E P R E S S YO R K P A
 P REFA CE

The inability to balance a chemi cal equation is a most

common difficulty of students of chemi stry The writer .

when teaching at a large u ni versity actually encountered

graduate students of chemi stry who were unable to
balance an incomplete ionic equation that involved
o xidation and reduction not to mention the large ,

number of first and second year students who had only

a very ha zy idea of the principles
'

I n order to supply students with necessary m a te rial

and to expound the general prin ciple s of balancing equa
tions this concise volume was written I t does not enter
,
.

into a detailed discussion of physico chemi cal equations -

but confines itself mainly to a consideration of purely

chemi cal equations from a technical and arithmetical
standpoint The writer hopes that a study of this
.

volume ( which to the writer s knowledge is the only

, ,
’
,

one of its kind on the sub! ect ) in connection with any

good text will aid toward a clearer understanding of
,

chemistry on the part of the student A detailed study .

'

of the fo llowing pages should enable anyone to balance

any chemical equation rapidly and correctly .

With pleasure the writer acknowledges hi s gratitude

to Dr H enr y D zA rcy P ower for many valuable sugge s
.

tions and criticisms in reading the manuscript and to ,

his students M essrs J ordan K onrad and Magee for

,
.
, ,

read ing the ma nuscript and proofs H e also feels .

much indebted to his teachers P rofs E dmond O Neill , .

’
,

G N Lewis and J oel H H ildebrand

. .
,
. .

SA N F R AN CI S CO , CA L .
 TA BL E O F CO NTENT S

CH A P T E R I

SY MB O L S
Atom s , m ol ec u les ons on zation
,
I ,
I i .

CH A P T E R I I
FoIIMU L A S
E m iri c a l ,
p rational c onstitutional an d struc tural f orm ulas
, , .

Vale nc y an d v ale nce num be rs Oxida tion an d r educ tion . .

N om e nc la ture an d te rm inology of c om poun ds .

Sum m a ry of inform ation c ontain e d in a form ula .

CH A P T E R I I I

E Q U A T I O N S ( IN VO LVI N G N o OX ID AT I O N A ND RE D U TI O N ) C
M olec ular an d ionic e quations finis hing an d b alancing . e qua
tions . Calc ula tions an d p robl em s .

CH A P T E R I V
EQ U ATI O N S ( INv C L e C OX ID ATI O N A ND RE D U CT I O N )
M olec ular an d Ionic e quations . Th e three steps In ba l n cing
a .

E x am p l es an d proble m s .

CH A P T E R V
RE A CT I O N S A ND T HE I RRO L CO NT
T he s pee d of c he m i c a l reac tions an d t he c he m i c a l e quilib rium .

M ec ha nica l control by s urfac e c ata lysts c onc e ntration an d

, , ,

pre ss ure Therma l c ontrol an d t he in flue nce of hea t

. .

E le c tric al c ontrol e l e c trom otive force ga lv a nic ce lls e le c trolysis

, , , .

CH A P T E R VI
T YP E S or CHE MI C AL RE A CTI O N S A ND EQ U AT I O N S .

An alysis sy nthesis an d m e tathes is N eutrali zation

, , . an d
hydr olysis C om bination diss ociation displac em ent
.
, , , an d
s ubs titutio n
viii TAB L E OF CO NTE N TS
A P P E ND IX
P A G E

1 . K EY NO M E NC LATU R E WI T H A L I ST or RAD I C A L S, IO NS
To ,
A N D

V ALE NCE NU MB E RS .

II D I SP LA CE M E NT SE RIE S or T H E E L E ME NTS
. .

III P E RI ODI C SY ST E M A ND CL A SSIP I CA T I ON O F T H E E LE ME N T S

.

I V SO LUB I L I T Y T AB L E O F CO MP O U ND S
_

V P RE P AR AT I O N or SALTS
.

K E Y T o T H E EQ U ATI O NS

INDEX A ND G LO SS A RY OF CHE MI CA L T E R MS
 CH EMICA L REA CT IO NS A ND T H EIR
EQUAT IO NS

CH A PTE R I

SYMB O L S

P age 3: line 13
. Pla ce c o m m a afte r the re fore an d take out c o mm a

P g
a e ques tion
47 , 27 , las t se nte n ce woul d re a d : Fe c os ts 3d , AI sh . 1 3d ,
an d M g
.

sh . 1 6d. .

Pa ge 45 q ues tion
, 2 . P ri ce of Zn 2 sh.

B A c xH , C H E MI CA L Ru m “
or A ll ! ) T H E IR E Q U A T I o Ns .

b u u zs a vu m e 0 1 “ A U men t a l
ma nu r e cu m u me ( 10 1 0 11 11 an e le

m olecul e an d aggre gate t o an element W hile unlike ,

at oms com b in e to form a compound molecule and

a ggre gate t o a compoun d Molecules are capable of .

in depen de n t existence that is they may exist separ at ely , ,

a n d not in aggregation with si milar molecul es Thus .

a m olecule is the sm allest imaginable particle of a

c om p oun d an atom the smallest i magina ble part icle

,

of an element While at oms are chemically inde

.
2 CH E MICAL R E ACTI O NS A ND TH E IR E QUATIO N S

t
s r u c t ible , the molecu le s ar e susceptible to endless
l

chemical change S uch cha n ges and interchanges are

.
!

expressed in the form of lh m ic al equations f

'
c .

A chemical symbol has three distinct uses as it may

represent an atom m olecu le or ion To distinguish
, .

whether a symbol represents an atom molecule or ion , ,

a n um eral or or sign is used

—
.

A tom . The a tom of an element is shown by the

symbol alon e Thus H represents an atom of hydrogen
.

with an atomic weight Of CI stands for an atom

of chlorine with an atomic weight of and Fe is
an atom of iron ( ferru m ) with atomic weight
—
M ol e cule The molecu le of an element is shown by
.

the symbol with a small numeral at t ached indicating the

n umber of atoms : H z or H is a molecule of hydrogen
2

containing two atoms of hydrogen the molecular weight ,

being the sum of the atomic weight 2 X

S ; or S is a molecule of sulfur Containing four
4

atoms of sulfur the molecular weight being 4 X

,

S, or S is a molecule of sulfur with Six atoms

6

of sulfur the molecular weight of this molecule is

,

6 X S or S is a mole ule of sulfur t

,
c
containi ng an unknown number of atoms of sulfur .

A ll gaseous elements have ordinarily two atoms in their

molecule e g 0 2 N C12 which indicates respectively
,
. .
, ,

a molecule of oxygen nitrogen and chlorine as gases

, ,
.

T he fa c t that ato m s are c hem i cally in d estruc tibl e do es not e x c lud e

1

t he po ssib ility th at th ey m ay b e tra nsform e d by p hys ic al m e an s Mod .

ern resea rc h both theore ti c al a n d p ra c tic al p oint to still s m a ll e r c or

, ,

p us cles or e l e c trons as t he b uil d ing s ton es of a to m s N e v e rt h e l e ss .

t he conc ep tion of a s tru c ture of t he a tom s will not afie ct t he olde r

“
”

c on ce p t ion of an a to m as t he c he m i c al u ni t or an ele m e nt as a type of ”

,

a to m s . Chem is ts will thus continue to deal with a tom s an d future ,

progress in t he subatom ic realm will m e re ly increase th e knowle dge of

t he re l ation am ong e le m e nts a n d the ir p rob abl e e volution bu t w ill not ,

m a te rially c ha nge t he applic ation of t he atom ic theory .

 SYMB OL S 3
.

Only in a few cases have the number of atoms in a

molecule been determined for solid elements e g P 4 ,
. .
,

P 3 A S2
, ,
If the number of atoms in a molecule
of a solid element is unknown the molecule should be ,

written with x e g N a Fe A I C,
. .H owever in
,” z, 3 .
,

metals this number is assumed to be one so that in

, ,

this case N a would represent not only an atom but als o ,

a molecule of sodium ( natrium )

—
.

Ion . The i on of an element is indicated by the

symbol with one or more negative
signs attached whi ch represent the number of positive
,

or negative charges attached to the atom of an element .

A n Ion therefore Is an electrified ato m or an atom with

,

a certain number of electrical c OI pu scle s attached .

These charges are also written as dots and dashes thus ,

H or H hydrogen ion H atom with one positive

‘
+ -

charge C1 or C1
,
chloride ion CI atom with one
’
,
-

“
negative charge Ca ++ or Ca ,
calcium ion Ca atom ,
-

“
with two positive charges S or S sulfide ion ”

—
, ,

S atom with two negative charges or A I ,

aluminum ion A I atom with three positive charges

,
-
.

These ions ordinarily exist only in solutions The .

ma! ority of salts dissolved in water become ionized

because their component atoms become electrified .

T liu s N a Cl ( sodium chloride ) when dissolved in water

will form N a ( so dium ion ) and CI ( chloride ion )
+
,

whil e a small amount of the original sodium chloride

remains as N aCI ( molecular or non ioni zed sodium -

chloride ) Some salts will ionize slightly that is they

.
, ,

will break apart ( dissociate ) only to a small degree .

A mmonium chloride ( NH 4 C1) when dissolved in water

forms a few ammonium ions ( NH 4 ) and a few +

chloride ions ( CI — the larger percentage of the sub

stance remaining in molecular combination ( N H 4 CI) .
4 CH E MI CAL R E AC TIONS A ND T H E IR EQ UATIO NS

I onization or electric dissociation therefore is the , ,

breaking apart of the molecul e in solution whereby

t he atoms or groups of atoms ( radicals ) acquire a
positive or negative charge It mus t be borne in .

mi nd that the properties of the ions are distinctly

diff erent from the properties of the atoms S odium is .

diff erent from sodium ion iron metal ( Fe ) diff ers from
,

ferrous ion and f erric ion for the ions

are always electrified or charged atoms
—
.

Summ ary The three ways of using a chemi cal symbol

.

are summarized as follows

H on e hydrogen a tom which e xists in compoun d s
, ,

2H tw o h y drogen atoms ,

H2 on e hydrogen molecu le which exists in hydro

,

gen gas,

2H 2 tw o hydrogen molecu les ,

H + one hydrogen i on which exists in the solution

,

of acids
,

2H + tw o h ydrogen i on s .

A ccordinglythe symbol s Cl S 2 8 38 Fe A l stand , , , , , ,

respectively for one atom of chlorine one atom of sulfur , ,

two atoms of sulfur three atoms of sulfur on e atom

, ,

of iron one atom of aluminum while their respective

, ,

atomic weights ; 0 12 So 2 8 0 38 6 Fe A l means On e

, , , , z, , ,

molecule of chl orine ( two atoms ) one molecule of sulfur ,

( six atoms ) two molecules

, of su l fu r ( twe l ve atoms ) ,

three molecules of sulfur ( eightee n atoms ) one m olecule ,

of iron (un kn own number of atoms) one molecule of ,

“
alum inum (unknown number of atoms) ; Cl S
"

, ,

Fe ”
, represent respectively
one chloride ion ( chlorine atom with one negative
charge ) one sulfide ion ( sulfur atom with two negative
,

charges ) two sulfide ions ( two sulfur atoms with four

,
 SYMB OLS 5

negative charges) three sulfide ions ( three sulfur atoms

,

with six negative charges ) one ferrous ion ( one iron atom ,

with two positive charges ) one ferric ion ( one iron atom ,

with th ree positive charges) on e aluminum ion ( one ,

aluminum atom with three positive charges) .

QUE ST I O NS

1 . De fine s ym bol , m olec ule ,

ion ioni zation
atom , , .

2 What is t he sym bol for a n atom of b rom ine sele nium potass ium
.
, , ,

nitroge n co ppe r m agnesium p hosp horus ?

, , ,

8 What is t he sym b ol for a m ole c ule of t he ele m e nts give n in q ues tion
.

2?
4 . Wha t is t he sym bol for an ion of t he elem e nts give n in q uest ion 2 ?
What is the ddIere n ce b e twee n N ; a n d 2 N, Oz a nd 0 11 30 2 2 0 , a n d
'

5 .
, ,

60 , F2, 2F an d 2 F7
6 . Sta te a ll t he inform ation co ntaine d in t he s ym b ols : Na , Na +
,
“
se t 8 0 47 Se 0 ) A 3; A 8 ” A S4: H g; H g +
Hg H
‘

, 1
 CH A PTE R I I

FO RM UL A S

Formula —The . vocabulary of chemistry consists o f

formulas A ch emi cal formula is a combination of
.

symbols which show s tfhe' number and kind of atoms ..

in a molecule hence t he formula tells the chemical

, ,

c om p osition of a s ubst a nce and represents the molecule

‘

of a com pound H owever as the symbols not only

.
,

indicate the kind of atom but also a c ertain quantity , ,

called the ato mi c weight it is evident that a formula ,

must also include the quantitative composition of a

compound and the molecular weight
, .

For instance N a Cl means a molecule of sodium

,

chloride containing one atom of sodium or 2 3 parts by

w eight and one atom of chlorine or
, parts by weigh t .

The total or molecular weight is naturally the sum of

the atomi c weights that is 2 3 ,
From ,

t his proportion the percentage can be calculated for ,

as parts of sodium chloride contain 2 3 parts of

so dium then
,
: 23 1 00 : x and x 2 3 X 1 00 ,

that is per cent sodium ; while the per

centage of chlorine is found by the proportion
1 00 : x and a: ,
X 1 00 which
means per cent of chlorine Two molecules of .

sodium chlorid e may be written either 2 NaCl or ( N a Cl) 2 .

In the first case the two in front refers to the whole

following formula in the second case the parenthesis
,

is necessary as otherwise the formula N 3 0 12 would

, ,

indicate a compound molecule containi n g one atom of

sodium and two atoms of chlorine which is wrong .

6
 F O RM U LA S 7

N a 2 8 0 4 means one molecule of so dium sulfate contain

ing two atoms of sodium or 2 X 2 3 4 6 parts of sodium ,

one atom of sulfur or 32 parts of sulfu r ,

four atoms of oxygen or 4 X 1 6 64 parts of oxygen ,

which added together make 14 2 parts of sodium

sulfate and the molecular weight therefore is
N 8 2 8 0 4 7 H 2 0 means a molecule of crystallized sodium
.

sulfate in which there are in addition to the sodium ,

sulfur and oxygen seven molecules of water This

, ,
.

water which forms an essential part Of the crystal is

called the water of crystallization The water of crystal
.

liza tion can be driven off by heat and the substance

becomes anhydrous .

The formula for ammonium aluminum sulfate ,

In dica tes a more complex

compound a molecule of which cont ains one molecule
,

of aluminum sulfate one molecule of a m

m oniu m sulfate and twenty four molecules
-

of water A dding these molecules together the number

.
,

of individual atoms in this compound are :

2 atoms of aluminum or 2 X parts of A l

3 1 4 atoms of sulfur or 4 X 32 pa rts of S
2 atoms of nitrogen or 2 X 1 4 parts of N
( 3 X 4 ) 4 0 a t om s of
oxygen or 4 0 X 1 6 parts of O
( 2 X 4 ) ( 2 4 X 2 ) 5 6 atoms
of h ydrogen or 56 X 1 parts of H

making altogether parts of

crystallized ammonium aluminum sulfate having the ,

molecular weight of
8 CH E MICAL R E ACTIONS A ND TH E IR UA TIONS
EQ

T ype s of Formula s —
formula for this compound
The .

may also be written A l ANzomfl sa Such a formula is .

called an empirical formula for only the number and kind

of atoms are given From such a formul a the quantita
.

tive composition of the substance can be calculated but ,

it does not indicate the way in which the atoms are

arranged in the molecule The arrangement of the .

atoms that is the way in which they group themselves

, , ,

is shown by the rationa l formula The rational formula .

given above for ammonium alum shows that sulfur is

present in the sulfate radical and nitrogen is
present in the ammonium radical ( NH T) while some of ,

the oxygen and hydrogen is present as water of crystalliz a

tion Thus the rational form
. ula here shows (a ) two
atoms of aluminum are linked to three sulfate radicals ,

( )
b two ammon ium radi cals are linked to one sulfate
radical and ( c) the crystals cont ai n twenty four mole
,
-

cules of water .

There are f our types of formulas : The empirical the ,

rational the constitutional and the structural or graph

,

ical The characteristics of each type are as follows

.

E m pirical Formula The empirical formula shows

.
-

only the number and kind of atoms from which ( to

repeat ) the mole cular weight and the percentage com
position can be calculated Thus F.S.o1 2 simply means .
,

a molecule containing two atoms of iron three at oms ,

of sulfur and twelve atoms of oxygen the molecular

, ,

weight being (2 X ( 3 X 32 ) ( 1 2 X 1 6 )
Such a type of formula gives nothing further regarding
the chemi cal nature and is practically never used in
inorganic che mi stry they are used howev er in organi c
, , ,

chemistry for compounds of which only the percentage

composition is known and w hich have not been fully
,

investigat ed .
10 CH E MICAL RE ACTI ON S A ND TH E I R E QUATIO NS

and six oxygen atoms and finally six double b onds ,

between three sulfur and six oxygen atoms In a .

structural formula the radicals are resolved into their

—
simplest components single atoms and the connection ,

between each atom is shown Thus the abov e structure .

formula indicates that oxygen is always bivalent as ,

it has two bonds while the sulfur is hexavalent havin g

,

Six bonds .

In inorganic c hemistry the rational formula is gen

erally used while the constitutional and st ru ctu ral
,

formulas together with the empirical formula are mainly

employed in organic chemi stry In organic chemistry .

the structure theory has yielded the most magnificent

results for without the recognition of a structure none
, ,

of the synthetic substances could be manufactured such

as indigo camphor dyestu ffs and pharmaceuticals
, , ,
.

A modern simplification of structure formulas for organic

compounds has been devised in the form of structure
symbols (see Canadian Chemical J ournal vol 2 p 1 35 ,
.
,
.
,

1 9 18 ; Science vol 4 8 p 333 1 9 1 8 ; Chem N ews v ol

, .
,
.
,
.
,
.

1 18 p 28 9
,
.
,

Sum m ary — Summarized the four typ es of formula are :

.
,

E mpirical 1112 0 30 . C3H O .L

Rational : A 12 ( 0 0 3) 3 CH z ( COzH ) 2
Constitutional A lz COa COOH
CO CH 2/
\ COOH
Alz CO :
S tructural or graphic 0
/ 0
 F ORMULA S 11

—
Val e n cy What is a bond or valency ? H ow is it
.

possible to depict graphically the intramolecular arrange

ment of the atoms ? Logically we reason that the
number of atoms in a molecule must depend upon the
force which holds the atoms together ; furthermore we
find that certain groups of atoms such as the sulfate ,

radical are very stable and pass through a number of

,

chemical changes as un its and in such cases the force ,

holding the atoms together must be especially strong .

A t present we have no means of measuring this force

nor do we know its mechanism H owever one of its .
,

manifestations is that property of the element which

is termed valency Valency is sometimes defined as the
.

combining power of an atom in regard to hydrogen but ,

it is more exact to define valency as the combining

capacity of an atom or group of atoms ( radicals ) using
an atom of hydrogen as a unit of c omparison H ence .

if an atom of element X combines with one atom of

H and forms a compound H X then X is said to have ,

a valency of one If the atom of element Y can combine

.

with two atoms of hydrogen to form a compound of

the type H 2 Y then the valency of Y is two and like
, ,

wise if an atom of element Z combines with three atoms

of hydrogen to give a molecule of the type H 3Z then ,

Z has a valency of three The structural formulas .

H H
\
for these three molecules are H X, -

H> ,
—
Y and H Z
H /
in which each valency is shown by a line In a com .

pound the atoms whic h have a valency of one are

called monovalent (e g H N a K Cl of two
. .
, , , ,

bivalent (e g 0 Ca B a. . of three
, trivalent
, ,

( g
e. A.I) of four
, tetravalent (e g C Si of five . .
, ,
~
12 CH E MICAL R E ACTIO NS A ND T H E IR EQ UATIONS

pentavalent of six hexavalent of seven

, heptavalent
.
,

and of eight octo valen t

—
.

Valen c e Number It has be come necessary to di vide

.

the elements into negative and positive groups (se e

Chapter 5) and accordingly in each compound there is
a negative and positive constituent This assumption .

leads to the consideration of positive an d negative va len ce

n u mbers ( also called p olar n u mbers ) The basis for the .

assignment of valence numbers is hydrogen with a positive

valence number of one or In all stable compounds
the su m of the valence numbers must equal zero and
by considering H al ways as 1 the p ositive or nega
tive character of the other elements can be established .

Thus in H X the atom X must have a valence numbe r of

1 in H gY the atom Y h as a valence number of — 2 in
,

H SZ the atom Z has a valence num ber of 3 Therefore — .

,

it follows that CI in H CI must have a valence number of

, ,

1 that O in H zO has a valence num b er of 2 and N

—
-

, , , , ,

in NH 3 has a valence number of

,
3 .

In some cases elements do not com bine with hydrogen ,

but replace hydrogen ( see displacement series ) because ,

they are more positive than hy drogen and accordingly ,

have a positive valence num ber Thus N a which .

,

replaces one atom of H has a valence numbe r of

, 1;
calcium replaces two atoms of h ydrogen and has a
valency of two and valence number of + 2 The .

positive valence numbe rs range from + 1 to + 8 while ,

the negative valence numbers range from 1 to 4 -

.

The elements in their free s tate (uncombined ) are

assumed to have a valence number of 0
—
.

U nivale n t an d P olyvale n t H owever it is a common

.
,

misapprehension to assume that a gi ven element can

on
ly in avery few c ases has H a valen ce n umbe r of 1, s uc h com
poun ds are the hyd rides , NaH L iH , .
 P oRMU L A s 13

form only one type of comp ound that is can have o nly ,

one defini te v alency or valence number for in many

cases an element can form two or more series of com
pounds that is have two or more definite valencies or
, ,

valence numbers The first class of elements are spoken

.

of as uni valent elements ( which must not be confus ed

with monovalent elements) while the second class of ,

elements are call ed polyvalent elements In general .

the alkali metals ( N a K , ea rthalkali metals

,

( C a,
B a etc
, ) . an d earth metals ( A l etc ) are univalent , .
,

while the non metals and heavy metals are polyvalent .

A u ni valent element may consist of monovalent atoms

( g
.e . N a ) ,bivalent atoms ( g
e C a ) trivalent . atoms
.
,

( g
.e . Al ) ,and s o on A polyvalent
. element may consist
of mono and biv alent atoms ( Cu ) mon o and trivalent ,

atoms (A u ) bi and trivalent atoms ( Fe ) bi tri

, ,

and hexavalent atoms ( Cr) mono tri penta and ,

hexavalent atoms ( Cl) and s o on , .

Se rie s of Com poun d s A polyvalent element that

.
-

is an element having two or more valencies will form

, ,

two or more series of compounds a nd these series of

compounds will hav e distinct p roperties and diff erent
’

names Thus iron has three series of compounds

.
,

namely f err ou s compounds such as Fe Clz Fe O etc in , ,

.

which the valency is two and the valence number

+ ; f
2 e rr i c compounds such as Es Cla Fe 2 0 3 etc in , ,
.

which the v alency of iron is three and the valence number

+ 3 and fina l ly the f erra tes such as N3 2 F8 0 4 in which
the valency of iron is six and the valence number + 6 .

Chlorine has four series of compounds: the chlorides

( N Cl B a Cl e t c ) in which chlorine has a valency of
—
a , g , .

one and a valence number of 1 ; the chlori tes ( NaOCl ,

Ca ( OCl) 2 ) in which chlorine has a valency of three ,

and a valence number of + 3; the chlor ates ( K ClO a)

14 CH E MICAL R E ACTION S A ND T H E IR E QUA TION S

with a valency of fi ve and valence number + 5 ; and

finally the perchlora tes ( KCIQ 4 ) with a valency of seven
and valence number of + 7 Though chlorine is a nega
.

tive element like all non metals it has in only one series
, ,

of compounds the chlorides a negative valence number

, , ,

and in the other three series a positive valence number .

This positive character of the valence number for a

negative element is caused by assu mi ng the valence
number of oxygen in a compound to be always
—2 .

This conception aids in understanding oxidation and .

reduction as explained further on

—
.
,

Fin d in g th e Vale n c e Num b e r From the formula of

.

a compound the valence number of the atoms and their

positive or negative character can readily be found by
remembering that hydrogen in a compound is always
+ 1 and oxygen in a compound is always
,
— 2 and that ,
“
the sum of the valence numbe rs in a saturated and
stable compound must always be zero Thus in water
—
.
,

( H O ) there is H 2 X + 2 and O 2
—
z 2 , ,

therefore 2) 0 In lime ( Ca O) oxygen

—
.

is 2 so calcium must be + 2 In ferric oxide ( Fe a )

—
.
,

there are thre e oxygen atoms that is 3( 2 ) , so

the two iron atoms must be + 6 and one iron atom + 3 , ,

and the valence number of iron in that compound is + 3 .

In a similar way the valence numbers for all other

atoms are determi ned and can readily be found by the
difference necessary to make the sum zero hence it is ,

simply an arithmetical problem A few examples will .

illustrate this .

P otassium permanganate has the formula K Mn O 4 .

To find the valence number for the Mn atom add t he

valence number of K to the sum of the valence
numbers of oxygen 4 ( 2 ) — 8 and get — 7 thus Mn -

mus t have + 7 T o m ak e this clearer write the known

.
 ORM ULAS
F 15

valence numbers under the symbols and form an

arithmetical equation thus
K Mn 04
a: 4( -
2) 0 and hence a: +7 .

The valence number of ni trogen in so dium nitrate is

Na N
a: —
3( 2 )
this cas e a: + 5 thus
0 . In ,

the valence number of nitrogen is + 5 Likewise the .

valence number of chro mium in potassium bichromate

is found : K2 Cl g '
O7

2x —
7( 2)
from this follows 0,
that 2 3: 12 and the valence number of one chromium
atom is + 6
—
.

O xid ation an d Re du ction

element has several . If an
valence numbers that is if it forms several series of
, ,

compounds we speak of di fferent stages of oxidation

, .

A s a rule oxi da tion can be defined as the incre ase or

augmentation of the valence number that is a change , ,

from a lower to a higher valence number ; while redu ction

is the decreas e or diminution of the valence number ,

that is the change from a higher to a lower valence

,

number The transformation of ferrous compounds

.

into ferric com p ounds is thus oxidation ,

while the transformation of a ferrous compound

into metallic iron ( 0) is reduction In the former the .

ferrous compound has bee n oxidized in the latter it has ,

been reduced A gain if a chloride

. 1 ) is transformed
into chlorine gas the valence number has been
increased and the chlorine atom in the chloride is oxi
dized to free chlorine If chlorine gas (0) is further
.

oxidized to a chlorite chlorate or perchlorate

16 C E H MI CA L REA CT I oNs A ND TH E IR Eq U A T I oNs

the valen ce numbe r is further in creas e d an d

therefore the chlorine atom further oxidiz ed Re duction .

is a chan ge in the opposite direction e g the chlorine ,

. .

atom in a perchlorate can be reduce d t o chlorate ,

chlorite chlorine or chlori de S chematically the case

, , .

is illu strate d by the followin g :

Val nc num b
e e ers l 0 +3 +5 +7
Type of c om po unds : chlorid es ch lorin e chlorites ch lora tes perchlorates
Form ula X CI

—— Cl : X 0 10 3
OX I DA T ION
K O10 3 X 0 10 4

RE D U CT IO N

in whi ch X is a monovalent element .

A n y change fr om lef t to right is oxi da ti on .

A n y cha n ge fr om right to lef t is r edu ction .

It is eviden t from t he diagram that the chloride s c an

not be further re duced that the per chlorate s can not
,

be fur ther oxidiz ed and th at fr ee chlorin e gas can be

,

eith e r reduce d to chlorides or oxidi ze d to chlorites

, ,

chl orates or perchlorates

,
.

Similar ly there ar e several series of sulfur compoun ds

Val nce num b ers
e 0 +4
Types of com pounds s ulf ur sul fites
Form ula 8 X 38 0 3

— OX I D A T I O N
RE D U CT ION

The conclu sions drawn from this diagram a re

Su lfides can be oxidized to free sulfur sulfite s , , or
s ulfates .

Su lf atcs can be reduced to sulfit e s free sulfur , , or

Free f su l ur
can be oxid i z ed to sulfit e s and sulfates or ,

reduced to sulfides .

Su lfites can be oxidiz ed to su lf ates an d reduced to free ,

sulfur an d sulfides .
18 CH E MICAL R E ACTIO NS A ND TH E IR EQ UA TIONS

lower positive valence number (ferrous arsenous me rcur , ,

ous cuprous nickelous plumbous

, , , ,

ic i ndicating the higher form of oxidation the hi gher

-

positive valence number ( ferric arsenic mercuric cupric , , , ,

nickelic plumbic , ,

K e y to Nom e n clature — A list of the more common

elements io n s and radicals with their valence numbers
, ,

can be found in the appendix and t his key to the nomen ,

c la tu re of chemical compounds should enable the stu d ent

to write the correct formula for any compound or to ,

give the correct name for any formula of inorganic

chemistry .

Sum m ary of Inf orm a tion Con tain e d in a Form ula .

From any chemical form ula there can be deduced :

( )
a The kind of elements and the number of atoms
which constitute the molecule .

b
( ) The weight relation of these elements and the
molecular weight of the compound .

( 0 ) The percentage of weight of the elements comp os

ing the molecule .

d
( ) T h e valency of the elements and therefore their , ,

stage of oxidation .

Whenever the formula refers to a gas or gaseous com

pound there is furthermore expressed by a formula :
, ,

( )
e The volume relation of the gaseous consti t uents .

A ccording to A vogadro s law there are under the same

’
,

pressure and at the same temperature in the same volume ,

of any gas the same number of molecules so it follows ,

that in 1 liter of oxygen there are the same number of

m olecules as in 1 liter of hydrogen and as in the form a ,

tion of water 2 molecules of H 2 react with 1 molecule of

,

0 2 so 2 liters of H 2 are required to combine with 1 liter

,

Of 02 .

(f ) The specific gravity or density of the gas . D ensity

 F ORMULA S 19

can be expressed in three ways according to the unit

chosen ( )
1 . D ensity with regard to oxygen D m,
refers to oxygen gas for comparison and its molecular
weight 0 2 32 is take n as a unit hence the molecular ,

weight of any other gas is also its density or D 0 2 ,

Mol Wt For H z the D a m, is 2 for N2 the D m , is 2 8
. .
, ,

etc (2 ) D ensity with regard to hydrogen

. D a m)
refers to the lightest known gas as unity In this case .

the molecular weight of the gas must be divided by the

molecular weight of hydrogen that is D 01 2 , Mol Wt 2 ,
. . .

H ence f or 0 2 the D 0 1 2 , is 1 6 for N2 the D ( H 2) is ,

14 .
( )
3 D ensity in regard to air as unity D om)
A certain volume filled with 32 grams oxygen will weigh ,

when filled with air grams hence if the density of

, ,

air is taken as unity the density of oxygen ,

D om) is
a n d accordingly the D a m of all

other gases is found by divi di ng their molecular weight

by t ha t is D a m Mol Wt
. . .

(g) The weight of 1 liter of gas The volume occupied .

by a mole (gramm olecu le) of any gas is liters Thus .

a mole of H g or 2 grams of hydrogen will fill

,
liters , ,

‘
a mole of oxygen or 32 grams of oxygen gas will also
, ,

occupy liters under standard conditions of pressure

and temperature hence the simple proportion
,
:M

1 : x and x , M will give the weight of 1 liter

of any gas In the above equation M represents the
.

molecular weight in grams mole) and a: the weight ,

of 1 liter of gas in grams .

( )
h The volume occupied by 1 gram of any gas I n .

this case the above proportion becomes M :y ,

and y M for if M grams will fill

, liters then ,

1 gram will occupy 22 4 / M liters

—
. .

E xa mp le The formula NH 3 for ammonia means

.

( )
a The molecule c on sists of one atom of ni trogen an d
20 CH E M I CAL R E ACT IONS A ND TH E I R E QUATI ONS

three a toms of hydrogen ma kin g al t ogether fo ur at oms

in the molecu l e .

( )
b The mol e c ula r w e ight is the su m of the ato m i c

we igh ts thus 14 parts of ni trogen ( by weigh t not vol

,
—
ume) an d 3 X 1 3 parts of hydrogen give 1 7 parts of
—
ammonia hence the molecular w eight is 1 7 .

( )
c The p e rc e ntage of n i trogen and hydrogen is c a lc u

la ted from the d a ta given in ( b) thus in 1 7 parts am

,

moni a there are 14 parts of ni trogen then 1 7 : 14 z: ,

1 00 : x hence 14 X
, , x and a: per
cent nitrogen while 1 7 : 3 z: 1 00 : y an d y
, 3 X 1 00 / 17
gives for y the percentage of hydrogen as per
cen t .

d
( ) The valence number of H being + 1 three a t oms
,

of H are t hus equal t o 3 therefore the valence number

of nitrogen must be —3
,

From t he table in the ap

—
.

p e n d ix we see tha t 3 is t h e lowest stage of oxidat ion

for nitrogen and it is e viden t tha t ammonia can not be
further reduced but can be oxidized to free nitrogen
, ,

nitrites or ni trates
,
.

( )
e N itrogen and hydrogen are both gases therefore
,

on e volume of ni trogen gas and t hree volumes of hydro

gen gas will combine and form ammonia .

(f ) T h e specific gravity or density of ammonia ( )

1
compared with 0 2 32 equals the molec ular weight
which is D m , 1 7 for ammonia ; ( 2 ) compared with
H2 1 it equals
, that is D are) ( )
3 com
pared with air 1 it equals
, that is D a m
A mmonia is thus a little over half as light as air
and oxygen but , times as heavy as hydrogen .

(g) I f liters of a m monia weigh 1 7 grams then ,

1
liter will weigh gram .

( )
h I f 1 7 grams of ammonia occupy liters t hen 1 ,

gram will occupy liters.

 P O RMU L A S 21

QU E ST IO NS

1 . De fine (a )
form ul a (b) vale ncy (c) valence num be r (d) o x idation
, , , ,

(e) re d uc tion 0) radic als (a) m ono vale nt an d univ alent ele m e nts
, , .

2 Write out all t h e inf orm ation c ontaine d in t he form ul as ( a) K I

.
,

( b) A gNOa, (c ) H 3P 0 4, (d ) K QH P O A ( 6 ) MgSOA 5H zO , . .

3 . Write out inform ation c ontaine d in the form ulas for the
a ll t he
following gaseous com poun ds (a ) H Cl (b) N 0 (c ) N 0 (d) CH , 1 3, 3 5, 4.

4 C al c ulate t h e m ole c ul a r w e ights of th e following c ompounds

.

(a ) fe rrous sulfate Fe SO. (b) fe rric sulfate Fe ( 8 0 ) (6 ) gluc os e C H u O

, z 4 ay o s,

( ) C q O ( ) bism uth nitrate B i ( NO ) (f ) potass ium alum

'

d sug ar e z u, a a,

(9 ) n itroglyce rin C H ( NO ) ( h) h e m oglob in Cu z 5 a l, e

H I I I I N I M OSI SSS o

5 . alc ula te t he
C e rc e nta g e c o m os ition of
p (a ) m e rc uri c c hlori e p d
H gClg, (b) m e rc urous c hlori e H gCl, ( c ) m ang anes e ioxi e Mn OY,
d d d
( d ) c o e r
pp s ulf a te Cu SO . 5 H gO, ( ) so ium c arbonate Na gCoa, ( f )
e . d
c rys talli ze s o iu m c a rb on ate
d d N
a gCOg 7 H gO, (a) s ug a r Cn H u O u , ( h) .

a m m o niu m nitrate N H 4N 0 3, (i ) a m m o n ium s u lf a te ( ! ) sil e r v

c hlori de AgCl ( k) silv e r ace ta te A n H 0 NB In (d ) an
, 3 3. . d ( f ) c alc ulate
t he p e rc e ntag e of w ate r not hy d rog e n a n d oxyge n, .

6 Wha t is t he rational form ula for s uc h a c om poun d as

.

(0 ) Na
“
N S IC.

fi
/
7 . Wha t is t he st ruc t ural form ula for the co m p ound s given in 6 ?
8 . D e te rm in e t he
valen c e num bers of the following elem e nts
( a ) sulfur in ms N8 8 0 Na SO Fe S Na s Fe SO. Ca S Ca sO . 8 0
, 3 3, g I, , g , , , , 2,

80 3, H SO ; (b) nitroge n in NH
Q A N H O H N 0 N 0 N 0 NO N 0 ;, g , 3 3, 3 , 2 3, , 2,

H NO K NO N H Cl K NO N H NO ; ( 6 ) iron in F8 0 Fe Cl
z, a, g , z, g a , g,

Fe ( O H ) a, Fe CN S, FO (ON) 3, NO TE T he
—
.

“
c ya n rad ic a l ( CN ) has a v al e n ce num b e r Of 1 lik e CI ; in it w e
—
‘

ass um e C with 4, an d N with + 3 .

9 Give an e x am pl e of the low es t a n d highes t s tag e of ox id a tion of

.

(a ) sulfur, ( b) c hlorine, (c ) nitrog e n , (d ) m angan es e , (e) iron, (f ) chrom ium ,

(a) m e rc ury , (h) copp er, (i ) le ad .

1 0 Write four or m ore form ul as of d iff e re nt c o m pounds for eac h se ri es

.

of c om poun ds or stag es of ox idation of (a) su lfur, (b) c hlorin e, (0 ) iron ,

(d ) nitroge n , an d give the p ro p e r nam es to th es e com pounds
‘

1 1 Write out t h e rationa l form ulas for t he following c om poun ds

.

( a ) ars e nou s c hlori d e , ( c ) a rs e ni c c hlori d e , ( b) c e rou s nitr at e , ( d ) c e ri c

s ulfa te , (e) potass iu m m a ng a na te , (f ) so d ium pe rm ang a na te , (0) ca l c ium

c hlori d e , ( h) c a l c ium c hlorite , (i ) c a lc i um c hlorate , (! ) p otas sium p e r

22 C H E MICAL R E ACTION S A ND T H E IR E QU A T I O N S
ch lorat e ( k) m e rcuri c brom ate (l) m e rc urous a rse nate ( m ) m e rc uri c
, , ,

a rse n ite , ( n ) f e rrous b ro m id e ( o) fe rri c brom id e ( p) fe rrous b rom a te

, , ,

( q) fe rric b ro m ate (r ) potass ium s ta nnate (8 ) sod ium stan n ite (t) lithium
, , ,

plum bite ( u ) potassium plu mb a te (v) nic colous carbonate ( w) ni c coli c

, , ,

c a rb ona te ( z ) plu m bi c bi chro m a t e ( y) plum b ous c hro m a te (z ) p lum b i c

, , ,

c hrom a te . NO TE .Consult the k ey to nom en clature in t he appe n d ix .

1 2 Whi c h of t he following ores c onta ins the highes t pe m e n t a ge of iron

.

( a ) he m atite FO 0 3 (b) m agne tite Fe o (c ) lim onite

3, s 4,

(d ) si d e rite FeCO (e) pyrite F8 8 ?

a, 2

1 8 C alcula te the p e rce nta g es of c arbon an d hy d rog e n in th e firs t

.

five m e m be rs of t he m etha ne se ries of hyd ro c arbons whi c h hav e t h e

ge ne ral form ula ( In this c as e the v alu e of n is 1 2 3 4 , , , ,

1 4 How m a ny m ol ec ul e s of wa te r of c ry s talli zation we re p rese nt in

.

t h e c rys talli ze d sa lts w he n (a ) 10 gra m s of c rys t N8 0 0 lose .

3 3

gram s of wate r by heating ( b) 1 0 gram s Of cryst B a Cl leave afte r

, . ,

heating a resid ue of gram s a nhyd rous salt (0 ) c rystalliz e d Z n SO , I

los es afte r hea ting p e r c e nt of it s w e ight ?

1 5 Giv e t h e n am e a n d form ula of a c om poun d c om pos e d of (a )
.

pe r c e nt s od iu m , p er c e nt c hlorine per c e nt oxyg e n ; ,

( b) p e r c e nt sil v e r p
, e r c e nt oxyge n p e r c e nt nitrog e n ; ,

(c ) p e r c e nt l e a d , p e r c e nt c a r b on p er c e nt oxyg e n
,
.

1 6 T e n gram s of t he c hlorid e of a univ al ent ele m ent 2: c ont a in

.

per c e nt of c hlorin e If t he a to m i c we ight of c hlorin e is

. what is the
a tom i c we ight of t he e le m e nt x a n d wh a t is its n am e ? ,

1 7 Fin d t he a nhy d ri d es of th e following s ubstan c es by sub trac tion of

.

H 0 ( a ) H NO ( b) H SO (c ) H ClO (d ) H P 0 ( e) C u ( O H ) (f )
3 z, , 4, s, 3 4, 2,

(0) L iO H ( h) H 8 i0 (i ) Fe ( O H ) (! ) H P O
, 4 4, 3,Classify these a nhyd rides ;.

as b as i c a n d a c i d a nhyd ri d es .

18 . gram s of the oxi d e of a bivale nt e lem e nt whe n re d uc ed

g a ve gram of a fin e m e talli c p owde r What is the a to m ic we ight of .

t he m e tal an d wha t is its nam e ?

,

1 9 Cal c ul a te t he s im ples t form ula of t he following c om poun ds

.

(a) p e r c e nt m e r c ury p e
,
r c e nt io d i ne ; ( b) 4 0 p e r ce nt c al c ium ,

1 2 p e r c e nt c a rb on 48 pe r c e nt oxyg e n ; (c )
, p er c e nt hy d rog e n ,

pe r c e nt nitrog e n ,p e r c e nt oxyg e n .
 CH A PT E R III

E QUA TIO NS V V
IN O L ING NO O XIDA TIO N OR
RE DU CTIO N

E quations are the sentences of chemistry as they

express chemical changes which take place A chemi cal .

change or chemical reaction is a molecular phenomena

in which the composition of the molecule is altered .

U sually a chemical reaction is brought about by

mixing solutions of tw o diff erent substances The .

evidence that a reaction has taken place is (a ) the

formation of a precipitate (insoluble substance) ( b) th e ,

formation of gas bubbles ( gaseous substance) or (c) the ,

change or formation of a color (diff erently colored

s ubstance ) For example ( a ) by mixing a solution of
.
,

po tassium iodide and lead nitrate a yellow precipitate

is produced for the following reaction has taken place :
,

nitrate an d potassium iodi de

will give
pot a s s m m n t
i t ra e

lead io di de
( ins olu b l e a n d yellow )

If hydrochloric acid (hydrogen chloride) is added

( )
b
to a solution of sodium sulfide gas bubbles will be
observed for the following exchange has taken place :
,

23
24 H MICA L RE A CTI ONS
C E A ND T H E IR E QU AT IONS
hyd rogen c hlori d e and so diu m sul fide

w ill give so dium c hloride

hyd roge n s ulfid e

(gaseous )

( )
If aefew drop s of ferric chloride are added to a
solution of potassium sulfocyanate an intensely red color
will be produced due to the formation of ferric
,

sulfocyanate
c hlori d e an d potassium sulfocyanate

wi ll give potass ium c hloride

\
ferric sulfocyanate
( dark red colored )

In
all three c ases as may be see n on e part of each
, ,

molecule has changed places with the part of a diff erent

molecule In order to write chemical equations for
.

these reactions the formulas for the s ubstances which

ac t upon each other are placed t o the left and connected

by the addition Sign while the reaction products

are written t o the right separated by the Sign of equ ality
which means that the number and kind of atoms
on both sides of an equation mu s t be e qual Thus an .

equation demons trates the principle that nothing is los t

or gained in the course of transformation and implies ,

that the molecules to the left are converted into those

t o the righ t In reading an equation the plus Sign is
.

ren dered by an d and the equality Sign by gi ve B alan o

, .
26 CH E MICAL R E ACTIO N S A ND T H E IR E QU ATIO N S

to ionization The number and kind of atoms are

.

identical on each side of the equality S ign In balancing .

equations the correct formula for each compound

involved is of fundamen t al importance for the first step ,

is always to write the formulas of all the compounds ,

as in (a ) ( b) and
,
K nowledge of the correct formula
naturally requires due consideration of the valency of
the elements and radicals concerned The valency of .

the common elements must be memorized and the ,

valency of the radicals can be deduced from the familiar

formulas of a few acids and bases Thus a knowledge
.

of the common acids and bases is essential for the

derivati o n of the formulas of the salts This derivation.

is demonstrated in the following equations

A ll
these equations illustrate that a base and an acid
will give a sa lt and wa ter This type of reaction is called
.

neutralization The equations above are given in the

.

molecular or non ionic form in the ionic form they

-

become :
 E QU A TIO NS 27

( )
4 a Na +
OH
“
H + Cl
‘

N
a.+ Cl
“
H 20
( )
5 8 K + OH
"

H + N0 3 “
K +
N0 3“
H 20
1 "
( 0 ) 2 N a + 2 OH 2H 2 Na +
'
a
‘

SO 4 2 11 2 0
_ _

“
( 1 1 a ) 3K +
30 11 3H + P0 4 3K +

P0 4 3H 2 0 and so on .

An exami nation of the ionic equations (4 a) ( 5a ) ( 1 0a ) , , ,

( l l a ) shows that some ions have n ot changed E g in . . .

“
( )
4 a the N a + and 0 1 on the left appear also on the right ,

and therefore have undergone n o change Similarly .

the K and N0 3 of equation ( 5a ) remain unchanged

+ “
.

The purpose of an equation is to Show a chemical rea o

tion that is any chemi cal chan ge and if all the ions which
, ,

have n ot changed are cancelled there remains from the ,

above equations

( )
1 6 OH H + H 20
"

This is the gen eral equa tion for neutralization and ,

defin es neutralization as the combination of one hydroxyl

ion with one hydrogen ion to give one molecule of water .

B y using this universal statement all the particular

cases can readily be found by adding to t he negative
hydroxyl ion (OH ) the positive metal of any base and
‘

to the positive hydrogen ion ( H ) the negative non

+

metal or radi cal of any acid From the proportion 1 1 .

it is evident that any monoacid base requires one a di ,

acid base two a triacid base

,
three hydrogen ions ;
whi le a monobasic acid requires one a dibasic acid two , ,

a tribasic acid three hydroxyl ions Thus in equa .

tion ( 10) two molecu les of a monoacid base are needed

for neutralization of one molecule of a dibasic acid .

If only one of the reaction products is known in a

reaction the other reaction product is found by sub
28 CHE MICAL R E ACT IONS A ND TH E IR E QU ATI O NS

tracting the atoms of the right from those on the left

Thus if the unfini shed equation is B aClg
, N a2 S0 4
B as O, the following scheme will give the unknown
reaction product :
On the left B a Cl, Na, S 0 4
On the righ t Ba S O;
Remain d er 0 12 N3 2

These remaining tw o c hlorine and two sodium at oms

naturally give t w o molecules of sodium c hlori d e hence ,

the completed equation is

1
( )7 B aClg N a gSOI B aSO , 2 NaCl

Writing this equation in the ionic form

“
B a + + 2 Cl 2 Na + SO , B as O , 2 Na +

2 C]

and cancelling those ions which remain unchanged ( Cl

and N a ) the equation becomes
+

“
( )
1 8 B a + + so . B a so .

This is again a general statement namely that every ,

soluble barium salt (furnishing the barium ion ) with any

soluble sulfate ( which furnished the sulfate ion) will give
a prec ipitate of barium sulfate ( which is insoluble) I t .

is eviden t that an ionic equation cov ers ma ny c as es ,

for one may t ake as the soluble barium sa lt either B a Clz ,

etc an d for the soluble sulfate ei ther N aQSO r

.
, ,

K s I etc but it refers only t o on e specific reaction

, .
, ,

e g
. .the formation Of barium sulfate A non io n ic
,
.
-

or molecula r equation covers only on e particula r c ase ,

for from such an equa tion as ( 1 7) we can not make t he

deductions which were possible from
B alan cin g Mole cular E quation s A n unfinished equa .
-

tion may be given in which there are more atoms in the

 EQUA T IO NS 29

reaction product tha n in the reacting substances A .

simple case is Cu O R C] 0 11 0 12 and as 2 0 1

can not be subtracted from 1 Cl the number of H Cl ,

must be doubled
On the left Cu 0 2 B 2 C]
On the right Cu Ch
Remainder O 2H

which will form one molecule of water thus ,

1
( )9 Cu O 2 H Cl CuClz H 20

The problem be comes more difficult when two or more

compounds are forme d and In this case greater knowledge
,

of chemistry is required For example an experiment

.

shows that on addin g a solution of sodi um carbonate to a

,

solution of alu mi num sulfate a white precipitate as w e ll ,

as gas bubbles are formed H ence the reaction products

.

are (a ) an insoluble compound and ( b) a gaseous com ,

pound A S neither the A l the N a nor the SO, radical

.
, ,

form gaseous compounds but as the carbonates yield ,

readily 0 0 2 the unknown gas must be 0 0 2 and the u n

,

finished equation is
A12 ( SO 4 ) 3 N3 2 0 0 3 002

The white precipitate whi ch is the insoluble compound

,

formed in this reaction must be a c om pou n d of aluminum

,

for all so dium compound s are soluble A t first it appears .

to be the carbonate but as carboni c acid is given Off this

, ,

can not be the case The other possible compounds to

.

consider would be the oxide and the hydroxide of alumi

num for in this reaction the other insoluble alumin u m
,

compounds like the phosphates silicates etc can not , ,

.

be regarded as possible reac tion products as n either of ,

these acid r adicals are present The reaction occurred in .

30 CH E MICAL R E AC TIO NS A ND TH E IR E QU A TIO NS

watery solution hence the hydroxide is probably formed ;

if so then water must have taken part in the reaction
, ,

and the unfinished equation becomes :

A 12 ( SO I ) 3 Nac 3 H zO C0 2 A l( OH ) 3
The nex t metal to account for in this equation is so dium ,

which loses the carbonate radical and must combine ,

with the sulfate radical to form sodium sulfate

A lg( SO 4 ) 3 Na 2 C0 3 H gO C0 ; AJ ( 0 H ) 3
N3 2 8 0 4
An examination of this unbalanced equation shows that
there are t w o aluminum to the left an d hence 2 A l( OH ) 3
—
must be formed There are 3SO 4 radicals to the left
—
.
,

thus 3Na 2 S0 4 are produced r this in turn requires -

3Na zCOa and these three molecules will yield 30 0 2

,
.

Finally as 2 A] ( OH ) 3 are formed there are 2 X 3 6 ,

hydrogen atoms necessary and these a re presen t in

3H 2 0 M aking these corrections the finished and
.
,

b alanced equation is :
( )
2 0 A 12 SO
( I) 3 3Na 2 C0 3 3H 2 0
3C0 2 + 2 A l (OH ) 3 3N a 2 8 0 4
As a test of correctness the following checking scheme is
used
Al ( SO I ) N a C O H
To the left 2 3 6 3 6
To the right 2 3 6 3 6

From this we see that one atom of oxygen from each of

the three carbonate radicals reappears in a molecule of
the hydroxide .

To write equation (2 0) in the ionic form the soluble

salts are written as ions while those ions whi ch appear
,

on both sides are cancelled and there remains : ,

“
2
( )1 30 0 3 3H 2 0 2 A l( OH ) 3 3COz
 E QUATIO N S 31

The general rule drawn from this equation is that every

soluble aluminum salt will react with soluble carbonates
and water to give insoluble aluminum hydroxide and
gaseous carbon di oxide I t is again evident that.

equation (20 ) referred to a particular case while equation ,

( ) refers to a specific reaction which covers a number

2 1
of particular cases for the aluminum su lfate may be
,

substituted by aluminum chloride or alu mi num nitrate , ,

etc and the sodium carbonate by potassium carbonate

.
, ,

or lithium carbonate etc ,

.

B alan c in g Ioni c E qu ation s — In balancing an u n fin

is he d ionic equation the charges on the ions must also be
balanced A S a rule the balancing is simple if the
.

charges are ba lan ced first before the atoms are balance d .

“
Thu s in 003 there are three positive
charges on the iron and two negative charges on the
,

carbonate radi cal and to make their sum zero converse

,

and add and 3( that is two ferric ions

( together six positive charges ) and three carbonate ions
( together six negative charges ) t herefore : ,

22
( ) 30 0
) F6 2 ( 0 0
_

3 3 3

It is not necessary that the sum of the charges on each side

of an equation be zero as in it can be any integer
, ,

pr ovid ed this sum is the same on both sides of the equation .

Thus in (23) Pb as
++ P bs 2H +

there are two positive charges on the left which equal

the two positive charges on the right Similarly in .

the equation
2
( )4 Z n ( OH ) z 2 OH l 02 2 H 20
"

there is on both sides of the equations an excess of tw o

negative charges while in ,

“
( )
2 5 CI 2 0 7 2 0 11 ZCrOr 2H 20
" "
’
32 CH E MICAL R E ACT IONS A ND T H E IR E QU A TIO NS

the sum is four negative charges on both sides The sum .

of the ionic charges may thus be diff erent for diff erent
reactions but must be equal on both sides of the
,

equation .

The general meani ng of the last four ionic equations

is that
( )
2 2 any soluble ferric salt w ith any soluble carbonate
w ill form an insoluble precipitate of ferric carbonate ;

( )
2 3 any soluble lead s alt and hydrogen sulfide will give
insoluble lead sulfide and liberate hydrogen ions ;
( 2 4 ) zinc hy d roxide dissolves in ba s es ( OH and
forms zincates and water ;
( 2 5 ) soluble bichromates with bases g ive soluble chromates
—
.

Rule s f or Finishin g an d B alan cin g E quation s The .

rules in balancing and finishing equations are summarized

as fol lows :

A
( ) U nfinished equations in wh i ch on ly the rea cting
substances are given and none or one of the reaction
,

products ( compare equations ( )

2 0 I n

such cases there is usually an exchange of the positive

atoms or radi cals accordi ng to the type MN
, M N
’ ’

M N ’
M N where M and M are positive elements and
’
,
'
,

N and N negati ve elements or radicals The finishing

’
.

of such problems requires

First the correct formulas for the reacting substances
, ,

( to the left ) and the correct formulas of the reaction

products ( to the right) T he reaction products are
.

usually go t ten by exchanging the positive or the negative

constituents of the molecules giving due consideration
,

to the valency .

Secon d balance the atoms as given under B

, ,
.

B
( ) B alancing equations means equa lizing the number
and kind of atoms on both sides of the equation : B egin
wit h an y sym b ol on t he l ef t an d c heck the same numb er
34 CH E MICAL R E AC TIO NS A ND T H E IR E QUA TION S
little water and conce ntrate d sulp huric ac id is adde d How m a ny gram s .

of H 8 0 sho uld be used and how m a ny gram s of boric aci d are obtai ned ?
3 4 ,

N3 2 B 40 7 1 0 H 2 0 . H 38 0 4Na zSO 4 4 H 3B 0 3 5 H 30 . .

6 . How m any kilogram s of K NO; can be m ade from a m etric ton of

Na NO; , how an d m an y kilogra m s of K CI m ust be used ? ( A m e tric ton
e qu a ls kg ) .

7 C alc ula te t h e lo ss in we ight if 1 5 gr am s of m arble are he a te d until

.

t he ch a nge is c o m ple te .

8 To 32 gr am s of a solution of s ul p huric ac i d an e x cess of B a Cl w as

. z

a d ded T he B a SO o b tain ed we ighed

. 4 gram s Calc ul ate the .

pe rc e ntage Of sulp huric ac id in the sulp huric ac id solution .

9 How m a ny gram s of H FI c a n be m a d e fro m 2 0 grams of fluorsp ar

.

( Ca Fl ) a n d how m a ny gra m s of sulp huri c ac i d m us t be ad ded ? Wh a t

z ,

will be t he volum e of H F] gas if on e m ole o cc upies li te rs ?,

1 0 How m a ny gram s Of N H c an be o b ta ine d fro m 50 gr a m s of

.
;

a m m onium c hlori d e a n d how m a ny gr a m s of c a lc iu m hy d roxid e a re

,

necessa ry ? Wh at will be t he volum e of the N H gas ? ;

11 How m any gram s Of nitric ac id will be obtained by : (a ) hea ting

.

2 50 kg of sod i um nitra te with s ul phuri c ac i d ; ( b) heating 2 50 kg of

. .

potass ium nitrate with sulphuric ac id

1 2 How m a ny gram s Of c rystallized c up ri c nitrate ( conta in ing 3 m ol
.
'
.

H O) m ust be he ate d to r e d ne ss to m ak e 50 gram s of c u p ric oxi d e ?

z

18 How m a ny gr am s of nitric ac i d are n ee de d to convert : ( a ) 500

.

grams so d ium hyd roxi d e into so d i u m nitrate ; ( b) 500 gr am s potass ium

hyd roxide in to potass ium nitrate ; (c) 500 gram s c alc ium hyd roxi de into
c a lc iu m nitra te ; ( d) 500 gra m s c al c ium oxi d e into c a lc i um nitra te ; (e) 500

gram s ba rium hyd roxi d e into barium nitr a te ?

1 4 A solution c ontains e x a c tly
. gram s of so dium hyd roxide in
1 lite r Calc ula te t he qua ntities by we ight of (a ) H CI (b) H N O
.

( c) H SO ( d) H P 0 whic h w ill be re quire d to neutrali ze 10 c c of this

z 4, 5 4 . .

solution .

1 5 In asc e rt aining the stre ngth of a d il ute solution of H CI 50 c c we re

.
,
. .

m e as ured out an d n eutra li zed with a s ol ution of sodium hy d roxid e ,

c onta ining gram s Na OH in 1 c c Thirty fiv e c ubic c e ntim ete rs ‘

-
. .

Of this s olution w as re q uire d Wh a t is t h e stre ngth of the H CI? How

.

m a ny gr am s H CI are in 1 c c ? . .

1 9 F orty c ub ic c e ntim e te rs of a solution of potas sium hy roxid e

.

c ontaining gram s of K OH in 1 c c we re required to neutrali ze . .

4 0 c c of a solution of H SO
. . How many gra ms of sulphur ic ac id d id
, I.

1 5 c c of t h e sulp huri c ac i d sol ution c ont ain ?

. .

1 7 Three hun dred and e ighty gr am s of m er c uri c c hlorid e are d issolve d

.

in wa ter How m any gra m s of K 1 m us t be ad ded to preci pitate all th e

.

m e rc ury ? How m any gr am s of H gI will be ob taine d ? ,

1 8 If 5 gram s Of c rystallize d c Oppe r sulf ate Cu SO 5H O are d is solv e d

.
, I. z ,
 E QUATI O NS 35
I

in w ate r how m any grams of H 8 are necess ary to prec i pitate all th e
, 2

c o pp e r as c o pp e r sul fi de ? How m any gram s of F9 8 an d 2 5 pe r ce nt

H Cl are re quired to g e ne rate e nough ms for this pur p o se ?
1 9 How would you m ak e a norm al solution of the follo w ing sub
.
,

s ta n c es : ( a ) H CI (b) H N O ,(c ) s o (d) Na OH (0 ) N H OH ? How

a, s, s
,

would you m ak e a N/1 0 solution of (f ) (g) N aCl ( h) 8 0 ; , 3

a 2 N s olutio n of (i ) H F] (! ) B P 0 , ( k) Fe SO .?
3 4,

2 0 A nsw e r t he following prob le m s by inspection

.

( a ) How m uc h K O H will b e re quired to n e utralize 1 lite r N solution of

H NO 1 lite r N solution of H SO
;, 1 lite r N sol ution of H P 0 ? ( b)
z i, 3 4

How m any gram s of Ca (OH ) ? g

2 1 Write t he e q uations for p re p aration Of the followi n g

.

( a ) C up ri c oxid e from c u p ric c a rbon ate ;

( b) C up ric c hlorid e fro m cu p ric oxid e ;
(c ) Fe rric hyd roxide from fe rric s ulp hate ;
( d ) Fe rrous sulfide fro m fe rrous s ulp ha te ;
(c ) Alum inum c arb ona te fro m a lum inum nitra te ;
(f ) Alum inum hy d roxi de from alum inum c hlorid e .

Sta te in eac h c ase w hic h substa nc es are n e c essary for the re ac tion a n d
whic h s ubsta nces are p rec ipitate d .

22 How w oul d you m ak e t he following c om poun d s

.

( a ) Cu p ric c hlori de from c up ri c s ulf a te ?

( ) Cup ric sulphate fro m c up ric c hlorid e ?
b
(c ) Fe rro us s ul ph ate from fe rrous s ulfid e ?
(d) Fe rric c hlorid e from fe rric sulph ate ?
(e) Alum in um su lfate fro m alum inum c hlori de ?
0) Alum in um c hlori de from alum inum s ulfate ?

A s none Of these c o mpoun d s are ins oluble in which w ay should the y ,

be p re pare d Base your an swe rs on e quations wh ic h Show p os sible

reac tions .

2 8 Y ou are giv e n a q ua ntity of lea d a ce ta te solution

. How woul d .

you p re pa re : (a ) le ad c hlorid e (b) lea d nitrate (0 ) le ad sulfate

, , le ad ,

c hro m a te (e) le ad oxi d e (f ) lea d c a rb on a te fro m this solution ?

, ,

2 4 Sta rting with li m e Ca O how wo uld y ou m ak e ( a ) 0 8 0 1

. ( 5) 2,

0 8 8 0 4, (C) CR ( NO S) 2’ (CI) 0 3 0 0 3, (8 ) BO lld

2 5 D es c ribe a t l e as t three ways of m aking
. fe rric c hloride from fe rri c
s ulpha te .

26 . Write quations for t he form ation of : (a ) P russ ian b l ue

t he e

from fe rric ions an d fe rrocy ani de io ns ; an d (b) T h um bull s ’

b lue from ferrous ions a n d fe rric yanid e ions .

27 . Finis h t he following e q uations

(0 ) Z II H as ++

( b) NICO :
(0 ) Ni “
H 28 0 4
( NH 4 ) 2 S
36 CH E MICAL R E AC TION S A ND EQ UA T IONS
“ “
(d) H gNOs I C l
“

(6 ) OH “

(f ) A R
CH ) : A 130 : I
“
(a) FGS I H
“ +
s
( h) Ca 7
(i ) Ba H
B a CO a
‘ ’

V 4“
(1) A ”
A R
CH ) : H
( lo) Ca ( OH ) z 7 Ca ( SH ) z H zO
(1) Na Cl N H 4H COa Na H COs 7
(m ) Cu O H zO B a ( OH ) z Cu S
(n ) CO Clg 6H 30 CO H
’

(0 ) CO CI: 6H 30 . 0 0 0 13 I
(p) M110 1: ( NH 4 ) 38 Mu ( sH ) z
(q) 6K CN Fe so4 K 4Fe ( CN) o I 7 13 5 0 4
““
,

28 . B alan c e th e following e quations

(a) 0 3 0 0 3 +2H N0 3 0 & (N 0 3) 3 1130 00 :
(b) D 10 14 NH ; m
SI H 2 ) 4 “ I NH 4CI
"

(c ) 8n H zO 2 H 38 SiOg
( d) K zSt I K O H K F K .Si0 .
““

(8 ) SiF4 H gO H ; SiO4 H gSiF.

0) P0 15 ASFS P Fs A B OI;
 CH A PTE R I V
V V
E QU A TI O NS IN O L ING O IH DA T IO N A ND
RE DU CTI O N

Oxidation an d Re du ction —
Oxi d ation
an d reduction
.

are d efined in a previous chapter as the incre ase or d e

creas e in the valence numbers In an equation thi s .

increase or d ecreas e of the valence number must als o be

balanced . Thus an increase of two in the valence
number of one element must be balanced by a d ecrease
.

of two in the valence number of some other element .

In other words oxidation cann ot take place unless there

,

is a reduction in some other element In its simplest .

form this principle is illustrated in the displacement

reaction
( )
26 Cu “ Fe Cu Fe ++

In this cas e the metallic iron ( Fe valence number 0 )

acquired two positive charges from the cupric ion (Cu ++

valence number +2 ) an d was oxidized (increas ed it s

valence number) to ferrous ion ( Fe H valence number - "

while at the same time the cupric ion w as reduced

( d ecrease d it s v alence nu mber ) to metallic copper ( Cu

valence number The exp eriment is readily per

forme d by p lacing a piece of blank iron in a solution of
any copper salt e g blue vitriol and the iron will be
,
. .
, ,

cov ered by a film of finely divided copper in the form of

a brownish precipitate If sufficient time is gi ven for
.

the reaction to take place all of the copper may be pre

c ipit ate d an d the blue color of the solution will change
,

to the greenish color of the ferrous ion In thi s case .

37
38 CH E MICAL R E ACTION S A ND TH E IR EQ UATIO NS

the metallic iron has replaced the co pper ( see also

Chapter
N ot only with positiv ely charge d elements but also ,

with negativ ely charged elements such a displacement

takes place
'“
2
( )7 0 12 2B I 20 1 B T2
"

In this case chlorine (O) w as reduce d to chloride ion

and the bromi de ion —
1 ) was oxi dize d to bromine
It should be note d that in equation ( 2 6) the transforma
tion of an element to its ion w as oxidat on while in ,

equation (2 7) this transform ation w as a red uction in the ,

first case the val ence number increase d in the secon d ,

case the valence number decrease d

—
.

Me tals an d Non m e tals A s a general rule metals

-
.

are oxidized an d non metals are re duced to binary

,
-
1

compounds an d oxi dized to tertiary compounds A n

,
2
.

exception to this rule is the direct oxidation of non

metals by oxygen e g burnin g sulfur phosphorus or
,
. .
, , ,

carbon in air as in these reactions b inary compounds

,

are formed e g SOs P 2 0 5 CO or 0 0 2 The reason for

, . .
, , , .

this is foun d in the assumption that oxygen is always

considered negative or 2 and therefore in non metal
, , ,
-

oxides the non metal is positi ve with regard to oxygen ;

,
-

while in non metal hydrides

-

s NH a CH 4 ) an d , ,

the binary salts K CI CaS A lN FOO2 ) the non metal , , ,

-

is always negative as hydrogen is p ositive

,
and all
metals are positi ve .

I n the equation

( )
28 2 118 0 2H g I 0 2 " ”

the mercury of mercuric oxide w as re duced the valence ,

l
Bin ary com pounds ha ve o n ly two kinds o f atom s e g NaCl Fe Cl , . .
, , ,.
2
Tertiary com poun ds ha ve three di ffere nt kind s atom s e g K CN ,
. .
, ,

B 3 8 0 4, Na sP OA
 E QUATIO N S 39

number being decrease d from 2 to 0 while the oxygen of ,

mercuric oxi d e w as oxidi zed the v alence number being

—
,

increased from 2 to 0 H owev er in the equation

.
,

29
( ) 4Na 02 2 N a 20

metallic so dium (0 ) is oxidize d to sodium oxi de ( N a

while the oxygen gas ( 0 3) w as reduced to an oxide

B alan cin —
g Oxidation an d Re duction A s seen in these
.

equations oxidation is exactly counter balanced by re

,
-

duction for the increase in v alence nu mber is the re

,

ciproc al of the decrease in v alence number in other ,

words if the increase is a d de d to the decrease the sum is

,

zero Thus in equation :

.

oxidation of iron to ferric ion increase of two ,

reduction Of cupric to copper ion decrease of two ;

oxidation of two bromid e ions to bromine increase
of 2 X 1 2
reduction of chlorine to chloride ions decrease of
2 X 1 2 —
oxidation of two oxi d es to oxygen increase of
2 X 2 4
reduction of two mercuric to merc ury decrease
of 2 X 2 4 —
oxyd ation of four so dium increase of 4 X 1 4
re duction of two oxygen oxi d e decrease of
—
to
2 X 2 4

Sum Is Z erO
.
—The sum of this increase an d decrease
isalways zero in a correct equation . A more complex
example is

( )
30 SD 2 H N0 3 H ao H 4SIIO4 N20 3 .
40 CH E MICAL R E ACTION S A ND T H E IR EQUA TION S

In this equation metallic tin ( 0 ) has been oxidized to a

stanni c compound (4 ) —
stanni c acid while the ni trogen ,

of ni tric acid ( 5) has been reduced to nitrous oxide

thus the tin has incre ased by 4 an d tw o n itrogen atoms
ha ve ea ch decrea sed by 2 an d 2 , 2) 4
,

— —.

This increase or d ecreas e of the valance number is

perhaps best illustrated by writing the val ence numbers
which change under the respective symbols :
( )
31 2H B r H .so . so2 B r.
—1) ( )
6 ( )
4 ( )
0

In this reaction two bromine atoms 1 ) of hydrobromic

acid have been oxidized to free bromin e ( O) and the ,

sulfur ( 6) of sulfuric acid has been reduced to sulfur (4 )

of sulfur dioxi d e However in
.

m
'

32
( ) 2 H B Mn o2 o. Mu so . B r.
—1)
r

( )
4 ( )
2 ( )
0

not the sulfur of sulfuric acid but the manganese (4 ) of

,

manganese dioxi d e has been reduced to manganes e ( 2 )

of manganous sulfate Writing the later equation in
.

the ion ic form

33
( ) 2B r M D Oz 4H + M n + + B ra 2 H 20

illustrate s the rule that any soluble bromide in t he

presence of hyd rogen ion ( any acid ) will give with ,

manganese dioxide a manganous compound and free

,

bromine .

In balancing an unfini she d equation it is always

adv an tageous and in many cases absolutly neces sary
, ,

to strictly follow the rules .

Th e T h re e Rule s —Firs t balance the valence numbers

,

of the elements Write under each symbol its v alenc e

.

n um b er then O b serv e whic h elemen t s are oxidize d or

,
42 CH E MICAL R E ACTIONS A ND TH E IR EQ UATIONS

dotte d line s shows that ma nganese has bee n reduced

from 7 to 2 ( 5 steps ) while the iron is oxidized from 2
,

to 3 ( 1 step ) In order that oxidation and re duction are

.

balanced the factors are re versed : 1 X 5 steps

, 5 X 1
step which means that 1 molecule of permanganate is
,

sufficient to oxidize 5 molecules of a ferrous compound

an d the unfini shed equation becomes :

Mn Oi "

5Fe + + M n ++

The proportion of a to 5Fe mus t be kept throughout

the succeedin g operations it may be d oubled — or
tripled — but the proportion of 1 to 5 must be
preserved .

The second step is balancing the ionic charges They .

are counted and ad de d together separately for each side

of the equation thus : ,
0

on the left :
one negative charge on the perm an gan te
5 X 2 positi ve charges on the iron
therefore excess of positi ve charges
on the right
t w q positive C
harges on the manganese
5 X 3 positive charges on the iron
a total of positiv e charges
As the number of charges on both Sides mus t be equal ,

for nothing can be gained or lost during a chemic a l

reaction some other substan ce must have reacted which
,

furnis hed either 8 pos itive charges to the left or yielded ,

8 negativ e charges to the right side Of the equation .

The p ositive charges are usually furni shed by H +

( acid ) d the negati v e cha ges by OH ( ba es ) d

"

s an
,
r s an ,
 EQ UATIO N S 43

as it w as specified that the reaction occurred in aci d

solution 8 H must be added to the left in ord er to
+
, ,
.

balance the charges :

Mn Or '

5Fe ++ SE + M
n + +

The sum of the ionic charges is thus eq ual on both sides

for — 1) ( )
2 1 7 ; and the
first and secon d ste p of balancing is accomplished It .

remains to balance the atoms Checking off the atoms .

leaves 4 oxygen atoms and 8 hydrogen atoms on the

left which will naturally gi ve 4 molecules of water .

Therefore the complete d equation is

( )
84 M n O r 5F e + + 8 H + M n ++ 4H 20 .

Thi s ionic equation is the general statement of the

problem and enables the construction of many equations
for particular cases by simply supplying the ions with
~

the corresponding radicals or elements In other words .

,

t he permanganate ( Mn Or ) can b e any soluble per

manganate either of sodium potas sium etc ; the ferrous
, , , .

salt can be any solub le salt either sulfate chloride , , ,

ni trate
, etc ; an d the acid can be either H CI s OJ
.
, ,

H NOa etc
—
.
,

P r oblem 2 A ni trite solution is oxi di z ed to a nitrate

.

solution by an aci difie d bichromate solution

First the valence numbers are written under the ions
,

“
N0 2 Cl zO f
‘ ‘ "

N0 3
3 5
12 6

The nitrogen of the nitrite therefore has been oxidized

—
from 3 to 5 increased 2 steps The chromium of the .

chromate has been reduced from 12 to 6 decreased 6 .

-
44 CH E MICAL R E ACTIONS A ND TH E IR E QU ATIONS

steps . To balance the factors are r ev erse d ,

therefore ,

“
6N0 2 2 Cr2 0 7 6N0 3
‘

The proportion 6 2 can in this c a se be simplified to 3 1

an d the unfi ni shed equation becomes :

3N0 2 Cl zO 7 3N0 3
"
’

Secon d, the charges are counted on both sides thus ,

on the left there are 3 ni trites 3 negative charges

1 bichromate 2 negative charges
a total of 5 negative charges
on the right there are 3 ni trates 3 negative charges
2 chromic ions 6 positi v e charges
a total of 3 positive charges

To ba lance + 3 and requi res either 8 positive —5

charges to the left ; or 8 negative charges to the right .

A s the reaction occurs in aci d so lution eight hydrogen ,

ion s must be added which give the neces sary eigh t

p ositive charg es to the l eft Side and the equation be ,

com es :
3NO2 8H " 3N0 3
l
" ‘
" ”

'

an d the sum on both sides equal s 3 positive charges

3( —2) 3( 3

T hird, the atoms are balance d N it rogen and chromium .

balance O n the left are ( 3 X 2)

. 7 1 3 oxygen
atoms while on the right there are only ( 3 X 3)
,
9 .

T his excess of 4 oxygen atoms at the left will give with

the 8 hydrogen atoms four molecules of water and the
fini she d equation becomes :
“
N 3N0 3
“
5
( )
3 3 02 Cr20 7 SH * ZC T + + 4 H 20
"

r
 EQ UATION S 45

In a few cases it may happen that a substance is

oxidize d and reduced in the same reaction that is one , ,

part of the substance is being oxidized and the other is

being reduced It is then advisable to write the formul a
.

of thi s substan ce twice :

K ClOs K OIO . K CI K CIO.

—1)

This diagram shows that the chlorine of the

c hlorate is reduce d to chloride while another par t
of the chlorate is oxidize d to perchlorate In the
first case the valence number has decreased 6 steps and
in the second it has increas ed 2 steps I t follows that .
,

for every 2 molecules of potassium c hlorate giving 2

molecules of potassium chloride 6 molecules of pot as ,

sium chlorate are transformed to 6 molecules of potae

sium perchlorate hence 8 molecules of potassium chlorate
,

give 2 molecules of potassium chloride and 6 mole

c ules of potassium perchlorate which can be simplified to
,

QUE ST I ONS

1 De fin e ( a ) oxi d ation an d r e duc tion , ( b) d i s p la c em e nt , ( c ) st a g es of

.

oxid ation, (d ) ionic e quation , an d (e) non io n i c e quation

-
.

2 Wh at is t he c o st of p re p aring 5 kg of hy d roge n gas fro m zinc a n d

. .

sulfuri c ac i d ? ( Ass um e the p ric e of Zn to be 50 9! pe r kilogram , an d tha t

of H 38 0 4 6 9! pe r kilogram ) .

8 Wha t we ight of p ho s p horus will co m ple te ly re m o ve t he oxyge n

.

from 2 kg of air ? ( Ass um e th at air contains 2 3 pe r c e nt of oxyge n

.

by we ight ) .

4 H ow m a ny gr am s Of oxy ge n c an b e o bt ain e d fro m 75 gram s of a

.

3 pe r c e nt solution of hyd ro ge n p e rox ide ?

5 How m any gra m s of a 6 p er c e nt solution of hy d rogen p e roxid e will
.

c on ve rt 5 gra m s Of le a d s ul fide into lead s ulfate

6 How m an y gram s of pot ass ium c hlora te are ne c e ss ary to furnis h
.
46 CH E MICAL R E AC TIO N S A ND TH E I R E QUA TIO N S
th e oxyge n for conversion Of 25 grams m e tallic co ppe r into cup ric oxide ?
( 5) How m any gra m s O f K CI will be form e d ? (c ) Ca n this re a ction be
writte n in t he ionic form ? ( Give re asons ) .

7 How m a ny gram s of am m onium nitra te a re ne c ess a ry to m ak e 1 00

.

grams Of nitrou s oxid e whic h is formed by he a ting t he salt ?

,

8 Wh at are t he sub s ta n c es form e d whe n a b ro m ine solution is add ed

.

to a potass ium hyd roxid e sol ution ?

9 Write an e qu ation for t he re ac tion O f ( a ) b ro m id e m a nga n e se
.
,

d io xid e s ulfuric ac id to gi ve free bro m ine ; (b) so d ium b rom ide m a ng a

, ,

ne se d ioxide sulf uric ac id to give free bro m ine ; (c) potass ium bro m ide
, ,

m a nga n e se d ioxid e p ho sp horic a c id to give b ro m ine

,
.

1 0 How m a ny gram s of 50 p er c e nt s ulf uric a c id c a n be m a d e fro m

.

1 0 gram s of s ulfur by burning t he sulf ur in air an d p ass ing t he s ulf u r ,

d ioxide thus form e d o ve r finely d iv id ed p latinum whic h ac ts as c atalys er ,

thus p ro d uc ing sulf u r trioxide ? ( Give co m p le te se t of eq u ations ) .

1 1 T we nty kilogram s of p hO Sp hat e ro ck Ca ( P 0 ) are h e at e d with

.
, a 4 2,

s a n d SiO, a n d coke C in a n e l ec tri c furn a c e

z, , ,
T h e cok e b urns to C O .
,

t h e p ho s ph at e is re d uc e d to p ho sp horus a nd Ca Si0 is form e d How ‘

, 4 .

many gra m s of p ho sp horus a re Obt aine d ?

1 2 T wo gr am s of a n a lloy of C u an d Ag a re d is solv e d in nitri c ac i d
. .

To this sol ution H CI is add e d T he p re cip itat ed A gCl w eighs gram s

. .

( )
a How m a ny gr a m s of A g a n d C u w e r e p r e se nt ? ( b) W h a t is t h e pe r

c e nt age of Ag a n d C u in t he a lloy ?

1 8 T hirty kilogram s of an ore c onta ining 60 pe r c e nt s s are hea t e d

. ;,

with iron How m any kilogram s of anti m ony are form e d ?

.

1 4 A m e tric ton
. 1 000 kg ) of pyrite s c ont a ining 8 p e r c e nt of
.

foreign s ubstan ces is burne d in a sulfuric aci d plant (a ) How m any .

kilogram s of fe rric oxi de rem ain ? ( b) How m any kilogram s of sulfur

d ioxide are for m e d ?
1 5 How m a ny gr a ms of ( a ) bro m in e ( b) io d in e are p ro d uc e d by
.
,

p ass ing a c urrent of c hlorin e gas through a solution of (a ) 2 5 gra m s Of

m a gn e s iu m bro m id e ( b) 10 gra m s of potassiu m io d i d e ?
,

1 6 How m a ny gra m s of ( a ) w at e r ( b) c arbon d ioxid e a re for m e d by

.
,

b urning 1 kg of m ethan e ( CH )
. 4

1 7 T he hyd rog e n ob t ain ed from

. gram s of zinc an d hyd rochloric
ac id is p as se d ov e r h e a te d m e rc uri c oxi d e How m any gram s of wate r
.

a n d how m a ny gra m s of m e rc ury a re p ro d u c e d ?

1 8 How m a ny gram s of nitri c oxid e N O a re form e d whe n 7 5 gra m s

.
, ,

of c o pp e r are diss olved in nitri c acid ?

1 9 How m a ny gram s of c hlorine c a n b e Obta ine d by h e ating
.

gram s of m anganese dioxid e with hyd rochlori c ac id ?

2 0 How m a ny gram s of c rys t c o ppe r nitra te m us t b e he ated to
. .

re d ness in ord e r to obtain gram s of NO ? T he othe r p rod ucts ;

form ed in this reaction are 0 R o and CuO 3, i ,

.
 EQ UATIO NS 47

21 . H ow m any
gram s of (a ) iron (b) zin c (c ) alum inum are re quire d
, ,

to p reci pitate gram s of silve r from a silve r nitrate solution ?

22 How m a ny gram s of io d ine will be p re cip itate d from a p otassium
.

iod id e solution by t he c hlorine whi c h is form e d from

,
gram s m ang a
nese dioxide an d hyd rochlori c acid
2 8 How m a ny kilogram s of iron a n d s ulfuri c ac i d will b e nee d e d to
.

m a ke 100 kg of hyd rog en gas ?

.

(a ) Zn
“
Ag+
Zn Ag “
24 B alan ce t he following e qua tions :

(b) S CI S Cl :

(0 ) P 0 13 K ClOs FOCla K CI
(d ) mm . C
P H . 1 H .P o.
(e) Sb CI, Sb gCla
( I) s os Sb os I 0 2
“ “

(a) K OCl H OCl K ClOs H CI

(11) N O CI: NOCl
(i ) Cd 8 0 4 Cd S Cd O SO:
(! ) Cl Clz I H :
‘““ Cl Clg ‘
H CI
2 5 Finis h an d balan c e t he following e quation s
.

(a ) H gO C l: H gClz H OCI
( 5) Bi H N O; B i ( NOs) a
(0 ) N8 I H I O
““ 7+
“
(d) A S I CI:
“ I
(e) ( NH 4) 2P LQCIQ Pt 2 0 13
( I) FeS I 0 2
“ “ F9 20 :
(9 ) K O H CI: K oCl K CI
( h) K CI F,
(i ) Al H CI
( J ) 0 110 I H 2
““

(ll ) H B CIII I H 8
““ I
2 6 Ord in ary gun p owd e r is a m ixtu re of saltpete r, c a rbon , an d sulfur
. .

T he reac tion p ro d uc ts are K 30 0 3, K zSO4, K .S., 8 0 2 , a n d N2 .

Com plete the following reac tions :

(a ) K NO; I C ““ K 30 0 3 I CO:
““ N:
( b) K N Oa I C -
S K 28 0 4 C O: N 2
““
(0 ) K NO: I C ‘ ‘
S K zs 4 0 0 2 I N:
Ass um ing that these are all t he rea c tions c onc e rned in an e x plosion ,
ca cl ulate t he c orre ct prop ort ion of saltp ete r c arbon an d sulf ur
, .

27 Construc t e q uations for the re d uc tion of p otass ium f rom p otass ium
sulfi de b y m ea ns of (a) iron (b) a lum inum (c) m anganese T he re actio n
, , .

pro ducts are (a) Fe S (b) A l S an d (c) Mgs Whic h m etal per poun d
, s s, .

will yie ld t he largest q uantity of potassium Whic h m etal is m os t

e c onom i cal ? ( A poun d of Fe c osts AI 2 5 16 a n d Mg
,

Whi c h re ac tion will tak e p lac e m ost rapi d ly ?

 CH A PTE R V

CO NTRO L O F RE A CTI O NS

A chemical reaction is a molecular phenomenon by

which the composition of the molecule is changed The .

most frequent type of reactions are th ose in which one

part of the molecule is exchanged by a part of a diff erent
—
molecul e thus in the reaction A B CD AD CB
we may say that B has changed places with D or A ,

h as been exchanged by B for C and we draw the infer

,

ence that either A has a greater attractive force to D

,

than to B or that B has a greater attractive force to

,

C than to A P ostponing a discussion of this force of

.

attraction holding the atoms in the molecules together ,

we find that a reaction is practically never 1 00 per cent

efficient This means that not all of the AB and not
.
,

all of the CD has been transformed to A D and CB In .

every reaction there is a certain and definite percentage

of transformation and this percentage form s the basis
,

of the measurements in physical chemi stry H owever .

,

the percentage of reacting substances and reaction pro d

u c t s is not the only factor which can be experimentally

determined for a given reaction E very reaction requires

.

a certain space of time ; some may be instantane

ous ; some may be so extremely slow as to be hardly recog
n iz able . I oni c reactions or reactions which occur in
solutions are usually instantaneous while molecular ,

reactions usually require a measurable period of time .

For both kinds of reactions ionic and molecular it is

, ,

essential that the ions or molecules come in close contact ,

for if the two ions or molecules are far apart they cannot ,

48
50 CH E M ICAL RE ACT IO NS A ND T H E IR EQ UATIONS

In crea s e Of Surfac e by Subd ivision

increase of .
—
A n

the con tact surface be tween two substances will naturally

i n crease the number of diff erent molecules comin g into
close contact and hence increase the possibility of the
,

molecules colliding B y placing a cube of iron contain .

in g 1 c c in hydrochl oric acid it is e viden t that the

. .
,

contact surface be tween the solid an d liquid is 6 sq cm . .

,

for the e d ges of the cube are each 1 cm lon g an d each .

,

side has a surface of 1 sq cm and there are six sides on . .

,

the cube If this cube is cut into eight smaller cubes as

.
,

shown in Fig l the volume an d mass of the iron as well

.
, ,

FIG . l .
—r
Inc e as in g th e su r fa
ce by s u bd ivisio n.

as the total number of iron molecule s has not been

changed but the surface h as been double d making it
, ,

1 2 sq cm and consequently twice as man y molecules

. .
,

Of iron are in contact with hydrochloric acid If we .

di vide thes e cube s again into a total of 64 smaller cubes ,

the total surface of the same amount of iron will be 2 3

sq cm It is e vident that this division can be theoretically
. .

continue d until we have single iron molecules It is also .

evident that the smaller the cubes the greater the su r ,

fac e and the greater the contact surface between the

,

solid and the liquid therefore the greater the possi bility , ,

of molecular co llisions I t is thus possible to pre di ct th a t .

'
the single large iron cube will dissol ve more slo wly tha n
the four small ones and that the 64 smaller ones will dis,
 CON T ROL O F RE AC TION S 51

sol ve faster than the four small ones . The following

table will be of interest
IN CR E A SI N G THE SU R FA C E OF A l -
C C.. CU B E BY SUB DIVI S IO N

E dge len gt h

( a ) 1 m ( m e te r )
. 1 00 c m ( ce n t m e te r )
. i mm . i i
( m ll m e t er )
i
( m c rons )
( ) 0
5 1 3
,

an d 1 0
, ,

“
1 0 00 00 0 00 0ms ( m ll m crons ) ii i in c h es .

( )
c C m ’
. cm X em . . i
s q u are ce n t m e t e r : m .
’
m . X In . s q u a re m e te r .

( d ) B lood c orp us cles t o 1 5m a c ll 1 t o 1 0sb ii , h ydr oge n m ole c ules 0 2 0mi .. c hl i

or n e
m olec ule 0 4 0MM. .

Colloid s .
—
Finely divi ded substances usually react
faster than coarse ones For this reason finely powdered .

substance s and substances in the colloidal state are

reactive as well as gases and substances in solutions
,
.

Colloids are simply finely divided particles of ultramicro

sc op ic a l size which form the transition from single
molecules to aggregations of molecules of microscopical
Si ze
—
.

In cr e a s e of Surf ac e by M e ltin g A rea ction may also

be started when the surface of contact between two solid
su bstances is increased not by subdi vision but by melt , ,

ing on e substance Thus in Fig 2 it is e vident that the

. .

points of contact between two substances is restricted

when both are solid particles but is greatly increased ,

when one substance is liquid A n example is furnished .

by finely divide d sulfur and iron which can be kep t mixed ,

52 CH E MICAL RE AC TIONS A ND T H E IR E QUATION S

together indefi ni tely without a reaction occurring A s .

soon however as the sulfur is molten the reaction

, , ,

begins In this c ase not only the number of sulfur

.

molecules and iron molecules colliding with each other

has increased but another factor heat has been intro
, , ,

du c e d the eff ect of which forms the sub! ect of a later

,

paragraph
—
.

Catalyze rs A reaction may also be either ac celerated

.

or retarded by the presence Of a third substance a ,

catalyzer or catalyst which is or appears to be unchanged

, , ,

throughout the reaction but whose presence is essential

for the procedure of the reaction The action of a .

FIG . 2 .
-
I nc re a s in g t h e s urf a c e by m e lt in g.

catalyzer is either of a mechanical or chemical nature .

The mechanical catalyzers are such substances which ,

when finely divided have the property to adsorb upon

,

their surface the molecules of other substances Thus .

,

finely di vided palladium will adsorb hydrogen gas and

the su rface of the metal will be cov ered with a layer of
hydrogen molecules Th ese densely packed hydrogen
.

molecules are much more reactive than the widely

—
scattered hydrogen molecules in hydrogen gas in other
words the hydrogen molecules have been concentrated
and the gas has been condensed to a solid substance .

Many important processes in industrial manufacture

depend upon the use of catalyzers ( fixation of atmos
p he ric n itrogen manufacturi n
,
g sulfur ic acid ,
 CO NTROL O F R E AC TION S 53

—
Ma s s A ction The dependence of a chemical reaction
.

on the concentration of the molecules is expressed in

the law of mas s action by G uldberg and Waage which
holds that the chemical eff ect of molecules par ticipating
in a chemical reaction is proportional to their mass that ,

is the amount or number of molecules pre sent in a

,

certain volume In the case of solutions this mass is

.

e xpress ed as concen tr ation which is the amount of

substance ( gram molecules or moles ) dissolved in a
-

g i v en volume of sol v ent ( 1 liter ) I n the case of gas es .

this mass is expressed as pressure for the pressure is an ,

indication of the number of molecules present in a

FI G . 3
.
—I r n c e a s in g the s ur f a c e by c on c e n tr a tion or p r e s s ur e .

certain volume of a gas This is best illustrated by .

Fig 3 in which there is in one cas e 1 0 mole cules each

.

in a given volume and in the second case 2 0 molecules

,

each in a given v olume The kinetic theory assumes .

that the molecules of a gas are in free movement and

will therefore collide and bombard the sides of the
vessels The sum of these impacts upon the walls of
.

the container is shown as pressure hence by doubling ,

the number of molecules in the same yolu m e the pres ,

sure is doubled for the number of collisions and impacts

,

has been dou bled I t has been found that under normal
.

conditions (atmospheric pressure of 760 mm at 0 C .

°
.
,

an d at sea level ) on e mole of an y gas will occu py a

-
54 CH E MICAL R E AC TIONS A ND T H E IR E QUATIO N S

volume of liters ( A mole is the molecular weight

.

of a substance in grams that is a mole of H 2 is 2 grams

, , ,

a mole of 0 2 is 32 grams etc ) The kinetic theory ,

.

of gases has been extended to molecules in solutions

which means that the molecules and ions in a solution
—
are also free moving and exert pressure the osmotic
pressure
—
.

P r e s s u re The more moles there are in a liter of gas

or a liter of solution the more molecules there are in
,

this unit volume and the higher the concentration or

,

pressure hence the greater the possibility for the mole

,

cules to collide and react The tendency to react is

.

generally increased with an increase in the number of

molecules or ions present in a certain volume ; b u t as ,

during the reaction some of these molecules or ions

,

have been used up or exhausted by being transformed ,

their concentration becomes less as the reaction pro

c e e ds
, yet at the same time the concentration of the
,

reaction products is increased and the tendency to

again form the original molecules becomes greater .

A che m ical reaction therefore is never complete if the

reaction products can again form the original su b
stances If two molecules ( A B and CD) react to form
.

t wo other molecules ( A D and CB ) as reaction products ,

then after a certain tim e there will be a chemical system

in which all four types of molecules ( A B CD A D and , , ,

and CB ) are present The percentage of the diff erent

.

molecules w ill depend upon the speed of the reactions

—
.

AB CD AD > CB and A D CB AB CD It -
> .

is evident that the speed of the first reaction is greatest

at the beginning for the reaction is started with a high
,

concentration of A B and CD and the absence ( zero ,

concentration ) of A D and CB but this speed will dimin ,

ish more and more as the react ion product s A D and CB

 CONTROL O F RE AC TIONS 55

are formed The speed of the secon d reaction is at

.

first null as no A D and CB is present but this speed

, ,

increases slowly with an increase in the amount or

concentration of A D and CB A s the speed of the. .

first reaction diminishes and the speed of the second

reaction increases there will come a time when the speed
,

of both reactions are equal and a chemical equilibrium

,

is established
—
.

E quilibrium In a chemi cal equilibrium the visible

.

eff ects of a reaction are at stand still and the reaction -

appears to have stoppe d this does n ot imply however

, , ,

that the molecules hav e ceased to collide with each

other . The molecular c ollisions still take place ,

but the formation of A B and CD h as become equal

to the formation of A D and CB in other wor ds the ,

exchange of the con stituents of the molecules is balanced .

The sam e con dition of equilibrium is reached when the

origin al substances are A D and CB instead of A B and
CD . U nder defini te con di tions ( temperature con een ,

t ration or pressure ) there is for any system o f sub stances

only one equilibrium which is established whether the
reaction is starte d with A B and CD or with A D and CB
—
.

E xam ple of E quilibrium A concrete example is

.

gi ven by the following experiment In on e closed .

vess el hydrogen gas and ferrous ferric oxide is heated -

and in another closed vessel iron granules and steam

( water ) . A f ter heating a certa in tim e and keeping at a
c e rtain temperature both vessels will contain the same
,

proportion of hydrogen gas to steam In the first .

container the reaction w as

( )
4 0 4 H 2 I F3 30
““
4 3Fe I 4 H 2 0 ““

while in the second vessel the reaction w as

( )
4 1 3Fe 4 H 20 F9 30 4 4H 2 .
56 CH E M ICAL RE AC TIONS A ND T H E IR EQ UATIONS

A ccor di ngly reaction is the reverse of the other a

on e ,

fact which can be expressed by using the sign of a

reversible reaction namely two arrows :
,

( )
4 2 3Fe 4 H 2 0 z Fe 30 4 4 11 2

In both cases the same equilibrium w as obtained though ,

the original su bsta nces were diff erent The percentage .

of steam an d hy drogen will depen d upon temperature ,

but at the same temperature this percentage is the same

in both cases
—
.

Sh iftin g th e E quilibrium The experimental con di

.

tions can b e so arranged that du ring the reaction one

or the other of the gases is remo v ed In this cas e the .

removal Of one gas w ill constantly shift or destroy the

equilibrium an d the reaction may proceed to completion
,
.

Thus by heatin g the iron granules in a tube open at one

end and pas sin g a strong current of steam into this
,

tube hydrogen gas will emerge from the open end until all
,

the iron is oxi di ze d In thi s cas e the hyd rogen molecules

.
,

as s oon as forme d are carried away and thus remo v ed

,

by the excess of steam flowing into the tube and the ,

reaction will be complete in one direction

( )
4 3 3Fe 4H 2 —
0 E9 I 04
3 4H 2

The concentration of hydrogen molecules under these

condi tions w as ne ver high enough to initiate the reverse
reaction O n the other hand if the tube is fill ed with
.

ferrous ferric oxide and a stream of hydrogen gas is

-

passed int o it steam will be forme d until all the iron

,

oxide is redu c e d to metallic iron

( )
44 Fe 30 4 I ““ 4 H
2
—3F > e 4 H 20

In this case likewise the re action pro duct steam as , ,

soon as formed is carrie d away by the current of hydro

,
 58 CH E MICAL RE AC TION S A ND T H E IR E QUA TIONS
9

brium , which is formed whenever a substance is dis

solved in water is di sturbe d by either ad ding or
,
“
removing AB A or B to or from solution (a ) or by add
4
,
"

, ,
“
ing or removing CD or D to or from solution ( b)
, .

The addition or removal of molecul es or ions is ac c om

p lis h e d by : ( )
a adding more molecu l es by di ss olving
more of the substance ( b) diluting the solution (c)
, ,

removing some ions in the form of molecular or non

ionized soluble compounds (like wa ter weak acids weak , ,

bases or weak salts) ( d) remo ving some ions in an

, ,

insoluble compound ( precipitates ) (e) removing some ,

ions in a gas eous compound ( gas bu bbles ) ( f ) the forma ,

tion of complex ions In each case the ionic equilibrium

.

is shifted
—
.

Form ation of W ate r N eutralization means the ad d

.

“
ing of H to an ionic equilibrium containing OH
+

whereby water is formed and as water is practically not

,
“
ionized the removal of H an d OH from the ionic
,
+

eq uilibrium will be practically complete that is a rea c ,

“
tion will tak e place until all H or OH present have
+

been used up Therefore whenev er there is the possi

.

bility that water can be formed from two solutions a

reaction is likely to take place
—
.

Form ation of P re cipitate In precipitation a mole

.

c ula r and insoluble compound is formed from ionic

constituents an d by this precipitate certain ions are

taken from the solution and there by the ionic equilibri um
is shifted The ionic equilibrium B aCls
. Ba ++

“
2 Cl can be mad e to proceed from lef t to right by either
( )
a add i ng more b arium chloride ( )
b remo v ing B a +
,
+
as

a precipitate (B aSOi ) by the addition of or ( c )

“
removing Cl as a precipitate (A gCl) by adding A g + .

In the last two cases the ions have b e e n remove d by a

precipitate hence more of the molecular b arium chlori d e
 CONTROL or RE AC T I ONS 59

“
will ionize and if su fficient SO,
,
or A g is added all +
,

of the ions may be precipitated and thereby the reaction ,

c ontroll ed
—
.

Form ation Of G a s A n ionic equilibrium is likewise

shifted by the formation of a gas from certain ions an d ,

th e liberation of the gas w ill remove certain ions from

the sol ution Thus by adding an acid ( H ) to a solution
.
,
+

of sodium sulfide N a gs 2Na + the formation of

gaseous non ionized hydrogen sulfide will remove the
-

from the equilibriu m hence more Na gS will ioni ze

,
““
S ,

and if su fficient acid is added all of the sulfide ions may

, ,

be remo ved as 11 2 8 Such reactions can be accelerated

.

by mechanical means (e g agitation or passing a current

. .

of air t hrough the solution ) or thermal means ( e g . .

heating) or both together for by these means the escape ,

or liberation of the ga s from the solution is facilitated .

Form ation Of We ak A cid s — The formation of weak

a éid s ( acids which are little ionized ) will remove hydrogen

ions A solution of sulfuric acid contains much H

.
+
,

that is ,

11 2 8 0 4 2H + ““ 80
I 4

( small (large ( large

and when this is added to a soluble acetate citrate oxalate , , ,

or other salts of a weak acid the ac idity or hydroge n ion ,

concentration will be reduced as the respective slightly ,

ionized acetic acid citric acid or oxalic acid is formed :

, ,

“
( 5)
4 H + AC HAc

To illustrate this by experiment fill a t est tube with ,

very dilute sulf uric acid and color it with an indicator

( litmus methyl
, orange methyl violet congo red
, , ,

if the n eutral salt (e g sodium acetate sodium citrate )

. .
,

is added the color will change and indicat e a neutral

,

reaction .
60 CH E MICAL RE AC TIONS A ND T HE IR EQ UATIONS

Form ation W e ak B a s e s The formation of weak

Of .
-

bases ( bases which are little ion ized) will remove hydroxyl
ions Thu s when a solution of so dium hy droxide ( strong
.

“
bas e) containing a la rge percentage of OH is adde d to ,

a solid am monium sal t th e reaction product w ill be am

,

m oniu m hy droxide ( weak b ase) which is but little ionize d

“
4
( )6 OH NH 4 + NH 4 OH
Try the following experiment : Color a diluted so dium
hydroxi d e solution with a few drops of in dicator an d
add some ammonium sulfate or ammonium chloride
note the change in c olor .

Form ation of W e ak Salt an d Com ple x Ion A weak .

-

salt is a compound which while soluble is little ionize d

, , ,

MN rMt + N with a large percentage of MN an d a

“
, ,

ver y small percentage of M an d N+ “

If such a com .

pound is formed during a reaction it s f ormation will

remove certain anions and cations and there by destroy
the ionic equilibrium l i kewise the f ormation of com
.

plex ions d estroys the ionic equili brium by the remo val
of ions A complex ion is a charged group of atoms
.

or an ion combined with a neutral molecule such ,

as the ammonia complexes Cu (NH 3) N i( NH 3)

etc ; the cyanide complexes
.

et c ; cert ain halogen compounds

. oxalates , ,

ferro and ferricyanides etc

—
.
,

P r e diction of Re action To summ ari ze the facts of

ionic equilibrium and ioni c concentration : A reaction is
likely to occur whenever there is a possibility that the
ions of two diff erent molecules in solution (ionic equilib
riu m ) may form ( a) water ( )
b precipitate ( ) g
0 a s , , ,

weak aci ds (e) weak base (1) weak salt or (g) complex
, , ,

ions for by the formation of these substances the ioni c

,

con centration is changed ( d ecreased ) B y applying .

 CONTROL O F R E AC TIONS 61

this rule it can be predicte d whether or not a reaction

w ill occur if two substances in solution are brought
together l
.

T H E T H E RM A L CO N T RO L

In cre a s e or D e c re as e Of T e m pe rature
th ermal —The
means which influence the frequency of molecular collisions
are those by whi ch not the number but the velocity of the
molecules is regulat ed The faster the molecules move
.

the more numerous are the collisions ; the slower their

movement the less becomes the frequency of collisions
,
.

H eat or a rise in temp erature in creases the molecul ar

movement hence increases the n n m ber of molecular colli s
,

9
ions and therefore accelerates a reaction A rise of 1 0 0 . .

will generally double the speed of a reaction

—
.

State s of A ggre g ation It is as sumed that the three

states of aggregations solids liquids and gases are due
, , , ,

to the rate of vibrations of the molecules In solid an d .

liquid substances the vibrations are comp aratively slow ,

while in di ssolv ed and gas eous substances the vibrations

are fast and the molecules can move freely The .

change from the solid to the liquid state and from the ,

liquid to the gaseous state is thus always a change from

slower t o faster vibrating molecules A n y change in .

the v elocity or vibrating speed of the molecules manifests

itself either in an absorp tion or liberation of heat We .

speak therefore of heat of fusion or melting as well as

heat of vaporization and mean thereby the amount of
heat necessary to transform a solid at its melting point
into a liqui d or a liquid at its boiling point into a gas
—
.
,

E xoth e rm ic an d E n d oth e rmic During a chemical

.

reaction heat may be produced or consumed If the .

1
For a full d isc ussion of the c ontrol of c hem ic al reactions and equilib
,
—
r i um see Hil d eb r an d s P rin c ip les of C he m istry C hap s xi x iv
’
. .
62 CH E MICAL RE AC TIO NS A ND TH E IR EQ UAT IONS

reaction liberat es heat ( exothermic reaction ) then a

compound ( exothermic compound ) has been form ed as
reaction product whi ch contains less heat than the previ
ous molecules for the molecules of one or the other
,

reaction product will vibrate at a lower speed than the

original reacting substances Such molecules of exo
.

thermic compo unds are as a rule stable and not readily

, ,

decomposed If on the other hand during a reaction a

.
, ,

certain amount of heat is used up ( endothermic reaction )

then a compound ( endothermic compound ) has been
formed whose molecules vibrate more rapidly E ndo .

thermic compounds are as a rule unstable and may

, ,

decompose so rapidly as to cause explosions The .

relation between these two types of reactions and com ~

pou nds is sho wn in the Sketch :

E X O T H E RM I C RE A CT IO N

( proceeds rapidly from left to right and l

i berates heat )
AB CD AD CB

E N DO T H E RM I C CO M P O U N DS E X O T H E RM I C CO M P O U N DS
( unstable ) ( stable )

E NDO T H E RMI C RE A CT IO N

( proceeds slowly from right to left and absorbs heat ) .

An exothermic reaction is the change from endothermi c

—
to exothermic compounds from faster to slower vibra t
ing molecules This change requires no heat only a n
.
,

external start and the reaction will proceed rapidly

and completely with the liberation of heat it may b e ,

even explosive A n endothermic reaction is the change

.

from an exothermic to endothermic compound from — ,

slower to faster vibrating molecules This chan g e .

 CONTROL O F RE AC TIONS 63

requires a constant influx of heat and the reaction

will proceed slowly and be limited by the tendency of
the reaction products to again decompose (di ssociation) .

The general ten d ency of chemical reactions is to

produce exothermic compounds that is reaction products , ,

which develop the largest amount of heat ( Thomson s rule ’

,

B erthelot s p rinciple ) In other wor d s rapi dly vibrating

’
.
,

molecules have the tendency to rearrange themselves and

form slower vibrating molec ules thereby lib erating a defi
,

nite amount of heat However if external heat is applied

.

to two exothermic compounds their molecular vibrations

,

may be accelerated su fficiently to form an endothermic

compound .

Con trol Of Ve locity The rise or fall of temperature

.
-

therefore is a mea ns to increase or decrease the velocity

of molec ular vibrations whi ch in turn controls the speed
of molecular reactions T h e application of heat
.

generally has no eff ect upon ionic reactions .

It is also evident that the increasing v elocity of

molecular vibrations can aid combination as well as
decomposition or dissociation D issociation or the
, .

brea king apart of molecul es may be caused by the two

—
external means heat and electricity The thermic .

dissociation ( commonly called di ssociation) is produced

by higher temperatures and continues only as long as
the external cause (heat ) is active ; the electric dis
sociation ( prop erly called ionization ) is produced by

dissolving electrolytes
—
.

Dis s ociation . Thermic dissociation proceeds slowly

with the rise of temperature and diminishes accordingly
with a fall of temperature I e hydro gen and oxygen
. . .

begin to combine at 200 C and form steam ; at 1 2 OO C

°
.
,
°
.

dissociation begins for some molecules of H 2 0 will

,
°
d ecompose into hydro gen and oxygen ; at 2 500 C ,
.
64 CH E MICA L R E ACTION S A ND TH E IR E QUATION S

there is ab out half of the steam dissociate d into H 2 an d

0 2 an d with a further rise of temperature all the mole
,

cules of steam are finally dissociated B y lowering the .

temperature combination takes place again and at

C only steam will b e present
. .

D iss ociation does not depen d solely upon temperature ,

but also upon pressure I ncrease in pressure dimi nishes

.
,

while a d ecrease in pressure increas es dissociation For .

each defi nite pressure at a definite temperature the

amount of dissociation th at is the percentage of dis
, ,

sociate d molecules o f the sam e substance will be con

stant The diss ociation may be diminishe d by adding

.

more of one of the gaseous components f or then the ,

equilibrium is shifte d by the introduction of a larger

amount of one gas D issociation is not restricted to
.

gaseous compounds and another example that heat can

combine as well as d ecompose is the cl assical experiment
of L avoisier of making oxygen from mercuric oxi d e .

A t ordinary temperature mercury is not attacked by the

oxygen of the air but heating slowly transforms it into
,

mercuric oxide an d if heated to a hi gher temperature

, ,

it decomposes again into mercury vapor and oxygen .

The expl anation of dissociation is foun d in the assum p

tion that not only the molecules but also the atoms are
in movement or rather vibratin g Therefore a rise of .

temperature will not only increase the speed of the

molecules but wil l also increase the spee d of the vi b ra
,

tions of the atoms an d finally the atomic vibrations will

,

become so rapid that the atoms will leave their attraction

—
spheres and travel as indepen dent units thusz split t in g

the molecules
—
.

A c tion of L igh t The action of light is probably of a

S imilar n ature Light rays either combine or decomp ose
. .

Thus a mixture of C12 an d H 2 when kep t in the dark

66 CH E MICAL R E ACT ION S A ND T H E IR E QUATION S

tion of the electrolyte but merely a se paration of the

ions already pres ent The cause of thi s separation or
.

migration of the ions to the poles or electro des is found

in the charge of the atoms The ani ons are negatively
.

charge d atoms an d will migrate or move to the ano d e or

pos itive p ole while the cations or negatively charged
,

atoms move toward the catho de or negatively charged

electro de a n d there deliver their charges The cha rges .

of the ions are taken up by the electrodes or poles and

the ions which lo se their ch arge are then deposite d as
atoms or molecules of the free elements .

I n the electrolysis of any acid the hyd roge n is fou nd

at the cathode and the aci d radical at the anode In
,
.

the electrolysis of any bas e the metal is liberated at the

cathode while the hydr oxyl group moves to the an ode
,
.

In the electrolysis of any salt its metallic constituent is

found at the catho de while the non metal or acid radical
,
-

is deposite d at the anode . Thus hydrogen and metals

a re cons i d ered positive elements while non metals and
,
-

acid radicals are negative elements or radicals The .

atoms or group of atoms deposited at the electrodes an d

deprive d of their charges can not exist in free state ,

hence will combine and form molecules

—
.

Se con dary Re a ction P rodu cts In many cases the se

.

newly formed molecules react either with the material

of the electrode or with the solvent pro ducing new com
pounds as secondary reaction produ cts I n such cases .
,

not the elements of the ele ctrOlyt e but secondary rea c

,

tion produ cts are found If an electric cu rrent is

.

passed through a solution of sodium chloride ( electro

lyte) the sodium ( cation) migrates to the negativ e
electro d e ( cathode) a n d the chlorine ( anion) moves t o
,

the positive electrode ( anode ) and forms respectively

sodium metal an d chlorine gas but these free elemen t s
,
 CONTROL O F RE ACTIONS 67

both react with water an d thus give sodium hydroxide ,

at the cathode and at the anode hydrochloric acid

and hypochloric acid Thes e important secondary rs
.

action produc ts account for many phe n omena a n d

their formation is utilized in many industrial processes
for the manufacture of chemicals Formerly it w as .

believed that the electric current electrolyzed or de

composed water into hydrogen and oxygen gas N ow .

we know that absolutely pure water is a very poor

electrolyte and will not conduct the electric curren t ,

hence it cannot be decomposed H owever if an electro .

lyte is added i e if the water is acidulated w ith sulfuric

,
. .
,

acid then these two gases w ill be produced not as

, ,

primary bu t as the secondary reaction products What

,
.

really happe ns is the decomposition of the sulfuric acid

whi ch is dissociated or ionized into the cations H and
+

“
anions SO, The elect ri c current simply separates
these ions locally and the H of the sulfuric acid delivers
+

it s charge at the cathode and forms H 2 molecules ;

“
while the anions SO, migrate to the anode deliver ,

their charges and react with water to form su lfuric acid

,

and oxygen
4H + 2H , at cathode ,

28 0 4 “
I“ 2H
2 0 “ “
2 11 2 8 0 4 I 0 2 I 4 (
“ “ at anode
Combining the se two reactions and cancelling the su l

furi o acid there remains :

“
( )
4 7 2H 20 2H 2 I 0
“
2

which is the visible part of thi s electrolysis for when the ,

gases are collected the volume of hydrogen will be

exactly t w ice the volume of oxygen The sulfuric acid .

formed at the anode dissociates again :

( )
48 2 11 2 8 0 4 4H + “
I“ 28 0
4
68 CH E MICAL R E AC TIONS A ND TH E IR E QU ATIO NS

and its res pective cations and anions migrate o n ce more

to the cathode an d anode and repeat the process In .

the electrolysis of acidulated water the re is thus a

con tinu ous dissociation and c ombination of the aci d in
whi ch the constituent s of water take p art and by which ,

hydro gen an d oxygen are forme d as s econ d ary rea ction

products
—
.

Ele c troch emical E quivalen t The amount of substance

d eposited or liberate d at t he electrodes depends upon
the amount of electricit y which pas ses through the .

solution . The amount of electricity is measure d in

coulom bs or ampere seconds The same quan tity of
-
.

electricity in the same length of time will sepa rate the

ions at both electr o d es in prop or tion to their e q ui valent
weight (Faraday s rule) The equivalent wei ght is the
’
.

a tomi c weight divided by the valency To deposit a .

gram equivalent (atomic weight / valence a: grammes )

of an y ion requires coulombs H ence of copper .

grams of Silver ( A g ) +
,

grams of ferrous ion

, 56/ 2 2 8 grams of f erric ,

ion gram s will be deposite d by

co ulombs The total elec trical charge on a gram
.

equivalent of any ion is therefore coulombs as

thi s amount of electricity is r eq uire d t o neutr ali ze the
total charge of the gram equivalent ; and the total
c harge on a mole or gram atom of a n ion is times
it s v al enc y
—
.

E le ctro m otive Forc e

-
The force with which the
.

ions hold this charge is call ed electro affinit y or electro -

motive force This force varies for different ions To

. .

the stro n g ions belong the cati ons K + N a Li and

+ +
, , ,
“
the anion s NO3 F Cl“ “
, ,
while to the weak ions
,

be long the cations an d the anions

“ “
CN
“
O , S , ( It is we
. l l to note the distinction
 CONTROL O F R E AC TIONS 69

between the ionic charge and the force with whi ch the
ionic charge i s held
—
.

A substance of strong ele ctro motive force Is one which

produces strong Ions that Is the atoms hold the electrical
, ,

charge firmly A substance of weak electro motive

.
-

force is one whose atoms hold the electrical charge less

firmly and thus gives weak ions
—
.
,

Displa c em e n t If a substance capable of yielding

strong ions be added to a solution of weak ions then the ,

weak ions will give up their charge and become elec tri
cally neutral while the solution wi ll contain the strong
,

ions When a piece of metallic zinc ( strong electro

.

motive force) is placed in a solution containing lead

—
ions ( weak electro motive force) zinc ions are formed , ,

and metallic lead is deposited as a black spongy mass

4
( )9 Zn Pb ++ z n ++ Pb

Metallic lead in turn will precipitate copper ( weaker

electro motive force ) from a solution of cupric ions
-

( )
50 Pb Cu + + Pb ++
Cu

Metalli c copper will discharge mercuric ions and deposit

mercury
51
( ) Cu Hg ++
C u + + Hg
The weak el ectro motive force of mercury is stronger
—
-

than the electro motive force of silver therefore it will ,

take the ionic charge from the silver ions and crystalline
silver will be deposited

( )
52 Hg 2A g +
Hg i +
2A s

In the same manner electro negative elements of -

stronger electro motive force will become ionized and

-

form anions if they come in contact with anio n s of

'
70 CHE MICAL RE ACTION S A ND T H E IR E QU ATIONS

weaker electro motive f orce

-

, hence chlorine gas will

react with bromine ions
“
(53) C1,
“
2B r 20 1 B r,
B romine will react with iodide ions :
“
( )
54 B r, 2I 2B r I,
“

I odine is stronger than sulfide ion

“ “
(55) 12 S 2I S
“

Displ ac em e n t Se rie s
The sequence in which the
.
-

elements act in this manner is according to the preceding

equations for the positive metals Zn Pb Cu Hg
> A g and for the negative non metals Cl
, Br> I> S -
.

Zinc is thus more positive than silver and silver more ,

negative than zinc Chlorine is more negative than

.

sulfur or sulfur is more positive than chlorine P ositive

, .

and negative are thus relative terms and it is possible

to place all elements in such a relative series which is
terme d the displacement series In the displacement .

series given in the appendix the most negative elements

, ,

are at the beginning and these will displace as anions all

,

that follow ; whi le the elements at the end are the most
positive and will displace as cations all above them .

From the above it becomes evident that if a piece of ,

iron is dipped into a copper salt solution metalli c copper ,

will be deposited and the iron will go into solution :

( )
56 Fe Fe + + Cu

The cupric ion h as given its charges to the iron an d has

become electrically neutral copper while the previously ,

electrically neutral iron has taken this charge and become

ferrous ion This transmission of the electric charge
.

takes place simultaneously and may occur at any point

of contact between the iron an d the copper ions .
 CONTROL or R E ACTIO NS 71

Volta ic Ce lls —The

. transformation of chemical energy
into electrical energy is demonstrate d by voltaic cells or
batteries Thus the experimental conditions of the above
.

reaction ( 56) can be so arranged that the direct contact of

iron and copper ions is prevented but the exchange of the ,

charges or electrons is made possi ble by a conducting

connection b etween the iron and the copper ion s which
causes a stream of electrons to pass thus producing an ,

electric current in the conducting connection ( metal

FIG 4 . .
—A v
olt aic c e ll or e le c tr ic a l b at te ry .

wire) These experimental conditions are illustrated in

.

a galvanic battery or voltaic cell It is essential in .

such experimental conditions that the reacting sub

stances are locally separated yet connected by a con
,

ducting media for only then are the electrons forced to

,

travel through the conductor and produce an electric

current when the circuit is closed The conditions are .

schematically represented in Fig 4 . .

The farther apart the two metals selected as electrodes

stand in the displacement series the greater will be the
,

produced electro motive force or potential measured in

-

,
72 CH E MICAL RE AC T IO NS A ND T H E IR E QU ATION S

volt s f H ence Fe and Zn will produce a smaller voltage

than A l and P b or Mg and Cu ; likewise Zn and Cu
or Zn and A g w ill produce a greater voltage than Zn
and Fe
—
.

E xampl e Of Ce ll In the figure a rod of iron and a rod

of copper are used as electrodes The iron stands in .

a solution of ferrous sulfate the copper in a solution of ,

cupric su lfate and the solutions are separated by a

,

porous wall or semi permeable membrane If the -

.

concentration of the ferrous sulfate solution is low and ,

the concentration of the copper sulfate solution is high

the metallic iron tends to go into solution that is acquire , ,

two positive charges and thus form ferrous ions while , ,

at the same moment a cupric ion w ill deliver two positive

,

charges to the copper rod and be deposited as metalli c

copper The iron rod will lose weight ; the copper rod
“
.

will gain weight The iron electrode becomes less

“
.

” ”
positive that is more negative and the copper ,

electrode b e c omes m ore positive The reactions which .

take place are

at the cathode (57 ) Fe F
e ++

at the anode ( 58 ) Cu + + Cu

and by adding these two equations and cancelling the ,

two positive charges which appear on both sides equa ,

tion (56) results .

B oth reactions ( 57 and 58 ) occur simultaneously

and proceed until an equilib rium is established ,

and the current ceases If the ferrous ion concentra.

tion is very low in the beginning and the cupric ion

concentr ation very hi gh the battery will live longer , .

If however at the beginning the ferrous ion concentra

, ,

tion is high and the cupric ion concentration is low

, ,

little or no current will be produced .

74 CHE MICAL RE ACT IONS A ND TH E IR E QU ATIONS

The e n dprodu c t in both cases is thus lead sulfate and

theoretically the accumulator is entirely exhausted or
di sc harged when all the lead and lead oxide has been
transformed into lead sulfate ; but practically this
condition never h appens as the reaction is reversible .

When an accumulator is exhausted a chemical e quilib

riu m is established in w hi ch the reactio ns 59 to 63 have

ceased and a large amount of lead sulfate is present .

B y passing an electric current from an outside source

through the accumulator the lead sulfate is decomposed
again into P b and P ho g as the reactions have bee n
,

reversed I n charging the accumulator the reactions

.

are at the anode

64 P hso4 Pb “
I 0
( ) ++ “8
4

6
( )
5 Pb

A dding these two reactions together

A
( ) P b 8 0 4
“
Pb I“ “
I“ 80 4

The reactions at the cathode are

'

66
( ) P eso , 2H ,o 2H + so,
P hog “
( )
67 Hs 02 I“ 2H +

( )
68 P hOe P bo2 2(
"

A dding these three reactions together

( )
B P bSO, 2 H eO P b Oz SO t - 4H +
+ 2(
and comparing equation ( A ) with ( B ) we find the t w o
negative charges liberated in (B ) counterbalanced by
the two positive charges of (A ) B y the ad dition of
.

( )
A to ( )
B it is possible to represent the reactions occur
ring at the electrodes during charge and d ischarge of
the accumulator :
 CO NTROL O F RE ACTIO NS 75

cathode
2P bSO , 2 H 20 P bO z 2(
discharge
anode
electrolyte
I 28 0 4
““ “
I“ 4H +

i
e le c t olyt e

Ch e m ic al A fin ity —T he
preceding paragraphs Show
the in fluence of mechanical thermal and elec trical m
.

, eans,

and the corresponding pheno m ena have been discusse d

as m ass action kinetic or free energy and electro motive
, ,
-

force of the atoms H owever some reactions are aff ected

.

by another factor whi ch can not be grouped under these

three headings T hi s fourth factor depends upon the
.

nature of the substance and is expressed by a certain selec

tive tendency or chemical affinity of one type of atoms
for another type of atoms The chemical affinity mani .

fests itself in certain elements which are grouped together

in the periodic chart ( see appendix ) Thus the elements .

located around boron have an affini ty for nitrogen and

y ield nitrides ( B N while those
,
in the neighbor
hood of lithium have an a fli n ity for hydrogen and give
hydrides (L iH The reason of chemical affinity
,

is not due to electro motive force and is yet unknown

-
1

—
.

Summ ary B y physical means ( mechanical thermal

.
-
r
, ,

electrical) the speed of a reaction can be (a ) accelerated ,

( b) re t arded (
,
c ) stopped or ( )
d reversed ,
.

M echanical means when applied to ioni c and molecular

r eactions control the number of molecules per u ni t

volume : ( a) sub division of solid substances ( colloids ) ,

( ) concentration of solutions (6 ) pressure of gases ( d)

b , ,

1
For a discussion of affinity see Am e rican J ournal of Scien ce vol 46 , .
,

p age 490, 19 18 .
76 CH E MICAL RE AC TIONS A ND T H E IR E Q U ATIO NS

catalysers In molecular reactions an increase in the

.

number of molecules will increase the frequency of

molecular collisions and thereby increa se the possibility
of reaction I n ionic reactions the control of the c on c en
.

t ra tion is b rought about by the removal of anions or

cations ; thus the possible formation of (a) water removes
“
H + a n d OH ( )
b precipitate remo
, v es either cation or
anion (c) gas removes either cation or anion ( d) weak
, ,

acid re moves H (6 ) w e ak base removes OH (f ) weak

+
,
“
,
'

salt removes cation or anion (g) complex ions remove ,

cation or anion .

Thermal means are generally applie d to molecular

reactions an d consist in control of temperature or the
velocity of molecular vibrations Raising the tempera .

ture increases the velocity of the molecules thus in c re as ,

ing the frequency of molecular collisions and hence

accelerating the spee d of a reaction .

E lectrical means when applie d to ionic reaction s

control the local separation of ions The density of th e .

electric current will determine the spee d of the re action .

QUEST I O NS A ND P RO B L E MS

1 . What will be t he effec t of (a ) little (5) m uch water on the hy drolys is

,

of B iCl, (eq uation 1 60)

2 . Write q uations for t he re action of b rom in e with
e alum inum ,

( )
b i ron ( c
,) m a gn es i um ( d ) s o,d ium an d, a rrang e t he m ac c o rding to th e ir

relative Speed s as ded uc ed from the disp lacem en t series .

3 By he ating the hy d roxi des an d c arb on ates of ( a) c alciu m ( b) c oppe r

.
, ,

( )
c iron ( )
,
d ni c k e l ( 6 ), s il v e r t h e, respective m et al oxides are form e d .

Write e quations and state whic h c om poun d re quires t he lowes t a n d ,

whi c h com p ound the highest tem pe rature for its decom position .

4 By ad ding water to (a ) Ca N
. a(b) Ca n (c) Ca A m cal c iu m
z, , z ,

hyd roxi de is formed What are the other reaction p ro ducts an d whic h
.

ofit hese thre e reac tion s will p ro cee d m ost rap id ly an d why
5 By heating alum inum with (a ) an tim ony (b) arse ni c (c) b is m uth
.
, , ,

( d ) p ho sp horu s t h e,
r es p e c ti v e b i n a ry c o m p oun ds a re for m e d W h ic h .

c o m p oun d w ill req uire t he leas t am ount of he at

6 If t he m etals Al G a Fe In M g Zn are he ated in a c urre nt o f

.
, , , , , ,
 CO NTROL O F RE AC TIO NS 77

chlorine gas t he respective chlorides are form ed Write t he equ ations

, .

and s ta t e w hi c h m e tal req uires t he lowes t an d w hi c h m e tal re q ires t h e , u

highest te m pe rature to sta rt the reac tion .

7 By hea ting T iCl w ith m etalli c Zn or Sn the T iCl is red uced to

. , , ,

TiCl an d t he b ic hlorid es of Zn or Sn are form ed

a Write equ ation s .

an d sta te whi c h reac tion oc c urs m ore rea d ily .

8 A rran ge ac c o rding to v e lo c ity t he re ac tio n s of wa te r w ith m e tal lic

.

(a ) c a l c iu m ( b
,) c Opp e r ( c) a lu m,inum , ( d ) lithiu m ( e) iro n 0 ) m a gn es iu,m , ,

(g) p otassium ( h) sod ium , .

9 G 6 0 c an b e re d uc ed to m e t a lli c G e with e ithe r H or C

. , Which , .

re action p rocee ds m ore readily ? Whic h c om p oun d d oes hy drogen

g as r e d u c e m o re r e a d ily G e o or G c s ? W rit
ge e q u a
z tion s f or e a ch .

1 0 P re d i ct what will happ e n if m e talli c m agnesiu m is hea ted with

.

( a ) S i O ( 5) G e O (0 ) P b O
,, ,, Whi c h reac tion p ro c eed s m ore re adily ?
,.

1 1 C arb on d iox i de can be re d uc ed to c arb on by ( a ) cal cium ( b)

.
,

m agnesium ,(c) potass ium (d) sod ium Write t he equatio ns an d

, .

arr a nge the m in t he o rd e r of the ir sp ee d of re ac tion .

1 2 Point out whi c h m e ta ls are soluble in sulfuric ac id un de r t he evolu

.

tion of hy d roge n gas : (a ) alum inum ( b) c opp er (6 ) iron (d) m agnesium , , , ,

( a) s il v e r, 0) tin ( g) z in ,c?

1 3 Whi c h e lem e nt red u c es H A u Cl m ost re a dily : (a ) c o pp e r ( 5) iron

.
, , ,

(6 ) p hosp horus (d) tin ,

1 4 A rran ge t he following oxid es in t he o rde r in whic h carb on will

.

reduc e them m ost readily to m etals : (a ) alum inum oxide ( b) iron oxide , ,

(c ) le ad oxi de (d) m agnesium oxid e ( 6 ) tin oxide (f ) zinc oxid e Write

, , , .

t he respective eq u ation s .

1 5 Giv e a reason why i od ine re p la c es c hlorine in t he e qu ation

.

2 K ClO , I 2 K IO
, C l ( This reaction occur s in t he p res enc e
, ,.

of H NO as c ata lyse r)
, .

1 6 By heating m e tallic M g an d Rb OH t he followin g re ac tion oc c urs

.

2 Mg 2 Mgo Why is hy d roge n gas forme d ?

'

2 Rb OH 2 Rb H 2.

Why is it not p oss ib le for t he reac tion Mg( OH ) 2 Rb 2 Rb O H 3

M g to occur ?
1 7 If am m oniu m bic hrom ate is hea ted gre e n Cr O is form e d
. W h at g , .

a re t he po ss i b le re a c tion p rod u c ts How c o uld you tes t by e xpe rim e nt

whethe r the oxy gen or nitrogen is oxidi ze d ? ( Write two or m ore eq u a
t ions of p oss ibl e re ac tions ) .
 CH A PT E R VI
TYP E S OF REA CTIO NS A ND T H E IR E QUA TIO NS

Reactions and their equations are divided into types .

Thus if a complex molecule is broken apart into simpler

,

or elementary constituents th e process is called an a lysis ;

,

the reverse process of constructing or building up

complex molecules from elementary constituents is
called syn thesis ; whi le the exchange of parts of one
molecule with parts of another molecule is termed
meta thes is The first two term s are explained by the
.

following scheme

m ar
b le
(c a lc ium c a rb on ate )

'

lI m e
A NA L Y SIS
(c alc ium oxide )
Ca O

l iu m oxyg en
ca c carbon oxyg e n l
e e m e nt
Ca 0 C 0 2

SYNT H E SIS

l ium
ca c ca rb onate

78
 r u ns on R E AC T IONS A ND T HE IR E QU AT I ONS 79

A nalysis in the above example involves the reactions

—
9
( )
6 CflCOa '
fl c aO 002
( )
7 0 2 C O
a 0 > z a 02

while synthesis is expressed by the equations

—C Co
—
( )
7 2 CaO CO z r a s

( )
7 3 20 a O 20 z > a0

4
( )
7 C Oz

An exam ination of these two sets of equations reveals

the fact that in ( 69) and (72 ) there are no changes in the
valence numbe r of the elements involved while in ,

and ( 74 ) there is a change in the valence

number of the elements therefore analysis and synthesis
,

may or may not involve oxydation and reduction It .

is also evident that ( 72 ) is the reverse of ( )

73 the
reverse of ( )
7 4 the reverse of A n analytical
reac tion of type (69) is termed decomposition while the
—
,

reverse synthetical reaction ( 72 ) is addition in these

two types there is no change of valency The analytical .

reaction of type (7 0) or (7 1 ) is known as red uction whil e ,

the reverse synthetical reaction (73) or (74 ) is usually

termed oxydation B u t the terms oxydation and re du c
.

tion are am bigiu ou s for they also mean an increase or

decrease in the valence number of an element therefore ,

it is more exact to use combination for oxydation and ,

division for reduction when sp eaking of reactions .

A n example of metathesis :

( )
7 5 Ca Cl, Na zCoa CaCOs 2 Na Cl

shows that there is an exchange of parts in a molecule

without change in the valence number O ne of the .

most c ommon types of m et athesic al reacti ons is neutrali

z a t ion which has previously been defined as the reaction
80 CHE MICAL RE A CT IONS A ND TH E IR EQU A TI ONS

bet ween an acid an d a base to give wate r an d a sa lt .

A n ex am ple is :

( )
7 6 Ca (OH ) 2 ZH Cl 0 8 0 12 2 11 2 0

while t he reverse reac tion is hydrolysis :

( )
77 CaClz ZE QO Ca ( OH ) z 2 H Cl

The in terrelation of t hese diff erent type s of reactions

is shown in the followin g diagram in which the arrow
indic ates the dire ction of the reaction M and X a metal ,

or positive radic al N an d Y a non metal or negati ve

,
-

radic al .

T YP E S or RE A CT IO NS

A . Reactions inv ol ving oxidation an d reduction

no

( i . increase
e. n o or decrease in the v alence numbers of
the e lements)
I A DD IT IO N
.

MN XN MN X N
.

II . D E COMP OSIT ION MX N z

III . M E T A T HE SI S MN XY MY XN

I V NE U T RAIJIZA T ION
.

MOH + H N MN + H OH
V H YD ROL YSIS
.

B . Reactions in volvin g oxidation reduction (i a

an d . .

increase or decre as e in the valence numbe rs of t he

elemen ts)
VI . COM B I NA TION
M N MN
VII . V
DI ISION
82 CH E MICAL RE AC TIONS A ND TH E IR EQ UA T IONS

Ni “
+x
6NH 3 Ni( NH 3)
C u ++ 4 NH 4 OH 4 H 20

Z II ( OH ) 2 2 NH 4 0 1.+ 4 NH 3 Z I1 ( NH ) 50 12
3

2 H 20
NaOH CO NaH COz or H COONa
A 8 28 ; 3( NH 4 ) 2 S 2 ( NH 4 ) 3A 8 8 3
SH S ( N H 4 ) 2 8 2 ( N H 4 ) 2 SI1 8 3

SIlSz ( N H 4 ) 2 S ( N H 4 ) 2 SI1 8 3

Fe ( CN) z 4 K ON K .Fe ( CN) 5

Zn ( CN) 2 2 K CN K zZ n ( CN) 4
Ni ( CN) z 2 K CN K zNi ( CN) 4
CO ( N0 2 ) 3 3K N0 2 K 30 0 ( N0 2 ) 5

II . D E CO MP O SIT IO N

D ecomposition is a chemical reaction in which a

complex compound is br oken apart into simpler com

pounds without any change in the valence numbers of
—
the elements in volved it is the re verse reaction of
addition

( 1 0 1 ) NH I CI NH 3 H CI
( 1 0 2 ) On ( oH )2 0 110 H 20
( 1 03) H I Sn O I H zSIlOa H 20
( 1 04 ) CU ( N0 3) 2 0 11 0 N2 0 5
'
( 1 0 5) re o8 3H , o
( 1 06) 2 13 mm) , B , ( NH ) 3 NH , 2B N 4 NH ,

T o thi stype belon gs dehydration which is the reaction,

taking place when crysta ls containing water of crystal

liz at ion are heated and lose part or all of their water .

D ehydration usually proceeds in steps depending upon ,

temperature thus ,
 TY P E S OF R E ACT I O NS A ND T H E IR E QUATIO NS 83

°
b eginning at 19 C

MgSO . 7H zO
. MgSO 4 6H gO . H gO
°
beginning at 3S O . :

MgSO . 6H zO
. M gSO 4 . 2 H zO 4H 20
°
b egin ni ng at 1 12 C

MgSO . 2 H 20
. M gSO 4 . H 20 H zO
°
beginning at 2 03 C

M gSO d IzO
‘
MgSO o H zO

The complete dehydration is expressed by

( 1 0 7 a ) MgSO 4 . 7H gO MgSO . 7H 2 0

In t hi s case the dehydrated magnesium sulfate when ,

heated to about 4 00 C will begin to decompose accord°

.
,

ing to
( 1 0 7 b ) M gSO . MgO 80 3
M any other sulfates b ehave Si milarly The dehydration .

and decomposition Of copper sulfate is express ed in the

equations :
CU SO 5H 0 CU S0 3H 0 2 11 0 b e gin s at 2 7 G
O
;. 3 4. 3 1 ,
.

Cu SO 3H O Cu SO . H O 2 H O b e gin at 9 3 C d hydration °
..
g .
g g ,
s . e

Cu SO H O 0 11 8 0 H O b e gin s at 1 1 5 C
°
..
, 4 z ,
.

2 Cu SO Cu SO. Cu O
. 80 b egins at 660 C dec om pos i
.
3,
°
.

Cu 80 CuO
4. 2 Cu O 80 begins at 7 10 C f tion °
.

The complete dehydration is thus

1
( 8 a)
0 Cu SO 4 7H 2 0 . Cu sO 4 7 H 20
and the complete decomposition
( 1 o8 b ) Cu 8 0 4 Cu O 80 3

III . ME T A T H E SIS

Metathesis is a common reaction The ge neral type .

MN XY MY X N in dicates a d ouble decomp osi

84 C H E MICAL R E A CT I O N s A N D T H E IR E QUATION S

tion in which an exchange of the eleme nts or radicals

has taken place.
.

Some examples are

( 1 09 A
) g N O . N a Cl A g Cl N a N O a

( 11 0 ) C a O 2 H C l G a o l .

( 11 1 ) C a S 2 H Cl 0 3 0 12 H 2 8
( 1 1 2 ) Ca s 6H Cl 0 3 0 12 2P H 3
( 1 13 ) A12 0 ; 6H Cl 2 A 1Cla 3H 2 0

( 115) A l ea 6H Cl 4 2 11161. 3H .s e

FCS ZH Cl = Fe Clz H 28
( 11 8 ) 2 Na sA s 6H Cl 2A s GNa Cl
( 119 ) Sn Clz H zs Sn S 2 H Cl
( 1 20 ) Ca O s G as 1 H 2 0
““

( 1 2 1 ) Ca CO a Nags CaS Na 2 C0 3

( 1 23) 3Ca 0 Na aA lF¢ 3CaF2 Na gA 10 3

Al( 0 Na ) a)
0 11 8 10 H F = SiF. Car .
( 1 24 ) . 3 2 2
( 1 2 5) W0 3 2 K OH = K 2 W 0 4 H 20
( 1 2 6 ) K 2 W O 4 H 2 8 0 4 H 2 0 K 2 8 0 4 WO ( O R ) 4
( 1 2 7 ) 2 Al ( OH ) 3 3 0 8 2 A l a 3 H z S 3C0 2
( 1 28 ) H 2 8 0 4 P 2 0 5 so. m m .

( 1 2 9 ) 8 11 0 12 N& 2 0 0 3 H 20 SII ( OH ) 2
2 NaCl 00 2
2H 20 ( 3s CR( OH ) 2
A 14 C3 12 H 20 3OH 4 4 A l( OH ) 3
PH J K OH PH 3 KI H 20
2 H 3B 0 3 3P Cl5 B 20 3 3P OCla 6H Cl
2 Cu Cl Na20 0 3 0 11 2 0 2 Na Cl 002
0 11 0 12 N& 2 0 0 3 0 11 0 0 3 2 Na Cl
M0 0 3 2 K OH K 2 MO O 4 H 2 ()
Aua 2 K OH 2K A q H 20
 TYP E S O E RE A CT IO N s A ND TH E IR E QUAT ION S 85

In the preceding list only molecular equations are

—
given s ome of which can be put into ionic form T ypi .

cal ionic equations of m e tathe sic reactions are :

138
“ CI A gCl
( ) g
A
“
( 139 ) B a + + 80 4 B asO.
Ba
“ CrOr
( 14 0 ) + + B a CrO .
(
(
141
14 2
)
)
Cu
C0 “ 2 OH
2 OH
“
Cu ( OH ) 2
CO ( OH ) 2
( 14 3) Zn + + 2 OH Z n ( OH ) 2

“
( 144 ) Z n ( OH ) z 2 OH Zn Oz 2 11 2 0
( 145) Fe 2 CN Fe ( CN) 2
( 14 6) Ni
“ 2 CN Ni( CN) 2
++

Zn 2 CN Zn ( CN) 2
( 1 48 ) 2 C u ++
Cu zFe ( CN) 5
( 1 4 9 ) C11 ( OH )2 4 N H 4OK 2 0 11
4H 2 0

“
( 1 50 ) 2 N a 38 bS 6H +
Sb2 8 5 6N a +
3H 2 8
( 1 5 1 ) B & 0 2 2H + Ba H 20 2

( 1 53) Cu ++
s CuS 2H +

I V NEU T RA LIZA T IO N
.

As previously stated the general equation for neu

,
“
traliz at ion is H + OH H zO This equation is .

irrespective of the acid and base employed The salt .

formed diff ers in accordance with the acids and bases

‘

used but the formation of water is the principal earmark

,

of neutralization ( compare equations 4 to By

attaching a negative nonmetal or acid radical N to the
.
, ,

positive hydrogen ion and to the negative hydroxyl ion

a positive metal or bas ic radical M the general type of , ,

neutrali zation is M ( OH ) HN MN HOH and

hence it is a m et athesic al reaction B y substituting any .
 86 CH E MICAL RE A CT I O N s A N D T H E IR E QUATIONS

metal or p ositive radical for M and any nonmetal or ,

negative radical for N a great number of particular

,

reactions are possible some of which are given in equa

,

tions 4 t o 1 5 .

V H YDROLYSIS
.

H ydrolysis is a m e tat hes ic al change brought about

by the action of water and is the reverse reaction of
—
neutralization the general type is M N
, HOH
M ( OH ) HN H ydrolysis takes place when the salt
.

of a weak acid of a weak base or a compound whose

, , ,

constituents are not far apart in the displacement series ,

is dissolved or brought into contact with water .

H ydrolysis of salts of a weak acid :

CH 3COONa 11 2 0 Na OH CH sCOOH
( 1 55) N3 2 0 0 3 H 2O NaOH Na H COs
( 1 56) Na H COz H zO NaOH H zCO s Na OH
H zO C0 2
( 1 57 ) 2 B aS 2 H QO B a ( OH ) 2 B a ( sH ) z
( 1 58 B
) a ( sH ) 2 2 H zO B a ( OH ) 2 2 H 28

H ydrolysis of salts of a weak base

2H 20 0 11 ( OH ) 2 H 28 0 4

V ( 1 60) B iCla H 2 () B iOCl ZH Cl

B ioCl mm B i ( OH ) a H CI
( 1 62 ) A 10 1. mm A l( oH ) a 3H CI

H ydrolysis of compounds whose constituent elements

are not far apart in the displacem ent series :

( 164 ) P 0 15 5H 2 0 5H CI P ( OH ) 5 ( = H 3P O 4

H zO) .

V0 ) 65 Sh Cla H zO SbOCl H CI
( 1 66) SiCl4 2 H 20 8 10 2 2 H Cl
( 1 67 ) C0 1; H 20 0 0 0 12 2 H Cl
 TYP E S or RE A CT IO Ns A ND T H E IR UATIO NS
EQ 87

( 1 68 ) BN 2 H 20 H B Oz NH;
( 1 6 9 ) 0 & 3A S2 CH 2 O 2 A SH 3 3Ca (OH ) 2
( 1 70 ) W Cle 5H 2 0 H 4 W0 5 6H Cl
( 1 7 1 ) P R, 3H .o 3H B r
( 1 72 ) PBI 5 ’
11 20 P OB I 3 ’
ZH E I '

( 1 73 ) P OCla 3H 2 0 H 3P 0 4 3H Cl

U nder certain conditions even distinct polar compounds

hydroly se :
( 1 74 ) MgClz H .o MgO 2 110 1
“
2 Na Cl 1 H 2 0
“ Na zO ZH Cl

These polar compounds are called strong salts wh ile

the compounds enumerated in the list which ha ve con
s t it u en t s near together in the displacement series are
termed “weak salts The former ionize strongly
”
.
,

the latter ionize but slightly if at all .

V
I . CO M B INA T IO N

Combination is the union of two elements resulting

in the formation of a compound : M N MN .

Whi le this equation apparently is the simplest type of

reaction it involves the principles of oxidation and
,

red uction for M is usually oxidized and N is reduced .

O rdinarily combination is called oxidation and the ,

reverse reaction is termed reduction In a strict sense .

,

however combination as well as division invol ves

,

oxidation a n d reduction T h e common term inology .

,

while practical in some respects is thus am bigiou s and ,

should be avoided S ome examples of combination or

“
.

oxidation are
Q
( 1 7 6) 2H 2 02 2 11 20
( 1 7 7 ) Ca 0 12 0 3 0 12
1
( 8)
7 Fe S Fe S
88 CH E H I CA I. RE A CT I ONs A ND T H E I R E QU A T IO Ns

( 179 ) 4Fe 30 .
( 1 8 0 ) N. 20 . mm
( 1 8 1 ) H. F. ZH F
( 1 8 2 ) P. 50 1. 4 P Cl.
( 1 83) w 30 1. w 0 1.
( 54 )
1 Bi 31 1311.
( 185) 3Z n 28 5 Z n .Sb.
( 1 86) 3Z n 2 11. Z n .A s.

Not only metals/ and nonmetal s combine, but l o

as

elements and compounds The element in most c as es is

—
.

oxygen therefore the obs olete term oxidation :

Fe S 20 . Fe SO.
( 188 ) Zn s 20 . Z n SO .
( 1 8 9 ) 2 NO O. 2 NOz
( 190) 4 NO 30 2 2 H 20 4 H N0 3
( 1 9 1 ) 4 MgO 20 0 0 . O. 4 MgCoO .
( 192) 6CO 6K C.O oK e
( 1 9 3 ) 2 G aCl. Ga 3G aCl.
( 1 9 4 ) H 8 ( Noa) 2 Hg 2 H gN0 :
1
( 5)9 FC2 ( SO 4 ) 3 Fe 3FCSO 4

V
II . V
DI ISI O N

Di vision , commonly called

reduction is the revers e ,

reaction of Com bination ! ust as decomposition is the

,

rev erse of addition Typ ical examples are :

.

( 1 96 ) 2H Cl = H 2 Cl:
( 1 9 7 ) 2 H gO 2H g O.
( 1 98 ) Zn Cl. Zn Cl.
( 1 99 ) 2H I H2 2I

More complex compounds

( 200) K .P t Cl. = 2 K Cl 2 0 1. Pt
( 20 1 ) 4 c ro.c 1. 2 0 1. o.
90 CH E MICAL RE A CT I ON s A ND T H E IR E QUATION S

D isplacement by nonmetals
( 2 13) B r. 2 A gI 2 A gB r 21
( 2 14 ) C1. 2 A gB r 2 A gCl B r.
( 2 1 5) F. 2 A gCl 2 A gF Cl.
( 21 6) 3F. 3H .O 6H F O.
( 2 1 7 ) 2 F. 2 H .O 2 H .F. O.

( 2 1 9 ) O. 2 MgCl. 2 MgO 2 Cl.

( 2 2 0 ) 50 . 4 P B r. 2 P .O . 6B r.
( 2 2 1 ) B r. H .S 2H B r S

The many displacement reactions which involve hy

drogen can be grouped into two types In the first type
of displacement the hydrogen of acids or bases is being
replaced by a more electro positive metal In t hi s case
-
.

hydrogen is reduced and hence acts as an oxidizing agent :

( 22 2 ) Z 1] H 28 0 4 Z D SOA H2
( 2 23) 2 A l 6H Cl 2A lCl. 3H .
( 2 24 ) Mg l " ‘
2 H N0 3 M 8 ( N0 8 ) 2 H2
( 2 2 5) 2 11 2 K OH Z II ( OK ) 2 H2 K 2 Z II0 2 )
( 2 2 6) A l 2 K OH K A lOz K H2
( 2 2 7 ) 2 M g 2 K OH MgO 2K H.
In the other cases the hydrogen is oxidized and so acts
,

a reducing agent
'

as

( 2 28 ) 2 Na .O H 2 Na OH 2Na
( 229 ) Cu O H. H .O Cu
( 230 ) Fe .O. 3H . 3H .O 2 Fe
( 231 ) 2 A gCl H. 2 H Cl 2A g
( 2 32 ) W0 . 3H . 3H .O W
The first set of reactions ( 2 22 in which hydrogen
is replaced by a metal depends upon the ele ctromotive
,

force of the metal and the following general rule is

deduced : Wh enever the metal M is more positive , ,
 TY P E S O F RE A CT I O Ns A ND T H E IR E QU A T I O Ns 91

than hydrogen ( see displacement series) it will take

the charge from the hydrogen ion and liberate hydrogen
gas hence these metals are all soluble in acids according
,

to the general equation 2 M 2H + 2M + H. .

IX . SU B STITUTIO N

Substitution is a chemical reaction which resembles

displacement ; however t he element which interacts
,

with a compound does not liberate the replaced element

but combines with it according to the general type
'

2X MN XN K M in the case of metals and ,

2Y MN MY N Y in the case of nonmetals :

( 33)
2 2 NH . H gCl. NH .CI H gNH .Cl

2
( 35) C1. H zO = H Clo
H OCl
( 235) 51 5A gF IF . 5A gI
( 237 ) 30 . 2 P bS 28 0 . 2 P bO

A related reaction is
( 38 )
2 4Na 3SiF. Si 2 Na .siF.

X RE STITUT IO N
.

The reverse reaction of substitution is re substitution -

or restitution the general type being MN

, MY
M N Y T o this class belong
.

2
( 39) 2 P hO P bS 3P b 80 2
( 24 0 ) 2 Cu O 0 u .s 4 Cu $0 2
2
( 4 1) Cu .S Cu SO. 3Cu 28 0 .

S imilar and related reactions are

( 24 3) 3B a sO . B aS 4 B aO SO.
( 244 ) B a CO a C B aO 2 CC
4
( 5)
2 N2 CaCN. C
92 CH E MICAL RE AC T IONS A ND THE IR EQ UATIONS

( 24 6) 4 B aSO. 40 4 B aO SO . 40 0
( 24 7 ) B aCO. 3Mg C B aCz 3MgO
( 248 ) 2 K NOa 1 0K 6K zO N2

XI . OXIDA T I O N A ND RE DU CTI O N

There are many reactions n ot classified under the

previous titles which are characterized by oxidation
and reduction These reactions must be studied and
.

in each c as e it should be determined which elements

are oxidize d and which are reduced for only thus is it ,

possible t o get a clea r concep tion of the meaning of

oxidation and reduction .

A num b er of such reactions are

24
( 9) 2 8 0 2 02 28 0 3
(250) 2 K N0 3 2 K N0 2 02
( 2 5 1 ) P C] . P Cl. Cl.
( 2 52 ) 2 CrO. 2 NH 3 N2 3H 2 O
( 2 53 ) 2 Cr0 3 1 2 H Cl 2 CrCls 3C]: GH 2 0
( 2 54 ) 2 Cu SO. 4 K ON 2 Cu CN 2 K zSO4 CzNz
4 CO SO 4 O. l OH .O
( 2 56 ) 3 K ClO K Cloa ZK Cl
( 2 57 ) 2 K ClO . K ClO. K CI 02
( 2 58 ) N 4C Nags 4 CC
( 2 59 ) 2 M11 0 2 2 K 2O 02 2 K 2 M110 4

( 2 60 ) H .T eCl¢ 28 0 . Te 2 H .SO 4
6H Cl
2 K OH 2 NO2 K NO. K NO . H .0
2 K OH 2 0 10 2 K ClO. K CIO. H .0
21°
5131 . me
ti 1 0H B r 2H P 0 .
N3 28 2 0 3 B T2 H 2O N8 2 8 0 4 2H B r
I ON0 6 K Mn 0 4 9H .SO4 1 0H N O .
6MDSO4 3K 2 SO4 4 11 2 0
Au 4 H Cl H NO. H A u Cl. NO 2 H .0
 '

94 CH E MICAL R E AC TIO NS A ND T IIE I R E Q UAT IO NS

The abo ve reactions are all in the non ionic or m ole cu -

lar form ; it is a helpful exercise to transc ribe these equa

tions into the io ni c form in cases where the substances
are ionized E xamples of typical ionic equations are :
.

0 X1 d3 ff10 11 1) y H 20 2
°

°
/vay
2 9
( 5) 2M n + + 11 2 0 2 34 4 oH 2 Mn ( OH ) 3 .

( 29 6) 2 Fe + + 12 2 0 2 4 OH 2 Fe ( OH ) 3
( 29 7 ) H 20 2 4 0 11
"

2 0 0 ( OH ) 3
2
( 9s) 20 + + 11 2 0 2 4 oH 2 Or ( OH ) 3
“
r
“
( 299 ) 2K I H zo2 2 K OH 12

The metals Cr and Mn can be further o xidized

.

( 300) 2 M I1 ( OH )3 H 20 2 2 Mn 0 2 4H 20
(30 1 ) 2 M 0 H 20 2 20 H 2 Mn 0 3 2H 2O
" "

n 2
“
( 302 ) 2 0 ( OH )s 2 OH 2 0 r0 2 + 4 H 2 0
"

( 303) 2 0 0 3H 2 0 2 20 H 20 I0 4 4H 2O
" _
1 2

By adding the equations for manganese (2 95 300) and ,

chromium (2 98 302 303) together the total equation

, , ,

of the reaction taking place becomes

M 2 Mn 0 2
“
( 304 ) 2 n + + 2H 20 2 4 OH 4H 20
“
( 30 5) 0
2 r + + 4 11 2 0 9 80 H 2 0 10 4 8 11 2 0

As shown by these equations hydrogen peroxide will act ,

as an oxidizing agent in alkaline solution In acid .

solution however it will act as a reducing agent :

,
.
,

( 300) CI 2 O 7 3H 2 0 2 8H + 7H 2 O
30 2
(307 ) 2 Mn 0 4 3H 2 0 2 2H +
2 Mn 0 § 4H 20 30 2
"

( 308 ) 2 M IIO2 2 H 2O 2 4H + 2M n + + 4 H 2O
20 2

By adding the last two equations (307 308 ) together , ,

and cancelling Mn Og whi ch appears on both si d es the ,

t otal equation b ecomes :

 TY P E S OF R E ACT IO NS A ND TH E IR E QUATIO N S

(309 ) 2 M n 0 4
“
5H 2 0 2 6H + 2M n ++ 8 H 20

Reduction by N0 2

( 31 0 ) 3N0 2 8H +
"

( 31 1 ) 2 M n 0 4
"

5N0 2
"

6H + 2M n ++

Reduction by H I
“
( 31 2 ) 0 r 2 0 7 GH I 8H +
3I 2 7H 20
( 31 3) 2 M n 0 4
“
I OH I 0H + 2M n + +
51 2 8 H 2O

( 31 6) H 2 8 04 8H I s 4I2 4 H 20 ,

Reduction by

( 31 7 ) OT 20 7 fiF e + + I4 H +

7H 2 0
( 31 8 ) Mn O r 5Fe ++
8H + M n ++

4 H 20
( 31 9 ) 3H g
++
6Fe ++
3H g

Reduction by ms
( 320 ) H 3A 30 4 s H 3A 30 3 S H 20
( 321 ) 2 H 3A 8 0 3 3H 2 S A S2 S3 GH 2 O
( 322 ) 2 H aA s O 4 511 2 3 A 32 3, 23 311 2 0

Oxidation by H N0 3

( 32 3) 3Z n 8H +
2 N0 3 3 Zn + + 2 NO 4 H 20
( 324 ) 3C u 3H + 2 N0 3 30 u ++
2NO 4 H 20
2 N0 2 NO
“
( 32 5) 3H g 3H +
3 3H g ++
4H 20
( 32 3) BSn 4H + 4 N0 3 311 2 8 110 3 4 NO
( 32 7 ) 3P bs 3H + 2 N0 3P b ++
38 2 N0
"

4 H 20
96 CH E MICAL RE AC TION S A ND TH E IR E QU ATION S

Oxidation by H 28 0 4
( 328 ) H 2SO 4 $0 2 “
1“H 0
2

(
“
329 ) Cu O 2H +
Cu ” H 20
“
( 0) Cu
33 4H +
80 4 Cu 802 2 H 20

Oxidation by H N0 2

( 331 ) CO ( N0 2 ) 2 2 H NO2 CO ( N0 2 ) 3 NO H 20
Oxidation and reduction of Hg

( 332 ) Hg
2 + H 2S Hg H gs 2H +

( 333 ) 2 H gC l 2 NH 3 NH 40 1 H g( NH z) Cl
\ Hg
( 334 ) 2 H g
+ 2 CN Hg H g( CN) 2

The student should devise laboratory experiments to

prove the correctness of these reactions and should be ,

able to pre dict what will hap p en if certain chemi cals

react upon each other H e should tell whether the
.

solutions mu st be acidified or made alkaline ; he should

k now what color changes or precipitations to expect an d
-

be able to write the specific non ionic equations for the -

above ionic reactions .

XII CO MP L E X REA CTI O NS

.

There are many c as es in which the reaction pro ducts

interact u p on each other an d produce a second set of
reaction products The equations of these reactions
.

seem most complex when secondary reactions are

included in a single equation ; but thi s com plexity disap
pears when more than one equation is written The .

following shows the various steps of such reactions in

different equations and these ad d e d together form the
, , ,

equation of a complex reaction .

( 335 ) 2 A lCla 3H 2 0 M ( OH ) : 6H Cl (hy d rolysis )

( 336) 3N a 2 8 2 0 3 6H Cl 6 N a0 1 38 38 0 2
( d ecom pos ition )
98 CH E MICAL RE AC TION S A ND T H E IR EQ UA TIONS

( 352 ) H 2 SD 0 2 2 N3 0 H N a2 8 n0 2 2H 20
( 353) 8 11 0 12 -
4 Na OH 2 NaCl NaQSn Oz 2 H zO

Ip a similar way some su lfides are formed :

( 354 ) 3H 0
g 21 2 11 2 3 4 H Cl 2 H gS H gClz .

( 355) 2 H gS H Cl
g z . 2 H Cl 3H g s
3H gClz 3s 6H Cl 3H gS

and
( 357 ) 2 P b 0 12 H gS 2 H Cl P bS P b0 12
.

( 358 ) P b S P b
. 0 12 s 2 H Cl 2 P bs
( 359 ) 2 P b 0 12 2 s 4H 0 1 2 P bs

Itmay be that only a part of a double salt w ill react ,

and the resultin g equation will appear complex ,

( 300 ) (
2 NH 4 ) 3A SSa 0H CI 0NH 4CI A 8 28 3 311 2 8

H owever this equation becomes Simple if the double salt

,

is considered as composed of two salts ,

( 361 ) (
2 NH 4 ) 3A s 8 3 A s zsa 3( NH 4) 2 S
.

and one of these reacts :

( 332 ) 3 ( N H 4 ) 2 8 GH Cl 3NH .CI

O ther examples are

( 363) 2 K M D 0 4 3H 2 SO 4 5H 2 0 2 K 28 0 4
2 M D SO 4 8 11 2 0 50 2

which is composed of the three steps

( 304 ) 2 K M D 0 4 H 2 SO4 2 H M11 0 4 K 2SO 4
( 365 ) 2 H M I104 5H 2 O2 2 MI1 ( 0 H ) 2 4 H 20 50 2
( 306) 2 M D ( 0 H )2 2 H 2 SO4 2 MII SO 4 4 H 20

or again
( 367 ) 2 A u 0 13 3H 2 0 2 6NaOH 2A u 6N a0 1
30 2 011 2 0
 TY P E S OF RE A CTI ONS A ND THE I R E QU AT I O N S

which consists of the three reactions

( 368 ) 2A u Cla 6Na O H 2 A u ( OH ) 3 6 N a0 1
( 36 9 ) 2 A U ( O H ) 3 A U 2 0 3 3 H 2 O
( 37 0 ) A U 2 O 3 3 H 2 0 2 2 A u 3 0 2 3H 2 O
I n the following complex reactions two or more steps
can be recognized and accordingly two or more equations
,

should be written for every case

( 37 1 ) Mn Oz 4 H Cl Mn Clz 2H 20 C12
( 37 2 ) 2 B 3 Cl2 K 2 0 1 20 ‘
7 H zo 2 B a CrO . 2 K CI
2 H Cl
( 37 3) Mn Clz 2 K OH H 20 2 2 K CI H QO
M D O (OH ) 2

When problems involve a series of incomple te oxida

tions and reductions it is well to construct separate
,

equations for each reaction A n example of this type is .

'

ofle re d by the following experiment : B y adding sulfuric

acid to potassium iodide a number of reaction products

are formed These reaction products are hydroiodic
.

acid iodine sulfur sul fur dioxide and hydrogen sulfide

, , , ,

besides potassium sulfate and water It is impossible to .

see from a single equation the changes which have

occurred and each oxidation and reduction must be

,

treated separately :
A The formation of hydroiodic acid
.

( 5)
37 ZK I H 28 0 4 K 28 0 4 HI
B . The formation of sulfur dioxide and iodine
( 37 6) 2 K I 2H 28 0 4 K 28 0 4 21 80 2 2H 20
C . The formation of sulfur and iodine
( 37 7 ) 6 K I 4H 28 0 4 3K 2 8 0 4 61 S 4 H 20
D: The formation of hydrogen sulfide and iodine :
( 37 8 ) SK I 5H 2 8 0 4 4 K 28 0 4 81 H 2S 2 H 20
1 00 C H E MI CAL R E A CTI ON S A ND THE I R E QU A T I ON S

These e quations show that in A there is a simple meta

thesis the replacement oi a weaker acid by a stronger
,

acid ; in B the iodide is oxidized to iodine and the hexa ,

valent sulfur is reduced to tetravalent sulfur in C to free ,

sulfur and finally in D to sulfide It is quite p ossible

,
.

that the reactions B C and D are secondary reactions

, , , ,

as the H I formed in re action A may be decomposed by

the sulfuric acid If such is the case the K I of the equa
.

tions should be replaced by H I and the unfinished equa ,

tions are
“
( )
b H I H +
$0 1 I 80 2 H 2O
( ) C 2
—I + S + H O
“
( )
d H I H +
$ 0 5 I H 2 S H 2O

I f the equations ( 377 ) and ( 7 8 ) are added

“
3
the following monster equation results
( 379) I SK I 12 H 28 0 4 9K 28 0 4 2H I 1 61
80 2 S H 2S 1 OH 2 O

QU E S T O NS A ND P I
ROB L E M S
1 C lassify t he following reac tions according to typ e an d note part ic
.

ularly whe the r oxi d ation a n d red uc tion is involv ed If so whi c h e le .

,

m e nts are oxi di z ed an d whic h are re d u ced

(380) AgNO . Na NO, AgNO , Na NO a
(38 1 ) Na Cl A gOH Na OH A3 0 1
(382 ) 2H g +
Or or H ggCr0 4
‘

(383) F8 ( OH ) 3 3H B I Fe B r .
‘
311 2 0
(38 4 ) P tS H2 Pt H gS
(38 5) Mn Clg Mn COa 2 Na Cl
( 6)
38 2 K 3Mn 0 4 H ,O 2 K OH K za os 02
(387 ) Mn ++
20 1
*

4 H 30 Mn Cl, 4 H gO .

(388 ) Cd Clz 4 B h Cl Rb 4 0 d 0 16
(389) Hg ++
H8 2Hg +

(390 ) B OO H ,O B 8 (0 H ) 3
(39 1 ) TI +
Cl “ =
T lCl
( 392 ) T i NO ; Na Cl T lCl Na NO.
(393) 2 Mn 0 2 2 11 38 0 4 2 MDSO4 2 H 30 03
(395) T iCl. 4 H 30 H 4 T i0 4 4 H Cl
102 C H E MI CAL R E A CT I O N S A ND TH E IR EQU ATI ONS

(44 1 ) ZA gO H A g, o H aO
(4 4 2 ) 2A I 6H Cl 2 AlCls 3K :
(4 4 3) 2 AlCls 2 AI 30 12
(444 ) A 10 1: 3H zO M (OH ) s 3H Cl
(44 5) M ( OH ) 3 3H Cl A lCls 3H zO
(44 6) 2A I 38 A1.s.
2 . Write
reac tions (38 0) an d (38 1 ) in the ionic form an d de duc e their
gene ral m eaning and t he e xp erim e ntal c onditions .

3 De vise a labor atory e x p e ri m e nt to p rov e t h e c orre c tne ss of reac tions

.

an d 434 .

Translate t he m e aning of reac tion ( 38 7 ) into c omm on langu age

4 . .

5 What is th e diff e re n ce be twee n t he re ac tions

.
( 408 ) an d
What equation res ults if (4 08 ) is added to a n d ( 409 ) is a dd e d to

(4 1 1 )
6 Can
. you pred ic t fro m the d isplac e me nt se rie s that the reac tions
shown in e q u ations a n d ( 4 1 6 ) will tak e

pla ce ? On what groun ds do you base your pred ic tions ?

7 Wh at is t he m e a ning of e quations
.
( 42 8 ) an d a n d what

a c tu a l ph e nom e n a or re ac tions c or re sp on d to th ese e qu ations ?

8 Is the re an esse ntial d i ff e re n ce b et we en t he rea c tions e x p re sse d in

.

( 4 30 ) an d

9 . What is t he diff e rence or sim ilarity between ( 4 31 ) an d (4 2 6 )

an d (396) an d ( 403) an d

10 Com pare e quations (38 7 ) an d (42 8 ) an d state if e ithe r of the se

.

re actions is a reve rsible on e ?

1 1 What will happ en if Br is substituted for F . in re ac tion
. ,

Wh at will hap pe n if H B r is tak en instead of H CI?

12 Write th e c om pl e x reac tion ob tain ed b y add ing e qu a tion s ( 4 37 )
.

an d (4 38 ) tog et h e r Desc rib e t h e ex pe rim e nta l con ditions

. .

1 3 What is t he m eaning of eq uations

. an d D e v is e
e x p e ri m e nts for eac h reaction .

1 4 Sta te in c omm on term s t he in form ation c ontain ed in e quation s

.

Suggest for each equation the e xpe rim e nta l

c on d itions un d e r whi c h t h e rea c tion tak es p lac e .

1 5 How will t he sp eed of r eac tion ( 44 6 ) b e aff e c te d if S is re p lac e d b y

.

( a ) Se, ( b) T e, (c) O?
16 . Why d o es t he T e in (4 36 ) rob the S of a part of its 0 ? Sugges t a n
ex planation .

1 7 Wha t is t he di ff e ren c e b etwee n eq uation s ( 39 1 ) an d

1 8 Wha t tak es plac e in t he re ac tions ex p resse d in e q u ations
. ( 400 ) an d

Gi ve a com m on te rm for the p he nom e na .

1 9 Does S re p l ac e 0 or d oes 0 rep lac e S in re ac tion

.
,
Is this
reaction in harm ony with t he dis p lace m e nt se ries ?
 A P P E ND IX I

K E Y T O NO ME NCL A T U RE O F CH E MICA L
CO MP OU ND S

This key to the nomenclature of inorganic compounds

enables the beginner to const ruct numerous formul as
of compounds whose names are given and likewise to ,

find the correct name for a given formula I t will also .

aid in finding possible reaction products in cas es where a

precipitate or a change of color occurs during the reaction .

To construct the formula for a compoun d it is only

necessary to ! oin the radicals or ions in such a way
that all the valencies or charges are satisfie d or neutral
iz e d
. The formula for cupric sulfate is found by
“
! oining Cu ++
( cupric ion ) and S O . ( sulfa t e ion ) to
Cu SOI The formula for ferric chromate is foun d by
.
”

! oining six positive char g )es with 3C r O I

( six negative charges

chlorate requires Cu
)
“
to
an d
Fe 2 ( Cr 0 4 ) 3 . L ikewise cupric
that is Cu ( ClOs) 2 .

Cuprous phosphide is Cu sP and cupric phosphi d e is

,

CU 3P 2 .

By finding the ion or radical under the formul as t he

name of a given formula can be constructed : Fe s shows
iron to be bivalent hence ferrous sulfi d e while ,

in Fe 2 S3 the iron is trivalent hence ferric

w
sulfide Like ise the formulas NaCl NaClOz NaClOa
.
,

NaClOI represent respectively sodium chloride sodium

, ,

chlori te sodium ch lora te and sodium per chlorate

, , .

The column indicating the color of the ion or radical

is of advantage in laboratory work where the formation
1 03
104 A PP E NDIX

i
alum n um ion Ar i 0+
-

“
alumi na to ion A10 3

bi s m ut hy l

br om id e

cad m u m i

bi c hrom a t e

c opper a m m on um i
1 06 A PPE NDIX

Silic on

ot r on tiu m

0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

ad icalc

of a distinctive color in the test tube will show the

respective ion or compoun d Thus if during a chemi cal .
,

reaction the yellow solution of a chromate turns green

chromic ion has been form
,

ed ,if the purple permanganate

s olution turn s green
—manganate ion has been produced ,

and so on Wh ere no color is given the substance is

.

colorless or white .

If necessary the stu d ent may enlarg e the list to meet

sp ecial requirements A frequent use of this key in the .

laboratory is recommended .
 A P P E ND IX II

D I SP L A CE ME NT SE RIE S

( E lements printe d in capitals to be memorized by the

student )
In th e di splacementseries the elements are arranged
according to their electro motive force , that is the
-

capacity of holding the ionic charges more or less firmly .

V
NE G AT I E c olum b iuin

ca dm ium
I R ON
Z I NC
m anganese
uranium
gad olinium

A L L U M INIU M
te llurium rare e a rth m e tals
-

P HO SP HOR U S b eryllium
c hrom ium scan d ium

vanad ium H YD R O G E N yttrium

tungste n M A G NE SI U M
m olybd e num
CARB O N
b oron
G OL D
osm i um
p latinum
ir id ium
P OSIT IVE
1 08 APP E N D IX

At the top of the list are the most negative elements

which displace all following anions The elements near
.

the end of the list are the most positive and will displace
each cation above them Thus B r will displace I and S
.
,

but F w lll displace Cl and B r Ca will displace Mg A l

.
, ,

and Fe but K will displace N a and Ca etc

, ,
.

The farther apart the elements the more stable their

,

compounds Thus K F is the most stable compound

.
,

while a compound of O and F is so unstable that it

cannot exist .
1 10 A PP E ND IX

presented the first table of a system of elements which

w as generally accepted M e n de leefi p redicted the .

properties of three unknown elements from three em pty

sp aces occuring in his table and when these elements ,

were later discovered it w as found that his predictions

,

came true with an astounding accuracy Since that .

time numerous discoveries have been made and the

system has gradually been completed Today we may .

assume with great confidence that only five elements

remain undiscovered and that the total number of
elements in the series from hydroge n to uran ium inclusive
is 92 The five unknown elements with atomic numbers
.

4 3 6 1 75 8 5 and 8 7 would complete the table

, , , ,
.

I f all elements ar e arranged in the order of increasing

atomic weights then the 92 elements between H ( A t No
,
. .

1 ) and U ( A t N o 92 ) in clusive are divided into six perio d s

. .
,

the terminals of each period being the no ble gases Thus .

there are in
Pe riod 1 e xte nd ing from He to Ne
, 8 l nts
e em e 2 X 2 ) 3

Pe riod II exte nd ing from Ne to Ar

, 8 e le m e nts 2 X 2 )
2

Pe riod III e xte nd ing from Ar to Kr

,
1 8 e le m e nts 2 X 3 )
3

Period IVexte nd ing from Kr to X e

, 1 8 e le m e nts 2 X 3 )
2

Pe riod Ve xte nd ing from X e to Nt

, 32 e lem e nts 2 X 4 )
2

Pe riod VI e xte n d in g from N t to U

, 7 e l e m e nts

E ach pe riod has the following characteristics

The terminals of each period are electrically neutral
( noble gases ) .

The first three elements of each period are strongly

electropositive ( light metals) .

The last three elements of each pe riod are strongly

electronegative ( non metals) -
.

The central members of each period are amphoteric

( heavy metals) .

The members of the carbon family are the framework

 AP P E NDIX

of the system and form a transition between the diff erent

groups of elements ( 0 the life element S i the rock -

formin g element ) .

B esides the horiz oa division into periods there is

the ver tical division into gr ou ps The general rule of .

the periodic chart is

The similarity among the elements in the upper half

The P erio di c S yst em

NO N ME TAL S -
INE RT E LE ME NTS LIG HT ME TAL S
G r ou p 4 5a Ga 7a 0 la 2a 3a 4a
‘
6
i
a

3 53 3 a3 s:
o
53
D
C
5

'
Iron cd Ir on riod
I I '
II I?

58 59 60 6 1 62 63 64 6 5 66 67 68 69 7 0 7 1 7 2 Ra re e a rt h
Ce P r Nd Sm E u G d T b D y H o E r D b T m Y b L u

d
G ol
ne
w}

90 91 92
Th Bv U

G r ou p 4 5b 6h 7b 8 8 8 lb 2b 3b 4
H AV
E Y ME TALS
l 12 AP P E NDIX

of the table is most pronounced in the vertical direction ,

therefore these elements possess group analogy -

.

The similarity am dn g the elements of the lower half

of the table is most pronounced in the horizontal direct
ion therefore these elements possess period analogy
,
-
.

ATO MI C NU MB E RS A ND A TOMI C WE I G H TS
I m or ta n c e of the e le m e n ts is i di
n c at e d by d Th
an t mi mb o. e a o c nu ers s e r ve a s

w in a n t o t he p e ri o dic b
t a le .

144 3

P olon i um

P ot ass u m i
dy
P r ase o m i u m
o Radi u m
h i
R od u m
bi i
Ru d u m

R th i m
u en u
S m i m
a ar u
Sca n di m u
o S l i m
e en u
Sili c on

0 0 0 0 0 0 0 0 0 0

l 008
. 0 i i
T t a n um
1 14 8 T u ngs t e n
i
.

0 U ra n um
Va na dium
.

19 3 l

X e n on
Y t ter i u m b
Y t tr u mi
i
o Z nc
i
Z rc on u m i
O l ( lu cin um ) is B e ( B er ll u m y i
o Ma ngan e se .
f bi m
N b ni o u ) is Cb ( C olu m u m )
F1 1 5 F ; X e 1 3 X ; Y t 1 3 Y
bi
.

A : ( n ote ) is N ; J ( ! od ) is I .
l 14 APP E N DIX

with bol d typ e and for they c onstitute 99 per cent of

the known e art h su rface and are a bundant in the lith o
sphere hydrosphere atmosphere These elements are
, ,
.

es se ntial to all living matter ( biosphere) an d are of

fundamental imp ortance in every industry A b out 4 0 .

elements are of secondary importan ce ( marked o) for ,

they are less abundant and are used only for specific
pu rposes in industry and techni c A b out 33 elements are .

of more or l ess scientific interest on ly for they very rarely

occur an d are of l ittle or no present use .

The student must be familiar with the fourteen im

portant an d fundamental elements know their position ,

in the tabl e and b e fami liar with their chemistry for

, ,

they are most common on the surface of ou r earth and

their comp ound s are used in every industry in every ,

material science and in every day life E lementary ,

-
.

chemistry confines itself mainly to these elements as

they are the b asis for a study of the other elements .

Thus e g with chlorine as type or examp le the proper

,
. .
,

ties oi fluorine b romine and io dine can readily be

, ,

memorized ; while w ith sulfur as typ e or exam p le the

characteristics of selenium an d te llurium are easily
learned ; potassium an d s odium is the typ e for lithium ,

rubidium an d cesium ; manganese is similar to chromium

—
, ,

iron similar to cobalt an d n ickel and so on .

RE FE RE NCE S
Classification of chem ical ele m ents Scie ntific Ame ric an Suppleme nt ; ,

vol 8 7 p 1 46 1 9 19
.
, .
, .

M odification of the pe riod ic tab le A m J our of Scie nce vol 4 6 p 4 8 1

, . .
, .
, .
,

19 18 .

Distrib ution of c hem ca i l e le m e nts Science Progress vol

, , . 1 4, p . 602 ,
1 920 .

BOOK S SUB J E CT
ON T H E

Rudorf G T he Pe riod ic Sys te m

,
.
,
.

Garre tt A E T he Pe riod ic L aw
, . .
,
.
 A P P E ND IX I V
SO L UBIL IT Y T AB L E O F CO MP O U ND S

( T o be Memorized by Students)
SOLU B LE in water
A L L CH LOR I D E S except A gCl P hCl2 H gCl;
, , ,

A L L NI T RA T E S except bismuth subnitrate ;

, ,

A L L SUL F A T E S except bari um sulfate strontium

, ,

sulfate calcium sulfate lead sulfate ;

, ,

A L L A CE T A T E S except basic ferric acetate and basic

,

aluminum acetate ;
A L AL K AL I SAL T S except acid potassium tartrate
L
, , ,

acid ammonium tartrate potassium platin chloride

, ,

amm o n ium platin chloride and sodium pyro ,

antimoni ate .

I NSOLU B LE in water
O) II E
I III
"
SU I I ) BS
except those of the alkalies
and earth alkali metals ;
ALL H YD RO XI D E S

fi:PHO
HHHATES
l ( I 1

l I except those of the alkali

metals ?
A LL SI L I CA T E S
A L L CH RO MA T E S, except those of the alkalies ;
Ca , Sr .

SO L U B I L I TY T AB L E OF CO M P O U N D S
( for reference )
A CE T AT E S are SOLU B LE , except A gA c , H gA c ,
H gA C2 .
1 16 A PP E N DIX

A R SE NI T E S are I NSOLUB LE except those of the ,

alkalies .

AR SE NAT E S are I NSOLU B LE except those of the ,

alkalies and the acid arsenates of the earth alkali

metals .

B ORAT E S are SOLUB LE .

B RO MAT E S are SOLUB LE leas t soluble are ,

H gB rOs, A gB rO s .

B RO M I D E S are SOLU B LE , except Cu B r ,

A gB r ,
H gB r, P bB I 2 ’
.

CAR B O NA T E S are insolu ble except those of alkalies

,

and T I .

CH LORAT E S ar e SOL U B LE except H gClOa , .

CH LOR I D E S are SOLU B L E except A gCl , , H gCl ,

Cu Cl, A u Cl, P t Cl2 , P bCl2 .

CH RO MAT E S are I NSOLU B LE , except those of

alkalies and G aCrO4 , Sr CrO4 and MgCrO4 .

CY A NI D E S are IN SOLU B LE except those of alkalies ,

and earth alkalies .

F E RRO CY A NI D E S are I NSOL U B LE except tho se ,

of alkalies and earth alkalies .

F E RR I CYA NI D E S are I NSOL U B LE except those of ,

alkalies and earth alkalies .

FLU OR I D E S are I NSOLU B LE except those of ,

alkalies and A gF Fe Sa Se and O s, , ,

.

I O D AT E S are I NSOLU B LE except those of alkalies , .

I O D I D E S are SOLU B LE except A gI Cu I H gI z , , , ,

P bI z B il a SbI a P t metals
, , ,
.

M A NG A NAT E S are I NSOLU B LE except those of ,

the alkalies .

MOLYBD AT E S are I NSOLU B LE except those of ,

the alkalies .

NI T RAT E S are SOLU B LE .

NI T R I T E S are SOLU B LE except A gNOz , .

 AP P E ND IX V
P RE P ARAT I O N O F SAL T S

A M etallic Salt May b e P repare d in A n y On e of t he

Following Ways ( T o be Memorized by t he S tu d ent )

Reaction between
1 . ME T AL and H ALO G E N
Zn

la . ME T AL and ACI D
Z 1] H 2 SO4 Z D SO4 H2

2 . ME T AL O XI D E and A CI D
- -
A NH Y D R I D E
Z IIO $0 3 Z II SO 4

2a . ME T AL O XI DE a
n d A CI D
-

l o H 28 0 4 Z D SO4 H 20

3 . ME T AL H Y D RO XI D E and A CI D A NH Y D R I D E
Z D (0 H ) 2 80 3 Z IISO4 H 20

3a . ME T AL H Y D R OXI D E an d A CI D
Z n ( OH ) 2 H 2 S0 4 Z n SO4 2H 20

4 . ME T AL C A R B O NA T E an d A CI D
Zn 0 0 3 H 28 0 4 Z II SO4 002 H 20

5 . ME T AL SULFI D E and ACI D

Z IIS H 2 SO4 Z D SO4 11 2 8

6 . I nteraction of t w o ME T AL SAL T S
Z II ( N0 3) 2 Na 2 so 4 Z II SO4 2 N3 N0 3
1 18
 A PP E ND IX 1 19

K E Y T o T H E E QU A T I O NS

The following is a systematic in dex of the equations

u sed in this book The numbers to the left of the
.

formula refer to the reacting substances ( which stand

at the left of an e quation ) and the numbers to the
,

right refer to reaction products ( which stand at the

right si de of an equation) .

This index makes it possible to find at a glance how

—
some of the su b stances are prepared thus under oxygen
there is a score of equations showing how this gas may
be made It also gives the analytical tests for many
.

comp ounds that is the reactions use d for their detection

, , .

Furthermore it will facilitate the const r uction of similar

equations for reactions taking place w ith related ele
ments Thus many reac tions given under sulfur occur
.

also with selenium and tellurium likewise those of ,

arsenic compounds have a relation to those of antimony

and bismuth compounds .

I t is well for students to make a comparativ e stu dy

of reactions by consulting the p eriodic system and the
displ acement series an d extend this index to the labora
tory and lecture note book for further reference .

4 42 ,

1 52, 335, 337, 34 2, 34 5, 4 43, 1 1 3 5, 442 , 44 5

-

4 44
1 13 0 0
g 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

1 14
1 15
1 15
1 31
9, 34 3, 344, 42 5, 4 4 5 . 2 0, 2 1 , 1 31, 1 52 , 335, 337
338 , 342 , 4 44

0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
1 20 APP E NDIX

n /
1 0 1, 1 05, 168 , 2 82, 29 4

4 5, 8 6, 374
88 , 233,

0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

O O O O O O O O O O O O O O O O O O O O O O O

O O O O O O O O O O O O O O O O O O O
 A PP E N DIX
2 74 , 2 7 5

42 0

o o o o o o o o o o o o o o o o o o

o o o o o o o o o o o o o o o o o

o o o o o o o o o o o o o o o o o o o 2 4 5, 2 4 4 , 258 , 2 73, 2 74, 2 7 5

2 0 , 2 1 , 59 , 1 34 , 2 42 , 2 8 8 ,
4 00, 4 0 1, 4 20 , 4 30 , 4 31

2 7, 53, 17 7 , 18 2 , 1 8 3, 2 1 4 , 195 , 1 98 , 2 00, 2 0 1 , 2 1 5, 2 18 ,

2 34 , 2 75, 2 8 0, 2 92 2 1 9, 2 51 , 2 53, 37 1, 4 10, 4 1 1 ,
4 15 4 37, 4 4 3
38 7, 39 1 . 2 7, 53
2 , 4 , 6, 8 , 1 9, 1 1 0, 1 18 , 196, 10 1, 235, 2 8 3, 2 8 4 ,
2 2 3, 2 8 7 , 37 1 372 ,
2 62
2 35, 2 8 2

2 98 , 305
306 310
303 302
1 4 0, 38 2 , 4 33
2 5, 35, 2 8 1 , 306, 310, 31 2 ,

2 53
20 1 , 2 52 , 2 58 28 1
 A PP E NDIX 123

COB A L T

CO P P E R
2 5, 50, 55, 2 08 , 22 9,
5 1, 32 4 , 32 9 , 330
1 34

1 04
l o8 b, 1 59, 24 1, 254

F L U O RI N E

12 4 1 8 1, 2 1 5, 2 1 7, 4 1 5, 4 1 8
2 35

G A L L IU M
1 24 A PP E NDIX

4 0, 4 4, 1 7 5, 18 1 , —
2 2 8 2 32 , 4 2 , 4 3, 4 1 , 222 22 7, 4 1 5, 44 2 -

2 93, 38 4
1 5, 33, 34 , 35, 4 5, 305 to 31 5, 2 3, 332
323 to 331
1 5, 2 4 , 2 3, 4 5, 2 95 to 2 98 , 302 ,

—
304 8 , 44 0
-

4 1 3, 2 1 5, 335, 4 1 5, 8 2 8 5, 2 18 , 300 331

—
- - -

295 309 , 353, 357, 370, 37 3 . 40 7

55, 18 4 , 2 35, 2 8 5, 4 14 54 , 1 99, 2 1 3, 2 8 7, 2 99 , 31 2

31 5, —
37 5 37 9 ,
4 19
55
379 , 4 1 4

2 5, 4 1 , 4 2 , 4 3, 55, 1 78 , 1 7 9, 4 0, 4 4 , 2 05, 20 9
1 9 5, 2 05, 208 , 2 1 2
34 , 1 4 5, 2 95, —
31 7 319

O O O O O O O O O O O O O O O O O O

o o o o o o o o o o o o o o o o

o o o o o o o o o o o o o o o o o o
126 APP E NDIX
332 ,
5 1,
333
207, 233, 2 7 0 , 354 , 355
2 59

1 94

0 0 0 0 0 0

1 36 .

28 7

(see ammonia)
2 66
30
1 8 0, 18 9, 2 04 , 2 61 . 2 8 8 , 2 8 9 ,
2 90

29 1

28 2
29 1

2 9, 1 75, 1 79, 1 8 0, 1 8 7, 1 9 1, 2 8 , 4 7, 1 97, 2 0 1 , 2 02 , 2 05,

205, 2 18 , 2 1 9, 220 , 2 37, 24 9, 2 1 7, 2 55, 2 57, 2 58 , 2 77, 2 79 ,
305 9, 353, 355,
-
357, 370 ,
 APPE N DIX 12 7

1 8 2,

1 54 , 2 5 1 , 8 7, 1 33

0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

O O O O O O O O O O O O O O O O O O O O O O O

200 , 38 4

0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

22 5, 2 2 7

3, 2 57
1 , 2 99, —
375 9 ,

4 13 .

78 , 2 59
22 5 , 22 7
12 8 APP E ND IX

1 25

388

27 4 , 2 7 5 399
1 22

235 2 15

2 14 2 13
. 2 35
439 . . 39 341
3 , ,
44 1

34 1, 3 1 ,8 441
109, 2 72 , 339, 340, 38 0 .

2 9, 238 , 4 1 6 .
1 30 APP E N D IX

O O O O O O O O O O O O O O O O O

O O O O O O O O O O O O O O O O O O O O O

O O O O O O O O O O O O O O O O O O O O O O O

0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
0 0 0 0 0 0 0 0

0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

4 9, 1 8 5, 18 5, 209
222 , 2 2 5, 32 3 19 8 , 2 1 0

211
A PP E N DIX 1 31
134 IN D EX AN D G LO SSARY
CLA SSI FI C A TI ON OF ELE M EN TS is deri ved from the periodi c
sys te m

COLLO ID S are partic les of ultra m icrosc0 pic siz e -

—
C OLOR often in dicates the stage of ox id ation
c han g e in di cates a c he m ic al r eac tion

C OM BI N A TI O N is a chemical reac tion in whic h two elements unite

and form a compoun d one element being reduced the other
, ,

oxidiz ed
COMPLEX I ON is a radi cle or group of atoms w hic h is elec trically
-

c harg ed either positively or negatively

,
.

C OM PLEX REAC TI ON results from chem ical c hanges in w hic h

two or m ore types of reac tion simultaneous ly take p lace 96

—
COM P OUN D S are m ole cules with u nlike atoms
the sum of v alence numbers in stable compoun ds is zero
6
14
the weight relation of their cons tituents is s hown in a formu la
-
6 .

—
the p ercentage compositio n is calcul ated from fo rmul a 6 19
-

the sam e elem ent may form difle ren t series of compounds 13 .

the nam es of difleren t series depend upon valence number

-
1 7 1 03 ,

C ON C EN TRA TI ON is the amount of ato ms or m olecules in a cer

tain volume ; cone of gas es is exp ressed in te rms of pressure
.

— cone of s ubs ta nces i

. solutions is e xp ress e d in m ol es per lite r

c ha n g e in c on c entration afi
n

ec ts the c he m i ca l eq uilib rium

DE COM P O SITI O N is the revers e reac tion of addition

DI S PL AC E M EN T is a c he m ica l rea c tion in whic h one elem ent
ex c han ges c harges —
with an other element it is either oxidation
or re duc tion 69 8 9 .
,

D I S PLAC E M EN T SER I ES is an a rran g em ent of the ele m ents in

the order in w hic h they hold their elec tric c harges 70 1 0 7 ,

in di cates the elec tro m otive forc e of ele m ents

-
68
D I SSOC I A TI O N is the b re akin g apart of m olecu les 63

— thermal dissoci ation takes place u nder the influen c e of heat 64

-

e l ec trica1 diss o c i ation or ioni zation is p ro du c e d b y elec tric ity 3 65 .

,

DIV ISI ON is the reverse reac tion of combin ation in whic h a com
pound breaks apart one elem ent b eing oxidized the other
, ,

88

E
'
M F elec tro m otive forc e
. . .
-
68
EAR TH ALK AL I M E TALS are the elem ents of the se cond group
— of the periodic sys te m : M g Ca Sr B a
they are b iv alent but u nivalent
,

13
.

E AR TH M E TAL S arethe elem ents of the third g roup of the periodic

, , .

,
111
1 10

sys te m e g Al Sc . .
, ,

they are trivalent but univalent

-
,
 I N DEX AN D G L O SSA RY 135

ELE M EN TS are c hem ically in divis able and indest ruc table sub
s tances whos e m olecu l es c o nsis t of like atoms
-
in their free s ta te they have a v alen c e num b er of z ero
-
thos e havin g in their compou nds but one vale nc e number are
un ivalent thos e wit h two or m ore are poly valent
,

ELE C TRI C B ATTERY is formed when t wo c lments are connec ted

by a conduc tin g m edi a but are locally separated so that a dis
placem ent reac tion can take plac e
ELEC TRI C DI SSOC I A TI ON is ioni zation
E LE C TRO AFFI N ITY or e m f is the forc e with whic h the ato ms
. . .

hold their equ ally large ioni c c ha rges 68

ELE C TROD E is the positive or neg ative pole 65 .
, 71
E L E C T ROLYSI S is the spac i al or local se paration of io ns (catio ns
an d anions ) b y a n e le ct ric current 65
ELE CTRO MOTIVE FORC E is the power of an atom to
-

retain ele c trical c h arg es as ex p ress ed I n t he dis p lac e m ent series 68

ELE C TRO P OTEN TIAL is the tens ion b etween two difie ren t sets
-

of atoms and their ions exp ress ed in volts

,

ELE M EN T is an aggreg ation of matte r c onsis ting of one typ e of

EN D O THERM I C C OM PO U N D req uires heat for its formation ,

and lib era tes he at in its d eco mp os ition .

E ND OT H E RMIC RE AC TI ON a lw ays pro c ee ds s lowly a nd

req u ir es h e at whic h it ab sor bs

EQUA TI O N Is the ex pression of a c hem ic al reaction

—there are non ionic or molecular and Ionic equations
-

balanc ing of equations

—finishin g of inco mplet e equations “
-

—the universal equation of neutralizatIOn 1s H+ OH H O “

g .

EQUIL IB R IU M Is the balanced state reac hed m a chemical reac tion

when the concentration b etween the reacting substances has
be com e su ch th at decomposition and re comb ination p roc eeds
,
—
with equal sp ee d
-
the rem oval of one reac tion product shifts the equilib rium and the
-

reaction m ay proc eed to comp letion

EX OTH ERM I C C OM P OU N D liberates heat in its formation and ,

requires or absorbs heat in its d ecomposition

EX OTHERM I C R EAC TI O N proc eeds rapidly and lib erates heat .

EX PLOSI O NS are exothermic re actions

FORM ULA is a co mbin ation of symbols show ing the compos ition of
a m olec ule 6 .
, 10
-
T here are four ty pes of fo rmul a e mpiri ca l constitution al
.
, ,

ration al an d structural
, .
1 36 IN DE X AND G L O SSA RY

—S m mary of the info mation c

u r o ntained in formula :

—
G A S formation in d icates a che m i cal re ac tion
d ensity, weig ht of 1 lite r, s pec ific g ravity,
.

a nd volum e relation
of a gas is shown In the form ula .

G OLD P ER I OD 18 compose d of the elem ents of the fifth sub p eri od -

of the periodic syste m

G RAM MOLEC ULE is the m olecu lar weight of a compound in
gram s
H EA T increases the sp ee d of reac tions
—p roduc es thermal dissociation
—is absorbed in endothermic reac tions and liberated in exotherm ic
,
.

reactions
—is absorbed in the formation of endothermic compounds and
,

liberate d in the formation of exotherm ic compo unds ,

H EA V Y M E TALS are the elem ents of the sub perio ds of the -

é i di y tem (lower part of char t ) 1 10 1 1 3

—are all polyvalent therefore have diff erent se ries of compounds
p r o c s s ,

ous and ic com po u nds ) 13 17

—m ay be amphoteric and form many complex compoun ds
- -

, 1 13
HY D ROGEN is the b asis of v alency and v alence numb ers 11
—E lem ents combining with H have a negative v alence numb er 12
—
.

E lem ents rep lacing H h ave a pos itive v alen ce nu mb er 12

HY D ROLYSI S is the reverse reac tion of neutralis ation 86

INE RT ELE M EN TS ( or nob le gas es ) do not com bine with any

other elem ent 111 , 1 13
I O N I C R EAC TI O NS occur only when the s ubstance is in solution 57
—proc eed very rap idly and de pe nd upon the forma tion of one of
,

7 c omp ou nds
I ON IZ A TI ON or electric dissociation is the b reakin g apart of
molecules (electrically ne utral) into electrified atom s (c harged
positively or neg ati vely ) taking plac e when certain substances
are d issolved in w ater .

IONS a re elec tri cally c ha rg ed atom s or gro ups of

-
T hey m ay have one or m ore pos itive ( cations ) or neg ative ( anion s )
c harges
— Ionic charges are balanced before the atom s are balan ced
—and after oxidation and reduction 5 balanced 1

IRON PER I OD the ele m ents Of the third sub period of the peri odic
”

- -

syst e m C r M n Fe C o Ni Cu
, , , , ,
. . 1 13

LI G HT M E TALS are th e elem ents of the a s ub

- -
perio ds of the
1 38 IN DEX A ND G O L SSARY
RADI OAC TIVE ELE M EN TS are the ele m ents Of highes t ato mi c
weight w hich spontaneo us ly d is integrate or b reak apart l11
RARE EA R TH M E TALS are the elem ents of the V sub period
" -
11 1
REAC TI ON is a c hem ical ch ange or in te raction of m olecu les
—
Control of re ac tion dep ends on c oncentration velocity and the ,
23

48 , 7 5
—Control of ionic reaction depend on
.

s s t he formation of one of
even substanc es
s 57 75
RE DUC TI O N 8 the d ecreas e or di m inution of the v
,

1 alence nu mber
RESTITUTI O N Is the reverse reaction of substitu tion . 91

SALTS are generally form ed from acids and bases ( neutralization )

—T hey may be prepared from metal m e taloxides m etalhydroxides , ,

m e talc arbon at es m etal s u lfid es

,

S ILVER PERI OD are the elem ents of the fourths ub p eriod -

.

S OLUBILITY TA BLE
m
.

SUB STITUTI ON is a c hem ica l re action In whic h an ele ent is

either oxidised or reduc ed and comb ines with the dis plac ed
element
SULFUR GROUP are the ele m ents of the sixth g roup of the periodic
sy s te m 0 S Se T e
.
, , ,
. .

SYM B OL is one or two lette rs representing an atom and its relative

mas s
—is us ed to represent an atom molecule or Ion
.

, ,

VALEN CE N U M B ER the arith metical express ion of v alency

is
—
.

It can b e either or an d is b ase d upon H l and O 2 12 14

—of the same element may be diflerent and then it indicates diff erent , ,
.

'

s eries of compo un ds
—of free elements is always zero
.

—the sum in a stable compo und is always zero

VALEN CY is the capacity of an atom to combine with other atoms
in a d efinite p roportion 11
—is m easured with regard to H and can b e any integer from 1 8 12
—when u nknown may be calc ulate d from the formula 14

W A TE R form ation is the ch aracteris tic earma rk of neutrali zation 27

WA TE R OF CRYSTAL LI Z A TI O N is the water contain ed in
c rystals