Ill

г " л

PR EFA C E

O ver th re e y e a rs of w ork h a v e gone in to a careful rev isio n b a se d on th e exp erien ces of a u r

own te a c h in g a n d th e su g g estio n s a n d id eas of o u r m a n y u s e rs a n d colleagues. D u rin g th e r e ­
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W e h av e also p re p a re d th e books experim ents for chem istry a n d teacher's manual for
chemistry П
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th in g s o cc u rrin g a ro u n d us.
T h is textbook w as designed for a one y e a r ch e m istry course. T he te x t is ap p lica b le to h ig h
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on ch em istry . To h e ig h te n s tu d e n ts ' in te re s t a n d to m a k e ch e m istry enjoyable:
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T h e A u th o rs
 ...... и.......... и.............................. и... у

CONTENTS

1 .a r a t e s of c h e m ic a l r e a c t io n s ................................ l

1.1 Meaning and measurement of reaction rate ............................................................................3

1.2 Collision theory ..................................................................................... 6

1.3 Energy changes during a reaction ........................................................................................... 8

1.4 Factors affecting reaction rates ................................. 12
1.4.1 Nature of reactants .................................................................................................... 12
1.4.2 Concentration of reactants ........................................................................................13
1.4.3 Tem perature ..................... 16
1.4.4 Catalysts .................................................................. 17
1.4.5 Interacting area between reacting substances.................................................... 18
1.5 Reaction mechanism ............ 19
1.6 The effect of catalyst on a reaction with m echanism ............................................................22
Some New Terms ...................................................................................................................... 25
Review Questions and problems ............................................................................................ 25
Self Test .........................................t ............................................................... 32

2. C H E M IC A L E Q U IL IB R IU M ................. 35

2.1 The nature of chemical equilibrium ............................................... ............................... 37

2.2 The equilibrium constant .................... ............................................. ............................... 39
2.2.1 Derivation of equilibrium constant from rate expressions ............................... 39
2.2.2 Heterogeneous equilibrium ............................................... ...............................41
2.2.3 Calculation of equilibrium constant .................................. ............................... 42
2.2.4 Calculation of equilibrium concentrations ........................ ...................47
2.2.5 Equilibrium constant expressed in pressures...................... ............................... 49
2.2.6 Variation of equilibrium constant with the balanced form of equation................54
% 2.3 Reaction quotient ................................................................................. ...............................57
2.4 Equilibrium changes - Le Chatelier's Principle................................ ................ 59
2.4.1 Changes in concentration .................................................... 60
2.4.2 Changes in volume and pressure........................................ 62
2.4.3 Changes in temperature ............ 1......................................... ............................... 65
2.4.4 Addiation of a catalyst ....................................................... ............................... 67
2.5 Quantitative calculations based on Le Chatelier’s Principle............ 68
2.6 Factors that cause equilibrium ......................................................... ............................... 74
Some new terms .................................................................................
Review questions and problems .......................................................
Self test.....................................................................................................

3 . SO LU B ILIT Y EQ U ILIB R IA .............................................................................. 93

3.1 Solubility of ionic solids ............ 95

3.2 Factors that affect the solubility ............................................... 96
3.2.1 Maximum randomness and minimum energy ........................................................... 96
3.2.2 Tem perature ..................................................... *.......................................................... 97
3.2.3 Pressure ......................................................................................................................... 98
3.2.4 Effect of solvent on solubility...... ............................................................................ 99
3.3 Experimental determination of solubility product ............................................................... 100
3.4 Calculations from Ksp ............................................................................................................102
3.4.1 Calculation of solubility .........................................:............................................... 102
3.4.2 Will a precipitate form?............................................................................................103
llllllllilllllllllllllllllllilllllllllllllilllllllllllllllllllMlllilllllllltliililllllllllllllllllllllllllllMllllllllllllllllllllllllllllllllillllllllllltlllllllllllllllllllllllllllilllllllllllllllllllllllllllllllllllllllllllt

3.4.3 Selective precipitation .............................................................................................108

3.5 Common ion effect ...............................................................................................................109
Some new term s .................................................................................................................... .fll4
Review questions and problems ............................................................ %14
Self test .......................................................................................................................................120

ACIDS AND BASES ............................................................................................................. 123

4.1 Electrolytes ............................................................................................. 125

4.2 Water as a weak electrolyte .................................................................................................. 125
4.3 Hydronium or hydroxonium ion ........................................................................................... 126
4.4 pH and pOH ................................................................................ 127
4.5 Acid - base theories ................................................................................................................127
4.5.1 Arrhenius acid - base theory ...................................................................................127
4.5.2 Bronsted - Lowry acid - base theory ......................................................................128
4.5.3 Lewis acid - base theory .........................................................................................129
4.6 Monoprotic and polyprotic acids............................................................................................130
4.7 The strength of acids and bases ............................................................................................131
4.8 Acid strength and molecular structure ..................................................................................132
4.9 Properties of acids and bases ................................................................................................ 134
4.10 Quantitative calculations aboutstrongh acids and bases.......................................... 137
4.11 N eutralization ................................................................................... 138
4.11.1 Titration .................................................................................................................... 144
4.12 Calculations based on weak acids and weak b a s e s .............................................................. 147
4.12.1 Calcultion of Ka or К ь...~ ...................................................................................... 147
4.12.2 Calculations of [H+], [OH ], pH and pOH...........................................................149
4.13 Ions acting as acids or bases: hydrolysis............................................................................ 151
4.13.1 Quantitative investigation of hydrolysis............................................................... 152
4.14 Common ion effec: buffer solutions ....v............................................................. /............156
Some new terms ..................................................................................................................... fot?
Review questions and problems ......................................................................................... 160 |
Self test ................................................... ,1 6 8 /

O X ID A TIO N - R EDUCTIO N R EACTIO NS AND

ELECTROCHEMICAL CELLS .......... 171

5.1 Oxidation - reduction processes ............................................................................................ 173

5.2 Balancing oxidation - reduction reactions.. .........................................................................175
5.2.1 Half - reaction method.............................................................................................. 175
5.2.2 Oxidation number method .......................................................................................179
5.2.2.1 Oxidation numbers .......................................................................................... 179
5.2.2.2 Balancing equations by using oxidation n u m b ers.........................................180
5.3 Electrochemical cells ...............................................................................................................186
5.3.1 The construction of a Voltaic cell...........................................................................186
5.3.2 Standard electrode potentials ................................. 191
5.3.3 Standard hydrogen electrode (SHE) ........................................................................191
5.3.3.1 The zinc-SHE cell.............................................................................................192
5.3.3.2 The copper-SHE cell........................................................................................ 193
5.3.4 The use of standard electrode potentials ................................................................ 195
5.3.5 Effect of concentrations on electrode po ten tials.................................................... 199
5.4 Electrolytic cells and electrolysis ......................................................................................... 202
5.4.1 The electrolysis of molten sodium chloride ...................................................... :203
Illll 11111111........ Illlllllllllllllllllllllllllllllllll...... УП

5.4.2 The electrolysis of aqueous sodum sulfate .......................................................203

5.4.3 The electrolysis of aqueous copper sulfate solution ............................................. 204
5.4.4 The importance of electrolysis ........... 205
5.4.5 Quantitative aspects of electrolysis ....................................................................... 206
5.5 Some important oxidation - reductions in our l i f e ........................................................... 207
5.5.1 Corrision ..................................................................................................................... 207
5.5.2 Dry cell .................................................. 208
5.5.3 M ercury cell ............................................................................................................. 209
5.5.4 Lead storage battery .................................................................................................209
5.5.5 Nickel-Cadmium cell ................................................................... 209
Some new term s........................................................................... 210
Review questions and problem s........................................................................ 211
Self test .............................................. 219

6. THE THIRD ROW OF THE P E R IO D IC T A B L E .............................................. . 2 2 3

6.1.Physical properties ...................................................................................................................225

6.2 Chemical properties ................................................................................................................ 225
6.2.1 Metallic solids (sodium, magnesium and aluminum) ........................................... 226
6.2.2 A network solid (silicon) ........................................................................................226
6.2.3 Molecular solids (phosphorus, sulfur and chlorine) .............................................. 227
6.3 The elements as oxidizing and reducing agents .................................................................. 228
6.4 The acidic and basic properties of oxides qnd hydroxides................................................... 230
6.4.1 Oxides ......................................................................................................................... 230
6.4.2 Hydroxides ............................................................................................................... 231
6.5 Occurrence, preparation, and usage ...................................................................................... 233
Some new term s ...................................................................................................................... 236
Review questions and problems ........................................................................................... 236
S elf test ...................................................................................................................................... 237

l \ THE SECO N D COLUMN OF THE PERIODIC TABLE:

THE ALKALINE-EARTH METALS ................................241

7.1 Electron configurations of the alkaline earth metals..... ....................................................... 243

7.2 Trends in physical properties ................................................................................................244
7.2.1 Atomic radii in solids...............................................................................................244
7.2.2 Ionization energies..................................................................................................... 244
7.2.3 Metallic properties..................................................................................................... 244
7.3 Trends in chemical properties................................................................................................ 245
7.3.1 Oxidation and reduction........................................................................ ,..................245
7.3.2 Acid and base properties .........................................................................................245
7.3.3 Solubilities of alkaline earth compounds in w a te r................................................. 247
7.4 Occurrence and preparation of the alkaline earth elem ents..................................................249
Some new term s............................................................................. 250
Review questions and problems ........................................................................................... 250
S elf test......................................................................................................................................... 252

8- THE FO U RTH ROW TR AОN SITIO N ELEM EN TS ........................................ ...255

8.1 Definition of transition elements ......................................................................................... 257

8.2 Electronic configuration of 3d-transition elements...............................................................257
VIII

8.3 General properties of 3dtransition elements .......................................................................258

8.4 Complex ions ........ 260
8.5 Occurence and preparation .............................. 262
8.5.1 Scandium ........................ 262
8.5.2 Titanium ................................................................................. 262
8.5.3 Vanadium ...................................................................... 262
8.5.4 Chromium........ ............................................................................................................. 262
8.5.5 M anganese....... ............................................................................................................. 263
8.5.6 Iron ..............................................................................................................................263
8.5.7 C obalt........................................................................................................................... 264
8.5.8 Nickel .........................................................................................................................264
8.5.9 C opper............................... .........................................................................................264
8.5.10 Z in c............................................................................................................................. 265
Some new term s........................................................................................................................ 266
Review questions and problem s.............................................................. ................. .......... 266
S elf test......................................................................:................................................................. 267

9. A P P E N D IC E S ........................................................................................................... .............

Appendix I : Solubility Product Constants ..................................................................... v...... ; 271

Appendix II : Ionization Constants of Acidsand Bases at 25 °C................................................... 272
Appendix III : Standard Reduction Potentials at 25°C ............................................................... 273
Appendix IV : Table of logarithms ............................................................................................'275
Answers To Self Tests ................................................................................................................277
 CHAPTER

RATES OF CHEMICAL REACTIONS

The objectives o f this chapter are to enable the student t o :

1 - State the m eaning, m easurem ent, and expression o f reaction rates.
2 - Describe the collision theory.
3 - State the factors that affect the rates o f chem ical reactions.
4 - E xplain w hat is m eant by a reaction m echanism for a chem ical reac­
tion.
5 - D escribe th e role o f a catalyst in a chem ical reaction and how it func­
tions.
6 - Establish the relation betw een activation energies and reaction heats.
7 - Write rate equations o f reactions from their m echanism s and from the
data collected experimentally.
 штш1ш111ш11штшйн1111инш11111111тштж1ш11ш<ншн1шшш1иимш1нш1шиш1ш1111ш1111111ии1 Rates o f Chemical Reactions
1 1 3

In the previous year w e have assum ed a com plete conversion o f reactants

into products in a reaction. B ut we have not considered how long this conver­
sion takes place. In daily life w e encounter m any reactions for w hich the speed
o f reaction has vital importance. Extinguishing fire, keeping m ilk w ithout sour­
ing, preventing m etals from rusting, relieving pain... are the outstanding ex ­
am ples for w hich speed o f reaction is very im portant to control the reaction.
The cases m entioned suggest a need to be able to m easure, control, or predict
the rates o f chem ical reactions. These topics are all parts o f the unit titled as
"Rates o f C hem ical R eactions." The branch o f chem istry concerned w ith the
rates at w hich chem ical reactions occur is called C h em ical K inetics.
FIGURE 1.1 A graph
of concentration versus
time for the reaction 1.1 MEANING AND MEASUREMENT OF
X2 (g)+Y2 (g)-> 2 X Y (g ) REACTION RATE
A s the reaction p ro ­
ceeds the concentra­
C onsider a hypothetical reaction : X 2 (g) + Y2 (g) —> 2X Y (g). D u rin g
tion of X2 or Y2 de­
the progress o f the reaction, X 2 and Y 2 are used up, XY is produced. Therefore
cre a s e w h ile the
concentration o f X Y in­
the concentration o f X 2 (usually denoted by [X2 ] ) and the [Y2 ] decrease while
creases. the [XY] increases. See Figure 1.1. By the rate o f this reaction w e m ean how
fast these concentrations are changing. So several rate expressions can be w rit­
ten about this reaction. (To indicate change in any property the sym bol delta (Д)
is used in science).

A [XY] _ The change in the concentration cf XY

R a te i =
Icone | =0.03 5 mol/L :
At time needed for change
Al=l 10s jj:
R = 3.2xl0’4 mol L -1 -1.-:
* * ,- = 4 5 1 =
(at time 100s) At At
T he m inus sign preceding the whole expression indicates that the concentra­
tions o f the reactants are decreasing during the course o f the reaction. One im ­
portant point is that the num erical values o f ra te !, rate2, rate3 m ay or m ay not be
equal. Suppose that at a given time interval the concentration o f X2 is decreasing
at a rate o f 0.05 M /s, the rate o f decrease in concentration o f Y2 w ill also be
loo ;ij 200 •: 300 0.05 M/s. (From the balanced equation it can be seen that the consum ption o f 1
; : :::::::: time(s)
mol o f X 2 m eans the consum ption o f 1 m ol o f Y2 too). Therefore w e can write
Rate2 = Rate3
On the other hand the chemical equation shows that 2 m ol o f XY will be pro­
FIGURE 1.2 The reac­ duced for every m ole o f X2 and Y 2 used. Then the rate o f form ation o f XY will
tion rate at any time is
be tw ice as m uch as the rate o f the consum ption o f X 2 or Y 2. T he rate w ritten
given by the slope of tan­
gent to the curve at that with respect to XY will be 2 x 0.05 = 0.1 M /s or
time.
R ate]
= - R a t e o - - R a te ?
4 Chapter 1 имишшшшишшишшшшшишшишшшшииишшшшинпшиппишишишшишшишшмшишшншшшшшшишишнниишмшшиии

The concentration changes in a reaction can be show n graphically. By m eans

o f graphs the rate o f the reaction can be determ ined. T he rate at any tim e is
equal to the slope o f the tangent to the curve at that time.See Figure 1.2
tan a = rate
The rate o f a reaction usually changes during the reaction. B ecause the rates
o f m ost reactions depend on the concentration o f reactants. As these substances
are used up the reactions slow down. Therefore the rate at the start o f the reac-
time >tion (so called initial rate) is fast but it slows dow n as the reaction proceeds.
FIGURE 1.3 The rate See Figure 1.3.
of a reaction slows down
as the concentration of
reactants used up.

EXAMPLE 1.1 Calculating the Rate of a Reaction

Problem : When ammonia (NH3) is burned, the fate of disappearance of NH3is measured to be 4 x 10" 2 M/s.
Calculate the rate of the appearance of products. The equation is
4NH3 (g) + 502 (g) -> 4NO (g) + 6H20 (g)
Solution : The balanced equation shows that the consumption of 4 mol of NH3 causes the production of 4
mol of NO and 6 mol of H20 .
- 2
4 x 4 x 10
Then
If 4 mol of NH3 produce 4 mol of NO
4 x 10" 2 mol of NH3 will produce x mol of NO
x =
}
= 4 x 10 mol

4 mol of NH3 produce 6 mol of H20 1 = 6 x l 0 " 2mol

4 x 10" 2 mol of NH3 will produce x mol of H20 ) X

Then the rate of the appearance of NO = 4 x 10" 2 M/s

The rate of the appearance of H20 = 6 x 10“ 2 M/s
or
T o w rite the re la tio n s h ip s am ong
A[NH3] = _ Л [ 0 ^ = A [NO] = A [H P] th e r a te s o f re a c ta n ts a n d p r o d ­
Rate
4 At 5At 4 At 6 At u c ts, th e ra te o f e a c h s u b s ta n c e
is d iv id e d b y th e c o e ffic ie n t o f
th e s u b s ta n c e in th e b a la n c e d
Rate Ratef Rate NO Rate HjO
e q u atio n . W e w ill n o t p a y a tte n ­
4 5 4 6 tio n to th e sig n s o f th e ra te s in
n u m e ric a l v a lu e s.
From this relationship, RateNH3 = Rate^o = 4 x 10"2 M/s
-2
6 x RateNH3 6 x 4 x 10 -2
Rate 1 ^ 0 = = 6 x 10 M/s

EXERCISE 1.1 For the reaction

2N20 5 4 N 0 2 + Ог
it was found that at a certain time the rate of appearance of 0 2 was 0.09 mol L 'V 1.
(a) What is the rate of appearance of N 0 2 ?
(b) What is the rate of disappearance of N2Os (a) 0.36 mol L ^ s '1 (b)0.18 mol L 'l s
тмшштшшштнишшппшпмппиншшшпмиммпиншшшшшшшнмттнмншншииитшнн Rates o f Chemical Reactions 5

EXAM PLE 1.2 Finding the Rate of a Reaction

Problem: The decomposition of dinitrogen pentoxide can be represented by the equation :
2N 2 0s (g) —> 4N 0 2 (g) + 0 2 (g)
If the concentration of N 2 0 5 decreases from 0.0080 mol/L to 0.0040 mol/L in 20 seconds, what is the average
rate of formation of either N 0 2 or 0 2 gases?
Solution : Find the change in concentration of N 2 0 5 in 20 sec.
A [N2 Os ] = 0.0080 mol/L - 0.0040 mol/L = 0.0040 mol/L.
The rate in terms of decomposition of N 2 0 5 is Rate = - —
.A t
or R = - -(L004() n?.°J/ k = _ 2 x i()~ 4 mol/Ls
2 0 sec

The sign (-) shows the decrease in [N2 0 5]

On the other hand, the equation shows that N 0 2 is formed two times as fast as N 2 0 5 is used up.
Therefore,
Rate = A = 2x = 2 x 2 x 10' 4 = 4 x 10 4 mol/Ls
At At
The equation also shows that the N 2 0 5 is used up twice as fast as 0 2 is formed. Therefore

Rate . - ^ 10' , , x 10" 4m0|/Ls

2 At At 2

EXERCISE 1.2 When the gaseous SO2 CI2 is heated, it decomposes to S 0 2 and CI2 . If the concentration
of S 0 2 Cl2 changes from 8 x 10 3 mol/L to 2 x 10 3 mol/L in 900 sec, what is the average rate of formation of
S 0 2 in mol/L.min ? 4x 1 O'4 m o l l L . m i n

EXAM PLE 1.3 Finding the Equation from the Rate Expressions
Problem : The rate expressions for the rate in terms of molecules involved in a reaction are given as follows.

Rate = A ^ 2°1 - A fN 0l = А И . a N
2 At 2At 2 At 5At
Write the equation for this reaction.
Solution : The relationship, Rate - -■£?-? *5 - - A I n Q ] - __ ; shows that the rate of
2 At 2 At 2 At 5At
consumption of NO is equal to the rates of productions of NH 3 and H 2 0 . Therefore, the coefficients of NO, NH 3 '
and H 2 0.m ust be equal and each has a coefficient of 2.
The equation also shows that the consumption of H2is 5/2 times as fast as that of NO. Therefore, the coefficient
of H2 is 5.
Since the NO and H 2 are used up they are written on the left as reactants and the NH 3 and H20 are formed they
must be written on the right as products. Hence the equation is
2NO + 5H2 -» 2NH 3 + 2H20

The m easurem ent o f concentration changes during the reaction is usually dif­
ficult w ithout disturbing reaction. The best m ethod in the m easurem ent o f the
rate o f a reaction is based on the continuous and easily m easurable property
w hich changes during the reaction. This property, m ay be, changes in p res­
su re /c o lo r (appearance or disappearance o f a colored substance), acidity, elec­
trical co n d u ctiv ity /v o lu m e, viscosity... Som e reactions and th eir properties
which can be used in the rate determ ination are given below.
6 Chapter 1 ш ............... I....... .................шшишишии... пиши........ пи.... .......mill... .................шиш....... ........ .

R e a c tio n R a te = Д ( Р г ° Р е г ‘У)
At
D e cre a se in p re s s u re a t c o n s ta n t volum e
N 2 (g) + 3H 2 (g) -4 2 N H 3 (g)

H 2 (g) + I 2 (g) -> 2H I (g) D isa p p e a ra n c e o f v io le t color.

(c o lo rle s s) (v io le t) c o lo rle s s

5Fe2 +(aq) + M n C >4(aq) + 8 H+(aq) -> 5Fe3+(a q) + Mn +(aq) + 4H2(X1) D is a p p e a ra n c e of v io le t color.

(p a le yellow) (v io le t) (c o lo rle s s)

W eig h t o f p re c ip ita te o r th e decrease

A g+ (aq) + СГ (aq) -> AgCl (s)
in e le c tric a l c o n d u c tiv ity

NO (g) + 0 3 (g) -> N 0 2 (g) + 0 2 (g)

A p p e a ra n c e o f b ro w n color.
(colorlessX c o lo rle s s ) (re d -b ro w n )

1.2 THE COLLISION THEORY

This theory describes reactions in term s o f collisions betw een reacting parti­
cles. Suppose the reaction,
X2 (g) + Y2 (g) —» 2XY (g),
will take place. According to this theory, first X2 and Y2 molecules m ust collide
with each other, the bonds between X — X and Y — Y atoms m ust be broken
and new bonds betw een X — Y atoms m ust be formed. Then a sim ple reaction
requires:
a) Collisions between reacting particles
b) B ond breakages in the reacting particles
c) B ond form ations in the products
L et us discuss these conditions :
It is calculated that 1031 collisions per second are possible betw een X2 and Y2
m olecules in one liter o f container at a pressure o f 0.5 atm each at room tem per­
ature. If every collision o f a X2m olecule with a Y2 m olecule led to reaction, the
reaction would be over alm ost instantaneously. In fact very few reactions take
place rapidly. M ost reactions are very m uch slow er because m ost collisions do
not cause reaction. For a collision to lead to a reaction, the follow ing m ust o c­
cur:
1) the molecules m ust collide with sufficient energy
2) the molecules m ust collide with a proper collision geometry.
A collision w hich has the properties cited above is called effective collision.
The rate o f a reaction is directly proportional to the num ber o f effective colli­
sions. B ut ju st a sm all fraction o f total collisions is effective. T herefore m ost
reactions are slow at room conditions.
If X2 and Y2 m olecules collide w ith each other gently, the bonds in
X — X and Y — Y m olecules m ay not be broken, X2 and Y2 molecules
 Hates o f Chemical Reactions 7

rebound unchanged. G enerally w hen two slow -m oving m olecules approach

one another closely, they rebound because o f the repulsion o f the negative
charges o f the electron clouds in the outer part o f the m olecules. W hen fiyo
faster-m oving m olecules approach one another, they overcom e the repulsive
force o f the electron clouds o f the m olecules and the bonds in X 2 and Y 2 m ay be
broken, and atom s rearrange to produce XY. If X 2 and Y 2 m olecules approach
one another in such a way that will break X — X and Y — Y bonds we will
expect this collision to be an effective collision. See Figure 1.4 and 1.5

FIGURE 1.4 Effective collision between X 2 and Y2 FIGURE 1.5 The collision with improper geometry
molecules does not result in a reaction.

EXAMPLE 1.4 Proper Collision Geometry

Problem : Decide which collision geometry is proper in the figure given below for the reaction :
NO (g) + 0 3 (g) -> N 0 2 (g) + 0 2 (g)

Solution : In (I) the molecules are correctly oriented for transfer of an oxygen atom from O 3 to NO to give
NO 2 and O 2 . So (I) has a proper collision geometry.
8 Chapter 1 ШШШШШИШШШШПИШШШШШШШИНШНШШИШИ..........I.....ШШН1ШШШШ1Ш.....Hllllllllllllllll.......... II......I... HIM
.....Ill.....

F o r exam ple, in the reaction o f N 0 2 C1 w ith Cl, the proper and im proper o r­
ientation betw een these species can be represented'as in F igure 1.6. T he colli­
sion in Figure 1.6 (a) can not produce a Cl2 m olecule, but the collision in Figure
1.6 (b) can produce N 0 2 and Cl 2 molecules.

After a successful
Collision collision

FIGURE 1.6 (b) shows the production of NO2 and CI2 after a proper collision geometry.

1.3 ENERGY CHANGES DURING A REACTION

L et us investigate how the energy changes during the occurrence o f the re­
action : X2 (g) + Y2 (g) 2XY(g)
1. X 2 and Y 2 m olecules are far apart from each other. T hey have a specific
am ount o f potential energy and specific am ount o f kinetic energy. Assum e
their total potential energy is zero. As the m olecules approach one another
closely, their electron - cloud repulsions becom e m ore and m ore effective,
molecules slow down, as a result, their kinetic energies decrease and potential
energies increase. See Figure 1.7 (a), (b), (c), and (d).
p o ten tial energy

(a) (b) (c) (d)

FIGURE 1.7 The potential energy changes during the course of the reaction : X2 (g) + Y2 (g) - * 2XY (g) (a) M
cules are apart from each other, (b) Molecules are approaching each other, (c) An activated complex is formect.
(d) New molecules, XY, are formed.
ш иш ш и п и ....................... ш и ш и ........... и ............................................. Rates o f Chemical Reactions 9

2. W hen X 2 and Y 2 that have sufficient kinetic energy have collided in proper
A n a c tiv a te d c o m p le x is
a c o m b in a tio n o f r e a c t­ geom etry, all their kinetic energy is converted into potential energy, so a high-
ing m o le c u le s a n d is an ly-energetic, short - lived (transitory) state o f reacting m olecule will be formed.
in te rm e d ia te b e tw e e n re ­ This group o f atom s o f reacting particles is called activated complex (an u n ­
actan ts and p ro d u c ts. A n stable arrangem ent o f atom s that exist only for a m om ent). B ecause o f its high
a c tiv a te d c o m p le x c a n ­
energy, activated com plex is not stable. To reach stability it m ust decrease its
n o t b e iso late d .
energy, to give either reactants or products depending on the conditions under
which the reaction takes place.
3. To decrease its energy the activated com plex m ay follow tw o ways.
(1) It can split into X 2 and Y 2 again, X 2 and Y 2 m olecules get away from each
other. In this case m olecules are converted into their original states, and no re­
action takes place. The energy o f the activated com plex is released in the form
o f kinetic energy to X 2 and Y 2 molecules.
(2) If the activated com plex splits into XY m olecules, the energy o f the acti­
vated com plex is released as kinetic energy to the XY molecules, and XY m ole­
cules m ove apart from each other. In this case there is a net reaction.
A ctivation Energy, Eaf :
The minimum amount o f energy necessary to convert reacting molecules into
activated complex is called the activation energy (threshold energy) fo r the
' forward reaction. This energy is the difference betw een the potential energy of
activated com plex and the potential energy o f reactants. The P.E. difference b e­
tw een the activated com plex and products is called the activation energy for the
reverse reaction and shown as Ear (r refers to reverse). See F igure 1.8.

x2+y2
E 3 f — P E a c lj vatecj co m p lex " P E r e a c ta n ts

E a r —PEact;vated com plex " P E p ro d u c ts

re ac tio n co o rd in ate

FIGURE 1.8 Activation energy barrier for forward and reverse reaction.

Reaction Heat, AH :
The reaction heat is always the energy difference betw een products and reac­
tants. See Figure 1.8.
F or a chem ical reaction, A H —E A Hproducts - E A Hreactants
ДН —P E products - P E reactants
The enthalpy change for a reaction can also be w ritten in term s o f the activa­
tion energies o f forward and reverse reactions.
I f AH > О reaction is endo thermic
AH = Eaf - Ear
AH < О reaction is exothermic
1 0 C h a p te r 1 пшпшшшшишшшшнмшшпишшпншишишшитшшишишшитишишшииишшишшишшшмштшшншишпмшшшшшшшшн

The sum o f potential energies o f reactants is always larger than the sum o f po­
tential energies o f products for exotherm ic reactions. In this case, the heat is
given off. See Figure 1.9 and 1.10 for exotherm ic and endotherm ic reactions.

T \
AH > 0 E af AH < 0
Eaf

1
T AH
ДН
I P E ri A ..
T £ P E products --------
IP E r £PEproc|utiS
_ 1_
reaction co o rd in ate re a c tio n c o o rd in a te
Ms ~V
FIGURE 1.9 Exothermic reaction FIGURE 1.10 Endothermic reaction

EXAM PLE 1.5 Working with PE - RC (Reaction Coordinate) Diagram.

Problem : The Potential Energy - Reaction Coordi­
nate diagram for the reaction
X2 (g) + Y 2 (g) —> 2XY (g)
is given aside.
(a) What is the energy of activated complex ?
(b) What is the activation energy for the forward reac­
tion?
(c) What is the activation energy for the reverse reaction?
(d) What is the heat of this reaction ?
Solution :
(a) The energy of activated complex is the highest ener­
gy level on the graph which is +18 kcal/mol.
(b) Activation energy for the forward reaction is the difference ofcnergics of activated complex and reactants.
Eaf = PE of activated complex - PE of reactants
Eaf = + 18 kcal / mol
(c) The difference of energies of activated complex and products gives the activation energy for the reverse reac­
tion. Eaj = PE of activated complex - PE of products E ar = + 18 kcal/mol - ( - 10 kcal/mol) = + 28 kcal/mol
(d) Reaction Heat is the PE difference between products and reactants.
ДН = PE of products - PE of reactants
ДН = - 10 kcal/mol - 0 = - 10 kcal/mol
or
ДН = Eaf - E ar
ДН = + 18 kcal/mol - ( + 28 kcal/m ol) = -10 kcal/mol
These calculations can easily be found by means of
graph as shown in the figure given aside.
ишмйшштийштжйшшшнмшшшнитнпшпшшшнништяпяттишгошшшшмтяшям Rates o f Chemical Reactions 11

EXAM PLE 1.6 Drawing PE - RC Diagram for a Given Reaction

Problem : For the reaction, (N = N ...O ...N = O )
N20 (g) + NO (g) -4 N 2 (g) + N 0 2 (g)
50 - activ ated
the activation energy for forward reaction is 50 kcal/mol
. com plex
and the reaction heat is - 33 kcal/mol. Draw a PE - Re­
action coordinate diagram for this reaction, indicate the
critical parts of the curve.
Solution : To draw the PE-RC diagram for a reac­ n 2+ n o 2
tion the values of AH, Eaf and Ear must be known. -33
Eaf = 50 kcal/mol, AH = -33 kcal/mol (exothermic)
AH = Eaf - Ear -> Ear = 50 - (-33) = 83 kcal/mol
Then we can draw the PE-RC diagram as shown aside. R eactio n c o o rd in a te

EXAM PLE 1.7 Calculating Eaf

Problem : Given the reaction, C 2 H40 -> CH4 + CO. The activation energy for the reverse
reaction is 50 kcal/mol and the standard heats of formation of C 2 H4 0 , CH 4 and CO are - 40 kcal/mol, - 18 Kcal/
mol and - 26.4 kcal/mol respectively. Calculate the activation energy for the forward reaction.
Solution : To calculate Eaf, according to the equation
AH = Elaf-Ear
AH and Ear must be known. Ear is given. AH can be calculated as follows.
AH0 = AH° (products) - AH° (reactants)
AH° = [AH°f (Ch4) + ДН° (со)] -[AH° (c 2 h4 0 )]
AH° = [(- 18 kcal/mol) + (-26.4 kcal/mol)] - [(- 40 kcal/mol)]
AH° = - 4.4 kcal/mol.
AH = Eaf - Ear
- 4.4 kcal/mol = Eaf - 50 kcal/mol => Eaf = 45.6 kcal/mol

EXERCISE 1.3 Given the reaction, CH 4 (g) + 4Cl2 (g) -» CC 14 (g) + 4HC1 (g)
The activation energy of the forward reaction is 85 kcal/mol and the standard heats of formation of CH4 , CC14 and
HC1 are -18, -96 and -22 kcal/mol respectively. Draw a potential energy diagram for the reac­
tion. E a r=2Sl kcal/mol

EXAM PLE 1.8 Drawing PE - RC Diagram.

Problem : (I) N 0 2 C1 (g) + NO (g) —> N 0 2 (g) + NOCl Eaf= 6.9 kcal/mol
(II) N 0 2 (g) + NOCl (g) —> NO (g) + N 0 2 C1 Eaf = 10 kcal/mol
Draw PE - RC curve for the reaction N 0 2 C1 (g) + NO (g) —» N 0 2 (g) + NOCl (g)
Solution : For the reaction, N 0 2 C1 (g) + NO (g) —» N 0 2 (g) + NOCl (g),
Eaf = 6.9 kcal/mol. Since reaction (II) is РЕ(ксаГ
the reverse of this reaction then, Ea, = 10 kcal/mol.
and
AH = Eaf - Ear
AH = 6.9 - 10 = - 3.1 kcal/mol
See Figure drawn for the reaction
RC
12 Chapter 1 НИШ ................... I........................ НИМШИШШ
П..........................................ШИНН... НИ.......... II... II.........

1.4 FACTORS AFFECTING REACTION RATES

Experim ents show that the rate o f a reaction is influenced by the follow ing
factors.
1. Nature of reactants
2. Concentration of reactants
3. Temperature
4. Catalysts
5. Interacting area (area o f contact betw een reactants)

1.4.1 NATURE OF REACTANTS

The rate at which a reaction occurs depends on the nature and physical states
o f reacting substances. C onsider the following reactions and their rates.
(I) Fe 2 + (aq) + Ce 4 + (aq) -> Fe 3 + (aq) + Ce 3 + (aq) (instantaneous)
(II)5 F e 2 + (aq) + M n 0 4 (aq) + 8 H+ (aq) -»
5Fe3+ (aq) + M n2+ (aq) + 4H 20 (1) (fast)
(III) 5C 2 0£ "(aq) + 2 M n 0 '4 (aq) + 16H+ (a q )-*
2M n 2 + (aq) + 10CO 2 (g) + 8H20 (1) (slow)
R eaction (I) involves no bond breakage and no bond form ation. It involves
ju st an electron transfer from Fe2+ to Ce4+. This occurs as soon as reacting par­
ticles are m ixed. Therefore this reaction has an instantaneous rate.
R eaction (II) requires the bond breakages in one M n 0 4 ion, and the bond
form ations in four w ater m olecules. A ccording to the collision theory; bond
breakages and bond form ations depend on the num ber o f effective collisions.
A s the num ber o f the bond breakages and bond form ations increases, the num ­
ber o f effective collisions w ill naturally decrease, and the rates o f these types o f
reactions w ill be slower. Therefore reaction (II) has a slow er rate than reaction
(I). But its rate can be considered "fast" w ith respect to the rates o f m ost reac­
tions.
F or the occurrence o f reaction (III), the bonds in five oxalate (C 2 0 2 ' ) ions
and two permanganate (M n 0 4 ) ions m ust be broken, and the bonds in ten C 0 2
m olecules and eight H 20 m olecules m ust be form ed. This process naturally
takes up long time. Therefore reaction (III) has the slow est rate am ong the three
reactions.
A sum m ary for the effect o f nature o f reacting substances on the reaction rate
is given below.
a) The reactions between simple m onatomic ions are fast. .
b) The rate o f a reaction is inversely proportional to the num ber and kind o f
bond breakages in the reacting species. The larger the number o f bond breakag­
es the slower the reaction rate.
c) The p h ysica l states o f reacting substances a ffect reaction rate. (W hite
phosphorus burns spontaneously in air, but red one does not)
d) I f the reacting substances are at different states o f matter (we call these re­
actions "heterogeneous reactions") th esta te o f subdivisions o f solids affects the
reaction rate.
e) A ll these ju s t give an estimate fo r the rate o f the reaction .The real rate o f
the reaction may or may not be the same as our estimate rate.
 Цинтии ..... шипим............. Rates o f Chemical Reactions 13

EXAM PLE 1.9 Comparing the Rates of Reactions

Problem : Given the reactions :
I. Ag+ (aq) + СГ (aq) -> AgCl (s)
II. C 8 H 1 8 (1) + 25/202 (g) -> 8C 0 2 (g) + 9H20 (g)
III. Fe3+ (aq) + SCN‘ (aq) -> FeSCN2+ (aq)
IV. 2NO (g) + 0 2 (g) -> 2N 0 2 (g)
V. 2M n0 4 (aq) + 5Sn2+ (aq) + 16H+ (aq) ^ 2Mn2+ (aq) + 5Sn4+ (aq) + 8H20 0)
Compare the rates of these reactions if the reacting substances are all under the same conditions.
Solution : In reactions (I) and (III), two ions are attracted electrostatically to form a large product. Both of
these reactions are expected very fast. But the temperatures and kinetic energies of these species are equal. Then,
the ions with smaller mass move faster than the ions with greater mass. As a result, the rate of reaction (III) is
faster than that of the rate of reaction (I).
Reaction (II) has the largest number of bond breakages and bond formations, so it must be the slowest reac­
tion. When compared with Reaction (II), reaction (IV) has less number of bond breakages and bond formations,
then it is expected to have an average rate.
In reaction (V), the bond breakage and bond formation are found only in M n04' ions and H20 molecules.
Therefore, the rate of this reaction is slower than each of the reactions (I) and (III) and is greater than the reactions
(II) and (IV). The expected rate order of the reactions is : III > I > IV > V > II.
All of these explanations are logical predictions. Many other factors may play role in the rates of reactions
and then our predictions may be different from the experimental results.

EXERCISE 1.4 Given the reactions:

I.Ba2+ (aq) + S 0 4 (aq) -> BaS0 4 (s)
H-H2 (g) + Cl2 (g) -» 2HC1 (g)
III.CH4 (g) + 2 0 2 (g) -» C 0 2 (g) + 2H2 0(g)
Compare the rates of these reactions if the reacting substances are all under the same conditions.

1.4.2 CO NC EN TR A TIO N OF REACTANTS

R eaction rates usually depend on the concentrations o f reacting substances.

The effect o f concentration on reaction rates can be explained on the basis o f the
collision theory. As the concentrations o f reacting substances increase, the fre­
quency o f the collisions betw een reacting substances w ill increase, and conse­
quently the num ber o f effective collisions will increase and the reaction will be
(a) m ore rapid. See F ig 1.11
F or each chemical reaction there is a m athem atical expression that relates the
concentrations o f reacting substances to the reaction rate. T his expression is
called "rate equation" or "rate expression" o r "rate law."
, 4 \ ' F or a general reaction,
■ 5 ^9 3 aA (g) + bB (g) + ... -> cC (g) + dD (g) + ...
the rate equation is :
Rate = k[A]x [B]>...
H ere к is called "specific rate constant", к is affected by tempera­
FIGURE 1.11 The effect ture and activation energy o f the reaction, x and у are the pow ers to
o f concentration on the rate w hich the concentrations are raised. T he values o f x, у and к can be determ ined
o f reaction. Container (b) only experim entally and have no relationship w ith the coefficients o f the bal­
contains more m olecules anced equation. The values o f x and у are usually integers, but are seldom frac­
than (a) . So the number of tional.
collisions in (b) is larger than
that of (a)
14 C h a p te r 1

T h e d ep en d e n ce o f к on
te m p e re a tu re and a c tiv a ­
tio n e n e rg y is g iv e n by The sum o f the exponents x + y, on the concentration term s in the rate ex
A rrh e n iu s eq u atio n ,
Ea pression is called the order of reaction. F or exam ple, the experim entally d e­
к = Z . e kt rived rate expression for the reaction
w here Z —> a co n stan t d e ­ 2NOz (g) + F 2 (g) —>2N02F (g)
p e n d in g o n the re a c tio n
is rate = к [N 0 2] [F J.
e —» n a tu ra l lo g a ritm base
R —> id eal gas c o n stan t. Thus, the reaction is first order with respect to either N 0 2 o r F 2 but second
Ea —» A c tiv a tio n en erg y order overall. T hat is, the sum o f the exponents is
T —» T em p eratu re 1 + 1 = 2 .

EXAMPLE 1.10 Finding the Rate Equation of a Reaction

Problem : The tabulated data below represent the experimentally measured concentrations and rates of forma­
tion of С Г for the reaction,
2HgCl2 (aq) + C 2 O2' (aq) -» 2СГ (aq) + 2COz (g) + Hg2 Cl2 (s)

In itia l (a) Find the rate equation for this reaction.

T ria l [H gC l2] [C 2 0 24 -] (b) What is the value of the rate constant, к ?
r a te M /s
(c) What would be the initial rate of this reaction if
1 0 .1 0 0.15 3.0 x 10 ' 7
[HgCl2]=0.04 M and [C2 0421 =0.25 M (at the same
2 0 .1 0 0.30 1 .2 x 1 0 ' 6
temperature) ?
3 0.05 0.30 6 .0 x 1 0 ' 7

Solution : (a) We expect this reaction to have a rate equation of Rate = k[ H gC ^]* [ C20 ^ '] y. Now we
will find the values of x and y. We observe that the initial concentrations of [HgCl2] in trials 1 and 2 are the
same, so any change in the reaction rate is due to the different initial concentrations of C 2 O 2 '. Doubling
[C2 0 2~] increases the rate of the reaction by a factor of 4 = 22. So the rate is directly proportional to the square
of the concentration changes of C 2 O 2 'o r the value of у = 2
Similarly the comparison of [ C2 0 2 ' ] in trials 2 and 3 shows that they are the same. Then the change in
rate in trials 2 and 3 must be due to the concentration change of HgCl2. Halving the [HgCl2] decreases the rate of
the reaction by a factor of 2=2!. Then the rate of this reaction is directly proportional to the [HgCl2] or the value
of x is 1. Thus the rate equation is
R ate= k [H gC l 2 ][C 2 0 4 ] 2
(b) To find the value of the rate constant, substitute any of three sets of data into the rate equation. Substitution
for the data from the first trial gives:
Rate=k[HgCl2 ][C 2 O 4 " ] 2
3 x l 0 ' 7= k [0 .1 ][0 .1 5 ]2
k=1.33xl0 ’ 4
We can find the same result for к from the other sets of data
(c) To calculate the rate when [HgCl2]=0.04 M and [ C 2 O 2 " ] = 0.25 M we substitute the value of concentra­
tions and specific rate constant.
We obtain:
R ate= k[H gC l 2 ][C 2 0 2' ] 2

R a t e = l .3 3 x 1 0 ’ 4 (0.04)(0.25)2
R a te = 3 .3 x l0 ’ 7
 Rates o f Chemical Reactions 15

An alternative method for finding the values of x and у is given below.

We write the rate equations for the trials 1 and 2 under each other, and approportionate them side by side. This
will give
2 - У
Rate! = k/H gC lJ [С2р4~]
Rate
kfHgClJ [C 2 0 4 _f

3x10' ( 0 .1)* ( 0 .1 5 / 1
- /10 .1 5'/ = > 1_ = /_l / = > 2 = 2a= > y = 2 and,
7

- 6 rn rrs o \ y 4 I 0 .3 4 2
1 .2 x 1 0 (0.1) (0.3)

R a te , = к (0.1)" (О .з / ^ 1.2 x l O '6 _ / 2 / _ 0 _ ox _ „ _ 1 _ o_

~ = || j => 2= 2X =>x = l= * So Rate = к Гтт_™ 1 л 2'-,2
[H gC l2] [C2 o /
Rat03 к (0.05)* (О .З/ 6x10

EXERCISE 1.5 At a certain temperature the following data were obtained for the reaction
2IC1 + H2 I2 + 2HC1
Exp. [IC1] [H2] Initial rate (mol/L.s) Determine the rate law and rate
1 0 .2 0 0.20 3.0 x 10'J constant for the reaction.
2 0.40 0 .2 0 6 . 0 x lO- 3

3 0 .2 0 0.10 1.5 x 10 3

EXAM PLE 1.11 Finding the Rate Equation for a Reaction.

Problem : The following data were obtained for the given reaction at room temperature. Find
(a) the rate equation for the reaction, ЗА + 2B + С —> 2D.
(b) the order of this reaction.
(c) the value of rate constant.

Experiment Initial rate of

Initial [A] Initial [B] Initial [C]
number formation of D
1 0.10 M 0.10 M 0.1 M 4.0 x 10 ' 5 Ms ' 1

2 0.10 M 0.30 M 0.2 M 1.2 x 10 -4 Ms - 1

3 0.10 M 0.1 0 M 0.3 M 4.0 x 10 "5 Ms " 1

4 0.20 M 0.20 M 0.4 M 3.2 x 10 ' 4 Ms - 1

Solution : (a) Rate = к [A]* [B]y [CJZ

The comparison of the data in trial 1 and 3, reveals that the change in the concentration of С has no effect on the
rate. So z = 0
The comparison of the data in trial 1 and 2 reveals that у = 1
Evaluating the data in trial 1 and 4 (or 3 and 4), reveals that x = 2. So the rateequation for the reaction is
Rate = к [A]2 [B]
(b) Since the order of a reaction is the sum of exponents on the concentration terms,
the order is (x + у + z) or 2 + 1 + 0 = 3
(c) Let us substitute for the data from the first experiment. Rate = k[A]2[B]
4.0 x 10"5 = k(0.10 ) 2 (0.10) => к = 4.0 x 10' 2
Note: To check if this equation is true, find the value of к for each trial. If the values of к in each trial are the
same, the equation is correct.
16 Chapter 1 МИНИН ППИНПППШ ППНШШНННШН I ........................ ппппш ..... НИ......11111...........ПИИ... и н н п п ..... п п п н и п ш ...........

EXERCISE 1.6 Use the following experimental data to determine (a) the rate equation (b) specific rate
constant (c) the order of the reaction X 2 (g) + 2Y (g) + Z (g) - » 2D (g) + С (g)

Trial The rate of formation of

[X JM [Y] M [Z]M
no С (Ms4 )
1 0 .1 0 0 .2 0 0 .1 0 2 .0 x lO' 2
(a)Rate=k[Y] [Z]'
2 0 .2 0 0 .2 0 0 .1 0 2 .0 x 1 0 '2 ( b ) k - 1 0 (c)3

3 0 .2 0 0 .1 0 0 .2 0 4.0 x lO’ 2
4 0 .1 0 0.30 0 .2 0 1.2 x lO' 1

EXAM PLE 1.12 U sing P a r tia l P re s s u re s to W rite R a te E x p re s sio n

Problem : The rate expression for the reaction, H 2 (g) + h (g) -> 2HI (g) is found to be
Rate = k[H2] [I2], Rewrite the rate expression by using partial pressures of gases.
Solution : If the reactants are all gases in a one-step reaction, we can use the partial pressure of each reactant
instead of its molar concentration. Because the concentration or the partial pressure of a gas is directly propor­
tional to the number of moles of the gas. Then Rate = к x Р ц 2 x P [2
— .......... 1 . m .................. g --------- — —
EXERCISE 1.7 Given the reaction : S 0 2 (g) + l/2 0 2 (g) -> SO 3 (g)
Write the rate expression of the reaction in terms of molar concentrations and partial pressures of reactants. As­
sume the reaction has no mechanism.

1.4.3 TE M P E R A TU R E
The average kinetic energy of, m olecules in a gas sam ple is proportional to
the absolute tem perature. A t any tem perature the kinetic energy distribution
am ong the m olecules is show n in Figure 1.12

Most probable energy at T2

T 2 > T!

Kinetik energy
for a reaction to occur

FIGURE 1.12 The distribution of kinetic energies in a sample of gas molecules at two different temperatures.
The number of molecules which make effective collisions increases when the temperature is raised
T he m olecules w hich have at least the activation energy o r m ore can cause
effective collisions, and cause a reaction. T he num ber o f m olecules w hich will
produce a reaction is shown by the area a at tem perature T j. W hen the tem pera­
ture is increased to T 2, the num ber o f m olecules w hich will cause a reaction is
proportional to the area (a+ b) as show n in F igure 1.12. Increasing the tem ­
perature causes a sharp increase in the num ber o f m olecules w hich will produce
effective collisions. Increasing the num ber o f effective collisions naturally in ­
creases the rate o f the reaction.
The rates o f all the reactions increase w hen the tem perature is increased. In
m any cases the rate.of a reaction in a hom ogeneous system is approxim ately
doubled by an increase in tem perature o f only 10°C.
штнмшннншниижтипииншшнншншниинмнтншшнтниппплвнмиижшитшшнвнишн Rates o f Chemical Reactions 17

EXAM PLE 1.13 Comparing the Rates of Reactions by Using Their Activation Energies
Problem : At a certain temperature the activation energies of three different reactions are 84 kcal/mol, 72
kcal/mol, and 19 kcal/mol under the same conditions. Which reaction would you expect to be the most rapid
one, and, the slowest one?
Solution : In the figure given, the area, a, represents
the number of molecules which produce the reaction with j
Eaf = 84 kcal/mol. The area, (a + b), represents the number j
of molecules which produce the reaction with Eaf = 72 kcal/ i Jfy,
mol. In other words as the activation energy of a reaction 4 /
decreases, the number of molecules which produce the reac­
tion increases, the rate of the reaction increases too. Simply '
the rate of a reaction is inversely proportional to its activa- t
tion energy. Under the same conditions of temperature,
pressure, and concentration, the reaction with the lowest ac­
tivation energy will be the most rapid.
The reaction with the lowest activation energy of 19
kcal/mol, among the three reactions, is the fastest one. The 19kcal 72kcal 8 4kcal
reaction which has an activation energy of 84 kcal/mol will
E x am p le 1.13
be the slowest one.

1.4.4 C A TA LYSTS
The rates o f some reactions can be speeded up by introducing a specific sub­
stance w hich is not used up in the reaction. Such substances are called cata­
lysts, and their effect.is called catalysis.
F or example, oxygen can be obtained by decom posing K C 10 3 at high tem pera­
tures. If som e M n 0 2 is added to K C 10 3 and heated, the reaction w ill becom e
m uch m ore rapid at a low er temperatures. At the end o f this reaction M n 0 2 can
be recovered unchanged. Using M n 0 2 does not increase am ount o f 0 2 that can
be obtained from a specific m ass o f K C 103. But it just makes the reaction to go
faster. Here M n 0 2 is a catalyst.
Alm ost all the chemical reactions in hum an body are catalyzed reactions. The
catalysts in the hum an body are called enzymes. Enzym es are am azingly ef­
ficient catalysts that increase the rates o f reactions by a factor o f lO2 0 or so.
H o w does a catalyst increase rate?
The function o f a catalyst in a chemical reaction is to open a new, low energetic
pathw ay by w hich the reaction takes place. T hen a catalyzed reaction takes
place by a different pathw ay than the pathw ay o f the uncatalyzed reaction. See

R e ac tio n co o rd in a te

FIGURE 1.13 rhe catalyst functions to de­ FIGURE 1.14 A catalyst decreases the activation
crease the activation energy for reaction. energy. Decreasing the activation energy increases
the number o f molecules that cause effective colli­
sions.
18 Chapter 1 ннишшнжншшшиншшшимииишшиишншммиииишпиннииииишишиишшиииммипминпииишмиинишшшшпшшшинишшпи

A catalyst decreases the activation energy fo r the fo rw a rd and reverse reactions

equally. It is assumed that catalyst forms an intermediate activated com plex with
low er activation energy than that formed without a catalyst.
W hen a catalyst is present, m ore m olecules possess the activation energy for the
reaction. Therefore the reaction speeds up. Figure 1.14
The properties o f a catalyst can be sum m arized as follows:
A catalyst,
1. decreases the activation energy fo r the fo rw a rd and reverse reactions equally.
2. A H = Eaf - E an since Eaf and E ar are decreased by the sam e am ount, their
difference, AH, remains unchanged.
3. m ay or m ay not enter into the chemical equation but it undergoes no p erm a ­
nent change at the end o f reaction. Therefore, its form ula does not appear in the
net equation.
4. cannot cause a nonprobable reaction to take place but ju s t increases the rate
o f a probable reaction.
5. does not change the nature o f reactants and products.
6. does not change the yield o f the reaction, but it ju s t shortens the time o f f o r ­
mation o f products.

EXAM PLE 1 .1 4 Finding the Catalyst

Problem : A reaction takes place in the following steps. Which species is the catalyst in this reaction?
NO + O 3 —^ NO 2 + O 2
N 0 2 + О —> NO + 0 2
and the overall reaction is 0 3 + О —> 2 0 2
Solution : NO is a catalyst. Because it is used up in the first step but regenerated in the second step. There
is not a net consumption of NO, it does not appear in the overall reaction either. These properties define a cata­
lyst.

1.4.5 INTERACTING AREA BETW EEN REACTING

SUBSTANCES

In the previous sections we have said that the physical states o f reacting sub­
stances affect the rates o f reactions. Especially fo r heterogeneous reactions the
surface o f contact between reacting substances is important. A s this surface in­
creases the number o f collisions between reacting particles w ill increase, and
the reaction will speed up.
Consider the reaction
Zn (s) + 2HC1 (aq) -» ZnCl2 (aq) + H2 (g)
iNiiiiiiiiiiiMiiiMiiiiiiiiiiiiiiiiiiiiiMiiiiMiiiiiiiiiiiiiMiiMiiiiiMMMiiiiiiiimiiiiiitiiiiMiniiiiiiiiiiiiiiiiiiiftitnimiiiHn Rates o f Chemical Reactions 19

T he rate o f this reaction depends on the surface area o f zinc m etal in contact
w ith HC1. The rate o f the reaction in w hich pow dered zinc is used w ill be faster
than the reaction in w hich large chunks o f zinc m etal are used. B ecause pow ­
dered m etal zinc has larger surface o f contact w ith HC1 than that o f large
chunks.
Sim ply, fo r heterogeneous reactions as the interacting area betw een reacting
particles increases, the rate o f the reaction w ill increase too.

1.5 REACTION MECHANISM

To deduce the exact effect o f concentration changes on the rate o f a reaction,

the detailed description o f the reaction m ust be know n. M ost reactions do not
occur in a single step as written, but rather take place in a series o f sim ple reac­
tions w hose sum gives the overall reaction. The series o f these reactions is
called its reaction mechanism. \
Consider the reaction;

H 20 2 + ЗГ + 2 H + -> 2 H 20 + I-

F or this reaction to take place, one H 2 0 2 m olecule, three Г ions and two H + ions
having at least the activation energy m ust collide w ith each other in a proper
collision geom etry. But the probability o f such an event occurring is calculated
to be extrem ely low. Therefore this reaction is expected to have an im m easura­
ble rate under norm al conditions. B ut it does have a slow rate. How can this
discrepancy be explained?
To explain this discrepancy w e take the advantage o f "the reaction mech­
anism" concept. According to reaction m echanism concept;
1. T he reactions in w hich a single m olecule decom poses (unimolecular re­
action), or tw o m olecules collide (bimolecular) are m uch m ore probable
than the reactions requiring the sim ultaneous collisions o f three particles (ter-
molecular reactions). T herefore the unim olecular or bim olecular reactions,
(sometimes some reactions requiring three body collisions) usually take place in
single steps.
2. A term olecular reaction does not occur in a single step but rather proceed
through a sequence o f step reactions w hich involve tw o body collision in gen­
eral. The sequence o f these sim ple reactions is called the reaction m echanism
o f the reaction. The sum o f the reactions in the m echanism gives the net reac­
tion. T he reaction cited above requires six body collision, therefore it is expect­
ed to have a m echanism .The m echanism o f a reaction cannot be deduced from
the net equation directly, but rather may be found experim entally. In the light o f
the experiments performed about this reaction the mechanism is believed to be :
20 Chapter 1 ПШШШиНШШИШШ1ШПШШ1ШШ111ШШШШШШМ1ШШ11111111ШШ111Ш1111Ш11Ш1111Ш1Ш11И
Н1ИНШШ11Ш11Ш11Ш11111ШШШ111ШШ11ШШШ1ШШ!111

(I) H 2 0 2 + I" —> H20 + 1 0 ' (slow) (bim olecular reaction)

(II) 1 0 ' + H+ —» HOI (fast) (bim olecular reaction)

(III) HOI + H+ + 1" —> H20 + 12 (fast) (termolecular reaction)

(IV) I" + I 2 —> Ij (fast) (bim olecular reaction)

The rate o f the net reaction depends on the rates o f the reactions in the m ech­
anism. But the slowest reaction in the m echanism determ ines the rate o f the net
reaction. Because 10" produced in reaction (I) is quickly used up in reaction
(II), and the sam e argum ent is true for HIO and I 2 too. To increase the rate o f
this reaction, the slow est reaction m ust be m ade faster. T herefore the rate o f
the reaction depends on the slow est reaction in the m echanism . The slow est re­
action in the mechanism is called Rate Determining Step. Then as the concentra­
tions o f reacting substances in the rate determ ining step (H 2 0 2 and I") are in ­
creased, the probability o f collisions betw een reacting substances will increase
and the rate o f the rate determining reaction will increase.
Quantitatively, the rate expression o f the net reaction m ay be w ritten by m eans
o f rate determ ining step. T he rate is proportional to the concentrations o f reac­
tants o f the rate determining step reaction.
Rate=k[H20 2 ] [ ! ' ]

EXAM PLE 1.15 Finding the Slowest Step in the Reaction Mechanism.
Problem : The rate expression for the reaction. 2A (g) + 3B (g) -» С (g) + 2D (g)
is found to be Rate = к [A] 2 [B]
(a) Does this reaction have a mechanism?
(b) If it has a mechanism, write the slowest (rate determining) step.
Solution : (a) Yes, it has a reaction mechanism. Because if there were no reaction mechanism (If it were one
step reaction), the rate expression of the given reaction would be
Rate=k[A] 2 [B] 3
But, the given rate expression is different from the rate expression we find. In that case the reaction has a mecha­
nism.
(b) The rate expression of the reaction can be written by means of the slowest step in the mechanism.
Rate=k[A]2 [B) given. Then the slowest step will be 2A (g) + В (g) -> products

EXAM PLE 1.16 Finding the Rate Expression of a Reaction

Problem : The mechanism proposed for the reaction, 2IC1 + H2 —> 2HC1 + I2 , is as follows.
(I) H 2 + IC1 —> HI + HCl (slow)
(II) HI + IC1 -> HCl + I2 (fast)
(a) Which is the rate determining step reaction?
(b) What is the rate expression for this reaction ?
(c) If the concentrations of H 2 and IC1 are doubled, how many times will the rate of the reaction change?
(d) If the concentrations of HI and HCl are tripled, how many times will the rate change?
Solution : (a) The rate determining step is the slowest step in the mechanism. Then step (I) is the rate deter­
mining step.
(b) The rate expression can be written from the rate determining step directly. The rate of the reaction is directly
proportional to the concentration of the reactants of the rate determining step. The rate expression is :
шшшшмнимшммшшнпишшпшшшшшшпипшшппшшшшшшшшшшшшшишншшшнишRates o f Chemical Reactions 21

R ate=k [H 2 ][IC l]
(c) When the [H2] and [IC1] are doubled, the rate will increase by a factor of 4. Because the rate of the reaction is
direcdy proportional to the concentrations of both H2 and IC1.
(d) HI and HCl do not appear on the rate equation, therefore changes in [HI] and [HCl] do not cause any change
on the rate.

EXERCISE 1.8 The mechanism proposed for the reaction 4HBr + 02 -» 2H20 + 2Br2 is as follows :
(I) HBr + 02 -» HOOBr (slow)
(II) HOOBr + HBr —> 2HOBr (fast)
(III) 2(HOBr + HBr -> H20 + Br2) (fast)
(a) Which is the rate determining step ?
(b) What is the rate expression for this reaction ?
(c) If the concentrations of HBr and 0 2 are doubled, how many times does the rate increase ?
(d) If the concentrations of HBr and HOBr are tripled, how many limes does the rate increase ?

EXAM PLE 1.17 Finding the Rate Determining Step.

Problem : The rate equation for the reaction, 2NO (g) + Cl2 (g) —> 2NOC1 (g) is found to be
Rate = к [NO] 2 [C1J
Which of the following mechanisms will likely belong to this reaction?
A. 2NO (g) - 4 N 2 0 2 (slow)
N 2 0 2 (g) + Cl2 (g) -> 2NOC1 (g) (fast)
B. Cl 2 (g) -> 2C1 (slow)
NO (g) + Cl (g) -> NOCl (g) (fast)
C . NO (g) + NO (g) + Cl2 (g) -> 2NOC1 (g)
Solution : The rate equation can be written from the rate determining step in the mechanism. When the rate
equations of the rate determining steps are written we will see that only the rate equation of the reaction in part С
is consistent with the given rate equation.
R a te = k [N O ] 2 => for the mechanism A
R a te = k [C l2] => for the mechanism В
R a te= k [N O ][N O ][C I2] = k[NO]2 [C l2] =* for the reaction С
Although this reaction is a termolecular reaction, it is a single step reaction, it has no mechanism.

EXAM PLE 1.18 Suggesting a Reaction Mechanism

Problem : The following data are collected for a three step reaction,
2A + В + С —^ 2D + H
Expt
[A] M [B] M [C]M r a te M/s
no.
1 1 .0 x 1 0 ' 3 2.5 x 10 - 4 4 x 10 - 3 6 .0 x 10 ' 6

2 2.5 x 10 ' 3 2.5 x 10 - 4 4 x 10 - 3 1.5 x 1 0 ' 5

3 1 .0 x 1 0 ‘ 3 2.5 x 10 - 4 8 x 1 0 ' 3 6 .0 x 1 0 ' 6

4 1 .0 x lO ' 3 3.75 x 10 - 4 6 x 10 - 3 9.0 x 10 - 6

(a) What is the rate expression for this reaction ?
(b) What is the value of rate constant ?
(c) What is the order of this reaction ?
(d) Suggest a reaction mechanism possible for this reaction.
22 Chapter 1 ИЙЙИШШНШЛИЖК Illlllllillllllll ||||Ш|||М|||||||||||Н|||Н||Ш||||||||||Ш11|||||||1ШШ||Ш1Ш1Ш|||||

Solution : (a) The rate equation for this reaction is

Rate = к [A]* [B? [C]z
From the trials 1 and 2, [B] and [C] are constant, the change in rate will be only due to the changes in [А]. In­
creasing [A] by a factor of 2.5 increases the rate by the same factor. Then x=l
From the trials 1 and 3, [A] and [B] are kept constant, doubling [C] has no effect on the rate. So, z = 0. Then
neglect the effect of changes in [C] for next "reasoning"
From the trials 3 and 4, increasing [B] by a factor of 1.5, increases the rate by the same factor. So, у = 1 and
Rate = к [A] [B]
(b) To find the rate constant, k, we can substitute any of four sets of data given in the table into the rate equation
Let's use the first trial.
6.0 x 10' 6 = k(1.0 x 10‘3) (2.5 x 10~4) ^ к = 24
(c) The order of the reaction is(x + y + z) = l + l + 0 = 2
(d) A and В are the reactants of the rate determining step. The rest of the steps in mechanism are so selected that
their sum gives the overall reaction. A possible mechanism is:
A + В —> AB (slow) => This is certain
AB + C -> G + D (fast) 1
_ „ 1 These reactions are imaginary reactions
G + A E + D (fast) J &

2A + В + С —> 2D + E (overall reaction)

1.6 THE EFFECT OF CATALYST ON A

REACTION WITH MECHANISM

The rate of a reaction with mechanism is determined by the slowest

reaction in the mechanism. If the rate of the slowest reaction is in­
creased, the rate of overall reaction increases. Among the steps in the
mechanism, the slowest step has the highest activation energy. If a cat­
alyst is used in a reaction which has a mechanism, the activation energy
of the slowest step is lowered. As a result, the rate of the slow. . step
and then the rate of overall reaction increases. Figure 1.15 shows the ef­
fect of catalyst on an endothermic reaction with mechanism.
Catalyst decreases In general, catalysts provide a new reaction path in which a different,
the Ea of slowest step only lower-energy, activated complex can form. For example, the decomposi­
tion of formic acid, HCOOH into CO and H 2 O is a single-step reaction
without catalyst and is very slow.
If sulfuric acid (H 2 SO4 ) is used as catalyst, the decomposition reac­
tion speeds up and proceeds on steps. The elementary steps constitute
the mechanism of reaction as follows.
HCOOH + H+ -> HCOOH2+
HCOOH2+ HCO+ + H20
HCO+ —> CO + H+__________________
HCOOH CO + H20 (overall reaction)
FIGURE 1.16 The PE-RC diagram The potential energy-reaction coordinate diagram for uncatalyzed and
for the uncatalyzed and catalyzed catalyzed decomposition of formic acid is shown in Figure 1.16.
decomposition of formic acid.
............................... uni......................... Rates o f Chemical Reactions 23

EXAM PLE 1 .1 9 Effect of Catalyst on the Reaction Rates.

Problem : The potential energy - reaction coordinate diagram for a reaction which has three steps in its
mechanism is as follows.

E x a m p l e J .19
If a catalyst is added to the reaction system, what effect does it have on the PE - Reaction coordinate diagram?
Solution : Catalysts decrease the activation energy of the slowest step for which the activation energy is the
highest. Therefore catalysts increase the rate of the slowest reaction. Its effect can be shown in the figure above.

EXAM PLE 1 .2 0 Finding the Rate Expression

Problem : The reaction, 2A + B + K - > L + F + 120 kcal, has a mechanism with three steps. The first two
steps of the mechanism are as follows:
2A + В -> С + D ■(fast)
С + E -> К + L (fast)
(a) Deduce the rate expression for the reaction.
(b) Find the order of this reaction.
(c) How many times does the rate increase when the concentration of К and D are tripled?
(d) Which species is the catalyst in the reaction?
(e) Draw a PE - RC diagram for the reaction.
Solution : (a) The sum of the reactions in the mechanism gives the net (overall) reaction. Therefore, the
slowest step which is not given can be found by subtracting the given steps from the net equation.
#A + # + К —> 1/ + F (overall reaction)
~2/A ± # -+ -£ ± D (fast)
-t ± E -+ 'К ± t _________ (fast)
K -E - K - D + For
2K + D -> E + F which is the slowest step.
Hence, the rate expression is R = к [К ] 2 [D]
(b) The order of a reaction is the sum of the exponents of the concentration terms. According to the rate expres­
sion, the order of the reaction with respect to К is 2 and the order with respect to D is 1, and the sum, 2 + 1 = 3,
is the overall order of the reaction.
24 Chapter 1 П1111111Ш 1Ш 1111111Ш 11Ш Ш 1Ш Ш 11Ш 1 И111Ш 111111111Ш 1Ш Ш Ш Ш 1111111Ш 1Ш Ш !Ш 11111Ш 1Ш Ш 1111Ш Ш 11Ш Ш Ш 1 Ш 1 | 1| 1Ш Ш Ш 111И111ИШ 1ШИШ Ш 1 Ш 11Ш 11Ш 1Ш 11

(c) The rate of the reaction is directly proportional to the square of the [K] andthe[D],
If only the [K] is tripled, the rate increases 32 = 9 times.
If only the [D] is tripled, the rate increases 3 times.
If both are tripled, the rate increases 32 x 3 = 27 times.
(d) The catalyst opens a new pathway by decreasing the activation energy of the slowest step but it is not used
up in the reaction. It also doesn't appear in the net reaction.
2A + B -> С +t> (fast)
t+ t -» t +L (fast)
ffiS-1> -> % + F_________ (slow)
2A + B + K - > L + F (net reaction)
As shown, C, D, and E appear in the single reactions but don't appear inthenet equation. If you give atten­
tion, С and D are intermediates, then E is a catalyst.
(e) Since the mechanism consists of three steps, the graph must have three peak points, but the slowest step has
the highest activation energy as shown in the figure given down.

' -------------------------------------------------------------------------------------------------------
EXERCISE 1.9 Given the mechanism for a reaction as follows.
2 NO 2 (g) -» NO 3 (g) + NO (g) (slow)

N 0 3 (g) + CO (g) -> N 0 2 (g) + C 0 2 (g) (fast)

(a) What is the overall reaction for which the mechanism was given ?
(b) What is the rate expression for this reaction ?
(c) What is the order of the reaction ?
(d) If the concentrations of NO 2 and CO are tripled, how many times does the rate increase ? (c) 2
 .......... Rates o f Chemical Reactions 25

SOME NEW TERMS

Activated complex : A shortlived, high energet­ Effective collision : The collision which re­
ic group of atoms of reacting substances. sults in a reaction. The collisions with sufficient en­
Activation energy : The minimum amount of ergy and with proper collision geometry.
energy necessary to convert reacting substances into Rate determining step : The slowest step in
activated complex. the mechanism. This reaction also determines the
Catalyst : A substance that increases the rate of a rate of the overall reaction.
reaction. Rate equation : The equation that relates the rate
Chemical Kinetics : The branch of chemistry of the reaction to the concentrations of reactants.
which deals with reaction rates. Reaction mechanism : The sequence of step re­
Collision theory : A theory that assumes the re­ actions by which reactants are transferred into prod­
actions in terms of collisions between reacting parti­ ucts.
cles.

REVIEW QUESTIONS AND PROBLEMS

Reaction Rate and Its Measurement
1.1 Write three rate expressions by using concen­ Write the equation for the reaction. f
tration changes for the reaction,
2N 2 0 5 (g) —» 4 N 0 2 (g) + 0 2 (g) 1.5 Given the reaction
Set up the relationship among these three expres­ N 0 2 (g) —» NO (g) + l/2 0 2 (g)
sions. If the rate of formation of N 0 2 is 2.5 x 10' 5 The concentration of N 0 2 changes from 0.5 mol/L
M/s, what are the numerical values of the other to 0.4 mol/L in 600 seconds. What is the average
rates? rate of formation of 0 2 gas in mol/L. min?
N 20 5: 1 . 2 5 x 1 0 ' 5M I s , 0 2: 6 . 2 5 x l O' 6M / s R o 2= e . e $ 5 m o l / L : m i n

1.2 Write three different expressions that can be

1.6 If 0.96 gram Mg metal is completely used up
used to express the rate of the following reaction,
in hydrogen chloride solution in 50 seconds by the
and show the relationship between these expressions.
reaction Mg + 2HCI —> MgCl2+‘!H 2 (g)
16H+ (aq) + 2MnO; (aq) + 10Г (aq) ->
what is the rate of formation of hydrogen gas in li­
2Mn2 + (aq) + 8H20 (1) + 5I2 (s)
ter/second at STP? 0 . 01 8 L / s

1.3 At high temperatures, N 2 0 3 (g) decomposes to

N 0 2 (g) and NO (g). If the rate of appearance of N 0 2 ^) 1-7 What properties other than concentration chang­
is 1.4 x 10‘ 3 atm/s, what must be the rate of disap­ es may be used to measure the rate of the reaction,
pearance of N 2 0 3? 1 . 4 x 1 0 ' 3 A t m/ s 2N 2 0 5 (g) —> 4 N 0 2 (g) + 0 2 (g)

\ 1.8 Given the reaction:

1.4 The relationships among the rate expressions
Zn (s) + 2HC1 (aq) -> ZnCl2 (aq) + H 2 (g)
for the rate of a reaction in terms of the changes in
Suggest a method to measure the rate of this reac­
concentrations in a time interval are given as fol-
tion.
A[OJ A[N 2j Д[Н2 0]
‘K ? ' = . « 1
4Д t 3At 2Д t 6 Дt 1 .9 Which properties should be used to determine
the rate of each of the following reactions?
 2 6 Chapter 1 mill .

d * (a) 2N 0 2 (g) —> N 2 O4 (g) Make a graph of concentration versus time and deter­
v (b) S 0 2 (g) + l/2 0 2 (g) —> S 0 3 (g) mine the rate of the reaction at t = 150 seconds and
(c) Cu (s) + 2Ag+ (aq) -> Cu2+ (aq) + 2 Ag (s) t = 350 seconds. (Hint : The rate is the slope of the
(colorless) (blue) curve)
(d) Fe (s) + 2HC1 (aq) -> H2 (g) + FeCl2 (aq)
(e) 2HI (g) -> H 2 (g) + I2 (g) 1 .1 1 The rate equation for the reaction,
(violet) 2A (g) + В (g) —> 2C (g), is к [A] 2 [B]
1.10 The following data were collected for the re­ Compare the initial rate of reaction if a mixture of
action, 0.06 mol A and 0.04 mol В in a liter container with
S 0 2 C12 —» S 0 2 + Cl2, at a certain temperature. (a) the rate of the reaction when half of A has been
[S0 2 C12] (mol/L) time (s') consumed.
0.050 ................................................... 0 (b) the rate of the reaction when half of В has been
0.041 ..................................................... 50 consumed.
0.034 ................................................. 100 (c) the rate of the reaction when one-third of A has
been consumed.
0.028 ................................................. 150
0.022 200 (d) the rate of the reaction at the beginning in 0.5 L
container.
0.018 ................................................. 250
0.015 ................................................. 300 (a)Ratej=32/5R a t e 2 (b)Ratej =l 8R a t e 3
0.012 350 (c)Rate1- 3 R a t e 4 (d)8Ratej=Rate5
0.010 400

Collision Theory and Energy Changes During a Reaction

1.12 What are the basic assumptions of collision (b) How much heat is produced when 12.4 g of
theory? phosphorus burn? 71.2kcal.
у j
1 .1 3 Draw potential energy diagrams for two reac­ 1 .1 6 The activation energy for the reaction
tions that have the same heat of reaction, except that CH 4 (g) + 2 0 2 (g) -* C 0 2 (g) + 2H20 (g) is 15.40
one reaction is fast and the other is slow. kcal. If the enthalpies of formation of methane
(CH4), carbon dioxide (C 02) and water (H2 0 ) are
1 .1 4 Graphite can hardly be converted into dia­ -17.89 kcal/mol, -94.05 kcal/mol and -5 7 .8 0
mond,even though its reaction heat is 0.45 kcal/mol kcal/mol respectively,
С (graphite) —> С (diamond) Л H = 0.45 kcal/mol. (a) What is the activation energy for the reverse reac­
How can you explain this property of the reaction in tion?
terms of collision theory and activation energies. Il­ (b) Draw Potential Energy diagram j p r this reaction.
lustrate it graphically by drawing a suitable P.E - E a r= 2 0 7 .1 6 kcal
Reaction coordinate curve. ,/7
\ 1 .1 7 Given the reaction,
1 .1 5 Phosphorus, P4, exposed to air burns sponta­ • iP ' C 0 2 + NO —> CO + N 0 2
neously to give P4 O 10. AH for this reaction is - 712 The activation energy, Eaf, for the forward reac­
kcal per mole of P4. (a) Draw an energy diagram for tion and the activation energy for the reverse reaction
the net reaction. Explain the critical parts of the are 8 6 kcal/mol and 32 kcal/mol respectively. If
curve. enthalpies of formation of C 0 2 , NO, and CO
 пт ним .... шммшш........... Rates o f Chemical Reactions 27

-94.05 kcal/mol, 21.60 kcal/mol and -2 6 .4 2 1.20 Given the reactions:

kcal/mol respectively, what is the enthalpy of forma­ N2 (g) + 2 0 2 (g) + 16.0 kcal -> 2N 0 2 (g)
tion of N 0 2 gas? 7.97 kc al/mol С (s) + 0 2 (g) -> C 0 2 (g) + 94 kcal
N 2 (g) + 0 2 (g) + 43.2 kcal -> 2NO (g)
* 1 .1 8 Given the PE - RC diagram for the reaction If the forward and reverse activation energies for the
C 2 H6 (g) -> C 2 H4 (g) + H 2 (g) in the figure given be­ reaction
low. Calculate CO (g) + N 0 2 (g) -> C 0 2 (g) + NO (g)
(a) the activation energy for forward reaction. are Eaf = 32 kcal, Ear = 8 6 kcal respectively, what is
(b) the activation energy for the reverse reaction. the enthalpy of formation of CO ?
(c) the potential energy of activated complex. -26.4 k ca l/m o l
(d) the enthalpy change for the reaction.
(e) Is this an exothermic or endothermic reaction? Use the Potential Energy diagram in the fig­
ure to answer the following questions.

Problem 1.18 Problem 1.21

(a) What is the activation energy for the forward reac­
1 .1 9 The reaction, tion?
CH 3 C H O (g )-* C H 4 (g) + CO (g) (b) What is the activation energy for the reverse reac­
has an activatioh energy of 41 kcal. If the standard tion?
heat of formations of CH 3 CHO, CH4 , and CO are (c) What is the enthalpy of this reaction?
- 42 kcal/mol, - 17.9 kcal/mol and - 26.4 kcal/mol (d) Is this reaction exothermic or endothermic?
respectively, find the reaction heat and draw a PE-RC (e) Draw a similar graph for the catalyzed reaction.
diagram for this reaction. A H = + 5 . 5 kcal 1 .2 2 Summarize briefly the factors which affect

Factors That Affect The Rate of Reactions

1.22
the rates of reactions. CH 3 COOC 3 H7 (1) + H20 (1) ->
CH3COOH (1) + C 3 H7OH (1)
1 .2 3 Compare the rates of the following pairs under
the same conditions of temperature, pressure, and con­ 1 .2 4 Consider two gases, A and В , in a container at
centration. room temperature. These two gases may produce the
A) Ca2+ (aq) + C O f (aq) -> C aC 0 3 (s) following reaction, A + В —» С + D. State and ex­
C2 H5OH (1) + 3 0 2 (g) -> 2C 0 2 (g) + 3H20 (g) plain the effect of each of the following changes on
B) S2 0 82 taq)+3T (aq) -> 2S0 2 (aq) + 1'(aq) the reaction rate . (a) The pressure is doubled (b) The
2 8 Chapter 1 m ill I ............ ram.....«гаи..... immmmw...

the reaction rate . (a) The pressure is doubled (b) The 1 .3 6 For the reaction 2X —> Y + Z, the following
number of molecules of gas A is doubled (c) The data are obtained for [X] as a function of time.
temperature is decreased at constant volume. Time (mini 1X1 mol/L

0 0.80
1 .2 5 An increase in temperature by 10°C nearly
8 0.60
doubles the rate of a reaction. How can this be ex­
24 0.35
plained?
40 0.20

1 .2 6 What is a catalyst? Describe the way in

(a) By a suitable method determine the order of the
which catalysts function in a chemical reaction.
reaction.
(b) Calculate the rate of formation of Y at t = 30
1 .2 7 Why does a log burn slowly in air, while
min.
sawdust made from the same tree burns explosively
if scattered throughout the room and ignited?
1 .3 7 Given the reaction,
AB 2 (g) + AB (g) —> CD2 (g) + E (g)
1.28 What is rate law ? What name is given to the
Eaf = 39.7 kcal/mol and Ea,. = 54.7 kcal/mol
proportionality constant in the rate expression ?
(a) Draw a PE - Reaction coordinate diagram for the
reaction (assume it has no mechanism). Indicate the
1.29 What is meant by the order of a reaction ?
critical parts of the curve.
(b) Suppose a catalyst is added, show its effect on
1.30 What are the units of the rate constant for (a)
the same curve. Compare the following properties
a first - order reaction, (b) a second - order reaction,
for the catalyzed and uncatalyzed reaction ( 1 ) activa­
and (c) a third - order reaction ?
tion energies, (2) reaction heat, (3) rate of reaction,
(4) number of effective collisions, (5) nature of reac­
1 .3 1 Is there any relationship between the coeffi­
tants and products, (6 ) the nature of the activated
cients of the balanced overall equation for a reaction
complex, (7) the amounts of products that will be
and the powers to which concentrations are raised in
obtained at the end of the reaction.
the rate equation?

1 .3 8 For the reaction,

1.32 How must the exponent in a rate law (rate
2A (g) + В (g) —> С (g) + D (g)
equation) be determined ?
the following data were obtained.

1.33 If the concentration of a reactant is doubled, Ш . mi Rate of formation of С

and the reaction rate doubles, what must be the order 0.2 M 0.1 M 5 x 10* 4 Ms* 1
of the reaction with respect to that reactant ? 0.4 M 'Ч & M ' 4 x 10* 3 Ms* 1
0.2 M 0 .2 M 1 x 10* 3 Ms* 1

1.34 if the concentration of a reactant is tripled, by (a) What is the rate equation for the reaction?
what factor will the rate increase if the reaction is (b) What is the order of this reaction ?
second order with respect to that reactant ? (c) What is the numerical value of the rate constant?
(d) If the [A] = 1M, [В] = 1M, what would the rate
1.35 What kind of experiments must be done to be?
determine the exponents in the rate equation for a re­ a ) R a t e = k [ A ] 2[B],b)3 c)0.125, d)0.125.
action ?
iiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiHiiiiiiiiiiiiiiiiiiMiiiiiiiiiiiiiiiii Rates o f Chemical Reactions 29

1 .3 9 The rate of the reaction, (a) Write the rate expression for the reaction.
2HgCl2 + C20 \ -> 2СГ+2С0 2 (g)+Hg2 Cl2 (s) (b) Find the order of the reaction.
is followed by measuring the number of moles of (c) Find the value of rate constant, к ?
Hg2 Cl2 that precipitates per liter of solution per min­ a)Rate=k[A][C] b)2 c)k=0.2
ute.
1 .4 2 The following data are for the reaction
IHgClJ [C2 C # ] Rate
2X + 3 Y + Z -> E + 2 F
- 5
0.105 0.15 1 .8 x 10 [X] M [Y] M [Z]M Rate
- 5 - 5
0.105 0.30 7.2 x 10 0 .1 0 .2 0 .2 lx 10

0.052 0.30 3.6 x 10 " 5

0 .2 0.4 0.4 8 x 10
.6
0.052 0.15 9.0 x 10 0.3 0 .2 0.4 9 x 10 ' 5

(a) What is the rate law for the reaction ?

0 .2 0 .8 0 .2 16 x 1 0 ’ 5
(b) What is the value of the rate constant, k?
(c) What is the order of the reaction with respect to (a) Determine its rate expression.
c 2o \- ? (b) Calculate the value of k.
(d) What would be the initial rate of reaction if (c) Find the order of reaction with respect to each of
[HgCl2] = 0.02 M and [ C2 O l' ] = 0.2 M X, Y, and Z and then overall.
( a ) R a t e = k [ H g C l 2 ] [ C 2 0 24 ' ] 2 ( a ) R = k [ X ] 2[Y ] (b)5xl0~3

( b ) 7 . 6 x 1 0 ' 3l 2 m o l ~ 2m i n ~ I , ( c ) 2 (c)respectively 2,1,0, and 3

( d) 6 . 1 x 1 O'6 m o l L ' 1 m i n ' 1

1.43 The rate expression for the reaction :
1 .4 0 The following data were recorded to determine 2X + Y + 2Z —> К + 2L
the rate equation of the reaction; is Rate = k[X ] 2 [Z], Fill in the blanks in the follow­
0 3 (g) + NO (g) —» 0 2 (g) + N 0 2 (g) ing table.
I. When the concentrations of 0 3 and NO were dou­ [X] (mol/L) [Y] (mol/L) [Z] (mol/L) Rate (mol/L. s)
bled, the rate increased 4 times. 0 .0 2 0.025 0 .0 1 2 . 0 x 1 0 ' (’

II. When the concentration of NO was held constant 0.050 0 .0 2 16 x 1 0 ‘ 6

but the concentration of 0 3 was tripled, the rate was 0 .0 2 0.025 0 .0 2

tripled too. 0 .0 2 0.0125 0 .0 2 4.0 x 10’ 6

(a) Find the rate equation for the reaction.
(b) If both [0 3] and [NO] had tripled what would 1.44 The reaction, xA + yB —> С + D is a one -
have been the rate? step irreversible reaction and the following data are
( a ) R a t e = k [ N О ] [ О 3] , (b)Rate would have i n­ given for this reaction,
creased 9 times. Trial [A] (mol/L) [B] (mol/L) Rate (mol/L.s)
1 1 . 0 x 1 0 _1 1 .0 x 10~2 1 .0 x 1 0 '4
1.41 The following data are given for the reaction:
2 5.0 x 10’ 2 4.0 x 10' 2 8 .0 x 1 0 '4
2A + B + C - > D + 2E
3 1 .0 x 1 0 '1 2 .0 x 1 0 '2 4.0 x 1 0 ' 4
[A] M [B] M [C ]M Initial rate (M/min)
0 .1 0 0 .2 0 0 .2 0 4.0 x 10' 3 (a) What are the numerical values of x and у ?
0 .1 0 0.40 0 .2 0 4.0 x 10' 3
(b) If [A] = 0.1 mol/L and [B] = 0.2 mol/L, what is
0 .2 0 0 .2 0 0 .2 0 8 .0 x 1 0 '3
the instant rate for the reaction ?
0.30 0 .1 0 0 .2 0 1 .2 x 1 0 '2
( a )x = l ,y=2 (b)4xl0'2m ol/L . s
0 .1 0 0.40 0.60 1 .2 x 1 0 '2
30 C h a p ter 1 ЫШ 1 НШШИШШН1 1 .................... Illlllll......... ..........Ill..... ..

Reaction Mechanism
1.45 Explain what is meant by "reaction mecha­ [ s 2o l _] м [P]M Rate (M/s)
nism". 0.038 0.060 1.4 x 10' 5
0.076 0.060 2.8 x 1 0 '5
1.46 Would you expect the reaction,
0.076 0.030 k 1.4 x 10' 5
N 2 (g) + 3H2 (g) -> 2NH 3 (g)
to have a mechanism ? Why ? Does this reaction have a mechanism ? Why ? Yes

1-47 To determine the rate expression for the reac­ 1.50 For the reaction,
tion, 2NO (g) + 0 2 (g) - a 2 N 0 2 (g), the rate law, ex­
2NO + 2H 2 -> N 2 + 2H20 pressed as the rate of formation of N 0 2, is found to
the following data were obtained. (I) When the con­ be, Rate = k[NO ] 2 [0 2]
centration of H 2 is doubled and the concentration of (a) Is the rate law consistent with one-step mecha­
NO is kept constant, the rate increases four times. nism, 2NO + 0 2 - a 2N 0 2 ?
(II) When the concentration of NO is doubled by (b) Why is this one-step mechanism not very plausi­
holding the concentration of H 2 constant, the rate in­ ble?
creases twice.
Write the slowest step reaction in the mechanism of The mechanism of a reaction is given below :
this reaction. (I) ОСГ + H20 -> HOC1 + OH’ (fast)

1-48 The following data are given for the reaction (И) Г + HOC1 -> HOI + СГ (slow)
2A + 4B -> 2C + D + 114 kcal (III) HOI + OH- -> H20 + OF (fast)
[A] (mol/L) [B] (mol/L) Rate of formation of D
(a) Write the overall reaction which has this mecha­
0 .1 0 . 0 .1 0 . 2 x 1 0 ‘4
nism.
0 .2 0 0 .1 0 8 x 1 0 ‘4 (b) Draw a suitable PE diagram for the reaction. As­
0.40 0 .2 0 64 x 10‘4 sume the reaction is endothermic.
(c) What would be your suggestions to increase the
(a) Determine its rate expression.
rate of this reaction ?
(b) Calculate the value of k.
(c) Does this reaction have a mechanism ? If it has, The mechanism for the reaction.
write the slowest step. H2 0 2 (aq) + 2Г (aq) + 2H3 0 + (aq) ->
(d) Explain the effect of temperature on the rate by I2 (s) + 4H20 (1)
drawing a diagram. is as follows :
(e) Explain the effect of addition of a catalyst on the
H2 0 2 (aq) + 1" (aq) - a H20 (1) + IO" (aq) (slow)
rate by drawing two different diagrams. (PE diagram
and KE diagram) lO* (aq) + H3 0 + (aq) - a HIO (aq) + H20 (1) (fast)
( a ) R a te = k[A ] 2[B],(b)k=0.2 ,(c)2A + B HI0(aq)+H 3 0 + (aq)+ r (aq) -> 2H2 0(1)+I2 (s) (fast)
(a) Write the rate expression for this reaction.
Experimental data for the reaction : (b) How many times does the rate increase if the
S2 Og' + ЗГ -» 2 SO 4 ' + I3 concentration of I" is doubled ?
(c) How many times does the rate increase if the con­
centration of H3 0 + is doubled ?
 I пн inn mu................... Rates o f Chemical Reactions 31

1.53 The mechanism for the reaction, 1 .5 6 The following data have been obtained for the
ЗА (g) + В (g) -> 2C (g) + D (g) instantaneous rate of the reaction occurring in solu­
tion,
is as follows:
ЗА + 2B - a A3B2 + heat
2A (g) + В (g) - a С (g) + E (g) (slow) [A] И Rate
E (g) + A (g) -> С (g) + D (g) (fast) 0.1 0.1 6.0 x 10'4
(a) How many times does the rate of the reaction in­ 0.3 0.5 5.4 x 10'3
crease if the concentration of A is doubled ? 0.5 0.1 1.5 x 10'2
(b) How many times does the rate of the reaction in­ 0.5 0.5 1.5 x 10'2
crease if the volume of the container is halved by
(a) What is the rate equation for the reaction ?
doubling the pressure at constant temperature ?
(b) What is the numerical value of the rate constant?
(a)4 (b)8
(c) Would you expect this reaction to have mecha­
1.54 The reaction
nism ? If it has, write the rate determining step reac­
N 0 2 (g) + CO (g) -> NO (g) + C 0 2 (g)
tion,
is believed to take place by the two bimolecular reac­
(a ) R a te = k [ A ] 2, ( b ) k = 6 x ! 0 ' 2, (c)2A -A ...
tions. One of them is given below.
N 0 3 (g) + CO (g) N 0 2 (g) + C 0 2 (g) (fast)
(a) What is the rate expression for this reaction ? 1.57
(b) What is the order of this reaction ?
(c) If the concentration of N 0 2 (g) and CO (g) is
doubled how many times does the rate of the reaction
increase ?
(d) What is the reaction rate when
[N 0 2] = [CO] = 0.02 mol/L ? The rate constant, k,
is 4.0 x 10' 3
( a ) R = k [ N O 2] 2 ( b) 2 (c)4 (d)R=1.6xlO'6

1.55 The mechanism proposed for the reaction,

4HBr (g) + 0 2 (g) 2H20 (g) + 2Br2 (g) consists
of three steps. The equations for the fast steps are as
follows:
The PE-RC diagram given above is for the reaction,
(II) HOOBr + HBr -> 2HOBr (fast)
A + 3B + 2C —> 2D + E
(III) HOBr + HBr H20 + Br2 (fast)
(a) How many steps does the mechanism of the reac­
(a) Determine the rate equation for this reaction.
tion have ? Which step is the rate determining step?
(b) Determine the order of the reaction with respect ■.
(b) What is the activation energy for the rate deter­
to HBr, with respect to 0 2, with respect to HOBr,
mining step ?
and overall.
(c) What is the enthalpy change for the reaction ?
(c) How many times does the rate of the reaction in­
(d) Show the change in the graph when a catalyst is
crease if the concentration of HBr, 0 2 and HOOBr is
used in the reaction ?
doubled ?
(d) Draw a PE-RC diagram for the reaction when (1)
uncatalyzed, (2) catalyzed. (Assume it is an exother­
mic reaction)
32 Chapter 1 It I I Illllllllllllll Ill Ш
1ШИШ1ШШ Illllllll mini nnnn II

i «tfbani&do пээй svfiri < SELF

1. Given the reaction :
4NH 3 (g) + 5 0 2 (g) -* 4N 0 (g) + 6H20 (g)
Which one of the following expressions is WRONG
for the rates of appearance or disappearance of sub­
stances involved in the reaction ?

/j {fi T esl 4
C) RateNH3= ----- — °-2 D) RateNH3 = RateNO
The PE-RC diagram for the reaction,
2NOC1 (g) -> 2NO (g) + Cl2 (g)
0 2 x Ratetl2o is given above. Which one of the following is
' Rate N0 -------
WRONG for the activation energy of forward reac­
tion (Eaf), the activation energy of reverse reaction
2 . In which one of the following reactions, the (Ear) and enthalpy change (ДН) of the reaction ?
rate can be determined by measuring decrease in Eaf (kcal) Ear (kcal) AH (kcal)
pressure in a time interval? A) 23.4 5.2 18.2
A) H2 (g) + I2 (g) —» 2HI (g) B) 23.4 18.2 5.2
B) CH4 (g) + 2 0 2 (g) -> C 0 2 (g) + 2H20 (g) C) 5.2 23.4 18.2
C) N 2 (g) + 3H2 (g) -> 2NH 3 (g) D) 18.2 5.2 23.4
D) 2Fe3+ (aq) + Sn2+ (aq) -> 2Fe2+ (aq) + Sn4+ (aq) E) 23.4 5.2 -18.2
E) C aC 0 3 (s) CaO (s) + C 0 2 (g)
5 . The rate of a reaction slows down with time at
3 . Given the reaction : constant temperature because
H 2 0 2 -> H20 + l/2 0 2 + 26 kcal A) the concentration of reactants decreases.
If the Ear for this reaction is 44 kcal, which one of B) the concentration of products decreases.
the following is its PE-RC diagram ? C) the temperature decreases.
D) the catalyst is used up.
Ai B) Cl
E) the energy of activation increases.

6 . 2 0 grams of marble chips were placed in a

flask. Which one of the following would you add to
obtain 100 mL of carbon dioxide as quickly as pos­
sible?
A) 20 mL of 1 M HCl B) 40 mL of 1 M HCl
C) 30 mL of 1.5 M HCl D) 20 mL of 1.2 M HCl
E) 40 mL of 2 M HCl

7 . A + 2B -> AB 2 Rate = к [A] [B] 2

Doubling the concentration of В increases the rate of
 Ш ШШ ММ М
М1111Ш1Ш
11 1111111 111 111111111111 1 111111 11М
Ш 11Ш!Ш1Ш11ШШШ11<
Ш 1Ш111Ш1ШШ1Ш1Ш111Ш
ШШШМ11111 Rates o f Chemical Reactions 33

the reaction by a factor of If the initial concentrations of A, В and С were 0.2

A) 2 В) 3 C) 4 D) 6 E) 8 M each, what would be the initial rate at the same
temperature?
8 . The following data were obtained for the reac­ A) 2 x 10- 2 B) 4 x 10' 2 C) 8 x lO* 2
tion X + Y -4 Z D) 8 x 10- 3 E) 1.6 x 10‘ 2
Initial Initial Initial Rate of
Exp
Concentration Concentration Formation of Z 1 1 . Given the reaction A + В —» 2C, doubling the
no.
of X of Y m m ol/litre.s
concentration of A doubles the rate of the reaction,
1 0.20 M 0.20 M 0.06 but doubling the concentration of В does not change
2 0.20 M 0.40 M 0.24 the rate. The rate equation is
3 0.40 M 0.40 M 0.24 A) Rate=k[A] 2 B) Rate=k[C] 2 /[A] [B]
The rate of the reaction is proportional to C) Rate=k[A] D) Rate=k[A] [B]
A) (X] [Y] B) [Y] С) [X] 2 [Y] E) Rate=k[A] [B] 2
D) [Y] 2 E) [X] [Y] 2
1 2 . The most important effect of increasing tem­
9 . The following data were obtained for the reac­ perature of a reaction is to
tion A) change the reaction mechanism
X + 2Y + Z — > K + 2L B) lower the energy of activation
[X] [Y] [Z] Rate (M/s) C) increase the number of collisions
- 4 D) increase the number of effective collisions
0 .0 1 0 .2 0 .1 1 .8 x 10
E) increase the activation energy for reverse reaction
- 4
0 .0 2 0 .2 0 .1 3.6 X 10
13. Increasing the temperature for a reaction
- 4
0 .0 1 0.4 0 .1 1 .8 x 10 I. increases the heat of reaction.
- 4 II. increases the average kinetic energy of molecules.
0 .0 1 0 .2 0 .2 7.2 x 10 III. increases the number of effective collisions.
Which one of the following is the rate expression for Which one (s) of these statements is correct ?
the reaction? A) Only II В) I and II С) I, II and III
A) Rate=k[X] [Z] 2 D) II and III E) Only III
B) Rate=k[X] [Y] [Z]
C) Rate=k[X] [Y] 2 [Z] 1 4 . Which one of the following graphs is wrong
D) Rate=k[X] 2 [Y] [Z] 2 for the reaction
E) Rate=k[X] [Y] [Z] 2 A2 (g) + B2 (g) -> 2AB (g) + heat

1 0 . At a certain temperature the following data

were collected for the reaction
A + B + 2C -> D + E
[A] [B] [C] Rate

0 .1 0 .1 0 .0 1 2 x 1 0 ’ 3

- 3
0 .2 0 .2 0 .0 1 4x10
- 3
0 .2 0 .1 0 .0 1 4 x 10

0 .2 0.3 0 .0 2 8 x 1 0 ’ 3
34 Chapter 1 НИ Illllllllllll I II Ill ...... Illlllllllllll

1 5 . A marble chip weighing one gram and one 19. The reaction,
gram of powdered chalk (both CaC03) were placed in 2N 0 2 C1 (g) -4 2N 0 2 (g) + Cl2 (g),
two similar beakers half full of 1 M HCl. The chalk has a mechanism with two steps. One of the steps is
dissolved in seconds whereas the marble chip was given as
still visible after a few minutes. The most likely ex­ N 0 2 C1 (g) + Cl (g) -> N 0 2 (g) + Cl2 (g) (fast).
planation of this is that What is the rate expression for the reaction ?
A) different reactions were taking place. A) Rate = k[N 0 2 Cl] 2
B) the chalk dissolved quickly because of its degree B) Rate k[N 02] [Cl2]
of purity. C) Rate = k[N 0 2 Cl] [Cl]
C) acids react quickly with all powdered substances. D) Rate = k[N 0 2 Cl] [Cl]
D) the rate of reaction depended on particle size. E) Rate = k[N 0 2 Cl]
E) chalk is more soluble in HCl.
20. The reaction,
1 6 . Which is not a correct statement about a 2N 2 0 5 (g) + heat -> 4 N 0 2 (g) + 0 2 (g),
catalyst? and its mechanism are given,
A) It changes the reaction mechanism. 2[N 2 0 5 —> N 0 2 + NO 3 ] (slow)
B) It lowers the energy of activation.
N 0 2 + N 0 3 —> NO + N 0 2 + 0 2 (fast)
C) It increases the number of molecules with the ne­
cessary energy to react. NO + N 0 3 —> 2N 0 2 (very fast)
D) It alters the heat of reaction. Which one of the following PE-RC diagrams be­
E) It changes the potential energy diagram of the re­ longs to this reaction ?
action.

1 7 . The mechanism of a reaction is given as fol­

lows:
AB + С -> DE + F
DE + G К+L
L + F -> M + С
Which one of the species involved in the mechanism
is a catalyst?
A) DE B) F C) G D) L E) С

18 . The rate expression for the reaction,

3A2 + 2B2 - 4 2A 3 B2, is Rate = к [AJ [B J 1^
Which one of the following reactions is the rate de­
termining step in the mechanism of this reaction?
A) A2B + 1/2 B2 —^ A 2 B2
B) A2 + 1/2 B2 -> A2B
C) A2 + B2 —> A 2 B2
D) A2 + B2 -> 2AB
E )A 2 + 2B 2 -> 2AB2
 CHAPTER

CHEMICAL EQUILIBRIUM

The objectives o f this chapter are to enable the student t o :

1 - Explain th e dynam ic nature o f equilibrium.
2 - Describe the conditions of a dynam ic equilibrium state.
3 - Write equilibrium constant expression, Kc and Kp.
4 - D erive th e equilibrium constant expressions for situations w here ch e­
m ical reactions are reversed or m ultiplied by coefficients, or added to­
gether.
5 - C alculate th e nu m erical valu e o f Kc, from equilibrium co n cen tra ti­
ons.
6 - U se th e "Le Chatelier's Principle" to m ake p red iction s o f how eq u ili­
brium is affected w hen an equilibrium m ixture is disturbed.
7 - Evaluate the value o f reaction quotient and decide the direction o f reac­
tion w hich w ill take place.
8 - State the driving forces that are responsible for the existence o f chem i­
cal equilibrium .
ШЙНМ11111111ШН1Ш11111111М
1111111111Ш|11Ш11111Ш111111Ш1111Ш1М
1М1Ш1111111111Ш11111111М
1111111ШЩ|||||||11М
1Ш1Ш111111ШШ11 Chemical E quilibrium 37

An important question about a reaction is its extent to which it takes place.

Does the reaction proceed until one of the reactants is completely used up? Does
it proceed to only a slight extent? In this chapter we will discuss the fact that the
conversion of reactants into products is not complete for the most of the reac­
tions in a closed system. These reactions are reversible and do not go to
completion.
2.1 NATURE OF CHEMICAL EQUILIBRIUM
Consider the reaction
X2 (g) + Y2 (g) -> 2XY (g)
Suppose that one mole of each of X2 and Y2 are placed into a closed-one liter
container at a certain temperature. According to the collision theory; the more
energetic molecules of X2 and Y2 collide effectively to produce the activated
complex. And then the activated complex decomposes into the product, XY. At
the beginning of the reaction, the concentrations of X2 and Y2 are the highest.
As the time passes, the [X2] and [Y2] gradually decrease. So the rate of the
forward reaction decreases. On the other hand, the rate of the reverse reaction is
zero at the beginning, because the [XY] is zero. As soon as forward reaction
takes place, some XY molecules are produced, and they begin to collide with
each other to form the activated complex. The activated complex may produce
reactants X2 and Y2. The rate of the reverse reaction is very low initially but it
increases in the course of time because the [XY] increases as the reaction pro­
ceeds. As the [XY] increases the rate of the reverse reaction increases too. Fi­
nally a situation is reached at which the rates of the forward and reverse reac­
tions are equal. This situation is called dynamic equilibrium condition. A
double arrow ( <=^) is used to indicate the equilibrium. These changes can be
shown graphically as follows. See Figure 2.1 and Figure 2.2.

concentration (mol/L) Rate

Equilibrium Nonequilibrium —«-Equilibrium

forward reaction
X2 + Y2 -> 2XY

X2 Of Y2 :

iiiiiiiiiii-iii-iit:::®™? Icq time

FIGURE 2.1 The variation o f concentrations of re­ FIGURE 2.2 The variation o f the rates o f for­
actants and products as the reaction reaches equilibri­ ward and reverse reactions as a function of time.
um. At equilibrium the concentrations of both reactants At the time, tgq, the rates become equal, and the
and products remains unchanged.
reaction reaches equilibrium.
38 Chapter 2 i ............. n i i i i i i i ...... .......n il! ....I... НШПНШШ ... I............. I....................... НИШ...... H ill ....... н ш н ш п ш ш п .......

In Figure 2.1 the curves show changes in concentrations o f reactants and prod­
ucts with time for the reaction
X 2 (g) + Y2 (g) *=* 2XY(g)
In Figure 2.2 the curves show the rates o f forw ard and reverse reactions w ith
time for the reaction
X 2 (g) + Y2 (g) <=^ 2XY(g)
The sam e equilibrium can be established by placing some XY into the sam e
vessel at the sam e tem perature. It does not m atter to establish the equilibrium
beginning with either reactants or products or a m ixture o f both, unless the con­
ditions are m aintained constant. It m eans that if the reaction is started w ith two
m oles o f XY instead o f 1 m ol o f X 2 and 1 m ol o f Y 2 in the sam e container at the
sam e tem perature, the identical equilibria will be established. See Figure 2.3.

concentration (mol/L)
Nonequilibrium Equilibrium ^
v
2 0

mm
Concentration changes during approach to equilibrium, (a) The reac­
tion is started with 1 mol of X 2 and 1 mol of Yp in one liter vessel, (b) The reaction is
started with 2 mol of XY alone. The same equilibrium mixture is attained whether it is
started from the left or from the right.

W hen the reaction has reached equilibrium , the reactants X 2 (g) and Y 2 (g)
react and form XY (g) at exactly the same rate as XY decom poses and forms X 2
and Y2. Therefore there is no observable (macroscobic) changes in the concen­
tration o f any material, but microscobic changes (changes in molecular state)
still go on. The equilibrium state o f a reaction is not the state in which all the ac­
tivities have stopped, but the state in w hich there are two opposing changes
w hose effects exactly cancel each other. Such an equilibrium state is called
"dynamic equilibrium state". To m ention from a dynam ic equilibrium ,
FIGURE 2.4 A dy­ (1) the reaction must be carried out in a closed system. A closed system
nam ic equilibrium state contains a constant amount o f matter. In other words there must be no matter
in a saturated solution
addition to or removal from the system.
o f C aC O j. The rates o f
dissolving and p re cip i­
(2) there must be two opposing changes taking place at the same rate.
tation equal. (3)яЬе temperature must be the same throughout the system
(имнмимшшшцмцшцншийи^ижшшнишишцшшшцициншшшшшишшмтшшмищщшшьцикшChemical E quilibrium 39

F or exam ple, consider a saturated solution o f C a C 0 3 in a closed flask at

room temperature. The rate o f dissolving and the rate o f precipitation are equal.
So there is no m easurable change in any property at constant tem perature. All
these properties describe a dynam ic equilibrium state. See Figure 2.4.

EXAMPLE 2.1 Recognizing Equilibrium

Problem : Consider some water in a closed bottle. Is there an equilibrium be­
tween water and its vapor?
Solution : Yes. At the beginning, the molecules with high kinetic energy over­
come the attraction of neighboring molecules and escape from liquid state (evapora­
tion). As the number of H20 molecules in the vapor state increases, the number of
collisions between H20 (g) molecules increases. And during these collisions some
molecules lose some of their KE. When these molecules with low KE pass near the
surface of the liquid, they are attracted by the molecules in the liquid, and finally re­
turn to the liquid state (condensation). After a while the rate of evaporation and
condensation become equal to each other at room temperature. We conclude that the
reaction has reached the equilibrium. We can observe that at the beginning the level of
water decreases and then it becomes constant. The vapor pressure increases at first and
then becomes constant.
V If the amount of water is not enough to produce vapor which exerts equilibrium
vapor pressure, equilibrium will not be established. All the water will evaporate.
Figure for example 2.1

2.2 THE EQUILIBRIUM CONSTANT

2.2.1 DERIVATION OF EQUILIBRIUM CONSTANT
FROM RATE EXPRESSIONS

Assum e that the forward and reverse reactions are sim ple one step reactions
for the reaction
X 2 (g) + Y 2 (g) <=> 2XY (g)
the rate o f the forward reaction is
Ratef = kf[X2] [Y2] (f —» forward reaction)
and the rate o f the reverse reaction is
Rater = kr[XY]2 (r —> reverse reaction)
A t equilibrium, these two rates are equal, therefore
Ratep = Rater
kf [X2] [Y2] =kr [XY]2
by rearranging the equation we obtain

kf _ [XY]2
kr [X2][Y 2]

Since specific rate constants kf and k r are constant at constant tem perature, their
ratio, k f / kr , is also constant. It is called equilibrium constant, Kc w here
the subscript, c, refers to concentrations.
40 Chapter 2 НННННИПННШНЫННННШННННННННПНПНННН НИН ннниннннпшннннннннннннннннн шнннпнннпнннннннншнннп

The concentration terms o f products

appear in the numerator and those
fo r reactants in the denominator.

N otice that the num erical value o f the equilibrium constant does not depend
on the initial concentrations o f reactants and products. Its value at any given
tem perature is determ ined by the equilibrium concentrations o f products and re­
actants. H ow ever the value o f Kc varies w ith temperature.
A large value o f K c indicates that reactants are converted into products to a
large extent or vice versa.
W e have dealt w ith a sim ple one step reaction. N ow consider a reaction
w hich has a tw o-step mechanism.
(ki)f
S te p I. 2X <= 2 - X2
(kiX

(k2)f
S te p I I . x9 + y 9 2XY
K )r

The overall reaction is 2X + Y 2 2X Y

The equilibrium constant for the overall reaction can be found as follows. E qui­
librium constants for each step are

^ к _<Ц,_ [X Y f
1 no, p f 2 <M, Р Ч И

To elim inate X 2 (w hich does not appear in the overall reaction) let us m ultiply
Kj and K2.

к х к , = И х _ е т 1 = _ и 1
[xf Р Ч И [ x] 2 [ y 2]

R e m e m b er th a t the ra te
Since Ki and K 2 are constants their product gives a new constant, Kc.
e x p re s s io n is w r itte n
fro m th e s lo w e s t step
re a c tio n in th e m e c h a ­
n ism . B u t the e q u ilib ri­
u m c o n s ta n t e x p r e s ­
m m
s io n is w r itte n fro m Pay attention that the coefficients o f the substances in the balanced overall reac­
the b a la n ce d o v e rall r e ­
tion become the exponents o f the related substances.
a ctio n d ire c tly .
R egardless o f the m echanism by w hich a reaction occurs, the equilibrium con­
stant expression can be w ritten from the balanced overall reaction directly. For
a reaction, in general terms
aA + bB + ... cC + dD + ... V
the equilibrium constant expression is given by
 Chemical Eauilibrium 41

v _ [C] [D] ... products

_ b
[A I M — > reactants

EXAMPLE 2.2 Writing the Equilibrium Constant Expressions

Problem : Write the equilibrium constant expressions together with their units for the following balanced re­
actions.
(a)N 2 (g) + 2 0 2 (g) *=*• N 2 0 4 (g)
(b) N 2 (g) + 3H 2 (g) 2NH 3 (g)
(c) 4HC1 (g) + 0 2 (g) 2C12 (g) + 2H20 (g)
Solution : The concentration terms for substances that appear on the right side of the chemical equation are
written in the numerator of the expression for Kc. The concentration terms for substances that appear on the left
side are written in the denominator. And the coefficients of substances in the balanced equation become the expo­
nents of the related substances.
92 r _ -,2 r ,2
[n 2 o 4] mol/L 1 [NH3] 1 _ [Cl j [H 2 0 |
(a)K c = (b)K c (c)K c = M
2 2 2 2
M M 2 mol/L x mol / L mol / L mol [ n 2] [H 2] 3 M 2 [HCl] 4

EXERCISE 2.1 Write the equilibrium constant expressions for the following reactions.
(a) CO (g) + H20 ( g ) ^ > C 0 2 (g) + H2 (g) . (b) 2 S 0 2 (g) + 0 2 (g) 2S 0 3 (g)
(c)2N O B r(g)«=> 2NO (g) + Br2 (g) (d) 2NH 3 (g) + 3Cb (g)^= * N 2 (gj + 6HC1 (g)

2.2.2 H E TE R O G E N E O U S EQ U ILIB R IU M

An equilibrium involving reactants and products that are in different phases is

called a heterogeneous equilibrium. As an exam ple, consider the equilibri­
um reaction,
C (s ) + C 0 2 (g) < = ^ 2CO (g)
The equilibrium m ixture contains a solid, C, and tw o gaseous substances, CO
and C 0 2. Its equilibrium constant is

K’ - Ec c > ] 2
c [C ][C 0 2]

Since С is a solid, how do we express its concentration ? The concentration o f

a pure solid or a liquid is constant at a constant tem perature and pressure, and is
detennined by its density. T heir concentrations do not change during the reac­
tion either. Then the concentration o f С is constant. Therefore its constant value
m ay be included in the value o f K(.

K 'JC I =-[C0]
[COJ
The product, Kc'.[C] gives a new constant K c
42 Chapter 2

[СО]
K„ =
[СО 2]
Conventionally the concentration term s o f pure solids (or liquids) do not appear
in the equilibrium constant expressions. B ut we keep in m ind that the concen­
tration effect o f pure substances is hidden in the value o f K c.

EXAMPLE 2 .3 Writing Equilibrium Constant Expressions

Problem : Write the equilibrium constant expressions of the given reactions.
(a) 3Fe (s) + 4H20 (g) < ^> Fe 3 0 4 (s) + 4H 2 (g)
(b) CaO (s) + S 0 3 '(g) CaS0 4 (s)
(c) Ca(HC0 3 ) 2 (aq) C aC 0 3 (s) + H20 (1) + C 0 2 (g)
Solution : The concentration terms of the pure solids and liquids do not appear in the equilibrium constant
expression. 4

_ [H 2]
a) Kc = b) К = __ — с ) К = ___ ________
[H 2o ]
W c [S03] c [Са(НСОз)2]

Notice that solutions arc liquids but not pure.

EXERCISE 2.2 Write the equilibrium constant expressions for the following reactions.
(a)Z n (s) + C u 2 + (aq) <=> Zn 2 + (aq) + Cu (s) (b) 2A1 (s) + 3/2 0 2 (g) A12 0 3 (s)
(c) C aC 0 3 (s)<=* CaO (s) + C 0 2 (g) (d) H C 03_ (aq) «=> H+ (aq) + C O |“ (aq)

2.2.3 CALCULATIO N OF EQ U ILIB R IU M C O NSTANT

T he num erical values o f K c m ay be determ ined experim entally. T he follow ing

examples illustrate how to calculate Kc .

EXAMPLE 2.4 U n d ersta n d in g E q u ilib riu m C on cep t

Problem : The given graph shows
how the concentrations of reactants and
products change with time for a reaction.
a) What are the reactants and products ?
b) What is the initial concentration of
each of the substances ?
c) What is the change in the concentration
of each of the substances ?
d) What is the balanced equation of the
equilibrium reaction with the smallest
whole number coefficients ?
e) What is the equilibrium constant for
the reaction ?
 imiiiiiiiiiiiiiiiiii Chemical E quilibrium 43

Solution :
a) A and В are the reactants. Because their concentrations decrease with time. С and D are the products. Because
their concentrations increase with time.
b) From the graph we see the initial concentrations as follows:
[A] = 0.6 M , [B] = 0.5 M , [ C ] = 0 M , [D] = 0 M.
c) The change in the concentration of each substance can be calculated by subtracting the initialconcentration
from the final concentration.
Д[А] = 0.4 —0.6 = —0.2 М. 1 T h e n e g a tiv e sig n in d ic a te s the
д [B ] = 0.2 - 0.5 = —0.3 M J c o n su m p tio n o f a su b stan ce.
A[C] = 0.2 - 0.0 = +0.2 M 1 T h e p lu s sig n in d icates the pro-
A[D] = 0.1 - 0.0 = +0.1 M J d u c tio n o f a su b stan ce.
d) The consumption or production of a substance is related with its coefficients in the balanced equation. By tak­
ing the advantage of this concept we may write the equation as follows :
0.2A (g) + 0.3B (g) 0.2C (g) + 0.1D (g)
We may write it with whole number coefficients as follows :
2A (g) + 3B (g) ^ 2C (g) + D (g)
e) The equilibrium constant expression is :

K„ = [C]2 PP]
2 3
[A] [B]
The concentrations in the Kc must be the equilibrium concentrations, the concentrations which remains un­
changed with time.
These are : [A] = 0.4 M ; [B] = 0.2 M ; [C] = 0.2 M ; [D] = 0.1 M

K c = J M L J P i i l = 3 .1 2 5

[0.4] 2 [0.2] 3

EXERCISE 2.3 The graph shows the variation of the concen­

trations of substances with time as it approaches the equilibrium.

(a) Write the equation for the reaction.

(b) At what lime does the reaction reach equilibrium?
!(c)What is the value of Kc for this reaction at that certain temperature?
a ) A( g ) + 3B(g) <=> 3C(g) + 2D(g) b) 10sec. c)Kc = 3 6

mm,
Graph fo r exercise 2.3

EXAMPLE 2.5 Calculating the Equilibrium Constant

Problem : The analysis of an equilibrium mixture has the following composition at a certain temperature for
the reaction, X 2 (g) + Y2 (g) 2XY (g)
[X2] = [Y2] = 2 x 10‘ 2 M , [XY] = 3 x 10' 2 M. Calculate the numerical value of Kc for this reaction.
44 Chapter 2 ............... НПИНППШННШЖНИМ... Ill.............IIIII1IIIIIIIIIII............................................ III!...... Illl

Solution : To calculate the Kc, the equilibrium concentrations of XY, X2 and Y 2 given in the problem are
substituted into the equilibrium constant expression.
X 2 (g) + Y2 (g) *=* 2 XY(g)

Kc = rX Y f = ( 3 X 1 ^ 2) 2 = (9 x 10~4) = 2 25

fX?l ^ 2J (2 x 1(f) (2 x lO”2) (4 x 10~4)

EXERCISE 2,4 NO (g) , 0 2 (g) , and NO 2 (g) are at equilibrium in a steel tank at a certain temperature.
An analysis of the contents of the tank shows [NO] = 0.05 M , [0 2] = 0.15 M and [N 02] = 15 M. What is the
value of Kc for the reaction 2NO (g) + O 2 (g) < = »,r 2NQ 2 (g) ? 6x10s

EXAMPLE 2.6 Calculating the Equilibrium Constant

Problem : A mixture of 0.10 mol of H 2 and 0.10 mol of I2 is placed in a ten-liter container at 550° C. When
the equilibrium is established the mole number of HI is found to be 0.16. What is the value of Kcat 550° С for
the reaction H 2 (g) + I2 (g) < = ? 2HI (g) ? y
Solution : Practically in all equilibrium calculations, it is better to write down the values of initial concen­
trations, changes in concentrations during the establishment of equilibrium, and the concentrations at equilibrium
as shown below.
In itia l c o n c e n tra tio n o f H 2 and I 2 are:
n H2 0 .1 0
H 2 (g) + I2 (g) 2HI (g) [H ,l = 0 .0 1 M
L II V 10
In itia l 0.01 M 0.01 M 0M
n l2 _ 0 .1 0
C hange __________________ ?________________?_____________ ? __ _ 0 .0 1 M
at Equilibrium ? ? ?
Ы 10
[HI] = 0

H 2 (g) + I2 (g) ^ 2HI (g) S in c e th e e q u ilib riu m m o le n u m b e r

In itia l 0.01 M 0.01 M 0M o f H I is 0 .1 6 , th e e q u ilib riu m c o n ­

C hange 7 ? ? c en tratio n o f H I is

at Equilibrium ? ? 0.016 M [Ш1 = M i = 0 .0 1 6 M

L J 10

T h e c o m p a ris o n o f th e in itia l a n d
e q u ilib riu m v a lu e s o f H I re v e a ls th a t
H 2 (g) + I2 (g) ^ 2HI (g) d uring the re a c tio n 0.0 1 6 M o f H I is
p ro d u c ed . T h e n the c h an g e in [H I] is
Initial 0.01 M 0.01 M 0M (+ 0 .0 1 6 M ). T h e p ro d u c tio n o f
Chanse______________ -_0 .0 Q8 _________- 0.008 +0.016 0 .0 1 6 M H I m e a n s th e c o n s u m p ­
at Equilibrium ? ? 0.016 tio n s o f 0 .0 0 8 M o f H 2 a n d 0.0 0 8
M o f I2 fro m th e b a la n c e d e q u atio n .
So the c h an g e in [H 2 ] is (- 0 .0 0 8 ) M
a n d the ch an g e in [I2 ] is (-0 .0 0 8 M ).
mHnnitiiiniiitiiiHiTii)tiiHuiiMi!iiiiiiitiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiMMiHiiiiiiiiHiiiiiitiiHiiiiiiHiiitiiiiiiiitiii)iitinti(itiHiiMiitiiiiii Chemical Equilibrium 45

H2 (g) + I2 (g) < = ^ 2HI (g) A t e q u ilib riu m , th e [H 2J and [I2 ] re ­

Initial o.Ol M 0.01 M 0M m a in e d a re 0.01 - 0 .0 0 8 = 0 .0 0 2 M
C hange . q.008 M - 0.008 M + 0.016 each
at Equilibrium 0.002 M 0.002 M 0.016 M

Now we substitute the equilibrium concentrations into the equation for the equilibrium constant.

к - [Hlf - -64
[H 2] [ I 2] ( 0 .0 0 2 ) ( 0 .0 0 2 )

If we start w ith pure HI at any m olar concentration, or w ith any m ixture o f

H 2, h or w ith any m ixm re o f H 2 ,1 2 and HI and hold the tem perature at 550°C
until the equilibrium is established, the m olar concentrations o f the three sub­
stances w ill have changed so that the reaction quotient, [H I ] 2 / [H2] [I2] is al­
ways equal to 64.

EXERCISE 2.5 Starting with 0.20 of HI in a 10 L vessel, for the reaction

H 2 (g) + I2 (g) 2HI (g)
it is found that 0.02 mol of H2 is present at equilibrium at 550°C. Calculate the equilibrium constant for the re­
action at 550°C. Kc=64

EXERCISE 2.6 The reversible reaction 2A (g) + 3B (g) С (g) + 2D (g) is started with 1.5 tnol of
A and 2.5 mol of В in a 1 L vessel at a certain temperature. At equilibrium the concentration of D is measured to
be 1 M.Calculate theKc for the reaction at the given temperature. Kc=2

EXAMPLE 2 .7 Calculating the Equilibrium Constant

Problem : At 800 K, 2 mol of NH 3 are introduced into a two-liter container. At the temperature of the exper­
iment 25 % of NH 3 is decomposed when the equilibrium is established.
2NH3 (g) N 2 (g) + 3H2 (g)
Calculate the value of Kc for the equilibrium at 800 K.
Solution : The initial concentrations of substances are

[NH3] = M M - = I M [N^ = 0 [H2] = 0

Since the NH 3 is 25% dissociated, 25 % of 1 M of NH 3 dissociates, that is 1 x (25 / 100) = 0.25 M.

We can calculate the molarities of N 2 and H 2 which are produced by 0.25 M of NH 3 from the coefficients of
chemical equation. Since 2 M of NH 3 produce 1 M of N2, 0.25 M of NH 3 produces 0.125 M of N2. The equation
shows that 2 M of NH 3 produce 3M of H2, therefore 0.25 M of NH 3 produces 0.375 M of H2.
The equilibrium concentrations are:
The equilibrium concentration = initial concentration - change in concentration (used or produced)
[NH3] = 1 - 0.25 = 0.75 M
[N2] = 0.125 M (it was zero initially)
[H2] = 0.375 M (it was zero initially)
46 Chapter 2

All these can be tabulated as follows.

2N H 3 (g) ^ N 2 (g) 3H2 (g)
In itia l 1M 0M ОМ
Change - 0.25 M + 0.125 M + 0.375 M
at Equilibrium 0.75 M 0.125 0.375 M.

We substitute the equilibrium concentrations into the equation for equilibrium constant and solve the equation
for the Kc

K = [N 2] [ H 2f = (0.125) (0.375)3_ 0 Q12

[n h | (0 . 7 5 ) 2

EXERCISE 2.7 A 5 liter closed container which has 2 mol of S 0 3 is heated to 700K. 20 % of S 0 3 de­
composes into S 0 2 and 0 2 to give the equilibrium mixture represented by the equation
2S 0 3 (g) 2S 0 2 (g) + 0 2 (g)
Calculate the Kc for the reaction at 700 K. Kc =2.5xl0-3

EXAMPLE 2.7 C alcu latin g the E q u ilib riu m C on stan t for a H eterogen eou s
E quilibrium
Problem : 2 mol of C 0 2 and 4 mol of С are introduced into a two liter reaction vessel at 1500 K. When the
equilibrium is established at 1500 K, the mole number of C 0 2 is found to be 1. What is the value of Kc at 1500
К for the following reaction ? C 0 2 (g) + С (s) 2CO (g)
Solution : The examination of the phases of the substances in the reaction reveals that it is a heterogeneous
equilibrium. The simple rule for heterogeneous equilibrium is that the concentrations of pure solids and liquids
are omitted from the equilibrium constant expression. After this explanation, let us follow the usual procedure to
calculate the Kc.
C 0 2 (g) + С (s) 2CO (g) Initially :
Initial 1M - 0M [C] = constant (pure solid)
C hange - 0.5 M - 1M [C 02] = 2 mol/2 L = 1 M
------------------ [CO] = 0
A t Equilibrium 0.5 M 1 M

, At equilibrium:
г i2 2 [C 02] = 1 mol/2 L = 0.5 M
К =& = j - = 2
° [CO 2 ] 0.5

EXERCISE 2.8 When steam is passed over hot coke, water gas, an important industrial fuel, is produced
according to the reaction.
С (s) + H20 (g) CO (g) + H2 (g)
When a mixture of 1 mol of С and 1 mol of H20 are placed in a 1 L vessel at 1000 K, at equilibrium
[H 2] = 5 x 10" 2 M. Calculate Kc ' K c = 2.6 x 10 ~3.
 ..... Chemical E quilibrium '47

2.2.4 CALCULATIO N OF EQ UILIBRIUM

C O N C E N T R A T IO N S

W e have seen that the equilibrium constant for a given reaction can be cal­
culated from the equilibrium concentrations at a certain temperature. Rem em ber
th at the equilibrium constant is constant only if the tem perature does not
change. Once w e know the value o f K c, we m ay use it to calculate the quilibri-
um concentrations o f the sam e reaction at the sam e tem perature. N ow let us see
how to do this.

EXAMPLE 2 .9 Calculating the Equilibrium Concentrations

Problem : At 600° C, the Kc for the following reaction is 4 x 10"2 .
C 0 2 (g) + H2 (g) <=> C 0 (g ) + H 2 0 (g )
If 0.2 mol of C 0 2 and 0.2 mol of H 2 are placed into a 2 liter container, what equilibrium concentration of each
species will result?
Solution : The initial molarities of C 0 2 and H2 are 0.2 mol / 2 liter = 0.1 M, and the initial molarities of
CO and H20 are zero. From the coefficients of the balanced equation, we can deduce that 1 mol of C 0 2 combines
with 1 mol of H2 and they produce 1 mol of CO and 1 mol of H 2 0 . If we accept thatx M of C 0 2 and x M of H 2
are combined, then x M of CO and x M of H20 will be produced.
In that case the equilibrium concentrations are:
[C 0 2] = (0.1 -x ) M [H2] = (0.1 - x) M [CO] = x M [H2 0] =x M
Let us tabulate them.
C 0 2 (g) + H2 (g) < = ^ CO (g) + H20 (g)
In itia l 0.1 M 0.1 M
Change -x M -x M xM xM
A t Equilibrium (0.1 -x) M (0.1 -x) M x M x M

_ [со] [нр] _ (x) (x) _ (.x)2 _ 4 до’ 2

[C 0 2] [H2] (0.1 - x) (0 .1 -x ) _ (рЛ _х )*

By taking the square root of both sides of the equation and solving for x

2 x 10 ~ 1 = — — => x = 0.017 M
0 .1 - x

Now we can calculate the equilibrium concentrations.

[C 02] =. [H2] = 0.1 - x = 0.1 - 0.017 = 0.083 M.
[CO] = [H2 0 ] = x = 0.017 M
These values may be substituted into the equilibrium constant expression to.check the solution of the prob­
lem. If Kc is found as 4 x 10‘ 2 , we will be convinced that the solution of the problem is correct.

\ ,
_ (0.017)^ _ 4 x jg solution is correct.
(0.083)
48 Chapter 2 ишишнпншинниншшпииииииннннмииниинииншииишшииимииииишпшшииншшишншшишшшииинишшнпмниииниипнш

EXERCISE 2.9 The equilibrium constant for the reaction, H2 (g) + I2 (g) <=^ 2HI (g), is 64 at a given
temperaiure. If one mole of H2 and one mole of I2 are introduced into a one liter reaction vessel, (a) what is the
equilibrium concentration of each species? (b) what percent of H2 is used to reach equilibrium? (c) If the equilibri­
um were started with 2 moles of HI, what would be your answer to the part a ?
( a ) [ H 2 ] = [ I 2] = 0 . 2 M , [ H I ] = 1 . 6 M , ( b ) 8 0 % o f H 2

EXERCISE 2.10 At a certain temperaiure Kc for the reaction, PC15 (g) < = ? PC13 (g) + Cl2 (g) , is
4 x 10'2 . If 0.8 mol of PC15 is placed in a closed 4 liter container at this temperature, what percent of PCl5
will be decomposed when equilibrium is established? 36%

EXAMPLE 2.10 C a lcu la tin g th e E q u ilib riu m C o n cen tra tio n s F or H eterogen eou s
E quilibrium
Problem : Solid ammonium carbamate, N 2 H 6 C 0 2, decomposes into ammonia, NH3, and carbon dioxide,
C 0 2, at high temperatures.
ы дам з) <=> 2n h 3 (g) + c o 2 (g)
At a certain temperature Kc = 4 x 10' 6 for this reaction. Calculate the number of moles of each species, when
39 grams of ammonium carbamate are put into a 1 liter container at a certain temperature and allowed the reac­
tion to reach equilibrium. (N2 H 6 C 0 2 = 78 g/mol)
Solution : Ammonium carbamate is solid. We learned that its concentration is constant. The concentration
of N 2 H 6 C 0 2 is not contained in equilibrium constant. The mole of N 2 H 6 C 0 2 = 39 / 78 = 0.5 mol. From the
equation of the reaction, we deduce that, when 1 mol of N 2 H 6 C 0 2 decomposes, 2 mol of NH 3 and 1 mol of C 0 2
are produced. If x mol/L of N 2 H-,C02 decomposes, 2x molar of NH 3 and x molar of C 0 2 are produced.

N2H6C 0 2 (s) * = * 2NH3 (g) + C 0 2 (g)

In itia l constant (solid) 0M 0M
C hange - X mol/L 2x M x M

A t Equilibrium 2x M x M

Kc = [NH 3] 2 [C 02] = (2x) 2 (x) = 4x3 = 4 x № 6 => x = 0.01 M

Mole numbers at equilibrium,

[NH3] = 2x = 0.02 M -> n = M x V = 0.02 x 1 = 0.02 mol NH 3
[C 0 2] = x = 0.01 M -» n = M x V = 0.01 X 1 = 0.01 mol C 0 2
nN„tbco„
2 6 2
= 0.5 - x = 0.5 - 0.01 = 0.49 mol

EXAMPLE 2.11 C a lcu la tin g th e E q u ilib riu m C o n cen tra tio n s For H etero g en eo u s
E quilibrium
Problem : The Kc for the equilibrium, A (s) + 2B (g) 4= ^ 2C (g), is 0.49. What concentration of С will
be in equilibrium with 0.2 mol of A and 0.8 mol of В per liter?
Solution :
A (s) + 2B (g) 2C (g)
m oles at equilibrium 0.2 mol 0.8 mol X mol
Cone at equilibrium constant 0.8mol/L x mol/L
0.8 M x M
ш!ш1м1ш11ш1ш1шм1111шш1ш11ш1шшшшшш111ш111мш!1шшш11ш11ш1шш1пш1мнш1шш111ш1111шншшшш1111 Chemical Equilibrium 49

Substituting equilibrium concentrations into the Kc expression, and by taking the square root of both
sides, we obtain the value of Kc .
Г -2 2
Kc = 0.49 = x = 0.56 [С] = X M = 0.56 M
Г -i 2 2
И (0.8)

EXERCISE 2.11 For the equilibrium, CO (g) + 2H 2 (g) < = ^ CH3OH (g), at a certain temperature Kc
is 2. Calculate the equilibrium concentration of H2 , if the [CO] and [CH3 OH] are 0.20 M and 0.40 M respective­
ly at equilibrium. 1 M

2.2.5 EQUILIBRIUM CONSTANT EXPRESSED IN

PR ESSU R ES (K p)

F or equilibria involving gases, the equilibrium constant is frequently ex ­

pressed in term s o f partial pressures rather than in term s o f equilibrium concen­
trations. Because the m easurem ent o f pressure o f gases is easier than the m eas­
urem ent o f their concentrations. The equilibrium constant expressed in terms o f
partial pressures o f gases is called Kp. The subscript p refers to the pressure
F or example, for a reaction in general terms
aA (g ) + b B (g ) + ... <=> cC (g ) + d D (g ) + ...

r c f p p f . .. P
" cc x P~ D...
d
K c=-
К =— H—
P . т^а „Ь
[Af [B]b... A ^ В '' ‘
U n le ss o th e rw is e n o t­
P A , P B , P c , P D represent the equilibrium partial pressure o f each species.
e d , th e p a r tia l p r e s ­
su re s are e x p re ss e d in
Kp and K c o f a reaction are related to each other, le t us derive the form ula
a tm in a К p e x p r e s ­ that relates Kp to Kc.
s io n . First we set up the relation betw een the concentration o f a gas and its partial
pressure. C onsider the gas A.

[A] = ^ and P . , V = n A. R . T or RT
V V
by inserting [A] instead o f nA / V we obtain P A : [A] R T .
Similarly we can write:
P B = [B] RT , P c = [C] R T , P D = [D] R T
by substituting these into the Kp expression
с d „ j

P c x P D... ( [C] RT ) x ( [D] RT )

Kr =
P Ax P b ■ ( [A] RT )Sx ( [B] RT )b

by rearranging the equation gives:

г -,c г- nd c+d
(c + d) - (a + b)
i t - [D] ( R T ) Ke (R T.)
[A] [B] ( R T )
50 Chapter 2 ||||||||Ш Ш 1 М Ш 1 1 Ш 1 1 1 Ш 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 Ш Ш 1 1 1 1 1 1 1 Ш 1 Ш 1 1 1 Ш 1 1 1 1 1 !Ш 1 1 1 1 1 1 Ш Ш 1 Ш Ш 1 Ш Ш Ш 1 1 Ш 1 1 1 1 1 1 1 1 1 1 1 Ш 1 1 1 Ш 1 1 1 1 1 1 1 !Ш 1 1 1 1 М 1 Ш Ш 1 1 1 1 1 1 1 Ш Ш 1 1 Ш 1 1 Ш 1 1 Ш Ш 1 1 1 1 1 1 1

Since, (с + d) is the sum o f m ole num bers o f products and (a + b) is the sum
o f m ole num bers o f reactants w e can shorten (c + d) - (a + b) to A n and
obtain a general equation :
К p —> equilibrium constant in term s o f pressures
K c —> equilibrium constant in term s o f concentrations
R —> ideal gas constant (0.082 L .atm /m ol.K )
A n
K, K c (R T ) T —> tem perature in К
A n —> the difference in the coefficients o f gaseous
products and reactants.

F or exam ple ; for the reaction, N 2 (g) + 3H 2 (g) 2N H 3 (g)

-2
Д n = 2 - (3 + 1) = - 2 and Kp = Kc (RT) or Kp = K c (RT)

F or the reaction,
2C12 (g) + 2H20 (g) 4HC1 '(g) + 0 2 (g)
A n = (4 + 1) - (2 + 2) = 1 and Kp = K C(R T )! or Kp = K c RT

EXAM PLE 2 .1 2 W r itin g the K p and K c

Problem : Write the Kp and Kc relationships for the following reactions in general terms.
(a) H 2 (g) + I2 (g) <=> 2HI (g) (b) 4NO (g) + 3 0 2 (g) <=* 2N 2 Os (g) (c) C aC 0 3 (s)<=^ CaO (s) + C 0 2 (g)
S o lutio n : а) Д n = 2 - (1 + 1) = 0 therefore Kp = Kc (RT)° -> Kp = Kc
b) Д n = 2 - (4 + 3) = - 5 therefore Kp = Kc (RT) ~ 5 -> Kp = Kc / (RT ) 5
c) Д n = 1 - 0 = 1 therefore Kp = Kc (RT) 1 —> Kp - Kc RT
Note that we only consider gaseous substances. Since C aC 0 3 and CaO are solid substances, their mole num­
bers (coefficients) are not taken into account.

E X E R C IS E 2 .1 2 Write the Kp and Kc relationships for the following reactions.

(a)N 2 0 4 (g) * = * 2N 0 2 (g) (b )2 S 0 2 (g) + 0 2 (g) <=> 2S 0 3 (g)
(с) С (s) + H20 (g) <:=i CO (g) + H 2 (g) (d) S 0 2 (g) + N 0 2 (g) S 0 3 (g) + NO (g)

EXAMPLE 2.13 K p a n d K c R e la tio n s h ip

Problem : Calculate Kp for the reaction, N 2 (g) + 3H2 (g) 2NH 3 (g) at 500° С if its Kc is 6 x 10' 2.
S olution : Д n = 2 - (1 + 3) = - 2 and Kp = Kc (RT)-2
R = 0.082 L atm/mol К, T = 500 + 273 = 773 K, and Kc = 6 x 10' 2
Substituting these values into the equation gives
Kp = 6 x 10" 2 x (0.082 x 773)' 2 =* Kp = 1.5’ x 10' 5

EXERCISE 2.13 At a certain temperature, the equilibrium reaction, 2N 0 2 (g) 2NO (g) + 0 2 (g),
has a Kp = 0.6 and a Kc = 0.01. Calculate the equilibrium temperature in degrees Kelvin. R = 0.08 L atm/mol K.
750 К
!ШШ!Ш11ШМШ
Щ1ШШ1Ш11Ш 1ШШШ1Ш|||Ш||Ш1111!1ШШШШШШиШ1ШШШ11МПШ
МИШ ИШ1Ш|иШШЫШШ1!ШШ|Ш Chemical Equilibrium 51
Ш

EXAMPLE 2 .1 4 Calculation for Kp

Problem : At 500° С the equilibrium partial pressures of substances lor the reaction,
2HI (g) H 2 (g) + I2 (g), are as follows. P H 2 = 8.0 x 10" 2 atm, Pl 2 = 9.8 x 10" 3 atm, Рш = 4.0 x 10' 3 atm.
Calculate Kp for the reaction at 500° C.
Solution :
2HI(g) «=* H 2 (g) + I2 (g)
Equilibrium partial pressures: 4.0 x 10 " 3 atm 8.0 X 10 " 2 atm 9.8 X 10 " 3 atm

K = p nzx p i2 = 8.0 X IQ- 2 X 9.8 X 10 ' 3 = 49

’ (4 .0 Х Ш -1 2

EXERCISE 2.14 At a certain temperature Kp for the reaction, POBr3 (g) <=> POBr (g) + Br2 (g) is 8 .
If the partial pressures of Br2 and POBr arc 0.50 atm each, what is the equilibrium partial pressure of POBr3?
0 .0 3 a tm

EXAMPLE 2.15 Calculation of Equilibrium Partial Pressures

Problem : The Kp for the reaction, COCl2 (g) <=.-> CO (g) + Cl2 (g), is 5 x 10~9 at 127°C. What are the
equilibrium partial pressures of COCI2 , CO, and CI2 after 9.9 g of COCl2 has placed into a 0.41 L of vessel and
allowed the reaction to reach equilibrium ? COCl2 = 99 g/mol
Solution : The initial number of moles of COCl2 is (9.9 g/99 g/mol) = 0.1 mol

The initial pressure of COCI2 (g) is : p = n P i = ^ x 0.082 x 400 = 8 atm.

0.41
COCl2 (g) «=» CO (g) + Cl2 (g)
Initial pressure 8 atm 0 atm 0 atm
Change in pressure - x atm +x atm +x atm
Equilibrium pressure ( 8 - x) atm x atm x atm
Substituting these equilibrium partial pressure into Kp expression gives :
Pco x P Qj 2 -9
Kp = ------------- = —— = 5 x 10
P p co a 2 * -x
Anranging this gives the quadric equation : x2 + 5 x 10 x - 4 x 10- 8 = 0
Solving this equation for x gives x = 2.0 x 10" 4 atm. (Remember that the negative value of x has no meaning
here.) The equilibrium partial pressures of gases a r e :
p co = рсь = x = 2 .0 x 10"4 atm and P coci 2 = 8 -x= 8 - 2 .0 x 1 0 -1 4 = 8 atm.

EXERCISE 2.15 4 moles of NH 3 in a two-liter vessel is allowed to come toequilibrium at a total pres­
sure of 3.6 atm. The number of mole of N 2 (g) in the equilibrium mixture is measured to be 1mol.What is Kp
for the following reaction below ?
2NH 3 (g) « = * N 2 (g) + 3H 2 (g) 2.43
52 Chapter 2 ПИПШ
Ш1Ш
И1Ш
|1Ш
ШШ1Ш
11Ш
ШН11Ш
1Ш1П1Ш
Ш11Ш
И11111|1111Ш
1111Ш
1111Ш
Ш1Ш
Ш|111Ш
Ш1Ш
ИИ1Ш
|11Ш
ШШ111Ш
1111Ш
111Ш
ШтШ
Ш1Ш
11111111|1И1Ш
Ш11

EXAMLE 2 .1 6 Calculation for Kp

Problem : At 357° С, 1 mol of PC15 is introduced into a closed container, and the equilibrium
PCI5 (g) < » PCI3 (g) + Cl2 (g) is established. At the equilibrium, 80% of PC15 decomposes and the total
pressure is found to be 2 atm. Calculate the Kp and Kc for this reaction at 357°C.
Solution :
PCI 5 (g ) <=> 3
P C I (g ) +Cl 2 (g ) 80 % of 1 m ol o f PC I 5 is
In itia l m ole num bers 1 mol 0 mol 0 mol lx (8 0 /1 0 0 ) = 0.8 m ol
Change in reaction - 0.8 mol + 0.8 mol + 0.8 mol
A t Equilibrium 0.2 mol 0.8 0.8 mol

The total mole number = nT = (0.2 + 0.8 + 0.8) = 1.8 mol, and total pressure (given) = PT = 2 atm
Partial pressures of gases:

P = ^ x pT = № x 2 = 0.22 atm Рраз = — x P T = M . x 2 = 0.89 atm

5 nT 1 .8 nT 1 .8

P ci2 = P раз = 0-89 atm

... ,
and the value of Kn is
■ rr Рраз x p a 2
KD = ----------------- =
0.89 x 0.89 - л
= 3.6
P P Ppcis 0.22
and the value of Kc is Kp = Kc (R T)л n => 3.6 = Kc (0.082 x 630)1 => Kc = 0.07

EXERCISE 2 .1 6 One mole sample of CH20 is put into a vessel and heated to 367°C. Atequilibrium
it is found that 80 % of CH20 has decomposed into H2 (g) and CO (g) and the total pressure of the gas mixture
is measured to be 3.6 atm. What is Kp for the reaction, CH20 (g) H2 (g) + CO (g) ? What is Kc ?
Кp =6 .4 ,K c= 0.1 2

EXERCISE 2.17 A sample of ammonium bisulfide was heated in a closed container.

NH 4 HS (s) NH 3 (g) + H2S (g). At equilibrium the toLal pressure in the container was foundto be 0.8
atm. What is Kp for the reaction ? 0.16

EXERCISE 2.18 At a certain temperature, sufficient amount of A and some В which has a partial pres­
sure of 2 atm are placed in a closed container. When the reaction,
2A (s) + В (g) 2C(g)
has reached equilibrium, the total pressure in the container is measured as 3 atm. Calculate the Kp for the reac­
tion at this temperature. 4

EXAM PLE 2 .1 7 C a lc u la tio n o f K c a n d K p

Problem : When the reaction 2 S 0 3 (g) < = ^ 2 S 0 2 (g) + 0 2 (g) reaches the equilibrium at 227° С and 2.87
atm, the density of gas mixture is found to be 4.8 g/L.
a) What is the percentage dissociation of S 0 3? b) What is the partial pressure of each gas at equilibrium?
c) What is the value of either Kp or Kc?
Solution ; (a) Assume that the volume of the container is 1 liter. Then the total mole number in the con­
tainer at the equilibrium state is ? 87 v 1
PV = nRT -> n T = 1x 1 = 0.07 mol
0.082 x 500
 iiniinм11111itIiIи Chemical E quilibrium 53

On the other hand, the initial mass of SO 3 = V x d = 1 L x 48 g/L = 48 g

Mole number of SCh , n so = — §— = 0.6 mol
3 80 g/mol
Let's make a table to show changes in moles.
2S 0 3 (g) <=> 2S 0 2 (g) + 0 2 (g)
Initial moles 0.6 mol 0 mol 0 mol
Change in moles - 2x +2x +X
Moles at equilibrium (0.6 - 2x) mol 2x mol x mol => ntotal = 0.6 - 2x + 2x + x = 0.6 + x

0.6 + x = 0.7 —> x = 0.1 mol, 2x 2 x 0 .1 = 0 .2 mol

% dissociation of S 0 3 = x 100 = 33.3 %
0.6

(гил r\ r Ao a i
dj n so, = 0.6 - 0.2 = 0.4 mol
dP Scn = ------
nRT = 0.4 x 0.082 x 500 = 16.4. atm
.
V I

nS02 = 2 x = 0 .2 mol P S02 = 0 ,2 X °-(|8 2 = 8 .2 atm

Пег = x = 0 .1 mol P^ = ^-500 = 4 ,1 atm

(с) К , - Р Ч Х Р и = <8-2>' * <4Л > = 1.025 atm

pL 3 ( i6.4)2

Kp = Kc (RT)An An = 3 - 2 = 1, Kp = KCRT —> K = = 1 -0 2 5 K 0.025 = 2.5 x 10 2

c RT 0.082 x 500
We can also find the Kc by using the concentration terms

[S 0 3] = °-4i ^ 0l = 0.4 M , [S 0 2] = °-2 ^ 0l = 0.2 M , [0 2] = -Q- 1 ^ 01 = 0.1 M

Kc = [soj2N = mL m= 0.025 = 2.5 x ю ‘ 2

[S 0 3f (0.4) 2

EXAM PLE 2.18 Calculation of K c and K p

Problem : Equal volumes of S 0 2 and 0 2 gases at the same pressure and temperature are introduced into a 4 li­
ter container and heated to 127° C. When the equilibrium is established at this temperature the equilibrium con­
centration of S 0 2 is three times larger than that of S 0 3. If the equilibrium pressure is measured as 61.5 atm,
(a) what is the mole of S 0 2 introduced initially into\the container?
(b) What are the numerical values of Kc and Kp?
Solution : (a) Since the pressures and volumes of gases are the same, their mole numbers are equal. Let x be
the number of mole of each gas initially. к
2 S 0 2 (g) + 02(g) *=* 2S 0 3 (g)
In itia l m oles x m ol X m ol 0 m ol
C hange in m oles - 2y m o l - у m ol + 2 у m ol
M oles at equilibrium (x - 2y) m o l (x - y) m o l 2y m o l
Cone, at equilibrium X - 2y jyj X -у jyj 2y_ jyj
4 4 4
54 Chapter 2 шшишшпшшшшпишиинпшшпшшишшшиишиииииишишшиншпшпшшшппинишиишшишншшшнишшишшшшшшшиши

The [S02] at equilibrium is three times larger than the [S03],

Therefore we may write - —— = 3 x —

4 4
The solution of this equation for у gives у = — mol
8
On the other hand, the total mole number at equilibrium is

nT = = _ 6 L 5 x ± _ = 7.5 mol
RT 0.082 x 400
nx in terms of x and у at equilibrium is: x - 2y + x - у + 2y = 2x - у = 7.5
If у is substituted for x / 8 in 2x - у = 7.5, x is found as 4 mol
x = 4 mol = initial mol of S 0 2, у = — = — = 0.5 mol
8 8
(b) Now we can find the number of mole and concentration of each species at equilibrium as follows.
-species mole number concentration (mol/L)
502 x - 2y = 3 0.75
02 x - у = 3.5 0.875
503 2y = 1 0.25

К. , H 2 = - < °f> 2 = 0.127

[S02f [0 2] (0.75)2(0.875)

Kp = Kc (RT)4n , Дп = 2 - 3 = -1, Then Kp = Ь . = _ => Kp = 3.9 x 10~ 3

F p RT 0.082 x 400 p

2.2.6 VARIATION OF EQUILIBRIUM CONSTANT WITH

THE BALANCED FORM OF EQUATION

Suppose the equilibrium constant for the reaction below is K c. W hat is the
value o f the Kc o f the reverse o f this reaction?

A (g) + В (g) С (g) + D (g) Kc им

[А] [в]
I f a n e q u a tio n is r e ­
v e rsed , the v a lu e o f K c
K' 1/K r
is in v erted . С (g) + D (g) A (g) + В (g) K 'c = M Гв
[Cj [D]
W hen the Kc and Kc' are com pared, it is easily seen that K c' = 1/K C
That is, the equilibrium constant o f a reverse reaction is the reciprocal o f that
o f fo rw a rd reaction. i-
Consider another case,
A (g) + В (g) <: С (g) + D (g ) Kc =
[A] [B
MiiiMiiiitiiHiiiiiiiitiHtiiiiiiiiiiiiiiiiiiiiiiiiiHiiiitiiiiiiiiiiiiiiiniitiiiiiiiitiiiiiiiiiiiiiiiiiiiiiiiiiiniiiiiiiiiiiiiiiiiMiiiiiiiiiiiiiiiiiiiiiiii C hem ical E q u ilib r iu m 5 5

nA (g) + nB (g) «=> n C (g ) + nD (g) Kc' = ?

W here n is a num ber. To derive the relation betw een K c’ and K c for these re­
actions, let us write K c’ and express it in term s o f K c and n.

к' - IcT ГРГ _ ( rcl ГР or K ’c = K c"

C - [ A]n [B]n " l [ A ] [ B

I f the c o e ffic ie n ts in the In general, i f a reaction is m ultiplied by a certain fa cto r, n, the equilibrium
b a la n ce d e q u atio n is m u l­ constant fo r the new reaction, K c', is the nthp o w er o f the old value o fK c.
tip lie d b y a c o m m o n fa c ­
tor, the n e w e q u ilib riu m
c o n s ta n t w ill b e the o ld It is often necessary to add two reactions together to obtain a third reaction.
o n e r a is e d to th e c o m ­ Consider the following example:
m o n fa cto r po w er.
(I) 2NO (g) + H 2 (g) < ^> N 20 (g) + H 20 (g) K<h
(И) N20 (g) + H 2 (g) <— > N 2 (g) + H20 (g) Kc2
(III) 2NO (g) + 2H 2 (g) <-=> N 2 (g) + 2H20 (g) Kc3
The third reaction can be obtained by adding the reactions I and II side by side.
The relationship among K Cl, Kc2 and K Cj can be derived easily.

T h e e q u ilib riu m c o n sta n t

fo r the o v e rall re a c tio n is
к = мм
[NO]' [H2]
Kc =
Щ M
N P ] [H;
_ [n 2] [H P]
and K r =
the p ro d u c t o f eq u ilib riu m
[NO] 2 [Щ 2
c o n sta n ts fo r th e in d iv id ­
u a l re a c tio n s th o s e a re Comparing the three equilibrium constants we see that
added.
Kf K Cl x K C2.

W hen two or m ore reactions are added the equilibrium constants fo r these reac­
tions m ust be multiplied to fin d the equilibrium constant o f the overall reaction.

EXAM PLE 2.19 E q u ilib r iu m C o n s ta n t R e la tio n s h ip B e tw e e n R e a c tio n s

Problem : Suppose that the Kc for the reaction below is 4 at a certain temperature.
A2 (g) + 1/2 B2 (g) A2B (g) Find the equilibrium constants for each of the following reactions at the
same temperature.
(a) 2A2 (g) + B2 (g) 2A2 B(g)
(b) 3A2B (g) 3A2 (g) + ЗДВ 2 (g)
(c) 1/2A2B (g) 1/2A2 (g) + 1/4B2 (g)

Solution :
(a) The reaction is obtained by multiplying the original reaction by 2. Then the equilibrium constant is :

Kc= K2 or Kc= 4 and K[. = 16

56 Chapter 2 Ш Ш Ш Ш П М Ш П Ш П И Ш И ............................. I ............... Ш П Ш Ш Ш Ш И Н П Ш Ш ............................ I .............................. H i l l ........... I ................. l l l l l l ............... I l l l l l l l l ..................... ..

(b) The original reaction is reversed and multiplied by three to obtain the given reaction. Then the equilibri­
um constant is:

к; = Ш =1-1 => к:= 1

Kj HI 64

(c) The given reaction is obtained by reversing the original reaction and then multiplying it by 1/2. Thus the
equilibrium constant Kc " is:
1/2
1/2 1/2
1/2

к - IШ1 !1 =
- I 1—1
fl| and k '=- or к" = 0.5
t
k JI “ I
" HI

EXERCISE 2.19 X 2 (g) + Y2 (g) X 2Y (g) + Y (g) has a Kp = 2 at a certain temperature. What
is the Kp of each of the following reactions at the same temperature ?
(a) 3X2 (g) + 3Y2 (g) < = ^ 3X2Y (g) + 3Y (g) (b) 1/2X2Y (g) + 1/2Y (g) ^=> 1/2X2 (g) + 1/2Y2 (g)
a) 8 b )-L
V2

EXAMPLE 2 .2 0 Finding Kc When two or more Reactions are Added.

Problem : Find the equilibrium constant for the reaction,
A (g) + 3B (g)<г=» 2C (g) + D (g), in terms of the equilibrium constants of the following reactions.
(I) A (g) + В (g) E (g) K, ,
(П) F (g) + G (g) В (g) + E (g) K2
(П1) F (g) + G (g) + В (g) 2C (g) + D (g) K3
Solution : To obtain the reaction A (g) + 3B (g) 2C (g) + D (g), the first reaction, the reverse of the
second reaction and the third reaction must be added together.
A (g) + В (g) <=> E (g) K,
B (g) + E (g) F (g) + G (g) 1/K2
F (g) + G (g) + В (g) <=* 2C (g) + D (g) K3
A (g) + 3B(g) <=> 2C (g) + D (g) к = К, x± x K3
K2

EXERCISE 2.20 At a certain temperature :

(I) S 0 3 (g) + NO (g) <=* S 0 2 (g) + N 0 2 (g) Kc = 0.25
(II) NO (g) + 1/2 0 2 (g) * = * N 0 2 (g) Kc = 2
Find the value of Kc for the reaction, S 0 2 (g) + 1/2 0 2 (g) < = ^ S 0 3 (g), at the same temperature. 8

EXERCISE 2.21 At a certain temperature some reactions and their equilibrium constants are given be­
low.
A + r>
В <. = ^ ^С +, Т
DЛ 1 j
K,
В < -* c + E K:2
A <---> E + F К
3 К? x K 3
Find the equation of the reaction which has an equilibrium constant К
2
K2
'ммпн^нгнпмпиппппмпннппипнппниннииппгиммпшмммпппппппппшпипмшппмптпитниггтшгтпшп Chemical E quilibrium 57

2.3 REACTION QUOTIENT

R e a c tio n q u o tie n t is u se d The equilibrium constant helps us predict the direction in w hich a reaction
to p re d ic t the d ire c tio n in
m ixture will proceed to reach equilibrium . Suppose w e started w ith a m ixture
w h ic h a re a c tio n o c c u rs
o f both reactants and products. Is the given m ixture at equilibrium ? If not, in
to e s ta b lis h e q u ilib riu m .
It is u s u a lly a p p lie d to which direction will it take place to achieve equilibrium ? T he answ ers to these
n o n e q u ilib riu m c o n d i­ questions m ay be found by introducing a new concept, reaction quotient.
t io n s . The reaction quotient, Q, is written below for a general reaction.

aA (g) + bB (g) ... <=2- cC (g) + dD (g) + ... Q = M [p ]

[a ]3 [B]b
The reaction quotient has the sam e expression as the equilibrium constant.
But the reaction quotient does not necessarily involve the equilibrium concen­
trations o f the species. The concentrations in the reaction quotient expression
m ay be concentrations at any time during the progress o f the reaction. How ever
if they are equilibrium concentrations, then
Qc = K c
The concept o f reaction quotient is usefull for a reaction under a given set o f
concentrations to decide whether the forward or reverse reaction will proceed to
establish the equilibrium.
If Q c < K c the reaction is not at equilibrium . To establish the equilibrium ,
the value o f Qc m ust increase to the value o f Kc. To do so, the num erator of me
reaction quotient m ust increase and the denom inator o f the reaction quotient
m ust decrease. The only way to reduce the denom inator and to increase the nu­
m erator is the reaction betw een A and В to produce С and D, o r forward reac­
tion.
If Q c > K c, to decrease the value o f Qc to Kc, the reverse reaction takes place
to a greater extent to establish the equilibrium.
If Q c = K c, the reaction is at equilibrium . The forw ard and reverse reactions
occur at the same rate.
W e may summarize these three cases as follows :

Qc = k c The systemis at equilibrium. The initial concentrations are equal to

the equilibrium concentrations.
Qc> kcReverse reaction takes place to establish equilibrium.
Qc < kcForw ard reaction takes place to reach the equilibrium.

EXAM PLE 2.21 Predicting the Direction of a Reaction to Establish Equilibrium

Problem : 1 mol of H2, 1 mol of I2 and 2 mol of HI are placed into a one liter container at a certain tempera­
ture to establish the equilibrium H 2 (g) + I2 (g) 2HI (g). What will be the equilibrium concentration of
each species, if Kc is 64 at this temperature?
58 Chapter 2 ншшшлшишнишшшшшшшшшиишшшшпишшшшшшниишншишшшшшшиишшншшшншшшшшншшшиишшишшшшш

S o lu tio n :
н 2 (g) + h (g) 2Ш (g) Kc = 64
In itia l 1M 1M 2M
C hange ? ? ?
at Equilib ? ? ?

To determine the change during the reaction, we must know which reaction will take place to establish the
equilibrium. To do so, we must calculate the value of reaction quotient by substituting the initial concentrations
into the reaction quotient expression.
г Л 2
О - M - 2 - \
‘ “ N H 1 x 1

Since Qc = 4 < Kc = 64, then the forward reaction takes place to establish the equilibrium. Let x mol of H 2 and x
mol of I2 react to give 2x mol of HI. In this case,

H2 (g) + i 2 (g) «г=> 2 Ш (g) ^ _ pHi] 2 _ (2 + 2 x )2 _

In itia l 1M 1M 2M Kc - rj-pj—jpr ^ —64
C hange ______________ -_xM_______-_xM_____ + 2x M L 2 J L ?l (l - x)
at Equilibrium (1 - x) M (1 - x ) M (2 + 2x) M

Solving the equation forx, we getx = 0.6 M. The equilibrium concentrations are:
[H2] = [I2] = 1 - x = 0.4 M, [HI] = 2 + 2x = 3.2 M.

Check : Kc = И = — = 64
[H2] [l2] (0.4) (0.4)

EXERCISE 2.22 The equilibrium constant (Kc) is 36 at a certain temperature for the reaction,
CO (g) + H20 (g) 4 = ^ C 0 2 (g) + H2 (g). Predict the direction in which the reaction will proceed to reach
equilibrium if it is started with
(a) 1 mol of CO, 1 mol of H2 0 , 1 mol of C 0 2 , and 1 mol of H2 in one-liter container.
(b) 0.5 mol of CO, 0.5 mol of H2 0 , 3 mol of C 0 2 and 3 mol of H 2 in two liter container.
(c) 0.5 mol of CO, 0.5 mol of H2 0 , 5 mol of C 0 2 and 5 mol of H2 in five liter container.
Calculate the equilibrium concentrations in each part. a) f o r w a r d b) a t e q ui l i b r i um c) revers e

EXERCISE 2.23 Given the reaction : S0 2 (g) + N0 2 (g) 4 = ^ S0 3 (g) + NO (g)

A mixture of 2 mol of S 0 2 , 2 mol of N 0 2 , 1 mol of S 0 3 and 1 mol of NO are introduced into a 1 L tank at a
certain temperature at which Kc = 4 for the reaction.
a) Is the mixture at equilibrium ?
b) If not, in which direction will the reaction proceed to achieve equilibrium ?
c) What is the equilibrium concentration of each of the species ?
[SO2] = [N
02]= /, [S0 3]= [N
O]= 2
 ...... шин Chemical Equilibrium 59

EXAMPLE 2.22 Application of Reaction Quotient Concept

Problem : A vessel contains NO (g), N 2 (g), and 0 2 (g). The partial pressures of these gases are
pn 2 = Po 2 = 0.1 atm and P ^o = 0.2 atm. The equilibrium constant, Kp, for the reaction
2NO (g) <-•■> N 2 (g) + 0 2 (g) is 0.04. Is the reaction at equilibrium ? If not, in which direction will the reac­
tion proceed to achieve equilibrium ? Predict the partial pressure of each gas when the reaction is reached equili­
brium. Calculate the equilibrium partial pressure of each of the gases.
Solution : To decide whether a reaction mixture is at equilibrium, first we should findthe numericalvalue of
Qp, by using the partial pressures of gases.
p N2 x P o 2 _ ( 0 .1 ) ( 0 . 1 )
= 0.25
NO, ( 0 -2)

Second we should compare the Qp and Kp. Since Qp = 0.25 > Kp = 0.04, the mixture is not at equilibrium, the
reverse reaction will take place predominantly to establish equilibrium.
In the reverse reaction, N 2 and 0 2 combines to give NO. As a result, during the establishment of equilibrium the
partial pressure of NO increases but the partial pressures of N 2 and 0 2 decrease. At equilibrium PNO > 0.2 atm,
P n 2= Po 2 <0.1 atm.
The equilibrium partial pressures can be calculated as follows :

2NO (g) N 2 (g) 0 2 (g) A s w e sta te d b e fo re , th e e q u ilib riu m

In itia l pressure 0 . 2 atm 0 . 1 atm 0 .1 atm m ay b e a p p ro a c h e d fro m b o th sides.
Change in pressu re + 2 x atm -x atm -x atm Y o u m a y c h a n g e the p la c e o f r e a c ­
Equilibrium pressu re (0.2+2x) atm (0.1-x) atm (0.1-x) atm tan ts a n d p ro d u c ts in th is re a c tio n
lik e :

P n x P r
N 2 (g) + 0 2 (g) *=> 2 N O (g)
Kp=- 0.04 (0Л m 0.2 = ()Л ~x- =>x = Q.043 B u t in th is c ase the e q u ilib riu m c o n ­
0 .2 + 2 x
sta n t K p m u st b e ta k e n as 1/0.04.
NO, (0 . 2 + 2 x)'
Thus,
NO : : 0.2 + 2x = 0.2 + 0.086 = 0.286 atm and PiN2 : ■P o 2 =0.1 - x = 0.1 -0.043 : 0.057 atm

EXERCISE 2.24 At a given temperature, a mixture of the following gases is prepared from the gases
with partial pressures p n o 2 - 0-5 atm, p n 2o4 = 0-5 atm. At this temperature, Kp for the reaction,
2N 0 2 (g) < = ^ N 2 0 4 (g), is 1. Will there be a net reaction ? Calculate the partial pressures of gases when the
reaction attains equilibrium. Q p = 2 < K p r e v e r s e r e a c t i o n, P ^ q 2 =0. 6S, P ^ 2 o 4 = 0 . 4 2 5

2.4 EQUILIBRIUM C H A N G E S'-

LE CHATELIER’S PRINCIPLE

Once a reaction has reached equilibrium it remains at equilibrium forever un­

til it is disturbed by a change o f condition. R eactions at equilibrium are d is­
turbed by adding or rem oving reactants or products, by changing the tem pera­
ture, p ressu re or volum e o f reaction vessel. N ow w e w ill exam ine the
relationship betw een the new equilibrium state w ith the old one, and we will
60 Chapter 2 шишшшшишшшшншишшшшнпжшшмшннпишииинишишшишшиишиишишшшшшниишшшшшшииишшишшншшпши

describe how to predict the way in which the reaction reaches the new equilibri­
um. The effects o f several factors (a change in concentration, pressure, v o l­
T h e v ery la rg e v a lu e o f um e, or tem perature) can be predicted by m eans o f a principle suggested by
K c in d icates th a t the for- I H enry L e C hatelier* (1850 - 1936). This principle is called "L e C h a te lie r's
w ard r e a c tio n is a lm o st p rin cip le."It states :" I f an external stress is applied to a reaction at equilibri­
c o m p le te , b u t it tells us um, the reaction w ill respond in such a way that m inim izes the stress in reach­
n o th in g a b o u t h o w fa st
ing a new equilibrium state."
the re a c tio n o c cu rs. T h is
L et us look at this principle in action by studying the equilibrium state o f the re­
re a c tio n ta k e s p la c e so
action :
slo w ly a t 2 5 °C th a t no
c o n s id e ra b le a m o u n t o f
N 2 (g) + 3H 2 (g) < = ^ 2N H 3 (g) ДН = - 22 Kcal.
3
N H is produced. K c for this reaction is 4.0 x 10s at 25°C.

2.4.1 CHANGES IN C O N C EN TR A TIO N

L et us add som e N 2 (g) to the reaction vessel w hich contains H 2, N 2 and

NH 3 at equilibrium at 25° C. The external stress applied to the reaction increases
the [N2], W hen the [N2] is increased, the equilibrium will be upset. According
to Le Chatelier's principle, the reaction will go to a new equilibrium state in a
way that decreases the stress, in this case by decreasing [N2], To decrease the
[N2], some o f the N 2 - but not all - m ust be used up by the reaction. This m eans
that N 2 and H 2 com bine to give N H 3, or sim ply the forw ard reaction takes
place to a greater extent to establish the new equilibrium state. The net result of
addition o f N 2 is a decrease in concentration o f H 2, and an increase in concentra­
tion o f N H 3. All these changes are shown graphically in Figure 2.5.

1 concentration (mol/L)

H2

1 3 x
N 2 ___________ _ .

: J2 X
::::::::: a ’.. :. i ;
: : -
*- e q u ilib r iu m • * •!» "°.1 a t ■*■!-■=- e q u ilib r iu m
j e q u ilib r iu m j

It l2 * time
FIGURE 2.5 Effect of the addition of N 2 on the equilibrium
N2 (g) + ЗН2 (g) 2 NH3 (g). When N2 is added, some N2 reactswith H2 and more
NH 3 is formed asthe reaction returns to a new equilibrium.
* H enry L o u is L e C h a te lie r : A F ren ch p ro fe s so r o f C h e m istry at the U n iv e rsity o f P aris. H e w as k n o w n fo r his
sk ills in in d u stria l m a n a g em e n t.
|1мш111!м111111н11м1ш111111!11111111м1ш11мш11111шммм11ш1111111шн1111м1111111шшшммммммм11ш111111ш11ммш1ш111ш1111 Chemical Equilibrium 61

At the tim e ti the equilibrium is upset by adding some N 2, and at the tim e t 2 the
new equilibrium is established. C om pare the new and old equilibrium concen­
trations o f each participant.
The same conclusion can be drawn by com paring reaction quotient and Kc.
[N H J 2
At the first equilibrium state : Qc - K c L----- —-
[N 2] [H2]
W hen som e N 2 is added, the reaction is no m ore at equilibrium . B ecause the
addition o f N 2 increases the [N2] , therefore the denom inator gets larger and
Qc < K c. To reestablish equilibrium , the value o f Qc m ust increase and becom e
equal to the original K c value. There would be two things to increase the value
o f Qc; a decrease in [H2], and an increase in [NH3], B oth are produced by the
forward reaction. As a result o f addition o f N 2 the forw ard reaction proceeds to
a greater extent and the [H2] decreases, the [NH3] increases.
Now suppose that some H 2 is rem oved from the reaction vessel. T he rem ov­
al o f H 2 decreases the [H2], then the external stress applied to the reaction at
equilibrium state decreases the [H2], According to L e Chatelier's principle, the
response o f the reaction to reestablish a new equilibrium state is to increase the
[H2], which is carried out by the reverse reaction. The net result o f the rem oval
o f H 2 is an increase in [N2], and a decrease in [NH3], O r graphically

FIGURE 2.6 Effect of the removal of H2- When H2 is removed, more NH 3 decompos­
es into N2 and H2 as the system again comes back to equilibrium.

In Figure 2.6 you see the effect o f rem oval of some H 2 on the equilibrium.
By com paring Qc and K c, we reach the sam e result. The rem oval o f H 2, or
decreasing the [H2] increases the value o f Qc and Qc > K c. To restore equilibri­
um the value o f Qc m ust decrease and m ust becom e equal to K c.

To decrease the value o f Qc, the [NH3] m ust be decreased and the [N2] m ust
be increased. These are made by the reverse reaction.
62 Chapter 2 miiiiimiiiimitmiHin ...... шиш...................II................................... I........шпини..... iiiii ...........

As a summary : F or the reaction N 2 (g) + 3H 2 (g) 2N H 3 (g)

direction o f Change in
Stress applied response o f the reaction
reaction [N21 [H2] [NH3]
Addition o fN 2 or
decreasing [N2] forward —> - Dec. Inc.
Increasing [N2]
removal o fH 2 or
Increasing [H2] reverse <— Inc. - dec.
decreasing [H2I
Addition ofNH 3 or
decreasing [NH3] reverse <— Inc. Inc. -
Inc INHj]

The removal ofN H 3 Increasing [NH3] forward —» dec. dec. -

Increasing [H2] decreasing [H2] forward —> dec. - Inc.

EXERCISE 2.25 Consider the equilibrium : 4 NH 3 (g) + 5 0 2 (g) 4NO (g) + 6 H2 0 (g). How will
the amount of NH 3 at equilibrium be affected by (a) addition of 0 2 (b) addition of NO (c) removal of H20
(d) removal of 0 2 a,с decrease;b,d increase
--------------------------

2.4.2 CHANGES IN VOLUME AND PRESSURE

Volum e and pressure changes do not significantly affect the concentrations
o f solids or liquids, since they are alm ost incom pressible. H ow ever, they
change concentrations o f gases.
Suppose the volum e o f the container in w hich N 2, H 2 and N H 3 are at equili­
brium is decreased. W hen the volum e o f the reaction vessel is decreased the
concentrations o f all the species w ill be increased, and the m olecules becom e
m ore crowded. Then, the stress applied to the reaction is a decrease in the dis­
FIGURE 2.7 The ef­ tance betw een m olecules. As a response, the reaction tries to increase the dis­
fect of decreasing vol­ tance betw een m olecules. This can be done if the num ber o f m olecules is re­
ume in equilibrium duced. C onsequently if the volum e is decreased, the reaction w hich w ill
Ыз+ЗНг 2NH3 produce few er num ber o f m olecules will take place. All these are show n in F ig­
(a) In the reaction ure 2.7 and 2.8.
N2 + 3 H 2 «= > 2N H 3
(b) (c)
if the volume of the re­
action vessel is de­
creased to half its origi­
n a l value, (b) the
concentrations (partial
pressures) of N2 , H2 ,
and NH 3 are all dou­
bled, and the total pres­
sure is therefore dou­
bled. The equilibrium
thus shifts to the right, 0 5
(c), which decreases
the total num ber of
molecules and thereby
decreases the to ta l
pressure. When equili­
brium is reestablished,
the final pressure Pf is n 2 + зн 2 <=> 2NH 3 N 2+ 3H 2 <=> 2N H 3 N 2+ 3H 2 «=> 2N H 3
less than 2P- but great­
er than Pj. E quilibrium N o t at eq u ilib riu m E q u ilib riu m is re e sta b lise d
||Ш
Ж11Ж
ШШШ
Ш!1!111Ш
1111||||Ш
111Ш
11111Ш
1Ш!11Ш
1111111111Ш
111Ш
1ШШ
1Ш1111111111111Ш
111111НШ
1!1М
11111111Ш
1|1Ш
11М
Ш1111 Chemical Equilibrium 63

W h en th e v o lu m e o f ah In the case, N 2 (g) + 3H 2 (g) 2 N H 3 (g) ; w hen one m olecule o f N 2

e q u ilib r iu m m ix tu re i n ­ reacts with three m olecules o f H 2, two m olecules o f N H 3 are form ed. In other
v o lv in g g a s e s is d e ­ w ords the num ber o f m olecules is reduced from four to tw o by the forw ard re-
c r e a s e d , a n e t r e a c tio n i
action.Therefore a decrease in volum e o f the reaction vessel causes the forward
p ro c e e d s in the d ire c tio n 1 reaction to take place further to reestablish the new equilibrium . T he net result
th at p ro d u c es fe w e r n u m ­
b e r o f m o lecu les. is an increase in [NH3], a decrease in both [N2] and [H2],
The same result can be reached by reasoning the values o f Qc and K c.
concentration (mol/L)
2

equilibrium none _ equilibrium at the first equilibrium state, Q = К = — 3]__

quilibrium
3z
Nw 3
W hen the volume is decreased,
I z -.2
n NH3
V n
_ g j
Ш1 _ х У 2
f 2z
м и 3
N V
n '
H2

V
П~ 2 * %

t2 the value o f Qc will decrease too. Since Qc < Kc the equili­

brium is upset. To reestablish the new equilibrium , the value
FIGURE 2.8 When the volume of the o f Qc m ust increase and becom e equal to the value o f K c. To
equilibrium system, do so, the forward reaction will take place, and the [N2], [H2]
N2 (g) + 3H2 ( g ) ^ 2NH3 (g) will decrease and the [NH3] will increase.
is reduced, Л/2 and W2 react to form more
NH3 , thereby decreasing the number of
molecules from four to two.

EXAM PLE 2.23 The Effect of Volume Changes on Equilibrium Concentrations

Problem : Predict the direction of the net reaction in each case as a result of decreasing volume (increasing
pressure) on the system at constant temperature.
(a) 2 S 0 2 (g) + 0 2 (g) < =* 2S 0 3 (g)
(b) 2C12 (g) + 2H20 (g) « = * 4HC1 (g) + 0 2 (g)
(c) N 2 (g) + 0 2 (g) «=> 2NO (g)

Solution : (a) Since a decrease in volume always favors the reaction which decreases number of molecules,
we must count the number of molecules of gaseous products and reactants. On the reactants side there are three
molecules (two S 0 2 and one 0 2), and on the products side there are two molecules (two SO3 ). Then, when the
forward reaction takes place, three molecules disappear and two molecules appear, as a result the number of mole­
cules in the system decreases. Therefore the [S02] and [0 2] decrease, and the [SQ3] increases.
(b) By using the same reasoning given above, we can deduce that the reverse reaction takes place to reach a new
equilibrium state, in which the [HCl], and the [0 2] decrease, and the [Cl2], [H2 0 ] increase.
64 Chapter 2 Ml M ill I ......... ......................................................................................

(c) Since the number of molecules on both sides of the reaction is the same (two); neither of the forward or re­
verse reaction will decrease the number of molecules. So, volume changes do not disturb the equilibrium state of
the reacLion.
We may reach the same results for parts a, b, and с by investigating the changes in Qc as follows.

(a) Q = [s o f ASCH
x V
n so2x n o 2 **

Decreasing volume of the container, (the value of V in Qc expression) decreases the value of Qc and then Qc
becomes smaller than IQ. The forward reaction takes place to reestablish the new equilibrium state.

JI O
. [на][о2] V V пна х п о 2 1
:-------------- X —
(b) Q„ 2 2 V
[а2]2[н2оу а2 п а 2х пн р
V V

Since a decrease in volume causes Qc > Kc, the reverse reaction takes place to reestablish the new equilibrium.
-,2
NO

V n NO
(0 Q - W
() c [N2] [ 0 2] % 2 x n o2
V V

Since the reaction quotient or Kc expression is independent of V, the volume does not change the equality be­
tween Qc and Kc, or volume changes does not disturb equilibrium.

EXERCISE 2.26 What effect will increasing the volume of the reaction vessel have on the equilibrium
concentration of each species for the equilibrium, 2H2S (g) + CH4 (g) CS2 (g) + 4H 2 (g) ?
I H 2 S] and [ C H 4I wi l l decrease, /C S 2/ a n d [ H 2 I wi l l i nc r e a s e .

T he effect o f pressure changes due to volum e changes can be deduced by

P re s s u re C h a n c e s h a v e
m eans o f the foregoing argum ents about volum e changes. An increase in pres-
n o e r le c t o n re a c tio n s . -- . .
in v o lv in g o n ly lie[Uid s sure has ^ lc same effect as a decrease in volum e on the equilibrium or vice ver-
o r so lid s. B e c a u s e th ese Sa.
su b sta n c e s a re p ra c tic a l- H ow ever, if the total pressure o f a gaseous reaction is increased by adding
|'an inert gas by holding the volum e o f the reaction vessel constant, the partial
pressures (or concentrations) o f reactants and products do not change, therefore
the equilibrium state o f the reaction is not disturbed. W hen an inert gas is added
at constant pressure, this will have the sam e effect as increasing volum e. To
keep the pressure constant the volum e m ust increase due to the addition o f the
inert gas.
 Chemical Equilibrium 65

EXAM PLE 2.24 The Effect of Pressure Changes on Equilibrium Concentrations

Problem : Indicate the effect of the following changes on the equilibrium as shown by the equation,
N 2 0 4 (g) * = * 2N 0 2 (g)
a - The internal pressure of the reaction vessel is increased at constant temperature,
b - Some helium gas is added to the reaction vessel at constant volume and temperature.
Solution : a) When the pressure is increased, the volume of the reaction vessel decreases. As a result, the re­
verse reaction takes place to establish a new equilibrium state, and the [N2 0 4] increases, the [N 02J decreases.
b) The helium gas does not react with anyspecies present in the container, therefore it does not
change the mole number of any species. Since the volume is heldconstant, the equilibrium concentrations and
therefore the equilibrium state of the reaction does not change.

EXERCISE 2.27 Predict the direction of change for the reaction

2NO (g) + Cl2 (g) <=* 2NOC1 (g)
which is originally at equilibrium, when the following change is applied.
(a) The pressure of the system is increased.
(b) The volume of the system is increased.
(c) Some neon gas is added by keeping volume constant.
(d) Some chlorine gas is added.
(e) Some NO gas is removed.
a, d favors the fo rw a r d reaction; b, e favors t he reverse reaction; с has no change on equili­
brium state.
________________________________________________________________

2.4.3 CHANGES IN TEM PERATURE

Since the value o f depends on temperature, a change in tem perature natu­
rally changes the value o f Kc, or a change in tem perature upsets the equilibrium
state o f a reaction.
Consider the reaction
N 2 (g) + 3H 2 (g) <=> 2N H 3 (g) + 22 kcal.
Suppose the tem perature o f the reaction m edium is increased. As a response,
the reaction tries to decrease tem perature. This is done by consum ing energy.
T he energy is consum ed by the reverse reaction. T hen the reverse reaction p ro­
ceeds until the new equilibrium state is reached at that tem perature. In other
w ords, w hen the tem perature o f a system is increased ,the equilibrium is dis­
placed in such a way that heat is used up. In general, increasing temperature f a ­
vors endothermic reaction and decreasing temperature favors exothermic reac­
tion.
F or an endotherm ic reaction increasing tem perature increases the quantities
г T h e o nly fa cto r that can
o f products and decreases the quantities o f reactants. Since K c shows the ratio
c h an g e th e v a lu e o f K c I
o f products to reactants, increasing tem perature then increases the value o f K c
or Kp fo r a g iv e n r e a c ­
for an endotherm ic reaction. For an exotherm ic reaction, increasing tem perature
tio n is a c h a n g e in te m ­
favors the reverse reaction and decreases the ratio o f products to reactants and
p e ratu re.
therefore decreases the magnitude o f Kc. In general, Kc and temperature vary di­
rectly fo r endothermic reactions, but vary indirectly fo r exothermic reactions.
66 Chapter 2 Ш1111111ШШ111И11ШШ1111ШШ11ШШ111ШШШШШ1Ш1111111ШШШ1Ш1И11111111Ш1Ш
!

In the reaction, N 2 (g) + 3H 2 (g) 2N H 3 (g) + 22 kcal, an increase in

I n c re a s in g te m p e ra tu r e
I sh ifts e q u ilib riu m in a tem perature w ill cause a decrease in its K c, since it is an exotherm ic reaction.
d ire c tio n th a t p ro d u c e s To decrease the value o f K c in
I an e n d o th e rm ic ch an g e .
P r a c tic a lly , in c r e a s in g
te m p e ra tu re s h if ts the
i e q u ilib riu m to the o p p o ­ N H
site' sid e o f th e re a c tio n
; at w h ic h th e h e a t term the [NH3] m ust decrease and the [N2], [H2] m ust increase. This is m anaged by
1 is w ritten . the reverse reaction. The net result o f increasing tem perature on the equilibrium
is an increase in both the [N2] and the [H2], and a decrease in the [NH3] with re­
spect to the equilibrium concentrations at the original temperature.

(a) (b)

FIGURE 2.9 The variation of concentrations of N 2, H 2 and N H 3 when

(a) temperature is increased, (b) temperature is decreased.

EXAMPLE 2.25 Effect of Temperature Change on Equilibrium

Problem : Is the decomposition of COCl2 into CO (g) and Cl2 (g) favored at high or low temperatures ?
COCl2 (g) CO (g) + Cl2 (g) AH = + 29.9 kcal.
Solution : This is an endothermic reaction. Since raising temperature favors the endothermic reaction, (the
forward reaction above), we expect COCl2 to decompose more at high temperatures. Therefore we say that COCl2
is less stable at high temperatures.

EXERCISE 2.28 Indicate the temperature change necessary for increasing the equilibrium concentrations
of products for the following reactions.
a) H20 (g) ^ H2 (g) + l/2 0 2 (g) AH = + 6 8 . 3 kcal.
b) H2 (g) + I2 (g) 2H1 (g) AH = + 6.2 kcal.
c) N20 (g) + H 2 (g) ^ N 2 (g) + H20 (1) AH = - 87.9 kcal.
d) 2NH 3 (g) + 3C12 (g) N 2 (g) + 6HC1 (g) AH = - 110.4 kcal.
( a, b require an increase in temperature; c, d require a decrease in temperature)
 IIIIIU IIIIIIN IIIIIIIIIII Chemical Equilibrium 67

EXAMPLE 2.26 Effect of Temperature Change on Equilibrium

Problem : Will the value of Kc of the following reactions increase or decrease as the temperature of the sys­
tem is increased?
(a) 2S 0 3 (g) <=> 2S 0 2 (g) + 0 2 (g) AH = + 47.3 kcal.
(b) CO (g) + H20 (g) <=> C 0 2 (g) + H2 (g) AH = -9.8 kcal.
Solution :
(a) The reaction is endothermic. Therefore anincrease in temperaturewill cause the endothermic reaction to take
place further. This will increase the [S 02] and the [0 2] , but will decrease the[S03]. Consequently the numerical
value of Kc will increase.
(b) In the light of the foregoing argument we deduce that increasing the temperature favors the reverse reaction
(the endothermic reaction), and therefore an increase in temperature decreases the value of Kc.

EXERCISE 2.29 The value of the equilibrium constant, Kc, for the reaction
2 S 0 2 (g) + 0 2 (g)*= * 2 S 0 3 (g)
is 280 at 1000 K, and it is 19000 at 630 K. Is the reaction exothermic or endothermic ? e x o t h e r mi c

2.4.4 ADDITION OF A CATALYST

T he addition o f a catalyst increases the rates o f the forward and reverse reac­
tions equally. The equality o f the rates o f forward and reverse reactions is not
disturbed by the addition o f a catalyst. T herefore a catalyst does not upset the
com position o f the equilibrium system . H ow ever a catalyzed reaction attains
equilibrium m ore quickly than it otherwise would.

A SU M M A R Y OF LE CHA TELIER 'S PRINCIPLE

S tre ss a p p lie d D irection o f sh ift o f equilibrium

An increase in concentration o f any reactant forw ard
A decrease in concentration o f any reactant reverse
A n increase in concentration o f any product reverse
A decrease in concentration o f any product forw ard
A n increase in volume or decreasing pressure toward the reaction increasing molecule number
A decrease in volume (or increase in pressure) toward the reaction decreasing molecule number
An increase in temperature toward the endothermic reaction
A decrease in temperature toward the exothermic reaction
Addition o f a catalyst no change
68 Chapter 2

EXAM PLE 2 .2 7 Usage of Le Chatelier's Principle

Problem : Indicate the direction of reaction favored on the application of the stress given below for the equi­
librium reaction:
4NH 3 (g) + 5 0 2 (g) 4NO (g) + 6H20 (g) (exothermic);
(a) the addition of NH 3 (g) (b) the removal of 0 2 (g)
(c) the addition of NO (g) (d) the removal of H20 (g)
(e) An increase in volume (f) An increase in total pressure by decreasing volume
(g) An increase in temperature (h) the addition of a catalyst
(i) the addition of argon gas at constant volume (j) the addition of argon gas at constant total pressure
Solution :
(a) the addition of NH 3 forces the equilibrium to the right, (forward)
(b) the removal of 0 2 shifts the equilibrium to the left (reverse)
(c) the addition of NO shifts the equilibrium to the left (reverse)
(d) the removal of H2 0 favors the reaction to the right (forward)
(e) An increase in volume favors the reaction which increases molecule number. Therefore the forward reaction is
favored.
(f) An increase in total pressure has the same effect as a decrease in volume. A decrease in volume favors the re­
action which decreases molecule number. This is the reverse reaction.
(g) An increase in temperature causes the endothermic reaction to take place to return to a new equilibrium. Since
the forward reaction is exothermic and the reverse reaction is endothermic, then increasing temperature forces the
reaction to the left (reverse).
(h) The equilibrium is not affected by a catalyst.
(i) Addition of argon gas at constant volume does not change equilibrium concentration of any substance, there­
fore the equilibrium is not affected by the addition of argon gas.
(j) Since argon gas is added at constant total pressure, then the volume must increase. When the volume is in­
creased the forward reaction is favored.

EXERCISE 2.30 Consider the reaction : 2 H2S (g) + 3 0 2 (g) <==^ 2 H2 0 (g) + 2 S0 2 (ф ДН < 0

What will happen to the concentration of S 0 2 at equilibrium if

(a) more H2S is added.
(b) 0 2 is removed.
(c) more H20 is added.
(d) the volume of the system is increased.
(e) the pressure on the system is increased.
(f) the temperature of the system is increased.
(g) a catalyst is added.
(h) some argon is added to the system at constant volume.
(i) some argon gas is added at constant pressure. t he [ S O 2 ] will be i nc r e a s e d b y o nl y a a n d e.

2.5 Q U ANTITATIVE C A LC U LA TIO N S BASED

ON LE CHATELIER'S PRINCIPLE
T he qualitative predictions together with the equilibrium constant o f a reac­
tion can be used for calculating the new equilibrium concentrations o f substanc­
es. The following examples illustrate how these calculations are made.
 Hill Chemical Equilibrium 69

EXAMPLE 2 .28 Quantitative Aspects of Le Chatelier's Principle

Problem : Consider the reaction : 2HI (g) H2 (g) + I2 (g)
An equilibrium mixture of the H2,12 and HI present at a given temperature was found to contain 2 mol of HI, 1
mol of H2, and 1 mol of I2 in a 2 L vessel. Maintaining the same temperature 1 mol of HI is added to the vessel.
Calculate the concentration of each substance when the new equilibrium is established.
Solution : From the number of moles of substances we can calculate their concentrations and the valueof
equilibrium constant as follows. [H2] = 1 то1Д L = 0.5 M , [I2] = 1 mol/2 L = 0.5 M , [HI] = 2 mol/2 L =1M
т и , ( 0 . 5 ) ( 0 . 5 ) =025
0 2 2
[HI] (1 )
Since the temperature is kept constant the value of Kc does not change. According to Le Chatelier's principle, the
addition of HI will shift the equilibrium to the right. Suppose that 2x M of HI is decomposed to establish the
equilibrium. In that case x M of H2 and x M of I2 will be produced.

2H I (g) H 2 (g) 2
I (g)
1st Equilibrium 1 M 0.5 M 0.5 M
Stress + 1/2 M - -

Start o f 2 nd Eq 1.5 M 0.5 M 0.5 M

Change -2x M +* M +* M
2 ”^ Equilibrium ( 1 .5 -2 * ) (0 .5 + * ) (0 .5 + * )

The concentrations of the substances in the second equilibrium must satisfy the value of Kc. So substituting
them into the Kc expression we get:

K c= ^ ^ = (°-5+x) (0-5±]0 = 0 . 2 5 => Q.5 = 9 A ± E. => x = 0.125 M

[HI] (1.5-2*) 1 .5 -2 *
The equilibrium concentrations are :
[H2] = [I2] = 0.5 + x = 0.5 + 0.125 = 0.625 M ; [HI] = 1.5 - 2* = 1.5 - 0.25 = 1.25 M.

EXERCISE 2.31 Upon analysis an equilibrium mixture of the substances present at a given temperature
was found to contain 0.2 mol of H2, 0.2 mol of I2 and 1.6 mol 6 f HI in a liter. Maintaining the same tempera­
ture, 3 mol of HI is added to the container. Calculate the number of moles of each substance at new equilibrium.
H 2 (g) j*- h (g)<=^ 2 HI (g) n u 2=ni2=0.s mol n jjj =4 m o l

EXERCISE 2 .3 2 0.25 mol of N20 4 and 0.5 mol of N 0 2 are at equilibrium in one-liter container at a
certain temperature. Calculate the new equilibrium concentrations when 0.5 mol of N 0 2 is added to the container
at the same temperature. 2N 02 (g) <=> N 20 4 (g) . [NO2j=0.6S M,[N20 4M .4 2 5 M

EXAM PLE 2 .2 9 Quantitative Aspects of Le Chatelier's Principle

Problem : At a certain temperature the analysis of an equilibrium mixture presented by the equation
S 0 2 (g) + N 0 2 (g) * = * S 0 3 (g) + NO (g)
shows [SO2] = 0.6M [N 02] = 0.2 M [S 03] = 0.3 M [N O ]= 0.4M
What is the new equilibrium concentration of each species when 0.1 mol of N 0 2 is removed from a liter of equi­
librium mixture?
70 Chapter 2 1 Ш Ш Ш Ш Ш Ш 1 1 1 И 1 Ш 1 1 Ш Ш 1 1 1 1 1 1 1 1 Ш ............. 11I I 1I I I I I I I I I I I H I I I 1............. ............. шкшиишшшшшшш........

Solution : The equilibrium constant for the reaction is:

^ _ [ s o 3][n o ] . 0.3 X 0.4
[so 2] [no 2] 0 .6 x 0 .2

The molarity of N 0 2 removed is [NO2 ] = 0.1 mol/L = 0.1 M

According to Le Chatelier's Principle the removal of N 0 2 will shift the equilibrium to the left. Let x be the mo­
larity of N 0 2 produced by the reverse reaction to restore equilibrium. The summary of equilibrium changes is
shown below.
S0 2 (g) + N0 2(g) S0 3 (g) + N O (g)
First equilibrium 0.6 M 0 .2 M 0.3 M 0 .4 M
Stress applied - -0.1 M - -

Start o f 2nd Equilib. 0.6 M 0.1 M 0.3 M 0 .4 M

Change +x M +x M -x M -x M
Second Equilib. (0 .6 + x ) M (0 .1 + x ) M (0 .3 -x ) M (0 .4 -x ) M

Substituting these into Kc expression and rearranging the equation give

1 = ( ° - 4 - A .. _> 0.06 + O.lx + x 2 =0.12 - O J x + x 2 =1 I A x = 0.06 => x = 0.04

(0 . 6 + x) (0 . 1 + x)

The new equilibrium concentrations are :

[S 0 2] = 0.6 + x = 0.64 M, [N 02] = 0.1 + x = 0.14 M , [S 03] = 0.3 - x = 0.26 M , [NO] = 0.4 - x = 0.36M

EXERCISE 2.33 Consider the equilibrium represented by the equation: X(g) + Y (g) < = ^ Z (g) + T (g)
One liter vessel at a given temperature contains the following equilibrium concentrations : [X] = 0.4 M, [Y] = 1
M, [Z] = 0.4 M and [T] = 0.2 M. How many moles of Y must be removed from the vessel in order to decrease
the new equilibrium concentration of T to 0.1 M ? 0.8 mol

EXAM PLE 2.30 A p p lication o f L e C h a telier’s P rin cip le

Problem : 0.4 mol of C 0 2 and 0.6 mol of*H2 gases are introduced into a 1 liter container at 227° C.
When the reaction C 0 2 (g) + H 2 (g) < = ^ CO (g) + H20 (g) reached equilibrium at this temperature it is found
that 50% of C 0 2 remained unreacted.
(a) How many moles of C 0 2 must be added to the container at the same temperature to make the number of mole
of CO 0.4 at the new equilibrium?
(b) Draw a concentration - time graph to show the equilibrium changes.
Solution : (a) Using the information given we find the Kc for the reaction. Since 50% of C 0 2 is unreaeted,
50% of it must be reacted.

Mole of C 0 2 (reacted) = 0-^0 x 50 _ q 2 moj

2 100
Now let us find the number of moles and concentrations of substances at equilibrium.
c o 2(g) + H2 (g) < = » C O (g) + H2 0 (g )
Initial moles 0.4 mol 0 . 6 mol 0 mol 0 mol

Change in moles - 0 . 2 mol - 0 . 2 mol + 0 . 2 mol + 0 . 2 mol

Moles at eq. 0 . 2 mol 0.4 mol 0 . 2 mol 0 . 2 mol

Cone, at eq (n/v) 0.2 mol/L 0.4 mol/L 0.2 mol/L 0.2 mol/L
 iiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiitiiitiiiiii Chemical Equilibrium 71

Kc for the reaction : K c = = 0 2 x 0 2 = 0.5

[C 0 2] [H2] 0.2 x 0.4
When the reaction was at equilibrium, we applied a stress by increasing the mole number of C 0 2. Therefore the
equilibrium shifts to the right to establish a new equilibrium in which the mole number of CO is 0.4.

C 02 (g) + H2 (g) <=* C O (g ) + H 20 (g)

Moles at 1st equilib. 0.2 m o l 0 .4 m ol 0.2 m o l 0.2 m o l
Stress applied +x m o l
Start o f 2nd Equilib. 02
( . + x ) m ol 0.4 m o l 0.2 m o l 0.2 m o l
Changes - 0.2 m o l - 0.2 m o l + 0.2 m o l + 0.2 m ol
Moles at 2nd Equilib. x m ol 0.2 m ol 0 .4 m o l 0 .4 m o l
Cone, at 2nd Equilib. x M 0.2 M 0 .4 M 0 .4 M

We substitute the concentration terms into equilibrium constant expression to find the value of x.

_ M M ^ (0.4) m = 0.5 _ , .
[C 0 2] [H2] (x) (0.2)

(b) We may draw the concentration versus time graph as follows.

Initial concentrations :
[COJ = 0.4 M [H2] = 0.6 M
First equilibrium concentrations:
[COJ = 0.2 M, [H2] = 0.4 M
[CO] = [H2 0 ] = 0.2 M
Final equilibrium concentrations:
[COJ = 1.6 M, [H J = 0.2 M
[CO] = [H2 0 ] = 0.4 M

t (stress is applied) time (s)

EXERCISE 2.34 At a certain temperature, the composition of an equilibrium mixture of the reaction,
C 0 2 + H 2 (g) CO (g) + H20 (g), is as follows:
H 2 = 0.4 mol , C 0 2 = 0.4 mol , CO = 0.8 mol , H20 = 0.8 mol.
a) Calculate the new equilibrium concentrations when 0.9 mol of C 0 2 and 0.9 mol of H 2 are added to the contain­
er of one liter, b) Draw a concentration versus time graph, representing the equilibrium changes.
[C O 2]=[H2]=0.7 M [CO]=[H26]^1 .4 M
72 Chapter 2 1
:M !;;tlllllllllllilll!lillllllllllllllllllllllllllillllllll!lllllin iilllllllllllllilllllllllillllillllllllllllllllll! ! llllllilllllllilllllllllllllllllllllll! llill! lll lililillIII

EXAM PLE 2.31 Quantitative Aspects of Le Chatelier's Principle

Problem : At a certain temperature the number of moles of substances in a 2 - liter container are given below
for the reaction, 2NH 3 (g) N 2 (g) + 3H 2 (g). NH 3 = 3 mol, N 2 = 0.6 mol, H 2 = 1.8 mol. How many
moles of NH 3 must be added to the container to increase the mole number of N 2 to 0.8 in the new equilibrium at
the same temperature?
Solution : Let x be the number of moles of NH 3 added.
2N H 3( g ) ^ > N 2 (g) + 3H 2 (g) D u rin g th e r e a c tio n re a c h e s e q u ili­
Moles at 1st equilib. 3 m ol 0.6 m ol 1.8 m o l b riu m , 0.2
m o l o f N m u st b e p r o ­2
Stress applied +x m ol d u c e d , so th a t th e m o le n u m b e r o f

Start o f 2nd Equilib. (3 + x ) m ol 0.6 m ol 1.8 m o l N 2 in c re a s e s 0.8 fro m 0 .6 . I f th e

Changes -0 .4 m o l + 0.2 m o l + 0.6 m o l

n u m b e r o f m o le s o f N 2 in cre ases by
At Second Equilib. 26
( . +x) m ol 0.8 m ol 2.4 m o l
0 .2 , th at o f H 2 in cre ases by 0.6 and
Cone, at 2nd Equilib. [2.6+ X /2] M [0.8/2] M [2.4/2] M
th a t o f N H 3 d ecre ases by 0.4 m ol.

The equilibrium concentrations must satisfy the Kc, which may be calculated by using the initial concentrations.
Then it is used to find the value of x.
Initial concentrations

[N H 3] = - = 1.5M Kc= № 1 = (0,3) (° ' 9) = 0.0972 s 0.1

2 [N H 3f (1 .5 )2

[N 2] = = 0.3 M

[H 2] = H = 09M 0 1 = (0 .8 /2 ) ( 2 .4 /2 ) 3 _ ( 0 .4 )(1 .2 )3 x 4 _ 2.7648

2 v2 2 2
2 .6 + x\ ( 2 . 6 + x) ( 2 . 6 + x)

( 2.6 + * ) 2 = 27.6
by taking the square roots of both sides, we obtain 2.6 + x = 5.25 => x = 2.65 mol

EXERCISE 2.35 Consider the reaction : 2 S 0 3 (g) 2S 0 2 (g) + 0 2. A 0.8 mol of SQ 3 is put into
a 1 L vessel at a certain temperature. At equilibrium the vessel contains 0.4 mol of S 0 3 as well as some S 0 2
and 0 2. How many moles of S 0 3 must be removed from the container so that the number of moles of S 0 2 de­
creases to 0.2 in the final equilibrium at the same temperature ? 0.46

EXAM PLE 2.32 A p p lic a tio n o f E q u ilib r iu m C h a n g e

Problem : The graph shows the concentration changes of all species for the reaction taking place in a 1 liter
container
2 S 0 2 (g) + 0 2 (g) * = * 2 S 0 3 (g) + Q
under a given set of conditions.
(a) How much time was required for the reaction to reach equilibrium?
(b) Find the value of Kc.
iiiiiiiiiiiiiiiiiiiiiiiiiiiiiiMiiiiMiiiiiiiiiiiiiiiiiiimiiuiiiiiiiMHKmiiiMiHiHiiiiiHiHiiiiiiiiiiiiiiiiiiiiiiiimmiiiiiiHiiiiiiiiimiiiiiiiiii Chem ical E qu ilibriu m 73

(c) Explain what kind of stresses should have been

applied on the system at 25th s.
(d) If the change is made by removing some S 0 2 (g)
conccniralion (mol/L) at 25th s , how many moles of S 0 2 should have
been removed from the system at 25th s ?
(e) Calculate the concentration of each species in the
new equilibrium.
(f) Complete the graph.

Solution :
(a) The equilibrium is established approximately at
20 s. Hence 20 s was needed to reach equilibrium.
(b) The equilibrium concentrations from the graph
are: [S02] = 2.0 M [0 2] = 0.5 M [S 03] = 3 M
The value of Kc can be found by means of these
equilibrium concentrations.
15 20 25 lime (s)
K„ = [SOaf (3) = 4.5
For example 2.32
[S 0 2] Щ (2) (0.5)

(c) Since the concentration of S 0 3 (g) begins to decrease at 25th s, the reaction must shift to the left. This may
be because of (1) rempval of S 0 2 (2) removal of 0 2 (3) increasing volume or decreasing pressure (4) increasing
temperature.
(d) We can make a table to show the change in the concentration of each species as follows:
2S0 2 (g) + o 2 (g) < = S’ 2S0 3 (g)
Initial eq.conc. 2 M 0.5 M 3 M
Stress applied -x M
A t the start o f 2nd Eq. (2 -х ) M 0.5 M 3 M
Change in conc. + 0 .5 M + 0.25 M -0.5 M (from the graph)
Cone, at 2nd Equilib. (2 .5 -x ) M 0.75 M 2.5 M

To find the value of x, we substitute these concentration terms into Kc

(2.5)
-» 4.5 = -> (2.5 - x ) 2 1.85
4.5 x 0.75
[ S o / [ 0 2] (2.5 - x) (0.75)

Taking the square root of both side gives.

2.5 - x = 1.36 -» x = 1.14 M. This is the stress applied.
The volume of the system is 1 liter,
therefore, n s c ,2 = [S 02] x VSq 2 = 1 .1 4 m o l/L x lL = 1.14 mol
e) Now the equilibrium concentration of each species is as follows.
[S 03] = 2.5 M
[S 0 2] = 2.5 - x = 2.5 - 1.14 = 1.36 M
[0 2] = 0.75 M
74 Chapter 2 М Ш Ш Ш П Ш М Ш Ш Ш Ш Ш Ш Ш Ш Ш П Н Ш И Ш Н Ш Ш Ш И М Н И П М М Ш М П П Ж И Ш М П М Ш М Ш М И П Ш И Н П И Ш И П М Ш М М Ш Н П Ш М М Н Ш Ш Н Н Ш П П Ш Ш Ш М Ш И Ш

(f) To complete the graph, we use the new eauilibrium concentrations.

EXERCISE 2.36 The equilibrium mixture in 1 L container for the reaction

2NO (g) + Brj (g) < = * 2NOBr (g)
is as follows; nNO = 1 mol/L, nBr = 2.5 mol/L, nNOBr = 1 mol/L. How many moles of NO must be added to
the container at constant volume and temperature to make the mole number of NOBr equal to 2 ? 2.24

EXERCISE 2.37 A 0.6 mol sample of PCI5 is put into a 1 L vessel and heated. At equilibrium the ves­
sel contains 0.4 mol of PCI5 . a) What arq the equilibrium concentrations of PCI5 , PCI3 and CI2 ? b) At the
same temperature, what must be the volume of the vessel so that the equilibrium mole number of PCI3 is to be
0.4 ? - a ) [ P C l s ]=0.4 M, [PCl3] = [ C l 2]=0.2 M b)8 L

2.6 FACTORS THAT CAUSE EQUILIBRIUM

A fter learning w hat equilibrium is, let us try to answ er the question why
equilibrium exists.
C hanges in nature can be classified as spontaneous and nonspontane-
ous. A spontaneous change is the one that occurs by itself. F or exam ple, a
A ny c h an g e th a t lo w ers
tightly w ound clock runs dow n spontaneously, but the clock cannot rew ind it­
the e n e rg y o f a sy ste m
tends to o c cu r sp o n ta n e ­
self. The w inding o f a clock is a nonspontaneous change. A ball rolls dow n
o u s ly . spontaneously, but its rolling up process is a nonspontaneous change. The
A ny e v e n t th at in cre ases rusting o f iron is a spontaneous process. From the exam ples the follow ing con­
th e r a n d o m n e s s o f a clusions m ay be drawn:
s y s te m te n d s to be.
1. The reverse o f a spontaneous process is a nonspontaneous process.
s p o n ta n e o u s .
2. B oth spontaneous and nonspontaneous processes are possible, but only
spontaneous changes take place naturally. These spontaneous changes occur
W e a re h a p p y b e c a u s e because o f the follow ing tendencies.
s y s te m s a re d riv e n t o ­ a - T endency to reach low er energetic state (minimum enthalpy),
w a rd m in im u m e n e rg y . b - T endency to reach m ore disordered state (maximum entropy).
W h a t w o u ld y o u th in k if
y o u d ro p p e d a b o o k and
it ro s e to th e c eilin g ?
Tendency Toward Minimum Energy : From daily life experience we
 ..... Chemical Equilibrium 75

m ay say that a change proceeds spontaneously if the change decreases the ener­
M o s t, b u t n o t a ll, gy o f the system. F or example a hot object cools dow n to the tem perature o f the
e x o th e rm ic re a c tio n s surroundings, but it never gets hotter than its environm ent spontaneously.
o c c u r sp o n ta n e o u sly . C hem ical reactions also proceed spontaneously to reach a less energetic state.
Therefore we conclude that spontaneous changes tend to be exotherm ic. In the
preceeding statem ent to word "tend to" should be em phasized. T here are m any
nonspontaneous exotherm ic reactions as w ell as m any spontaneous endother­
m ic reactions. The im portant point is that an energy decrease in the system is
one factor that favors spontaneity.
R em em ber that the energy order o f the sam e quantity o f the sam e m atter is

solid < liquid < gas

Tendency Toward Maximum Randomness : T here are exam ples o f

endotherm ic spontaneous changes such as evaporation o f water, and dissolving
salt in water. These changes m ust have a com m on driving force causing a high­
er energetic state. This driving force is an increase in the random ness, or disor­
der, o f the system . As w ater evaporates, the m ovem ent o f w ater m olecules b e ­
com es freer. Instead o f being confined to a liquid they m ove random ly and
violently in the atm osphere. The situation o f dissolving salt in w ater is similar.
T he ions form ed from the dissolution o f salt in w ater are able to leave th eir
highly ordered crystal arrangem ent and m ove random ly throughout the solu­
tion. Therefore we can say that any event that is accom panied by an increase in
random ness (the scientific term , entropy, is used to describe the random ness
o f a system ) tends to be spontaneous. W e can com pare the random ness o f sys­
tem s using the following clues.
I. The degrees o f disorder in three states o f m atter is :
solids < liquids < gases.
II. A system containing larger number of particles is usually m ore ran­
dom than a system containing fewer number of particles.
III. A system at a higher temperature is m ore random than the sam e sys­
tem at a lower temperature.
IV . A m ixture (or an im pure substance) is m are random than a p u re sub­
stance. (Random ness decreases when a gas is dissolved in water.)
T he energy order for the sam e am ount o f substance is solid, liquid, gas. The
degree o f disorder for the sam e substance is solid, liquid and gas. As the ener­
gy (tem perature) o f a substance increases, its random ness increases too. In oth­
er words these tw o tendencies oppose each other. T he solid state o f a substance
has less energy but it is m ore ordered.
Chem ical reactions reach equilibrium because o f these tw o opposing factors.
If the forw ard reaction takes place because o f the tendency tow ard m inim um
energy, the reverse reaction will take place because o f the tendency tow ard
m axim um randomness or vice versa. At a certain temperature, these tw o oppos­
ing tendencies will becom e equal to each other, and both forw ard and reverse
reactions will take place at the same rate, o r the reaction will reach equilibrium.
76 Chapter 2 Н Ш Ш Ш И Ш Н Ш Н Н Н И П П Н П И Ш Н Н П Н Н Н Н П Н Н П П И И Н П П П Illllll Illlllllllllll I IN I II I l l l l l l l .......................... I l l ......... H i l l .......... .........H I

The equilibrium state is a com prom ise between m inim um energy and m axim um
randomness. Some illustrative examples are given below.
Consider the m elting o f ice at 0°C. It is represented by the equation:
H 20 (s) + 1.44 kcal ^ H20 (1)
Since H 20 (1) is m ore random (disordered) than H 20 (s), then
the forward reaction takes place to increase random ness. On the
other hand the energy o f one mole H 20 (s) is less than that o f one
m ole H 20 (1). Therefore, the reverse reaction takes place to d e ­
crease the energy. These tw o tendencies are in balance at 0° С
and 1 atm. Hence this reaction is at equilibrium at 0°C. W hen the
tem perature is increased, the randomness will increase more, and
the forward reaction overpowers the reverse one and all o f the ice
melts and no m ore equilibrium exist. A t low er tem peratures than
0°C, the energy factor overpowers the random ness factor, and all
the liquid becomes ice, (no equilibrium state again).
In a few cases both factors favors the reaction in one d irec­
tion. F or example: C onsider the dissolving process o f alcohol in
water. C 2 H 5OH (1) -> C 2 H 5 OH (aq) ЛН < 0
FIGURE 2.10 Randomness of oxy­ Both the tendency toward m inim um energy and the tendency
gen as a function of temperature. At tow ard m axim um random ness favor C 2 H 5 OH (aq). T herefore
the m.p and b.p there are abrupt in­ this changes proceeds in only forward direction, and alcohol dis­
creases in the randomness. solves in w ater in all proportions.

EXERCISE 2.38 Decide which of the following will have higher randomness ?
a) 18 grams of ice at 0°C or 18 grams of water at 0°C.
b) Solid NaCl or a solution of NaCl in water.
c) A pack of game cards arranged in suits or a pack of cards randomly shuffled.

EXAM PLE 2 .3 3 Factors Fixing Equilibrium

Problem : For each of these reactions, indicate :
( 1 ) whether the tendency toward minimum energy favors the forward or the reverse reaction.
(2 ) whether the tendency toward maximum randomness favors the forward or the reverse reaction.
(a) H20 (1) + 68.3 kcal * = * H 2 (g) + l/2 0 2 (g)
(b) N 2 (g) + 3H2 (g) < = ^ 2NH3 (g) AH = - 22 kcal.
(c) C aC 0 3 (s) CaO (s) + C 0 2 (g) AH = + 43 kcal.
Solution ;
(a) Since the reaction is endothermic, the energy or the randomness of products is greater than that of reactants.
Therefore tendency toward maximum randomness favors the forward reaction. The tendency toward minimum en­
ergy favors the reverse reaction.
m a x .ra n d o m n e s s

H20 (1) + 68.3 kcal < => H2 (g) + l/2 0 2 (g)

m in . e n e r g y

(b) Since the reaction is exothermic, the energy or the randomness of reactants is greater than that of products.
Then the tendency toward minimum energy favors the forward reaction, and the tendency toward maximum ran­
domness favors the reverse reaction.
iiwuuuiiiittftftiiHttiiMHtHNiiMiiiiiiiiHKiiHiiifiiiiiiiiiuiMiiiiiiitiiiiKiiiiiiiiiiitiiitiiiiHiiiiiiiHifiifiiienfiMimiiuiHtiiuitiiiiiiii C h e m ic a l E q u i l i b r i u m 77

m in . e n e r g y

N 2 (g) + 3H 2 (g) 2NH 3 (g)

m a x .ra n d o m n e s s

(c) The foregoing argument for part (a) is applicable to this reaction too. The rule of thumb is the tendency to­
ward minimum energy always favors exothermic reaction.
m a x .ra n d o m n e s s

C aC 0 3 (s)< — Ca O (s) + C 0 2 (g)

m in .e n e r g y

EXERCISE 2.39 Which tendency is in favor of products in the following reactions?

(a) 2C 2 H2 (g) + 5 0 2 <=* 4 C 0 2 (g) + 2HzO (g) AH = - 586 kcal.
(b) N 2 (g) + 0 2 (g) 2NO (g) AH = + 41.4 kcal.
( a ) m in i m u m energy, (b)m axim u m random ness

EXERCISE 2.40 Decide which of the following reactions to be exothermic.

(a) HC1 (g) + NH 3 (g)<=^ NH 4 C1 (s) (b) NaCl (s) +=^N a+ (aq) + Cl“ (aq)
(c) H2 (g)<—? 2H (g) (d) H20 (!)<=? H2 (g) + I/ 2 O 2 (g) °nh (a)

SOME NEW TERMS

Chemical Equilibrium : a chem ical state reactants and all products are gases or liquids or
where the forward and reverse reactions proceed solids.
at equal rate, and no observable changes can be Heterogeneous equilibria : equilibria in ­
detected. volving species in m ore than one phase.
Equilibrium constant : a quantity that Le Chatelier's Principle : If a reaction at
shows the relationship am ong the concentrations equilibrium is disturbed by an external stress, the
(or partial pressures) o f products and those of re­ equilibrium will be upset, the reaction w hich re­
actants in an equilibrium state. Its value varies lieves the stress will take place to reach a new
with temperature. equilibrium state.
K c : the equilibrium constant obtained by us­ Reaction quotient (Q) : T he ex p ressio n
ing equilibrium concentrations o f reactants and the sam e as equilibrium constant, but any set o f
products. conditions (not necessarily equilibrium condi­
K p : the equilibrium constant obtained by us­ tions) can be used to find the value o f reaction
ing the partial pressures o f gaseous substances in quotient. Its m agnitude relative to Kc o r K p d e­
a reaction at equilibrium. term ines the direction in which reaction m ust oc­
Homogeneous equilibria: eq u ilib ria in ­ cur to reach equilibrium.
volving substances ju st in a single phase, i.e, all
78 Chapter 2 И 1Ш 1111Ш 1111Ш 1111111Ш 11Ш 11111Ш 1Ш 11Ш 11111111Ш 1111Ш 1Ш 1111111Ш Ш 1Ш Ш !Ш Ш 11Ш 111П 1Ш 1Ш Н Н 11Ш 1Ш 1111111Ш 11Ш И Ш 1И 1Ш 11Ш 1Ш Ш 1Ш И Ш Ш 111111Ш 111И 1

REVIEW QUESTIO NS AND PROBLEMS

Recognizing Equilibrium and Equilibrium Constant

2 • 1 Define dynamic equilibrium and state the con­ ( 2.8 Write the Kc expression for each of the follow­
ditions of equilibrium. What is the difference between ing reactions.
static equilibrium and dynamic equilibrium ? (a) H 2 (g) +=> 2H(g)
(b) N 2 (g) + 0 2 (g) 2NO (g)
2 .2 What is the difference between homogeneous (c) 2N2 0 5 (g) ^ 4N 0 2 (g) + 0 2 (g)
equilibrium and heterogeneous one ? Indicate which (d) H2S (g) ^ H 2 (g) + S (g)
ones of the following equilibrium reactions are ho­ (e) N 2 H 4 (g) + 6H 2 0 2 (g)«=*
mogeneous and which are heterogeneous ? 2N 0 2 (g) + 8H20 (g)
(a )H 2 (g) + I2 (g )< = ^ 2 H I (g) \
(b) 2 C 0 2 (g) *= * 2CO (g) + 0 2 (g) 2-9 Write the Kc expression for each of the follow­
(c) Ag+ (aq) + 2NH 3 (aq) ^ > A g (N H 3)J (aq) ing reactions involving pure solids and pure liquids.
(d) Z nS 0 3 (s) ZnO (s) + S 0 2 (g) (a) M gC0 3 (s) ^ MgO (s) + C 0 2 (g)
(e) 6 C 0 2 (g) + 6H20 (1)^=->C6 H 1 2 0 6 (s) + 6 0 2 (g) (b) H2 (g) + S (1) ^ H2S (g)
(c)H 2 (g) + S (s) H2S (1)
2 3 w hat is equilibrium constant? How is it relat (d) 5Fe2+ (aq) + Mn04' (aq) + 8 H+ (aq) <=>
edto 5Fe3 + (aq) + Mn+ 2 (aq) + 4H20 (1)
(a) specific rate constants of forward and reverse reac­
tions?
concentration (mol/L)
(b) temperature?

2 •4 What is the meaning of a value of Kc that is

(a) very small (b) very large (c) about one

2 •5 Why do the units of Kc differ from reaction to

reaction? Under what conditions does Kc have no
units?

2 .6 why are not the concentrations of pure solids

or pure liquids included in the equilibrium constant The graph shows how the concentrations of the reac­
expression for a heterogeneous equilibrium? tants and products of a typical reaction vary with
time.
1 Which of the following three reactions would (a) What are the initial concentrations of the sub­
tend to proceed furthest to completion when they stances ?
reach equilibrium ? (b) What is the change in concentration of each sub­
( 1 ) 2 NO (g) + 0 2 (g) 2N 0 2 (g) Kc = 4 x 10 13 stance during the establishment of the equilibrium ?
(2) N 2 (g) + 3H 2 (g) . 2NH 3 (g) Kc = 6 x КГ (c) What is the reaction of equilibrium with the
(3) 2H2 (g) + 0 2 (g) . 2H20 (g) Kc = 9 x 10:,80 smallest-whole number coefficients ?
(d) What is the equilibrium concentration of each
шшшшпшш Chemical Equilibrium 79

substance ? 2 .1 6 A 0.60 mol of N 0 2 (g) is placed into a sealed

(e) What is the value of the equilibrium constant ? 4.00 liter container, and heated to a certain tempera­
(c)3A +4B <=^2D+6C , Kc = 4 3 .2 ture. At equilibrium it is found that 0.2 mol of N 0 2
2.11 The rate of the reaction (g) remained unreacted. Calculate K c for the reaction
X 2 (g) + Y 2 (g) -> 2XY (g) at 25°C is given by 2N 0 2 (g) < =* 2NO (g) + 0 2 (g)
Rate = 4 x 10' 3 [X2] [Y2], and the rate of the reac­ К c =0 .2
tion 2XY (g) —> X 2 (g) + Y2 (g) at 25°C is given by
Rate = 2 x 10"4 [XY]2. What is the equilibrium con­ 2 .1 7 A 0.80 g sample of S 0 3 placed in a 1.00 liter
stant for the formation of XY from the gaseous X2 container decomposes 80% to establish equilibrium
and Y 2 ? 20 represented by the equation
2 S 0 3 (g) ^ 2 S 0 2 (g) + 0 2 (g) at 1100 K. Cal­
2 .1 2 For the reaction : culate Kc for this reaction at 1100 K.
N 2 (g) + 3H2 (g) < = ^ 2NH3 (g) K c = 0.064
the equilibrium concentrations in mol/L found at
257°C are: [H2] = 0.5 [N2] = 0.2 [NH3] = 2.0 2 .1 8 A2 (g) + 3B (g) ^ 2C (g)
(a) Calculate Kc for this equilibrium reaction. The reaction was started with 2 mol of A 2 and 4 mol
(b) What would be the value of Kc for the reverse re­ of В in a 1-liter container. When the reaction reached
action? K c=160, Kc '= 6 .2 5 x l0 '3 equilibrium, 1 mol of В remained behind. Calculate
the Kc. 4
2.13 0.5 mol of C 0 2, and 0.2 mol of H 2 are put
into a 5 L vessel at a certain temperature. When the 2 .1 9 The following reaction was allowed to come
reaction, C 0 2 (g) + H2 (g) <=+ CO (g) + H20 (g), equilibrium.
is reached equilibrium, the vessel contains 0 . 1 mol 2H2S (g) + 3 0 2 (g) <=> 2H20 (g) + 2 S 0 2 (g).
of CO. Calculate the equilibrium constant, Kc, for The initial amounts of H 2 0 , and S 0 2 present in a
the reaction at the given temperature. 0.25 two - liter container were 3 mol and 2 mol respec­
tively. The amount of S 0 2 at equilibrium was found
2.14 At a certain temperature a mixture of A (g) to be 60% of its initial amount. What is the value of
and В (g) was prepared by placing 1 mol of A and K c for this reaction? K c = 12.6
2.5 mol of В into a 2 L flask. After a period of time
the equilibrium 2 . 2 0 A 1 mol sample of H 2 0(g), and an excess
A (g) + 3B (g) 2C (g) + D (g) amount of Fe (s) are placed in a one-liter container,
was established. It was determined that the concentra­ the amount of H 2 (g) at equilibrium is found to be
tion of С was 0.5 mol/L at equilibrium. Calculate 0.75 mol. Calculate the value of Kc for the equilibri­
the value of Kc for this reaction at this temperature. um.
2 3Fe (s) + 4H20 (g) « = * Fe 3 0 4 (s) + 4H 2 (g)
2 .1 5 The equilibrium, K c = 81
PCI5 (g) PC13 (g) + Cl2 (g),
is established by heating 20.85 g of PCI5 to a certain 2.21 It was found that when A and В were mixed
temperature in a one-liter container. If the equilibri­ and allowed to react according to the equation.
um mole number of Cl2 is measured to be 5 x 10' 2, A (g) + 2B (g) <=*• С (g)
calculate the value of equilibrium constant (Kc), and The concentrations of the substances at equilibrium
the percent dissociation of PC15? PCI5 = 208.5 were as follows. [A] = 0.1 M, [B] = 1 M, and
К c=5 x 1 O' 2,50 %
80 Chapter 2 Illllll IIIIIIIIIIK IIIIIIII I Illllllllll Illlllllllllllll Illlllllllllll Illllllllll

[С] = 0.1 M. What is the value of the equilibrium At equilibrium the total number of moles of gases
constant, Kc for the reaction ? What were the initial was found to be 3.75. Calculate the value of Kc for
concentrations of A and В ? this reaction. 0.04
K c=l, [A]=0.2M, [B]=1.2 M
2.24 Suppose that some P b(N 0 3 ) 2 was put into a
2.22 Starting with a mixture of H 2 and I2, an equi­ 4.0 L tank and heated to 227°C. At this temperature
librium was established for the reaction РЬ(Ж>з) 2 partially decomposed according to the reac­
H 2 (g) + I2 (g) 2HI (g) . At equilibrium the tion
following concentrations were found in the reaction 2Pb(N 0 3 ) 2 (s)« = * 2PbO (s) + 4 N 0 2 (g) + 0 2 (g)
vessel. [H2] = [I2] = 0.02 M and [HI] = 0.16 M. De­ At equilibrium the total pressure of the gases in the
termine the value of Kr and the initial concentrations tank was measured to be 1 0 atm.
of H 2 and I2. K c =64, 0.1 M e a ch a) What are the number of moles of NO and 0 2 at
equilibrium ?
2.23 A 3 mol sample of N2Os was placed and heat­ b) What is the equilibrium constant, Kc, for the reac­
ed in a 1 L vessel. Some of N 2 0 3 decomposed ac­ tion at 227°C. (R = 0.08 L.atm/mol.K)
cording to the reaction, a) 0 .8m o lN O 2 and 0 .2 m o l O 2 b ) 8 x l 0~3
2N 2 0 5 (g) <=> 4 N 0 2 (g) + 0 2 (g)

Equilibrium C oncentrations
2.25 At a certain temperature Kc for the equilibrium brium concentration of each species ? Compare your
2A (g) + В (g) 3C (g) results for part (a) and (b)
is 4. If the equilibrium concentrations of A and С are a) [ H 2] = [ C 0 2] = 0 . 0 4 M
0.2 M each, what is the equilibrium concentration of [H20 ] = [ C O ] = 0 . 08 M
В? 0. 05 M b) The same

2 . 2 6 For the reaction 2.28 At a certain temperature the Kc for the reac­
H 2 (g) + Br2 (g b 2HBr (g) KC=1 tion PCls(g) PCl 3 (g) + Cl2 (g) is 4.0 x 10-2.
at a certain temperature, (a) Determine the composi­ How many grams of PC15 must be put into a 2 -
tion of the equilibrium reaction mixture if the initial liter container to obtain 7. 1 g of Cl2 at equilibri­
mixture consisted of 3 mol of H 2 and 3 mol of Br2 in um ? PC15 = 208.5 g/mol Cl2 = 71 46.9 g
1 L container, (b) What would be your answer if the
reaction were started with 6 mol of HBr in 1 L ves­ 2 . 2 9 The equilibrium constant, Kc for the reaction
sel at the same temperature ? FeO (s) + CO (g) Fe (s) + C 0 2 (g) at a cer­
( a ) H 2 = Hr 2 = H B r = 2 m o l tain temperature is 1. Find the equilibrium concen­
( b ) H 2 = Br2 = H Br = 2 mol trations of the CO and C 0 2 if the reaction is started
2.27 At a certain temperature the Kc for with a mixture of 14 g of CO and 54 g of FeO dust
H 2 (g) + C 0 2 (g) <=> H20 (g) + CO (g), in a 5 L vessel. CO = 28 FeO = 72
is 4.00. (a) Calculate the concentration of each sub­ [ С О ] = 0 . 0 5 M , [ C O 2] = 0 . 0 5 M
stance in the equilibrium obtained by mixing 0 . 6
mol of each of H 2 and C 0 2 in a 5-liter box? 2.30 At a certain temperature the Kc for the reac­
(b) If the equilibrium were obtained by mixing 0.6 tion, N 2 0 4 (g) 2 N 0 2 (g) is 0.04. If 1 mol of
mol H20 and 0.6 mol CO what would be the equili- N 2 0 4 is injected into a one liter closed container,
 .... и................ Chemical Equilibrium 81

what will be the equilibrium concentrations of N 2 0 4 2.33 At a certain temperature Kc for the reaction
and N 0 2? What is the degree of dissociation of N 20 4 X 2 (g) + 2Y 2 (g) 2XY 2 (g)
to establish equilibrium? is 4. The reaction is started with a mixture of 1.6
[ N 2 O 4] = 0 .9 0 5 M [N O 2] = 0 . 1 9 M, 9.5% mol of Y2 and some X 2 in a two-liter container and
is allowed to reach equilibrium. The equilibrium
2.31 The equilibrium constant, Kc, is 0.2 at 100°C concentration of XY2 is measured to be 0.4 M. Cal­
for the reaction. culate the number of mole of X2 initially put into
2ABC (g) 2AB (g) + C 2 *(g) the mixture ? 0.4 m ol
An equilibrium mixture in one-liter flask at 100°C
contains 0.1 mol of AB, 0.2 mol ABC and 28.4 g of 2 . 3 4 A mixture of N 2 0 , N 2 0 4, and 0 2 gases are
C 2 . What is the atomic mass of С ? 35.5 g /m o l put into a 1 0 -liter flask at a certain temperature at
which Kc = 5 x 105 for the reaction
2.32 At a certain temperature an equilibrium mix­ 2N20 (g) + 3 0 2 (g) 2N 2 0 4 (g). If the equili­
ture in a one liter vessel has the following composi­ brium mole number of N 2 0 4 is twice that of N 2 0 ,
tion; 0.2 mol of A, 0.3 mol of B, 0.3 mol of С and what will be the mole number of 0 2 at equilibrium?
64 g of D for the reaction : 0 .2 mol
2 A(g) + B(g) C(g) + D(g) 2.35 The equilibrium constant, Kc, is 0.16 at a cer­
When 0.9 mol of В and 2.4 mol of D are added to tain temperature for the reaction
the vessel at the same temperature, the system re­ 3X (s) < =* Y (s) + 2Z (g).
mains at equilibrium. Calculate the formula mass of At least how many moles of X must be placed in a 5
D. 80 g /m o l L flask to establish the equilibrium at the given tem­
perature ? 3 m ol

Equilibrium Constant in Terms of Pressure, Kp

2.36 What is Kp? How is it related to Kc? In what um is as follow s.
conditions are they equal ? Ppci5 = 1 .8 x l0 ‘2 atm, P pci3 = P ci2 = 6.0x1 O’3 atm.
What is the equilibrium constant, Kp, for the reac­
2.37 Prove that Kp = KC.RT for the reaction с tion at 27°C. ? 2 .0 x l0 '3 atm
COCl 2 (g )< = > CO (g) + Cl2 (g)
2 . 4 0 An equilibrium mixture contains 2 mol of
2.38 Write the relationship between Kp and Kc for NH3, 2 mol of N 2 and 1 mol of H2 at 227° С in a 2
each of the following reactions. Indicate the unit of liter container. For the reaction
Kp in atm in each case. N 2 (g) + 3H 2 (g) 2NH 3 (g)
a) 4H 2 (g) + CS 2 (g) <=* CH 4 (g) + 2H2S (g) Calculate (a) Kc (b) Kp
b) CO (g) + S 0 3 (g) < = ^ S 0 2 (g) + C 0 2 (g) K c =8 K p = 4 . 7 6 x 1 0~3
c) NH4HS ( s ) <=* NH 3 (g) + H2S (g)
d) S n 0 2 (s) + 2H 2 (g) < = ^ Sn (s) + 2H20 (g) 2.41 Nitrosyl bromide, NOBr, dissociates on heat­
2* ing:
2.39 In the reaction 2NOBr (g) «=> 2NO (g).^ Br2 (g)
P C I 5 (g) < =* PCI3 (g) + Cl 2 (g) When 44 g of NOBr is placed in a 4 liter container
at 27°C the partial pressures of the gasesaTcquilibri- and heated to 127°C, the equilibrium pressure is 4.1
 \
82 Chapter 2 ШННШНШНШШНШШННИШ IIIII........................................................................... I ................. IIIIIIII...... 1111.................

atm. Calculate (a) the percentage dissociation of NH 3 into N 2 and H2

(a) the partial pressure of each gas at equilibrium. (b) Kp for the reaction at 273° C.
(b) the value of Kp and Kc (a)30% (b)0.29
(c) the degree of dissociation of NOBr.
( a ) p N O B r= p N O = 1 6 4 a t m ; P Br2= 0 . 8 2 a t m 2.46 Consider the following equilibrium process :
(b)K p=0.82 K c =26.9 c) 50 % NH 4 C 0 2 NH 2 ( s ) < = ^ 2NH 3 (g) + C 0 2 (g)
At a certain temperature, the reaction started with
2 . 4 2 One mole of N 0 2 (g) is placed in a sealed some NH 4 C 0 2 NH 2 and the total pressure at equili­
container and heated to a certain temperature. At brium is found to be 1.5 atm. Calculate the equili­
equilibrium it is found that the amount of 0 2 is 0 . 2 brium constant, Kp, for the reaction. 0. 5 a t m 3
mol, and the total pressure of gases is 2.4 atmos­
phere. Calculate Kp for the reaction 2.47 A sample of pure SO 3 gas decomposes :
2NOz (g) <=> 2NO (g) + 0 2 (g) 2 S 0 3 (g) <=> 2S 0 2 (g) + 0 2 (g)
0.18 atm The equilibrium constant, Kp, is 25. Analysis shows
that the partial pressure of 0 2 is 0.25 atm at equili­
2 . 4 3 Some NH 3 (g) at a pressure of 1.2 atm was brium. Calculate the partial pressure of S 0 2 and SO 3
injected into a reaction vessel. When the reaction, in the equilibrium mixture.
2NH3 (g) <=$■ N 2 (g) + 3H2 (g), reached equilibrium, P s# = 0 .5 0 atm, P s o ,=0.05 atm.
the total pressure in the container was measured 1 . 6
atm. What would be the Kp? 0.0675

2 . 4 4 A container at a certain temperature contains

C 0 2 at a pressure of 0.5 atm, solid graphite is added
to the container and some of the carbon dioxide is
converted to carbon monoxide. At equilibrium the
total pressure of gases in the container is 0.75 atm.
Calculate Kp for the reaction:
С (s) + C 0 2 (g) 2CO (g) Figure I shows the start of the following reaction at
Kp = 1 a certain temperature
2 . 4 5 A 3.4 g sample of NH 3 is put into a 2.8 liter 2 N 0 2 (g) * = * N 2 (g) + 2 0 2 (g)
container at 273°C. At this temperature the reaction Figure II represents the situation of the same reac­
2NH 3 (g) <=^ N 2 (g) + 3H 2 (g) reaches equilibri­ tion at equilibrium at the same temperature. Calcu­
um. If the total pressure of the gases at equilibrium late the equilibrium constant (Kp) for the reaction.
is 4.16 atm, calculate 0.25

Relationship of К and The Balanced Equation

2 -4 9 How is an equilibrium constant related to ing reaction is 0.64 at 600 K.
the equilibrium constant for N 2 (g) + 3H 2 (g) < = * 2NH 3 (g)
(a) reverse reaction? (a) What is the value of Kc for
(b) the reaction enlarged by a factor of n? 2NH 3 (g) ^ N 2 (g) + 3H2 (g)
(b) What is the value of Kc for
2.50 The equilibrium constant (Kc) for the follow­ 1/2N2 (g) + 3/2H 2 (g) NH 3 (g)
iiiiiiiiiiiiiiiiiiiiiiiiiiiitin iiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiH iiiiiiiiiiiiiiiiiiiiiiiiiiiiiiH iiiiiiiiiiiiiiiiiiiiiiiiiriiiiiiiiiiiiiiii Chemical Equilibrium 83

(c) What is the value of Kc for 2 . 5 3 Given the reactions with their equilibrium
' 2N 2 (g) + 6 H2 (g) 4NH 3 (g) constants
(d) What are the values of Kp for the original reac­ A(g) + 2B (g) < =* C (g ) + D(g) (fast) K, = 8
tion, and for the reactions described (a), (b), and (c), G (g) + E (g) «=> D (g) + К (g) (fast) K 2 = 1
• , К c= 2 .5 x l O ' 4 К (g) + G (g) < = ^ E (g) + С (g) (slow) K 3 = 2
2 . 5 1 At 2000,К the values of Kc are given for the What is the equilibrium constant for the reaction
reactions. A(g) + 2B(g) 2G(g)
2CO (g) + 0 2 (g) 2C 0 2 (g) Kc = 1.0 x Ю8 4
i
H20 (g) < = > H 2 (g) + 1/2 0 2 (g) Kc /= 2.5 x 10-5 -.2.54 Given the reactions with their equilibrium
Find the value of Kc at 2000 К for the reaction constants
H2 (g) + C 0 2 (g) < =* H20 (g) + CO (g) I. 2A (g) + В (g) С (g) + D (g) K 1 = 32
Kc=4 II. С (g) + E (g) ^= > К (g) + L (g) K2 = 0.5
2 . 5 2 From the values of Kc given '*III. 4K (g) + 2D (g) < = ^ 2E (g) + 2F (g) K 3 = ?
С (s) + 2H 2 (g) CH4 (g) Kt If the equation and Kc for overall reaction is given as
С (s) + 0 2 (g) ^ C 0 2 (g) K2 follow
CH 4 (g) + 2 0 2 (g) * = * C 0 2 (g) + 2H20 (g) K3 2A(g) + B(g) + L(g) + F (g )^ = >
determine the value of Kc in terms of Kb K 2 and K 3 2C(g) + 2D(g) + К K4 = 256
for the reaction What is the value of K 3?
H20 (g) <=> H 2 (g) + l/2 0 2 (g) К 3= 0 . 0 6 2 5

Reaction Quotient.
2 . 5 5 What is reaction quotient, why is it used for? 2 . 5 7 Can a mixture of 2 mol of H 2 0 , 2 mol of
CO, 3 mol of H 2 and 3 mol of C 0 2 exist in equili­
2.56 Consider the reaction : brium in a 5 liter flask at 600 К at which Kc = 36
N 2 (g) + 0 2 (g) 2NO (g) IQ = 0.04 for the reaction
In several experiments the gases were mixed as indi­ CO (g) + H20 (g) ^ C 0 2 (g) + H 2 (g)
cated below. In each of the cases decide whether a net If not, in which direction will a reaction take place?
reaction will occur, and if so in what direction ? Cal­ Calculate the concentration of each component in the
culate the final equilibrium concentration of each final equilibrium. N o , f o r w a r d r e ac t i on,
component. [ C O ] = [ H 2O ] = 0 . 1 4 M
(a)'0.1 mol of N2, 0.1 mol of 0 2, and 0.02 mol of [ C O 2 ] = [ H 2] = 0 . 8 6 M
N O in 1 L box.
Щ 0.1 mol of N2, 0.1 mol of 0 2, and 0.02 mol of 2 . 5 8 For the reaction,
NO in 10 L box. N 2 (g) + 3H2 (g) «=> 2NH 3 (g), IQ = 2.5 x 10" 3
(c) 0.1 mol N2, 0.01 mol of 0 2, and 0.01 mol of at 1000 K. (a) Will a mixture of 1 mol of each N2,
NO in 50 L box. H2, and NH 3 produce a net reaction in a 2 liter flask?
(d) 0.2 mol N2, 0.2 mol of 0 2, and 0.02 mol of NO (b) If not, will NH 3 be produced or consumed? (c)
in 100 L box. What must be the voiume of the flask if the mixture
(a)and (b)at equilibrium; (c)reverse and described in part (a) to be at equilibrium?
[ N O ] = S . 4 6 x l O "5 M ; (d)forward, Yes, consumed, V=0.05 L
[N O ]=3.8xlO ' 4 M
84 Chapter 2 НИШШШНШ НШШНШНШНШНННШШИШШШИНШ ............. II....Illllllllllllllllllillllll....1Ш
Ш1Ш
1И............Ill.... mint

2 . 5 9 A2 (g) + B 2 (g) 2AB (g) Kc = 4 В (g) + 2D (g) <=> A (g) (fast)

Initially 1 mol of A2, 1 mol of B 2 and 3 mol of AB 2C (g) <=> В (g) + 2F (g) (fast)
are placed into a 5 - liter container. What will be the The mechanism of a reaction is given. The equilibri­
molarity of each substance at equilibrium? um constant, Kc, of the reaction is 0.16 at a certain
[ Л 2] = [ В 2] = 0 . 2 5 M, [A B ]= 0 .5 M temperature. If the reaction is started with 3.1 mol of
A, 3.1 mol of В and 1 mol of F in a one-liter con­
2.60 At a certain temperature the equilibrium con­ tainer, what will be the equilibrium concentrations?
stant (Kc) is 0.36 for the reaction [A ]= [ B ] = 3 M, [F ]= 1 .2 M
S 0 3 (g) + NO (g) S 0 2 (g) + N 0 2 (g)
Decide whether a net reaction will occur if 0.30 mol 2.62 The equilibrium constant (Kp) at 100°C for
of each of S 0 3, NO, S 0 2 and N 0 2 are mixed in a the following reaction
3.0 L box ? If so, in which direction will it proceed N 2 0 4 (g) <=-> 2 N 0 2 (g)
to establish equilibrium ? Calculate the equilibrium is 6.4. A vessel contains N 0 2 and N 2 0 4. The pres­
concentration of each component. sures of these gases are N 0 2, 1.6 atm; N 2 0 4, 0.4
[ S O 3]= [N O ]= 0 .1 2 5 [ S 0 2] = [ N 0 2] = 0 . 0 7 5 atm. Calculate the partial pressure of each gas at
equilibrium.
2 . 6 1 2A (g) + В (g) 2C (g) + 2D (g) (slow) P n 0 2=1-6 atm, PN l o 4 = 0 .4 atm

Factors Affecting Equilibrium - Le C hatelier's Principle

2 . 6 3 What is the statement of Le Chatelier's Prin­ d) an increase in temperature ? ^
ciple? Suggest four ways to increase the equilibrium e) the injection of a catalyst 1 )^
concentration of S 0 3 in the reaction
2 S 0 2 (g) + 0 2 (g) 2 S 0 3 (g) (endothermic) l.ftl The reaction
PCI 5 (g) <=^PC1 3 (g) + Cl2 (g), is endothermic
2.64 Under what conditions do changes in pressure with AH = +21 kcal. What will happen to the con­
and volume affect the equilibrium of a reacdon ? centration of Cl2 at equilibrium if (a) more PCI5 is
added ? (b) PC13 is removed ? (c) the volume of the
2.65 Which of the following equilibria will not be container is decreased ? (d) the temperature of the
affected by a change in volume or pressure ? system is decreased ?
a) CH20 (g) H 2 (g) + CO (g) How (at all) will each of these changes affect the val­
b) 2CH 4 (g) ^ C2 H 6 (g) + H2 (g) ue of Kc for the reaction ?
c) 2NO (g) + 2CO (g) N 2 (g) + 2C 0 2 (g)
d) C aC 0 3 (s) + 2HF (g) 2.68 The equilibrium constant (Kp) for the reaction
CaF 2 (s) + H20 (g) + C 0 2 (g) 2N20 (g) ^ 2N 2 (g) + 0 2 (g)
is 1.8 x 103 6 at 25°C. It is 5.0 x 103 5 at 40°C. Is
2.66 Consider the reaction : the reaction exothermic or endothermic ? Explain
2NO (g) + Cl2 (g) < = ^ 2NOC1 (g) AH = -18.4 kcal your answer. Is N20 more stable at low temperatures
How will the equilibrium be affected by or at high temperatures ? Why ?
a) the addition of NOC1 ?
b) the removal of NO ? ^ 2 . 6 9 G iven the reaction
/C^a decrease in the volume of the container CH4 (g) + 2 0 2 (g) ^ C 0 2 (g) + 2H20 (g)
AH < О
iiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiitiiiiiitiiiiiiiiiiiiiiiiiiiiMiiiiiiiiiiiiiiiiiiiiiitiiiiiiiiiiiiiiiiiiiiiiiiiiiiiii Chemical Equilibrium 85

Which direction does the reaction shift when the fol­ (e) Calculate the value of Kc using the concentra­
lowing changes are applied to the reaction? tions at t = 45 s.
(a) the addition of 0 2 f) How could you account for the differences in the
(b) the removal of CH4 value of the equilibrium constants at the times, t = 7
(c) the removal of C 0 2 s and t = 45 s ?
(d) an increase in temperature (g) What differences would you have observed on the
(e) a decrease in volume graph if a catalyst had been introduced during the en­
(f) a decrease in pressure tire course of this reaction ?
(g) the addition of a catalyst (h) List the necessary changes to produce maximum
(h) addition of helium gas at constant volume quantity of CH 3 OH at equilibrium.
(1) addition of helium gas at constant pressure. (a)5 s, (b ) K c = 0 .01 7 (c)S om e CO was a d d ­
ed a t t= 10 s. Som e C H j O H was re m o v e d at
2.70 t= 20 s.V o lu m e o f th e c o n ta in e r was de­
c re a s e d a t t= 30 s. T e m p e ra tu re was in ­
c re a s e d at t= 40 s. (e ) K c = 0.010
(f )B e c a u s e of th e d if f e r e n c e s in tem pera­
ture. (g ) E q u ilib r iu m w o u ld have been e s ta ­
b lish ed more r a p i d ly .

2.71 An equilibrium mixture for the reaction

H 2 (g) + I2 (g) < = ^ 2HI (g)
contain 1 mol of H2, 1 mol of I2 and 2 mol of HI in
one liter container at a certain temperature. What
will be the concentration of each of the components
at final equilibrium when
Graph for question 2.70 (a) 1 mol of H 2 and 1 mol of I2 are added to the mix­
The given graph shows the variation of the concen­ ture ?
trations of CO, H 2 and CH3OH with respect to time (b) 1 mol of HI is added to the original mixture ?
during the establishment of the equilibrium repre­ (c)lmol of HI is removed from the original mixture?
sented by the equation (d) 0.5 mol of each of H 2 and I2 are removed from
CO (g) + 2H 2 (g) CH 3 OH (g) AH < 0 the original mixture ?
Under a given set of conditions. ( a) [ H 2] = [ 1 2] - l - 3 M ,[ H I ] = 3 M,
(a) How much time was required for the reaction to ( b) [ H 2] = [ 1 2] = 1 .25 M , [ H I ] = 2 .5 M
reach equilibrium ? ( c ) [ H 2 ] = [ I 2] = 0 .7 S M ,[ H I ] = 1 .5 M,
(b) Calculate the value of Kc using the concentra­ ( d ) [ H 2] = [ I 2]= 0 .7 5 M ,[H I]= 1 .5 M
tions at 7th second.
(c) What change might have been imposed on the 2 . 7 2 An equilibrium mixture in a one liter con­
system at (1) 10th second, (2) 20th second, (3) 30th tainer for the reaction,
second, (4) 40th second 2 S 0 2 (g) + 0 2 (g) < = ? 2 S 0 3 (g), has the follow­
(d) Explain the events taking place between the time ing composition. [S 02] = 0.20 mol/L,
intervals of (1) s and 5 s, (2) 10 s and 20 s, (3) 20 s [0 2] = 0.20 mol/L, [S 03] = 0.40 mol/L.
and 30 s, (4) 30 s and 40 s (5) 40 s, and 50 s. (a) How many mol of S 0 3 must be added to increase
86 Chapter 2 iiiiiiiiiiiiiiiiiiiiiiiiiHiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiinmiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiHiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiitiiiiiiiiiii

the equilibrium concentration of S 0 2 to 0.40 M? volume of the container in which the reaction is at
(b) How many mol of S 0 3 must be removed from equilibrium is suddenly doubled at constant tempera­
the original equilibrium mixture to decrease the equi­ ture, what will the new equilibrium concentrations
librium concentration of 0 2 to 0.15 mol/L? be? [ P C l 5] = 1 .0 6 8 ,[ P C l 3] = [ C l 2] = 0 . 2 0 7
(c) Draw a concentration versus time diagram for
both (a) and (b) a )0 .7 8 m o lS O 3 b )0 .3 3 m o lS O 3 2 . 7 7 Given : SbCl5 (g) ^ SbCl3 (g) + Cl2 (g)
At 250°C 1 mol of SbCl5, 2 mol of SbCl3 and 0.5
2 . 7 3 The equilibrium constant for the reaction mol of Cl2 are at equilibrium in one liter container.
X 2 (g) + Y2 (g) 2XY (g), is 64 at a given When the temperature is decreased to 200°C, 10% of
temperature. If 1 mol of X 2 and 1 mol of Y2 are put SbCl3 in the container decomposes to reestablish the
in a one liter container, equilibrium. Calculate the equilibrium constants at
a) calculate the equilibrium concentration of each 250°C and at 200°C. Decide whether the reaction is
substance. exothermic or endothermic. Account for your rea­
b) to increase the equilibrium concentration o f sons. 1 a n d 0.45, E n d o th e rm ic .
XY to 1.7 M, how many m oles o f X2 must be ad3ed
to the co n ta in e r? a) [X 2 ] = [ Y 2 ] = 0 .2 M, 2 . 7 8 Given : 2S 0 2 (g) + 0 2 (g) 2 S 0 3 (g).
[X Y ]= 1 .6 M b) 0.15 mol X2 When the reaction is at equilibrium at a certain tem­
2 . 7 4 If 2 mol of AB are placed in a 1-liter vessel, perature the mole numbers in a 5-liter container are
the equilibrium reaction; found to be S 0 3 = 3.0 mol, S 0 2 = 2.0 mol, 0 2 = 1.5
A2 (g) + B2 (g) < = ^ 2AB (g) will take place. If mol. Being careful to keep the temperature constant,
the equilibrium concentration of В is 0,2 M the volume of the reaction vessel is reduced to 2 li­
a) calculate the Kc. ter/and some S 0 3 is added to the vessel. When the
b) to decrease the equilibrium concentration of new equilibrium has attained the mole number of 0 2
A 2 to 0.1 M, how many moles of AB must be re­ is found to be 2 , what is the number of moles of
moved from the container? S 0 3 added ? 6.2 m ol
K c= 6 4 ,lm o lo f A B m u s tb e r e m o v e d .
2 . 7 f Given : A (g) + В (g) 2C (g) 2 . 7 9 2A (g) + В (g) 2C (g)
An equilibrium mixture contains 0.5 mol of each of At equilibrium a 6 -liter container has 6 mol of
A and В and 3.5 mol of С in one-liter container at a A, 0.18 mol of В and 3.6 mol of C. At a constant
certain temperature. temperature the volume of the container is decreased
(a) How many moles of С must be added to the con­ to 4 liter and some С is added. When the new equili­
tainer to increase the new equilibrium mole number brium is attained, the mole number of В is found to
of A to 0.75? be 0.3. Find the mole number of С added.
(b) If 1 mol of each of A, В and С is added to the 2 .5 6 mol
first equilibrium mixture, what will be the new equi­
librium concentration of each species at the same 2.80 An equilibrium mixture for the reaction
temperature? 2X (g) + Y (g) <=*• 2Z (g)
a )2 .2 5 m o l b )[A ]= [B ]= 0 .8 3 M [C ]= 5 .8 4 M contains 2 mol of X, 1 mol of Y and 2 mol of Z in
2 . 7 6 Given : PC15 (g) PC13 (g) + Cl2 (g). one liter vessel. How many moles of Y must be add­
When the reaction is at equilibrium at a certain ed to the mixture to increase the number of mole of
temperature, the concentrations are found to be Z to 3 at new equilibrium at the same temperature ?
[PC13] = [Cl2] = 0.30 M and [PC15] = 2.25 M. If the 8 .5
iiiiiiiiiiiiiiiiiiifH w n iiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiim iH iiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiii Chemical Equilibrium 87

Factors Causing Equilibrium

2.81 What is a spontaneous change ? List three 2.84 For each of the following reactions, decide if
spontaneous changes that you have encountered in (i) tendency toward minimum energy favors reactants
your daily life. or products.
(ii) tendency toward maximum randomness favors re­
2 . 8 2 Why does equilibrium exist in nature? actants or products.
(a) 2A12 0 3 ( s ) < = > 4A1 (s ) + 3 0 2 (g)
2.83 Will the randomness (entropy) increase or de­ (b) CaO (s) + H20 (g) Ca(OH ) 2 (s)
crease for each of the following changes ? (c) 2C1 (g) < =* Cl2 (g)
(a) The condensation of moisture on the surface of a (d) CO(NH2 ) 2 (aq) + H20 (1)
cold mirror.
C 0 2 (g) + 2NH 3 (g) AH = +28.4 kkal
(b) Increasing the pressure of a gas at constant tem­
(e) N2 0 4 (g) 2N 0 2 (g) AH = +14 kkal
perature.
(f) 2 0 3 (g) < = ^ 3 0 2 (g) AH = -6 8 kkal
(c) The dissolving sugar in water.
(g) 2NH 3 (g) <=> N 2 (g) + 3H 2 (g) AH = +22 kkal
(d) The vaporization of cologne.

M iscellaneous Problem s
2 . 8 5 3 mol of A and 2 mol of В are introduced 2.87 The equilibrium,
into an evacuated container at a certain temperature. PC15 (g) PC13 (g) + Cl2 (g) is set up by heat­
When the equilibrium is ing 104.3 g of PCI5 (g) at 227°C in'a volume of 4.0
A (g) + 2B (g) ^ С (g) L. If the equilibrium pressure is 6.15 atm, calculate
established, 12.5% of the mixture by moles is found the equilibrium concentrations and the value of Kc.
to be C. What is the percentage by moles of В in [ P C l 5 ]=0.1 M [P C l3 ] = 0 . 0 2 5 M
equilibrium? 25 % [ C l 2 ] = 0 .0 2 5 M K c= 6 . 2 5 x l O '3

2 . 8 6 At 700 K, Kc for the reaction 2 . 8 8 The density of an equilibrium mixture esta­

С (s) + 2H2 (g) CH 4 (g) is 0.15. If 1 mol of blished by decomposing some PC15 according to the
CH 4 is injected into a one liter reaction vessel at reaction, PCI5 (g) < = ^ PC13 (g) + C12 (g), is 8.35
700 K, Calculate g/L at 327° С and 2.952 atm. What is the equilibri­
(a) the equilibrium concentration of each gas. um constant, Kc, at 327°C for the reaction?
(b) the amount of solid С present in the container at 2 x 1 O '2
equilibrium, in grams.
(c) the partial pressure of each gas at equilibrium. 2 . 8 9 At high temperatures H2S (g) is partially dis­
(d) Kp for the reaction by means of the partial pres­ sociated into H 2 (g) and S (g). At 14Q0 К it was
sures of gases calculated in part (c) found that when the total pressure is 1 atm, 30% of
(e) Kp by means of Kp = Kc(RT)An 1 mol of H2S is dissociated. Calculate the density of
a ) [ H 2] = 1 .4 M, [C H 4] = 0 .3 M ,b ) 8 . 4 g gas mixture at equilibrium represented by the equa­
c ) P и 2 = 8 0 .3 6 a t m , P Cj j 4 = 1 7 .2 2 atm . tion. H2S (g) ^ H 2 (g) + S ( g )
d) 0 .00 27 e ) 0 .0 0 2 6 0.23 g/L
88 Chapter 2 ш ц ш м ш ш н ш ш п и ш п ш ж ш и ш ш и п ш ш ш ш ш м ш н н м ш и и м ш ш м ш м ш п ш м ш ш ш ш ш н п ш п ш м и п ш и ж н и и ш ш ш н ш ш ш ш ш ш м и и м п

2 . 9 0 2 mol of CH4 and 2 mol of H2S gases are in­ a) How much time was needed for the reaction to
troduced into an evacuated container and heated to 57° reach equilibrium?
C. When the equilibrium, b) Calculate the value of equilibrium constant, Kc
CH4 (g) + 2H2S (g) <=> CS 2 (g) + 4H 2 (g), is es­ c) Explain the effect of change applied at 40 sec and
tablished at this temperature, the partial pressure of find how many moles of Cl2 was added at 40 sec.
H2 and the total pressure in the container are found to d) Calculate the concentration of each species in the
be 0.3 atm and 1.65 atm respectively. new equilibrium.
(a) What is the volume of the container? e) Complete the graph
(b) What is the equilibrium concentration for b )K c= 8 c)1.2S mol d)(PCls ) = l .2 5 ,
each species? ( P C l 3)=0.25 , ( C l 2) = 0 . 6 2 5 M
V = 72.16L , [ C H 4] = 0 . 0 2 5 M
[ H 2S]=0.022 M 2.93 One mol of 0 2 and an excess quantity of С
are placed in a closed container.
2 . 9 1 Equal volumes of S 0 2 and 0 2 gases at the 2C (s) + 0 2 (g) < = ^ 2CO (g)
same pressures and temperatures are introduced into a Kp = 0.4 at a certain temperature. When the reaction
2.0 liter container and heated to 127° C. When the reaches the equilibrium, the total pressure inside the
equilibrium is established at this temperature, the container is measured to be 2.4 atm. Calculate the
number of moles of S 0 3 is found to be 4 and the number of mole of CO at equilibrium. 0.4 mol
pressure is measured as 164 atm.
(a) What is the number of moles of S 0 2 initially 2.94 Carbon monoxide and chlorine react to give
introduced into the container? phosgene:
(b) How many moles of S 0 2 must be added to CO + Cl2 -+ COCl2
the container to make the number of moles of S 0 3 Find the rate expression if the reaction proceeds by
twice the mole number of 0 2? the following mechanism :
(a)6 mol, (b)3.46 mol Cl2 2C1 (equilibrium)
Cl + CO <=^COCl (equilibrium)
2.92 The graph shows the number of moles of COC1 + Cl2 -> COCl2 + Cl (slow)
species in a 2 liter system as a function of time R=k [CO] [ C l 2 ] 312

PC13 (g) + Cl2 (g) «= > PCI5 (g)

under a given set of conditions.
пшншншнишштшттшнишишшпншшшшшшшшшшшшииишншшншшттштшшттшштншш Chemical Equilibrium 89

SELF TEST

1. For a reaction to be at equilibrium : 5 . At a certain temperature, some X was used to

I. The reaction must occur in a closed vessel at a cer­ establish the equilibrium:
tain temperature. X (s) < = ^ Y (g) + 2Z (g). When the equilibrium
II. The number of moles of reactants and products was established the partial pressure of Y was meas­
must be equal. ured to be 0.2 atm. The value of Kp at that tempera­
III. The rates of forward and reverse reactions must ture is :
be equal. A) 0.01 B) 0.02 C) 0.04 D) 0.08 E) 0.032
IV. The reaction must be homogeneous.
Which ones of these requirements are necessary ? 6. Given the reaction :
A) I. II, III B) I, III, IV C) II, IV N 2 (g) + 3H 2 (g) ^ 2NH3 (g)
D) I, III E) I, II. Ill IV The unit of Kc for this reaction is:

2 . B) mol2 L2 C) mol . L 2
2
D) E) mol К
mol

7 The mechanism of the reaction;

A (g) + В (g) +=> 2F (g) is given below
2A (g) + В (g) <= 5 - 2C (s) + 2D (g) (slow)
В (g) + 2D (g) «=> A (g) (fast)
2C (s) <=> В (g) + 2F (g) (fast)
The figure shows the establishment of equilibrium Which is the equilibrium constant expression for the
for С (s) + C 0 2 (g) < = ^ 2CO (g) at a certain tem­ reaction?
2 2 2 ГД1
perature in a one liter container. The value of Kc for A) TO B) [C] [D] C) LAJ
this reaction is : (C = 12, C 0 2 = 44, CO = 28) [B] [D]
[A] [B] [A]2 [B]
A) 3.14 B) 16.0 C) 0.90 D) 2.12 E) 6.00

3 . Given : A (g) + 3B (g) ^ 2C (g) + D (g) И

D) E) CB] [F]
One mole of A and one mole of В are placed in a one [A] [B]
liter container. After the equilibrium has been esta­
8 . The reaction, 2 S 0 3 (g) 2S 0 2 (g) + 0 2 (g)
blished, 0.4 mol of С is present in the container. Kc
for this reaction is: is started with 3 mol of S 0 3. At equilibrium the re­
A) 0.250 B) 0.625 C) 1.560 D) 1.100 E) 2.785 action mixture contains 0.5 mol of 0 2, and exerts a
pressure of 7 atm. Which of the following is the
4 . At 1000 K, 0.3 % of 1 mol of I2 dissociates to equilibrium constant, Kp, for the reaction ? \ . x
establish the equilibrium represented by the equation, A) 0.25 B) 0.5 C) 1.0 D) 1.5 feT2.0
I2 (g) <=> 21 (g), in one liter container. The value
of Kc at 1000 К is: 9 . For the reaction,
A) 3.6 x 10" 5 B) 6.0 x 10- 3 C) 3.7 x 10' 3 A 2 (g) + 3B2 (g) < = ^ 2 A B 3 (g),
D) 6.0 x 10 ' 5 E) 2.8 x 10 - 3 Kp = 0.01 and Kc = 67.24 at the same temperature.
90 Chapter 2 Ш Ш ИШ IIIIIIH IIII ШНМНПН МНИШ НПШШШНШШНННШПНННПШПШШШНПННШПННННШМНПШПШШНШПМШППШШ

What is the equilibrium temperature in K? 1 4 . Given the reaction :

A) 1000 B) 820 C) 727 D) 1.8 E) 0.15 2NO (g) <=> N 2 (g) + 0 2 (g) AH = -21.6 kcal.
I. Addition of NO
10. The equilibrium constant, Kc, for the reaction II. Removal of N 2
H 2 (g) + I2 (g) 2HI (g) is 64 at 400°C. Which III. Increasing temperature
will be the equilibrium concentration of HI if 1 mol IV. Increasing pressure
of HI is placed into a 10 L container at 400°C ? Which of these increases the equilibrium concentra­
A) 0.01 B) 0.08 C) 0.10 D) 0.20 E) 0.80 tion of 0 2?
A) I, II, III, IV В) II, III, IV С) I, III, IV
1 1 . Given : D) I, II E)I, IV
2 S 0 2 (g) + 0 2 (g) < = * 2 S 0 3 (g) Kc = 4
2CO (g) + 0 2 (g) < = ^ 2C 0 2 (g) Kc = 1/9 1 5 . Assuming equilibrium is reached in the reac­
Calculate Kc for the reaction: tion
CO (g) + S 0 3 (g) S 0 2 (g) + C 0 2 (g) 2CO (g) + 0 2 (g) ^ 2C 0 2 ( g ) ;
AH = -135.2 kcal
A) 4/9 B) 1/6 C) 3/2 D) 9/2 E) 2/3
A greater equilibrium yield of carbon dioxide will be
1 2 . At 500 K, 2 mol of N2, 4 mol of H2, and 0.8 best obtained by
mol of NH 3 are put into a two liter closed container. A) raising the temperature and pressure
At this temperature Kc for the reaction, B) lowering the temperature and pressure
N 2 (g) + 3H2 (g) <=> 2NH 3 (g) + 22 kcal, is 0.2. C) raising the temperature and lowering the pressure
Which of the following is true about this system? D) lowering the temperature and raising the pressure
A) The reaction is at equilibrium. E) adding a catalyst and raising the pressure
B) The total pressure of the gases increases while the
reaction reaches equilibrium. 1 6 . At 227°C, 0.1 mol of A, 0.5 mol of B, 0.2
C) The mole number of NH 3 at equilibrium is great­ mol of С and 0.5 mol of D are at equilibrium in a
er than 0 . 8 one liter container. When some A is added to the
D) As the temperature of the system increases, the container, the mole number of С at new equilibrium
value of Kc increases too. is found to be 0.3. Which is the mole number of A
E) The reaction continues until all N 2 is used up. added?
A (g) + 2B (g) ^ C(g) + D(g)
1 3 . For the reaction, A) 0.15 B) 0.50 C) 1.7 D) 2.4 E) 3.1
2 S 0 2 (g) + 0 2 (g) <==> 2 S 0 3 (g), Kc = 9 x 102
at 800 K, and Kc = 1 x 106 at 635 K. Which of the 1 7 . Which of the following procedures leads to a
following is w rong about this reaction? change in the value of the equilibrium constant of a
A) It is an exothermic reaction. chemical reaction?
B) At 800 K, S 0 3 molecules are more stable than
A) a change in the pressure
those at 635 K.
B) a change in the temperature
C) The heat content of S 0 3 molecules is less than
C) replacement of the catalyst
that of S 0 2 molecules.
D) Kp is smaller than Kc at 800 K. D) a change in concentration of reactants.
E) The ratio of specific rate constant for forward re­ E) a change in concentration of products.
action to that of the reverse reaction at 635 К is
lxlO6.
iiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiii C h em ica l E q u ilib r iu m 91

1 8 . Given the following equilibrium constant data.

N 2 (g) + 0 2 (g) ^ 2NO(g)
N 2 (g) + 1/2 0 2 (g) <=> N20 (g)
What is the equilibrium constant for the reaction?
N20 (g) + l/2 0 2 (g) <=► 2NO (g)
A) 2 x lO' 13 B) 4 x 10' 17 C) 8 x 10' 4 9
D) 5 x 10" 12 E) 2 x 10’ 3

19. Consider the reaction

P b(N 0 3 ) 2 (s)< =^ PbO (s) + 2N 0 2 (g) + l/2 0 2 (g)
I. Tendency toward minimum energy favors prod­
The given graph shows the concentration changes as
ucts.
function of time for the reaction:
II. Tendency toward maximum randomness favors
2 N 0 2 (g) N 2 0 4 (g) + heat
products.
Which stresses are applied to the equilibrium system
III. The reaction should be exothermic.
at times ti , t2 and t3
IV. Pb(N 0 3 ) 2 is less stable at high temperatures.
t2 t3
Which one(s) of these four statements is COR­
A) N2 0 4 added Temp.increased MTj added
RECT?
B) N 2 0 4 removed Temp.increased temp.dec.
A) I, II, III, IV B) I, IV C) II, IV C) N2 0 4 added Temp.decreased V dec.
D) I, III E) И, III, IV D) N2 0 4 added Temp.decreased V inc.
E) N2 0 4 added Temp.increased P inc.
 CHAPTER

SOLUBILITY EQUILIBRIA

The objectives o f this chapter are to enable the student to :

1 - Recognize that an equilibrium exists in a saturated solution of slightly
soluble solid.
2 - Write dissociation reaction o f an ionic solid into its component ions.
3 - Write solubility product expression, K^, for slightly soluble ionic sol­
ids.
4 - Calculate K*p from experimentally determined solubility of a substan­
ce.
5 - Calculate solubility in various units from known value of
6 - Describe the effect o f common ions on the solubilities o f slightly soluble
ionic compounds, and solve problems involving common ion effect.
7 - Express and apply criterion for precipitation from solutions.
8 - Learn how a mixture of ions can be separated.
iiiiiiiiiiiiiiiiiiiiiiiiiiiiiiM iiiiiiiiiiiiiiiiiM iiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiH iiiiiiiiiiiiiiiiiiiiiiii Solubility Equilibria 95

In the process o f form ing a solution, one substance m ixes com pletely w ith
another to form a hom ogeneous mixture. W hen sodium chloride, NaCl, (called
solute) is added to water (called solvent), the ions form ed are uniform ly distrib­
uted among the m olecules o f water. The solid particles (Na+ and С Г ions in this
case) diffuse continueously throughout the water.
A solution is saturated w hen the dissolved solute exists in equilibrium with
undissolved solute. In other words, if m ore solute is added to a saturated solu­
tion, it will not dissolve. B ut it settles down. In this chapter we will study satu­
rated aqueous solutions o f slightly or insoluble ionic com pounds.

3,1 SOLUBILITY OF IONIC SOLIDS

W hen a negligibly soluble ionic solid is placed in water, an equilibrium is es­
tablished betw een the ions in the saturated solution and the solid rem ained un­
dissolved. In a saturated solution o f slightly soluble AmB n, the rate o f dissolu­
tion o f AmBn into the ions A n+ and Bm' is equal to the rate o f precipitation o f
AmBn from its ions as shown in Figure 3.1. T hen a solubility equilibrium is set
up between the slightly soluble AmBn and the ions o f An+ and Bm~ . A t equilibri­
um, the concentrations o f ions of An+ and Bm_ are constant at constant tem pera­
ture as indicated in Figure 3.2.

TABLE 3 .1 K sp oj
Some S ligh tly So
ble Salts a t 25® С

PbB r 2 4 .6 x l0 -5
A gB r 5 .0 x l0 ‘13
C aC 0 3 4 . 7 x l 0 '9
M gC 03 L.OxlO "15
A g 2C 0 3 8.2х 10"12
S rC 0 3 7 .0 x l0 -!° tim e
FIGURE 3.1 The rate of dissolution is FIGURE 3.2 in the cource of dissolu­
P b C l2 1 .7 x l0 -5 equal to the rate of precipitation at equi­ tion, the concentration of each ion in­
A gC l 1 .7 x lO -10 librium. creases, and is constant at equilibrium.
C aF2 3 .4 x l0 -n
PbF 2 -8
2 .4 x l0 The dissolving reaction o f AmBn can be represented by the equation :
M gF 2 8.0x l 0"8
A l(O H )3 5 . 0 x l 0 '33
AmBn (s) «=> m A " + (aq) + nBm" (aq)
B a(O H )2 5 . 0 x l 0 -3 A ccording to the general procedure for writing equilibrium constants we m ay
C a(O H )2 1 . 4 x l 0 -6 w rite :
P b l2 8 .3 x lO -9
K c= [ A n T [Bm']n
A gl 8 . 5 x l 0 -17
Ca 3( P 0 4)2 1 . 3 x l 0 -32 As pointed out in the previous chapter, conventionally the constant concen­
A g 3TO4 1. 8x lO -18 trations o f pure solids are om itted from Kc expression. T he equilibrium con­
B aS04 l .S x lO "9 stant, K c , for solubility equilibria is referred to as K sp , w hich is called the
A g2S 5 . 5 x l 0 -51 solubility product o r the solubility product constant. T he expression,
96 Chapter 3 М 1Ш 1иш Н !И 1Ш Ш 111Н 111Ш 11И Ш даШ 1Ш Ш 1НМ 11111111Ш Ш Ш 1111111Ш 111111Ш И 111Ш 11Ш 1111111111Ш 1111Ш 11Ш Ш Ш Ш 11Ш 11Ш 1Ш 11111Ш 111Ш 1Ш Ш 11111111Ш 11Ш И

[A n+]m [Е Г 'Г , corresponding the reaction quotient o f the heterogeneous equili­

brium is called ion product, or Q sp. For a saturated solution o f a slightly soluble
substance, K sp m ust equal Qsp.
The num erical value o f Ksp can be determ ined experim entally. Once deter­
m ined it can be tabulated for future use. Since the solubility o f a substance usu­
ally varies widely with tem perature, the num erical value for K sp for a substance
changes w ith tem perature. A table o f solubility products o f som e typical sub­
stances is given in T able 3.1. A com plete list o f solubility product constants is
given in Appendix I at the end o f the book.

EXAM PLE 3.1 Writing Ksp Expression

Problem : Write a solubility product constant expression for each of the following substances.
(a) AgCl (b) CaF 2 (c) MgNH 4 P 0 4 (d) Ca3 (P 0 4 ) 2
Solution : The solubility product constant expression can be written by means of the balanced dissolution
reaction written per mole of solid.
(a) AgCl (s) <=> Ag+ (aq) + СГ (aq) Ksp = [Ag+][CF]
(b) CaF2 (s) Ca2 + (aq) + 2 F (aq) Ksp = [Ca2 +][F 1 2
(c) MgNH4 P 0 4 (s) <=*• Mg2+ (aq) + NH 4 (aq) + PO 2 - (aq) Ksp = [Мё 2 +][1ЧЩ] [ P 0 4~]
(d) Ca3 (P 0 4 ) 2 (s) 3Ca2+ (aq) + 2 P 0 4‘ (aq) Ksp = [Ca2 +] 3 [P 0 4~] 2

EXERCISE 3.1 Write the solubility product constant for each of the following substances.
(a) La(OH ) 3 (b) Bi2 S 3 (c) Ag 2 CrQ 4 (d) C aC 0 3

3.2 FACTORS THAT AFFECT THE SOLUBILITY

3.2.1 MAXIMUM RANDOMNESS AND MINIMUM
ENERGY
As explained in Section 2.6, there are two factors that fix the state o f equili­
brium . One o f these factors is the energy and the other is random ness. The
equilibrium results from a balance betw een m inim um energy and m axim um
randomness.

(a) R a n d o m n e s s :
Liquid solutions are m ore random than solids. In solvents, the dissolving
process destroys the regular (ordered) crystal lattice o f solids. T he dissolving
process, therefore, increases randomness. T he tendency toward m axim um ran­
dom ness tends to cause solids to dissolve.
The gaseous state is m ore random than the liquid state. B ecause the m ole­
cules in gaseous state m ove freely through a larger space. W hen a gas dissolves
in a liquid, random ness decreases. U nlike solids, the tendency tow ard m ax i­
m um random ness favors the gas phase and opposes the dissolution o f a gas.
In general, decom position o f large m olecules (particles) into sm aller m ole­
cules (or ions) increases randomness.
 iiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiii Solubility Equilibria 97

(b) Minimum energy :

M inim um energy opposes random ness. T he solid state o f a substance has
the least energy w hen com pared w ith liquid or gas state but it is the m ost ran­
dom. Hence, the tendency toward m inim um energy favors precipitation. To in ­
crease random ness, solids tend to dissolve. To low er energy, solids tend to
precipitate.
W hen gas m olecules enter a liquid, they com e close to the solvent m olecules
and they attract each other. So the potential energy decreases. Unlike solids, the
dissolution o f a gas releases heat. As a result, the tendency tow ard m inim um
energy favors the dissolving process.

EXAMPLE 3.2 Maximum Randomness

Problem : Given the following reactions. Explain whether the tendency toward maximum randomness favors
reactants or products
(a) BaS0 4 (s) Ba2+ (aq) + SO2 " (aq)
(b) CaC0 3 (s) <=> CaO (s) + C 0 2 (g)
(c) H2 0 (g ) ^ H20 (1)
(ф N20 (g) N20 (aq)
J e ) 2S 0 3 (g) ^= > 2 S 0 2 (g) + 0 2 (g)
Solution : (a) Dissociation of a solid into ions increases randomness. Then, the tendency toward maximum
randomness favors products.
(b) As explained in (a), the decomposition of a large particle into smaller particles increases randomness.
Then, products are more random than reactant particles.
(c) The gas phase is always more random than the liquid phase. So, the tendency toward maximum random­
ness favors reactant.
(d) The foregoing argument for part (c) is also applicable to this example. The tendency toward maximum
randomness favors reactants.
(e) When a large molecule is decomposed into smaller molecules, the randomness increases. Because the
smaller molecules can move freely when compared with large molecules from which they are produced. There­
fore, the tendency toward maximum randomness favors products.

EXERCISE 3.2 Explain whether the tendency toward minimum energy favors reactants or products in the
I following processes.
(a) Mg(OH ) 2 (s) < = ^ Mg2+ (aq) + 20H~ (aq)
(b) 0 2 (aq) «==> 0 2 (g)
(c) Ag+ (aq) + Cl" (aq) AgCl (s)
(d) С 12 Н 2 2 0 ц (s) Ci 2 H2 2 0 n (aq)
(e) 2NO2 (g) <=*■ N20 4 (g) ДН = -14.1 kcal
(0 2HI (g) .?=> H2 (g) + I2 (g) AH = - 6.2 kcal/mol

3.2.2 TEMPERATURE

Increasing the tem perature always increases the random ness. Therefore, the
solubility o f m ost solids increases with increase in tem perature. But there are
98 Chapter 3 1 Ш 1 |Ш Ш Ш Ш Ш Ш 1 1 1 1 Ш 1 1 1 1 1 Ш Ш 1 Ш Ш 1 Ш |1 Ш 1 |1 1 1 1 1 Ш 1 1 1 1 Ш Ш Ш 1 1 1 И 1 1 1 И 1 1 1 1 1 Ш Ш Ш Ш 1 1 Ш 1 1 1 1 1 1 Ш 1 Ш Ш Ш 1 1 |Ш ||1 1 |1 1 1 1 1 1 Ш Ш Ш Ш 1 Ш 1 1 1 1 Ш Ш И 1 1 1 Ш Ш Ш 1 1 1 1 1 1 1 1 1

som e exceptions. F or exam ple the solubilities o f anhydrous N a 2 S 0 4 , С а С О з ,

C a S 0 4 , and Ce 2 (S 0 4 ) 3 .9 H 2 0 decrease w ith increasing tem perature. A m ajor
com ponent o f som e boiler scale is calsium sulfate, w hich is less soluble in hot
w ater than in cold water. W hen w ater is heated in your teapot, a precipitation o f
C a S 0 4, C a C 0 3, ... etc occurs to form a boiler scale.
In the case o f gases, we find a contrast to the behavior o f solids. The solu­
bility o f gases decreases as tem perature is raised. B ecause the gas phase is al­
w ays m ore random than the liquid phase. F or exam ple, 1.713 L C 0 2 dissolve
in 1 L w ater at 1 atm and 0°C, but only 0.878 L dissolve at 20°C. M ost gase;s
can be expelled from solvents by boiling their solutions.
On the other hand, the dissolution o f m ost solids is endotherm ic. B ut the
dissolution o f gases is exothermic. See the follow ing examples.
NaCl (s) + 0.93 kcal —> Na+ (aq) + СГ (aq)
Cl2 (g) Cl 2 (aq) + 6.0 kcal/m ol (at 20°C and 1 atm)
If we assum e that the entropy (random ness) o f solutions for tw o gases is
about the same, then the gas with the larger negative Д Н 0 solution is m ore solu­
ble.

EXERCISE 3.3 The following solubility equilibria for different gases are given under the same condi­
tions.
0 2 (g) <=> 0 2 (aq) + 3 kcal
N20 (g) <=> N20 (aq) ДН° = -4.8 kcal
CI2 (g) <==^ Cl2 (aq) + 6 kcal
Which gas has the largest solubility in water under the same conditions ?

3.2.3 PRESSURE

T he effect o f pressure on the solubility o f solids and liquids is negligible but

the solubility o f gases increases with increasing the pressure on it. This can be
explained by Le Chatelier's Principle. C onsider the dissolution o f C 0 2 gas in
soft drinks,
C 0 2 (g) C 0 2 (aq)
If the partial pressure o f C 0 2 is increased, the system tries to decrease the
pressure. This is possible w hen some o f C 0 2 is dissolved.
If there is a reaction betw een gas and solvent, the solubility o f the gas also
increases. W hen am m onia gas is dissolved in water, it reacts w ith w ater in the
following way and this reaction increases the solubility o f N H 3 in water
N H 3 (g) + H 2 0 (1 ) ^ N H 4 (aq) + OH" (aq)
|1мш1111111111Ш
111Ш1шш1Ш1пшш1|1шши11шш1ншштш!1мшшшнАнтш!т11111111Ш111111111111111111Ш11м111ммш1М
1 Solubility Equilibria 99

3.2.4 EFFECT OF SOLVENT ON SO LUBILITY

A ccording to their bond formations, solvents are classified as polar coval­

ent solvents and nonpolar covalent solvents. Ionic and polar covalent sub­
stances are soluble to varying degrees in polar covalent solvents. F or exam ­
ple, w ater is a polar covalent solvent. H ydrogen end o f w ater m olecule is
partially positive (5+) and oxygen side is partially negative ( 8 "). See Figure
3.3. C onsider the dissolution o f sodium chloride in water. As soon as N aCl
crystals are added to water, the hydrogen (positive) end o f a polar w ater
m olecule is attracted to a negative chloride ion (СГ) at the surface o f the sol­
id, and the oxygen (negative) end is attracted to a positive sodium ion (Na+).
Then the w ater m olecules surround individual N a+ and С Г ions at the sur­
face of the solid. Because o f the electrostatic attraction betw een the charged
ion and the dipole o f water, several w ater m olecules associate with each ion
in solution. As a result, the ions o f the solid are separated from the solid and
becom e part o f the solution. Ionic com pounds dissolve in polar solvents
only w hen the polar solvent m olecules can solvate and insulate the ions.
Since sugar and alcohol are com posed o f polar m olecules, they are also sol­
uble in water. Because there are attractive forces betw een the opposite poles
1 * «- o f ethyl alcohol or sugar molecules and w ater molecules.
FIGURE 3.3 D issolution N onpolar solvents such as benzene or carbon tetrachloride will not dis­
of salt in water. solve ionic o r polar m olecular substances, because nonpolar m olecules have
no sites o f partial charge ( 8 + o r 8 ~). M any substances com posed o f nonpolar
covalent m olecules dissolve in nonpolar solvents. F or exam ple, nonpolar
substances, such as iodine (I2 ) and sulfur (S8), are soluble in a nonpolar sol­
vent such as carbon tetrachloride, CC14 , or, toluene, СбН 5 С Н 3 . Sim ply
speaking like dissolves like.

EXAM PLE 3.3 Effect of Solvent on Solubility ^

Problem .'Given the compounds : H 2 S, CH4, CH 3 OH, KC1, Вг2, HC1, C 6 H6.
(a) Which of these compounds can be dissolved in water which is a polar covalent solvent ?
(b) Which of these compounds can be dissolved in carbon tetrachloride which is a nonpolar covalent compound ?
Solution : (a) Water is a polar covalent solvent. Polar covalent solvents can dissolve ionic and polar covalent
substances. Among the given substances, KC1 is ionic; H 2 S, CH3 OH, HC1 are polar covalent compounds.
Therefore these substances can be dissolved in water.
(b) Since nonpolar solvents can dissolve nonpolar substances. The nonpolar substances, СН 4 ,СбН6, and Br2 can
be dissolved in nonpolar solvent, carbon tetrachloride (CCI4 ).

EXAM PLE 3.4 Solubilities in Different Solvents

Problem : Given the solubility equilibrium for I2 in different solvents.
I2 (s) + 1 . 6 kcal —> I2 (alcohol)
I2 (s) + 5.8 kcal - + I2 (carbon tetrachloride)
I2 (s) + 4.1 kcal —>I2 (benzene)
In which one of these solvents is the solubility of iodine maximum ?
Solution : If it is expected that the increase in randomness is the same for the dissolution of a given nonpo­
lar solute in different solvents under the same conditions, the relative solubilities in these solvents can be com-
100 Chapter 3 Ш 111Ш 1Ш 1111И 11111111111И И 111М Ш Ш Ш И Ш Ш 1Ш 111Ш 1Ш 1111И И Ш 11Ш 1Ш 11Ш 1Ш 11Ш Ш 11Ш Ш 1Ш 1Ш 1Ш 1111Ш 111111111Ш Ш 1Ш 1Ш !Ш 1Ш Ш | 11Ш И 11Ш | 11Ш 1Ш 1111

pared in terms of the energy factor. The solubility is greater in the system which absorbs the least amount of en­
ergy. Therefore, the solubility of iodine is maximum in alcohol. Because there is more interaction between io­
dine and alcohol molecules.

3.3 EXPERIMENTAL DETERMINATION OF

SOLUBILITY PRODUCT

If the solubility o f a com pound is known, its solubility product can be calcu­
lated as illustrated in the following examples.

EXAM PLE 3.5 C alculation o f Ksp

Problem : The eohcentration of each ion of Sr2+ and C 0 3_ is 2.5х ЦГ5 mol/L in the saturated solution of
БгСОз at 25°C. What is the solubility product for БгСОз at this temperature ?
Solution : ( 1 ) Write the dissolution equation and Ksp expression for SrC'Cb .
S rC 0 3 (s) <=^ Sr2+ (aq) + CO]~ (aq) Ksp = [Sr2+] [C 032“ ]
(2) Substitute the equilibrium concentrations of the ions into the solubility product expression for SrCC>3 .
Ksp = (2.5 x 10’5) (2.5 x 1(T5) = 6.25 x 1СГ1 0

EXERCISE (3.4 If the solubility of CaF2 is 2 . 0 x 1 0"4 mol/L at 25°C,'what is the solubility produc
C aF 2? v '• ’ ■ 3.2xlk

EXAM PLE 3 .6 Determination of Ksp

Problem : A weighed amount of solid AgCl is ground up and thoroughly shaked with a liter of water at
25°C, until the saturated solution is formed. Then the saturated solution is filtered, the residual solid AgCl is
dried and weighed. If the loss in mass of AgCl is found 0.0019 g, calculate the solubility product constant for
AgCl at 25°C. AgCl = 143.5 g/mol.
Solution : 1 - Write the equation representing the dissolution of AgCl, and Ksp expression.
AgCl (s) Ag+ (aq) + СГ (aq) Ksp = [Ag+] [СГ]
2 - Determine molar solubility of AgCl, then the molar concentrations of ions in the saturated solution.
Since the loss in mass, 0.0019 g, corresponds to the amount of solid AgCl dissolved in 1 liter of solution at
25°C, the molar solubility of AgCl can be calculated by using the equation
V
M (mol/L) = 2 m (grams of solute) x ------------ 1________
MW (molecular weight of solute) V (liters of solution) \

[AgCl] = - ё x J - = 1 .3 x 10~5 mol/L

143.5 g/mol 1L

Reference to the dissolution equation of AgCl, we can say that the mole of CF is equal to the mole of Ag+.
Then, [Ag+] = [CLJ = 1.3x10’ 5 M.
3 - Substitute the equilibrium concentrations of the ions into the solubility product expression for AgCl, and
find the result.
Ksp = [Ag+] [СГ] = (1.3 x 10’5) ( 1.3 x 10’ 5) = 1.7 x 10' 10
 ....... Solubility Equilibria 101

EXAM PLE 3.7 C a lc u la tio n o f Ksp

Problem : A 2.5 L saturated solution of ferrous hydroxide at 25°C contains 2.92 mg of Fe(OH)2. Calculate
the solubility product constant for Fe(OH ) 2 . Fe(OH ) 2 = 90 g/mol.
Solution : Follow the same procedure as in example 3.6.
1- Fe(OH)2 (s) <=*■ Fe2 + (aq) + 2 0 H ' (aq) Ksp= [Fc2 +j [OH' ] 2

2- [Fe(OH)2l = 2 9 2 x K)—& x —— = 1.3 x 10 5 M.

L J 90 g/mol 2.5 L

Fe(OH) 2 (aq) <=> Fe2 + (aq) + 20H '(aq)

1.3 x 1 0 ' 5 M 1.3 x 1 0 ' 5 M 2.6 x 10' 5 M.
3 - Ksp = [Fe2 +] [OH' ] 2 = (1.3 x 10"5) (2.6 x 1 0 ' 5 f = 8 .8 x 10' 15

Let us compare the solubility and solubility product constants of the substances mentioned in example 3.6 and
Compound molar solubility

AgCl 1.3 x 10' 5 mol/L [Ag+] [СГ] =1.7 x 10- 10

Fe(OH) 2 1.3 x 10" 5 mol/L [Fe2+] [OH" ] 2 = 8 .8 x 10' 15

The data show that care must be taken in comparing solubilities of different compounds. Even though
Fe(OH ) 2 has a smaller value of Ksp, its solubility is the same as that of AgCl.

EXERCIS^ 3.5 It is found that 3.32 x1 0 2 g of Ag2 Cr 0 4 is all that canbe dissolved in500 mL of wa­
ter at 25°C. Fmd-the Ksp for Ag2 C r 0 4 at 25°C. Ag2 C r 0 4 = 332 g/mol 3.2xl0'n

E XAM PLE 3.8 C alculation of Ksp

Problem : The concentration of PC)2 ' ions is found to be 3.0 x 10' 7 M in a saturated zinc phosphate solu­
tion in pure water. What is the concentration of Zn2+ ions? What is the solubility product of Zn 3 (P 04)2?
Solution : Zn3 (P0 4 ) 2 (s) < = ^ 3Zn2 + (aq) + 2P 0 2 ‘ (aq)
The equation reveals that 3 mol of Zn2 + appear in saturated solution for every 2 mol of PO2 ' appeared.
Thus the mole number of Zn 2 + is 3/2 times larger than the mole number of PO2 " , then
[ 2+1 -7 -7 -7
[Zn J = —x 3.0 x 10 = 4.5 x 10 M
1 J 2
The value of solubility product constant is
Ksp = [Zn2 + ] 3 [PO3 'I 2 .= (4.5 x 10' 7 ) 3 (3.0 x 10' 7) 2 = 8.2 x 10' 33

EXERCISE 3.6 2 L saturated solution of Ag3 P 0 4 contains 1 .2 x 1 0 '4 molof Ag+ions at 25°C. What is
the Ksp for Ag 3 P 0 4 at 25°C. 4 . 3 2 x l 0 ' 18

EXAMPLE 3.9 C alculation o f Ksp

Problem : Some Al(OH ) 3 is added to water to form 1 liter of
solution and shaked at laboratory temperature. Then the change in
concentrations of ions is represented in a graph as a function of
time. What is the solubility product constant for Al(OH ) 3 at this
temperature ?
Solution : The concentrations of Al3+ and OH- ions at equili­
brium from graph are 4 x 10"9 mol/L and 12 x 10"9 mol/L respec­
tin g
102 Chapter 3 п и ш и ш и и ш ш и ш н ж п м п и ш и ш и ш ш и ш ш ш ш ш и и ш и и ш и и ш и ш и ш ш и ш н ш ш н и и и и ш и н ш и ш ш ш н ш ш ш ш ш ш ш ш и ш ш ш п ш и

tively. The dissolution equation and Ksp expression for Al(OH) 3 is as follows :
Al(OH ) 3 (s) <=>A13+ (aq) + 3 0 IT (aq) Ksp = [Al3+] [OH“ ] 3
Now, substitute the concentrations of ions into the Ksp expression.
K sp = (4 x 1(T9) (12 x 10‘ 9 ) 3 = 6.9 x 10' 3 3

EXERCISE 3.7 The total number of ions in 5 L saturated solutions of SrC r0 4 at 25°C is 3.6 x 1022.
What is the solubility product, Ksp, for S rC r0 4 ? 3.6x10°

3.4 CALCULATIONS FROM Ksp

3.4.1 CALCULATION OF SO LU B ILITY

If the solubility product for a com pound is known, the solubility o f the com ­
pound can be calculated easily as illustrated in the following examples.

EXAMPLE 3.10 Calculation of Solubility

Problem : Barium carbonate, B aC 03, has a solubility product of 1.6 x 10' 9 at 25°C. Find the solubility of
B aC 0 3 in (a) mol/L (b) g/L. B aC 0 3 = 197 g/mol
Solution : (a) (1) Write the equation for the dissolution reaction of B aC 03, and its Ksp expression
B aC 0 3 (s) Ba2+ (aq) + CO2- (aq) Ksp = [Ba2+] [C 02~ ] = 1.6 x 10" 9
(2) Let s be the solubility of B aC 0 3 in mol/L. If s mol of ВаСОз is dissolved in 1 liter, s mol/L of Ba2+ and s
2—
mol/L of C 0 3 ions are formed.
H e re w e do n o t s u g g e s t th a t
B aC 0 3 (s) Ba2+ (aq) + C0^~ (aq) the c o n c e n tra tio n o f B a C 0 3 is
s mol/L <—- x mol/L s mol/L s m o l/L , in ste a d , o n ly th a t s
(3) Substitute the ion concentrations into the Ksp expression and solve the m o le o f so lid B a C 0 3 d isso lv e s
to p ro d u c e sa tu rated solu tio n .
equation fof s.
Ksp = [Ba2+] [CO2' ] -> (s) (s) = s2 = 1.6 x 10"9
Taking the square root of both sides gives that the molar solubility of B aC 0 3 at 25°C is 4 x 1СГ5 mol/L.
(b) To calculate the mass of ВаСОз in one liter of saturated solution, we convert moles of ВаСОз into grams.
Mass of ВаСОз = n x MW of ВаСОз = 4 x 10' 5 mol/L x 197 g/mol = 7.88 x 10' 3 g/L.

EXERCISE 3.8 Given that silver chloride, AgCl, has a solubility product of 1.7 x 10"’° at 25°C. Cal­
culate the solubility of AgCl (a) in mol/L (b) in g/L. AgCl = 143.5 g/mol. ( a ) l . 3 x l 0 ' s mol/ L,
(b) 1 . 9 x l 0 ' 3 g/L

EXAMPLE 3.11 C alcu lation o f Ion C oncentration

Problem : Calculate the concentration of I 0 3 in a saturated solution of La(I0 3 ) 3 for which Ksp= 4.32x10"’° at
a given temperature.
Solution : Let s be the number Of moles of L a(I0 3 ) 3 that dissolves per liter. This forms s moles of La3+ and
3s moles of I 0 3. Thus the equilibrium concentrations are :
La(I0 3 ) 3 (s) < = ^ La3+ (aq) + 3I0 3 (aq) • Ksp = [La3+] [Ю 3 ] 3
At equilibrium s mol/L s mol/L 3s mol/L
Substituting these into the Ksp expression, we get
4.32 x 10"’° = (s) (3s) 3 = 27s4 and s4 = 1.6 x 10'” mol/L => s = 2 x 10‘ 3 mol/L
Since the concentration of Ю 3 is asked, which is 3s we get [ I0 3 ] = 3 x 2 x 10" 3 M = 6 x 10" 3 M.
rrfmfiiniiiiimrrffiriiiiniiiiimiimMiiiiiiHmnfnmtiiniMiininitimnnmtHiiiiiriiiimiiiinnTfitnmmninmmnimfliimnrnm Solubility Equilibria 103

EXERCISE 3.9 Ksp for lilhium carbonate, Li2 C 0 3, is 4 x 10“ 3 at a certain temperature. How many
grams of Li 2 C 0 3 will be dissolved in 250 mL of saturated solution? Li2 C 0 3 = 74 g/mol 1.85 g

EXAMPLE 3.12 Calculation on the Solubility of a Slightly Soluble Solid

Problem : How many liters of water are needed to dissolve 9.22 grams of Pbl2 for which Ksp = 4 x l0 “ 9 at
25°C ? Pbl 2 = 461 g/mol
Solution : Using the usual procedure, let us calculate the solubility of Pbl2 in grams per liter. Let s be the
molar solubility of Pbl2.
Pbl 2 (s) <=> Pb2+ (aq) + 21" (aq) Ksp = [Pb2+] [Г ] 2
s mol/L s mol/L 2s mol/L
4 x 10“ 9 = (s)(2s ) 2 = 4s3 => s3 = 1 x 10“ 9mol/L = > j = l x 10“3 mol/L

Since the molecular weight of Pbl 2 is 461 g/mol, 9.22 g P bl 2 —» C)'~~ &— = 2 x 10 2mol
461 g/mol
If 1 x 10“ 3 mol of Pbl2 can be dissolved in 1 liter x = 20 L
2 x 10"2 mol of Pbl 2 x liter J

or M = i L - » V = — = 2 x 1 0 .2 _mol_ = 2 QL
V M -3
1 x 10 mol/L

EXERCISE 3.10 How many B" ions will be present in 100 mL of saturated solution of AB3 for which
Ksp = 4.32 x 10“ 18 at 25°C ? 3 .6 x 1 0 18

3.4.2 WILL A PRECIPITATE FORM?

One o f the m ost useful applications o f Ksp is to predict w hether a precipita­
tion will occur when tw o solutions are m ixed. If the ions o f a slightly soluble
I f Q Sp = K sp , so lu tio n is
substance are brought together, three types o f com parisons will be possible.
satu rated
If Q Sp < K Sp, so lu tio n is
1 - I f the ion product or Qsp= Ksp, the system is at equilibrium and the so ­
lution is saturated.
unsatu rated
I f Q Sp > K Sp, so lu tio n is
2 - //Q sp < K sp, the system is not at equilibrium. To establish equilibrium
su p e r satu rated
Qsp m ust increase to the value o fK sp, w hich m eans the concentrations o f ions
are not sufficient to give a saturated solution. Sim ply the solution is unsaturat­
ed.
3 - I f Qsp > K sp. the system is not at equilibrium . To establish equilibrium ,
the value o f Qsp m ust decrease to the value o fK sp, w hich m eans the concentra­
tions o f ions m ust be decreased. To do so ions com bine to give solid. Sim ply a
precipitate w ill be fo rm e d i f Qsp > K sp. The fo llo w in g exam ples illustrate the
subject clearly.

EXAMPLE 3.13 Formation of Precipitation

Problem : Will a precipitate of CaF2 form when 100 mL of 2.0 x 10“ 3 M C a(N 0 3 ) 2 is mixed with 100 mL
of 2.0 x 10' 3 M KF solution? Ksp for CaF2is 4 x 10“ 11 at 25°C
104 Chapter 3 Ш1111Ш11ИШ!Н11Н11И11Ш111Ш111111Ш11Ш1|1ШШШ1И1ИШ1111111111Ш1ШШШШ11И11И1И11Ш11111111111Ш1Ш11Ш1ШШИ1111Ш11ШШ11ШШ111||1||11ШШШШИ

Solution : To solve this problem;

( 1 ) calculate the concentration of the ions in the mixture of solutions assuming no precipitation occurs.
Number of moles of C a(N 0 3 ) 2 = V x M = 0 .1 L x 2 x 10' 3 mol/L = 2 x 10~4 mol.
Number of moles of ions produced by Ca(N 0 3 ) 2 is :
Ca(N0 3 )2 (aq) -> Ca2 +(aq) + 2 N 0 3 (aq)
2xl0 ‘ 4 mol 2xl0 ' 4 mol 4x l0 ' 4 mol
Number of moles of KF = V x M = 0.1 L x 2 x 10' 3 mol/L = 2 x 1СГ4 mol.
Number of moles of ions produced by KF is :
KF (aq) -» K+ (aq) + F" (aq)
2 x l 0 "4mol 2 x l 0 " 4 mol 2 x l 0 ‘ 4 mol

The total volume of the solutibn = 0.1 L + 0.1 L = 0.2 L.

The concentration of ions which will cause the precipitation of CaF2 in the mixture is :

[Ca2+] = — = 2 x 1 0 m o1 = 1 x 10~3M [F~] = — = 2 x 1 0 m o 1 = 1 x 10_3 M.

V 0.2 L V 0.2 L

(2) calculate the value of Qsp or ion product for CaF2 .

CaF2 (aq) Ca2+ (aq) + 2 F (aq)
Qsp = [Ca2+] [F‘ ] 2 = (1 x 1 0 '3) (1 x 10' 3 )2 = 1 x 10" 9

(3) compare the values of Qsp and Ksp. Qsp = 1 x 10’ 9 > Ksp = 4 x 10' 11
We conclude that the reaction should occur in the reverse direction until the concentration of Ca2+ and F '
ions just satisfy Ksp for CaF2.
Shortly since, Qsp exceeds Ksp, CaF2 will precipitate.

EXERCISE 3.11 A 1 0 0 mL volume of 0.04 M Ca(N 0 3 ) 2 solution is added to 300 mL of 0.008M

(NH 4 )?S 0 4 solution. Will C aS0 4 precipitate? Ksp for C aS0 4 is 6 x 10' 5 atequilibrium

EXAMPLE 3.14 Form ation o f a Precipitation

Problem : What must be the minimum mass of solid Ba(OH) 2 which will start the precipitation of Ca(OH) 2
from one liter of 0.01 M CaCl2 solution? Ksp for Ca(OH ) 2 is 9 x 10" 6 at 25°C. Ba(OH ) 2 = 171 g/mol.
Solution : To start the precipitation of Ca(OH) 2 , Qsp must be equal to Ksp.
Ca(OH) 2 (s) Ca2+ (aq) + 20H- (aq) Qsp = [Ca2+] [OH' ] 2 = Кф
Since the concentration of Ca2+ ions in 0.01 M CaCl2 solution is 0.01 M,
~6 -2
(0.01) [ОН' ] 2 = 9 x 10' 6 [OH“f = 9 x 10 => [OH“] = 3.0 x 10 M
0.01
Then if [OH-] > 3.0 x 10' 2 M, Ca(OH ) 2 will precipitate. To supply 3.0 x 10' 2 M OH", the concentration of
Ba(OH ) 2 in thesolution must be just half of [OH"] as it can be found from the equation.
Ba(OH) 2 (aq) -» Ba2+ (aq) + 20H" (aq).
1.5 x 10" 2 M 3.0 x 10" 2 M
n B a (O H )2 = V x M = l L x l . 5 x 10" 2 mol/L = 1.5 x 10' 2 mol.
m B a (O H )2 = n x MW = 1.5 x 10' 2 mol x 171 g/mol = 2.6 g.
If 2.6 grams of Ba(OH ) 2 is added to a 1 liter of 0.01 M CaCl2 solution, Ca(OH ) 2 will just begin to precipitate.
 .... iniiiiiiiMiiiiiiiiiiiiiiiiiiiiiiiiiiniiiiiiii Solubility Equilibria 105

EXAMPLE 3.15 P redicting the F orm ation o f Precipitate

Problem : Suppose we mix 200 mL of 0.80 M KC1 (aq) with 300 mL of 0.01 M AgNC>3 (aq).
(a) Will a precipitate form ?
(b) If so, how many grams of AgCl will precipitate from the solution ? AgCl = 143.5 g/mol
(c) What will be the concentration of each ion after precipitation ? Ksp for AgCl = 1.7 x 10" 1 0
Solution : (a) ( 1 ) Find the number of mole of each ion and the concentrations of ions which belong to the
slightly soluble substance, AgCl.
AgNQ3 KC1
V = 300 mL = 0.3 L V = 200 mL = 0.2 L
M = 0.01 M M = 0.80 M
n AgN 0 3 = M x V = 0.01 x 0.3 = 3x 10' 3 mol n j x i = 0.80 x 0.2 = 0.16 mol
AgN0 3 (aq) -» Ag+ (aq) + NO 3 (aq) KC1 (aq) -» K+ (aq) + С Г (aq)
3x10 ' 3 mol 3xlO "3 mol 3xlO ' 3 mol 0.16 mol 0.16 mol 0.16 mol

The total volume of the mixture is 0.3 + 0.2 = 0.5 L

-3

[Ag+] = — = 3 x -1(- - = 6 x 10 M [Cl“] = — = 0.32 M

VT 0.5 0.5

(2) Find Qsp (ion product) for AgCl

AgCl (s) * = * Ag+ (aq) + С Г (aq) Qsp = [Ag+] [СП = (6 x 10 '3) (0.32) = 1.92 x 1 0 '3

Since QSp = 1.92 x 10_:S > Ksp = 1.7 x 10" 1 0 , a precipitate of AgCl will form,
(b) To find the mass of precipitate, we write the precipitation reaction for AgCl.
Cl ions are in ex ce ss, th en
Ag+ (aq) + C l-(aq) * = * AgCl (s)
p ra c tic a lly all o f A g + io n s
1 mol 1 mol 1 mol
p re c ip ita te , b u t so m e o f Cl~
B efore reaction 3x10 mol 0.16 mol
io n s w ill r e m a in u n re a c te d .
C hange by reaction - 3 x l 0 ' 3 mol - 3 x l 0 ' 3 mol
A fter reaction negligible 0.157 mol 3xlO ' 3 mol

3 x 10"3 mol of AgCl is precipitated.

3 x 10‘ 3 mol AgCl -» 3.0 x 10' 3 mol x 143.5 g/mol = 0.43 g
(c) Let us make a table including the ions, the number of mole of ions and the concentration of ions in the mix­
ture after precipitation.

Ions Moles of ions Concentration of ions K + and NO 3 io n s are sp e c ta to r

Ag+ negligible ? ions. B e c a u se th e y do n o t par-
NO 3 3xlO "3 [NO3 ] = n/V = 3.0xl0" 3 /0.5 = 6x10 ' 3 M tic ip ita te in th e p re c ip ita tio n
r e a c tio n .
K+ 0.16 [K+] = 0.16/0.5 = 0.32 M
СГ 0.157 [С Г ] = 0.157/0.5 = 0.314 M
Even though all Ag+ ions appear to be precipitated in the precipitation reaction, there will be some Ag+ ions
formed from the dissolution of precipitate, AgCl, as shown below. Let.? be the solubility of AgCl.
AgCl (s) < = ^ Ag+ (aq) + С Г (aq)
5 M 5 M s M
106 Chapter 3

Ksp = [Ag+] [СП =» 1.7 x Ю' 1 0 = (s) (s + 0.314)

Since the soiumlity of AgCl is very small, the value of s is expected to be very small, then
0.314 » x or 0.314 + s = 0.314 M
(s) (0.314) = 1.7 x Ю' 1 0 => x = [Ag+] = 5.4 x Ю' 1 0 M
As seen, the concentration of Ag+ ions falls from 6 x 10' 3 M to 5.4 x Ю' 1 0 M after precipitation.

EXERCISE 3.12 Assume that we mix 200 mL of 0.10 M РЬ(Ж )з ) 2 (aq) with 200 mL of 0.5 M NaCl
(aq). If Ksp for PbCl2 = 1.6 x 10' 5
(a) Will a precipitate of PbCl2 form ?
(b) If a precipitate forms, what is the mass of the precipitate ? PbCl2 = 278 g/mol
(c) What are the concentrations of Pb2+ and С Г ions after precipitation ?
(a)Yes (b)5.S6g ( c ) [ A g +] = 7 . 1 x ! 0 ' 4M [С Г ]= 0 .1 5 М

EXAMPLE 3.16 F o rm ation o f a Precipitation

Problem : 400 mL of 5.0 x 10' 5 M A gN 0 3 and 100 mL of Na 3 P 0 4 solutions are mixed. What must be
the minimum concentration of Na 3 P 0 4 solution to initiate the precipitation of Ag3 P 0 4 ? Ksp for Ag 3 P 0 4 is
1.28 x Ю' 2 0 at 25°C.
Solution : To begin precipitation, Qsp = Ksp.
Ag3 P 0 4 (s) <=> 3Ag+ (aq) + PO3' (aq) Ksp = [Ag+ ] 3 [PO3'] = 1.28 x Ю' 2 0
The concentration of Ag+ ions in the mixture of solutions is calculated as follows.
n A gN o 3 = V x M = 0.4 x 5.0 x 10' 5 = 2.0 x 10° mol

AgN0 3 (aq) -> Ag+ (aq) + NO,' (aq)

2 .0 x 1 0 ' 5 mol 2 . 0 x 1 0 ' 5 mol 2 . 0 x 1 0 ' 5 mol

The total volume of the mixture = 0.4 L + 0.1 L = 0.5 L.

|..\g ' | = ПдР = 2 -° x 1 0 . nu)l = 4 x 1 0 ~ 5 M.

VT 0.5 L
Substituting [Ag+] into the Qsp expression gives
1.28 x 10' 2 0 = (4 x 10' 5 ) 3 [PO3-] => [PO3'] = 2 x 10' 7 M.
2 x 10' 7 M is the concentration of P043' ions or Na3 P 0 4 in 500 mL mixture.
The concentration of Na 3 P 0 4 in 100 mL original solution is
Morig x Vorig= Mmix X Vmix => Morig X 100 = 2 x 10* 7 x 500 => Morig = 1.0 x 10' 6 M
Consequently, if the concentration of Na3 P 0 4 is 1.0 x 10' 6 M, Ag3 P 0 4 will precipitate.

EXERCISE 3.13 Equal volumes of 2 .8 x l 0 ' 4 M Pb(N 0 3 ) 2 and an unknown concentration of KI solu­
tions are mixed. What must be the maximum concentration of KI solution not to precipitate Pbl 2 for which Ksp
is 1 .4xl0 ' 8 ? 2 x l 0 '2 M
...... ■
■1i 1 i 1 s............... -...... 1Щ Щ...........'..... .
EXAMPLE 3.17 Calculation of Ksp
Problem : 500 mL of 5 x 10' 4 M P b(N 0 3 ) 2 solution is added to 500 mL of 9 x 10' 4 M Na 2 S 0 4 solution.
If the concentration of SO2 ' ions is five times greater than the concentration of Pb 2 + ions after precipitation,
what is the solubility product for PbS04?
Solution : Both Pb(N 0 3 ) 2 and Na2 S 0 4 are soluble substances.
Then the concentration of Pb2+ or SO 2 ' ions is equal to the concentration of Pb(N 0 3) 2 and Na2 S 0 4 solutions.
Pb(N 0 3 ) 2 (aq) -> Pb2+ (aq) + 2N0 3'(aq) Na2 S0 4 (aq) -> 2Na+ (aq) + SO2 ' (aq)
5 x 1 0 '4 M 5x 10'4 M 9x 10’4M 9x 10'4 M
1!Ш1Ш1111|ГШШ11111111Ш1М11||1!1М!1|111|1Ш1Ш11111ШШ1Ш11!1Ш111111Ш1111111111МШШМММ1!Ш1Ш11ШШШ!1Ш11Ш11|||1!ШШ1Ш SolllbiUty EquiUbHCC 107

Aftermixing, [Pt/*] = ° ’5 Lx 10 M = 2 .5 x lo " * M , [SO^] = ° '5 Lx 10 M = 4 . 5 x 10'4M

Now, let us write the equation for precipitation reaction.

Pb2+ (aq) + SO2 " (aq) <—? PbS0 4 (s)

Initial conc. 2.5 x 10" 4 M 4.5 x 10" 4 M -
Change in cone - x M______________ - x M__________
Conc. at eq. (2.5 x 10" 4 - x) M (4.5 x 10" 4 - x) M rcr>2. _
. „ч _ ( л <r v in - 4. _ v 4 [SO24 " ] is 5 times greater than [Pb2+]J
5 x (2.5 x 10’ 44 - x) = (4.5 x 10" 4 - x) 6

Solving this equation for x gives 2 x 10" 4 M.

The concentrations at equilibrium are :
[Pb2+] = 2.5 x 10’ 4 - 2 x 10" 4 = 5 x 10" 5 M , [SO2 "] = 4. 5 x 10" 4 - 2 x 10" 4 =2.5 x 10’4 M
The value of the Ksp is :
IQp = [Pb2+] [SO2 ' ] = ( 5 x 10 ) (2.5 x 10" ) => Ksp = 1 .25x10

EXAM PLE 3 .1 8 C a lc u la tio n o f Ksp

Problem : We have two salt solutions of barium. The concentration of Ba2+ ions in each solution is equal to
each other. 1.02 x 10" 4 mol of Na 2 C 0 3 is added to one of these solutions and 0.2 mol of KFto other one. The
volume of each solution is one liter. If the mass of B aC 0 3 and BaF2 is 1.97 x 10" 2g and 0.028 g in each solu­
tion respectively, what is the solubility product for BaF2? Ksp for B aC 0 3 is 1.8 x 10"9 .
B aC 0 3 = 197 g/m ol; BaF 2 = 175 g/mol
Solution : First, we find the initial concentration of Ba2+ ions. Let x be the concentration of Ba2+ initially
and let у be the concentration of Ba2+ or CO2’ ions removed from the solution as B aC 03.
Ba2 + (aq) + C 0 32 " (aq) <—? BaC0 3 (s) T h e m ass o f p re c ip ita te o f В а С О з Is 1-97x10’ g
In itia l : x mol/L 1.02 x 10" 4 mol/L T h en the n u m b e r o f m o le o f В а С О з 1S:
C hange : -1 x 10'4 mol/L_____ -1 x 10" 4 mol/L +1 x 10'4 m ol 1 .9 7 x l0 “ g , in4 .
v =----------------^ - = 1x 10 m o l
At Eq. : (x - 1 x 10"4) mol/L 2 x 10" 6 mol/L 1 9 7 g /m o l
Ksp = [Ba2+] [C 032-] —4
2+ 2— 1x10 mol -4
(x- 1 x 1 0 " 4) ( 2 x 1 0 " 6) = 1 . 8 x 1 0 " 9 [Ba ] = [C 0 3 ]=y =1x10 M
(x- 1 x 10" 4) = 9.0 x 10" 4 => x = [Ba2 +]=1.0xl0" 3 M.

We use the initial concentration of Ba2+ to calculate the Ksp of BaF2. Let z be the concentration of Ba2+ re-
moved from solution which will be the mole number of BaF2. T h e m ass o f B a F 2 fo rm ed is 0.0 2 8 g. T h e
Ba2+ (aq) + < = ^2 F "(aq ) BaF2 (s) n u m b e r o f m o le o f B a F 2 is:
In itia l : 1.0 x 10" 3 mol/L 0.2 mol/L 0 .0 2 8 g , , ,
Change : -1 .6 x 10" 4 -3.2 x 10" 4
Z = n BaFo=
2 1 7 5 g /m—o l = 1 .6 x 1 0 m o l
Ar eq. : 8.4 x 10" 4 mol/L -0.2 mol/L S ince th e-v o lu m e is 1 L, [B a 2+]= 1 .6 x lO ’4M ,

Ksp = [Ba2+] [F" ] 2 and [F~] = 3 .2 x l0 ‘4M .

Ksp = (8.4 x 10"4) (0.2) 2 = 3.36 x 10" 5
Ksp for BaF 2 is 3.36 x 10" 5
108 Chapter 3 1111.... Mil...............ШНМН1НИИ1........ МММ.............................. IMM................. MMMI...........................MMIMI

3.4.3 S ELE C TIV E P R EC IP ITA TIO N

In som e cases it is desirable to rem ove som e ions from a solution w hile
leaving other ions in the solution. C onsider a solution containing Cl- and I-
ions. W hen we exam ine the solubility products table we w ill see that both
A gCl and A gl are slightly soluble substances. K sp(AgCl) = 1.7x 10 " 10 and
K sp(AgI)=8.5xlO~17. The solubility products show that A gl is less soluble than
AgCl. If A g N 0 3 solution is slowly added to the solution containing I- and Cl-
ions, first A gl will begin to precipitate first. By keeping [Ag+] w ithin a certain
range, it is possible to let ju st A gl precipitate, later the precipitate form ed is fil­
tered out, the clear solution now contains Cl- ions only. T he follow ing exam ­
ples illustrates the subject best.

EXAM PLE 3.19 Selective Precipitation

Problem : Solid A gN 0 3 is added to a solution containing 1.0 x 10" 3 M each of Cl- and I- ions. What must
be the minimum and maximum concentration of Ag+ ions just to precipitate I- as Agl?
Solution .'L et us calculate the minimum concentration of Ag+ to start the precipitation of Agl.
Agl (s) Ag+ (aq) + Г (aq) Ksp = [Ag+] [П = 8.5 x IO" 1 7

-17
-3 t S S у 1 ft -M
To start precipitation Q sp= K sp fi ] = 1 x 10 M => [Ag ] = —-------------= 8.5 x 10 M
1 x 10~3

Then if [Ag+] >8.5 x 10' 1 4 M, Agl will begin to precipitate. Let us calculate the minimum concentration of
Ag+ ions to start the precipitation of AgCl.
AgCl (s) Ag+ (aq) + СГ (aq) Ksp = [Ag+] [СГ] = 1.7 x IO" 10
-io
[Ag+] = 1 /7 x 10 = 1.7 x 10 M.
1 x 10~3

If [Ag+] > 1.7 x 10" 7 M, AgCl will precipitate too.

Thus, 8.5 x 10" 14 < [Ag+] < 1.7 x 10" 7 is needed to precipitate I- only as A g l.

EXAM PLE 3.20 Selective Precipitation.

Problem : A solution contains 1 x 10" 2 mol/L Cl- and lxlO " 3 mol/L CrO 2 "ions. Solid A gN 0 3 is added to
this solution. What will be the concentration of Cl- ions,in one liter solution when the precipitation of
Ag2 C r0 4 starts? Ksp for AgCl = 1.7 x 10" ! 0 and Ksp for Ag2 C r0 4 = 1.6 x 10' 1 2 (Assume that addition of A gN 0 3
does not change the volume)
Solution : When solid A gN 0 3 which provides Ag+ ions is added, AgCl begins to precipitate when the prod­
uct of [Ag+] and [СГ] is equal to Ksp for AgCl.
-to
That is, [Ag+] [СГ] = 1.7 x IO" 1 0 => [Ag+]= L? * = 1.7 x 10" 8 M.
1 x 10~2
 llllllillllllllllllllllllllllllllllllllllll!!llllllll!l!l!ltillll!llllllllllliilllilllll!li!llllllll!l!lllllllllllli!lllllllllllllllll!IIIIIIIIIIIIIIIIIIIIIIIII|

If the concentration of Ag+ ions is 1.7 x 10" 8 M, AgCl starts to precipitate. Even though the Ksp for Ag 2 C r0 4
is smaller than the Ksp for AgCl, the precipitation of Ag 2 C r0 4 will not still take place. For the precipitation of
Ag2 C r0 4, the concentration of Ag+ ions must be :

-12

[Ag+ ] 2 tCrC^" ] = 1.6 x IO" 1 2 => [Ag+ ] 2 = 1 -6 x l ° — = 1.6 x 10" 9 =» [Ag+] = 4 x 10" 5 M
1 x 10~3

Ag2 C r0 4 does not precipitate until the [Ag+] is 4 x 10" 5 M

Therefore, at the start, AgCl will precipitate. Addition of Ag+ causes silver chloride to precipitate and decreases
the concentration of Cl~ ions. To continue the precipitation of AgCl, we must add more Ag+ ions. At last the
concentration of С Г ions is so small that we have to add some more Ag+ to the solution. Finally the concentra­
tion of Ag+ will be 4x 10" 5 M. At this point Ag2 C r0 4 starts to precipitate. The concentration of С Г ions when
Ag2 C r0 4 begins to precipitate is:
[Ag+] [СГ] = 1.7 x IO' 1 0 => (4 x IO"5 ) [СГ] = 1.7 x IO" 1 0 => [СГ] = 4.25 x IO" 6 M

EXERCISE 3.14 A solution contains 0.001 M of each of Ba2+ and Ca2+ ions. In what range must the
concentration of CrO2 ' ions be kept to precipitate Ba2+ effectively, but not to precipitate any Ca2+ ions. Ksp
for B aC r0 4 =2x1 O' 1 0 , Ksp for CaCrO 4 = 7 x l0 " 4. 2 x l0 '7<, [CrO$']< 7 x 1 0 ''M
- - - -• ■ ................

3.5 THE CO M M O N -IO N EFFECT

The solubility o f a negligibly soluble substance is sharply decreased by the

presence o f another solute that produces one o f the ions o f negligibly soluble
T h e so lu b ility o f a so lid
m ay b e d e c re a s e d by a d ­ substance in the solvent. This effect is know n as common-ion effect. This
d ing a n o th e r so lid (or so ­ result can be obtained by applying Le Chatelier's Principle to solubility equili­
lu tio n ) th at has an ion in bria. C onsider the equilibrium represented by the equation :
c o m m o n w ith the solid.
M g(OH ) 2 (s) Mg2+ (aq) + 2 0 H ' (aq) Ksp = 1.5 x 10 " 11
If either M g2+ or OH- is added to the reaction m edium , the equilibrium will
be shifted tow ard left. In other words, M g2+ and OH" com bine to give solid
M g(OH)2 ; or the am ount o f M g(O H ) 2 dissolved is decreased by the presence o f
any o f M g2+ or OH- ions. This is illustrated in the following example.

EXAM PLE 3.21 Common Ion Effect

Problem : Ksp for CaF2 is 4 x 10" 12 at a certain temperature. How many moles of CaF2 can be dissolved
(a) in one liter of water? (b) in one liter of 1 M C a(N 0 3 ) 2 solution? (c) in one liter of 1 M NaF solution?
Solution : (a) The equilibrium will be : CaF 2 (s) < = ^ Ca2+ (aq) + 2F" (aq)
Let ^ be the number of moles of CaF2 that dissolves in a liter saturated solution. When 5 mol/liter of CaF 2 dis­
solves, then according to the equation given above, we would get s mol/L of Ca2+and 2s mol/L of F", Or
[Ca2+] = 5 mol/L, [F"] = 2s mol/L
Substituting these into the K5p expression gives :
Ksp = [Ca2+] [F' ] 2 => 4 x IO" 12 = (s) (2s)2 => 4 x 10" 12 =4.v3 => л- =1х10 " 4 mol/L
110 Chapter 3 ПИШИ! N ............................ «вши.............. 1 Ш Ш Ш Ш ....... III! .... I .......... ........... It ... И Ш Н

(b) Since the solution is М C a(N 03)2. C a(N 0 3 ) 2 will dissolve in water as follows :
1

Ca(N0 3) 2 (s) -> Ca2+ (aq) + 2NO; (aq)

1M 1M 2M
And CaF 2 will establish the equilibrium:
CaF 2 (s) Ca2+ (aq) + 2F" (aq)
If we let x = moles per liter of CaF2 that dissolve to establish the equilibrium, we obtain x mol/L of Ca2 +
and 2x mol/L of F" at equilibrium.
But there is already 1 M of Ca2+ in the solution, therefore the total concentration of Ca2+ will be 1 + x, and
the total concentration of F ' will be 2x.
Ca(N0 3) 2 (s) + 2NO'3 (aq)
2M
CaF2 (s) < > + 2F" (aq)
2xM.
[Ca2+] = (1 + x) M [F‘] = 2 x M
Substituting the concentrations into Ksp expression we get
KsP = [Ca2+] [K ] 2 -> 4 x 10' 1 2 = (1 + x) (2x) 2
We know that x would be equal to the value of s in part (a) if CaF 2 were dissolved in water. In this case the
value of x will be even smaller than s because of the common ion effect. Thus we can safely assume that
x « s = 1 x 1 0 ' 4 and 1 + x = 1
4 x 10' 12 = 1 (2x) 2 => x = 1.x 10' 6 mol/L
Since we defined x to be the number of moles of CaF 2 dissolved per liter of 1 M Ca(N 03)2, then the number
of mole of CaF2 that can be dissolved in 1 M Ca(N 0 3 ) 2 is 1 x 10" 6 mol/L
Since x = 1 x 10"6« 1, x can easily be neglected with respect to 1, then (1 + x = 1) assumption is valid.
If the value of x were very close to 1, then we would not neglect x with respect to 1, and we would solve
the cubic equation obtained from the equation 4 x 10" 1 2 = ( 1 + x) (2x) 2
As you see, the solubility of CaF 2 is (1 x 10'4/1 x IO 6 =) 100 times greater in water than that in
1 M Ca(N0 3 ) 2 (aq)

(c) Using the same principles in part (b) we find the number of mole of CaF2 as follows:
NaF(s) Na+ (aq) +
1M 1M
CaF 2 (s) Ca2 + (aq) +
x M
[Ca2 +] = x M [F"] = ( l + 2 x ) M
4 x 10" 12 = [Ca2 +][F " ] 2 -> 4 x 10" 12 = (x) (1 + 2x) 2 assuming 1 + 2x = 1 gives => x = 4 x 10" 1 2 mol/L
Thus it is found that the number of mole of CaF 2 that dissolves in 1 L of 1 M NaF solution is 4 x 10" 12
Then the solubility of CaF 2 is (1 x 10"4/4 x 10" 1 2 =) 2.5 x 107 times greater than that in 1M NaF (aq).
The comparisonof the results of part a, b, с indicates how effectively a common ion decreases the solubility
of a substance.
Solvent solubility (mol/Li
pure water 1x 1 0 " 4

1 M Ca(N0 3 ) 2 1 x IO" 6
1 M NaF 4x 10" 12
 Solubility Equilibria 111

EXERCISE 3.15 A saturated solution of Ca(OH ) 2 is prepared by using 0.10 M NaOH solution as sol­
vent. What is the molarity of Ca2+ ions in the solution. Ksp(Ca(OH) 2 ) = 1.3 x 10' 6 1.3xl0'4 M

EXAMPLE 3.22 C alculation o f Solubility P rod u ct and C o m m on Ion.

Problem : The solubility of AgCl in 0.20 M NaCl solution is 8.5 x 10" 10 mol/L. Find the solubility prod­
uct of AgCl.
Solution :
NaCl (s) - 4 Na+ (aq) + CT (aq)
0.20 M 0.20 M 0.20 M
AgCl (s) « = » Ag+ (aq) + C l' (aq)
8.5xlO ' 1 0 M 8.5xl0 ' 10 M 8.5xl0 ' 10
Finally in the solution: [Ag+] = 8.5xlO ' ! 0 M [Cl'] = 0.20 + 8.5 x 10' 1 0 = 0.20 M.
Substituting these into Ksp gives : Ksp = [Ag+] [СГ] = 8.5 x 10" 10 x 0.20 = 1.7 x 10" 10

EXAMPLE 3.23 Calculation of Ksp

Problem : 0.248 mg of MgF 2 is the maximum quantity that can be dissolved in 0.5 L of 0.10 M KF. What
is the solubility product of MgF2 ? MgF 2 = 62 g/mol
Solution : First, find the number of mole of MgF2 that can be dissolved in0.5 L of 0.10 M KF solution.

n MgF = 0 - 2 4 8 X 1 0 = 4 X 10 6 mol , |MgFol = 4 x 1 0 ..... m o 1 = 8 x lO ^ M .

2 62 g/mol 0.5 L
Now, write the equation for the dissolution of MgF2.
MgF2 (s) Mg2+ (aq) + 2 F (aq)
8 xl0 " 6 M 8x1 O' 6 M 1.6xlO'5 M
The concentration of each ion in the solution is:
[Mg2+] = 8 x 10'6 M
[F"] = (1.6 x 10' 5 + 0.1) M. (0.1 M F ' comes from KF solution)
Ksp = [Mg2+] [F ' ] 2 = ( 8 x 10'6) (1.6 x 10' 5 + 0.1) 2
1.6 x 10' 5 M is negligible when compared with 0.1 M, so it is cancelled, then 1.6 x 10' 5 + 0.1 = 0.1 M
Hence Ksp = ( 8 x 10'6 ) x (0.1) 2 = 8 x 10' 8

EXERCISE 3.16 The solubility of BaS 0 4 is 3.0 x 1 0 '8 mol/L in 0.05 M Na 2 S 0 4 solution. What is
the solubility product constant for B aS 04? 1.5x10"9

EXAMPLE 3.24 C alcu la tion K sp and C om m on Ion Effect

Problem ;T he solubility of ВаСОз in 0-05 M BaCl2 solution is 3.2 x 10' 8 mol/L. What isthe solubility of
ВаСОз in pure water ?
Solution : First of all, we should find the Ksp for ВаСОз.Since we know thesolubility of ВаСОз in
0.05 M BaCl2, we may find the Ksp as follows :
BaCl2 (aq) 2СГ (aq)
0.05 M 0.1 M
ВаСОз (s) C 0 32- (aq)
3.2xl0 ' 8 M 3.2xl0 ' 8 M
112 Chapter 3 lllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllillN lllllllllllllllllllilllM I II I IM II II I II IllI II II II

The concentrations of ions in equilibrium are :

[Ba2+] = 0.05 + 3.2 x 10' 8 = 0.05 M , [CO|“ ] = 3.2 x 10' 8 M
Now, substituting the values for the equilibrium concentrations into the Ksp expression gives
Ksp = [Ba2+] [COf~ ] = (0.05) (3.2 x IO'8) = 1.6 x IO' 9
To find the solubility of ВаСОз i° Purc water, we follow the usual way as shown below.
B aC 0 3 (s) <=> Ba2+ (aq) + COf"(aq)
x mol/L x mol/L x mol/L
Ksp = [Ba2+] [COf~ ] -» 1.6 x 10' 9 = (x) (x) = x2
Taking the square root of both sides gives :
x = [ВаСОз] = 4 x 1O' 5 mol/L

E X E R C I S E 3 . 1 7 The mass o f Р Ь О г that can be dissolved in 500 mL of 0.2 M NaCl solution at a cer­
tain temperature is 0.1112 g. What is the mass of РЬС1г that can be dissolved in (a) 5 L pure water ? (b) 2 L of
-0.5 M Р Ь(Ю з)г solution ? (c) 500 mL of 0.5 M ВаС1г solution ? РЬС1г = 278 g/mol
(a)27.H g (b)2.224 g (c )4 .4 5 x I0 3 g

EXAMPLE 3 .2 5 Ion Concentration After Precipitation

Problem : Suppose that 100 mL of 0.1 M A gN 03and 50 mL of 0.20 M KBr solutions are mixed. What
should be the final concentrations of Ag+ and B r' ions ? Ksp for AgBr = 2.5 x 10"b
Solution : First let us decide whether precipitation occurs. To do so, we will find the value of Qsp assuming
no precipitation occurs.
n A gN 0 3 = V x M = 0 .1 L x 0 .1 mol/L = 0.01 mol A gN 0 3

AgN0 3 (aq) -> Ag+ (aq) + N03' (aq)

0 . 0 1 mol 0 . 0 1 mol 0 . 0 1 mol

n K B r = V x M = 0.05 L x 0.2 mol/L = 0.01 mol KBr

KBr(aq) -> K+(aq) + Br‘ (aq)

0 . 0 1 mol 0 . 0 1 mol 0 . 0 1 mol

The total volume of the solution = 0.1 + 0.05 = 0.15 L.

[Ag+] = ° - Q 1 m o 1 = 6.7 x 10_2 M. [Br_] = 0 ' 0 1 m o 1 = 6.7 x 10_2 M.

b 0.15 L 0.151
AgBr (s) < = ^ Ag+ (aq) + Br'(aq)

Qsp = [Ag+] [Br“] = (6.7 x 10'2) (6.7 x IO'2) = 4.5 x IO' 3

Since Qsp = 4.5 x 10v-3 — о s v in-13
' 3 >Ksp = 2.5 x 10' 13 ,then AgBr will precipitate.

Now let us examine whether an excess ion is present, assuming no dissolution of AgBr.

Ag+ (aq) + Br' (aq) <=+• AgBr(s)

Moles at start 0.01 0.01 0
Change by reaction - 0.01 - 0.01 + 0.01
Mol es at equilib 0 0 0.01

Since Ag+ and Br" are being mixed in a proper ratio, the equilibrium system will be the same system as the
system set up by dissolving only AgBr in water.
ii ii ii ii iii ii ii iii ii ii ii iii ii i i i i i j i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i M i i i i n i i i i i i i i H i i i i i i i i i i M i i i i i i i i i n i i i i i i i i i i i i i i i i i t i i i i i i M i i i i i f i i n i i i i i i i i i n i i Solubility Equilibria, 113

Therefore all we do is to solve usual solubility problem.

AgBr (s) Ag+ (aq) + Br" (aq) Ksp = 2.5 x 10" 13
s mol/L s mol/L
2.5 x 10' 13 = [Ag+] [Br‘] = (x) (s) s = 5 x 10“ 7 mol/L
In the final solution [Ag+] = [Br-] = 5 x 10" 7 M

EXERCISE 3.18 Suppose that 40 inL of 0.5 M Pb(N 0 3 ) 2 and 60 mL of 0.5 M KI solutions are mixed.
What will be the concentration of each ion present in the resulting solution? Ksp for Pbl 2 is 8.0 x IO"9 .
[ l ' b 2+J =0 . 0 5 M, [ Г ] - 1 4 x 1 0~4 M, INO'3] - 0 , 4 M , (K*]--0.3M

EXAMPLE 3.26 Io n C o n c e n tra tio n A fte r P re c ip ita tio n

Problem :Suppose that 200 mL of 1 M A gN 0 3 and 300 mL of 0.20 M Na 3 P 0 4 solutionsare mixed. What
will be the final concentration of Ag+ and PO3 ' ions in the resulting solution? Ksp for Ag 3 P 0 4 = 1.28 x IO" 2 0
Solution : Again let us examine whether Ag3 P 0 4 precipitates.
n AgN o 3 = 0.2 L x 1 mol/L = 0.2 mol
The number of moles of Ag+ and NO," ions are 0.2 mol and 0.2 mol respectively.
nNa po = 0.3 L x 0.20 mol/L ■ 0.06 mol
The mole number of Na+ , and PC)] " are 0.18 mol and 0.06 mol respectively.
The total volume of the solution = 0.2 + 0.3 = 0.5 L.
[Ag+] = 0 , 2 mo1- = 0.4 M [P 0 4~] = M>6 mol. = 0 1 2 м .
B 0.5 L 0.5 L
Ag3 P 0 4 (s) 3Ag+ (aq) + P 0 3 '(aq)
Qsp = [Ag+ ] 3 [РОГ ] = (0.4) 3 (0.12) = 7.68 x 10" 3
Since Qsp = 7.68 x 10" 3 >Ksp = 1.28 x 10"2° , Ag3 P 0 4 will precipitate.
Now let us examine whether there is an excess ion after precipitation. Assuming no dissolution of Ag 3 P 0 4
occurred,
3Ag+ (aq) + PO3 ' (aq) Ag3 P 0 4 (s)
M oles at start 0 .2 0 0.06 0

Change by reaction -0.18 -0.06 0.06

M oles after p recipitation 0 .0 2 . 0 0.06
C oncentrations o f ions 0.02/0.5 = 0.04 M.

Now the problem is similar to the one in which Ag3 P 0 4 is dissolved in a solution with a [Ag+] = 0.04 M. Un­
der these conditions the solubility of Ag3 P 0 4 is calculated in the way discussed in Example 3.16.
Ag3 P 0 4 (s) < = ^ 3Ag+ (aq) + P 0 4 '(aq)
s mol/L (3x + 0.04) mol/L x mol/L
Ksp = [Ag+ ] 3 [PO3 " ] => 1.28 x IO" 2 0 = Qs + 0.04)3 (s)
Since x « 0.04, then 3 s + 0.04 = 0.04 1.28 x IO' 2 0 = (0.04)3 (s) => s = 2 x 10' 1 6 mol/L
Then the final concentrations are:
[Ag+] = 0.04 + 3s s 0.04 M and [PO 3 ' ] = j = 2 x 10"1 6 M.
To be sure, substitute these values into the Ksp expression and compare the value of Ksp calculated with the
value of Ksp given.

EXERCISE 3.19 What will be the final concentration of each ion when 100 mL of 0.001 M CaCl2 and
400 mL of 0.025 M Na2 C 0 3 are mixed? Ksp for C aC 0 3 = 4.8 x 10" 9
[ C a 2 * ] = 2 . 4 x 1 0 ~7M , I C 0 3 2 - ] s 2 . 0 x ! 0 ' 2 M, [ С Г ] = 4 х Ю ' 4 M, [ N a + l = 4 x l 0 "2 M
114 Chapter 3 ШМИШШШШШШШИШШНШШППНИННШМШШПННШММПНППННПНИНПНШМПНПНШМИИШШНПНШШШНШШШИМШШНШМИШШШШШШ

SOME NEW TERMS

The common ion effect ; effect of decreas­ Molar solubility is the number of moles of so­
ing the solubility of a slightly soluble substance by lute that dissolves to produce a liter of saturated so­
the presence of common ions of solid derived from a lution.
dissolved salt. For example, NaCl, when added to a Precipitate is solid formed by mixing two solu­
saturated solution of AgCl, produces СГ ions, which tions containing constituent ions of insoluble com­
reduce the solubility of AgCl. Its effect may be de­ pound.
duced by means of Le Chatelier's Principle. Solubility product constant, K sp, e q u ilib ri­
Fractional precipitation ; removal of some um constant that applies to the dissolution of slight­
ions from solution by precipitation while leaving ly soluble solids.
other ions in solution. Qsp is the same as Ksp but the concentrations are not
necessarily equilibrium concentrations.
REVIEW QUESTIONS AND PROBLEMS
Dissolution, Solubility and Solubility Product

3.1 Define the dissolution and solubility and ex­ 3.5 Under what conditions will an equilibrium exist
plain the differences between them. when a negligibly soluble substance is added to wa-
ter?
3.2 (a) Define the terms "soluble", "slightly solu­
ble" and "insoluble" substances. (Refer to Table 5.5 3.6 Write the expression for the solubility product
in Chemistry I Section 5, Page 171 for the solubili­ constant for the solubility equilibrium in water for
ty rules for ionic compounds.) each of the following slightly soluble substances.
(a) aluminum hydroxide (b) lead (II) iodide
3.3 Using the same table mentioned in question (c) silver phosphate (d) calcium oxalate
3.2, differentiate the following substances whether
3.7 Write solubility product constant expressions,
they are soluble or insoluble in water.
Ksp , for the following slightly soluble substances.
(a) NaCl (b) B aS0 4 (c) CaCl2 (d) Mg(OH ) 2
(a) BaF2 (s) < = ^ Ba2 + (aq) + 2F‘ (aq)
(e) K2 S 0 4 (f)PbI 2 (g) Ag2 C r0 4 (h) (NH4 ) 3 P 0 4
(b)P bS 0 4 (s) <=> Pb 2 + (aq) + SO 2 ' (aq)
(c)Sb 2 S3 (s) 2Sb3 + (aq) + 3S 2 "(aq)
3.4 Write the ionic equations representing the disso­
(d) Fe(OH) 3 (s) <=> Fe3 + (aq) + ЗОН’ (aq)
lution of the following soluble compounds in water,
(a) NaOH (s) - 4 (b) BaCl2 (s) -> 3.8 Why does not the concentration term of a solid
(c) A12 (S 0 4 ) 3 ( s ) (d) Pb(N0 3 ) 2 (s) -> appear in its Ksp expression?
3.9 Is an insoluble substance actually insoluble?

Factors That Affect Solubility

3.10 What factors affect the rate of dissolution of silver nitrate in water ?
(a) a solid in water ? (a) increasing temperature t i & r
(b) a gas in water ? (b) crashing AgN0 3 cyrstals ~v
(c) stirring the solution «bw t.
3.11 Explain the effect of each of the following fac­
(d) adding more A gN 0 3 into the solution.
tors on the solubility and the rate of dissolving of
1п111>мш11п1>пш11ш1тшм111ш11ш111111м111п1шмш111шшм1шгм1н1|щпш11№шшпнм1ш11ш1111ш11мим1гм1шш11м|] Solubility Equilibria 115

3.12 For each of the following reactions, decide (b) C 0 2 (g) C 0 2 (aq)
whether the reactants or products have more potential (c) H20 (g) <: H2 0 (1 ) + 10 kcal (е л
- . 2—
energy. (d) Ag2 C r0 4 (s) <= 2Ag+ (aq) + C r0 4~ (aq)
(a) M gC 0 3 (s) <=> MgO (s) + C 0 2 (g) f f o (e) I2 (s) + 1 . 6 kcal - I2 (in alcohol)
(b) 4Fe (s) + 3 0 2 (g) «?=* 2Fe2 0 3 (s) (
(c) N 2 (g) + 3H2 (g) 2NH 3 (g) * 3.14 Given the equation ;0 2 (g) < = Ю 2 (aq)+3 kcal
(d) X e0 3 (s) Xe (g) + 3/20 3 (g) S r* What is the effect of each of the following factors on
the solubility of 0 2 (g) in water ?
3.13 For each of the following reactions, explain (a) Increasing the temperature.
( 1 ) whether the tendency toward minimum energy fa­ (b) Increasing the pressure on the gas.
vors reactants or products, (2 ) whether the tendency
3.15 What should be done (a) to increase (b) to de­
toward maximum randomness favors reactants or
crease the solubility of slightly soluble substance
products.
BaF2 ?
(а) 2СГ (aq) + Pb 2 + (aq) <=> PbCl2 (s)

Calculating The Solubility Product (Ksp)

3.16 The concentrations of Ag+ and S2' ions in the 3.20 8.38 x 10' 4 g of Ag 3 P 0 4 can be dissolved in
saturated solution of Ag2S are 2.0x10 ' 1 7 M and 100 mL saturated solution at most. Calculate the
1.0x10 " 1 7 M respectively. What is the solubility solubility product constant for this substance.
product, Ksp, for Ag2S ? K sp= 4 x l 0 -51 A g 3 P 0 4 = 419 g/mol 4 . 32 x 1 O' 18
3.21 T he fig u re
3.17 A solution of Mg(OH ) 2 in equilibrium with given aside shows
its solid contains 2x l0 " 4 mol of Mg2+ per liter. Cal­ the concentration
culate Ksp for Mg(OH)2. 3. 2x1 O' 11 changes of ions pro­

/jp/w
duced when a negli­
3.18 A 250 mL sample of saturated solution of gibly soluble solid
MgF 2 at 25°C is evaporated to dryness and 31 mg of was dissolved in wa­
solid residue is obtained. What is Ksp for MgF 2 at ter at 25°C. If some
2 5 °C? MgF 2 = 62 g/mol 3.2xl0'8 solid remained in ex­
cess, what would be
3.19 The solubility of C aC 0 3 is 7 x 10 g/L. Cal- the value of Ksp for
culate K sp for C aC 0 3 C aC 0 3 = 1 0 0 g/mol this solid?
4.9x10
1 . 0 8 x 1 O' 3 3
Calculating Solubility From Ksp
3.22 Consider these slightly soluble substances. 3.24 The value of the solubility product constant
(1) Agl Ksp = 8.1 x 10‘ 17 for CaF 2 is 4.0 x 10"12at a certain temperature. What
(2) Ag3 P 0 4 Ksp = 4.32 x IO' 18 is the solubility of CaF 2 in mg per liter?
(3) Ag2 C 0 3 Ksp = 4.0 x 10- 12 C aF 2 = 78 g/mol. 7.8 mg/ L
Which are the most and least soluble compounds?
3.25 if the solubility product constant for Cd(OH ) 2
A g 2C O з a n d A g l
is 3.2 x 10' 1 4 ,
3.23 What is the concentration of each ion present
(a) what is the solubility of Cd(OH ) 2 in mol/L ?
in a saturated solution of Ag2 C 0 3 ? Ksp for Ag2 C 0 3
(b) what are the concentrations of Cd2+ and OH”
is 4.0 x 10" 12
ions?
[ A g +] = 2 x l O ' 4 M, [ C O 2 ' ] = 1 x 1 O' 4M
116 Chapter 3 Н1 ! 1 1 1 Ш 1 ! 1 1 Ш 1 Ш Ш 1 МШ1 1 1 1 Ш 1 1 Ш 1 1 1 1 1 1 1 Ш Ш 1 1 1 1 1 1 1 Ш 1 1 1 1 1 1 1 1 Ш Ш 1 1 1 Ш Ш Ш 1 1 1 | 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 М1 1 Ш 1 Ш 1 М1 1 1 1 1 1 1 1 Ш 1 1 1 1 Ш 1 иМШ 1 Ш Ш Ш Ш 1 1 | 1 1 1 Ш 1 Ш 1 1 1 Ш 1 1 » 1 1 1 1 1 1

(c) what is the total number of ions in 500 mL of ter and shaken, what percent of SrCr0 4 dissolves in
saturated solution ? water by mass?Ksp forS rC r0 4 at 25°C is 1.6xl0"5.
(d) what is the mass of Cd(OH ) 2 dissolved in 500 S rC r0 4 = 204 g/mol. 20 %
mL of solution ? Cd(OH ) 2 = 146 g/mol
( a ) 2 x l 0 ' 5 M ( b) [Cd2 + ] = 2 x l O ' 5 M, What is the maximum mass of Ag+ that can
[ O H ~ ] = 4 x l O ' S M ( c ) 1 . 8 0 6 x 1 0 1 9 ( d ) 1 . 4 6 x 1 O' 3 g exist in equilibrium with 1x10" 3 mol of I" ions in
How many liters of water are necessary to dis­ 500 mL of solution? Ksp for Agl = 8 x 10" 15
solve 1.38 g of Ag2 C 0 3, for which Ksp= 3.2xl0"n at Ag = 108 g/mol 2.16x1 O'10 g
a certain temperature? 25 L
0.59 mg of BiX 3 is used to prepare a 100 mL
How many mL of saturated solution can be saturated solution. Find the atomic weight of the ele­
prepared by using 33.4 mg of CH3COOAg for which ment, X. Ksp for BiX3= 2.7xl0 ' 19 , Bi=209 g/mol
Ksp = 1.6 x IO' 3 ? CH3COOAg = 167 g/mol 5 mL
127 g / m o l
In the saturated solution of Ag 3 P 0 4, the mass
The solubility product constant for B aC 0 3 at
of Ag+ ions is twice the mass of P 0 4 ' ions. What is
25°C is 1.6 x IO'9, what is the number of Ba2+ ions
the mass of PO 3 " ions per liter solution? Ksp for
in 250 mL of saturated solution ? 6.02x1018
Ag3 P 0 4 is 1.8 x IO’18. P= 31, 0=16, Ag=108
If 3.06 g of SrCr0 4 is added to 500 mL of wa- 2 .2 8 x 1 O'3 g

Solubility and Precipitation

What is precipitation? How can you write the (d) 50 mL of 0.04 M C a(N 0 3 ) 2 and 150 mL of
net ionic equation for a precipitation reaction ? 0.008 M Na 2 S 0 4, Ksp(C aS04) = 6 x 10' 5
Yes,N o,N o,N o.
If the aqueous solutions of the following pairs When equal volumes of 4 x 10" 3 M M g(N0 3 ) 2
of substances are mixed, will a precipitate form ? If and 2x10 " 4 M NaOH solutions are mixed, a saturated
yes, write the ionic and net ionic equation for each solution of Mg(OH ) 2 is obtained. Find the Ksp for
reaction. M g (O H )2. 2 x l0 -n
(a) Na2 C 0 3 (aq) + CaF2 (aq) -»
What is the concentration of sulfide ions, S2",
(b) KN 0 3 (aq) + CaCl2 (aq) ->
above which precipitation of Cu2S will take place in
(c) AgN0 3 (aq) + KI (aq)
l x l 0 4 M C uN 0 3 solution? Ksp for Cu2S isl.6 x l0 - 48
(d) BaCl2 (aq) + K2 S 0 4 (aq) ->
1 . 6 x 1 0~4 0
(e) Mg(N0 3 ) 2 (aq) + NaOH (aq) ->
Will a precipitate exist at equilibrium if one
(f) NaCl(aq)+Pb(N0 3 ) 2 ->
liter of 2 x IO" 4 M Ba(N 0 3 ) 2 and one liter of 4 x 10" 5
Ш Is there any difference between Qsp and Ksp?
M Na3 P 0 4 solutions are mixed and diluted to 100 L?
Will a precipitate form if the following vol­ Ksp for Ba3 (P 0 4 ) 2 is 1.3 x IO' 2 9 . No

umes of the indicated solutions are mixed? A solution has a Mg2+ ion concentration of
(a) 100 mL of 4x10 " 4 M A gN 0 3 and 100 mL of 1x10" 4 M. Will Mg(OH) 2 precipitate if
2x10' 4 M NaCl, Ksp(AgCl) =1.7xlO - 10 (a) 4 mg of NaOH is added to a one liter of this solu­
(b) 1.0 L of 1x10" 4 M Na2 C 0 3 and 0.1 mL of tion?
1 x 10’ 2 M CaCl2, K sp (CaC03) = 1 x IO’ 10 (b) 40 mg of NaOH is added to a one liter of this so­
(c) 40 mL of 1 x 10" 2 M BaCl2 and 60 mL of lution? Ksp for Mg(OH) 2 = lxlO " 11 NaOH=40 g/mol
1 x IO' 2 M NaF, K sp (BaFj) = 2.4 x 10' 5 (a)no, (b)yes
 ШШШШШПШШПШШШШШПШШШШШШШШ Ш
1Ш1Ш1Ш Illlllllllll............ШИШ...............1...... Solubility Equilibria 117

3 .4 1Solid barium hydroxide, Ba(OH ) 2 is added to a 46 100 mL of 0.01 M CaBr2 solution is mixed
2 liter solution which contains 3 .9 x l0 '4 g of Zn2+ with 100 mL of 0.01 M AgNCb solution. What are
ions. How many grams of Zn(OH ) 2 precipitate when the concentrations of Ag+ and Br- ions in the result­
the concentration of OH' ions becomes 2x l0 " 6 M in ing solution ? Ksp(AgBr) = 5xl0 " 1 3
the solution? Ksp for Zn(OH ) 2 = 1.0 x 10" 17 [ A g +] = 1 x l 0 ' 1 0 M, [B r- ]= 5 x lO '3M
9.9x10 'sg
What concentration of S2" is necessary to start
3 .4 :’ 3.47 300 mL of 0.01 M F e(N 0 3 ) 2 solution is
the precipitation of FeS from a saturated solution of mixed with 200 mL of 0.1 M NaOH solution. If the
Fe(OH)2? Ksp (FeS)=4xlO“ 19 Ksp(Fe(OH)2 )=4xlO- 15 Ksp for Fe(OH ) 2 is 8 x 10'15,
4 x 1 0 ~14 (a) will a precipitate form ?
3.43 Ksp for B aC 0 3 is l-6xl0"9. How many grams (b) if yes, what is the mass of Fe(OH ) 2 precipitated ?
of solid Na2 C 0 3 must be added to 500 mL of 2x l0 ' 4 (c) what is the concentration of each ion after precip­
M BaCl 2 solution to start the precipitation of itation ? Fe(OH ) 2 = 90 g/mol
B a C 0 3? Assume that the total volume doesn't ( a ) ye s (b ) 2 7 0 mg ( c ) [ N a +] = 4 x l 0 ' 2M ,
change significantly after the addition of solid [ N O j ] = 1 . 2 x 1 O'2 M, [ O H ~ ] = 2 . 8 x 1 O' 2 M,
N a 2 C 0 3. Na 2 C 0 3 = 106 g/mol 4.24xl0'4 g [ F e 2 +] = 1 . 0 2 x l 0~11 M
3.48 Silver carbonate (Ag2 C 0 3) is a slightly solu­
3 .4 4Ksp for PbCl2 is 1.6х10'5. 200 mL of 0.02 M ble substance and has a solubility product of
P b (N 0 3 ) 2 solution is mixed with 200 mL of un­ 9.0 x 10' 1 2 at a certain temperature. If 300 mL of
known concentration of NaCl solution. What must 2 x 10" 2 M A gN 0 3 solution is added to 200 mL of
be the minimum concentration of NaCl solution to 4 x 10' 2 M Na2 C 0 3 solution,
start the precipitation of lead chloride? 0.08 M (a) will a precipitate form?
(b) If so, how many grams of Ag 2 C 0 3 will be
3.45 Equal volumes of 4 x 10"4 M C a(N 0 3 ) 2 and formed? Ag2 C 0 3 = 276 g/mol
unknow concentration of KF solution are mixed. (c) What will be the concentration of Ag+ and
What must the concentration of KF to start the pre­ CQj2' ions after precipitation?
cipitation of CaF 2 ? Ksp for CaF 2 is 3.2 x 10' 11 (a)Yes (b)0.828g ( c ) [ A g +] = 3 . 0 x l O' 5 M,
8 x 1 O' 4 M [C O 2' ] = 0 . 0 1 M

Selective Precipitation

3.49 Using the numerical values of the solubility contains 0.01 M Pb(N 0 3 ) 2 and 0.01 M A gN 03.
product constants, discuss which cations may be (a)Which compound will precipitate first?
— 2— —
used to separate the ions, Cl , C r0 4 , and OH se­ (b)Within what range should the sulfate ion concen­
lectively in a mixture. tration be held to separate Pb 2 + ions from Ag+ ions?
Assume that the addition of K 2 S 0 4 does not change
3.50 Suppose you have a solution containing the total volume. Kspis 2 x l0 ' 8 for P b S 0 4 and is
M g 2+, Pb 2 + , Ba2 + ions. You also have NaOH, 2 x l 0 ' 5 for Ag 2 S 0 4. (a) P b S O 4 will precipitate
NaCl, Na 2 S 0 4 solutions, and a list of solubility- fi rst , ( b ) 2 x l O' 6 < [ S 0 24 ' ] < 2 x l 0 ' 1
product constants of compounds. Suggest a suitable
method to separate each ion from the solution. 3.52 A solution contains 2 x l0 ' 2 M Ba2 + and
lxlO " 3 M Ag+ ions. If chromate ions are added to the
3.51 Solid K 2 S 0 4 is added slowly to a solution that solution gradually,
118 Chapter 3 НШ
НННННПШ
ШШНШ НИШ НИШ
И IIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIII............1...1111.... И....... ..... IIIIIIII...... I.........Ill

(a) which cation precipitates first? What must be the 3.53 0.1 M AgN0 3 solution is added qradually to a
concentration of chromate ion to start the precipita­ solution which contains 0.1 M each of С Г and Br“
tion? ions. If Ksp for AgCl is Ksp = 1 x IO" 1 0 and Ksp for
(b) What must be the concentration of chromate ion AgBr is 5 x IO 13,
to start the precipitation of the second cation? (a) which salt precipitates first ?
(c) What is the concentration of the first cation when (b) what is the concentration of anion for the first
the second cation starts to precipitate? (Ksp for salt when the second salt starts to precipitate ?
BaCr0 4 =8.0xl0"n and Ksp for Ag2 CrO 4 =2.0xl0'12) (c) what is the percentage separation of the anion of
(a) B a 2+, 4 x l O - 9M ( b ) 2 x l O ' 6M ( c ) 4 x l 0 ~5 M the first salt from the other ? (The term "first salt"
means the salt that starts to precipitate first.)
(a)AgBr (b)SxlO' 4 M (c) 9 9. 5%
Common Ion Effect
3.54 What is meant by the common ion ?
3.60 Given that 6.2 x 10' 3 g of MgF 2 can be dis­
3.55 What is the effect of common ion on solubili­ solved in 0.25 L of 0.10 M M g(N 0 3 ) 2 solution. Cal­
ty ? culate Ksp for MgF2. MgF 2 = 62 g/mol 6.4x1 O' 8

3.56 Given the solubility equilibrium for BaS04, 3.61 If the solubility product for B aC 0 3 at 250°C
B aS 0 4 (s) <=* Ba2+ (aq) + SO ^(aq) is 1.6 x IO' 9 , calculate the mass of B aC 0 3 that can
According to Le Chatelier's Principle explain what be dissolved in
happens the solubility of B aS04> when each of, the (a) 500 mL pure water.
following substances is added to the solution. As­ (b) 500 mL of 0.01 M BaCl2 (aq)
sume no volume change. (c) 500 mL of 0.02 M Na 2 C 0 3 (aq)
(a) more B aS0 4 (b) B a(N 0 3 ) 2 (c) Na 2 S 0 4 B aC 0 3 = 197 g/mol
( a ) 3 . 9 4 x 1 O'3 g ( b ) l , 5 7 6 x l 0 ' Sg ( c ) 7 . 8 8 x l 0 ' 6g
3.57 The Ksp for AgCl at a certain temperature is
1 x IO"10. Find its solubility in 3.62 Calculate the mass of PbBr2 that will precipi­
(a) pure water, (b) 0.01 M NaCl, tate when 0.1 mol NaBr is added to 1 L of saturated
(c) 0.01 M A gN 0 3 PbBr2 solution. Ksp for PbBr2 is 4 x 10" 6 ,
( a ) l x l O' 5 m o l / L , ( b ) l x l O ' 8 mol /L, Pb=207g/mol, Br = 80 g/mol. 3.52 g
(c )lx lO '8 m ol/L
3.63 The solubility of N iC 0 3 in 0.05 M K2 C 0 3
3.58 The solubility product for CaF 2 is 3.2 x 10' 11 solution is 3.2 x IO' 6 M. What is the solubilty of
at a certain temperature. What is the solubility of N iC 0 3 in
CaF2, in (a) pure water ? (b) 0.4 M NiCl2 solution
(a) pure water ? (b) 0.01 M CaCl2 (aq) ( a ) 4 x l O' 4 M (b)4xl0' 7 M
(c) 0.2 M NaF (aq) 3.64 The mass of Ag2 C r0 4 that can be dissolved in
( a ) 2 x l0 '4 M (b)2.8xlO'S M ( c ) 8 x l 0 ' 10 M 5 L of 0.04 M A gN 0 3 solution is 3.32 x 10"2 mg.
Find the mass of Ag2 C r0 4 that can be dissolved in
3.59 How many mg of C aS0 4 can be dissolved in (a) 5 L pure water.
500 mL of 0.015 M K2 S 0 4 solution? Ksp for CaS0 4 (b) 5 L of 0.02 M K 2 C r0 4 solution? Ag2 C r0 4= 332
is 1.5 x 10"5. C aS 0 4 =136 g/mol 64 mg (a)0.332 g (b )3.32xl0\2 g
 in n in n ........................... nun ...... ........... Solubility Equilibria 119

M iscellaneous Problems
3.65 The insoluble compound AgCl gives Ag+ and degree of hardness is accepted to be one. Assume that
СГ ions when dissolved in water. 500 mL Ag+ solu­ Terkos's water has a hardness degree of 12.5, and all
tion which contains 5.4xl0 ' 2 mg/mL Ag+ is added to the hardness is due to Ca2 + ions calculate the grams
500 mL СГ solution which contains 1.204xl0'2 of Na 2 C 0 3 necessary to start Ca2+ ions in 100 L of
mg/mL СГ. The precipitation of AgCl continues Terkos's water to precipitate as C aC 0 3 for which
until the reaction reaches the equilibrium at which K sp= l x l O '10. 8.48xl0'3 g
the number of moles of Ag+ is 40 times greater than
the number of mole of СГ ions. What is the solubil­ 3.69 The electrolysis of aqueous solution of MgCl2
ity product for AgCl? AW of Ag = 108, Cl = 35 can be represented by the equations.
1 .6x 1 0 ' 10 Anode : 2СГ -> Cl2 + 2e~
3.66 500 mL solution which contains 0.012 g Ca2+ Cathode: 2H20 + 2e- -> H 2 + 2 0 H '
ions are mixed with 500 mL another solution which How long does it take to start the precipitation of
contains 0.0156 g of CO2' ions. If the mass of Ca2+ Mg(OH ) 2 if 0.10 Amp of electricity is used to elec-
ions is twice the mass of CO2' ions after precipita­ trolyze 1 L of 0.001 M MgCl2 solution?
tion, what is the solubility product for C aC 03? K sp= l x l 0 ' n for M g(OH ) 2 96.5 sec
Ca=40, C=12 , 0=16 1.2x10' 9
2
3.70 The concentration of Cr 4 ions in 400 mL sat­
3.67 A mixture of P b S 0 4 (s) and P b C 0 3 (s) is urated solution of AgCl and Ag2 C r0 4 is 5 x 10' 5 M.
shaken with pure water until a saturated solution is What is the number of Cl" ions in the solution? Ksp
formed. Both solids remain in excess. What is the for AgCl =1.7xlO " 10 and Ksp for
[CQj2' ] in the saturated solution? The values of solu­ A g 2 C r 0 4 = 2 x 1 0 ' 12 2 . 05 x l 017
bility product constants of P bS0 4 and P bC 0 3 are
1 x 1 0 * 8 and 1 . 6 x 1 0 " 13 respectively. 3.71 The solubility product constant for СаСОз is
H int : Since the Ksp of P bS0 4 is much larger 1x10 8 at 100°C. A 5 L saturated solution of СаСОз
than that of P bC 0 3 you can assume that Pb2 + ions is prepared at 100°C. If the solution is cooled to
in solution are only produced by PbS0 4 20°C, 20 mg of СаСОз precipitates out of the solu­
1 . 6 x 1 O' 9 tion. Calculate the solubility product constant of
3.68 Water containing Ca 2 + ions is called hard wa­ C aC 0 3 at 20°C. C aC 0 3 = 100
ter. If 100 L of water contain 0.04 g of Ca2+ ions its З.бхЮ ' 9
120 Chapter 3 ШШШПИШШШГШНШМШШШНИШИШИШШИНШШШ .............. н ш ш ш ш п ш и ш п ш ш ............... ш ш н ш ш ш м ш п м

SELF TEST
1. Which one of the following statements is [Y"' change in concentra-
wrong for the equilibrium in the saturated solution tion of ions produced
of Ag 2 C r0 4 ? by the solid versus
Ag2 C r0 4 (s) 2Ag+ (aq) + C r0 4“ (aq) time. Which is the
A) The rate of dissolution is equal to the rate of pre­ solubility product
cipitation. constant of this sub-
2_
B) The concentrations of Ag and C r0 4 ions are ~ s ta n c e ?
ume
constant. A) 4.3 x IO' 38
C) The dissolution of Ag2 C r0 4 no longer continues. B) 7.2 x 10' 29
D) The mass of Ag2 C r0 4 remains constant. C) 2.4 x IO' 29
E) The equilibrium is dynamic. D) 1.2 x IO' 19
E) 4.8 x 10' 39
2. Given the equations :
CO (g) < = * CO (aq) AH = -3.4 kcal 5. Experiments show that 3.5 grams of XY2can be
C 0 2 (g) < = ^ C 0 2 (aq) + 4.8 kcal dissolved in a liter of saturated solution. Which is
I. The randomness increases in both dissolution. the atomic weight of X ? Ksp for XY 2 = 3.2 x 10" 5
II. The dissolutions of both gases are exothermic. Y = 19 g/mol.
III. The tendency toward minimum energy supports A) 260 B) 207 C) 175 D) 156 E) 137
the dissolution of both gases.
IV. The solubility of CO (g) is larger than that of 6 . 74 mg of Ca(OH ) 2 is all that can be dissolved in
C 0 2 (g) under the some conditions. 100 mL solution at a certain temperature. Which is
Which one (s) of the statements given above is (are) the value of solubility product constant for Ca(OH)2?
correct ? Ca(OH ) 2 = 74 g/mol.
A) I and II В) I, II and III С) II and IV A) 5 x 1 0 ' 3 В) 1 x 10' 6 C) 4 x 10' 6
D) II and III E) II, III and IV D) 2 x 10' 4 E) 4 x 10' 5

3. Given the solubility equilibrium for NaHC 0 3 , 7. Ksp is 4 x 10" 9 for Pbl 2 at a certain temperature.
NaH C0 3 (s) Na+ (aq) + HCO3 (aq) AH > 0 Which is the solubility of Pbl 2 in moles per liter ?
I. Increasing temperature increases the solubility. A) 1 x 10' 3 B) 2 x 10' 3 C) 3 x 10" 3
II. Increasing pressure increases the solubility. D) 4 x 10' 3 E) 5 x 10' 3
III. The tendency toward maximum randomness de­
creases the solubility. 8. How many grams of C aS0 4 can be dissolved in
IV. The total potential energy of products is larger 100 L of water at 25°C? Ksp for C aS0 4 = 2.5 x 10'5.
than that of the reactants. Which ones of the state­ CaS0 4 = 136 g/mol *
ments given above are wrong ? A) 0.68 B) 1.36 C) 3.4 D) 6 8 E) 136
A) I and II В) II and III С) I and IV
D) III and IV E) II, III and IV 9. How many grams of PbBr2 are necessary to pre­
pare 250 mL of saturated solution?
4. A slightly soluble solid is added to water until no PbBr2 = 367 gmol"1, Ksp = 3.2 x 10' 5 for PbBr2.
more solid can be dissolved. Figure 3.2 shows the A) 7.3 B) 73 C) 9.2 D) 1.1 E) 1.8
iiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiH iiiiiiiiiiiiiiiiiiiiiiiiin iiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiii Solubility Equilibria 121

10. How many mg of Ag+ per mL is present in a 15. The addition of 10 g of P b(N 0 3 ) 2 to a liter ol
saturated solution of Ag2 C r0 4 for which saturated aqueous solution of PbCl2 will :
KsP= 4xl0"12? Ag = 108 g/mol A) decrease [Pb2+]
A) 4.3 x 10' 3 B) 1.1 x 10' 2 C) 1.0 x 10‘ 4 B) decrease [СГ]
D) 8.4 x 10' 3 E) 2.2 x 10' 2 C) decrease the amount of solid PbCl2
D) have no effect
11. Consider the following silver compounds and E) increase the solubility of PbCl2.
their Ksp's. Which of these is the most soluble in
mole per liter of water? 16. A sample of seawater contains 400 g Ca2 + ions
13
О

per m3. What must be the minimum concentration

1

A) AgBr Ksp = 5
X

о
10
0

B) AgCl Ksp = 2 of PO 4 to start the precipitation of Ca 2 + ions as

X

16
0

Ca 3 (P0 4 ) 2 for which Ksp = 1.6 x 10' 25 Ca = 40

1

C) Agl Ksp = 2
X

12
D) Ag2 C 0 3 Ksp = 8 A) 3 x 10' 7 B) 4 x 10' 17 C) 2 x 10' 2 3
X

E) Ag2S Ksp =: 1 X 10'■49 D) 1 x 10' 19 E) 4 x 10' 1 0

17. Equal volumes of 0.2 M Nal and 0.2 M

12. The solubility product for РЬСОз at 25°C is
P b(N 0 3 ) 2 solutions are mixed. Which is the I' ions
1.6 x 10'15. Which one of the following statements
concentration after the precipitation reaction has
is wrong for 500 mL of saturated solution in which
reached equilibrium? Ksp = 8x10 ' 9 for Pbl2
solid РЬСОз is at equilibrium with its ions ?
P bC 0 3 = 267 g/mol A) 4.0 x 10' 4 B) 8 .9 x 1 0 ' 5 C) 1 .0 x 1 0 3
- 4
A) The concentration of C 0 3 ions in solution is D) 2.6 x 10' 4 E) 8.0 x 10
4 x l0 ' 8 M.
B) The maximum mass of РЬСОз dissolved in solu­ 18. B a S 0 4 (s) is added to water until some solid
tion is 5.34 x 10' 3 mg. B aS 0 4 remains in excess. Later solid B a(N 0 3 ) 2 is
C) The solubility of P b C 0 3 at 25°C is 4 x 10" 8 gradually added to the same solution. Which of the
mol/L. following curves represents best the change in con­
D) The total number of ions in solution is centrations of Ba2 + and SO2 " ions from the begin­
2 .4 x l0 '16. ning of addition of BaS0 4 ?
2+ 2-
E) The concentration of each of Pb and C 0 3 ions
at 50°C is 4 x КГ8 M.

13. Which is the solubility in moles per liter of

Ca(OH ) 2 in 0.5 M NaOH solution?
Ksp = 8 x 10' 6 for Ca(OH)2.
A) 2.1 x 10" 4 B) 3 .2 x 1 0 ' 5 C) 1 .6 x 1 0 ' 5
D) 1.3 x 10' 2 E) 3.0 x 10' 3

14. The slightly soluble solid Fe(OH ) 2 is expected

to be the least soluble in:
A) pure water
B) 0.1 M FeCl2 solution.
C) 0.1 M K N 0 3 solution.
D) 0.01 M Fe(N 0 3 ) 2 solution.
E) 0.1 M NaOH solution.

4
122 Chapter 3 ||М1 !||||Ш 1 1 !||||||Ш Ш 1 М |||||||||П | 1 1 | 1 | 1 1 ! 1 1 1 1 Ш 1 1 Ш || 1 Ш |||Ш |Ш М |||!|||||!Ш |||!!!!||||Н ||Ш |||||||||Ш 1 ||||||||| 1 |! 1 Ш 1 ! 1 Ш ||Ш Ш ||Ш ||||||| 1 !М|1 Ш 1 !||||||!|||||||| 1 !

19. Which will be true when 100 mL of 0.2 M 20. A 100 mL aqueous saturated solution of
A g N 0 3 and 400 mL of 0.5 M K2 S 0 4 solutions are BaC 2 0 4 can react completely with 1.6 mL of 0.01 M
mixed? Ksp = 8 x 10' 5 for Ag2 S 0 4. KM n0 4 solution according to the reaction,
A) The resulting solution will not be saturated with 5C2 042 '(aq) + 16H+ (aq) + 2Mn04'(aq)
Ag2 S0 4 2Mn2 + (aq) + 8H20 (1) + 10CO2 (g)
B) [Ag+] will be 0.04 M Which is the solubility product constant for BaC 2 0 4?
C) [SO2 '] will be 0.38 M A) 1 .6 x 1 0 ' 7 B) 4 .0 x 1 0 ' 5 C) 1 .6 x 1 0 ' 9
D) 0.02 mol of solid will be formed. D) 2.6 x 10" 8 E) 5.2 x 10" 10
E) [K+] will be 0.4 M
 CHAPTER

ACIDS AND BASES

The objectives of this chapter are to enable the student to :

1 - Define and classify electrolytes and nonelectrolytes.
2 - Recognize water as an extremely weak electrolyte with a Kw= 1 x 10'14.
3 - Use pH and pOH notation to express the [H+] or [0H‘].
4 - Define acids, bases in three ways, and describe the similarities and
differences among the Arrhenius, Bronsted - Lowry, and Lewis theo­
ries of acids and bases.
5 - Identify the Bronsted - Lowry conjugate acid - base pairs in a reaction,
and write equations to represent acid - base reactions.
6 - Identify strong acids, strong bases, weak acids, weak bases, and write
ionization constant expressions for weak acids and bases.
7 - Calculate ionic concentrations in aqueous solutions of strong acids,
strong bases and weak acids and weak bases.
8 - Explain the acidity, neutrality, or basicity of salt solutions in terms of
hydrolysis equilibria.
9 - Describe buffer solutions in terms of common ion effect.
10 - Know the technique and theory of titration.
11 - Predict the relative strengths of acids and bases from their molecular
structure.
 Illlllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllliillllllillllllllllllllllllllllllilllllllllllllllilllillllllllllllllllllllililtllllllll! Acids and Bases 125

4.1 ELECTROLYTES

E le c tric iy is c o n d u c te d If the electrical conductivities o f the solutions o f 1 M N aC l, 1 M

b y e le c tro n s in m eta ls K N 0 3, 1 M CH 3 COOH, 1 M N H 3, 1 M C 2 H 5OH and 1 M C 1 2 H 2 2 0 „ are
b u t it is c o n d u c te d by m easured by m eans o f the apparatus show n in Figure 4.1, w e w ill o b ­
io n s in so lu tio n s . serve that NaCl, K N 0 3 solutions conduct electricity very well. The solu­
tions o f N H 3, and C H 3COOH conduct electricity poorly and the solutions
o f C 2 H5OH and C 1 2 H 2 2 O n do not conduct electricity.
In chem istry we classify substances according to the conductivities o f
their solutions. Substances whose solutions conduct electricity are called
electrolytes. E lectrolyte substances produce ions in their aqueous so-
lutions.T hen N aCl, K N 0 3 N H 3, and CH 3C O O H are electrolytes. The
(a) strong electrolyte term s strong and weak are used to distinguish qualitatively betw een elec­
trolytes. NaCl and K N 0 3 solutions conduct electric current well, they are
called strong electrolytes. T he solutions o f N H 3, and C H 3C O O H
conduct electric current poorer because these substances dissociate into
ions only to a sm all extent. H ence these are called weak electrolytes.
The solutions o f C 2 H5OH or C 1 2 H 2 2 O n do not conduct electric current b e­
cause these substances do no t dissociate into ions in water. Such sub­
stances are called nonelectrolytes.
It is im portant not to confuse the relative solubility o f an electrolyte
w ith its strength. F or exam ple the substances cited above are all soluble
in water. But they are in different groups o f substances.Г/ге strength o f
an electrolyte is directly proportional to its ability to separate into ions,
but not to its ability to dissolve. T he nonelectrolytes w hen dissolved in
w ater separate into neutral molecules.
FIGURE 4.1 Equipment for
demonstrating the conductivity
of solutions 4.2 WATER AS A WEAK ELECTROLYTE
(a) A strong electrolyte solution
contains a large number of ions
and the lamp is brightly lit. The precise m easurem ent o f the conductivity o f the pure w ater reveals
(b) A weak electrolyte solution
that w ater does conduct electricity to an extrem ely sm all extent. T h ere­
contains a sm all num ber o f
ions, and the lamp is dimly lit. fore w ater can be classified as an extrem ely w eak electrolyte. Then ju st a
(c) A nonelectrolyte solution small fraction o f w ater molecules dissociates into hydrogen, H+, and hy­
does not contain ions. The lamp
is not lit. droxide, O H ' ions. The equilibrium betw een these ions and undissociat­
ed w ater molecules m ay be represented by the equation.

H 2 0 (1 ) ^ H+ (aq) + O H '(a q ) ДН = +13.6 kcal

The equilibrium constant for this reaction is called the ion product
of water and represented by Kw (Kwater). T he ion product o f w ater is
[H+] [OH '] = £ w
The value o f K w is lx lO ' 14 at 25°C but it increases as the tem perature
o f w ater increases. See Table 4.1.
126 Chapter 4 мииш ш ш ш мш м м ш ш пш им м ш нш м ш ш ш нм м м пш ш ипш ш иш ш ш ш ш нш ш ш ш ш ш пм ш пш ш ш ш ш ш иим ш иш ш ш ш ш ш ш ш ш нм

TA B LE 4.1
at various temperatures
FIGURE 4.2 In aqueous so­
Temperature Kv
lutions [H +] and [O K ] vary in-
versly so that their product is
o °c 1.5 X 1 0 ' 15
25°C 1 .0 X 1 0 '
•14
always 1 x 10'14 at 25°C.
50°C 5.5 X 10'•14
100°C '5.5 X 10' 13

EXAMPLE 4.1 Calculating Hydronium and Hydroxide Ion Concentration of Water

Problem : Calculate (a) the [H+] and [OH'] in pure water at 25°C. Kw = lxlO ' 14 (b) percentage ionization
o f water.
Solution : (a) One liter of water nearly weighs 1000 g. So the mole number of water is
1000 g / 18 g/mol = 55.5 mol
Let x be the number of mole of water molecules that dissociate into H+ and OH" to establish the equilibrium in
one liter of water at 25°C.
H20 (1) < = ^ H+ (aq) + OH“ (aq) Kw = [H+] [OH']
At start : 55.5 mol — —
Changes :_____________- x mol__________ x mol______x mol
At eq. (55.5-x) mol x mol x mol
Substituting the equilibrium concentrations into Kw expression gives lxlO ' 14 =x2 => x = lxlO " 7 So
In p u re w a te r [H+] = [OH“ ] = 1 x 10' 7 M

(b) The percentage ionization is : (1 x 10 ' M/55.5 M) x 100 = 2 x l 0 9 M o r 2 x лl-90 v %

EXERCISE 4.1 The concentration of H+ ions in household ammonia cleaning solution is 4x1 O' 1 2 M.
Calculate the concentration of H+ ions in the solution. 2 . 5 x l O ' JM
_________

4.3 HYDRONIUM OR HYDROXONIUM ION,

h 3 o ^ ™ 1

Hydrogen ion, H+, is a lone proton. B ecause o f its very sm all size and
quite high positive charge, hydrogen ions are surrounded by negative
charge centers o f w ater m olecules. Thus, hydrogen ions in w ater are in
[Н $ О Ш ]+ or H 3 0 + ion the fonm o f [H(H 2 0 ) n]+, which is called hydronium or hydroxonium
ion. Here n shows the num ber o f w ater m olecules surrounding a hydro­
gen ion. R ecent evidence suggests that the value o f n = 4, corresponding
a form ula H+(H 2 0 ) 4 or H 9 O 4 . See Figure 4.3. H ow ever in general we
shall speak o f the hydrogen ion and use the sym bol H+, or H30 + in ter­
changeably, but keep in m ind that experim ents favor the form ula H 9 O4 .

Hydronium ion
Ш1Ш11Ш111Ш1ШШШ1ШШ1Ш1ШШШ1ШШШ1ШШШ11Ш!11Ш11ШШШ11ШНШМШ11ШШ111ШШШШШ11111ШШ1Ш11ШШ!ШН Acids and Bases 127

[H+] = a X 10'" => pH = n - toga 4.4 pH and pOH

If a = 1 => pH = n or
If p H = n => [H +] = 1 0 'n The concentrations of H+ and OH- in aqueous solutions are very small
exponential numbers in general. To express the [H+] and [OH"] of a solu­
tion a more convenient way was developed by Soren Sorensen in 1909.
He defined pH as the negative logarithm of the [H+] of the solution. Or
pH = - lo g [H+]
In pure water [H+] = 1 x 10' 7 M and pH = -lo g 10" 7 = 7
pOH is defined as the negative logarithm of the [OH- ].

pOH = - l o g [O H -]
The pOH of pure water is
pOH = -lo g [OH'] = -lo g IO" 7 = 7 pOH = 7
for a given solution,
FIGURE 4.4 The sum o f pH and pH + pO H =14
pOH o f an aqueous solution is 14. The same result may be obtained by using the formula above.

EXAM PLE 4.2 C a lc u la tio n o f pH

Problem : Calculate the pH and pOH of the solutions given below.
a) A solution with a [H+] = 1 x 10'* M log 1 = 0
b) A solution with a [H+] = 1.5 x 10" 3 M log 1.5 = 0.18
c) A solution with a [OH"] = 3 x 10" 4 M log 3 = 0.48
d) A solution with a [OH'] = 9 x 10" 1 2 M log 9 = 0.95
Solution :
(a) pH = -lo g 1 x 10"x pH = - (log 1 + log 10'*) = - (0 - x) = x
pH + pOH = 14, pOH = 14 - p H -) p O H = 14 - x
(b)pH = -lo g (1.5 x 10"3) = 3-log 1.5 = 3 - 0 .1 8 = 2.82 -> pOH = 14 - 2.82 = 11.18
(c)pO H = -lo g (3 x IO"4) = 4-log 3 = 4 - 0.48 = 3.52 -» pH = 1 4 -3 .5 2 = 10.48
(d)pO H = -lo g (9 x 10"12) = 12-log 9 = 1 1 .0 5 -) pH = 14 - 11.05 = 2.95

EXERCISE 4.2 A sample of vinegar has a pH of 3. Calculate the [H+], [OH- ], and pOH of the solution.
lx lO '3, l x l O ' 1 1 , 11
---
EXERCISE 4.3 Lemon juice has a hydrogen ion concentration of 4 x 10' 3 M. Calculate the [OH"], pH,
and pOH of the lemon juice, log 4 = 0.6 2 . 5 x l 0 ' 12 M, 2.4, 11.6

4.5 ACID-BASE THEORIES

4.5.1 A RRHENIUS A CID-BASE THEORY

Arrhenius *defined an acid as a substance that produces H + ions, and a base

as a substance that p ro duces O H " ions in aqueous solution. HC1, H N 0 3,
* S v an te A u g u st A rrh e n iu s (1 8 5 9 -1 9 2 7 ). A S w ed ish C h em ist, m ak in g im p o rta n t c o n trib u tio n s to the stu d y o f e le c ­
tro ly te so lu tio n s a n d ra te s o f re ac tio n s. H e w as aw arded the N o b el P rize in C h e m istry in 1903.
 128 Chapter 4 ПШШНШНШШНШШИШШШПШШШШШШИИИШИШ II1IIIIIIIIIIIII Illllllllllll Illlllllllllllllllllllllllll ........

[ H +] [ O H ] pH pO H C H 3C O O H are exam ples o f acids. These substances produce

IO '14 10'° 14 0
H+ o r H 3 0 + ions in aqueous solutions according to the reactions:
В 10‘13 IO '1 13 1
Л t o - 12 IO'2 12 2 н а + н2о н3о+ + a*
s 1 0 '11 10-3 11 3 H N 0 3 + H 20 -» H 3 0 + + NO"
E t o - 10 10'4 10 4
CH3COOH + H20 <=> H 3 0 + + C H 3 COO"
10-9 t o -5 9 5
Since H + ions are produced by acids, therefore the [H30 +] o f an
IO'8 IO'6 8 6
Neutral Н Г 7 IO'7 7 acid solution is greater than 10 " 7 M or p H o f an acid solution is
W
10'6 10-8 6 8 less than 7.
10‘5 10-9 5 9 N aO H , B a(O H )2, N H 3 are com m on exam ples o f bases. T hese
Л IO'4 t o 10 4 10 substances produce OH- ion in aqueous solutions according to
С 10'3 to - 11 3 11 the reactions:
I 10‘2 n r 12 2 12 N aO H (s) -> Na+ (aq) + OH’ (aq)
D I O '1 t o 13 1 13
Ba(OH ) 2 (s) -> Ba2+ (aq) + 2 0 H ‘ (aq)
10"° t o - 14 0 14
N H 3 (g) + H 20 (1) < = * N H 4+ (aq) + O H ' (aq)
FIGURE 4.5 The relationships
In base solutions [OH~] > 10~7 M and p H > 7. See Figure 4.6
among [hC], [Ol-Г], pH, and pOH
for acids and bases. for acidity and basicity o f some com m on substances.

1 M NaOH
4.5.2 B R O N STED-LO W R Y A C ID -B A SE THEORY

The A rrhenius concept o f acids and bases is applicable to the aqueous solu­
household
ammonia
tions only. Because o f this lim itation a m ore general theory o f acids and bases
11 _ L milk of was proposed independently by N. B ronsted in D enm ark and T.M . Low ry in
m agn esia G reat Britain in 1923.
This theory defines an acid as a proton donor substance and a base as a
seaw ater
proton acceptor substance.
Consider the reaction

N H 3 (aq) + H 2 0 (1 ) NH 4 (aq) + OH" (aq)

Neutral

Ch + 1
N H 3 becom es N H J in the forward reaction. N H 3 then captures a H + from
H 2 0 . In the forward reaction, H 20 acts as a proton donor and N H 3 as a proton
acceptor. So H20 is an acid (name it as acid-1), and N H 3 is a base (nam e it as
base-2). In the reverse reaction, NH* gives a proton to OH- , therefore NH* is
an acid (name it as acid -2 because o f its relation with NH3), and OH" is a base
2 - igastric {name it as base -1 because o f its relation with H20 )
'juices N H 3 acting as a base in the forw ard reaction becom es N H 4 an acid in the re­
verse reaction or vice versa. N H 3 and NH* or H 20 and OH- are called conju­
gate acid-base pairs. In reactions conjugate acid-base pairs are show n by
1MHCI
the sam e set o f num bers. The only difference betw een a conjugate acid-base
FIGURE 4.6 The pfy scale pair is a proton, H +.
and pH values of some com­ NH 3 (aq) + H 2 0 (1 ) <==> NH^ (aq) + OH" (aq)
mon materials base-2 acid-1 acid-2 base-1
|ШН1НШ1НМШНМШШШтШШШШ1ШШШШ1ШШШШШШШИШШ1ШШШШ1ИШШ1ШШШ111||Ш||Н1ШШ1ШШШ11ШШШШШШШШ|Acids and Bases 129

Another example i s :
H2S (g) + H 20 (1) H 3 0 + (aq) H S'(aq)
acid-1 base-2 acid-2 base-1
I

The conjugate acid-base pairs in this reaction are (1) H 2S (acid) and H S“ (base)
(2) H 3 0 + (acid) and H 20 (base). N ote that w ater can play the role o f either a
Bronsted-Low ry acid or a Bronsted-Low ry base in reactions.

EXAMPLE 4 .3 Determining Conjugate Acid-Base Pairs

Problem : Indicate the conjugate acid-base pairs in the following reactions.
(a) CN- (aq) + H20 (1) <=> HCN (aq) + OH' (aq)
(b)N H ;(aq) + H2 0(1) ^ NH 3 (aq) + H 3 0 +(aq)
Solution : (a) HCN (acid) and CN" (base), H20 (acid) and OH" (base) are the conjugate acid-base pairs.
(b) NH^ (acid), NH 3 (base); H 3 0 + (acid) and H20 (base) are the conjugate acid-base pairs.

EXERCISE 4.4 Identify the conjugate acid - base pairs in the following reactions.
(a) CO3 ' (aq) + H20 (1) <= HCO 3 (aq) + OH" (aq)
(b) CH 3 OH (1) + NH 2 (aq) > CH 3 O- (aq) + NH 3 (aq)

EXERCISE 4.5 Write the conjugate acids of the following bases.

(a) OH" (b) CN" (c) CIO" (d)NH 3

EXERCISE 4.6 Write the conjugate bases of the following acids.

(a)H C q- (b)H30 + (c) CH3 NH^ . (d)HS"

4.5.3 LEWIS ACID-BASE THEORY

T h e e le c tr o n - d o t sy m b o l (o r L ew is
sy m b o l) fo r an e le m e n t c o n sists o f the
A cids and bases w ere defined by G. N. L ew is in 1923 in a
c h e m ic a l sy m b o l fo r th e c le m e n t p lu s broader sense, by using the electronic structure o f the m olecules.
a d o t for e a c h v a le n ce electro n . L ew is defined an acid as an electron pair acceptor, an d a
E le c tro n -d o t base as an electron pair donor su bstance. If a substance has
E le m en t sym bol em pty orbitals, it m ay accept electron pairs, this acts as an acid. If
3Li : Is 2 2s 1 Li-
a substance has lone pair o f electrons for sharing, it will act as a
base. Exam ine the following examples.
4B c : I s 2 2s2 ■Be-

5B : I s 2' i s 2 2p* • B- BF 3 + N H 3 F 3B — N H 3
6C : Is2 2s2 2p2 • c -

7N J I s 2 2 s 2 2 p 3 •N •
:F : H :F : H
gO : I s 2 2s 2 2p 4 ■О •
.. I I
9F : I s 2 2 s2 2 p 5 • F- — В + :N — H :F— В— N— H
10N e : I s 2 2 s 2 2 p 6
I I
■ Ne- I I
:F : H :F • H
n N a : I s 2 2s 2 2p^ 3 s 1 Na-
acid base
130 Chapter 4 |1ИвИНИ!1|111Ш1111111111Ш11ШШШ1Ш111ШИ11ШШШШШИ111111Ш11ШШ1111Ш1Ш1ШШ111Ш11Ш1111Ш11ШШ11Ш111|1ШШШ11111Ш111ШШт1ШШШШШШ

Here В has not completed its octet. It has lack o f electrons in its outer energy
A ll B ro n ste d -L o w ry ac ­ level. Therefore it may accept electrons to complete its octet. The В m ay behave
ids and b a se s a re L ew is
as an electron pair acceptor. It is a Lewis acid. On the other hand N in N H 3 has
a c id s, a n d b a s e s , b u t
com pleted its octet, but it has one pair o f unshared electrons. In chem ical reac­
the re v e rse is n o t true.
tions, N H 3 m ay behave as an electron pair donor substance. So it is a Lew is
base in the reaction given above. The bond betw een В and N atom s is form ed
by m eans o f the electrons supplied by N atom only.Exam ine the follow ing ex­
ample.
Cd2+ (aq) + 4 Г (aq) <=> C d # (aq)
Cd2+ has a vacant 5s orbital so it can act as Lew is acid. Г has unshared elec­
tron pairs so it can act as a base.

EXAM PLE 4.4 Determining Lewis Acid-Base

P r o b le m ; Indicate the Lew is acid and base in the follow ing reaction. 15P , 9F
PF 5 + F -» PF6~
Solution : •F : :F-
15P : Is 2 2s 2 2p 6 3s2 3p3 => P , 9 F“ : Is 2 2s 2 2p 6 => [ F ]A * у•
:fi- * A.
In this example, P has 5 valence electrons but all of them are used in • • p . p
the formation of PF5. So phosphorus has no available electrons for an ■ • A. * . V
A.
extra bonding. In this reaction F" acts as an electron pair donor, a Le­ F
wis base, and PF5 as an electron pair acceptor, a Lewis acid.

EXERCISE 4.7 identify the Lewis acid and base in the following reaction
:0 : :0 :
Ca2+[:0 :]2‘ + S:0 : -> Ca2+[:'6 :S:0 :]2'
:0 : :0 :

EXERCISE 4.8 Indicate the Lewis acids in the following species.

(а )С Н з (b) CH3 NH2 ( c) A1C13 (d)OH'
H in t: Draw the Lewis structures of the molecules to reach a conclusion.

4.6 MONOPROTIC AND POLYPROTIC ACIDS

T he acids that produce only one H + per m olecule are called monoprotic ac­
ids. Some acids m ay contain m ore than one hydrogen atom in the m olecule but
they can donate ju st one proton, therefore they are also m onoprotic acids. HC1,
H N 0 3, C H 3 COOH, HCN are all m onoprotic acids. If an acid can produce m ore
than one H+ per m olecule it is called a polyprotic acid. H 2 S 0 4, H 2 C 0 3, H 2 S,
H 3 P 0 4, H 3 P 0 3 are all polyprotic acids. But H 2 S 0 4, H 2 C 0 3, H 2S are usually
called diprotic acids, and H 3 P 0 4, H 3 P 0 3 triprotic acids. H 4 P 2 0 7 (pyro-
phosphoric acid) is a tetraprotic acid.
Likew ise, depending upon the num ber o f O H ' ions produced per m olecule
o f base, bases m ay be classified as monohydroxy, dihydroxy, or trihy-
 Acids and Bases 131

droxy bases. N aO H , K O H , N H 3 ... are m onohydroxy bases. C a(O H )2,

Ba(O H ) 2 are dihydroxy bases. Al(OH ) 3 is a trihydroxy base.

4.7 THE STRENGTH OF ACIDS AND BASES

I f an acid or base is extensively dissociated into ions it is called strong acid

or strong base. G enerally strong acids o r strong bases are assum ed to be ful­
ly, (100 %), ionized. HC1 is a strong acid w hen 1 M o f its solution is prepared
it will dissociate into 1 M o f H 3 0 + and 1 M o f Cl" ions as show n by the eq u a­
tion :

TABLE 4 .2
H Q (g) + H20 (1) H 3 0 + (aq) + Cl" (aq)
Some co m m o n strong
acids a n d bases
- 1M 1M 1M

A cids B ases
Ba(O H ) 2 is a strong base. 1 M o f B a(O H ) 2 solution contains 1 M o f Ba2+ and
HCI NaOH 2 M o f OH" ions as shown by the equation :
HBr KO H
HI RbOH
НСЮ 4 CsOH
Ba(OH ) 2 (aq) Ba2+ (aq) + 20H " (aq)
H N 03 C a(O H )2 -1 M 1M 2M
H 2s o 4 S r(O H )2
B a(O H )2
Some com m on strong acids and strong bases are given in Table 4.2.
I f an acid or base dissociates into ions to a slight extent, such an acid or base
is called weak acid or weak base. In w eak acid o r base solutions ju st a sm all
fraction o f acid or base m olecules dissociate into ions and an equilibrium exists
betw een undissociated m olecules and the ions. If HB represents a w eak acid,
W c re p re se n te d a w eak the equilibrium m ay be shown:
acid as HB in te n tio n a l­
ly. A s u b s ta n c e h a v in g
*HB (aq) + H20 (1) H 3 0 + (aq) + B" (aq)
acidic c h a ra c te r beco m es
The equilibrium constant fo r this reaction is shown by Ka (Kmid) which is called
a c o n ju g a te b a s e w h e n
it lo se s its p ro to n . In
dissociation constant, or ionization constant of the acid.
H B , H d e n o te s a c id ic
c h a ra c te r, В its c o n ju ­ |H 30 +][B~ ]
g a te b ase.
[HB]
As the value o f К a increases, the strength o f the acid and the degree o f dissocia­
tion o f the acid increase too.
In the sam e m anner, if В represents a w eak base, the equilibrium in its solution
m ay be shown

В (aq) + H20 G) BH+ (aq) + OH- (aq) Kb =

In many reference books this equation is simplified by eliminating H20 from the equation
HB (aq) H+ (aq) + B" (aq)
132 Chapter 4 ШИШИ INI II IIIIMI Ш ИШ ................ НИШ..................... .

See Table 4.3 to learn the equilibrium equations and the K a or K b values o f
very com m on weak acids or bases.

TA B L E 4.3 Ionization Constants fo r some W eak A cids and W eak

Bases in Water A t 25 °C
Ionization ^
Ionization equilibrium constant, К

Acid Ka =
acetic HC 2 H 3 0 2 + H20 H 3 0 + + C 2 H3 0 - 1 .8 x 1 0 -5

benzoic HC 7 H 5 0 2 + H20 H 3 0 + + C 7 H5 0 - 6.4 x 1 0 -5

chlorous HC10 2 + H20 h 3o + + a o j 1 .2 x IO ' 2

formic H C H 0 2 + H20 H 30 + + C H 02 1 .8 x 1 0 '4

hydrocyanic H C N + H 20 H 3 0 + + CN- 4.0 x 10 - 10

hydrofluoric H F + H 20 H 3 0 + + F- 6.7 x IO' 4
hypochlorous н е ю + H 20 н 3о + + a o - 3.0 X 10 ' 8
monochloroacetic HC 2 H 2 C10 2 + H20 h 3 o ++ c 2 h 2 q o 2- 1.4 x 1 0 -3

nitrous h n o 2 + H 20 H30 + + n o 2 5.0 x 10" 4

phenol HOC 6 H 5 + H 20 H 3 0 + + c 6 H5 o - 1.6 X IO’ 10
Base Kb =
ammonia N H 3 + H20 <“ n h ; + OH- 1 .8 x 1 0 '5

aniline C 6 H 5 NH 2 + H20 < c 6 h 5 n h ; + OH- 4.3 x 10 - 10

ethylamine C 2 H 5 NH 2 + H 20 - C 2 H 5 N H j + OH- 4.3 x 10‘ 4
hydroxylam ine HONH 2 + H20 < H O N H 3 + OH- 9.0 X IO' 9
methylamine CH 3NH 2 + H20 < CH 3 N H 3 + OH- 5.0 X 1 0 -4

pyridine c 5 h 5n + H20 < C 5 H 5 N H + + OH- 2.0 x IO’ 9

A full list of Ka and Kb values are given in appendix II.

4.8 ACID STRENGTH AND MOLECULAR

STRUCTURE
The strength o f an acid is ultim ately related to the ease with w hich a proton is
lost. There are m ainly tw o factors that affect the release o f proton from an acid
molecule.
1) The electronegativity of the element bonded to H in the acid
molecule. As the electronegativity increases the acid strength increases too.
The m ore polar the bond, the more readily the acid is ionized.
2) The size of the atom bonded to hydrogen atom. As the size o f
the atom increases the acid strength increases too. Increasing the size o f atom
decreases the bond strength betw een atoms. W eak bonds are m ore easily ion­
ized than stronger ones.
iiiH tn m m m m m iitiiiiiiiiiin iiiiH iiiif t iiit iiiiiiiiif iiiiiiiiiiiiiH iiiiiiiit iiiiiiiiiiiiH iiiiiiiiiit iiiiiiiiiiH it n iiiit iiiH f iiiiit iiH iiiiiH iiiiiii! iiiiit iim iiT Acids and Bases 133

Consider a binary acid, HX. As the electronegativity o f the X atom increases

F or b in ary acids; the acid
H — X bond becom es m ore ionic, and the m olecule easily produces H + ions,
stre n g th in cre ases d o w n a and the acid becom es stronger. C onsider hydrides o f N, O, F, o f the second
g ro u p , fro m le ft ю rig h t period o f the periodic table. Their electronegativity order is N < О < F, and the
acid strength o f their hydrides increases in the sam e order. N H 3 < H 20 < HF.
In reality N H 3 is a base, w ater is neutral, H F is a w eak acid.
The sam e argum ent is true for the m em bers o f the third period elem ents. In
electronegativity P < S < Cl, in acid strength
PH 3 < H2S < HC1.
W ithin a group the electronegativity o f atoms decreases (an effect to decrease
the acid strength) from top to bottom but size o f atom s increases (an effect to
increase the acid strength). These tw o factors w ork against each other, but the
effect o f atom ic size outweighs the electronegativity effect. The acid strength o f
the hydrides o f a given group o f elem ents increases from top to bottom.
C onsider V IIA group elements: F, Cl, Br, I

Electronegativity order F > Cl > B r > I

A cid strength order when
only electronegativity is H F > HC1 > H B r > HI
considered
H -F b o n d is th e stro n g e st
b o n d in fo u r h y d ro g e n h a ­ A cid strength w hen only HI > H B r > HC1 > H F
lid e s. M o re e n e rg y is r e ­
atomic size is considered
q u ired to break th is bond
c o n s e q u e n t ly H F is a
w eak acid. T he a c tu a l a c id s tre n g th : HI > H B r > HC1 > HF

F o r o x y a cid s in the form In oxyacids, H — О — Z, as the electronegativity o f the elem ent Z increases,
o f H -O -Z , the stre n g th is j
the tendency o f the attraction o f the electrons in H — О bond will in ­
d ir e c tly p r o p o rtio n a l to j
th e e le c tr o n e g a tiv ity of! crease, therefore the ease o f releasing H + will increase, and acid will becom e
Z . If Z is a m etal w ith aj stronger. F or exam ple HOC1 is a stronger acid than HOI because the electro­
lo w e le c tro n e g a tiv ity the j negativity o f Cl is greater than I. If som e m ore atom s with a high electronega­
e le c tro n s o f Z are com-' tivity are bonded to Z, this will cause Z to have a higher ability to attract elec­
p le te iy tra n s fe rre d to o x -1 trons in H — О bond, thus the acid strength will further increase.
y g e n atom a n d an io n ic j
com pound in v o lv in g ) :0 : :0 :
I
OH is fo rm ed . In th a t; C o n sid e r: H - O - C l: , H - O - C l- O : , H - O - C l- O : , H -O -C l-O :
case Z - O H p ro d u c es O H
io n s in s o lu tio n s and ; :0 :
a cts as a b ase. Since О is more electronegative than Cl, as the num ber o f О atoms bonded to
N aO H , K O H , C a (O H )2are Cl increases, the acid strength increases, therefore the acid strength o f these ac­
b ases. ids will be:
НСЮ4 > H d 0 3 > HC102> н е ю
134 Chapter 4 ш п ш м м ш ш м п ш ш ш ш м м м п п м ш м п м п ш ш и и и ш ш н ш и ш ш ш ш н н н п н н п ш ш ш ш ш м ш ш ш ш м и н ш н н ш ш ш ш м п ш ш ш ш м п ш ш п ш п

EXAMPLE 4 .5 Comparing the Strength of Acids

Problem : Compare the acid strengths of the following pairs.
(a) H2S and H2Te (b)H2TeandH I (c) H N 0 2 and H N0 3

H O Cl О
I I! I II
(d) H - С - С - OH and Cl - С - С - ОН
I I
H Cl

Solution :
(a) S and Те are in the same group. In a group the acid strength increases with increasing size, therefore H2Te is
a stronger acid than H 2 S.
(b) Те and I are in the same period. In a period as the electronegativity of the element bonded to H increases the
strength of the acid increases too. Therefore HI is a stronger acid.
(c) Both H N 0 2 and H N 0 3 are oxyacids. In H N 03, one more О atom is bonded to N, which will cause N to be­
come more positive. This will weaken H — О bond, therefore H N 0 3 is a stronger acid.

:0 : •
H - О - N = О: , H - О - N = О:

(d) The Cl atoms bonded to С atom will cause this С atom to be more positive, consequently this carbon
will attract the electrons in the other C, which will cause a weakening in the O -H bond. For this reason
CC13 - COOH will more readily release H+ than will CH 3 COOH. So CCl3COOH is a stronger acid.

EXERCISE 4.9 Compare the acid strengths of the following pairs.

H O H O
1 I! I II
(a) HF and HBr (b) H2 S 0 3 and H2 S0 4 (с) H - С - С - OH and H - С - С - ОН (d) НС104 and НВЮ 4
1 I
F С1

4.9 PROPERTIES OF ACIDS AND BASES

Aqueous solutions o f acids have a set o f com m on properties, w hich are the
properties o f hydronium ion.
S om e c o m m o n acidic 1 - A cids have a sour taste. T hink o f the taste o f vinegar, (a 5% solution o f
su b s ta n c e s : acetic acid), the taste o f lem on juice (a m ixture o f citric acid), the taste o f green
le m o n -citric acid
grapes ( a mixture o f tartaric acid).
o ra n g e -c itric acid
v in e g a r-a c e tic acid 2 - A cids affect dye materials. F or exam ple, acids turn blue litm us (a dye
rh u b a rb -o x a lic acid m aterial) to red. R em em ber that the color o f a glass o f tea gets pale w hen som e
g reen g ra p e s-ta rta ric acid lem on juice is added to water.
g re en a p p le s-m a lo n ic acid.
I ............................. Acids and Bases 135

3 - A cids fo r m conducting solutions. B ecause acids are w holly o r partially

dissociated into ions in aqueous solutions.
4 - A cids react with m ost o f the m etals, and produce H2 gas.
Zn (s) + 2HC1 (aq) -> ZnCl 2 (aq) + H 2 (g)

2A1 (s) + 3H 2 S 0 4 (aq) -» A12 (S 0 4 ) 3 (aq) + 3H 2 (g)

F e (s) + 2HC1 (aq) -> FeCl 2 (aq) + H 2 (g)
B ut Cu, Ag, Fig, Au, Pt are not affected by the binary acids. Strong ternary
acids such as H N 0 3, H 2 S 0 4 affect Cu, Ag, Hg only as oxidizing agents, as
show n below.
Cu (s) + 4 H N 0 3 (aq) -> C u(N 0 3 ) 2 (aq) + 2 N 0 2 (g) + 2H20 (1)
2Ag (s) + 2H 2 S 0 4 (aq) -> Ag 2 S 0 4 (aq) + S 0 2 (g) + 2H 2 0 a )

5 - Acids affect m etal carbonates, and produce C 0 2 gas.

C a C 0 3 (s) + 2HCI (aq) -> CaCl 2 (aq) + C 0 2 (g) + H20 (1)

N a 2 C 0 3 (s) + 2HC1 (aq) -> 2NaCl (aq) + C 0 2 (g) + H20 (1)

6 - A cids react with bases. The reaction betw een an acid and a base is called
"neutralization reaction"
HC1 (aq) + NaOH (aq) -> NaCl (aq) + H20 (1)

H 2 S 0 4 (aq) + Ba(OH ) 2 (aq) -> B aS 0 4 (s) + 2H20 (1)

The neutralization reactions will be studied in details later in this

chapter.
The common properties of bases:
A m p h o terism d e sc rib e s th e a b ility o f 1 - Bases have bitter taste.
a su b sta n c e to re a c t e ith e r an acid o r 2 - They have slippery feeling. Rem em ber the slippery feeling o f
a b ase. G e n e ra lly the o x id e s o f a m ­
p h o te ric m eta ls are also a m p h o te ric .
soaps, which are mildly basic substances.
For e x am p le : 3 - They fo r m conducting solutions, because they are ionized.
A120 3 + 6HC1 - * 2A1C13 + 3 H 20 4 - They change the colors o f m any dye materials. F or exam ple
A120 3 + 6N aO H -> 2 N a3A 1 0 3 + 3 H 20
bases change red litm us to blue, o r colorless phenolphthalein to
M o s t n o n m e ta llic o x id e s are a c id ic
o x id e s, th a t is, th e ir re a c tio n s w ith
pink.
w ater pro d u ce acids. 5 - A l, Z n, Pb, Sn m etals react w ith strong bases N aO H , and
c o 2 + H 20 -> H 2C 0 3 KO H , to produce H2 gas. Since these m etals react w ith both acids
s o 3 + H20 H 2S 0 4
and bases to produce a salt and H2 gas, these m etals are called am­
N 20 5 + H 20 - » 2 H N 0 3
M o st m eta llic o x id es are u su a lly b a s ­ photeric metals.
ic, th at is, th e ir re a c tio n s w ith w ater Zn + 2NaOH -> Na 2 Z n 0 2 + H 2 (g)
p ro d u c e bases:
sodium zincate
N a 20 + H 20 —> 2N aO H
C aO + H 20 -> C a(O H )2 2A1 + 6 N aOH -> 2Na 3 A10 3 + 3H 2 (g)
sodium aluminate
136 Chapter 4 lllllllllltllH llllllllllllllllllllllllllllllllllllllH IIIIIIIIII I I I ........................................ ................ I I I ! ............................................ I .................... . Ш И Н ................ I .................. ..... M i n i

6 - They react with acids to fo rm salt and water.

3M g(OH ) 2 + 2H 3 P 0 4 -» M g 3 (P 0 4 ) 2 + 6H20

A Comparison o f the Properties o f Acids And Bases

s N
Acids Bases

(1) electrical conductors (1) electrical conductors

(2) taste sour (2) taste bitter
(3) make blue litmus red (3) make red litmus blue
(4) destroy the basic properties (4) destroy the acidic properties
(5) corrosive to skin (5) corrosive to skin
(6) react with metals to give H2(g) (6) only specific ones react
(7) react with carbonates to give C 02 with specific metals to give H2 (g)
(7) feel slippery
V J

EXAM PLE 4.6 R e a c tio n o f A cid s w ith M e ta ls

Problem ; A 10 g impure sample of Mg is reacted with an excess amount of HC1 solution. If 4.48 L of H 2
gas are collected at STP, what will be the percentage purity of the magnesium sample by mass? Mg = 24.
Solution : Mg and HC1 react with each other according to the equation.

24 g 22.4 L
4 48 x 24
Mg (s) + 2HC1 (aq) > MgCl2 (aq) + H2 (g) * = ■ = 4 -8 S

xg 4.48 L

To produce 4.48 L of H 2 gas, there must be 4.8 g of Mg in 10 g sample. So the percentage of Mg in the
sample is

If 10 g sample has 4.8 g of Mg 1 ^ = 1 0 0 x 4 .8 = 48 „ ^ 48 %

then 1 0 0 g sample__________ x_________ J ю

EXERCISE 4.10 1.23 L of H 2 gas at 27°C and 2 atm was obtained by thereactionof 4 grams of M
metal with excess HC1 solution. Calculate the atomic weight of the metal M.
M (s) + 2HC1 (aq) -» MC12 (aq) + H2 (g) 40 g/mol

EXERCISE 4.11 If 200 mL of HNO 3 solution react completely with 21.2g of Na2 C 0 3,findthe molari­
ty of the acid solution. Na 2 C 0 3 = 106 g/mol. 2 M

EXERCISE 4.12 A test lube contains pieces of an alloy of copper and zinc, and chips of marble,
C aC03. If concentrated H N 0 3 is added to this test tube, which gas (es) will be produced? And write the equations
for the reactions. H 2, N 0 2, C 0 2
111М11111111ММ|||!1Ш1Ш|Ш1М!||Ш1М!1МН|М||ЩШ|!1Ш|||Ш||ММ||Ш1ШШН!||11||11ШШШ||ШШ||||1Н|Ш||Ш1ШШ111111!Ш||| A dds CLTld BdSeS 137

EXERCISE 4 .1 3 A 23.8 g alloy of zinc and aluminum is allowed to react with an excess quantity of
KOH solution. At the end of the reaction, 12 L of H 2 measured at 27°C and 1.64 atm is collected. Calculate the
mass of zinc in the alloy sample. Zn = 65 A1 = 27 13 g

4.10 QUANTITATIVE CALCULATIONS ABOUT

STRONG ACIDS AND BASES
N ow we w ill restrict o u r discussion to only strong acids and bases. T he
equilibria o f weak acids and weak bases will be studied in details later.

EXAM PLE 4 .7 Calculating [H30 +], [OH-], pH", and pOH of a Strong Acid Solution
Problem ; Calculate [H30 +], [O H '],.pH , and pOH of 0.01 M HC1 solution.
Solution ; Hydrochloric acid ionizes 100%, because it is a strong acid.
In a strong acid so lution,
we ignore [H 30 +] o f w ater HC1 (g) + H20 (1) —> H30 + (aq) + C l' (aq)
and assum e that the [II30 +] - 0 .0 1 M 0.01 M 0.01 M.
of the solution is prim arily
determ ined by the acid.
The OH" ions are produced From the equation we see that 1 mol HC1 produces 1 mol o f H30 + and
by d iss o c ia tio n o f w ater.
1 mol C l'.Therefore 0.01M HC1 produces 0.01M of H 30 + and 0.01M of СГ.
Since w ater produces equal
am ounts o f H30 + and OH" , Then
from the dissociation of w a­ [H30 +] = 0.01 M and pH = - log [H30 +] = - log (0.01) => pH = 2
ter lx lO " 12 M of H30 + will
also be p roduced. B ut this In all aqueous solutions [H30 +] [OH'] = 1 x 10~14. Therefore
am o u n t is n e g lig ib le r e la ­
к ~ 14
tive to the H 30 + produced by
[O ff! = ---------------=> [OH~] = l x l Q - = 1 x 10_12M
the acid . (1 x 1 0 '12) «
0.01, So th e [H30 +] o f the
[H p + ]
so lu tio n is e q u a l to the pOH = - lo g [OH-] = - lo g (1 x 10'12) => pOH = 12
[H30 +] produced by the acid.

EXERCISE 4.14 100 mL of 10 M HC1 solution is diluted to 100 L with pure water. Find [H+], [OH- ],
pH, and pOH of the resulting solution. 0.01M,1 x 10'12M,2,12

EXERCISE 4 .1 5 1.6 g of a strong acid HX is dissolved in 1250 L o f water. If the pH of the solution is
5, what is the atomic weight of X ? H = 1 127 ghnol

EXAM PLE 4 .8 Calculating [OH-], [H30 +], pH and pOH of a Strong Base Solution
Problem : W hat are the concentrations of OH", and H30 +, pH and pOH of a 0.005 M Ba(OH)2 solution?
Solution : Ba(OH)2 is a strong base that dissociates into Ba2+ and O H ' ions, 100%.
Ba(OH)2 (s) —> Ba2+ (aq) + 2 0 H ' (aq)
0.005 M 0.005 M 0.010 M
138 Chapter 4 |>№"^>4,^ |||>||и|||п|||иж|ш,|иш1|и,||п,,||,,т|,ии,мшшш1,,№>и,>|)||,т11п,,'г1,|,ишииин|||ии||ш,и||п|пии,и||,,им,и|и,,,,,п,и|||||||п

W e ignored the [OH"] pro­ Then, [OH'] = 0.010 M pOH = - log (0.01) => pOH■= 2
duced by d isso ciatio n of
water. Since it is extrem e­ -14
ly sm all com pared to 0.01 Кш
[H p ] = [ H P ] = 1 4 10 = 1 X 10 12 =* pH = 12
M. 0.01
pH + pO H = 14 [OH
[НэО+] = 10"pH
[I130 +] = " M.
10 12 or pH + pOH = 1 4 ; pH = 14 - 2 = 12

EXERCISE 4.16 A 4.88 grams sample of Sr(OH )2 , a strong base, is dissolved in enough water to make
800 mL of solution. Determine (a) [OH""] and [H+J (b) pOH and pH of the solution. Sr(OH)o = 122 g /m o l.
(a)0.1M and l x l O ' 1 3 M , . (b)13 and I

EXERCISE 4.17 A 7 grams impure sample of KOH is used to prepare 500 mL of solution. If the pH of
the solution is 13, what is the percentage purity of KOH sample ? KOH = 56 40%

EXERCISE 4.18 Complete the following table by appropriate calculations.

Solution [H30 +] [OH- ] pH pOH

0.05 M HC1
...... M H N 0 3 2
0.05 M Ba(OH)2 ......
......M NaOH 1 x 10"n

EXAMPLE 4 .9 Calculating pH of a Negligibly Soluble Strong Base

Problem : Ca(OH)2 is a strong base but it has negligible solubility in water. Calculate the pH of the saturat­
ed Ca(OH)2 solution. Ksp for Ca(OH)2 = 4.0 x 10"6
Solution : The equilibrium in saturated Ca(OH)2 solution is
Ca(OH)2 (s) <=^ Ca2+ (aq) + 2 0 H - (aq)
- x mol/L x mol/L 2x mol/L

W e see that x mol of Ca(OH)2 dissolved produces x M of Ca2+ and 2x M of OH- .

Ksp = [Ca2+] [OH"]2
Inserting the equilibrium concentrations into Ksp expression gives 4.0 x 10"6 = (x) (2x)2.
Solving this equation for x gives x = 0.01 M , and [OH"] = 2x = 0.02 M.
pOH = - log [OH"] => pOH = - log (0.02) = 2 - log 2 = 2 - 0 . 3 = 1.7
pH = 14 - pOH = 14 - 1.7 =* pH = 12.3

4.11 NEUTRALIZATION

Suppose that we added 0.1 m ol o f N aOH to one liter o f 0.1 M HC1 solution.
The concentrations o f H + and OH- would be 0.1 M each. The trial ion product
for the equilibrium
H20 G) <*=* H+ (aq) + O H - (aq) Kw = [H+] [OH- ] = 1 x 10 " 14
и и ш и ш и и и ш ш ш н ш ш и ш ш ш ш ш ш ш ш и ш ш ш ш п ш и п ш ш ш ш и и и и ш м ш и ш н н ш и ш и ш ш ш ш и п ш ш ш ш г Acids and Bases 139

would be Q w = [H+] [OH"] = (0.1) x (0.1) = 0.01

R em em ber that if Q > K, the reverse reaction takes place until Q becomes equal
to the K. Since Qw > K w, to establish equilibrium , the reverse reaction w ould
take place. In the reverse reaction, H+ and OH" ions would com bine to form w a­
ter. The reaction is:

H + (aq) + OH- (aq) <=> H20 (1) K = — = l x 10U

(acid.) (base) (neutral ) Kw

The very large value o f К = 1 x 10 14 indicates that alm ost all the H + and OH-
ions are converted into water. W hen a strong acid and a strong base are m ixed
in proper am ounts, both acid and base lose their characteristic properties and
form a neutral substance, w ater, therefore, the reaction between an acid
and a base is called neutralization reaction. T he large value o f К for
neutralization reaction reveals that the neutralization reaction nearly goes to com ­
pletion. One m ore fact about a neutralization reaction is that exactly 1 m ol o f H+
ion neutralizes 1 m ol o f OH- or vice versa. If equal m ole num bers o f H+ and
OH" ions are m ixed, we obtain a neutral solution where
[H+] = [OH- ] = 1 x 10" 7 M or pH = pO H = 7.
If the num ber o f moles o f H+ ions and OH~ ions are not equal a partial neutrali­
zation occurs. Briefly i f :
n u + - n on~ >a com plete neutralization occur, and the fin a l solution is neu­
tral.
hji+> n () i r , then (пц+ - пон~) mole o f H + ions remains in excess and the f i ­
nal solution is acidic.
п он~ > п н + >then (пон~ - ni t ) m ole ofO H ~ remains in excess, and the fin a l
_______________ solution is basic._______________________________ ___________
The following examples illustrate how to cope with neutralization reactions.

EXAM PLE 4.10 Neutralization of Acids and Bases

Problem : How many mL of 0.1 M HC1 solution are required to neutralize 25 mL of 0.4 M NaOH solu­
tion?
Solution :
TYPE (I) The neutralization reaction in general is:
H+ (aq) + OH- (aq) « = > H20 (1)
1 mol 1 mol
The equation shows that 1 mol of H+ neutralizes 1 mol of OH". Since we know the volume and molarity of
NaOH solution, we can calculate the number of mole of NaOH.

nNaOH = M x V = 0.4 mol/L x 0.025 L = 0.01 mol

The number of mole of OH- produced by 0.01 mol of NaOH is

NaOH (s) — » Na+ (aq) + OH- (aq)

0.01 mol 0.01 mol
0.01 mol of OH- neutralizes 0.01 mol of H+, then the number of mole of H+ produced by the acid, HC1, must
140 Chapter 4 Шйптишиншшишшнииннптшшншштишншшнитнтинтиишнттниюинмиимишннншишниимшнмшшшниншишип

be 0.01, and the number of mole of the acid, HC1, is:

HC1 (aq) —> H+ (aq) + СГ (aq)
? = 0.01 mol 0.01 mol

Now we know the mole number (0.01), and molarity of the solution (0.1), so the volume o f HC1 is:

M = — => V = — V = °-01 mo1- = 0.1 L V = 100 mL.

V M 0.1 mol/L

TYPE (II) In complete neutralization reactions : nn+ - noir or M j,+ x V H+ M o ir x ^ o i r

The advantage o f this equation is that the volumes may be expressed in any units on both sides of equation.
M H+ хx V
м н+ VH+ = MOH. xx VVOH.
MI. =>
= > 00.1
. 1 :x Vn+ = 0.4 x 25 -> VH+ = 100 mL
The volume of the acid solution is 100 mL.

TYPE (III) The neutralization reaction between NaOH and HC1 is :

NaOH + HC1 — > NaCl + H20

The number of mole of NaOH used in this reaction is :

n = M x V = 0.4 mol/L x 0.025 L = 0.01 mol

The number of mole of HC1 necessary for 0.01 mol of NaOH is :

1 mol 1 mol
NaOH + HC1 — > NaCl + H20
0.01 mol x = 0.01 mol

The volume of HC1 is : v = — = = 0 1L => V = 100 mL

M 0.1
TYPE (IV) In neutralization reactions 1 equivalent weight of acid always neutralizes 1 equivalent weight of
base. Or to obtain a neutral solution, the numbers of equivalent weights of acid and base must be equal.

14 acid = 1 4 base (neq = number equivalent weight o f )

In solutions, we have learned that Пел

N = — n eq = N x V (N => normality)
V
Inserting this equation into the previous one gives :
N acid x V acid = N base x V base
Rem em ber that N = a x M where M shows the molarity, and a shows the number o f moles of H+ or
OH- furnished per mole of acid or base.

M,NaOII = 0 .4 M => N NaOH = 0.4 N

fNaOH = 25 mL N a cid ^ ^ a c id ” I^ b a se ^ ^b ase
M HC1 0.1 M N,HCl = 0.1 N 0.1 N X V hci = 0.4 N x 25 mL
^HCl - ■ V = 100 mL
1 1 1 1 1 1 1 1 ■ 1 1 1 1 1 1 1 1 1 1 ■■ 1 1 1 1 1 1 1 1 1 1 1 1 ! 1 1 н и i f I i i f п н h i I ш и п и м ш и п и i i i I ■ 1 1 1 1 1 ! 1111 ■ 1 1 1 1 1 1 1 n u t п и н 1 1 1 1 1 1 ! 1 1 1 1 1 n i i i i i u n i п н 1 1 1 1 1 1 1 1 1 111 1 11 111111м 11 ............A cids a n d Bases 141

EXERCISE 4.19 20 mL of KOH solution is required to neutralize 50 mL of 0.1 M HC 1 . Calculate the

molarity of the KOH solution. 0.25 M

EXAMPLE 4.11 Calculation about Neutralization

Problem : A 50 mL sample of 0.1 M H 2 S 0 4 solution is completely neutralized by 20 mL of KOH solution.
What is the molarity of the base solution?
S olutio n:
TYPE (I) The number of mole of H+ produced by 50 mL 0 1 M H 2 S 0 4 is :
nH+ = MIi2 so4 x V„2 so4 x 2 => nH+ = 0 .1 x 0 .0 5 x 2 = 0 .0 1 mol.
Then the number of mole of OH- in 20 mL of KOH solution must be 0.01. (Remember 1 mol H+ neutralizes 1
mol OH- ). Hence,
nOH' = ^ koh x VK0II x 1

0.01 mol = Mjjqjj x x 1 M кон = ——— = 0.5 M

0.02
T Y P E (II)
Мц+ x ^ ii+ - MOH- x VOH-
MH.so,
u2so4 x 2 x VH so -= JvlK
n2so4 MK0HOI-I лx VKO
т конH (Remember H2 S 0 4 is a diprotic acid.)
0.1 x 2 x 50 = MK0H x 20 => MK0H = 0.5 M.

TYP E (III) nIl2SC >4 = 0.1 mol/L x 0.05 L = 0.005 mol.

1 mol 2 mol

H2 S 0 4 + 2KOH — > K 2 S 0 4 + 2H20

0.005 mol x = 2 x0.005 mol
= 0.01 mol KOH => M = — = ° :01 m o1 = 0.5 M
T Y P E (IV) V 0 0 2 L

N acid X V acid = N base X V base

M I I 2S 0 4 x 2 X V h 2s o 4 = MK0U x 1 x VK0H
0.1 x 2 x 50 = MKOn x 20 => MKOH = 0.5 M

EXERCISE 4.20 How many mL of 0.1 M H 3 P 0 4 are necessary to neutralize 150 mL of 0.1 M
B a(O H ) 2 solution? 100 mL

EXERCISE 4.21 When a 4.0 L of unknown concentration of NaOH solution is added to 400 mL of 0.05
M H2 SO 4 solution, the pH of the resulting solution is 7. Calculate the pH of the NaOH solution. (Remember
pH = 7 means a complete neutral solution.) pH -12

EXAMPLE 4.12 C alcu latin g P ercen tage P u rity of a B ase Sam p le

Problem : A 1 0 g impure sample of Ba(OH ) 2 is completely neutralized by 200 mL of 0.25 M H 2 S 0 4 solu­
tion. Calculate the percentage of Ba(OH ) 2 by mass in the original sample? (Assume that impurities are inert to
H 2 S 0 4) Ba(OH ) 2 = 171 g/mol
142 Chapter 4 Ш Ш Ш Ш Н Ш Н Illlllllllllllllllllllllllllll Ш Ш Ш Ш Н Ш И Ш Н Ш Н Ш Ш

Solution : The number of moles of H 2S 0 4 used in neutralization is :

nH2so4 = M x V = 0.25 mol/L x 0.2 L = 0.05 Mol.
1 mol 1 mol
H 2S 0 4 + Ba(OH )2 — >B a S 0 4 + 2H20
0.05 mol x = 0.05 mol
0.05 mol o f H 2S 0 4 can neutralize 0.05 mol of Ba(OH)2 . The mass of 0.05 mol of Ba(OH ) 2 is:
0.05 mol x 171 g/mol = 8.55 g. Hence, the mass percentage of Ba(OH ) 2 is
10 g sample have 8.55 g of Ba(OH ) 2 л „
1 0 0 g - 18 I х ’ S5S%

or neq H2so 4 = N x V = M x 2 x V = 0 . 2 5 x 2 x 0 . 2 = 0.1 eq.

For neutralization n4 . base = 0.1 eq.

1 eq. o f Ba(OH ) 2 = = — = 8 5 .5 g
a 2

So 0.1 eq. of Ba(OH ) 2 is 0.1 eq x 85.5 g/eq = 8.55 g

and the mass percentage of Ba(OH )2 in the sample is

?.S5g Ba(OH) 2
x lOOg = 85.5g =» 85.5%
lOg sample

EXERCISE 4.22 A 0.5 g impure sample of a diprotic acid, which is % acid by mass is completely
90
neutralized by 50 mL of 0.2 M KOH solution. Find the molecular weight of the acid. 90 g/mol

EXERCISE 4.23 A 50 mL of H3 X O 4 solution with a density of 1.42 g/m L and containing 10 %

H 3 XO 4 by mass is completely neutralized by 300 mL of 0.5 M NaOH solution. Find the atomic weight of X.
H = 1 0 = 16 75 g/mol

EXAMPLE 4.13 C alculating the M ass Percentage of C H 3C O O H in a Vinegar Sam ple

Problem : Vinegar is a solution of acetic acid, HC 2H 30 2. If a 25 mL sample of vinegar which hasa density
of 1.06 g/mL is completely neutralized by 40 mL of 0.5 M NaOH solution, what will be the percentage of acetic
acid by mass in the vinegar sample? HC 2H 30 2 = 60 g/mol.
Solution : First let us calculate the mole number of base, NaOH, used.
n = M xV = 0.5 M x 0.04 L = 0.02 mol.

The mole number of acetic acid neutralized by 0.02 mol of NaOH may be calculated by means of the neutral­
ization reaction as shown below.

1 mol mol
1
NaOH + HC 2H 30 2 NaC 2H 30 2 + H20
0 .0 2 mol x = 0 .0 2 mol.

The mass of 0.02 mol of acetic acid, HC 2H 30 2 is 0.02 mol x 60 g/mol = 1.2 g.
 muni IIIUHII
Acids and Bases 143

The mass of 25 mL of vinegar solution is : 25 mL x 1.06 g/mL = 26.5 g.

26.5 g o f vinegar solution have 1.2 g of HC 2H 30 2 1 inn * 1 9

1ПП „ , „ „ f jc = = 4.53 g or 4.5% acid by mass
lOOg _ xg J 26.5
- ---------------------------------

EXERCISE 4.24 W hal volume of a solution of KOH with a density of 1.06 g/ntL and is 5.6% KOH by
mass is required to neutralize 20 mL of a vinegar sample which has a density of 1.05 g/mL, and is 10% acetic
acid by mass. 33 mL

EXAMPLE 4.14 C alculating pH and pOH After Partial Neutralization

Problem : 3.42 g of Ba(OH ) 2 is added to a 200 mL of 0.1 M HC1 solution. Calculate the pH and pOH of
the resulting solution. Ba(OH ) 2 = 171 g/mol

S olution : The number of mole of 3.42 g of Ba(OH )2 is n = ——— = — — — = 0.02 m o l .

MW 171 g /m o l
The number of mole of OH- produced by 0.02 mol of Ba(OH ) 2 is 0.02 x 2 = 0.04 mol.
The number of mole of HC1 in 200 mL of 0.1 M solution is n = M x V = 0.1 x 0.2 =0.02 mol.
and the number of mole of H+ = the number of mole of HC1 = 0.02 mol.
The neutralization reaction between H+ and OH~, and the change in mole numbers of H+ and OH- are shown be­
low.
H+ (aq) + OH~ (aq) < = ^ H20 (1)
m oles at start : 0.02 0.04 —
change : - 0.02 - 0.02 + 0.02
after reaction : n e g lig ib le 0.02 0 .02

After neutralization 0.02 mol of OH- remains behind. Therefore the final solution is basic and the [OH'] in the
final solution is

[OH"] = ~ = — = 0.1 M = 10_1M and pOH = - log [OH~~] = - log 10' 1 = 1

Vt ° ’2 and pH = 14 - pOH = 1 4 - 1 = 13

EXERCISE 4.25 W hat is the pH of each of the following solutions ?

(a) A solution prepared by adding 100 mL of 2 x 10~3 M HC1 to 100 mL of 1 x 10~3 M Sr(OH) 2 -
(b) A solution prepared by adding 200 mL of 0.5 M H 2 SO 4 to 300 mL of 0.5 M KOH.
(c) A solution prepared by adding 300 mL of solution with pH = 3 to 200 mL of soluLion with pH = 11. (Re­
member that pH > 7 means a basic solution) Log 2 = 0.3, log 5 = 0.7 (a)7 (b )l (c)3.7
.......................................... a ....................................i ха. . ■,.„. „„,.,■,■■....1 i - ........................................................... Щ ..................................................................................

EXAMPLE 4.15 P artial N e u tra liza tio n

Problem : When a 22 g impure solid sample of a triprotic acid is dissolved in 500 mL of 0.7 M KOH solu­
tion, the pH of the resulting solution is measured to be 13. Calculate the mass percentage of the acid in the sam­
ple. The acid has a molecular weight of 176 g/mol. Neglect volume change in mixing.
S olution : Since the pH of the final solution is 13, then the final solution is basic, and pOH of the solution
is 1. Thus [OH-] = 10' 1 M in the final solution. The mole number of OH- in the final solution is:
n = M x V = 10' 1 x 0.5 = 0.05 mol

\
144 Chapter 4 ................. И...... I......i...... .

The mole num ber of OH~ in 500 mL of 0.7 M KOH is 0.5 x 0.7 = 0.35 mol. Then the difference between
0.35 and 0.05, which is 0.30, must be used in the neutralization reaction, that can be represented by the equa­
tion:
1 mol 3 mol
H3A + 3KOH -> K3A + 3H20
x = 0.1 mol 0.3 mol

W e can deduce that 0.1 mol of acid is present in 22 g of impure acid sample. The weight of 0.1mol of acid is:
0.1 mol H 3A x 176 g / 1 mol H 3 A = 17.6 g.

The mass percentage of the acid in the sample is (17.6 g acid/22 g impure sample) x 100 = 80 g.
The sample is 80% acid by mass.

EXERCISE 4.26 A 4.5 g of oxalic acid, H2 C 20 4 and 3.42 g of Ba(OH ) 2 are dissolved in enough water
to make 600 mL of solution. Calculate the pH of the solution. l

EXERCISE 4.27 W hen 300 mL o f NaOH solution is added to 200 mL of 0.4 M H2 SO 4 , the pH of the
resulting solution is measured as 13. Calculate the concentration of the NaOH solution. 0.7 M

4.11.1 TITR A TIO N

N eutralization reactions are quite com m on in chemistry.
Generally a neutralization is perform ed by using a technique
called titration, in which a know n volum e and concentra­
tion o f one solution in a buret (so called stan d ard so lu ­
tion) is gradually added to a know n volum e o f another so­
lution until a neutral solution is obtained (end point or
equivalence point). To control the neutrality o f the final
solution, we m ake use o f the acid -b ase ind icators. A n
acid-base indicator is a substance whose color is sensitive to
the [H 3 0 +] or pH o f the m edium . F or exam ple the indicator, 5

phenolphthalein is colorless in acidic solutions but is red (or

pink) in basic solutions. If phenolphthalein is added to an
unknow n solution o f acid, the solution w ill be colorless.
Standard base should be added from buret until the solution
turns from colorless to red to understand that neutralization
is com plete. Some com m on indicators and their colors are
given in Table 4.4.
TABLE 4.4 Range and Color Changes of some Common Acid - Base Indicators
10 11 12 1 ^ pH scale
in d ica to rs H-
M ethyl orange
Methyl red
IBromthymol blue
Neutral red
Phenolphthalein colorless beyond 13.0
 ...... Acids and Bases 145

H ere w e w ill focus our attention on the titration o f strong acids o r strong
bases. T he titration o f weak acids and weak bases will be discussed at the end
o f this chapter.

EXAM PLE 4 .1 6 pH Changes During Titration of a Strong Acid with Strong Base
Problem : A O.l M of 50 mL HCl solution is titrated with 0.1 M NaOH solution. Calculate the pH of the
final solutions in each of the following cases and draw a curve showing pH versus volume of NaOH added.
(a) in the original acid solution (b) after 10 mL of NaOH solution has been added,
(c) after 49 mL of NaOH solution has been added. (d) after 49.9 mL of NaOH solution has been added,
(e) after 50 mL of NaOH solution has been added. (f) after 50.1 mL of NaOH solution has been added,
(g) after 51 mL of NaOH solution has been added. (h) after 60 mL of NaOH solution has been added.
( i ) after 100 mL of NaOH solution has been added.
Solution : (a) The molarity of H+ is the same as that of HCl solution.Because HCl is a strong monoprotic
acid. Hence [H+] = 0.1 M and pH = 1
(b) The mole number of H+ in 50 mL of 0.1 M HCl solution is n = M x V = 0 .1 x 0.05 = 0.005 mol
The mole number of OH- in 10 mL of 0.1 M NaOH solution is n = M x V = 0.1 x 0.01 = 0.001 mol
Since 1 mol H+ neutralizes 1 mol OH- , then 0.001 mol H+ out of 0.005 mol H+ will be neutralized by 0.001
mol of OH" added. The mole number of H+ remained is:

(0.005 - 0.001) = 0.004 mol and [H+] = = (^ i = 0.067M a n d pH = 1.17

VT 0.06
(c) In the same manner in part (b) the mole number of OH- added = 0.1 x 0.049 = 0.0049 mol
The mole number of H+ remained after neutralization = 0.005 - 0.0049 = 0.0001 mol
The volume of the solution is 50 mL + 49 mL = 99 mL => 0.099 L

[H+] = ° - 0 0 Q 1 = 1 x 10~ 3 and pH = 3

0.099

(d) Themole number of OH- added is 0.1 mol/L x 0.0499= 0.00499 mol
The mole number of H+ remained in excess is 0.005- 0.00499 = 1 x 10' 5 mol.
The volume of the final solution is 50 + 49.9 = 99.9 mL
-5
[IT] = 1 x 10 = 1 X 10 pH = 4
0.0999

(e) The mole number of OH added is 0.1 mol/L x 0.05 L = 0.005 mol
The solution now contains equal mole numbers of H+ and OH- , therefore the solution is neither acidic nor
basic, it is neutral like pure water and pH = 7

(f) The mole number of OH- added is 0.1 mol/L x 0.0501 L = 0.00501 mol
The mole number of OH- remained excess is 0.00501 - 0.005 = 0.00001.-
The volume of the final solution is (50mL + 50.1mL = lOO.lmL)

[OH- ] = ° -0Q 0Q 1 = 9.99 x 10~ 5 and pOH = 4 and pH = 10

0.1001
 ......... Illllllllllll.................... Hill......II.......
146 Chapter 4

g) The mole number of OH remained in excess is 0.0051 - 0.005 = 0.0001 mol.

-4 ^
[OH- ] = 1 x 10 = 9.9 X 10 pOH = 3 and pH = 11
0.101

h) The mole number of OH remained in excess is 0.006 - 0.005 = 0.001 mol.

0 .0 0 1 , _ , n _3
[O H ' ] = 9 .1 x 10 " 3 pO H = 2.04 a n d pH = 11.96
0 .1 1

i) The mole number of OH remained excess is 0.01 - 0.005 = 0.005 mol

0.005
[O H ' ] - = 0.033 pO H = 1.48 a n d pH = 12.52
0.15

The progress of the titration may be best shown by drawing the graph representing the pH changes versus vol­
ume of NaOH added. See the following figure.
1 pH
13 --
Volume of 1 2 -■
0.1 M NaOH pH
11 --
1 .0 0
0 .0 10 --
10 1.17
9 -•
49 3
8 --
49.9 4
50 7 7 --
50.1 10 6 --

51 11 5 ;-
60 11.96
4--
100
12.52
3--
2-
1 -■
v N aOH (m L )
-i— I— i— i— —I ---- 1---- 1— t-
1
20 40 60 80 100

EXERCISE 4.28 Determine pH values pertaining to the titration of 50 mL of 0.1 M H N 0 3 with 0.1 M
Ba(OH) 2 solution.
(a) in the original acid solution. (b) after 10 inL of Ba(OH) 2 has been added.
(c) after 20 mL of Ba(OH) 2 has been added. (d) after 25 mL of Ba(OH) 2 has been added.
(e) after 25.1 mL of Ba(OH) 2 has been added. (f) after 30 mL of Ba(OH) 2 has been added.
(g) after 50 mL of Ba(OH ) 2 has been added. ( b ) l . l 7 (d)7 (f)12.1
 Acide and Bases 147

4,12 CALCULATIONS BASED ON WEAK ACIDS

Д tUTf4! ' X fit C A h f О ОСТ О

W hen we deal with the solution o f any w eak acid, or weak base we keep in
m ind that there is an equilibrium betw een undissociated m olecules and the ions
produced.

As explained in Section 4.7, a sm all fraction o f a w eak acid o r base dissoci­

ates into ions and an equilibrium exists betw een undissociated m olecules and
the ions. See Section 4.7 to write the equilibrium equations and ionization con­
stant expression for weak acids and bases.

EXAM PLE 4 .1 7 Calculation of Ka for HCN

Problem : If 0.1 M HCN solution has a [H3 0 +] = 6 x 10~б M, what will be the dissociation constant for
HCN?
S olution : The equation for equilibrium is :

HCN (aq) + H20 (1) - H 3 0 + (aq) + CN' (aq)

T o p ro d u c e6 6 3
x 1СГ M o f H 0 + at
eq u ilib riu m ,6 "6
x 10 M o f 0.1 M
At start 0.1 M — = 0 = 0 o f H C N so lu tio n m u st b e d isso c i­
Change -6 x 10‘ 6 M +6 - x 10' 6 M + 6 x 10' 6 M 3
ated in to H 0 + and C N " ions. So
th e e q u ilib r iu m c o n c e n tr a tio n s
At equilib : (0.1 - 6 x 10" 6 M) 6 x IQ"6 M 6 x 10' 6 M are:
[H C N ]= 0.1- 6 x 10-6 = 0 .1 M
(B e c a u s e 6 x l 0"6 is v e ry sm a ll
Substituting these equilibrium concentrations into the Ka expression and 01
w h e n c o m p a re d to . , so it is
n e g le c te d a n d [H C N ] m ay b e a s­
solving the equation for Ka gives
su m e d to be 0.1 M )
3
[H 0 +] = 6 "6 x 10
[H 3 0 +] [CN" ] 6x10 X 6x10
-6
-to [C N "] = 6 "6 x 10
= 3.6 X 10
[HCN] 0 .1

EXERCISE 4.29 Formic acid, HCOOH, is a monoprotic acid. It is the irritant that causes the bodies re­
action to an ant's sting. If the pH of 0.5 M HCOOH is 2, calculate its acid ionization constant, Ka, and its per­
centage ionization. 2x1 O'4, %2

EXAM PLE 4 .1 8 Calculating Ka from Percentage Dissociation

Problem : 0.05 M Acetic acid, HC 2 H 3 0 2, solution has an ionization degree of 2%. Calculate the value of
dissociation constant for acetic acid.
S olution : Since the acid dissociates 2 %,
100 M of acid solution ionize 2 parts 1 ^ 1 x 10" 3
0.05 M of acid solution ionizes x i

To understand the changes in molarities during the establishment of equilibrium, examine the following table
carefully.
148 Chapter 4

HC2 H3 0 2 (aq) + H20 (1) H3 0 +(aq) + C 2 H3 0 2 (aq)

At start : 0.05 M — —- —
Change by reaction : -1 x 10" 3 M — + lx l0 3M + lx l0 3M

At equilibrium : (0.05 - 1 x 10'3) M 1 x 10' 3 M 1 x 10‘ 3 M

Substituting equilibrium concentrations into Ka expression gives:

[ H f f +] [C H £ O Q ~ ] _ ( i x i q ~ ) x ( i x 1Q~3 ) _ 0 -5

a_ " (0 .0 5 - I x l O - 3)

EXERCISE 4.30 Benzoic acid, a monoprotic acid with a formula of HC7 H 5 O 2 , is used as a preservative
in certain foods to retard spoilage caused by bacteria. A 0.01 M solution of benzoic acid 8 percent ionized. Calcu­
late Ka for benzoic acid. 6.4x10' 5

EXAMPLE 4.19 C a lc u la tin g K b from pOH

P r o b le m : Ammonia is a weak base. Its solution is suitable for cleaning windows. A household ammonia,
NH3, solution is 10% NH 3 by mass and has a density of 1 g/mL. If the pOH of this solution is 2, calculate its
dissociation constant, Kb. NH 3 = 17 g/mol.
S o l u t i o n : We must first find the molarity of the ammonia solution from the data given in the problem. One
liter or 1000 mL of ammonia solution is : 1000 mL x 1 g/mL = 1000 g
Since 10% of the mass of the solution is ammonia, 1000 g of solution contains: 1000 x 10/100 = 100 g of NH 3

m 100 g
The mole number of NH 3 is: n = = 5.88 m o l
MW 17 g /m o l

n 5 .8 8 m o l
and the molarity of the solution is: M = 5.88 M
V 1L

The equilibrium reaction of NH 3 in water solution is:

S ince the p O H o f the
NH 3 (aq) + H20 (1) NH+ (aq) + OH' (aq)
so lu tio n is , 2
At start : 5.88 M — — — 2 = - log [O H -]
Change by rxn : -0.01 M +0.01 M +0.01 M
[ОНГ] = 1 0 'P ° H = lO’ 2 M
At eq. 5.87 M 0.01 M 0.01 M
Substituting the equilibrium concentrations for equilibrium constant expression of NH 3 gives:

[NH4 ] [OIL (0 .01) (0 .01) -5

Ku = = 1.7 x 10
[NH3I (5.87)

EXERCISE 4.31 Cocaine is a monohydroxy weak base. If the pH of 5 x 10" 3 M cocaine solution is 10,

what is its K b? 2x1 O '6

 111111111111М1|1|1М1!Ш!1ШП1П!1!!!11111111Ш1Ш1!111111111111Ш111ШШ111111Ш11111111111111111111111М11111Ш11Ш111М1М11Ш11111!Ш111!111|1|11!1111111М111М A t i d e CLTld B a S e S 149

EXAMPLE 4.20 Calculating the Dissociation Constant of a Base

Problem : A 0.5 M weak base solution, corresponding to the equation,

В (aq) + H20 (1) BH+ (aq) + OH" (aq)

has the same hydroxide ion concentration as a 0.02 M NaOH solution.
(a) What is the degree of dissociation of the base in its solution?
(b) What is the value of its Kb?
Solution : (a) Since NaOH is a strong base, it is dissociated in water 100%. So the hydroxide ion concentra­
tion in 0.02 M NaOH solution is 0.02 M. The degree of dissociation of the base may be found as follows.

If 0.5 M base solution dissociates 0.02 M } ^00 x 0 02

then 100 M " ? J x = — = 4%
0.5
(b) We may calculate its Kh as follows :
В (aq) + H20 (1) BH+ (aq) + OH* (aq)
At start : 0.5 M — — —
<Change by rxn : —0.02 M + 0.02 M + 0.02 M T h e [ O H ! is 0 .02 M at
e q u ilib riu m .
At eq. : 0.48 M 0.02 M 0.02 M

K _ [BH H O H 'J _ (0.02) (0.02) = 8 3 x 10-4

b [B] (0.48)

EXERCISE 4.32 A 0 . 1 M solution of a monohydroxy base has a [H+] = 1 x 10" 10 M. What is its base
constant, Kb? lx l0 ~ 7

EXERCISE 4.33 Calculate the pH of 1 x 10*7 M NaOH solution. (Attention: pOH is not equal to 7)
7 .2
I I______________

4.12.2 CALCULATIONS OF [H+], [OH-], pH, and pOH

In these types o f questions, generally K a or K b is given, and [H+], [OH*] or

pH and pO H o f the solution are asked.

EXAMPLE 4.21 Calculation of H30 + ion in a Weak Acid Solution

Problem ; If you dissolve 0.675 g of HCN in enough water to make 100 mL of solution, what will be the
concentration of H 3 0 +, and HCN in the final solution? Ka = 4 x 10*10, HCN = 27 g/mol.
Solution : We must calculate the initial concentration of HCN

Пнш = °-6 7 5 ё = 0.025 mol [HCN] = ( U I2 5 11 1 0 1 = 0.25 M

27 g/mol 0.1 L

If none of HCN dissociated, then the molarity of HCN would be 0.25 M. But HCN dissociates as shown below.
150 Chapter 4

HCN (aq) + H20 (1) <=^ H 3 0 + (aq) + CN' (aq)

At start 0.25 M — — — let x m o l/L o f H C N d isso c iate s
Change by rxn -x M +x M +x M to e s ta b lis h th e e q u ilib riu m .

At eq. (0.25 -x ) M xM x M
3
T h is p ro d u c e s x M o f H 0 +,

and x M o f C N ’, leaving
(0.25 - x) M o f H C N u n d is s o ­
g _ [H 3 0 +] [CN~ ] _ (*) (x) i n -io _ x 2 cia te d .
[H C N ] (0 .2 5 -ж ) X 0 .2 5 -л:

Since the value of Ka, 4 x Ю’10, is so small that HCN dissociates into НзО+ and CN- to very slight extent
and, x is certainly negligible compared to 0.25. So we may simplify 0.25 - x = 0.25.

to 2
Solving x from 4 x 10 = — ------ gives* = 1 x 10’ 5 M
0.25 - *

At equilibrium we will have : [H 3 0 +] = x = 1 x 10' 5 M and [HCN] = 0.25 M

To check the validity of our assumption, compare the value of * calculated to 0.25. The value of * found,
1 x 10'5, is very small with respect to 0.25 indeed. Then our assumption is correct. The solution of the problem
is valid. If the value of x found, was close to 0.25, our assumption would not be correct. Then we would solve
the equation, 4 x Ю’ 1 0 = x 2 / (0.25 - x), for x, without any neglection. Solve Exercise 4.36 to emphasize your
knowledge about the situation where you cannot neglect "ж".

EXERCISE 4.34 The acid dissociation constants for the acids HOC1, HCN, and HF are 3 x 10"8,
4 x Ю"10, and 8 x 10' 4 respectively. Compare the pH of 0.1 M of these acid solutions ?

EXERCISE 4.35 60 grams of acetic acid CH 3 COOH, is dissolved in enough water to make 5 L of so­
lution. Calculate the [OH- ] in the solution. Ka = 2 x 10° CH 3 COOH = 60 5 x l0 '12 M

EXERCISE 4.36 Calculate the pH of 0 . 1 M solution of HI0 4, for which Ka = 2.3 x 1 0 '2 and
log 3.8 = 0.58 1 .4 2

EXAM PLE 4.22 C alcu latin g th e pH o f a S olu tion o f H yd roxylam in e, (N H 2 O H )

Problem : What is the pH of a 0.075 M solution of hydroxylamine, (NH2 OH), a weak base, for which
Kb = 1.2 x lO’8?
Solution : Let us tabulate the concentration changes during the establishment of the equilibrium.
NH2OH (aq) + H20 (1) NH 3 OH+ (aq) + OH’ (aq)
At start 0.075 M 0M 0M
Change by rxn -* M +x M +x M
A t Eq. (0.075 - x) M x M x M

[NHgOH"] [OH ] 8 x can b e n e g le cte d , b e ca u se

Kh = 1 .2 x 10 =
[N H 2OH] 0 .0 7 5 -x x « 0 .0 7 5 .

Solving the equation for x gives 3 x 10"5. Therefore, pOH = -lo g [OH"! = -lo g 3 x 10’ 5 = 5 -lo g 3 = 4.5
And pH = 14 - pOH = 14 - 4.5 = 9.5
 I ll iiiiiiiiit iiiiiiiiiiiiiiiit iiiit iiit iiiiit iiiiiiiiiin iiiiiiiiiiiiiiiiiiiiiiM iiiiiii! Acids and Bases 151

EXERCISE 4.37 A 37.2 g sample of aniline, C 6 H 5NH 2 , is dissolved in water to make 1 liter solution.
If Kb for C 6H5NH 2 is 4 x КГ9, calculate (a) [Q H 5N H ; ], [OH*], [Q H jN H J, and IH+]. (b) the percentage disso­
ciation of C 6 H5 NH2. ( c ) pH and pOH. C 6 H5 NH 2 = 93 g/mol and log 4 = 0.6
( a ) [ O H - ] = 4 x l O - 5 M , [ C eH 5N H 2]= 0 .4 M, [ H +] = 2 . 5 x l O - 10 M ( b ) 0 .0 1 % (c)p H = 9 .6, p O H = 4 .4

EXAM PLE 4.23 C a lc u la tin g th e C o n c e n tra tio n o f a B ase fro m its pOH
Problem : What concentration of ethylamine, C2 H5 NH2 , is needed to prepare a solution whose pOH = 2?
Kb for ethylamine = 4.3 x 10' 4
Solution: Let a be the molarity of ethylamine providing a pOH = 2 according to the equilibrium :
C2 H5 NH2 (aq) + H20 (1) < = ^ C2 H5 NI^+ (aq) + OH* (aq)
S ince p O H = 2
At start : a ■
— 0 0
th en [O H ’ ] = 10-2 M
Change by rxn - 0.01 + 0.01 + 0.01
at e q u ilib riu m
At Eq. : a - 0.01 0.01 0.01

TZ ,o m -4 [C 2 H 5 N H +a] [ O H " ] (0.01) (0.01)

K b = 4 . 3 x l 0 = ----------------------------- = ------------------
[C aH gN H J ( a - 0 .0 1 )

Solving this equation for a gives a = (1 x 10' 4 + 4.3 x 10'6) /4 .3 x 10~4 = 0.24 M

EXERCISE 4.38 Pyridine (C5 H 5 N) is a weak monohydroxy base. What concentration of pyridine solu­
tion has a pH value of 9 ? Kb = l x l 0 ' 9 0.1 M

EXERCISE 4.39 0.16 g of X 2 H 4 , a weak base, is used to prepare a 500 mL of solution with a
pOH = 4. Find the atomic weight of X if Kb for X 2 H 4 is I x 10"6 . H = 1 14 g/m ol

4.13 IONS ACTING AS ACIDS OR BASES:

A ll h y d ro ly s is re a c tio n s are
H Y D R O LY S IS
a c id -b a se re a c tio n s. T h e re are Any ionic solid w hen dissolved in w ater produces oppositely charged
tw o acids c o m p e tin g for H + in ions. Some ions react with water and change the neutrality o f pure water.
a re a c tio n . T h e e q u ilib riu m is The reaction o f an ion with w ater is called h y d ro ly sis. W hat types o f
fa v o re d th e s id e w h e re the ions undergo hydrolysis?
w eak er acid is found. In the re ­
1. A nions derived fro m w eak acids (such as C2H 30~2 , C N ', C 0 2f ,
a c tio n
NO] fro m HC2H 30 2, HCN, H 2C 0 3, H N 0 2) respectively react with w ater
C N '+ H 20 zz± HCN + O H ~ and fo rm basic solutions as show n below.
B oth H 20 and H C N are the ac­
ids co m p etin g for H + . C N ' (aq) + H20 (1) H C N (aq) + OH* (aq)
O O f (aq) + H20 (1) HCO 3 (aq) + O H ' (aq)

C o m m o n m eta l io n s th a t do 2. Cations derived fro m w eak bases (N H 4 , Fe3+ , A l3+fro m NH4OH,

n o t h y d ro ly ze are: Fe(OH)3, Al( OH)3 ...) react with w ater to fo rm acidic solutions.
L i+, N a+ , K + , M g2+, C a2+, NH* (aq) + H 20 (1) « = * NH 3 (aq) + H 3 0 + (aq)
.2 +
B a 2+ , SC Fe3+ (aq) + 2H20 (1) Fe(OH)2+ (aq) + H 3 0 + (aq)
C o m m o n a n io n s th at do n o t
3.Anions o f strong acids or cations o f strong bases do not react with
h y d ro ly ze are:
water. So the salts containing ions o f strong acids a n d strong bases do
C l- , B r- , I- , N O 3 , СЮ 4
not hydrolyze.H ence, the solutions o f such salts are neutral. See T able
4 .5.
152 Chapter 4

Both anions and cations hydrolyze w hen a salt containing the anion o f a w eak
acid and the cation o f a weak base is dissolved in water. The acidity or basicity
o f the solution is determ ined by the acid-base strengths o f these ions.See E xam ­
ple 4.25 (e).

E XAM PLE* 4.24 P r e d ic tin g H y d ro ly s is o f a S alt.

Problem : Does each of the following salts hydrolyze, and if it does, is its aqueoussolution acidic or basic ?
(a) M g(N 0 3 ) 2 (b) Na2 C 0 3 (c) NH 4 N 0 3
Solution :
(a) M g(N0 3 ) 2 is a salt of a strong acid, H N 03, and a strong base Mg(OH)2. Neither Mg2+, nor N 0 3 hydrolyzes.
Therefore its aqueous solution is neutral.
(b) Na2 C 0 3 is a salt of a strong base; NaOH, and weak acid H 2 C 0 3. Na+ ions donot hydrolyze. But the anion of
a weak acid, C 0 3_ , hydrolyzes producing OH~ ions according to the reaction.
C 0 3" (aq) + H20 (1) < = ^ H C 0 3 (aq) + OH~ (aq)
So the aqueous solution of Na2 C 0 3 is basic.
(c) N 0 3 is anion of a strong acid, H N 03. It does not hydrolyze. NH 4 is a cation of a weak base, NH 4 OH. It hy­
drolyzes producing H 3 0 + or H+ ions as follows.
NH4 (aq) + H20 (1) < =* NH 3 (aq) + H3 0 + (aq)
So the aqueous solution of NH 4 N 0 3 is acidic.

TA B LE 4.5 H ydrolysis o f Salts

S a lt D e riv e d E x a m p le s Io n s th a t h y d ro ly z e A c i d it y o r
F ro m b a s ic ity

S tro n g acid and N aC l, K N 0 3 none n e u tra l

S tro n g b a se C a B r 2 , S rl 2 pHs7

S tro n g acid and 4

N H C1, A1C1 3 C ations o f w eak base Acid
W ea k base CuS0 4, Z nB r 2 NFLt , A l3+, C u2+, Z n 2+ pH < 7

W eak acid and 3

C H CO O N a, K N 0 2 A nions o f w eak acid B a se
S tro n g b a se N aC N , K F, N a 2C 0 3 3
C H CO O “ , N 0 2 , C N ” , F~, C 0 3~ pH > 7

W eak acid and A nion and c atio n

W eak base И Н ^О г n h 4+ , n o 2 K a > K b => p H < 7
4
N H CN NH^ , C N ~ K a s K b => p H - 7
3
CH COO NH 4 4 3
NH , C H C O O ~ K b > K a => p H > 7
.

4.13.1 Q U A N TITA TIVE IN VESTIG A TIO N OF

HYDROLYSIS
Let us consider anion o f a weak acid, B ~ from HB. If B ~ is added to water, it
will react with water and increase the concentration o f the OH- ion.

(I) В " (aq) + H20 (1) « = * HB (aq) + OH” (aq) K b= [HB ] [QH ]
IB "]
шш1111шшш11шш1н111111111ш1м111шш111111шп11111111ш1111ш1шп1111ш11ш11111м1шшшнншш1111шш1ш1шш1н1ш|111|||мм111111ш A cids a n d Bases 153

T h e e q u ilib riu m c o n ­ W e can find the equilibrium constant o f this reaction by using Ka for HB and
s ta n t r e la te d to h y ­ K w as fo llo w s:
d r o ly s is o f a n io n
m a y b e r e p re s e n te d [ Н Р Ш “]
b y K b m e a n in g h y ­
(II) HB (aq) + H20 (1) - H 3 0 + (aq) + B '(aq) Ka =
[HB]
d ro ly sis c o n sta n t.
(III)H 2 0 (1 ) + H 2 0 (1 ) H 3 0 + (aq) + OH-(aq) Kw = [H 3 0 +] [OH*]

T o obtain reaction (I), reaction (III) and the reverse o f reaction (II) m ust be
added side by side, the equilibrium constant o f reaction (I) is obtained by m ulti­
plying the equilibrium constants o f the reactions being added.

[HB]
IW + (aq) + B“ (aq) HB (aq) + tt$> (1) K=
K.
[H P '] [ B ]
H20 (1) + H 2 p t l ) ] (aq) + O H ' (aq) K w = [H 3 0 +] [OH']

T h e p ro d u ct o f Ka and K b
B -(a q ) + H 2 O a ) < ^ HB (aq) + OH- (aq) K b= i - x K w
fo r a c o n ju g ate acid-base or a
p a ir is equal to K w or
K a x K b = K„
K a x K b = 1 x 10 '14

W here Ka is the dissociation constant for the acid and Kb is the dissociation con­
stant for the conjugate base o f the acid. Then for a conjugate acid-base pair
Ka x Кь = Kw. This equation reveals that a weak acid (small K J has a stronger
conjugate base (large K b) or vice versa.
For exam ple Ka for HCN = 4 x Ю"10, K w = 1 x 10"14, Kb for CN" = ?

-14
Ka (HCN) x Kb ( C N > Kw => Kb= —— - = 2.5 x 10
-10

A s tro n g a c id h a s a
4x Ю
w e ak e r c o n ju g a te base.
A w e a k a c id h a s a T he value o f Kb for CN" indicates that CN" is a stronger base than N H 3 w hen
stro n g e r c o n ju g a te b ase. equal concentrations are considered. Because
F or e x am p le
K a= 4 x l0 for HCN Kb(CN-) = 2.5 x IO- 5 > K b(NH3) = 1.8 x 10' 5
"5 3
K a= 2 x l0 for C H C O O H If we consider an anion o f a strong acid (such as CT, N O ; ...)
3
C H C O O H is a stro n g e r j
Kw
acid than H C N . B u t C N - K b for anion = . Since the value o f K a for a strong acid is practically infi-
is a stro n g e r b a se th an | a
3
C H COO- nite, so the value o f Kb for the anion will be zero. It m eans the anion o f a strong

acid do not act as a base. Simply it does not hydrolyze.

154 Chapter 4 lilllllllllllllllilHllllllllllllllllillilillllllllllllllllilllllllllllllllllililiiillll!!!

EXA M PLE 4.25 Prediction of the Acidity or Basicity of Salt Solution

Problem : Indicate the solutions of the following salts as acidic, basic or neutral.
Khh = 6.7 x КГ4 KH2 co 3 = 4 x 1 0 '7 КШз = 1 .8 x 1 0 '5 K HCn = 4 x 1 0 ' 10

(a) NaF (b) NaCl (c) N aHC0 3 (d)MH4 Cl (e) NH4 CN

Solution : (a) NaF solution has Na+ and F ' ions. Na+ is an ion of a strong base NaOH. Therefore it does not
hydrolyze. But F" is an ion of a weak acid HF (Ka = 6.7 x 10'4). Hence F* will hydrolyze to produce a basic so­
lution (pH > 7)
-14
F- (aq) + H20 (1) <=> HF(aq) + OH' (aq) Kb = — = - M i O = 1.5 x l ( f “ pH > 7
Ka -4
6.7 x 10

(b) The ions in NaCl solution are Na+ and CT. Both are the ions of a strong base (NaOH) and a strong acid
(HCl). Therefore neither Na+ nor CT hydrolyzes. The NaCl solution is neutral and pH = 7.
(c) In this solution HCC£ (aq) hydrolyzes as a base.
H C q (aq) + H20 (1) H 2 C 0 3 (aq) + OH' Kb = 1 * 10 = 2.5 x 10~*
4 x 10
(d) Just NH* hydrolyzes to produce acid solution.
К -1 4 10
NH* (aq) + H2 0(1) NH3 (aq)+ H 3 0 +(aq) Ka = —^ = 1 x 10 = 5.6 x 10 ” pH < 7
Kb -5
1.8x10

(e) Both NH* and CN' are derived from weak base and weak acid. Therefore both hydrolyze as shown below:
К ~ 14 10
NH+ (aq) + H20 (aq) < = ^ NH 3 (aq) + H 3 0 + (aq) Ka = —^ = -1 * 1 2 = 5.6 x 10~'°
4 Kb -5
1.8x10
К -5
CN" (aq) + H 2 0(1) HCN(aq) + O H '(aq) Kb = — 1 x 10 = 2.5 x 10
Kb -1 0
4 x 10
Because of the larger value of Kb for CN' than Ka value of NH4 we would expect CN' to hydrolyze to a larger ex­
tent than NH*. So the solution of NH4CN will be basic, pH > 7.

EXAM PLE 4 .2 6 Hydrolysis of KCN Solution

Problem : Calculate the concentrations of K+, CN', HCN, OH" and H 3 0 + in a 0.2 M KCN solution. Calcu­
late the degree of the percentage of hydrolysis of CN" in the solution. Ka for HCN = 4 x 10'10.
Solution : KCN completely dissociates into 0.2 M K+ and 0.2 M of CN' ions in water. K+, being a cation
of a strong base (KOH), does not hydrolyze. But CN', being an anion of a weak acid (HCN), hydrolyzes accord­
ing to the reaction: K -1 4 _5
CN' (aq) + H20 (1) HCN (aq) + OH' (aq) Kb = ----- = x 10 = 2.5 x 10
At start : 0.2 -— 0 0 4 x 10 '°

Changes : -x +X M +x M

At Eq. : (0.2 - x) M x M x M

When we substitute these equilibrium concentrations into the hydrolysis equilibrium, we obtain
 Acids a nd Bases 155

К _ [HCN] [OH ] 2 .5 x 10 = ^ ^ , since x « 0.2 because Kbis small,

(0 . 2 - x)
[CN ]

"5 x ~3
the equation may be simplified as 2.5 x 10 = , solving this equation we get x = 2.24 x 10 .

So at equilibrium :
[K+] = 0.2 M (The initial concentration of K+ io n ), [CN'] = 0.2 - x s 0.2 M
-14

[HCN] = [ O H " ] = x -2 .2 4 x 10_3M and [H 3 0 % - ^ - = 1 x 10 -----= 4.5 x 10_12M .

[OH ] 2.24 x 10~ 3

The degree of percentage dissociation is: (2.24 x 10' 3 M / 0.2 M) x 100 = 1.1 or 1.1 %
1 •' "" 1 ..и "I I'."-.......... . .—-II. ".-....л 1,-1 ’m "" „................. ...................

EXERCISE 4.40 What is the [OH~] of 0 .1 0 M NaN 0 2 solution ? Ka for H N 0 2 = 5 x 1 0 '4 1.4xl0'6

EXERCISE 4.41 Calculate the mass of sodibm acetate, CH 3 COONa, that must be dissolved in water to
make 0.5 L solution which has a pH value of 9. Ka for CH3COOH = 1.8 x 10- 5 CH3COONa = 82 g/mol
Hint : Lei the initial concentration o f CH3COO~ be a M, and follow the usual procedure. 7.38 g

EXAM PLE 4.27 Hydrolysis of NH4C1 Solution

Problem : What is the pH of a 0.50 M NH 4 C1 solution? Kb for NH 3 = 1.8 x 10' 5
Solution : Just NH* undergoes hydrolysis.
-14
NH; (aq) + H20 (1) NH 3 (aq) + H 3 0 + (aq). Ka = -L ii® = 5.6 x 10_1°
At start : 0.5 M — 0 0 l 8 x 10_ 5
Changes '. -x M +x M +x M
At Eq. : (0.5 - x) = 0.5 M x M x M

5.6 x 10 ~ 10 = ^ - ^ => x = 1.67 x 10”5= [H 3 0 +]

(0.5)
pH = - log [H 3 0 +] = - log 1.67 x 10' 5 = 5 - log 1.67 = 5 - 0.22 = 4.78 => pH = 4.78

EXERCISE 4 .4 2 What is the pH of 0.001 M (CH 3 COO)2Ca solution? Ka (CH 3 COOH) = 2 x 10' 5
p H =8

EXERCISE 4.43 The pH of a 0.2 M solution of KX is 10. What is the dissociation constant of the
weak acid HX? 2x10~7

EXERCISE 4.44 What concentration of hydrazine hydrochloride (N 2 H5 C 1) will produce a solution with a
pH of 5? Kb= l x l 0 ' 7 for N2 H 4 . lxlO -3
156 Chapter 4 ii k ii if ir v ii ii t i iii ii ii ii iii ii ii iii ii ii in i ii iii ii ii ii iii ii ii iii ii ii ii M f ii M i ii iii ii ii ii iii ii M i M i ii ii iii ii ii ii iii ii ii iii in iii ii ii iii ii ii ii iii iM ii ii M i ii ii iii ii ii iii ii ir ii ii iii ii ii ii iii ii iM i

4.14 COMMON ION EFFECT: BUFFER

S O L U T IO N S
A solution which contains relatively high concentrations o f both a w eak acid
and its corresponding conjugate base or a w eak base and its conjugate acid is
called a b u ffe r so lu tio n . T ypical com ponents o f a buffer solution include
C H 3 COOH, and CH 3 C O O - (CH3CO O N a dissolved in CH3C O O H solution),
NH* and N H 3 (NH 4 C1 dissolved in N H 3 solution), HCN and CN- , (NaCN dis­
solved in H C N solution). B uffer solutions are capable o f m aintaining their pH
nearly constant even when sm all am ounts o f acid o r base are added. C onsider
an C H 3 COOH and CH 3 COO- buffer system . If H 3 0 + (an acid) is added to the
solution, m ost o f the H 3 0 + is used up by the acetate ions according to the reac­
tion
CH 3 COO- (aq) + H 3 0 + (aq) <=> CH3COOH (aq) + H20 (1)
So the H 3 0 + added is converted into m olecular CH 3 COOH, therefore the pH o f
the buffer solution hardly changes. C onversely, if O H ' (a base) is added to the
sam e buffer, m ost o f it is removed by CH3COOH according to the reaction.
CH 3 COOH (aq) + OH- (aq) CH 3 COO- (aq) + H20 (1)
P r o te in s a re a m p h o te r Since the OH- added is partially converted to CH 3 COO- , the pH o f the solu­
s u b s ta n c e s , th a t is they tion changes hardly again. T here is always some pH change when acid or base
h a v e b o th a c id ic and is added to a buffer solution, but the change is far less than it w ould be if it
b a sic c h ara c te r. A s they
were not buffered. This is illustrated in Exam ple 4.29.
g a in o r lo s e p r o to n s
th e ir sh a p e a lso ch an g e . B uffer solutions play a vital role in biochem ical reactions. A change in the
T h e ir fu n c tio n d e p e n d s pH o f a living organism can be fatal. T herefore, all organism s are equipped
c ritic a lly o n th e ir shape, with naturally occurring chem ical buffer systems to m aintain their proper m eta­
and th e p H m u st re m a in bolism . F or exam ple hum an blood is buffered to a pH o f 7.4 by m eans o f
c o n s ta n t so th a t th e y
HCO- (bicarbonate), phosphate (PO- 3 ), and com plex protein system s. These
keep th e ir p a r tic u la r
sh a p e and fu n ctio n .
buffer system s absorb the effect o f a shock caused by the addition o f any acid
or base to the body.

EXAM PLE 4 .2 8 C a lc u la tin g pH o f a B u ffe r S o lu tio n

Problem : Calculate the pH of a buffer solution prepared by dissolving 26.75 g of NH 4 C1 and 4.25 g of NH 3
in enough water to form 0.5 L of solution. NH 3 = 1 7 g/mol, NH4 C1 = 53.5 g/mol, Kb for NH 3 = 2.0 x 10" 5
Solution : The solution contains a weak base, NH3, and its conjugate acid NH4. Hence it is a buffer solu­
tion. The relevant equilibrium between them is: NH 3 (aq) + H20 (1) < = ^ NH 4 (aq) + OH' (aq)
The initial concentrations of NH 3 and NH 4 are:
4.25 g / 17 g/mol + 26.75 g / 53.5 g/mol
[N H J= - ■= 0.50 M [NH4] = ---------^2------- E ----- = i m
0.5 L 0.5 L

NH 3 (aq) H20 (1) NH +4 (aq) OH' (aq) T o e sta b lish th e e q u ilib riu m
so m e O H " io n s h a v e to b e
At start 0.5 M 1.0 M 0M
p ro d u c e d by the d e c o m p o si­
Changes -x +x +x tio n o f so m e N H 3
At Eq. : (0.50 - x) M (1.0 + x) M x M
x is small enough to be neglected when added to 1.0, or subtracting from 0.5. Substitution of the equilibri­
um concentrations into the equilibrium expression gives:
 miiiiiiiimmiiiiiiiiiiiiiiiiiimiMiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiinmiiiiiiiiiiiiuuiimniiiiiiiiiiiiiiiiiiiiiiiiiiniiiiiiiiiiiii A cids a n d Bases 157

-5
[NH4] [OH ] ^ 2 .0 x 1 0 5 = illM =* x = 1 x 10
[NHj 0.5

[О Щ = 1 x IQ' 5 => pOH = - log [OH-] = - log (1 x lO'5) = 5 => pH = 9

+
Practically for an acidic buffer : K _ [Salt] [H ] For a basic buffer : K _ [Salt] [OH ]
[Acid] [base]

EXERCISE 4.45 Calculate the pH of the buffer solution prepared by adding 0.45 mol of sodium for­
mate, HCOONa, and 0.25 mol of formic acid, HCOOH to enough water to make 250 mL of solution.
К 1 . 8 x 1 O' 4

EXERCISE 4.46 Calculate the ratio of the masses of CH3COONa and CH3COOH necessary to prepare a
buffer solution with pH=5. Ka= 2 . 0 x l 0 ' 41/15

EXAM PLE 4.29 Calculating pH Change of a Buffer Solution

Problem : 0.15 mol sodium acetate (NaCH 3 COO) and 0.1 mol acetic acid (CH 3 COOH) are added to enough
water to make 1 liter buffer solution. If Ka for CH3COOH is 1. 8 x 10"5,
(a) What is the pH of the solution?
(b) What will be the pH of the solution if 0.01 mol H N 0 3 is added?
(c) What will be the pH of the solution if 0.01 mol NaOH is added?
Solution : (a) Sodium acetate, CH 3 COONa, being a strong electrolyte, will dissociate into CH 3 COO_ and
Na+ ions 100%. Therefore the concentration of CH 3 COO“ produced by sodium acetate is 0.15 M.
The existence of CH 3 COO~ ion affects the acetic acid equilibrium represented by the equation: (It will be
shifted to the left)
In s p ite o f th e e x is te n c e o f
CH3COOH (aq) + H20 (1) СН3 СОСГ (aq) + H 3 0 + (aq)
0.15 M o f C H 3 C O O - ion in i­
At start : 0.1 M — 0.15 0 tially, x M o f th e C H 3C O O H
C hanges : -x +X +x w ill d is s o c ia te to e s ta b lis h
Н ^ О + a t equilibrium .
At eq. : (0.1 - x ) (0.15 + x) x M

Since the acid is a weak one, its dissociated portion, x, will be very smaller than both 0.1 and 0.15. Therefore we
can simplify [CH3 COOH] as 0.1 and [CH3 COO- ] as 0.15 by neglecting x. The satisfaction of equilibrium con­
stant expression for the equation gives. O H - io n s are p ro d u c e d
b y th e h y d r o ly s is o f
[ C H £ 0 0 ] [H p ] 1 .8 х 1 0 - 5 = (0 Л 5 Ш С Н 3С ОСГ as follow s
K a=
[CHPOOH] (0.1) СН 3СОСГ+Н2О ^
C H 3C O O H + O H ~
Solving the equation for x gives 1.2 x 10‘ 5 . [H3 0 +] = [H+] = x = 1.2 x 10" 5 And pH of A s Н з О + is add ed it re ­
the solution is: pH = -lo g [H+] = -lo g 1,2 x 10" 5 => pH = 4.92 (Remember that the pH of m o v es O H - by n e u tra liz ­
the pure acetic acid solution was 2.9) ing th em . A s O H - is re ­
(b) 0.01 mol of H3 0 + from H N 0 3 will combine with 0.01 mol of CH 3 COO~ to produce m o v e d fro m the so lu tio n
0.01 mol ofC H 3 COOH. th e h y d r o ly s is re a c tio n
is sh ifte d to the rig h t to
CH3COOH (aq) + H20 (1) < = ^ СН3 СОСГ (aq) + H3 0 + (aq)
p ro d u c e m o re O H - . F i­
In original buffer : 0.1 M — 0.15 M 1.2 x 10‘ 5 M n a lly 0.01 m o l H 3 0 + re ­
Addition + 0.01 M m o v es 0.01 m o l o f O H -
Changes : + 0.01 M — - 0.01 M - 0.01 M w h ic h is p ro d u c e d by
In final buffer : 0.11 M — 0.14 M x M th e c o n s u m p tio n of
0.01 m o l o f C H 3C O O - .
158 Chapter 4

To satisfy the equilibrium condition the value o f x must be:

1.8 x Ю~ 5 = (0Л4) {x)- => i = 1.4 x lO" 5 and pH =4.85

(0 . 1 1 )
Thus, the addition of 0.01 mol of H+ to the buffer causes a pH change of 0.07 pH units. If it were added to water,
the pH change would be 5 pH units (from 7 to 2).
(c) The 0.01 mol of O H' from NaOH will combine with 0.01 mol of CH3COOH and 0.01 mol of CH3COONa
(0.01 mol of CH 3 COCT) will be formed.
CH3COOH (aq) + H20 (1) CH3 COO‘ (aq) + H3 0 + (aq)
In the original buffer : 0.1 M — 0.15 M 1.2 x 10~5 M
Addition 0.01 mol OH' •
Changes - 0.01 M ________________+ 0.01 M X M
In final buffer : 0.09 M 0.16 M JtM

1.8
x 1 Q"S= ( ° - M W x - i o i x 10~ 5 and pH = 4.99
(0.09)
Thus the pH change is 4.99 - 4.92 = 0.07 pH units. 0.01 mol of NaOH were added to pure water, the pH
change would be 5 pH units (from 7 to 12).

EXERCISE 4.47 Suppose you have a 1 L buffer solution that contains 0 . 2 M NH 3 and 0 . 2 M NH4 C 1 .
What will be the pH change if (a) 224 mL of HCl at STP is dissolved in the solution ? Kb for NH 3 = 1.8x10 ' 5
(b) 0.01 mol of NaOH is dissolved in the solution ? 0.0S a n d 0.04 p H unit

EXERCISE 4.48 How many grams of NaX must be added to 0.5 L of 0.5 M HX solution to yield a so­
lution that has a pH of 5? K HX = 2.0 x 10‘5, NaX = 82 g/mol 41 g

In the neutralization o f weak acids o r weak bases, we m ust pay attention to

buffer system s produced by the reaction. This is explained in exam ple 4.30.

EXAM PLE 4.30 T itr a tio n o f a W e a k B ase

Problem : Determine pH values pertaining to the titration of 50 mL of 0.1 M NH 3 solution with 0.1 M
HCl. Kb forN H 3 = 1.8 x 10' 5 ■
(a) before the addition of any HCl. (b) after the addition of 20 mL HCl. (c) after the addition of 50 mL HCl.
(d) after the addition of 60 mL HCl. (e) draw a curve to show the changes in pH as a function of NH 3 .
S olutio n: (a) NH3 (aq) + H20 (1) NH4 (aq) + OH'(aq) 1 -5 _ x
At eq : 0.1 - x =0.1 xM xM J L 8 x 10
Solving the equation for x gives x = 1.34 x 10' 3 = [OH“] => pOH = 2.87 and pH = 11.13
(b) The number of mole of NH 3 present in the solution is: (0.1 mol/L) x 0.05 L = 0.005mol.Thenumber of
mole of HCl added is: (0.1 mol/L) x 0.02 L = 0.002 mol. 0.002 mol of HCl will reactwith 0-002 mol of NH 3
to produce 0.002 mol of NH 4 C1.
NH 3 (aq) + HCl (aq) < = ^ NH+ (aq) + СГ (aq)
Initial : 0.0 0 5 mol 0.002 mol — .—
Change : -0.002 mol -0.002 mol 0.002 mol 0.002 mol
After neutralization '■ 0.003 mol — 0.002 mol 0.002 mol
Consequently the solution will contain 0.002 mol of NH4 and 0.003 mol of NH3 simultaneously. A conjugate
acid-base pair is present in (50 + 20) mL of the solution (A buffer solution).
[NHj = Q-003l^ i = 0.043 м [ n h 4] = = 0 ,0 2 9 м
a 0.07 L 0.07 L
 A cids a n d Bases 159

NH 3 (aq) H20 (1) NH; (aq) OH* (aq)

At start 0.043 M 0.029 M
Changes -x +x +x
At equilib : (0.043 - x) M (0.029 + x) M x M
Assuming that x « 0.029 and substituting equilibrium concentrations into Kb expression for NH 3 gives:
-5 m П90Л м - -5
1.8x 10 = (0-029) (x) =» x = [OH ] = 2.67 x 10 pOH =4.57 and pH = 9.43
(0.43)

(c) The number of mole of HCl added is: (0.1 mol/L) x 0.05 L = 0.005 mol.
So, 0.005 mol of HCl and 0.005 mol of NH 3 will react to form 0.005 mol of NH4 CI which will dissociate into
0.005 mol of NH^, and 0.005 mol of C P . Now the final solution which is (50 + 50) mL contains NH^ which
hydrolyzes according to the equation : [NH4 ] = 0.005 mol/0.1 L = 0.05 M
-14
NH4+ (aq) + H20 (1) NH3 (aq) + H3 0 + (aq) K. 1 x 10
Ka = = 5.56 x 10
At start : 0.05 M — — 0 Kb
1 .8 x 1 0
Changes : - x M +x M +x M
At Eq. (0.05 - x) M xM x M
x « 0.05, so, 0.05 - x = 0.05 M
-10
5.56 x 10 =- => x = 5.27 x 10 M [H30 ] = x = 5.27 x 10 pH = 5.28
0.05

(d) The number of mole of HCl added is: (0.1 mol/L) x 0.06 L = 0.006 mol
After the neutralization of 0.005 mol of NH3, the solution that is (50 + 60) mL contains 0.005 mol of NH +4 ,
and (0.006 - 0.005) 0.001 mol of H 3 0 + (excess). The equilibrium in the solution is:
NH; (aq) + H20 (1) * = * NH 3 (aq) + H 3 0 + (aq) [№Л = 2 ^ 5 = 0 045 M
At start 0.045 M — 9.1 x 10'3 M 0 .1 1

Changes : -X +x +X
0 .0 0 1
At eq. : (0.045 - x) M x M (9.1 x 10‘ 3 + x)M [H £> ] = = 9.1 x 10 M
0 .1 1

Since x « 9.1 x 10‘ 3 then [H 3 0 +] = 9.1 x 10' 3 M

and pH = 2.04
e) See the following graph to understand the changes
in pH.

V h c i (m L) PH
0 1 1 .1 3
20 9 .4 3
50 5 .2 8
60 2 .0 4

EXERCISE 4.49 Determine the pH values pertaining to the titration of 40 mL of 0.1 M HC 2 H 3 0 2 with
0.1 M NaOH solution. Ka for acetic acid is 2 x lO" 3 (a) the original acid solution, (b) after the addition of 20
mL NaOH solution, (c) after the addition of 40 mL NaOH solution, (d) after, the addition of 60 mL NaOH solu­
tion. 2 .8 5 ;4 .7 0 ;8 .7 0 ;1 2 .3
160 Chapter 4 llllllllllllllllllllllllllll Illllllllllllllllll Illllllilllllll Illlllllllllllllllllllllllllllllllllllllllllllllllillllllllllllllllllll Illllllllillll Illlllllllllllil

SOME NEW TERMS

Acid: 1) A substance which produces H30 +in aque­ Hydration: The process by which water molecules
ous solutions. bind to ions or molecules in aqueous solution.
2) A proton donor substance (Bronsted acid). Hydrolysis : The reaction of an ion with water to
3) An electron pair acceptor substance (Lewis produce acidic or basic solution. Salts of weak acids
acid). or weak bases undergo hydrolysis.
Amphoterism : Ability of a substance to behave Hydronium ion ( = Hydroxonium ion) : The
as either acid or base. hydrated H+ ion, H 3 0 + or H9 0*
Base: 1) A substance which produces OH" in aque­ Indicator : A pH sensitive dye material.
ous solution. Ionization constant : The equilibrium constant
2) A proton acceptor substance. of a weak electrolyte. Ka, Kb, Kw are specific ioniza­
3) An electron pair donor substance. tion constants for acids, bases and water respectively.
Buffer solution: A solution containing either a Monoprotic acid : (or monobasic acid): An acid
weak acid and soluble ionic salt of the acid, or a having one acid, H+ per molecule of acid, like HB.
weak base and soluble ionic salt of the base. Monohydroxy base : A base producing one OH"
Conjugate acid-base pair: In Bronsted - Lowry per molecule.
terminology, a reactant and product that differ by a Neutralization : A general type of reaction be­
H+. tween an acid and a base.
Electrolyte : A substance that produces ions in Titration : The process in which a solution of
aqueous solutions. known concentration (a standard solution) is
End point : (or equivalence point) : In titra­ added to a solution of unknown concentration until a
tion, the point that is reached when a neutral solu­ chemical reaction is complete between two reactants.
tion is obtained. Titration curve : A plot of pH versus volume of
acid or base in titration process.
REVIEW QUESTIONS AND PROBLEMS
Definitions of Acids, Bases, pH, and pOH
4.1 Define the following terms. 4.5 What is pH and pOH ? How are they related to
(a) Acid (b) Base each other ?
(c) Strong acid (d) Strong base
(e)Weak acid (f) Weak base 4.6 (a) How are acidic, basic, and neutral aqueous
solutions defined
4.2 Why is water an extremely weak electrolyte? (1) in terms of [H+] ? (2) in terms of [OH"] ?
Why is the value of the ion product constant for wa­ (3) in terms of pH ? (4) in terms of pOH ?
ter very small? (b) Indicate whether the following solutions are
acidic, basic or neutral at 25°C.
H20 (1)+13.6 kcal < = ^ Hf(aq) + OH'(aq) (a) [H+] = 1 x 1(K3 M (b) [OH'] = 1 x 10' 6 M
Kw = 1 0 ' 14 (c) pH = 7 (d) pOH = 4 (e) pH = 7.4
If the temperature of the pure water is raised, will it
still be neutral? 4.7 The compounds, HCl, NH3, CH 3 COOH, CH4,
all contain H atoms. But HCl and CH3COOH have
4.4 What is the difference between hydrogen ion, acidic properties, NH 3 has basic properties whereas
and hydronium or hydroxonium ion ? C H 4 has the properties of neither acids nor bases.
 ................ н и ш ............. . ........................................................................ i n n .... Acids a n d Bases 161

Explain. Write an equation for the reaction of each Bronsted-Lowry bases.

substance with water if possible. (1) F~ (2) OH" (3) NH 3 (4) СН 3 СОСГ (5) S2-

4.8 Define an acid or a base in three different ways. 4.12 Write equations for the reactions between the
Explain your definitions by giving examples. following acid base pairs. Indicate the conjugate
pairs.
4.9 Indicate the Bronsted-Lowry acid base pairs in (a) bicarbonate ion and water
the following equations. (b) ammonium ion and water
(a) h s o ; + HP042' н 2г о : + s o / (c) acetic acid and water
4
(b) NH 3 + H- m q + h2
(c) HC2 0 ‘ + HS- C2 o2- + H2s 4.13 Complete the following table by appropriate
(d )N ff + H20 < H 3 0 + + NH 3 calculations.
S o lu tio n [H+l fo m pH pO H A c id ity o r b a sicity
4.10 The following reactions contain conjugate A 5x10
acid-base pairs. Complete these reactions. В 5 x 10 '7
(a) HCl + NH 3 < = ^ + С 9
(b) NH 3 + CN ' + D 7
(c)Н 2 Ю / + CO2" < = ^ + E 1.0
(d) HCOOH + H20 <=> + 4.14 Decide if each of the following substances is a
Lewis acid or Lewis base.
4.11 Write (a) the conjugate bases of each of the (a) BCI3 (b) H+ (c) NH 3 (d) AIF3 (e) OH-
following Bronsted-Lowry acids.
(1) HCN (2) NH 4 (3) HCO 3 (4) H2 P O / (5) H20 4.15 When pH changes by one unit say from 3 to
(b) the conjugate acids of each of the following 4, by what factor does [H+] change ? 10

Properties of Acids and Bases

4.16 What are the general properties of acids ? Bas­ 4.20 Exactly 106 cm 3 of a solution of Na 2 C 0 3 was
es ? What properties do they have in common ? reacted with 200 cm 3 of 2.5 M HCl. If the density of
Na 2 C 0 3 solution is 1.25 g/mL, what is the percent­
4.17 What is neutralization? age by mass of Na2 C 0 3 in the solution ? 20%

4.18 Complete and balance ihe following equations 4.21 Copper does not react with binary acids, but
about acids and bases. reacts with concentrated H2 S 0 4 according to the
(a) A1 + H2 S 0 4 -> equation:
(b) H 3 P 0 4 + NaOH -> Cu (s) + 2H 2 S 0 4 (aq) ->
(c) HCl + Na2 C 0 3 -> C uS0 4 (aq) + 2H20 (1) + S 0 2 (g)
(d) CH3COOH + KOH -> How many liters of S 0 2 measured at 2 atm and
(e) Zn + НС1-» 27 °C will be produced by the reaction of 16 g of
(f) Cu + HNO 3 (cone) -> copper with excess of H 2 S 0 4 ? 2.46 L
(g) H N O 3 + H20 -»
4.22 A 50 g sample of magnalium alloy (Mg + Al)
4.19 How many liters of H2 at STP would be pro­ is reacted with excess amount of concentrated NaOH
duced by the reaction of 500 cm 3 of HCl solution solution. If 6.72 L of H2 are obtained at STP, what
whose pH = 0 and 32.5 g of zinc? Zn = 65 is the mass percentage of Mg in the alloy?
5.6 L Mg=24, Al=27 89.2%
162 Chapter 4 Ш Ш Ш Ш Ш Ш И Н Ш Н Ш И Ш Ш Ш Ш Ш Ш М Ш Ш I l l l l l l l l l l l l l l l l l l l ............................. I l l l l l l l l l l l l l l l l l l l l l l l l l l l l ............. l l l l l l l l M l l l l l l l l l i l l ......... I .................. . ............ Illlllll

4.23 H N O 3 is a strong acid. But HCN is a weak protic acid, (b) Give an example of a monohydroxy
one. Compare these acids in terms of following and a dihydroxy base?
properties. 4.26 Compare the acid strengths of H 2 0 , H 2 S,
(a) Solubilities in water. H 2 Se, H 2 Te. gO, jgS, 3 4 Se, 5 2Te
(b) Percentage ionization.
(c) The conductivities of 0.1 M solutions. 4.27 Compare the acid strengths of LiH, BeH2,
(d) pH values of 0.1 M solutions. BH 3 , CH4, NH3, H 2 0 , and HF.

4.24 Classify each of the following compounds as 4.28 Choose the stronger acid.
strong acid, strong base, weak acid, or weak base. (a) HIO 3 or HIO 4 (b) H 3 ASO3 or H 3 PO 3
(a) HCl (b) KOH (c) HF (d) H N 0 3 (c) H2S or HBr (d) H 3 SO 3 or Н2СОз
(e) NaOH (f) Ba(OH ) 2 (g) NH 3 (h) CH 3 NH 2
(i) HCN 4.29 Which factors affect the strength of a binary
acid, HX ? The compound X-O-H may act as an acid
4.25 What is a polyprotic acid? a polyhydroxy or a base. Which factors favor for this substance to
base? (a) Give an example of a diprotic acid, a tri- be an acid or a base ? Why ?

Strong Acids and Bases

4.30 Calculate the |H +] and [OH'] in 0.1 M solu­ dissolving
tion of (a) HCl (b) NaOH (c)Ba(OH ) 2 (a) 2.24 L of HCl at STP in enough water to pro­
( a) 1 O' 1 M , 1 O'13M , ( b ) 1 O'13M , 1 O' 1M , duce 10 L of solution.
( c ) S x l О '14M , 0 .2 M (b) 17.1 g of Ba(OH ) 2 in 2 L of solution.
(c) 0.1 mol of K20 in enough water to make 20 L
4.31 Why is the concentration of [H+] produced by solution. a)2 b)13 c)12
the ionization of water neglected in calculating the
concentration of H+ in a 0.1 M HCl solution? 4.35 200 mL of 0.4 M solution of НСЮ 4 is dilut­
4.32 Fill the following table for each solution ed to 8 liters. Calculate the pH of the final solution.
2
Solution [H+] [OH'] pH pOH
4.36 1.68 g of KOH is dissolved in water to make
0.05 M 0.3 liter of solution. Calculate the pH and pOH of
NaOH the solution. p H = 13 , p O H - l
0.05 M
HNO3 4.37 820 mL of HCl gas at 27°C and 3 atm is dis­
0.05 M solved in enough water to make 1 0 0 liters of solu­
Ca(OH)2 tion . What is the pH of the solution? pH=3

4.33 Complete the following table by appropriate 4.38 What volume of concentrated hydrochloric acid
calculations. (33.2% HCl by mass and d = l.l g/mL) is required
to prepare a 10 L solution with pH = 1.
Solution [H+] [OH'] pH pOH
100 mL
0.01 M 4.39 10 g sample of NaOH is dissolved in 200 mL
НСЮ 4 ? ? 7 ?
of solution. If the pH of the solution is measured to
?M be 14, find the percentage purity of NaOH sample by
HCl ? 7 3 ? mass? 80%
?M
Ba(OH) 2 7 ? 7 3 4.40 A solution was made by dissolving 5.13 g of
X(OH ) 2 in 6 L final volume. If pH of the solution
4.34 Calculate the pH of the solution obtained by was 12, what is the atomic weight of X ?
0=16H =1 137
 ..... Acids a n d Bases 163

4.41 A solution is prepared by diluting 100 mL of 4.43 Determine the mass of acid or base in each of
2.5 x 10' 3 M H N 0 3 to 25 L. What is the ratio of the following solutions.
pH to pOH in the solution ? 5/9 (a) A 4 L Ba(OH ) 2 solution whose [OH- ] = 0.02 M
(b) 1250 mL HI solution whose [OH- ] = 2.5xl0 ' 1 2
4.42 The pH of 1.0 x 10"9 M solution of HBr is (c) A 100 mL NaOH solution whose pOH = 2.
not 9.0. Why not ? (d) A 800 mL of HBr solution whose pH = 2
HI = 128, Ba(OH) 2 = 171 HBr = 81
(a)6 .8 4 g (b )0 .6 4 g (c)0 .0 4 g (d )0 .6 5 g

Neutralization and Titration

4.44 What is titration? Describe the technique of ti­ the same NaOH solution, calculate the molecular
tration. weight of the acid? 180 g

4.45 Complete the following neutralization reac­ :■ 4.51 A 100 mL sample of HCl solution is com­
tions. pletely neutralized by 80 mL of NaOH solution. A
(a) HCl + Ba(OH ) 2 -> (b) H3 PO 4 + KOH -> 10 g sample of C aC 0 3 is allowed to react with 30
(c) H2 S 0 4 + Sr(OH) 2 -» (d) HI + NaOH mL of the same acid solution. If the remaining acid
is neutralized by 8 mL sample of NaOH solution
4.46 What volume of 0.2 M NaOH solution will given above, find the molarity of the acid solution.
be needed to neutralize each of the following? 10 M
(a) 50 mL of 0.2 M HCl 4.52 A 20 mL of H 2 S 0 4 solution with a density
(b) 1 0 m L o f0 .4 M H 2 S 0 4 4 of 1.225 g/mL is neutralized by 50 mL of 0.5 M
(c) 0 . 2 mol of a strong triprotic acid. Mg(OH ) 2 solution. Calculate the mass percentage of
(a)50m L (b ) 4 0 m L (c )3 L H 2 S 0 4 in the acid solution. 10%

4.47 A 6.4 g impure sample of NaOH is complete­ 4.53 A 23.4 g mixture of Ca(OH ) 2 and NaOH is
ly neutralized by 50 mL of 0.4 M HCl. Calculate completely neutralized by 300 mL of 2 N H 2 S 0 4
the percentage purity by mass of NaOH in the sam­ solution, (a) Calculate the percentage by mass of
ple? 1 2 .5 % Ca(OH ) 2 in the original mixture, (b) What volume
of H 2 S 0 4 solution with a density of 1.84 g/mL and
4.48 To neutralize 5.88 g solution of a triprotic is 98% H 2 S 0 4 by mass is needed for this neutraliza­
acid that is 50% acid by mass, a 200 mL of 0.15 M tion? ( a ) 3 1 .6% ( b ) 1 6 .3 m L
NaOH solution is used. Find the molecular weight
of the acid. 2 9 4 g /m o l 4.54 Calculate the pH value of each of the solu­
tions obtained by mixing
4.49 A diprotic acid has the following composition (a) 200 mL of 0.014 M HCl and 300 mL of 0.011
by mass: 26.68% C, 71.1% О and 2.22% H. If 50 M NaOH.
mL of 1 M NaOH may neutralize 2.25 g of this (b) 100 mL of 0.2 M HBr and 100 mL of 0.1 M
acid, what is the molecular formula of this acid? Ba(OH)2.
C=12, 0=16, H=1 C2H 20 4 (c) 10 mL of 0.4 M HCl and 30 mL of 0.12 M
KOH.
4.50 800 mL of NaOH solution are required to neu­ (d) 100 mL of a solution with a pH = 2 and 100 mL
tralize a 90 g sample of a diprotic acid. If 500 mL of of a solution with a pOH = 12.
0.75 M H 2 S 0 4 solution can neutralize 600 mL of (e) 100 mL of a solution with a pH = 3 and 100 mL
164 Chapter 4 НИНИШШИИННШМИШНН IIIIIIIIIIIIIIIIIIIIIIIII I lllll .

of a solution with a pH = 11. the solution. What volume of CO 2 at STP is

(f) 450 mL of a solution with a pH = 4 and 550 mL formed? KOH = 56 2.24 L
of a solution with a pH = 10.
(a )ll (b )7 (c)2 (d )2 (e)7 (f)9 4.58 6.30 gram sample of hydrated oxalic acid,
4.55 What volume of 0.6 M H2 S 0 4 must be added H 2 C 2 O 4 .XH2 O, is used to prepare 500 mL aqueous
to 200 mL of 0.4 M KOH solution so that the pH solution, and 50 mL of this solution requires 20 mL
of the resulting solution will be 12? 64 mL of 0.50 M NaOH for neutralization. Determine the
numerical value of x in the formula of the hydrate.
4.56 A 200 mL of solution with pH = 2 and anoth­ 2
er 300 mL of solution with pH = 12 are mixed. 4.59 Draw a titration curve showing pH as a func­
What volume of 0.05 M NaOH or 0.05 M H2 S 0 4 tion of volume of NaOH solution added when the
will be needed to neutralize the resulting solution? following volumes of 1 M NaOH solution are added
10 mL H2 S 0 4 to 100 mL of 1 M HI solution, (a) 0 mL (b) 10 mL
(c) 20 mL (d) 50 mL (e) 90 mL (1) 99.9 mL (g) 100
4.57 A quantity of 5.6 g of KOH is added to 300 mL (h) 101 mL
mL of 1.0 M HCl. Excess СаСОз is then added to

Weak Acids and Weak Bases

4.60 HNO 2 , HCOOH, H2 C O 3 are examples of 4.64 A solution of nitrous acid, (H N 02) contains
weak acids, and NH 3 , CH 3 NH 2 , C 6 H5 NH2 , N 2 H4 are 1.41 g of H N 0 2 in 10 L and has a pH value of 3.
examples of weak bases. Write the acid or base dis­ What is the dissociation constant of the acid?
sociation constant expressions for each of these sub­ 5x1 0'4
stances. 4.65 An aqueous solution of a weak acid, HB, has
the following composition: [H+] / LHB] = 2 x 10" 5
4.61 The ionization constants for a series of acids and [OH- ] / [H+] = 2 x 10~5 . Calculatethe value of
with the general formula, HB, are given below. Ar­ К a for the acid. 4 x 1 0 ' 10
range the acids in order of increasing their strengths.
(a) Ka (HCN) = 5 x Ю" 10 4.66 Calculate (a) the [H+], [OH"], pH, and pOH of
(b) Ka (HCIO) = 3 x 10" 8 the following acid solutions.
(c) Ka (CH 3 COOH) = 2 x lO' 5 (a) 0.1 M HF (b) 0.01 M HF
(d) Ka (HCOOH) = 2 x 10"4 (c) 0.01 M HCN (d) 0.01 M HCOOH
Refer to the table 4.2 for ionization constants of ihe
4.62 A 9.4 g sample of the acid, HB, is dissolved acids.
in 500 mL of solution, has a [H+] = 1 x 10" 4 M.
If the molecular weight of the acid is 188 g/mol, cal­ 4.67 What molarity of C 6 H5COOH solution is re­
culate quired to prepare a solution which has a pH = 2 ?
(a) the molarity of the acid solution. K a for Q H 5 COOH = 5 x 10" 5 2M
(b) the degree of the percentage dissociation of the
acid solution. 4.68 A 0.1 M ethylamine, C 2 H 5 N H2, solution is
(c) the [B'] 8 % dissociated into C2 H5 NH 3 , and OH". Calculate

(d) the value of Ka for HB the value of Kb for this base. 6.5x1 O'4
a)0.1 M b) 0.1% c ) l x l 0 ~4 d) IxlO ' 7
4.63 A 0.05 M CH 3 COOH solution is 2 % dissoci­ 4.69 170 mg of piperidine, the active constituent of
ated. What is the dissociation constant for acetic acid the black pepper, is dissolved in 2 L of water. Calcu­
(С Н 3 СООН)? 2 x 1 O' 5 late the pH of this solution.
Kb = 1.6 x lO" 3 and C 5 H „N = 85 g/mol.
 I I п и п и ..... inn.... ш п и н и ..... in.... .....
п н п и ш и ............. и м и ... .......A cids a n d Bases 165

C 5 H „N + H20 <==r CsHn NH+ + OH- 4.76 Many of nonmctal oxides such as SO 2 , N 2 O 5 ,
10.8 NO 2 , CO 2 dissolve in water to produce acids. There­
4.70 Calculate (a) the hydroxide ion concentration, fore acid rain is a result of these oxides. Assuming
(b) the percentage ionization of the following aque­ that the acidity is due to the presence of HNO2 in the
ous base solutions. rain, what is the total concentration of HNO 2 in a
(1) 0.05 M NH 3 (Kb = 2 x 10"5) rain sample whose pH = 4? K hno 2 = 5 x 10' 4
(2) 1.4 M C 2 H5 NH2, (Kb = 6.4 x 10'4) 1.2x l 0 '4
(3) 0.012 M N 2 H4 (Kb = 1.2 x lO '6) 4.77 Calculate the concentration of each ion in a
(4) 1 x 10' 2 M C6 H5 NH 2 (Kb = 4.0 x Ю '10) solution prepared from 2 mol of H 2 S 0 4 and enough
(2)[OH~]=0.03M ; (4)[OH-]=2xlO'6 M water to make 2 L of solution.
I - HjSO,, (aq) H+ (aq) + HS0 4 (aq)
4.71 A 1.58 g sample of a monohydroxy base, B, Kj = large
is dissolved in enough water to form 0.4 L of solu­ II - HS04"(aq) <=> H+ (aq) + SO2" (aq)
tion. If the pH of the solution is 9, what is the mo­ K 2 = 1.2 x КГ 2
lecular weight of the base? Kb for base is 2 x 10‘ 9 (Assume that the first reaction is complete. Use the
79 g /m ol H+ and HSO4 produced by reaction I for the second
equilibrium).
4.72 What molarity of NH 3 solution provides a pH [H +] = 1 . 0 1 1 7 M , [ S 0 4 ~] = 0 . 0 1 1 7 M
value of 11? (Kb= 2 x l0 "5) 0.051M
4.78 Hydrogen sulfide, H 2 S, is a diprotic acid with
4.73 The weak acid, HXO, has a Ka = 2 x 10"8. A Kj = 1 x 10" 7 and K2 = 1 x 10"14. Calculate the con­
quantity of 1.05 g of HXO is dissolved in enough centrations of H2 S, HS", S2' , and H 3 0 + in a 0.1 M
water to make 4.0 L of solution whose pH is 5. solution of H 2 S?
Find the atomic weight of X. 35.5 g/m ol [ H 2S] =0.1 M , [H3 O +] = [ H S - ] = l x l 0 - 4 M,
[ S 2~ ] = l x l 0 ~I4M
4.74 Calculate the pH of 500 mL of 0.1 M solu­ 4.79 A monohydroxy weak base, B, is 0.1% ion­
tion of HCIO 2 to which 0.01 mol of HCl has been ized in 1 M solution. At what concentration is the
added. К п сю 2 = 1 x Ю"2, log 4 = 0.6 1.4 base 1 % ionized? 0.01 M

4.75 Saccharin, an artificial sweetner as a sugar 4.80 A solution is prepared by dissolving 1.00 mol
substitute, is a weak monoprotic acid, HNC 7 H 4 SO2 , of HF in 1000 g of water. If the solution freezes at
with a Ka = 2.0 x 10"12. Calculate the [H+], [OH-J, -1.89°C , calculate the value of Ka for HF at
pH and pOH of 0.01 M solution of this substance. -1.89°C. (Remember that 1 mol of particle lowers
p H = 6 .8 5 the f.p of 1 kg of water by 1.86°C.) 2 .6x 1 O' 4

Hydrolysis
4.81 What is hydrolysis? What types of ions under­ (a) NaCl (b) KF (c) (NH 4 ) 2 S 0 4
go hydrolysis? (d) K2 C 0 3 (e) CH3COONa (f) KC10 4
Classify each of them as acidic, basic, or neutral.
4.82 What factors will determine the solution of an
4.84 Decide whether the solution of HCOONH 4 is
ionic salt to be
acidic or basic.
(a) acidic ? (b) basic ? (c) neutral ?
Kb(NH3) = 2 x 10"5 Ka(HCOOH) = 2 x 10"4
a c id ic
4.83 Consider 0.5 M aqueous solutions of the fol­
4.85 What are the [H+], [OH'], pH, pOH of the
lowing compounds.
each of the following salt solutions? (Sec Table 4.2)
166 Chapter 4 ишштунишшггшмкнмшптшггшпшшшгшмтшттншшгмншшпгшшштшшншшшшшшншшшишшшшшшшшиин

(a) 0.05 M N aN 02 (b) 0.1 M N H 4 C1 reactions, decide whether Na2 HP0 4 solution is acidic
(с) 0.2 M NaCN (d) 0.001 M CH3COONa or basic.
(е) 0.1 М C2H5NH3C1
4.87 What concentration of sodium acetate solution
4 .8 6 (a) Arrange the following ions in the order of provides a pH=9? Ka for CH 3 COOH=2xlO " 5 0.2M
increasing base strength 4.88 The pH of a 0.1 M NaX solution is 10 and
(l)C H 3COO- (2) С Г (3 )N 0 2 (4)F~ NaX is a salt of the weak acid, HX. Find the dissoci­
(You may use Table 4.2 for Ka and Kb values.) ation constant for HX. lx lO '7
(b) HPO 4 ' may act as an acid or a base on dissolving
in water. Write these possible reactions. Depending 4.89 NaCN solution has a higher pH value than
that of NaF. Which acid will have a higher value of
on the values of the equilibrium constants of these
Ka? Explain.

Buffer Solutions
4.90 What do we mean by a buffer solution? Why ed to 50 mL of 0.1 M CH 3 COOH.
are buffer solutions important? (a) 0 mL (b) 25 mL (c) 50 mL (d) 75 mL

4.91 Calculate the [OH"] of each of the following 4.96 How many grams of NH 4 CI is necessary to
solutions. (Use Table 4.2) prevent the formation of a Mg(OH ) 2 precipitate in a
(a) 0.1 M NH 3 and 0.1 M NH 4 C1 one liter solution that is 0.01 M in Mg2+ and 0.05
(b) 0.2 M NH 3 and 0.1 M (NH4 )2 S 0 4 M in NH3? The Ksp for Mg(OH ) 2 is 9 x 10" 12
(c) 0.05 M HCN and 0.05 M Ba(CN ) 2 K b( N H 3) = 1.8 x 10 " 5 1.6 g
(d) 0.05 M HCIO and 0.1 M NaCIO
4.97 Lactic acid is a component of sour milk. It is
4.92 Calculate the [H+] in a buffer solution pre­ a monoprotic acid with the formula, HC 3 H 5 0 3.
pared by mixing 500 mL of 0.1 M NaF and 500 mL When 8.96 g of NaC 3 H 5 0 3 is added to 100 mL of
of 0.02 M HF. (Ka for HF = 6.7 x 10"4) 0.05 M solution of lactic acid, the pH of the solu­
1 ,3 4 x l0 '4 M tion is 4.0. Determine the ionization constant of the
4.93 Hypobromous acid, HOBr, is a weak acid with lactic acid. NaC 3 H 5 0 3 = 1 1 2 1.6x10 -3
K a = 2 x 10"9. If you mix 7.3 g of HCl and 23.8 g
of NaOBr in enough water to make 4 liters of solu­ 4.98 When 1 liter of 0.3 M solution of formic acid,
tion, what will be the pH of the solution? p H = 5 Н С 0 2 Н, and 0.5 L of solution of sodium formate
(H C 0 2 Na) are mixed, the pH of the final solution is
4.94 How many grams of NH 4 N 0 3 must be added found to be 4. What is the concentration of the sodi­
to 100 mL of 0.4 M NH 3 to prepare a buffer solu­ um formate solution? Ka = 2 x 10 for formic acid.
tion with a pH of 10? Kb = 2 x 10' 5 6.4g 1.2 M
4.99 Calculate the [OH- ] of a solution resulting
4.95 Draw a titration curve showing pH as a func­ from mixing equal volumes of 0.30 M NH 3 and 0.1
tion of volume of NaOH solution added when the M HNO 3 . Kb for NH 3 = 2 x 10"5 4x10'
following volumes of 0.1 M NaOH solution are add-

Miscellaneous Problems
4.100 Alkali metals react with water to give basic 4.101 A solution has a pH = 2. Another solution
solutions. has a pH = 9. In what volume ratio must these solu­
M (s) + H20 (1) -> M+ (aq) + OH- (aq) + 1/2H2 (g) tions be mixed so that the resulting solution has a
Calculate the pH of the solution resulted from the re­ pH = 7 ?
action of 1.56 g of potassium with 400 mL of wa­ 1 0 0 0 /1
ter. К = 39 13
 пп1111!111111111...............in и ................ пиши.......... пн пни mi A c id s a n d B a s e s 167

4.102 Phenol, C 6 H 5 OH, is a weak monoprotic acid 4.112 Given that Kb = 1.6 x 10" 5 for
with Ka = 1.6 x 1СГ10. The pH of a saturated solu­ NH3 + H20 < = » N H + + OH",
tion of phenol is 5. Calculate the solubility of phen­ how much H 20 would you need to add to 200 mL of
ol in grams/liter. C 6 H 5 OH = 94 g/mol 150.4g/L 4 M NH3 to double the percent conversion of NH3
into NH* ? Assume additive volumes. 600 mL
4.103 Will a precipitate of Fe(OH ) 2 form in a
4.113
0.0001 M solution of Fe(N 0 3 ) 2 if the pH of the so­
lution is adjusted to 9? Ksp (Fe(OH)2) = 1.6 x 10"14.
No
4.104 How many moles of Mg(OH ) 2 will dissolve
in one-liter of a solution of NaOH with a pH of 12?
K sp(M g (O H )2) = 9 x 10" 1 2 9 x l 0 ' 8 m ol

4.105 A saturated solution of a slightly soluble hy­

droxide, M(OH)2, has a pH of 10. What is the Ksp of
M (O H )2? S x l O ' 13

4.106 Explain the fact that the solubility of slight­

The given graph is plotted by using the data obtained
ly soluble salts containing basic anions is higher in
in the titration of (1) NaOH solution (2) NH 3 solu­
acidic solutions than in pure water.
tion with 0.1 M HCl solution.
(a) Which curve belongs to the titration of the solu­
4.107 A volume of 50 mL of 0.1 M NH 3 is mixed
tion with NaOH ?
with an equal volume of a solution containing 0 . 0 1
(b) Which curve belongs to the titration of the solu­
mol of Cd(N03)2.
tion with NH 3 ? Account for your answer.
(a) Will Cd(OH ) 2 precipitate ?
(c) What are the initial concentrations of NaOH and
(b) How many grams of NH 4 NO 3 must be added to
NH 3 solutions. Kb(NH3) = 2 x 10"5 and for
the resulting solution to prevent the precipitation of
pH = 1 1 .2 = 7 [H+] = 7.1 x 10" 1 2
Cd(OH)2. Ksp for Cd(OH ) 2 is 1.6 x 10'14.
(d) Even though NaOH is strong base and NH 3 is a
K b(NH3) = 2 x 10' 5 NH 4 NO 3 = 80 g/mol (b)20 g
weak one, approximately equal volumes of base so­
lutions are used for the neutralization. How can you
4.108 How many liters of water must be added to
explain this ? (Remember Le Chatelier's principle)
change the pH of 1 liter of solution from 2 to 4?
99 lite r s 4.114 Can we have a strong electrolyte in dilute
4.109 How much water must be added to 300 mL solution? Explain.
of a 0.2 M solution of acetic acid for the degree of
4.115 Consider the equation :
dissociation of the acid to double? 900 mL
CH3COOH (aq) + CO5 (aq) <=>
4.110 One liter of a 0.01 M solution of acetic acid CH 3 COO- (aq) + HCO3" (aq)
contains 6.26 x 1021 of its molecules'and ions. De­ (a) Ka(CH3 COOH)=1.8 x 10"5 and Ka(HCO)j=5x КГ7,
termine the degree of dissociation of the acid. 0.04 Decide qualitatively whether the reactants or products
\ -are favored by the equilibrium.
4.111 Suppose you mix equal volumes of NaOH (b) Calculate the value of the equilibrium constant
for the reaction.
solutions that have pOH's of 0 and 1 respectively.
What will be the pH of the resulting solution? (c) What will be the concentration of each species in
1 3 .7 4 a solution that is prepared by dissolving 1 mol of
CH3COOH and 1 mol of Na 2 C 0 3 in enough water
to make 1 L solution?
168 Chapter 4 Ш Ш Ш Ш Ш Н Ш Н И Ш Н Н Н Ш Ш Ш Н Ш Н ............................. I ............................................ П И Ш И ........... Ш И П ............. Н И Ш И ......... .

SELF TEST

1. Which statement is correct about acids and bas­ 7. A 0.75 g sample of a diprotic strong acid can be
es? neutralized by 37.5 mL of 0.2 M KOH solution.
A) If [OH"] = [H+], the solution is acidic. Which is the molecular weight of the acid in g/mol?
B) If pH > 7, the solution is acidic. A) 100 B) 156 C) 200 D) 246 E) 375
C) If pOH < 7, the solution is acidic.
D) If pOH = 0, the solution is acidic. 8. A 20 mL sample of 0.2 M H 2 S 0 4 is added to 20
E) If [H+] = I x 10" 6 M, the solution is acidic. mL of 0.2 M NaOH. Which is the [OH'] of the re­
sulting mixture ?
2. Which pairs of the species in the following reac­ A) 1 x 10" 13 M В) 1 x 10" 8 M
tions are Bronsted bases? C) 1 x 10" 7 M D) 1 x 10" 6 M
H20 + CN" HCN + OH" E) 1 x 10"4 M
h 2o + n h ; H 3 0 + + NH 3
A) H 2 0 , HCN and H 2 0 , H 3 0 + 9. One molar solution of HCN ionizes 0.01% at
B) CN", OH" and NH+, NH 3 20°C. Which is the dissociation constant of HCN ?
C) H 2 0 , OH" and H2 0 , OH" A) 1 x 10" 4 В) 1 x 10" 5 С) 1 x 10" 7
D) CN", HCN and NHa , NH 3 D) 1 x 10"s E) 1 x Ю" 10
E) CN", OH" and H2 0 , NH 3
10. Which one of the following is the [H 3 0 +] of
3. Which is the ratio of the pH of 0.1 M HCl to 0.02 M CH3COOH solution? Ka = 1.8xl0 " 5
that of 0.05 M Ba(OH ) 2 solution : A) 1. 8 x 10" 3 B) 6 x 10 "4 C) 3 x 10" 5
A) 1/2 B) 1/10 C) 1/13 D) 1/11 E) 2/1 D) 4.2 x 10" 3 E) 4 x 10" 6

4. The pH of a solution is 6 times greater than its 11. What molarity of the acid, HX, provides a solu­
pOH. The solution may be: tion whose pH = ...? Ka = 2 x 10" 9
A) 0.2 M HCl B) 0.2 M NaOH A) 0.05 B) 0.025 C) 0.2 D) 0.4 E) 0.5
C) 0.01 M H N 0 3 D) 0.01 M Ba(OH) 2
E) 0.01 M KOH 12. The [H+] of a solution prepared by dissolving
0.2 mol of C6 H 3 NH 2 in 200 mL of solution is 2 x
5. Equal volumes of solution A with [H+] = 1 x 10" 8 M. Which is the base constant for C 6 H5 NH 2 ?
10" 4 M and solution В with [H+] = 1 x Ю" 10 M are A) 4 x 10" 16 B) 5 x 10" 7 C) 2.5 x 10" 12
mixed, which is the pH of the resulting solution ? D) 5 x 10" 15 E) 2.5 x 10" 13
A) 9 B) 8 C) 7 D) 6 E) 5
13. Consider equal concentrations of the following
6 . A 10 g sample of vinegar, CH 3 COOH, solution, acids and the statements about them.
is neutralized by 12.5 mL of 0.8 M NaOH solution. Acid Ka
Which is the mass percentage of the acid in the solu­ HCl very large
tion ? CH3COOH = 60 g/mol. HN 0 2 ’ 5 x 10' 4
A) 3% B) 5% C) 6 % D) 8 % E) 10% HCIO 3 x 10"8
1. HCl solution has the highest pH value.
II. HCIO solution has the highest [OH-].
 inn ...... mi.... ...............и...... inn.................. Acids a n d Bases 169

III. H N 0 2 is a weaker acid than HCIO. pH of 8 ? KN 0 2 = 85 g/mol, К 1 Шо 2 = 5 x 1 0 ^

IV. HNO 2 solution conducts electricity better than A) 0.85 B) 1.7 C) 3.4 D) 5.1 E) 8.5
HCIO solution.
Which one (s) of these statements are correct ? 18. Which one of the following bases is the weak­
A) I, III, IV В) II, IV C )I,IV D) И, III E) I, II est?
A) NH3 (Kb = 2 x lO"5)
14. What percent of a 0.01 M NH 3 dissociates in B) CN" (Ka = 2 x 1O' 9 for HCN)
aqueous solution? Kb = 1 x 10" 6 C) CH 3 COO- (Ka = 2 x lO' 5 for CH 3 COOH)
A) 0.1% B) 0.5% C) 1% D) 2% E)5% D )F- (Ka = 7 x 10"4 for HF)
E) C102 (Ka = 1 x lO’ 3 for HC102)
15. Kb for hydrazine, N 2 H 4 , is 4 x 10'6. Which is
the pH of 0.25 M N 2 H 4 solution ? 19 - Which is the molar ratio of CH3COOH to
A) 3 B) 9 C) 10 D) 11 E) 12 CH3COONa necessary to prepare a buffer solution
with pH = 3?
16. What must be the minimum [Mg2+] to start the Ka = 2 x lO' 5 for CH3COOH
precipitation of Mg(OH ) 2 in a 0.01 M NH 3 solution? A) 30 B) 40 C) 50 D) 60 E) 80
Kb for NH 3 = 2 x lO" 5
Ksp = 2 x 10' 1 2 for Mg(OH)2. 20 - How many moles of NH4 C1 must be dissolved
A) 1 x lO" 5 В) 1 x 10' 8 С) 1 x lO" 9 in 1 L of 1 M NH 3 solution to prepare a buffer with
D) 1 x 10"n E) 1 x 10" 14 a pH of 10? Kb = 2 x 10" 5 for NH 3 (Assume no
volume change)
17. How many grams of K N 0 2 have to be dis­ A) 0.1 B) 0.2 C )0.3 D) 0.4 E) 0.5
solved in 400 mL of water to have a solution with a
 CHAPTER

OXIDATION - REDUCTION
REACTIONS
AND ELECTROCHEMISTRY

The objectives o f this chapter are to enable the student to :

1 - Identify an oxidation - reduction reaction.
2 - Separate an oxidation reduction reaction into half - reactions.
3 - Identify oxidizing and reducing agents.
4 - Balance oxidation - reduction reactions by means of half-reaction met­
hod and oxidation - number method.
5 - Assemble an electrochemical cell, using electrodes, electrolytes and a
salt bridge.
6 - Write the electrode reactions, and the cell reaction from the changes
taking place in the cell.
7 - Describe the standard hydrogen electrode (SHE) and explain how ot­
her standard electrode potentials are measured with respect to SHE.
8 - Tabulate the standard reduction potentials of half - reactions.
9 - Use the values of standard reduction potentials
a - to calculate Eccli
b - to decide whether a given reaction occurs spontaneously.
10 - Describe the affect of concentration changes on the cell potentials, bo­
th qualitatively and quantitatively.
11 - Use Faraday's laws o f electrolysis to calculate the amounts o f chan­
ges and quantity o f electric charge.
12 - Desribe corrosion, and some common voltaic cells: the dry cell, the
mercury cell, the lead storage battery, the nickel - cadmium cell.
iiiu u u iiiu u u iiiiu iiiu m iiiiiiiiiiiiiiiu u u iu iu iiim u u iiiiiiiiiiiiiiiiiiiiiiiu iu iiiiiiiiiiiiiu iiiH iiiiiiiiiiiiiiiti Oxidation - Reduction Reactions 173

In chapter 4 we considered the acid - base reactions. An acid - base reaction

involves a proton transfer from a species to another. N ow we w ill consider an­
other type o f reaction that involves electron transfer. These reactions are called
oxidation - reduction reactions.
L G
0 a 5.1 OXIDATION - REDUCTION PROCESSES
s i
s n W hen m agnesium m etal bum s in air, it com bines w ith oxygen, m agnesium
oxide, a white pow der, is formed.
0 о
f f M g (s) + l / 2 0 2 (g) — > M gO (s)
e W hat is the reason for the occurrence o f this reaction? T he electron configu­
0 R
1
e +2 e rations for M g and О are
x с
E
с
t t 12M g : ls 2 2s 2 2p 6 3s2 and 80 ; ls 22s22 tf
1 r
r
0 о M agnesium has 2 m ore electrons than the inert gas, Ne, and oxygen has two
D U
n n less electrons than the inert gas, Ne. To reach the inert gas-like electron popula­
s s
A С tion, m agnesium gives tw o electrons to oxygen, and M g2+ and O 2' ions are
M M form ed. B ecause o f their opposite electric charges, they attract each other and
T 0 T
о form M gO. A lthough electron loss and electron gain m ust occur sim ultaneous­
r r
I I
e e ly, it is often convenient to consider them as two separate processes: E lectron
-1
О n О loss process and electron gain process. The equations which show either elec -
P
0 e tron loss or electron gain alone are called half-reactions. Simply in the reaction
N N
s g there are two half-reactions.
1 -2 a
t t (1) The half - reaction in which electrons are lost.
i 1
v v Mg Mg2+ + 2e_
e e
(2) The half reaction in which electrons are gained.
с с 2 -

h h l/2 0 2 + 2 e- — > О
a a
r г The sum o f these two half reactions gives the overall or net reaction.
g g
с e
Mg — > Mg2+ + 2e-
l/2 0 2 + 2e- — ■» O2-
Mg + l/2 0 2 MgO 2
M g +0 2_ : M gO

A chemical change involving electron transfer is called an oxidation-

reduction reaction, or a redox reaction. An oxidation-reduction reaction
consists o f two h alf reactions.
(1) Oxidation-half reaction : T he h a lf reaction in w hich electrons are
lost is called the oxidation-half reaction. In our exam ple the oxidation-half reac­
tion i s :
Mg Mg2+ + 2c~
The process o f loss electrons is called "oxidation".
(2) Reduction - half reaction : T he h a lf reaction in w hich electrons are
gained is called the reduction half reaction. In our exam ple the reduction half re­
action is:
174 Chapter 5 ш и м м м м м м ш м м м ш м и и ш ш п п н м ш п ш м ш ш п и ш ш ш м м м ш м ш п и м п и м м м ш м м и ш ш ш ш м м п ш п ш п ш ш м м м м м м ш ш ш ш ш и п п п ш п ш !

1 / 2 0 2 + 2 e- — > 0 2‘
T he process o f gain o f electrons is called "reduction".
T he num ber o f electrons lost in the oxidation - h alf reaction is always equal
to the num ber o f electrons gained in the reduction - h alf reaction. T he sum o f
these two half reactions gives the overall reaction or oxidation - reduction reac­
tion after cancelling the electrons.
M g + l/2 0 2 — > MgO
The species w hich undergoes the oxidation process is called "the oxidized
substance". The species w hich undergoes the reduction process is called "the
reduced substance". In our exam ple M g is the oxidized substance, and oxy­
gen is the reduced one.
The electrons given by the oxidized substance causes the reduction o f the re­
duced substance. H ence the oxidized substance is called "the reducing
agent" o r "reductant". And the reduced substance causes the oxidation o f the
oxidized substance by accepting the electrons. H ence it is called "the oxidiz­
ing agent" or "oxidant". In our exam ple m agnesium is the reducing agent
O x id iz in g a g e n t g a in s
and the oxygen is the oxidizing one.
e le c tro n s . R e d u c in g
a g e n t lo s e s e le c tro n s .
These term s are summarized in the following table.
R e d u ce d su b stan ce is a l­
Mg o2
w ays o x id iz in g a g en t.
loses electrons gains electrons
undergoes oxidation half reaction undergoes reduction half reaction
the oxidized substance the reduced substance
the reducing agent the oxidizing agent

EXAMPLE 5.1 Basic Terms for Oxidation Reduction - Reactions

Problem : When the metallic copper is immersed in a
solution containing Ag+ ions, the metallic copper dissolves
deposit of solution develops
in the solution producing Cu2+ ions, and the metallic silver
solution is metallic silver Cu
colorless I
a blue color
is deposited on the surface of the copper metal. See the fig­
ure given aside.
Ag+ ‘3 N03
к ' (a) Write the balanced oxidation and reduction half reac­
о.

i n°3
I у tions.
(b)
(b) Write the oxidation - reduction reaction.
(c) Indicate the oxidized substance, the reduced substance,
the oxidizing agent and the reducing agent.
Solution : (a) In the reaction Cu2+ ions are formed from neutral metallic copper. This is represented by the
half reaction:
Cu — > Cu2+ + 2e* (oxidation - half reaction)
Since the metallic silver (neutral silver atom) is produced from Ag+ ions, the reaction representing this
change is:
Ag+ + le ' — » Ag (reduction - half reaction)
(b) The oxidation - reduction half reaction is the sum of the two half reactions, but the number of electrons
||шш1ш111111111ш|111111ш11шшм11111111шм111ш1111пш111!11111111шш1!шш1м111111111шшм11м1м1ш1п0хг£/а£шн - Reduction Reactions 175

lost and gained must be equal on both half reactions so that the electrons cancel when the reactions are added.
2Ag — > 2Ag+ + 2e‘ (We multiply this reaction by two)
Cu2+ + 2e‘ — > Cu
2Ag + Cu2+ — > 2Ag+ + Cu
(c) Each copper atom loses two electrons, therefore it is the oxidized substance but it is the reducing agent or
rcductant.
Each silver ion gains one electron, therefore it is the reduced substance but it is the oxidizing agent or oxi­
dant.

E X E R C IS E 5.1 Determine the oxidation - half reaction, the reduction - half reaction, the oxidized sub­
stance, the reduced substance, oxidizing and reducing agents in each of the following reactions.
(a) 5Fc2+ + Mn7+ — » 5 F c 3+ + Mn2+
(b) Zn + 2H+ — > Zn2+ + H 2 (g)
(c) Cu + S6+ — > C u2+ + S4+
o x id ized s u b s ta n c e s a r e : F e 2+ in (a ) ,Z n 2+ in (b),Cu in (c)

E X E R C IS E 5.2 Write the following oxidation - reduction reactions.

(a) Ferrous ions (Fc2+) tire reduced by Al.
(b) Sulfide ion (S2‘) is oxidized by N5f to S6+ meanwhile N5+ is reduced to N2+
(c) Bromide (B O ion is oxidized by CI2 to Br2. Meanwhile Cl2 is reduced to chloride ion.
( a ) 3 F e 2 * + 2 A l -> 3F e+ 2/\l3* (b)3Sz ' + 8 N s+ -* 3 S 6 ++ 8 N 2+ (c)2Br-+C I2 -> Вг2 + 2 С Г

5.2 BALANCING OXIDATION - REDUCTION

R EA C TIO N S
The oxidation - reduction reactions m ay be balanced by noticing the fact that
the num ber o f electrons lost in oxidation h a lf reaction is alw ays equal to the
num ber o f electrons gained in reduction h alf reaction. To balance an oxidation -
reduction reaction we are going to use two methods.
(1) Half - reaction method or ion - electron method.
(2) Oxidation number method.

5.2.1 H A L F - R E A C T IO N METHOD
The procedure in the h alf reaction m ethod (or ion electron m ethod) m ay be il­
lustrated as follows. Consider the reaction o f dichrom ate and ferrous ions in ac­
idic solution.
Fe2+ + Cr2 0 * ~ + H + — > Fe3+ + Cr3+ + H20
To balance this skeleton equation we will proceed through the follow ing seven
steps.

K e ep in m in d th a t each
S T E P - 1 : T he equation is divided into tw o h a lf reactions each involving the
h a lf-re a c tio n m u st h a v e species in either oxidation h a lf - reaction or reduction-half reaction. These half -
th e s a m e e le m e n ts o n reactions a r e :
b o th sid e s.
Fc2+ — > Fe3+ (oxidation)
Cr 2 0 72 — > Cr3+ (reduction)
176 Chapter 5 Ш П Ш И П П Illllillflllllllllllllll Illllllllltllllllllll Illl Illl Illlllllllllllllllllllllllllllll

In ste p 2, w e b a la n c e S T E P - 2 : Balance these h a lf reactions in terms o f the atoms except " H " and
atom s th at u n d e rg o o x i­ "O ".
d atio n and red u ctio n .
F e2+ — > F e3+ (balanced in term s o f " F e " atoms)
C r 2 C^" — > 2 C r 3+ (balanced in term s o f " C r " atoms.)
S T E P - 3 : Balance the equations in terms o f" O" by adding the p ro p er num ­
In a c id ic s o l u t io n s
ber o fH 20 to whichever side is d eficien t in " O " atoms.
th ere are la rg e su p p lies
2
o f H + and H 0 . Fe2+ — ► Fe3+
Cr 2 0 7' — > 2Cr3+ + 7H20
S T E P - 4 : Balance the equations in terms o f " H " atom s by adding p ro p er
number o f H + (remember that the solution is acidic, therefore there is large num­
ber o f H + in the solution) to whichever side is d e fic ie n t in " H " .
Fe2+ — > F e 3+
1 4H + + Cr 2 0 7* — •> 2C r3+ + 7H 20
S T E P - 5 : Balance the equations in terms o f c h a rg e by adding proper num ­
E v en th o u g h th e re a re
ber o f electrons to whichever side has greater positive charge totally.
eq u al n u m b e rs o f e a c h
k in d o f a to m o n b o th F e2+ — > Fe3+ + le - W ith o u t le " is b e in g added, the re a c ta n t has
sides o f th e e q u a tio n at (2 + ) c h a rg e , w h ile th e p r o d u c t h a s (3 + )
(2+ ) (3 +) + (1 -)
the end o f 4 th step, the c h arg e . T o b a la n c e the c h arg e , o n e e le c tro n
e q u a tio n s till n e e d s to (2 +) = (2 +) 1
(o r ( -) c h arg e) is added to the p ro d u c t side.
b e b a la n ce d in term s o f
c h a rg e . Proceeding similarly with the other half-reaction we have :
14H + + Cr 2 0 7‘ — » 2Cr3+ + 7H 20
14 (1 +) + 1 (2 -) 2 0 + ) + 1 (0)
( 1 2 +) * (6 +) ■;
The total charge o f the reactants is (12+), w hile that o f the products is ( 6 +).
Charge can be balanced by adding six electrons to the products so that the net
charge on both sides o f the equation becomes ( 6 +).
6e- + 14H+ + Cr 2 0 7" — > 2Cf»+ + 7H20
6 ( 1 - ) + (14 +) + (2 -) = ( 6 +) + 0
(+ 6 ) = (+ 6 )
S T E P - 6 : E quate the num ber o f electrons lost in o xidation-half reaction to
the number o f electrons gained in the reduction-half reaction. Use the least com ­
m on m ultiple o f the num ber o f electrons on both equations to equate them. Add
the resulting half-reactions and elim inate any com m on term s to obtain the bal­
anced equation. Examination o f the balanced half reactions
O n e e le c lro n is lo st
in th e o x id a tio n p r o ­
Fe2+ — > F e3+ + le - c e s s, w h ile six e le c ­
tro n s a re n e e d e d fo r
Cr2 0 2' + 14H+ + 6 e > 2Cr3+ + 7H20 the re d u c tio n p ro c ess.

indicates that the first should be m ultiplied by six to balance the electron trans­
fer. The addition o f the resulting half reactions term by term gives
ш1шшш1шшш1ш1шшш1ш11111!1шшшшншш!ш!!шш:шшш)1п11(ш1!шшш1!шш1ш11ш1ш O xidation - Reduction Reactions 177

6 Fe2+ — > 6 Fe3+ + 6 c

Cr 2 0 7 + 14H+ + 6 e » 2Cr3+ + 7H20
6 Fe2+ + Cr 2 0 7" + 14H+ — > 6 Fe3+ + 2СГ3* + 7H20
S T E P - 7 : C heck that the fin a l equation obtained conserves
(a) atoms. (b) electric charge.
Fe Cr H 0 Charge

On the left 6 2 14 7 6x(2 +)+l(2 -)+14(l +) = (24 +)

On the right 6 2 14 7 6x(3 +)+2(3 +) = (24 +)

EXERCISE 5.3 Balance the equation: H2S + MnC>4 -» S + Mn2+ (acid solution)
5 H 2S + 2 M n O 4
' + 6H * -> 2 M n 2 + + 5 S + 8 H 2 0

EXAMPLE 5.2 B a la n c in g a n E q u a tio n in A cidic M e d iu m

Problem : Balance the following equation.
Sb 2 S3 + NO' -> Sb 2 S5 + S 0 4' + N 0 2 (acid solution)
Solution :
STEP 1 : Sb 2 S 3 —> Sb 2 0 5 + 5 SO4 NO 3' - ^ n o 2
STEP II : Sb 2 S 3 —> Sb 2 0 5 + 3 S 0 2 n o 3' - + n o 2

STEP III : 17H20 + Sb 2 S 3 -> Sb2 0 5 3 SO 4 N O i - > N 0 2 + H20

STEP IV : 17H20 + Sb 2 S 3 -> Sb 2 0 5 3S 02' + 34H+ 2H + + NO 3 - > N 0 2 + H 20
STEP V : 17H20 + Sb 2 S 3 Sb2 0 5 +3SOf' + 34H+ + 28e‘ 2H+ + N 0 3' + l e ' N 0 2 + H20
л2-
STEP VI 1 x [17H20 + Sb2 S 3 -> Sb2 0 5 + 3 SO4 " + 34H+ + 2 8 e ']
28 x [2H+ + NO 3 + e~ -> NQ 2 + H 2 0 ]______________
17H20 + Sb 2 S 3 -> Sb 2 0 5 + 3SO|- + 34H+ + 28e'
56H+ + 2 8 NO 3 + 28e~ -> 28NQ2 + 28H2Q_________________
Sb 2 S3 + 2 8 NO 3 + 2 2 H+ -> S b 2 0 5 + 3 S 0 2' + 2 8 N 0 2 +11H 20

Sb S N 0 H Charge

On the left 2 3 28 84 22 1 x (0 ) + 28 x (1 -) + 2 2 x (1 +) = (6 -)

On the right 2 3 28 84 22 1 x (0) + 3 x (2 -) + 28 x (0) + 11 x (0) = (6 -)

E x e r c i s e 5.4 Balance the following equations in acidic solutions

(a) Cl2 + S 0 2 — * SCf' + C l' (b) H2 0 2 + CP — > Cl2 + H20
(c)Cr2<^‘ + I' — > Cr3+ + I2 (d) Zn + NO 3 — > Zn2+ + NH4+
( a )C l2 + S О 2+ 2 H 2 0 - > S 0 24' + 2 C l - + 4 H * (b) 2 H * + H 2 0 2 + 2 C l ' -> C l 2 + 2 H 2 0
(с) 1 4 H + + С r 2 0 2~ + 6 Г - * 2 C t >* + 3 I 2 + 7 H 2 0 (d)4Z n+ N O f+ 10H + 4 Z n * + N H 4 + 3 H 20

An additional step is added to balance equations in basic solutions. These equa­

tions are balanced initially as if they occurred in acidic solution by following the
178 Chapter 5 !111Ш1ШШШШ|11111ИШ1ШШШ11111ШШШШШШ11111ШШ1111111Ш111ШШ1ШШШ|1ШШ1|1Ш11Ш1Ш11Ш1111И1ШШ1Ш11Ш11Ш11111111Ш1111Ш1Ш|1|1И1Ш1Ш

steps I through VI. The H+ ions are then converted into H20 by adding an equal
num ber o f OH- ions to both sides o f the equation. This procedure is show n in
Exam ple 5.3.

EXAM PLE 5.3 Balancing Equation in a Basic Solution

Problem : Balance the following reaction in basic solution.
Zn + NO; - .NH
,..3 +, ^Zn(OH)2'
..Vv ^ V4

Solution : The step from I to VI are the same as those for the equations in acid solution
STEP I : Zn — ; Zn(OH)2' NOj > NH3
STEP II : Z n — = Z n(O H,2-
j no; ► NH 3
STEP III : Zn + 4H20 — ^ Z n (O H f no; -» NH 3 + 3H20
STEP IV : Zn + 4 H 20 — з Zn(OH)2' + 4H+ NOj + 9H + -> NH 3 + 3H20
STE P V : Zn + 4H20 — з Zn(OH)42' +. 4H+ + 2 e- n o ; + 9H+ + 8 e- — > NH 3 + 3H20
STEP VI : 4 x (Zn + 4H20 Zn(OH)2" + 4H+ + 2e-)
1 x (NOj + 9H+ + 8 e- NH 3 + 3H2 0 )
4Zn + 16H20 -> 4Zn(OH)2' + 16H+ + 8 e-
NOj + 9H+ + 8 e' -> NH 3 + 3H20
4Zn + NOj ’3H20 4Zn(OH) + NH 3 + 7H+

STEP V II :
Additional step : Since H+ cannot exist in any appreciable concentration in a basic solution, it must be re­
moved from the equation by adding an appropriate amount of OH- , and converting H+ to H 2 0 . So 70H - ions
must be added to both sides of the equation to convert excess H+ ions into water.
4Zn + NOj + 13H20 4Zn(OH)2' + NH 3 + 7H +
7H+ + 70H - = 7H?6 !
70H - 70H -
4Zn + NOj + 13H20 + 70H - — > 4Zn(OH)2' + NH 3 + 7H20
The equation now contains H20 on both sides. It may be simplified. Subtracting seven H20 from each side
leaves six H20 on the left.
4Zn + NOj + 6H20 + 70H - — > 4Zn(OH)2" + NH 3
STEP V III Check :

Zn N H 0 Charge

On the left 4 1 6 x (2) + 7x1 = 19 3x1+6x1+7x1=16 lx (l -)+7x(l -)=(8 -)

On the right 4 1 4 x4 + 1x3 = 19 4 x 4 = 16 4 x (2 -) = (8 -)

EXER C ISE 5.5 Balance the following equations in basic solution.

(a) MnOj + CN- MnOj + CNO- (Ь)СЮ 2‘ + HSnOj HSnOj + CrOj
(c) H 2 0 2 + C10 2 C102' + 0 2 (d) Cl2 — ► ClOj + Cl-
(Hi nt: In part (d) chlorine is both oxidized and reduced. Such reactions are called disproportionation (or auto
redox) reactions. The two half reactions a re : Cl2 — > ClOj and Cl2 — > C l'
( a ) H 2 0 + 2 M n 0 '4 + 3 C N - - > 2 M n 0 2 + 2 0 H - + 3 C N 0 - ( b ) 2 C r 0 24 ' + 3 H S n 0 ' + H 2 0 - i 2 C r O \ +3H SnOj +20Я '
(c) H 2 0 2 + 2 C 1 0 2 + 2 0 H ~ -> 2CIO J + 0 2 + 2 H 2 0 (d ) 3 C l 2 +60H ' ^ SC I' +C70j + 3 H 20
 ни ...................... O xidation - Reduction Reactions 179

5.2.2 O XID A TIO N NUMBER METHOD

5.2.2.1 OXIDATION NUMBERS
O x id a tio n n u m b e rs are In the reaction, M g (s) + 1/2 0 2 (g) — > M gO , w e say that M g loses two
a rb itra ry n u m b e rs th a t electrons, and gains an apparent charge o f (2 +), and oxygen gains an apparent
h e lp u s to d e te rm in e charge o f (2-). Since these num bers com e from an oxidation - reduction p ro ­
th e o x id a tio n sta te o f
cess, they are called oxidation numbers. It is no t so easy to determ ine the
an e le m e n t in its c o m ­
p o u n d s.
oxidation num bers o f elem ents in m ost com pounds as in M gO . B ut the follow ­
O x id a tio n n u m b e rs are ing rules help us to determ ine the oxidation numbers o f elements.
u s u a lly in te g e r s , b u t Rules for determining oxidation numbers.
th ere are frac tio n a l o x i­ 1 - The oxidation num ber o f an elem ent in fre e , or in allotropic fo r m
d a tio n n u m b e rs too. is zero. All the elements in the following species have an oxidation num ­
ber o f zero. Fe, Си, Al, Zn, H 2, 0 2, Cl2, P4, S 8
2 - The oxidation num ber o f a m onatom ic ion is equal to its charge.
Exam ine the following examples.
monatomic ion oxidation number
Fe2+ +2
Cr3+ +3
O x id a tio n n u m b ers:
o 2- -2
F ree e le m en ts: z e r o
In C om p o u n d s: 3 - In compounds
O x y g e n : (2 -) in H 0 , 2 a) O xygen usually has an oxidation num ber o f -2. T here are tw o ex­
N aO H , ... ceptions.
1 22
( - ) in H O , N a 202 ...
1) W hen oxygen is com bined w ith fluorine as in OF2, its oxidation
H y d r o g e n : ( l + ) in HC1,
2
H 0 , H N O ... 3 num ber is + 2 .
(1-) in N aH , C a H ... 2 2) In com pounds containing oxygen - oxygen bonds such as hydro­
A l k a li m e t a l s : gen peroxide, H20 2, its oxidation num ber is -1.
(Li, N a, K , R b, Cs, Fr) b) H yd ro g en usually has an oxidation num ber o f + 1 . B ut in m etal
1
( +) in all co m p o u n d s. hydrides such as NaH, CaH 2, its oxidation num ber is -1.
E a r t h a lk a lin e m e ta ls :
(B e, M g, C a, Sr, B a, Ra)
c) H a logen s usually have an oxidation num ber o f -1 in binary com ­
2
( +) in all c o m p o u n d s. pounds. B ut if they are com bined w ith a m ore electronegative elem ent
H a lo g e n s : such as oxygen, their oxidation num ber changes from +1 up to +7. R e­
(F, C l, B r, I) m em ber that fluorine always has an oxidation num ber o f - 1 .
1
( -) in b in a ry c o m p o u n d s d) A lk ali m etals (Li, N a, K , ....................) alw ays have an oxid a ­
s u c h as HC1, N a B r, K I,
tion num ber of+ 1.
C a B r2 .
(1 + to 7+) in te r n a r y e) Earth alkaline m etals (M g, Ca, Sr, B a ............. ) alw ays have
c o m p o u n d s su c h as Н С Ю , an oxidation num ber o f +2.
4
К С Ю , H IO ... 3 f) Silver, A g , and zinc, Z n , and alum inum , A l, have the oxidation
num bers o f +l,+2 and +3 respectively.
S o m e tim es it is h e lp fu l to 4 - The sum o f the oxidation num bers o f a ll the atom s in a neutral
re m e m b e r th e fo rm u la o f com pound is zero, and in an polyatom ic ion is equal to the charge o f the
the co m p o u n d b etw ee n A m+
ion. Some com m on polyatomic ions and their charges are :
and B n ~ ions is A nB m . B y
the re v e rse p ro c e ss w e d e ­ N H 4 , CN~ , M n 0 4 , N O J , O H " , H C O J , SO^~ , C O ^ , C r O ^ ,
d u ce th a t in A nB m the o x i­ СГ2 О7 - , and PO 4 - .
d a tio n n u m b ers o f A an В T his rule helps us to find the oxidation num bers o f atom s in com ­
are (m +) and (n-). pounds and ions. Some illustrative examples are given below.
180 Chapter 5 ..... . I !• iiiiiiii ill

EXAMPLE 5 .4 Determining Oxidation Number

Problem : Determine the oxidation number of the element written in boldface in the following species,
a) K M n0 4 b )H 2 S 0 4 c)B aC r 20 7 d )C r 2 C$~ e)NH+ (f) Cu(N0 3 ) 2 (g) C3 H60
Solution : Let x be the oxidation number of the element written in boldface in each specis. Write the oxida­
tion number of each element with the help of rules on the top of the symbol of the element in the compound.
+1 x -2
a) KMn04
К is an alkali metal, hence its oxidation number is +1, oxygen has the oxidation number of -2.
Now multiply the number and oxidation number of each element in the compound. The sum of these prod­
ucts must be equal to zero since KM n04,is neutral. , , __ v
1 x (+1) + l~x—(x) + 4 x (- 2) = 0
Solving this equation for x gives x = +7. Therefore the oxidation number of Mn in KM n0 4 is +7.
+1 x -2 +2 x -2
b) H 2 S 0 4 с) ВaC r2 0 ;
2 x (+ 1) + 1 x (x) + 4x (- 2) = 0 1 x (+ 2) + 2 x (x) + 7 x (- 2) = 0
x = + 6 x = + 6
Recall that the sum of the oxidation numbers of all the atoms in a polyatomic ion is equal to the charge of
the ion.
x -2 x +1
d) Cr2 Of- 'e )N H ;
2 x (x) + 7 x (-2) = -2 1 x (x) + 4 x (+1) = +1
x =+6 x=-3
x -1 x +1 - 2
(f) C u(N 0 3 ) 2 =>1 x ( x ) + 2 x (-1)= 0=> x = +2 (g) C 3 H60 => 3x (x) +6 x (+1) + (-2 ) = 0 => x = -4/3
(The nitrate ion has a charge of -1,which we take (Oxidation numbers do not have to be whole numbers.)
it to be the net oxidation number of one N and three
О atoms.)

EXERCISE 5.6 D eterm ine the oxidation num ber o f the elem ent, written boldface in the follow ing
species.
a) H 3 B 0 3 b) N aN0 3 c) Cr2 (S 0 4 ) 3 d)Ca(OCI ) 2 e)H 2 0 2 f)K H g ) I 0 3' h) S2 0 2'
(a)(+ 3) b )( + 5 ) c )(+ 3 ),(+ 6 ) d)(+ I) e)(-l) f)(-l) g)(+S) h)(+2)

5 .2.2.2 BALANCING EQUATIONS USING OXIDATION

NUMBER METHOD
In any reaction, the net change in oxidation num bers o f elem ents m ust be
zero. This rule provides a basis for balancing oxidation-reduction reactions. Let
us see how this rule works in balancing equations
Fe2+ + Cr2C f + H+ — Fe3+ + Cr3+ + H20
which we have balanced it by the half-reaction method.
 111! Ш Ш Ш 11! 11! | 11111! 111: ! Ш ! 1! 111Ш 1111! 1Ш 1! ! 11Ш 1! ! ! 1Ш 1Ш 1М 1! 1Ш ! 111111! 11Ш Ш 111Ш 1Ш 1! ! ! И 1! Ш ! 1| 1Ш Ш Ш № OxidtXtiOTl - RedUCtiOTl RedCtiOUS 181

S T E P I: D eterm ine the oxidation num ber o f each elem ent in the equation, us­
ing the rules given before.
+2 + 6 -2 +1 +3 +3 + 1 -2
O x id a tio n is any c h a n g e Fe2+ + Cr2C f + H + — > Fe3+ + Cr3+ + H 20
in w h ic h th e o x id a tio n
n u m b e r o f a n a to m i n ­
S T E P II : D eterm ine the elem ents w hose oxidation num bers have changed,
creases.
R e d u c tio n is a n y c h an g e because o f electron loss and gain.
in w h ic h th e o x id a tio n +6-2
+2 +3 +3
n u m b e r o f art a to m d e ­
Fe2+ Cr2C f + H + > Fe3+ + Cr3+ + H20
c re a se s.
red u c ed /
t t t
o x id iz e d

S T E P I I I: Indicate the num ber o f electrons lost in oxidation and gained in re­
duction p e r atom, and p er form ula unit.

A n o th e r a p p ro a c h to b a la n c e
h a lf r e a c tio n s is to u s e th e Fe2+ Fe3+ +le~ (oxidation)
c h a n g e s in o x id a tio n n u m b e rs Cr3+ (reduction)
C i^ +3e-
ra th e r th a n u sin g e le c tro n s . In
th is m e th o d , th e d if fe r e n c e in
o x id atio n n u m b e r o f a sp e c ie s is Since Cr exists in diatom ic state in Cr2 0 2" we m ust m ultiply the latter equa­
w ritte n a b o v e th e a rro w in the tion by two to find the change in oxidation num ber per form ula unit o f Cr2 C ^'.
h a lf re a c tio n , th en th e in c re a s e
and d e c re a s e in o x id a tio n n u m ­
b e rs a re b a la n c e d u s in g a p p ro ­ 2 C i^ + 6 e » 2C r3+
p riate c o efficie n ts. F o r e x am p le
Fe
2+ 3+ S T E P IV : To balance the num ber o f electrons lost and gained in the overall
T h e d iffe re n c e in th e o x id a tio n reaction ,use their least common multiple.
states o f iro n after and b e fo re re ­
6 x (Fe2+ — > Fe 3 ++ le-)
action is
[(3+) - (2+) ] or (1+ ) 1 x (2СГ6* + 6 e- — > 2СГ3*
T h is is e x p ressed as
Fe 2+ (1+)- p e 3 + S T E P V: A d d the equations obtained in step IV side by side.
S im ila rly
Fe2+6 > 6 Fe3+ + 6 e~
C r6+ -— > C r 3+ (p er atom ) 2 C i^ + 6 e- — > 2 Q 3*

.6 +
(6 -)
2 C r' 2 C r 3+ (p er form ula 6 Fe2+ + 2CC* — > 6 Fe3+ + 2Cr3+
u n it o f C r20 7)
S T E P V I : Transfer the coefficients fo u n d in step V into the w hole skeleton
6x [Fe
2+ ( 1+)
FeJ equation. Pay attention that two Cr6* present in one form ula unit o f Cr2 C ^'.
l x [2 C f,6 + <*± 2C r.3+ 6 Fe2+ + Cr2 Of- + H+ — > 6 Fe3+ + 2Cr3+ + H 2 O

2
6F e ++ 2 C r6+ • 6
F e 3++ 2 C r3+
S T E P V I I : Balance c h a rg e , an d " O " atom s
T h e sa m e c o e ff ic ie n ts a re o b ­
tain e d . 6 Fe2+ + Cr2C f + H+ — > 6 Fe3+ + 2Cr3+ + H20
6(2+) + 1(2-) + ?(1+) = 6(3+) + 2(3+) + lx (0 ) => ? = 14
6 Fe2+ + Cr2C f + 14H+ — > 6 Fe3+ + 2Cr3+ + H 20
 ш п ш и и ........................... m u ..................................... ш п и н и ................... .. ...................................... п и ш и

There are seven oxygen atoms on the left. There m ust be seven oxygen atoms
on the right. The coefficient o f H20 m ust be seven.
6 Fe2+ + Cr2 Of‘ + 14H+ — > 6 Fe2+ + 2C r3+ + 7Ш О

S T E P V III : C heck i f the fin a l equation conserves all the atom s and electric
charge.
Fe Cr 0 H C harge

On th e left 6 2 7 14 6x(2 +)+l(2 -)+14(l +) = (24 +)

On th e rig h t 6 2 7 14 6x(3 +)+2(3 +)+7(0) = (24 +)

Since the equation conserves both the atoms and the charge , it has been bal­
anced.

EXAM PLE 5.5 B a la n c in g E q u a tio n U sin g O x id a tio n N u m b e rs

Problem : Balance the following equation by using oxidation number method.
I" + NOj — > I 2 + NO (acid solution)
Solution : Apply the steps I through VIII.
S T E P S I and II:
-1 + 3 -2 0 +2 - 2
I" + NOj — > I2 + NO
I t re d u c e d t
o x id iz e d

STEPS III and IV and V:

1 x (2 1 " — > Ij* + 2 e“ ) (oxidation)

2 x (N3+ + le“ — > N2+) (reduction)

21" + 2N3+ — > I2 + 2N2+

STEP VIII :
To balance electric charge, add H+fo r acidic, (or O W for basic solutions).

2Г + 2NQj + 4K" — > I2 + 2NO

To balance "O " add water, to the side that needs "O ".

21" + 2NOj + 4H+ — > I2 + 2NO + 2H20

The hydrogen atoms have already been balanced.

STEP V III: Check if the final equation conserves all the atoms and charge.

I N 0 H C h a rg e

On th e left 2 2 4 4 0

O n th e rig h t 2 2 4 4 0
н и ш ............... ш п и н и ......... н и ............... ш и н .... ... .O xiddtion - Reduction Redctions
и 183

EXERCISE 5.7 Balance the following equations occurring in acidic solutions

(a) 10“ + AsOj3- — » Г + AsO/~ (b) Mn2+ + BiOf — > M n04_ + Bi3+
(a)Iof+ 3AsOf~ — >r+3Aso/~
(b) 2 M n ++ 5 B i o f + 1 4 H + -----> 2 M n O f + 5Bi3 + + 7 H 20

EXAMPLE 5 .6 Balancing Equation Using Oxidation Number Method

Problem : Balance the following equation by using oxidation number method.

PH 3 + HPO2- (basic solution)

Solution :
STEPS I, II :
0 -3 +1 +1+3 -2
P4 PH 3 + H P O f
Ir e d u c e d
o x id ized
STEPS III, IV, and V

1 x (P4 + 12e 4P3")

lx ( P ^ 4P3+ + 12e“ )

2 P£ 4P3" + 4P3+

STEP VI : 2P4 — > 4PH 3 + 4 HPO2"

STEP V I I : To balance electric charge, add OH" since the solution is basic.

2P 4 + 80H" — > 4PH 3 + 4HPO2"

To balance "O", addH 2 0 .

2P 4 + 80H" + 4H20 — > 4PH 3 + 4H P 02"

STEP VIII : C heck

P 0 H Charge
On the left 8 8 + 4 = 12 8 + 8 = 16 2 x (0) + 8(1-) + 4 x (0) = (8-)
On the right 4 + 4 =8 4x3 = 12 4x3 + 4x 1 = 16 4 x (0) + 4 (2 -) = (8 -)
So the balanced equation is:
2P4 + 80H" + 4H20 — > 4PH 3 + 4 HPO2'
If you wish you may divide all the coefficients by two to obtain a simpler equation. Namely
P 4 + 40H" + 2H20 — > 2PH 3 + 2HPO2"

EXERCISE 5.8 Balance the following equations occurring in basic solutions.

(a) C103" + N2H4 — > NO + СГ (b) Br2 — > bV + ВЮ4‘
(a) 4 C 1 0 3 + 3 N 2H 4 -----> 6 N 0 + 4 C r + 6 H 20 (b) 4Br2 + 8 0 H " 7Br~+B rO f + 4H 20
184 Chapter 5

— ■■■ .

EXAMPLE 5.7 Balancing Equation by Oxidation Number Method

Problem : Balance the equation:
As2 S3 + N aN 0 3 + Na 2 C 0 3 — > Na 3 A s0 4 + Na2 S 0 4 + C 0 2 + NaNOz

Solution : All the steps are applied to the equation:

+3 -2 +1 +5 -2 +1 +4 -2 +1 + 5 - 2 + 1 + 6 -2 +4 -2 +1 +3- 2
As2 S3 + N aN 0 3 + Na 2 C 0 3 ---- > Na 3 AsQ 4 + Na 2 S 0 4 + C 0 2 + NaNOz
A /
| red u c ed ' \ t
o x id iz e d
o x id iz e d

To determine the oxidation numbers of As and S in As2 S 3 recall how to write the formula of compound,
AnBmbetween Am+ and Bn' ions. As and S have the oxidation numbers (3+) and (2-) respectively.
There are two oxidized and one reduced substance in this reaction, first the total change in oxidation number
per formula unit of As2 S3 must be determined. Then the usual procedure is followed.

2As3+ — > 2Ass+ + 4e“ oxidation

3S2‘ — > 3S6+ + 24e_ oxidation

2As3+ + 3S2* — > 2As5+ + 3S6++ 28e- total oxidation reaction

1 x (2As3+ + 3S2" —> 2As5+ + 3S6++ 28e- ) oxidation

14 x (N5+ + 2e~ — > N3+) reduction

2As3+ + 3S2" + 14N 5+ — » 2A s5+ + 3S6+ + 14 N3+

Transfer these coefficients to the original equation.
As2 S3 + 14NaN03 + Na 2 C 0 3 — > 2Na3 A s0 4 + 3Na2 S 0 4 + C 0 2 + 14NaN02
Finally balancing the rest of the elements gives the overall balanced equation. In balancing we should prefera­
bly begin with the elements that appear in the equation less frequently and leave H and О to the end.
As2 S 3 + 14NaN03 + 6Na2 C 0 3 — ^ 2Na3 A s0 4 + 3Na2 S 0 4 + 6C 0 2 + 14NaN02
We can check if it has been balanced by comparing the number of atoms of each kind and electric charge on
both sides of the equation.

As S Na N С 0 Charge
On the left 2 3 26 14 6 60 0
On the right 2 3 26 14 6 60 0
Since it conserves the atoms and electric charge, it is a balanced equation.

EXERCISE 5.9 Balance’ the following equations using oxidation numbers.

(a) Nal +HOC1 — * N aI0 3 + HC1 (b) H N 0 3 + I2— * НЮ 3 + NOz + H20
(c) ASj Sj + C lOj — > C f + HjAsOj" + S (acid solution)
(a) N a l + ЗЦОС1 — > N a I 0 3 + 3HCI (b) 10H N O 3 + I2 — > 2 Н Ю 3 + 1 0 N O 2 + 4 Н г О
(c) 3 A s 2S 3 + S C l O f + 9H 20 — > 6H2A s O ~ + 5Cl~ + 6H + + 9S
I I I I I I I I I I I I I I I I I I I I I I I I I l l l I I I I I I I I I I H I I H I t l l l l i l l l l l l l H l l l H M t l H l l l l l l t l l l l l l l l l l l l l l i l i l l i l l l l l l l i n t t M I I I I I M in ilM IIIM tl Oxidation - Reduction Reactions 185

EXERCISE 5.10 Balance the following equations by an appropriate method.

(a) S 03" + Mn04" — > S04~+ Mn2+ (acidic solution)
(b) Cr(OH ) 3 + CIO- — > C rO f + СГ (basic solution)
(c) Cu + HNO 3—> C u(N 0 3 ) 2 + NO + H20
(d) Crl3 + H2 0 2 + OH* — > C rO f + 10 ; + H20
a) 5 S 0 3 '+ 2 M n 0 4- + 6H + — =► 5 S 0 /2 + 2 M n 2+ + 3 H 2 0

b) 2 C r ( O H )3 + З С Ю - +40H - > 2 C r 0 /2 + 3 C I "+ S H 20

c) 3 C u + 8 H N O 3 -----> 3 C u ( N 0 3) 2 + 2 N O + 4 H 20
d) 2 C r l 3 + 2 7 H 2 0 2 +10OH- -----> 2 C r 0 /2 + 6 1 0 ; + 3 2 H 20

EXAMPLE 5.8 Balancing Equations and Calculations.

2_ _
Problem : When sulfite ion (SCL ) and iodate ion (I0 3 ) are mixed in an acidic solution, the products of the
reaction are sulfate ion (S 0 4
2— ), and iodine (I2).
(a) Write the balanced equation.
2~
(b) What volume of 0.2 M K I0 3 solution is required for the complete oxidation of S 0 3 in 200 mL of 0.1 M
H2 S 0 3 ? K I0 3 = 214
Solution : (a) We start the solution to the problem by writing the skeleton equation in ionic form.
4+ 5+ 6 + _0
so32~+io~ —> so42_+ i2
We see from the oxidation number changes that S is the element oxidized from (4+) to (6 +) and I is the element
reduced from (5+) to zero.
5 x (S4+ — > S6+ +2e~)
T o eq u alize the ch an g e in o x id atio n n u m b e r we
1 x (2 I5+ + 1 0 c~— > 1° ) m u ltip ly S by 5 . '

5S4+ + 2I5+ — > 5S6+ + I2

Transferring the coefficients to the skeleton equation, and then balancing the equation in terms of charge, H, and
О gives the following balanced equation.
2H+ + бБОз^- 2 I0 3“ — > 5S 04^ + I2 + H20
(b) The number of moles of SOj2" in 200 inL of 0.1 M H 2 S 0 3 is:
nH2 so 3 = (0-1 mol/L ) (0.2 L) = 0.02 mol => = 0.02 mol
The number of moles of I 0 3 reduced is found by means of the coefficients in the balanced equation.
(0.02 mol SOj2- ) x (2 mol IO 3" /5 mol SOj2-) = 0.008 mol I 0 3_ => 0.008 mol K I0 3
The volume of the КЮ 3 solution is V k io 3 = (0.008mol) / (0.2mol/L) = 0.04 L or 40 mL.
We can solve the problem in a different way by using the concept of equivalent and norm ality. In any re­
dox reaction, the number equivalents of oxidizing agent is always equal to that of reducing agent.

neq (oxidizing agent) = neq (reducing agent) Nqx x Vox —Nrccj x V recj

We should keep in mind that the normality of a substance depends not only on its molarity but also change in
its oxidation number in the reaction. The relationship between the molarity and normality of solution of a solute

V
186 Chapter 5 шшпн IIIIIIIIIHIIIIIIIIIIIIIIIIIIIIIIIIIIIHIUIIIIIII Illlllll Illl Illllll! Illlll Illl.........Illllll....... I..... Illllll.....I

is given by the Formula

N = M x a - 4 The number of electrons transferred per formula unit of the substance
■> The molar concentration of the solution (mol/L)
> The normal concentration of the solution (eq/L)
In this reaction S is oxidized from (4+) to (6 +), giving up two electrons per formula of S 0 3 .S o a= 2 for S.
Nh 2 so 3 = m h 2 so 4 x a = > Nh 2 so 3= (0.1 mol/L)( 2 eq/mol) = 0 .2 eq/L = 0.2N
The value of a for K I0 3 is 5, because I 0 3"~gains five electrons per formula unit of K I0 3 . (I5+ is reduced to 1°)
NKI0 3 = М к ю 3 x a N k io 3 = (0.2 mol/L) (5 eq/mol) = 1 eq/L or 1 N
N h 2 s o 3 x v h 2 s o 3 = NKI0 3 x v k io 3
(0.2 N) (200 mL) = (1 N) (VKI03) V k io 3 = 40 mL

EXERCISE 5.11 The following reaction occurs when As2 0 3 and I2 are allowed to react in basic solution.

As 2 0 3 + 12 — > H 2 A s0 4~ + Г
(a) Complete and balance the equation.
(b) What is the equivalent mass of As2 0 3 in this reaction? How many equivalents of As2 0 3 are used in the reac­
tion ?
(c) If 0.99 g of As2 0 3 reacts completely with 50 mL solution of I2 , what is the molarity of the solution of I2 ?
A s 2 0 3 = 198 g/mol (b)198/4 g ie q ; 0.02 eq ;(c)0 .2M

, Zn
5.3 ELECTROCHEMICAL CELLS
W e have stated that electrons are transferred from reducing agent to
oxidizing agent in an oxidation reduction reaction. If this electron trans­
fer is forced to take place through an external pathw ay rather than di­
rectly betw een reacting substances, w e will obtain a flow o f electrons,
o r electric current. The devices in w hich spontaneous oxidation - reduc
tion reactions produce electric energy or electrical potential are called
e le c tro c h e m ic a l ce lls o r V o lta ic cells o r G a lv a n ic cells. In a
voltaic cell, a difference o f electrical potential betw een the electrodes is
produced by the chem ical reactions occurring' spontaneously at each
electrode.
In an electrochem ical cell, the oxidation and the reduction h alf reac­
tions are allowed to take place in separate containers, so that the electron
transfer is forced to occur by the passage o f electrons through an exter­
F I G U R E 5.1 A simple redox nal wire. Thus, useful electrical energy is obtained.
reaction (a) A strip o f zinc is
placed in a 1M Cu2+ solution. 5.3.1 THE CONSTRUCTION OF A VOLTAIC CELL
The solution is blue due to Cu2+ W hen a piece o f Zn is dipped into a solution containing Cu2+ ions, a
ions, (b) Electrons are trans­ spontaneous reaction will take place. See Figure 5.1.
ferred from Zn atoms to Cu2+
ions so that zinc metal is eaten Z n (s) + Cu2+ (aq) — > Zn2+ (aq) + Cu (s)
away and copper deposites on W hen this reaction takes place in the m anner described, it is useless
the surface o f the zinc strip. as a source o f energy. Because w hen Cu2+ ions and Zn are in direct con­
During this process the [Zn2+] in tact, the C u2+ ions go to the zinc electrode and take electrons from zinc
the solution increases while electrode. So the flow o f electrons cannot be used to generate electricity.
[C u 2+] decreases. Therefore To use this reaction as an electrochemical cell its oxidation and reduction
the characteristic blue 'color ot reactions m ust be separated. Let us see how this happens.
Си2* ions in the solution fades.
 1111111Ш11Ш11Ш!Ш1Е!1|1|1Ш1111Ш1||||!ШШ!1||||||||||1Ш111!111111Ш1ШШ111!!Ш11Ш111Ш1ШШШ1ШШ1111!11! OxidCttWTl - RedllCtiOTl ReClCtiOTlS 187

V oltm eter

A galvan­
ic cell utilizing the reac­
tion
Zn (s) + Си2+ (aq)
FIGURE 5 . 2 Z r?+ (aq) + Cu(s)

Zn —> Zn + 2e Cu2+ + 2e —> Cu

Oxidation Reduction

Consider the cell illustrated in Figure 5.2. The zinc electrode dips into a 1 M
Z n S 0 4 solution, and the copper electrode dips into a 1 M C u S 0 4 solution. The
inverted U tube containing a saturated solution o f K N 0 3 connects the two beak­
ers electrically. The cotton plugs prevent the K N 0 3 solution to run out w hen the
tube is inverted. T he U tube w ith the solution in it is usually called s a lt
T h e s o lu tio n in th e sa lt b rid g e . The salt bridge has tw o Tunctions. It avoids m ixing the solutions in the
b rid g e m ay b e a n y strong h alf - cells, thus prevents the direct electron transfer from zinc atom to Cu2+ ion.
e le c tro ly te s o lu tio n w h o ­ It also m akes an electrical contact betw een tw o solutions, thereby enabling an
se io n s do n o t re a c t w ith
electrical circuit to be com pleted. To understand the function o f the salt bridge
th e o th e r io n s in th e
w ell let us exam ine the reactions taking place at each electrode o f the electro­
c e ll.
chemical cell.
As the cell operates, zinc is oxidized to Zn2+ and Cu2+ is reduced to m etallic
copper. The electrode a t w hich the oxidation occurs is called anode, a n d the
A n e le ctro c h em ica l c e ll is electrode a t w hich the reduction occurs is called c a th o d e . Thus the h a lf reac­
o fte n re p re se n te d b y u s ­ tion
in g s in g le v e r tic a l lin e s
to s e p a ra te a n e le c tro d e Z n (s) — > Zh2+ (aq) + 2e-
fro m a s o lu tio n a n d a
occurs at the anode. Zn2+ ions becom e part o f the solution and tw o electrons
d o u b le v e r tic le lin e to
re p re s e n t th e sa lt b rid g e flow through the external wire, voltm eter, and reach copper electrode at which
th a t s e p a ra te s th e s o lu ­ the reduction reaction
tio n s . B y c o n v e n tio n
Cu 2 +(aq) + 2e- — > Cu (s)
anode is w ritte n first.
T h e e le c tro c h e m ic a l c e ll occurs. Since (dipositive) Zn2+ ions enter the solution in the anode com partm ent
b e tw e e n Z n a n d C u h a lf (Electrons given up zinc atoms do not enter the solution. They m ove tow ard Cu
c ells m ay be re p re se n ted .
electrode through the external w ire and voltm eter.) it becom es positively
2
Z n/Z n +//C u 2+/C u
charged. To keep the neutrality o f the solution, N O 3 ions from the salt bridge
m igrate into the anode com partm ent to balance the increase in positive charge.
The solution in the cathode com partm ent becom es negatively charged because
Cu2+ are rem oved from the solution by m eans o f reduction h alf reaction. T here­
fore K+ ions m ove from salt bridge into the cathode com partm ent to balance the
decrease in positive charge.
W hen the copper - zinc cell is constructed as described, the follow ing experi­
m ental observations can be made.
188 Chapter 5 ННПНИНПИШИПИШ I НИ I lll ШИШИШШ .

•In th e e x te rn a l c irc u it
1. The voltm eter reading is 1.10 volts.
e le c tro n s m ig ra te from 2. The zinc electrode loses weight and the concentration o f Zn2+ in the solu­
a n o d e to w a rd c a th o d e . tion around the zinc electrode increases as the cell operates. These observations
In s a lt b r id g e a n io n s are consistent with the oxidation reaction o f zinc.
m o v e to w a rd anode, c a ­
tio n s m o v e to w a rd c a ­ Z n (s) Zn2+ (aq) + 2e-
th o d e.
3. The copper electrode gains weight, and the concentration o f Cu2+ ions de­
creases in the solution around the copper electrode as the cell operates. These
observations are also consistent w ith the reduction reaction o f Cu2+ ions to Cu.
Cu 2 + (aq) + 2e- — > C u (s)
4. The overall reaction is :
E x p e r i m e n t a l l y it is
fo u n d th a t th e c e ll p o ­
Zn (s) — > Zn2+ (aq) + 2e- (anode reaction)
te n tia l is in d e p e n d e n t Cu2+ (aq) + 2e- — > Cu (s) (cathode reaction)
o f size and sh ap e o f the Z n (s) + Cu 2 + (aq) Zn2+ (aq) + Cu (s)
so lid e le ctro d e s.

5. T he cell voltage, 1.10 V, depends on the concentrations o f Zn2+ and Cu2+

ions. But it is independent o f the shape, and m agnitude o f the zinc and copper
electrodes.
To gain m ore experience about construction and principles o f operation o f
voltaic cell, let us now exam ine another electrochem ical cell, the copper - silver
cell. See Figure 5.3.
V oltm eter

FIGURE 5.3 77)e Cu/Aq

Voltaic cell.

im c u SO 1M AgNQj

The following experimental observations can be made.

1. The initial voltm eter reading is 0.46 volt.
2. The copper electrode loses weight, and Cu2+ ion concentration increases
as the cell operates.
3. The silver electrode gains weight and the Ag+ ion concentration decreases
as the cell operates.
From these observations we can deduce the reactions taking place at each
electrode.
Cu (s) — * Cu2+ (aq) + 2 e~ (anode reaction)
_________ 2 (Ag+(aq) + e~ — > Ag(s)) (cathode reaction)
C u (s) + 2A g+ (aq) Cu2+ (aq) + 2Ag (s) (overall reaction)
 ..... O xidation - Reduction Reactions 189

So N O j , K+ ions from the salt bridge m igrate into anode and cathode solutioas
respectively to keep the electrical neutrality and to complete the circuit.
R em em ber that in the zinc - copper cell, the copper electrode is the cathode,
w hile in the copper - silver cell the copper electrode is the anode. Thus we see
that w hether a particular electrode acts as an anode o r a cathode depends on
w hat the other electrode o f the cell is. T he tw o cells w e have considered show
We se e th a t Z n re a d ily that C u2+ ion is a stronger oxidizing agent (electron acceptor) than Zn2+, and
g iv e s e le c tro n s to C u 2+, Cu2+ ion oxidizes metallic zinc to Zn2+ .
a n d C u g iv es e le ctro n s to Conversely, metallic zinc is a stronger reducing agent (electron donor) strongest
A g + . T h e e le c tro n d o n o r than m etallic silver. Comparing the species gives the following orders.
su b sta n c e (red u c in g agent)
is Z n am ong Z n, C u, and Oxidizing agents reducing agents
Ag. O r A g + is the stro n g ­
e st e le c tro n a c c e p to r o r Zn2+ < Cu2+ < Ag+ Zn > Cu > Ag
> — ■
—»
o x id iz in g a g e n t a m o n g increasing strentgh decreasing strength.
th re e e le m en ts.
By constructing new voltaic cells we can increase the num ber o f elem ents or
ions in our list o f oxidizing agents or reducing agents. Exam ine the follow ing
example.

EXAMPLE 5 .9 Constructing an Electrochemical Cell

Problem : A strip of magnesium immersed in 1 M magnesium nitrate, and a strip of zinc immersed in 1 M
zinc nitrate solutions. A wire, a voltmeter, and a salt bridge complete the circuit. During the cell operates it is
observed that the weight of magnesium electrode decreases, while the mass of zinc electrode increases.
(a) Draw a diagram representing this cell.
(b) Which electrode is the anode, what is the anode reaction?
(c) Which electrode is the cathode, what is the cathode reaction?
(d) What is the overall cell reaction?
(e) Indicate the direction of migration of ions through the salt bridge.
(£) Which is the stronger oxidizing agent Mg2+ or Zn2+, the stronger reducing agent magnesium or zinc?
(g) What are the places of Mg2+, and Mg in the list of elements we have written before?
Solution : a) The diagram of the cell is shown below.
Voltmeter

Anode C a th o d e

b) The observation reveals that during the operation of cell the magnesium electrode dissolves in the solution.
Therefore it must be oxidized according to the half reaction :
Mg (s) — > Mg2+ (aq) + 2e-
Since the electrode at which oxidation occurs is called anode, then Mg electrode is the anode.
190 Chapter 5 Ш1Ш!||Ш|ШИ1|11|||Ш||Ш||||ШШ1Ш1Ш||||Ш|ШШШ1ИШ1|||||||||||Ш|1Ш|11||ИМ||||||||||Ш|||||||Ш1ШШШШ||ШШ||||||||||||||1Ш||Ш|Ш1Ш111111||11|||Ш

с) Since the zinc electrode gains weight, the reduction reaction takes place at the zinc electrode according to the
reaction:
Zn2+ (aq) + 2e- — > Zn (s)
Because of the deposition of Zn2+ ions as Zn at the zinc electrode it gains weight. Hence the zinc electrode is the
cathode.
d) The summation of the anode and cathode reactions gives the overall reaction after cancelling electrons.
Mg (s) — *■ Mg 2+ (aq) + 2e- (anode reaction)
Zn2+ (aq) + 2e_ — > Zn (s) (cathode reaction)
Mg (s) + Zn2+ (aq) — > Mg2+ (aq) + Zn (s)

e) Through the salt bridge anions migrate toward anode, and cations toward cathode. In the cell we built, N 03"
ions migrate toward Mg compartment, K+ ions migrate toward zinc compartment.
0 Since Zn2+ ion can oxidize Mg, than Zn2+ is a stronger oxidizing agent than Mg2+ ion. Conversely Mg is a
stronger reducing agent than Zn.
g) Mg2+ < Zn2+ < Cu2+< Ag*
— >
oxidizing strength
Mg > Zn > Cu > Ag
>
reducing strength

EXERCISE 5.12 Suppose that an electrochemical cell is constructed between magnesium and silver
electrodes.
(a) which electrode would be the anode?
(b) write the net reaction taking place in the cell.
(c) which electrode would gain mass as the cell operated? (a) M g (b) M g + 2 A g * —> M g2 ++ 2 A g

EXAM PLE 5.10 Determination of the Strength of Oxidizing Agents

Problem : Use the following observations to determine the strengths of the oxidizing agents involved in all
the reactions.
I. A strip of nickel dipped in copper sulfate solution becomes coated with reddish brown layer of metallic
copper.
II. A coil of copper wire suspended in silver nitrate solution becomes coated with "whiskers" of metallic sil­
ver.
III. Pieces of granulated nickel in aluminum nitrate solution remains unchanged.
IV.A strip of magnesium in aluminum nitrate solution dissolves producing Mg2+ ions.
Solution : The observations may be represented by the equations.
I. Ni (s) + Cu2+ (aq) — > Ni2+ (aq) + Cu (s)
II. Cu (s) + 2Ag+ (aq) — »•' Cu2+ (aq) + 2Ag (s)
III. Ni (s) + Al3+ (aq) — > no reaction
IV. 3Mg (s) + 2A13+ (aq) — > 3Mg2+ (aq) + 2A! (s)
Since these reactions take place spontaneously the oxidizing strengths of the ions are
I) Cu2+ > Ni2+ II) Ag+ > Cu2+ III) Ni2+ > Al3+ IV) Al3+ > Mg2+
The order of oxidizing strengths of ions is Ag+ > Cu2+ > Ni2+ > Al3+ > Mg2+

EXERCISE 5.13 Use the following data to determine the reducing strengths of the elements H, Mg, Cr,
Fe and Zn.
I. Zn, Fe, Cr, and Mg when reacted with acids produce H2.
II. Zn does not react with Mg2+, but reacts with Cr3* and Fe2+.
III. Fe does not react with Zn2+, Cr3+ and Mg2+, Mg > Zn > Cr > Fe > H
 .... inn O xidation - R ed u ctio n R eactions 191

EXERCISE 5.14 Using the knowledge you have gained so far about the reducing or oxidizing strengths
jof the elements Mg, Zn, Ni, and Ag, decide in which of the following beakers a reaction is to be observed?
•v if Ag Mg

Ni2+ Zn2+ Ag+

— —
4__ ....->
I П Ш IV

5.3.2 STANDARD ELECTRODE PO TENTIALS

So far we have not considered the m eaning o f cell voltage. The cell voltage
o f a voltaic cell indicates the tendency for the cell reaction to occur. The higher
the cell voltage, the greater the tendency for the forw ard reaction to occur.
H owever, the cell voltage o f a given cell also depends on the concentration o f
H a lf - c ell p o te n tia ls are ions involved in the cell reaction. To com pare the spontaneities o f two different
also c a lle d ele ctro d e p o ­
cell reactions, their cell voltages m ust be m easured at the sam e concentrations
te n tia ls .
o f ions and at the same temperature. A standard cell is defined to m ake com pari­
sons easier. A standard cell contains ions at 1 M concentrations and gases at 1
atm pressure at 25°C. The voltage o f such a standard cell is called s ta n d a r d
cell v o ltag e or s ta n d a r d cell p o te n tia l and show n by e°.
The potentials o f the standard zinc - copper and copper - silver voltaic cells
are 1.10 volts and 0.46 volts, respectively. T he com parison o f these voltages
reveals that the oxidation o f zinc by copper ions has greater tendency to go for­
ward com pletion than does the oxidation o f m etallic copper by silver ions. In
the sam e way, the tendencies o f occurrence o f tw o different h a lf - reactions
m ay be com pared if their standard half - cell potentials can be m easured. B ut it
is impossible to determine experimentally the potential o f a single h alf - cell or a
single electrode, because every oxidation m ust be accom panied by a reduction
— * H2(g) (that is the electrons m ust have som ew here to go). H ow ever, we can m easure
the difference betw een the potentials o f two h alf - reactions. Thus, if one half
reaction taking place at standard conditions is arbitrarily assigned a standard
half- cell potential o f zero, the standard potential o f other half - reactions can be
determ ined relative to that reference. T herefore it is necessary to establish a
2H*‘( a q )+ 2 e ‘ ^ H ( g )
standard reference electrode whose standard potential is arbitrarily taken to be
zero volt.

5.3.3 STAN DA R D HYDROGEN ELEC TR O D E (SHE)

By international agreement, the standard hydrogen electrode is chosen as the

FIGURE 5.4 The sta n ­ standard reference electrode w hich is illustrated in Figure 5.4. It consists o f a
dard hydrogen electrode platinum electrode im m ersed in a 1 M H + solution. H ydrogen gas is bubbled
(SHE). It consists of a plati­ through the glass envelope over the platinum electrode at 1 atm pressure and
num electrode in a solution
25°C. The standard hydrogen electrode is arbitrarily assigned a potential o f ex­
in which the [H +] is 1 M with
actly 0 . 0 0 0 volt.
H 2 gas at a pressure o f 1
atm bubbled over the elec­
trode.
192 Chapter 5

H 2 — > 2Н+ + 2е“ £° = 0.000 V (as anode)

2Н + + 2е“ -— > Н 2 е° = 0.000 V (as cathode)
W hen a cell is assembled from a standard hydrogen electrode, and another stan­
dard h alf cell, then the standard cell potential, e°ceu, is regarded as the standard
half - cell voltage o f the other cell. Now let us consider two cells.

5.3.3.1 THE ZINC - SHE CELL

The zinc - SHE cell is shown in Figure 5.5.

Zn(s) I Zn2+ (1M) 11 H + (1M) H 2 (latm ) I Pt(s)

V oltm eter

FIG U RE 5.5 M eas­

urement o f the elec­
trode potential of zinc
using the standard hy­
drogen electrode as the
reference■

Zn —» Zn + 2e 2H 2e
Oxidation (anode) Reduction (cathode)

The following observations can be m ade w hen the cell operates.

1. The initial cell voltage is 0.76 V.
2. The zinc electrode loses weight.
3. T he [H+] in the hydrogen electrode decreases.
From these observations we can deduce the following reactions.
Zn — > Zh2+ + 2e* e° = ? (anode reaction)
2H+ + 2e- — > H 2 e° = 0.00 V (cathode reaction)
Zn + 2H+ — > Zn2+ + H 2 e°cell = 0.76 V (cell reaction)
The voltage produced by the cell is the sum o f the h alf cell potentials o f the
T h e h a lf - c ell p o te n tia l anode and cathode reactions.
fo r any re d u c tio n r e a c ­
tio n is e q u a l in m a g n i­ cell = e anode + e cathode or cell = £ „, + e red

tu d e b u t o p p o s ite in Inserting the values o f the cell into the equation gives
sig n to th a t o f o x id a ­
0.76 V = £°anode + 0.00 V
tion. £,
£°a„ode = 0 .7 6 V -
Shortly the standard oxidation potential o f zinc half cell is equal to the poten­
tial o f the cell, 0.76 V.
Zn — > Zn2+ + 2e- £° = 0.76 V
I f we consider the standard reduction potential o f the zinc h alf - cell, its re­
duction potential is ( - 0.76) V or
. Zn2+ + 2e > Zn £° = - 0 . 7 6 V
I f w e reverse a reaction, w e m ust change the sign o f its potential.
 пни in ним .......... ^O xidation - Reduction Reactions 193

5.3.3.2 COPPER - SHE CELL

This cell is show n in Figure 5.6. D uring the operation o f the cell the follow ­
ing observations can be made.
1. The initial cell voltage is 0.34 V.
2. T he copper electrode gains weight.
3. T he [H+] o f the solution o f the SHE increases.

V oltm eter

F I G U R E 5 . 6 M e a s u re ­
ment of the electrode p o ­
tential of copper using the
standard hydrogen elec­
trode as the reference.

lMHCKaq) 1 MCuS04(aq)

T he following half - reactions, and cell reaction are consistent with die equa­
tions,
H 2 — > 2H+ + 2e- e° = 0.00 V (as anode)
Cu2+ + 2e_ — > Cu 6 ° = ? (as cathode)
H 2 + Cu2+ — > Cu + 2H + £°cell = 0.34 (cell reaction)
p° — p° i p°
c cell c anode 0 cathode

0.34 = 0.00 + £ ° ca*ode

£°cathode = 0.34 V
By m easuring the standard half cell potentials o f several other half - cells ver­
sus SHE in the sam e m anner we described before, a series o f standard h alf cell
potentials can be obtained. To com pare the standard potentials o f the h alf cells
easily, they are tabulated for reduction reactions (cathode processes) by interna­
tional agreem ent. T he table thus obtained is called the table o f standard reduc­
tion potentials. The standard reduction potentials o f some selected half reactions
are shown in Table 5.1. R em em ber the reverse o f any reaction in this table is an
oxidation reactioft (anode process). The oxidation potential o f the reaction will
have the same m agnitude fo r the reduction potential but opposite in sign.
194 Chapter 5 III! I lllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllll

TABLE 5.1 Standard Reduction Potentials

Reaction e° (volt) Reaction e° (volt)

2
F (g) + 2e~ —> 2F~ 2 .8 7 . 2 2
H g C l (s) + 2e- -+ 2H g(l) + 2 С Г 0 .2 7

MnGT + 8H + + 5e- -> M n2+ + 4 H 20 1 .5 1 A g C l (s) + e- - » A g (s) + Cl- 0.22

A u3+ + 3e- -+ A u 1 .5 0 C u2+ + e- C u+ 0 .1 5

2
P b 0 (s) + 4 H + + 2e- -> P b 2+ + 2 H 20 1 .4 7 S(s) + 2H + + 2e- -+ H 2S 0 .1 4

2
C l (g) + 2e- -+ 2 C P 1 .3 6 H S0 4 + 3 H + + 2 e --> S 0 2(g) + 2 H 20 0 .1 4

C r 20 2' + 14H + + 6e- -+ 2 C r3+ + 7 H 20 1 .3 3 S4C ^' + 2 e - - > 2 S 20 2‘ 0 .0 9

0 2(g) + 4 H + + 4 e - -+ 2 H 20 1 .2 3 2 H + + 2e" —> H 2(g) 0.00

2 I0 3' + 12H + + 10e- -> I 2(s) + 6 H 20 1 .1 9 P b 2+ + 2e- -> Pb(s) - 0 .1 3

B r 2(l) + 2e~ —> 2 B r‘ 1 .0 7 N i2+ + 2e- ^ N i(s) - 0 .2 5

C u 2+ + Г + e- -+ C u l(s) ' 0 .8 5 F e 2+ + 2e- F e(s) - 0 .4 4
A g + + e- -> A g(s) 0 .8 0 Z n 2+ + 2e" Z n (s) - 0 .7 6
F e 3+ + e - -> Fe2+ 0 .7 7 A l3+ + 3e- -+ A l(s) - 1.66
2
0 (g) + 2 H + + 2e- -> H 0 22 0 .6 9 M g 2+ + 2 e _ —» M g(s) - 2 .3 7

^ + 2e- -+ 3 T 0 .5 4 N a+ + e - - ^ N a(s) - 2 .7 0

2
I (s) + 2e- -+ 2Г 0 .5 3 K + + e- -+ K (s) - 2 .93
C u 2+ + 2e- - » C u(s) 0 .3 4 L i+ + e~ - 4 L i(s) - 3 .0 3
* a large list is given in appendix III

EXAM PLE 5.11 Understanding Reference Electrode.

Problem : If the standard reference electrode had been chosen as the standard zinc electrode, what would have
been the standard reduction potentials of (a) aluminum electrode? (b) hydrogen electrode? (c) chlorine electrode?
Solution : Let us list the reduction potentials of these electrodes with reference to the standard hydrogen elec­
trode. (Use Table 5.1)
A1 Zn Cl2
— —t------- —------ '----------------- 1 1 >£°red (V) (with respect to SHE)
-1.66 -0.76 0.00 +1.36
By chosing the zinc electrode as a reference electrode (an electrode that has a reduction potential of 0.00V) we in­
creased its reduction potential by 0.76 V [ffom(-0.76) to (0.00)]. The reduction potentials of all the other elec­
trodes must be increased by the same amount 0.76 V.The reduction potentials would be :
A1 Zn Щ , Cl2
*----------------- 1------------------*-------------------- 1— >£0red (V) (with respect to SZnE)
1.90 0.00 + 0.76 +2.12

EXERCISE 5.15 If the standard reference electrode were the standard silver electrode, what would be the
standardreductionpotentials of (a) zincelectrode (b) hydrogenelectrode (c) gold electrode.
(a ).1 .5 6 V, (b) -0 .8 0 V, (c)+ 0 .7 0 V
 HiiiiiMMiMiiMiiiiiiiiMMiiiMiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiHiiiiHiiiiiiiiiiiiiiiiiiiiiiiiiiMiiMiiiiiiniiiiMiiiiiiiiiiii!O xidation - Reduction Reactions 195

5.3.4 THE USE OF STANDARD ELECTRODE

P O T E N T IA L S
The standard electrode potentials can be used in m any ways.
1. They help to calculate £°ceM of a voltaic cell.
C onsider a cell constructed from N i/N i2+ and A g/A g+ h a lf cells. If w e take
their standard reduction potentials from the table, we see that

(I)N i2+ + 2e- — * Ni £°red = -0 .2 5 V

(II) Ag+ + le- — > Ag e 0^ = + 0.80 V
Since the electrode potentials indicate the tendency o f a reaction to occur, then
S in c e th e v a lu e o f £ ° i s
reaction (II) w hich has greater reduction potential will take place as w ritten (the
n o t d ep en d e n t o n the size
reduction h alf - reaction). And reaction (I) has to take place in the opposite di­
a n d s h a p e o f th e e le c ­
tro d e s ,c h a n g in g th e c o e f ­ rection (oxidation h a lf - reaction). So the h a lf reactions and their potentials in
fic ie n ts o f re a c tio n d o e s the cell are
n o t c h an g e its v a lu e o f £ ° Ag+ + l e ' — > Ag £°red = + 0.80 V (cathode)
Ni — > Ni2+ + 2e- £°ox = + 0.25 V (anode)
To obtain the cell reaction, the reduction o f Ag+ m ust be m ultiplied by 2 be­
fore the addition so that the electrons lost and gained in the h alf - reactions will
cancel. N otice that £°Ag/Ag+ is not m ultiplied by 2. The potential o f a h a lf - cell
reaction does not depend on the coefficients o f the reaction. It ju st depends on
tem perature and concentrations. The cell reaction and cell potential m ay be ob­
tained by adding the reactions side by side.

2Ag+ + 2e » 2Ag £°ted = + 0.80 V

Ni — » N i2+ + 2e- £°ox = + 0.25 V

2Ag+ + Ni — > 2Ag + N i2+ E0^ , = £°red + £°ox = 1.05 V

B riefly : To calculate £°ссц from the table

1) Select the electrode w hich has greater reduction potential. This electrode
acts as the cathode.
2) Reverse the other cell reaction and its sign o f the h a lf cell potential.
3) Balance the num ber o f electrons gained and lost by m ultiplying the h a lf
reactions by suitable numbers. Do not m ultiply the h a lf cell potentials.
4) A dd the reactions side by side, this gives the cell reaction after cancelling
electrons. The addition o f £°redand £°ox gives £°cM.

EXAM PLE 5.12 Calculating £°cell from the Standard Half Cell Potentials
Problem : Calculate the standard cell potential of a cell composed of standard zinc and chromium electrodes.
What is the reaction taking place in the cell?
Solution : We must first determine the half reactions and their potentials from Table 5.1.

Zn2+ + 2e > Zn £°red = - 0.76 V

Cr3+ + 3e- — > Cr £°red = - 0.74 V

Since the reduction potential of Cr3+ is greater than that of Zn2+, then Cr3+ ions will be reduced, and metallic
zinc will be oxidized to Zn2+ ions.
196 Chapter 5 ШИП Ш ИШ I lllllllllll I ll Ш Ш Ш Ш Ш Ш Ш Ш Ш ПП ШИШ I ll II I

Сг3+ + Зе > Сг Е0^ = - 0.74 V

Zn — > Zn2+ + 2е- Е°ох = + 0.76 V
То balance electron numbers, multiply the reduction reaction by 2 and the oxidation reaction by 3. The addi­
tion of the reactions obtained gives the cell reaction. The sum of the £°rcd and £°ox gives £°cen-

2Cr3+ + 6 e- — » 2Cr £°red = - 0.74 V

3Zn — » 3Zn2+ + 6 e- £°ox = + 0.76 V

2Cr3+ + 3Zn — > 2Cr + 3Zn2+ £°ceU = + 0.02 V

EXERCISE 5.16 Write the cell reactions and calculate the standard cell potentials for the following cells
constructed by
a) Sn/Sn2+ and Pb/Pb2+ electrodes. b) Mg/Mg2+ and СУСГ electrodes.
a) S n + P b 2* -> S n 2* + P b £ ° c t „ = 0.01 V b) M g+ Cl2 -> M g 2* + 2CI- £ ° eell = 3.73 V

EXAM PLE 5 .1 3 Calculating Half - Cell Potential

Problem :
I. 2A1 + 3Cd2+ — > 2A13+ + 3Cd £°celI = 0.26 V
II. Al3+ + 3e~ — > A1 £°red = - 0.66 V
Using the data given above, calculate the standard oxidation potential of Cd to Cd2+
Solution : First let us divide reaction (I) into itshalf reactions. .
— P°
2A1 — » 2A13+ + 6 e“ £°ox = +1.66 V \ £°cell — ox -I- ^P ° red
3Cd2+ + 6 e~— » 3Cd________________£°red = ?___________ f £°red = 1.26 — 1.66 = - 0.40 V
2A1 + 3Cd2+ — > 2A13+ + 3Cd £°ceU = - 0.26 V
a Cd2+ + 2e— > C d £°red = - 0.40 V => Cd — > Cd2+ + 2e E°ox = + 0.40 V

E XE R C IS E 5.17 I.T i + 2 Ag+ > Ti2+ + 2 Ag £°ceU = 2.43 V.

II. Ag+ + le » Ag £°red = 0.80 V.
III. Cu2+ + 2e > Cu £°red = 0.34 V.
Use the data given above to determine a) the standard half cell potential for Ti2+ + 2e > Ti
b) the cell potential of the cell constructed by Cu/Cu2+ and Ti/Ti2+ electrodes.

a ) e °Ti2* m = ‘ 163 V’ b )e ° " 11 = L97 V

T h e v a lu e of £ ° ccll te lls
2- They help us to determine the spontaneity of a given reaction.
u s t h e d i r e c ti o n in I f the £°ceii o f a given reaction is positive the reac.tion w ill take place spontane­
w h ic h a re a c tio n m a y ously as written. I f the £°ceU is negative, it w ill h o t take place spontaneously as
sp o n ta n e o u sly go, b u t it
te lls u s n o th in g a b o u t written. B ut the reverse o f the given reaction w ill take place spontaneously b e­
th e r a te a t w hich a re a c ­ cause it w ill have a positive £°cM.
tio n w ill occur.
C onsider the reaction : M n + Co2+ — > Mn2+ + Co
D oes this reaction take place spontaneously? To answ er this question, let us
divide the reaction into reduction and oxidation half reactions.

Mn > Mn2+ + 2e~ In the re a c tio n M n is o x id iz e d to

Co2+ + 2e~ > Co M n 2+ and C o2+ is red u ced to Co
 11Ш
Ш 111111111М
111111М
11М
1Ш1Ш
1ШМ11Ш
Ш Ш1Ш
11111Ш
Ш11111Ш
Ш11Ш
1Ш1!!11М
111Ш
11Ш
!Ш1!Ш
Ш 1Ш111!>1!Е! Oxidation - Reduction Reactions 197

If we take the potentials o f the h alf reactions from Table 5.1 we see that

Co2+ + 2e------ » Cb 8 ° ^ = - 0.28 V

M i — > Mn2+ + 2e- £°ox = + 1.18 V
Then the standard cell potential is (+ 0.90 V).
So the reaction M n + Co2+ — > M n2+ + Co will take place spontaneously
under standard conditions. O r Co2+ is a better oxidizing agent than M n2+.
P ractically w e m ay reach the sam e result by com paring the oxidizing
strengths o f Co2+ and M n2+. If we com pare the oxidizing strengths (or the re­
duction potentials) o f the half reactions,
Mn2+ + 2e- — > M i £°red = - 1.18 V
Co2* + 2e------ > Cb £°red = - 0.28 V
we see that C o2+ has greater tendency to gain electrons than M n2+ does, and
Co2+ is a stronger oxidizing agent than M n2+, so in this reaction Co2+ can oxidize
M n to M n2+.
Sim ply the species at the bottom o f the table o f the standard reduction poten­
tials in Table 5.1 m ay oxidize the species at the top o f the table.

EXAM PLE 5.14 Predicting the Spontaneity of Reactions

Problem : Is the reaction, Cr3+ + Fe2+ — > Cr2+ + Fe3+ , spontaneous under standard conditions?
Solution : The inspection of the reaction indicates that its half reactions are
Cr3+ + le - — > Cr2+ £°red = - 0 . 4 1 V (The values are taken from the table)
Fe2+ — > Fe3+ + le- £°ox = - 0.77 V
The cell potential is

£°CeU = e°red + e ° ox => £°cell = (~ 0.41) + ( - 0.77) = - 1.18 V.

Beacuse the potential of the given reaction is negative, it does not take place as written under standard condi-
tions.lt means that Cr3+ cannot oxidize Fe2+ to Fe3+. Instead Fe3+ can oxidize C r2+ to C r3+. O r th e rev erse re ­
action is sp o n ta n e o u s u n d e r s ta n d a rd conditions.

EXERCISE 5.18 Which of the following reactions are spontaneous under standard conditions?
(a) Sn + Cu2+ — ► Cu + Sn2+
(b) 3Fe + 2A13+ — > 3Fe2+ + 2A1
(c) 2A13+ + 3H2 — > 2A1 + 6 H+
„ (a) s p o n ta n e o u s ; (b) and (c) n o n s p o n ta n e o u s

EXAMPLE 5.15 Predicting Spontaneous Reaction

Problem : Decide, by co n su ltin g th e tab le, w hich one of th e Cu, N i, Ag, produces H 2 g as from
1 M HC1 solution?
Solution : This question is a different form of the question which metal may reduce H+ to H2. Let us assume
all the metals may reduce H+ to H2. Hence the reactions of the metals and the cell voltages are,
Cu + 2H+ — *• Cu2+ + H 2 £°сец = £° (Cu/Cu2+) + £° (2H+/H2) = (-0.34) + (0.00) = - 0.34 V
Ni+ 2H+ — > Ni2+ + H 2 £°ceU = £° (Ni/Ni2+) + £° (2 H+/H2) = (+0.25) + (0.00) = + 0.25 V
2 Ag + 2H+ — > 2Ag+ + H2 £°ceU = £° (Ag/Ag+) + £° (2H+/H2) = (- 0.80) + (0.00) = - 0.80 V
Only £°cell of Ni - SHE is positive. Only Ni metal can produce H 2 when reacted with HC1.
198 Chapter 5 IIIIIIIUIIIIII П И Ш И .

EXAM PLE 5 .1 6 Determining Spontaneous Reaction

Problem : Will cadmium (II) ions oxidize metallic zinc to zinc ions or will zinc ions oxidize cadmium to
cadmium (II) ions?
Solution : One of the two reactions is spontaneous. To determine the spontaneous one, let us choose the
appropriate half reactions from the table of standard reduction potentials.

Cd2+ + 2e- — » Cd e°red = - 0.40 V

Zn2+ + 2e- — > Zn £°red = - 0.76 V
Since the half reaction with greater potential takes place as written, and the other in the reverse direction,
then the spontaneous reaction between the two half reactions is

Cd2+ + Zn — > Cd + Zn2+ £°cell = (-0.40) + (+0.76) = +0.36 V

So we deduce that Cd2+ ions can oxidize Zn to Zn2+ ions. The reverse of this reaction,
Cd + Zn2+ — > Cd2+ + Zn, has a cell potential of (-0.36 V). So this will be a nonspontaneous reaction. Or
Zn2+ ions cannot oxidize Cd to Cd2+.

E X E R C IS E 5.19
(a) Will Fe2+ oxidize Sn2+ to Sn4+?
(b) Will Cl2 oxidize Г to I2?
(c) Will permanganate ions oxidize hydrogen peroxide (H2 0 2) to free oxygen (Ог) in acidic solution?
(a) N o , (b) Y es, (c) Yes.

EXAM PLE 5 .1 7 . Determining Spontaneous Reaction

Problem : In which of the following beakers there will be no reaction? (Consult Table 5 .P
Fe Cu Zh Cu AL

I П Ш IV V
Solution : The probable reactions and their cell potentials are
I. Fe + Cu2+ -> Fe2+ + Cu e°cell = + 0.78 V => probable reaction

II. Cu + 2Ag+ -—> Cu2+ + 2Ag £°ceU = + 0.46 V => probable reaction
III. Zn + Ni2+ -—> Zn2+ + Ni e°Ceii = + 0.51 V => probable reaction

IV. Cu + 2H+ - - > Cu2+ + H2 e°cell = - 0.34 => nonprobable reaction

V. 2A1 + 3Zn2+ — >2A13+ + 3Zn £°cell = + 0.90 V => probable reaction
So, there will be no reaction in beaker IV.
 пшшплттитпшшшппшишпшшшшиишшиппиннмппшшпшимммммипшшшшимн! Oxidation - Reduction Reactions 199

EXERCISE 5 . 2 0 Given the following three containers.

Pb Ag Zn

ZnS04 PbS04 AgN03

V ... ..... J v >

A reaction takes place only in one of these containers. If 3.24 g of metal deposite in this container, how
many grams of the other metal will.dissolve in the same container? 0.975g Zn

3 - The table helps us to determine the reactions which take place

at the electrodes during the electrolysis. T his w ill be explained in this
chapter in section 5.4

5.3.5 EFFECT OF CONCENTRATIONS ON ELECTRODE

POTENTIALS
So far, we have discussed standard potentials, that is, potentials when con­
centrations o f all dissolved substances are 1 M and the pressures o f gases are 1
atm. But we often encounter electrochem ical cells whose com ponents are not in
the standard states.
W e m ay predict the effect o f concentration changes on the cell potential by
applying Le Chatelier's Principle to the cell reactions. Since the potential o f the
cell indicates the tendency o f the forward reaction to take place, then we can de­
duce that any fa cto r which forces the reaction in the fo rw a rd direction will cause
an increase in the cell potential or vice versa.
Consider the equilibrium for the cell reaction
Cu 2 + (aq) + Z n (s ) C u (s) + Zn 2 + (aq) E0^ = 1.10 V
T he positive value o f e°show s that the reaction proceeds in the forward direc­
tion spontaneously, decreasing [Cu2+] and increasing [Zn2+], A ccording to the
"Le Chatelier's Principle", both decreasing the [Cu2+] and increasing the [Zn2+]
causes the equilibrium to shift to the reverse direction, w hich will decrease the
cell voltage increasing. W hen the concentrations o f ions reached the values o f
the [Zn2+] and [Cu2+] w hich satisfy the equilibrium constant o f the reac­
tion, Kc =[Zn2+] / [Cu2+], there will be no further net reaction. T he system will
be at equilibrium. Since the forward and reverse reactions take place at the sam e
rate at equilibrium , the voltage o f the cell will be zero. W e say that the cell is
"dead". T hus, at equilibrium the cell voltage is zero and the concen­
trations oMons are equilibrium concentrations.
The effect o f concentration changes on the cell voltage m ay be calculated by
m eans o f the N em st equation.

0.059
n log Q
p °
t cell

W here £ceUis the potential o f the electrochem ical cell at a nonstandard condi­
tions, n is the num ber o f m oles o f electrons transferred in the overall cell reac-
200 Chapter 5 .... I .......... ниш........ I ..... INI................ iiiiiii

R e m e m b er th a t Q has the tion, and Q is the reaction quotient for the cell reaction. As an exam ple o f how
sa m e fo rm as the e q u ili­ N em st equation m ight be used consider the reaction :
b riu m c o n sta n t К Zn(s) + Cu 2 +(aq) Zn 2 +(aq) + Cu(s)

0.059, [a 2 + ]
8 ceU= 1.10V - log-
M

EXAM PLE 5.18 Predicting e cenat Nonstandard Conditions

Problem : Consider an electrochemical cell for which the overall reaction is,
Pb2+ (aq) + Sn (s) — > Pb (s) + Sn2+ (eq)
(a) Calculate e°cell.
(b) Will the cell potential increase or decrease when
(1) the [Pb2+] in the lead half - cell is increased?
(2) the [Sn2+] in the tin half - cell is increased?
(3) some Nal in dissolved in the solution of the lead - half cell? (Pbl2 is a negligibly soluble solid)
(c) Calculate £ccll under the conditions
(1) [Sn2+] = 1 M, [Pb2+] = 0.1 M.
(2) [Sn2+] = 0.1 M, [Pb2+] = 1 M.
(3) [Sn2+] = 0.5 M, [Pb2+] = 0.05 M.
Solution : (a) The potentials of the half - cell reactions taking place in the cells are,
C ath o d e : Pb2+ + 2e' — > Pb £°red = - 0 .1 3 V

A node : Sn — > Sn2+ + 2e" £ ° ox = + 0 . 1 4 V

Overall : Pb2+ + Sn — > Sn2+ + Pb £°ceU = 0.01 V.

(b) According to the Le Chatelier's Principle,
(1) Increasing the [Pb2+] increases the tendency of the occurrence of the forward reaction, hence the cell volt­
age increases.
(2) Increasing the [Sn2+] decreases the tendency of the occurrence of the forward reaction, therefore decreases
the cell voltage.
(3) The addition of I" ions (Nal) will precipitate Pb2+ ions as Pbl2. So decreasing the [Pb2+] will shift the re­
action to the left, hence the cell voltage will decrease.
(c) (1) By using Nemst equation we can determine the cell potentials at nonstandard conditions.
2 +
0.059 0.059 Sn
£ cell = £ cell log Q Ecc.i — £ cell log
2 +
Pb

0-059 , .r , 1
Ecell = 0 .0 1 lO g ^ - = 0.01 log 1 0 = e° ceii = o.oi - о.оз cell = - 0.02 V

The negative value of the cell potential indicates that the reaction will now proceed spontaneously in the re­
verse direction.
(2) £ceU = 0.01 - °-0 5 9 log ^ = 0.01 - ^ 9 log 10 1 ecell = 0.01 - ( - 0.03) = 0.04 V
2 2
0.059 l o g - M . = 0 .0 1 0.059
(3) Eeeu = 0.01 . loglO = 0.01 - 0.03 = - 0.02 V
0.05

* Hermann W alther Nemst (1864 - 1941). A German chemist, and founder of same theoretical parts of electrochemistriy.
|1!ш11!1ш1ш1ш1шшшш!ш1шшш1м|м|ш!ш11111мш1шш!шш1ш1шшшш1111шш!1шшш1ш1ш11 O xidation - Reduction Reactions 201

So, for a reaction with a small £°cell value, changes in electrolyte concentrations can reverse the direction in
which reaction spontaneously proceeds.

EXERCISE 5.21 What conditions increase the cell potential for the reaction,
Fe2+ (aq) + Ag+ (aq) — Fc3+ (aq) + Ag (s) ?

EXERCISE 5.22 For the cell, Cd (s) + 2 Ag+ (aq) — > Cd 2 + (aq) + 2Ag (s) £°ceU = 1 .2 V, what is
the cell potential if the concentrations of ions are as follows? [Cd2+] = 1 M, [Ag+] = 0.1 M. 1.14 Volt

EXAM PLE 5 . 1 9 A C o n c e n tra tio n C ell

Problem : Any electrochemical cell consisting of two identical half - cells but different ion concentrations
only is called a concentration cell. Suppose that we set up a concentration cell illustrated below.

Voltm eter

What are the anode, cathode and overall cell reactions and the cell potential for this cell ?
Solution : Both half - cells are copper half - cells. But the concentrations of Cu2+ ions are different. To deter­
mine anode and cathode let us look at the potentials of the half cell reactions.
Cu2+ (1 M) + 2e- —» Cu £° = + 0.34 V
Cu2+ (0.1 M) + 2e- — > Cu £ = ?
According to the Le Chatelier's Principle, decreasing the Cu2+ concentration will decrease the tendency of the
occurrence of the forward reaction, hence the potential of the half cell which has lower [Cu2+] will be smaller.
Cu2+ (1 M) + 2e- — > Cu £° = + 0.34 V
Cu2+ (0.1 M) + 2e- — » Cu £ < 0.34 V
By comparing the magnitudes of the reduction potentials of these half cells we may determine the cathode,
the anode and the overall reactions as follows.

C ath o d e : Cu2+(1 M) + 2e_ — > Cu => the reaction with greater reduction potential.
A node : Cu — > Cu 2 + (0.1 M) + 2 c => the reaction with lower reduction potential.
O verall : Cu2+ (1 M) — > Cu2+ (0.1 M)

This cell will operate until the concentrations of Cu2+ ions become equal in both anode and cathode compart­
ments. Or we may find the reduction potential of the copper half cell at nonstandard conditions by using Nemst
equation.
202 Chapter 5 illllllllllllllllN N IIIIIIN IIIIIIIIIIIIIIIIIIIIIN IIIIIIIIIIIIIIIIIN IIIN lIIIIIIIIIII ... 11ШШШ1ШШШШШ1Ш1111Ш11Ш111ШШ1111Ш111ШШШ1Н11111111111...............

The reduction potential for the half - reaction, Cu2+ (0.1 M) + 2e_ > Cu , is

„ 0.059 , 1 0.059 , 1
e = e° log^ T e = 0.34 - —— log— e = 0.34 - о.оз => e = o.3i v
n л 2+l ' 2 0 .1
Cu

So, the half reactions and their potentials are

Cu2+ (1 M ) + 2e- — > Cu £° = + 0.34 V

Cu2+ (0.1 M ) + 2e- — > Cu £ = + 0.31 V
Applying the usual procedure to get the overall reaction gives
C ath o d e : Cu2+ (1 M ) + 2e > Cu £° = 0.34 V
A node : Cu — » Cu2+ (0.1 M) + 2e~ £ = - 0.31 V
O v e ra ll: Cu2+ (1 M) — > Cu2+ (0.1 M) £ceU = 0.03 V

EXERCISE 5.23 An electrochemical cell consists of two hydrogen electrodes. One is the standard hydro­
gen electrode, and the other is a hydrogen electrode immersed in a solution of 0.1 M HC1. The two half - cells are
joined by a salt bridge. Write the overall cell reaction. Determine the anode and the cathode of the concentration
cell. 2H * (1 M) -> 2 H+ (0.1 M)

5.4 ELECTROLYTIC CELLS. AND ELECTROLYSIS

Electrolytic cells are electrochem ical cells in which n o n sp o n tan eo u s oxida­
tion - reduction reactions are made to take place by the input o f electrical energy.
T his process is called electrolysis. Sim ply in an electrolysis reaction, electric
energy is used to produce a chem ical change that will not occur spontaneously.

Electrolysis o f Molten
Sodium Chloride. The electric current
outside the electrolytic cell is carried by
the electrons, which are pushed around
the ciruit by the battery. Inside the mol­
ten electrolyte the current is carried by
the movement o f the positive and nega­
tive ions toward the electrodes. At the
anode СГ ions give up electrons to the
electrode to give Cl atoms, which com­
bine to give Cl2 molecules. A t the ca­
thode Na+ ions accept electrons from the
electrode to give Na atoms, which form
liquid sodium metal.
O xid a tio n Reduction
2CI — > C I 2 (g) + 2e |yja+ + q*— ^ Na(l)

A n electrolytic cell consists o f a container fo r the reaction m aterial, plus elec­

trodes im mersed in the reaction m aterial and connected to a source o f direct cur­
rent. Inert electrodes such as graphite o r platinum are usually used so that the
electrodes are not involved in the chem ical change. F igure 5.7 show s a sim pli­
fied electrolytic cell for the electrolysis o f m olten NaCl.
 O xidation - Reduction Reactions 203

5.4.1 THE ELECTROLYSIS OF MOLTEN SODIUM

CHLORIDE
W e se e th a t the e le c tro ly sis o f In this electrolytic cell in which a direct source o f electricity is connected by a
m o lte n N aC l p ro d u c e s N a and wire to two inert graphite electrodes that are immersed in molten NaCl (Molten
C l2.B ut so d iu m c an n o t b e p re ­
NaCl is obtained by heating NaCl above its melting point, 801°C). Electrons en­
p a re d b y th e e le c tr o ly s is o f
ter the liquid at the cathode. They are accepted by N a+ ions, the only species in
a q u e o u s N a C l s o lu tio n . In
the medium that is capable o f accepting electrons. This can be shown by
aq u eo u s so lu tio n o f N a C l the
p o s s ib le r e d u c tio n r e a c tio n s Na+ + e* — > Na
that w ill tak e p la c e a t t h e c a ­
thode are. This is the reduction half - reaction o f Na. Meanwhile СГ ions are attracted
2
(1) 2 H 0(1) + 2e~ by the anode, and are oxidized to Cl2 according to the half reaction
2
H (g ) + 2 0 H ~ e ° rcd = - 0.83 V
СГ — » 1/2 Cl2 + le-
(2) N a + (aq) + e~ —>
N a(s) 8° red = - 2.71 V
As we see cations migrate toward cathode and gain electrons that enter the
S in ce re a c tio n I h a s h ig h e r r e ­
system. Anions migrate to the anode to release electrons that leave the system.
d u c tio n p o te n tia l th an re a c tio n
Thus the current is maintained in the system by the movement o f ions, not o f
II, w ater w ill b e re d u ce d at c a ­
electrons.
2
thode and H (g) w ill b e lib e ra t­
The overall electrolysis reaction o f molten NaCl is
ed.
C a th o d e : Na+ + l e - > Na (1)
A node : Cl" — > \[2 Cl2 (g) + le -
O v e ra ll :N a+ + Cl" — > Na (1) + l/2 C l 2 (g)
NaCl (1) — > Na (1) + l/2 C l 2 (g)

In the electrolysis o f molten NaCl, NaCl is converted into its component ele­
ments Na, and Cl2, and the electrical energy put into the system is converted
into chemical energy stored in Na, and Cl2.

5.4.2 THE ELECTROLYSIS OF AQUEOUS SODIUM

SULFATE
N ow let us consider the electrolysis o f a solution o f sodium sulfate in water,
using inert electrodes. See Figure 5.8.

F I G U R E 5 . 8 E le c tro l­
ysis aqueous Na2 S 0 4
solution.

Anode Cathode
Oxidation Reduction
2H20 -> 0 2(g) + 4H* + 4e- 2H20 + 2e' -> H(g) + 20H'
204 Chapter 5 П Ш Ш Ш Ш Ш Ш Н Ш Ш Ш Ш ..................... ..................... ................ I .................. ... ....... .............. ............. .............. .............. .............. ........ Ш Ш Ш Ш Н П .......................... Ш И Ш И .................................. .. ..........................

The solution contains Na+, SO2", H 2 0 , in large quantities and H+, OH" are in
little quantity. So there are two probable oxidation and two probable reduction
reactions.
Reduction : Na+ + le- — > Na £°red= - 2.71 V
H20 + le > 1/2 H 2 + OH" £°red= - 0.83 V
Oxidation: 2 S 0 2' — » S ^ " + 2e- £°0x = -2 .0 1 V

H20 — > 1/2 0 2 + 2H+ + 2e- £°ox = - 1.23 V

As far as reduction reaction is concerned, the greater reduction potential o f

H20 than that o f Na+ indicates that water has greater tendency to be reduced.
Hence at the cathode water w ill be reduced and H 2 gas will be released. The
comparison o f the oxidation potentials o f SO2' and H20 gives the clue that the
oxidation o f water occurs preferentially. The half reactions taking place at each
electrode are

C a th o d e : 2 (H20 + le ' — > 1/2 H2 + OH")

A node : H20 — > 1/2 0 2 + 2H+ + 2e"

O v e rall : 3H20 — > H2 + 1/2 0 2 + 2H+ + 20H"

2H20

So the net reaction is

H20 — > H 2 (g) + 1/2 OaCg)
The net reaction describes the electrolysis o f pure water, which takes place
because water is more easily reduced than Na+, and more easily oxidized than
SO^'. The ions o f Na 2S 0 4 conduct the current through the solution and take no
part in the reaction.

EXERCISE 5.24 Why are different products obtained when molten MgCl 2 is electrolyzed than
when a solution o f MgCl2 is electrolyzed? Why do a solution of CuCl2 and molten CuCl2 give the same
products on electrolysis?

5.4.3 THE ELECTROLYSIS OF AQUEOUS COPPER

SULFATE SOLUTION
The solution now contains Cu2+, SO2", H2 0 , (H+, OH") and copper metal im ­
mersed in the solution.
The possible cathode (reduction) reactions are

Cu2+ + 2e- — > Cu £° = + 0.34 V

2H20 + 2e > H 2 + 20H" £° = - 0.83 V
The magnitude o f the half - cell potentials indicates that Cu2+ ions will be re­
duced at the cathode.
The possible anode (oxidation) reactions are
2SO^ — > S ^ " + 2e- £° = -2 .0 1 V
 uni O xidation - Reduction Reactions 205

The oxidation half reaction o f Cu to Cu2+ is favored because o f its high oxi­
dation potential with respect to the others.
So the net electrolysis reaction o f aqueous C uS0 4 solution is
C ath o d e : Cu2+ (aq) + 2 c — > Cu (s)
A node : Cu (s) — > Cu2+ (aq) + 2 e _
O verall : Cu (s) (anode) Cu (s) (cathode)
That is, copper from the anode dissolves at the same rate that Cu2+ ions are
deposited at the cathode. The [Cu2+] in the solution does not change.

5.4.4 THE IMPORTANCE OF ELECTROLYSIS

The method described in section 5.4.3 is used to refine copper. The impure
copper and the pure copper electrodes are used as the anode and cathode o f the
electrolytic cell, and C u S 0 4 solution is electrolyzed. During the electrolysis,
copper is transported continuously through the solution (as Cu2+) from the
anode to cathode. See Figure 5.9.

Impure Cu anode Pure Cu

P u re C u c a t h o d e ^
Electrolyte now
contains Zn2+, Fe2+
E le c tro ly te
other active metal
H2 S 0 4 + C uS Q ions
Source of
direct current
Cathode Anode
"Anode Sludge" containing Ag, Au, Pt
silver cyanide
bath
F I G U R E 5 . 9 The electrolytic refining o f copper. Since the oxidation of copper is
easier than that of H20 , the copper in the impure copper anode dissolves away as
Cu2+. The C if + ions are reduced at the cathode so the copper cathodes grow in size.
Copper or the other metals such as silver, nickel, chromium can be plated
onto other objects by the same method. In the elecroplating process the object to
FIGURE 5 . 1 0 E le c ­
be plated is taken as the cathode; the metal which w ill be used in plating as the
troplating o f an object
with silver. The object to anode, and a solution o f the same metal is used as the electrolyte. Examples o f
be plated is made the ca­ metal - plated articles are common in our society. Jewelry is often plated with
thode whereas the plating silver or gold. "Tin cans" are steel cans plated with tin. Figure 5.10 shows the
metal is made the anode. electroplating o f a spoon.
The electrodes are im ­
M ost o f the metals are obtained by the electrolysis o f molten compounds o f
mersed in a solution of
the salt o f plating metal. these metals. Na, К, Ca, A 1.... are common examples. M ost chlorine is cheap­
ly produced by the electrolysis o f aqueous sodium chloride.

EXAMPLE 5.20 Predicting Electrode Reactions

Problem : Predict the probable products when the following substances are electrolyzed with inert electrodes.
Consult the table o f the reduction potentials o f substances.
(a) Molten M gCl 2 (b) H 2 S 0 4 solution
S olution : (a) There is just one possible reduction reaction, Mg2+ + 2e_ — > M g
206 Chapter 5 1Ш Ш Ш 1Ш 1Ш 111Ш 111Ш 11Ш П Ш 1Ш Ш 1Ш 1111Ш ! 1111Ш Ш Ш Ш 111111Ш 1Ш 111| 1| 1| | 11111111М 1Ш 111111Ш Ш 1111| 1| | | | 1| М М | | 1Ш 1П 111М 1М 111111Ш 11Ш Ш 11Ш Ш Ш 1Ш Ш Ш 1

and just one possible oxidation reaction, 2СГ — > Cl2 + 2e"
The overall reaction is Mg2+ + 2СГ — > Mg + Cl2
MgCl2
In the electrolysis of molten MgCl2, Mg will be deposited at the cathode, and Cl2 gas will be released at the
anode.

(b) In H2 S 0 4 solution, there are H+, SO2' , OH', H20 species in the medium.

The possible reduction reactions are:

2HzO + 2 e- — > H2 + 20НГ" e° = - 0.83 V

2H+ + 2e_ — >.H 2 6 ° = 0.00 V

and the possible oxidation reactions are :

2SO^~ — > S i0 f+ 2 e - e° = - 2.01V

2HzO — » 0 2 + 4H+ + 4e- 6 ° = - 1.23 V

but the latter ones are favored because of their higher potentials. So in the electrolysis of H2 S 0 4, H2 will be lib­
erated at the cathode, and 0 2 gas at the anode. The net reaction is
C a th o d e : 2H+ + 2e' — > H2 (g)

A node : 1/2 x (2H20 — > 0 2 (g ) + 4H++ 4e')

O verall : H20 — > H2 (g) + 1/2 0 2 (g)

EXERCISE 5.25 If a mixture of molten compounds of NaCl, MgCl2 , A1C13 is electrolyzed, which
metal will be preferentially deposited at the cathode first? AI

1 F a ra d ay = 1 m o l e '
= 9 6 5 0 0 C . I F o f e le c ­
tric ity a lw a y s d e p o - 5.4.5 QUANTITATIVE ASPECTS OF ELECTROLYSIS
s ite s 1 e q u iv a le n t o f The quantitative relationships between electricity and chemical change were
any su b sta n c e . first described by Michael Faraday in the early 1830’s. These relationships are
F o r e x am p le 1 m o l e ' called Faraday's Laws. These laws and their applications were explained in our
d e p o s ite s 1 m ol, o f
book "Chemistry I" on pages 143, 144 and 145. To remind them some illus­
N a, 1/2 m ol o f Z n or
1/3 m ol o f A l. trative examples are given below.

EXAMPLE 5.21 Quantitative Problems on Electrolysis

P roblem : (a) What volume of 0 2 at STP is liberated when 100 mL of 1 M CuS0 4 solution is electrolyzed
by a current of 0.6 A for 13.4 minutes, using platinum electrodes? (b) What is the pH of the solution at the end
of electrolysis? Assume there is no volume change.
Solution : (a) The number of coulombs used may be calculated as follows.
Q (coulombs) = I (amperes) x t (sec)
Q = 0.6(A) x 13.4 (min) x 60 (sec/min) = 482.4 С
The anode reaction in the electrolysis of CuS0 4 solution is:
 нтмимнмйммяпптнжшшжишшммшшнммшшшнжншшшшшммшшшшшншпм! O xidation - Reduction Reactions 207

The half reaction shows that 4 mol of electrons (4 x 96500 C) or 4 F (Faraday) produce 1 mol 0 2 or 22.4
liters of 0 2 at STP.
If 4 x 96500 С produce 22.4 L 0 2 at STP \ 4 0 7 4 x 22 4
/too л пС
482.4 x Lг j\ x = 4 x: 9 6 5 0 0— = 0.028 L of 0 22

(b) The anode reaction also indicates that 4 x 96500 С also produce 4 mol of H+,

1( 4 x 9 ^5s°0° .Ci >r0dUCe 4 m d H+ \ x = [(482.4) (4)] / [4 x 96.500] = 5 x 1(T3 mol of H+

v_* X |j

The [H+] of the solution is

+ _ 5 x 10 mol = 5 x 1 0 ~2 M
0.1 L

and the pH of the solution is pH = - log [H+] = - log 5 x 10 => pH = 1.3

EXERCISE 5.26 In the electrolysis of sodium sulfate solution, the anode reaction may be written
2H20 — > 4H+ + 0 2 + 4e-
If a current of 2.5 A is passed through the solution for 2 hours, what volume of oxygen measured at 27°C
and 1 atm pressure is released? 1.16 L

EXAMPLE 5.22 Calculations about Faraday's Laws of Electrolysis

Problem : Electrolysis of molten XC13 with a certain amount of electric current produces 1.12 g X at the ca­
thode and 672 mL of Cl2 at the anode. What is the atomic weight of element X?
S olution : The net electrolysis reaction of molten XC13 is

2X 3 x 22.4 L
2XC13 (1) — » 2 X (s) + 3 Cl2 (g) let X be the atomic weight of X
1.12 g 0.672 L

If 0.672 L of Cl2 is produced together with 1.12 g of X

then 67.2 L of Cl2 will be produced together with 2 X g of X

X = 67'2 x L 1 2 => X = 56 g/mol

0.672x2

EXERCISE 5.27 Two electrolytic cells containing molten salts CuCl2 and XC13 are connected in series
and electrolyzed for a while.At the end of the electrolysis, it is found that 1.92 g of Cu is deposited at the cathode
of the first cell and 3.94 g of X at the cathode of the other cell. Calculate the atomic weight of element X.
________________________________________ ■
____________ ‘___________________1 9 7 g /m o l

5 .5 SO M E IM PO RTANT O XIDATION - R E D U C TIO N

R E A C T IO N S IN O U R LIFE
5 .5 .1 C O R R O S IO N

Metals will undergo corrosion, an oxidation - reduction reaction, unless they

are protected in some way. In the corrosion o f metals, they undergo the oxida-
208 Chapter 5 ш ш ш ы п т ш т п и ш и н и м п п п п п п м

tion process,
М —> Mn+ + ne-
The reduction reactions occur because of the moist and C02 of air. (C02 in air
makes it acidic). These reactions may be
2H+ + 2e- —> H2 (g) (acid solution)
0 2 + 4H+ + 4 c —■» 2H20 (acid solution)
0 2 + 2H20 + 4e- —> 40H" (neutral or alkaline solution)
Figure 5.11 shows schematically how iron corrodes.
To protect metals from corrosion, metal surfaces must not come in contact with
0 2 and H20. Therefore metals
(1) may be painted.
(2) may be plated with a thin layer o f less oxidized substance such as gold,
platinum, tin...
(3) may be allowed to form a protective film o f oxide o f metal. Zinc, alumi­
num, lead, chromium, tin... may be protected in this way.
(4) may be galvanized. Galvanizing is coating steel or iron with zinc metal.
(5) may be connected to a more active metal, "sacrificial anode”. This meth­
od is also called "cathodic p ro tectio n ” . Suppose that an iron pipe is con­
nected to a strip o f magnesium. Any oxidizing agent, that causes corrosion, will
oxidize magnesium preferentially to magnesium ions because magnesium
oxidizes easier than iron does. (Compare their oxidation potentials). O f course
any other more reactive metal than iron may be used instead o f magnesium here.
See Figure 5.12.

Air Magnesium anode

Mg -> Mg2+ + 2e"

Iron pipe (cathode)

0 2 + 2H20 + 4e’ -> 40H

F I GURE 5.11 The Rusting of Iron. Iron in FIGURE 5 . 1 2 Cathodic Protection. When a block
contact with water forms the anode, where iron of magnesium or zinc is attached to an iron pipe or
is oxidized to Fe2*. Iron in contact with air forms tank buried underground, the magnesium forms the
the cathode where oxygen is reduced to water. anode in an electrolytic cell and the iron becomes the
cathode.

5.5.2 DRY CELL

The most familiar examples of voltaic cells are "dry cells".
Figure 5.13 shows a typical dry cell. Here zinc metal is the anode, and car-
 I ниши inn и шпини...................... m\Oxidation - Reduction Reactions 209

bon rod in the center is the cathode. A moist mixture of ammonium chloride,
zinc casi ng NH4C1, manganese (IV) oxide, Mn02, zinc chloride, ZnCl2, and a porous inert
filler occupies the space between electrodes. The simplified anode, cathode and
Manganese o v e r a 1 1 c c l 1 r e a c t i o n ЭГС,
Dioxide
( M n 0 2) A node Zn - -> Zn2+ + 2e-
C ath o d e 2NH+4 + 2e > 2NH3 + H2
Moist Paste
O v e rall Zn + 2NH+4 -> Zn2+ + 2NH3 + H2 eceU = 1.6 V
Carbon Rod
5.5.3 MERCURY CELL
Another important though more expensive modem battery is the mercury
cell. See Figure 5.14. The strongly basic electrolyte is saturated with zinc in the
form of Zn(OH)^' ions. The electrode reactions are :
F IG U R E 5.13 The bas­
ic structure o f an ordinary
A node : Zn (amalgam) + 20H' ZnO (s) + H20 + 2e-
dry cell type o f battery is C a th o d e : HgO (s) + H?0 + 2e~ Hg (1) + 2QH~
shown in this cutaway
drawing. : Zn (amalgam) + HgO (s)
O verall ZnO (s) + Hg (1)
Since the concentrations of the species involved in the overall reaction remain
constant, the voltage of this cell, 1.34 V, remains constant during its entire life.

5.5.4 LEAD STORAGE BATTERIES

In a lead storage battery the electrodes are plates of lead alloy, that interstices
being filled with spongy lead at the anode, and the lead (IV) oxide at the ca­
thode. The electrolyte is sulfuric acid solution. See Figure 5.15. The electrode
reactions during the discharge are,
moist paste of Hg,
HgO, and KOH- A node : Pb (s) + SO42-. > PbS04 (s) + 2 c
FIGURE 5.14 M ercu- C ath o d e : Pb02 (s) SO*'
4
+ 4H+ + 2e > PbS04 (s) + 2H20
ry Cell.
: Pb (s) + Pb02 (s) + 2H2S04 -> 2PbS04 + 2H20
O verall £ceU= 2 V
A lead storage battery usually consists of three or six electrolytic cells con­
nected in series to produce 6 or 12 V.
As the lead storage battery discharges, some of the sulfuric acid is used up,
and the density of the electrolyte decreases. It is there fore possible to determine
the condition of the battery by measuring the density of the electrolyte in the bat­
tery.
During the recharging of the lead storage battery, the overall reaction is re­
versed by the application of an external potential. After many repeated charge -
discharge cycles, some of the lead sulfate falls to the bottom of the container,
and the sulfuric acid concentration decreases. In this case the battery can not be
recharged fully.

FIGURE 5.15 L e a d
5.5.5 NICKEL - CADMIUM CELL
Storage Cell. Another important storage cell is the nickel - cadmium cell, The overal dis­
charge reaction is,
Cd (s) + 2 Ni(OH)3 —> CdO (s) + 2 Ni(OH)2 (s) + H20 (1) £cell = 1.35 V
This cell is more expensive but handier, lighter and has longer life. It is used
in cordless electric toothbrushes, electric razors, pocket calculators and other
small portable appliances.
210 Chapter 5 I ш ш и ш н н н m i l l ................................. ш и ш и ......................................... Н И ......... Н Н Н Н Н Ш Н Н Н Н И Н Н Н Н Н Н Н ........................ I I I I I ................. ........... н и

SOME NEW TERMS

Activity of metal: The tendency of the metal to Faraday : The charge of one mole of electrons that
release electrons. is 96500 C.
Anode : Electrode at which oxidation occurs. Faraday's laws of electrolysis : The passage
Cathode : Electrode at which reduction occurs. of 1 mol of electrons through an electrolytic cell
Cathodic protection : Protection o f a metal produces one gram - equivalent change at each elec­
against corrosion by connecting it to a more easily trode.
oxidized metal. Galvanic cell : Electrochemical cells in which
Cell potential : The potential difference between spontaneous chemical reactions produce electricity.
oxidation and reduction half reactions. Half - cell : The compartment in which either
Corrosion : The oxidation of metals by moist, half of an oxidation - reduction reaction occurs.
oxygen and carbon dioxide. Nernst equation : The equation used for calculat­
Coulomb : The unit of electrical charge. ing the cell potentials at nonstandard conditions.
Electrochemistry : The branch o f chemistry that Oxidizing agent : A substance that makes oxida­
involves chemical changes produced by electrical cur­ tion possible. It itself is reduced.
rent, and production of electricity by chemical chang­ Reducing agent : A substance that makes reduc­
es. tion possible it itself is oxidized.
Electrodes : The surfaces at which oxidation, re­ Sacrificial anode : A more active metal at
duction reactions occur in electrochemical cells. against corrosion.
Electrode potential : The potential of a half - Salt bridge : A U - shaped tube containing a
cell versus the standard hydrogen electrode. strong electrolyte, which connects two half - cells of
Electrolysis : The process that occurs in electro­ an electrochemical cell.
lytic cells. Standard electrode potential : The reduction
Electrolytic cell : Electrochemical cell in which potential of a half reaction relative to the standard
electrical energy causes a nonspontaneous redox reac­ hydrogen electrode.
tion to occur. Voltage : The measure of chemical potential for a
Electrolytic conduction : The conduction of redox reaction to occur; potential between two elec­
electric current by ions through a solution. trodes.
Electroplating : Plating a metal onto a material Voltaic cell : See Galvanic cell
by electrolysis.
тпиттшп|н1шш1ш11ши1ш111ш11шш1шшп!шм11ш1ш11шшм11т 111нш1н1п1шнш1шнтп1и O xidation - Reduction Reactions 211

REVIEW QUESTIONS AND PROBLEMS

Oxidation - Reduction Reactions

5.1 Define and distinguish the following terms. (II) Zn metal does not react with 1M MgCl2.
(a) oxidation - process, reduction - process. (III) Mg metal reacts with Pb((N03 ) 2 producing
(b) oxidation half reaction, reduction half reaction. Mg(N0 3 ) 2 and metallic Pb.
(c) oxidizing agent, reducing agent. (IV) Zn, Mg, and Pb all react with 1M HC1 to
(d) anode, cathode. produce H2 (g).
(a) Write the net ionic equation representing the
5.2 Why do oxidation and reduction occur simulta­ change for each observation.
neously in a reaction? (b) Arrange the elements, Zn, Mg, Pb and H 2 in
order of increasing reducing tendencies.
5.3 Complete and balance the following half - reac­ (c) Arrange the ions Zn2+, Mg2+, Pb2+, H+ in or
tions. In each case indicate whether oxidation or re­ der of oxidizing tendencies
duction occurs. (d) Arrange these species in order of increasing
(b) Au3*- -> Au strength as reducing agents.
и

(a) К -
t

(d) Sn4+- > Sn2+ (e) W ill a reaction occur if a piece of Pb metal
(c) C12-—> СГ
is dipped into 1M Zn(N0 3 ) 2 (aq) ?
(e) s -—> S2" (f) s 2- - -> S6+
(f) I f a piece of Cu metal reacts with neither
Pb(N0 3 ) 2 (aq) nor HC1, where w ill be the place of
5.4 Which of the following reactions are redox reac­
Cu metal in the list you have prepared for part (b)?
tions?
(a) Formation of lead (II) iodide from aqueous 5.7
solutions of lead (II) nitrate and potassium iodide I Pb
(b) Formation of iodine and sodium bromide
from sodium iodide and bromine
(c) Formation of metallic copper and water from Cu2+ Ag+
copper (II) oxide and H2.

5.5 Does the reaction,

Ce3+ (aq) + Fe3 +(aq) —-> Ce4 +(aq) + Fe2 +(aq), If a reaction is observed in all the containers, arrange
involve oxidation - reduction? If it does, identify these elements in order of increasing strength as re­
(a) the oxidation half - reaction and the reduction half ducing agents.
reaction,
(b) the substance oxidized, and the substance reduced. 5.8 The following reactions occur spontaneously.
(I) X(s)+2Y+(aq) X 2 +(aq) + 2Y(s)
5.6 Observations: (II) 2Z(s) + 3Y2 +(aq) ►2Z3 +(aq) +3Y(s)
2+/
(I) Zn metal reacts with 1M Pb(N03 ) 2 solution (III) 2Z(s) + 3XiT(aq)— > 2Z3 +(aq) + 3X(s)
producing metallic Pb and Zn(N03)2. Arrange the elements X, Y and Z in order of increas­
ing strength as oxidizing agents.

Electrochem ical Cells

5.9 Define the following terms, 5.11 Is there any relationship between the ioniza-
(a) electrolyte (b) electrode (c) anode tion energy and the standard reduction potential of an
(d) cathode (e) standard electrode element? Explain.

5.10 Why is a salt bridge necessary in a voltaic 5.12 Is the standard reduction potential of the stan-
cell? Explain. dard hydrogen electrode actually zero? Explain.
212 Chapter 5 ШШШШШШШШ ..... I....Ill.......II.....Illllll....... .

5 .1 3 What is the significance o f an overall cell po­ 5.20 What would be the standard cell potential for a
tential having a value of magnesium - silver cell if the standard reference elec­
(a) positive (b) negative (c) zero? trode were zinc half - cell? £°Mg2+/Mg = ~ 2.37 V

5 .1 4 Is it possible to measure the half-potential o f e °Z n2+/Z n = - 0.76 V, e°Ag+/Ag = 0.80 V

3 .1 7 V
an isolated half-cell? Explain your answer.
5.21 a galvanic cell was assembled as follows. In
5 .1 5 Draw an electrochemical cell in which the re­
the anode compartment, a chromium electrode was
action is
immersed in a 1.00 M solution of Cr(N03)2 . In the
3Cd(s) + 2A u 3 +(aq) — > 3Cd 2 +(aq) + 2Au(s)
other compartment, an indium electrode was im­
(a) Show the anode and cathode.
mersed in a 1.00 M solution of In(N03)3 . The po­
(b) Show the direction in which ions move in
tential of the cell was measured to be 0.40 V. What
the salt bridge.
is the value of the reduction potential for indium
(c) Show the direction in which the electrons
electrode? Use Table 5.1
move in the external circuit. 0.07V

5 .16 A cell is devised by dipping a nickel wire into 5.22 The value of 8 °ccU for the following reaction is
N i(N 0 3 ) 2 solution, and a silver wire into A g N 0 3 so­ found to be +0.62 V
lution. During the operation o f the cell, it is ob­
3Cu(s) + 2NO“(aq) + 8 H+(aq) — ■>
served that nickel electrode decreases in mass and sil­
3Cu2 +(aq) +2NO(g)+ 4H20 (1)
ver electrode increases in mass. W rite the cell
reaction, and indicate the anode and cathode. What is the standard reduction potential for the fol­
lowing half-reaction if the standard reduction poten­
5 .1 7 Diagram a voltaic cell by using the following tial of Cu2+ to Cu is +0.34 V?
standard half cells. (Consult 8 ° table) N 07 + 4H+ + 3e~ — > NO + 2H20 8° =?
(a) Zn / Zn2+ and N i/ N i2+ 0.96V
(b) A 1 / A l3+ and Cu / Cu2+
5.23 Predict whether each of the following reactions
(c) Pt / (C l 2 / С Г ) and Co/Co2+
will occur spontaneously. Consult Table 5.1
(d) Pt / ( 0 2 / H 2 0 2) and Sn / Sn2+ (a) Mg + Cu2+ — > Mg2+ + Cu
(e) Pb / Pb2+ and P l/ ( H 2 / H +) (b) 2 Ag + Zn2+ — » 2 Ag+ + Zn
In each case,
(c) 2 Fe3+ + 2 Г — > 2 Fc2+ + I2
( 1 ) write the balanced cell reaction,
(2 ) calculate the standard cell potential (d) Cl2 + H2 0 2 — » 0 2 + 2 H+ + 2 СГ
(3) indicate the anode, the cathode
(e) С Г + MnO; + H+ — > Cl2 + Mn2+ + H20
(4) indicate the direction o f electron flow, and the di­
rection o f migration o f ions through the salt bridge. (not balanced)
(f) Mn2++ Cr2 0 2' + H+ — ->
5 .18 From the half - reactions below, determine
the cell reaction and the standard cell potential. МПО4 + Cr3+ + H20 (not balanced)
F c 3 +(aq) + l e " — > Fe 2 +(aq) 8 ° = + 0 .77V (g) Mn0 2 + 4H+ + Sr — >
Mn2+ + Sr2+ + 2H20
МПО4 (aq) + 8 H+(aq) + 5c“ — >
(h) 2A13+ + 3H2 — > 2A1 + 6 H+
Mn 2 +(aq) + 4H 20 8 ° = 1.4 3 V
0 .6 6 V (i) Cr3+ + Fe2+ — > Cr2+ + Fc3+
5 .19 If the standard copper electrode had been cho­
sen as a reference electrode with a potential o f 5.24 Refer to the table of the standard reduction po­
0.00 V , what would be the standard reduction poten­ tentials to predict whether
tial of the standard (a) hydrogen electrode? (b) silver (a) Zn will displace Sn2+ in aqueous solution.
electrode? (c) aluminum electrode? (c) -2.00V (b) Pb will dissolve in 1 M HC1 solution.
inn I и........................................... O x id a tio n - Reduction Reactions 213

(c) I2 will displace Br" in aqueous solution to 5.31 Certain substances can act only as oxidizing
agents, others as reducing agents.But some substanc­
produce Br2.
es can act as both oxidizing agent and reducing
(d) H2 will displace Cu2+ in aqueous solution.
agent. Refer to the table o f the standard reduction po­
(e) Cr2C^" will oxidize Sn2+ to Sn4+ in acidic so­ tentials to indicate the situation for each o f the fol­
lution. lowing.
(a) Mg ( b )I 2 (c)C r 2 0 2-
5.25 Silver will not dissolve in 1 M HC1 but it
does dissolve in 1M H N0 3 solution producing (d) Sn2+ (e) Fe2+
Ag+ and NO
(a) Explain this difference. 5.32 Observations :
(I) A1 metal reacts with the aqueous solutions o f
(b) Write the equation representing the reaction
both M nCl 2 and N iC l2.
between Ag and H N03.
(II) N i does not react with aqueous solution o f
5.26 Predict whether a reaction will occur when M nC l2.
(a) a piece of iron wire is dipped into a CuS0 4 (III) The e°ccll for A1 - Mn cell is 0.48 V.
solution.
(IV) The e °ceU for A1 - Ni cell is 1.4 1 V.
(b) a piece of zinc metal is dipped into a
Co(N0 3) 2 solution. a) List the elements A l, N i, Mn in order o f in­
creasing oxidizing strengths.
(c) chlorine gas is bubbled through a KF solu­
b) What is the cell reaction which takes place in
tion. (Use Table 5.1)
A l - Ni cell?
5.27 Can 1M Pb(N0 3) 2 solution be safely stored c) What is the £ °cell for Mn-Ni standard cell?
in a container made of (a) iron metal? (b) copper ( c ) 0 .9 3 V
metal? (a) No (b) Yes
5.33 Observations :
5.28 What spontaneous reaction will occur in aque­ (I) Magnesium can reduce Cr3+ and Sn2+ ions.
ous solution, under standard conditions, among the (II) Sn2+ can oxidize Cr.
ions Cc4+, Ce3+, Sn4+, Sn2+ ? (Use Table 5.1). (III) The 8 °ceU for M g-Cr cell is 1.6 3 V.

5.29 Consider the following half - reactions: (IV) The 8 ° ceU for M g-Sn cell is 2.23 V.

Cr20 72"(aq) + 14H+(aq) + 6 c~— >2Cr 3 +(aq) + 7H20 (a) L ist these elements in order o f reducing
strengths.
£ ° = 1.33 V
(b) Determine £ °cell for Cr - Sn cell. 0.60 V
M n0 2 (s) + 4H+(aq) + 2e~ — > Mn2+(aq) + 2H20
5.34 Consider a galvanic cell that uses A g/A g+ and
e ° = 1.23 V
Zn/Zn2+ half - cell reactions. B y using the standard
Predict whether Cr2 0 2 ions oxidize Mn2+ to Mn0 2 half - cell potentials in Table 5.1, answer the follow ­
under standard conditions. ing questions.
(a) Draw a diagram for the cell and label the
5.30 (i) Refer to Table 5.1 to select the better oxi­
parts o f the cell.
dizing agent.
(b) Explain the operation o f the cell.
(a) Mg2+ or Al3+ (b) Sn2+ or Sn4+
(c) Find the standard cell potential.
(c) Cl2 or Br2 (d) Cr20^ or F2 (d) What should be done to increase the poten­
(II) Refer to Table 5.1 to select the better re­ tial o f the cell?
ducing agent.
(a) Cu or H2 (b) Ce3+ or Cu 5.35 A voltaic cell is set up as follow s : An alumi­
num electrode is dipped into a beaker containing a
(c) Be or Ga (d) Г or Hg
solution a f 1M A l3+. A silver elecrodc is dipped into
214 Chapter 5 И Н Ш Ш Ш Ш И И Ш ......... И Н Ш И Ш Ш П Ш П И ................... Ш И И Ш Н И Ш ............................ ..... 4
I II I I I I I I I I I I I H III

a solution o f 1 М Н+ in another beaker.A salt bridge (a) Write the overall cell reaction and calculate
is used to join the beakers. The two electrodes are the cell potential under standard conditions.
connected to a vollmeter.Use Table 5 .1. (b) Draw a diagram for this cell and indicate (i)
(a) What is the reaction occurring in the cell? the direction of electron flow (ii) anode and cathode
(b) What is its voltmeter reading? (iii) (+) positive and (-) negative electrodes.
(c) What would be the voltmeter reading if the (c) If H2S gas is passed through the solution into
[Al3+ ] were decreased to 0.01 M? which silver electrode is immersed, what kind of
( b ) 1 .6 6 V (c ) 1 .7 0 V change can be observed in the cell potential? Ex­
plain. Ksp(A g 2 S) = 5xl0 " 5 1 (a) 3.17 V
5.36 A voltaic cell is assembled by using
Cu/Cu2+ (1 M) and Cu / C u 2+ (0.1 M) electrodes. 5.38 The following two reactions have the 8 °
(a) Diagram this cell. values given :
(b) Indicate the anode and the cathode. A + B2+ — > A2+ + В 8 ° = 0.37 V
(c) Calculate its cell voltage.
2C + 3B2+ — > 2C3+ + 3B 8° = 1.26 V
(d) Suggest several ways to increase the cell
(i) If the potential for the reaction В — > B2+ + 2e~
voltage.
is +0.40 V, calculate the potential for the half reac­
(e) How can you "dead" the cell? (c) 0.03 V
tions
5.37 Given the standard reduction potentials for the (a) A — > A2+ + 2e~ (b) C3+ + 3e"— > С
cells, (ii) If the potential for the reaciton В — -> B2+ +2e"
A g+ (aq) + e~ — > A g (s) £ ° = 0.80 V is assigned a value of zero, calculate the oxidation
M g2+ (aq) + 2e* — > M g (s) 8 ° = - 2 .37 V potentials of В and С elements.
(a )0 .7 7 V (b )-1 .6 6 V

Balancing Equations

5.39 C lassify each o f the follow ing changes as an (d)MnO2' — > M n0 2 + Mno;
oxidation or reduction, and write the balanced half re­
(e) H20 2 + CH3 OH — > C 0 2 + H20
action in acid solution.
(O p h; + cr 2o 2' — > p 4 + Cr3+
(a) Fe3+ to Fe2+ (b) C l 2 to С Г (g) Ti2+ + N O3 — » N2 Hs+ + T i02+
(с) Cr3+ to Cr 2 0 2~ (d) N 0 “ to N 0 2
(h) NH* + Mn04 — > NO3' + Mn2+
5.40 C lassify each o f the following changes as an (1 ) As2 S3 + C103 — > СГ+ H2 A s0 4 + SO2'
oxidation or reduction and write a balanced half reac­
tion in basic solution. 5.42 Balance the following reactions which occur
(a) CN “ to C N C T (b) С Г to C IO "
in basic aqueous solution by using half - reaction
method.
(c) M n 0 7 to M n 0 2 (d) Zn to Zn(OH)4"
(a) Pb0 2 + СГ —> CIO' + Pb(OH) 3
5.41 Balance the follow ing reactions, which occur
(b)HP03' + BrO‘ —> Br' + PO3'
in acidic aqueous solution by using half reaction 2_
(c) H2 0 2 + Cr(OH)4 —> C1 O 4 + H20
method.
(a) 1 0 7 + S O 2" — -> I 2 + S O 2- (d)Cu(NH3 )42 ++S 2 6 2- —> S 0 32~ + Cu + NH3
(b) S 2~ + I 2 — > I” + S (e) Crl3 + Cl2 —> СЮ4 + I0 4 + Cl
Ш11Ш1ШИ11Ш111111П1Ш11Ш1ШШ111Ш11Ш111И11Ш1111ШШШШШ1Ш111И1111111Ш11Н11Ш1П111М1И111И11111Н O xidation - Reduction Reactions 215

(0 A s2S3 + N 03 + NO + S04 + H3A s0 4 (h) Mn02 + N 02 — > N 03 + Mn2+

(g)Cr07 + CN- > CNO' + Cr(OH)3 (acid solution)
(h) P4 PH3 + H2PO^
(i) Br2 + OH' — > Br' + Br03’ + H20
(1 ) CIO' c io : t- ci2 (j) N2H4 + Cu(OH)2 — > N2 + Cu
,3 -
(j) As02 + o2 AsQ
5.47 How many grams of C 0 2 will be produced
when 12.6 g of H N 03 reacts with sufficient amount
5.43 Find the oxidation numbers of the species un­
of carbon according to the skeleton equation.
derlined in these formulas.
H N 03 + С — > C 0 2 + N 0 2 + H20
(a) KCJ03 (b) Na2Pb02 (c)Bi2S3
2 .2 g
(d) Pb(N03)2 (e)NH3 (f)(NH4)2S04
5.48 Oxalate ion, C20 2’ is oxidized to C 0 2 by
2-
(g) Mn 30 4 (h) S i03 (i) IO;
2-
Mn04 which is reduced to Mn2+ in acidic solution.
,2 -
0 ) s 2O| (k) N 03" (1)MdQ (a) Write the balanced net ionic equation for this
5 .4 4 Identify the redox reactions, and indicate the reaction.
oxidized substance, reduced substance, oxidizing (b) A 50 mL of a solution of Mn04 is required to
agent, reducing agent for each redox reaction. react completely with 20.1 g of Na2C20 4. Find the
(a) 3C + 2Fe20 3 — > 3C 02 + 4Fe concentration of Mn04 solution.
(b) H2S + Cl2 — > 2HC1 + S 2
, -
(a) 5 C 2 0 J + 2 M n O '4 + 1 6 H + —>
(c) PbO + 2NaOH — > Na2Pb02 + H20
(d) 2Ba + 0 2 — > 2BaO 1 0 C O 2 + 2 M n 2+ + 8H 2 0 , ( b ) l .2 M

5.45 Complete and balance all the equations in

problems 5.41 and 5.42 by using oxidation number 5.49 When Br03 oxidizes Zn to Zn2+, the product of
method. Identify the species oxidized and the species the reduction is Br2. If a 5.0 g sample of zinc metal
reduced. is completely oxidized by 60 mL of 0.40 M sodium
bromate, NaBr03, solution, find the percentage of
5.46 Balance these equations by oxidation number
zinc metal in the sample?
method. 78%
(a) Cu + N 0 3 — > Cu2+ + NO (acid solution)

(b) C2H5OH + Mn04' — > 5.50 Suppose that H20 2 is to be oxidized by Cr20 2’
OH' + C2H30£ + M n02 + H20 in acidic solution to form 0 2 and Cr3+. How many
2- liters of 0 2 gas at STP could you get from the reac­
(c) HSnO
J2 + Cr0 4 HSnOj + Cr02
(basic solution) tion resulting from mixing a 30 mL of 0.15 M H20 2
and a 30 mL acidified solution of 0.25 M K2Cr20 7?
(d) Al + N 0 3 + OH’ + H20
0.1 L
Al(OH); + NH3

(e) Sn(OH)J + Bi(OH)3 + OH' 5.51 M n 0 4 and I" react with each other to form
Sn(OH)2' + Bi Mn2+ and I2 in acidic solution. How many moles of
(0 A s2S3 + OH' + H20 2 I2 will be formed when 100 mL of 0.2 M KMn04
and 500 mL of 0.1 M KI solutions are allowed to
A s0 4" + S 0 4' + H20
react? 0.025 mol
(g) H2S + Cr20 2" — > Cr3+ + S (acid solution)
 216 Chapter 5 iiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiii

5.52 Consider the skeleton reaction in basic solu­ 5 .5 5 Basic solutions of Na4 X e0 6 are powerful oxi­
tion. dizing agents. What mass of Mn(N0 3) 2 . 6H20 will
react with 200 mL of 0.25 M basic solution of
Bi(OH) 3 + Sn0 2 ~ —» SnO2 - + B i
Na4 Xc06 if the products include Xe and a solution of
(a) What is the balanced oxidation half-reaction ? sodium permanganate ?
(b) What is the balanced reduction half-rcaclion M n (N 0 3 ) 2 . 6H20 = 287 g/mol 22.96 g
(c) Which element is oxidized, which is reduced ?
5.56 A 20.0 mL sample of an unknown copper so­
5.53 A 30.0 mL acidified solution of 0.1 M sodi­ lution is treated with excess potassium iodide in ac­
um oxalate (Na2 C 2 0 4) is titrated with 20.0 mL of idic solution, and the liberated iodine is treated with
K2 Cr2 0 7 solution of unknown concentration. What 0.02 M solution of sodium thiosulfatc (Na2 S2 0 3). If
is the molarity of K2 Cr2 0 7 solution if the products 10 mL of the thiousulfate solution arc required for
of the reaction include Cr3+ and C 02. the completion of the reaction, what is the molar
(b) How many mL of C 0 2 gas at 0.9 atm and concentration of the unknown copper solution? The
27°C will be formed ? 0.05M, 164 mL skeleton equations are:
Cu2 +(aq) + Г —
^ Cul + I2
2-
5.54 In a typical analysis of Ca2+ in human blood I2 + S2 0 : Г + S4C>6
sample, the Ca2+ ions were precipitated as CaC2 0 4
5 .5 7 When CuS reacts with N 0 3 in acidic solu­
from a 10 cm 3 portion of this blood sample. After
tion, the following equation can be written :
the precipitate had been dissolved in H2 S 0 4, it re­
quired 1 cm3 of lxlO ' 3 M KMn0 4 solution to titrate CuS + N 0 7 -> Cu2+ + SO 4 + NO
to the end point. What is the mass of Ca2+ ions in (a) Balance the equation .
mg per cm3 of the blood. (b) An excess quantity of H N 0 3 is completely react­
CaC2 0 4 + KMn0 4 + H2 S 0 4 ^ ed with 5.76 g of CuS. How many liters of NO gas
K2 S 0 4 + MnS0 4 + CaS0 4 + C 0 2 + H20 at 1.64 atm pressure and 27°C will be formed?
(not balanced) CuS = 96 2.4 L
1 mg

Electrolysis

5.58 What is the difference between a voltaic cell 5.62 How many coulombs of electricity are required
and an electrolytic cell? to produce each of the following?
(a) 5.6 L of Cl2 at STP from aqueous NaCl solu­
5.59 How many coulombs of electricity would be tion.
required to reduce 1 mol of each of the following ca­ (b) 54 kg of Al from molten A12 0 3.
tions to the free element? (a) Fc3+ (b) Cu2+ (c) H+
(c) 22.4 mL of H2 at STP from an aqueous Na2S 0 4
solution.
5.60 What are the products of the electrolysis of the
following substances with inert electrodes? 5.63 Aluminum is obtained from bauxite,
(a) molten CaCl2 (c) aqueous Cu(N0 3) 2 A12 0 3 .x H 2 0 . How long does the electrolysis of
(b) aqueous HI (d) aqueous FeCl2 molten A12 0 3 take to produce 648 g of aluminum at
5.61 Explain why different products are obtained in the cathode at a current of 20 ampere? What volume
the electrolysis of molten MgCl2 and aqueous solu­ of 0 2 is collected at 2 atm and 127°C in the same
tion of MgCl2 . period of time? 96.5 h, 295.2 L
iiiiiiiiiiiiiiiiiiiiiiiiiiiiiiitiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiniii O xidation - Reduction Reactions 217

5.64 A current of 6 A was passed through a very di­ how often w ill a 6.5 g zinc electrode need replacing?
lute aqueous solution of sulfuric acid for 1.5 hours. ( a) 1 .9 9 V ( b) 1 0 7 .2 h

Calculate
(a) the volume of H 2 and 0 2 liberated at each 5.70 A constant current flows through two electro­
electrode at STP. lytic cells connected in series. One contains A l3+
(b) the mass of water decomposed. ions and the second Xn+ ions. 2.16g of Al were depo­
(a )3 .7 6 L of H 2 ,1 .88 L o f 0 2 (b)3.02 g sited at the cathode of the first cell and 7.68 g of
metal X at the cathode of the second cell. What is
5.65 When a current of 1.5 A is passed through a the value of "n” if the atomic weights of Al and X
solution of a trivalent metal for 30 min, 1.071 g of are 27 g/mol and 96 g/mol respectively? 3

the metal is deposited at the cathode. Calculate the

atomic weight of the metal. 1 1 4 .8 g /m o l 5.71 (a) How many Faradays o f electricity are re­
quired to produce 0.56 L of Cl2 at STP from an
5.66 A current of 2.5 A passing through an electro­ aqueous solution of KC1?
lyte solution deposites 2.77 g of metal in 30 min. (b) I f the volume o f the KC1 solution is 500 mL,
Find the equivalent mass of the metal. what w ill be the value of the pH of the solution at
5 9 .4 g the end of electrolysis? (Assume that the volume of
the solution does not change)
5.67 An electrolytic cell containing a solution of 0 .0 5 F, 13
copper (II) chloride is connected in series with anoth­
er electrolytic cell containing aqueous solution of 5.72 A steady current of 5.79 A was passed through
chloride of metal, M. After the electrolysis of these a 300 mL aqueous CuS04 solution for 500 seconds.
solutions for a while, 19.2 g of Cu and 39 g of M (a) What are the anode and cathode reactions?
are deposited at the cathode of each electrolytic cell. (b) What mass of each of the products w ill be lib­
I f the atomic weights of Cu and of M are 64 and erated?
195 g/mol respectively, (c) What w ill be the pH of the solution at the end
(a) what is the formula of the chloride of M? of electrolysis?
(b) how long must a current of 8 A be applied to (Assume the volume of the solution does not chan­
the circuit to deposite 19.2 g of Cu? ge) (b)0.96 g Cu a n d 0.24 g 0 2 ( c ) l
( a ) M C l 3 (b)2h
5.73 I f you wish to plate out a copper spoon with
5.68 The same quantity o f electricity that causes silver, would you make it anode or cathode in an
0.54 g o f aluminum to be plated out from molten electrolytic cell? Use half - reactions in your expla­
salt of aluminum also deposites 3.36 g of X from a nation. How many minutes are required to plate out
molten salt of metal X. What is the formula of the 10.8 g of silver from a solution of AgN 0 3 using a
sulfate of metal X? A l = 27 X = 112 current of 3.86 A?
XS04
4 1.7 m in .

5.69 A possible method for producing power for a

5.74 200 mL of 1 M NiS0 4 solution is electrolyzed
heart pacemaker is to implant a zinc and a platinum
electrode into the body tissues. These electrodes by the passage of .0 . 0 2 mol of electrons through the
2+
cause the formation of a "biogalvanic" cell. In the solution. What are the final concentrations of Ni ,
cell, zinc is oxidized, and oxygen in the body tissues SO42” , H+, and OH- remaining in the solution?
is reduced. [ N i 2 +]= 1 M , [ H +] = l x l 0 ~ ?M
(a) Estimate the voltage of such a pacemaker.
(b) I f a current of 50 mA is drawn from the cell
218 Chapter 5 и ................................ и ш ................ пи.................. ни... .....

Miscellaneous Problems
5 .7 5 A n aluminum rod is dipped into 1 L o f 1 M 5.78 A 15.8 g mixture of H2S and C2 H 6 gases is
A g N 0 3 solution. After a while the aluminum rod is burned in enough oxygen. After drying the products,
taken out o f the solution, dried and weighed. I f the the mole fraction of S0 2 in the mixture is found to
weight o f the aluminum rod increased 2 .16 g, what be 0.25. What volume of 0.1 M KM n0 4 solution is
w ill be the concentration o f metal ions in the solu­ necessary to react with the S0 2 in the burning prod­
tion? A l3+]=7.3 x lO '3 M, [A g +1=0.978 M ucts? S = 32, С = 12, H =1, О = 16
S0 2 + KM n0 4 + H20 — >
5.76 Four hypothetical metallic elements X , Y , Z,
MnS0 4 + K 2 S0 4 + H 2 S0 4
and T form the aqueous ions X 2+, Y 2+, Z 2+, and T2+.
0.8 L
Using the following observations, arrange the metal
o_
- ion couples into a short oxidation - reduction po­ 5.79 Cr2 0 7 (dichromate) and H2 C2 0 4 (oxalic acid -
tential series, putting the oxidation h alf reaction a weak acid) react with each other to form Cr3+ and
that has the greatest tendency to release electrons at
C 0 2 in acidic solution. Find the molarities of N 0 3,
the top. Observations :
I Y 2+ + T — > T2+ + Y Cr2 C^", K+, H+, Cr3+ ions when 200 mL of 0.1 M
II. Y 2+ + X — > no reaction K 2 Cr2 0 7, 100 mL of 0.3 M H2 C2 0 4 and 200 mL of
III. T 2+ + Z — > Z 2+ + T 2 M HN0 3 solutions are mixed and allowed to react.

5.77 Balance the follow ing oxidation - reduction [ N 0 3] = 0 . 8 M , [ K +] = 0 . 0 8 M , [ C r 2 0 72' ] = 0 . 0 2 M ,

reactions by an appropriate method. [ С r 3+]= 0 . 0 4 M , [ H +] - 0 . 6 4 M .
(a) Cu + H2S 0 4 — > C u S 0 4 + S 0 2 + H20
5.80 A 2.50 g impure sample of Na2 Cr2 0 7 is dis­
(b) Zn + N a N 0 3 + NaOH + H20 — >
solved in 1.0 M H2 S 0 4 solution when an excess
Na2Zn(OH)4 + NH3 2~
quantity of Nal is added to the solution, Cr2 0 7 is
(c) SO2’ + CrO2’ — > S 0 2' + Cr(OH)4 reduced to Cr3+ and 1“ is oxidized to I2. If the I 2
(basic solution) formed is reduced to I " by 300 mL of 0.16 M
2- 2-
(d) Cu2S + 0 2 + H20 — > C u S 0 4 + Cu(OH)2 Na2 S2 0 3 (meanwhile S2 0 3 is oxidized to S4 0 6 )
(e) Cu2S + Fe2( S 0 4)3 + H20 — + Calculate the percentage by mass of Na2 Cr2 0 7 in the
C u S 0 4 + F e S 0 4 + H2S 0 4 impure sample. Na2 Cr2 0 7 = 262g/mol. 84 %

(f) FeA sS + N 0 3 — > 5.81 A 48 g sample of an ore that is known to con­

H3A s 0 4 + NO + SO2’ + F e3+ (acidic soln) tain Cu2S was added to 300 mL of 1.2 M HN0 3 so­
lution. The following reaction took place.
(g) [Fe(CN)6]3’ + N 2FL, — >
[Fe(CN)6]4" + N 2 (basic solution)
Cu2S +HNO3 — > Cu(N0 3 )2 +H 2 S0 4 + NO +H20
(skeleton equation)
(h) СЮ 2 + H 0 2 (peroxide) — > CrO2" After the completion of the reaction, 2000 mL of
(basic solution) 0.1 N NaOH solution was required to neutralize the
(i) K M n 0 4 + NH3 — > acids in the reaction medium.
K N 0 3 + M n 0 2 + KO H + H20 (a) Balance the equation.
0) M n (N 0 3)2 + N a B i0 3 + H N 0 3 — > (b) Assuming that all the impurities in the ore
H M n 04 + B i(N 0 3)3 + N a N 0 3 +H 20 were inert to H N 0 3 and H 2 S04, determine the per­
centage by mass of Cu2S in the ore. Cu2S=160 1 0%
(k) MnS + C 10 4 — > M n 0 2 + S 0 42" + С Г
(acid in solution) 5.82 The following reactions have the £° values
(1) C 3H7CH 2OH + м п о ; —> given.
C 3H7CHO + Mn2+ (acid solution) M n2+ + 2e“ — > Mn(s) £° = 1.18V
|1м111111111111шшш1шшш11111!1ш!мшш111111ш11111ш1111111111111ш1111111111м1111111111ш11111ш11111111111м1 O xidation - Reduction Reactions 219

the following reaction takes place.

Pb2+ + 2H20 — > Pb0 2 + 4H+ + 2 e- e°= l .45V
KI(aq) + KOH(aq) + Cl2 (g)
(a) What is the spontaneous reaction uses these
two half - reactions? K I0 3 (aq) + KCl(aq) + H2 0(1)
(b) What is the standard cell potential? What volume of Cl2 at STP will be required to react
completely with KI in the solution?
5.83 If chlorine gas is bubbled through 50 mL of
0.1.M solution of KI in aqueous solution of KOH,

SELF TEST

1. In which of the following species sulfur, S, has 6.How many moles of KOH are required to react
the smallest oxidation number? with 0 . 2 mol of I2?
I2+KOH — > KI+KI03 +H20 (not balanced)
A) H2S B) S 0 2 C) SO2'

D) S20 32" v E) H2 S 0 4 A) 1 B) 0.6 C) 0.4 D) 0.2 E) 0.1

2. Which statement is true for the following bal­ Use the following data to answer the questions
anced equation?
7, 8, 9, 10, 11, 12, 13, 14, 15
Al + 3NaOH — -> Na3 A10 3 + 3/2H2
e°(Mg 2 +/Mg) = -2.37 V, £° (Со2 +/Со) = -0.28 V
A) Al is reduced e 0 (Zn2 +/Zn) = -0.76 V, e°(Ni2+/Ni) = -0.25 V
B) Al is oxidizing agent
£°(Fe2 7Fe)=-0.44 V, e°(Cu2 +/Cu) = +0.34 V
C) Na is reducing agent
D) H+ is reduced £°(Cd2 7Cd)= -0.40 V, £°(Ag+/Ag) = +0.80 V
E) Al is a better oxidizing agent than H2
7. Which is the standard cell voltage of the galvanic
3. Which is the coefficient of NO 2 when the fol­ cell constructed by the standard magnesium and sil­
lowing skeleton equation is balanced with the small­ ver electrodes?
est whole - number coefficients?
P + HNO3— > H3PO4 + N 0 2 + H20 A) 0.77 V B) 1.57 V C) 2.07 V
D) 2.87 V E) 3.17 V
A) 1 B) 2 C )3 D) 4 E) 5
8.Which of these species can oxidize Mg to Mg2+
4. Which is the coefficient of H20 when the follow­
but not Cd to Cd2+ ?
ing skeleton equation is balanced with the smallest
whole number coefficients?
A) Fe2+ В) Co2+ C) Ni2+
Zn +NOj — > Zn2+ + N20 (acid solution) D) Cu2+ E) Ag+
A) 8 B) 5 C) 4 D) 3 E) 1
9. Which would be the standard cell voltage of the
5. Which is the coefficient of OH' ions when the electrochemical cell set up by using the standard Co
following equation is balanced with the smallest and Cu electrodes if the standard reference electrode
whole number coefficients? were the standard silver electrode?
S20 32'+ MnO’ — > M n0 2 + SO2'
A) 1.14 V B) 0.62 V C) 0 J 2 V
(basic solution)
D) 0.28 V E) 0.06 V
A) 5 B) 4 C )3 D) 2 E) 1
2 2 0 Chapter 5 ШИН .... III!................... mi... .............. Ill..... ......................... ШИН...... .. ............... ............... ............................ .

10. In which of these beakers will a chemical 13. Which will be wrong for the galvanic cell
change occur? above?
A) £°ceU = 1.56 V.
B) Zn is the anode and Ag is the cathode.
Cu Ag Mg
C) Zn electrode loses mass during the operation.
D) When Na2S is added to Zn2+ compartment,
the cell voltage decreases (ZnS is negligibly soluble
A 1+ XT.2+
Ag Ni Ni in water).
I __ ✓ __ /
Fe n Co III E) When some A gN 0 3 is dissolved in Ag+ com­
partment, the cell voltage increases.

14. Which will be correct about this electrochemi­

Zn2+ M g24
— cal cell? Mg = 24 e ° ( M g / M g 2+) - 2.37 V
I ____/ к
IV (Cu/Cu ) = - 0.34 V, £ 0 (Ag/Ag+) = -0.80 V

V oltm eter
A) Only I B) Only II € ) I and III
D) IV and V E) III and V

11. Which one of the following reactions will be

spontaneous at standard conditions?

A) Zn + Mg2+ Zn2+ + Mg
B) Cu + Co2+ Cu2+ + Co
C) Fe + Zn2+ Fe2+ + Zn
D) Cd + Co2+ Cd2+ + Co
E) 2Ag + Ni2+ 2Ag+ + Ni
A) £° ceU = 2.03 V
12. Consider an electrochemical cell made up of the B) As the cell operates, magnesium loses mass
standard (Fe2+ / Fe) and (Ni2+ / Ni) electrodes. Which and silver is oxidized.
one of the following factors would decrease the cell C) The reaction occurring in the cell is
voltage of this electrochemical cell? Mg + 2Ag+ — » Mg2+ + 2Ag
I. S2' ions were added to Ni2+ compartment (Kso for D) As the cell operates the concentration of Cu2+
NiS = 3 x 10‘19). decreases.
II. Fe2+ ions were added to Fe2+ compartment. E) The passage of 1 mol of electron will decrease
III. The size of iron electrode were doubled. the mass of magnesium electrode by 2.4 g.
IV. The same amount of water were added to both
compartments. 15. Which is correct for the electrochemical cell
A) Only I B) Only IV С) I and II given below?
D) I and IV E) Only III

V oltm eter V oltm eter

 Oxidation - Reduction Reactions 221

A) The anode compartment of the cell is the half cell A) If 0.2 mol of Al is changed to Al3+, 0.3 mol
on the left side. of Mg deposites on the surface of Mg electrode.
B) e°ceU = 0.80 v . B) If the mass of Al electrode decreases 0.5 mol,
C) The addition of 0.09 mol of Ag+ to the anode the mass of magnesium electrode will increase
compartment decreases the cell voltage to zero. 0.75 mol
D) The addition of 100 mL of water to the beak­ C) The concentration of Al3+ increases as the cell
er (I) increases the cell voltage. operates.
E) As the cell operates the concentration of Ag+ D) Electrons flow from Al through the wire.
in the beaker (I) increases. E) Mg is oxidized during the operation of the
cell.
16. The value of £° for the cell using standard Ag -
18. The quantity of the electrical charge that causes
Ni electrodes is 1.05 V, the value of £° for the cell
the deposition of 3.9 g of Zn from Zn2+ also depo­
using standard Ag - Cu electrodes is 0.46V. If the
sites 2.4 g of X from a molten salt of X metal.
silver electrode is the cathode in both cells, which is
Which is the formula of the oxide of X metal?
the value of £° for the cell using the reaction
Zn = 65, X = 60
Ni + Cu2+ — > Ni2+ + Cu ?
A) X20 В) XO C) X2 0 3
A) 0.28 B) 0.34 C )0.46 D) 0.59 E) 0.80
D) X 0 2 E) X 0 3

17. Mg2+ + 2e- — > Mg £° = -2.37 V 19. Consider the electrolysis of a solution of
Al3+ + 3e- — > Al £° = -1.66 V MgCl2 with inert electrodes. Hydrogen gas and chlo­
rine gas are liberated at the electrodes. Which will be
Which will bewrong about this electrolytic cell?
the final concentration of СГ ions after 0.02 Faraday
of electricity has passed through 100 mL of 0.5 M
MgCl2 solution? (Assume no volume change)

A) 1 M B) 0.8 M C) 0.6 M
D) 0.4 M E) 0.2 M

20. How long would it take to electrodeposite all

the Cu2+ ions in 0.36 L of 0.5 M Cu(N0 3) 2 solution
with a current of 9.65 A?
A) 0.5 hour В) 1 hour C) 1.5 hours
D) 2 hours E) 3 hours
 CHAPTER

THE THIRD ROW OF

THE PERIODIC TABLE

The objectives of this chapter are to enable the student t o :

1 - Becom e a c q u ain te d w ith th e properties, uses a n d p re p a ra tio n of th e
th ird period elements.
2 - Recognize how th e general principles of chem istry w e have learned so
fa r (kinetics, bonding, acid - b ase concept, p e rio d ic ity ..............) can
be u sed to explain th e chem istry of a given element.
3 - U n d erstan d th a t elem ents in a given period have some regularities in
th e ir physical a n d chem ical p ro p erties, in th e ir perfo rm an ce as oxi­
dizing a n d reducing agent, an d in th eir acid - base behavior.
4 - P red ic t m etallic a n d nonm etallic behavior, acidity a n d basicity of th e
oxides of elem ents of a given period.
5 - Define allotropy an d am photerism .
6 - D escribe m eth o d s th a t c an b e u sed to p re p a re th e th ird p e rio d ele­
m ents.
iiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiniiiiiiiiiii The T h ird Row O f The Periodic Table 225

Having discussed the fundamental principles o f chemistry we can now con­

sider the detailed descriptive chemistry o f the other elements. We shall begin
with the third period elements o f the periodic table.
The elem ents o f the third period are Na, M g, A l, Si, P, S, Cl, Ar. A s
stated before, the properties o f the elements change gradually as w e go across
the period. N ow let us examine their physical and chemical properties, their
performance as oxidants and reductants, and the acid-base behavior o f their hy­
droxides.

6.1 PHYSICAL PROPERTIES

Na, M g, Al are metals. They reflect all the properties o f metals. They have
a silvery luster when cut freshly, are good conductors o f electricity and heat,
malleable (workable) and ductile (can be drawn into wires). Sodium is so soft
that it can be cut with a knife. Magnesium and aluminum can be bent easily.
Silicon, a semimetal (metalloid), is much harder than magnesium and alumi­
num. Phosphorus and sulfur, which are nonmetals, have yellow ish and yellow
colors. Chlorine, a nonmetal, is a diatomic gas with a greenish color. Argon is
a monatomic inert gas.

6.2 CHEMICAL PROPERTIES

The chemical properties o f elements are closely related to their electron con­
figurations. Since each element in a period has a different electron configura­
tion, the chemical properties o f elements change stepwise across a period. Now
let us look at the electron configurations o f the elements. See Table 6.1.

TABLE 6.1 Some Properties of Third Period Elements

I o n iz a tio n E n e rg ie s (k c a l/m o l) m .p . d e n s ity

E le m e n t E le c tro n c o n fig u ra tio n
I. h I3 (°C ) ( g /c m 3)
„N a Is 2 2s22p6 3s1 3pv° 3pv° 3p° 118 1091 1653 98 0.97
12M8 l s 2 2s22p6 3s23 p ° 3 p ° 3 p 7° 175 345 1838 650 1.74
13A1 Is" 2s22p6 3s23 p i 3pv° 3 p ° z 138 434 656 660 2.70

14Sl I s 2 2s22p6 3s23px 3py 3 p °z 188 376 772 1410 2.33

15P 1 s2 2s22p6 3s23px 3py 3pz 242 454 696 44 1.82
16S Is 2 2s22p6 3s23p2 3Py 3 p i 239 537 803 113 2.07
n Cl 1s2 2s22p6 3s23p2 3p2 3p'z 300 549 920 - -101 1.5 (-34°C)
<

Is 2 2s22p6 3s23p2 3p2 3p2 363 636 943 -189 1.4 (-189°C)
ОС
226 Chapter 6 Ш П И Ш Ш Ш И Ш И Ш Ш И П Ш Ш Ш Ш Ш П Ш П И Ш Ш Н Ш Ш Ш Ш Ш И Ш И И Ш Ш Ш Ш Н И И П Ш I Ш Ш Ш Ш Н Ш Ш П II .

6 .2 .1 METALLIC SOLIDS
(SODIUM, MAGNESIUM, AND ALUMINUM )

The elements have low ionization energies and a number o f vacant valence
orbitals, In other words, the outer electrons in the atom are not strongly attract­
ed to the nucleus o f the atom. Therefore these electrons in the solid are not lo ­
calized, but are free to move throughout the crystal. The electrostatic attraction
force between the mobile electrons and the atomic kernels causes all the atoms
to connect to each other. Such type o f bonding is called m etallic bonding.
See Figure 6.1. So sodium, magnesium and aluminum are metallic solids. The
nonlocalized electrons are responsible for metallic luster (reflectivity ofligh t),
high electrical and heat conductivity, and workability. As the ionization energy
o f these elements increases, the metallic bond becomes stronger. Then the melt­
ing point and boiling points o f the metals increase.

F I G U R E 6.1 [yietallic Bonds in Sodium, Magnesium, and Aluminum.The number of electrons contributed
to the metallic bond increases from one per sodium atom, to two for each magnesium atom, to three for
each aluminum atom. Thus the strength of the metallic bond increases from sodium to magnesium to alumi­
num.

6.2.2 A NETWORK SOLID (SILICON)

For silicon having four valence electrons, it is questionable if the atom
would find it energetically favorable to lose or gain electrons. Silicon shares
electrons and forms covalent compounds. Therefore it cannot be classified as a
pure metal. It reflects some properties o f metals (such as metallic luster, electri­
cal conductivity) and some properties o f nonmetals (hardness). Consequently
silicon is a sem im etal or m etalloid .
 11Ш
Ш1Ш
11111111|1Ш
11Ш
1111Ш
11111111Ш
1111М1!11111М1Ш
111!111Ш
111!1Ш
11МШ
1ШШ
111Ш
1ШШ 11111ш7716 T hird Row O f The Periodic Table 227
!11Ш

The packing o f atoms in the silicon crystal depends to a large extent on the
directional characteristics o f the bonding sp3 hybrid orbitals. Experimental data
'Ф show that each silicon atom in a silicon crystal is surrounded by four other sili­
con atoms, which form a tetrahedral shape. See Figure 6.2. Since each o f these
'f f -ф silicon atoms in turn is tetrahedrally bonded to four silicon atoms the result is
an interlocked structure extending in three dimensions. In such a crystal each
silicon atom shares one electron with each o f four other silicon atoms, thus fill­
V ing all available sp3 hybrid orbitals, and providing a stable outer octect electrons
for each atom. Such solids are called netw ork solids in which atoms are
Silicon
joined by covalent bonds. Therefore the network solids are hard and poor con­
ductors o f electricity.
Si-Si distance=2.35 A°

F I G U R E 6 . 2 The crystal 6 .2 .3 MOLECULAR SOLIDS

structure o f silicon (PHOSPHORUS, SULFUR AND CHLORINE)

The electron configurations and ionization energies o f these elements are

shown below.

Element Group No Ionization energy (kcal/mol)

151 ls 2 2s2 2p6 3s2 3p3 VA 254

16- ls 2 2s2 2p6 3s2 3p4 VIA 240

Cl ls 2 2s2 2p6 3s2 3p5 VILA 301
17

Since they have no vacant orbitals and high ionization energies, they have no
mobile electrons. Therefore these elements do not conduct electricity and heat.
These are completely nonmctals. Phosphorus forms discrete P 4 molecules. See
Figure 6.3. The P 4 molecules pack together to form a molecular solid. There
are no strong bonds among P 4 m olecules as happened in network solids. In­
stead weak van der Waals forces hold the P 4 m olecules together in the solid.
Therefore it has very low melting point (44 °C ) compared to that o f silicon
(1410 °C ). Phosphorus element exists in two forms in nature (1) white phos­
phorus (2) red phosphorus. These two forms differ in their crystal structure and
FIG U R E 6.3 Struc­
tures o f White and Red physical properties. Such different forms o f an element are called allotropes
Phosphorus, (a) White o f that element. Graphite and diamond are allotropes o f carbon, and oxygen gas
phosphorus consists o f ( 0 2) and ozone ( 0 3) are allotropes o f oxygen.
tetrahedral P4 molecules,
(b) Red phosphorus also
has a pyramidal arrange­
m ent o f three bonds
around each phosphorus
atom, but the atoms are
connected to form a cor­
rugated sheet o f atoms P:
that extend indefinitely in
two dimensions.

(b)
И
 228 Chapter 6 |||||Ш |М |М Ш 1 |1 1 Ш Ш 1 1 П |||||1 1 1 1 1 1 1 1 1 1 1 1 1 1 М 1 1 Ш 1 Ш Ш |М ||||||М 1 Ш 1 Ш Ш Ж П ||1 М 1 ||||||Ш Ш ||Ш Ш 1 Ш 1 Ш |||||Ш Ш 1 ||Ш Ш П 1 Ш Ш 1 Ш ||М ||Ш Ш Ш Ш Ш Ш 1 П Ш |||||||

Ordinary sulfur has a puckered-ring structure which contains eight atoms per
molecule, S 8. This molecule is shown in Figure 6.4. The van der Waals Forces
operate to hold the molecules in the solid. Therefore S g has low melting point
(119 °C).
Chlorine being a halogen exists in nature in a state o f diatomic m olecules,
Cl2. It is a gaseous substance at STP.
F I G U R E 6 . 4 P u cke re d - Argon is a noble gas. Since it does not combine with any other element it is a
ring structure o f S8 molecule. monatomic gas.

EXAMPLE 6.1 C om p arin g M etallic P rop erties o f M etals

P roblem : Compare the metallic properties and melting points of the elements 19 X, 2 0 Y, 3 2 Z, 3 3 R.

S o lu tio n : 1 9 X: [Ar] 4 s 1 2 0 Y :[A r ]4 s 2

3 2 Z: [Ar] 4s 2 3d 10 4p 2 3 3 R: [Ar] 4s 2 3d 10 4p 3

As we can deduce from their electron configurations, X and Y are completely metals because they have
one and two valence electrons respectively. Metallic properties are the properties arising from the ease o f
releasing electrons (low ionization energy). Therefore we expect X to be a stronger metal than Y. Z has
four valence electrons. It is a semimetal or a metalloid. R has five valence electrons it is a nonmetal.
As to their melting points , for metals as the number o f valence electrons increases, the metallic bond be­
comes stronger, therefore melting point o f the metals increases. So we expect
m.pz > m.py > m.px
Since R is a nonmelal we expect its melting point to be lower than that of Z.

EXERCISE 6.1 Comp arc the melting points of ihc solids NaCl and CaCl2. Give your reasons.

6.3 THE ELEMENTS AS OXIDIZING AND

REDUCING AGENTS

The first three members, Na, Mg, Al have low ionization energies, and have
great tendency to release electrons. Therefore these elements are very powerful
reducing agents. Because o f their high chemical reactivity they cannot exist
freely in nature but only as positively charged ions in the compounds.
The last member argon has no tendency to gain or lose electrons, therefore it
is neither an oxidizing nor a reducing agent. On the other hand, clilorine, CI2 ,
has quite high ionization energy and has tendency to gain electrons, therefore it
is a very strong oxidizing agent and a reducing agent in intermediate strength.
The oxidation potentials o f Na, Mg, and Al elements are 2.71 V, 2.37 V,
and 1.66 V respectively. As mentioned before the oxidation potential measures
the tendency o f a species, compared to that o f hydrogen, to act as a reducing
agent. For these metals namely sodium, magnesium and aluminum the oxida­
tion potentials are very high. So we say that these elements are all excellent re-
1шшш1шпшш11ш1мшш11111ш111шшшш1шш111ш1шш1шшшшш1шш11щ|м1шш11ш111 The T hird Row O f The Periodic Table 229

ducing agents and sodium is the best one.

Examine the following examples to learn the reducing effects o f these ele­
ments.

2M g (s) + C 0 2 (g) -> 2MgO (s) + С (s)

2A1 (s) + Fe 2 0 3 (s) -» 2A12 0 3 (s) + 2Fe (s)
6 Na (s) + A12 0 3 (s) -> 2A1 (s) + 3Na20 (s)

The ionization energy o f silicon is very high. It has a very stable crystal
structure. Therefore its tendency to release electrons is extremely weak. But it
may reduce oxygen,
Si (s) + 0 2 (g) -> Si 0 2 (s)
Phosphorus and sulfur can act as reducing agents against strong oxidizing
agents only such as oxygen and halogens. Even white phosphorus gives a vio ­
lent reaction with oxygen spontaneously. Therefore it is kept in water.
P4 (s) + 5 0 2 (g) —> P4 0 io(s)
P 4 (s) + 6 Cl2 (g) -> 4PCl3 (g)

Phosphorus also reacts with strong reducing agents and produce phos­
phides.
P4 (s) + 6 H 2 (g) —> 4 PH 3 (g)
P4 (s) + 6 M g (s) —» 2M g 3 P 2 (s)
P 4 (s) + 12Na (s) —>4Na3P (s)
P4 (s) + 4A1 (s) -> 4A1P (s)

Sulfur, like phosphorus,may act as oxidizing or reducing agent in chemical

reactions.
8 Zn (s) + Ss (s) —> 8 ZnS (s)
16A g(s) + S s ( s ) -> 8 A g 2 S(s)
S 8 (s) + 8 0 2 (g) -> 8 S 0 2 (g) (sulfur acts as reductant)

Chlorine has a very high ionization energy. It is not expected to release elec­
trons. Instead it has a tendency to gain electrons to form stable (1-) charged
ion. It is a powerful oxidizing agent,
KI (aq) + l/2C l 2 (g) KC1 (aq) + 1/2I2 (s)

However, in some compounds which have oxygen, chlorine may have the
oxidation states o f + l,+ 3 ,+5,+7.
Argon, being an inert gas has no tendency to gain or to lose electrons. It is
neither an oxidizing nor a reducing agent.
230 Chapter 6 ш ж ж ж ж ж м ж ж ж ж ж ж ж ж ш и и ж ж ж ж ж ж ж ш м ж ш ж ж ж ш и ж ж м ж ж ж ж ж ж ж ж ж м ж ж м ш ж ш и и ж ж ж ж ж м ж м ж ж ж ж ш ш

EXAMPLE 6 .2 . R edu cin g S tren gth of S 0 2

Problem : Water saturated with S 0 2 is a quite useful reducing agent. Decide if Fe3+ might be reduced
to Fe2+ by S 0 2 .
S olution: To answer the question, let us compare their reduction potentials
Fe3+ (aq) + le' -> Fe2+ (aq) E° = -0.77 V
S0 2 _ (aq) + 4H+ (aq) + 2e“ -> S 0 2 + 2H20 e° = +0.17 V
The spontaneous reaction between these species is
SO 24 (aq) + 4H+(aq) + 2Fe2+ (aq) -> S 0 2+ 2HzO + 2Fe3+ E° = 0.94 V
The reverse of this spontaneous reaction (reduction of Fe3+ to Fe2+ by S 0 2) is nonspontaneous. Therefore we
may deduce that S 0 2 cannot reduce Fe',+ to Fe2+.

EXERCISE 6.2. Chlorine is commonly used as germicide in swimming pools. When chlorine dissolves
in water it produces hypochlorous acid and hydrochloric acid.
(a) Write equation representing the dissolution of СЦ in water
(b) Which will propably affect as germicide Cl or CIO ? Explain ClO~

6.4 THE ACIDIC AND BASIC PROPERTIES

OF OXIDES AND HYDROXIDES
6.4.1 OXIDES
Because o f the high electronegativity o f oxygen, most metals react with oxy­
gen to form ionic oxides such as N a ^ , MgO, A12 0 3. Many o f these metal ox­
ides react with water to form bases. Such oxides are called b asic a n h y ­
d r id e s .
Na20 (s) + H20 —> 2Na+ (aq) + 2 0 H - (aq)
BaO (s) + H20 -» Ba2+ (aq) + 2 0 H ~ (aq)
There are a number o f metal oxides that are insoluble in water, but dissolve
in acid solutions. For example
MgO(s) + 2H+(aq) —>Mg 2 +(aq) + H20
These oxides are also considered to be basic, for they react with a known
acid.
Some ionic metal oxides are am photeric. A12 0 3, ZnO are common exam ­
ples o f am photeric oxides. They react with both acids (metal oxide behaves
like a base) and bases (metal oxide behaves like an acid)
Al2 0 3 (s) + 6 H+(aq) -> 2A13+ (aq) + 3H20
A12 0 3 (s) + 20H " + 3H20 -> 2Al(OH)“ (aq)

Reactions o f nonmetals with oxygen produce covalent nonmetallic oxides

such as S 0 2, P 4 O 1 0 . These molecular oxides o f nonmetals generally produce
acid when reacted with water so the nonmetal oxides are acid anhydrides.
S 0 2 + H20 —> H 2 S 0 3 (Sulfurous acid)
P4 O 10 + 6H20 —> 4 H 3 PO 4 (Phosphoric acid)
 1||и|11[|т1ш1шш11ш11л1шш1ши11111ш 1111ш11п111ш1нк«ш1штшшшш11111111ш11м11(шшгт'л.е Third, Row O f The Periodic Table 231

Since the metallic properties decrease from left to right across a period, the
oxides o f elements on the left have basic character and those on the right acidic
character. See Table 6.2.

TABLE 6.2 A cidic and B a s ic A m p h oteric Oxides with no

A cid ic O xides
basic properties o f oxides O x id es O x id es acidic or basic
o f Periods 2 and 3. On properties
the left o f the periodic
Li20 BeO b 2o 3 co2 N 20 3
table the oxides are bas­ o 2 f 2o
ic. On the right they are
n 2o 5
acidic (except 0 2 and
F20). Na20 MgO A12 0 3 S i0 2 P 2 0 3 502 C120

p 2o 5 503 C12 0 3

6.4.2 H Y D R O X ID E S
Let MOH represent a hydroxide o f a third period element. If the atom M has
low ionization energy (low electronegativity) the M - 0 bond is polar with the
oxygen having a negative charge and M a positive charge
+ 5 - s
M -O -H

+ _
When this is the case, MOH dissociates to give M and OH , apparently the
hydroxide o f such an element will be a base as in NaOH and Mg(OH ) 2

MOH -* M+ +O H “

When M has high ionization energy (high electronegativity) the M - 0 bond

becomes less polar but the О - H bond becomes more polar.
- 5 +8

M -O -H

Hence there is an increasing tendency for the M -O -H to be ionized as MO~

and H+. Thus acid strength increases with increasing the electronegativity o f M,
and base strength decreases.
So we can say that the hydroxides o f the elements that have high electroneg­
ativity have acidic character.
Sodium has very low ionization energy. Therefore NaOH dissolves in wa­
ter, and dissociates into Na+ and OH- ions 100 %. So NaOH is a very strong
base.
NaOH (s) -> Na+ (aq) + OH~ (aq)

M agnesium also has low ionization energy. So Mg(OH ) 2 is a strong base.

232 Chapter 6 HI ' ...................... HHHHIHIIH....... НИИ................ ........ I....................................... н и ................................................

But it has very low solubility in water.

Mg(OH ) 2 (s) -> Mg2+ (aq) + 20H " (aq) Ksp= 9 x l0 ' 12

But it neutralizes acids according to the equation.

\

Mg(OH ) 2 (s) + 2H+ (aq) -> Mg2+ (aq) + 2H20

Aluminum hydroxide, Al(O H )3, has both acidic and basic properties. It is
rather insoluble in water.

Al(OH ) 3 (s) -> Al3+ (aq) + ЗОН" (aq) Ksp= 5x10 ‘ 33

But it dissolves in either strong acids or strong bases:

Al(OH ) 3 (s) + 3H+ (aq) -» Al 3 +(aq) + 3H 2 0(1)

Al(OH ) 3 (s) + OH" (aq) Al(OH)" (aq)

Such substances that react with acids and bases are said to be am photeric.
Aquesous solutions o f Al3+ are acidic because o f the hydrolysis o f Al3+ ion.
It is hydrated because o f its small size and high charge.

Al3+ + 6H20 - » [A1(H2 0 )5 OH]2+ + H+

Si(OH ) 4 or S i0 2 has weak acidic properties. S i0 2 is insoluble in water but

react with strong bases to form soluble salts:

S i0 2 (s) + 2NaOH -» 2Na+ (aq) + S i0 3 "(aq)

When phosphorus is burned, it forms the oxide o f P 4 0 6 which is the anhy-

ride o f the phosphorus acid, H 3 P 0 3. But phosphorus may have the oxidation
states o f +1, +3, +5 in its acid compounds. Examine the following acids.
H
I
H 3 P 0 9 (The oxidation number o f P is (+1) HO - P = О
hypophosporus acid.) '
H
H
I
H 3 P 0 3 (The oxidation number o f P is (+3) HO - P = О
Phosphorus acid.) ^

OH
I
H 3 P 0 4 (The oxidation number o f P is (+5) HO - P = 0
Phosphoric acid.). I
OH
iiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiHiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiHiiiiiiiiiiiiiiiiiiiiiiiiiiiiiii СРДв Third Row O f The Periodic Table 233

The strengths o f acids may be deduced from their dissociation constants.

-2
H3 p ° 2 ►H+ (aq) + H 2 PO -(aq) K j = 1.0x10
H3PO3 - H + (aq) + H 2 P O - (aq) K ,= 1.6 x 1 0 '
-3
H 3 PO 4 • H + (aq) + H 2 PO“ (aq) K ,= 7.5 xlO

The oxides o f sulfur (S 0 2, S 0 3) are also acid anhyrides. Their reactions with
water produce H2 S 0 3 (sulfurous acid), and H 2 S 0 4 (sulfuric acid). H 2 S 0 4 is a
strong acid whereas H 2 S 0 3 is a weak one.

H2so4 H+(aq) + H S 0 4 (aq) K ,= very large

H S04 H+(aq) + SO 2_ (aq) K2= 1.2 x 10 ' 2
H,SCL H+(aq)+ HSO 3” (aq) Kj= 1.3 x 10 ' 2
h so ; H+(aq) + S 0 32" (aq) K2= 5.6 x 10 ' 8

Chlorine exists in the structures o f many acids where it has the oxidation
states o f +1, +3, +5, +7 in the following acids respectively. HC10 (hypochlor-
ous acid), HC10 2 (chlorous acid), HC10 3 (chloric acid), HC10 4 (perchloric
acid).
As the oxidation number o f the chlorine atom in the acid molecule increases
the strength o f the acid increases too. So НСЮ is the weakest and HC10 4 is the
strongest acid.
A comparison can be given for the hydroxides o f third period elements in
Table 6.3.

T A B L E 6.3 H y d r o x id e s o f Third P erio d E lem en ts

IA 11A IIIA IVA VA V IA V IIA

0
NaOH Mg(OH ) 2 Al(OH ) 3 Si(OH ) 4 0 = P (0 H ) ) 3 0 = S (0 H ) ) 2
0=C1 - OH
II
0
0

S tro n g b a se W ea k base A m photeric W eak acid W ea k acid S trong acid S tro n g acid

6.5 OCCURRENCE, PREPARATION AND

USAGE
Sodium is a very reactive element therefore it cannot exist freely in nature,
but occurs as (+1) ions in its compounds. Sodium is the sixth abundant e le ­
ment. It mainly exist in salt rocks as NaCl. It is prepared by electrolysis o f m ol­
ten NaCl or NaOH. It is used in nuclear power plants to conduct heat energy
from the center o f a nuclear reactor to exterior where it can be changed into use­
ful work.
 234 Chapter 6 шшшшшшшшшншншшшшишшшшшшшмшшшнншшиишпшпшшшшшшншшишшиишшшшиишшшшшшшшшшннш

M agnesium also found only in compounds as (+2) ions. It is the eighth

m ost abundant elem ent in the earth's crust. Its com m on m inerals are
CaMg 3 Si 4 0 1 2 (asbestos), M gC 0 3 (magnesite) and M gC 03. C aC 0 3 (dolomite).
Magnesium also exists in seawater. Magnesium is generally prepared by the ex­
traction o f magnesium from seawater. In the process, the M g2+ in seawater is
precipitated as Mg(OH ) 2 by the addition o f lime water, Ca(OH)2. The precipitate
is filtered o ff and converted to MgCl 2 by adding HC1. The molten M gCl 2 is
electrolyzed to obtain pure magnesium.

MgCl2 (s) -> M g(s) + Cl 2 (g)

Alum inum is the third most abundant element (the most abundant metal) in
the earth's crust. It occurs only in compounds as (+3) ions. Its common miner­
als, are A12 0 3 .xH 20 (bauxite), K A lSi 3 O g (feldspar) and N a 3 AlF 6 (cryolite).
CQ, (g)• Aluminum is prepared from purified bauxite. Bauxite, dissolved in a molten
mixture o f fluorides such as cryolite and calcium fluoride, is electrolyzed. See
Figure 6.5. Because aluminum alloys have very low densities they find many
uses in aircraft, space vehicles. Pure aluminum is also used as wrapping materi­
als, and high-voltage transmission lines.
Silicon, the second most abundant element in the earth's crust, does not
occur freely in nature. It is found in nature as S i 0 2, it accounts for sand, flint,
quartz, and opal. Silicon is usually prepared by reduction o f silica (silicon diox­
FIGURE 6 .5 Electro­ ide) from sand with coke, at high temperature.
lytic cell for the production
of aluminum by the Hall
Process. A crossection S i0 2 + 2C —^ Si + 2CO
through the cell is shown.
The carbon anodes are This rather crude silicone is converted to SiC l 4 (silicone tetrachloride).SiCl4,
oxidized to C02(g) and as
being a volatile substance, is distilled carefully to remove impurities. The pure
they are consumed they
are lowered further into SiCl 4 is reduced with an active metal such as Na or Mg.
the molten mixture of
Al20 3 and Na^lFg. Alumi­ SiC l 4 + 4Na 4NaCl + Si
num ions are reduced to
aluminum at the carbon
The ultrapure silicon is used in the electronics industry for the manufacture
cathode. Aluminum is a
very reactive metal. But o f transistors and solar cells.
the aluminum oxide formed P h osp h oru s is the twelfth most abundant elem ent in nature and occurs
at the surface of the metal most frequently in the form o f phosphates like Ca 3 (P 0 4) 2. It may be prepared
is very though and almost
invisible. This coating film by reduction o f Ca 3 (P 0 4) 2 with silica and coke at high temperatures.
protects the metal under­
neath from further oxida­ 2C a,(P0 4) 2 + 6Si0 7 + IOC -> 6 C a S i0 3 + 10CO + P 4
tion.
Like nitrogen, phosphorus is an essential constituent o f living cells. Bones
contain about 60 % Ca 3 (P 0 4)2. Since phosphorus is an essential nutrient, and
 ниш \\\The T hird Row O f The Periodic Table 235

since nature's phosphorus cycle is very slow, soluble phosphate compounds

(superphosphates) are used as fertilizers. Red phosphorus is used in smoke
bombs, fireworks and matches.
S u lfu r, although not very abundant, occurs in large beds o f free element
and as a variety o f sulfide and sulfate minerals, such as ZnS (zinc blend),
CuFeS 2 (chalcopyrite), C a S 0 4 .2 H 20 (gypsum). Most o f the sulfur is used in
the production o f H 2 S 0 4. Sulfur is also a component o f gunpowder and is used
vulcanization o f rubber. Plants cannot grow in sulfur defficient soil. Therefore
such soil must be fertilized with one of the sulfur containing water soluble com ­
pounds such as ammonium sulfate [(NH 4) 2 S 0 4], potassium sulfate (K 2 S 0 4).
C hlorine, the most abundant halogen, is not found in the free state, but in
the form o f compounds. Naturally occurring minerals o f Cl2 are chlorides o f al-
kalie and alkaline earth metals. It is prepared by the electrolysis o f aqueous
NaCl solution. It is used for making plastics (PVC), insecticides, dry cleaning
agents and bleaching materials.
A rgon, an inert gas, is found freely in the atmosphere, 1 % o f atmosphere
is argon. It may be isolated by fractional distillation o f liquefied air. Since it is
chemically inert, it is used to produce an inert atmosphere for metallurgical op­
erations such as welding. It is also used for filling incandescent light bulbs.
236 Chapter 6 шшшшишнн ни шшнии гашиш мшгашшш................... шшшшшпшшшшшшш

SOME NEW TERMS

Acid anhydride: the oxide o f nonmetal that oms or ions in which each atom or ion is bound
reacts with water to form an acid. S 0 2, N 0 2 are strongly to its neighbors and the regular net­
acid anhydrides. work extends indefinitely throughout the crystal.
Allotropy: different forms o f the same ele­ Metallic bonding: Type o f bond that holds
ment in the same physical state. Such as graphite atoms together in the metal. It is the force o f at­
and diamond or white and red phosphorus. traction between mobile electron clouds and pos­
Basic anhydride: the oxide o f a metal that itively charged atomic kernels.
reacts with water to form a base. Na 2 0 , CaO are Metalloid: An element which exhibits both
basic anhydrides. metallic and nonmetallic properties.
Network solid: A continuous network o f at­

REVIEW QUESTIONS AND PROBLEMS

6.1 List several characteristics that distinguish met­ 6.9 Write balanced equations for the following reac­
als from nonmetals. tions
(a) Sulfur dioxide with water
6.2 What is a metalloid? (b) Sulfur trioxide with water.
(c) Tetraphosphorus dccoxidc with water.
6.3 Arrange the elements Na, K, Al, Si in order of (d) Sodium oxide with water.
increasing melting points. Give your reasons.
6.10 What is amphoterism? Explain.
6.4 Arrange the individual bonds in NaCl MgCl2,
А1СЦ in order of increasing ionic character. 6.11 Which oxide would you describe as being
more basic A12 0 3 or S i0 2 or S 0 2?
6.5 What is allotropy? Give examples.
6.12 What will be the molarity of 500 mL of phos­
6 .6 .How do the following properties change from phoric acid solution produced by the action of 14.2 g
left to right across the third period? of P4 O 10 ? Assume complete reaction. 0.4 M
(a) Atomic number
(b) Atomic size 6.13 Write the balanced equations for the reactions
(c) Ionization energy of the following oxides with water.
(d) Acidities of oxides (a) C 0 2 (b) P2 0 5 (c) CaO D) C12 0 ?
(e) Reducing property
(0 Base strength o f hydroxides. 6.14 Why is rainwater generally slightly acidic even
in air that is not polluted with oxides of nitrogen and
6.7 Write equations describing; sulfur?
(a) reducing property of Na,
(b) reducing property of Al 6.15 Explain the increase in acid strength in the
(c) oxidizing property of Cl2, following series •
(d) amphoteric property of Al. Si(OH) 4 OP(OH) 3 0 2 S(0H ) 2 0 3C10H

6.8 Classify the following oxides as acid anhydride 6.16 How do the acid strengths change in the fol­
and basic anhydride; Na2 0 , MgO, P2 0 5, S 0 2 . Ex­ lowing acids? H2S 0 3, H2S04. Explain.
plain why they are called acidic and basic anhydrides.
 шшппнншшшшппшшмпшшшшшшшшшшТ'Де Third Row O f The Periodic Table 237

2-
6.17 Why can aluminum not be prepared by the 6.20 (a) Does S2 0 3 act as oxidizing or reducing
electrolysis of aqueous solution of A1C13 ? agent in the following reaction.

CIO- + S2 0 3 —> S 0 4 + Cl (basic)

6.18 Give reactions illustrating the
(a) preparation of Mg from sea water. (b) What are the final concentrations of K+ , C F ,
2- _
(b) preparation of Si from silica. S 0 4 and OH in a solution made by mixing 10 mL
of 0.1 M K2 S2 0 3 and 20 mL of 0.2 M KOH and 30
6.19 A 0.4 A current is applied to molten sodium
О mL of0.30M K C IO ?
chloride. The chlorine gas collected at 27 С and
(b) [K +] = 0 . 2 5 M , [Cl~] = 0 . 0 6 7 M ,
1.64 atm occupies a volume of 1.5 liters.How many
[ S 0 2f l = 0 . 0 3 3 M , [ O H ] = 0 .0 3 3 M
grams of sodium chloride must have been electro­
lyzed ? How long did this electrolysis take ?
11.7 g, 1 3 .4 hr

SELF TEST

1. Some elements show the metallic and nonmetal­ 6.The element X can form the compounds X2 0 3
lic properties. Such elements are called and X2 Os with oxygen. The compounds of X with Y
A) transition elements B) heavy metals which has the atomic number of 17 are
C) allotropes D) amphoters E) metalloids A) X2 Y3 and X 2Y5 B)XY 3 andXY 5
C) X3Y and X5Y D) X3 Y2 and X5 Y2
2 .Which is the atomic number of the fifth element E) XY and XY2
of the third period ?
A) 11 B) 12 C) 14' D) 15 E) 17 7. Which will be wrong when the acid strengths
arc compared ?
3. Sulfur element can exist in different physical A) H2 S 0 4 > H2 S 0 3 B) H N0 3 > H N0 2
forms such as S2, S6, S8. The existence of an ele­ C) H3P 0 4 > H3 P 0 3 D) HC103 > HC102
ment in such different forms is known as E)H 2 S 0 4 > h 3p o 4
A) allotropy B) isomerism C) isotopic
D) isotopic forms E) amphoterism 8.Given the reactions ?
I. P4 + 10C12 -> 4PC15
4. Which is the strongest reducing agent ? II. P4 + 6 H2 4PH 3
A) n Na B ) 12Mg C ) 1 3 A1 III. P4 +12Na -> 4Na3P
D) 14Si E) 15P Phosphorus can act as both reducing and oxidizing
agents. In which one(s) of these reactions it acts as
5. X, Y and Z are the third period elements; oxidizing agent ?
I. Z is a better reducing agent than X A) I, II В) II, III С) III alone
II. The basic character of the oxide of X is strong­ D) I, III e) I alone
er than that of Y. Which one of the following repre­
sents the order of increasing atomic numbers of these
elements ?
A) X,Y,Z B) Z,X,Y C) Z,Y,X
D) Y,Z,X E) X,Z,Y
238 Chapter 6 1 Ш Ш 1 1 ИШ Ш Ш Ш Ш Ш Ш Ш Ш 1 Ш 1 Ш 1 1 1 1 Ш 1 1 1 1 1 1 1 1 1 Ш 1 1 1 1 1 1 1 1 1 1 1 Ш 1 1 Ш Ш Ш Ш 1 1 М1 1 Ш 1 Ш Ш Ш иШ Ш 1 Ш 1 ШШ ИШ 1 ШШП 1 !Ш 1 1 1 1 1 1 1 1 1 1 1 Ш 1 1 1 Ш Ш 1 1 ШПШ 1 1 Ш Ж 1 Ш

9. Gonsider the elements given in the table. X Y Z

A) Mg Al Fe
B) Mg Cu Al
C) Cu Mg Al
X R // Y T D) Fe Mg Cu
z // E) Al Cu Mg
-/ /-
14. To prove that M(OH) 2 is an amphothcric hy­
droxide, which ones of the following trials may be
used?
Which is wrong about these elements ? I. Its aqueous solution turns litmus red.
A) T is a stronger oxidizing agent than R. II. Its aqueous solution turns litmus blue.
B) YmOn is probably an acid anhydride. III. It reacts with 5 M HC1 solution.
C) ZOH is a stronger base than XOH. IV. It reacts with 5 M NaOH solution.
D) The melting point of R is higher A) I and II В) I and III С) III and IV
than that of X. D) II and III e) I and IV
E) R is a more reactive metal than X.
15. The production of aluminum metal from baux­
10. When powdered aluminum is mixed with iron ite ore by electrolysis is the cornerstone of the alu­
(III) oxide and ignited a reaction occurs with large minum industry. Which one of the following is the
amount of energy release? If the products of the reac­ time needed for a current of 9.65 A to deposite 54 g
tion are aluminum oxide and metallic iron (thermite of metallic aluminum ? Al= 27 g/mol
reaction), how many kcal of energy will be released A) 2 x 103 sec B) 4 x 104 sec C) 6 x 104 sec
during the production of 1 mol of iron? D) 5 x 105 sec D) 8 x 10s sec
(Al20 3)=-400 kcal/mol
(Fe20 3)=-200 kcal/mol 16. Consider the elements of third period nX, 12 Y,
A) -100 B) -200 C) -300 13z
D) -400 E) -600 I. 2X (s) + Y2+ (aq) -> 2X1+ (aq) + Y(s)
II. 2Z (s) + 3Y2+ (aq) 2Z3 +(aq) + 3Y (s)
11. Which will be the formula and molecular shape II. 3X (s) + Z3+ (aq) -> 3X1+ + Z(s)
of hydride of phosphorus The nonspontaneous reactions are;
A) I В) И С) III D) II and III E) I and II
A) PH4,tetrahedral B) PH2, linear
C) PH3, triangular D) PH3, pyramidal 17. A typical seawater contains 0.3 % M gS0 4 and
E) PH2, triangular 0.4 % MgCl2 by mass. How many kg of magne­
sium metal can be obtained from 1 ton of seawater ?
12. Which is the pH of 4 liters of solution that is MgS04= 120, MgCl2= 95
prepared by dissolving 1.24 g of sodium oxide in A) 0.7 B) 1.2 C) 1.6 D) 2.1 E) 2.7
enough water ? Na=23,0 = 16
A) 2 B) 4 C) 7 D) 9 E) 12 18. Sulfur, S8, is converted into H2 S 0 4 through a
series of reactions. How many kg of S8 are required
13. Given the data about the metals, X,Y,Z: to prepare one liter of H2 S 0 4 solution that has a den­
I. X reacts with HCl(aq) and produce H2 gas. sity of 1.84 g/mL and is 98 % H2 S 0 4 by mass ? As­
II. Z metal reacts with both HC1 (aq) and NaOH (aq) sume the yield of the reaction is 98 %.
III. Y reacts with neither HC1 (aq) nor NaOH (aq) H =l, S=32, 0 = 16
Which may be the metals X,Y and Z A) 0.6 B) 0.9 C) 1.2 D) 1.6 E) 2.0
iiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiuiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiii The T hird Row O f The Periodic Table 239

19. How many mL of 0.25 M NaOH solution are (2000 °C) according to the equation.
required to neutralize a 500 mL solution in which 2Al2 0 3 (s)^ 4 A 1 0 (g ) + 0 2 (g)
2.84 g P4 O 10 dissolved ? P4 O10= 284 g/mol If the total pressure of such an equilibrium is about
1 x 10 atm, the value of К for this reaction at 2 0 0
A) 120 B) 240 C) 480 D) 960 E) 1920 °C is
A) 1 x 1012 B) 1.6 x 10' 14 C) 2.6 x 10' 28
20. A12 0 3 dissociates at high temperatures D) 1 x IQ’ 30 E) 8.2 x 10' 32
 CHAPTER

THE SECOND COLUMN OF THE

PERIODIC TABLE :
THE ALKALINE - EARTH METALS

The objectives o f this chapter are to enable the student t o :

1 - R ecognize th a t elem ents in th e sam e group exhibit sim ilar chem ical
properties.
2 - In te rp re t th e p roperties of elem ents in term s of th e ir electron configu­
ration.
3 - P red ict an d w rite chem ical equations involving th e alkaline e a rth m e­
tals.
4 - D escribe m ethods of p re p a ra tio n of th e alk alin e - e a r th m etals from
th e ir n atu rally o ccu rring compounds.
5 - G ain ex perience in applying th e g eneral chem istry principles to spe­
cific subject.
6 - U n d erstan d w h a t 'b a r d w ater" is, a n d w h at problem s it causes in in ­
dustry.
Ш
111Ш
ШН1111111Ш
1Ш1111111М
111М
111111М
111Ш
11!1111Ш
1Ш11111111111111111М
111Ш
111Ш
111Ш
Ш111Ш
111111111Ш 1ШThe Alkaline - Earth Metals
111111111111111111Ш 243

In the preceding chapter we saw how the properties o f elements in the third
period change systematically, when electrons are added to the outer orbitals o f
the atom. We saw that there was a trend from metallic behavior to nonmetallic,
from basic properties o f oxides to acidic properties, from ionic compounds to
molecular compounds.
In this chapter we shall examine how these properties change within a group.
Even though the elements have similar chemical properties, there are also im ­
portant differences among them. Many o f these differences may be explained in
terms o f atomic size.

7.1 ELECTRON CONFIGURATIONS OF THE

ALKALINE EARTH METALS.
Electronic configurations and some properties o f the alkaline earth metals are
given in Table 7.1.

TABLE 7.1 Properties o f the G roup IIA M etals

Property Beryllium M agnesium Calcium Strontium Barium Radium

outer electrons 2 s2 3s2 4s2 5s2 6 s2 7s2

melting point (°C) 1283 650 845 770 725 700
boiling point (°C) 2470 112 0 1420 1380 1640 1140
density (g/cm3) 1.85 1.74 1.55 2.60 3.51 5
atomic radius (A0) 1.11 1.60 1.97 2.15 2.17 2 .2 0

ionic radius, M2+ (A°) 0.31 0.65 0.99 1.13 1.35 _

electronegativity 1.5 1.2 1.0 1.0 1.0 1.0

standard reduction
potential (V)
M2+ (aq) + 2e— »M (s) - 1.85 - 2.37 -2.87 -2.89 -2.90 -2.92
ionization energy (eV)
M (g) - > M + (g) + e- 9.28 7.61 6.09 5.67 5.19 5.27
M+ (g) >M2 +(g) + e* 18.1 14.96 11.82 10.98 9.95 10 .10
heat of hydration of
gaseous ion (kcal/mol)
(approx).
M2+ (g) — >M2+ (aq) - 460 395 355 105 -

Each atom has an electron configuration consisting o f a noble gas core plus
two electrons in its outer s orbital. We can expect these two electrons to be easi­
ly removed to produce a stable ion that is isoelectronic with a noble gas and
with a monopositive alkalie metal ion. Since they can only give electrons in
chemical reactions, they are all metal. The alkaline earth metals are all silvery -
white, malleable, ductile, and somewhat harder than their immediate predeces­
sors in group IA. They all have the same configuration ending s2, so they have
nearly the same chemical behaviors. H owever they have differences in their
properties. Let us investigate the detailed differences among them.
244 Chapter 7 | || || || | || || || | || || || | || || | || || || I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I U I I I I I I I I N I I I lllllllllllllllllllllllllin illllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllll

7.2. TRENDS IN PHYSICAL PROPERTIES

7.2.1 ATOMIC RADII IN SOLIDS

In a real sense, it is impossible as the way we measure the diameter o f a golf

ball. An indirect approach is necessary. This approch is to measure interatomic
distances in the solids.
We see that the alkaline earth atoms become larger and larger from the top to
the bottom within the group. In other words the atomic size increases in the se­
quence Be < M g < Ca < Sr < В a. The differences in the properties o f the alka­
line earth metals can be explained by means o f their differences in atomic sizes.

7.2.2 IONIZATION ENERGIES

The Table 7.1 also shows their first and second ionization energies. The ion­
ization energies o f elements are dependent on the size and the symmetry in elec­
tron configuration o f atoms. These elements all have the same configuration
ending. (Therefore the same symmetry in electron configuration). Then the
change in atomic size is responsible for the changes in the ionization energies o f
the elements. Because the atomic size increases downward in a given group, the
ionization energies decrease downword in the sequence Be > M g > Ca > Sr >
В a.

7.2.3. METALLIC PROPERTIES

The metallic properties o f an element depend on th ease with which element

will release electrons. Therefore we expect the metallic properties o f the alkaline
earth metals to increase from top to bottom in the sequence B e - M g - Ca - Sr -
Ba. But some metals deviate from this sequence because o f their crystal struc­
ture in their metallic state.

EXAMPLE 7.1. Predicting Melting Points of the Elements

Problem : Predict the melting points of the alkaline earth metals Be, Mg, Ca, Sr, Ba.
S olution : The melting points of metals increases with
(I) the increase in the number of valence electrons.
(II) the increase in the ionization energy of the atoms.
Since they all have the same number of valence electrons, then the second factor determines the changes in
the melting points of the metals.
The order of increasing ionization energies : Be > Mg > Ca > Sr > Ba
The order of increasig melting points : Be > Mg > Ca > Sr > Ba

EXERCISE 7.1 Compare the melting points of the following pairs (a)u Na and 12Mg (b) 19K and 1 3 Al.

EXERCISE 7.2 Compare the following properties of the neighboring alkali metal and alkaline earth met­
al
(a) atomic size (b) first, second and third ionization energies, (c) reduction potentials
(d) charge densities (charge to volume ratio) of their stable ions.
iiiiiiiiiiiiii)iiiiiiiiiiiiii!!iiiiiiiiiiii!iiiii!!!iiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiii!iiiiiiiiiiiiiiiiiii!iiii)iiiiiiiiiiiiiiiiii!iiiiii!M iE i!iiii The Alkaline - Earth Metals 245

7.3 TRENDS IN CHEMICAL PROPERTIES

W e have already seen that the elements with the same number o f valence
electrons (similar electron configuration) have similar chemical properties. Now
let us see the chemical trends among these elements.

7.3.1 OXIDATION AND REDUCTION

They have low ionization energies therefore their oxidation potentials are
quite high. Their reduction potentials are given in Table 7.1.
Since they readily release electrons, they are strong reducing agents. The
chemistry o f an alkaline earth metal is largely a reflection o f its ease o f oxida­
tion. Some reactions o f the elements are given in Table 7.2.

TABLE 7.2 Reactions of the Group IIA Metals

Reaction Remarks
M + X2 MX2 X2 = all halogens
2M + 0 2 - -» 2MO Ba also gives Ba0 2
M + s —> MS also with Se and Те
3M + N 2 - -> m 3 n 2 at high temperatures
6 M + p4 - -» 2M3P2 at high temperatures
M + 2C -» MC2 all except Be which forms Be2C;
at high temperatures
M + H2 —> MH2 M =Ca, Sr, Ba; at high temperatures;
Mg with H2 under pressure
M + 2H20 —>M(OH) 2 + H2 M=Ca, Sr, Ba; room temperature;
steam
Be does not react at red heat
Mg + H20 —^ m 2o + H2
M + 2H+ - > M2+ + H2
Be + 20H" + 2H20 —>Be(OH)24 + H2 Be only
M + 2NH3 —» M(NH2 )2 + H2 M= Ca, Sr, Ba; liquid ammonia
in presence of catalysts
3M + 2NH3 —> M3 N 2 + 3H2 gaseous NH3; high temperatures

* M=any IIA metal, except where noted.

7.3.2 ACID AND BASE PROPERTIES

As w e explained in the previous chapter, the behavior o f the compound M-O-
H as an acid or a base depends on the electronegativity (ionization energy) o f the
element M .If the atom M attracks electrons щоге and more strongly there is an
increasing tendency toward acidic properties. Since the alkaline earth metals
have low ionization energies, we expect that the basic character o f these hydrox­
ide compounds increases toward the bottom o f the periodic table. Thus the base
strength o f the alkaline earth hydroxides is in the sequence of,
Be(OH ) 2 < Mg(OH ) 2 < Ca(OH) 2 < Sr(OH ) 2 < Ba(OH ) 2
Experimentally it is found that Be(OH ) 2 is an amphoteric hydroxide and Sr
(OH ) 2 and Ba(OH ) 2 are strong bases.
246 Chapter 7 иишшишиииишшншшшиишшшшшиишшшшишшншиииишиииииишшшшишнпишшшшншшишшпшшшшшшишшнш

EXAMPLE 7.2 Writing Reactions of Bases with Acids

Problem : Write the reactions of the hydroxides of the alkaline earth metals with strong acid.
S o lu tio n : Since these hydroxides are bases, they give neutralization reactions with acids. These ionic equa­
tions are:
Be(O H ) 2 (s) + 2H + (aq) -> Be2+ (aq) + 2H 20
Mg(OH ) 2 (s) + 2H + (aq) -> Mg2+ (aq) + 2H 20
Ca(OH ) 2 (s) + 2H + (aq) -> Ca2+ (aq) + 2H20
Sr(OH ) 2 (s) + 2H + (aq) -» Sr2+ (aq) + 2H 20
Ba(OH ) 2 (s) + 2H + (aq) -> Ba2+ (aq) + 2H20

EXERCISE 7.3 Be(OH) 2 dissolves appreciably in strong base solutions to produce BcOf and water. Write
the balanced equation for this reaction. Which property of Bc(OH) 2 is reflected by this reaction?
B e ( O H ) 2 (s) + 2 0 H~ — eO о + 2 H 20 am photeric

The hydroxides o f these metals can be prepared by the reaction o f metal ox­
ides with water. Therefore the metal oxides are basic anhydrides.
BeO (s) + H20 (1) — » Be(OH ) 2 (s) Л Н = - 2.5 kcal

MgO (s) + H20 (1) —» Mg(OH ) 2 (s) AH = - 8.9 kcal

CaO (s) + H2 0 (1 ) Ca(OH ) 2 (s) AH = -1 5 .6 kcal
SrO (s) + H20 (1) —» Sr(OH ) 2 (s) AH = - 19.9 kcal
B aO (s) + H 2 0 (1 ) —> Ba(OH)2 (s) AH = - 24.5 kcal
Notice that dissolving reactions o f metal oxides are exothermic. The reaction
heat is progressively increasing moving downward in the group IIA. From the
reaction heats we can deduce that the tendency o f BaO to produce a base is
greatest among the oxides of the alkaline earth metals.
The formation o f Ca(OH ) 2 from CaO is called "slaking lim e”.
CaO (s) + H20 (1) —> Ca(OH ) 2 + 15.6 kcal
lime slaked lime

EXAMPLE 7.3 Calculation of Heat Evolved During Slaking Lime

Problem : Lime (CaO), can be prepared by the decomposition of limestone, CaC03, at 1000°C.
(a) How many kg of lime can be obtained from one ton of limestone that is 70 % pure?
(b) How many kcal of heat will be released during the slaking the lime produced?
(c) How many kg of water can be evaporated with this heat? (Assume that water is initially at 25°C, and the heat
of evaporation of water is 540 kcal/kg. CaC0 3 = 100, CaO =56
S o lu tio n : (a) Since 70 percent of limestone is CaC03, then the mass of CaC0 3 in 1 ton (1000 kg) of ore
will be:

- 70 ^ 8 CaC0 3 x 1000 kg ore = 7 0 0 k g C a C 0 3

1 0 0 kg ore

The mass of lime (CaO) can be calculated 100kg 56 kg. ^ _ 700 x 56 QOOi,„
by means of the decomposition reaction: CaC0 3 —> CaO + C 0 2 ioo
700 kg x kg
iiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiM iiiiiiiiiiiiiiiiiiiiiiiiiiii The Alkaline - Earth Metals 247

(b) The heat evolved is

CaO + H20 —> Ca(OH) 2 + 15.6 kcal

If 56 g CaO produce 15.6 kcal \ 3

I *„ =
_ ---------
392 x 10 x 15.6
_ ------- l_ _ 1Л x 10s kcal
392 x 103 g CaO produce x

(c) Let m represent the mass of water evaporated in kg. Firstly it will warm up by gaining energy:
Q! = m x с x At = m x l x (100 - 25) = 75 m kcal
Then it will evaporate by gaining the energy: Q2=540 m kcal.
The total heat energy gained by water is equal to the heat energy lost by the reaction. Therefore
Qi + Q2 = Q released
75 m + 540 m = 1.1 x 105
615 m = 1.1 x 105
m = 179 kg.

7.3.3 SOLUBILITIES OF ALKALINE EARTH

COMPOUNDS IN WATER
The solubility product constants o f some alkaline earth compounds are given
in Table 7.3.

TABLE 7.3 So lu b ility P ro d u ct C onstants

O ff sc£ cof C2 0 ,2- F’ сю*-

Be2f 1.6 x 1 0 - 26 _ _ _ _ _
Mg2+ 8.9 x 10-12 - 1.0 x 1 0 ‘5 8 .6 x 10 -5 8 .0x 1 0 '8 -

Ca2+ 1.3 x 10-6 2.4 x 10-5 4.0 x 10-9 1.3 x 10-9 1.7 x 10-10 7.1 x 10 4
Sr2+ 3.2 x 10-4 7.6 x 10' 7 7 x 10ЛО 5.6 x 10-8 7.9 x 10-10 3.6 x 10-5
Ba2+ 5.0 x IQ' 3 1.5 x 10' 9 1 .6 x 1 0 '9 1.5 x 10’ 8 2.4 x 10-5 8.5 x 10‘u

When the solubilities o f hydroxides are considered, the solubility increases

going down the group in a regular order.
The trend in the solubility o f sulfates is the reverse o f that o f hydroxides.
The solubility decreases down the group. B e S 0 4 is the m ost soluble, and
B aS 0 4 is the least soluble. The same argument is almost true for the carbonates.
The solubility o f C aC 0 3 is 4 .7 x l0 '9. Though it may seem quite small, the ex­
istence o f large natural beds o f C aC 0 3 creates a special problem for water sup­
plies. The solubility o f C aC 0 3 increases in solutions containing C 0 2. Since our
atmosphere contains 0.04 % C 0 2, all the ground water contains C 0 2 dissolved
in it. These ground water sources (solutions o f C 0 2) dissolve limestone accord­
ing to the reaction,

CaC0 3 (s) + C 0 2 + H20 —» Ca2+ (aq) + 2HCO 3 (aq)

The result is that we get an appreciable concentration o f Ca2+ ions in most

 248 Chapter 7 ш и п п и ш и

ground water. The water containing Ca2+, M g2+ and Fe2+ions is called hard
water. Hard water makes washing difficult because Ca2+ ions form unpleasant,
scummy precipitate with soap (sodium stearate, C 17 H 35 COONa). The precipitate
is calcium stearate, Са(С 17 Нз5 СОО)2
This insoluble calcium stearate is the familiar scum or bathtub ring. Hard wa­
ter is also an industrial problem. Salts o f calcium such as C aC 03, C aS 0 4 tend to
precipitate and form scale in boilers and other water tanks.
Hard water is acceptable for some applications, but for others it must be
"softened". The "softening water" refers to the removal o f Ca2+ and M g2+ ions
N aC l
s o lu tio n
which make water hard. When water containing bicarbonates o f these ions are
in le t boiled, the hardness disappears. Boiling causes the soluble metal bicarbonates
to precipitate as insoluble metal carbonates, and therefore removes Ca2+ or Mg2+
ions from the solution.
Ca2+ (aq) + 2H C 0 '3 (aq) CaC0 3 (s) + H2 0 (1 ) + C 0 2 (g)
The hardness due to metal bicarbonates (temporary hardness) may be re­
moved by boiling. But water containing calcium or magnesium sulfate is unaf­
fected by boiling (permanent hardness).
The temporary or permanent hardness may be removed by the treatment o f
FIGURE 7.1 Softening
hardwater by ion exchange hard water with sodium carbonate. The soluble Ca2+ ions are converted into in­
method. soluble C aC 03, while Na+ ions remain in the solution.
Ca2+ (aq) + S 0 2 '(aq) + 2Na+ (aq) + C 0 2 ~(aq) —» C aC 0 3 (s) + 2Na+ (aq) + S 0 2 '(aq)
Another method for softening water is to exchange Ca2+ or M g2+ ions with
Na+ ions. Zeolite (NaAlSi 2 0 6) or a synthatic resinous matecial are used for this
process. If zeolite is involved, the symbol Z is used and if a synthatic resin, R
■2+
NajZ + M MZ + 2Na+
2+
Na 2R+ M: MR + 2Na+ See Figure 7.1 and Table 7.4.

TABLO 7.4 So ften in g H a rd W ater

Type of Method of
hard water Contents softening Reaction
Temporary Ca } (HC0 3) 2 Heating Ca2+ + 2H C 0 3 -4> CaC0 3 (s) + H20 + C 0 2
Mg
Adding Ca2+ + 2HCO’ + Ca2+ + 20IT —» 2CaC0 3 + 2H20
Ca(OH) 2
Permanent CaS0 4 Adding Ca2 +-bS02 '+2Na++C02~ —» CaCQ3+2 Na++ S 02'
Na2 C 0 3
Temporary Ca } (HC0 3) 2 Ion exchange: Na2Ze + Ca2+ + SO2'
4
—> CaZe + 2Na+ + SO2'
4
or Mg zeolites
permanent CaS0 4 or resins

The dissolving action o f C 0 2 containing water is also responsible for the

caves found in limestone regions. These caves are produced by partly dissolv­
ing action and by partly reprecipitation o f C aC 03.The optimum conditions for
C aC 0 3 precipitation are slow seepage o f ground water, steady evaporation, and
no disturbing air currents. Ground water containing Ca2+ and H C 0 3 may seep
through a fissure in the roof and hang as a drop from the ceiling. As the water
evaporates along with carbon dioxide the dissolving reaction reverses to depo-
 inn шпини huh The Alkaline - Earth Metals 249

site a drop o f C aC 0 3
Ca2+ (aq) + 2H C 0‘ (aq) —> CaC0 3 (s) + H20 + C 0 2 (g)
Later another drop o f ground water seeps on the limestone speck and the pro­
cess goes on. In a time o f long period, a cylinderical deposit reaching down
from roof may be built up in the form o f a limestone, which is called stalactite.
Occasionally drops o f ground water may drip o ff the stalactite to the floor o f the
cave, where they evaporate to form a spire or stalagmite o f C aC 03. See Figure
7 .2 .

7.4 OCCURRENCE AND PREPARATION OF

THE ALKALINE EARTH ELEMENTS
In nature, the alkaline earth metals are found only in compounds as (2+)
ions. They are usually prepared by electrolysis o f their molten chlorides.
FIGURE: 7.2 Stalactites M G 2 (molten) —> M (l) + Cl2 (g)
and stalagmites. Beryllium, the forty-fourth most abundant element., is rather rare. Its most
important mineral is aluminum beryllium silicate (beryl) Be 3 A l 2 ( S i0 3) 6 the gem
stone emerald is beryl containing traces amount o f chromium. It is prepared ei­
ther electrolysis o f molten BeCl 2 or Be2+, or by reduction o f BeF 2 with Mg.
Since beryllium silicates are fluorescent, it is used to coat the inner walls o f flu­
orescent tubes.
Magnesium is the eighth most abundant element in the earth's crust. Its com ­
mon compounds are asbestos (CaMg 3 ( S i0 3)4, magnesite (M g C 0 3), dolomite
(C a C 0 3 .M g C 0 3). It is prepared from seawater as explained in the previous
chapter. It may also be prepared by the electrolysis o f molten MgO obtained by
heating dolomite.
Calcium, the sixth most abundant element, is found in lim estone (C aC 03),
gypsum (C aS 0 4 .2H 2 0 ) , and calcium phosphate (Ca 3 ( P 0 4)2). Calcium is
prepared by electrolysis o f calcium compounds in nonaqueous media at high
temperatures. Calcium compounds are essential to life, and has great industrial
importance.
Strontium, the thirty - eighth most abundant element, is quite rare. It occurs as
celestine, S rS 0 4, and strontianite S rC 0 3. Its compounds are used in the fire­
works, and in sugar refining.
Barium, the eighteenth most abundant element, is also rather rare. Its principal
mineral is barite, B a S 0 4. The properties o f compounds o f barium resemble
those o f calcium but are poisonous. Its compounds are used in the manufacture
o f paint, glass, and fireworks.
Radium, is very rare, radioactive metal. Uranium ores such as pitchblende,
U 3 Og, are principal sources o f radium. Because the nuclear breakdown o f urani­
um produces radium.
250 Chapter 7 нишшшшшшшншшшшЛ ........... .

SOME NEW TERMS

Hard water : The water containing minerals in causes hardness from water. This is made either by
significant concentrations. If the hardness is due to the addition of washing - soda or by use of zeolites
HCOj and associated 2+ charged cations it is called Zeolite : The natural hydrated silicate of sodium
temporary hardness. If the hardness is due to an­ and aluminum. When hard water is passed through a
ions other than HCOj, for example SOj‘ and asso­ suitable zeolite, the Ca2+ in the water are replaced by
ciated 2 + charged cations, it is called permanent Na+ in the zeolite. The process may be reversed and
hardness. the zeolite restored by washing it with sodium chlo­
W ater softening : The removal of ions which ride solution.

REVIEW QUESTIONS AND PROBLEMS

7.1 Compare the properties of an alkali metal and (d) CaC0 3 .MgC03 —»
its neighboring alkaline earth metal with respect to (e) Mg + H20 (steam) —>
(a) first, second, and third ionization energies,
(b) stable ionic size, 7.5 Compare the melting points of the fluorides
(c) melting point and boiling point, of IIA group elements.
(d) hardness. Account for similarities and differenc­
7.6 Show that oxides of alkaline earth metals are
es.
base anhydrides.
7.2 Explain the observed trends in
(a) atomic size, How do the basic strengths of hydroxides of
(b) ionic size, alkaline earth metals change going down the group?
(c) oxidation potentials within the alkaline earth 7.8 What is "hard water"? What problems does it
group. cause in industry?
7.3 Write balanced equations to represent the reac­ 7.9 Which compounds cause (a) temporary hard-
tion of nes (b) permanent hardness?
(a) sodium with oxygen gas.
(b) calcium with chlorine gas. 7.10 How does the softening temporary hard wa­
(c) barium with water. ter differ from the softening permanent hard water?
(d) magnesium with nitrogen gas. Explain.
(e) thermal decomposition of CaC0 3
(f) electrolysis of molten MgCl2 Water containing dissolved calcium sulfate
(g) Formation of scum from soap (C17 H35 COONa) can be softened by means of washing soda (Na2C 0 3.
1 0 H 2 O), but the same treatment cannot be used to
and Ca2+ in hard water.
soften hard water containing magnesium sulfate, (a)
7.4 Complete the following reactions Explain the reason for this difference, (b) What treat­
(a) CaO + H20 —» ment other than ion exchange could you use to soft­
(b) Be + HC1 —> en this type of hard water?
(c) Be + NaOH —> H2 + ...
iiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiu i The Alkaline - Earth Metals 251

7.12 How many kg of lime can be prepared from *7.20 A typical seawater contains Mg2+ ions at a
1 ton of limestone containing 15% impurity? concentration of 0.04 M and Ca2+ ions 440 ppm (i.e
476 kg 440 g in 106 g of seawater). To precipitate Mg2+
ions only from the solution, in what range must the
7.13 Calcite is a crystalline form of pure CaC03.
concentration of OH' ions be kept? Ksp for Ca
It has an unusual property of double refraction. If 0.5
(OH) 2 and for Mg(OH) 2 are 5.5 x 10" 5 and 2xl0"n
g of calcite reacts with exactly 40 mL of hydrochlor­
respectively. The density of seawater is 1.03 g/mL.
ic acid solution, what will be the molarity of the
acid solution? CaC0 3 = 100 g/mol 0.25 M
2x10 s £[O
H~] < 0.07

7.21 What weight of calcium hydroxide would be

7.14 What is the pH of 80 mL of aqueous solu­
needed to soften 1 m3 of water containing 8 . 1 mg
tion in which 55 mg of Ba are dissolved? Reaction
calcium bicarbonate per liter? Ca(OH) 2 = 74 g/mol.
for the process is
C a(H C 0 3 ) 2 = 162 g/mol 3.7 g
Ba + 2HzO —> Ba(OH) 2 + H2 (g) 12
7.22 What mass of "bathtub ring" will form if
7.15 The solubility of Ca(OH) 2 is about 0.148
10 L of water sample having 8 8 g Ca2+ per m3 of
g/L. What is the pH of saturated solution of
water is treated with soap? 13.3 g
Ca(OH) 2 (limewater)? Ca(ON) 2 =74 g g/mol 11.6
7.23 A suitable method for softening temporary
7.16 (a) How many liters of C 0 2 at,STP can be
hard water is to treat it with lime (CaO). The reac­
prepared from 400 kg of dolomite that is 92% pure?
tions involved in this process are.
(b) How may kg of Ca and Mg can be prepared
from the same sample? I. CaO (s) + H20 —> Ca2+ (aq) + 20H ' (aq)
( a ) 8 . 9 6 x l 0 4 L, (b )8 0 kg Ca, 48 kg M g II. HCOj (aq) + OH' (aq) —» H20 + C0 32 (aq)
IIL Ca2+ (aq) + CO2' (aq) -» CaC0 3 (s)
*7.17 When a 14.2 g mixture of CaC0 3 and How many kg of CaO must be added to 5 x 106 g of
M gC 0 3 is decomposed by heating, 7.6 g of oxides water which contain 183 ppm HCOj ? 0.42 kg
of elements is obtained. How many liters of C 0 2 gas
at 730 mm Hg and 1027°C will be produced by de­ 7.24 A 10 g mixture of Na20 and BaO is dis­
composing 71 g of this sample ? 83.2 I solved in water. This solution is then treated with di­
lute H2 S 0 4 solution. The precipitate formed is fil­
7.18 The electrolysis of an aqueous solution of tered and is found to weigh 3.5 g. What is the
CaCl2 can be represented by the equation. percentage of Na20 in the original sample of mixed
Ca2+ (aq) + 2СГ (aq) + 2H20 —» oxides? 77%
Ca2+ (aq) + 20H ' (aq) + H2 (g) + Cl2 (g)
The electrolysis of a 500 mL sample of 0.01 M 7.25 Radium is a radioactive alkaline earth metal.
CaCl2 is continued until 0.56 L of Cl2 at STP has Ra - 222 has a half-life of 1620 years. How many
been collected. Will Ca(OH) 2 precipitate when the years will it take for 1 0 g of radium to decay to
electrolysis is carried out to this point? Ksp for 1.25 g? 4 8 6 0 yea rs
Ca(OH) 2 = 5.5 x 10"6 Yes
7.26 Calculate the molar heat of formation of Ca
7.19 The quantity of Mg2+ ions in seawater is (OH) 2 from the following data
1.272 g/ton. How many grams of CaO must be add­ H2 + l/2 0 2 —» H20 AH = - 68.3 kcal.
ed to 1 m3 of seawater to start the precipitation of CaO + H20 —>Ca(OH ) 2 AH = -15.3 kcal.
Mg(OH) 2 for which Ksp = 9 x 10" 1 2 (The density of Ca + l/2 0 2 —>CaO AH = - 151.8 kcal.
seawater is 1.03 g/mL) 11.2 g - 2 35 .4 kcal
252 Chapter 7 I iiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiin I н ш ш ш ш н ш ..................................... .... i i .................................... I ........... .. ......... и ................... I I I I I I I I ..................................... n u n

SELF TEST
1. Which is wrong for IIA group elements down­ 7. The first and second ionization energies of Mg
ward the group? atom are 175 kcal and 345 kcal/mol. How much en­
(a) Atomic size increases ergy in kcal must be needed to produce 0 . 6 g of
(b) Metallic character increases Mg2+ ions from gaseous magnesium atoms?
(c) Ionization energy decreases Mg = 24
(d) Oxidation potential decreases A) 5.2 B) 10.4 C) 13 D) 18.2 E) 24
(e) Melting point decreases
8 . X, Y and Z represent the elements of the same
2. X and Y are two adjacent elements of IA and group.
IIA groups of periodic table. I. X is more electronegative than Y
I. The metallic character of X is greater than Y II. The oxidation potential of Z is smaller than Y
II. X20 and YO are basic oxides and is greater than X. Which of the following repre­
III. X1+ and Y2+ are isoelectronic. sents the increasing order of atomic numbers of these
IV. The ionic radius of Y2+ is greater than that of X1+ elements.
Which of these statements are true? A) X,Y,Z B) Z,Y,X C) Y,Z,X
A) I and II В) I,И,III С) И,IV D) X,Z,Y E) Z,X,Y
D) II,III,IV E) I,II,III,IV
9. Which is the pH of the solution resulting from
3. Which of the following compounds has the great­ the reaction of 0.8 g of Ca with 4 L of water?
est ionic character? Ca = 40 g/mol
A) BcCl2 B) MgCl2 C) CaCl2 A) 2 В) 3 C) 8 D) 9 E) 12
D) SrCl2 E) BaCl2
10. The water containing 10 mg of CaC0 3 per liter
4. When a 20 g impure sample of calcium is treated of solution is said to have a hardness degree of one.
with water, 4.1 liters of hydrogen gas are produced at Which is the hardness degree of a saturated solution
1.2 atm pressure and 27°C. What is the percentage of CaC0 3 for which Ksp is 4.9 x 10' 9 ?
purity of Ca by mass in the original sample? CaC0 3 = 100 g/mol
Ca = 40 A) 0.7 B) 1.4 C) 2.1 D) 3.5 E) 7.0
A) 10 B) 25 C) 40 D) 55 E) 80
11. A sample of marble weighing 2.0 g requires 20
5. Which is the strongest base ? ml of 1.5 M HC1 to react with the CaC0 3 in the
A) Be(OH) 2 B) Mg(OH) 2 C) Ca(OH) 2 marble. What percent of the marble is
D) Sr(OH) 2 E) Ba(OH) 2 CaC03? CaC0 3 = 100 g/mol.
A) 53 B) 75 C )82 D )91 E )96
6 . Which species are represented by X, Y, Z, L and
M in the equations respectively? 12. If calcium ions are to be removed from a city
I. Ca (s) + . ... H20 - ■» Ca(OH) 2 + X water by the addition of soda ash, Na2 C 0 3, what fi­
II. CaH2 (s) + ,...H 20 —» Y + H2 nal concentration of CO3 ' is required to reduce
III. ...Mg (s) + . .. n 2 —> Z [Ca2+] in water to
IV. CaC0 3 + .... HC1 — > L + H2o + M (g) 1 x lO’ 5 M? Ksp for CaC0 3 = 5 x 10' 9
_X Y Z L M A) 1 x lO’ 5 B) 2 x 10' 4 C) 5 x 10‘ 4
A)H2 CaO Mg3N 2 CaCl2 co2 D) 2.5 x 10' 6 E) 5 x lO' 9
B)H2 Ca(OH) 2 Mg3N2 СОг CaCI
C )0 2 CaO Mg3N2 CaCl2 co2 13. What concentration of aqueous NH 3 is necessary
D)H2 Ca(OH) 2 Mg3N2 CaCl2 co 2 to just initiate the precipitation of Mg(OH) 2 from
E )0 2 CaO Mg3N2 CaCl2 co2 0.2 M Mg(N03)2?
iiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiM iiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiM iiiiiiiiiiiii The Alkaline - Earth Metals 253

Ksp for Mg(OH) 2 is 2 x 10 1 1 and Period Group

Kb(NH3) = 2 x 10' 5 A) 4 IIA
A) 1 x 10' 5 В) 1 x 10' 6 C) 2 x 10' 6 B) 3 ПВ
D) 5 x 10' 6 E) 8 x 10' 6 C) 3 IIA
D) 5 VIB
14. When an 80 g sample of limestone is reacted E) 5 ПА
with HC1,41 liters of C 0 2 are liberated at 227°C and
380 mm Hg. What is the percentage of CaC0 3 in 18. A strip of magnesium weighing 30 g is passed
the limestone sample? CaC0 3 = 100 g/mol through steam at 120°C. If the mass of strip be­
A) 37.5 B) 50 C) 62.5 D) 75 E) 82 comes 33.2 g, what percent of magnesium is oxi­
dized? Mg = 24, О =16
15. A calorimeter has a heat capacity of 300 cal/°C A) 8 B) 16 C) 32 D) 64 E) 90
and contains 600 g of water.A strip of magnesium
with a mass of 1 . 8 g is burned completely in excess 19. When the same concentrations of 400 ml of Ba
oxygen in the calorimeter. If the temperature increas­ (OH) 2 and 600 mL of H N0 3 solutions are mixed, the
es by 12°C, which will be the heat of formation of pH of the resulting solution is found to be 13.
magnesium oxide in kcal/mol? Mg = 24 g/mol Which is the molarity of Ba(OH) 2 solution?
A) 48 B) 96 C) 144 D) 240 E) 288 A) 0.1 B) 0.25 C )0.50 D) 0.8 E) 1

16. A solution is containing 0.01 M of each of the 20 - At 1200 К the partial pressure of C 0 2 in equi­
ions Ba2+, Sr2+, Mg2+. If a 1 M NH 3 solution is add­ librium with CaC0 3 and CaO is
ed to this solution, which precipitate (s) will be 4.5 x 10' 2 atm. The equilibrium constant for the re­
formed? action,
Ksp(Ba(OH)2) = 5.0 x 10*3, Ksp(Sr(OH)2) =3.2 x 10'4, 2CO (g) - > С (s) + C 0 2 (g)
Ksp(Mg(OH)2 )=9.0 x 10' 12 and Kb(NH3) =1.8 x 10'5. is 0.5 L/atm at the same temperature. What is the
A) Mg(OH) 2 alone B) Sr(OH) 2 alone equilibrium pressure CO in atm of in an equilibri­
um mixture represented by the equation?
C) Ca(OH) 2 alone D) all.
CaC0 3 (s) + С (s) CaO (s) + 2CO
E) Ba(OH) 2 and Mg(OH) 2
at 1200 K.

17. A quantity of electrical charge that causes the

A) 0.25 B )0.30 C) 0.35 D) 0.40 E) 0.45
deposition of 4 g of Ca from molten CaCl2, also de­
posites 8 .8 g of X metal from molten XC12. If X has
50 neutrons, which will be its period and group
number ? Ca = 40
 CHAPTER

THE FOURTH ROW

TRANSITION ELEMENTS
The objectives of this chapter are to enable th e student t o :
1 - E x p lain th e w ays in w h ic h tra n s itio n elem ents differ from A g ro u p
elem ents.
2 - W rite th e electro n configurations of tra n sitio n elem ents, a n d explain
th e relatio n sh ip s betw een electronic s tru c tu re a n d p ro p erties o f ele­
m ents.
3 - S ta te th e ty p ical ox id atio n sta te s of th e first tra n sitio n series of ele­
m ents.
4 - W rite equations for some im portant oxidation - reduction reactions in ­
volving MnO", CrO^" , C r20^' ions.
5 - Illu strate th e shapes, p roperties of complex ions.
6 - W rite chem ical eq u atio n s to illu stra te th e am p h o teric p ro p e rtie s of
complexes of Zn2+ an d Cr3*
7 - Describe sources, uses an d p rep aratio n of th e elements.
iiiMiiiiiiiiiiiiiiimiiiMHiiiiiiiiiiiiiitiliiiiiiiiiiiiiiifiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiHiiiiiiiiiiiiiiiiiiiiiiiii The Fourth riow Transition Elements 257

In the preceding chapters, we have studied the chemistry o f elements in a

group and in a period. N ow w e shall consider the elements located between
groups IIA and IIIA in the periodic table, which are usually called transition
elements. Thus in the fourth period the transition elements are scandium
(Z = 21), titanium (22), vanadium (23), chromium (24), manganese (25), iron
(26), cobalt (27), nickel (28), copper (29), and Zinc (30). Each o f these ele­
ments heads a subgroup named after itself, such as scandium subgroup or
group 111B, titanium subgroup or group 1VB...

8.1 DEFINITION OF TRANSITION ELEMENTS

The elements in d block and f block o f periodic table are called transition
elem ents. Strictly speaking for an clement to be d- transition element, it
must have a partially filled set o f d orbitals. The group IIB elements (Zn, Cd,
Hg) therefore are not really transition elements. However these are often includ­
ed in transition group because o f the similarities o f their properties to those o f
transition elements. All o f the other elements except Cu, Ag, Au (the group IB
elements) have partially filled d orbitals.

8.2 ELECTRONIC CONFIGURATION OF

3d - TRANSITION ELEMENTS
The energies o f the 3d and 4s orbitals are nearly equal. Generally the 3d or­
bitals fill gradually after 4s orbital is filled. Therefore the electrons in 4s and 3d
may be considered as valence electrons. The exceptions are chromium and cop­
per, for both o f which there is only one electron in 4s orbital and one "extra"
electron in the 3d orbitals. In the case o f chromium the half - filled 3d and 4s or­
bitals result., and for copper filled 3d orbitals and a half - filled 4s orbital result.
Both are favorable configurations with respect to Hund's Rule. Sim ply any
electron configuration which will normally end with either ns 2 (n-l)d4 or
ns 2 (n- 1 ) d9 is converted into ns 1 (n-l)d 5 or ns 1 (n -l)d 10 respectively because o f
the stability o f completely half-filled, and completely filled d orbitals. See Table
8.1. The stability o f the half-filled or filled set o f d-orbitals is reflected in the
chemistry o f the chromium and copper.

TABLE 8.1 E lectron C onfigurations o f the F o u rth Row Transition

E le m e n ts
ATOMIC ELECTRON
ELEMENT SYMBOL NUMBER, Z CONFIGURATION

scandium Sc 2 1
Is 2 2s 22p 6 3s 2 3p6 3d’4s 2
titanium Ti 22 S d^ s 2
vanadium V 23 3d 34s 2
chromium Cr 24 3d 54s!
manganese Ml 25 Each fourth - row tran­ 3d54s 2
iron Fe 26 sition element has these 3d 64s 2
cobalt Cb 27 levels filled. 3d74s 2
nickel Ni 28 3d 84s 2
copper
rrv Cu 29 3d 10 4 s 1
zinc Zn ’ 30 3d 10 4s 2
258 Chapter 8 o il) M ill! Ill ш ш iiiiim iiiiiii .................... .
ш м ш м м п и ............... .. ........................................ .

■" -------
EXAMPLE 8.1 Writing the Electron Configuration of Transition Elements
Problem : Write the electron configurations of transition metals 42 M0 , and 47 Ag,
S o lu tio n : Expected real
42Mo : [Kr] 4d4 5s2 — > [Kr]4d5 5s1
47Ag : [Kr] 4d9 5s2 — » [Kr] 4d10 5s!

EXERCISE 8.1 Write the electron configuration of 79 Au.

8.3 GENERAL PROPERTIES OF 3d

TRANSITION ELEMENTS
Some specific properties o f 3d transition elements are shown in Table 8.2.
N ow let us discuss some outstanding properties o f these elements.

TABLE 8.2 Properties o f the F irst Transition Series

Properties Sc Ti V Cr Mn Fe Co Ni Cu Zn
melting point (°C) 1541 1660 1890 1900 1244 1535 1495 1453 1083 420
boiling point (°C) 2831 3287 3380 2672 1962 2750 2870 2732 2567 907
density (g/cm3) 3.0 4.51 6 .11 7.9 7.2 7.87 8.7 8.91 8.94 7.13
atomic radius (A°) 1.62 1.47 1.34 1.25 1.29 1.26 1.25 1.24 1.28 1.38
ionic radius, МЗ^А0) - 0.94 0 .8 8 0.89 0.80 0.74 0.72 0.69 0.70 0.74
electronegativity 1.3 1.4 1.5 1 . 6 1.6 1.7 1.8 1 .8 1.8 1.6

std. red. pot. (V) for

M2 +(aq)+2e* M(s) -2.08* -1.63 - 1 . 2 -0.91 -1.18 -0.44 -0.28 -0.25 + 0.34 -0.7 6
I. IE (ev) 6.56 6.83 6.74 6.76 7.43 7.90 7.86 7.63 7.72 9.39
II. IE (ev) 12.89 13.63 14.2 16.49 15.64 16.18 17.05 18.15 20.29 17.96
*for Sc3+(aq)+3e- —> Sc(s)

1. They are all metals. This is not suprising because they have few elec­
trons in their outermost energy level. However most are harder, more brittle,
and have higher melting points and boiling points than non-transition metals.
These properties indicate that the metallic bond in these elements is stronger.
The strength o f metallic bonding increases with the availability o f the delocal­
ized electrons over the lattice. Since alkalie, and alkaline earth metals have only
one or two valence electrons, their melting points and boiling points are quite
low with respect to the other solids. But the increasing availability o f d elec­
trons especially unpaired electrons causes an increase in melting point o f transi­
tion metals from the beginning toward the center o f each transition series, as
seen in Table 8.2.
The exceptional elements in this respect are the group IIB elem ents, zinc,
cadmium and mercury.
2. Most transition metal compounds are colored. T his property
suggets that in the compounds there are electronic energy levels close enough
together so that electrons can easily absorb light in the visible region (w ave­
length o f 4000 A°- 7000 A°).
3. They exhibit multiple oxidation states. The outer 4s electrons are
always the first ones-lost in ionization. Because electrons in 3d orbitals may be
lost along with 4s electrons, the transition metals display variable oxidation
 The Fourth Row Transition Elements 259

states. The maximum oxidation state is given by the group number o f the metal,
but this is not usually the most stable oxidation state. For example, manganese
can exist in all oxidation states ranging from +2 to +7 as shown in Table 8.3.

TABLE 8.3 N onzero O xidation States o f the 3d - Transition M etals

IVB VB VIB VIIB VIIIB IB IIB
1 1
Ti V Cr Mn Fe Co Ni Cu Zn
+1 red. +1 red. +1 red. +1 red. +1 red. +1 red.
+2 red. + 2 red. +2 red. +2 +2 red. +2 +2 +2 +2

+3 red. +3 red. +3 +3 ox. +3 +3 ox. +3 ox. +3 ox.

+4 +4 +4 ox. +4 ox. +4 ox. +4 ox. +4 ox.
+5 ox. +5 ox. +5 ox. +5 ox.
+6 ox. + 6 ox. + 6 ox.
+7 ox.
+ Most common oxidation states are boldface italic.

EXAMPLE 8.2 Determining Oxidation Number

P ro b le m : What is the oxidation number and electron configuration of chromium in each of the following
compounds: CrO, Cr2 0 3, Cr2O f
S o lutio n : Cr2+ O2' — > 24C r: [Ar] 3d4 4s
Cr3+ O f — » 24 C r: [Ar] 3d3 4s

C if O f — ■* MC r: [Ar] 3d 4s

EXERCISE: 8.2 What is the oxidation number and electron configuration of vanadium in each of the fol­
lowing compounds VO, V2 0 3, V 0 2 NH4, V 0 3, V20 5?

4. Their atomic sizes and ionization energies are fairly constant

across the period. The essential difference in atomic structures between suc­
cessive elements is an increase in nuclear charge and addition o f one electron to
the d orbitals. The increase in nuclear charge along the series tends to decrease
atomic size, but the addition o f an electron has an opposing effect. Consequent­
ly the size o f atoms remains nearly constant, and decrease only slow ly in the
transition series.
The first ionization energies o f neighboring atoms which are closely related
to atomic size, are very nearly the same, but as the atomic number increases, the
ionization energy o f the element increases. The values o f first ionization ener­
gies are about the same as for the alkaline earth metals. As parallel to the in­
crease in ionization energies across the fourth period, the oxidation o f Cu to
Cu2+ is an exception in, this respect. A ll o f the elements except Cu are more
readily oxidized than hydrogen, that is, they dissolve in acidic solutions and
produce H 2 gas.

EXERCISE: 8.3 Show that all the transition metals dissolve in 1 M H+ solution except Cu. (Calculate
e° values of the probable reactions). Consult the table.
260 Chapter 8 1....... ИШ Ш Ш Ш Ш ......... Ш Ш Ш Ш Ш Ш Ш Ш Ш Ш Ш Ш Ш Ш Ш Ш Ш Ш Ш Ш Ш Ш Ш ИШ ПШ Ш Ш Ш Ш ....... ШИПП..........ШШШ1111Ш1Ш11............ ш и ш

5. They are different in chemical reactivity: Some elem ents, such as

iron can be polished, so they have metallic luster for a while, but they will lose
their bright metallic color soon on exposure to air because o f corrosion. Some
are quite reactive such as Zn. Each element has its own characteristic chemical
properties. For example chromium metal is highly reactive toward oxygen. A
polished piece o f chromium keeps its luster almost indefinitely when exposed to
air. This is because o f formation o f a thin transparent coat o f Cr2 0 3 , which
protects the underlying metal from further reaction. Consequently chromium is
used as a protective and decorative coating for other metals.
6. The complex-ion formation is characteristic for transition
elements. This property is due to- the existence o f vacant orbitals. N ow we
shall consider the complex ions in some details.

8.4 COMPLEX IONS

Most d-transition metal ions have vacant d orbitals which can accomodate
electron pairs o f other species. For example, consider Cr3+ , and N H 3 m ole­
cule.
H

*№ : [Ar] O O tS O O О ООО and : N : H

3d 4s 4p н

The electron configuration o f Cr3+ indicates that there are completely empty
two 3d, one 4s, and three 4p orbitals. These six empty orbitals are able to share
six pairs o f electrons. Since one NH 3 m olecule has one pair o f unshared elec­
trons, then one Cr3+can accomodate six ammonia molecules.
Cr3+ + 6 NH 3 = Cr(NH3)3+

c o m p le x io n a n io n s Here Cr(NH3)3+ is a complex ion. A complex ion consists o f a central metal

cation to which several anions or neutral molecules (called ligands) are direct-
[Co(NH3)6]3+ За-
lyl bonded. Ligands have the property o f donating electrons to the central atom
(Lewis bases).
Here Cr3+ is the central metal ion, NH 3 is the ligand (a Lewis base), and
lig a n d s c o n o rd in a tio n the number o f ligands surrounding central ion ( 6 ) is the coordination number o f
n u m b er
central ion. The central ions and its surrounding ligands act as a single chemical
a c o o rd in a tio n entity. By convention, the central atom and the ligands o f a com plex ion are
co m p o u n d shown in brackets to emphasize that they act as a single chemical unit. The com ­
plex ion mentioned above must be written as [Cr(NH3)6]3+.
In the complex ion [Co(NH 3 ) 5 Cl]Cl2, the species five NH 3 and one Cl are li­
gands, two Cl outside the bracket are the counter ions balancing the charge o f
Co2+ (In complex ion the oxidation number o f Co is 3+.) When one mole o f this
substance is dissolved in water, one m ole o f [Co(NH 3) 5 C1]2+ and two moles o f
СГ ions will be formed. In a complex ion the central atom is usually a transition
atom, and the common ligands are F', СГ, Br', Г, CN~, OH', H 2 0 , NH 3...
нн1ш«тнтшщшшшшш11шинн11111111111мш1111м111ш11шш111ш1ш11ш11111111111шш1ш111111 The Fourth Row Transition Elements 261

EXAMPLE 8.3 D eterm in ation o f C entral A tom , L igand and C oord in ation N um ber
P roblem : Indicate the central atom, ligands and coordination number of central atom in the following com­
plex ions. Predict its shape if possible (a) [Zn(OH)4]2' (b) [Ag(NH3)2]+
(c) [Co(H2 0 ) 6l3+
S o lu tio n :
Comnlex ion central ion ligand coordination number shape
[Zn(OH)4P Zn2+ OFT 4 tetrahedral
[Ag(NH3)2]+ Ag+ NH3 2 linear
[CbCHaPM* Co3+ H20 6 octahedral

H N --------------A g +------------ NH
з 3
0
L in e a r

OH
te tra h e d ra l

o c ta h e d ra l

F ig u r e 8 .1 . S tr u c tu r e s o f so m e c o m p le x ions.

EXAMPLE 8.4 W ritin g Form ula o f a C om plex Ion

P ro b le m : Write the formulas of complex compounds CrCl3 . 6H2 0 , CrCl3 . 5NH3,
CrCl3 . 4NH3, and CrCl3. 3NH3. Use the fact that the coordination number of Cr3+ is 6 .
S o lution: In every case there must be six ligands surrounding the central ion Cr3+. Thus the general formula
of the complex ion is [Cr(?)6]3+. In compound CrCl3 . 6H2 0 , six H20 are ligands and three СГ ions are the coun­
ter ions balancing (3+) charge of complex ion. So its formula [Cr(H2 0 ) 6]Cl3. In compound CrCl3 . 5NH3 one СГ
and five NH3 are ligands. The formula of complex ion and compound are [Cr(NH3 )5 Cl]2+ and [Cr(NH3 )5 Cl]Cl2.
Similarly we can write the formulas of complex compounds.
CrCl3 . 4NH 3 =» [Cr(NH3)4Cl2]Cl
CrCl3 . 3NH 3 => [Cr(NH3)3Cl3]

EXERCISE. 8.4 Suppose 1 mol of each of the compounds cited in example 8.4 is dissolved in water. If
some silver nitrate solution is added to each solution to preciplatc AgCl, will AgCl precipitate in each solution?
The so lutio n o f C rC l3 . 3NH3 w ill not ca u se p r e c i p it a ti o n

C om p lex io n s p lay im p o rta n t roles in certa in b io lo g ica l p r o ­

cesses. T w o such com pou n ds are hem in a part o f hem oglobin (the red
pigment in the red corpuscles o f the blood), and chlorophyll (the green coloring
material in plants containing Mg as central atom).
Hemin is a complex compound containing iron as central atom. Its most im­
portant function is carrying oxygen from the lungs to the tissue cells. This is
done through a complex between iron in the hemin and 0 2 is readily released to
the cells where it is used for oxidation o f food.
Hemoglobin + 0 2 —> oxyhemoglobin + H20
Hemoglobin also reacts with CO to form a complex (carboxy hemoglabin)
which is more stable than oxyhemoglobin. If w e breathe a mixture o f CO and
0 2, the CO moleculc.s are preferentially picked up by hemoglobin and our blood
cannot carry 0 2to the tissue cells. Hence the tissue cells starve for lack o f 0 2 .
262 Chapter 8 Ш 1 Ш 1Ш Ш Ш !1 !!1 Ш Ш 1 1 1 П 1 Ш 1 Ш 1 Ш 1 1 Ш 1 1 1 Ш 1 Ш 1 Ш 1 !Ш Ш Ш Ш 1 Ш Ш 1 1 Ш 1 1 Ш Ш 1 Ш Ш Ш 1 1 Ш 1 1 1 1 1 Ш 1 Ш И Ш 1 1 1 1 1 1 1 1 1 1 Ш Ш Ш 1 И 1 Ш !Н Ш 1 1 Ш |1 Ш 1 1 1 Ш 1 1 И Ш Ш |1 1 Ш 1

Therefore CO is a toxic gas. A remedial measure for a man who has breathed
CO is to inject methylene blue directly into his blood stream. CO bonded to the
hemoglobin, is picked up quickly by methylene blue forming another more
stable complex this makes hemoglobin free, from CO for its normal 0 2 transport
function.
Complex ions can be used as catalysts, for dissolving precipitates (AgCl can
be dissolved in NH3 by forming [Ag(NH3)2]+). New uses for complex com­
pounds in industry are being developed.

8.5 OCCURRENCE AND PREPARATION

8.5.1 S C A N D IU M
Scandium is a rare metal which occurs in nature only in combined form in
minerals such as monazite (a complex phospate) and gadolinite (a complex sili­
cate). Not much is known about the element except its vigorous reaction with
water.

8.5.2 TITANIUM
Titanium is a malleable and ductile metal resembling iron. The principal
sources of titanium are rutile (Ti02), ilmenite (FeTi03). Compounds are fairly
widely distributed in nature. It is very difficult to extract the pure metal beacuse
of its great affinity for carbon, oxygen and hydrogen. To prepare titanium, Ti02
and Cl2 are heated to form TiCl4 and then TiCl4 is reduced with magnesium.
Pure titanium is extremely strong and resistant to corrosion (because of protec­
tive surface coatings of oxide and nitride). It is used as structural material in jet
engines, as an additive to iron for hardening and toughening steel.

8.5.3 VANADIUM
Vanadium is a very hard metal (and occurs in a few rather rare minerals such
as patronite (V2S5), vanadite (Pb5V30 i2Cl). The pure metal is very hard to pre­
pare, and since it is used as an additive to steel alloys, it is usually prepared as
ferrovanadium. A few percent of vanadium makes steel tougher, stronger, more
resistant to corrosion. Its most important compound is vanadium pentoxide,
V20 5 which is used as a catalyst in various oxidation reactions, namely in the
conversion of S02 to S03 which is anhydride of sulfuric acid.

8.5.4 CHROMIUM
Chromium is a very hard and inert metal to corrosion (because of impervious
protective oxide coating). Its principal mineral is chromite, FeO. Cr20 3. The re­
duction of chromite with carbon produces an iron - chromium mixture, that is
used in the manufacture of steel.
FeO. Cr20 3 + 4C —> 2Cr + Fe + 4CO
To prepare pure chromium, the chromite is first oxidized by strong heating in
air in the presence of K2C03or Na2C03.
8K2C03+ 4Fe0.Cr20 3+ 702 —* 8K2Cr04 + 2Fe20 3 + 8C02
and then potassium chromate, K2Cr04 is reduced to Cr20 3 with carbon, C,
2K2Cr04 + 2C —» K2C03 + K20 + CO + Cr20 3
||Ш111111!11111111111111111Ш11Ш!1ШШШМ11ШШШ1Ш1Ш1Ш1!Ш1!11Ш11М
ММ1111111!111!1Ш111!111!11!111111ЕШThe Fourth Row Transition Elements 263

finally, Cr2 0 3 is reduced with aluminum in the Goldschmidt reaction :

Cr2 0 3 + 2A1 — > A120 3 + 2Cr
The common oxidation states o f chromium are +2, +3, and + 6 . The solutions
o f chromium ions are colored. Aqueous solutions o f chromium (III) can be ob­
tained by dissolving Cr2 0 3 in acid or base, that is, Cr2 0 3 is an amphoteric oxide.

Cr2 0 3 (s) + 6 H+ — » 2Cr3+ (aq) + 3H20

Cr2 0 3 (s) + 2 0 H ' + 3H20 — > 2Cr(OH)'4

It is well known that Cr3+ forms a complex ion [Cr(H2 0 ) 6]3+ which has violet
color, and hydrolyzes to give an acid solution.
[С г О Ш б Р — > [Cr(H2 0 ) 5 0 H ]2+ + H+
In the +6 oxidation state, chromium is known as the chromates (CrO2') with
bright yellow color, and dichromates (Cr 2Q^) with orange color. When solu­
tions o f chromate ion are acidified the yellow color is replaced by orange color
which indicates the formation o f Cr2 0 2- from Cr04'

2 G O f + 2H+ — > Cr2C^' + H20

The dichromate ion is a very powerful oxidizing agent as shown by the re­
duction potential

Cr20 ^ + 14H+ + 6 e_ — 2Cr 3+ (aq) + 7H20 e° = 1.33 volts.

The solution o f Na 2 Cr2 0 7 and H 2S 0 4 has extremely powerful oxidizing prop­

erties, and is used to clean chemical glassware in the laboratory.

8,5.5 M A N G A N E SE
Manganese is a reddish white, hard, brittle metal. Its most important minerals
are pryrolusite, M n 02, and braunite, Mn 2 0 3, and hausmannite, Mn 3 0 4. It is ex­
tracted from its mineral by reduction with carbon or aluminum. The major use
o f manganese is in the production o f steel, during which manganese reacts with
oxygen and sulfur in the molten iron and prevents the formation o f bubbles
when the iron solidifies (The holes due to the bubbles in the steel weakens its
structure). It also gives special hardness and toughness to the steel.
The common compounds o f manganese are M n 0 2 a dark-brown powder
used in the manufacture o f dry cells as oxidizing agent, and K M n 04, a deep
purple-colored substance used as oxidizing agent and as disinfectant.

8.5.6. IRON
Iron is the fourth most abundant element in the earth’s crust after O, Si, and
Al. This abundance, inexpensive preparation, and its desirable mechanical prop­
erties especially when alloyed with other elements make iron an important ele­
ment in foremost technology. Its important source minerals are hematite
(Fe 2 0 3), limonite (Fe2 0 3 .H 2 0 ) , magnetite (Fe 3 0 4), siderite (F eC 0 3). Pyrite or
fool's gold (FeS2) is also quite abundant but it is not used as a source o f iron
because sulfur is an objectionable impurity in iron. Iron also exists in the ele­
mental state in some meteorites, and in the center o f earth.
M etallic iron is produced by reduction o f oxides o f iron with carbon in a
264 Chapter 8

blast furnace, a huge vertical reactor. The blast furnace is charged from above
with a mixture o f ore, limestone (C aC 03) and coke (C). The coke is ignited at
the bottom o f the furnace by blowing hot air.
2C (s) + 0 2 (g) — > 2CO (g) AH= 53.7 kcal
The carbon monoxide so produced reduces iron oxide to iron
Fe2 0 3 (s) + 3CO (g) — > 2Fe (1) + 3 C 0 2 (g)
The lime (CaO) combines with the sand (S i0 2) and other impurities in the ore
to form a molten lava-like slag (C aS i03), which floats on the molten iron and
protects it from oxidation by incoming oxygen.
CaO (s) + S i0 2 (s) —» CaSi0 3 ©
The crude product o f the blast furnace (called pig iron) contains about 4 % C,
2 % Si, and traces amount o f P, S, and Mn. The impure iron is refined into
steel by burning out the impurities to leave small controlled amounts o f С (0.1
% to 1.5 %). During this process usually manganese, vanadium, and chromium
are added to the steel to obtain desired properties. For example stainless steel
contains (70-90) % Fe, (2-20) % Cr, and (0.1-0.7) % C.

8.5.7 COBALT
Cobalt is a hard silvery-white metal, occurs in nature as linnaeite, Co 3 S4 and
arsenide, CoAs2. To prepare Co, the ores are first roasted to CoO which is then
reduced with С to Co. It is used to produce blue color in glass and ceramics.

8.5.8 NICKEL
The principal minerals o f nickel are pentlandite and gamierite. Since most
ores are very poor in nickel content, it is enriched by flotation. In this process
froth: m ass o f sm a ll b u b ­ the ore is ground up and then agitated briskly with water to which wetting
b les; foam agents have been added. The impurities are wet by the water and hence sink,
sm elt: to w e lt (o re) se p a r­ whereas the fine particles o f mineral are not wet by water and get carried o f with
ate (m e ta l) fro m o re b y
the froth. The concentrated ore is then roasted to form nickel oxide, which is re­
d o in g this.
duced to nickel by carbon or hydrogen. The pure metal can be prepared by re­
fining the final product electrolytically.
The properties o f nickel resemble those o f cobalt, except nickel is more inert
to chemical oxidation. It is used as an additive in iron alloys to increase their
strength and corrosion resistance and as a catalyst for hydrogenation reactions.
(The addition reaction o f Fl2 to organic compounds containing double and triple
carbon to carbon bonds.) It is also used for plating steel.

8.5.9 COPPER
Copper occurs as free metal as w ell as in compounds o f oxides or sulfides.
Its chief minerals are chalcocite, (Cu 2 S), chalcopyrite (CuFcS2), cuprite (Cu2 0 ),
malachite [Cu(OF12). C uC 03].
To prepare the metal, the minerals are concentrated by flotation (see nickel),
roasted in air and then smelted. The simplified equation representing these pro­
cesses is
2CuFeS 2 (s) + 5 0 2 (g) — > 2Cu (s) + 2FeO (s) + 4SO z (g)
The copper obtained from this process is about 99 % pure. But it must be
iiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiitiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiii The Fourth Row Transition Elements 265

purified further for most uses, especially those involving electrical conductivity.
This can be done best in a C uS0 4 electroly-tic cell as described earlier.
Metallic copper is malleable, ductile and a very good conductor o f heat and
electricity. Except for silver, it has lowest, electric resistance and therefore used
extensively in wires, switches. Since it has a reduction potential o f 0.34 V
(Cu2+ to Cu), it is a poorer reducing agent than hydrogen and does not dissolve
in acids unless they contain oxidizing ions such as N 0 3 , SO2"

Cu (s) + H+ — > no reaction.

Cu (s) + 4H+ (aq) + 2NO'3 (aq) — ► Cu2+ (aq) + 2 N 0 2 (g) + 2H20
Cu (s) + 4H+ (aq) + S 0 24(aq) — * Cu2+ (aq) + S 0 2 + 2H20
It is mainly used in electrical industry, and in making alloys, such as brass
(zinc plus copper), bronze (tin plus copper).

8.5.10 ZINC
Zinc is a hard bluish metal. It occurs as calamine (Z n C 03), zincite (ZnO), and
zinc blende (ZnS). The metal is extracted by roasting the ore and then reducing
the oxide with carbon.The reactions are
2ZnS (s) + 3 0 2 (g) — > 2ZnO (s) + 2 S 0 2 (g)
ZnO (s) + С (s) — » Zn (s) + CO (g)

Since the second reaction takes place over 1200°C (above the boiling point o f
zinc, 907°C), the metal is produced in the vapor state, which is then condensed
to give fine powder known as zinc dust.
Zinc has quite good metallic properties, and is a moderately active metal. It
reacts with acids to produce H2, zinc can even reduce water to hydrogen at high
temperatures. In air it tarnishes slightly because o f the formation o f a very thin
protective coat o f basic zinc carbonate.
Zinc, its oxide and hydroxide are amphoteric.
Zn (s) + 2H+ (aq) — > Zn2+ (aq) + H 2
Z n (s) + 2HO" — > ZnO^'(aq) + H 2 zincateion
ZnO (s) + 2H+ (aq) — > Zn2+ (aq) + H20

ZnO (s) + 2 0 H ' — > ZnO^(aq) + H20

It is a very good reducing agent in both acidic and basic solutions.

Zn (s) —-» Zh2+ (aq) + 2e- (acidic solution) e° = + 0.76 V

Zn (s) + 4 0 H ~— > Zn(OH)2' + 2e_ (basic solution) e° = + 1.22 V

It forms many complex ions with ligands, especially with NH 3, CNT and OH'
In all these complex ions its coordination number is four.
. It is used in alloys (brass, bronze...), and galvanizing iron (made by dip­
ping iron into molten zinc so as to give a thin adhering layer o f zinc over iron).
Zinc sulfide (ZnS) is used as white pigment, as luminescent material in many
television tubes. Zinc phosphide (Zn 3 P2) is used as rat poison. Zinc sulfate
(Z n S 04) is used as m ordant.
266 Chapter 8 I И Ш Ш Ш Ш Ш 1
Ш Ш Ш Ш Ш Ш Ш Ш Ш Ш ................................. ............................................................. I I I I H ............................................... ншмшшш......... шшшшш......

SOME NEW TERMS

Blast furnace : A vertical, high furnace for car­ of Cr2 0 3 by aluminum.
bon reduction of iron ores. Hydrogenation reaction : a reaction in which
Complex ion : a combination of a central metal H2 adds across double or triple bonds.
ion and its surrounding ligands. Ligand : An atom, ion or molecule which acts a
Coordination number : the number of ligands Lewis - base.
which attach themselves directly to the central metal Roasting : The process of heating a metal ore
in a complex. in air, usually used to convert sulfides and carbonates
Flotation : A method for enrichment of metal to oxides.
ores. The finely crushed ore is mixed with a suitable Slag : Unwanted material produced during smelt­
liquid and water in a large tank. Agitation of the ing.
mixture with air produces a froth containing mineral Smelting : A high temperature - reduction pro­
particles, which is skimmed off. cess in which a free metal is obtained from its con­
Goldschmidt reaction ; The reduction reaction centrated and purified ore.

REVIEW QUESTIONS AND PROBLEMS

8.1 What is a transition metal ? Why are the ele­ mg.
ments with atomic numbers 21 to 30 called 3d- (a) roasting zinc blend.
transition elements? (b) dissolving zinc in basic solution
(c) dissolving copper in H2 S 0 4 solution
8.2 Ferrocyanide ion is a complex ion in which co­ (d) preparation of iron in blast furnace
ordination number of ferrous ion is six. Write its
structural formula, and predict its shape. 8 .8 What are the raw materials used in blast fur­
nace? What is the function of each component?
8.3 Why does NH 3 act as a ligand but NH* does
not? 8.9 What is "the cathodic protection"? (Recall activ­
ity of metals).
8.4 What are the oxidation numbers of transition
elements in the following complex compounds or 8.10 Why is CO toxic?
ions?
(a) C u C f (b) Zn(NH3)2+ 8.11 Write a balanced equation to show the dis­
solving of each of
(c)Cr(H20 ) f (d) [Cr(NH3)6]Cl3
Cu(OH)2, Zn(OH)2, Co(OH) 2 in NH3
(e) FeSCN2+ (SCN‘ is tiocyanate ion)
solution. Explain, using Le Chatelier's principle
8.5 Why are most transition metal compounds col­ why the hydroxides of metals precipitate by the addi­
ored? tion of an acid to these solutions.

8 .6Identify each of the following terms (a) com­ 8.12 Decribe the purification of Cu by electrolytic
plex ion, (b) ligand, (c) pig iron, (d) steel, (e) flota­ method.
tion process, (0 Goldschmidt reaction, (g) galvaniz­
ing, an impervious protective coat of oxide. 8.13 Write the balanced equation representing au-
toxidation of Mn3+ to M n0 2 and Mn2+ in acid solu­
8.7 Write balanced equations for each of the follow- tion.
iiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiii The Fourth Row Transition Elements 267

8-14 a saturated solution of Mn(OH) 2 has a pH of The dichromate is reduced to Cr3+. Find the percent­
10. What is Ksp for Mn(OH)2? 5xl0'13 age by mass of manganese in the steel. 10.56 %

8.15 How many ml of 0.02 M KMn0 4 solution is 8.20 How many kg of pig iron containing 4% of
needed to convert all the SO2" ions in 30 ml 0.02 M impurity can be prepared from 1 ton of hematite ore
Na2 S 0 3 into SO2' in basic solution? (Mn04" is re­ which contains 40% gang (the substances other than
duced to M n02) 20 mL hematite). 2 9 1 .7 kg

8.16 a i _2 mol mixture of Fe2+ and Fe3+ ions is 8 .2 1How many kg of copper may be prepared from
completely oxidized by 200 mL of 0.5 M KMn0 4 1 ton of chalcopyrite ore that is 20% pure? Assume
solution in acidic solution. Find the mole number of that the efficiency of the reaction is 90%.
Fe3+ in the original mixture. 0.7 m ol 6 2 .3 kg
*8.22 a 100 mL of HC1 is allowed to react with
8.17 A 32.2 g sample of brass can completely react zinc metal. The H2 gas so obtained is used to reduce
with 200 mL of 2 M HC1 solution. What is the CuO to metallic copper. During this reduction the
mole percentage of copper in the alloy? 60 % mass of CuO is decreased by 0.8 g. Find the molari­
ty of the acid solution. 1 M
8.18 How many liters of H2 measured at 0°C and 2
atm will be produced by the reaction of 0 . 1 mol zinc *8.23 A 10 g alloy of aluminum and zinc is dis­
and 30 mL of 1 M NaOH? 0.168 L solved in concentrated KOH solution. The hydrogen
produced has a volume of 4.92 L at 27°C and 786
*8.19 A 0.2 g sample of steel is dissolved in acid mm Hg when collected over water. Find the percent­
solution. The manganese ion is oxidized to perman­ age composition of the alloy. PH 0 = 26 mm Hg at
ganate ion. The permanganate ion is then reduced to 27°C Al = 27 Zn = 65
Mn2+ by addition of 50 mL 0.06 M Fe2+ solution. 11 .5 % A l, 8 8 .5 % Zn
The excess Fe2+ remaining behind is completely re­
acted with 18 mL of 0.01 M dichromate solution.

SELF TEST

1 - In which species does vanadium have the highest state.

oxidation number? B) low ionization energy, and multiple oxidation
A) VC12 B) VOCl2 C) V 0 2+ state.
D) NILVOa E) V20 3 C) low ionization energy, low melting point.
D) high electronegativity, low melting point.
2 - Which is wrong about the element 2 3 X? E) high number of valence electrons, colorless
A) It is in the 4th period. compounds.
B) It is in the 5 В group.
5- The action of the metals X, Y, Z on HC1, NaOH,
C) It is a 3d-transition metal.
and on H N 0 3 are given in the following table. The
D) Its highest oxidation state is (+3).
plus sign indicates the reaction.
E) It has three half -filled atomic orbitals.

3 - Which element has an electron configuration m etal HC1 N aO H H N 03

ending with s 1 d5
X + + +
A) 21X B) 22Y C) 23Z D) 24Q E) 25R
Y - - +
4 - The transition metals are characterized by
A) high ionization energy and single oxidation Z + - +
268 Chapter 8 ш и н ш п ............................................. Ш Ш П Ш Ш ............................ I I I I I .......... ....... 1111...................... I l l ............... I

Which metals do X, Y, and Z represent 12 - Which is the Goldschmidt reaction

x Y Z A) 2A1 + 6HC1 2A1C13 + 3H2
A) Zn Mg Cu В) 4A1 + 3 0 2 2A120 3
B) Zn Cu Mg С) A120 3 + 6K 3K20 + 2A1
C) Cu Zn Mg D) A120 3 + 6NaOH 2Na3A103 + 3H20
E) Mg Zn Cu E) 2A1 + Cr20 3 A120 3 + 2Cr
E) Mg Cu Zn
13 - A 24.5 g alloy of Mg, Zn and Cu elements is
6 - Which is wrong for K3 [Fc(CN)6] first treated with concentrated NaOH solution. The
A) This is a complex compound. solid residue which has a mass of 16.4 g is then
B) CN' is a ligand. treated with concentrated HC1 solution. If 12.8 g of
C) The coordination number of Fe is 8 . solid metal remains undissolved, the mole number of
D) The central atom in the complex ion is iron. Mg in the alloy is
E) It is a colored substance. Mg = 24, Zn = 65, Cu = 64
A) 0.10 B) 0.15 C) 0.20
7 - If each of 1 mol of the following solutes is
D) 0.34 E) 0.50
completely dissociated in a liter solution, which has
the highest [СГ]? 14 - Chromium metal may be prepared by reduction
A) [Cr(H20 ) 6]Cl3 of chromium (III) oxide by aluminum. How many
B) [Co(NH3 )5 C1]C12 grams of chromium may be prepared from a mixture
C) [Co(NH3 )4Cl2 ]Cl of 228 grams of aluminum and 228 grams of chro­
D) [Zn(NH3)4]Cl2 mium (III) oxide? Al = 27, Cr = 5 2 , О = 16
E)Na[Cr(Cl)4 (H20 ) 2] A) 26 B) 52 C) 78 D) 156 E) 208

8 - An 840 g piece of red- hot iron becomes 904 g 15 - In the electrolytic refining process of crude
when passed through steam. If the product is Fe3 0 4, copper, crude copper is used as anode and copper (II)
the mass percentage of iron oxidized is Fe = 56 sulfate solution is used as electrolyte, and pure cop­
A) 17 B) 20 C) 23 D) 27 E) 3 per is used as cathode. Which will be the mass of Cu
transferred from anode to cathode if 96.5 Amp cur­
9 - How many grams of CuS0 4 can be prepared at rent is passed through the electrolytic cell for 1 0 0 0
most, when 50 g of H2 S 0 4 solution that is 49% seconds? Cu = 64 g/mol
H2 S 0 4 by mass acts on copper? A) 16 g B) 32 g C) 64 g
CuS0 4 = 160, H2 S 0 4 = 98 D) 96 g E) 128 g
A) 10 B) 20 C )30 D) 40 E) 50
16 - A 10 g sample of brass produces 2.24 L H2
10 - Which is not a raw material used directly in when allowed to react with excess H2 S 0 4. The mass
percentage of copper in the brass sample is
the production of iron in blast furnace?
Cu = 64, Zn = 65, S = 32, 0 = 16
A) F e ^ (hematite)
A )40 B )35 C )30 D )25 E) 20
B) CaC0 3 (limestone)
C) S i0 2 (sand) 17 - A 50 g alloy of magnesium and zinc produces
D) FeS2 (pyrite) 6.72 L H2 at STP when excess amount of concen­
E) С (coke) trated NaOH is added. The percentage of magnesium
11 - The oxidation states of iron in in the alloy is
Fe4 [Fe(CN) 6] 3 are Mg = 24, Zn = 65
First iron second iron A) 19.5 % B) 39 % C) 61 %
A) 4 + 3+ D) 80.5 % E) 97.5 %
B) 2+ 3+
C) 3+ 3+ 18 - In the preparation of zinc from calamine
D) 2+ 2+
(ZnC03), the ore is first decomposed to ZnO which
E) 3+ 2 +
||||||||||1ш111шшш1ш11ш|||||||||||||1111111!111111111111111шшш1ш11ш11ш11шшш111шш11ш111ш1 The Fourth Row Transition Elements 269

is then reduced to Zn by C. How many kg of zinc 20 - The metal X may be prepared according to the
metal can be prepared from 1 ton of ore containing reaction
25% ZnC0 3 and 18 kg of C? Zn = 65, С = 12 0=16 X 2 0 3 + 3CO — » 2X + 3C 0 2
A) 130 B) 97.5 C) 65 D) 32.5 E) 13 If 64 g of X 2 0 3 may be completely reduced by 1.2
mol of CO gas, and the X has 30 neutrons in its nu­
19 - How many mL of 0.05 M KMn0 4 solution is cleus, the number of electrons in its 3d orbital is
required to oxidize 25 mL of 0.1 M FeS0 4 to Fe2 0=16 g/mol
(S 0 4) 3 in H2 S 0 4 solution? (Manganese is reduced to A) 4 B) 5 C) 6 D) 7 E) 8
Mn2+)
A) 10 B) 20 C) 50 D) 100 E) 250
 ii ii ii i i i i i i i i i i i i i i i i i i i i i M i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i M i i i i i i i i i i i i i i i i i i i i N i M i i i i i i i i i i i i i i i i i i i i i i i i i i i i N N H i i i i i i i i Appendix 271

APPENDIX I
SOLUBILITY PRODUCT
CONSTANTS
B ro mi des Hydroxides Sul t a t e s

PbBr2 4.6 X 10“ 6 AI(OH)3 5 x 1 0 “ 33 BaS04 1.5 X 10“ 9

H g 2C r 2

cn
1 .3 X 10-” B a ( O H) 2 10 3 CaS04 2.4 10“ 3

о
X
X

AgBr 5.0 X 1 0 “ 13 Cd( OH) 2 2.0 x 1 0 “ 14 PbS04 1.3 X 10“ 8

Ca ( OH) 2 1.3 x 1 0 “ 6 Ag:S 0 4 1.2 X 10 “ 3
Car bo na tes
Cr (OH), 6. 7 x 1 0 " 31 SrS04 7.6 X 10"7

ВаСОэ 1.6 X 10 “ 9 Co( OH) 2 2. 5 x 1 0 “ 16

Sullides
CdC03 5. 2 X 1 0 “ 12 Co( OH) 3 2. 5 x 1 0 43

CaC03 4.7 10“ 9 Cu( OH) 2 1 6 X 1 0 “ 19

X B i 2S 3 1.6 X 1 0 “ 72
CuC03 2. 5 X 10 10 Fe( OH) 2 1 . 8 x 1 0 “ 13 CdS 1.0 X 1 0 “ 28
FeC03 2. 1 X 10“ " Fe ( OH) , 6 X 1 0 “ 38 CoS 5 X 10 22
PbC03 1.5 X 1 0 “ 15 Pb( OH) 2 4.2 x 1 0 “ 15 CuS 8 X 1 0 “ 37
MgC03 1 X 1 0 “ 13 Mg( OH) 2 8.9 x 1 0 “ 12 FeS 4 X 1 0 “ 19
Mn( OH) 2 2 x 1 0 “ 13
CD

MnC03
CO

X 10“ ” PbS 7 X 1 0 “ 29
H g 2C 0 3 9.0 X 1 0 “ 12 Hg( OH)2 (HgO) 3 x 10 26 MnS 7 X 1 0 “ 16
NiC03 1.4 X 1 0- 1 Ni (OH) 2 1.6 X 1 0 “ 16
HgS 1.6 X 1 0 “ 34
А д 2С О э 8.2 X 1 0 “ 12 AgOH ( A g 20 ) 2. 0 x 1 0 “ 8
Ni S 3 X 1 0 “ 21
со
C\i

SrC03 7 1 0 “ '° Sr ( OH) 2 10“4

X

X
A g 2S 5.5 X 1 0 “ 31
ZnCQ3 2 X 10“ ’° S n( OH) 2 3 x 10 27
SnS 1 X 1 0 “ 26
Zn( OH) 2 4. 5 x 1 0 “ 17
ZnS ' 2. 5 X 1 0 “ 22
Chlorides
Iodi des
Mi scel laneous
PbCI2 1 .6 X 10“ 3
Hg ; CI2 1.1 X 1 0 “ 18 Pbl2 8.3 x 1 0 “ 9
NaHC03 1.2 X 10 3
AgCl 1.7 X 1 0 “ 10 H g 2l 2 4. 5 x 1 0 - 20
kcio 4 8.9 X 10“ 3
Agl 8.5 x 1 0 “ 17
K 2[PtCI6] 1.4 X 10'*
Chr omat es
A g C 2H30 2 2. 3 X 10“ 3
Ox a l a t e s
BaCr04 8.5 X 1 0 “ 11 AgChl 1.6 X 10 14
PbCr04 2 X 10 '“ B a C 20 4 1.5 x 1 0 “ 8 AgCNS 1.0 X 1 0 “ 12
H g 2C r 0 4 2 X 10 9 C a C 20 4 1.3 x 1 0 “ 9
A g 2C r 0 4 1.9 X 1 0 “ 12 P b C 20 4 8. 3 x 1 0 “ 12
SrCr04 3.6 X 10“ 5 M g C 20 4 8.6 x 1 0 “ 3
A g , C 20 4 1.1 X 10“ "
Fl uor i de s
S r C 20 4 5.6 x 1 0 “ 8

BaF2 2.4 X 10"5 Phosphat es

CaF2 3.9 X 1 0 ' 11
PbF3 4 X 10“ 8 B a , ( P 0 4)2 6 X 1 0 “ 39
MgF2 8 X 10“ s C a 3( P 0 4)2 1 . 3 x 1 0 “ 32
SrF2 7.9 X 1 0 " 10 P b 3( P 0 4)2 1 X 10 34
Ag,P04 1 . 8 x 1 0 “ 18
S r 3( P 0 4)2 1 X 1 0 “ 31
272 Appendix и н н н м н н н и ш н и н ш ш н н ш н и н и и и п н и ш и н и ш н и н ш и и м н и н и ш и н и ю п и н н и п и и ш ш и ш н н и ш ш н и н н и н н п н и ш ш и п ш и ш ш н п и ш и и

APPENDIX II
IONIZATION CONSTANTS OF
ACIDS AND BASES AT 25 °C
M o n o p rcitic A cid s

HCjH,02 H4 + 1.8 10 ' 5

О
О
a c e tic X

b e n z o ic HC,H.O, =^=* H4 + C,H,Oj 6.0 X 1 0 '5

c h lo ro u s HCIOj *=* H4 + CIOJ 1 .1 X 1 0 '3
c y a n ic HOCN H4 + OCN” 1 .2 X 1 0 '4
to rm ic HCHO,*=* H’ + CHOJ 1.8 X 1 0 '4
h y d ra z o ic HN, H' 4 NJ 1.9 X 10 ' 5
h y d ro c y a n ic HCN = * H* 4 CN' 4 .0 X 1 0 ' 10
h y d ro flu o ric HF 5==i H 4 4 F~ 6 .7 X 1 0 '4
h y p o b ro in o u s HOBr H 4 4 O B r' 2 .1 X 10 ' 4
h y p o c h lo ro u s HOCI H4 4 ocr 3.2 X 1 0 '*

n itro u s UNO, H4 4 NOJ 4 .5 X 10 "4

P o ly p ro tic A cid s

a rs e n ic H ,A s 0 4 H4 4 h 2A so; К. i — 2 5 х 10' 4
H 2 A s 0 4'— > H 4 4 H A s O j'
- к. г = 5 6 х 1 0 "•
1
(Л
»u

H A s O j' = 3 х 1 0 ,J
>
О

H4 4 к .,
c a rb o n ic C 02 4 H jO 5 ^ 5 H 4 4 HCO,' к., = 4.2 х 10 ' 7

H C O , 5--5. H 4 4 c o l К .г 4.8 х 10 11

h y d ro s u ltu ric H jS 5 = 5 H 4 4 H S ' к., = 1 .1 х 1 0 ' 7

HS H 4 4 S 2' К .г = 1 . 0 10 х 14

o x a lic H 2 C 2 0 4 5=5 H J 4 h c 2 o ; К .г = 5.9 х 10 3

H C jO i v=-— H 4 4 C ; O j ' К.1 = 6.4 х 1 0 ' 5

p h o s p h o ric h ,p o 4 H 4 4 h 2 p o 4- к., = 7.5 х 10 ' 5

H 2 P 0 4 5=5 H 4 4 HPO j ‘ К .г = 6 .2 х 10 *
н р о Г 5=5 H 4 4 р о Г К = 1 х 1 0 13

p h o s p h o ro u s H ,P O , 5=5 H 4 4 H 2 PO,' к., х 10 ' 1.6 3

(d ip ro tic ) H jP O ji 5 = 5 H 4 4 н 2 р о Г К .г = 7 х 10 " 7
s u lfu ric h 2s o 4 5 = H4 4 hso; s tro n g
H S O i 5 = 5 H 4 4 S O j" К .г = 1.3 х 10 3

s u lfu ro u s S02 4 H jO 5= 5 H 4 4 h s o ; к.. = 1.3 х 10 " 2

rx i-1
</)

HSO; —
О

H4 4 К .г — 5.6 х 10 *

B ases

a m m o n ia N H , 4 H 20 * = * N H 4 4 O H “ 1.8 X 1 0 ' 5

a n ilin e C 6 H ,N H 2 4 H 20 C kH ,N H j 4 O H " 4 6 x 1 0 " 10

d im e th y la m in e (C H ,)2NH 4 H 20 =r=^ (C H ,) 2 N H 24 4 O H " 7.4 x 1 0 " 4

O)
CO

N 2 H 4 4 H 20 * = * N 2 H? 4 O H '
X

h y d ra z in e 1 0 ' 7

m e th y la m in e C H ,N H 2 4 H 20 C H ,N H , 4 O H " 5.0 x 1 0 ' 4

p y rid in e C ,H ,N 4 H 20 C 5H5NH4 4 OH" 1.5 x 1 0 9

trim e th y la m in e (C H ,),N 4 H 20 * = * (C H ,),N H 4 4 O H ' 7.4 x 1 0 "’