JEE-11-Chemistry-Physical Chemistry 3 PDF

CONTENTS
PHYSICAL CHEMISTRY-3 Pages
 Chemical Equilibrium – Theory 1 – 11

 Ionic Equilibrium – Theory 12 – 21
 Some Basic Concepts of Chemistry – Theory 22 – 39
 Chemical Equilibrium – Exercise – 1 A1 – A9
 Ionic Equilibrium – Exercise – 1 A10 – A18
 Some Basic Concepts of Chemistry – Exercise – 1 A19 – A26
 Chemical Equilibrium – Exercise – 2 B1 – B3
 Ionic Equilibrium – Exercise – 2 B4 – B6
 Some Basic Concepts of Chemistry – Exercise – 2 B7 – B9
 Chemical Equilibrium – Exercise – 3 C1 – C13
 Ionic Equilibrium – Exercise – 3 C14 – C27
 Some Basic Concepts of Chemistry – Exercise – 3 C28 – C39
 Chemical Equilibrium – Exercise – 4 D1 – D4
 Ionic Equilibrium – Exercise – 4 D5 – D11
 Some Basic Concepts of Chemistry – Exercise – 4 D12 – D14
CHEMICAL EQUILIBRIUM
1. INTRODUCTION 2.3 Concept of Chemical Equilibrium
Equilibrium represents the state of a process in which the

proprties like temperature, pressure, concentration of the
system do not show any change with the passage of time.
If the opposing processes involve only physical changes,

the equilibrium is called physical equilibrium. If the
opposing processes involve chemical changes, i.e., the
opposing processes are chemical reactions, the equilibrium
is called chemical equilibrium.
2. EQUILIBRIA IN CHEMICAL PROCESSES

x It is the state of minimum Gibb’s energy
2.1 Reversible Reactions
x dG = 0 and 'G = 0 at this state
A reaction in which not only the reactants react to form the
products under certain conditions but also the products x Rate of forward reaction = Rate of backward reaction
react to form reactants under the same conditions is called
a reversible reaction. In other words a reaction which takes x This equilibrium is dynamic and stable in nature
place not only in the forward direction but also in the
backward direction under the same conditions is called a Dynamic Nature of Chemical Equilibrium
reversible reaction.
In the Haber’s process, starting with definite amounts of
A reversible reaction between A and B to form C and D is N2 and H2 and carrying out the reaction at a particular
represented as : temperature, when equilibrium is attained, the
concentrations of N2, H2 and NH3 become constant. If the
ZZX C + D experiment is repeated by taking deuterium (D2) in place of
A + B YZZ
H2 but with the same amounts and exactly similar conditions
2.2 Irreversible Reactions as before, equilibrium is attained containing D2 and ND3 in
place of H2 and NH3 but in the same amounts. Now, if the
If a reaction cannot take place in the reverse direction, i.e., two reaction mixtures are mixed, then after some time, it is
the products formed do not react to give back the reactants found that the concentrations of ammonia and hydrogen
under the same conditions, it is called an irreversible are same except that now all forms of ammonia (i.e., NH3,
reaction. NH2D, NHD2, ND3) and all forms of hydrogen (i.e., H2, HD,
2
) are present. This shows that at equilibrium, the reaction
A + B
o C+D is still going on, i.e., equilibrium is dynamic in nature.
1
't o0
Units of rate : conc/time or mol/Ls
3.2 Overall rate of a reaction
aA + bB lcC
l + dD
Overall Rate =
– (1/a) 'A/'t = – (1/b) 'B/'t = + (1/c) 'C/'t = + (1/d) 'D/'t
Overall rate :
Rate of forward reaction – Rate of backward reaction
“At equilibrium the overall rate of a reversible reaction
becomes zero”.
4. EQUILIBRIUM CONSTANT (K)
2.4 Characteristics of Chemical Equilibrium

4.1 Law of Mass Action
(i) At equilibrium, the concentration of each of the reactants
and the products becomes constant. The rate of a reaction is proportional to the product of the
active masses of the reactants, each raised to the power
(ii) At equilibrium, the rate of forward reaction becomes equal equal to its stoichiometric coefficient as represented by
to the rate of backward reaction and hence the equilibrium the balanced chemical equation.
is dynamic in nature.
(iii) A chemical equlibrium can be established only if none of aA + bB + cC + ......

o Products
the products is allowed to escape out or separate out as a
Rate of reaction v [A]a [B]b [C]c .....
solid.
Law of Chemical Equilibrium is a result obtained by applying
e.g. if CO2 gas escapes out in case of decomposition of
the Law of Mass Action to a reversible reaction in
CaCO , the reaction will no longer remain reversible.
equilibrium.
Similarly, the reaction is irreversible if one of the products
separates out as solid, ZZX C + D
A + B YZZ
o AgCl p + KNO
AgNO3 + KCl Rate of the forward reaction v [A] [B] = kf [A] [B]
(iv) Chemical equilibrium can be attained from either direction, Rate of the backward reaction v [C] [D] = kb [C] [D]
i.e., from the direction of the reactants as well as from the
At equilibrium,
direction of the products.
Rate of forward reaction = Rate of backward reaction
3. RATE OF A REACTION
[C][D] kf
k f [A] [B] k b [C] [D] or K
[A][B] kb
Average Rate = Change in concentration/Time taken
= 'c/'t
At constant temperature, as kf and kb are constant, therefore,
'c = Final Concentration – Initial concentration
kf
3.1 Instantaneous rate k b = K is also constant at constant temperature and is
called ‘Equilibrium constant’.
Lim 'c/'t = dc/dt
2
The product of the molar concentrations of the products,

each raised to the power equal to its stoichiometric 4.4 Reaction Quotient (Q)
coefficient divided by the product of the molar
concentrations of the reactants, each raised to the power aA + bB lcC
l + dD
equal to its stoichiometric coefficient is constant at constant
Q = [C]c [D]d/ [A]a [B]b
temperature and is called Equilibrium constant.
Q > Kc : Reaction will tend towards backward direction
4.2 Characteristics of Equilibrium Constant Q > Kc : Reaction will tend towards forward direction
Q > Kc : Reaction will be at equilibrium
(i) The value of the equilibrium constant for a particular
reaction is always constant depending only upon the
temperature of the reaction and is independent of the Note :
concentrations of the reactants with which we start or the
Q is a variable which always approaches Keq which is a
direction from which the equilibrium is approached.
constant.
(ii) If the reaction is reversed, the value of the equilibrium
constant in inversed.
(iii) If the equation (having equilibrium constant K) is divided 4.5 Calculating Equilibrium Concentrations
by 2, the equilibrium constant for the new equation is the
Suppose we are given the following data :
square root of K (i.e., K ).
1. The balanced reaction and value of Kc
(iv) If the equation (having equilibrium constant K) is multiplied 2. The initial concentration of the reactants, or the initial moles
by 2, the equilibrium constant for the new equation is the
3. Volume of the container
square of K (i.e., K2)
And we need to find the final equilibrium concentration of
(v) If the equation (having equilibrium constant K) is written the reactants and products. Then we can follow the
in two steps (having equilibrium constant K1 and K2) then following steps :
K1 × K2 = K.
Step-1
(vi) The value of the equilibrium constant is not affected by the Write down the balanced chemical equation for the reaction
addition of a catalyst to the reaction.
Step-2
This is because the catalyst increases the speed of the
Under every reactant and product, write down the initial
forward reaction and the backward reaction to the same
moles/concentration
extent.
Step-3
4.3 Extent of Reaction Subtract the amount reacting and add the amount produced
in terms of a variable x and note down the equilibrium
High value of Kc (Kc > 103) o At equilibrium reaction is concentration in terms of x. If we are dealing in moles then
forward dominant we will need to divide the moles by volume to obtain
Low value of Kc (Kc < 10–3) o At equilibrium reaction is concentrations.
backward dominant Step-4
Moderate value of Kc (between 10 and 10 ) o At
3 –3
Substitute the equilibrium concentration in the expression
equilibrium neither direction dominates of Kc and equate it to the value of Kc.
Step-5
Solve the above equation and calculate the value of x and
in case of multiple solutions select the value which is
sensible from reaction point of view. Then back substitute
3
the value of x in the equilibrium concentration expression

and obtain the actual value of the same. POINTS TO REMEBER
Whether the reaction is exothermic or endothermic on
4.6 Equilibrium constant Kp increasing the temperature, it will tend towards
endothermic direction.
aA + bB l cC + dD
Kp = (PCc × PDd)/ (PAa × PBb) 5. HOMOGENOUS EQUILIBRIA
where PC, PD, PA, PB are partial pressures of A, B, C and D
respectively. Reactions in which all reactants and products are in the
same phase Homogenous Reactions can further be divided
Kp = Kc (RT)'n into three sub-categoreis :
R = 0.0821 L atm/mol–K 5.1 Those reactions where gaseous moles increase
('n = +ve)
4.7 Relationship of Keq and 'G PCl5 (g) lPCl3 (g) + Cl2 (g)
5.2 Those reactions where gaseous moles remain the same
For any reaction :
('n = 0)
'G = 'Gº + RT InQ Where Q is the reaction quotient.
H2 (g) + I2 (g) l 2HI (g)
At equilibrium 'G = 0 5.3 Those reactions where gaseous moles decrease
'Gº = –RT lnKeq = – 2.303RT log10Keq ('n = – ve)
where K eq is generally taken as Kp. It depends on the 2NO2 (g) l N2O4 (g)
definition of standard values to define 'Gº.
If the standard active masses are taken as 1 M each then
6. DEGREE OF DISSOCIATION, D
we will take Keq = KC and if they are taken as 1 atm each
It is defined as the fraction of molecules dissociating. For
then we will take Keq = Kp.
example, if 100 molecules are present and only 40 dissociate
then the degree of dissociation is 0.4 or 40%.
4.8 Dependence of Keq on temperature
7. HETEROGENEOUS EQUILIBRIA
Van’t Hoff Equation :
ln (K2/K1) = ('H/R) (1/T1–1/T 2) or Category of reactions where various phases/states exist in
log10 (K2/K1) = ('H/2.303R) (1/T1–1/T2) the same reaction.
Exothermic Reactions In presence of gases the activity of solids and excess liquids
is constant. Therefore we can assume the active masses of
'H = negative solids and excess liquids as constant.
On increasing the temperature the equilibrium constant will
CaCO3(s) l CaO(s) + CO2(g)
decrease i.e. The reaction will become more backward
dominant. Kc = [CO2]
Endothermic Reaction Kp = PCO
2
'H = possitive
On increasing the temperature the equilibrium constant will 8. LE CHATELIER’S PRINCIPLE
increase. The reaction will become more forward dominant.
If a distrubance is introduced in an equilibrium mixture it
will behave so as to undo the distrubance and re-establish
equilibrium.
4
8.5 Effect of a Catalyst

8.1 Effect of Change of Concentration
If in a reaction in equilibrium, the concentration of any A catalyst increases the rate of the chemical reaction by
reactant is increased, the equilibrium shifts in the forward making available a new low energy pathway for the
direction. On the other hand, if the concentration of any conversion of reactants to products. It increases the rate
product is increased, the equilibrium shifts in the backward of forward and reverse reactions that pass through the same
direction. The reverse happens if the concentrations are transition state and does not affect equilibrium. Catalyst
decreased. lowers the activation energy for the forward and reverse
reactions by exactly the same amount. Catalyst does not
8.2 Effect of change of temperature affect the equilibrium composition of a reaction mixture. It
does not appear in the balanced chemical equation or in
Exothermic reactions are favoured by low temperature the equilibrium constant expression.
whereas endothermic reations are favoured by high
temperature. eg contact process,
8.3 Effect of change of pressure 2SO2 (g) O2 (g) U 2SO3 (g); Kc 1.7 u1026
Low pressure favours those reactions which are Practically the oxidation of SO2 to SO3 is very slow. Thus,
accompanied by increase in total number of moles and high platinum or divanadium penta-oxide (V2 O5) is used as
pressure favours those reactions which take place with
catalyst to increase the rate of the reaction.
decrease in total number of moles. However, pressure has
no effect on an equilibrium reaction which proceeds with 8.6 Effect of adding an inert gas to a reaction mixture
no change in total number of moles. in equilibrium.
8.4 Effect of change in volume

(a) If the reaction takes place at constant volume addition of
The effect of decrease of volume is equivalent to the effect an inert gas will not change the molar concentrations of the
of increase of pressure. reactants and products. Hence, the state of equilibrium will
remain unaffected.
hence the effect of decrease in volume will be to shift the
equilibrium in the direction in which the number of moles (b) If the reaction takes place at constant pressure, addition of
decreases. inert gas must accompany in increase in the total volume to
keep pressure constant. Thus, reaction shifts towards larger
number of moles.
5
SOLVED EXAMPLES
Example - 1 Example - 3
The following reaction has attained equilibrium One mole of H2O and one mole of CO are taken in a 10
litre vessel and heated at 725 K. At equilibrium 40% of
CO(g) 2H 2 (g) CH 3 OH(g), 'H o 92.0kJ mol1 water (by mass) reacts with CO according to the
equation:
What will happen if (i) volume of the reaction vessel is
suddenly reduced to half? (ii) the partial pressure of H 2 O(g) CO(g) H 2 O(g) CO2 (g)
hydrogen is suddenly doubled? (iii) an inert gas is added
to the system? Calculate the equilibrium constant for the reaction.
CH 3 OH PCH3 OH
Kc , Kp 1 0.40
Sol.
CO H 2
2
PCO u p2H 2 Sol. At equilibrium H 2 O mol L1 = 0.06 mol L–1,
10
[CO]= 0.06 mol L–1.
(i) When volume of the vessel is reduced to half, the
concentration of each reactant or product becomes double.
0.4
2 CH3OH 1 H2 mol L1 0.04 mol L1 ,
Thus, Qc
2[CO] u (2[H2 ]) 2
4
Kc As Q c K c , equilibrium 10
will shift in the forward direction, producing more of [CO2] = 0.04 mol L–1,
CH 3OH to make Q c Kc .
H 2 CO2 0.04 u 0.04
PCH3 OH 1 K 0.444
(ii) QP u (2 p H2 ) 2
Kp . H 2 O CO 0.06 u 0.06
p CO 4
Again Qp < Kp, equilibrium will shift in the forward direction Example - 4
to make Qp= Kp.
At 700 K, equilibrium constant for the reaction
(iii) As volume remains constant, molar concentration will not H 2 (g) I2 (g) 2HI(g) is 54.8. If 0.5 mol L–1 of HI
change. Hence there is no effect on the state of equilibrium.
(g) is present at equilibrium at 700K, what are the
Example - 2 concentrations of H2(g) and I2(g) assuming that we
initially started with HI (g) and allowed it to reach
A sample of HI (g) is placed in a flask at a pressure of
equilibrium at 700 K.
0.2 atm. At equilibrium, the partial pressure of HI (g) is
0.04 atm. What is Kp for the given equilibrium?
1
Sol. 2HI(g) H 2 (g) I2 (g) Sol. 2HI(g) H 2 (g) I2 (g), K
54.8
Initial pressure 0.2 atm 0 0
At equilibrium [HI]= 0.5 mol L–1,
0.16 0.16
At eqm. 0.04 atm atm atm
2 2 xu x 1
H2 [I 2 ] x mol L1 ? K
(0.5) 2 54.8
= 0.08 atm
(Decrease in the pressure of HI = 0.2–0.04=0.16 atm.) This gives x 0.068. i.e., [H2]= [I2] = 0.068 mol L–1
p H 2 u pI 2 0.08atm u 0.08atm
? Kp 2
4.0.
p HI (0.04atm)2
6
(ii) CH3COOH C2 H5OH CH3COOC2 H5 H2O

Example - 5
What is the equilibrium concentration of each of Initial 1.00 mol 0.180 mol
substances in the equilibrium when the initial
concentration of ICI was 0.78 M? At eqm.1–0.171 0.180–0.171 0.171 mol 0.171 mol
2I Cl(g) I 2 (g)+Cl 2 (g),K c =0.14 = 0.829 mol = 0.009 mol
Sol. Suppose at equilibrium, I2 = Cl2 =xmolL-1 . Then Molar
2ICl I 2 (g) + Cl 2 (g) concs 8.29/V 0.009/V 0.171/V 0.171/V
Initial conc. 0.78M 0 0 CH 3 COOC 2 H 5 H 2 O 0.171/ V 0.171/ V

Kc 3.92
CH 3COOH C 2 H5 OH 0.829 / V 0.009 / V
At eqm. 0.78-2x x x
(iii) CH3COOH C2 H5OH CH3COOC2 H5 H2O
I 2 Cl2 xu x
Kc = ? 0.14
ICl
2
(0.78 2 x) 2 Initial 1.000 mol 0.500 mol
After time t 1–0.214 0.500–0.214 0.214 mol 0.214 mol

x
or x2 0.14(0.78 2x)2 or 0.14 0.374
0.78 2x = 0.786 mol = 0.286 mol
or x 0.292 0.748 x or 1.748 x 0.292 or x 0.167

0.214 / V (0.214 / V)
Reaction quotient (Qc) = 0.204
Hence, at equilibrium, (0.786 / V)(0.286 / V)
I 2 = Cl2 =0.167M, ICI =0.78-2×0.167M=0.446M

As Q c z K c , equilibrium has not been attained
Example - 6
Example - 7
Ethyl acetate is formed by the reaction between ethanol A sample of pure PCl5 was introduced into an evacuated
and acetic acid and the equilibrium represented as: vessel at 473 K. After equilibrium was attained,
CH 3 COOH(l ) C2 H 5 OH(l ) CH 3COOC 2 H5 ( ) H 2 O(l ) concentration of PCl5 was found to be 0.5×10–1 mol L–1.
If value of Kc is 8.3 × 10–3, what are the concentrations
(i) Write the concentration ratio (reaction quotient), of PCl3 and Cl2 at equilibrium?
Qc for this reaction (Note: water is not in excess
and is not a solvent in this reaction) Sol. PCl5 (g) PCl3 (g) Cl2(g)
(ii) At 293 K, if one starts with 1.00 mol of acetic acid
and 0.18 mol of ethanol, there is 0.171 mol of ethyl At eqm 0.5× 10–1 mol L–1 x mol L–1 x mol L–1 (suppose)
acetate in the final equilibrium mixture. Calculate
the equilibrium constant. x2
? Kc 8.3 u103 (Given)
(iii) Starting with 0.5 mol of ethanol and 1.0 mol of 0.5 u10 1
acetic acid and maintaining it at 293 K, 0.214 mol
of ethyl acetate is found after some time. Has or x2 (8.3 u 10 3 )(0.5 u 101 ) 4.15 u 104 or
equilibrium been reached?
CH 3 COOC2 H5 H 2 O x 4.15 u104 2.04 u102 M 0.02M

Sol. (i) Qc CH 3 COOH C2 H5 OH
Hence, PCl3 eq
Cl2 eq
0.02M
7
Equilibrium constant, K c for the reaction, Dihydrogen gasused inHaber’sprocessisproduced by reacting
N 2 (g) 3H 2 (g) 2NH 3 (g) at 500 K is 0.061. At a methane fromnatural gas with high temperature steam. The
first stage of two stage reaction involves the formation of CO
particular time, the analysis shows that composition of
and H2. In second stage, CO formed in first state is reacted
the reaction mixture is 3.0 mol L–1 N2, 2.0 mol L–1 H2
with more steam in water gas shift reaction,
and 0.5 mol L–1 NH3. Is the reaction at equilibrium? If
not, in which direction does the reaction tend to proceed CO(g) H2 O(g) CO2 (g) H2 (g) . If a reaction
to reach equilibrium? vessel at 400ºC is charged with an equimolar mixture
of CO and steam such that pCO pH2O = 4.0 bar, what
2 2
NH 3 0.5 will be the partial pressure of H2 at equilibrium? Kp =
Sol. Qc 3 3
0.0104
N2 H2 3.0 2.0 0.1 at 400ºC.
As Q c z K c , reaction is not in equilibrium Sol. Suppose the partial pressure of H2 at equilibrium= p bar
CO(g) H 2 O(g) CO2(g) + H2 (g)

As Q c K c , reaction will proceed in the forward direction.
Initial pressure 4.0 bar 4.0 bar
Example - 9
At eqm (4–p) (4–p) p p
The equilibrium constant for the reaction
H 2 (g) Br2 (g) 2HBr(g) at 1024 K is 1.6 ×105. Find p2 p
Kp 0.1(given) ? 0.1 0.316
the equilibrium pressure of all gases if 10.0 bar of HBr (4 p)2 4p
is introduced into a sealed container at 1024 K.
p = 1.264–0.316p or 1.316p=1.264 or p=0.96 bar. Hence,
1 (pH2 )eq = 0.96 bar

Sol. 2HBr(g) H2 (g) Br2 (g). K
(1.6 u105 )
Example - 11
Initial 10 bar Predict which of the following reaction will have
appreciable concentration of reactants and products:
At eqm. 10–p p/2 p/2
(a) Cl 2 (g) 2Cl(g), K c 5 u 10 39
2
(p / 2)(p / 2) 1 p 1
Kp
(10 p) 2 1.6 u10 4(10 p)2
5
1.6 u105 (b) Cl2 (g) 2NO(g) 2NOCl(g),Kc 3.7 u108
Taking square root of both sides, we get (c) Cl2 (g) 2NO2 (g) 2NO2 Cl(g) Kc 1.8
p 1
2(10 p) or 4 u 10 2 p 2(10 p) or
4 u 10 2 Sol. For reaction (c), as Kc is neither high nor very low, reactants
and products will be present in comparable amounts.
20 Example - 12
402p 20 or p 4.98 u10 2 bar
402 The value of Kc for reaction, 3O2(g) 2O3 (g), is
2.0 × 10 at 25ºC. If the equilibrium concentration of O2
–50
Hence, at equilibrium pH2 pBr2 in air at 25ºC is 1.6 × 10–2, what is the concentration of O3?
2 2
= p/2 = 2.5×10–2 bar, p HBr 10 p | 10 bar O3 50
O3
Kc ? 2.0 u 10
Sol. 3 3
O2 1.6 u102
8
or [O3]2 = (2.0 × 10–50) (1.6×10–2)3 = 8.192×10–56 or Example - 15

–28
[O3]= 2.86×10 M Prove that the pressure necessary to obtain 50%
dissociation of PCl5 at 500 K is numerically equal to
Example - 13
three times the value of the equilibrium constant, Kp.
The reaction, CO(g)+3H2(g) CH4(g) + H2O (g), is at
equilibrium at 1300 K in a 1 L flask. It also contains Sol. PCl5 PCl3 Cl2
0.30 mol of CO, 0.10 mol of H2 and 0.02 mol of H2O and
an unknown amount of CH4 in the flask. Determine the Initial moles 1 0 0
concentration of CH4 in the mixture. The equilibrium Moles at eqm. 1–0.5=0.5 0.5 0.5 Total=1.5 moles
constant, Kc, for the reaction at the given temperature
is 3.90. If P is the total required pressure, then
0.5 P 0.5 P
CH 4 H 2 O p PCl5 uP ,PPCl3 uP
Sol. Kc 3 1.5 3 1.5 3
CO H 2
0.5 P
p Cl2 uP
CH 4 0.02 1.5 3
? 3.90 3 (molar conc= No. of moles
0.30 0.10
p PCl3 u pCl2 (P / 3)(p / 3) P
because volume of flask = 1L) ? Kp or P 3K p.
p PCl5 (p / 3) 3
–2
or [CH4]= 0.0585 M=5.85×10 M
At emperature T, a compound AB 2(g) dissociates What is the effect of reducing the volume on the system
according to the reaction described below?
2AB 2 2AB(g) + B 2 (g) 2C(s) O 2 (g) 2CO(g)
with a degree of dissociation, x, which is small compared Sol. On reducing the volume, the pressure will increase. By Le
with unity. Deduce the expression for x in terms of the Chatelier’s principle, equilibrium will shift to the side
equilibrium constant Kp and the total pressure, P. accompanied by decrease of pressure, i.e., decrease in the
number of gaseous moles, i.e., backward direction.
Sol. 2AB 2 2AB(g) B2 (g)
Initial 1 mole 0 0 Example - 17
At equilibrium 1 – x 2x x The degree of dissociation is 0.4 at 400 K and 1.0 atm

for the gaseous reaction
Total number of moles at equilibrium = 1–x+2x+x=1+2x
PCl5 PCl3 + Cl2.
1 x 2x x
pAB2 u P, p AB u P, p B2 uP
1 2 x 1 2x 1 2x Assuming ideal behaviour of all the gases, calculate
the density of the equilibrium mixture at 400 K and 1.0
2
p AB u p B2 2
§ 2x u P · § x u P ·§ 1 x ·
2
atmosphere. (Atomic mass of P = 31.0 and Cl = 35.5)
? Kp ¨ ¸ u¨ ¸¨ uP¸
p 2AB2 © 1 2x ¹ © 1 2x ¹© 1 2x ¹
Sol. PCl5 PCl3 + Cl2
3
4x P Initial 1 mole 0 0
or K p
1 x 1 2x
At eqm. 0.6 0.4 0.4 moles
Neglection x in comparison to unity,
Average molecular mass of mixture
1/ 3
3 § Kp ·
Kp 4x P or x ¨ ¸
© 4P ¹
9
Step 2. To calculate extra CO2 to be added

0.6(31 5 u 35.5) 0.4(31 3u 35.5) 0.4(2 u35.5)
0.6 0.4 0.4 Suppose extra CO2 to be added = x mole. Then writing the
reverse reaction, we have
125.1 55 42.6
148.92 CO2 + H2 CO + H2O
1.4
initial moles after
For ideal gases,
addition 0.2 + x 0.6 0.4 0.3
w w
PV nRT RT or PM RT d RT Moles (Molar
M V
Conc.)at new (0.2+x –0.2) (0.6–0.2) 0.6 (0.3+0.2)
PM 1u148.92 equilibrium =x = 0.4 = 0.5
?d = 4.5374 g L–1
RT 0.08205 u 400
(V=1L) (given)
Example - 18
1 0.6 u 0.5
At 540 K, 0.10 mol of PCl5 are heated in a 8.0 L flask. Kc ' 1 or x 0.75 moles
Kc x u 0.4
The pressure of the equilibrium mixture is found to be
1.0 atm. Calculate Kp and Kc for the reaction.
Example - 20
Sol. PCl5 PCl3 Cl2 The degree of dissociation of N2O4 into NO2 at one
atmospheric pressure and 313 K is 0–310. Calculate
Initial 0.1 mol
Kp of the dissociation reaction at this temperature. What
At eqm. 0.1 – x x x will be the degree of dissociation at 10 atmospheric
Total no. of moles at eqm. = 0.1 + x pressure at the same temparture?
PV 1u 8 Sol.
PV nRT, i.e., n 0.18
RT 0.0821u 540
For the dissociation
? 0.1 x 0.18 or x 0.08
reaction N 2 O 4 (g) 2NO2 (g)
(0.08 / 8)(0.08 / 8)
? Kc 0.04 Initial moles 1 0
(0.02 / 8)
Moles at eqm. 1–0.310=0.69 2×0.310=0.62 (D 0.310,Given)
'n
Kp K c (RT) 0.04(0.0821u 540) 1
1.77
Total = 0.69+0.62=1.31 moles
Example - 19 At one atmospheric
An equilibrium mixture,
0.69 0.62
pressure, p N 2 O4 u 1 atm, p NO2 u1atm
CO(g) H 2 O(g) CO 2 (g) H 2 (g), present in a 1.31 1.31
vessel of one litre capacity at 1000 K was found to
contain 0.4 mole of CO, 0.3 mole of H2O, 0.2 mole of p 2NO2 (0.62 /1.31atm) 2
CO2 and 0.6 mole of H2. If it is desired to increase the Kp 0.425atm
p N 2O 4 (0.69 /1.31atm)
concentration of Co to 0.6 mole by adding CO2 into the
vessel, how many moles of it must be added into At 10 atmoshperic pressure, suppose degree of dissociation = D .
equilibrium mixture at constant temperature in order Then
to get this change.
N 2 O4 2NO 2
Sol. Step 1. To calculate Kc of the reaction.
Initial moles 1 0
CO(g) H 2 (g) 0.2 u 0.6 Moles at eqm 1 D Total = 1+ D
Kc 1 2D ,
CO(g) H 2 O(g) 0.4 u 0.3
10
1 D 2D Example - 23
p N 2 O4 u 10atm, p NO2 u 10atm
1 D 1 D
0.1 mole of N2O4 (g) was sealed in a tube under
atmospheric condition at 25ºC. Calculate the number
[20D /(1 D )]2 40D 2 40D 2 of moles of NO2(g) present if the equilibrium N2O4(g) is
Kp
[10(1 D ) /(1 D)] 1 D (1 D ) 1 D2 reached after some time (Kp = 0.14).
Sol. N 2 O 4 (g) 2NO2(g)

40D 2
? 0.425
1 D2 Initial amount 0.1 mole 0
At equilibrium (0.1–x) 2x, Total=0.1+x moles
Neglecting D2 in comparison to 1, 40 D2 = 0.425
0.1 x 2x
or D = 0.103 = 10.3 % As P=1 atm, p N2O4 , p NO2 atm
0.1 x 0.1 x
Example - 21
p 2NO2 (2x /(0.1 x)) 2
When α - D glucose is dissolved in water, it undergoes Kp
p N 2O 4 (0.1 x) /(0.1 x)
mutarotation to form an equilibrium mixture of
α - D glucose and β - D glucose containing 63.6% of 4x 2 4x 2
the latter. Calculate Kc for the mutarotation. (0.1 x)(0.1 x) 0.01 x 2
Sol. α-D glucose E - D glucose

4x 2
? 0.14 or 4.14 x2 = 0.0014 or x=0.018
At equilibrium 36.4% 63.6% 0.01 x 2
? No. of moles of NO2 at equilibrium = 2x=2×0.018= 0.036

63.6 mole
Kc 1.747
36.4
Example - 22
At 77ºC and one atmoshpheric pressure, N2O4 is 70%

dissociated into NO2. What will be the volume occupied
by the mixture under these conditions if we start with
10g of N2O4?
Sol. Molar mass of N 2 O4 28 64 92g mol 1
N 2 O4 2NO2
10
Initial moles 0
92
10 70 10
After dissociation u 2×0.076
92 100 92
= 0.109–0.076=0.033 = 0.152
11
IONIC EQUILIBRIUM
IONIC EQUILIBRIUM
Ionic equilibrium is the study of equilibrium in the reactions The major drawback of this theory is that the basis of all
where formation of ions take place in aqueous solution. definitions is water.
BOH l B+ + OH–
1. ELECTROLYTES
1.2.2 Bronsted-Lowry concept
Electrolytes are those compounds which on dissolving in Acids : Those compounds which can transfer protons that
+
polar solvents like water break into ions. The solution of is H to other compounds
electrolytes conducts electricity because of the presence Bases: Those compounds which can accept protons.
of ions.
That is, Bronsted acids are “proton donors” and Bronsted
1.1. Classification of electrolytes bases are “Proton acceptors”.
HCl + H2 O l H 3O + + Cl
1.1.1 Electrolytes can be classified on the basis of their
Acid-1 Base-1 Acid-2 Base-2
strength into two categories:
Conjugate Acid-Base pairs: Pairs which are separated by a
Strong electrolytes : Those electrolytes which easily break
proton and exhibit opposite behaviours in the two directions
into ions and give almost complete dissociation. Eg. HCl, -
of the same reaction. Eg. In the above reaction HCl and Cl
NaOH, NaCl, HNO3, HClO4, H2SO4, CaCl2 etc
are conjugate acid-base pairs.
Weak electrolytes : Those electrolytes which dissociate
partially. Eg. CH3COOH, NH4OH, HCN, H2C2O4, and all Note : In a conjugate pair if acid is strong the base is weak
organic acids and bases etc. and vice-versa.
1.1.2 Electrolytes can be further classified on the basis of 1.2.3 Lewis Concept
the kind of compound they are. Acid: A compound which can accept a pair of electrons.
Acids Base: is a compound which can transfer its lone pair of
Bases electrons.
Salts Eg. BF3 + NH3 l H3N oBF3
In the above reaction BF3 is a lewis acid and NH3 is a lewis
1.2 Acids and Bases
base.
The definition of acids and bases varies from theory to

2. DISSOCIATION OF WEAK ACIDS AND BASES
theory:
1.2.1 Arrhenius theory HA l H+ + A–
This theory defines acids and bases from the perspective
Ka = cD2/(1 – D)
of water as a solvent.
Ka is called “ionisation constant” or the “Dissociation
Arrhenius acids: Those compounds which will increase
+ constant” of the acid.
H ion concentration in water. Eg HCl, H2SO4, CH3COOH
etc For low dissociation : 1 – D | 1
HA l H+ + A– Ka = cD2
Arrehenius bases: Those compounds which will increase
– D ( K a / C) This expression will be valid only when
OH ion concentration in water. Eg. NaOH, Ca(OH)2,
NH4OH etc D< 0.05 (5%)
12
IONIC EQUILIBRIUM
[H+] = cD = cK a = [A–] 6. BUFFER SOLUTIONS

Similarly for a Weak base Ka = cD/(1 – D)
Solutions which can resist any change in pH on addition of
K b is called “ionisation constant” or “dissociation small amount of acid or base.
constant” for the base. Buffer solutions are of three types:
D ( K b / C This expression will be valid only when 6.1 Acidic Buffer Eg.
D< 0.05 (5%)
CH3COOH + CH3COONa
[B+] = [OH–] = cK b
Henderson-Hasselbalch equation
Note : pH = pKa + log [salt]/[acid]
D weak electrolytes increase on dilution
6.1.1 Buffer Range:
pKa– 1 dpH d pK + 1
a
3. SELFIONISATION OF WATER
6.2 Basic Buffer Eg.
H2O lH+ + OH–

NH4OH and NH4Cl
+ –
Kw = [H ] [OH ] pOH = pKb + log [salt]/[base]
Kw is called ionic product of water. 6.2.1 Buffer range:
For pure water: [H+] = [OH–] pKb – 1 d pOH d pKb+ 1
+ – –14
At 25º C we know that [H ][OH ] = 10
6.3 Mixed Buffer Eg.
[H+] = [OH–] = Kw 10 7 M
CH3COONH4
Acidic: [H3O+] > [OH–]
Neutral: [H3O+] = [OH–] Note :
Basic: [H3O+] < [OH–] pH of a buffer solution does not change on dilution.
Note: Kw increases as temperature increases. For any acid-conjugate base pair Ka.Kb=Kw
4. pH SCALE
pH = – log10[H+]
7. POLYPROTIC ACIDS
pH + pOH = pKw = 14 (at 25º)
At 25ºC Those acids which can furnish more than one H +
pH < 7 Acidic permolecule. Eg. H2SO4, H2CO3, H3PO4
pH > 7 Basic For any polyprotic acid : K1 > K2 > K3 ....so on
pH = 7 Neutral For dissociation of H2A [A2–] | K

i.e. The concentration of the second ion of a polyprotic
5. MIXTURE OF TWO WEAK ACIDS acid is almost equal to the second dissociation constant.
[H+] = (x + y) = c1K 1 c 2 K 2
13
IONIC EQUILIBRIUM
8. SALT HYDROLYSIS 9. SPARINGLY SOLUBLE SALTS & PRECIPITATION
Depending on the nature of the parent acid and base there When a salt is dissolved in water then it starts breaking
can be 4 type of salts: into ions and after sometime the solubility process attains
equilibrium.
8.1 Salt of strong acid and strong base (NaCl)
AgCl(s) l Ag+(aq) + Cl–(aq)
This type of salt do not get hydrolysed. Ksp = [Ag+] [Cl–] = Q = I.P.
Neutral solution with pH = 7
I.P. < Ksp forward reaction, more salt can be dissolved
8.2 Salt of weak acid and strong base (CH3COONa) I.P. = K saturation, no more salt can be dissolved
sp
This type of salt give acidic solution on hydrolysis. I.P. > Ksp backward reaction, precipitation of solid salt
will take place
Kh = CDh2/ (1 – Dh) = Kw/Ka ; pH = 7 + ½ pKa – ½ log C
8.3 Salt of Strong acid and weak base (NH4Cl)
This type of salt give basic solution on hydrolysis.

Kh = CDh2/ (1 – Dh) = Kw/Kb ; pH = 7 – ½ pKb – ½ log C
8.4 Salt of weak acid and weak base (CH3COONH4)
This type of salt may give acidic,basic or neutral solution.

Kh = Dh2/ (1 – Dh)2 = Kw/(Ka × Kb) ; pH = 7 + ½ pKb – ½ pKb
14
IONIC EQUILIBRIUM
SOLVED EXAMPLES
Example - 1 (d) M1V1 M 2 V2 ?13.6M u 1mL M 2 u 1000mL
Calculate the pH of the following solutions: ? M2 = 1.36 × 10–2 M

(a) 2g of TlOH dissolved in water to give 2 litre of the ª¬ H º¼ HCl 1.36 u10 2 M.
solution
(b) 0.3 g of Ca(OH)2 dissolved in water to give 500 mL pH log(1.36 u 102 ) 2 0.1335 1.87
of the solution
(c) 0.3 g of NaOH dissolved in water to give 200 mL of Example - 2
the solution The degree of ionization of a 0.1 M bromoacetic acid
(d) 1 mL of 13.6 M HCl is diluted with water to give 1 solution is 0.132. Calculate the pH of the solution and
litre of the solution. the pKa bromoacetic acid.
2g 1 Sol. CH 2 (Br)COOH CH 2 (Br)COO H

Sol. Molar conc. of TlOH = (204 16 1)gmol1 u 2L
Intial Conc C 0 0
= 4.52 ×10–3 M Conc at eqm C – CD CD CD
? ª¬ OH º¼ TlOH 4.52 u10 3 M CD.CD CD2

Ka 0.1u (0.132)2 1.74 u103
C(1 D) 1 D CD
2
ª¬ H ¼º 1014 /(4.52 u 10 3 ) 2.21u 10 12 M

pK a log(1.74 u 10 3 ) 3 0.2405 2.76
pH log(2.21 u 10 12 ) 12 (0.3424) 11.66
ª¬ H º¼ CD 0.1u 0.132 1.32 u 10 2 M
0.3g 1 3
Molar conc. of Ca(OH)2 = 40 34 gmol1 u 0.5L 8.11u10 M pH log(1.32 u 102 ) 2 0.1206 1.88
Example - 3
Ca(OH) 2 o Ca 2 2 OH
The pH of 0.005 M codeine (C18H21NO3) solution is 9.95.

ª¬ OH ¼º 3 Calculate the ionization constant and pKb.
? 2 Ca(OH) 2 2 u (8.11 u 10 ) M
= 16.22×10–3 M Sol. Cod H 2 O CodH OH
pOH log(16.22 u 103 ) 3 1.2101 1.79 pH 9.95 ? pOH 14 9.95 4.05i.e.
log ª¬ OH ¼º 4.05
pH 14 1.79 12.21

(c) Molar conc. of NaOH or log ª¬ OH ¼º 4.05 5.95 or
0.3g 1 ª¬ OH ¼º 8.913 u 105 M

u 3.75 u 10 2 M
40g mol 1 0.2L
2 2
ª¬CodH º¼ ª¬OH º¼ ª¬ º¼ 8.91u105
ª¬ OH ¼º 2
3.75 u 10 M Kb
Cod Cod 5 u103
pOH log(3.75 u10 2 ) 2 0.0574 1.43 = 1.588 × 10–6

? pH 14 1.43 12.57
pK b log 1.588 u 10 6 6 0.1987 5.8
15
IONIC EQUILIBRIUM
Calculate the hydrogen ion concentration in the The solubility of Sr(OH)2 at 298 K is 19.23 g/L of
following biological fluids whose pH are given: solution. Calculate the concentration of strontium and
hydroxyl ions and the pH of the solution. (Atomic mass
(a) Human muscle–fluid, 6.83 of Sr = 87.6)
(b) Human stomach fluid, 1.2
Sol. Molar mass of Sr(OH)2= 87.6+34=121.6g mol–1
(c) Human blood, 7.38
Solubility of Sr(OH)2 in moles
(d) Human saliva, 6.4
19.23gL1
Sol. (a) log[H ] pH 6.83 7.17 L–1 = 0.1581M
121.6gmol1
?[H ] Antilog 7.17 1.479 u10 7 M
Assuming complete dissociation,
(b) log[H ] pH 1.2 2.8
Sr(OH)2 o Sr2+ + 2 OH–
2
? [H ] Antilog 2.8 6.31u 10 M
? [Sr 2 ] 0.1581M.[OH ] 2 u 0.1581 0.3162M

(c) log[H ] pH 7.38 8.62
pOH log 0.3162 0.5, ? pH 14 0.5 13.5
?[H ] Antilog 8.62 4.169 u 10 8 M
(d) log[H ] pH 6.4 7.60 Example - 8

The pH of 0.1M solution of cyanic acid (HCNO) is 2.34.
?[H ] Antilog 7.60 3.981 u10 7 M Calculate the ionization constant of the acid and its
degree of ionization in the solution.
Example - 5
The pH of milk, black coffee, tomato juice, lemon juice Sol. HCNO H CNO
and egg white are 6.8, 5.0, 4.2, 2.2 and 7.8 respectively.
Calculate corresponding hydrogen ion concentration pH=2.34 mean –log[H+]= 2.34 or log [H+]=–2.34= 3.66
in each.
or ª¬ H º¼ Anti log 3.66 4.57 u 10 3 M
–7 –5
Sol. Similar to Q. 7.55 [Ans 1.5×10 M, 10 M,
6.31×10–3 M, 1.58×10–8 M] ª¬ CNO ¼º
¬ª H ¼º 4.57 u 10 3 M
Example - 6
(4.57 u10 3 )(4.57 u 103 )
If 0.561 g KOH is dissolved in water to give 200 mL of Ka 2.09 u 104
0.1
solution at 298 K, calculate the concentration of
potassium hydrogen and hydroxyl ions. What is its pH?
D Ka / C 2.09 u104 / 0.1 0.0457
0.561 1000
Sol. KOH u M 0.050M Example - 9
56 200
The ionic product of water at 310 K is 2.7 ×10–14. What

As KOH o K OH ,? ª¬ K ¼º ¬ªOH ¼º 0.05M is the pH of neutral water at this temperature?
ª¬ H ¼º K w / ¬ª OH ¼º 10 14 / 0.05 1014 /(5 u 102 ) Sol. ª¬ H º¼ Kw 2.7 u10 14 1.643 u107 M
= 2.0×10–13 M.
pH log ª¬ H ¼º log(1.643 u 107 )
+ –13
pH =–log [H ]=– log (2.0×10 )= 13–0.3010= 12.699
7 0.2156 6.78
16
IONIC EQUILIBRIUM
One the basis of the equation pH =– log [H ], the pH of + Prove that the degree of dissociation of a weak
10–8 mol dm–3 solution of HCl should be 8. However, it is monoprotic acid is given by
observed to be less than 7.0. Explain the reason.
1
Sol. pH of 10 –8 M HCl solution is not 8 because this D where Ka is the dissociation constant
1 10(pK a pH)
concentration is so low that H+ ion produced from H2O in
of the acid.
the solution (viz. 10–7M) cannot be neglected. Total [H+]
= 10–8 + 10–7 M. Solving and calculating pH, we get the Sol. Suppose we start with C mol L–1 of the weak monoprotic
value close to 7 but less than 7 as the solution is acidic. acid HA. Then
HA H+ + A–
Example - 11
Initial molar conc. C
pH of a solution of a strong acid is 5.0. What will be the
pH of the solution obtained after diluting the given Molar conc C– CD CD CD
solution 100 times?
after dissociation= C(1– D )
+ –5
Sol. pH = 5 means [H ]= 10 M. On diluting 100 times,
CD.CD CD 2 Ka (1 D)
5 Thus, Ka or C ..(i)
10
107 M C(1 D) 1 D D2
¬ª H º¼ 100

Also, ª¬ H º¼ CD
This should give pH =7 but it cannot be so because
solution is acidic and pH should be less than 7. The reason Substituning the value of C from eqn. (i), we get
is that [H+] from H2O cannot be neglected. Thus, total [H+]
= 10–7 M (from HCl) + 10–7 M (from H2O) = 2 × 10–7 M K a (1 D) K a (1 D )
ª¬ H ¼º uD
D2 D
? pH log(2 u 10 7 ) 7 0.3010 6.699.
? log ¬ªH ¼º [log Ka log(1 D) log D]
Example - 12 or pH pK a log(1 D ) log D

pH of 0.08 mol dm–3 HOCl solution is 2.85. Calculate
its Ionisation constant. 1 D 1 D
or log pK a pH or 10pK a pH
D D
Sol. pH of HOCl=2.85 i.e., –log [ H+] = – 2.85
1
or 1 10 pK a pH
D
or log [H+] = – 2.85 = 3.15
1 1
or [H+] = antilog 3.15 = 1.413 × 10–3 M or 1 10pK a pH or D
D 1 10pK a pH
For weak monobasic acid HA H+ + A– Example - 14

Arrange the given compounds in the decreasing order
2 3 2
ª¬ H º¼ 1.413 u10 of basicity on the basis of Bronsted–Lowry concept:
Ka = 2.4957 × 10–5. BaO, CO2, SO3, B2O3, Cl2O7
HA 0.08
Sol BaO + H2O Ba(OH)2 (Basic)
CO 2 H 2 O H 2 CO3 (weakly acidic)
17
IONIC EQUILIBRIUM
SO 3 H 2 O H 2SO 4 (Strongly acidic) Example - 18
B2 O3 3H 2 O 2H3 BO3 (Very weaky acidic) Why PO 43- ion is not amphiprotic?
Cl 2 O 7 H 2 O 2HClO4 (Very strongly acidic) Sol. An amphiprotic ion is one which can donate proton as
Hence, in the decreasing order of basicity, we gave well as accept proton. PO 34 ion can accept proton(s) but
BaO ! B 2 O 3 ! CO 2 ! SO 3 ! Cl 2 O7 . cannot donate any proton. Hence, PO34 is not amphiprotic.
What are the conjugate bases of the following?
In the reaction between BF3 and C2H5OC2H5 which one
3+
CH3OH, HN3, [Al(H2O)6] . of them will act as an acid? Justify your anwer.
Sol. The reaction between BF3 and C2H5OC2H5 is

Sol. CH 3O N 3 [Al(H 2 O)5 OH]2 (H+ ion has been removed
methoxideion , azideion
from one H2O molecule).

Example - 16
Glycine is an D –amino acid which exists in the form of
+
Zwitter ion as N H 3CH 2COO- . Write the formula of As BF3 accepts a pair of electrons, hence BF3 is the Lewis
its conjugate base. acid.
Example - 20
Sol. Conjugate acid =
Which is a stronger base in each of the following pairs
and why?
N H 3 CH 2 COO H N H3 CH 2 COOH
(i) H2O, Cl– (ii) CH3COO–, OH–
Conjugate base =
Sol (i) H2O (ii) OH–

N H 3 CH 2 COO H NH 2 CH 2 COO
Refer to Bronsted – Lowry concept for relative strengths.
Example - 17
Example - 21
Write reaction for autoprotolysis of water. How is ionic
Classify the following species as Lewis acids and Lewis
product of water related to ionization constant of water?
bases
Derive the relationship.
NH3, BF3, SnCl4, C5H5N, CO, Ni2+
Sol. Autoprotolysis of H2O takes place as:
Sol. Lewis acids: BF3, SnCl4, Ni2+

H2O H2O H 3 O OH Lewis bases: NH3, C5H5N, CO.
Example - 22
For ionization of H2O, H 2 O H OH
Explain why pH of 0.1 molar solution of acetic acid will
be higher than that of 0.1 molar solution of HCl?
[H ][OH ] K2 Kw
Ki or
[H 2 O] [H 2 O] 55.55mol L1 Sol. Acetic acid is a weak electrolyte. It is not completely ionized
and hence gives less H+ ion concentration. HCl is a strong
acid. It is completely ionized giving more H + ion
Kw K i u 55.55.
concentration. As pH =–log [H+]; less the [H+], greater
will be the pH.
18
IONIC EQUILIBRIUM
HA + OH– A– + H2O
Example - 23
Calculate the approximate pH of a 0.100 M aqueous [A ]
K .......(i)
H2S solution. K1 and K2 for H2S are 1.00 ×10–7 and [HA][OH ]
1.30 ×10–13 respectively at 25ºC,
Further, for the weak acid, HA H+ + A–,
Sol. K2 < < K1. Hence H+ ions are mainly from 1st dissociation,
i.e. H2S H+ +HS– [H ][A ]
Ka ......(ii)
2
[HA]
ª¬ H º¼ ª¬ HS º¼

ª¬ H º¼

K1 or ª¬ H º¼ K1[H 2S] Also Kw = [H+] [ OH–] .....(iii)

H 2S H 2S
From eqns. (i), (ii) and (iii),
? [H ] 107 u 10 1 10 4
Ka 104
K 1010
Hence, pH=4 Kw 1014
Calculate the pH at equivalence point when a solution of
The pH of 0.05 M aqueous solution of diethylamine is
0.10 M acetic acid is titrated with a solution of 0.10 M
12.0. Calculate its Kb
NaOH solution, Ka for acetic acid = 1.9×10–5
Sol. At the equivalence point, CH3COONa is formed and its Sol. (C 2 H 5 ) 2 NH H 2 O (C 2 H 5 ) 2 NH 2 OH
0.1 As pH = 12, ? [H ] 1012 M or [OH – ] = 10 –2 M,

concentration = M 0.05M . It is a salt of weak acid
2
and strong base. The formula for finding the pH of such a [(C 2 H 5 ) 2 NH] 0.05 0.01 0.04M
salt is
[(C 2 H 5 ) 2 N H 2 ][O H ] 10 2 u 10 2
K 2.5 u 10 3
[(C 2 H 5 ) 2 N H ] 0.04
1
pH [log K 2 log K a log c]
2
[(C 2 H 5 ) 2 NH 2 ] [OH ]
1
? pH [log1014 log(1.9 u105 ) –log (5×10–2)] Example - 27
2
An aqueous solution contains 10% ammonia by mass
1
[14 (5 0.2788) (2 0.6990)] and has a densityof 0.99 g cm–3. Calculate hydroxyl and
2 hydrogen ion concentration in this solution. Ka for
NH 4+ = 5.0×10-10 M
1
(14 5 0.2788 2 0.6990)
2 Sol. 10% ammonia by mass means 10g NH3 are present in 100g
of the solution.
17.42
8.71 ? Molarity of the solution
2
10 1
Example - 25 u u 1000 = 5.82 M
17 100 / 0.99
A certain weak acid has Ka = 1.0×10–4. Calculate the
equilibrium constant for its reaction with a strong base. NH 3 H 2 o NH 4 OH U NH 4 OH
Initial conc. C mol L–1

Sol. HA BOH BA + H2O
weak strong
After dissociation C – C D C D CD
+ – + –
or HA + B + OH B + A +H2 O or = C (1 –D)
19
IONIC EQUILIBRIUM
Total volume after mixing = 500 ml

Kh
? [OH ] C D C KhC ? In the final solution, after mixing , [OH – ]=
C
102 1014
2 u 103 M or[H ] 5 u 10 12
Kw 10 14 5 2 u 10 3
uC u 5.82 = 1.079 × 10–2 M
Ka 5.0 u10 10
? pH log[H ] log(5 u10 12 ) 12 0.69 11.31
Kw 10 14
?[H ] Example - 30
[OH ] 1.079 u10 2
Calculate the degree of dissociation of 0.5 M NH3 at
= 0.9268 × 10 –12
M = 9.268 × 10 –13
M 25ºC in a solution of pH=12.
Example - 28 Sol. NH 4 OH NH 4 OH
The ionization constant of NH 4+ in water is Initial conc. C mol L–1 0 0

5.6 × 10–10 at 25ºC. The rate constant for reaction of After disso. C CD CD CD
+ – 10
NH and OH to form NH3 and H2O at 25ºC is 3.4×10 s
4
litre mol–1 sec–1. Calculate the rate constant for prton pH 12 means[H ] 10 12 or [OH ] 10 2
transfer from water of NH3.
102
? [OH ] CD 102 or D
Sol. NH +4 H 2 O NH4OH+H+, Ka = 5.6 ×10–10 C
NH3 + H2O NH 4 OH , k 3.4 u 1010 102

2 u 10 2 or 2%.
0.5
Aim. To find kf
Example - 31
We know that for a conjugate acid–base pair
K acid u K base K w ,i.e., K a u K b Kw Calculate the ratio of pH of a solution containing 1 mole
of CH3COONa + 1 mole of HCl per litre to that of a
solution containing 1 mole of CH3COONa + 1 mole of
Kw 10 14
?K CH3 COOH per litre.
Ka 5.6 u10 10
Sol. Case I. Calculation of pH of solution containing 1 mole of
kf CH3COONa + 1 mole of HCl per litre
But K ?k f Kb u k
k
CH 3COONa HCl o CH3 COOH NaCl
10 14 Initial moles 1 mole 1 mole 0 0

u3.4 u1010 0.607 u106 6.07 u105
5.6 u10 10 Moles after
reaction 0 0 1 1
Example - 29
What will be the resultant pH when 200 ml of an aqueous i.e [CH 3 COOH] 1mol L1
solution of HCl (pH=2.0) is mixed with 300 ml of an
aqueous solution of NaOH (pH=12.0)? CH 3 COOH CH3COO– + H+
Sol. pH = 2 means [H+] = 10–2M Initial conc. C mol L–1
pH = 12 means [H+]= 10–12or [OH–]= 10–2 M After dissociation C CD CD CD

Thus, 200 ml of 10–2 M HCl are mixed with 300 ml of 10–2 M
Ka
NaOH. After neutralisation NaOH left = 100 ml of 10–2 M ? [H ] CD . But D
C
20
IONIC EQUILIBRIUM
(ii) When 3/4th of the acid has been neutralized

Ka
? [H ] C Ka C Ka K1/a 2 ('C 1molL ) 1
C CH 3COOH NaOH o CH 3 COONa H 2 O
1 1 Initial conc. 0.1M

? log[H ] log K a ,i.e.(pH)1 log K a ...(i)
2 2
Case II. Calculation of pH of solution containing 1 mole of 1 3

After 3/4th 0.1 u M 0.1 u M
CH3COONa + 1 mole of CH3 COOH per litre 4 4
Applying Henderson equation, neutralization = 0.025 M = 0.075 M
[Salt] 0.075
(pH)2 = pKa + log pK a log K a ...(ii) ? pH = – log 10–5 + log = 5 + 0.4771 = 5.4771.
[Acid] 0.025
[Salt] [Acid] 1mol L1 ] Example - 33

Calculate the amount of (NH4)2 SO4 in g which must be
Example - 32 added to 500 mL of 0.2 M NH3 to yield a solution of
0.1 M CH3 COOH (pH=3) is titrated with 0.05 M NaOH pH = 9.35. Kb for NH3 = 1.78×10–5.
solution. Calculate the pH when (i) 1/4th of the acid has
[Salt]
been neutralized. (ii)3/4th of acid has been neutralized. Sol. As it is a basic buffer, pOH = pK b + log
[Base]
Sol. Calculation of dissociation constant of the acid
[NH 4 ]
log K log
As pH = 3, ?[H ] 103 M, [CH3COO ] [H ] 103 M [NH 4 OH]
As pH = 9.35, ?pOH 14 9.35 4.65

[CH 3COO ][H ] 103 u103 5
Ka 10
[CH3 COOH] 0.1 Millimoles of NH4OH is solution = 0.2×500 = 100 Suppose
millimoles of NH 4 to be added=x
(i) When 1/4th of the acid has been neutralized
x / 500
? 4.65 log(1.78 u 105 ) log
CH 3COOH NaOH o CH 3COONa H 2 O 100 / 500
Initial conc. 0.1 M x

(5 0.2504) log
100
After 1/4th
x
3 1 or log 0.0996 1.004 0.1
0.1u 0.1u 100
4 4
or log x = 2.1 or x = 125.9
0.075M 0.025M
125.9
? Millimoles of (NH4)2SO4 to be added = 62.95
2
[Salt] 0.025
?pH pK a log log10 5 log
[Acid] 0.075 ( '1 millimole of (NH 4 )2 SO 4 { 2 millimoles of NH 4+ )
5 0.4771 4.5229 ? Mass of (NH4)2SO4 to be added = (62.95 × 10–3 moles)

(132 g mol–1) = 8.3094 g.
21
SOME BASIC CONCEPTS OF CHEMISTRY
1. CHEMISTRY 2. MATTER
Chemistry is defined as the study of the composition, Matter is defined as any thing that occupies space
properties and interaction of matter. Chemistry is often possesses mass and the presence of which can be felt by
any one or more of our five senses.
called the central science because of its role in connecting
the physical sciences, which include chemistry, with the Matter can exist in 3 physical states viz. solid, liquid, gas.
life sciences and applied sciences such as medicine and Solid - a substance is said to be solid if it possesses a
engineering. definite volume and a definite shape, e.g., sugar, iron, gold,
wood etc.
Various branches of chemistry are
Liquid- A substance is said to be liquid, if it possesses a
1.1 Physical chemistry definite volume but no definite shape. They take up the
shape of the vessel in which they are put, e.g., water, milk,
The branch of chemistry concerned with the way in which oil, mercury, alcohol etc.
the physical properties of substances depend on and Gas- a substance is said to be gaseous if it neither possesses
influence their chemical structure, properties, and reactions. definite volume nor a definite shape. This is because they
fill up the whole vessel in which they are put, e.g., hydrogen,
1.2 Inorganic chemistry
oxygen etc.
The branch of chemistry which deals with the structure, The three states are interconvertible by changing the
composition and behavior of inorganic compounds. All the conditions of temperature and pressure as follows
substances other than the carbon-hydrogen compounds
are classified under the group of inorganic substances.
1.3 Organic chemistry
The discipline which deals with the study of the structure,

composition and the chemical properties of organic
compounds is known as organic chemistry.
1.4 Biochemistry
The discipline which deals with the structure and behavior

of the components of cells and the chemical processes in
living beings is known as biochemistry.
1.5 Analytical chemistry 3. CLASSIFICATION OF MATTER AT

MACROSCOPIC LEVELL
The branch of chemistry dealing with separation,
identification and quantitative determination of the At the macroscopic or bulk level, matter can be classified as
compositions of different substances. (a) mixtures (b) pure substances.
22
These can be further sub-divided as shown below

Pure substances can be further classified into elements
and compounds.
Element- An element is defined as a pure substance that

contains only one kind of particles. Depending upon the
physical and chemical properties, the elements are further
subdivided into three classes, namely (1) Metals (2) Non-
metals and (3) Metalloids.
Compound- A compound is a pure substance containing

two or more than two elements combined together in a fixed
proportion by mass. Further, the properties of a compound
are completely different from those of its constituent
elements. Moreover, the constituents of a compound
cannot be separated into simpler substances by physical
(a) Mixtures : A mixture contains two or more substances
methods. They can be separated by chemical methods.
present in it (in any ratio) which are called its
components. A mixture may be homogeneous or
4. PROPERTIES OF MATTER
heterogeneous.
Homogeneous mixture- in homogeneous mixture the Every substance has unique or characteristic properties.
components completely mix with each other and its These properties can be classified into two categories –
composition is uniform throughout i.e it consist of only physical properties and chemical properties.
one phase. Sugar solution and air are thus, the examples of
homogeneous mixtures. 4.1 Physical Properties
Heterogeneous mixtures- In heterogeneous mixture the
Physical properties are those properties which can be
composition is not uniform throughout and sometimes the
different phases can be observed. For example, grains and measured or observed without changing the identity or the
pulses along with some dirt (often stone) pieces, are composition of the substance. Some examples of physical
heterogeneous mixtures. properties are color, odor, melting point, boiling point,
density etc.
4.2 Chemical properties
Any distinct portion of matter that is uniform throughout Chemical properties are those in which a chemical change
in composition and properties is called a Phase. in the substance occurs. The examples of chemical properties
are characteristic reactions of different substances; these
(b) Pure substances :- A material containing only one
include acidity or basicity, combustibility etc.
substance is called a pure substance.
5. MEASUREMENT
5.1 Physical quantities

In chemistry, a substance is a form of matter that has
constant chemical composition and characteristic All such quantities which we come across during our
properties. It cannot be separated into components by scientific studies are called Physical quantities. Evidently,
physical separation methods, i.e. without breaking the measurement of any physical quantity consists of two
chemical bonds. They can be solids, liquids or gases. parts
23
(1) The number, and (2) The unit International d’Unités – abbreviated as SI) was established
by the 11th General Conference on Weights and Measures
A unit is defined as the standard of reference chosen to (CGPM from Conference Generale des Poids at Measures).
measure any physical quantity. The CGPM is an inter governmental treaty organization
created by a diplomatic treaty known as Meter Convention
5.2 S.I. UNITS which was signed in Paris in 1875.
The International System of Units (in French Le Systeme The SI system has seven base units and they are listed in
table given below.
These units pertain to the seven fundamental scientific quantities. The other physical quantities such as speed, volume,
density etc. can be derived from these quantities. The definitions of the SI base units are given below :
Definitions of SI Base Units
Unit of length metre The metre is the length of the path travelled by light in
vacuum during a time interval of 1/299 792 458 of a second.
Unit of mass Kilogram The kilogram is the unit of mass; it is equal to the mass of
the internationl prototype of the kilogram.
Unit of time second The second is the duration of 9 192 631 770 periods of the
radiation corresponding to the transition between the two
hyperfine levels of the ground state of the caesium-133
atom.
Unit of electric current ampere The ampere is that constant current which, if maintained in
two straight parallel conductors of infinite length, of
negligible circular cross-section, and placed 1 metre apart
in vacuum, would produce between these conductors a
force equal to 2 × 10–7 newton per metre of length.
Unit of thermodynanic kelvin The kelvin, unit of thermodynamic temperature, is the

temperature fraction 1/273. 16 of the thermodynamic temperature of the
triple point of water.
Unit of amount of substance mole 1. The mole is the amount of substance of a system
which contains as many elementary entities as there
are atoms in 0.012 kilogram of carbon-12; its symbol
is “mol.”.
2. When the mole is used, the elementary entities must

be specified and may be atoms, molecules, ions,
electrons, other particles, or specified groups of such
particles.
Unit of luminous intensity candela The candela is the luminous intensity, in a given direction,
of a source that emits monochromatic radiation of
frequency 540 × 1012 hertz and that has a radiant intensity
in that direction of 1/683 watt per steradian.
24
7. LAW OF CHEMICAL COMBINATION

The mass standard is the kilogram since 1889. It has been
defined as the mass of platinum-iridium (Pt-Ir) cylinder 7.1 Law of conservation of mass
that is stored in an airtight jar at International Bureau of
“In a chemical reaction the mass of reactants consumed
Weights and Measures in Sevres, France. Pt-Ir was chosen
and mass of the products formed is same, that is mass is
for this standard because it is highly resistant to chemical
conserved.” This is a direct consequence of law of
attack and its mass will not change for an extremely long
conservation of atoms. This law was put forth by Antoine
time.
Lavoisier in 1789.
6. SOME IMPORTANT DEFINITION 7.2 Law of Constant / Definite Proportions
6.1 Mass and Weight The ratio in which two or more elements combine to form a
compound remains fixed and is independent of the source
Mass of a substance is the amount of matter present in it of the compound. This law was given by, a French chemist,
while weight is the force exerted by gravity on an object. Joseph Proust.
The mass of a substance is constant whereas its weight
7.3 Law of Multiple Proportions
may vary from one place to another due to change in gravity.
The SI unit of mass is the kilogram (kg). The SI derived When two elements combine to form two or more compounds
unit (unit derived from SI base units) of weight is newton. then the ratio of masses of one element that combines with
a fixed mass of the other element in the two compounds is a
6.2 Volume
simple whole number ratio. This law was proposed by Dalton
Volume is the quantity of three-dimensional space enclosed in 1803.
by some closed boundary, for example, the space that a
7.4 Law of Reciprocal Proportions
substance (solid, liquid, gas, or plasma) or shape occupies
or contains. Volume is often quantified numerically using
the SI derived unit, the cubic meter. When three elements combine with each other in
combination of two and form three compounds then the
6.3 Density ratio of masses of two elements combining with fixed mass
of the third and the ratio in which they combine with each
The mass density or density of a material is defined as its other bear a simple whole number ratio to each other. This
mass per unit volume. The symbol most often used for Law was given by Richter in 1792.
density is U (the lower case Greek letter rho). SI unit of
density is kg m–3. 7.5 Gay Lussac’s Law of Gaseous Volumes
6.4 Temperature This law was given by Gay Lussac in 1808. He observed
that when gases combine or are produced in a chemical
Temperature is a physical property of matter that
reaction they do so in a simple ratio by volume provided all
quantitatively expresses the common notions of hot and
gases are at same temperature and pressure.
cold. There are three common scales to measure temperature
— °C (degree celsius), °F (degree fahrenheit) and K (kelvin).
7.6 Avogadro Law
The temperature on two scales is related to each other by
the following relationship: In 1811, Avogadro proposed that equal volumes of gases at
°F = 9/5 (°C) + 32 the same temperature and pressure should contain equal
number of molecules.
K = °C + 273.15
25
8. DALTON’S ATOMIC THEORY 9.3 Method 2
In 1808, Dalton published ‘A New System of Chemical Mass of 6.022 × 10 23 atoms of that element taken in grams.
Philosophy’ in which he proposed the following: This is also known as molar atomic mass.
1. Matter consists of indivisible atoms.
2. All the atoms of a given element have identical properties

including identical mass. Atoms of different elements differ
in mass. Mass of 1 atom in amu and mass of
6.022 × 1023 atoms in grams are numerically equal.
3. Compounds are formed when atoms of different elements
combine in a fixed ratio. When atomic mass is taken in grams it is also called
the molar atomic mass.
4. Chemical reactions involve reorganization of atoms. These
are neither created nor destroyed in a chemical reaction. 6.022 × 1023 is also called 1 mole of atoms and this
number is also called the Avogadro’s Number.
9. ATOM
Mole is just a number. As 1 dozen = 12;
Atom is the smallest part of an element that can participate in a
chemical reaction. {Note : This definition holds true only for 1 million = 10 6; 1 mole = 6.022 × 1023.
non-radioactive reactions}
9.1 Mass of an Atom

10. MOLECULES
A group of similar or dissimilar atoms which exist together in

There are two ways to denote the mass of atoms. nature is known as a molecule. e.g. H2, NH3.
9.2 Method 1 The mass of molecules is measured by adding the masses of
the atoms which constitute the molecule. Thus, the mass of
Atomic mass can be defined as a mass of a single atom which a molecule can also be represented by the two methods used
is measured in atomic mass unit (amu) or unified mass (u) for measuring the mass of an atom viz. amu and g/mol.
where
1 a.m.u. = 1/12th of the mass of one C12 atom
26
is called the Excess Reagent. e.g. if we burn carbon in air

11. CHEMICAL REACTIONS (which has an infinite supply of oxygen) then the amount
of CO2 being produced will be governed by the amount of
A chemical reaction is only rearrangement of atoms. Atoms
carbon taken. In this case, Carbon is the LR and O2 is the
from different molecules (may be even same molecule) rearrange ER.
themselves to form new molecules.
13. PERCENT YIELD
Points to remember :
As discussed earlier, due to practical reasons the amount of
Always balance chemical equations before doing any product formed by a chemical reaction is less than the amount
calculations
predicted by theoretical calculations. The ratio of the amount
The number of molecules in a reaction need not to be of product formed to the amount predicted when multiplied
conserved e.g. by 100 gives the percentage yield.
N2 + 3 H2 Æ 2 NH3. The number of molecules is not
conserved Actual Yield
Percentage Yield = Theoretical Yield × 100
If we talk about only rearrangement of atoms in a
balanced chemical reaction then it is evident that the
mass of the atoms in the reactants side is equal to the
14. REACTIONS IN AQUEOUS MEDIA
sum of the masses of the atoms on the products side. Two solids cannot react with each other in solid phase
This is the Law of Conservation of Atoms and Law of and hence need to be dissolved in a liquid. When a solute
Conservation of Mass. is dissolved in a solvent, they co-exist in a single phase
called the solution. Various parameters are used to measure
the strength of a solution.
12. STOICHIOMETRY
The strength of a solution denotes the amount of solute
The study of chemical reactions and calculations related which is contained in the solution. The parameters used to
to it is called Stoichiometry. The coefficients used to balance denote the strength of a solution are:
the reaction are called Stoichiometric Coefficients.
Mole fraction X : moles of a component / Total moles
of solution.
Mass% : Mass of solute (in g) present in 100g of
The stoichiometric coefficients give the ratio of
solution.
molecules or moles that react and not the ratio of
masses. Mass/Vol : Mass of solute (in g) present in 100mL of
solution
Stoichiometric ratios can be used to predict the moles of
product formed only if all the reactants are present in the v/v : Volume of solute/volume of solution {only for
stoichiometric ratios. liq-liq solutions}
Practically the amount of products formed is always g/L : Wt. of solute (g) in 1L of solution
less than the amount predicted by theoretical
calculations mass of solute
ppm : mass of solution u 10
6
12.1 Limiting Reagent (LR) and Excess Reagent (ER)

moles of solute
If the reactants are not taken in the stoichiometric ratios Molarity (M) : volume of solution (L)
then the reactant which is less than the required amount
determines how much product will be formed and is known moles of solute
as the Limiting Reagent and the reactant present in excess Molality (m) : mass of solvent (kg)
27
IMPORTANT RELATIONS e.g. molality remains unchanged with temperature. Formulae

involving volume are altered by temperature e.g. Molarity.
1. Relation between molality (m) Molarity (M), density (d) of
solution and molar mass of solute (MO) 17. INTRODUCTION TO EQUIVALENT CONCEPT
d : density in g/mL Equivalent concept is a way of understanding reactions
and processes in chemistry which are often made simple
MO : molar mass in g mol–1
by the use of Equivalent concept.
M u 1000 17.1 Equivalent Mass

Molality, m
1000d MM O
2. Relationship between molality (m) and mole fraction (XB) of “The mass of an acid which furnishes 1 mol H+ is called
the solute its Equivalent mass.”
“The mass of the base which furnishes 1 mol OH– is called

XB 1000 1 X A 1000
m u m u its Equivalent mass.”
1 XB MA XA MA
17.2 Valency Factor (Z)
Valency factor is the number of H+ ions supplied by 1
Molarity is the most common unit of measuring
molecule or mole of an acid or the number of OH- ions
strength of solution.
supplied by 1 molecule or 1 mole of the base.
The product of Molarity and Volume of the solution
gives the number of moles of the solute, n = M × V Molecular Mass
Equivalent mass, E
All the formulae of strength have amount of solute. Z
(weight or moles) in the numerator.
17.3 Equivalents
All the formulae have amount of solution in the
denominator except for molality (m).
wt. of acid / base taken
No. of equivalents =
15. DILUTION LAW Eq. wt.
When a solution is diluted, more solvent is added, the moles

of solute remains unchanged. If the volume of a solution
having a Molarity of M1 is changed from V1 to V2 we can
write that: It should be always remembered that 1 equivalent of an
acid reacts with 1 equivalent of a base.
M1V1 = moles of solute in the solution = M2V2
16. EFFECT OF TEMPERATURE 18. MIXTURE OF ACIDS AND BASES
Volume of the solvent increases on increasing the Whenever we have a mixture of multiple acids and bases
temperature. But it shows no effect on the mass of solute in we can find whether the resultant solution would be acidic
the solution assuming the system to be closed i.e. no loss of or basic by using the equivalent concept. For a mixture of
mass. multiple acids and bases find out the equivalents of acids
and bases taken and find which one of them is in excess.
The formulae of strength of solutions which do not involve
volume of solution are unaffected by changes in temperature.
28
22. EQUIVALENT VOLUME OF GASES

19. LAW OF CHEMICAL EQUIVALENCE
Equivalent volume of gas is the volume occupied by 1
According to this law, one equivalent of a reactant
equivalent of a gas at STP.
combines with one equivalent of the other reactant to
give one equivalent of each product . For, example in a Equivalent mass of gas = molecular mass /Z.
reaction aA + bB o cC + dD irrespective of the
Since 1 mole of gas occupies 22.4L at STP therefore 1
stoichiometric coefficients, 1 eq. of A reacts with 1 eq. of
equivalent of a gas will occupy 22.4/Z L at STP. e.g. Oxygen
B to give 1 eq. each of C and 1eq of D
occupies 5.6L, Chlorine and Hydrogen occupy 11.2L.
20. EQUIVALENT WEIGHTS OF SALTS 23. NORMALITY
To calculate the equivalent weights of compounds which
The normality of a solution is the number of equivalents of
are neither acids nor bases, we need to know the charge on
solute present in 1L of the solution.
the cation or the anion. The mass of the cation divided by
the charge on it is called the equivalent mass of the cation
equivalents of solute
and the mass of the anion divided by the charge on it is N
volume of solution (L)
called the equivalent mass of the anion. When we add the
equivalent masses of the anion and the cation, it gives us
the equivalent mass of the salt. For salts, Z in the total The number of equivalents of solute present in a solution is
amount of positive or negative charge furnished by 1 mol given by Normality × Volume (L).
of the salt. On dilution of the solution the number of equivalents of
the solute is conserved and thus, we can apply the
21. ORIGIN OF EQUIVALENT CONCEPT
formula : N1V1 = N2V2
Equivalent weight of an element was initially defined as
Caution :
weight of an element which combines with 1g of hydrogen.
Later the definition wad modified to : Equivalent weight of Please note that the above equation gives rise to a lot of
an element is that weight of the element which combines confusion and is a common mistake that students make.
with 8g of Oxygen. This is the equation of dilution where the number of
equivalents are conserved. Now, since one equivalent of
a reactant always reacts with 1 equivalent of another
reactant a similar equation is used in problems involving
titration of acids and bases. Please do not extend the same
logic to molarity.
Same element can have multiple equivalent weights
depending upon the charge on it. e.g. Fe2+ and Fe3+.
Relationship between Normality and Molarity
N = M × Z ; where ‘Z’ is the Valency factor
29
SOLVED EXAMPLES
Classify the following substances into elements, What is the S.I. unit of mass ?
compounds and mixtures.
Sol. S.I. unit of mass is kilogram (kg).
(i) Air (ii) Diamond (iii) LPG (iv) Dry ice (v) Graphite
(vi) Steel (vii) Marble (viii) Smoke (ix) Glucose
(x) Laughing gas. Example - 6
In the reaction, A + B2 o AB2, identify the limiting
Sol. reagent, if any, in the following mixtures
Elements : Diamond; Graphite (i) 300 atoms of A + 200 molecules B2
Compounds : Marble; Glucose; Laughing gas; Dry ice
(ii) 2 mol A + 3 mol B2
Mixtures : Air; LPG; Steel; Smoke
(iii) 100 atoms of A + 100 molecules of B2
Example - 2
(iv) 5 mol A + 2.5 mol B2
Classify the following mixtures as homogeneous and
heterogeneous. (v) 2.5 mol A + 5 mol B2
(i) Air (ii) Smoke (iii) Petrol (iv) Sea water (v) lodized Sol. (i) According to the given reaction, 1 atom of A reacts
table salt (vi) Aerated water (vii) Mixture of sand and with 1 molecule of B2.
common salt (viii) Gun powder (ix) Milk (x) Muddy water.
? 200 molecules of B2 will react with 200 atoms of A and
Sol. Homogeneous : Air; Petrol; Iodized table salt; Sea water; 100 atoms of A will be left unreacted. Hence, B2 is the
Aerated water; Milk. limiting reagent while A is the excess reagent.
Heterogeneous : Smoke; Gun powder; Mixture of sand (ii) According to the given reaction, 1 mol of A reacts
common salt; Muddy water. with 1 mol of B2 . Hence A is limiting reagent.
Example - 3 (iii) No limiting reagent.

Why Law of conservation of mass should better be called (iv) 2.5 mol of B2 will react with 2.5 mol of A. Hence, B2 is
as Law of conservation of mass and energy ? the limiting reagent.
Sol. In nuclear reactions, it is observed that the mass of the (v) 2.5 mol of A will react with 2.5 mol of B2. Hence, A is
products is less than the mass of the reactants. The the limiting reagent.
difference of mass, called the mass defect, is converted
into energy according to Einstein equation, E = ' m c2. Example - 7
Hence, we better call it as a low of conservation of mass Is the law of constant composition true for all types of
and energy. compounds ? Explain why or why not.
Example - 4
Sol. No, law of constant composition is not true for all types of
If the speed of light is 3.0 × 108 m s–1, calculate the compounds. It is true only for the compounds obtained
distance covered by light in 2.00 ns. from one isotope. For example, carbon exists in two common
isotopes, 12C and 14C.
Sol. Distance covered = Speed × Time = 3.0 × 108m s–1 × 2.00 ns
10 9 s
= 3.0 × 108m s–1 × 2.00 ns × = 6.00 × 10–1m
1 ns
= 0.600 m
30
Example - 8
Example - 11
Why atomic masses are the average values ?
Carbon and oxygen are known to form two compounds.
Sol. Most of the elements exist in different isotopes, i.e., atoms The carbon content in one of these is 42.9% while in
with different masses, e.g., Cl has two isotopes with mass the other it is 27.3%. Show that this data is in agreement
numbers 35 and 37 existing in the ratio 3 : 1 Hence, average with the law of multiple proportions.
value is taken.
Sol. Oxide 1 Carbon Oxygen
Example - 9 42.9% 57.1%
What mass of sodium chloride would be decomposed by
? Amount of oxygen that combines with 1 g carbon
9.8 g of sulphuric acid, if 12 g of sodium bisulphate and
2.75 g of hydrogen chloride were produced in a reaction
57.1
assuming that the law of conservation of mass is true ? = 1.33 g
42.9
Sol. NaCl + H2SO4 = NaHSO4 + HCl
Oxide 1 Carbon Oxygen
According to law of conservations of mass,
27.3% 72.7%
Total masses of reactants = Total masses of products
? Amount of oxygen that combines with 1 g carbon
Let the mass of NaCl decomposed be x g; so
x + 9.8 = 12.0 + 2.75 72.7
= 2.66 g
27.3
= 14.75
x = 4.95 g Ratio of oxygen in oxide (1) and (2) = 1 : 2
Thus, Law of multiple proportion is verified.

Example - 10
In an experiment, 2.4 g of iron oxide on reduction with
Example - 12
hydrogen yield 1.68 g of iron. In another experiment
2.9 g of iron oxide given 2.03 g of iron on reduction with In three moles of ethane (C2H6), calculate :
hydrogen. Show that the above data illustrate the law of
constant proportions. (i) Number of moles of carbon atoms
(ii) Number of moles of hydrogen atoms

Sol. In the first experiment
(iii) Number of molecules of ethane
The mass of iron oxide = 2.4 g
The mass of iron after reduction = 1.68 g Sol. (i) 1 mole of C2H6 contains 2 moles of carbon atoms
The mass of oxygen = Mass of iron oxide – Mass of iron ? 3 moles of C2H6 will C-atoms = 6 moles
= (2.4 – 1.68) = 0.72 g
(ii) 1 mole of C2H6 contains 6 moles of hydrogen atoms
Ration of oxygen and iron = 0.72 : 1.68
? 3 moles of C2H6 will contain H-atoms = 18 moles
= 1 : 2.33
(iii) 1 mole of C2H6 contains Avogadro’s no., i.e.,
In the second experiment
6.02 × 1023 molecules
The mass of iron oxide = 2.9 g
The mass of iron after reduction = 2.03 g ? 3 moles of C2H6 will contain ethane molecules
The mass of oxygen = (2.9 – 2.03) = 0.87 g = 3 × 6.02 × 1023

Ratio of oxygen and iron = 0.87 : 2.03 = 18.06 × 1023 molecules
= 1 : 2.33
31
Example - 16
Example - 13
Zinc sulphate crystals contain 22.6% of zinc and 43.9% Calculate the mass per cent of different elements
of water. Assuming the law of constant proportions to be present in sodium sulphate (Na2SO4).
true, how much zinc should be used to produce 13.7 g of
zinc sulphate and how much water will they contain ? Sol. Mass % of an element
Sol. 100 g of zinc sulphate crystals are obtained from Mass of that element in the compound
u 100
Molar mass of the compound
= 22.6 g zinc
1 g of zinc sulphate crystals will be obtained from Now, molar mass of Na2SO4 = 2 (23.0) + 32.0 + 4 × 16.0
= 22.6/100 g zinc
= 142 g mol–1
13.7 g of zinc sulphate crystals will be obtained from
46
22.6 Mass percent of sodium = u 100 = 32.39 %
× 13.7 = 3.0962 g of zinc 142
100
100 g of zinc sulphate crystals contain water = 43.9 g 32

Mass per cent of sulphur = u 100 = 22.54 %
142
1 g of zinc sulphate crystals contain water = 43.9/100 g
13.7 g of zinc sulphate crystals shall contain water 64
Mass per cent of oxygen = u 100 = 45.07%
142
43.9
× 13.7 = 6.0143 g
100
Example - 17
Example - 14 Calculate the amount of carbon dioxide that could be
What will be the mass of one 12C atom in g ? produced when
(i) 1 mole of carbon is burnt in air.

Sol. 1 mol of 12C atoms = 6.022 × 1023 atoms = 12g
(ii) 1 mole of carbon is burnt in 16 g of dioxygen.
Thus, 6.022 × 1023 atoms of 12C have mass = 12g
(iii) 2 moles of carbon are burnt in 16 g of dioxygen.
12
? 1 atom of 12C will have mass = g
6.022 u10 23 Sol. The balanced equation for the combustion of carbon in
dioxygen/air is
= 1.9927 × 10–23 g
Example - 15 C (s) O2 (g)

o CO2 (g)
1 mole 1 mole 1 mole
(32 g ) (44 g)
Calculate the molecular mass of :
(i) H2O (ii) CO2 (iiii) CH4 (i) In air, combustion is complete. Therefore, CO2
produced from the combustion of 1 mole of carbon =
Sol. (i) Molecular mass of H2O = 2 (1.008 amu) + 16.00 amu 44 g.
= 18.016 amu (ii) As only 16 g of dioxygen is available, it can combine

only with 0.5 mole of carbon, i.e., dioxygen is the limiting
(ii) Molecular mass of CO2 = 12.01 amu + 2 × 16.00 amu
reactant. Hence, CO2 produced = 22 g.
= 44.01 amu
(iii) Here again, dioxygen is the limiting reactant. 16 g of
(iii) Molecular mass of CH4 = 12.01 amu + 4 (1.008 amu) dioxygen can combine only with 0.5 mole of carbon.
= 16.042 amu CO2 produced again is equal to 22 g.
32
Hydrogen chloride (HCl) on oxidation gives water and Boron has two isotopes boron-10 and boron-11 whose
chlorine. How many litres of chlorine at STP can be percentage abundances are 19.6% and 80.4%
obtained starting with 36.50 g HCl ? respectively. What is the average atomic mass of boron ?
Sol. Oxidation of HCl takes place according to the following

Sol. Average atomic mass of B =
equation :
4HCl O 2
o 2Cl2 2H 2O (10 u19.6) (11u 80.4)
4 mol 2 mol = 10.804 amu
100
Mass 36.5 Example - 22
Moles of HCl = Molecular mass 1 mole
36.5
Carbon occurs in nature as a mixture of carbon-12
and carbon-13. The average atomic mass of carbon is
' 4 moles HCl give 2 moles Cl2
12.011. What is the percentage abundance of carbon-12
2 in nature ?
? 1 mole will give moles Cl2 = 0.5 moles Cl2
4
Sol. Let x be the percentage abundance of carbon-12; then
Volume of Cl2 at STP = 22.4 × 0.5 = 11.2 litre (100 – x) will be the percentage abundance of carbon-13.
Example - 19 12x 13 (100 x)

Therefore, 12.011
Why is air sometimes considered as a heterogeneous 100
mixture ?
or 12x + 1300 – 13x = 1201.1
Sol. This is due to the presence of dust particles which form a x = 98.9
separate phase.
Abundance of carbon-12 is 98.9%
Calculate the mass of sodium acetate (CH3COONa) Calculate the mass of 2.5 gram atoms of oxygen.
required to make 500 mL of 0.375 molar aqueous solution.
Molar mass of sodium acetate is 82.0245 g mol–1.
Sol. We know that
Sol. 0.375 M aqueous solution means that 1000 mL of the Mass of an element in grams
solution contain sodium acetate = 0.375 mole Number of gram atoms = Atomic mass of the element in grams
? 500 mL of the solution should contain sodium acetate

So, Mass of oxygen = 2.5 × 16 = 40.0 g
0.375 Example - 24
= mole
2
Calculate the gram atoms in 2.3 g of sodium.
Molar mass of sodium acetate = 82.0245 g mol–1
?Mass of sodium acetate acquired 2.3

Sol. Number of gram atoms = 0.1
23
0.375
= mole × 82.0245g mol–1 [Atomic mass of sodium = 23 g]
2
= 15.380 g.
33
Calculate the mass of 1.5 gram molecule of sulphuric What is the concentration of sugar (C12H22O11) in mol
acid. L–1 if its 20 g are dissolved in enough water to make a
final volume up to 2 L ?
Sol. Molecular mass of H2SO4
Sol. Molar mass of sugar (C12H22O11) = 12 × 12 + 22 × 1 + 11 × 16
= 2 × 1 + 32 + 4 × 16 = 98.0 amu
= 342 g mol–1
Gram-molecular mass of H2SO4 = 98.0 g
20g
Mass of 1.5 gram molecule of H2SO4 = 98.0 × 1.5 = 147.0g No. of moles in 20 g of sugar = 342g mol 1 = 0.0585 mole
Example - 26 Volume of solution = 2 L (Given)

Calculate the actual mass of one molecule of carbon
dioxide (CO2). Moles of solute 0.0582 mol
Molar concentration = Volume of sol in L 2L
Sol. Molecular mass of CO2 = 44 amu = 0.0293 mol L–1 = 0.0293 M

1 amu = 1.66 × 10–24 g Example - 29
So, the actual mass of CO2 = 44 × 1.66 × 10–24 How many molecules of water and oxygen atoms are
present in 0.9 g of water ?
= 7.304 × 10–23g
Sol. Given :
Example - 27
Mass of water = 0.9 g
Calculate the mass of a single atom of sulphur and a
single molecule of carbon dioxide. Molar mass of water = 18 g mol–1
Number of molecules of water and number of oxygen atoms

Sol. Gram-atomic mass of sulphur = 32 g present in water are to be calculated.
Gram atomic mass To find :

Mass of one sulphur atom =
6.02 u10 23
Mass
Number of moles, n = Molar mass
32
= 5.31 × 10–23 g
6.02 u 1023
Number of molecules = n × 6.02 × 1023
Formula of carbon dioxide = CO2 Solution :
Molecular mass of CO2 = 12 + 2 × 16 = 44
0.9
n 0.05
Gram-molecular mass of CO2 = 44 g 18
Number of molecules of water = 0.05 × 6.02 × 1023

Gram molecular mass
Mass of one molecule of CO2=
6.02 u 1023 = 3.01 × 1022
As one molecule of water contains one oxygen atom,

44
= 7.308 × 10–23 g
6.02 u 1023 So, number of oxygen atoms in 3.01 × 1022 molecules of
water
= 3.01 × 1022
34
Example - 30 One molecule of methane has = 6 + 4 = 10 electrons
What is the mass of 3.01 × 1022 molecules of ammonia ? So, 6.02 × 1022 molecules of methane have
= 10 × 6.02 × 1022 electrons

Sol. Gram-molecular mass of ammonia = 17 g
= 6.02 × 1023 electrons
Number of molecules in 17 g (one mole) of NH3 = 6.02 × 1023
Example - 33
Let the mass of 3.01 × 1022 molecules of NH3 be = x g
Calculate the number of moles in 25 g of calcium
carbonate and number of oxygen atoms.
3.01 u 10 22 x
So,
6.02 u 10 23 17
Sol. Formula mass of calcium carbonate
17 u 3.01 u 10 22
(CaCO3) = 100
or x = 0.85 g
6.02 u10 23
Mass in grams 25
Example - 31 No. of moles of CaCO3 = Formula mass
100
How many molecules and atoms of oxygen are present
in 5.6 litres of oxygen (O2) at NTP ? = 0.25 mole
No. of oxygen atoms in one mole of CaCO3

Sol. We know that 22.4 litres of oxygen at NTP contain 6.02 ×
1023 molecules of oxygen. = 3 × 6.02 × 1023
So, 5.6 litres of oxygen at NTP contain No. of oxygen atoms in 0.25 mole of CaCO3
5.6 = 0.25 × 3 × 6.02 × 1023

×6.02 × 1023 molecules
22.4
= 4.515 × 1023
= 1.505 × 1023 molecules
1 molecule of oxygen contains Example - 34
= 2 atoms of oxygen One atom of an element weighs 6.644 × 10 –23 g.

Calculate the number of gram atoms in 40 kg of it.
So, 1.505 × 1023 molecules of oxygen contain
= 2 × 1.505 × 1023 atoms Sol. Atomic mass of the element

23
= 3.01 × 10 atoms = Mass of one atom × 6.02 × 1023
Example - 32
= 6.644 × 10–23 × 6.02 × 1023
How many electrons are present in 1.6 g of methane ?
= 40 g
Sol. Gram-molecular mass of methane
40 kg = 40,000 g
(CH4) = 12 + 4 = 16 g
0ass of the element in grams
1.6 Number of grams atoms = Atomic mass in grams
Number of moles in 1.6 g of methane = 0.1
16
Number of molecules of methane in 0.1 mole 40000
= 1000
= 0.1 × 6.02 × 10 23 40
= 6.02 × 1022
35
250 cm3 of sulphuric acid solution contain 24.5 g of How much copper can be obtained from 100 g of copper
sulphate (CuSO4) ? (Atomic mass of cu = 63.5 amu)
H2SO4. If the density of the solution is 1.98 g cm–3,
determine (i) molarity and (ii) molality.
Sol. 1 mole of CuSO4 contains 1 mole (1 g atom) of Cu
Sol. (i) Molecular mass of H2SO4 = 2 + 32 + 64 = 98 Molar mass of CuSO4 = 63.5 + 32 + 4 × 16 = 159.5 g mol–1
Thus, Cu that can be obtained from 159.5 g of CuSO4
24.5
No. of moles of H2SO4 in solution = 0.25 = 63.5 g
98
? Cu that can be obtained from 100 g of CuSO4
Volume of solution = 250 cm3 = 0.250 L
63.5
= u 100g
0.25 159.5
Molarity =1M
0.250 = 39.81 g
(ii) Mass of solution = 250 × 1.98 = 495.0 g Example - 38

If the density of methanol is 0.793 kg L–1, what is the
Mass of solvent = Mass of solution – Mass of solute volume needed for making 2.5 L of its 0.25 M solution ?
= 495.0 – 24.5 = 470.5g = 0.4705 kg
Sol. Molar mass of methanol (CH3OH) = 32 g mol–1
0.25 = 0.032 kg mol–1
Moality = = 0.53 m
0.4705
0.793 kg L1
Example - 36 Molarity of the given solution
0.032 kg mol 1
Calculate the concentration of nitric acid in moles per = 24.78 mol L–1
–1
litre in a sample which has a density, 1.41 g mL and
mass per cent of nitric acid in it being 69%. Applying M uV
1 1 M V 2 2
(Given solution ) (Solution to be prepared)
24.78 × V1 = 0.25 × 2.5 L or V1 = 0.02522 L = 25.22 mL

Sol. Mass percent of 69% means that 100 g of nitric acid solution
contain 69 g of nitric acid by mass. Example - 39
Pressure is determined as force per unit area of the
Molar mass of nitric acid (HNO3) = 1 + 14 + 48 = 63 g mol–1 surface. The S.I. unit of pressure, pascal, is
69 g 1 Pa = 1 N m–2
? Moles of 68 g HNO3 = 63 g mol 1 = 1.095 mole If mass of air at sea level is 1034g cm–2, calculate the
pressure in pascal.
100 g
Volume of 100 g nitric acid solution = 1.41g mL1 Sol. Pressure is the force (i.e., weight) acting per unit area
But weight = mg
= 70.92 mL = 0.07092 L 1034g u 9.8 ms 2
? Pressure = Weight per unit area =
cm 2
1.095 mole
? Conc. of HNO3 in moles per litre =
0.07092L 1034g u 9.8 ms 2 1kg 100 cm 100cm 1N 1Pa
u u u u 2
u
cm 2
1000g 1m 1m kg ms 1N m 2
= 15.44 M
= 1.01332 × 105 Pa
36
Example - 42
Example - 40
Calculate the number of atoms in each of the following
Calculate the empirical formula of a compound that samples:
contains 26.6% potassium, 35.4% chromium and
38.1% oxygen [Given K = 39.1; Cr = 52; O = 16] (a) 800 amu of Ca (b) 800 grams of Ca
Sol. Element Percentage Atomic mass Sol :

(a) Atomic Mass of Ca = 40 amu
Potassium 26.6 39.1
40 amu is the mass of 1 Ca atom
Chromium 35.4 52.0
Thus, 800 amu is the mass of 800/40 Ca atoms
Oxygen 38.1 16.0 = 20 Ca atoms Ans.
Relative no. Simplest ratio Simplest whole (b) Atomic mass of Ca = 40 g/mole
of atoms no. ratio 40g is the mass of 1 mole Ca atoms
= 6.022 × 1023 Ca atoms
26.6 0.68
0.68 1 1×2=2 Thus, 800g is the mass of (800 × 6.022 × 1023)/40 Ca atoms
39.1 0.68
= 20 mole Ca atoms
35.4 0.68 = 1.2044 × 1025 Ca atoms Ans.
0.68 1 1×2=2
52 0.68
Example - 43
38.1 2.38 Calculate the mass of carbon in 1kg of sugar (C12H22O11)
2.38 3.5 3.5 × 2 = 7
16 0.68
Therefore, empirical formula is K2Cr2O7. Sol : Molecular mass of sugar = 12 × 12 + 22 × 1 + 11 × 16

= 342 g/mol
Example - 41 342g sugar contains = 144g carbon
1000g sugar contains = 421g carbon

(a) Calculate the mass of KClO3 necessary to produce
1.23 g O2.
Example - 44
(b) What mass of KCl is produced along with this
Find the amount of weight of NH3 being produced when
quantity of oxygen ?
1kg of N2 reacts with 1kg of H2. Which reactant is in
excess and how much?
Sol. (a) The reaction involved is :
2KClO3
o 2KCl 3O2 Sol : N2 + 3H2 Æ 2NH3
2 mol 2 mol 3 mol
2 u 122.5 g 2 u 74.5 g 3 u 32 g
1 mole of N2 reacts with 3 moles of H2 to produce
' 3 × 32 g O2 is produced by 2 × 122.5 g KClO3 2 moles of NH3. Thus, 28g N2 reacts with 6g of H2
to produce 34g of NH3.
245
? 1.23 g O2 will be produced by × 1.23 = 3.139 g Since the weight of N2 and H2 taken are equal, so
96
N2- will be consumed before H2. So, N2 is th LR and
(b) ' 2 × 122.5 g KClO3 give 2 × 74.5 g KCl
H2 is the ER.
2 u 74.5 u 3.139 Since, 28g N2- reacts with = 6g H2;
? 3.139 g KClO3 will give = 1.909 g
2 u122.5
37
1000g N2 reacts = with 1000 × 6/28 = 214.3g H2 Moles of NaOH in 2 nd solution = 3 × 5 = 15.
So, H2 is the ER and the amount of H2 in excess Thus on mixing the total moles of NaOH = 24.
= 1000-214.3 = 785.7g Ans. Final Molarity = 1M
Also, 28g N2 produces = 34g NH3; Final moles = 24
so, 1000g N2 produces = 1000 × 34/28 Total Volume of solutions = 8L.
= 1.214kg NH3 Ans. § n·

V = 24L ¨ As M ¸ Ans.
© v¹
Example - 45
The mixture needs to be diluted 3 folds
Calculate the Molarity and molality of a 98%
by mass of H2SO4 solution having a density of 1.25g/cc. Example - 47
An organic containing C,H and N gave the following
Sol : H 2SO 4 taken = 98% 100g of solution contains analysis: C: 40% H:13.3%, N:46.67%. If its molecular
98g H2SO4. formula weight is three times its empirical formula
weight then find out its empirical and molecular formula
mass of solution = 100g of the compound.
mass of solute, H2SO4 = 98g

Sol: Relative no. of atoms of C = 40/12 = 3.33
mass of solvent = 100 – 98 = 2g = 0.002 kg
Relative no. of atoms of H = 13.3/1 = 13.3 and that for N =
98 46.67/14 = 3.33
moles of solute, H2SO4 = 1
98
Thus, simplest atomic ratio C:H:N
mass of solution
volume of solution = = 3.33:13.33:3.33 = 1:4:1
density
Therefore the empirical formula of the compound is CH4N
100
80mL 0.08L Ans.
1.25
Molecular Formula Mass
moles of solute 1 Also, given: Empirical Formula Mass = 3 = n-factor
Molarity, M volume of solution (L) 0.08
= 12.5 M Ans. Therefore, molecular formula is (CH4N)3 i.e. C3H12N3
moles of solute 1 Example - 48

molality, m
mass of solvent (kg) 0.02 Calculate the number of equivalents in the following
samples:
= 500 m Ans.
(a) 490g H2SO4 (b) 1600g NaOH
Example - 46
(c) 730g HCl (d) 0.37g Ca(OH)2
A 3M 3L solution of NaOH is mixed with another 3M
5L solution of NaOH. How much should the mixture be Sol : Eq. wt. of H2SO4 = 98/2 = 49; NaOH = 40/1 = 40;
diluted so that the final Molarity of the solution become
1M ? HCl = 36.5/1 = 36.5; Ca(OH)2 = 74/2 = 37
(a) No. of eq. of H2SO4 = 490/49 = 10 Ans.

Sol : Moles of NaOH in 1 st solution = MV = 3 × 3 = 9.
(b) No. of eq. of NaOH = 1600/40 = 40 Ans.
38
(c) No. of eq. of HCl = 730/36.5 = 20 Ans. N Na 2CO3 = 3.948

?
(d) No. of eq. of Ca(OH)2 = 0.37/37 = 0.01
Now Na2CO3 fresh solution reacts with H2SO4
= 10 milli-eq. Ans
Wt. of Na2CO3 solution = 125 g
Example - 49
A mixture of three acids 3.65 g of HCl, 4.9 g H2SO4 and 125
? Volume of Na2CO3 solution = 100 mL
9 g H2C2O4 is made to react with a mixture of two bases x 1.25
g NaOH and 7.4 g Ca(OH)2. Calculate w for complete
? Meq. of H2SO4 = Meq. of Na2CO3
neutralisation.
0.84 × V = 100 × 3.948
Sol : We know that total equivalents of acids must be equal to
? Volume of H2SO4 required = 470 mL
total equivalents of bases.’
Example - 52
6 (w/E)ACIDS = 6 (w/E)BASES
5 mL of 8N HNO3, 4.8 mL of 5N HCl and a certain
3.65/36.5 + 4.9/49 + 9/45 = x/40 + 7.4/37 volume of 17M H2SO4 are mixed together and made
x = 8g upto 2 litre 30 mL of this acid mixture exactly
neutralizes 42.9 mL of Na2CO3 solution containing 1g
Example - 50 of Na 2CO3. 10H2O in 100 mL of water. Calculate the
amount of sulphate ions in g present in solution.
Calculate the Equivalent mass of Al2 (SO4)3 ?
Sol. Meq. of HNO3 = 5 × 8 = 40
Sol : 1 equivalent of Al2(SO4)3 = 1 equivalent of Al3+ + 1 equivalent
Meq. of HCl = 4.8 × 5 = 24
of SO42-
Meq. of H2SO4 = V × 17 × 2 = 34 V (Let V mL of H2SO4)
E (Al2(SO4)3) = E (Al3+) + E (SO42-)
? Total Meq. of acid in 2 litre solution = 40 + 24 + 34V
§ 27 · § 96 ·
¨ ¸ ¨ ¸ 9 48 57g = 64 + 34V
© 3 ¹ © 2¹
Now Meq. of acid in 30 mL solution = Meq. of Na2CO3 used
This can be tallied by the method for the salt. For this salt z = for it
6 and M = 342 g therefore E = 342/6 = 57 g.
Meq. of Na2CO3
Example - 51
1u1000 § 1 1000 ·
25 mL of a solution of Na2CO3 having a specific gravity 42.9 u 3 ¨ N Na 2CO3 u ¸
286 / 2 u100 © 286 / 2 100 ¹
of 1.25g mL–1 required 32.9 mL of a solution of HCl
containing 109.5 g of the acid per litre for complete 3 u 2000
neutralization. Calculate the volume of 0.84 N H2SO4 ? Meq. of acid in 2 litre solution = 200
30
that will be completely neutralized by 125g of Na2CO3
solution. ? 64 + 34V = 200 ? 34V = 200 – 64 = 136
109.5 Now Meq. of H2SO4 = Meq. of SO42 = 34V = 136

Sol : equivalents of HCl = 3
36.5
w
? Meq. of SO 4 2 = 136 ? u1000 136
3 96/ 2
N HCl 3
1
? Weight of SO 4 2 = 6.528g
Since Na2CO3 is completely neutralized by HCl
? Meq. of Na2CO3 = Meq. of HCl

N × 25 = 32.9 × 3
39
EXERCISE - 1 : BASIC OBJECTIVE QUESTIONS
Equilibrium : Definition 1 1
(a) (b)
4 2
1. In chemical reaction A B, the system will be known
(c) 1 (d) 4
in equilibrium when
7. On a given condition, the equilibrium concentration of HI,
(a) A completely changes to B
H2 and I2 are 0.80, 0.10 and 0.10 mole/litre. The equilibrium
(b) 50% of A changes to B
constant for the reaction H2 + I2 2HI will be
(c) The rate of change of A to B and B to A on both the
sides are same (a) 64 (b) 12
(c) 8 (d) 0.8
(d) Only 10% of A changes to B
2. According to law of mass action rate of a chemical reaction 8. For the system A(g) + 2B(g) C(g),the equilibrium
is proportional to concentrations are (A) 0.06 mole/litre (B) 0.12 mole/litre
(C) 0.216 mole/litre. The Keq for the reaction is
(a) Concentration of reactants
(b) Molar concentration of reactants (a) 250 (b) 416
–3
(c) 4 × 10 (d) 125
(c) Concentration of products
(d) Molar concentration of products 9. For the reaction A + 2B C, the expression for
equilibrium constant is
3. The active mass of 64 gm of HI in a two litre flask would be
(a) 2 (b) 1 [A ] [B]2 [A] [B]
(a) (b)
(c) 5 (d) 0.25 [C ] [C]
4. The rate constant for forward and backward reactions of
[C ] [C]
hydrolysis of ester are 1.1 × 10–2 and 1.5 × 10–3 per minute (c) [A ] [B]2 (d) 2 [B] [ A ]
respectively. Equilibrium constant for the reaction is
CH3COOC2H5 + H2O CH3COOH + C2H5OH 10. For which of the following reactions does the equilibrium
constant depend on the units of concentration
(a) 4.33 (b) 5.33
(c) 6.33 (d) 7.33 1 1
(a) NO(g) N 2 (g) O2 (g)
Equilibrium Constant : Expression 2 2
5. For the system 3A + 2B C, the expression for (b) Zn (s) Cu 2 (aq) Cu (s) Zn 2 (aq)
equilibrium constant is (c) C2H5OH (l) + CH3COOH CH3COOC2H5(l)+ H2O (l)
[C] (Reaction carried in an inert solvent)
[3A][2B]
(a) (b) [3A][2B]
C (d) COCl2(g) CO(g) + Cl2(g)
[A]3[B]2 [C] 11. Unit of equilibrium constant for the reversible reaction
(c) (d) [A]3[B]2 H2 + I 2 2HI is
[C]
6. 4 moles of A are mixed with 4 moles of B. At equilibrium for (a) mol–1 litre (b) mol–2 litre
the reaction A + B C + D, 2 moles of C and D are (c) mol litre–1 (d) None of these
formed. The equilibrium constant for the reaction will be
A-1
12. In a reaction A + B C + D, the concentrations of A, B, 19. An equilibrium mixture of the reaction

C and D (in moles/litre) are 0.5, 0.8, 0.4 and 1.0 respectively. 2H2S(g) 2H2 (g) + S2(g)
The equilibrium constant is
had 0.5 mole H2S, 0.10 mole H2 and 0.4 mole S2 in one litre
(a) 0.1 (b) 1.0 vessel. The value of equilibrium constant (K) in mole litre-1
(c) 10 (d) f is
13. The suitable expression for the equilibrium constant of (a) 0.004 (b) 0.008
the reaction 2NO (g) + Cl2(g) 2NOCl (g) is (c) 0.016 (d) 0.160
20. For the equilibrium N2 + 3H2 2NH3, Kc at 1000K is
2 –3
[2 NOCl] [ NOCl] 2.37 × 10 If at equilibrium [N2] = 2M, [H2] = 3M, the
(a) K c (b) K c
[2 NO] [Cl 2 ] [ NO]2 [Cl 2 ] concentration of NH3 is
(a) 0.00358 M (b) 0.0358 M
[ NOCl]2 [ NOCl]2
(c) K c (d) K c (c) 0.358 M (d) 3.58 M
[ NO] [Cl 2 ]2 [ NO]2 [Cl 2 ]2
21. Two moles of NH3 when put into a previously evacuated
14. A+ B C + D. If finally the concentration of A and B vessel (one litre), partially dissociate into N2 and H2. If at
are both equal but at equilibrium concentration of D will equilibrium one mole of NH3 is present, the equilibrium
be twice of that of A then what will be the equilibrium constant is
constant of reaction. (a) 3/4 mol2 litre–2 (b) 27/64 mol2 litre–2
(a) 4 / 9 (b) 9 / 4 (c) 27/32 mol2 litre–2 (d) 27/16 mol2 litre–2
(c) 1 / 9 (d) 4 22. In Haber process 30 litres of dihydrogen and 30 litres of
dinitrogen were taken for reaction which yielded only 50%
15. For the reaction 2SO2 + O2 2SO3, the units of Kc are of the expected product. What will be the composition of
gaseous mixture under the aforesaid condition in the end
(a) litre/mole (b) mol/litre
–1 2 (a) 20 litres ammonia, 25 litres nitrogen, 15 litres hydrogen
(c) (mol litre ) (d) (litre mole–1)2
(b) 20 litres ammonia, 20 litres nitrogen, 20 litres hydrogen
16. The equilibrium concentration of X, Y and YX2 are 4, 2 (c) 10 litres ammonia, 25 litres nitrogen, 15 litres hydrogen
and 2 moles respectively for the equilibrium
(d) 20 litres ammonia, 10 litres nitrogen, 30 litres hydrogen
2X + Y YX2. The value of Kc is
23. For the reaction equilibrium N2O4 2NO2(g), the
(a) 0.625 (b) 0.0625 concentrations of N 2 O4 and NO2 at equilibrium are
(c) 6.25 (d) 0.00625 4.8 × 10–2 and 1.2 × 10–2 mol litre–1 respectively. The value
17. In a 500 ml capacity vessel CO and Cl2 are mixed to form of Kc for the reaction is
COCl2. At equilibrium, it contains 0.2 moles of COCl2 and (a) 3.3 × 102 mole litre–1 (b) 3 × 101 mol litre–1
0.1 mole of each of CO and CO2. The equilibrium constant (c) 3 × 10–3 mol litre–1 (d) 3 × 103 mol litre–1
Kc for the reaction CO + Cl2 COCl2 is 24. The equilibrium constant for the reaction
N2(g) + O2(g) 2NO (g) at temperature T is 4 × 10–4.
(a) 5 (b) 10
(c) 15 (d) 20 The value of Kc for the reaction
18. 4.5 moles each of hydrogen and iodine heated in a sealed 1 1

NO (g) N 2 (g ) O 2 (g ) at the same temperature
ten litre vessel. At equilibrium, 3 moles of HI were found. 2 2
The equilibrium constant for H2(g) + I2(g) 2 HI(g) is is
(a) 1 (b) 10 (a) 4 × 10–4 (b) 50

(c) 5 (d) 0.33 (c) 2.5 × 10 2
(d) 0.02
A-2
25. In the reaction, H2 + I2 2HI. In a 2 litre flask 0.4 moles of Position of Equilibrium : Extent of a Reaction
each H2 and I2 are taken. At equilibrium 0.5 moles of HI are 30. In which of the following, the reaction proceeds towards
formed. What will be the value of equilibrium constant, Kc completion
(a) 20.2 (b) 25.4 (a) K = 103 (b) K = 10–2

(c) 0.284 (d) 11.1 (c) K = 10 (d) K = 1
26. 2 mol of N2 is mixed with 6 mol of H2 in a closed vessel of 31. A 1 M solution of glucose reaches dissociation equilibrium
according to equation given below 6HCHO C6H12O6
one litre capacity. If 50% of N2 is converted into NH3
What is the concentration of HCHO at equilibrium if
at equilibrium, the value of K c for the reaction
equilibrium constant is 6 × 1022
N2(g) + 3H2(g) 2NH3(g) is
(a) 1.6 × 10–8 M (b) 3.2 × 10–6 M
(a) 4/27 (b) 27/4
(c) 3.2 × 10–4 M (d) 1.6 × 10–4 M
(c) 1/27 (d) 24
Equilibrium Constant : Effect of Stoichiometry Kp and Kc Relationship
27. Equilibrium constants K1 and K 2 for the following 32. In which of the following reaction, the value of K p will be
equilibria equal to K c
(a) H2 + I2 2HI (b) PCl5 PCl3 + Cl2

1
NO(g) + O NO2(g)
2 2 (c) 2NH3 N2 + 3H2 (d) 2SO2 + O2 2SO3
and 2NO2(g) 2NO(g) + O2(g) are related as 33. For N2 + 3H2 2NH3 + heat
1 (a) Kp = Kc (RT) (b) Kc = Kp (RT)

(a) K 2 K1 (b) K 2 K12 (c) Kp = Kc (RT) –2
(d) Kp = Kc (RT)–1
34. In which of the following equilibria, the value of Kp is less
K1 1
(c) K 2 (d) K 2 than Kc
2 K12
(a) H2 + I2 2HI
28. Two gaseous equilibria
(b) N2 + 3H2 2 NH3
1 1 (c) N2 + O2 2NO
SO 2 (g ) O 2 (g ) SO 2 (g ) O 2 (g ) SO3(g)
2 2 (d) CO + H2O CO2 + H2
and
35. For the reaction H2(g) + I2(g) 2HI(g) at 721K the
2SO3(g) 2SO2(g) + O2(g) have equilibrium constants
value of equilibrium constant (K c) is 50. When the
K1 and K2 respectively at 298 K. Which of the following
equilibrium concentration of both is 0.5M, the value of Kp
relationships between K1 and K2 is correct
under the same conditions will be
(a) K1 = K2 (b) K2 = K12
(a) 0.002 (b) 0.2
(c) K2 = 1/K12 (d) K2 = 1/K1
(c) 50.0 (d) 50 / RT
29. At a given temperature, the equilibrium constant for
36. The reaction between N2 and H2 to form ammonia has
reaction PCl5(g) PCl3(g) + Cl2(g) is 2.4 × 10–3. At the
same temperature, the equilibrium constant for reaction Kc = 6 × 10–2 at the temperature 500°C. The numerical
PCl3(g) + Cl2(g) PCl5(g) is value of Kp for this reaction is
(a) 2.4 × 10–3 (b) – 2.4 × 10–3 (a) 1.5 × 10–5 (b) 1.5 × 105
(c) 4.2 × 102 (d) 4.8 × 10–2 (c) 1.5 × 10–6 (d) 1.5 × 106
A-3
37. For the reversible reaction, 42. 40% of a mixture of 0.2 mol of N2 and 0.6 mol of H2 reacts to
N2(g) + 3H2(g) 2NH3(g) give NH3 according to the equation :
at 500°C, the value of Kp is 1.44 × 10–5 when partial pressure N 2 (g) 3H 2 (g) U 2NH 3 (g)
is measured in atmospheres. The corresponding value of
at constant temperature and pressure. Then the ratio of
Kc with concentration in mole litre-1, is the final volume to the initial volume of gases are
(a) 1.44 × 10–5/(0.082 × 500)–2 (a) 4 : 5 (b) 5 : 4
–5 –2 (c) 7 : 10 (d) 8 : 5
(b) 1.44 × 10 /(8.314 × 773)
(c) 1.44 × 10–5/(0.082 × 773)2 43. XY2 dissociates as :

–5 –2
(d) 1.44 × 10 /(0.082 × 773) XY2 (g) U XY(g) Y(g)
Equilibrium : Analysis
Initial pressure of XY2 is 600 mm Hg. The total pressure at
38. A mixture of 0.3 mole of H2 and 0.3 mole of I2 is allowed to equilibrium is 800 mm Hg. Assuming volume of system to
react in a 10 litre evacuated flask at 500ºC. The reaction is remain constant, the value of Kp is
H2 + I 2 2HI, the K is found to be 64. The amount of
(a) 50 (b) 100
unreacted I2 at equilibrium is
(c) 200 (d) 400
(a) 0.15 mole (b) 0.06 mole
44. 15 mol of H2 and 5.2 moles of I2 are mixed and allowed to
(c) 0.03 mole (d) 0.2 mole
attain equilibrium at 500ºC. At equilibrium, the
39. 0.6 mole of NH3 in a reaction vessel of 2dm3 capacity was concentration of HI is found to be 10 mol. The equilibrium
brought to equilibrium. The vessel was then found to constant for the formation of HI is.
contain 0.15 mole of H2 formed by the reaction (a) 50 (b) 25
2NH3(g) N2(g) + 3H2(g) (c) 200 (d) 15
Which of the following statements is true 45. For the equilibrium AB (g) U A(g) + B(g). Kp is equal to
(a) 0.15 mole of the original NH3 had dissociated at four times the total pressure. Calculate the number moles
of A formed if one mol of AB is taken initially.
equilibrium
(b) 0.55 mole of ammonia is left in the vessel (a) 0.45 (b) 0.30
(c) 0.60 (d) 0.90
(c) At equilibrium the vessel contained 0.45 mole of N2
(d) The concentration of NH3 at equilibrium is 0.25 mole 46. I 2 I U I 3

per dm3 This reaction is set-up in aqueous medium. We start with
–
40. 5 moles of SO2 and 5 moles of O2 are allowed to react to 1 mol of I2 and 0.5 mol of I in 1L flask. After equilibrium is
form SO3 in a closed vessel. At the equilibrium stage 60% reached, excess of AgNO 3 gave 0.25 mol of yellow
of SO2 is used up. The total number of moles of SO2, O2 precipitate. Equilibrium constant is
and SO3 in the vessel now is (a) 1.33 (b) 2.66
(a) 10.0 (b) 8.5 (c) 2.00 (d) 3.00
(c) 10.5 (d) 3.9
47. One mole of N2O4(g) at 100 K is kept in a closed container
41. The equilibrium P4 (s) + 6 Cl2 (g) ZZX 4 PCl3(g) is attained at 1.0 atm pressure. It is heated to 400 K, where 30% by
YZZ
mass of N2O4(g) decomposes of NO2(g). The resultant
by mixing equal moles of P4 and Cl2 in an evacuated vessel.
pressure will be
Then at equilibrium
(a) 4.2 (b) 5.2
(a) [Cl2] > [PCl3] (b) [Cl2] > [P4]
(c) 3.2 (d) 6.2
(c) [P4] > [Cl2] (d) [PCl3] > [P4]
A-4
Equilibrium Constant and 'G

to yield NH3 and H2 S gases in the flask. When the
48. 'Gº(HI; g) # 1.7 kJ. What is the equilibrium constant decomposition reaction reaches equilibrium, the total
pressure in the flask rises to 0.84 atm. The equilibrium
at 25ºC for 2HI(g) H2(g) + I2(g)
constant for NH4HS decomposition at this temperature is
(a) 24.0 (b) 3.9 (a) 0.30 (b) 0.18
(c) 2.0 (d) 0.5 (c) 0.17 (d) 0.11
49. Calculate 'Gº for conversion of oxygen to ozone 55. Calculate the partial pressure of carbon monoxide from
the following
3/2 O2(g) o O3(g) at 298 K, if Kp for this conversion is
2.47 × 10–29 CaCO3 (s) CaO(s) + CO2 n; Kp = 8 × 10–2
(a) 163 kJ mol–1 (b) 2.4 × 102 kJ mol–1 CO2(g) + C (s) o 2CO (g) ; Kp = 2
–1 6 –1
(c)1.63 kJ mol (d) 2.38 × 10 kJ mol (a) 0.2 (b) 0.4
(c) 1.6 (d) 4
Homogeneneous and Heterogeneous Equilibria,
56. Change in volume of the system does not alter the number
Degree of Dissociation of moles in which of the following equilibrium
50. Pure ammonia is placed in a vessel at temperature where (a) N2(g)+ O2(g) 2NO(g)
its dissociation ( D ) is appreciable. At equilibrium
(b) PCl5 (g) PCl3 (g) + Cl2(g)
(a) Kp does not change significantly with pressure
(c) N2(g) + 3H2(g) 2NH3(g)
(b) D does not change with pressure
(d) SO2Cl2(g) SO2(g) + Cl2(g)
(c) Concentration of NH does not change with pressure
57. The equilibrium constant (K p ) for the reaction
(d) Concentration of H2 is less than that of N2
PCl5(g) o PCl3(g) + Cl2(g) is 16. If the volume of the
51. At a certain temp. 2HI H2 + I2 Only 50% HI is container is reduced to one half its original volume, the
dissociated at equilibrium. The equilibrium constant is value of Kp for the reaction at the same temperature will be
(a) 0.25 (b) 1.0 (a) 32 (b) 64
(c) 3.0 (d) 0.50 (c) 16 (d) 4
52. 3.2 moles of hydrogen iodide were heated in a sealed bulb 58. Consider the following equilibrium in a closed container :
at 444°C till the equilibrium state was reached. Its degree N2O4 (g) U 2 NO2(g)
of dissociation at this temperature was found to be 22%. At a fixed temperature, the volume of the reaction container
The number of moles of hydrogen iodide present at is halved. For this change, which of the following
equilibrium are statements, holds true regarding the equilibrium constant
(a) 2.496 (b) 1.87 (Kp) and degree of dissociation (D) ?
(c) 2 (d) 4 (a) neither Kp nor D changes
53. The vapour density of completely dissociated NH4Cl (b) both Vp and D change
would be (c) Kp changes but D does not change
(a) Slight less than half that of NH4Cl (d) Kp does not change but D changes
59. Calculate the partial pressure of carbon monoxide from
(b) Half that of NH4Cl the following data :
(c) Double that of NH4Cl '
CaCO3 (s) o CaO (s) CO 2 n, Kp = 8 × 10–2
(d) Determined by the amount of solid NH4Cl in the
experiment CO2(g) + C (s)
o 2 CO (g), Kp = 2
54. An amount of solid NH4HS is placed in a flask already (a) 0.2 (b) 0.4
containing ammonia gas at a certain temperature and 0.50 (c) 1.6 (d) 4
atm. pressure. Ammonium hydrogen sulphide decomposes
A-5
60. A small amount of NH4HS is placed in a flask already 64. At the equilibrium of the reaction,
containing ammonia gas at a certain temperature and
N2O4 (g) U 2 NO2 (g),
0.50 atm pressure. Ammonium hydrogen sulphide
decomposes to yield NH3 and H2S gases in the flask. When the observed molecular weight of N2O4 is 80 g mol–1 at 350
the decomposition reaction reaches equilibrium, the total K. The percentage of dissociation of N2O4 (g) at 350 K is
pressure in the flask rises to 0.84 atm. The equilibrium
constant for NH4HS decomposition at this temperature is (a) 10% (b) 15%
(a) 0.30 (b) 0.18 (c) 20% (d) 18%
(c) 0.17 (d) 0.11 Le Chatelier’s Principle
61. The vapour density of completely dissociated NH4Cl is 65. What is the effect of halving the pressure by doubling the
(a) double than that of NH4Cl volume on the following system at 500°C
(b) half than that of NH4Cl H2(g) + I2(g) 2HI(g)
(c) same as that of NH4Cl
(a) Shift to product side
(d) determined by the amount of solid NH4Cl taken
(b) Shift to product formation
62. The following two equilibria exist simultaneously in a
closed vessel : (c) Liquifaction of HI
ZZX PCl3(g) + Cl2 (g)

PCl5(g) YZZ (d) No effect
ZZX CO (g) + Cl2 (g)

COCl2 (g) YZZ 66. In equilibrium CH3COOH + H2O CH COO– + H+
If some CO is added into the vessel, then after the The equilibrium constant may change when
equilibrium is attained again, concentration of
(a) CH COO– are added (b) CH COOH is added
(a) PCl5 will increase (b) PCl5 wil decrease
(c) Catalyst is added (d) Mixture is heated
(c) PCl5 will remain unaffected
67. Which of the following statements regarding a chemical
(d) Cl2 will increase
equilibrium is wrong
63. The equilibrium constant (Kp) for the decomposition of
gaseous H2O (a) An equilibrium can be shifted by altering the
temperature or pressure
1
H2O (g) U H2 (g) + O (g) (b) An equilibrium is dynamic
2 2
(c) The same state of equilibrium is reached whether one
is related to degree of dissociation (D) at a total pressure
starts with the reactants or the products
p, given by
(d) The forward reaction is favoured by the addition of a
D p1/ 2 catalyst
(a) K p
(1 D) (2 D)1/ 2
68. In the reaction, A2(g) + 4 B2(g) 2AB4(g)
D p3 / 2 'H 0 the formation of AB4 is will be favoured at

(b) K p
(1 D ) (2 D)1/ 2
(a) Low temperature, high pressure
D3 / 2 p2 (b) High temperature, low pressure

(c) K p
(1 D ) (2 D )1/ 2 (c) Low temperature, low pressure
(d) High temperature, high pressure
D 3 / 2 p1/ 2
(d) K p
(1 D ) (2 D)1/ 2
A-6
69. The formation of SO takes place according to 75. In the reaction A(g) + 2B(g) C(g) + Q kJ, greater
the following reaction, product will be obtained or the forward reaction is favoured
by
2SO2 + O2 2SO3 ; 'H = – 45.2 kcal
(a) At high temperature and high pressure
The formation of SO is favoured by
(b) At high temperature and low pressure
(a) Increasing in temperature
(c) At low temperature and high pressure
(b) Removal of oxygen
(d) At low temperature and low pressure
(c) Increase of volume
76. Following gaseous reaction is undergoing in a vessel
(d) Increasing of pressure
C2H4 + H2 C2H6; 'H = – 32.7 Kcal
70. N2 + O 2 2NO - Q cals
Which will increase the equilibrium concentration of C2H6
In the above reaction which is the essential condition for
the higher production of NO (a) Increase of temperature
(a) High temperature (b) High pressure (b) By reducing temperature
(c) Low temperature (d) Low pressure
(c) By removing some hydrogen
71. Which of the following reactions proceed at low pressure
(d) By adding some C2H6
(a) N2 + 3H2 2NH (b) H2 + I2 2HI
77. The effect of increasing the pressure on the equilibrium
(c) PCl5 PCl3 + Cl2 (d) N2 + O2 2NO
2A + 3B 3A + 2B is
72. In the following reversible reaction
(a) Forward reaction is favoured
2SO2 + O2 2SO + Q Cal
(b) Backward reaction is favoured
Most suitable condition for the higher production of SO
(c) No effect
is
(d) None of the above
(a) High temperature and high pressure
(b) High temperature and low pressure 78. The exothermic formation of ClF is represented by the
(c) Low temperature and high pressure equation
(d) Low temperature and low pressure Cl2(g) + 3F2(g) 2ClF3(g); 'H = – 329 kJ
73. The reaction A + B C + D +heat has reached Which of the following will increase the quantity of ClF
equilibrium. The reaction may be made to proceed
forward by in an equilibrium mixture of Cl2, F2 and ClF
(a) Adding more C (a) Increasing the temperature

(b) Adding more D (b) Removing Cl2
(c) Decreasing the temperature
(c) Increasing the volume of the container
(d) Increasing the temperature
(d) Adding F2
74. According to Le-chatelier principle, if heat is given to solid-
liquid system, then 79. In which of the following system, doubling the volume of
(a) Quantity of solid will reduce the container cause a shift to the right
(b) Quantity of liquid will reduce (a) H2(g) + Cl2(g) 2HCl(g)
(c) Increase in temperature (b) 2CO(g) + O2(g) 2CO2(g)
(d) Decrease in temperature
(c) N2(g) + 3H2(g) 2NH3(g)
(d) PCl5(g) PCl3(g) + Cl2(g)
A-7
80. Which of the following information can be obtained on 83. The formation of nitric oxide by contact process
the basis of Le-chatelier’s principle N2 + O 2 2NO. 'H = 43.200 kcal is favoured by
(a) Entropy change in a reaction (a) Low temperature and low pressure
(b) Dissociation constant of a weak acid (b) Low temperature and high pressure
(c) Equilibrium constant of a chemical reaction (c) High temperature and high pressure
(d) Shift in equilibrium position on changing value of a (d) High temperature and excess reactants concentration
constant
84. The yield of product in the reaction
81. The equilibrium SO2Cl2 (g) SO2(g) + Cl2(g) is attained
A2(g)+ 2B(g) C(g) + Q.kJ. would be high at
at 25°C in a closed container and an inert gas helium is
introduced which of the following statement is correct (a) High temperature and high pressure
(a) More chlorine is formed (b) High temperature and low pressure
(b) Concentration of SO2 is reduced (c) Low temperature and high pressure
(d) Low temperature and low pressure
(c) More SO2Cl2 is formed
(d) Concentration of SO2Cl2(SO2) and Cl2 does not change
82. H2(g) + I2(g) 2HI(g) 'H = + q cal, then formation of HI

(a) Is favoured by lowering the temperature
(b) Is favoured by increasing the pressure
(c) Is unaffected by change in pressure
(d) Is unaffected by change in temperature
A-8
ANSWER KEY
EXERCISE 1 : (Basic Objective Questions)
1. (c) 2. (b) 3. (d) 4. (d) 5. (d) 6. (c) 7. (a) 8. (a) 9. (c) 10. (d)
11. (d) 12. (b) 13. (b) 14. (d) 15. (a) 16. (b) 17. (b) 18. (a) 19. (c) 20. (c)
21. (d) 22. (c) 23. (c) 24. (b) 25. (d) 26. (a) 27. (d) 28. (c) 29. (c) 30. (a)
31. (d) 32. (a) 33. (c) 34. (b) 35. (c) 36. (a) 37. (d) 38. (b) 39. (d) 40. (b)
41. (c) 42. (a) 43. (b) 44. (a) 45. (d) 46. (a) 47. (b) 48. (d) 49. (a) 50. (a)
51. (a) 52. (a) 53. (b) 54. (d) 55. (b) 56. (a) 57. (c) 58. (d) 59. (b) 60. (d)
61. (b) 62. (b) 63. (d) 64. (b) 65. (d) 66. (d) 67. (d) 68. (a) 69. (d) 70. (a)
71. (c) 72. (c) 73. (c) 74. (a) 75. (c) 76. (b) 77. (c) 78. (d) 79. (d) 80. (d)
81. (d) 82. (c) 83. (d) 84. (c)
Dream on !!
[\]^[\]^
A-9
IONIC EQUILIBRIUM

11. Conjugate base of NH3 is
Theory of Electrolytes, AcidBase Strength Comparison
1. Which one of the following substance has the highest (a) NH4 (b) NH2
proton affinity
(c) NH24 (d) N2
(a) H2O (b) H2S
12. According to Bronsted principle, an aqueous solution
(c) NH3 (d) PH3
of HNO3 will contain
2. Which of the following is not a Lewis acid – –
(a) NO2 (b) NO3
(a) BF3 (b) FeCl3 + +
(c) NO2 (d) NO
(c) SiF4 (d) C2H4
13. Ammonium ion is
–
3. The conjugate base of NH2 is (a) Neither an acid nor base
2–
(a) NH3 (b) NH (b) Both an acid and a base
(c) NH4
+
(d) N3
– (c) A conjugate acid (d) A conjugate base
4. Which of the following is the weakest acid 14. Which shows weak ionisation in water
(a) HF (b) HCl (a) H2SO4 (b) NaCl

(c) HBr (d) HI (c) HNO3 (d) NH3
2–
5. Among the following, the weakest Lewis base is 15. The conjugate acid of HPO4 is
– – – 3–
(a) H (b) OH (a) H2PO4 (b) PO4
– –
(c) Cl (d) HCO3 (c) H3PO4 (d) H3PO3
6.
–
Cl is the conjugate base of Weak Acids and Bases : Analysis
(a) HClO4 (b) HCl 16. A monoprotic acid in 1.00 M solution is 0.01% ionised.
The dissociation constant of this acid is
(c) HOCl (d) HClO3 –8 –4
(a) 1 × 10 (b) 1 × 10
7. Which one is the weakest acid –6 –5
(c) 1 × 10 (d) 10
(a) HNO3 (b) HClO4
17. If D is the degree of ionization, C the concentration of a
(c) H2SO4 (d) HBr weak electrolyte and Ka the acid ionization constant, then
8. Which one is lewis acid the correct relationship between D, C and Ka is
– +
(a) Cl (b) Ag
Ka 2 C
(b) D
2
(c) C2H5OH (d) S
2– (a) D Ka
C
9. The correct order of acid strength is
Ka C
(a) HClO < HClO2 < HClO3 < HClO4 (c) D (d) D Ka
C
(b) HClO4 < HClO < HClO2 < HClO3
18. For a weak acid HA, Ostwald’s dilution law is represented
(c) HClO2 < HClO3 < HClO4 < HClO by the equation
(d) HClO4 < HClO3 < HClO2 < HClO
Dc D 2c
10. Which of the following is the weakest base (a) K a (b) K a
1 D 2
1 D
(a) NaOH (b) Ca(OH)2
Kac D 2c
(c) NH4OH (d) KOH (c) D (d) K a
1 c 1 D2
A-10
IONIC EQUILIBRIUM
19. In which of the following dissociation of NH4OH will be 27. Review the equilibrium and choose the correct statement
+ –
minimum HClO4 + H2O YZZZ H3O + ClO4
ZZZX
(a) NaOH (b) H2O (a) HClO4 is the conjugate acid of H2O
(c) NH4Cl (d) NaCl +
(b) H3O is the conjugate base of H2O
20. The following equilibrium exists inaqueous solution, (c) H2O is the conjugate acid of H3O
+
– +
CH3COOH YZZZZZX Z CH3COO + H if dil HCl is added, –
(d) ClO4 is the conjugate base of HClO4
without change in temperature, the
–
28. In the reaction 2H2O H3O+ + OH–, water is
(a) Concentration of CH3COO will increase
(a) A weak base
–
(b) Concentration of CH3COO will decrease
(b) A weak acid
(c) The equilibrium constant will increase (c) Both a weak acid and a weak base
(d) The equilibrium constant will decrease (d) Neither an acid nor a base
21. The degree of dissociation of 0.1 M HCN solution is 29. The unit of ionic product of water Kw are
0.01%. Its ionisation constant would be
–1 –1 –2 –2
–3 –5
(a) Mol L (b) Mol L
(a) 10 (b) 10
–2 –1 2 –2
–7 –9
(c) Mol L (d) Mol L
(c) 10 (d) 10
30. Ionic product of water increases, if
22. The hydrogen ion concentration in weak acid of +
(a) Pressure is reduced (b) H is added
dissociation constant Ka and concentration c is nearly
–
equal to (c) OH is added (d) Temperature increases
31. At 90ºC, pure water has [H3O+] = 10–6 mole litre–1. What is
(a) Ka / c (b) c/Ka
the value of Kw at 90º C ?
(c) Kac (d) Kac (a) 10–6 (b) 10–12
23. Degree of dissociation of 0.1 N CH3COOH is (c) 10–14 (d) 10–8

–5 32. HCOOH and CH3COOH solution have equal pH. If K1/K2
(Dissociation constant = 1 × 10 )
(ratio of acid dissociation constants) is 4, ratio of their
–5 –4
(a) 10 (b) 10 molar concentration will be :
(c) 10
–3
(d) 10
–2 (a) 2 (b) 0.5
24. 0.2 molar solution of formic acid is ionized 3.2%. Its (c) 4 (d) 0.25
ionization constant is 33. 2H2O H3O+ + OH–, Kw = 1 × 10–14 at 25ºC hence Ka is:
–3 –4
(a) 9.6 × 10 (b) 2.1 × 10 (a) 1 × 10
–14
(b) 5.55 × 10–3
–6 –5
(c) 1.25 × 10 (d) 4.8 × 10 (c) 18 × 10–17 (d) 1.00 × 10–7
25. The values of dissociation constants of some acids (at 34. For a “c molar” concentrated solution of a weak electrolyte
25°C) are as follows. Indicate which is the strongest acid AxBy, the degree of dissociation is given as
in water
–2 –4 (a) D K eq / c ( x y )
(a) 1.4 × 10 (b) 1.6 × 10
–10 –7
(c) 4.4 × 10 (d) 4.3 × 10 (b) D K eq c /( xy )
– –10
26. Concentration CN in 0.1 M HCN is [Ka = 4 × 10 ]
1 /( x y )
(a) 2.5 × 10 M
–6
(b) 4.5 × 10 M
–6 (c) D K eq / c x y 1x x y y
–6 –6
(c) 6.3 × 10 M (d) 9.2 × 10 M
(d) K eq / xyc
A-11
IONIC EQUILIBRIUM
35. The pH of a 0.1 M aqueous solution of a weak acid (HA) is 44. For a pure water,
3. What is its degree of dissociation ? (a) pH increases and pOH decreases with increase in
(a) 1% (b) 10% temperature
(c) 50% (d) 25% (b) pH decreases and pOH increases with increase in
36. Autoprotolysis constant of NH3 is temperature
(c) both pH and pOH increase with increase in temperature
(a) [NH 4 ] [NH 3 ] (b) [NH 2 ] [NH 3 ]
(d) both pH and pOH decrease with increase in

(c) [NH ] [NH ]4 2
(d) [NH ] /[NH ]
4 2
temperature
pH of Solutions 45. Equal volumes of two solutions of hydrochloric acid are

mixed. One solution has a pH 1 while the other has a pH5.
37. What is the pH value of N/1000 KOH solution The pH of the resulting solution is :
–11
(a) 10 (b) 3 (a) less than 1 (b) Between 1 and 2
(c) 2 (d) 11 (c) 3 (d) Between 4 and 5
38. The pH of a 0.001 M NaOH will be
46. The dissociation constants of monobasic acids A, B, C
(a) 3 (b) 2 –4
and D are 6 × 10 , 5 × 10–5, 3.6 × 10–6 and 7 × 10–10
(c) 11 (d) 12 respectively. The pH values of their 0.1 molar aqueous
–9 solutions are in the order :
39. The pH of a 10 M solution of HCl in water is
(a) A < B < C < D (b) A > B > C > D
(a) 8 (b) – 8
(c) Between 7 and 8 (d) Between 6 and 7 (c) A = B = C = D (d) None of these
40. A is an aqueous acid; B is an aqueous base. They are 47. The pH of a solution is increased from 3 to 6; its H+ ion
diluted separately, then concentration will be :
(a) pH of A increases and pH of B decreases (a) reduced to half (b) doubled
(b) pH of A increases and pH of B decreases till pH in (c) reduced by 1000 times (d) increased by 1000 times
each case is 7
48. Aspirin (acetyl salicyclic acid, molar mass = 180 g mol–1)
(c) pH of A and B increase used as analgesic has pKa value of 2. Two tablets of aspirin
(d) pH of B and A decrease each weighing 90 mg are dissolved in 100 mL of water. The
41. Pure water is kept in a vessel and it remains exposed to pH of the solution is
atmospheric CO2 which is absorbed, then its pH will be (a) 0.5 (b) 1.0
(a) Greater than 7 (b) Less than 7 (c) 2.0 (d) 4.0
(c) 7 49. A patient is said to suffer from acidosis when the pH of his
(d) Depends on ionic product of water blood
42. An acid solution of pH = 6 is diluted hundred times. The (a) falls below 7.35
pH the solution becomes :
(b) rises above 7.35
(a) 6.95 (b) 6
(c) Shows sudden fall and rise
(c) 4 (d) 8
(d) has strong basic character
43. The number of H+ ions present in 1 mL of a solution having
pH = 13 is : 50. What is the pH of a 0.015 M Ba(OH) 2 solution ?
(a) 1013 (b) 6.023 × 1013 (a) 1.82 (b) 1.52
(c) 6.023 × 107 (d) 6.023 × 1010 (c) 12.48 (d) 12.18
A-12
IONIC EQUILIBRIUM
51. Equal volumes of two solutions of HCl are mixed. One 59. How many moles of HCOONa must be added to 1L of 0.1
solution has a pH = 1, while the other has a pH = 5. The M HCOOH to prepare a buffer solution with a pH of 3.4 ?
pH of the resulting solution is (Given : Ka for HCOOH = 2 × 10–4)
(a) < 1 (b) Between 1 and 2
(a) 0.01 (b) 0.05
(c) 3 (d) Between 4 and 5
(c) 0.1 (d) 0.2
52. At a certain temperature the value of pK w is 13.4 and
the measured pH of soln is 7. The solution is 60. What is the pH of a buffer solution which is 0.250 M in
benzoic acid, C 6 H5 COOH, and 0.150 M in sodium
(a) Acidic (b) Basic
benzoate, C 6 H 5 COONa, if Ka for benzoic acid is
(c) Neutral (d) Unpredictable
6.5 × 10 –5 ?
Buffer Solutions
(a) 3.40 (b) 3.97
53. For preparing a buffer solution of pH 6 by mixing sodium
acetate and acetic acid, the ratio of the concentration of (c) 4.19 (d) 4.41
–5
salt and acid should be (Ka = 10 ) 61. Calculate the pH of a buffer prepared by mixing 0.10
mol of sodium formate and 0.05 mole of formic acid in
(a) 1 : 10 (b) 10 : 1
1.0 L of solution. [HCO2H : Ka =1.8 × 10 –4]
(c) 100 : 1 (d) 1 : 100
(a) 1.8 × 10 –4 (b) 3.44
54. In a mixture of a weak acid and its salt, the ratio of
concentration of acid to salt is increased ten-fold. The (c) 4.05 (d) 5.31
pH of the solution 62. 100 mL of a buffer solution contains 0.1 M each of weak
(a) Decreases by one (b) Increases by one-tenth acid HA and salt NaA. How many gram of NaOH should
be added to the buffer so that its pH will be 6 ?
(c) Increases by one (d) Increases ten-fold
–10
(Ka of HA = 10–5).
55. The dissociation constant of HCN is 5 × 10 . The pH of
(a) 0.328 (b) 0458
the solution prepared by mixing 1.5 mole of HCN and
0.15 moles of KCN in water and making up the total volume (c) 4.19 (d) None
3
to 0.5 dm is 63. Two buffer solutions, A and B, each made with acetic
(a) 7.302 (b) 9.302 acid and sodium acetate differ in their pH by one unit, A
has salt : acid = x : y, B has salt : acid = y : x. If x > y, then
(c) 8.302 (d) 10.302 the value of x : y is
56. The principal buffer present in human blood is (a) 10,000 (b) 3.17
(a) NaH2PO4 + Na2HPO4 (c) 6.61 (d) 2.10
(b) H3PO4 + NaH2PO4 64. Buffer solutions can be prepared from mixtures of
(c) CH3COOH + CH3COONa (a) HCl and NaCl (b) NaH2PO4 and Na2HPO4
(d) H2CO3 + HCO 3 (c) CH3COOH + NaCl (d) NH4OH + NH3
57. 0.1 mole of CH3NH2 (Kb = 5 × 10–4) is mixed with 0.08 mole 65. A certain buffer solution contains equal concentration
4
of HCl and the solution diluted to one litre. The H+ ion of X4 and HX. The K b for X is 10 –10. The pH of the
concentration in the solution will be buffer is
(a) 1.6 × 10–11 (b) 8 × 10–11 (a) 4 (b) 7
(c) 5 × 10 –5
(d) 8 × 10 –2
(c) 10 (d) 14
58. The pKa of weak acid (HA) is 4.5. The pOH of an aqueous 66. The pKb of CN 4 is 4.7. The pH of solution prepared by
buffered solution of HA in which 50% of the acid is ionized mixing 2.5 mol of KCN of 2.5 mol of HCN in water and
is making the total volume upto 500 mL is
(a) 7.0 (b) 4.5 (a) 10.3 (b) 9.3
(c) 2.5 (d) 9.5 (c) 8.3 (d) 4.7
A-13
IONIC EQUILIBRIUM
67. The pH of a dilute solution of acetic acid was found to 74. Which one of the following statements is true with
be 4.3. The addition of a small crystal of sodium acetate regard to a 0.10 M H2 SO4 solution ?
will cause pH to
(a) [H2SO4] > [H+] (b) [H+] = [SO 24 ]
(a) Become less than 4.3 (b) Become more than 4.3
(c) Remain equal to 4.3 (d) Unpredictable (c) [SO 24 ] > [HSO 4 ] (d) [H+] > [HSO 4 ]
68. To 1.0 L solution containing 0.1 mol each of NH3 and
75. What is the pH of 0.01 M glycine solution ? For glycine
NH 4Cl, 0.05 mol NaOH is added. The change in pH will
be (pKa for CH3COOH = 4.74) K a1 4.5 × 10–3 and K a2 1.7 × 10–10 at 298 K
(a) 0.30 (b) –0.30
(a) 3.0 (b) 10.0
(c) 0.48 (d) –0.48
(c) 6.1 (d) 7.2
69. The pH of blood is maintained by the balance between
Salt Hydrolysis
H2CO3 and NaHCO 3. If the amount of CO 2 in the blood
is increased, how will it effect the pH of blood ? 76. Aq. solution of sodium cyanide is
(a) pH will remain same (b) pH will be 7 (a) Acidic (b) Amphoteric
(c) pH will increase (d) pH will decrease (c) Basic (d) Netural
70. Fixed volume of 0.1 M benzoic acid (pKa = 4.2) solution 77. The solution of strong acid and weak base (FeCl3) is
is added into 0.2 M sodium benzoate solution and (a) Acidic (b) Basic
formed a 300 mL, resulting acidic buffer solution. If pH
of the resulting solution is 3.9, then added volume of (c) Neutral (d) none of these
benzoic acid is 78. Which one of the following salts gives an acidic solution
in water
(a) 240 mL (b) 150 mL
(a) CH3COONa (b) NH4Cl
(c) 100 mL (d) None
(c) NaCl (d) CH3COONH4
Polyprotic Acids and Bases
79. An aqueous solution of aluminium sulphate would show
71. In a 0.010 M solution of oxalic acid, H 2 C 2 O 4 ,
Ka1 = 5.9 × 10 –2, Ka2 = 6.4 × 10 –5, the species present in (a) An acidic reaction
the lowest concentration is (b) A neutral reaction
(a) H2C2O4 (b) H3O+ (c) A basic reaction
(d) Both acidic and basic reaction
(c) HC2 O 4 (d) C2 O42
80. An aqueous solution of sodium carbonate is alkaline
72. Calculate the carbonate ion concentration in a 0.10 M because sodium carbonate is a salt of
solution of the weak acid, carbonic acid are (H 2CO3).
(a) Weak acid and weak base
The dissociation constants of carbonic acid are
(b) Strong acid and weak base
Ka1 = 4.5 × 10 –7 and Ka2 = 4.7 × 10 –11.
(c) Weak acid and strong base
(a) 4.7 × 10 –11 M (b) 1.0 × 10 –7 M
(d) Strong acid and strong base
(c) 4.5 × 10 –7 M (d) 2.1 × 10 –4 M
81. The aqueous solution of ammonium chloride is
73. In a saturated solution of H2S, DECREASING the pH of
the solution will cause (a) Neutral (b) Basic
(c) Acidic (d) Amphoteric
(a) the S2– concentration to decrease
(b) the H 2S concentration to decrease 82. The aqueous solution of FeCl3 is acidic due to
(c) the S 2– concentration to increase (a) Acidic impurities (b) Ionisation
(d) no change in either the H2S or S 2– concentration (c) Hydrolysis (d) Dissociation
A-14
IONIC EQUILIBRIUM
83. Which is the correct alternate for hydrolysis constant of Solubility Equilibria
NH4CN 91. The solubility product of a salt having general formula
–12 2+
MX2, in water is : 4 × 10 . The concentration of M ions
Kw Kw in the aqueous solution of the salt is
(a) Ka (b) K u K –6 –4
a b (a) 2.0 × 10 M (b) 1.0 × 10 M
–4 –10
(c) 1.6 × 10 M (d) 4.0 × 10 M
Kb Ka
(c) (d) K 92. Let the solubility of an aqueous solution of Mg(OH)2 be
c b
x then its ksp is
84. The pH 0.1 M solution of the following salts increases in
3 5
the order : (a) 4x (b) 108x
(a) NaCl < NH4Cl < NaCN < HCl (c) 27x
4
(d) 9x
(b) HCl < NH4Cl < NaCl < NaCN
93. The solubility in water of a sparingly soluble salt AB2 is
(c) NaCN < NH4Cl < NaCl < HCl –5 –1
1.0 × 10 mol l . Its solubility product number will be
(d) HCl < NaCl < NaCN < NH4Cl. –15 –10
(a) 4 × 10 (b) 4 × 10
85. The pK a1 and pK a 2 of an amino acid are 2.3 and 9.7 –15 –10
(c) 1 × 10 (d) 1 × 10
respectively. The isoelectric point of amino acid is :
(a) 12 (b) 7.4 94. The solubility of CaF2 is a moles/litre. Then its solubility
product is........
(c) 6.0 (d) 3.7
2 3
86. HCN is a weak acid (Ka = 6.2 × 10–10). NH4OH is a weak (a) s (b) 4s
2 3
base (Kb = 1.8 × 10–5). A 1M solutionk of NH4CN would (c) 3s (d) s
be : 95. Which is the correct representation of the solubility
(a) strongly acidic (b) weakly acidic product constant of Ag2CrO4
(c) neutral (d) weakly basic + 2 –2 + –2
(a) [Ag ] [CrO4 ] (b) [Ag ] [CrO4 ]
87. The equilibrium constant for this reaction is 3.6×10 –7.
+ –2 + 2 –2
(c) [2Ag ] [CrO4 ] (d) [2Ag ] [CrO4 ]

OCl (aq.) H 2 O(l ) U HOCl(aq.) OH (aq.)
96. A precipitate of AgCl is formed when equal volumes of
What is Ka for HOCl ? the following are mixed. [Ksp for AgCl = 10 ]
–10
–8 –7
(a) 2.8 × 10 (b) 3.6 × 10 –4 –7
–4
(a) 10 M AgNO3 and 10 M HCl
(c) 6 × 10 (d) 2.8 × 10 –6
–5 –6
88. Ka for hydrofluoric acid is 6.9 × 10–4 . What is the (b) 10 M AgNO3 and 10 M HCl
equilibrium constant K for the following reaction ? –5
(c) 10 M AgNO3 and 10 M HCl
–4
F (aq.) H 2 O(l ) U HF(aq.) OH (aq.) –6

(d) 10 M AgNO3 and 10 M HCl
–6
(a) 6.9 × 10–11 (b) 1.4 × 10 –11 97. The correct representation for solubility product of SnS2
(c) 2.6 × 10 –9 (d) 8.3 × 10 –6 is
89. Ka for HF is 3.5 × 10 –4. Calculate Kb for the fluoride ion. (a) [Sn ] [S ]
4+ 2– 2
(b) [Sn ] [S ]
2+ 2– 2
–4 –7
(a) 3.5 × 10 (b) 1.0 × 10 2+ 2– 4+ 2– 2
–11
(c) [Sn ] [2S ] (d) [Sn ] [2S ]
(c) 2.9 × 10 (d) 1.0 × 10 –14
–9
90. Ka for ascorbic acid (HASc) is 5 × 10–5. Calculate the 98. Solubility product of BaCl2 is 4 × 10 . Its solubility in
moles/litre would be
[H ] in an aqueous so lution in whic h t he
–3 –9
4
(a) 1 × 10 (b) 1 × 10
concentration of ASc ions is 0.02 M.
–27 –27
(a) 2 × 10 –6
(b) 2 × 10 –7 (c) 4 × 10 (d) 1 × 10
(c) 5 × 10–9 (d) 5 × 10 –10
A-15
IONIC EQUILIBRIUM
99. Solubility of AgCl will be minimum in 107. Ksp of Mg(OH)2 is 4.0 × 10 –6. At what minimum pH,
(a) 0.001 M AgNO3 (b) Pure water Mg2+ ions starts precipitating 0.01 MgCl
(a) 2 + log 2 (b) 2 – log 2
(c) 0.01 M CaCl2 (d) 0.01 M NaCl
–6
(c) 12 + log 2 (d) 12 – log 2
100. At 298 K, the solubility product of PbCl2 is 1.0 × 10 .
108. The pH of an aqueous solution of Ba(OH)2 is 10. If the Ksp
What will be the solubility of PbCl2 in moles/litre of Ba(OH)2 is 1 × 10–9, then the concentration of Ba2+ ions
(a) 6.3 × 10
–3
(b) 1.0 × 10
–3 in the solution in mol L–1 is
–3 –14
(a) 1 × 10–2 (b) 1 × 10–4
(c) 3.0 × 10 (d) 4.6 × 10
(c) 1 × 10–1 (d) 1 × 10–5
–6
101. Ksp for Ca(OH)2 is 5.5 × 10 . What is the maximum pH that 109. CaCO 3 and BaCO 3 have solubility product values
can be attained in a sewage tank treated with slaked lime ? 1 × 10–8 and 5 × 10–9, respectively. If water is shaken up
(a) 9.35 (b) 10.35 with both solids till equilibrium is reached, the
concentration of CO32 ion is
(c) 11.35 (d) 12.35
(a) 1.5 × 10–8 (b) 1.225 × 10–4
102. For a sparingly soluble salt Ap Bq, the relationship of its
(c) 2.25 × 10–9 (d) None of these
solubility product (LS) with its solubility (S) is :
Indicators and Titrations
(a) LS = Sp+q . pp. qq (b) LS = Sp+q . pq . qp
110. What will be the pH of a solution formed by mixing 40 ml
(c) LS = Spq . pp . qq (d) LS = Spq (pq)p+q of 0.10 M HCl with 10 ml of 0.45 M NaOH
103. When equal volumes of the following solutions are mixed, (a) 12 (b) 10
–10
precipitation of AgCl (Ksp = 1.8 × 10 ) will occur only (c) 8 (d) 6
with :
111. The rapid change of pH near the stoichiometric point of
(a) 10–4 M (Ag+) and 10–4M (Cl–) an acid-base titration is the basis of indicator detection.
pH of the solution is related to ratio of the concentrations
(b) 10–5 M (Ag+) and 10–5 M (Cl–) –
of the conjugate acid (HIn) and base (In ) forms of the
(c) 10–6 M (Ag+) and 10–6 M (Cl–) indicator by the expression
(d) 10–10 M (Ag+) and 10–10 M (Cl–)
[HIn]
(a) log pH pK In
104. The solubility product of different sparingly soluble [In ]
salts are :
1. XY = 4 × 10 –20 2. X2Y = 3.2 × 10–11 [In ]
(b) log pH pK In
3. XY3 = 2.7 × 10–31 [HIn ]
The increasing order of solubility is :
(a) 1, 3, 2 (b) 2, 1, 3 [In ]
(c) log pK In pH
[HIn]
(c) 1, 2, 3 (d) 3, 1, 2
105. Solubility of AgCN is maximum in :
[HIn]
(d) log pK In pH
(a) acidic buffer solution (b) basic buffer solution [In ]
(c) in pure water (d) equal in all solution
112. The pH indicators are :
106. The solubility of CH3COOAg in a buffer solution with
(a) salts of strong acids and strong bases
104
pH = 4, whose K sp = 10 –12 and Ka = is (b) salts of weak acids and weak bases
3
(c) either weak acids or weak bases
(a) 10 –6 (b) 0.5 × 10 –6
(d) either strong acids or strong bases
(c) 5 × 10 –6 (d) 2 × 10 –6
A-16
IONIC EQUILIBRIUM
113. In which of the following acid-base titration, pH is greater (a) (i) o A, (ii) o B, (iii) o C
than 8 at the equivalence point ? (b) (i) o A, (ii) o C, (iii) o B
(a) Acetic acid versus ammonia (c) (i) o B, (ii) o C, (iii) o A
(b) Acetic acid versus sodium hydroxide (d) (i) o C, (ii) o A, (iii) o B
(c) Hydrochloric acid versus ammonia 119. In which of the following acid-base titration, pH is
(d) Hydrochloric and versus sodium hydroxide greater than 8 at the equivalence point ?
114. Why are strong acids generally used as standard (a) Aceitic acid vs ammonia
solutions in acid-base titrations ? (b) Acetic acid vs sodium ammonia
(a) The pH at the equivalent point will always be 7 (c) Hydrochloric acid vs ammonia
(b) They can be used to titrate both strong and weak (d) Hydrochloric acid vs sodium hydroxide
bases 120. 20 cm3 of x M solution of HCl is exactly neutralised by
(c) Strong acids form more stable solutions than weak 40 cm3 of 0.05 M NaOH solution, the pH of HCl solution
acids is
(d) The salts of strong acid do not hydrolyze (a) 1.0 (b) 2
115. The best indicator for detection of end point in titration of (c) 1.5 (d) 2.5
a weak acid and a strong base is : 121. Phenolphthalein does not act as an indicator for the
(a) methyl orange (3 to 4) titration between
(b) methyl red (5 to 6) (a) HCl and NH4OH (b) Ca(OH)2 and HCl
(c) bromothymol blue (6 to 7.5) (c) NaOH and H 2SO4 (d) KOH and CH3COOH
(d) phenolphthalein (8 to 9.6) 122. Methyl orange gives red colour in
116. Which of the following mixture will have the pH close to 1 ? (a) KOH solution (b) HCl solution
(a) 100 ml of M/10 HCl + 100 ml of M/10 NaOH (c) Na 2CO3 solution (d) NaCl solution
(b) 55 ml of M/10 HCl + 45ml of M/10 NaOH 123. Which acid-base indicator should be used in an
(c) 10 ml of M/10 HCl + 90 ml of M/10 NaOH aqueous solution titration which is complete at about
(d) 75 ml of M/5 HCl + 25 ml of M/5 NaOH 0.001 M H+ (aq) ? The transition range in pH is given in
117. Consider the titratiokns listed below. In which is the parenthesis.
pH at the equivalence point described incorrectly ? (a) Methyl violet (0.5 – 1.5)
Acid Base pH at equiv.pt. (b) Methyl red (4.2 – 6.3)
(a) CH3COOH NaOH > 7.00 (c) Methyl yellow (2.9 – 4.0)
(b) HNO3 Ca(OH)2 = 7.00 (d) Phenol red (6.4 – 8.0)
(c) HCl NH 3 < 7.00 124. A sample of 50.0 mL of 0.10 M NH3 (Kb = 1.8 × 10–5) is
(d) HF NaOH < 7.00 titrated with 0.10 M HCl. Calculate the pH at the
118. Which indicator is suitable for the titrations : equivalence point.
Titration Indicator (a) 6.98 (b) 2.87
(i) HCOOH/NaOH (A) Bromothymol blue or (c) 7.78 (d) 5.28
phenolphthalein or methyl
orange or thymolphthalein
(ii) HBr/KOH (B) Methyl orange or methyl
red or bromocresol green
(iii) NH4OH.HNO3 (C) Phenolphthalein or
thymolphthalein
A-17
IONIC EQUILIBRIUM
Answer Key
Exercise1 (Basic Objective Questions)
1. (c) 2. (d) 3. (b) 4. (a) 5. (c) 6. (b) 7. (a) 8. (b) 9. (a) 10. (c)
11. (c) 12. (b) 13. (c) 14. (d) 15. (a) 16. (a) 17. (c) 18. (b) 19. (a,c) 20. (b)
21. (d) 22. (d) 23. (d) 24. (b) 25. (a) 26. (c) 27. (d) 28. (c) 29. (d) 30. (d)
31. (b) 32. (d) 33. (c) 34. (c) 35. (a) 36. (c) 37. (d) 38. (c) 39. (d) 40. (a)
41. (b) 42. (a) 43. (c) 44. (d) 45. (b) 46. (a) 47. (c) 48. (c) 49. (a) 50. (c)
51. (b) 52. (b) 53. (b) 54. (a) 55. (c) 56. (d) 57. (b) 58. (d) 59. (b) 60. (b)
61. (c) 62. (a) 63. (b) 64. (b) 65. (a) 66. (b) 67. (b) 68. (c) 69. (d) 70. (a)
71. (d) 72. (a) 73. (a) 74. (d) 75. (c) 76. (c) 77. (a) 78. (b) 79. (a) 80. (c)
81. (c) 82. (c) 83. (b) 84. (b) 85. (c) 86. (d) 87. (a) 88. (b) 89. (c) 90. (c)
91. (b) 92. (a) 93. (a) 94. (b) 95. (a) 96. (c) 97. (a) 98. (a) 99. (c) 100. (a)
101. (d) 102. (a) 103. (a) 104. (a) 105. (a) 106. (d) 107. (c) 108. (c) 109. (b) 110. (a)
111. (b) 112. (c) 113. (b) 114. (c) 115. (d) 116. (d) 117. (d) 118. (d) 119. (b) 120. (a)
121. (a) 122. (b) 123. (c) 124. (d)
Dream on !!
[\]^[\]^
A-18
Atoms Molecules
1. Which of the following contains atoms equal to those in 8. The number of molecules in 4.25 g of ammonia is about
12 g Mg ? (At. wt. Mg = 24)
(a) 1.0 × 1023 (b) 1.5 × 1023
(a) 12 gm C (b) 7 gm N2
(c) 2.0 × 1023 (d) 2.5 × 1023
(c) 32 gm O2 (d) None of These
9. If 20% nitrogen is present in a compound, its minimum
molecular weight can be
1
2. If 1 moles of oxygen combine with Al to form Al2O3, the
2 (a) 144 (b) 28
weight of Al used in the reaction is (Al = 27)
(c) 100 (d) 70
(a) 27 g (b) 54 g
11. The weight of molecule of the compound C60H122 is
(c) 40.5 g (d) 81 g
(a) 1.4 × 10–21 g (b) 1.09 × 10–21 g
3. Which has the highest mass ?
(c) 5.025 × 1023 g (d) 16.023 × 1023 g
(a) 50 g of iron (b) 5 moles of N2
11. Choose the wrong statement :
(c) 0.1 mol atom of Ag (d) 1023 atoms of carbon
(a) 1 mole means 6.02 × 1023 particles
4. The number of atoms present in 0.5 mole of nitrogen is
same as the atoms in (b) Molar mass is mass of one molecule
(a) 12 g of C (b) 64 g of S (c) Molar mass is mass of one mole of a substance
(c) 8 g of O (d) 48 g of Mg
(d) Molar mass is molecular mass expressed in grams
5. Which of the following weighs the least ?
12. Which among the following is the heaviest ?
(a) 2 g atom of N (at. wt. of N = 14)
(a) One mole of oxygen
(b) 3 × 1023 atoms of C (at. wt. of C = 12)
(b) One molecule of sulphur trioxide
(c) 1 mole of S (at. wt. of S = 32)
(d) 7 g silver (at. wt. of Ag = 108) (c) 100 amu of uranium
6. If A is Avogadro’s number then number of valence (d) 44g of carbon dioxide

electrons in 4.2 g of nitride ions (N3–) is
13. Rearrange the following I to IV in order of increasing
(a) 2.4 NA (b) 4.2 NA masses and choose the correct answer [At. wt. of N = 14 u,
O = 16 u, Cu = 63 u]
(c) 1.6 NA (d) 3.2 NA
I 1 molecule of oxygen
7. Haemoglobin contains 0.33% of iron by weight. The
molecular weight of haemoglobin is approximately 67200. II 1 atom of nitrogen
The number of iron atoms (at. wt. of Fe = 56) present in III 1 × 10–10 mol molecule of oxygen
one molecule of haemoglobin is
IV 1 × 10–10 mol atom of copper
(a) 6 (b) 1
(a) II < I < III < IV (b) IV < III < II < I
(c) 4 (d) 2
(c) II > I > III > IV (d) I < II < IV < III
A-19
14. The number of moles of SO2Cl2 in 13.5 g is : 21. A sample of pure calcium weighing 1.35 g was
(a) 0.1 (b) 0.2 quantitatively converted to 1.88 g of pure calcium oxide.
Atomic mass of calcium would be :
(c) 0.3 (d) 0.4
15. The largest number of molecules is in (a) 20 (b) 40
(a) 36 g of water (c) 16 (d) 35.5

(b) 28 g of carbon monoxide 22. 30g of magnesium and 30g of oxygen are reacted, then the
(c) 46 g of ethyl alcohol residual mixture contains
(d) 54 g of nitrogen pentoxide. (a) 60g of Magnesium oxide only
16. Which of the following contains maximum number of
(b) 40g of Magnesium oxide and 20 g of oxygen
atoms ?
(a) 6.023 × 1021 molecules of CO2 (c) 45 g of Magnesium oxide and 15g of oxygen
(b) 22.4 L of CO2 at STP (d) 50 g of Magnesium oxide and 10g of oxygen
(c) 0.44 g of CO2 23. Silicon carbide, is produced by heating SiO2 and C to high
temperatures according to the equation :
(d) None of these
Stoichiometric Calculations SiO2 (s) + 3C (s) o SiC (s) + 2CO (g)
17. If 0.5 mol of BaCl2 is mixed with 0.2 mol of Na3PO4, the How many grams of SiC could be formed by reacting 2.00
maximum number of mole of Ba3(PO4)2 that can be formed g of SiO2 and 2.0 g of C ?
is (a) 1.33 (b) 2.56
(a) 0.7 (b) 0.5
(c) 3.59 (d) 4.0
(c) 0.30 (d) 0.10
24. Given the reaction
18. One mole of a mixture of CO and CO2 requires exactly 20 gram
Pb(NO3)2 (aq) + 2KI o PbI2 (s) + 2KNO3 (aq)
of NaOH in solution for complete conversion of all the CO2
into Na2 CO3. How many moles more of NaOH would it require What is the mass of PbI2 that will precipitate if 10.2 g of
for conversion into Na2CO3 if the mixture (one mole) is Pb(NO3)2 is mixed with 5.73 g of KI in a sufficient quantity
completely oxidised to CO2. of H2O ?
(a) 0.2 (b) 0.5
(a) 2.06 g (b) 4.13 g
(c) 0.4 (d) 1.5
(c) 7.96 g (d) 15.9 g
19. The number of water molecules present in a drop of water
(volume = 0.0018 ml) at room temperature is (density of 25. If 9 moles of O2 and 14 moles of N2 are placed in a container
H2O = 1 g/mL) and allowed to react according to the equation :
(a) 6.023 × 1019 (b) 1.084 × 1018 3O2 + 2N2 o 2N2O3
(c) 4.84 × 1017 (d) 6.023 × 1023 The reaction proceeds until 3 moles of O2 remain, how
many moles of N2O3 are present at that instant ?
20. What is the weight of oxygen required for the complete
combustion of 2.8 kg of ethylene ? (a) 6 (b) 3
(a) 2.8 kg (b) 6.4 kg (c) 4 (d) 12
(c) 9.6 kg (d) 96 kg
A-20
26. Iron (III) oxide can be reduced with CO to foum metalic 32. Mole fraction of ethanol in ethanol - water mixture is 0.25.
iron as described by unbalanced chemical reaction Hence, percentage concentration of ethanol (C2H6O) by
Fe2O3 + CO o Fe + CO2 weight of mixture is
(a) 25 (b) 75
The number of moles of CO required to form one mole of
Fe from its oxide is (c) 46 (d) 54
(a) 1 (b) 1.5 Strength : Molality
(c) 2 (d) 3 33. A molal solution is one that contains one mole of a
solute in
Percentage Purity
(a) 1000 g of the solvent
27. The mass of CaO that shall be obtained by heating 20 kg
of 90% pure lime-stone (CaCO3) is (b) one litre of the solvent
(a) 11.2 kg (b) 8.4 kg (c) one litre of the solution
(c) 10.08 kg (d) 16.8 kg (d) 22.4 litres of the solution
28. If potassium chlorate is 80% pure, then 48 g of oxygen 34. An aqueous solution of ethanol has density 1.025 g/mL
would be produced from (atomic mass of K = 39) and it is 2 M. What is the molality of this solution ?
(a) 153.12g of KClO3 (b) 122.5 g of KClO3 (a) 1.79 (b) 2.143
(c) 245 g of KClO3 (d) 98.0 g of KClO3 (c) 1.951 (d) None of these
Percentage Yield
35. What volume of 0.4 M FeCl3 . 6H2O will contain 600 mg of
29. Antimony reacts with sulphur according to the equation
Fe3+ ?
2Sb(s) + 3S(s) o Sb2S3(s)
(a) 49.85 mL (b) 26.78 mL
The molar mass of Sb2S3 is 340 g mol–1.
(c) 147.55 mL (d) 87.65 mL
What is the percentrage yield for a reaction in which 1.40
g of Sb2S3 is obtained from 1.73 g of antimony and a slight 36. A sample of H2SO4 (density 1.8 g/ml) is 90% by weight.
excess of sulphur ? What is the volume of the acid that has to be used to make
(a) 80.9 % (b) 58.0 % 1 litre of 0.2 M H2SO4?
(c) 40.5 % (d) 29.0 % (a) 16 mL (b) 10 mL
30. NH3 is produced according to the following reaction :
(c) 12 mL (d) 18 mL
2
(g) + 3H2(g) o 2NH3(g)
37. The density (in g mL–1) of a 3.60 M sulphuric acid
In an experiment 0.25 mol of NH3 is formed when 0.5 mol of
solution that is 29% H2SO4 (molar mass = 98 g mol–1) by
2
is reacted with 0.5 mol of H2. What is % yield ?
mass will be
(a) 75% (b) 50%
(c) 33% (d) 25% (a) 1.45 (b) 1.64
Strength : Mass Percent (c) 1.88 (d) 1.22

31. What is the weight % sulhuric acid in an aqueous solution 38. An antifreeze mixture contains 40% ethylene glycol
which is 0.502 M in sulphuric acid ? The specify gravity of
(C2H6O2) by weight in the aqueous solution. If the density
the solution is 1.07
of this solution is 1.05 g mL, what is the molar
(a) 4.77 % (b) 5.67 % concentration?
(c) 9.53 % (d) 22.0 % (a) 6.77 M (b) 6.45 M
(c) 0.0017 M (d) 16.9 M
A-21
39. What is the molarity of SO 24 ion in aqueous solution that 46. A sample of H2SO4 (density 1.8 g mL–1) is 90% by weight.
What is the volume of the acid that has to be used to make
contain 34.2 ppm of Al2(SO4)3 ? (Assume complete 1 L of 0.2 M H2SO4 ?
dissociation and density of solution 1 g/mL)
(a) 16 mL (b) 18 mL
(a) 3 × 10–4 M (b) 2 × 10–4 M
(c) 12 mL (d) 10 mL
–4
(c) 10 M (d) None of these
Strength : Stoichiometric Calculations
Strength : Mole Fraction
47. What is the concentration of nitrate ions if equal volumes
40. The mole fraction of a given sample of I2 in C 6 H 6 is 0.2. of 0.1 M AgNO3 and 0.1 M NaCl are mixed together ?
The molality of I2 in C6H6 is (a) 0.1 M (b) 0.2 M
(a) 0.32 (b) 3.2 (c) 0.05 M (d) 0.25 M

(c) 0.032 (d) 0.48 48. How many grams of NaBr could be formed if 14.2 g of NaI
are reacted with 40.0 mL of a 0.800 M Br2 ?
Strength : Variation
2NaI + Br2 o 2NaBr + I2
41. In which mode of expression, the concentration of a
solution remains independent of temperature ? (a) 3.30 (b) 4.80
(a) Molarity (b) Normality (c) 6.59 (d) 9.75
(c) Formality (d) Molality 49. If AgBr is assumed to be completely insoluble, What mass
of AgBr precipitates when 30.0 mL of a 0.500 mol/L solution
42. With increase of temperature, which of these changes ? of AgNO3 is added to 50.0 mL of an 0.400 mol/L solution of
NaBr ?
(a) molality
(a) 3.76 g (b) 1.28 g
(b) weight fraction of solute
(c) 2.82 g (d) 3.76 kg
(c) fraction of solute present in unit volume of water
50. In a titration, 15.0 cm3 of 0.100 M HCl neutralizes 30.0 cm3
(d) mole fraction. of Ca(OH)2. What is the molarity of Ca(OH)2 solution ?
43. Molarity and Normality changes with temperature (a) 0.0125 (b) 0.0250
because they involve :
(c) 0.0500 (d) 0.200
(a) Moles (b) equivalents
51. 10 mL of 1 M BaCl2 solution and 5 mL 0.5 M K2SO4 are
(c) weights (d) volumes mixed together to precipitate out BaSO4. The amount of
BaSO4 precipated will be
44. When 500.0 mL of 1.0 M LaCl3 and 3.0 M NaCl are mixed.
What is molarity of Cl– ion ? (a) 0.005 mol (b) 0.00025 mol
(a) 4.0 M (b) 3.0 M (c) 0.025 mol (d) 0.0025 mol
(c) 2.0 M (d) 1.5 M Molar Volume of Gas based Calculations
45. When 50 mL of 2.00 M HCl, 100 mL of 1.00 M HCl and 100 52. M g of a substance when vaporised occupy a volume of
5.6 litre at NTP. The molecular mass of the substance will
mL of 0.500 M HCl are mixed together, the resulting HCl
be :
concentration of the solution is
(a) M (b) 2M
(a) 0.25 M (b) 1.00 M
(c) 3M (d) 4M
(c) 3.50 M (d) 6.25 M
A-22
53. Number of molecules in 1 litre of oxygen at NTP is : 61. The Ew of an element is 13. It forms an acidic oxide which
with KOH forms a salt isomorphous with K2SO4. The atomic
6.02 u10 23 6.02 u10 23 weight of element is
(a) (b)
32 22.4
(a) 13 (b) 26
32 (c) 52 (d) 78
(c) 32 × 22.4 (d)
22.4
62. A hydrate of Na2SO3 losses 22.2% of H2O by mass on
54. The number of molecules in 89.6 litre of a gas at NTP are : strong heating. The hydrate is
(a) 6.02×1023 (b) 2×6.02×1023 (a) Na2SO3 4H2O (b) Na2SO3 6H2O
(c) 3×6.02×1023 (d) 4×6.02×1023 (c) Na2SO3 H2O (d) Na2SO3 2H2O
3
55. The mass of 112 cm of CH4 gas at STP is Laws of Chemical Combination
(a) 0.16 g (b) 0.8 g 63. One of the following combinations illustrate law of
(c) 0.08 g (d) 1.6 g reciprocal proportions
Empirical Formula (a) N 2 O 3 , N 2 O 4 , N 2 O 5 (b) NaCl, NaBr, Nal
56. An oxide of metal (M) has 40% by mass of oxygen. Metal M (c) CS 2 , CO 2 , SO 2 (d) PH 3 , P2 O 3 , P2 O 5
has atomic mass of 24. The empirical formula of the oxide is
64. If water samples are taken from sea, river, clouds, lake or
(a) M2O (b) M2O3
snow, they will be found to contain H 2 and O2 in the
(c) MO (d) M3O4 approximate ratio of 1 : 8. This indicates the law of
57. What is the empirical formula of a compound composed (a) Multiple proportion (b) Definite proportion
of O and Mn in equal weight ratio ?
(c) Reciprocal proportions (d) none of these
(a) MnO (b) MnO2 65. The law of multiple proportion is illustrated by
(c) Mn2O3 (d) Mn2O7 (a) Carbon monoxide and carbon dioxide
58. Determine the empirical formula of Kelvar, used in making (b) Potassium bromide and potassium chloride
bullet proof vests, is 70.6% C, 4.2% H, 11.8% N and 13.4%
(c) Water and heavy water
O:
(d) Calcium hydroxide and barium hydroxide
(a) C7H5NO2 (b) C7H5 2
O
66. The percentage of copper and oxygen in samples of CuO
(c) C7H9NO (d) C7H5NO obtained by different methods were found to be the same.
59. A compound contains atoms of three elements A, B and C. This illustrates the law of
If the oxidation number of A is +2, B is +5 and C is –2, the (a) constant proportions (b) conservation of mass
possible formula of the compound is :
(c) multiple proportions (d) reciprocal proportions
(a) A(BC3)2 (b) A3(BC4)2
67. Two samples of lead oxide were separately reduced to
(c) A3(B4C)2 (d) ABC2 metallic lead by heating in a current of hydrogen. The
60. The carbonate of a metal is isomorphous (similar formula) weight of lead from one oxide was half the weight of lead
with magnesium carbonate and contains 6.091 percent of obtained from the other oxide. The data illustrates.
carbon. The atomic weight of metal is (a) law of reciprocal proportions
(a) 24 (b) 56 (b) law of constant proportions
(c) 137 (d) 260 (c) law of multiple proportions

(d) law of equivalent proportions
A-23
68. One part of an element A combines with two parts of 73. H2S contains 5.88% hydrogen, H2O contains 11.11%
another element B. Six parts of the element C combine
hydrogen while SO2 contains 50% sulphur. These figures
with four parts of the element B. If A and C combine
illustrate the law of :
together the ratio of their weights will be governed by
(a) law of definite proportions (a) conservation of mass (b) constant proportions
(b) law of multiple proportions (c) multiple proportions (d) reciprocal proportions
(c) law of reciprocal proportions 74. Hydrogen combines with chlorine to form HCl. It also
(d) law of conservation of mass. combines with sodium to form NaH. If sodium and chlorine
69. n g of substance X reacts with m g of substance Y to form also combine with each other, they will do so in the ratio of
p g of substance R and q g of substance S. This reaction their masses as :
can be represented as follows : (a) 23 : 35.5 (b) 35.5 : 23
X+Y=R+S
(c) 1 : 1 (d) 23 : 1
The relation which can be established in the amounts of
the reactants and the products will be
Principle of Atom Conservation
(a) n – m = p – q (b) n + m = p + q 75. x g of Ag was dissolved in HNO3 and the solution was
treated with excess of NaCl when 2.87 g of AgCl was
(c) n = m (d) p = q
precipitated. The value of x is
70. Which one is the best example of law of conservation of
mass ? (a) 1.08 g (b) 2.16 g
(a) 6 g of carbon is heated in vacuum, there is no change (c) 2.70 g (d) 1.62 g
in mass 76. A 1.50 g sample of an ore containing silver was dossolved,
(b) 6 g of carbon combines with 16 g of oxygen to form 22 g and all the Ag+ was converted to 0.125 g Ag2S. What was
of CO2 the percentage of silver in the ore ?
(a) 14.23% (b) 10.8%

(c) 6 g water is completely converted into steam
(d) A sample of air is heated at constant pressure when its (c) 8.27% (d) 720%
volume increases but there in no change in mass. 77. NaOH is formed according to the reaction
71. SO2 gas was prepared by (i) burning sulphur in oxygen,

1
2Na O 2 o Na 2O
(ii) reacting sodium sulphite with dilute H 2SO 4 and 2
(iii) heating copper with conc. H2SO4. It was found that in
Na 2O H 2 O o 2NaOH
each case sulphur and oxygen combined in the ratio of
1 : 1. The data illustrates the law of : To make 4g of NaOH, Na required is
(a) conservation of mass (b) multiple proportions (a) 4.6g (b) 4.0g
(c) constant proportions (d) reciprocal proportions
(c) 2.3g (d) 0.23g
72. A sample of CaCO3 has Ca = 40%, C = 12% and O = 48%. If
Equivalent Concept
the law of constant proportions is true, then the mass of
Ca in 5 g of CaCO3 from another source will be : 78. 2H3PO4 + 3 Ca(OH)2 o Ca3(PO4)2 + 6 H2O
(a) 2.0g (b) 0.2g Equivalent weight of H3PO4 in this reaction is
(c) 0.02g (d) 20.0g (a) 98 (b) 49
(c) 32.66 (d) 24.5
A-24
79. The Ew of H3PO4 in the reaction is 87. Normality of 0.74 g Ca(OH)2 in 5 mL solution is
Ca(OH)2 + H3PO4 o CaHPO4 + 2H2O (a) 8 N (b) 4 N
(Ca = 40, P = 31, O = 16) (c) 0.4 N (d) 2 N
(a) 49 (b) 98 88. Normality of a 2 M sulphuric acid is
(c) 32.66 (d) 147 (a) 2 N (b) 4 N
80. What weight of a metal of equivalent weight 12 will give (c) N / 2 (d) N / 4
0.475 g of its chloride ? 89. 1 L of a normal solution is diluted to 2000 ml. The
(a) 0.12 g (b) 0.24 g resulting normality is :
(c) 0.36 g (d) 0.48 g (a) N / 2 (b) N/ 4
81. How many grams of phosphoric acid would be needed to (c) N (d) 2 N
neutralise 100 g of magnesium hydroxide ? (The molecular
90. What volume of 0.232 N solution contains 3.17
weights are : H3PO4 = 98 and Mg (OH)2 = 58.3)
milliequivalent of solute ?
(a) 66.7 g (b) 252 g
(a) 137 mL (b) 13.7 mL
(c) 112 g (d) 168 g
(c) 27.3 mL (d) 12.7 mL
82. 0.116 g of C4H4O4 (A) is neutralised by 0.074 g of Ca(OH)2.
Hence, protonic hydrogen (H ) in (A) will be 91. 1L solution of NaOH contains 4.0 g of it. What shall be
the difference between molarity and the normality ?
(a) 1 (b) 2
(a) 0.10 (b) zero
(c) 3 (d) 4
83. 4.2 g of metallic carbonate MCO3 was heated in a hard (c) 0.05 (d) 0.20
glass tube and CO2 evolved was found to have 1120 mL of 92. 100 ml of 0.3 N HCl is mixed with 200 ml of 0.6 N H2SO4. The
volume at STP. The EW of the metal is
final normality of the resulting solution will be
(a) 12 (b) 24
(a) 0.1 N (b) 0.2 N
(c) 18 (d) 15
(c) 0.3 N (d) 0.5 N
84. 1.0 g of a monobasic acid when completely aceted upon
Mg gave 1.301 g of anhydrous Mg salt. Equivalent weight 93. Normality of a mixture of 30 mL of 1N H2SO4 and 20 mL
of acid is
of 4N H 2SO4 is
(a) 35.54 (b) 36.54
(a) 1.0 N (b) 1.1 N
(c) 17.77 (d) 18.27
85. 0.1 g of metal combines with 46.6 mL of oxygen at STP. The (c) 2.0 N (d) 2.2 N
equivalent weight of metal is
94. Normality of solution obtained by mixing 10 mL of
(a) 12 (b) 24 1N HCl, 20 mL of 2N H2SO4 and 30 mL of 3N HNO3 is
(c) 6 (d) 36
(a) 1.11 N (b) 2.22 N
Normality
(c) 2.33 N (d) 3.33 N
86. When 100 ml of 1 M NaOH solution and 10 ml of 10 N
(Use the Final volume as sum of all volumes).
H2SO4 solution are mixed together, the resulting solution
will be :
(a) alkaline (b) acidic
(c) strongly acidic (d) neutral
A-25
ANSWER KEY
Exercise1 : (Basic Objective Questions)
1. (b) 2. (b) 3. (b) 4. (a) 5. (b) 6. (a) 7. (c) 8. (b) 9. (d) 10. (a)
11. (b) 12. (d) 13. (a) 14. (a) 15. (a) 16. (b) 17. (d) 18. (d) 19. (a) 20. (c)
21. (b) 22. (d) 23. (a) 24. (c) 25. (c) 26. (b) 27. (c) 28. (a) 29. (b) 30. (a)
31. (a) 32. (c) 33. (a) 34. (b) 35. (b) 36. (c) 37. (d) 38. (a) 39. (a) 40. (b)
41. (d) 42. (c) 43. (d) 44. (b) 45. (b) 46. (c) 47. (c) 48. (c) 49. (c) 50. (b)
51. (d) 52. (d) 53. (b) 54. (d) 55. (c) 56. (c) 57. (d) 58. (d) 59. (a,b) 60. (c)
61. (d) 62. (d) 63. (c) 64. (b) 65. (a) 66. (a) 67. (c) 68. (c) 69. (b) 70. (b)
71. (c) 72. (a) 73. (d) 74. (a) 75. (b) 76. (d) 77. (c) 78. (c) 79. (a) 80. (a)
81. (c) 82. (b) 83. (a) 84. (b) 85. (a) 86. (d) 87. (b) 88. (b) 89. (a) 90. (b)
91. (b) 92. (d) 93. (d) 94. (c)
Dream on !!
[\]^[\]^
A-26
EXERCISE - 2 : PREVIOUS YEAR AIEEE/JEE MAINS QUESTIONS

6. What is the equilibrium expression for the reaction
1. In which of the following equilibrium change in the volume
(2004)
of the system does not alter the number of moles (2002)
P4 (s) + 5O2 (g) P4O10 (s) ?
(a) N2(g) + O2 (g) 2NO (g)
(b) PCl5 (g) PCl3 (g) + Cl2 (g) [P4 O10 ] 1

(a) K c 5 (b) K c
[P4 ] [O 2 ] [O 2 ]5
(c) N2 (g) + 3H2 (g) 2NH3 (g)
(d) SO2Cl2 SO2 (g) + Cl2 (g) [P4 O10 ]

(c) Kc = [O2]5 (d) K c 5 [P4 ] [O 2 ]
2. For the reaction (2002)
7. For the reaction (2004)
1
CO (g) + O (g) CO2 (g), Kp/Kc is
2 2 CO(g) + Cl2 (g) COCl2 (g),
(a) RT (b) (RT)–1 Kp

–1/2 1/2 the is equal to
(c) (RT) (d) (RT) Kc
3. In which of the following reactions, increase in the pressure

at constant temperature does not affect the moles at 1
(a) (b) 1.0
equilibrium (2002) RT
(a) 2NH3(g) N2(g) + 3H2(g) (c) RT (d) RT

(b) C(g) + 1/2O2(g) CO(g) 8. The equilibrium constant for the reaction
(c) H2(g) + 1/2O2(g) H2O(g) N2(g) + O2(g) 2NO(g)
(d) H2(g) + I2(g) 2HI(g) at temperature T is 4 × 10–4. The value of Kc for the reaction
4. For the reaction equilibrium
1 1
NO2(g) N2(g) + O2(g)
N2O4 (g) 2NO2 (g) 2 2
the concentrations of N2O4 and NO2 at equilibrium are at the same temperature is (2004)
–2 –2 –1
4.8 × 10 and 1.2 × 10 mol L respectively. The value of (a) 2.5 × 102 (b) 0.02
Kc for the reaction is (2003)
(c) 4 × 10–4 (d) 50
3 –1 2 –1
(a) 3 × 10 mol L (b) 3.3 × 10 mol L
9. A small amount of NH4HS is placed in a flask already
(c) 3 × 10–1 mol L–1 (d) 3 × 10–3 mol L–1 containing ammonia gas at a certain temperature and 0.50
atm pressure. Ammonium hydrogen sulphide decomposes
5. The conditions favourable for the reaction
to yield NH 3 and H2S gases in the flask. When the
2SO2(g) + O2(g) 2SO3(g); 'Hº = – 198 kJ decomposition reaction reaches equilibrium, the total
are (2003) pressure in the flask rises to 0.84 atm. The equilibrium
constant for NH4HS decomposition at this temperature is
(a) Low temperature, high pressure
(a) 0.30 (b) 0.18
(b) Any value of T and P
(c) 0.17 (d) 0.11
(c) Low temperature and low pressure
(d) High temperature and high pressure
B-1
10. For the reaction 13. The equilibrium constants K p and K p for the reactions
1 2
2NO2(g) 2NO (g) + O2(g)

X 2Y and Z P + Q, respectively are in the ratio
–6 of 1 : 9. If the degree of dissociation of X and Z be equal
(Kc = 1.8 × 10 at 184ºC)
then the ratio of total pressure at these equilibria is
(R = 0.0831 kJ/(mol.K)
(2008)
When Kp and Kc are compared at 184ºC it is found that
(a) 1 : 36 (b) 1 : 1
(2005)
(c) 1 : 3 (d) 1 : 9
(a) Whether Kp is greater than, less than or equal of Kc
depends upon the total gas pressure 14. For the following three reactions 1, 2 and 3 equilibrium
constants are given
(b) Kp = Kc
(1) CO(g) + H2O(g) CO2(g) + H2(g); K1
(c) Kp is greater than Kc
(d) Kp is greater than Kc (2) CH4(g) + H2O(g) CO(g) + 3H2(g); K2
11. Phosphourus pentachloride dissociates as follows, in a (3) CH4(g) + 2H2O(g) CO2(g) + 4H2(g); K
closed reaction vessel,
Which of the following relations is correct ? (2008)
PCl5 (g) PCl3(g) + Cl2(g) (2006)
(a) K 1 K 2 K (b) K 2 K K1
If total pressure at equilibrium of the reaction mixture is P
and degree of dissociation of PCl5 is x, the partial pressure
(c) K3 = K1K2 (d) K3 . K 2 K12
of PCl3 will be
15. A vessel at 1000 K contains CO2 with a pressure of 0.5 atm.
§ x · § 2x ·
(a) ¨ ¸P (b) ¨ ¸P Some of the CO2 is converted into CO on the addition of
© x 1¹ ©1 x ¹ graphite. If the total pressure at equilibrium is 0.8 atm, the
value of Kp is (2011)
§ x · § x ·
(c) ¨ ¸P (d) ¨ ¸P (a) 1.8 atm (b) 3 atm
© x 1 ¹ ©1 x ¹
(c) 0.3 atm (d) 0.18 atm
12. The equilibrium constant for the reaction
1
SO3(g) SO2(g) + O (g)
2 2
is KC = 4.9 × 10–2. The value of KC for the reaction
2SO2 + O2(g) 2SO3(g) will be (2006)
(a) 416 (b) 2.40 × 10–3
(c) 9.8 × 10–2 (d) 4.9 × 10–2
B-2
ANSWER KEY
EXERCISE 2 : (Previous year AIEEE/JEE Mains Questions)
1. (a) 2. (c) 3. (d) 4. (d) 5. (a) 6. (b) 7. (a) 8. (d) 9. (d) 10. (d)
11. (a) 12. (a) 13. (a) 14. (c) 15. (a)
Dream on !!
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B-3
IONIC EQUILIBRIUM
EXERCISE - 2 : PREVIOUS YEAR AIEEE/JEE MAINS QUESTIONS
1. The molar solubility (in mol L–1) of a sparingly soluble salt 7. The first and second dissociation constant of an acid H2A
MX4 is ‘s’. The corresponding solubility product is Ksp. are 1.0 × 10–5 and 5.0 × 10–10 respectively. The overall
‘s’ is given in terms of Ksp by the relation (2004) dissociation constant of the acid will be (2007)
1/ 4 1/ 5
(a) 5.0 × 10–5 (b) 5.0 × 1015
§ K sp · § K sp ·
(a) s ¨ ¸ (b) s ¨ ¸ (c) 5.0 × 10–15 (d) 0.2 × 1015
¨ 128 ¸ ¨ 256 ¸
© ¹ © ¹
8. Four species are listed below
(c) s = (256 Ksp)1/5 (d) s = (128 Ksp)1/4 (i) HCO3 (ii) H 3O
2. The conjugate base of H 2 PO 4 (2004)
(iii) HSO 4 (iv) HSO 3 F
(a) PO34 (b) HPO 24 Which of the following is the correct sequence of their
acid strength ? (2008)
(c) H3PO4 (d) P2O5
(a) iv < ii < iii < i (b) ii < iii < i < iv
3. The solubility product of a salt having general formula (c) i < iii < ii < iv (d) iii < i < iv < ii
MX2; in water is 4 × 10–12. The concentration of M2+ ions
9. The pKa of a weak acid, HA, is 4.80. The pKb of a weak
in the aqueous solution of the salt is (2005)
base, BOH, is 4.78. The pH of an aqueous solution of the
(a) 4.0 × 10–10 M (b) 1.6 × 10–4 M corresponding salt, BA, will be (2008)
(c) 1.0 × 10–4 M (d) 2.0 × 10–6 M (a) 8.58 (b) 4.79
(c) 7.01 (d) 9.22
4. What is the conjugate base of OH– ? (2005)
10. Solid Ba (NO3)2 is gradually dissolved in a 1.0 × 10–4 M
2– –
(a) O (b) O
Na2CO3 solution. At what concentration of Ba+2 will a
(c) H2O (d) O2 precipitate being to form ? (Ksp for BaCO3 = 5.1 × 10–9);
5. The pKa of a weak acid (HA) is 4.5. The pOH of an aqueous (2009)
buffered solution of HA in which 50% of the acid is
(a) 4.1 × 10–5 M (b) 5.1 × 10–5 M
ionized is (2007)
(c) 8.1 × 10–8 M (d) 8.1 × 10–7 M
(a) 4.5 (b) 2.5
11. At 25ºC, the solubility product of Mg(OH)2 is 1.0 × 10–11.
(c) 9.5 (d) 7.0
At which pH, will Mg2+ ions start precipitating in the form
6. In a saturated solution of the sparingly soluble strong
of Mg(OH)2 from a solution of 0.001 M Mg2+ ions ? (2010)
electrolyte AgIO3 (molecular mass = 283) the equilibrium
which sets in is (a) 9 (b) 10
(c) 11 (d) 8
AgIO3(s ) Ag (aq .) + IO 3( aq .)
12. Solubility product of silver bromie is 5.0 × 10–13. The
If the solubility product constant Ksp of AgIO3 at a given quantity of potassium bromide (molar mass taken as
temperature is 1.0 × 10–8, what is the mass of AgIO3 120 g mol–1) to be added to 1L of 0.05 M solution of silver
contained in 100 mL of its saturated solution ? (2007) nitrate to start the precipitation of AgBr is (2010)
(a) 28.3 × 10–2g (b) 2.83 × 10–3g (a) 1.2 × 10–10 g (b) 1.2 × 10–9 g
(c) 1.0 × 10–7g (d) 1.0 × 10–4g (c) 6.2 × 10–5 g (d) 5.0 × 10–8 g
B-4
IONIC EQUILIBRIUM
13. In aqueous solution, the ionisation constants for carbonic 15. The Ksp for Cr(OH)3 is 1.6 × 10–30. The molar solubility of
acid are (2010) this compound in water is (2011)
K1 = 4.2 × 10–7 and K2 = 4.8 × 10–11
(a) 2 1.6 u1030 (b) 4 1.6 u1030
Select the correct statement for a saturated 0.034 M solution
of the carbonic acid. (c) 4 1.6 u1030 / 27 (d) 1.6 u10 30 / 27
(a) The concentration of CO32 is 0.034 M 16. An acid HA ionises as
ZZX H A
HA YZZ
(b) The concentration of CO32 is greater than that of
The pH of 1.0 M solution is 5. Its dissociation constant
HCO3
would be (2011)
(c) The concentration of H+ and HCO3 are approximately (a) 1 × 10–10 (b) 5
equal (c) 5 × 10–8 (d) 1 × 10–5
(d) The concentration of H+ is double that of CO32
14. Three reactions involving H 2 PO 4 are given below :
(2010)
I. H3PO4 + H2O o H3O+ + H 2 PO 4
II. H 2 PO 4 H 2O o HPO24 H3O
III. H 2 PO4 OH o H 3PO4 O2
In which of the above does H 2 PO 4 act as an acid ?
(a) II only (b) I and II

(c) III only (d) I only
B-5
IONIC EQUILIBRIUM
Answer Key
Exercise2 (Previous Year AIEEE/JEE Mains Questions)
1. (b) 2. (b) 3. (c) 4. (a) 5. (c) 6. (b) 7. (c) 8. (c) 9. (c) 10. (b)
11. (b) 12. (b) 13. (c) 14. (a) 15. (c) 16. (a)
Dream on !!
[\]^[\]^
B-6
EXERCISE - 2 : PREVIOUS YEAR AIEEE QUESTIONS
1. The molarity of a solution obtained by mixing 750 mL of 7. Density of a 2.05 M solution of acetic acid in water is
0.5 (M) HCl with 250 mL of 2 (M) HCl will be (2013) 1.02 g/mL. The molality of the solution is (2006)
(a) 0.875 M (b) 1.00 M (a) 0.44 mol Kg–1 (b) 1.14 mol kg–1
(c) 1.75 M (d) 0.0975 M (c) 3.28 mol kg–1 (d) 2.28 mol kg–1
2. The density of a solution prepared by dissolving 120g of
8. If we consider that 1/6, in place of 1/12, mass of carbon
urea (mol. mass = 60 u) in 1000 g of water is 1.15g/mL. The atom is taken to be the relative atomic mass unit, the mass
molarity of this solution is (2012) of one mole of a substance will (2005)
(a) 0.50 M (b) 1.78 M
(a) be a function of the molecular mass of the substance
(c) 1.02 M (d) 2.05 M
(b) remain unchanged
3. The mass of potassium dichromate crystals required to
(c) increase two fold
oxidise 750 cm3 of 0.6 M Mohr’s salt solution is (Given
molar mass = 392) (2011) (d) decrease twice
(a) 0.49 g (b) 0.45 g 9. 25 mL of a solution of Ba(OH)2 on titration with a 0.1 M

solution of HCl gave a titre value of 35 mL. The molarity
(c) 29.4 g (d) 2.2 g
of barium hydroxide solution was (2003)
4. Amount of oxalic acid present in a solution can be (a) 0.07 (b) 0.14
determined by its titration with KMnO4 solution in the
presence of H2SO4. The titration gives unsatisfactory (c) 0.28 (d) 0.35
result when carried out in the presence of HCl because
10. What volume of H 2 gas at 273 K and 1 atm pressure
HCl (2008)
will be consumed in obtaining 21.6 g of boron (At.
(a) gets oxidised by oxalic acid to chlorine mass 10.8 u) from reduction of boron trichloride by H 2
(2003)
(b) furnishes H+ ions in addition to those from oxalic acid
(a) 89.6 L (b) 67.2 L
(c) reduces permanganate to Mn2+
(c) 44.8 L (d) 22.4 L
(d) oxidises oxalic acid to carbon dioxide and water
11. 6.023 × 10 20 molecules of urea are present in 100 mL of
5. The density (in g mL–1) of a 3.60 M sulphuric acid
its solution. The concentration of urea solution is
solution that is 29% H 2SO4 (Molar mass = 98g mol–1)
(2004)
by mass will be (2007)
(a) 0.001 M (b) 0.1 M
(a) 1.64 (b) 1.88
(c) 0.02 M (d) 0.01 M
(c) 1.22 (d) 1.45
12. To neutralize completely 20 mL of 0.1 M aqueous
6. How many moles of magnesium phosphate, Mg3 (PO4)2 solution of phosphorus (H3PO 3) acid, the volume of
will contain 0.25 mole of oxygen atoms ? (2006) 0.1 M aqueous KOH solution required is (2004)
(a) 0.02 (b) 3.125×10–2 (a) 60 mL (b) 20 mL
(c) 1.25×10–2 (d) 2.5×10–2 (c) 40 mL (d) 10 mL
B-7
13. Number of atoms in 560g of Fe (atomic mass 56 g

mol–1) is (2002)
(a) twice that of 70 g N (b) half that of 20 g H
(c) Both (a) and (b) (d) None of the above
14. In an organic compound of molar mass 108 g mol–1C, H

and N atoms are present in 9 : 1 : 3.5 by weight.
Molecular formula can be (2002)
(a) C6H8 2
(b) C7H10
(c) C5H6 3
(d) C4H18 3
15. Number of atoms in 558.5 Fe (at. wt. 55.85) is

(2002)
(a) Twice that in 60 g carbon
(b) 6.023 × 10 22
(c) Half in 8 g He (d) 558.5 × 6.023 × 1023
B-8
ANSWER KEY
Exercise 2 : (Previous Year AIEEE Questions)
1. (a) 2. (d) 3. (c) 4. (a) 5. (c) 6. (b) 7. (d) 8. (b)
9. (a) 10. (b) 11. (d) 12. (c) 13. (c) 14. (a) 15. (a)
Dream on !!
[\]^[\]^
B-9
EXERCISE - 3: ADVANCED OBJECTIVE QUESTIONS
1. All questions marked “S” are single choice questions
2. All questions marked “M” are multiple choice questions
3. All questions marked “C” are comprehension based questions
4. All questions marked “A” are assertion–reason type questions
(A) If both assertion and reason are correct and reason is the correct explanation of assertion.
(B) If both assertion and reason are true but reason is not the correct explanation of assertion.
(C) If assertion is true but reason is false.
(D) If reason is true but assertion is false.
5. All questions marked “X” are matrix–match type questions
6. All questions marked “I” are integer type questions
Equilibrium : Definition and Expression 4. (S) For a reversible reaction : A + B C
1. (A) Assertion : For a reaction at equilibrium, the free energy

§ dx ·
¨ ¸ = 2.0 × 103 L mol–1 s–1 [A] [B] – 1.0 × 102 s–1 [C]
for the reaction is minimum. © dt ¹
Reason : The free energy for both reactants and
where x is the amount of ‘A’ dissociated. The value of
products decreases and become equal. equilibrium constant (Keq) is :
(a) A (b) B (a) 10 (b) 0.05
(c) C (d) D (c) 20 (d) Can’t be calculated
2. (A) Assertion : Chemical equilibrium represents a state of a 5. (A) Assertion : The reaction quotient, Q has the same form
as the equilibrium constant Keq and is evaluated using
reversible reaction in which measurable properties of
any given concentrations of the species involved in the
the system (pressure, concentration, colour etc.) reaction, and not necessarily equilibrium concentrations.
become constant under the given set of conditions.
Reason : If the numerical value of Q is not the same as
Reason : The chemical equilibrium is an apparent state the value of equilibrium constant, a reaction will proceed.
of rest in which two opposing reactions are proceeding
(a) A (b) B
at the same rate.
(c) C (d) D
(a) A (b) B
6. (A) Assertion : The active mass of pure solids and pure
(c) C (d) D liquids is taken unity.
3. (S) Which of the following statements about the reaction Reason : The active mass of pure solids and liquids
quotient, Q are correct ? depends on density and molecular mass. The density
and molecular mass of pure liquids and solids are
(a) the reaction quotient, Q and the equilibrium constant
constant.
always have the same numerical value
(b) Q may be lesser than, equal to or greater than Keq (a) A (b) B
(c) Q (numerical value) varies as reaction proceeds (c) C (d) D
(d) Q = 1 at equilibrium
C-1
7. (A) Assertion : If some PCl 5 (g) containing labelled 11. (S) Equilibrium constant Kc for the following reaction at
phosphorus p31 is added to a system with following 800K is, 4.
equilibrium, after sometime the system was found to
1
contain radioactive PCl3. NH 3 (g) U N 2 (g) H 2 (g)
2 2
PCl5(g) PCl3(g) + Cl2(g)
The value of kp for the following reaction will be :
Reason : Chemical equilibrium is dynamic in nature.
N 2 (g) 3H 2 (g) U 2NH 3 (g)
(a) A (b) B
(c) C (d) D 2
§ 800R ·
(a) ¨ ¸ (b) 16 × (800R)2
8. (A) Assertion : As a reversible system approaches © 4 ¹
equilibrium, entropy of the system increases.
2
Reason : The state of equilibrium is the most disordered ª 1 º
state of a reversible system. (c) « » (d) (800R)1/2 4
¬ 4 u 800R ¼
(a) A (b) B
Equilibrium : Analysis
(c) C (d) D
12. (S) N2O4 2NO2, Kc = 4. This reversible reaction is
§1· §1· studied graphically as shown in the given figure. Select
9. (M) N 2O2 U 2KO K1 ; ¨ ¸ N 2 ¨ ¸ O 2 U NO K 2
©2¹ ©2¹ the correct statement out of I, II and III.
I : Reaction quotient has maximum value at point A
II : Reaction proceeds left to right at a point when [N2O4]
§1· §1·
2NO U N 2 O 2 K ; NO U ¨ ¸ N 2 ¨ ¸ O 2 K 4 = [NO2] = 0.1 M
©2¹ ©2¹
III : Kc = Q when point D or F is reached :
Correct relation(s) between K1, K2, K3 and K4 is/are :
(a) K2 × K4 = 1 (b) K1 u K 4 1
(c) K u K2 1 (d) K u K2 1
p
and KC
10. (X) Match the following systems with their K p /K c
relationship
Equilibrium types Kp/Kc (a) I, II (b) II, III
relationship (c) II (d) I, II, III
(a) NO(g) NO 3 (g) U 2NO 2 (g) (p)Kp > Kc 13. (S) I2 + I – I
This reaction is set-up in aqueous medium. We start

(b) N 2 (g) 3H 2 (g) U 2NH 3 (g) (q) Kp= Kc (RT)2
with 1 mol of I2 and 0.5 mol of I– in 1L flask. After
equilibrium is reached, excess of AgNO3 gave 0.25 mol
(c) 2O 3 (g) U 3O 2 (g) (r) Kp= Kc
of yellow ppt. Equilibrium constant is : [Given : AgNO
gives yellow ppt with I–]
1 5
(d) BrF5 (g) U Br2 (g) F2 (g) (s) Kp< Kc
2 2 (a) 1.33 (b) 2.66
(c) 2.00 (d) 3.00
C-2
14. (I) Given the hypothetical reaction : respectively, what is the molarity of HBr ?
–2 –1
2A(s) + nB(g) U 3C(g) Kp = 0.0105 (a) 1.8 × 10 M (b) 6.7 × 10 M
0 1
(c) 1.5 × 10 M (d) 3.6 × 10 M
and Kc = 0.45 at 250ºC. What is the value of coefficient
‘n’ ? 21. (S) For the all gas reaction at 1000 K : 2HI U H2 + I2,
15. (S) In the reaction : A + B U 2C + D. The initial K = 0.0344. If you were to begin with 8.0 M of HI in a
fixed volume container, what would be the equilibrium
concentration of A and B are 1M each. The value of Kc
8 concentration of H2 ?
is 10 . What is the equilibrium concentration of A ?
–4 4
(a) 1.10 M (b) 0.48 M
(a) 2 × 10 M (b) 2 × 10 M
(c) 5.8 M (d) 2.92 M
(c) 0.005 M (d) 0.0025 M
k
22. (S) ZZZ
In reversible reaction A YZZ
1
X
Z B , the initial
16. (S) Equilibrium constant for two complexes are : k 2
37 concentration of A and B are a and b in moles per litre

A : K4 [Fe(CN)6] 2.6 × 10 (for dissociation)
17
and the equilibrium concentration are (a – x) and (b – x)
B : K3 [Fe(CN)6] 1.9 × 10 (for dissociation) respectively ; express x in terms of k1, k2, a and b.
(a) A and B are equally stable
k1a k 2 b k1a k 2 b
(b) A is more stable than A (a) (b)
k1 k 2 k1 k 2
(c) B is more stable than A
(d) the predictable stability k1a k 2 b k1a k 2 b
(c) (d)
17. (S)
–
For the reaction, [Ag(CN)2] U Ag + 2CN , the
+ – k1k 2 k1 k 2
–19 +
equilibrium constant Kc at 25ºC is 4 × 10 ; then Ag
Equilibrium Constant and 'G
concentration in a solution which has 0.1 M KCN and
0.03M AgNO3 is : 23. (S) If for the heterogeneous equilibrium
18 –18
(a) 7.5 × 10 (b) 7.5 × 10 CaCO3(s) U CaO(s) + CO2 (g) ; K = 1 at 1 atm,
19 –19
(c) 7.5 × 10 (d) 7.5 × 10 the temperature is given by :
18. (S) A vessel at 1000 K contains CO2 with a pressure of 'Sº 'Hº
0.5 atm. Some of the CO2 is converted to CO on addition (a) T (b) T
'Hº 'Sº
of graphite. If the total pressure at equilibrium is 0.8 atm,
the value of K is :
'Gº 'Gº
(c) T (d) T
(a) 0.18 atm (b) 1.8 atm R 'Hº
(c) 3 atm (d) 0.3 atm 24. (X) Match the Column-I with Column-II :
19. (S) The equilibrium reaction : 2AB(aq) U 2A(aq) + B2(g) Column-I Column-II
has an equilibrium constant equal to 1.28. If the (Equations) (Type of process)
concentrations of AB and A are 5 mol/L and 4 mol/L
(a) Kp > Q (p) Non spontaneous
respectively, what is [B2] ?
(b) 'Gº < RT loge Q (q) Equilibrium
(a) 0.50 M (b) 1.60 M
(c) Kp = Q (r) Spontaneous and
(c) 2.00 M (d) 2.84 M
endothermic
20. (S) Consider the reaction NaBr(aq) + H 2 SO 4(aq) U
NaHSO4(aq) + HBr(aq). The equilibrium constant is 'H
–2 (d) T ! (s) Spontaneous
8.3 × 10 . If the equilibrium concentrations of NaBr, 'S
H2SO4 and NaHSO 4 are 6.0 M, 9.0 M and 3.0 M
C-3
Passage (For Questions 25 to 27) 26. (C) For exothermic reaction is 'Sº < 0, then the sketch of log
Effect of temperature on the equilibrium process is K vs 1/T may be
analyzed by using the thermodynamics. From the
thermodynamics relation.
'Gº = – 2.303 RT logK ...(i)
'Gº : Standard free energy change
'Gº = 'Hº – T'Sº ...(ii)
(a)
'Hº : Standard heat of the reaction
From (i) and (ii)
–2.303 RT log K = 'Hº – 7'Sº
'Sº : Standard entropy change
'Hº 'Sº
logK ...(iii)
2.303RT 2.303R
If a plot of log K vs 1/T is made then it is a straight line
(b)
'Hº 'Sº
having slope and Y intercept
2.303R 2.303R
If at temperature T1, equilibrium constant be K1 and at
temperature T2, equilibrium constant be K2 then the
above equation reduces to :
'Hº 'Sº
log K1
2.303RT1 2.303R
(c)
'Hº 'Sº
log K 2
2.303RT2 2.303R
Substracting (iv) from (v) we get.
K2 'Hº § 1 1 ·
log K ¨ ¸
1 2.303R © T1 T2 ¹
From the above relation we can conclude that the value

of equilibrium constant increases with increase in (d)
temperature for an endothermic reaction and the same
decreases with the increase in temperature for an
exothermic reaction. Answer the following three
questions based on the above information.
27. (C) If for a particular reversible reaction : Kc = 57 at 355ºC
25. (C) If standard heat of dissociation of PCl5 is 230 cal, then and Kc = 69 at 450º, then
1 (a) 'H < 0
slope of the graph of log k vs is
T (b) 'H > 0
(a) +50 (b) –50 (c) 'H = 0
(c) 10 (d) None of these (d) Sign of 'H can’t be determined
C-4
28. (M) Variation of equilibrium constant K for the reaction

d log e K ½ 'H
2A(s) B(g) U C(g) 2D(g) (b) ® ¾
¯ dT ¿P RT
is plotted against absolute temperature T in figure as :
ln K Vs (1/T)
RT
(c) loge K = Constant
'H
'H
(d) loge K = Constant
RT
Homogeneneous and Heterogeneous Equilibria,

Degree of Dissociation
32. (S) Volume of the flask in which the following equilibria are
ln K vs 1/T separately established are transferred to a flask that is
(a) the forward reaction is exothermic double the size of the earlier flask. In which of the
(b) the forward reaction is endothermic following cases, equilibrium constants are affected ?
(c) the slope of line is proportional to 'H
(a) N 2 3H 2 2 NH 3 , exothermic
(d) adding ‘A’ favours forward reaction (g ) (g) (g)
29. (M) Which is/are correct ?

(b) N 2 O 2 2 NO, endothermic
(g )
'Hº 'Sº (g ) (g )
(a) 2.303 log K
RT R
(c) PCl 5 PCl Cl 2 , endothermic
(b) 'Gº = – 2.303 RT log K (g) (g ) (g )
'Hº 'Sº (d) none of these

(c) –2.303 log K
RT 2 R 33. (S) In each of the following, total pressure set-up at
equilibrium is assumed to be equal and is one atm with
1
(d) 2.303 log K ('Hº 'Sº ) equilibrium constants KP given :
RT
–1 I : CaCO3 (s) CaO (s) + CO2 (g), K1
30. (S) The free energy of formation of NO is 78 kJ mol at the
temperature of an automobile engine (1000 K). What is II : NH4HS (s) NH3 (g) + H2S (g), K2
the equilibrium constant for this reaction at this reaction
at 1000 K ? III : NH2COONH4 (s) 2NH3 (g) + CO2 (g), K
1 1 In the increasing order :

N 2 (g) O2 (g) U NO(g)
2 2
–5 –9
(a) K1 = K2 = K (b) K1 < K2 < K
(a) 8.4 × 10 (b) 7.1 × 10
–10 –19
(c) K3 < K2 < K1 (d) None of these
(c) 4.2 × 10 (d) 1.7 × 10
34. (S) During thermal dissociation, the observed vapour
31. (M) The variation of equilibrium constant K with temperature
is represented by : density of N2O4 (g) is 26.0. The extent of dissociation of
N2O4 (g) is :
'H T2 § 1 ·
R ³T1 © T ¹
(a) log e K 2 log e K1 ¨ ¸ dT (a) 50% (b) 87%
(c) 77% (d) 23%
C-5
35. (S) For the reaction N2O4 (g) 2NO2 (g), the value of Kp 38. (I) For the equilibrium AB(g) U A(g) + B(g), at a given
3 4
is 1.7 × 10 at 500 K and 1.78 × 10 at 600 K. Which of the
1 P
following is correct ? temperature rd of AB is dissociated, then will
Kp
I. The proportion of NO2 in the equilibrium mixture is
be numerically equal to _____.
increased by decreasing the pressure
39. (I) SO2Cl2 and Cl2 are introduced into a 3L vessel. Partial
II. The standard enthalpy change for the forward
reaction is negative pressure of SO2Cl2 and Cl2 at equilibrium are 1 atm and
2 atm respectively. The value of Kp for the following
III. units of Kp are atm reaction
IV. at 500 K, the degree of dissociation N2O4 decreases SO2Cl2(g) U SO2(g) + Cl2(g) is 10.
by 50% by increasing the pressure by 100%.
The total pressure in atm at equilibrium would be ____.
The correct choice is :
40. (I) What weight of solid ammonium carbamate
(a) I, III (b) I
(NH2COONH4) when vaporised at 200ºC will have a
(c) II, IV (d) III
volume of 8.96 litre at 1 atm ? Assume that solid
36. (S) Consider the equilibrium completely decomposes into CO2 and NH3 at 200ºC and
1 atm.
1
CO2 U CO(g) O2 (g) 41. (A) Assertion : The dissociation of CaCO 3 can be
2
represented as, CaCO3(s) U CaO(s) + CO2(g). Some
The equilibrium constant K is given by (when D <<< 1) : solid CaCO3 is placed in an evacuated vessel enclosed
by a piston and heated so that a portion of it is
D 3/ 2 D decomposed. If the piston is moved so that the volume
(a) K (b) K of the vessel is doubled, while the temperature is held
2 2
constant, the number of moles of CO2 in the vessel
increases.
D 3/ 2 D 3/ 2
(c) K (d) K Reason : The pressure of CO2 in the vessel will remain
2
the same.
37. (X) Match the Column-I with Column-II :
Passage : For Questions (42 to 44)
Column-I Column-II
These 3 questions deal with the following chemical
(Reaction) (Effect on equilibrium) reaction:
(A) N2(g) +3H2(g) U 2NH (q) Forward shift by lowering of

Ni 2 (aq) 6NH3 (aq) U [Ni(NH3 )6 ]2 (aq)
(green solution) (blue solution)
'H = –ve temperature
(B) N2(g) + O2(g) U 2NO(g) (q) Forward shift by rise in When H+(aq) is added, the colour green is favoured.
Use one or more of the following interpretations to
'H = +ve temperature answer the questions.
(c) PCl5(g) U PCl3(g)+Cl2(g) (r) No effect of pressure I. Some unreacted Ni2+ (aq) is present in the solution
at equilibrium.
'H = +ve change
II. Some unreacted NH3 (aq) is present in the solution
(d) 2SO2(g)+O2(g) U 2SO3(g) (s) Forward shift by rise in
at equilibrium.
'H = –ve pressure
C-6
III. The colour change indicates new equilibrium 46. (C) The deepening of colour on addition of KSCN supports
conditions with reduced [Ni(NH3)6]2+(aq).
(a) A only (b) A and D only
IV. The colour change indicates new equilibrium
(c) A and B only (d) B and D only
conditions with increased [Ni(NH3)6]2+(aq).
47. (C) The disappearance of colour on addition of Na2HPO4
42. (C) The deepening colour on dissolving more Ni(NO3)2
supports
supports interpretation(s)
(a) I only (b) I and IV only (a) A only (b) A and D only
(c) II and IV only (d) I and II only (c) A and B only (d) C only
43. (C) The deepening colour on addition of more NH3(aq) 48. (M) An industrial fuel, ‘water gas’ which consists of a mixture
supports intepretation(s) of H2 and CO can be made by passing steam over red-
hot carbon. The reaction is
(a) I only (b) I and IV only
(c) I and II only (d) II and IV only C(s) + H2O(g) U CO(g) + H2(g) ; 'H = + 131 kJ
44. (C) The disappearance of colour on addition of H+ (aq) The yield of CO and H2 at equilibrium would be shifted
supports interpretation(s) to the product side by
(a) I only (b) II and IV only (a) raising the relative pressure of steam
(c) I and II only (d) III only (b) adding hot carbon
Passage : For Questions (45 to 47) (c) raising the temperature
These 3 questions refer to the following experiment.
(d) reducing the volume of the system
Some Fe(NO3)3 solution is added to KSCN solution and
a dark red colour appears. This colour is caused by 49. (S) For the reaction, N2O4(g) U 2NO2(g) ; if percentage
FeSCN2+, which is formed by the reaction : dissociation of N2O4 are 25%, 50%, 75% and 100%, then
3+ – 2+ the sequence of observed vapour densities will be :
Fe (aq) + SCN (aq) U FeCN (aq).
(a) d1 > d2 > d3 > d4 (b) d4 > d3 > d2 > d1
Experiments show this colour becomes deeper upon
addition of more Fe(NO 3 )3 or KSCN. The colour (c) d1 = d2 = d3 = d4 (d) (d1 = d2) > (d3 = d4)
disappears when Na2HPO4 is added. Use one or more
of the interpretations below. 50. (S) The equilibrium constant for the decomposition of water,
(a) Unreacted Fe 3+ (aq) is present in the original

ª 1 º
equilibrium mixture. « H 2O(g) U H 2 (g) 4 O2 (g) »
¬ ¼
(b) Unreacted SCN– (aq) is present in the original
equilibrium mixture. is given by :
(c) Colour change indicates a new equilibrium ;

D p1/ 2
[FeSCN2+ (aq)] has been reduced. (a) K
(1 D)(2 D)1/ 2
(d) Colour change indicates a new equilibrium ;
[FeSCN2+ (aq)] has been increased. D 3/ 2 p1/ 2
(b) K
45. (C) The deepening of colour on addition of more Fe(NO3) (1 D)(2 D)1/ 2
supports
(a) A only (b) A and D only D p1/ 2 D p3/ 2
(c) K (d) K
(c) A and B only (d) B and D only 2 (1 D)(2 D)1/ 2
C-7
51. (S) The equilibrium constants K p1 and K p2 for the 56. (M) Yield of NH in Haber’s process
reactions X U 2Y and Z U P Q ; respectively are N 2(g ) 3H 2(g ) 2NH3(g), 'H = – 22 kcal;

in the ratio of 1 : 9. If the degree of dissociation of X and
can be increased by
Z be equal, then the ratio of total pressures at these
equilibria is : (a) compressing the reaction system
(a) 1 : 9 (b) 1 : 36 (b) raising the temperature
(c) 1 : 1 (d) 1 : 3 (c) decreasing the temperature
52. (S) In the preparation of CaO from CaCO 3 using the
(d) using the catalyst to lower down the activation
equilibrium, CaCO3 (s) U CaO(s) CO 2 (g), energy
57. (M) The volume of the reaction flask is reduced to half of
8500
Kp is expressed as log Kp = 7.282 . its initial value, temperature being constant. In which
T of the following cases the position of the equilibrium
For complete decomposition of CaCO3 the temperature would shift ?
is celsius to be used is :
(a) NH4HS(s) NH3(g) + H2S(s)
(a) 1167 (b) 894
(c) 8500 (d) 850 (b) 2NOCl(g) 2NO(g) + Cl2(g)
Le Chatelier’s Principle (c) CO(g) + H2O(g) CO2(g) + H2(g)

53. (A) Assertion : For the reaction (d) I2(g) 2I(g)
A g B g YZZZC g Dg
ZZZX
58. (M) KNO3(s) dissociates on heating as :
at the given temperature, there will be no effect by
addition of inert gas either at constant pressure or at 1
KNO3(s) KNO2(s) + O 2(g )
constant volume. 2
Reason : For the reaction where 'n = 0, there is no At equilibrium in a closed container
effect of inert gas either at constant volume or at
(a) addition of NaNO3(s) favours forward reaction
constant pressure because Kp becomes purely a number.
(a) A (b) B (b) addition of KNO2(s) favours reverse reaction
(c) C (d) D
(c) increasing temperature favours forward reaction
54. (A) Assertion : Addition of an inert gas at constant pressure
(d) decreasing pressure favours forward reaction
equilibrium will support the dissociation of PCl5 at the
same temperature. 59. (M) The dissociation of phosgene, which occurs according
Reason : The addition of an inert gas will tend to increase to the reaction :
the total pressure. COCl2(g) CO(g) + Cl2(g)
(a) A (b) B
(c) C (d) D is an endothermic process. Which of the following factors
55. (A) Assertion : The addition of an inert gas under constant will increase the degree of dissociation of COCl2 ?
volume condition cause the total pressure of the system
(a) Adding Cl2 to the system
to increase. This would thus lower the degree of
(b) Adding helium to the system at constant pressure
dissociation of PCl5.
Reason : Addition of inert gas at equilibrium increase (c) Decreasing the temperature of the system
the kinetic energy of molecules. (d) Reducing the total pressure
(a) A (b) B
(c) C (d) D
C-8
60. (M) The dissociation of ammonium carbamate may be 64. (S) To the system H2 (g) + I2 (g) 2HI (g)
represented by the equation
in equilibrium, some N2 gas was added at constant
NH4CO2NH2(s) 2NH3(g) + CO2(g) volume. Then,
'H° for the forward reaction is negative. The equilibrium (a) Kp will remain constant and Kc will change
will shift from right to left if there is
(b) Kc will remain constant and Kp will change
(a) a decrease in pressure
(c) Both Kp and Kc will remain constant
(b) an increase in temperature
(d) Both Kp and Kc will change
(c) an increase in the concentration of ammonia
65. (S) In a 1.0 L aqueous solution when the reaction
(d) an increase in the concentration of carbon dioxide
2 Ag (aq ) Cu (s ) Cu (2aq

) 2 Ag ( s )
61. (M) Which of the following factors will increase solubility
of a well known weak base, NH3(g), in H2O ? reaches equilibrium, [Cu2+] = x M and [Ag+] = y M.
NH3(g) + H2O(aq) NH4OH(aq) If the volume of solution is doubled by adding water,

then at equilibrium :
(a) increase in pressure (b) addition of water
2 x y
(c) addition of an acid to water (a) [Cu ] M, [ Ag ] M
2 2
(d) addition of a base to water
2 x y
(b) [Cu ] ! M, [Ag ] ! M
62. (M) For the following endothermic equilibrium established 2 2
by dissociation of NH4HS to its components,
2 x y
(c) [Cu ] M, [Ag ] ! M
NH4HS(s) NH3(g) + H2S(g) 2 2
partial pressure of NH3 will increase 2 x y

(d) [Cu ] M, [Ag ] M
2 2
(a) if NH3 is added after equilibrium is established
66. (S) For the reaction PCl5 (g) PCl3 (g) + Cl2 (g)
(b) if H2S is added after equilibrium is established
Which of the following sketch may represent above
(c) temperature is increased equilibrium ? Assume equilibrium can be achieved from
either side and by taking any one or more components
(d) volume of the flask is decreased
initially. (Given KC for the reaction < 2) ?
63. (M) Volume of the flask in which the following equilibria are
separately established are transferred to a flask that is
double the size of the earlier flask. In which of the following
cases, equilibrium concentrations are affected ? (a)
(a) N 2 3H 2 2 NH 3
(g) (g ) (g)
(b) N 2 O 2 2 NO
(g ) (g ) (g)
(c) PCl 5 PCl 3 Cl 2 (b) 3

5
(g) (g) (g)

2
(d) 2 NOBr N 2 O2
( g) (g) (g )
C-9
(c) A2(g) U 2A(g) ; Kp = 2. At (r) n(A) > n(A2) at

5
equilibrium the total pressure equilibrium
3
(c) is 2.0 atm.
2
(d) 2A(g) U A2(g)Kp = 2. A (s) n(A) < n(A2) at
mixture, initially containing equilibrium

both A and A2 at 1.0 atm
partial pressure is prepared.
(d)
69. (X) Match the Column–I with Column–II
Column–I Column–II
(A) N2(g) + 3H2(g) U 2NH3(g) (p) Forward shift by

67. (S) For the following reaction through stages I, II and III
increase in pressure
I II III
A
o B o C o D
(B) N2(g) + O2(g) U 2NO(g) (p) No effect of
quantity of the product formed (x) varies with
temperature (T) as given. Select correct statement : pressure change
(C) CaCO3(s) U CaO(s)+CO2(g) (r) No effect of inert
gas addition at
constant volume
(D) NH2COONH4(s) U 2NH3(g)
+ CO2(g)
(s) Addition of inert gas
will favour backward
(a) Stages I and III are endothermic but II is exothermic direction (Not at
(b) Stages I and III are exothermic but II is endothermic constant volume)
(c) Stages II and III are exothermic but I is endothermic Passage : For Questions (70 to 72)
(d) Stage I is exothermic but stages II and III are Le-Chatelier’s principle : If a system at equilbrium is
endothermic subjected to a change of any one of the factors such as
68. (X) Match the conditions on the left column with states on concentration, pressure or temperature, the system
the right column. adjusts itself in such a way as to “Nullify” the effect of
that change.
Equilibrium types Kp/Kc
Change of Pressure :
relationship
If a system in equilibrium consists of gases, then the
(a) A2(g) U 2A(g); Kc = 1. (p) System is at
concentrations of all components can be altered by
Mixture of 1.0 mole of each equilibrium changing the pressure. When the pressure on the
is prepared in a 1.0 L flask. system is increased, the volume decreases
proportionately. The total number of moles per unit
(b) A(g) + 2B(g) U AB2(g) (q) Goes to right volume will now be more and the equilibrium will shift in
Kc= 2. A mixture of 2.0 moles that direction in which there is decrease in number of
moles i.e, towards the direction in which there is decrease
of each A, B and AB2
in volume.
is prepared in a 1.0 L flask.
C-10
Effect of Pressure on Melting Point :
1 1
There are two types of solids : 72. (C) For the reaction : N 2 (g) O2 (g) U NO(g)
2 2
(a) Solids whose volume decreases on melting e.g., ice, If pressure is increased by reducing the volume of the
diamond, carborundum, magnesium nitride and quartz. container, then
Solid (higher volume) U liquid (lower volume) (a) total pressure at equilibrium will change
The process of melting is facilitated at higher pressure, (b) concentration of all the components at equilibrium
thus the melting point is lowered. will change
(b) Solids whose volume increase on melting e.g. Fe, (c) concentration of all the components at equilibrium
Cu, Ag, Au, etc. will remain same
(d) equilibrium will shift in the forward direction
Solid (lower volume) U liquid (higher volume)
73. (M) For the reaction : PCl5(g) U PCl3(g) + Cl2(g),
In this case, the process of melting becomes difficult at
high pressure ; thus melting point becomes high. The forward reaction at constant temperature is
favoured by
(c) Solubility of substances : When solid substances
are dissolved in water, either heat is evolved (exothermic) (a) introducing an inert gas at constant volume
or heat is absorbed (endothermic) : (b) introducing chlorine gas at constant volume
KCl + aq U KCl(aq) + heat (c) introducing an inert gas at constant pressure
(d) increasing the volume of the container
In such cases, solubility increases with increase in
temperature. Consider the case of KOH; when this is 74. (M) Which of the following factors will favour the backward
dissolved, heat is evolved; reaction ?
KOH + aq U KOH(aq) – heat Cl2(g) + 3F2(g) U 2ClF3(g) ; 'H = –ve
In such cases, solubility decrease with increse in (a) Addition of inert gas at constant pressure
temperature. (b) Addition of Cl2 gas
(d) Solubility of gases in liquids : When a gas dissolves (c) Increase in the temperature of reaction
in liquid, there is decrease in volume. Thus, increase of (d) Increasing the volume of the container
pressure will favour the dissolution of gas in liquid.
Answer the following three questions based on the 75. (M) For the gas phase reaction,
–1
above information. C2H4(g) + H2(g) U C2H6(g) ; 'Hº = –136.8 kJ mol
70. (C) When a gas “X” is dissolved in water, the heat is evolved. carried out in a vessel, the equilibrium concentration of
Then solubility of ‘X’ will increase at C2H4 can be increased by :
(a) low pressure, high temperature (a) increase in temperature(b) decrease in pressure
(b) low pressure, low temperature (c) removing some H2 (d) adding some C2H6
(c) high pressure, high temperature
Physical Equilibria
(d) high pressure, low temperature
76. (S) Densities of diamond and graphite are 3.5 and 2.3 g/mL
71. (C) Au(s) U Au(l) respectively. Increase of pressure on the equilibrium
Above equilibrium is favoured at C (diamond) U C (graphite)
(a) high pressure low temperature (a) favours backward reaction
(b) high pressure high temperature (b) favours forward reaction
(c) low pressure, high temperature (c) has no effect
(d) low pressure, low temperature (d) increase the reaction rate
C-11
77. (S) Some quantity of water is contained in a container as If initially only NO and NO2 are present in a 3 : 5 mole
shown in figure below. As neon is added to this system ratio and the total pressure at equilibrium is 5.5 atm with
at constant pressure, the amount of liquid water in the the pressure of NO2 is 0.5 atm, calculate K p (in 10–1).
vessel : 1
82. (I) Two solids A and C dissociate into gas products as

follows.
A(s) U B(g) + D(g); K p = 400
1
C(s) U E(g) + D(g); K p = 900

2
At 25ºC, the pressure over excess solid A only is 40

atm, and that over solid C only is 60 atm. Find the
pressure over the solid mixture.
83. (S) On heating a mixture of SO2Cl2 and CO, two equilibria
are simultaneously established :
(a) increases (b) decrease SO 2 Cl 2 (g) U SO 2 (g) Cl 2 (g)
(c) remains same (d) change unpredictably
CO(g) Cl 2 (g) U COCl 2 (g)
78. (S) Solubility of a substance which dissolves with a decrease
in volume and absorption of heat will be favoured by On adding more SO2 at equilibrium what will happen ?
(a) high p and high T (b) low p and low T (a) Amount of CO will decrese
(c) high p and Low T (d) low p and high T (b) Amount of SO2Cl2 and COCl2 will increase
79. (S) A solution is transferred to a 1 L flask, some pure ice is (c) Amount of CO will remain unaffected
added and a stopper is inserted to close the flask. After (d) Amount of CO2Cl2 and CO will increase
the system has reached constant temperature, there are 84. (S) Two solid compounds X(s) and Y(s) undergo
still a few cubes of ice left in the flask, but no other dissociation as follows :
solid. Which of the following statements is false relative
to this system at equilibrium ? X(s) U A(g) 2B(g) ; K 1
9 u 10 3 bar 3
(a) The system is a heterogeneous one.
Y(s) U 2B(g) C(g) ; K 2
4.5 u 10 3 bar 3
(b) There are four phases present in the system, not
including the container and stopper. The total pressure of gaseous mixture at equilibrium will
be :
(c) The vapour pressure is constant.
(a) 4.5 bar (b) 0.45 bar
(d) The temperature of the system is below 0ºC.
(c) 0.6 bar (d) 1.2 bar
80. (S) When a liquid in equilibrium with its vapour is heated
85. (S) Given the following reactions and associated equilibrium
(a) the rate of the reaction, vapour o liquid, is constants, select the correct expression for the third
increased equilibrium constant in terms of the first two.
(b) the same equilibrium mixture is re-established (A) 2CO(g) O 2 (g) U 2CO 2 (g)K c
1
(c) a new equilibrium mixture with a higher vapour

pressure is established 1
(B) H 2 (g) O 2 (g) U H 2 O(g)K c2
(d) a new equilibrium mixture is established in which the 2
rate of evaporation is greater than the rate of
condensation (C) CO(g) H 2 O(g) U CO 2 (g) H2 (g)K c3
Simultaneous Equilibria K c1 K c1
1/ 2
81. (I) Two equilibria are simultaneously existing in a vessel (a) K c3 K c2 (b) K c3
K c2
at 25ºC
NO(g) + NO2(g) U N2O3(g); K p (say) 1/ 2
1 (c) K c3 K c1 u K c2
2NO2(g) U N2O4(g); K p = 8 atm–1 1/ 2 1/ 2

2
(d) K c3 Kc1 u K c2
C-12
ANSWER KEY
Advanced Objective Questions
1. (a) 2. (a) 3. (b,c) 4. (c) 5. (b) 6. (a) 7. (a) 8. (a) 9. (a,c) 11. (c)
12. (b) 13. (a) 14. (0004) 15. (a) 16. (c) 17. (b) 18. (b) 19. (c) 20. (c) 21. (a)
22. (a) 23. (b) 24. (A–s), (B–p), (C–q), (D–r) 25. (b) 26. (b) 27. (b) 28. (a,c,d)
29. (a,b) 30. (a) 31. (a,d) 32. (d) 33. (c) 34. (c) 35. (a) 36. (a)
37. (A–p,q,s), (B-q,r), (C–q), (D–p,s) 38. (0008) 39. (0008) 40. (0006) 41. (b) 42. (c) 43. (b) 44. (d)
45. (d) 46. (b) 47. (d) 48. (a,c) 49. (a) 50. (b) 51. (b) 52. (b) 53. (a) 54. (a)
55. (d) 56. (a,c) 57. (a,b,d) 58. (c,d) 59. (b,d) 60. (b,c,d) 61. (a,b,c) 62. (a,c) 63. (a,c) 64. (c)
65. (c) 66. (d) 67. (a) 69. (A-p,r,s), (B-q,r), (C-r), (D-r) 70. (d) 71. (c) 72. (b)
73. (c,d) 74. (a,c,d) 75. (a,b,c,d) 76. (a) 77. (b) 78. (a) 79. (b) 80. (c) 81. (0004)
82. (0072) 83. (d) 84. (b) 85. (b)
Dream on !!
[\]^[\]^
C-13
IONIC EQUILIBRIUM
IONIC EQUILIBRIUM
Theory of Electrolytes, AcidBase Strength Comparison 5. (S) Arrange the following acids in increasing order of their
acid strength :
1. (A) Assertion : [Al(H 2O) 6] 3+ is a stronger acid than
[Mg(H2O)6]2+. I. HClO4 II. H2SO4
2+ III. H3PO4
Reason : Size of [Al(H2O)6]3+ smaller than [Mg(H2O)6]
(a) III < II < I (b) I < II < III
and possesses more effective nuclear charge.
(c) II < III < I (d) III < I < II
(a) A (b) B
6. (S) Consider the following reaction which proceeds
(c) C (d) D
predominantly from
2. (M) Which among the following represent the conjugate
acid/base pairs ? HSO 4 NH3 U NH4 SO42
(a) H3O+/H2O (b) H2SO4/ SO 24 From the information given it is clear that
(a) HSO4 is a stronger acid than NH 4 .

(c) HCO3 / CO32
(d) All are conjugate acid/base paires (b) NH3 is a weaker base than SO 24
3. (S) The equilibrium constant for this reaction is
approximately 10–3. (c) HSO4 t onge e th n NH 4
HPO42 (aq.) HCO3 (aq.) U H2 PO4 (aq.) CO32 (aq.) (d) NH3 is a weaker base than NH 4
Which is the strongest conjugate base in this 7. (A) Assertion : H2SO4 acts as a base in the presence of
reaction ? HClO4.
(a) HPO 24 (aq.) (b) HCO3 (aq.) Reason : Perchloric acid is stronger acid than H2SO4.
(a) A (b) B
(c) H2 PO4 (aq.) (d) CO32 (aq.)
(c) C (d) D
4. (S) In the following reaction : Weak Acids and Bases : Analysis
2 8. (S) A mixture of weak acid is 0.1 M in HCOOH
HCO H 2 O U CO H3O
3 3 –4 –4
(Ka = 1.8 × 10 ) and 0.1 M in HOCN (Ka = 3.1 × 10 ).
Which two substances are Bronsted bases ?
Hence, [H3O ] is
(a) CO32 and H3O (b) HCO3 and H3O+ –3 –4
(a) 7.0 × 10 M (b) 4.1 × 10 M
(c) HCO3 and CO32 (d) CO32 and H2O (c) 0.20 M (d) 4.1 × 10 M
–3
C-14
IONIC EQUILIBRIUM
9. (S) Like water, ammonia (NH3) is an amphoteric substance

[H ]Total C1K a1 C 2 K a 2 (When two weak acids are
that can be used as a solvent for acid base reactions.
The phase label (am) means solvated by ammonia mixed)
(ammoniated). Which statement is correct, extrapolating [H+] of polyprotic acid (weak, H3A) (has dissociation
from your knowledge of acid base reactions in water ?
constants K a1 !! K a 2 !! K a 3 ); will be contributed by
(a) Auto-ionization of ammonia is described by
first dissociation at the most.

2NH3 (l ) U NH (am) NH (am)
4 2 12. (C)
+ –6
What will be the value of [H ] of 10 M CH3COOH ?
–5
(b) The strongest acid that can exist in ammonia (Ka = 1.8 × 10 )
solution is H3O+ (am). (a) 4.24 × 10 M
–6
(b) 10 M
–6
(c) The strongest base, which can exist in ammonia (c) 9.5 × 10 M
–7
(d) 10 M
–8
solution, is NH 4 (am). 13. (C) What will be sulphide ion concentration of a dilute
(d) The addition of an acid to an ammonia solution solution that has been saturated with 0.1 M H2S if the
will increase the concentration of NH2– (am). pH of the solution is 3 ?
–8
10. (S) The concentration of NaOH solution is 10 M. Find K a1 1u 107 ; K a 2 1.3 u 10 13
–
out the (OH ) concentration –11 –13
–8 –6
(a) 1.25 × 10 (b) 1.3 × 10
(a) 10 (b) Greater than 10 –9 –15
–6 –6 –7
(c) 1.45 × 10 (d) 1.30 × 10
(c) 10 (d) Lies between 10 and 10 –4
14. (C) The pH of 0.01 M HCOOH (Ka = 1.4 × 10 ) will be :
11. (M) The percentage ionization of a weak base is given by
(a) 2.926 (b) 3.296
§ Ka · § 1 · (c) 4.962 (d) 5.926
¨ ¸
(a) ¨ c ¸ u100 (b) ¨ pK b pOH
¸ u100
© 1 10
–12
© ¹ ¹ 15. (I) Ionic product of water is 10 . pH of water is _____.
16. (M) Which of the following statements is/are correct about
§ Kb · the ionic product of water ?
¨ ¸
(c) ¨ c ¸ u 100
© ¹ (a) Ka (equilibrium constant of water) < Kw (ionic
product of water)
§ Kw ·
¨ ¸ u 100 (b) pK > pKw
(d) ¨ c u K of conjugate acid ¸
© a ¹ (c) At 100ºC, Kw of water becomes 10
–12
–14
Comprehension (d) Ionic product of water at 25ºC is 10
The concentration of hydrogen ion is a measure of 17. (A) Assertion : Water acts as levelling solvent for various
acidity or alkalinity of a solution. acids.
For mono basic acids : Reason : Levelling effect of water is due to high
dielectric constant and strong proton accepting
CH 3COOH U CH3COO H
tendency.
Ka (a) A (b) B
D
C (c) C (d) D
18. (A) Assertion : Addition of HCl(aq.) to HCOOH(aq.)
where, Ka = Dissociation constant of acid
decreases the ionization of HCOOH.
C = molarity of acid +
Reason : Common ion effect of H ion, reduces the
Ka ionization of HCOOH.
[H ] CD,[H ] , [H ] CK a
D (a) A (b) B
+
pH of a weak acid can be calculated using [H ] by any (c) C (d) D
of above methods.
C-15
IONIC EQUILIBRIUM
19. (S) The charge balance equation of species in 0.1 M 25. (A) Assertion : pH of HCl solution is less than that of acetic
CH3COOH solution is given by : acid of the same concentration.
+ –
(a) [H ] = [OH ] Reason : In equimolar solutions, the number of titrable
+ – protons present in HCl in less than that present in acetic
(b) [H ] = [CH3COO ] acid.
+ – –
(c) [H ] = [OH ] + [CH3COO ] (a) A (b) B
+ – –
(d) 2[H ] = [OH ] + [CH3COO ] (c) C (d) D
20. (S) A solution of 2M formic acid (HCOOH) is 0.95% ionized. 26. (A) Assertion : pH of water increases with an increase in
What is the Ka of formic acid ? temperature.
–2 –4
(a) 1.9 × 10 (b) 1.8 × 10 Reason : Kw of water increases with increase in
(c) 9 × 10
–5
(d) 4.5 × 10
–5 temperature.
– (a) A (b) B
21. (S) What is the Kb of a weak base that produces one OH
per molecule if a 0.05 M solution is 2.5% ionized ? (c) C (d) D
–8 –6 –8
(a) 7.8 × 10 (b) 1.6 × 10 27. (A) Assertion : pH of 10 M HCl lies between 6 and 7.
–5 –3 +
(c) 3.2 × 10 (d) 1.2 × 10 Reason : For very dilute solutions of acids, H ion
contribution from water is also taken into consideration.
22. (M) A solution is prepared by mixing 100 mL 0.50 M
–4 (a) A (b) B
hydrazoic acid (HN3), whose Ka = 3.6 × 10 , with 400
–4
mL of 0.10M cyanic acid (HOCN), whose Ka = 8 × 10 . (c) C (d) D
Which of the following is (are) true regarding 28. (S) In our body, carbon dioxide (CO2) combines with water
+
(a) [H ] = 10 M
–2 –3
(b) [N3 ] = 3.6 × 10 (H2O) to form carbonic acid.
–
(c) [OCN ] = 4.57 × 10
–3 –
(d) [OH ] = 7.14 × 10
–13
H2O + CO2
o H2CO3
23. (M) At 25ºC, pH of a 0.01 M solution of a monobasic acid Carbonic acid undergoes dissociation as,
(HA) is 4. The correct statement(s) regarding HA and
H 2 CO3 U H HCO3
its given solution is (are)
(a) HA is a weak acid During the physical and mental stress, the rate of
respiration increses, which results in the decrease in
(b) The ionization constant (Ka) of acid is approximately
–6 concentration of CO2 in the blood. What will be the
10 at 25ºC effect on pH of human blood during the stress ?
(c) Increasing the temperature of solution would cause (a) Decreases (b) Remains same
the pH to decrease
(c) Increases (d) Cannot be predicted
(d) Addition of 0.1 M HCl solution would lower pH by –3 –4
increasing degree of ionization. 29. (S) Assertion : If Ka of HA is 10 and Ka of HB is 10 at
25ºC, pH of an aqueous solution of HB will be one unit
pH of Solutions greater than pH of equimolar solution of HA.
24. (S) The pKa of acetylsalicylic acid (aspirin) is 3.5. The pH Reason : For weak acids, both concentration and
of gastric juice in human stomach is about 2-3 and the ionization constant affects the pH.
pH in the small intestine is about 8. Aspirin will be :
(a) A (b) B
(a) unionised in the small intestine and in the stomach
(c) C (d) D
(b) completely ionized in the small intestine and in the
30. (S) Assertion : Increasing the temperature of an aqueous
stomach
acetic acid solution decreases pH.
(c) ionised in the stomach and almost unionised in the
Reason : Ionization of acetic acid is endothermic in
small intestine
nature.
(d) ionised in the small intestine and almost unionised
(a) A (b) B
in the stomach
(c) C (d) D
C-16
IONIC EQUILIBRIUM
31. (S) What is the pH of a solution at 25ºC that is 0.010 M in 38. (M) Which of the following is (are) correct for buffer
HCl and 0.025 M in HNO3 ? solution ?
(a) 1.49 (b) 1.60 (a) Acidic buffer will be effective within in the pH range
(c) 1.82 (d) 3.60 (pK a r 1)
32. (S) If 112 mL of HCl(g) at S.T.P. conditions become the
(b) Basic buffer will be effective within the pH range
solute in 500 mL of water solution, what will be the pH
of this mixture ? (pK w pK b r 1)
(a) 0.5 (b) 1.0 (c) H3PO4 + NaH2PO4 is not a buffer solution
(c) 1.5 (d) 2.0
(d) Buffer behaves most effectively when the [Salt]/
33. (S) Why is it necessary to take the acid-base properties of [Acid] ratio equal to one
water into account when computing the hydronium ion
concentration of very dilute solutions of strong acids ? 39. (A) Assertion : pH value of HCN solution decreases when
NaCN is added to it
(a) The hydroxide ion produced from the dissociation
+
of water reacts with most of the H ion produced Reason : NaCN provides a common ion CN– to HCN.
from the acid.
(a) A (b) B
(b) The dissociation constant for water is larger in
dilute rather than in concentrated solutions of acids. (c) C (d) D
+
(c) The amount of H ion produced by the dissociation Comprehension
of water is significant compared to that produced
by the acid. Hydrogen carbonate and phosphate buffers in the
+
(d) The conjugate base of the strong acid reacts with blood prevent excess hydrogen ions [H ] produced by
the hydroxide ion produced from the dissociation metabolic activity, from decreasing the pH of the blood.
of water. Carbon dioxide released into the blood during
respiration is regulated by this system and prevented
34. (S) When one drop of a concentrated HCl is added to from causing changes in plasma pH prior to its excretion
1 L of pure water at 25ºC, the pH drops suddenly from from the lungs. Excessive change in blood chemistry
7 to 4. When the second drop of the same acid is added, which would change the plasma pH from its normal
the pH of the solution further drops to about level 7.4. This excretes hydrogen ions and retains
(a) 0 (b) 1.0 hydrogen carbonate ions and retains hydrogen ions if
(c) 2.0 (d) 3.7 the pH rises. This may produce change in the pH of the
–5 urine from 4.5 to 8.5. A fall in pH also stimulates the
35. (S) The pH of 10 M HCl solution if 1 ml of it is diluted to
1000 ml is : kidney cells to produce the base ion ammonia (NH4 )
(a) 5 (b) 8 which combines with acids brought to the kidney and
is then excreted as ammonium salts.
(c) 7.02 (d) 6.98
40. (C) The normal pH of blood is
Buffer Solutions
(a) 4.5 (b) 8.5
36. (S) On diluting a buffer solution, its pH :
(a) increases (b) decreases (c) 7.32 (d) 7.4
(c) remains same (d) can’t say 41. (C) Which of the following buffer present in the blood ?
37. (M) Choose the correct statement :
(a) HCO 3 H 2 CO3 and PO34 HPO 24
(a) pH of acidic buffer solution decreases if more salt
is added (b) HCO3 CO 32 and HPO 24 H 2 PO 4
(b) pH of acidic buffer solution increases if more salt is
added (c) HCO 3 H 2 CO 3 and PO 34 H 3 PO 4
(c) pH of basic buffer decreases if more salt is added (d) None of these
(d) pH of basic buffer increases if more salt is added
C-17
IONIC EQUILIBRIUM
49. (S) Which of these aqueous solutions are buffers ?

42. (C) Assuming that the buffer in blood is CO 2 HCO3 .
Calculate the ratio of conjugate base to acid necessary 1. A solution that is 0.1 M HNO3 and 0.1 M HCl.
to maintain blood at its proper pH. 2. A solution that is 0.1 M NaH2PO4 and 0.1 M
–7
(K1 of H2CO3 = 4.2 × 10 ) Na2HPO4.
(a) 15 (b) 16 3. A solution made by mixing 10 mL of 0.1 M HF and

(c) 14 (d) 11 5.0 mL of 0.1 M NaOH.
43. (A) Assertion : An aqueous solution of ammonium acetate 4. A solution made by mixing 10 mL of 0.1 M KOH
can act as a buffer. and 20 mL of 0.1 M HCl.
Reason : Acetic acid is a weak acid and NH4OH is a (a) 1 and 2 (b) 2 and 3
weak base. (c) 3 and 4 (d) 1 and 4
(a) A (b) B 50. (S) A solution was prepared by mixing 10.0 mL of 0.50 M
(c) C (d) D NaOH with 10.0 mL of 1.00 M acetic acid, Ka=1.8 ×10–5.
44. (M) Which of the following will function as buffer ? Find the pH of solution.
(a) NaCl + NaOH (b) Borax + Boric acid (a) 2.45 (b) 1.67
(c) NaH2PO4 + NaHPO4 (d) NH4Cl + NH4OH (c) 2.37 (d) 4.74
45. (M) Which of the following mixtures is (are) buffer ? 51. (S) How many milliliters (mL) of a 0.0500 M NaOH (a strong
base) solution should be added to 1.00 L of 0.100 M
(a) 10 mL 0.1 M NH4Cl + 10 mL 0.08 M NaOH H3PO4, solution to produce a buffer of pH = 2.00 ? For
(b) 20 mL 0.22 M CH3COOH + 30 mL 0.15 M NaOH H3PO4, K a1 = 6.67 × 10–3
(c) A 0.10 M NaHCO3 solution
Given : H3PO4 + OH– (from NaOH) o H2PO4– + H2O
(d) 15 mL 0.12 M CH3NH2 + 10 mL 0.07 M HCl
(a) 200 (b) 400
46. (S) Calculate the [NH 3]/[NH 4+] ratio in an ammonia-
(c) 600 (d) 800
ammonium chloride buffer with a pH of 9.00.
(Kb = 1.8 × 10–5 for ammonia) 52. (I) A buffer solution is formed by mixing 100 mL 0.01 M
CH3COOH with 200 mL 0.02 M CH3COONa. If this
(a) 0.56 : 1.00 (b) 0.74 : 1.00
buffer solution is made to 1.0 L by adding 700 mL of
(c) 0.86 : 1.00 (d) 1.12 : 1.00 water, pH will change by a factor of
47. (S) How many milliliters of 0.250 M NH4Cl would have to 53. (S) What volume of 0.40 M NH3 solution must be added to
be added to 450 mL of 0.350 M KOH in order to produce 1.0 L of 0.10 M NH4Cl solution to give a buffer having
a buffer solution with a pH of 9.10 ? (K b (NH 3 ) pH of 10.00 ? For NH3, Kb = 1.8 × 10–5
= 1.8 × 10–5)
(a) 1.4 L (b) 1.1 L
(a) 450 mL (b) 600 mL
(c) 0.97 L (d) 0.61 L
(c) 750 mL (d) 350 mL
54. (S) For the overall reaction
48. (S) A buffer solution of pH = 9.00 is made by dissolving
ammonium chloride and ammonia in water. How many H 2S(aq) U 2H (aq) S2 (aq) , the value of K a is
moles of ammonium chloride must be added to 1.0 L of
0.25 M ammonia to prepare this buffer ? 1×10–22. The Ksp for ZnS is 1.2 × 10–23. What would be
the maximum concentration of Zn+2(aq) ion in a 0.01 M
NH3 (aq) H 2 O U NH 4 (aq) OH (aq); K b =1.8 × solution of H2S that has its pH adjusted to 5 by mixing
10–5 a strong acid with the H2S ?
(a) 0.25 mol (b) 0.45 mol (a) 1.2 × 10–9 M (b) 2.4 × 10–6 M
(c) 0.65 mol (d) 2.2 mol (c) 3.8 × 10–4 M (d) 1.8 × 10–1 M
C-18
IONIC EQUILIBRIUM
55. (S) For the overall reaction H2S(aq) U 2H+(aq) + S2– (aq), 10–3 M H3PO4 (pH = 7) is used in fertilisers as an
the value of KA is 1 × 10–22. The Ksp for FeS is 4 × 10–19. aqueous soil digesting. Plants can absorb zinc in water
What would be the maximum concentration of Fe+2 (aq) soluble form only. Zinc phosphate is the source of zinc
ion in a 0.1 M solution of H2S that has has its pH and PO34 ions in the soil. Ksp of zinc phosphate
adjusted to 2 by mixing a strong acid with the H2S ? = 9.1 × 10–33.
(a) 4 × 10–38 M (b) 6 × 10–10 M
59. (C) [PO34 ] ion in the soil with pH = 7, is
(c) 6 × 10–6 M (d) 4.0 M
(a) 10–3 M (b) 1.2 × 10–4 M
Polyprotic Acids and Bases
(c) 2.2 × 10–4 M (d) 1.1 × 10–10 M
56. (S) H3 PO 4 H 2 O U H3O H2 PO 4 ; pK1 = 2.15 60. (C) [Zn2+] ion in the soil is
(a) 2.9 × 10–11 M (b) 4.0 × 10–10 M
H 2 PO4 H 2O U H3O HPO 24 pK2 = 7.20
(c) 3.0 × 10–6 M (d) 9.1 × 10–5 M
Hence pH of 0.01 M NaH2PO4 is : Salt Hydrolysis
(a) 9.35 (b) 4.675 61. (S) A 100 mL portion of water is added to each of the
(c) 2.675 (d) 7.350 following two solutions.
(i) 100 mL of 0.02 M KCl (ii) 100 mL of 0.02 M HCl
57. (S) Calculate the molar concentrations of H3O+, HSO4–, and
Which of the following statements is correct ?
SO42– in a 0.250 M solution of H2SO4. Assume K a1 is
(a) There will be no change in pH of solution (i) and (ii)
very large ; K a 2 = 1.20 × 10–2.
(b) The pH of solution (i) will remain the same but pH of
solution (ii) will increase
[H3O+], M [HSO4–], M [SO 24 ], M
(c) The pH of solution (i) will remain same but of
(a) 0.250 0.250 0.000 solution (ii) will decrease
(d) The pH of solution (ii) will remain same but of
(b) 0.250 0.250 0.0120
solution (i) will increase
(c) 0.500 0.000 0.500
62. (S) The correct order of increasing [H3O+] in the following
(d) 0.261 0.239 0.0110 aqueous solution is :
58. (S) What is the equilibrium [OH–] in 0.1413 M H2CO3 ? (a) 0.01 M H2S < 0.01 M H2SO4 < 0.01 M NaCl < 0.01 M
NaNO3
H 2 CO3 H 2 O U H3 O HCO3 (Ka = 4.30 ×10–7) (b) 0.01 M NaCl < 0.01 M NaNO3 < 0.01 M H2S < 0.01 M
H2SO4
(a) 7.07 × 10–14 M (b) 2.46 × 10–4 M
(c) 0.01 M H2S < 0.01 M NaNO3 = 0.01 M NaCl < 0.01 M
(c) 4.06 × 10–11 M (d) 6.84 × 10–6 M
H2SO4
Comprehension (d) 0.01 M H2S < 0.01 M NaNO3 < 0.01 M NaCl < 0.01 M
H2SO4
H3PO4 is a tribasic acid with pK a1 , pK a 2 and pK a 3
63. (S) pH of water is 7. When a substance Y is dissolved in
2.12, 7.21, and 12.32, respectively. It is used in fertiliser water, the pH becomes 11. The substances Y is a salt
productions and its various salts are used in food, of :
dtergent, toothpaste, and in metal treatment.
(a) weak acid and weak base
Small quantities of H3PO4 are used in imparting the
(b) strong acid and strong base
sour or tart taste to soft drinkes, such as Coca Cola,
and beers, in which H3PO4 in present 0.05% by weight (c) strong acid and weak base
(density = 1.0 g mL–1). (d) weak acid and strong base
C-19
IONIC EQUILIBRIUM
64. (M) Degree of hydrolysis for a salt of strong acid and weak 69. (X) Match the Column-I with Column-II :
base is : Column-I Column-II
(a) independent of dilution
(Salt) (Nature of hydrolysis)
(b) increase with dilution
(A)NH4CN (p) Only cation hydrolysis
(c) increase with decrease in Kb of the bases
(B) CH3COONa (q) Only anion hydrolysis
(d) decreases with decrease in temperature
(C) NaClO4 (r) Both cation and anion
65. (M) A 0.1 M sodium acetate solution was prepared. The
–10 hydrolysis
Kh = 5.6 × 10
–5 (D) Fe(NO3)2 (s) No hydrolysis
(a) The degree of hydrolysis is 7.48 × 10
70. (X) Match the Column-I with Column-II :
– –3
(b) The [OH ] concentration is 7.48 × 10 M Column-I Column-II
– –6
(c) The [OH ] concentration is 7.48 × 10 M (A)NH4Cl (p) No hydrolysis
(d) The pH is approximately 8.88
(B) NaCl (q) h Kh / C
66. (X) Match the following :
Column I Column II Kw
(C) CH3COONa (r) h CK b
(A) Degree of hydrolysis (P) the hydrolysis of anion
for salts of strong which is irreversible.
(D) CH3COONH4 (s) h Kh
acid and weak base
(B) Hydrolysis constant (Q) is not possible because where, C = Concentration of Salt ; Kh = hydrolysis constant
of the reaction of strong Kw = Ionic product of water ; Kb = Dissociation constant of

base with strong acid. weak base
(C) Na2O in water is basic (R) is affected when 71. (A) Assertion : When aqueous, solution of CH3COONH4
due to temperature is changed is diluted, then its degree of hydrolysis increases.
and concentration is Reason : Ammonium acetate is the salt of weak acid
changed. and weak base, its degree of hydrolysis does not
+ depend on the concentration.
(D) Na + H2O (S) is independent of volume
+ (a) A (b) B
NaOH + H of solution taken but
depends upon temperature. (c) C (d) D
67. (A) Assertion : Aqueous solution of ammonium carbonate 72. (M) Which among the following salts will give basic
is basic. solution on hydrolysis ?
Reason : Acidic or Basic nature of a salt solution of a (a) NaH2PO4 (b) NH4Cl
salt of weak acid and weak base depends on Ka and Kb (c) NaCl (d) K2CO3
of the acid and base forming it.
73. (S) Calcium lactate is a salt of weak acid i.e., lactic acid
(a) A (b) B having general formula Ca(Lac)2. Aqueous solution of
(c) C (d) D salt has 0.3 M concentration. pOH of solution is 5.60. If
90% of the salt is dissociated then what will be the
68. (A) Assertion : H3BO3 is aprotic acid.
value of pKa ?
Reason : Borax is salt of H3BO3 and NaOH ; its aqueous
(a) 2.8 – log (0.54) (b) 2.8 + log (0.54)
solution is alkaline in nature.
(c) 2.8 + log (0.27) (d) None of these
(a) A (b) B
(c) C (d) D
C-20
IONIC EQUILIBRIUM
74. (S) If 0.1 mol of salt is added to 1L water, which of these 80. (S) A solution of 0.1 M NaZ has pH = 8.90. The Ka of HZ is
salts is expected to produce the most acidic solution ? –11 –10
(a) 6.3 × 10 (b) 6.3 × 10
(a) NaC2H3O2 (b) NH4NO3 –5 –6
(c) 1.6 × 10 (d) 1.6 × 10
(c) CuSO4 (d) AlCl3 81. (S) If pKb for fluoride ion at 25ºC is 10.83, the ionisation
75. (S) Hydrolysis constants of two salts KA and KB of weak constant of hydrofluoric acid in water at this temperature
–8 –6
acids HA and HB are 10 and 10 . If the dissociation is
–2 –5 –3
constant of third acid HC is 10 . The order of acidic (a) 1.74 × 10 (b) 3.52 × 10
–4 –2
strengths of three acids will be : (c) 6.75 × 10 (d) 5.38 × 10
(a) HA > HB > HC (b) HB > HA > HC Solubility Equilibria
(c) HC > HA > HB (d) HA = HB = HC 82. (S) The solubility of silver benzoate (C6H5COOAg) in H2O
76. (M) The equilibrium constant (Kc) for the reaction of a weak and in a buffer solution of pH = 2, 3, and 4 are S1, S2, S3
9 and S4 respectively. The decreasing order of solubility
acid HA with strong base NaOH is 10 at 25ºC. Which
of the following are correct deduction ? is
–5 (a) S1 > S2 > S3 > S4 (b) S4 > S3 > S2 > S1
(a) The ionization constant (Ka) at 25ºC is 10 for HA.
(c) S2 > S3 > S4 > S1 (d) S3 > S2 > S4 > S1
(b) pH of a 0.01 M aqueous solution of HA at 25ºC will
be 3.5 83. (S) Ksp of Mg (OH)2 is 1 × 10–12. 0.01 M MgCl2 will be
precipitating at the limiting pH :
(c) pH of a 0.10 M aqueous solution of NaA at 25ºC
(a) 8 (b) 9
will be 9.
–4
(c) 10 (d) 12
(d) If Kb of a weak base BOH is 10 at 25ºC, equilibrium 84. (S) The solubility products of MA, MB, MC and MD are
constant for neutralization of HA with BOH at 25ºC
–5 1.8 × 10–10, 4 × 10–3, 4 × 10–8 and 6 × 10–5 respectively.
will be 10
If a 0.01 M solution of MX is added dropwise to a
77. (I) If the equilibrium constant of the reaction of a weak mixture containing A–, B–, C– and D– ions then the one
9
acid HA with a strong base is 10 , then pH of a 0.10 M to be precipitated first will be :
NaA solution is (a) MA (b) MB
78. (A) Assertion : If HA and HB are two weak non-basic acids (c) MC (d) MD
with Ka(HA) < Kb(HB), then, the aqueous solution of 85. (M) A solution containing a mixture of 0.05 M NaCl and 0.05
NaA will have higher pH than pH of aqueous solution M Nal is taken. (K sp of AgCl = 10 –10 and Ksp of
of NaB of same concentration. AgI = 4 × 10–16). When AgNO3 is added to such a
Reason : Conjugate base of a weaker acid is stronger solution:
than the same of stronger acid. (a) the concentration of Ag+ required to precipitate Cl–
(a) A (b) B is 2 × 10–9 mol/L
(c) C (d) D (b) the concentration of Ag+ required to precipitate I–
is 8 × 10–15 mol/L
79. (A) Assertion : Knowing K a 2 of CO2 can determine pH of
(c) AgCl and AgI will be precipitate together
an aqueous solution of Na 2 CO 3 of known (d) first AgI will be precipitated
concentration. 86. (M) Which of the following is (are) correct when 0.1 L of
0.0015 M MgCl2 and 0.1L of 0.025 M NaF are mixed
Reason : Only first hydrolysis of CO32 ion is
together ?
significant because for most of the dibasic acids,
(Ksp of MgF2 = 3.7 × 10–8)
K a1 !! K a2 . (a) MgF2 remains in solution
(a) A (b) B (b) MgF2 precipitates out
(c) MgCl2 precipitates out
(c) C (d) D
(d) Cl– ions remain in solution
C-21
IONIC EQUILIBRIUM
Comprehension 91. (I) How much AgBr could dissolve in 1.0 L of 0.4 M NH3 ?
Solubility of a salt is defined as the maximum amount of Assume that Ag ( NH 3 ) 2 is the only complex formed
a salt which can be dissolved in a given amount of Given : The dissociation constant for
solvent at a particular temperature. Unit of solubility is
mole per litre of solution. The solubility of a salt of + –8
Ag( NH 3 ) 2 Ag + 2NH3; Kd = 6.0 × 10 and
weak acid with strong base (CH3COOAg) in acidic
buffer can be calculated as
– + –13
CH3COOAg YZZ Ksp (AgBr) = 5.0 × 10 .
Z CH3COO (aq) + Ag (aq)
ZZZX
S–X S (As in 10–3 M)
S = Solubility of salt
92. (I) HN3 (hydroazoic acid) is a weak acid dissociating as :
– +
CH3COO (aq) + H Z CH3COOH
ZZZX
YZZ +
HN3 H + N 3 .
(S – X) (from acidic buffer) X
+ – +
Ksp = [Ag ] [CH3COO ] = S (S – X) Find the concentration of Ag ions, if excess of solid
Dissociation constant of weak acid AgN3 is added to a solution maintained at ph = 4. The
–5
ionisation constant Ka of HN3 is 2.0 × 10 . The
(S X) [H ] solubility of AgN 3 in pure water is found to be
(K a ) –3
X 5.4 × 10 M at 25ºC.
87. (C) The solubility of LiOH in a solution with pH = 8 is Comprehension
–12
(Ksp = 1.8 × 10 )
–18 –6 The product of the concentrations of the ions of an
(a) 1.8 × 10 (b) 1.8 × 10
electrolyte raised to power of their coefficients in the
–6 –4
(c) 10 (d) 1.8 × 10 balanced chemical equation in the solution at any
concentration. Its value is not constant and varies with
88. (C) The solubility of AgCl is maximum in change in concentration. Ionic product of the saturated
(a) 0.1 M NaCl (b) 0.1 M HCl solution is called solubility product Ksp.
(c) 55.5 M H2O (d) None of these
(i) When Kip = Ksp, the solution is just saturated and
89. (C) The solubility of CaCO3 is 7 mg/L. Calculate the no precipitation takes place.
solubility product of BaCO3 from this information and
from the fact that when Na2CO3 is added slowly to a (ii) When Kip < Ksp, the solution is unsaturated and
2+ precipitation will not take place.
solution containing equimolar concentration of Ca
2+ 2+
and Ba , no precipitate is formed until 90% of Ba (iii) When Kip > Ksp, the solution is supersaturated and
has been precipitated as BaCO3. precipitation takes place.
–10 –5
(a) 4.9 × 10 (b) 5.9 × 10 93. (C) Which of the following is most soluble ?
–10 –5
(c) 6.9 × 10 (d) 8.3 × 10
(a) Bi2S3 (Ksp = 1× 10–70) (b) MnS (Ksp = 7 × 10–16)
90. (X) Match the following :
(c) CuS (Ksp = 8 × 10–37) (d) Ag2S (Ksp = 6 × 10–51)
Column I Column II
+Y X –X Y
(A) [A ] [B ] > Ksp (P) Precipitation just starts 94. (C) The concentration of Ag+ ions in a given saturated
+Y X –X Y solution of AgCl at 25ºC is 1.06 × 10–5 g ion per litre.
(B) [A ] [B ] < Ksp (Q) Buffer capacity The solubility product of AgCl is :
+Y X –X Y
(C) [A ] [B ] = Ksp (R) The solid AXB4 will
(a) 0.353 × 10–10 (b) 0.530 × 10–10
precipitate out
(D) d(n)/dpH (S) No precipitation (c) 1.12 × 10–10 (d) 2.12 × 10–10
C-22
IONIC EQUILIBRIUM
95. (C) If the solubility of Li3Na3 (AlF6)2 is x mol L–1, then its 101. (C) The factor by which the solubility of AgCN is increased
solubility product is equal to : in the above solution as compared to its solubility in
pure water is
(a) 12x3 (b) 18x3
(a) 10 (b) 100
(c) x8 (d) 2916x8
–9 –3 (c) 1250 (d) 5000
96. (I) M(OH)x has Ksp of 4 × 10 and its solubility of 10 M.
The value of x is ______ . –10
102. (S) How many grams of AgCl (Ksp = 1.8 × 10 ) will dissolve
–6 2+ –5
97. (A) Assertion : On miximg 500 mL of 10 M Ca ion and in 1.0 L of 6.0 M NH3 (Kb = 1.8 × 10 ). The Kformation
–6 – + 7
500 mL of 10 M F ion, the precipitate of CaF2 will be for Ag(NH3)2 is 1.7 × 10 .
–18
obtained Ksp (CaF2) = 10 .
(a) 0.0013 g (b) 43 g
Reason : If Ksp is less than ionic product, precipitate
will be obtained. (c) 1.3 g (d) 12 g
2+
(a) A (b) B 103. (S) What is the highest pH at which 0.050 M Mn remains
entirely in a solution that is saturated with H2S, at a
(c) C (d) D concentration of, [H2S] = 0.10 M. Given for the reaction,
98. (S) Solubility of calcium phosphate (molecular mass, M) in
–15
water is W g per 100 mL at 25ºC. Its solubility product MnS(s) U Mn 2 S2 , Ksp = 3.6 × 10
at 25ºC will be approximately :
–8 –15
5 5 For H2S : K a1 = 9.2 × 10 , and K a 2 = 1.2 × 10
9§W· 7§W·
(a) 10 ¨ ¸ (b) 10 ¨ ¸
©M¹ ©M¹ (a) 2.9 (b) 3.9
5 5 (c) 4.4 (d) 4.9

5§W· 3§W·
(c) 10 ¨ ¸ (d) 10 ¨ ¸
©M¹ ©M¹ –12
104. (S) For Ag 2 CO 3 , K sp = 6.2 × 10 , For AgCl, K sp
–10
= 2.8 ×10 . Solid Ag2CO3 and solid AgCl are added to
Comprehension
a beaker containing 1.00 M Na2CO3(aq). Under these
2– –
The solubility product constant of AgCN is 2.5×10– conditions the [CO3 ] = 1.00 M. Calculate the [Cl ] in
16
. The acid dissociation constant of HCN is 6.2 × solution when equilibrium is established.
10 –10 . Now solid AgCN is dissolved in a buffer –4 –6
(a) 1.1 × 10 (b) 1.26 × 10
solution of pH 3.
–6
Answer the following questions : (c) 0.15 (d) 2.8 × 10
–
99. (C) The concentration ratio of HCN to CN in the solution 105. (S) Given the following K sp values : for M(OH) 4 ,
–19 –14
is Ksp(M) = 4.0 × 10 ; for Z(OH)2, Ksp(Z) = 1.0 × 10 .
–7 6 One mole of each of the above solids is placed in a
(a) 6.25 × 10 (b) 1.6 × 10 beaker containing 1 (one) litre of pure water. These solids
9 –10 go into equilibrium with their ions. Calculate the pH
(c) 1.6 × 10 (d) 6.2 × 10
required for the metal ion concentrations to be equal,
4+ 2+
–1
100. (C) The solubility of AgCN (mol-L ) in the above solution [M ] = [Z ].
is
(a) 12.6 (b) 9.6
–8 –10
(a) 1.58 × 10 (b) 6.2 × 10
(c) 6.7 (d) 11.8
–5 –7
(c) 2 × 10 (d) 4 × 10
C-23
IONIC EQUILIBRIUM
106. (I) Solubility product constant of a springly soluble salt Which of the following is/are correct for the given
–12
MCl2 is 4 × 10 at 25ºC. Also, at 25ºC, solubility of curve ?
8
MCl2 is an aqueous solution of CaCl2 is 4 × 10 times (a) The solution being titrated is a base and the titrant
less compared to its solubility in pure water. Hence, is an acid
concentration (molarity) of CaCl2 solution is
(b) The pH at the equivalence point must be less than 7
107. (I) The solubility product constant of a metal carbonate
–12
MCO3 is 2 × 10 at 25ºC. A solution is 0.1 M in (c) The titrated solution is strong acid
M(NO3)2 and it is saturated with 0.01 M CO2. Also the (d) The titrated solution is strong base
–7
ionization constant of CO2 are K a1 = 4 × 10 and K a 2 110. (A) Assertion : The pH of the solution at the mid point of
–11
= 5 × 10 at 25ºC. The minimum pH that must be the weak acid strong base titration becomes equal to
the pKa of the acid.
maintained to start any precipitation is
Indicators and Titrations Reason : The molar concentrations of proton acceptor
and proton donor become equal at mid point of a weak
108. (M) Titration curve for a weak acid with a strong base is acid.
(a) A (b) B
(c) C (d) D
111. (I) The equivalence point in a titration of 40.0 mL of a
solution of a weak monoprotic acid occurs when 35.0 mL
of a 0.10 M NaOH solution has been added. The pH of
the solution is 5.5 after the addition of 20.0 mL of NaOH
solution. What is the dissociation constant of the
–6
acid ? (in 10 )
112. (I) When a 40 mL of a 0.1 M weak base, BOH is titrated
with 0.10 M HCl, the pH of the solution at the end point
is 5.5. What will be the pH if 10 mL of 0.10 M NaOH is
Which of the following s/are correct for the above added to the resulting solution ?
curve ? 113. (X) Match the Column-I with Column-II :
(a) At the half-neutralization point pH = pKa Column-I Column-II
(b) The pH is greater than 7 at the equivalence point
(A) has highest pH at end (p) CH3COOH
(c) The colour change in basic medium –5
point when titrated against Ka = 1.8 × 10
(d) The solution at the half neutralization is buffer
solution standard NaOH
109. (M) The titration curve given below involves 1.0 M (B) has lowest pH at the end (q) HCN
solutions of an acid and a base. –10
point when titrated against Ka = 5 × 10
standard NaOH
(C) release maximum heat (r) HF
–4
when neutralized with Ka = 5 × 10
NaOH
(D) release equal amount (s) NH4OH
–5
of heat when neutralized Kb = 1.8 × 10
with strong acid or base
C-24
IONIC EQUILIBRIUM
114. (X) Match the Column-I with Column-II : 118. (C) Determine the pH after 20.0 mL of 0.100 M NaOH has
Column-I Column-II been added.
(Titration) (Indicator used) (a) 3.25 (b) 5.33
(A) Strong acid versus (p) Methyl orange (3 – 4.4) (c) 5.50 (d) 6.18
strong base
119. (C) Determine the pH after a total of 50.0 mL of 0.100 M
(B) Weak acid versus (q) Methyl red (4.3 – 6.3) NaOH has been added.
strong base
(a) 5.50 (b) 7.00
(C) Strong acid versus (r) Phenolphthalein (8 – 10)
(c) 8.41 (d) 9.24
weak base
(D) Weak acid versus (s) No suitable indicator 120. (C) Determine the pH after a total of 75.0 mL of 0.100 M
NaOH has been added.
weak base
115. (X) Match the Column-I with Column-II : (a) 8.41 (b) 9.24
Column-I (Indicator) Column-II (pH range) (c) 11.24 (d) 11.32
(A) Phenolphthalein (p) 4.2 – 6.3 Comprehension
(B) Litmus (q) 3.1 – 4.4
100 mL of a solution of X is titrated with a 0.1 M solution
(C) Methyl red (r) 8.3 – 10.0 of Y giving the following titration curve :
(D) Methyl orange (s) 5.0 – 8.0
116. (S) During the titration of weak diprotic acid H2A against
strong base NaOH, the pH of the solution half-way to
the first equivalence point and that at first equivalence
point are given respectively by :
pK a1 pK a 2
(a) pK a1 and pK a 2 (b) pK a1 and
2
(c) pKa and (pK a1 pK a 2 )
pK a1 pK a 2
(d) CK a1 and
2
117. (S) 0.2 g sample of benzoic acid, C6H5COOH is titrated with
0.12 M Ba (OH)2 solution. What volume of Ba(OH)2
solution is required to reach the equivalence point ?
–1 Answer the following four questions based on the
Molar mass of benzoic acid is 122 g mol information provided.
(a) 6.82 mL (b) 13.6 mL
121. (C) Y is a
(c) 17.6 mL (d) 35.2 mL
(a) strong acid (b) strong base
Comprehension
(c) weak base (d) weak acid
Consider the titration of a diprotic acid (H 2 A ;
122. (C) X is a
K a1 = 3.1 × 10 –6, K a 2 = 4.8 × 10–12) with a solution
(a) strong acid (b) strong base
of NaOH. Specifically, you titrate 50.0 mL of 0.100 M
H2A with 0.100 M NaOH. (c) weak base (d) weak acid
Answer the following question based on this
titration experiment.
C-25
IONIC EQUILIBRIUM
123. (C) The initial concentration of X is

(a) 0.10 M (b) 0.02 M
(c) 0.05 M (d) 0.01 M
124. (C) The approximate value of ionization constant (Ka/Kb)

of X is
–9 –6
(a) 5 × 10 (b) 5 × 10
–4 –5
(c) 2 × 10 (d) 3 × 10
125. (S) Following figure represents simulated titration curves
for solutions of four acids titrated with the same
standard base solution. Based on these titration curves,
we can accurately predict that
(a) Curve 4 represents the smallest concentration and

the weakest acid.
(b) Curve 1 represents the largest concentration and
the strongest acid.
(c) The dissociation constant for the acid represented
–4 –4
by curve 3 is about 1 × 10 (i.e., Ka = 1 × 10 ).
(d) All the responses above are correct.
C-26
IONIC EQUILIBRIUM
Answer Key
1. (a) 2. (a,c) 3. (d) 4. (d) 5. (a) 6. (a) 7. (a) 8. (a) 9. (a) 10. (d)
11. (c,d) 12. (a) 13. (d) 14. (a) 15. (0006) 16. (a,b,c,d) 17. (a) 18. (a) 19. (c) 20. (b)
21. (c) 22. (a,b) 23. (a,b,c) 24. (d) 25. (c) 26. (d) 27. (a) 28. (c) 29. (d) 30. (a)
31. (a) 32. (d) 33. (c) 34. (d) 35. (d) 36. (c) 37. (b,c) 38. (a,b,d) 39. (d) 40. (d)
41. (a) 42. (d) 43. (b) 44. (b,d) 45. (a,c,d) 46. (a) 47. (b) 48. (b) 49. (a) 50. (d)
51. (d) 52. (0000) 53. (a) 54. (a) 55. (d) 56. (b) 57. (d) 58. (c) 59. (c) 60. (a)
61. (b) 62. (b) 63. (d) 64. (b,c,d) 65. (a,c,d) 66. A o R, B o S, C o P, D o Q 67. (a) 68. (b)
69. (A-r), (B-r), (C-s), (D-p) 70. (A-q,r), (B-p), (C-q), (D-s) 71. (d) 72. (a,d) 73. (a) 74. (b)
75. (c) 76. (a,b,c,d) 77. (0009) 78. (a) 79. (a) 80. (c) 81. (c) 82. (c) 83. (b) 84. (a)
85. (a,b,d) 86. (b,d) 87. (b) 88. (c) 89. (a) 90. A o R, B o S, C o P, D o Q 91. (0001) 92. (0000)
93. (b) 94. (c) 95. (d) 96. (0002) 97. (d) 98. (b) 99. (b) 100. (c) 101. (c) 102. (b)
103. (d) 104. (a) 105. (d) 106. (0002) 107. (0004) 108. (a,b,c,d) 109. (a,b,c) 110. (a) 111. (0004)
112. (0009) 113. (A–q), (B–r), (C–r), (D–p,s) 114. (A–p,q,r), (B–r), (C–p,q), (D–s) 115. (A–r), (B–s), (C–p), (D–q)
116. (b) 117.(a) 118. (b) 119. (d) 120. (d) 121. (a) 122. (c) 123. (b) 124. (c) 125. (d)
Dream on !!
[\]^[\]^
C-27


Atoms Molecules
1. (S) If we consider that 1/6 in place of 1/12, mass of carbon 5. (S) If 1021 molecules are removed from 200mg of CO2, then
atom is taken to be the relative atomic mass unit, the the number of moles of CO2 left are
mass of one mole of a substance will
(a) 2.85 × 10–3 (b) 28.8 × 10–3
(a) decrease twice
(c) 0.288 × 10–3 (d) 1.68 × 10–2
(b) increase two fold
6. (S) A gaseous mixture contains oxygen and nitrogen in
(c) remain unchanged the ratio of 1 : 4 by weight. Therefore, the ratio of
(d) be a function of the molecular mass of the substance their number of molecules is
(a) 1 : 4 (b) 1 : 8
2. (A) Assertion : Both 138 g of K2CO3 and 12 g of carbon
have same number of carbon atoms. (c) 7 : 32 (d) 3 : 16
Reason : Both contains 1 g atom of carbon which 7. (S) A compound possesses 8% sulphur by mass. The least
contains 6.022 × 1023 carbon atoms. molecular mass is
(a) 200 (b) 400
(a) A (b) B
(c) 155 (d) 355
(c) C (d) D
8. (M) 8 g O2 has same number of molecules as that in :
3. (A) Assertion : 1 Avogram is equal to 1 amu.
(a) 14 g CO (b) 7 g CO
Reason : Avogram is reciprocal of Avogadro’s number.
(c) 11 g CO2 (d) 22 g CO2
(a) A (b) B
9. (M) Which of the following have same number of atoms ?
(c) C (d) D
(a) 6.4 g of O2 (b) 0.1 mol of NH
4. (X) Column I Column II (c) 4.0 g of He (d) 22.4 L of Cl2 at STP
(A) 5.4 g of Al (P) 0.5 NA electrons 10. (A) Assertion : Number of molecules present in SO2 is
twice the number of molecules present in O 2.
(B) 1.2 g of Mg2+ (Q) 15.9994 amu
Reason : Molecular mass of SO2 is double to that of
(C) Exact atomic weight of (R) 0.2 mole atoms mixture
O2.
of oxygen isotopes (a) A (b) B
(D) 0.9 ml of H2O (S) 0.05 moles (c) C (d) D
C-28
Stoichiometric Calculations
Or KClO {2Al.
11. (S) P and Q are two elements which forms P 2Q3 and PQ2.
If 0.15 mole of P 2Q3 weights 15.9g and 0.15 mole of I : CaO + 3C o CaC2 + CO
PQ 2 weights 9.3g, the atomic weight of P and Q is
(respectively) : II : CaC2 + 2H2O o Ca(OH)2 + C2H2
(a) 18, 26 (b) 26,18 CaC2 (calcium carbide) is prepared in step I. It is used to
(c) 13, 9 (d) None of these
prepare acetylene (C2H2) in step II. Suppose we want to
12. (S) 1 mole of oxalic acid is treated with conc. H2SO4. The
resultant gaseous mixture is passed through a solution determine amount of CaO that can give enough CaC2 to
of KOH. The mass of KOH consumed will be (where converted required amount of C2H2. Amount of CaO is
KOH absorbs CO2.)
determined in step I and then amount of C2H2 in step II.
(COOH)2 CO + CO2 + H2O
We can relate CaO and C2H2 stoichiometrically by writing
2 KOH + CO2 K2CO3 + H2O
net reaction which is
(a) 28 g (b) 56 g
CaO + 3C + 2H2 O o Ca(OH)2 + C2H2 + CO
(c) 84 g (d) 112 g
13. (M) 0.2 mole of K3PO4 and 0.3 mole of BaCl2 are mixed in 1 L of Thus, CaO { C2H2
solution. Which of these is/are correct ?
14. (C) NX is produced by the following step of reactions
(a) 0.2 mole of Ba3(PO4)2 will be formed
M + X2 o M X2
(b) 0.1 mole of Ba3(PO4)2 will be formed
MX2 + X2 o M3X8
(c) 0.6 mole of KCl will be formed
M3X8 + N2CO3 o N X + CO2 + M3O4
(d) 0.3 mole of KCl will be formed
How much M (metal) is consumed to produce 206 gm of
Comprehension
NX. (Take At. wt of M = 56, N=23, X = 80)
Often more than one reaction is required to change
starting materials into the desired product. This is true (a) 42 gm (b) 56 gm
for many reaction that we carry out in the laboratory and
for many industrial process. These are called sequential 14 7
(c) gm (d) gm
reactions. The amount of desired product from each 4
reaction is taken as the starting material for the next
15. (C) The following process has been used to obtain iodine
reaction.
from oil-field brines in California.
I : 2KClO3 o 2KCl + 3O2
NaI + AgNO o AgI + NaNO
II : 4Al + 3O2 o 2Al2 O
AgI + Fe o FeI2 + Ag
KClO3 decomposes in step I to give O2, which in turn, is
used by Al to form Al2O3 in step II. First we determine FeI2 + Cl2 o FeCl3 + I2
O2 formed in step I and then Al used by this O2 in step II. If 381 kg of iodine is produced per hour then mass of
Both reactions can be added to determine amount of
AgNO required per hour will be
KClO3 that can give required amount of O2 needed for
Al. [atomic mass Ag– 108, I– 127, Fe–56, N–14, Cl–35.5]
Net : 2KClO3 + 4Al o 2KCl + 2Al2O (a) 170 kg (b) 340 kg
Thus, 2KClO {4Al (c) 255 kg (d) 510 kg
C-29
16. (C) 120 gm Mg was burnt in air to give a mixture of MgO and 18. (S) If 7.0 moles of Y is placed in a container and allowed to
react with X until equilibrium is reched according to the
Mg3N2. The mixture is now dissolved in HCl to form reaction :
MgCl2 and NH4Cl, if 107 grams NH4Cl is produced. The
2X + Y o 2Z
reaction are follows
It is found that the equilibrium mixture contains 8.0 moles
1 of X and 5.0 moles of Y. How many moles of X were
I. Mg + O2 o MgO ,
2 present in the original container ?
II. 3Mg N2 o Mg 3 N2 (a) 10 (b) 12
III. MgO + 2HCl o MgCl2 + H2O, (c) 14 (d) 16

19. (S) Consider the given reversible reaction at equilibrium
IV. Mg3 N2 + 8HCl o 2NH4Cl + 3MgCl2
2NO + Cl2 o 2ClNO(g)
Then the moles of MgCl2 formed is : (At. wt.
Suppose that 0.30 mol NO, 0.20 mole of Cl2 and 0.50 mole
Mg = 24, N = 14, Cl = 35.5)
of ClNO were placed in a 25.00L vessel and allowed to
reach the equilibrium. At equilibrium, the concentration
(a) 3 moles (b) 6 moles
of ClNO was found to be 0.024 molar. Molar
concentration of NO present at equilibrium is
(c) 5 moles (d) 10 moles
(a) 0.004 M (b) 0.006 M
17. (X) On the left column, some reactions are indicated and on
the right column, properties of reactions are described. (c) 0.008 M (d) 0.01 M
Match them appropriately, and select the correct code.
20. (I) A mixture of FeO and Fe3O4 when heated in air to a
Column I Column II constant weight, gains 5% of its weight. Find the
percentage of Fe3O4.
(A) N 2 (5.00g) H 2 (1.00g) (p) First reactant is the limiting
21. (I) Igniting MnO2 in air converts it quantitatively to Mn3O4.

o NH reagent. A sample of pyrolusite is of the following composition :
MnO2 = 80%, SiO2 and other inert constituents = 15%
(B) N 2 (3g) F2 (10g) (q) Mass of reactant = Mass and rest bearing H2O. The sample is ignited to constant
weight. What is the % of Mn in the ignited sample ?

o N 2 F4 of product
22. (I) A mixture contains equi-molar quantities of carbonates
of two bivalent metals. One metal is present to the extent
(C) S (1.0g) + O2 (1.0 g) (r) Stoichiometric amounts of of 13.5% by weight in the mixture and 2.50 gm of the
mixture on heating leaves a residue of 1.18 gm. Calculate

o SO 2 reactants. the % age by weight of the other metal.
23. (I) A 0.01 moles of sample of KClO was heated under such
conditions that a part of it decomposed according to the
(s) Second reactant is the equation :
limiting reactant. (a) 2KClO3 o 2KCl + 3O2 and the remaining undergoes
p q r s change according to the equation :
(a) B A A C (b) 4KClO3 o 3KClO4 + KCl
(b) B C B A If the amount of O2 evolved was 134.4 mL at S.T.P.,

calculate the % age by weight of KClO4 in the residue.
(c) B C C A
(d) C A B C
C-30
24. (M) Three metals of alkaline earth metal group (A, B, and C) 27. (M) Which of the following statements is/are correct ?
when reacted with a fixed volume of liquid Br2 separately The following reaction occurs :
gave a product (metal bromides) whose mass is plotted
'
against the mass of metals taken as shown in the figure. 2Al 3MnO o CCl4 S2Cl 2
108.0g of Al and 213.0g of MnO was heated to initiate

the reaction . (Mw of MnO = 71, atomic weight of
Al = 13)
(a) Al is present in excess.
(b) MnO is present is excess.
(c) 54.0g of Al is required.
(d) 159.0g of MnO is in excess.
From the plot, predict what relation can be concluded Percent Purity
between the atomic weights of A, B, and C ?
28. (S) To 1 L of 1.0 M impure H2SO4 sample, 1.0 M NaOH
(a) C > B solution was added and a plot was obtained as follows :
(b) B > A
(c) C < A < B
(d) Data is insufficient to predict
25. (I) One commercial system removes SO2 emission from
smoke at 95ºC by the following set of reaction :
SO 2 (g) Cl2 (g)

o SO 2 Cl 2 (g)
SO 2Cl2 (g) H 2 O(l )

o H 2SO 4 HCl
H 2SO 4 C (OH) 2
o C SO 4 H 2O
How many grams of CaSO4 may be produced from 3.78g

of SO2 ?
The % purity of H 2 SO 4 and the slope of curve,
26. (M) Which of the following statements is/are correct ?
respectively, are :
1.0g mixture of CaCO3(s) and glass beads liberate 0.22g
(a) 75%, –1/2 (b) 75%, –1
of CO2 upon treatment with excess of HCl. Glass does
(c) 50%, –1/3 (d) 50%, –1/2
not react with HCl.
Percent Yield
CaCO3 2HCl
o CO 2 H 2O CaCl2
29. (S) In the preparation of iron from haematite (Fe2O3) by the
[Mw CaCO3 = 100. Mw of CO2 = 44, [Atomic weight of reaction with carbon
Ca = 40]
Fe 2O3 C
o Fe CO 2
(a) The weight of CaCO3 in the original mixture is 0.5g.
How much 80% pure iron could be produced from 120 kg
(b) The weight of calcium in the original mixture is 0.2g.
of 90% pure Fe2O3 ?
(c) The weight percent of calcium in the original mixture
is 40% Ca. (a) 94.5 kg (b) 60.48 kg
(d) The weight percent of Ca in the original mixture is (c) 116.66 kg (d) 120 kg
20% Ca.
C-31
30. (S) NH3 is formed in the following steps : 36. (C) Volume of acid that contains 63g pure acid is.
I. Ca + 2C o CaC2 50% yield (a) 100 mL (b) 40.24 mL
II. CaC2 + N2 o CaCN2 + C 100% yield (c) 63.38 mL (d) 70.68 mL
III. CaCN2 + 3H2O o 2NH3 + CaCO3 50% yield 37. (C) Volume of water required to make 1N solution from 2 mL
conc. HNO3.
To obtain 2 mol NH3, calcium required is :
(a) 1 mol (b) 2 mol (a) 29.56 mL (b) 30.56 mL
(c) 3 mol (d) 4mol (c) 28.56 mL (d) 31.56 mL

Strength : Mass Percent 38. (S) An aqueous solution of glucose (C6H12O6) is 0.01 M. To
31. (S) If 100 ml of H2SO4 (A) and 100 ml of H2O (B) are mixed. 200 mL of this solution, which of the following should
be carried out to make it 0.02 M ?
Then the mass per cent of H2SO4 would be (Given density
of H2SO4 = 0.9 g/ml; density of H2O = 1.0 g/ml) I. Evaporate 50 ml of solution
(a) 60 (b) 50 II. Add 0.180 gm of glucose
(c) 47.36 (d) 90
III. Add 50 mL of water
32. (S) If 100 mL of H2SO4 and 100 mL of H2O are mixed, the
The correct option is :
mass percent of H2SO4 in the resulting solution is
(a) I (b) II
(d H2SO4 0.09g mL1 , d H2O 1.0g mL1 )
(c) I, II (d) I, II, III
(a) 90 (b) 47.36
39. (S) Equal volumes of 0.200 M HCl and 0.400M KOH are mixed.
(c) 50 (d) 60
The concentrations of the ions in the resulting solution are :
Strength : Molality
(a) [K+] = 0.40M, [Cl–] = 0.20 M, [H+] = 0.20 M
33. (A) Assertion : Molality and mole fraction units of
concentration do not change with temperature. (b) [K+] = 0.20 M, [Cl–] = 0.10 M, [OH–] = 0.10 M
Reason : These concentration units are defined in terms
(c) [K+] = 0.10 M, [Cl–] = 0.10 M, [OH–] = 0.10 M
of mass rather in terms of volume and mass is
independent of temperature. (d) [K+] = 0.20 M, [Cl–] = 0.10 M, [OH–] = 0.20 M
(a) A (b) B
40. (M) You are provided with 1 M solution of NaNO3 whose
(c) C (d) D
density = 1.25 g/ml
34. (M) Select dimensionless quantity(ies) :
(a) The percentage by mass of NaNO3 = 6.8
(a) vapour density (b) molality
(c) specific gravity (d) mass fraction (b) The percentage by mass of H2O = 93.2
Comprehension (c) The molality of the solution is 10.72
–1
HNO3 used as a reagent has specific gravity of 1.42g mL
(d) The solution has 0.2 moles of NaNO3.
and contains 70% by strength HNO3.
41. (A) Assertion : In laboratory, reagents are made to a specific
35. (C) Normality of acid is.
molarity rather molality.
(a) 16.78 (b) 15.78
Reason : The volume of sulution is easier to measure
(c) 14.78 (d) 17.78 than its mass.
(a) A (b) B
(c) C (d) D
C-32
COMPREHENSION Strength : Mole Fraction

The analytical molarity of a solution gives the total 47. (M) The mole fraction of NaCl in aqueous solution is 0.2.
number of moles of a solute in one litre of the solution. The solution is
The equilibrium molarity represents the molar
(a) 13.9 m
concentration of particular species in a solution at
equilibrium. In order to specify the equilibrium molarity (b) Mole fraction of H2O is 0.8
of a particular species it is necessary to know how the (c) acidic in nature
solute behaves when it is dissolved in a solvent. e.g., if
(d) neutral
analytical molarity of HCl is 0.1 M then equilibrium
molarity of NaOH equal to zero because HCl is Strength : Variation
completely dissociated.
48. (M) When 100 ml of 0.1 M KNO3, 400 ml of 0.2 M HCl and 500
42. (C) Calculate the analytical molarity of Cl– ion in solution ml of 0.3 M H2SO4 are mixed. Then in the resulting
which is prepared by mixing 100 ml of 0.1 M NaCl and solution
400 ml of 0.01 M BaCl2.
(a) The molarity of K+ = 0.01 M
(a) 0.018 M (b) 0.036 M
(b) The molarity of SO42– = 0.15 M
(c) 0.084 M (d) 0.046 M
(c) The molarity of H+ = 0.38 M
43. (C) The molarity of 68 % of H2SO4 whose density is 1.84 g/
cc is (d) The molarity of NO3– = 0.01 M and Cl– = 0.08 M
(a) 12.76 M (b) 6.84 M 49. (A) Assertion : Molality of solution is independent of
(c) 18.4 M (d) 6.8 M temperature while mole fraction depends on temperature.
Reason : Normality is the ratio of moles of solute and
44. (C) HCl is 80% ionised in 0.01 M aqueous solution. The volume of solution while mole fraction is the ratio of
equilibrium molarity of HCl in the solution is moles of solute and weight of solvent present in solution.
(a) 0.002 (b) 0.06 (a) A (b) B
(c) 0.02 (d) 0.008 (c) C (d) D
45. (M) Which of the following statements is/are correct ?
50. (A) Assertion : When a solution is diluted from volume V1
20.0 mL of 6.0 M HCl is mixed with 50.0 mL of 2.0 M to V2 by adding solvents, its molarity before dilution
Ba(OH)2, and 30 mL of water is added.
M1 and after dilution M2 are related as :
(a) The concentration remaining in solution is 0.8 M1V1 = M2V2
M.
Reason : During dilution, moles of the solute remains
(b) The concentration of remaining in solution is 1.2 conserved.
M.
(a) A (b) B
2+
(c) The concentration of Ba remaining in solution is (c) C (d) D
1.0M
51. (A) Assertion : For a binary solutiokn of two liquids, A and
(d) 80 mmoles of is in excess. B, with the knowledge of density of solution, molarity
can be converted into molality.
46. (M) The density of a solution of H2SO4 is 1.84 gm/ml and it
Reason : Molarity is defined in terms of volume and
contain 93% H2SO4 by volume. Then
molality in terms of mass, and mass and volume are related
(a) Molarity of H2SO4 is 10.42 by density.
(b) Mass of H2O = 91 gm (a) A (b) B

(c) C (d) D
(c) Mass of 100 gm solution = 184 gm
(d) None of the above
C-33
52. (I) 50 mL of 1 M HCl, 100 mL of 0.5 M HNO3, and x mL of 5 (d) 100 mL of 2.0 M HCl (s) [Ca2+] = 1.2 M
M H2SO4 are mixed together and the total volume is
made upto 1.0 L with water. 100 mL of this solution exactly +200 mL of 1.0 M NaOH [Na ] = 0.4 M
neutralises 10 mL of M/3 Al2(CO3)3. Calculate the value
of x. +150 mL of 4.0 M CaCl2 [Cl 4 ] = 2.8 M
53. (I) How many mL of a solution of concentration 100 mg
+50 mL of H2O
Co2+ per mL of a solution of concentration 20 mg Co2+
per mL. 58. (S) 100 mL of mixture of NaOH and Na2SO4 is neutralised
54. (I) A solution contains 75 mg NaCl per mL. To what extent by 10 mL of 0.5 M H2SO4. Hence, NaOH in 100 mL
must it be diluted to give a solution of concentration 15 solution is
mg NaCl per mL of solution.
(a) 0.2 g (b) 0.4 g
Strength : Stoichiometric Calculations
(c) 0.6 g (d) None
55. (S) How much NaNO3 must be weighed out to make 50 ml of
an aqueous solution containing 70 mg of Na+ per ml? 59. (S) BrO34 5Br 4 o Br2 3H2 O
(a) 12.394 g (b) 1.29 g
1f 50 mL 0.1 M BrO34 is mixed with 30 mL of 0.5 M Br 4
(c) 10.934 g (d) 12.934 g
solution that contains excess of H ions, the moles of
56. (S) 11.4 gm of a mixture of butene, C4H8 and butane C4H10,
was burned in excess oxygen. 35.2 gm of CO2 and 16.2 Br2 formed are
gm of H2O were obtained. Calculate the percentage by (a) 6.0 × 10–4 (b) 1.2 × 10–4
mass of butane in original mixture.
(a) 50.87% (b) 49.13% (c) 9.0 × 10–3 (d) 1.8 × 10–3
(c) 50% (d) None of these Molar Volume of Gas based Calculations
57. (X) Match the solution mixtures given in column I with the 60. (S) 1 g alloy of Cu and Zn reacted with excess of dil. H2SO4
concentrations given in column II.
to give H 2 gas which occupies 60 ml at STP. The
Column I Column II percentage of Zn in the alloy (Given only Zn reacts with
H2SO4)
(a) 11.1 g CaCl2 and 29.25g (p) [Ca2+] = 0.8 M
(a) 17% (b) 34%
of NaCl are diluted [Na ] = 1.2 M
(c) 83% (d) 40%
with water to 100 mL [Cl 4 ] = 2.8 M 61. (S) A solution of NaOH is prepared by dissolving 4.0 g of
NaOH in 1 L of water. Calculate the volume of the HCl
(b) 3.0 L of 4.0 M NaCl and (q) [Ca2+] = 0.001 M gas at STP that will neutralize 50 mL of this solution.
(a) 224 mL (b) 56 mL
4.0 L of 2.0 M CaCl2 are [Na ] = 0.005 M
(c) 112 mL (d) 448 mL
combined and diluted [Cl4 ] = 0.007 M 62. (M) 11.2 L of a gas at STP weighs 14 g. The gas could be :
to 10.0 L (a) N2 (b) CO
(c) 3.0 L of 3.0 M NaCl (r) [Ca2+] = 1.6 M (c) NO2 (d) N2O
is added to 200 mL of [Na ] = 1.8 M
4.0 M CaCl2 [Cl4 ] = 5.0 M
C-34
Empirical Formula Laws of Chemical Combination

63. (M) An oxide of nitrogen has 30.43% nitrogen (At. wt. of 69. (S) Two elements X and Y have atomic weights of 14 and 16.
N=14) and its one molecule weight 1.527 × 10–22 g. Which They form a series of compounds A, B, C D and E in
of the following statement regarding the oxide is (are) which for the same amount of element X, Y is present in
true ? the ratio 1 : 2 : 3 : 4 : 5. If the compound A has 28 parts by
weight of X and 16 parts by weight of Y, then the
(a) Its empirical formula is N2O
compound C will have 28 parts by weight of X and
(b) Its empirical formula is NO2. (a) 32 parts by weight of Y
(c) Its molecular formula is N2O4. (b) 48 parts by weight of Y
(d) Its molecular formula is N4O2. (c) 64 parts by weight of Y
Comprehension (d) 80 parts by weight of Y
A crystalline hydrated salt on being rendered anhydrous 70. (S) One part of an element A combines with two parts of B
loses 45.6% of its weight. (another element). Six parts of element C combine with
The percentage composition of anhydrous salt is : Al = four parts of element B. If A and C combine together, the
10.5%, K = 15.1 %, S = 24.8% and oxygen = 49.6% Answer ratio of their masses will be governed by :
the following four questions based on these information.
(a) law of definite proportions
[Molar masses are : Al = 27, K = 39, S = 32]
64. (C) What is the empirical formula of the salt ? (b) law of multiple proportions
(c) law of reciprocal proportions

(a) K 2 AlS2O7 (b) K 2 Al2S2O7
(d) law of conservation of mass
(c) KAlS2O8 (d) K 3AlS2O12
71. (S) Zinc sulphate contains 22.65% Zn and 43.9% H2O. If the
65. (C) What is the empirical formula of the hydrated salt ? law of constant proportions is true, then the mass of
(a) K 2 AlS2O7 .10H 2 O (b) K 2 Al2S2O7 .16H 2 O zinc required to give 40g crystals will be :
(a) 90.6 g (b) 9.06 g
(c) K 3AlS2O12 .8H 2O (d) KAlS2O8 .12H 2O
(c) 0.906 g (d) 906 g
66. (C) If 50 g of the above hydrated salt is dissolved in 150
gram of water, molality of the resulting solution will be 72. (S) 3 g of a hydrocarbon on combustion in excess of oxygen
produces 8.8g of CO2 and 5.4 g of H 2O. The data
(a) 0.7 (b) 0.6 illustrates the law of :
(c) 0.5 (d) 0.4 (a) conservation of mass(b) multiple proportions
3+
67. (S) The percentage of Fe in Fe in Fe0.93O1.00 is (c) constant proportions (d) reciporcal proportions
(a) 15.0% (b) 84.2% 73. (S) Potassium combines with two isotopes of chlorine
(35Cl and 37Cl) respectively to form two samples of KCl.
(c) 16.98% (d) 18.49 %
Their formation follows the law of :
68. (S) When a hydrate of Na2CO3 is heated until all the water is
(a) constant proportions (b) multiple proportions
removed, it loses 543 per cent of its mass. The formula of
the hydrate is (c) reciprocal proportions
(a) Na2CO3.10H2O (b) Na2CO3.7H2O (d) none of these.
(c) Na2CO3.5H2O (d) Na2CO3.3H2O
C-35
Principle of Atom Conservation 80. (A) Assertion : 1mole of H2SO4 is neutralised by 2 moles of
74. (S) 2.76 g of silver carbonate on being strongly heated yields NaOH but 1 equivalent of H2SO4 is neutralised by 1
a residue weighing equivalent of NaOH.
(a) 2.16 g (b) 2.48 g Reason : Equivalent weight of H2SO4 is half of its
(c) 2.32 g (d) 2.64 g molecular weight while equivalent weight of NaOH is 40.
75. (I) Igniting MnO2 in air converts it quantitatively to Mn3O4. (a) A (b) B
A sample of pyrolusite is of the following composition :
(c) C (d) D
MnO2 = 80%, SiO2 and other inert constituents = 15%,
and rest bearing H2O. The sample is ignited to constant 81. (A) Assertion : Equivalent volume of H2 is 11.2 L at 1 atm
weight. What is the percent of Mn in the ignited sample ? and 273 K.
76. (S) How many moles of ferric alum Reason : 1/2 mole H2 has produced when 1 mole of H+(aq)
accepted 1 mole of e–.
(NH 4 )2 SO 4 Fe 2 (SO 4 )3 . 24H 2O can be made from the
(a) A (b) B
sample of Fe containing 0.0056 g of it ?
(c) C (d) D
(a) 10–4 mol (b) 0.5 × 10–4 mol
82. (A) Assertion (A) : The equivalent mass of an element is
(c) 0.33 × 10–4 mol (d) 2 × 10–4 mol variable.
77. (I) A sample of a mixture of CaCl2 and NaCl weighing 4.22g Reason (R) : It depends on the valency of the element.
was treated to precipitate all the Ca as CaCO3, which (a) A (b) B
was then heated and quantitatively converted to 0.959g (c) C (d) D
of CaO. Calculate the percentage of CaCl2 in the mixture.
83. (S) N2 + 3H2 o 2NH3
(Ca = 40, O = 16, C = 12 and Cl = 35.5)
Molecular weight of NH 3 and N 2 are x 1 and x 2 ,
Equivalent Concept respectively. Their equivalent weights are y1 and y2,
respectively. Then (y1 – y2) is
78. (S) A metal oxide has the formula Z2O3. It can be reduced by
hydrogen to give free metal and water. 0.16 gm of the
§ 2x1 x 2 ·
metal oxide requires 6 mg of hydrogen for complete (a) ¨ ¸ (b) (x1 – x2)
reduction. The atomic weight of the metal is : © 6 ¹
(a) 27.9 (b) 159.6 (c) (3x1 – x2) (d) (x1 – 3x2)
(c) 79.8 (d) 55.8 84. (S) The vapour density of a chloride of an element is 39.5.
The Ew of the elements is 3.82. The atomic weight of the
79. (M) For the reaction element is
H3PO4 + Ca(OH)2 o CaHPO4 + 2 H2O (a) 15.28 (b) 7.64
1 mol 1 mol (c) 3.82 (d) 11.46

85. (M) Which of the following statements regarding the
Which are true statements?
compound AxBy is/are correct ?
(a) Equivalent weight of H3PO4 is 49
(a) 1 mole of AxBy contains 1 mole of A and 1 mole B
(b) Resulting mixture is neutralised by 1 mol of KOH
(b) 1 equivalent of AxBy contains 1 equivalent of A and
(c) CaHPO4 is an acidic salt 1 equivalent of B
(d) 1 mol of H3PO4 is completely neutralized by 1.5 mol (c) 1 mole of AxBy contains x moles of A and y moles of B
of Ca(OH)2 (d) equivalent weight of AxBy = equivalent weight of B
C-36
86. (M) Which of the statements are true ? 92. (X) Match the items given in column I with those in column
II.
(a) The equivalent weight of Ca3(PO4)2 is Mw/6.
Column I Column II
(b) The equivalent weight of Na3PO4. 12H2O is Mw/3. (a) 9.8% H2SO4 by weight (p) 3.6 N
–1
(c) The equivalent weight of K2SO4 is Mw/2. (density = 1.8g mL )
(d) The equivalent weight of potash alum (b) 9.8 % H3PO4 by weight (q) 1.2 M
K2SO4Al2(SO4)3. 24H2O is Mw/8. (density = 1.2g mL–1)
Normality (c) 1.8 NA molecules of (r) 1.8 Equivalents
87. (S) 10 mL of N/2 HCl, 20 mL of N/2 H2SO4 and 30 mL N/3 HCl is 500 mL
HNO 3 are mixed together and solution made to one (d) 250 mL of 4N NaOH (s) 1.10 m
litre. The normality of the resulting solution is + 250 mL of 1.6 M Ca(OH)2
(a) 0.20 N (b) 0.10 N 93. (S) 10 mL of 0.2 N HCl and 30 mL of 0.1 N HCl together
exactly neutralises 40 mL of solution of NaOH, which is
(c) 0.50 N (d) 0.025 N also exactly neutralised by a solution in water of 0.61 g
of an organic acid.What is the equivalent weight of the
88. (S) 0.115 g of pure sodium metal was dissolved in 500 ml organic acid ?
distilled water. The normality of the above solution,
(a) 61 (b) 91.5
whose resulting volume is 400 mL, would be
(c) 122 (d) 183
(a) 0.010 N (b) 0.0115 N
94. (M) 1 gm Mg sample is treated with 125 ml 0.1 N HCl and the
(c) 0.0125 N (d) 0.046 N excess of HCl is neutralised by 50 ml 0.5 N NaOH
completely. The correct statement is/are :
89. (S) 50 ml of 10 N H2SO4, 25 ml of 12 N HCl and 40 ml of 5N
(a) Mass of Mg present in the sample is 0.12 gm
HNO 3 were mixed together and the volume of the
(b) Mass of Mg sample unreacted is 0.88 gm
mixture was made 1000 ml by adding water. The
normality of the resulting solution will be (c) % of Mg present in the sample is 12%
(d) Mass of impurities present in the sample is 0.88 gm.
(a) 1 N (b) 2 N
95. (X) Match the Column
(c) 3 N (d) 4 N Column Column
–1
90. (S) Which of the following 1 g L solution has the highest (a) 20 ml (N) HCl reacts (p) No. of molecules of HCl
normality ? N
with 50 mL NaOH. left = 0
5
(a) NaOH (b) H2SO4
N
(c) HCl (d) HNO3 (b) 10 ml HCl reacts (q) No. of molecules of HCl
2
91. (A) Assertion :- 0.1 M H3PO3 (aq) solution has normality N
with 50 ml NaOH. left = 6.02 × 1021
equal to 0.3N when completely reacted with NaOH. 10
N
Reason : H3PO3 is dibasic acid. (c) 50 ml HCl reacts (r) No. of molecules of HCl
10
(a) A (b) B N
with 100 ml NaOH. left = 2.71 × 1022
(c) C (d) D 50
N
(d) 100 ml HCl reacts (s) No. of molecules of HCl
2
N
with 50 ml NaOH. left = 1.8 × 1021
10
C-37
96. (M) An aqueous solution of phosphoric acid (H3PO4) being

titrated has molarity equal to 0.25 M. Which of the
following could be normality of this solution ?
(a) 0.25 N (b) 0.50 N
(c) 0.75 N (d) 1.00 N
97. (M) An aqueous solution of 6.3g of a hydrated oxalic acid

(H2C2O4.xH2O) is made up to 250 mL. The 40 mL of 0.10
N NaOH was required to completely neutralize 10mL of
the above prepared stock solution. Which of the
following statements(s) about is (are) correct ?
(a) The acid is dehydrate.
(b) Equivalent weight of the hydrated acid is 45.
(c) Equivalent weight of the anhydrous acid is 45.
(d) 20 mL of the same stock would require 40 mL of 0.10
M Ca(OH)2 solution for complete neutralization.
C-38
ANSWER KEY
1. (c) 2. (a) 3. (c) 4. (A) o (R) (B) o (P, S), (C) o (Q), (D) o (P),(S) 5. (a)
6. (c) 7. (b) 8. (bc) 9. (ab) 10. (d) 11. (b) 12. (d) 13. (bc)
14. (a) 15. (d) 16. (c) 17. (c) 18. (b) 19. (c) 20. (0080) 21. (0059)
22. (0014) 23. (0060) 24. (a,b) 25. (0008) 26. (abd) 27. (ac) 28. (b) 29. (a)
30. (d) 31. (c) 32. (b) 33. (a) 34. (a,c,d) 35. (b) 36. (c) 37. (a)
38. (c) 39. (d) 40. (a,b) 41. (a) 42. (b) 43. (a) 44. (a) 45. (abcd)
46. (abc) 47. (abd) 48. (a,b,c,d) 49. (d) 50. (a) 51. (d) 52. (0010) 53. (0002)
54. (0005) 55. (d) 56. (a)
57. (a o q), (b o p), (c o r), (d o s) 58. (b) 59. (c) 60. (a) 61. (c) 62. (ab)
63. (bc) 64. (c) 65. (d) 66. (b) 67. (a) 68. (a) 69. (b) 70. (c)
71. (b) 72. (a) 73. (d) 74. (a) 75. 59.36% 76. (b) 77. 45.04% 78. (d)
79. (abcd) 80. (b) 81. (a) 82. (a) 83. (a) 84. (b) 85. (b,c,d) 86. (abcd)
87. (d) 88. (c) 89. (a) 90. (c) 91. (d)
92. (a – p, s; b – p, q, s; c – p, r; d – r) 93. (c) 94. (abcd ) 95. (a – q; b – q; c – s; d – r)

96. (abc) 97. (acd)
Dream on !!
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C-39
EXERCISE - 4: PREVIOUS YEAR IIT QUESTIONS
1. The oxidation of SO2 by O2 to SO3 is an exothermic 6. For the reversible reaction, N2(g) + 3H2(g) 2NH3(g)
reaction. The yield of SO3 will be maximum if (1981) at 500ºC, the value of Kp is 1.44 × 10–5 when partial pressure
(a) temperature is increased and pressure is kept constant is measured in atmospheres. The corresponding value of
Kc, with concentration in mole litre–1 is (2000)
(b) temperature is reduced and pressure is increased
(c) both temperature and pressure are increased 1.44 u 10 5 1.44 u10 5
(a) (b)
(d) both temperature and pressure are reduced (0.082 u 500) 2 (8.314 u 773) 2
2. For the reaction :
H2(g) + I2(g) 2HI (g) 1.44 u 10 5 1.44 u10 5
(c) (d)
(0.082 u 773) 2
(0.082 u 773) 2
The equilibrium constant Kp changes with (1981)
(a) total pressure (b) catalyst 7. When two reactants, A and B are mixed to give products C
(c) the amounts of H2 and I2 present and D, the reaction quotient Q, at the initial stages of the
reaction (2000)
(d) temperature
(a) is zero (b) decreases with time
3. Pure ammonia is placed in a vessel at a temperature where
its dissociation constant (D) is appreciable. At equilibrium (c) is independent of time (d) increases with time
N2 + 3H2 NH3 (1984) 8. At constant temperature, the equilibrium constant (Kp) for
the decomposition reaction N2O4 2NO2 is expressed
(a) Kp does not change significantly with pressure
by K = (4x2P) (1 – x2), where P = presssure, x = extent of
(b) D does not change with pressure decomposition. Which one of the following statements is
(c) concentration of NH3 does not change with pressure true ? (2001)
(d) concentration of hydrogen is less than that of nitrogen (a) Kp increases with increase of P
4. For the reaction ; (b) Kp increases with increase of x
CO (g) + H2O(g) CO2 (g) + H2 (g),
(c) Kp increases with decrease of x
at a given temperature, the equilibrium amount of CO2(g)
(d) Kp remains constant with change in P and x
can be increased by (1998)
(a) adding a suitable catalyst 9. Consider the following equilibrium in a closed container
(b) adding an inert gas N2O4 (g) 2 2NO2(g)

(c) decreasing the volume of the container At a fixed temperature, the volume of the reaction container
(d) increasing the amount of CO(g) is halved. For this change, which of the following
statements hold true regarding the equilibrium constant
5. For the chemical reaction
(Kp) and degree of dissociation (D) ?
3X (g) + Y (g) X3Y (g)
(a) Neither Kp nor D changes
the amount of X3Y at equilibrium is affected by (1999)
(b) Both Kp and D changes
(a) temperature and pressure
(b) temperature only (c) Kp changes but D does not change
(c) pressure only (d) Kp does not change but D changes

(d) temperature, pressure and catalyst
D-1
10. N2 + 3H3 2NH3 14. For the reaction, PCl5 (g) PCl3(g) + Cl2(g)
Which is correct statement if N2 is added at equilibrium The forward reaction at constant temperature is favoured
condition ? (2006) by (1991)
(a) The equilibrium will shift to forward direction because (a) introducing chlorine gas at constant volume
according to IInd law of thermodynamics the entropy (b) introducing an inert gas at constant pressure
must increase in the direction of spontaneous reaction
(c) increasing the volume of the container
(b) The condition for equilibrium is G N 2 3G H 2 2G NH3 (d) introducing PCl5 at constant volume
where G is Gibbs free energy per mole of the gaseous
Fill in the Blanks
species measured at that partial pressure. The
condition of equilibrium is unaffected by the use of 15. For a given reversible reaction at a fixed temperature,
catalyst, which increases the rate of both the forward equilibrium constant Kp and Kc are are related by ..............
and backward directions to the same extent
(1994)
(c) The catalyst will increase the rate of forward reaction
by E 16. A ten-fold increase in pressure on the reaction, N2(g) +
3H2 (g) 2NH3 (g) at equilibrium, results in ................
(d) Catalyst will not alter the rate of either of the reaction.
in Kp. (1996)
Objective Questions (One or more than one correct
option) 17. For a gaseous reaction 2B o A, the equilibrium
constant Kp is ........... to/than Kc.
11. For the gas phase reaction
True/False
C2H4 + H2 C2H6 ('H = – 32.7 kcal)
18. When a liquid and its vapour are at equilibrium and the
carried out in a vessel, the equilibrium concentration of
pressure is suddenly decreased, cooling occurs. (1984)
C2H4 can be increased by (1984)
(a) Increasing the temperature 19. If equilibrium constant for the reaction, A2 + B2
1
(b) decreasing the pressure 2AB, is K, then for the backward reaction AB
2
(c) removing some H2
1 1
(d) adding some C2H6 A 2 B2 , the equilibrium constant is . (1984)
2 K
12. When NaNO3 is heated in a closed vessel, oxygen is
20. Catalyst makes a reaction more exothermic. (1987)
liberated and NaNO2 is left behind. At equilibrium (1986)
21. The rate of an exothermic reaction increases with
(a) addition of NaNO2 favours reverse reaction increasing temperature. (1993)
(b) addition of NaNO3 favours forward reaction Subjective Questions
(c) increasing temperature favours forward reaction 22. One mole of nitrogen is mixed with three moles of
(d) increasing pressure favours reverse reaction hydrogen in a four litre container. If 0.25 per cent of nitrogen
is converted to ammonia by the following reaction
13. The equilibrium SO2Cl2(g) SO2 (g) + Cl2(g) is
attained at 25ºC in a closed container and an inert gas, N2(g) + 3H2 (g) 2NH3 (g), then
helium is introduced. Which of the following statements
are correct ? (1989) calculate the equilibrium constant, Kc in concentration
units. What will be the value of Kc for the following
(a) Concentration of SO2, Cl2 and SO2Cl2 change
equilibrium ?
(b) More chlorine is formed
1 3
(c) Concentration of SO2 is reduced N2 (g) + H 2 (g) NH3 (g) (1981)
2 2
(d) All the above are incorrect
D-2
23. One mole of Cl2 and 3 moles of PCl5 are placed in a 100 litre 29. 0.15 mole of CO taken in a 2.5 L flask is maintained at 750 K
vessel heated at 227ºC. The equilibrium pressure is 2.05 along with a catalyst so that the following reaction can
atmosphere. Assuming ideal behaviour, calculate the take place :
degree of dissociation for PCl5 and Kp for the reaction CO (g) + 2H2(g) CH3OH(g)
PCl5(g) PCl3 (g) + Cl2 (g) (1984)
Hydrogen is introduced until the total pressure of the
24. The equilibrium constant of the reaction system is 8.5 atm at equilibrium and 0.08 mole of methanol
A2(g) + B2(g) 2AB (g) at 100ºC is 50. If a one litre is formed. Calculate (i) Kp and Kc and (ii) the final pressure
flask containing one mole of A2 is connected to a two litre if the same amount of CO and H2 as before are used, but
flask containing two moles of B2, how many mole of AB with no catalyst so that the reaction does not take place.
will be formed at 373ºC ? (1985)
(1993)
25. At a certain temperature, equilibrium constant (Kc) is 16
30. The progress of reaction,
for the reaction ;
A nB
SO 2 (g) + NO 2 (g) SO3(g) + NO(g)
with time, is represented in fig. given below. Determine
If we take one mole of each of all the four gases in a one
litre container, what would be the equilibrium concentration
of NO and NO2 ? (1987)
26. N2O4 is 25% dissociated at 37ºC and one atmosphere

pressure. Calculate (i) K P and (ii) the percentage
dissociation at 0.1 atmosphere and 37ºC. (1988)
27. The equilibrium constant Kp of the reaction,
2SO2(g) + O2 (g) 2SO3 (g)
is 900 atm at 800 K. A mixture containing SO3 and O2 having (i) the value of n
initial pressure of 1 and 2 atm respectively is heated at (ii) the equilibrium constant, K and
constant volume to equilibrate. Calculate the partial
pressure of each gas at 800 K. (1989) (iii) the initial rate of conversion of A. (1994)
28. For the reaction 31. The degree of dissociation is 0.4 at 400 K and 1.0 atm for
the gaseous reaction PCl5 PCl3 + Cl2. Assuming
CO(g) + 2H2 (g) CH3OH(g) ideal behaviour of all the gases, calculate the density of
hydrogen gas is introduced into a five litre flask at 327ºC, equilibrium mixture at 400 K and 1.0 atm (relative atomic
containing 0.2 mole of CO(g) and a catalyst, until the mass of P = 31.0 and Cl = 35.5) (1998)
pressure is 4.92 atm. At this point 0.1 mole of CH3OH(g) is 32. When 3.06 g of solid NH4SH is introduced into a two litre
formed. Calculate the equilibrium constant, Kp and Kc. evacuated flask at 27ºC, 30% of the solid decomposes into
gaseous ammonia and hydrogen sulphide.
(1990)
(i) Calculate Kc and Kp for the reaction at 27ºC.
(ii) What would happen to the equilibrium when more solid

NH4SH is introduced into the flask ? (1999)
D-3
ANSWER KEY
Previous Year IIT Questions

1. (b) 2. (d) 3. (a) 4. (d) 5. (a) 6. (d) 7. (d) 8. (d) 9. (d) 10. (b)
11. (a,b,c,d) 12. (c,d) 13. (d) 14. (bcd) 15. Kp = Kc (RT)'n 16. no change 17. smaller
18. (T) 19. (F) 20. (F) 21. (F) 22. 0.468 L2 mol–2, 0.68 23. 0.33 24. 1.76 26. 0.266 atm; 63%
175 85
27. atm , atm 28. Kp = 0.11 atm–2 , Kc = 277.77 M–2 29. 220 30. (i) n = 2, (ii) 1.2 31. 4.54g/L
87 87
–5 –2
32. 8.1 × 10 , 4.84 × 10 , (ii) No effect
Dream on !!
[\]^[\]^
D-4
IONIC EQUILIBRIUM
1. The pH of 10–8 M solution of HCl in water is (1981) 8. An example of a reversible reaction is (1985)
(a) 8 (b) –8 (a) Pb(NO3)2 (aq) + 2NaI (aq) = PbI2 (s) + 2NaNO3 (aq)
(c) between 7 and 8 (d) between 6 and 7 (b) AgNO3 (aq) + HCl (aq) + AgCl (s) + HNO3 (aq)
+ –6 –1
2. At 90ºC, pure water has [H3O ] as 10 mol L . What is (c) 2Na (s) + 2H2O(l) = 2 NaOH (aq) + H2(g)
the value of Kw at 90ºC ? (1981)
(d) KNO3 (aq) + NaCl (aq) = KCl (aq) + NaNO3 (aq)
(a) 10–6 (b) 10–12 9. The best indicator for detection of end point in titration of
(c) 10 –14
(d) 10 –8 a weak acid and a strong base is (1985)
3. Of the given anions, the strongest base is (1981) (a) methyl orange (3 to 4) (b) methyl red (5 to 6)
(c) bromothymol blue (6 to 7.5)
(a) ClO– (b) ClO 2
(d) phenophthalein (8 to 9.6)

(c) ClO 3
(d) ClO 4
10. The compound that is not a Lewis acid is (1985)
4. An acidic buffer solution can be prepared by mixing the (a) BF3 (b) AlCl3
solution of (1981) (c) BeCl2 (d) SnCl4
(a) solution of acetate and acetic acid
11. The conjugate acid of NH 2 is (1985)
(b) ammonium chloride and ammonium hydroxide
(c) sulphuric acid and sodium sulphate (a) NH3 (b) NH2OH
(d) sodium chloride and sodium hydroxide (c) NH 4 (d) N2H4
–10
5. The precipitate of CaF2 (Ksp = 1.7 × 10 ) is obtained,
12. The pKa of acetyl salicylic acid (aspirin) is 3.5. The pH of
when equal volumes of the following are mixed (1982)
gastric juice in human stomach is about 2–3 and the pH in
(a) 10–4 M Ca2+ + 10–4 M F– the small intestine is about 8. Aspirin will be (1988)
(b) 10–2 M Ca2+ + 10–3 M F– (a) unionised in the small intestine and in the stomach
(c) 10–5 M Ca2+ + 10–3 M F– (b) completely ionised in the small intestine in the small
–3 2+ –5 – intestine
(d) 10 M Ca + 10 M F
(c) ionised in the stomach and almost unionised in the
6. A certain buffer solution contains equal concentration of
small intestine
X– and HX. The Kb for X– is 10–10. The pH of the buffer is
(d) ionised in the small intestine and almost unionised in
(1984) the stomach
(a) 4 (b) 7
13. When equal volumes of the following solutions are mixed,
(c) 10 (d) 14 precipitation of AgCl (Ksp = 1.8 × 10–10) will occur only
7. A certain weak acid has a dissociation constant of with (1988)
1.0 × 10–4. The equilibrium constant for its reaction with a
(a) 10–4 M (Ag+) and 10–4 M (Cl–)
strong base is (1984)
(b) 10–5 M (Ag+) and 10–5 M (Cl–)
(a) 1.0 × 10–4 (b) 1.0 × 10–10
(c) 1.0 × 1010 (d) 1.0 × 10–14 (c) 10–6 M (Ag+) and 10–6 M (Cl–)
(d) 10–10 M (Ag+) and 10–10 M (Cl–)
D-5
IONIC EQUILIBRIUM
14. Which of the following is the strongest acid ? (1989) 21. A solution which is 10–3 M each in Mn2+, Fe2+, Zn2+ and
Hg2+ is treated with 10–16 M sulphide ion. If Ksp of MnS,
(a) ClO3 (OH) (b) ClO2 (OH)
FeS, ZnS and HgS are 10 –15, 10 –23 , 10 –20 and 10 –54
(c) SO(OH)2 (d) SO2 (OH)2 respectively, which one will precipitate first ? (2003)
15. Amongst the following hydroxides, the one which has the (a) FeS (b) MgS
lowest value of Ksp at ordinary temperature (about 25ºC)
(c) HgS (d) ZnS
is (1990)
22. HX is a weak acid (Ka = 10–5). It forms a salt NaX (0.1 M) on
(a) Mg(OH)2 (b) Ca(OH)2
reacting with caustic soda. The degree of hydrolysis of
(c) Ba(OH)2 (d) Be(OH)2 NaX is (2004)
16. Which of the following solutions will have pH close to (a) 0.01% (b) 0.0001%
1.0 ? (1992)
(c) 0.1% (d) 0.5%
(a) 100 Ml of (M/10) HCl + 100 mL of (M/10) NaOH
23. The pH of 0.1 M solution of the following salts increases
(b) 55 mL of (M/10) HCl + 45 mL of (M/10) NaOH in the order (2004)
(c) 10 mL of (M/10) HCl + 90 mL of (M/10) NaOH (a) NaCl < NH4Cl < NaCN < HCl
(d) 75 mL of (M/5) HCl + 25 mL of (M/5) NaOH (b) HCl < NH4Cl < NaCl < NaCN
17. The solubility of A2X3 is y mol dm–3. Its solubility product (c) NaCN < NH4Cl < NaCl < HCl
is (1997)
(d) HCl < NaCl < NaCN < NH4Cl
4 4
(a) 6y (b) 64y
24. A weak acid HX has the dissociation constant 1 × 10–5M.
5 5 It forms a salt NaX on reaction with alkali. The precentage
(c) 36y (d) 108y
hydrolysis of 0.1 M solution of NaX ? (2004)
18. The pH of 0.1 M solution of the following salts increase in
the order (1999) (a) 0.0001% (b) 0.01%
(a) NaCl < NH4Cl < NaCN < HCl (c) 0.1% (d) 0.15%
(b) HCl < NH4Cl < NaCl < NaCN 25. A 0.004 M solution of Na2SO4 is isotonic with 0.010 M
solution of glucose at same temperature. The percentage
(c) NaCN < NH4Cl < NaCl < HCl
dissociation of Na2SO4 is (2004)
(d) HCl < NaCl < NaCN < NH4Cl
(a) 25% (b) 50%
19. For a sparingly soluble salt ApBq, the relationship of its (c) 75% (d) 85%
solubility product (Ls) with its solubility (S) is (2001)
26. CH3NH2 (0.1 mole, Kb = 5 × 10–4) is added to 0.08 moles of
p+q p q p+q q p
(a) Ls = S . p .q (b) Ls = S . p .q HCl and the solution is diluted to one litre, resulting
hydrogen ion concentration is (2005)
(c) Ls = Spq . pp.qq (d) Ls = Spq. (p.q)(p+q)
(a) 1.6 × 10–11 (b) 8 × 10–11
20. Identify the correct order of solubility of Na2S, CuS and
ZnS in aqueous medium (2002) (c) 5 × 10–5 (d) 8 × 10–2
(a) CuS > ZnS > Na2S (b) ZnS > Na2S > CuS
(c) Na2S > CuS > ZnS (d) Na2S > ZnS > CuS
D-6
IONIC EQUILIBRIUM
27. Ag+ + NH3 [Ag(NH3)]+ ; k1 = 3.5 × 10–3 2

31. 2.5 mL of M weak monoacidic base (Kb = 1 × 10–12 at
5
[Ag(NH3)]+ + NH3 [Ag (NH3)2]+ ;
2
k2 = 1.7 × 10–3 25ºC) is titrated with M HCl in water at 25ºC. The
15
concentration of H+ at equivalence point is (Kw = 1 × 10–14
then the formation constant of [Ag(NH3)2]+ is (2006)
at 25ºC) (2008)
(a) 6.08 × 10–6 (b) 6.08 × 106 (a) 3.7 × 10–13 M (b) 3.2 × 10–7 M
(c) 6.08 × 10–9 (d) None of these (c) 3.2 × 10–2 M (d) 2.7 × 10–2 M
Objective Questions (One or more than one
28. The species present in solution when CO2 is dissolved in
water are (2006) correct option)
32. Which of the following statement (s) is (are) correct ?
2
(a) CO2, H2CO3, HCO , CO 3 3 (1998)
–8
(a) The pH of 1.0 × 10 M solution of HCl is 8
(b) H 2CO3 , CO32
(b) The conjugate base of H 2 PO 4 is HPO 24
(c) HCO3 , CO32 (d) CO 2 , H 2CO3 (c) Autoprotolysis constant of water increases with
temperature
29. N2 + 3H3 2NH3 (d) When a solution of a weak monoprotic acid is titrated
against a strong base, at half-neutralisation point pH =
Which is correct statement if N2 is added at equilibrium
condition ? (2006) §1·
¨ ¸ pK a
©2¹
(a) The equilibrium will shift to forward direction because
according to IInd law of thermodynamics the entropy 33. A buffer solution can be prepared from a mixture of
must increase in the direction of spontaneous reaction (1999)
(a) sodium acetate and acetic acid in water
(b) The condition for equilibrium is G N 2 3G H 2 2G NH3
(b) sodium acetate and HCl in water
where G is Gibbs free energy per mole of the gaseous
species measured at that partial pressure. The (c) ammonia and ammonium chloride in water
condition of equilibrium is unaffected by the use of (d) ammonia and sodium hydroxide in water
catalyst, which increases the rate of both the forward
and backward directions to the same extent
Fill in the Blanks
(c) The catalyst will increase the rate of forward reaction 34. The conjugate base of HSO4 in aqueous solution is
by E ................. (1982)
(d) Catalyst will not alter the rate of either of the reaction. 35. An element which can exist as a positive ion in acidic
solution and also as a negative ion in basic solution is
30. Solubility product constant (Ksp) of salts of types MX, said to be ............... (1984)
MX2 and M3X at temperature ‘T’ are 4.0 × 10–8, 3.2 × 10–14 36. Silver chloride is sparingly soluble in water because its
and 2.7 × 10–15, respectively. Solubilities (mol, dm–3) of the lattice energy is greater than ................ energy. (1987)
salts at temperature ‘T’ are in the order (2008)
37. In the reaction I– + I2
o I3 , the Lewis acid is ............
(a) MX > MX2 > M3X (b) M3X > MX2 > MX
(1997)
(c) MX2 > M3X > MX (d) MX > M3X > MX2
38. (CH3OH2)+ is ............... acidic than ( CH3 NH3 ). (1997)
D-7
IONIC EQUILIBRIUM
True/False is solution ? The dissociation constant of formic acid is

2.4 × 10–4 and the degree of dissociation of sodium formate
39. Aluminium chloride (AlCl3) is a Lewis acid because it can
is 0.75. (1985)
donate electrons. (1982)
40. Solubility of sodium hydroxide increases with increase in 48. The solubility of Mg(OH)2 in pure water is 9.57 × 10–3 g/litre.
temperature. (1985) Calculate its solubility (in g/litre) in 0.02 M Mg(NO3)2
solution. (1986)
41. The following species are in increasing order of their acidic
property : ZnO, Na2O2, P2O5, MgO (1985) 49. What is the pH of the solution when 0.2 mole of
hydrochloric acid is added to one litre of a solution
Subjective Questions containing
42. How many moles of sodium propionate should be added (i) 1 M each of acetic acid and acetate ion ?
to 1 L of an aqueous solution containing 0.020 moles of
propionic acid to obtain a buffer solution of pH 4.75 ? (ii) 0.1 M each of acetic acid and acetate ion ?
What will be pH if 0.010 moles of HCl are dissolved in the Assume the total volume is one litre. Ka for acetic acid
above buffer solution ? Compare the last pH value with
= 1.8 × 10–5. (1987)
the pH of 0.010 M HCl solution. Dissociation constant of
propionic acid, Ka at 25ºC is 1.34 × 10–5. (1981) 50. Freshly precipitated aluminium and magnesium hydroxides
are stirred vigorously in a buffer solution containing 0.25
43. 20 mL of 0.2 M sodium hydroxide is added to 50 mL mol/L of NH4Cl and 0.05 M of ammonium hydroxide
of 0.2 M acetic acid solution to give 70 mL of the calculate the concentration of alminimum and magnesium
solution. What is the pH of this solution ? Calculate ions in solution
the additional volume of 0.2 M NaOH required to make –5
the pH of the solution 4.74. (Ionisation constant of Kb[NH4OH] = 1.8 × 10
–12
CH3COOH = 1.8 × 10–5). (1982) Ksp[Mg(OH)2] = 8.9 × 10
–32
44. Give reason for the statement that “the pH of an aqueous Ksp[Al(OH)3] = 6 × 10 (1989)
solution of sodium acetate is more than seven”. (1982) 51. What is the pH of 1.0 M solution of acetic acid ? To what
45. The dissociation constant of a weak acid HA is 4.9 × 10–8. volume must one litre of this solution be diluted so that
the pH of the resulting solution will be twice the original
After making the necessary approximations, calculate : value ?
(i) pH Given : Ka = 1.8 × 10–5. (1990)

–11
(ii) OH– concentration in a decimolar solution of the acid. 52. The solubility product of Ag2C2O4 at 25ºC is 1.29 × 10
3 –3
Water has a pH of 7. (1983) mol L . A solution of K2C2O4 containing 0.1520 mole in
500 mL water is shaken at 25ºC with excess of Ag2CO3 till
46. A solution contains a mixture of Ag+ (0.10 M) and Hg2+
the following equilibrium is reached
(0.10 M) which are to be separated by selective
precipitation. Calculate the maximum concentration of Ag2CO3 + K2C2O4 Ag2C2O4 + K2CO3
iodide ion an which one of them gets precipitated almost At equilibrium, the solution contains 0.0358 mole of K2CO3.
completely. What percentage of that metal ion is
Assuming the degree of dissociation of K2C2O4 and
precipitated ? (1984)
K2CO3 to be equal, calculate the solubility product of
Ksp : AgI = 8.5 × 10–17, HgI2 = 2.5 × 10–26 Ag2CO3. (1991)
47. The concentration of hydrogen ions in a 0.20 M solution 53. A 40 mL solution of a weak base, BOH is titrated with 0.1N
HCl solution. The pH of the solution is found to be 10.04
of formic acid is 6.4 × 10–3 mol/L. To this solution, sodium
and 9.14 after the addition of 5.0 mL and 20.0 mL of the
formate is added so as to adjust the concentration of
acid respectively. Find out the dissociation constant of
sodium formate to one mole per litre. What will be the pH
the base. (1991)
of this solution ? The dissociation constant of formic acid
D-8
IONIC EQUILIBRIUM
54. The solubility product (Ksp) of Ca(OH) 2 at 25ºC is 60. What is the pH of a 0.50 M aqueous NaCN solution ?
–5
4.42 × 10 . A 500 mL of saturated solution of Ca(OH)2 is
(pKb of CN– = 4.70) (1996)
mixed with equal volume of 0.4 M NaOH. How much
Ca(OH)2 in milligrams is precipitated ? (1992)
61. The ionisation constant of NH 4 in water is 5.6 × 10–10 at
55. The pH of blood stream is maintained by a proper balance
25ºC. The rate constant for the reaction of NH 4 and OH–
of H2CO3 and NaHCO3 concentrations. What volume of
5 M NaHCO3 solution should be mixed with a 10 mL sample to form NH3 and H2O at 25ºC is 3.4 × 1010 L/mol/s. Calculate
of blood which in 2 M in H2CO3, in order to maintain a pH the rate constant per proton transfer from wate to NH3.
of 7.4 ? (Ka for H2CO3 in blood is 7.8 × 10–7) (1993)
(1996)
56. An aqueous solution of a metal bromide MBr2 (0.05 M) is
62. A sample of AgCl was treated with 5.00 mL of 1.5 M Na2CO3
saturated with H2S. What is the minimum pH at which MS
solution to give Ag2CO3. The remaining solution contained
will precipitate ?
0.0026 g of Cl– ions per litre. Calculate the solubility product
Ksp for MS = 6.0 × 10–21, conc. of saturated H2S = 0.1 M of AgCl. (1997)
and K1 = 10–7 and K2 = 1.3 × 10–13, for H2S. (1993)
[Ksp (Ag2CO3) = 8.2 × 10–12]
57. For the reaction,
63. An acid type indicator, HIn differs in colour from its
[Ag(CN)2]– Ag+ + 2CN– conjugate base (In–). The human eye is sensitive to colour
differences only when the ratio [In–]/[HIn] is greater than
The equilibrium constant, at 25ºC, is 4.0 × 10–19. Calculate
10 or smaller than 0.1. What should be the minimum change
the silver ion concentration in a solution which was
in the pH of the solution to observe a complete colour
originally 0.10 M in KCN and 0.03 M in AgNO3. (1994)
change ? (Ka = 1.0 × 10–5) (1997)
58. The progress of reaction,
64. The solubility of Pb(OH)2 in water is 6.7 × 10–6M. Calculate
A nB
the solubility of Pb(OH)2 in a buffer solution of pH = 8.
with time, is represented in fig. given below. Determine
(1999)
65. The average concentration of SO2 in the atmosphere over

a city on a certain day is 10 ppm, when the average
temperature is 298 K. Given that the solubility of SO2 in
water at 298 K is 1.36653 mol/L and pKa of H2SO3 is 1.92,
estimate the pH of rain on that day. (2000)
66. 500 mL of 0.2 M aqueous solution of acetic acid is mixed

with 500 mL of 0.2 M HCl at 25ºC.
(i) the value of n (i) Calculate the degree of dissociation of acetic acid in
the resulting solution and pH of the solution.
(ii) the equilibrium constant, K and
(iii) the initial rate of conversion of A. (1994) (ii) If 6 g of NaOH is added to the above solution,
determine the final pH. [Assume there is no change in
59. Calculate the pH of an aqueous solution of 1.0 M volume on mixing : Ka of acetic acid is 1.75 × 10–5 mol L–1.]
ammonium formate assuming complete dissciation
(2002)
(pKa of formic acid = 3.8 and pKb of ammonia = 4.8)
(1995)
D-9
IONIC EQUILIBRIUM
67. (a) In the following equilibrium

N2O4 (g) 2NO2 (g)
when 5 moles of each are taken, the temperature is
kept at 298 K the total pressure was found to be 20 bar.
Given that
'G of (N 2 O4 ) 100kJ
'G of (NO2 ) 50kJ
(i) Fina 'G of the reaction

(ii) The direction of the reaction in which the equilibrium
shifts
(b) A graph is plotted for a real gas which follows van der
Waals’ equation with pVm taken on Y-axis and p on
X-axis. Find the intercept of the line where Vm is molar
volume. (2004)
68. 0.1 M of HA is titrated with 0.1 M NaOH, calculate the pH

–6
at end point, Given, Ka (HA) = 5 × 10 and D < < 1. (2004)
69. The dissociation constant of a substituted benzoic acid at
–4
25ºC is 1.0 × 10 . The pH of 0.01 M solution of its sodium
salt is (2009)
D-10
IONIC EQUILIBRIUM
Answer Key
1. (d) 2. (b) 3. (a) 4. (a) 5. (b) 6. (a) 7. (c) 8. (d) 9. (d) 10. (c)
11. (a) 12. (d) 13. (a) 14. (a) 15. (d) 16. (d) 17. (d) 18. (b) 19. (a) 20. (d)
21. (c) 22. (a) 23. (b) 24. (b) 25. (c) 26. (b) 27. (a) 28. (a) 29. (b) 30. (d)
31. (d) 32. (bc) 33. (abc) 34. SO2 35. amphoteric 36. hydration 37. I2 38. more
39. (F) 40. (F) 41. (F) 45. (i) 4.15, (ii) 1.43 × 10–10m 46. 5 × 10–13M, 99.83 47. 4.20
–4 –15 4
48. 8.7 × 10 g/lit 49. 4.5686 ; 1 50. 1.28 × 10 m, 0.68 M 51. 2.3724 ; 2.78 × 10 lit.
–11 –5 –18 +
52. 9.675 × 10 53. Kb = 1.8 × 10 54. 747.4 mg 55. 80mL 56. 1 57. 7.50 × 10 M Ag
5 –8
58. (i) n = 2, (ii) 1.2 59. 6.50 60. 11.5 61. 6.12 × 10 62. 2 × 10 64. 1.2 × 10–3 M
–4
65. 4.86 66. (i) 1.75 × 10 (ii) 4.75 67. (a) (i) O, (ii) Forward direction 68. (9)
69. (8)
Dream on !!
[\]^[\]^
D-11
1. Dissolving 120g of urea (mol. wt. 60) in 1000g of water 6. 6.3g of oxalic acid dihydrate have been dissolved in
gave a solution of density 1.15 g/mL. The molarity of water to obtain a 250 mL solution. How much volume of
0.1 N NaOH would be required to neutralise 10 mL of
the solution is (2011)
this solutions ? (2001)
(a) 1.78 M (b) 2.00 M
(a) 40 mL (b) 20 mL
(c) 2.05 M (d) 2.22 M (c) 10 mL (d) 4 mL
2. Given that the abundances of isotopes 54

Fe, 56
Fe and 7. The normality of 0.3 M phosphorous acid (H3PO3) is
57
Fe are 5%, 90% and 5%, respectively, the atomic mass (1999)
of Fe is (2009)
(a) 0.1 (b) 0.9
(a) 55.85 (b) 55.95
(c) 0.3 (d) 0.6
(c) 55.75 (d) 56.05
8. The weight of 1 × 1022 molecules of CuSO4. 5H2O is
3. Mixture X = 0.02 mole of [Co(NH3)5SO4] Br and 0.02
mole of [Co(NH3)5Br] SO4 was prepared in 2 L solution. (1991)
(a) 41.59 g (b) 415.9g

1 L of mixture X + excess of AgNO 3 solution o Y
(c) 4.159 g (d) none of the three
1 L of mixture X + excess of BaCl2 solution o Z
9. The sulphate of a metal M contains 9.87% of M. This
Number of moles of Y and Z are (2003) sulphate is isomorphous with ZnSO4.7H2O. The atomic
weight of M is (1991)
(a) 0.01, 0.01 (b) 0.02, 0.01
(a) 40.3 (b) 36.3
(c) 0.01, 0.02 (d) 0.02, 0.02
(c) 24.3 (d) 11.3
4. Which has maximum number of atoms ? (2003)
10. If 0.5 mol of BaCl2 is mixed with 0.2 mol of Na3PO4, the
(a) 24g of C (12) (b) 56g of Fe (56)
maximum number of moles of Ba3 (PO4)2 that can be formed
(c) 27g of Al (27) (d) 108g of Ag (108) is (1981)
5. How many moles of electron weighs one kilogram ? (a) 0.7 (b) 0.5
(c) 0.30 (d) 0.10

1
(a) 6.023 × 10 23
(b) u 1031
9.108 11. The total number of electrons present in 18 ml of water
(density of water is 1 g ml–1) is (1980)
6.023 1 (a) 6.02 × 1023 (b) 6.02 × 1023

(c) u 1054 (d) u 108
9.108 9.108 u 6.023
(c) 6.02 × 1024 (d) 6.02 × 1025
D-12
12. 29.2% (w/W) HCl stock solution has density of

1.25 g mL–1. The molecular weight of HCl is 36.5g mol–1.
The volume (mL) of stock solution required to prepare
a 200 mL solution 0.4 M HCl is (2013)
13. 20% surface sites have adsorbed N2. On heating N 2

gas evolved from sites and were collected at 0.001 atm
and 298 K in a container of volume is 2.46 cm3. Density
of surface sites is 6.023 × 1014/cm2 and surface area is
1000 cm2, find out the number of surface sites occupied
per molecule of N2. (2005)
14. In a solution of 100 mL 0.5 M acetic acid, one gram of

active charcoal is added, which adsorbs acetic acid. It
is found that the concentration of acetic acid becomes
0.49 M. If surface area of charcoal is 3.01 × 10 2m2,
calculate the area occupied by single acetic acid
molecule on surface of charcoal. (2003)
15. Calculate the molarity of water if its density is
1000 kg/m3. (2003)
16. 3 g of a salt of molecular weight 30 is dissolved in 250

g of water. The molality of the solution is : ..........
(1983)
17. The weight of 1×1022 molecules of CuSO4 5H 2O is :

....... (1991)
18. A sugar syrup of weight 214.2 g contains 34.2 g of

sugar (C 12H22O11). Calculate : (i) molal concentration
and (ii) mole fraction of sugar in the syrup. (1988)
D-13
ANSWER KEY
1. (c) 2. (b) 3. (a) 4. (a) 5. (d) 6. (a) 7. (d) 8. (c)
9. (c) 10. (d) 11. (c) 12. (8) 13. (2) 14. 5 × 10–19 m2 15. 55.55M
16. 0.4m 17. 4.14g 18. (i) 0.56, (ii) 0.0099
Dream on !!
[\]^[\]^
D-14

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JEE-11-Chemistry-Physical Chemistry 3 PDF

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CONTENTS

PHYSICAL CHEMISTRY-3 Pages

 Chemical Equilibrium – Theory 1 – 11

1. INTRODUCTION 2.3 Concept of Chemical Equilibrium

Equilibrium represents the state of a process in which the

If the opposing processes involve only physical changes,

2. EQUILIBRIA IN CHEMICAL PROCESSES

3.2 Overall rate of a reaction

4. EQUILIBRIUM CONSTANT (K)

2.4 Characteristics of Chemical Equilibrium

(iii) A chemical equlibrium can be established only if none of aA + bB + cC + ...... 

The product of the molar concentrations of the products,

the value of x in the equilibrium concentration expression

8.5 Effect of a Catalyst

8.4 Effect of change in volume

(ii) CH3COOH  C2 H5OH CH3COOC2 H5  H2O

Sol. Suppose at equilibrium, I2 = Cl2 =xmolL-1 . Then Molar

2ICl I 2 (g) + Cl 2 (g) concs 8.29/V 0.009/V 0.171/V 0.171/V

Initial conc. 0.78M 0 0 CH 3 COOC 2 H 5 H 2 O 0.171/ V 0.171/ V

After time t 1–0.214 0.500–0.214 0.214 mol 0.214 mol

or x 0.292  0.748 x or 1.748 x 0.292 or x 0.167

I 2 = Cl2 =0.167M, ICI =0.78-2×0.167M=0.446M

CH 3 COOC2 H5 H 2 O x 4.15 u104 2.04 u102 M 0.02M

CO(g)  H 2 O(g) CO2(g) + H2 (g)

1 (pH2 )eq = 0.96 bar

or [O3]2 = (2.0 × 10–50) (1.6×10–2)3 = 8.192×10–56 or Example - 15

2AB 2 2AB(g) + B 2 (g) 2C(s)  O 2 (g) 2CO(g)

At equilibrium 1 – x 2x x The degree of dissociation is 0.4 at 400 K and 1.0 atm

Step 2. To calculate extra CO2 to be added

Sol. N 2 O 4 (g) 2NO2(g)

Sol. α-D glucose E - D glucose

? No. of moles of NO2 at equilibrium = 2x=2×0.018= 0.036

At 77ºC and one atmoshpheric pressure, N2O4 is 70%

Sol. Molar mass of N 2 O4 28  64 92g mol 1

The definition of acids and bases varies from theory to

[H+] = cD = cK a = [A–] 6. BUFFER SOLUTIONS

H2O lH+ + OH–

pH > 7 Basic For any polyprotic acid : K1 > K2 > K3 ....so on

pH = 7 Neutral For dissociation of H2A [A2–] | K

8. SALT HYDROLYSIS 9. SPARINGLY SOLUBLE SALTS & PRECIPITATION

8.3 Salt of Strong acid and weak base (NH4Cl)

This type of salt give basic solution on hydrolysis.

8.4 Salt of weak acid and weak base (CH3COONH4)

This type of salt may give acidic,basic or neutral solution.

Calculate the pH of the following solutions: ? M2 = 1.36 × 10–2 M

2g 1 Sol. CH 2 (Br)COOH CH 2 (Br)COO   H 

= 4.52 ×10–3 M Conc at eqm C – CD CD CD

? ª¬ OH  º¼ TlOH 4.52 u10 3 M CD.CD CD2

ª¬ H  ¼º 1014 /(4.52 u 10 3 ) 2.21u 10 12 M

= 16.22×10–3 M Sol. Cod  H 2 O CodH   OH

pOH  log(16.22 u 103 ) 3  1.2101 1.79 pH 9.95 ? pOH 14  9.95 4.05i.e.

0.3g 1 ª¬ OH  ¼º 8.913 u 105 M

pOH  log(3.75 u10 2 ) 2  0.0574 1.43 = 1.588 × 10–6

(d) log[H  ] pH 6.4 7.60 Example - 8

Example - 12 or pH pK a  log(1  D )  log D

For weak monobasic acid HA H+ + A– Example - 14

CO 2  H 2 O H 2 CO3 (weakly acidic)

SO 3  H 2 O H 2SO 4 (Strongly acidic) Example - 18

Sol. The reaction between BF3 and C2H5OC2H5 is

from one H2O molecule).

 Sol (i) H2O (ii) OH–

K1 or ª¬ H  º¼ K1[H 2S] Also Kw = [H+] [ OH–] .....(iii)

Sol. At the equivalence point, CH3COONa is formed and its Sol. (C 2 H 5 ) 2 NH  H 2 O (C 2 H 5 ) 2 NH 2  OH 

(iii) A chemical equlibrium can be established only if none of aA + bB + cC + ......

(ii) CH3COOH C2 H5OH CH3COOC2 H5 H2O

or x 0.292 0.748 x or 1.748 x 0.292 or x 0.167

CH 3 COOC2 H5 H 2 O x 4.15 u104 2.04 u102 M 0.02M

CO(g) H 2 O(g) CO2(g) + H2 (g)

2AB 2 2AB(g) + B 2 (g) 2C(s) O 2 (g) 2CO(g)

Sol. Molar mass of N 2 O4 28 64 92g mol 1

2g 1 Sol. CH 2 (Br)COOH CH 2 (Br)COO H

? ª¬ OH º¼ TlOH 4.52 u10 3 M CD.CD CD2

ª¬ H ¼º 1014 /(4.52 u 10 3 ) 2.21u 10 12 M

= 16.22×10–3 M Sol. Cod H 2 O CodH OH

pOH log(16.22 u 103 ) 3 1.2101 1.79 pH 9.95 ? pOH 14 9.95 4.05i.e.

0.3g 1 ª¬ OH ¼º 8.913 u 105 M

pOH log(3.75 u10 2 ) 2 0.0574 1.43 = 1.588 × 10–6

(d) log[H ] pH 6.4 7.60 Example - 8

Example - 12 or pH pK a log(1 D ) log D

CO 2 H 2 O H 2 CO3 (weakly acidic)

SO 3 H 2 O H 2SO 4 (Strongly acidic) Example - 18

Sol (i) H2O (ii) OH–

K1 or ª¬ H º¼ K1[H 2S] Also Kw = [H+] [ OH–] .....(iii)

Sol. At the equivalence point, CH3COONa is formed and its Sol. (C 2 H 5 ) 2 NH H 2 O (C 2 H 5 ) 2 NH 2 OH

0.1 As pH = 12, ? [H ] 1012 M or [OH – ] = 10 –2 M,

NH3 + H2O NH 4 OH , k 3.4 u 1010 102

10 14 Initial moles 1 mole 1 mole 0 0

pH = 12 means [H+]= 10–12or [OH–]= 10–2 M After dissociation C CD CD CD

[Salt] [Acid] 1mol L1 ] Example - 33

As pH = 9.35, ?pOH 14 9.35 4.65

5 0.4771 4.5229 ? Mass of (NH4)2SO4 to be added = (62.95 × 10–3 moles)

Example - 15 C (s) O2 (g)

Example - 19 12x 13 (100 x)

Gram atomic mass To find :