CBSE Class 11 Chemistry-Equilibrium

7.
Equilibrium(Part-I)
Some Important Points and Terms of the Chapter
1. Equilibrium represents the state of a process in which the properties like

temperature, pressure etc do not show any change with the passage of time
2. Chemical equilibrium: When the rates of the forward and reverse reactions
become equal, the concentrations of the reactants and the products remain
constant. This is the stage of chemical equilibrium. This equilibrium is dynamic in
nature as it consists of a forward reaction in which the reactants give product(s)
and reverse reaction in which product(s) gives the original reactants. Equilibrium
is possible only in a closed system at a given temperature. A mixture of reactants
and products in the equilibrium state is called an equilibrium mixture.
3. In a Homogeneous system, all the reactants and products are in the same phase.
For example, in the gaseous reaction, N2 (g) + 3H2(g) 2NH3(g), reactants and
products are in the homogeneous phase.
4. Equilibrium in a system having more than one phase is called heterogeneous
equilibrium. The equilibrium between water vapor and liquid water in a closed
container is an example of heterogeneous equilibrium. H2O(l) H2O(g)
KENDRIYA VIDYALAYA SANGATHAN
Zonal Institute Of Education And Training; Bhubaneswar
Study Material- Chemistry- Class XI
5. Henry Law:-It states that the mass of a gas dissolved in a given mass of a solvent
at any temperature is proportional to the pressure of the gas above the solvent
6. Law of Chemical Equilibrium: It may be stated as, at a given temperature the
ratio of product of equilibrium concentration of the products to that of the reactants
with each concentration terms raised to power equal to the respective
stoichiometric coefficient in the balanced chemical reaction has a constant value.
This constant value is known as Equilibrium constant. For a general reaction of the
type aA + bB  cC + dD
Kc = [C]c[D]d /[A]a [B]b This expression is known as Law Of Chemical
Equilibrium
7. Relationship between Kp and Kc: Kp = Kc(RT)  n
8. Units of Equilibrium Constant: The value of equilibrium constant Kc can be
calculated by substituting the concentration terms in mol/L and for Kp partial
pressure is substituted in Pa, kPa, bar or atm. This results in units of equilibrium
constant based on molarity or pressure, unless the exponents of both the numerator
and denominator are same. For the reactions (i)H2(g) + I2(g) 2HI, Kc
and Kp have no unit.(ii)N2O4(g)  2NO2 (g), Kc has unit mol/L and Kp has unit
bar
9. Characteristics Of Equilibrium Constant
 Equilibrium constant is applicable only when concentrations of the reactants
and products have attained their equilibrium state.
 The value of equilibrium constant is independent of initial concentrations of
the reactants and products.
 Equilibrium constant is temperature dependent having one unique value for
aparticular reaction represented by a balanced equation at a given temperature.
 The equilibrium constant for the reverse reaction is equal to the inverse of the
equilibrium constant for the forward reaction.
 The equilibrium constant K for a reaction is related to the equilibrium constant
of the corresponding reaction, whose equation is obtained by multiplying or
dividing the equation for the original reaction by a small integer.
10. Applications of equilibrium constant :
 Predict the extent of a reaction on the basis of its magnitude.
 Predict the direction of the reaction, and
 Calculate equilibrium concentrations.
11. Le Chatelier’s Principle: It states that if a system in equilibrium is subjected to a
change of concentration, temperature or pressure, the equilibrium shifts in a
direction that tends to undo the effect of the change imposed.
 Effect of change of concentration: When the concentration of any of the
reactants or products in a reaction at equilibrium is changed, the composition of
the equilibrium mixture changes so as to minimize the effect of concentration
change. For eg:- H2(g) + I2(g)  2HI(g)
If H2 is added to the reaction mixture at equilibrium, the equilibrium of the
reaction is disturbed. In order to restore it, the reaction proceeds in a direction
whereas H2 is consumed i.e more of H2 and I2 react to form HI and finally the
equilibrium shifts in forward direction.
 Effect of change of pressure: When the pressure is increased the equilibrium
shifts in the direction in which the number of moles of the gas decreases.
Consider the reaction, CO (g) + 3H2 (g)  CH4 (g) + H2O (g) Here, 4 mol of
gaseous reactants (CO + 3H2) become 2 mol of gaseous products (CH4 (g) + H2O).
so by Le Chatelier‘s principle. The increase in pressure will shift the equilibrium
in the forward direction, a direction in which the number of moles of the gas or
pressure decreases.
 Effect of change of Temperature: When a change in temperature occurs, the
value of equilibrium constant changes. In general, the temperature dependence of
the equilibrium constant depends on the sign of ΔH for the reaction. The
equilibrium constant for an exothermic reaction (-ve ΔH) decreases as the
temperature increases. The equilibrium constant for an endothermic reaction (+ve
ΔH) increases as the temperature increases. When the Temperature is increased the
equilibrium shifts in the direction in of endothermic reaction.
Consider a reaction N2(g) + 3H2(g)  2NH3(g) ΔH = -92.38Kj/mol
According to Le Chatelier‘s principle, raising the temperature shifts the equilibrium
to left (backward direction i.e direction of endothermic reaction) and decreases the
equilibrium concentration of ammonia.

 Effect of Inert Gas Addition: If the volume is kept constant and an inert gas such
as argon is added which does not take part in the reaction, the equilibrium remains
undisturbed. It is because the addition of an inert gas at constant volume does not
change the partial pressures or the molar concentrations of the substance involved
in the reaction. The reaction quotient changes only if the added gas is a reactant or
product involved in the reaction.
 Effect of a Catalyst: A catalyst increases the rate of the chemical reaction by
making available a new low energy pathway for the conversion of reactants to
products. It increases the rate of forward and reverse reactions that pass through
the same transition state and does not affect equilibrium. Catalyst lowers the
activation energy for the forward and reverse reactions by exactly the same
amount. Catalyst does not affect the equilibrium composition of a reaction
mixture. It does not appear in the balanced chemical equation or in the equilibrium
constant expression.
Summary of Le Chatelier’s Principle
Type of Effect or Change Direction of Equilibrium

Addition of more reactants Forward direction
Addition of more products Backward direction
Increase in temperature Towards endothermic reaction

Decrease in temperature Towards exothermic reaction
Addition of Catalyst No effect
Increase in Pressure where the no. of gaseous moles are less
Decrease in Pressure where the no. of gaseous moles are more

Addition of Inert gas at const.Volume No effect
Addition of Inert gas at const.pressure where the no. of gaseous moles are more
Unit-7
EQUILIBRIUM(Part-I)
1.Question based on law of chemical equilibrium, Equilibrium constant,
Applications of Equilibrium Constants, Relation Between Kp & Kc.
1. What do mean by law of chemical equilibrium? Explain with an example.

2. Write the expression for the equilibrium constant, Kc for each of the
following reactions:
3. Find out the value of Kc for each of the following equilibria from the value
of Kp:
4. Wri
te the balanced chemical equation corresponding to this equilibrium
constant expression for a gas reaction. \
5. What is Kc for the following equilibrium when the equilibrium

concentration of each substance is: [SO2]= 0.60M, [O2] = 0.82M and [SO3]
= 1.90M 2SO2(g) + O2(g)  2SO3(g)
6. The following concentrations were obtained for the formation of NH3 from
N2 and H2 at equilibrium at 500K. [N2] = 1.5 × 10–2M. [H2] = 3.0 ×10–2 M
and [NH3] = 1.2 ×10–2M. Calculate equilibrium constant.
7. At equilibrium, the concentrations ofN2=3.0 × 10–3M, O2 = 4.2 × 10–3M and
NO= 2.8 × 10–3M in a sealed vessel at800K. What will be Kc for the
reaction:N2(g) + O2(g)  2NO(g)
8. PCl5, PCl3 and Cl2 are at equilibrium at 500 K and having concentration
1.59M PCl3, 1.59M Cl2 and 1.41 M PCl5.Calculate Kc for the reaction,PCl5
 PCl3 + Cl2
9. For the equilibrium,2NOCl(g)  2NO(g) + Cl2(g) the value of the
equilibrium constant, Kc is 3.75 × 10–6 at 1069 K. Calculate the Kp for the
reaction at this temperature?
2.Question based on Calculating Equilibrium Concentrations, Le
Chatelierís principleEffect of Pressure Change, Concentration
Change, Temperature Change, Inert Gas Addition & Catalyst

10. The value of Kc = 4.24 at 800K for the reaction, CO (g)
+ H2O (g)  CO2 (g) + H2 (g) Calculate equilibrium concentrations of
CO2, H2, CO and H2O at 800 K, if only CO and H2O are present initially at
concentrations of 0.10M each.The value of Kp for the reaction,CO2 (g) + C
(s)  2CO (g) is 3.0 at 1000 K. If initially p CO2= 0.48 bar and p CO = 0
bar and puregraphite is present, calculate theequilibrium partial pressures of
CO and CO2.
11. A sample of pure PCl5 was introduced into an evacuated vessel at 473 K.
After equilibrium was attained, concentration of PCl5 was found to be0.5 ×
10–1 mol L–1. If value of Kc is 8.3 × 10–3, what are the concentrations of
PCl3 and Cl2 at equilibrium?PCl5 (g)  PCl3 (g) + Cl2(g)
12. What do you mean by Lechatelier‘s principle? Explain with an example?
13. Does the number of moles of reaction products increase, decrease or remain
same when each of the following equilibria is subjected to a decrease in
pressure by increasing the volume?
14. Which of the following reactions will get affected by increasing the
pressure?Also, mention whether change will cause the reaction to go into

forward or backward direction.
15. Dihydrogen gas is obtained from natural gas by partial oxidation with
steam as per following endothermic reaction:
CH4[g] + H2O [g] CO [g] + 3H2[g]
a) Write as expression for Kp for the above reaction.
b) How will the values of Kp and the composition of equilibrium mixture
be affected by
i) Increasing the pressure
ii) Increasing the temperature
iii) Using a catalyst
16. Describe the effect of: - a) Addition of H2 b) Addition of CH3OH c)
Removal of CO d) Removal of CH3OH On the equilibrium of the
reaction: 2 H2[g] + CO[g] CH3OH [g]
17. At 473 K, equilibrium constant Kc for decomposition of phosphorus

pentachloride, PCl5 is 8.3 ×10-3. If decomposition is depicted as, PCl5
(g) PCl3 (g) + Cl2 (g) ΔrH0 = 124.0 kJ mol–1
a) write an expression for Kc for the reaction.
b) what is the value of Kc for the reverse reaction at the same temperature. c)
what would be the effect on Kc if (i) more PCl5 is added (ii) pressure is
increased(iii) the temperature is increased ?
3.Question based on Relationship Between Equilibrium Constant K,
And Gibbs Energy G

18. The value of ΔG0 for the phosphorylation of glucose in glycolysis is 13.8
kJ / mol. Find the value of Kc at 298 K
19. Hydrolysis of sucrose gives, Sucrose + H2O Glucose + Fructose
Equilibrium constant Kc for the reaction is 2 X 1013 at 300K. Calculate ΔG0
at 300K.
20. Calculate a) ΔG0 and b) the equilibrium constant for the formation of NO2
from NO and O2 at 298K NO (g) + ½ O2 (g) NO2 (g) where ΔfG0 (NO2)
= 52.0 kJ/mol ΔfG0 (NO) = 87.0 kJ/mol ΔfG0 (O2) = 0 kJ/mol.
Question 7.1:
A liquid is in equilibrium with its vapour in a sealed container at a fixed
temperature. The volume of the container is suddenly increased.
a) What is the initial effect of the change on vapour pressure?
b) How do rates of evaporation and condensation change initially?
c) What happens when equilibrium is restored finally and what will be the final
vapour pressure?
 Answer
(a) If the volume of the container is suddenly increased, then the vapour pressure
would decrease initially. This is because the amount of vapour remains the same,
but the volume increases suddenly. As a result, the same amount of vapour is
distributed in a larger volume.
(b) Since the temperature is constant, the rate of evaporation also remains constant.
When the volume of the container is increased, the density of the vapour phase
decreases. As a result, the rate of collisions of the vapour particles also decreases.
Hence, the rate of condensation decreases initially.
(c) When equilibrium is restored finally, the rate of evaporation becomes equal to
the rate of condensation. In this case, only the volume changes while the

temperature remains constant. The vapour pressure depends on temperature and
not on volume. Hence, the final vapour pressure will be equal to the original
vapour pressure of the system.
Question 7.2:
What is Kc for the following equilibrium when the equilibrium concentration of
each substance is: [SO2] = 0.60 M, [O2] = 0.82 M and [SO3] = 1.90 M?
 Answer
The equilibrium constant (Kc) for the give reaction is:
Hence, Kc for the equilibrium is .

Question 7.3:
At a certain temperature and total pressure of 105 Pa, iodine vapour contains
40% by volume of I atoms
Calculate Kp for the equilibrium.

 Answer
Partial pressure of I atoms,
Partial pressure of I2 molecules,

Now, for the given reaction,
Question 7.4:
Write the expression for the equilibrium constant, Kc for each of the following
reactions:
(i)
(ii)
(iii)
(iv)
(v)
 Answer

Question 7.5:
Find out the value of Kc for each of the following equilibria from the value of
Kp:
 Answer
The relation between Kp and Kc is given as:
Kp = Kc (RT) Δn
(a) Here,
Δn = 3 – 2 = 1
R = 0.0831 barLmol–1K–1

T = 500 K
Kp = 1.8 × 10–2
Now,
Kp = Kc (RT) Δn
(b) Here,
Δn = 2 – 1 = 1
R = 0.0831 barLmol–1K–1
T = 1073 K
Kp= 167
Now,
Kp = Kc (RT) Δn
Question 7.6:
For the following equilibrium,
Both the forward and reverse reactions in the equilibrium are elementary
bimolecular reactions. What is Kc, for the reverse reaction?
 Answer
It is given that for the forward reaction is
Then, for the reverse reaction will be,

Question 7.7:
Explain why pure liquids and solids can be ignored while writing the equilibrium
constant expression?
 Answer
For a pure substance (both solids and liquids),
Now, the molecular mass and density (at a particular temperature) of a pure
substance is always fixed and is accounted for in the equilibrium constant.
Therefore, the values of pure substances are not mentioned in the equilibrium
constant expression.
Question 7.8:
Reaction between N2 and O2 takes place as follows:
If a mixture of 0.482 mol of N2 and 0.933 mol of O2 is placed in a 10 L reaction

vessel and allowed to form N2O at a temperature for which Kc = 2.0 × 10–37,
determine the composition of equilibrium mixture.
 Answer
Let the concentration of N2O at equilibrium be x.
The given reaction is:

Therefore, at equilibrium, in the 10 L vessel:
The value of equilibrium constant i.e., = 2.0 × 10–37 is very small. Therefore,
the amount of N2 and O2 reacted is also very small. Thus, x can be neglected from
the expressions of molar concentrations of N2 and O2.
Then,
Now,
Question 7.9:
Nitric oxide reacts with Br2 and gives nitrosyl bromide as per reaction given
below:

When 0.087 mol of NO and 0.0437 mol of Br2 are mixed in a closed container at
constant temperature, 0.0518 mol of NOBr is obtained at equilibrium. Calculate
equilibrium amount of NO and Br2.
 Answer
Now, 2 mol of NOBr are formed from 2 mol of NO. Therefore, 0.0518 mol of
NOBr are formed from 0.0518 mol of NO.
Again, 2 mol of NOBr are formed from 1 mol of Br.
Therefore, 0.0518 mol of NOBr are formed from mol of Br, or

0.0259 mol of NO
The amount of NO and Br present initially is as follows:
[NO] = 0.087 mol [Br2] = 0.0437 mol
Therefore, the amount of NO present at equilibrium is:
[NO] = 0.087 – 0.0518
= 0.0352 mol
And, the amount of Br present at equilibrium is:
[Br2] = 0.0437 – 0.0259
= 0.0178 m
Question 7.10:
At 450 K, Kp= 2.0 × 1010/bar for the given reaction at equilibrium.
What is Kc at this temperature?

 Answer
For the given reaction,
Δn = 2 – 3 = – 1
T = 450 K
R = 0.0831 bar L bar K–1 mol–1
= 2.0 × 1010 bar –1
We know that,
Question 7.11:
A sample of HI (g) is placed in flask at a pressure of 0.2 atm. At equilibrium the
partial pressure of HI (g) is 0.04 atm. What is Kp for the given equilibrium?
 Answer
The initial concentration of HI is 0.2 atm. At equilibrium, it has a partial pressure
of 0.04 atm. Therefore, a decrease in the pressure of HI is 0.2 – 0.04 = 0.16. The
given reaction is:
Therefore,

Hence, the value of Kp for the given equilibrium is 4.0.
Question 7.12:
A mixture of 1.57 mol of N2, 1.92 mol of H2 and 8.13 mol of NH3 is introduced
into a 20 L reaction vessel at 500 K. At this temperature, the equilibrium
constant, Kc for the reaction

Is the reaction mixture at equilibrium? If not, what is the direction of the net
reaction?
 Answer
Now, reaction quotient Qc is:
Since , the reaction mixture is not at equilibrium.
Again, . Hence, the reaction will proceed in the reverse direction.
Question 7.13:
The equilibrium constant expression for a gas reaction is,

Write the balanced chemical equation corresponding to this expression.
 Answer
The balanced chemical equation corresponding to the given expression can be
written as:
Question 7.14:
One mole of H2O and one mole of CO are taken in 10 L vessel and heated to
725 K. At equilibrium 40% of water (by mass) reacts with CO according to the
equation,
Calculate the equilibrium constant for the reaction.

 Answer
Therefore, the equilibrium constant for the reaction,
Question 7.15:
At 700 K, equilibrium constant for the reaction
is 54.8. If 0.5 molL–1 of HI(g) is present at equilibrium at 700 K, what are the
concentration of H2(g) and I2(g) assuming that we initially started with HI(g) and
allowed it to reach equilibrium at 700 K?
 Answer
It is given that equilibrium constant for the reaction
is 54.8.
Therefore, at equilibrium, the equilibrium constant for the reaction
will be .
Let the concentrations of hydrogen and iodine at equilibrium be x molL–1
Hence, at equilibrium,
Question 7.16:
What is the equilibrium concentration of each of the substances in the
equilibrium when the initial concentration of ICl was 0.78 M?
 Answer

Question 7.17:
Kp = 0.04 atm at 899 K for the equilibrium shown below. What is the equilibrium
concentration of C2H6 when it is placed in a flask at 4.0 atm pressure and
allowed to come to equilibrium?
 Answer
Let p be the pressure exerted by ethene and hydrogen gas (each) at equilibrium.
Now, according to the reaction,
We can write,

Question 7.18:
Ethyl acetate is formed by the reaction between ethanol and acetic acid and the
equilibrium is represented as:
(i) Write the concentration ratio (reaction quotient), Qc, for this reaction (note:
water is not in excess and is not a solvent in this reaction)
(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 acetate in the final equilibrium mixture. Calculate the
equilibrium constant.
(iii) Starting with 0.5 mol of ethanol and 1.0 mol of acetic acid and maintaining
it at 293 K, 0.214 mol of ethyl acetate is found after sometime. Has equilibrium
been reached?
 Answer
(i) Reaction quotient,

(ii) Let the volume of the reaction mixture be V. Also, here we will consider that
water is a solvent and is present in excess.
Therefore, equilibrium constant for the given reaction is:
(iii) Let the volume of the reaction mixture be V.
Therefore, the reaction quotient is,
Since , equilibrium has not been reached.

Question 7.19:

A sample of pure PCl5 was introduced into an evacuated vessel at 473 K. After
equilibrium was attained, 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 of PCl3 and Cl2 at
equilibrium?
 Answer
Let the concentrations of both PCl3 and Cl2 at equilibrium be x molL–1. The given
reaction is:
Now we can write the expression for equilibrium as:
Therefore, at equilibrium,
Question 7.20:
One of the reactions that take place in producing steel from iron ore is the
reduction of iron (II) oxide by carbon monoxide to give iron metal and CO2.
FeO (s) + CO (g) Fe (s) + CO2 (g); Kp= 0.265 at 1050 K.

What are the equilibrium partial pressures of CO and CO2 at 1050 K if the initial
partial pressures are: pCO = 1.4 atm and = 0.80 atm?

 Answer

Since , the reaction will proceed in the backward direction.
Therefore, we can say that the pressure of CO will increase while the pressure of
CO2 will decrease.
Now, let the increase in pressure of CO = decrease in pressure of CO2 be p.
Then, we can write,
Therefore, equilibrium partial of
And, equilibrium partial pressure of
Question 7.21:
Equilibrium constant, Kc for the reaction
at 500 K is 0.061.
At a particular time, the analysis shows that composition of the reaction mixture
is 3.0 mol L–1 N2, 2.0 mol L–1 H2 and 0.5 mol L–1 NH3. Is the reaction at
equilibrium? If not in which direction does the reaction tend to proceed to reach
equilibrium?
 Answer
Now, we know that,
Since , the reaction is not at equilibrium.
Since , the reaction will proceed in the forward direction to reach

equilibrium.
Question 7.22:
Bromine monochloride, BrCl decomposes into bromine and chlorine and
reaches the equilibrium:
for which Kc= 32 at 500 K. If initially pure BrCl is present at a concentration of

3.3 × 10–3 molL–1, what is its molar concentration in the mixture at equilibrium?
 Answer
Let the amount of bromine and chlorine formed at equilibrium be x. The given
reaction is:
Now, we can write,

Question 7.23:
At 1127 K and 1 atm pressure, a gaseous mixture of CO and CO2 in equilibrium
with solid carbon has 90.55% CO by mass
Calculate Kc for this reaction at the above temperature.

 Answer
Let the total mass of the gaseous mixture be 100 g.
Mass of CO = 90.55 g
And, mass of CO2 = (100 – 90.55) = 9.45 g
Now, number of moles of CO,
Number of moles of CO2,

Partial pressure of CO,

Partial pressure of CO2,

Δn = 2 – 1 = 1
We know that,
Question 7.24:
Calculate a) ΔG°and b) the equilibrium constant for the formation of NO2 from
NO and O2 at 298 K
where ΔfG° (NO2) = 52.0 kJ/mol

ΔfG° (NO) = 87.0 kJ/mol
ΔfG° (O2) = 0 kJ/mol
 Answer
(a) For the given reaction,
ΔG° = ΔG°( Products) – ΔG°( Reactants)
ΔG° = 52.0 – {87.0 + 0}
= – 35.0 kJ mol–1
(b) We know that,
ΔG° = RT log Kc
ΔG° = 2.303 RT log Kc
Hence, the equilibrium constant for the given reaction Kc is 1.36 × 106
Question 7.25:
Does the number of moles of reaction products increase, decrease or remain
same when each of the following equilibria is subjected to a decrease in pressure
by increasing the volume?
(a)
(b)
(c)
 Answer
(a) The number of moles of reaction products will increase. According to Le
Chatelier‘s principle, if pressure is decreased, then the equilibrium shifts in the
direction in which the number of moles of gases is more. In the given reaction, the
number of moles of gaseous products is more than that of gaseous reactants. Thus,
the reaction will proceed in the forward direction. As a result, the number of moles
of reaction products will increase.
(b) The number of moles of reaction products will decrease.
(c) The number of moles of reaction products remains the same
Question 7.26:
Which of the following reactions will get affected by increasing the pressure?

Also, mention whether change will cause the reaction to go into forward or
backward direction.
(i)
(ii)
(iii)
(iv)
(v)
(vi)
 Answer
The reactions given in (i), (iii), (iv), (v), and (vi) will get affected by increasing the
pressure.
The reaction given in (iv) will proceed in the forward direction because the number
of moles of gaseous reactants is more than that of gaseous products.
The reactions given in (i), (iii), (v), and (vi) will shift in the backward direction
because the number of moles of gaseous reactants is less than that of gaseous
products.
Question 7.27:
The equilibrium constant for the following reaction is 1.6 ×105 at 1024 K.
Find the equilibrium pressure of all gases if 10.0 bar of HBr is introduced into a
sealed container at 1024 K.
 Answer
Given,
for the reaction i.e.,
Therefore, for the reaction the equilibrium constant will

be,

Now, let p be the pressure of both H2 and Br2 at equilibrium.
Now, we can write,
Question 7.28:
Dihydrogen gas is obtained from natural gas by partial oxidation with steam as
per following endothermic reaction:
(a) Write as expression for Kp for the above reaction.

(b) How will the values of Kp and composition of equilibrium mixture be affected
by
(i) Increasing the pressure
(ii) Increasing the temperature
(iii) Using a catalyst?
 Answer
(a) For the given reaction,
(b) (i) According to Le Chatelier‘s principle, the equilibrium will shift in the
backward direction.
(ii) According to Le Chatelier‘s principle, as the reaction is endothermic, the
equilibrium will shift in the forward direction.
(iii) The equilibrium of the reaction is not affected by the presence of a catalyst. A
catalyst only increases the rate of a reaction. Thus, equilibrium will be attained
quickly.
Question 7.29:
Describe the effect of:
a) Addition of H2
b) Addition of CH3OH
c) Removal of CO
d) Removal of CH3OH
on the equilibrium of the reaction:
 Answer
(a) According to Le Chatelier‘s principle, on addition of H2, the equilibrium of the
given reaction will shift in the forward direction.
(b) On addition of CH3OH, the equilibrium will shift in the backward direction.
(c) On removing CO, the equilibrium will shift in the backward direction.
(d) On removing CH3OH, the equilibrium will shift in the forward direction.
Question 7.30:
At 473 K, equilibrium constant Kc for decomposition of phosphorus
pentachloride, PCl5 is 8.3 ×10-3. If decomposition is depicted as,
ΔrH° = 124.0 kJmol–1

a) Write an expression for Kc for the reaction.
b) What is the value of Kc for the reverse reaction at the same temperature?
c) What would be the effect on Kc if (i) more PCl5 is added (ii) pressure is
increased? (iii) The temperature is increased?
 Answer
(a)
(b) Value of Kc for the reverse reaction at the same temperature is:
(c) (i) Kc would remain the same because in this case, the temperature remains the
same.
(ii) Kc is constant at constant temperature. Thus, in this case, Kc would not change.
(iii) In an endothermic reaction, the value of Kc increases with an increase in
temperature. Since the given reaction in an endothermic reaction, the value of Kc
will increase if the temperature is increased.
Question 7.31:
Dihydrogen gas used in Haber’s process is produced by reacting methane from
natural gas with high temperature steam. The first stage of two stage reaction

involves the formation of CO and H2. In second stage, CO formed in first stage is
reacted with more steam in water gas shift reaction,
If a reaction vessel at 400°C is charged with an equimolar mixture of CO and
steam such that 4.0 bar, what will be the partial pressure of H2 at
equilibrium? Kp= 10.1 at 400°C
 Answer
Let the partial pressure of both carbon dioxide and hydrogen gas be p. The given
reaction is:
It is
Now,
Hence, at equilibrium, the partial pressure of H2 will be 3.04 bar.
Question 7.32:
Predict which of the following reaction will have appreciable concentration of
reactants and products:
a)
b)
c)
 Answer
If the value of Kc lies between 10–3 and 103, a reaction has appreciable
concentration of reactants and products. Thus, the reaction given in (c) will have
appreciable concentration of reactants and products.
Question 7.33:
The value of Kc for the reaction
3O2 (g) 2O3 (g)

is 2.0 ×10–50 at 25°C. If the equilibrium concentration of O2 in air at 25°C is 1.6
×10–2, what is the concentration of O3?
 Answer
Then, we have,
Hence, the concentration of
Question 7.34:
The reaction, CO(g) + 3H2(g) CH4(g) + H2O(g) is at equilibrium at 1300 K

in a 1L flask. It also contain 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 concentration

of CH4 in the mixture. The equilibrium constant, Kc for the reaction at the given
temperature is 3.90.
 Answer
Let the concentration of methane at equilibrium be x.
It is given that Kc = 3.90.

Therefore,
Hence, the concentration of CH4 at equilibrium is 5.85 × 10–2 M.
Question 7.35:
What is meant by the conjugate acid-base pair? Find the conjugate acid/base for
the following species:
 Answer
A conjugate acid-base pair is a pair that differs only by one proton.
The conjugate acid-base for the given species is mentioned in the table below.
Species Conjugate acid-base
HNO2
CN– HCN (acid)

HClO4
F– HF (acid)
OH– H2O (acid) /O2– (base)
S2– HS– (acid)
Question 7.36:
Which of the followings are Lewis acids? H2O, BF3, H+, and
 Answer
Lewis acids are those acids which can accept a pair of electrons. For example, BF3,
H+, and are Lewis acids.
Question 7.37:
What will be the conjugate bases for the Brönsted acids: HF, H2SO4 and HCO3?
 Answer
The table below lists the conjugate bases for the given Bronsted acids.
Bronsted acid Conjugate base
HF F–
H2SO4
Question 7.38:
Write the conjugate acids for the following Brönsted bases: NH2–, NH3 and
HCOO–.
 Answer
The table below lists the conjugate acids for the given Bronsted bases.
Bronsted base Conjugate acid
NH3
NH3
HCOO– HCOOH

Question 7.39:
The species: H2O, , and NH3 can act both as Brönsted acids and
bases. For each case give the corresponding conjugate acid and base.
 Answer
The table below lists the conjugate acids and conjugate bases for the given species.
Species Conjugate acid Conjugate base
H2 O H3 O+ OH–
H2CO3
H2SO4
NH3
Question 7.40:
Classify the following species into Lewis acids and Lewis bases and show how
these act as Lewis acid/base: (a) OH– (b) F– (c) H+ (d) BCl3.
 Answer
(a) OH– is a Lewis base since it can donate its lone pair of electrons.
(b) F– is a Lewis base since it can donate a pair of electrons.
(c) H+ is a Lewis acid since it can accept a pair of electrons.
(d) BCl3 is a Lewis acid since it can accept a pair of electrons.
Question 7.41:
The concentration of hydrogen ion in a sample of soft drink is 3.8 × 10–3 M.
what is its pH?
 Answer
Given,
pH value of soft drink

Question 7.42:
The pH of a sample of vinegar is 3.76. Calculate the concentration of hydrogen
ion in it.
Question 7.43:
The ionization constant of HF, HCOOH and HCN at 298K are 6.8 × 10–4, 1.8 ×
10–4 and 4.8 × 10–9 respectively. Calculate the ionization constants of the
corresponding conjugate base.
 Answer
It is known that,
Given,
Ka of HF = 6.8 × 10–4
Hence, Kb of its conjugate base F–
Given,
Ka of HCOOH = 1.8 × 10–4
Hence, Kb of its conjugate base HCOO–

Given,
Ka of HCN = 4.8 × 10–9
Hence, Kb of its conjugate base CN–
Question 7.44:
The ionization constant of phenol is 1.0 × 10–10. What is the concentration of
phenolate ion in 0.05 M solution of phenol? What will be its degree of ionization
if the solution is also 0.01M in sodium phenolate?
 Answer
Ionization of phenol:

Now, let α be the degree of ionization of phenol in the presence of 0.01 M
C6H5ONa.
Also,
Question 7.45:
The first ionization constant of H2S is 9.1 × 10–8. Calculate the concentration of
HS– ion in its 0.1 M solution. How will this concentration be affected if the
solution is 0.1 M in HCl also? If the second dissociation constant of H2S is 1.2 ×
10–13, calculate the concentration of S2– under both conditions.
 Answer
(i) To calculate the concentration of HS– ion:
Case I (in the absence of HCl):
Let the concentration of HS– be x M.

Case II (in the presence of HCl):
In the presence of 0.1 M of HCl, let be y M.
(ii) To calculate the concentration of :

Case I (in the absence of 0.1 M HCl):

(From first ionization, case I)
Let
Also, (From first ionization, case I)
Case II (in the presence of 0.1 M HCl):

Again, let the concentration of HS– be X' M.
(From first ionization, case II)
(From HCl, case II)
Question 7.46:
The ionization constant of acetic acid is 1.74 × 10–5. Calculate the degree of
dissociation of acetic acid in its 0.05 M solution. Calculate the concentration of
acetate ion in the solution and its pH.
 Answer

Degree of dissociation,
c = 0.05 M
Ka = 1.74 × 10–5
Thus, concentration of CH3COO– = c.α
Hence, the concentration of acetate ion in the solution is 0.00093 M and its Ph is
3.03.
Question 7.47:
It has been found that the pH of a 0.01M solution of an organic acid is 4.15.
Calculate the concentration of the anion, the ionization constant of the acid and
its pKa.
 Answer
Let the organic acid be HA.

Concentration of HA = 0.01 M
pH = 4.15
Now,
Then,
Question 7.48:
Assuming complete dissociation, calculate the pH of the following solutions:
(a) 0.003 M HCl (b) 0.005 M NaOH (c) 0.002 M HBr (d) 0.002 M KOH
 Answer
(i) 0.003MHCl:
Since HCl is completely ionized,
Now,
Hence, the pH of the solution is 2.52.

(ii) 0.005MNaOH:

(iii) 0.002 HBr:

(iv) 0.002 M KOH:
Question 7.49:
Calculate the pH of the following solutions:
a) 2 g of TlOH dissolved in water to give 2 litre of solution.

b) 0.3 g of Ca(OH)2 dissolved in water to give 500 mL of solution.
c) 0.3 g of NaOH dissolved in water to give 200 mL of solution.
d) 1mL of 13.6 M HCl is diluted with water to give 1 litre of solution.
 Answer
(a) For 2g of TlOH dissolved in water to give 2 L of solution:
(b) For 0.3 g of Ca(OH)2 dissolved in water to give 500 mL of solution:

(c) For 0.3 g of NaOH dissolved in water to give 200 mL of solution:
(d) For 1mL of 13.6 M HCl diluted with water to give 1 L of solution:
13.6 × 1 mL = M2 × 1000 mL
(Before dilution) (After dilution)
13.6 × 10–3 = M2 × 1L
M2 = 1.36 × 10–2
[H+] = 1.36 × 10–2
pH = – log (1.36 × 10–2)
= (– 0.1335 + 2)
Question 7.50:
The degree of ionization of a 0.1M bromoacetic acid solution is 0.132. Calculate
the pH of the solution and the pKa of bromoacetic acid.
 Answer
Concentration, c = 0.1 M
Thus, the concentration of H3O+ = c.
= 0.1 × 0.132
= 0.0132
Now,
Question 7.51:
The pH of 0.005M codeine (C18H21NO3) solution is 9.95. Calculate its ionization
constant and pKb.
 Answer
c = 0.005
pH = 9.95
pOH = 4.05
pH = – log (4.105)
Question 7.52:

What is the pH of 0.001 M aniline solution? The ionization constant of aniline
can be taken from Table 7.7. Calculate the degree of ionization of aniline in the
solution. Also calculate the ionization constant of the conjugate acid of aniline.
 Answer
Kb = 4.27 × 10–10
c = 0.001M
pH =?
α=?
Thus, the ionization constant of the conjugate acid of aniline is 2.34 × 10–5.
Question 7.53:
Calculate the degree of ionization of 0.05M acetic acid if its pKa value is 4.74.
How is the degree of dissociation affected when its solution also contains (a)
0.01 M (b) 0.1 M in HCl?
 Answer

When HCl is added to the solution, the concentration of H+ ions will increase.
Therefore, the equilibrium will shift in the backward direction i.e., dissociation of
acetic acid will decrease.
Case I: When 0.01 M HCl is taken.
Let x be the amount of acetic acid dissociated after the addition of HCl.
As the dissociation of a very small amount of acetic acid will take place, the values
i.e., 0.05 – x and 0.01 + x can be taken as 0.05 and 0.01 respectively.
Case II: When 0.1 M HCl is taken.

Let the amount of acetic acid dissociated in this case be X. As we have done in the
first case, the concentrations of various species involved in the reaction are:

Question 7.54:
The ionization constant of dimethylamine is 5.4 × 10–4. Calculate its degree of
ionization in its 0.02 M solution. What percentage of dimethylamine is ionized if
the solution is also 0.1 M in NaOH?
 Answer
Now, if 0.1 M of NaOH is added to the solution, then NaOH (being a strong base)
undergoes complete ionization.
And,

It means that in the presence of 0.1 M NaOH, 0.54% of dimethylamine will get
dissociated.
Question 7.55:
Calculate the hydrogen ion concentration in the following biological fluids
whose pH are given below:
(a) Human muscle-fluid, 6.83
(b) Human stomach fluid, 1.2
(c) Human blood, 7.38
(d) Human saliva, 6.4.
 Answer
(a) Human muscle fluid 6.83:
pH = 6.83
pH = – log [H+]
6.83 = – log [H+]
[H+] =1.48 × 10–7 M
(b) Human stomach fluid, 1.2:
pH =1.2
1.2 = – log [H+]
[H+] = 0.063
(c) Human blood, 7.38:
pH = 7.38 = – log [H+]

[H+] = 4.17 × 10–8 M
(d) Human saliva, 6.4:
pH = 6.4
6.4 = – log [H+]
[H+] = 3.98 × 10–7
Question 7.56:
The pH of milk, black coffee, tomato juice, lemon juice and egg white are 6.8,
5.0, 4.2, 2.2 and 7.8 respectively. Calculate corresponding hydrogen ion
concentration in each.
 Answer
The hydrogen ion concentration in the given substances can be calculated by using
the given relation:
pH = –log [H+]
(i) pH of milk = 6.8
Since, pH = –log [H+]
6.8 = –log [H+]
log [H+] = –6.8
[H+] = anitlog(–6.8)
=
(ii) pH of black coffee = 5.0
5.0 = –log [H+]
log [H+] = –5.0
=
(iii) pH of tomato juice = 4.2
4.2 = –log [H+]
log [H+] = –4.2

=
(iv) pH of lemon juice = 2.2
2.2 = –log [H+]
log [H+] = –2.2
=
(v) pH of egg white = 7.8
7.8 = –log [H+]
log [H+] = –7.8
=
Question 7.57:
If 0.561 g of KOH is dissolved in water to give 200 mL of solution at 298 K.
Calculate the concentrations of potassium, hydrogen and hydroxyl ions. What is
its pH?
 Answer

Question 7.58:
The solubility of Sr(OH)2 at 298 K is 19.23 g/L of solution. Calculate the
concentrations of strontium and hydroxyl ions and the pH of the solution.
 Answer
Solubility of Sr(OH)2 = 19.23 g/L
Then, concentration of Sr(OH)2

Question 7.59:
The ionization constant of propanoic acid is 1.32 × 10–5. Calculate the degree of
ionization of the acid in its 0.05M solution and also its pH. What will be its
degree of ionization if the solution is 0.01M in HCl also?
 Answer
Then, representing propionic acid as HA, we have:
Question 7.60:
The pH of 0.1M solution of cyanic acid (HCNO) is 2.34. Calculate the ionization
constant of the acid and its degree of ionization in the solution.
 Answer
c = 0.1 M
pH = 2.34

Question 7.61:
The ionization constant of nitrous acid is 4.5 × 10–4. Calculate the pH of 0.04 M
sodium nitrite solution and also its degree of hydrolysis.
 Answer
NaNO2 is the salt of a strong base (NaOH) and a weak acid (HNO2).
Now, If x moles of the salt undergo hydrolysis, then the concentration of various
species present in the solution will be:

Therefore, degree of hydrolysis
= 2.325 × 10–5
Question 7.62:
A 0.02 M solution of pyridinium hydrochloride has pH = 3.44. Calculate the
ionization constant of pyridine
 Answer
pH = 3.44
We know that,
pH = – log [H+]

Question 7.63:
Predict if the solutions of the following salts are neutral, acidic or basic:
NaCl, KBr, NaCN, NH4NO3, NaNO2 and KF
 Answer
(i) NaCl:
Therefore, it is a neutral solution.

(ii) KBr:
Therefore, it is a neutral solution.

(iii) NaCN:
Therefore, it is a basic solution.

(iv) NH4NO3
Therefore, it is an acidic solution.

(v) NaNO2

(vi) KF

Question 7.64:
The ionization constant of chloroacetic acid is 1.35 × 10–3. What will be the pH
of 0.1M acid and its 0.1M sodium salt solution?
 Answer
It is given that Ka for ClCH2COOH is 1.35 × 10–3.

ClCH2COONa is the salt of a weak acid i.e., ClCH2COOH and a strong base i.e.,
NaOH.
Question 7.65:
Ionic product of water at 310 K is 2.7 × 10–14. What is the pH of neutral water at
this temperature?
 Answer
Ionic product,

Hence, the pH of neutral water is 6.78.
Question 7.66:
Calculate the pH of the resultant mixtures:
a) 10 mL of 0.2M Ca(OH)2 + 25 mL of 0.1M HCl
b) 10 mL of 0.01M H2SO4 + 10 mL of 0.01M Ca(OH)2
c) 10 mL of 0.1M H2SO4 + 10 mL of 0.1M KOH
 Answer
(a)
Thus, excess of = .0015 mol
(b)

Since there is neither an excess of or , the solution is neutral. Hence, pH
= 7.
(c)
Excess of = .001 mol
= 1.30
Question 7.67:
Determine the solubilities of silver chromate, barium chromate, ferric hydroxide,
lead chloride and mercurous iodide at 298K from their solubility product
constants given in Table 7.9 (page 221). Determine also the molarities of
individual ions.
 Answer
(1) Silver chromate:
Let the solubility of be s.
Molarity of = 2s = 2 × 0.65 × 10–4 = 1.30 × 10–4 M

Molarity of = s = 0.65 × 10–4 M
(2) Barium chromate:
Let s be the solubility of
Thus, = s and =s
Molarity of = Molarity of
(3) Ferric hydroxide:
Molarity of
Molarity of
(4) Lead chloride:
Let KSP be the solubility of

Molarity of
Molarity of chloride =
(5) Mercurous iodide:
Molarity of
Molarity of
Question 7.68:
The solubility product constant of Ag2CrO4 and AgBr are 1.1 × 10–12 and 5.0 ×
10–13 respectively. Calculate the ratio of the molarities of their saturated
solutions.
 Answer
Let s be the solubility of Ag2CrO4.

Let s´ be the solubility of AgBr.
Therefore, the ratio of the molarities of their saturated solution is
Question 7.69:
Equal volumes of 0.002 M solutions of sodium iodate and cupric chlorate are
mixed together. Will it lead to precipitation of copper iodate? (For cupric iodate
Ksp = 7.4 × 10–8).
 Answer
When equal volumes of sodium iodate and cupric chlorate solutions are mixed
together, then the molar concentrations of both solutions are reduced to half i.e.,
0.001 M.
Then,
Now, the solubility equilibrium for copper iodate can be written as:
Ionic product of copper iodate:
Since the ionic product (1 × 10–9) is less than Ksp (7.4 × 10–8), precipitation will not
occur.
Question 7.70:
The ionization constant of benzoic acid is 6.46 × 10–5 and Ksp for silver benzoate
is 2.5 × 10–13. How many times is silver benzoate more soluble in a buffer of pH
3.19 compared to its solubility in pure water?
 Answer
Since pH = 3.19,
Let the solubility of C6H5COOAg be x mol/L.

Then,
Thus, the solubility of silver benzoate in a pH 3.19 solution is 1.66 × 10–6 mol/L.
Now, let the solubility of C6H5COOAg be x’ mol/L.

Hence, C6H5COOAg is approximately 3.317 times more soluble in a low pH
solution.
Question 7.71:
What is the maximum concentration of equimolar solutions of ferrous sulphate
and sodium sulphide so that when mixed in equal volumes, there is no
precipitation of iron sulphide? (For iron sulphide, Ksp = 6.3 × 10–18).
 Answer
Let the maximum concentration of each solution be x mol/L. After mixing, the
volume of the concentrations of each solution will be
reduced to half i.e., .
If the concentrations of both solutions are equal to or less than 5.02 × 10–9 M, then
there will be no precipitation of iron sulphide
Question 7.72:

What is the minimum volume of water required to dissolve 1g of calcium
sulphate at 298 K? (For calcium sulphate, Ksp is 9.1 × 10–6).
 Answer
Let the solubility of CaSO4 be s.
Molecular mass of CaSO4 = 136 g/mol
Solubility of in gram/L = 3.02 × 10–3 × 136

= 0.41 g/L
This means that we need 1L of water to dissolve 0.41g of CaSO4
Therefore, to dissolve 1g of CaSO4 we require of water.
Question 7.73:
The concentration of sulphide ion in 0.1M HCl solution saturated with hydrogen
sulphide is 1.0 × 10–19 M. If 10 mL of this is added to 5 mL of 0.04 M solution of
the following: FeSO4, MnCl2, ZnCl2 and CdCl2. in which of these solutions
precipitation will take place?
 Answer
For precipitation to take place, it is required that the calculated ionic product
exceeds the Ksp value.
Before mixing:
After mixing:

This ionic product exceeds the Ksp of ZnS and CdS. Therefore, precipitation will
occur in CdCl2 and ZnCl2 solutions.
********************************* THE END************************


CBSE Class 11 Chemistry-Equilibrium

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CBSE Class 11 Chemistry-Equilibrium

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7.

1. Equilibrium represents the state of a process in which the properties like

KENDRIYA VIDYALAYA SANGATHAN

Summary of Le Chatelier’s Principle

Type of Effect or Change Direction of Equilibrium

Addition of more products Backward direction

Increase in temperature Towards endothermic reaction

Decrease in Pressure where the no. of gaseous moles are more

KENDRIYA VIDYALAYA SANGATHAN

Applications of Equilibrium Constants, Relation Between Kp & Kc.

1. What do mean by law of chemical equilibrium? Explain with an example.

KENDRIYA VIDYALAYA SANGATHAN

5. What is Kc for the following equilibrium when the equilibrium

Chatelierís principleEffect of Pressure Change, Concentration

Change, Temperature Change, Inert Gas Addition & Catalyst

KENDRIYA VIDYALAYA SANGATHAN

17. At 473 K, equilibrium constant Kc for decomposition of phosphorus

3.Question based on Relationship Between Equilibrium Constant K,

And Gibbs Energy G

KENDRIYA VIDYALAYA SANGATHAN

KENDRIYA VIDYALAYA SANGATHAN

Hence, Kc for the equilibrium is .

Calculate Kp for the equilibrium.

Partial pressure of I2 molecules,

KENDRIYA VIDYALAYA SANGATHAN

KENDRIYA VIDYALAYA SANGATHAN

KENDRIYA VIDYALAYA SANGATHAN

For the following equilibrium,

It is given that for the forward reaction is

Then, for the reverse reaction will be,

KENDRIYA VIDYALAYA SANGATHAN

If a mixture of 0.482 mol of N2 and 0.933 mol of O2 is placed in a 10 L reaction

KENDRIYA VIDYALAYA SANGATHAN

KENDRIYA VIDYALAYA SANGATHAN

Therefore, 0.0518 mol of NOBr are formed from mol of Br, or

What is Kc at this temperature?

KENDRIYA VIDYALAYA SANGATHAN

constant, Kc for the reaction

Now, reaction quotient Qc is:

Since , the reaction mixture is not at equilibrium.

Again, . Hence, the reaction will proceed in the reverse direction.

KENDRIYA VIDYALAYA SANGATHAN

Calculate the equilibrium constant for the reaction.

Therefore, the equilibrium constant for the reaction,

It is given that equilibrium constant for the reaction

Therefore, at equilibrium, the equilibrium constant for the reaction

Let the concentrations of hydrogen and iodine at equilibrium be x molL–1

KENDRIYA VIDYALAYA SANGATHAN

KENDRIYA VIDYALAYA SANGATHAN

(i) Reaction quotient,

Therefore, equilibrium constant for the given reaction is:

(iii) Let the volume of the reaction mixture be V.

Therefore, the reaction quotient is,

Since , equilibrium has not been reached.

KENDRIYA VIDYALAYA SANGATHAN

Now we can write the expression for equilibrium as:

FeO (s) + CO (g) Fe (s) + CO2 (g); Kp= 0.265 at 1050 K.

partial pressures are: pCO = 1.4 atm and = 0.80 atm?

KENDRIYA VIDYALAYA SANGATHAN

Therefore, equilibrium partial of