EXERCISE II

Q.1 At high temperatures phosgene, COCl2 decompose to give CO & Cl2. In a typical experiment 9.9 × 104
kg of COCl2 is injected into a flask of volume 0.4105 dm3 at 1000 K. When equilibrium is established
it is found that the total pressure in the flask is 3.039 × 10 5 pascals. Calculate the equilibrium constant
(Kp) for this reaction at 1000 K.

Q.2 2 moles of A & 3 moles of B are mixed in 1 litre vessel and the reaction is carried at 400°C according
to the equation; A + B l 2 C. The equilibrium constant of the reaction is 4. Find the number of moles of
C at equilibrium.

Q.3 2 NOBr (g)l 2 NO (g) + Br2 (g). If nitrosyl bromide (NOBr) is 33.33% dissociated at 25° C & a
total pressure of 0.28 atm . Calculate Kp for the dissociation at this temperature.
Q.4 At 90°C , the following equilibrium is established :
H (g) + S(s) l H S(g) K = 6.8 × 102
2 2 p
If 0.2 mol of hydrogen and 1.0 mol of sulphur are heated to 90°C in a 1.0 litre vessel, what
will be the partial pressure of H2S at equilibrium?

Q.5 The equilibrium constant for the reaction is 9.40 at 900°C S 2(g) + C(s) l CS2(g) . Calculate the pressure
of two gases at equilibrium, when 1.42 atm of S2 and excess of C(s) come to equilibrium.

Q.6 A mixture of 2 moles of CH4 & 34 gms of H2S was placed in an evacuated container, which was then
heated to & maintained at 727º C. When equilibrium was established in the gaseous reaction
CH4 + 2 H2S l CS2 + 4 H2 the total pressure in the container was 0.92 atm & the partial pressure of
hydrogen was 0.2 atm. What was the volume of the container ?

Q.7 At 817° C, Kp for the reaction between pure CO2 and excess hot graphite to form 2 CO(g) is 10 atm.
(a) What is the analysis of the gases at equilibrium at 817°C & a total pressure of 4.0 atm ? What is the
partial pressure of CO2 at equilibrium ?
(b) At what total pressure will the gas mixture analyze 6%, CO2 by volume ?

Q.8 The equilibrium mixture SO2 + NO2 l SO3 + NO was found to contain 0.6 mol of SO 3, 0.40 mol of NO,
0.8 mol of SO2 & 0.1 mol of NO2 in a 1L vessel. One mole of NO was then forced into the reaction
vessel with V & T constant. Calculate the amounts of each gas in the new equilibrium mixture.

Q.9 For the reaction N2O4 l 2NO2, equilibrium mixture contains NO 2 at P = 1.1 atm & N 2O4 at
P = 0.28 atm at 350 K. The volume of the container is doubled. Calculate the equilibrium pressures of
the two gases when the system reaches new equilibrium.

Q.10 In the preceding problem, calculate the degree of dissociation,  at both pressures corresponding to
mean molar masses of 65 & 76.667. Use data from the preceding problem.

Q.11 PCl5 dissociates according to the reaction PCl 5 l PCl3(g) + Cl2(g) . At 523 K, K p = 1.78 atm. Find the
density of the equilibrium mixture at a total pressure of 1 atm .

Q.12 The reaction 3/2H2(g) + 1/2 N2(g) l NH3(g) was carried out at T = 620 K & P = 10 atm with an initial
mixture of H2 : N2 = 3 : 1, the mixture at equilibrium contained 7.35 % NH3. Find Kp and Kc.
Q.13 For the reaction SO2(g) + 1/2 O2(g) l SO3(g) H°298 =  98.32 kJ/mole,
S°298 =  95.0 J/K/mole . Find the Kp for this reaction at 298 K.

Q.14 The following data for the equilibrium composition of the reaction
2Na(g) l Na2(g)
at 1.013 MPa pressure and 1482.53 K have been obtained.
mass % Na (monomer gas) = 71.3
mass % Na2 (dimer gas) = 28.7
Calculate the equilirium constant Kp.

Q.15 The degree of dissociation of HI at a particular temperature is 0.8 . Find the volume of 1.5M sodium
thiosulphate solution required to react completely with the iodine present at equilibrium in acidic
conditions, when 0.135 mol each of H2 and I2 are heated at 440 K in a closed vessel of capacity 2.0 L.

Q.16 A reaction system in equilibrium according to the equation 2 SO2 + O2 l 2 SO3 in 1 litre reaction vessel
at a given temperature was found to contain 0.11 mol of SO 2, 0.12 mol of SO3 and 0.05 mol of O2.
Another 1 litre reaction vessel contains 64 g of SO 2 at the same temperature. What mass of O2 must be
added to this vessel in order that at equilibrium half of SO2 is oxidised to SO3 ?

Q.17 A mixture of hydrogen & iodine in the mole ratio 1.5 : 1 is maintained at 450º C. After the attainment of
equilibrium H2(g) + I2(g) l 2 HI(g), it is found on analysis that the mole ratio of I 2 to HI is 1 : 18.
Calculate the equilibrium constant & the number of moles of each species present under equilibrium, if
initially, 127 grams of iodine were taken.

Q.18 In a closed container nitrogen and hydrogen mixture initially in a mole ratio of 1:4 reached equilibrium.
It is found that the half hydrogen is converted to ammonia. If the original pressure was 180 atm, what
will be the partial pressure of ammonia at equilibrium. (There is no change in temperature)

Q.19 The equilibrium constant for the reaction CO(g) + H 2O(g) l CO2(g) + H2(g) is 7.3 at 450º C & 1atm
pressure . The initial concentration of water gas [CO + H 2] & steam are 2 moles & 5 moles respectively.
Find the number of moles of CO, H2, CO2 & H2O (vapour) at equilibrium.

Q.20 At 1200°C, the following equilibrium is established between chlorine atoms & molecule:
Cl2(g) l 2Cl (g)
The composition of the equilibrium mixture may be determined by measuring the rate of effusion of the
mixture through a pin hole. It is found that at 1200°C and 1 atm pressure the mixtureeffuses 1.16 times
as fast as krypton effuses under the same condition. Calculate the equilibrium constant K c.
Q.21 Two solids X and Y disssociate into gaseous products at a certain temperature as follows:
X(s) l A(g) + C(g), and Y(s) l B(g) + C(g). At a given temperature, pressure over excess
solid X is 40 mm and total pressure over solid Y is 60 mm. Calculate:
(a) the values of Kp for two reactions (in mm)
(b) the ratio of moles of A and B in the vapour state over a mixture of X and Y.
(c) the total pressure of gases over a mixture of X and Y.
Q.22 SO3 decomposes at a temperature of 1000 K and at a total pressure of 1.642 atm. At equilibrium, the
density of mixture is found to be 1.28 g/l in a vessel of 90 literes. Find the degree of dissociation of SO 3
for SO3 lSO2 + 1/2O2.

Q.23 Consider the equilibrium: P(g) + 2Q(g) lR(g). When the reaction is carried out at a certain temperature,
the equilibrium conceentration of P and Q are 3M and 4M respectively. When the volume of the vessel
is doubled and the equilibrium is allowed to be reestablished, the concentration of Q is found to be 3M.
Find (A) Kc (B) concentration of R at two equilibrium stages.

Q.24 When PCl5 is heated, it dissociates into PCl 3 and Cl2. The vapor density of the gaseous mixture at 200°C
and 250°C is 70.2 and 57.9 respectively. Find the % dissociation of PCl5 at 200°C and 250°C.

Q.25 The density of an equilibrium mixture of N 2O4 and NO2 at 101.32 KPa is 3.62g dm3 at 288 K and 1.84
g dm3 at 348K. What is the heat of the reaction for N2O4 l 2NO2 (g) .

Q.26 Two solid compounds A & C dissociates into gaseous productat temperature as follows
A(s) B(g) + E (g)
C(s) D(g) + E (g)
At 20° C pressure over excess solid A is 50atm & that over excess solid C is 68atm. Find the total
pressure of gases over the solid mixture.

Q.27 The equilibrium constant for the following reaction at 1395 K.

2H2O l 2H2 + O2 K1 = 2.1 × 10–13
2CO2 l 2CO + O2 K2 = 1.4 × 10–12
Calculate the value of K for the reaction : H2 + CO2 l CO + H2O

Q.28 A saturated solution of iodine in water contains 0.33g I 2 / L. More than this can dissolve in a KI solution
because of the following equilibrium : I 2(aq) + I aq)l I3 aq. A 0.10 M KI solution (0.10 M I)
actually dissolves 12.5 g of iodine/L, most of which is converted to I 3. Assuming that the
concentration of I2 in all saturated solutions is the same, calculate the equilibrium constant for the
above reaction. What is the effect of adding water to a clear saturated of I 2 in the KI solution ?

Q.29 The equilibrium pXyloquinone + methylene white l pXylohydroquinone + methylene blue may be
studied convinently by observing the difference in color methylene white and methylene blue. One
mmol of methylene blue was added to 1L of solution that was 0.24 M in pXylohydroquinone and 0.012
M in pXyloquinone. It was then found that 4% of the added methylene blue was reduced to methylene
white. What is the equilibrium constant of the above reaction? The equation is balanced with one mole
each of 4 substances.

Q.30 A mixture of N2 & H2 are in equilibrium at 600 K at a total pressure of 80 atm. If the initial ratio of N 2
and H2 are 3:1 and at equilibrium NH3 is 10% by volume. Calculate KP of reaction at given temperature.

Q.31  Gº (298 K) for the reaction 1/2 N 2 + 3/2 H2 NH3 is  16.5 kJ mol1 . Find the equilibrium
constant (K1) at 25°C .What will be the equilibrium constants K2 and K3 for the following reactions:
N2 + 3H2 2NH3

NH3 1/2 N2 + 3/2 H2

Q.32 A certain gas A polymerizes to a small extent at a given temperature & pressure, nA l An . Show that the

gas obeys the approx. equation is the volume of the

conatiner. Assume that initially one mole of A was taken in the container.
Q.33 103 mol of CuSO4.5H2O is introduced in a 1.9 L vessel maintained at a constant temperature of 27°C
containing moist air at relative humidity of 12.5%. What is the final molar composition of solid mixture?
For CuSO4.5H2O(s) l CuSO4(s) + 5H2O(g), Kp(atm) = 10–10. Take vapor pressure of water at 27°C as 28
torrs.

Q.34 When 1 mol of A(g) is introduced in a closed 1L vessel maintained at constant temperature, the
following equilibria are established.
A(g) l B(g) + 2C(g) ; = ?
C(g) l 2D(g) + 3B(g) ; =?

The pressure at equilibrium is times the initial pressure.

Calculate & if = .

Q.35 When NO & NO2 are mixed, the following equilibria are readily obtained;
2NO2 l N2O4 Kp = 6.8 atm–1
NO + NO2 l N2O3 Kp = ?
In an experiment when NO & NO2 are mixed in the ratio of 1 : 2, the total final pressure was 5.05 atm &
the partial pressure of N2O4 was 1.7 atm. Calculate
(a) the equilibrium partial pressure of NO.
(b) Kp for NO + NO2 l N2O3

Q.36 Solid NH4I on rapid heating in a closed vessel at 357°C develops a constant pressure of
275 mm Hg owing to partial decomposition of NH 4I into NH3 and HI but the pressure gradually
increases further (when the excess solid residue remains in the vessel) owing to the dissociation of HI.
Calculate the final pressure developed at equilibrium.
NH4I (s) l NH3(g) + HI(g)
2HI (g) l H2(g) + I2(g), Kc = 0.065 at 357°C

Q.37 Given are the following standard free energies of formation at 298K.
CO(g) CO2(g) H2O(g) H2O(l)
rG° / kJ mol–1 –137.17 –394.36 –228.57 –237.13
0
(a) Find rG° and the standard equilibrium constant Kp at 298 K for the reaction
CO(g) + H2O(g) l CO2(g) + H2(g)
(b) If CO, CO2 and H2 are mixed so that the partial pressure of each is 101.325 kPa and the mixture is
brought into contact with excess of liquid water, what will be the partial pressure of each gas when
equilibrium is attained at 298K. The volume available to the gases is constant.

Q.38 For the reaction

C2H6(g) l C2H4(g) + H2(g)
 Kp0 is 0.05 and rG° is 22.384 kJmol–1 at 900 K. If an initial mixture comprising 20 mol of C 2H6 and 80
mol of N2(inert) is passed over a dehydrogenation catalyst at 900K, what is the equilibrium percentage
composition of the effluent gas mixture? The total pressure is kept at 0.5 bar. Given : rS° = 135.143 J
K–1 mol–1 at 300K. Calculate rG° at 300K. (Assume rCp = 0)
Q.39(a) The equilibrium H 2 (g) + CO 2 (g) H 2 O(g) + CO(g) is established in an evacuated vessel
at 723 K starting with 0.1 mole of H 2 & 0.2 mole of CO 2 . If the equilibrium mixture
contains 10 mole per cent of water vapour, calculate K p , given that the equilibrium
pressure is 0.5 atm. Calculate the partial pressures of the component species & the volume
of the container.
(b) If now, into the flask (mentioned in the preceding problem), solid CoO & solid Co are
introduced two new equilibria are established.
CoO(s) + H 2 (g) lCo(s) + H 2 O(g) ; CoO(s) + CO(g) lCo(s) + CO 2 (g)
The new equilibrium mixture contains 30 mole precent of water vapour. Calculate the
equilibrium constants for the new equilibria.

Q.40 Some iodine is dissolved in an aqueous solution of KI of concentration 0.102 mole/1, and the solution is
then shaken with equal volume of CCl 4 until equilibrium is reached (at 15°C). The total amount of
iodine (present as I3 (aq) or as I2 (aq) ) at equilibrium is found to be 0.048 mol/1 in the aqueous layer
and 0.085 mol/1 in the CCl4 layer. The distribution coefficient of iodine between CCl 4 and water is 85.
Calculate the equilibrium constant at 150C for the reaction:
I3 (aq) l I2 (aq) + I (aq)
EXERCISE III
Q.1 Consider following reactions in equilibrium with equilibrium concentration 0.01 M of every species
(I) PCl5 (g) l PCl3(g) + Cl2(g) (II) 2HI(g) l H2(g) + I2 (g)
(III) N2(g) + 3H2(g) l 2NH3(g)
Extent of the reactions taking place is:
(A) I > II > III (B) I < II < III (C) II < III < I (D) III < I < II

Q.2 For the reaction 3 A (g) + B (g) l 2 C (g) at a given temperature , K c = 9.0 . What must be the
volume of the flask, if a mixture of 2.0 mol each of A , B and C exist in equilibrium?
(A) 6L (B) 9L (C) 36 L (D) None of these

Q.3 Sulfide ion in alkaline solution reacts with solid sulfur to form polysulfide ions having formulas
S22, S32, S42 and so on. The equilibrium constant for the formation of S 22 is 12 ( K1) & for the
formation of S32 is 132 (K2 ), both from S and S2.What is the equilibrium constant for the formation of
S32 from S22 and S?
(A) 11 (B) 12 (C) 132 (D) None of these

Q.4 For the following gases equilibrium. N2O4 (g) l 2NO2 (g)
Kp is found to be equal to Kc. This is attained when
(A) 0°C (B) 273 K (C) 1 K (D) 12.19 K

Q.5 1 mole N2 and 3 mol H2 are placed in a closed container at a pressure of 4 atm. The pressure falls to 3
atm at the same temperature when the following equilibrium is attained.
N2(g) + 3H2(g) l 2NH3(g). The equilibrium constant KP for dissociation of NH3 is:
 (A) × (1.5)3 atm–2 (B) 0.5 ×(1.5)3 atm2 (C) atm2 (D) atm–2

Q.6 One mole of N2O4 (g) at 300 K is left in a closed container under one atm . It is heated to 600 K
when 20 % by mass of N2O4 (g) decomposes to NO2 (g) . The resultant pressure is :
(A) 1.2 atm (B) 2.4 atm (C) 2.0 atm (D) 1.0 atm
Q.7 For the reaction : 2Hl (g) l H2(g) + I2(g), the degree of dissociated () of Hl(g) is related to equilibrium
constant KP by the expression

(A) (B) (C) (D)

Q.8 The vapour density of N2O4 at a certain temperature is 30. What is the % dissociation of N 2O4 at this
temperature?
(A) 53.3% (B) 106.6% (C) 26.7% (D) None

Q.9 For the reaction PCl5(g) l PCl3(g) + Cl2(g), the forward reaction at constant temperature is favoured by
(A) introducing an inert gas at constant volume
(B) introducing chlorine gas at constant volume
(C) introducing an inert gas at constant pressure
(D) increasing the volume of the container
(E) introducing PCl5 at constant volume.
Q.10 When N2O5 is heated at temp. T, it dissociates as l , Kc = 2.5. At the same time N 2O3 also decomposes
as : N2O3 l N2O + O2. If initially 4.0 moles of N2O5 are taken in 1.0 litre flask and allowed to attain
equilibrium, concentration of O2 was formed to be 2.5 M. Equilibrium concentration of N2O is
(A) 1.0 (B) 1.5 (C) 2.166 (D) 0.334

Q.11 Densities of diamond and graphite are 3.5 and 2.3 gm/mL.
C (diamond) l C (graphite) rH = –1.9 kJ/mole
favourable conditions for formation of diamond are
(A) high pressure and low temperature
(B) low pressure and high temperature
(C) high pressure and high temperature
(D) low pressure and low temperature

Q.12 When NaNO3 is heated in a closed vessel, oxygen is liberated and NaNO2 is left behind. At equilibrium
(A) addition of NaNO2 favours reverse reaction
(B) addition of NaNO3 favours forward reaction
(C) increasing temperature favours forward reaction
(D) increasing pressure favours reverse reaction

Q.13 The equilibrium SO2Cl2(g) l SO2(g) + Cl2(g) is attained at 25°C in a closed rigid container and an inert
gas, helium is introduced. Which of the following statements is/are correct.
(A) concentrations of SO2, Cl2 and SO2Cl2 do not change
(B) more chlorine is formed
(C) concentration of SO2 is reduced
(D) more SO2Cl2 is formed
Q.14 For the gas phase reaction, C2H4 + H2 l C2H6 (H = – 32.7 kcal), carried out in a closed vessel, the
equilibrium concentration of C2H4 can be increased by
(A) increasing the temperature (B) decreasing the pressure
(C) removing some H2 (D) adding some C2H6

Q.15 An exothermic reaction is represented by the graph :

(A) (B) (C) (D)

Q.16 The correct relationship between free energy change in a reaction and the corresponding equilibrium
constant K is
(A) –G° = RT ln K (B) G = RT ln K (C) –G = RT ln K (D) G° = RT ln K

Q.17 The value of of gaseous mercury is 31 K J/mole. At what total external pressure mercury start
boiling at 25°C. [R = 8.3]
(A) 10–5.44 (B) 10–12.5 (C) 10–6.52 (D) 10–3.12
Q.18 What is rG (KJ/mole) for synthesis of ammonia at 298 K at following sets of partial pressure:
N2(g) + 3H2(g) l 2NH3(g) ; rG° = –33 KJ/mole. [Take R = 8.3 J/K mole, log2 = 0.3; log3 = 0.48]
Gas N2 H2 NH3
Pressure (atm) 1 3 0.02
(A) + 6.5 (B) – 6.5 (C) + 60.5 (D) – 60.5

Q.19 In a 7.0 L evacuated chamber , 0.50 mol H2 and 0.50 mol I2 react at 427°C .
H2(g) + I2(g) l 2HI(g) . At the given temperature, KC=49 for the reaction.
(i) What is the value of Kp ?
(A) 7 (B) 49 (C) 24.5 (D) None

(ii) What is the total pressure (atm) in the chamber?

(A) 83.14 (B) 831.4 (C) 8.21 (D) None

(iii) How many moles of the iodine remain unreacted at equilibrium?

(A) 0.388 (B) 0.112 (C) 0.25 (D) 0.125

(iv) What is the partial pressure (atm) of HI in the equilibrium mixture?

(A) 6.385 (B) 12.77 (C) 40.768 (D) 646.58
Q.20 Equilibrium constants are given (in atm) for the following reactions at 0° C:
SrCl2 6H2O(s) l SrCl2  2H2O (s) + 4H2O(g) Kp = 5 × 1012
Na HPO  12 H O(s) l Na HPO  7 H O (s) + 5H O(g) K = 2.43 × 1013
2 4 2 2 4 2 2 p
Na2SO4 10 H2O(s) l Na2SO4 (s) + 10 H2O (g) Kp = 1.024 × 1027
The vapor pressure of water at 0°C is 4.56 torr.
(i) Which is the most effective drying agent at 0°C?
(A) SrCl2  2H2O (B) Na2HPO47 H2O (C) Na2SO4 (D) all equally

(ii) At what relative humidities will Na2SO4 10 H2O be efflorescent when exposed to air at 0°C?
(A) above 33.33% (B) below 33.33 % (C) above 66.66% (D) below 66.66%
(iii) At what relative humidities will Na2SO4 be deliquescent (i.e. absorb moisture) when exposed to the air
at 0°C?
(A) above 33.33% (B) below 33.33 % (C) above 66.66% (D) below 66.66%

EXERCISE II

Q.1 K p (atm) = 1.13

Q.2 2.4 mole Q.3 K p = 0.01 atm Q.4 0.379 atm
Q.5 P CS2 = 1.284 atm, P S2 = 0.1365 atm
Q.6 300L
Q.7 (i) x co = 0.765, x co2 = 0.235; p(CO 2 ) = 0.938 atm (ii) P Total = 0.68 atm
Q.8 (Kc= 3), nSO2= 0.92, nSO3= 0.48, n NO =1 .28, n NO2 = 0.22
Q.9 P NO2 = 0.64 atm, P N2O4 =0.095 atm Q.10 = 0.415 and 0.2
Q.11 2.7 g / lit Q.12 K c = 1.337, K p = 0.0263 Q.13 K p =1.862 × 10 12 atm 1/2
Q.14 p Na = 0.843 M Pa; p Na2 = 0.170 M Pa; =0.239 Q.15 V = 144 mL
Q.16 9.34 g Q.17 K c =54, n HI =0.9 mol, n I2 = 0.05 mol, n H2 = 0.3 mol
Q.18 48 atm Q.19 n CO2 = 0.938, n H2 = 1.938, n CO = 0.062, n H2Og = 4.062
Q.20 6.71 × 10 –4 Q.21 (a) 400mm 2 , 900mm 2 (b) 4: 9, (c) 72.15 mm Hg
Q.22  = 0.5
Q.23 K c = 1/12, [R] = 4 (initial), = 1.5 (final) Q.24 dissociation = 48.5%, 80.05% Q.25
–1
 r H = 75.5 kJ mol Q.26 Total pressure = 84.34 atm
Q.27 K = 2.58 Q.28 K=707.2, backward reaction is favoured
Q.29 K c = 480 Q.30 1.32 × 10 –3
Q.31 K A = 779.4, K B = 6.074 × 10 5 ; K c = 1.283 × 10 3
Q.32 To be proved Q.33 CuSO 4 .5H 2 O = 9.2 × 10 4 mol, CuSO 4 = 8 × 10 5
moles
Q.34 k C1 = 0.111; k C2 = 0.14 Q.35 (a) 1.05 atm, (b) 3.43 atm –1 Q.36 314.1 atm
Q.37 = 202.65 kPa; = 3.16 kPa; p CO = 0.124 kPa
Q.38 103.47 kJ/mol
Q.39 (a) K p =7.563 × 10 –2 , v = 35.62, p(H 2 O)=p(CO)=0.05atm, p(H 2 )=0.1167atm,
p(CO 2 )=0.2833atm (b) K 1 =9, K 2 =119
Q.40 K = 1.17 × 10 –3
EXERCISE III

Q.1 B Q.2 A Q.3 A Q.4 D

Q.5 B Q.6 B Q.7 D Q.8 A
Q.9 C,D,E Q.10 D Q.11 C Q.12 C,D
Q.13 A Q.14 A,B,C,D Q.15 A Q.16 A
Q.17 A Q.18 D Q.19 (i) B ,(ii) C,(iii) B,(iv) A
Q.20 (i) A, (ii) B, (iii) A