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Contents
Topic Page No.
Theory 01 - 05
Exercise - 1 06 - 20
Exercise - 2 20 - 34
Exercise - 3 35 - 38
Exercise - 4 38 - 41
Answer Key 42 - 43
Syllabus
Chemical Equlibrium :
Types of Equlibrium, Relation between Kp and Kc, Homogeneous and Hetrogeneous Equlibrium,
Relation Between Degree of Dissociation and Vapour Density, Reaction Quotient, Factors Affecting
Equlibrium Constant, Le-Chateliers Principle, Simultaneous Equlibrium.
3 Do not attain equilibrium state. 3 Attain the equilibrium state and never go to completion.
4 Such reactions are represented by single arrow {} 4 Represented by double arrow ( ) or ( )
5 Examples – 5 Examples :–
(a) Precipitation reactions e.g. (a) Homogeneous reactions- only one phase is present
NaCl(aq) + AgNO3(aq) NaNO3(aq) + AgCl (i) Gaseous phase–
(b) Neutralization reactions e.g H2(g) + I2(g) 2HI(g)
HCl(aq) + NaOH(aq) NaCl(aq) + H2O N2(g) + O2(g) 2NO(g) [Birkland eyde process (HNO3)]
(c) 2KClO3 (s) 2KCl(s) + 3O2(g) N2(g) + 3H2(g) 2NH3(g) (Haber’s process)
(d) Reactions in open vessel :– (ii) Liquid phase
Even a reversible reaction will become irreversible if it is CH3 COOH(l) + C2H5OH(l) CH3COOC2H5(l)+ H2O(l)
carried out in open vessel. Ex. Heterogeneous reactions– More than one phases are present
CaCO3(s) CaO(s) + CO2(g) Open CaCO3(s) CaO(s) + CO2(g)
NH4HS(s) NH3(g) + H2S(g) vessel (b) NH4HS(s) NH3(g) + H2S(g) Closed
vessel
Homogeneous equilibrium Heterogeneous equilibrium
When all reactants and products When more than one phase are
are in same phase present
H2(g) + Cl2(g) 2HCl(g) 3Fe(s) + 4H2O(g) Fe3O4(s) + 4H2(g)
SO2(g) + NO2(g) SO3(g) + NO(g) 2Na2O2(s) + 2H2O() 4NaOH + O2(g)
A catalyst can alter the rate of approach of equilibrium but does not change the state of equilibrium. By using
catalyst, the equilibrium can be achieved in different (more/less) time, but the relative concentrations of
reactants and products are same irrespective of the presence or absence of a catalyst.
Equilibrium can be observed by constancy of some observable properties like colour, pressure, concentration,
density, temperature, refractive index etc.which may be suitable in a given reaction.
At equilibrium, free energy changeG = 0
Equilibrium state can be affected by altering factors like pressure, volume, concentration and temperature
etc.(Le chateliers Principle).
System moves toward an equilibrium state spontaneously even if it is disturbed. It will return to original state.
k f [C]c [D]d
or,
k r [A]a [B]b
kf [C]c [D]d
or Kc
kr [A]a [B]b
Where, Kc is the equilibrium constant in terms of molar concentration.
Equilibrium Constant (Kp) in terms of Partial Pressures:
PCc PDd
Kp …(2)
PAa PBb
K p K c (RT) n
Where, n = (c + d) – (a + b)
Applications of Equilibrium constant :
Predicting the direction of the reaction
Reaction Quotient (Q)
At each point in a reaction, we can write a ratio of concentration terms having the same form as the
equilibrium constant expression. This ratio is called the reaction quotient denoted by symbol Q.
It helps in predicting the direction of a reaction.
[C]c [D] d
The expression Q = at any time during reaction is called reaction quotient.The concentrations
[ A ]a [B]b
[C], [D] , [A], [B] are not necessarily at equilibrium.
Predicting the extent of the reaction :
[Pr oduct ] eq
K = [Re ac tan t ]
eq
Case-I If K is large (K > 103) then product concentration is very very larger than the reactant ([Product] >>[Reactant])
Hence concentration of reactant can be neglected with respect to the product. In this case, the reaction is
product favourable and equilibrium will be more in forward direction than in backward direction.
k2 H 1 1
log k = 2.303 R T T ; H = Enthalpy of reaction
1 1 2
a.Mth
=
a(1 (n 1) )
Mth
Mobs =
[1 (n 1)]
MA n
Mmixture = , MA n = Molar mass of gas An
[1 (n 1)]
Vapour density (V.D). : Density of the gas divided by density of hydrogen under same temp &
pressure is called vapour density.
MA n
D = vapour density without dissociation =
2
Mmix
d = vapour density of mixture = observed v.d. =
2
D
= 1 + (n – 1)
d
Dd M Mo
T
(n 1) d (n 1)M0
where MT = Theoritical molecular wt. M0 = observed molecular wt. or molecular wt. of the mixture at equilibrium.
pcC pdD
G G 0 RT ln = G0 + RTlnQp
p aA p Bb
the condition for a system to be at equilibrium is that
G = 0
Thus at equilibrium
pc pdD
0 G 0 RT ln Ca b
G 0 RT ln K 0p
pA pB
Whence G0 = – RTlnK0p
0 G 0
Hence ln K p
RT
Section (A) : Equilibrium, Equilibrium constant ,law of mass action, Reaction Quotient
A-1. A chemical reaction, A B, is said to be in equilibrium when :
(A) rate of forward reaction is equal to rate of backward reaction
(B) conversion of A to B is only 50% complete
(C) complete conversion of A to B has taken place
(D) only 25% conversion of A to B taken place
A-2. The equilibrium concentration of x, y and yx 2 are 4, 2 and 2 respectively for the equilibrium
2x + y yx2. The value of equilibrium constant, KC is
(A) 0.625 (B) 6.25 (C) 0.0625 (D) 62.5
A-3. 4 mole of A are mixed with 4 mole of B and 2 mole of C are formed at equilibrium, according to the reaction,
A+B C+D
the equilibrium constant is :
(A) 2 (B) 2 (C) 1 (D) 4
A-4. For the following reaction at 250°C, PCl3(g) + Cl2(g) PCl5(g) the value of KC is 26 then the value of Kp
at same temperature will be
(A) 0.57 (B) 0.61 (C) 0.83 (D) 0.91
A-5. For a reversible reaction, the rate constants for the forward and backward reactions are
2.38 ×10–4 and 8.15 × 10–5 respectively. The equilibrium constant for the reaction is –
(A) 0.342 (B) 2.92 (C) 0.292 (D) 3.42
A-6. If different quantities of ethanol and acetic acid were used in the following reversible reaction,
CH3COOH() + C2H5OH() CH3COOC2H5() + H2O()
the equilibrium constant will have values which will be ?
(A) different in all cases
(B) same in all cases
(C) higher in cases where higher concentration of ethanol is used
(D) higher in case where higher concentration of acetic acid is used
A-7. Chemical equilibrium is dynamic in nature because –
(A) The equilibrium in maintained quickly
(B) Conc. of reactants and products become same at equilibrium
(C) Conc. of reactants and products are constant but different
(D) Both forward and backward reactions occur at all times with same speed
A-9. Starting with the reactants , At any moment before a reversible reaction attains equilibrium it is found
that –
(A) The rate of the forward reaction is increasing and that of backward reaction is decreasing
(B) The rate of the forward reaction is decreasing and that of backward reaction is increasing
(C) The rate of both forward and backward reactions is increasing
(D) The rate of both forward and backward reactions is decreasing
A-12. Which of the following statements is not correct about the equilibrium constant ?
(A) Its value does not depend upon the initial conc. of the reactants
(B) Its value does not depend upon the initial conc. of the products
(C) Its value does not depend upon temperature.
(D) Its value does not depend upon presence of catalyst.
A-13. In a chemical equilibrium, the equilibrium constant is found to be 2.5. If the rate constant of backward
reaction is 3.2 × 10–2, the rate constant of forward reaction is -
(A) 8.0 × 10–2 (B) 4.0 × 10–2 (C) 3.5 × 10–2 (D) 7.6 × 10–3
A-14. K1 and K2 are the rate constants of forward and backward reactions. The equilibrium constant K of the
reaction is -
K1 K1 K 2
(A) K1 × K2 (B) K1 – K2 (C) (D)
K2 K1 – K 2
A-15. The value of KP for the reaction H2(g) + I2(g) 2HI(g) is 50. What is the value of KC
(A) 30 (B) 40 (C) 50 (D) 70
A-17. Select the correct expression regarding the relation between KP and KC for the reaction
aX(g) + bY(g) bZ(g) + aW (g) -
KC
(A) KP = KC(RT)a+b (B) KP = (C) KP = KC RT (D) KP = KC
(a b) 2
A-18. The equilibrium constant KC for the decomposition of PCl5 is 0.625 mole / lit at 300ºC. Then the value
of KP is -
(A) 2.936 atm (B) 0.0625 atm (C) 6.25 atm (D) 0.00625 atm
A-19. The reaction A(g) + B(g) C(g) + D(g) proceeds to right hand side upto 99.9% when starting bwith
equal moles of A and B. The equilibrium constant K for the reaction will be -
(A) 104 (B) 105 (C) 106 (D) 108
A-20. For the reaction, 2NO2 (g) 2NO (g) + O2(g), KC = 1.8 × 10–6 at 185ºC. At 185ºC, the
value of KC for the reaction -
1
NO(g) + O (g) NO2(g) is -
2 2
(A) 0.9 × 10 6 (B) 7.5 × 102 (C) 1.95 × 10–3 (D) 1.95 × 103
A-22. The equilibrium concentration of X, Y and YX2 are 4, 2 and 2 moles respectively for the equilibrium
2X(g) + Y(g) YX2(g).The value of KC is -
(A) 0.625 (B) 0.0625 (C) 6.25 (D) 0.00625
1
A-23. At 444º C, the equilibrium constant K for the reaction 2AB(g) A2(g) + B2(g) is . The
64
degree of dissociation of AB will be -
(A) 10% (B) 20 % (C) 30% (D) 50%
A-24. For the reaction A(g) + B(g) C(g) + D(g), the degree of dissociation would be –
K
(A) (B) K +1 (C) K 1 (D) K–1
K 1
A-25. For the reaction : N2O3(g) NO(g) + NO2(g) ; total pressure = P, degree of dissociation = 50%.
Then Kp would be –
P P
(A) 3P (B) 2P (C) (D)
3 2
A-28. Equilibrium concentration of HI, I2 and H2 is 0.7, 0.1 and 0.1 moles/litre. Calculate the equilibrium
constant for the reaction :
I2(g) + H2(g) 2HI(g) –
(A) 0.36 (B) 36 (C) 49 (D) 0.49
A-29. The equilibrium constant for the reaction Zn (s)+CO2(g) ZnO (s) + CO (g) is -
KP
A-32. for the gaseous reaction –
KC
(a) 2 A + 3 B 2C
(b) 2 A 4B
(c) A + B + 2C 4D
would be respectively -
(A) (RT)–3 , (RT)2, (RT)º (B) (RT)–3 , (RT)–2, (RT)–1
(C) (RT)–3 , (RT)2, (RT) (D) None of the above
A-34. In a reversible reaction A B, the initial concentration of A and B are a and b in moles per litre and the
equilibrium concentrations are ( a x) and (b + x) respectively; express x in terms of k1, k2, a and b.
k 1a k 2b k 1a k 2b k 1a k 2b k 1a k 2b
(A) k 1 k 2 (B) k1 k 2 (C) k1k 2 (D) k 1k 2
A-35. The equilibrium constant of the reaction SO2(g) + ½O2(g) SO3(g) is 4 × 10–3 atm–1/2. The equilibrium
constant of the reaction 2SO3(g) 2SO2(g) + O2(g) would be :
(A) 250 atm 3
(B) 4 × 10 atm (C) 0.25 × 104 atm (D) 6.25 × 104 atm
D
B-4. In the dissociation of N2O4 into NO2, (1 + ) values with the vapour densities ratio is as given by :
d
[-degree of dissociation, D-vapour density before dissociation, d-vapour density after dissociation]
D
B-5. In the above question, varies with according to :
d
B-7. The degree of dissociation of PCl5 () obeying the equilibrium, PCl5 PCl3 + Cl2 , is approximately
related to the presure at equilibrium by (given << 1) :
1 1 1
(A) P (B) (C) 2 (D)
P P P4
B-8. For the reaction N2O4 (g) 2NO2 (g), if percentage dissociation of N2O4 are 20%, 45%, 65% & 80%,
then the sequence of observed vapour densities will be :
(A) d20 > d45 > d65 > d80 (B) d80 > d65 > d45 > d20
(C) d20 = d45 = d65 = d80 (D) (d20 = d45) > ( d65 = d80)
B-10. N2O4 dissociates as N2O4(g) 2NO2(g) at 273 K and 2 atm pressure. The equilibrium mixture has
a density of 41. What will be the degree of dissociation -
(A) 14.2% (B) 16.2% (C) 12.2% (D) None
B-11. At 250ºC and 1 atmospheric pressure, the vapour density of PCl5 is 57.9 . What will be the dissociation
of PCl5 –
(A) 1.00 (B) 0.90 (C) 0.80 (D) 0.65
C-2. In the melting of ice, which one of the conditions will be more favourable –
(A) High temperature and high pressure (B) Low temperature and low pressure
(C) Low temperature and high pressure (D) High temperature and Low pressure
C-3. In the reaction, 2SO2 (g) + O2 (g) 2SO3 (g) + X cals, most favourable condition of temperature
and pressure for greater yield of SO3 are -
(A) Low temperature and low pressure (B) High temperature and low pressure
(C) High temperature and high pressure (D) Low temperature and high pressure
C-4. On adding inert gas to the equilibrium PCI5(g) PCI3(g) + CI2(g) at constant pressure. The degree
of dissociation will remain –
(A) Unchanged (B) Decreased (C) Increased (D) None of these
C-6. Adding inert gas to system N2(g) + 3H2(g) 2NH3(g) at equilibrium at constant volume will lead to :
(A) N2 and H2 are formed in abundance
(B) N2, H2 and NH3 will have the same molar concentration
(C) The production of ammonia increases
(D) No change in the equilibrium
C-7. In the reaction N2(g) + 3H2(g) 2NH3(g), the forward reaction is exothermic and the backward
reaction is endothemic. In order to produce more heat it is necessary –
(A) To add ammonia
(B) To add N2 and H2
(C) Increasing the concentration of N2,H2 and NH3 equally
(D) None of the above
C-8. The reaction in which the yield of the products can not be increased by the application of high pressure
is –
(A) PCl3 (g) + Cl2 (g) PCl5 (g) (B) N2 (g) + 3H2 (g) 2NH3 (g)
(C) N2 (g) + O2 (g) 2NO (g) (D) 2SO2 (g) + O2 (g) 2SO3 (g)
C-10. In the reaction A (g) + B (g) C (g), the backward reaction is favoured by -
(A) Increase in pressure (B) Decrease in pressure
(C) Neither increase nor decrease in pressure (D) Data unpredictable
C-11. Which among the following conditions, increase the yield of the product in the equilibrium,
3 A(g) + B(g) 4C(g) + heat
(A) Increase in pressure (B) Increase in volume
(C) Increase in temperature (D) Decrease in temperature
C-12. When H2 is added to an equilibrium mixture 2HI(g) H2(g) + I2(g), at constant temperature, the -
(A) Value of Kp decreases
(B) Value of Kp increases
(C) The degree of dissociation of HI decreases
(D) Degree of dissociation of HI increases
C-13. For the reaction PCl5 (g) PCl3 (g) + Cl2 (g), the forward reaction at constant temperature is
favoured by -
(A) Increasing the volume of container
(B) Introducing an inert gas at constant pressure
(C) Introducing PCl5 at constant volume
(D) All of these
C-15. In what manner will increase of pressure affect the equation C (s) + H2O (g) CO(g) + H2(g) -
(A) Shift in the forward direction (B) Shift in the reverse direction
(C) Increase in the yield of H2 (D) No effect
C-18. According to Le Chatelier principle, an increase in the temperature of the following reaction will
N2 + O 2 2NO – 43200 cal
(A) Increase the yield of NO (B) Decrease the yield of NO
(C) Not effect on the yield of NO (D) Not help the reaction to proceed
C-21. For the reaction CO(g) + H2O(g) CO2(g) + H2(g) at a given temperature the equilibrium amount of CO2 (g)
can be increased by :
(A) adding a suitable catalyst (B) adding an inert gas
(C) decreasing the volume of container (D) increasing the amount of CO(g)
C-22.* For the reaction : PCl5 (g) PCl3 (g) + Cl2 (g)
The forward reaction at constant temperature is favoured by
(A) introducing chlorine gas at constant volume
(B) introducing an inert gas at constant pressure
(C) increasing the volume of the container
(D) introducing PCl5 at constant volume
C-23. Given the following reaction at equilibrium N2(g) + 3H2(g) 2NH3(g). Some inert gas at constant pressure
is added to the system. Predict which of the following facts will be affected.
(A) More NH3(g) is produced (B) Less NH3(g) is produced
(C) No affect on the equilibrium (D) Kp of the reaction is decreased
C-24. For an equilibrium H2O(s) H2O() which of the following statements is true.
(A) The pressure changes do not affect the equilibrium
(B) More of ice melts if pressure on the system is increased
(C) More of liquid freezes if pressure on the system is increased
(D) The pressure changes may increase or decrease the degree of advancement of the reaction depending
upon the temperature of the system
C-25. When a bottle of cold drink is opened, the gas comes out with a fizz due to :
(A) Decrease in temperature
(B) Increase in pressure
(C) Decrease in pressure suddenly which results in decrease of solubility of CO2 gas in water
(D) None
C-26. The equilibrium, SO2Cl2(g) SO2(g) + Cl2(g) is attained at 25°C in a closed container ,if an inert gas,
helium, is introduced at constant volume. Which of the following statement(s) is/are correct.
(A) Concentrations of SO2, Cl2 and SO2Cl2 are changed
(B) No effect on equilibrium
(C) Concentration of SO2 is reduced
(D) Kp of reaction is increasing
C-31. In the reaction, 2SO2(g) + O2(g) 2SO3(g) + X cal, most favourable conditions of temperature and
pressure for greater yield of SO3 are :
(A) low temperature and low pressure (B) high temperature and low pressure
(C) high temperature and high pressure (D) low temperature and high pressure
C-33. In a vessel containing SO2, SO3 and O2 at equilibrium, some helium gas is introduced so that total pressure
increases while temperature and volume remain the same. According to the
Le Chatelier’s principle, the dissociation of SO3 :
(A) increases (B) decreases (C) remains unaltered (D) change unpredictably
C-34. The equilibrium SO2Cl2(g) SO2(g) + Cl2(g) is attained at 25°C in a closed container and an inert gas,
helium, is introduced. Which of the following statements is correct ?
(A) concentrations of SO2Cl2, SO2 and Cl2 do not change
(B) more Cl2 is formed
(C) concentration of SO2 is reduced (D) more SO2Cl2 is formed
D-1. The two equilibria, AB(aq) A+(aq) + B(aq) and AB(aq) + B(aq) AB2(aq) are simultaneously
maintained in a solution with equilibrium constants, K1 and K2 respectively. The ratio of concentration of A+
to AB2 in the solution is :
(A) directly proportional to the concentration of B– (aq.).
(B) inversely proportional to the concentration of B– (aq.).
(C) directly proportional to the square of the concentration of B– (aq.).
(D) inversely proportional to the square of the concentration of B– (aq.).
D-2. In the preceeding problem, if [A+] and [AB2] are y and x respectively, under equilibrium produced by adding
the substance AB to the solvents, then K1/K2 is equal to
y y 2 (x y) y 2 (x y) y
(A) ( y x )2 (B) (C) (D) (x y)
x x x x
E-1. Which is/are correct relation (s) for thermodynamic equilibrium constant
(A) Gº = –2.303 RT log K (B) G = Gº + 2.303 RT log K
0.0591 0.0591
(C) Eºcell = log K (D) E = Eº – logK
n n
E-2. Which is/are correct relation (s) for equilibrium constant K?
2.303 RT log K
(A) Gº = – 2.303 RT log K (B) Ecellº =
nF
Ó [Pr oduct] H
(C) K = (D) log K = log A –
Ó [Re ac tan t] 2.303 RT
1
E-4. Variation of log10 K with is shown by the following graph in which straight line is at 45°, hence H° is :
T
(A) + 4.606 cal (B) – 4.606 cal (C) 2 cal (D) – 2cal
K2 H º 1 1
log K = then,
1 2.303R T2 T1
(A) K2 > K1 if T2 > T1 for an endothermic change
(B) K2 < K1 if T2 > T1 for an endothermic change
(C) K2 > K1 if T2 > T1 for an exothermic change
(D) K2 < K1 if T2 > T1 for an exothermic change
E-6. Which one of the following oxides is most stable? The equilibrium constants are given at the same temperature:
(A) 2N2O5(g) 2N2(g) + 5O2(g) ; K = 1.2 × 1034
(B) 2N2O(g) 2N2(g) + O2(g) ; K = 3.5 × 1035
(C) 2NO(g) N2(g) + O2(g) ; K = 2.2 × 1030
(D) 2NO2(g) N2(g) + 2O2(g) ; K = 6.71 × 1016
E-7. The equilibrium constant for a reaction A + B C + D is 1 × 10–2 at 298 K and is 2 at 273 K. The
chemical process resulting in the formation of C and D is :
(A) exothermic (B) endothermic
(C) unpredictable (D) there is no relationship between H and K
(b) Solids whose volume increase on melting, e.g., Fe, Cu, Ag, Au, etc.
Solid (lower volume) Liquid (higher volume)
In this case the process of melting become difficult at high pressure; thus melting point becomes high.
(c) Solubility of substances : When solid substance are dissolved in water, either heat is evolved (exothermic)
or heat is absorbed (endothermic).
KCl + aq KCl(aq) – heat
In such cases, solubility increase with increase in temperature. Consider the case of KOH; when this is
dissolved, heat is evolved.
KOH + aq KOH(aq) + heat
In such cases, solubility decrease with increase in temperature.
(d) Solubility of gases in liquids : When a gas dissolves in liquid, there is decrease in volume. Thus,
increase of pressure will favour the dissolution of gas in liquid.
1. A gas 'X' when dissolved in water heat is evolved. Then solublity of 'X' will increase :
(A) Low pressure, high temperature (B) Low pressure, low temperature
(C) high pressure, high temperature (D) high pressure, low temperature
2. Au(s) Au()
Above equilibrium is favoured at :
(A) High pressure low temperature (B) High pressure high temperature
(C) Low pressure, high temperature (D) Low pressure, low temperature
1 1
3. For the reaction, N2(g) + O2(g) NO(g)
2 2
If pressure is increased by reducing the volume of the container then :
(A) Total pressure at equilibrium will change.
(B) Concentration of all the component at equilibrium will change.
(C) Concentration of all the component at equilibrium will remain same
(D) Equilibrium will shift in the forward direction
Hº
Clearly if a plot of log k vs 1/T is made then it is a straight line having slope =
2.3 R
S
and Y intercept = 2.3 R
Hº S º
log K2 = .......... (5)
2.3 R T2 2.3 R
Substracting (4) from (5) we get
K2 Hº 1 1
log
K1 2.30 R T1 T2
From the above relation we can conclude that the value of equilibrium constant increases with increase in
temperature for endothermic reaction but value of equilibrium constant decreases with the increase in
temperature for exothermic reaction.
1
4. If standard heat of dissociation of PCl5 is 230 cal then slope of the graph of logk vs is :
T
(A) +50 (B) – 50 (C) 10 (D) None
1
5. For exothermic reaction if S0 < 0 then the sketch of logk vs may be :
T
1/T
Comprehensions # 3
Equilibrium constants are given (in atm) for the following reactions at 0° C:
SrCl2 6H2O(s) SrCl2 2H2O (s) + 4H2O(g) Kp = 5 × 1012
Na2HPO4 12 H2O(s) Na2HPO4 7 H2O (s) + 5H2 O(g) Kp = 2.43 × 1013
Na2SO4 10 H2O(s) Na2SO4 (s) + 10 H2O (g) Kp = 1.024 × 1027
The vapor pressure of water at 0°C is 4.56 torr.
8. At what relative humidities will Na2SO4 10 H2O be efflorescent (release moisture) when exposed to air at
0°C?
(A) above 33.33% (B) below 33.33 % (C) above 66.66% (D) below 66.66%
9. 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%
Comprehensions # 4
If we know the equilibrium constant for a particular reaction, we can calculate the concentrations in the
equilibrium
mixture from the initial concentrations. Commonly only the initial concentration of reactants are given.
(B) Introduction of inert gas at (Q) PCl5 (g) PCl3 (g) + Cl2 (g)
constant pressure will decrease
the concentration of reactants
(D) Temperature increase will shift (S) NH3 (g) + HI (g) NH4I (s)
the reaction on product side.
23. Statement - 1. Reaction quotient Q is equal to Keq when the reaction is in equilibrium.
Statement - 2. If a catalyst is added to the reaction at equilibrium, the value of Q remains no
longer equal to Keq.
24. Statement - 1. In the presence of catalyst, the value of equilibrium constant K increases.
Statement - 2. Catalyst increases the rate of forward and backward reaction to same extent.
25. Statement - 1. For the reaction, N2 + O2 2NO, increase in pressure at equilibrium has no effect
on the reaction.
Statement - 2. The reaction is not accompanied by any change in number of moles of gaseous species.
26. Statement-1 : In dilute aqueous solution water is present in such large excess that its concentration remains
essentially constant during any reaction involving water.
Statement-2 : The term [H2O] does not appear in any equilibrium constant expression for a reaction taking
place in dilute aqueous solution.
27. Statement-1 : A net reaction can occur only if a system is not at equilibrium.
Statement-2 : All reversible reactions occur to reach a state of equilibrium.
28. Statement-1 : No term in the concentration of a pure solid or a pure liquid appears in an equilibrium constant
expression.
Statement-2 : Each pure solid or pure liquid is in a phase by itself, and has a constant concentration at
constant temperature.
29. Statement-1 : The reaction quotient , Q has the same form as the equilibrium constant Keq, and is evaluated
using any given concentrations of the species involved in the reaction, and not necessarily equilibrium
concentrations.
Statement-2 : If the numerical value of Q is not the same as the value of equilibrium constant, a reaction will occur.
30. Statement-1 : If the equation for a reaction is reversed, the equilibrium constant is inverted and if the
equation is multiplied by 2, the equilibrium constant is squared.
Statement-2 : The numerical value of an equilibrium constant depends on the way the equation for the
reaction is written.
31. Statement-1 : The dissociation of CaCO3 can be represented as, CaCO3(s) CaO(s) + CO2(g). Some
solid CaCO3 is placed in an evacuated vessel enclosed by a piston and heated so that a portion of its
decomposes. If the piston is moved so that the volume of the vessel is doubled, while the temperature is held
constant, the number of moles of CO2 in the vessel increase.
Statement-2 : The pressure of CO2 in the vessel will remain the same.
32. Statement-1 : A catalyst does not influences the values of equilibrium constant.
Statement-2 : Catalysts influence the rate of both forward and backward reactions equally.
33. Statement-1 : For . If more Cl2 is added the equilibrium will shift in backward
direction hence equilibrium constant will decrease.
Statement-2 : Addition of inert gas to the equilibrium mixture at constant volume, does not alter the equilibrium.
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TRUE / FALSE
34. A catalyst does not alter the equilibrium point.
35. For the equilibrium, H2 + I2 2HI, the value of equilibrium constant increases with increase in
concentration of H2.
36. For any reaction greater the value of equilibrium constant greater is the extent of completion of reaction.
38. For the reaction PCl5 PCl3 + Cl2, the degree of dissociation of PCl5 increases with increase in
pressure.
39. The value of equilibrium constant does not depend upon pressure.
40. When a liquid and its vapour are at equilibrium and the pressure is suddenly decreased, cooling occurs.
41. If equilibrium constant for the reaction, A2 + B2 2AB, is K, then for the backward reaction
1 1 1
AB A2 + B2, the equilibrium constant is .
2 2 K
44. A catalyst increases the value of the equilibrium constant for a reaction.
45. In case of endothermic reactions, the equilibrium shifts in backward direaction on increasing the temperature.
2. XY2 dissociates as :
XY2(g) XY(g) + Y(g)
Initial pressure of XY2 is 600 mm Hg. The total pressure at equilibrium is 800 mm Hg. Assuming volume of
system to remain constant, the value of Kp is :
(A) 50 (B) 100 (C) 200 (D) 400
Px 3 Px 2 Px 3 Px 2
(A) (B) (C) (D)
2 3 3 2
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4. In the equilibrium SO2Cl2 SO2 + Cl2 at 2000 K and 10 atm pressure, % Cl2 = % SO2 = 40 by volume.
Then
n (SO 2 Cl 2 ) 1
(A) Kp = 2 atm (B) = at equilibrium
n (SO 2 ) 4
(C) Kp = 8 atm (D) n(SOCl2) = n(SO2) = n(Cl2)
5. The KC for the reaction A + B C + D is 9. If one mole of each of A and B are mixed and there
is no change in volume, the number of moles of C formed is–
(A) 0.50 (B) 0.75 (C) 0.90 (D) 1.5
7. The equilibrium constant of the reaction A + B C + D is 10. If rate constant of forward reaction
is 203, the rate constant of backward reaction is –
(A) 20.3 (B) 10.3 (C) 2.03 (D) 203
8. The equilibrium constants for the reaction X 2 2X at 300K and 600K are 10 –8 and
10–3 respectively. The reaction is –
(A) Exothermic (B) Endothermic (C) Thermo neutral (D) Slow
12. The equilibrium constant for the reaction 2 X (g) + Y (g) 2Z (g) is 2.25. What would be
the concentration of Y at equilibrium with 2.0 moles of X and 3.0 moles of Z in one litre vessel at
equilibrium–
(A) 1.0 moles (B) 2.25 moles (C) 2.0 moles (D) 4.0 moles
15. In a 10 litre box 2.5 mole iodic acid is taken. After equilibrium
2HI H2 + I2
the concentration of HI is found to be 0.1 mol l –1 The concentration of [H2] at equilibrium in mol –1, is –
(A) 2.4 (B) 0.15 (C) 1.5 (D) 7.5 × 10–2
17. At 27°C NO and Cl2 gases are introduced in a 10 litre flask such that their initial partial pressures are
20 and 16 atm respectively. The flask already contains 24 g of magnesium. After some time, the
amount of magnesium left was 0.2 moles due to the establishment of following two equilibria
2NO(g(g)) Cl2(g) 2NOCl(g)
ClCl Mg
2(g)
2(g) Mg(s)(s)
MgCl
MgCl
2(s) ; ; KKp p0.2
2(s) atm–1
0.2atm
The final pressure of NOCl would be
(A) 7.84 atm (B) 18.06 atm (C) 129.6 atm (D) 64.8 atm.
18. The CaCO3 is heated in a closed vessel of volume 1 litre at 600 K to form CaO and CO 2 . The minimum
weight of CaCO3 required to establish the equilibriumCaCO
CaCO3(s) CaO
3(s)
CaO(s)(s) CO
CO2(g2(g)
) is
(K p 2.25 atm)
(A) 2g (B) 4.57 g (C) 10g (D) 100 g.
19. One mole of N2O(g) is kept in a closed container along with gold catalyst at 450 K under one atmosphere. It
is heated to 900 K when it dissociates to N2(g) and O2(g) giving an equilibrium pressure of 2.4 atm. The degree
of dissociation of N2O(g) is
(A) 20% (B) 40% (C) 50% (D) 60%.
20. KP will be equal to KC under which of the following conditions for the reaction–
aA + bB cC + dD
(A) (a + b) > ( c+ d ) (B) (a + b) – ( c+d ) = 0
(C) (c + d) > ( a+ b ) (D) (a + c) = ( b+d )
22. The value of ng for the reaction : 2Hg(l) + Cl2 (g) Hg2Cl2 (s) is –
(A) – 1 (B) + 2 (C) – 2 (D) 0
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23. For the reaction H2 (g) + I2 (g) 2HI (g) at 721 K, the value of equilibrium constant KC is 50.
When the equilibrium concentration of both is 0.5 M, value of KP under the same conditions will be–
(A) 0.02 (B) 0.2 (C) 50.0 (D) 50/RT
24. For an exothermic reaction in which the number of moles of reactants are more than the number of
moles of products. In order to displace the reaction in the reverse direction, what are the favourable
conditions .
(A) High pressure, low temp. and high conc. of the product
(B) Low pressure, high temp. and high conc. of the products
(C) Low pressure, low temp. and high conc. of the products
(D) High pressure, high temp. and low conc. of the products
28. A 2B, Kp; C D + E; K 'p . If degrees of dissociation of A and C are same and Kp = 2 K 'p , then
the ratio of total pressure p/ p ' = ?
(A) 1/2 (B) 1/3 (C) 1/4 (D) 2
29. For the reaction 2NO2 N2O4, if degrees of association of N2O4 are 25%, 50% 75% and 100%, the
gradation of observed vapour densities is :
(A) d1 > d2 > d3 > d4 (B) d4 > d3 > d2 >d1 (C) d1 = d2 = d3 = d4 (D) None of these
30. N2O4 2NO2, Kc = 4. This reversible reaction is studied graphically as shown in figure. Select the
correct statements out of I, II and III.
A D E
Concentr ation
F G
B Ti me
33. For dissociation of PCl5,mole fraction of Cl2 at equilibrium is 0.3. The total pressure is 1.0 atmosphere.
The partial pressure of PCl3 at equilibrium is –
(A) 1.3 (B) 0.3 (C) 0.7 (D) 0.4
34. The value of KP for the reaction 2H2 S (g) 2H2 (g) + S2 (g) is 1.2 × 10–2 at 1065º C. The value
of KC for this reaction is–
(A) 1.2 × 10–2 (B) < 1.2 × 10–2 (C) 83 (D) > 1.2 × 10–2
36. If KP for the reaction A (g) + 2B (g) 3 C (g) + D (g) is 0.05 atm. at 1000 K. Its KC in
terms of R will be –
5 10 5
(A) 20000 R (B) 0.02 R (C) 5 × 10–5 R (D)
R
37. The equilibrium constant for a reaction N2 (g) + O2 (g) 2NO (g) is 4 × 10–4 at 2000 K. In the
presence of catalyst, the equilibrium is attained 10 times faster. The equilibrium constant in the
presence of catalyst, at 2000 K is –
(A) 40 × 10–4 (B) 4 × 10–4
(C) 4 × 10–2 (D) Difficult to compute without more data
38. At 250º C, the vapour density of PCl5 is Y (at equilibrium) and molar mass is Q (Initially). Its degree
of dissociation is then equal to -
Q–Y Y–Q Y – 2Q Q – 2Y
(A) (B) (C) (D)
Y Q 2Q 2Y
43. In the formation of nitric acid, N2 and O2 are made to combine. Thus
N2 + O 2 2NO – Heat
Which of the following condition will favour the formation of NO –
(A) Low temperature (B) High temperature (C) Freezing point (D) All are favourable
44. The oxidation of SO2 to SO3 by oxygen is an exothermic reaction. The yield of SO3 will be maximum
if –
(A) Temperature is increased and pressure is kept constant
(B) Temperature is reduced and pressure is increased
(C) Both temperature and pressure are increased
(D) Both temperature and pressure are decreased
45. Which of the following conditions will be favourable for the formation of HX according to the gaseous
equilibrium :
H2 X2 + heat 2HX –
(A) High temperature and high pressure (B) High temperature and low pressure
(C) Low temperature and low pressure (D) High pressure and low temperature
46. A (l) + B (l) C (l) + D ( l)
One mole of A and one mole of B are mixed in a volume of one litre. If 0.9 mole per litre of C is found
at equilibrium, the equilibrium constant K is –
(A) 1 (B) 81 (C) 10 (D) 10–1
47. X2(g) + Y2(g) 2XY(g) reaction was studied at a certain temperature. In the beginning 1 mole of X2 was
taken in a one litre flask and 2 moles of Y2 was taken in another 2 litre flask and both these containers are
connected so equilibrium can be established. What is the equilibrium concentration of X2 and Y2? Given
Equilibrium concentration of [XY] = 0.6 moles/litre.
1 2 1 2
(A) 0.3 , 0.3 (B) 0.6 , 0.6
3 3 3 3
(C) (1 – 0.3) , (2 – 0.3) (D) (1 – 0.6) , (2 – 0.6)
48. Ammonia dissociates into N2 and H2 such that degree of dissociation is very less than 1 and equilibrium
pressure is P0 then the value of is [if Kp for 2NH3(g) N2 (g) + 3H2(g) is 27 × 10–8 P02:
(A) 10–4 (B) 4 × 10–4 (C) 0.02 (D) can’t be calculated.
49. At a temperature T, a compound AB4(g) dissociates as 2AB4(g) A2(g) + 4B2(g) with a degree of dissociation
x, which is small compared with unity. The expression of KP in terms of x and total pressure P is ;
(A) 8P3x5 (B) 256P3x5 (C) 4Px2 (D) None of these
51. A 10 litre box contains O3 and O2 at equilibrium at 2000 K. KP = 4 × 1014 atm for 2O3 (g) 3O2(g).
Assume that PO2 PO3 and if total pressure is 8 atm, then partial pressure of O3 will be :
(A) 8 × 10–5 atm (B) 11.3 × 10–7 atm (C) 9.71 × 10–6 atm (D) 9.71 × 10–2 atm
52. For the reaction CaCO3(s) CaO(s) + CO2(g), the pressure of CO2(g) depends on :
(A) the mass of CaCO3(s) (B) the mass of CaO(s)
(C) the masses of both CaCO3(s) and CaO(s) (D) temperature of the system
53. Ammonia gas at 15 atm is introduced in a rigid vessel at 300 K. At equilibrium the total pressure of the vessel
is found to be 40.11 atm at 300ºC. The degree of dissociation of NH3 will be:
(A) 0.6 (B) 0.4 (C) Unpredictable (D) None of these
Dd
56. The equation = is correctly matched for :
(n 1)d
(A) A(g) nB/2(g) + nC/3(g) (B) A(g) nB/3(g) + (2n/3)C(g)
(C) A(g) (n/2)B(g) + (n/4)C(g) (D) A(g) (n/2)B(g) + C(g)
59. For the reaction 3 A (g) + B (g) 2 C (g) at a given temperature , Kc = 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
60. 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) 2NH3(g). The equilibrium constant KP for dissociation of NH3 is:
1 0.5 (1.5) 3 3 3
(A) × (1.5)3 atm–2 (B) 0.5 ×(1.5)3 atm2 (C) atm2 (D) atm–2
0 .5 3 3 0.5 (1.5) 3
66. A 20.0 litre vessel initially contains 0.50 mole each of H2 and I2 gases. These substances react and finally
reach an equilibrium condition. Calculate the equilibrium concentration of HI if Keq = 49 for the reaction H2 +
I2 2HI.
(A) 0.78 M (B) 0.039 M (C) 0.033 M (D) 0.021 M
68. At 675 K, H2(g) and CO2 (g) react to form CO(g) and H2O (g), Kp for the reaction is 0.16.
If a mixture of 0.25 mole of H2(g) and 0.25 mol of CO2 is heated at 675 K, mole % of CO(g) in equilibrium
mixture is :
(A) 7.14 (B) 14.28 (C) 28.57 (D) 33.33
69. In which of the following reactions, increase in the pressure at constant temperature does not affect the
moles at equliibrium :
1
(A) 2NH3(g) N2(g) + 3H2(g) (B) C(g) + O (g) CO(g)
2 2
1
(C) H2(g) + O (g) H2O(g) (D) H2(g) + I2(g) 2HI(g)
2 2
70. The exothermic formation of ClF3 is represented by the equation :
Cl2(g) + 3F2(g) 2ClF3(g) H = – 329 kJ
Which of the following will increase the quantity of ClF3 in an equilibrium mixture of Cl2, F2 and ClF3 :
(A) Increasing the temperature (B) Removing Cl2
(C) Increasing the volume of container (D) Adding F2
72. The equilibrium SO2Cl2(g) 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
75. What is the effect of the reduction of the volume of the system for the equilibrium 2C(s) + O2(g) 2CO (g)?
(A) The equilibrium will be shifted to the left by the increased pressure caused by the reduction in volume.
(B) The equilibrium will be shifted to the right by the decreased pressure caused by the reduction in volume.
(C) The equilibrium will be shifted to the left by the increased pressure caused by the increase in volume.
(D) The equilibrium will be shifted to the right by the increased pressure caused by the reduction in volume.
76. The vapour density of N2O4 at a certain temperature is 30. What is the % dissociation of N2O4 at this
temperature?
(A) 53.3% (B) 106.6% (C) 26.7% (D) None of these
77. The equilibrium constant KP (in atm) for the reaction is 9 at 7 atm and 300 K.
A2 (g) B2(g) + C2 (g)
Calculate the average molar mass (in gm/mol) of an equilibrium mixture.
Given : Molar mass of A2, B2 and C2 are 70, 49 & 21 gm/mol respectively.
(A) 50 (B) 45 (C) 40 (D) 37.5
80. When N2O5 is heated at temp. T, it dissociates as N 2 O 5 N 2 O 3 O 2 , Kc = 2.5. At the same time N2O3
also decomposes as : N2O3 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
87. For the equilibrium 2SO2(g) + O2(g) 2SO3(g), H = -198 kJ, the equilibrium concentration of SO3 will
be affected by
(A) doubling the volume of the reaction vessel
(B) increasing the temperature at constant volume
(C) adding more oxygen to the reaction vessel
(D) adding helium to the reaction vessel at constant volume
88. The following reaction attains equilibrium at high temperature
N2(g) + 2H2O(g) + heat 2NO(g) + 2H2(g)
The yield of NO is affected by
(A) increasing the nitrogen concentration (B) decreasing the hydrogen concentration
(C) compressing the reaction mixture (D) none of these
89. N2(g) + 3H2(g) 2NH3 + heat
In this reaction, the direction of equilibrium will be shifted to the right by
(A) increasing the concentration of nitrogen (B) compressing the reaciton mixture
(C) removing the catalyst (D) decreasing the concentration of ammonia
N2(g) + 3H2(g) 2NH3 + heat
92. Which of the following factors will increase solubility of NH3(g) in H2O?
NH3(g) + H2O(aq) NH4OH(aq)
(A) increase in pressure (B) addition of water.
(C) liquefaction of NH3 (D) decrease in pressure
93. Which of the following factors will affect solubility of CaO in H2O?
(A) pressure (B) temperature (C) addition of water (D) volume
97. The reactions in which the yield of the products cannot be increased by the application of high pressure
(A) 2SO2(g) + O2(g) 2SO3(g) (B) NH4HS(s) NH3(g) + H2S(g)
(C) N2O4(g) 2NO2(g) (D) N2(g) + 3H2(g) 2NH3(g)
1 1
(iv) NO(g) N (g) + O (g) ; K4
2 2
2 2
Correct relation between K1, K2 and K4 is/are :
(A) K1 × K3 = 1 (B) K1 K 4 = 1 (C) K3 K2 = 1 (D) None
99. When NaNO3 is heated in a closed vessel, oxygen is liberated and NaNO2 is left behind. At equilibrium,
1
NaNO3 (s) NaNO2 (s) + O (g)
2 2
(A) addition of NaNO2 favours reverse reaction
(B) addition of NaNO3 favours forwards reaction
(C) increasing temperature favours forward reaction
(D) increasing pressure favours reverse reaction
101. For the reaction PCl5(g) 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) introducing PCl5 at constant volume.
102. 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
103. For the gas phase reaction, C2H4 + H2 C2H6 (H = – 32.7 kcal), carried out in a closed vessel, the
equilibrium moles of C2H4 can be increased by
(A) increasing the temperature (B) decreasing the pressure
(C) removing some H2 (D) adding some C2H6
104. For the gas phase exothermic reaction, A2 + B2 C2, carried out in a closed vessel, the equilibrium moles
of A2 can be increased by
(A) increasing the temperature (B) decreasing the pressure
(C) adding inert gas at constant pressure (D) removing some C2
105. Consider the equilibrium HgO(s) + 4I– (aq) + H2O (l) HgI42– (aq) + 2OH– (aq), which changes will decrease
the equilibrium concentration of HgI42–
(A) Addition of 0.1 M HI (aq) (B) Addition of HgO (s)
(C) Addition of H2O (l) (D) Addition of KOH (aq)
106. Decrease in the pressure for the following equilibria : H2O (s) H2O(l) result in the :
(A) formation of more H2O (s) (B) formation of more H2O(l)
(C) increase in melting point of H2O(s) (D) decrease in melting point of H2O(s)
1
1. For the reaction NOBr (g) NO(g) +
Br2 (g)
2
KP = 0.15 atm at 90°C. If NOBr, NO and Br2 are mixed at this temperature having partial pressures 0.5 atm,
0.4 atm and 0.2 atm respectively, will Br2 be consumed or formed ?
2. The KP values for three reactions are 10–5 , 20 and 300 then what will be the correct order of the percentage
composition of the products.
3. 1 mole of N2 and 3 moles of H2 are placed in 1L vessel. Find the concentration of NH3 at equilibrium, if
4
equilibrium pressure is 1 atm and the equilibrium constant at 400K is
27
4. The value of Kc for the reaction, N2(g) + 2O2(g) 2NO2(g) at a certain temperature is 400. calcualte the
value of equilibrium constant for.
(i) 2NO2(g) N2(g) + 2 O2(g) ; (ii) 1/2 N2(g) + O2(g) NO2(g)
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5. From the following data :
(i) H2(g) + CO2(g) H2O(g) + CO(g)
K2000K = 4.4
6. In an experiment starting with 1 mole of ethyl alcohol, 1 mole of acetic acid and 1 mole of water at T0C, the
equilibrium mixture on analysis shows that 54.3% of the acid is esterfied. Calculate the equilibrium constant
of this reaction.
8. The degree of dissociation at a certain or given temperature of PCl5 at 2 atm is found to be 0.4. At
what pressure, the degree of dissociation of PCl5 will be 0.6 at the same temperature? Also calculate
the equilibrium constant for the reverse reaction.
9. (i) Calculate the percentage dissociation of H2S(g), if 0.1 mole of H2S is kept in 0.4 litre vessel at
1000K. For the reaction, 2H2S(g) 2H2(g) + S2(g), the value of Kc = 1.6 × 10–6
(ii) A sample of HI was found to be 22% dissociated when equilibrium was reached. What will be the
degree of dissociation if hydrogen is added in the proportion of 1 mole for every mole of HI originally
present, the temperature and volume of the system being kept constant?
10. Calculate the degree of dissociation and Kp for the following reaction.
PCl5(g) PCl3(g) + Cl2(g)
t=0 a 0 0
t=t a –x x x
Since for a mole, x moles are dissociated
11. The vapour density of PCl5 at 250ºC is found to be 57.9. Calculate percentage dissociation at this
temperature.
12. The vapour density of a mixture containing NO2 and N2O4 is 38.3 at 33°C calculate the no. of moles of
NO2 if 100g of N2O4 were taken initially.
13. What is the effect on the following equilibrium if each of the indicated stresses is applied?
1
N2(g) +O2(g) NO 2(g) + heat
2
(a) Increase in N2 concentration
(b) Decrease in temperature
(c) Increase in volume of vessel
(d) addition of a catalyst
15. Calculate the pressure of CO 2 gas at 700K in the heterogeneous equilibrium reaction
CaCO3(s) CaO(s) + CO2(g) if G0 for this reaction is 130.2 kJ mol–1.
16. For the equilibrium NiO(s) + CO(g) Ni(s) + CO2(g), G0 (J mol–1) = – 20,700 – 11.97 T. Calculate
the temperature at which the product gases at equilibrium at 1 atm will contain 400 ppm (parts per
million) of carbon monoxide.
17. (i) Calculate the partial pressure of HCl gas above solid a sample of NH4Cl(s) as a result of its
decomposition according to the reaction:
NH4Cl(s) NH3(g) + HCl(g) Kp = 1.04 × 10–16
(ii) Calculate the equilibrium constant of a reaction at 300 K if G0 at this temperature for the
reaction is 29.29 kJ mol–1.
18. For the formation of ammonia the equilibrium constant data at 673K and 773K respectively are
1.64 × 10–4 and 1.44 × 10–5 respectively. Calculate heat of the reaction. Given R=8.314 JK–1mol–1.
19. The equilibrium constant KP for the reaction N2(g) + 3H2(g) 2NH3(g) is 1.6 10-4 atm at
400oC. What will be the equilibrium constant at 500oC if heat of the reaction in this temperature
range is 25.14 k cal?
20. The equilibrium constant for the reaction H2 + I2 2HI; is found to be 64 at 450°C. If 6 mole of hydrogen
are mixed with 3 mole of iodine in a litre vessel at this temperature; what will be the concentration of each
of the three components, when equilibrium is attained ? If the volume of reaction vessel is reduced to half;
then what will be the effect on equilibrium?
21. 5 gm of PCl5 were completely vaporized at 250°C in a vessel of 1.9 litre capacity. The mixture at equilibrium
exerted a pressure of one atmosphere. Calculate the degree of dissociation KC and Kp for this reaction.
22. If a mixture of N2 and H2 in the ratio 1 : 3 at 50 atmosphere and 650°C is allowed to react till equilibrium is
reached. Ammonia present at equilibrium was at 25 atm pressure. Calculate the equilibrium constant for
the reaction. N2(g) + 3H2(g) 2NH3(g)
23. 0.96 g of HI were heated to attain equilibrium 2HI(g) H2 (g) + I2(g). The reaction mixture on titration
requires 15.7 mL of N/10 hypo solution. Calculate degree of dissociation of HI.
24. Would 1% CO2 in air be sufficient to prevent any loss in weight when M2CO3 is heated at 120oC ?
M2CO3(s) M2O(s) + CO2(s)
Kp = 0.0095 atm at 120oC. How long would the partial pressure of CO2 have to be to promote this reaction
at 120oC ?
25. In a container of constant volume at a particular temparature N2 and H2 are mixed in the molar ratio of 9:13.
The following two equilibria are found to be coexisting in the container
N2 (g) + 3H2 (g) 2NH3 (g)
N2 (g) + 2H2 (g) N2H4 (g)
The total equilibrium pressure is found to be 3.5 atm while partial pressure of NH3 (g) and H2(g) are 0.5 atm
and 1 atm respectively. Calculate of equilibrium constants of the two reactions given above.
27. For the reaction Ag(CN)2– Ag+ + 2CN–, the KC at 25°C is 4 10–19. Calculate [Ag+] in solution which
was originally 0.1 M in KCN and 0.03 M in AgNO3.
28. When baking soda is heated in a sealed tube, following equilibrium exits:
2NaHCO3(s) Na2CO3(s) + CO2(g) + H2O(g)
If the equilibrium pressure is 1.04 atm at 398 K, calculate the equilibrium constant for the reaction at 398 K.
1 3
NH3(g) N2(g) + H2(g)
2 2
Show that degree of dissociation of NH3 is given as :
1 / 2
3 3 P
1
4 K p
where ‘P’ is equilibrium pressure. If Kp of the above reaction is 78.1 atm at 400°C, calculate KC.
30. (i) The vapour density of a mixture consisting of NO2 and N2O4 is 38.3 at 26.7°C. Calculate the
number of moles of NO2 in 100 gm mixture.
(ii) Establish a relationship between Kc and Kp for the following reactions.
(a) N2(g) + O2(g) 2NO(g)
(b) (NH4 4)2
(NH )2CO
CO3(s)
3(s) 2NH2NH + CO
3(g)3(g) + CO 2(g)2+
2(g) +H OH(g) 2 O(g)
31. Calculate the Kc and Kp for the following reactions and also deduce the relationship between Kc
and Kp
1 3
(i) 2SO2(g) + O2(g) 2SO3(g) (ii) N2(g) + H2(g) NH3(g)
2 2
2. For a chemical reaction 3X(g) + Y(g) X3 Y(g), the amount of X3 Y at equilibrium is affected by
[JEE-1999, 2/80]
(A) temperature and pressure (B) temperature only
(C) pressure only (D) temperature, pressure and catalyst
3. For the reversible reaction, N 2 (g) + 3H 2(g) 2NH 3 at 500°C, the value of K P is 1.44 × 10 –5 when
partial pressure is measured in atmospheres. The corresponding value of K C, with concentration in
mole litre –1, is [JEE 2000, 1/35]
4. When two reactants, A & B are mixed to give products C & D, the reaction quotient Q, at the initial stages of
the reaction. [JEE-2000, 1/35]
(A) is zero (B) decrease with time
(C) is independent of time (D) increases with time
5. At constant temperature, the equilibrium constant (KP) for the decomposition reaction N2O4 2NO2 is
2
( 4 x P)
expressed by KP = , where P = pressure, x = extent of decomposition. Which one of the following
(1 x 2 )
statements is true ? [JEE 2001, 1/35]
(A) KP is increases witn increase of P (B) KP is increases witn increase of x
(C) KP is increases witn decrease of x (D) KP remains constant with change in P and x
9. STATEMENT-1 : For every chemical reaction at equilibrium, standard Gibbs energy of reaction is zero.
STATEMENT-2 : At constant temperature and pressure, chemical reactions are spontaneous in the direction
of decreasing Gibbs energy. [JEE 2008, 3/163]
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for Statement-1.
(C) Statement-1 is True, Statement-2 is False.
(D) Statement-1 is False, Statement-2 is True.
(E) Statement-1 and Statement-2 both are False.
10.* The thermal dissociation equilibrium of CaCO3(s) is studied under different conditions :
CaCO3(s) CaO(s) + CO2(g) [JEE_2013]
For this equilibrium, the correct statement(s) is(are)
(A) H is dependent on T
(B) K is independent of the initial amount of CaCO3
(C) K is dependent on the pressure of CO2 at a given T
(D) H is independent of the catalyst, if any
11. The Ksp of Ag2CrO4 is 1.1 × 10–12 at 298 K. The solubility (in mol/L) of Ag2CrO4 in a 0.1 M AgNO3 solution is:
[JEE_2013]
(A) 1.1 × 10–11
(B) 1.1 × 10 –10
(C) 1.1 × 10 –12
(D) 1.1 × 10 –9
1. Change in volume of the system does not alter the number of moles in which of the following equilibriums :
[AIEEE 2002]
(1) N2(g) + O2(g) 2NO(g) (2) PCl5(g) PCl3(g) + Cl2(g)
(3) N2(g) + 3H2(g) 2NH3(g) (4) SO2Cl2(g) SO2(g) + Cl2(g)
2. In which of the following reactions, increase in the volume at constant temperature don’t effect the number of
moles of at equilibrium : [AIEEE 2002]
(1) 2NH3 N2 + 3H2 (2) C (g) + (1/2) O2 (g) CO (g)
(3) H2 (g) + O2 (g) H2O2 (g) (4) none of these
4. For the reaction equilibrium, N2O4 (g) 2NO2 (g) the concentrations of N2O4 and NO2 at equilibrium are
4.8 × 10–2 and 1.2 × 10–2 mol L–1 respectively. The value of Kc for the reaction is [AIEEE 2003]
2 3
(1) 3.3 × 10 mol L –1
(2) 3 × 10 mol L
–1 –1
(3) 3 × 10 mol L
–3 –1
(4) 3 × 10 mol L–1
6. For the reaction, CO(g) + Cl2 (g) COCl2 (g) then Kp / Kc is equal to : [AIEEE 2004]
(1) 1/RT (2) 1.0 (3) RT (4) RT
7. The equilibrium constant for the reaction, N2 (g) + O2 (g) 2NO(g) at temperature T is 4 × 10–4 . The value
1 1
of Kc for the reaction, NO(g) N2 (g) + O (g) at the same temperature is [AIEEE 2004]
2 2 2
1 1
NO(g) N (g) + O (g)
2 2 2 2
(1) 2.5 × 102 (2) 0.02 (3) 4 × 10–4 (4) 50
10. An amount of solid NH4HS is placed in a flask already containing ammonia gas at a certain temperature at
0.50 atm pressure. Ammonium hydrogen sulphide decomposes to yield NH3 and H2S gases in the flask.
When the decomposition reaction reaches equilibrium, the total pressure in the flask rises to 0.84 atm? The
equilibrium constant for NH4HS decomposition at this temperature is : [AIEEE 2005]
(1) 0.11 (2) 0.17 (3) 0.18 (4) 0.30
x 2x x x
(1) P (2) P (3) P (4) P
x 1 1– x x 1 1– x
1
12. The equilibrium constant for the reaction, SO3(g) SO2(g) + O (g)
2 2
is KC = 4.9 × 10–2. The value of KC for the reaction 2SO2(g) + O2(g) 2SO3(g) will be [AIEEE 2006]
(1) 416 (2) 2.40 × 10–3 (3) 9.8 × 10–2 (4) 4.9 × 10–2
13. For the following three reactions a, b and c, equilibrium constants are given:
(A) CO(g) + H2O(g) CO2(g) + H2(g); K1
(B) CH4(g) + H2O(g) CO(g) + 3H2(g); K2
(C) CH4(g) + 2H2O(g) CO2(g) + 4H2(g); K3
Which of the following relations is correct ? [AIEEE 2008, 3/105]
(1) K2 K3 = K1 (2) K3 = K1K2 (3) K3 K23 = K12 (4) K 1 K 2 K 3
ratio of 1 : 9. If the degree of dissociation of X and Z be equal then the ratio of total pressures at these
equilibria is [AIEEE 2008, 3/105]
(1) 1 : 1 (2) 1 : 3 (3) 1 : 9 (4) 1 : 36
15. If 10–4 dm3 of water is introduced into a 1.0 dm3 flask at 300 K, how many moles of water are in the vapour
phase when equilibrium is established ? [AIEEE 2010, 4/144]
(Given : Vapour pressure of H2O at 300 K is 3170 Pa ; R= 8.314 J K–1 mol–1)
(1) 5.56 × 10–3 mol (2) 1.53 × 10–2 mol (3) 4.46 × 10–2 mol (4) 1.27 × 10–3 mol
16. A vessel at 1000 K contains CO2 with a pressure of 0.5 atm. Some of the CO2 is converted into CO on the
addition of graphite. If the total pressure at equilibrium is 0.8 atm, the value of K is : [AIEEE 2010, 4/144]
(1) 1.8 atm (2) 3 atm (3) 0.3 atm (4) 0.18 atm
NCERT QUESTIONS
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 ?
2. 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)
3. At a certain temperature and total pressure of 105Pa, iodine vapour contains 40% by volume of I atoms
I2 (g) 2I (g)
Calculate Kp for the equilibrium.
4. Write the expression for the equilibrium constant, Kc for each of the following reactions:
(i) 2NOCl (g) 2NO (g) + Cl2 (g)
(ii) 2Cu(NO3)2 (s) 2CuO (s) + 4NO2 (g) + O2 (g)
(iii) CH3COOC2H5 (aq) + H2O(l) CH3COOH (aq) + C2H5OH (aq)
3
(iv) Fe + (aq) + 3OH (aq)
– Fe(OH)3(s)
(v) I2 (s) + 5F2 2IF5
5. Find out the value of Kc for each of the following equilibria from the value of Kp :
(i) 2NOCl (g) 2NO (g) + Cl2 (g); Kp = 1.8 × 10–2 at 500 K
(ii) CaCO3 (s) CaO(s) + CO2(g); Kp = 167 at 1073 K
7. Explain why pure liquids and solids can be ignored while writing the equilibrium constant expression?
10. At 450K, Kp = 2.0 × 1010 bar for the given reaction at equilibrium.
2SO2(g) + O2(g) 2SO3 (g)
What is Kc at this temperature ?
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 ?
2HI (g) H2 (g) + I2 (g)
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 N2 (g) + 3H2 (g) 2NH3 (g) is 1.7
2
10 . Is the reaction mixture at equilibrium ? If not, what is the direction of the net reaction ?
[NH3 ]4 [O2 ]5
kc
[NO]4 [H2 O]6
Write the balanced chemical equation corresponding to this expression.
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,
H2O (g) + CO (g) H2 (g) + CO2 (g)
Calculate the equilibrium constant for the reaction.
assuming that we initially started with H2(g) HI(g) allowed it to reach equilibrium at 700K ?
16. What is the equilibrium concentration of each of the substances in the equilibrium when the initial concentration
of ICl was 0.78 M ?
2ICl (g) I2 (g) + Cl2 (g); Kc = 0.14
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 ?
C2H6 (g) C2H4 (g) + H2 (g)
18. Ethyl acetate is formed by the reaction between ethanol and acetic acid and the equilibrium is represented as :
CH3COOH (l) + C2H5OH (l) CH3COOC2H5 (l) + H2O (l)
(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 ?
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 ?
PCl5 (g) PCl3 (g) + Cl2 (g)
22. Bromine monochloride, BrCl decomposes into bromine and chlorine and reaches the equilibrium :
2BrCl (g) Br2 (g) + Cl2 (g)
for which Kc = 32 at 500 K. If initially pure BrCl is present at a concentration of 3.3 × 10–3 mol L–1, what is its
molar concentration in the mixture at equilibrium ?
23. At 1127 K and 1 atm pressure, a gaseous mixture of CO and CO2 in equilibrium with soild carbon has
90.55% CO by mass
C (s) + CO2 (g) 2CO (g)
Calculate Kc for this reaction at the above temperature.
Calculate a) f G and b) the equilibrium constant for the formation of NO2 from NO and O2 at 298K
24.
NO (g) + 1/2O2 (g) NO2 (g)
f G (NO2) = 52.0 kJ/mol
f G (O2) = 0 kJ/mol
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) PCl5 (g) PCl3 (g) + Cl2 (g)
(b) CaO (s) + CO2 (g) CaCO3 (s)
(c) 3Fe (s) + 4H2O (g) Fe3O4 (s) + 4H2 (g)
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) COCl2 (g) CO (g) + Cl2 (g)
(ii) CH4 (g) + 2S2 (g) CS2 (g) + 2H2S (g)
(iii) CO2 (g) + C (s) 2CO (g)
(iv) 2H2 (g) + CO (g) CH3OH (g)
(v) CaCO3 (s) CaO (s) + CO2 (g)
(vi) 4 NH3 (g) + 5O2 (g) 4NO (g) + 6H2O(g)
27. The equilibrium constant for the following reaction is 1.6 × 105 at 1024K
H2(g) + Br2(g) 2HBr(g)
Find the equilibrium pressure of all gases if 10.0 bar of HBr is introduced into a sealed container at 1024K.
28. Dihydrogen gas is obtained from natural gas by partial oxidation with steam as per following endothermic
reaction :
CH4 (g) + H2 O (g) CO (g) + 3H2 (g)
(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 ?
30. At 473 K, equilibrium constant Kc for decomposition of phosphorus pentachloride, PCl5 is 8.3 × 10-3. If
decomposition is depicted as,
PCl3 (g) + Cl2 (g) r H = 124.0 kJ mol–1
PCl5 (g)
(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 ?
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,
CO (g) + H2O (g) CO2 (g) + H2 (g)
If a reaction vessel at 400 °C is charged with an equimolar mixture of CO and steam such that pCO = pH O =
2
4.0 bar, what will be the partial pressure of H2 at equilibrium ? Kp = 10.1 at 400°C
32. Predict which of the following reaction will have appreciable concentration of reactants and products:
(a) Cl2 (g) 2Cl (g) Kc = 5 × 10–39
(b) Cl2 (g) + 2NO (g) 2NOCl (g) Kc = 3.7 × 108
(c) Cl2 (g) + 2NO2 (g) 2NO2Cl (g) Kc = 1.8
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 , what is the concentration of O3 ?
–2
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.
EXERCISE # 2
1. (C) 2. (B) 3. (A) 4. (C) 5. (B) 6. (B) 7. (A)
8. (B) 9. (B) 10. (C) 11. (B) 12. (A) 13. (B) 14. (B)
15. (D) 16. (C) 17. (B) 18. (B) 19. (B) 20. (B) 21. (A)
22. (A) 23. (C) 24. (B) 25. (B) 26. (A) 27. (C) 28. (A)
29. (B) 30. (B) 31. (A) 32. (A) 33. (B) 34. (B) 35. (C)
36. (D) 37. (B) 38. (D) 39. (A) 40. (A) 41. (B) 42. (A)
43. (B) 44. (B) 45. (B) 46. (B) 47. (A) 48. (C) 49. (A)
50. (B) 51. (B) 52. (D) 53. (B) 54. (B) 55. (D) 56. (B)
57. (A) 58. (C) 59. (A) 60. (B) 61. (B) 62. (D) 63. (A)
64. (A) 65. (B) 66. (B) 67. (A) 68. (B) 69. (D) 70. (D)
71. (C) 72. (A) 73. (B) 74. (D) 75. (A) 76. (A) 77. (C)
78. (C) 79. (A) 80. (D) 81. (A) 82. (AB) 83. (BD)
84. (ABCD) 85. (AB) 86. (AC) 87. (ABC) 88. (ABC) 89. (ABD) 90. (BCD)
91. (BC) 92. (AB) 93. (B*C) 94. (ACD) 95. (ABCD) 96. (BCD) 97. (BC)
98. (ABC) 99. (CD) 100. (BCD) 101. (CD) 102. (CD) 103. (ABCD) 104. (ABC)
105. (CD) 106. (AC)
16 x 2 ( 2 x ) 2
5. reaction is exothermic. 6. 4.0 7. 8. 0.677 atm
27(1 x ) 4 P 2
2 . P
9. (i) 2.34% (ii) 0.29 10. KP = 11. 80% 12. 0.435
1 2
13. (a) Right (b) Right (c) Left (d) No shift will occur
14. – 19.67 lit atm 15. 1.94 × 10–10 atm 16. T = 399K.
17. (i) 1.02
× 10 atm –8
(ii) 7.91 × 10 –6
18. – 105.216kJ
19. 1.43 × 10–5 20. 0.16 21. 1 22. 1.677 10–3
23. 0.209 24. – 0.0005. 25. 0.6 atm–2 26. 708
27. 7.5 10–18 28. 0.2704 atm 29. 1.413 moles litre–1
1. (i) 8.1 10 5 mol/, 0.049 atm2 (ii) No change. 2. (A) 3. (D) 4. (D)
5. (D) 6. (D) 7. (B) 8. (B) 9. (D) 10.* (ABD)
11. (B)
PART # II
1. (1) 2. (4) 3. (3) 4. (3) 5. (2) 6. (1) 7. (4)
8. (4) 9. (1) 10. (1) 11. (1) 12. (1) 13. (2) 14. (4)
15. (4) 16. (1)
EXERCISE # 4
2. 12.229 3. 2.67 × 104 5. (i) 4.33 × 10–4 (ii) 1.90 6. 1.59 × 10–15
8. [N2] = 0.0482 mol L–1, [O2] = 0.0933 mol L–1, [N2O] = 6.6 × 10–21 mol L–1
9. 0.0352 mol of NO and 0.0178 mol of Br2 10. 7.47 × 1011 M–1 11. 4.0
12. Qc = 2.379 × 103. No, reaction is not at equilibrium. 14. 0.44
15. 0.068 mol L eact of H2 and I2 16.
–1 [I2] = [Cl2] = 0.167 M, [ICI] = 0.446 M
17. [C2H6]eq = 3.62 atm
18. (i) [CH3COOC2H5] [H2O] / [CH3COOH] [C2H6OH] (ii) 3.92
(iii) Value of Qc is less than Kc therefore equilibrium is not attained.
19. 0.02 mol L–1 for both. 20. [PCO] = 1.739 atm, [PCO2] = 0.461 atm
21. No, the reaction proceeds to form more products. 22. 3 × 10–4 mol L–1 23. 0.149
24. (a) – 35.0( kJ, (b) 1.365 × 10 6 27. [PH ]eq = [PH ]eq = 2.5 × 10 bar, [PHBr] = 10.0 bar
–2
2 2
30. (b) 120.48 31. [H2]eq = 0.96 bar 33. 2.86 × 10–28 M 34. 5.85 × 10–2