Lec.

Rana Hassan Tariq

Chapter 8
CHEMICAL EQUILIBRIUM
SOLVED OBJECTIVE EXERCISE
Q1: Multiple choice question:
(i) For which system does the equilibrium constant Kc has a unit of (concentration)1?
(a) N 2 3H 2 2NH3
(b) H 2 I2 2HI
(c) 2NO2 N2O4
(d) 2HF H2 + F2
(ii) Which statement about the following equilibrium is correct
2SO2(g) + O2(g) 2SO3(g) H = 188.3 KJ mol1.
(a) The value of Kp falls with rise in temperature
(b) Value of Kp falls with increases in pressure
(c) Adding V2O5 catalyst increase the equilibrium yield of sulphur
trioxide
(d) Value of Kp is equal to Kc
(iii) The pH of 103 mol dm3 of an aqueous solution of H2SO4 is:
(a) 3.0 (b) 2.7
(c) 2.0 (d) 1.5
(iv) Solubility product of AgCl is 2.0 1010 mol2 dm6 Maximum concentration of Ag+1 ions in
solution is:
(a) 2.0 1010 mol dm3 (b) 1.4 105 mol dm3
(c) 1.0 1010 mol dm3 (d) 4.0 1020 mol dm3
(v) An excess of aqueous silver nitrate is added to aqueous barium chloride and precipitate is
removed by filtration. What are main ions in filtrate:
(a) Ag+, NO13 only (b) Ag+, Ba+2, NO13
(c) Ba+2, NO13 only (d) Ba+2, NO13, Cl1

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ANSWERS
(i) c (ii) a (iii) b (iv) b (v) b
Q2: Fill in the blanks:
(i) Law of mass action states that the ________ at which a reaction precedes is directly
proportional to the product of active masses of ________.
(ii) In an exothermic reversible reaction ________ temperature will shift equilibrium towards the
forward direction.
(iii) The equilibrium constant for a reaction 2O3 3O2 is 1055 at 25o C, it tells that ozone is
________ at room temperature.
(iv) In a gas phase reaction, if the number of moles of reactants are equal to the number of moles of
product, Kc of reaction is ________ to Kp.
(v) Buffer solution is prepared by mixing together a weak base, and its salt with ________ or a
weak acid and its salt with ________.
ANSWERS
(i) rate of reaction, reactants (ii) low temperature
(iii) unstable (iv) equal
(v) strong acid, strong base

Q 3: Label the sentences as true or False:

(i) When a reversible reaction attains equilibrium both reactants and products are present in the
reaction mixture.
[C][D]
(ii) The Kc for the reaction A + B C + D is given as Kc = [A][B] so it is assumed that [A] = [B]
= [C] = [D].
(iii) A catalyst is a compound which speeds up reaction and consequently increases yield of product.
(iv) Ionic product Kw of pure water at 25oC is 1014 mol2 dm6 and is represented by an expression
Kw = [H+][OH] = 1014 mol2 dm6.
(v) AgCl is sparingly soluble ionic solid in water. Its solution contains excess of Ag+ and Cl ions.
ANSWERS
(i) True (ii) False (iii) False (iv) True (v) False
 Lec. Rana Hassan Tariq

ADDITIONAL MCQS
1. Rate of chemical reaction is directly proportional to product of molar concentrations of:
(a) Reactants (b) Products
(c) Both of them (d) None of them
2. Law of mass action was given by:
(a) Goldstein (b) Lechatelier
(c) Goldberg & Waage (d) Ostwald
3. Chemical reactions which proceeds only in one direction are:
(a) Reversible (b) Irreversible
(c) Non-spontaneous (d) None of these
4. If the reactant and products are in same physical states then equilibrium is called.
(a) Chemical equilibrium (b) Dynamic equilibrium
(c) Homogenous equilibrium (d) Static equilibrium
5. If the reactants and products are in different physical states then the equilibrium established is
called.
(a) Heterogeneous equilibrium (b) Static equilibrium
(c) Homogenous equilibrium (d) Dynamic equilibrium
6. Unit of concentration generally taken is:
(a) mol1 dm3 (b) mol dm3
(c) mol2 dm6 (d) mol2 dm6
7. When the rate of forward reactions becomes equal to rate of backward reaction, a system is said
to be in a state of:
(a) Homogenous equilibrium (b) Heterogeneous equilibrium
(c) Static equilibrium (d) Dynamic equilibrium
8. 2 HI(g) H2(g) + I2(g) Unit for Kc for the above reaction is:
(a) mol dm3 (b) mol2 dm6
(c) mol dm3 (d) No unit
9. In the above reaction, the forward reactions speed can be increased by adding:
(a) H2O (b) H2
(c) HI (d) I2
10. For which value of Kc, the forward reaction is almost complete:
(a) 1010 (b) 1030
(c) 100 (d) 1055

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11. Direction and extent of a chemical reaction can easily be given by:
(a) Rydbergs constant (b) Rate constant
(c) Equilibrium constant (d) Planck constant
12. Unit of equilibrium constant for the following reaction is:
N2(g) + 3H2 2NH3(g)
(a) mol dm3 (b) g dm3
(c) mol2 dm6 (d) mol2 dm6
13. Ethanol and ethanoic acid (acetic acid) can react together in the presence of some mineral acid
to produce water and:
(a) Ester (b) Aldehyde
(c) Ketone (d) Alcohol
14. Writing equilibrium constants, concentration of products are written as:
(a) Exponent (b) Denominator
(c) Numerator (d) None of these
15. Correct relationship b/w Kc and Kp can be written as:
(a) Kp = Kc (R)n (b) Kc = Kp (RT)n
(c) Kp = Kc (RT)n (d) Kp = Kc (R/N)n
16. Which of the following reactions has no unit for Kc:
(a) PCl5(g) PCl3(g) + Cl2(g) (b) H2(g) + I2(g) 2HI(g)
(c) 3H2(g) + N2(g) 2NH3(g) (d) 2SO2(g) + O2(g) 2SO3(g)
17. From the above options, which reaction has a unit of (mol dm3):
(a) a (b) b
(c) c (d) d
18. If ratio of [Product]/[Reactant] = Kc then reaction moves in a direction:
(a) Towards right (b) Towards left
(c) Remains at equilibrium (d) None of these
19. Kp = Kc (RT)n. In this equation possibility of Kp = Kc when n is equal to a value of:
(a) Positive integer (b) Negative integer
(c) One (d) Zero
20. If n is positive then by increasing the pressure reaction will move towards:
(a) Right (b) Left
(c) Remains in center (d) None of these
 Lec. Rana Hassan Tariq

21. 2O3(g) 3O2(g) Kc = 1055 at 25o C tells that decomposition of O3 at room temperature into
oxygen molecule is:
(a) Zero (b) Complete
(c) Incomplete (d) None of these
22. In a non-equimolar gaseous equilibrium mixture, the change in volume can be effected by
changing:
(a) Temperature (b) Pressure
(c) Concentration (d) Catalyst addition
23. Effect on equilibrium by adding a catalyst is:
(a) No effect on it (b) Equilibrium shifts to right
(c) Equilibrium quickly (d) Equilibrium shifts to left
established
24. At equilibrium an exothermic reaction is favoured by:
(a) Boiling (b) Cooling
(c) Compressing (d) None of these
25. If stress is applied to a system at equilibrium, system acts is such a way as to nullify the effect of
that change. This is statement of:
(a) Ostwalds law (b) Le Chateliers principle
(c) Hesss law (d) Law of mass action
26. What would be direction of reaction, if one of the reactant is removed at equilibrium?
(a) Forwards (b) Remain unchanged
(c) Backwards (d) Not predictable
27. CO(g) + H2O(g) H2(g) + CO2(g) H = 41.84 KJ mol1. According to Le Chateliers
principle, forward reaction is favoured by:
(a) Increasing Pressure (b) Decreasing Pressure
(c) Increasing Temperature (d) Decreasing Temperature
28. PCl5(g) PCl3(g) + Cl2(g). At equilibrium, concentration of chlorine gas can be increased by:
(a) Adding PCl5 (b) Adding PCl3
(c) Increasing temperature (d) None of these
29. Catalyst merely speeds up establishment of equilibrium by lowering:
(a) Enthalpy (b) Entropy
(c) Internal energy (d) Activation energy
30. Effect of pressure is not applicable to a system of:
(a) Equimolar gases (b) Solids
(c) Liquids (d) All of these

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31. For Habers process low temperature is fovourable for:

(a) Forward reaction (b) Backward reaction
(c) Equilibrium (d) None of these
32. Optimum temperature for the manufacture of NH3 by Habers process is:
(a) 300o C (b) 400o C
(c) 500o C (d) 600o C
33. Optimum pressure during NH3 manufacture is:
(a) 200300 atm (b) 300400 atm
(c) 400500 atm (d) 500500 atm
34. Catalyst used in Habers process:
(a) Finely divided Ni (b) V2O5
(c) NO2 (d) iron crystals in MgO,
Al2O3, SiO2
35. 80% of produced NH3 is utilized in the manufacture of:
(a) Explosives (b) Nylon
(c) Fertilizers (d) All of them
36. King of chemicals is:
(a) NH3 (b) HCl
(c) H2SO4 (d) NaOH
37. A catalyst used in production of SO3 in contact process is:
(a) Finely divided Ni (b) V2O5
(c) Pt metal (d) NO2
38. Formation of SO3 from SO2 in contact process is favoured by:
(a) Low temperature (b) Excess of O2
(c) Adding V2O5 (d) All of them
39. Value of pH for a solution is:
(a) Positive (b) Negative
(c) Zero (d) All of them
40. pH of human blood is:
(a) 7.0 (b) 7.32
(c) 8.0 (d) 8.32
41. Neutral solution shows of pH of:
(a) 0 (b) 7
(c) 14 (d) 3
 Lec. Rana Hassan Tariq

42. pH of 0.01 M HCl is:

(a) 0 (b) 1
(c) 2 (d) 3
43. Term pH was introduced by:
(a) Sorenson (b) Goldstein
(c) P. Waage (d) Handerson
44. Fizzy drinks has a pH related to neutral water:
(a) More basic (b) More acidic
(c) Neutral (d) None of them
45. pH of milk of magnesia is:
(a) 3.1 (b) 4.5
(c) 5.0 (d) 10.5
46. A solution has [H+] = 1 1010. It is:
(a) Acidic (b) Basic
(c) Neutral (d) None of them
47. Lowest pH is of a solution:
(a) 0.1 M NaOH (b) 0.1 M HCl
(c) 0.1 M KOH (d) 0.1 M Ba (OH)2
48. A solution has pH = 6. Its [OH] concentration is:
(a) 108 mol dm3 (b) 107 mol dm3
(c) 106 mol dm3 (d) 100 mol dm3
49. Water is a poor electrolyte. Its ionic product Kw has a unit of:
(a) mol dm3 (b) mol2 dm3
(c) mol dm3 (d) mol2 dm6
50. Ionization constant of water is represented by:
(a) Ka (b) Kw
(c) Kb (d) pKw
51. Negative log of ionization constant of water is:
(a) pKw (b) pKa
(c) pKb (d) pH
52. Stronger acid is that which has a pKa of:
(a) 1.0 (b) 2.0
(c) 2.5 (d) 4.6
53. Strength of an acid is described by its dissociation constant represented by:

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(a) Ka (b) pKa

(c) Kb (d) pKb
54. Kb is called:
(a) Ebullioscopic constant (b) Ionization constant of base
(c) Binary rate constant (d) Boiling constant
55. Acetic acid is 1.33% ionizable. It means that out of 1000 molecules of 0.1 M actic acid,
ionizable molecules are:
(a) 1.33 (b) 13.3
(c) 133 (d) 13.35
56. Greater the value of Ka for acid tells that acid is:
(a) Strong (b) Weak
(c) Very weak (d) None of them
57. If difference of pKa for two acids is 2 then the acid with lower pKa is stronger than other by:
(a) 2 times (b) 20 times
(c) 10 times (d) 100 times
58. Weakest conjugate base among the following is:
(a) CH3COO (b) HCOO
(c) Cl (d) None of these
59. If acid is weak, its conjugate base is:
(a) Very weak (b) Very strong
(c) Moderately weak (d) None of these
60. Electrolyte which dissociated to a greater extents is:
(a) Strong (b) Weak
(c) Very weak (d) Not predictable
61. Purification of rock salt by passing HCl through the saturated salt solution is due to:
(a) Solubility effect (b) Ionization effect
(c) Common ion effect (d) Catalytic effect
62. Capability of a buffer solution to resist a change in its pH is called its:
(a) pKa (b) pKb
(c) Buffer capacity (d) None of these
63. pKa value of CH3COOH is 4.74. A buffer solution containing equi molar quantities of
CH3COOH + CH3COONa has a pH of:
(a) 3.74 (b) 4.74
(c) 5.74 (d) 6.74
64. Which pair can be used to make a buffer:
 Lec. Rana Hassan Tariq

(a) NaOH + Na2CO3 (b) NaOH + CH3COOH

(c) H2SO4 + FeSO4 (d) NH4OH + NH4Cl
65. pH of a buffer solution can be calculated by:
(a) Arrhenius equation (b) Bohr equation
(c) Schrodinger equation (d) Handerson equation
66. Solution which can resist a change in pH by small addition of acid or base is:
(a) Ideal (b) Real
(c) Buffer (d) Non-ideal
67. A solution of CH3COOH with CH3COONa can give rise to:
(a) A buffer (b) Acidic buffer
(c) Basic buffer (d) None of these
68. Ionization of NaCl can be suppressed by adding:
(a) HCl (b) NH4OH
(c) CH3COOH (d) H2O
69. During group identification of basic radicals in salt analysis, by adding NH4Cl in NH4OH, its
ionization is:
(a) Decreased (b) Increased
(c) Remains same (d) Not predictable
70. Solubility of KClO3 is suppressed by:
(a) HCl (b) NaCl
(c) KCl (d) Na2CO3
71. Best buffer is prepared when concentration of acid solution and salt solution is equal. pH of that
solution can be taken as:
(a) pH = 0 (b) pH = pKa
(c) pH > pKa (d) pH < pKa
72. ksp for PbSO4 is 1.8 10 mol dm . Maximum concentration of Pb+2 ion is:
8 2 6

(a) 3.6 1016 mol dm3 (b) 1.8 108 mol dm3
(c) 1.84 104 mol dm3 (d) 1.34 104 mol dm3
73. Product of concentration of ions raised to the power equal to the coefficients of ions in balanced
chemical equation for ionization of saturated. Salt solution is called.
(a) Ka (b) Kb
(c) Ksp (d) Kw
74. To determine the solubility of a salt, from ksp value, what other information is need:
(a) Name of compound (b) Mass
(c) Structure (d) Formula
75. A sparingly soluble salt among the others is:

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(a) AgCl (b) PbCrO4

(c) PbSO4 (d) All of them
76. Not a fairly soluble salt among the others:
(a) NaCl (b) KCl
(c) NH4Cl (d) AgCl
ANSWERS
1. a 2. c 3. b 4. c 5. a
6. b 7. d 8. d 9. c 10. d
11. c 12. d 13. a 14. c 15. c
16. b 17. a 18. c 19. d 20. b
21. b 22. b 23. c 24. b 25. b
26. c 27. d 28. a 29. d 30. d
31. a 32. b 33. a 34. d 35. c
36. c 37. b 38. d 39. d 40. b
41. b 42. c 43. a 44. b 45. d
46. b 47. b 48. a 49. d 50. b
51. a 52. a 53. a 54. b 55. b
56. a 57. d 58. c 59. b 60. a
61. c 62. c 63. b 64. d 65. d
66. c 67. b 68. a 69. a 70. c
71. b 72. d 73. c 74. d 75. d
76. d

SHORT ANSWERS TO EXERCISE

Q4c. Write Kc for the following reactions:
(i) Sn+2 + 2Fe+3 Sn+4 + 2Fe+2
[Product] [Sn 4 ][Fe2 ]2
Kc = [Reactants] =
[Sn 2 ][Fe3 ]2
(ii) Ag+ + Fe+2 Fe+3 + Ago
[Fe3 ][Ag o ]
Kc
[Ag ][Fe2 ]
 Lec. Rana Hassan Tariq

(iii) N2 + O2 2NO
[NO]
Kc
[N 2 ][O 2 ]
(iv) 4NH3 + 5O2 4NO + 6H2O
[H 2O]6 [NO]4
Kc
[NH3 ]4 [O 2 ]5
(v) PCl5 PCl3 + Cl2
[PCl3 ][Cl2 ]
Kc
[PCl5 ]
Q5a. Reversible reactions attain dynamic equilibrium and not static why? Def of reversible
reaction.
Ans. A chemical equilibrium state in a reversible reaction is a state where the rate of forward reaction
is equal to rate of reverse reaction so system is dynamic (in function) at equilibrium.
If it would be static all type of reactions would stop.
Q5b. Why do rates of forward reactions slow down when a reversible reaction approaches the
equilibrium stage?
Ans. (i) According to law of mass action: Rate of reaction is proportional to the concentrations of
reactants.
As reactants go on decreasing with passage of time the rate of reaction also slows down
near equilibrium.
(ii) In start effective collisions of reactants is greater so a sharp decrease of concentration or
steepness of slope of graph is observed. With the formation of products, hindrance is
created for effective collisions so rate of reaction is decreased.

Q6. When a graph is plotted between time on x-axis and the concentration of reactants and
products on y-axis for a reversible reaction, the curves becomes parallel to time axis at a
certain stage:
(a) At what stage the curve become parallel?

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Ans. In a reversible reaction, the concentration of reactants and products become constant at
equilibrium stage but the reaction does not stop. Therefore, at the equilibrium stage the curves
of the concentration of reactants and products become parallel.
(b) Before the curve become parallel, the steepness of curve falls
Ans. At the beginning of the reversible reactions, the concentration of the reactants decreases and
concentration of the product increases rapidly. As a result of this two curve show greater
steepness but as reaction approaches to equilibrium stages both rate of forward and reverse
reaction become slow according to law of mass action. Due to this near, the equilibrium point
the steepness of the curves fall before becoming parallel to x-axis.
(c) The rate of decrease of concentration of any of the reactants and rate of increase of
concentration of any of the products may or may not be equal, for various types of
reactions, before the equilibrium time. Explain it.
Ans. When no. of moles of reactants and products are equal, then rates of increase and decrease of
products and reactants are equal. But when no. of moles in a balanced chemical equation are
different then rate of change of concentration of a species will be different from other. e.g.,
N2O4 2NO2
Speed of rising curve is greater than falling curve in the said reactions are number of moles of
product are greater than number of moles of reactants.
Q7a. Give relationship of Kc & Kp for following
aA + bB cC + dD
[Products] [C]c [D]d
Kc = so
[Reactants] [A]a [B]b
Kp = Kc(RT)n
n = no. of moles of P no. of moles of R.
(c + d) (a + b) = y moles
So Kp = Kc(RT)y
(b) Decide comparative magnitudes of Kp and Kc for
(i) NH3 synthesis
N2 + 3H2 2NH3
[NH3 ]2
Kc =
[H 2 ]3[N 2 ]
Kp = Kc(RT)n
Kp = Kc(RT)2 as [n = 2 4 = 2]
so Value of Kp < Kc
(ii) Dissociation of PCl5
PCl5 PCl3 + Cl2
[PCl3 ][Cl2 ]
Kc =
[PCl5 ]
 Lec. Rana Hassan Tariq

Kp = Kc(RT)n
Kp = Kc(RT)1 as n = 2 1 = 1
So value of Kp > Kc as it is obtained by multiplying Kc RT.
Q8. Write down Kc expression for the following:
(i) CH3COOH + C2H5OH CH3COOC2H5 + H2O
moles at t = 0 a mol b mol 0 mol 0 mol
moles at t = equilibrium (a x) + (b x) (x) + (x)
ax bx x x
conc. in mol/v (dm3) so
v v v v
x x


[CH3COOC2 H5 ][H 2O] v v
Kc =
[CH3COOH][C2 H 5OH] a x x
b

v v
x2 v2
= 2
v (a x)(b x)
x2
so Kc =
(a x)(b x)
(ii) H 2 + I2 2HI
moles at t = 0 a mol + b mol 0 mol
[HI]2
at t = equilibrium (a x) + (b x) 2x Kc =
[H 2 ][I 2 ]
ax bx 2x
conc. mole/dm3 so
v v v
2
2x
4x 2
Kc = v
a x b x (a x)(b x)

v v

(iii) 2HI H 2 + I2
t=0 1a 0+0
t = equilibrium (a 2x) x+x
1a 2x x x
concentration ,
v v v
[Product
Kc = [Reactant]

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x x

[H 2 ][I 2 ] v v x2
Kc =
[HI]2 1a 2x
2
(4a 2x)2

v

(iv) PCl5 PCl3 + Cl2

moles at t = 0 a 0+0
moles at t = equilibrium (a x) x+x
ax x x
concentration in moles/Vdm3 ,
v v v
[Product
Kc = [Reactant]
x x
x2
[PCl3 ][Cl2 ] v v
Kc =
[PCl5 ] a x v(a x)

v

(v) N2 + 3H2 2NH3

moles at t = 0 a+b 0
moles at t = equilibrium (a x) + (b 3x) 2x
a x b 3x 2x
concentration in moles/V dm3
v v v
[Product
Kc = [Reactant]

[NH3 ]2
Kc =
[H 2 ]3[N 2 ]
2
2x
4x 2 v 2
So Kc = v =
a x b 3x
3
(a x)(b 3x)3

v v

b. How some reactions are effected by volume at equilibrium stage.

Ans. (i) If reaction mixture is in gaseous state then at equilibrium if volume is changed it will
effect the equilibrium
 Lec. Rana Hassan Tariq

(ii) If number of moles of reactants are not equal to number of moles of product then those
gaseous reactions are effected by volume change at equilibrium

Q10. Explain the following with reasons:

(a) The change in volume disturbs the equilibrium positions for some reactions in gaseous
phase but not the equilibrium constant.
Ans. Same as given in Answer of Q8(b).
b. The change of temperature disturbs both equilibrium position and constant of reaction.
Ans. The change of temperature disturbs both value of Kc and its position because change in
temperature changes heat contents of reaction mixture without changing concentration of
reactants and products so with a change in position of equilibrium with temperature value of Kc
is also changed.
(c) The solubility of glucose in water is increased by increasing temperature.
Ans. Solubility of glucose is an endothermic reaction
High pressure less no. of moles
Low pressure high no. of moles
C6H12O6(s) C6H12O6(aq) H = +ive value
So increase in temperature favours the forward reaction.
Q14. In dissociation of PCl5 what is effect on position and value of equilibrium by
1) Position 2) Direction 3) Ke
[PCl5 PCl3 + Cl2]
Ans. (i) Temp is increased: Both Kc and its position are changed and equilibrium is shifted to right
as reaction is more towards forward direction.
(ii) Volume is increased: As number of moles of product is greater than reactant so increased
volume favours the forward reaction so position is changed to right but Kc remains constant.
(iii) A catalyst is added: Catalyst has no effect on position of equilibrium as well as
equilibrium constant. It only helps to establish equilibrium earlier.
(iv) Cl2 is added: By increased concentration of Cl2 (Product) the equilibrium is shifted to left
and reaction will move in a backward direction and Kc is not effected.
Q15. Synthesis of ammonia by Habers process is an exothermic reaction.
N2 + 3H2 2NH3 H = 92.46 KJ
(a) What should be the possible effect of change of temperature at equilibrium stage?
Ans. Effect of temperature: Forward reaction is exothermic so decrease in T favours more
production of NH3 & vice versa.
(b) How does the change of pressure or volume shift the equilibrium position of this reaction?
Ans. Effect of P/V: No. of moles of reactants is greater than products. So decrease in
volume/increased P favours a forward direction and vice versa.
(c) What is the role of the catalyst in this reaction?
Ans. Effect of catalyst: Catalyst speeds up the reaction. Kc or its position is not effected by it.
(d) What happens to equilibrium position of thus reaction if NH3 is removed from the reaction
vessel from time to time?
Ans. Removal of NH3: Continuous removal of NH3 disturbs the position of equilibrium according to
Le Chateliers principal and favours a forward reaction as

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[NH3 ]2
KC =
[H 2 ]3[N 2 ]
Q16a. Write balanced equation for production of SO3.
2SO2 + O2 2SO3 H = 194 KJ/mol
b. Effect of P: According to LeChateliers principal increased P favours forward direction which
has less no. of moles.
c. Although reaction is exothermic, still a temperature of 400500oC is required to have a best
yield of SO3 because the rate of reaction is so slow that economically it is not favourable at low
temperature.

NUMERICAL OF EXERCISE
Q19. Kc value for the following reaction is 0.016 at 520oC.
2HI(g) H2(g) + I2(g)
Equilibrium mixture contains [HI] = 0.08 M. [H2] = 0.01 M,
[I2] = 0.01 M. To this mixture more HI is added so that its new concentration is 0.096 M.
What will be the concentrations of [HI], [H2], [I2] when equilibrium is re-established.
Ans. Given data:
Initial concentration of [HI] = 0.08 M
Initial concentration of [H2] = 0.01 M
Initial concentration of [I2] = 0.01 M
New concentration of [HI] = 0.096 M

Requirement:
[HI], [H2] and [I2] = ?
Solution:
2HI H2 + I2
Initial concentration
0.08 M 0.01 M + 0.01 M
At equilibrium, the new concentrations
(0.096 2x) (0.01 + x) + (0.01 + x)
concentration of product [H 2 ][I2 ]
KC = =
concentration of reactants [HI]2
[0.01 x][0.01 x]
0.016 =
[0.096 2x]2
(0.01 x)2
0.016 =
(0.096 2x)2
Taking square root of both sides
 Lec. Rana Hassan Tariq

(0.01 x)2
0.016 =
(0.096 2x)2
0.01 x
0.126 =
0.096 2x
0.126(0.096 2x) = 0.01 + x
0.012096 0.252x = 0.01 + x
0.012096 0.01 = x + 0.252x
0.002096 = 1.252x
0.002096
x =
1.252
x = 1.68 103 M or 0.00168 M
Concentrations at equilibrium can be calculated as follows
(i) [HI] = (0.096 2x)
= 0.096 0.00168
= 0.0926 M
(ii) [H2] = 0.01 + x
= 0.01 + 0.00168
= 0.01168 M
(iii) [I2] = 0.01 + x
= 0.01 + 0.00168
= 0.01168 M
[HI] = 0.0926 M
[H2] = 001168 M
[I2] = 0.01168 M

Q20. Equilibrium constant for reaction between acetic acid and ethyl alcohol is 4. A mixture of
3 moles CH3COOH, and one mole C2H5OH is allowed to attain equilibrium. Calculate
amount of ethyl acetate present at equilibrium in moles and grams. Also calculate masses
of reactants left behind.
Ans. Given data: KC = 4
Moles of acetic acid = 3
Moles of ethyl alcohol = 1
Requirement:
Moles of ethyl acetate = ? , Amount of ethyl acetate = ?
Moles of acid = ? , Amount of acid = ?
Moles of alcohol = ? , Amount of alcohol = ?
Solution:
CH3COOH + C2H5OH CH3COOC2H5 + H2O
at t = 0, moles 3 mol + 1 mol 0 mol + 0 mol
at t = equilibrium moles (3 x) + (1 x) x + x

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[Product] [CH3COOC2 H5 ][H 2 O]

Kc =
[Reactants] [CH3COOH][C2 H5 OH]
(x)(x) x2
4 =
(3 x)(1 x) x 2 4x 3
x2 = 4(x2 4x + 3)
x2 = 4x2 16x + 12
4x2 x2 16x + 12 = 0
3x2 16x + 12 =0
It is a quadratic equation. To evaluate the value of x,
The formula used is:
b 2 4ac
x = b
2a
Let us consider that [a = 3, b = 16, c = 12] for above reaction
(16)2 4 3 12
Thus x = (16)
23
16 256 144
=
6
16 112 16 10.58
=
6 6
16 10.58
so x= 4.43 moles or
6
16 10.58
x= 0.90 moles
6
From the above two values of x
x 4 as initial concentration of CH3COOH is less i.e., 3 moles. So value of x = 0.90 moles.
(i) Concentration of (CH3COOH) at equilibrium
= 3 x = 3 0.9 = 2.1 moles
(ii) Concentration of (C2H5OH) at equilibrium
= 1 x = 1 0.9 = 0.1 moles
(iii) Concentration of ethyl acetate = x = 0.9 moles
(iv) Mass (g) = Moles Mol. mass
(a) Amount of CH3COOH = 2.1 60 = 126 g
(b) Amount of C2H5OH = 0.1 46 = 4.6 g
(c) Amount of ethyl acetate = 0.9 88 = 79.46 g
Moles of ethyl acetate = 0.9 moles
Mass of ethyl acetate = 79.46 g
Mass of acid left behind = 126 g
 Lec. Rana Hassan Tariq

Mass of alcohol left = 4.6 g

Q21. Study the equilibrium

H2O(g) + CO(g) H2(g) + CO2(g)
When 1.00 mol of steam and 1 mol of CO are allowed to react and reach to equilibrium
33.3% of equilibrium mixture is hydrogen. Calculate the value of Kp. State the units of Kp.
Ans. Given data:
Moles of steam = 1.00
Moles of CO = 1.00
% of H2 at equilibrium = 33.3%
Requirement:
(i) Value of Kp = ?
(ii) Unit of Kp =?
Solution:
H2O + CO H2 + CO2
concentration at t = 0 1 + 1 0 + 0
concentration at t = eq (1 x) + (1 x) x + x
Total moles of reaction mixture = 1 + 1 = 2 mol.
Moles of H2 at equilibrium = 33.3%
x conc. of H2
It means that
2 100
x 33.3

2 100
2 33.3
x 0.666 moles
100
So [H2O] = 1 x
= 1 0.666 = 0.333 moles
[CO] = 1 x
= 1 0.666 = 0.333 moles
[H2] = [CO2] = x = 0.666 moles
Kp = Kc(RT)n as n = 0 so
Kp = Kc
[P] [CO2 ][H 2 ] 0.666 0.666
Kp =
[R] [CO][H 2O] 0.333 0.333
Kp = 4 `

[CO2 ][H 2 ] mol dm3 . mol dm3

Units of Kp =
[CO][H 2O] mol dm3 . mol dm3
= no unit

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Kp = 4 `

Kp has no unit.

Q22a. Calculate the pH of 104 mol dm3 of HCl.

Ans. Given data:
concentration of HCl = 104 mol dm3
Requirement:
pH of HCl = ?

Solution:
HCl H+ + Cl (ionization)
if moles are 1 1+1
4
Then 10 104 + 104
So [H+] = 104 mol dm3
pH = log[H+]
= log 104
pH = 4

Q22b. Calculate the pH of 104 mol dm3 of Ba(OH)2

Ans. Given data:
concentration of Ba(OH)2 = 104 mol dm3
Requirement:
pH of Ba(OH)2 = ?
Solution:
Ba(OH)2 2OH + Ba+2
if moles 1 2+1
4
Then 10 2 104 + 104
So [OH] = 2 104 mol dm3
pOH = log[OH]
= log[2 104]
= 3.698
pH + pOH = 14
pH = 14 pOH
pH = 14 3.698 = 10.302

Q22c. Calculate the pH of 1 mol dm3 of H2X which is 50% ionized.

Ans. Given data:
concentration of H2X = 1 mol dm3
Ionization = 50%
 Lec. Rana Hassan Tariq

Requirement:
pH of H2X = ?

Solution:
H2X 2H+ + X (if 100% is its)
moles 1 2 +1 ionization
But as 50% dissociation is there.
So 1 H2X gives mol of H+ = 1
[H+] = 1 mol dm3
pH = log[H+]
= log[1]
pH = 0

Q22d. Calculate the pH of 1 mol dm3 NH4OH which is 1% dissociated.

Ans. Given data:
Ionization of NH4OH = 1%
concentration of NH4OH = 1 mol dm3
Requirement:
pH of NH4OH = ?
Solution:
NH4OH OH + NH+4
(100% ionization) 1 1 + 1 (mol)
(1% ionization) 1 0.01 + 0.1 (mol)
3
So [OH ] = 0.01 mol dm
pOH = log[OH] = log 0.01
=2
pH + pOH = 14
pH = 14 pOH
= 10
= 14 2
pH = 12

Q23. Benzoic acid C6H5COOH is a weak acid Ka = 6.4 105 mol dm3. What is the pH of the
buffer containing 7.2 g of C6H5COONa and 0.02 mol C6H5COOH.
Ans. Given data:
Ka = 6.4 105 mol dm3
[C6H5COOH] = 0.02 mol dm3
[C6H5COONa]= 7.2 g
Requirement:

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pH of Buffer = ?

Solution:
Using Hander sons equation
[Salt]
pH = pKa + log
[acid]
We need moles of C6H5COONa:
Mol. mass of C6H5COONa = 144 g mol1
Mass(g) 7.2
No. of moles =
Mol. mass 144
= 0.05 mol dm3
Applying Handersons equation
[0.05]
pH = pKa log , [pKa log Ka ]
[0.02]
0.05
= log 6.4 105 log
0.02
= 4.19 + 0.39
pH = 4.58

Q23b. A buffer solution has been prepared by mixing 0.2 M CH3COONa and 0.5 M CH3COOH
in dm3 of solution. Calculate the pH of buffer. pKa of acid = 4.74 at 25oC. How the values
of pH will change by adding 0.1 mol NaOH or 0.1 mol HCl respectively.
Ans. Given data:
[CH3COOH] = 0.5 M
[CH3COONa] = 0.2 M
pKa of acid = 4.74 at 25oC
Requirement:
(i) pH = ?
(ii) Change in pH by adding acid
Solution:
According to Handersons equation
[Salt]
pH = pKa + log
[acid]
[0.2]
= 4.74 log 4.74 log 0.4
[0.5]
pH = 4 + 0.39 = 4.39
Change in pH by adding 0.1 M NaOH:
It results in an increase in concentration of salt and decrease in that of an acid so
New data:
 Lec. Rana Hassan Tariq

[CH3COOH] = 0.5 0.1 = 0.4 M

[CH3COONa] = 0.2 + 0.1 = 0.3 M
[Salt]
pH = pKa + log
[acid]
0.3
= 4.74 + log
0.4
= 4.74 0.12
pH = 4.62
Change in pH by adding 0.1 M HCl:
It results in a decrease in concentration of salt and increase in concentration of H+ ions of acid.
New data:
[CH3COOH] = 0.5 + 0.1 = 0.6 M
[CH3COONa] = 0.2 0.1 = 0.1 M
[Salt]
pH = pKa + log
[acid]
[0.1]
= 4.74 + log
[0.6]
= 4.74 0.778
= 3.962
pH of Buffer = 4.35
pH after adding 0.1 M HCl = 3.962
pH after adding 0.1 M NaOH = 4.62

Q24. The solubility of CaF2 in water at 25oC is found to be

4 3
2.05 10 mol dm . What is the value of Ksp at this temperature.
Ans. Given data:
Solubility of CaF2 = 2.05 104 mol dm3 at 25oC
Requirement:
CaF2 Ca+2 + 2F `

1 mol 1 mol + 2 mol `

4
2.05 10 mol 2.05 104 mol + 2 2.05 104 mol
Ksp = [Cation][Anion]
Ksp = [Ca+2][F]2
= [2.05 104][2 2.05 104]2
= [2.05 104][4.1 104]2
= 3.446 1011
Ksp of CaF2 = 3.446 1011

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Q25. Solubility product of Ag2CrO4 is 2.6 102 at 25oC. Calculate the solubility of this
compound.
Ans. Given data:
Ksp of Ag2CrO4 = 2.6 102 at 25oC
Requirement:
Solubility of Ag2CrO4 = ?
Solution:
Ag2CrO4 2Ag+ + CrO42
Let the solubility of salts is supposed as S so
S 2S + S
2
Ksp = [Ag+]2[ CrO4 ]
= (2S)2(S)
2.6 102 = 4s3
2.6 102
S3 = 6.5 103
4
3
S3 = 3 6.5 103
S = 0.1866 mol dm3
Solubility of Ag2CrO4 = 0.1866 mol dm3

PREVIOUS BOARD QUESTIONS

1. N2 + 3H2 2NH3
At 300oC in a 5 dm3 container has a concentration of 0.1 mol NH3, 0.1 mol N2 and 3 mol H2.
Calculate Kc for reaction.
(Lhr. Board 2001)
2. Discuss the conditions of T and P to obtain a maximum yield of following:
(Grw. Board 2002)
(i) N2 + 3H2 2NH3 H = ive
(ii) N2 + O2 2NO H = +ive
(iii) 2SO2 + O2 2SO3 H = ive
3. Explain that exothermic reactions are favoured by lowering the temperature.
(Grw. Board 2001)
4. Define Le Chateliers principle and discuss effect of T and P on production of NH3 and PCl3.
(Grw. Board 2001)

N2 + 3H2 2NH3
 Lec. Rana Hassan Tariq

PCl5 PCl3 + Cl2

5. Give application of Kc.
6. State and derive an equation for law of Mass Action.
(Rwp. Board 2005) (Lhr. Board 2003)
7. Define pH and Kw. How are they related? (Lhr. Board 2003)
8. What are buffers? Give their uses in daily life. (Lhr. Board 2002)
9. Give industrial applications of equilibrium. (Grw. Board 2003)
10. What is meant by Buffer capacity? (Bwp. Board 2005)
11. Define pH and pOH. (Bwp. Board 2005)
12. Solubility of PbF2 at 25oC is 0.64 g dm3. Calculate Ksp of PbF2.
(Bwp. Board 2005)
13. Define and explain Ksp. (Rwp. Board 2005)
14. What is effect of catalyst on equilibrium? (Mtn Board 2005)
15. Explain Lowry-Bronsted concept.
(Lhr. Board 2001) (Lhr. Board 2005)
16. Define LeChateliers principle. (Lhr. Board 2005)
17. Describe the effect of common ion on solubility by giving examples.
(Grw. Board 2005)
18. State and explain law of mass action and derive the expression for equilibrium constant.
(Grw. Board 2005)
19. How NaCl is purified by common ion effect? (Grw. Board 2006)
20. Define Lowry-Bronsted idea of acids and bases. Explain conjugate acid and base.
(Grw. Board 2006)
21. What is ionic product of water? Define pH. (Lhr. Board 2006)
22. Why the equilibrium constant value has its unit for some of reversible reactions but has no units
for some other reactions?
(Grw. Board 2007)
23. When concentrations of salt is increased in acidic buffer, its pH increases why?
(Grw. Board 2007)
24. What will be the effect of change in pressure on NH3 synthesis?
(Grw. Board 2007)

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25. Calculate pH of a buffer solution in which 0.11 molar CH3COONa and 0.09 molar CH3COOH
are present. Ka for CH3COOH is
1.85 105. (Grw. Board 2007) (Lhr. Board 2007)
26. Derive Handersons equation. (Lhr. Board 2003)
27. What are buffers? How are they formed? Why do we need buffer?
(Lhr. Board 2003)
28. What is percentage ionization of CH3COOH for which 0.1 mol is concentration of solution?

SOME POSSIBLE SHORT QUESTIONS

29. Solubility of glucose in water is increased by increasing temperature. Why?

30. How would you prove that 25oC, 1dm3 of water contain 10-7 moles of H3O+ and 10-7 moles of
OH-1?
31. What is the difference between reversible and irreversible reactions?
32. State the Kc?
33. Define active mass?
34. Give applications of Kc?
35. What are conditions to get a maximum yield from a reversible reaction?
36. Why solid ice at 0oC can be melted by applying pressure without supply of heat from outside?
37. A catalyst does not effect equilibrium constant? Justify it.
38. Differentiate between pH and pOH?
39. Describe the percentage of ionization of an acid?
40. How common ion effect help in salt analysis for the detection of 3rd group basic radicals?
41. What is the principle of common ion effect?

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