PHYSICAL CHEMISTRY By: Shailendra Kumar

PHYSICAL CHEMISTRY
by: SHAILENDRA KR.
Meq. Approach
Classes at: -
SCIENCE TUTORIALS; Opp. Khuda Baksh Library, Ashok Rajpath, Patna
PIN POINT STUDY CIRCLE; House No. 5A/65, Opp. Mahual Kothi, Alpana Market, Patna

Topic: Ionic Equilibrium

01. 0.2 M solution of monobasic acid is dissociated to 0.95%. Calculate its dissociation constant.
Ans: 1.8 105
02. Calculate concentration of H+ and degree of dissociation of 0.2 M acetic acid solution having
Ka = 1.8 105.
Ans: 0.0095 or 0.95 %
03. Ka for HA is 4.9 108. After making the necessary approximation. Calculate for its decimolar
solution.
(a) % dissociation. (b) OH concentration. (c) pH.
Ans: 1.43 1010
04. Nicotinic acid (Ka = 1.4 105) is represented by the formula HNiC. Calculate its percent disso-
ciation in a solution which contains 0.10 moles of nicotinic acid per 2.0 litre of solution.
Ans: 1.67 102 or 1.67 %
05. A solution of 0.01 M concentration of NH4OH is 2.6% dissociated. Calculate [H+], [OH],
[NH4+], [NH4OH] and pH of solution.
Ans: 10.4145
06. Calculate the concentration of fluoroacetic acid which is required to get [H+] = 1.50103 M . Ka
of acid = 2.6 103.
Ans: 237 103 M
07. Determine degree of dissociation of 0.05 M NH3 at 25C in a solution of pH = 11.
Ans: 2 102 or 2%
08. Calculate pH of (i) 103 N HNO3, (ii) 103 M H2SO4, (iii) 103 N H2SO4, (iv) 0.01 N HCl,
(v) 108 N HCl, (vi) 102 M HCl.
Ans: (i) pH = 3, (ii) pH = 2.6989, (iii) pH =3, (iv) pH = 2, (v) pH = 6.9586 or pH = 6.9788,(vi) pH=2
09. Calculate pH for acid solutions having [H+] as (a) [H+] = 0.05 M (b) [H+] = 5.0 M (c) [H+] = 108 M.
Ans: (a) pH = 1.3010 (b) pH = 2 (c) pH = 6.9586
10. Calculate pH for
(a) 0.001 N NaOH (b) 0.01 N Ca(OH)2 (c) 0.01 M Ca(OH)2
8 2
(d) 10 M NaOH (e) 10 M NaOH (f) 0.0008 M Mg(OH)2

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PHYSICAL CHEMISTRY By: Shailendra Kumar
Ans: (a) pH = 11 (b) pH = 12 (c) pH = 14 1.6989 = 12.3010
(d) pH = 6.9586 (e) pH = 2 (f) pH = 12.6989
11. Calculate pH of
(a) 0.002 N acetic acid having 2.3% dissociation.
(b) 0.002 N NH4OH having 2.3% dissociaton.
Ans: (a) pH = 4.3372 (b) pH = 9.6627
12. Calculate pH of 0.10 N acetic acid having Ka = 1.8 105.
Ans: pH = 2.8726
13. What is [H+] for a solution in which (i) pH = 3 (ii) pH = 4.75 ?
Ans: (i) [H+] = 103 M (ii) [H+] = 1.7782 105 M
14. The pH of 0.1 M solution of weak monoprotic acid is 4.0. Calculate its [H+] and Ka.
Ans: [H+] = 104 M, Ka = C2 = 104 103 = 107
15. The pH of 0.05 M aqueous solution of diethyl amine is 12.0. Calculate Kb.
Ans: Do Yourself
16. The Kw for 2H2O H3O+ + OH change from 1014 at 25C to 9.62 1014 at 60C. What is
pH of water at 60C ? What happen to its neutrality ?
Ans : Do Yourself
17. A solution of HCl has a pH = 5. If one mL of it is diluted to 1 litre, what will be pH of resulting
solution ?
Ans: pH = 6.9788
18. Two gm of NaOH are dissolved in water to make 1 litre solution. What is pH of solution ?
Ans: pH = 12.6989
19. Calculate the [Cl], [Na+], [H+], [OH] and pH of resulting solution obtained by mixing 50 mL of 0.6
N HCl and 50 mL pf 0.3 N NaOH.
Ans: [Cl] = 0.3 M, [Na+] = 0.15 M, [H+] = 0.15 M, [OH] = 6.6 1014 M, pH = 0.8239
20. Calculate the pH of solution obtained by mixing 10 mL of 0.1 M Hcl and 40 mL of 0.2 M H2SO4.
Ans: pH = 0.4685
21. Calculate the pH of a solution which contains 100 mL of 0.1 M Hcl and 9.9 mL of 1.0 M NaOH.
Ans: pH = 3.0409
22. Calculate the pH of a solution which contains 9.9 mL of 1 M Hcl and 100 mL of 0.1 M NaOH.
Ans: pH = 10.9591
23. A solution contains 0.1 M H2S and 0.3 M HCl. Calculate the conc. of S2 and HS ions in solution.
Given Ka for H2S are 107 and 1.3 1013 respectively.
Ans: Do Yourself
24. Calculate the change in pH of 1 litre buffer solution containing 0.1 mole each of NH3 amd NH4Cl
up on addition of,
(i) 0.02 mole of dissolved gaseous HCl. (ii) 0.02 mole of dissolved NaOH.
Assume no change in volume. KNH = 1.8 105
3
Ans: Do Yourself
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PHYSICAL CHEMISTRY By: Shailendra Kumar
25. 20 mL of 0.2 M NAOH are added to 50 mL of 0.2 M acetic acid (Ka = 1.8 105).
(i) What is pH of solution ?
(ii) Calculate volume of 0.2 M NaOH required to make the pH of solution 4.74.
Ans: (i) pH = 4.5686 (ii) V = 25 mL
26. What volume of 0.1 M sodium formate solution should be added to 50 mL of 0.05 M formic acid
to product a buffer solution of pH = 4.0; pKa of formic acid = 3.80.
Ans: V = 3962 mL
27. Calculate the ratio of pH of a solution containing 1 mole of CH3COONa + 1 mole of HCl per litre
and fo other solution containing 1 mole CH3COONa + 1 mole of acetic acid per litre.
Ans: Do Yourself
28. Calculate the composition of an acidic buffer solution made up of HA and NaA of total molarity
0.29 having pH = 4.4 and Ka = 1.8 105.
Ans: [Salt] = 0.09 M, [Acid] = 0.20 M
30. A certain buffer solution contains equal concentration of X and HX.Kb for X is 1010. Calculate
pH of buffer.
Ans: pH = 4
31. 0.1 M CH3COOH solution is titrated against 0.05 M NaOH solution. Calculate pH at 1/4th and 3/
4th stages of neutralization of acid. The pH for 0.1 M CH3COOH is 3.
Ans: Do Yourself
32. KSP of AgCl is 2.8 1010 at 25C. Calculate solubility of AgCl in;
(a) Pure water (b) 0.1 N AgNO3 (c) 0.1 M KCl or 0.1 M NaCl
5 1 9 1
Ans: (a) 1.673 10 mole litre (b) 2.8 10 mole litre (c) 2.8 109 mole litre1
33. The solubility product of SrF2 in water is 8 1010. Calculate its solubility is 0.1 M NaF aqueous
solution.
Ans: 8 108 M
34. The solubility of AgCl in water at 25C is 1.79 103 g/litre. Calculate KSP of AgCl at 25C.
Ans: 1.55 1010 mole litre1
35. KSP of AgBr is 4 1013 and [Ag+] in a solution is 1 106 mole litre1. What is the [Br] in that
solution ?
Ans: 4 107 mole litre1
36. The [Ag+] ion in a saturated solution of Ag2CrO4 at 25C is 1.5 104 M. Determine KSP of
Ag2CrO4 at 25C.
Ans: 1.688 1012 mole litre3
37. Equal volumes of 0.02 M CaCl2 and 0.0004 M Na2SO4 are mixed. Will a precipitate form ?
Ans: Do Yourself
38. An acid type indicator, HIn differs in colour from its conjugate base (In). The human eye is
sensitive to colour differences only when the ratio [In] / [HIn] is greater than 10 or smaller than
0.1. What should be the minimum change in the pH of the solution to observe a complete
colour change (Ka = 1.0 105)?
Ans: Do Yourself
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PHYSICAL CHEMISTRY By: Shailendra Kumar
39. Calculate pH at which Mg(OH)2 begins to precipitate from a solution containing 0.10 M Mg+2
ions. KSP of Mg(OH)2 = 1 1011.
Ans: pH = 9
40. Calculate pH of a saturated solution of Mg(OH)2. KSP for Mg(OH)2 is 8.9 1012.
Ans: pH = 10.4168
41. Will a precipitate of Mg(OH)2 be formed in a 0.001 M solution of Mg(NO3)2, if the pH solution is
adjusted to 9 ? KSP of Mg(OH)2 = 8.9 1012.
Ans: Do Yourself
42. Zn salt is mixed with (NH4)2S of molarity 0.021 M. What amount of Zn+2 will remain unprecipitated
in 12 mL of the solution ? KSP of ZnS = 4.51 1024.
Ans: 1.677 1022 g/12 mL
43. A solution has 0.05 M Mg+2 and 0.05 M NH3. Calculate the concentration of NH4Cl required to
prevent the formation of Mg(OH)2 in solution. KSP of Mg(OH)2 = 9.0 1012 and ionisation con-
stant of NH3 is 1.8 105.
Ans: 0.067 M
44. Calculate the solubility of AgCN in a buffer solution of pH = 3. Given KSP of AgCN = 1.2 1016
and Ka for HCN = 4.8 1010.
Ans: 1.58 105 mole litre1
45. Calculate the hydrolysis constant of the salt containing NO-2 ions. Given Ka for HNO2 = 4.5
1010.
Ans: 2.2 105
46. What is the pH of a 0.5 M aqueous NaCN solution ? pKb of CN = 4.70.
Ans: 11.5
47. Calculate the pecentage hydrolysis in 0.003 M aqueous solution of NaOCN. Ka for HOCN =
3.33 104.
Ans: 102
48. Calculate degree of hydrolysis and pH of 0.2 M solution of NH4Cl. Given Kb for NH4OH is 1.8
105.
Ans: 4.9771
49. Find out the amount of NH4Cl dissolved in 500 mL to have pH = 4.5. Kb for NH4Cl is 1.8 105.
Ans: 48.15 g
50. Calculate for 0.01 N solution of sodium acetate,
(a) Hydrolysis constant. (b) Degree of hydrolysis. (c) pH.
5
Given Ka = 1.9 10
Ans: (a) 5.26 1010 (b) 2.29 104 (c) pH = 8.36
51. Ka for butyric acid is 2.0 105. Calculate pH and hydroxyl ion concentration in 0.2 M aqueous
solution of sodium butyrate.
52. Ka for ascorbic acid (HAsc) is 5 105. Calculate the hydrogen ion concentration and percent-
age of hydrolysis in an aqueous solution in which the concentration of Asc ions is 0.02 M.
Ans: 104
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PHYSICAL CHEMISTRY By: Shailendra Kumar
53. Calculate the pH at the equivalence point when a solution of 0.1 M acetic acid is titrated with a
solution of 0.1 M NaOH.
Ka for acid = 1.9 105.
Ans: 8.71
54. Calcium lactate is a salt of weak acid and represented as Ca(LaC)2. A satirated solution of
Ca(LaC)2 contains 0.13 mole of salt in 0.50 litre solution. The pOH of this is 5.60. Assuming
complete dissociation of salt, calculate Ka of lactic acid.
Ans: Ka = 8.25 104
55. Calculate pH of the follwing mixture. Given that Pka = 4.7, Pkb = 4.74.
(a) 50 mL of 0.10 M NaOH + 50 mL 0.05 M CH3COOH.
(b) 50 mL of 0.05 M NaOH + 50 mL 0.10 M CH3COOH.
(c) 50 mL of 0.10 M NaOH + 50 mL 0.10 M CH3COOH.
(d) 50 mL of 0.10 M NH4OH + 50 mL 0.05 M HCl.
(e) 50 mL of 0.05 M NH4OH + 50 mL 0.10 M HCl.
(f) 50 mL of 0.10 M NH4OH + 50 mL 0.10 M HCl.
(g) 50 mL of 0.05 M NH4OH + 50 mL 0.05 M CH3COOH.
Ans: (a) 12.3979 (b) 4.7447 (c) 8.7218 (d)9.2553 (e) 1.6021 (f) 5.2782 (g) 7
56. Calculate the pH at the equivalence point when 40 mL of 0.1 M CH3COOH is neutralized by 0.2
M NaOH. Given Ka for CH3COOH = 105.
Ans: 8.9122
57. Equilibrium constant for the acid ionisation of Fe+3 to Fe(OH)+2 and H+ is 6.5 103. What is the
maximum pH which could be used so that at leat 95% of the total Fe+3 in a dilute solution exists
as Fe+3.
Ans: 0.9083
58. Calculate pH of 0.001 M solution of ZnCl2.Kb for Zn(OH)2 = 2.2 1012.
Ans: 6.3486
59. Calculate the pH of 0.1 M K3PO4 solution. The third dissociation constant of orthophosphoric
acid is 1.3 1012. Assume that the hydrolysis proceeds only in the first step.
Ans: 12.4366
60. The ionisation constant of NH+4 in water is 5.6 1010 at 25C. The rate constant for the
reaction of NH+4 and OH to form NH3 and H2O at 25C is 3.41010 litre mole1 sec1. Calcu-
late the rate constant for proton transfer from water to NH3.
Ans: 6.07 105

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