IONIC EQUILIBRIUM 147

LDA - 1

Electrolytes Theory, Theory of Acids and Bases, Dissociation of Weak Acids and Bases
1. (a) What is the conjugate base of
O-

H2PO4- HPO4 2- NH2- S2- H2O OCl- CH3O-

– +
(i) H3PO4, (ii) H2PO4 , (iii) NH3, (iv) HS , (v) H3O , (vi) HOCl (vii) CH3OH, and (viii) phenol ?

(b) What is the conjugate acid of

HF– H20– HP4 2- NH4+ NH3 H2S
– CH3OH2 + CH3OCH4+ C6H5NH3+
(i) F , (ii) OH , (iii) PO34 , (iv) NH3, (v) NH2 , (vi) HS (vii) CH3OH, (viii) CH3OCH3 and (ix) C6H5NH2 ?

2. Identify the Bronsted acids and bases in the following :

–
(i) NH3 + HCl NH4 + Cl
–
(ii) NH4 + OH NH3 + H2O
– – 2–
(iii) HS + OH S + H2O
+ –
(iv) H3O + HS H2S + H2O
–
(v) H2SO4 + CN HCN + HSO4

3. Each of the following reaction is displaced to the right.

(a) Arrange all the Bronsted acids that appear in these equations in the order of deceasing acid strength.
(b) Make a similar list for the Bronsted bases.

H3O H2PO4  H3PO4 H2O correct order-NH2- >OH- >CN- ..

– –
HCN + OH  H2O + CN
–
H3PO4 + CN  HCN + H2PO4

H2O NH2  NH3 OH

4. (i) Which of the following reagents are strong electrolytes ?
– +
(a) NH3 (b) NH4Cl (c) CH3COOH (d) CH3COO Na (e) HCl (f) NaCl
(ii) Write the formulas for the conjugate bases of the following acids :

(a) HCN (b) HCO3 (c) N2H5 (d) C2H5OH CN-, CO3 2-, N2H4, C2H5O-

(iii) Write the formulas for the conjugate acids of the following bases :
CH3COOH2+ , H2CO3
(a) CH3COOH (b) HCO3 (c) Pyridine (d) N2H5

NH+ N2H6 2+
148 IONIC EQUILIBRIUM

NH3+NH3=NH4+ + NH2-
5. (i) Liquid NH3, like water, is an amphiprotic solvent. Write the equation for the autoionization of NH3.

(ii) Which one (s) of the following reactions is (are) Lewis acid-base reactions ?
2+ 2–
NH3 + BF3 H3N:BF3 Ca + S Ca + S
Lesser oxygens, oxygen->EN
6. (i) Give an explanation for the decreasing acid strength in the series HClO4, HClO3, HClO2. higher so it pulls e- from OH
bond
(ii) What would be the relative basic strengths of ClO4 , ClO3 , ClO2 ?

(iii) Keeping in mind the discussion of (a), how do you account for the fact that there is very little difference in acid
strength in the series H3PO4, H3PO3, H3PO2? oxygen are not directly attached to P, they are in OH bond

7. A conjugate acid differs from its conjugate base by

(a) electron pair (b) proton (c) electron (d) neutron
8. Which of the following can act both as a Bronsted acid and a Bronsted base ?

(a) HCl (b) H3PO4 (c) HCO3– (d) O2–

9. Which one of the following is a dibasic acid ?
(a) H3PO4 (b) H3PO3 (c) H3BO3 (d) H3AsO4

Answer Key
– – –
1. (a) (i) H2PO4 , (ii) HPO24 , (iii) NH2 , (iv) S2 , (v) H2O, (vi) OCl (vii) CH3O , (viii) C6H5O
+
(b) (i) HF, (ii) H2O, (iii) HPO24 , (iv) NH4 , (v) NH3, (vi) H2S, (vii) CH3OH2 , (viii) CH3 (OH) CH3;
(x) C6H5NH3

2. (i) NH4 /NH3 ;HC /C (ii) NH4 /NH3 ;H2O/OH

(iii) HS /S2 ;H2O/OH (iv) H3O /H2O;H2S/HS

(v) H2SO4 /HSO4 ;HCN/CN

3. Order of decreasing acid and base strengths are

+
(a) H3O > H3PO4 > HCN > H2O > NH3 (b) NH2 OH CN H2PO4 H2O
– –
4. (i) b, d, e, f (ii) (a) CN (b) CO23 , (c) N2H4, (d) C2H5O
+
(iii) (a) H2C2H3O2 , (b) H2CO3, (c) C5H5NH , (d) N2H62

5. 
(i) 2NH3  NH4 NH2 , (ii) First reaction
6. (i) greater the terminal oxygens, stronger the acid

(ii) decreasing basic strength is ClO2 , ClO3 , ClO4

7. (b) 8. (c) 9. (b)
 IONIC EQUILIBRIUM 149

LDA - 2

Dissociation of Weak Acids and Bases, pH Scale, Auto-ionization of Solvent

+ 10^-4, 2.5*10^-4 (log2.5
1. (i) Change the following pH values to [H ] values : (a) 4 (b) 3.6 =log5+log5-log10
~0.4)
(ii) Calculate the pH of each of the following solutions from the given hydronium ion molarity : n=1
3 –3 10.52–11 7.4 –8 0.82 14.92–15 0 -0.3
(a) 1.0 × 10 (b) 3.0 × 10 (c) 3.9 × 10 (d) 0.15 (e) 1.23 × 10 (f) 1.0 (g) 2.0

2. (i) What is the pH of a 500-mL aqueous solution containing 0.050 mol of NaOH ? 13
10^-8
(ii) (a) Calculate Ka for an acid whose 0.10 M solution has a pH of 4.50.

(b) Calculate Kb for a base whose 0.10 M solution has a pH of 10.50. 10^-6

3. (i) Determine pH of a solution obtained by mixing 100 mL of a HCl solution of pH = 2 with 400 mL of another HCl solution
of pH = 3.

(ii) Determine pH of a solution obtained by mixing 100 mL of 0.1 M HCl with 500 mL 0.01 NaOH solution.
– –10
4. (i) What is the CN ion concentration in a 0.010 M solution of HCN ? (Ka = 6.2 × 10 ) 2.48*10^-6

(ii) Calculate the ionization constant of formic acid, HCHO2, which ionizes 4.2% in 0.10 M solution. 1.8*10^4

5. Calculate the percent dissociation of acetic acid in a solution 0.200 M in HC2H3O2 and 0.100 M in HCl.
–5 0.018%
(Ka of CH3COOH = 1.8 × 10 )
10^-3 3.6*10^-4 6.3* " "
+
6. Calculate [H ], [C2H3O2 ] , and [C7H5O2 ] in a solution that is 0.0200 M in HC2H3O2 and 0.0100 M in HC7H5O2. Ka
–5 –5
values for HC2H3O2 and HC7H5O2 are 1.8×10 and 6.3×10 , respectively.

7. pH of a 0.2 M aqueous solution of hydrofluoric acid (HF) is 2. To what volume, a 1.0 L HF solution of molarity 0.2, must be
diluted in order to double its pH ?

8. In an aqueous solution, a 0.5 M tri-methyl amine is 2.5% ionized. Determine :

– + +
(a) [OH ], [(CH3)3NH ], [(CH3)3N] and [H ] and pH of solution ?

(b) Determine degree of ionization if concentration is decreased to 0.01 M ?

9. Which one of the following is a dibasic acid ?

(a) H3PO4 (b) H3PO3 (c) H3BO3 (d) H3AsO4

10. Which of the following is the weakest ?

(a) C6H5NH2 : Kb = 3.8 × 10–10 (b) NH4OH : Kb = 1.6 × 10–5

(c) C2H5NH2 : Kb = 5.6 × 10–4 (d) C9H7N : Kb = 6.3 × 10–10.

150 IONIC EQUILIBRIUM

11. If the dissociation constants of two weak acids HA1 and HA2 are K1 and K2, then the relative strengths of HA1 to HA2 are
given by

(a) K1/K2 (b) K2/K1 (c) K1 /K 2 (d) K 2 /K1 .

12. Solution A has pH = 3 and solution B has pH = 6. Which one of the following is correct ?
(a) Solution A is twice as acidic as B (b) Solution B is twice as acidic as A
(c) Solution A is 1000 times more acidic than B (d) Solution B is 1000 times more acidic than A

Answer Key

–4 –4
1. (i) (a) 10 , (b) 2.5 × 10

(ii) (a) 3.00, (b) 10.52, (c) 7.41, (d) 0.82, (e) 14.910, (f) 0.00, (g) – 0.30
–8 –6
2. (i) 13, (ii) (a) 1.0 × 10 , (b) 1.0 × 10
–6 –4
3. (i) 2.55, (ii) 2.08 4. (i) 2.5 × 10 M, (ii) 1.8 × 10 5. 0.018%
–3 –4 –4
6. 1.0 × 10 M, 3.6 × 10 M, 6.3 × 10 M 7. 1680L 8. (a) pH = 12 (b) 0.16

9. (a) 10. (a) 11. (c) 12. (c)

 IONIC EQUILIBRIUM 151

LDA - 3

pH of Solution, Buffer Solution

1. The pH of 0.1 M acetic acid solution is
(a) < 0 (b) > 1 (c) 1 (d) 7
2. The pH of a solution is 6. It is diluted ten times. The resulting solution will be
(a) Neutral (b) Acidic (c) Basic (d) Unaffected.
3. On dilution, the pH of a basic solution :
(a) remains the same (b) decreases
(c) increases
(d) may increase or decrease depending upon the nature of the solution.

1
4. For a weak electrolyte, a plot of vs gives a^2=k/C
C
(a) straight line (b) parabola (c) hyperbola (d) exponential curve
5. The correct statement(s) regarding the following reaction is/are

[Cu(H2O)3 (OH)]  [Al(H2O)6 ]3 

 2
 [Cu(H2O)4 ]  [Al(H2O)5 (OH)]
2

A B C D

(a) A is acting as an acid while B is a base. (b) A is base while B is an acid.

(c) C is conjugate acid of A and D is conjugate base of B.
(d) C is conjugate base of A and D is conjugate base of B.
6. pH of a 1000 cc solution is 2. It will not change if
(a) 100 cc of water is added to it (b) 100 cc of 0.1 M HCl is added to it
(c) 100 cc of N/100 HCl is added to it (d) 1 cc of 0.1 M HCl is added to it.
7. What must be the ratio of acetate ion concentrated to acetic acid concentration in an aqueous solution in order to provide a
–5
solution of pH 5 ? The Ka of acetic acid is 1.8 × 10 .
(a) 0.056 (b) 1.0 (c) 1.8 (d) 5.0
–4
8. What is the pH of the solution that results when 10.0 mL of 0.10 HF (Ka = 6.7 × 10 ) and 10.0 mL of 0.04 M NaOH are mixed ?
(a) 1.0 (b) 1.2 (c) 1.5 (d) 3.0
+ –6
9. At 90ºC, pure water has [H ] = 10 M. Based on this, the correct statement(s) is (are)
(a) Increasing the temperature, increases the degree of ionization of water.
(b) At 60ºC, pH of pure water will be less than 6.
–6
(c) At 90ºC, pH of a 10 M HCl solution will be less than 6.
–12
(d) Ionization constant of H2O (Ka) at 90ºC is 10 .] strong ionize full
10. (i) Explain why a solution containing a strong base and its salt does not act as a buffer solution.
(ii) (a) What is the hydronium ion concentration in a solution of 0.0200 M NaC2H3O2 and 0.0500 M HC2H3O2 ?
–5
(Ka = 1.8 × 10 ) 4.46666 *10^-5
(b) Determine the pH of the solution. 4.35
–10 9.7
(iii) What is the pH of a solution that is 0.0100 M in HCN and 0.0200 M in NaCN ? (Ka of HCN = 4 × 10 )
152 IONIC EQUILIBRIUM

11. It is desired to prepare a buffer solution consisting of 0.10 M HC2H3O2 and 0.10 M NaC2H3O2. Assuming no volume Change
upon the addition of the pure compounds, state what reagents and in what quantities should be added to 1.00 L of each of the
following solutions to prepare the desired buffer solution :

(a) 0.10 M HC2H3O2 (b) 0.20 M HC2H3O2 (c) 0.20 M NaC2H3O2 (d) 0.10M NaC2H3O2

(e) 0.10 M NaOH

12. Which of the following combinations of solutes would result in the formation of a buffer solution ?
(a) NaC2H3O2 + HC2H3O2 (b) NH4Cl + NH3 (c) HCl + NaCl (d) HCl + HC2H3O2
(e) NaOH + HCl (f) NaOH + HC2H3O2 in a 1 : 1 mole ratio
(g) NH3 + HCl in a 2 : 1 mole ratio (h) HC2H3O2 + NaOH in a 2 : 1 mole ratio
–
13. (i) Determine [OH ] of a 0.050 M solution of ammonia to which has been added sufficient NH4Cl to make the total NH 4
–5
equal to 0.100. (Kb of NH3 = 1.8 × 10 ) 9*10^-6
(ii) Calculate the pH of a solution made by mixing 50.0 mL of 0.200 M NH4Cl and 75.0 mL of 0.100 M NaOH.
–5
(Kb of NH3 = 1.8 × 10 ) 4.25,9.75

Answer key

1. (b) 2. (b) 3. (b) 4. (d) 5. (b) 6. (b,c) 7. (c)

8. (c) 9. (ac)

–5
10. (ii) (a) 4.5 × 10 (b) 4.35, (iii) 9.69

11. (a) 0.10 mol NaC2H3O2, (b) 0.10 mol NaOH, (c) 0.10 mol HCl, (d) 0.10 mol HC2H3O2 (e) 0.20 mol HC2H3O2

–6
12. (a), (b), (g), (h) 13. (i) 9.0 × 10 , (ii) pOH = 4.27, pH = 9.73
 IONIC EQUILIBRIUM 153

LDA - 4

Buffers, Polyprotic Acids and Bases, Hydrolysis

1. Assuming that the final volume in each case remains the same, compare the effect of adding 0.010 mol of solid sodium
hydroxide to
–5
(a) 1.0 L of a solution 1.8 × 10 M in HCl and
–5
(b) 1.0 L of a solution containing 0.10 mol of NaC2H3O2 and 0.10 mol of HC2H3O2. (Ka of CH3COOH : 1.8 × 10 )

2. Acid dissociation constants of the phosphoric acid (H3PO4) are :

K a1  7.5105 ; H3PO4  H  H 2 PO4

K a 2  6.2108 ; H 2 PO4  H  HPO 42

K a 3  1012 ; HPO42  H  PO34

If a solution of phosphoric acid has pH = 3 and [H3PO4] = 0.1, determine the concentrations of PO34 , HPO 24 and H 2 PO
4
in the same solution.

3. Hydrazine, N2H4, can interact with water in two stages :

N 2 H 4 (aq)  H 2 O(l )  N 2 H 5 (aq)  H 2 O (aq); K b1  8.5107

N 2 H5 (aq)  H 2 O(l )  N 2 H 62 (aq)  HO (aq); K b2  9 1016

–
(a) What is the concentration of OH , N 2 H5 and N 2 H 62 in a 0.01 M aqueous solution of hydrazine ? 9.2*10^-5

(b) What is the pH of 0.01 M aqueous solution of hydrazine ? 9.96

–2 –5
4. Determine pH of a 0.2 M solution of oxalic acid. (K1 = 6.5 × 10 , K2 = 6 × 10 ). 1.065

5. What volume of a 2 M HCl and what weight of CH3COONa should be mixed and finally diluted to 100 mL to get a solution of
– –5
pH = 5 with [CH3COO ] ion equal to 0.5M ? Ka of CH3COOH = 2 × 10 .

6. Addition of a 100 mL of 0.2 M HCl solution to a 100 mL solution of a weak base lowers the pH from 11 to 8.48. Determine Kb of
the weak base.
154 IONIC EQUILIBRIUM

7. Calculate the pH of a buffer solution that is 0.20 M in HCN and 0.12 M in NaCN. Will the pH change if the solution is diluted
by a factor of 2 ? Explain. (Ka = 4 × 10–10) 9.17
no, cause log neqs/neqacid same
8. (i) Explain why a solution of NH4Cl is acidic.
wb+sa
– –5 10^-5.6
(ii) What is the OH concentration of a 0.010 M solution of NaC2H3O2 ? (Ka of CH3COOH = 1.8 × 10 )

–5 0.0223
(iii) Calculate the extent of hydrolysis in a 0.0100 M solution of NH4Cl. (Kb of NH3 = 1.8 × 10 )

9. What is the change in pH that results from the addition of 20 mL. of 0.10 M NaOH to a buffer made by combining 200 mL of 0.070
–5
M benzoic acid (C6H5COOH, Ka = 6.4 × 10 ) with 100 mL of 0.070 M sodium benzoate ?

(a) + 0.31 (b) + 0.20 (c) + 0.18 (d) – 0.20

10. When some NH4Cl is added to an aqueous solution of NH3 ?

(a) The pH decreases and [NH3] increases (b) The pH increases and [NH3] increases

(c) The pH increases and [NH3] decreases (d) The pH decreases and [NH3] decreases

Answer Key

1. (a) pH has changed from 4.74 to 12, (b) pH has changed from 4.74 to 4.82

2. [H 2 PO 3 2 7 3
4 ]  7.5 10 M [HPO 4 ]  4.65 10 M [PO 4 ]  4.65 10
, , 16
M

3. (a) [OH ]  [N 2 H 5 ]  9.2 105 M (b) pH = 9.96 4. 1.065

–6 –6
5. 12.5 mL, 6.15g 6. 2×10 7. pH = 9.17. 8. (ii) 2.4 × 10 M (iii) 0.023%

9. (c) 10. (a)

 IONIC EQUILIBRIUM 155

LDA - 5
Salt Hydrolysis, Solubility Equilibria
– –5
1. (i) What is the OH concentration of a 0.010 M solution of NaC2H3O2 ? (Ka = 1.8 × 10 )
–5
(ii) Calculate the extent of hydrolysis in a 0.0100 M solution of NH4Cl. (Kb = 1.8 × 10 )
– –4
2. (i) Calculate [OH ] in a 1.00 M solution of NaOCN. (Ka of HOCN = 3.3 × 10 )

(ii) Calculate the pH in a 0.100 M solution of NH4OCN.

–4 –5
(Ka of HOCN = 3.3 × 10 Kb of NH3 = 1.8 × 10 )
–5
(iii) Calculate the pH of 0.10 M NH4NO3 solution. (Kb of NH3 = 1.8 × 10 )
– +
3. What is the [OH ] in a 0.0100M solution of aniline hydrochloride which contains the C6H5 NH3 ?
–7 –14
4. What is the pH of a 0.0050 M solution of Na2S ? K1 (H2S) = 10 , K2 = 10 .
–3 –8 –13
5. Consider the triprotic acid H3PO4 with Ka values of ; Ka1 = 7.5 × 10 , Ka2 = 6.2 × 10 , and Ka3 = 2.2 × 10 .
Which one of the following statements is false ?

(a) A solution of H3PO4 is acidic. (b) A solution of NaH2PO4 is acidic.

(c) A solution of Na2HPO4 is neutral (d) A solution of Na3PO4 is basic.

6. The pH value of 10–3 M aqueous solution of NaCl is

(a) 7 (b) 3 (c) 11 (d) 14

7. Which is the correct representation for the solubility product constant of Ag2CrO4 ?

2 2
(a) Ag CrO24 (b) 2 Ag CrO24 (c) Ag CrO24 (d) 2 Ag CrO24

–5
8. (i) When a sample of solid AgCl is shaken with water at 25 ºC, a solution containing 1.0 × 10 M silver ions is produced.
Calculate Ksp.

(ii) Calculate the solubility of A2X3 in pure water, assuming that neither kind of ion reacts with water.
–23
For A2X3, Ksp = 1.1 × 10 .

9. Calculate the solubility product constants of the following compounds. The solubilities are given in mol/L.
–5 –3
(a) BaSO4, 1.05 × 10 mol/L (b) TlBr, 1.9 × 10 mol/L
–4 –4 –4
(c) Mg(OH)2, 1.21 × 10 mol/L (d) Ag2C2O4, 1.15 × 10 mol/L (e) La(IO3)3, 7.8 × 10 mol/L.

10. (i) Which has a greater molarity in water, AgCl or Mg(OH)2 ? Can relative solubilities be predicted on the basis of the relative
magnitudes of the Ksp values alone ? Explain.
–10 –11
Ksp AgCl = 10 , Ksp of Mg (OH)2 = 1.2 × 10
156 IONIC EQUILIBRIUM
–18
(ii) The values of Ksp for the slightly soluble salts MX and QX2 are each equal to 4.0 × 10 . Which salt is more soluble ?
Explain your answer fully.

Answer Key

–6 –6
1. (i) 2.35 × 10 M (ii) 0.0234% 2. (i) 5.5 × 10 , (ii) 6.39, (iii) 5.13

–11
3. 2.0 × 10 M 4. 11.23 5. (b) 6. (a) 7. (a)

–10 –5
8. (i) 1.0 × 10 , (ii) 1.0 × 10 mol/L

–10 –6 –12 –12 –11

9. (a) 1.1 × 10 (b) 3.6 × 10 (c) 7.09 × 10 (d) 6.1 × 10 (e) 1.0 × 10 10. (i) Mg(OH)2; No, (ii) QX2
 IONIC EQUILIBRIUM 157

LDA - 6

Solubility Equilibria
1. The solubility product of Hg2I2 is equal to

2 2
(a) Hg 2 I (b) Hg I (c) Hg 2 I (d) Hg I

2. The precipitate of CaF2 (Ksp = 1.7×10–10) is obtained on mixing equal volumes of

(a) 10–4 M Ca2+ and 10–4 M F– (b) 10–2 M Ca2+ and 10–3 M F–

(c) 10–5 M Ca2+ and 10–3 M F– (d) 10–3 M Ca2+ and 10–5 M F–

3. If the solubility of lithium sodium hexafluoro-aluminate, Li 3Na 3(AlF 6) 2 is ‘a’ mole/litre, the solubility product is equal to

(a) a8 (b) 12a3 (c) 18a3 (d) 2916a8

4. For the sulphides below the solubility product are shown within brackets, the least soluble sulphide is

(a) Cos (Ksp = 3 × 10–25) (b) MnS (Ksp = 1.5 × 10–10)

(c) ZnS (Ksp = 1.2 × 10–28) (d) NiS (Ksp = 1.5 × 10–24)

5. The ionic product of an electrolyte

(a) is always equal to its solubility product (Ksp) (b) can be equal to or less than Ksp

(c) is always less than Ksp (d) can be less than, equal to or greater than Ksp
–8
6. What is the molar solubility of MgF2, Ksp = 8.0 × 10 , in a 0.20 M solution of KF ?
–8 –7 –6 –4
(a) 8.0 × 10 M (b) 4.0 × 10 M (c) 2.0 × 10 M (d) 2.7 × 10 M

A solution is 0.10 M in Ag , Ca , Mg and Al ions. Which compound will precipitate at the lowest [PO34 ] when a solution
+ 2+ 2+ 3+
7.
of Na3PO4 is added ?
–16 –33
(a) Ag2PO4(Ksp = 1 × 10 ) (b) Ca3(PO4)2 (Ksp = 1 × 10 )
–24 –20
(c) Mg3(PO4)2 (Ksp = 1 × 10 ) (d) AlPO4 (Ksp = 1 × 10 )

8. A 1.000L solution is prepared in which Ni2 , Ag  , and Mn2 ions are present in solution, all at a concentration of
0.0010M. A solution of sodium sulfide Na2S is slowely added. Which compound will begin to precipitate FIRST ? The Ksp of
–21 –49 –15
NiS = 3.0 × 10 ; Ag2S = 1.0 × 10 ; MnS = 5.1 × 10 .
(a) Ag2S (b) NiS (c) MnS (d) Na2S
9. (i) The solubility of PbSO4 in water is 0.038 g/L. Calculate the solubility product constant of PbSO4. (Atomic mass : Pb = 207.2)
–10
(ii) Calculate the solubility of AgCl in 0.20 M AgNO3 solution. Ksp AgCl = 10
158 IONIC EQUILIBRIUM

–11 –9
10. (i) Calculate the simultaneous solubility of CaF2 and SrF2. Ksp (CaF2) = 3.4 × 10 , Ksp (SrF2) = 2.9 × 10
–12
(ii) How many mol CuI (Ksp = 5 × 10 ) will dissolve in 1.0 L of 0.10 M NaI solution ?

11. The concentration of sulphide ion is 1.0 × 10–19M. If 10 mL of this is added to 5 mL of 0.04 M solution of the following : FeSO4,
MnCl2, ZnCl2 and CdCl2. in which of these solutions precipitation will take place ?
–8 –13 –24 –27
Ksp : FeS (6.3 × 10 ); MnS (2.5 × 10 ); ZnS (1.6 × 10 ); CdS (8 × 10 )

12. How much AgBr could dissolve in 1.0L of 0.40 M NH3? Assume that Ag(NH3 )2 is the only complex formed.

–13
Ksp (AgBr) = 5 × 10 , Kf Ag(NH3 )2 108

Answer Key

1. (c) 2. (b) 3. (d) 4. (c)

5. (d) 6. (c) 7. (b) 8. (a)

–8 –10 – –3 –11
9. (i) 1.6 × 10 , (ii) 5 × 10 M 10. (i) [F ] = 1.8 × 10 M , (ii) 5 × 10 M
–3
11. ZnCl2 and CdCl2 12. 2.8 × 10 M
 IONIC EQUILIBRIUM 159

LDA - 7

Indicators, Indicator Curves, Titrations

1. Which of the following curves corresponds to the titration of a weak base (i.e., analyte) with a strong acid (i.e., titrant) ?

(a) (b)

(c) (d)

2. Which of the following describes the following titration curve ?

14

7
pH

0
mL added

(a) A strong base is added to a strong acid (b) A strong base is added to a weak acid
(c) A strong acid is added to a strong base (d) A strong acid is added to a weak base
3. What is the pH at the equivalence point in a titration of 0.02 M NH3 (aq) with 0.02 M HBr (aq) For the ammonia
–5
Kb = 1.8 × 10 ?
(a) 5.5 (b) 5.6 (c) 7.0 (d) 8.5
4. Which of the following is (are) true for an acid-base titration ?
+
(a) Indicators catalyze the titration by releasing or accepting H .
(b) Indicators don’t affect significantly the pH of the solution to which it is added.
(c) Indicators are essential for neutralization to occur.
(d) Indicators have different colours in dissociated and undissociated forms.
–5
5. Imagine an indicator HIn that is red in strong acid and green in strong base. KIn = 4.0 × 10 . Which of the following
statements is false ?
–
(a) The colour of the HIn molecule is red (b) The colour of the In ion is green
(c) The indicator changes colour when pH is about equal to pKIn
–
(d) At pH = 7.00 [HIn] = [In ]
160 IONIC EQUILIBRIUM

6. When phenolphthalein is used as the indicator in a titration of an HCl solution with a solution of NaOH, the indicator
undergoes a colour change from clear to red at the end point of the titration. This colour change occurs abruptly because
(a) phenolphthalein is a very strong acid that is capable of rapid dissociation.
(b) the solution being titrated undergoes a large pH change near the end point of the titration.
(c) phenolphthalein undergoes an irreversible reaction in basic solution.
–
(d) OH acts as a catalyst for the decomposition of phenolphthalein.

7. In the figure below, 40.00 mL of 0.1000 M ACID is titrated with 0.1000 M BASE.
Which reaction is most likely illustrated by this titration curve ?

(a) HCl(aq) + KOH(aq)  KCl(aq) + H2O(l ) (b) HNO3(aq) + NaOH(aq)  NaNO3(aq) + H2O(l )
(c) H2SO4(aq) + Ba(OH)2(aq)  BaSO4(aq) + H2O(l )

(d) CH3CH2COOH + NaOH  CH3CH2COONa(aq) + H2O(l )

8. In the figure below, 40.00 mL of 0.1000 M weak base (B) is titrated with 0.1000 M HCl. Consider the data on this titration
curve to calculate the Kb of the weak base, B.

–5 –6
(a) Kb = 1.77 × 10 (b) Kb = 5.37 × 10
–10 –10
(c) Kb = 5.62 × 10 (d) Kb = 1.87 × 10
 IONIC EQUILIBRIUM 161

9. Solution of X is being titrated against a solution of Y. If phenolphthalein is found to be a suitable indicator, X and Y could
be respectively.
(a) NaOH and HCl (b) HCl and NaOH
(c) CH3COOH and NaOH (d) HCl and NH3(aq)

10. What is the pH at the equivalence point when 50.0 mL of 0.500 M CH3COOH is titrated with 0.500 M NaOH ? (The Ka of
–5
CH3COOH is 1.8 × 10 ).
(a) 4.74 (b) 9.26 (c) 7.00 (d) 9.07

Answer Key

1. (d) 2. (c) 3. (b) 4. (bd)

5. (d) 6. (b) 7. (d) 8. (a)

9. (abc) 10. (d)

162 IONIC EQUILIBRIUM

LDA - 8

1. All questions marked “S” are single choice questions

2. All questions marked “M” are multiple choice questions
3. All questions marked “C” are comprehension based questions
4. All questions marked “A” are assertion–reason type questions
(A) If both assertion and reason are correct and reason is the correct explanation of assertion.
(B) If both assertion and reason are true but reason is not the correct explanation of assertion.
(C) If assertion is true but reason is false.
(D) If reason is true but assertion is false.
5. All questions marked “X” are matrix–match type questions
6. All questions marked “I” are integer type questions

Comprehension
Consider the following titration curves for answering the next four questions :

1. (C) Which of the above titration curves corresponds to titration of a weak acid (in flask) with a strong base (in burette) ?

(a) 1 (b) 2 (c) 3 (d) 4

2. (C) Consider the titration curve 2, what was the original concentration of acid or base in the flask if the original volume was
100 mL and it was titrated with a standard solution (in burette) that had a concentration of 0.1 M ?

(a) 0.1 M (b) 0.15 M (c) 0.20 M (d) 0.25 M

3. (C) What is the approximate value of ionization constant of weak acid being titrated in Q. no. 1 question ?
–4 –5 –6 –8
(a) 10 (b) 10 (c) 10 (d) 10

4. (M) A buffer solution can be prepared from a mixture of

(a) sodium acetate and acetic acid in water (b) sodium acetate and HCl in water

(c) NH4Cl and NaOH in water (d) NH3(aq) and NaOH(aq)

 IONIC EQUILIBRIUM 163

–10
5. (M) Ksp of CaF2 is 1.7 × 10 . Which of the following combinations will bring about precipitation of CaF2 ?
–4 2+ –3 – –5 2+ –2 –
(a) 10 mL 10 M Ca + 10 mL 2 × 10 M F (b) 10 mL 10 M Ca + 10 mL 2 × 10 M F
–2 2+ –3 – 3 2+ –5 –
(c) Equal volumes of 10 MCa and 10 MF (d) 10 mL 10 MCa + 10 mL 10 M F

6. (M) In H3PO4, which of the following is true ?

(a) K a K a1 K a 2 K a 3 (b) K a1 Ka2 K a3 (c) K a1 Ka2 K a3 (d) K a1 Ka2 K a3

7. (M) Which of the following salts will not undergo hydrolysis ?

(a) NaCl (b) KCl (c) NH4Cl (d) CH3COONa

8. (I) If a 1.0 mL 1M HCl solution is added to 99 mL of water at 25ºC, pH of water will change by x unit. The value of x is

9. (I) Sum of Basicity of H 3PO4, H3PO3 and H3PO2 is equal to _____.

10. (X) Match the Column-I with Column-II :

Column–I Column–II

(Salt) (Solubility product)

(A) Zirconium phosphate (p) 27 S4

(B) Aluminium phosphate (q) 108 S5

(C) Calcium phosphate (r) 6912 S7

(D) Sodium phosphate (s) S2

11. (A) Assertion : pH of an aqueous solution of 10 –7 M NaOH at 25ºC is greater than 7.

Reason : In the given concentration range, contribution of autoionization of water to total [OH –] becomes significant.

(a) A (b) B (c) C (d) D

12. (A) Assertion : pH of a 0.001 M H2SO4 solution is 3.

Reason : H2SO4 is a strong acid and [H+] in its aqueous solution can be determined stoichiometrically assuming its
complete ionization.

(a) A (b) B (c) C (d) D

13. (A) Assertion (A) : Ionic reactions are not instaneous

Reason (R) : Oppositely charged ions exert strong forces.

(a) A (b) B (c) C (d) D

14. (A) Assertion : Addition of a small amount of either HCl or NaOH to an acetic acid sodium acetate buffer does not
change the pH significantly.

Reason : pH of a buffer solution never changes.

(a) A (b) B (c) C (d) D

164 IONIC EQUILIBRIUM

Answer Key

1. (a) 2. (d) 3. (b)

4. (a,b,c) 5. (b,c) 6. (a,c) 7. (a,b)

8. (0005) 9. (0006) 10. (A–r), (B–s), (C–q), (D–p)

11. (a) 12. (d) 13. (d) 14. (c)