IONIC EQULIBRIUM (Physical Chemistry)

EXERCISE-I
DPP-1
Dissociation of Water & pH
1. Select the number of correct options for degree of dissociation
(i) It is independent of nature of solvent
(ii) It increases as dilution increases
(iii) It may get affected by presence of other ions
(iv) It always increases with increase in temperature.
(A) 1 (B) 2 (C) 3 (D) 4
2. Select the number of correct options for dissociation of water
(i) It produces equal number of H + and OH –
(ii) K W = Ionic product of water = [H + ][OH − ]
(iii) K diss [H2O] = K W
[H+ ][OH− ]
(iv) K diss = [H2 O]

(A) 1 (B) 2 (C) 3 (D) 4

3. Select the correct option
(A) If [H + ] = 2 × 10−5 then pH = 5.3
(B) If [H + ] = 5 × 10−8 then pH = 7.3
(C) If [H + ] = 4 × 10−4 then pH = 3.6
(D) If [H + ] = 5 × 10−5 then pH = 5.5
4. Select the correct option
(A) If pH = 4.3 then [H + ] = 3 × 10−4
(B) If pOH = 6.7 then [OH − ] = 2 × 10−7
(C) If pH = 5.4 then [H + ] = 6 × 10−5
(D) If pOH = 6.3 then [OH − ] = 5 × 10−6
5. Select the correct option (at 298 K)
(A) [H + ][OH − ] = 14
(B) [H + ][OH − ] = 10−12
(C) pH + pOH = K W
(D) pH + pOH = 14
6. The pH of solution is increased from 3 to 6. Its H + ion concentration will be:
(A) Reduced to half (B) Doubled
(C) Reduced by 1000 times (D) Increased by 1000 times

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7. Ionic product of water will increase, if:

(A) Pressure is decreased (B) H+ is added

(C) OH– is increased (D) Temperature is increased

8. pH of water is 7 at 25 °C. If water is heated to 70 °C then choose the correct statement-
(A) pH will decrease and solution becomes acidic
(B) pH will increase
(C) pH will remain constant as 7
(D) pH will decrease but solution will remain neutral
9. Select the correct option
(A) At a given temperature, as [H + ]increases, [OH − ] remain same in pure water
(B) At a given temperature as [H + ]increases, [OH − ]also increases in pure water
(C) As temperature increases [H + ]increase but [OH − ]decreases in pure water
(D) As temperature increases [H + ]increases, [OH − ]also increases in pure water
10. At 60°C, pure water has [H3 O+ ] = 10−6.7mol/lit. what is the value of K W at 60 °C:
(A) 10−6 (B) 10−12 (C) 10−67 (D) 10−13.4

11. Calculate the number of H+ present in one ml of solution whose pH is 13.

(NA = 6 × 1023 )
12. At 60 °C Kw for H2 O is 9 × 10−14 .
(i) What is pH of pure water at 60 °C. (log 3 = 0.47)
(ii) What is the nature of solution at 60 °C having
(a) pH = 6.7 (b) pH = 6.35
13. Percentage ionisation of water at certain temperature is 3.6 × 10−7 %. Calculate Kw and pH of
water at this temperature. 2H2 O ⟶ H3 O+ + OH −
14. At −50∘ C, liquid NH3 has ionic product is 10−30 M 2. How many amide (NH2− ) ions are present
per mm3 in pure liquid NH3 ? (Take NA = 6 × 1023 )

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DPP-2
pH of Strong Acid or Base
1. The pH of 4.0 × 10–4 M HNO3 solution is (log 2 = 0.3)
(A) 4.6 (B) 3.4 (C) 3.6 (D) 4.0
2. What is the quantity of NaOH present in 250 cc of the solution, so that it gives a pH= 13:

(A) 10–13 g (B) 10–1 g (C) 1.0 g (D) 4.0 g

3. How many moles of HCl must be removed from 1 litre of aqueous HCl solution to change its pH
from 2 to 3:
(A) 1 (B) 0.02 (C) 0.009 (D) 0.01
M M
4. 10 ml of 200 H2 SO4 is mixed with 40 ml of 200 H2 SO4 . The pH of the resulting solution is

(A) 1 (B) 2 (C) 2.3 (D) none of these

5. An aqueous solution of HCl is 10−9 M HCl. The pH of the solution should be:
(A) 9 (B) Between 6 and 7 (C) 7 (D) Unpredictable
6. What is the pH of 10–7 M HCl solution at 25 °C?
(A) 7.0 (B) 6.70 (C) 6.62 (D) 6.79
7. Find concentration of HCl in solutions having pH = 6.7 at 298 K. [Given ∶ log2 = 0.3]
(A) 2 × 10–7 M (B) 10–7 M (C) 1.5 × 10–7 M (D) 3 × 10−7 M
8. Calculate pH of following solutions :
(a) 0.1 M HCl
(b) 10–8 M HCl [Use √401 = 20.02 and log 1.051 = 0.03]
(c) 10–10 M NaOH
9. Calculate pH of following solutions :
(a) 10–3 mole of KOH dissolved in 100 L of water.
(b) Decimolar solution of Baryta (Ba(OH)2 ), diluted 100 times.
10. 0.1 mole HCl is dissolved in distilled water of volume V. Then, at lim , pH of solution is equal to
V→∞

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DPP-3
pH of WeaK Acid or Base
1. For two monobasic acids A and B, pKa1= 1.2, pKa2 = 2.8 respectively in value, then which is
true:
(A) A & B both have equal acidic strength
(B) A is stronger than B
(C) B is stronger than A
(D) Depends on concentration
2. The pH of a 0.02 M ammonia solution which is 5% ionised will be:
(A) 2 (B) 11 (C) 5 (D) 7
3. Find H+ of 0.1 M CH3COOH is: (Dissociation constant = 1 × 10−5 )

(A) 10−5 (B) 10−4 (C) 10−3 (D) 10−2

4. What is the pK b of a weak base whose 0.1 M solution has pH = 9.5?
(A) 7.5 (B) 8 (C) 9 (D) 10
5. pH of a weak monoacidic base is 12. What will be concentration of base (K b = 10–4 ):–
(A) 1 M (B) 0.1 M (C) 0.01 M (D) 0.001 M
6. Calculate pH of following solutions:
(b) 0.1 M CH3 COOH (Ka = 1.8 × 10−5 ) (log√1.8 = 0.13)
(c) 0.1 M NH4 OH (K b = 1.8 × 10−5 )
(f) 10−7 M CH3 COOH (K a = 10−5 )
(g) 10−8 M CH3 COOH (K a = 1.8 × 10−5 ) [√401= (20.02)] [log 1.051 = 0.03]
7. Calculate:
(a) K a for a monobasic acid whose 0.10 M solution has pH of 4.50.
(b) K b for a monoacidic base whose 0.10 M solution has a pH of 10.50.
8. Calculate the ratio of degree of dissociation (α2 /α1 ) when 1 M acetic acid solution is diluted
100 times. [Given K a = 10−5 M]
9. The solution of weak monoprotic acid which is 0.01 M has pH = 3. Calculate K a of weak acid.
10. Boric acid is a weak monobasic acid. It ionizes in water as
B(OH)3 + H2 O ⟶ B(OH)4 + H + : Ka = 5.9 × 10−10
Calculate pH of 0.3 M boric acid. [log(√1.77) = 0.13]

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DPP-4
pH of Mixture of Acid or Base
1. Consider an aqueous solution, 0.1 M each in HOCN, HCOOH, (COOH)2 and H3 PO4 . For HOCN ,
[H+ ][OCN− ]
we can write: K a (HOCN) = ⋅ [H + ]in this equation is:
[HOCN]

(A) H + ions released by HOCN

(B) Sum of H + ions released by all monoprotic acids
(C) Sum of H + ions released only the first dissociation of all the acids.
(D) Overall H + ion concentration in the solution.
2. The pH of the solution produced when an aqueous solution of strong acid having pH = 5 is
mixed with equal volume of an aqueous solution of strong acid of pH = 3 is:
(A) 3.3 (B) 3.5 (C) 4.5 (D) 4.0
3. What are [H + ]in a solution that contains 0.03 M HA and 0.07 M HB. K a for HA and HB are
3.0 × 10−4 and 1.0 × 10−4 respectively.
(A) [H + ] = 4 × 10−3 M (B) [H + ] = 0.1
(C) [H + ] = 4 × 10−6 M (D) [H + ] = 0.01
4. An aqueous solution contains 0.01 M RNH2 ( K b = 2 × 10−6 ) & 10−4 M NaOH. The concentration
of OH − is nearly:
(A) 2.414 × 10−4 (B) 10−4 M (C) 1.414 × 10−4 (D) 2 × 10−4
5. pH of a solution obtained by mixing equal volumes of 0.1 M Triethyl amine (K b = 6.4 × 10−5 ) &
4
M NH4 OH(K b = 1.8 × 10−5 ) will be:
45

(A) 11.3 (B) 10.3 (C) 12.3 (D) 11.45

6. Calculate pH if equal volume of HCl solution (pH = 4) + 0.0019 N HCl solution
7. Calculate pH of following solutions:
(a) 0.1 M H2 SO4 (50ml) + 0.4 M HCl (50ml)[log 0.3 = −0.522]
(b) 0.1 M HA + 0.1 M HB [Ka(HA) = 2 × 10−5 ; Ka(HB) = 4 × 10−5 ][log = 0.39]
8. Upon passing 0.01 mole HCl gas through 100 mL of 0.05 M Formic acid solution
(K a = 1.8 × 10−4 M) determine change in pH of solution and [HCOO− ]in resulting solution.
9. Calculate [H + ]and [CHCl2 COO− ]in a solution that is 0.01 M in HCl and 0.01 M in CHCl2 COOH.
Take (K a = 3 × 10−2 )(√30 = 5.5)
10. Calculate [H + ], [CH3 COO− ]and [C7 H5 O−
2 ]in a solution that is 0.02 M in acetic acid and 0.01 M in

benzoic acid. K a ( acetic ) = 1.8 × 10−5 , K a ( benzoic ) = 6.4 × 10−5.

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DPP-5
pH of Polyprotic Acid or Base
1. In aqueous solution the ionization constants for carbonic acid are
K1 = 4.2 × 10−7 and K 2 = 4.8 × 10−11
Select the correct statement for a saturated o.034 M solution of the carbonic acid :-
(A) The concentration of H + is double that of CO2−
3

(B) The concentration of CO2−

3 is 0.034 M

(C) The concentration of CO2−

3 is greater than that of HCO3
−

(D) The concentrations of H + and HCO−

3 are approximately equal

2. Approximate pH of 0.10 M aqueous H2 S solution having K1 and K 2 for H2 S at 25 ∘ C 10−7 and

10−13 respectively is :
(A) 4 (B) 5 (C) 9 (D) 8
3. Find concentration of PO3−
4 in I M H3 PO4 .

(Given K a1 = 10−4 M; K a2 = 10−7 M, K a3 = 10−11 )

(A) 10−11 M (B) 10−18 M (C) 10−16 M (D) 10−7 M
4. Find concentration of enH22+ in 0.1 M en(aq.) solution (en = ethylene diamine)
Given K b1 = 10−5 M K b2 = 10−11 M
(A) 10−11 M (B) 10−5 M (C) 10−9 M (D) 10−7 M
5. In a solution containing 0.1 M HCl and 0.1M H3 PO4 (having dissociation constants
K a1 , K a2 & K a3 ), Given: α ≪ 1 for H3 PO4 :
(A) [PO3−
4 ] = 100 K a1 K a2 K a3 (B) [PO3−
4 ] = 10 K a1 K a2 K a3

(C) [PO3−
4 ] = 1000 K a1 K a2 K a3 (D) [PO3−
4 ] = K a1 K a2 K a3

6. Calculate the pH of a 0.1 M solution of H2 NCH2 CH2 NH2 [ethylenediamine (en)].

K b1 and K b2 values of ethylenediamine are 8.5 × 10−5 and 7.1 × 10−8 respectively.
7. Calculate [H + ], [H2 PO−
4 ], [HPO4 ] and [PO4 ] in a 0.01 M solution of H3 PO4 .
2− 3−

Take K1 = 10−3 , K 2 = 10−8 , K 3 = 10−13 .

8. What are the concentrations of H + , HSO−
4 , SO4 and H2 SO4 in a 0.20 M solution of sulphuric
2−

acid?
Given: H2 SO4 ⟶ H + + HSO−
4; strong
HSO− + 2−
4 ⟶ H + SO4 ; K 2 = 10−2 M

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DPP-6
Bronsted Conjugate Acid Base Theory
1. The conjugate acid of NH2− is
(A) NH3 (B) NH2 OH (C) NH4+ (D) N2 H4
2. In the reaction, HNO3 + H2 O ⟶ H3 O+ + NO3 , the conjugate base of HNO3 is:
(A) H2 O (B) H3 O+ (C)NO−
3 (D) H3 O+ and NO3−
3. Which of the following is not a Bronsted acid:
(A) CH3 NH4+ (B) CH3 COO− (C) H3 O+ (D) HSO−
4

4. If equilibrium constant of CH3 COO− + H2 O ⟶ CH3 COOH + OH − is 5.55 × 10−10 at 25∘ C,

calculate equilibrium constant of CH3 COOH + H2 O ⟶ CH3 COO− + H3 O+ at 25∘ C.
(A) 1.8 × 10−4 (B) 1.8 × 109 (C) 5.55 × 104 (D) 1.8 × 10−5
5. If K a for RNH3+ (aq.) is 10−5 M at 25∘ C, then equilibrium constant of the given reaction is
RNH2 (aq) + HCl(aq) ⟶ RNH3+ (aq) + Cl− (aq)
(A) 10−5 M (B) 105 M (C) 10−9 M (D) 109 M
6. If pK b for fluoride ion at 25∘ C is 10.83 , the ionisation constant of hydrofluoric acid in water at
this temperature is:
(A) 1.74 × 10−5 (B) 3.52 × 10−3 (C) 6.75 × 10−4 (D) 5.38 × 10−2
7. If equilibrium constant of
CH3 COOH + H2 O ⟶ CH3 COO− + H3 O+ is 1.8 × 10−5 ,
equilibrium constant for CH3 COOH + OH − ⟶ CH3 COO− + H2 O is
(A) 1.8 × 10−9 (B) 1.8 × 109 (C) 5.55 × 10−9 (D) 5.55 × 1010
8. If pK b for fluoride ion at 25∘ C is 10.83, the ionisation constant of hydrofluoric acid in water at
this temperature is:
(A) 1.74 × 10−5 (B) 3.52 × 10−3 (C) 6.75 × 10−4 (D) 5.38 × 10−2
9. A certain weak acid has K a = 1 × 10−4. Calculate the equilibrium constant for its reaction with
strong base -
(A) 106 (B) 108 (C) 1010 (D) 10−10
10. What happen when NH4 Cl is added to solution of NH4 OH :-
(A) pH increases
(B) pH decreases
(C) pH remains same
(D) pH may increase or decrease

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11. Which of the following ions or compounds in a solution tend to produce an acidic, a basic or a
neutral solution?
(a) C2 H5 O− (b) Cu+2 (c) SO2−
3 (d) F −
(e) NH4+ (f) CH3 COONa (g) KNO3 (h) NaOCl
(i) Na2 CO3 (j) ZnCl2
12. What is ionisation constant of HOCl, if K b of OCl− = 4 × 10−10 ? Also find its pK a .

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DPP-7
pH of Bronsted Acid-Base(Salt Hydrolysis)
1. pH of an aqueous solution of NaCl at 85∘ C should be
(A) 7 (B) > 7 (C) < 7 (D) 0
2. 1 cc of 0.1 N HCl is added to 99 cc solution of NaCl . The pH of the resulting solution will be
(A) 7 (B) 3 (C) 4 (D) 1
3. The highest pH value is of:
(A) 0.1 M NaCl (B) 0.1 M NH4 Cl
(C) 0.1 M CH3 COONa (D) 0.1 M HCl
4. What is the pH of a 0.4 M NaCN (aq) solution ? ( pK b of CN − = 4.70)
(A) 9.15 (B) 11.45 (C) 11.85 (D) 5
N
5. Degree of Hydrolysis of 100 solution of KCN is (Given Ka = 1.4 × 10−9 )

(A) 2.7 × 10−3 (B) 2.7 × 10−2 (C) 2.7 × 10−4 (D) 2.7 × 10−5
6. What is the OH − concentration of a 0.1 M solution of CH3 COONa.
[K a (CH3 COOH) = 10−5 M]
7. Calculate the pH of a 2.0 M solution of NH4 Cl. [K b (NH3 ) = 1.8 × 10−5 ]
8. 0.25 M solution of pyridinium chloride C5 H6 N+ Cl− was found to have a pH of 2.699. What is Kb
for pyridine, C5 H5 N ? ( log 2 = 0.3010 )
9. Calculate the percent hydrolysis in a 0.06 M solution of KCN . [K a (HCN) = 6 × 10−10 ]
10. Calculate the pH of 1.0 × 10−3 M sodium phenolate, NaOC6 H5. Ka for HOC6 H5 is 1.0 × 10−10 . log
27 = 1.43

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DPP-8
pH of Polyvalent Cation or Anion
1. A solution of FeCl3 in water acts as acidic due to:
(A) Acidic impurities (B) Hydrolysis of Cl−
(C) Hydrolysis of Fe3+ (D) Dissociation
2. pH of K 2 S solution is:
(A) 7 (B) Less than 7 (C) More than 7 (D) 0
3. Conjugate acid of HPO2−
4 is

(A) H2 PO−
4 (B) PO3−
4 (C) H3 PO4 (D) H3 O+
4. Find K b of HPO2−
4 in terms of dissociation constant K a1 , K a2 and K a3 of H3 PO4
K Kw K Kw
(A) K w (B) (C) K w (D) K
a3 K a1 a2 a1 , Ka

5. Select the correct option for the relationship between K b1 , K b2 and K b3 of PO3−
4 and K a1 , K a2

and K a3 of H3 PO4
(A) K a1 × K b1 = K w (B) K b1 × K a2 = K w
(C) K b3 × K a1 = K w (D) K a2 + K b2 = K w
6. Find equilibrium constant for the reaction
H2 PO−
4 + H2 O → H3 PO4 + OH
−

Given for H3 PO4 K a1 = 10−4 M, K a 2 = 10−7 M, K a 3 = 10−11 M

(A) 10−7 (B) 10−3 (C) 10−10 (D) 10−11
7. For a CM3 A (potassium salt of a tribasic acid H3 A ) solution:
(Dissociation constants of acid are K a1 , K a2 & K a3 ; h << 1 )
1
(A) pH = 2 (pK W + pK a3 + log C)
1
(B) pH = (pK W + pK a2 + log C)
2
1
(C) pH = 2 (pK W + pK a1 + log C)
1
(D) pH = 2 (pK W − pK a3 − log C)

8. K a1 , K a2 and K a3 values for H3 PO4 are 10−3 , 10−8 and 10−12 respectively.
If K W (H2 O) = 10−14 , then:
(i) What is dissociation constant of HPO2−
4 ?

(ii) What is K b of HPO2−

4 ?

(iii) What is K b of H2 PO−

4?

(iv) What is order of K b of PO3−

4 (K b1 ), HPO4 (K b2 ) and H2 PO4 (K b3 ) ?
2− −

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9. Calculate the OH − concentration and the H3 PO4 concentration of a solution prepared by

dissolving 0.1 mol of Na3 PO4 in sufficient water to make 1 L of solution.
K1 = 7.1 × 10−3 , K 2 = 6.3 × 10−8 , K 3 = 4.5 × 10−13 .
10. Calculate the extent of hydrolysis of 0.005 M K 2 CrO4 . [K 2 = 3.1 × 10−7 for H2 CrO4 ] (It is
essentially strong for first ionization).
1
= 0.26
√5 × 3.1
11. The acid ionization (hydrolysis) constant of Zn2+ is 1.0 × 10−9
(a) Calculate the pH of a 0.001 M solution of ZnCl2
(b) What is the basic dissociation constant of Zn(OH)+?

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DPP-9
pH of Salt of Weak Acid or Weak Base and Amphiprotic Salt
1. The pK a of a weak acid, HA is 4.80 . The pK b of a weak base, BOH, is 4.78 . The pH of an
aqueous solution of the corresponding salt BA will be:
(A) 8.58 (B) 4.79 (C) 7.01 (D) 9.22
2. The degree of hydrolysis of a salt of weak acid and weak base in it is 0.1 M solution is found to
be 50%. If the molarity of the solution is 0.2 M , the percentage hydrolysis of the salt should be
(A) 100% (B) 50% (C) 25% (D) none of these
3. Out of the following, amphiprotic species in aqueous medium are
I. HPO3 2− II. OH − III. H2 PO−
4 IV. HCO−
3

(A) I, III, IV (B) I and III (C) III and IV (D) All
4. Find pH of 0.1M Na2 HPO4 (aq.) solution
Given for H3 PO4 K a1 = 10−4 M, K a 2 = 10−7 M, K a 3 = 10−11 M
(A) 9 (B) 5.5 (C) 7.5 (D) 11
5. Find [CO2−
3 ] in 0.2 M NaHCO3 (aq.) solution

Given K a1 and K a2 of H2 CO3 are 10−8 and 10−10 respectively

(A) 0.2 (B) 2 × 103 (C) 5 × 10−3 (D) 5 × 10−4
6. Find K h of NH4 CN(aq)
Given K a (HCN) = 10−7 M K b (NH4 OH) = 10−5 M
7. The pH of 0.02 M CH3 COONH4.
[K b (NH3 ) = 1.8 × 10−5 , K a (CH3 COOH) = 1.8 × 10−5 ]
8. What is the pH of 0.1 M NaHCO3 ?
K1 = 4.5 × 10−7 , K 2 = 4.5 × 10−11 for carbonic acids.
log(4.5) = 0.66
9. Calculate pH of 0.05 M potassium hydrogen phthalate, KHC8 H4 O4 .
H2 C8 H4 O4 + H2 O ⟶ H3 O+ + HC8 H4 O−
4 pK1 = 2.94
HC8 H4 O− +
4 + H2 O ⟶ H3 O + C8 H4 O
2−
pK 2 = 5.44
10. Find the ratio of concentration of [PO3−
4 ] and [H2 PO4 ] in 0.5M Na 2 HPO4 (aq) solution
−

Given K a1 , K a 2 and K a3 for H3 PO4 are 10−4 M, 10−7 M &10−11 M respectively.

11. Find ratio of [CH3 COO− ] to [CH3 COOH] in 0.2 M CH3 COOHNH4 (aq) solution.
Given K a (CH3 COOH) = 10−5 ; K b (NH4 OH) = 10−5

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DPP-10
pH of Buffer Solution
1. 1 M NaCl and 1 M HCl are present in an aqueous solution. The solution is
(A) not a buffer solution and with pH < 7 (B) not a buffer solution with pH > 7
(C) a buffer solution with pH < 7 (D) a buffer solution with pH > 7
2. pK b for NH4 OH at certain temperature is 4.74. The pH of basic buffer containing equimolar
concentration of NH4 OH and NH4 Cl will be:
(A) 7.74 (B) 4.74 (C) 2.37 (D) 9.26
3. 500 ml of 0.2 M acetic acid are added to 500 ml of 0.30 M sodium acetate solution. If the
dissociation constant of acetic acid is 1.5 × 10−5 then pH of the resulting solution is:
(A) 5.0 (B) 9.0 (C) 3.0 (D) 4.0
4. K a for HCN is 5 × 10−10 at 25o C. For maintaining a constant pH of 9, the volume of 5 M KCN
solution required to be added to 10 ml . of 2 M HCN solution is-
(A) 4 ml (B) 7.95 ml (C) 2 ml (D) 9.3 ml
5. Henderson equation pH − pK a = 5 will be applicable to an acidic buffer when:
(A) [ Acid ] = [ Conjugate base ] (B) [ Acid ] × 105 = [ Conjugate base ]
(C) [ Acid ] = [ Conjugate base ] × 105 (D) [acid] = 2 [conjugate base]
6. Find the pH of Buffer solution containing 0.2 M H3 PO4 (aq.) and 0.4 M NaHPO4 (aq.)
Given K a1 , K a2 and K a3 for H3 PO4 are 10−4 M, 10−7 M & 10−11 M
(A) 4 (B) 7.3 (C) 6.7 (D) 4.3
7. Find pH of Buffer solution made by mixing 20 ml 0.1M Na3 PO4 with 40 ml 0.2 M
Given K a1 , K a2 and K a3 for H3 PO4 are 10−4 M, 10−7 M & 10−11 M(Na2 HPO4 ) (aq.)
(A) 7.3 (B) 11.6 (C) 10.4 (D) 4.6
8. 50 ml of 2 M acetic acid mixed with 10 ml of 1 M sodium acetate solution will have an
approximate pH of (K a = 10−5 ) :
9. Determine [OH − ]of a 0.050 M solution of ammonia to which sufficient NH4 Cl has been added to
make the total [NH4+ ]equal to 0.1M. [K b(NH3) = 1.8 × 10−5 ]
10. A buffer of pH 9.26 is made by dissolving x moles of ammonium sulphate and 0.1 mole of
ammonia into 100 mL solution. If pK b of ammonia is 4.74, calculate value of x.
11. (a) Determine the pH of a 0.2 M solution of pyridine C5 H5 N ⋅ Kb = 1.5 × 10−9
(b) Predict the effect of addition of pyridinium ion C5 H5 NH + on the position of the equilibrium.
Will the pH be raised or lowered?
(c) Calculate the pH of 1.0 L of 0.10 M pyridine solution to which 0.3 mol of pyridinium chloride
C5 H5 NH + Cl, has been added, assuming no change in volume. (log 3 = 0.48)

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DPP-11
Change in pH of Buffer Solution
1. In a buffer solution the ratio of concentration of NH4 Cl and NH4 OH is 1: 1. When it changes in
2: 1 ratio. What will be the value of pH of buffer:
(A) Increase (B) Decrease (C) No effect (D) None
2. 10 ml of a solution contains 0.1 M NH4 Cl + 0.01 M NH4 OH.
Which addition would not change the pH of solution:
(A) Adding 1 ml water (B) Adding 5 ml of 0.1 M NH4 Cl
(C) Adding 5 ml of 0.1 M NH4 OH (D) Adding 10 ml of 0.1 M NH4 Cl
3. How many gm of solid NaOH must be added to 100 ml of a buffer solution which is 0.1 M each
w.r.t. acid HA and salt Na+ A− to make the pH of solution 5.5.
Given pk a (HA) = 5.
(Use antilog (0.5) = 3.16 )
(A) 2.08 × 10−1 (B) 3.05 × 10−3 (C) 2.01 × 10−2 (D) None of these
4. When 0.02 moles of NaOH are added to a litre of buffer solution, its pH changes from 5.75 to
5.80. What is its buffer capacity:
(A) 0.4 (B) 0.05 (C) – 0.05 (D) 2.5
5. During a practical examination AKK sir prepared following three buffer solution and asked
student to select the best one
Concentration Of Acid Concentration of Base
Buffer -1 0:6 0:3
Buffer -2 0:3 0:3
Buffer -3 0:4 0:2
(A) Buffer -1 (B) Buffer -2 (C) Buffer -3 (D) All are best.

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6. A buffer solution is prepared by mixing 'a' moles of CH3 COONa and 'b' moles of CH3 COOH such
that (a + b) = 1, into water to make 1 L buffer solution. If the instantaneous (differential)
buffer capacity of this buffer solution is plotted against moles of salt CH3 COONa (a), then the
plot obtained will be (to the scale) approximately

0.25
Buffer capacity

0.20

(A) 0.15 (B)

0.10
0.0 0.2 0.4 0.6 0.8 1.0
a

0.55
0.50
Buffer capacity

0.45

0.40
(C) (D)
0.35

0.30
0.0 0.2 0.4 0.6 0.8 1.0
a

7. pH when solution containing HA(K a = 10−6 ) & NaA show maximum buffer action will be :-
8. When 0.05 mole of HCl is added in 200 ml of a buffer solution, the pH of the solution decreases
by 0.05 unit. What is the buffer capacity of the solution?
9. (i) Calculate the pH of 0.5 L of a 0.2 M NH4 CI and 0.2 M NH3 buffer.
(ii) Also calculate pH after addition of (a) 0.05 mole of NaOH and (b) 0.05 mole of HCl. Assume
that the volume remains constant.
[Given: pK b of NH3 = 4.74][log 3 = 0.48]

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DPP-12
Acid Base Titration Based Questions
1. 8 gm NaOH and 4.9gm H2 SO4 are present in one litre of the solution. What is its pH
(A) 1 (B) 13 (C) 12 (D) 2
2. Which of the following solution will have pH close to 1.0 ?
M M
(A) 100 ml of 100 HCl + 100ml of 10 NaOH
M M
(B) 55 ml of 10 HCl + 45ml of 10 NaOH
M M
(C) 10 ml of HCl + 90ml of NaOH
10 10
M M
(D) 75 ml of HCl + 25ml of NaOH
5 5

3. Which can act as buffer:

(A) NH4 OH + NaOH
(B) HCOOH + HCl
(C) 40 ml of 0.1 M NaCN + 20ml of 0.1 M HCl
(D) 20 ml of 0.1M NaCN + 40ml of 0.1 M HCl
4. On addition of NaOH to CH3 COOH solution, 60% of the acid is neutralised. If pK a of CH3 COOH is
4.7 then the pH of the resulting solution is: [log 3 = 0.48]
(A) More than 4.7 but less than 5.0 (B) Less than 4.7 but more than 4.0
(C) More than 5.0 (D) Remains unchanged
5. If 40 ml of 0.2 M KOH is added to 160 ml of 0.1 M HCOOH[K a = 2 × 10−4 ], the pOH of the
resulting solution is
(A) 3.4 (B) 3.7 (C) 7 (D) 10.3
6. 10 mL of 0.2 M CH3 COONa solution is titrated with 0.2 M HCl solution. The pH value at
equivalence point is: (pK a (CH3 COOH) = 4.76)
(A) 0.7 (B) 1 (C) 1.88 (D) 2.88
7. Calculate the pH of the resulting solution formed by mixing the following solutions:
(a) 20 mL of 0.2 M Ba(OH)2 + 30 mL of 0.1 M HCl
(b) 2 mL of 0.1 M HCl + 10 mL of 0.01 M Sr(OH)2
(c) 10 mL of 0.1 M H2 SO4 + 10 mL of 0.1 M KOH.

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8. How many of the following statement(s) is/are correct for making a buffer solution ?
(i) It can be formed by mixing equal moles of HCl and CH3 COONa
(ii) It can be formed by mixing equal moles of HNO3 and NH3
(iii) It can be formed by mixing equal moles of HCN and Aniline.
(iv) It can be formed by mixing unequal moles of NH4 OH and HCl .
(v) It can be formed by mixing unequal moles of HCN and KOH.
9. Calculate the pH of a solution made by mixing 50.0 ml of 0.2 M NH4 Cl & 75.0 ml of 0.1 M NaOH.
[Kb(NH3 ) = 10−5 ][log 3 = 0.48]
10. Calculate the pH of a solution which results from the mixing of 50.0 ml of 0.3 M HCl with
50.0 ml of 0.4 M NH3 . [K b (NH3 ) = 1.8 × 10−5 ][log 3 = 0.48]
11. Calculate OH − concentration at the equivalent point when a solution of 0.2 M acetic acid is
titrated with a solution of 0.2 M NaOH. K a for the acid = 10−5 .

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DPP-13
Acid Base Titration Based Questions
1. Which of the following solutions does not act as buffer:
(A) H3 PO4 + NaH2 PO4 (B) NaHCO3 + H2 CO3
(C) NH4 Cl + HCl (D) CH3 COOH + CH3 COONa
2. H2 A is a diprotic acid for which K a1 = 10−7 and K a2 = 10−11. The solution which will have pH
closest to 9 is:
(A) 0.1MH2 A (B) 0.1MNa2 A
(C) 0.1 M NaHA (D) 0.1MNaHA + 0.1MNa2 A
3. The total number of different kinds of acidic buffers obtained during the titration of H3 PO4
with NaOH are:
(A) 3 (B) 1 (C) 2 (D) 0
4. pH when 100 ml of 0.1MH3 PO4 is titrated with 150 ml 0.1 M NaOH solution will be :-
(A) pKa1 + log 2 (B) pKa2 + log 2 (C) pKa2 (D) pKa1
5. 50 mL of 0.05MNa2 CO3 is titrated against 0.1 M HCl. On adding 40 mL of HCl pH of the solution
will be [Given :For H2 CO3 , pK1 = 6.35, pK 2 = 10.33; log 3 = 0.48 ]
(A) 6.35 (B) 6.526 (C) 8.34 (D) 6.17
6. 50 mL of 0.1 M NaOH is added to 60 mL of 0.15MH3 PO4 solution (K1 , K 2 and K 3 for H3 PO4 are
10−3 , 10−8 and 10−13 respectively). The pH of the mixture will be
H A
7. 10 ml of 0.1 M tribasic acid H3 A is titrated with 0.1 M NaOH solution. What is the ratio of [ A33− ]

at 2nd equivalence point is 10−x . Find X . Given K1 = 10−4 , K 2 = 10−8 , K 3 = 10−12

8. 50 ml 0.1 M Na 3 A in tilrated with 0.2 M HCl find ratio of pH at 2nd equivalence point to 1st
equivalence point.
Given k a1 , K a2 and K a3 for H3 A are 10−3 M, 10−7 M and 10−11 M

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DPP-14
Solubility and Ksp
1. The solubility of A2 X 3 is ' s ' mol dm-3. Its solubility product is
(A) 6y 2 (B) 64y 4 (C) 36y 5 (D) 108y 5
2. If the solubility of AgCl (formula mass = 143 ) in water at 25∘ C is 1.43 × 10−4 gm./100ml. of
solution then the value of Ksp will be:
(A) 1 × 10−5 (B) 2 × 10−5 (C) 1 × 10−10 (D) 2 × 10−10
3. One litre of saturated solution of CaCO3 is evaporated to dryness, 7.0 g of residue is left. The
solubility product for CaCO3 is:
(A) 4.9 × 10−3 (B) 4.9 × 10−5 (C) 4.9 × 10−9 (D) 4.9 × 10−7
4. Which of the following is most soluble in water?
(A) MnS (K sp = 8 × 10−37 ) (B) ZnS(K sp = 7 × 10−16 )
(C) Bi2 S3 ( K sp = 1 × 10−72 ) (D) Ag 3 (PO4 )(K sp = 1.8 × 10−18 )
5. K sp of Ag 2 CrO4 at a certain temperature is 8.64 × 10−13 . How many times is its solubility in
water greater than in 0.6 M Na2 CrO4 solution?
(A) 10 (B) 10 (C) 1000 (D) 129
6. SrCO3 ( K sp = 10−10 ) and ZnCO3 ( K sp = 1.5 × 10−11 ) are dissolved together in a solution. The
ratio of [Sr 2+ ]/[Zn2+ ] in the solution is:
10 3 20 3
(A) (B) 10 (C) (D) 20
3 3

7. Calculate the solubility of A2 X3 in pure water, assuming that neither of ion reacts with water.
For A2 X3 , [ K sp = 1.08 × 10−23 ]
8. The solubility of PbSO4 water is 0.038 g/L. Calculate the solubility product constant of PbSO4 .
380
Molar mass PbSO4 = 304 g/mole; 304 = 1.25; (1.25)2 = 1.56
9. A solution of saturated CaF2 is found to contain 4.1 × 10−4 M fluoride ion. Calculate the K sp of
4.1 3
CaF2 . Use 4 ( 2 ) = 34.

10. The values of K sp for the slightly soluble salts MX and QX2 are each equal to 4.0 × 10−18 .
Which salt is more soluble? Explain your answer fully.
11. Determine the solubility of AgCl in 0.1 M BaCl2 . [K sp for AgCl = 1 × 10−10 ]
12. Calculate the Simultaneous solubility of AgSCN and AgBr.
1.1 5
K sp (AgSCN) = 1.1 × 10−12 , K sp (AgBr) = 5 × 10−13 ⋅ (1.26 ≃ 0.9, 1.26 ≃ 4)

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DPP-15
Precipitation
1. Solid Ba(NO3 )2 is gradually dissolved in a 1.0 × 10−4 M Na2 CO3 solution. At what concentration
of Ba2+ will a precipitate begin to form? (K sp for BaCO3 = 5.1 × 10−9 )
(A) 4.1 × 10−5 M (B) 5.1 × 10−5 M (C) 8.1 × 10−8 M (D) 8.1 × 10−7 M
2. Solubility product of Mg(OH)2 is 1 × 10−11 . At what pH , precipitation of Mg(OH)2 will begin
from 0.1 M Mg 2+ solution:
(A) 9 (B) 5 (C) 3 (D) 7
3. What will happen if the pH of the solution of 0.001 M Mg(NO3 )2 solution is adjusted to pH = 9
(K sp of Mg(OH)2 = 8.9 × 10−12 )
(A) ppt will take place (B) ppt will not take place
(C) Solution will be saturated (D) None of these
4. 50 litre of a solution containing 10−5 mole of Ag + is mixed with 50 litre of a 2 × 10−7 M HBr
solution. [Ag + ]in resultant solution is: [Given: K Sp (AgBr) = 5 × 10−13 ]
(A) 10−5 M (B) 10−6 M (C) 10−7 M (D) 10−8 M
5. The remaining molar concentration of Ag + ion if 100 ml of 0.1 M AgNO3 solution is mixed with
400 ml of 0.2 M K 2 Cr2 O4 solution is,
[Given K sp (Ag 2 CrO4 ) = 1.5 × 10−11 M 3 ]
(A) 10−10 (B) 2.5 × 10−3 (C) 5 × 10−3 (D) 10−5
6. The moles of Ag + which must be added to decrease the concentration of Cl− from 4 × 10−5 M to
10−5 M in 100 ml solution, if K sp for AgCl is 10−10 M 2 at 25∘ C
(A) 4 × 10−5 mole (B) 2 × 10−5 mole (C) 3 × 10−6 mole (D) 4 × 10−6 mole
7. K sp of AgCl, Ag 2 CrO4 and AgBr are 10−10 , 10−13 &10−12 respectively. If to a solution of 0.1 M
each of Cl− , CrO2−
4 and Br ions AgNO3 is added slowly, which will precipitate first :
−

(A) AgCl (B) Ag 2 CrO4 (C) AgBr (D)All simultaneously

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8. In a saturated solution of AgCl, NaCl is added gradually. The concentration of Ag + is plotted

against the concentration of Cl− . The graph appears as:

[Ag+] [Ag+]
(A) (B)
[Cl–] [Cl–]

[Ag+] [Ag+]
(C) (D)
[Cl–] [Cl–]

9. A solution has a Mg 2+ concentration of 0.0010 mol/L. Will Mg(OH)2 precipitate if the OH −

concentration of the solution is [K sp = 1.2 × 10−11 ]
(a) 10−5 mol/L (b) 10−3 mol/L ?
10. 8 × 10−6 M AgNO3 solution is gradually added in 1 L of 10−4 MKCl solution. Up to what volume
AgNO3 solution being added (in L), precipitation of AgCl will not take place? (K Sp of AgCl =
2 × 10−10 )
11. Solubility of Ag 2 CrO4 in water at 25 ∘ C is 10−3 M. If 0.1 moles of K 2 CrO4 are added to 1 litre
saturated solution of Ag 2 CrO4 . Then find moles of Ag 2 CrO4 precipitated at 25∘ C. If your answer
is x × 10−y then fill ' x ' in OMR. Where ' x ' is single digit number.
12. What mass of Pb2+ ion is left in solution when 50.0 mL of 0.20 M Pb(NO3 )2 is added to 50.0 mL
of 1.5 M NaCl ? [Given K sp for PbCl2 = 1.7 × 10−4 ]
1.7
[5.6 × 208 = 1.2 × 103 ] [Atomic mass of Pb = 208, = 5.6]
(0.55)2

13. The solubility of CaCO3 is 7mg/ litre. Calculate the solubility of BaCO3 (in mol/L) from this
information and from the fact that when Na2 CO3 is added slowly to a solution containing
equimolar concentration of Ca+2 and Ba+2 , no precipitate of CaCO3 is formed until 90% of Ba+2
has been precipitated as BaCO3 . (Assume no hydrolysis of CO2−
3 ion).

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DPP-16
Effect of Complex Formation and Hydrolysis
1. What is the effect of pH on the solubility of M(CN)2 ? (Neglect hydrolysis of M 2+ ion)
(A) As pH decreases, solubility decreases.
(B) As pH decreases below 7 or increases above 7, solubility increases in both cases.
(C) As pH decreases, solubility increases.
(D) No dependence on pH of solution.
2. At 300 K in which of the one litre solution, the solubility of Ag 2 CO3 will be maximum:
(A) 0.05 M Na2 CO3 (B) Pure water (C) 0.05 M AgNO3 (D) 0.05 M NH3
3. Find solubility of AgCl in 2 M NH3 (aq) solution Given K form of Ag(NH3 )+
2 =

106 M −2 ; K sp (AgCl) = 10−10

(A) 10−5 M (B) √2 × 10−2 M (C) 2 × 10−2 M (D) 2 × 10−5 M

4. 1 mole of AgNO3 is added to 10 litre of 1 M NH3 . What is the concentration of Ag(NH3 )+ in
solution?
[Given : For Ag(NH3 )+
2 , K f1 = 2.0 × 10 ; K f2 = 10 ]
3 4

(A) 8 × 10−5 (B) 1.25 × 10−5 (C) 4 × 10−6 (D) 1.25 × 10−4
5. Find solubility of CH3 COOAg(s) in a solution of pH = 3
Given K sp = 10−12 M 2 ; K a of (CH3 COOH) = 10−5
6. pH of a saturated solution of silver salt of monobasic acid HA is found to be 9. Find the K sp of
sparingly soluble salt Ag A(s).
Given: K a (HA) = 10−10
(A) 1.1 × 10−11 (B) 1.1 × 10−10 (C) 10−12 (D) 10−10
7. A recent investigation of the complexation of SCN − with Fe3+ led of 130,16 , and 1.0 for K1 , K 2 ,
and K 3 , respectively. What is the overall formation constant of Fe(SCN)3 from its component
ions, and what is the dissociation constant of Fe(SCN)3 into its simplest ions on the basis of
these data?
8. How much AgBr could be dissolved in 1.0 L of 0.40 M NH3?
[K f (Ag(NH3+ )2 ) = 1 × 108 ; K sp (AgBr) = 5 × 10−13 ][√50 ≃ 7]
9. At 25∘ C, the solubility of Ag 2 CO3 ( K Sp = 4.3 × 10−13 ) would be in what order in the following
solutions?
(a) 0.01 M AgNO3 (b) 0.04 M K 2 CO3 (c) pure water (d) in a buffer of pH = 4
10. Calculate solubility of AgCN (K sp = 4 × 10−16 ) in a buffer solution of pH = 3.
(K a = 9 × 10−10 for HCN)

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DPP-17
Indicators
1. The rapid change of pH near the equivalence point of an acid-base titration is the basis of
indicator detection. pH of the solution is related to ratio of the concentrations of the acid (HIn)
and conjugate base (In− ) forms of the indicator by the expression:
[HIn] [HIn]
(A) log [In− ]
= pK In − pH (B) log [In− ]
= pH − pK In
[In− ] [In− ]
(C) log = pH + pK In (D) log = pK In − pH
[HIn] [HIn]

2. Calculate the pH range in which an acid indicator with K acid (indicator) = 1.0 × 10−5 changes
colour when the concentration of the indicator is 1 × 10−3 M.
(A) 5 ± 1 (B) 11 ± 1 (C) 3 ± 1 (D) 8 ± 1
3. pH -range of Methyl red indicator is:
(A) 4.2-6.3 (B) 8.5-10.3 (C) 8.3 − 10 (D) 3.1 − 4.4
4. Indicator which is used in the titration of CH3 COOH & NaOH :
(A) Methyl orange (B) Methyl red (C) Phenolphthalein (D) Litmus
5. In the volumetric estimation of HCl , if we make use of phenolphthalein as an indicator, which
base is unsuitable for the titration:
(A) NaOH (B) RbOH (C) KOH (D) NH4 OH
6. Phenolphthalein does not act as an indicator for the titration between:
(A) KOH and H2 SO4 (B) NaOH and CH3 COOH
(C) Oxalic acid and KMnO4 (D) Ba(OH)2 and HCl
7. 20 ml of 0.2MRNH2 ( K b = 10−5 ) is titrated against 0.2 M HCl . Which of the following graph is
correct-

(A) (B)

(C) (D)

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8. The range of most suitable indicator which should be used for titration of X − Na+ (0.1M, 10ml)
with 0.1 M HCl should be (Given: k b(X−) = 10−6 )
(A) 2 − 3 (B) 3-5 (C) 6 – 8 (D) 8 − 10
9. An acid-base indicator has a K a = 1.0 × 10−5 . The acid form of the indicator is red and the basic
form is blue. Calculate the pH change required to change the colour of the indicator from 80%
red to 80% blue.
(A) 1.20 (B) 0.80 (C) 0.20 (D) 1.40
10. A mixture of NaOH & Na2 CO3 when titrated against 0.1 NH2 SO4 solution, it requires 30 ml to
decolorise the phenolphthalein. Now methyl orange is added to it and further 20 ml of same
acid are added it observe methyl orange end point then millimoles of NaOH & Na2 CO3 in
mixture respectively -
(A) 2&2 (B) 2&4 (C) 1&2 (D) 2&1
11. For the acid indicator thymol blue, pH is 2.0 when half the indicator is in unionised form. Find
the % of indicator in unionised form in the solution with [H + ] = 4 × 10−3 M.
12. An acid indicator has a Ka of 3 × 10−5 . The acid form of the indicator is red & the basic form is
blue. By how much must the pH change in order to change the indicator form 75% red to 75%
blue? [log 3 = 0.4771]
13. At what pH does an indicator change colour if the indicator is a weak acid with K ind =
4 × 10−4 . For how many following titrations this indicator will be useful?
(a) NaOH + CH3 COOH (b) HCl + NH3 (c) HCl + NaOH
14. 100 ml solution containing Na2 CO3 & NaHCO3 is titrated with 0.1 M solution of triprotic strong
acid then following results were obtained
(i) 25 ml solution required 10 ml of acid using phenolphthalein as indicator
(ii) 20 ml solution required 20 ml of acid using methyl orange indicator
What will be the value of sum of millimoles of Na2 CO3 and NaHCO3 in original solution.

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EXERCISE-II
One or More than one correct
1. Which of the following is true for alkaline aqueous solution?
pKw pKw
(A) pH > (B) pH > pOH (C) pOH < (D) pH < pOH
2 2

2. Choose the correct statement(s)

(A) If pOH of aq. solution at 70 ∘ C is 7 , then solution will be acidic
(B) If [H + ]concentration is decreases 100 times, pH of solution increases by 2 units
(D) On dilution degree of dissociation of weak electrolytes increases.
(D) Larger the value of pK a weaker is the acid.
3. Which of the following increases with dilution at a given temperature:
(A) pH of 10−3 M acetic acid solution
(B) pH of 10−3 M aniline solution
(C) degree of dissociation of 10−3 M acetic acid solution
(D) degree of dissociation of 10−3 M aniline solution
4. In a solution containing 0.1 M HCl & 0.1 M H3 PO4 (having dissociation constants K a1 , K a2 & K a3
), assuming α ≪ 1 for H3 PO4 :
(A) pH = 1 (B) αH3PO4 = 10 K a1
(C) [HPO2−
4 ] = 10Ka1 Ka 2 (D) PO3−
4 = 100 Ka1 Ka 2 Ka 3

5. A buffer solution of a weak acid and its sodium salt NaA is excessively diluted. What can be the
possible outcome of the experiment.
(A) The ratio of [A− ]/ [HA] must remain constant.
(B) The ratio of [A− ]/[HA] may decrease.
(C) The ratio of [A− ]/[HA] may increase.
(D) If [A− ]0 = [HA]o , upon dilution, [A− ]and [HA] may remain constant.
6. Choose the incorrect statement(s)
(A) When a solution of a weak monoprotic acid is titrated against a strong base, at half
1
neutralization point, pH = 2 pK.

(B) The pH of a solution which is 0.1 M in sodium acetate and 0.01 M in acetic acid
(pK a = 4.74) would be 5.74 .
(C) In a mixture of weak acid and its conjugate base, the ratio of concentration of conjugate
base to acid is increased ten times. The pH of the solution would Increase by one unit.
(D) A buffer has maximum buffer capacity when the ratio of salt to acid is 10.

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7. Select the correct statement(s):

(A) K a for an acid HA is 1 × 10−6 . K b for A− would be 10−8
(B) Salts of strong acids and weak bases undergo cationic hydrolysis.
(C) If solution of CH3 COONa (aq.) is diluted then pH increases.
(D) Buffer capacity remains constant with dilution.
8. Select correct statement for 50ml 0.1 M HHA (aq.) solution; K a1 = 10−5 ; K a2 = 10−8
(A) [H + ] = 2[ A2− ]
(B) pH of 0.1 M HH2 A solution is 3
(C) In above H2 A solution when 5 millimoles of NaHA are added then pH increases by 2 units
(D) 50 ml of 0.1 M NaOH required to neutralised completely 50 ml of 0.1MH2 A solution
9. When equal volumes of the following solutions are mixed, precipitation of AgCl (K Sp =
1.8 × 10−10 ) will occur
(A) 10−4 M (Ag + )and 10−4 M(Cl− ) (B) 10−5 M (Ag + )and 10−5 M (Cl− )
(C) 10−6 M(Ag + )and 10−6 M (Cl− ) (D) 10−10 M (Ag + )and 10−10 M (Cl− )
10. Choose the correct statement(s)
(A)From an equimolar solution of Cl− and Br − ions, the addition of Ag + will precipitates Br − ion
first ( K Sp of AgCl & AgBr are 1 × 10−10 & 1 × 10−13 respectively).
(B) If the salts M2 X, QY2 and PZ3 have same solubilities ( <<< 1 ), their K sp values are related
as M2 X = QY2 > PZ3
(C) If the solubility of the salt Li3 Na3 (AlF6 )2 is x , then its solubility product would be 2916x 8 .
(D) K sp of Fe(OH)3 in aqueous solution is 3.8 × 10−38 at 298 K . The concentration of Fe3+ will
increase when [H + ]ion concentration decreases
11. Choose the correct statement(s)
(A) AgCl is less soluble in aqueous sodium chloride solution than in pure water.
(B) In the presence of a common ion (incapable of forming complex ion), the solubility of salt
decreases.
(C) The solubility of CH3 COOAg in water considering hydrolysis of CH3 COO− ions would be
greater than that ignoring the hydrolysis.
(D)The solubility of AgCl in NH3 is greater than the solubility in pure water because of complex
ion, [Ag(NH3 )2 ]+formation.

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12. A solution containing 0.01 M each of Pb2+ , Ag + , Zn2+ & Cr 3+ ion. If solid Na2 S is added slowly to
the solution then correct statement is based on given data -
Precipitate PbS Ag 2 S ZnS Cr2 S3
K sp 10−11 10−12 10−8 10−10
(A) Pb2+ will start precipitating first
(B) Cr 3+ will start precipitating last
(C) Zn2+ will start precipitating before Ag +
(D) When Zn2+ just starts precipitating then Pb2+ ion gets 90% precipitated

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 IONIC EQULIBRIUM (Physical Chemistry)

COMPREHENSION BASED
Paragraph for Question 13 to 15
1 litre of 1M CHCOOH3 COO (very weak acid) taken is a container initially. Now this solution is diluted
upto volume V (litre) so that pH of the resulting solution becomes the twice of the original value.
(Ka(CH3 COOH) = 10−6 ). Now equal volume of 0.5 × 10−6 M NaOH solution is added to this resulting
solution. So that a buffer solution is obtained.
[ Anion ] [ Cation ]
pH( acidic buffer ) = pKa + log10 ( ) and pOH( Basic buffer ) = pKb + log10 ( )
[ Acid ] [ Base ]

13. Find [H + ] in original solution

(A) 1 M (B) 10–3 M (C) 10–7 M (D) 10–11 M
14. Find value of V (litre)
(A) 5 × 105 litre (B) 1 litre (C) 2 litre (D) 2 × 10−6 litre
15. Find pH of final solution (log 3 = 0.477)
(A) 6 (B) 6.477 (C) 5.523 (D) 3
Paragraph for Q.16 to Q.18
100 ml of 1 M Na3 PO4 is titrated with 1 M HCl the following observation were made
Stage of titration pH
I half equivalence point 12
I equivalence point 10
II equivalence point 6
16. pH at III equivalence point should be -
(A) 4 (B) 4 − log 2 (C) 3 − log 5 (D) 2 − log 5
17. pH at II half equivalence point will be -
(A) 4 (B) 8 (C) 11 (D) 12
18. What is the value of equilibrium constant for the reaction -
Na3 PO4 (aq.) + H2 O (l) ⟶ Na2 HPO4 (aq.) + NaOH (aq.)

(A) 10−2 (B) 10−4 (C) 10−6 (D) 10−8

Paragraph for question nos. 19 to 21
To find the K sp of AgBrO3 a student prepared one litre of a just saturated solution by adding AgBrO3 at
27∘ C. He found that a copper wire left in the solution overnight became covered with silver and Cu+2
(aq) ions were also formed in solution. The wire was cleaned to remove silver, dried, and found to
weight 7.04 mg less than it did originally. (R = 8 J/mol/K; ln x = 2.3log x )
Given : Cu(s) + 2Ag + (aq) ⟶ Cu+2 (aq) + 2Ag(s) ΔG∘ = 110.4 kJ.
19. The number of moles of Cu which reacted was
(A) 1.1 × 10−4 (B) 1.1 (C) 0.11 (D) 1.1 × 10−3

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20. The [Ag + (aq)] in the original saturated solution have been
(A) 1.1 × 10−2 (B) 1.1 × 10−4 (C) 2.2 × 10−4 (D) 5.5 × 10−5
21. The K sp for AgBrO3 as calculated from the above data is about
(A) 1.21 × 10−8 (B) 3.025 × 10−9 (C) 1.7 × 10−4 (D) 4.84 × 10−8
Paragraph for Q.22 to Q.24
Consider the following equilibrium:
HCl(g) ⟶ H + (aq) + Cl− (aq)
In a closed vessel HCl(g) was in equilibrium with H + (aq) and Cl− (aq). The total volume of solution was
one litre and temperature of solution was 300 K and equilibrium partial pressure of HCl(g) was 10−8
bar. The aqueous solution was labelled as "solution I ". Another solution (K b = 10−5 ) to the 90 ml of
pure water.
Given: ΔGf∘ (HCl, g) = −23kcal/mol; ΔGf∘ (Cl− , aq) = −31.28kcal/mol; R = 2cal/K − mol ln x = 2.3log x
22. What was the ΔG∘ of the reaction?
HCl(g) ⟶ H + (aq) + Cl− (aq) at 298 K.
(A) 0 (B) −54.2kcal/mol (C) +54kcal/mol (D) −8.28kcal/mol
23. What was the pH of the "solution I"?
(A) pH = o (B) pH = 1 (C) pH = 2 (D) pH = 3
24. If 10 ml of "solution I " was added to 90 ml of "solution II" and thus "solution III" was prepared.
What was the pH of "solution III"?
(A) 2.1 (B) 4.7 (C) 8.3 (D) 9.3
Paragraph for Q.25 & Q.26
Radioactive tracers provide a convenient mean of measuring the small concentration encountered in
determining k sp values. Exactly 30 ml of 0.001MgNO3 solution containing radioactive silver, with an
activity of 40000 counts per ml was mixed with 10 ml of 0.002 M KIO3 solution and the mixture is diluted
to exactly 400 ml . After equilibrium was reached, a portion of sample was filtered to remove any solid
and was found to have an activity of 2000 counts per ml.
25. The k sp of AgIO3 is -
(A) 6 × 10−10 (B) 1.25 × 10−9 (C) 6 × 10−12 (D) 4 × 10−10
26. Number of moles of solid AgIO3 formed -
(A) 10−5 (B) 10−4 (C) 10−2 (D) 0.4 × 10−3

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MATCH THE COLUMN

27. Match the effect of addition of 1(M)NaOH to 100 ml of 1 (M) weak acid (HA) in (List-I) with pH
in (List-II)

List-I List-II
(P) 25 ml of NaOH (1) pK a
(Q) 50 ml of NaOH (2) pK a + log 3
(R) 75 ml of NaOH (3) pKa − log 3
1
(S) 100 ml of NaOH (4) [pKw + pKa − log 2]
2

Codes :
P Q R S
(A) (4) (3) (1) (2)
(B) (3) (1) (2) (4)
(C) (4) (2) (3) (1)
(D) (2) (1) (4) (3)
28. When K 2 CrO4 (aq.) react with AgNO3 (aq.) there may be the precipitation of
Ag 2 CrO4 ( K sp = 4 × 10−12 ). Then match the column I with Column-II.
Column-I Column-II
𝐊 𝟐 𝐂𝐫𝐎𝟒 (𝐚𝐪. ) 𝐀𝐠𝐍𝐎𝟑 (𝐚𝐪. )
(A) 100 ml 300 ml (P) Precipitation occurs.
10–5 M 4 × 10–7 M
(B) 100 ml 300 ml (Q) CrO2−
4 ion concentration in final solution is
16
4 × 10–5 M × 10–7 M 10–4 M
3

(C) 100 ml 300 ml (R) CrO2−

4 ion concentration in final solution is 10 M
–5

2
3 × 10–2 M 3
× 10–2 M

(D) 100 ml 200 ml (S) Ag + concentration in final solution is 3 × 10–7 M

10–2 M 10–2 M
(T) Ag + concentration in final solution is 4 × 10–5 M
29. There are five solutions in five different containers, match the correct pH for the given solution-

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Column-I Column-II
(Solution mixed) (pH of resultant solution)
(A) I + II (P) 2.85
(B) I + III (Q) 3
(C) I + IV (R) 3.15
(D) II + IV + V (S) 5
(T) 9
30. When K 2 CrO4 (aq.) react with AgNO3 (aq.) there may be the precipitation of Ag 2 CrO4
( K sp = 4 × 10−12 ). Then match the column I with Column-II.
Column-I Column-II
(A) Equimolar mixture of H3 A and (P) 12.0
NaH2 A.
(B) Equimolar mixture of NaH2 A (Q) 8.0
and Na2 HA.
(C) Equimolar mixture of Na2 HA (R) 4.0
and Na3 A.
(D) Equimolar mixture of H3 A (S) 6.0
And NaOH.
(E) Equimolar mixture of NaH2 A (T) 10.0
and NaOH.

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INTEGER
31. Determine the [S 2− ] in a saturated (0.1M) H2 S solution to which enough HCl has been added to
produce a [H + ]of 2 × 10−4 . K1 = 10−7 , K 2 = 10−14 .
32. Calculate the pH of the following solutions.
[For H3 PO4 : K1 = 7.5 × 10−3 M; K 2 = 6.2 × 10−8 M; K 3 = 1.0 × 10−12 M ]
(a) 50 ml of 0.12 M H3 PO4 + 20ml of 0.15 M NaOH ;
(b) 50 ml of 0.12 M H3 PO4 + 40ml of 0.15 M NaOH ;
(c) 40 ml of 0.12 M H3 PO4 + 40ml of 0.18 M NaOH ;
(d) 40 ml of 0.10 M H3 PO4 + 40ml of 0.25 M NaOH .
33. The indicator phenol red is half in the ionic form when pH is 7.2. If the ratio of the undissociated
form to the ionic form is 1: 5, find the pH of the solution. With the same pH for solution, if
indicator is altered such that the ratio of undissociated form to dissociated form becomes 1:4,
find the pH when 50% of the new indicator is in ionic form.
34. What minimum pH must be maintained in a saturated H2 S solution ( 0.1 M ) to cause
precipitation of both Mn2+ & Fe2+ from a solution, in which each ion is present at a
concentration of 0.01 M ?
(K1 K 2 of H2 S = 9.6 × 10−21 ; K Sp of MnS = 2.5 × 10−13 ; K Sp of FeS = 6.4 × 10−18 )
35. Determine the concentration of NH3 solution whose 1 L can dissolve 0.1 mole CuCO3 . Given:
K sp of CuCO3 = 1.4 × 10−10 and K f of [Cu(NH3 )4 ]2+ = 2 × 1013 .
4 1000
Take √ = 4.4. Assume no other reaction to take place.
2.8

36. A solution contains HCl, Cl2 HCCOOH & CH3 COOH at concentrations 0.09 M in HCl, 0.09M in
Cl2 HCCOOH & 0.1M in CH3 COOH. pH for the solution is 1. Ionization constant of CH3 COOH =
10−5. What is the value of K a for dichloroacetic acid?
37. When a 40 mL of a 0.1 M weak base is titrated with 0.16 M HCl , the pH of the solution at the
end point is 5.23 . What will be the pH if 15 mL of 0.12 M NaOH is added to the resulting
solution.
38. Mixtures of solution. Calculate the pH of the following solution.
[For H3 PO4 : K1 = 7.5 × 10−3 M; K 2 = 6.2 × 10−8 M; K 3 = 1.0 × 10−12 M ]
[For H2 CO3 : K1 = 4.2 × 10−7 M; K 2 = 4.8 × 10−11 M ]
(a) 40 ml of 0.05 M Na2 CO3 + 50ml of 0.04 M HCl ;
(b) 40 ml of 0.02 M Na3 PO4 + 40ml of 0.04 M HCl ;
(c) 50 ml of 0.1 M Na3 PO4 + 50ml of 0.1M NaH2 PO4 ;
(d) 40 ml of 0.1 M H3 PO4 + 40ml of 0.1 M Na3 PO4 .

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39. If 5 × 10−4 mol NaHCO3 is added to 1 litre of a buffered solution at pH 8.00 , how much
material will exist in each of the three forms H2 CO3 , HCO−
3 and CO3 ?
2−

For H2 CO3 , K1 = 5 × 10−7 , K 2 = 5 × 10−13 .

40. A solution of weak acid HA was titrated with base NaOH . The equivalence point was reached
when 36.12 ml of 0.1 M NaOH has been added. Now 18.06 ml of 0.1 M HCl were added to titrated
solution, the pH was found to be 4.92 . What will be the pH of the solution obtained by mixing 10
ml of 0.2 M NaOH and 10 ml of 0.2 M HA .
41. A buffer solution was prepared by dissolving 0.05 mol formic acid & 0.06 mol sodium format in
enough water to make 1.0 L of solution. K a for formic acid is 1.80 × 10−4 .
(a) Calculate the pH of the solution.
(b) If this solution is diluted 10 times, what would be the pH ?
(c) If the solution is diluted 100 times, what would be the pH ?
42. Find the pH of the solution prepared by mixing equal moles of H2 CO3 , NaHCO3 & Na2 CO3 in
1 litre H2 O(ℓ). [Given pK a1 , and pK a2 of H2 CO3 are 6,11]
(A) 6 (B) 11 (C) 8.5 (D) 2.5
43. 500 ml of 0.01AgNO3 is mixed with 250 ml each of NaBr and NaCl , each having molarity 0.02 M
each. Find equilibrium concentration of Br − (moles/L).
Given: K sp (AgBr) = 5 × 10−13 M 2 ; K sp (AgCl) = 10−10 M 2 .
44. In Mohr's method, solution of Cl− is titrated against standard AgNO3 . During the titration, a small
quantity of K 2 CrO4 solution is added as an indicator. As AgCl is less soluble than Ag 2 CrO4 , the
added Ag + reacts first with Cl− than with CrO2−
4 . At the equivalence point, when Cl is precipitated
−

quantitatively as AgCl , the slight excess of Ag + reacts with CrO2−

4 to give intensely red precipitate

of Ag 2 CrO4 . 50.0 mL of 0.1 M Cl− solution is titrated against 0.1 M standard AgNO3 . What must
be the theoretical molar concentration of CrO2−
4 in the solution so that Ag 2 CrO4 will start

precipitating at the equivalence-point.

Given: K sp (AgCl) = 10−10 M 2 ; K sp (Ag 2 CrO4 ) = 4 × 1O−12 M 3
[Fill your answer by multiplying it with 104.]
45. Most ordinary soaps are sodium salt of long-chain fatty acids and are soluble in water. Soaps of
divalent cations such as Ca2+ are only slightly soluble and are often seen in the common soap is
calcium palmitate Ca[CH3 (CH2 )14 COO]2 . A hand book lists the solubility of this soap as 0.0055
gm per 100 ml at 25 ∘ C. If sufficient sodium soap is used to produce a final concentration of
calcium palmitate would precipitate in a bowl containing 10 L of this water sample?

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EXERCISE # JEE-MAIN
1. The solubility in water of a sparingly soluble salt AB2 is 1.0 × 10−5 mol L−1. Its solubility
product will be [JEE-2003]
(A) 1 × 10−15 (B) 1 × 10−10 (C) 4 × 10−15 (D) 4 × 10−10
2. The solubility of Mg(OH)2 is x mole/lit. then its solubility product is: [JEE-2002]
(A) x 3 (B) 5x 3 (C) 4x 3 (D) 2x 2
3. The molar solubility in mol L−1 of a sparingly soluble salt MX4 is 's'. The corresponding
solubility product is K SP 's' is given in terms of K sp by relation: [JEE-2004]
(A) s = (K SP /128)1/4 (B) s = (128 K SP )1/4
(C) s = (256 K SP )1/5 (D) s = (K SP /256)1/5
4. The conjugate base of H2 PO−
4 is [JEE-2004]
(A) H3 PO4 (B) P2 O5 (C) PO3−
4 (D) HPO2−
4

5. Hydrogen ion concentration in mol/L in a solution of pH = 5.4 will be: [JEE-2005]

(A) 3.88 × 106 (B) 3.98 × 108 (C) 3.98 × 10−6 (D) 3.68 × 10−6
6. The solubility product of a salt having general formula MX2 , in water is: 4 × 10−12 . The
concentration of M 2+ ions in the aqueous solution of the salt is: [JEE-2005]
(A) 1.0 × 10−4 M (B) 2.0 × 10−6 M (C) 4.0 × 10−10 M (D) 1.6 × 10−4 M
7. What is the conjugate base of OH − ? [JEE-2005]
(A) O2− (B) O− (C) H2 O (D) O2
8. The first and second dissociation constants of an acid H2 A are 1.0 × 10−5 and 5.0 × 10−10
respectively. the overall dissociation constant of the acid will be [JEE-2007]
(A) 0.2 × 105 (B) 5.0 × 10−5 (C) 5.0 × 1015 (D) 5.0 × 10−15
9. The pK a of a weak acid (HA) is 4.5. The pOH of an aqueous buffer solution of HA in which 50%
of the acid is ionised is [JEE-2007]
(A) 7.0 (B) 4.5 (C) 2.5 (D) 9.5
10. In a saturated solution of the sparingly soluble strong electrolyte AgIO3 (molecular mass
= 283) the equilibrium which sets in is: [JEE-2007]
AgIO3 ⇋ Ag + −
(aq.) + IO3
If the solubility product constant Ksp of AgIO3 at a given temperature is 1.0 × 10−8 , what is the
mass of AgIO3 contained in 100 ml of its saturated solution?
(A) 28.3 × 10−2 g (B) 2.83 × 10−3 g
(C) 1.0 × 10−7 g (D) 1.0 × 10−4 g
11. Solution of the corresponding salt. BA, will be: [JEE-2008]
(A) 9.58 (B) 4.79 (C) 7.01 (D) 9.22

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12. Solid Ba(NO3 )2 is gradually dissolved in a 1.0 × 10−4 M Na2 CO3 solution. At what concentration
of Ba2+ will a precipitate begin to form? (K sp for BaCO3 = 5.1 × 10−9 ) [JEE-2009]
(A) 8.1 × 10−8 M (B) 8.1 × 10−7 M
(C) 4.1 × 10−5 M (D) 5.1 × 10−5 M
13. Solubility product of silver bromide is 5.0 × 10−13 . The quantity of potassium bromide (molar
mass taken as 120 g mol−1 ) to be added to 1 litre of 0.05 M solution of silver nitrate to start the
precipitation of AgBr is: [JEE-2010]
(A) 5.0 × 10−8 g (B) 1.2 × 10−10 g
(C) 1.2 × 10−9 g (D) 6.2 × 10−5 g
14. In aqueous solution the ionization constants for carbonic acid are [JEE-2010]
K1 = 4.2 × 10−7 and K 2 = 4.8 × 10−11
Select the correct statement for a saturated 0.034 M solution of the carbonic acid:
(A) The concentration of H + is double that of CO2−
3

(B) The concentration of CO2−

3 is 0.034 M

(C) The concentration of CO2−

3 is greater than that of HCO3
−

(D) The concentrations of H + and HCO−

3 are approximately equal

15. At 25∘ C, the solubility producct of Mg(OH)2 is 1.0 × 10−11 . At which pH, will Mg 2+ ions start
precipitating in the form of Mg(OH)2 from a solution of 0.001 M Mg 2+ ions ? [JEE-2010]
(A) 8 (B) 9 (C) 10 (D) 11
16. Three reactions involving H2 PO−
4 are given below: [JEE-2010]
(i) H3 PO4 + H2 O → H3 O+ + H2 PO−
4 (ii) H2 PO4 − + H2 O → HPO2−
4 + H3 O
+

(iii) H2 PO− −
4 + OH → H3 PO4 + O
2−

In which of the above does H2 PO−

4 act as an acid?

(A) (ii) only (B) (i) and (ii) (C) (iii) only (D) (i) only
17. The Ksp for Cr(OH)3 is 1.6 × 10−30 . The molar solubility of this compound in water is:
[JEE-2011]
2 4
(A) √1.6 × 10−30 (B) √1.6 × 10−30
4
(C) √1.6 × 10−30 /27 (D) 1.6 × 10−30 /27
18. An acid HA ionises as
HA ⇌ H + + A−
The pH of 1.0 M solution is 5. Its dissociation constant would be: [JEE-2011]
(A) 1 × 10−10 (B) 5 (C) 5 × 10−8 (D) 1 × 10−5

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19. If K sp of CaF2 at 25∘ C is 1.7 × 10−10 , the combination amongst the following which gives a
precipitate of CaF2 is: [JEE MAIN 2012]
(A) 1 × 10−2 M Ca2+ and 1 × 10−5 M F −
(B) 1 × 10−4 M Ca2+ and 1 × 10−4 M F −
(C) 1 × 10−3 M Ca2+ and 1 × 10−5 M F −
(D) 1 × 10−2 M Ca2+ and 1 × 10−3 M F −
20. The pH of a 0.1 molar solution of the acid HQ is 3 . The value of the ionization constant, Ka of
this acid is: [JEE MAIN 2012]
(A) 1 × 10−7 (B) 3 × 10−7 (C) 1 × 10−3 (D) 1 × 10−5
21. Solid Ba(NO3 )2 is gradually dissolved in a 1.0 × 10−4 M Na2 CO3 solution. At which
concentration of Ba2+ , precipitate of BaCO3 begins to form?
(K sp for BaCO3 = 5.1 × 10−9 ) [JEE MAIN 2013]
(A) 5.1 × 10−5 M (B) 8.1 × 10−7 M (C) 4.1 × 10−5 M (D) 7.1 × 10−8 M
22. NaOH is a strong base. What will be pH of 5.0 × 10−2 MNaOH solution? (log 2 = 0.3)
[JEE MAIN 2013]
(A) 13.70 (B) 13.00 (C) 14.00 (D) 12.70
23. Which one of the following arrangements represents the correct order of solubilities of
sparingly soluble salts Hg 2 Cl2 , Cr2 (SO4 )3 , BaSO4 and CrCl3 respectively? [JEE MAIN 2013]
1 1 1 1
Ksp 3 Ksp 8 Ksp 4
(A) ( 4 ) , (108) , ( K sp ) 2
, ( 27 )
1 1 1 1
Ksp 3 Ksp 4 Ksp 3
(B) (K sp ) 2
, ( 4 ) , ( 27 ) , (108)
1 1 1 1
Ksp 3 Ksp 4 Ksp 3
(C) (K sp ) 2
, (108) , ( 27 ) , ( 4 )
1 1 1 1
Ksp 3 Ksp 4 Ksp 3
(D) (108) , ( 27 ) , ( K sp ) 2
,( 4 )

24. What would be the pH of a solution obtained by mixing 5 g of acetic acid and 7.5 g of sodium
acetate and making the volume equal to 500 mL? [JEE MAIN 2013]
(Ka = 1.75 × 10−5 , pKa = 4.76)
(A) 4.76 < pH < 5.0
(B) pH < 4.70
(C) pH of solution will be equal to pH of acetic acid
(D) pH = 4.70

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25. How many litres of water must be added to 1 litre of an aqueous solution of HCl with a pH of 1
to create an aqueous solution with pH of 2? [JEE MAIN 2013]
(A) 0.1 L (B) 0.9 L (C) 2.0 L (D) 9.0 L
26. In some solutions, the concentration of H3 O+ remains constant even when small amounts of
strong acid or strong base are added to them. These solutions are known as: [JEE MAIN 2014]
(A) Colloidal solutions (B) True solutions
(C) Ideal solutions (D) Buffer solutions
27. Zirconium phosphate [Zr3 (PO4 )4 ] dissociates into three zirconium cations of charge +4 and
four phosphate anions of charge -3. If molar solubility of zirconium phosphate is denoted by S
and its solubility product by K sp then which of the following relationship between S and K sp is
correct? [JEE MAIN 2014]
1/7
(A) S = {K sp /144} (B) S = {K sp /(6912)1/7 }
1/7 7
(C) S = (K Sp /6912) (D) S = {K sp /6912}
28. pK a of a weak acid (HA) and pK b of a weak base (BOH) are 3.2 and 3.4 , respectively. The pH of
their salt (AB) solution is [JEE MAIN 2017]
(A) 7.2 (B) 6.9 (C) 7.0 (D) 1.0
29. An alkali is titrated against an acid with methyl orange as indicator, which of the following is a
correct combination? [JEE MAIN 2018]
Base Acid End Point
(A) Strong Strong Pink to colourless
(B) Weak Strong Colourless to pink
(C) Strong Strong Pinkish red to yellow
(D) Weak Strong Yellow to Pinkish red
30. An aqueous solution contains an unknown concentration of Ba2+ . When 50 mL of a 1 M
solution of Na2 SO4 is added, BaSO4 just begins to precipitate. The final volume is 500 mL . The
solubility product of BaSO4 is 1 × 10−10 . What is the original concentration of Ba2+ ?
[JEE MAIN 2018]
(A) 1.0 × 10−10 M (B) 5 × 10−9 M (C) 2 × 10−9 M (D) 1.1 × 10−9 M
31. An aqueous solution contains 0.10 M H2 S and 0.20 M HCl . If the equilibrium constants for the
formation of HS − from H2 S is 1.0 × 10−7 and that S 2− from HS − ions is 1.2 × 10−13 then the
concentration of S 2− ions in aqueous solution is [JEE MAIN 2018]
(A) 5 × 10−19 (B) 5 × 10−8 (C) 3 × 10−20 (D) 6 × 10−21

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32. Which of the following salts is the most basic in aqueous solution? [JEE MAIN 2018]
(A) Pb(CH3 COO)2 (B) Al(CN)3 (C) CH3 COOK (D) FeCl3
33. The minimum volume of water required to dissolve 0.1 g lead (II) chloride to get a saturated
solution ( K sp of PbCl2 = 3.2 × 10−8 ; atomic mass of Pb = 207u) is: [JEE MAIN 2018]
(A) 0.36 L (B) 0.18 L (C) 17.98 L (D) 1.798 L
34. Following four solutions are prepared by mixing different volumes of NaOH and HCl of different
concentrations, pH of which one of them will be equal to 1? [JEE MAIN 2018]
M M M M
(A) 75 mL 5 HCl + 25 mL 5 NaOH (B) 100 mL 10 HCl + 100 mL 10 NaOH
M M M M
(C) 55 10 HCl + 40 mL 10 NaOH (D) 60 mL 10 HCl + 40 mL 10 NaOH

35. 20 mL of 0.1 M H2 SO4 solution is added to 30 mL of 0.2 M NH4 OH solution. The pH of the
resultant mixture is: [pKb of NH4 OH = 4.7]. [JEE MAIN 2019]
(A) 9.4 (B) 5.0 (C) 9.0 (D) 5.2
36. A mixture of 100 m mol of Ca(OH)2 and 2 g of sodium sulphate was dissolved in water and the
volume was made up to 100 mL . The mass of calcium sulphate formed and the concentration
of OH − in resulting solution, respectively, are: (Molar mass of Ca(OH)2 , Na2 SO4 and CaSO4 are
74, 143 and 136 g mol−1 , respectively; Ksp of Ca(OH)2 is 5.5 × 10−6 ) [JEE MAIN 2019]
(A) 13.6 g, 0.14 mol L−1 (B) 1.9 g, 0.14 mol L−1
(C) 1.9 g, 0.28 mol L−1 (D) 13.6 g, 0.28 mol L−1
37. If K sp of Ag 2 CO3 is 8 × 10−12 , the molar solubility of Ag 2 CO3 in 0.1 M AgNO3 is:
[JEE MAIN 2019]
(A) 8 × 10−10 M (B) 8 × 10−13 M (C) 8 × 10−12 M (D) 8 × 10−11 M
38. If solubility product of Zr3 (PO4 )4 is denoted by K sp and its molar solubility is denoted by S,
then which of the following relation between A and K sp is correct? [JEE MAIN 2019]
1 1 1 1
Ksp 7 Ksp 6 Ksp 9 Ksp 7
(A) S = (6912) (B) S = (144) (C) S = (929) (D) S = (216)

39. In an acid-base titration, 0.1 M HCl solution was added to the NaOH solution of unknown
strength. Which of the following correctly shows the change of pH of the titration mixture in
this experiment? [JEE MAIN 2019]

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

(A) D (B) A (C) C (D) B
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40. Consider the following statements [JEE MAIN 2019]

(a) The pH of a mixture containing 400 mL of 0.1 M H2 SO4 and 400 mL of 0.1 M NaOH will be
approximately 1.3.
(b) Ionic product of water is temperature dependent.
(c) A monobasic acid with K a = 10−5 has a pH = 5. The degree of dissociation of this acid is
50%.
(d) The Le Chatelier's principle is not applicable to common-ion effect.
The correct statements are:
(A) (a), (b) and (c) (B) (a) and (b) (C) (b) and (c) (D) (a), (b) and (d)
41. The pH of a 0.02 M NH4 Cl solution will be [given K b (NH4 OH) = 10−5 and log 2 = 0.301 ]
[JEE MAIN 2019]
(A) 5.35 (B) 4.65 (C) 4.35 (D) 2.65
42. What is the molar solubility of Al(OH)3 in 0.2 M NaOH solution? Given that, solubility product
of Al (OH)3 = 2.4 × 10−24 : [JEE MAIN 2019]
(A) 12 × 10 −23
(B) 3 × 10 −22
(C) 12 × 10 −21
(D) 3 × 10 −19

43. The molar solubility of Cd(OH)2 is 1.84 × 10−5 M in water. The expected solubility of Cd(OH)2
in a buffer solution of pH = 12 is: [JEE MAIN 2019]
(A) 6.23 × 10 −11
M (B) 2.49 × 10 −10
M (C) 1.84 × 10 M−9
(D) 10 M
−9

44. Arrange the following solutions in the decreasing order of pOH : [JEE MAIN 2020]
(A) 0.01 M HCl (B) 0.01 M NaOH
(C) 0.01 M CH3 COONa (D) 0.01 M NaCl
(A) (B) > (C) > (D) > (A) (B) (A) > (C) > (D) > (B)
(C) (B) > (D) > (C) > (A) (D) (A) > (D) > (C) > (B)
45. An acidic buffer is obtained on mixing : [JEE MAIN 2020]
(A) 100 mL of 0.1 M HCl and 200 mL of 0.1 M NaCl
(B) 100 mL of 0.1 M HCl and 200 mL of 0.1M CH3 COONa
(C) 100 mL of 0.1 M CH3 COOH and 100 mL of 0.1 M NaOH
(D) 100 mL of 0.1M CH3 COOH and 200 mL of 0.1 M NaOH
46. Given below are two statements. [JEE MAIN 2021]
Statement I: In the titration between strong acid and weak base methyl orange is suitable as
an indicator.
Statement II: For titration of acetic acid with NaOH phenolphthalein is not a suitable indicator.
In the light of the above statements, choose the most appropriate answer from the options
given below:
(A) Statement I is false but Statement II is true
(B) Statement I is true but Statement II is false
(C) Both Statement I and Statement II are true
(D) Both Statement I and Statement II are false

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47. The solubility of Ca(OH)2 in water is: [JEE MAIN 2021]

[Given : The solubility product of Ca(OH)2 in water = 5.5 × 10−6 ]
(A) 1.77 × 10−6 (B) 1.11 × 10−6 (C) 1.11 × 10−2 (D) 1.77 × 10−2
48. When 35 mL of 0.15 M lead nitrate solution is mixed with 20 mL of 0.12 M chromic sulphate
solution, _____ × 10−5 moles of lead sulphate precipitate out. [JEE MAIN 2021]
49. The solubility of AgCN in a buffer solution of pH = 3 is x. The value of x is: (Assume : No cyano
complex is formed; K sp (AgCN) = 2.2 × 10−16 and K a (HCN) = 6.2 × 10−10 ] [JEE MAIN 2021]
(A) 0.625 × 10−6 (B) 1.9 × 10−5 (C) 2.2 × 10−16 (D) 1.6 × 10−6
50. The number of moles of NH3 , that must be added to 2 L of 0.80 M AgNO3 in order to reduce the
concentration of Ag + ions to 5.0 × 10−8 M(K formation for [Ag(NH3 )2 ]+ = 1.0 × 108 ) is
[Assume no volume change on adding NH3 ] [JEE MAIN 2021]
51. K a for butyric acid (C3 H7 COOH) is 2 × 10−5 . The pH of 0.2 M solution of butyric acid is
____ × 10−1. [Given log 2 = 0.30 ] [JEE MAIN 2022]
52. 200 mL of 0.01 M HCl is mixed with 400 mL of 0.01 M HSO4. The pH of the mixture is .
[JEE MAIN 2022]
(A) 1.14 (B) 1.78 (C) 2.34 (D) 3.02
53. Class XII students were asked to prepare one litre of buffer solution of pH 8.26 by their
chemistry teacher. The amount of ammonium chloride to be dissolved by the student in 0.2 M
ammonia solution to make one litre of the buffer is (Given pK b (NH3 ) = 4.74; Molar mass of
NH3 = 17 g mol−1; Molar mass of NH4 Cl = 53.5 g mol−1 ) [JEE MAIN 2022]
(A) 53.5 g (B) 72.3 g (C) 107.0 g (D) 126.0 g
54. In base vs. Acid titration, at the end point methyl orange is present as [JEE MAIN 2022]
(A) quinonoid form (B) heterocyclic form
(C) phenolic from (D) benzenoid form
55. The solubility of AgCl will be maximum in which of the following? [JEE MAIN 2022]
(A) 0.01 M KCl (B) 0.01 M HC 1 (C) 0.01 M AgNO3 (D) De-ionised water
56. The dissociation constant of acetic is x × 10–5. When 25 mL of 0.2 M CH3COONa solution is
mixed with 25 mL of 0.02 M CH3COOH solution, the pH of the resultant solution is found to be
equal to 5. The value of x is _______. [JEE MAIN 2023]
57. A litre of buffer solution contains 0.1 mole of each of NH3 and NH4Cl. On the addition of 0.02
mole of HCl by dissolving gaseous HCl, the pH of the solution is found to be _________× 10–3
(Nearest integer) [JEE MAIN 2023]
[Given: pKb(NH3) = 4.745
log 2 = 0.301 log 3 = 0.477 T = 298 K]

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58. 600 mL of 0.01M HCl is mixed with 400 mL of 0.01 M H2SO4. The pH of the mixture is________×
102. (Nearest integer) [JEE MAIN 2023]
[Given log2 = 0.30, log3 = 0.48
log5 = 0.69, log7 = 0.84
log11 = 1.04]
59. At 298 K, the solubility of silver chloride in water is 1.434 × 10–3 g L–1. The value of –log Ksp for
silver chloride is ______. [JEE MAIN 2023]
(Given mass of Ag is 107.9 1 g mol–1 and mass of Cl is 35.5 g mol–1)

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EXERCISE # JEE-ADVANCED
1. What will be the resultant pH when 200 ml of an aqueous solution of HCl (pH = 2.0) is mixed
with 300 ml of an aqueous solution of NaOH (pH = 12.0)? [JEE 1998]
2. The solubility of Pb(OH)2 in water is 6.7 × 10−6 M. Calculate the solubility of Pb(OH)2 in a
buffer solution of pH = 8. [JEE 1999]
3. A buffer solution can be prepared from a mixture of [JEE 1999]
(A) sodium acetate and acetic acid in water
(B) sodium acetate and hydrochloric acid in water
(C) ammonia and ammonium chloride in water
(D) ammonia and sodium hydroxide in water.
4. The pH of 0.1 M solution of the following salts increases in the order [JEE 1999]
(A) NaCl < NH4 Cl < NaCN < HCl
(B) HCl < NH4Cl < NaCl < NaCN
(C) NaCN < NH4 Cl < NaCl < HCl
(D) HCl < NaCl < NaCN < NH4Cl
5. The average concentration of SO2 in the atmosphere over a city on a certain day is 10 ppm ,
when the average temperature is 298 K . Given that the solubility of SO2 in water at 298 K is
1.3653 moles litre −1 and the pK a of H2 SO3 is 1.92, estimate the pH of rain on that day.
[JEE 2000]
6. An aqueous solution of 6.3 g oxalic acid dihydrate is made up to 250 mL . The volume of 0.1 N
NaOH required to completely neutralise 10 mL of this solution is [JEE 2001]
(A) 40 mL (B) 20 mL (C) 10 mL (D) 4 mL
7. For sparingly soluble salt ApBq, the relationship of its solubility product (Ls) with its solubility
(S) is: [JEE 2001]
(A) Ls = S , p . q
p+q p q
(B) Ls = S , p . q
p+q p p

(C) Ls = S , p . q
pq p q
(D) Ls = S pq , (p. q)p+q
8. 500 ml of 0.2 M aqueous solution of acetic acid is mixed with 500 mL of 0.2 M HCl at 25∘ C.
(a) Calculate the degree of dissociation of acetic acid in the resulting solution and pH of the
solution.
(b) If 6 g of NaOH is added to the above solution, determine final pH . Assume there is no
change in volume on mixing. K a of acetic acid is 1.75 × 10−5 M. [JEE 2002]
9. Will the pH of water be same at 4 ∘ C and 25 ∘ C ? Explain. [JEE 2003]
10. A solution which is 10−3 M each in Mn2+ , Fe2+ , Zn2+ and Hg 2+ is treated with 10−16 M sulphide
ion. If K Sp , MnS, FeS, ZnS and HgS are 10−15 , 10−23 , 10−20 and 10−54 respectively, which one will
precipitate first? [JEE 2003]
(A) FeS (B) MnS (C) HgS (D) ZnS
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11. HX is a weak acid (K a = 10−5 ). It forms a salt NaX(0.1M) on reacting with caustic soda. The
degree of hydrolysis of NaX is [JEE 2004]
(A) 0.01% (B) 0.0001% (C) 0.1% (D) 0.5%
12. 0.1 M of HA is titrated with 0.1 M NaOH, calculate the pH at end point.
Given Ka(HA) = 5 × 10−6 and h ≪ 1. [JEE 2004]
13. CH3 NH2 (0.1 mole, K b = 5 × 10−4 ) is added to 0.08 moles of HCl and the solution is diluted to
one litre, resulting hydrogen ion concentration is [JEE 2005]
(A) 1.6 × 10−11 (B) 8 × 10−11 (C) 5 × 10−5 (D) 2 × 10−2
14. The species present in solution when CO2 is dissolved in water: [JEE 2006]
(A) CO2 , H2 CO3 , HCO3 2− (B) H2 CO3 , CO2−
3

(C) CO2− −
3 , HCO3 (D) CO2 , H2 CO3
15. Solubility product constants ( K sp ) of salts of types MX, MX2 and M3 X at temperature ' T ' are
4.0 × 10−8 , 3.2 × 10−14 and 2.7 × 10−15 , respectively. Solubilities (moldm−3 ) of the salts at
temperature " T " are in the order: [JEE 2008]
(A) MX > MX2 > M3 X (B) M3 X > MX2 > MX
(C) MX2 > M3 X > MX (D) MX > M3 X > MX2
2 2
16. 2.5 mL of 5 M weak monoacidic base (K b = 1 × 10−12 at 25∘ C) is titrated with 15 MHCl in water
at 25∘ C. The concentration of H + at equivalence point is (K W = 1 × 10−14 at 25∘ C) [JEE 2008]
(A) 3.7 × 10−13 M (B) 3.2 × 10−7 M (C) 3.2 × 10−2 M (D) 2.7 × 10−2 M
17. The dissociation constant of a substituted benzoic acid at 25∘ C is 1.0 × 10−4 . The pH of a 0.01 M
solution of its sodium salt is [JEE 2009]
18. Aqueous solutions of HNO3 , KOH, CH3 COOH and CH3 COONa of identical concentrations are
provided. The pair(s) of solutions which form a buffer upon mixing is(are) - [JEE -2010]
(A) HNO3 and CH3 COOH
(B) KOH and CH3 COONa
(C) HNO3 and CH3 COONa
(D) CH3 COOH and CH3 COONa
19. In 1 L saturated solution of AgCl[K Sp (AgCl) = 1.6 × 10−10 ], 0.1 mol of CuCl [K sp (CuCl) =
1.0 × 10−6 ] is added. The resultant concentration of Ag + in the solution is 1.6 × 10−x . The value
of ' x ' is. [JEE -2011]
20. The K sp of Ag 2 CrO4 is 1.1 × 10−12 at 298 K . The solubility (in mol/L) of Ag 2 CrO4 in a 0.1 M
AgNO3 solution is (K W = 1 × 10−14 at 25∘ C) [JEE 2013]
(A) 1.1 × 10−11 (B) 1.1 × 10−10 (C) 1.1 × 10−12 (D) 1.1 × 10−9

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21. The initial rate of hydrolysis of methyl acetate (1M) by a weak acid (HA, 1M) is 1/100th of that
of a strong acid (HX, 1M), at 25∘ C. The K a of HA is [JEE 2013]
(A) 1 × 10−4
(B) 1 × 10−5
(C) 1 × 10−6
(D) 1 × 10−3
Paragraph For Questions 22 and 23
When 100 mL of 1.0 M HCl was mixed with 100 mL of 1.0 M NaOH in an insulated beaker at
constant pressure, a temperature increase of 5.7∘ C was measured for the beaker and its
contents. (Expt-1). Because the enthalpy of neutralisation of a strong acid with a strong base is
a constant (−57.0kJmol−1 ), this experiment could be used to measure the calorimeter constant.
In a second experiment (Expt-2), 100 mL of 2.0 M acetic acid (K a = 2.0 × 10−5 ) was mixed
with 100 mL of 1.0 M NaOH (under identical conditions to (Expt-1)) where a temperature rise
of 5.6 ∘ C was measured. (Consider heat capacity of all solutions as 4.2Jg −1 K −1 and density of
all solutions as 1.0 g mL− 1)
22. Enthalpy of dissociation (in kJmol−1 ) of acetic acid obtained from the Expt-2 is
(K W = 1 × 10−14 at 25∘ C) [ЈEE ADVANCED 2015]
(A) 1.0
(B) 10.0
(C) 24.5
(D) 51.4
23. The pH of the solution after Expt-2 [ЈEE ADVANCED 2015]
(A) 2.8
(B) 4.7
(C) 5.0
(D) 7.0
24. The solubility of a salt of weak acid (AB) at pH 3 is Y × 10−3 mol L−1 . The value of Y is .
(Given that the value of solubility product of AB(K Sp ) = 2 × 10−10 and the value of ionization
constant of HB(K a ) = 1 × 10−8 [ЈEE ADVANCED 2018]

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25. Dilution processes of different aqueous solutions, with water, are given in LIST-I. The effects of
dilution of the solutions on [H + ]are given in LIST-II.
(Note: Degree of dissociation (a) of weak acid and weak base is << 1; degree of hydrolysis of
salt << 1; [H + ]represents the concentration of H + ions) [ЈEE ADVANCED 2018]
LIST-I LIST-II
(P) (10 mL of 0.1 M NaOH + 20 mL of (1) the value of [H + ] does not change
0.1 M acetic acid) diluted to 60 mL on dilution
(Q). (20 mL of 0.1 M NaOH + 20 mL of (2) the value of [H + ] changes to half
0.1 M acetic acid) diluted to 80 mL of its initial value on dilution
(R) (20 mL of 0.1 M HCl + 20 mL of (3) the value of [H + ] changes to two
0.1 M ammonia solution) diluted to 80 mL times of its initial value on dilution
1
(S) 10 mL saturated solution of Ni(OH)2 in (4) the value of [H + ] changes to
√2

equilibrium with excess solid Ni(OH)2 is times of its initial value on dilution
diluted to 20 mL (solid Ni(OH)2 is still
present after dilution). (5) the value of [H + ] changes to √2
times of its initial value on
dilution
Match each process given in LIST-I with one or more effect(s) in LIST-II. The correct option is
(A) P → 4; Q → 2; R → 3; S → 1 (B) P → 4; Q → 3; R → 2; S → 3
(C) P → 1; Q → 4; R → 5; S → 3 (D) P → 1; Q → 5; R → 4; S → 1

26. A solution of 0.1M weak base (B) is titrated with 0.1M of a strong acid (HA). The variation of pH
of the solution with the volume of HA added is shown in the figure below. What is the pK b of
the base? The neutralization reaction is given by [ЈEE ADVANCED 2020]
B + HA and rarr; BH + + A− .

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27. An acidified solution of 0.05 M Zn2+ is saturated with 0.1 M H2 S. What is the minimum molar
concentration (M) of H + required to prevent the precipitation of ZnS?
Use K sp (ZnS) = 1.25 × 10−22 and overall dissociation constant of H2 S, K NET = K1 K 2 =
1 × 10−21 . [ЈEE ADVANCED 2020]
28. A solution is prepared by mixing 0.01 mol each of H2 CO3 , NaHCO3 , Na2 CO3 , and NaOH in 100
mL of water. pH of the resulting solution is
[Given pK a1 and pK a2 of H2 CO3 are 6.37 and 10.32, respectively; log 2 = 0.30 ]
[ЈEE ADVANCED 2022]
29. Concentration of H2 SO4 and Na2 SO4 in a solution is 1 M and 1.8 × 10−2 M, respectively. Molar
solubility of PbSO4 in the same solution is X × 10−Y M (expressed in scientific notation). The
value of Y is [ЈEE ADVANCED 2023]
[Given: Solubility product of PbSO4 (K sp ) = 1.6 × 10−8 . For H2 SO4 , K a1 is very large and Ka2 =
1.2 × 10−2 ]
30. On decreasing the pH from 7 to 2 , the solubility of a sparingly soluble salt (MX) of a weak acid
(HX) increased from 10−4 mol L−1 to 10−3 mol L−1. The pK a of HX is [ЈEE ADVANCED 2023]
(A)3 (B) 4 (C) 5 (D) 2

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ANSWER KEY
EXERCISE-I
DPP-1
1. (C) 2. (D) 3. (B) 4. (B) 5. (D) 6. (C) 7. (D)
8. (D) 9. (D) 10. (D) 11. 6 × 107
12. (i) 6.53 ; (ii) (a) Basic , (b) Acidic 13. K w = 4 × 10−14 , pH = 6.7
14. 600 ions /mm3

DPP-2
1. (B) 2. (C) 3. (C) 4. (B) 5. (B) 6. (D) 7. (C)
8. (a) + 1, (b) 6.97, (c)7, 9. (a) 9 (b) 11.30 10. (7)
DPP-3
1. (B) 2. (B) 3. (C) 4. (B) 5. (A)
6. (a) 2.87, (b) 11.13 (c) 6.78, (d) 6.97 7. (a) K a = 10−8 , (b) Kb = 10−6
8. (10) 9. 1.11 × 10−4 10. (4.87)
DPP-4
1. (D) 2. (A) 3. (D) 4. (D) 5. (A) 6. (3) 7. (2.61)
8. 1.52, 9 × 10–5 M 9. [H + ] = 1.75 × 10−2 M, [CHCl2 COO− ] = 0.75 × 10−2 M
10. [H + ] = 10−3 M, [CH3 COO− ] = 3.6 × 10−4 M, [C7 H5 O− −4
2 ] = 6.4 × 10 M

DPP-5
1. (D) 2. (A) 3. (C) 4. (A) 5. (A) 6. pH = 11.46
7. [H + ] = [H2 PO− −3 2− −8 3−
4 ] = 2.7 × 10 , [HPO4 ] = 10 , [PO4 ] = 3.7 × 10
−19

8. [H + ] = 0.209M [SO2–
4 ] = 0.009 M [HSO4– ] = 0.191 M
DPP-6
1. (A) 2. (C) 3. (B) 4. (D) 5. (B) 6. (C) 7. (B)
8. (C) 9. (C) 10. (B)
11. (a) Basic (b) acidic (c) basic (d) basic (e) acidic (f) basic
(g) neutral (h) basic (i) basic (j) acidic
12. 2.5 × 10−5 ; 4.6
DPP-7

1. (C) 2. (B) 3. (C) 4. (B) 5. (B) 6. [OH − ] = 10–5

7. pH = 4.477 8. K b = 6.25 × 10−10 9. 1.66 % 10. pH = 10.43
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DPP-8
1. (C) 2. (C) 3. (A) 4. (B) 5. (C) 6. (B) 7. (A)
8. (i) 10−12 (ii) 10−6 (iii) 10−11 (iv) K b1 > K b2 > K b3

9. [OH − ] = 3.73 × 10−2 M, [H3 PO4 ] = 6 × 10−18 M 10. 4.19 11. (a) 6, (b) 1 × 10−5
DPP-9
1. (C) 2. (B) 3. (C) 4. (A) 5. (B) 6. (0.1) 7. pH = 7
8. (8.34) 9. (4.19) 10. (1) 11. 100
DPP-10
1. (A) 2. (D) 3. (A) 4. (D) 5. (B) 6. (D) 7. (C)
8. (4) 9. [OH − ] = 9.0 × 10−6 10. 0.05 mol
11. (a) pH = 9.24 (b) lowered (c) pH = 4.699
DPP-11
1. (B) 2. (A) 3. (A) 4. (A) 5. (A) 6. (B) 7. (6)
8. (5) 9. (i) pH = 9.26; (ii)(a) pH = 9.74; (b) 8.78
DPP-12
1. (B) 2. (D) 3. (C) 4. (A) 5. (D) 6. (A)
7. (a) 13; (b) 7; (c) 1.3. 8. (3) 9. 9.48 10. 8.78 11. 10−5 M
DPP-13
1. (C) 2. (C) 3. (A) 4. (C) 5. (D) 6. (3.1) 7. (6)
8. (1.8)
DPP-14
1. (D) 2. (C) 3. (A) 4. (D) 5. (A) 6. (C)
7. 1.0 × 10−5 mol/lit 8. 1.56 × 10−8 9. 3.4 × 10−11 10. QX2 is more soluble
11. 5 × 10−10 M 12. 4 × 10−7 mol/LAgBr, 9 × 10−7 mol/LAgSCN
DPP-15
1. (B) 2. (A) 3. (B) 4. (C) 5. (D) 6. (D) 7. (C)
8. (C) 9. (a) no precipitation will occur, (b) a precipitate will form 10. (1)
11. (9 × 10–4); OMR ANS (9) 12. 12 mg 13. 4.9 × 10–10

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DPP-16
1. (C) 2. (D) 3. (C) 4. (B) 5. 10−5 6. (A)
7. 69K d = 1/K f = 4.8 × 10−4 Q. 700.444M 8. 2.8 × 10–3 mole
9. (d) > (c) > (b) > (a) 10. 2.1 × 10−5
DPP-17
1. (A) 2. (A) 3. (A) 4. (C) 5. (D) 6. (C) 7. (D)
8. (B) 9. (A) 10. (C) 11. [HIn ] = 28.57% 12. ΔpH = 0.954
13. 2 14. (018)
EXERCISE-II
1. (ABC) 2. (ABCD) 3. (ACD) 4. (ABCD) 5. (BCD)
6. (AD) 7. (AB) 8. (BC) 9. (A) 10. (ABC)
11. (ABCD) 12. (ABD) 13. (B) 14. (A) 15. (C)
16. (C) 17. (B) 18. (A) 19. (A) 20. (C) 21. (D) 22. (D)
23. (B) 24. (D) 25. (B) 26. (A) 27. (B)
28. (A)-S ; (B)-R ; (C)-P,T ; (D) - P, Q 29. (A)- S ; (B)- R ; (C) -S ; (D) – S
30. (A)- R ; (B)- Q ; (C) -P ; (D) – S; (E) – T
31. [S 2− ] = 2.5 × 10−15 32. (a) 2.12 (b) 4.66 (c) 7.2 (d) 12
33. pH = 7.3; pH = 7.898, pH = 7.29 34. 5.21 35. 0.444 M 36. K a = 1.12 × 10−2
37. 9.168 38. (a) 8.34 (b) 4.66 (c) 9.6 (d) 7.20
39. [H2 CO3 ] = 10−5 M; [HCO3 − ] = 5 × 10−4 [CO3 2− ] = 2.5 × 10−8
40. 8.96 41. (a) pH = 3.83 (b) pH = 3.85, (c) = 4 42. (8.25)
43. 2.49 × 10–5 or 2.50 × 10–5 44. 400 45. 5500 mg
EXERCISE # JEE-MAIN
1. (C) 2. (C) 3 (D) 4. (D) 5. (C) 6. (A) 7. (A)
8. (D) 9. (D) 10. (B) 11. (C) 12. (D) 13. (C) 14. (D)
15. (C) 16. (A) 17. (C) 18. (A) 19. (D) 20. (D) 21. (A)
22 (D) 23. (A) 24. (A) 25. (D) 26. (D) 27. (C) 28. (B)
29. (D) 30. (D) 31. (C) 32. (C) 33. (B) 34. (A) 35. (C)
36. (C) 37. (A) 38. (A) 39. (B) 40. (A) 41. (A) 42. (B)
43. (B) 44. (D) 45. (B) 46. (B) 47. (C) 48. (525) 49. (B)
50. (4) 51. (27) 52. (2) 53. (C) 54. (A) 55. (D) 56. (10)
57. (9079) 58. (186) 59. (10)
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EXERCISE # JEE-ADVANCED
1. pH = 11.3010 2. 𝐬 = 𝟏. 𝟐𝟎𝟑 × 𝟏𝟎–𝟑 𝐌 3. (A, B, C)
4. (B) 5. pH = 4.86 6. (A) 7. (A)
8. (a) 0.0175% , (b) 4.757 9. No it will be > 7 10. (C) 11. (A)
12. pH = 9 13. (B) 14. (A) 15. (D)
16. (D) 17. (8) 18. (CD) 19. (7)
20. (A) 21. (A) 22. (A) 23. (B)
24. (4.47) 25. (D) 26. 3.3
27. [𝐇 + ] ≥ 𝟎. 𝟐 28. ∴ 𝐩𝐇 = 𝟏𝟎. 𝟎𝟐29. 𝐘 = 𝟔 30. (B)

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SOLUTION
DPP-1
6. pHi = 3 ⇒ [H + ]i = 10−3 M
pHf = 6 ⇒ [H + ]f = 10−6 M
[H + ]i Vi = [H + ]f Vf
10−3 × Vi = 10−6 × Vf
Vf = 1000 Vi
Ci = 1000Cf
7. H2 O ⟶ H + + OH + ΔH = + ive
10. Kw = [H + ] × [OH − ]
for pure water [H + ] = [OH − ]
Kw = 10−6.7 × 10−6.7 = 10−13.4
PROPERTIES OF WATER & pH-SCALE
11. pH = 13
[H + ] = 10−13 M
= 10−13 mol/L
= 10−13 × 6 × 1023 ions /L
∵ 1 L contains 6 × 1010 ions
∴ 10−3 L will contain = 6 × 1010 × 10−3 = 6 × 107 ions
12. (i) K w = [H + ][OH − ] = 9 × 10−14
In pure water
[H + ] = [OH −2 ] = 3 × 10−7
pH = 7 − log 3 = 6.53
(ii) At 60∘ C neutral pH = 6.53
If pH < 6.53 then solution will be acidic and pH > 6.52. Then solution will be basic.
13. 2H2 O ⟶ H3 O+ + OH −
C(1 − α) Cα Cα
1000
[H + ] = × 3.6 × 10−9 = 2 × 10−7 M
18

K w = [H + ][OH − ] = 2 × 10−7 × 2 × 10−7 = 4 × 10−14

14. 2NH3 ⟶ NH4+ + NH2−
[NH4+ ][NH2− ] = 10−30
[NH2− ] = [NH4+ ] = 10−15 M
[NH2− ] = 10−15 × 6 × 1023 ions /L

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∵ 1 L contains 6 × 108 NH2− ions

∴ 10−6 L(1 mm3 ) will contain = 6 × 108 × 10−6 = 600NH2− ions
DPP-2
1. P H = −log (4 × 10−4 ) = 3.4
2. pH = 13, so pOH = 1 ⇒ [OH − ] = 0.1
Moles of OH −
0.1 =
0.25
Moles of OH − = 0.025
Mass of NaOH = 0.025 × 40 = 1 g
3. [[H + ]i = 10−2 [H + ]𝑓 = 10−3
initial moles = 10−2 final moles of H + = 10−3
Moles of H + should be removed = 10−2 − 10−3 = 0.009
1 1
10× ×2+40× ×2 1
4. [H + ]𝑓 = 200 200
= 100 ⇒ pH = 2
50

5. pH of acid < 7
So pH sol should ⇒ 6 − 7
6. As the acid is very dilute, the contribution of water should be taken. Let H2 O dissociates only up
to xM in presence of HCl .
H2 O ⟶ H + + OH −
Equilibrium (𝑥 + 10−7 )MM
Now, [H + ][OH − ] = K w ⇒ (x + 10−7 ) ⋅ x = 10−14
⇒ x = 6.18 × 10−8
∴ [H + ] = (x + 10−7 )M = 1.618 × 10−7 M
⇒ pH = 6.79
7. H2 O ⟶ H + + OH −
(C + x) (x) = 10 − 14
Given C + x = 10−6.7 = 10−7 × 100.3 = 2 × 10−7
(2 × 10−7 )(x) = 10−14 x = 1/2 × 10−7 = 0.5 × 10−7
C + x = 2 × 10−7
C = 1.5 × 10−7
8. (a) [H + ] = 10−1 ⇒ pH = 1
(b) H2 O ⟶ H + + OH −
x + 10−8 x
K w = (x + 10−8 )x = 10−14
x = 9.5 × 10−8

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[H + ] = 10.51 × 10−8 M
pH = 8 − log 10.51 = 8 − 1.03 = 6.97
(c) H2 O ⟶ H + + OH −
x 10−10 + x
K w = (x + 10−10 )x = 10−14
x ≈ 10−7
pH = 7
10−3
9. (a) [OH − ] = = 10−5 M
100

pOH = 5 ⇒ pH = 9
1 2
(b) [OH − ] = 10 × 10 = 2 × 10−3

pOH = 3 − log 2
pH = 11 + log 2 = 11.3
10. If V → ∞, then solution will almost neutral. So pH = 7
DPP-3
1. Higher the 𝐾𝑎 , stronger the acid
2. NH4 OH ⟶ NH4+ + OH −
𝑐(1 − 𝛼) c𝛼 c𝛼
5
[OH − ] = c𝛼 = 0.02 × = 10−3
100

pOH = 3 ⇒ pH = 11
3. CH3 COOH ⟶ CH3 COO− + H +
0.1(1 − 𝛼) 0.1𝛼 0.1𝛼
0.1𝛼 × 0.1𝛼
10−5 =
0.1(1 − 𝛼)

−5
0.1𝛼 2 𝛼2
10 = ⇒ = 10−4 ⇒ 𝛼 = 10−2
1−𝛼 1−𝛼
[H + ] = c𝛼 = 10−3
1
4. pOH = 2 [pK b − log C]

9 = pK b − log (0.1)
pK b = 8 Ans.
x2
5. Kb = ; x = [OH − ] = 10−2
C−x

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6. (b) CH3 COOH ⟶ CH3 COO− + H +

0.1 − x x x
x2
1.8 × 10−5 =
0.1 − x
x 2 = 1.8 × 10−6
[H + ] = x = 1.36 × 10−3
pH = 3 − log 1.3 = 2.87
(c) NH4 OH ⟶ NH4+ + OH −
0.1 − x x x
𝑥2
1.8 × 10−5 = 0.1−𝑥

[OH − ] = x = 1.34 × 10−3

pOH = 2.87 ⇒ pH = 11.13
(f) 10−7 MCH3 COOH
CH3 COOH ⟶ CH3 COO− + H +
Acid will completely dissociate, so 𝛼 ≈ 1
Taking contribution of water
[H + ] = 1.62 × 10−7 ⇒ pH = 6.78
Ka 1.8×10−5
(g) = = 1.8 × 100
C 10−8

Acid will completely dissociate, so 𝛼 ≈ 1

CH3 COOH ⟶ CH3 COO− + H +
10−8 10−8 + x
H2 O ⟶ H + + OH −
10−8 + x x
K w = (10−8 + x)x = 10−14
x = 9.51 × 10−8
[H + ] = 10.51 × 10−8 ⇒ pH = 6.97
7. (a)HA ⟶ H + + A−
10−4.5 10−4.5
10−4.5 ×10−4.5 10−9
Ka = = = 10−8
0.1−10−4.5 0.1

(b) BOH ⟶ B+ + OH −
10−3.5 10−3.5
10−3.5 × 10−3.5
Kb = = 10−6
0.1 − 10−3.5

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C1 𝛼12 C 𝛼2
8. 2 2
= 1−𝛼
1−𝛼1 2

𝛼2 𝛼
𝛼12 = 10−2 𝛼22 ⇒ 𝛼22 = 100 ⇒ 𝛼2 = 10
1 1

9. HA ⟶ H + + A−
10−3 10−3
10−6 10−6 1
K a = 10−2 −10−3 = 9×10−3 = 9 × 10−3
𝑥2
10. 5.9 × 10−10 = 0.3−𝑥

𝑥 2 = 5.9 × 0.3 × 10−10

x = √1.77 × 10−5
pH = 5 − log √1.77 = 4.87
DPP-4
10−3 +10−5 101
2. [H + ]f = = × 10−5
2 2
101
pH = 5 − log = 3.3
2
3. [H + ] = √Ka1 C1 + Ka2 C2 == 4 × 10−3 M
4. RNH2 + H2 O ⟶ RNH3 + + OH −
0.01-x x x
x−(x+10−4 )
2 × 10−6 = 0.01−x

x 2 + 10−4 x − 2 × 10−8 = 0
x = 10−4
[OH−] = 2 × 10−4
0.1 4 1
5. [OH − ] = √Ka1 C1 + Ka2 C2 = √6.4 × 10−5 × + 1.8 × 10−5 × 45 × 2
2

8
= √ × 10−6 = 2 × 10−3 M
2

pOH = 3 − log 2
pH = 11 + log 2 = 11.3
10−4 19
6. [H + ] = + × 10−4 = 10 × 10−4 = 10−3
2 2

⇒ pH = 3
10+20 30
7. (a) [H + ] = =
100 100

pH = 1 − log 3 = 0.52
(b) [H + ] = √2 × 10−5 × 0.1 + 4 × 10−5 × 0.1 = √6 × 10−3
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pH = 3 − 0.39 = 2.61
8. HCOOH ⎯→ H+ + HCOO–
0.05–x x x
x2
1.8×10–4 =
0.05 − x
x2 = 1.8×10–4×0.05
x2 = 9×10–6
pHi = 2.52
HCOOH ⎯→ H+ + HCOO–
0.05–x 0.1+x x
(0.1 + x) x
1.8×10–4 =
0.05 − x
x2 + 0.1x – 9×10–6 = 0
x = 0.9×10–4
[H+] = 0.1
pHf = 1
pH = 1 – 2.52 = –1.52
0.1 [HCOO − ]
1.8×10–4 =
0.05
[HCOO–] = 0.9×10–4 = 9×10–5 M
9. CHCl2COOH ⎯→ CHCl2COO– + H+
0.01–x x x+0.01
x(x + 0.01)
3×10–2 =
0.01 − x
x2 + 4×10–2x–3×10–4 = 0
x = 0.64×10–2
[H+] = 1.64×10–2 M
[CHCl2COO–] = x = 0.64×10–2 M

10. [H+] = 1.8 10−5  0.02 + 6.4 10−5  0.01 = 10–3 M

[CH3COO − ] 10−3
1.8×10–5 =
0.02 − 10−3
[CH3COO–] = 1.8×10–2×19×10–3 = 3.42×10–4 M
C7 H5O2−  10−3
6.4×10–5 =
0.01 − 10−3

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C7 H5O2−  = 6.4×10–2×9×10–3 = 5.76×10–4 M

DPP-5
POLYPROTIC ACIDS & BASES
5. HPO42– ⎯→ H+ + PO43–
6. → enH + + OH −
en + H 2O ⎯⎯ kb1 = 8.5 × 10–5

0.1–x x–y x+y

x x

enH+ + H2O ⎯⎯
→ enH22+ + OH− kb2 = 7.1 × 10–8

x–y y x+y
x x
kb1 >> kb2 so x >> y
x2
8.5 × 10–5 =  x2 = 8.5 × 10–6  x = 2.91 × 10–3
0.1 − x
[OH–] = 2.91 × 10–3 M  pH = 11.46
7. H3PO4 ⎯→ H+ + H2 PO4−
10–2–x x+y+z x–y
H2 PO4− ⎯→ H+ + HPO24−
x–y x+y+z y–z
HPO24− ⎯→ H+ + PO34−
y–z x+y+z z
Ka1 >> Ka2>> Ka3, so x >> y >> z
(x + y+z)(x − y)
10–3 =
10−2 − x
x2
10–3 =
10−2 − x
x2 + 10–3x – 10–5 = 0  x = 2.7×10–3

(x + y + z)(y − z)
10–8 =
x−y
xy
10–8 =  y = 10–8
x

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(x + y + z)  z
10–13 =
y−z

x  z 2.7 10−3  2
10–13 = =
y 10−8
1
z= ×10–18 = 3.7×10–19
2.7
[H+] = [ H2 PO4− ] = 2.7×10–3 M

[ HPO−4 ] = 10–8 M

[ PO34− ] = 3.7×10–19

H3PO4 = 7.3×10–3 M

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8. → H+ + HSO4−
H2SO4 ⎯⎯

0.2 0.2 0.2

H2SO4− ⎯⎯
→ H+ + SO24−

0.2–x 0.2+ x 0.2

(0.2 + x)
10−2 =
0.2 − x
x2 + 21 × 10–2x – 2 × 10–3 = 0
x = 0.9127 × 10–2
[H+] = 0.209 M
[SO42–] = 0.009 M
[HSO4–] = 0.191 M
DPP-6
1. NH2– + H+ ⎯→ NH3
Base conjugate acid
2. HNO3 + H2O ⎯→ H3O+ + NO3–
Acid Base C.A C.B.
3. Bronsted acid ⎯→ which can give H+
5. RNH3+ ⎯→ RNH2 + H+ ; Ka

1
ka
6. Ka HF × Kb F– = Kw
pKa = 14 – 10.83= 3.17
Ka = 10–3.17 = 6.75 × 10–4
7. CH3COOH + OH–⎯→CH3COO– + H2O
1 Ka 1.8  10−5
Keq = = = = 1.8 × 109
Kh Kw 10−14
8. Ka HF × Kb F– = Kw
pKa = 14 – 10.83 = 3.17
Ka = 10–3.17 = 6.75 × 10–4
11. All cations (Cu2+, NH4+)are acid and all anions (C2H5O– ,F–, SO32− )are base

Solution of salt of SA + SB ⎯→ Neutral (KNO3)

Solution of salt of SA + WB ⎯→ Acidic (ZnCl2)
Solution of salt of WA + SB ⎯→ Basic (NaOCl, CH3COONa, Na2CO3)
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10−14
12. Ka(HOCl) = = 3.5×10–5
4  10 −10
DPP-7
1. At 85ºC neutral pH < 7
0.01
2. [H+] = = 10–3 M  pH = 3
100
3. (A) 0.1 M NaCl  pH = 7
(B) 0.1 M NH4Cl  pH < 7
(C) 0.1 M CH3COONa  pH > 7
(D) 0.1 M HCl  pH = 1
4. pKa for HCN = 14 – 4.70 = 9.30
Due to small degree of anionic hydrolysis
1 1 1
pH = [pKw + pKa + log C] = [14 + 9.30 + log 0.4] = [23.30 – 0.4 ] = 11.45
2 2 2
5. CN− + H2O ⎯→ HCN + OH −

0.01(1 − h) 0.01h 0.01h

10−14 0.01h 2
=
1.4  10 −9 1− h
10
h2 = 10−4
1.4
h = 2.67 × 10–2
% h = 2.67% K b3  K b2  K b1

6. CH3COO– + H2O ⎯→ CH3COOH + OH–

0.01–x x x
7. NH+4 +H2O ⎯→ NH4OH + H+
2–x x x
10−14 x2
=
1.8 10−5 2 − x
2 10−9
x2 =
1.8
10
x = [H+] = ×10–5  pH = 4.48
3

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8. C6H5N + H2O ⎯→ C5H5N + H3O+

0.25–x x x
10−14 4 10−6
=
Kb 0.25 − 2 10−3

10−14 4 10−6
=
Kb 0.25

0.25  10 −14 1
Kb = −6
= ×10–8 = 6.25×10–10
4  10 16
9. CN− + H2O ⎯→ HCN+ OH −

0.06(1 − h) 0.06h 0.06h

10−14 .06h 2
=
6  10 −10 1− h
1 0.06h 2
×10 =
–14
6 1− h

0.06h2 = ×10–4
6

h2 = ×10–2
36
1
h= = 0.0166= 1.66 %
60
10. C6 H5O− + H2O ⎯⎯
→ C6H5OH+ OH−

10–3–x x x
10−14 x2
=
1.05 10−10 10−3 − x

−4 x2
10 = −3
10 − x
x2 + 10–4x – 10–7 = 0

41 − 1
[OH–] = x = 10−4 = 2.7 × 10–4
2
pH = 10 + log2.7 = 10.43
DPP-8
1. Fe3+ + H2O ⎯→ Fe(OH)2+ + H+
2. S2– + H2O ⎯→ HS– + OH–
4. HPO2− −
4 + H2 O → H2 PO4 + OH
−

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Kw
Kb =
Ka2
7. A3– + H2O ⎯→ HA2– + OH–
Kw
Kh1 =
Ka 3
1
pH = (pKw + pKa3 + logC)
2
8. H3PO4 ⎯→ H+ + H2 PO4−

H2 PO4− ⎯→ H+ + HPO24−

HPO24− ⎯→ H+ + PO34−

(i) Dissociation constant of HPO24− = K a3 = 10−12

(ii) Ka H2 PO4− ×Kb HPO−42 = Kw

10−14
Kb HPO−42 = = 10–6
10−8

(iii) KaH3PO4 ×Kb H2 PO4− = Kw

10−14
Kb H2 PO4− = = 10–11
10−3
K w 10−14
(iv) Kb PO34− = = = 10–2
K a 3 10−12

9. PO34− + H2O ⎯⎯
→ HPO42− + OH−
0.1− x x x

10−14 x2
=
4.5 10−13 0.1 − x
x2 1
=
0.1 − x 45
45x2 + x – 0.1 = 0
[OH–] = x = 4.911 × 10–1
[H2PO4–] = 6.2 × 10–8 M
H2PO4– + H2O ⎯→ H3PO4 + OH–
10. CrO 24− + H2O ⎯→ HCrO −4 + OH −

0.005–x x x

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k w 0−14 x2
kh1 = =
k a 2 3.110−7 0.005 − x

10−7 −10
=
x2
 x2 = 5  10
3.1 5 10−3 3.1
x = h =1.26×10–5
.26  10 −5
h= = 2.52×10–3
5  10 −3
2+ + +
11. (a) Zn + H2O ⎯→ Zn(OH) + H

0.001–x x x
x2
10–9 =
10−3 − x
x2 = 10–12
x = [H+] =10–6 M  pH = 6

(b) Ka Zn+ ×Kb Zn(OH)+ = Kw

10–9 × Kb Zn(OH)+ = 10–14
Kw Zn(OH)+ = 10–5
DPP-9
1 1
1. pH = (pKw + pKa – pKb) = × (14 + 4.8 – 4.78) = 7.01
2 2
h
2. = Kh (for salt of WA + WB)
1− h
h does not depend on conc.
3. Amphiprotic species → which can give as well as take H+ ion.
1
5. pH = 2 (pK a 2 + pK a1 ) = 8 ⇒ [H + ] = 10−8

HCO− + 2−
3 → H + CO3 K a 2 = 10−10
[H+ ][CO2−
3 ]
Ka2 = [HCO3 − ]

10−8 ×[CO2−
3 ]
10−10 = 0.2

[CO2−
3 ] = 2 × 10−3
Kw 10−14
6. K h = √K = √10−7 ×10−5 = 10−1
a Kb

1
7. pH = (pKw + pKa – pKb)
2

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pH = 7
pK 2 + pK1 10.34 + 6.34
8. pH = = = 8.34
2 2
pK 2 + pK1 5.44 + 2.94
9. pH = = = 4.19
2 2
1
11. pH = 2 (14 + 5 − 5) = 7

⇒ H2 O + CH3 COO− → CH3 COOH + OH −

Kw [CH3 COOH]×10−7
= 10−9 = [CH3 COO− ]
Ka

DPP-10
1. For 1 M NaCl & 1 M HCl solution
 pH < 7
2. pOH = pKb = 4.74
pH = 9.26
[CH 3COO – ]
3. pH = pKa + log
[CH 3COOH]
3
= 4.82 + log =5
2
5  VmL
4. pH = 10 – log5 + log =9
10  2
5VmL
log = log0.5
20
VmL = 2 mL
[C.B]
5. pH = pKa + log
[Acid]
[C.B]
Ph – pKa = log = 5 = log 105
[Acid]
[C.B.] = 105 × [Acid]
10 1
8. pH = 5 + log =5–1=4
50  2

[NH +4 ][OH − ]
9. Kb =
[NH 4 OH]

0.1 [OH − ]
1.8×10–5 =
5  10 −2
[OH–] = 1.8×5×10–6 = 9×10–6 M

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10. Moles of (NH4)2SO4 = x

Moles of NH3 = 1
 NH +4 ]
pOH = pKb + log
[NH 3 ]
2x
4.74 = 4.74 + log
0.1
0.1
2x = 0.1  x = = 0.05
2
11. (a) C5H5N + H2O ⎯→ C5H5N+ + OH–
0.2–x x x
x2
1.5×10–9 =
0.2 − x
x2 = 3×10–10
[OH–] = x = 3 ×10–5 M
1 1
pOH = 5 – log3  pH = 9 + log3 = 9.24
2 2
(b) Equilibrium will shift to backward reaction so [OH–], pOH , pH
[C5 H 5 NH + ]
(c) pOH = pKb + log
[C5 H 5 N]
0.3
= 9 – log1.5 + log = 9 – log1.5 + log3= 9.3
0.1
pH = 4.7
DPP-11
1. If [NH4OH] , [OH–], pH 
2. On moderate dilution pH of buffer solution does not change.
3. HA + NaOH ⎯→ NaA + H2O
10 mmol x mmol 10 mmol –
10–x 0 10+x –
[A – ]
pH = pKa + log
[HA]
10 + x
5.5 = 5 + log
10 – x
10 + x
3.16 =  x = 5.2
10 – x
Mass of NaOH added = 5.2 × 40 × 10–3g= 2.08 × 10–1g

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0.02
4. Buffer capacity = = 0.4
0.05
6. Buffer capacity is max when a = b = 0.5
8. Buffer capacity,
[H + ]added 0.05 / 0.2
=− =− =5
P H
(−0.05)

9. (a) NH4OH + NaOH ⎯→ NH4OH– + NaCl

0.1 0.05 0.1 – (initial moles)
0.05 0 0.15 – (moles at equilibrium)
pOHi = 4.74  pHi = 9.26
0.05
pOHf = 4.74 + log = 4.74 – log3
0.15
pHf = 9.26 + log3 = 9.74
(b) NH4OH + HCl ⎯→ NH4Cl + H2O
0.1 0.05 0.1 (initial moles)
0.05 0 0.05 (moles at equilibrium)
pOHi = 4.74  pHi = 9.26
0.05
pOHf = 4.74 + log = 4.74 + log3
0.15
pHf = 9.26 – log3 = 8.78
DPP-12
8 1
1. Moles of OH– = =
40 5
4.9 1
Moles of H+ = 2 =
98 10
0.1
[OH–] = = 0.1
1
pOH = 1  pH = 13
2. m Moles of H+ = 15
m Moles of OH– = 5
10 1
[H+]ƒ = =  pHƒ = 1
100 10
3. NaCN + HCl ⎯→ HCN + NaCl
mmi 4 2 0 0
mmƒ 2 0 2 2

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0.6
4. pH = 4.74 + log = 4.92
0.4
5. HCOOH + KOH ⎯→ HCOOK + H2O
mm : 16 8 0 0
mmƒ 8 0 8 -
8
pH = 3.7 + log = 3.7
8
pOH = 10.3
6. CH3COONa + HCl ⎯→ CH3COOH + NaCl
mmi 2 2 0 0
mmƒ 0 0 2 -
2
[CH3COOH] = = 0.1
20
− +
CH 3COOH ⎯⎯
→ CH3COO + H
0.1− x x x

x2
1.8 × 10–5 =
0.1 − x
−3
[H+] = x = 1.8 10
pH = 2.88
7. (a) millimoles of OH– = 8
millimoles of H+ = 3
5
[OH–] = = 0.1
50
pOH = 1  pH = 13
(b) millimoles of H+ = 0.2
millimoles OH– = 0.2
Hence solution will be neutral, so pH = 7

(d) millimoles of H+ = 1×2

millimoles of OH– = 1
1
[H+] =
20
pH = log20 = 1.3
8. In case of (iii) buffer can be prepared
In case of (iv) and (v) buffer can be prepared if moles of weak acid or weak base is more

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9. NH4Cl + NaOH ⎯→ NH4OH + NaCl

10m mol 7.5m mol – –
2.5m mol 0 7.5m mol –
pOH = 5 + log(2.5/7.5)= 5 + log1/3 = 4.52
10. NH3 + HCl ⎯→ NH4Cl
20m mol 15m mol –
5m mol 0 15m mol
15
pOH = 4.74 + log = 4.74 + log3
5
pH = 9.26 – log3 = 8.78
11. CH3COO− H2O ⎯→ CH3COOH+ OH−

0.1–x x x
10 −14 x2
=
10−5 0.1 − x
x2
10–9 =
0.1
x2 = 10–10
x = [OH–] = 10–5
pOH = 5  pH = 9
DPP-13
1. (A) H3PO4 + NaH2PO4 (W.A + its salt)
(B) H2CO4 + NaHCO3 (W.A + its salt)
(C) NH4Cl + HCl (W.A + its salt)
(D) CH3COOH + CH3COONa (W.A + its salt)
2. For 0.1 M NaHA
7 + 11
pH = =9
2
for 0.1 M H2A pH < 7
for 0.1 M Na2A pH > 7
for 0.1 M NaHA + 0.1 M Na2A  pH = pKa2 = 11
3. N3PO4 + NaH2PO4
NaH2PO4 + Na2HPO4
Na2HPO4 + Na3PO4
4. H3PO4 + NaOH → NaH2PO4 + H2O

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10 15 –
0 5 10
NaH2PO4 + NaOH → Na2HPO4 + H2O
10 5 0
5 0 5
5
pH = pKa2 + log = pKa2
5
5. Na2CO3 + HCl ⎯→ NaHCO2 + NaCl
2.5m mol 4m mol
NaHCO3 + HCl ⎯→ H2CO3 + NaCl
Final m moles NaHCO3 = 1 m mol.
H2CO3 = 1.5 m mol.
Above is a buffer solution of H2CO3 & NaHCO3
1
pH = pKa1 + log
1.5
=6.17
6. H3PO4 + NaOH ⎯→ NaH2PO4 + H2O
mmi 9 5 0 0
mmƒ 4 0 5 -
5
pH = 3 + log = 3.1
4
7. At second equivalence point the only species present at appreciable conc. = HA2–
pk 2 + pk 3 8 + 12
So, pH = = = 10
2 2
[H+] = 10–10

 H3A H 
+ 3

And = = 10–6 Ans.

A3− k1k 2 k 3
DPP-14
1. Ksp = (2s)2 × (3s)3 = 108 s5
14.3  10 −4
2. s= = 10–5 M
143
Ksp = s2 = 10–10 M2
7
3. s= = 7 × 10–2 M
100
Ksp = s2 = 4.9 × 10–3
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4. (A) Ksp = s2

s= 80 × 10–19 M
(B) Ksp = s2

s= 7 × 10–8 M
(C) Ksp = 108 s5 = 1 × 10–72
1
 1000  5
s=   × 10–15 M
 108 
(D) Ksp = 27 s4
 180 
s=   × 10 M
–5
 27 
5. 4s3 = 8.64 × 10–13
s3 = 216 × 10–15
s = 6 × 10–5 M (in water)
Ag2CrO4 ⎯→ 2Ag + + CrO 24−
2s s + 0.6
 0.6

(2s)2 × 0.6 = 8.64 × 10–13

4s2 = 14.4 × 10–13
s2 = 3.6 × 10–13
s = 6 × 10–7 M
6. SrCO3 ⎯→ Sr 2+ + CO32−
s1 s1 +s2

ZnCO3 ⎯→ Zn 2+ + CO32−
s2 s2 +s1

(s1 + s 2 )s1 10 −10 100

= =
(s1 + s 2 )s 2 1.5  10 −11
15

s1 20
=
s2 3

SOLUBILITY & SOLUBILITY PRODUCT'S

7. A3X3(s) ⎯→ 2A3+(aq) + 3X2–(aq)
2s 3s
Ksp = (2s)2 ×(3s)3 = 108s5 =1.08×10–23
s = 10–5 M
0.038
8. s= = 1.25×10–3 M
3.04

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Ksp = s2 = (1.25)2×10–8 = 1.56×10–8 M

9. CaF2 ⎯→ Ca2+ + 2F–
10−4
4.1× 4.1×10–4
2
4.110−4
Ksp =  (4.110−4 ) 2 = 3.44×10–11
2
10. For MX
s2 = Ksp = 4×10–18
s = 2×10–9 M
For QX2
4s2 = Ksp = 4×10–18
s = 10–6 M
Solubility of QX2 is more
11. AgCl ⎯→ Ag+ + Cl–
s s+0.2
s×0.2 = 1×10–10
s = 5×10–10 M
12. AgSCN ⎯→ Ag+ + SCN–
s1+s2 s1
AgBr ⎯→ Ag+ + Br –
s1+s2 s2
(s1 + s2)s1 = 1.1×10–12
(s1 + s2)s2 = 5×10–13
(s1 + s2)2 = 1.6×10–12
s1 + s2 = 1.6 10−6

1.110−12
s1 = = 9×10–7 M
1.6 10−6

5 10−13
s2 = = 4×10–7 M
1.6 10−6
DPP-15
1. [Ba2+] [CO32–] = Ksp
5.1 × 10–9 = [Ba2+] × 10–4
[Ba2+] = 5.1 × 10–5 M
2. Ksp = [Mg2+] [OH–]2

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1 × 10–11 = 0.1 × [OH–]2

[OH–] = 10–5 M
pOH = 5  pH = 9
3. QIP = 10–3 × 10–10 = 10–13
QIP < Ksp (no ppt)
4. Ag+ + Br– ⎯→ AgBr
Ci 10–7 M 10–7 M 0
Qip=10–7 × 10–7 =10–14 ,Qip < Keq,
So there will be no precipitation
5. Ag2CrO4 2Ag+ + CrO 24 −

10mmol 80mmol
5 0 75
x 75
500 500
2
 x   75 
then     = 15 × 10 12
–
 500   500 
x
= 10–5
500
x = 5 × 10–3

5  10−3
[Ag+] = = 10–5
500
6. AgCl(s) ⎯→ Ag+ (aq.) + Cl– (aq.)
y x–y 4 × 10–5 – y
4 × 10–5 – y = 10–5
y = 3 × 10–5
(x – y) (4 × 10–5 – y) = 10–10
(x – y) (10–5) = 10–10
x – y = 10–5
x – 3 × 10–5 = 10–5
x = 4 × 10–5

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8. Ksp = [Ag+] [Cl–]

[Ag+]

[Cl–]

9. For pptn Ksp= QIP

(a) QIP = 10–3 ×(10–5)2 = 10–13
So QIP < Ksp No pptn
(b) QIP = 10–3×10–6 = 10–9
QIP > Ksp pptn will occur
8 10−6  v 10−4
10.  = 2×10–10
v +1 v +1
(v–1)2 = 0  v = 1 L
11. Ksp = 4s3 = 4 × (10–3)3 = 4 × 10–9
4 × 10–9 = [Ag+]2 [Cr O24− ]

= [Ag+]2 [10–1]
[Ag+] = 2 × 10–4 M
[Ag+] moles precipitated = 2 × 10–3 – 2 × 10–4 = 18 × 10–4
moles of Ag2CrO4 precipitated = 9 × 10–4
1
12. Pb2+ + 2Cl− ⎯⎯
→ PbCl2 (s) k=
ksp
0.1x 0.75 M 0
x 0.55 M 0.1M
1 1
−4
=
1.7 10 x  (0.55) 2
1.7
x= 2
10−4 = 5.6 × 10–4
(0.55)
[Pb2+] = 5.6 × 10–4
Moles of Pb2+ = 5.6 × 10–5
Mass of Pb2+ = 5.6 × 208 × 10–5= 1.2 × 10+3 × 10–2 mg= 12 mg
13. CaCO3 ⎯→ Ca2+ + CO32−

7×10–5
BaCO3 ⎯→ Ba2+ + CO32−

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7×10–5
10−5  [CO32− ] 5 10−10
=
7 10−5  0.1 [CO32− ] K sp (BaC O3 )

Ksp(BaCO3) = 4.9×10–10

DPP-16
1. CN– + H2O ⎯→ HCN + OH–
Solubility if [OH–] , [H+] , pH
2. Solubility of Ag2CO3 will be max. in NH3 due to complex formation.
4. Ag+ + 2NH3 Ag(NH3) +2

x 0.8 0.1
Ag (NH3) +2 Ag (NH3)+ + NH3

0.1 – x x 0.8 + x
0.1 0.8
1 1 (0.8)x
= 4=  x = 1.25 × 10–5
K f2 10 0.1

6. Ag A (s) ⎯→Ag+ (aq) + A–(aq)

S S–x
A–(aq) + H2O ⎯→AH (aq) + OH–(aq)
S–x x x

Kw x2 10−10 10−10
10–4 = =   (S – x) = = 10–6
Ka S − x S− x 10−4

 S = x + 10–6 {but x = 10–5}  S = (1.1 × 10–5)

Ksp = [Ag+ (aq)] [A–(aq)]  1.1 × 10–5 × 10–6
Ksp = 1.1 × 10–11
7. Fe3+ + 3SCN– ⎯→ Fe(SCN)3
Kf = K1×K2×K2 = 130×16×1 = 2080

Kd = = 4.8×10–4
Kf

8. → Ag + + Br −
AgBr ⎯⎯ x × s = 5 × 10–13

x s

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Ag + + 2NH3 ⎯⎯
→ Ag(NH3 )2+ keq = 1 × 108
s 0.4 0
x 0.4− 2s s

s
= 1108
x(0.4 − 2s)
2
 s 
  = 108 × 5 × 10–13
 0.4 − 2s 
s
= 50 10−3
0.4 − 2s

s = 50 × 10–3 × 0.4= 2.8 × 10–3 M

9. As [H+] increases, solubility of Ag2CO3 increases.
d>c>a>b
DPP-17
[In − ]
1. pH = pKIn + log
[H I n]
2. pH = pKIn ± 1
3. pH range of methyl red
 4.2 – 6.3
4. pH at equivalence point is (5.5 – 11)
5. For HCl Vs NH4OH  pH range (3 – 8.5)
6. Oxalic acid vs KMnO4 titration is a redox titration.
20
9. pHi = pKa + log
80
80
pHƒ = pKa + log
20
pH = 2 log4 = 1.2
11. pKIn = 2
KIn = 10–2
[H + ][In − ] 4 10−3[In − ]
KIn =  10–2 =
[HIn] [HIn]

[In − ] 0
= = 2.5
[HIn] 4
1
% of [HIn] = ×100 = 28.57 %
3.5

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25 1
12. pHi = pKa + log = pKa = log
75 3
5
pHf = pKa + log = pKa + log3
25
pH = 2log3 = 0.96
13. For (b), (c)
PH = pKIn ± 1
pH range of indicator = 2.4 – 4.4

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EXERCISE-II
One More than one correct
2. (A) As, T , Kw and [H+] [OH–] also increase, so neutral pH < 7
If pOH =7, then pH < 7 solution will be acidic.
(B) pH = –log [H+]
(C) HA ⎯→ H+ + A–
C(1–) c c
C 2 1
Ka =  
1−  C
1
(D) TRUE Acidic strength  Ka 
pKa

3. Degree of dissociation of WA & WB will increase.

[H+] in WA and [OH–] in WB will decrease so pH of WA and pOH of WB will increase.

4. 0.1 M HCl + 0.1 M H3PO4 ( << 1)
H3PO4 ⎯→ H+ + H2PO–
0.1(1 – ) 0.1 + 0.1 0.1
 0.1
[H+] = 0.1  pH = 1
0.1 0.1
Ka1 =  = 10 Ka1
0.1
H2PO4– ⎯→ H+ + HPO42–
0.1 0.1 2
0.1 [HPO 24− ]
Ka2 =
0.1
[HPO42–] = K2 = 10 Ka1 Ka2
6. (A) FALSE At half equivalence point pH = pKa
0.1
(B) TRUE pH = 4.74 + log = 5.74
0.01
[C.B.]
(C) TRUE pH = pKa + log
[Acid]
S
(D) FALSE Buffer capacity is max when =1
a

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Kw 10 −14
7. (A) TRUE Kb A– = = −6 = 10–8
KaHA 10

(B) TRUE Salt of SA + WB ( NH4Cl) undergoes cationic hydrolysis.

(C) For CH3COONa(aq)

kw
[OH–] = C  [OH–]  C
Ka

On dilution [OH–], pOH, pH

s.a
(D) Buffer capacity = 2.303
s+a
9. For ppt Qip  Ksp
Ksp of AgCl = 1.8 × 10–10
10 –4 10 –4 1
(A) Qip =  = × 10–8
2 2 4

Qip > ksp (ppt will take place)

10 –5 10 –5 1
(B) Qip =  = × 10–10
2 2 4

Qip < ksp (ppt does not take place)

10 –6 10 –6 1
(C) Qip =  = × 10–12
2 2 4

Qip < ksp (ppt does not take place)

10 –10 10 –10 1
(A) Qip =  = × 10–20
2 2 4
Qip < ksp (ppt does not take place)
10. (A) TRUE Ksp AgCl > Ksp AgBr
So AgBr will ppt first
(B) TRUE For M2x Ksp = 4s3
For Qy2 Ksp = 4s3
For Pz3 Ksp = 27s3
(C) FALSE Li3Na3 (AlF6)2 ⎯→ 3Li+ + 3Na+ + 2AlF63–
3s 3s 2s
Ksp = 2916 ×s8
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11. (A) TRUE due to common – ion effect of Cl–.

(B) TRUE
(C) TRUE Due hydrolysis of CH3COOH solubility increases.
CH3COO– + H2O ⎯→ CH3COOH + OH–
(D) TRUE
COMPREHENSION BASED
13. In original solution

[H+] = Ka  C = 10−6 1 = 10–3M

14. Let resulting solution (After dilution) have concentration Co

CH3COOH ⎯→ CH3COO– + H+
Co 0 0
Co–X X X
pH = 2 × 3 = 6 [H+ ] = x = 10–6

[CH3COO− ][H + ] x.x

Ka = =
[CH3COOH] (Co − x)

(10−6 )2
10–6 =
Co − 10−6
Co = 2 × 10–6 M
Now, for CH3COOH
1 M × 1 litre = 2 × 10–6 M × V
V = 5 × 105 litre.
15. CH3COOH + NaOH ⎯→ CH3COONa + H2O
2 × 10–6 ,V 0.5 × 10–6, V

1.5  10 −6  V 0.5 10−6  V

0
2V 2V
 anion 
pH = pKa + log10  
 acid 
= 6 – log10 3 = 5.523

16. pH at I half equivalence point = p = 12

Ka3

+p
Ka2 K a3
p
pH at I equivalence point = = 10
2
p
Ka 2
=8

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+p
K a1 Ka2
p
pH at II equivalence point = =6
2
p
K a1
=4
At III equivalence point
Na3OP4 + 3HCl ⎯⎯→ 3NaCl + H3PO4
100 300 – –
× × 100 100
100 1
C= = M
400 4

(H + ) 2
Ka1 = 10–4 =  (H+) = ka1C
C
10−2
=
2
= 5 × 10–3
pH = 3 – log 5
17. at II half equivalence point
Na2HPO4 + HCl ⎯⎯→ NaCl + NaH2PO4
100 50 – –
50 × 50 50
50
+ log
K
pH = p = p a2 = 8
Ka 2

50
18. Equilibrium constant = Kw / k a3

7.04
19. Number of moles Cu oxidised = × 10–3
64
= 1.1 × 10–4

20. Cu + 2Ag+ ⎯→ Cu+2 + 2Ag

Since equilibrium constant is very large
[Ag+] = 2.2 × 10–4
21. Ksp = [Ag+]2 [BrO3]
= 4.84 × 10–8
22. Go= 0 + –31.28 + 23.0
= 8.28 kcal/mol

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23. G° = –RT ln Keq

Keq = 10+6
[H + ]2
10+6 = ; [H+] = 0.1  pH = 1 Ans.
10−8
+
24. RNH2 + H+ ⎯⎯→ R N H3
Milli moles 3 1
After reaction 2 – 1
Resultant solution is basic buffer solution
+
[R N H 3 ] 1
pOH = pKb + log ; = 5 + log
[RNH 2 ] 2

MATCH THE COLUMN

27. (A) CH3COOH + NaOH ⎯→ CH3COONa + H2O
10 mmol 2.5 mmol 0 0
7.5 mmol 0 2.5 mmol
2.5
pH = pKa + log = pKa – log 3
7.5
(B) CH3COOH + NaOH ⎯→ CH3COONa + H2O
10 mmol 5 mmol
5 mmol 0 5 mmol
at half equivalence point pH = pKa
(C) CH3COOH + NaOH ⎯→ CH3COONa + H2O
10 mmol 7.5mmol – –
2.5 mmol 0 7.5 mmol
pH = pKa + log 3
(D) It volume of final solution is doubled then conc. will be half.
1 1 1
pH = (pKw + pKa + log )= (pKw + pKa – 2)
2 2 2
28. QSP = [Ag+] [Cr O24− ]

 10−5  
2
−1 3 
(A) QSP =     4 10  < KSP
 4   4 

no ppt
2
 16 3 −1 
  10 
(B) QSP =  3 4  (10–5) < KSP

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no ppt
2
2 3   1
(C) QSP =   10−2   3 10−2   > KSP
3 4   4
ppt
2AgNO3 + K2 CrO4 Ag3 CrO4  + 2KNO3
2 3 — —
1 1
[Cr O24− ] = = × 10–2
400 4

1
−2 
KSP = 4 × 10–12 = [Ag+]2   10 
4 
(D) QSP > KSP  ppt.
2AgNO3 + K2 CrO4 Ag2 CrO4  + 2KNO3
2 — —
× × 1
[Ag+] = 2S = 2 × 10–4
[Cr O24− ] = S = 10–4

29. (A) I + II (salt of WA & WB)

1
pH = (pKw + pKa – pKb) = 5
2
(B) I + III (simply pH of WA)
1
pH = (PKa – logC)
2
= 3.15
(C) I + IV (buffer solution of CH3COOH / CH3COONa)
CH3COOH + NaOH → CH3COONa + H2O
10 5 0 0
5 0 5 5
[Salt]
pH = pKa + log
[Acid]
(D) I + IV (buffer solution of RNH2 / RNH3 Cl)
NaOH + HCl → NaCl + H2O
5 10 0 0
0 5 5 0
RNH2 + HCl → RNH3Cl

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10 5 0
5 0 5
[Salt]
pOH = pKb + log
[Base]
pOH = 9
pH = 5

K a1 [H 2 A − ]O
30. (A) pH = P + log = 4.0
[H 3A]O

Ka2 [HA 2− ]O
(B) pH = P + log = 8.0
[H 2 A − ]O

K a3 [A3− ]O
(C) pH = P + log = 12.0
[HA 2− ]O
1 K a1 1
(D) pH =
K
(P + P a 2 ) = (4 + 8) = 6.0
2 2
1 K K 1
(E) pH = (P a 2 + P a3 ) = (8 + 12) = 10.0
2 2
INTEGER
31. → H + + HS−
H 2S ⎯⎯

0.1–x x +2×10–4 x–y

 2×10–4 x

HS− ⎯⎯
→ H + + S2−

x–y 2×10–4 y
x

−7 2 10−4  x 2 10−4  x
10 = =
0.1 − x 0.1
x = [HS–] = 5 × 10–5 M
2 10−4  y
10–14 =
5 10−5
y = [S2–] = 2.5 × 10–15 M

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32. (a) H3PO4 + NaOH ⎯⎯

→ NaH2PO4 + H2O

6 3 0 (initial mmoles)
3 0 3 (equilibrium mmoles)
pH = pka1 = 3 – log 7.5= 2.12

(b) H3PO4 + NaOH ⎯⎯

→ NaH2PO4 + H2O

6 6 0 (initial mmoles)
0 0 6 (equilibrium mmoles)
pka 2 + pka1 7.2 + 2.12
pH = = = 4.66
2 2
(c) H3PO4 + NaOH ⎯⎯
→ NaH2PO4 + H2O

4.8 7.2 0 (initial mmoles)

0 2.4 4.8 (equilibrium mmoles)
NaHPO4 + NaOH ⎯⎯
→ Na 2HPO4 + H2O

4.8 2.4 0 (initial mmoles)

2.4 0 2.4 (equilibrium mmoles)

pH = pka2 = 7.2
(d) H3PO4 + NaOH ⎯⎯
→ NaH2PO4 + H2O

4 10 0 (initial mmoles)
0 6 4 (equilibrium mmoles)
NaH2 PO4 + NaOH ⎯⎯
→ Na 2 HPO4 + H2O

4 6 0 (initial mmoles)
0 2 4 (equilibrium mmoles)
NaHPO4 + NaOH ⎯⎯
→ Na 3PO4 + H2O

4 2 0 (initial mmoles)
2 0 2 (equilibrium mmoles)

pH = pka3 = 12

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33. pH = pKIn = 7.2

5
pH = 7.2 + log = 7.2 + 0.7 = 7.9
1
for new indicator
7.9 = pKIn + log21  pKIn = 7.3
pH = pKIn = 7.3 (when 50% is ionized)
34. When MnS start to ppt, FeS has already ppt. for ppt of MnS
0.01 × [S2–] = 2.5 × 10–13
[S2–] = 2.5 × 10–11 = 25 × 10–12
[H + ]2  25 10−12
9.6 × 10–21 =
0.1

9.6 9.6
[H+]2 = 10−10  [H+] = 10−5
25 25
pH = 5.21
CuCO3(s) + 4 NH3 → Cu(NH3 )4  (aq) + CO32− (aq)
2+
35.

0.1 x 0 0
0 x–0.4 0.1 0.1

Cu ( NH ) CO
3
2+ 2−
3

= ksp  kf =2.8× 103
 NH  3 4

0.1  0.1
= 2.8  103  x = 0.444 M
( x − 0.4) 4

43. [AgNO3]0 = 0.05 mole / L

[NaBr]0 = 0.005 mole / L
[NaCl]0 = 0.005 mole / L
Assume : AgNO3 + NaBr → AgBr (s) + NaNO3
0.005 0.005 0.005
0.005 moles of solid AgBr in presence of 0.005 moles of [Cl–]
AgBr (s) + Cl– → AgCl(s) + Br–
(5 × 10–3 –x) x

K sp (AgCl)  X 
= (5 × 10–3) =  −3 
K sp (AgCl)  5 10 − x 
x  25 × 10–6 M
= 2.5 × 10–5

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44. At equivalence point [Ag+] = K SP = 10–5

10–10 [CrO 24− ] = 4 × 10–12

[CrO 24− ] = 4 × 10–2 = 0.04 M

0.0055 1000
45. Solubility, s =  = 1 × 10–4 M
550 100
ksp of Ca [CH3 (CH2)14 COO]2 = 4S3 = 4 × 10–12 M

40 (10 )
3

Now, [Ca2+]present initially = 6 = 10–3 M

10 40
k sp 4 10−1
and [Ca2+]remained = = = 4 × 10–10 M
CH3 ( CH2 )14 COO  ( 0.1)
− 2 2

 [Ca2+]remained = 10–3 – 4 × 10–10  10–3 M

Hence, mass of calcium palmitate precipitated = 10–3 × 10 × 550 gm = 5.5 gm = 5500 mg. Ans.

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EXERCISE # JEE-MAIN
1. Ksp = 4s3= 4 × (1.0 × 0–5)3= 4 × 10–15
2. Ksp = 4s3
= 4x3
3. MX4 ⎯→ M4+ + 4X–
s 4s
Ksp = s × (4s)4
= 256 s5
1/5
 Ksp 
s=  
 256 

4. H2PO4– ⎯→ H+ + HPO42–
Acid C.B.

5. pH = 5.4
[H+] = 10–5.4 = 100.6 × 10–6= 4 × 10–6

6. MX2 ⎯→ M2+ + 2x–

s 2s
Ksp = 4s3 = 4 × 10–12
s = 10–3 M
[M2+] = 10–3 M

7. OH– ⎯→ H+ + O2–
Acid C.B.
8. H2A ⎯→ H+ + HA– Ka1
HA– ⎯→ H+ + A2– Ka2
––––––––––––––––
H2A ⎯→ 2H+ + A2– Koverall = Ka1 × Ka2

[A − ]
9. pH = pKa + log
[HA]
pH = pKa= 4.5(if acid is half ionize)
pOH = 9.5
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10. Ksp = s2 = 1.0 × 10–8

s = 0–4 M
= 10–6 × 283 g/L
= 283 × 10–5 g/100 mL
= 2.83 × 10–3 g/100 mL

1 1
11. pH = (pKw + pKa – pKb) = (14 + 4.8 – 4.78)
2 2
1
= × 14.02 = 7.01
2

12. For pptn to start

Ksp = Qip
[Ba2+] × 10–4 = 5.1 × 10–9
[Ba2+] = 5.1 × 10–5 M

13. For pptn to start

Ksp = Qip
0.05 × [Br] = 5 × 10–13
[Br–] = 10–11 M
moles of Br– = 1 × 10–11
mass of KBr = 1 × 10–11 × 120 = 1.2 × 10–9 g

14. K1 >> K2
H2CO3 ⎯→ H+ + HCO3–
c–x x x–y
» x
HCO3– ⎯→ H+ + CO32–
x–y x+y y
» x » x
[H+] » [HCO3–] = 1.2 × 0–6 M
[CO32–] = Ka2 = 4.8 × 10–11 M

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15. Ksp = Qip

10–3 × [OH–]2 = 1.1 × 10–11
[OH–]min = 10–4
pOH = 4  pH = 10

16. In reaction (ii) H2PO42– given H+ ion.

17. Ksp = 27s3
27s3 = 1.6 × 10–30
1/3
 1.6 10−30 
s=  
 27 

18. HA H+ + A– pH = 5
1–x x x [H+] = 10–5
10 −5  10 −5
Ka = = 10–10
1

19. If Ksp < Qip

Ksp = 1.7 × 10–10
For option (4)
Qip = 1 × 10–2 × (1 × 10–3)2 = 10–8

20. HQ ⎯→ H+ + Q– pH = 3
0.1 – x x x [H+] = 10–3
10 −3  10 −3
Ka = = 10–5
0.1

21. For pptn to start

Ksp = Qip
5.1 × 10–9 = [Ba2+] × [CO32–]
[Ba2+] × 10–4 = 5.1 × 10–9
[Ba2+] = 5.1 × 10–5 M

22. [OH–] = 5 × 10–2

pOH = 2 – log5
Þ pH = 12 + log5 = 12.7
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23. Hg2Cl2 ⎯→ Hg22+ + 2Cl–

s 2s
1/3
 Ksp 
Ksp = 4s3 Þ s=  
 4 
Cr2(SO4)3 ⎯→ 2Cr3+ + 3SO42–
2s 3s
1/5
 Ksp 
Ksp = 108s5 Þ s=  
 108 
For BaSO4 Ksp = s2 Þ s = (Ksp)1/2
1/4
 Ksp 
For CrCl3 Ksp = 27s4 Þ s=  
 27 

5
24. Moles of CH3COOH = = 0.083
60
7.5
Moles of CH3COONa = = 0.091
62
0.091
pH = 4.76 + log
0.083
pH > 4.76
Range of pH Þ pKa ± 1

25. pHi = 1 [H+]i = 0.1

pHƒ = 2[H+]ƒ = 0.01
MiVi = MƒVƒ
0.1 × 1 = 0.01 × Vƒ  Vƒ = 10 L
water should be added = 9L

26. Refer notes.

27. Zr3(PO4)4 ⎯→ 3Zr+4 + 4PO43–

3s 4s
Ksp = (3s)3 × (4s)4 = 6912 s7

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1/7
 Kps 
s=  
 6912 

1
28. pH = (pKw + pKa – pKb)
2
1
= (14 + 3.2 – 3.4)
2
1
= ×13.8 = 6.9
2

29. pH range of methyl orange = 3.1 – 4.4

in titration of W.A. Vs SA at end point pH should be less than 7.
30. pptn to start
Ksp = Qip
[Ba2+]ƒ [SO42–]ƒ = Ksp BaSO4
50 1 Mi  450
 = 1×10–10
500 500
Mi = 1.1 × 10–9 M

31. H2S H+ + HS– Ka1 = 1.0 × 10–7

HS– H+ + S2– Ka2 = 1.2 × 10–13

–––––––––––––––––––

H2S 2H+ + S2– Ka = 1.2 × 10–20

[H + ]2  [S2− ]
1.2 × 10–20 =
[H 2S]

(0.2) 2  [S2− ]
1.2 × 10–20 =
0.1
[S2–] = 3 × 10–20 M
32. CH3COOK is salt of WA + S.B.
So pH > 7

33. Ksp PbCl2 = 3.2 × 10–8 = 4s3

s = 2 × 10–3 M = 0.414 g/L

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0.1
Vol. of water require to dissolve 1g of PbCl2= = 0.241 L
0.414

34. (i) M Mol of H+ = 15

M Mol of OH– = 5
10
[H+]ƒ = = 0.1  pH = 1
100

35. 2NH4OH + H2SO4 ⎯→ (NH4)2SO4 + H2O

6 2 0 –
2 0 2 –
[NH +4 ] 4
pOH = pKb + log = 4.7 + log = 4.7 + log2
[NH 4 OH] 2

pH = 9.3 – log2 = 9

36. Ca(OH)2 + Na2SO4 ⎯→ CaSO4 + 2NaOH

0.1 m mole 0.014 m mole 0 0
0.086 m mole 0 0.014 m mol 0.014 m mole
Mass of CaSO4 = 0.014 × 136 = 1.90 g
0.014
[OH–] = = 0.28 M
0.2

37. Ag2CO3 2Ag+ + CO32–

s1 2s1 + 0.1 s1
» 0.1
8 × 10–12 = (0.1)2 × s1
s1 = 8 × 10–10 M

38. Zr3(PO4)4 ⎯→ 3Zr4+ + 4PO43–

s 3s 4s
Ksp = 6912 s7

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1/7
 Ksp 
s=  
 6912 

39. Initial pH > 7 ,at equivalence point pH = 7

400  0.1 2 − 400  0.1
40. (a) [H+] = = 0.05 M
800
pH = 1.3
(b) Kw = [H+] [OH–]
T, Kw
(c) HA ⎯→ H+ + A–
c(1 – a) ca ca
c 2 2 1
Ka = Þ 10–5 = 10–5 × Þ =
1−  1−  2

(d) Le-Chatelier principle is applicable to common ion effect.

1 1
41. pH = (pKw – pKb – logc) = (14 – 5 – log2 × 10–2) = 5.35
2 2

42. Al(OH)3 ⎯→ Al3+ + 3OH–

s 3s + 0.2
» 0.2
(0.2)3 × s = 2.4 × 10–24  s = 3 × 10–22 M

43. Ksp = 4s3 = 4 × (1.84 × 10–5)3

Cd(OH)2 Cd2+ + 2OH–

s 28 + 0.01
» 0.01
s × (0.01)2 = 4 × (1.84 × 10–5)3
s = 2.49 × 10–10 M

44. pH of 0.01 M HCl = 2

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pH of 0.01 M NaOH = 12
pH of 0.01 M CH3COONa > 7
pH of 0.01 M NaCl = 7
order of pOH : A > D > C > B
45. Acidic buffer solution contains weak acid and its salt with strong base.
Option (A) : Solution is containing strong acid and its salt with strong base.
0.1100mm 0.1200mm
Option (B) : HCl(aq) + CH 3COONa (aq) ⎯⎯
→ CH 3COOH (aq) + NaCl(aq)
0 10mm 10mm

Resulting solution contains weak acid and its salt with strong base.
0.1100mm 0.1100mm
Option (C) : CH 3COOH (aq) + NaOH (aq) ⎯⎯
→ CH 3COONa (aq) + H 2O(l )
0 0 10mm

Resulting solution contains only salt of weak acid and strong base.

46. Titration curve for strong acid and weak base initially a buffer of weak base and conjugate acid
is:

Formed, thus pH falls slowly and after equivalence point, so the pH falls sharply so methyl
arrange,
having pH range of 3.2 to 4.4 will weak as indicator. So statement-I is correct.

Titration curve for weak acid and strong base (NaOH) Initially weak acid will form a buffer so
pH
increases slowly but after equivalence point. It rises sharply covering range of phenolphthalein
so it will
be suitable indicator so statement-II is false.

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50. Let moles added = a

+ +
Ag (aq) + 2NH3(aq) Ag(NH3 )2(aq.)

a
t=0 0.8  
2
a 
t= 5×10–8  − 1.6  0.8
2 

0.8
2
= 108
a 
(5 10−8 )  − 1.6 
 2 
a
 − 1.6 = 0.4  a = 4
2

51. Ka of Butyric acid  2×10–5 pKa = 4.7

pH of 0.2 M solution
1 1
pH = pK a − log C
2 2
1 1
= (4.7) log(0.2)
2 2
= 2.35 + 0.35 = 2.7
pH= 27 × 10–1

52. HCl + H2SO4

(0.01 200) + (0.01 2  400)
 H+  =
600
2 + 8 10 1
= = =
600 600 60
1
pH = − log  
 60 
= 1.78

53. pOH = 14 – 8.26

[NH +4 ]
= pKb + log
[NH 3 ]

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[NH +4 ]
= 5.74 = 4.74 + log  [NH +4 ] = 2
0.2
Hence, NH4Cl = 2 × 53.5 = 107 g

54.

(QUINONOID FORM)

55. In deionized water no common ion effect will take place so maximum solubility
56. Buffer of HOAc and NaOAc
0.1
pH = pKa+ log 0.01
5 = pKa + 1
pKa = 4
Ka = 10–4
x = 10
57. In resultant solution
nNH3 = 0.1 − 0.02 = 0.08
nNH4Cl = nNH+4 = 0.1 + 0.02 = 0.12
[NH+
4]
pOH = pK b + log NH3
0.12
= 4.745 + log 0.08
3
= 4.745 + log 2

= 4.745 + 0.477 – 0.301

pOH = 4.921
pH = 14 – pH
= 9.079

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58. Total milimoles of H+ = (600 × 0.01) + (400 × 0.01 × 2)

=14
14
[H + ] = = 14 × 10−3
1000

pH = 3 – log 14
= 1.86
= 186 × 10–2
59. AgCl(s) → Ag+(aq.) + Cl¯(aq.)
S S
1.43 2
K sp = S 2 = (143.4 × 10−3 ) = 10−10

–log Ksp = 10

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EXERCISE # JEE-ADVANCED

1. HCl + NaOH ⎯→ NaCl + H2O

2m mol 3mmol 10 -
0 1mmol 2m mol -
1
[OH–] = = 2×10–3
500
pH = 11 + log2 = 11.3

2. pH = 8  pOH = 6
[OH–] = 10–6 M
Pb(OH)2 ⎯→ Pb2+ + 2OH–
Ksp = 4s2 = 4×(6.7)3×10–18 = 1.2×10–15
Pb(OH)2 ⎯→ Pb2+ + OH–
s 2s+10–6
s(2s + 10–6) = 1.2×10–15
s×10–2 = 1.2×10–15
s = 1.2×10–3 M

4. HCl  pH < 7 NaCl  pH = 7

NaCN  pH > 7 NH4Cl  pH < 7
NaCN < NaCl > NH4Cl > HCl

10
5. Amount of SO2 in atmosphere = = 10×10–6
106
Molar conc. of SO2 in water = Amount of SO2 × Solubility of SO2
= 10×10–6×1.3653
= 1.3653×10–5 M
H2SO3 ⎯→ H+ + HSO3−

1.3653×10–5 – x x x
x2
Ka = = 10–1.92
1.3653 10 −5 − x
x = 1.364×10–5 pH = 4.865

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6. Equation of H2C2O4.2H2O = Equation of NaOH

10 63
  2 = 0.1×V(L)
250 126
1
V(L) =
25
V(mL) = 40

7. ApBq(s) ⎯→ pAq+(aq) + qBp–(aq)

s ps qs
Ksp = (ps)p(qs)q
= ppqq(s)p+q

8. [CH3COOH]f = 0.1 M
[HCl]f = 0.1 M
(a) CH3COOH ⎯→ CH3COO– + H+
0.1–x x x+0.1
x(x + 0.1)
1.75×10–5 =
0.1 − x
x = 1.75×10–5
0.1× = 1.75×10–5
a = 1.75×10–4
[H+] = 0.1  pH = 1

6
(b) Moles of NaOH = = 0.15 mol
40
CH3COOH + NaOH ⎯→ CH3COONa + H2O
ni 0.1 0.05 0 -
nf 0.05 0 0.05 -
0.1 moles NaOH will be consumed by 0.1 mol of HCl
pH = pKa = 4.75

9. T increases , Kw increases , H+, pH ¯

10. Which has minimum value of Ksp i.e. HgS

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11. X– + H2O ⎯→ 4X + OH–

0.1(1–h) 0.1 h 0.1 h
Kw 10−14
Kh = = −5 = 10–9
K a (HX) 10

Ch 2 0.1h 2
Kh = = = 10–9
1− h 1− h
0.1 h2 = 10–9
h2 = 10–8
h = 10–4
% h = 0.01 %

12. At end point HA will completes reacts with NaOH

HA + NaOH ⎯→ NaOH + H2O
[A–] = 0.05 M
1
pH = (pKw + pKa + logC)
2
1
= (14 + 6 – log5 + log0.05)
2
1
= (20 – log5 – log20)
2
 pH = 9

13. CH3NH2 + HCl ⎯→ CH3 NH3+ Cl−

0.1 mol 0.08 mol 0

0.02 mol 0 0.05 mol
[CH 3 NH 2 ]
[OH–] = Kb×
[CH 3 NH 3+ ]

0.02 5
= 5×10–4 × = ×10–4
0.08 4
Kw 
[H+] = −
= ×10–10 = 8×10–11 M
[OH ] 5

14. CO2 + H2O ⎯→ HCO3− + H+

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HCO3− ⎯→ CO32− + H+

15. For MX
Ksp = s2 = 4×10–8
s = 2×10–4 M
For MX2
Ksp = 4s2 = 32×10–14
s2 = 8×10–15
s = 2×10–5 M
For M3X
Ksp = 27s4 = 2.7×10–15
s = 10–14 M
MX > M3X > MX2
16. BOH + HCl ⎯→ BCl + H2O
It equivalence point
Moles of BOH = moles of HCl
2 2
2.5× = ×V(mL)
5 15
V(mL) = 7.5 mL
Vf = 10 mL
1
[BCl] = = 0.1 M
10
+
B+ + H2O ⎯→ BOH+ H
0.1(1− h) 0.1− h 0.1− h

K w 10−14
Kh = = = 10–2
K b 10−12

0.1 − h 2
10–2 =
1− h
h = 0.27
Þ [H+] = 0.1×h = 0.027 M

1
17. pH = (pKw + pKa + logC)
2
1 1
= (14 + 4 + log0.01) = ×16 = 8
2 2

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18. (A) HNO3 + CH3COOH (S.A. + W.A.)

It can’t be a buffer
(B) KOH + CH3COONa (S.B. + Salt)
It can’t be a buffer
(C) CH3COONa + HNO3 ⎯→ CH3COOH + NaNO3
It can form buffer if volume of CH3COONa and HNO3 is different.
(D) CH3COOH + CH3COONa
It is a buffer

19. For CuCl

Ksp = s2 = 10–6
s = 10–3
AgCl(s) ⎯→ As+(aq) + Cl– (aq)
s s+10–3
s(s + 10–3) = 1.6×10–10
s×10–3 = 1.6×10–10
s = 1.6×10–7

20. For Ag2CrO4 Ksp = 1.1×10–12

Ag2CrO4 ⎯→ 2Ag+ (aq) + CrO24−

2s+0.1 s
» 0.1
(0.1)2 ×s = 1.1×10–12
8 = 1.1×10–10 M

21. r  [H+]1

Ka  C 1
=
1 100
K a  C = 10–2

Ka = 10–4

22. From exp.-1

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5.7×1000 = C×5.7
From exp-2
q = C×5.6
q = 5.65 kJ
5.6
H = − = –56 kJ. / mol
0.1
Hion = –56 + 57= 1 kJ/ mol

23. CH3COOH + NaOH ⎯→ CH3COONa + H2O

0.2 mol 0.1 mol 0 0
0.1 mol 0 0.1 mol 0
pH – pKa = 4.7

 H+ 
24. s= Ksp  + 1
 Ka 

−10  10−3 
= 20  10  −8 + 1 
 10 

= 2 10−5 = 4.47×10–3 M

25. (P) CH3COOH + NaOH ⎯→ CH3COONa + H2O

2m mol 1m mol 0 -
1m mol 0 1m mol -
If forms a buffer and pH does not change with dilution.
(Q) CH3COOH + NaOH ⎯→ CH3COONa + H2O
2m mol 2m mol 0 -
0 0 2m mol -
CH3COO– + H2O ⎯→ CH3COOH + OH–

K w  Ka
CH+ =
C
1
[H+] 
C
(R) NH3 + HCl ⎯→ NH4Cl
2m mol 2m mol 0

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0 0 2m mol
NH+4 + H2O ⎯→ NH4OH + H+

Kw
[H+] = C Þ [H+]  C
Kb

(S) Ni(OH)2(s) ⎯→ Ni2+(aq) + 2OH–(aq)

On dilution [OH–] remains same in saturated solution of Ni(OH)2

26. B + HA ⟶ BH ⊕ + A−
0.1M 0.1M
0mL pH = 13
3 mL → 50% Neutralization pH = 11
6 mL → equivalence point pH = 3 to 9
Equivalence point
B + HA ⟶ BH + + A−
0.1 × 6 0.1 × 6
= 0.6 m mol = 0.6 m mol
0 0 0.6 m mol
Total volume = 12ml
0.6
Concentration of Salt =
12
k 10−14 ×0.6
pH = 6 = √ kw × c = √ {pH = 0.6, [H + ] = 10−6 }.
b kb ×12

K w 0.1 × 6
⇒ [H + ] = 10−6 = √ ×
Kb 12

−12
10−14 × 10−1 1
10 = ×
Kb 2
k b = 5 × 10−4
pk b = −log k b = −log (5 × 10−4 ) = −log 5 + 4log 10
pk b = 4 − 0.7
pk b = 3.3
27. [Zn+2 ][S 2− ] ≤ K sp (ZnS)

5 10−22
[S 2− ] ≤ ×
4 0.05

H2 S ⇔ 2H + s 2−+

Knet ×[H2 S]
[S 2− ] = [H+ ]2

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Knet ×[H2 S] 5 10−22

[H+ ]2
≤ 4 × 10−2 ×5
10−21 ×10−1 ×4
[H + ]2 ≥
10−20

[H + ] ≥ 2 × 10−1 = 0.2
Alternate:
[Zn+2 ][S 2− ] ≤ K sp
5 10−22 1
[S 2− ] ≤
× = × 10−20
4 0.05 4
H2 S ⇔ 2H + + S 2−
K1 K2 ×[H2 S] 10−21 ×0.1
[H + ]2 = =
[S2− ] [ S2− ]

10−22 1
[S 2− ] = ≤ 4 × 10−20
[H+ ]2

[H + ] ≥ 0.2
28. First acid base reaction between H2 CO3 and NaOH takes place.
In the final solution, we have 0.01 mole Na2 CO3 and 0.02 moles of NaHCO3 .
Here, we have a buffer of NaHCO3 and Na2 CO3 .
[ Salt ]
∴ pH = pK a2 + log
∣ Acid ]
0.01
( 0.1 )
= 10.32 + log
0.02
( 0.1 )

1
= 10.32 + log
2
= 10.32 − log 2
= 10.32 − 0.3
= 10.02
∴ pH = 10.02
+
29. H2 SO4 ⟶ HM 4 (K a1 is very large )
+ HSO2−
1M
1M4
HSO4 ⇌ H + SO2−
− +
4 K a2 = 1.2 × 10−2
[SO24 2 ] coming from Na2 SO4 = 1.8 × 10−2

[SO24 ][H + ] 1.8 × 102 × 1

= > K a2
[HSO4 ] 1

∴ Rather than dissociation of HSO4 − into H + andS O4 2− ions, association between already
present H + and SO4 2− will take place.

∴ [SO2−
4 ] = 1.8 × 10
−2
−x

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[H + ] = 1 − x ≈ 1
} ( assuming x << 1)
[HSO− 4] = 1 + x ≈ 1

(1.8 × 102 − x)1

= 1.2 × 10−2
1

⇒ x = 0.6 × 10−2

[SO2− −2
4 ] = 1.2 × 10 M

PbSO4 (s) ⇌ Pb2+ (aq) + SO2−

4 (aq)

If solubility of PbSO4 = sM

∴ [Pb2+ ] = s

[SO24 ] = s + 1.2 × 10−2 ≈ 1.2 × 10−2

(assuming s ≪ 1.2 × 10−2 )

∴ s × 1.2 × 10−2 = 1.6 × 10−8

1.6
s= × 10−6 = 1.33 × 10−6
1.2

On comparing with X × 10−Y

Y=6
30. MX ⇌ M ⊕ + X ⊖
X ⊖ + H ⊕ ⇌ HX
H⊕
S = √K sp (+ K )
a

10−7
10−4 = √K sp (1 + )
Ka

10−2
10−3 = √K sp (1 + )
Ka

Squaring Equation [(1)/(2)] gives

10−7
(1 + )
Ka
10−2 =
10−2
(1 + )
Ka

−2
10−4 10−7
10 + =1+
Ka Ka
10−4 − 10−7
= 0.99
Ka

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10−4
= 0.99
Ka
10−4 1
Ka = = × 10−2
0.99 99
K a = 2 + log 99 = 4

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