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Ionic Equilibrium

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Ionic Equilibrium
EXERCISE 1 JEE MAIN/BOARDS
Q.1 The degree of dissociation of acetic acid in
a 0. 1 N solution is 1. 32 × 10–2. At what
concentration of nitrous acid, its degree of
dissociation will be same as that of acetic acid?
Ka (HNO2) = 4 × 10–4
Q.2 How many times is the H+ concentration in
the blood (pH = 7. 36) greater than in the spinal
fluid (pH = 7. 53)?
Q.3 A 0. 400 M formic acid solution freezes at
– 0. 758°C. Calculate the Ka of the acid at that
temperature. (Assume molarity equal to
molality). Kf (H2O) is 1. 86°mol–1 kg.
Q.4 A sample of AgCl was treated with 5 mL
of 1. 5 M Na2CO3 solution to give Ag2CO3 the
remaining solution contained 0. 00266625
g/litre Cl– ion. Calculate the solubility of AgCl in
(a) 0. 1 M AgNO3
(b) 0. 1 M BaCl2
(c) 0. 2 M NaNO3.
Given that solubility of Ag2CO3 in 500mLH2O
=13. 8 mg.
Q.5 100 mL of solution S1 contains 0. 17 mg of
AgNO3. Another 200 mL solution S2 contains 0.
117 mg of NaCl. On mixing these two solutions
predict whether the precipitate of AgCl will
appear or not Ksp AgCl = 10–10 M2
Q.6 An indicator is a weak acid and the pH
range of its colour is 3. 1 to 4. 5. If the neutral
point of the indicator lies in the centre of the
hydrogen ion concentrations corresponding to
given pH range, calculate the ionization
constant of the indicator.
Q.7 Calculate the hydrolysis constant of NH4Cl
; determine the degree of hydrolysis of this salt
in 0. 01 M solution and the pH of the solution.
Kb (NH4OH)= 1. 8 × 10–5
Q.8 Calculate the pH of 0. 1 M acetic acid
solution if its dissociation constant is 1. 8 × 10–
5
. If 1 litre of this solution is mixed with 0. 05
mole of HCl, what will be the pH of the mixture
Q.9 What is the solubility product of Ag2CrO4 if
0. 0166 g of the salt dissolves in 500 ml of water
at 18°C?
Q.10 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.
Q.11 A chemist needs a buffer with pH 4. 35.
How many milliliters of pure acetic acid (density
= 1. 049 g/mL) must be added to 465 mL of 0.
0941 M NaOH solution to obtain such buffer?
(Ka = 1. 8 × 10–5)
Q.12 It is found that 0. 1 M solution of three
sodium salts NaX, NaY and NaZ have pHs 7. 0,
9. 0 and 11. 0, respectively. Arrange the acids
HX, HY and HZ in order of increasing strength.
Where possible, calculate the ionisation
constants of the acids.
Q.13 Given a solution that is 0. 5 M CH3COOH.
To what volume at 25°C must one dm3 of this
solution be diluted in order to (a) double the
pH; (b) double the hydroxide-ion
concentration.
Given that Ka = 1. 8 × 10–5M.
Q.14 The solubility of Mg(OH)2 is increased by
addition of NH4 ion. Calculate –
(a) Kc for the reaction,
Mg(OH)2 +2 NH4 ⇌2NH3+2H2O + Mg2+
(b) Find solubility of Mg(OH)2 in a solution
containing 0. 5 M NH4Cl before addition of
Mg(OH)2 (Ksp of Mg(OH)2= 1 × 10–11, Kb for
NH4OH = 1. 8 × 10–5)
Q.15 A buffer solution was prepared by
dissolving 0. 05 mol formic acid and 0. 06 mol
sodium formate in enough water to make 1. 0
L of solu-tion. Ka for formic acid is 1. 80 × 10–4.
(a) Calculate the pH of the solution.
(b) If this solution were diluted to 10 times its
volume, what would be the pH?
(c) If the solution in (b) were diluted to 10 times
its volume, what would be the pH?
Q.16 An unknown volume and unknown
concentration of weak acid HX is titrated with
NaOH of unknown concentration. After
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Ionic Equilibrium
addition of 10. 0 cm3 of NaOH solution, pH of
solution is 5. 8 and after the addition of 20. 0
cm3 of NaOH solution, the pH is 6. 4. Calculate
the pH of aqueous solution of 0. 1 M NaX.
Q.17 A solution containing zinc and
manganese ions each at a concentration of 0.
01 mol dm3 is saturated with H S2 . Calculate
(i)pH at which the MnS will form a precipitate
(ii) conc, of Zn+2 ions remaining.
Given: [H2S] = 0. 1 mol/lit,
K sp(ZnS) = 1 ×10–22mol2 lit–2,
Ksp (MnS) = 5. 6 × 10–16mol2 lit–2 .
K1 and K2 for H2S are 1 × 10–7
and 1. 1 × 10–14
Q.18 For the indicator thymol blue, the value of
pH is 2. 0, when half of the indicator is present
in an unionized form. Calculate the percentage
of the indicator in the unionized form in a
solution of 4. 0 × 10–3 mol/dm3 hydrogen ion
concentration.
Q.19 One of the substances sometimes
responsible for the hardness of water is CaSO4.
A particular water sample has 131 ppm CaSO
(4131 g CaSO4 per 106 g of water). If this water
boiled in a tea kettle, approximately what
fraction of water must be evaporated before
CaSO4(s) begins to deposit? Assume that
solubility of CaSO4 does not change with
temperature in the ange 0 to 100°C, Ksp (CaSO4)
= 9. 1 × 10–6 .
Q.20 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.
Q.21 The first ionization constant of H2S is 9.
1×10–8. Calculate the concentration of HS– ion
in its 0. 1 M solution. How will this
concentration be affected if the solution is 0. 1
M in HCl also? If the second dissociation
constant of H2S is 1. 2 × 10–13. Calculate the
concentration of S2– under both conditions.
Q.22 The ionization constant of acetic acid is 1.
74 × 10–5. Calculate the degree of dissociation
of acetic acid in its 0. 05 M solution. Calculate
the concentration of acetate ion in the solution
and its pH.
Q.23 It has been found that the pH of a 0. 01
M solution of an organic acid is 4. 15. Calculate
the concentration of the anion, the ionization
constant of the acid and its pKa
Q.24 Assuming complete dissociation,
calculate the pH of the following solutions:
(a) 0. 003 M (b) 0. 005 M NaOH
(c) 0. 002 M HBr (d) 0. 002 M KOH
Q.25 Calculate the pH of the following
solutions:
(a)2 g of TlOH dissolved in water to give 500 ml
of solution.
(b)0. 3 g of Ca (OH)2 dissolved in water to give
2 litre of solution
(c)0. 3 g of NaOH dissolved in water to give 200
mLof solution.
(d)1 mL of 13. 6 M HCl is diluted with water to
give 1 litre of solution
Q.26 If the solubility product of silver oxalate is
1 × 10–11, what will be the weight of Ag2C2O4 in
2. 5 litres of a saturated solution?
Q.27 Calculate the hydrolysis constant of KF.
Determine the degree of hydrolysis of salt in a
0. 01 M solution and the pH of the solution.
Ka(HF) = 6. 6 × 10–4.
Q.28 Assuming that the buffer in blood is
CO3  HCO3 , calculate the ratio of conjugate
base to acid necessary to maintain blood at its
proper pH, 7. 4 K1 (H2CO3)= 4. 5 × 10–7.
Q.29 How does the solubility of CaC2O4 in a 0.
1 M solution of ( NH4)2C2O4 decrease in
comparison with its solubility in water? Assume
that the ionisation of (NH4)2C2O4 is complete.
[Ksp (CaC2O4) = 2 × 10–9]
Q.30 How many moles of sodium hydroxide
can be added to 1. 0 L of a solution 0. 10 M in
NH3 and 0. 10 M in NH4Cl without changing the
pOH by more than 1 unit. Assume no change
in volume. Kb= 1. 8 × 10–
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Ionic Equilibrium

EXERCISE 2 JEE MAIN

Q.1 The conjugate acid of NH2– is Q.9 Which of the following solution will have
(A) NH3 (B) NH2OH pH close to 1. 0?
 (A)100 ml of M/100 HCl + 100 ml of M/10
(C) NH4 (D) N2H4
(B)55 ml of M/10 HCl + 45 ml of M/10 NaOH
Q.2 Out of the following, amphiprotic species (C)10 ml of M/10 HCl + 90 ml of m/10 NaOH
(D)75ml of M/5 HCl + 25ml of M/5 NaOH
are
I HP O32 II OH– Q.10 What is the percentage hydrolysis of
III H2P O 4 IV HC O3 NaCN in N/80 solution when the dissociation
(A) I, III, IV (B) I and III constant for HCN is 1. 3 × 10–9 and Kw = 1. 0 ×
(C) III and IV (D) All 10–14
(A) 2. 48 (B) 5. 26
Q.3 pH of an aqueous solution of NaCl at 85°C (C) 8. 2 (D) 9. 6
should be
(A) 7 (B) > 7 Q.11 The compound whose 0. 1 M solution is
(C) < 7 (D) 0 basic is
(A) Ammonium acetate
Q.4 1 cc of 0. 1 N HCl is added to 99 cc solution (B) Ammonium chloride
of NaCl. The pH of the resulting solution will be (C) Ammonium sulphate
(A) 7 (B) 3 (D) Sodium acetate
(C) 4 (D) 1
Q.12 The pH of the neutralisation point of 0.
M 1 N ammonium hydroxide with 0. 1 N HCl is
Q.5 10 ml of H2SO4 is mixed with 40 ml of
200 (A) 1 (B) 6
M (C) 7 (D) 9
H2SO4. The pH of the resulting solution is
200
Q.13 If equilibrium constant of
(A) 1 (B) 2
CH3COOH + H2O  CH3COO– + H3O+
(C) 2. 3 (D) none of these
Is 1. 8 × 10–5, equilibrium constant for
Q.6 If pKb for fluoride ion at 25° C is 10. 83, the CH3COOH + OH–⟶ CH3COO– + H2O is
ionisation constant of hydrofluoric acid in (A) 1. 8 × 10–9 (B) 1. 8 × 10–9
water at this temperature is: (C) 5. 55 – l0–9 (D) 5. 55 × 1010
(A) 1. 74 × 10–5 (B) 3. 52 × 10–3
Q.14 The pKa of a weak acid, HA, is 4. 80. The
(C) 6. 75 × 10–4 (D) 5. 38 × 10–2
pKb of a weak base, BOH, is 4. 78. The pH of an
Q.7 The pH of an aqueous solution of 1. 0 M aqueous solution of the corresponding salt, BA,
solution of a weak monoprotic acid which is 1% will be:
ionised is (A) 8.58 (B) 4.79
(A) 1 (B) 2 (C) 7.01 (D) 9.22
(C) 3 (D) 11
Q.15 The range of most suitable indicator
Q.8 If K1 & K2 be first and second ionization which should be used for titration of X– Na+ (0.
constant of H3PO4 and 1 M, 10 ml) with 0. 1 M HCl should be
K1> > K2 which is incorrect. 6
(Given: Kb(X  )  10 )
(A) [H+] = [H2 PO 4 ]
(A) 2-3 (B) 3-5
(B) [H+] = K1 [H3PO4 ]
(C) 6-8 (D) 8-10
(C) K2 = [H PO 4 ]
(D) [H+] = 3[ PO34 ] Q.16 The solubility of A2X3 is y mol dm–3. Its
solubility product is
(A) 6y2 (B) 64y4
(C) 36y5 (D) 108y5

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Ionic Equilibrium
2

Q.17 If Ksp for HgSO4 is 6. 4 × 10–5, then Keq = [M ][H

 2
2S]
[H ]
solubility of this substance in mole per m3 is
The value of keq is given for few metal sulphide.
(A) 8 – 10–3 (B) 6. 4 × 10–5
If conc, of each metal ion in solution is 0. 01 M,
(C) 8 × 10–6 (D)None of these
which metal sulphides are selectively ppt at
Q.18 The solubility of a sparingly soluble salt total [H+]= 1M in saturated H2S solution.
AB2 in water is 1. 0 × 10–5 mol L–1. Its solubility Metal sulphides
2
product is: Keq = [M ][H
 2
2S]

(A) 10 –15 (B) 10 –10 [H ]

(C) 4 × 10 –15
(D) 4 × 10 –10 Mns ZnS CoS PbS
3  1010 3  10 2 3 3  10 7
Q.19 Which of the following is most soluble in
(A) MnS, ZnS, CoS (B) PbS, ZnS, CoS
water?
(C) PbS, ZnS (D) PbS
(A) MnS (Ksp = 8 × 10 –37)
(B) ZnS(Ksp =7 × 10 –16) Q.25 Solid Ba(NO3)2 is gradually dissolved in a
(C) Bi2S3 (Ksp =1 × 10 –72) 1. 0 × 10–4 M Na2CO3 solution. At what
(D) Ag3(PO4) (Ksp =1. 8 × 10 –18) concentration of Ba2+ will a precipitate begin to
form? (Ksp for BaCO3, = 5. 1 × 10–9)
Q.20 When equal volumes of the following
(A) 4. 1 × 10–5M (B) 5. 1 × 10–5M
solutions are mixed, precipitation of AgCl (Ksp
(C) 8. 1 × 10–8M (D) 8. 1 × 10–7M
=1. 8 × 10 –10) will occur only with:
(A) 10–4M (Ag+) and 10–4 M (Cl–) Q.26 Ksp of MX4 and solubility of MX4 is S
(B) 10–5M (Ag+) and 10–5 M (Cl–) mol/litre is related by:
(C) 10–6M (Ag+) and 10–6 M (Cl–) (A) S = [KSP/256]1/5
(D) 10–10M (Ag+) and 10–10 M (Cl–) (B) S = [128/KSP]1/4
(C) S = [256KSP]1/5
Q.21 The precipitate of CaF2
(D) S = [KSP/128]1/4
(Ksp = 1. 7 × 10–10) is obtained when equal
volumes of the following are mixed Q.27 Which of the following statement(s) is/are
(A) 10–4 M Ca3++ 10–4 M F– correct?
(B) 10–2 M Ca2++ 10–3 M F– (A) the pH of 1. 0 × 10–8 M solution of HCl is 8
(C) 10–5 M Ca2++ 10–3 M F– (B) the conjugate base of H2 PO 4 is HPO24
(D) 10–3 M Ca2++ 10–5 M F– (C)autoprotolysis constant of water increases
with temperature
Q.22 50 litre of a solution containing 10–5 mole
(D)when a solution of a weak monoprotic acid is
of Ag+ is mixed with 50 litre of a 2 × 10–7 M HBr
titrated again a strong base, at half neutralization
solution. [ Ag+] in resultant solution is:
point pH = (1/2) pKa .
[Given: Ksp(AgBr) = 5 × 10–13]
(A) 10–5 M (B) 10–6 M Q.28 A 2. 5 gm impure sample containing weak
–7
(C) 10 M (D)None of these monoacidic base (Mol. wt. = 45) is dissolved in
100 ml water and titrated with 0. 5 M HCl when
Q.23 pH of a saturated solution of silver salt of th
monobasic acid HA is found to be 9.  1 of the base was neutralised the pH was
 
5
Find the Ksp of sparingly soluble salt AgA(s).
Given: Ka(HA) =10–10 found to be 9 and at equivalent point pH of
solution is 4. 5 . Given: All data at 25°C & log 2
(A) 1. 1 × 10–11 (B) 1. 1 × 10–10
(C) 10–12 (D) None of these = 0. 3.
Select correct statement(s).
Q.24 The solubility of metal sulphides in (A) Kb of base is less than 10–6
saturated solution of H2S {[H2S]= 0. 1 M} can be (B)Concentration of salt (C) at equivalent point
represented by is 0. 25 M
MS + 2H+  M2++ H2S; (C)Volume of HCl is used at equivalent point is

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Ionic Equilibrium

100 ml ionization of phthalic acid in an aqueous

(D)Weight percentage of base in given sample solution.
is 80%. (A) KCl (B) H2SO
(C) HNO3 (D) NaOH
Q.29 Select incorrect statement(s).
(A)Phenolphthalein is suitable indicator for the Assertion and Reason:
titration of HCl (aq) with NH4OH (aq). (A)Statement-1 is true, statement-2 is true and
(B) An acid-base indicator in a buffer solution statement-2 is correct explanation for
of pH = pKIn + 1 is ionized to the extent of 90%. statement-1.
(C)In the titration of a monoacidic weak base (B)Statement-1 is true, statement-2 is true and
with a strong acid, the pH at the equivalent statement-2 is NOT the correct explanation for
point is always calculated by statement-1.
1 (C)Statement-1 is true, statement-2 is false.
pH= [pKw – pKb – logC ]
2 (D)Statement-1 is false, statement-2 is true.
(D)When Na3PO4 (aq) is titrated with HCl (aq),
the pH of solution at second equivalent point Q.35 Statement-1: pH of 10–7 M NaOH solution
1 is exist between 7 to 7. 3 at 25°C.
is calculated by [pKa1 + pKa2] Statement-2: Due to common ion effect
2
ionization of water is reduced.
Q.30 Which of the following is true for alkaline
aqueous solution? Q.36 Statement-1: In general phenolphthalein
pK w is used as an indicator for the titration of weak
(A) pH > (B) pH > pOH acid (HA) against strong base (NaOH).
2
pK w Statement-2: At equivalent point solution is
(C) pOH < (D) pH < pOH basic.
2

Q.31 An acid-base indicator has a Ka of 3. 0 × Q.37 Statement-1: Moles of Sr2+ furnished by

10–5. The acid form of the indicator is red and
the basic form is blue, then:
(A)pH is 4. 05 when indicator is 75% red
(B) pH is 5. 00 when indicator is 75% blue.
(C) pH is 5. 00 when indicator is 75% red
(D) pH is 4. 05 when indicator is 75% blue.
sparingly soluble substance Sr(OH)2 decreases
due to dilution.
Statement-2: Solubility product constant of
Sr(OH)2 is not affected by dilution.

Q.32 The equilibrium constant for the reaction

HONO(aq) + CN–(aq)⇌ HCN(aq) + ONO– (aq)
is 1. 1 × 10+6.
From the magnitude of this Keq one can
conclude that
(A) CN– is stronger base than ONO-
(B)HCN is a stronger acid than HONO
(C)The conjugate base of HONO is ONO–
(D)The conjugate acid of CN– is HCN

Q.33 All of the following are acid-base

conjugate pairs:
(A) HONO, NO2 (B) H3O+, OH–
(C) CH3 NH3 , CH3NH2 (D) HS– , S2

Q.34 Which of the following will suppress the

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Ionic Equilibrium

PREVIOUS YEARS QUESTIONS JEE MAIN

Q.1 A 0.004 M solution of Na2SO4 is isotonic (C) Autoprotolysis constant of water
with a 0. 010 M solution of glucose at same increases with temperature
temperature. The apparent degree of (D)When a solution of a weak monoprotic acid
is treated against a strong base, at half-
association of Na2SO4 is [IIT Screening 2004]
1
(A) 25% (B) 50% neutralization point pH =   pKa
 
2
(C) 75% (D) 85%
Q.8 A buffer solution can be prepared from a
Q.2 Ksp for Cr(OH)3 is 2. 7 × 10–31. What is its
mixture of [IIT JEE 1999]
solubility in moles/litre. [Orissa JEE 2004]
–8
(A) Sodium acetate and acetic acid in water
(A) 1 × 10 (B) 8 × 10–8 (B) Sodium acetate and hydrochloric acid in
(C) 1. 1 × 10–8 (D)0. 18×10-8 water
(C)Ammonia and ammonium chloride in water
Q.3 pKa of acetic acid is 4. 74. The
(D) Ammonia and sodium hydroxide in water
concentration of CH3COONa is 0. 01 M. The
pH of CH3COONa is [Orissa JEE 2004] Q.9 Assertion: BaCO3 is more soluble in HNO3
(A) 8. 37 (B) 4. 37 than in plain water.
(C) 4. 74 (D) 0. 474 Reason: Carbonate is a weak base and reacts
with the H+ from the strong acid, casuing the
Q.4 A weak acid HX has the dissociation barium salt to dissociate.
constant 1 × 10–5 M . It forms a salt NaX on
reaction with alkali. The degree of hydrolysis Q.10 Assertion: CHCl3 is more acidic than CHF3
of 0. 1 M solution of NaX is Reason: The conjugate base of CHCl3 is more
[IIT Screening 2004] stable than CHF3.
(A) 0. 0001% (B) 0. 01%
(C) 0. 1% (D) 0. 15%

Q.5 In the given reaction, the oxide of

sodium is
 4Na  O2  2Na2O 
Na O  H O  2NaOH [Orissa JEE
 2 2 
2002]
(A) Acidic (B) Basic
(C) Amphoteric (D) Neutral
Q.6 The dissociation of water at 25°C is 1. 9 ×
10–7% and the density of water is 1. 0 g/cm3.
The ionisation constant of water is
[IITJEE 1995]
–6
(A) 3. 42 × 10 (B) 3. 42 ×10–8
–14
(C) 1. 00 × 10 (D) 2. 00 ×10–16
Q.7 Which of the following statement (s) is (are)
correct [IITJEE 1998]
(A) The pH of 1. 0 × 10–8M solution of HCl is 8
(B)The conjugate base of H2PO4 is HPO24

6.6
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Ionic Equilibrium
EXERCISE 1 JEE ADVANCED
Q.1 Calculate the number of H+ present in one
ml of solution whose pH is 13.
Q.2 Calculate change in concentration of H+ ion
in one litre of water, when temperature
changes from 298 K to 310 K.
Given Kw(298) = 11–14 (310) =2. 56 × 10–14.
Q.3 (i) Kw for H2O is 9. 62 × 10–14 at 60°C.
What is pH of water at 60°C.
(ii)What is the nature of solution at 60°C whose
(a) pH = 6. 7 (b) pH = 6. 35
Q.4 The value of Kw at the physiological
temperature (37°C) is 2. 56 × 10–14. What is the
pH at the neutral point of water at this
temperature?
Q.5 Calculate pH of following solutions:
(a) 0. 1 M H2SO4 (50 ml)
+ 0. 4 M HCl 50 (ml)
(b)0. 1 M HA + 0. 1 M HB
[Ka(HA) = 2 × 10–5 ;
Ka (HB) = 4 × 10–5]
Q.6 What are the concentration of H+, H2C2O4,
HC2 O 4 and C2O24 in a 0. 1 M solution of oxalic
acid?
[K1= 10–2 M and K1 = 10–5M]
Q.7 What are the concentrations of H , +
HSO4
and H2SO4 in a 0. 20 M solution of
SO24
sulphuric acid?
Given: H2SO4  H+ + HSO4 ;
strong HSO4 1 H++ SO24 ; K2=10–2 M
Q.8 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 MNH3.
[Kb(NH3)= 1. 8 × 10–5]
Q.9 Calculate the pH of a solution made by
mixing 50. 0 ml of 0. 2M NH4Cl & 75. 0 ml of 0.
1 M NaOH.
[Kb(NH3) = 1. 8 × 10–5]
Q.10 What indicator should be used for the
titration of 0. 10 M KH2BO3 with 0. 10 M HCl?
Ka(H3BO3) = 7. 2 × 10–10
Q.11 An acid indicator has a Ka of 3 × 10–5. The
a 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?
Q.12 What is the OH– concentration of a 0. 08
M solution of CH3COONa.
[Ka(CH3COOH) = 1. 8 × 10–5]
Q.13 Calculate the pH of a 2. 0 M solution of
NH4Cl.
[Kb(NH3)=1. 8 × 10–5]
Q.14 Calculate OH– concentration at the
equivalent point when a solution of 0. 1 M
acetic acid is titrated with a solution of 0. 1 M
NaOH. Ka for the acid = 1. 9 × 10–5]
Q.15 Calculate the hydronium ion
concentration and pH at the equivalence point
in the reaction of 22. 0 mL of 0. 10M acetic acid,
CH3COOH, with 22. 0 mL of 0. 10 M NaOH.
[Ka = 1. 8 × 10–5]
Q.16 The values of Ksp 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
Q.17 Calculate the Simultaneous solubility of
, AgSCN and AgBr. Ksp (AgSCN) = 1. 1 × 10–12
Ksp(AgBr) = 5 ×10–13.
Q.18 A recent investigation of the
complexation of SCN–with Fe3+ led of 130, 16,
and 1. 0 for K1, K2, and K3, 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?
Q.19 Calculate the percent error in the [HO+]3
concentration made by neglecting the
ionization of water in a 10–6 M NaOH solution.
Q.20 A solution was made up to be 0. 01 M in
chloroacetic acid, ClCH2COOH and also 0. 002
M in sodium chloroacetate ClCH2COONa. What
is [H+] in the solution?
Ka = 1. 5 × 10–3.
Q.21 A solution contains HCl, Cl2HC COOH &
CH3COOH at concentrations 0. 09 M in HCl, 0.
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Ionic Equilibrium

09 M in Cl2HC COOH & 0. 1 M in CH3COOH. change in volume. Kb(NH3)= 1. 8 × 10–5.

pH for the solution is 1.
Ionization constant of CH3 COOH = 10–5. What
is the magnitude of K for dichloroacetic acid?
Q.22 Determine the [S2–] in a saturated (0. 1M)
H2S solution to which enough HCl has been
added to produce a [H+] of 2 × 10–4 . K1 = 10–7,
K2= 10–14.
Q.23 What is the pH of a 1. 0 M solution of
acetic acid? To what volume must 1 litre of the
solution be diluted so that the pH of the
resulting solution will be twice the original
value. Given Ka =1. 8 × 10–5.
Q.24 It is desired to prepare 100 ml of a buffer
of pH 5. 00. Acetic, benzoic and formic acids
and their salts are available for use. Which acid
should be used for maximum effectiveness
against increase in pH? What acid-salt ratio
should be used? pKa values of these acids are:
acetic 4. 74; benzoic 4. 18 and formic 3. 68.
Q.28 20 ml of a solution of 0. 1 M CH3COOH
solution is being titrated against 0. 1 M NaOH
solution. The
pH values after the addition of 1 ml & 19 ml of
NaOH are (pH) &1(pH)2,what is pH?
Q.29 A weak base BOH was titrated against a
strong acid. The pH at l/4th equivalence point
was 9. 24. Enough strong base was now added
(6m. eq. ) to completely convert the salt. The
total volume was 50ml. Find the pH at this
point.
Q.30 An organic monoprotic acid [0. 1M] is
titrated against 0. 1 M NaOH. By how much
does the pH change between one fourth and
three fourth stages of neutralization? If at one
third stage of neutralization, the pH is 4. 45
what is the dissociation constant of the acid?
Between what stages of neutralisation may the
pH change by 2 units?

Q.25 When a 40 mL of a 0. 1 M weak base is

titrated with 0. 16M 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.

Q.26 A buffer solution was prepared by

dissolving 0. 05 mol formic acid & 0. 06 mol
sodium formate in enough water to make 1. 0
L of solution. Ka for formic acid is 1. 80 × 10–4.
(a) Calculate the pH of the solution.
(b) If this solution were diluted to 10 times its
volume, what would be the pH?
(c) If the solution in (b) were diluted to 10 times
its volume, what would be the pH?

Q.27 How many moles of sodium hydroxide

can be added to 1. 00 L of a solution 0. 1 M in
NH3 & 0. 1 M in NH4Cl without changing the
pOH by more than 1. 00 unit? Assume no

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Ionic Equilibrium

EXERCISE 2 JEE ADVANCED

Q.1 A solution with pH 2. 0 is more acidic than (C) 6 – 8 (D) 8 –10

the one with pH 6. 0 by a factor of:
(A) 3 (B)4 Q.9 How many gm of solid NaOH must be
(C) 3000 (D) 10000 added to 100 ml of a buffer solution which is 0.
Q.2 The first and second dissociation constants 1 M each w. r. t. Acid HA and salt Na+ A– to
of an acid H2A are 1. 0 × 10–5 and 5. 0 × 10–10 make the pH of solution 5. 5. Given pka(HA)= 5.
respectively The overall dissociation constant (Use antilog (0. 5) = 3. 16)
of the acid will be: (A) 2. 08 × 10–1 (B) 3. 05 × 10–3
(A) 5. 0 × 10–5 (B) 5. 0 × 1015 (C) 2. 01 × 10–2 (D)None of these
–15
(C) 5. 0 × 10 (D) 0. 2 × 105
Q.10 If 40 ml of 0. 2 M KOH is added to 160 ml
Q.3 An aqueous solution contains 0. 01 M RNH2 of 0. 1 M HCOOH [Ka = 2 × 10–4], the pOH of
(Kb = 2 × 10–6) & 10–4 M NaOH. the resulting solution is
The concentration of OH is nearly:
(A) 3. 4 (B) 3. 7
(A) 2. 414 × 10–4 (B) 10–4 M
–4 (C) 7 (D) 10. 3
(C) 1. 414 × 10 (D) 2 × 10–4
Q.11 1 M NaCl and 1M HCl are present in an
Q.4 The degree of hydrolysis of a salt of weak
acid and weak base in it's 0. 1 M solution is aqueous solution. The solution is
found to be 50%. If the molarity of the solution (A) Not a buffer solution and with pH < 7
is 0. 2 M, the percentage hydrolysis of the salt (B) Not a buffer solution with pH > 7
should be (C) A buffer solution with pH < 7
(A) 100% (B) 50% (D) A buffer solution with pH > 7
(C) 25% (D) None of these
Q.12 The pKa of a weak acid (HA) is 4. 5. The
Q.5 The pH of the neutralisation point of 0. 1N pOH of an aqueous buffered solution of HA in
ammonium hydroxide with which 50% of the acid is ionized is:
0. 1N HCl is
(A) 4. 5 (B) 2. 5
(A) 1 (B) 6
(C) 9. 5 (D) 7. 0
(C) 7 (D) 9
Q.13 The solubility of A2X3 is y mol dm–3. Its
Q.6 If equilibrium constant of
CH3COOH+H2OCH3COO– + H3O solubility product is
Is 1. 8 × 10–5, equilibrium constant for (A) 6 y2 (B) 64 y4
CH3COOH + OH–1 CH3COO– + H2O is (C) 36y5 (D) 108y5
(A) 1. 8 × 10–9 (B) 1. 8 × 109
–9 Q.14 If Ksp for HgSO4 is 6. 4 × 10–5, then solubility
(C) 5. 55 × 10 (D) 5. 55 × 1010
of this substance in mole per m3 is
Q.7 The pKa, of a weak acid, HA, is 4. 80. The (A) 8 × 10–3 (B) 6. 4 × 10–5
pKb of a weak base, BOH, is 4. 78. The pH of an (C) 8 × 10–6 (D) None of these
aqueous solution of the corresponding salt,
BA,will be: Q.15 The solubility of a sparingly soluble salt
(A) 8. 58 (B) 4. 79 AB2, in water is 1. 0 × 10–5 mol L–1. Its solubility
(C) 7. 01 (D) 9. 22 product is:
(A) 10–15 (B) 10–10
Q.8 The range of most suitable indicator which
should be used for titration of X– Na+ (0. 1 M, (C) 4 × 10–15 (D) 4 ×10–10
10 ml) with 0. 1 M HCl should be (Given: K b(x  ) Q.16 Which of the following is most soluble in
–6
= 10 ) water?
(A) 2 – 3 (B) 3 – 5 (A) MnS (Ksp = 8 × 10–37)

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Ionic Equilibrium

(B) ZnS (Ksp = 7 × 10–16) (B) Na2CO3 + NaHCO3

(C) Bi2S3 (Ksp = 1 × 10–72) (C) NaCl + HCl
(D) Ag3(PO4) (Ksp=1. 8 × 10–18) (D) NH4Cl + (NH4)2SO4
Q.17 The precipitate of CaF2(Ksp = 1. 7 × 10–10)
is obtained when equal volumes of the Q.24 Which of the following mixtures
following are mixed constitute a buffer?
(A) 10–4 M Ca3++ 10–4M F– (A) Na2CO3 + HCl
(B) 10–2 M Ca2++ 10–3M F– (B) NaOH + CH3COOH
(C) 10–5 M Ca2++ 10–3M F– (C) NH3 + CH3COONH4
(D) 10–3 M Ca2++ 10–5M F– (D) NaOH + BaCl2

Q.18 50 litre of a solution containing 10–5 mole Q.25 In which of the following pairs of solutions
of Ag+ is mixed with 50 litre of a 2 × 10–7M HBr is there no effect on the pH upon dilution?
solution. [Ag+] in resultant solution is: (A) 0. 1 M NH3 and 0. 1 M(NH4)2SO4
[Given: Ksp(AgBr) = 5 × 10–13] (B) 0. 1 M NaH2PO4 and 0. 1 M Na2HPO4
(A) 10–5 M (B) 10–6M (C) 0. 1 M HCl and 0. 01 M NaOH
–7
(C) 10 M (D)None of these (D) 0. 1 M KCl and 0. 1 M HCl
Q.19 pH of a saturated solution of silver salt of Paragraph 1
monobasic acid HA is found to be 9. 1. 2 g of a monoprotic acid HA, is titrated with
Find the Ksp of sparingly soluble salt AgA(s). 0. 222 M NaOH solution. The pH of the solution
Given: Ka (HA) = 10–10 is monitored with pH meter. A portion of the
(A) 1. 1 × 10–11 (B) 1. 1 × 10–10 titration curve is shown in the diagram.
(C) 10–12 (D)None of these Q.26 How many mL of NaOH is required to
Q.20 In the following reaction: Expanded titration
[Cu(H2O)3 (OH)]++ [Al(H2O)6]3+ 12. curve of
AB 00
HA vs NaOH
 [Cu(H2O)4]2+ + [Al(H2O)5(OH)]2+ 11.
CD 00
(A) A is an acid and B the base 10.
(B) A is a base and B the acid 00
(C) C is the conjugate acid of A, and D is the
9. 00
conjugate base of B
(D) C is the conjugate base of A, and D is the 8. 00
conjugate acid of B 7. 00
15 16 17 18 19 20
Q.21 Which does not react with NaOH or which Volume of NaOH(mL)
is not acid salt?
bring about the titration to its equivalence
(A) NaH2PO2 (B) Na2HPO3
point?
(C) Na2HPO4 (D) NaHCO3
(A) 4. 00 (B) 9. 00
Q.22 pH of the following solution is not (C) 19. 00 (D)None of these
affected by dilution:
Q.27 What is the pH of solution at the
(A) 0. 01 M CH3COONa
equivalence point?
(B) 0. 01 M NaHCO3
(A) 3. 50 (B) 7. 00
(C) buffer of 0. 01 M CH3 COONa and 0. 01 M
(C) 8. 40 (D) None of these
CH3COOH
(D) 0. 01 M CH3COONH4 Q.28 What is the molar mass of HA?
Q.23 Which of the following mixtures (A) 180 (B) 222
constitute a buffer? (C) 282 (D) None of these
(A) CH3COOH + CH3 COONa

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Ionic Equilibrium

Paragraph 2 indicator)
Potash alum is K Al(SO4)2. 12H2O. As a strong (A) 200 ml of H2SO4 (P) Phenol Red (6.8
electrolyte, it is considered to be 100 % solution (specific to 8.4)
dissociated into K+, Al3+ and SO24 . The gravity 1. 225
solution is acidic because of the hydrolysis of containing 25%
Al3+, but not so acidic as might be expected, H2SO4 by weight) +
because the SO24 can sponge up some of the 800 ml of 0. 525 M
 strong triacidic base
H3O+ by forming HS0 4 . Given a solution made X (OH)3
by dissolving 11. 85 gm of K Al(SO4)2 . 12H2O in (B) 50 ml of 0. 1 M (Q)Propyl red (4. 6 to
enough water to make 100 cm3 of solution. HCO3 +50 ml of 0. 8 6. 4)
What is [H3O+] of the solution if M CO32 (H2CO3: Ka1
Q.29 None of the ion is hydrolyzing. = 4 × 10–7, Ka2 = 2 ×
(A) 10–7 M 10–11)
(B) less than 10–7 M (C) 50 ml of 0. 2 M (R) Phenolphtalein
(C) More than 10–7 M HA(aq) (Ka= 10–5) + (8. 3 to 10. 1)
(D) 0. 0 50 ml of 0. 1 M
HCl(aq) + 100 ml of0.
Q.30 Only Al3+ is hydrolysing and its first
13M NaOH (aq)
hydrolysis constant is 1. 4 × 10–5M
(S)Malachite green
(A) 1. 87 × 10–3 M (B) 6. 24 ×10–4M
(11. 4 to 13)
(C) 0. 09 M (D) None of these

Q.31 Only SO24 is hydrolysing and acid

dissociation constant of H SO 4 in water is 1. 25
× 10–2.
(A) 1. 26 × 10–3 M (B) 6. 32 × 10–7 M
(C) 1. 58 ×10–8M (D) None of these

Q.32 Both Al3+ and SO24 are hydrolysing.

(A) 2. 93 × 10–4M (B) 0. 0114M
(C) 5. 43 ×10–6M (D) None of these

Match the Column

Q.33 Match the following
List I List II weak

(A) CH3COOH (P) Base

(B) H2SO4 (Q)Weak acid
(C) NaOH (R) Strong acid
(D) NH3 (S) Strong base

Q.34
Column I Column II
(pH of resultant (Exist between
solution) Colour transition
range of an

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Ionic Equilibrium

PREVIOUS YEARS QUESTIONS JEE ADVANCED

Q.1 The precipitate of CaF2(Ksp=1. 7×10–10) is HCl in water at 25°C. The concentration of H+
obtained, when equal volumes of the following at equivalence point is (Kw = 1 × 10–14 at 25°C)
arE mixed (1982) (2008)
(A) 10–4 M Ca2+ + 10–4M F– (A) 3. 7 × 10–13 M
(B) 10–2 M Ca2+ + 10–3M F– (B) 3. 2 × 10–7 M
(C) 10–5 M Ca2+ + 10–3M F– (C) 3. 2 × 10–2 M
(D) 10–3 M Ca2+ + 10–5M F– (D) 2. 7 × 10–2 M

Q.2 Pure ammonia is placed in a vessel at a Q.7 Aqueous solutions of HNO3 KOH,
temperature where its dissociation constant () CH3COOH, and CH3COONa of identical
is appreciable. At equilibriumN2 + 3H2 ⇌NH3 concentrations are provided. The pair(s) of
(1984) solutions which form a buffer upon mixing
(A) Kp does not change significantly with is(are) (2010)
pressure (A) HNO3 and CH3COOH
(B)  does not change with pressure (B) KOH and CH3COONa
(C) concentration of NH3 does not change with (C) HNO3 and CH3COONa
pressure (D) CH3COOH and CH3COONa
(D) concentration of hydrogen is less than that
of nitrogen Q.8 The equilibrium 2 CuI ⇌ Cu0 + CuII in
aqueous medium at 25°C shifts towards the left
Q.3 A certain buffer solution contains equal in the presence of . (2011)
concentration of X– and HX. The Kb for X– is 10– (A) NO3
(B) Cl –

10
. The pH of the buffer is (1984) (C) SCN– (D) CN–
(A) 4 (B) 7
(C) 10 (D) 14 Q.9 The solubility of Mg(OH)2 in pure water is
9. 57 × 10–3 g/L. Calculate its solubility (in g/L)
Q.4 A certain weak acid has a dissociation in 0. 02M Mg(NO3 )2 solution. (1986)
constant of 1. 0 × 10–. The equilibrium constant
for its reaction with a strong base is (1984) Q.10 What is the pH of the solution when 0. 20
–4 –10
(A) 1. 0 × 10 (B)1. 0 × 10 moles of HCl is added to one litre of a solution
(C) 1. 0 × 1010 (D) 1. 0 × 1014 containing:
(i) 1 M each of acetic acid and acetate ion
Q.5 Solubility product constant (Ksp) of salts of (ii)0. 1 M each of acetic acid and acetate ion
types MX, MX2 and M3X at temperature ‘T’ are Assume the total volume is one litre. Ka for
4. 0 × 10–8, 3. 2 ×10–14 and 2. 7 × 10–15, acetic acid =1. 8 × 10–5 (1987)
respectively. Solubilities (mol. dm–3 )of the salts
at temperature ‘T’ are in the order (2008) Q.11 At a certain temperature, equilibrium
(A) MX > MX2 > M3X constant (Kc) is 16 for the reaction;.
(B) M3X > MX2 > MX SO2(g) +NO2(g) ⟶SO3(g) + NO(g)
(C) MX2 > M3X >MX
If we take one mole of each of all the four gases
(D) MX > M3X > MX2
in a one litre container, what would be the
2 equilibrium concentrations of NO and NO2?
Q.6 2. 5 mL of M weak monoacidic base (Kb
5 (1987)
2
= 1 × 10–12 at 25°C) is titrated with M
15

6.13
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Ionic Equilibrium

Plancessential Questions
JEE MAIN/BOARDS EXERCISE 1
Q.1 Q.4 Q.6 Q.8 Q.13 Q.17 Q.19
Q.28 Q.29

JEE MAIN EXERCISE 2

Q.5 Q.8 Q.9 Q.13 Q.17 Q.22 Q.24
Q.29 Q.31 Q.37

PREVIOUS YEARS QUESTIONS JEE MAIN

Q.4 Q.7 Q.11

JEE ADVANCED EXERCISE 1

Q.2 Q.6 Q.9 Q.11 Q.16 Q.21 Q.24
Q.25 Q.29 Q.30

JEE ADVANCED EXERCISE 2

Q.1 Q.4 Q.7 Q.8 Q.9 Q.13 Q.16
Q.19 Q.21 Q.27 Q.28 Q.29 Q.32

PREVIOUS YEARS QUESTIONS JEE ADVANCED

Q.3 Q.5 Q.8 Q.10

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Ionic Equilibrium

ANSWER KEY

EXERCISE 1 JEE MAIN/BOARDS

Q.1 2.3mol/lit Q.17 (i) pH = 4.35 (ii) 1.79 × 10–9 mol/lit

Q.2. 1.5 times Q.18 (i) 28.57% (ii) 4.11 × 10–4 mol dm-3

Q.19 67%
Q.3 1.44 × 10–4
Q.20 pH = 7.3
Q.4 (a) 1.76 × 10–4 mg/L,
(b) 8.8 × 10–5 mg/L, Q.21 [HS–] 9.54 × 10–5 ,in 0.1 M HCl[HS–] = 9.1
(c) 1.588 mg/L × 10–8 M,
[S2–] = 1.2 × 10–13 M, in 0.1 M HCl [S2–] = 1.09
Q.5 No
× 10–19 M
Q.6 4.11 × 10–4 M
Q.22 [Ac–] = 0.00093, pH = 3.03
Q.7 5.6 × 10–10, 2.4 × 10–4 , 5.63
Q.23 [A–] = 7.08 × 10–5 M, Ka= 5.08 × 10–7,
Q.8 2.87,1.3 pKa= 6.29

Q.9 Ksp(Ag,CrO4) = 4 × 10–12 Q.24 (a) 2.52 (b) 11.70 (c) 2.7(d) 11.30

Q.10 pH = 9.168 Q.25 (a) 11.65 (B) 12.21 (c) 12.57 (d) 1.87

Q.11 8.7mL
Q.26 0.103g
–5
Q.12 HZ< HY< HX , Ka(HY) = 10 M, Ka(HZ)=
Q.27 pH = 7.59, kH = 1.5 × 10–11
10–9 M
Q.28 11
Q.13 (a) 3.7 × 104 dm3 (b) 4 dm3
1
Q.14 Kc = 3.02 × 10–2 , S = 0.123 M Q.29 of its solubility in water solubility
2200
Q.15 (a) pH = 3.83 (b)pH = 3.85 (c) 3.99 decreases

Q.16 9.55 Q.300.0 82 mol of NaOH can be added

EXERCISE 2 JEE MAIN

Q.1 A Q.8 D Q.15 B Q.22 C Q.28 B,C Q.32 Q.36
Q.2 C Q.9 D Q.16 D Q.23 A Q.29 A,C,D A,B
Q.3 C Q.10 A Q.17 D Q.24 D A,B,C Q.33 D Q.37
Q.4 B Q.11 D Q.18 C Q.25 B Q.30 Q.34 A,B
Q.5 B Q.12 B Q.19 A Q.26 A A,B,C B,C,D
Q.6 C Q.13 B Q.20 B Q.27 Q.31 Q.35
Q.7 B Q.14 C Q.21 B B,C A,B A,B

PREVIOUS YEARS QUESTIONS JEE MAIN

Q.1 C Q.2 A Q.3 A Q.4 B Q.5 B Q.6 D
Q.7 B,C Q.8 A,C Q.9 A Q.10 A

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Ionic Equilibrium

EXERCISE 1 JEE ADVANCED Q.16 QX2 is more soluble

Q.17 4 × 10–7mol/LAgBr, 9 × 10–

Q.1 6.022 × 107 7
mol/LAgSCN
Q.2 0.6 × l0–7
Q.18 Kd= 1/Kf = 4.8 ×10–4

Q.3 (i) 6.51 ; (ii) (a) Basic, (b)Acidic Q.19 error = 1%

Q.4 6.81 Q.20 [H+]= 2.5 × 10–3

Q.5 (a) 0.522, (b) 2.61 Q.21 Ka= 1.25 × 10–2

Q.6 0.027 M, 0.073 M, 0.027 M, 10–5M Q.22 [S2–] = 2.5 × 10–15

Q.7 0.2116 M, 0.1884 M, 0.0116 M, 0 Q.23 V = 2.77 × 104 litre

Q.8 8.7782 Q.24 acetic acid, salt-acid molar ratio 1.8: 1

Q.9 9.7324 Q.25 9.168

Q.10 (methyl red), one with pH = 5.22 as Q.26 (a)pH = 3.83 (b) pH = 3.85, (c) = 3.99
midpoint of colour range
Q.27 0.0818 moles
Q.11 ApH = 0.954
Q.28 2.558
Q.12 [OH–] = 6.664 × 10–6
Q.29 11.22
Q.13 pH = 4.477
1 10
–6 Q.30 0.9542, pKa = 4.751, th & th stages
Q.14 5.12 × 10 M 11 11
of neutralisation
Q.15 8.71

EXERCISE 2 JEE ADVANCED

Q.1 A Q.6 D Q.11 A Q.16 A Q.21A Q.26 B,C Q.31 C
Q.2 C Q.7 C Q.12 C Q.17 B Q.22 B Q.27 B Q.32 A
Q.3 D Q.8 B Q.13 D Q.18 C Q.23 C Q.28 C
Q.4 B Q.9 A Q.14 D Q.19 A Q.24 C Q.29A
Q.5 B Q.10 D Q.15 C Q.20 A,C,D Q.25 A,B Q.30 A
Q.33 A-Q, B-R, C-S, D-P
Q.34 A-S, B-S, C-Q

PREVIOUS YEARS QUESTIONS JEE ADVANCED

Q.1 B Q.2 A Q.3 A Q.4 C Q.5 D Q.6 D Q.7 C,D
Q.8 B,C,D Q.9 8.7×10-4 gL-1 Q.10 (i)4.56 (ii)1
Q.11 [NO]=0.80M;[NO2]=0.20M

6.16
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Ionic Equilibrium

SOLUTIONS

EXERCISE – I JEE MAIN 1.5M

2AgCl(s)  Na2CO3
(1.50.0000366)
Ka 1.5M
Sol.1.   0  initialconc
C
will be equal, equate the terms on R.H.S.
Ag2 (CO)3 (s)  2NaCl
 0.0000732 M  eqb. conc.
for both the acids.
K sp (Ag2CO3 ) 8.2  1012
CH COOH HNO2 [Ag ]  
3 1.5
Ka [CO32 ]
Ka
C  2.338  106 M
C
 K sp  [Ag ][Cl ]  (2.338  10 6 )(0.0000732)
Sol.2.
Blood Spinal fluid  1.71  1010

[H ]  107.36 [H ]  107.53 5

Sol.7. Kb (NH4 OH)  1.8  10 ;C  0.01M
 4.36  108  2.95  108
Kw
 cx2 (x = degree of hydrolysis)
Sol.3. The freezing point depression is given Kb

by T  K f  m Kh  cx2 ( Kh  hydrolysis constant)

1.86 K mol-1 kg x m = 0.758 K so, m = 0.40752 1
pH  (pK w  pKb  log C)
mol kg-1 . If this can be taken to be 0.40752 2
mol L-1 for this question.
Sol.8. C = 0.1 M
0.40752
The van’t Hoff factor i   1.0188 K a  1.8  105
0.400
Ans: van’t Hoff factor i = 1.02 CH3COOH CH3COO   H
x
(ii) Formic acid ionizes in water according to: 0.1 x

HCOOH HCOO  H [CH3COO  ][H ] 2

Ka  ; 1.8  105  x
If the initial concentration before ionization is [CH3COOH] 0.1
0.400 mol L-1 and x mol L-1 ionizes then the (i) [H ]  x  pH   log[H ]


final number of particles in the solution is

(ii) Vol. of CH3COOH = 1L
(0.400 mol L-1 - x mol L-1) + 2x mol L-1 = 0.400
Addition of 0.05 mole of HCl increases the
mol L-1 + x mol L-1 .
concentration of CH3COOH by 0.05 and
Now, 0.400 mol L-1 + x mol L-1 = 0.40752 mol 
L-1 reduces the conc. of CH3COO by 0.05 mol /
x mol L-1 = 7.52  10-3 mol L-1 = [H+] = L.
[HCOO-]  [CH3COOH]  0.1  0.05  0.15 M
  3 1
[H ][HCOO ] [7.52  10 molL ]
Ka   [CH3COO ]  1.34  103  0.05  0.05134 M
[HCOOH] [0.400  7.52  103 ]molL1
[salt] 0.05134
 1.44  104 pH  pK a  log   log1.8  10 5  log
[acid] 0.15
2
Sol.5. Initial[Na2CO3 ]  [CO3 ]  1.5 M pH=1.3
0.0026 Sol.10. Solved on a similar basis in solved
Equilibrium [Cl ]  [NaCl]   0.0000732M
35.5 example (1) of Jee Advanced.

S 6.1
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Ionic Equilibrium

Sol.17. In order to prevent precipitation of Zns,

[ Zn2 ][S2 ]  K sp (ZnS)  1  1021
(ionic product)

or (0.1)[S2 ]  1  1021
or [S2 ]  1  1020
2
This is the maximum value of [S ] before ZnS
will precipitate.
 2
Let [H ] to be maintained [S ] be x.
Thus for
H2S 2H  S2

[H ]2 [S2 ] x2 (1  10 20 )

Ka    1.1  1021
[H2S] [H2S]

Or x  [H ]  0.1M
 no ZnS will precipitate at a concentration of
H greater than 0.1 M.


Sol.21. Similar to Sol.22. of Jee Advanced

Exercise -1.

5 Ka
Sol.22. K a  1.74  10 
C

Sol.23. RCOOH RCOO  H

0.01 (0.01 ) (0.01 )

pH = 4.15
conc. = 0.01 M
Get conc. of H from pH. Calculate  and Ka.

Sol.25. Calculate H / OH conc. using the

volume and weight. Thus, calculate pH.

Sol.26. Calculate solubility and then calculate

it using volume of 2.5 L.

Sol.28. CO2 with H2O forms H2CO3 .

CO2  H2O H  HCO3

[H ][HCO3 ]
K1   4.5  10 7
[CO2 ]

Now, pH =  log[H ]  7.4; [H ] = 4  108


[HCO3 ] 4.5  10 7
Thus,   11
[CO2 ] 4  10 8
Sol.30. Similar to Sol.27. of Jee Advanced
Exercise 1.

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Ionic Equilibrium

EXERCISE – II JEE MAIN (3  105 )(25)

[H ] 
For 75% blue: 75
5
 1  10  pH  5
Sol.22 K sp (AgBr)  5  1013 The change in pH = 5 – 4.05 = 0.95
AgBr Ag  Br 
[S] [S]

K sp  S2 ; S  K sp ..... (1)

Ag  HBr  AgBr  H [Ag ]

105 mol 2107 mol
50 L 50 L

M = mole / V
From eSol.(1), the obtained [Ag+] should be
subtracted from the available 50 L Ag+
solution.

 9
Sol.23 pH (HA) = 9  [H ]  10
Ksp(AgA) = [Ag+] [A-]
Ka (HA) = 10-10
HA H  A

[H ][A  ]
Ka  . Get conc. of [A-]
[HA]
Thus, calculate Ksp.
Sol.26 MX 4 M4  4X
 Ksp  [S][4S]4  256
1/4
 K sp 
S 
 256 
 
mass
Sol.28 M 
molar mass
1
 At of experiment
5
 At equivalent point molarity is 0.25.

Sol.31 HIn H  In

[H ][In ] [H ][base]

K In  K a  
[HIn] [acid]
[acid]
[H ]  K a
[base]
5
For 75 % red: [H ]  (3  10 )(75)
25
 9  10 5
pH  4.05

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Ionic Equilibrium

PREVIOUS YEARS’ QUESTIONS JEE MAIN

Q.1 Na2So4 2Na + + SO24 [H ][OH ]
K= = c2
(0.004 –x) 2x (H2O)
x 1000
= 1.9 × 10–9 × 1.9 × 10–9 ×
18
Since both the solution are isotonic
0.004 + 2x = 0.01 = 2.0 × 10–16

 x = 3 × 10–3 Q.7 (bc) pH of 1 × 10–8 M is below to7

H2PO4 + H2O HPO24 + H3O+
 Percent dissociation
conjugate base of
3  103 H2PO4 acid
=  100 = 75%
0.004 H2O + H2O OH– + H3O+
K (Auto protolysis constant of water
Q.2 (a) Cr(OH)3 Cr+3 + 3OH– i.e., with ionic product of water)
increases with temperature. For half
neutralization of a weak acid by a weak
x 3x base
Ksp = x.(3x)3 = 27x4 [Salt]
pH = pKa + log
[Acid]
K sp 2.7  10 31 [Salt] = [Acid] pH = pKa.
x= 4 ;x= 4
27 27 Q.8 (ac) A buffer solution can be prepared
x = 1 × 10–8 mole/litre. by mixing weak acid/base with salt of
its Conjugate base/acid.

1 Q.9 (a) Barium carbonate is more soluble in

Q.3 (a) pH = 7 + [pKa + logC]
2 HNO3 than in water because carbonate
1 is a weak base and reacts with the H+
=7+ [4.74 + log10–2]
2 ion of HNO3 causing the barium salt to
1 dissociate.
= 7+ [4.74 – 2] BaCO3 + HNO3  Ba(NO3 )2 + CO2 +
2
H2O
2.74 Q.10 (a) The conjugate base of CHCl3 is more
=7+ = 8.37
2 stable than conjugate base of
CHF3(CF3). CCl3 stabilized by –I effect of
Q.4 X– + H2O HX + OH– chlorine atoms as well as by the
electrons. But conjugate base of
10 14 109 CH3(CH3) is stabilized only by –I effect
Kh = so h = = 10–4
10 5 101 of flourine atoms. Here both assertion
and reason are true and reason is
100 × 10–4 = 10–2 correct explanation of assertion.
So% of hydrolysis = 0.01%.

Q.5 Na2O from NaOH. So that it is basic

oxide.
1000
Q.6  = 1.9 × 10–9 ; C =
18

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Ionic Equilibrium

EXERCISE – I JEE ADVANCED

Sol.1 pH = 13 4.69  1011  6.73  105
 4.8  1011
 [H ]  10  pH 6.61  105
 conc. & volume is given, no. of moles of H mole/litre
can be calculated. Using NA calculate number Sol. 8 & 9. Similar to (5)
of H Sol.11. Similar to Sol.31 of Jee-Main Exercise-2
5
14
Sol.3 K w  2.56  10  60C Sol.12. K a (CH3COOH)  1.8  10
1
Apply pH  (pK w )
CH3COONa(0.08 M)
2
Calculate [H ] from K a .

14
Sol.4. K w  2.56  10
Similar to 3 Assuming concentration of CH3COOH as 0.08
Sol.5. (a) 0.1 M H2SO4 (50 ml) + 0.4 M HCl M.
(50 ml). Calculate number of H in both cases
and calculate pH. Sol.13. Kb (NH3 )  1.8  10
5

(b) 0.1 M HA + 0.1 M HB

2M NH4 Cl solution of strong acid and weak
K a  2  105 K a  4  10 5
base.
pH  Ka  C1  K a  C2 1
(HA) (HB) pH  [pK w  pKb  logC]
2

Sol.6 & 7: We have, pH = - log [ H ]; Sol.17. Apply Ksp expression.
3 
4.18 = - log [ H ]
 Sol.18. Fe  SCN  Fe(SCN)3

Or log[H ]  4.18  5.82 K1  130 ; K 2  16 ; K3  1.0
 5 Refer sub – topic 4.5. Stability constant
Taking antilog: [H ]  6.61  10 mole / litre
Sol.20. Similar to (12)
Now, for equilibrium
Sol.22. Refer to Illustration 8 in the content.
H2CO3 HCO3  H Sol.23. Use pH = - log [H+] for 1 M.
1
[HCO3 ][H ]
Ka  CH3COOH CH3COO  H
[H2CO3 ] 1 x x x

[HCO3 ](6.61  105 ) x2

7 Ka   x2  1.8  105 ; x  4.2  103  [H ]
or 4.45  10  1x
0.01
7  pH   log[H ]   log(4.2  103 )  2.37
4.45  10  0.01
[HCO3 ] 
6.61  105 Now, let 1 litre of 1 M CH3COOH be diluted
to V litres so that the pH of the solution
 6.73  106 mole / litre .
doubles. Let the concentration of the diluted

Again for the dissociation of HCO3 , we have solution be c moles / litre. Thus,
c
HCO3 CO32  H
CH3COOH CH3COO   H
(c  x') x' x'
[CO32 ][H ] [HCO3 ]  K a
Ka   [CO32 ]   x'.x'
[HCO3 ] [H ] Ka   1.8  10 5 .... (1);
(c  x')
Further pH   log x'  2  2.37  4.74 (pH
doubles on dilution)

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Ionic Equilibrium

Calculate pH
Or log x'  4.74  5.26 ; x'  1.8  105 .
Sub. x’ in (1) we get, c  3.6  105
As the number of moles of CH3COOH before
and after dilution will be the same.
 moles of CH3COOH = molarity  volume in
litres.
 Initial molarity  1 
 3.6  10 5  V  1  1  
 Initial volume  1 
V  2.78  104 litres
Sol.25. At the end point, m.e. (on millimoles)
of the salt produced
= m.e. of NaOH  0.1  36.12  3.612
(Since salt formed will be univalent and so for
such salts m.m. = m.e.)
m.e. (millimole) of HCl added
 0.1  18.06  1.806
The addition of 1.806 m.e. of HCl will produce
the same number of m.e. of the unknown acid
and reduce the amount of the salt by 1.806
m.e.
 m.e. (millimole) of the unknown acid =
1.806
And m.e. (or millimole) of the salt = 3.612 –
1.8006 = 1.806.
Using,
millimole of salt
pH = pKa + log
millimole of acid

Sol.26. Let us find [H ] of HCOOH before
adding HCOONa.
For the equilibrium,
HCOOH H  HCOO

[H ][HCOO ] [H ]2

Ka  
[HCOOH] [HCOOH]
( [H ] = [HCOO  ] )
 [H ]  K a .[HCOOH]  1.8  10 4  0.2

 6  103
Now, on the addition of sodium formate in
the acid, we have,
[acid] 0.2
[H ]   1.8  10 4   3.6  104
[salt] 0.1

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Ionic Equilibrium

EXERCISE – II JEE ADVANCED

 1 Sol.5. NH4 OH  HCl  NH4 Cl  H2O
Sol.1. pH   log [4 ]  
or 0.1N 0.1N
log10 [4 ]
x2 x
[4 ]  10pH K
2
; K
(0.1  x) 0.1  x
 2  6
 [4 ]  10 and [H ]  10 12
6
102  106 12
 factor = 10 4
Sol.6.
Sol.2. Overall dissociation CH3COOH  H2O  CH3COO  H3O
5 10
Constant of the  1.0 10  5.0  10 K a  1.8 10 5
15
Acid (H2 A) = 5.0  10 CH3COOH  OH  CH3COO  H2O

6 Kw 10 14
Sol.3. kb  2 10 ; 0.01 M RNH2 Kb    5.55  1010
Ka 1.8 10 5
104 M NaOH
  Sol.7. pK a  4.80 ; pK b  4.78

RNH2  H2O  RNH  OH
 3
1
1 0 0 pH  (pR w  pK a  pKb )
  2
1
Common ion effect due to NaOH  
Sol.8. (x Na ) 0.1M 10 ml

[RNH3 ][OH ]  HCl 0.1M
kb 
[RNH2 ] kb (x  )  10 6
[C. A]
POH= -log kb  log K a  Kb  K w
[Base]
6 Kw 1014
=-log (2  10 ) + log (0.01) ka    108
10 4 Kb 10 6

= - log 2 + 6 + log 0.01 + 4 [H ][In ] [H ] [base]

= 10 – 2 – 0.3010 = 7.699 k In  K a  
[HIn ] [acid]

POH = - log [OH ] [acid] [0.1]
[H ]  K a   10 9
[base] [0.1]
[OH ] = 107.699
1
pH  (pK w  pKb  log a)
Sol.4. Salt of WB & WA 2
pKa
Degree of hydrolysis = 50 % ; M = 0. 1 M
M2  0.2 M Sol.9. Vol. of buffer soln. = 100 ml

% hydrolysis of salt = ?
Mbuffer  0.1M
pH  5.5
Kh Kh
h1  h2 
C1 C2 pK a (HA)  5
h12 C1  Kh h22 C2  Kh NaOH  (HA  NaA)  pH (5.5)
0.1M 0.1M
pKa 5
h12 C1  h22 C2 100 ml

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Ionic Equilibrium

[salt] [0.1] will halved. Let us calculate the ionic

pH  pK a  log  5  log 5
[acid] 0.1 product in each case.
Contributing pH  0.5 by NaOH (a) Ionic product  [Ca ] [F ]
2  2


0.5 = - log [H ] 1  1  1
2

   104   104     1012   K sp ;
 2 2 8
A log (-0.5)= [H ]     
no precipitation
[H ] =3.16
(K sp  1.7  1010 )
[OH ]  10.84  no. of moles

2
vol. 1  1 
(b) Ionic product    102   103 
2  2 
Sol.10.
KOH HCOOH 1 
   108   Ksp ; precipitation
0.2M 0.1M 8 
40ml 160ml 2
1  1 
(c) Ionic product    105   103 
K a  2 104  2  2 
No. of millimoles = M  Vol 1 
 milimoles of KOH = 0.2  40=8
   1011   Ksp ; precipitation
8 
milimoles of HCOOH = 0.1  160=16 2
milimoles of HCOOK produced = 8 1  1 
(d) Ionic product    103   105 
milimoles of HCOOH remained = 16 - 8 = 8 2  2 
millimoles of salt 1 
pH  pKa  log    1013   Ksp ; no precipitation
milimoles of acid 8 
8 Hence correct answer is (b).
  log(2  104 )  log 4  0.3010  3.699
8
pOH  14  3.699  10.3 Sol.18. K sp (AgBr)  5  1013

Ag HBr
Sol.12. Weak acid HA pKa = 4.5
50 ltr. 50 ltr.
3 2
Sol.13. A2 X3 2A  3X
2y 3y 105 mole 2  107 mole
Ksp  [A]2 [X]3  (2 y)2 (3y)3  108y5 105
[Ag ]   0.2  106  2  107 M
50
Sol.14. HgSO4 Hg2  SO 42 K sp  [Ag ][Br  ]

K sp (HgSO4 )  6.4  105  [Hg2 ][SO 42 ] K sp  [Ag ]  [Br  ]

K sp  solubility 0.7  106 or 7  107 M

0.64  104  solubility(mole per litre) Sol.19. pH of AgA = 9

c Ksp(AgA)= ?
Sol.15. Similar to Sol.13. Ka (HA) = 1010
Sol.16. Lesser the Ksp , more the solubility. AgA Ag  A  ;K sp (AgA)  [Ag ][A  ]
Sol.17. We know that precipitation occurs
only when ionic product exceeds the value HA H  A ;Ka  1010
of solubility product. [Ag ]  109 ; K a  [H ][A  ] ;
When equal volumes of solutions containing
K sp  [Ag ][A  ]105  [H ][A  ]
Ca2 and F are mixed, [Ca2 ] and [F ]

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Ionic Equilibrium

PREVIOUS YEARS’ QUESTIONS JEE ADVANCED

Q.1 For precipitation : QI.P. > Ksp . 15
end point mL
(B) QIP = [Ca2+] [F–]2 2
2
 Total volume at the end point
 102   103  15
= × = + 2.5 = 10 mL
 2   2  2
Q.7 In HNO3 and CH3COONa combination, if
= 1.25 × 10–9> Ksp , HNO3 is present in limiting amount, it will
precipitate will be formed. be neutralised completely, leaving
behind some excess of CH3COONa :
Q.2 Kp for a given reversible reaction
depends only on
temperature.

Kw
Q.3 Ka (HX) = = 10–4 Q.8 Cl–, CN– and SCN– forms precipitate with
Kb
Cu (I), remove Cu (I) ion from equilibrium
[X  ] and reaction shift in backward direction
 pH = pKa + log
[HX] according to Le-Chatelier's principle.
Q.9 In pure water, solubility
= pKa
9.57
= × 10–3
–
[ [X ] = [HX]] = 4 58
= 1.65 × 10–4 M
Q.4 The reaction of HA with strong base is : Ksp = 4S3 = 4(1.65 × 10–4)3
HA + OH– H2O + A– = 1.8 × 10–11
In 0.02 M Mg(NO3)2;
[A  ] [H ] solubility of Mg(OH)2
K= 
 
[HA][OH ] [H ] K sp 1
= 2

[mg ] 2
K 104
= a  14 =1010 = 1.5 × 10–5 mol L–1
K w 10
= 1.5 10–5 × 58g L–1
Q.5 MX: Ksp = S2 = 4 × l0–8 = 8.7 × 10–4 g L-1

   S = 2 × 10–4 Q.10 (i) 0.20 mole HCl will neutralise 0.20

MX2 : Ksp = 4S3 = 3.2 × 10–4 mole CH3COONa, producing 0.20 mol
   5 = 2 × 10–5 CH3COOH. Therefore, in the solution
M3 X : Ksp = 27S4 moles of CH3COOH = 1.20
= 2.7 × 10–15 moles of CH3COONa = 0.80
   S = 10–4 [Salt]
pH = pKa + log
Order of solubility is: [Acid]
(0.80)
MX > M3X > MX2 = -log (1.8 × 10–5) + log
1.20
2 = 4.56
Q.6 m mol of base = 2.5 × =1
5 (ii) CH3COONa + HCl  CH3COOH+ NaCl
m mol of acid required to reach the end
Initial 0.10 0.20 0 0
point = 1
 Volume of acid required to reach the Final 0 0.10 0.10 0.10
Now the solution has 0.2 mol acetic acid

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Ionic Equilibrium

and 0.1 mole HCl. Due to presence of HCl,

ionisation of CH3COOH can be ignored
(common mainly due to HCl.
  [H+] = 0.10
  pH = – tog (0.10) = 1.0
Q.11 SO2(g)+NO2(g)  SO3(g)+NO(g)
1–x 1–x x x
Qc = l < Kc, ie, reaction proceed in forward
direction to attain equilibrium.
2
x 
 16 =  
1x
 x = 0.80
 [NO] = 0.80 M, [NO2] = 0.20 M

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