(Physical Chemistry) IONIC EQUILIBRIUM

SECTION–I(i)
Straight Objective Type
1. The dissociation constant of acetic acid is 0.000018 and that for cyanoacetic acid is 0.0036 at
298 K. What would be the ratio of volumes of the two acid solutions, each containing equal
moles of the acids, so that the solutions becomes isohydric?
(A) 1 : 1 (B) 1 : 200 (C) 1 : 200 (D) 200 : 1
2. Calculate the pH of 0.02 M-HA solution. The value of Ka for HA = 2×10–12 (log2 = 0.3, log3 =
0.48).
(A) 6.65 (B) 6.70 (C) 6.85 (D) 6.52
3. A solution has initially 0.1 M-HCOOH and 0.2 M-HCN. The value of Ka for HCOOH = 2.56×10–5, Ka
of HCN = 9.6×10–10. The only incorrect statement for the solution is (log2 = 0.3)
(A) [H+] = 1.6×10–3 M (B) [HCOO–] = 1.6×10–3 M
(C) [CN–] = 1.2×10–7 M (D) pOH = 2.8
4. An amount of 0.15 mole of pyridinium chloride has been added into 500 mL of 0.2 M pyridine
solution. Calculate pH of the resulting solutions assuming no change in volume. The value of Kb
for pyridine = 1.5×10–9 (log2 = 0.3, log0.3 = 0.48).
(A) 9.0 (B) 5.0 (C) 8.64 (D) 5.36
5. The correct order of increasing [OH–] in the following aqueous solutions is
(A) 0.01 M-NaHCO3 < 0.01 M-NaCN < 0.01 M-KCl
(B) 0.01 M-KCl < 0.01 M-NACN < 0.01 M-NaHCO3
(C) 0.01 M-KCl < 0.01 M-NaHCO3 < 0.01 M-NACN
(D) 0.01 M-NaCN < 0.01 M-KCl < 0.01 M-NaHCO3
6. Given Ag(NH3 )2+ Ag+ + 2NH3 , Kc = 7.2×10–8 and Ksp of AgCl = 1.8 × 10–10 at 298 K. If
ammonia is added to a water solutions containing excess of AgCl(s) only, then calculate the
concentration of the complex in 1.0 M aqueous ammonia.
(A) 1.0 M (B) 0.091 M (C) 0.0455 M (D) 0.023 M
7. Ksp of AgCl, Ag2CrO4 and AgBr are 10–10, 10–13 & 10–12 respectively. If to a solution of 0.1 M each
of Cl–, Cr O 24 − and Br– ions AgNO3 is added slowly, which will precipitate first :

(A) AgCl (B) Ag2CrO4 (C) AgBr (D)All simultaneously

8. A volume of 50 mL of a solutions which is 0.05 M in the acid HA (pKa = 3.80) and 0.08 M in HB
(pKa = 8.20) is titrated with 0.2 M-NaOH solution. The pH of solution at the first equivalent
point is (log2 = 0.3, log1.6 = 0.2)
(A) 6.0 (B) 9.2 (C) 4.8 (D) 5.9

APNI KAKSHA 1
(Physical Chemistry) IONIC EQUILIBRIUM
SECTION–I(ii)
One or More than One Correct Type (4, –1)
1. Which of the following results) is/are correct for the equilibrium state in a solutions originally
having 0.1 M-CH3COOH and 0.1 M-HCl? The value of Ka for CH3COOH = 1.8×10–5.
(A) [H+] = 0.1 M
(B) [CH3COO–] = 1.8×10–5 M
(C) Degree of dissociation of acetic acid = 1.8×10–4
(D) [H+] from water = 10–13 M
2. Which of the following statement(s) is/are correct?
(A) The pH of 10–8 M-HCl solution is 8.
(B) The conjugate base of H 2 PO−4 is HPO 24−

(C) Ionic product of water increases with the increase in temperature

(D) When a solution of a weak monoprotic acid is titrated against a strong base, at half
neutralization point, pH = pKa/2
3. A buffer solution can be prepared from a mixture of
(A) NH4Cl and NaOH in 2 : 1 mole ratio
(B) CH3COONa and HCl in 1 : 1 mole ratio
(C) CH3COONa and HCl in 2 : 1 mole ratio
(D) CH3COONa and HCl in 1 : 2 mole ratio
4. 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

5. 0.1 mol of H3PO4 is added to 1 litre buffer solution having pH = 2, then -
(for H3PO4 K1 = 10–4 M ; K2 = 10–8 M ; K3 = 10–13 M)
(A) concentration of H2PO −4 is 10–3 (B) concentration of HPO −4 2 is 10–8

(C) concentration of PO −4 3 is 10–20 (D) concentration of OH– is 10–12

6. The solubility of sparingly soluble salt CH3COOAg in a buffer solution of pH = X(X < 7)
(A) Increases as the value of X decreases
(B) Decreases as the value of X decreases
(C) Solubility of salt is more compare to that in a pure water.
(D) Will be smaller if the Ka value of the CH3COOH is greater
APNI KAKSHA 2
(Physical Chemistry) IONIC EQUILIBRIUM
SECTION–I(iii)
Linked Comprehension Type
Paragraph for Question 14 & 15
Amino acid glycine (NH2–CH2–COOH) exists as a zwitterion in aqueous solution. The Ka and Kb
values of glycine are 1.6 × 10–10 (pKa = 9.8) and 2.5×10–12 (pKb = 11.6), respectively. The Ka and
Kb values are zwitterion of amino acid with the following structure [NH3–CH2–COO–]
1. What is the value of Kb for –NH2 group in glycine?
(A) 4×10–3 (B) 1.6×10–10 (C) 6.25×10–5 (D) 2.5×10–12
2. An aqueous solution of glycine has pH
(A) nearly 7 (B) nearly 7.9 (C) nearly 6.1 (D) nearly 11.5

APNI KAKSHA 3
(Physical Chemistry) IONIC EQUILIBRIUM
SECTION–I(iv)
Subjective Type Questions
1. The pH range of a basic indicator (InOH) is 3.4 – 4.6. Determine the ratio [In+]/[InOH] above
which the solution appears only in the colour of In+? (log2 = 0.3)
2. The pH of blood stream is maintained by a proper balance of H2CIO3 and NaHCO3
concentrations. What volume of 5M-NaHCO3 solution should be mixed with a 10 mL sample of
blood which is 2M in H2CO3 in order to maintain a pH of 7.4? The value of Ka for H2CO3 in blood
is 8.0×10–7 (log2 = 0.3).
3. Solubility of Ag2CrO4 in water at 25ºC is 10–3M. If 0.1 moles of K2CrO4 are added to 1 litre
saturated solution of Ag2CrO4. Then find moles of Ag2CrO4 precipitated at 25ºC.
If your answer is x × 10y then fill ‘x’ in OMR. Where ‘x’ is single digit number.
4. A sample of 100 ml, 0.1M weak acid, HA (Ka = 1.0 × 10–5), is titrated with standard 0.1M KOH.
How many ml of KOH will have been when the pH in the titration flask is 5.

APNI KAKSHA 4
(Physical Chemistry) IONIC EQUILIBRIUM
JEE ADVANCED Previous Year's Questions
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 6.7×10–6M. 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 < NH4Cl < NaCN < HCl (B) HCl < NH4Cl < NaCl < NaCN

(C) NaCN < NH4Cl < 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 pKa of H2SO3 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 = Sp+q, pp. qq (B) Ls = Sp+q, pp. qp

(C) Ls = Spq, pp. qq (D) Ls = Spq, (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. Ka 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]

APNI KAKSHA 5
(Physical Chemistry) IONIC EQUILIBRIUM
10. A solution which is 10–3 M each in Mn2+, Fe2+, Zn2+ and Hg2+ is treated with 10–16M

sulphide ion. If Ksp, 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

11. HX is a weak acid (Ka = 10–5). It forms a salt NaX (0.1 M) 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 CH3NH2 (0.1 mole, Kb = 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, H2CO3, HCO32– (B) H2CO3, CO32–

(C) CO32– , HCO3– (D) CO2, H2CO3

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 [JEE 2008]

(K w = 1 × 10−14 at 25∘ C)
(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 0.01M
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

APNI KAKSHA 6
(Physical Chemistry) IONIC EQUILIBRIUM
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 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 Advance 2013]
(A) 1 × 10−4 (B) 1 × 10−5 (C) 1 × 10−6 (D) 1 × 10−3
21. 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
0.1MAgNO3 solution is: [JEE Advance 2013]
(A) 1.1 × 10−11 (B) 1.1 × 10−10 (C) 1.1 × 10−12 (D) 1.1 × 10−9
22. The solubility of a salt of weak acid (AB) at pH3 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 ) [JEE Advance 2018]
23. 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. [JEE Advance 2018]
(Note: Degree of dissociation (α) of weak acid and weak base is ≪< 1; degree of hydrolysis of
salt ≪< 1; [H + ]represents the concentration of H + ions)
LIST-I LIST-II
P (10 mL of 0.1MNaOH + 20 mL of 0.1M acetic acid) 1. the value of [H + ]does not
diluted to 60 mL change ondilution
Q (20 mL of 0.1MNaOH + 20 mL of 0.1M acetic acid) 2. the value of [H + ]changes to
diluted to 80 mL half of its initial value on
dilution
R (20 mL of 0.1MHCl + 20 mL of 0.1M ammonia 3. the value of [H + ]changes to
solution) diluted to 80 mL two times of its initial value
on dilution
S 10 mL saturated solution of Ni(OH)2 in equilibrium 4. the value of [H + ]changes to
with excess solid Ni(OH)2 is diluted to 20 mL (solid 1
times of its initial value on
√2
Ni(OH)2 is still present after dilution).
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

APNI KAKSHA 7
(Physical Chemistry) IONIC EQUILIBRIUM
24 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 [JEE Advance 2020]
B + HA &rarr; BH + + A− .

25 An acidified solution of 0.05MZn2+ is saturated with 0.1MH2 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 . [JEE Advance 2020]

26. 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 ] [JEE Advance 2022]
27. Concentration of H2 SO4 and Na2 SO4 in a solution is 1M 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
[Given: Solubility product of PbSO4 (𝐾𝑠𝑝 ) = 1.6 × 10−8 . For H2 SO4 , 𝐾𝑎1 is very large and 𝐾𝑎2 =
1.2 × 10−2 ] [JEE Advance 2022]

APNI KAKSHA 8
(Physical Chemistry) IONIC EQUILIBRIUM
ANSWER KEY
SECTION–I(i)
1. (C) 2. (A) 3. (D) 4. (B) 5. (C) 6. (C) 7. (C)
8. (D)
SECTION–I(ii)
1. (ABCD) 2. (BC) 3. (AC) 4. (ACD) 5. (ACD) 6. (ACD)
SECTION–I(iii)
1. (C) 2. (C)
SECTION–I(iv)
1. (4) 2. (0080) 3. (9 × 10–4) (9) 4. (50)
JEE ADVANCED Previous Year's Questions
1. pH = 11.3010 2. s = 1.203 × 10–3M
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 (C, D)
19. (7) 20. (A) 21. (B) 22. (4.47)
23. (D) 24. (3.3) 25. (0.2) 26. (10.02) 27. (6)

APNI KAKSHA 9
(Physical Chemistry) IONIC EQUILIBRIUM
SOLUTION
SECTION–I(i)
1. [H+ ]CH3COOH = [H+ ]CH2 (CN)COOH

n n V 1
Or 0.000018  = 0.0036   1=
V1 V2 V2 200

2. [H+] = K a .C = 2 10−12  0.02 = 2×10–7 M

As [H+] is very small, contribution of H+ from water must be considered.

HA H+ + A–
Equilibrium (0.02 – x)M (x+y)M xM
H2O H+ + OH–
Equilibrium (x+y)M yM
H + ][A − ]
Now, Ka =
[HA]
(x + y).x (x + y).x
 2×10–12 = =
(0.02 − x) 0.02
or, 4×10–14 = (x+y).x .......(1)
and Kw = p[H+][OH–]  10–14 = (x+y).y .......(2)

From (1) + (2) , (x+y) = 5 10−14 M = [H+]

pH = –log(5×10–14)1/2 = 6.65
3. HCN H+ + CN–
Equilibrium (0.2 – x)M (x+y)M xM
(x + y).x y.x
9.6×10–10 = 
(0.2 − x) 0.2

HCOOH H+ + HCOO–
Equilibrium (0.1 – x)M (x+y)M yM
(x + y).y y.y
2.56×10–5 = 
(0.1 − y) 0.1
 y = 1.6×10–3 and x = 1.2×10–7
Option (d) may be answered without solving because solution is acidic.
k 6 .[Pyridine] 1.5 10−9  0.2
4. [OH–] = =
[Pyridinium ion]  0.15 
 1000 
 500 
= 1×10–9 M
APNI KAKSHA 10
(Physical Chemistry) IONIC EQUILIBRIUM
 pOH = –log(10–9) = 9.0 pH = 5.0
5. The order of acidic strength is HCl > H2CO3 > HCN
6. AgCl(s) + 2NH3(aq) Ag(NH3)2+(aq) + Cl–(aq)
1.0 M 0 0
Equ. (1–2x)M xM xM
[Ag(NH 3 ) 2+ ][Cl − ] [Ag + ] K sp
Now, Keq =  =
[NH 3 ]2 [Ag + ] K c

1.8 10−10 1
= −8
=
7.2 10 400
x.x 1 1
Now, = x= = 0.045 M
(1 − 2 x) 2
400 22
8. As HA is stronger acid, it will react first. For first equivalent point VNaOH × 0.2 = 50×0.05 VNaOH
= 12.5 mL
At first equivalent point,
0  0.05
[A–] = = 0.04 M
62.5
0  0.08
[HB] = = 0.064 M
62.5
Now, A− + HB B− + HA ;
0.04− x 0.064− x x x
=0.04 =0.064

K a (HB) 10−8.2
Keq = = = 10–4.4 = 4×10–5
K a (HA) 10−3.8

x.x
4×10–5 = x = 3.2×10–4
0.04  0.064
[H + ][A − ]
Now, Ka(HA) =
[HA]

[H + ]  0.04
 1.6×10–4 =
3.2 10−4
 [H+] = 1.28×10–6  pH = 5.9

SECTION–I(ii)
APNI KAKSHA 11
(Physical Chemistry) IONIC EQUILIBRIUM
1. CH3COOH CH3COO – + H+
(0.1− x) M xM (0.1+ x) M
= 0.1M = 0.1M

x  0.1
Now, 1.8×10–5- =  x = 1.8×10–5
0.1
x
and a = = 1.8×10–5
0.1
w
Now, [HT]from water = [OH–] = = 10–13 M
[H + ]acid

2. (C) H2O + H2O H3O+ + OH–; H° = +ve

(D) HA + OH – A – + H 2O
a a 0
2
a a
final
2 2

a/2
PH = p K a + log = p Ka
a/2

3. NH 4Cl + NaOH NH 4OH + NaCl

a b 0
For Buffer:(a − b) 0 b  a b

4. 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.

CH3COONa + HCl CH3COOH + NaCl
a b 0
For Buffer:(a − b) 0 b  a b

5. H3PO4 H2PO −4 + H+ : K1

0.1 – x x 10–2
 0.1
H2PO −4 HPO 24 − + H+ : K2

x–y y 10–2
x
HPO 24 − PO 34− + H+ : K3

y+z z 10–2
y

x 10−2
K1 = 10–4 =  x = 10–3
0.1
y 10−2
K2 = 10–8 =  y = 10–9
x

APNI KAKSHA 12
(Physical Chemistry) IONIC EQUILIBRIUM
z  10−2
K3 = 10–13 =  x = 10–20
y
[H+] [OH–] = 10–14

10−14
[OH–] = = 10–12
10−2
SECTION–I(iii)
+
K b 2 = 2.510−12
1. NH3 − CH3 − COOH K a1 = 410−3

+ K a 2 =1.610−10
NH3 − CH3 − COO− K b1 = 6.2510−5

NH2–CH2–COO–
Required Kb = K b1 = 6s.25×10×10–5

 Ka1
2.  pH =
2
( 1
2
)
p + p K a 2 = (2.4 + 9.8) = 6.1

SECTION–I(iv)
1. For appearance of only ln+ colour,
[ln + ] 4.6 − 3.4
log = = 0.6 = log
[lnOH] 2

[ln + ]
 =4
[lnOH]
[NaHCO3 ]O
2. pH = p Ka + log
[H 2 C O3 ]O

V5
Or, 7.4 = 6.1 + log  V = 80 mL
10  2
3. Ksp = 4s3 = 4 × (10–3)3 = 4 × 10–9
4 × 10–9 = [Ag+]2 [Cr O 24 − ]

= [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
4. HA + KOH ⎯⎯→ kA + H2O
10 0.1M, Vml
(10–0.1V) (0.1V)

APNI KAKSHA 13
(Physical Chemistry) IONIC EQUILIBRIUM
 0.1V 
5 = 5 + log  
 10 − 0.1V 
 10 – 0.1 V = 0.1 V
0.2 V = 10
V = 50 ml

APNI KAKSHA 14
(Physical Chemistry) IONIC EQUILIBRIUM
JEE ADVANCED Previous Year's Questions
1. HCl + NaOH ¾→ NaCl + H2O
2m mol 3mmol 10 -
0 1mmol 2m mol -
1
[OH–] = = 2×10–3
500
pH = 11 + log2 = 11.3
2 pH = 8 Þ pOH = 6
[OH–] = 10–6 M
Pb(OH)2 ¾→ Pb2+ + 2OH–
Ksp = 4s2 = 4×(6.7)3×10–18 = 1.2×10–15
Pb(OH)2 ¾→ 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
10 6
Molar conc. of SO2 in water = Amount of SO2 × Solubility of SO2
= 10×10–6×1.3653
= 1.3653×10–5 M
H2SO3 ¾→ H+ + HSO 3−

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
6. Equation of H2C2O4.2H2O = Equation of NaOH
10 63
  2 = 0.1×V(L)
250 126
1
V(L) =
25
V(mL) = 40
APNI KAKSHA 15
(Physical Chemistry) IONIC EQUILIBRIUM
7. ApBq(s) ¾→ 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 ¾→ 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×a = 1.75×10–5
a = 1.75×10–4
[H+] = 0.1 Þ pH = 1

6
(b) Moles of NaOH = = 0.15 mol
40
CH3COOH + NaOH ¾→ CH3COONa + H2O
ni 0.1 0.05 0 -
nf 0.05 0 0.05 -
Q 0.1 moles NaOH will be consumed by 0.1 mol of HCl
pH = pKa = 4.75
9. T, Kw , H+, pH ¯
10. Which has minimum value of Ksp i.e. HgS
11. X– + H2O ¾→ 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 %

APNI KAKSHA 16
(Physical Chemistry) IONIC EQUILIBRIUM
12. At end point HA will completes reacts with NaOH
HA + NaOH ¾→ 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 ¾→ CH 3 NH 3+ Cl −

0.1 mol 0.08 mol 0

0.02 mo 0 0.05 mol
[CH3 NH 2 ]
[OH–] = Kb×
[CH3 NH3+ ]
0.02 5
= 5×10–4 × = ×10–4
0.08 4
Kw 
[H+] = −
= ×10–10 = 8×10–11 M
[OH ] 5

14. CO2 + H2O ¾→ HCO3− + H+

HCO3− ¾→ 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

APNI KAKSHA 17
(Physical Chemistry) IONIC EQUILIBRIUM
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

 [H+] = 0.1×h = 0.027 M

1
17. pH = (pKw + pKa + logC)
2

1 1
= (14 + 4 + log0.01) = ×16 = 8
2 2
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 HNO3is different.

(D) CH3COOH + CH3COONa

APNI KAKSHA 18
(Physical Chemistry) IONIC EQUILIBRIUM
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. r  [H+]1

Ka  C 1
=
1 100

K a  C = 10–2

Ka = 10–4
21. For Ag2CrO4 Ksp = 1.1×10–12

Ag2CrO4 ⎯→ 2Ag+ (aq) + CrO 24 −

2s+0.1 s

 0.1

(0.1)2 ×s = 1.1×10–12

8 = 1.1×10–10 M

 H+ 
22. s= K sp  + 1
 Ka 

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

= 2 10−5 = 4.47×10–3 M
23. (P) CH3COOH + NaOH ⎯→ CH3COONa + H2O
2m mol 1m mol 0 -
1m mol 0 1m mol -

APNI KAKSHA 19
(Physical Chemistry) IONIC EQUILIBRIUM
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–

Kw  Ka
CH+ =
C

1
[H+] 
C

(R) NH3 + HCl ⎯→ NH4Cl

2m mol 2m mol 0
0 0 2m mol

NH +4 + H2O ⎯→ NH4OH + H+

Kw
[H+] = C  [H+]  C
Kb

(S) Ni(OH)2(s) ⎯→ Ni2+(aq) + 2OH–(aq)

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

24. 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

APNI KAKSHA 20
(Physical Chemistry) IONIC EQUILIBRIUM

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
25. [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

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
+ 2−
H2 S ⇔ 2H + S
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
26. 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

APNI KAKSHA 21
(Physical Chemistry) IONIC EQUILIBRIUM
= 10.32 − log⁡ 2
= 10.32 − 0.3
= 10.02
∴ pH = 10.02
+
27. H2 SO4 ⟶ HM 4 ⁡(K a1 is very large )
+ HSO2−
1M
4
HSO− +
4 ⇌ H + SO4 ⁡
2− 1M
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

[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

APNI KAKSHA 22