Ionic Equilibrium (Advanced)

IONIC EQUILIBRIUM-II

 Marked questions are recommended for Revision.

PART - I : SUBJECTIVE QUESTIONS
Section (A) : pH calculation : Buffer solutions generated from Polybasic acid /
Polyacidic base, Buffer capacity
Commit to memory :
pH calculation : Buffer solutions generated from Polybasic acid (HnX) :
[Hn–1X– ] [Hn–2 X2– ]
(i) HnX + Hn–1X– : pH = p K a1 + log (ii) Hn–1X– + Hn–2X2– : pH = p K a2 + log
[Hn X] [Hn–1X– ]
[Xn– ]
(iii) HX(n–1)– + Xn– : pH = p K an + log
[HX(n–1)– ]
Buffer capacity : Moles of a strong acid or strong base required to change the pH of 1 L of a buffer by
one unit.
Let there be a buffer solution of volume 1 L with ‘b’ mole of anion (coming from salt) and ‘a’ mole of
weak acid.
dx (a + x)(b – x) ab
B.C. = = 2.303  2.303
dΔpH a+b a +b
Condition for maximum buffer capacity : [Acid] = [Anion of salt]

A-1. An enviromental chemist needs a carbonate buffer of pH 10 to study the effects of the acidification of
limestone–rich soils. How many grams of Na2CO3 must be added to 1.5 L of freshly prepared 0.2 M
NaHCO3 to make the buffer ? For H2CO3, K a1 = 4.7 × 10–7; K a2 = 4.7 × 10–11.
Section (B) : pH calculation : Monobasic acid - Monoacidic base Titrations
Commit to memory :
pH calculation : Monobasic acid-Monoacidic base Titrations :
Carry out chemical reaction between the two components, apply mole concept, observe the final
composition of the mixture and then calculate pH accordingly (using different cases dealt in Ionic
Equilibrium-I).
In titration of WA by SB :
x
At half equivalence point : pH = pKa ; pHx % neutralisation = pKa +
100 − x
In titration of WB and SA :
x
At half equivalence point : pOH = pKb ; pOHx % neutralisation = pKb +
100 − x
B-1. Calculate pH of the following mixtures. Given : Ka of CH3COOH = 2 × 10–5 and Kb of NH4OH = 2 × 10–5.
(a) 50 mL of 0.10 M NaOH + 50 mL of 0.10 M HCl.
(b) 50 mL of 0.10 M NaOH + 50 mL of 0.05 M CH3COOH.
(c) 50 mL of 0.05 M NaOH + 50 mL of 0.10 M CH3COOH.
(d) 50 mL of 0.10 M NH4OH + 50 mL of 0.05 M HCl.
(e) 50 mL of 0.10 M NH4OH + 50 mL of 0.10 M HCl.
(f) 50 mL of 0.05 M NH4OH + 50 mL of 0.05 M CH3COOH.
B-2. 0.1 M CH3COOH solution is titrated against 0.05 M NaOH solution. Calculate pH at 1/4th and 3/4th
stages of neutralization of acid. Given : pH of 0.1 M CH 3COOH solution is 3.
 Ionic Equilibrium (Advanced)
Section (C) : pH calculation : Titration of Salts, Polyprotic acid, Polyacidic base
Commit to memory :
pH calculation : Titration of Polyprotic acid, Polyacidic base :
Carry out chemical reaction between the two components, apply mole concept, observe the final
composition of the mixture and then calculate pH accordingly (using different cases dealt in Ionic
Equilibrium-I).
In titration of HnX by strong base :
At half equivalence point w.r.t 1st neutralisation : pH = p K a1 ;
pK a2 + pK a1
At equivalence point w.r.t 1st neutralisation : pH = ;
2
At half equivalence point w.r.t 2nd neutralisation : pH = p K a2 ;
pK a3 + pK a2
At equivalence point w.r.t 2nd neutralisation : pH = ;
2
1
At equivalence point w.r.t last neutralisation : pH = (pK w + pK an + logC) .
2
In titration of Polyacidic base B by strong acid :
At half equivalence point w.r.t 1st neutralisation : pOH = p K b1 ;
pK b2 + pK b1
At equivalence point w.r.t 1st neutralisation : pOH = ;
2
At half equivalence point w.r.t 2nd neutralisation : pOH = p Kb2 ;
pKb3 + pKb2
At equivalence point w.r.t 2nd neutralisation : pH = ;
2
1
At equivalence point w.r.t last neutralisation : pH = (pK w – pK bn – logC) .
2

C-1. 50 mL of 0.05 M Propane-1,2-diamine solution is titrated with 0.1 M HCl solution at 25ºC. Determine the
pH of solutions obtained by adding following volumes of HCl solution :
(a) 12.5 mL (b) 25 mL (c) 30 mL
Given : p K b1 and p Kb2 of weak base are 4.18 and 7.39 respectively.

C-2. Determine the [H+] at half-equivalence point and pH at equivalence point during the titration of a 50 mL,
0.1 M NH4Cl solution with 0.1 M NaOH solution at 25ºC. Given : Kb of NH3 = 2 × 10–5.
 Ionic Equilibrium (Advanced)

PART - II : ONLY ONE OPTION CORRECT TYPE

Section (A) : pH calculation : Buffer solutions generated from Polybasic acid /
Polyacidic base, Buffer capacity
Commit to memory :
pH calculation : Buffer solutions generated from Polybasic acid (HnX) :
[Hn–1X– ] [Hn–2 X2– ]
(i) HnX + Hn–1X– : pH = p K a1 + log (ii) Hn–1X– + Hn–2X2– : pH = p K a2 + log
[Hn X] [Hn–1X– ]
[Xn– ]
(iii) HX(n–1)– + Xn– : pH = p K an + log
[HX(n–1)– ]
Buffer capacity : Moles of a strong acid or strong base required to change the pH of 1 L of a buffer by
one unit.
Let there be a buffer solution of volume 1 L with ‘b’ mole of anion (coming from salt) and ‘a’ mole of
weak acid.
dx (a + x)(b – x) ab
B.C. = = 2.303  2.303
dΔpH a+b a +b
Condition for maximum buffer capacity : [Acid] = [Anion of salt]

A-1. The pH of a solution resulting from the addition of 12.5 ml of 0.1 M HCl to 50 ml of a solution containing
0.15 M CH3COOH & 0.2 M CH3COONa will be : (Given : pKa of CH3COOH= 4.74)
(A) 4.74 (B) < 4.74 (C) > 4.74 (D) > 9.26

A-2. What % of the carbon in the H2CO3 – HCO3– buffer should be in the form of HCO3–, so as to have a
neutral solution ? ( K a1 of H2CO3= 4 × 10–7)
(A) 20 % (B) 40 % (C) 60 % (D) 80%

A-3. Buffer capacity of a buffer solution is x. The volume of 1 M NaOH solution added to 100 mL of this
solution if change the pH by 1 is :
(A) 0.1 x mL (B) 10 x mL (C) 100 x mL (D) x mL

Section (B) : pH calculation : Monobasic acid - Monoacidic base Titrations

Commit to memory :
pH calculation : Monobasic acid - Monoacidic base Titrations :
Carry out chemical reaction between the two components, apply mole concept, observe the final
composition of the mixture and then calculate pH accordingly (using different cases dealt in Ionic
Equilibrium-I).
In titration of WA by SB :
x
At half equivalence point : pH = pKa ; pHx % neutralisation = pKa +
100 − x
In titration of WB and SA :
x
At half equivalence point : pOH = pKb ; pOHx % neutralisation = pKb +
100 − x

B-1. Upon titrating 50 mL of 1.96% (w/v) H2SO4 with a KOH solution (containing 11.2 g KOH per litre of
solution), on adding 50 mL KOH solution :
(A) Equivalence point has been just reached. (B) Equivalence point has been crossed.
(C) pH of resulting solution = 1 (D) pH of resulting solution = 7
 Ionic Equilibrium (Advanced)
B-2. 100 mL of 0.02 M benzoic acid (pKa = 4.2) is titrated using 0.02 M NaOH. pH after 50 mL and
100 mL of NaOH have been added are :
(A) 2.1, 8.1 (B) 4.2, 7 (C) 4.2, 8.1 (D) 4.2, 8.25

B-3. In the above question, upon 75% neutralisation of Benzoic acid, select the INCORRECT statement :
(A) Resulting solution will be a buffer solution. (B) pH = 4.2 + log 3
(C) Both (A) & (B) (D) None of these

B-4. Which of the following solutions have different pH ?

(i) 100 mL of 0.2 M HCl + 100 mL of 0.4 M NH3
(ii) 50 mL of 0.1 M HCl + 50 mL of 0.2 M NH3
(iii) 100 mL of 0.3 M HCl + 100 mL of 0.6 M NH3
(A) i & ii (B) ii & iii (C) i & iii (D) All will have same pH.
B-5. Upon titrating a solution of weak monoprotic acid with a weak monoacidic base solution, at equivalence
point :
(A) pH in general would increase if both solutions are first diluted to 10 times the original volume & then
titration is carried out.
(B) pH in general would decrease if both solutions are first diluted to 10 times the original volume &
then titration is carried out.
(C) pH in general would remain same (= 7) if both solutions are first diluted to 10 times the original
volume & then titration is carried out.
(D) pH in general could be less than, greater than or equal to 7 if both solutions are first diluted to 10
times the original volume & then titration is carried out.

Section (C) : pH calculation : Titration of Salts, Polyprotic acid, Polyacidic base

Commit to memory :
pH calculation : Titration of Polyprotic acid, Polyacidic base :
Carry out chemical reaction between the two components, apply mole concept, observe the final
composition of the mixture and then calculate pH accordingly (using different cases dealt in Ionic
Equilibrium-I).
In titration of HnX by strong base :
At half equivalence point w.r.t 1st neutralisation : pH = p K a1 ;
pK a2 + pK a1
At equivalence point w.r.t 1st neutralisation : pH = ;
2
At half equivalence point w.r.t 2nd neutralisation : pH = p K a2 ;
pK a3 + pK a2
At equivalence point w.r.t 2nd neutralisation : pH = ;
2
1
At equivalence point w.r.t last neutralisation : pH = (pK w + pK an + logC) .
2
In titration of Polyacidic base B by strong acid:
At half equivalence point w.r.t 1st neutralisation : pOH = p K b1 ;
pK b2 + pK b1
At equivalence point w.r.t 1st neutralisation : pOH = ;
2
nd
At half equivalence point w.r.t 2 neutralisation : pOH = p Kb2 ;
pKb3 + pKb2
At equivalence point w.r.t 2nd neutralisation : pH = ;
2
1
At equivalence point w.r.t last neutralisation : pH = (pK w – pK bn – logC) .
2
 Ionic Equilibrium (Advanced)
C-1. The total number of different kind of buffers obtained during the titration of H 3PO4 with NaOH are :
(A) 3 (B) 1 (C) 2 (D) Zero

C-2 (
Upon titration a solution of Ethylene diamine Kb1 = 8  10−5 ; Kb2 = 2.7  10−8 ) with HCl solution, pH
value of solution at Ist equivalence point depends upon :
(A) Initial concentration of weak base solution (B) Initial concentration of strong acid solution
(C) Both (A) & (B) (D) None of these

C-3. What will be the pH at the equivalence point during the titration of a 100 mL 0.2 M solution of
CH3COONa with 0.2 M solution of HCl ? Ka = 2 × 10–5.
(A) 3 – log 2 (B) 3 + log 2 (C) 3 – log 2 (D) 3 + log 2

 Marked questions are recommended for Revision.

PART - I : SINGLE AND DOUBLE VALUE INTEGER TYPE

1. 15 mL sample of 0.15 M NH3(aq) is titrated against 0.1M HCl(aq). What is the pH at the end point ? Kb
of NH3(aq) = 1.8 × 10–5. Report the answer rounding it off to the nearest whole number.

2. A 0.252 g sample of unknown organic base is dissolved in water and titrated with a 0.14 M HCl solution.
After the addition of 20 mL of acid, a pH of 10.7 is recorded. The equivalence point is reached when a
total of 40 mL of HCl is added. If the base and acid combine in a 1 : 1 molar ratio, then 'a' g is the
molar mass of the organic base and 'b' is the ionisation constant of base. Report your answer as
 a 
 .
 1000 b 

PART - II : ONE OR MORE THAN ONE OPTIONS CORRECT TYPE

1. Aniline behaves as a weak base. When 0.1 M, 50 mL solution sample of aniline was mixed with 0.2 M,
12.5 mL solution of HCl, the pH of resulting solution was 8. Then :
(A) pH of 0.01 M solution of anilinium chloride is 5.
(B) pH of original solution of aniline is 3.5.
(C) Upon adding the same aniline sample to the above mixture, pH of resulting solution becomes 8.48.
(D) Upon adding the same HCl sample to the above mixture, pH of resulting solution becomes 4.59.

2. Which of the following mixtures will act as buffer ?

(A) H2CO3 + NaOH (1.5 : 1 molar ratio) (B) H2CO3 + NaOH (1.5 : 2 molar ratio)
(C) NH4OH + HCl (5 : 4 molar ratio) (D) NH4OH + HCl (4 : 5 molar ratio)

3. Titration curves for 0.1M solutions of three weak acids HA 1, HA2 and HA3 with ionization constants K1,
K2 and K3 respectively with a strong base are plotted as shown in the figure. Which of the following
options is/are true ?
 Ionic Equilibrium (Advanced)

12

10

pH 8

6 K3
4 K2
K1
2

Volume of strong base added

(A) K2 = (K1 + K3)/2 (B) pK1 < pK3 (C) K1 > K2 (D) K2 > K3

PART - III : COMPREHENSION

Read the following passage carefully and answer the questions.
Comprehension # 1
[Base]
The pH of basic buffer mixtures is given by : pH = pKa + log , whereas pH of acidic buffer
[Salt]
[Salt]
mixtures is given by : pH = pKa + log . Addition of little acid or base although shows no
[Acid]
[Base] [Salt]
appreciable change in pH for all practical purposes, but since the ratio for changes, a
[Salt] [Acid]
slight decrease or increase in pH results.
1. A solution containing 0.2 mole of dichloroacetic acid (Ka = 5 × 10–2) and 0.1 mole sodium
dichloroacetate in one litre solution has [H+] :
(A) 0.05 M (B) 0.025 M (C) 0.10 M (D) 0.005 M
2. The volume of 0.2 M NaOH needed to prepare a buffer of pH 4.74 with 50 mL of 0.2 M acetic acid is :
(pKb of CH3COO– = 9.26)
(A) 50 mL (B) 25 mL (C) 20 mL (D) 10 mL
3. The ratio of pH of solution (I) containing 1 mole of CH 3COONa and 1 mole of HCI and solution (II)
containing 1 mole of CH3COONa and 1 mole of acetic acid in one litre is :
(A) 1 : 2 (B) 2 : 1 (C) 1 : 3 (D) 3 : 1
Comprehension # 2
Phosphoric acid ionizes according to the following equations :
H3PO4(aq) H+ (aq) + H2PO4– (aq) ; K1 = 7 × 10–3
–
H2PO4 (aq) + 2–
H (aq) + HPO4 (aq) ; K2 = 6 × 10–8
2–
HPO4 (aq) + 3–
H (aq) + PO4 (aq) ; K3 = 4.5 × 10–13
4. If you are asked to prepare a buffer with a pH = 7.00, what may be the molar ratio of the species that
should be used in the solution ?
(A) 0.6 (B) 0.8 (C) 2 (D) 4
5. Assume 50 mL of the buffer prepared in the previous part is available in which more abundant species
has a concentration of 0.1 M. If to this solution, 20 mL 0.1 M NaOH is added further, what will be the
new pH ?
(A) 6.56 (B) 7.44
(C) 7.78 (D) Same as before as it's a buffer
 Ionic Equilibrium (Advanced)
* Marked questions may have more than one correct option.
PART - I : JEE (ADVANCED) / IIT-JEE PROBLEMS (PREVIOUS YEARS)
1. 500 ml of 0.2 M aqueous solution of acetic acid is mixed with 500 mL of 0.2 M HCl at 25ºC.
(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. [JEE-2002, 5/60]
2. 0.1 M NaOH is titrated with 0.1 M HA till the end point. K a for HA is 5.6 × 10–6 and degree of hydrolysis
is less compared to 1. Calculate pH of the resulting solution at the end point. [JEE-2004, 2/60]
3. 0.1 mole of CH3NH2 (Kb = 5 × 10–4) is mixed with 0.08 mole of HCl and diluted to one litre. What will be
the H+ concentration in the solution ? [JEE-2005, 3/84]
(A) 8 × 10–2 M (B) 8 × 10–11 M (C) 1.6 × 10–11 M (D) 8 × 10–5 M
2 2
4. 2.5 mL of M weak monoacidic base (Kb = 1 × 10–12 at 25°C) is titrated with M HCl in water at
5 15
25°C. The concentration of H+ at equivalence point is : (Kw = 1 × 10–14 at 25°C) [JEE-2008, 3/163]
(A) 3.7 × 10–14 M (B) 3.2 × 10–7 M (C) 3.2 × 10–2 M (D) 2.7 × 10–2 M
5.* Aqueous solutions of HNO3, KOH, CH3COOH and CH3COONa of identical concentrations are provided.
The pair(s) of solutions which form a buffer upon mixing is (are) : [JEE-2010, 3/163]
(A) HNO3 and CH3COOH (B) KOH and CH3COONa
(C) HNO3 and CH3COONa (D) CH3COOH and CH3COONa
Comprehension #
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 5.7ºC was measured for the beaker and its contents (Expt. 1).
Because the enthalpy of neutralization of a strong acid with a strong base is a constant (–57.0 kJ
mol–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 (Ka = 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 5.6ºC was measured.
(Consider heat capacity of all solutions as 4.2 J g–1 K–1 and density of all solutions as 1.0 g mL–1)
6. Enthalpy of dissociation (in kJ mol–1) of acetic acid obtained from the Expt. 2 is :
[JEE (Advance)2015, 4/168]
(A) 1.0 (B) 10.0 (C) 24.5 (D) 51.4
7. The pH of the solution after Expt. 2 is [JEE (Advance)2015, 4/168]
(A) 2.8 (B) 4.7 (C) 5.0 (D) 7.0
8. Dilution processes of different aqueous solutions, with water, are given in LIST-I. The effects of dilution
of the solution on [H+] are given in LIST-II.
(Note : degree of dissociation () of weak acid and weak base is <<1; degree of hydrolysis of salt <<1;
[H+] represents the concentration of H+ ions) [JEE (Advance)2018, 3/120]
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 of
0.1 M acetic acid) diluted to 80 mL 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 →  ; 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
 Ionic Equilibrium (Advanced)
PART - II : JEE (MAIN) (PREVIOUS YEARS)
JEE(MAIN) OFFLINE PROBLEMS
1. An alkali is titrated against an acid with methyl orange as indictor, which of the following is a correct
combination? [JEE(Main)-2018, 4/120]
Base Acid End point
(1) Weak Strong Yellow to pinkish red
(2) Strong Strong Pink to colourless
(3) Weak Strong Colourless to pink
(4) Strong Strong Pinkish red to yellow

EXERCISE - 1
PART - I
A-1. K A-2. 15 g Na2CO3 B-1. (a) 7, (b) 12.4, (c) 4.7, (d) 9.3, (e) 5.3, (f) 7
B-2. 4.52, 5.48 C-1. (a) 9.82 (b) 8.215 (c) 7.21 C-2. 5 × 10–10 M; 11
PART - II
A-1. (A) A-2. (D) A-3. (C) B-1. (C) B-2. (C)
B-3. (D) B-4. (D) B-5. (D) C-1. (A) C-2 (D)
C-3. (A)

EXERCISE - 2
PART - I
1. 5 (exact answer = 5.24) 2. 90 (a = 45 & b = 5 × 10–4)
PART - II
1. (ACD) 2. (ABC) 3. (BCD)
PART - III
1. (A) 2. (B) 3. (A) 4. (A) 5. (B)

EXERCISE - 3
PART - I
1. (a) 0.0175%, 1 (b) 4.757 2. 8.98  9 3. (B) 4. (D)
5.* (CD) 6. (A) 7. (B) 8. (D)

PART - II
JEE(MAIN) OFFLINE PROBLEMS

1. (1)