Chemical Changes Page 1 of 10

First Paper
Fourth Chapter
Chemical Changes

Sheet-02

Acid-Base Equilibrium

Compiled by:
Md. Ibrahim Khan
Lecturer in Chemistry
Adamjee Cantonment College
Dhaka Cantonment
Mob. 01789139136, 01917660225
Chemical Changes Page 2 of 10

Buffer Solution
An acidic solution has a certain pH. Now adding a small amount of acid or base in this solution the
pH should be changed due to the changing of concentration of H+ ion. But if no change of pH after
adding of a small amount of acid or base is termed as buffering/ resisting of pH or buffer solution.

Definition of Buffer solution: A solution which resists the change of pH after adding a small
amount of acid or base is termed as buffer solution.
Again, the capacity of a buffer solution to resist the change of pH is termed as buffer capacity. Or,
the number of moles of strong mono basic acid or mono acidic base should be added in a 1L buffer
solution to change the pH by 1 unit is called buffer capacity of that buffer solution.
Again, the mechanism or process through which the change of pH resists is termed as buffer action.

Types of buffer solution: Buffer solutions are basically two types. These are-

1. Acidic buffer solution and 2. Basic buffer solution.

1. Acidic buffer solution: A mixture or solution of a weak acid and a salt of this acid with strong
base is acidic buffer solution. Very commonly the pH of an acidic buffer solution is 3.7 to 5.6.
Example: Mixture of CH3COOH and CH3COONa, mixture of HCOOH and HCOONa, Mixture of
HF and NaF etc.

2. Basic buffer solution: A mixture or solution of a weak base and a salt of this base with strong
acid is basic buffer solution. Very commonly the pH of a basic buffer solution is 8.5 to 10.0.
Example: Mixture of NH4OH and NH4Cl, mixture of MOH (a weak base) and MA (salt of this base
with strong acid) etc.

Mechanism of basic buffer solution:

Buffer mechanism: the mechanism or process through which the change of pH resists is termed as
buffer action.

Mechanism of acidic buffer solution: For the explanation of an acidic buffer solution we can take
here an example of ethanoic acid and sodium ethanoate. Both the components of this buffer
dissociate as follows-
CH3COOH ⇌ CH3COO─ + H+ (Weak acid. Dissociates partially and establishes an
equilibrium)
CH3COONa → CH3COO─ + Na+ (Ionic salt. Dissociates completely in solution)

1. Elimination of external H+ ion:

If a small amount of acid i.e., H+ ion is added, this H+ ion adds with CH3COO─ ion to form
undissociated CH3COOH. That’s the above-mentioned equilibrium shifts backward and thus the
external H+ ion eliminated.
H+(aq) + HCOO-(aq) ⇌ CH3COOH(aq)
Moreover, ethanoic acid, produces, is a weak acid. So, in presence of ethanoate ion this ethanoic acid
dissociates negligible amount. That’s why the concentration of H+ ion doesn’t change. As a result,
pH remains same even after the addidtion of external acid (H+).
Notice that, the neutralization of external acid produces same amount (mole) of undissociated weak
acid and decreases the same amount (mole) of salt.

2. Elimination of external OH─ ion:

If a small amount of base i.e., OH─ ion is added from an external source, H+ ion neutralizes that OH─
ion and forms neutral H2O. In this case, the concentration of H+ ion decreases. To minimize the
deficiency of H+ ion the above-mentioned equilibrium shifts forward. Thus, the pH of the solution
remains constant.
H+(aq) + OH-(aq) → H2O(l)
CH3COOH(aq) ⇌ CH3COO-(aq) + H+(aq)
Chemical Changes Page 3 of 10

Notice that, for the neutralization of external OH─ ion, the amount (mole) of salt increases but that
of weak acid decreases.

Mechanism of basic buffer solution: For the explanation of mechanism of basic buffer solution we
can take here a mixture of ammonium hydroxide (NH4OH) and ammonium chloride (NH4Cl). These
two components ionize as follows-
NH4OH ⇌ NH4+ + OH─ (Weak base. Dissociates partially and establishes an equilibrium)
NH4Cl → NH4+ + Cl─ (Ionic salt. Dissociates completely in solution)

1. Elimination of external OH─ ion:

If a small amount of base i.e., OH─ ion is added, this OH─ ion adds with NH4+ ion to form
undissociated NH4OH. That’s the above-mentioned equilibrium shifts backward and thus the
external OH─ ion eliminated.
NH4+(aq) + OH─(aq) ⇌ NH4OH(aq)
Moreover, ammonium hydroxide produces is a weak acid. So, in presence of ammonium ion,
ammonium hydroxide dissociates negligible amount. That’s why the concentration of OH─ ion
doesn’t change. As a result, pH remains same even after the addition of external base (OH─).
Notice that, the neutralization of external base produces same amount (mole) of undissociated weak
base and decreases the same amount (mole) of salt.

2. Elimination of external H+ ion:

If a small amount of acid i.e., H+ ion is added from an external source, OH─ ion neutralizes that H+
ion and forms neutral H2O. In this case, the concentration of OH─ ion decreases at first. To minimize
the deficiency of OH─ ion the above-mentioned equilibrium shifts forward. Thus, the pH of the
solution remains constant.
H+(aq) + OH─(aq) → H2O(l)
NH4OH(aq) ⇌ NH4+(aq) + OH─(aq)
Notice that, for the neutralization of external H+ ion, the amount (mole) of salt increases but that of
weak base decreases.

Calculation of pH of buffer solution: Henderson-Hasselbalch Equation

Calculation of pH of acidic buffer solution:
For the calculation of pH of acidic buffer solution. Let’s consider the buffer made of ethanoic acid
sodium ethanoate.
CH3COOH ⇌ CH3COO─ + H+
CH3COONa → CH3COO─ + Na+
For the above-mentioned equilibrium, we can write,
[CH3 COO− ][H+ ]
Ka = [CH3 COOH]
+ [CH3 COOH]
Or, [H ] = Ka × [CH −
3 COO ]
+ [Acid]
Or, [H ] = Ka × [Salt]
+ [Acid]
Or, -log[H ] = -log(Ka × )
[Salt]
[Acid]
Or, -log[H+] = -logKa +[-log ( [Salt] )]
[Acid]
Or, -log[H+] = -logKa ─ log ( [Salt] )
[Salt]
Or, pH = pKa + log ([Acid])
This equation is Henderson-Hasselbalch equation for the calculation of pH of acidic buffer solution.

Applications:
1. pH can be determined for a buffer solution of unknown pH.
2. For the preparation of a buffer of certain pH, we can determine the ratio of mole of weak acid and
salt.
Chemical Changes Page 4 of 10

Significance: According to the equation,

1. If the concentration or mole number of salt = the concentration or mole number of acid, pH = pKa.
2. If the concentration or mole number of salt > the concentration or mole number of acid, pH > pKa.
3. If the concentration or mole number of salt < the concentration or mole number of acid, pH < pKa.

Calculation of pOH of basic buffer solution:

For the calculation of pOH of basic buffer solution. Let’s consider the buffer made of ammonium
hydroxide and ammonium chloride.
NH4OH ⇌ NH4+ + OH─
NH4Cl → NH4+ + Cl─
[NH+ −
4 ][OH ]
Kb = [NH4 OH]
─ [NH4 OH]
Or, [OH ] = Kb × [NH+4]
─ [Base]
Or, [OH ] = Kb × [Salt]
─ [Base]
Or, -log[OH ] = -log(Kb × )
[Salt]
[Base]
Or, -log[OH─] = -logKb +[-log ( [Salt] )]
[Base]
Or, -log[OH─] = -logKb ─ log ( [Salt] )
[Salt]
Or, pOH = pKb + log ([Base])
This equation is Henderson-Hasselbalch equation for the calculation of pOH of basic buffer solution.

Applications:
1. pOH can be determined for a buffer solution of unknown pOH.
2. For the preparation of a buffer of certain pOH, we can determine the ratio of mole of weak base
and salt.

Significances: According to the equation,

1. If the concentration or mole number of salt is equal than that of base, pOH = pKb.
2. If the concentration or mole number of salt is greater than that of of base, pOH > pKb.
3. If the concentration or mole number of salt is less than that of base, pOH < pKb.

Important formula:
[Salt]
10. For acidic buffer solution, pH = pKa + log ([Acid])
[Salt]
11. For acidic buffer solution, pOH = pKb + log ([Base])

Problem-1: Find out the pH of 0.1 M acetic acid and 0.1 M sodium acetate. [Ka = 1.8 × 10-5]
Solution: We know, for acidic buffer solution
[Salt]
pH = pKa + log ([Acid])
[sodium acetate]
= -logKa + log ( )
[Acetic Acid]
-5 0.1
= -log (1.8 × 10 ) + log (0.1)
= 4.745 (Ans.)

Problem-2: At 298 K temperature how to prepare a buffer of pH = 5.0 of acetic acid? [Here,
pKa = 4.76]
Solution: We know, for acidic buffer solution
[Salt]
pH = pKa + log ([Acid])
[Salt]
Or, 5.0 = 4.76 + log ([Acid])
[Salt]
Or, 0.24 = log ([Acid])
Chemical Changes Page 5 of 10
[Salt]
Or, 1.738 = [Acid]
[Salt]
Or, [Acid] = 1.738
1.738
= 1
So, the mole ratio of sodium acetate and acetic acid should be 1.738:1 for the preparation of desired
buffer.

Problem-3: Decimolar 100 mL formic acid and 0.15 M 30 mL sodium hydroxide are mixed
together. What is the nature of the mixture determine by considering pH. [pKa = 3.8]
Answer: Since the components are acid and base so, we must calculate the pH for rest of the
components present in the mixture after the completion of neutralization reaction.
SV 0.1 ×100
Here, mole number of HCOOH is, n = 1000 = 1000 = 0.01
SV 0.15 ×30
Again, mole number of NaOH is, n = 1000 = = 0.0045
1000

The reaction between A and B is-

HCOOH + NaOH → HCOONa + H2O
Before reaction: 0.01 0.0045 0
After reaction: 0.01-0.0045 0.0045-0.0045 0.0045
= 0.0055 =0
Here, after reaction the number of mole of HCOOH, n = 0.0055 and mole of HCOONa, n = 0.0045.
So the mixture is acidic buffer. Total volume of mixture is = 130mL
1000×0.0055
 The concentration of HCOOH, [HCOOH] = Dear student, in Henderson-
130
= 0.0423M Hasselbalch equation the ratio of
1000×0.0045 concentration of salt and acid or
And the concentration of HCOONa, [HCOONa] = 130 base is considered in the mixture
= 0.0346M and the volume of the mixture is
We know,
same for each component. So we
pH = pKa + log [CH3COONa]/ [CH3COOH]
can consider the ratio of mole of
= pKa + log [CH3COONa]/ [CH3COOH]
= 3.8 + log (0.0346/ 0.0423) salt and acid or base during the
= 3.8 + (-0.087) calculation of pH or pOH of buffer
= 3.713 (Ans.) solution instead of concentration.

Problem-5:
CH3COOH Mixture
+ CH3COONa =
0.01M 60mL pH = 4, pKa = 3.8
0.1M

For the preparation of mixture what mL of CH3COONa is needed?

𝑆𝑉 0.01 ×60
Solution: Number of mole of CH3COOH is, n = 1000 = 1000
Let’s consider the volume of CH3COONa is = xmL
SV 0.1 × x
So number of mole of CH3COONa, n = 1000 = 1000
We know,
pH = pKa + log [CH3COONa]/ [CH3COOH]
0.1 × x
1000
4 = 3.8 + log( 0.01 ×60 )
1000
0.1x
0.2 = log 0.6
0.1x
= 100.2
0.6
 x = 100.2×0.6/0.1 = 9.51mL
That’s the volume of HCOONa is 9.51mL (Ans.)
Chemical Changes Page 6 of 10

Creative Question-1

CH3COOH NaOH HCl

0.1M 180ml 100ml, pH 150ml, pH =0.823
=13
A B C
a. Write down the Ostwald’s dilution law.
b. With increasing temperature KW increases-Explain.
c. If pH of mixture of A and B is 4.84, determine the Ka value of CH3COOH.
d. Whether the pH of mixture of B and C changes or not? Explain this mathematically.

Answer to the Question No-1 (c)

SV 0.1 ×180
Here, the number of mole of CH3COOH is, n = 1000 = 1000 = 0.018
Again, pH of NaOH =13, So pOH = 14 – 13 = 1,  [OH─] = 10-1 = 0.1M
SV 0.1 ×100
So mole number of NaOH is, n = 1000 = 1000 = 0.01
The reaction between A and B is-
CH3COOH + NaOH → CH3COONa + H2 O
Before reaction: 0.018 0.01 0
After the reaction: 0.018-0.01 0.01-0.01 0.01
= 0.008 =0
Total volume of mixture is = 280mL
After the reaction mole number of CH3COOH is, n = 0.008
1000×0.008
 Concentration of CH3COOH is, [CH3COOH] = = 0.0286
280
And mole number of CH3COONa is, n = 0.01
1000×0.01
 Concentration of CH3COONa is, [CH3COONa] = 280 = 0.0357
We know,
pH = pKa + log [CH3COONa]/ [CH3COOH]
4.84 = pKa + log(0.0357/0.0286)
pKa = 4.84 – 0.096
pKa = 4.744
Ka = 10-4.744 = 1.8 ×10-5(Ans.)

Answer to the Question No-1 (d)

Here, for HCl pH = 0.823,  [H+] = 10-0.823 = 0.15M
𝑆𝑉 0.15 ×150
Mole number of HCl is, n = 1000 = 1000 = 0.0225
Mole number of NaOH is, n = 0.01 (from-c)
The reaction between B and C is-
HCl + NaOH → NaCl + H2O
Before reaction: 0.0225 0.01 0
After reaction: 0.0225-0.01 0.01-0.01 0.01
= 0.0125 =0
Total volume of the mixture is = 100 + 150 = 250mL
So after the neutralization the number of mole of HCl is, n = 0.0125
Since, in the mixture strong acid and salt is present. So the mixture is not buffer and for the
calculation of pH we should only consider the concentration of acid only.
1000×0.0125
Concentration of HCl, [HCl] = = 0.05M
250
 Concentration of H ion is, [H ] = 0.05M
+ +

The pH of mixture is, pH = -log[H+] = -log(0.05) = 1.30

That’s why the pH of the mixture of B and C will change.
Chemical Changes Page 7 of 10

Creative Question-2

CH3COOH
0.1M, 100ml NaOH
Ka = 1.8×10-5 0.15M, 30ml

Container: A Container: B
a. Define degree of dissociation.
b. H2SO4 is stronger than HClO4-explain.
c. Determine the pH of container-A.
d. If 2mL 0.01 mL HCl is added in the mixture of containers A and B, explain the result
mathematically.

Answer to the Question No-2 (d)

𝑆𝑉 0.1 ×100
Here, mole number of CH3COOH is, n = 1000 = 1000 = 0.01
𝑆𝑉 0.15 ×30
Again, mole number of NaOH is, n = 1000 = 1000 = 0.0045
Reaction of A and B is-
CH3COOH + NaOH → CH3COONa + H2O
Before reaction: 0.01 0.0045 0
After reaction: 0.01-0.0045 0.0045-0.0045 0.0045
= 0.0055 =0
Total volume of mixture is, = 130mL
So after the neutralization, mole number of CH3COOH is, n = 0.0055
And, mole number of CH3COONa is, n = 0.0045. Since the mixture contains a weak acid and a salt.
So the mixture is acidic buffer solution.
We know,
pH = pKa + log [CH3COONa]/ [CH3COOH]
= -logKa + log [CH3COONa]/ [CH3COOH]
= -log(1.8×10-5) + log (0.0045/ 0.0055)
= 4.745 + (-0.087)
= 4.66
Again, by adding 2mL, 0.01M HCl-
𝑆𝑉 0.01 ×2
Mole number of external H+ ion is, n = 1000 = 1000 = 2×10-5
From the mechanism of buffer solution, we know that mole number of weak acid increases and same
amount of salt decreases during the elimination of external H+ ion.
So, the changed mole number of CH3COOH is, n = 0.0055 + 2×10-5
= 0.00552
And changed mole number of CH3COONa is, n = (0.0045 − 2×10-5
= 0.00448
Again,
pH = pKa + log [CH3COONa]/ [CH3COOH]
= -logKa + log [CH3COONa]/ [CH3COOH]
= -log(1.8×10-5) + log (0.00448/ 0.00552)
= 4.745 + (-0.091)
= 4.65
Here, before the addition of HCl or, H+ ion pH of the mixture was 4.66 but after the addition of H+
the pH of the mixture is 4.65.
So the pH of the mixture decreases by (4.66 – 4.65 = 0.01). Which is not so significant.
Chemical Changes Page 8 of 10

Creative Question-3

HF
0.15M, 25mL NaOH
Ka = 6.6×10-4 0.1M, 30mL

Container: A Container: B
a. What is buffer capacity?
b. Blood is a buffer solution- explain.
c. Determine the pH and degree of dissociation of solution in container-A.
d. If a small amount of acid or base is added in the mixture of A and B whether the pH of the mixture
changes or not-explain this mathematically.

Answer to the Question No-3 (c)

Since, the value of Ka of HF is less than 1, so HF is a weak acid and it partially dissociates in
aqueous solution.
Concentration of H+ ion is, [H+] = √K a C
= √6.6 × 10−4 × 0.15
= 9.95 × 10─3 M
+
We know, pH = -log[H ]
So, pH = -log[H+] = - log (9.95 × 10─3) = 2.0 (Ans.)
𝐊𝐚
Again, degree of dissociation, α = √ 𝐂
6.6 × 10−4
=√ 𝟎.𝟏𝟓
= 0.066 , 6.6% (Ans.)

Answer to the Question No-3 (d)

Since the components are acid and base so, we must calculate the pH for the rest of the components
present in the mixture after the completion of neutralization reaction.
SV 0.15 ×25
Here, number of mole of HF is, n = 1000 = = 3.75 × 10-3
1000
𝑆𝑉 0.1 ×30
Again, mole number of NaOH is, n = 1000 = 1000 = 3.00 × 10-3
The reaction between A and B is-
HF + NaOH → NaF + H2O
-3 -3
Before reaction: 3.75 × 10 3.00 × 10 0 0
After reaction: (3.75 - 3.00)×10-3 (3.00 - 3.00)×10-3 3.00 × 10-3 3.00 × 10-3
= 0.75 ×10-3 =0
Here, the mixture contains weak acid HF of mole number, n = 0.75×10-3 and mole number of salt
NaF is 3.00 × 10-3. So the mixture is an acidic buffer solution. The pH of this solution doesn’t
change by adding a small amount of acid or base which is explained below with proper mechanism.
Dear student, for the completion of this answer you must explain the mechanism. The mechanism is
explained in 4.3.8.3.1. That’s why it is not explained again here.
Chemical Changes Page 9 of 10

Creative Question-4

Neutralization curve of 0.1 M, 20 mL HCl

A

Here, dissociation constant

pH of NH4OH is 1.8 × 10-5.

8 mL 20mL
Added volume of 0.2 M NH4OH
a. What is base dissociation constant?
b. Why the value of pH of pure water is 7 at 25 ºC?
c. Determine the pH of alkaline substance.
d. Which of the mixture between A and B has a capability to make constant the pH? Explain
mathematically?

Answer to the Question No-4 (d)

At point –A
A mixture of 0.1 M, 20 mL HCl and 20mL 0.2 M NH4OH is present.
SV 0.1 ×20
So the number of mole of HCl is, n = 1000 = 1000 = 2×10-3
SV 0.2 ×20
Again, the number of mole of NH4OH is, n = 1000 = 1000 = 4 × 10-3
The reaction in the mixture is-
HCl + NH4OH → NH4Cl + H2O
Before reaction: 2×10-3 4×10-3 0 0
After reaction: 0 4×10-3−2×10-3 2×10-3 2×10-3
= 2×10-3
Here, mole number of NH4OH is, n = 2×10-3
And mole number of NH4Cl is, n = 2×10-3
Since at-A there are a weak acid and a salt present. That’s why the mixture at A is a buffer and has a
capability to keep constant the pH.

Again at point-B
A mixture of 0.1 M, 20 mL HCl and 20mL 0.2 M NH4OH is present.
SV 0.1 ×20
So mole number of HCl is, n = 1000 = 1000 = 2×10-3
SV 0.2 ×8
And mole number of NH4OH is, n = = = 1.6 × 10-3
1000 1000
The reaction in the mixture is-
HCl + NH4OH → NH4Cl + H2O
Before reaction: 2×10-3 1.6 × 10-3 0 0
After reaction: 2×10-3─1.6×10-3 0 1.6×10-3 1.6×10-3
= 0.4×10-3
Now, after the neutralization, mole number of HCl is, n = 0.4×10-3
And mole number of NH4Cl is, n = 1.6×10-3
Since, at point-B a strong acid HCl and a salt is present so the mixture is not buffer and it has no
capability to keep constant pH.
 Chemical Changes Page 10 of 10

Creative Question-5

HA B(OH)3 HC
0.1M, 200mL 50mL, 0.1M 100 mL, 0.1M
Ka = 1.8 × 10-5 Strong base Ka = 1.7 × 10-6
A B C
Here, D = A + B and E = B + C
a. What is the pH of stomach?
b. For the aqueous solution prove that, pKa + pKb = 14.
c. Determine the pH and degree of dissociation of A.
d. Which of the mixture between D and E have a capability to make the pH constant? Explain
mathematically?
Dear student, you can solve this creative question if you practice the previous questions perfectly.
Multiple Choice Question
21. Buffer of blood- 26. For the stem solution-
i. Protein buffer i. An acidic buffer solution
ii. Phosphate buffer ii. Equilibrium shifts forward for the
iii. Carbonate buffer neutralization of base
Correct answer is- iii. pH becomes 5.74 when the ratio of acid
a. i, ii b. ii, iii c. i, iii d. i, ii, iii and salt is 10:1
22. If the ratio of carbonic acid and a. i, ii b. ii, iii c. i, iii d. i, ii, iii
bicarbonate in human blood is 0.06:1 and pH 27. In case of pH-
= 7.4, what is Ka? i. Acidic medicine ionizes less in stomach
a. 1.80 × 10─5 b. 1.85 × 10─7 ii. In small intestine acidic substances ionizes
─7 ─9
c. 6.64 × 10 d. 5.24 × 10 more
23. What is the pH of human stomach? iii. To decrease pH of soil application of TSP
a. 1.5-3.5 b. 4.5-8.0 c. 6.6-7.6 d. 7.4 a. i, ii b. ii, iii c. i, iii d. i, ii, iii
Answer 24, 25 and 26 based on the 28. Which of the following is a buffer?
following stem. a. 1 mol CH3COOH + 1 mol NaOH
CH3COOH ⇌ CH3COO─ + H+; Ka = 1.8 × b. 2 mol CH3COOH + 1 mol NaOH
10─5 c. 2 mol CH3COOH + 3 mol NaOH
─ +
CH3COONa ⇌ CH3COO + Na d. 2 mol H2SO4 + 1 mol NaOH
24. If extra amount of CH3COONa is added in 29. Which of the following doesn’t take place
the stem solution, what will be the change of during the neutralization of external H+ ion in
pH? a basic buffer solution?
a. Increases b. Decreases a. Increases the amount of salt
c. Remains same d. Becomes 7 b. Increases the amount of weak base
25. Which of the following participates in c. Decreases the amount of weak base
chemical reaction when a small amount of d. In solution pOH > pKb
acid is added? 30. By adding 0.06 mole mono basic acid in
a. CH3COOH b. CH3COONa 1L buffer solution the pH of the buffer
c. CH3COO─ d. Na+ decreases by 0.5, what is the buffer capacity?
a. 0.5 b. 4.05 c. 8.33 d. 12.5

Answer of MCQs
MCQ No. 1 2 3 4 5 6 7 8 9 10
Ans. d c b C a c d d d b
Sheet-1
MCQ No. 11 12 13 14 15 16 17 18 19 20
Ans. a c d B c c a d b a
MCQ No. 21 22 23 24 25 26 27 28 29 30
Sheet-2
Ans. a c a A c a d b b c