Buffer solution

Ionic Equilibrium
Basic terms

Electrolytes ; Can ionize in fused condition or aqueous system & pass

electric current

Types; 1. Strong electrolyte, eg HCl, NaCl, KOH (almost completely ionized)

2. Weak electrolyte, eg CH3COOH, NH4OH (feebly ionized)

NaOH Na+ + OH- (completely ionization)

CH3COOH CH3COO- + H+ (feebly ionized)

pH and pH scale

pH = - log [H+]

pOH = - log [OH-]

pH+ pOH = 14

pH scale
Common ion effect and Le-chateliers principle

Ionization of weak electrolyte is highly suppressed in presence of strong

electrolyte which gives common ion. Eg ionization of ammonia in presence
of ammonium chloride

(At equilibrium)
 Buffer solution

1 ml 0.1M HCl 1 ml 0.1M HCl

pH= 5 pH= 5
No buffer A 100 ml B
buffer

pH= 1 pH = 4.9

A buffer solution is a solution that resists changes in pH (or maintain

pH almost constant) either when diluted or when limited amounts of
strong acid or base are added to it. Such a solution can be
generally prepared by combining a weak acid and its salt with a
strong base (conjugated base) or, analogously, a weak base and its
salt with a strong acid (conjugated acid).
 Important of buffer

1. In biosystem (METABOLISM)

2. In industry (pharmaceuticals)

3. In laboratory (different titration)

 Types of Buffer solution

Acidic buffer (pH<7); it is a mixture of weak acid & its salt with strong base

CH3COOH + NaOH CH3COONa + H2O

WA SB salt of WA with SB

Ie mixture of CH3COOH & CH3COONa is acidic buffer

2. Basic buffer (pH>7); it is a mixture of weak base & its salt with strong acid

NH4OH + HCl NH4Cl + H2O

WB SA salt of WB with SA

Ie mixture of NH4OH and NH4Cl is basic buffer

 Some examples
• Acidic buffer;
1. CH3COOH + CH3COONa
2. HCOOH + HCOONa
3. Oxalic acid + sodium oxalate
• Basic Buffer;
1. NH3 + NH4Cl
2. NH4OH + NH4NO3
3. Methylamine+Methyl ammonium chloride
A buffer solution
• contains a combination of acid–base conjugate
pairs, a weak acid and a salt of its conjugate base,
such as
CH3COOH(aq) and CH3COO−(aq)

CH3COOH CH3COO −
weak acid its conjugate base

• Should have equal concentration of a weak acid

and its salt.
In the buffer with acetic acid (CH3COOH) and sodium
acetate (CH3COONa),

• the salt produces acetate ions and sodium ions.

CH3COONa(aq) = CH3COO−(aq) + Na+(aq)

• the salt is added to provide a higher concentration of

the conjugate base CH3COO− than from the weak
acid alone.

CH3COOH(aq) + H2O(l) CH3COO−(aq) + H3O+(aq)

Large amount Large amount
 Mechanism of buffer action (VI)
The mechanism of buffer action can be explained with the help of common
Ion effect and Le-chateliers principle. Let us take acidic buffer of acetic acid
& sodium acetate where acetic acid being a weak electrolyte is partially
Ionized where as salt is completely ionized as given in equation (a) and (b),
respectively.
When small amount of strong base (eg NaOH) is added , OH- ion of base combines
with H+of buffer system and decreases the amount of H+ in system which makes
the disturbance of equilibrium state of eq (a). But according to Le-chateliers
principle, this disturbance is minimized by shifting the equilibrium state of eq (a)
towards right side (to fulfill the decresed amount of H + ion), ie,. amount of H+ remains
constant and therefore, there is no change in pH of buffer solution

(a) (Partially ionized)

(b) (Completely ionized)

Similarly, when small amount of strong acid (eg HCl) is added , H+ concentration
In buffer system is increased which makes the disturbance of equilibrium state of
eq (a). But according to Le-chateliers principle, this disturbance is minimized by
shifting the equilibrium state of eq (a) towards left side, ie,.H+ of HCl combines with
CH3COO- of sodium acetate to give CH3COOH. In this way we are adding strong
acid but there is formation of unionized weak acid and therefore, there is no change
in H+ concentration which maintain pH almost constant.

(a) (Partially ionized)

(b) (Completely ionized)

For basic buffer action mechanism
explain yourselves
 Buffer capacity

Buffer capacity (β) is defined as the amount of a strong acid or a

strong base that has to be added to 1 litre of a buffer to cause pH
change of 1 pH unit: ie.,

The buffer capacity depends on the amounts of substance of the weak

acid and its conjugated base (or weak base and its conjugate acid) in
the buffer. The buffer capacity is maximum with 1:1 ratio of conjugate
acid base pair. Moreover, its value decreases with increasing dilution

Question; which has highest buffer capacity

a. 0.1 M HF and 0.1M NaF
b. 1M HF and 1M NaF
c. 0.001M HF and 0.001M NaF
d. 1M HF anf 0.1M NaF
 Calculation of pH of buffer solution
Henderson Equation
Derivation;
Let us take acidic buffer of acetic acid (HA) and sodium acetate
(NaA)

(a) HA + H2O A + H3O+ (feebly ionized)

(b) NaA A- + Na+ (completely ionized)
By applying law of mass action at equilibrium state of eq (a)
[H3O+] [A-]
Keq = …….(1)
[HA [H2O]]
[H3O+] [A-]
Or, Keq x [H2O] =
[HA ]
[H3O+] [A-]
Or, Ka =
[HA ]
[HA]
Or, [H3O+] = Ka …….(2)
[A- ]
Taking log of this equation (2)
[HA]
Or, log10 [H3O+] = log10 Ka + log
[A- ]
[HA]
Or, - log10 [H3O+] = - log10Ka - log
[A- ]

[A-]
pH = pKa + log10
[HA ]
[Salt]
pH = pKa + log10 …….(3)
[Acid]

For basic buffer solution

[Salt]
pOH = pKb+ log10 …….(4)
[Base]

Equation (3) and (4) are Henderson equation

Q1. Calculate the pH mixture containing 100 ml of 0.5M NH4OH and
400 ml of 0.1M NH4Cl (Kb of NH4Cl = 1.8 x 10-5).

Solution; Total volume = 100 + 400 = 500 ml

New concentration of NH4OH ; N1V1 = N2V2
0.5 x 100 = N2 x 500
N2 = 0.5 x 100/500 = 0.1M
New concentration of NH4Cl; N1V1 = N2V2
0.1 x 400 = N2 x 500
N2 = 0.1 x 400/500 = 0.08M
Click [Salt]
to add text
pOH = pKb+ log10
[Base]
(0.08)
pOH = 4.74 + log10
(0.1)

pOH = 4.74 + (- 0.0967)

= 4.64
Q2. Calculate the weight in gram of CH3COONa required to make acidic buffer
having pH= 5.2 with acetic acid having 1.2 L of 0.1 M CH3COOH (PKa = 4.74).
[Salt]
Solution; pH = pKa + log10
[Acid]
(Salt)
5.2 = 4.74 + log10
(0.1)
(Salt)
log = 0.46
(0.1)
[Salt]
= 10 0.46
0.1
= 0.2884

[Salt] = 0.2884M
M = wt in gm/molecular weight x vol. in ltr
0.2884 = x / 82x1.2
X = 28.37 g
 Q3. 4 millimole of NaOH is added to 200 ml of a buffer which is 0.1 M acetic acid
and 0.1 M in sodium acetate. Calculate the change in pH of the solution.
Solution;
Before the addition of NaOH After the addition of NaOH
Molarity of NaOH = no of millimole/vol in ml
[Salt] = 4/200 = 0.02M
pH = pKa + log10
[Acid] 0.02
(0.1)
pH = 4.74 + log10
(0.1) 0.1
pH = 4.74
0.1

Now, concentration of acid = 0.1- 0.02

Concentration of salt = 0.1 + 0.02
(0.12)
pH = 4.74 + log10
pH = 4.74 + 0.176 (0.08)
Change of pH = 4.91-4.74 pH = 4.91
= 0.17
Question for examination

1 . What is buffer solution?

2. Give the mechanism of buffer action.

3. What do you mean by buffer capacity?

4. Write down five example of basic buffer.

5. Is our blood a buffer system? If yes, what are the components

for this buffer?
 Project work

1. Is there any acidic buffer having pH > 7? Find out the answer and explain
with suitable example.

2. List out the product applied in health care technology (BIOMEDICAL

ENGINEERING) using buffer system for their industrial production.
Submission date of Tutorial

2078/3/15

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