MONICA BEDI

Ph.D Chemistry
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BUFFER SOLUTION

A buffer solution is

the solution which resists changes in the hydrogen ion concentration on the addition
of small amount of acid or base.

Human blood is an excellent example of natural buffer solution.

Blood maintains its pH value around 7.35 ( inspite of a wide variety of foods we take)
 Buffer action

The ability of the buffer solution to resist the changes in pH value on the addition
of small amount of an acid or a base, is called buffer action.
Types of Buffer

Simple buffer solution Mixed buffer solution

(A) Simple buffer solution – A salt of weak acid and weak base in water.
Ex- CH3COONH4, protein and amino acid.
 Buffer Action of Simple buffer

Consider a simple buffer solution of CH3COONH4

CH3COONH4 ⇌ CH3COO– + NH4+

if a strong acid such as HCl is added then

HCl ⇌ H+ + Cl–
 MIXED BUFFER SOLUTION

Mixed Buffer solutions are of two types:

(a) Acidic buffer.

Acidic buffer solution contains “Equimolar” quantities of a weak acid and its salt
with strong base. For example, acetic acid (CH3COOH) and sodium acetate
(CH3COONa).
Making of acidic buffer (Titrations)

Aim: Mixture of WASB salt and weak acid. CH3COOH + CH3COONa

Process: Mixing of WA and strong base [Note: Condition [WA] > [SB]]
CH3COOH + NaOH  CH3COONa + H2O (Level: 50% Titration)
1 mole 0.5 mole 0 0
0.5 mole 0 0.5 mole 0.5 mole

Acidic buffer
Buffer Action: Mechanism

The H+ ions from the added acid combine with CH3COO– ions to form CH3COOH.
Thus there is no rise in [H+] and the pH remains constant.

CH3COONa + HCl ⇌ CH3COOH + NaCl

(Limiting)
CH3COO– + H+ ⇌ CH3COOH (weak acid)

If a strong base is added such as KOH

KOH ⇌ K+ + OH–
CH3COOH + KOH ⇌ CH3COO –K+ + H2O
(Limiting)
Thus change in [OH–] is resisted by CH3COOH and pH remain constant.

NOTE: [Salt] + [Acid] = Constant

 Buffer Action of Mixed Buffers

When a few drops of an acid is added to it. The H+ ions from the added combine
with excess of CH3COO– ions to form CH3COOH.

Thus, there is no rise in [H+] and the pH remains constant.

CH3COO – + H+ ⇌ CH3COOH

On the other hand, when a few drops of base NaOH are added the OH– of added
base react with acetic acid to form unionised water and acetate ions.

CH3COOH + OH– ⇌ H2O + CH3COO–

Thus, there is no increase in [OH–] and hence the pH remains constant.
MIXED BUFFER SOLUTION

(b) Basic buffer.

Basic buffer solution contains equimolar quantities of a weak base and its salt
with a strong acid. For example, ammonium hydroxide (NH4OH) and ammonium
chloride (NH4Cl)
 Crack it

1. Which of the following solutions will act as a buffer?

(a*) HNO2 and NaNO2
(b) HCI and KCI
(c) HNO3 and NH4NO3
(d) NaOH and NaCI
 Crack it

2. An acidic buffer solution can be prepared by mixing the solution of

(a*) sodium acetate and acetic acid
(b) ammonium acetate and ammonium hydroxide
(c) sodium chloride and sodium hydroxide
(d) potassium sulphate and sulphuric acid.
 Henderson – Hasselbalch Equation
To calculate the pH of a buffer solution made up of a weak acid and its salt with a strong
base.
We have
HA ⇌ A– + H+ Eg. CH3COOH ⇌CH3COO– + H+
NaA  A– + Na+ CH3COONa  CH3COO– + Na+
Henderson – Hasselbalch Equation: Assumptions
Henderson – Hasselbalch Equation for Basic Buffer (WB + WBSA)

For a buffer made up of weak base and its salt with a strong acid the Henderson’s
equation looks like this

pOH = pKb + log

 Practice: Henderson – Hasselbalch equation

1. Calculate the pH of a buffer solution containing 0.2 mole of NH4Cl and 0.1 mole of
NH4OH per litre. Kb for NH4OH = 1.85 x 10–5
 Lets Practice
2. How much CH3COONa should be added to 1 litre of 0.1 M CH3COOH to make
a buffer of pH= 4.0? Ka = 1.8 x 10–5.
Crack it
Crack it
Crack it
Practice: Henderson – Hasselbalch equation

4 gm of NaOH were dissolved in 1 liter of a solution containing 1 mole of

CH3COOH and 1 mole of CH3COONa.
Calculate [H+] in the resultant solution.
(Given Ka(CH3COOH) = 1.8×10–5)
Keep in mind for Buffer Numericals

Buffer solution can be used for practical purposes when ???

0.1 < [Salt]/[Acid] < 10
0.1 < [Salt]/[Base] < 10

means, pH (or pOH) lies within the range of (pKa ± 1) or (pKb ± 1).

For example,
Acetic acid (pKa = 4.75 at 250C) and sodium acetate mixture can be used for
preparing buffer solutions whose pH values are roughly in the range of 3.75 to
5.75.

Outside this range, the buffer capacity of acetic acid–sodium acetate solution is
too small to be used for any practical purpose.
Buffer Capacity ()

The capacity of a solution to resist alteration in its pH value is known as buffer capacity.
It is defined as amount of H+ or OH– to be added per liter to change the pH by unit value.

Amt. of H+ or OH– to be added per liter

Buffer Capacity  = change the pH

By Differentiating Henderson – Hasselbalch equation

𝑆𝑎𝑙𝑡 [𝐴𝑐𝑖𝑑]
We get ,  = 2.303 , here 𝑆𝑎𝑙𝑡 + 𝐴𝑐𝑖𝑑 = constant
[𝑆𝑎𝑙𝑡]+[𝐴𝑐𝑖𝑑]

 is maximum at 𝑆𝑎𝑙𝑡 = 𝐴𝑐𝑖𝑑 (can be proved using maxima-minima )

Home work PYQ

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