Buffer Solutions:

Those solutions, which resist the change in their pH when a small amount of an
acid or a base is added to them, are called buffer solutions.

They have a specific constant value of pH and their pH values do not change on
dilution and on keeping for a long time.

Types of Buffer Solutions:

1. Acidic Buffers
2. Basic Buffers

Acidic Buffers:
Acidic Buffers are made by mixing a weak acid and a salt of it with a strong base. Such solutions give
acidic buffers with pH less than 7. Mixture of acetic acid and sodium acetate is one of the best
examples of such a buffer.

Basic Buffers:
Basic Buffers are made by mixing a weak base and a salt of it with a strong acid. Such solutions will
give basic buffers with pH more than 7. Mixture of ammonium hydroxide and ammonium chloride is
one of the best examples of such a basic buffer.

Principle:
Buffer solutions act on the principle of the common ion effect.

Actions of Buffer Solutions:

CH₃COOH, being a weak electrolyte undergoes very little disassociation. When CH₃COONa, which is a
strong electrolyte, is added to CH₃COOH solution then the disassociation of the CH₃COOH is
suppressed, due to common ion effect of CH₃COOˉ.

CH₃COOH (aq) + H₂O (l) CH₃COOˉ (aq) + H₂O⁺ (aq)

CH₃COOHNa (aq) CH₃COOˉ (aq) + Na⁺ (aq)

If someone goes on adding CH₃COONa in CH₃COOH solution, then the added concentrations of
CH₃COOˉ decreases the disassociation of CH₃COOH and the pH of solution increases. Greater is the
concentration of CH₃COOH as compared to CH₃COOHNa, lesser if the pH of solution.

Actually the buffer mentioned above is the largest reservoir of CH₃COOH and CH₃COOˉ components.
When an acid or H₂O⁺ ion are added to this buffer, they will react with CH₃COOˉ to give back acetic
acid and hence the pH of the solution will almost remained unchanged. The reason is that CH₃COOH
being a weak acid will prefer to remain undissociated. The buffer solution consisting of NH₄Cl and
NH₄OH can resist the change of pH and pOH, when acid or base is added from outside. When a base
or OHˉ ions are added in it they will react with the H₃O⁺ to give back H₂O and the pH of the solution
again will remain unchanged.

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Department of Pharmacy
 Calculating the pH of a Buffer:
Consider a weak acid HA and it’s salt NaA with a strong base say NaOH. The
reversible reactions for the dissociation of HA are as follow:

HA H⁺ + Aˉ

NaA Na⁺ + Aˉ

The dissociation constant of a weak acid HA is given by:

Kₐ = ¿ ¿

Rearranging the equation,

Kₐ[HA ]
[H⁺] =
[ Aˉ ]
the concentration of Aˉ in the reaction mixture is predominately being supplied by the NaA which is
a stronger electrolyte then HA, and the ionization of HA is being suppressed by the common ion
effect (Aˉ is the common ion in the buffer solution.

Taking log of the equation:

Kₐ[HA ]
log [H⁺] =log
[ Aˉ ]
[ HA ]
log [H⁺] = log Kₐ + log
[ Aˉ ]
Multiplying with negative on both the sides

[ HA ]
-log [H⁺] = -log Kₐ -log
[ Aˉ ]
Since,

-log[H⁺] = H and -log(Kₐ) = pKₐ

So,

[ HA ]
pH = pKₐ - log
[ Aˉ ]
[Aˉ] refers to the concentration of the salt; actually, maximum possible concentrate of Aˉ is given by
NaA, being a strong electrolyte.

Hence,

[acid]
pH = pKₐ - log
[base ]
Interchanging the numerator and the denominator the sign of the log changes

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1 KM, Defence Road, Lahore
Department of Pharmacy
 [base ]
pH = pKₐ + log
[acid]
This relationship is called the Henderson’s equation. This equation shows that the
two factors evidently govern the pH of the buffer solution. First the pKₐ of the acid
used and second is the ratio of the concentrations of the salt and the acid. The
best buffer is prepared by taking equal concentration of salt and acid. So, pH is
controlled by pKₐ of the acid. For example, for acetic acid sodium acetate buffer, if

[CH₃CHOOH] = [CH₃COONA]

Then,

[CH ₃ COONa]
pH = pKₐ + log
[CH ₃ COOH ]
pH = pKₐ + log(1)

So,

pH = pKₐ + 0 = pKₐ

pH = 4.74

It means that the pH of this buffer is just equal to the pKₐ of the acid.

Preparation of a buffer of a definite pH:

To prepare a buffer of a definite pH, we need suitable acid for that purpose. We can also manage the
buffer of our own required pH by suitably selecting the concentration ratio of the salt and the acid. If
[CH₃COOH] is 0.1 molar dmˉ³ and that of [CH₃COONa] is 1.0 mole dmˉ³ then

[salt ]
pH = 4.74 + log
[acid]
[1.0]
pH = 4.74 + log = 4.74 + log10
[0.1]
Since,

log10 = 1

pH = 4.74 + 1

pH = 5.74

Factors Influencing the pH of the Buffer Solution:

The addition of neutral salts to buffers changes the pH of the solution by altering the ionic strength.
Changes in the ionic strength and hence in the pH of a buffer solution can also be brought about by
dilution. The addition of water in moderate amounts although not changing the pH, may cause a
small positive or negative deviation because it alters activity coefficients and because water itself
can act as a weak acid or base.

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1 KM, Defence Road, Lahore
Department of Pharmacy
 Temperature also influences the buffer. E.g. the pH of acetate buffers was found
to increase with temperature, whereas the pH of boric acid-sodium borate buffers
decrease with temperature.

Importance of Buffer Solutions:

 The pH of the human blood is maintained at 7.35. If it changes to 7.0 or
8.0 the person may die. The pH of the blood remains constant due to the presence of HCOˉ₃,
PO₄ˉ³ and proteins.
 Buffers are widely used in chemistry and allied science like Molecular Biology, Soil Sciences,
Nutrition and Chemical Analysis.
 Sometimes one want to study a reaction under conditions that would suffer any associated
change in the pH of the reaction mixture, so by suitable choice of the solutes, a chemist can
assure that a solution will not experience more than a very small change In the pH, even if a
small amount of acid or base is added.

Buffers in Pharmaceutical Systems:

Buffers are used in pharmaceutical systems widely:

 Drugs as buffers
 Pharmaceutical buffers

Drugs as Buffers:
It is important to recognize that solutions of drugs that are weak electrolyte also manifest buffer
action. Salicylic Acid solution in a soft glass bottle is influenced by the alkalinity of the glass. It might
be thought at first that the reactions would result in an appreciable increase in pH; however, the
sodium ion of the oft glass combine with the salicylate ions to form sodium salicylate. Thus, there
arises a solution of salicylic acid and sodium salicylate-a buffer solution that resists the change in pH.

Pharmaceutical Buffers:
Buffer solutions are used frequently in pharmaceutical practice, particularly in the formulation of
ophthalmic solutions. They also find application in the colorimetric determination of pH and for the
research studies in which pH must be held constant. E.g. Gifford suggested to stock solutions, one
containing boric acid and the other mono hydrated sodium carbonate, which, when mixed in various
proportions, yields buffer solution with pH values from about 5 to 9.

Buffers in Biological Systems:

Blood is maintained at a pH of about 7.4 by the so called primary buffers in the plasma and the
secondary buffers in the erythrocytes. The plasma contains carbonic acid/bi carbonate and acid
/alkali sodium salts of phosphoric acid as buffers. Plasma proteins, which behaves as acids in blood
can combine with bases and so act as buffers. In the erythrocytes, the two buffers system consists of
hemoglobin/ oxy-hemoglobin and acid/alkali potassium salts of phosphoric acid.

References:
 Martins Physical Pharmacy and Pharmaceutical Sciences 5 th Edition by Patrick J. Sinko
 S. R. Gifford, Arch. Ophthalmol. 13, 78, 1935
The University of Lahore
1 KM, Defence Road, Lahore
Department of Pharmacy
The University of Lahore
1 KM, Defence Road, Lahore
Department of Pharmacy