buffers Flashcards
buffers
Buffers are compounds or mixture of compounds that by their presence in their solution resists change
in pH upon the addition of small quantities of acid or alkali. The resistance to a change in pH is known
as buffer action.
The substances used to produce buffer action are called buffers and usually consists of mixture of:
o Type “A”: A weak acid and its conjugate base that is a salt
o Type “B”: A weak base and a conjugate acid
types of buffer solutio
On the basis of constituents of buffer solution, the buffer solution can be grouped into two types:
1. Acidic Buffers
2. Basic Buffers
acidic buffers
- ACIDIC BUFFER: Those buffer solutions, which are prepared by mixing a weak acid with its salt with
strong base e.g. CH3COOH / CH3COONa, H2CO3 / Na2CO3 etc.
basic buffers
- BASIC BUFFER: These are buffer solution which are formed by mixing base with its salt with strong
acid e.g. NH4OH / NH4Cl & ephedrine / ephedrine HCl, etc.
mechanism
The resistance, which is offered to the change in pH of buffer solution is said to be buffer action or
mechanism of buffer solution.
As an acidic buffer has weak acid & salt of strong base, so buffer solution contains an acidic species
which react with base added to the solution & a basic species which react with incoming acid in order to
maintain pH of buffer solution. And this whole process reversed in case of basic buffer.
For example, buffer solution CH3COOH / CH3COONa has acidic species H3O
+ & basic species
CH3COOH. When a basic species (e.g. OH-
) is added to this buffer solution. CH3COOH react with it &
neutralizes it. And in the same way if acidic species (e.g. H3O
+
) is added to this buffer solution, the CH3COO-
react with it & neutralizes it.
CH3COOH → CH3COO
− + H
+
CH3COONa → CH3COO
− + Na+
common ion effect type A
This expression is developed by considering the effect of a salt on the ionization of a weak acid when
the salt and acid has a common ion e.g. when sodium acetate is added to acetic acid, the dissociation
constant for a weak acid is:
Ka =
[Ac−][H3O
+]
[HAc]
= 1.75 × 10−5
distributed due to the acetate ion supplied by the salt. Hence in order to maintain the constant 1.75 ×
10-5
, the hydrogen ion in nominator will decrease and the HAc in demoniatior increases. So that the constant
Ka remains unaltered and the equilibrium is subjected towards the reactants. The ionization of acetic acid is
represented:
HAc + H2O ⟶ Ac− + H3O
+
by the addition of common ion Ac-
. This is an example of common ion effect.
The pH of the final solution is obtained by arranging the equilibrium equation of dissociation constant.
[H3O
+] =
Ka [HAc]
[Ac−]
If the acid is weak and ionized only slightly then the expression HAc may be considered to represent
the total concentration and it may be simply written as acid in a slightly ionize acetic solution. The Acion
only comes from the salt that is sodium acetate since one mole of sodium acetate yields one mole of acetate
ion. The total concentration of Acion may be replaced by the term salt.
[H3O
+] =
Ka [Acid]
[Salt]
Equation may be expressed in term of log,
− log [H3O] = − logKa – log [Acid] + log [Salt]
From this buffer equation is obtained for weak acid and its salt,
pH = pKa + log
[Salt]
[Acid]
This equation can give you calculation in range of 4 – 10 pH.
type B
Buffer solution of weak bases and their salts are ordinarily not prepared because of volatility and
instability of the base and secondly because of the dependence of pH on pKw which is often affected by
temperature change e.g. ephedrine and ephedrine HCl is often used in pharmaceutical solution as buffer. Their
buffer equation can also derive analogous to deserve weak acid buffer.
[OH−] =
Kb [Base]
[Salt]
[OH−] =
Kw
[H3O−]
Comparing both equations we get,
Kw
[H3O−]
=
Kb [Base]
[Salt]
pH = pKw – pKb + log
[Base]
[Salt]
conclusions
The strength of an acid can be expressed in terms of either Ka or the Kb if its conjugate base is known.
The Ka of an acid can be calculated if the Kb of its conjugate base is known.
The stronger an acid is, the weaker is its conjugate base and vice versa.
factors affecting pH
There are some factors which influence the pH of buffer solution. Among these factors some are as
follows:
1. NEUTRAL SALT: By the addition of small quantity of neutral salt, there is no effect on the pH of the
buffer solution. But when the concentration of added neutral salt is increased, then pH of buffer solution
changes due to change in ionic strength.
2. DILUTION: Dilution of buffer solution i.e. the addition of H2O in moderate quantities may not change
pH but can cause small positive or negative deviation because it can act as weak acid or base.
3. TEMPERATURE: The pH of acetate buffers increases with temperature whereas pH of boric acid and
sodium borate buffer decreases with increase in temperature and basic buffers are more effected by change in
temperature.
buffer capacity
The magnitude of a resistance of a buffer to pH change is reffered as buffer capacity β.
It is also called buffer efficiency, buffer index and buffer value.
It is the ratio of the increment of strong base (or acid) to the small change in pH brought by this
addition.
β =
∆B
∆pH
Δ β is the small increment in gram equivalent per liter of strong base added to a buffer solution to
produce a pH change of ΔpH.
According to equation, the buffer capacity has a value of one when one gram equivalent of base
produce a pH change of 1 in one-liter buffer solution.
maximum buffer capacity
The capacity of a solution will be maximum, when salt to acid ratio of buffer solution is one (i.e. pH
= pKa). According to buffer equation:
pH = pKa + log
[Salt]
[Acid]
If [salt] = [acid]
pH = pKa + log 1
pH = pKa + 0
pH = pKa
biological buffers
The buffer which are present in different biological systems are called Biological or In-vivo buffers.
Biological buffers are classified into two groups:
1-primary
2-secondar
primary buffers
These buffers help in maintaining the pH of the blood. The normal value blood pH is 7.4. If it exceeds
8 alkalosis & if lower than 7 acidosis is resulted.
These are the buffers which are present in human blood plasma. Plasma has three types of buffer
systems.
o Carbonic acid & its salt i.e. H2CO3 / NaNCO3
o Phosphoric acid & its salt i.e. H3PO4 / Na3PO4
o Plasma protein in acts as acid & salt is formed. This resultant salt & uncombined protein forms
a system, which acts as buffer.
secondary buffers
The buffers are present in the RBC’s or erythrocytes are called secondary buffer. Following are some
examples of secondary buffers.
o Hemoglobin & oxy – hemoglobin (oxidizing buffer)
o Phosphoric acid & potassium salt of phosphoric acid.
buffers in pharmaceutical and in biological systems
Blood is maintained at a pH of about 7.4 by 8.0 called primary buffers in erythrocytes. The plasma
contains carbonic acid/ bicarbonates and acid/alkali Na salts of H3PO4 as buffers. Plasma proteins
which behave as acid in blood can combine with bases and so act as buffers. In erythrocytes two buffer
systems consist of hemoglobin / oxhemoglobin and acid/alkali K salts of H3PO4. When the pH of
blood goes 7 or above 7.8 Life is in serious danger. The pH of blood in diabetic coma is alleged to
drop as low as 6.8. Lacrimal fluids or tears have pH of 7.4. They have a high dilution value of 1:15
with neutral distilled water before an alternation in pH is noticed.