Buffer Solutions

A buffer is a solution that resists changes in pH upon addition of small quantities of

acids or bases. In other words, a buffer is a solution that keeps its pH almost constant.
A buffer is a solution containing a weak acid and its conjugate base or a weak base
and its conjugate acid. Below is an explanation of how buffers work:
Let us look at a buffer formed from a weak acid (like acetic acid) and its conjugate
base (e.g. sodium acetate); we have the following equilibria:
HOAc = H+ + OAcOAc- + H2O = HOAc + OHIn the first equilibrium, acetate is produced from the dissociation of acetic acid.
However, there is a lot of acetate added to solution from the sodium acetate.
Therefore, the first equilibrium does not occur to any significant degree. We can fairly
assume that HOAc will practically not dissociate. The same applies for the second
equilibrium where acetic acid is produced. Since a great excess of acetic acid is
present in solution from the first equilibrium, one can say that acetate will not
practically associate in water. Therefore, neither acetic acid nor acetate equilibria will
proceed to any significant extent. The equilibrium constant for dissociation of acetic
acid can be written as:
Ka = [OAc-][H+]/[HOAc]
Where the [OAc-] = COAc- and [HOAc] = CHOAc
When an acid is added to the buffer above, H+ from the acid will combine with OActo form HOAc which is reflected by an increase in HOAc and a decrease in OAc-. In
case the amount of H+ added is not very large, the ratio [OAc-]/[HOAc] will only
change slightly. A similar argument can be presented when a small amount of base is
added to the buffer solution. However, we will treat the buffer problem as we
described for the common ion effect (see examples below).

Buffer Capacity
The degree of buffer resistance to changes in pH is referred to as buffer capacity. The
buffer capacity is defined as the concentration of acid or base ( in moles ) needed to
cause a pH change equal to dpH where:
= dCbase/dpH = - dCacid/dpH
The minus sign is because addition of an acid causes a decrease in pH. A more
practical relation to use for calculation of buffer capacity is:
= 2.303 Cacid Cconjugate base / (Cacid + Cconjugate base)

Example
Calculate the buffer capacity of a solution containing 0.10 M acetic acid and 0.10 M
acetate. Find the pH change when you add NaOH so that the solution becomes 0.005
M in NaOH

Solution
= 2.303 Cacid Cconjugate base / (Cacid + Cconjugate base)
= 2.303 * 0.10 * 0.10/( 0.10 + 0.10) = 0.115 M
= dCbase/dpH
0.115 = 0.005/dpH
dpH = 0.005/0.115 = 0.043

Hasselbalch-Henderson Equation
In the acetic acid/acetate buffer described above, we have:
Ka = [OAc-][H+]/[HOAc]
Pka = pH log [OAc-]/[HOAc]
pH = pka + log [OAc-]/[HOAc]
The above equation is referred to as Hasselbalch-Henderson equation. This equation
was a major equation in buffer calculations but we will prefer to just use the
equilibrium relations in setting up buffer problems. However, this equation can be
useful to describe buffer limits where the maximum pH limit for a buffer is when the
salt to acid ratio is 10 and the minimum pH limit of the buffer is when the acid to salt
ratio is 10. Inserting these values, one in a time, in the Hasselbalch equation gives
pH = pka + 1
Therefore, the buffer acts well within two pH units and the midpoint pH value is
equal to pka. One should first look at the pka or pkb to choose the correct buffer
system which can be used within a specific pH range.
Example
Calculate the pH of the buffer containing 0.5 M formic acid (HA, ka = 1.8x10-4) and
and 0.25 M sodium formate (NaA).

Solution
First, write the acid equilibrium equation
HA = H+ + ABefore Equilibrium

0.5

0.25

Equation

HA

H+

A-

At Equilibrium

0.5 - x

0.25 + x

Ka = x (0.25 + x)/(0.5 x)
Assume that 0.25 >> x
1.8x10-4 = 0.25 x /0.5
x = 3.6x10-4
Relative error = (3.6x10-4/0.25) x 100 = 0.14%
The assumption is therefore valid and we have
[H+] = 3.6x10-4 M
pH = 3.44
Example
Calculate the pH of the buffer solution prepared by mixing 10 mL 0.10 M HOAc (ka =
1.75x10-5) with 20 mL of 0.20 M sodium acetate.
Solution
Let us first calculate the concentrations after mixing (final concentrations of the acid
and its conjugate base)
mmol HOAc = 0.10 x 10 = 1.0 mmol
[HOAc] = 1.0/30
mmol OAc- = 0.20 x 20 = 4.0 mmol
[OAc-] = 4.0/30
The equilibrium equation is

HOAc = H+ + OAc-

Before Equilibrium

1.0/30

4.0/30

Equation

HOAc

H+

OAc-

At Equilibrium

1.0/30 - x

4.0/30 + x

Ka = x (4.0/30 x)/ (1.0/30 x)

Assume 1.0/30 >> x
1.75x10-5 = x (4.0/30)/1.0/30
x = 1.75x10-5 /4.0
x = 4.38x10-6
Relative error = {4.38x10-6/(1.0/30)} x 100 = 0.013%
The assumption is valid therefore:
[H+] = 4.38x10-6 M
pH = 5.36
Example
Calculate the pH of the solution resulting from adding 25 mL of 0.10 M NaOH to 30
mL of 0.20 M acetic acid.
Solution
Let us find what happens when we mix the two solutions. Definitely the hydroxide
will react with the acid to form acetate which also results in a decrease in the acid
concentration.
mmol OH- = 0.10 x 25 = 2.5 mmol
mmol HOAc = 0.20 x 30 = 6.0 mmol
Now the mmol base added will react in a 1:1 mole ratio with the acid . Therefore we
have
mmol OAc- formed = 2.5 mmol
[OAc-] = 2.5/55 M
mmol HOAc left = 6.0 2.5 = 3.5 mmol
[HOAc] = 3.5/55 M
HOAc = H+ + OAcBefore Equilibrium

3.5/55

2.5/55

Equation

HOAc

H+

OAc-

At Equilibrium

3.5/55 - x

2.5/55 + x

Ka = x (2.5/55 x)/ (3.5/55 x)

Assume 2.5/55 >> x
1.75x10-5 = x (2.5/55)/3.5/55
x = 1.75x10-5 x 2.5/3.5
x = 2.45x10-5
Relative error = {2.45x10-5/(2.5/55)} x 100 = 0.054%
The assumption is valid
pH = 4.61