Chemistry, The Central Science, 2nd edition

BUFFERS

Aqueous
Equilibria

Buffers:
Solution that resists
change in pH when a
small amount of acid or
base is added or when
the solution is diluted.
A buffer solution consists
of a mixture of a weak
acid and its conjugate
base or a weak base
and its conjugate at
predetermined
Aqueous
Equilibria
concentrations or ratios.

Buffers

If a small amount of hydroxide is added to an

equimolar solution of HF in NaF, for example, the HF
Aqueous
reacts with the OH to make F and water.

Equilibria

Buffers

If acid is added, the F reacts to form HF and water.

Aqueous
Equilibria

Buffered Solutions
H+(aq) + X(aq)

HX(aq)
Ka =

[H+] [X]
[HX]

1. If -OH is added:
-OH(aq)

+ HX(aq) H2O(l) + X(aq)

2. If H+ is added:

H+(aq) + X-(aq) HX(aq)

Aqueous
Equilibria

 There are two forms of buffers:

Acidic buffers solutions which
maintain a pH < 7 (components - weak
acid and salt of a weak acid)
Basic buffers - solutions which maintain
a pH > 7 (components - weak base and
salt of a weak base)
Aqueous
Equilibria

Buffers of pH < 7

weak acid + salt of weak acid

CH3COOH CH3COO- Na+

acetic acid

Sodium acetate

The weak acid is there to react with any OHions which might be introduced into the system.
CH3COOH(aq) + OH- CH3COO- (aq) + H2O(l)
Aqueous
Equilibria

 The effective result of this reaction is to

convert a strong base (OH-) into a weak
base CH3COO- (aq) .
Thus although the pH will increase due
to more base being present, the
increase will be relatively small as the
acetate ion is a weak base (Kb = 5.7 x
10-10).
Aqueous
Equilibria

 The salt of the weak acid is there to react

with any H3O+ ions which might be
introduced into the system.
CH3COO- (aq) + H3O+ CH3COOH(aq) + H2O(l)

Again the effective result of this reaction is to

convert a strong acid H3O+ into a weak acid
(Ka (CH3COOH) = 1.75 x 10-5 ). The pH will
decrease but only by a small amount.
Aqueous
Equilibria

Buffers of pH > 7
weak base +

NH3

Ammonia

salt of a weak base

NH4Cl
Ammonium chloride

The weak base is there to react with

any H3O+ ions.

NH3 (aq) + H3O+(aq) NH4+ (aq) + H2O(l)

Aqueous
Equilibria

 The salt of the weak base is there to

react with any OH- ions.

NH4+ (aq) + OH-(aq) NH3 (aq) + H2O (l)

Aqueous
Equilibria

Buffer Calculations
Consider the equilibrium constant
expression for the dissociation of a
generic acid, HA:

HA + H2O

H3O+ + A

[H3O+] [A]
Ka =
[HA]
Aqueous
Equilibria

Buffer Calculations
[base]
pH = pKa + log
[acid]

This is the HendersonHasselbalch equation.

Aqueous
Equilibria

HendersonHasselbalch
Equation
What is the pH of a buffer that is 0.12 M
in lactic acid, HC3H5O3, and 0.10 M in
sodium lactate? Ka for lactic acid is
1.4 104.
pKa = log(Ka) ( correct this)
Aqueous
Equilibria

HendersonHasselbalch
Equation
[base]
pH = pKa + log
[acid]
pH = log (1.4

104)

(0.10)
+ log (0.12)

pH = 3.85 + (0.08)
pH = 3.77
Aqueous
Equilibria

Buffer Capacity and pH Range

The pH range is the range of pH values
over which a buffer system works
effectively.
It is best to choose an acid with a pKa
close to the desired pH.
The useful pH range of a buffer is:
pKa 1
Aqueous
Equilibria

Addition of Strong Acids

or Bases to Buffers
Calculating pH Changes in Buffers
A buffer is made by adding 0.300 mol
HC2H3O2 and 0.300 mol NaC2H3O2 to
enough water to make 1.00 L of
solution. The pH of the buffer is 4.74.
Calculate the pH of this solution after
0.020 mol of NaOH is added.
Aqueous
Equilibria

Calculating pH Changes in Buffers

Before the reaction, since
mol HC2H3O2 = mol C2H3O2
pH = pKa = log (1.8 105) = 4.74

Aqueous
Equilibria

Calculating pH Changes in Buffers

The 0.020 mol NaOH will react with 0.020 mol of the
acetic acid:
HC2H3O2(aq) + OH(aq) C2H3O2(aq) + H2O(l)
HC2H3O2

C2H3O2

OH

Before reaction

0.300 mol

0.300 mol 0.020 mol

After reaction

0.280 mol

0.320 mol 0.000 mol

Aqueous
Equilibria

Calculating pH Changes in Buffers

Now use the HendersonHasselbalch equation to
calculate the new pH:

(0.320)
pH = 4.74 + log
(0. 280)
pH
= 4.74 + 0.06
pH
= 4.80
What is the change in pH?
pH = pH final pH initial
= 4.80 4.74 = 0.06

Aqueous
Equilibria