Chapter 21 Further Aspects of Equilibria

CHAPTER 21 FURTHER ASPECTS OF
EQUILIBRIA
The ionic product of water, Kw
Water is able to act as either an acid (by donating
protons, H+) or a base (by accepting protons)
H2O(l) + H2O(l) H3O+(aq) + OH–(aq)
Simplify into : H2O(l) = H+(aq) + OH–(aq)
The equilibrium expression for this reaction is:
Kc = [H+(aq)][OH–(aq)] / [H2O(l)]
-the concentration of water as being constant.
Kw = [H+][OH–]
Kw is called the ionic product of water. Its value at 298K
is 1.00 × 10–14mol2dm–6.
Kw = [H+]2
pH calculations
The lower the hydrogen ion concentration, the higher

the pH
pH is defined as the negative logarithm to the base 10
of the hydrogen ion concentration. In symbols this is
written: pH = –log10 [H+]
Note that:
 the negative sign is introduced to make the pH
values positive in most cases
 the logarithms used are to the base 10 (not to the
base e), so make sure that when doing calculations
you press the log or lg button on your calculator
(not the ln button)
 we can use this equation to convert [H+ ] to pH or
pH to [H+ ].
Weak acids – using the acid dissociation constant, Ka
The equilibrium law can be applied to aqueous solutions

of weak acids and weak bases.
Ka is called the acid dissociation constant
For the dissociation of a monobasic acid the units are
moldm–3. We can write the general formula for a
monobasic acid as HA
HA(aq)= H+(aq) + A–(aq)
Ka = [H+][A–]/[HA]
The value of Ka indicates the extent of dissociation of
the acid.
 A high value for Ka (for example, 40moldm–3)
indicates that the position of equilibrium lies to the
right. The acid is almost completely ionised.
 A low value for Ka (for example, 1.0 × 10–4moldm–
3) indicates that the position of equilibrium lies to
the left. The acid is only slightly ionised and exists
mainly
pKa = –log10Ka
-the less positive the value of pKa , the more acidic is
the acid.
Indicators and acid–base titrations

An acid–base indicator is a dye or mixture of dyes that
changes colour over a specific pH range.
HIn =
H+ + In–
un-ionised colour A conjugate base
indicator colour B
 Adding an acid to this indicator solution shifts the
position of equilibrium to the left. There are now
more molecules of colour A.
 Adding an alkali shifts the position of equilibrium to
the right. There are now more ions of colour B.
 The colour of the indicator depends on the relative
concentrations of HIn and In–. The colour of the
indicator during a titration depends on the
concentration of H+ ions present.
Indicators usually change colour over a pH range of
between 1 and 2 pH units
Buffer solutions
A buffer solution is a solution in which the pH does not
change significantly when small amounts of acids or
alkalis are added. A buffer solution is used to keep pH
(almost) constant
One type of buffer solution is a mixture of a weak acid
and one of its salts. An example is an aqueous mixture
of ethanoic acid and sodium ethanoate
An increase in hydrogen ion concentration would
greatly lower the pH of water, but when H+ ions are
added to the buffer solution:
 addition of H+ ions shifts the position of
equilibrium to the left because H+ ions combine
with CH3COO– ions to form more CH3COOH until
equilibrium is re-established
 the large reserve supply of CH3COO– ensures that
the concentration of CH3COO– ions in solution does
not change significantly
 the large reserve supply of CH3COOH ensures that
the concentration of CH3COOH molecules in
solution does not change significantly
 so the pH does not change significantly
An increase in hydroxide ion concentration would
greatly increase the pH of water, but when OH– ions are
added to the buffer solution:
 the added OH– ions combine with H+ ions to form
water
 this reduces the H+ ion concentration
 the position of equilibrium shifts to the right
 so CH3COOH molecules ionise to form more H+
and CH3COO– ions until equilibrium is re-
established
 the large reserve supply of CH3COOH ensures that
the concentration of CH3COOH molecules in
solution does not change significantly
 the large reserve supply of CH3COO– ensures that
the concentration of CH3COO– ions in solution does
not change significantly
 so the pH does not change significantly
We can calculate the pH of a buffer solution if we know:
 the Ka of the weak acid
 the equilibrium concentration of the weak acid
and its conjugate base (salt).
[H+] = Ka × [acid]/ [salt]
we can use the expression:
pH = pKa + log10 ( [salt]/ [acid]
Equilibrium and solubility

For any solid, the concentration of the solid phase
remains constant and can be combined with the value
of Kc .
Solubility product is the product of the concentrations of
each ion in a saturated solution of a sparingly soluble
salt at 298K, raised to the power of their relative
concentrations.
K sp = [Cy+(aq)]a[Ax–(aq)]b
where a is the number of Cy+ cations in one formula
unit of the compound and b is the number of Ax– anions
in one formula unit of the compound
The common ion effect is the reduction in the solubility
of a dissolved salt achieved by adding a solution of a
compound which has an ion in common with the
dissolved salt. This often results in precipitation.
The solubility of an ionic compound in aqueous solution
containing a common ion is less than its solubility in
water.
Partition coefficients
The principle of partition of a solute between two
solvents helps us to understand more fully how the
components in a mixture are separated in
chromatography
We can calculate a value for the equilibrium constant
We call this the partition coefficient (K pc).
The partition coefficient is the equilibrium constant that
relates the concentration of a solute partitioned
between two immiscible solvents at a particular
temperature.
In paper chromatography the different partition
coefficients of the components in a mixture correspond
to their relative solubilities in the two solvents.
The greater the relative solubility in the mobile phase,
the faster the rate of movement as the mobile phase
passes over the stationary phase.
Kpc = [X(solvent A)]/ [X(solvent B)]

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Chapter 21 Further Aspects of Equilibria

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CHAPTER 21 FURTHER ASPECTS OF

The lower the hydrogen ion concentration, the higher

The equilibrium law can be applied to aqueous solutions

Indicators and acid–base titrations

Equilibrium and solubility

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