Effect of Electrolytes

on Ionic Equilibria

The Effect of Electrolytes on Chemical

Equilibria

Thermodynamic equlibrium constant

(K) vs concentration-based equilibrium
constant (K).
At low electrolyte concentrations, K
approaches K (limiting value).
The dashed line represents ideal
behavior, K represents experimental
behavior.
The effect is not unique to NaCl, we
would see nearly identical curves if
KNO3 or NaClO4 were substituted for
NaCl.
The effect doubles for Ksp of BaSO4.
The origin of the effect is the
electrostatic attraction between the ions
of the electrolyte and the ions of
reacting species of opposite charge.

Kw H2O
Ka HOAc
Ksp BaSO4

The Effect of Ionic Charges on Equilibria

The magnitude of the electrolyte effect is
highly dependent on the charges of the
participants in an equilibrium.
When only neutral species are involved, the
position of equilibrium is essentially
independent of electrolyte concentration.
With ionic participants, the magnitude of the
electrolyte effect increases with charge.
The Effect of Ionic Strength
Systematic studies have shown that the effect
is independent of the chemical nature of the
electrolyte but depends on a property of he
solution called the ionic strength.

Example
Calculate the ionic strength of (a) a 0.1 M solution of KNO3 and (b) a 0.1 M
solution of Na2SO4.
What is the ionic strength of a solution that is 0.05 M in KNO3 and 0.1 M in
Na2SO4?

For solutions with ionic strengths of 0.1 M or less, the electrolyte effect is
independent of the kind of ions and dependent only on the ionic strength.
Note that this independence with respect to electrolyte species disappears
at high ionic strengths.
The Salt Effect
Results from the electrostatic attractive and repulsive forces between the
ions of an electrolyte (for example NaCl) and the ions involved in an
equilibrium.
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The Salt Effect

Each ion from the dissociated reactant is surrounded by a sheath of
solution that contains a slight excess of electrolyte ions of opposite charge.
These charged layers make the cations appear to be somewhat less positive
and the anions somewhat less negative than in the absence of NaCl.
The result is a decrease in overall attraction between cations and anions.
In other words, the effective concentration (activity) of cations and anions
in an equilibrium process becomes less as the ionic strength of the medium
becomes greater.

Activity Coefficient
The activity, or effective concentration, of species X depends on the ionic
strength of the medium and is defined by
X is a dimensionless quantity called the activity coefficient.
Application to equilibrium (eg Ksp) gives
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Properties of Activity Coefficients

The activity coefficient of a species is a measure of the effectiveness with
which that species influences an equilibrium in which it is a participant.
In very dilute solutions in which the ionic strength is minimal, this
effectiveness becomes constant, and the activity coefficient is unity.
The
activity and the molar concentration are identical (as are thermodynamic
and concentration equilibrium constants).
As the ionic strength increases, however, an ion loses some of its
effectiveness, and its activity coefficient decreases.
At high ionic strengths (> 0.1 M), activity coefficients often increase and
may even become greater than unity.

In solutions that are not too concentrated, the activity coefficient for a given
species is independent of the nature of the electrolyte and dependent only
on the ionic strength.
For a given ionic strength, the activity coefficient of an ion decreases more
dramatically from unity as the charge on the species increases.
The activity coefficient of an uncharged molecule is approximately unity,
no matter what the level of ionic strength.
At any given ionic strength, the activity coefficients of ions of the same
charge are approximately equal.
The small variations among ions of the same charge can be correlated with
the effective diameter of the hydrated ions.
The activity coefficient of a given ion describes its effective behavior in all
equilibria in which it participates. For example, the same activity
coefficient applies to any equilibrium reactions

The Debye-Hckel Equation

Uses the ionic atmosphere model to derive an equation that permits the
calculation of activity coefficients of ions from their charge and their
average size.

The constants 0.51 and 3.3 are applicable to aqueous solutions at 25C.
Other values must be used at other temperatures.
X 0.3 nm for most singly charged ions

denominator 1 + .

For ions with higher charge, X may be as large as 1.0 nm.

The second term of the denominator is small with respect to the first when
the ionic strength is less than 0.01 M
uncertainties in X have little effect
on calculating activity coefficients.
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Kiellband Values

Equilibrium Calculations Using Activity Coefficients

Produce results that agree with experimental data more closely than those
obtained with molar concentrations.
Equilibrium constants found in tables are usually based on activities and
are thus thermodynamic constants.
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Example
Find the relative error introduced by neglecting activities in calculating the
solubility of Ba(IO3)2 in a 0.033 M solution of Mg(IO3)2. The thermodynamic
solubility product for Ba(IO3)2 is 1.57 x 10-9
Solution

Replacing activities in this equation with activity coefficients and

concentrations yields

Lets calculate the activity coefficient, we ignore ions coming from Ba(IO3)2

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From the table we find for a total concentration of 0.1 M

Calculating solubity from the common ion effect we find

If we directly calculate from Ksp

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Example
Use activities to calculate the hydronium ion concentration in a 0.120 M
solution of HNO2 that is also 0.050 M in NaCl. What is the relative percent
error incurred by neglecting activity corrections?
Solution

Since HNO2 has no charge

Since Ka = 7.1 x 10-4

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If we calculate directly from Ka

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[H3O+] = 9.2 x 10-3 M