An ideal solution may be defined
as one in which the interactions between all the species present
are equal (equivalent to saying ΔH of mixing is zero).
Ionic solutions are strongly non-ideal, primarily due to the
strong, long-range Coulombic interactions between ions.
To compensate for the non-ideality, we introduce the activity
of the solute as an effective concentration in all thermodynamic
calculations. The concept of activity was first introduced in
the discussion of the chemistry of solutions, here,
and it is this section that should be consulted for further
details.
Recall that the activity, a, of a solute of molality
b is given by a = γb/bº
where bº is the molality of the standard state, numerically
equal to 1 mol kg-1 , and γ
is the activity coefficient for the solution at that particular
temperature and molality.
For any ionic solution, there are activity coefficients γ+
and γ- for the cations
and anions respectively, the deviation from ideality of the
solution being related to the product of these two quantities.
There is no experimental way of separating the product γ+γ-
into distinct contributions from the cations and anions, so
a compromise is adopted whereby a mean activity coefficient,
γ± , is defined to assign
responsibility for the non-ideality equally to both types of
ion. For a compound MpXq which dissolves
in solution to give p cations and q anions for each formula
unit, we define

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