To discuss the thermodynamic properties of liquid mixtures,
it is necessary to establish how the chemical potential of a
liquid varies with its composition. To calculate the value of
the chemical potential of the liquid we use the fact that at
equilibrium the chemical potentials of a substance in its liquid
and vapour phases are identical.
It is necessary at this stage to specify that quantities relating
to pure substances will be labeled with a * i.e. the chemical
potential of a pure substance A is written μA*.
We know that the chemical potential of a perfect gas at pressure
p can be written μ = μº + RT ln (p/pº) , and since
the vapour pressure of the pure liquid is pA* it
follows that the chemical potential of A in the vapour phase,
which at equilibrium is equal to the chemical potential of the
liquid phase, is given by the following expression: μA*
= μAº + RT ln (pA*/pº)
If there is a solute present in the liquid, then the chemical
potential of A in the liquid is μA, and the
vapour pressure is pA. Thus, by analogy with the
pure liquid situation, we may write: μA
= μAº + RT ln (pA/pº).
These two equations may be combined to give:

which relates the chemical potential of the pure substance
to the chemical potential of the impure substance.
We now use the empirical result known as Raoult's
Law: The law states that the ratio of the partial vapour
pressure of a liquid in a mixture to the vapour pressure of
the pure liquid is approximately equal to the mole fraction
of the liquid in the mixture. i.e:

The
law indicates that for a mixture of two components, this
diagram of vapour pressure against composition should
be obtained: |
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Some mixtures obey Raoult's Law very well, especially if the
components of the mixture are structurally similar. Mixtures
which obey the law at all compositions, from pure A to pure
B, are called ideal solutions.
From the previous two equations, we may derive the following
expression for an ideal solution:

This equation may now be used as the definition of an ideal
solution. i.e. an ideal solution is one which obeys this equation
at all compositions. Note that this definition does not require
us to assume the vapour is perfect. Further, this definition
of an ideal solution rather than being based upon Raoult's Law
now implies it instead.
Some solutions show very significant deviations from Raoult's
Law, but even in these cases, agreement becomes closer for the
component in excess (which we usually identify as the solvent)
as it approaches complete purity. i.e. Raoult's Law is usually
applicable to the solvent in a dilute solution.
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