We have already remarked that, for a pure substance, the chemical
potential is just another name for the molar Gibbs energy. For
a substance in a mixture, the chemical potential is defined
as being the partial molar Gibbs energy:

i.e. the chemical potential is the slope of a plot of the Gibbs
energy of the mixture against the amount of component J, with
all other variables held constant:
In the above plot, the partial molar Gibbs energy
is greater at I than at II.
The total Gibbs energy of a binary mixture is given by:

(Compare the expression for the total volume of a binary solution
in terms of its partial molar volumes given on the previous
page.) The above expression may be generalised quite trivially
to a mixture with an arbitrary number of components:

where the sum is across all the different substances present
in the mixture, and the chemical potentials are those at the
composition of the mixture.
This indicates that the chemical potential of a substance in
a mixture is the contribution that substance makes to the total
Gibbs energy of the mixture.
In general, the Gibbs energy depends upon the composition,
pressure and temperature. Thus G may change when any of these
variables alter, so for a system that has components A, B, etc,
it is possible to rewrite the equation dG = Vdp - SdT (which
is a general result that was derived here)
as follows:

which is called the fundamental equation
of chemical thermodynamics.
At constant temperature and pressure, the equation simplifies
to:

Under these conditions, dG = dwn,max (as was demonstrated
here),
where the n indicates that the work is non-expansion work. Therefore,
at constant temperature and pressure:

The idea that the changing composition of a system can do work
should be familiar - this is what happens in an electrochemical
cell, where the two halves of the chemical reaction are separated
in space (at the two electrodes) and the changing composition
results in the motion of electrons through a circuit, which
can be used to do electrical work.
On a final note, it is possible to use the relationships between
G and H, and G and U, to generate the following relations:

Note particularly the conditions (the variables that must be
held constant) under which each relation applies.
|