We start with the definition of the Gibbs energy, G
= H - TS . When the system undergoes a change
of state, we may write, for any general change:

Since H = U + pV (by definition) we can write dH = dU + pdV + Vdp.
Now, the First Law of Thermodynamics states that dU
= dw + dq , which, if the change occurs
reversibly, may be substituted by the following relations: dwrev
= -pdV and dqrev
= TdS (by definition). This gives:

Crucially, since U is a state function, dU is an exact differential
and thus independent of path.
This means that the above equation may be applied in ANY
situation. The derivation was conducted for a reversible reaction
as this is the simplest case to consider.
It remains valid because for a non-reversible change, TdS >
dq (the Clausius inequality) and -pdV < dw . (Note
that numerically, -pdV is larger (more positive) than dw, but
since dw is considered as a negative quantity (the internal
energy lost by the system when it does work), it makes
more sense to say that -pdV < dw.) The two quantities adjust
so that their sum remains the same for a given process, regardless
of whether or not that process occurs reversibly.
We can substitute the expressions for dU and dH into the expression
for dG, to give:

This expression suggests that G may be correctly regarded as
a function of p and T. (Note that these are usually the variables
under experimental control in chemistry, confirming the use
and importance of G.)
The ability to regard G as a function of p and T means
that the following expression can be immediately be written
down, simply from the fundamental properties of a function of
two variables:

which in turn implies the relations:

From the first relation, we can tell that, since everything
has a positive volume, G always increases when the pressure
of the system is increased (at constant temperature and composition).
Recall that the partial derivative gives us the slope of a graph
of the top variable in the derivative against the bottom variable.
Since the molar volumes of gases are much greater than those
of solids or liquids, the Gibbs energies of gases are much more
sensitive to pressure than those of solids or liquids. Liquids
usually have slightly larger molar volumes than solids, so their
Gibbs energies are usually slightly more pressure sensitive
than those of solids:
To find the Gibbs energy at one pressure, f,
in terms of its value at another pressure, i, at a constant
temperature, we integrate the above expression relating Gibbs
energy and pressure, to give:

For liquids and solids, their volume changes only slightly
with changing pressure (consider the difficulty in compressing
a liquid or particularly a solid by applying pressure to it).
This means V may be treated as a constant and taken outside
the integral, allowing us to write, in terms of molar quantities:

Under the conditions typically encountered in a lab,
VmΔp is very small, and may be neglected. Thus
we can often make the assumption that Gibbs energies of solids
and liquids are pressure-independent. However, if the pressures
involved in the situation under consideration are large, their
effect on the Gibbs energy may be important, and the complete
expression involving the integral of Vdp must be used.
The molar volumes of gases vary greatly with pressure, meaning
we cannot treat V as a constant and take it outside the integral.
We must instead substitute for V with an expression which
shows the pressure dependence of the volume. For a perfect gas,
we make the substitution V = nRT / p , which gives:

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