Thermodynamic potentials and

Maxwells relations
Dr. Mohammed Sultan
2014
 The energy equation
The goal: To express the internal energy in terms of measurable quantities.
The entropy is defined by the exact differential

= = = + +

Dividing both sides by T, we obtain an exact differential:
1
= + +

which must be of the form

= +

This yields:
1
= , = +

ince differentiation is a commutative operation, we have

=

Hence
1
= +

 The left-hand side can be written as T-1 CV/V, since T is kept fixed for
the differentiation. Using CV = U/T, we can rewrite the last equation in
the form
1 1 1
= 2 + + +

After canceling identical terms on both sides, we obtain the energy
equation

=

This is the expression of the internal energy in terms of measurable
quantities
Since the internal energy for an ideal gas depends only on the
temperature, and not the volume, i.e. (U/V)T = 0. Now we can show
that this is implied by the second law, through the energy equation.
Using the equation of state for the ideal gas, we have

= ideal gas

Therefore, by the energy equation,

= 0 ideal gas

 Some measurable coefficients
The energy equation relates the experimentally inaccessible quantity (U/V)T
to (P/T)V. The latter, in turn, can be related to other thermodynamic
coefficients. Using the chain rule for partial derivatives, we can write

1
= = =



where a and KT ore among some directly measurable coefficients:
1
= coefficient of thermal expansion

1
= isothermal compressibility

1
= adiabatic compressibility

Substituting the new form of (P/T)V into (U/V)T and then the latter into the
dQ equation (3.1), we obtain

= +

This equation gives the heat absorbed in terms of directly measurable coefficients.
Using T and P as independent variables, we have
=
If V and P are used as independent variables, we rewrite dT in
terms of dV and dP:
1
= + = +

In summary the TdS equations are

= +

=

= +

 Entropy and loss
The entropy of an isolated system remains
constant during a reversible process, but it
increases during an irreversible process, when the
system goes out of thermal equilibrium. Useful
energy is lost in the process, and the increase of
entropy measures the loss.
 Condition for equilibrium
The first law states
=
Using Clausius' theorem

One gets

Thus 0 for a system with S = W = 0.
This means that the internal energy will seek the lowest possible value,
when the system is thermally and mechanically isolated.
For infinitesimal reversible changes:
=
Thus, the natural variables for U are S and V.
If the function U(S, V) is known then one can obtain all thermodynamic
properties through the formulas

= , =

These are known as Maxwell relations.
 Helmholtz free energy
It is difficult to manipulate S and V in the laboratory', but it is far easier to
change T and V. It is thus natural to ask. "What is the equilibrium condition at
constant T, V?"
In order to answer this question, we go back to the inequality U TS - W. If T
is kept constant, we can rewrite it in the form

If W= 0, then (U TS) 0. One can define a new thermodynamic function, the
Helmholtz free energy (or simply free energy)
=
The earlier inequality now reads

If W = 0, then A 0. This equilibrium condition for a mechanically isolated
body at constant temperature is that the free energy be minimum.
For infinitesimal reversible transformations, we have dA = dU TdS - SdT.
Using the first law, we can reduce this to:
=
Knowing the function A(T, V), then all thermodynamic properties can be
obtained through the Maxwell relations:

= , =

The first of these reduces to the intuitive relation P = - U/V at absolute zero.
 Gibbs potential
The thermodynamic properties of a system can be obtained from the
function U(S, V) or from A(V, T), depending on the choice of independent
variables. The replacement of U by A = U - TS was motivated by the fact
that dU = T dS -PdV, and we want to replace the term TdS by SdT. This is
an example of a Legendre transformation.
Let us now consider P and T as independent variables. We introduce the
Gibbs potential G, by making a Legendre transformation on A,
= +
Then,
= + + = + +
= +
The condition for equilibrium at constant T, and P is that G be at a
minimum. We now have further Maxwell relations:

= , =

The Gibbs potential is useful in describing chemical processes, which
usually take place under constant atmospheric pressure.
 Maxwell relations
The following basic functions are related to one
other through Legendre transformations:
, : =
, : =
, : = +
, : =
Each quantity at the center of a row or column is flanked by its
natural variables.

The partial derivative with respect to one variable, with the

other kept fixed, is arrived at by following the diagonal line
originating from that variable. Attach a minus sign if you go
against the arrow.
 Chemical potential
If the number of particles N is not constant (N changes):
- The first law is generalized to the form
= +
where is called the chemical potential, the energy needed to add one
particle to a thermally and mechanically isolated system.
- For a gas-liquid system:
= +
- The change in free energy is given by
= +
which gives the Maxwell relation

=
,
For processes at constant P and T, the change in the Gibbs potential:
= +
and obtain

=
,