Maxwell's relations are a set of equations in thermodynamics which are derivable from

the symmetry of second derivatives and from the definitions of the thermodynamic
potentials. These relations are named for the nineteenth-century physicist James Clerk
Maxwell.

Contents
 1 Equations
 2 The four most common Maxwell relations
o 2.1 Derivation
 3 Derivation based on Jacobians
 4 General Maxwell relationships
 5 See also

Equations
See also: symmetry of second derivatives

The structure of Maxwell relations is a statement of equality among the second

derivatives for continuous functions. It follows directly from the fact that the order of
differentiation of an analytic function of two variables is irrelevant (Schwarz theorem).
In the case of Maxwell relations the function considered is a thermodynamic potential
and xi and xj are two different natural variables for that potential:

Schwarz' theorem (general)

where the partial derivatives are taken with all other natural variables held constant. It is
seen that for every thermodynamic potential there are n(n − 1)/2 possible Maxwell
relations where n is the number of natural variables for that potential. The substantial
increase in the entropy will be verified according to the relations satisfied by the laws of
thermodynamics

The four most common Maxwell relations

The four most common Maxwell relations are the equalities of the second derivatives of
each of the four thermodynamic potentials, with respect to their thermal natural variable
(temperature T; or entropy S) and their mechanical natural variable (pressure P; or
volume V):

Maxwell's relations (common)

where the potentials as functions of their natural thermal and mechanical variables are
the internal energy U(S, V), enthalpy H(S, P), Helmholtz free energy F(T, V) and Gibbs
free energy G(T, P). The thermodynamic square can be used as a mnemonic to recall
and derive these relations. The usefulness of these relations lies in their quantifying
entropy changes, which are not directly measurable, in terms of measurable quantities
like temperature, volume, and pressure.

Derivation

Maxwell relations are based on simple partial differentiation rules, in particular the total
differential of a function and the symmetry of evaluating second order partial
derivatives.

Derivation
Extended derivation

Derivation based on Jacobians

If we view the first law of thermodynamics,

as a statement about differential forms, and take the exterior derivative of this equation,
we get

since . This leads to the fundamental identity

The physical meaning of this identity can be seen by noting that the two sides are the
equivalent ways of writing the work done in an infinitesimal Carnot cycle. An
equivalent way of writing the identity is

The Maxwell relations now follow directly. For example,

The critical step is the penultimate one. The other Maxwell relations follow in similar
fashion. For example,
General Maxwell relationships
The above are not the only Maxwell relationships. When other work terms involving
other natural variables besides the volume work are considered or when the number of
particles is included as a natural variable, other Maxwell relations become apparent. For
example, if we have a single-component gas, then the number of particles N is also a
natural variable of the above four thermodynamic potentials. The Maxwell relationship
for the enthalpy with respect to pressure and particle number would then be:

where μ is the chemical potential. In addition, there are other thermodynamic potentials
besides the four that are commonly used, and each of these potentials will yield a set of
Maxwell relations.

Each equation can be re-expressed using the relationship

which are sometimes also known as Maxwell relations.