Euler and Gibbs-Duhem Equations

Since U is a homogeneous first order function of extensive variables S, V , N1 , N2 , etc., for

any scalar it should satisfy
U (S, V, N1 , N2 , . . .) = U (S, V, N1 , N2 , . . .)

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Differentiating Eqn. 1 with respect to and utilizing chain rule of differentiation, we get

U (S)
U (V )
U (N1 )
+
+
+ . . . = U
(S)
(V )
(N1 )
U
U
U

S+
V +
N1 + . . . = U
(S)
(V )
(N1 )

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Since these equations are valid for any value of , we try to put a specific value, viz. = 1.
Using previous definitions of the first partial derivatives of U , we now get:

U = TS PV +

r
X

i Ni

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i=1

This is the Euler equation in thermodynamics.

Taking an exact differential of the Euler equation, we get

dU = T dS + SdT P dV V dP +

r
X

i dNi +

i=1

r
X

di Ni

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i=1

Comparing with our previously defined/derived relation

dU = T dS P dV +

r
X

i dNi

i=1

we see that
SdT V dP +

r
X

Ni di = 0

i=1

This is the Gibbs-Duhem equation.

References
[1] H.B. Callen: Introduction to Thermodynamics and Thermostatistics

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