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Energies, Thermodynamic Identities, Maxwell Relations, and the Magic Square

Professor A. J. Mallinckrodt, Physics Department, Cal Poly Pomona, November 2001

Thermodynamic identity for energy Magic Square VAT, UG, SHP (Vat Ugh Ship)
dU = TdS PdV( +dN + ...) Notice that 1) each side has V A T
an energy, 2) each energy is
Additional energies flanked by its two most
U G
H = U + PV (Enthalpy) important natural variables,
A = U TS (Helmholtz free energy) 3) conjugate variables
G = U + PV TS (Gibbs free energy) occupy opposite ends of each S H P
diagonal, 4) crossed arrows
Additional thermodynamic identities point upward toward V and T and away from S and P.
dH = TdS + VdP( +dN +... )
Partial derivatives from the Magic Square
dA = SdT PdV (+dN + . .). Starting at any energy, read toward one of the natural
dG = SdT + VdP( +dN + . .). variables Partial of wrt and away from the other at
constant and look across for the result and its sign (as
Natural variables indicated by the arrow head) is . For instance:
U S & V (& N & ...)
=+V A T V A T
H S & P (& N & ...)
A T & V (& N & ...)
U G U G
G T & P (& N & ...)

Conjugate variables
(S) H P =-S H (P)
S & T, P & V, ( & N, ...)
1) Partial of H wrt P at constant S is +V
Partial derivative relations 2) Partial of G wrt T at constant P is S
U U
= T, = P, ... Thermodynamic identities from the Magic Square
S V ,N,... V S, N,... Intimately related to the partial derivative relations. For any
H H energy read toward both of its natural variables and across for
= T, = V , ...
S P, N,... P S, N,... the conjugate variables and signs. For instance,
A A 1) dH is +V times dP plus +T times dS
= S , = P , ... 2) dG is -S times dT plus +V times dP
T V , N,... V T, N ,...
G G Maxwell Relations from the Magic Square
= S, = V , ...
T P, N,... P T ,N ,... Using only corners, start at any corner and read clockwise or
counterclockwise Partial of wrt at constant .
Maxwell relations Proceed in the same direction to the next corner and then
(obtained by equating reordered second derivatives of each reverse direction to obtain the other side of the equation.
energy with respect to its natural variables) Insert a minus sign if the arrows do not point toward or away
T P from both starting points. For example:
=
V S S V
V A T
V T
=
S P P S
U G
S V
=
P T T P
P S S H P
=
T V V T Partial of T wrt V at constant S and partial of P wrt S at
constant V are opposites. (Since T has an arrowhead and P
doesnt.)