ME 7002 (522 M1460) Advanced Thermodynamics

Fall, 2018
Topic 5. Alternative Formulations and Legendre Transformations
Instructor: Kuo-Long Pan

Contents
I. The Energy Minimum Principle
II. Legendre transformations
III. Thermodynamic potentials
IV. Generalized Massieu functions

Reading
H. B. Callen, Thermodynamics and An Introduction to Thermostatistics, 2nd Ed., Chap. 5.

I. The Energy Minimum Principle

Entropy maximum principle
․ The equilibrium value of any unconstrained internal parameter is such as to maximize the
entropy for the given value of the total internal energy.

Energy minimum principle

․ The equilibrium value of any unconstrained internal parameter is such as to minimize the
energy for the given value of the total entropy.

Demonstration
․ Physical elucidation (or starting with a geometrical intuition)
․ Mathematical derivation

1
  S   2S 
  0  2   0
 X U  X U
 S 
 
 U   X U  S 
P    T   0
 X  S  S   X U
 
 U  X
Since S = S(U, X), P = P(U, X) (or from the derivative of U with respect to X at constant S).

  2U   P   P   U   P   P   P   P 
 2             P    at P  0
 X  S  X  S  U  X  X  S  X U  U  X  X U  X U

  S    2S  2S
   2 
   X U  X U  S  XU 2S S
         T  0 at 0
X   S    S   X U  S 
2
X 2
X
  U    
 U  X
 
 X U  U 

Equivalence of the two alternative extremal criteria

․ Analogy to the geometrical construction of a circle (maximum area for given perimeter vs.
minimum perimeter for given area).
․ An example of attaining equilibrium via two different processes: a piston with constraint
removed  Independent of whether the equilibrium is brought about by either of these
processes, or by any other process, the final equilibrium state in each case satisfies both
extremal conditions.

Thermal equilibrium condition constructed via energy minimum principle

U  U 1 S 1 , V 1 ,  , N j1 ,   U 2  S 2  , V 2  , , N j2  , 

dU  T 1dS 1  T 2 dS 2 
 T 1  T 2  dS 1  0
T 1  T 2 

II. Legendre Transformations

Interchange of extensive parameters and intensive parameters
․ Frequently the experimenter finds that the intensive parameters are the more easily
measured and controlled; it is likely to think of the intensive parameters as operationally
independent variables and of the extensive parameters as operationally derived quantities,

2
 e.g. the conjugate variables S and T.

Direct transformation
․ Change of independent variables Y  Y  X 0, X 1 ,, X t 
․ An example of unacceptable formalism: Y
Pk 
Y(X)  Y(P), but certain information is lost. X k

Legendre transformation
․ Point geometry  line geometry    P   Y  PX
․  : Legendre transform of Y Y  Y X 
P  P X 
Inverse transformation
․ Symmetrical relation between (X, Y) and (P, ) except for a sign
d
d  dY  PdX  XdP   XdP  X  
dP
Y  Y(X )    ( P)
dY d
P X 
dX dP
  Y  PX Y    XP
eliminatio
     ( P )
n of X and Y
eliminatio
 n of P and 
  Y  Y ( X )

Legendre transformation to functions of multiple independent variables

․ The hypersurface Y  Y  X 0, X 1 ,  , X t      P 0 , P1 , , Pt 
․ The partial slope  Y 
Pk   

 k i  0...t ,i  k
X
t
  Y   Pk X k
k 0
t
  
d    X k dPk   X k   
k 0 
 k i  0...t ,i  k
P

Partial Legendre transformation

․ The transformation can be made for only in some (n + 2) dimensional subspace of the (t +
2) space while the other variables are treated as constants. Y[P0, P1,…, Pn] = func(P0, P1, …
Pn, Xn+1,…, Xt)

3
 Y  Y  X 0, X 1 ,  , X t  Y P 0 , P1 ,  , Pn 
Y Y P 0 , P1 ,  , Pn 
Pk   Xk  kn
X k Pk
t
Y P 0 , P1 ,  , Pn 
dY   Pk dX k Pk  k n
0 X k
n
Y P 0 , P1 ,  , Pn   Y   Pk X k
n t
dY P 0 , P1 ,  , Pn    X k dPk   Pk dX k
0 0 n 1
n
Y  Y P 0 , P1 ,  , Pn    Pk X k
0

Lagrangian versus Hamiltonian mechanics

III. Thermodynamic Potentials

Helmholtz potential (Helmholtz free energy): F  U[T]
U  U S ,V , N1 , N 2 , F  F T , V , N1 , N 2 ,
U F
T S 
S T
F  U  TS U  F  TS
eliminatio
   F  F T , V , N1 , N 2 ,
n of U , S
eliminatio
  U  U S , V , N1 , N 2 , 
n of F , T

dF   SdT  PdV  1dN1   2 dN 2  

Enthalpy: H  U[P]
U  U S ,V , N1 , N 2 , H  H S , P, N1 , N 2 ,
U H
P V
V P
H  U  PV U  H  PV
eliminatio
   H  H S , P, N1 , N 2 ,
n of U , V
eliminatio
 U  U S ,V , N1 , N 2 , 
n of H , P

dH  TdS  VdP  1dN1   2 dN 2  

4
Gibbs potential (Gibbs free energy): G  U[T, P]
U  U S ,V , N1 , N 2 , G  G T , P, N1 , N 2 ,
U U G G
T P S  V
S V T P
G  U  TS  PV U  G  TS  PV
eliminatio
   G  G T , P, N1 , N 2 ,
n of U , S , V
eliminatio
  U  U S , V , N1 , N 2 , 
n of G , T , P

dG   SdT  VdP  1dN1   2 dN 2  

Grand canonical potential: U[T, ]

U  U S , V , N  U T ,    U T ,  T , V ,  
U U U T ,   U T ,  
T  S  N 
S N T 
U T ,    U  ST  N U  U T ,    TS  N
eliminatio
  U T ,    U T ,  T , V ,  
n of U , S , N
eliminatio
  U  U S ,V , N 
n of U T ,  , T , 

dU T ,     SdT  PdV  Nd

Complete Legendre transform: U[T, P, 1 , 2,..., r]

U T , P, 1 ,,  r   U  TS  PV  1 N1   2 N 2     r N r
0 by the Euler equation

IV. Generalized Massieu Functions

Legendre transformation on the entropy
1 1 F
S   S  U  
T  T T

P P
S    S  V
T  T

1 P 1 P G
S  ,   S  U  V  
T T  T T T
․ S[P/T] is not trivially related to the thermodynamic potentials.

5
S  S U , V , N1 , N 2 ,  S P T   S P T U , P T , N1 , N 2 ,
P T  S V S P T 
V 
S P T   S  P T V  P T 
 P  P  S  S P T   P T V
eliminatio
  S  U , , N1 , N 2 , 
n of S , V

 T  T  eliminatio
   S U ,V , N1 , N 2 ,
n of S  P T , P T

dS P T   1 T dU  Vd P T   1 T dN1   2 T dN 2 

Homework #5
․ 5.1-2
․ 5.2-1, 5.2-2
․ 5.3-1, 5.3-10, 5.3-13