Ch.

5: Thermodynamic Relations

1. Enthalpy

Enthalpy is defined by the relation

H  U  PV .

If a system undergoes an infinitesimal process from an initial equilibrium state to a

final equilibrium state, then

dH  dU  P dV  V dP .

But dQ  dU  P dV . Therefore,

dH  dQ  V dP.

Dividing by dT yields

dH dQ dP
 V 
dT dT dT

If P is a constant, then

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  dQ   H 
CP      .
 dT  P  T  P

By integrating the equation above, we get

Q  H .

If a system undergoes an infinitesimal reversible process, then

dH  T dS  V dP .

From this equation, we get

 H   H 
T   and V   .
 S  P  P  S

2. The Throttling Process

Pi, Vi

Initial equilibrium state

Porous plug

Pf, Vf

Final equilibrium state

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The throttling process is an irreversible process in which both pistons move

simultaneously in such a way that a constant pressure Pi is maintained on the left-

hand side of the porous plug and a constant lower pressure Pf on the right-hand side.

Since Q = 0, the first law of thermodynamics is

U f Ui   W .

Vf 0 Vf

W 
Vi
P dV   Pi dV 
Vi

0
Pf dV   Pi Vi  Pf V f .

Pi Vi  Pf V f  U f  U i ;

U i  Pi Vi  U f  Pf V f

Hi  H f .

3. The Helmholtz Function

The Helmholtz function (or the Helmholtz free energy) is defined by the relation

F U T S .

For an infinitesimal reversible process,

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 dF  dU  T dS  S dT .

But dU  T dS  P dV . Therefore,

dF   S dT  P dV .

From this equation, we get

 F   F 
S    and P    .
 T V  V  T

For a reversible isothermal process,

dF   P dV .

Integrating the equation above, we get

Vf

F f  Fi    P dV  W ;
Vi

W   F .

This equation means that the work done by a system in a reversible isothermal

process is equal to the decrease of the Helmholtz function.

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4. The Gibbs Function

The Gibbs function (or the Gibbs free energy) is defined by the relation

G  U  T S  PV  F  PV  H  T S .

For an infinitesimal reversible process,

dG  dF  P dV  V dP .

But dF   S dT  P dV . Therefore,

dG  V dP  S dT .

From this equation, we get

 G   G 
V   and S    .
 P  T  T  P

For reversible isothermal and isobaric processes (such as phase

transformations), we have

dG  0 ;

G  constant.

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5. Maxwell's Thermodynamic Relations

Since U, H, F and G are mathematical functions, their differentials are exact and

have the form

dz  X dx  Y dy ,

where z, X and Y are all functions of x and y. The differential of z is

 z   z 
dz    dx    dy .
 x  y  y  x

By comparison,

 z   z 
X   and Y    ;
 x  y  y  x

 X  2z  Y  2z
   and    
 y  x y x  x  y x y

Therefore,

 X   Y 
     
 y  x  x  y

Let's apply this equation:

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 dU  T dS  P dV ;

 T   P 
     .
 V  S  S V

dH  T dS  V dP ;

 T   V 
    .
 P  S  S  P

dF   S dT  P dV ;

 S   P 
    .
 V  T  T V

dG  V dP  S dT ;

 V   S 
     .
 T  P  P  T

6. The T dS Equations

If S is a function of T and V, then

 S   S 
dS    dT    dV ,
 T V  V  T

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  S   S 
T dS  T   dT  T   dV .
 T V  V  T

 S   S   P 
But CV  T   and     . Therefore,
 T V  V  T  T V

 P 
T dS  CV dT  T   dV .
 T V

If S is a function of T and P, then

 S   S 
dS    dT    dP ,
 T  P  P  T

 S   S 
T dS  T   dT  T   dP .
 T  P  P  T

 S   S   V 
But C P  T   and       . Therefore,
 T  P  P  T  T  P

 V 
T dS  C P dT  T   dP .
 T  P

Example: An ideal gas undergoes a reversible isothermal pressure change from Pi to

Pf. How much heat is transferred?

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  V  nR
PV  n RT     
 T  P P

 V  dP
dQ  T dS   T   dP   n RT ;
 T  P P

Pf
dP Pf
Q   n RT 
Pi
P
  n RT ln 
Pi

If S is a function of P and V, then

 S   S 
dS    dP    dV ,
 P V  V  P

 S   S 
T dS  T   dP  T   dV .
 P V  V  P

 S   S   T   S   S   T 
But        and       . Therefore,
 P V  T V  P V  V  P  T  P  V  P

 T   T 
T dS  CV   dP  C P   dV .
 P V  V  P

Example: Reversible adiabatic process of an ideal gas.

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 PV
T ;
nR

 T  V T  T  P T
    and     
 P V n R P  V  P n R V

Thus,

dP dV
CV  CP  0,
P V

dP dV
 0  P V   constant.
P V

7. Internal Energy Equations

If a system undergoes an infinitesimal reversible process, then

dU  T dS  P dV ;

dU dS
T  P.
dV dV

If T is held constant, then

 U   S 
  T  P.
 V  T  V  T

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  S   P 
But     . Therefore,
 V  T  T V

 U   P 
  T   P.
 V  T  T V

 U 
Example: For an ideal gas, show that    0.
 V  T

 P  nR
PV  n RT     
 T V V

 U  nRT
    P  P  P  0.
 V  T V

This means that U does not depend on V at constant T.

Also, from the first law,

dU dS dV
T P 
dP dP dP

If T is held constant, then

 U   S   V 
   T    P  .
 P  T  P  T  P  T

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  S   V 
But       . Therefore,
 P  T  T  P

 U   V   V 
   T   P  .
 P T  T  P  P T

 U 
Exercise: For an ideal gas, show that    0.
 P  T

Problems

3.

For one mol of the gas,

RT a  P  R
P  2     
V b V  T V V  b

From the first T dS equation,

 P 
dQ  T dS  T   dV ;
 T V

Vf  b 
Vf
dV
Q  RT 
Vi
V b
 R T ln   .
 Vi  b 

4.

RT a
P  2 ;
 b 

 f  RT a a
   P    2  f   R T ln(  b)   fcn (T ) .
   T  b  

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5.

H  Q  (1 g) (540 cal / g)  (1 g) (0.48 cal / g.  C) (500  C)  780 cal.

9.

(a) Q  H

541 kcal / kg  641 kcal / kg  H i  H i  100 kcal / kg.

(b) We use G  H  T S for saturated water and saturated steam:

G  100 kcal / kg  (373 K) (0.3 kcal / kg.K)  12 kcal / kg.

G  641 kcal / kg  (373 K) (1.75 kcal / kg.K)  12 kcal / kg.

14.

RT a  P  R
P  2     
 b   T    b

 u   P  RT RT a a
  T   P   2  2
  T  T   b  b  

a a
du  c dT  d  u   c dT   constant.
 2


2a RT 
h  u  P   c dT    constant.
  b

If c is constant, then

2a RT 
h  c T    h0 .
  b

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