C

C
O
O
R
R
N
N
E
E
L
L
L
L

U N I V E R S I T Y
C
C
O
O
R
R
N
N
E
E
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L
L
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U N I V E R S I T Y
Lecture 19, 10/30/07
Lecture 19, 10/30/07
GENERAL THERMODYNAMIC
GENERAL THERMODYNAMIC
RELATIONS: THE J ACOBIAN
RELATIONS: THE J ACOBIAN
METHOD
METHOD
+
+
CLASIUS
CLASIUS
-
-
CLAPEYRON RELATION
CLAPEYRON RELATION
C
C
O
O
R
R
N
N
E
E
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L
L
L

U N I V E R S I T Y
C
C
O
O
R
R
N
N
E
E
L
L
L
L

U N I V E R S I T Y
Maxwell relations
Maxwell relations
C
C
O
O
R
R
N
N
E
E
L
L
L
L

U N I V E R S I T Y
C
C
O
O
R
R
N
N
E
E
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L
L

U N I V E R S I T Y
Playing with the definitions
Playing with the definitions
More such relations with the entropy!
1. From second law
2. Total differential of entropy in terms of
P and T
3. Constant pressure
C
C
O
O
R
R
N
N
E
E
L
L
L
L

U N I V E R S I T Y
C
C
O
O
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R
N
N
E
E
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U N I V E R S I T Y
Playing with the definitions
Playing with the definitions
4. Combining with
gives
Relate specific heat with entropy
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C
O
O
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R
N
N
E
E
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L

U N I V E R S I T Y
C
C
O
O
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R
N
N
E
E
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U N I V E R S I T Y
Playing with the definitions
Playing with the definitions
1. Total differential of entropy in terms of
V and T
2. Constant volume
3. Combining with
C
C
O
O
R
R
N
N
E
E
L
L
L
L

U N I V E R S I T Y
C
C
O
O
R
R
N
N
E
E
L
L
L
L

U N I V E R S I T Y
Functional relations to P and T
Functional relations to P and T
Showed functional dependence of entropy is
related to heat capacities. Now convert
thermodynamic quantities to functions of T and
P
First step: Write dS and dV in terms of T and P
C
C
O
O
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R
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N
E
E
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L

U N I V E R S I T Y
C
C
O
O
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R
N
N
E
E
L
L
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L

U N I V E R S I T Y
Functional relations to P and T
Functional relations to P and T
First step: Write dS and dV in terms of T and P
Substituting
gives
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C
O
O
R
R
N
N
E
E
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L
L
L

U N I V E R S I T Y
C
C
O
O
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R
N
N
E
E
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L
L
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U N I V E R S I T Y
Functional relations to P and T: U
Functional relations to P and T: U
Covert the four energy functions in terms
of these quantities
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C
O
O
R
R
N
N
E
E
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L

U N I V E R S I T Y
C
C
O
O
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R
N
N
E
E
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L
L
L

U N I V E R S I T Y
Functional relations to P and T: H
Functional relations to P and T: H
Writing the enthalpy H
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C
O
O
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R
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N
E
E
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L
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L

U N I V E R S I T Y
C
C
O
O
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R
N
N
E
E
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U N I V E R S I T Y
Functional relations to P and T: F
Functional relations to P and T: F
Writing the Helmholtz free energy, F
C
C
O
O
R
R
N
N
E
E
L
L
L
L

U N I V E R S I T Y
C
C
O
O
R
R
N
N
E
E
L
L
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U N I V E R S I T Y
Functional relations to P and T
Functional relations to P and T
Writing the Gibbs free energy, G
C
C
O
O
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R
N
N
E
E
L
L
L
L

U N I V E R S I T Y
C
C
O
O
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R
N
N
E
E
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U N I V E R S I T Y
General relations using the
General relations using the
Jacobians
Jacobians
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C
O
O
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R
N
N
E
E
L
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L

U N I V E R S I T Y
C
C
O
O
R
R
N
N
E
E
L
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U N I V E R S I T Y
General relations using the
General relations using the
Jacobians
Jacobians
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C
O
O
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R
N
N
E
E
L
L
L
L

U N I V E R S I T Y
C
C
O
O
R
R
N
N
E
E
L
L
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U N I V E R S I T Y
Example: S=S(T,V)
Example: S=S(T,V)
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C
O
O
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R
N
N
E
E
L
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U N I V E R S I T Y
C
C
O
O
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R
N
N
E
E
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U N I V E R S I T Y
Example: S=S(T,V)
Example: S=S(T,V)
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C
O
O
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R
N
N
E
E
L
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U N I V E R S I T Y
C
C
O
O
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R
N
N
E
E
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U N I V E R S I T Y
Example: S=S(T,V)
Example: S=S(T,V)
C
C
O
O
R
R
N
N
E
E
L
L
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L

U N I V E R S I T Y
C
C
O
O
R
R
N
N
E
E
L
L
L
L

U N I V E R S I T Y
S=S(P,V)
S=S(P,V)
C
C
O
O
R
R
N
N
E
E
L
L
L
L

U N I V E R S I T Y
C
C
O
O
R
R
N
N
E
E
L
L
L
L

U N I V E R S I T Y
S=S(P,V)
S=S(P,V)
C
C
O
O
R
R
N
N
E
E
L
L
L
L

U N I V E R S I T Y
C
C
O
O
R
R
N
N
E
E
L
L
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L

U N I V E R S I T Y
F=F(P,V)
F=F(P,V)
C
C
O
O
R
R
N
N
E
E
L
L
L
L

U N I V E R S I T Y
C
C
O
O
R
R
N
N
E
E
L
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L

U N I V E R S I T Y
H=H(S,V)
H=H(S,V)
C
C
O
O
R
R
N
N
E
E
L
L
L
L

U N I V E R S I T Y
C
C
O
O
R
R
N
N
E
E
L
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L

U N I V E R S I T Y
H=H(S,V)
H=H(S,V)
C
C
O
O
R
R
N
N
E
E
L
L
L
L

U N I V E R S I T Y
C
C
O
O
R
R
N
N
E
E
L
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L

U N I V E R S I T Y
H=H(S,V)
H=H(S,V)
C
C
O
O
R
R
N
N
E
E
L
L
L
L

U N I V E R S I T Y
C
C
O
O
R
R
N
N
E
E
L
L
L
L

U N I V E R S I T Y
H=H(S,V)
H=H(S,V)
C
C
O
O
R
R
N
N
E
E
L
L
L
L

U N I V E R S I T Y
C
C
O
O
R
R
N
N
E
E
L
L
L
L

U N I V E R S I T Y
P is a dependent variable: P(S,F)
P is a dependent variable: P(S,F)
C
C
O
O
R
R
N
N
E
E
L
L
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L

U N I V E R S I T Y
C
C
O
O
R
R
N
N
E
E
L
L
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L

U N I V E R S I T Y
P is a dependent variable: P(S,F)
P is a dependent variable: P(S,F)
C
C
O
O
R
R
N
N
E
E
L
L
L
L

U N I V E R S I T Y
C
C
O
O
R
R
N
N
E
E
L
L
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L

U N I V E R S I T Y
Useful simplification
Useful simplification
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C
O
O
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N
E
E
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U N I V E R S I T Y
C
C
O
O
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R
N
N
E
E
L
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L

U N I V E R S I T Y
Clapeyron
Clapeyron
equation
equation
Lets look at a phase transition (e.g. the water-
vapor transition).
During phase transition: dG=0 (equilibrium
condition)
0
H
G H T S S
T

= = =
C
C
O
O
R
R
N
N
E
E
L
L
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L

U N I V E R S I T Y
C
C
O
O
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R
N
N
E
E
L
L
L
L

U N I V E R S I T Y
Clapeyron
Clapeyron
equation
equation
From the Maxwell relation:
There is no V dependence here.
fg
f g
h
s
T
=
| | |
T V sat
S P dP
V T dT

= =

| | |
g f
T v sat
g f
s s
s P dP
v T dT v v

= = =

|
( )
g f
sat
g f
h h
dP
dT T v v

C
C
O
O
R
R
N
N
E
E
L
L
L
L

U N I V E R S I T Y
C
C
O
O
R
R
N
N
E
E
L
L
L
L

U N I V E R S I T Y
Clausius
Clausius
-
-
Clapeyron
Clapeyron
equation
equation
Assume and that
ideal gas conditions apply:
Then:
|
( )
g f
sat
g f
h h
dP
dT T v v

g f
v v
g
RT
v
P
=
2
|
( ) /
g f fg
sat
g f
h h h
dP
dT T v v RT P

= =

2
ln
|
fg
sat
h
d P
dT RT
=
2
1 1 2
1 1
ln ( )
fg
h
P
P R T T
=