Thermodynamic Potentials

Why are thermodynamic potentials useful

Consider U=U(T,V)
Complete knowledge of equilibrium properties of a simple thermodynamic
System requires in addition
P=P(T,V) equation of state
U=U(T,V) and P=P(T,V) complete knowledge of equilibrium properties
However
U(T,V) is not a thermodynamic potential
We are going to show: U=U(S,V)
complete knowledge of equilibrium properties
U(S,V): thermodynamic potential
The thermodynamic potential U=U(S,V)
Consider first law in differential notation W d Q d dU =
inexact differentials
W d
Q d
expressed by exact differentials
PdV W d
TdS Q d
=
=
2
nd
law
PdV TdS dU =
Legendre Transformations
PdV TdS dU = dU: differential of the function U=U(S,V)
natural coordinates
Note: exact refers here to the
coordinate differentials dS and dV.
T dS and PdV are inexact
as we showed previously.
PdV TdS dU =
Legendre transformation
Special type of coordinate transformation
Example:
coordinates
Partial derivatives of U(S,V) (vector field components)
Legendre transformation: One (or more) of the natural coordinates becomes
a vector field component
while the
associated coefficient becomes new coordinate.
PdV TdS dU =
Back to our example
becomes a coordinate
becomes a coefficient in front of dP
Click for
graphic example
( ) VdP TdS PV d dU + = +
( ) VdP PV d TdS dU + =
easy check: ( ) PdV VdP PdV VdP VdP PV d = + = +
Product
rule
( ) VdP TdS PV U d + = +
=:H (enthalpy)
H=H(S,P) is a thermodynamic potential
VdP TdS dH + =
Enthalpy
0.0 0.5 1.0 1.5 2.0
-2
0
2
4
6
8


Y

X
0 1 2 3 4 5 6 7 8
-8
-6
-4
-2
0
2


Y
-
Y
'
x
Y'
Geometrical interpretation of the
Legendre transformation
- 1-dimensional example
) x x )( x ( Y ) x ( Y ) x ( T
0 0 0
' + =
) x ( Y x ) x ( Y ) 0 ( T
0 0 0
'
=
) Y ( xd ) x Y ( d dx Y dY ' ' = ' =
) Y ( xd ) x Y Y ( d ' = '
f : =
Note: natural variable of f is Y Y and X have to be expressed as Y=Y(Y) and x=x(Y)
Y e Y
x
' = =
mapping between the graph of the function and
the family of tangents of the graph
Legendre transformation:
Legendre transformation
from (S,V)
to
(T,V): PdV TdS dU =
PdV SdT ) TS ( d =
PdV SdT ) TS U ( d =
F : = Helmholtz free energy
(T,P):
PdV SdT dF =
VdP ) PV ( d SdT + =
VdP SdT ) PV F ( d + = +
G : = Gibbs free energy
TS H PV TS U PV F G = + = + =
equilibrium thermodynamics and potentials
complete knowledge of equilibrium properties
Consider Helmholtz free energy F=F(T,V)
PdV SdT dF =
Differential reads:
V
T
F
S |
.
|

\
|
c
c
=
and
T
V
F
P |
.
|

\
|
c
c
=
Entropy
Equation of state
Response functions from 2
nd
derivatives
V
V
T
S
T C |
.
|

\
|
c
c
=
V
2
2
T
F
T
|
|
.
|

\
|
c
c
=
T
T
V
P
V B |
.
|

\
|
c
c
=
2
2
T
F
V
V
| | c
=
|
c
\ .
and
P T
T V
T
V
V
P
B |
.
|

\
|
c
c
|
.
|

\
|
c
c
= o
V
T
P
|
.
|

\
|
c
c
=
V T
F
2
c c
c
=
etc.
thermodynamics potential
Maxwell relations

PdV SdT dF = differential of the function F=F(T,V)
dF is an exact differential
V
2 2
T
T
P
V T
F
T V
F
V
S
|
.
|

\
|
c
c
=
c c
c
=
c c
c
= |
.
|

\
|
c
c

V T
T
P
V
S
|
.
|

\
|
c
c
= |
.
|

\
|
c
c
In general: relations which follow from the exactness of the differentials
of thermodynamic potentials are called Maxwell relations
Properties of an ideal gas derived from the Helmholtz free energy
Helmholtz free energy F=U-TS
Reminder:
) V , T ( S
V
V
ln nR
T
T
ln nc ) V , T ( S
r r
r r
V
+ + =
0 v
nu T nc ) V , T ( U + =
| |
r 0
r r
V
Ts u n
V
V
ln nRT
T
T
ln 1 T nc ) V , T ( F +
|
|
.
|

\
|
=
Equation of state:
T
V
F
) V , T ( P |
.
|

\
|
c
c
=
V
nRT
=
| |
0
1 ln ln
V r
r r
T
T V
nc T nRT n u Ts
V T V
| |
| | c
= +
|
|
c
\ .
\ .
T
r
V
V
V
ln nRT
|
|
|
|
.
|

\
|
c
c
=
Equation of state derived from F
Note: U derived from F
S(T,V)
V
T
F
S |
.
|

\
|
c
c
=
obtained from ) V , T ( S
V
V
ln nR
T
T
ln nc ) V , T ( S
r r
r r
V
+ + =
U(T,V) obtained from U=F+TS
V
T
F
T F |
.
|

\
|
c
c
=
0 v
nu T nc ) V , T ( U + =
Heat capacity at constant volume
V
V
V
nc
T
U
C =
|
.
|

\
|
c
c
=
Isothermal bulk modulus
T
T
V
P
V B |
.
|

\
|
c
c
= P
V
nRT
V
nRT
V
2
= =
|
|
.
|

\
|
=
etc.
System
E



Heat Reservoir R
Systems in Contact with Reservoirs
Entropy statement of 2
nd
law: entropy always increased in an
adiabatically isolated system
What can we say about evolution of systems which are not adiabatically isolated
T=const.
adiabatic wall
E changes from initial state with
o o o o
PV TS U G + =
to final state with
f f f f
PV TS U G + =
V P S T U G G G
0 f
A + A A = = A
remain constant
Consider system at constant temperature and pressure
V P S T U G A + A A = A
From Entropy change of E:
T
G V P U
S
A A + A
= A
Entropy change
Aim: Find the total entropy change
R tot
S S S A + A = A and apply 2
nd
law
of the reservoir:
R
S A
}
= A
L
R
R
T
Q d
S
}
=
L
R
Q d
T
1
T
Q
R
=
Heat Q
R
that, e.g., leaves the reservoir flows into the system E
Q = -Q
R

R tot
S S S A + A = A
T
Q
T
G V P U
R
+
A A + A
=
With 1
st
law:
V P Q W Q U A = = A
T
Q
T
G Q
R
+
A
=
tot
S A
T
G A
=
Heat reservoir: T=const.
Entropy statement of 2
nd
law: 0 S
tot
> A
0
T
G
>
A
for an adiabatically isolated system
0 Gs A
Gibbs free energy never increases in a process at fixed pressure
in a system in contact with a heat reservoir.

Gibbs free energy will decrease if it can, since in doing so
it causes the total entropy to increase.
(T=const, P=const.)
System with V=const. in contact with a heat reservoir
Special case, very important for problems in solid state physics
S T U F A A = A
T
F U
S
A A
= A
T
F Q A
=
R tot
S S S A + A = A
T
Q
R
+
T
F A
=
0 Fs A
(T=const, V=const.)
Q = -Q
R

T
F Q A
=
Summary: Thermodynamic potentials for PVT systems
T=const,P=const

T=const,V=const

Isobaric
process

1
st
law:

Properties
Maxwell
relations
Vector field
components
dG=-SdT+VdP dF=-SdT-PdV dH=TdS+VdP dU=TdS-PdV differential
Gibbs free
energy
G(T,P)
G=U TS+PV

Helmholtz free
energy
F(T,V)
F=U -TS
Enthalpy
H(S,P)
H=U+PV
Internal energy
U(S,V) Potential
V
S
U
T |
.
|

\
|
c
c
=
S
V
U
P , |
.
|

\
|
c
c
=
P
S
H
T |
.
|

\
|
c
c
=
S
P
H
V , |
.
|

\
|
c
c
=
V
T
F
S |
.
|

\
|
c
c
=
T
V
F
P , |
.
|

\
|
c
c
=
P
T
G
S |
.
|

\
|
c
c
=
T
P
G
V , |
.
|

\
|
c
c
=
V S
S
P
V
T
|
.
|

\
|
c
c
= |
.
|

\
|
c
c
V T
T
P
V
S
|
.
|

\
|
c
c
= |
.
|

\
|
c
c
S T
T
V
P
S
|
.
|

\
|
c
c
= |
.
|

\
|
c
c

W Q U = A
Q H= A
0 Fs A 0 Gs A
P S
S
V
P
T
|
.
|

\
|
c
c
=
|
.
|

\
|
c
c
Open Systems and Chemical Potentials
Open system Particle exchange with the surrounding allowed

Heat Reservoir R
T=const.
Thermodynamic potentials depend on variable particle number N
Example: U=U(S,V,N)
Particle reservoir
U( S, V, N) = 2 U(S,V,N) 2 2 2
In general:
) N , V , S ( U ) N , V , S ( U =
c
c
c
c
|
|
.
|

\
|
c
c
+
c
c
|
|
.
|

\
|
c
c
+
c
c
|
|
.
|

\
|
c
c

) N (
) N (
U ) V (
) V (
U ) S (
) S (
U
V , S N , S N , V
) N , V , S ( U =
S V N
holds and in particular for =1
) N , V , S ( U N
N
U
V
V
U
S
S
U
V , S N , S N , V
= |
.
|

\
|
c
c
+ |
.
|

\
|
c
c
+ |
.
|

\
|
c
c
(homogeneous function of first order)
) N , V , S ( U N
N
U
V
V
U
S
S
U
V , S N , S N , V
= |
.
|

\
|
c
c
+ |
.
|

\
|
c
c
+ |
.
|

\
|
c
c
keep N constant as in closed systems
T
S
U
N , V
= |
.
|

\
|
c
c
, S N
U
P
V
c
| |
=
|
c
\ .
= |
.
|

\
|
c
c
:
N
U
V , S
Chemical potential
N PV TS ) N , V , S ( U + =
dN
N
U
dV
V
U
dS
S
U
dU
V , S N , S N , V
|
.
|

\
|
c
c
+ |
.
|

\
|
c
c
+ |
.
|

\
|
c
c
=
dN PdV TdS dU + =
Intuitive meaning of the chemical potential
First law:
W d Q d dU =
with
TdS Q d =
W d TdS dU =
mechanical work PdV work dN required to change
# of particles by dN
+
How do the other potentials change when particle exchange is allowed
Helmholtz free energy F=U-TS
SdT TdS dU ) TS ( d dU dF = =
dN PdV TdS dU + =
dN PdV SdT dF + =
Gibbs free energy G=U -TS+PV
VdP PdV dF + + = ) PV ( d dF dG + =
dN PdV SdT dF + =
dN VdP SdT dG + + =
P , T V , T V , S
N
G
N
F
N
U
|
.
|

\
|
c
c
= |
.
|

\
|
c
c
= |
.
|

\
|
c
c
=
Properties of
With and
N PV TS U + = PV TS U G + =
N
G
=
both extensive
) P , T ( =
intensive (independent of N)
F
Equilibrium Conditions

Adiabatically isolating
rigid wall
System1:
T
1
,P
1
,
1

System2:
T
2
,P
2
,
2

Q d
From
differentials of entropy changes
dN PdV TdS dU + =
1
1
1
1
1
1
1
1
1
dN
T
dV
T
P
T
dU
dS

+ =
2
2
2
2
2
2
2
2
2
dN
T
dV
T
P
T
dU
dS

+ =
Total entropy change
1 2
S S S 0 A = A + A >
2
nd
law
In equilibrium
1 2
dS dS dS 0 = + =
With conservation of
-total internal energy
1 2
U U const. + =
1 2
dU dU =
-total volume
1 2
V V const. + =
1 2
dV dV =
-total # of particles
1 2
N N const. + =
1 2
dN dN =
1 2 1 2
1 1 1
1 2 1 2 1 2
1 1 P P
dS dU dV dN 0
T T T T T T
| | | | | |

= + =
| | |
\ . \ . \ .
1 2 1 2
1 1 1
1 2 1 2 1 2
1 1 P P
dS dU dV dN 0
T T T T T T
| | | | | |

= + =
| | |
\ . \ . \ .
small changes dU
1
, dV
1
, dN
1

0 0 0
Equilibrium conditions
T
1
= T
2
, P
1
= P
2
,
1
=
2

Remark:
) P , T ( =
T
1
= T
2
, P
1
= P
2

and
1
=
2

1
=
2
no new information for system in a single phase
but
Important information if system separated into several phases (see next chapter)