The Third Law of

Thermodynamic
T
C
T
S
P
P
A
= |
.
|

\
|
c
A c
Introduction

Recall :



C
P
always +, and so T
If T is reduced to nearly zero, T T=0 therefore:

C
P
0 so AC
P
0 then AS 0
(Nernst heat law)
T
C
T
S
P
P
=
|
.
|

\
|
c
c
Formulation (third law) :

Entropy for all pure solid, perfect crystal, at
zero Kelvin is equal to zero

S
0
T
= standard entropy ( P = 1 atm, T = 0K)
S
T
= entropy of solid at pressure P and temp T

FREE ENERGY

2 Types :
Helmholtz free energy, A
- concerns with expansion and compression
Gibbs free energy, G
- concerns with chemical reactions
Define :
A = U TS
G = H TS
Equilibrium
dA = 0, dG = 0 equlibrium
dA < 0, dG < 0 inequilibrium

Fundamental equation
first law dU = dq PdV
dU = dq
rev
PdV = TdS PdV
dU = TdS PdV .. (1)

from definition of H, A and G , we obtain

dH = TdS + VdP . (2)
dA = - PdV SdT .(3)
dG = VdP SdT .(4)
Equations (1) to (4) are known as Fundamental
equations of thermodynamics

Maxwell equations
since dU, dH, dA and dG are exact differentials in
the form of
dz = Mdx + Ndy
Then:






These equations are known as Maxwell
equations/relationships.


y
x
x
N
y
M
|
.
|

\
|
c
c
=
|
|
.
|

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

\
|
c
c
=
|
.
|

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

\
|
c
c
=
|
.
|

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

\
|
c
c
=
|
.
|

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

\
|
c
c
=
|
.
|

\
|
c
c
These equations can easily be written using this
phrase
Good Physicists Have Studied Under Very Fine
Teachers
a) first step b) Second step






Properties of A


G P
H
S
U V
F A
T
+
+