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V S
S V
T
V
S
S
p
V T T V
S
V
T p
p T
James Clerk
Maxwell
Example 1:
The Maxwell relation based on G can be derived as follows.
G SdT Vdp
hence
G
S
T p
G
G
dG
dT
dp
T p
p T
and
G
V
2G 2G
S
V
p T T p
T
p
V S
S V
T
V
S
p
dF SdT pdV
S
p
V T T V
dG SdT VdP
S
V
dU TdS pdV
dH TdS Vdp
T p
For example,
describe how the volume changes as the
temperature while keeping the pressure fixed.
This is related to a quantity called the isobaric expansivity and is a
quantity that can easily imagine being something one could measure in
a laboratory.
S
For
, this term is much more mysterious and it is not obvious how
a change of entropy with pressure at constant temperature could
actually be measured.
T
T V
S
Cp
V T p
isobaric expansivity
1 V
S
V T S
adiabatic expansivity
1 V
T
V p T
isothermal compressibility
1 V
S
V p S
adiabatic compressibility
Example 2:
Find expressions for
, and .
and
in terms of ,
Q
S
CV
T V
T V
Define and
Q
S
Cp
T p
T p
Q
S
Cp
T p
T p
Now,
S
S
S
C p
T p
p T
p T
V
2V
C p
T
2
p p
2 p
CV
V T
2
Example 3:
By considering = (, ), show that
C p CV VT 2p T .
dV
dT
T p T V
V T T p
V T T V
V T T p
Hence,
C p CV
VT 2p
T
Example 4:
Find the entropy of 1 mole of ideal gas.
For one mole of ideal gas = . Consider the entropy as a
function of volume and temperature ,
= (, )
S
S
dS
dT
dV
T V
V T
CV
p
dT
dV
T
T V
R
p
T V V
dS
CV
R
dT
dV
T
V
Question 1:
Find the ratio of the isothermal and adiabatic compressibilities.