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Thermodynamic

Property Relations
General
Relations, Part 2
Objectives
Understand how thermodynamicists find
properties that cant be directly
measured
What can be measured?
Temperature, pressure, volume, mass
Other properties?
Entropy, Joule Thompson coefficient, . . .
General relations for property changes
Ideal Gases
Entropy Change via h
Find Entropy change in terms of things we can
measure
Well start with h and get to s. From Calculus
h h
h h(T,P) dh dT dP
T P P T
Using the definition of Cp
h
dh CpdT dP
P T
Entropy Change
Hold that thought, well be back
From Calculus
s s
s s(T,P) ds dT dP
T P P T
Put the above in 1st Law: dh = Tds + vdP
s s
dh T dT dP vdP
T P P T
Entropy Change
Group like terms
s s
dh T dT T v dP
T P P T
h
Recall: dh CpdT dP
P T
s s CP
Cp T
T P T P T
Entropy Change
Focusing on the change in s with respect to P,
from one of the Maxwell equations (12)
s v
P T
T P
So the total derivative is
Cp v
ds dT dP Eq. 1
T T P
Entropy Change
Cp v
ds dT dP
T T P
This can be integrated to find an entropy
change
2 2 Cp 2 v
1 ds 1 T dT 1 T P dP
2 Cp 2 v
s2 s1 dT dP
1 T 1
T P
Entropy Change Ideal Gas
2 Cp 2 v
s2 s1 dT T dP
1 T 1
P
What if Pv = RT?
v R
T P
P
2 v 2R P2
1 T P dP 1 P dP R ln P1
2 Cp P2
s2 s1 dT R ln
1 T
P1
Entropy Change Ideal Gas
2 Cp P2
s2 s1 dT R ln
1 T
P1
If Cp is a (strong) function of Temperature, we
cant pull it out of the integrand
2 Cp
1 T
dT s02 s10

0 P2
0
s2 s1 s s R ln
2 1
P1
Entropy Change Ideal Gas
2 Cp P2
s2 s1 dT R ln
1 T
P1
If Cp isnt a strong function of Temperature, or
T is small, we can pull it out of the integrand
2 Cp 2 dT T2
1 T
dT Cp,avg
1 T
Cp,avg ln
T1
T2 P2
s2 s1 Cp,avg ln R ln
T1 P1
Entropy Change via u
Find Entropy change in terms of things we can
measure
Well start with u and get to s. From Calculus
u u
u u(T,v) du dT dv
T v v T
Using the definition of Cv
u
du Cv dT dv
v T
Entropy Change
Hold that thought, well be back
From Calculus
s s
s s(T,v) ds dT dv
T v v T
Put the above in 1st Law: du = Tds - Pdv
s s
du T dT dv Pdv
T v v T
Entropy Change
Group like terms
s s
du T dT T P dv
T P v T
u
Recall: du Cv dT dv
v T
s s Cv
Cv T
T P T P T
Entropy Change
Focusing on the change in s with respect to P,
from one of the Maxwell equations (11)
s P
v T
T v
So the total derivative is
Cv P
ds dT dv
T T v
Entropy Change
Cv P
ds dT dP
T T v
This can be integrated to find an entropy
change
2 2 Cv 2 P
1 ds 1 T dT 1 T v dv
2C 2 P
s2 s1 v
dT dv
1 T 1
T v
Entropy Change Ideal Gas
2 Cv 2 P
s2 s1 dT dv
1 T 1
T v
What if Pv = RT?
P R
T v
v
2 P 2R v2
1 T v dv 1 v dv R ln v1
2C v2
s2 s1 v
dT R ln
1 T
v1
Entropy Change Ideal Gas
Cv
2 v2
s2 s1 dT R ln
1 T
v1
If Cv isnt a strong function of Temperature, or
T is small, we can pull it out of the integrand
2 Cv 2 dT T2
1 T
dT Cv,avg
1 T
Cv,avg ln
T1
T2 v2
s2 s1 Cv,avg ln R ln
T1 v1
Enthalpy Change Ideal Gas
We proved a while ago that for an Ideal gas,
the enthalpy change is
2
h 2 h1 CpdT
1

h 2 h1 Cp,avg T2 T1
Wed really like to be able to conclude that
enthalpy is not a function of pressure for an
Ideal Gas, but what if Cp depends on pressure?
Specific Heat
Earlier (Eq. 1) we found that
Cp v
ds dT dP
T T P
s CP
T T
P
s v
P T
T P
Specific Heat
Cross differentiating the partial derivatives
s s

P T P T T P T P
CP v

P T T T T P P

CP v
2
T 2
P T P
Specific Heat Ideal Gas
If Pv = RT
v R 2v
T P ; 2 0
P T P
CP v
2
T 2 0
P T P
So CP is NOT a function of pressure for an
Ideal Gas
So h is not a function of pressure for an Ideal
Gas
Joule-Thomson Coefficient
When we were dealing with refrigeration
cycles, we considered throttling valves or
capillary tubes to have refrigerants undergo
isenthalpic pressure drops.
The temperature of some fluids drop when
they undergo an isenthalpic pressure drop.
What were concerned with is
T
P JT Joule-Thomson coefficient
h
Joule-Thomson Coefficient
If the temperature goes down (T is negative)
when the pressure decreases (P is negative)

T
P JT Joule-Thomson coefficient
h
the Joule-Thomson coefficient is positive and
the fluid can be used as a refrigerant.
Joule-Thomson Coefficient
We found a general expression for enthalpy
change
v
dh CpdT v T dP
T P
Were interested in throttling processes, when
the enthalpy change is zero.
v
0 CpdT v T dP
T P
Joule-Thomson Coefficient
v
0 CpdT v T dP
T P
v
CpdT T v dP
T P h

T 1 v
JT T v
P h Cp T P
Ideal gas - JT
Can we use an ideal gas, like air, Pv = RT, as a
refrigerant? Can we throttle air and make its
temperature drop?
T 1 v
JT T v
P h Cp T P
RT v R v RT
v T v
P T P P T P P
1 v
JT,Ideal Gas T v 0
Cp T P
Collecting Results
Entropy Change:
2 Cp 2 v
s2 s1 dT dP
1 T 1
T P
2C 2 P
s2 s1 v
dT dv
1 T 1
T v
Entropy Change, Ideal Gas, large T:

0 0 P2
s2 s1 s s R ln
2 1
P1
Collecting Results
Entropy Change, Ideal Gas, small T:
T2 P2
s2 s1 Cp,avg ln R ln
T1 P1
T2 v2
s2 s1 Cv,avg ln R ln
T1 v1

Specific Heat, Cp: CP v


2
T 2
P T P
Collecting Results
Joule-Thomson Coefficient

T 1 v
JT T v
P h Cp T P
Problems?
To be solved in class!