The Joule-Thomson expansion

The Joule-Thomson experiment is deceptively easy to describe

and correspondingly difficult to perform. The experiment
consists of forcing a gas at constant backing pressure through a
porous plug and measuring the change in temperature.
P1 The Joule-Thomson
coefficient is equal to

∂T
µJT =
∂P
P2
 The Joule-Thomson expansion...
∂T
The Joule-Thomson coefficient is µJT =
∂P
The most straightforward way to measure the coefficient is to
measure the temperature of the gas entering and leaving the
porous plug and divide the change in temperature by the
change in pressure:
 ∂T  ∆T T2 − T1
≈ =
 ∂P  ∆P P2 − P1
 The Joule-Thomson expansion...
∂T
The Joule-Thomson coefficient is µJT =
∂P
As usual, we need to decide what is being held constant when
we take the partial derivative. In this case, since q=0, the
change in internal energy of the gas is just w, so that
∆U = U 2 − U 1 = P1V1 − P2V2
or,
U1 + P1V1 = U 2 + P2 V2
H 1 = H2
 ∂T 
so that the expansion is isenthalpic. µJT =
 ∂P  H
Some thermodynamic identities
 ∂T   ∂H   ∂H 
 ∂T   ∂H  P  ∂P  T  ∂P  T
µJT = =− =− =−
 ∂P  H  ∂P   ∂H  CP
 ∂H  T  ∂T  P

dH = dU + PdV + VdP ⇒ dU = dH − PdV − VdP 

dH V
dU P  ⇒ dS = − dP
dS = − dV  T T
T T
Some thermodynamic identities...
dH V
dS = − dP
T T

 ∂H   ∂H   ∂H 
dH = dT + dP = CP dT + dP
 ∂T  P  ∂P  T  ∂P  T
 ∂H 
CP dT + dP
 ∂P  T V
dS = − dP
T T
  ∂H  
C   ∂P  T V 
= P dT + − dP
T  T T
 
Some thermodynamic identities...
CP 1   ∂H   This is an exact differential
dS = dT +  − V  dP
T T   ∂P  T 
 ∂  CP    ∂  1   ∂H   
=  −V 
 ∂P  T   T  ∂T  T   ∂P  T  
P

1  ∂  ∂H   1  ∂H   1  ∂ 2 H   ∂V  
=− 2 −V + −
 
T  ∂P ∂T P  T  
T  ∂P T  
 T  ∂P∂T   ∂T  P 


1   ∂H   1  ∂V 
0=− 2 
− V  −
T  ∂P T   T  ∂T  P
  ∂H    ∂V 
− V = −T
  ∂P  T   ∂T  P
 ∂H   ∂V 
= V−T
 ∂P  T
 ∂T  P
Some thermodynamic identities...
 ∂H 
 ∂P  T 
µJT = −
CP 1   ∂V  
 µJTJT = T
 
−V
 ∂H   ∂V   C P
P
 ∂T P
P

= V−T
 ∂P  T  ∂T  P

This expression can be used to predict the Joule-Thomson

coefficient from any equation of state which allows the
calculation of (∂V/∂T)P, so long as the heat capacity at
constant pressure is also known. (Recall that the heat
capacity can be measured from the speed of sound.)
 An example
Suppose the compressibility Z=PV/RT of the gas follows a
virial equation of the type
B (T ) C (T )
(
Z T ,V = 1+) V
+
V 2
+L

The Joule-Thomson coefficient may be written

1   ∂V  
µ JT = T −V

CP  ∂T P  

where we now need (∂V/∂T)P from the equation of state.

 An example...
Finding (∂V/∂T)P from the equation of state:

PV B(T ) C (T )
= 1+ + 2 +L
RT V V
RT B C
P= + RT 2 + RT 3 + L
V V V
R RT R   ∂B   B
dP = dT − 2 dV + 2 B + T dT − 2RT 3 dV + L
V V V   ∂T   V
dP = 0

 + 2 B(T ) + T  ∂B    dT =  RT2 + 2RT B(T3 ) dV

 R R 
V V   ∂T    V V 
 An example...
Having set dP=0 we can solve for (∂V/∂T)P:

 + 2  B(T ) + T  ∂B    dT =  RT2 + 2RT B(T3 ) dV

R R  
V V   ∂T    V V 
 R R 
 + 2 B + T  ∂B   
V V   ∂T     ∂V 
= 
 RT B  ∂T  P
+ 2RT
 V2 V3

 V +  B + T  dB   
 ∂V    dT   
  =
 ∂T  P  B
T + 2T
 V
 An example

 V +  B +T  dB   
 ∂V     dT   
  =
 ∂T  P 
T + 2T 
B
 V

We can expand the denominator using the binomial

expansion, provided we work at sufficiently large molar
volumes (i.e., low pressures):
1 
2 3
1 B  B  B
= 1−2 + 2 − 2 + L
 B  T  V  V   V  
T 1+2
 V
 An example
Doing so, the derivative becomes
 ∂V     dB    1  B  B
2
 B
3

  = V + B +T ⋅ 1−2 + 2 − 2 + L
 ∂T  P    dT    T  V  V   V  
Keeping only the leading terms,
 ∂V 
  = 1  V + B + T  dB − 2B
 ∂T  P T   dT  

1  dB 
= V − B + T
T  dT  
 An example
Substituting this into the equation for µJT gives

1   ∂V  
µJT =  
CP T  ∂T  − V 
 P 
1   dB 
=  V − B + T − V 
CP  dT
1   dB  
= T
  dT  − B
CP

in the low-pressure limit.

 An example
1   dB 
µJT = T
  dT  − B
CP
The point at which the two terms on the right are equal
specifies the inversion temperature of the gas. Above this
temperature, µ is negative (the gas warms as it expands);
below this temperature, it is positive.
A more realistic equation of state predicts that the inversion
temperature is a function of pressure and that a gas may in
principle have more than one inversion temperature at a
given pressure.
 An alternative approach
We could use the Euler permutation to evaluate (∂V/∂T)P.
Again taking
RT B C
P= + RT 2 + RT 3 + L
V V V
We can easily evaluate (∂P/∂T)V and (∂P/∂V)T :
 ∂P  R RB RT dB RC RT dC
= + + + + +L
 ∂T  V V V 2 V 2 dT V 3 V 3 dT
 ∂P  RT B C
= − 2 − 2RT 3 − 3RT 4 +L
 ∂V  T V V V
 An alternative approach...
From these expressions we can again evaluate the Joule-
Thomson coefficient:
  ∂P  
1   ∂T  V 
µJT = −T −V
CP   ∂P  
  ∂V  T 
 R RB RT dB RC RT dC
+ + + + +L 
1  V V 2 V 2 dT V 3 V 3 dT 
= −T RT B C − V
CP  − 2 − 2RT 3 − 3RT 4 +L 
 V V V 
 dB C T dC 
1  V + B + T + + +L
= dT V V dT −V
CP  B C 
1 + 2 + 3 2 +L
 V V 
 Another example
It we take the van der Waals equation of state
RT a
P= − 2
V −b V
We again evaluate (∂P/∂T)V and (∂P/∂V)T :
 ∂P  R
=
 ∂T  V V − b
 ∂P  RT a
=− 2 +2
 ∂V  T ( )
3
V −b V
 Another example...
From these expressions we can again evaluate the Joule-
Thomson coefficient:
  ∂P  
1   ∂T  V 
µJT = −T −V
CP   ∂P  
  ∂V  T 
  R  
1   V − b 
= −T − V
CP  −
RT a
+2 3
 
 (
V − b
2
) V

 
1  1 
=  1 −V
CP V −b a
 −2 
 (
V − b )RT V 3
