The Joule-Thomson expansion

The Joule-Thomson experiment is deceptively easy to describe and correspondingly difcult to perform. The experiment consists of forcing a gas at constant backing pressure through a porous plug and measuring the change in temperature. The Joule-Thomson coefcient is equal to

!T JT = !P

The Joule-Thomson expansion...

The Joule-Thomson coefcient is The most straightforward way to measure the coefcient 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 JT = !P

" !T % )T T2 * T1 = $ '( # !P & )P P2 * P1

The Joule-Thomson expansion...

The Joule-Thomson coefcient is 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 or,

!T JT = !P

!U = U 2 " U1 = P1V1 " P2V2

U1 + P1V1 = U 2 + P2V2 H1 = H 2 " !T % JT = $ ' so that the expansion is isenthalpic. # !P & H

Some thermodynamic identities

" !T % " !H % " !H % $ ' $ ' $ ' " !T % # !H & P # !P &T # !P &T JT = $ ' = ( =( =( " !P % " !H % # !P & H CP $ ' $ ' # !H &T # !T & P
dH = dU + PdV + VdP ! dU = dH " PdV " VdP # % $ dU P dS = " dV % & T T dH V ! dS = " dP T T

Some thermodynamic identities

" !T % " !H % " !H % $ ' $ ' $ ' " !T % # !H & P # !P &T # !P &T JT = $ ' = ( =( =( " !P % " !H % # !P & H CP $ ' $ ' # !H &T # !T & P
dH = dU + PdV + VdP ! dU = dH " PdV " VdP # % $ dU P dS = " dV % & T T This gives us an dH V ! dS = " dP exact differential T T involving dH and dP.

Some thermodynamic identities...

dS = dH V ! dP T T

" !H % " !H % " !H % dH = $ ' dT + $ ' dP = CP dT + $ ' dP # !T & P # !P &T # !P &T " !H % CP dT + $ ' dP V # !P &T dS = ( dP T T )" !H % , +$ ' . CP V # & ! P T = dT + + ( .dP T T. + T + . * -

Some thermodynamic identities...

dS = dH V ! dP T T

" !H % " !H % " !H % dH = $ ' dT + $ ' dP = CP dT + $ ' dP # !T & P # !P &T # !P &T " !H % CP dT + $ ' dP V # !P &T dS = ( dP T T This gives us an )" !H % , +$ ' . exact differential CP V # & ! P T = dT + + ( .dP involving dT and dP. T T T + . + . * -

Some thermodynamic identities...

dS = dH V ! dP T T

" !H % " !H % " !H % dH = $ ' dT + $ ' dP = CP dT + $ ' dP # !T & P # !P &T # !P &T " !H % CP dT + $ ' dP V # !P &T dS = ( dP T T This gives us an )" !H % , +$ ' . exact differential CP V # & ! P T = dT + + ( .dP involving dT and dP T T T + . that will allow us to + . * -

solve for (H/P)T.

Some thermodynamic identities...

, CP 1 )" !H % dS = dT + +$ ' ( V .dP T T *# !P &T -

This is an exact differential

,%% " ! " CP %% " ! " 1 )" !H % $ +$ ' ( V .'' $ $ '' = $ $ # & # !P T &T # !T # T *# !P &T -&' &P , 1 )" ! 2 H % " !V % , 1 " ! " !H % % 1 )" !H % $ $ ' ' = ( 2 +$ ' ( V . + +$ ' ($ ' . T # !P # !T & P &T T *# !P &T T ! P ! T & # !T & P *# , 1 " !V % 1 )" !H % 0 = ( 2 +$ ' ( V . ( $ ' T *# !P &T - T # !T & P )" !H % , " !V % ( V = ( T $ ' +$ ' . # & # !T & P ! P * T " !H % " !V % $ ' = V ( T$ ' # !P &T # !T & P

Some thermodynamic identities...

JT = !
# "H & % $ "P ( 'T CP

" !H % " !V % = V ( T $ $ # !P ' &T # !T ' &P

This expression can be used to predict the JouleThomson coefcient 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 + + 2 +! V V
The Joule-Thomson coefcient may be written

% 1 " " !V % JT = $ T$ ' ( V ' C P # # !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:
B(T ) C (T ) PV = 1+ + 2 +! RT V V RT B C P= + RT 2 + RT 3 + ! V V V # "B && R RT R# B dP = dT ! 2 dV + 2 % B + T% ((dT ! 2 RT 3 dV + ! $ "T '' V V V $ V dP = 0 #R R # # RT # "B &&& B (T ) & % + 2 % B(T ) + T% ((( dT = % 2 + 2 RT 3 (dV $ "T ''' V ' $V $V V $

An example...
Having set dP=0 we can solve for (V/T)P:
"R R " " RT " !B %%% B (T ) % $ + 2 $ B(T ) + T$ ''' dT = $ 2 + 2 RT 3 'dV # !T &&& V & #V #V V # "R R " " !B %%% $ + 2 $ B + T$ ''' # !T &&& " !V % #V V # =$ ' " RT % B # !T & P $ 2 + 2 RT 3 ' #V V & " " " dB %%% $V + $ B + T$ ''' " !V % # dT &&& # # $ ' = " B% # !T & P $ T + 2T ' # V&

An example
" " " dB %%% $V + $ B + T$ ''' " !V % # dT &&& # # = $ ' " B% # !T & P $ T + 2T ' # V&

We can expand the denominator using the binomial expansion, provided we work at sufciently large molar volumes (i.e., low pressures):
2 3 + 1( B ! B$ ! B$ = *1 ' 2 + # 2 & ' # 2 & + !! $ B T) V " V% " V% , T#1 + 2 & " V%

An example
Doing so, the derivative becomes
2 3 + " !V % ( " " dB %%+ 1 ( B " B% " B% $ ' = *V + $ B + T$ ''- . *1 / 2 + $2 ' / $2 ' + !# dT &&, T ) V # V& # V& # !T & P ) # ,

Keeping only the leading terms,

" !V % , " dB % 1) $ ' = +V + B + T$ ' ( 2 B. # dT & # !T & P T * " dB %, 1) = +V ( B + T$ '. # dT &T*

An example
Substituting this into the equation for JT gives
, 1 ) " !V % JT = +T$ ' ( V . C P * # !T & P , " dB % 1 ) = +V ( B + T$ ' ( V . # dT & CP * 1 ) " dB % , = +T$ ' ( B. CP * # dT & -

in the low-pressure limit.

An example
1 ( ! dB $ + JT = *T# & ' BCP ) " dT % ,
The point at which the two terms on the right are equal species the inversion temperature of the gas. Above this temperature, 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 + ! V V V

We can easily evaluate (P/T)V and (P/V)T :

R RB RT dB RC RT dC " !P % = + 2 + 2 + 3 + 3 +! $ ' # !T & V V V V dT V V dT RT B C " !P % = ( 2 ( 2 RT 3 ( 3RT 4 + ! $ ' # !V & T V V V

An alternative approach...
From these expressions we can again evaluate the JouleThomson coefcient:
) # "P & , % ( . 1 + $ "T ' V + !T JT = !V. CP + # " P & . % ( + . * $ "V ' T R RB RT dB RC RT dC ) , + + + + + ! 2 2 3 3 . 1 + V V V dT V V dT = !V. + !T RT B C CP + . ! 2 ! 2 RT 3 ! 3RT 4 + ! * V V V dB C T dC ) , V + B + T + + + ! . 1 + dT V V dT = !V. + B C CP + . 1+ 2 + 3 2 +! * 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 :

R " !P % = $ ' # !T & V V ( b RT a " !P % =( $ ' 2 +2 3 # !V & T V (V ( b )

Another example...
From these expressions we can again evaluate the JouleThomson coefcient:
JT
) 1 + + !T = CP + + * , # "P & % ( . $ "T ' V !V. # "P & . % ( . $ "V ' T -

) , # R & + . % ( $ ' 1 + V !b = !T !V. . CP + ! RT + 2 a 2 + . 3 V V ! b ( ) + . * ) , + . 1 + 1 = !V. . V !b a CP + 1 !2 + . 3 RT V V ! b ( ) * -

Another example...
From these expressions we can again evaluate the JouleThomson coefcient. Once again taking the limit at large molar volume,
* $ R ' , / & ) % ( 1 V #b = lim , #T #V/ / CP V !" , # RT + 2 a 2 , / 3 V V # b ( ) , / + .

V !"

lim JT

* #2 ab 2 + 4 abV # 2 aV 2 + bRTV 2 1 = lim , #V 2 2 3 V CP !" , # 2 ab + 4 abV # 2 aV + RTV + = 1 CP * 2a # b , / + RT .

)/
/ .

and an important limiting case

When the gas is ideal, a and b are zero
JT
" % $ ' 1 $ 1 = !V' ' V !b a CP $ 1 ! 2 $ ' 3 RT V V ! b ) #( & " % $ ' 1 $ 1 = !V' ' V !0 0 CP $ 1 ! 2 $ ' 3 RT V V ! 0 ( ) # & " % ' 1 $ 1 = ! V $ ' CP $ 1 ! 0 ' #V & =0