The Joule-Thomson Effect

After devising several methods to measure the internal pressure ! T = ( "U "V )T of a real gas, James Joule and William Thomson (later Lord Kelvin) turned their attention to experimentally determining a partial derivative that kept showing up in thermodynamic relations:
" !T % JT = $ ' # !P & H

now called the Joule-Thomson coefficient

The following apparatus is a particularly clever way to obtain isenthalpic conditions:

To simplify the mathematics, we assume the following two-step process: a) The left piston is shut with constant pressure until the volume goes from V1 to zero b) The right piston is opened with constant pressure from zero to V2 The total work performed is then:
w = wa + wb = ! " P1 dV ! " P2 dV = !P1 ( 0 ! V1 ) ! P2 (V2 ! 0 ) = P1V1 ! P2V2
0 V2 V1 0

Since this pipe is adiabatic, there is no heat exchange to the surroundings. Therefore, U = w:
U 2 ! U1 = P1V1 ! P2V2 " U 2 + P2V2 = U1 + P1V1 " H 2 = H 1

Experimentally, T and P can be measured between the two regions, giving reasonably good approximations for the Joule-Thompson coefficient. This phenomenon is commonly called throttling, where a gas [usually] cools as it passes from a high to low-pressure state. Applications include the liquefaction of gases and air-conditioning systems. Negative values for the Joule-Thomson coefficient can be dangerous, depending on the nature of the gas. The modern method of measuring JT is indirect and involves experimentally determining the isothermal Joule-Thomson coefficient:
" !H % T = $ # !P ' T &

It is a straightforward application of the cycle rule to show that JT = !

1 T CP