Combining with the preceding Gibbs free-energy Maxwell relation gives
Setting and solving for yields the Joule-Thomson coefficient
When , a negative pressure change produces cooling.
For a simple system of fixed composition, the first law of thermodynamics and
give
Thus
Equality of mixed derivatives gives the Gibbs free-energy Maxwell relation
The heat capacity at constant volume and heat capacity at constant pressure are
Regarding as a function of and differentiating along a constant-pressure curve gives
The Maxwell relation from the Helmholtz free energy is
Therefore the difference between constant-pressure and constant-volume heat capacities is
Along the liquid-gas phase coexistence curve, the molar Gibbs free energies agree. Differentiating along the curve gives
Hence the Clausius-Clapeyron relation is
where is the molar latent heat.
If and the gas is ideal, then , so
For constant , integration yields
where is constant over the range in which the approximations apply.
This is the Joule-Thomson coefficient, , describing a temperature change during an isenthalpic pressure change. Here is enthalpy, is the heat capacity at constant pressure, and is volume, all for the same chosen amount of substance. Starting with and using the Gibbs free-energy Maxwell relation gives
Setting proves
In a steady insulated throttle or porous plug, negligible kinetic- and potential-energy changes make the upstream and downstream enthalpies equal. A positive coefficient gives cooling on a pressure decrease; a negative one gives warming. For an ideal gas, at fixed , so the coefficient is zero. Real-gas interactions permit cooling and an inversion curve, making the effect useful in gas refrigeration and liquefaction.
The measurement of the Joule-Thomson effect with a porous plug compares pressures and thermometers on the two sides of an insulated flow restriction. Suppressing external heat exchange and separating the readings from high-speed jets are part of making the enthalpy argument applicable; an arbitrary adiabatic expansion need not be isenthalpic.