Joule-Thomson coefficient Created 2026-10-06 Updated 2026-10-14
The Joule-Thomson coefficient is the local temperature response to changing pressure at fixed enthalpy and fixed amount and composition:It describes the equilibrium endpoints of a Joule-Thomson effect experiment meeting the steady-flow energy balance assumptions. With , a sufficiently small drop gives . Thus means cooling, warming, and no first-order change. At zero coefficient, a finite drop can still change temperature. For a chosen illustrative local value and , the linear prediction is ; these are stipulated numbers, not measured gas properties.
For a fixed-composition simple compressible system, the measurable form isHere is the whole sample's heat capacity at constant pressure and its volumetric coefficient of thermal expansion; alternatively use molar volume and molar heat capacity consistently. An ideal gas has , so . Its enthalpy depends only on temperature; positive heat capacity at constant pressure then makes any such finite throttle preserve temperature. A real gas can have either sign. For , compare with one: the thermal expansion response decides the sign, not insulation alone.[ref]
Joule-Thompson Throttling. Fitzpatrick, Joule-Thompson Throttling, equations 6.175–6.182: ideal-gas limit and coefficient
A short derivation uses and the Maxwell relation :Setting gives the coefficient. These are equilibrium state function identities, not a claim of a reversible thermodynamic process inside the throttle. For a finite drop, solve the endpoint enthalpy equality or integratealong the constant-enthalpy equilibrium curve. The coefficient can change sign during that integration, as the Van der Waals throttling model illustrates.
Van der Waals throttling model 2026-10-14
A hypothetical Van der Waals equation model illustrates positive and negative Joule-Thomson coefficient regions and a finite throttle that first warms, then cools. Use the molar convention already distinguished in Van der Waals equation:Here is molar volume, the molar gas constant, internal energy per mole, and the stipulated constant molar heat capacity at fixed volume. The second equation is an additional caloric assumption: an equation of state alone does not specify the temperature dependence of internal energy. It satisfies the equilibrium identity . The arbitrary energy reference is set to zero.
Hypothetical Van der Waals throttling model: Joule-Thomson inversion curve and finite temperature responses
. All curves are original model calculations, not nitrogen, carbon dioxide or other gas measurements. Colors label the response along constant molar enthalpy; arrows point toward lower pressure. The displayed states are above the model Van der Waals critical point temperature and have positive isothermal compressibility. The purple path crosses the zero-coefficient curve and has a temperature maximum. Details.Define dimensionless variables , , and , where is molar enthalpy. These differ from the critical-value scaling in Van der Waals law of corresponding states. The throttle calculation reduces toThus a prescribed inlet fixes , and solving the first and last equations at the outlet pressure gives the final temperature. For an inlet and outlet , the model gives , a decrease of . The inlet instead gives , an increase of . The purple inlet initially warms but ends at for the same outlet pressure. These are reduced toy values, not kelvin readings or experimental evidence. No physical gas parameters were fitted.
For a short inversion derivation, implicit differentiation of the Van der Waals equation at fixed pressure givesInsert this into and substitute back into the equation of state. The Joule-Thomson inversion curve isPositive inversion pressure requires . Its maximum pressure is at , while the upper dilute limit is . Using Van der Waals critical point values, the latter is . The inversion locus depends on the equation of state; the chosen molar heat capacity additionally determines how much temperature changes along each finite throttle.[ref]
Joule-Thompson Throttling. Fitzpatrick, Joule-Thompson Throttling, equations 6.188–6.190 and following paragraph: inversion locus, maximum temperature and limits of the van der Waals prediction
The displayed region has , above the model's critical temperature, and uses only , , and positive . Subcritical calculations require attention to phase coexistence, metastability and the Maxwell construction; an unstable homogeneous continuation is not an equilibrium throttle endpoint. Even on a stable branch, this mean-field theory with constant is a qualitative model, not an accurate inversion map for a particular real gas. Phase transitions, changing composition, appreciable heat leakage or bulk kinetic energy changes require a different property calculation or steady-flow energy balance. At phase coexistence, the smooth single-thermodynamic phase coefficient formula cannot replace a balance involving the phase fraction.
