Isenthalpic process 2026-10-14
An isenthalpic process preserves enthalpy for a fixed amount of material, or preserves specific enthalpy between inlet and outlet when comparing a flowing fluid of fixed composition. It need not preserve temperature or entropy. An insulated throttle satisfying the steady-flow energy balance assumptions is an important example.
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 is
Here 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]
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 integrate
along the constant-enthalpy equilibrium curve. The coefficient can change sign during that integration, as the Van der Waals throttling model illustrates.
Joule-Thomson effect 2026-10-14
The Joule-Thomson effect is the temperature response of a fluid flowing from higher to lower pressure through a valve or a plug of porous medium, when the throttle is insulated and the other steady-flow energy balance assumptions hold. Its equilibrium endpoints have equal specific enthalpy. The Joule-Thomson coefficient determines whether a small drop cools or warms; cooling is not universal.
Figure 1.
Enthalpy accounting for an insulated Joule-Thomson effect throttle
. Original schematic of the steady-flow energy balance, with denoting internal energy per unit mass. The arrows include inlet and outlet pressure work. The reduced balance requires negligible bulk kinetic energy and potential energy changes. No particular apparatus or measured temperature drop is depicted. Details.
A useful contrast is between three insulated expansions. In free expansion of a gas-only closed system into a vacuum, no external work occurs and ; an ideal gas returns to its initial equilibrium temperature. In a throttle, continuous flow carries pressure work across the boundary and preserves specific enthalpy under the stated assumptions; an ideal gas again has no endpoint temperature change. In a reversible adiabatic expansion of a loaded closed system, the gas supplies work, loses internal energy and cools, even if it is an ideal gas. That process preserves entropy; throttling generally produces entropy. For a small constant-enthalpy step, gives when and . This equilibrium comparison computes endpoint entropy differences without supplying a reversible path through the plug.
The effect is useful in refrigerators because an appropriately prepared real gas can cool while passing through a simple valve. The inlet must lie in a suitable positive-Joule-Thomson coefficient region. The Joule-Thomson inversion curve makes that requirement precise; a pressure drop by itself is not a guarantee of refrigeration.
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.
Figure 1. . 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 to
Thus 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 gives
Insert this into and substitute back into the equation of state. The Joule-Thomson inversion curve is
Positive 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]
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.