Molar enthalpy 2026-10-14
Molar enthalpy is enthalpy per amount of substance , measured in . With and molar volume , . Its fixed-pressure temperature derivative is the corresponding molar heat capacity , at fixed composition.
For steady flow through a fixed control volume with one inlet and one outlet, the first law of thermodynamics and conservation of mass give
Here is the mass flow rate, incoming heat per unit time, outgoing non-flow work per unit time, the flow speed, elevation and gravitational acceleration. The specific enthalpy includes both the transported internal energy per unit mass and the pressure work needed to push volume through the boundary; is mass density. The inlet supplies that pressure work, while the outlet consumes it to displace the downstream fluid.[ref]
For an insulated stationary throttle, require negligible heat transfer, no shaft or other non-flow work, and negligible changes in bulk kinetic energy and gravitational potential energy. Then . With unchanged composition this is also equality of molar enthalpy. The upstream and downstream states must admit equilibrium pressure, temperature and property values, although the constriction itself is irreversible and can be far from thermodynamic equilibrium. Start-up storage of energy in the walls and fluid, heat leakage, or a large outlet speed invalidates the reduced balance. A nozzle can convert specific enthalpy into bulk kinetic energy even when it is insulated.
The same accounting for a fixed transported amount is , hence . This explains why dropping the two pressure work terms would give the wrong conserved quantity.[ref]
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.