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.
Vapor-compression refrigeration circulates a working fluid through cold and hot coils. In the cold coil, liquid becomes gas while absorbing heat from the refrigerated region. Compression supplies work and raises the pressure and temperature; the hot coil releases heat as the gas returns to liquid. A restriction reduces the pressure before the next cold-side passage. Changing the pressure changes the temperature of the phase transition, letting one circulating fluid receive and release heat at different temperatures. This physical implementation serves both refrigerators and heat pumps; its ordinary dissipative operation differs from the reversible Carnot cycle used to bound performance. [ref] [ref]
An ideal gas law measurement obtains amount of substance without knowing the chemical formula in advance:
Here is vapor pressure, is its occupied volume, is absolute temperature, is the molar gas constant, and is the mass of vapor occupying that volume at those conditions.
Santa Monica College's teaching experiment uses a Erlenmeyer flask with a pinhole foil cap, a water bath on a hot plate, a thermometer, and a barometer. Excess volatile liquid displaces air. A dissolved dye loses its colour and deposits when the liquid evaporates; three more minutes of heating follow. Cooling condenses retained vapor. Subtracting the dry assembly mass from the cooled assembly mass supplies . The flask volume comes from brim-full water mass and mass density at its measured temperature. Controls include a dry exterior, excluding bath water, and three trials.[ref]
The inference assumes vapor pressure equals atmospheric pressure, vapor and bath reach thermal equilibrium, the retained vapor mass is recovered on cooling, and the vapor obeys the ideal gas law. Residual air, thermal expansion of the flask, and vapor temperature below bath temperature are explicit error questions in the teaching experiment. Repeating trials assesses repeatability; it does not remove a shared bias.[ref]
Vapor pressure 2026-10-14
The equilibrium pressure of a vapor in contact with its liquid or solid at a specified temperature. For pure liquid–gas phase coexistence with negligible interface effects, it is the pressure on their phase coexistence curve. In a gas mixture, distinguish the component's partial pressure from the total pressure; the pure-substance Integrated Clausius-Clapeyron relation does not describe the total pressure of arbitrary humid air.
Vertical dynamical timescale of a disk Created 2026-10-05 Updated 2026-10-07
The time for a vertical pressure or gravity response. A sound-crossing time and a small vertical oscillation period have this scale in a thin disk. It need not equal a damping time.
Vertically averaged alpha closure for a mixed-pressure layer Created 2026-10-07 Updated 2026-10-14
For the constant gas-radiation ratio vertical disc structure, the integrated alpha prescription gives the displayed mean kinematic viscosity and . Uniform dynamic viscosity and nonuniform pressure are compatible because this prescription is an integrated equality. Imposing the corresponding pointwise equality would not preserve the exact vertical solution.
Vertical velocity Created 2026-10-06 Updated 2026-10-14
The vertical velocity is the component of a fluid velocity field along the selected upward vertical direction. In incompressible flow, impermeable horizontal boundaries impose . Eliminating pressure often yields a closed hydrodynamic stability equation for this component.
Virial expansion Created 2026-09-24 Updated 2026-10-13
The virial expansion describes the first departures from the ideal gas law as a power series in number density. For a homogeneous, single-species gas in three dimensions at thermal equilibrium, write , with the volume, and define the dimensionless compressibility factor by
Here is absolute pressure, is absolute thermodynamic temperature, and is the Boltzmann constant. The second virial coefficient determines the initial slope away from ; higher coefficients describe further corrections. The symbol here is an equation of state ratio, not a canonical partition function. [ref]
Figure 1.
Controlled gas expansion and extraction of a dilute-gas slope: schematic apparatus and explicitly chosen toy curves
. Details.
The left panel sketches the measurement principle; the right panel uses deliberately chosen polynomials, with and , where is a reference length. These curves are not measured data. Their initial slopes have opposite signs, but both bend because of the quadratic term. Using a finite secant from to gives , rather than : reducing the fitting range reduces this particular truncation bias. This algebra explains why measuring one nonideal pressure is insufficient to extract a reliable second virial coefficient.
Waxman and Hastings's 1971 Burnett experiment used sample and expansion chambers in a thermostatic bath, with a valve between them and a pressure transducer linked to a piston gauge. They measured successive isothermal expansions: evacuate the expansion chamber, open the valve, record the equilibrated pressure, isolate and evacuate that chamber again, then repeat. This avoids separately measuring the absolute gas amount and chamber volumes. For carbon dioxide at , their measurements below bar gave a molar second virial coefficient of approximately . [ref]
An idealized reduction makes the signal explicit. Let be the calibrated chamber volume ratio, the pre-expansion pressure, and the post-expansion pressure. Particle conservation during one valve opening gives . At the same temperature, division of the two equations of state yields
Thus the intercept determines , while the dilute-limit slope determines the second virial coefficient. In the actual experiment, helium runs calibrated the cell constant and chamber deformation corrections were included. Agreement of the carbon dioxide low-pressure intercept with the helium calibration, and the absence of an anomalous low-pressure upturn, checked for gas adsorption on chamber walls. [ref]
For a limited dilute-gas fit, hold temperature fixed, allow thermal equilibrium after every expansion, calibrate absolute pressure and the chamber ratio, and check leaks and sample composition. Repeat the analysis with a smaller upper pressure cutoff and an added curvature term; compare the resulting second virial coefficients with their uncertainties. Too wide a range mixes in higher coefficients; too narrow a range makes the nonideal signal hard to distinguish from instrument error. The displayed chamber equation neglects deformation, dead spaces and adsorption, so it is a teaching reduction rather than the complete experimental analysis.
Units matter. With number density in , has units and has units . For molar density in , the same equation of state is
Here is the Avogadro constant and is the molar gas constant; the molar coefficients have units and . A coefficient tabulated per mole must therefore multiply molar density, not number density.
For the classical formulas below, use a nondegenerate gas with thermal de Broglie wavelength satisfying , negligible quantum corrections to relative motion, and a stable, sufficiently short-ranged pair potential. Diluteness must also control the omitted interaction terms: alone is not enough when positive and negative contributions cancel. A finite truncation is a local low-number density approximation, not an equation of state for a dense liquid or across a phase transition. [ref] [ref]