Excluded-volume ideal gas 2026-10-18
For one mole, a simple repulsive-volume model uses with and domain . The Maxwell relation and first law of thermodynamics give , so . If its molar heat capacity at constant volume is temperature independent, it is constant, and . Reversible adiabatic processes obey or . All positive-temperature isotherms are strictly decreasing and convex; this single-phase model contains no attractive liquid-gas coexistence mechanism. The parameter is an effective unavailable molar volume, not automatically the literal geometric volume of the molecules.
Isotherm 2026-10-18
An isotherm is a curve of equilibrium states at fixed temperature, often drawn in the pressure-volume plane. For an ideal gas of fixed amount it obeys . The curve is not itself a specification of the rate, reversibility or experimental mechanism by which the states are visited.
Label the initial state 1, the end of compression 2, the end of constant-pressure heating 3, and the end of adiabatic expansion 4. The volume sequence is , with . The Diesel cycle has a compression adiabat , a horizontal constant-pressure heat-input segment , an expansion adiabat , and a vertical constant-volume cooling segment .
Figure 1. . Original dimensionless example with V2/V1=0.2, V3/V1=0.4 and gamma=1.4. The curved segments are reversible adiabats, the upper horizontal segment adds heat at fixed pressure and the right vertical segment rejects heat at fixed volume. The enclosed area is the positive net work output. Details.
For an ideal gas, a reversible adiabat obeys , so it falls more steeply than an isotherm. The expansion adiabat lies above the compression adiabat at equal volume between and , giving a clockwise cycle with positive work output.
An equation of state relates equilibrium state variables such as pressure, volume, temperature and material amount. At fixed composition, it reduces the number of independent thermodynamic variables. It does not by itself specify all caloric properties: information such as heat capacity or internal energy is also needed.
At a liquid-gas first-order transition, an equilibrium isotherm can contain a constant-pressure interval in which changing total volume changes the phase fractions. A metastable single-phase extrapolation can instead show a region with ; that region has negative isothermal compressibility and is mechanically unstable. Thermodynamic phase coexistence requires equal temperature, pressure and chemical potential, and a consistent free-energy description replaces the unstable region by coexistence. For an appropriate analytic fluid equation of state, a liquid-gas critical point occurs where .
These tests diagnose the phase behaviour represented by that equation of state. They do not guarantee detection of every possible transition involving an additional order parameter which the mechanical equation omits.
For the given one-mole model,
At fixed positive temperature its isotherm is an ideal-gas hyperbola shifted right by : pressure diverges as and tends to zero as . Higher temperatures give higher pressure at any fixed allowed volume.
Figure 1. . Original dimensionless isotherms with a common vertical asymptote at V=b. They are monotonically decreasing and have no coexistence plateau or critical inflection. Details.
For positive , the volume is the effective volume available to molecular motion. Thus describes excluded-volume repulsion or an effective incompressible molecular core. It is a molar volume in this one-mole equation, not necessarily the literal sum of molecular geometric volume. Setting recovers the ideal gas law. No attractive-energy term is included.