Macroscopically, an adiabatic process exchanges no heat with its surroundings: . A reversible adiabatic process is therefore isentropic, since . Microscopically, the system is thermally isolated, so changes in its energy arise from work done by changing external parameters rather than random energy exchange with a heat bath; in a sufficiently slow change, the populations of the corresponding microscopic states are carried along without producing entropy.
For repeated operation the working substance must execute a thermodynamic cycle. Reversible isothermal contact at absorbs heat , a reversible adiabat changes the temperature to , reversible isothermal contact at rejects heat , and a second adiabat returns to the initial state. This is the Carnot cycle. Reversibility and zero net entropy change give
The thermal efficiency is the net work output divided by the absorbed heat:
Consequently
The Carnot theorem shows that any irreversible cycle has smaller efficiency, so the two isotherms joined by two adiabats are optimal.
For one molecule whose translational motion separates from its internal degrees of freedom, the classical one-particle partition function is
where contains rotational, vibrational, and other internal states. For indistinguishable noninteracting molecules, the classical ideal-gas partition function is . The thermodynamic pressure therefore obeys
so
The internal structure changes the energy, entropy, and heat capacity through , but it does not change the ideal gas law while the internal partition function is independent of volume and the molecules have negligible interactions.
For a dilute monatomic gas . Using the Stirling formula in and differentiating the Helmholtz free energy gives the Sackur-Tetrode equation
With fixed, an isentropic process therefore satisfies , or . Eliminating with the ideal-gas law yields the monatomic reversible ideal-gas adiabat