Heat capacity ratio ($\gamma$)

The heat capacity ratio compares heat capacity at constant pressure $C_p$ with heat capacity at constant volume $C_V$ at the same equilibrium state and fixed composition:Here $C_p,C_V$ refer to the whole sample, in $\mathrm{J}{\mathrm{K}}^{-1}$; molar heat capacities $C_{p,\mathrm{m}}=C_p/n$ and $C_{V,\mathrm{m}}=C_V/n$ are per mole; specific heat capacities $c_p=C_p/m$ and $c_V=C_V/m$ are per unit mass. The amount of substance $n$ or mass $m$ cancels only when both capacities use the same normalization. Thus heat capacity ratio is dimensionless and independent of sample size. For a fixed-composition ideal gas with positive finite $C_V$, Mayer's relation giveswhere $R$ is the molar gas constant. More ways to store internal energy make a given temperature increase require more heat, bringing heat capacity ratio closer to unity. ^[ref]

The equipartition theorem predicts $C_{V,\mathrm{m}}=fR/2$ when $f$ independent quadratic terms in molecular energy are thermally active and their number stays fixed; consequently $\gamma =1+2/f$. A classical monatomic gas with no appreciable electronic excitation has $f=3$, giving $C_{V,\mathrm{m}}=3R/2$ and $\gamma =5/3$. For an ideal gas of diatomic molecules with three translational and two rotational terms active, but its vibrational normal mode effectively frozen, $f=5$ gives $C_{V,\mathrm{m}}=5R/2$ and $\gamma =7/5$. A fully classical harmonic vibration adds both kinetic energy and potential energy, giving $f=7$ and $\gamma =9/7$. These are model regimes, not universal constants of every gas: rotational freezing, electronic excitation, and changing composition invalidate the simple count.^[ref]

The mechanical significance of heat capacity ratio follows from the first law of thermodynamics. For a fixed amount of ideal gas in a reversible adiabatic process, $C_V(T)dT=-pdV$. Combining this with the ideal gas law gives the local relationThe partial derivative holds at fixed entropy and composition even when heat capacity ratio varies with temperature. The finite-path formulas $p{V}^{\gamma }=\mathrm{constant}$ and $T{V}^{\gamma -1}=\mathrm{constant}$ require the additional approximation of constant heat capacity ratio. A rapid compression also needs internal equilibration to approximate this path; rapid motion alone does not ensure reversibility. The same local response gives isentropic compressibility $1/(\gamma p)$ and, for small sound disturbances in this ideal gas regime, speed of sound $a=\sqrt{\gamma p/\rho }$, where $\rho$ is mass density. Thus thermal storage controls mechanical stiffness, sound propagation and the measurements in Rüchardt experiment and Clément-Desormes experiment.