Past exam of the mathematics course of the University of Cambridge / 2023 / ii / Paper 4 / 35A (Statistical Physics)

The Clausius statement of the second law says that no cyclic device can have as its sole effect the transfer of heat from a colder reservoir to a hotter one. The Kelvin-Planck statement of the second law says that no cyclic device can have as its sole effect the extraction of heat from one reservoir and its complete conversion into work.

Suppose first that the Clausius statement fails. Use the forbidden device to return to a hot reservoir the heat $Q_C$ rejected by an ordinary heat engine. The combined device extracts $Q_H-Q_C$ from the hot reservoir and converts all of it into work, violating the Kelvin--Planck statement.

Conversely, suppose the Kelvin--Planck statement fails. Use the work produced by the forbidden one-reservoir engine to drive an ordinary refrigerator. The engine's heat withdrawal and the refrigerator's heat discharge cancel by the work-energy balance, leaving only a transfer of heat from the cold reservoir to the hot reservoir with no external work. This violates the Clausius statement. Each statement therefore implies the other, so the two forms of the Second law of thermodynamics are equivalent.

For $N$ particles, the ideal gas equation of state isThe internal energy of an ideal gas depends only on temperature and obeysFor constant heat capacity and a convenient choice of energy zero,

An adiabatic process has no heat transfer, $\delta Q=0$. With work done by the gas taken as positive, the first law of thermodynamics givesUsing $dE=C_{V}dT$ and $p=N{k}_{B}T/V$,Integration, followed by the Mayer relation $N{k}_B/C_V=\gamma -1$, yieldsEliminating $T$ with the equation of state gives the reversible ideal-gas adiabat

This is the ideal Diesel cycle. In the $(p,V)$ plane, $A\to B$ is an adiabatic curve running up and left, $B\to C$ is a horizontal constant-pressure segment running right, $C\to D$ is an adiabatic curve running down and right, and $D\to A$ is a vertical constant-volume segment running down. The traversal is clockwise, so the enclosed area is positive work output.

In the $(T,S)$ plane, the two reversible adiabats are vertical because entropy is constant: $A\to B$ rises at $S_A=S_B$, and $C\to D$ falls at $S_C=S_D$. Along $B\to C$, the heat increment at constant pressure issoAlong the constant-volume curve $D\to A$,which givesThus $B\to C$ runs up and right and $D\to A$ runs down and left between the two vertical adiabats.

Heat enters only during the constant-pressure step, so the heat capacity at constant pressure givesThe positive magnitude of the heat rejected during constant-volume cooling isBecause the working gas returns to its initial state, the thermodynamic cycle has zero net change in internal energy and $W=Q_1-Q_2$. Its thermal efficiency is therefore