Temperature sensitivity of a free-expansion experiment

The gas-only condition $\Delta U=0$ requires negligible heat exchange with the apparatus. If the insulated isolated system instead includes the walls, sensors and water, the first law of thermodynamics fixes their combined energy. Once everything returns to a common final temperature, a constant apparatus heat capacity $C_a$ givesDefine $A=U_g(T_1,V_2)-U_g(T_1,V_1)$, the gas's internal energy increase for the same expansion evaluated at the initial temperature. For a small temperature change, linearizing at the final volume givesHere $C_{V,g}$ is the whole gas sample's heat capacity at constant volume at the reference state. Compared with an isolated gas sample's $-A/C_{V,g}$, the common final signal is reduced by $C_{V,g}/(C_{V,g}+C_a)$. This energy accounting explains why a massive bath can conceal a real-gas effect. Fitzpatrick gives the corresponding apparatus correction for the Van der Waals equation. ^[ref]

For a toy calculation, stipulate $A=5\mathrm{J}$, $C_{V,g}=10\mathrm{J}{\mathrm{K}}^{-1}$ and $C_a=990\mathrm{J}{\mathrm{K}}^{-1}$, all constant in this example. The predicted cooling magnitude changes from $0.5\mathrm{K}$ for the gas alone to $0.005\mathrm{K}$ for the combined apparatus. An illustrative effective detection threshold of $0.01\mathrm{K}$ would miss the latter. These are chosen numbers, not Joule's measurements. In this approximation a null observation only bounds $|A|\lesssim (C_{V,g}+C_a){ϵ}_T$, where ${ϵ}_T$ is the detectable temperature change after allowing for drift and other experimental uncertainties; a display's smallest digit is not automatically this threshold.

The historical limitation was recognized explicitly: Joule and Thomson later estimated that the common apparatus in Joule's experiment would cool by only about $0.003\mathrm{K}$, explaining why the earlier external thermal effect was undetectable. This was a later calculation about the apparatus, not a measured cooling trace. ^[ref]