Free expansion

Free expansion occurs when a gas spreads into an initially evacuated region without driving an external load. The standard idealization uses a rigid, insulated vessel: initially a partition confines the gas to volume $V_1$, while the remaining compartment contains vacuum. Open a passage and wait for thermodynamic equilibrium; the same fixed amount of substance $n$ now occupies the larger accessible volume $V_2$. The outer vessel never changes size. This simple release separates three questions: what energy is conserved, whether temperature changes, and why entropy increases. ^[ref]

Choose the gas as the closed system, neglect heat exchange with the walls, and assume negligible changes in bulk kinetic energy and potential energy between the equilibrium endpoints. Insulation gives $Q_{\mathrm{in}}=0$; no moving outer boundary or external load receives work, so $W_{\mathrm{out}}=0$. The first law of thermodynamics therefore givesThe gas can develop internal motion during the release; this does not supply external work. The intermediate state need not have one equilibrium pressure or temperature, so there is no actual quasistatic process curve $p(V)$ to integrate. In particular, substituting the equilibrium ideal gas law into $\int pdV$ would describe a different process. ^[ref]

For an ideal gas, internal energy of an ideal gas depends only on temperature. With positive heat capacity at constant volume, $U(T_2)=U(T_1)$ implies $T_2=T_1$, and the ideal gas law gives $p_2/p_1=V_1/V_2$. Doubling the accessible volume thus halves the final pressure without changing the final temperature. This is an endpoint statement; it does not assert a spatially uniform, constant temperature during the rush. Insulation alone does not imply constant temperature: a reversible adiabatic expansion cools an ideal gas because it supplies work. ^[ref]

For a real gas, $U(T,V)$ can depend on volume as well as temperature, so unchanged internal energy need not mean unchanged temperature. For a fixed-composition simple compressible system in a single thermodynamic phase, equilibrium identities using a Maxwell relation giveHere $C_V$ is the whole sample's heat capacity at constant volume. The sign depends on the equation of state; for an ideal gas the numerator vanishes. For a finite free expansion, solve $U(T_2,V_2)=U(T_1,V_1)$, or integrate this slope along equilibrium states of equal internal energy; that mathematical curve does not describe the actual release. ^[ref]

Free expansion is useful because it tests how internal energy depends on number density while eliminating external expansion work. Its beautiful surprise is that an ideal gas can finish with the same temperature and internal energy but greater entropy: a thermometer alone cannot diagnose reversibility. See entropy change in free expansion for the calculation and temperature sensitivity of a free-expansion experiment for the experimental qualification. The continuous-flow throttling associated with the Joule-Thomson coefficient has a different balance: under its usual assumptions it preserves enthalpy, whereas the gas-only idealization here preserves internal energy. ^[ref]

For the classical monatomic caloric model, energy conservation in expansion from $V_i$ to $V_f$ gives $T_f-T_i=2aN(1/V_f-1/V_i)/(3k_B)$. Attractions make the gas cool. The formula assumes homogeneous equilibrium states, not a two-phase coexistence state.

In his paper published in 1845, Joule connected two copper receivers with stopcocks, filled one with compressed dry air, and evacuated the other with an air pump. He immersed the connected receivers in water in an insulated arrangement, stirred the water, and read a sensitive thermometer. He then opened the stopcocks, let the air redistribute, stirred again, and compared the water's temperature with its initial value. Alternating control trials accounted for effects such as stirring and evaporation. The observation was no detectable net cooling of the common bath, rather than a record of the gas temperature at every instant. ^{[ref] [ref]}

Joule also immersed the receivers and their connecting piece in separate water vessels. The source receiver cooled while the receiving side warmed, with nearly cancelling thermal effects. ^[ref]

This distinguishes local transient changes from the final observation for the combined apparatus. Insulating its outer boundary suppresses external heat exchange; it does not prevent heat exchange between the gas, the receivers and the water inside that boundary.

An idealized modern version can use two rigid chambers joined by a valve, with thermometers in the chambers and on the walls. Prepare one chamber with gas and the other evacuated, disconnect the pump, close the apparatus to matter exchange, and let the initial temperature settle. Record initial and final equilibrium pressure and temperature, along with the wall response. Repeated closed-valve runs can reveal drift and valve-actuation effects; independent heating calibrations can estimate the heat capacity of the participating apparatus. This is a proposed measurement protocol, not a claim of a particular measured result. Fast local readings can characterize the release, but they cannot replace the final equilibrium readings in the endpoint internal energy balance.

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]

For the insulated gas-only free expansion of an ideal gas, the equilibrium endpoints are $(T,V_1)$ and $(T,V_2)$ with $V_2>V_1$. Because entropy is a state function, calculate their difference along a hypothetical reversible thermodynamic process: an isothermal expansion using a frictionless piston and a thermal reservoir at $T$. This comparison process receives heat and delivers work, even though the actual free expansion does neither. Its reversible heat increment is $\delta Q_{\mathrm{rev}}=pdV=nRTdV/V$, soHere $R$ is the molar gas constant, and the logarithm acts on a dimensionless ratio. The reversible reference gives the correct endpoint entropy difference because entropy is a state function; putting the actual $Q=0$ into $\Delta S=Q/T$ would misuse a relation requiring reversible heat transfer. For the actual isolated gas, all this increase is entropy production. Thus an adiabatic process can increase entropy and need not be an isentropic process. ^[ref]

In the figure's volume doubling, the ideal gas law gives $p_1=99.768\mathrm{kPa}$ and $p_2=49.884\mathrm{kPa}$, while $\Delta S=R\ln 2\simeq 5.763\mathrm{J}{\mathrm{K}}^{-1}$. The reference process receives and delivers $nRT\ln 2\simeq 1728.85\mathrm{J}$ as heat and work; its thermal reservoir loses the same entropy that the gas gains. The actual free expansion has $Q_{\mathrm{in}}=W_{\mathrm{out}}=0$ and produces that entropy internally. Reversibly compressing the gas back at $300\mathrm{K}$ would require $1728.85\mathrm{J}$ of work input and rejection of equal heat. Restoring the gas alone therefore changes the surroundings: the actual release is irreversible.

For a real gas the final temperature may differ, so the ideal-gas logarithm formula cannot simply be copied. Evaluate $S(T_2,V_2)-S(T_1,V_1)$ using that gas's equilibrium properties or a suitable reversible comparison path. If the walls and water exchange heat with it, the Second law of thermodynamics constrains the total entropy of the isolated apparatus; the gas alone is then not an isolated system.