Thermodynamic system

A thermodynamic system is the part of the physical world selected for an energy and matter balance. Draw its boundary before classifying an interaction as heat, work or transported matter. The boundary may move: a sealed piston encloses a closed system even while its volume changes. An isolated system additionally excludes all external energy transfers.^[ref]

Boundary choice changes the ledger. If an electrical heater warms water, choosing only the water counts incoming heat; including the heater counts electrical work entering through its leads. The combined internal energy records storage, without separate stored categories for the two transfer mechanisms.^[ref]

An equilibrium thermodynamic state specifies sufficient independent macroscopic properties, together with material identity and constraints, to determine the other equilibrium properties. For a uniform fixed-composition ideal gas, its amount of substance, temperature and volume determine its pressure through the ideal gas law. These properties specify a state, without specifying a thermodynamic process that prepared it.^[ref]

A thermodynamic process changes a thermodynamic system between states. A quasistatic process supplies equilibrium intermediate states and therefore a path on equilibrium coordinates. An irreversible thermodynamic process can have equilibrium endpoints while lacking a uniform intermediate temperature or pressure. Endpoint values still determine changes in a state function; computing heat and work requires the actual interaction history.

A thermodynamic system for which the reversible mechanical work is entirely pressure-volume work. At fixed composition its internal energy is specified by entropy and volume; additional work modes require additional state variables.

A thermodynamic system is in thermodynamic equilibrium when its macroscopic state has no spontaneous tendency to change through any exchange allowed by its constraints. For an isolated system, stable thermodynamic equilibrium maximizes entropy over the accessible states at fixed total energy and conserved material inventories. A wall can forbid an exchange, so always specify what can cross or move. Thermal, mechanical and chemical conditions answer different questions about that same constrained state. ^[ref]

For example, two compartments separated by a rigid, impermeable wall that transmits heat can reach thermal equilibrium while retaining different pressures and compositions. Allowing an unloaded piston to move adds a mechanical equilibrium condition. Allowing one chemical species to cross adds chemical potential equality for particle exchange; allowing a chemical reaction adds its chemical equilibrium condition. A fixed barrier can therefore support a constrained thermodynamic equilibrium that ceases to be an equilibrium when the barrier is removed.

Uniformity is not the definition of thermodynamic equilibrium. An isothermal atmosphere in hydrostatic equilibrium can have a common temperature while its pressure and mass density vary with height: the pressure gradient balances gravity. In an external field, the exchange condition must include the relevant potential energy; for charged matter this leads to the electrochemical potential. Relativistic gravitational corrections to thermal equilibrium are described separately by the Tolman temperature law.

A steady state only says that the macroscopic description is constant in time. A bar maintained between hot and cold thermal reservoirs has steady heat flux and produces entropy, so it is not in thermodynamic equilibrium. Even matching temperatures at one perfect-contact interface can coexist with heat transfer through the surrounding material; matching those two local values does not establish equilibrium of the whole apparatus. See thermal conduction for that spatial transport problem.

The useful simplification is that equilibrium conditions predict an endpoint without computing every collision or flow during relaxation. The first law of thermodynamics supplies the conserved quantities, and the Second law of thermodynamics supplies the direction of change. For a system held at fixed temperature and volume, the corresponding criterion is minimization of Helmholtz free energy; at fixed temperature and pressure, it is minimization of Gibbs free energy, with the material and exchange constraints still imposed.

Coexistence without a thermodynamic driving force for further exchange. Phases able to exchange heat and constituents have equal temperature and chemical potentials of the exchanging species. Mechanical balance is also needed; interface curvature can require a pressure jump rather than equal bulk pressures.

Mechanical equilibrium requires force balance for the mechanical displacements that are allowed. Two uniform fluids separated by a freely moving, unloaded, frictionless piston with equal face areas require equal pressures. A supported piston can sustain a pressure difference, and a fluid in gravity instead obeys hydrostatic equilibrium. For an upward height coordinate $z$, that balance is $dp/dz=-\rho g$, where $\rho$ is mass density and $g$ is the downward gravitational acceleration. Mechanical equilibrium alone does not establish thermal equilibrium or chemical equilibrium.

Two fluids at a stationary, freely movable interface require equal pressures when surface tension and other normal stresses are negligible. This local pressure equilibrium does not require equal temperatures or mass densities. Curvature with nonzero surface tension or an applied load changes the normal-stress balance. Comparing points at different heights also requires the hydrostatic equilibrium condition.

For a mechanical coordinate $x$ at fixed temperature, total volume and particle numbers, the relevant thermodynamic potential is the Helmholtz free energy $F(x)$. Its generalized force is $f=-F^{\prime }(x)$. At mechanical equilibrium, $f(x_{\ast })=0$, and a linearly restoring force has $f^{\prime }(x_{\ast })<0$, equivalently $F^{\prime \prime }(x_{\ast })>0$. A Taylor expansion then proves a strict local free-energy minimum. If $F$ is a strictly convex function throughout the accessible domain, the stationary state is the unique global minimum.

A closed system exchanges no matter with its surroundings, but can exchange energy through heat or work. A sealed cylinder with a moving piston is a typical idealized example. “Closed” fixes the material inventory, rather than the volume or the internal energy. An insulated cylinder can receive compression work; a rigid sealed vessel can receive heat. Neither is necessarily an isolated system.

An isolated system exchanges neither matter nor energy with its surroundings. Its total energy is fixed, while the Second law of thermodynamics requires its total entropy to be nondecreasing. Its internal energy alone is fixed when bulk kinetic energy and external potential energy also remain unchanged. For example, an initially spinning stirrer inside an insulated rigid vessel can lose kinetic energy while the contents gain internal energy, with no external input.

An isolated system need not yet be in thermodynamic equilibrium. Two enclosed bodies at different temperatures can exchange heat internally until they reach thermal equilibrium; their combined energy stays constant. Their internal transfer is absent from the outer boundary ledger. A vacuum-insulated container is only an approximation to isolation: residual thermal conduction and thermal radiation can still carry energy across its boundary.