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A free energy is a thermodynamic potential that compares possible states under specified environmental constraints. For a closed system of fixed composition, treated as a simple compressible system with only pressure-volume work, stable thermodynamic equilibrium minimizes Helmholtz free energy at fixed temperature and volume, or Gibbs free energy at fixed temperature and pressure. The choice follows the experiment: a rigid sealed vessel and a sealed cylinder with a freely moving loaded piston impose different constraints. Both may exchange heat with a thermal reservoir. See W. C. Carter, MIT thermodynamics notes, sections 2-1.14 and 2-1.19.

The useful insight is that internal energy alone cannot rank these alternatives: exchanging heat also changes the surroundings' entropy. Subtracting $TS$ packages that accounting into a property of the chosen system. Adding $pV$ additionally accounts for displacing the surroundings at fixed pressure. A free energy is a state function; supplied heat describes a transfer during a process. Under the stated constraints, supplied heat is $Q=\Delta U$ at fixed volume or $Q=\Delta H$ at fixed pressure, whereas neither $\Delta F$ nor $\Delta G$ generally equals $Q$.

A lower free energy identifies a thermodynamic preference, without specifying a timescale. A barrier can trap a system in a local minimum, producing metastability although a lower global minimum exists. The enzyme example illustrates the corresponding distinction for chemical reactions: changing the route can change the reaction rate while preserving the endpoint Gibbs free energy difference and chemical equilibrium.

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.

Thermodynamics studies energy transfers and the constraints on macroscopic changes. Its vocabulary connects internal energy, entropy, temperature, pressure and volume to heat and work. The first law of thermodynamics balances energy; the Second law of thermodynamics decides which changes can occur spontaneously and limits how much work a heat engine can deliver. These principles let us bound performance before choosing a material or a detailed machine design. Applications include power generation, propulsion and refrigerators. ^[ref]

Start by choosing a system boundary. A closed system can exchange energy but no matter; an isolated system exchanges neither. A state function, such as internal energy or entropy, depends on the equilibrium state. A process specifies how that state changes. Thus a body's temperature is a property it has, whereas heat records energy crossing its boundary during a process. A body contains internal energy, rather than a stored quantity of heat.

Two insulated bodies initially at different positive temperatures approach thermal equilibrium when brought into thermal contact. Their combined energy is conserved, but their combined entropy increases. They do not spontaneously separate again into a hotter body and a colder one. This familiar asymmetry makes thermodynamics interesting: conserving energy leaves many imaginable changes available, and entropy supplies a further constraint. The same distinction underlies both entropy maximization under thermal contact and the thermal efficiency limit in Carnot's theorem.

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 thermometer measures temperature through a physical response whose relation to temperature is known. Examples include the length change from thermal expansion, a change in electrical resistance, and the pressure of a gas thermometer. If the response function $X=f(T)$ is an injective function over the working range, its measured value determines $T=f^{-1}(X)$ through the inverse function. Thermometer calibration establishes that relation for the particular instrument and measurement conditions. Two matching readings are meaningful only after calibration to a common scale and with the probes sampling comparable equilibrium states. ^[ref]

For a contact thermometer, the sensing part must reach thermal equilibrium with the region being measured. That region may differ from the rest of the object: an immersed probe near a heater can read a local temperature while the surrounding water remains cooler. A stable reading can also be a steady state set by competing heat transfer paths to the sample and the room. Good contact, adequate immersion, mixing where appropriate, and checks for spatial differences help establish which temperature the reading represents. These are measurement controls inferred from the thermal equilibrium requirement, not a guarantee that every flat trace is equilibrium.

A thermometer also changes the sample it touches. Consider an original toy calculation with an initially uniform sample at $T_o=350\mathrm{K}$, a probe at $T_p=300\mathrm{K}$, and constant whole-body heat capacities $C_o=100\mathrm{J}{\mathrm{K}}^{-1}$ and $C_p=1\mathrm{J}{\mathrm{K}}^{-1}$. Suppose together they form an isolated system, with no work or phase transition and negligible contact energy. The first law of thermodynamics and thermal equilibrium giveThe final thermometer reading underestimates the sample's original temperature by about $0.495\mathrm{K}$, although it correctly measures their new common temperature. The disturbance becomes small when the participating probe heat capacity is small compared with the sample's. A large controlled heat bath is a different limit: it supplies or removes heat while approximately maintaining its own temperature.

Waiting time is a separate issue from disturbance. Under a toy Newton's law of cooling model for a uniform probe in a maintained heat bath, a constant contact conductance $G$ givesThe time constant $\tau$ controls this exponential decay. For stipulated values $T_b=350\mathrm{K}$, $T_p(0)=300\mathrm{K}$ and $\tau =5\mathrm{s}$, the probe reads about $331.61\mathrm{K}$ after one time constant and $347.51\mathrm{K}$ after three. These are calculated values, not an instrument specification or measured data. Real probes may have multiple relaxation times and additional heat transfer paths; choose an equilibration criterion from the required accuracy, rather than assuming that a fixed waiting time works universally.

For smooth radial variation on scale $r$, $c_s\sim \Omega H$, $\nu \sim \alpha \Omega H^2$, $u_r\sim \nu /r$ and $u_z\sim H{u}_r/r$. The exact point-mass vertical gravity differs from ${\Omega }_K^{2}z$ by relative order $(H/r{)}^2$. Radial pressure support changes the rotation and dominant shear heating by the same order. Meridional viscous forces, radial radiative-flux divergence, thermal advection and compressional work are at most order $(H/r{)}^2$ relative to their retained vertical terms for $\alpha \lesssim 1$. These estimates require secular disk evolution and exclude sharp radial boundary layers or independently rapid vertical motion.

// Target: gravitational-instability-of-an-astrophysical-disk.bigb

Let a strong shock wave of radius $R$ and speed $V$ sweep a uniform mass density ${\rho }_0$ into a shell of mass $4\pi {\rho }_0{R}^3/3$ and speed $2V/(\gamma +1)$. If the cavity pressure is $\alpha$ times the immediate post-shock pressure, shell momentum balance gives $R\dot{V}=3(\alpha -1)V^2$. Constant total energy gives $R^3{V}^2=\mathrm{constant}$ and hence $\alpha =1/2$. Including shell internal and kinetic energy, and treating the cavity volume as $4\pi R^3/3$ to thin-shell accuracy, yields $R=\xi (E/{\rho }_0{)}^{1/5}{t}^{2/5}$ with ${\xi }^5=75(\gamma -1)(\gamma +1{)}^2/[16\pi (5\gamma -3)]$. This coefficient is approximate; resolving the shell's finite volume changes it.

A point injection of volume at rate $Q$ produces the displayed radial potential flow in three dimensions. Its velocity potential is $-Q/(4\pi r)$, and every enclosing sphere has outward volume flux $Q$. The divergence vanishes away from the source and is $Q$ times the three-dimensional Dirac delta distribution at it. The field is also a Stokes flow with constant pressure away from its singularity.

Differential gravitational acceleration, multiplied by the affected mass, across a spatially extended body. In the linear approximation the acceleration difference is $T\Delta \mathbf{r}$, where $T$ is the tidal tensor. Stellar tidal forces limit the domain of a circumplanetary orbit; sufficiently strong ones can produce tidal disruption.

To isolate a tidal force, subtract the gravitational acceleration shared by the body as a whole. Let a reference test particle follow $\ddot{\mathbf{R}}=\mathbf{g}(\mathbf{R})$, and let another have position $\mathbf{R}+\mathbf{x}$. In a translating accelerated reference frame with parallel, nonrotating axes,for a source point mass, when $|\mathbf{x}|/R\ll 1$. Here $\mu =GM$ is its standard gravitational parameter and the last term uses Big O notation. This Taylor expansion removes the common inward pull and keeps the spatial variation. The near side has an excess pull toward the source; the far side has a deficit of inward pull, which is an outward relative acceleration. Both sides can stretch apart while both still accelerate toward the source.^[ref]

For a material element of mass $m$, the residual external force in this translating accelerated reference frame is $m[\mathbf{g}(\mathbf{R}+\mathbf{x})-\mathbf{g}(\mathbf{R})]$. Actual deformation also depends on elasticity, pressure and self-gravity. A rigid body approximation suppresses deformation but can still have internal forces that resist the tidal force. The point-mass tidal stretching and squeezing pattern describes freely falling, noninteracting test particles, rather than promising the same shape for every solid, star or ocean. A rotating reference frame introduces centrifugal acceleration and Coriolis acceleration, which must be included separately.

A triple point is a temperature–pressure pair at which three distinct bulk thermodynamic phases of a one-component substance coexist in thermodynamic equilibrium. In the familiar solid–liquid–gas case, their three phase coexistence curves meet. Other combinations, such as two crystal polymorphs and a liquid, also qualify: “triple” counts thermodynamic phases, rather than states-of-matter categories.

For the same substance, the chemical potential in each thermodynamic phase must agree:There are two independent equality conditions for two controls, temperature and pressure. Generically they select an isolated pair $(T_t,p_t)$; the third pairwise equality follows from the first two. Equivalently, the phase rule gives $F=1-3+2=0$. This counts independent intensive controls, not phase fractions: changing the amounts of the three thermodynamic phases need not change the ideal bulk temperature and pressure, provided all three remain present. Different sets of crystal polymorphs can give different triple points for the same substance.^[ref]

At a liquid-gas critical point, the two fluid thermodynamic phases instead merge, and their mass density difference and latent heat vanish. It is the endpoint of the liquid–gas phase coexistence curve, rather than a meeting of three distinct thermodynamic phases. The regular independent-equality count used for a triple point cannot explain this merger. A triple point can retain finite mass density and entropy differences between all three thermodynamic phases.^[ref]

Turgor pressure is the internal hydrostatic pressure above the external pressure in a biological cell. When water enters a walled biological cell by osmosis, expansion loads the cell wall. Rising pressure can oppose further net entry while the cell membrane retains its selective permeability. Mechanical support therefore does not require the cell wall to block water.

As an original mechanical check, idealize a small flat patch of cell wall of surface area $A$ under uniform turgor pressure $\Delta P=P_{\mathrm{in}}-P_{\mathrm{out}}$. Its outward force is $F=\Delta PA$. Doubling $A$ at fixed pressure doubles the load; equal internal and external pressures give zero net pressure load. This is a force balance, not a measured wall strength or a complete model of a curved, growing biological cell. It says nothing about which solutes cross the cell membrane.