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For radiation in vacuum with isotropy, energy is distributed equally per solid angle: write $u_{\Omega }=u/(4\pi )$ for energy density per unit solid angle. Let $\theta$ be the angle between a ray's path and the wall normal. Its normal velocity $c\cos \theta$ determines the arrival rate, while normal momentum per energy is $\cos \theta /c$. Their product is ${\cos }^2\theta$. For a perfectly reflecting cavity wall,The leading two is the normal momentum reversal; the incoming hemisphere contains half of the field's directional energy density. This is also the normal component of the bulk pressure tensor, $P_{nn}={\int }_{4\pi }{u}_{\Omega }{\cos }^2\theta d\Omega =u/3$. Isotropy makes all three diagonal components equal, while their sum is $u$ because the squared direction components sum to one. The factor one third therefore depends on three-dimensional angular geometry, not on the shape of the blackbody radiation spectrum.

A perfectly absorbing wall exposed to this incoming hemisphere receives only $u/6$ from absorption. If it is in thermal equilibrium with the isotropic radiation, its outgoing emission supplies another $u/6$ of recoil, recovering $u/3$. A cold absorber before equilibrium is a different boundary condition. Similarly, the one-way incident energy flux is $cu/4$, whereas the net energy flux across a plane in the undisturbed isotropic field is zero. Dividing $cu/4$ by $c$ misses the extra normal-momentum projection and does not give the cavity pressure.

For a stipulated isotropic radiation energy density $u=6\mu \mathrm{J}{\mathrm{m}}^{-3}$, the bulk pressure is $2\mu \mathrm{Pa}$ regardless of its spectral shape. In thermal equilibrium, blackbody radiation supplies $u=a_{\mathrm{rad}}{T}^4$ with radiation constant $a_{\mathrm{rad}}=4\sigma /c$, so $p_{\mathrm{rad}}=a_{\mathrm{rad}}{T}^4/3$; Stefan–Boltzmann law defines $\sigma$. The equilibrium photon gas derives this same equation of state from its free energy.^[ref]

The 1975 experiment mixed powdered sodium chloride and 0.5%-chromium ruby in a 4:1 volume ratio. An Inconel gasket, initially $0.15\mathrm{mm}$ thick with a $0.3\mathrm{mm}$ hole, held the powder and 4:1 methanol–ethanol. At $25{}^{\circ }\mathrm{C}$, X-ray diffraction rings on film $12\mathrm{cm}$ away gave salt compression; a reference equation of state assigned pressure. After decreasing load, they waited at least five hours and bracketed diffraction exposures with $R_1$ readings to check drift.^[ref]

The recommended linear slope was $2.740\mathrm{GPa}\mathrm{n}{\mathrm{m}}^{-1}$, with a $95\%$ fit confidence interval of $\pm 0.016\mathrm{GPa}\mathrm{n}{\mathrm{m}}^{-1}$, to $19.5\mathrm{GPa}$. Reference-scale systematic measurement uncertainty remained separate. Above about $10.4\mathrm{GPa}$ the medium was only quasihydrostatic; separate range fits checked consistency.^[ref]

The logical chain is compression to reference pressure, paired with optical shift, then a fitted response. X-ray diffraction supplies the reference comparison during calibration; subsequent ruby readings transfer that scale to other samples. The reference equation of state is therefore part of the meaning of the reported pressure. Changing it can move all calibrated readings together, even if the optical measurements repeat perfectly. A regression residual tests agreement with the chosen reference within the sampled conditions; it cannot independently certify that reference.

During continued compression of a first hydrostatic core, molecular hydrogen dissociation absorbs energy and softens the effective equation of state. This can trigger a second rapid contraction before a compact stellar core becomes pressure-supported. It is distinct from the initial nearly isothermal collapse and from later Kelvin-Helmholtz contraction at roughly fixed mass.

The equation of state of isotropic blackbody radiation is $p=\rho /3$. The barotropic hydrostatic first integral gives $\rho N^4=C$. The Stefan–Boltzmann law $\rho \propto T^4$ then yields the Tolman–Ehrenfest relation $TN=\mathrm{constant}$. Here $N=\sqrt{|K^a{K}_a|}$ for the stationary timelike Killing vector field; its normalization only changes the constants.

A perfect fluid with equation of state $P=\rho$ is called a stiff fluid. For positive energy density, its constant equation-of-state parameter is $w=1$. The cosmological continuity equation gives $\rho \propto a^{-6}$. In a flat universe dominated by this fluid, the Friedmann equation then gives $a(t)\propto (t-t_B{)}^{1/3}$. This statement assumes a nonzero fluid density and negligible other components.

For a smooth simple compressible system, $C_V=T(\partial S/\partial T{)}_V$ and the Maxwell relation $(\partial S/\partial V{)}_T=(\partial p/\partial T{)}_V$ give $(\partial C_V/\partial V{)}_T=T({\partial }^{2}p/\partial T^2{)}_V$. Thus an equation of state $p=a(V)T+b(V)$ implies that $C_V$ depends on temperature alone within a smooth phase. It does not require $C_V$ to be temperature independent.

For a simple compressible system at fixed composition and particle number, the internal pressure is the partial derivative of internal energy with respect to volume at fixed temperature. From $dU=TdS-pdV$ and the Maxwell relation $(\partial S/\partial V{)}_T=(\partial p/\partial T{)}_V$, it has the measurable expression in the title. It is distinct from the mechanical pressure $p$.

For an ideal gas, $p=nRT/V$ gives ${\pi }_T=0$, so its internal energy depends only on temperature at fixed amount of gas. For the Dieterici equation $p=nRT\exp [-an/(VRT)]/(V-nb)$, direct differentiation givesThus an equation of state determines this volume sensitivity even without determining the full caloric function $U(T,V)$.

Thermometer calibration compares an instrument's response with assigned reference temperatures under specified conditions. In a proposed two-reference procedure, thermalize the sensing part at $T_0$ and $T_1$, record responses $X_0$ and $X_1$, and, only if a linear response is justified over that interval, useAdditional reference temperatures test curvature; returning to the first reference tests drift. A gas thermometer instead obtains its response from an equation of state, with a reference and corrections for its apparatus. In either case, uncertainty in the reference propagates to the inferred temperature. Calibration determines the response relation; it cannot by itself remove the finite-sample disturbance or incomplete thermal equilibrium described in thermometer. A reference established on a practical scale can also differ slightly from true thermodynamic temperature; the BIPM distinguishes the International Temperature Scale of 1990 readings from their thermodynamic counterparts.^[ref]

A reduced model with warm and cold mixed reservoirs whose signed exchange volume flux is proportional to their density difference. For fixed temperature contrast and reference-salinity freshwater forcing, the stationary salt budget is $|q|\Delta S=E{S}_0$. A linear equation of state then gives $q|q|-k\alpha \Delta T|q|+k\beta S_{0}E=0$. Positive circulation has two branches below a saddle-node bifurcation; the stronger positive branch and the reversed branch are stable under the usual salt budget dynamics.

The equation of state $p=-\varrho$ makes the cosmological continuity equation imply constant energy density ${\varrho }_0$. For ${\varrho }_0>0$, put $H_{\Lambda }^2=8\pi G{\varrho }_0/3$. Solving both the Friedmann equation and Friedmann acceleration equation givesUp to shifts of cosmic time and time reversal, the positive scale factors are $A{e}^{H_{\Lambda }t}$ for $k=0$, $H_{\Lambda }^{-1}\cosh (H_{\Lambda }t)$ for $k=1$, and $H_{\Lambda }^{-1}\sinh (H_{\Lambda }t)$ on $t>0$ for $k=-1$. They are the flat, closed and open slicings of de Sitter spacetime. The open zero is a coordinate boundary with finite Ricci scalar $12H_{\Lambda }^2$ and finite Kretschmann scalar $24H_{\Lambda }^4$.

For the expanding flat branch, the cosmological event horizon has comoving radial distance ${\int }_t^{\infty }ds/a(s)=1/[H_{\Lambda }a(t)]$ and proper distance in cosmology $H_{\Lambda }^{-1}$. An event on the horizon reaches the central comoving observer only at infinite reception time; events beyond it never do.

The liquid-gas critical point of the Van der Waals equation occurs where its two subcritical stationary points merge into a horizontal inflection point. The conditions are $(\partial p/\partial v{)}_T=({\partial }^{2}p/\partial v^2{)}_T=0$. The short calculation isDividing these relations gives $2/(v_c-b)=3/v_c$, henceSubstitution gives the Van der Waals law of corresponding states and the parameter-independent ratio $p_c{v}_c/(k_B{T}_c)=3/8$. That ratio belongs to this equation of state; reducing a real fluid's variables does not enforce it.^[ref]

An exact rearrangement of the reduced critical Van der Waals isotherm makes its flatness visible:The first nonzero departure near $x=1$ is $-3(x-1{)}^3/2$. On the critical particle volume approached from $t>1$, $(\partial q/\partial x{)}_{x=1}=-6(t-1)$ andThe divergent isothermal compressibility and cubic flattening explain why the critical region is mechanically soft. These are mean-field theory predictions; thermal fluctuations limit their use for real fluids very close to a thermodynamic critical point.

The Van der Waals equation is a simple real gas equation of state that can also describe a liquid-gas critical point. With particle count $N$ fixed, write the volume per particle as $v=V/N$:or equivalently $(p+a{N}^2/V^2)(V-Nb)=N{k}_{B}T$. Here $p$ is pressure, $T$ is absolute temperature, and $k_B$ is the Boltzmann constant. In SI, $v$ and $b$ have units ${\mathrm{m}}^3$ per particle, $a$ has units $\mathrm{Pa}{\mathrm{m}}^6=\mathrm{J}{\mathrm{m}}^3$, and $k_B$ has units $\mathrm{J}{\mathrm{K}}^{-1}$; the particle count is dimensionless. The pole at $v=b$ excludes smaller volume values from this model.

The $b$ correction represents excluded volume; the attraction term lowers pressure at fixed temperature and particle number density $1/v$. This is a mean-field theory, replacing detailed intermolecular structure by two parameters. At $v\gg b$ with $a/v^2\ll k_{B}T/v$, it approaches the ideal gas law $pv=k_{B}T$. It supplies a useful qualitative route from a dilute gas to phase coexistence, without a claim of quantitative accuracy for every fluid.^[ref]

Do not mix this particle convention with the molar volume convention elsewhere in this article. With amount of substance $n_{\mathrm{mol}}=N/N_A$, Avogadro constant $N_A$, and molar gas constant $R=N_A{k}_B$, one has $v_m=N_{A}v$, $b_m=N_{A}b$, and $a_m=N_A^{2}a$, so $p=RT/(v_m-b_m)-a_m/v_m^2$. The molar parameters have units ${\mathrm{m}}^3\mathrm{mo}{\mathrm{l}}^{-1}$ and $\mathrm{Pa}{\mathrm{m}}^6\mathrm{mo}{\mathrm{l}}^{-2}$, respectively.

Johannes Diderik van der Waals introduced this equation of state in 1873, connecting molecular attraction with departures from the dilute ideal gas law. Its historical significance is the unified treatment of gases and liquids, rather than a universally exact fit.^[ref]

A hypothetical Van der Waals equation model illustrates positive and negative Joule-Thomson coefficient regions and a finite throttle that first warms, then cools. Use the molar convention already distinguished in Van der Waals equation:Here $v_{\mathrm{m}}$ is molar volume, $R$ the molar gas constant, $u_{\mathrm{m}}$ internal energy per mole, and $C_{V,\mathrm{m}}$ the stipulated constant molar heat capacity at fixed volume. The second equation is an additional caloric assumption: an equation of state alone does not specify the temperature dependence of internal energy. It satisfies the equilibrium identity $(\partial u_{\mathrm{m}}/\partial v_{\mathrm{m}}{)}_T=T(\partial p/\partial T{)}_{v_{\mathrm{m}}}-p=a_{\mathrm{m}}/v_{\mathrm{m}}^2$. The arbitrary energy reference is set to zero.

Define dimensionless variables $r=v_{\mathrm{m}}/b_{\mathrm{m}}$, $\theta =R{b}_{\mathrm{m}}T/a_{\mathrm{m}}$, $\pi =b_{\mathrm{m}}^{2}p/a_{\mathrm{m}}$ and $\eta =b_{\mathrm{m}}{h}_{\mathrm{m}}/a_{\mathrm{m}}$, where $h_{\mathrm{m}}$ is molar enthalpy. These differ from the critical-value scaling in Van der Waals law of corresponding states. The throttle calculation reduces toThus a prescribed inlet fixes $\eta$, and solving the first and last equations at the outlet pressure gives the final temperature. For an inlet $({\theta }_1,{\pi }_1)=(0.8,0.12)$ and outlet ${\pi }_2=0.025$, the model gives ${\theta }_2\simeq 0.752287$, a decrease of $0.047713$. The inlet $(2.2,0.12)$ instead gives ${\theta }_2\simeq 2.205786$, an increase of $0.005786$. The purple inlet $(1.45,0.30)$ initially warms but ends at ${\theta }_2\simeq 1.437585$ for the same outlet pressure. These are reduced toy values, not kelvin readings or experimental evidence. No physical gas parameters were fitted.

For a short inversion derivation, implicit differentiation of the Van der Waals equation at fixed pressure givesInsert this into $T(\partial v_{\mathrm{m}}/\partial T{)}_p=v_{\mathrm{m}}$ and substitute back into the equation of state. The Joule-Thomson inversion curve isPositive inversion pressure requires $r>3/2$. Its maximum pressure is $\pi =1/3$ at $r=3$, while the upper dilute limit is ${\theta }_{\mathrm{inv}}\to 2$. Using Van der Waals critical point values, the latter is $T_{\mathrm{inv},\max }/T_c=27/4$. The inversion locus depends on the equation of state; the chosen molar heat capacity additionally determines how much temperature changes along each finite throttle.^[ref]

The displayed region has $\theta >8/27$, above the model's critical temperature, and uses only $r>1$, $p>0$, $(\partial p/\partial v_{\mathrm{m}}{)}_T<0$ and positive $C_{p,\mathrm{m}}$. Subcritical calculations require attention to phase coexistence, metastability and the Maxwell construction; an unstable homogeneous continuation is not an equilibrium throttle endpoint. Even on a stable branch, this mean-field theory with constant $C_{V,\mathrm{m}}$ is a qualitative model, not an accurate inversion map for a particular real gas. Phase transitions, changing composition, appreciable heat leakage or bulk kinetic energy changes require a different property calculation or steady-flow energy balance. At phase coexistence, the smooth single-thermodynamic phase coefficient formula cannot replace a balance involving the phase fraction.

The virial expansion describes the first departures from the ideal gas law as a power series in number density. For a homogeneous, single-species gas in three dimensions at thermal equilibrium, write $n=N/V$, with $V$ the volume, and define the dimensionless compressibility factor $Z$ byHere $p$ is absolute pressure, $T$ is absolute thermodynamic temperature, and $k_B$ is the Boltzmann constant. The second virial coefficient determines the initial slope away from $Z=1$; higher coefficients describe further corrections. The symbol $Z$ here is an equation of state ratio, not a canonical partition function. ^[ref]

The left panel sketches the measurement principle; the right panel uses deliberately chosen polynomials, $Z=1+bx+6x^2$ with $x=n{\ell }^3$ and $b=\pm 2$, where $\ell$ is a reference length. These curves are not measured data. Their initial slopes have opposite signs, but both bend because of the quadratic term. Using a finite secant from $x=0$ to $x=h$ gives $(Z(h)-1)/h=b+6h$, rather than $b$: reducing the fitting range reduces this particular truncation bias. This algebra explains why measuring one nonideal pressure is insufficient to extract a reliable second virial coefficient.

Waxman and Hastings's 1971 Burnett experiment used sample and expansion chambers in a thermostatic bath, with a valve between them and a pressure transducer linked to a piston gauge. They measured successive isothermal expansions: evacuate the expansion chamber, open the valve, record the equilibrated pressure, isolate and evacuate that chamber again, then repeat. This avoids separately measuring the absolute gas amount and chamber volumes. For carbon dioxide at $50{}^{\circ }\mathrm{C}$, their measurements below $35$ bar gave a molar second virial coefficient of approximately $-102.2\mathrm{c}{\mathrm{m}}^3\mathrm{mo}{\mathrm{l}}^{-1}$. ^[ref]

An idealized reduction makes the signal explicit. Let $q=(V_A+V_B)/V_A$ be the calibrated chamber volume ratio, $p_i$ the pre-expansion pressure, and $p_f$ the post-expansion pressure. Particle conservation during one valve opening gives $n_f=n_i/q$. At the same temperature, division of the two equations of state yieldsThus the intercept determines $q$, while the dilute-limit slope determines the second virial coefficient. In the actual experiment, helium runs calibrated the cell constant and chamber deformation corrections were included. Agreement of the carbon dioxide low-pressure intercept with the helium calibration, and the absence of an anomalous low-pressure upturn, checked for gas adsorption on chamber walls. ^[ref]

For a limited dilute-gas fit, hold temperature fixed, allow thermal equilibrium after every expansion, calibrate absolute pressure and the chamber ratio, and check leaks and sample composition. Repeat the analysis with a smaller upper pressure cutoff and an added curvature term; compare the resulting second virial coefficients with their uncertainties. Too wide a range mixes in higher coefficients; too narrow a range makes the nonideal signal hard to distinguish from instrument error. The displayed chamber equation neglects deformation, dead spaces and adsorption, so it is a teaching reduction rather than the complete experimental analysis.

Units matter. With number density in ${\mathrm{m}}^{-3}$, $B_2$ has units ${\mathrm{m}}^3$ and $B_3$ has units ${\mathrm{m}}^6$. For molar density $c=n/N_{\mathrm{A}}$ in $\mathrm{mol}{\mathrm{m}}^{-3}$, the same equation of state isHere $N_{\mathrm{A}}$ is the Avogadro constant and $R=N_{\mathrm{A}}{k}_B$ is the molar gas constant; the molar coefficients have units ${\mathrm{m}}^3\mathrm{mo}{\mathrm{l}}^{-1}$ and ${\mathrm{m}}^6\mathrm{mo}{\mathrm{l}}^{-2}$. A coefficient tabulated per mole must therefore multiply molar density, not number density.

For the classical formulas below, use a nondegenerate gas with thermal de Broglie wavelength ${\lambda }_{\mathrm{th}}$ satisfying $n{\lambda }_{\mathrm{th}}^3\ll 1$, negligible quantum corrections to relative motion, and a stable, sufficiently short-ranged pair potential. Diluteness must also control the omitted interaction terms: $|B_{2}n|\ll 1$ alone is not enough when positive and negative contributions cancel. A finite truncation is a local low-number density approximation, not an equation of state for a dense liquid or across a phase transition. ^{[ref] [ref]}