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A gas thermometer infers temperature from the equation of state of a confined gas. The constant-volume version measures pressure; the constant-pressure version measures volume. For an ideal gas,Here $N$ is particle number, $n$ is amount of substance, $k_B$ is the Boltzmann constant, and $R$ is the molar gas constant. The reference and test states must be internally equilibrated, and $T_0$ must be known on the absolute thermodynamic temperature scale. A pressure ratio cancels the unknown gas inventory and bulb size in the ideal constant-volume limit. This cancellation is the method's appeal: a mechanical measurement transfers an absolute temperature scale between different materials. The Maxwell speed distribution and ideal gas pressure from wall collisions explain the microscopic origin of the response. ^[ref]

For an original ideal-model calculation, choose $T_0=300\mathrm{K}$, $P_0=120\mathrm{kPa}$ and $P=160\mathrm{kPa}$. Then $T=400\mathrm{K}$. These are stipulated values, not observations. Both pressures must be absolute, referred to vacuum. If the surrounding atmospheric pressure were $100\mathrm{kPa}$, the corresponding gauge pressures would be $20$ and $60\mathrm{kPa}$; their ratio is three, which would incorrectly predict $900\mathrm{K}$. A pressure difference from the atmosphere cannot be substituted into the ideal gas law.

A motivating calibration experiment. Schooley's account of the NBS/NIST work describes a helium-filled metal bulb, a capillary, a capacitance diaphragm gauge, and a mercury pressure standard. Circulating bath liquid passed the bulb assembly and platinum resistance thermometers. The resistance probes checked the surrounding temperature; gas pressure supplied the independent thermodynamic comparison. In an early series, workers filled the cleaned bulb with purified helium at the highest test temperature, checked pressure over three hours, then measured at lower temperatures and near a reference at $0{}^{\circ }\mathrm{C}$. Six filling pressures allowed extrapolation toward zero pressure. ^[ref]

To turn this principle into a readable measurement protocol, use the following controls. These steps are a proposed teaching interpretation of the cited apparatus, rather than additional reported NBS observations:

The corresponding NBS apparatus used a protective case with an outer helium layer held close to the bulb pressure, reducing pressure deformation while aiding thermal contact. Thermal expansion was measured on bulb material. Gas in the capillary remained partly outside the hot region, requiring a measured tube temperature profile and geometry. Pure working gas also mattered: contaminants that sorb on surfaces can change the freely circulating inventory. These are physical effects to measure or bound, rather than scatter that disappears by averaging. ^[ref]

For illustration, neglect connecting-tube gas and describe a uniform bulb with a dilute virial expansion in particle number density ${\rho }_N=N/V$:Here $Z=PV/(N{k}_{B}T)$ and $B_2$ is the second virial coefficient in the particle-density convention; a molar-density convention rescales the coefficient. The second relation follows exactly from the definition of $Z$ for the same $N$, and shows the signs of the corrections. If the bulb expands by $0.1\%$ and $Z=1$ at both states, the toy pressure ratio above gives $400.4\mathrm{K}$, rather than $400\mathrm{K}$. Improved expansion and helium nonideality models really changed the temperatures inferred from the 1989 NIST data: Harvey's 2023 reanalysis found expansion updates of roughly $1$–$3\mathrm{mK}$ and nonideality updates of roughly $-0.1$ to $-0.5\mathrm{mK}$. Those are reported corrections to historical results, not the much larger illustrative correction just calculated. ^[ref]

With equal corrected bulb volumes, negligible or corrected connecting-tube gas, fixed reference and test temperatures, and a dilute classical single gas phase,Repeat the reference/test comparison for several sealed fills, reducing $N$ between comparisons but keeping it fixed within each pair. The extrapolation varies density at fixed endpoint temperatures; it does not cool one fill toward zero temperature. Real gases have different finite-density corrections but share the classical ideal gas intercept under these assumptions. The limit does not remove leaks, bulb expansion, gauge offsets, or the gas thermometer dead-space correction. At very low pressures, thermal transpiration can make remote sensor and bulb pressures differ through a nonisothermal capillary; this must be corrected too. The NBS work measured this pressure correction using a separate comparison of narrow and wider tubes. ^[ref]

At $x=1$, the toy models give $T_{\mathrm{app}}=407.92\mathrm{K}$ and $388.12\mathrm{K}$, respectively, although their imposed true test temperature is the same. Their zero-density intercept is the reusable quantity. Measuring several low-density points permits a fit and a check for curvature; asserting a straight line from one finite-density point supplies neither. A practical fit must balance nonideality against increasing relative pressure error and the capillary corrections, and keep its extrapolation uncertainty.

A hard-sphere gas is a classical model of identical impenetrable spheres, each of diameter $\sigma$ and radius $\sigma /2$. Its pair potential is $u(r)=+\infty$ for centre separation $r<\sigma$ and $u(r)=0$ for $r\ge \sigma$; the convention at exact contact has no effect on the integral. It isolates the effect of particle size without an attractive potential energy.

The upper-left panel is a cross-section of a three-dimensional forbidden region: the second centre cannot enter a sphere of radius $\sigma$ around the first centre. The particles themselves have radius $\sigma /2$. Consequently, with particle volume $v_{\mathrm{s}}$ and pair excluded volume $v_{\mathrm{ex}}$,The last equality follows directly from the Mayer f-function: $f=-1$ throughout the forbidden volume and zero outside it. Confusing particle radius with contact separation changes the answer by a factor of eight; omitting the unordered-pair factor changes it by a further factor of two.

Define the packing fraction $\eta =n{v}_{\mathrm{s}}$, where $n$ is number density. Then the virial expansion beginsFor example, at the toy value $\eta =0.01$, the leading correction predicts $Z\approx 1.04$; the omitted terms still matter if accuracy beyond this approximation is needed. The classical second virial coefficient is independent of temperature because the geometry of forbidden configurations does not change when the gas is warmed. The pressure itself still scales with temperature at fixed number density.

This model makes the positive correction particularly clear: eliminating overlapping configurations changes the dependence of the available configuration space on volume, even though the allowed configurations all have zero interaction energy. The figure's other panels add a toy attractive shell and show how its Boltzmann factor competes with that geometry. The hard-sphere gas is a useful reference model, while a low-order virial expansion remains a dilute-gas approximation rather than a dense sphere packing formula.

The Mayer f-function measures how a pair potential changes a pair's Boltzmann factor relative to the noninteracting value one:It vanishes where $u=0$, lies between $-1$ and $0$ for repulsion, and is positive for attraction. Even an infinite hard-core potential energy produces the finite value $f=-1$. This is why expanding in Mayer f-functions handles a hard-sphere gas more naturally than a Taylor series in $u$. ^[ref]

For pairwise-additive potential energy $U={\sum }_{i<j}u(r_{ij})$, the exact identityturns the configurational part of the canonical partition function into a sum of products associated with pairs. Drawing one edge for each chosen factor $f(r_{ij})$ gives the graphs used in the cluster expansion. The second virial coefficient uses just one pair's relative-position integral, $B_2=-\frac{1}{2}\int f{d}^3\mathbf{r}$.

For the square-well toy pair potential in second virial coefficient, $f=-1$ in the core, $f=e^{1/T^{\ast }}-1$ in the attractive shell, and $f=0$ beyond it. Its positive plateau need not be small: low number density, rather than small $f$ at every separation, controls the dilute-gas approximation. The integral weights each plateau by spherical-shell volume; equal-looking unweighted areas on a plot of $f$ versus $r$ need not cancel in $B_2$.

Let the pair potential be $u(r)$, so that in the dilute limit only one interacting pair need be retained at a time. The leading Mayer f-function expansion isFor each pair, translation of its center coordinate supplies $V$ and the other $N-2$ particles supply $V^{N-2}$. Neglecting boundary corrections,The Taylor expansion $\log (1+x)=x+O(x^2)$ and $N(N-1)\simeq N^2$ in the thermodynamic limit giveUsing $P=-(\partial F/\partial V{)}_{T,N}$ and the ideal gas free energy,With number density $n=N/V$, this is $P/(nT)=1+B(T)n+O(n^2)$, so $B(T)$ is precisely the second virial coefficient.

For a dilute stack, the membrane number per unit normal length is $1/d=\varphi /\delta$. Dividing the fluctuation repulsion per area by the repeat distance gives its free-energy density

The short-range electrostatic repulsion and long-range van der Waals attraction enter at second-virial order. In general, for an effective pair energy $U_{A_H}(\Gamma )$ over relative configurations $\Gamma$, the second virial coefficient has the Mayer-integral formwith a fixed normalization by the microscopic membrane thickness making $B_2$ dimensionless here. The mean-field contribution is quadratic in membrane concentration. The required two-power free energy can therefore be writtenChanges of microscopic normalization merely rescale $B_2$ by a positive constant and do not affect the transition.

The second virial coefficient is the leading interaction correction to the ideal gas law: at fixed temperature, $B_2(T)={\lim }_{n\to 0}(Z-1)/n$, where $Z=p/(n{k}_{B}T)$ and $n$ is number density. For identical classical particles in a homogeneous three-dimensional gas, with an isotropic pair potential $u(r)$ and $r$ the centre-to-centre separation,The function $f$ is the Mayer f-function. The factor $4\pi r^{2}dr$ counts the volume of a thin spherical shell; the factor $1/2$ counts each unordered pair once. The result has units of volume. Repulsive regions, $u>0$, contribute positively, while attractive regions, $u<0$, contribute negatively. ^[ref]

This is a striking bridge from a microscopic pair potential to a macroscopic pressure reading. At sufficiently small number density, $B_2>0$ raises pressure relative to an ideal gas at the same temperature and number density, while $B_2<0$ lowers it. A single value of $B_2$, however, cannot determine the entire pair potential: many different functions have the same weighted integral. Measurements over several temperatures supply more information.

The integral must exist. For example, a bounded short-range attraction outside a hard core has no difficulty. If instead $u(r)\sim A/r^s$ as $r\to \infty$, then $1-e^{-u/(k_{B}T)}\sim u/(k_{B}T)$ and the radial tail behaves like $\int r^{2-s}dr$: it converges only for $s>3$. A bare unscreened Coulomb potential therefore falls outside this formula's ordinary short-range setting. This condition on the tail does not by itself establish the stability or convergence of the full virial expansion.

For an exactly integrable toy attraction, choose the following square-well pair potential, with diameter $\sigma >0$, attraction depth $ϵ>0$, and range multiplier $a>1$:Set $T^{\ast }=k_{B}T/ϵ$ and $b_{\mathrm{HS}}=2\pi {\sigma }^3/3$, the second virial coefficient of a hard-sphere gas. Integrating the core and attractive shell separately gives the exact toy resultThe core contributes $b_{\mathrm{HS}}$; the shell contributes $-b_{\mathrm{HS}}(a^3-1)(e^{1/T^{\ast }}-1)$. Heating weakens the relative Boltzmann factor enhancement of attractive configurations, so $B_2$ approaches the positive hard-core value as $T^{\ast }\to \infty$. For the illustrative choice $a=3/2$, the zero occurs atAt this temperature, $Z=1+B_3{n}^2+\cdots$: cancellation removes the linear correction, not every correction. At low $T^{\ast }$, the negative shell contribution becomes large, requiring a correspondingly smaller number density for a useful truncated virial expansion. The square well is a deliberately chosen model, not a fit to the carbon dioxide experiment.

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]}