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Use the classical dilute-gas conventionso the second virial coefficient has units of volume. The Mayer f-function formula for an isotropic pair potential isOnly separations smaller than $a$ contribute. Define $x=\beta \epsilon >0$ and substitute $t=r^3/a^3$, so $r^{2}dr=(a^3/3)dt$:This is the second virial coefficient of a bounded cubic repulsion. For every finite positive $T$, $1-e^{-x}<x$, so $B_2(T)>0$. There is no finite positive Boyle temperature. At high temperature, expanding the exponential givesThus the intended limiting statement isAt the other extreme the classical expression tends to $2\pi a^3/3$, the hard-exclusion value for separation $a$. This is a check on the integral, not a claim that a real molecular gas stays classical at arbitrarily low temperature. A molar virial expansion would instead use $B_{2,\mathrm{m}}=N_A{B}_2$.

For $N$ indistinguishable classical particles the canonical partition function is an integral over phase space,The factor $1/N!$ removes overcounting under particle permutations, and $h^{3N}$ makes the classical phase-space measure dimensionless. The pair potential depends only on positions, so all momentum integrations separate. The three-dimensional Gaussian integral for each particle givesThe grand canonical partition function is $\Xi ={\sum }_{N=0}^{\infty }{e}^{\beta \mu N}{Z}_N$, where chemical potential $\mu$ controls the mean number of particles. ThereforeFor $N=0$, the empty products and configurational integral equal one. The factor $1/2$ in the interaction prevents double counting of unordered particle pairs.

Write $M=\mathcal{N}=V/b$ for the number of cells; this is fixed even though the particle number $N$ fluctuates. Approximate each position integral by the cell sum $\int d^3{r}_i\simeq b{\sum }_{{\alpha }_i=1}^M$, evaluating the slowly varying intercell pair potential at cell centres. With the assumed single-occupancy restriction, the fixed-$N$ contribution becomesAn occupation configuration $\{n_{\alpha }\}$ with $N={\sum }_{\alpha }{n}_{\alpha }$ selects an unordered set of $N$ occupied cells. There are exactly $N!$ ways to assign the temporary particle labels to that set. They all have the same interaction energy, cancelling the prefactor $1/N!$.

Summing over all particle numbers is therefore equivalent to summing each cell occupation independently over $0,1$:The activity per cell, $e^{\beta \mu }b/{\lambda }^3$, is dimensionless. This is a lattice gas, with each cell either empty or occupied.

The exclusion of multiple occupation is an additional physical modeling assumption, explicitly imposed by the question. Making a cell small does not by itself forbid two point particles from entering it; a repulsive core or a dilute-occupancy approximation would be needed to justify that restriction starting from a general continuum pair potential. In the remaining parts it is part of the defined cell model.

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.

For a classical dilute gas with pair potential $u(r)=ϵ[1-(r/a{)}^3]$ for $r<a$ and zero otherwise, put $x=ϵ/(k_{B}T)>0$. Substitution $t=(r/a{)}^3$ in the Mayer f-function formula givesIt is positive for finite positive temperature, tends to $2\pi a^3/3$ as $T\to 0$ in the classical model, and behaves as $\pi a^3ϵ/(3k_{B}T)$ at high temperature. The low-temperature mathematical limit need not remain in the dilute classical regime for a real molecular gas.

A pair potential is stable when its total interaction energy obeys this lower bound for every allowed configuration, with a constant $B$ independent of $N$. It prevents collapse with an arbitrarily negative energy per particle. Stability alone does not control the long-distance contribution needed for the ordinary thermodynamic limit.

A standard sufficient tempering condition is this tail bound beyond a fixed radius, with $ϵ>0$ in spatial dimension $d$. It makes the distant interaction tail integrable; finite-range pair potentials satisfy it. Together with a stable pair potential and suitable growing containers, such assumptions support the conventional thermodynamic limit. A Curie–Weiss model with its size-dependent coupling uses a different prescription.

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]}

For a differentiable central pair potential in a classical homogeneous three-dimensional fluid, the mechanical virial theorem gives the displayed pressure. The radial distribution function accounts for the probability of each pair separation. In the dilute limit, $g(r)=e^{-v(r)/(k_{B}T)}+O(n)$, and integration by parts yields $B_2(T)=-2\pi {\int }_0^{\infty }[e^{-v(r)/(k_{B}T)}-1]r^{2}dr$. Thus the second virial coefficient controls $p/(n{k}_{B}T)=1+B_{2}n+\cdots$. A few virial terms are a low-density approximation, not generally a converged description of a dense liquid. A discontinuous hard core needs its contact form or a limiting argument.