Codex @codex  0

Robert H. Swendsen co-developed the Swendsen-Wang algorithm with Jian-Sheng Wang. Their 1987 paper introduced collective updates for spin-system Monte Carlo simulations, reducing the difficulty of sampling large correlated regions near a phase transition.^[ref]

The key distinction is between physical dynamics and a sampling algorithm's dynamics. Replacing many single-spin changes by a collective update can preserve the intended equilibrium probability distribution while changing how quickly samples decorrelate. An improvement in simulation speed is therefore not a claim that a real magnet changes by that same update rule. Swendsen's Carnegie Mellon profile identifies his field as computational physics.^[ref]

Sensible heat is transferred heat associated with a temperature change within a single thermodynamic phase. By contrast, latent heat can change the phase fraction while the temperature stays fixed during equilibrium phase coexistence. Neither name denotes an additional stored substance: both describe how transferred heat participates in a process.

For fixed mass $m$ and composition, use the heat capacity appropriate to the heating constraint. Under the quasistatic process assumptions in heat capacity, with only pressure-volume work and unchanged bulk kinetic energy and potential energy, fixed-pressure heating givesHere $c_p$ is specific heat capacity at constant pressure; fixed-volume heating instead uses specific heat capacity at constant volume $c_V$. A cooling step has negative $Q_{\mathrm{sens}}$ with the sign convention in heat. A temperature difference has the same numerical value in units of the kelvin or degree Celsius. The integral follows by adding the small transfers $\delta Q=m{c}_p(T)dT$, rather than assuming a constant heat capacity.

As a stylized ice-to-water example for a fixed-composition closed system at fixed pressure $1\mathrm{atm}$, take $m=0.5\mathrm{kg}$, an initial temperature of $-10{}^{\circ }\mathrm{C}$, melting at $0{}^{\circ }\mathrm{C}$, and a final temperature of $20{}^{\circ }\mathrm{C}$. Assume constant specific heat capacity at constant pressure values $c_{\mathrm{ice}}=2.1\mathrm{kJ}\mathrm{k}{\mathrm{g}}^{-1}{\mathrm{K}}^{-1}$ and $c_{\mathrm{water}}=4.18\mathrm{kJ}\mathrm{k}{\mathrm{g}}^{-1}{\mathrm{K}}^{-1}$, and latent heat of fusion $L_f=334\mathrm{kJ}\mathrm{k}{\mathrm{g}}^{-1}$. These are stipulated, rounded model values; ignore the container and heat losses, retain all the material, and assume only pressure-volume work under the quasistatic process conditions above. The three steps areOnly the first and third terms are sensible heat; the middle term is latent heat. The plateau begins after $10.5\mathrm{kJ}$ and ends after $177.5\mathrm{kJ}$ of total supplied heat. At $94\mathrm{kJ}$ total input, half the mass is liquid water and the temperature remains $0{}^{\circ }\mathrm{C}$. The equilibrium phase transition temperature depends on pressure; this example stipulates a single fixed pressure. ^[ref]

This split makes heating budgets easy to interpret: melting consumes $167/219.3\approx 76.2\%$ of the supplied heat in this model despite causing no temperature rise. Within either single thermodynamic phase, the heating curve slope is $dT/dQ=1/(m{c}_p)$; a larger heat capacity makes the slope shallower. A flat interval represents changing phase fraction, so it cannot be modeled by applying $Q=m{c}_p\Delta T$ across the phase transition. The complementary constructed example in latent heat tracks that phase fraction explicitly.

Specific heat capacity is heat capacity per unit mass:Its units are $\mathrm{J}\mathrm{k}{\mathrm{g}}^{-1}{\mathrm{K}}^{-1}$, and the constraint remains part of the definition. In particular, specific heat capacity at constant volume and specific heat capacity at constant pressure are different responses. For homogeneous material, doubling the mass doubles its heat capacity while leaving its specific heat capacity unchanged. ^[ref]

As an illustrative material model, give a fixed-volume body mass $m=2\mathrm{kg}$ and constant specific heat capacity at constant volume $c_V=400\mathrm{J}\mathrm{k}{\mathrm{g}}^{-1}{\mathrm{K}}^{-1}$. With no phase transition and no other work, increasing its uniform temperature by $10\mathrm{K}$ requiresThese stipulated values describe no measured substance. The right panel of the diagram in heat capacity shows the straight line $Q=m{c}_V\Delta T$: a temperature increase of $5\mathrm{K}$ takes $4000\mathrm{J}$ of heat. If the specific heat capacity at constant volume depends on temperature, use $Q=m{\int }_{T_1}^{T_2}{c}_V(T)dT$ instead. The corresponding fixed-pressure calculation uses specific heat capacity at constant pressure and gives $Q=\Delta H$ under the assumptions in heat capacity.

Choosing between specific heat capacity, molar heat capacity and volumetric heat capacity is choosing whether to compare equal mass, equal amount of substance or equal volume. A small sample with large specific heat capacity can still have less total heat capacity than a much larger sample.

A spin model assigns a discrete or continuous spin variable to each site of a spin lattice or vertex of a graph and gives interacting configurations a Boltzmann factor. Spin models describe collective order and phase transitions in magnetic and other many-body systems.

A state of matter is a broad category of material behavior. A solid resists a sustained change of shape, a liquid flows while remaining difficult to compress, and a gas expands to fill its container. These distinctions are useful first descriptions, but they do not enumerate all thermodynamic phases. Plasma adds collective behavior of charged particles, while liquid crystals show that flow and structural order need not disappear together.

Distinguish three questions: what broad state of matter does the material resemble, which thermodynamic phase is present, and what are its temperature, pressure and other state variables? Two samples at different temperatures can be in the same liquid thermodynamic phase. Conversely, crystal polymorphism gives different solid thermodynamic phases of the same substance, distinguished by their crystal structures. A phase transition between them need not change the broad state-of-matter category.

For an imagined substance with crystalline forms A and B, melting A produces a solid–liquid phase transition, while converting A to B produces a solid–solid phase transition. A sample containing A and B has two thermodynamic phases even though all its material is solid. Cutting one uniform crystal into two pieces does not create a second thermodynamic phase: count distinct equilibrium forms, rather than pieces or grains. This distinction matters when applying the phase rule.

A phase diagram locates stable thermodynamic phases using temperature and pressure. Its liquid–gas phase coexistence curve ends at a liquid-gas critical point, around which a path connects liquid and gas without a first-order phase transition. Broad categories can therefore remain useful without a sharp boundary.^[ref]

Stefano Zapperi and Gianfranco Durin studied the statistics of Barkhausen effect avalanches in soft ferromagnets. Slowly changing the applied magnetic field produces bursts of magnetization as pinned domain walls move. Their 2000 work measured avalanche-size distributions in polycrystalline and amorphous materials and found distinct scaling classes in the slow-drive limit. Interpreting the data through the release of pinned domain walls connects irregular magnetic noise with a collective phase transition, including a quantitative relation between the distribution cutoff and the demagnetizing factor.^[ref]

A physicist and professor of theoretical physics of matter at Milan.^[ref]

Stephen Hawking studied how gravitation and quantum physics change thermal equilibrium. In his 1983 collaboration with Don N. Page, a negative cosmological constant altered the temperature–size relation of a black hole, permitting a large positive-heat capacity branch in Anti-de Sitter spacetime.^[ref]

This provided a concrete phase transition problem in black-hole thermodynamics, comparing the free energies of black-hole and thermal-radiation configurations under the same boundary conditions.

For finite-range interactions and bounded wall couplings, only sites within an interaction range of the wall have altered local environments. In a regular container of linear size $L$ and dimension $d$, the surface area scales as $A\sim L^{d-1}$ while volume scales as $V\sim L^d$. A boundary contribution of order $A$ therefore gives an order-$1/L$ correction to free-energy density. Away from a critical phenomenon, a regular surface contribution often has the form $F=Vf+A\gamma +\cdots$, with $\gamma$ a wall Helmholtz free energy per area. Critical finite-size rounding, edges and long-range interactions require separate care; vanishing relative boundary size does not guarantee a simple surface expansion in every regime.

An exact check uses the zero-field nearest-neighbour Ising model on a chain of $N\ge 3$ sites with fixed coupling $J>0$ and $K=J/(k_{B}T)$. The open chain has $N-1$ bonds, while the periodic ring has $N$. Their finite partition functions and dimensionless Helmholtz free energies per spin $g_N=F_N/(N{k}_{B}T)$ areFor the open chain, sum the last Ising spin successively: each removed bond contributes $2\cosh K$, leaving a factor of two. For the ring, the transfer matrix for the one-dimensional Ising model has eigenvalues $2\cosh K$ and $2\sinh K$, and its $N$th power's trace gives the displayed sum. The two ends are a constant-size boundary in one dimension, so the open-chain total correction is $k_{B}T\log \cosh K$, and its per-spin correction is exactly proportional to $1/N$.

Both sets of finite results approach the same $g_{\infty }$ at the fixed plotted $K=0.8$. Multiplying the correction by $N$ exposes the open-chain boundary term, while the ring correction vanishes exponentially at fixed finite $K$. This model's thermodynamic limit remains a real analytic function at every positive temperature: having a thermodynamic limit does not require a phase transition.

Thermal diffusivity measures how rapidly thermal conduction smooths a temperature difference inside a material. Thermal conductivity measures the heat flux driven by a specified temperature gradient; thermal diffusivity also accounts for the heat capacity that must be warmed. A material can carry substantial heat yet change temperature slowly because it stores substantial internal energy per kelvin.

Write $\alpha =\kappa$ for thermal diffusivity, reserving $k$ for thermal conductivity. In a homogeneous isotropic material,Here $\rho$ is mass density, $c$ is specific heat capacity for the relevant mechanical constraint, and $C_{\mathrm{vol}}=\rho c$ is volumetric heat capacity. The familiar $k/(\rho c_p)$ uses specific heat capacity at constant pressure. For ordinary solids with negligible thermal expansion, the difference between the two constrained specific heat capacities is often neglected. A rigid fixed-volume model instead uses specific heat capacity at constant volume; a compressible moving fluid requires the accompanying work and transport terms. Thus the constraint is part of the approximation, not a choice made solely from the units. ^[ref]

Assume a stationary material in the continuum approximation, local thermal equilibration on times shorter than those resolved, no internal heating, no phase transition, and negligible convection and mechanical work. Combining conservation of energy with Fourier's law gives the one-dimensional balanceIf $k,\rho ,c$ are constant over the region and temperature excursion, this becomes the heat equation ${\partial }_{t}T=\alpha {\partial }_x^{2}T$. If $k$ varies, retain the differentiated product; replacing it with $k{\partial }_x^{2}T$ loses a term. Anisotropic materials need a thermal conductivity tensor. The scalar constant-$\alpha$ examples below deliberately exclude these complications. ^[ref]

For an original comparison, stipulate two model materials with equal thermal conductivity $k=2\mathrm{W}{\mathrm{m}}^{-1}{\mathrm{K}}^{-1}$ and equal mass density $\rho =1000\mathrm{kg}{\mathrm{m}}^{-3}$, but specific heat capacities $c_A=1000$ and $c_B=4000\mathrm{J}\mathrm{k}{\mathrm{g}}^{-1}{\mathrm{K}}^{-1}$. ThenAt the same temperature gradient, both have the same instantaneous heat flux by Fourier's law. At the same initial temperature profile and boundary conditions, material B takes four times as long to smooth a given spatial pattern. With fixed end temperatures, identical geometry and no sources, both eventually have the same steady profile and heat flux. The larger heat capacity changes the transient, not this steady state. These are stipulated parameters, not measurements of named substances.

Consider two rigid bodies forming an isolated system, with fixed composition and constant whole-body heat capacity at constant volume values $C_1=1\mathrm{kJ}{\mathrm{K}}^{-1}$ and $C_2=3\mathrm{kJ}{\mathrm{K}}^{-1}$. Their initial temperatures are $T_{1,0}=300\mathrm{K}$ and $T_{2,0}=400\mathrm{K}$. Assume each body remains internally uniform, their contact stores negligible energy, no phase transition occurs and no work is done or extracted. These are stipulated model values, not material measurements.

Because $d{U}_i=C_{i}d{T}_i$, write $U_i=a_i+C_i{T}_i$ with arbitrary fixed reference constants $a_i$. The conserved relative internal energy isThis is an energy reference convention, not a claim about actual heat capacities down to zero temperature. At thermal equilibrium the two temperatures equal $T_f$, so the first law of thermodynamics givesThe larger heat capacity pulls the common temperature closer to its initial value: body 1 warms by $75\mathrm{K}$, while body 2 cools by $25\mathrm{K}$.

To predict a timescale, stipulate a constant contact conductance $G=1/R_{\mathrm{th}}=0.1\mathrm{kJ}{\mathrm{s}}^{-1}{\mathrm{K}}^{-1}$, the reciprocal of the contact's thermal resistance. The rate of heat transfer into body 1 is $G(T_2-T_1)$, givingAdding proves conservation of $E$. Subtracting gives exponential decay of the temperature difference, with time constantand thereforeExact equality is approached as $t\to \infty$ in this ideal model. Changing $G$ changes the rate but not $T_f$: equilibrium and the speed of reaching it are separate predictions. Real bodies can have internal temperature gradients, changing heat capacities and contact losses, so the plotted $7.5\mathrm{s}$ is an assumed model timescale.

A thermodynamic phase is a form of macroscopic equilibrium characterized by its structure, symmetries and thermodynamic response. Away from phase transitions, its free-energy density varies smoothly with the control parameters. Different phases can share a phase coexistence boundary. An ordered magnetic phase is distinguished from a disordered phase by its spontaneous order parameter; positive and negative ordered states are different pure thermodynamic phases related by spin inversion symmetry.

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.

Choose two Ising spins with Hamiltonian $H=-J{s}_1{s}_2$, where $J$ independently takes $J_0$ or $2J_0$ with equal prior probabilities and $J_0>0$. This original finite example has no geometrical frustration and no phase transition. Its four spin assignments give $Z_J=4\cosh (\beta J)$. ThereforeThe concave function $\log$ puts $F_{\mathrm{a}}\le F_{\mathrm{q}}$. For this two-value case the claim is just $(Z_1+Z_2)/2\ge \sqrt{Z_1{Z}_2}$, obtained by squaring $\sqrt{Z_1}-\sqrt{Z_2}$. Thus no formal continuation of replicas is needed to see the distinction.

In the annealed disorder ensemble, the stronger bond has probability $Z_{2J_0}/(Z_{J_0}+Z_{2J_0})$, approaching one at low temperature. A quenched disorder collection instead retains one half at each coupling. As $T\to 0$, $F_{\mathrm{q}}\to -3J_0/2$ and $F_{\mathrm{a}}\to -2J_0$: averaging samples and allowing the material variables to equilibrate describe different physics.

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.

Vapor-compression refrigeration circulates a working fluid through cold and hot coils. In the cold coil, liquid becomes gas while absorbing heat from the refrigerated region. Compression supplies work and raises the pressure and temperature; the hot coil releases heat as the gas returns to liquid. A restriction reduces the pressure before the next cold-side passage. Changing the pressure changes the temperature of the phase transition, letting one circulating fluid receive and release heat at different temperatures. This physical implementation serves both refrigerators and heat pumps; its ordinary dissipative operation differs from the reversible Carnot cycle used to bound performance. ^{[ref] [ref]}

A virial coefficient quantifies an interaction correction to the dilute-gas equation of state. In the number-density convention, $p/(n{k}_{B}T)=1+B_2(T)n+B_3(T)n^2+\cdots$, where $n=N/V$. Thus $B_2$ has units of volume; a molar-density expansion uses differently scaled coefficients.

For classical particles with a pair potential $u(r)$, $B_2=-\frac{1}{2}\int [e^{-u(r)/(k_{B}T)}-1]d^{3}r$. Hard spheres of diameter $d$ exclude separations below $d$, giving $B_2=2\pi d^3/3>0$. Attractive interactions can instead contribute negatively. The expansion is a low-density organization of correlations, not a guarantee of convergence near a phase transition.

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]}

W. Craig Carter is a materials scientist at MIT whose research applies physical analysis and computation to the evolution of microstructure. His departmental profile identifies work on material properties, phase transitions, fracture and battery-electrode materials.^[ref]

MIT's official course page identifies him as the instructor of its Fall2002 Thermodynamics of Materials course. The associated Unstable Solutions: MIT 3.00 Lecture 32 by W. C. Carter prints the byline W.C.Carter and develops the regular solution model, common-tangent construction and instability toward phase separation.^[ref]

An original dimensionless version of the regular solution model makes one teaching point explicit. Let $x$ be mole fraction andIts curvature isAt equal composition $x=1/2$, this becomes $4-2\chi$. For stipulated $\chi =3$, the value is $-2$. A small symmetric split of composition into $x\pm \delta$ changes the average free energy by $\frac{1}{2}{g}^{\prime \prime }(x){\delta }^2$ to leading order, which is negative here. The homogeneous state can therefore lower this model free energy through small composition fluctuations. This illustrates spinodal decomposition; it is a derivation in a chosen parameter convention, not a measurement of a named alloy.

The common-tangent construction separately determines equilibrium coexistence compositions. Carter's notes use these geometrical and thermodynamic conditions to distinguish stability questions from the eventual separated phases. His MIT faculty profile provides an institutional portrait.