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For equal-size molecules, let $f$ be the mixing Helmholtz free energy per lattice site. Flory–Huggins solution theory reduces to the regular solution model:The first two terms are minus the combinatorial entropy of mixing; the last is the excess cost of unlike contacts. A positive Flory interaction parameter penalizes such contacts. Additive terms linear in composition change the chosen pure-component reference but do not change stability.

A small composition fluctuation at fixed mean composition costs energy proportional to $f^{\prime \prime }$. Thus local stability requires $f^{\prime \prime }>0$, and the spinodal isInside this curve, $f^{\prime \prime }<0$ and arbitrarily small composition fluctuations grow. The minimum of ${\chi }_s$ is at $\varphi =1/2$, giving the critical value ${\chi }_c=2$. At the thermodynamic critical point, $f^{(2)}=f^{(3)}=0$ while $f^{(4)}>0$.

For $\chi =0$, $f$ is strictly convex with its minimum at $1/2$. At $\chi =2$, the central quadratic term vanishes but a positive quartic term remains. At $\chi =2.5$, there are two minima and a central maximum; the spinodal compositions are $(1\pm \sqrt{1-2/\chi })/2\simeq 0.2764,0.7236$. The common-tangent construction gives coexisting compositions ${\varphi }_b\simeq 0.1448$ and $1-{\varphi }_b$, satisfying $\ln [{\varphi }_b/(1-{\varphi }_b)]+\chi (1-2{\varphi }_b)=0$. Between a binodal endpoint and the spinodal, the homogeneous state is locally stable but metastable; global stability requires the convex envelope of $f$.

For two species of chains with the same polymerization degree $N$, the number of independently translating objects per occupied site is reduced by $N$. The symmetric Flory-Huggins polymer blend hasThe symmetry still places the thermodynamic critical point at ${\varphi }_c=1/2$, but nowThe entropy of mixing per monomer is much smaller than for simple liquids, so even a weak unfavorable interaction can cause phase separation for long chains. If the energetic interaction parameter is $\chi =A/T$ with $A>0$, this model gives $T_c=AN/2$; the conclusion relies on that specified temperature law.

For the symmetric regular solution model, the dimensionless mixing free energy is $f/(k_{B}T)=\varphi \log \varphi +(1-\varphi )\log (1-\varphi )+\chi \varphi (1-\varphi )$. At the thermodynamic critical point, its second and third derivatives in composition vanish. The third derivative gives ${\varphi }_c=1/2$; the second then gives $4-2{\chi }_c=0$. ThereforeThis uses the equal-size, composition-symmetric mixture model.

Diffuse-interface free energy. A sharp boundary assigns one mathematical surface to two uniform fluids. Molecular mixing instead changes composition over a finite distance. In square-gradient theory of a liquid interface, let $\varphi (\mathbf{r})$ be a dimensionless local composition and writeThe bulk free-energy density $f_b$ favors the equilibrium phase compositions, while the gradient term penalizes changing composition too abruptly. Since $f_b$ has units $\mathrm{J}{\mathrm{m}}^{-3}$ and $\varphi$ is dimensionless, $K$ has units $\mathrm{J}{\mathrm{m}}^{-1}$. The theory balances bulk mixing cost against this smoothness cost, rather than imposing a zero-width surface from the start.

At coexistence the two compositions ${\varphi }_{-},{\varphi }_{+}$ have a common-tangent construction for phase coexistence. Subtract this tangent from $f_b$ to define an excess grand-potential density $\Delta \omega (\varphi )$, zero at both bulk compositions. For a planar profile varying along $z$, minimizing the excess free energy givesMultiply by ${\varphi }^{\prime }$ and integrate using ${\varphi }^{\prime }\to 0$ in the bulk:It follows that the interfacial surface tension isThis connects a continuous composition profile to a positive interfacial energy per area.

Broadening near criticality. Close to a symmetric mean-field thermodynamic critical point, an order parameter $m$ measuring departure from the critical composition has bulk densityThe coexistence values are $m=\pm m_0$, $m_0=\sqrt{|r|/u}$. The scalar quartic domain wall profile isThe curvature at either bulk minimum is $f_b^{\prime \prime }(m_0)=2|r|$, so the bulk correlation length is $\xi =\sqrt{K/(2|r|)}$ and this convention gives $w=2\xi$. As $T\to T_c^{-}$, the bulk distinction between phases weakens, its free-energy curvature and barrier decrease, and composition can vary gradually over an increasing distance at little bulk cost. The gradient penalty then favors a wider profile:The same model gives $\gamma =2\sqrt{2K}|r{|}^{3/2}/(3u)$, which vanishes at criticality. The exponents here are mean-field results, not universal exact values for every real mixture.

The figure uses two illustrative parameter values in this quartic model, not experimental parameters supplied by the paper. In addition to the intrinsic gradient-theory width, thermal capillary waves move and roughen an interface. Their increasing amplitude as surface tension decreases can broaden the spatially averaged measured profile further. Thus a measured broad interface can include both intrinsic composition smoothing and long-wavelength interface-position fluctuations.

At the thermodynamic critical point, the two spinodal branches merge: $f^{\prime \prime }=0$ and $f^{(3)}=0$. The third derivative isFor $0<\varphi <1$, its zero gives $1-{\varphi }_c=\sqrt{N}{\varphi }_c$. Substitution in the spinodal relation yieldsAn absolute critical temperature requires an interaction–temperature relation. Under the usual energetic approximation $\chi =C/T$, define the theta temperature $\Theta =2C$, at which an infinite chain has $\chi =1/2$. ThenThus $T_c$ tends to a nonzero constant, $T_c\sim N^0$, while $\Theta -T_c\sim N^{-1/2}$. It is the temperature deficit, not $T_c$ itself, that scales as $N^{-1/2}$.

More generally, if a smooth $\chi (T)$ obeys $\chi (\Theta )=1/2$ and ${\chi }^{\prime }(\Theta )\ne 0$, thenThis is the critical point of a Flory–Huggins polymer solution. The same leading chain-length exponent follows for a smooth temperature law, while its coefficient depends on the omitted solvent thermodynamics. The lattice interpretation connects the chain-length dependence of mixing entropy to the theta condition $\chi =1/2$.^[ref].

Equilibrium requires $h=am+b{m}^3$. On the critical isotherm $a=0$, soHere $\delta$ is defined by $h\propto \mathrm{sgn}(m)|m{|}^{\delta }$ at the critical temperature, or equivalently $|m|\propto |h{|}^{1/\delta }$. The positive quartic coefficient selects a stable equilibrium, including the flat but stable zero-field thermodynamic critical point.

The mean-field approximation replaces the fluctuating environment of each microscopic variable by a uniform average field. For spins, write $S_i=S+\delta S_i$ and drop products $\delta S_i\delta S_j$ between different sites. The resulting single-site problem can be solved independently, and its average spin must reproduce the assumed order parameter $S$: this is the self-consistency equation.

It is reliable when correlated thermal fluctuations about the mean are small, for example with many interacting neighbours, long-range interactions or high spatial dimension. Near a thermodynamic critical point the quantitative test is the Ginzburg criterion. For short-range scalar ordering the upper critical dimension is four, with logarithmic qualifications at four; a two-dimensional nearest-neighbour lattice is below this and its asymptotic critical region of a phase transition is not described accurately by simple mean-field theory.^[ref]

A regular solution keeps the ideal combinatorial entropy of mixing while allowing a nonzero energetic preference for unlike contacts. For a symmetric binary mixture with equal molecular sizes, the displayed free energy per site combines mixing entropy with a contact penalty $\chi \varphi (1-\varphi )$. Its spinodal satisfies $1/\varphi +1/(1-\varphi )-2\chi =0$. At the symmetric thermodynamic critical point, the third composition derivative also vanishes, giving ${\varphi }_c=1/2$ and ${\chi }_c=2$. If $\chi =A/T$, the critical temperature is $A/2$. This is the equal-size limit of Flory–Huggins solution theory.

A diffuse-interface free energy balances the bulk preference for coexisting compositions against a positive penalty for sharp composition gradients. For dimensionless composition $\varphi$, $f_b$ is a bulk energy density and $K$ has units of energy per length. Subtract the bulk coexistence common tangent to define $\Delta \omega (\varphi )$, with equal zero minima at the two compositions. A planar equilibrium profile obeys $K{\varphi }^{\prime \prime }=\Delta {\omega }^{\prime }(\varphi )$ and $K({\varphi }^{\prime }{)}^2/2=\Delta \omega (\varphi )$. Its surface tension is $\int K({\varphi }^{\prime }{)}^{2}dz$. As a thermodynamic critical point is approached, the composition contrast and bulk curvature vanish, the correlation length grows, and the intrinsic interface broadens. A scalar quartic domain wall gives the mean-field hyperbolic-tangent profile. Thermally excited capillary waves can broaden a measured profile further.

For two equal-site-volume polymers of chain length $N$, the mixing free energy per lattice site is $f/(k_{B}T)=[\varphi \ln \varphi +(1-\varphi )\ln (1-\varphi )]/N+\chi \varphi (1-\varphi )$. Each chain is one translating object, reducing the entropy of mixing per monomer by $N$ relative to the regular solution model. Its curvature is $f^{\prime \prime }/(k_{B}T)=1/[N\varphi (1-\varphi )]-2\chi$. The symmetric thermodynamic critical point has ${\varphi }_c=1/2$ and ${\chi }_c=2/N$. Long chains can therefore demix under a very small unfavorable Flory interaction parameter.

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.