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Take $b>0$ for a stable quartic Landau free energy. The cubic-term removal in a conserved quartic Landau free energy uses $\varphi =\psi -c/(3b)$ and gives, apart from a constant,For a closed binary fluid mixture, the compositional order parameter has fixed integral. Adding $d\int \varphi$ therefore adds the same constant to every allowed state. Equivalently, in the common-tangent construction for phase coexistence, a linear term changes the tangent slope, hence the chemical potential, by $d$, but leaves the coexistence compositions unchanged. This is why linear composition bias leaves coexistence compositions unchanged; it would not mean an unchanged composition at a fixed externally imposed chemical potential.

In the shifted variable, the binodal compositions are ${\psi }_{\pm }=\pm \sqrt{-a^{\prime }/b}$ for $a^{\prime }<0$. They merge atThe continuous phase transition therefore has the same scalar quartic Landau theory as the symmetric binary fluid mixture, with a shifted critical composition and control parameter. In the mean-field approximation, the composition difference vanishes with order-parameter critical exponent $1/2$. This argument presumes the critical composition lies in the physically accessible composition range; conservation affects the dynamics, not this static phase coexistence construction.

The two binodal compositions ${\varphi }_1<0<{\varphi }_2$ are the contact points of the common-tangent construction. Equivalently, they solveThe first equality is equality of chemical potential; the second is equality of pressure. Heretogether with the intercept equation determines the two densities. As $C\downarrow a$, both contact points approach zero continuously with scale $|{\varphi }_{1,2}|\propto \sqrt{C-a}$, so this mean-field onset of phase separation is continuous.

Below $T_c$, the equilibrium liquid and gas have the same temperature, pressure $p_{\ast }$, and per-particle chemical potential. For macroscopic bulk thermodynamic phases, neglect interface contributions. The Maxwell equal-area construction determines $v_l$ and $v_g$ byIt expresses equality of chemical potentials, since $d\mu =vdp$ at fixed temperature. Equivalently, the equilibrium Helmholtz free energy per particle follows a common tangent line between the two endpoint states, lying below the homogeneous continuation between them. The construction uses that mathematical continuation to compare endpoints; it is not a physical compression path through negative isothermal compressibility states.^[ref]

Here is a reproducible calculated example at $t=0.9$. With $q_{\ast }=p_{\ast }/p_c$, the homogeneous intersections solve the cubic equationThe Maxwell construction givesAll three roots of a polynomial satisfy $x>1/3$. Only the smallest and largest are the phase coexistence endpoints; the middle one has negative isothermal compressibility. Equal pressures at three admissible values of volume therefore do not imply three stable thermodynamic phases. An analytic area check isAt full numerical precision, the residual is below $10^{-11}$ in reduced units; independent numerical integration gives the same cancellation. At $t=0.9$, the spinodal points are instead $x\simeq 0.718597189$ and $1.528504964$.

The equilibrium plateau changes the phase fraction rather than the endpoint densities. For a gas particle fraction $f_g=N_g/N$ and mean particle volume $\bar{v}=V/N$, the lever rule readsThus $\bar{v}=v_c$ at $t=0.9$ gives $f_g\simeq 0.227219$: this is a particle fraction, not the volume fraction occupied by gas. Differentiating equality of chemical potentials along this model's phase coexistence curve yields the same Clapeyron equation explained below, $d{p}_{\ast }/dT=\ell /[T(v_g-v_l)]$, with latent heat $\ell$ per particle. Both endpoint differences vanish as the Van der Waals critical point is approached; the equation's critical limit must be taken as a ratio.