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Regular rank form of the finite-component phase dimension count

Statement

Let C≥1 be the number of components and P≥1 the number of phases. Use common positive real coordinates T,p, expressed in fixed units if they are given a physical interpretation, and, for each phase α, an interior composition vector

xα∈ΩC:={x∈RC−1:xi>0, ∑i=1C−1xi<1},

with the convention R0={0} and Ω1={0}. The final component fraction is 1−∑i<Cxi>0. The ambient coordinate domain U=(0,∞)2×ΩCP is open in Rn, where n=2+P(C−1). For each phase α and component i, let μiα(T,p,xα) be a real-valued C1 coordinate function; these are mathematical maps and no thermodynamic potential or physical realization is assumed.

For P≥2, define the q=C(P−1) coexistence equations

Fi,α(T,p,x1,…,xP)=μiα(T,p,xα)−μi1(T,p,x1)=0(1≤i≤C, 2≤α≤P).

At a solution z∗∈U, assume some q×q derivative minor of F:U→Rq is invertible. Then the local solution set is a graph of dimension

n−q=2+P(C−1)−C(P−1)=C−P+2.

For P=1 there are no coexistence equations and the coordinate domain itself has dimension n=C+1=C−P+2. In a specified reactive variant with R≥1, let ν1,…,νR∈RC be linearly independent dimensionless stoichiometric vectors and add the R affinity equations Ar=∑i=1Cνirμi1=0. If the combined equation map has an invertible (q+R)×(q+R) derivative minor at a solution and q+R≤n, its local zero set has dimension

n−q−R=C−P+2−R.

These are conditional local dimensions under the displayed nonsingular-minor assumptions. No dimension formula follows at singular solutions, on composition boundaries, or from equation counting alone; no empirical or general physical phase rule is asserted.

Facts & Assumptions

Given: The finite integers, open coordinate domain, C1 chemical-potential coordinate functions, coexistence equations, and nonsingular-minor assumptions in the Statement.

[F1]

Continuously differentiable maps, local inverses, and local diffeomorphisms: C1 means total differentiability with continuous derivative-matrix entries.

[L1]

Local graph form at a nonsingular derivative minor: for an open V⊆Rn, a C1 map H:V→Rk, 1≤k≤n, and a zero z∗∈V with an invertible k×k derivative minor, the local zero set is a C1 graph over n−k coordinates when k<n, and an isolated point when k=n.

[L2]

Sums and scalar multiples of totally differentiable maps are totally differentiable with the expected derivatives: if f,g are totally differentiable at z and c∈R, then f+g and cf are totally differentiable there, with D(f+g)(z)=Df(z)+Dg(z) and D(cf)(z)=cDf(z). Repeated application gives the derivative of every finite linear combination; continuity of its derivative entries must also be checked to establish C1 regularity.

Proof

technique · direct
1.1F1L1L2givenalgebraconstruct

For each phase let πα:U→(0,∞)2×ΩC select (T,p,xα), and write μ~iα=μiα∘πα. The same coordinate selection on increments is linear and satisfies ∥παh∥2≤∥h∥2. Substituting παh into the first-order expansion of μiα gives derivative Dμ~iα(z)=Dμiα(παz)πα and remainder o(∥h∥2), with zero remainder when παh=0. Its derivative entries are selected entries of Dμiα(παz) or zero; they are continuous because πα does not increase distances and the original entries are continuous. For P≥2, F has q=C(P−1) scalar components, each a difference of these lifted maps. By [L2] their derivative rows are Dμ~iα−Dμ~i1; the entries are continuous since the increment of each difference is bounded by the sum of the two entry increments. The finitely many scalar remainders assemble to a vector remainder o(∥h∥2), since its norm is at most q times their largest absolute value. Thus F is C1 by [F1]. The assumed q×q minor entails 1≤q≤n, so [L1] gives local graph dimension n−q=2+P(C−1)−C(P−1)=C−P+2, including an isolated point if q=n.

1.2givenalgebra

If P=1, no phase-equality equations are indexed because there is no α≥2. The local solution set is all of the open domain U, which has n=2+(C−1)=C+1=C−P+2 coordinates.

2.1step 1.1F1L1L2givenalgebra∎

In the reactive variant put q=0 if P=1. The lifted maps constructed in step 1.1 are C1 for every P≥1. By [L2], DAr(z)=∑i=1CνirDμ~i1(z). For each derivative entry, its increment is bounded by the finite sum of ∣νir∣ times the corresponding continuous entry increments, which tends to zero. Thus the affinity derivative entries are continuous. As in step 1.1, the finitely many scalar remainders assemble to a vector remainder o(∥h∥2), so the combined map is C1 by [F1] and has q+R scalar equations. Since 1≤q+R≤n, its stated minor lets [L1] give graph dimension n−q−R=C−P+2−R, with an isolated point if q+R=n. Linear independence of the νr identifies R distinct reaction directions, while the nonsingular derivative minor remains a separate assumption.

Depends on

Dependency tree · 2 levels

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