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Attained entropy-maximizing mixtures on compact phase domains

Physical scope

Mixtures of a compact set of declared phase-generator states with continuous entropy and a fixed barycenter; every feasible Borel probability mixture is included, while no attainment claim is made for noncompact domains or a different physical normalization.

Statement

Let d≥1 and let K⊆Rd be a nonempty compact set of dimensionless generator coordinates. Each x∈K labels one model-specified phase-generator state; the model assigns it entropy per mole s(x)∈J mol−1K−1, and s:K→R is continuous, using the numerical entropy value in that fixed unit. Define conv⁡K to be the set of all finite convex combinations of points of K, and fix xˉ∈conv⁡K. Use the Borel sigma algebra relative to K. A Borel probability mixture is a countably additive probability measure P on that sigma algebra; its barycenter and entropy per mole are the coordinatewise integrals ∫Kx dP and ∫Ks dP. For x∈K, define the unit point mass δx by δx(A)=1 if x∈A and δx(A)=0 otherwise, for Borel A⊆K. Assume every Borel probability mixture with barycenter xˉ is feasible and has entropy per mole ∫Ks dP. Then there are m≤d+1, points x1,…,xm∈K, and weights θi≥0 with ∑i=1mθi=1 such that P∗:=∑i=1mθiδxi is a feasible Borel probability mixture and ∫Ks dP∗≥∫Ks dP for every feasible mixture P.

Here integrals use the measure convention of Measure space and integral. The entropy map is part of the model; this theorem derives neither its microscopic meaning nor compactness of a physical phase domain.

Facts & Assumptions

Given: The nonempty compact set K⊆Rd, d≥1, continuous entropy map s, prescribed xˉ∈conv⁡K, coordinatewise integral convention, and feasibility of every Borel probability mixture with that barycenter. The normalization is per mole and no system-size limit is taken.

[A1]

Phase branches and coexistence domains: A generator point is a model-specified state label; the theorem's mixture feasibility is an additional model assumption and does not assert that every phase collection is physically available.

[A2]

Concave macroscopic fundamental entropy: Entropy is a finite state function on the declared physical states. Continuity of s on this compact K is the explicit regularity hypothesis here.

[F1]

The Borel sigma-algebra of a topological space and Probability measures and probability spaces: The Borel sigma algebra is generated by the relatively open subsets of K, and each probability measure has total mass one.

[F2]

Measure space and integral and The thermodynamics measure integral agrees with the shared nonnegative integral: The local nonnegative integral is the supremum of simple-function integrals and agrees with the shared nonnegative Lebesgue integral. Since both signed-integral conventions use the difference of the positive and negative part integrals, they agree on bounded real functions as well.

[F3]

Integrable real and complex functions, and their integrals, The Lebesgue integral is linear on L1(μ), Monotonicity and nonnegative homogeneity of the nonnegative integral, and The modulus of an integral is bounded by the integral of the modulus: Bounded Borel real functions are integrable under a finite probability measure; their integrals are linear, order-preserving, and satisfy ∣∫f dP∣≤∫∣f∣ dP.

[L1]

A continuous real-valued function on a nonempty compact metric space is bounded and attains a greatest and a least value: A continuous real function on a nonempty compact metric space is bounded and attains its minimum and maximum.

[L3]

Rank-nullity: dim⁡FV=nullity⁡T+rank⁡T: For a linear map between finite-dimensional vector spaces, domain dimension equals kernel dimension plus image dimension.

Proof

Given: The data in [A1]–[A2] and [F1]–[F3]. Write h:K→Rd+1 for the continuous map h(x)=(x,s(x)), and let H:=h[K] and C:=conv⁡H, where convex hull means finite convex combinations.

1.1givenA2F1F3L1L2construct

The map h is continuous, so [L2] makes H compact. For every Borel probability P on K, each coordinate of h is bounded and Borel. Compactness and [L1] give boundedness. If ∣f∣≤M for one such coordinate, [F3] gives ∫K∣f∣ dP≤MP(K)=M, so f is integrable.

2.1givenL1L2L3step 1.1constructalgebra

Every point of C is a finite convex combination of points h(xi). If such a representation has N>d+2, the linear map T:RN→Rd+2 defined by T(c)=(∑icih(xi),∑ici) has a nonzero kernel vector c by [L3], because the coordinate bases give domain dimension N and codomain dimension d+2. Thus ∑ici=0 and ∑icih(xi)=0, so c has both positive and negative coordinates. After dropping zero weights from the representation, set t=min⁡ci>0θi/ci and replace each weight θi by θi−tci. The new weights remain nonnegative, still sum to one, represent the same point, and at least one is zero. Repeating reduces every combination to at most d+2 terms. Hence C is the image of Kd+2×Δd+2 under Θ((xi),(θi))=∑i=1d+2θih(xi), where Δd+2:={(θi):θi≥0,∑iθi=1}; shorter combinations are padded with zero weights and any fixed point of nonempty K. Each factor K is closed and bounded by [L2], and Δd+2 is closed by continuity of the finite coordinate sum and its coordinate inequalities; it is bounded since 0≤θi≤1. Their product is therefore closed and bounded in R(d+1)(d+2), so compact by [L2]. To check Θ is continuous on this compact parameter set, fix a parameter ((xi),(θi)). Each coordinate hj is bounded by some M on K and is continuous at each of the finitely many xi. For any ϵ>0, choose neighborhoods of the xi making ∣hj(xi′)−hj(xi)∣<ϵ/(2N) for every output coordinate j, and require ∣θi′−θi∣<ϵ/(2N(M+1)). Since 0≤θi′≤1 and ∣hj(xi)∣≤M, each product difference ∣θi′hj(xi′)−θihj(xi)∣<ϵ/N; summing over i makes each output-coordinate difference smaller than ϵ. Thus Θ is continuous. The continuous-image clause of [L2] makes its image C compact, and [L2] also makes C closed.

3.1givenF1F2F3L2step 2.1construct

Fix any Borel probability P on K and let y(P):=(∫Kx dP,∫Ks dP)=∫Kh dP, with coordinatewise integration. For ϵ>0, compactness of H gives a finite cover of H by open Euclidean balls of radius ϵ. Their preimages under h are Borel; disjointifying them in a fixed finite order gives a finite Borel partition (Ai) of K. For every nonempty part choose zi∈Ai and put θi=P(Ai). Then yϵ:=∑iθih(zi) belongs to C. For x∈Ai, both h(x) and h(zi) lie in the same radius-ϵ ball, so each coordinate difference is at most 2ϵ. The simple map equal to h(zi) on Ai has integral yϵ by the simple-integral definition. By linearity and the integral triangle inequality in [F3], each coordinate of y(P)−yϵ has absolute value at most 2ϵ∑iP(Ai)=2ϵ. Consequently ∥y(P)−yϵ∥2≤2ϵd+1, so the sequence obtained with ϵ=1/n converges to y(P). Since C is closed by step 2.1, y(P)∈C.

3.2givenL1L2step 2.1algebra

Because xˉ∈conv⁡K, a finite convex combination of generators has barycenter xˉ; its corresponding combination of points h(x) shows that Exˉ:={r∈R:(xˉ,r)∈C} is nonempty. The set Exˉ is bounded because C is bounded, and it is closed because C is closed and r↦(xˉ,r) is continuous. By [L2] it is compact in R, so [L1] applied to the identity function yields a maximum r∗∈Exˉ.

4.1givenL3step 3.2constructalgebra

Represent (xˉ,r∗)∈C by a finite convex combination ∑i=1Nθi(xi,s(xi)), dropping zero weights. If N>d+1, the linear map R:RN→Rd+1 given by R(c)=(∑icixi,∑ici) has a nonzero kernel vector by [L3], since its domain dimension is N and its codomain dimension is d+1. Hence ∑ici=0 and ∑icixi=0, with both signs among the ci. If ∑icis(xi)≠0, choose the sign of c so that this sum is positive. For sufficiently small t>0, the weights θi+tci are nonnegative, preserve total mass and barycenter, and increase the last coordinate above r∗, contradicting maximality in step 3.2. Thus ∑icis(xi)=0. Now take t=min⁡ci>0θi/ci and replace θi by θi−tci. This removes at least one positive weight while preserving total mass, barycenter, and entropy value r∗. Repeating finitely many times leaves at most d+1 positive weights.

5.1givenA1F1step 3.1step 3.2step 4.1algebra∎

Let P∗:=∑iθiδxi be the probability measure from step 4.1. Each δxi is countably additive because among disjoint Borel sets at most one contains xi, and δxi(K)=1; hence P∗ is a Borel probability measure. It has barycenter xˉ and entropy r∗, so it is feasible by the model assumption. For any other feasible Borel probability P, step 3.1 gives (xˉ,∫s dP)∈C, so ∫s dP≤r∗. Thus P∗ attains the entropy maximum among all Borel mixtures and has at most d+1 atoms. No finite generator menu was assumed.

Remarks

The proof treats every feasible Borel probability mixture, not just finite mixtures. It proves that the vector of integrated generator coordinates and entropy lies in a compact finite-dimensional convex hull, then uses maximality at the prescribed barycenter to reduce the support to d+1. It does not establish that a physical system has a compact generator domain or that every mathematical mixture is physically feasible; those remain explicit model hypotheses.

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