For the ideal dilute Maxwell-Boltzmann gas implicit in a single-particle partition function, indistinguishability gives . With Stirling's approximation,
Differentiate at fixed :
This is a thermodynamic-limit ideal-gas result; arbitrary interacting classical gases do not have .
Equilibrium constraints and the Gibbs minimum. The open-system equilibrium contacts allow exchange of heat, volume and matter. For unconstrained contacts without external-field or interface corrections, equilibrium requires equal temperatures, pressures and each exchangeable species' chemical potentials across the contacts. These conditions follow by maximizing total entropy under conserved total energy, volume and species amounts.
The next minimization statement fixes the system's particle number. For a system in a reservoir at , with fixed and only pressure-volume work, the reservoir entropy change gives
For candidate states at the imposed , , the expression in parentheses is . Thus the Fixed-particle-number Gibbs minimum selects stable equilibrium at fixed , with stationary first variation and nonnegative allowed second variation. If particle exchange remains unconstrained, is not fixed and this minimization statement must be replaced by one incorporating the particle reservoir; it is not a justification for minimizing over arbitrary .
The simple-compressible-system first law gives
For a homogeneous extensive single-component phase, the Single-component Gibbs Euler relation follows from , yielding . For a mixture, the corresponding identities are and . Surface effects or other nonextensive contributions require additional terms.[ref]
Reaction equilibrium. Let be an allowed reaction extent for the forward process, so and . At fixed ,
For an interior equilibrium allowing both reaction directions, the coefficient vanishes:
At fixed , minimizing gives the same condition. The reaction formula-unit conservation gives , not the total number of gas particles. This conservation law replaces fixed total particle number for the reacting mixture.
Using the stipulated single-particle functions,
The number-based dissociation equilibrium ratio is therefore
This number-based quantity has a factor of volume; the corresponding concentration ratio depends on temperature alone in the stated ideal model. A standard activity-based equilibrium constant would additionally specify reference states. No bond-energy factor is added to the functions given in the paper.
Define the dissociated fraction of original A formula units by . Then and , so
The dissociation fraction versus conserved density follows because the left side increases monotonically from zero to infinity on . At fixed , increasing decreases , hence decreases dissociation. Equivalently, at fixed compression raises and favours A. Association produces fewer independent translating particles; at high density the translational-entropy advantage of the two-particle side is smaller, so equilibrium shifts toward the one-particle side.
Figure 1.
At fixed temperature the dissociated fraction falls as the conserved formula-unit density increases
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