PhysicsLogic / Onsager 1931

Conserved Amount and Chemical Forces

Three chemical forms, two independent variations: inspect what the free-energy derivative actually determines.

Definitions and assumptions

Scope and physical limitations

This is the ideal-solution chemical analogy in Onsager Part I, not a general reaction-network or transport theorem. The fixed-amount variation is a derivative along a conserved direction. The selected logarithmic forces fix a representative; the constrained derivative alone determines only differences. Equation (3.9) is an actual first-order expansion at the reference state. Equation (3.10) uses its linearized forces and a stationary reference to reproduce mass-action rates, not an exact nonlinear kinetic claim about substituting logarithmic forces.

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Examples and distinctions

Constructed examples of this model; each answer includes the Lean statement.

Exact root statement

∀ {Process : Type u} (readout : ChemicalTriangleFormulaReadout Process),
  readout.SourceFormulaAt →
    ∀ (deltaA deltaB deltaC : ℝ),
      deltaA + deltaB + deltaC = 0 →
        HasDerivAt
          (fun parameter =>
            readout.idealFreeEnergyAt (readout.amountAValue + parameter * deltaA)
              (readout.amountBValue + parameter * deltaB) (readout.amountCValue + parameter * deltaC))
          (readout.freeEnergyVariationValueAt deltaA deltaB deltaC) 0
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