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Chemistry · Ch 4 — Chemical Thermodynamics

Gibbs function and equilibrium constant

4.11.9

Gibbs function and equilibrium constant

Gibbs energy change for a chemical reaction is given by

ΔG=ΔG0+RT ln⁡Q...(4.42)\Delta G = \Delta G^0 + RT\,\ln \mathrm{Q} \qquad \text{...(4.42)}

where ΔG0\Delta G^0 is the standard Gibbs energy change — that is, the Gibbs energy change when the reactants and products in a reaction are in their standard states. QQ is called the reaction quotient. QQ is analogous to the equilibrium constant, and involves nonequilibrium concentrations — or partial pressures, in the case of a gaseous reaction.

Consider

aA+bB⟶cC+dDa\mathrm{A} + b\mathrm{B} \longrightarrow c\mathrm{C} + d\mathrm{D}

ΔG=ΔG0+RT ln⁡Qc=ΔG0+RT ln⁡[C]c [D]d[A]a [B]b...(4.43)\Delta G = \Delta G^0 + RT\,\ln \mathrm{Q_c} = \Delta G^0 + RT\,\ln \frac{[\mathrm{C}]^c\,[\mathrm{D}]^d}{[\mathrm{A}]^a\,[\mathrm{B}]^b} \qquad \text{...(4.43)}

or

ΔG=ΔG0+RT ln⁡Qp=ΔG0+RT ln⁡PC  c×PD  dPA  a×PB  b...(4.44)\Delta G = \Delta G^0 + RT\,\ln \mathrm{Q_p} = \Delta G^0 + RT\,\ln \frac{P_C^{\;c} \times P_D^{\;d}}{P_A^{\;a} \times P_B^{\;b}} \qquad \text{...(4.44)}

(the stoichiometric coefficients appear as superscripts on the concentrations or partial pressures, and the species as subscripts, exactly as the book sets them).

When the reaction reaches equilibrium, ΔG=0\Delta G = 0, and Qc\mathrm{Q_c} and Qp\mathrm{Q_p} become KcK_c and KpK_p, respectively. Thus,

0=ΔG0+RT ln⁡Kcand0=ΔG0+RT ln⁡Kp0 = \Delta G^0 + RT\,\ln K_c \quad \text{and} \quad 0 = \Delta G^0 + RT\,\ln K_p …