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For $A+B\rightleftharpoons AB$, a concentration association constant is $K_a=[AB]/([A][B])$. Comparisons require matched solvent, temperature and standard-state conventions.

A dissociation constant is an equilibrium constant for a reaction in which a combined species separates into components. For $AB\rightleftharpoons A+B$, a concentration convention writesIt has units of concentration. The dimensionless thermodynamic form instead uses thermodynamic activities, $K_d^{\circ }=a_A{a}_B/a_{AB}$. For ideal concentration activities, $K_d^{\circ }=K_d^{(c)}/c^{\circ }$, with specified standard concentration $c^{\circ }$. The choice of quantity and reference is therefore part of quoting the constant.^[ref]

In the simple dilute $1:1$ model with free $c_A$ held fixed, the fraction of B present as AB is $c_A/(K_d^{(c)}+c_A)$. A smaller $K_d^{(c)}$ therefore means more association at the same free concentration. The inverse association constant describes the reversed reaction only when conventions, solvent conditions and temperature match. A dissociation rate is a kinetic quantity and is not specified by this equilibrium ratio alone.

Association in solution includes replacement of solute–solvent contacts, not just formation of the isolated dimer. cyclohexane solvates the benzene surface well through dispersion. Much of the London dispersion gained on bringing two benzene molecules together replaces comparable benzene–cyclohexane contacts, leaving only a modest net gain before the translational and orientational entropy penalty. cyclohexane cannot provide the complementary donor/acceptor interactions available when two waters hydrogen-bond, so water association gains a more distinctive interaction relative to its separated solvated monomers.

Using the same concentration standard state, $K^{\circ }=K_c{c}^{\circ }$ and $\Delta G_{\mathrm{assoc}}^{\circ }=-RT\ln K^{\circ }$. For illustration at 298 K and $c^{\circ }=1\mathrm{mol}{\mathrm{L}}^{-1}$, the ratio of the two supplied association constants corresponds toThus the water-molecule pair can associate more favourably in this solvent even though the stipulated isolated-pair binding energies are similar. Gas-phase potential energy alone omits both differential solvation and the entropy of association.

The important change is preorganization of the chloride-binding amide groups. In the hydroxylated host, intramolecular hydrogen bonds from the phenolic OH groups to the amide carbonyl oxygens restrict rotation and favor a geometry in which the amide NH donors converge on the anion-binding cavity. chloride can therefore accept two favorable hydrogen bonds with a smaller conformational penalty than in the unsubstituted host. The hydroxyl groups need not be counted as two additional freely available chloride donors: their role includes organizing the existing donors.

The association constant increases by $5230/195=26.8$. At $298\mathrm{K}$, the corresponding difference in standard Gibbs free energy isThis is a modest molecular free-energy advantage amplified into a substantial change in the equilibrium constant. solvent competition and changes in solvation also contribute to measured binding; the structures chiefly suggest the preorganization explanation.