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Concept
Determination of equilibrium constants
Summary
Equilibrium constants are determined in order to quantify chemical equilibria. When an equilibrium constant K is expressed as a concentration quotient,
it is implied that the activity quotient is constant. For this assumption to be valid, equilibrium constants must be determined in a medium of relatively high ionic strength. Where this is not possible, consideration should be given to possible activity variation.
The equilibrium expression above is a function of the concentrations [A], [B] etc. of the chemical species in equilibrium. The equilibrium constant value can be determined if any one of these concentrations can be measured. The general procedure is that the concentration in question is measured for a series of solutions with known analytical concentrations of the reactants. Typically, a titration is performed with one or more reactants in the titration vessel and one or more reactants in the burette. Knowing the analytical concentrations of reactants initially in the reaction vessel and in the burette, all analytical concentrations can be derived as a function of the volume (or mass) of titrant added.
The equilibrium constants may be derived by best-fitting of the experimental data with a chemical model of the equilibrium system.
There are four main experimental methods. For less commonly used methods, see Rossotti and Rossotti. In all cases the range can be extended by using the competition method. An example of the application of this method can be found in palladium(II) cyanide.
A free concentration [A] or activity {A} of a species A is measured by means of an ion selective electrode such as the glass electrode. If the electrode is calibrated using activity standards it is assumed that the Nernst equation applies in the form
where E0 is the standard electrode potential. When buffer solutions of known pH are used for calibration the meter reading will be a pH.
At 298 K, 1 pH unit is approximately equal to 59 mV.
When the electrode is calibrated with solutions of known concentration, by means of a strong acid–strong base titration, for example, a modified Nernst equation is assumed.
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