Activity (chemistry)

Activity (chemistry)

In chemical thermodynamics, activity (symbol a) is a measure of the “effective concentration” of a species in a mixture, meaning that the species' chemical potential depends on the activity of a real solution in the same way that it would depend on concentration for an ideal solution.

By convention, activity is treated as a dimensionless quantity, although its actual value depends on customary choices of standard state for the species. The activity of pure substances in condensed phases (solid or liquids) is normally taken as unity (the number 1). Activity depends on temperature, pressure and composition of the mixture, among other things. For gases, the effective partial pressure is usually referred to as fugacity.

The difference between activity and other measures of composition arises because molecules in non-ideal gases or solutions interact with each other, either to attract or to repel each other. The activity of an ion is particularly influenced by its surroundings.

Activities should be used to define equilibrium constants but, in practice, concentrations are often used instead. The same is often true of equations for reaction rates. However, there are circumstances where the activity and the concentration are significantly different and, as such, it is not valid to approximate with concentrations where activities are required. Two examples serve to illustrate this point:

• In a solution of potassium hydrogen iodate at 0.02 M the activity is 40% lower than the calculated hydrogen ion concentration, resulting in a much higher pH than expected.
• When a 0.1 M hydrochloric acid solution containing methyl green indicator is added to a 5 M solution of magnesium chloride, the color of the indicator changes from green to yellow—indicating increasing acidity—when in fact the acid has been diluted. Although at low ionic strength (<0.1 M) the activity coefficient approaches unity, this coefficient can actually increase with ionic strength in a high ionic strength regime. For hydrochloric acid solutions, the minimum is around 0.4 M.