In
chemical thermodynamics activity (symbol:
a) is a measure of the “effective concentration” of a species in a mixture. By convention, it is a
dimensionless quantity. The activity of pure substances in condensed phases (solid or liquids) is normally taken as unity. 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 decreases with increasing ionic strength, 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.
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