![Acetic acid, CH3COOH, is composed of a methyl group, CH3, bound chemically to a carboxylate group, COOH. The carboxylate group can lose a proton and donate it to a water molecule, H20, leaving behind an acetate anion CH3COO- and creating a hydronium cation H3O+. This is an equilibrium reaction, so the reverse process can also take place.](http://upload.wikimedia.org/wikipedia/commons/thumb/c/cd/ProtonTransfer.png/305px-ProtonTransfer.png)
An acid dissociation constant, Ka, (also known as acidity constant, or acid-ionization constant) is a quantitative measure of the strength of an acid in solution. It is the equilibrium constant for a chemical reaction known as dissociation in the context of acid-base reactions. The equilibrium can be written symbolically as
- HA ⇌ A− + H+,
where HA is a generic acid which dissociates into A−, known as the conjugate base of the acid, and the hydrogen ion or proton, H+, which, in the case of aqueous solutions, exists as a solvated hydronium ion. The chemical species HA, A− and H+ are said to be in equilibrium when their concentrations do not change with the passing of time. The dissociation constant is usually written as a quotient of the equilibrium concentrations, denoted by [HA], [A−] and [H+]:
Due to the many orders of magnitude spanned by Ka values, a logarithmic measure of the acid dissociation constant is often preferred in practice. pKa, which is equal to −log10 Ka, may also be referred to as an acid dissociation constant. The larger the value of pKa, the smaller the extent of dissociation. A weak acid has a pKa value in the approximate range −2 to 12 in water. Acids with a pKa value of less than about −2 are said to be strong acids; a strong acid is almost completely dissociated in aqueous solution, to the extent that the concentration of the undissociated acid becomes undetectable. pKa values for strong acids can, however, be estimated by theoretical means or by extrapolating from measurements in non-aqueous solvents such as acetonitrile and dimethyl sulphoxide.
The acid dissociation constant for an acid is a direct consequence of the underlying thermodynamics of the dissociation reaction; the pKa value is directly proportional to the standard Gibbs free energy change for the reaction. The value of the pKa changes with temperature and can be understood qualitatively based on Le Chatelier's principle: when the reaction is endothermic, the pKa increases with increasing temperature; the opposite is true for exothermic reactions. The underlying structural factors that determine the magnitude of pKa values include Pauling's rules for acidity constants, inductive effects, mesomeric effects, and hydrogen bonding.
The quantitative behaviour of acids and bases in solution can only be understood if their pKa values are known. For example, many compounds used for medication are weak acids or bases, so a knowledge of the pKa and water–octanol partition coefficient is essential for an understanding of the extent to which the compound enters the blood stream. There are many other applications, including aquatic chemistry, chemical oceanography, buffer solutions, acid-base homeostasis and enzyme kinetics. A knowledge of pKa values is also a prerequisite for a quantitative understanding of the interaction between acids or bases and metal ions to form complexes in solution. Experimentally, pKa values can be determined by potentiometric (pH) titration, but for values of pKa less than about 2 or more than about 11 spectrophotometric or NMR measurements may be required due to practical difficulties with pH measurements.