Definition
The Hammett acidity function, H0, can replace the pH in concentrated solutions. It is defined using an equation analogous to the Henderson-Hasselbalch equation:
where lg(x) = log10(x) is the common logarithm of x, and pKBH+ is −lg(K) for the dissociation of BH+, which is the conjugate acid of a very weak base B, with a very negative pKBH+. In this way, it is rather as if the pH scale has been extended to very negative values. Hammett originally used a series of anilines with electron-withdrawing groups for the bases.
Hammett also pointed out the equivalent form
where a is the activity, and the γ are thermodynamic activity coefficients. In dilute aqueous solution (pH 0-14) the predominant acid species is H3O+ and the activity coefficients are close to unity, so H0 is approximately equal to the pH. However beyond this pH range, the effective hydrogen-ion activity changes much more rapidly than the concentration. This is often due to changes in the nature of the acid species; for example in concentrated sulfuric acid, the predominant acid species ("H+") is not H3O+ but rather H3SO4+ which is a much stronger acid. The value H0 = -12 for pure sulfuric acid must not be interpreted as pH = -12 (which would imply an impossibly high H3O+ concentration of 10+12 mol/L in ideal solution). Instead it means that the acid species present (H3SO4+) has a protonating ability equivalent to H3O+ at a fictitious (ideal) concentration of 1012 mol/L, as measured by its ability to protonate weak bases.
Although the Hammett acidity function is the best known acidity function, other acidity functions have been developed by authors such as Arnett, Cox, Katrizky, Yates, and Stevens.
Read more about this topic: Hammett Acidity Function
Famous quotes containing the word definition:
“According to our social pyramid, all men who feel displaced racially, culturally, and/or because of economic hardships will turn on those whom they feel they can order and humiliate, usually women, children, and animalsjust as they have been ordered and humiliated by those privileged few who are in power. However, this definition does not explain why there are privileged men who behave this way toward women.”
—Ana Castillo (b. 1953)
“The definition of good prose is proper words in their proper places; of good verse, the most proper words in their proper places. The propriety is in either case relative. The words in prose ought to express the intended meaning, and no more; if they attract attention to themselves, it is, in general, a fault.”
—Samuel Taylor Coleridge (17721834)
“One definition of man is an intelligence served by organs.”
—Ralph Waldo Emerson (18031882)