An acidity function in ethanol – sulfuric acid based on the protonation of diphenylamines

A Hammett H 0 acidity function based on the protonation of 17 diphenylamines in 20 volume % ethanol – aqueous sulfuric acid has been established. The H 0 value for the most acidic solution studied (11.2 M sulfuric acid) is −6.97. This acidity function differs from that based on the protonation of azobenzenes in the same solvent system; the latter diverges to more negative H 0 values as the sulfuric acid concentration increases.The [Formula: see text] values for the protonation of the diphenylamines vary from +1.36 for 4-methoxy-diphenylamine to − 6.21 for 4,4′-dinitrodiphenylamine. A plot of [Formula: see text] versus the Hammett σ constants for five monosubstituted diphenylamines yields a ρ value of +3.36. The [Formula: see text] values for 4-methoxy-, 4-methyl-, 4-methylsulfonyl-, and 4-nitro-diphenylamine are all less (more negative) than expected from the Hammett substituent constants. The substituent effects on the basicities of aniline and diphenylamine are the same.The basicities of several nitro-substituted diphenylamines appear to vary regularly, and do not reflect the presence of a strong interaction between the nitro group and sulfuric acid.