Thermodynamic nitration rates of aromatic compounds. Part 1. The nitration of benzene and some benzene derivatives in aqueous sulphuric and perchloric acids. A comparison of the results referred to water as standard state

Abstract

Thermodynamic nitration rates, k₂⁰, referred to water as standard state, are recorded for some aromatic compounds which are nitrated via Wheland intermediates. The values have been calculated by a new mechanistic criterion involving the M_C activity coefficient relationship, and using experimental rate constants, k_{2, obs.}, measured both in sulphuric and perchloric acid. The validity of the results and the confidence intervals of the values are discussed. A new nitration scale of reactivity, relative to benzene, is given for some substituted benzene derivatives. Discussions on the rate-determining step of benzene are also reported, accounting for the results in the range 51–82% H₂SO₄ and 57–65% HClO₄