Quantum Chemical Studies on the Formation of Ozone Adducts to Aromatic Compounds in Aqueous Solution

Abstract

The rate constants of the reactions of ozone with nitrobenzene, chlorobenzene, benzene, methylbenzene, methoxybenzene, phenol, 1,3,5-trimethoxybenzene and phenolate ion in aqueous solution span ten orders of magnitude. The logarithms of the rate constants correlate with the Gibbs free energies of adduct formation (ranging from +18.5 to −21.6 kcal mol⁻¹) calculated with the help of the Jaguar 7.5 program using a dielectric continuum model to account for solvent effects. The electrophilic nature of these reactions is reflected by good correlations with Mulliken charge and similar parameters of these compounds accessible to quantum chemical calculations. Data on the Gibbs free energies of Criegee ozonide formation are also provided.

Keywords:

• Ozone
• Aromatic Compounds
• Rate constants
• Quantum Chemistry
• Kinetics
• Nitrobenzene
• Chlorobenzene
• Benzene
• Methylbenzene
• Methoxybenzene
• Phenol
• 1,3,5-trimethoxybenzene
• Phenolate Ion