The process of gasoline compounding is a difficult multistage industrial technology. Octane number is a numerical equivalent of gasoline detonation resistance, the main operational characteristic of trade gasoline. Prediction of octane numbers of individual hydrocarbons was performed with calculations of dissociation energy of their molecules. In this paper, a new approach is proposed for optimization and prediction of the unit operation modes for processing of multicomponent hydrocarbon mixtures, based on a complex mathematical model that considers reactivities of hydrocarbons of wide gasoline fraction in the reforming, isomerization, and compounding processes. The accuracy of calculations is confirmed with huge massive of experimental data obtained from catalytic reforming, catalytic cracking (FCC), isomerization and alkylation units. (C) 2015 Elsevier BA/. All rights reserved.