We study correlations among uncertain Arrhenius rate parameters in a chemical model for hydrocarbon fuel–air combustion. We consider correlations induced by the use of rate rules for modeling reaction rate constants, as well as those resulting from fitting rate expressions to empirical measurements arriving at a joint probability density for all Arrhenius parameters. We focus on homogeneous ignition in a fuel–air mixture at constant-pressure. We outline a general methodology for this analysis using polynomial chaos and Bayesian inference methods. We examine the uncertainties in both the Arrhenius parameters and in predicted ignition time, outlining the role of correlations, and considering both accuracy and computational efficiency.