Bath Gas Mixture Effects on Multichannel Reactions: Insights and Representations for Systems beyond Single-Channel Reactions

• DOI: 10.1021/acs.jpca.8b10581
• Publication Date: 2018-12-26T19:32:48Z
• Authors: Lei Lei; Michael P. Burke
• Keywords: Branching (polymer chemistry); Branching fraction

Nearly all studies of and available data for pressure-dependent reactions focus on pure bath gases. Of the comparatively fewer gas mixtures, important to combustion planetary atmospheres, nearly single-channel reactions. The present study explores, seeks reliable representations of, mixture effects multichannel Analytical numerical solutions master equation here reveal several unique manifestations reactions, including behavior completely opposite trends observed most common way evaluating rate constants from components, classic linear rule, is found yield errors exceeding a factor ∼10. A new rule based reduced pressure, instead absolute be accurate within ∼30% (and ∼50% branching ratio). nonlinear that additionally incorporates analytically derived activity coefficients ∼10% ratios. These rules are therefore recommended use in fundamental applied chemical kinetics investigations reacting flow codes experimental interpretations third-body efficiencies.