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Licensed Unlicensed Requires Authentication Published by Oldenbourg Wissenschaftsverlag September 11, 2015

The Kinetics of the Reaction C2H5 + HI → C2H6 + I over an Extended Temperature Range (213–623 K): Experiment and Modeling

Nicholas Leplat, Jozef Federič, Katarína Šulková, Mária Sudolská, Florent Louis, Ivan Černušák and Michel Jean Rossi

Abstract

The present study reports temperature dependent rate constants k1 for the title reaction across the temperature range 213 to 293 K obtained in a Knudsen flow reactor equipped with an external free radical source based on the reaction C2H5I + H → C2H5 + HI and single VUV-photon ionization mass spectrometry using Lyman-α radiation of 10.2 eV. Combined with previously obtained high-temperature data of k1 in the range 298–623 K using the identical experimental equipment and based on the kinetics of C2H5 disappearance with increasing HI concentration we arrive at the following temperature dependence best described by a three-parameter fit to the combined data set: k1 = (1.89 ± 1.19)10−13(T/298)2.92±0.51 exp ((3570 ± 1500)/RT), R = 8.314 J mol1 K1 in the range 213–623 K. The present results confirm the general properties of kinetic data obtained either in static or Knudsen flow reactors and do nothing to reconcile the significant body of data obtained in laminar flow reactors using photolytic free radical generation and suitable free radical precursors. The resulting rate constant for wall-catalyzed disappearance of ethyl radical across the full temperature range is discussed.

Highly correlated ab initio quantum chemistry methods and canonical transition state theory were applied for the reaction energy profiles and rate constants. Geometry optimizations of reactants, products, molecular complexes, and transition states are determined at the CCSD/cc-pVDZ level of theory. Subsequent single-point energy calculations employed the DK-CCSD(T)/ANO-RCC level. Further improvement of electronic energies has been achieved by applying spin-orbit coupling corrections towards full configuration interaction and hindered rotation analysis of vibrational contributions. The resulting theoretical rate constants in the temperature range 213–623 K lie in the range E-11–E-12 cm3 molecule1 s1, however experiments and theoretical modelling seem at great odds with each other.


Supplementary material

the online version of this article (DOI: 10.1515/zpch-2015-0607) provides supplementary material for authorized users.


Acknowledgement

NL and MJR would like to thank the Swiss State Secretariat of Education and Innovation for providing generous funds in the framework of the COST project CM0901 “Cleaner Combustion” through grant SBF No. C11.0052. IČ, KŠ and JF appreciate the support from Slovak Grant Agencies APVV (projects APVV-0059-10 and LPP-0150-09) and VEGA (grant 1/0092/14). MS would like to acknowledge the support from the Ministry of Education, Youth and Sports of the Czech Republic (project No. LO1305). Computer time for part of the theoretical calculations was kindly provided by the Centre de Ressources Informatiques de Haute Normandie (CRIHAN) and the Centre de Ressources Informatiques (CRI) of the University of Lille1. FL appreciates the support from the French ANR agency under Contract No. ANR-11-LABX-0005 “Chemical and Physical Properties of the Atmosphere” (CaPPA). MJR would like to acknowledge insightful discussions with John R. Barker (University of Michigan) and David M. Golden (Stanford University) on the relationship between theory and experiment for elementary (or not?) free radical-molecule reactions. We explicitly thank professor John R. Barker for pointing out the possible molecular geometry dependence of the applied SO corrections in the review process. MJR also thanks Dr. Hualin Xiao (PSI) for statistical calculations.

Received: 2015-3-30
Accepted: 2015-8-15
Published Online: 2015-9-11
Published in Print: 2015-10-28

©2015 Walter de Gruyter Berlin/Boston