High-Temperature Unimolecular Decomposition of Diethyl Ether: Shock-Tube and Theory Studies

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2019-08, Vol.123 (32), p.6813-6827
• Main Authors: Sela, Paul, Sakai, Yasuyuki, Choi, Hang Seok, Herzler, Jürgen, Fikri, Mustapha, Schulz, Christof, Peukert, Sebastian
• Format: Article
• Language: English
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/acs.jpca.9b04186

The unimolecular decomposition of diethyl ether (DEE; C2H5OC2H5) is considered to be initiated via a molecular elimination and a C–O and a C–C bond fission step: C2H5OC2H5 → C2H4 + C2H5OH (1), C2H5OC2H5 → C2H5 + C2H5O (2), and C2H5OC2H5 → CH3 + C2H5OCH2 (3). In this work, two shock-tube facilities were used to investigate these reactions via (a) time-resolved H-atom concentration measurements by H-ARAS (atomic resonance absorption spectrometry), (b) time-resolved DEE-concentration measurements by high repetition-rate time-of-flight mass spectrometry (HRR-TOF-MS), and (c) product-composition measurements via gas chromatography/MS (GC/MS) after quenching the test gas. The experiments were conducted at temperatures ranging from 1054 to 1505 K and at pressures between 1.2 and 2.5 bar. Initial DEE mole fractions between 0.4 and 9300 ppm were used to perform the kinetics experiments by H-ARAS (0.4 ppm), GC/MS (200–500 ppm), and HRR-TOF-MS (7850–9300 ppm). The rate constants, k total (k total = k 1 + k 2 + k 3) derived from the GC/MS and HRR-TOF-MS experiments agree well with each other and can be described by the Arrhenius expression, k total(1054–1467 K; 1.3–2.5 bar) = 1012.81±0.22 exp­(−240.27 ± 5.11 kJ mol–1/RT) s–1. From the H-ARAS experiments, overall rate constants for the bond fission channels, k 2+3 = k 2 + k 3 have been extracted. The k 2+3 data can be well described by the Arrhenius equation, k 2+3(1299–1505 K; 1.3–2.5 bar) = 1014.43±0.33 exp­(−283.27 ± 8.78 kJ mol–1/RT) s–1. A master-equation analysis was performed using CCSD­(T)/aug-cc-pvtz//B3LYP/aug-cc-pvtz and CASPT2/aug-cc-pvtz//B3LYP/aug-cc-pvtz molecular properties and energies for the three primary thermal decomposition processes in DEE. The derived experimental data is very well reproduced by the simulations with the mechanism of this work. With regard to the branching ratios between bond fissions and elimination channels, uncertainties remain.