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Zeitschrift für Physikalische Chemie

International journal of research in physical chemistry and chemical physics

Editor-in-Chief: Rademann, Klaus

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Volume 218, Issue 4


Direct Kinetic Study of Reactions of Hydroxyl Radicals with Alkyl Formates

István Szilágyi / Sándor Dóbé / Tibor Bérces / Ferenc Márta / Béla Viskolcz
Published Online: 2009-09-25 | DOI: https://doi.org/10.1524/zpch.218.4.479.29198


Rate coefficients were determined for the gas phase reactions of hydroxyl radicals with a series of alkyl formats. Experiments were carried out using the isothermal fast flow method coupled with resonance fluorescence detection. The obtained room temperature rate coefficients are (in 10−13cm3 molecule−1s−1 units): 1.83 ± 0.33 (methyl formate), 9.65 ± 0.43 (ethyl formate), 18.73 ± 0.83 (isopropyl formate), 6.77 ± 0.38 (tert-butyl formate) and 1.62 ± 0.13 (methyl chloroformate). These results are compared with the literature data. In addition estimations are made for the partial reactivities of the formate group and for the hydrocarbon groups adjacent to HC(O)O. Moreover, it has been found that the partial reactivity of the HC(O)O group (in reactions of OH with formates) is two orders of magnitude smaller than that of the HC(O) group (in reactions of OH with aldehydes). This has been explained using the results of ab initio calculations at the G3MP2//MP2(full)/6-31G(d) level of theory.

About the article

Published Online: 2009-09-25

Published in Print: 2004-04-01

Citation Information: Zeitschrift für Physikalische Chemie, Volume 218, Issue 4, Pages 479–492, ISSN (Online) 2196-7156, ISSN (Print) 0942-9352, DOI: https://doi.org/10.1524/zpch.218.4.479.29198.

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