Publication Details

Category Text Publication
Reference Category Journals
DOI 10.1021/acs.jpca.7b05782
Document accepted manuscript
Title (Primary) What controls selectivity of hydroxyl radicals in aqueous solution? Indications for a cage effect
Author Kopinke, F.-D.; Georgi, A.
Source Titel Journal of Physical Chemistry A
Year 2017
Department TUCHEM
Volume 121
Issue 41
Page From 7947
Page To 7955
Language englisch
UFZ wide themes RU3;
Abstract The oxidation of three isotopologues of methylcyclohexane (MCH: C7H14, C7D14, c-C6D11-CH3) by OH-radicals (OH) in aqueous solution was investigated. Intermolecular and intramolecular H/D kinetic isotope effects (KIE = kH:kD) for the abstraction of H and D atoms by OH were measured. These KIEs reflect inter- and intramolecular selectivities of hydrogen abstraction, i.e., the selection of OH attack on carbon–hydrogen bonds in different molecules and in different positions of one molecule, respectively. The intermolecular selectivity of OH attack in aqueous solution is largely discriminated against in comparison with the intramolecular selectivity. The observed extent of discrimination cannot be explained by partial diffusion control of the overall reaction rates. A cage model, where OH and hydrocarbon molecules are entrapped in a solvent cage, is more appropriate. The much higher intramolecular KIEs compared to the intermolecular KIEs of the same chemical reaction, R–H + OH → R + H2O, indicate a high degree of mobility of the two reaction partners inside of the solvent cage. This mobility is sufficient to develop an intramolecular selectivity comparable to that of gas-phase reactions of OH. Furthermore, literature data on KIEs of H-abstraction by OH in aqueous and gas phases are discussed. There is a general tendency toward lower selectivities in the aqueous phase.
Persistent UFZ Identifier
Kopinke, F.-D., Georgi, A. (2017):
What controls selectivity of hydroxyl radicals in aqueous solution? Indications for a cage effect
J. Phys. Chem. A 121 (41), 7947 - 7955 10.1021/acs.jpca.7b05782