Water Catalysis of the Reaction Between the Hydroxyl Radicals and Linear Saturated Alcohols (ethanol and n-propanol) at 294 K

TACCONE, RAUL

PHYSICAL CHEMISTRY CHEMICAL PHYSICS

ROYAL SOC CHEMISTRY

Año: 2018

1463-9076

p class="MsoNormal" style="text-indent: 36pt; line-height: 150%;">The rate coefficients for the reactions of OH with ethanol andn-propanol were determined by a relative method in a smog chamber at 294 K, 1atm of air or N2 and a wide range of humidity. The rate coefficientsfor both reactions show a quadratic dependence on the water concentration as inthe case of the reaction of OH with methanol (Jara-Toro et al. Angew. ChemieInt. Ed. 2017, 56, 2166). The detailed mechanism responsible for the reactionacceleration was studied theoretically at the uMP2/aug-cc-pVDZ theory while theelectronic energies of all the structures were refined at theuCCSD(T)/aug-cc-pVDZ level. From these results it is suggested that thecatalytic effect of two water molecules is due to two cooperative effects inthe reactions between the ROH(H2O) and OH(H2O)equilibrium complexes: 1) an enhanced capture cross-section as a consequence ofthe larger dipolar moment of the