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An experimental and theoretical kinetic study of the reactions of hydroxyl radicals with tetrahydrofuran and two deuterated tetrahydrofurans

Ádám Illés, Zsófia Borbála Rózsa, Ravikumar Thangaraj, Erzsébet Gombos, Sándor Dóbé, Binod Raj Giri, Milán Szöri

2021Chemical Physics Letters13 citationsDOIOpen Access PDF

Abstract

Rate coefficient expressions for the reactions of OH radicals with tetrahydrofuran (THF) (1), 2,2,5,5-tetradeutero-tetrahydrofuran (THF–d4) (2) and perdeuterated-tetrahydrofuran (THF–d8) (3) were determined from relative kinetic experiments over the temperature range T = 260–360 K displaying a small negative T-dependence. The following rate coefficients were determined at T = 298 K in 10–11 cm3 molecule–1 s−1: k1 = (1.73 ± 0.23), k2 = (0.85 ± 0.11) and k3 = (0.81 ± 0.12). The experimental k (T) values agree reasonably well with the high-pressure limit rate coefficients obtained from conventional transition state theory using input data from CCSD(T)/cc-pV(T,Q)Z//MP2/aug-cc-pVDZ computations. Standard enthalpies of formation for THF and two product furanyl radicals were also computed and compared with literature.

Topics & Concepts

TetrahydrofuranChemistryRadicalKinetic energyDeuteriumMoleculeThermodynamicsPhysical chemistryComputational chemistryOrganic chemistryAtomic physicsPhysicsQuantum mechanicsSolventAtmospheric chemistry and aerosolsCatalysis and Oxidation ReactionsAdvanced Chemical Physics Studies