Thermodynamic properties (S298, Cp(T), internal rotations and group additivity parameters) in vinyl and phenyl hydroperoxides

Abstract

Thermodynamic properties, S₂₉₈° and C_p,298(T) (300 ⩽ T/K ⩽ 1500)) and internal rotational barriers for trans-CH₃CHCHOOH, cis-CH₃CHCHOOH, (CH₃)₂CCHOOH and CH₃CHC(CH₃)OOH are calculated using density functional calculations at the B3LYP/6-311G(d,p) levels. Entropies (S₂₉₈° in cal mol⁻¹ K⁻¹) and heat capacities C_p298(T) in cal mol⁻¹ K⁻¹) were calculated using the B3LYP/6-311G(d,p) determined frequencies and geometries. Thermodynamic properties for the oxygenated carbon group O/C_d/O are determined with existing literature values of group parameters and data on trans-CH₃CHCHOOH, cis-CH₃CHCHOOH, (CH₃)₂CCHOOH, CH₃CHC(CH₃)OOH, CH₂C(CH₃)OOH. The O/C_b/O group was estimated by using the data calculated on C₆H₅OOH. The moments of inertia and vibrational frequencies as well as the structure parameters have been reported in an earlier study.