Thermodynamic properties (S298, Cp(T), internal rotations and group additivity parameters) in vinyl and phenyl hydroperoxidesElectronic supplementary information (ESI) available: Internal rotation barriers, Fourier expansion coefficients for internal rotation potentials for vinyl and phenyl hydroperoxides. See http://www.rsc.org/suppdata/cp/b2/b207030h/

Abstract

Thermodynamic properties, S298° and Cp,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 Cp298(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/Cd/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/Cb/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.