Enthalpies of formation of organic free radicals of alcohol and ether derivatives

Abstract

Numerical values of the enthalpies of formation of oxygen containing organic radicals of alcohol and ether derivatives (Δ f H°) were analyzed. For seven out of 25 compounds the corre sponding Δ f H° values were determined more accurately. For 35 radicals, the Δ f H° values were determined for the first time based on the published values of bond dissociation energies in molecules and on the corresponding enthalpies of their formation. Based on the analysis of the Δ f H° values for 60 radicals studied, a structure-property (enthalpy of formation) correlation was established, described in the framework of the group additivity scheme. The parameters for calculations of Δ f H° values for the title radicals were recommended.

Highly Electrophilic Titania Hole as a Versatile and Efficient Photochemical Free Radical Source

“…Equation 7illustrates the cleavage for the radicals derived from DMM, and the corresponding enthalpy of reaction estimated from known thermodynamic data (Scheme S1). 17 In fact, CH 2 O can be detected during the early stages of reaction, and quickly reaches a plateau at 8−10 mM, attributed to the fact that CH 2 O is an excellent SED, quickly reaching steady state concentration when it is consumed as fast as it is generated. Initial formaldehyde formation can be observed with an increasing rate of H 2 generation within the first 15 min of the reaction (Figure S4).…”