Peroxyl dipole moments

The peroxyl radical is polar and possesses a high dipole moment ft. For the values of /a calculated by the quantum-chemical method, see below [98, 102] ... 

Alcohols are polar compounds. They have dipole moment and this influences their reactivity in reactions with polar peroxyl radicals (see later). The values of the dipole moments /r for selected alcohols are given below [6]. 

Another factor that influences the reactivity of two polar reactants, acylperoxyl radical with aldehyde, is the polar interaction of carbonyl group with reaction center in the transition state. Aldehydes are polar compounds, their dipole moments are higher than 2.5 Debye (see Section 8.1.1). The dipole moment of the acylperoxyl radical is about 4 Debye (/jl = 3.87 Debye for PhC(0)00 according to the quantum-chemical calculation [54]). Due to this, one can expect a strong polar effect in the reaction of peroxyl radicals with aldehydes. The IPM helps to evaluate the increment Ain the activation energy Ee of the chosen reaction using experimental data [1], The results of Acalculation are presented in Table 8.10. 

---