+ + +

We may obtain an expression for concentration of radicals-translators of valency, applying stationary radical concentration condition to these block schemes:

(where gs is the HP concentration in s-zones). We also obtain the expression for the s,v-transfer rate:

Vtr = '< [PH] [R · ] = ktrkm[R; ] = Oktrkmkosgs r m k_m + ktr 2k2s(k_m + ktr )

which equals the rate of reactionary v-chain termination Vtr == 2k2[P· ]2; the concentration of radicals attacking hydroperoxide:

and the rate of chain HP decomposition in v-zones:

By taking into account the current concentration of HP that is dissociating in s-zones, characterized by the exponent

gs == gso exp (-kost) and consider that the amount ofHP in s-zones is low, compared with the amount in v-zones, and that the HP concentration in v-zones is at least equal to that in the amorphous phase (gy ~ g), we obtain a reduced final expression for the HP decomposition rate:

- ~~ = J<,.J&Og exp(-0.5kost) = keg exp (-0.5kost) (1) Integrating this expression, we obtain Eq. (2), the HP anaerobic decomposition curve:

g = go exp{ (O.~~os)rexP(-0.5kost) - 1]} (2) Equation (2) is approximated to the first-order equation for significantly small t~O:

and the determined constants of spontaneous decomposition kos x 104s-1 == 1.14; 2.48; 5.06; 10.00 are generalized as follows:

8 (Eos)kos == 6.5 x 10 exp - RT ' Eos == (93.6 ± 5) kJImol (5)

Curves 2a and 3a, calculated according to Eq. (3), are shown in Fig. 2 for comparison. It is clear that they deviate from the experimental points, whereas theoretical curves 2 and 3 are in complete agreement with the experiment.