Mathematical simulation of the kinetics of radiation induced hydroxyalkylation of aliphatic saturated alcohols

Abstract

The paper reports on the development of the kinetics of radiation hydroxymethylation and hydroxypropylation chain processes relating to aliphatic saturated alcohols in the γ-radiolysis of the alcohol-unsaturated compound systems to give 1,2- and 1,4-diols respectively. These processes were simulated mathematically. The kinetic curves computed are in good agreement with the experimental dependences. The kinetic parameters of the processes, including the rate constants for the addition of α-hydroxyalkyl radicals from the saturated alcohols to the double bond of the unsaturated component, viz. formaldehyde or 2-propene-1-ol in the systems, were estimated. The constants (in dm³/mol·s) for the saturated alcohol-formaldehyde systems incorporating ethanol as the saturated alcohol were found to be (1.5±0.3)·10⁴ at 413 K and (2.1±0.5)·10⁴ at 443 K; incorporating 1-propanol-(6.0±1.3)·10³ at 413 K; for the saturated alcohol-2-propene-1-ol systems incorporating methanol, ethanol, 1- and 2-propanol-(2.5±0.3) ·10⁴, (6.5±0.9)·10⁴, (2.7±0.4)·10⁴ and (1.0±0.1)·10⁵, respectively, at 433 K.