The kinetics of vapor-phase nitration of cellulose 2. Nitration with nitric acid under static conditions

The regularities of vapor-phase nitration of cellulose with HNO₃ under conditions of natural convection and hindered heat removal in the absence of air were studied using the nonisothermal kinetic method. It was established that the nitration rate at the depth of conversion of 0.08 to 0.7 is described by the kinetic law d/dt =k₁p/(1+), wherek₁ = 10^4.49±0.6 exp(–A/RT) s^–1 atm^–1, = 10^{–35.5±15.7}exp(B/RT),A = 36.6±3.8 kl mol^–1, andB = 203±88 kJ mol^–1. The diffusion mechanism of vapor-phase nitration of cellulose, which explains the high value of activation energies, is discussed. The effective diffusion coefficient of HNO₃ in cellulose at 25 °3.7 · 10^–7 cm² s^–1) and the activation energy of diffusion (38.3±4.2 kJ mol^–1) were estimated.For Part 1, see Ref. l.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1981–1985, August, 1996.