STUDY OF C2H5O2 USING MODULATED PHOTOLYSIS - ULTRA-VIOLET SPECTRUM AND SELF-REACTION KINETICS IN THE TEMPERATURE-RANGE 233-363 K

To study the reaction of peroxy radicals, we have set up the experimen tal technique of modulated photolysis In this work, the UV absorption spectrum of C2H5O2 and the kinetics of its self-reaction have been inv estigated Experiments have been made, firstly to check our apparatus i n comparing our results with previous measurements, then to obtain new : information in a temperature range where conflicting results were ob tained by previous authors, The room temperature rate constant k(obs) has a value of (10.3+/-0.5)x10(-14) cm(3).molecule(-1).s(-1). In the r ange [253-363] K, the Arrhenius expression is k(obs)=1.56x10(-13) x ex p(-128/T) (cm(3).molecule(-1).s(-1)). The real rate constant of this r eaction was determined from the experimental results of k(obs) and fro m the branching ratio. The Arrhenius expression of real rate is: k(rea l)=6.4x10(-14) x exp(-23/T) (cm(3).molecule(-1).s(-1)).