The decomposition of ethylene by pulsed CO2 laser radiation at pressures from 500 to 3000 torr and the use of the 2 C2H4?cyclobutane equilibrium as an internal thermometer

Abstract

The decomposition of ethylene by pulsed, unfocussed CO2-laser radiation has been studied at pressures from 500 to 3000 Torr, using the P(14) line of the 10.6μm band (v=949.48cm−1) at incident fluences from about 0.1 to 1.0J/cm2. Major products in order of decreasing importance were 1,3-butadiene, acetylene, ethane, propane, 1-butene and methane. These are known products of the thermal free-radical chain decomposition, and it is concluded that the laser-induced decomposition under our conditions is a transient bulk thermal reaction occurring in a thin disc of heated gas close to the entrance window of the reaction vessel at temperatures ranging from about 1000 to 1500K. As in the thermal decomposition, cyclobutane was observed to be a minor product, which in a sequence of laser pulses approached a final constant concentration. The possibility that this corresponded to an equilibrium concentration at some “effective” reaction temperature was explored. Computer simulation was used to model the accumulation of cyclobutane in the system, both in a single pulse and in a sequence of pulses, and predictions of this model were compared with experiment. It was concluded that cyclobutane could be used in this way as an approximate internal thermometer, within certain limits. Mechanisms of formation of the free-radical chain products are discussed. It is concluded that the chains are initiated by the bimolecular disproportionation reaction, 2C2H4 → C2H3+C2H5, and that secondary initiation by dissociation of the product, 1-butene, becomes increasingly important as the reaction proceeds, leading to autocatalysis. It is further concluded that the radical chain decomposition in this system is a transient process occurring in a brief time interval following the short laser pulse (FWHM=110ns), and is far from steady-state conditions.