Shock tube pyrolyses. Part I. The thermal decomposition of isopropyl chloride, ethyl fluoride, and n-propyl fluoride
A comparative shock tube technique has been developed based on Tsang's method which is capable of measuring reaction rates accurately. By use of this technique irreproducibility of results, found in conventional static studies and associated with heterogeneous effects, are overcome. Errors due to uncertainties in the reaction temperature inherent in standard shock tube studies are also greatly reduced. The technique has been applied to the thermal dehydrohalogenations of isopropyl chloride, ethyl fluoride, and n-propyl fluoride. The rate constants for these three compounds have been found to be given by equations (i), (ii), and (iii). PriCl log k(sec.–1)=(13·56 ± 0·45)–(50,800 ± 1400)l 2·3RT(i), EtF log k(sec.–1)=(13·42 ± 0·30)-(59,900 ± 1000)l 2·3RT(ii), PrnF log k(sec.–1)=(13·26 ± 0·30)–(58,300 ± 1000)l 2·3RT(iii).