The New Jersey Institute of Technology's
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Title:	Conversion and kinetics in the reaction of chloroform with water vapor at high temperatures
Author:	Hwang, Chii-Guang
View Online:	njit-etd1985-022 (92 pages ~ 2.2 MB pdf)
Department:	Department of Chemical Engineering, Chemistry and Environmental Science
Degree:	Master of Science
Program:	Chemical Engineering
Document Type:	Thesis
Advisory Committee:	Bozzelli, Joseph W. (Committee chair) Wong, Wing T. (Committee member) [illegible signature] (Committee member)
Date:	1985-01
Keywords:	Chloroform Rate of chemical reaction Thermochemistry Atmospheric water vapor
Availability:	Unrestricted
Abstract:	This is an experimental study on thermolytic reactions of chloroform with excess water vapor where kinetic parameters are determined and complete product analysis made at atmospheric pressure over a temperature range from 550to 1050°C. In this study, water vapor was introduced as a reactant to convert chlorine in chlorocarbons to stable HCl which is an easily neutralized end-product and thereby completely destroy chloroform. Substantial amounts of thermodynamically stable species: HCl, CO, CO2, C(s) etc. were observed as products. The reaction was studied in a 46cm tubular flow reactor mounted in a furnace that had three independently temperature-controlled heating zones and was capable of operating temperatures to 1200°C with a constant temperature (+/- 5 °C) profile, over its central (80%) region. Complete end-product analysis was performed by flame ionization/ thermal conductivity gas chromatography (FID/TCD GC) and GC/Mass Spectrometer. The major products below 700 °C are hydrogen chloride, tetrachloroethylene and carbon tetrachloride, with vinyl chloride, dichloroethylene, trichloroethylene as minor products.Complete destruction of the parant chloroform took place at temperature around 750 °C and residence time of 0.5 sec.. All the chlorocarbon products were destroyed at temperature above 1000 °C. Kinetic parameters are determined as a function of reagent residence time, temperature, concentration and reactor diameter. The results show that the wall reaction contributes to the overall conversion at the higher temperatures (kw/kb = 0.25 ~ 0.5) and the wall reaction has a higher activation energy than the bulk reaction. The vapor phase activation energy of 28.4 kcal/mol is in fair agreement with unimolecular decomposition data in the literature,indicating that the initial step in this study consists primarily of chloroform decomposition via unimolecular reaction.