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On‐line monitoring by membrane introduction mass spectrometry of chlorination of organics in water. Mechanistic and kinetic aspects of chloroform formation
Author(s) -
Rios Rachel V. R. A.,
da Rocha Lilian L.,
Vieira Tales G.,
Lago Rochel M.,
Augusti Rodinei
Publication year - 2000
Publication title -
journal of mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 1076-5174
DOI - 10.1002/(sici)1096-9888(200005)35:5<618::aid-jms986>3.0.co;2-4
Subject(s) - chemistry , chloroform , chlorobenzene , nitrobenzene , phenol , benzene , aniline , toluene , cyclohexanol , organic chemistry , mass spectrometry , phenols , trihalomethane , chromatography , chlorine , catalysis
Chloroform formation during the chlorination of simple organic molecules modeling humic substances, such as phenol and di‐ and trihydroxybenzenes, was studied by on‐line membrane introduction mass spectrometry (MIMS). Under the reaction conditions employed, chloroform was rapidly formed from 1,3‐dihydroxybenzene, 1,4‐dihydroxybenzene, phenol and 1,2,3‐trihydroxybenzene with yields of 17, 13, 7 and 5%, respectively. With the exception of aniline, which afforded a 17% chloroform yield, non‐phenolic compounds, such as nitrobenzene, chlorobenzene, toluene, benzene and cyclohexanol, furnished low yields. Mechanistic studies showed that phenol is chlorinated consecutively and produces initially chlorophenol. It is suggested that chloroform might be formed mainly from chlorinated 3,5‐cyclohexadienone‐type intermediates. MIMS was also used to determine the reaction rates and to study the kinetics of the chlorination. A good Hammett linear correlation for an electrophilic substitution mechanism was found for the compounds C 6 H 5 X (X = NH 2 , OH, CH 3 , H, Cl and NO 2 ). Copyright © 2000 John Wiley & Sons, Ltd.