Direct VUV photolysis of chlorinated methanes and their mixtures in a nitrogen stream

被引:21
作者
Alapi, T.
Van Craeynest, K.
Van Langenhoeve, H.
Dewulf, J.
Dombi, A.
机构
[1] Univ Szeged, Dept Inorgan & Analyt Chem, H-6701 Szeged, Hungary
[2] Univ Ghent, Fac Agr & Appl Biol Sci, Dept Organ Chem, EnVOC,Res Grp Environm Organ Chem, B-9000 Ghent, Belgium
基金
匈牙利科学研究基金会; 美国国家科学基金会;
关键词
184.9 nm VUV light; chlorine radical reaction; direct photolysis; low-pressure mercury lamp;
D O I
10.1016/j.chemosphere.2006.04.090
中图分类号
X [环境科学、安全科学];
学科分类号
08 ; 0830 ;
摘要
The gas-phase decomposition of CCl4, CHCl3 and CH2Cl2 and their binary mixtures was studied in a flow-type reactor in a nitrogen gas stream, using a low-pressure mercury vapour lamp covered with a high-purity silica quartz sleeve. The 184.9 nm vacuum-ultraviolet (VUV) light emitted is able to rupture the C-Cl bond in these target substances. For H-containing compounds, the decomposition takes place not only by direct photolysis, but also by H abstraction by Cl-. formed during the direct photolysis of the target substances. The relative contributions of direct photolysis and Cl-.-sensitized reactions to the decomposition were estimated at different initial concentrations. The addition of CCl4 to CHCl3 or CH2Cl2 increased their decomposition rates via increase of the Cl-. concentration, whereas the addition of CH2Cl2 to CHCl3 decreased its degradation rate, suggesting that CH2Cl2 acts as a Cl-. radical scavenger. The variation of the product distribution confirms the effect of the composition of the irradiated gas mixtures on the relative contributions of Cl-.-sensitized reactions and direct photolysis. (c) 2006 Elsevier Ltd. All rights reserved.
引用
收藏
页码:139 / 144
页数:6
相关论文
共 22 条
[1]  
Atkinson R., 2001, SOC RES UPDATE, V33, P1, DOI DOI 10.1111/J.1442-2018.2010.00541.X
[2]   ULTRAVIOLET PHOTOOXIDATION FOR THE DESTRUCTION OF VOCS IN AIR [J].
BHOWMICK, M ;
SEMMENS, MJ .
WATER RESEARCH, 1994, 28 (11) :2407-2415
[3]   Kinetics and mechanisms of UV-photodegradation of chlorinated organics in the gas phase [J].
Chen, FY ;
Pehkonen, SO ;
Ray, MB .
WATER RESEARCH, 2002, 36 (17) :4203-4214
[4]   Comparative study of removal of volatile organic compounds by cryogenic condensation and adsorption by activated carbon fiber [J].
Dwivedi, P ;
Gaur, V ;
Sharma, A ;
Verma, N .
SEPARATION AND PURIFICATION TECHNOLOGY, 2004, 39 (1-2) :23-37
[5]   Catalytic combustion of volatile organic compounds [J].
Everaert, K ;
Baeyens, J .
JOURNAL OF HAZARDOUS MATERIALS, 2004, 109 (1-3) :113-139
[6]   Direct photolysis of trichloroethene in air: Effect of cocontaminants, toxicity of products, and hydrothermal treatment of products [J].
Haag, WR ;
Johnson, MD ;
Scofield, R .
ENVIRONMENTAL SCIENCE & TECHNOLOGY, 1996, 30 (02) :414-421
[7]   Absolute chlorine atom quantum yield measurements in the UV and VUV gas-phase laser photolysis of CCl4 [J].
Hanf, A ;
Läuter, A ;
Volpp, HR .
CHEMICAL PHYSICS LETTERS, 2003, 368 (3-4) :445-451
[8]   A NEW SENSITIVE CHEMICAL ACTINOMETER .2. POTASSIUM FERRIOXALATE AS A STANDARD CHEMICAL ACTINOMETER [J].
HATCHARD, CG ;
PARKER, CA .
PROCEEDINGS OF THE ROYAL SOCIETY OF LONDON SERIES A-MATHEMATICAL AND PHYSICAL SCIENCES, 1956, 235 (1203) :518-536
[9]   ULTRAVIOLET-ABSORPTION OF SOME HALOGENATED METHANES AND ETHANES OF ATMOSPHERIC INTEREST [J].
HUBRICH, C ;
STUHL, F .
JOURNAL OF PHOTOCHEMISTRY, 1980, 12 (02) :93-107
[10]  
Huybrechts G, 1996, INT J CHEM KINET, V28, P27, DOI 10.1002/(SICI)1097-4601(1996)28:1<27::AID-KIN4>3.3.CO