二甲胺盐酸盐与氯胺生成NDMA动力学研究
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摘要
研究了二甲胺盐酸盐与氯胺反应生成N,N-亚硝基二甲胺(NDMA)的动力学.采用隔离法测定得到反应物浓度与时间的变化关系,进而采用尝试法求解反应级数、速率常数、速率方程和活化能.结果表明:对于二甲胺盐酸盐与氯胺反应生成中间体的第一步过程,反应物两者的反应级数均为一级,反应速率常数在5,15和25℃下分别为1.5361×10~(-3),1.8707×10~(-3),7.7217×10~(-3)mol~(-1)×min~(-1),反应活化能Ea为51.27kJ/mol.由反应速率常数和活化能数值可以看出温度高有利于反应的进行.所得结果可为含二甲胺基及其同系物与氯胺整体反应的动力学研究,以及原水处理过程中消毒副产物NDMA生成风险的判定提供实验依据.
The kinetics of NDMA formation from dimethylamine hydrochlorate reacted with chloramine were studied. The correlation between the reactant concentration and reacting time was measured by the isolation method, and then the order of reaction,the reaction rate constant, and rate equation as well as the activation energy of dimethylamine hydrochlorate reacted with chloramine were obtained by the tentative method. The reaction of dimethylamine hydrochlorate with chloramine in first step to form an intermediate was second order and first order for both the salt and chloramine. The rate constants of dimethylamine hydrochlorate reacted with chloramines were 1.5361×10~(-3), 1.8707×10~(-3) and 7.7217×10~(-3) mol~(-1)×min~(-1) at 5, 15 and 25℃, respectively. The reaction activation energy Ea was 51.27 kJ/mol. The observed rate constants and the activation energy suggested that the reaction was better under high temperatures. Our results could provide experimental data for the reaction kinetics of dimethylamine and its derivatives with chloramines to form NDMA, and for the risk analysis of NDMA as disinfection by-products in the raw water treatment.
The kinetics of NDMA formation from dimethylamine hydrochlorate reacted with chloramine were studied. The correlation between the reactant concentration and reacting time was measured by the isolation method, and then the order of reaction,the reaction rate constant, and rate equation as well as the activation energy of dimethylamine hydrochlorate reacted with chloramine were obtained by the tentative method. The reaction of dimethylamine hydrochlorate with chloramine in first step to form an intermediate was second order and first order for both the salt and chloramine. The rate constants of dimethylamine hydrochlorate reacted with chloramines were 1.5361×10~(-3), 1.8707×10~(-3) and 7.7217×10~(-3) mol~(-1)×min~(-1) at 5, 15 and 25℃, respectively. The reaction activation energy Ea was 51.27 kJ/mol. The observed rate constants and the activation energy suggested that the reaction was better under high temperatures. Our results could provide experimental data for the reaction kinetics of dimethylamine and its derivatives with chloramines to form NDMA, and for the risk analysis of NDMA as disinfection by-products in the raw water treatment.
引文
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[18]GB 5750.11-2006生活中饮用水标准检验方法消毒剂指标[S].GB 5750.11-2006 Standard examination methods for drinking water disinfectants parameters[S].
[19]张勇,韩建荣,王春艳,等.环境空气中二甲胺的测定[J].干旱环境监测,2008,22(4):193-195.Zhang Y,Han J R,Wang C Y,et al.Determination on dimethylamine in air[J].Arid Environmental Monitoring,2008,22(4):193-195
[2]Nawrocki J,Andrzejewski P.Nitrosamines and water[J].Journal of Hazardous Materials,2011,189(1/2):1-18
[3]Chowdhury S,Rodriguez M J,Sadiq R.Disinfection byproducts in Canadian provinces:Associated cancer risks and medical expenses[J].Chemical Hazards in Industry,2011,187(1):574-584.
[4]Mitch W A,Sharp J O,Trussell R R,et al.N-Nitrosodimethylamine(NDMA)as a drinking water contaminant:A review[J].Environment Engineering Science,2003,20(5):389-404.
[5]Charrois J W A,Boyd J M,Froese K L,et al.Occurrence of N-nitrosamines in Albertapublic drinking-water distribution system[J].Environment Engineering Science,2007,6(1):103-114.
[6]Bei E,Shu Y,Li S,et al.Occurrence of nitrosamines and their precursors in drinking water systems around mainland China[J].Water.Research,2016,98:168-175.
[7]Wang W,Yu J,Wei A,et al.Occurrence and profiling of multiple nitrosamines in source water and drinking water of China[J].Science of the Total Environment,2016,551-552:489-495.
[8]吕娟,沈静,曹先仲,等.药物对A/A/O系统中NDMA及其总前体物去除的影响[J].中国环境科学,2015,35(5):1335-1342.Lv J,Shen J,Cao X Z,et al.Effects of pharmaceuticals on the removal of NDMA and NDMA total precursors in an anaerobic/anoxic/oxic System[J].China Environmental Science,2015,35(5):1335-1342.
[9]韩莹,王济禾,李军,等.氧化铜催化零价铁还原水中亚硝基二甲胺[J].中国环境科学,2017,36(6):2100-2105.Han Y,Wang J H,Li J,et al.Copper oxide-catalyzed reduction of N-nitrosodimethylamine with zero-valent iron in water[J].China Environmental Science,2017,36(6):2100-2105.
[10]Ontario Ministry of the Environment and Energy.Drinking water protection-larger water works[EB/OL].(2000-08-26)
[11]California Department of Health Services.NDMA in Californiadrinking water[EB/OL].(2002-03-15)
[12]Leaveyroback S L,Krasner S W,Suffet I H.The effect of natural organic matter polarity and molecular weight on NDMA formation from two antibiotics containing dimethylamine functional groups.[J].Science of the Total Environment,2016,572:1231-1237.
[13]Sharma V K.Kinetics and mechanism of formation and destruction of N-nitrosodimethylamine in water-A review[J].Separation purification Technology,2012,88(2):1-10.
[14]Choi J,Valentine R L.Formation of N-nitrosodimethylamine(NDMA)from reaction of monochloramine:a new disinfection by-product[J].Water.Research,2002,36(4):817-824.
[15]Lim S,Lee W,Na S,et al.N-nitrosodimethylamine(NDMA)formation during ozonation of N,N-dimethylhydrazine compounds:Reaction kinetics,mechanisms,and implications for NDMA formation control[J].Water.Research,2016,105:119-128.
[16]West D M,Wu Q,Donovan A,et al.N-nitrosamine formation by monochloramine,free chlorine,and peracetic acid disinfection with presence of amine precursors in drinking water system.[J].Chemosphere,2016,153:521-527.
[17]李潇潇.含PDMDAAC复合混凝剂的强化混凝脱浊效能及机制[D].南京:南京理工大学,2012.Li X X.Studies on turbidity removel and mechanisms by enhanced coagulantion using composite coagulants containing polydimethyldiallylammonium[D].nanjing:Nanjing University of Science and Technology,2012.
[18]GB 5750.11-2006生活中饮用水标准检验方法消毒剂指标[S].GB 5750.11-2006 Standard examination methods for drinking water disinfectants parameters[S].
[19]张勇,韩建荣,王春艳,等.环境空气中二甲胺的测定[J].干旱环境监测,2008,22(4):193-195.Zhang Y,Han J R,Wang C Y,et al.Determination on dimethylamine in air[J].Arid Environmental Monitoring,2008,22(4):193-195