新显色剂NPBPDT的合成及在环境监测中的应用研究.pdf

新显色剂NPBPDT的合成及在环境 监测中的应用研究 张春牛 郑云法 顾勇冰 赵桂丹 丽水学院化学系, 浙江 323000 摘要 研究了 1 - 4-硝基苯基 -3 - 5-溴-吡啶 三氮烯 NPBPDT 的合成及其与汞的显色反应。 在 TX -100存在下, pH 值 为 11. 5的 Na2B4O7-NaOH 缓冲溶液中, 该试剂能与汞发生显色反应, 汞与NPBPDT 形成摩尔比为 1∶ 2 型的黄色配合物, 在 440 nm处有一最大正吸收峰, 在 535 nm 处有一最大负吸收。 以 440 nm 为参比波长, 535 nm 为测量波长进行双波长 测定, 表观摩尔吸光系数为 2. 80105L molcm, 汞的浓度在0～ 12μ g 25 mL 范围内符合比尔定律。 用拟定方法测定废 水中的微量汞, 有较高的准确度和精密度。 关键词 1- 4 -硝基苯基 -3 - 5 -溴-吡啶 三氮烯 汞 显色反应 1 引言 三氮烯试剂是测定微量镉、汞、锌、镍、铜等金属 离子的高灵敏显色试剂 [ 1～ 3] ,其中含氮杂环的三氮烯 试剂的显色效果更佳 [ 4～ 6] 。为改善试剂的分析性能, 提高此类试剂的灵敏度和选择性 , 本研究合成了 1- 4-硝基苯基 -3 - 5 -溴-吡啶 三氮烯 NPBPDT , 并 对其分析性能及与汞的显色反应进行了研究。结果 表明 ,在表面活性剂 Triton X-100 存在下 ,该试剂与汞 有灵敏的显色反应, 其选择性也较理想 。用拟定方法 测定废水中微量汞 ,结果与原子吸收法相符 , 5 次测 定的 RSD20 mg 时对测定结果无影响 ,试验了常见离子的共存允许量 如下 以 μ g 计 为共存允许最大量 K 、 Na 、 NH 4、 F - 、Cl - 、Br - 、I - 、NO - 3、SO 2- 4、SO 2- 3、C2O 2- 4、PO 3- 4、 SiO 2- 3 1 000, 未做上限 , Ca 2 、Mg 2 、Ba 2 800 , Al 3 300 , Pb2 、 Fe 3 50 , Zn2 4 , Cd2 4 , Cu2 8 ,Ag 15 ,Co2 10 ,Ni2 10 。以 20mg NH 4F 的 和20 mg Na2S2O3作为混合掩蔽剂时可容许 Cd 2 8 ,Zn 2 12 ,Cu2 15 ,Ni2 15 ,Co2 20 共存。 3. 8 样品分析 移取一定量工业废水样品 , 置于烧杯中, 加入王 水3 mL , 在不断搅拌下, 加热至近干 。再加入盐酸 2 mL, 加热至近干。冷却后加入一定量水,移入50 mL 容量瓶中, 以去离子水定容到刻度线并混合均匀。然 后移取一定量的试样溶液于 25 mL 的容量瓶中 ,加入 混合掩蔽剂 20 mg Na2S2O3和 20 mg NH4F , 以下按 实验方法进行测定, 分析结果见附表 。 附表 样品中汞的测定结果 n5μ g mL 样品AAS 本法 测定值 加入 镉量 测得量 RSD 回收率 废水 12. 342. 442. 004. 502. 1103. 0 废水 21. 571. 622. 003. 572. 597. 5 4 结论 设计合成了一种新的三氮烯类显色剂,用于微量 汞的定量分析的方法 。通过试剂与汞显色反应条件 的探讨和对工业废水中微量汞的测定结果表明,该试 剂具有高灵敏度和较好的选择性, 测定方法简便快 速,优于经典的双硫腙法 ,省去了用有毒有机溶剂萃 取繁琐地操作。测定结果与原子吸收法相符 ,5 次测 定的 RSD 3,具有较高的准确度和精密度 。 参考文献 1 夏心泉, 丁海军, 崔微. 水中微量汞的分光光度测定研究. 工业水处 理, 2001. 21 3 28～ 30. 2 夏心泉, 崔微, 丁海军. 新试剂的合成及与镉的显色反应. 环境工 程, 2001. 19 2 37～ 39. 3 张春牛, 杨明华, 郑云法. 1 - 2 -羟基 -5 -硝基苯基 -重氮氨基偶氮苯 与汞的显色反应化学研究与应用, 2003. 15 3 405～ 406. 4 汪朝存, 哈成勇. 2-吡啶重氮氨基偶氮苯与镉 Ⅱ 的显色反应及其 应用. 分析化学,1998. 26 10 1260～ 1263. 5 龚楚儒, 杨明华, 金传明等. 1 -偶氮苯基 3 - 5 -硝基 -2 -吡啶 -三氮烯 与镉的显色反应及其应用, 2001. 29 2 246～ 247. 6 张春牛, 郑云法, 王智敏. 6 -硝基 -2 -苯并噻唑重氮氨基偶氮苯的合 成及与镍的显色反应. 冶金分析, 2004. 24 2 16～ 18. 作者通讯处 张春牛 323000 浙江省丽水市 丽水学院化学系 2004- 10-08 收稿 76 环 境 工 程 2005年 8 月第23 卷第4 期 Abstract A technique using the waste slag to treat chromium dregs has been advanced in order to eliminate environmental pollution. Using the high temperature and reduction of the blast furnace slag, the chromium dregs were mixed at appropriate proportion with blast furnace slag, which could make chromium dregs detoxify. In the present study, the detoxification mechanism of chromium dregs was analyzed theoretically. The experiment results show that the blast furnace slag can remove the toxic of Cr6completely while the mass quantity of added chromium dregs was less than 10 percent. Keywords chromium dregs, blast furnace slag and detoxification mechanism DISCUSSION ON PRODUCTION OF SOLID FUEL USING INDUSTRIAL SOLID WASTES WITH HEAT VALUELin Guangqing et al 67 Abstract A large amount of solidwastes are produced every year by industrial enterprises. If the wasteswith heat value are used to research and produce mixed RDF solid fuel, the advantages of recycling resources and recovering energy can be realized. It can control effectively the secondary pollution while the reduction of environmental pollution can also be realized, whose economic, social and environmental benefits have strong attraction, which is worth exploring . Keywords waste plastic film, sludge, RDF and solid fuel INFLUENCE OF LANDFILL STRUCTURE ONLEACHATE CHARACTERISTICS Wang Qi et al 69 Abstract Two large scale landfilling installations were built according to semi-aerobic landfilling and anaerobic landfilling theories. The concentrations of CODCr, BOD5andNH3-N were detected regularly . The results showed that, the concentration of pollutants in leachate of semi- aerobic landfilling structure reduced more quickly than that in anaerobic landfilling structure. The pollutant concentrations in leachate of semi- aerobic landfilling structure reduced regularly , but which in aerobic landfilling leachate varied greatly in early period of experiment. Keywords semi -aerobic, municipal solid waste, landfill and leachate APPLICATION OFMODIFIEDOSCULATINGINENVIRONMENTALQUALITY ASSESSMENT ON SURFACE WATERCao Jianrong et al 72 Abstract As a multi-objective decision optimization , osculating has been used in assessment on environmental quality of surface water. Modified osculating considers environmental criteria as samples of environmental matrix. Osculating value of every sample is given to make sure the qualities of all surface water sections. Moreover, analytic hierarchy process was used to decide the contribution of each index . It makes the result of environmental quality assessment on surface water more scientific. Keywords osculating , analytic hierarchy process, surface water and environmental quality assessment STUDY ON THE SYNTHESIS OF A NEW CHROMOGENIC REAGENT AND ITS APPLICATION IN ENVIRONMENTAL MONITORINGZhang Chunniu et al 75 Abstract This paper reports the synthesis of the new reagent 1- 4 -nitrophenyl -3 - 5 -bromopyridyl -triazene NPBPDTand the color reaction of NPBPDT with mercury. In the presence of the surface active agent Triton X -100 and in the Na2B4O7-NaOH medium of pH 11. 5, the reagent a yellow complex withmercury in the molar ratio of 1∶ 2. The molar absorptivity is 2. 80105L mol cm by dual -wavelengh of 440 nm and determination wavelengh of 535 nm. Beer s law is obeyed in the range of 0 ～ 12 μ g 25 mL. The has been applied to the direct determination of mercury in waste water with satisfactory results. Keywords 1 - 4 -nitrophenyl -3 - 5 -bromopyridyl -triazene, mercury and color reaction STUDYONTHESFORDETERMININGTRACEALDEHYDEBY PHLOROGLUCINOLZhang Shulin 77 Abstract This article studies a new of determining trace aldehyde by phloroglucinol. The application conditions of color reagent are investigated. This is simple, convenient and less sort of reagent and the degree of accuracy and precision is higher. Keywords aldehyde, phloroglucinol and color reaction STUDYONATMOSPHERICENVIRONMENTALCAPACITYANDATMOSPHERIC ENVIRONMENTAL MANAGEMENT IN ENERGY HEAVY INDUSTRY AREALin Jiquan et al 79 Abstract The atmospheric environmental capacity in Longmen Energy Heavy Industry Area is calculated using a box model of different frequency of wind speed. The result shows that the capacity of sulfur dioxide andTSP is respectively 21 097. 72 t and 63 293. 15 t in a year. The of selecting data and benefit transfer approach are respectively put into use to add up systematically discharging capacity and calculate the unsystematically discharging amounts, and the amount of sulfur dioxide is 13 728. 79 t a, and TSP is 68 555. 97 t a. The using ratio of SO2of atmospheric environmental capacity is 71. 2, and TSP is 108. 1 on small wide speed and still wind occasion. The using ratio of SO2of atmospheric environmental capacity is 30. 1, and TSP is 109. 6 on gale occasion. The result shows air pollution is different in different conditions, that is to say, SO2comes from systematically discharging, comparative spare capacity is 7 368. 93 t a. And TSP is in excess of its capacity, flying dust about coal and uncovered floor are main pollution sources on gale occasion, and atmospheric pollution is produced by 5 ENVIRONMENTAL ENGINEERING Vol. 23,No. 4, Aug . , 2005