模拟环境条件下δ-MnO2氧化As(III)的搅拌流动动力学特征.pdfVIP

中国环境科学 2014,34(4) ：966~975 China Environmental Science 模拟环境条件下 δ-MnO 氧化 As(III) 的搅拌流动动力学特征 2 王 鹍,夏平平,刘 凡,谭文峰,邱国红,冯雄汉* (华中农业大学资源与环境学院,农业部长江中下游耕地保育 重点实验室,湖 武汉 430070) 摘要：采用搅拌流动法研究了酸性水钠锰矿及水羟锰矿 2 种 δ-MnO2 矿物氧化 As(Ⅲ) 的动力学过程,构建了可用于多相体系的搅拌-流动 氧化还原反应动力学模型.经过 As 吸附量的校正后,该模型对酸性水钠锰矿及水羟锰矿氧化 As(III)动力学数据拟合度分别为 0.980 和 0.951, 模型拟合得到 pH 7 时 2 种矿物单位比表面上氧化 As(III) 的初始反应速率常数 k 分别为 0.131,0.014min- 1⋅m-2 .相比而言,该速率常数明显高 于批量法得到的表观速率常数 kobs,0.021,0.001min- 1⋅m-2 更接近真实的化学动力学参数.搅拌流动法与批量法得到的不同矿物的速率常数大 小趋势一致,即尽管酸性水钠锰矿对 As(III) 的氧化率低于水羟锰矿,单位比表面上酸性水钠锰矿氧化 As(III)初始反应速率却远高于水羟锰 矿.反应过程分析表明,反应初始阶段,As(III)的吸附为主要限速步骤;而随着反应的进行,矿物表面反应位点逐渐钝化或减少,反应位点数量 成为限速步骤. 关键词：As(III) ；δ-MnO2 ；搅拌流动法；动力学；速率常数；反应位点 中图分类号：X131.2 文献标识码：A 文章编号：1000-6923(2014)04-0966-10 Kinetic characteristics of As (III) oxidation by δ-MnO in the simulated environment: A stirred flow study. WANG 2 Kun, XIA Ping-ping, LIU Fan, TAN Wen-feng, QIU Guo-hong, FENG Xiong-han* (Key Laboratory of Arable Land Conservation (Middle and Lower Reaches of Yangtze River), Ministry of Agriculture, College of Resources and Environment, Huazhong Agricultural University, Wuhan 430070, China). China Environmental Science, 2014,34(4)：966~975 Abstract ：In this study, As (III) oxidation at the surfaces of two δ-MnO2 minerals, birnessite and vernadite, was investigated using stirred-flow technique, and the corresponding model was established to describe the kinetics of the redox reactions in the stirred-flow heterogeneous system. Following correction of As adsorption, the degree of fitting of the stirred-flow kinetic data of As (III) oxidation by birnessite and vernadite using the established model was 0.980and 0.951, respectively.