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Effects of Iron Purity and Groundwater Characteristics on Rates and Products in the Degradation of Carbon Tetrachloride by Iron Metal

机译:铁纯度和地下水特征对金属铁降解四氯化碳速率和产物的影响

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Carbon tetrachloride (CT) batch degradation experiments by four commercial irons at neutral pH indicated that iron metal (Fe{sup}0) purity affected both rates and products of CT transformation in anaerobic systems. Surface-area-normalized rate constants and elemental composition analysis of the untreated metals indicate that the highest-purity, least-oxidized Fe{sup}0was the most reactive on a surface-area-normalized basis in transforming CT. There was also a trend of increasing yield of the hydrogenolysis product chloroform (CF) with increasing Fe{sup}0 purity. Impurities such as graphite in the lower purity irons could favor the alternate CT reaction pathway, dichloroelimination, which leads to completely dechlorinated products. High pH values slowed the rates of CT disappearance by Peerless Fe° and led to a pattern of decreasing CF yields as the pH increased from 7 to 12.9. The Fe/0 atomic ratio vs depth for Peerless Fe° filings equilibrated at pH 7 and 9.3, obtained by depth profiling analysis with X-ray photoelectron spectroscopy, indicated differences in the average oxide layer composition as a function of pH, which may explain the pH dependence of rate constants and product yields. Groundwater constituents such as (HS){sup}-~, (HCO{sub}3){sup}(-)~, and Mn{sup}(2+) had a slight effect on the rates of CT degradation by a high-purity Fe{sup}0 at pH 7, but did not strongly influence product distribution, except for the HS~ amended Fe{sup}0 where less CF was produced, possibly due to the formation of carbon disulfide (CS{sub}2).
机译:四种商用铁在中性pH下的四氯化碳(CT)批处理降解实验表明,铁金属(Fe {sup} 0)的纯度影响厌氧系统中CT转化的速率和产物。未经处理的金属的表面积归一化速率常数和元素组成分析表明,在转变CT时,以表面积归一化为基础,最高纯度,最低氧化度的Fe {sup} 0具有最高的反应活性。还存在随着Fe {sup} 0纯度增加而增加氢解产物氯仿(CF)的产率的趋势。较低纯度铁中的杂质(例如石墨)可能会影响CT反应的另一途径,即二氯消除,从而导致产品完全脱氯。高pH值减缓了Peerless Fe°造成的CT消失速率,并导致pH值从7增加到12.9时CF产量下降的趋势。通过X射线光电子能谱的深度轮廓分析获得的在pH 7和9.3下平衡的无对Fe°申请的Fe / 0原子比与深度的关系,表明平均氧化物层组成随pH的变化,这可能解释了pH对速率常数和产物产率的依赖性。 (HS){sup}-〜,(HCO {sub} 3){sup}(-)〜和Mn {sup}(2+)等地下水成分对CT降解速率的影响很小。在pH 7时的纯Fe {sup} 0,但对HS分布的影响不大,除非经过HS〜修正的Fe {sup} 0产生较少的CF,这可能是由于二硫化碳(CS {sub} 2 )。

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