Zhou H, He Y, Lan Y, Mao J, Chen S
College of Sciences, Nanjing Agricultural University, Nanjing 210095, PR China.
Chemosphere. 2008 Jun;72(6):870-4. doi: 10.1016/j.chemosphere.2008.04.010. Epub 2008 May 19.
The removal of Cr(VI) by zero-valent iron (Fe(0)) and the effect of three complex reagents, ethylenediaminetetraacetic acid (EDTA), NaF and 1,10-phenanthroline, on this reaction were investigated using batch reactors at pH values of 4, 5 and 6. The results indicate that the removal of Cr(VI) by Fe(0) is slow at pH 5.0 and that three complex reagents play different roles in the reaction. EDTA and NaF significantly enhance the reaction rate. The zero-order rate constants at pH 5.0 were 5.44 microM min(-1) in the presence of 4mM EDTA and 0.99 micrM min(-1) in the presence of 8 mM NaF, respectively, whereas that of control was only 0.33 micrM min(-1), even at pH=4.0. This enhancement is attributed to the formation of complex compounds between EDTA/NaF and reaction products, such as Cr(III) and Fe(III), which eliminate the precipitates of Cr(III), Fe(III) hydroxides and Cr(x)Fe(1-)(x)(OH)(3) and thus reduce surface passivation of Fe(0). In contrast, 1,10-phenanthroline, a complex reagent for Fe(II), dramatically decreases Cr(VI) reduction by Fe(0). At pH=4.0, the zero-order rate constant in the presence of 1mM of 1,10-phenanthroline was 0.02 micrM min(-1), decreasing by 99.7% and 93.9%, respectively, compared with the results in the presence and absence of EDTA. The results suggest that a pathway of the reduction of Cr(VI) to Cr(III) by Fe(0) may involve dissolution of Fe(0) to produce Fe(II), followed by reduction of Cr(VI) by Fe(II), rather than the direct reaction between Cr(VI) and Fe(0), in which Fe(0) transfers electrons to Cr(VI).
采用间歇式反应器,在pH值为4、5和6的条件下,研究了零价铁(Fe(0))对六价铬(Cr(VI))的去除效果以及三种络合剂乙二胺四乙酸(EDTA)、氟化钠(NaF)和1,10 - 菲啰啉对该反应的影响。结果表明,在pH 5.0时,Fe(0)对Cr(VI)的去除速率较慢,且三种络合剂在反应中发挥不同作用。EDTA和NaF显著提高了反应速率。在pH 5.0时,4 mM EDTA存在下的零级反应速率常数为5.44 μM min⁻¹,8 mM NaF存在下为0.99 μM min⁻¹,而即使在pH = 4.0时,对照实验的零级反应速率常数仅为0.33 μM min⁻¹。这种增强作用归因于EDTA/NaF与反应产物(如Cr(III)和Fe(III))之间形成络合物,消除了Cr(III)、Fe(III)氢氧化物和Cr(x)Fe(1 - x)(OH)₃沉淀,从而减少了Fe(0)的表面钝化。相比之下,Fe(II)的络合剂1,10 - 菲啰啉显著降低了Fe(0)对Cr(VI)的还原作用。在pH = 4.0时,1 mM 1,10 - 菲啰啉存在下的零级反应速率常数为0.02 μM min⁻¹,与EDTA存在和不存在时的结果相比,分别降低了99.7%和93.9%。结果表明,Fe(0)将Cr(VI)还原为Cr(III)的途径可能是Fe(0)溶解生成Fe(II),然后Fe(II)还原Cr(VI),而不是Cr(VI)与Fe(0)直接反应,即Fe(0)将电子转移给Cr(VI)。