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Iron(Ⅵ) and Irqn(Ⅴ) Oxidation of Copper(Ⅰ) Cyanide

机译:氰化铜(Ⅰ)的铁(Ⅵ)和铱(Ⅴ)氧化

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Copper(Ⅰ) cyanide (Cu(CN)_4~(3-)) in the gold mine industry presents the biggest concern in cyanide management because it is much more stable than free cyanide. Cu(CN)_4~(3-) is highly toxic to aquatic life; therefore, environmentally friendly techniques are required for the removal of Cu(CN)_4~(3-) from gold mine effluent. The oxidation of Cu(CN)_4~(3-) by iron-(Ⅵ) (Fe~(Ⅵ)0_4~(2-), Fe(Ⅵ)) and iron(Ⅴ) (Fe~Ⅴ0_4~(3-), Fe(Ⅴ)) was studied using stopped-flow and premix pulse radiolysis techniques. The stoichiometry with Fe(VI) was determined to be 5HFeO_4~- + Cu(CN)_4~(3-) + 8H_20 → 5Fe(OH)_3 + Cu~(2+) + 4CNO~- +3/20_2 + 60H~-, The rate law for the oxidation of Cu(CN)_4~(3-) by Fe(Ⅵ) was found to be first-order with each reactant. The rates decreased with increasing pH and were mostly related to a decrease in concentration of reactive protonated Fe(Ⅵ) species, HFe0_4~-. A mechanism is proposed that agrees with the observed reaction stoichiometry and rate law. The rate constant for the oxidation of Cu(CN)_4~(3-) by Fe(V) was determined at pH 12.0 as 1.35 ± 0.02 x 10~7 M~(-1) s~(-1), which is approximately 3 orders of magnitude larger than Fe(Ⅵ). Results indicate that Fe(Ⅵ) is highly efficient for removal of cyanides in gold mill effluent.
机译:金矿行业中的氰化铜(Ⅰ)(Cu(CN)_4〜(3-))在氰化物管理方面引起了最大的关注,因为它比游离氰化物稳定得多。 Cu(CN)_4〜(3-)对水生生物有剧毒;因此,需要采用环保技术从金矿废水中去除Cu(CN)_4〜(3-)。铁(Ⅵ)(Fe〜(Ⅵ)0_4〜(2-),Fe(Ⅵ))和铁(Ⅴ)(Fe〜Ⅴ0_4〜(3-)对Cu(CN)_4〜(3-)的氧化),使用停止流和预混合脉冲放射分解技术研究了Fe(Ⅴ)。 Fe(VI)的化学计量确定为5HFeO_4〜-+ Cu(CN)_4〜(3-)+ 8H_20→5Fe(OH)_3 + Cu〜(2+)+ 4CNO〜-+ + 3 / 20_2 + 60H 〜-,发现每种反应物对Fe(Ⅵ)氧化Cu(CN)_4〜(3-)的速率规律都是一阶的。该速率随pH值的升高而降低,并且主要与反应性质子化的Fe(Ⅵ)物种HFe0_4〜-的浓度降低有关。提出了一种与观察到的反应化学计量和速率定律一致的机理。在pH 12.0下测定Fe(V)氧化Cu(CN)_4〜(3-)的速率常数为1.35±0.02 x 10〜7 M〜(-1)s〜(-1)比Fe(Ⅵ)大大约3个数量级。结果表明,Fe(Ⅵ)对金厂废水中氰化物的去除非常有效。

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