Kinetics of Thiocyanate Formation by Reaction of Cyanide and Its Iron Complexes with Thiosulfate

IF 1.7 4区地球科学 Q3 GEOCHEMISTRY & GEOPHYSICS Aquatic Geochemistry Pub Date : 2019-11-07 DOI:10.1007/s10498-019-09361-y

Irina Kurashova, Alexey Kamyshny Jr.

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引用次数: 5

Abstract

Reactions between cyanide and compounds, which contain S–S bonds, in aqueous media result in formation of thiocyanate. In this work, we studied the kinetics of reactions of thiosulfate with free cyanide and its complexes under environmental conditions. Rates of reactions between cyanide species and thiosulfate decrease in the following order: CN^??>?HCN?>?[Fe(CN)₆]^3??>?[Fe(CN)₆]^4?. However, at neutral and slightly acidic pH range, reaction of thiosulfate with iron-cyanide complexes outcompetes its reaction with free cyanide, which exists in equilibrium with complexed cyanide. At environmentally relevant conditions, the characteristic time of reaction between free cyanide and thiosulfate was found to be tens of thousands of years, while for iron-cyanide complexes it was found to be hundreds to millions of years. Examples of application of kinetic parameters for calculation of rates of cyanide consumption in industrial (coke oven wastewater) and non-polluted natural aquatic system (Delaware Great Marsh) are provided.

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氰化物及其铁配合物与硫代硫酸盐反应生成硫氰酸盐的动力学

在水介质中，氰化物与含有S-S键的化合物发生反应，生成硫氰酸盐。本文研究了环境条件下硫代硫酸盐与游离氰化物及其配合物的反应动力学。氰化物与硫代硫酸盐的反应速率依次递减:CN?>? HCN?>?[Fe(CN)6]3? >?[Fe(CN)6]4?。然而，在中性和微酸性pH范围内，硫代硫酸盐与铁氰化物配合物的反应优于与游离氰化物的反应，游离氰化物与络合氰化物平衡存在。在环境相关条件下，游离氰化物与硫代硫酸盐的反应特征时间为数万年，而铁氰化物的反应特征时间为数亿年至数百万年。给出了动力学参数在工业(焦炉废水)和无污染的自然水体系统(特拉华大沼泽)中氰化物消耗速率计算中的应用实例。

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来源期刊

Aquatic Geochemistry 地学-地球化学与地球物理

CiteScore

4.30

自引率

0.00%

发文量

审稿时长

1 months

期刊介绍： We publish original studies relating to the geochemistry of natural waters and their interactions with rocks and minerals under near Earth-surface conditions. Coverage includes theoretical, experimental, and modeling papers dealing with this subject area, as well as papers presenting observations of natural systems that stress major processes. The journal also presents `letter''-type papers for rapid publication and a limited number of review-type papers on topics of particularly broad interest or current major controversy.