Oxidation of ethanethiol in aqueous alkaline solution by ferrate(VI): Kinetics, stoichiometry and mechanism

Jing Wang; Tong Zheng; Chen Cai; Yanxiang Zhang; Huiling Liu

doi:10.1016/j.cej.2018.11.005

Oxidation of ethanethiol in aqueous alkaline solution by ferrate(VI): Kinetics, stoichiometry and mechanism

Jing Wang
, Tong Zheng^*
, Chen Cai
, Yanxiang Zhang
, Huiling Liu

^*Corresponding author for this work

School of Materials Science and Engineering

Harbin Institute of Technology
School of Environment, Harbin Institute of Technology
Tongji University

Research output: Contribution to journal › Article › peer-review

16 Scopus citations

Abstract

The oxidation of ethanethiol (C₂H₅SH), as a representative odorous pollutant, by ferrate (Fe(VI)) in aqueous alkaline solution was investigated to understand its kinetics, stoichiometry, and reaction pathways. The reaction kinetics and fraction of different intermediates were found highly dependent on pH. The reaction behaved as a 5/2-order reaction in a pH range of 8.0–10.0, and a second-order reaction in a pH range of 10.5–12.0. The rate constants decreased with increased pH, and the speciation of Fe(VI) and C₂H₅SH during the reaction were further discussed. C₂H₅SH was finally oxidized to nonvolatile and odorless sulfonic acid (C₂H₅SO₃H) with the intermediates of sulfinic acid (C₂H₅SO₂H) and disulphide (C₂H₅SSC₂H₅). A plausible mechanism involving two competing reactions for C₂H₅S^[rad] radicals was proposed to explain the pH-dependent reaction order. In addition, kinetics and products of C₂H₅SH degradation by Fe(VI) were compared with other oxidants (O₃, chlorine, ClO₂, KMnO₄, H₂O₂, and ^[rad]OH). Our results provided a deep understanding of C₂H₅SH degradation by Fe(VI) in aqueous alkaline solution.

Original language	English
Pages (from-to)	1557-1564
Number of pages	8
Journal	Chemical Engineering Journal
Volume	361
DOIs	https://doi.org/10.1016/j.cej.2018.11.005
State	Published - 1 Apr 2019

Keywords

Diethyl disulfide
Ethanethiol
Ferrate(VI)
Kinetics
Stoichiometry

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10.1016/j.cej.2018.11.005

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@article{d35a4058d59846c69e3a6297986b5f7c,

title = "Oxidation of ethanethiol in aqueous alkaline solution by ferrate(VI): Kinetics, stoichiometry and mechanism",

abstract = "The oxidation of ethanethiol (C2H5SH), as a representative odorous pollutant, by ferrate (Fe(VI)) in aqueous alkaline solution was investigated to understand its kinetics, stoichiometry, and reaction pathways. The reaction kinetics and fraction of different intermediates were found highly dependent on pH. The reaction behaved as a 5/2-order reaction in a pH range of 8.0–10.0, and a second-order reaction in a pH range of 10.5–12.0. The rate constants decreased with increased pH, and the speciation of Fe(VI) and C2H5SH during the reaction were further discussed. C2H5SH was finally oxidized to nonvolatile and odorless sulfonic acid (C2H5SO3H) with the intermediates of sulfinic acid (C2H5SO2H) and disulphide (C2H5SSC2H5). A plausible mechanism involving two competing reactions for C2H5S[rad] radicals was proposed to explain the pH-dependent reaction order. In addition, kinetics and products of C2H5SH degradation by Fe(VI) were compared with other oxidants (O3, chlorine, ClO2, KMnO4, H2O2, and [rad]OH). Our results provided a deep understanding of C2H5SH degradation by Fe(VI) in aqueous alkaline solution.",

keywords = "Diethyl disulfide, Ethanethiol, Ferrate(VI), Kinetics, Stoichiometry",

author = "Jing Wang and Tong Zheng and Chen Cai and Yanxiang Zhang and Huiling Liu",

note = "Publisher Copyright: {\textcopyright} 2018 Elsevier B.V.",

year = "2019",

month = apr,

day = "1",

doi = "10.1016/j.cej.2018.11.005",

language = "英语",

volume = "361",

pages = "1557--1564",

journal = "Chemical Engineering Journal",

issn = "1385-8947",

publisher = "Elsevier B.V.",

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TY - JOUR

T1 - Oxidation of ethanethiol in aqueous alkaline solution by ferrate(VI)

T2 - Kinetics, stoichiometry and mechanism

AU - Wang, Jing

AU - Zheng, Tong

AU - Cai, Chen

AU - Zhang, Yanxiang

AU - Liu, Huiling

PY - 2019/4/1

Y1 - 2019/4/1

N2 - The oxidation of ethanethiol (C2H5SH), as a representative odorous pollutant, by ferrate (Fe(VI)) in aqueous alkaline solution was investigated to understand its kinetics, stoichiometry, and reaction pathways. The reaction kinetics and fraction of different intermediates were found highly dependent on pH. The reaction behaved as a 5/2-order reaction in a pH range of 8.0–10.0, and a second-order reaction in a pH range of 10.5–12.0. The rate constants decreased with increased pH, and the speciation of Fe(VI) and C2H5SH during the reaction were further discussed. C2H5SH was finally oxidized to nonvolatile and odorless sulfonic acid (C2H5SO3H) with the intermediates of sulfinic acid (C2H5SO2H) and disulphide (C2H5SSC2H5). A plausible mechanism involving two competing reactions for C2H5S[rad] radicals was proposed to explain the pH-dependent reaction order. In addition, kinetics and products of C2H5SH degradation by Fe(VI) were compared with other oxidants (O3, chlorine, ClO2, KMnO4, H2O2, and [rad]OH). Our results provided a deep understanding of C2H5SH degradation by Fe(VI) in aqueous alkaline solution.

AB - The oxidation of ethanethiol (C2H5SH), as a representative odorous pollutant, by ferrate (Fe(VI)) in aqueous alkaline solution was investigated to understand its kinetics, stoichiometry, and reaction pathways. The reaction kinetics and fraction of different intermediates were found highly dependent on pH. The reaction behaved as a 5/2-order reaction in a pH range of 8.0–10.0, and a second-order reaction in a pH range of 10.5–12.0. The rate constants decreased with increased pH, and the speciation of Fe(VI) and C2H5SH during the reaction were further discussed. C2H5SH was finally oxidized to nonvolatile and odorless sulfonic acid (C2H5SO3H) with the intermediates of sulfinic acid (C2H5SO2H) and disulphide (C2H5SSC2H5). A plausible mechanism involving two competing reactions for C2H5S[rad] radicals was proposed to explain the pH-dependent reaction order. In addition, kinetics and products of C2H5SH degradation by Fe(VI) were compared with other oxidants (O3, chlorine, ClO2, KMnO4, H2O2, and [rad]OH). Our results provided a deep understanding of C2H5SH degradation by Fe(VI) in aqueous alkaline solution.

KW - Diethyl disulfide

KW - Ethanethiol

KW - Ferrate(VI)

KW - Kinetics

KW - Stoichiometry

UR - https://www.scopus.com/pages/publications/85056822139

U2 - 10.1016/j.cej.2018.11.005

DO - 10.1016/j.cej.2018.11.005

M3 - 文章

AN - SCOPUS:85056822139

SN - 1385-8947

VL - 361

SP - 1557

EP - 1564

JO - Chemical Engineering Journal

JF - Chemical Engineering Journal

ER -

Oxidation of ethanethiol in aqueous alkaline solution by ferrate(VI): Kinetics, stoichiometry and mechanism

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