Insights into the Kinetics of Intermediate Formation during Electrochemical Oxidation of the Organic Model Pollutant Salicylic Acid in Chloride Electrolyte

Noëmi Ambauen , Jens Muff, Ngoc Lan Mai, Cynthia Halle, Thuat T. Thrin, Thomas Meyn

Publikation: Bidrag til tidsskriftTidsskriftartikelForskningpeer review

2 Citationer (Scopus)
3 Downloads (Pure)

Resumé

The present study investigated the kinetics and formation of hydroxylated and chlorinated intermediates during electrochemical oxidation of salicylic acid (SA). A chloride (NaCl) and sulfate (Na 2SO 4) electrolyte were used, along with two different anode materials, boron doped diamond (BDD) and platinum (Pt). Bulk electrolysis of SA confirmed the formation of both hydroxylated and chlorinated intermediates. In line with the density functional theory (DFT) calculations performed in this study, 2,5- and 2,3-dihydroxybenzoic acid, 3- and 5- chlorosalicylic acid and 3,5-dichlorosalicylic acid were the dominating products. In the presence of a chloride electrolyte, the formation of chlorinated intermediates was the predominant oxidation mechanism on both BDD and Pt anodes. In the absence of a chloride electrolyte, hydroxylated intermediates prevailed on the Pt anode and suggested the formation of sulfonated SA intermediates on the BDD anode. Furthermore, direct oxidation at the anode surface only played a subordinate role. First order kinetic models successfully described the degradation of SA and the formation of the observed intermediates. Rate constants provided by the model showed that chlorination of SA can take place at up to more than 60 times faster rates than hydroxylation. In conclusion, the formation of chlorinated intermediates during electrochemical oxidation of the organic model pollutant SA is confirmed and found to be dominant in chloride containing waters.

OriginalsprogEngelsk
Artikelnummer322
TidsskriftWater
Vol/bind11
Udgave nummer7
ISSN2073-4441
DOI
StatusUdgivet - 26 jun. 2019

Fingerprint

salicylic acid
Salicylic Acid
Electrochemical oxidation
pollutant
electrolyte
Electrolytes
electrolytes
Chlorides
chlorides
pollutants
chloride
oxidation
Anodes
Electrodes
kinetics
platinum
Diamond
Kinetics
Boron
Platinum

Citer dette

@article{670d59ccaa5146d397da8a06af15d538,
title = "Insights into the Kinetics of Intermediate Formation during Electrochemical Oxidation of the Organic Model Pollutant Salicylic Acid in Chloride Electrolyte",
abstract = "The present study investigated the kinetics and formation of hydroxylated and chlorinated intermediates during electrochemical oxidation of salicylic acid (SA). A chloride (NaCl) and sulfate (Na 2SO 4) electrolyte were used, along with two different anode materials, boron doped diamond (BDD) and platinum (Pt). Bulk electrolysis of SA confirmed the formation of both hydroxylated and chlorinated intermediates. In line with the density functional theory (DFT) calculations performed in this study, 2,5- and 2,3-dihydroxybenzoic acid, 3- and 5- chlorosalicylic acid and 3,5-dichlorosalicylic acid were the dominating products. In the presence of a chloride electrolyte, the formation of chlorinated intermediates was the predominant oxidation mechanism on both BDD and Pt anodes. In the absence of a chloride electrolyte, hydroxylated intermediates prevailed on the Pt anode and suggested the formation of sulfonated SA intermediates on the BDD anode. Furthermore, direct oxidation at the anode surface only played a subordinate role. First order kinetic models successfully described the degradation of SA and the formation of the observed intermediates. Rate constants provided by the model showed that chlorination of SA can take place at up to more than 60 times faster rates than hydroxylation. In conclusion, the formation of chlorinated intermediates during electrochemical oxidation of the organic model pollutant SA is confirmed and found to be dominant in chloride containing waters.",
keywords = "Boron doped diamond, Chlorinated intermediates, Density functional theory, Disinfection by-products, Electrochemical oxidation, Hydroxyl radicals, Organic pollutant, Salicylic acid",
author = "No{\"e}mi Ambauen and Jens Muff and {Lan Mai}, Ngoc and Cynthia Halle and Thrin, {Thuat T.} and Thomas Meyn",
year = "2019",
month = "6",
day = "26",
doi = "10.3390/w11071322",
language = "English",
volume = "11",
journal = "Water",
issn = "2073-4441",
publisher = "M D P I AG",
number = "7",

}

Insights into the Kinetics of Intermediate Formation during Electrochemical Oxidation of the Organic Model Pollutant Salicylic Acid in Chloride Electrolyte. / Ambauen , Noëmi; Muff, Jens; Lan Mai, Ngoc; Halle, Cynthia; Thrin, Thuat T.; Meyn, Thomas.

I: Water, Bind 11, Nr. 7, 322, 26.06.2019.

Publikation: Bidrag til tidsskriftTidsskriftartikelForskningpeer review

TY - JOUR

T1 - Insights into the Kinetics of Intermediate Formation during Electrochemical Oxidation of the Organic Model Pollutant Salicylic Acid in Chloride Electrolyte

AU - Ambauen , Noëmi

AU - Muff, Jens

AU - Lan Mai, Ngoc

AU - Halle, Cynthia

AU - Thrin, Thuat T.

AU - Meyn, Thomas

PY - 2019/6/26

Y1 - 2019/6/26

N2 - The present study investigated the kinetics and formation of hydroxylated and chlorinated intermediates during electrochemical oxidation of salicylic acid (SA). A chloride (NaCl) and sulfate (Na 2SO 4) electrolyte were used, along with two different anode materials, boron doped diamond (BDD) and platinum (Pt). Bulk electrolysis of SA confirmed the formation of both hydroxylated and chlorinated intermediates. In line with the density functional theory (DFT) calculations performed in this study, 2,5- and 2,3-dihydroxybenzoic acid, 3- and 5- chlorosalicylic acid and 3,5-dichlorosalicylic acid were the dominating products. In the presence of a chloride electrolyte, the formation of chlorinated intermediates was the predominant oxidation mechanism on both BDD and Pt anodes. In the absence of a chloride electrolyte, hydroxylated intermediates prevailed on the Pt anode and suggested the formation of sulfonated SA intermediates on the BDD anode. Furthermore, direct oxidation at the anode surface only played a subordinate role. First order kinetic models successfully described the degradation of SA and the formation of the observed intermediates. Rate constants provided by the model showed that chlorination of SA can take place at up to more than 60 times faster rates than hydroxylation. In conclusion, the formation of chlorinated intermediates during electrochemical oxidation of the organic model pollutant SA is confirmed and found to be dominant in chloride containing waters.

AB - The present study investigated the kinetics and formation of hydroxylated and chlorinated intermediates during electrochemical oxidation of salicylic acid (SA). A chloride (NaCl) and sulfate (Na 2SO 4) electrolyte were used, along with two different anode materials, boron doped diamond (BDD) and platinum (Pt). Bulk electrolysis of SA confirmed the formation of both hydroxylated and chlorinated intermediates. In line with the density functional theory (DFT) calculations performed in this study, 2,5- and 2,3-dihydroxybenzoic acid, 3- and 5- chlorosalicylic acid and 3,5-dichlorosalicylic acid were the dominating products. In the presence of a chloride electrolyte, the formation of chlorinated intermediates was the predominant oxidation mechanism on both BDD and Pt anodes. In the absence of a chloride electrolyte, hydroxylated intermediates prevailed on the Pt anode and suggested the formation of sulfonated SA intermediates on the BDD anode. Furthermore, direct oxidation at the anode surface only played a subordinate role. First order kinetic models successfully described the degradation of SA and the formation of the observed intermediates. Rate constants provided by the model showed that chlorination of SA can take place at up to more than 60 times faster rates than hydroxylation. In conclusion, the formation of chlorinated intermediates during electrochemical oxidation of the organic model pollutant SA is confirmed and found to be dominant in chloride containing waters.

KW - Boron doped diamond

KW - Chlorinated intermediates

KW - Density functional theory

KW - Disinfection by-products

KW - Electrochemical oxidation

KW - Hydroxyl radicals

KW - Organic pollutant

KW - Salicylic acid

UR - http://www.scopus.com/inward/record.url?scp=85068565179&partnerID=8YFLogxK

U2 - 10.3390/w11071322

DO - 10.3390/w11071322

M3 - Journal article

VL - 11

JO - Water

JF - Water

SN - 2073-4441

IS - 7

M1 - 322

ER -