Semi-quantitative determination of ion transfers at an interface between water and quaternary ammonium polybromide droplets through stochastic electrochemical analysis

Semi Lee, Sangeun Park, Kyung Mi Kim, Jinho Chang

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

In this article, we present stochastic electrochemical analyses for the semi-quantitative determination of ion transfers (ITs) at an interface between water and electrochemically generated quaternary ammonium polybromide (QBr2n+1) droplets (water|QBr2n+1) in QBr aqueous solutions containing different acids (HAs). The concentration of Br in QBr2n+1, CBr(QBr2n+1) is linearly proportional to CA(aq) with the proportionality constant, which was estimated from the difference between the two partition coefficients of H+ and A from water toward QBr2n+1, KH+ −KA , and the ratio of the mean activity coefficient of the aqueous over that of the QBr2n+1 phase, γ±,aq±,QBr2n+1 . CBr(QBr2n+1) also shows the linear function of CQ+(aq) with (γ±,aq±,QBr2n+1 )KQ+ as its proportionality constant. The stochastic chronoamperometric analyses of QBr2n+1 droplets during their particle-impacts on Pt UME in acidic solutions containing either N-methyl-N-ethyl pyrrolidinium bromide (MEPBr) or ethylpyridinium bromide (EPyBr) as model QBrs can provide indirect information about CBr(QBr2n+1), and we estimated the relative order to be KC+(Li+orNa+), KH+ , and KA : KC+(Li+orNa+)<KH+ <KA , where KHSO4 <KClO4 <KCl in KA and KNa+ <KLi+ in KC+ . Also, we found that Br-IT at water|QBr2n+1 is effectively limited by A-IT in the acidic solutions, and Cl is most significantly transferred to QBr2n+1, leading to the complete inhibition of Br-IT into QBr2n+1.

Original languageEnglish
Pages (from-to)454-463
Number of pages10
JournalElectrochimica Acta
Volume271
DOIs
StatePublished - 2018 May 1

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Ammonium Compounds
Ions
Water
Activity coefficients
Bromides
Hydrogen
Acids

Keywords

  • Ion transfer
  • Particle impact
  • Quaternary ammonium polybromide
  • Stochastic electrochemistry
  • Zn/Br redox flow battery

Cite this

@article{665b5d015efa462797a3eb18e07bb048,
title = "Semi-quantitative determination of ion transfers at an interface between water and quaternary ammonium polybromide droplets through stochastic electrochemical analysis",
abstract = "In this article, we present stochastic electrochemical analyses for the semi-quantitative determination of ion transfers (ITs) at an interface between water and electrochemically generated quaternary ammonium polybromide (QBr2n+1) droplets (water|QBr2n+1) in QBr aqueous solutions containing different acids (HAs). The concentration of Br− in QBr2n+1, CBr−(QBr2n+1) is linearly proportional to CA−(aq) with the proportionality constant, which was estimated from the difference between the two partition coefficients of H+ and A− from water toward QBr2n+1, KH+ −KA− , and the ratio of the mean activity coefficient of the aqueous over that of the QBr2n+1 phase, γ±,aq/γ±,QBr2n+1 . CBr−(QBr2n+1) also shows the linear function of CQ+(aq) with (γ±,aq/γ±,QBr2n+1 )KQ+ as its proportionality constant. The stochastic chronoamperometric analyses of QBr2n+1 droplets during their particle-impacts on Pt UME in acidic solutions containing either N-methyl-N-ethyl pyrrolidinium bromide (MEPBr) or ethylpyridinium bromide (EPyBr) as model QBrs can provide indirect information about CBr−(QBr2n+1), and we estimated the relative order to be KC+(Li+orNa+), KH+ , and KA− : KC+(Li+orNa+)<KH+ <KA− , where KHSO4 − <KClO4 − <KCl− in KA− and KNa+ <KLi+ in KC+ . Also, we found that Br−-IT at water|QBr2n+1 is effectively limited by A−-IT in the acidic solutions, and Cl− is most significantly transferred to QBr2n+1, leading to the complete inhibition of Br−-IT into QBr2n+1.",
keywords = "Ion transfer, Particle impact, Quaternary ammonium polybromide, Stochastic electrochemistry, Zn/Br redox flow battery",
author = "Semi Lee and Sangeun Park and Kim, {Kyung Mi} and Jinho Chang",
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Semi-quantitative determination of ion transfers at an interface between water and quaternary ammonium polybromide droplets through stochastic electrochemical analysis. / Lee, Semi; Park, Sangeun; Kim, Kyung Mi; Chang, Jinho.

In: Electrochimica Acta, Vol. 271, 01.05.2018, p. 454-463.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Semi-quantitative determination of ion transfers at an interface between water and quaternary ammonium polybromide droplets through stochastic electrochemical analysis

AU - Lee, Semi

AU - Park, Sangeun

AU - Kim, Kyung Mi

AU - Chang, Jinho

PY - 2018/5/1

Y1 - 2018/5/1

N2 - In this article, we present stochastic electrochemical analyses for the semi-quantitative determination of ion transfers (ITs) at an interface between water and electrochemically generated quaternary ammonium polybromide (QBr2n+1) droplets (water|QBr2n+1) in QBr aqueous solutions containing different acids (HAs). The concentration of Br− in QBr2n+1, CBr−(QBr2n+1) is linearly proportional to CA−(aq) with the proportionality constant, which was estimated from the difference between the two partition coefficients of H+ and A− from water toward QBr2n+1, KH+ −KA− , and the ratio of the mean activity coefficient of the aqueous over that of the QBr2n+1 phase, γ±,aq/γ±,QBr2n+1 . CBr−(QBr2n+1) also shows the linear function of CQ+(aq) with (γ±,aq/γ±,QBr2n+1 )KQ+ as its proportionality constant. The stochastic chronoamperometric analyses of QBr2n+1 droplets during their particle-impacts on Pt UME in acidic solutions containing either N-methyl-N-ethyl pyrrolidinium bromide (MEPBr) or ethylpyridinium bromide (EPyBr) as model QBrs can provide indirect information about CBr−(QBr2n+1), and we estimated the relative order to be KC+(Li+orNa+), KH+ , and KA− : KC+(Li+orNa+)<KH+ <KA− , where KHSO4 − <KClO4 − <KCl− in KA− and KNa+ <KLi+ in KC+ . Also, we found that Br−-IT at water|QBr2n+1 is effectively limited by A−-IT in the acidic solutions, and Cl− is most significantly transferred to QBr2n+1, leading to the complete inhibition of Br−-IT into QBr2n+1.

AB - In this article, we present stochastic electrochemical analyses for the semi-quantitative determination of ion transfers (ITs) at an interface between water and electrochemically generated quaternary ammonium polybromide (QBr2n+1) droplets (water|QBr2n+1) in QBr aqueous solutions containing different acids (HAs). The concentration of Br− in QBr2n+1, CBr−(QBr2n+1) is linearly proportional to CA−(aq) with the proportionality constant, which was estimated from the difference between the two partition coefficients of H+ and A− from water toward QBr2n+1, KH+ −KA− , and the ratio of the mean activity coefficient of the aqueous over that of the QBr2n+1 phase, γ±,aq/γ±,QBr2n+1 . CBr−(QBr2n+1) also shows the linear function of CQ+(aq) with (γ±,aq/γ±,QBr2n+1 )KQ+ as its proportionality constant. The stochastic chronoamperometric analyses of QBr2n+1 droplets during their particle-impacts on Pt UME in acidic solutions containing either N-methyl-N-ethyl pyrrolidinium bromide (MEPBr) or ethylpyridinium bromide (EPyBr) as model QBrs can provide indirect information about CBr−(QBr2n+1), and we estimated the relative order to be KC+(Li+orNa+), KH+ , and KA− : KC+(Li+orNa+)<KH+ <KA− , where KHSO4 − <KClO4 − <KCl− in KA− and KNa+ <KLi+ in KC+ . Also, we found that Br−-IT at water|QBr2n+1 is effectively limited by A−-IT in the acidic solutions, and Cl− is most significantly transferred to QBr2n+1, leading to the complete inhibition of Br−-IT into QBr2n+1.

KW - Ion transfer

KW - Particle impact

KW - Quaternary ammonium polybromide

KW - Stochastic electrochemistry

KW - Zn/Br redox flow battery

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DO - 10.1016/j.electacta.2018.03.162

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