Phase behaviour and conductivity study of electrolytes in supercritical hydrofluorocarbons

Philip N. Bartlett; David C. Cook; Michael W. George; Jie Ke; William Levason; Gillian Reid; Wenta Su; Wenjian Zhang

doi:10.1039/c0cp01202e

Phase behaviour and conductivity study of electrolytes in supercritical hydrofluorocarbons

Philip N. Bartlett
, David C. Cook
, Michael W. George
, Jie Ke
, William Levason
, Gillian Reid
, Wenta Su
, Wenjian Zhang

Research output: Journal Publication › Article › peer-review

14 Citations (Scopus)

Abstract

The purpose of this work was to characterise supercritical hydrofluorocarbons (HFC) that can be used as solvents for electrodeposition. The phase behaviour of CHF₃, CH₂F₂, and CH ₂FCF₃ containing [NBuⁿ₄][BF ₄], [NBuⁿ₄][B{3,5-C₆H ₃(CF₃)₂}₄] and Na[B{3,5-C ₆H₃(CF₃)₂}₄] was studied and the conditions for forming a single supercritical phase established. Although all three HFCs are good solvents for [NBuⁿ ₄][BF₄] the results show that the CH₂F ₂ system has the lowest p_r for dissolving a given amount of [NBuⁿ₄][BF₄]. The solubility of Na[B{3,5-C₆H₃(CF₃)₂}₄] in CH₂F₂ was found to be unexpectedly high. Studies of the phase behaviour of CH₂F₂ containing [NBuⁿ ₄][BF₄] and [Cu(CH₃CN)₄][BF ₄] showed that the copper complex was unstable in the absence of CH₃CN. For CHF₃, [Cu(hfac)₂] was more soluble and more stable than [Cu(CH₃CN)₄][BF₄] and only increased the phase-separation pressure by a moderate amount. Studies of the conductivity of [NBuⁿ₄][B(C₆F₅) ₄], [NBuⁿ₄][B{3,5-C₆H ₃(CF₃)₂}₄], [NR_fBu ⁿ₃][B{3,5-C₆H₃(CF₃) ₂}₄] (R_f = (CH₂)₃C ₇F₁₅), and Na[B{3,5-C₆H₃(CF ₃)₂}₄] were carried out in scCH ₂F₂. The results show that these salts are more conducting than [NBuⁿ₄][BF₄] under the same conditions although the increase is much less significant than that reported in previous work in supercritical CO₂ + CH₃CN. Consequently, either [NBuⁿ₄][BF₄] or the corresponding BARF salts would be suitable background electrolytes for electrodeposition from scCH ₂F₂.

Original language	English
Pages (from-to)	190-198
Number of pages	9
Journal	Physical Chemistry Chemical Physics
Volume	13
Issue number	1
DOIs	https://doi.org/10.1039/c0cp01202e
Publication status	Published - 7 Jan 2011
Externally published	Yes

ASJC Scopus subject areas

General Physics and Astronomy
Physical and Theoretical Chemistry

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10.1039/c0cp01202e

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@article{29ecdb4c6d5340ba913b1e2413852117,

title = "Phase behaviour and conductivity study of electrolytes in supercritical hydrofluorocarbons",

abstract = "The purpose of this work was to characterise supercritical hydrofluorocarbons (HFC) that can be used as solvents for electrodeposition. The phase behaviour of CHF3, CH2F2, and CH 2FCF3 containing [NBun4][BF 4], [NBun4][B\{3,5-C6H 3(CF3)2\}4] and Na[B\{3,5-C 6H3(CF3)2\}4] was studied and the conditions for forming a single supercritical phase established. Although all three HFCs are good solvents for [NBun 4][BF4] the results show that the CH2F 2 system has the lowest pr for dissolving a given amount of [NBun4][BF4]. The solubility of Na[B\{3,5-C6H3(CF3)2\}4] in CH2F2 was found to be unexpectedly high. Studies of the phase behaviour of CH2F2 containing [NBun 4][BF4] and [Cu(CH3CN)4][BF 4] showed that the copper complex was unstable in the absence of CH3CN. For CHF3, [Cu(hfac)2] was more soluble and more stable than [Cu(CH3CN)4][BF4] and only increased the phase-separation pressure by a moderate amount. Studies of the conductivity of [NBun4][B(C6F5) 4], [NBun4][B\{3,5-C6H 3(CF3)2\}4], [NRfBu n3][B\{3,5-C6H3(CF3) 2\}4] (Rf = (CH2)3C 7F15), and Na[B\{3,5-C6H3(CF 3)2\}4] were carried out in scCH 2F2. The results show that these salts are more conducting than [NBun4][BF4] under the same conditions although the increase is much less significant than that reported in previous work in supercritical CO2 + CH3CN. Consequently, either [NBun4][BF4] or the corresponding BARF salts would be suitable background electrolytes for electrodeposition from scCH 2F2.",

author = "Bartlett, \{Philip N.\} and Cook, \{David C.\} and George, \{Michael W.\} and Jie Ke and William Levason and Gillian Reid and Wenta Su and Wenjian Zhang",

year = "2011",

month = jan,

day = "7",

doi = "10.1039/c0cp01202e",

language = "English",

volume = "13",

pages = "190--198",

journal = "Physical Chemistry Chemical Physics",

issn = "1463-9076",

publisher = "Royal Society of Chemistry",

number = "1",

}

TY - JOUR

T1 - Phase behaviour and conductivity study of electrolytes in supercritical hydrofluorocarbons

AU - Bartlett, Philip N.

AU - Cook, David C.

AU - George, Michael W.

AU - Ke, Jie

AU - Levason, William

AU - Reid, Gillian

AU - Su, Wenta

AU - Zhang, Wenjian

PY - 2011/1/7

Y1 - 2011/1/7

N2 - The purpose of this work was to characterise supercritical hydrofluorocarbons (HFC) that can be used as solvents for electrodeposition. The phase behaviour of CHF3, CH2F2, and CH 2FCF3 containing [NBun4][BF 4], [NBun4][B{3,5-C6H 3(CF3)2}4] and Na[B{3,5-C 6H3(CF3)2}4] was studied and the conditions for forming a single supercritical phase established. Although all three HFCs are good solvents for [NBun 4][BF4] the results show that the CH2F 2 system has the lowest pr for dissolving a given amount of [NBun4][BF4]. The solubility of Na[B{3,5-C6H3(CF3)2}4] in CH2F2 was found to be unexpectedly high. Studies of the phase behaviour of CH2F2 containing [NBun 4][BF4] and [Cu(CH3CN)4][BF 4] showed that the copper complex was unstable in the absence of CH3CN. For CHF3, [Cu(hfac)2] was more soluble and more stable than [Cu(CH3CN)4][BF4] and only increased the phase-separation pressure by a moderate amount. Studies of the conductivity of [NBun4][B(C6F5) 4], [NBun4][B{3,5-C6H 3(CF3)2}4], [NRfBu n3][B{3,5-C6H3(CF3) 2}4] (Rf = (CH2)3C 7F15), and Na[B{3,5-C6H3(CF 3)2}4] were carried out in scCH 2F2. The results show that these salts are more conducting than [NBun4][BF4] under the same conditions although the increase is much less significant than that reported in previous work in supercritical CO2 + CH3CN. Consequently, either [NBun4][BF4] or the corresponding BARF salts would be suitable background electrolytes for electrodeposition from scCH 2F2.

AB - The purpose of this work was to characterise supercritical hydrofluorocarbons (HFC) that can be used as solvents for electrodeposition. The phase behaviour of CHF3, CH2F2, and CH 2FCF3 containing [NBun4][BF 4], [NBun4][B{3,5-C6H 3(CF3)2}4] and Na[B{3,5-C 6H3(CF3)2}4] was studied and the conditions for forming a single supercritical phase established. Although all three HFCs are good solvents for [NBun 4][BF4] the results show that the CH2F 2 system has the lowest pr for dissolving a given amount of [NBun4][BF4]. The solubility of Na[B{3,5-C6H3(CF3)2}4] in CH2F2 was found to be unexpectedly high. Studies of the phase behaviour of CH2F2 containing [NBun 4][BF4] and [Cu(CH3CN)4][BF 4] showed that the copper complex was unstable in the absence of CH3CN. For CHF3, [Cu(hfac)2] was more soluble and more stable than [Cu(CH3CN)4][BF4] and only increased the phase-separation pressure by a moderate amount. Studies of the conductivity of [NBun4][B(C6F5) 4], [NBun4][B{3,5-C6H 3(CF3)2}4], [NRfBu n3][B{3,5-C6H3(CF3) 2}4] (Rf = (CH2)3C 7F15), and Na[B{3,5-C6H3(CF 3)2}4] were carried out in scCH 2F2. The results show that these salts are more conducting than [NBun4][BF4] under the same conditions although the increase is much less significant than that reported in previous work in supercritical CO2 + CH3CN. Consequently, either [NBun4][BF4] or the corresponding BARF salts would be suitable background electrolytes for electrodeposition from scCH 2F2.

UR - https://www.scopus.com/pages/publications/78650103704

U2 - 10.1039/c0cp01202e

DO - 10.1039/c0cp01202e

M3 - Article

C2 - 21072413

AN - SCOPUS:78650103704

SN - 1463-9076

VL - 13

SP - 190

EP - 198

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

IS - 1

ER -

Phase behaviour and conductivity study of electrolytes in supercritical hydrofluorocarbons

Abstract

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