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Phase behaviour and conductivity study of electrolytes in supercritical hydrofluorocarbons

Phase behaviour and conductivity study of electrolytes in supercritical hydrofluorocarbons
Phase behaviour and conductivity study of electrolytes in supercritical hydrofluorocarbons
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 CH2FCF3 containing [NBun4][BF4], [NBun4][B{3,5-C6H3(CF3)2}4] and Na[B{3,5-C6H3(CF3)2}4] was studied and the conditions for forming a single supercritical phase established. Although all three HFCs are good solvents for [NBun4][BF4] the results show that the CH2F2 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 [NBun4][BF4] and [Cu(CH3CN)4][BF4] 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-C6H3(CF3)2}4], [NRfBun3][B{3,5-C6H3(CF3)2}4] (Rf = (CH2)3C7F15), and Na[B{3,5-C6H3(CF3)2}4] were carried out in scCH2F2. 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 scCH2F2
1463-9076
190-198
Bartlett, Philip N.
d99446db-a59d-4f89-96eb-f64b5d8bb075
Cook, David C.
0fca0ffb-eef4-422f-b513-ce9a1f7de7cc
George, Michael W.
09040935-b1da-4a63-ad2e-5ba29e39f80a
Ke, Jie
e4b531d4-7642-4367-9a4e-d06f126c2599
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Su, Wenta
78e12e98-09de-461d-8af3-91e5b0e018b7
Zhang, Wenjian
1f80ac5e-d4c2-4720-b19e-be700cd411e7
Bartlett, Philip N.
d99446db-a59d-4f89-96eb-f64b5d8bb075
Cook, David C.
0fca0ffb-eef4-422f-b513-ce9a1f7de7cc
George, Michael W.
09040935-b1da-4a63-ad2e-5ba29e39f80a
Ke, Jie
e4b531d4-7642-4367-9a4e-d06f126c2599
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Su, Wenta
78e12e98-09de-461d-8af3-91e5b0e018b7
Zhang, Wenjian
1f80ac5e-d4c2-4720-b19e-be700cd411e7

Bartlett, Philip N., Cook, David C., George, Michael W., Ke, Jie, Levason, William, Reid, Gillian, Su, Wenta and Zhang, Wenjian (2011) Phase behaviour and conductivity study of electrolytes in supercritical hydrofluorocarbons. Physical Chemistry Chemical Physics, 13 (1), 190-198. (doi:10.1039/c0cp01202e). (PMID:21072413)

Record type: Article

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 CH2FCF3 containing [NBun4][BF4], [NBun4][B{3,5-C6H3(CF3)2}4] and Na[B{3,5-C6H3(CF3)2}4] was studied and the conditions for forming a single supercritical phase established. Although all three HFCs are good solvents for [NBun4][BF4] the results show that the CH2F2 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 [NBun4][BF4] and [Cu(CH3CN)4][BF4] 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-C6H3(CF3)2}4], [NRfBun3][B{3,5-C6H3(CF3)2}4] (Rf = (CH2)3C7F15), and Na[B{3,5-C6H3(CF3)2}4] were carried out in scCH2F2. 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 scCH2F2

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Published date: January 2011

Identifiers

Local EPrints ID: 177659
URI: https://eprints.soton.ac.uk/id/eprint/177659
ISSN: 1463-9076
PURE UUID: adab1812-dab8-4c82-8e4c-c74b14f8b6cd
ORCID for Philip N. Bartlett: ORCID iD orcid.org/0000-0002-7300-6900
ORCID for William Levason: ORCID iD orcid.org/0000-0003-3540-0971
ORCID for Gillian Reid: ORCID iD orcid.org/0000-0001-5349-3468

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Date deposited: 18 Mar 2011 11:38
Last modified: 20 Jul 2019 01:28

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Contributors

Author: David C. Cook
Author: Michael W. George
Author: Jie Ke
Author: William Levason ORCID iD
Author: Gillian Reid ORCID iD
Author: Wenta Su
Author: Wenjian Zhang

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