Characterization of decamethylferrocene and ferrocene in ionic liquids : Argon and vacuum effect on their electrochemical propertiesce Torriero,AAJ 2014, Characterization of decamethylferrocene and ferrocene in ionic liquids : Argon and vacuum effect on their electrochemical propertiesce, Electrochimica Acta, vol. 137, pp. 235-244, doi: 10.1016/j.electacta.2014.06.005. Attached Files Name Description MIMEType Size Downloads Title Characterization of decamethylferrocene and ferrocene in ionic liquids : Argon and vacuum effect on their electrochemical propertiesce Author(s) Torriero,AAJ orcid.org/0000-0001-8616-365X Journal name Electrochimica Acta Volume number 137 Start page 235 End page 244 Total pages 10 Publisher Elsevier Ltd Place of publication Doetinchem, Netherlands Publication date 2014-08-10 ISSN 0013-4686 Keyword(s) argon Decamethylferrocene Ferrocene ionic liquids vacuum Summary The electrochemistry of decamethylferrocene (DmFc) has been studied in organic solvent systems and proven to be a superior internal reference redox standard to ferrocene (Fc). However, the electrochemical information on this redox couple in ionic liquids is still limited. Therefore, the voltammetric and amperometric behaviour of DmFc was investigated under argon and vacuum conditions in six different ionic liquids and compared to that of Fc under the same experimental conditions. Consequently, the concentration, the heterogeneous electron-transfer rate constant (k0), volatility, and diffusion coefficients (D) of Fc and Fc+, as well as the solubility, k 0, and D values for DmFc and DmFc+ were determined under argon and vacuum conditions by fitting the experimental chronoamperometric and voltammetric data with numerical and digital simulations. The rate of mass transport of ferrocene and decamethylferrocene was observed to decreases between 6-37% by changing the working atmosphere from argon to vacuum. The D Fc/DFc+ ratios are in the range 1.31-2.01 in the different ILs. Importantly, the DDmFc/DDmFc+ ratio is ≈ 1 in 1-methyl-3-butylimidazolium bis(trifluoromethylsulfonyl)amide, 1-methyl-1-butylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate, and 1-methyl-3-ethylimidazolium tris(pentafluoroethyl)trifluorophosphate. The experimental mid-point potential and half-wave potential of Fc0/+ vs. DmFc0/+, as well as the formal potential obtained after correction for inequality in the respective diffusion coefficients of both redox processes are presented. Even though DmFc is not freely soluble in the different ILs, the results presented in this work suggest that the DmFc0/+ redox process is less dependent than Fc on the IL nature. This is a very relevant finding for the application of this transition-metal sandwich complex as an internal reference redox system in IL solutions. © 2014 Elsevier Ltd. Language eng DOI 10.1016/j.electacta.2014.06.005 Field of Research 030604 Electrochemistry Socio Economic Objective 970103 Expanding Knowledge in the Chemical Sciences HERDC Research category C1 Refereed article in a scholarly journal ERA Research output type C Journal article Copyright notice ©2014, Elsevier Persistent URL http://hdl.handle.net/10536/DRO/DU:30067689 Document type: Journal Article Collection: School of Life and Environmental Sciences Related Links Link Description Connect to Elements publication management system Go to link with your DU access privileges   Connect to published version Go to link with your DU access privileges     Unless expressly stated otherwise, the copyright for items in DRO is owned by the author, with all rights reserved. Versions Version Filter Type Mon, 24 Nov 2014, 15:45:01 EST Mon, 24 Nov 2014, 15:45:55 EST Tue, 25 Nov 2014, 04:00:59 EST Tue, 25 Nov 2014, 11:11:59 EST Mon, 23 Mar 2015, 10:52:45 EST Thu, 09 Apr 2015, 06:05:41 EST Thu, 09 Apr 2015, 09:35:00 EST Thu, 09 Apr 2015, 09:38:59 EST Thu, 09 Apr 2015, 09:40:46 EST Filtered Full Citation counts:   Cited 0 times in TR Web of Science Cited 12 times in Scopus Search Google Scholar Access Statistics: 226 Abstract Views, 2 File Downloads  -  Detailed Statistics Created: Mon, 24 Nov 2014, 15:45:55 EST

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