期刊
JOURNAL OF MOLECULAR LIQUIDS
卷 352, 期 -, 页码 -出版社
ELSEVIER
DOI: 10.1016/j.molliq.2022.118607
关键词
Ionic Liquid; Phosphonium; Viscosity; Conductivity; Walden Plot
资金
- US Department of Energy through the Critical Materials Institute [DE AC07 05ID14517]
This study measured and calculated the properties of two phosphonium ionic liquids and compared them with piperidinium-based ionic liquids. The results showed slight differences in properties between wet and dried states, and the ionicity of phosphonium ionic liquids increased with dilution in propylene carbonate.
The viscosity, conductivity, electrochemical window and related thermodynamic properties such as excess volume and dynamic viscosity deviation of two phosphonium ionic liquids were measured and calculated for as-supplied and dried neat liquids and also v/v mixtures of 99/1, 95/5, 90/10, 75/25, and 50/50 of the ionic liquids with propylene carbonate (PC). Tetradecyltrihexylphosphonium dicyanamide ([P-6,P-6,P-6,P-14](+)dicyanamide), Cyphos 105, and tetradecyltrihexylphosphonium bis(trifluororomethane sulfonyl)imide (called bistriflimide) ([P-6,P-6,P-6,P-14](+)bistriflimide), Cyphos 109, ionic liquids were studied. Generally speaking, there were slight differences in the measured properties of the wet and dried IL solutions which were reflected in differences if the calculated properties. The measured and calculated properties were compared with those collected and derived from a piperidinium-based ionic liquid, methylpropyl piperidinium bistriflimide. Arrhenius plots for both the viscosity and conductivity were linear, with the linearity of the Litovitz plots being slightly higher. The viscosity and conductivity of the phosphonium solutions yielded Walden Plots that differed from Walden plots of piperidinium solutions and other ionic liquid solutions. For the phosphonium based ionic liquids, the ionicity was found to increase with increasing dilution in propylene carbonate. The electrochemical windows of the ionic liquids were determined as a function of the concentration of the ionic liquid present in the solution. The size of the window generally initially decreased and then increased with the addition of PC for the [P-6,P-6,P-6,P-14](+)dicyanamide ionic liquid increasing from 3.4 V in the 95/5 v/v (volume Cyphos 105) to volume of PC solvent) to 3.7 in the 50/50 dried IL case. The electrochemical windows of the dried liquids were slightly larger 3.5 V for the 95/5 v/v and 4.2 V for the 50/50 v/v Cyphos 105/PC solutions. The electrochemical window was larger and the conductivity was higher for the piperidinium IL solutions, but since the ionicity increases with dilution, the phosphonium based IL solutions may prove favorable for processes such as electrochemical reduction. (C) 2022 Elsevier B.V. All rights reserved.
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