Transport Properties of N-Butyl-N-methylpyrrolidinium Bis(trifluoromethylsulfonyl)amide

被引:99
作者
Harris, Kenneth R. [1 ]
Woolf, Lawrence A. [1 ]
Kanakubo, Mitsuhiro [2 ]
Ruether, Thomas [3 ]
机构
[1] Univ New S Wales, Sch Phys Environm & Math Sci, Univ Coll, Australian Def Force Acad, Canberra Bc, ACT 2610, Australia
[2] Natl Inst Adv Ind Sci & Technol, Miyagino Ku, Sendai, Miyagi 9838551, Japan
[3] Commonwealth Sci & Ind Res Org, Energy Technol, Clayton, Vic 3169, Australia
关键词
LIQUIDS 1-METHYL-3-OCTYLIMIDAZOLIUM HEXAFLUOROPHOSPHATE; VELOCITY CORRELATION-COEFFICIENTS; FRACTIONAL STOKES-EINSTEIN; SELF-DIFFUSION COEFFICIENT; TEMPERATURE IONIC LIQUIDS; PRESSURE-DEPENDENCE; PHYSICOCHEMICAL PROPERTIES; VOLUMETRIC PROPERTIES; DENSITY-DEPENDENCE; VISCOSITY;
D O I
10.1021/je2006049
中图分类号
O414.1 [热力学];
学科分类号
摘要
The viscosities (eta) and ion self-diffusion coefficients (D-i) of the ionic liquid N-butyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide ([PYr(14)][Tf2N] or [C(4)mpyr][Tf2N]) are reported between (0 and 90)degrees C and at pressures to 103 MPa and between (25 and 80)degrees C to 250 MPa, respectively. A falling-body high-pressure viscometer was employed, supplemented by a Stabinger rotating-cylinder viscometer for atmospheric pressure. Self-diffusion coefficients were measured by the steady-gradient spin-echo NMR technique. The overall uncertainties are +/- 2% and +/- 3%, respectively. Conductivities (0 and densities obtained between (0 and 90)degrees C at 0.1 MPa are reported. Ion self-diffusion coefficients and densities at 0.1 MPa are included for N-methyl-N-propyl-3-azabicyclo[3.2.2]nonaneium bis(trifluoromethylsulfonyl)amide ( [3-ABN(13)] [Tf2N]). The transport properties are examined using the fractional Stokes-Einstein and Nernst-Einstein relations, velocity correlation coefficients, and density scaling. For [Pyr(14)] [Tf2N], the fractional Stokes Einstein exponents are (0.93 +/- 0.05). There is very good consistency between the diffusion and molar conductivity (Lambda) data, with a slope of (0.99 +/- 0.05) for a plot of ln (T Lambda) against In(D++D-). The Nernst Einstein deviation parameter, Delta, is (0.313 +/- 0.013): it is consistent with the relationf f(+-) > (f(++) + f(-) )/2for the ion ion velocity cross-correlation coefficients, f(ii). Density scaling to the temperature-volume function (TV gamma) has been applied to both unreduced and reduced viscosities and self-diffusion coefficients for [Pyr(14)][Tf2N]. Consistent scaling parameters y are obtained for each of eta, D+, and D- with both the Casalini-Roland model and a simple polynomial fit in (TV gamma), and for the reduced quantities, (eta) over tilde, and (D) over tilde (+) and (D) over tilde (-) At a fixed temperature, the self-diffusion coefficients for the series [BMIM] [Tf2N], [PYr(14)] [Tf2N], and [3-ABN(13)] [Tf2N] decrease with increasing salt molar volume, but the ratio of D(cation) to D(anion) changes from values greater than unity to less than unity, in common with what is generally observed for ionic liquid families.
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收藏
页码:4672 / 4685
页数:14
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