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- W1990998876 abstract "We report on data for the concentration dependence of the static dielectric constant εS of solutions of tetra-n-butylammonium naphtylsulfonate (TBNAS) in toluene derived from measurements of the frequency-dependent complex permittivity. The system shows an upper consolute point at Tc=329 K and a mole fraction Xc=0.0235 of the salt. The measurements were performed along a slightly supercritical isotherm at 338.15 K at mole fractions 0.01⩽X⩽0.068. εS increases with increasing salt concentration. At the critical point εS=(3.1±0.05) compared with εS=2.35 for pure toluene. In the concentration range covered by the experiments, the effective dipole moments calculated from these data are of the order of μeff=5 D, which is distinctly lower than an estimate for the isolated molecule, μ0≅18 D. The difference is attributed to compensation effects due to preferred antiparallel ion pair orientations, as described by a Kirkwood–Fröhlich-type theory with correlation factors of gK<1. At the critical point we find gK≅0.05. Due to these orientational correlations, dipole–dipole interactions between ion pairs may provide a significantly smaller contribution to the free energy than predicted by theory. This may explain the good performance of theories that ignore dipole–dipole interactions between pairs." @default.
- W1990998876 created "2016-06-24" @default.
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- W1990998876 date "2001-03-22" @default.
- W1990998876 modified "2023-10-18" @default.
- W1990998876 title "Ion pair correlations near critical points of ionic fluids: Experimental investigation of the static permittivity" @default.
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- W1990998876 doi "https://doi.org/10.1063/1.1349093" @default.
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