Ion-pairing effects on viscosity/conductance relations in Raman-characterized polymer electrolytes: LiClO4 and NaCF3SO3 in PPG(4000)

M. G. McLin, Charles Angell

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Abstract

Precise measurements of viscosity and conductivity have been made of the solutions of sodium triflate and lithium perchlorate in poly(propylene oxide) of MW 4000 (PPG(4000)) studied spectroscopically by Torell and co-workers for the extent of ion association. Viscosity, but not conductivity, data conform very well to the VTF equation and yield ideal glass transition temperatures that track the measured glass transition temperatures as closely as in the case of glass-forming aqueous solutions. The differences in temperature dependences of the two processes are demonstrated by using Walden rule plots. Using the data of Torell et al. at ambient temperature as a calibration point, we show that the deviations of conductivity from viscosity-dictated behavior predict almost quantitatively the strong temperature dependence of the free ion concentration found by Torell et al. up to the high temperature limit of their measurements.

Original languageEnglish (US)
Pages (from-to)9464-9469
Number of pages6
JournalJournal of Physical Chemistry
Volume95
Issue number23
StatePublished - 1991

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Electrolytes
Polymers
electrolytes
Viscosity
Ions
viscosity
conductivity
glass transition temperature
polymers
lithium perchlorates
temperature dependence
ions
propylene oxide
perchlorates
ion concentration
polypropylene
Polypropylene oxides
Temperature
ambient temperature
plots

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

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abstract = "Precise measurements of viscosity and conductivity have been made of the solutions of sodium triflate and lithium perchlorate in poly(propylene oxide) of MW 4000 (PPG(4000)) studied spectroscopically by Torell and co-workers for the extent of ion association. Viscosity, but not conductivity, data conform very well to the VTF equation and yield ideal glass transition temperatures that track the measured glass transition temperatures as closely as in the case of glass-forming aqueous solutions. The differences in temperature dependences of the two processes are demonstrated by using Walden rule plots. Using the data of Torell et al. at ambient temperature as a calibration point, we show that the deviations of conductivity from viscosity-dictated behavior predict almost quantitatively the strong temperature dependence of the free ion concentration found by Torell et al. up to the high temperature limit of their measurements.",
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AU - McLin, M. G.

AU - Angell, Charles

PY - 1991

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AB - Precise measurements of viscosity and conductivity have been made of the solutions of sodium triflate and lithium perchlorate in poly(propylene oxide) of MW 4000 (PPG(4000)) studied spectroscopically by Torell and co-workers for the extent of ion association. Viscosity, but not conductivity, data conform very well to the VTF equation and yield ideal glass transition temperatures that track the measured glass transition temperatures as closely as in the case of glass-forming aqueous solutions. The differences in temperature dependences of the two processes are demonstrated by using Walden rule plots. Using the data of Torell et al. at ambient temperature as a calibration point, we show that the deviations of conductivity from viscosity-dictated behavior predict almost quantitatively the strong temperature dependence of the free ion concentration found by Torell et al. up to the high temperature limit of their measurements.

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