Phase equilibria, electrical conductance, and density in the glass-forming system zinc chloride + pyridinium chloride. A detailed low-temperature analog of the silicon dioxide + sodium oxide system

A. J. Easteal, Charles Angell

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Abstract

In a study of ZnCl2-based binary chloride melts which may serve as analogs of the well known and technologically important glass-forming binary systems based on SiO2 and BeF2 as first component, a detailed phase-equilibrium, electrical conductance, and density study of the system zinc chloride + pyridinium chloride has been carried out. In contrast to the better known zinc chloride + alkali halide systems, this present system reproduces in great detail the phase relations and physicochemical behavior of the classic Na2O + SiO2 system, though at temperatures reduced by a factor of about 1/3. Electrical conductance data have been analyzed in terms of the three parameter equation κ = AT-1/2 exp B/(T -T0), and the "ideal" glass transition temperature T0 found to closely parallel the experimentally measured glass transition temperature Tg. T0 and Tg show complex composition dependences. A minimum at 33.3 mol % ZnCl2 is interpreted in terms of formation of the orthochlorozincate ion ZnCl4 2-, an approximately linear increase from 33.3 to 66 mol % is probably due to the formation of polymeric chains based on linked ZnCLi tetrahedra, and a plateau region at ZnCl2-rich compositions (65-90 mol %) is associated with the tendency to, or occurrence of, subliquidus liquid-liquid phase separation. The classical concept of "network-breaking" satisfactorily explains dramatic changes in conductivity in the region 90-100 mol % ZnCl2. There is some suggestion that the rapid decrease in "activation energy" for transport in this region may be associated primarily with changes in equilibrium thermodynamic properties (configurational heat capacity) rather than with changes in a purely kinetic energy barrier as is generally assumed.

Original languageEnglish (US)
Pages (from-to)3987-3999
Number of pages13
JournalThe Journal of Physical Chemistry
Volume74
Issue number22
StatePublished - 1970
Externally publishedYes

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zinc chlorides
Zinc chloride
Silicon Dioxide
Phase equilibria
glass transition temperature
Chlorides
chlorides
Silica
Sodium
sodium
analogs
silicon dioxide
Glass
Alkali halides
Oxides
oxides
glass
Energy barriers
Liquids
alkali halides

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

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title = "Phase equilibria, electrical conductance, and density in the glass-forming system zinc chloride + pyridinium chloride. A detailed low-temperature analog of the silicon dioxide + sodium oxide system",
abstract = "In a study of ZnCl2-based binary chloride melts which may serve as analogs of the well known and technologically important glass-forming binary systems based on SiO2 and BeF2 as first component, a detailed phase-equilibrium, electrical conductance, and density study of the system zinc chloride + pyridinium chloride has been carried out. In contrast to the better known zinc chloride + alkali halide systems, this present system reproduces in great detail the phase relations and physicochemical behavior of the classic Na2O + SiO2 system, though at temperatures reduced by a factor of about 1/3. Electrical conductance data have been analyzed in terms of the three parameter equation κ = AT-1/2 exp B/(T -T0), and the {"}ideal{"} glass transition temperature T0 found to closely parallel the experimentally measured glass transition temperature Tg. T0 and Tg show complex composition dependences. A minimum at 33.3 mol {\%} ZnCl2 is interpreted in terms of formation of the orthochlorozincate ion ZnCl4 2-, an approximately linear increase from 33.3 to 66 mol {\%} is probably due to the formation of polymeric chains based on linked ZnCLi tetrahedra, and a plateau region at ZnCl2-rich compositions (65-90 mol {\%}) is associated with the tendency to, or occurrence of, subliquidus liquid-liquid phase separation. The classical concept of {"}network-breaking{"} satisfactorily explains dramatic changes in conductivity in the region 90-100 mol {\%} ZnCl2. There is some suggestion that the rapid decrease in {"}activation energy{"} for transport in this region may be associated primarily with changes in equilibrium thermodynamic properties (configurational heat capacity) rather than with changes in a purely kinetic energy barrier as is generally assumed.",
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T1 - Phase equilibria, electrical conductance, and density in the glass-forming system zinc chloride + pyridinium chloride. A detailed low-temperature analog of the silicon dioxide + sodium oxide system

AU - Easteal, A. J.

AU - Angell, Charles

PY - 1970

Y1 - 1970

N2 - In a study of ZnCl2-based binary chloride melts which may serve as analogs of the well known and technologically important glass-forming binary systems based on SiO2 and BeF2 as first component, a detailed phase-equilibrium, electrical conductance, and density study of the system zinc chloride + pyridinium chloride has been carried out. In contrast to the better known zinc chloride + alkali halide systems, this present system reproduces in great detail the phase relations and physicochemical behavior of the classic Na2O + SiO2 system, though at temperatures reduced by a factor of about 1/3. Electrical conductance data have been analyzed in terms of the three parameter equation κ = AT-1/2 exp B/(T -T0), and the "ideal" glass transition temperature T0 found to closely parallel the experimentally measured glass transition temperature Tg. T0 and Tg show complex composition dependences. A minimum at 33.3 mol % ZnCl2 is interpreted in terms of formation of the orthochlorozincate ion ZnCl4 2-, an approximately linear increase from 33.3 to 66 mol % is probably due to the formation of polymeric chains based on linked ZnCLi tetrahedra, and a plateau region at ZnCl2-rich compositions (65-90 mol %) is associated with the tendency to, or occurrence of, subliquidus liquid-liquid phase separation. The classical concept of "network-breaking" satisfactorily explains dramatic changes in conductivity in the region 90-100 mol % ZnCl2. There is some suggestion that the rapid decrease in "activation energy" for transport in this region may be associated primarily with changes in equilibrium thermodynamic properties (configurational heat capacity) rather than with changes in a purely kinetic energy barrier as is generally assumed.

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