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 ZnCl42-, 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 language||English (US)|
|Number of pages||13|
|Journal||The Journal of Physical Chemistry|
|State||Published - Dec 1 1970|
ASJC Scopus subject areas
- Physical and Theoretical Chemistry