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Low-temperature heat capacity of diopside glass (CaMgSi2O6): A calorimetric test of the configurational-entropy theory applied to the viscosity of liquid silicates

Geochimica et Cosmochimica Acta

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Abstract

Heat-capacity measurements have been made between 8 and 370 K on an annealed and a rapidly quenched diopside glass. Between 15 and 200 K, Cp does not depend significantly on the thermal history of the glass. Below 15 K Cp is larger for the quenched than for the annealed specimen. The opposite is true above 200 K as a result of what is interpreted as a secondary relaxation around room temperature. The magnitude of these effects, however, is small enough that the relative entropies S(298)-S(0) of the glasses differ by only 0.5 J/mol K, i.e., a figure within the combined experimental uncertainties. The insensitivity of relative entropies to thermal history supports the assumption that the configurational heat capacity of the liquid may be taken as the heat capacity difference between the liquid and the glass (??Cp). Furthermore, this insensitivity allows calculation of the residual entropies at 0 K of diopside glasses as a function of the fictive temperature from the entropy of fusion of diopside and the heat capacities of the crystalline, glassy and liquid phases. For a glass with a fictive temperature of 1005 K, for example, this calorimetric residual entropy is 24.3 ?? 3 J/mol K, in agreement with the prediction made by RICHET (1984) from an analysis of the viscosity data with the configurational-entropy theory of relaxation processes of Adam and Gibbs (1965). In turn, all the viscosity measurements for liquid diopside, which span the range 0.5-4?? 1013 poise, can be quantitatively reproduced through this theory with the calorimetrically determined entropies and ??Cp data. Finally, the unclear significance of "activation energies" for structural interpretations of viscosity data is emphasized, and the importance of ??Cp and glass-transition temperature systematics for determining the composition and temperature dependences of the viscosity is pointed out. ?? 1986.

Additional Publication Details

Publication type:
Article
Publication Subtype:
Journal Article
Title:
Low-temperature heat capacity of diopside glass (CaMgSi2O6): A calorimetric test of the configurational-entropy theory applied to the viscosity of liquid silicates
Series title:
Geochimica et Cosmochimica Acta
Volume
50
Issue:
7
Year Published:
1986
Language:
English
Larger Work Type:
Article
Larger Work Subtype:
Journal Article
Larger Work Title:
Geochimica et Cosmochimica Acta
First page:
1521
Last page:
1533
Number of Pages:
13