Heat capacity equations for nonstoichiometric solids

The equations for heat capacity measured under isodynamical conditions (fixed activity of a single component) are derived for partly open systems exchanging one component with the surroundings while keeping the contents of all other components constant. Compared to conventional isobaric (and isoplet...

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Bibliographic Details
Published in:Journal of thermal analysis and calorimetry 2013-07, Vol.113 (1), p.239-245
Main Authors: Holba, P., Sedmidubský, D.
Format: Article
Language:English
Subjects:
Analytical Chemistry
Chemical thermodynamics
Chemistry
Chemistry and Materials Science
Constants
Deviation
Exact sciences and technology
General and physical chemistry
General. Theory
Heat capacity
Inorganic Chemistry
Mathematical analysis
Measurement Science and Instrumentation
Open systems
Physical Chemistry
Polymer Sciences
Saturation
Specific heat
Stoichiometry
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Summary:The equations for heat capacity measured under isodynamical conditions (fixed activity of a single component) are derived for partly open systems exchanging one component with the surroundings while keeping the contents of all other components constant. Compared to conventional isobaric (and isoplethal) heat capacity of a strictly stoichiometric phase, the isodynamical heat capacity of a nonstoichiometric phase is found to involve two additional terms—the saturation contribution due to incorporation (or release) of the free component and the contribution due to deviation from stoichiometry reflecting a different number of the involved phonon modes (due to different free component content) and in some cases a variation of free component incorporation mechanism.
ISSN:1388-6150
1588-2926
1572-8943
DOI:10.1007/s10973-012-2886-1