Calorimetric and photoacoustic investigation of KNO3 phase transitions

Publisher Website
Google Scholar
Abstract
Results of a thermodynamic study of the phase transitions of powdered KNO3 at two impurity concentrations (99.999% pure and 99.9% pure) are reported. Transition onset and peak temperatures have been measured between 350 and 420 K using both heat flow and photoacoustic calorimetry. The transition temperatures and characteristics observed with both techniques show excellent agreement. Specific‐heat values calculated from scanning and stepped temperature heat‐flow data, utilizing both positive and negative temperature increments, compare well with previously reported values. Enthalpies for the II‐I, I‐III, and III‐II phase transitions were measured as 5.065, 2.603, and 2.084 kJ/mol, respectively, for 99.999% pure KNO3 powder using heat‐flow calorimetry. The transition enthalpies and temperatures measured for 99.9% pure powder were slightly lower for all three transitions. Entropy changes for the II‐I, I‐III, and III‐II transitions were 12.53, 6.61, and 5.30 J/mol K, respectively. Enthalpy, entropy, and Gibbs free‐energy curves are presented with emphasis on the temperature range over which the ferroelectric phase transition occurs. The experimental data and calculated thermodynamic functions indicate that the ferroelectric phase III in bulk KNO3 is a metastable state at atmospheric pressure, which was not observed to exist below 350 K contrary to previous reports.