Heat capacity and entropy of low structural state plagioclases

The heat capacity of 11 different compositions of the low structural state plagioclase binary was measured between 5 and 773 K. The results are compared to those obtained from synthetic high structural state samples investigated in a previous study and obtained from a heat-treated natural sample of this study. The heat capacity of anorthite samples with slightly different order parameters shows large differences at ~500 K, where the Ibar1-Pbar1 phase transition occurs, which affects petrological calculations. At T = 298.15 K, the vibrational entropy versus composition behaviour of the low structural state plagioclases is almost ideal, in contrast to the high structural state plagioclases with positive excess vibrational entropies. At higher temperatures, the low structural state plagioclases show a negative deviation from ideal vibrational entropy composition behaviour in the Na-rich region

Physical Chemistry Chemical Physics / Vibrational entropy of disorder in Cu3Au with different degrees of short-range order

L12 ordered Cu3Au and fcc-disordered samples with different degrees of short-range order were synthesised by annealing and/or quenching experiments. Low-temperature heat capacities were determined by relaxation calorimetry. From these data the vibrational entropy of disorder was derived. The calorimetric results show that the vibrational entropy does not depend on the degree of short-range order. The calorimetric investigations were complemented by density functional calculations with different functionals simulating various atomic configurations by super cells of different size. Using super cells containing 32 atoms, the computed entropies show only small variations with the change of short-range order in good agreement with the calorimetric results. Using, however, super cells with only 8 atoms, the results depend strongly on the chosen atomic configuration at variance with the calorimetric data. This result is important for investigating substances with larger molecules (e.g., silicate solid solutions) because such investigations are typically limited on super cells containing only a few sites on which substitution takes place.(VLID)283690

Heat capacity and entropy of low structural state plagioclases

The heat capacity of 11 different compositions of the low structural state plagioclase binary was measured between 5 and 773 K. The results are compared to those obtained from synthetic high structural state samples investigated in a previous study and obtained from a heat-treated natural sample of this study. The heat capacity of anorthite samples with slightly different order parameters shows large differences at ~500 K, where the Ibar1-Pbar1 phase transition occurs, which affects petrological calculations. At T = 298.15 K, the vibrational entropy versus composition behaviour of the low structural state plagioclases is almost ideal, in contrast to the high structural state plagioclases with positive excess vibrational entropies. At higher temperatures, the low structural state plagioclases show a negative deviation from ideal vibrational entropy composition behaviour in the Na-rich region