Heat capacity and enthalpy of palladium: A critical analysis of experimental information

IF 1.9 3区 材料科学 Q4 CHEMISTRY, PHYSICAL
María L. Alí , Susana B. Ramos , A. Fernández Guillermet
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引用次数: 0

Abstract

A description of the thermodynamic properties of FCC Pd above room temperature was developed by Dinsdale (1991) by relying on the heat capacity (CP) measurements by Vollmer and Kohlhaas (1969). A subsequent assessment by Arblaster (1995) relied upon a combination of the enthalpy measurements by Cordfunke and Konings (1989) with the CP data reported by Miiller and Cezairliyan (1980). For temperatures in the range 400 K < T < 1200 K the CP values recommended by Dinsdale are smaller than those by Arblaster, with a maximum discrepancy of about 1.5 J/K.mol at 800 K. Later on, Milošević and Babić (2013) reported new CP data, which suggest that the discrepancy in the mentioned temperature range might be diminished. However, in the re-assessment reported by Arblaster (2018), the results by Milošević and Babić were not relied upon. Motivated by these various problems, exploratory Molecular Dynamics (MD) simulations of the thermal properties of FCC Pd were performed using the LAMMPS code and the Embedded Atom Model (EAM) interatomic potential developed by Sheng et al. (2011). The MD work predicted enthalpy values that are in reasonable agreement with the data of Milošević and Babić (2013). In view of this result, the full experimental database of CP and enthalpy measurements has been reanalyzed using a Maier-Kelley type thermodynamic model which accounts phenomenologically for the vibrational and electronic contributions to CP. Systematic discrepancies between the enthalpy measurements and the direct determinations of CP are reported. An expression representing what is considered as the best possible account of the reliable experimental information available is presented.

钯的热容量和焓:对实验信息的批判性分析
Dinsdale (1991 年)根据 Vollmer 和 Kohlhaas(1969 年)的热容量测量结果,对室温以上催化裂化钯的热力学性质进行了描述。Arblaster (1995 年)随后根据 Cordfunke 和 Konings(1989 年)的焓测量值以及 Miiller 和 Cezairliyan(1980 年)报告的 CP 数据进行了评估。对于 400 K < T < 1200 K 范围内的温度,Dinsdale 推荐的 CP 值小于 Arblaster 推荐的 CP 值,800 K 时的最大差异约为 1.5 J/K.mol。然而,在 Arblaster(2018 年)报告的重新评估中,并未依赖 Milošević 和 Babić 的结果。在这些问题的推动下,使用 LAMMPS 代码和 Sheng 等人(2011 年)开发的嵌入式原子模型 (EAM) 原子间势,对催化裂化钯的热特性进行了探索性分子动力学 (MD) 模拟。MD 工作预测的焓值与 Milošević 和 Babić(2013 年)的数据基本一致。考虑到这一结果,我们使用 Maier-Kelley 型热力学模型重新分析了完整的 CP 和焓测量实验数据库。报告了焓测量值与 CP 直接测定值之间的系统差异。报告中提出了一个表达式,该表达式被认为是对现有可靠实验信息的最佳解释。
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来源期刊
CiteScore
4.00
自引率
16.70%
发文量
94
审稿时长
2.5 months
期刊介绍: The design of industrial processes requires reliable thermodynamic data. CALPHAD (Computer Coupling of Phase Diagrams and Thermochemistry) aims to promote computational thermodynamics through development of models to represent thermodynamic properties for various phases which permit prediction of properties of multicomponent systems from those of binary and ternary subsystems, critical assessment of data and their incorporation into self-consistent databases, development of software to optimize and derive thermodynamic parameters and the development and use of databanks for calculations to improve understanding of various industrial and technological processes. This work is disseminated through the CALPHAD journal and its annual conference.
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