Thermodynamic modeling of the Pb-S and Cu-Pb-S systems is presented. All available experimental data in these systems are collected, assessed and used to optimize the model parameters. For the liquid phase, a solution (Cu I , Pb II , S II ) is developed using the modified quasichemical model in pair approximation. Liquid copper, liquid lead metal, as well as matte phases are described using single solution with miscibility gaps. Earlier thermodynamic assessments available in the literature did not include all the data on the solubility of Cu and S in liquid Pb at low temperatures, < 750 °C (1023 K), which is important for lead fire refining. In the present study, these additional data points are used in the optimization. For the composition of lead in equilibrium with matte at temperatures > 900 °C (1123 K), a significant discrepancy among different sets of literature data and existing thermodynamic assessments is revealed. Preliminary experiments are performed with the goal to understand the nature of the problem and to develop the methodology based on high-temperature equilibration, rapid quenching and electron probe x-ray microanalysis. The results of this study help to select accurate literature results in the optimization of model parameters. The resulting database is applicable to calculate slag/matte/metal distribution of lead in copper smelting and converting, as well as for predictions in the lead smelting and fire refining.

中文翻译：

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铅精炼条件下 Pb-S 和 Cu-Pb-S 系统的热力学建模

介绍了 Pb-S 和 Cu-Pb-S 系统的热力学模型。这些系统中所有可用的实验数据都被收集、评估并用于优化模型参数。对于液相，使用修正的准化学模型在成对近似中开发溶液（Cu I 、Pb II 、S II ）。液态铜、液态铅金属以及哑光相使用具有混溶性间隙的单一溶液进行描述。文献中提供的早期热力学评估并未包括在低温下（< 750 °C (1023 K)）Cu 和 S 在液态 Pb 中的溶解度的所有数据，这对于铅火精炼很重要。在本研究中，这些额外的数据点用于优化。对于在温度 > 900 °C (1123 K) 下与哑光平衡的铅的成分，揭示了不同组文献数据和现有热力学评估之间的显着差异。进行初步实验的目的是了解问题的性质并开发基于高温平衡、快速淬火和电子探针 X 射线微量分析的方法。本研究的结果有助于在模型参数的优化中选择准确的文献结果。所得数据库适用于计算铜冶炼和转化过程中铅的熔渣/锍/金属分布，以及用于铅冶炼和火法精炼的预测。进行初步实验的目的是了解问题的性质并开发基于高温平衡、快速淬火和电子探针 X 射线微量分析的方法。本研究的结果有助于在模型参数的优化中选择准确的文献结果。所得数据库适用于计算铜冶炼和转化过程中铅的熔渣/锍/金属分布，以及用于铅冶炼和火法精炼的预测。进行初步实验的目的是了解问题的性质并开发基于高温平衡、快速淬火和电子探针 X 射线微量分析的方法。本研究的结果有助于在模型参数的优化中选择准确的文献结果。所得数据库适用于计算铜冶炼和转化过程中铅的熔渣/锍/金属分布，以及用于铅冶炼和火法精炼的预测。