用电动势法测定了AgGaGe3Se8化合物在Т≤500k时的热力学性质

M. Moroz, P. Demchenko, M. Prokhorenko, B. Rudyk, L. Soliak, O. Mysina, O. Pereviznyk, O. Reshetnyak
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引用次数: 0

摘要

利用电磁场法对GeSe-Se-Ga2Se3-AgGaGe3Se8-GeSe切片中Ag-Ga-Ge-Se体系的浓度空间进行了划分。Ag-Ga-Ge-Se体系的浓度空间包含GeSe2-Se-Ga2Se3-AgGaGe3Se8 (I)和gese2 - gee2 - Ga2Se3 - AgGaGe3Se8 (II)四个相区,用这些相区相对于银点的空间位置表示合成AgGaGe3Se8化合物的整体细胞反应方程:2Ag + 6GeSe2 + Ga2Se3 + Se = 2AgGaGe3Se8和2Ag + 7GeSe2 + Ga2Se3 = GeSe + 2AgGaGe3Se8。在以下电化学电池(ECCs)的正极上进行反应:(−)С | Ag | SЕ | R(Ag+) | PЕ | С(+),其中C为石墨,Ag为左(负)电极,SE为纯Ag+离子导电固体电解质(ag3ges3br -玻璃),PE为右(正)电极,R(Ag+)为PE与SE接触的区域。由于热力学原因,从左电极转移到R(Ag+)区,Ag+离子作为小成核中心,在热力学稳定的混合物中重建亚稳化合物混合物。利用电动势与ECCs温度的线性关系计算AgGaGe3Se8平衡在(I)和(II)区域的标准热力学性质:∆_f G_(I))^〇= -(575,0±8,9)kJ·mol - 1,∆_f H_(I))^〇= -(577,7±12,0)kJ·mol - 1,∆_f H_(I))^〇=(515,9±14,1)J·(mol·K) - 1,∆_f G_(I))^〇= -(588,4±9,4)kJ·mol - 1,∆_f H_(II))^〇= -(590,6±12,9)kJ·mol - 1, S_(II))^〇=(507,8±13,2)J·(mol·K) - 1。计算值∆_f G_((I))^〇与∆_f G_((II))^〇在~2.3%范围内的相对差值以及不确定区间的重叠表征了公式组成化合物组合的四相部分(I)和(II)。此外,还计算了AgGaGe3Se8化合物的电位决定组分Ag的部分热力学函数值。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
THERMODYNAMIC PROPERTIES OF THE AgGaGe3Se8 COMPOUND AT Т≤500 K DETERMINED BY THE EMF METHOD
The division of the concentration space of the Ag–Ga–Ge–Se system in the GeSe–Se–Ga2Se3–AgGaGe3Se8–GeSe section was carried out by the EMF method. The concentration space of the Ag–Ga–Ge–Se system contains the four-phase regions GeSe2–Se–Ga2Se3–AgGaGe3Se8 (I) and GeSe–GeSe2–Ga2Se3–AgGaGe3Se8 (II). The spatial positions of these phase regions vs the point of silver were used to express equations of the overall cell reactions of synthesis of the AgGaGe3Se8 compound: 2Ag + 6GeSe2 + Ga2Se3 + Se = 2AgGaGe3Se8 and 2Ag + 7GeSe2 + Ga2Se3 = GeSe + 2AgGaGe3Se8. Reactions were performed in the positive electrodes of the following electrochemical cells (ECCs): (−) С | Ag | SЕ | R(Ag+) | PЕ | С (+), where C is graphite, Ag is the left (negative) electrode, SE is the purely Ag+ ion conducting solid electrolyte (Ag3GeS3Br-glass), PE is the right (positive) electrode, and R(Ag+) is the region of PE that contact with SE. Shifted from the left electrode to the R(Ag+) region for thermodynamic reasons Ag+ ions acted as the small nucleation centers for reconstruction of the metastable mixtures of compounds in the thermodynamically stable mixture of phases. Linear dependences of EMF vs temperature of ECCs were used to calculate the standard thermodynamic properties of the AgGaGe3Se8 equilibrium in the regions (I) and (II): ∆_f G_((I))^○= –(575,0 ± 8,9) kJ·mol −1, ∆_f H_((I))^○= –(574,7 ± 12,0) kJ·mol−1, S_((I))^○ = (515,9 ± 14,1) J·(mol·K)−1 and ∆_f G_((II))^○ = –(588,4 ± 9,4) kJ·mol−1, ∆_f H_((II))^○ = –(590,6 ± 12,9) kJ·mol−1, S_((II))^○ = (507,8 ± 13,2) J·(mol·K)−1, respectively. The relative difference between the calculated values ∆_f G_((I))^○ and ∆_f G_((II))^○ within ~2.3% and the overlap of the uncertainty intervals characterize the four-phase sections (I) and (II) by the combination of compounds of the formula composition. Moreover, values of the partial thermodynamic functions of the potential-determining component (Ag) of the AgGaGe3Se8 compound were calculated.
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