Ag3PO4微晶表面热力学函数的温度及形貌效应

doi:10.7503/cjcu20150011

高等学校化学学报 ›› 2015, Vol. 36 ›› Issue (7): 1385.doi: 10.7503/cjcu20150011

Ag₃PO₄微晶表面热力学函数的温度及形貌效应

刘作娇¹, 范高超¹, 何良明², 刁开盛¹, 黄在银^1,^3,⁴(), 谭学才^1,^3,⁴

1. 广西民族大学化学化工学院, 南宁 530008
2. 理学院, 南宁 530008
3. 广西林产化学与工程重点实验室, 南宁 530008
4. 广西高校食品安全与药物分析化学重点实验室, 南宁 530008

收稿日期:2015-01-07 出版日期:2015-07-10 发布日期:2015-06-17
作者简介:联系人简介: 黄在银, 男, 教授, 主要从事物理化学和材料化学方面的研究. E-mail:hzy210@163.com
基金资助:
国家自然科学基金(批准号: 20963001, 21273050)、广西民族大学研究生教育创新计划项目(批准号: YCSW2012065, gxun-chx2013093)和广西高等学校高水平创新团队及卓越学者资助计划(批准号: 桂教人[2014]7)资助

Temperature and Morphology Effect on Surface Thermodynamic Functions of Ag₃PO₄ Microcrystals^†

LIU Zuojiao¹, FAN Gaochao¹, HE Liangming², DIAO Kaisheng¹, HUANG Zaiyin^1,^3,^4,^*(), TAN Xuecai^1,^3,⁴

1. College of Chemistry and Chemical Engineering,Nanning 530008, China 2. Faculty of Science,3. Key Laboratory of Forest Chemistry and Engineering,4. Guangxi Colleges and Universities Key Laboratory of Food Safety and Pharmaceutical Analytical Chemistry,Guangxi University for Nationalities, Nanning 530008, China
2. Faculty of Science,Nanning 530008, China3. Key Laboratory of Forest Chemistry and Engineering,4. Guangxi Colleges and Universities Key Laboratory of Food Safety and Pharmaceutical Analytical Chemistry,Guangxi University for Nationalities, Nanning 530008, China
3. Key Laboratory of Forest Chemistry and Engineering, Nanning 530008, China
4. Guangxi Colleges and Universities Key Laboratory of Food Safety and Pharmaceutical Analytical Chemistry,Guangxi University for Nationalities, Nanning 530008, China

Received:2015-01-07 Online:2015-07-10 Published:2015-06-17
Contact: HUANG Zaiyin E-mail:hzy210@163.com
Supported by:
† Supported by the Nationcal Natural Science Foundation of China(Nos.20963001, 21273050), the Graduate Education Innovation Program of Guangxi, China(No;YCSW2012065) and the High-level Innovation Team and Outstanding Scholar Project of Guangxi Higher Education Institutes, China

摘要/Abstract

摘要：

在室温下采用离子交换法制备了四足状、立方体状和十二面体状Ag₃PO₄微晶及Ag₃PO₄块体, 并进行了表征. 以Ag₃PO₄微/纳米和块体材料热力学性质的区别为基础, 结合化学热力学理论和热动力学基本原理, 导出摩尔表面热力学关系式. 在此基础上, 采用原位微量热技术获取Ag₃PO₄的化学反应动力学信息和表面热力学函数, 讨论了形貌和温度对表面热力学性质变化的影响. 结果表明, 四足状Ag₃PO₄的摩尔表面焓( $H m s$ )、摩尔表面Gibbs自由能( $G m s$ )和摩尔表面熵( $S m s$ )最大, 立方体状次之, 十二面体状最小; $H m s$ 和 $S m s$ 随温度的升高而增大, $G m s$ 则随温度的升高而减小.

关键词: Ag3PO4, 形貌效应, 微量热技术, 表面热力学

Abstract:

Different morphologies of Ag₃PO₄ microcrystals, such as dodecahedrons, cubes, and tetrapods, were synthesized by ion-exchange method at room temperature. Based on the essential difference between thermodynamic properties of nano and bulk Ag₃PO₄, the equations for acquiring molar surface thermodynamic functions of nano Ag₃PO₄ were derived via combining the basic theory of chemical thermodynamics with thermokinetic principle. According to the derived equations, molar surface thermodynamic properties such as molar surface Gibbs free energy, molar surface enthalpy and molar surface entropy of the prepared Ag₃PO₄ microcrystals were gained by in-situ microcalorimetry. Moreover, the temperature and morphology effect on these obtained surface thermodynamic functions were discussed. The results revealed that the surface thermodynamic functions of tetrapod Ag₃PO₄ were maximum, followed by cube and dodecahedron Ag₃PO₄. Along with the increase of the temperature, molar surface enthalpy and molar surface entropy increased, whereas molar surface Gibbs free energy decreased.

Key words: Ag3PO4, Morphology effect, Microcalorimetry, Surface thermodynamics

中图分类号:

TrendMD:

刘作娇, 范高超, 何良明, 刁开盛, 黄在银, 谭学才. Ag₃PO₄微晶表面热力学函数的温度及形貌效应. 高等学校化学学报, 2015, 36(7): 1385.

LIU Zuojiao, FAN Gaochao, HE Liangming, DIAO Kaisheng, HUANG Zaiyin, TAN Xuecai. Temperature and Morphology Effect on Surface Thermodynamic Functions of Ag₃PO₄ Microcrystals^†. Chem. J. Chinese Universities, 2015, 36(7): 1385.

图/表 3

Fig.1 SEM images of the prepared Ag3PO4 with morphologies of tetrapods(A), cubes(B) and dodecahedrons(C), respectively

Table 1 Logarithmic values of rate constants for Ag3PO4 reaction systems at different temperatures

T/K	lnk_{nano, tetrapods}	lnk_{nano, cubes}	lnk_{nano, dodecahedrons}	lnk_bulk
298.15	-5.629	-5.694	-5.730	-5.824
303.15	-5.580	-5.641	-5.674	-5.729
308.15	-5.517	-5.582	-5.615	-5.660
313.15	-5.463	-5.524	-5.558	-5.597
318.15	-5.421	-5.479	-5.501	-5.527

Fig.2 Curves of molar surface thermodynamic functions vs. temperature(A) Sms-T; (B) Hms-T; (A) Gms-T. a. Dodecahedrons; b. tetrapods; c. cubes.

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Ag₃PO₄微晶表面热力学函数的温度及形貌效应

Temperature and Morphology Effect on Surface Thermodynamic Functions of Ag₃PO₄ Microcrystals^†

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