基于溶解热力学原理对纳米卤化银热力学性质的研究

doi:10.7503/cjcu20180509

高等学校化学学报 ›› 2018, Vol. 39 ›› Issue (10): 2214.doi: 10.7503/cjcu20180509

基于溶解热力学原理对纳米卤化银热力学性质的研究

覃方红¹, 邱江源¹, 肖碧源¹, 米艳^1,²(), 黄在银^1,²()

1. 广西民族大学化学化工学院, 南宁 530006
2. 广西高校食品安全与药物分析化学重点实验室, 南宁 530006

收稿日期:2018-07-17 出版日期:2018-09-29 发布日期:2018-09-29
作者简介:
联系人简介: 黄在银, 男, 教授, 主要从事纳米物理化学方面的研究. E-mail: huangzaiyin@163.com;米艳, 女, 博士, 讲师, 主要从事纳米物理化学方面的研究. E-mail: miyan@gxun.edu.cn
基金资助:
国家自然科学基金(批准号: 21273050, 21573048, 21873022)和广西研究生教育创新计划项目(批准号: gxun-chxzs2018062)资助.

Investigation into the Thermodynamic Properties of Nano-silver Halides Based on the Principle of Dissolution Thermodynamics^†

QIN Fanghong¹, QIU Jiangyuan¹, XIAO Biyuan¹, MI Yan^1,^2,^*(), HUANG Zaiyin^1,^2,^*()

1. College of Chemistry and Chemical Engineering, Guangxi University for Nationalities, Nanning 530006, China
2. Guangxi Colleges and Universities Key Laboratory of Food Safety and Pharmaceutical Analytical Chemistry, Nanning 530006, China

Received:2018-07-17 Online:2018-09-29 Published:2018-09-29
Contact: MI Yan,HUANG Zaiyin E-mail:miyan@gxun.edu.cn;huangzaiyin@163.com
Supported by:
† Supported by the National Natural Science Foundation of China(Nos. 21273050, 21573048, 21873022) and the Innovation Project of Guangxi Graduate Education, China(No. gxun-chxzs2018062).

摘要/Abstract

摘要：

在室温下, 可控制备了系列纳米卤化银(AgX)材料, 并对其组成、形貌及结构进行了表征. 基于块体卤化银与纳米卤化银热力学性质的本质差异, 结合溶解热力学Debye-Hückel等基本理论公式, 通过与块体材料对比, 导出了纳米卤化银的表面热力学、偏摩尔表面热力学和规定热力学函数的关系式. 为测定难溶盐类纳米材料的表面热力学和规定热力学函数提供了行之有效的新方法.

关键词: 纳米卤化银, 溶解热力学法, 热力学函数, 温度效应

Abstract:

A series of nano-silver halide(AgX, X=Cl, Br, I) materials was prepared at room temperature. Their composition, morphology and structure were characterized. The surface thermodynamics, partial molar surface thermodynamics and specified thermodynamic functions of nano-silver halide were derived based on the essential difference between bulk-silver halide and nano-silver halide combined with Debye-Hückel formula of dissolution thermodynamics. A new effective and universal method for the determination of surface thermodynamics and thermodynamic function of insoluble salt nanomaterials is provided.

Key words: Nanometer silver halide, Dissolution thermodynamics method, Thermodynamic function, Temperature effect

中图分类号:

O645

TrendMD:

覃方红, 邱江源, 肖碧源, 米艳, 黄在银. 基于溶解热力学原理对纳米卤化银热力学性质的研究. 高等学校化学学报, 2018, 39(10): 2214.

QIN Fanghong,QIU Jiangyuan,XIAO Biyuan,MI Yan,HUANG Zaiyin. Investigation into the Thermodynamic Properties of Nano-silver Halides Based on the Principle of Dissolution Thermodynamics^†. Chem. J. Chinese Universities, 2018, 39(10): 2214.

图/表 11

Fig.1 SEM images of bulk-AgCl(A), bulk-AgBr(B) and bulk-AgI(C)

Fig.2 SEM images of nano-AgCl(A), nano-AgBr(B) and nano-AgI(C)

Fig.3 Particle size distribution histogram of nano-AgCl(A), nano-AgBr(B) and nano-AgI(C)

Fig.4 XRD patterns of nano-AgCl(A), nano-AgBr(B) and nano-AgI(C)

Table 1 Standard equilibrium constant of AgX

T/K	k_sp/(L·mol^-1)
T/K	Nano-AgCl	Bulk-AgCl	Nano-AgBr	Bulk-AgBr	Nano-AgI	Bulk-AgI
288.15	2.11×10^-9	7.33×10^-11	4.24×10^-11	5.71×10^-13	5.23×10^-15	7.42×10^-16
298.15	2.59×10^-9	7.89×10^-11	5.48×10^-11	8.46×10^-13	2.26×10^-14	2.32×10^-15
308.15	3.26×10^-9	1.49×10^-10	6.53×10^-11	1.81×10^-12	4.24×10^-14	6.10×10^-15
318.15	5.51×10^-9	2.94×10^-10	8.52×10^-11	2.11×10^-12	7.78×10^-14	1.29×10^-14
328.15	1.05×10^-8	4.72×10^-10	1.02×10^-10	4.01×10^-12	1.36×10^-13	2.36×10^-14

Table 2 Standard molar dissolved Gibbs free energy of AgX

T/K	Δ $G m 0 —$ /(kJ·mol^-1)
T/K	Nano-AgCl	Bulk-AgCl	Nano-AgBr	Bulk-AgBr	Nano-AgI	Bulk-AgI
288.15	53.46	56.41	55.21	67.53	72.13	83.45
298.15	54.71	57.17	57.31	68.93	72.37	83.52
308.15	55.96	58.15	59.72	70.36	72.95	83.85
318.15	56.34	58.27	61.33	71.12	73.75	84.65
328.15	56.82	58.59	62.76	71.59	74.58	85.28

Table 2 Standard molar dissolved Gibbs free energy of AgX

T/K	Δ $G m 0 —$ /(kJ·mol^-1)
T/K	Nano-AgCl	Bulk-AgCl	Nano-AgBr	Bulk-AgBr	Nano-AgI	Bulk-AgI
288.15	53.46	56.41	55.21	67.53	72.13	83.45
298.15	54.71	57.17	57.31	68.93	72.37	83.52
308.15	55.96	58.15	59.72	70.36	72.95	83.85
318.15	56.34	58.27	61.33	71.12	73.75	84.65
328.15	56.82	58.59	62.76	71.59	74.58	85.28

Fig.5 Standard molar dissolved Gibbs free energy of AgX vs. T

Table 3 Standard molar dissolved enthalpy and entropy of AgX

System	Δ $H m 0 —$ /(kJ·mol^-1)	Δ $S m 0 —$ /(J·mol^-1·K^-1)
Nano-AgCl	32.11	-75.52
Bulk-AgCl	39.89	-57.61
Nano-AgBr	3.43	-181.12
Bulk-AgBr	38.14	-103.10
Nano-AgI	51.48	-89.14
Bulk-AgI	67.19	-55.30

Table 3 Standard molar dissolved enthalpy and entropy of AgX

System	Δ $H m 0 —$ /(kJ·mol^-1)	Δ $S m 0 —$ /(J·mol^-1·K^-1)
Nano-AgCl	32.11	-75.52
Bulk-AgCl	39.89	-57.61
Nano-AgBr	3.43	-181.12
Bulk-AgBr	38.14	-103.10
Nano-AgI	51.48	-89.14
Bulk-AgI	67.19	-55.30

Table 4 Partial molar surface and molar surface Gibbs free energy of AgX

T/K	$G NP s$ /(kJ·mol^-1)			$G m s$ /(kJ·mol^-1)
T/K	Nano-AgCl	Nano-AgBr	Nano-AgI	Nano-AgCl	Nano-AgBr	Nano-AgI
288.15	2.95	12.32	11.32	4.43	18.48	16.98
298.15	2.46	11.62	11.15	3.69	17.43	16.73
308.15	2.19	10.64	10.90	3.28	15.96	16.35
318.15	1.93	9.79	10.90	2.90	14.69	16.35
328.15	1.77	8.83	10.70	2.66	13.24	16.05

Table 4 Partial molar surface and molar surface Gibbs free energy of AgX

T/K	$G NP s$ /(kJ·mol^-1)			$G m s$ /(kJ·mol^-1)
T/K	Nano-AgCl	Nano-AgBr	Nano-AgI	Nano-AgCl	Nano-AgBr	Nano-AgI
288.15	2.95	12.32	11.32	4.43	18.48	16.98
298.15	2.46	11.62	11.15	3.69	17.43	16.73
308.15	2.19	10.64	10.90	3.28	15.96	16.35
318.15	1.93	9.79	10.90	2.90	14.69	16.35
328.15	1.77	8.83	10.70	2.66	13.24	16.05

Table 5 Partial molar surface as well as molar surface enthalpy and entropy of nano-AgX

System	$H NP s$ /(kJ·mol^-1)	$H m s$ /(kJ·mol^-1)	$S NP s$ /(J·mol^-1·K^-1)	$S m s$ /(J·mol^-1·K^-1)
Nano-AgCl	7.78	11.66	17.09	25.64
Nano-AgBr	34.70	52.05	78.02	117.03
Nano-AgI	15.71	23.56	33.84	50.76

Table 5 Partial molar surface as well as molar surface enthalpy and entropy of nano-AgX

System	$H NP s$ /(kJ·mol^-1)	$H m s$ /(kJ·mol^-1)	$S NP s$ /(J·mol^-1·K^-1)	$S m s$ /(J·mol^-1·K^-1)
Nano-AgCl	7.78	11.66	17.09	25.64
Nano-AgBr	34.70	52.05	78.02	117.03
Nano-AgI	15.71	23.56	33.84	50.76

Table 6 Standard molar formation thermodynamic functions of AgX

System	Δ_f $H m 0 —$ /(kJ·mol^-1)	Δ_f $G m 0 —$ /(kJ·mol^-1)	$S m 0 —$ /(J·mol^-1·K^-1)
Bulk-AgCl	-127.01^[25]	-109.80	96.25
Nano-AgCl	-115.35	-105.38	121.88
Bulk-AgBr	-100.37^[25]	-96.90	107.11
Nano-AgBr	-48.32	-78.42	224.14
Bulk-AgI	-61.48^[25]	-66.19	115.50
Nano-AgI	-37.92	-49.21	64.74

Table 6 Standard molar formation thermodynamic functions of AgX

System	Δ_f $H m 0 —$ /(kJ·mol^-1)	Δ_f $G m 0 —$ /(kJ·mol^-1)	$S m 0 —$ /(J·mol^-1·K^-1)
Bulk-AgCl	-127.01^[25]	-109.80	96.25
Nano-AgCl	-115.35	-105.38	121.88
Bulk-AgBr	-100.37^[25]	-96.90	107.11
Nano-AgBr	-48.32	-78.42	224.14
Bulk-AgI	-61.48^[25]	-66.19	115.50
Nano-AgI	-37.92	-49.21	64.74

参考文献 25

[1]	Zayats A.V., Smolyaninov I. I., Maradudin A. A., Phys. Rep., 2005, 408(3), 131—314
[2]	Skomski R., J. Phys-Condens Mat., 2003, R841—R896
[3]	Polshettiwar V., Varma R.S., Green Chem., 2010, 12(5), 743—754
[4]	Wan T., Li X.X., Huang Z. Y., Qiu J. Y., Zuo C., Tan X. C., Chem. J. Chinese Universities, 2017, 38(12), 226—230
	(万婷, 李星星, 黄在银, 邱江源, 左晨, 谭学才. 高等学校化学学报, 2017, 38(12), 226—230)
[5]	Liu Z.J., Fan G. C., Li X. X., Tan X. C., Zhong L. Y., Huang Z. Y., Chem. J. Chinese Universities, 2015, 36(2), 212—214
	(刘作娇, 范高超, 李星星, 谭学才, 钟莲云, 黄在银. 高等学校化学学报, 2015, 36(2), 212—214)
[6]	Wagne R.F., Macedo L. J., Opdahl A., Anal. Chem., 2015, 87(15), 7825—7832
[7]	Bai L.C., Wang X., Chen Q., Ye Y. F., Zheng H. Q., Guo J. H., Yin Y. D., Gao C. B., Angew. Chem. Int. Ed., 2016, 55, 15656—15661
[8]	Tang H.F., Huang Z. Y., Xiao M., Acta Phys-Chim. Sin., 2016, 32(11), 2678—2684
	(汤焕丰, 黄在银, 肖明. 物理化学学报, 2016, 32(11), 2678—2684)
[9]	Xiao M., Huang Z.Y., Tang H. F., Lu S. T., Liu C., Acta Phys-Chim. Sin., 2017, 33(2), 399—406
	(肖明, 黄在银, 汤焕丰, 陆桑婷, 刘超. 物理化学学报, 2017, 33(2), 399—406)
[10]	Lai W.P., Xue Y. Q., Lian P., Ge Z. X., Wang B. Z., Zhang Z. Z., Acta Phys-Chim. Sin., 2007, 23(4), 508—512
	(来蔚鹏, 薛永强, 廉鹏, 葛忠学, 王伯周, 张志忠. 物理化学学报, 2007, 23(4), 508—512)
[11]	Alexandra N., Phys. Chem. Miner., 1977, 2(1/2), 89—104
[12]	Lai S.S., Mhaske S. T., Carbohydr. Polym., 2018, 291, 266—279
[13]	Tang H., Wang Y., Zhang D., Wu K., Huang H., J. Mater. Sci.:Mater. Electron., 2016, 27(7), 6955—6963
[14]	Najafi M., Javanmard S., Mohammad-Hosseinzadeh F., Int. J. Environ. Sci. Technol., 2015, 12(1), 87—104
[15]	Li J., Study on Syntheis of Silver Chloride Nanopaticles and Surface Modification, Jilin University,Changchun, 2007
	(李静. 氯化银纳米粒子的制备及其表面改性的研究, 长春: 吉林大学, 2007)
[16]	Xu Y., The Study on Syntheis of Silver Bromide Nanopaticles and Its Photocatalytic Acitivity, Jilin University,Changchun, 2011
	(徐瑶. 纳米溴化银的制备及其光催化性能的研究, 长春: 吉林大学, 2011)
[17]	Zhang J.H., Jin D. T., Liu X. L., Liang J. S., Li G. Y., Jiang Z. H., Journal of Jilin University(Engineering and Technology Edition), 2010, 40(1), 77—81
	(张景红, 金德镇, 刘先黎, 连建设, 李光玉, 江中浩. 吉林大学学报(工学版), 2010, 40(1), 77—81)
[18]	Li X.X., Huang Z. Y., Zhong L. Y., Wang T. H., Tan X. C., Chin. Sci. Bull., 2014, 59(25), 2490—2498
	(李星星, 黄在银, 钟莲云, 王腾辉, 谭学才. 科学通报, 2014, 59(25), 2490—2498)
[19]	Fan G.C., Ma Z., Huang Z. Y., J. Therm. Anal. Calorim., 2013, 116(1), 485—489
[20]	Tang H.F., Huang Z. Y., Xiao M., Liang M., Chen L. Y., Acta Phys-Chim. Sin., 2016, 32(12), 2891—2897
	(汤焕丰, 黄在银, 肖明, 梁敏, 陈栎莹. 物理化学学报, 2016, 32(12), 2891—2897)
[21]	Fu X.C., Shen W. X., Yao T. Y., Physical Chemistry(4th Edition), Higher Education Press, Beijing, 1990
	(傅献彩, 沈文霞, 姚天扬. 物理化学(第4版), 北京: 高等教育出版社, 1990)
[22]	Xue Y.Q., Yang X. C., Cui Z. X., Lai W. P., J. Phys. Chem.B, 2010, 115(1), 109—112
[23]	Xue Y.Q., Du J. P., Wang P. D., Wang Z. Z., Acta Phys-Chim. Sin., 2005, 21(7), 758—762
	(薛永强, 杜建平, 王沛东, 王志忠. 物理化学学报, 2005, 21(7), 758—762)
[24]	Li W., Cui Z., Duan H., Xue Y., Appl. Phys.A:Mater. Sci. Process., 2016, 122(2), 99
[25]	Dean J.A., Lange’s Handbook of Chemistry, Science Press, Beijing, 1991
	(J. A.迪安. 兰氏化学手册, 北京: 科学出版社, 1991)

基于溶解热力学原理对纳米卤化银热力学性质的研究

Investigation into the Thermodynamic Properties of Nano-silver Halides Based on the Principle of Dissolution Thermodynamics^†

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 11

参考文献 25

相关文章 15

编辑推荐

Metrics

本文评价

[1]	贺子君, 肖明, 马祥英, 邱江源, 肖碧源, 覃方红, 黄在银. Ag₃PO₄溶解热力学函数的晶面效应与温度效应[J]. 高等学校化学学报, 2019, 40(5): 959.
[2]	刘晓林, 王路得, 黄在银, 刘作娇, 李星星. 纳米氧化锌热力学函数的微量热法及电化学法测量[J]. 高等学校化学学报, 2015, 36(3): 539.
[3]	孙晓红 ; 刘源发 ; 谭志诚 ; 贾婴琦 ; 王美涵 . 苯氧乙酸嘧霉胺盐的低温热容和热力学性质研究[J]. 高等学校化学学报, 2006, 27(6): 1109.
[4]	甘文君, 李华, 李善君. 温度效应对氟链封端聚醚酰亚胺改性环氧树脂相分离的影响[J]. 高等学校化学学报, 2004, 25(11): 2161.
[5]	赵剑曦, 游毅, 朱永平, 杨齐愉. C₁₂-s-C₁₂·2Br与低碳醇混合水溶液胶团化行为的温度效应和焓/熵补偿[J]. 高等学校化学学报, 2003, 24(5): 845.
[6]	金明, 杨庆鑫, 卢然, 潘凌云, 赵英英. 偶氮苯取代吡唑啉衍生物PMMA薄膜的光诱导双折射性质研究[J]. 高等学校化学学报, 2003, 24(1): 143.
[7]	贡雪东, 肖鹤鸣. 氟、氯和甲基取代丁二酰亚胺的结构、红外光谱和热力学性质的密度泛函理论研究[J]. 高等学校化学学报, 1999, 20(6): 918.
[8]	庄乾坤, 陈洪渊. 微电极的温度效应及其在动力学参数测定中的应用[J]. 高等学校化学学报, 1996, 17(2): 224.
[9]	陈新斌, 郭灿城, 梁本熹, 饶宗海, 杨治国. 金属卟啉的合成及其对细胞色素P-450的模拟(ⅪⅤ)--钴卟啉对环己烷的单充氧催化作用[J]. 高等学校化学学报, 1995, 16(7): 1051.
[10]	胡正水, 傅洵, 潘莹, 丁江. 叔铵盐-烷烃-醇-水四元体系的热力学函数与结构研究[J]. 高等学校化学学报, 1995, 16(7): 1116.
[11]	张保林, 王文清, 陶祖贻. D－葡萄糖、D－果糖与Ca²⁺、Mg²⁺、Cu²⁺、Zn²⁺、Cd²⁺反应的热力学函数[J]. 高等学校化学学报, 1994, 15(8): 1225.
[12]	潘懿, 杨玉良, 李莉. 紫外光固化PDLC膜性能的温度效应[J]. 高等学校化学学报, 1994, 15(11): 1710.
[13]	康敬万, 卢小泉, 高锦章, 白光弼. 差示脉冲极谱法对镉(Ⅱ)-草酸-琥珀酸混配三元配合物的研究[J]. 高等学校化学学报, 1993, 14(5): 610.
[14]	黄志贞, 陈宗淇, 薛美玲, 石彩云. 盐类和温度对非离子型表面活性剂溶液粘度的影响[J]. 高等学校化学学报, 1992, 13(6): 824.
[15]	鞠熀先, 陈洪渊, 高鸿. 碳纤维微电极研究(Ⅺ)——利用温度效应测定电极反应的热力学和动力学参数[J]. 高等学校化学学报, 1992, 13(11): 1374.

基于溶解热力学原理对纳米卤化银热力学性质的研究

Investigation into the Thermodynamic Properties of Nano-silver Halides Based on the Principle of Dissolution Thermodynamics†

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 11

参考文献 25

相关文章 15

编辑推荐

Metrics

本文评价

Investigation into the Thermodynamic Properties of Nano-silver Halides Based on the Principle of Dissolution Thermodynamics^†