UF4在空气、氧或湿氧中热化学反应研究

doi:10.3866/PKU.WHXB2014Ac08

摘要/Abstract

摘要：

分别采用显微激光拉曼光谱(MLRS)、X射线光电子能谱(XPS)、称重及形貌观察等手段, 开展了UF₄在不同环境气氛(空气, 氧气, 湿氧)中的热化学反应实验. 研究不同温度时效下UF₄质量、颜色及失重情况, 获取反应前后不同铀化合物的拉曼(Raman)和XPS特征图谱. 结果表明, UF₄在不同气氛中加热至200 ℃时, 性质稳定, 其拉曼光谱图基本无变化; 但在250 ℃以上, 样品表面颜色发生明显变化, Raman光谱和XPS分析发现有UO₂、UO₂F₂、U₃O₈等多种铀化合物生成; 通过实验, 测定并计算了UF₄与环境气氛中活性气体热化学反应的表观活化能, 建立了相应的反应速率与温度之间的关系式.

关键词: UF₄, 拉曼光谱, X射线光电子能谱, 化学反应, 环境气氛

Abstract:

We have preliminarily developed the experimental study of UF₄ and its thermal chemical reaction characteristics in environmental atmospheres such as air, O₂, and hydrated O₂. Various analytical techniques such as micro-laser Raman spectroscopy (MLRS), X-ray photoelectron spectroscopy (XPS), and metallography were used. Based on the physical and chemical properties of UF₄, we obtained the Raman and XPS spectra of different uranium compounds after heating at specific temperatures for specific times. The experimental results indicate that UF₄ is stable up to 200 ℃ in various atmospheres. Raman spectra were almost unchanged. However, above 250 ℃, the surface color of UF₄ changed significantly. Raman spectrum and XPS analyses showed that a variety of uranium compounds such as UO₂, UO₂F₂, and U₃O₈ were formed. In this work, we calculated the apparent activation energies of the reactions of UF₄ with active gases in the environment, and studied the relationship between the reaction rate and temperature in detail.

Key words: UF₄, Raman spectroscopy, X-ray photoelectron spectroscopy, Chemical reaction, Environmental atmosphere

仲敬荣, 邵浪, 余春荣, 任一鸣. UF₄在空气、氧或湿氧中热化学反应研究[J]. 物理化学学报, 2015, 31(Suppl), 25-31. doi: 10.3866/PKU.WHXB2014Ac08

ZHONG Jing-Rong, SHAO Lang, YU Chun-Rong, REN Yi-Ming. Study of Thermal Chemical Reactio[J]. Acta Phys. -Chim. Sin. 2015, 31(Suppl), 25-31. doi: 10.3866/PKU.WHXB2014Ac08

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB2014Ac08

https://www.whxb.pku.edu.cn/CN/Y2015/V31/ISuppl/25

参考文献

(1) Katz, J. J.; Rabinowitz, E. The Chemistry of Uranium; McGraw-Hill Book Co. Ltd.: New York, 1951.
(2) Cordfunke, E. H. P. The Chemistry of Uranium; Elsevier Publ Co.: Amsterdam-London-New York, 1969.
(3) Walker, S. M.; Halasyamani, P. S.; Allen, S. J. Am. Chem. Soc. 1999, 121, 10513. doi: 10.1021/ja992145f
(4) Ludwing, F. J.; Kennelley, J. A. The Pyrohydrolysis of Green Salt; USAEC Rep MCW-1419, 1958.
(5) Matae, I.; Niro, I. J. Nucl. Sci. Technol. 1983, 20 (5), 400. doi: 10.1080/18811248.1983.9733409
(6) Song, W. D. Study on Kinetics Mechanism of Pyrohydrolysis Reaction about UF₄ and UO₂F₂ with Steam-Gas; Technological Information Institute of China: Beijing, 1965. [宋维端. UF₄ 和 UO₂F₂ 与过热蒸汽作用的动力学机理的研究. 北京: 中国科技情报研究所, 1965.]
(7) Kang, S. F.; Zhao, J. Journal of Nuclear and Radiochemistry 1998, 20 (4), 202. [康仕芳, 赵君. 核化学与放射化学, 1998, 20 (4), 202.]
(8) Dong, X. Y.; Zheng, X. B.; Song, Y. L. Journal of Nuclear and Radiochemistry 2014, 36 (3), 181. [董晓雨, 郑小北, 宋昱龙. 核化学与放射化学, 2014, 36 (3), 181.]
(9) Wu, J. G. Recent Advances and Application in Technology of Fourier Transform Infrared Spectroscopy; Science Techniques and Literature Press: Beijing, 1994. [吴瑾光. 近代傅里叶变换红外光谱技术及应用(上册). 北京: 科学技术文献出版社, 1994.]
(10) Chu, M. F.; Zou, L. X.; Zhong, J. R. Chinese Journal of Rare Metals 2005, 29 (1), 106. [褚明福, 邹乐西, 仲敬荣. 稀有金属, 2005, 29 (1), 106.]
(11) Ruan, C.; Luo, W.; Wang, W. Analytica Chimica Acta 2007, 605, 80. doi: 10.1016/j.aca.2007.10.024
(12) Siekhaus, W. J. Composition of Uranium Oxide Surface Layers Analyzed by μ-Raman Spectroscopy; UCRL-CONF-201179, 2003.
(13) Zhong, J. R.; Chu, M. F.; Xiao, S. Journal of Nuclear and Radiochemistry 2010, 23 (1), 27. [仲敬荣, 褚明福, 肖洒. 核化学与放射化学, 2010, 23 (1), 27.]
(14) Zhong, J. R.; Xiao, S.; Chu, M. F. China Measurement & Test 2009, 35 (2), 112. [仲敬荣, 肖洒, 褚明福. 中国测试, 2009, 35 (2), 112.]
(15) Chu, M. F.; Meng, D. Q.; Zou, L. X. Rare Metal Materials and Engeering 2009, 38 (4), 627. [褚明福, 蒙大桥, 邹乐西. 稀有金属材料与工程, 2009, 38 (4), 627.]
(16) Nagelberg, A. S.; Ottesen, D. K. Corrosion Behavior of Lean Uranium-Titanium Alloys; SAND80-8215, 1980.
(17) Yu, B. Z.; Hansen, W. N. Mikrochim. Acta 1988, I, 189.
(18) Caculitan, N.; Siekhaus, W. J. The Growth of Epitaxial Uranium Oxide Observed by Micro-Raman Spectroscopy; UCRL-CONF-217799, 2005.
(19) Lefevre, G.; Kneppers, J.; Fedoroff, M. J. Colloid Interface Sci. 2008, 327, 15. doi: 10.1016/j.jcis.2008.07.044
(20) Roeper, D. F.; Chidambaram, D.; Halada, G. P. Electrochimica Acta 2006, 51, 4815. doi: 10.1016/j.electacta.2006.01.027
(21) Liu, S. H.; Wang, D. H.; Pan, C. H. X-ray Photoelectron Spectra Analysis; Science Press: Beijing, 1980. [刘世宏, 王当憨, 潘承璜. X 射线光电子能谱分析. 北京: 科学出版社, 1980.]
(22) Pointurier, F.; Marie, O. Spectrochimica Acta Part B 2010, 65, 797. doi: 10.1016/j.sab.2010.06.008
(23) Anderson, S. P. A Study of the Hydrolysis of Uranium Hexafluoride by Fourier Transform Infrared Spectroscopy; DE85 012871, 1985.
(24) Bostick, W. D.; McCulla, W. H.; Pickrell, P.W. Sampling, Characterization, and Remote Sensing of Aerosols Formed in the Atmospheric Hydrolysis of Uranium Hexafluoride; DE86 006341, 1984.
(25) Zuo, C. M.; Zhao, C. P.; Wang, X. L. Transaction of Sichuan University (Natural Science) 1998, 35 (3), 424. [左长明, 赵纯培, 汪小琳. 四川大学学报(自然科学版), 1998, 35 (3), 424.]
(26) Wang, X. L.; Fu, Y. B.; Xie, R. S. Nuclear Techniques 1997, 20 (4), 210. [汪小琳, 傅依备, 谢仁寿. 核技术, 1997, 20 (4), 210.]

[1]	戴久翔, 龚忠苗, 徐诗彤, 崔义, 姚美意. 锆合金初始氧化行为的原位近常压XPS研究[J]. 物理化学学报, 2022, 38(3): 2003026 - .
[2]	张月皎, 朱越洲, 李剑锋. 拉曼光谱在燃料电池领域的应用[J]. 物理化学学报, 2021, 37(9): 2004052 - .
[3]	林锦亮, 张雅敏, 张浩力. 单分子器件中的新颖静电场效应[J]. 物理化学学报, 2021, 37(12): 2005010 - .
[4]	张宗辉, 任进军, 胡丽丽. 利用固态核磁共振研究100LiO_1/2-(100-x)PO_5/2-xTeO₂快离子导电玻璃的结构[J]. 物理化学学报, 2020, 36(11): 2001048 - .
[5]	刘芳,张鲁凤,董倩,陈卓. 小尺寸金石墨纳米颗粒的合成与表征[J]. 物理化学学报, 2019, 35(6): 651 -656 .
[6]	郑东,熊鹏飞,钟北京. NOFBX新型绿色推进剂燃烧化学反应动力学模型[J]. 物理化学学报, 2019, 35(11): 1241 -1247 .
[7]	王岩,李雄,胡善玮,徐倩,鞠焕鑫,朱俊发. Ca掺杂的CeO₂模型催化剂的形貌和电子结构及其与CO₂分子的相互作用[J]. 物理化学学报, 2018, 34(12): 1381 -1389 .
[8]	赵新飞,陈浩,吴昊,王睿,崔义,傅强,杨帆,包信和. 氧化锌有序结构在Au(111)和Cu(111)上的生长[J]. 物理化学学报, 2018, 34(12): 1373 -1380 .
[9]	张英杰,朱子翼,董鹏,邱振平,梁慧新,李雪. LiFePO₄电化学反应机理、制备及改性研究新进展[J]. 物理化学学报, 2017, 33(6): 1085 -1107 .
[10]	韩磊,彭丽,蔡凌云,郑旭明,张富山. 液态聚乙二醇CH₂剪切振动和扭转振动——拉曼光谱和密度泛函理论计算[J]. 物理化学学报, 2017, 33(5): 1043 -1050 .
[11]	吴元菲,李明雪,周剑章,吴德印,田中群. 密度泛函理论研究银上吸附对巯基吡啶的SERS化学增强效应[J]. 物理化学学报, 2017, 33(3): 530 -538 .
[12]	金璐頔,徐晶晶,张勇,余跃洲,刘畅,赵东平,叶安培. 软骨细胞体外增殖去分化的拉曼光谱分析[J]. 物理化学学报, 2017, 33(12): 2446 -2453 .
[13]	金颖淳,郑旭明. 2, 4-二硫代尿嘧啶的紫外吸收光谱和共振拉曼光谱[J]. 物理化学学报, 2017, 33(10): 1989 -1997 .
[14]	方永进,陈重学,艾新平,杨汉西,曹余良. 钠离子电池正极材料研究进展[J]. 物理化学学报, 2017, 33(1): 211 -241 .
[15]	张小宁,HOLLIMON Valerie,BRODUS DaShan. 硅(111)衬底上直接接枝巯基的方法[J]. 物理化学学报, 2016, 32(9): 2364 -2368 .

UF₄在空气、氧或湿氧中热化学反应研究

Study of Thermal Chemical Reactio

PDF

赞

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

Metrics

推荐阅读 0