高等学校化学学报 ›› 2018, Vol. 39 ›› Issue (10): 2272-2279.doi: 10.7503/cjcu20180170

• 物理化学 • 上一篇    下一篇

硫酸氢钾及其熔体结构的原位高温拉曼光谱与分解热力学研究

杨冶金, 尤静林(), 王建, 王敏, 何莹霞, 吴志东   

  1. 省部共建高品质特殊钢冶金与制备国家重点实验室,上海市钢铁冶金新技术开发应用重点实验室, 上海大学材料科学与工程学院, 上海 200072
  • 收稿日期:2018-03-04 出版日期:2018-09-29 发布日期:2018-09-29
  • 作者简介:

    联系人简介: 尤静林, 男, 博士, 教授, 博士生导师, 主要从事分子光谱和无机结构研究. E-mail: jlyou@staff.shu.edu.cn

  • 基金资助:
    国家自然科学基金(批准号: 21773152)、 上海市科学技术委员会项目(批准号: 12520709200)、 国家“111”引智项目(批准号: D17002)、 省部共建高品质特殊钢冶金与制备国家重点实验室开放课题(批准号: SKLASS2015-01, SKLASS2017-02)和科技部中央引导基金(批准号: YDZX20173100001316)资助.

In-situ High Temperature Raman Spectroscopic and Decomposition Thermodynamic Study of the Structure of Potassium Hydrogen Sulfate and Its Melt

YANG Yejin, YOU Jinglin*(), WANG Jian, WANG Min, HE Yingxia, WU Zhidong   

  1. State Key Laboratory of Advanced Special Steel, Shanghai Enhanced Laboratory of Ferrometallurgy, School of Materials Science and Engineering, Shanghai University, Shanghai 200072, China
  • Received:2018-03-04 Online:2018-09-29 Published:2018-09-29
  • Contact: YOU Jinglin E-mail:jlyou@staff.shu.edu.cn
  • Supported by:
    † Supported by the National Natural Science Foundation of China(No. 21773152), the Shanghai Committee of Science and Technology Fund, China( No. 12520709200), the National “111” Project(the Programme of Introducing Talents of Discipline to Universities) of China(No. D17002), the Open Project of State Key Laboratory of Advanced Special Steel, Shanghai University, China(Nos. SKLASS2015-01, SKLASS2017-02), the Special Fund Project of Shanghai Municipality for Science and Technology Development, China(No. YDZX20173100001316).

摘要:

运用原位高温拉曼光谱技术研究了KHSO4从室温至550 ℃的相变过程, 分别基于密度泛函理论及量子化学从头算分析KHSO4晶体和K2S2O7熔体的分子振动和拉曼光谱散射活性, 对拉曼光谱特征峰进行归属, 并获取KHSO4与K2S2O7熔体团簇特征振动的拉曼散射截面, 建立特征峰面积与物种浓度的直观关系, 并通过Factsage数据库研究KHSO4分解过程的热力学性能. 结果表明, 210 ℃下KHSO4链状结构向二聚体结构转换, KHSO4由正交α相变为单斜β相; 220-550 ℃分解为K2S2O7, 由平衡常数K计算得到反应焓ΔH=(72.59±2.40) kJ/mol.

关键词: 高温拉曼光谱, 硫酸氢钾, 微观结构, 密度泛函理论, 热力学

Abstract:

In-situ high temperature Raman spectroscopic technology was used to study the phase transitions of KHSO4 from ambient temperature to 550 ℃. Raman vibrational wavenumber and scattering activity of KHSO4 crystal and K2S2O7 melt were calculated based on Density functional theory(DFT) and ab initio quantum chemical studies, respectively. The major vibrational modes were assigned, Raman scattering cross sections were also obtained, which led to establish the relationship between the area of the characteristic peak and species concentrations. And thermodynamic enthalpy were also calculated through the Factsage database as a comparison in the process of decomposition to confirm the experimental calculated thermodynamic enthalpy. Results show that the structure of KHSO4 transforms from chain to dimer at 210 ℃, along with the crystal symmetry changing from monoclinic to orthogonal one. It decomposes during 220—550 ℃, which results in the formation of K2S2O7. The reaction enthalpy(ΔH) of (72.59±2.40) kJ/mol was calculated from the equilibrium constant.

Key words: High temperature Raman spectroscopy, Potassium hydrogen sulfate, Microstructure, Density functional theory(DFT), Thermodynamics

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