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  

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

作　　者：杨冶金 尤静林[1] 王建[1] 王敏[1] 何莹霞 吴志东 YANG Yejin;YOU Jinglin;WANG Jian;WANG Min;HE Yingxia;WU Zhidong(State Key Laboratory of Advanced Special Steel,Shanghai Enhanced Laboratory of Ferrometallurgy, School of Materials Science and Engineering,Shanghai University,Shanghai 200072,China)

机构地区：[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

出　　处：《高等学校化学学报》2018年第10期2272-2279,共8页Chemical Journal of Chinese Universities

基　　金：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.

摘　　要：运用原位高温拉曼光谱技术研究了KHSO_4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KHSO_4晶体和K_2S_2O_7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KHSO_4与K_2S_2O_7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KHSO_4分解过程的热力学性能.结果表明,210℃下KHSO_4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K_2S_2O_7,由平衡常数K计算得到反应焓ΔH=(72.59±2.40) kJ/mol.In-situ high temperature Raman spectroscopic technology was used to study the phase transitions of KHSO 4 from ambient temperature to 550℃.Raman vibrational wavenumber and scattering activity of KHSO 4 crystal and K 2S 2O 7 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 KHSO 4 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 K 2 S 2 O 7.The reaction enthalpy(ΔH)of(72.59±2.40)kJ/mol was calculated from the equilibrium constant.

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 

分 类 号：O641.3[理学—物理化学]