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
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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_2S_2O_7.The reaction enthalpy (ΔH) of (72.59 ± 2.40) kJ/mol was calculated from the equilibrium constant.
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_2S_2O_7.The reaction enthalpy (ΔH) of (72.59 ± 2.40) kJ/mol was calculated from the equilibrium constant.
引文
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[3]Paulino J.F.,Busnardo N.G.,Afonso J.C.,Hazardous Materials,2008,150(3),843-849
[4]Pérez M.,Ruiz D.,Autino J.,Sathicq A.,Romanelli G.,Comptes Rendus Chimie,2016,19(5),551-555
[5]Parry G.S.,Glasser L.,Crystalline,1960,113(1-6),57-64
[6]Goypiron A.,de Villepin J.,Novak A.,Raman Spectroscopy,1980,(9),297-303
[7]Bukleski M.,Vladimir V.,Vladimir P.,Vibrational Spectroscopy,2011,57(1),15-22
[8]Matsuo Y.,Ferroelectrics,2004,302(1),85-90
[9]Hamma H.,Rasmussen S.B.,Rogez J.,Elbelghiti M.A.,Eriksen K.M.,Fehrmann R.,Thermochemica Acta,2006,440(2),200-204
[10]Hatem G.,Eriksen K.M.,Fehrmann R.,Thermal Analysis and Calorimetry,2002,68(1),25-30
[11]Swain D.,Bhadram V.S.,Pradhan G.K.,Venkataprasad,Bhat S.V.,Narayana C.,Rao C.N.R.,Physical Chemistry,2010,114(37),10040-10044
[12]Periasamy A.,Muruganand S.,Palaniswamy M.,Rasayan Journal of Chemistry,2009,2(4),9781-9789
[13]Sharon M.,Kalia A.K.,Solid State Chemistry,1980,31(3),295-303
[14]Fehramnn R.,Hansen N.H.,Bjerrum N.J.,Inorganic Chemistry,1983,22(26),4009-4014
[15]Walrafen G.E.,Irish D.E.,Young T.F.,Chemical Physics,1962,37(3),662-670
[16]Swain D.,Row T.N.,Inorganic Chemistry,2008,47(19),8613-8615
[17]Knudsen C.B.,Kalampounias A.G.,Fehrmann R.,Boghosian S.,Physical Chemistry B,2008,112(38),11996-12000
[18]Dey B.,Jain Y.S.,Verma A.L.,Raman Spectroscopy,1982,13(3),209-212
[19]Merinov B.V.,Solid State Ionics,1996,84(1/2),89-96
[20]Eriksen K.M.,Fehrmann R.,Hatem G.,Escard M.G.,Lapina O.B.,Mastikhin V.M.,Physical Chemistry,1996,100(25),10771-10778
[21]You J.L.,Novel High Temperature Raman Spectroscopic Techniques,Spectral Calculation and Their Application in Micro-structure Study of Inorganic Materials,Shanghai University,Shanghai,2006(尤静林.高温拉曼光谱创新技术、光谱计算和在无机化合物微结构研究中的应用,上海:上海大学,2006)
[22]Li S.P.,Wu G.M.,Zheng X.M.,Chem.J.Chinese Universities,2004,25(8),1495-1498(李少鹏,吴光明,郑旭明.高等学校化学学报,2004,25(8),1495-1498)
[23]Kalampounias A.G.,Boghosian S.,Applied Spectroscopy,2009,63(9),1050-1056
[24]Hatem G.,Eriksen K.M.,Fehrmann R.,Thermal Analysis and Calorimetry,2002,68(1),25-30
[25]Hatem G.,Eriksen K.M.,Escard M.G.,Fehrmann R.,Catalysis,2002,19(3),323-331