高氯酸盐/有机溶剂的作用及计算
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摘要
溶液化学是人们广泛研究的领域之一,并且越来越引起众多研究学者的兴趣。从分子水平研究溶液的离子溶剂化、离子缔合及溶液的微观结构等性质,对现代化学发展具有重大指导意义,将促进溶液与生物环境中离子运动控制研究的发展。溶液分子的空间结构在材料科学和生命科学上也有重要的影响。本文在总结前人工作的基础上,以研究电解质溶液微观结构为背景,借助傅里叶变换红外光谱技术和量子化学理论,对碱金属碱土金属电解质溶液中的离子溶剂化和离子缔合作用进行了研究,主要的研究内容如下:
1.利用红外光谱对一系列不同浓度的高氯酸锂—甲醇、高氯酸钠—甲醇、高氯酸镁—甲醇溶液进行测定和探索研究。谱图首先以C-H的伸缩振动作内标峰进行归一化处理。通过比较O-H伸缩振动峰的变化趋势来了解电解质溶液中的氢键变化情况。通过对C-O伸缩谱带分峰处理计算阳离子在甲醇溶液中的溶剂化数。
2.在数据归一化处理基础上,通过研究高氯酸锂—甲醇、高氯酸钠—甲醇、高氯酸钠—DMF及硝酸钠—DMF溶液中阴离子的谱带变化并对特征谱带进行分峰处理,计算出电解质溶液中的离子缔合平衡常数,并讨论不同条件对离子缔合平衡常数的影响。
3.运用量子化学理论,在B3LYP/3-21G的理论水平对溶液中离子溶剂化团簇进行模拟,得出恰当的几何构型。计算中保证无虚频出现以得到局域势能最低点的稳定构型。在此基础上对团簇进行热力学性质的计算,验证溶剂化过程的可能性。
Solution chemistry has been identified as one of the major field of chemistry, and more and more researchers have been interest in it. The properties of onic solvation, ion association and the micro-structure of solution were studied at the molecular level . It has the great guiding significance to the development of modern chemistry and will promote the study of control of ion which move in solution orbiological environment. Spatial structure of molecular in solution, in the area of materials science and life science, has an important influence . In this paper, based on the previous work experience, microscopic structures of electrolyte solutions and the tecknoledge of fourier transform spectroscopy and theory of quantum chemistry , we reseached on ionic solvation and ion association of the alkaline-earth metal electrolyte solution. The main contents of the research as follows:
1、Used infrared spectroscopy ,we determined and researched on a series of different solution concentrations of LiClO4- CH3OH, NaClO4- CH3OH,Mg(ClO4)2-- CH3OH. In the spectra, C-H stretching vibrations has been as the internal standard. We knew the changes of hydrogen bonds of aqueous electrolyte solutions through compared the O-H Stretching Vibration changes. The solvation number of the cation were computed by processing the peak area of C-O stretching band.
2、Based on the normalized data processing. We reseached the changes of characteristic bands of the LiClO4- CH3OH, NaClO4- CH3OH, NaClO4—DMF and—NaNO3—DMF solution. characteristic spectral bands were treated by deconvolution。Constants of ion association were computed. And the effects of constants of ion association were discussed.
3、The clusters were optimized by minimizing their total energy at the DFT/B3LYP level with the 3-21G basis set. we used quantum chemistry theory to get the appropriate geometry configuration. In order to get the stability configuration of the local potential energy in the lowest point, we must ensure that no imaginary frequency appears. On this basis, the possibility of Solvent process was verified through computed the thermodynamics properties of cluster.
1.利用红外光谱对一系列不同浓度的高氯酸锂—甲醇、高氯酸钠—甲醇、高氯酸镁—甲醇溶液进行测定和探索研究。谱图首先以C-H的伸缩振动作内标峰进行归一化处理。通过比较O-H伸缩振动峰的变化趋势来了解电解质溶液中的氢键变化情况。通过对C-O伸缩谱带分峰处理计算阳离子在甲醇溶液中的溶剂化数。
2.在数据归一化处理基础上,通过研究高氯酸锂—甲醇、高氯酸钠—甲醇、高氯酸钠—DMF及硝酸钠—DMF溶液中阴离子的谱带变化并对特征谱带进行分峰处理,计算出电解质溶液中的离子缔合平衡常数,并讨论不同条件对离子缔合平衡常数的影响。
3.运用量子化学理论,在B3LYP/3-21G的理论水平对溶液中离子溶剂化团簇进行模拟,得出恰当的几何构型。计算中保证无虚频出现以得到局域势能最低点的稳定构型。在此基础上对团簇进行热力学性质的计算,验证溶剂化过程的可能性。
Solution chemistry has been identified as one of the major field of chemistry, and more and more researchers have been interest in it. The properties of onic solvation, ion association and the micro-structure of solution were studied at the molecular level . It has the great guiding significance to the development of modern chemistry and will promote the study of control of ion which move in solution orbiological environment. Spatial structure of molecular in solution, in the area of materials science and life science, has an important influence . In this paper, based on the previous work experience, microscopic structures of electrolyte solutions and the tecknoledge of fourier transform spectroscopy and theory of quantum chemistry , we reseached on ionic solvation and ion association of the alkaline-earth metal electrolyte solution. The main contents of the research as follows:
1、Used infrared spectroscopy ,we determined and researched on a series of different solution concentrations of LiClO4- CH3OH, NaClO4- CH3OH,Mg(ClO4)2-- CH3OH. In the spectra, C-H stretching vibrations has been as the internal standard. We knew the changes of hydrogen bonds of aqueous electrolyte solutions through compared the O-H Stretching Vibration changes. The solvation number of the cation were computed by processing the peak area of C-O stretching band.
2、Based on the normalized data processing. We reseached the changes of characteristic bands of the LiClO4- CH3OH, NaClO4- CH3OH, NaClO4—DMF and—NaNO3—DMF solution. characteristic spectral bands were treated by deconvolution。Constants of ion association were computed. And the effects of constants of ion association were discussed.
3、The clusters were optimized by minimizing their total energy at the DFT/B3LYP level with the 3-21G basis set. we used quantum chemistry theory to get the appropriate geometry configuration. In order to get the stability configuration of the local potential energy in the lowest point, we must ensure that no imaginary frequency appears. On this basis, the possibility of Solvent process was verified through computed the thermodynamics properties of cluster.
引文
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[2] Bakker H. J. Structural Dynamics of Aqueous Salt Solutions [J]. Chemical Reviews, 2008, 108(4): 1456-1473.
[3] Dinadayalane T. C., Leszczynski Jerzy, Sastry G. Narahari. Comprehensive Study on the Solvation of Mono- and Divalent Metal Cations: Li+, Na+, K+, Be2+, Mg2+ and Ca2+ [J]. The Journal of Physical Chemistry A, 2008, 112(50): 12944-12953.
[4]卢雁,苏贵金,卢锦梭.碱金属盐和碱土金属盐溶液的红外光谱研究进展[J].化学研究与应用, 2001, 13(5): 485-490.
[5] Barthel J., Deser R. FTIR study on phase transitions in alkaline and alkaline earth metal salt solutions in acetonitrile [J]. Journal of Molecular Liquids, 1995, 67:95-103.
[6] Perelygin I.S, MA Klimchuk, EL Smolskaya. RussJPhysChem, 1987, 61(1): 51-55.
[7] D. Battisti, G. A. Nazri, B. Klassen, R. Aroca, Vibrational studies of lithium perchlorate in propylene carbonate solutions [J] . The Journal of Physical Chemistry,1993,97(22):5826-5823
[8] Alia J. M., Edwards H. FT-Raman spectroscopic study of ionic association and solvation in acrylonitrile solutions of calcium and magnesium perchlorate [J]. J Chem Soc Faraday trans, 1996, 92:1187-1196.
[9] Xuan Xiaopeng, Zhang Hucheng, Wang Jianji, et al. Vibrational Spectroscopic and Density Functional Studies on Ion Solvation and Association of Lithium Tetrafluorobrate in Acetonitrile [J]. The Journal of Physical Chemistry A, 2004, 108(37): 7513-7521.
[10] Xuan Xiaopeng, Wang Jianji, Zhao Yang, et al. FT-Raman spectroscopic evidences for the preferential solvation of sodium tetrafluorobrate in acetonitrile-based mixed solvents [J]. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2005, 62(1-3): 500-505.
[11] Fawcett W. Ronald, Liu Guojun. A study of ion pairing in acetonitrile solutions containing magnesium perchlorate using attenuated total reflection FTIR spectroscopy [J]. The Journal of Physical Chemistry, 1992, 96(11): 4231-4236.
[12] G.J.Peter, G.Bernard, J.L.Peter. Spectrochemistry of solutions.Part 21.-Inner-andouter-sphere complexes of lithium with thiocyanate in acetonitrile solutions [J]. JChemSocFaraday Trans, 1989, 85(7): 1835-1839.
[13] L.A.Solovieva, S.K.Akopyan. Determination of ion association constants by means of IR absorption band intensities of the molecules forming the first coordination spheres of the cations [J]. Spectrochimica Acta 1994, 50(4): 683-688.
[14]张运陶,周娅芬,肖盛兰.碱金属及碱土金属离子化合物溶解性变化规律[J].大学化学, 2006, 24(4): 62-69.
[15]沐来龙,冯长君.碱金属碱土金属化合物标准熵的拓扑研究[J].化学物理学报, 2003, 16(1): 19-25.
[16]李亚红,高世扬,宋彭生,等. Pitzer混合参数对HCl-NaCl-H2O体系溶解度预测的影响[J].物理化学学报, 2001, 17(1): 91-94.
[17]李亚红,宋彭生,高世扬,等.含HCl四元水盐体系溶解度预测及其在工艺上的应用Ⅰ:HCl的Pitzer参数的获得[J].盐湖研究, 1998, 6(1): 28-33.
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