利用超额拉曼光谱研究硝酸镁水溶液中的离子对

doi:10.3866/PKU.WHXB201205154

Abstract

Abstract:

We study the ion associations in magnesium nitrate solution by Raman spectroscopy. Utilizing the excess spectra and peak decomposition, we analyze the －OH stretching and NO₃^- symmetric stretching regions. Analysis of the －OH stretching region demonstrates that the amount of water molecules in the first hydration shell of the anion follows a linear relationship in the low concentration range (<2.3 mol·kg^-1), but deviates from this linear relationship at high concentrations (>2.3 mol·kg^-1). The contact ion-pairs at high concentration result in the nonlinear variation. In the NO₃^- symmetric stretching region, the contact ion-pairs and solvent separated ion pairs exist in the Mg(NO₃)₂ concentration region of 0.23-4.86 mol·kg^-1. From a global fitting of the Raman spectra over the whole concentration region, we deduce that the concentration of ion pairs varies. When the Mg(NO₃)₂ concentration is below 2.3 mol·kg^-1, the relative amounts of all ion-pairs increase with the concentration. However, above this concentration, the relative amount of contact ion pairs increases sharply, and solvent separated ion pairs either decrease or increase in their slower rate, until the Mg(NO₃)₂ concentration is 3.5 mol·kg^-1, and above this concentration the relative amount of one kind of solvent separated ion-pair does not change.

Key words: Aqueous magnesium nitrate solution, Contact ion pairs, Solvent separated ion pairs, Excess Raman spectra, Global fitting

WANG Chen-Chen, LIN Ke, HU Nai-Yin, ZHOU Xiao-Guo, LIU Shi-Lin. Ion Pairs in Aqueous Magnesium Nitrate Solution by Excess Raman Spectroscopy[J].Acta Phys. -Chim. Sin., 2012, 28(08): 1823-1829.

References

(1) Mahiuddin, S.; Ismail, K. Can. J. Chem. 1982, 60, 2883.
(2) El Guendouzi, M.; Marouani, M. J. Solut. Chem. 2003, 32, 535.
(3) Zhang, Y. H.; Choi, M. Y.; Chan, C. K. J. Phys. Chem. A 2004,108, 1712.
(4) Wahab, A.; Mahiuddin, S.; Hefter, G.; Kunz,W.; Minofar, B.;Jungwirth, P. J. Phys. Chem. B 2005, 109, 24108.
(5) Eigen, M.; Tamm, K. Z. Elektrochem. 1962, 66, 93.
(6) Eigen, M.; Tamm, K. Z. Elektrochem. 1962, 66, 107.
(7) Martínez, J. M.; Pappalardo, R. R.; Sánchez Marcos, E. J. Am. Chem. Soc. 1999, 121, 3175.
(8) Tomis?ic?, V.; Simeon, V. Phys. Chem. Chem. Phys. 2000, 2, 1943.
(9) Mason, P. E.; Neilson, G.W.; Dempsey, C. E.; Barnes, A. C.;Cruickshank, J. M. Proc. Natl. Acad. Sci. U. S. A. 2003, 100,4557.
(10) Buchner, R.; Chen, T.; Hefter, G. J. Phys. Chem. B 2004, 108,2365.
(11) Park, S.; Ji, M.; Gaffney, K. J. J. Phys. Chem. B 2010, 114, 6693.
(12) Bian, H. T.;Wen, X.W.; Li, J. B.; Chen, H. L.; Han, S.; Sun, X.Q.; Song, J.; Zhuang,W.; Zheng, J. R. Proc. Natl. Acad. Sci. U. S. A. 2011, 108, 4737.
(13) Funkner, S.; Niehues, G.; Schmidt, D. A.; Heyden, M.;Schwaab, G.; Callahan, K. M.; Tobias, D. J.; Havenith, M.J. Am. Chem. Soc. 2012, 134, 1030.
(14) Chandrasekaran, R.; Koh, M.; Yamauchi, A.; Ishikawa, M.Z. Elektrochem. 2009, 77, 51.
(15) Xu, M.; Larentzos, J. P.; Roshdy, M.; Criscenti, L. J.; Allen, H.C. Phys. Chem. Chem. Phys. 2008, 10, 4793.
(16) Robinson, R. A.;Wilson, J. M.; Ayling, H. S. J. Am. Chem. Soc.1942, 64, 1469. doi: 10.1021/ja01258a064
(17) Vollmar, P. J. Chem. Phys. 1963, 39, 2236. doi: 10.1063/1.1701424
(18) Chang, T. G.; Irish, D. E. J. Phys. Chem. 1973, 77, 52. doi: 10.1021/j100620a011
(19) Bol,W.; Gerrits, G. J. A.; van Panthaleon Eck, C. L. J. Appl. Crystallogr. 1970, 3, 486. doi: 10.1107/S0021889870006738
(20) Caminiti, R.; Licheri, G.; Piccaluga, G.; Pinna, G. Chem. Phys. Lett. 1979, 61, 45. doi: 10.1016/0009-2614(79)85081-2
(21) Righellato, E. C.; Davies, C.W. Trans. Faraday Soc. 1930, 26,592. doi: 10.1039/tf9302600592
(22) James, D.W.; Carrick, M. T.; Frost, R. L. J. Raman Spectrosc.1982, 13, 115. doi: 10.1002/jrs.1250130204
(23) Peleg, M. J. Phys. Chem. 1972, 76, 1019. doi: 10.1021/j100651a013
(24) Li, X. H.; Zhao, L. J.; Dong, J. L.; Xiao, H. S.; Zhang, Y. H.J. Phys. Chem. B 2008, 112, 5032. doi: 10.1021/jp709938x
(25) Zhao, L. J.; Zeng, Q. X.; Zhang, Y. H. J. Phys. Chem. A 2009,113, 215. doi: 10.1021/jp8084974
(26) Zhang, H.; Zhang, Y. H. J. Comput. Chem. 2010, 31, 2772. doi: 10.1002/jcc.21570
(27) Ramesh, S. G.; Re, S.; Boisson, J.; Hynes, J. T. J. Phys. Chem. A2010, 114, 1255. doi: 10.1021/jp903626t
(28) Li, Q. Z.;Wu, G. S.; Yu, Z.W. J. Am. Chem. Soc. 2006, 128,1438. doi: 10.1021/ja0569149
(29) Li, Q. Z.;Wang, N. N.; Zhou, Q.; Sun, S. Q.; Yu, Z.W. Appl. Spectrosc. 2008, 62, 166. doi: 10.1366/000370208783575663
(30) Wang, N. N.; Jia, Q.; Li, Q. Z.; Yu, Z.W. J. Mol. Struct. 2008,883-884, 55.
(31) Yu, X. C.; Lin, K.; Hu, N. Y.; Zhou, X. G.; Liu, S. L. Acta Phys. -Chim. Sin. 2010, 26, 2473. [余小春, 林珂, 胡乃银,周晓国, 刘世林. 物理化学学报, 2010, 26, 2473.] doi: 10.3866/PKU.WHXB20100922
(32) Yu, Y. Q.; Lin, K.; Zhou, X. G.;Wang, H.; Liu, S. L.; Ma, X. X.J. Phys. Chem. C 2007, 111, 8971. 10.1021/jp0675781
(33) Yu, Y. Q.; Lin, K.; Zhou, X. G.;Wang, H.; Liu, S. L.; Ma, X. X.J. Raman Spectrosc. 2007, 38, 1206. doi: 10.1002/jrs.1754
(34) Zhao, R. L.; Lin, K.; Zhou, X. G.; Liu, S. L. Acta Phys. -Chim. Sin. 2010, 26, 1915. [赵荣丽, 林珂, 周晓国, 刘世林. 物理化学学报, 2010, 26, 1915.] doi: 10.3866/PKU.WHXB20100728
(35) Lin, K.; Zhou, X. G.; Luo, Y.; Liu, S. L. J. Phys. Chem. B 2010,114, 3567. doi: 10.1021/jp9121968
(36) Lin, K.; Hu, N. Y.; Zhou, X. G.; Liu, S. L.; Luo, Y. J. Raman Spectrosc. 2012, 43, 82. doi: 10.1002/jrs.2997
(37) Liu, J. H.; Zhang, Y. H.;Wang, L. Y.;Wei, Z. F. Spectrochim. Acta A 2005, 61, 893. doi: 10.1016/j.saa.2004.06.030
(38) Omta, A.W.; Kropman, M. F.;Woutersen, S.; Bakker, H. J.J. Chem. Phys. 2003, 119, 12457. doi: 10.1063/1.1623746
(39) Näslund, L. Å.; Edwards, D. C.;Wernet, P.; Bergmann, U.;Ogasawara, H.; Pettersson, L. G. M.; Myneni, S.; Nilsson, A.J. Phys. Chem. A 2005, 109, 5995. doi: 10.1021/jp050413s

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Ion Pairs in Aqueous Magnesium Nitrate Solution by Excess Raman Spectroscopy

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