由~(13)C NMR化学位移测定值确定烷烃生成焓
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摘要
本文通过分析烷烃核磁共振碳谱(~(13)C NMR)化学位移与生成焓之间的关系,提出由~(13)C NMR化学位移的测定值来确定烷烃生成焓的新方法.用53个烷烃分子的~(13)C NMR化学位移总和(SCS)、三键数(P3)以及碳原子数目(n)与生成焓实验值进行相关,所得回归方程的相关性良好(相关系数R=0.998 2,标准偏差S=3.5 kJ/mol).进而,通过随机抽样和留一法证实该方程具有良好的稳定性和预测能力.将烷烃~(13)CNMR化学位移与其生成焓定量联系起来,不仅有利于深入理解分子结构与性能关系,还为预测那些难于测定且费时的物理化学性质提供了新思路.
The quantitative relationship between the ~(13)C NMR chemical shifts of alkanes and their formation enthalpy was studied. A new approach for calculating the formation enthalpy from the ~(13)C NMR chemical shifts was proposed. The experimentally measured formation enthalpy values of 53 alkanes were correlated with the parameters SCS(the sum of chemical shift), P3(path counts of length three bounds) and n(the number of carbon atoms). The regression results showed a good correlation(R = 0.998 2,S = 3.5 kJ/mol). The random sampling method and leave-one-out method were used to verify the stability and prediction ability of the model.
The quantitative relationship between the ~(13)C NMR chemical shifts of alkanes and their formation enthalpy was studied. A new approach for calculating the formation enthalpy from the ~(13)C NMR chemical shifts was proposed. The experimentally measured formation enthalpy values of 53 alkanes were correlated with the parameters SCS(the sum of chemical shift), P3(path counts of length three bounds) and n(the number of carbon atoms). The regression results showed a good correlation(R = 0.998 2,S = 3.5 kJ/mol). The random sampling method and leave-one-out method were used to verify the stability and prediction ability of the model.
引文
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[2]NEEDHAM D E,WEI I C,SEYBOLD P G.Molecular modeling of the physical properties of alkanes[J].J Am Chem Soc,1988,110(13):4186-4194.
[3]SCRETTAS C,MICHA-SCRETTAS M.Correlation of thermochemical data with gas-phase ionization potentials[J].J Org Chem,1989,54:5132-5137.
[4]NAU W M,ADAM W,KLAPSTEIN D,et al.Correlation of oxidation and ionization potentials for azoalkanes[J].J Org Chem,1997,62:5128-5132.
[5]KATRITZKY A R,GORDEEVA E V.Traditional topological indexes vs electronic,geometrical,and combined molecular descriptors in QSAR/QSPR research[J].J Chem Inf Comput Sci,1993,33(6):835-857.
[6]DONG W,YANG X J,ZHANG J,et al.Use of linear enthalpy relationship to predict standard enthalpies of formation of crystalline actinide dioxides[J].Mater Lett,2008,62:2894-2896.
[7]WINGET P,CLARK T.Enthalpies of formation from B3LYP calculations[J].J Comput Chem,2004,25(5):725-733.
[8]EMEL’YANENKO V N,KABO G J,VEREVKIN S P.Measurement and prediction of thermochemical properties:Improved increments for the estimation of enthalpies of sublimation and standard enthalpies of formation of alkyl derivatives of urea[J].J Chem Eng Data,2006,51(1):79-87.
[9]宁永成.有机化合物结构鉴定与有机波谱学[M].第二版.北京:科学出版社,2000.
[10]朱淮武.有机分子结构波谱解析[M].北京:化学工业出版社,2005.
[11]YI G Y,CAO C Z.Influence of substituent effects on the 13C NMR chemical shifts of aliphatic alcohols[J].Chinese J Magn Reson,2009,26(1):58-74.易贵元,曹晨忠.取代基效应对脂肪醇13C NMR化学位移的影响[J].波谱学杂志,2009,26(1):58-74.
[12]CAO C Z,LIU C,LIU,S S,et al.Carbon atom distance edge vector and 13C NMR chemical shifts of alkanes[J].Chinese J Magn Reson,1998,15(4):347-353.曹晨忠,刘超,刘树深,等.原子距边矢量、三键数与烷烃的13C NMR化学位移[J].波谱学杂志,1998,15(4):347-353.
[13]LIU S S,YU B M,CAO C Z,et al.Study of 13C NMR spectroscopy:the chemical shift of alkane?and the atom distance edge vectorμ[J].JAtom Mol Phys,1997,14(4):606-614.刘树深,余般梅,曹晨忠,等.核磁共振碳谱的研究:烷烃分子的化学位移?与原子距边矢量?[J].原子与分子物理学报,1997,14(4):606-614.
[14]LINDEMAN L P,ADAMA J Q.Carbon-13 nuclear magnetic resonance spectrometry.Chemical shifts for the paraffins through C9[J].Anal Chem,1971,43(10):1245-1252.
[15]HAYNES W M.CRC Handbook of chemistry and physics,91st ed[M].Boca Raton,FL:CRC Press,2010-2011.
[16]LABAUF A,GREENSHIELDS J B,ROSSINI F D.Heats of formation,combustion,and vaporization of the 35 nonanes and 75 decanes[J].JChem Eng Data,1961,6(2):261-263.
[17]CAO C Z,LIU S S,LI Z L.On molecular polarizability:2.Relationship to the boiling point of alkanes and alcohols[J].J Chem Inf Comput Sci,1999,39(6):1105-1111.
[18]CAO C Z,ZHOU F Y.Estimation formula for boiling point of hydrocarbon homologues and physical significance of coefficients[J].Chem Bull,1992,11:36-39.曹晨忠,周飞跃.烃类同系物沸点通式及式中各系数的物理意义[J].化学通报,1992,11:36-39.