极化效应及其在烃类化合物物理化学性能估算应用-polarization effect and its application in estimating physical and chemical properties of hydrocarbon compounds.docx

equationswereproposedforalkanesandalkenes,respectively.Theionizationpotentials(Ip)ofalkanesandalkeneswereevaluatedwiththeGMPEIandGMPEIπ,andgottheevaluatedIpvaluesmoreclosetotheexperimentalonesthanthatofcalculatedIpvaluesbysemi-empiricalquantumchemistrymethodAM1orbytheabinitio(#HF/6-31G**OPT,Gaussian98program)totheexperimentalones.Theconjugatedpolarizabilitypotential(CPP),effectivepolarizabilityeffectindex(PEI(ef))andtheircalculationequationswereproposed.Correlatedthetwoparameters,CPPandPEI(ef),totheenergyofultravioletabsorptionmaximum,agoodpredictiveequationwasobtained.Itspredictedresultsshowasimilarestimatedprecisioncomparingwiththecalculatedresultsbyabinitiocalculationofquantumchemistry(#HF/6-31G**OPT,Gaussian98program),andshowabetterestimatedprecisioncomparingwiththecalculatedresultsbysemi-empiricalquantumchemistrymethodAM1.Theinvestigatedresultsalsoindicatesthatitislesseffectivetoreducetheenergyofultravioletabsorptionmaximumbymeansofincreasethealkylsubstituentgroupsthanlengthentheconjugatedbackbonechainintheconjugatedalkenes.Therateconstantsofradicalandelectrophilicadditiontoalkenesaredominatedbydifferentfactors.Forthesimplealkeneswithonlyalkylgroups:(A)itsrateconstants-log(kOH)fortheadditionofOHradicalcanbecorrelatedwiththeGeometricMeanPolarizabilityEffectIndexofπbond(GMPEIπ);And(B)itsrateconstants(logK)fortheadditionofelectrophilicreagentscanbecorrelatedwiththetwoparametersPEI(L)andPEI(S).WherePEI(L)andPEI(S)representthelagerandsmallerpolarizabilityeffectofalkylgroupsconnectingwithtwocarbonatomsonthedoublebondofalkenes,respectively.Keywordsalkane,alkene,polarizabilityeffect,bondingorbital-connectionmatrix,heatofatomization,heatofformation,physicochemicalproperty,ionizationpotential,conjugatedpolarizabilitypotential,ultravioletabsorption,rateconstantsofaddition1绪论1.1化合物性能估算简述化合物的物理化学性质是化学工业中必不可少的基础数据，无论是化工设备的设计、化工生产中工艺流程的确定，还是化工过程的模拟与优化，都必须知道所涉及化合物诸如密度、蒸汽压、生成焓、导热系数等有关物理化学性质。由于这项工作的重要性，多年来，国际上工业技术先进的国家，都组织了相当规模的人力、物力，对化工基础数据进行工作。其工作的主要内容为收集整理大量的实验数据，并对这些数据进行分析、归