羥烷基胺功能化離子液體吸收SO2的量子化學(xué)計算.pdf

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1、物理化學(xué)學(xué)報(WuliHuaxueXuebao)1364Actaehys．一Chim．Sin．，2010，26(5)：1364—1372Mav【Article]www．whxb．pku．edu．cn羥烷基胺功能化離子液體吸收SO2的量子化學(xué)計算李學(xué)良陳潔潔羅梅陳祥迎李培佩(合肥工業(yè)大學(xué)化學(xué)工程學(xué)院，可控化學(xué)與材料化工安徽省重點實驗室，合肥2300091摘要：采用量子化學(xué)中的密度泛函理論(DFF)對羥烷基胺離子液體(HyAAILs)與二氧化硫(SO2)的相互作用進(jìn)行了研究．通過幾何結(jié)構(gòu)優(yōu)化，電荷分布和

2、熱力學(xué)參數(shù)計算等來確定離子液體中能夠有效吸收s0的官能團(tuán)．HyAAILs與SO反應(yīng)形成平均距離為0．240am的s—N鍵，導(dǎo)致電荷從ILs轉(zhuǎn)移到SO以及s一0鍵長和0一s—O鍵角的改變．氣態(tài)和液態(tài)模型的計算結(jié)果表明，標(biāo)準(zhǔn)吉布斯函數(shù)變(AGe)主要取決于陽離子的結(jié)構(gòu)和分子質(zhì)量．陽離子結(jié)構(gòu)影響了吸收反應(yīng)能壘，對于三種陽離子體系的反應(yīng)活化能順序為：Ea(secondary)

3、的實驗數(shù)據(jù)非常接近．本研究提供了一種預(yù)測和驗證功能離子液體性質(zhì)的有效方法．關(guān)鍵詞：密度泛函理論；羥烷基胺離子液體；熱力學(xué)性質(zhì)；活化能；實驗驗證中圖分類號：O641QuantumChemicalCalculationofHydroxyalkylAmmoniumFunctionalizedIonicLiquidsforAbsorbingSO2LIXue—LiangCHENJie—JieLUOMeiCHENXiang-YingLIPei—Pei(AnhuiKeyLaboratoryofControllab

4、leChemistryReactionandMaterialChemicalEngineering,SchoolofChemicalEngineering,HefeiUniversityofTechnology,Hefei23000~P．R．China)Abstract：Interactionsbetweenhydroxyalkylammoniumionicliquids(HyAAILs)andsulfurdioxide(SO2)wereinvestigatedbyquantumchemicalca

5、lculationsusingfirst—principlesdensityfunctionaltheory．Theoptimizedgeometry，chargedistribution，andthermodynamicparameterswereobtainedandusedtoidentifytheeffectivegroupsintheILsthatabsorbSO2．HyAAILsreactwithSO2andformS—Nbondswithanaveragedistanceof0．240

6、am．ThisreactionresultsinchargetransferfromILstoSO2aswellaschangesintheS一0bondlengthandthe0一S一0bondangle．Tl1ecalculatedresultsfromthegasandliquidstatemodelsindicatethatthestandardGibbsfreeenergychange(AG01oftheabsorptionreactioniSmainlydeterminedbythege

7、ometryofthesecationsandtheirmolecularweight．Thecationstructureinfluencestheenergybarrieroftheabsorptionreactionandtheactivationenergy(changesasfollows：Ea(secondary)

8、emolarfractionvaluesofSO2fortheprimaryammoniumIL—SO2systemareingoodagreementwiththeexperimentalresults．Thisworkprovidesaneffectivemethodforpredictingandverifyingthepropertiesof】nc石ona】jzedILs．KeyWords：Densityfunctionaltheory；Hydroxyalky