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1、FluidPhaseEquilibria180(2001)345359EntrainereffectinsupercriticalmixturesE.Ruckenstein∗,I.ShulginDepartmentofChemicalEngineering,StateUniversityofNewYorkatBuffalo,Amherst,NY14260,USAReceived14September2000;receivedinrevisedform16January2001;accepted25January2001Abstr
2、actTheobjectiveofthispaperistoproposeapredictivemethodfortheestimationofthechangeinthesolubilityofasolidinasupercriticalsolventwhenanothersolute(entrainer)oracosolventisaddedtothesystem.Toachievethisgoal,thesolubilityequationswerecoupledwiththeKirkwoodBuff(KB)theoryo
3、fdiluteternarysolutions.Inthismanner,thesolubilityofasolidinasupercriticalfluid(SCF)inthepresenceofanentraineroracosolventcouldbeexpressedintermsofonlybinarydata.TheobtainedpredictivemethodwasappliedtosixternarySCFsolutecosoluteandtwoSCFsolutecosolventsystems.Inthefor
4、mercase,theagreementwithexperimentwasverygood,whereasinthelatter,theagreementwasonlysatisfactory,becausethedatawerenotfortheverydilutesystemsforwhichthepresentapproachisvalid.©2001ElsevierScienceB.V.Allrightsreserved.Keywords:Cosolvent;Entrainer;Supercriticalfluid;Flu
5、ctuationtheory;Solubilityprediction1.IntroductionTheadditionofasmallamount(usuallylessthan5mol%)ofavolatilecosolventtoasupercriticalfluid(SCF)canleadtoaverylargeenhancementinthesolubilityofasolute(uptoseveralhundredpercent)[1].Similarly,theuseofmultiplesolutes(usually
6、binary)canenhancetheirsolubilities[1].Thesephenomena,oftencalledthecosolventandentrainereffects,haveattractedattentionbothamongexperimentalists[27]andtheoreticians[812].Twotypesofternarysupercriticalmixturesareofinterest.1.Mixturescontainingacosolvent:SCF(component1)
7、solute(usuallysolid)(2)cosolvent(usuallyasubcriticalliquid)(3).2.Mixturescontainingtwosolutes:SCF(1)solute(2)cosolute(3).ForthesolubilityofasolidinanSCF(binarysupercriticalmixtureSCF(1)+solidsolute(2)),onecanwritethewell-knownrelation[13]P0(P−P0)V0xbin=2exp22(1)2Pφbi
8、nRT2∗Correspondingauthor.Tel.:+1-716-645-2911;fax:+1-716-645-3822.E-mailaddresses:feaeliru@acsu.buffalo.edu(E.Ruckenstein),ishulgin
