hansen solubility parameters.ppt

hansensolubilityparameters,charlesm.hansen,whykeepgoing?,”evenifyoureontherighttrack,youllgetrunoverifyoujustsitthere.”willrogerstomethismeanshelpdevelopthehansensolubilityparametersinpractice(hspip)ebook/software,wholeequalssumofpartse=cohesionenergy=evap,e=ed+ep+ehd-dispersion(hydrocarbon)p-polar(dipolar)h-hydrogenbonds(electroninterchange)v-molarvolumee/v=ed/v+ep/v+eh/v2=2d+2p+2hhansensolubilityparameters(hsp)=squarerootofcohesionenergydensity,d,homomorphconcept(ed=eforsimilarhydrocarbon)correspondingstatetheory(cst)cstfigureforedforeachofaliphatic,cycloaliphatic,oraromaticstructureedversusvfortr=t298.15./tcritical,figureforedforaliphatichydrocarbons,p,bttcherequationcal/cm3,beerbowerequationmpa,p=37.4()/v,h,1.eh=e-ed-ep2.panayiotoustatisticalthermodynamicsdirectly3.groupcontributionsh=(eh/v)4.checkwherepossiblethat:2=2d+2p+2h,thermodynamicbasisofhsp,exchangeenergy(density)a12=11+22-212geometricmean12=(1122)scatcharda12=(11-22)2hildebrand(cohesiveenergydensity)11=e1/v1;22=e1/v1hildebrand/scottem=12(x1v1+x2v2)(1-2)2patterson/delmasgnoncomb=12vm(1-2)2,thermodynamicbasis(cont.),hansenhspra2=4(d1-d2)2+(p1-p2)2+(h1-h2)2hansenrelativeenergydifference(red)red=ra/roflory/hansenx/xc=(red)2prigogine(withgeometricmean)2=(2prig/4+92)whereprig=(2-1)/1prigogine/hansen2prig=(i1-i2)/o2for“i”=p,hpanayiotou-directcalculationofhydrogenbonding,statisticalthermodynamics-panayiotou,equationofstate:chemicalpotential:,panayiotou2d,2p,and2h,2h-comparison,hansenpanayiotoutoluene2.002.00tetralin2.902.90acetone6.957.00methylmethacrylate5.405.40ethanol19.4319.981-butanol15.8015.80dimethylsulfoxide10.2010.28water42.3242.17,2hpolymercomparison,hansenpanayiotoulin.polyethylene2.802.80polystyrene2.902.90pvc3.403.42pmma5.105.10pc6.906.90nylon6624.0023.90,freeenergychange,g,determinessolubilityornot,freeenergygmustbenegativeforsolutiong=(1/n)ln()+(1-)ln(1-)+(1-)isthesolventvolumefractionnisthenumberofmonomersinchain=vm/rt(d1-d2)2+0.25(p1-p2)2+0.25(h1-h2)2isthechiparameter,vmisthemolarvolume,pversushplot,hansensolubilityparameterdiagram,keyequations,ra2=4(d1-d2)2+(p1-p2)2+(h1-h2)2theexperimentallyverified”4”isalsofoundinprigoginescsttheoryred=ra/ro(distancetospherecenterdividedbyitsradius)(red)2=(ra/ro)2correspondsto12/cinhuggins/florytheory,spheroidsofsolubilityunless”4”isused,effectoftemperature,highertemperaturelowervalueslargereffectforh,changeofhwithtemperature(williams),table10.3.experimentallydeterminedvaluesofehand,.,hydrogen-bondparameter,eh,cn,cooh,typesofmaterials,solventspolymerspigmentsurfacesfibersurfacesdrugschemicalprotectiveclothingbiologicalmaterialssalts-bothorganicandinorganic,examplesofusesofhsp,solventselectionandsubstitution(reach,ozonedepletion,voc,etc.)solubility,swelling,relatedphenomenasurfacecharacterizationandadhesionpermeation,breakthroughtimesphysicalpropertiespolymerandbiologicalcompatibilitycontrolleddrugrelease,cholesterolnonsolventsynergism,boundarysolvents(mixtures)havetraditionallybeentheleastexpensive,xyleneplusn-butanolcanoftenapproachtheperformanceofotherwidelyusedsolvents,noncompatiblepolymersdissolvedinamixtureofnon-solvents,solventaffectspigmentdispersionstability,solvent1optimuminmostcasesbinderonpigmentsolvent2toogoodforbinderremovesbindersolvent3toogoodforpigmentreplacesbinder,replaceozonedepletersmatchsoilhspuseazeotropes,sbsmustbepartlycompatiblewithbitumen,varnishremovalfromoldpaintings,teastriangularplotforsolventselection,modificationofhansenparametersfd=100d/(d+p+h)fp=100p/(d+p+h)fh=100h/(d+p+h),teasplot,solubilityofcarbon-60,coc-solubilityshadedescclear,environmentalstresscrackingcorrelateswithrednumberandmolarvolume,escinpc,hspfor”carbon”materials,surfactantstwohspregionsrequired,surfacephenomenaepoxyfilm,a-spontaneousspreadingb-nodewettingc-spontaneousdewetting,fibersurfacecharacterization,aglassycarbonbcarbonfiberscppfibers,self-assembly,lowerenergypolymerissurfacelayerintwolayerfilmdepositedfromtruesolution,self-assemblythixotropicpaint,versamidsegmentsassociatealcoholswilldestroyeffectshearbreaksstructuretemporarily,breakthroughtimesmallermoleculeswithlinearstructureandlowreddiffusefaster-ptfe,hspforcytotoxicdrugsforgloveselection,chemicaldphvfluorouracil18.011.711.6118.3gemcitabine19.012.615.5260.6cyclophosphamide17.511.912.6279.1ifosfamide17.511.99.8261.1methotrexate18.010.214.2378.7etoposide20.07.512.5588.5paclitaxel(taxol)18.06.69.8853.9averagegroup118.310.312.3-cytarabine19.015.220.1187.1(pyrimidine/arabinose)carboplatin(organicpt)27.39.010.4185.1,cyclophosphamidebreakthroughtimesnitrile45minutes,butyl4hours,permeation-viablehumanskinursin,et.al.,j.am.ind.hyg.assoc.,56,651(1995).,sigmoidalabsorptiontimedelaywithsqrttime,absorptionlinearwithtimecaseii,absorptionfasterthanlinearwithtimesupercaseii,hspfororganicsalts,materialdphdmea-dimethylethanolamine16.19.215.3formicacid14.311.916.6aceticacid14.58.013.5dmea/formicacid17.221.522.5dmea/aceticacid16.819.819.8allvalueshigher,hspforionicliquids,ionicliquiddphtv,cc/molebmimcl19.120.720.735.0175.0bmimpf621.017.210.929.3207.6omimpf620.016.510.027.8276.0bmimbf423.019.010.031.5201.4bmimisbutylmethylimidazole(oisoctyl),solventshavingco2solubilitygreaterthanidealx=0.0229at25candpco2=1(williams),bestsolventscarbondioxide,hspforcarbondioxide,datafit=1.000forexperimentaldata2d=15.7mpa2p=6.3mpa2h=5.7mparo=3.3mpa,carbondioxidesolubility,hspforspecialchemicals,chemicaldphamphetamine17.54.36.3bisphenola19.25.913.8d-camphor17.89.44.72-ethylhexylphthalate(mehp)17.36.26.8hexanal15.88.55.4nicotine18.57.86.5l-menthol16.64.710.6paracetemol17.810.513.9paraquat19.58.85.9skatole20.07.16.22-tert-butyl-4-methylphenol17.33.710.5triacetin16.54.59.1triclosan20.07.710.0vanillin18.610.613.8,hspavailablefor1200chemicalsincluding:,adrenaline,ascorbicacid,bethoxazin,caffeine,carbondioxide,cholesterol,dna,dopamine,ecstasy,lignin,meclofenoxate,norephedrin,palmoil,quinine,saccarine,serotonin,spermidin,sucrose,urea,zein,etc.,etc.,similaritytotetrabromobisphenola,materialdphraredtbbpatbbpa20.29.113.8-0.0pentachloro-phenol21.56.912.83.5(close)lignin21.914.116.96.80.5rapidskinpermeability17.612.511.06.50.36psoriasisscaleswelling24.611.912.99.30.49,dioxinphysicalinteractions,dph20.09.27.6predictions:moderateskinpermeationrate(largesize)readyabsorptionintolignin(plants),ultrastructureofwoodhemicellulosesidechainsorient,boundaryhspmatch(lignin)(lignin)acacacac2323m14m14m14g14m14g14m14m14g3611mga(cellulose)(cellulose)goodhspmatch,hspforwater,dphrosinglemolecule15.516.042.31%solublein15.120.416.518.1datafit0.856good/total88/167totalmiscibility18.117.116.913.0datafit0.880good/total47/166,chemicalsaffectingdna-tsop.o.p.,et.al.natlacadsci.,usa,48,686-698,(1962),increasingactivitywasfoundtobe:adonitol,methylriboside(bothnegligible)cyclohexanolphenol,pyrimidine,uridinecytidine,thymidinepurine,adenosine,inosine,deoxyguanosinecaffeine,coumarin,2,6-dichloro-7-methylpurineplusformamideanddimethylsulfoxide,hspcorrelationfordna,hspfordna,chemicalsorderedcorrectlythosenotcalculatedhavemoleculesthataretoocomplicatedandtoolargetobedirectlycomparedwiththeothersmallermolecules.result(mpa)2d2p2h19.020.011.0ehis14%ofe,hspfordnabases,segmentdph“v”inh2oparts/100guanine20.012.712.5126.1insol.cytosine19.512.19.9107.80.77adenine20.010.213.7131.50.05thymine19.514.212.6121.70.4average19.7512.312.2-,essentiallyindenticalhsp:dnabases,cytotoxicdrugsandrapidskinpermeation,dphrara(bases)(gp1)rapidskinperm.17.612.511.04.472.91dnabases19.7512.312.2-3.52ave.group1drugs18.310.312.33.52-synergismwillbefoundforanyof:phthalateplasticicizers,tricresylphosphate,n-methyl-2-pyrrolidone,mixedwithanyof:ethanol,2-propanol,ethyleneglycol,propyleneglycol,orglycerol,hspdifferentfordnabases,dna,proteins,anddepotfat,dphrofitra(bases)dna19.020.011.011.01.0007.93(molecule)zein22.49.819.411.90.9649.28(protein)lard15.91.25.412.01.00015.87(depotfat),chemotherapydrugswithethanol/dopmixtures,cocktailforconsiderationmethylparaben+dop+ethanoltarget:chemodrughspsphere,optimumnmrsolventmixturesarepossible,hplcretentiontime,retentiontimebasedonhspofsolute,mobileandstationaryphases,wholeequalssumofpartse=cohesionenergy=evap,e=ed+ep+ehd-dispersion(hydrocarbon)p-polar(dipolar)h-hydrogenbonds(electroninterchange)v-molarvolumee/v=ed/v+ep/v+eh/v2=2d+2p+2hhansensolubilityparameters(hsp)=squarerootofcohesionenergydensit