hansen solubility parameters.ppt

HANSEN SOLUBILITY PARAMETERS,CHARLES M.HANSEN,WHY KEEP GOING?,”Even if youre on the right track,youll get run over if you just sit there.”Will RogersTo me this means help develop the Hansen Solubility Parameters in Practice(HSPiP)eBook/software,WHOLE EQUALS SUM OF PARTSE=COHESION ENERGY=Evap,E=ED+EP+EH D-Dispersion(Hydrocarbon)P-Polar(Dipolar)H-Hydrogen Bonds(Electron Interchange)V-Molar Volume E/V=ED/V+EP/V+EH/V 2=2D+2P+2H HANSEN SOLUBILITY PARAMETERS(HSP)=Square Root of Cohesion Energy Density,D,HOMOMORPH CONCEPT(ED=E FOR SIMILAR HYDROCARBON)CORRESPONDING STATE THEORY(CST)CST FIGURE FOR ED FOR EACH OF ALIPHATIC,CYCLOALIPHATIC,OR AROMATIC STRUCTUREED versus V for Tr=T298.15./TCRITICAL,FIGURE FOR ED FOR ALIPHATIC HYDROCARBONS,P,Bttcher Equation cal/cm3,Beerbower Equation MPa,P=37.4()/V,H,1.EH=E-ED-EP 2.Panayiotou statistical thermodynamics directly3.Group Contributions H=(EH/V)4.CHECK where possible that:2=2D+2P+2H,THERMODYNAMIC BASIS OF HSP,Exchange Energy(Density)A12=11+22-212 Geometric Mean12=(1122)ScatchardA12=(11-22)2Hildebrand(Cohesive Energy Density)11=E1/V1;22=E1/V1Hildebrand/Scott EM=12(x1V1+x2V2)(1-2)2Patterson/Delmas Gnoncomb=12VM(1-2)2,THERMODYNAMIC BASIS(CONT.),Hansen HSPRa2=4(D1-D2)2+(P1-P2)2+(H1-H2)2Hansen Relative Energy Difference(RED)RED=Ra/RoFlory/HansenX/XC=(RED)2Prigogine(With Geometric Mean)2=(2Prig/4+92)where Prig=(2-1)/1Prigogine/Hansen 2Prig=(i1-i2)/o2For“i”=P,HPanayiotou-Direct Calculation of Hydrogen Bonding,STATISTICAL THERMODYNAMICS-PANAYIOTOU,Equation of state:Chemical potential:,PANAYIOTOU 2D,2P,and 2H,2H-COMPARISON,HANSEN PANAYIOTOUToluene2.002.00Tetralin2.902.90Acetone6.957.00Methyl Methacrylate 5.405.40Ethanol 19.43 19.981-Butanol 15.80 15.80Dimethyl sulfoxide 10.20 10.28Water 42.32 42.17,2H POLYMER COMPARISON,HANSEN PANAYIOTOULin.Polyethylene2.802.80Polystyrene 2.902.90PVC 3.403.42PMMA 5.10 5.10PC 6.906.90Nylon 66 24.00 23.90,FREE ENERGY CHANGE,G,DETERMINES SOLUBILITY OR NOT,Free energy G must be negative for solutionG=(1/N)ln()+(1-)ln(1-)+(1-)is the solvent volume fractionN is the number of monomers in chain=Vm/RT(D1-D2)2+0.25(P1-P2)2+0.25(H1-H2)2 is the chi parameter,Vm is the molar volume,P VERSUS H PLOT,HANSEN SOLUBILITY PARAMETER DIAGRAM,KEY EQUATIONS,Ra2=4(D1-D2)2+(P1-P2)2+(H1-H2)2The experimentally verified”4”is also found in Prigogines CST theoryRED=Ra/Ro(Distance to sphere center divided by its radius)(RED)2=(Ra/Ro)2 corresponds to 12/c in Huggins/Flory Theory,SPHEROIDS OF SOLUBILITY UNLESS”4”IS USED,EFFECT OF TEMPERATURE,Higher temperature Lower values Larger effect for H,CHANGE OF H WITH TEMPERATURE(Williams),Table 10.3.Experimentally determined values of Eh and,.,Hydrogen-bond parameter,Eh,CN,COOH,TYPES OF MATERIALS,SOLVENTSPOLYMERSPIGMENT SURFACESFIBER SURFACESDRUGSCHEMICAL PROTECTIVE CLOTHINGBIOLOGICAL MATERIALSSALTS-BOTH ORGANIC AND INORGANIC,EXAMPLES OF USES OF HSP,Solvent Selection and Substitution(REACH,Ozone Depletion,VOC,etc.)Solubility,Swelling,Related PhenomenaSurface Characterization and AdhesionPermeation,Breakthrough TimesPhysical Properties Polymer and Biological CompatibilityControlled Drug Release,CHOLESTEROL NONSOLVENT SYNERGISM,BOUNDARY SOLVENTS(MIXTURES)HAVE TRADITIONALLY BEEN THE LEAST EXPENSIVE,XYLENE PLUS n-BUTANOL CAN OFTEN APPROACH THE PERFORMANCE OF OTHER WIDELY USED SOLVENTS,NON COMPATIBLE POLYMERS DISSOLVED IN A MIXTURE OF NON-SOLVENTS,SOLVENT AFFECTS PIGMENT DISPERSION STABILITY,Solvent 1 Optimum in most cases binder on pigmentSolvent 2 Too good for binder removes binder Solvent 3 Too good for pigment replaces binder,REPLACE OZONE DEPLETERSMatch Soil HSPUse Azeotropes,SBS MUST BE PARTLY COMPATIBLE WITH BITUMEN,VARNISH REMOVAL FROM OLD PAINTINGS,Teas Triangular Plot for Solvent Selection,MODIFICATION OF HANSEN PARAMETERSfd=100D/(D+P+H)fp=100P/(D+P+H)fh=100H/(D+P+H),TEAS PLOT,SOLUBILITY OF CARBON-60,COC-SOLUBILITY SHADEDESC CLEAR,ENVIRONMENTAL STRESS CRACKING CORRELATES WITH RED NUMBER AND MOLAR VOLUME,ESC in PC,HSP FOR”CARBON”MATERIALS,SURFACTANTS Two HSP regions required,SURFACE PHENOMENA EPOXY FILM,A-Spontaneous spreadingB-No dewettingC-Spontaneous dewetting,FIBER SURFACE CHARACTERIZATION,A Glassy CarbonB Carbon FibersC PP Fibers,SELF-ASSEMBLY,Lower energy polymer is surface layer in two layer film deposited from true solution,SELF-ASSEMBLY THIXOTROPIC PAINT,VERSAMID SEGMENTS ASSOCIATEALCOHOLS WILL DESTROY EFFECTSHEAR BREAKS STRUCTURE TEMPORARILY,BREAKTHROUGH TIMESmaller molecules with linear structure and low RED diffuse faster-PTFE,HSP FOR CYTOTOXIC DRUGS FOR GLOVE SELECTION,CHEMICAL D P H VFluorouracil18.011.711.6118.3Gemcitabine19.012.615.5260.6Cyclophosphamide17.511.912.6279.1Ifosfamide17.511.9 9.8261.1Methotrexate18.010.214.2378.7Etoposide20.0 7.512.5588.5Paclitaxel(Taxol)18.0 6.6 9.8853.9Average Group 118.310.312.3-Cytarabine 19.015.220.1187.1(Pyrimidine/arabinose)Carboplatin(Organic Pt)27.3 9.010.4185.1,CYCLOPHOSPHAMIDE BREAKTHROUGH TIMESNITRILE 45 MINUTES,BUTYL 4 HOURS,PERMEATION-VIABLE HUMAN SKINUrsin,et.al.,J.Am.Ind.Hyg.Assoc.,56,651(1995).,SIGMOIDAL ABSORPTION TIME DELAY WITH SQRT TIME,ABSORPTION LINEAR WITH TIMECASE II,ABSORPTION FASTER THAN LINEAR WITH TIME SUPER CASE II,HSP FOR ORGANIC SALTS,Material D P HDMEA-DimethylEthanolamine16.1 9.2 15.3Formic Acid14.3 11.9 16.6Acetic Acid14.5 8.0 13.5DMEA/Formic Acid17.2 21.5 22.5DMEA/Acetic Acid16.8 19.8 19.8ALL VALUES HIGHER,HSP FOR IONIC LIQUIDS,Ionic liquidDP Ht V,cc/molebmimCl19.1 20.720.735.0175.0bmimPF6 21.017.210.929.3207.6omimPF6 20.016.510.027.8276.0bmimBF423.019.010.031.5201.4 bmim is butyl methyl imidazole(o is octyl),Solvents having CO2 solubility greater than Ideal x=0.0229 at 25C and PCO2=1(Williams),BEST SOLVENTS CARBON DIOXIDE,HSP FOR CARBON DIOXIDE,Data Fit=1.000 for experimental data2D=15.7 MPa2P=6.3 MPa2H=5.7 MPaRo=3.3 MPa,CARBON DIOXIDE SOLUBILITY,HSP FOR SPECIAL CHEMICALS,Chemical D P H Amphetamine17.5 4.3 6.3Bisphenol A19.2 5.913.8d-Camphor17.8 9.4 4.72-Ethyl hexyl phthalate(MEHP)17.3 6.2 6.8Hexanal15.8 8.5 5.4Nicotine18.5 7.8 6.5L-Menthol16.6 4.710.6Paracetemol17.810.513.9Paraquat19.5 8.8 5.9Skatole20.0 7.1 6.22-Tert-butyl-4-methyl phenol17.3 3.710.5Triacetin16.5 4.5 9.1Triclosan20.0 7.710.0Vanillin18.610.613.8,HSP AVAILABLE FOR 1200 CHEMICALS INCLUDING:,Adrenaline,Ascorbic Acid,Bethoxazin,Caffeine,Carbon Dioxide,Cholesterol,DNA,Dopamine,Ecstasy,Lignin,Meclofenoxate,Norephedrin,Palm Oil,Quinine,Saccarine,Serotonin,Spermidin,Sucrose,Urea,Zein,Etc.,Etc.,SIMILARITY TO TETRABROMOBISPHENOL A,MATERIAL D P H Ra RED TBBPATBBPA20.2 9.1 13.8-0.0PENTACHLORO-PHENOL21.5 6.9 12.8 3.5(close)LIGNIN21.914.1 16.9 6.8 0.5RAPID SKIN PERMEABILITY17.612.5 11.0 6.5 0.36PSORIASIS SCALE SWELLING24.611.9 12.9 9.3 0.49,DIOXIN PHYSICAL INTERACTIONS,DPH20.09.27.6PREDICTIONS:Moderate Skin Permeation Rate(Large Size)Ready Absorption into Lignin(Plants),ULTRASTRUCTURE OF WOODHEMICELLULOSE SIDE CHAINS ORIENT,BOUNDARY HSP MATCH(LIGNIN)(LIGNIN)Ac Ac Ac Ac 2 3 2 3 M14M14M14G14M14G14M14M14G 3 6 1 1 M Ga(CELLULOSE)(CELLULOSE)GOOD HSP MATCH,HSP FOR WATER,D P H RoSingle molecule15.516.042.3 1%soluble in 15.120.416.5 18.1 Data Fit 0.856Good/Total 88/167Total miscibility18.117.116.9 13.0Data Fit 0.880Good/Total 47/166,CHEMICALS AFFECTING DNA-Tso P.O.P.,Et.Al.Natl Acad Sci.,U S A,48,686-698,(1962),Increasing activity was found to be:Adonitol,Methyl Riboside(both negligible)Cyclohexanol Phenol,Pyrimidine,Uridine Cytidine,Thymidine Purine,Adenosine,Inosine,Deoxyguanosine Caffeine,Coumarin,2,6-Dichloro-7-Methylpurine PLUS Formamide and Dimethyl Sulfoxide,HSP CORRELATION FOR DNA,HSP FOR DNA,Chemicals ordered correctlyThose not calculated have molecules that are too complicated and too large to be directly compared with the other smaller molecules.RESULT(MPa)2D 2P 2H19.0 20.0 11.0 EH is 14%of E,HSP FOR DNA BASES,Segment D P H“V”In H2O Parts/100Guanine20.012.712.5126.1 Insol.Cytosine19.5 12.1 9.9107.8 0.77Adenine20.0 10.2 13.7131.5 0.05Thymine19.5 14.2 12.6121.7 0.4Average19.75 12.3 12.2-,ESSENTIALLY INDENTICAL HSP:DNA BASES,CYTOTOXIC DRUGS AND RAPID SKIN PERMEATION,D P H Ra Ra(bases)(Gp 1)Rapid Skin Perm.17.612.511.0 4.47 2.91DNA bases19.7512.312.2-3.52Ave.Group 1 Drugs18.310.312.3 3.52-Synergism will be found for any of:Phthalate plasticicizers,tricresyl phosphate,N-methyl-2-pyrrolidone,Mixed with any of:Ethanol,2-propanol,ethylene glycol,propylene glycol,or glycerol,HSP DIFFERENT FOR DNA BASES,DNA,PROTEINS,AND DEPOT FAT,D P H Ro Fit Ra(Bases)DNA 19.020.011.011.0 1.000 7.93(Molecule)Zein 22.49.819.411.90.964 9.28(Protein)Lard 15.91.25.412.01.000 15.87(Depot Fat),CHEMOTHERAPY DRUGS WITHETHANOL/DOP MIXTURES,COCKTAIL FOR CONSIDERATIONMETHYL PARABEN+DOP+ETHANOLTARGET:CHEMODRUG HSP SPHERE,OPTIMUM NMR SOLVENT MIXTURES ARE POSSIBLE,HPLC RETENTION TIME,Retention time basedon HSP of solute,mobile and stationary phases,WHOLE EQUALS SUM OF PARTSE=COHESION ENERGY=Evap,E=ED+EP+EH D-Dispersion(Hydrocarbon)P-Polar(Dipolar)H-Hydrogen Bonds(Electron Interchange)V-Molar Volume E/V=ED/V+EP/V+EH/V 2=2D+2P+2H HANSEN SOLUBILITY PARAMETERS(HSP)=Square Root of Cohesion Energy Density,SUMMARY,HSP have now existed since 1967The first edition of HSPiP came in November,2008.Uses:Solubility(Gases,Liquids,Polymers,Solids),Compatibility,Swelling,Selection of ChemicalProtective Clothing,Permeation Rates,ControlledDrug Release,Environmental Stress Cracking,Self-Assembly,Physical Properties,Conservation ofPaintings,Surface Characterization,Improvement ofPhysical Adhesion,Bitumen,Asphalt,Organic Salts,Inorganic Salts,Explosives,Biologicals,Aromas,Surfactants,Subcritical Extraction,Supercritical gasesWhat Else?,Hansen Solubility Parameters in PracticeeBook,Software,and Examples,The HSPiP software:Finds HSP for solute(drug)with solubility dataOptimizes solvent blends for given target HSPShows which solvents can dissolve a soluteShows polymers that are likely to be compatibleModels absorption,desorption,and permeationHSP for chemicals/polymers with structureCalculates HPLC solvents and IGC results,Thank you for your attention!For further contact please visit:www.hansen-,