hansen solubility parameters.ppt

HANSEN SOLUBILITY PARAMETERS CHARLES M. HANSENWHY KEEP GOING?”Even if you’re on the right track, you’ll get run over if you just sit there.”-Will Rogers-To me this means help develop the -Hansen Solubility Parameters in Practice-(HSPiP) eBook/softwareWHOLE EQUALS SUM OF PARTSE = COHESION ENERGY = ΔEvapn E = ED + EP + EHn D - Dispersion (Hydrocarbon)n P - Polar (Dipolar)n H - Hydrogen Bonds (Electron Interchange)n V - Molar Volumen E/V = ED/V + EP/V + EH/V  2 =  2D +  2P +  2H HANSEN SOLUBILITY PARAMETERS (HSP)  = Square Root of Cohesion Energy Density DnHOMOMORPH CONCEPT (ED = E FOR SIMILAR HYDROCARBON)nCORRESPONDING STATE THEORY (CST)nCST 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 Böttcher Equation cal/cm3 Beerbower Equation MPa½ P = 37.4(µ)/V½ H1. EH = E - ED - EP 2. Panayiotou – statistical thermodynamics directly3. Group Contributions H = (EH/V)½4. CHECK where possible that:  2 =  2D +  2P +  2HTHERMODYNAMIC BASIS OF HSPExchange Energy (Density)A12 = ε11 + ε22 - 2ε12 Geometric Meanε12 = (ε11ε22)½ScatchardA12 = (ε½11 - ε½22)2Hildebrand (Cohesive Energy Density)ε11 = ΔE1/V1; ε22 = ΔE1/V1Hildebrand/Scott ΔEM = φ1φ2(x1V1 + x2V2)(1 - 2)2Patterson/Delmas ΔGnoncomb = φ1φ2VM(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)ν2 = (2Prig /4 + 9ρ2) where  Prig = (ε2 - ε1)/ε1Prigogine/Hansen  2Prig = [(i1 - i2)/o]2For “i” = P,HPanayiotou - Direct Calculation of Hydrogen Bonding STATISTICAL THERMODYNAMICS- PANAYIOTOUEquation 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 NOTnFree energy G must be negative for solutionnG = (1/N)øln(ø) + (1 - ø)ln(1 - ø) + Χø(1 - ø)n ø is the solvent volume fractionnN is the number of monomers in chainnΧ = Vm/RT[( D1 -  D2)2 + 0.25( P1 -  P2)2 + 0.25( H1 -  H2)2 ]nΧ is the chi parameter, Vm is the molar volumeP VERSUS H PLOTHANSEN SOLUBILITY PARAMETER DIAGRAMKEY EQUATIONSnRa2 = 4(D1 - D2)2 + (P1 - P2)2 + (H1 - H2)2nThe experimentally verified ”4” is also found in Prigogine’s CST theorynRED = Ra/Ro (Distance to sphere center divided by its radius)n(RED)2 = (Ra/Ro)2 corresponds to  12 /  c in Huggins/Flory TheorySPHEROIDS OF SOLUBILITY UNLESS ”4” IS USEDEFFECT OF TEMPERATUREHigher 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 FunctionalGroup EH Cal/mol dEH/dTCal/mol/°K -OH (aliphatic)4650  400-10-NH2 (aliphatic)1350  200-4.5-CN(aliphatic)500  200-7.0-COOH(aliphatic)2750  250-2.9TYPES OF MATERIALSnSOLVENTSnPOLYMERSnPIGMENT SURFACESnFIBER SURFACESnDRUGSnCHEMICAL PROTECTIVE CLOTHINGnBIOLOGICAL MATERIALSnSALTS - BOTH ORGANIC AND INORGANICEXAMPLES OF USES OF HSPnSolvent Selection and Substitution (REACH, Ozone Depletion, VOC, etc.)nSolubility, Swelling, Related PhenomenanSurface Characterization and AdhesionnPermeation, Breakthrough TimesnPhysical Properties nPolymer and Biological CompatibilitynControlled 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 nSolvent 1 – Optimum in most cases – binder on pigmentnSolvent 2 – Too good for binder – removes binder nSolvent 3 – Too good for pigment – replaces binderREPLACE OZONE DEPLETERSMatch Soil HSPUse AzeotropesSBS MUST BE PARTLY COMPATIBLE WITH BITUMENVARNISH REMOVAL FROM OLD PAINTINGSTeas Triangular Plot for Solvent SelectionMODIFICATION OF HANSEN PARAMETERSfd = 100 D/( D +  P +  H)fp = 100 P/( D +  P +  H)fh = 100 H/( 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 FILMnA - Spontaneous spreadingnB - No dewettingnC - Spontaneous dewettingFIBER SURFACE CHARACTERIZATIONnA – Glassy CarbonnB – Carbon FibersnC – PP FibersSELF-ASSEMBLY Lower energy polymer is surface layer in two layer film deposited from true solutionSELF-ASSEMBLY THIXOTROPIC PAINTnVERSAMID SEGMENTS ASSOCIATEnALCOHOLS WILL DESTROY EFFECTnSHEAR BREAKS STRUCTURE TEMPORARILYBREAKTHROUGH TIMESmaller molecules with linear structure and low RED diffuse faster - PTFE HSP FOR CYTOTOXIC DRUGS FOR GLOVE SELECTIONnCHEMICAL D P H VnFluorouracil18.011.711.6118.3nGemcitabine19.012.615.5260.6nCyclophosphamide17.511.912.6279.1nIfosfamide17.511.9 9.8261.1nMethotrexate18.010.214.2378.7nEtoposide20.0 7.512.5588.5nPaclitaxel (Taxol)18.0 6.6 9.8853.9nAverage Group 118.310.312.3 -nCytarabine 19.015.220.1187.1 (Pyrimidine/arabinose)nCarboplatin (Organic Pt)27.3 9.010.4185.1CYCLOPHOSPHAMIDE BREAKTHROUGH TIMESNITRILE 45 MINUTES, BUTYL >>4 HOURS D P H Cyclophosphamide17.511.912.6 MATERIAL D P H Ro Ra RED117NR 20 MIN17.507.306.505.107.641.50118NR 1 HR16.609.104.4010.008.850.88119NR 4 HR19.0012.603.8013.309.320.70120BR 20 MIN16.501.005.105.0013.382.68121BR 1 HR15.80-2.104.008.2016.782.05122BR 4 HR (2)17.602.102.107.0014.362.05125NAT 4 HR19.4013.207.7019.006.340.33126PVC 20 MIN16.107.105.909.308.700.94127PVC 1 H14.9011.103.8013.2010.250.78128PVC 4 HR24.404.909.9022.7015.710.69129PVA 20 MIN11.2012.4013.0012.1012.621.04130PVA 1 HR15.3013.2013.508.804.680.53131PVA 4 HR 17.2013.6015.4010.903.330.31132PE 20 MIN16.903.304.108.1012.151.50133PE 1 HR17.103.105.208.2011.531.41134PE 4 HR24.1014.900.3024.3018.290.75135VIT 20 MIN10.9014.503.1014.1016.471.17136VIT 1 HR16.508.108.306.606.080.92137VIT 4 HR13.6015.408.6014.409.440.66138NEO 20 MIN17.602.505.906.2011.551.86139NEO 1 HR19.008.000.0013.2013.531.02140NEO 4 HR14.6013.902.3015.9011.990.75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 SALTSMaterial 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 LIQUIDSnIonic liquidδDδP δHδt V, cc/molen[bmim]Cl19.1 20.720.7 35.0 175.0n[bmim]PF6 21.0 17.2 10.9 29.3 207.6n[omim]PF6 20.0 16.5 10.0 27.8 276.0n[bmim]BF423.0 19.0 10.0 31.5 201.4 [bmim] is butyl methyl imidazole (o is octyl)Solvents having CO2 solubility greater than Ideal x = 0.0229 at 25°C and PCO2 = 1 (Williams) Solventd dd(MPa)1/2d dp(MPa)1/2d dh(MPa)1/2Tributyl phosphate,(C12H27O4P)0.0355016.36.34.3Amyl acetate,(C7H14O2)0.0280015.83.36.1Butyl oleate,(C22H42O2)0.0279014.73.43.4Tetrahydrofuran(C4H8O)0.0270016.85.78.0Methyl oleate(C19H36O2)0.0269014.53.93.7Isobutyl acetate(C6H12O2)0.0250015.13.76.3Methyl ethyl ketone(C4H8O)0.0244416.09.05.1Propyl acetate(C5H10O2)0.0242915.34.37.6Ethyl acetate(C4H8O2)0.0230015.85.37.2Methyl acetate(C3H6O2)0.0225315.57.27.6BEST SOLVENTS CARBON DIOXIDEHSP FOR CARBON DIOXIDEnData Fit = 1.000 for experimental datan 2D = 15.7 MPa½n 2P = 6.3 MPa½n 2H = 5.7 MPa½nRo = 3.3 MPa½ CARBON DIOXIDE SOLUBILITY    HSP FOR SPECIAL CHEMICALSnChemical  D  P  H nAmphetamine17.5 4.3 6.3nBisphenol A19.2 5.913.8nd-Camphor17.8 9.4 4.7n2-Ethyl hexyl phthalaten (MEHP)17.3 6.2 6.8nHexanal15.8 8.5 5.4nNicotine18.5 7.8 6.5nL-Menthol16.6 4.710.6nParacetemol17.810.513.9nParaquat19.5 8.8 5.9nSkatole20.0 7.1 6.2n2-Tert-butyl-4-methyln phenol17.3 3.710.5nTriacetin16.5 4.5 9.1nTriclosan20.0 7.710.0nVanillin18.610.613.8 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 AMATERIAL  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 M14M14M14G14M14G14M14M14G– 3 6   1 1 M Ga (CELLULOSE) (CELLULOSE) GOOD HSP MATCHHSP FOR WATER D P H RonSingle molecule15.5 16.0 42.3 —n>1% soluble in 15.1 20.4 16.5 18.1 Data Fit 0.856Good/Total 88/167nTotal miscibility18.1 17.1 16.9 13.0Data Fit 0.880Good/Total 47/166CHEMICALS AFFECTING DNA - Ts'o 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 DNAnChemicals ordered correctlynThose not calculated have molecules that are too complicated and too large to be directly compared with the other smaller molecules. RESULT (MPa½) 2D  2P  2H19.0 20.0 11.0 EH is 14% of EHSP FOR DNA BASESSegment D P H“V” In H2O Parts/100Guanine20.0 12.7 12.5 126.1 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 FATD P H Ro Fit Ra (Bases) nDNA 19.020.011.011.0 1.000 7.93 (Molecule) nZein 22.49.819.411.90.964 9.28 (Protein)nLard 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 TIMERetention time basedon HSP of solute, mobile and stationary phasesWHOLE EQUALS SUM OF PARTSE = COHESION ENERGY = ΔEvapn E = ED + EP + EHn D - Dispersion (Hydrocarbon)n P - Polar (Dipolar)n H - Hydrogen Bonds (Electron Interchange)n V - Molar Volumen 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 ExamplesThe 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-www.hansen-。