WIXLIB

HANSEN SOLUBILITYPARAMETERSCHARLES M. HANSEN

WHY KEEP GOING?”Even if you’re on the right track, you’llget run over if you just sit there.”-To me this means help develop theHansen Solubility Parameters in Practice- (HSPiP) eBook/software--Will Rogers

WHOLE EQUALS SUM OF PARTSE COHESION ENERGY ΔEvap E ED EP EHD - Dispersion (Hydrocarbon)P - Polar (Dipolar)H - Hydrogen Bonds (Electron Interchange)V - Molar VolumeE/V ED/V EP/V EH/V 2 2D 2P 2HHANSEN SOLUBILITY PARAMETERS (HSP) Square Root of Cohesion Energy Density

D HOMOMORPH CONCEPT (ED E FORSIMILAR HYDROCARBON)CORRESPONDING STATE THEORY (CST)CST FIGURE FOR ED FOR EACH OFALIPHATIC, CYCLOALIPHATIC, ORAROMATIC STRUCTUREED versus V for Tr T298.15./TCRITICAL

FIGURE FOR ED FORALIPHATIC HYDROCARBONS

PBöttcher Equation cal/cm312108 122 n 2 D22V2 n D2P Beerbower Equation MPa½ P 37.4(µ)/V½

H1. EH E - ED - EP2. Panayiotou – statisticalthermodynamics directly3. Group Contributions½ H (EH/V)4. CHECK where possible that: D P H2222

THERMODYNAMIC BASIS OF HSPExchange Energy (Density)A12 ε11 ε22 - 2ε12Geometric Meanε12 (ε11ε22)½ScatchardA12 (ε½11 - ε½22)2Hildebrand (Cohesive Energy Density)ε11 E1/V1; ε22 E1/V1Hildebrand/Scott EM φ1φ2(x1V1 x2V2)( 1 - 2)2Patterson/Delmas Gnoncomb 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: lP T ln 1 H r z q zln1 ln 00 0r 2 2 Chemical potential: RT dpRT HRT zqzqqP1 ln l ln q ln 1 ln rr r r 2RT r2TT dp HRT r H d lnad a lna Hd H

PANAYIOTOU D, P, and H2 d rr qN r V m 2 2 rr qN r s r V p hb N H EHV22

2 H - COMPARISONHANSENTolueneTetralinAcetoneMethyl MethacrylateEthanol1-ButanolDimethyl PANAYIOTOU2.002.907.005.4019.9815.8010.2842.17

H – POLYMER COMPARISON2Lin. PolyethylenePolystyrenePVCPMMAPCNylon 03.425.106.9023.90

FREE ENERGY CHANGE, G,DETERMINES SOLUBILITY OR NOT Free energy G must be negative for solution G (1/N)øln(ø) (1 - ø)ln(1 - ø) Χø(1 - ø) ø is the solvent volume fractionN is the number of monomers in chainΧ Vm/RT[( D1 - D2)2 0.25( P1 - P2)2 0.25( H1 - H2)2 ]Χ is the chi parameter, Vm is the molar volume

P VERSUS HPLOT

HANSEN SOLUBILITYPARAMETER DIAGRAM p , Polar ParameterHansen Solubility Parameter DiagramInside:Plastic absorbs/dissolvesin liquidOutside:Plastic resists/stopsliquid H , Hydrogen Bonding Parameter

KEY EQUATIONS 222Ra 4( D1 - D2) ( P1 - P2) ( H1 - H2)2 The experimentally verified ”4” is also found inPrigogine’s CST theory RED Ra/Ro (Distance to sphere center dividedby its radius) (RED)2 (Ra/Ro)2 corresponds toHuggins/Flory Theory 12/ cin

SPHEROIDS OF SOLUBILITY UNLESS”4” IS USED

EFFECT OF TEMPERATUREHigher temperature – Lower valuesLarger effect for HT1 T2A1A2T1 PT2E1E2 H

CHANGE OF H WITH TEMPERATURE(Williams) 2.64 10 3 h h 22 T P h 1.32 10 3 2 parameter,Eh.HExperimentallydetermined values of Eh and COOH CNcaldEydrogen-bond dE Table 10.3.h h mole KdTdT HHFunctionalGroupEdE /dTCal/mol Cal/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 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 PropertiesPolymer and Biological CompatibilityControlled Drug Release

CHOLESTEROL NONSOLVENTSYNERGISM

BOUNDARY SOLVENTS (MIXTURES) HAVETRADITIONALLY BEEN THE LEASTEXPENSIVE

XYLENE PLUS n-BUTANOL CAN OFTENAPPROACH THE PERFORMANCE OFOTHER WIDELY USED SOLVENTS

NON – COMPATIBLE POLYMERSDISSOLVED IN A MIXTURE OF NONSOLVENTS

SOLVENT AFFECTSPIGMENT DISPERSION STABILITY Solvent 1 – Optimumin most cases –binder on pigmentSolvent 2 – Too goodfor binder – removesbinderSolvent 3 – Too goodfor pigment –replaces binder

REPLACE OZONE DEPLETERSMatch Soil HSPUse Azeotropes

SBS MUST BE PARTLYCOMPATIBLE WITH BITUMEN

VARNISH REMOVAL FROMOLD 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-60-10-9-8Log 10 (Mol fraction) Solubilities-7-6-5-4-3-2-1001234Red number567

COC - SOLUBILITY SHADEDESC CLEAR

ENVIRONMENTAL STRESS CRACKINGCORRELATES WITH RED NUMBER ANDMOLAR VOLUMETOPAS 6013 solubility D P HRO18.03.02.05.0SolubleESC3.0No ESC2.8DMFSevere deformationNEE2.6No problemat stress levelHSP, Red number for true solubility2.4CHKDAA2.2NMPACI2.02 405060708090 100 110 120 130 140 150 160 170Size parameter, V

ESC in PCCALCULATED ESC FOR PCAT CRITICAL STRAIN 0,62.5Glycerol 0,77 , 1,992RED NO1.52-Propanol 1,021Cyclohexanol 0,98 , 1,48Dimet hylf ormamide 1,550.50050100150200250MOL VOLUME - CC/MOL0-0,20,2-0,40,4-0,60,6-0,80,8-1,0 1300350

HSP FOR ”CARBON” MATERIALS20Carbon fiber, high181614"Carbon Black"12 P10Carbon Black 18Coal tar pitch64Carbon fiber, lowPetroleum CokeFullerene2002468 H10121416

SURFACTANTSTwo HSP regions required11cc Absorbed10 0.892128 P H3.13.72.78.77Hansen Plot - Lithium Stearate6 H54312112345 P6789

SURFACE PHENOMENA –EPOXY FILM A - SpontaneousspreadingB - No dewettingC - Spontaneousdewetting

FIBER SURFACECHARACTERIZATION A – Glassy CarbonB – Carbon FibersC – PP Fibers

SELF-ASSEMBLYPRIMERPolar solubility parameterLower energypolymer is surfacelayer in two layerfilm deposited fromtrue solutionTOPCOAT(lowest energy)Parametersrequired forcommon solventHydrogen bonding solubility parameter

SELF-ASSEMBLY THIXOTROPICPAINT VERSAMIDSEGMENTSASSOCIATEALCOHOLS WILLDESTROY EFFECTSHEAR BREAKSSTRUCTURETEMPORARILYAMineral spiritsBABB regions are not solubleand "precipitate" togetherBPolymer B (Versamid)BUTANOL PM.S.Polymer A (Alkyd) HA

BREAKTHROUGH TIMESmaller molecules with linear structure and low REDdiffuse faster - PTFE150D, P, H, R 16.6, 5.4, 4.0, 3.8FIT 0.997 for 68 MV 98Breakthrough time " " " No " 3 HR 3 HREvaluation uncertainBTCNoneBCNMIKBCLMolar TAEVEACAMAM BNZle CRP VAMMEKBTRTCLANLMANDOXbondTHF M POXARLMICCBBAACMBRAADAllATNMMA100500.01.02.03.0Red numberALANME4.05.0

HSP FOR CYTOTOXIC DRUGSFOR GLOVE SELECTION sfamideMethotrexateEtoposidePaclitaxel (Taxol)Average Group dine/arabinose)Carboplatin (Organic Pt)19.015.220.1187.127.39.010.4185.1

CYCLOPHOSPHAMIDE BREAKTHROUGH TIMESNITRILE 45 MINUTES, BUTYL 4 HOURSDPH11.912.6DPH117 NR 20 MIN17.507.306.50118 NR 1 HR16.609.10119 NR 4 HR19.00120 BR 20 105.0013.382.68121 BR 1 HR15.80-2.104.008.2016.782.05122 BR 4 HR (2)17.602.102.107.0014.362.05

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 LINEARWITH TIME – SUPER CASE II

HSP FOR ORGANIC SALTSMaterialDPHDMEA - DimethylEthanolamine16.1 9.2 15.3Formic Acid14.3 11.9 16.6Acetic Acid14.5 8.0 13.5DMEA/Formic Acid 17.2 21.5 22.5DMEA/Acetic Acid 16.8 19.8 19.8ALL VALUES HIGHER

HSP FOR IONIC LIQUIDS Ionic .020.023.0δP δH20.7 20.717.2 10.916.5 10.019.0 10.0δt V, cc/mole35.0 175.029.3 207.627.8 276.031.5 201.4[bmim] is butyl methyl imidazole (o is octyl)

Solvents having CO2 solubility greater than Ideal x 0.0229 at25 C and PCO2 1 (Williams)Solvent d p h(MPa)1/2(MPa)1/2(MPa)1/2Tributyl phosphate,(C12H27O4P)0.0355016.36.34.3Amyl acetate,(C7H14O2)0.0280015.83.36.1Butyl 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 SOLVENTSCARBON DIOXIDE

HSP FOR CARBON DIOXIDE Data Fit 1.000 for experimental data D 15.7 MPa2 P 6.3 MPa½2½ H 5.7 MPa½Ro 3.3 MPa2½

CARBON DIOXIDE SOLUBILITY

HSP FOR SPECIAL CHEMICALS P H17.54.36.3Bisphenol A19.25.913.8d-Camphor17.89.44.7 2-Ethyl hexyl phthalate(MEHP)17.36.26.8 Hexanal15.88.55.4 Nicotine18.57.86.5 L-Menthol16.64.710.6 Paracetemol17.810.513.9 Paraquat19.58.85.9 Skatole20.07.16.2 2-Tert-butyl-4-methylphenol17.33.710.5 Triacetin16.54.59.1 Triclosan20.07.710.0 Vanillin18.610.613.8 Chemical Amphetamine D

HSP AVAILABLE FOR 1200CHEMICALS 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 TOTETRABROMOBISPHENOL AMATERIAL D P HTBBPAPENTACHLOROPHENOLLIGNINRAPID SKINPERMEABILITYPSORIASIS 30.49Ra RED TBBPA

DIOXIN PHYSICAL INTERACTIONSD20.0P9.2H7.6PREDICTIONS:Moderate Skin Permeation Rate (Large Size)Ready Absorption into Lignin (Plants)

ULTRASTRUCTURE OF WOODHEMICELLULOSE SIDE CHAINS ORIENTBOUNDARY HSP MATCH(LIGNIN)(LIGNIN)Ac AcAcAc2323M1 4M1 4M1 4G1 4M1 4G1 4M1 4M1 4G–36 11MGa(CELLULOSE)(CELLULOSE)GOOD HSP MATCH

HSP FOR WATER Single molecule 1% soluble inData Fit 0.856Good/Total 88/167Total miscibilityData Fit 0.880Good/Total 47/166DPHRo15.5 16.0 42.3 —15.1 20.4 16.5 18.118.1 17.1 16.9 13.0

CHEMICALS AFFECTING DNA Ts'o P.O.P., Et.Al. Natl Acad Sci., U S A, 48, 686698, (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 PLUSFormamide and Dimethyl Sulfoxide

HSP CORRELATION FOR DNA

HSP FOR DNA Chemicals ordered correctlyThose not calculated have molecules thatare too complicated and too large to bedirectly compared with the other smallermolecules.RESULT (MPa½)222 D P H19.0 20.0 11.0EH is 14% of E

HSP FOR DNA H “V” In H2O Parts/10020.0 12.7 12.5 126.1 Insol.19.5 12.1 9.9 107.8 0.7720.0 10.2 13.7 131.5 0.0519.5 14.2 12.6 121.7 0.419.75 12.3 12.2 -

ESSENTIALLY INDENTICAL HSP:DNA BASES, CYTOTOXIC DRUGSAND RAPID SKIN PERMEATIONRapid Skin Perm.DNA basesAve. Group 1 DrugsDP17.619.7518.312.512.310.3HRa(bases)11.0 4.4712.212.3 3.52Ra(Gp 1)2.913.52-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 FATDPHRoFitRa (Bases) DNA19.0(Molecule)20.011.011.01.0007.93 Zein(Protein)22.49.819.411.90.9649.28 Lard15.9(Depot Fat)1.25.412.01.00015.87

CHEMOTHERAPY DRUGS WITHETHANOL/DOP MIXTURES

COCKTAIL FOR CONSIDERATIONMETHYL PARABEN DOP ETHANOLTARGET: CHEMODRUG HSP SPHERE

OPTIMUM NMR SOLVENTMIXTURES ARE POSSIBLE

HPLC RETENTION TIMERetention time basedon HSP of solute,mobile and stationaryphases

WHOLE EQUALS SUM OF PARTSE COHESION ENERGY ΔEvap E ED EP EHD - Dispersion (Hydrocarbon)P - Polar (Dipolar)H - Hydrogen Bonds (Electron Interchange)V - Molar VolumeE/V ED/V EP/V EH/V 2 2D 2P 2HHANSEN SOLUBILITY PARAMETERS (HSP) Square Root of Cohesion Energy Density

SUMMARYHSP 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?