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HANSEN SOLUBILITY PARAMETERS CHARLES M. HANSEN

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CHARLES M. HANSEN. HANSEN SOLUBILITY PARAMETERS. 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. - PowerPoint PPT Presentation

### Text of HANSEN SOLUBILITY PARAMETERS

• 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 Rogers

To 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

• DHOMOMORPH 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

• H1. 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 HSPExchange 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)/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 NOTFree energy G must be negative for solution

G = (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 EQUATIONSRa2 = 4(D1 - D2)2 + (P1 - P2)2 + (H1 - H2)2

The experimentally verified 4 is also found in Prigogines CST theory

RED = 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 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 MATERIALSSOLVENTSPOLYMERSPIGMENT SURFACESFIBER SURFACESDRUGSCHEMICAL PROTECTIVE CLOTHINGBIOLOGICAL MATERIALSSALTS - BOTH ORGANIC AND INORGANIC

• EXAMPLES OF USES OF HSPSolvent 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 PAINTINGSTeas Triangular Plot for Solvent SelectionMODIFICATION OF HANSEN PARAMETERS

fd = 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

Chart1

74740.944747474

52.652.61.16852.652.652.6

68.468.41.22868.468.468.4

0.91289.489.489.489.489.4

103.60.858103.6103.6103.6103.6

91.591.591.591.51.22691.5

132.50.996132.5132.5132.5132.5

76.80.69676.876.876.876.8

97.197.10.99797.197.197.1

1061061061061061.002

0.625104104104104104

195.9195.9195.9195.9195.91.228

191.8191.8191.8191.81.005191.8

2662660.583266266266

77777777770.861

1630.461163163163163

224.5224.5224.5224.5224.51.007

58.558.558.558.51.41958.5

156.6156.6156.6156.61.12156.6

66661666666

55.855.855.855.855.81.768

39.839.839.839.839.81.811

73.373.373.31.99173.373.3

147.4147.4147.4147.41.274147.4

294.1294.1294.1294.1294.11.161

131.6131.6131.6131.61.321131.6

124.9124.9124.91.079124.9124.9

117.4117.4117.4117.4117.41.47

40.740.740.740.740.71.676

79.779.70.96779.779.779.7

90.10.85490.190.190.190.1

106.7106.70.866106.7106.7106.7

102.7102.70.255102.7102.7102.7

71.571.571.50.97271.571.5

54.354.354.31.1454.354.3

163.5163.5163.5163.51.251163.5

157.7157.7157.7157.71.061157.7

116.2116.2116.2116.21.37116.2

108.6108.6108.6108.61.139108.6

75.275.275.275.21.29675.2

76.876.876.876.876.81.272

850.70385858585

73.673.673.673.673.61.588

261.3261.3261.3261.3261.31.172

1141141141141.37114

166.1166.1166.1166.1166.11.419

123.30.908123.3123.3123.3123.3

&L&D&C&F

Glycerol 0,77 , 1,99

2-Propanol 1,02

Cyclohexanol 0,98 , 1,48

Dimethylformamide 1,55

0-0,2

0,2-0,4

0,4-0,6

0,6-0,8

0,8-1,0

>1

MOL VOLUME - CC/MOL

RED NO.

CALCULATED ESC FOR PCAT CRITICAL STRAIN = 0,6

0,0 -0,2

Solubility parameter for polycarbonate

MOLCRITICAL STRAINCRITICAL

NO.SOLVENTVOLUME0-0,20,2-0,40,4-0,60,6-0,80,8-1,0>1RED NO.STRAIN

7ACETONE740.9440.9440.51

10ACETONITRILE52.61.1681.1680.57

30ALLYL ALCOHOL68.41.2281.2280.56

52BENZENE89.40.9120.9120.2

58BENZYL ALCOHOL103.60.8580.8580.26

921-BUTANOL91.51.2261.2260.83

102n-BUTYL ACETATE132.50.9960.9960.35

115GAMMA BUTYROLACTONE76.80.6960.6960.3

122CARBON TETRACHLORIDE97.10.9970.9970.46

182CYCLOHEXANOL1061.0021.0021.23

183CYCLOHEXANONE1040.6250.6250.15

196DECANE195.91.2281.2281.03

1971-DECANOL191.81.0051.0050.97

221DIBUTYL PHTHALATE2660.5830.5830.41

297DIMETHYL FORMAMIDE770.8610.8611.57

300DIMETHYL PHTHALATE1630.4610.4610.31

1075DODECANOL224.51.0071.0071.17

325ETHANOL58.51.4191.4191

3452-ETHYL-HEXANOL156.61.121.120.87

363ETHYLENE CARBONATE66110.52

368ETHYLENE GLYCOL55.81.7681.7681.9

397FORMAMIDE39.81.8111.8111.55

406GLYCEROL73.31.9911.9910.77

409HEPTANE147.41.2741.2740.91

417HEXANE131.61.3211.3210.86

9301-HEXANOL124.91.0791.0790.71

437ISOPENTANE117.41.471.471.07

456METHANOL40.71.6761.6761.19

464METHYL ACETATE79.70.9670.9670.59

481METHYL ETHYL KETONE90.10.8540.8540.32

499METHYL n-PROPYL KETONE106.70.8660.8660.5

531NITROBENZENE102.70.2550.2550.51

532NITROETHANE71.50.9720.9720.72

534NITROMETHANE54.31.141.140.69

540OCTANE163.51.2511.2510.92

5421-OCTANOL157.71.0611.0610.93

550PENTANE116.21.371.370.83

5521-PENTANOL108.61.1391.1390.91

5691-PROPANOL75.21.2961.2960.91

5702-PROPANOL76.81.2721.2721.02

584PROPYLENE CARBONATE850.7030.7030.28

585PROPYLENE GLYCOL73.61.5881.5881.46

657TRIETHYLENEGLYCOL1141.371.370.98

6702.2.4-TRIMETHYLPENTANE166.11.4191.4191.66

697XYLENE123.30.9080.9080.37

&L&D&C&F

2-propanol 1.02

Cyclohexanol

sheet 2

&L&D&C&F

sheet 2

11111

&L&D&COSpolycarbonate140801

Glycerol 0,77 , 1,99

Cyclohexanol

Dimethylformamide

2-Propanol

#REF!

#REF!

#REF!

#REF!

#REF!

MOL VOLUME - CC/MOL

RED NO.

CALCULATED ESC FOR PCAT CRITICAL STRAIN = 0,6

Sheet3

Glycerol 0,77 , 1,99

• HSP FOR CARBON MATERIALS

• SURFACTANTS Two HSP regions required

• SURFACE PHENOMENA EPOXY FILMA - Spontaneous spreadingB - No dewettingC - Spontaneous dewetting

• FIBER SURFACE CHARACTERIZATIONA 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 PAINTVERSAMID 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 SELECTIONCHEMICAL 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

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)17.602.102.107.0014.362.05

125NAT 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 LIQUIDS

Ionic liquidDP Ht V, cc/mole[bmim]Cl19.1 20.720.735.0175.0[bmim]PF6 21.017.210.929.3207.6[omim]PF6 20.016.510.027.8276.0[bmim]BF423.019.010.031.5201.4

[bmim] is butyl methyl imidazole (o is octyl)

• Solvents having CO2 solubility greater than Ideal x =0.0229 at 25C and PCO2 = 1 (Williams)

Solventdd(MPa)1/2dp(MPa)1/2dh(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 DIOXIDEData Fit = 1.000 for experimental data2D = 15.7 MPa2P = 6.3 MPa2H = 5.7 MPaRo = 3.3 MPa

• CARBON DIOXIDE SOLUBILITY

• HSP FOR SPECIAL CHEMICALSChemical 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 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

DPH20.09.27.6

PREDICTIONS: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 - 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 DNAChemicals 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 BASESSegment D P HV 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 FATD 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 TIMERetention 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 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-solubility.com

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