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HANSEN SOLUBILITY PARAMETERS

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1 HANSEN SOLUBILITY PARAMETERS
CHARLES M. HANSEN

2 WHY KEEP GOING? Will Rogers
”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

3 WHOLE EQUALS SUM OF PARTS E = COHESION ENERGY = ΔEvap
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

4 D HOMOMORPH CONCEPT (ED = E FOR SIMILAR HYDROCARBON)
CORRESPONDING STATE THEORY (CST) CST FIGURE FOR ED FOR EACH OF ALIPHATIC, CYCLOALIPHATIC, OR AROMATIC STRUCTURE ED versus V for Tr=T /TCRITICAL

5 FIGURE FOR ED FOR ALIPHATIC HYDROCARBONS

6 P Böttcher Equation cal/cm3 Beerbower Equation MPa½ P = 37.4(µ)/V½

7 H 1. EH = E - ED - EP 2. Panayiotou – statistical thermodynamics directly 3. Group Contributions H = (EH/V)½ 4. CHECK where possible that: 2 = 2D 2P 2H

8 THERMODYNAMIC BASIS OF HSP
Exchange Energy (Density) A12 = ε11 + ε22 - 2ε12 Geometric Mean ε12 = (ε11ε22)½ Scatchard A12 = (ε½11 - ε½22)2 Hildebrand (Cohesive Energy Density) ε11 = ΔE1/V1; ε22 = ΔE1/V1 Hildebrand/Scott ΔEM = φ1φ2(x1V1 + x2V2)(1 - 2)2 Patterson/Delmas ΔGnoncomb = φ1φ2VM(1 - 2)2

9 THERMODYNAMIC BASIS (CONT.)
Hansen HSP Ra2 = 4(D1 - D2)2 + (P1 - P2)2 + (H1 - H2)2 Hansen Relative Energy Difference (RED) RED = Ra/Ro Flory/Hansen X/XC = (RED)2 Prigogine (With Geometric Mean) ν2 = (2Prig /4 + 9ρ2) where Prig = (ε2 - ε1)/ε1 Prigogine/Hansen 2Prig = [(i1 - i2)/o]2 For “i” = P,H Panayiotou - Direct Calculation of Hydrogen Bonding

10 STATISTICAL THERMODYNAMICS - PANAYIOTOU
Equation of state: Chemical potential:

11 PANAYIOTOU 2D, 2P, and 2H

12 2H - COMPARISON HANSEN PANAYIOTOU Toluene 2.00 2.00
Tetralin Acetone Methyl Methacrylate Ethanol 1-Butanol Dimethyl sulfoxide Water

13 2H – POLYMER COMPARISON
HANSEN PANAYIOTOU Lin. Polyethylene Polystyrene PVC PMMA PC Nylon

14 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 fraction N is the number of monomers in chain Χ = Vm/RT[(D1 - D2) (P1 - P2) (H1 - H2)2 ] Χ is the chi parameter, Vm is the molar volume

15 P VERSUS H PLOT

16 HANSEN SOLUBILITY PARAMETER DIAGRAM

17 KEY EQUATIONS Ra2 = 4(D1 - D2)2 + (P1 - P2)2 + (H1 - H2)2
The experimentally verified ”4” is also found in Prigogine’s 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

18 SPHEROIDS OF SOLUBILITY UNLESS ”4” IS USED

19 EFFECT OF TEMPERATURE Higher temperature – Lower values
Larger effect for H

20 CHANGE OF H WITH TEMPERATURE (Williams)
Functional Group EH Cal/mol dEH/dT Cal/mol/°K -OH (aliphatic) 4650  400 -10 -NH2 1350  200 -4.5 -CN 500  200 -7.0 -COOH 2750  250 -2.9 CN COOH Hydrogen-bond parameter, Eh Table Experimentally determined values of Eh and .

21 TYPES OF MATERIALS SOLVENTS POLYMERS PIGMENT SURFACES FIBER SURFACES
DRUGS CHEMICAL PROTECTIVE CLOTHING BIOLOGICAL MATERIALS SALTS - BOTH ORGANIC AND INORGANIC

22 EXAMPLES OF USES OF HSP Solvent Selection and Substitution (REACH, Ozone Depletion, VOC, etc.) Solubility, Swelling, Related Phenomena Surface Characterization and Adhesion Permeation, Breakthrough Times Physical Properties Polymer and Biological Compatibility Controlled Drug Release

23 CHOLESTEROL NONSOLVENT SYNERGISM

24 BOUNDARY SOLVENTS (MIXTURES) HAVE TRADITIONALLY BEEN THE LEAST EXPENSIVE

25 XYLENE PLUS n-BUTANOL CAN OFTEN APPROACH THE PERFORMANCE OF OTHER WIDELY USED SOLVENTS

26 NON – COMPATIBLE POLYMERS DISSOLVED IN A MIXTURE OF NON-SOLVENTS

27 SOLVENT AFFECTS PIGMENT DISPERSION STABILITY
Solvent 1 – Optimum in most cases – binder on pigment Solvent 2 – Too good for binder – removes binder Solvent 3 – Too good for pigment – replaces binder

28 REPLACE OZONE DEPLETERS Match Soil HSP Use Azeotropes

29 SBS MUST BE PARTLY COMPATIBLE WITH BITUMEN

30 VARNISH REMOVAL FROM OLD PAINTINGS
Teas Triangular Plot for Solvent Selection MODIFICATION OF HANSEN PARAMETERS fd = 100D/(D + P + H) fp = 100P/(D + P + H) fh = 100H/(D + P + H)

31 TEAS PLOT

32 SOLUBILITY OF CARBON-60

33 COC - SOLUBILITY SHADED ESC CLEAR

34 ENVIRONMENTAL STRESS CRACKING CORRELATES WITH RED NUMBER AND MOLAR VOLUME

35 ESC in PC

36 HSP FOR ”CARBON” MATERIALS

37 SURFACTANTS Two HSP regions required

38 SURFACE PHENOMENA – EPOXY FILM
A - Spontaneous spreading B - No dewetting C - Spontaneous dewetting

39 FIBER SURFACE CHARACTERIZATION
A – Glassy Carbon B – Carbon Fibers C – PP Fibers

40 SELF-ASSEMBLY Lower energy polymer is surface layer in two layer film deposited from true solution

41 SELF-ASSEMBLY THIXOTROPIC PAINT
VERSAMID SEGMENTS ASSOCIATE ALCOHOLS WILL DESTROY EFFECT SHEAR BREAKS STRUCTURE TEMPORARILY

42 BREAKTHROUGH TIME Smaller molecules with linear structure and low RED diffuse faster - PTFE

43 HSP FOR CYTOTOXIC DRUGS FOR GLOVE SELECTION
CHEMICAL D P H V Fluorouracil Gemcitabine Cyclophosphamide Ifosfamide Methotrexate Etoposide Paclitaxel (Taxol) Average Group Cytarabine (Pyrimidine/arabinose) Carboplatin (Organic Pt)

44 CYCLOPHOSPHAMIDE BREAKTHROUGH TIMES NITRILE 45 MINUTES, BUTYL >>4 HOURS
17.5 11.9 12.6 MATERIAL Ro Ra RED 117 NR 20 MIN 17.50 7.30 6.50 5.10 7.64 1.50 118 NR 1 HR 16.60 9.10 4.40 10.00 8.85 0.88 119 NR 4 HR 19.00 12.60 3.80 13.30 9.32 0.70 120 BR 20 MIN 16.50 1.00 5.00 13.38 2.68 121 BR 1 HR 15.80 -2.10 4.00 8.20 16.78 2.05 122 BR 4 HR (2) 17.60 2.10 7.00 14.36 125 NAT 4 HR 19.40 13.20 7.70 6.34 0.33 126 PVC 20 MIN 16.10 7.10 5.90 9.30 8.70 0.94 127 PVC 1 H 14.90 11.10 10.25 0.78 128 PVC 4 HR 24.40 4.90 9.90 22.70 15.71 0.69 129 PVA 20 MIN 11.20 12.40 13.00 12.10 12.62 1.04 130 PVA 1 HR 15.30 13.50 8.80 4.68 0.53 131 PVA 4 HR 17.20 13.60 15.40 10.90 3.33 0.31 132 PE 20 MIN 16.90 3.30 4.10 8.10 12.15 133 PE 1 HR 17.10 3.10 5.20 11.53 1.41 134 PE 4 HR 24.10 0.30 24.30 18.29 0.75 135 VIT 20 MIN 14.50 14.10 16.47 1.17 136 VIT 1 HR 8.30 6.60 6.08 0.92 137 VIT 4 HR 8.60 14.40 9.44 0.66 138 NEO 20 MIN 2.50 6.20 11.55 1.86 139 NEO 1 HR 8.00 0.00 13.53 1.02 140 NEO 4 HR 14.60 13.90 2.30 15.90 11.99

45 PERMEATION - VIABLE HUMAN SKIN Ursin,et. al. ,J. Am. Ind. Hyg. Assoc

46 SIGMOIDAL ABSORPTION – TIME DELAY WITH SQRT TIME

47 ABSORPTION LINEAR WITH TIME CASE II

48 ABSORPTION FASTER THAN LINEAR WITH TIME – SUPER CASE II

49 HSP FOR ORGANIC SALTS Material D P H DMEA - Dimethyl
Ethanolamine Formic Acid Acetic Acid DMEA/Formic Acid DMEA/Acetic Acid ALL VALUES HIGHER

50 HSP FOR IONIC LIQUIDS Ionic liquid δD δP δH δt V, cc/mole
[bmim]Cl [bmim]PF [omim]PF [bmim]BF [bmim] is butyl methyl imidazole (o is octyl)

51 Solvents having CO2 solubility greater than Ideal x = 0
Solvents having CO2 solubility greater than Ideal x =  at 25°C and PCO2 = 1 (Williams) Solvent dd (MPa)1/2 dp dh Tributyl phosphate, (C12H27O4P) 16.3 6.3 4.3 Amyl acetate, (C7H14O2) 15.8 3.3 6.1 Butyl oleate, (C22H42O2) 14.7 3.4 Tetrahydrofuran (C4H8O) 16.8 5.7 8.0 Methyl oleate (C19H36O2) 14.5 3.9 3.7 Isobutyl acetate (C6H12O2) 15.1 Methyl ethyl ketone 16.0 9.0 5.1 Propyl acetate (C5H10O2) 15.3 7.6 Ethyl acetate (C4H8O2) 5.3 7.2 Methyl acetate (C3H6O2) 15.5

52 BEST SOLVENTS CARBON DIOXIDE

53 HSP FOR CARBON DIOXIDE 2D = 15.7 MPa½ 2P = 6.3 MPa½ 2H = 5.7 MPa½
Data Fit = for experimental data 2D = 15.7 MPa½ 2P = 6.3 MPa½ 2H = 5.7 MPa½ Ro = 3.3 MPa½

54 CARBON DIOXIDE SOLUBILITY

55 HSP FOR SPECIAL CHEMICALS
Chemical D P H Amphetamine Bisphenol A d-Camphor 2-Ethyl hexyl phthalate (MEHP) Hexanal Nicotine L-Menthol Paracetemol Paraquat Skatole 2-Tert-butyl-4-methyl phenol Triacetin Triclosan Vanillin

56 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.

57 SIMILARITY TO TETRABROMOBISPHENOL A
MATERIAL D P H Ra RED TBBPA TBBPA PENTACHLORO- PHENOL (close) LIGNIN RAPID SKIN PERMEABILITY PSORIASIS SCALE SWELLING

58 DIOXIN PHYSICAL INTERACTIONS
D P H PREDICTIONS: Moderate Skin Permeation Rate (Large Size) Ready Absorption into Lignin (Plants)

59 ULTRASTRUCTURE OF WOOD HEMICELLULOSE SIDE CHAINS ORIENT
BOUNDARY HSP MATCH (LIGNIN) (LIGNIN) Ac Ac Ac Ac M14M14M14G14M14G14M14M14G–   M Ga (CELLULOSE) (CELLULOSE) GOOD HSP MATCH

60 HSP FOR WATER D P H Ro Single molecule 15.5 16.0 42.3 —
>1% soluble in Data Fit Good/Total 88/167 Total miscibility Data Fit 0.880 Good/Total 47/166

61 CHEMICALS AFFECTING DNA - Ts'o P. O. P. , Et. Al. Natl Acad Sci
CHEMICALS AFFECTING DNA - Ts'o P.O.P., Et.Al. Natl Acad Sci., U S A, 48, , (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

62 HSP CORRELATION FOR DNA

63 HSP FOR DNA EH is 14% of E Chemicals ordered correctly
Those not calculated have molecules that are too complicated and too large to be directly compared with the other smaller molecules. RESULT (MPa½) 2D 2P 2H EH is 14% of E

64 HSP FOR DNA BASES Segment D P H “V” In H2O Parts/100
Guanine Insol. Cytosine Adenine Thymine Average

65 ESSENTIALLY INDENTICAL HSP: DNA BASES, CYTOTOXIC DRUGS AND RAPID SKIN PERMEATION
D P H Ra Ra (bases) (Gp 1) Rapid Skin Perm DNA bases Ave. Group 1 Drugs 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

66 HSP DIFFERENT FOR DNA BASES, DNA, PROTEINS, AND DEPOT FAT
D P H Ro Fit Ra (Bases) DNA (Molecule) Zein (Protein) Lard (Depot Fat)

67 CHEMOTHERAPY DRUGS WITH ETHANOL/DOP MIXTURES

68 COCKTAIL FOR CONSIDERATION METHYL PARABEN+DOP+ETHANOL TARGET: CHEMODRUG HSP SPHERE

69 OPTIMUM NMR SOLVENT MIXTURES ARE POSSIBLE

70 HPLC RETENTION TIME Retention time based on HSP of solute,
mobile and stationary phases

71 WHOLE EQUALS SUM OF PARTS E = COHESION ENERGY = ΔEvap
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

72 SUMMARY The first edition of HSPiP came in November, 2008.
HSP have now existed since 1967 The first edition of HSPiP came in November, 2008. Uses: Solubility (Gases, Liquids, Polymers, Solids), Compatibility, Swelling, Selection of Chemical Protective Clothing, Permeation Rates, Controlled Drug Release, Environmental Stress Cracking, Self-Assembly, Physical Properties, Conservation of Paintings, Surface Characterization, Improvement of Physical Adhesion, Bitumen, Asphalt, Organic Salts, Inorganic Salts, Explosives, Biologicals, Aromas, Surfactants, Subcritical Extraction, Supercritical gases What Else?

73 Hansen Solubility Parameters in Practice eBook, Software, and Examples
The HSPiP software: Finds HSP for solute (drug) with solubility data Optimizes solvent blends for given target HSP Shows which solvents can dissolve a solute Shows polymers that are likely to be compatible Models absorption, desorption, and permeation HSP for chemicals/polymers with structure Calculates HPLC solvents and IGC results

74 Thank you for your attention!
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