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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.

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Presentation on theme: "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."— Presentation transcript:

1 HANSEN SOLUBILITY PARAMETERS CHARLES M. HANSEN

2 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

3 WHOLE EQUALS SUM OF PARTS E = COHESION ENERGY = ΔE vap E = E D + E P + E H D - Dispersion (Hydrocarbon) P - Polar (Dipolar) H - Hydrogen Bonds (Electron Interchange) V - Molar Volume E/V = E D /V + E P /V + E H /V  2 =  2 D +  2 P +  2 H HANSEN SOLUBILITY PARAMETERS (HSP)  = Square Root of Cohesion Energy Density

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

5 FIGURE FOR E D FOR ALIPHATIC HYDROCARBONS

6 PP Böttcher Equation cal/cm 3 Beerbower Equation MPa ½  P = 37.4(µ)/V ½

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

8 THERMODYNAMIC BASIS OF HSP Exchange Energy (Density) A 12 = ε 11 + ε ε 12 Geometric Mean ε 12 = (ε 11 ε 22 ) ½ Scatchard A 12 = (ε ½ 11 - ε ½ 22 ) 2 Hildebrand (Cohesive Energy Density) ε 11 = ΔE 1 /V 1 ; ε 22 = ΔE 1 /V 1 Hildebrand/Scott ΔE M = φ 1 φ 2 (x 1 V 1 + x 2 V 2 )(  1 -  2 ) 2 Patterson/Delmas ΔG noncomb = φ 1 φ 2 V M (  1 -  2 ) 2

9 THERMODYNAMIC BASIS ( CONT.) Hansen HSP Ra 2 = 4(  D1 -  D2 ) 2 + (  P1 -  P2 ) 2 + (  H1 -  H2 ) 2 Hansen Relative Energy Difference (RED) RED = Ra/Ro Flory/Hansen X/X C = (RED) 2 Prigogine (With Geometric Mean) ν 2 = (  2 Prig /4 + 9ρ 2 ) where  Prig = (ε 2 - ε 1 )/ε 1 Prigogine/Hansen  2 Prig = [(  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  2 D,  2 P, and  2 H

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

13  2 H – 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 = V m /RT[(  D1 -  D2 ) (  P1 -  P2 ) (  H1 -  H2 ) 2 ] Χ is the chi parameter, V m is the molar volume

15  P VERSUS  H PLOT

16 HANSEN SOLUBILITY PARAMETER DIAGRAM

17 KEY EQUATIONS Ra 2 = 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) Table Experimentally determined values of E h and.Hydrogen-bond parameter, E h  CN  COOH Functional Group E H Cal/mol dE H /dT Cal/mol/°K -OH (aliphatic) 4650  NH 2 (aliphatic) 1350  CN (aliphatic) 500  COOH (aliphatic) 2750 

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 f d = 100  D /(  D +  P +  H ) f p = 100  P /(  D +  P +  H ) f h = 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 D P H Cyclophosphamide MATERIAL D P H Ro Ra RED 117NR 20 MIN NR 1 HR NR 4 HR BR 20 MIN BR 1 HR BR 4 HR (2) NAT 4 HR PVC 20 MIN PVC 1 H PVC 4 HR PVA 20 MIN PVA 1 HR PVA 4 HR PE 20 MIN PE 1 HR PE 4 HR VIT 20 MIN VIT 1 HR VIT 4 HR NEO 20 MIN NEO 1 HR NEO 4 HR

45 PERMEATION - VIABLE HUMAN SKIN Ursin,et.al.,J.Am.Ind.Hyg.Assoc., 56, 651 (1995).

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 liquidδ D δ P δ H δ t V, cc/mole [bmim]Cl [bmim]PF [omim]PF [bmim]BF [bmim] is butyl methyl imidazole (o is octyl)

51 Solvents having CO 2 solubility greater than Ideal x = at 25°C and P CO2 = 1 (Williams) Solvent  d (MPa) 1/2  p (MPa) 1/2  h (MPa) 1/2 Tributyl phosphate, (C 12 H 27 O 4 P) Amyl acetate, (C 7 H 14 O 2) Butyl oleate, (C 22 H 42 O 2) Tetrahydrofuran (C 4 H 8 O) Methyl oleate (C 19 H 36 O 2 ) Isobutyl acetate (C 6 H 12 O 2 ) Methyl ethyl ketone (C 4 H 8 O) Propyl acetate (C 5 H 10 O 2 ) Ethyl acetate (C 4 H 8 O 2 ) Methyl acetate (C 3 H 6 O 2 )

52 BEST SOLVENTS CARBON DIOXIDE

53 HSP FOR CARBON DIOXIDE Data Fit = for experimental data  2 D = 15.7 MPa ½  2 P = 6.3 MPa ½  2 H = 5.7 MPa ½ Ro = 3.3 MPa ½

54 CARBON DIOXIDE SOLUBILITY

55 HSP FOR SPECIAL CHEMICALS Chemical  D  P  H Amphetamine Bisphenol A d-Camphor Ethyl hexyl phthalate (MEHP) Hexanal Nicotine L-Menthol Paracetemol Paraquat Skatole 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 R a RED TBBPA TBBPA PENTACHLORO- PHENOL (close) LIGNIN RAPID SKIN PERMEABILITY PSORIASIS SCALE SWELLING

58 DIOXIN PHYSICAL INTERACTIONS DPH 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 2 3 M1  4M1  4M1  4G1  4M1  4G1  4M1  4M1  4G– 3 6   1 1 M Ga (CELLULOSE) (CELLULOSE) GOOD HSP MATCH

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

61 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 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 (MPa ½ )  2 D  2 P  2 H E H is 14% of E

64 HSP FOR DNA BASES Segment D P H“V” In H 2 O 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 = ΔE vap E = E D + E P + E H D - Dispersion (Hydrocarbon) P - Polar (Dipolar) H - Hydrogen Bonds (Electron Interchange) V - Molar Volume E/V = E D /V + E P /V + E H /V  2 =  2 D +  2 P +  2 H HANSEN SOLUBILITY PARAMETERS (HSP)  = Square Root of Cohesion Energy Density

72 SUMMARY HSP have now existed since 1967 The first edition of HSPiP came in November, 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! For further contact please visit:


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