Hansen Solubility Parameters

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. - To me this means help develop the Hansen Solubility Parameters in Practice - (HSPiP) eBook/software - - Will Rogers WHOLE EQUALS SUM OF PARTS E =COHESION E +E +E E= ENERGY = D - Dispersion (Hydrocarbon) E vap

P - Polar (Dipolar) D P H H - Hydrogen Bonds (Electron Interchange) V - Molar Volume E/V = ED/V + EP/V + EH/V 2 2 = 2 2

+ + D P H HANSEN SOLUBILITY PARAMETERS (HSP) = Square Root of Cohesion Energy Density 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=T298.15./TCRITICAL FIGURE FOR ED FOR ALIPHATIC HYDROCARBONS P Bttcher Equation cal/cm3

12108 1 2 2 2 n 2 D 2 V 2 n D 2 P Beerbower Equation MPa P = 37.4()/V H 1. EH = E - ED - EP 2. Panayiotou statistical

thermodynamics directly 3. Group Contributions H = (EH/V) 4. CHECK where possible that: = D + P + H 2 2 2 2 THERMODYNAMIC BASIS OF HSP Exchange Energy (Density) A12 = 11 + 22 - 212 Geometric Mean 12 = (1122) Scatchard A12 = (11 - 22)2 Hildebrand (Cohesive Energy Density) 11 = EE1/V1; 22 = EE1/V1 Hildebrand/Scott EEM = 12(x1V1 + x2V2)(1 - 2)2 Patterson/Delmas EGnoncomb = 12VM(1 - 2)2 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) 2 = (2Prig /4 + 92) where Prig = (2 - 1)/1 Prigogine/Hansen 2Prig = [(i1 - i2)/o]2 For i = P,H Panayiotou - Direct Calculation of Hydrogen Bonding STATISTICAL THERMODYNAMICS Equation of state: - PANAYIOTOU ~ ~ l P T ln 1 ~ ~ H r q z z

ln 1 ~ ~ ln 00 0 r 2 2 Chemical potential: dp H RT RT RT ~ 1 ~ z q zq q P ln l ln ~ q ln 1 ~ ~ ln rr ~ r ~ RT r 2 r 2 T T

dp H d a r H d ln a ln RT d H a H PANAYIOTOU D, P, and H 2 d rr qN r V m 2 2 rr qN r s r p V

hb N H EH V 2 2 2 H - COMPARISON Toluene Tetralin Acetone Methyl Methacrylate Ethanol 1-Butanol Dimethyl sulfoxide Water HANSEN PANAYIOTOU 2.00 2.90 6.95 5.40

19.43 15.80 10.20 42.32 2.00 2.90 7.00 5.40 19.98 15.80 10.28 42.17 2 H POLYMER COMPARISON HANSEN Lin. Polyethylene Polystyrene PVC PMMA PC Nylon 66 2.80 2.90 3.40

5.10 6.90 24.00 PANAYIOTOU 2.80 2.90 3.42 5.10 6.90 23.90 FREE ENERGY CHANGE, G, DETERMINES SOLUBILITY OR Free energy G must be negative for solution NOT G = (1/N)ln() + (1 - )ln(1 - ) + (1 - )(1 - ) is the solvent volume fraction N is the number of monomers in chain

(1 - ) = Vm/RT[(D1 - D2)2 + 0.25(P1 - P2)2 + 0.25(H1 - H2)2 ] (1 - ) is the chi parameter, Vm is the molar volume P VERSUS H PLOT HANSEN SOLUBILITY PARAMETER DIAGRAM p , Polar Parameter Hansen Solubility Parameter Diagram Inside: Plastic absorbs/dissolves in liquid Outside: Plastic resists/stops liquid H , Hydrogen Bonding Parameter KEY EQUATIONS

Ra2 = 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 Huggins/Flory Theory 12 / c in SPHEROIDS OF SOLUBILITY UNLESS 4 IS USED EFFECT OF TEMPERATURE Higher temperature Lower values Larger effect for H

T1 < T2 A1 A2 T1 P T2 E1 E2 H CHANGE OF H WITH TEMPERATURE (Williams) 2.64 10 3 h h 2

2 T P h 1.32 10 3 2 cal dE h COOH dE CN Hydrogen-bond Table 10.3. parameter, Experimentally Eh determined . values of Eh and h mole dT dT K Function

H H al Group E dE /dT Cal/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 SOLVENTS POLYMERS PIGMENT SURFACES FIBER SURFACES DRUGS CHEMICAL PROTECTIVE CLOTHING BIOLOGICAL MATERIALS SALTS - BOTH ORGANIC AND INORGANIC

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 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 pigment Solvent 2 Too good for binder removes binder Solvent 3 Too good for pigment replaces binder REPLACE OZONE DEPLETERS Match Soil HSP Use Azeotropes

SBS MUST BE PARTLY COMPATIBLE WITH BITUMEN VARNISH REMOVAL FROM OLD PAINTINGS Teas Triangular Plot for Solvent Selection MODIFICATION OF HANSEN PARAMETERS fd = 100D/(D + P + H) fp = 100P/(D + P + H) fh = 100H/(D + P + H) TEAS PLOT SOLUBILITY OF CARBON-60 -10 -9 -8 Log 10 (Mol fraction) Solubilities -7 -6

-5 -4 -3 -2 -1 0 0 1 2 3 4 Red number 5 6 7

COC - SOLUBILITY SHADED ESC CLEAR ENVIRONMENTAL STRESS CRACKING CORRELATES WITH RED NUMBER AND MOLAR VOLUME TOPAS 6013 solubility D 18.0 P 3.0 H RO 2.0 5.0

Soluble ESC 3.0 No ESC 2.8 DMF Severe deformation NEE 2.6 No problem at stress level HSP, Red number for true solubility 2.4 CHK DAA 2.2 NMP

ACI 2.0 2 NB 1.8 ESC possible 1.6 ISOPH EET THF 1.4 DOX 1.2 MCHL HXA ETA NTB ACETOPH

MIK BCN EDC 1.0 0.8 Solubility 0.6 0.4 0.2 0 10 20 30 40 50 60

70 80 90 100 110 120 130 140 150 160 170 Size parameter, V ESC in PC CALCULATED ESC FOR PC AT CRITICAL STRAIN = 0,6 2.5 Glycerol 0,77 , 1,99 2 RED NO. 1.5 2-P ropanol 1,02 1 Cyclohexanol 0,98 , 1,48 Dimethylformamide 1,55

0.5 0 0 50 100 150 200 250 MOL VOLUME - CC/MOL 0-0,2 0,2-0,4 0,4-0,6 0,6-0,8 0,8-1,0 >1

300 350 HSP FOR CARBON MATERIALS 20 Carbon fiber, high 18 16 14 "Carbon Black" 12 P 10 Carbon Black 1 8

Coal tar pitch 6 4 Carbon fiber, low Petroleum Coke Fullerene 2 0 0 2 4 6 8 H 10

12 14 16 SURFACTANTS Two HSP regions required 11 cc Absorbed 10 > 0.8 9 2 1 2 8 P H 3.1

3.7 2.7 8.7 7 Hansen Plot - Lithium Stearate 6 H 5 4 3 1 2 1 1 2 3 4 5

P 6 7 8 9 SURFACE PHENOMENA EPOXY FILM A - Spontaneous spreading B - No dewetting C - Spontaneous dewetting FIBER SURFACE CHARACTERIZATION

A Glassy Carbon B Carbon Fibers C PP Fibers SELF-ASSEMBLY PRIMER Polar solubility parameter Lower energy polymer is surface layer in two layer film deposited from true solution TOPCOAT (lowest energy) Parameters required for common solvent Hydrogen bonding solubility parameter SELF-ASSEMBLY THIXOTROPIC PAINT

VERSAMID SEGMENTS ASSOCIATE ALCOHOLS WILL DESTROY EFFECT SHEAR BREAKS STRUCTURE TEMPORARILY A Mineral spirits B A B B regions are not soluble and "precipitate" together B

Polymer B (Versamid) BUTANOL P M.S. Polymer A (Alkyd) H A BREAKTHROUGH TIME Smaller molecules with linear structure and low RED diffuse faster - PTFE 150 D, P, H, R = 16.6, 5.4, 4.0, 3.8 FIT = 0.997 for 68 < MV < 98 Breakthrough time " = " " No = " < 3 HR > 3 HR Evaluation uncertain BTC

None BCN MIK BCL Molar Volume MSO MMA 100 50 0.0 EAC CHA TCE STY EET CRB NTB

CHK DEN ATC DoubTTE ETA EVE ACA MAM BNZ le CRP VAM MEK BTR TCL ANL MAN DOX bond THF PRA ALC FFA PYR MVK EPC CRF VOC EDC DMF ACI ALN ALM

ACB ACE ACN DCM POX ARL MIC CBB AAC MBR AAD All ATN TCR 1.0 2.0 3.0 Red number ALA NME 4.0 5.0

HSP FOR CYTOTOXIC DRUGS FOR GLOVE SELECTION CHEMICAL Fluorouracil Gemcitabine Cyclophosphamide Ifosfamide Methotrexate Etoposide Paclitaxel (Taxol) Average Group 1 D 18.0 19.0

17.5 17.5 20.0 18.0 18.3 P 11.7 12.6 11.9 11.9 18.0 7.5 6.6 10.3 H 11.6 15.5 12.6 9.8 10.2 12.5 9.8 12.3 V 118.3 260.6

279.1 261.1 14.2 588.5 853.9 - Cytarabine (Pyrimidine/arabinose) Carboplatin (Organic Pt) 19.0 15.2 20.1 187.1 27.3 9.0 10.4 185.1 378.7

CYCLOPHOSPHAMIDE BREAKTHROUGH TIMES NITRILE 45 MINUTES, BUTYL >>4 P H HOURS D Cyclophosphamide MATERIAL 17.5 11.9 P 12.6 H D 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 5.10 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 2.10 7.00 14.36 2.05 PERMEATION - VIABLE HUMAN SKIN Ursin,et.al.,J.Am.Ind.Hyg.Assoc., 56, 651 (1995). SIGMOIDAL ABSORPTION

TIME DELAY WITH SQRT TIME ABSORPTION LINEAR WITH TIME CASE II ABSORPTION FASTER THAN LINEAR WITH TIME SUPER CASE II HSP FOR ORGANIC SALTS Material D P H DMEA - Dimethyl Ethanolamine 16.1 9.2 15.3 Formic Acid 14.3 11.9 16.6 Acetic Acid 14.5 8.0 13.5 DMEA/Formic Acid 17.2 21.5 22.5 DMEA/Acetic Acid 16.8 19.8 19.8 ALL VALUES HIGHER HSP FOR IONIC LIQUIDS

Ionic liquid D [bmim]Cl [bmim]PF6 19.1 20.7 20.7 35.0 175.0 21.0 17.2 10.9 29.3 207.6 [omim]PF6 20.0 16.5 10.0 27.8 276.0 [bmim]BF4 23.0 19.0 10.0 31.5 201.4 P

H t V, cc/mole [bmim] is butyl methyl imidazole (o is octyl) Solvents having CO2 solubility greater than Ideal x = 0.0229 at 25C and PCO2 = 1 (Williams) Solvent (MPa) (MPa) (MPa) d p 1/2 h 1/2 1/2

Tributyl phosphate, (C12H27O4P) 0.03550 16.3 6.3 4.3 Amyl acetate, (C7H14O2) 0.02800 15.8 3.3 6.1 Butyl oleate, (C22H42O2) 0.02790 14.7

3.4 3.4 Tetrahydrofuran (C4H8O) 0.02700 16.8 5.7 8.0 Methyl oleate (C19H36O2) 0.02690 14.5 3.9 3.7 Isobutyl acetate (C6H12O2)

0.02500 15.1 3.7 6.3 Methyl ethyl ketone (C4H8O) 0.02444 16.0 9.0 5.1 Propyl acetate (C5H10O2) 0.02429 15.3 4.3

7.6 Ethyl acetate (C4H8O2) 0.02300 15.8 5.3 7.2 Methyl acetate (C3H6O2) 0.02253 15.5 7.2 7.6 BEST SOLVENTS CARBON DIOXIDE HSP FOR CARBON DIOXIDE

Data Fit = 1.000 for experimental data D = 15.7 MPa = 6.3 MPa P = 5.7 MPa H Ro = 3.3 MPa 2 2 2 CARBON DIOXIDE SOLUBILITY HSP FOR SPECIAL CHEMICALS Chemical Amphetamine

P H 17.5 4.3 6.3 Bisphenol A 19.2 5.9 13.8 d-Camphor 17.8 9.4

4.7 2-Ethyl hexyl phthalate (MEHP) 17.3 6.2 6.8 Hexanal 15.8 8.5 5.4 Nicotine 18.5

7.8 6.5 L-Menthol 16.6 4.7 10.6 Paracetemol 17.8 10.5 13.9 Paraquat 19.5

8.8 5.9 Skatole 20.0 7.1 6.2 2-Tert-butyl-4-methyl phenol 17.3 3.7 10.5 Triacetin

16.5 4.5 9.1 Triclosan 20.0 7.7 10.0 Vanillin 18.6 10.6 13.8

D 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 A MATERIAL TBBPA 20.2 9.1 D P 13.8 -

H Ra RED TBBPA 0.0 PENTACHLOROPHENOL 21.5 6.9 12.8 3.5 LIGNIN 21.9 14.1 16.9 6.8 17.6 12.5 11.0

11.9 12.9 9.3 (close) 0.5 RAPID SKIN PERMEABILITY 6.5 PSORIASIS SCALE SWELLING 24.6 0.49 0.36 DIOXIN PHYSICAL INTERACTIONS D

20.0 P 9.2 H 7.6 PREDICTIONS: Moderate Skin Permeation Rate (Large Size) Ready Absorption into Lignin (Plants) ULTRASTRUCTURE OF WOOD HEMICELLULOSE 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 Single molecule >1% soluble in Data Fit 0.856 Good/Total 88/167 Total miscibility Data Fit 0.880 Good/Total 47/166 D P H Ro 15.5 16.0 42.3 15.1 20.4 16.5 18.1

18.1 17.1 16.9 13.0 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 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) 2 D 2 P

2 H 19.0 20.0 11.0 EH is 14% of E HSP FOR DNA BASES Segment Guanine Cytosine Adenine Thymine Average D P H V In H2O Parts/100 20.0 12.7 12.5 126.1 Insol. 19.5 12.1 9.9 107.8 0.77 20.0 10.2 13.7 131.5 0.05 19.5 14.2 12.6 121.7 0.4 19.75 12.3 12.2 - ESSENTIALLY INDENTICAL HSP: DNA BASES, CYTOTOXIC DRUGS AND RAPID SKIN D P

H Ra Ra PERMEATION (bases) (Gp 1) Rapid Skin Perm. DNA bases Ave. Group 1 Drugs 17.6 19.75 18.3 12.5 12.3 10.3 11.0 12.2 12.3 4.47 3.52 2.91 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 D P H FAT Ro Fit Ra (Bases) DEPOT DNA 19.0 (Molecule) 20.0 11.0 11.0 1.000 7.93

Zein (Protein) 22.4 9.8 19.4 11.9 0.964 9.28 Lard 15.9 (Depot Fat) 1.2 5.4 12.0

1.000 15.87 CHEMOTHERAPY DRUGS WITH ETHANOL/DOP MIXTURES COCKTAIL FOR CONSIDERATION METHYL PARABEN+DOP+ETHANOL TARGET: CHEMODRUG HSP SPHERE OPTIMUM NMR SOLVENT MIXTURES ARE POSSIBLE HPLC RETENTION TIME Retention time based on HSP of solute, mobile and stationary phases WHOLE EQUALS SUM OF PARTS E =COHESION E +E +E E= ENERGY =

D - Dispersion (Hydrocarbon) E vap P - Polar (Dipolar) D P H H - Hydrogen Bonds (Electron Interchange) V - Molar Volume E/V = ED/V + EP/V + EH/V 2 2 =

2 2 + + D P H HANSEN SOLUBILITY PARAMETERS (HSP) = Square Root of Cohesion Energy Density SUMMARY 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? Hansen Solubility Parameters in Practice

eBook, and Examples The HSPiP Software, 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 Thank you for your attention! For further contact please visit: www.hansen-solubility.com

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