HSP Application note #42
Hansen Solubility Parameters (HSP) Double Spheres2010.7.25
HSPiP Team Senior Developer, Dr. Hiroshi Yamamoto
HSPiP ver. 4 have the Power Tool, "Y-Fit". This power Tool is improved this analysis so much.
At the Quantitative Solubility, I explained about Oleic Acid solubility. Alcohol solvents play the abnormal behavior.
| Hcode | name | dD |
dP |
dH |
ScoreC | ScoreAmount |
122 |
carbon tetrachloride | 17.8 |
0 |
0.6 |
1 | 107.712 |
156 |
chloroform | 17.8 |
3.1 |
5.7 |
1 | 136.988 |
534 |
nitromethane | 15.8 |
18.8 |
5.1 |
0 | 0.6774 |
456 |
methyl alcohol | 14.7 |
12.3 |
22.3 |
0 | 24.9956 |
10 |
Acetonitrile | 15.3 |
18 |
6.1 |
0 | 0.8646 |
367 |
1,2-dichloroethane | 18 |
7.4 |
4.1 |
1 | 32.625 |
7 |
Acetone | 15.5 |
10.4 |
7 |
0 | 21.646 |
570 |
isopropyl alcohol | 15.8 |
6.1 |
16.4 |
1 | 43.175 |
481 |
methyl ethyl ketone | 16 |
9 |
5.1 |
0 | 26.9675 |
328 |
ethyl acetate | 15.8 |
5.3 |
7.2 |
1 | 39.688 |
92 |
butanol | 16 |
5.7 |
15.8 |
1 | 45.765 |
255 |
diethyl ether | 15.49 |
2.9 |
4.6 |
1 | 42.78 |
148 |
chlorobenzene | 19 |
4.3 |
2 |
1 | 94.01 |
181 |
cyclohexane | 16.8 |
0 |
0.2 |
1 | 62.32 |
102 |
butyl acetate | 15.8 |
3.7 |
6.3 |
1 | 42.336 |
417 |
hexane | 14.9 |
0 |
0 |
0 | 29.2596 |
698 |
o-xylene | 17.8 |
1 |
3.1 |
1 | 77.44 |
532 |
nitroethane | 16 |
15.5 |
4.5 |
0 | 2.2946 |
404 |
furfural | 18.6 |
14.9 |
7 |
0 | 1.5015 |
This abnormality is happen for Stearic Acid solubility.
So, Carboxylic acid and Alcohol make cluster and change it solubility I think.
Hansen SphereTo determine if the parameters of two molecules (usually a solvent and a polymer) are within range a value called interaction radius (R0) is given to the substance being dissolved. This value determines the radius of the sphere in Hansen space and its center is the three Hansen parameters.
From version 3.1.X, Double Spheres function is available. Pirika provide JAVA 3D Demo Applet to browse the Sphere(s). |
I added new function called "Double Spheres" to solve this type of problems.
Let's see What this "Double Spheres" function works.
Read the file of Oleic Acid (I assign score as 1 for more solubility than 30g/100CC). Then choose Double Spheres, and push Read & Run button. You will get 2 spheres. Sphere A, HSP is [16.9, 3.1, 4.0] and radius 5.82, Sphere B、HSP is [16.5, 0.3, 11.4] and Radius 7.88.
If JAVA 3D is already installed in your machine, please try 3D view of this Sphere.
2011.4.11
Drag=Rotate, Drag+Shift=Larger/Smaller, Drag+Alt or Command(Window key)=Translate.
If you are using HTML5 enable browser such as Chrome, Safari or FireFox (IE9 is out of support), you will see the Canvas. If you pick solvent, solvent name will appear.
if you are browsing with iOS machine (iPad, iPhone, iPodTouch) please browse with this program.
The solvents that scored 0, should not go inside to Sphere A and Sphere B. So both RED-A and RED-B should be larger than 1.
Then Solvents that scored 1, should go inside Sphere A or Sphere B. So either RED-A or RED-B should be shorter than 1. If both RED-A and RED-B is shorter than 1, that solvent belong to overlap area of Sphere-A and Sphere-B.
Oleic Acid case, there are no overlap.
It is very common for having different nature, if the molecular size become large. For such case this Double Spheres may work very well.
Next example is Fluoro Packing polymer. I analyze swelling grade with HSP. And this time, I use Double Spheres.
This polymer seems hydrophobic polymer, though swelling very well to gasoline-ethanol hydrophilic solvents. So this polymer may have double nature.
| Hcode | name | dD | dP | dH | score |
6 |
acetic anhydride | 16 | 11.7 | 10.2 | 1 |
7 |
acetone | 15.5 | 10.4 | 7 | 1 |
11 |
acetophenone | 18.8 | 10 | 4 | 1 |
17 |
acetylacetone | 16.1 | 10 | 6.2 | 1 |
25 |
acrylonitrile | 16 | 12.8 | 6.8 | 1 |
46 |
aniline | 20.1 | 5.8 | 11.2 | 0 |
52 |
benzene | 18.4 | 0 | 2 | 0 |
115 |
gamma-butyrolactone | 18 | 16.6 | 7.4 | 1 |
122 |
carbon tetrachloride | 17.8 | 0 | 0.6 | 0 |
156 |
chloroform | 17.8 | 3.1 | 5.7 | 0 |
181 |
cyclohexane | 16.8 | 0 | 0.2 | 0 |
182 |
cyclohexanol | 17.4 | 4.1 | 13.5 | 0 |
195 |
trans-decahydronaphthalene | 18 | 0 | 0 | 0 |
209 |
diacetone alcohol | 15.8 | 8.2 | 10.8 | 1 |
254 |
diethyl carbonate | 15.1 | 6.3 | 3.5 | 1 |
270 |
2-(2-methoxyethoxy)ethanol | 16.2 | 7.8 | 12.6 | 0 |
285 |
N,N'-dimethylacetamide | 16.8 | 11.5 | 10.2 | 1 |
297 |
N,N'-dimethylformamide | 17.4 | 13.7 | 11.3 | 1 |
306 |
1,4-dioxane | 17.5 | 1.8 | 9 | 1 |
325 |
ethyl alcohol | 15.8 | 8.8 | 19.4 | 0 |
328 |
ethyl acetate | 15.8 | 5.3 | 7.2 | 1 |
333 |
ethylbenzene | 17.8 | 0.6 | 1.4 | 0 |
366 |
1,2-dibromoethane | 19.2 | 3.5 | 6.6 | 0 |
385 |
ethylenediamine | 16.6 | 8.8 | 17 | 1 |
396 |
formaldehyde | 12.8 | 14.4 | 15.4 | 0 |
398 |
formic acid | 14.6 | 10 | 22.1289172 | 0 |
404 |
furfural | 18.6 | 14.9 | 7 | 0 |
417 |
hexane | 14.9 | 0 | 0 | 0 |
429 |
isopentyl acetate | 15.3 | 3.1 | 7 | 1 |
438 |
isophorone | 17 | 8 | 5 | 1 |
456 |
methyl alcohol | 14.7 | 12.3 | 22.3 | 0 |
464 |
methyl acetate | 15.5 | 7.2 | 7.6 | 1 |
467 |
methyl acrylate | 15.3 | 6.7 | 9.4 | 1 |
481 |
methyl ethyl ketone | 16 | 9 | 5.1 | 1 |
491 |
4-methyl-2-pentanone | 15.3 | 6.1 | 4.1 | 1 |
531 |
nitrobenzene | 20 | 10.6 | 3.1 | 0 |
598 |
pyridine | 19 | 8.8 | 5.9 | 1 |
617 |
tetrahydrofuran | 16.8 | 5.7 | 5.7 | 1 |
637 |
toluene | 18 | 1.4 | 2 | 0 |
649 |
trichloroethylene | 18 | 3.1 | 5.3 | 0 |
659 |
triethyl phosphate | 16.7 | 11.4 | 9.2 | 1 |
670 |
2,2,4-trimethylpentane iso-octane | 14.1 | 0 | 0 | 0 |
698 |
o-xylene | 17.8 | 1 | 3.1 | 0 |
814 |
p-chlorotoluene | 19.1 | 6.2 | 2.6 | 0 |
997 |
2-methyltetrahydrofuran | 16.9 | 5 | 4.3 | 1 |
1016 |
ethylacetoacetate | 16.5 | 7.3 | 8.3 | 1 |
1037 |
methyl acetoacetate | 16.4 | 8.6 | 8.9 | 1 |
1043 |
propionic anhydride | 15.8 | 9 | 7.7 | 1 |
1145 |
dimethyl maleate | 16.3 | 8.3 | 9.8 | 0 |
With the result of Double Spheres analysis, Sphere-A HSP is [15.5, 11.1, 5.9] radius 7.61, and Sphere-B HSP is[15.8, 4.0, 10.3] radius 4.47. Both dD are almost same, but dP and dH cover very wide range.
Drag=Rotate, Drag+Shift=Larger/Smaller, Drag+Alt or Command(Window key)=Translate.
If you are using HTML5 enable browser such as Chrome, Safari or FireFox (IE9 is out of support), you will see the Canvas. If you pick solvent, solvent name will appear.
When I plot this result with SOM(self organization map) method, result become above figure.
Ester solvents come to overlap area.
Sphere-A(red line area) include ketone, Amide that dP is fairly large.
Sphere-B(Blue line area) include Ester and ketone that dP is small.
If you use classic Sphere, overall polymer's HSP become [14.9, 6.8, 5.2].
When you want to improve packing swelling, which is reasonable thinking polymer have 2 different dP area or polymer have average dP=7 area.
It depend on you.
You can use Double Spheres function from HSPiP V3.1.X
HSPiP(Hansen Solubility Parameters in Practice)The first edition of HSPiP that appeared in November, 2008, greatly enhanced the usefulness of the Hansen solubility parameters (HSP). The HSP values of over 1200++ chemicals and 500 polymers are provided in convenient electronic format and have been revised and updated using the latest data sources in the second edition (March, 2009). A third edition of the HSPiP appeared in March, 2010. There are now 10,000 compounds in the HSP file which also includes data on density, melting point, boiling point, critical parameters, Antoine constants and much more. The user is able to carry out many different sorts of optimisations of solubility, evaporation, diffusion, adhesion, create their own datasets (automatically if required) and explore the huge range of applications for HSP in coatings, paints, nanoparticles, cosmetics, pharma, organic photovoltaics and much more. The 3rd Edition v3.1 was released on 12 December 2010. Current users can upgrade free (now v3.1.09) by downloading the latest .msi installer from http://hansen-solubility.com The 4th Edition v4.0.x was released on 2 Jan. 2013. The Current users can upgrade with free charge. 2013.1.28 The Visual How to manual of HSPiP. You can understand what HSPiP can do. |
