Purification by liquid liquid extraction using Hansen Solubility Parameters (HSP)

HSP Application note #60

2010.11.14

HSPiP Team Senior Developer, Dr. Hiroshi Yamamoto

I was asked by the very beginner of HSPiP.

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.
Please check the Functional Group List whether your targets are available with HSPiP.
How to purchase HSPiP
2013..1.2 The HSPiP ver. 4 include Power Tools for HSPiP power user.

He said, “ I bought HSPiP, but there are so many tab, button, pain and manual is so huge. Please lecture me so as even ape can understand!”.
So, I made hands on for him.
I can not reveal his target, but what he want to do is purification by liquid liquid extraction.
I search Patents and I found very good example about solvents for Lithium Ion battery.

In patent claim,
“The carbonate that have one Fluorine Atom at 1 position” is
“high efficiency of charge and discharge”
“Superior nature at low temperature”
and have other good properties.

But this solvent was contaminated by di-substitute or tri-substitute carbonate and these highly substituted or not 1 position substituted materials make worse for battery electrolyte solution.
(The patent itself is target for new process that prevent from byproducts production.)
I explain how to use HSPiP for this problem.

Hansen Solubility Parameters (HSP)

Hansen Solubility Parameters(HSP) were developed by Charles M. Hansen as a way of predicting if one material will dissolve in another and form a solution. They are based on the idea that "like dissolves like" where one molecule is defined as being 'like' another if it bonds to itself in a similar way.
Specifically, each molecule is given three Hansen parameters, each generally measured in MPa0.5:
dD:The energy from dispersion bonds between molecules
dP:The energy from dipolar intermolecular force between molecules
dH:The energy from hydrogen bonds between molecules.
These three parameters can be treated as Vector for a point in three dimensions also known as the Hansen space. The nearer two molecules HSP Vector are in this three dimensional space, the more likely they are to dissolve into each other.

What can perhaps be surprising is that one can assign HSP to so many different things. Gases like carbon dioxide, solids like carbon-60, sugar, and biological materials like human skin, depot fat, DNA, and even some proteins all have HSP. The list can be continued with drugs, polymers, plasticizers, and in fact any organic material and even many inorganic materials like salts. The only requirement for an experimental confirmation is that the material must behave differently in a sufficient number of test solvents upon contact.

Pirika JAVA Demo Applet calculate HSP. HSPLight is available here.
Please refer to e-Book of HSPiP if you want know more about HSP.
About the Power Tools that handle HSP more effectively.

The first thing to do is get Smiles Structure of these molecules.

Smiles(Simplified Molecular Input Line Entry Syntax)

SMILES is a string obtained by printing the symbol nodes encountered in a depth-first tree traversal of a chemical graph.
"Organic subset" of B, C, N, O, P, S, F, Cl, Br, and I, brackets can be omitted.
Branches are described with parentheses, as in CCC(=O)O for propionic acid
Double and triple bonds are represented by the symbols '=' and '#'
Ring closure labels are used to indicate connectivity between non-adjacent atoms in the SMILES

Pirika JAVA Demo Applet getting Smiles. Draw2Smiles is available here.
Now we have Power Tool "Draw 2 Smiles", GUI HTML5 software on HSPiP ver. 4.

<p>Please Use HTML5 Browser</p>

If you want to know how to draw molecules, please refer to Power Tools applications. The full version of this routine is implemented into Draw2Smiles Powert Tools in HSPiP ver. 4.

Draw molecules and get smiles like below figure.
Then paste it to Spreadsheet.

You can get these Smiles within 10 minutes.
Then run the HSPiP.

Then push δ button, You will get DIY panel.
Please confirm you select Y-MB.

Then Copy one smiles from spreadsheet, and paste it “Smiels or InchI Input” field, and push Calculate button.
Y-MB will break Smiles into functional groups and calculate a lot of properties.
These results are store in ClipBoard memory, so you can paste that results into spreadsheet.

In the ClipBoard memory, the title is also stored, so paste out position and copy again for each molecules.
(Please refer to DB-import article for batch break)

You can get HSP and other properties within 5 minutes.
If you need not other properties, please delete them.
(But viscosity or vapor pressure are very important properties for Litium ion battery’s solvent)

Happily enough, Main Product and ByProduct HSP are separated.

HSP Distance

To calculate the distance (Ra) between Hansen parameters in Hansen space the following formula is used:

HSP distance(Ra)={4*(dD1-dD2)2 + (dP1-dP2)2 +(dH1-dH2)2 }0.5

Hansen Sphere

To 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).
The HTML5 Sphere Viewer examples are available here.
Now we have Power Tool "Sphere Viewer", GUI HTML5 software on HSPiP ver. 4.

So, if I draw line from main product to by product (Red line), then the candidate liquid-liquid extraction solvents’ HSP is dD:16.5-17.5, dP: 7-9, dH: 1-4.
You can search solvents with HSPiP.

You can find solvents from FindMols menu.

Set the values and push calculate button, you can get candidate in a seconds.

From start to get candidate solvents, it take 20 minutes.

<p>Please Use HTML5 Browser</p>

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. Red small sphere means target chemical, Blue spheres are by products. The green sphere is 1,2-DichloroPropane. We can understand by-products are easily dissolve in 1,2-DichloroPropane.

All these candidate are halogenated compounds and suppose you do not want to use such solvents, you can search solvents mixture.
If you want to search No.1221, 1,2-DichloroPropane[17.3, 7.1, 2.9] like solvent mixture, select Solvents Optimizer button (O).

And set target value and just push 2 button.
Cyclohexane:gamma-butyrolactone =58:42 is the nearest with the target.

You can set your own solvents in the optimizer list.
If you are accustom to using HSPiP, please try by yourself.