Pirika logo
JAVA, HTML5 & Chemistry Site

Top page of Pirika


Official HP HSPiP(Hansen Solubility Parameters(HSP) in Practice)
HSPiP How to buy

Hansen Solubility Parameter (HSP)
  Basic HSP
  Applications
  Polymer
  Bio, Medical, Cosmetic
  Environment
  Properties Estimation
  Analytical Chemistry
  Formulating for Cosmetics
  Other
  DIY:Do It Yourself

Chemistry@Pirika
  Properties Estimations
  Polymer Science
  Chemical Engineering
  Molecular Orbital
  Chemo-Informatics
  Other Chemistry
  Academia
  DIY:Do It Yourself
  Programing

Other Writing

Ad Space for you

 

Ad Space for you

 

 

 

last update
29-Jan-2013

HSP Application note #32

Surfactant and Hansen Solubility Parameter (HSP)

2010.4.17

HSPiP Team Senior Developer, Dr. Hiroshi Yamamoto

 

Under CMC Surfactant begin to make Micelle
Critical Micelle Concentration(CMC)

Critical Micelle Concentration (CMC)

Name

C#

cmc(mmol)

melting point

logP

logS

butyric acid Na salt

4

-5.15

0.79

0.778

pentanoic acid Na salt

5

-33.95

1.39

0.3802

hexanoic acid Na salt

6

-3.85

1.92

-0.014

heptanoic acid Na salt

7

-7.27

2.42

-0.611

octanoic acid Na salt

8

360

16.55

3.05

-1.167

nonanoic acid Na salt

9

12.45

3.42

-1.75

decanoic acid Na salt

10

95

31.65

4.09

-2.44

undecanoic acid Na salt

11

28.53

4.42

-2.55

Lauric Acid Na salt

12

27.5

44.2

4.6

-3.318

tridecanoic acid Na salt

13

41.91

-2.57

myristic acid Na salt

14

7.2

54.4

6.11

-3.971

pentadecanoic acid Na salt

15

52.58

palmitic acid Na salt

16

1.9

62.9

7.17

-5.398

heptadecanoic acid Na salt

17

61.15

Stearic acid Na salt

18

0.5

69.6

8.23

-4.224

nonadecanoic acid Na salt

19

68.13

Oleic acid Na salt

18

1

13.4

7.73

-6

linoleic acid Na salt

18

2

-5.1

7.05

-5

Acid form

Acid form

Acid form

I compiled CMC data for surfactant.
I happen to plot logCMC to logP of Carboxylic Acid (Acid form).
There is so beautiful correlation!

So, I found that Critical Micelle Concentration is governed by logP value.
As I wrote in User’s Forum article, logP just means Volume.

I compiled more CMC data and check this phenomena.

As same with logP, logCMC has very beautiful correlation with HSP Volume.

I can estimate CMC from Volume and type of hydrophilic structure

Hydrophobic structure: it means just molecular volume.
Fluorinated, aromatic, hydrocarbon, that does not matter. JUST VOLUME!

Hydrophilic structure: almost all coefficient is around 2 except Ethylene Oxide.

Overall, logCMC is governed by only Hydrophobic structure’s volume.

So, logCMC estimation scheme and HLB scheme say same thing.
If you plot Fluoro-compounds with HLB (calculated by mass) fluoro-compounds are heavy and HLB become small.
But if you plot with molecular volume calculated by HSPiP, it become identical line.

If you draw molecule and put X atom at the hydrophpilic part, then calculate, program will calculate CMC. This program do not support -OCH2CH2- type of surfactants. If you want to know how to draw molecules, please refer to Helper applications.

How many molecules aggregate in Micelle?

Something dissolve into micelle,
Volume increase, then surface increase,
new surfactant fill new surface and surfactant hydrophobic part increase volume.

HLB and logP is very similar concept.
But both logP and HLB is not solubility indicate.
So, there is no correlation with HSP.

After surfactant make micelle, HSP play very important role.

I got the mail about CMC of sulfosuccinates surfactant.
Sulfosuccinates have two tails.
If the total hydrophobic volume is same, CMC is ten times larger for Sulfosuccinate.
For example, C6H13OOCCH2CH(SO3Na)COOC6H13 volume is 296 and CMC is 12.
C17H35So3Na, volume is 301 and CMC is 0.21.
C14H29-Ph-SO3Na, volume is 315 and CMC is 0.66.
So, with same hydrophobic volume, Sulfosuccinate have 10 time more micelle volume.
It will very good for detergent.

I search for aggregation number about Sulfosuccinates, but in vain.
If you have the data, please let me know.

Then I can say which size, how many micelle exist for certain surfactant.
Then I want to know how much oil solve to this system.
That case HSP will play very important role.
Please read article about liquid-liquid extraction .

2011.6.11
I made Charge Calculation program for my students. Just draw molecule and push calc. button, you will get charge. This Program may help understanding of these salts.