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Measurement of HLB (Hydrophile - Lipophile Balance) values by NMR

HLB (Hydrophilic - Lipophilic Balance) is the ratio of oil and water-soluble constituents of a non ionic surfactant.

Griffin, who proposed the following calculation method, originally developed the system in 1954:

HLB = MH/M * 20 or %MH/5

...where MH is the molecular mass of the hydrophilic portion of the Molecule, and M is the molecular mass of the whole molecule giving a result on an arbitrary sclae of 0 to 20.

The lower the HLB the more lipophilic or oil soluble the surfactant becomes. The higher the HLB the more water soluble or hydrophilic the surfactant becomes. HLB values are traditionally calculated for nonionic surfactants for example Oleyl alcohol 20 mole ethoxylate would have a calculated HLB of 880/1150 * 20 - 15.3

Alternatively, HLB may be determined experimentally by invert emulsion experiments, gas-liquid chromatography or NMR.

HLB Numbers

                

Ethylene Oxide % mole

                

Applications

4-6

 

20-30

 

W/O emulsifier

7-15

 

35-75

 

Wetting agent

8-18

 

40-90

 

W/O emulsifier

10-15

 

50-75

 

Detergent

10-18

 

50-90

 

Solubiliser

Comparison of NMR experimental derived HLB against supplied HLB: 

Non Ionic

          

HLB NMR

           

HLB Manufacturer

           

Difference

Tween 20

 

16.8

 

16.6

 

0.2

tween 21

 

11.8

 

13.3

 

-1.5

Tween 80

 

15.2

 

15.0

 

0.2

Tween 85

 

15.0

 

11.0

 

4.0

Tergitol 15s9

 

13.7

 

13.3

 

0.4

Lubrol 17A17

 

15.1

 

0.0

 

15.1

Brij C20PA

 

16.0

 

15.7

 

0.3

Brij C20PA

 

15.9

 

15.7

 

0.2

Lutensol NP 10

 

14.9

 

14.0

 

0.9

MYRJ 59

 

18.8

 

18.8

 

0.0

MYRJ 49P

 

15.3

 

15.0

 

0.3

MYRJ S20

 

15.3

 

15.0

 

0.3

MYRJ 53P

 

17.7

 

0.0

 

17.7

Arlatone 983

 

9.8

 

7.5

 

2.3

Arlatone 983

 

9.0

 

7.5

 

1.5

Atmer 154

 

14.6

 

14.5

 

0.1

Nonylphenol 10

 

14.9

 

13.3

 

1.6

Advantages: 

NMR provides a quick and accurate method for determination of HLB values

Disadvantages: 

This method works best with alcohol ethoxylates and fatty acid ethoxylate esters it becomes increasingly inaccurate with addition of PPG.  Therefore would not recommend this method for PPG containing non ionic's.  The system is yet untested on blends of non ionic ethoxylates consequently it needs validation with non ionic mixtures with known HLB values.

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