Akzo Nobel

Surface Chemistry LLC Technical Information

Surface Chemistry

HLB & Emulsification

Description of Hydrophile,
Lipophile Balance and use of
HLB in Producing Emulsions

http://surface.akzonobel.com

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Introduction to HLB:

Surfactants are often characterized by their hydrophilic/lipophilic balance or

HLB. High HLB values indicate good water, or polar solvent solubility, of the
surfactant while low HLB values are indicative of good solubility in non polar
systems, such as oil.

The water loving, or hydrophilic character, of a surfactant is determined by the

polarity of the head group. Typical head groups found in Akzo Nobel Surfactant
products include, amine, quaternary ammonium, ethoxylate, sulfate, phosphate
and carboxylate. The polarity of the head group may be altered in some cases
by altering the pH or by increasing the degree of ethoxylation, e.g. increasing
the ethoxylation levels increases the water loving character of the surfactant,
and thus the HLB increases. Conversely, increasing the size of the fatty tail, or
propoxylation of the head group will decrease the HLB.

The Hydrophile, Lipophile Balance, (HLB) system is a useful tool in finding a

suitable emulsifying system A vast number of emulsifiers (surfactants) are
available to the formulator and the HLB system can be used as a guide to
narrow the selection to those best suited to his specific system.

The following discussion covers the determination of HLB of a surfactant:

HLB Calculation:

HLB values of individual surfactant molecules can be calculated applying the

Davies formula. Akzo Nobel Surfactants uses the Davies formula as it is a wide
scale of 0 – 40, and can accommodate the types of products we offer.
According to this formula the HLB is derived by summing the
hydrophilic/hydrophobic contributions afforded by the structural components of
the surfactant..

HLB = Σ (Hydrophilic group contributions) – Σ (Hydrophobic group

contributions) + 7

Group contributions are listed in tables A - D. Tables A, B & C provide the group
contributions of the hydrophilic groups and table D gives the contribution of the
hydrophobic groups.

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Table A: anionic hydrophilic group contributions
hydrophilic group HLB contribution hydrophilic group HLB contribution
– COO- Na+ 19.1 – SO3- Na+ 20.7
– O - SO3- Na+ 20.8

Table B: cationic and betaine hydrophilic group contributions

Hydrophilic group HLB Hydrophilic group HLB
contribution
contribution
– NH3+ Cl- 20.0 – NH2+- CH2 - CH2 - CH2 – NH3+ 2 Cl-
>NH2+ Cl- 20.0 38.6
CH3 CH3
│ /
– N+- CH3 Cl- 22.0 > N+ Cl- 22.5
│ \
CH3 CH3
CH3 CH3
/ │
> N+ Cl- 19.7 – N+- CH2 ∅ Cl- 19.2
\ │
CH2 - ∅ CH3
CH2 - CH2 – OH CH2 - CH2 – OH
│ │
– N+– H Cl- 21.9 – N+- CH3 Cl- 24.9
│ │
CH2 - CH2 – OH CH2 - CH2 – OH
CH3 CH3 CH2 – CH2 – OH
│ │ /
– N+- CH2 - CH2 - CH2 - N+- CH3 2 Cl- – NH+- CH2 - CH2 - CH2 – NH+ 2 Cl-
│ │ │ \
CH3 CH3 CH2 - CH2 –- OH CH2 - CH2 – OH
43.5 41.4
CH3 CH2 - CH2 – OH
l l
–N→O 21.0 –N→O 2 3.8
l (at pH = 3) L (at pH = 3)
CH3 CH2 - CH2 – OH
CH3 CH3
│ │
– N+- CH2 - COOH Cl- 24.1 – N+- CH2 - COO- 38.0
│ │
CH3 CH3

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Table C: cationic and nonionic hydrophilic group contributions
hydrophilic group HLB hydrophilic group HLB
contribution contribution
– NH2 9.4 – NH - CH2 - CH2 – CH2 – NH2
> NH 9.4 17.4
CH3 CH2 - CH2 – OH
/ /
–N 8.5 –N 11.3
\ \
CH3 CH2 - CH2 – OH

CH2 - CH2 – OH O
/ ║
– N - CH2 - CH2 - CH2 - N – C - NH2 9.6
⏐ \
CH2 - CH2 – OH CH2 - CH2 – OH

20.2 –O– 1.3

– COOH 2.1 – CH2 - CH2 – O – 0.33

– OH 1.9 – CH2 - CH2 – OH 0.95

Table D: hydrophobic group contributions

hydrophobic group HLB contribution hydrophobic group HLB contribution
– CH3 0.475 – CH = 0.475
(unsaturated)
– CH2 - 0.475 – CH2 - ∅ 1.66
– CH - (branched) 0.475 – CH2 – CH – O – 0.15
⏐ ⏐
CH3

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Example Calculation:

The following calculation is based on tetradecyl trimethyl ammonium chloride:

Tetradecyl trimethyl ammonium chloride has the following structure:

CH3
l Cl-
CH3 - (CH2)13 - N+- CH3
l
CH3

Group contribution of the hydrophobic groups:

CH3 - 0.475
- CH2 - 0.475

Group contribution of the hydrophilic group:

CH3
l Cl-
- N+- CH3 22.0
l
CH3

HLB = 22.0 - (14 x 0.475) + 7 = 22.4

Surfactant Mixtures:

In this case, the HLB value of a surfactant system is the weight average values
of the respective surfactant components. For example, a mixture of 40 %
Armeen® 12D (HLB = 11.7) and 60 % Arquad 16 (as 100 % active) (HLB =
21.4) gives the following HLB value:

HLB = (0.4 x 11.7) + (0.6 x 21.4) = 17.5

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Cationic HLB Values:

The Akzo Nobel fatty amine products have surfactant properties that can offer
emulsifing properties. In literature HLB values for this class of surfactants are
hardly found. Following is a list of HLB values for these products:

Table 1: HLB values of Akzo Nobel fatty amines and derivatives

(accuracy: ± 10%). Some products convert to amine salts in acid
conditions, and their resulting HLB depends on the pH. The following table
is segmented by pH for those products that convert to salts. Products
whose HLB are independent of pH are given in the far right column.

HLB at pH >9 HLB at pH <8 HLB independent of pH

Armeen® 12D 10.7 Armeen 12D 21.3 Armac® C 22.9

Armeen CD 10.2 Armeen CD 20.8 Duomeen TDO 25.9
Armeen 16 8.8 Armeen 16 19.4 Arquad® 12 23.3
Armeen HTD 8.3 Armeen HTD 18.9 Arquad C 22.8
Armeen HT 8.3 Armeen HT 18.9 Arquad 16 21.4
Armeen OD 8.2 Armeen OD 18.8 Arquad HP 20.8
Armeen 18D 7.9 Armeen 18D 18.5 Arquad HT 20.9
Armeen 2C 4 Armeen 2C 14.6 Arquad S 20.8
Armeen 2HT 0.1 Armeen 2HT 10.7 Arquad DMCB 21.7
Armeen DMCD 9.3 Armeen DMCD 19.9 Arquad NF 21
Armeen DM16D 7.9 Armeen DM16D 18.5 Arquad 2C 17.1
Armeen DMHTD 7.3 Armeen DMHTD 17.9 Arquad 2HT 13.2
Armeen DMOD 7.2 Armeen DMOD 17.8 Duoquad® T 42.4
Duomeen® C 18.2 Duomeen C 39.4 Ethoquad® C/12 25.7
Duomeen T 16.3 Duomeen T 37.5 Ethoquad HT/25 28
Duomeen O 16.2 Duomeen O 37.4 Ethoquad O/12 23.7
Triameen® YT 24.2 Triameen YT 56 Ethoquad O/15 24.6
Ethomeen® C/12 12.1 Ethomeen C/12 21 Ethoquad 18/25 27.6

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Table 1 (continued): HLB values of derivatives
(accuracy: ± 10%), continued

HLB at pH >9 HLB at pH <8

Ethomeen C/15 13.3 Ethomeen C/15 23.7

Ethomeen C/25 16.4 Ethomeen C/25 27
Ethomeen T/15 11.1 Ethomeen T/15 21.7
Ethomeen T/20 12.8 Ethomeen T/20 23.4
Ethomeen T/30 16.1 Ethomeen T/30 26.7
Ethomeen S/12 10.1 Ethomeen S/12 20.7
Ethomeen 18/15 10.7 Ethomeen 18/15 21.3
Ethomeen O/12 9.8 Ethomeen O/12 20.4
Ethoduomeen T/25 23.1 Ethoduomeen T/25 44.3
Ethomid® O/15 11.2 Ethomid O/15 21.8
Aromox® 14DW-970 18.6 Aromox 14DW-970 21.4
Aromox C/12 21.8 Aromox C/12 24.6
Aromox DMC 21.9 Aromox DMC 24.7
Aromox T/12 19.9 Aromox T/12 22.7

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Nonionic HLB Values:

Our nonionic surfactants offer a wide range of HLB values.

Nonyl Phenol Alkoxylates:

Witconol™ nonyl phenol based nonionic surfactants are used in many

industries. They are very good at wetting, dispersion, and emulsification.

Table 3:
Product Name HLB
WITCONOL NP-40 8.9
WITCONOL NP-90 13
WITCONOL NP-100 13.1
WITCONOL NP-200 16
WITCONOL NP-400 17.8

Alkyl Alkoxylates:

The Ethylan™ family contains other nonionic surfactants.

Table 4:
Product Name HLB
ETHYLAN 1005 11.6
ETHYLAN 1008 14
ETHYLAN 1206 9.5
ETHYLAN 25-3 8
ETHYLAN 324 8
ETHYLAN DA-4 10.5
ETHYLAN LA-230 17
ETHYLAN SN-70 12
ETHYLAN SN-90 12.9
ETHYLAN TD-60 11.4

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Ethoxylated Castor Oil:

The Emulpon™ trade mark is for our castor oil ethoxylates. These are best for
emulsifying oil in water, or water in oil.

Table 5:
Product Name HLB
EMULPON CO-200 10.2
EMULPON CO-360 13.5
EMULPON CO-550 14.4

Fatty Esters:

We also offer a line of fatty esters under the Witconol™ product name. These
products find use as emulsifiers and dispersants in a variety of industrial and
consumer applications.

Table 6:
Product Name HLB
WITCONOL 14 6
WITCONOL H-31A 12.5
WITCONOL H-32 10
WITCONOL H-33 8.4

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Emulsification by HLB:

In order to emulsify a mixture of water and oil one or more emulsifiers is

required. Each surfactant system (pure or mixture) can be characterized by an
HLB value. Each oil/water system can be characterized by a so-called
“required HLB” value. This value depends on the nature of the oil and the
product application. Basically, there are two types of product application. In one
type water dominates; the oil forms droplets. This is designated as a oil in water
(O/W) system. In the other type it is reversed. The system is essentially water in
oil (W/O).

The HLB system predicts the optimum emulsion stability when the HLB value of
the surfactant systems matches the required HLB of the oil/water system. The
required HLB is the value at which enhanced emulsion stability will be attained.
Optimization of the performance can be achieved by only including surfactant
systems with similar HLB values.

The following figure illustrates the effect of different surfactant systems on the
stability of an emulsion. It shows the matching of the surfactant system HLB
and the required HLB of the oil/water system. For each surfactant system
emulsion stability reaches a maximum at the same HLB value.

Figure #1

40
preformance in
arbitrary units

30

20

10
C
0 B
6 7 8 A
9 10 11
12 13 14
15
HLB of surfactant mixture

Idealized model of enhanced performance. Regardless of the surfactant mixture (A,B or C)

at the required HLB of the system performance is enhanced. This effect may be stronger
(example C) or less pronounced (example B).

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When To Use the HLB System:

The HLB model can be used for applications including emulsification,

detergency, solubalization and other applications. Typically a HLB value will
dictate these properties, as shown in table 7:

Table 7: Suggested HLB values for a number of applications

Defoaming of aqueous systems 1-3
Detergency & cleaning 12 - 15
W/O emulsification 3-6
O/W emulsification 8 - 28
Solubilization 11 - 18
Wetting 7-9

Procedure for Using the HLB System:

The HLB system allows for a straightforward approach. Good results can be
achieved in three steps. First of all the required HLB of the formulation system
must be identified. Then, the best surfactant ingredient must be found. Several
(mixtures of) ingredients, all having an HLB equal to the required HLB, must be
included. The choice is determined by the test result. The final step is varying
the amount.

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Determine Required HLB:

For ordinary oil in water (O/W) or water in oil (W/O) emulsification the required
HLB are given in tables 8 (O/W emulsification) and 9 (W/O emulsification).

TABLE 8: Required HLB for O/W emulsions of a variety of oils (± 1)*

Acetophenone 14 Ethyl Aniline 13 Mineral Spirits 14
Arachidyl 7 Ethyl Benzoate 13 Mink Oil 5
Propionate
Benzene 15 Fatty Acids 14-16 Nitro Benzene 13
Benzonitrile 14 Fatty Alcohols 11-16 Nonylphenol 14
Bromobenzene 13 Fenchone 12 o-dichlorobenzene 13
Butyl Stearate 11 Glycerol 13 Palm Oil 10
Monostearate
Carbon 16 Hydrogenated 6-7 Petrolatum 7-8
Tetrachloride Peanut Oil
Castor Oil 14 Isopropyl 11-12 Petroleum Naphta 14
Myristate
Chlorinated 12-14 Isopropyl 14 Pine Oil 16
Paraffin Lanolate
Chlorinated 12-14 Isopropyl 11-12 Propene, tetramer 14
Paraffin Palmitate
Chlorobenzene 13 Jojoba Oil 6-7 Rapeseed Oil 6
Corn Oil 10 Kerosene 12 Silicone Oil 7-8
Cottonseed Oil 5-6 Liquid Lanolin 9 Soybeen Oil 6
Cyclohexane 10 Lauryl Amine 12 Styrene 15
Decyl Acetate 11 Mehadin Oil 12 Toluene 15
Diethyl Aniline 14 Methylphenyl 7 Trichlorotrifluoro 14
Silicone Ethane
Diisooctyl 13 Methyl Silicone 11 Tricresyl 17
Phthalate Phosphate
Diisopropyl 9 Mineral Oil 9-12 Xylene 14
Adipate
Diisopropyl 15
Benzene
Dimethyl 9 *LITERATURE
Silicone VALUES

Table 9: required HLB for W/O emulsions of a number of oils (± 1)*

Gasoline 7 Kerosene 6 Mineral Oil 6
*LITERATURE
VALUES

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It is likely that your oil system is not listed in the tables. In these cases one has
to determine the required HLB value. In essence such determination consists of
three steps. However the salinity, pH and temperature of these steps must be
consistent. First, choose a surfactant system containing at least two surfactants
with a significant difference in HLB value. Then, the product formulation? must
be made? including this surfactant system. It must be done several times. Each
time the surfactants must be mixed in another ratio in order to create different
HLB values. Finally, the performance must be determined and plotted vs. the
HLB (as shown in Figure 1). A maximum will appear in the plot. The
corresponding HLB maximum is equal to the required HLB. One can then use
statistical methods to determine the optimal level of ingredients for your
formula.

If no maximum value is noted in the above procedure then one can deduce that
HLB is not essential to your formulation.

To make choices of the surfactants more easily, table 10 provides indicative

values of required HLB’s of most common applications.

Table 10: indicative required HLB for a number of applications

defoaming of aqueous systems 1–3
detergency & cleaning 12 – 15
W/O emulsification 3–6
O/W emulsification 8 – 28
Solubilization 11 – 18
Wetting 7–9

FURTHER READING

• “The HLB System, a Time Saving Guide to Emulsifier Selection”, ICI

Americas Inc., version 1980
• Davies, J.T. & Rideal, E.K., “Interfacial Phenomena”, 2nd ed., p 371,
Academic Press, London, 1963
• Lin, I.J. & Marszall, L., Tenside Det., 15, 243 (1978)
• O Boen Ho, J. Colloid Interface Sci., 198, 249 (1998)

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 HLB & Emulsification

Customer Service

For additional information, samples or assistance please contact your

local sales representative or the Akzo Nobel Customer Service
Department at:

Akzo Nobel Surface Chemistry LLC

525 W. Van Buren Street
Chicago IL 60607-3823
(800) 906-9977
(312) 544-7000
http://www.surface.akzonobelusa.com

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©2008 Akzo Nobel Surface Chemistry LLC Publication: SC-08-06

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