CALCULATION

NON-IONIC

OF HLB VALUES
$URFACTANTS*

OF

By WILLIAM C. G.IIN
?it/asPowderCompany,ttilmington,Del.

IN THE PASTFIFTEENor twenty years, there has beena tremendous

growth in the field of surfactants. The term surfactants,as used here,
includesemulsifiers,wetting agents,suspendingagents,detergents,antifoam compounds,and many others. Despite widespreadinterest in all
types of surfactants,there has beenno utilitarian methodof classifying
them. There has been division accordingto ionization,chemicaltype,
and by popular (often ambiguous)nomenclature.
The surfactantused in practically all formulationsprior to the 1930's
wassoap. In the mid 1930'sthe supremacyof soapwas challenged,first
by sulfonatesand sulfate-typeionicsurfactants,and shortly thereafterby
the non-ionics. In the past few yearsblendsof non-ionicand anionicsurfactantshave becomeincreasinglypopular. Throughoutthis period,cationicsurfactantshaveseenincreasedusebut not to the samedegreeas that
of either anionicor non-ionicproducts.
The biggestdifficulty with surfactantstoday, at least from the standpoint of thosewho have to choosethem, is the staggeringnumberthat are
available. Each manufacturertries to provide one or more of his own
productsthat issuitablefor everyneedandthereforeeachhasa tremendous
selection. The large number of surfactantsavailable,coupledwith the
fact that applicationproblemsare becomingincreasinglydifficult,is making the needfor a suitablesystemof selectionof surfactantsmoreandmore
critical.

Any emulsionchemistwho workswith surfactantsfor a few yearssoon

recognizesthat there is a correlationbetween their behavior and their
solubilityin water. For example,he will use a water-solublesurfactant
or blend to make an oil-in-water

emulsion.

He will also use a water-

solublesurfactant for solubilizationand an almost completelywatersolublesurfactantas a detergent. All the productsof theseapplications
may be said to exhibit aqueouscharacteristics;that is, they dilute readily
* Presentedat the May 14, 1954,Meeting, New York City.
249

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with waterandconductelectricity. For thesepurposes

the emulsionchemist wouldunder no circumstances
use an oil-solublesurfactant. However,
to make a water-in-oil emulsion,to couplewater-solublematerialsinto an
oil, or to make a dry-cleaningdetergent,all of whicharenon-aqueous
systems,he would choosean oil-solublesurfactant.
This relationship
of behaviorandwatersolubilitythat is followedby most
experienced
emulsionchemistsis soinexactin its usualform that it isonly
of value as a basisof thinking. We have beensuccessful
in assigningnumericalvaluesto surfactants,therebyprovidinga systemof classification
that is related to their behavior and to their solubility in water. This
method,called the HLB methodfrom the term Hydrophile-Lipophile
Balance,is basedon the premisethat all surfactantscombinehydrophilicand
lipophilicgroupsin onemoleculeandthat theproportionbetweentheweight
percentages
of thesetwo groupsfor non-ionicsurfactantsis anindicationof
the behaviorthat may be expectedfrom that product. The HLB valueis
useful becauseit allowsa predictionof the action that may be expected
from a surfactant; for examplea low value, about4, will be a water-in-oil
emulsifier;a high value, about 16, will be a solubilizer. What is referred
to here is the type of behaviorthat can beexpected,
ratherthan the efficiency
with which this will be accomplished.
In ourlaboratorythebehaviorofsurfactantsin relationshipto theirhydrophilic nature wasfirst recognizedin emulsionstudies. When two non-ionic
emulsifiers,
onehydrophilicand the other lipophilic,weremixedin varying
ratiosthe efficiencyof the blendas an emulsifierfor a givenoil went through
a maximum. Usingpairsof differentsurfactantsto emulsifythe sameoil,
it wasapparentthat thismaximumoccurredat the sameweightpercentage
of hydrophilicsubstance
in the surfactantblend. Essentiallytherefore,
the HLB value is a functionof the weightpercentageof the hydrophilic
portionof the moleculeof a non-ionicsurfactant.
HLB valuesmay be calculatedfor non-ionicsurfactantsor may be determined experimentally. The experimentalprocedureis long and laborious
and was describeda few yearsago [J. Soc. COSMETIC
CHEM.,1,311-326
(1949)].

Formulas
forcalculating
HLB values
maybebased
oneitheranalytical
or compositiondata. For most polyhydricalcoholfatty acid estersapproximatevaluesmay be calculatedwith the formula

HLB=
20(1
Wherein:
S = saponificationnumberof the ester
A = acid number of the acid

HLB VALUES OF NON-IONIC SURFACTANTS

zSx

Examples: (A) Atmul 67 glycerylmonostearate(soapfree)

$ = saponification
number,161
A = acidnumberof fatty acid,198

HLB
=20(1- 16_1'
198]= 3.8
(B) Tween 20, polyoxyethylenesorbitanmonolaurate
$ = saponification
numberspec.,45.5 (mid-point)
A = acid numberof fatty acid, 276

HLB
=20(1--45.5'
276 ] =16.7
Many fatty acid estersdo not give goodsaponification
numberdata;
for example,tall oil and rosinesters,beeswaxesters,lanolin esters. For
thesea calculationmay be basedon the formula:
HLB

E+P

Wherein:

E = weightpercentageof oxyethylenecontent
P = weightpercentageof polyhydricalcoholcontent(glycerol,sorbitol,etc.)
Example: Atlas G-1441; polyoxyethylenesorbitollanolin derivative
E = weightpercentageof oxyethylenecontent,65.1
P = weightpercentageof polyhydricalcoholcontent,6.7
HLB-

65.1 + 6.7
5

14

In productswhereinonlyethyleneoxideisusedasthehydrophilicportion
andfor fatty alcoholethyleneoxidecondensation
products,equation2 may
be simplifiedto
HLB

Example: Myrj 49 polyoxyethylene

stearate
E = weightpercentageof oxyethylenecontent,76

HLB
= 7= 15
Theseformulasaresatisfactory
for non-ionic
surfactants
of manytypes.
However,non-ionic
surfactants
containing
propylene
oxide,butyleneoxide,
nitrogen,sulfur,etc., exhibit behaviorwhich has not beenrelated to composition. In addition, the HLB valuesof ionic surfactantsdo not follow a

weightpercentagebasisbecauseeven thoughthe hydrophilicportionis

low in molecularweightthe fact that it ionizeslendsextraemphasis
to
that portionand thereforemakesthe productmore hydrophilic. For
theseproducts,the experimentalmethodmust be used.
Reg.U.S. Pat. Off., Atlas PowderCompany.

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HLB values for a wide variety of surfactantshave beencalculatedor

observedand are listed in Table 1. As with any systemthat dealswith
surfactants,there are occasionalside effectswhich seemto alter the establishedvalue. Theseare oftenuniqueto the test that is beingrun and there
is no explanationfor themat the presenttime.
Becauseof the difficulty,time, and expenseinvolvedin carryingout the
experimentalprocedure,relatively few of the host of availablesurfactants
have had their HLB values determined. However, this is not the disadvantagethat it first appearsto be, sincea roughestimateof the HLB can
be madefrom the degreeof water solubilityand in many instancesthis is
adequate for screeningwork.
In its presentform, the HLB systemlacksexactness. A suitablesimple
laboratorymethodof measuringHLB valuesof surfactantsaccuratelyis
needed. We have tried a variety of methodsincludingsolubilityin water,
or varioussolvents,ratio solubilityin two solvents,solubilizationbehavior
both for oils and dyes, surfaceand interfacial tensiondata, cloud point
behavior,and manyotherproperties. Of thesethe mostpromisingis the

determination
of the cloudpointof an aqueous
sol'ution
of the surfactant.
However, this test still possesses
severelimitations.
In additionto hydrophile-lipophile
balance,it is believedthat surfactants
possess
a secondpropertywhichis related to their behavior. We call it
chemicaltype. For example,we may find that estersof a particularfatty
acid providebetter emulsification
in a givensystemthan any other fatty
acidesters;or polyoxyalkylene
fatty alcoholsmay give betterperformance

than esters. In all probability,chemicaltype is relatedto the attraction

of the lipophilicgroupin the surfactantfor the lipophilicmaterialwith
whichthe surfactantis beingused. This, we believe,governsthe efficiency
of a surfactant,providedit is of the properHLB. This secondcharacteristic point, the natureof the hydrophilicand lipophilicgroups,alsorequires
further study.
To selecta surfactantproperlyfor any application,we believethat one
must first have the optimumHLB value and secondlyhave the correct
chemicaltype. Since,at the moment we have correlationonly for the
HLB value our procedureis to establishthe requiredHLB and then try a
varietyof chemicaltypesat that optimumHLB. This procedureeliminates
trial of all surfactantsthat are of the wrongHLB and, thus, reducesthe
time and effort requiredto solvea problem.
Just as eachsurfactantor surfactantblendexhibitsan HLB value each
lipophilicmaterial or blendof lipophilicmaterialswith whichsurfactants
areusedexhibitsan optimumrequiredHLB valuefor anyspecific
formulation or application,'Fable2. The determinationof requiredHLB values
has also been studied both from the standpoint of calculation and

HLB

VALUES

OF NON-IONIC

TAn.E 1--CA.CV.ATEr)

Name

Mfr.*

SURFACTANTS

Ant) DETmmnr)

HLB

V^Lvs

ChemicalDesignation
Sorbitan trioleate
Sorbitan trioleate

Span 85

Arlacel 85
Atlas G-1706

1
1

Span 65

Arlacel 65
Atlas G-1050

1
1

Eracol EO-50
Emcol ES-50
Atlas G-1704

2
2
1

Ethvlene glycol fatty acid ester

Eracol PO-50
Atlas G-922

2
1

"Pure"
Atlas G-2158
Emcol PS-50
Emcol EL-50
Era col PP-50

6
1
2
2
2

Arlacel C
Arlacel 83
Atlas G-2859
Atmul 67
Atmul 84

253

Typet

HI,Bt'

N
N

1.8
1.8

N
N
N

2
2.1
2.1

Polyoxyethylene sorbitol beeswax

derivative
Sorbitan tristearate
Sorbitan tristearate

Polyoxyethylenesorbitol hexastearate

Eth3,leneglycolfatty acidester

2.6

2.7

2.7

Polyoxyethylenesorbitol beeswax
derivative

N
N
N
N
N
N
N
N
N
N
N
N
N
N
N

3.4
3.4
3.4
3.4
3.4
3.6
3.7
3.7
3.7
3.7
3.8
3.8
3.8
3.8
3.8

Tegin 515

Aldo 33
"Pure"
Atlas G-1727

4
6
1

Propyleneglycolfatty acidester
Propyleneglycolmonostearate
Propyleneglycolmonostearate
Propyleneglycolmonostearate
Propyleneglycolfatty acid ester
Ethyleneglycolfatty acidester
Propyleneglycolfatty acid ester
Sorbitan sesquioleate
Sorbitansesquioleate
Polyoxyethylenesorbitol4.5 oleate
Glycerol monosrearate
Glycerolmonostearate
Glycerolmonostearate
Glycerolmonostearate
Glycerolmonostearate
Polyoxyethylene sorbitol beeswax

Emcol PM-50

Propyleneglycolfatty acid ester

4.1

Sorbitan mono61eate
Sorbitan mono61eate

N
N

4.3
4.3

Propyleneglycolmonolaurate
Propyleneglycolmonolaurate
Propyleneglycolfatty acid ester

N
N
N

4.5
4.5
4.5

Sorbitan monostearate
Sorbitan monostearate

N
N

4.7
4.7

Diethyleneglycolmono61eate
Diethyleneglycolfatty acidester
Diethyleneglycolmonostearate
Diethyleneglycolfatty acidester
Polyoxyethylene sorbitol beeswax

N
N
N
N

4.7
4.7
4.7
4.7

5.1

5.5

A
N

5.5
5.6

N
N

6.1
6.1

N
N
N
N
N

6.5
6.7
6.7
7.5
7.7

1
1
1

derivative

Span 80
Arlacel 80
Atlas G-917
Atlas G-3851
Eracol PL-50

1
1
1
2

Span 60
Arlacel 60
Atlas G-2139
Emcol DO-50
Atlas G-2146
Emcol DS-50
Atlas G-1702

1
1
2
1
2
1

Emcol DP-50
Aldo 28

2
4

Tegin

Emcol DM-50
Atlas G-1725

2
1

Atlas G-2124

Emcol DL-50
Glaurin

2
4

Span 40

Ariaeel 40
Atlas G-2242
Atlas G-2147

1
1
1

derivative

Diethylene glycol fatty acid ester

Glycerol monostearate(self-emulsifying)
Glycerolmonostearate(self-emulsifying)
Diethyleneglycolfatty acid ester
Polyoxyethylene sorbitol beeswax
derivative

Diethylene glycol monolaurate

(soapfree)
Diethyleneglycolfatty acid ester
Diethylene glycol monolaurate
(soapfree)
Sorbitanmonopahnitate
Sorbitanmonopahnitate
Polyoxyethylenedioleate
Tetraethyleneglycol monostearate

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JOURNAL OF THE SOCIETY OF COSMETIC

CHEMISTS

TAB[ 1--(Continued)

Name

Mfr. *

ChemicalDesignation

Typet

HLB j''

Atlas G-2140
Atlas G-2800
Atlas G-1493

1
1
1

Tetraethyleneglycolmono61eate
Polyoxypropylene
mannitoldioleate
Polyoxyethylene sorbitol lanolin

Atlas G-1425

Polyoxyethylene sorbitol lanolin

AtlasG-3608

Polyoxypropylene
stearate

Span 20

Sorbitan monolaurate

8.6

oleate derivative
derivative

N
N

7.7
8

Arlacel :20

Sorbitan monolaurate

8.6

EmulphorVN-430
Atlas Go1734

3
1

Polyoxyethylenefatty acid
Polyoxyethylenesorbitol beeswax

Atlas G-2111

Polyoxyethylene
oxypropyleneole-

Atlas G-2125

Tetraethyleneglycol monolaurate

9.4

Brij 30

Polyoxyethylene
laurylether

9.5

Tween 61

Polyoxyethylenesorbitanmonoste-

Atlas G-2154
Tween 81

1
1

Hexaethyleneglycolmonostearate
Polyoxyethylene
sorbitanmono61e-

Atlas G-1218

Atlas G-3806
Tween65

1
1

Polyoxyethyleneesters of mixed
fatty and resin acids
Polyoxyethylenecetyl ether
Polyoxyethylenesorbitan tristea-

Atlas G-3705
Tween 85
Atlas G-2116

1
1
1

Polyoxyethylene
lauryl ether
Polyoxyethylenesorbitantrioleate
Polyoxyethylene
oxypropyleneole-

11

Atlas G-1790
Atlas G-2142
Myrj 45
Atlas G-2141
P.E.G. 400 monooleate

1
1
1
1

Polyoxyethylenelanolinderivative
Polyoxyethylene
mono61eate
Polyoxyethylene
monostearate
Polyoxyethylenemonobleate

N
N
N
N

11
11.1
11.1
11.4

Polyoxyethylene
mono61eate

11.4

7
1
4

Polyoxyethylene
mono61eate
Polyoxyethylenemonopalmitate
Polyoxyethylenemonostearate

N
N
N

11.4
11.6
11.6

Polyoxyethylenemonostearate

11.6

stearate
AtlasG-3300

7
1

Polyoxyethylenemonostearate
Alkyl aryl sulfonate

N
A

11.6
11.7

Atlas G-2127
Igepal CA-630
AtlasG-1431

1
3
1

Polyoxyethylenemonolaurate
Polyoxyethylene
alkyl phenol
Poloxyethylene
sorbitollanolinde-

AtlasG-1690
S-307

1
4

Polyoxyethylene
alkyl aryl ether
Polyoxyethylenemonolaurate

1
1
3
1

derivative
ate

arate

ate

rate

ate

P.E.G.

10.0

N
N

10.2
10.3

10.5

N
N

10.8
11

400 mono-

Triethanolamine

oleate

1:2

N
N

1:2.8
12.8

13

N
N

13
13.1

Polyoxyethylenemonolaurate

13.1

Polyoxyethylene
laurylether
Polyoxyethylene
castoroil
Polyoxyethylene
vegetableoil
Polyoxyethylenesorbitan mono-

N
N
N

13.1
13.3
13.3

13.3

rivative

P.E.G.

9.6

400 mono-

stearate
P.E.G.

9.6

400 mono-

oleate
Atlas G-2076
S-541
P.E.G.

400 mono-

laurate

AtlasG-2133
Atlas Go1794
EmulphorEL-719
Tween21

laurate

HLB VALUES OF NON-IONIC

SURFACTANTS

255

TaBLV-1--(Continued)

Name

Mr.*

Chemical
Designation

Typet

HLBt t

13.5

14

14.9

14.9

15

N
N
N
N
N
N

15.0
15.1
15.3
15.3
15.4
15.4

15.5

Renex20

Polyoxyethyleneesters of mixed
fatty and resin acids

AtlasG-1441

Pol.yox.yethylene
sorbitol
lanolin
de-

Atlas G-7596J

Polyoxyethylenesorbitan mono-

Tween60

Polyoxyethylene
sorbitanmonoste-

Tween 80

Polyoxyethylene sorbitan mono-

Myrj 49
AtlasG-2144
AtlasG-3915
AtlasG-3720
AtlasG-3920
EmulphorON.870

1
1
I
1
1
3

Polyoxyethylene
monostearate
Polyoxyethylene
mono61eate
Polyoxyethylene
oleylether
Polyoxyethylene
stearylalcohol
Polyoxyethylene
oleylalcohol
Polyoxyethylene
fatty alcohol

Tween40

Poly.
oxyethylene
sorbitan
monopal-

AtlasG-3820
AtlasG-2162

1
1

Polyoxyethylene
cetylalcohol
Polyoxyethylene
oxypropylene
ste-

AtlasG-1471

Pol.yox.yethylene
sorbitol
lanolin
de-

Myrj 51
AtlasG-7596P

1
1

Polyoxyethylene
monostearate
Polyoxyethylenesorbitan mono-

AtlasG-2129
Atlas G-3930
Tween20

1
1
1

Polyoxyethylene
monolaurate
Polyoxyethylene
oleylether
Polyoxyethylenesorbitan mono-

Brij 35
Myrj 52
Myrj 53

1
1
1

Polyoxyethylene
laurylether
Polyoxyethylene
monostearate
Polyoxyethylene
monostearate
Sodium oleate

18

AtlasG-2159

Polyoxyethylene
monostearate

18.8

Potassium oleate

20

AtlasG-263

N-cetyl N-ethyl morpholinium

Puresodiumlaurylsulfate

rivarive

burate
arate

oleate

AtlasG-2079

Polyoxyethylene
glycol monopalmitate

mtate

arate

nvauve

laurate

burate

ethosulfate

15.6

15.7

15.7

16

16.0

16.3

N
N

16.3
16.6

16.7

N
N
N

16.9
16.9
17.9

2540

App. 40

* 1 = AtlasPowderCompany,2 -- EmulsolCorporation,
3 = GeneralAniline& Film

Corporation,
4 -- GlycoProducts
Company,
Inc..5 -- Goldschmidt
Chemical
Corporation,
6 = Kessler
Chemical
Company,
Inc.,7 -- W. C.Hardesty
Company,
Inc.
t A -- Artionic,
C -- Cationic,N -- Non-ionic.
tt HLB values,eithercalculated
or determined,
believedto be correctto 4-1.

a varietyof physicaltests. Thereappears

to bea correlation
of required
HLB valuewith chemicalcomposition,
thoughthereare insufficient
data
to showa fixedrelationship
at the presenttime.
It seemspossiblethat, given(1) a suitablesorting-coding
systemfor

surfactants
based
on(a)HLB, and(b) chemical
type,and(2) a moreorless
parallelor complementary
sorting-coding
systemfor the lipophilicma-

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CHEMISTS

T.SLZ 2--"REo. ux-EDHLB" VALVES

w/o
Emulsion

Acid, stearic
Alcohol,cetyl

..

Lanolin,
anhydrous

Oil

}'

o/w
Emulsion

Solubilizing*

17
13

15

Cottonseed
Essential

..

7.5

Mineral,
heavy

1)'.

Mineral, light
Vitamin (with fats or oils)
Vitamin (fat free)

4
.....

10-12

Petrolatum

lb'.'5

Vitamins
Esters

.....

1;'.
1.5
15
16.5

Oils (see"Oils" above)

Wax

Beeswax

Microcrystalline

Paraffin
(household)

10-16

9.5

* O/W, i.e., solubilizingin water.

terialsusedwith surfactants,a crossrelationshipcould be set up. With

sucha system,it shouldbe possibleto screenall the availablesurfactantsin
a few minutesand selecta few that are worthy of extensivestudy.
In summary,two conditionsusuallymust be satisfiedin choosinga surfactantfor any desiredformulation. First, the properHLB or hydrophilic
content of the surfactantmust be used, and secondthe properchemical
type of the surfactantmust be chosen. Random choice,i.e., the old trialand-errormethod,canlead to many selectionsthat are wrongin two ways;
that is, both by chemicaltype and HLB. By first determiningthe optimum
HLB value and then selectingand testinga variety of chemicaltypes at
thisparticularvaluea largenumberof wrongtrials canbe eliminated. The
HLB methodpermitsa more systematizedtrial than possiblepreviously.
HLB valuesmay be calculatedfrom analytical or compositiondata or the
systemmay be usedwithout calculatingor determiningexact value sinceit
is a methodof operationthat hassomecorrelationwith water solubilityof
the surfactants.

There is need for further work in this field to establish a

rapid,moreexactexperimental
procedure
for observing
HLB values,fordetermining"requiredHLB's," and for classifyingand correlatingchemical
typesof surfactants.