J. Soc. CosmeticChemists,19, 129-136 (Feb.

5, 1968)

A Titration Determination
HLB's

Method of the

for the

of Emulsifiers
JAMES J. MIDDLETON, B.A., M.B.A.*

PresentedMay , 1967, New York City

Synopsis--A titration method for determining HLB's, particularly of emulsifiers, is presented. This is a color-migration procedure, similar to the Epton method for determining anionics or cationits. Parameters of variables are discussed,especially as to the control of errors and their magnitude for any one variation. Application to the determination of the HLB requirements of mixed-oil phasesis also discussed.

INTRODUCTION

The HLB concept (hydrophile-lipophilebalance of a nonionic emulsifier)was introducedby Griffin (1). It has sincebeen refinedand extendedby Griffin, Carter, and their group (2, 3), and summarizedby Griffin (4). The practicalvalue of the systemto technicalpeoplein the cosmetic, detergent,and emulsionfieldshas been amply demonstrated. This systemprovidesa unifying method which embracesseveralfamilies of surfactants, and dividesthe effort requiredto selectthe most effective agent to use in a particular project. The HLB of an emulsifier is a numberwhich expresses the ratio betweenwater-soluble groupsand oil-soluble groups in the molecule. The higher the HLB number, the more water-directed is the entire molecule. Surfactants of a givenchemical type canbe arranged in a series, starting with the most oil-directedand advancingto the most water-directedas
* Millmaster-OnyxCorp., Onyx ChemicalCo. Div., 190 Warren Street, JerseyCity,
N. J. 07302.
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the numbers increase. Suchseries include the Span * andTween * group and the Neutronyx surfactants. Thereare, of course, other
tradename series too numerous to list here.

Several authors have reported attempts to relate HLB to various other properties of the surfactant molecules(5-8). At present, however, the most direct method, which at the same time includes factors in

addition to the HLB itself, is actually to make a set of emulsions,using the desiredoil phase,and varying the HLB throughoutthe set in a regular manner. HLB values intermediate between those of commercial

productscan be achievedby mere mixing of these products. For example,blending70% Tween 80 (HLB of 15) and 30% Span 80 (HLB of 4.3) (0.70 X 15) + (0.30 X 4.3) = 11.8, HLB of the blend. Thus, a higher-HLB emulsifieris mixed with a lower-HLB emulsifierin suchproportions that the average HLB's of the severalmixtures as calculated show a regular variation. The emulsionsin the seriesare then completed, and their stabilitiesare observed. The most stable onescluster around a particular HLB range. Then, another set of emulsionsis made, to range more compactly aroundthis HLB stability-peak and subdivide the values more finely than in the first set. This narrowing down process can be carried out further until an almost infinitesimal range is covered; but there is a practical limit of refinement left to the judgment of the chemist.

It is perfectlyproperto speakof the HLB of a nonsurfactant, suchas mineral oil. In this sense, we refer to the HLB required by the mineral oil to becomeemulsified,even though the oil itself has no duality of both oil- and water-solubility. In fact, mineral oil requires an HLB of 10 to
become emulsified in water, and an HLB of 1.8 to form a water-in-oil system.

The author has found that, for preliminary screening,a rapid titration procedure is highly useful. Briefly, a water solutionof the higherHLB material is titrated with a solution of the lower-HLB material, in

the presence of the oil phase. An indicator is used,the most dependable found so far being a carbon black. At the end point, the carbon migratesfrom the water phaseinto the oil, with high visibility. Under the experimentalconditions detailedbelow, emulsification of the oil doesnot occurat the end point, and the phaseseparation is rapid. The crucial
effect seemsto be on the carbon black itself rather than on the oil phase, although this is still somewhatconjectural.
* Atlas Chemical Industries, Inc., Wilmington, Del. t Onyx Chemical Co., Jersey City, N.J.

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Figure 1. Titrationwith Neutronyx 640 and 626 , Lorol //5.

Left, before end point; Center, at end point; Right, after end point

EXPERIMENTAL

Ten per cent water solutions are made of the emulsifier under test,
and also of an emulsifier with known HLB. The lower HLB surfactants

ordinarily require a hydro-alcoholic solvent, but the alcohol content shouldbe kept as low as possible. Water solutionsare preferred, even if they are cloudy, as long as they are stable. Ten milliliters of the higher-HLB solution are added to a 100-ml graduated cylinder. About 0.1 g carbon black* is added, and the cylinder is shaken to wet out and dispersethe pigment. Water is added to total about 80 ml. Ten grams of the selectedoil phase is added and the container is shaken gently to mix the contents without generating a great
deal of foam. The low-HLB solution is added in increments from a

burette. Unless one can estimate in advance the probable titrant volume and thus approach it rapidly, it is well to start with 1-ml additions, shaking after each, then allowing the phases to separate. The end point is taken as an apparently even division of black between the two phases. Figure 1 shows such a titration. The oil phase is lauryl alcoholt and the two surfactantsused are ethoxylated nonyl phenols,Neu-

tronyx//640and //626, with emulsifying HLB's of 15 and10.7,respectively. The center cylinder shows the end point at the calculated mix-

* Carbon Black,Vulcan#9, Godfrey L. CabotCo., 125High St., Boston, Mass. ,+ Lorol#5, E. I. dupontde Nemours & Co.,Wilmington, Del.

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14

12

10

IHLB I (Tran, 'sfer)

12 14 16,

Figure2. Correlation of transferor titration end point HLB with o/w emulsification HLB

requirement: 1. Lorol#b , 2. ButylMyristate, and3. Klearol mineral oil

ture HLB of 12.66. On the left is a titration with 0.5 ml lesstitrant, and

onthe right,with 0.5 ml more. This is a fineexample of the precision of the methodwhencarefullyperformed, sincedespite the greatvisibledifferences, the HLB's are, from left to right, 12.70, 12.66,and 12.62,as calculatedfrom the known quantitiesof the two emulsifiers used,and their
known HLB values.

Similar titrations utilizing the sameNeutronyx, with mineraloil* as the oil phase,gave a value of 3.6 for the end point. Butyl myristate
showedan end point at 6.
CALCULATIONS

The published HLB requirements for the emulsification of lauryl alcoholor mineraloil into water are 14 and 10, respectively (9). The same reference includesthe HLB requirementof 11 for butyl myristate.
When theseemulsification valueswere comparedwith the valuesshown by our carbonblack migrationend points,a straight-line relationship, graphically, wasfound (Fig. 2). The line-locus is y = 0.45x -[- 8.3; y
* Klearol, Sonneborn Division (Witco Chemical Co.),277ParkAve.,NewYork,N.Y.

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beingthe O/W emulsification HLB requirement,and x the HLB foundby the carbon black titration. To date, all relatively pure chemicalswhich have been standardizedand which have O/W HLB values published agreewith this relationship. It might appear from the graph of Fig. 2 that oil phaseshaving an HLB requirement below 8 cannot be characterized by this titration method. In a few cases, the author has performedtitrations which gave negativevalues after calculatingthe end point HLB. When thesenegative values were substitutedinto the line equation,however,O/W HLB valuesresultedwhich were below 8, and quite verifiable by preparing a
stable emulsion therewith.
APPLICATIONS

Although this method has been applied successfully in severaltechnical serviceproblemshaving to do with emulsifying,no attempt to develop a library of HLB values for commercial emulsifiers,or for oils, has been made. Many emulsifiervalues have been publishedby suppliers or are available from the suppliersconcerned. As is true in all experimentalor analytical work, precautionsmust be taken, limitations of a method must be recognized,and good judgment must be used. Also, unfortunately, there will probably always be instanceswhen a method just won't work becauseof undetermined interferences.

The carbonblack selected is fine enoughto disperse into an intensely black suspension, but it is very important that it actually be well dispersedinitially. With certain types of nonionicswhich may not wetout well, even though the HLB is high, it is best to start a fresh cylinder with 1 ml of a 10% solutionof anothernonionicof known HLB that is a gooddispersant,add and wet-out the carbonblack, and make up to the 10 ml specified with the high-HLB solutionunder test. Oncethe carbon is dispersed, it will ordinarily remain so. The dispersantadded must be includedin the final calculationof the end point HLB. It is necessary to shakethe cylinder just before each addition of titrant. If titrant is addedto the oil phasedirectly,floating at the top as
it does, the local concentration of low-HLB
wet the carbon whether this HLB

titrant thus added into the

oil will usually distort the end point. A sufficientlylow HLB will oilis reached in the normal course of the

titration or accidentally. The carbon presumably cannot distinguish the intention of the chemist. Oncewet by the oil, the carbondoesnot readily divestitself to becomeoncemorewater-wet. This appearsto be

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the greatestsinglesourceof error both by preventinga thoroughmixing of the two emulsifiers in the water phase,and by coloringthe oil-layer prematurely. For this reason,the method calls for titrating a higher
HLB with a lower one, and does not offer the alternate choice.

It is possiblein some systems, especiallyin preliminary screening runs, to passthrough the optimum HLB for forming an O/W emulsion with the oil phase. While this is not the titration end point, it is still an analyticalnuisance. Continuingthe titration shouldbe attempted,and eventually the emulsionshouldbreak up. In the caseof lauryl alcohol,
however, the emulsion may be a quite compact mass and form more or lessof a plug at the top. In case of difficulty, two alternatives are offered. First, one can start all over again, using a different substrateto begin with, having an HLB below the value of 14 publishedas optimum for the O/W emulsification of lauryl alcohol. Or, one can set up a seriesof step-wisetitrations in which both the high and the low HLB solutionsare premixedin

the cylindersand brought up to volume before the lauryl alcoholis

added. Now, observationsafter shaking can be lined up, and the titration HLB closelyestimated. This alternative is reminiscentof the making of an emulsionseriesto determineHLB values,but it is far faster. Each phaseseparation will be completeenough to be evaluatedin under five minutes, even if the entire 10 ml of oil doesnot separate out in that
time.

To determine the HLB of an unknown emulsifier, a simple oil of known HLB requirement is selected,and titration is performed with solutions of the unknown surfactant and one of known HLB. Another

commonproblemis to determinethe properO/W emulsification HLB requirementof a mixed oil phasethat has alreadybeenselected. The author usually starts a trial with solutions of emulsifiers with extremes of HLB. Thus, a range for the end point is found quickly. This can be further refined by repeating the titration with two surfactants both
somewhat closerto this range.

One difficulty with this method is the evident requirementthat the oil phasemust be liquid at room temperature,so that the carboncan distribute, and so that the oil phasecan separateout homogeneously. Bearing in mind that not only are the HLB's of emulsifiers additive in mixtures, but that the sameholdstrue for oil-phaseHLB requirements, the author hasworkedwith toluenesolutions of petrolatum. It appears that the additive function works very well so long as the petrolatum remains dissolved; that is, as long as the concentration is below that of a

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saturated solution. HLB's of these mixtures titrated with increasing accuracy as the content of petrolatum was increased.
EFFECTS OF OTHER FACTORS

The effectsof added electrolyte, alcohol, and increasedtemperature are of minor influence when relatively small changesare made in these parameters. Above certain levels, the effectsbecomeso large that the author has not yet been able to measurethem completely with acceptable accuracy. Up to 1% electrolyte in the titration is tolerable, whether acetic acid, sodium or potassium chloride, or aluminum salts, so long as no chemicalreaction occursin the system. Up to about 10% alcohol,either ethyl or isopropyl, can also be accommodated. Temperatures to 35 C induce little change. Above this, titration HLB's rise rapidly (considerably more of the low HLB titrant must be added) and duplication of results becomes difficult.

The fact that these three factors change the HLB of a system is of great interest. Those who develop emulsion products are aware that any one of these can destroy an otherwise elegant formulation. It is thereforesuggested that titrations be performedafter including the electrolyte or alcoholin the water phase. This may easelater effortsto assure stability. As to temperature, stable emulsionshave been found to separateafter oven storage. The changeof HLB requirementreported here may be a sufficientexplanation,althoughnot a remedy. Possibly supplyingan HLB intermediatebetween the two may offer stability at both oven and room-temperature conditions. These three factors most likely operate by changingthe hydration of the ethylene oxide chains, thereby altering the micelle structure and critical micelie concentrationof the system.
The method has other built-in bonuses, which can be used with in-

genuity to solve many difficult cases,sometimesalmost accidentally. The author had occasion recently to emulsify a very dark colored oily material. Obviously, a prior determination of the HLB was desirable. While dubiousthat any darkening of the oil from the carbon migration would be observable,the titration was tried anyway. To observe the darkening was, indeed, hopeless. But, rewardingly, at one point the water phasesuddenlybecamealmostwhite as the carbontransferredinto the oil, not only demonstrating the end point, but alsogreatly relieving one anxious chemist. The HLB determined was, actually, quite cor-

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rect, as shownby the stable emulsions later compounded using the converted O/W HLB. This titration method, while probably not foolproof, is a convenient and easy means for rapidly developinginformation to prepare specific emulsionformulations. The choiceof emulsifiersis quickly narrowed down, and the application range of a new emulsifieris quickly determined. In the hands of a skilled chemist, many of its shortcomings can be avoided, and the procedureprobably can be improved into greater usefulness as experiencewith it grows.
(Received May 19, 1967)
REFERENCES

(1) Griffin, W. C., Classificationof surface-activeagents by "HLB," J. Soc. Cosmetic Chem~ ists, 1,311-26 (1949). (2) Griffin, W. C., Calculation of HLB Values of non-ionic surfactants, Ibid., 5, 249-55 (1954). (3) Griffin, W. C., Clues to surfactant selection offered by the HLB System, Q//c. Dig., FederationPaint & Varnish Production Clubs,28, 466-75 (1956). (4) Griffin, W. C., Emulsification, in Sagarin, E., Cosmetics:Science and Technology, IntersciencePublishers, New York, N.Y., 1957, pp. 998-1033. (5) Becher, P., The effect of the nature of the emulsifying agent on emulsioninversion,J. Soc. Cosmetic Chemists, 9, 141-8 (1958). (6) Ross, S., Chen, E. S., Becher, P., and Ranuto, H. J., Spreading coefficientsand hydrophile-lipophilebalance of aqueoussolutionsof emulsifyingagents, J. Phys. Chem.,63, 1681-3 (1959). (7) Becher, P., Spreading,HLB, and emulsionstability, J. Soc. Cosmetic Chemists, 11, 32532 (1960). (8) Greenwald, H. L., Brown, G. L., and Fineman, M. N., Determination of the hydrophilelipophilecharacterof surface-active agentsand oilsby a water titration, Anal. Chem., 28, 1693-7 (1956). (9) Atlas Chemical Industries, Inc., The Atlas HLB System,pamphlet, 1963.