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Presented
October11, 1971, Joint Symposium
of theSociety
of Cosmetic
Chemists
and theAssociation
of Ocial AnalyticalChemists,
Washington,
D.C.
Synopsis--Modern SHAMPOOS are designednot only to clean the hair and scalp,but to
impart conditioningproperties,fragrance,luster, and other attributes to hair. As a consequence,
the ANALYSIS of a shampoobecomesa complicated exercisein separationand identification
of components,calling on many of the disciplinesof modern analyticalchemistry.
The literature on shampooanalysisis reviewed and someolder schemesof analysisare discussed. A proposedschemefor the analysisof a modern shampoousing a combination of
SOLVENT EXTRACTION
SEPARATION
is presented.
INTRODUCTION
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ANALYSIS
OF
889
SHAMPOOS
Acidified
Alcohol
Weakly
Basic
Ion Exchange
Column
Alcohol
Eluate
I Amm.(NH412CO
3Eluate
I
[ Evap.-Dissolve
I
linWaterr:Na2C031
NH
4Alkyl
Sulfate
/Evap.-Ext.
Acer.
I
Sap-Na2C03
Residue
I Extract
Ext.
CHCI
3
Amine
Condensate
Hot
H20-Acid
I
Fatty
Acid-Alkanol
Fatty Acids
titativeanalysis
of surfactants
in shampoos.
He useda Teflon
* seal
with a backing plate on the back face of a KRS-5 attenuated total reflectance (ATR) prism forming a cell to contain a liquid shampoowhich can
be scannedby ir. Spectraobtained over the "fingerprint region" were
usedto identify an ethoxylatedalcohol, a sulfatedalcohol, and a sulfated
fatty alcoholethoxylate. The qualitative method wasadapted to a quantitative methodfor lauryl ether sulfateby measuringthe sulfateabsorbance
* E. I. dupont de Nemours Corporation, Wilmington, Del.
890
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at 1220 cm -.
OF
THE
Excellent
SOCIETY
correlation
OF
COSMETIC
of the method
sodium
CHEMISTS
titra-
It wasreportedthat
and triethanolamine
Schwarz(22) statedthat the analystmusthave someidea of the componentsto determine how to proceed with the shampooanalysis. He
made useof the titrationsof Epton (23) and Barr etal. (24) beforeand after
acid hydrolysis,and the hydroxyl number of the fatty alcoholor the acid
number of the fatty acid thus liberated. He advisedthe useof gaschromatographyto determinecarbon-chaindistributionof the acid or alcohol.
He alsodiscussed
the practicality of column chromatography,solventextraction, thin-layer and paper chromatography. An ir spectrummight
be usefulif the mixture is not too complex. A very seriousproblem to
analysisof shampoos,he pointedout, is that the raw materialsusedin the
surfactantsare not lure. Schwarzstatedthat, in the analysisof shampoos,
a compromisemust be made betweenthe costand the expenditureof time
and the desiredresults. It was Schwarz' opinion that often the results
obtainedare not worth the expenditure(22).
ANALYSIS
OF
SHAMPOOS
891
From the foregoing,one might concludethat there is no singleuniversal method which can be usedto analyze all kinds of shampoos. A more
PROPOSED METHOD
OF SHAMPOO ANALYSIS
.oo
0o0
2500
2000
1800
1600
1400
1:200
1000
800
600
FREQUENCY(CM-I)
Quantitative
Estimationof Total SoapandAnionicSulfated
(orSulfonated)
Surfactants
The soapand artionicsurfactantspresentare determined at an early
stage of analysisto decide what further proceduresto use. Absenceof
either soapor artionicsurfactantsmay simplifythe analysisby permitting
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Separation
of Cellulosic
Materials
Many shampooscontain cellulosic materials as thickening agents.
Newburger(19) suggested
usingethanolto precipitatewater-solublegums
and then preparing a dried film on which the ir spectrumis run with the
aid of water-repellentglassplates.
The presentauthorsfound that in many casessomewater must be removedfrom the samplein order to precipitate the cellulosicmaterialswith
ethanol. The coagulatedcellulosicmaterial can be removedby filtering
through glasswool and purified by washingwith freshethanol. To prepare the cellulosicmaterial for recordingits ir spectrum,it is preferableto
make a viscoussolution of it with water, deposit a thin film on a silver
chlorideopticalwindow,and dry in a 105C oven.
Separation
of Alkanolamide
from a Shampoo
Containing
lPropylene
Glycol,Soap,anda SulfatedDetergent
It was found that an alkanolamide can be isolated from a shampoo
containing propylene glycol, soap, and a sulfateddetergent by passinga
solutionof it through a cationic-anionicmixed bed ion exchangecolumn
In practice,a 2.4-cm i.d. glasscolumn is packedwith 50 ml of Amberlite MB-I resin, 20-50 mesh, and is back-flushed with distilled water to
obtain a good packing. A 2-g sample (preferably containing lessthan
To recover the
ANALYSIS
3500
3000
2500
2000
OF
1800
SHAMPOOS
1600
1400
893
1200
1000
80C
600
FREQUENCY(CM4)
Separation
of Soap,ArtionicSurfactant,
andNonionicSurfactant
in a Shampoo
Figure 4 is a schematicrepresentationof the followingprocedure:
Separation
ofSoap
In the analysisof a shampoocontaining soap, artionic surfactant,and
nonionic surfactant,soap is separatedby drying the sample with excess
sodium carbonate, and extracting the artionic and nonionic surfactants
with a mixed solventof 1: 1 diethyl ether and acetone.
About 5 g of the shampoosampleis thoroughlymixed with an equal
weight of pulverized, anhydrousNa2COa and the mixture is dried in a
105C oven until no further lossof weight. The sampleis cooledand
extracted with six 20-ml portionsof 1: 1 diethyl ether-acetone mixture and
the extract is filtered.
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IDried
Sample
I
n Na2CO
3
Ext. EtOEt-Acet.
Soap
and
(norgenies
Residue
I Fdtrate
ExtCHCl
3
1,1IPA-H20
Arnoinc
and
Nonlomc
Surfactants
I
Fatty
Acid
IAmberlite
IR-120
Stnp
wth
2NaOH
In1:1
IPA-H20
I
IAmberlite
IR-45
Effluent
Ion
Exchange
I
INeut.
with
H2S041
Nonionic ISat.
with
Na2CO31
Surfactant
! at60C.
I
Strip
with
2N HCI
Evap to
IPA LayerEvap
Dryness
I
Alkanolamlne
(ir)
HCI
1:1
Ether-Acetone
Purification
Sodium Salt of
Arnoinc Surfactant
(It)
Figure4.
20OO
1goo
16oo
143
1200
lo00
FREQUENCY(CM-I)
Figure5.
Infrared spectrum of a commercial shampoo from which soap has been removed
(dried residueon KBr plate)
ANALYSIS
OF
895
SHAMPOOS
in the column
effluent.
retained
in the
A sample(containingno more than 3 neq of total anionics)is prepared in 50 ml of 1: 1 IPA-water solventand the solutionispassedthrough
the sulfonicacid column mounted over the polyamine column and then
throughthe polyaminecolumnat 2 ml/min. Enoughsolventshouldbe
passedthrough both columnsuntil all the nonionicsurfactantis removed.
It usuallytakesabout 600 ml of the solventto elute all the nonionics. The
nonionic surfactantis recoveredby evaporatingoff the solventand its ir
spectrum is obtained. For accurate quantitative determination of nonionic surfactantsin the sample,oneshouldstart with a fresh sample (without drying with Na.COaand solventextraction)and carry through the
procedurefor separationof alkanolamidedescribedabove.
Recovery
of Alkanolamine
from theCationicExchanger
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3500
3000
OF
2500
THE
2000
SOCIETY
1800
OF
COSMETIC
1600
]4oo
7200
CHEMISTS
1000
80o
GO
4oo
FREQUENCY(CM-)
Figure 6.
ent is neutralized with H2SO4, heated to 60 C, and saturated at this temperature with anhydrousNa2COa to separatethe IPA layer from the water
layer. After it is cooled to room temperature, the IPA (top layer) is
drawn off and evaporatedto dryness.The residuecontainsthe sodiumsalt
of the anionic detergentplus somedissolvedinorganic salts. To purify
the anionic detergentfor recordingits ir spectrum,the residueis extracted
with a solventmixture of 1:1 acetone-diethylether (34), the extract is
filtered, then evaporatedto dryness.
Recoveryof the anionicdetergentby this procedureis not quantitative
in the authors' experience. However, the recovered material is pure
enoughfor identificationby comparisonof its spectrumto known spectra.
A sodiumalkyl sulfatespectrumseparatedby this procedureis shownin
Fig. 7.
3500
3000
2500
2000
1800
1600
1400
1200
10oO
800
600
400
FREQUENCY(CM-I)
ANALYSIS
OF
SHAMPOOS
897
SUMMARY
A comprehensiveliterature surveyof methodsfor the analysisof shampoos has been presented. A proposed schemeof analysis for complex
modern shampoosusinga combinationof solventextraction, ion exchange
separation,and infrared spectroscopy
is presented.
(ReceivedFebruary 2, 1972)
REFERENCES
898
JOURNAL
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SOCIETY
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CHEMISTS
(21) Puttnam, N. A., Baxter, B. H., Lee, S., and Stott, P. L., Application of attenuated total
reflectance infrared spectroscopyto toilet articles and householdproducts. II. Quantitative analysis,Ibid., 1779-16 (1966).
(22) Schwarz, G. W. G., Possibilitiesand limitations of shampooanalysis,Ibid., 17, 737-44
(1966).
(23) Epton, S. R., New methodsfor the rapid titrimetric analysisof sodiumalkyl sulfatesand
relatedcompounds,Trans.FaradaySoc.,44, 226 (1948).
(24) Barr, T., Oliver, J., and Stubbings,W. V., The determinationof surfaceactiveagentsin
solution, J. Soc.Chem.Ind., 67, 45-8 (1948).
(25) Yoshikawa, K., Nishina, T., and Takehana, K., Thin-layer chromatographyof detergents. I. Simultaneousanalysisof commercialliquid shampoos
and liquid dishwashing
detergentsby TLC, Yukagaku,
15, 65-72 (1966); Chem.Abstr.,64, 11445(h), (1966).
(26) Fairchild, (2. M., and Kabacoff, B. L., Analytical chemistryof zinc pyrithione,VI, presentedat semi-annualmeetingof the Societyof CosmeticChemists,New York, May 8,
1969.
(27) Graber, M. B., Domsky, I. I., and Ginn, M. E., Thin-layer chromatographicmethodfor
identificationof germicidesin personalcare products,J. Amer.Oil Chem.Soc.,46, 529-31
(1969).
(28) Jones,J. H., Newburger, S. H., Champion,M. H., Kottemann, C. M., and Gross,F. C.,
Gas chromatographyin cosmeticanalysis,Proc.Joint Conf.Cosmet.
$ci., 75-89 (1968),
Toilet GoodsAssoc.,Washington,D.C.; Chem.
Abstr.,70, 109096(g), (1969).
(29) Gross,F. C., and Jones,J. H., Determination of propyleneglycol in cosmeticsby gas
chromatography,J. Ass.Offc.Anal. Chem.,50, 1284-6 (1967).
(30) Fairchild, C. M., Analytical chemistryin the cosmeticsindustry, Anal. Chem.,$9 (10),
22A-24A, 26A, 28A, 30A, 32A, and 34A (1967).
(31) Jones, J. H., General colorimetric method for determination of small quantities of sulfonatedor sulfatedsurface-active
compounds,/. Ass.Offc.Agr. Chem.,28 398-409 (1945);
Chern.
Abstr.,$9, 3951 (q), (1945).
(32) Kecskemethy,L., Szamoskozi,Z., Weber, C., and Bozoki, G., Qualitative and quantitative analysisof perfumesby uv spectrophotometry,Olaj, Szappan,Kozmet,17, 23-6
(1968).
(33) Ginn, M. E., and Church, C. L., New columnar and mixed-bed ion exchangemethods
for surfactantanalysisand purification,Anal. Chem.$1,551-5 (1959).
(34) Ross,L. U., and Blank, E. W., Error in the determinationof the active ingredientin de-