j. Soc.

Cosmet.
Chem.,33, 281-295(September/October
1982)

Conversion
of aluminumchlorohydrate
to aluminumhydroxide

DIRK L. TEAGARDEN*, STANLEY L. HEM, Dept.of

Industrialand Physical
Pharmacy, andJOE L. WHITE, Dept.of
Agronomy, PurdueUniversity,IVestLafayette,IN 47907.
*Presentaddress.'
TheUpJohnCo.,Kalamazoo, M149001.

Received
October
22, 1980.Presented
at theSCCAnnualScientific
Meeting,New York,NY, Dec.11-12, 1981.

Synopsis
The structure
of aluminumchlorohydrate, a highlysolubleanti-perspirant,
andaluminumhydroxide,an
insoluble
antacid,arediscussed
in relationto themechanism of conversionof aluminumchlorohydrate
to
aluminum
hydroxide.
X-ray,IR, and27A1
NMR spectroscopic
dataindicate
thataluminum
chlorohydrate
is composed of a centralaluminumin tetrahedralconfiguration
surroundedby 12 aluminumseachin
octahedralconfiguration. This highly.chargedcomplexis neutralizedby 7 chloridecounterions. In
contrast, aluminumhydroxidehasa polymer-like structurewhosebasicunitisa ringof sixaluminums in
octahedralconfigurationjoined by double hydroxidebridges.Bayerite,an aluminumhydroxide
polymorph, readilyformswhenthe hydroxylto aluminumratioof aluminumchlorohydrate is raisedto 3
by titrationwith sodiumhydroxide.Dilution of aluminumchlorohydratesolutionswith water or 0.9%
NaCI leadsto the formationof gibbsite,anotheraluminumhydroxidepolymorph.Conversionof
aluminum
chlorohydrate
occurs
rapidly
enough
undersimulated
conditions
of antiperspirant
useto just!fy
theconclusionthatonemechanismof aluminumchlorohydrate's
antiperspirant
actionistheformationof
an obstructive
aluminumhydroxide
gelwithinthe sweatduct.

INTRODUCTION

The similarity between the empirical formulas for aluminum chlorohydrate,

AI2(OH)sCI
ß2H20(1),anda typeof aluminumhydroxide, whichisusedananantacid,
AI(OH)z55CI0.45
(2), suggestsa relationshipbetweenthesealuminumcompounds.
However,the extremedifferencein aqueoussolubilityof thesematerialsindicates
different
structural
arrangements.
A relationship
between
aluminum
chlorohydrate
a:•Jd
aluminumhydroxide isalsosuggested
by recentstudies
onthemechanism of action•6f
antiperspirants
(3-6),whichrevealanaluminum-containingplugin theductof eccrine
sweatglandsfollowingapplicationof aluminum-containing antiperspirants.
This
observationsupports the hypothesis
that aluminum-containing
antiperspirants
act by
formingan obstructivealuminumhydroxide gelwithinthesweatglandduct.It isthus
important to examine the structureof aluminum chlorohydrateand aluminum
hydroxide
to determine
if conversion
ispossible
under
theconditions
encountered
duringthe useof an antiperspirant.

281
282 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS

STRUCTURE OF ALUMINUM CHLOROHYDRATE

Figure1 showsa characteristic

X-ray diffractogramof aluminumchlorohydrate.
The
broadpeakintherangeof 4 to 10ø 20shows
a poorlyordered
material
witha d-spacing
of 11.8fit.Thelinebroadening
suggests
a crystallite
dimension
of about50fit (7).

11.8 A
!

I I I I I
28 22 16 I0 4
26, degrees
Figure 1. X-raydiffractogram
of aluminumchlorohydrate.
(Reproduced
by permission
fromref.7.)

Furtherinformationon the moleculardimensionsof aluminumchlorohydrate was

obtainedby observing
thatthe interlayer
spacingof montmorillonite
increased
by 8.9
fitasa result
ofintercalation
of aluminum
chlorohydrate
(7).
Examination
of the dimensions
of highlyhydrolyzed
aluminum
species
revealthatthe
AI•304(OH)24(H20)•27+
complex
proposed
byJohansson,
etal.,(8)wouldbeexpected to
causethe interlayer
spacing
of montmorillonite
to increase by 9 fit following
intercalation,
asit isessentially
a sphere
of9 fit diameter.
The9 fit dimension
ofthe
AI•304(OH)24(H20)•27+
complex
alsoagrees
withthe11.8fitd-spacingseen
intheX-ray
diffractogram
(Figure1)if a layerof waterof hydrationisassociated
withthealuminum
chlorohydrate.
Therepeating
unitofoneAl•304(OH•4(H•O)•27+
complex,
8.9fit,and
onewatermolecule,
2.9fit,yields
ad-spacing
of11.8A. Thecrystallite
dimension
of50
fit suggests
thatthebasic unitcontains
fivealuminum chlorohydrate
layers
andtheir
associated
waterlayers.
The curlingbehaviorof aluminumchlorohydrate seenby scanningelectronmicros-
copyfollowingair drying(Figure2) supports an alternating
aluminumchlorohydrate
and waterarrangement; waterwill diffusefrom betweenthe aluminumchlorohydrate
layersduringair drying,resultingin a curledfilm (Figure3).
 ALUMINUM CHLOROHYDRATE 283

i•.•
•.....
j. • (-:',•
. :
%:.

. •- .;,. • ' m-•

. ';. .• • ß;...
_t.','.? • ' ...'"•-.
•..

•'• • • . •..
.

.•.

• .. •. • .• .
• ..

...• • -... q • •.• •.•.

Figure 2. Scanning electronphotomicrographs

of aluminumchlorohydrate. Key:upperleft,lyophilized,
700X,lineof 50um;upperright,lyophilized,
5000X;lowerleft,spraydried,2000X,lineof 5 um;andlower
right,airdried10,000X.(Reproduced
bypermissionfromref.9.)

ACH•
H•O•!

DRYING
Figure 3. Schematiceffect of drying on materialcomposedof alternatinglayersof aluminum
chlorohydrate
(ACH) andwater.
284 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS

Table I

Comparison
of Empirical
Formula
forAluminum
ChIorohydrate,
A12(OH)sC1
ß2H20,and
AI•,O4(OH),4(H,O)•,C17
A12(OH)sC1.
2H20 Al•,O4(OH)24(H,O)•,CI7
AI:C1 2:1 13:7 (1.86:•)
Al:H20 1:1 13:12(1.08:1)
AI:OH 1:2.5 13:32(1:2.46)

Figure4. Structure (H 20)•2

of theAl•304(OH)24 7+ complex
showing
thetetrahedral
aluminumsurrounded
by 12aluminumsin octahedralconfiguration.
(Reproducedbypermission
fromR. MesmerandC. Baes,
TheHydrolysis
ofCations,Wiley,NewYork,N.Y. 1976,Chap.6.)
 ALUMINUM CHLOROHYDRATE 285

Theempirical formulaof aluminum chlorohydrate,AI2(OH)sCL. 2 H20 (1),compares

favorably
to theformula of theAI•304(OH)=4(H=O)•27+
complex if sevenchlorideanions
areassumed presentto neutralize
thechargeof thecomplexandit isrealized thatthe4
oxygenatomsin the proposedcomplexwill appearas 8 hydroxylanionsby the
techniquesusedto establishthestoichiometryof aluminum compounds (TableI) (10).
The small differencesbetweenthe generallyacceptedempiricalformulaand the
AI•304(OH)24(H20)•27+
complex maybedueto thepresence of otheraluminum species
in aluminumchlorohydrate, and to the relativelynonspecific methodsusedfor
establishing
theempiricalformula.
The structureof the AI•304(OH)24(H20)•27+
complex (Figure4) is unusual because it
containsa centralaluminumin a tetrahedralenvironmentsurrounded
by 12 aluminum
atoms in octahedral environments. Aluminum in a tetrahedral environment is character-
ized by aluminateanion,AI(OH)4-, whichexistsonly at high pH conditions(11).
Aluminumin octahedralconfigurationoccursat neutraland acidicpH, and is the
configuration
of aluminum in aluminumhydroxide(2).Thepresence of aluminum in
bothoctahedralandtetrahedralenvironments
canbe determined byinfraredand27A1
NMR spectroscopy.
Theinfraredspectrumof aluminum chlorohydrate showsa broadbandbetween 3100
and2500cm-•, whichrepresents the hydroxyl-stretchingvibrations'
of aluminum in
octahedral
configuration
(7).Infraredbandsfor aluminumin tetrahedral configuration
occurat 345(AIO4antisymmetric bending),640(AIO4symmetric stretching),
and 780
cm-• (AIO4antisymmetricstretching)
(7). Thesebandsagreecloselywith the infrared
bandsof sodiumaluminatewhichoccurat 325,625,and725cm-• (12).The occurence
of theAIO4symmetric-andantisymmetric-stretchingfrequenciesat higherfrequencies
in aluminumchlorohydrate thanin sodiumaluminateindicatesthat a slightlylonger
AI-O bondis presentin the tetrahedral
aluminumof aluminumchlorohydrate. The
AI-O bondswouldbeexpected to belongerin a tetrahedralaluminum in whicheach
oxygenwassharedby an octahedral aluminum.
The27AI-NMRspectrum of aluminum chlorohydrate at pH 4.8has3 distinct
signals:
a
sharppeakat 63.5ppmandtwobroadpeaksat 1.7and-0.4 ppm(Figure5)(7).The
relative chemical shift differences were referenced to an external standard of
AI(H20)63+
at pH 1. Forcomparison,
the27A1 NMR spectrum of sodium
aluminate is
alsoshownin Figure5. The peakat 63.5ppm indicatesan AI-O bondin an AIO4
tetrahedral
configuration.
The peak width of lessthan 40 Hz suggeststhat the
tetrahedralaluminumis not in equilibriumwith the aqueousenvironment.Conse-
quently,thetetrahedral
AIO4groupisbelieved to bebondedto otheraluminum atoms.
Thebroadresonances at 1.7and-0.4 ppmsuggest thepresenceof aluminum atomsin
octahedralenvironments whicharein rapidequilibrium withtheaqueous solution.
The degreeof interactionof the anion with the positivelychargedaluminum
chlorohydrate complexcouldbe studiedby infraredspectroscopy if the anionwere
infraredactive(13).Thus,aluminumchlorohydrate wastreatedwith silvernitrateto
replacetheinfrared-inactive
chloridewithnitrate.Nitratewaschosen because it isthe
sameapproximate sizeand chargeas chloride,but it is alsosymmetrical so any
perturbationsin symmetry dueto interaction
withthealuminum complex willcause a
shiftintheinfrared
spectrum.
Theinfrared
spectrum
ofaluminum
chlorohydrate
was
not affected
by thereplacementof chlorideby nitrateexceptfor theappearance
of
bands at1380and830cm-• (9).Bothbandscorrespond tothe1358and836cm-• bands
286 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS

6:3.5

80.5

ACH

120 80 40 0 -40
PARTS PER MILLION
Figure 5. 27A1-NMR
spectrum
of aluminumchlorohydrate
(ACH) and sodiumaluminate
(A104-).
(Reproduced
bypermission
fromref.7.)

for nitratein sodiumnitrate,indicating

thatthe anionin aluminumchlorohydrate is
readilyexchangeable.The smallshiftsof the nitratebandsindicatea weakinteraction
of nitrate with aluminumchlorohydrate. Thus, the chlorideanion is believedto
functionasa counterion in aluminumchlorohydrate.
The evidenceis strongthat the basicunit of aluminumchlorohydrate
consists
of a
central aluminumatom in tetrahedralenvironmentwhich is surroundedby 12
 ALUMINUM CHLOROHYDRATE 287

aluminumatomsin octahedral environments.

Tetrahedralaluminumis usuallyfound
onlywhenthe pH is above10.However,the pH of aluminumchlorohydrate solutions
is 4.5.The questionarisesasto howthissymmetrical
complexformswith a tetrahedral
aluminum in the center.

The major syntheticprocedurefor preparingaluminumchlorohydrate

involvesthe
reactionof 5 molesof metallicaluminumwith 1 mole of aluminumchloride(14).

5AI + AICI3+ 15H20 800, AI2(OH)2C1

ß2H20+ 15112

ThepH of thereactionbeginsnear3 andendsat approximately

4.5.SincethepH never
rises above 4.5, it would be difficult for a tetrahedral aluminum to form in such a
solution.However,regionsof highpH mayoccurduringthereactioneventhoughthe
bulk solutionis at a muchlowerpH. The main reactionswhichoccurduringthe
synthesisof aluminum chlorohydrateare the oxidation of metallic aluminum to
aluminumion andthereductionof protonsto producehydrogen
gas.
A1• AI 3+ -t- 3e - oxidation

2e - -I- 2H + • 82 reduction

Thesereactions occuronlyat the surfaceof the metallicaluminum.The protonsarise

from the dissociationof water.Sincethe protonsarequicklyconvertedto hydrogen
gas,a highhydroxylconcentration maybe presentat thealuminumsurface, resultingin
the initialformationof aluminumatomsin tetrahedral configuration(Figure6a).As a
clusterof tetrahedralaluminumatoms diffusesaway from the metallicaluminum
surface (Figure6b),the pH gradientcausesthetetrahedral configuration
to convertto
the octahedral configuration.
However,the tetrahedralaluminumin the middleof the
cluster is protected from the acidic bulk solution, thus forming the
AIt304(OH)24(H20)127+complex (Figure6c).Sevenchlorideanionsareassociated with
the complexascounterions.

AIø-',--AI
•++ 3e-
(• OH-
OH- H•O•--•--
H+ + OH-
2H++2e
---,,,-Ha !
OH-

AI'""'
OH-

OH-
OH-

Figure 6a.
288 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS

OH-
OH-

OH-

OH-
OH-

oo
oo
Figure 6b.

oo OH-
OH-
OH-

H* H+
oo OH-
OH-

OH-
OH-

o OH-
H+

OH-

oo OH- H+

OH-

oo pH DECREASES
/
Figure 6c.
Figure 6. Schematicformationof aluminumchlorohydrate.Key:A, Release of aluminumcationfrom
aluminummetal.;B, Formationof tetrahedral
aluminumin regionof highpH closeto thealuminummetal
surface.;
C, Formation
of AI•30•(OH)2•(H20)•27+
complex
astetrahedral
aluminums
diffuse
awayfrom
aluminummetalsurfaceandencountera decreasing
pH gradient.

STRUCTURE OF ALUMINUM HYDROXIDE

Aluminumhydroxidemayexistin the amorphous stateaswellasin severalcrystalline

forms(15).Regardless
of the polymorphicform,the aluminumatomsexistonlyin
octahedral
configuration.
The aluminumoctahedra may join at an edgeto form a
dimerby a deprotonation-dehydration
reactionto join the two aluminumoctahedra
througha doublehydroxidebridge(Figure7).Two protonsarereleased everytimea
 ALUMINUM CHLOROHYDRATE 289

Figure7. Dimeric
cation
A12(OH)2(H20)84+.
(Reproduced
bypermission
fromref.16.)

doublehydroxidebridgeforms.The basicunitcomprising aluminumhydroxideisa six

memberring of aluminumoctahedrajoined by 6 doublehydroxidebridges(16).
Aluminumhydroxidein thisstateisamorphous andreactsrapidlywithacidasall of the
hydroxylsare accessibleto protons.Crystallinitydevelopsas the six memberrings
combine(Figure8). Thisgrowthfirstoccursin oneplane,but stackinggivesriseto
X-ray diffractionpatternswhichare identifiedas gibbsite,bayerite,norstrandite,
or
boehmite(15).
The development of order in aluminumhydroxidemay be illustratedby infrared
spectroscopy (17).Deuteriumis heavierthanhydrogen. Thus,O-D stretching occursat
a lower frequencythan O-H stretching.When a freshlyprecipitatedaluminum
hydroxidegel isair driedandexposed to D20 vapor,all of the hydroxylsareconverted
to deuteroxyls,indicating thatall of thehydroxyls areaccessible for exchange (Figure
9a).As the aluminumhydroxidegel ages,the hydroxylsincorporated into orderedor
crystallinephasesbecomeunavailablefor exchangewith D20 (Figure9b). The
hydroxylswhich are not accessible for exchangebegin to show the characteristic
infraredspectrum of gibbsite(Figure9f). Thusit is clearthat aluminumhydroxideis
composed exclusively of aluminumin octahedral configuration andthatthe basicunit
is a sixmemberringof octahedral aluminumjoinedby doublehydroxidebridges.

STRUCTURAL CHANGES IN ALUMINUM CHLOROHYDRATE

FOLLOWING ADDITION OF BASE

The additionof sufficient

sodiumhydroxideto aluminumchlorohydrate to bringthe
hydroxylto aluminumratio from 2.5 to 3.0 initiatedstructuralchangeswhichwere
290 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS

+6
A16(OH)12
. 12H20
OH./A1 : 2.00

OH/A1 = 2.2O

OH/A1 = 2.5O

A132(OH'
+14' 28H20
J82
OH/A1 = 2.56

.+18
A154(OH}144
ß 36H20
OH/A1 -- 2.66

Figure 8. Development
of crystalline
aluminumhydroxide.
(Reproduced
by permission
fromref. 2.)

monitoredby infraredspectroscopy (Figure10).Indicationsof distinctabsorption

bandsin the hydroxyl-stretching
regionwereseenafteragingfor 10daysat 25ø. Sharp
hydroxyl-stretchingbandsat 3650,3540,and3460cm-• wereapparent after111days,
which correspond to the hydroxyl-stretching
vibrationsof bayerite(11). The X-ray
diffractogramafter 111daysconfirmsthat the aluminumchlorohydrate convertedto
bayeriteafter the addition-of base(Table II). Bayeriteis the aluminumhydroxide
polymorph whichformsunderbasicconditions (15).
 ALUMINUM CHLOROHYDRATE 291

UNTREATED DEUTERATED
A

B
B •
C

D E

3470 3520
, • i I I I

3500 3200 3500 3200

WAVE NUMBER, crn-I
Figure 9. Changein hydroxyl-stretching
frequencyregionof IR spectrum of aluminumhydroxidegelfor
untreatedand deuteratedsamplesduringagingat 25ø. Key: A, freshprecipitate;B, 42 days;C, 59 days;D,
74days;E, 81 days;F, 97 days;andG, 147days.(Reproduced bypermission fromref.17.)

STRUCTURAL CHANGES IN ALUMINUM CHLOROHYDRATE

FOLLOWING DILUTION

Aluminumchlorohydrate
is alsounstableupon dilutionwith water.When a commer-
cialaluminumchlorohyrate solution(6.2M in aluminum) wasdilutedto 2.5 x 10-2 M
in aluminum,the pH increased initiallybut later decreased(Figurell). The diluted
aluminumchlorohydrate solutionbecameturbid after 3 days,corresponding to the
time whenthe pH beganto decrease. The insolublephasewascollectedby filtration
andexaminedby infraredspectroscopy (Figure12).The hydroxyl-stretching
bandsof
the insolublephasecoincidewith the hydroxyl-stretching bands of gibbsite,the
polymorphof aluminumhydroxidewhich forms underacidicconditions(15). The
infraredspectrumof the lyophilizedtiltratewasidenticalto the referencespectrumof
aluminumchlorohydrate.
It is believedthat dilution of aluminumchlorohydratecausesthe highly charged
aluminumpolycationsto becomewidely separated, therebyreducingthe stabilizing
effectof the chloridecounterions andthe otheraluminumchlorohydratecomplexes.
The tetrahedral aluminum is exposed to the aqueous environment as the
Al•304(OH)24(H20)u
7+complex
dissociates.
Sincetheoctahedral
configuration
is the
stable form of aluminum in acidic solution, the tetrahedral aluminum converts to an
octahedralconfiguration. Exposureof the four negativelychargedoxygens,which
form the outershellof the aluminumtetrahedron, to the aqueousenvironment results
in the attractionof protonsandwaterto completethe octahedralconfiguration. The
adsorption of protonsis reflectedin the initialincreasein pH. However,the longterm
292

4000 :5500 :5000

WAVENUMBER,crrF•
Figure 10. Changein hydroxyl-stretching
frequencyregionof IR spectrumfollowingneutralization of
aluminumchlorohydrate.
Key:bottomcurve,initial;middlecurve,after10daysat 25ø;andtop curve,after
111daysat 25ø.(Reproduced
bypermission fromref.18.)

Table II
X-rayDiffractogram
of Aluminum
Chlorohydrate
BeforeandAfterNeutralization
Interplanar
Spacing,
•
Before 111DaysAfter
Neutralization Neutralization Bayerite
11.8 4.72 4.72
4.35 4.36
3.20 3.19
2.22 2.21
1.72 1.71
 ALUMINUM CHLOROHYDRATE 293

• 1.6
•
1.2•
ph •
0.8 •

0.4 o

12 24 :56
DAYS

Figure 11. Changein pH (•) andturbidity(I) followingdilutionof aluminumchlorohydrate

to 2.5 x
10-2 M inaluminum
duringagingat 25ø.(Reproduced
bypermission
fromref.18.)

pH trend is downward,which is consistentwith the polymerization

of octahedral
aluminumby the deprotonation-dehydroxylation
mechanism.

CONVERSION OF ALUMINUM CHLOROHYDRATE TO ALUMINUM

HYDROXIDE UNDER SIMULATED CONDITIONS OF ANTIPERSPIRANT
USE

The conversionof aluminumchlorohydrateto aluminumhydroxideby addition of

baseor dilutionrequires severaldays.However,whenaluminumchlorohydrate is used
asanantiperspirant,
it is simultaneously
dilutedwith sweatandexposedto a higherpH
at body temperature. Thus,it is importantto determineif conversion
of aluminum
chlorohydrateto aluminumhydroxidecan occur rapidly enoughunder simulated
conditionsof useto justifythe conclusionthat aluminumchlorohydrate actsas an
antiperspirant
by the formationof an obstructive
aluminumhydroxidegel withinthe
sweatglandduct.As seenin TableIII, an insolublephaseformedimmediately when
thepH of commercial aluminumchlorohydrate(6.2M in aluminum)wasadjustedto
pH 5 or above.Upon tenfold dilutionwith 0.9%NaC1,a solid phasestill formed
immediatelywhenthe pH wasraisedto 5 or above.A solidphaseappeared within24
hoursat pH 6 following100 fold dilutionwith 0.9%NaC1,and in 2 hoursat pH 7
following1000fold dilutionwith 0.9%NaC1.Thus,the combinationof elevatedpH
and dilution with 0.9%NaC1 at 37ø leadsto the rapid conversionof aluminum
chlorohydrateto aluminumhydroxide,and supports the mechanism
of antiperspirant
actionwhichis basedon a plug of aluminumhydroxideformingin the eccrinesweat
duct.

The conversion of aluminumchlorohydrate to aluminumhydroxideis expectedonce

the structuresof both compoundsare understood.Disintegrationof aluminum
chlorohydratereleases12 octahedralaluminumatoms and 1 tetrahedralaluminum
atom.Whenthe tetrahedral aluminumis exposedto the aqueousenvironmentof the
sweatduct,it convertsto an octahedral
configuration.
The octahedral
aluminumatoms
readilyorganizeinto aluminumhydroxideby the dehydration-deprotonationmecha-
nism.
 294

I
3612

I
3520L;•450
= I I I
39O0 3400 2900
W•VENUI•IBER,
•
Figure 12. Hydroxyl-stretching
frequencyregion of IR spectrumof solid dilution of aluminum
chlorohydrate
to 2.5 x 10 2 M in aluminum
(P) compared
to naturalgibbsite
(G). (Reproduced
by
permission
fromref. 18).

Table III

TimeforPrecipitate
to Appear
at37øFollowing
Dilution
with0.9%NaC1
aridpH Adjustment
pH
ACH, M 5.0 5.5 6.0 6.5 7.0

6.2 I I I I I
0.62 I I I I I
0.062 C C 24 hr I I
0.0062 C C C C 2 hr

I = Immediate Precipitate
C = Clearfor 3 days
 ALUMINUM CHLOROHYDRATE 295

ACKNOWLEDGEMENT

JournalPaper9083,PurdueUniversityAgriculturalExperimentStation,WestLafayette,
IN 47907.Copyright:
TheJournaloftheSocietyofCosmeticChemists.

REFERENCES

(1) TheMerckIndex,9thed.,(MerckandCo.,Inc.,Rahway,N.J.,1976),p 47.

(2) S. L. Nail,J. L. White,andS. L. Hem,Structure
of aluminumhydroxide
gel I: Initialprecipitate,
J.
Pharm.$ci.,65, 1188-1191(1976).
(3) H. H. RellerandW. L. Luedders, Pharmacologic
andtoxicologic effectsof topicallyappliedagents
ontheeccrinesweatglands.PartII. Mechanism
of actionof metalsaltantiperspirants,
Adv.Mod.Tox.
4, 18-54(1977).
(4) R. P. Quatrale,A. H. Waldman, J. G. Rogers,andC. B. Felger,The mechanism of antiperspirant
actionbyaluminum salts.I. Theeffectof cellophane
tapestripping
onaluminum salt-inhibited
eccrine
sweatglands,J.Soc.Cosmet. Chem.,32, 67-73(1981).
(5) R. P. Quatrale,
D. W. Coble,K. L. Stoner,andC. B. Felger,Themechanism of antiperspirant
action
by aluminumsalts.II. Histologicalobservations of humaneccrinesweatglandsinhibitedby
aluminumchlorohydrate,J.
Soc.Cosmet.
Chem.32, 107-136(1981).
(6) R. P. Quatrale,
D. W. Coble,K. L. Stoner,
andC. B. Felger,Themechanism
of antiperspirant
activity
by aluminumsalts.III. Histologicalobservations
of humaneccrinesweatglandsinhibitedby
aluminumzirconiumchlorohydrate glycinecomplex,J.Soc.Cosmet.
Chem.,32, 195-221(1981).
(7) D. L. Teagarden,
J. F. Kozlowski,
J. L. White,andS. L. Hem,Aluminumchlorohydrate I: Structure
studies,J.
Pharm.Sci.,70, 758-761(1981).
(8) G. Johansson, G. Lundgren,L. G. Sillen,and R. Soderquist,On the crystalstructureof a basic
aluminumsulfateandthe corresponding selenate,
ActaChem.Scand.,14, 769-771(1960).
(9) D. L. Teagarden, J. F. Radavich,J. L. White, and S. L. Hem, Aluminumchlorohydrate II:
Physicochemicalstudies,J.Pharm.Sci.,70, 762-764(1981).
(10) P. H. HsuandT. F. Bates,Formationof X-rayamorphous andcrystalline
aluminumhydroxides, Min.
Mag., 33, 749-768(1964).
(11) F. A. CottonandG. Wilkinson,Advanced InorganicChemistry,
4th Ed.,(Wiley,New York, 1980),p
334.
(12) R.J. Moolenaar, J. C. Evans,andL. D. McKeevet,The structure
of thealuminateion in solutionsat
highpH,J. Phys.Chem.,74, 3629-3636 (1970).
(13) C.J. Serna,J.L. White,andS. L. Hem,Anion-aluminum hydroxide
gelinteractions,SoilSci.Soc.
Amer.
Proc.,41, 1009-1013 (1977).
(14) W. HuehnandW. Haufe,Water-soluble basicaluminumcompounds, U. S. Patent2,196,016,
April2,
1940.
(15) P. H. Hsu,Aluminumhydroxides andoxyhydroxides,in Mineralsin SoilEnvironments,
J. B. Dixon
andS.B. Weed,eds.,(SoilSci.Soc.Amer.,Madison,Wisconsin, 1977),pp 99-143.
(16)J. D. Hem and C. E. Roberson,Formand stabilityof aluminumhydroxidecomplexes in aqueous
solution,U.S. GeologicalSurveyWater-Supply Paper1827-A,U.S. GovernmentPrintingOffice,
Washington,D.C., 1967.
(17) S.L. Nail,J. L. White,andS.L. Hem,IR Studiesof development
of orderin aluminumhydroxide gels,
J. Pharm.Sci.,65,231-234(1976).
(18) D. L. Teagarden, J. L. White,andS. L. Hem,Aluminumchlorohydrate III: Conversion
to aluminum
hydroxide,J. Pharm.$ci.,70, 808-810(1981).