THE SOLUBILITY OF ALUMINUM HYDROXIDE IN ACIDIC AND

BASIC MEDIA AT 25" C L , ?

ABSTRACT
The solubility of AI(OII)3 was measured in NaOH and I-ICIO.I solutions. I'ossible reactions
of AI(OH)$ i n dilute YaOH and IlClOa solutions are indicated along with the calculated
constants. The amphoteric hydroxide was found to be more acidic than basic. The isoelectric
point of Al(OH), was deternlined to be pH 7.7.
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I-IISTORICAL
T h e amphoteric nature of aluminum hydroxide has been studied by other investi-
gators, but owing to i~lcompleted a t a the extent of its amphoterism is still not entirely
determined. I t s isoelectric point has not been previously determined.
A number of equilibrium constant values are tabulated below:
--
Source Equilibrium constant Value
Heyrovslcy (1) Solubility product 1.06X at 26' C
Heprovsky (1) Ion product of alu~ninicacid 35 X lo-" a t 26" C
Icruyt and Troelstra (2) Solubility product l.00X10-32a t 2.5' C
Wood (3) Acid dissociation constant 6.30X 10P3a t 26' C
For personal use only.

Slade (41 Acid nio~~obasicdissociation oroduct anorox. constant 1X

Hildebrand ( 5 ) , in his study on the solubility of aluminum hydroxide, claimed t h a t

i t dissolved a s an acid. This claim was supported by the slight break in the solubility
curve correspo~ldillgto the addition of another equivalent of basc. Heyrovsky (6) stated
t h a t aluminum hydroxide dissolves in alltalies as follows:
IZI(OH)~ + OH- % rll(0H)t-.
Joseph (7) in plotting equivalent conductance against the ratio of sodium hydroxide
to aluminum hydroxide obtained no sharp breaks or irregularities and, therefore, con-
cluded t h a t aluminate ion A 1 0 ~
occurs.

EXPERIRiIENTXL
Procedure
T h e general procedure is similar t o that used by Garrett and Heilcs (8).
Preparation of Reagents
The preparation of conductivity water is t h a t of Gayer and Woontner (9).
Alurn,inaim hydroxide.-illumi~~l~mhydroxide was precipitated from aluminum chloride
by means of sodium hydroxide. T h e precipitate was washed several times beyond t h a t
required to give a negative flame test for sodium for both the solid and the supernatant
liquid. A sample of the precipitate was dried for 2 days a t 50° C. Followi~lgthis, it was
ignited a t 500° C. From the weight loss, the empirical formula was calculated to be
lManzlscript received A p r i l 8, 1968.
Contrzbz~tionf r o m the Cl~emistryDepartment, W a y n e State Universzty, Detroit, ilIichzgan.
=Froma dissertation sztbmztted by M r . Lancelot C. Thonzpso~zi ~ partial
z fulfillment of the requirements for the
Doctor of Philosophy degree a d a dissertation szlbntitted by M r . 0. T . Zajicek i7t partial fi~ljill~nentof the
reqztireme?zt for Ihe illaster of Science degree.
Can. J. Chem. Vol. 36 (1958)
 GAYER ET AL.: ALUMINUM I-IYDROSIDE 1269

A1203.3H20. An X-ray diffraction powder pattern showed the material to be crystalline.

The three major d values, in order of decreasing intensity, were found to be 4.62, 4.27,
and 2.20 A.
Aluminum chloride.-Baker and Adamson reagent grade aluminum chloride crystals
were used to prepare the hydroxide. Standard aluminum solutions: 1.76 g of aluminum
alum was dissolved in distilled water and made up to 1 liter. The standard solutio~l
contained 0.1 mg of aluminum per milliliter. From this solution spectrophotometric
determi~latiorlsof aluminum were made by diluting to make solutions of 2, 4, 8 , 12, 16,
20, 24, and 28 y/ml. The standard curve was prepared by means of the Becltman NIodel
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B spectrophotometer.
Chloroform.-Reagent grade chloroform was used for the extraction of the aluminum
quinolate.
8-Hydroxyquinoline.-Twent~1 grams of hydroxyquinoline was dissolved in 60 ml of
glacial acetic acid and diluted to 1 liter with distilled water.
Colorimetric analyses.-The aluminum analyses were made with a Becltman Model B
spectrophotometer using the method of Sherrington and Gentry (10). The absorbance
I was measured a t 400 mp against a reagent blank.
pH.-A Becltman Model G pH meter was used to determine the eq~iilibriumvalues
of the hydrogen and hydroxyl ion activities.

TABLE I
For personal use only.

SOLUBILITY
OF ALUMINUM HYDROXIDE I N SODIUM HYDROXIDE SOLUTIONS AT 25O C

Equilibrium,
Initial moles Equilibrium moles aluminum/
NaOH/1000 g activity of 1000 g H?O Ao~/rnoleof
H20X105 hydrosyl ion X 105 AOFIX 105 aluminum K
0 3.98X10-9 2.97 7460.
1.04 4.17X10-9 1.63 3910.
2.99 4.57X10-9 1.89 4136.
12.3 1.00X10-8 2.00 2000.
17.74 2.63X10-8 0.78 240.
33.79 1 . 12X10-7 0.445 40.
61.55 3.31X10-G 0.667 2.02

AOE = initial moles of base - equilibrium moles of base,

= base consumed by Al.

T H E DATA
The data are collected in Tables I and 11. The values for the activity coefficients for
NaOH and HC1O4 are given by Robinson and Stokes (11).
From the amounts of sodium hydroxide consumed and from the ratio of consumed
sodium hydroxide to dissolved aluminum, it can be concluded that a major portion of the
sodium hydroxide is simply adsorbed.
 1270 CANADIAN JOURNAL O F CHEMISTRY. VOL. 36. 1958

TABLE I1

--

Initial Eq~~ilibri~~m,
moles of E q ~ ~ i l i b r i ~ ~ ~moles
n
HCIOI/ activity of aluminum/
1000 g 1-120 hydrogen 1000 g Aa+/mole
X 10" ton H ~ Oxlo5 AH+ l o 5 AI x 1 K? KS
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For personal use only.

AH+ = initial moles of acid - esuilibrium moles of acid.

In view of the constancy of the equilibrium constant values and the relatively small
amounts of solid dissolved, we believe that the following reaction is predominant in the
concentrations of sodium hydroxide from 0.0008 molal to 0.08 molal.
AI(0H)z (s) + 01-1- = HL:I\IOI- + H20.
The form H2A103-, rather than Al(OH)4-, was chosen since it is felt that the equation
tends to better emphasize the acid-base character of the reaction. For the equation
written,
K = ~ H ~ A ~ O ~ - / ~ O=H -n6H2~103-'~H2b103-/aOH-.

According to the Debye-Hiiclcel limiting law, the activity coefficients for 1-1 electrolytes
should be equal a t equal ionic strengths; hence,

and

Using the above equilibrium constant and K,, the ioilizatioil constant for water a t
25" C, the ionization constant for the follo~vingreaction was calculated:
AI(OH), (s) = H+ + Hg103-
K = 2.98 x 10-15.
Taking into consideration (1) the amount of acid coilsumed to the amount of aluminum
hydroxide dissolved and (2) the fair constancy of the equilibrium constants over limited
ranges of acid, we can probably conclude that in very low acid concentrations from 0
to 2X10-4 molal, reaction [I] below predominates and in acid concentratio~lsfrom
 GAYER ET AL.: ALUMINUM HYDROXIDE 1271

2X molal to 2 X molal, and possibly higher, reaction [3] predominates. I n view

of the drift in values of K 2 , the range of reaction [2] cannot be determined. At most, we
can only conclude that it probably occurs simultaneously with reaction [3] in the inter-
nlecliate concentratioil of acid near 2 X lop4 molal.

AI(OH), (s) + 3H+ = AIC3 + 3H20 PI

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As before,

and

Since I<?was not constant, no attempt was made to select a representative value for it.

From the Debye-Hiickel limiting law, the activity coefficient of a 1-3 electrolyte may
be replaced by the cube of that for a 1-1 electrolyte; hence,
For personal use only.

Using the value obtained for K3 above and the cube of K,, the ionization constant
for water a t 25O C, the solubility product constant for the following reaction was cal-
culated :
Al(0N)a (s) = AIC3 + 30H-,

For an amphoteric hydroxide, the isoelectric point will represent the minimum solu-
bility. Plotting the logarithm of the reciprocal of the solubility against pH gives a curve
with a maximum a t pH 7.7.

REFERENCES
1. I-IEYROVSICY,J. J . Chem. Soc. 117, 11 (1920).
2. ICI~UYT,
13. R. and TROELSTRA, S. A. IColloid-Beih. 54, 262 (1943).
3. Woon, J . I<. J . Chem. Soc. 93, -111 (1908).
4. SLADE,R. E. Z. anorg. Chem. 77, 457 (1912).
5. HILDEBRAND, J . H. J . Am. Chem. Soc. 35, 864 (1913).
6. HEYROVSKY, J . J . Chem. Soc. 117, 1013 (1920).
7. JOSEPH,0 . J . Univ. Bombay, Sect. A, 20 (Pt. 3 ) , 39 (1051).
8. GARRETI,A. B. and HEIKS,R. E. 1. Am. Chem. Soc. 63, 562 (1941).
9. GAYER,K. H. and WOONTNER, L. J. Cliem. Educ. 33, 296 (1956).
LO. GENTRY, C. H. R. and SHERRINGTON, L. G. Analyst, 71, 432 (1946).
11. IIOBINSOX, R. A. and STOICES, R. M. Trans. Faraday Soc. 45, 612 (1949).