January, 1945 ANALYTICAL EDITION 37
vary, depending on the conditions employed, but under the same (6) Ritter, G. J., Seborg, R. M., and Mitchell, R. L., Ind. Eng.
conditions there is good correlation between the relative amounts
of sugar obtained from different woods by the two methods.
LITERATURE CITED
(1) Kiesel, A., and Semiganovski, N., Ber., 60B, 333-8 (1927).
(2) Klason, P., Cellulosechem., 4, 81 (1923).
(3) Lilers, H., Angew. Chem., 45, 369-76 (1932).
(4) Monier-Williams, C. W., J. Chem. Soc., 119, 803-5 (1921).
(5) Ritter, G. J., Mitchell, R. L., and Seborg, R. M., J. Am. Chem.
Soc., 55, 2989-91 (1933).
Rapid Volumetric Method for Aluminum
L. J. SNYDER, Ethyl Corporation, Baton Rouge, La.
A rapid and accurate procedure is described for the determination of
aluminum in the presence of 1 to 10% of impurities such as calcium,
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.
copper, chromium, iron, magnesium, manganese, and zinc. Experi-
mental data are presented showing the accuracy and the effects of
impurities commonly associated with aluminum. Five to 10 min-
Downloaded via UNIV OF PENNSYLVANIA on May 1, 2020 at 18:38:42 (UTC).
utes' time is required per analysis.
it has been common practice to determine
HERETOFORE,
aluminum by precipitation as the hydrous oxide followed
by ignition to constant weight. This procedure is time-consum-
ing and of such doubtful accuracy that materials high in alumi-
num content are analyzed by determining the other components
and calculating aluminum by difference. However, when the
impurities are present to the extent of only a few per cent and an
assay of the impurities is not required, a direct, rapid, and accu-
rate volumetric method is desirable.
The use of potassium fluoride in the acidimetric determination
of aluminum has been studied by a number of investigators
(1-6). The method described by Viebock and Brecher (6)
appears to have the widest application. Their procedure con-
sists of neutralizing the aluminum solution with sodium hydroxide
in the presence of sodium potassium tartrate to the phenol-
phthalein end point, adding neutral potassium fluoride, and
titrating the liberated potassium hydroxide as a measure of the
aluminum present. This reaction does not proceed stoichio
metrically, the end point appearing about 10% before the equiva-
lence point.
Aluminum hydroxide, formed by the neutralization of a solu-
tion of an aluminum salt to the phenolphthalein end point, re-
acts with potassium fluoride to form the neutral salt, AlFi.3KF,
and liberates 3 moles of potassium hydroxide permoleof aluminum
present. This reaction is slow even with heating (5), but in the
presence of sodium potassium tartrate it is practically instan-
taneous (S). The acid used to titrate the liberated base is a direct
measure of the aluminum present. The following are the re-
actions for the neutralization of the aluminum ion and the
liberation of the base by the potassium fluoride:
A1++++ 30H" —*- Al(OH),
Al(OH), + 6KF —>- A1F..3KF + 3KOH
The purpose of this paper is to show that the reaction between
aluminum hydroxide and potassium fluoride in the presence of
sodium potassium tartrate, with certain modifications of pre-
vious procedures, can be used for the quantitative determina-
tion of aluminum in the presence of small quantities of some of
the usually interfering ions.
EXPERIMENTAL
Reagents. All chemicals used were of Baker’s c.p.
with no further purification.
Chem., Anal. Ed., 4, 202-4 (1932).
(7) Saeman, J. F., Harris, E. E., and Kline, A. A., Forest Products
Lab. Report, R1459 (1944).
(8) Shaffer, P. A., and Somogyi, M., J. Biol. Chem., 100, 695 (1933).
(9) Willstátter, R., and Zechmeister, L., Ber., 46, 2401 (1913).
(10) Wohl, A., and Krull, H., Cellulosechem., 2, 1-7 (1921).
Presented before the Division of Cellulose Chemistry at the 108th Meeting
of the American Chemical Society, New York, N. Y. Based on studies
of the U. S. Forest Products Laboratory in cooperation with the Office of
Production Research and Development, War Production Board.
Barium hydroxide, saturated solution.
Hydrochloric acid, 0.3 N solution standardized with reference
to a·known aluminum chloride solution.
Standard aluminum chloride solution, 0.3 N. Weigh ac-
curately 2.5 to 2.7 grams of pure aluminum wire (Baker’s c.p.,
99.99%) and dissolve in 200 ml. of approximately 1 N carbonate-
free sodium hydroxide, make the solution just acidic with
hydrochloric acid (1 to 1), and boil slowly to expel carbon dioxide
before diluting to 1 liter. Use aliquots of the .standard solution
to standardize the hydrochloric acid by the procedure described
below.
Sodium potassium tartrate, 30% solution.
Potassium fluoride (KF.2H20), 30% solution, neutral to phenol-
phthalein and stored in a wax-lined bottle.
Procedure. To the aluminum chloride solution free of am-
monium ion and other interfering substances and containing
25 to 130 mg. of aluminum, add standard barium hydroxide
solution until the free acid is neutralized as indicated by a slight
precipitate of aluminum hydroxide. Introduce 30 ml. of the
sodium potassium tartrate solution and continue the titration
to the phenolphthalein end point. Add 30 ml. of neutral (to
phenolphthalein) potassium fluoride solution and titrate the
liberated base with 0.3 N hydrochloric acid to the disappearance
of the red color. The end point is considered permanent when
the color does not return after 30 seconds. The standard hydro-
chloric acid used to titrate the liberated base is equivalent to the
aluminum present.
Tests on Known Solutions. The reliability of the method
was determined by analyzing known aluminum chloride samples,
prepared by dissolving pure aluminum wire in 1 N sodium hy-
droxide (carbonate-free). The sodium alumínate was then
made slightly acidic with dilute hydrochloric acid and the solu-
tion diluted to a known volume. Aliquots were withdrawn
and the aluminum was determined by the procedure described.
The accuracy was found to be ±0.1 mg. Data showing the
analysis of known solutions are presented in Table I.
Table I. Analysis of Known Aluminum Solutions
A1 Added A1 Found Difference
Oram Gram Gram
0.1282 0.1282 0.0000
0.1026 0.1026 -0.0001
0.0769 0.0768 -0.0001
0.0513 0.0612 -0.0001
0.0256 0.0266 0.0000
0.1236 0.1237 + 0.0001
0.1236 0.1237 + 0.0001
0.1236 0.1236 -0.0001
0.1236 0.1238 +0.0002
0.1236 0.1235 -0.0001
0.1236 0.1235 -0.0001
Mean of difference 0.0001
Analysis of Aluminum in Presence of Interfering Sub-
stances. The effect of impurities was determined by adding
the ions in three concentrations to solutions containing known
amounts of aluminum and then analyzing the solutions for alumi-
num (mole ratios of aluminum to impurity were 2, 10, and 100).
At an aluminum-impurity ratio of 100, only phosphate, sulfate,
quality and silicate interfered, while calcium, chloride, carbonate, chro-
mium, copper, iron, magnesium, manganese, and zinc did not
 38 INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 17, No. 1

interfere. Sulfate caused high results, of the order of 1%, and
silicates caused very high results. At a mole ratio of 2, all the
ions tested interfered except sodium, potassium, carbonate, and
chloride (Table II).
tion of the potassium fluoride solution, the change in pH per drop
of standard base was so small that a satisfactory neutralization
could not be made. However, when using phenolphthalein a
sharp change was obtained with the addition of only one drop of
acid.
DISCUSSION

Table II. Effect of Interfering Substances Ip the titration of the liberated hydroxide with standard acid,
Impurity Mole Ratio, the end point fades the first time it appears and then becomes
Added Al-Impurity A1 Present A1 Found Difference
Gram Gram Gram permanent with the addition of a few drops of acid. This is
NaCi« 2 0.1501 0.1503 +0.0002 probably due to the fact that the aluminum potassium fluoride
KCl* 2 0.1601 0.1502 + 0.0001 precipitates from a basic solution and adsorbs some of the base
NaiCOi“ 2 0.1455 0.1454 -0.0001
ZnCli 2 0.1501 0.1486 -0.0015 which is desorbed near the end point. This effect may be mini-
10 0.1501 0.1500 -0.0001 mized by adding an excess of standard acid, shaking well, and
100 0.1501 0.1501 0.0000
CaClj 2
10
0.1501
0.1501
0.1488
0.1503
-0.0013
+ 0.0002
back-titrating with standard barium hydroxide.
100 0.1501 0.1502 + 0.0001 A serious error is possible if the sodium potassium tartrate is
CuCli 2 0.1489 0.1487 -0.0022 added to a strongly acid solution of the aluminum salt. The
10 0.1489 0.1489 0,0000
100 0.1489 0.1489 0.0000 tartrate forms highly insoluble potassium acid tartrate which
MgCli 2 0.1497 0.1463 -0.0034
10 0.1497 0.1488 -0.0009 precipitates immediately. The precipitate is acid in nature
100 0.1497 0.1495 -0.0002 and redissolves slowly, resulting in a fading end point to phenol-
Fe(NOj)j 2 0.1489 0.1553 -0.0064
10
100
0.1236
0.1236
0.1269
0.1236
+ 0.0033
0.0000
phthalein. The precipitation of potassium acid tartrate is
MnCli 2 End point obscured by color of Mn avoided by the addition of sodium potassium tartrate to the
10
100 0.1501 0.1500 +0.0001 solution only after most of the free acid has been neutralized.
CrCl. 2 0.1489 0.1358 -0.0131 This procedure will always give a clear, pink permanent phenol-
10 0.1489 0.1447 -0.0042
100 0.1489 0.1487 -0.0002 phthalein end point. If a precipitate of potassium acid tartrate
NaiPO, 2 0.1501 0.1015 -0.0486
10 0.1601 0.1406 -0.0095 forms, it may be dissolved by making the solution alkaline with a
100 0.1501 0.1496 -0.0005 1- to 2-ml. excess of barium hydroxide, heating to 60° to 70° C.
NaiSOi 2 0.1489 0.1504 +0.0015
10 0.1489 0.1604 + 0.0015 until all the precipitate dissolves, and adjusting the solution to
100 0.1489 0.1603 + 0.0013 the phenolphthalein end point before adding the fluoride.
NatSiOi 2 0.1489 0.1919 + 0.0570
10 0.1489 0.1641 + 0.0152 Theoretically, 6 moles of potassium fluoride are necessary to
100 0.1489 0.1639 + 0.0150
react with 1 mole of aluminum. This quantity is not enough,
e Assumed that no interference would occur in low concentration if high
concentration did not interfere. as the reaction does not go to completion and low results are ob-
tained. The use of at least twice the theoretical amount of
fluoride is recommended.

The neutralization of the aluminum chloride to the phenol-

phthalein end point must be done with barium hydroxide solu- Table IV. Analysis of Known Solutions with Hydrochloric Acid
tion, Ammonium hydroxide or ammonium salts buffer the solu- Standardized with Reference to Potassium Biphthalate
tion to the extent that the end point cannot be quantitatively A1 Added A1 Found Difference
Gram Gram Grom %
distinguished. If sodium or potassium hydroxide solution is 0.1282 0.1272 -0.0010 0.8
used, the end point is not so sharp as when barium hydroxide is 0.1026 0.1017 0.0009 0.8
-

0.0769 0.0762 -0.0007 0.9

used and lower results are obtained, as shown in Table III. 0.0513 0.0509 -0.0004 0.8
0.0256 0.0254 -0.0002 0.8
These results were found to support the statement made by
Viebock and Brecher (6), that the end point appeared about 10%
before the equivalence point. The reason for. obtaining low
results with sodium hydroxide is not evident and was not in- The analysis may be applied to the simultaneous determina-
vestigated. tion of free acid and an aluminum salt by adding neutral sodium
potassium tartrate, and neutralizing the free acid and aluminum
salt with barium hydroxide to the phenolphthalein end point,
which is a measure of the total acid plus aluminum salt. The
Table III, Neutralization of Aluminum Chloride with Barium
Hydroxide and Sodium Hydroxide subsequent titration of the liberated potassium hydroxide, after
A1 Added A1 Found Difference the addition of potassium fluoride, with hydrochloric acid is a
Grom Gram Gram . measure of the aluminum and the difference between the equiva-
Neutralisation with Ba(OH)» 0.1244 0.0000 lents of acid and base used is a measure of the free acid.
0.1244 -0.0001
0.1244 999 0.0000
0.1159 -0.0085 ACKNOWLEDGMENT
Neutralisation with NaOH 0.1244
(carbonate-free) 0.1244 0.1163 -0.0081
0.1244 0.1143 -0.0101 The author wishes to thank G. F. Kirby and W. H. Thomas
for their helpful comments in connection with this paper.

The hydrochloric acid must be standardized against a known
aluminum sample to obtain quantitative results. When the
hydrochloric acid is compared with standard alkali previously
standardized with potassium biphthalate, the kluminum analysis
was found to be consistently low, as shown in Table IV. The
same result may be obtained by increasing by 0.8% the nor-
mality obtained by standardizing against primary standards.
Phenolphthalein was found to be a suitable indicator. When
either phenol red or m-cresol purple was used in the neutraliza^
LITERATURE OTED
(1) Craig, T. J. I„ J. Soc. Chem. Ind., 30, 185 (1911).
(2) Malaprade, L., Conor, chim. ind., Compt. rend. 18me Conor.,
Nancy, p. 115, Sept.-Oct., 1938.
(3) Scott, W. W„ J. Ind. Eno. Chem., 7, 1059 (1915).
(4) Titus, A. C., and Cannon, M. C., Ind. Eno. Chem., Anal. Ed.,
11, 137 (1939).
(5) Travers, A., Compt. rend., 185, 893, 1043 (1927).
(6) Viebock, F„ and Brecher, C., Arch. Pharm., 270, 114 (1932).
Pbbsented before the Division of Analytical and Micro Chemistry at the
108th Meeting of the American Chemical Societt, New York, N. Y.