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Ion Exchange-Spectrophotometric Determination of Aluminum

A. D. HORTON and P. F. THOMASON


O a k Ridge N a t i o n a l Laboratory, O a k Ridge, Tenn.

An effort has been made to eliminate the large number in copper-aluminum, uranium-aluminum, and in tin-lead alloys,
of separations of interfering metals usually required in iron, and stainless steel.
the determination of aluminum by the aluminum- The method is made possible by the fact that Dowex 1 anion
aluminon method. Aluminum was separated from exchange resin in the chloride form adsorbs from a 931 hydro-
nearly all interfering metal ions by a strongly basic ion chloric acid solution of the sample nearly all ions that interfere in
exchange resin. Aluminum in the effluent from the the aluminon method for the determination of aluminum, whereas
column w-as determined as the ammonium aurintri- aluminum is not adsorbed in this medium ( 7 ) . The amount of an
carboxylate lake at a wave length of 525 mp with a ion adsorbed by the resin is dependent upon the hydrochloric acid
relative standard deviation of 1.5% in the range from concentration of the solu'tion containing the ion. Although 9JI
5 to 50 y of aluminuni. The method is applicable gen- hydrochloric acid is not optimum for the adsorption of all metal
erally to copper-aluminum, uranium-aluminum, and impurities in aluminum sample solutions, the adsorption coeffi-
tin-lead alloys, stainless steel, and iron alloys. cient of most metals found in the common alloys is large enough
to provide complete separation of aluminum from these metals.
Adsorption data reported by Kraus and Xelson (3) for metals
found in the alloys under investigation are shown in Table I .
A L U h l I Y O S reagent, the ammonium salt of aurintricarboxylic
acid, has been used for many years to determine small The distribution coefficient,
amounts of aluminum. When prepared as an aluminon buffer
solution by the method described by Craft and Makepeace ( I ) D'
amt. of metal adsorbed per cc. of dry resin + voids
a m t . of metal per cc. remaining in solution phase
and later by Luke and Braun (6),it has been shown to be a reali-
able reagent for aluminum that is free from interfering ions. is sufficiently large for most of the metals to permit their separa-
These authors have adequately established the optimum amount tion from aluminum in a single pass through the resin column.
of reagent and t'he p H required to obt,ain maximum sensitivity. Lead(II), which is not adsorbed from 931 hydrochloric acid, is
The principal problem in the use of aluminon to determine strongly adsorbed from 2111 hydrochloric acid. This element may
aluminum is the removal of interfering ions. I n the removal of be separated by adjusting the effluent from the 911 column to
interfering ions in alloys of aluminum with copper, tin, and lead, 2M in hydrochloric acid and passing it through a second ion
Luke ( 5 )makes use of a mercury cathode separation, a cupferron exchange column.
extraction, an oxine extraction, and finally the aluminon-alumi- Interferences. Of those ions that pass through the resin col-
num procedure. Craft and blakepeace ( 1 ) have used perchloric umn, the trivalent rare earths, manganese(II), vanadium(1s').
acid to remove silica and tungsten from steels, and an isopropyl chromium(III), nickel(II), titanium(II1 and Is'), beryllium(II),
ether extraction to remove iron. Teicher and Gordon (8) sepa- and thorium(1V) interfere in the determination of aluminum.
rated small amounts of iron(II1) from large amounts of alumi- Inteiference by nickel(I1) can be masked by pyridine. Chro-
num by complexing iron with thiocyanate and passing t'he sample mium(II1) is slightly adsorbed by the resin; if it is present in
through a chloride-form anion exchange column a t p H 1.0. This amount> greater than the aluminum present, the sample should be
method is impractical \Then several different metal contaminants treated with perchloric and hydrochloric acids ( 2 ) to remove all
are present. but traces of chromium. Titanium(II1 and Is') xi11 not interfere
if present in amounts equal to or less than the aluminum Man-
ganese(I1) can be tolerated in an amount 25 times that of aln-
minuni ( 1 ) . Beryllium, thorium, and the rare earths are uncom-
Table I. .idsorption by Dowex 1 Chloride-Form Resin of mon components of the copper-aluminum, uranium-aluminum
llIetals Found in Alloys of .iluminum with Iron, Copper, and tin-lead all01 s, iron, and stainless steels. Interference by
Uranium, Tin, and Lead
anions has been discussed by Craft and Makepeace (1).
Ions Adsorhed Distribution Ions N o t Adsorhed
fioin 9.1.1 HCl Coefficient from 9 M HC1
Solutions (Dt) Solutions (Du< 2 )
APPARATUS
High Al(II1)
High Mn(I1)
Hieh Cr(II1) Spectrophotometer. The Beckman Model B spectrophotom-
90 NiUI) eter uith cells of 1-em. cross section was used to determine the
8 Y(IV) absorbance of the aluminum-aluminon lake.
GO Ti(II1 and IT7
40 31g(II) Ion Exchange Column. A portion of a IO-ml. graduated pipet
4 Th(IV) was used for the ion exchange column. The tip was drair-ri out t o
3 x 10' Rare earths(II1) fit into the neck of a 50-ml. volumetric flask.
100 Be(1I)
500 Pb(I1)
50
5 x 103 REAGENTS
50
50
2 x 10; Standard Aluminum Solution (50 y of aluminum per nil.).
40 Prepared from spectrographically pure aluminum metal dissolved
High in hydrochloric acid.
Ion Exchange Resin. Dowex 1 chloride-form anion exchange
resin, 50 to 100 mesh, with 107, divinylbenzene (DT'B), supplied
by Don- Chemical Co., Midland, Mich.
Aluminon-Buff er Composite Solution. Reagent grade chem-
I n the present investigation, the purification of aluminum has icals were used. The solution was prepared by the procedure of
Luke and Braun (6) except that all TTeights and volumes were
been simplified so that 3 single operation is sufficient to separate halved to produce 1.5 liters of finished reagent instead of 3.
aluminum from nearly all interfering ions that li-ill be encountered Aurintricarboxylic acid-ammonium salt, Eastman Chemical
1326
V O L U M E 2 8 , N O . 8, A U G U S T 1 9 5 6 1327

Co., produced a highly reproducible calibration curve. T h e re- The results are shon-n in Table 11. P!ridine is an effective
agent has been in use for more than 6 months and is still good. masking agent for nickel in the presence of aluminon reagent.
The amounts of pyridine and hydrochloric acid probably will vary
EXPERIMENTAL slightlj-for different bottles of these reagents. The amount of frer
Adsorption Characteristics of Resin. I n the analysis of most pyridine is not too critical, but too much n ill upset the buffering
alloys, there is one major constituent that .iT-ill be adsorbed by action of the aluminon-buff er solution.
the resin. The amount of this constituent to be adsorbed de-
pends, of course, upon the ratio of the major constituent t o PROCEDURE
aluminum in the sample. Preliminary tests should be made to Preparation of Column. Prepare a slurry r i t h Don-ex 1 (10
tletermiiie that none of this constituent passes through the col- DVB) resin and 9-14 hydrochloric acid. Insert a plug of gla
umn when the proredure is follon-ed. If any passes through, the ~ o oinl the bottom of the column and add the slurry in increments,
re5in volume must lie increased. allon-ing the resin to drain after each increment, until the column
is filled to the desired level. (-1roluine of 4.5 nil. of wet resin
It \vas found, for example, that Dolvex 1 (107' DT-B) ion es- was used in this work.) Place a plug of glass \roo1 on top of t h r
change resin can adsorh from a 9 M hydrochloric acid solution about resin in the column t,o prevent disturbance of the resin n.heii
1.5meq. of uran>-lion per gram of dry resin and about 0.T5 meq. of adding solution to the column. Connect a 125-nil. separator!
c-iipric ion per gram of dry resin. One gram of Dowex 1 (10% funnel to the column ivith Tygon tubing after addition of the
sample t o provide 9JI hydrochloric acid for IT-ashing aluminum
IIT'B) resin saturated ivith 9 J I hydrochloric acid occupies a through the column. Connect a seyaratory funnel that contairiv
volume of about 2 mi. A resin volume allon-ance of plus 100% 0.23f hydrochloric acid t o the column Ivheri it is desired t o removr.
thould be made to riisure complete adsorption of the major con- adsorbed impurities. -411 of this equipment is attached to a ring
stituent plus other metal ions in the sample. Allovance must be stand or other convenient support. If the resin has not, been
m-ashed previously n-ith 9 M hydrochloric acid, pass 100 ml. of thc
iiiade also for tailing ions-that is, ions whose coefficient of acid through the column, after n-hich it is ready for use.
:idsorption in 9.V hydrochloric acid is low.
-1rinse consisting of a t least t v o column volumes (resin vol-
umes) of 9111 hydrochloric acid is required to ensure complete sepa-
ixtion of the aluminum from interfering metals. This must be T a b l e 11. Amounts of P y r i d i n e and H \ d r o c h l o r i c .kcid
taken into account in determining a practical size for the column. R e q u i r e d to Complex Varying .kniounts of Nickel
The column should not be too small in diameter, or the f l o of ~ solu- [Pyridine. 11.9.M (approx.); hydrochloric acid. 11.i.U (approx.); n i c k !
present as nickel sulfate; 10 y of A l ~ I I I ipresent]
tion n.ill be too slow. -1f l o of ~ about 1 nil. per minute is satis-
Ni(I1) Concd. HC1 Pyridine Al(II1) Range of
I':tctory. If the flow is too fast, the tailing ions may pass through Added, Added, .4dded, Found, Sickel(I1)
\\-ith the aluminum. The resin should be kept saturated a t all 3fg. 311. 311. f Covered, M y .
times to prevent channeling.
The regeneration of the ion exchange resin-that is, the elution
of adsorbed metals from the resin-presents few problems. Most
of the metals can be remoVed from the resin by elution n-ith
tlilute hydrochloric acid.
The elements technetium, tin, and molybdenum are difficult to
wmove from the resin (3). When the removal of these metals
i* incomplete, their adsorption bands are spread the ent'ire length Calibration Curve. Pipet 1 1x1. of standard aluminum solution
( i f the column, with the result that some of the ions pass into the (50 y of aluminum per ml.) into a 50-ml. volumetiic flask. Add
nest sample that is placed on the column. This difficulty, caused 0.25 ml. of concentrated hydrochloric acid and 0.4 ml. of pyridine.
.Idd 15 ml. of aluminon-buffer solution and place the flask in
I )y the presence of molybdenum, was encountered in the separa- briskly boiling mater for 5 minutes. Cool and dilute to volume.
tion of aluminum from the National Bureau of Standards st'eel Determine the spectral absorbance in cells of 1 em. cross section
s:;rniple, 111B. The cost of the Dowex 1 chloride-form resin is a t a wave length of 525 mp with distilled n-ater for a reference.
l t w than 5 cents for the amount specified in this method and it is
Repeat the procedure for 0.1, 0.2, 0.4, 0 6, and 0.8 ml. of the
standard aluminum solution. Prepare a new calibration curve
suggested that a large volume of resin be treated ivith 9.U hydro- for each fresh batch of aluminon-buffer solution.
chloric acid, so that fresh resin may be used for each determina- Determination of Aluminum. SAMPLES T H ~DoT SOT coh-
tion. TAIN LEAD. Dissolve solid samples in hydrochloric or perchloric
Pyridine a s Complexing Agent. Some of the sample solutions acid. Evaporate to dryness and dilute to volume with 931
hydrochloric acid. If the sample is a solution, evaporate it to
i l l which aluminum \\-as to be determined were known to contain dryness and dilute to volume with 9JI hydrochloric acid. If
nickel(II), which is not adsorbed by Doivex 1 resin (3). Craft chromium is present in an amount greater than the aluminum,
kind Makepeace ( 1 ) have shown t h a t this ion interferes in the it should be removed by the method of Hoffman and Lundell ( 2 ) .
determination of aluminum. Evaporate to dryness and dilute t o the desired volume with 9 J I
hydrochloric acid. Place the tip of the column in a 50-ml. volu-
Pyridinium chloride (4)has been used t o complex nickel( 11) metric flask. Pipet an aliquot of the sample onto the Donex 1
ion. The following experiments were carried out to shorn n-hether resin. Allow to drain almost completely. Attach the separatory
or not pyridine interferes Ivith the formation of the aluminum- funnel that contains 9-11 hydrochloric acid to the column and
tilnminon lake. allow 15 ml. t o pass through. (The volume is not critical, but it
should not be smaller than 15 ml,), Place the 50-ml. volumetric
-kn aliquot of a solution that contained 10 y of aluminum was flask on a hot plate and evaporate the effluent to dr) ness, being
pipetted into a 50-ml. volumetric flask and 25 mg. of nickel(I1) careful not to allow the residue t o bake on the glass. Cool the
n-as added. T o the flask x e r e added 5.0 ml. of concentrated flask and add concentrated hydrochloric acid and pyridine accord-
hydrochloric acid, 5.15 ml. of pyridine (11.9-4I), and 15 ml. of ing to the amounts listed in Table 11. .4dd 15 ml. of aluminon-
aluminon-buffer solution. The flask was placed in boiling water buffer solution and place the flask in briskly boiling water for 5
for 5 minutes. T h e solution was cooled, diluted to the mark, and minutes. Cool and dilute t o volume. Determine the spectral
the absorbance was determined a t 525 mp us. distilled water. absorbance in 1-em. cells a t a wave length of 525 mp, using dis-
This experiment was repeated for varying amounts of nickel with tilled water as a reference.
proportional amounts of pyridine and hydrochloric acid. When SAJm,Es THATCONTAIN LEAD Prepare the samples as just
0.25 ml. of concentrated hydrochloric acid and 0.4 ml. of pyridine described. Then, place the tip of the colu-mn in a graduated
\\-ere added t o 10 y of aluminum and the sample treated accord- cylinder and pipet an aliquot of the sample onto the ion exchange
ing to the above procedure, the absorbance was identical to that column. Allow t o drain almost completely, then add 15 ml. of
obtained when nickel was present. Additional tests n-ere made 9-11 hydrochloric acid. T17hen the column has drained, adjust
t o determine the range of nickel covered by each combination of the 9 X hydrochloric acid effluent to 2M by adding distilled water.
pyridine and hydrochloric acid. Prepare a 2 J I hydrochloric acid resin column and pass the ad-
1328 ANALYTICAL CHEMISTRY

Table 111. Composition of NBS Samples and Aluminum Content Determined by Proposed Method
Sample Compositiona
No. C hln P S Si Cu Ni Cr V M o 41 Zn Sn Ph Fe
Ni-Mo steel
lllB
hln-A1
.~hronae
.~.~.-.
0.193 0,706 0.012 0.014 0.302 0.028 1.81 0.070 0,003 0.255 0.043 ... .. .. Balance
164 . .. 4.68 . .. .. . 0.038 63.76 0.046 ., . ... .. . 6.21 21.89 0.63 0.22 2.52
Aluminum,-77 Diff.,
Present Found %
lllBb 0.043 0.044 +0.001
0.042 -0.001
0,042 -0.001
0.045 f0.002
164C 6.21 6.10 -0.11
6.19 -0.02
6.29 +0.08
6.30 +0.09
These values are NBS averages in per cent.
b Dissolved 1 gram in perchloric and hydrochloric acids. evaporated to dryness, and dissolved residue in 9.v hydrochloric acid. Diluted to 50 ml. with 9.1r
hydrochloric acid.
C Dissolved 0.1 gram in concentrated hydrochloric acid, evaporated to dryness, s n d dissolved residue in 9Jf hydrochloric acid. Diluted t o 100 ml. with 9.lii
hydrochloric acid.

Table IV. Determination of Aluminum in Synthetic


justed effluent through the column, this time collecting the Corrosion Sample of Uranyl Sulfate Solution in Contact
effluent in a beaker. Rinse the 2M effluent through the column with Stainless Steel
with 15 ml. of 2M hydrochloric acid. Evaporate the final effluent
to dryness, dissolve the residue in hydrochloric acid (Table 11), Solution Composition, Grams per Liter
and transfer the contents of the beaker to a 50-ml. volumetric Tranium(1V) 10
flask. .4dd pyridine according to the amounts listed in Table 11, CopperiII) 2
and continue the determination as described above. If lead is Nickel(I1) 0.1
Chrornium(II1) 0.1
present in an amount that is much smaller than the amount of Iron(II1) 0.1
aluminum in the sample, use the procedure for samples without Alurninum(II1) 0.05
lead.
Aluminum, y
Present Found Diff., y
RESC' LT S
50 49.5 -0.5
Table I11 shows the Bureau of Standards average values for 30 30 4 t0.4
20 I9 8 -0.2
percentages of the metals and impurities in alloys 164 and 111B, 10 9.4 -0.6
as well as results of the aluminum determination on these samples.
Table IV s h o m the results obtained from the determination of
aluminum in a synthetic sample which represents the corrosion
of stainless steel by uranyl sulfate solution under high temperature Hoffman, J. I., Lundell, G . E. F., J . Research Satl. Bur. Stand-
and pressure. ards 22, 465 (1939).
Kraus, K. A., Nelson, F., Paper S o . 837 (CSA), International
ACKNOWLEDGMENT Conference on the Peaceful Uses of Atomic Energy, Geneva,
Switzerland, August 1955.
The research on the adsorption characteristics of Dowex 1 ion Lingane, J. J., Kerlinger, H., IXD.ENG.CHEM.,. ~ N A L . ED. 13,
exchange resin by K . A. Kraus and Frederick Nelson of Oak 77 (1941).
Ridge National Laboratory, Chemistry Division, has been very Luke, C. L., ANAL.CHEM.24, 1122 (1952).
valuable to the authors in the development of this method. Luke, C. L., Braun, K. C., Ibid., 24, 1120 (1952).
Moore, G. E., Kraus, K. A., J . Am. Chem. SOC.72, 5792 (1950).
LITERATURE CITED Teicher, H., Gordon, L., ANAL.CHEM.23, 930 (1951).
(1) Craft, C. H., Makepeace, G. R., IND.
ENG.CHEM.,AA-AL.ED. 17,
206 (1945). RECEIVED
for review December 27, 1955. Accepted April 30, 1956.

C-H Vibrations in Aldehydes


D. F. EGGERS, JR., and W. E. LINGREN
University o f Washington, Seattle 5,Wash.

The infrared spectra of four monodeuterated aldehydes,


in which the deuterium was on the aldehyde group,
were measured. Comparison of any one of these spectra
C HARACTERISTIC regions in the infrared spectrum have
been listed for aldehydes ( 2 ) . While the C=O and C-H
stretching regions are well established, some of the other correla-
with that of its protium homolog shows many bands tions have been questioned (1). Four monodeuterated alde-
which are unchanged in frequency or intensity; other hydes recently became available to this laboratory, and an inves-
bands are shifted by large amounts. The method thus tigation of their infrared spectra was carried out.
enables one immediately to determine whether or not
the aldehyde hydrogen is involved in any band of any EXPERIMENTAL
aldehyde. Assignments in aldehyde spectra are dis- The four compounds studied were benzaldehyde, p-chloro-
cussed. benzaldehyde, piperonaldehyde, and butyraldehyde. The light