ANALYTICAL

SCIENCES

AUGUST

1995, VOL.

11

689

Notes

Solid-Liquid
the

Separation

Extraction

with

of Traces

an Ammoniacal

of Copper

from

EDTA

Solution

for

Aluminum

Masataka HIRAIDE,Yasushi MIKUNIand Hiroshi KAWAGUCHI

Department of Materials Science and Engineering, Nagoya University,Nagoya

Keywords

Extraction,

copper,

aluminum,

EDTA,

graphite-furnace

Although modern instrumental

determination
methods are highly sensitive and selective, preliminary
separation techniques are often required to improve the
precision and accuracy of analytical results. Solidliquid extraction is a useful separation technique: the
desired trace elements are quantitatively extracted from a
solid matrix with a simple
1 3 A metal sample is first dissolved in a solvent and then evaporated to
dryness to redistribute the trace elements on the surfaces
or in the interstitial spaces of agglomerates of pure matrix
crystals. The trace elements are selectively extracted
into an appropriate solvent for the determination by
instrumental analytical methods. Extraction solvents
used heretofore were mainly organic solvents containing
small amounts of acids.
In a previous work4, we proposed the use of diluted
nitric acid for the multielement extraction of impurities
in high-purity silver metal samples. Extraction with
such aqueous solvents allows the direct combination with
different determination methods, including inductively
coupled plasma-atomic emission spectrometry (ICPAES), ICP-mass spectrometry and different electrochemical techniques. The present communication describes the scope of solid-liquid extraction with aqueous
solvents, by taking the separation of copper(II) from an
aluminum matrix as an example. The aluminum was
converted into its hydroxide, through which traces of
copper were extracted with an ammoniacal EDTA
solution. The proposed separation technique has been
successfully applied to the determination of traces of
copper in high-purity aluminum.

Experimental
Apparatus
A Seiko I & E SAS-760
atomic
absorption
spectrometer
equipped
with an SAS-715
graphite
furnace
atomizer was used for the determination
of copper.
The
graphite
tube was gradually
heated to 150 C, held for
10 s and then heated during 5 s to 400 C and held for 15 s.
The tube was further
heated to the atomization
temperature

of 2400 C for 2 s for measuring

the absorbance

atomic

absorption

464, Japan

spectrometry

at 324.8 nm.
A Seiko SPS 1100H ICP-atomic emission spectrometer was employed for the determination of
aluminum under the following operating conditions:
wavelength 309.27 nm, RF power 1.2 kW; argon flow
rates (dm3 min 1)16, 0.7 and 0.6 for outer, intermediate
and carrier, respectively.
The evaporation apparatus consisted of a Yamato HF
41 heater and an aluminum heating block (12 holes,
25 mm diam.X65 mm depth), where Pyrex glass test
tubes (20 mm inside diam., 24 mm outside diam.,100 mm
height) were inserted to evaporate solvents.
A Tokyo Rikakikai AU-60C ultrasonic cleaning bath
(28 kHz, 210 W) was used for the extraction of copper
from the aluminum matrix. A Hitachi ECV-843 BY
clean bench was used for separation procedures.
Reagents
An aluminum solution (20 mg cm-3) was prepared by
dissolving aluminum chloride hexahydrate in 0.1
mol dm 3hydrochloric acid and purifying the solution by
extraction with APDC and chloroform.5,6 The purification was effective because no copper was detected, as
described below.
A standard copper(II) solution (1 g cm 3, in 0.1 mol
dm-3 hydrochloric acid) was prepared from a commercial
standard solution and diluted with 0.1 mol dm 3 hydrochloric acid to appropriate concentrations immediately
before use.
An ammoniacal EDTA solution (0.01 mol dm 3) was
prepared by dissolving EDTA (disodium salt dihydrate)
in 1 mol dm-3 aqueous ammonia.
Water was purified by distillation and ion exchange,
and then passed through a Millipore Milli-Q purification
system. All reagents used were of reagent grade and
were employed without further purification, unless
otherwise stated.
Procedure
A synthetic sample solution (containing 20 mg of
aluminum and nanogram amounts of copper), 2 cm3, was
placed in a Pyrex glass test tube and sealed with a
silicone-rubber
stopper bearing two glass tubes.
The

ANALYTICAL

690

solution was evaporated to dryness by heating at 150C

for 20 - 30 min. During the evaporation, nitrogen gas
(previously filtered through a 0.1-m membrane filter)
was introduced into the test tube at a flow rate of
0.5 dm3 min 1 to provide a clean atmosphere and to
sweep out the solvent vapor. The residue was cooled to
room temperature and pulverized with a Teflon rod.
After adding 2 cm3 of ammoniacal EDTA solution, the
test tube was irradiated with ultrasound for 10 min to
extract the copper from the aluminum matrix. The
extraction solvent was separated by centrifugation at
1000g for 15 min and a 10-mm3 aliquot (after dilution, if
necessary) was injected to the graphite cuvette for the
determination of copper by AAS. The measurement
was repeated three times and the absorption readings
were averaged. A calibration graph was prepared by
using ammoniacal EDTA solutions containing nanogram quantities of copper.

Results

and

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1995, VOL.

11

Table 1 Effect of ultrasonic irradiation on the extraction of

100 ng of copper(II) from 20 mg of aluminum

Discussion

Selection of extraction solvent

Generally, extraction solvents are selected from the
viewpoints of (1) sufficient solubility of the desired trace
elements, (2) minimum solubility of the matrix element,
and (3) no interference in the subsequent determination
step.
EDTA reacts with many elements to form stable and
water-soluble chelate compounds. Large amounts of
aluminum ions, however, generate bulky and amorphous
hydroxide precipitates from moderate alkaline solutions,
even in the presence of EDTA. Therefore, aqueous
ammonia containing EDTA was examined for the
extraction of copper from aluminum.
A sample solution (containing 20 mg of aluminum and
100 ng of copper) was evaporated to dryness and then the
residue was treated with the extraction solvent. With
0.01 mol dm-3 EDTA in 1 mol dm 3 aqueous ammonia,
the copper was quantitatively extracted with a recovery
of 94 -100%, while the dissolved aluminum was less than
4%.
The EDTA was essential for the complete extraction.
With aqueous ammonia alone, no copper was extracted
because the copper was strongly trapped in the flocculent
aluminum hydroxide.
Effect of ultrasonic irradiation on extraction
Because the application of a sound field accelerated the
extraction rates2'3,the effect of ultrasound was studied by
changing the irradiation time. As shown in Table 1,
almost constant and complete recoveries were obtained
by applying ultrasound for 3 - 30 min. This indicates
that the ammoniacal EDTA solution is a powerful
solvent, because the irradiation of 30 - 60 min was
usually required in the previous studies.2,3
Separation and determination of copper inaluminum solutions
Different amounts of copper ions were added to 1 cm3

Fig. 1 Extraction of copper(II) from 20 mg of aluminum with

2 cm3 of ammoniacal EDTA solution.

of aluminum
solution,
and evaporation,
extraction
and
determination
were carried out.
The copper added was
nearly completely
recovered,
as shown in Fig. 1.
The
aluminum
accompanying
the
copper
was
determined
by ICP-AES
and found to be 600 - 700 g;
this
amount
did not
interfere
in the
subsequent
determination
of copper.

Analysis ofhigh purity aluminum metal

The proposed method was applied to the analysis of
high-purity aluminum metal. A sample of commercial
metal was dissolved in aqua regia and diluted to 20 cm3
with water. An aliquot of the solution (containing
20 mg of aluminum) was placed in a test tube; the
separation and determination were carried out as described in Procedure.
Table 2 summarizes the results obtained for two
samples: No. 1 (99.999% purity, 3 mm diam.X10 mm
long rods, Mitsuwa Pure Chemicals) and No. 2 (99.99%
purity, l OX2OX1 mm chips, Nakarai Chemicals). Copper added previously to the sample was quantitatively
recovered and successfully determined. The relative
standard deviations were 4.9% (for No. 1) and 0.8% (for
No. 2). Blank values through the whole procedure were
less than the detection limits (<0.6 ng).
The proposed solid-liquid extraction technique can be
applicable to the multielement separation of impurities
from the aluminum matrix, because many trace elements

ANALYTICAL

Table

SCIENCES

Determination

metal

AUGUST

of copper

1995, VOL.

in high-purity

11

aluminum

691

(e.g., Co, Ni, Zn, Cd) are expected to behave similarly to

copper.

References

1. A. Mizuike, "Enrichment Techniques for Inorganic Trace

Analysis", p. 52, Springer, Berlin, 1983.
2. A. Mizuike, K. Fukuda and Y. Ochiai, Talanta, 19, 527
(1972).
3. M. Hiraide, Y. Mikuni and H. Kawaguchi, Analyst
[London], 119, 1451 (1994).
4. M. Hiraide, Y. Mikuni and H. Kawaguchi, Fresenius' J.
Anal. Chem., in press.
5. E. B. Sandell and H. Onishi, "Photometric Determination
of Traces of Metals: General Aspects", p. 529, Wiley, New
York, 1978.
6. 0. G. Koch and G. A. Koch-Dedic, "Handbuch der
Spurenanalyse (Tell 1)", p. 308, Springer, Berlin, 1974.
a.

50 ng of Cu was

added.

b. 100 ng of Cu was added.

(Received April 7, 1995)

(Accepted May 24, 1995)