1995, VOL.








of Traces

an Ammoniacal

of Copper






Masataka HIRAIDE,Yasushi MIKUNIand Hiroshi KAWAGUCHI
Department of Materials Science and Engineering, Nagoya University,Nagoya







Although modern instrumental
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.

A Seiko I & E SAS-760
with an SAS-715
atomizer was used for the determination
of copper.
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

of 2400° C for 2 s for measuring

the absorbance



464, Japan


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.
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 µg 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.
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
stopper bearing two glass tubes.

With aqueous ammonia alone.999% purity. Copper added previously to the sample was quantitatively recovered and successfully determined. The copper added was nearly completely recovered. extraction solvents are selected from the viewpoints of (1) sufficient solubility of the desired trace elements.3 Separation and determination of copper inaluminum solutions Different amounts of copper ions were added to 1 cm3 Fig. The proposed solid-liquid extraction technique can be applicable to the multielement separation of impurities from the aluminum matrix. 3 mm diam. During the evaporation. as shown in Fig. Analysis ofhigh purity aluminum metal The proposed method was applied to the analysis of high-purity aluminum metal. 1.2. 1 Extraction of copper(II) from 20 mg of aluminum with 2 cm3 of ammoniacal EDTA solution. The aluminum accompanying the copper was determined by ICP-AES and found to be 600 . An aliquot of the solution (containing 20 mg of aluminum) was placed in a test tube. 1) and 0.1-µm membrane filter) was introduced into the test tube at a flow rate of 0.700 µg. the copper was quantitatively extracted with a recovery of 94 -100%. because many trace elements . generate bulky and amorphous hydroxide precipitates from moderate alkaline solutions. (2) minimum solubility of the matrix element. The EDTA was essential for the complete extraction. nitrogen gas (previously filtered through a 0. The relative standard deviations were 4. Nakarai Chemicals). the separation and determination were carried out as described in Procedure. A sample of commercial metal was dissolved in aqua regia and diluted to 20 cm3 with water. This indicates that the ammoniacal EDTA solution is a powerful solvent.6 ng). this amount did not interfere in the subsequent determination of copper. With 0.the effect of ultrasound was studied by changing the irradiation time. A calibration graph was prepared by using ammoniacal EDTA solutions containing nanogram quantities of copper. because the irradiation of 30 .01 mol dm-3 EDTA in 1 mol dm 3 aqueous ammonia. The residue was cooled to room temperature and pulverized with a Teflon rod. extraction and determination were carried out.30 min. 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. of aluminum solution. the test tube was irradiated with ultrasound for 10 min to extract the copper from the aluminum matrix. After adding 2 cm3 of ammoniacal EDTA solution.5 dm3 min 1 to provide a clean atmosphere and to sweep out the solvent vapor. As shown in Table 1. 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. 2 (99. l OX2OX1 mm chips.60 min was usually required in the previous studies. 2).30 min. aqueous ammonia containing EDTA was examined for the extraction of copper from aluminum. Results and SCIENCES AUGUST 1995. even in the presence of EDTA.8% (for No. 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. however. Table 2 summarizes the results obtained for two samples: No. no copper was extracted because the copper was strongly trapped in the flocculent aluminum hydroxide. VOL. almost constant and complete recoveries were obtained by applying ultrasound for 3 . 1 (99. Effect of ultrasonic irradiation on extraction Because the application of a sound field accelerated the extraction rates2'3. and evaporation.X10 mm long rods. and (3) no interference in the subsequent determination step. EDTA reacts with many elements to form stable and water-soluble chelate compounds.ANALYTICAL 690 solution was evaporated to dryness by heating at 150°C for 20 . Therefore. Mitsuwa Pure Chemicals) and No. while the dissolved aluminum was less than 4%.9% (for No. Large amounts of aluminum ions. Blank values through the whole procedure were less than the detection limits (<0.99% purity. The extraction solvent was separated by centrifugation at 1000g for 15 min and a 10-mm3 aliquot (after dilution.

Y. Talanta. 50 ng of Cu was added. Onishi. 529. Hiraide. "Photometric Determination of Traces of Metals: General Aspects". 1995) . Mikuni and H. Ochiai. 6. 1995) (Accepted May 24. Springer. p.ANALYTICAL Table 2 SCIENCES Determination metal AUGUST of copper 1995. Springer. Koch-Dedic. Fresenius' J. 52. Y. 1451 (1994). Co. 119. p. K. Koch and G. 1983. 1978. Fukuda and Y. a. Zn. Mizuike. 1974. E. Anal. "Enrichment Techniques for Inorganic Trace Analysis". 308. M. 3. VOL. (Received April 7. Analyst [London]. M. Mizuike. b.. A. Kawaguchi. in high-purity 11 aluminum 691 (e. Berlin. Wiley. 0. 19. p. Ni. Hiraide. G. New York. Chem. B. 2. in press. A.g. "Handbuch der Spurenanalyse (Tell 1)". 100 ng of Cu was added. Sandell and H. Berlin. Mikuni and H. 527 (1972). A. Kawaguchi.. 4. 5. References 1. Cd) are expected to behave similarly to copper.