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Spectrophotometric Determination
of Cadmium(II) Using
p,pDinitroSYMDiphenylcarbazid in
Aqueous Solutions
a
To cite this article: Laura Bulgariu, Dumitru Bulgariu & Ioan Srghie (2005): Spectrophotometric
Determination of Cadmium(II) Using p,pDinitroSYMDiphenylcarbazid in Aqueous Solutions, Analytical
Letters, 38:14, 2365-2375
To link to this article: http://dx.doi.org/10.1080/00032710500316597
MOLECULAR SPECTROSCOPY
Spectrophotometric Determination of
Cadmium(II) Using p,p0 -Dinitro-SYMDiphenylcarbazid in Aqueous Solutions
Laura Bulgariu
Department of Analytical Chemistry, Faculty of Industrial Chemistry,
Technical University Gh. Asachi, Iasi, Romania
Dumitru Bulgariu
Department of GeologyGeochemistry, Faculty of Geography and
Geology, Al. I. Cuza University, Iasi, Romania
Ioan Sarghie
Department of Analytical Chemistry, Faculty of Industrial Chemistry,
Technical University Gh. Asachi, Iasi, Romania
cadmium(II)
determination,
2366
L. Bulgariu et al.
INTRODUCTION
Cadmium is one of the main elemental polluants in environment due to its
increasing utilization in industry and mining. In a 1997 U.S. Environmental
Protection Agency report (ATSDR/EPA 1999) cadmium appeared as # 7 in
a priority list of the top 20 hazardous substances. For this reason, the determination of this metal is very important, especially while evaluating the extent of
human exposure.
In determination of cadmium(II) various methods, including ICP-MS
(Rose et al. 2001), ion-chromatography (Muraviev 2000), anodic stripping
analysis (Adelaju et al. 1984; Osipova et al. 2000), and electrothermal
atomic absorption spectrometry (Kamata et al. 1982; Chakraborti 1987;
Sato and Uedo 2000), have been used. Many of these methods either are
time consuming or require complicated and expensive instruments. From
this point of view, the development of rapid, simple, and inexpensive analytical methods is one of the areas of growing interest, and becomes more
accepted, especially in the environment and industrial field.
Spectrophotometry is one of the most frequent methods, used for
cadmium(II) determination in environment samples. The simplicity of the
system design, low cost, easy automation, and feasibility of wide-range determination are some of the favorable characteristics of spectrophotometric
methods. But, the main inconvenience is that, in the case of cadmium(II)
determination, most of spectrophotometric methods occur in organic media,
and for this reason, they need supplementary precautions. In Table 1, the
main spectrophotometric methods for cadmium(II) determination are summarized, and they are presented in the reference studies for analytical chemistry.
In this paper, the reaction between cadmium(II) and p,p0 -dinitro-symdiphenylcarbazid, in aqueous media, was spectrophotometrically studied.
The blue complex of cadmium(II) with the organic reagent is obtained in
strong basic media and it has a good behavior from the point of view of the
spectrophotometric study. Used first, for qualitative identification of
cadmium (Ripan et al. 1963; Kekedy 1982) the reaction with p,p0 -dinitrosym-diphenylcarbazid (Fig. 1) can be a good alternative method for the determination of cadmium(II) directly in aqueous solutions. The proposed method,
showed high selectivity, good stability, and sensitivity for cadmium; and it
was evaluated for the cadmium determination in water samples.
Aqueous solution
3.6 104
226
o-Phenanthroline
CHCl3
9.8 104
505
PAR
CHCl3
5.3 103
380 390
Oxine
CHCl3
550 560
CHCl3
7.8 104
518
PAN
CCl4
8.8 104
520
Dithizone
Solvent
lmax (nm)
1 (L mol21 cm21)
Reagent
Table 1.
Ref.
Lacy et al. (1999); International Union of
Pure and Applied Chemistry (1963); Dean
(1995); Fresenius et al. (1988); Flaschka
and Barnard Jr. (1972)
International Union of Pure and Applied
Chemistry (1963); Dean (1995); Fresenius
et al. (1988); Flaschka and Barnard Jr.
(1972)
Lacy et al. (1999); International Union of
Pure and Applied Chemistry (1963); Dean
(1995); Fresenius et al. (1988); Flaschka
and Barnard Jr. (1972)
International Union of Pure and Applied
Chemistry (1963); Flaschka and Barnard
Jr. (1972)
Lacy et al. (1999); International Union of
Pure and Applied Chemistry (1963); Dean
(1995); Fresenius et al. (1988); Flaschka
and Barnard Jr. (1972)
Fresenius et al. (1988)
2368
L. Bulgariu et al.
Apparatus
Spectrophotometric measurements were done with an S 104 D Digital Spectrophotometer with a 1.0 cm glass cell. The pH measurements were carried
out with a pH/ion analyzer, OP-271 Radelkis, equipped with a combined
glass electrode. The infrared spectra were recorded with a DIGILAB SCIM
TAR series infrared (IR) spectrometer, using the KBr pellet method.
General Procedure
An aliquot containing 1 6 mg mL21 cadmium(II) was transferred into a
50 mL volumetric flask. One mL of 1 N sodium hydroxide solution and
2.0 mL of p,p0 -dinitro-sym-diphenylcarbazid ethanolic solution were added.
The solution was diluted to the mark with distilled water and mix. The absorbance was measured at 630 nm in a 1.0 cm glass cell against a blank solution,
which has the same composition, but without cadmium.
The selectivity coefficients were calculated as ratio between the cadmium
concentration and the interfering ion concentration, which gives a 5% absorbance change, in a reference solution.
2369
The recovery test was done using tap water, obtained from Gh. Asachi
Technical University laboratories, and sea water, obtained from the Black Sea,
after a preliminary treatment. The cadmium(II) content in an unknown sample
was determined using a preparated calibration graph.
The solid cadmium complex used in IR spectrometry analysis was
obtained by increasing the mixture component concentration by 10 times.
RESULTS AND DISCUSSION
Under the conditions of preliminary investigation of the proposed procedure,
the blue colored complex of cadmium(II) with the organic reagent is formed
only in a strong basic media. Better results were obtained by using a 1 N
sodium hydroxide solution. In a total volume of 50 mL, the composition
needed for the maximum color development was in the range of 0.51.25 mL.
Hence, 1 mL of 1 N sodium hydroxide solution (pH 11.8 12.0) was fixed
as reaction media. At a higher NaOH concentration, the color intensity
decreases. Other buffer solutions, including borate buffer with the same pH,
were tested and found to be unsatisfactory.
The absorption spectra, in the visible region of p,p0 -dinitro-sym-diphenylcarbazid reagent and the cadmium complex against water are shown in Fig. 2.
Under these conditions, the organic reagent has a maximum absorbance at
2370
L. Bulgariu et al.
550 nm and the cadmium complex exhibits one maximum at 580 nm. Because
the difference between maximum wavelength of the organic reagent and the
cadmium complex is smaller, we perform the absorption measurements
against a bank solution, which has the same composition, but without
cadmium. The absorption spectra of the cadmium complex, for different
cadmium(II) concentrations are shown in Fig. 3. The cadmium complex
shows a maximum absorbance at 630 640 nm, against a blank solution, and
can be successfully used for quantitative analysis of cadmium(II) in
aqueous solutions. The p,p0 -dinitro-sym-diphenylcarbazid reagent reacts
immediately with cadmium(II), forming a blue complex in strong basic
aqueous media (pH 11.8 2 12.0), and the absorbance reaches its
maximum in 5 min and remains stable for at least 24 h.
The complex composition was determined by the molar ratio method
(Christian 1994). The results demonstrated that the complex has a molar
ratio of 1 : 2 Cd(II) : p,p0 -dinitro-sym-diphenylcarbazid). These results were
confirmed also by analysis of IR spectra, recorded for organic reagent and
cadmium complex (Fig. 4). The 443 cm21 and 1398 1390 cm21 band from
cadmium complex IR spectra indicates the cadmium fixation at ketonic
Figure 4.
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L. Bulgariu et al.
oxygen atom and at a b-nitrogen atom towards the ketonic group. On the basis
of these observations, the cadmium fixation takes place, probably, according
to Reaction (1).
Analytical parameters
2373
at 630 nm
2.05 104 L mol21 cm21
0.093 mL mg21
0.9879
0.13 ppm
0.45 mg mL21
0.5 6.0 mg mL21
1.67%
Molar absortivity
Calibration sensitivity
Correlation coefficient
Limit of detection (3s)
Limit of quantification (10s)
Linear dynamic range
RDS (%)
Interfering, j
log aCd,j
Interfering, j
log aCd,j
K(I)
Ca(II)
Ba(II)
Mg(II)
Al(III)
23.120
22.424
23.063
21.258
22.454
Pb(II)
Zn(II)
Chloride
Nitrate
Sulphate
22.505
22.405
22.485
22.921
22.544
2374
Table 4.
L. Bulgariu et al.
The recovery test
Tap water
Cd(II) added
[mg mL21]
Cd(II) determineda
[mg mL21]
% Recovery
1.135
1.703
2.271
1.139
1.692
2.390
100.36 + 0.1
99.36 + 0.6
105.29 + 1.8
Seawater
Cd(II) determineda
[mg mL21]
% Recovery
1.132
1.683
2.254
99.40 + 0.4
99.01 + 0.6
99.26 + 0.7
to each flask. In all cases, the samples were analyzed according to the general
procedure. The cadmium(II) content was determined using a calibration graph
at 630 nm. The average recovery percentages obtained for the addition of
cadmium(II) spikes to water samples are shown in Table 4.
As Table 4 shows the good recovery of cadmium(II) was obtained for
both types of water samples, indicating that the constituents of water samples do not interfere significantly with the determination of cadmium(II).
Therefore, this method can be a good alternative device for the cadmium(II)
determination, directly in aqueous solutions.
CONCLUSIONS
The method using p,p0 -dinitro-sym-diphenylcarbazid as spectrophotometric
reagent for cadmium(II) determination is simple, rapid, and occurs in
aqueous media. The blue complex is formed immediately in strong basic
media (0.02 N NaOH solution) and its absorbance at 630 nm remains stable
for at least 24 h. The suitable detection limit (0.13 ppm), appropriate dynamic
range (0.5 6.0 mg mL21), and good selectivity towards cadmium(II) at the
presence of several ions are parameters that have pointed out the applicability
of this method. The results of the recovery test showed that the constituents of
water samples do not interfere significantly with the determination of
cadmium(II). Therefore, this method can be a good alternative device for the
direct cadmium(II) determination in real samples, in aqueous solutions.
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