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Spectrophotometric Determination
of Cadmium(II) Using
p,pDinitroSYMDiphenylcarbazid in
Aqueous Solutions
a

Laura Bulgariu , Dumitru Bulgariu & Ioan Srghie

Department of Analytical Chemistry, Faculty of Industrial Chemistry,


Technical University Gh. Asachi, Iai, Romania
b

Department of GeologyGeochemistry, Faculty of Geography and Geology,


Al. I. Cuza University, Iai, Romania
Available online: 02 Feb 2007

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

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Analytical Letters, 38: 23652375, 2005


Copyright # Taylor & Francis, Inc.
ISSN 0003-2719 print/1532-236X online
DOI: 10.1080/00032710500316597

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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

Abstract: A sensitive and selective spectrophotometric method is proposed for


the rapid determination of cadmium(II) using, p,p0 -dinitro-sym-diphenylcarbazid,
directly in aqueous solution. The reaction between cadmium(II) and p,p0 -dinitrosym-diphenylcarbazid occurs immediately in strong basic media (0.02 N sodium
hydroxide solution). The complex shows a maximum of absorption at 630640 nm,
and the absorbance remains stable for at least 24 h. The method allows the cadmium
determination over the range 0.5 6.0 mg mL21, with a molar absortivity of
2.05  104 L mol21 cm21 and features a detection limit of 0.13 ppm. The interferences
22
caused by several ions [Ca(II), K(I), Ba(II), Al(III), Pb(II), Zn(II), Cl21, NO2
3 , SO4 ],
which are present in most of environmental samples, were determined. The validation
of the spectrophotometric method was done by recovery test of cadmium(II) in tap water
and sea water. The results show that the proposed method has been successfully applied
to the determination of cadmium(II) in water samples.
Keywords:
p,p0 -Dinitro-sym-diphenylcarbazid,
spectrophotometric method, aqueous solution

cadmium(II)

determination,

Received 23 June 2005; accepted 12 July 2005


Address correspondence to Laura Bulgariu, Department of Analytical Chemistry,
Faculty of Industrial Chemistry, Technical University Gh. Asachi, 700050 Iasi,
Romania. E-mail: lbulg@ch.tuiasi.ro
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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.

MATERIALS AND METHODS


Reagents
Stock solution of 1000 mg mL21 of cadmium nitrate (Fluka) was prepared
by dissolving salt in distilled water and diluting the solution to 1000 mL.
The obtained solution was standardized according to the gravimetric and

Aqueous solution

3.6  104

PAN is 1-(2-pyridilazo)-2 naphtol; PAR is 4-(2-pyridilazo)-resorcinol.

226

o-Phenanthroline

CHCl3

9.8  104

505

PAR

CHCl3

5.3  103

380 390

Oxine

CHCl3

(4.9 5.1)  103

550 560

CHCl3

7.8  104

518

PAN

CCl4

8.8  104

520

Dithizone

Solvent

lmax (nm)

1 (L mol21 cm21)

Spectrophotometric methods used for cadmium(II) determination

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)

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Spectrophotometric Determination of Cadmium II


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L. Bulgariu et al.

Figure 1. The structure of p,p0 -dinitro-sym-diphenylcarbazid.

titrimetric procedures (Bilba et al. 1999; Macarovici 1979). Working solution


of cadmium was prepared by dilution from the stock solution with distilled
water. The reagent solution was obtained by dissolving 0.05 g p,p0 -dinitrosym-diphenylcarbazid (GMBH & CO, Munich, Germany) in 150 g of 96%
ethanol. The required reaction media was obtained using 1 N sodium
hydroxide (Merck) solution, freshly prepared. All other reagents were of
analytical reagents degree and were used without purification. The aqueous
solutions were prepared with distilled water. All glassware was shaken in
sulphochromic mixture, for at least 24 h and washed with distilled water.

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.

Spectrophotometric Determination of Cadmium II

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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

Figure 2. The absorbtion spectra of p,p0 -dinitro-sym-diphenylcarbazid (1) and of


cadmium complex (4.54 mg Cd(II) mL21) (2), against water.

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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 3. Spectral curves at different concentrations of cadmium(II) (A)


1.14 mg mL21, (B) 1.70 mg mL21, (C) 2.27 mg mL21, (D) 2.83 mg mL21, (E)
3.40 mg mL21, (F) 3.97 mg mL21, (G) 4.54 mg mL21, against a blank sample.

Figure 4.

The IR spectra of p,p0 -dinitro-sym-diphenylcarbazid (1) and of cadmium complex (2).

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Spectrophotometric Determination of Cadmium II


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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).

Under these conditions, the minimum volume of 0.037% reagent solution


required to guarantee total complex formation with 6 mg mL21 cadmium(II)
was 2.0 mL, which means that the minimum excess of the reagent in the
system is above 40%.
The calibration curve was made as described in the general procedure and
a satisfactory correlation coefficient was found. The Lambert Beer law is
obeyed from 0.5 6.0 mg mL21 of cadmium(II), with a molar absortivity coefficient of 2.05  104 L mol21cm21, at 630 nm against a blank solution. The
calibration sensitivity (that is the slope of the analytical curve), the
detection limit (which was calculated as three times the standard deviation
of the seven replicate measurements), the precision (RDS), as well as other
analytical characteristics of the procedure, are summarized in Table 2.
An important step in characterization of the applicability of this method is
the selectivity towards cadmium(II), in comparison with other interfering ions.
For the quantification of this characteristic, we use the selectivity coefficient
(aij), which is defined as ratio of cadmium(II) concentration (cCd) to the interfering ions concentration (cj), which gives a 5% absorbance change from the
reference solution.
In this study, the interfering ions were added to an identical reference
solution, with a constant cadmium content (3.4 mg mL21), until a 5%
change in absorbance was obtained. The calculated values of the selectivity
coefficients are summarized in Table 3. Copper(II), nickel(II), cobalt(II),
and iron(III) ions interfered seriously at all concentrations. These interferences are not necessarily caused by the reaction of these ions with organic
reagent but, probably due to the high basic media that favors the formation
of insoluble hydroxides.

Spectrophotometric Determination of Cadmium II


Table 2.

The analytical characteristics of the proposed method

Analytical parameters

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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 (%)

1-cm glass cell, s-standard deviation (n 7, ca 258C).

The selectivity coefficient values show that this method is selective


towards cadmium(II) in the presence of several common ions that were
fairly abundant in environmental samples. As Table 3 shows the K(I),
2
Ca(II), Ba(II), Al(III), Cl2, SO22
4 , and NO3 ions, practically do not
interfere, which means that the method can be used for quantitative determination of cadmium(II) in saline media. Another important fact is the selectivity of the method towards cadmium(II), in the presence of zinc(II) and lead(II)
ions, which might be present in various real samples and interfere in most of
cadmium determination methods.
In order to use the selectivity advantages, the recovery test was done using
two categories of water samples: the first, tap water, from Gh. Asachi
Technical University laboratories, and the second, sea water (with relative
high salinity), from the Black Sea. The water samples were filtered with a
glass filter (1-G-4), in order to remove the suspended matter and the
particles, and then they were alkalinized, by adding 2 3 drops of 1 N
sodium hydroxide solution (pH 9), for the removal of the Mg(II) interferences. To investigate the recovery of cadmium(II), 15 mL of treated water
was transferred to each of the three 50 mL volumetric flasks, and 1.0 mL,
1.5 mL, 2.0 mL cadmium(II) standard solution (56.76 mg mL21) was added
Table 3.

The select coefficients values

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

The aCd,j values were determined in a 3.40 mg mL21 Cd(II)


reference solution, and calculated for a 5% changing in absorbance
(n 3, ca 258C).

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Table 4.

L. Bulgariu et al.
The recovery test
Tap water

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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

Average of six determination + S%, calculated based on the calibration graph


(ca 258C).

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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Spectrophotometric Determination of Cadmium II

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