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A Rapid Spectrophotometric Method for the Determination of Trace Level Silver

Using 1, 5-diphenylthiocarbazone in Aqueous Micellar Solutions

Article  in  International Research Journal of Pure and Applied Chemistry · January 2014

DOI: 10.9734/IRJPAC/2014/8157

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 International Research Journal of Pure &
Applied Chemistry
4(4): 468-485, 2014

SCIENCEDOMAIN international
www.sciencedomain.org

A Rapid Spectrophotometric Method for the

Determination of Trace Level Silver Using 1, 5-
diphenylthiocarbazone in Aqueous Micellar Solutions

M. Jamaluddin Ahmed1* and Syeda Rahimon Naher1

1
Laboratory of Analytical Chemistry, Department of Chemistry, University of Chittagong,
Chittagong-4331, Bangladesh.

Authors’ contributions

This work was carried out in collaboration between both authors. Both of us carried out all
the laboratory works, performed the statistical analysis, managed the literature searches
and prepared the final manuscript. Both of us read and approved the final manuscript.

nd
Received 2 December 2013
th
Original Research Article Accepted 10 March 2014
th
Published 17 April 2014

ABSTRACT

The very sensitive, fairly selective direct spectrophotometric method is presented for the
rapid determination of silver at ultra-trace level using1, 5-diphenylthiocarbazone
(dithizone) as a new micellar spectrophotometric reagent (  max= 495 nm) in a slightly
acidic (0.1-1.0 M H2SO4) aqueous solution. The presence of a micellar system avoids the
previous steps of solvent extraction and reduces the cost, toxicity while enhancing the
sensitivity, selectivity and molar absorptivity. The average molar absorptive of the Ag -
dithionate complex formed in presence of anionic sodium deducible sulfate (SDS)
5 -1 -1
surfactant was found to be 1.6 x 10 L. mol. cm which was almost 10 times higher
4 -1 -1
than the value observed (1.0 x 10 L. mol. cm ) in the standard method, resulting in an
increase in the sensitivity of the method. The reaction is instantaneous and
the absorbance remains stable for over 24 h. The Sandell’s sensitivity was found to 12 ng
-2 -1
cm of Ag. Linear calibration graphs were obtained for 0.07-10 mg L of silver; the
stoichiometric composition of the chelate is 1:1 (Ag: dithizone). The method is
-1
characterized by a detection limit of 0.1 µg L of Ag. Large excess of over 50 cations,
anions and complexing agents (e.g. EDTA, tartrate, oxalate, citrate, phosphate, azide) do
not interfere in the determination. The method was successfully applied to a number of

___________________________________________________________________________________________

*Corresponding author: Email: pmjahmed55@gmail.com;

 International Research Journal of Pure & Applied Chemistry, 4(4): 468-485, 2014

environmental water samples (potable and polluted), biological samples (human blood
and urine), photographical samples and soil samples. The method has high precision and
-1
accuracy (s = ±0.01 for 0.1 mg L ).

Keywords: Micellar spectrophotometry; silver; 1, 5-diphenylthiocarbazone; sodium dodecyle

sulfate; environmental; biological; photographical; soil samples.

1. INTRODUCTION

Silver is a useful element in many respects, it has an important role in electrical and
electronic applications, photographic film production and the manufacturing of fungicides [1].
Silver compounds and alloys have been widely used in dental and pharmaceutical
preparations because of their marked antibacterial properties [2]. Silver is considered toxic
for humans and the recommendations of the World Health Organization (WHO) permit
–1
maximum concentrations of 0.01 mg L of silver ions in drinking water disinfection, but
–1
the United States Environmental Protection Agency (USEPA) recommends 0.05 mg L
as maximum [3]. Silver is both vital and toxic for many biological systems and its content in
environmental samples is increased with the increasing use of silver compounds and silver-
containing products in industry and in medicine [4]. Silver can enter into the environment via
industrial waters and might pose a potential risk as water pollutant. Thus, separation, pre-
concentration and sensitive determination of silver ion is of increasing interest [5].

1,5-Diphenylthiocarbazone is one of the most widely used photometric reagents and forms
colored water-insoluble complexes with a large number of metal ions. Metal-dithizone
complexes are water insoluble and thus their determination requires a prior solvent
extraction step into CHCl3 or CCl4 [6-7], followed by spectrophotometric determinations.
Since these methods involve solvent extraction are lengthy and time-consuming and lack
selectivity due to much interference [8], CHCl3 and CCl4 have been listed as toxic and as
environmental pollutants [9] i.e. carcinogens by the ATSDR and EPA [10], this problem has
been overcome in recent years by introducing a hydrophobic micellar system generated by
a surfactant similar to that employed in phase-transfer reactions [11- 12].

Micellar systems are convenient to use because they are optically transparent, readily
available, relatively non-toxic and stable [13]. Nevertheless, the addition of surfactants at
concentrations above the CMC to an aqueous medium to form a micellar solution is the
most commonly preferred procedure today. A non-ionic surfactant, like Triton X-100 [14-15]
and Sweed 80 [16], have been used for the spectrophotometric determination of several
metal ions. Similarly, a few anionic surfactants have been used [17].

The aim of the present study is to develop a simpler direct spectrophotometric method for
the trace determination of silver with dithizone in the presence of inexpensive anionic
micelles, such as sodium dodecyl sulfate, in aqueous solutions. This method does not
require a solvent-extraction step; hence, the use of carcinogenic CCl4 or CHCl3 is avoided.
The method described here has recorded for the first time the non-extractive direct
spectrophotometric determination of Ag in aqueous media without the recourse of any
“clean-up” step. This method is far more selective, sensitive, non-extractive, simple and
rapid than all of the existing spectrophotometric methods [18-22]. This method is very
-1
reliable and a concentration in the ng g range in an aqueous medium at room temperature
(25±5ºC) can be measured in a very simple and rapid way.

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 International Research Journal of Pure & Applied Chemistry, 4(4): 468-485, 2014

2. EXPERIMENTAL SECTION

2.1 Instrumentation

Shimadzu (Kyoto, Japan) (Model-1800) double beam UV/VIS the recording

spectrophotometer and a Jenway (England, U.K) (Model-30100) pH meter with a
combination of electrodes were used for the measurements of absorbance and pH,
respectively. A Varian (Australia) ICP – MS spectrophotometer was used for comparing the
results.

2.2 Chemicals and Reagents

All of the chemicals used were of analytical reagent grade or the highest purity available.
Doubly distilled deionized water, which is non-absorbent under ultraviolet radiation, was
used throughout. Glass vessels were cleaned by soaking in acidified solution of KMnO4 or
K2Cr2O7 followed by washing with concentrated HNO3 and rinsed several times with
deionized water. Stock solutions and environmental water samples (1000-mL each) were
kept in polypropylene bottles containing 1-mL of concentrated HNO3. More rigorous
contamination control was applied when the silver levels in the specimens were low.

2.2.1 Sodium dodecyl sulfate (SDS) solution (1%)

A 100 mL of SDS solution was prepared by dissolving 1g of pure sodium dodecyl sulfate
(SDS) (E. Merck, Darmstadt, Germany) in doubly distilled de-ionised water using ultrasonic
bath.
-3
2.2.2 15-diphenylthiocarbazone solution 1×10 M

This solution was prepared by dissolving the requisite amount (0.025%) of 1,5-
diphenylthiocarbazone ( E. Merck, Germany) in a known volume of absolute ethanol. More
dilute solutions of the reagent were prepared as required.
-3
2.2.3 Standard silver solution 9×10 M
-1
A stock solution (1000 mg L ) of Ag was prepared by dissolving 0.1575 g of silver nitrate
(Merck, Germany) in 100 mL of doubly distilled deionized water. The working standard of
silver solution was prepared by suitable dilutions of this stock solution.

2.2.4 Tartrate solution

A 100-mL stock solution of tartrate (0.01%) was prepared by dissolving 10 mg of A.C.S.

grade (99%) potassium sodium tartrate tetrahydrate in (100-mL) deionized water.

2.2.5 Dilute ammonium hydroxide solution (NH 4OH)

A 100-mL solution of dilute ammonium hydroxide was prepared by diluting 10-mL

concentration. NH4OH (28-30% A.C.S. grade) to 100-mL with deionized water. The solution
was stored in a polypropylene bottle.

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 International Research Journal of Pure & Applied Chemistry, 4(4): 468-485, 2014

2.2.6 1, 10-Phenanthrolin solution

A 0.1% 1, 10-phenanthrolin solution was prepared by dissolving 0.1 gm amount in 100-mL

slightly hot deionized water.

2.2.7 Sodium azide solution

A 100-mL sodium azide solution (2.5 % w/v) (Fluka purity > 99%) was freshly prepared by
dissolving 2.5 gm in 100-mL of deionized water.

2.2.8 EDTA solution

A 100-mL stock solution of EDTA (0.01%) was prepared by dissolving 10 mg of A.C.S.

grade (≥90%) ethylenediaminetetraacetic acid, dissodium salt dehydrate in (100-mL)
deionized water.

2.2.9 Other solutions

Solutions of a large number of inorganic ions and complexing agents were prepared from
their analytical grade or equivalent grade, water soluble salts. In the case of insoluble
substances, special dissolution methods were adopted [23].

2.3 General Procedure

To 0.1-1.0 mL of a slightly acidic solution containing 0.7-100  g of silver in a 10-mL

volumetric flask was mixed with 1.0-4.0 (preferably 1.0 mL ) of 1% sodium dodecyle sulfate
(SDS) and 1.0– 4.0 (preferably 1.0 mL) of 1 M sulfuric acid followed by the addition of a
-3
25 - 80 fold molar excess of a dithizone solution (preferably 1.0-mL of 1 x 10 M). The
mixture was diluted up to the mark with de-ionized water. The absorbance was measured at
495 nm against a corresponding reagent blank. The silver content in an unknown sample
was determined using a concurrently prepared calibration graph.

3. RESULTS AND DISCUSSIONS

3.1 Factors Affecting the Absorbance

3.1.1 Absorption spectra

The absorption spectra of bluish yellow color of the silver - dithizone system in presence of
1-mL 1M sulfuric acid solution were recorded using a spectrophotometer. The absorption
spectra of the silver - dithizone is a symmetric curve with maximum absorbance at 495 nm
5 -1 -1
and an average molar absorptivity of 1.6 x 10 L mol cm (Fig. 1). The reagent blank
exhibited negligible absorbance, despite having a wavelength in the same region. In all
instances, measurements were made at 495 nm against a corresponding reagent blank.
The reaction mechanism of the present method is as reported earlier [24].

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 International Research Journal of Pure & Applied Chemistry, 4(4): 468-485, 2014

Fig. 1. A, B and C absorption spectra of Ag-dithizone system in anionic micellar

media of sodium dodecyl sulfate, carbon tetrachloride media and the reagent blank
(  max = 495 nm), respectively

3.1.2 Effect of surfactant

Of the various surfactants [nonionic {polyoxyethylenedodecylether (Briz-35); cationic

{cetyltrimethylammonium bromide (CTAB) and anionic {cetylpyridinium chloride (CPC),
sodium dodecyl sulfate (SDS)] studied, SDS was found to be the best Surfactant for the
System. In the 1% SDS medium, however, the maximum absorbance was observed; hence,
1% SDS solution was used in the determination procedure. It also increases the solubility of
Silver-chelate complex and thus reduces the cost and toxicity. In this way, 1% SDS
enhances sensitivity, selectivity and molar absorptivity in this method.

Different volumes of 1% SDS solutions were added to a fixed metal ion concentration, in a
10 mL volumetric flask a` the absorbance was measured according to the standard
-1
procedure. Effect of surfactant concentration was studied on the absorbance of 1 mg L Ag-
chelate complex, and 1.0-4.0 mL of 1% SDS solution produced a constant absorbance of
the Ag-chelate. Outside this range of surfactant the absorbance decreased (Fig. 2). The
effect may be due to inadequate interactions of surfactant at lower concentrations, while the
micellar dilution effect is responsible for decreasing in the absorbance at higher surfactant
concentrations. For all subsequent measurements, 1-mL of 1% SDS solution was added.

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 International Research Journal of Pure & Applied Chemistry, 4(4): 468-485, 2014

Fig. 2. Effect of a surfactant on the absorbance of the Ag-dithizone system

3.1.3 Effect of acidity

Of the various acids (nitric, sulfuric, hydrochloric and phosphoric) studied, sulfuric acid was
found to be the best acid for the system. The variation of the absorbance was noted after
the addition of 0.05-5.0-mL of 1M sulfuric acid to every 10-mL of test solution. The
maximum and constant absorbance was obtained in the presence of 1-3.0-mL of 1 M
0
sulfuric acid at room temperature (25±5) C. Outside this range of acidity, the absorbance
decreased (Fig. 3). For all subsequent measurements 1-mL of 1 M sulfuric acid (pH 2) was
added.

3.1.4 Effect of time

The reaction is very fast. A constant maximum absorbance was obtained just after dilution
within few seconds to volume and remained strictly constant for 24h (Fig. 4).

3.1.5 Effect of temperature

Effect of various temperatures (10-90°C) on Ag-dithizone system was studied. The Ag-
dithizone system attained maximum and constant absorbance at room temperature
(25±5°C).

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 International Research Journal of Pure & Applied Chemistry, 4(4): 468-485, 2014

Fig. 3. Effect of the acidity on the absorbance of the Ag-dithizone system

3.1.6 Effect of reagent concentration

Different molar excesses of dithizone were added to a fixed metal-ion concentration and
the absorbance was measured according to the standard procedure. It was observed that a
-1
1 mg L of silver metal (optical path length 1 cm), the reagent molar ratios of 1:25 to 1:80
produced a constant absorbance of Ag - chelate (Fig. 5). A greater excess of the reagent
-3
was not studied. For all subsequent measurements, 1-mL of 1 ×10 M dithizone reagent
was added.

3.1.7 Calibration graph (Beer's law and sensitivity)

-1
The effect of the metal concentration was studied over 0.01-100 mg L , distributed in four
-1
different sets (0.01-0.1, 0.1-1.0, 1.0-10 and 10-100 mg L ) for convenience of the
-1
measurement. The absorbance was linear for 0.07-10.0 mg L of silver at 495 nm. From the
slope of the calibration graph, the average molar absorption co-efficient was found to be 1.6
5 -1 -1
x 10 L mol cm . The Sandell’s sensitivity [25] (concentration for 0.001 absorbance unit)
-2
was found to be 12 ng cm . Of these two calibration graphs, the one showing the limit of
the linearity range is given in (Fig. 6). The next one was straight-line graph passing through
2
the origin (R = 0.999).

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 International Research Journal of Pure & Applied Chemistry, 4(4): 468-485, 2014

Fig. 4. Effect of the time on the absorbance of the Ag-dithizone system

[Ag: Dithizone]

Fig. 5. Effect of reagent [Ag: dithizone molar concentration ratio] on the absorbance
of Ag–dithizone system in micellar media

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 International Research Journal of Pure & Applied Chemistry, 4(4): 468-485, 2014

-1
Fig. 6. Calibration graph: B, 1.0 -10 mg L of Ag

The selected analytical parameters obtained with the optimization experiments are
summarized in Table 1.

Table 1. Selected analytical parameters obtained with optimization experiments

Parameters Studied range Selected value

Wavelength /  max(nm) 200-800 495
Acidity/ M H2SO4 0.03-5.0 1.0-3.5
(preferably 1.0)
pH 3.5 – 1.3 2.0 – 1.5
(preferably 2.0)
Surfactant / 1% SDS / mL 0.1-7.0 1.0-4.0 (preferably 1.0)
Time / h 0-72 1 min-24 h
(preferably 1 min)
0
Temperature / C 25±5 25±5
Reagent (fold molar excess, M:R) 1:1 – 1:80 1:25 - 1:80
(preferably 1: 30)
-1
Linear range/mg L 0.01-100 0.07-10
4_ 5 5
Molar absorption coefficient/ 0.6 x 10 2.6 x 10 1.6 x 10
-1 -1
L. mol. cm.
-2
Sandell’s sensitivity/ ng. cm 1-100 12
Detection limit /  g L
-1
0.01-10 0.1
Reproducibility (% RSD) 0-10 0-2 %
2
Regression co-efficient (R ) 0.9890-0.999 0.999

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 International Research Journal of Pure & Applied Chemistry, 4(4): 468-485, 2014

3.1.8 Effect of foreign ions

The effect of over 50 cations, anions and complexing agents on the determination of only 1
-1
mg L of silver was studied. The criterion for interference [26] was an absorbance value
varying by more than 5% from the expected value for silver alone. There was no
interference from the following 10,000-fold amount of EDTA and tartrate, a 100-fold amount
of acetate, chloride or ammonium. EDTA prevented the interference of a 10-fold excess of
Al, 10-fold excess of Bi(III), 20-fold excess of Cr (VI), 100-fold excess of Pb (II), 100-fold
excess of Na or a 10-fold excess of Sn (II) and tartrate prevented the interference of a 10-
fold excess of V (V) or Zn . During interference studies, if a precipitate was formed, it was
removed by centrifugation. The quantities of these diverse ions mentioned were the actual
amounts studied but not the tolerance limit. However, for those ions whose tolerance limit
has been studied, their tolerance ratios are mentioned in Table 2.
a
Table 2. Tolerance limits of foreign ions, tolerance ratio [Species(x)]/Ag (w/w)

Species x Tolerance ratio Species x Tolerance ratio

[Species (x) /Ag (w/w)] [Species (x) /
Ag (w/w)]
Acetate 100 Iodide 10
b
Aluminum 10 Iron(II) 100
Ammonium 100 Iron(III) 100
b
Arsenic (III) 100 Lead (II) 100
Arsenic (V) 50 Magnesium 100
Ascorbic acid 100 Mercury (I) 200
Azide 100 Mercury (II) 200
Barium 50 Molybdenum (VI) 100
Beryllium 50 Nickel (II) 100
b
Bismuth 10 Nitrate 20
Bromide 100 Oxalate 100
Cadmium 50 Phosphate 100
Calcium 20 Potassium 10
Cerium (III) 200 Selenium (IV) 100
Chloride 20 Selenium (VI) 50
b
Chromium (III) 200 Sodium 100
b
Chromium (VI) 20 Strontium 20
Citrate 100 Tartrate 10000
Copper (II) 50 Titanium(IV) 10
b
Cyanide 50 Tin (II) 10
c
EDTA 1000 Vanadium (V) 10
c
Fluoride 20 Zinc 10
a
Tolerance limit defined as ratio that causes less than 5 percent interference.
b -1
with 1000 mg L , EDTA,
c -1
with 50 mg L tartrate

3.1.9 Composition of the complex

Job’s method [27] of continuous variation and the molar-ratio [28] method were applied to
ascertain the stoichiometric composition of the complex. A Ag: dithizone (1:1) complex was
indicated by both methods.

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 International Research Journal of Pure & Applied Chemistry, 4(4): 468-485, 2014

3.1.10 Precision and accuracy

The precision of the present method was evaluated by determining different concentration
of silver (each analyzed at least five times). The relative standard deviation (n=5) was 2-0%
for 0.7-100 µg of silver in 10-mL, indicating that this method is highly precise and
reproducible. The detection limit (3s/S of the blank) and Sandell’s sensitivity (concentration
for 0.001 absorbance unit) for silver were found to be 0.1  g L and 12  g L ,
-1 -1

respectively. The reliability of our Ag-chelate procedure was tested by recovery studies.
2
Regression analysis of Beer’s law plots at 495 nm revealed a good correlation (R = 0.999).
The method was also tested by analyzing several synthetic mixtures containing silver and
diverse ions (Table 3). The results for silver recovery were in good agreement with added
values (Table 4). The average percentage recovery obtained for the addition of silver spike
to some environmental water samples and real (certified reference materials) samples were
quantitative, as shown in (Table 4 and 5). The results of biological samples analyses by the
spectrophotometric method were in excellent agreement with those obtained by ICP-MS
(Table 6). Hence, the precision and accuracy of the method were found to be excellent.

Table 3. Determination of silver in some synthetic mixtures

-1
Sample Composition of mixtures Silver / mg L
-1 a b
(mg L ) Added Found Recovery ± s (%)
+
A Ag 0.50 0.49 980.5
1.00 1.00 1000.0
3+ 2+
B As in A + As (25) + Co (25) 0.50 0.49 980.6
1.00 0.99 990.3
3+ 3+
C As in B + Cr (25) + Fe (25) 0.50 0.50 1000.0
1.00 0.98 980.5
2+ 2+
D As in C + Mg (25) + Ni (25) 0.50 0.49 980.6
1.00 0.97 970.8
+ VI
E As in D + NH4 (25) + Mo (25) + 0.50 0.48 961.2
EDTA (100) 1.00 0.95 951.5
a
Average of five analyses of each sample
b
The measure of precision is the standard deviation (SD)

3.2 Applications

The present method was successfully applied to the determination of silver in series of
synthetic mixtures of various compositions (Table 3) and also in a number of real
samples (Table 4). The method was also extended to the determination of silver in a
number of environmental water samples, biological, photographical and soil samples. In
view of the unknown composition of environmental water samples, the same equivalent
portions of each sample was analyzed for silver content; the recoveries in both ‘spiked’
(added to the samples before the mineralization and dissolution) and the ‘unspiked’
conditions are in good agreement (Table 5). The results of biological analyses by
spectrophotometric method were found to be in excellent agreement with those obtained by
ICP-MS (Table 6). The results of photographical samples and soil samples analyses by the
spectrophotometric method are shown in (Table 7 and Table 8).

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Table 4. Analysis of high-speed steel and alloys

-1
Sample Certified reference material Silver / mg L
a b
(Composition, %) Added Found Recovery ± s (%)
1 BAS – 5g, high-speed steel (C, Si, 1.0 1.02 1021.0
Mn, Mo, V, Ni, Cr, W and Cu) 5.0 5.15 1030.8
2 BAS – 10 g , high tensil brass (Cu, 1.0 1.05 1051.5
Fe, Pb, Ni, Sn, Al, Zn and Mn) 5.0 5.30 1060.3
3 Brass – 5 f 1.0 1.03 1031.0
(Cu, Zn, Pb, Sn, Fe, Ni, Mn and P) 5.0 5.25 1051.2
4 GSBH – 40101 – 96 1.0 1.06 1061.5
Cr12MoV – Dies steel 5.0 5.35 1071.4
(Cr, Ni, Cu, Mo,V and Co)
5 YSBC – 1013 -1 – 95 1.0 1.08 1081.7
9 Cr17MoV – high tensil steel 5.0 5.45 1091.8
(C, Si, Mn, Cr, Mo, V and Co)
a
Average of five analyses of each sample
b
The measure of precision is the standard deviation (SD)

3.2.1 Determination of silver in synthetic mixtures

Several synthetic mixtures of varying compositions containing silver and diverse ions of
known concentrations were determined by the present method using EDTA as a masking
agent and the results were found to be highly reproducible. The results are shown in Table
3. The accurate recoveries were achieved in all solutions.

3.2.2 Determination of silver in alloys, steels and brass (certified reference materials)

A 0.1g amount of an alloy or steel or brass sample containing different composition of

metals was accurately weighed and placed in a 50-mL Erlenmeyer flask following a method
recommended by Ahmed et al. [29]. To it, 10-mL of concentrated HNO3 and 1-mL of
concentrated H2SO4 were carefully added and then covered with a watch-glass until the
brisk reaction subsides. The solution was heated and simmered gently after the addition of
another 5-mL of concentrated HNO3 until all carbides were decomposed. The solution was
carefully evaporated to dense white fumes to drive off the oxides of nitrogen and then
cooled to room temperature (25±5)ºC. After suitable dilution with deionized water, the
contents of the Erlenmeyer flask were warmed to dissolve the soluble salts. The solution
was then cooled and neutralized with a dilute NH4OH solution in the presence of 1-2-mL of
0.01% (w/v) tartrate solution. The resulting solution filtered, if necessary, through Whatman
no. 40 filter paper into a 25-mL calibrated flask. The residue (silica and tungstic acid) was
washed with a small volume ( 5-mL) of hot (1:99) sulfuric acid, followed by water, the
filtration and washing were collected in the same calibrated flask and the volume was made
up to the mark with deionized water.

A suitable aliquot (1-2-mL) of the above solution was taken into a 10-mL calibrated flask and
the silver content was determined as described under general procedure using citrate or
fluoride as masking agent. Based on five replicate analyses, the average silver
concentration determined by spectrophotometric method was in good agreement with the
spiked values. The average percentage recovery obtained for addition of a silver spike to
some certified reference material was quantitative as shown in Table 4.

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Table 5. Determination of silver in some environmental water samples

Sample Silver / µg L-1 Recovery ± s sr b (%)

Added Founda (%)
Tap water 0 15.00
100 116.0 100.8 ± 0.5 0.25
500 520.0 100.9 ± 0.6 0.28
Well water 0 12.0
100 115.0 102.7 ± 0.6 0.13
500 520.0 101.6 ± 0.4 0.15
Rain Water 0 5.00
100 106.00 100.9 ± 0.5 0.18
500 510.00 100.9 ± 0.6 0.24
River Karnafuly 0 25.00
water (upper) 100 125.00 100 ± 0.0 0.00
500 530.0 100.9 ± 0.8
Karnaphuly 0 28.00
(lower) 100 130.00 101.5 ± 1.0 0.16
500 535.00 101.3 ± 1.2 0.12
Halda 0 10.00
(upper) 100 110.00 100 ± 0.0 0.00
500 515.00 100.9 ± 1.3 0.15
Halda 0 12.00
(lower) 100 110.00 98 ± 1.3 0.18
500 520.00 101.5±1.5 0.26
Sea water Bay of 0 5.00
Bengal (upper) 100 106.00 100.9±0.8 0.39
500 510.00 100.9 ± 1.0 0.49
Bay of 0 6.00
Bengal (lower) 100 108.00 101.9±0.8 0.33
500 510.00 100.8±0.6 0.46
Drain Cable 0 45.00
water Factoryc 100 150.00 103±1.5 0.42
500 540.0 99±1.6 0.44
Paint Industryd 0 35.00
100 138.00 102±1.5 0.45
500 540.00 100.9±1.8 0.56
Jewellarye 0 23.00
100 125.00 101.6±1.6 0.35
500 520.0 99 ±1.7 0.46
a
Average of five replicate determinations.
b
The measure precision is the relative standard deviation (s r)
c
Estern Cables, Patenga, Chittagong.
d
Elite Paint, Nasirabad,Chittagong.
e
Jewellary Shop, Comilla.

3.2.3 Determination of silver in environmental water samples

Each filtered (with Whatman No. 40) environmental water sample (1000-mL) was mixed
with 10-mL of concentrated HNO3 and 1-mL of concentrated H2SO4 in a 2000-mL distillation
flask. The sample was digested in the presence of an excess potassium permanganate
solution following a method recommended by Greenberg et al. [30]. The solution was then
cooled and neutralized with dilute NH4OH solution. The resulting solution was then filtered

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and quantitatively transferred into a 25-mL calibrated flask and made up to the mark with
deionized water.

Table 6. Concentration of silver in blood and urine samples

-1
Serial no. Sample Silver / µg L Sample
a
ICP - MS Proposed method sources
(n = 5) (n = 5)
Found RSD, % Found RSD, %
1 Blood 13.80 1.0 13.75 1.0 Diabetes patient
Urine 3.53 1.2 3.45 1.3 (Female)
2 Blood 79.00 1.0 75.50 1.2 Rheumatoid
Urine 13.79 1.5 13.55 1.5 Arthritic patient
(Female)
3 Blood 7.55 1.3 7.45 1.5 Lupus
Urine 1.94 1.8 1.88 1.9 Gramutosis
patient (Male)
4 Blood 2.58 1.3 2.55 1.2 Normal adult
Urine 0.65 2.0 0.68 1.8 (Male)
a
Samples were from Chittagong Medical College Hospital, Chittagong.

Table 7. Determination of silver in photographical (X-ray) samples

-1 -1
Serial Sample Silver / mg L or µg g
a
No. Found RSD, % Sample sources
(n = 5)
1 4.89 1.5 Photographical solution
-1 -1
X-ray fixer (mg L ) (mg L )
2 X-ray develop 2.81 2.0 Photographical waste solution
-1 -1
(mg L ) (mg L )
3 X-ray hypo 6.25 1.0 Photographical solid material
-1 -1
(µg g ) (µg g )
a
Samples were from Studio University, Chittagong University campus, Chittagong

Table 8. Determination of silver in some surface soil samples

-1 a
Serial no. Silver / mg kg ± s Sample sources
(n=5)
b
S1 41.8±1.0 Jewellary soil
S2 104.2±1.2 Silver Industry soil
S3 105.8±1.5 Elite Paint soil
S4 58.9±1.0 Marine soil
S5 10.5±0.5 Agriculture soil (Chittagong University Campus)
a
The measure of precision is the standard deviation.
b
Composition of the soil samples: C, N, P, K, Na, Ca, Mg, Cu Fe, Pb, Zn, Mn, Mo, Co, NO 3, SO4 etc

An aliquot (1-2-mL) of this solution preconcentrated environmental water was pipetted into
a 10-mL calibrated flask and the silver content was determined as described under the
general procedure using EDTA or tartrate as a masking agent. The results of analyses of
environmental water samples from various sources for silver are given in Table 5.

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3.2.4 Determination of silver in biological samples

Regarding human blood (3-5 -mL) and urine (20-50 -mL) were collected in polyethane
bottles from the affected persons. The samples were taken into a 100-mL micro-Kjeldahl
flask and digested following the procedure [31]. A glass bead and 10 mL of concentrated
nitric acid were added and the flask was placed on the digester under gentle heating
following a method recommended by Stahr [32]. When the initial brisk reaction was over, the
solution was removed and cooled. 5 mL of concentrated HNO3 was added carefully,
followed by the addition of 0.5 mL of 70% HClO4, and heating was continued to dense
white fumes, repeating HNO3 addition if necessary. Heating was continued for at least 30
min; followed by cooling. The content of the flask was filtered and neutralized with dilute
ammonia. The resultant solution was then transferred quantitatively) into a 10-mL calibrated
flask and made upto the mark with de-ionized water.

An aliquot (1-2 -mL) of this digested biological sample was pipetted into a 10-mL calibrated
flask and the silver con4ent was determined as desc2i"ed under the general procedure
using EDTA and tartrate as a masking agents. The results of the biological sample analyses
by the spectrophotometric method were found to be in excellent agreement with those
obtained by ICP-MS. The results are given in Table 6.

3.2.5 Determination of silver in photographical samples

20 mL of photographical sample was transferred into a 50 mL flask to which 2 mL of H2O2

and 10 mL of concentrated HNO3 were added. The solution was heated on a hot plate and
evaporated to dryness. The residue was dissolved with 10 mL 5% HNO3. The resulting
solution was then neutralized with NH4OH and filtered and quantitatively transferred into a
25-mL calibrated flask and made up to the mark with de-ionized water [33].

An aliquot (1-2 -mL) of this digested photographical sample was pipetted into a 10-mL
calibrated flask and the silver content was determined as described under the general
procedure using EDTA or tartrate as a masking agent. The results of analyses of
photographical samples for silver are given in Table 7.

3.2.6 Determination of silver in soil samples

An air-dried homogenized soil sample (100g) was accurately weighed and placed in a 100-
mL micro-Kjeldahl flask following the method recommended by Ahmed et al [29]. The
sample was digested in the presence of an oxidizing agent following a method
recommended by Jackson [34]. The content of flask was filtrated through Whatman No. 40
filter paper into a 25-mL calibrated flask, and neutralized with dilute ammonia in the
presence of 1-2-mL of a 0.01% (w/v) EDTA solution. It was then diluted up to the mark with
deionized water.

Suitable aliquots (1-2-mL) were transferred into a 10-mL calibrated flask and the silver
content was determined as described under general procedure using fluoride or thiocyanide
solution as a masking agent and quantified from a calibration graph prepared concurrently.
The results are shown in Table 8.

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4. CONCLUSION

In the present work, a simple, sensitive, selective and inexpensive micellar method with
the Ag-dithizone complex was developed for the determination of silver in industrial,
environmental, photographical, biological and soil samples. The presence of micellar
system (altered environment) avoids the previous steps of solvent extraction and reduces
the cost and toxicity while enhancing the selectivity, sensitivity and molar absorptivity. The
average molar absorptivity of the Ag-dithizone complex formed in the presence of the
5 -1 -1
anionic SDS surfactants is almost the ten-times 1.6 x 10 L. mol. cm the value obtained in
4 -1 -1
the standard method (1.0 x 10 L. mol. cm ); the maxima of absorption is shifted by
about 15 nm when compared with standard method, resulting in an increase in the
sensitivity of the method. With suitable masking, the reaction can be made highly selective.
Although many sophisticated techniques, such as pulse polarography, HPLC, NAA, AAS
and ICP- MS, are available for the determination of Ag at trace levels in numerous complex
materials, factors such as the low cost of the instrument, easy handling, portable, lack of
any requirement for consumables, and almost no maintenance, have caused
spectrophotometry to maintain a popular technique, particularly in the laboratories of
developing countries with limited budgets. The sensitivity in terms of molar absorptivity
(  =1.6 x 10 L. mol. cm ) and precision in terms of relative standard deviation of the
5 -1 -1
-1
present method are very reliable for the determination of Ag in real samples down to (ng g
levels in an aqueous medium at room temperature (25±5ºC).

ACKNOWLEDGEMENTS

We are thankful to the authorities of Chittagong Medical College Hospital for supplying
biological samples. We are also thankful to the authority of BCSIR Laboratories, Dhaka for
analyzing biological samples by ICP-MS.

COMPETING INTERESTS

Authors have declared that no competing interests exits.

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