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Determination of trace amounts of palladium by

solution scanometric method

Ardeshir Shokrollahi & Kowsar Ramdar

To cite this article: Ardeshir Shokrollahi & Kowsar Ramdar (2017) Determination of trace amounts
of palladium by solution scanometric method, Journal of Taibah University for Science, 11:5,
782-787, DOI: 10.1016/j.jtusci.2016.12.001

To link to this article: https://doi.org/10.1016/j.jtusci.2016.12.001

© 2017 The Authors

Published online: 16 Apr 2018.

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Journal of Taibah University for Science 11 (2017) 782–787

Full Length Article

Determination of trace amounts of palladium by solution

scanometric method
Ardeshir Shokrollahi ∗ , Kowsar Ramdar
Department of Chemistry, Yasouj University, Yasouj, 75918-74831, Iran
Received 12 May 2016; received in revised form 26 October 2016; accepted 19 December 2016
Available online 16 January 2017

Abstract
In this study, solution scanometry is presented as a highly sensitive, simple and rapid method for the colorimetric determination
of palladium ion in water samples and walnut leaf. The method is based on the formation of a rose-brown complex between Pd2+
ion and an excess of iodide in acidic medium in Plexiglas cells, which are scanned by conventional flatbed-scanner, and the colour
of each cell is analysed by software written in Visual Basic (VB 6) media to determine red, green and blue values. The relative
standard deviation and linear range of the method were determined to be 1.0% and 0.1–72.0 ␮g mL−1 , respectively. The proposed
method was successfully applied for the determination of Pd2+ ion in water samples and walnut leaf.
© 2017 The Authors. Production and hosting by Elsevier B.V. on behalf of Taibah University. This is an open access article under
the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
®
Keywords: Palladium; Solution scanometric method; Plexiglas cell

1. Introduction the chemical industry has led to increasing concentra-

Palladium is an economically important metal of eco-
nomic importance due to its increasing applications in
the production of dental and medicinal devices and jew-
ellery [1,2]. Palladium is also used for the purification of
hydrogen gas [2] and in the electrical industry as contacts
in telephone relays [3]. In recent years, the extensive use
of palladium in automotive catalytic converters and in
∗ Corresponding author. Tel.: +9874 33223048. Fax: +98743
3242167.
E-mail address: ashokrollahi@mail.yu.ac.ir (A. Shokrollahi).
Peer review under responsibility of Taibah University.
tions of this metal in the environment [4]. It is a metal
with low toxicity but may still have deleterious effects on
the health of the general population [5], such as causing
asthma, allergy and other serious health problems [6,7].
Pd2+ ion shows a high ability to form complexes and
react with reagents of practically all types [8].
Many methods are known for the determina-
tion of palladium, such as spectrophotometry [9],
atomic absorption spectrometry [3], inductively coupled
plasma-mass spectrometry [10] and inductively coupled
plasma-optical emission spectrometry [11].
The flatbed scanner was used for the first time by
Suslik et al. in the development of a colorimetric sen-
sor array for the detection and identification of volatile
organic compounds [12,13]. It was then used to scan the
TLC (Thin Layer Chromatography) strip in the paptode
method. TLC acts as a substrate for the reaction between

http://dx.doi.org/10.1016/j.jtusci.2016.12.001
1658-3655 © 2017 The Authors. Production and hosting by Elsevier B.V. on behalf of Taibah University. This is an open access article under the
CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
 A. Shokrollahi, K. Ramdar / Journal of Taibah University for Science 11 (2017) 782–787
an analyte and a reagent [14]. The solution scanometric
method was introduced recently by Abbaspour et al. [15].
In this method, the reaction is performed in a solution in
®
Plexiglas cells. The solution is scanned, and finally, the
RGB (red, green and blue) colour model is used in colour
monitoring [16–18]. This method has been used for the
detection and determination of metal ions [19,20].
The solution scanometric method has the advantages
of being easy to handle and having the capability to test
various compounds simultaneously, with a high scanning
speed, a quick response and limited interferences. More-
over, it is inexpensive, has portable systems and, unlike
spectrometry, eliminates the need to find ␭max. Finally,
this method in comparison to other scanning methods
such as paptode, can produce more clear, symmetrical
and homogenous images.
In this work, solution scanometry was developed as
a simple, fast and inexpensive method to determine
Pd2+ ion based on the formation of a coloured complex
between Pd2+ ion and iodide in acidic medium and in
the presence of sodium sulphite as a reducing agent for
iodine.
2. Experimental
2.1. Apparatus
The cells used were built from sheets of Plexi-
glas, according to the previous report [15]. A flatbed
CanoScan LIDE 200 with a 3-colour (RGB) LED (cold
cathode fluorescent lamp (CCFL)) and charge-coupled
device (CCD) as the light source and detection system,
respectively, was used for scanning. The horizontal and
vertical resolution of the scanner were both set at 300 dpi.
The colour of each cell was analysed with software writ-
ten in Visual Basic 6 (VB 6) media to determine the red,
green and blue values. Three Biohit Proline pipettes with
different volumes (0.5–10, 10–100 and 100–1000 ␮L)
were used for injecting samples into the cells.
2.2. Chemicals and reagents
All chemicals used in this work were of analyti-
cal grade. In addition, double distilled water was used
throughout. Palladium chloride and potassium iodide
were purchased from Merck Company (E. Merck,
Darmstadt, Germany). A laboratory stock solution
(100 ␮g mL−1 ) was made by dissolving 0.0416 g pal-
ladium chloride in hydrochloric acid and diluting to
250 mL in a volumetric flask. The analytical-grade
783
sodium sulphite used in this study was obtained from
Fluka Company (Fluka, Buchs, Switzerland).
2.3. Principles of the red, green and blue (RGB)
colour systems
The RGB colour model is an additive colour model.
In this model, a colour is described by specifying the
intensity levels of the colours red, green, and blue. The
typical range of intensity values for each colour is 0–255,
which gives 16,777,216 different colours. In the RGB
system, any colour is represented in the form of (R, G,
B), such that black is represented by the RGB value ‘0
0 0’ (R = 0, G = 0 and B = 0), while white is represented
by the RGB value ‘255 255 255’ (R = 255 G = 255 and
B = 255). The values of all three colours are converted to
a single integer value using this formula:
V = R + 256G + 2562 B
where R, G and B are the red, green and blue values of
the main colour, and V is the basis of the RGB system
and is defined this way to identify a specific number for
each colour. For black and white, V is equal to 0 and 16
777 216, respectively. The flowchart, R, G and B values
of V for any colour can be extracted as described in the
literature [15].
It should also be mentioned that the R, G or B colour
value that has the same colour as the solution is usually
useless, as this value is often higher than 180 and does
not change significantly during the experiment. In this
experiment, two values of the RGB system (green and
blue) changed in different concentrations of the complex,
and therefore the one with the highest change, that is,
 B , was chosen.
2.4. Procedure
First, 125 ␮l of 100 ␮g ml−1 palladium solution,
100 ␮l of 6 mol L−1 hydrochloric acid, 125 ␮l of
4 mol L−1 iodide and 50 ␮l of 0.02 mol L−1 sodium sul-
phite as an reducing agent for iodine were transferred
into each cell, and an appropriate volume of double dis-
tilled water was added for a total volume of 500 ␮L in
each cell. A cell containing the desired volume of acid,
the colour-forming reagent solution and sodium sulphite
without any palladium (total volume of 500 ␮L) was set
as the blank. The cells were shaken to obtain a homoge-
nous colour, and the Plexiglas sheet was scanned with the
scanner. The image was transferred into the computer,
and any colour changes in each cell were analysed using
a program written in VB 6 media.
784 A. Shokrollahi, K. Ramdar / Journal of Taibah University for Science 11 (2017) 782–787
In this program, the colour of each cell is analysed
based on the RGB system to obtain R, G and B val-
ues. In the colour analysis program, a specific area for
analysis containing approximately 10000–300000 pix-
els was selected. The noise could thereby be vividly
decreased. The effective intensity for any colour value
was calculated as follows:
Ax = −log(Cs /Cb )
where Ax is the effective intensity for red, green or blue.
Cs and Cb are the red, green or blue colour values of a
sample and the blank, respectively.
2.5. Preparation of real samples
2.5.1. Water samples
First, 2 mL of 1 mol L−1 HNO3 was added to water
samples, which were used after 1 hour. The standard
addition method was applied to determine Pd2+ ion in
the water samples according to the procedure given in
the general procedure section. The Pd2+ ion in these
samples was also determined by atomic absorption spec-
troscopy (AAS). The conditions for determination of
Pd2+ by AAS were as follows: wavelength, 244.8 nm;
slit, 0.2 nm; flame; C2 H2 –Air, using a hollow cathode
lamp was used.
2.5.2. Walnut leaf
The walnut leaf sample was dried for 48 h at 70 ◦ C in
an electric oven, and 4.0000 g of dry sample was subse-
quently kept in a furnace for 1 h at 550 ◦ C until it ashed.
The ash was digested with 4 mol L−1 HNO3 and heated
on a hotplate. After dissolution, the contents were filtered
by filter paper and diluted to a final volume of 50 mL with
double distilled water. Finally, 200 ␮l of the resulting
solution was analysed according to the described proce-
dure. The Pd2+ ion was also determined in this sample
by atomic absorption spectroscopy (AAS).
3. Results and Discussion
In the reaction of Pd2+ ion with iodide, the precip-
itate of palladium iodide has been produced. However,
if a large iodide excess is added, the palladium iodide
precipitate dissolves because of the formation of a solu-
ble PdI4 2− complex with rose-brown colour, according
to the following reaction:
PdI2 + 2I− ↔ PdI4 2− (rose-browncolour)
The B parameter of the picture of this colour has a
good effective intensity. Accordingly, the determination
Fig. 1. Effect of time on effective intensity (Conditions: 500 ␮L solu-
tion containing 25 ␮g mL−1 Pd2+ ion, 1 mol L−1 iodide, 1.32 mol L−1
HCl and 2 × 10−3 mol L−1 sodium sulphite).
of Pd2+ ion in this research is based on the change in this
parameter.
3.1. Optimization of the system parameters
To obtain the maximum effective intensity of B as
a signal, it was necessary to investigate the effects of
reaction time, type and the concentration of reagents.
3.1.1. Effect of time
To attain the maximum signal, it was necessary for
the interaction between reagents to be completed. The
effect of the reaction time was studied in the range of
5–55 min. To examine the effect of reaction time on the
determination of palladium, A cell containing 500 ␮l of a
solution consisting of 25 ␮g ml−1 palladium, 1 mol L−1
iodide, 1.32 mol L−1 HCl and 2 × 10−3 mol L−1 sodium
sulphite was scanned at 5 minute increments at room
temperature, and after scanning of the sheet, the image
of the cell was analysed using the software. The results,
shown in Fig. 1, illustrate that the effective intensity is
maximum at an analysis time of 20 minutes.
3.1.2. Effect of iodide, sulphite and acid
concentrations
Fig. 2 illustrates the effect of iodide and sodium sul-
phite concentration as well as the effects of HCl and
H2 SO4 and their concentrations. The effective intensity
B increased with the addition of iodide and decreased
from the concentration of 1 mol L−1 onwards, at which
concentration the interaction between iodide and Pd2+
ion was complete. Therefore, 1 mol L−1 of iodide was
selected as the optimum concentration.
Because acid iodide solution slowly liberates iodine
on standing, a quantity of sodium sulphite was added to
the solution to reduce the iodine [21]. Optimization of
 A. Shokrollahi, K. Ramdar / Journal of Taibah University for Science 11 (2017) 782–787 785

Fig. 3. Calibration curve for determination of Pd2+ ion under optimum

Fig. 2. Effect of iodide and sodium sulphite concentration as well conditions.
as the effect of HCl and H2 SO4 and their concentration on effec-
Table 1
tive intensity (Conditions: 500 ␮L solution containing 25 ␮g mL−1
Effect of interfering species on the determination of 25 ␮g ml−1 Pd2+
Pd2+ ion, 1 mol L−1 iodide, 1.32 mol L−1 HCl, 0.42 mol L−1 H2 SO4 ,
under optimum conditions.
2 × 10−3 mol L−1 sodium sulphite; reaction time 20 min). For the other
two parameters, the investigated parameter was changed, and the others Interfering species Added as Tolerance Conc.
were fixed similarly. (␮g mL−1 )

Ca2+ , Ba2+ , Cu2+ Nitrate salt 5000

the concentration of sodium sulphite is one of the key ClO4 − , SO4 2− Sodium or 5000
optimization steps. According to observations without Potassium salt
sodium sulphite in the reaction medium, the false blue Ni2+ , Na+ Nitrate salt 2500
Hg2+ Chloride salt 2500
signal attributed to the released iodine was increased.
Cl− Potassium salt 2500
The highest signal was obtained at 2 × 10−3 mol L−1 Al3+ , K+ Nitrate salt 1000
of sodium sulphite. Thus, to provide sufficient sodium Br− Potassium salt 1000
sulphite, this amount was selected as the optimum con- Cr3+ , Cd2+ , Co2+ , Nitrate salt 500
centration. Mg2+ , Pb2+
Fe3+ , Ag+ Nitrate salt 25
The effect of HCl and H2 SO4 and their concentra-
tions on the formation of complex of Pd2+ ion with
iodide was also examined. As shown in Fig. 2, at
0.42 mol L−1 H2 SO4 and 1.32 mol L−1 HCl, the max- the RSD% (Relative Standard Deviation) for the B
imum colour intensity was observed. Because the colour value. The detection limit was found to be
effective intensity of the B parameter in the presence of 0.089 ␮g mL−1 based on the standard deviation of six
HCl acid at the optimum concentration is greater than for blanks.
H2 SO4 , HCl was accordingly used in subsequent studies.
In previous reports, because of obtaining higher sensitiv- 3.3. Interference study
ity and lower interference in the matrix, different acids
have been used for the measurement of palladium with To study the selectivity of the proposed method for
iodide reagent [21–23]. the determination of Pd2+ ion, the effect of various
ions on the determination of 25 ␮g ml−1 Pd2+ ion was
3.2. Analytical performance tested under optimum conditions. The tolerance limit
was defined as the concentration of added ion that causes
Fig. 3 illustrates the calibration curve under opti- less than ±5% relative error of the B value. The results
mum conditions. In the range of 0.1–72.0 ␮g mL−1 , are shown in Table 1. In this method, most of the species
a proper linear relationship was obtained between the do not interfere, because the scanometry is based on the
effective intensity of the product and the concentra- reflective properties of the samples.
tion of Pd2+ ion. The equation for the regression line
was Y = 0.0084C + 0.0234 (for B), where C is the con- 3.4. Application
centration of Pd2+ ion in ␮g mL−1 . To determine
the repeatability of the method, 5 sample solutions The applicability of the proposed method in determin-
of 25 ␮g mL−1 Pd2+ ion were analysed, and 1.0 was ing Pd2+ ion was examined with walnut leaf and three
786 A. Shokrollahi, K. Ramdar / Journal of Taibah University for Science 11 (2017) 782–787

Table 2
Determination of Pd2+ ion in real samples.
sample Solution scanometric method AAS

Regression equation R2 Added Found Recovery % Found

(␮g mL−1 ) (␮g mL−1 ) (␮g mL−1 )

Tap water (Yasouj city) A = 0.0069X − 0.0007 0.9915 00.00 Nd – Nd

20.00 19.48 97.38 –
32.00 31.97 99.90 –
Spring water (Ghalat A = 0.0062X + 0.0003 0.9988 00.00 Nd – Nd
village in Yasouj city)
20.00 19.73 98.63 –
32.00 31.48 98.36 –
River water (Beshar, A = 0.0051X − 0.0043 0.9934 00.00 Nd – Nd
Yasouj city)
20.00 19.91 99.53 –
32.00 32.10 100.30 –
Walnut leaf A = 0.0062X + 0.0039 0.9927 00.00 Nd – Nd
20.00 19.79 98.95 –
32.00 31.71 99.10 –

Table 3
Comparison of the results of solution scanometry and other methods for determination of Pd2+ ion.
Method Reagent Linear range (␮g mL−1 ) LOD (␮g mL−1 ) RSD% Ref

Spectrophotometry Bromide 40.0–200.0 ---- ---- [24]

Spectrophotometry Azide 1.3–4.6 0.03 ---- [25]
Spectrophotometry Promazine hydrochloride 2.0–17.0 ---- ---- [8]
Spectrophotometry Cefixime 0.75–16.50 0.07 ---- [26]
Solution scanometry Iodide 0.1–72.0 0.089 1.0 This work

different water samples, including tap (Yasouj city), Acknowledgement

river (Beshar in Yasouj city) and spring (Ghallat village
in Yasouj city) water, under optimum conditions. The We gratefully acknowledge the support of Yasouj
results are presented in Table 2. The results obtained University Research for this study.
by the proposed method were found to be in excellent
agreement with the results obtained by atomic absorption
spectrometry (AAS). References

4. Conclusions
Trace amounts of Pd2+ ion were determined using
solution scanometry as a new, simple, fast and inex-
pensive method. Table 3 compares the characteristics of
the proposed method with some other previous reported
methods for the determination of Pd2+ ion. As shown
in Table 3, the method has a wide linear range, good
precision and an acceptable limit of detection in com-
parison to the other methods. In addition, the method
has other advantages, such as simplicity of operation,
rapidity and low cost. The proposed method can be suc-
cessfully applied to determine trace amounts of Pd2+ ion
in real samples.
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