Determination of platinum and palladium in
environmental materials by inductively coupled plasma atomic emission spectrometric after
sorption on amberlite XAD-4 loaded with diphenylthiourea
Fan Zhefeng
(Center of Analysis and Testing, Shanxi Normal University, Linfen, Shanxi, 041004, China)
Abstract A solid phase extraction system for
separation and preconcentration of platinum and palladium in environmental materials is
proposed, It is based on the adsorption of platinum(IV) and palladium (II) as ion
associates of their chlorocomplexes onto an Amberlite XAD-4 resin loaded with
diphenylthiourea (DPTU) reagent. The parameters such as the effect of acidity on the
platinum and palladium extraction, the effect of flow rate and sample volume on the
extraction, the sorption capacity of the loaded resin, the platinum and palladium
desorption from the resin and the analytical characteristics of the procedure were
studied. The results demonstrate that palladium and platinum in the concentration range
10-500 ng ml-1, and 5 mol L-1 HCl contained in a sample volume of
25-100 ml, can be extracted by using 0.5 g Amberlite XAD-4 resin loaded with
diphenylthiourea (DPTU) reagent. The adsorbed platinum and palladium were eluted from the
resin by using 5 ml 0.4 mol L-1 thiourea in 1 mol L-1 HCl. The
extractor system has a sorption capacity of 1.59 mmol for platinum and 1.81 mmol for
palladium per g of Amberlite XAD-4 resin loaded with diphenylthiourea (DPTU). The
precision of the method, evaluated as the RSD obtained after analyzing a series of seven
replicates, was 2.5% for platinum, 3.6 % for palladium in a concentration of 25 ng ml-1.
Detection limits were 12 ng g-1 for palladium and 18 ng g-1 for
platinum. The proposed procedure was used for platinum and palladium in environmental
materials using an inductively coupled plasma atomic emission spectroscopy technique
(ICP-AES).
Keyword¡¡
1. INTRODUCTION
The determination of trace concentration of platinum and palladium in environmental
and biological samples has gained a considerable importance because of their toxicity and
increasing occurrence, which is mainly due to industrial and automobile catalysts [1-5].
The wide variety of environmental matrices and the ultra trace concentration of these
metals in them require reliable and efficient analytical methods. Inductively coupled
plasma atomic emission spectrometry [6,7] (ICP-AES), inductively coupled plasma
mass spectrometry [8,9](ICP-MS), electrothermal atomic absorption spectrometry [10]
(ETAAS) and neutron activation analysis [11] (NAA) are the most sensitive
techniques and find the wider application. However, the direct analysis of platinum and
palladium by these techniques are considerably restricted owing to interference caused by
matrix elements, especially in the case of environmental materials. The separation and
preconcentration steps prior to the final detection are necessary.
Many separation methods such as ion-exchang[12-15,23],
sorbent extraction [7,16,17], extraction with dithizone [18],
activated charcoal [19] and modified silica gel [20] have been
proposed. The interest of analysts has been focused on the wider application of various
sorbents and complexes for the effective separation and preconcentration of these metals.
Enhancement of selectivity may be achieved owing to differences in the tendency of
individual metals to form complexes in various media. An on-line sorbet extraction
preconcentration system has been developed for the determination of platinum and rhodium
by ETAAS and ICP-AES after accumulation of their bis(carboxymethyl)dithiocarbamate (CMDTC)
chelate on a micro-column packed with Amberlite XAD-4 resin [7]. Methods of
separation of the platinum metal based on liquid chromatography after their extraction in
the form of chelate with 1-(2-pyridylazo)-2-naphthol (PAN) have been presented [16,17].
The separation and determination of Pt, Os, Ir, Ru, Co, Ni with
2-(6-methyl-2-benzothiazolylazo) -5-diethylaminophenol (MBTAE) has been described [21].
Separation of Pt, Pd and Ru quinolin-8-olates on silasorb-600 with choroformpropan-2-o1
(98+2) has been examined [22].
This paper proposes an analytical procedure for the preconcentration
and determination of platinum and palladium in environmental materials using inductively
coupled plasma atomic emission spectrometry, after chelation onto a column containing
Amberlite XAD-4 resin loaded with diphenylthiourea (DPTU).
2.EXPERIMENTAL
2.1 Apparatus
Measurements were performed using Atomic Scan 25 inductively coupled plasma atomic
emission spectrometry (Thermo Jarrell-Ash, USA). Parameters of instrument and operating
conditions are presented below. The ICP source was a generator with frequency 27.12 MHz
operated at a power input of 1.2 kW. Gas flows (Ar) were adjusted to the following values:
plasma 15.0 l min-1, auxiliary 0.5 l min-1, carrier 0.8 l min-1.
The V-groove nebulizer was fed by a peristaltic pump (1.2 ml min-1),
integration time was 15 s and each result was the average of three measurements, the
spectral lines (nm) were used: pt II 214.432; pd II 340.458. A peristaltic pump IFIS-C (Xian Remax Electronic
Science-Tech Co. Ltd, China) was used for preconcentration. A microwave device MDS 2000
(CEM, USA) was used for sample preparation.
2.2 Reagents
All reagents were of super-pure grade chemical unless otherwise stated. The standard
stock solution containing 500 mg ml-1 of Pt and Pd in 20% HCl. Double distilled
water was used for the preparation of solutions. Diluted Pt and Pd solutions, ranging from
10-500 ng ml-1, containing interfering elements were freshly prepared in a
mixture of 5 M HCl + 0.2 M HNO3 from stock standard solutions. The thiourea
elute (0.4 mol L-1) solution was freshly made up by dissolving 1.52 g of
thiourea in 1 mol L-1 HCl in a volume 50 ml. The DPTU solution (0.10%) was
prepared by dissolving 0.25 g DPTU in 250 ml ethanol.
2.3 Preparation of the Amberlite XAD-4 Column loaded with DPTU ¡¡
Amberlite XAD-4 was treated with an ethanol-hydrochloric
acid-water (2:2:1 ) solution over night. ter, the resin was rinsed with distilled water
until it was neutral, being dried in an oven at a temperature of 110ºC
for 3h.
The packing of the column must be done using ethanol as elute because
with water the grains of resin float. The resin is satuted with the reagent by sorption of
15 ml of a 0.10 % DPTU solution in ethanol at a flow rate of 0.2 ml min-1.
Later it is rinsed with distilled water until the complete elimination of excess reagent
occurs. All experiments were done in glass column with a 0.5 cm i.d. and length of 5.0 cm
containing 0.5 g Amberlite XAD-4. Before the sample sorption, the column must be
preconditioned by passing a 10 ml of 5 mol L-1 HCl + 0.2 mol L-1 HNO3
at flow rate 2.0 ml min-1.
2.4 Procedure for the sorption of Pt and Pd on the AmberliteXAD-4 ¡¡
¡¡¡¡¡¡¡¡¡¡
The mixed standard solutions of Pt and Pd are pipeted into
beaker, the final volume was made up with 5 mol-1 HCl +0.2 mol L-1
HNO3 solution. This solution must be passed through the column at a flow rate
of 2.0 ml min-1. After passing this solution the column was rinsed with 10ml of
5 M HCl +0.2 M HNO3. The adsorbed Pt and Pd on the column was eluted with 5 ml
of 0.4 mol L-1 thiourea in 1 mol L-1 HCl at a flow rate of 0.50 ml
min-1. The elute solution was collected in a 5 ml volumetric flask and the Pt
and Pd determined by the ICP-AES.
2.5 Samples preparation
3 g of the samples were leached in a microwave device with 25 ml of HNO3+HCl+
HF (3:1:1). The blank solutions characterizing the whole procedure were prepared in the
same way. After cooling, sample were filtered and transferred into 100 ml volumetric
flasks. The final volumes were made up with 5 mol L-1 HCl +0.2 mol L-1
HNO3.
Fig.1 Effect of acidity on the Pt and Pd sorption on the
Amberlite XAD-4 column
3.RESULTS AND DISCUSSION
3.1 effect of acidity on adsorption ¡¡
The mixed stock standard solutions containing 25 ng ml-1of
Pt and Pd are concentrated by means of the column procedure described. The results
demonstrated that it is maximum and quantitative in the acidity rang 4-6 mol L-1
HCl (recoveries >95%) and that the recoveries of both elements are >97% at 5 mol L-1
HCl, as can be seen in Fig. 1. In order to determine these elements simultaneously, 5 mol
L-1 HCl is selected.
3.2 Effect of flow rate and sample volume
The effect of flow rate on Pt and Pd retention was examined by varying the flow rate
from 0.5 to 5.0 ml min-1under optimum conditions. The results demonstrated that
the retention of Pt and Pd on the resin is quantitative (>95%) and for a flow rate
lower than 2.0 ml min-1. The effect of the sample volume on the Pt and Pd
extraction was investigated by passing 25, 50, 100, 200 and 250 ml through the column at a
constant flow-rate of 2.0 ml min-1. The recovery obtained was higher than 95%
in the sample volume than 100 ml.
3.3 Influence of desorption acidity
In order to determine the Pt and Pd desorption from resin, 5.0 ml of 1-3 mol L-1
HCl +0.4 mol l-1thiourea were tested. The results demonstrated that the
desertion is acceptable (>95%)
for solutions with 1 mol l-1 HCl +0.4 mol l-1 thiourea solutions. In
this procedure a concentration of 1 mol l-1 HCl +0.4 mol l-1
thiourea is recommended.
3.4 Effect of desorption flow rate ¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡
When the column procedure is used, the influence of the flow
rate on desorption of the analytes from the column with 5 ml of 1 mol l-1 HCl
+0.4 mol l-1 thiourea is investigated. The results show that desorption
recoveries of Pt and Pd are >97% for a flow rate of 0.5 ml min-1. A 0.5 ml
min-1 flow rate is selected for the elute flow rate.
3.5 Sorption capacity
The sorption capacity of the Amberlite XAD-4 resin loaded with DPTU for the extraction
of Pt and Pd was also determined. Increasing amounts of Pt and Pd were added to a column
containing 0.5g of loaded resin. The adsorption capacity of the resin is calculated and is
found to be 1.56 mmol g-1 for Pt and 1.81 mmol g-1 for Pd.
3.6 Interference of other ions¡¡¡¡¡¡¡¡¡¡¡¡¡¡
Different potential interfering ions are added to dilute
analytes standards (25 ng ml-1 each of Pt and Pd). The analytes are
preconcentrated and determined as described above. The tolerance limits of various
concomitant ions are determined, when a relative error of ¡À5%
is used as the criterion the following ions have no effect: 1000-fold of by weight Ca(II), Mg(II), Cu(II),
Zn(II), Fe(II) and Al(III); 500-fold Mn(II), Ni(II),
Cd(II) and Bi(III); 10-fold Pb(II). The results show that these various concomitant precious and
heavy metals do not have the interference.
3.8 Application
The proposed procedure can be applied to the preconcentration and separation of Pt and
Pd, in the concentration range, contained in a solution volume of 100 ml by using of 0.5 g
Amberlite XAD-4 resin loaded with DPTU reagent. The precision of the method, evaluated by
the RSD obtained after analyzing a series of seven replicates was 2.5% for Pt and 3.6% for
Pd in a concentration of 25 ng ml-1. The limits of detection (LOD) calculated
as 3s is 12 ng g-1
for Pd and 18 ng g-1 for Pt. The method proposed was applied for Pt and Pd
determination in environmental materials. The standard addition technique was applied and
the recoveries obtained revealed that the proposed procedure has good accuracy. The
results are described in Table 1.
Table.1 Determination and recovery of Pt and Pd in
environmental samples (n=3)
Sample |
Initial (ng g-1) |
Added (ng ) |
Founda (ng g-1) |
Recovery (%) |
Pt |
Pd |
Pt |
Pd |
Pt |
Pd |
Pt |
Pd |
A-1 |
189¡À12 |
64¡À3 |
50.0 |
20.0 |
237¡À8 |
85¡À5 |
96 |
105 |
A-2 |
171¡À16 |
72¡À5 |
50.0 |
20.0 |
223¡À11 |
91¡À3 |
104 |
95 |
B-1 |
89¡À3 |
68¡À2 |
50.0 |
20.0 |
138¡À5 |
88¡À3 |
98 |
100 |
B-2 |
93¡À5 |
79¡À3 |
50.0 |
20.0 |
141¡À4 |
98¡À2 |
96 |
95 |
a At 95% confidence level.
4.CONCLUSIONS
The determination of Pt and Pd in environmental samples by 1CP-AES is possible after
on-line sorption using XAD-4 with DPTU and thiourea as an eluting agent. Mean recovery for
both metals amounts to 98%. The standard addition technique was used and the recoveries
obtained revealed that the proposed procedures show good accuracy.
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