Arab Journal of Nuclear Science and Applications, 47(1), (53-60) 2014

Separation and Purification of Palladium from Aqueous Solution by Thiol

Derivatives
H. G. Nowier
Hot Laboratories Centre, Atomic Energy Authority, 13759, Egypt
Received: 26/12/2013

Accepted: 15 /1/2014
ABSTRACT

The extraction of palladium from aqueous nitrate solution was studied with
solvents containing 3,4 dithio toluene (H2TDT), bis(2,4,4-trimethylpentyl)
phosphinic acid-monothio (CYANEX 302) and dithio (CYNAEX 301) analogues.
The effect of different parameters affecting the extraction of palladium was
investigated. Comparative data are presented to illustrate the effect of composition
(sulphur substitution) on the extraction and stripping characteristics of the three
reagents. The selectivity range of the studied extractants was found to be in the
order H2TDT > CYNAEX 301 > CYNAEX 302. The extraction of the Pd(II)
complexes with respect to
metal-thiol complexes has also been studied.
Experimental data relating to palladium have been analysed numerically to
determine the stoichiometry of the extracted species and its equilibrium constant. It
was found that Pd(II) was extracted into the organic phase by the formation of the
species RS-Pd(II).
Key words: Toluene-3,4-dithiol (H2TDT), CYNAEX301, CYNAEX302, Extraction,
stripping, stage and equilibrium.
INTRODUCTION
Due to their excellent physical and chemical properties, precious metals (PMG) have found new
applications outside jewelry and decorative industries, and there is a growing demand for their
recovery from primary and secondary resources. Intensive research has been done to develop solvent
extraction techniques replacing the tedious conventional routes for PMG recovery(1). Bina Gupta and
Indu Singh (2) explored the extraction behavior of platinum(IV), rhodium(III) and palladium(II) from
HCl, H2SO4 and HNO3 (0.106.0 mol L 1) media by toluene solution of Cyanex 923. Optimization of
the conditions for binary separations of certain associated metals namely gold, silver, iron, nickel,
cobalt, chromium, copper and aluminum has been carried out.
R. Ruhelaa et al. (3) evaluated the extraction properties of N,N,N',N'-tetra-(2-ethylhexyl)
dithiodiglycolamide (DTDGA) for separation and recovery of palladium from simulated high-level
liquid waste (SHLW) solution, and found that the extraction of Pd increases with the increase in nitric
acid concentration up to 4.0 M, above which the extraction remains almost constant. Acid uptake
studies show 1:1 stoichiometry between DTDGA and HNO3 at nitric acid concentration above 3.0 M.
Ana Paula Paivad et al (4). carried out a quantitative recovery of Pd(II) from 1 to 8 M HCl solutions
using liquid-liquid extraction by Thiodiglycolamide derivative ; N,N'-dimethyl-N,N'dicyclohexylthiodiglycol amide (DMDCHTDGA) in 1,2-dichloroethane (1,2-DCE). Chun-Yang Yin
et al. (5) conducted a microfluidic solvent extraction (SX) of platinum and palladium from chloride
leach solution of spent automotive catalysts using Alamine 336. In their study, a fast kinetic platinum
and palladium extraction (>99%) occurred at SX contact time as fast as 1.0 second with subsequent
marginal extraction efficiency increase for longer contact times with comparable extraction
performance to that of bulk SX. Machhindra et al. (6) studied the selective separation of low Pd (II)
concentrations from binary mixtures containing iron (III), cobalt(II), nickel(II), and copper(II) in
hydrochloric acid medium using 4-(4-methoxybenzylideneimino)-5-methyl-4H-1,2,4-triazole-3-

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Arab Journal of Nuclear Science and Applications, 47(1), (53-60) 2014

thiol(MBIMTT) dissolved in chloroform as extractant, and it was found that the time required for the
equilibrium is very short (30 seconds). Atefeh Najafi et al. (7) investigated the effect of diluents MIPS and chloroform -on the solvent extraction of palladium from chloride media by DC18-Crown-6
(dicyclohexyl-18-crown-6 ether) as the effective extractant. They found that using chloroform as
diluent is more suitable than MIPS for this extraction system in presence of KCl. James Cookson (8)
reviewed the chemical and electrochemical preparation of Pd nanoparticles using thiol derivatives for
their applications in catalytic processes. L. Pan et al. (9) investigated the solvent extraction
performances of Pd(II) and its separation behaviors from Pt(IV) using a synthetic sulfoxide MSO as
extractant from hydrochloric acid media. Cieszynska, Anna and Wisniewski Maciej (10) studied the
extractive recovery of Palladium (II) from hydrochloric acid solutions with CyphosIL 104. It was
found that the extractant was fast and very efficient at low acid concentrations and the extraction
mechanism is ion exchange mechanism. Ahmed, I.M., et al.(11) studied the extraction of Pd(II) with
triisobutylphosphine sulfide (CYANEX 471X) in kerosene from nitric acid medium. The
stoichiometry of the extracted species has been determined, and the feasibility of Pd(II) separation
from interfering transition metal ions has been evaluated in hydrochloric and sulphuric acid media as
well. Kamal Nayan Sharma et al. (12) synthesis and investigate palladium (II) complexes of
pyrazolated thio/selenoethers as single source precursors of Pd4Se and PdSe nano-particles and their
potential uses for catalyzing SuzukiMiyaura coupling. Palladium as a member of platinum group
metals (PGM), acts as a good catalyst and is widely used in hydrogenation / dehydrogenation
reactions, therefore it is useful in eliminating harmful emissions produced by internal combustion
engines and is extensively applied in automobile catalysts together with Pt and Rh where they convert
over 90 percent of hydrocarbons, carbon monoxide and oxides of nitrogen produced in the exhaust
from gasoline engines into carbon dioxide, nitrogen and water vapor (13-18).
In the present paper, three derivatives of thiol were used for the extraction of palladium form aqueous
nitrate solution. The different parameters affecting the extraction and stripping were investigated. The
extraction equilibrium of Pd extracted was evaluated and discussed.
EXPERIMENTAL
Materials:
All chemicals used were of analytical grade, Pd(NO3)2 was obtained from Merck. Sodium
sulphate and hydrochloric acid were BDH products. Sodium chloride, nitric acid and sulphuric acid
were obtained from Prolabo. Ammonium sulphate, sodium nitrate were obtained from Merck.
CYANEX 302.and CYANEX301 were kindly supplied by Cytec Inc. and used without further
purification. Odorless kerosene (non-aromatic) was obtained from Misr Petroleum company, Egypt.

Procedure:
The concentration of Pd(II), was determined using a Shimadzu UV/VIS double beam recording
spectrophotometer, Model 160-A, Japan. The concentration of Pd(II) was carried out by the formation
of dithizone complex followed by spectrophotometric determination of its maximum absorption at
max at 450 nm. Batch experiments were carried out by equilibrating equal volumes of 2.510-3M
toluene 3,4 dithiol (H2TDT), bis(2,4,4-trimethylpentyl) phosphinic acid (CYANEX 302) and
(CYNAEX 301) in kerosene, with 2.510-4 M Pd(II) in aqueous nitrate solution in stoppered glass
bottles using a thermostated shaking water bath adjusted at 25+.1oC. After equilibration and phase
separation, a suitable volume of the aqueous phase was subjected to spectrophotometric measurements
(19). The concentration of the metal in the organic phase was calculated from the difference between
its concentration in the aqueous phase before and after extraction. The distribution ratio D was

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Arab Journal of Nuclear Science and Applications, 47(1), (53-60) 2014

calculated as the ratio of the concentration of Pd(II) in the organic to the aqueous phase according to
the relation;
D = [(Co C) / C] . ( V/ V )
Where Co is the original metal concentration before extraction in the aqueous phase, C is the final
metal concentration after extraction, while V and V are the volumes of the aqueous and organic
phases, respectively.
RESULTS AND DISCUSSION
The different parameters affecting the extraction of Pd from nitric acid medium by H2TDT,
CYNAEX 301 and CYNAEX 302 were investigated by the batch technique. These include the effect
of shaking time, nitric acid, metal ion concentration, extractants concentration and phase ratio.
Effect of shaking time on the extraction of 3x10-5M Pd from 0.5M nitric acid using 2.5x10-3M of
H2TDT, CYNAEX 301 and CYNAEX 302 in kerosene is shown in Fig.1. The extraction of Pd
increased at first by increasing the shaking time. In the three cases the equilibrium was reached in one
step after 40 min.

100

Uptake, %

80

60

40

H2TDT
CYANEX301
CYANEX301

20

0
0

20

40

60

80

100

120

Time, min

Fig(1): Effect of shaking time on Palladium extraction from aqueous nitrate solution
Effect of nitric acid concentration (0.1-3.5M) on the extraction of 3x10-5M Pd using 2.5 x 10 -3 M of
H2TDT, CYNAEX 301 and CYNAEX 302 in kerosene, is shown in Fig 2. From this figure it is clear
that the extraction of Pd increases by increasing the nitric acid concentration reaching maximum at 3
M HNO3. Sole and Hiskey (20) suggested that the distribution coefficients shift to lower pH with
increasing sulfur substitution in thio-substituted organophosphinic acid extractants.

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Arab Journal of Nuclear Science and Applications, 47(1), (53-60) 2014

100

Uptake, %

80

60

40

H2TDT
20

CYANEX301
CYANEX302

0
0

Acid Conc, M

Fig.(2): Effect of Acid concentration on Palladium extraction

Effect of Pd concentration (0.5-4x10-4M) on its extraction by using 3x10-3 M of H2TDT, CYNAEX
301 and CYNAEX 302 in kerosene is shown in Fig.3. From this figure it is clear that the extraction of
Pd decreases by increasing the Pd concentration.
100
90
80

Uptake, %

70
60
50
40
30

H2TDT

20

CYANEX301
CYANEX302

10
1

-4

Metal Con, 10 M

Fig.(3):: Effect of Palladium feed concentration on its extraction from aqueous

nitrate solution
Effect of phase ratio (organic : aqueous) (0.5-6) on the extraction of 3x10-4M Pd by using 3x10-3 M
of H2TDT from nitric acid medium was investigated. The results shown in Fig.4 indicate that the
extraction of Pd increases by increasing the phase ratio.

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Arab Journal of Nuclear Science and Applications, 47(1), (53-60) 2014

100
90

Uptake, %

80
70
60

H2TDT

50
40
30
20
1

No. of Phase Ratio

Fig.(4): Effect of No. of phase ratio on the uptake of Palladium from aqueous nitrate solution by
H2TDT in kerosene
The effect of extractant concentration (0.25-3.5 x10-3M) on the extraction of 3x10-4M Pd from 0.5
M HNO3 was investigated. The results shown in Fig.5 indicate that the extraction of Pd increases by
increasing the extractant concentration.

100

H2TDT
CYANEX301
CYANEX302

Uptake, %

80

60

40

20

0
0.0

0.5

1.0

1.5

2.0

2.5

3.0

-4

Extract Con, 10 M

Fig.(5): Effect of extractant concentration on the uptake of Palladium from

aqueous nitrate solution
Extraction Equilibrium
From the aforementioned results it is clear that H2TDT is the extractant which is the highest to extract
Pd. Therefore, analysis of its equilibrium was carried out. Palladium was extracted with kerosene
solutions containing H2TDT, from nitrate medium. Slope analysis of [H+], [H2TDT] and [NO3-] on the
extraction of Pd are given in Fig.6. The results obtained show that in the case of extraction of Pd by
H2TDT 1mol of Pd chelate with 1mol H2TDT (slope = 1), 2H+ released in the aqueous medium (slope
= -2) and NO3- ions are present in the extracted species (slope = -2).
From these results the extraction equilibrium, under the used experimental conditions, could be
represented by:
____________

_________________

Pd2+ + 2NO3 - + H2TDT = Pd (NO3)2 TDT + 2 H+ (1)

(bars refer to organic phase),
with an extraction constant Kex , given by:
_______

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Arab Journal of Nuclear Science and Applications, 47(1), (53-60) 2014

Kex = D[H+]2/ [NO3-]2 [H2TDT]

(2)
The mean value of extraction constant of Pd Kex was found to be 9.27 0.02 x 108 M-1.
2.0
1.8

[H2TDT]

1.6

[H]
[Pd]

1.4

LogD

1.2
1.0
0.8
0.6
0.4
0.2
-2.0

-1.6

-1.2

-0.8

-0.4

0.0

0.4

0.8

1.2

Log[H2TDT],[H],[Pd]

Fig.(6): Slop analysis of [H+], [H2TDT] and [NO3-] on the extraction of Pd

Loading Capacity
The loading capacity of 3 x10-3 M H2TDT in kerosene was studied by shaking (3 x 10-5 M) Pd(II) in
aqueous solution of 3M HNO3 and 3 x10-3 M H2TDT / kerosene for 40 minutes at fixed organic to
aqueous phase ratio of 1:1 at 25oC. The two phases were separated, Pd(II) concentration was
determined and the same organic phase was shaken again with fresh aqueous Pd(II) solution . It was
found that the maximum concentration of Pd(II) in the organic phase is 1.01 x 10-3 M Pd(II) and was
reached after 4 stages, In this case, the experimental obtained capacity is 2.85 x 10-3 M Pd(II) per 3
x10-3 mole extractant. This supports the equilibrium given in equation (1), where one mole of
palladium is coordinated with one mole of H2TDT.
Stripping Investigations
The stripping investigations were carried out to choose a suitable stripping agent that can successfully
strip 2.85x 10-3 M Pd(II) from the loaded phase by 3 x10-3 M H2TDT in kerosene solution at aqueous
\ organic phase ratio of 1:1. In this respect, three different stripping agents were tested, i.e., HNO3,
HCl and H2SO4. The relation between the stripping agent concentration and the stripping percent of
Pd(II) from the organic phase is shown in Fig.7. The results obtained indicate that the stripping
percent of Pd(II) from the loaded organic phase increases by increasing the acid concentration.
0.20

Concentration of Pd g/l

0.18
0.16

HCl
H2SO4

0.14

HNO3

0.12
0.10
0.08
0.06
0.04
0.02
0.00
0.0

0.1

0.2

0.3

0.4

0.5

Stripping Concentration, M

Fig.(7): Effect of stripping agent concentration on the stripping percent of Pd(II)

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Arab Journal of Nuclear Science and Applications, 47(1), (53-60) 2014

Thermodynamic Parameters:
The effect of temperature on Pd(II) extraction was studied in the range 15C55C, Fig.8. and the
data were evaluated in terms of their thermodynamic parameters, in Table1. In this respect, the metal
concentration was 310-5 M Pd (II) from aqueous solution of 0.5M HNO3 using 3 x10-3 M H2TDT
/kerosene. The thermodynamic parameters are calculated using Vant Hoff equations. The negative
value of the enthalpy change (H) indicates that the extraction of Pd (II) in the investigated system is
an exothermic process, with a decrease in the randomness of the system shown by the high positive
value of the entropy change (S).
13.066

13.019

-5

Log Kex

Pd(II)= 3x10 M
-3
H2TDT=3 x10 M
12.972

12.925

0.0030

0.0031

0.0032

0.0033

1/T, K

0.0034

0.0035

-1

Fig.(8). Effect of temperature on the extraction of Pd(II) by H2TDT/ Kerosene from aqueous nitrate
solution
Table (1): Thermodynamic parameters for 2.510-4 M Pd(II) extracted by 2.5 x 10-3
M H2TDT/ Kerosene from 2M HNO3.
Thermodynamic parameter

Calculated value

Enthalpy Change (H)

-30.85 kJmole-1

Free Energy Change(G)

-25.35 kJmole-1

Entropy Change (S)

18.85 Jmole-1 K-1

CONCLUSION

From the results obtained in this work, it has been concluded that the selective recovery of Pd
from aqueous nitric acid solution using 2.5 x 10 -3 M of H2TDT / kerosene as a new extractant is
possible. The selectivity trend of Pd separation from nitric acid was observed to be H2TDT>,
CYNAEX 301 >CYNAEX 302 in kerosene The equilibrium was reached by the three extractants in
one step after 40 min. Slope analysis shows that 1mol of Pd(II) chelates with 1mol of H2TDT The
experimental capacity obtained is 2.85 x 10-3 M Pd(II) per 3 x10-3 mole extractant.. The results
obtained indicate that the stripping percent of Pd(II) from the loaded organic phase increases by
increasing the acid concentrations, and HCl is the best stripping agent. The negative value of the
enthalpy change (H) indicates that the extraction of Pd(II) in the investigated system is an
exothermic process, with a decrease in the randomness of the system shown by the high positive value
of the entropy change (S). The extraction of Pd from aqueous nitric acid solution by the three thiol
derivatives reaches its highest values at high acid concentrations.

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Arab Journal of Nuclear Science and Applications, 47(1), (53-60) 2014

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