Hydrometallurgy 106 (2011) 71–75

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Hydrometallurgy
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / h yd r o m e t

Rhodium recovery from rhodium-containing waste rinsing water via cementation

using zinc powder
Serdar Aktas ⁎
Istanbul Technical University, Institute of Science and Technology, Maslak, 34469, Istanbul, Turkey

a r t i c l e i n f o a b s t r a c t

Article history: The present work proposes the recovery of rhodium from rhodium-containing waste rinsing water through
Received 28 June 2010 cementation with metallic zinc powder. The effects of zinc content, reaction temperature, reaction time and
Received in revised form 3 December 2010 shaking on rhodium recovery are investigated in detail. In addition, the cementation kinetics of rhodium is
Accepted 5 December 2010
studied, and its activation energy was found to be 30 kJ/mol. After a detailed observation of the dissolution
Available online 15 December 2010
behavior of the zinc powder during the cementation process, it is demonstrated that most of the zinc is
Keywords:
preferentially consumed by free acid, a finding corroborated by pH measurements. The proposed process is
Rhodium simple, straightforward and economically feasible.
Waste plating solutions © 2010 Elsevier B.V. All rights reserved.
Recovery
Cementation

1. Introduction
Rhodium belongs to the platinum-group metals (PGM) and has a
special catalytic activity to reduce nitrogen oxides (NOx) to N2; thus,
rhodium is extensively used in automotive catalysts (Colombo, 2008).
Rhodium is one of the rarest elements, occurring in only one part in
109 in the earth's crust (Cardarelli, 1966). Its chemistry has not been
studied extensively. However, rhodium chemistry generally resem-
bles that of cobalt and, to an even greater extent, that of iridium
(Forrester and Ayres, 1959).
Its high and relatively uniform reflectivity and the ease with which
it produces hard, bright electrodeposits have led to the widespread
use of rhodium in jewelry, searchlight reflectors and electrical
contacts (Stwertka, 2002; Raub, 1994). In the 1930s, rhodium began
to be used as a plating metal for decorative purposes and for
applications in which corrosion resistance was needed (Ward, 2008).
Rhodium remains bright under atmospheric conditions at ordinary
temperatures and is completely resistant to a variety of corrosives; it
is also one of the most difficult materials to dissolve in aqueous
solutions (Kayanuma et al., 2004). Moreover, it is not oxidized in
atmospheric conditions, unlike silver, and has a high reflective index
(0.8) (Cardarelli, 1966). For this reason, rhodium-plating baths have
been extensively used in making jewelry. In jewelry workshops
where rhodium plating is practiced, 2.0 g of rhodium in the form of its
sulfate or phosphate is dissolved in 1 L of distilled water to ensure that
the plating solution contains 2000 ppm rhodium prior to application.
This solution can be used until the rhodium concentration falls below
500 ppm, after which matter deposits are obtained (information
provided by Hasar, S., Grand Bazaar, Istanbul, Turkey). Following the
plating of each gold or silver item with rhodium, the item is rinsed
with clean distilled water to remove solution drops. After the rinsing
water becomes contaminated the expensive rhodium can be
recovered from it. However, most workshops in the Grand Bazaar in
Istanbul do not bother to save this solution; rather, they discharge it
without considering its environmental impact or economic value.
The cementation technique has been used in industry for a long
time in both hydrometallurgy and in the purification of process
streams and wastewaters. The advantages of the cementation process
include its relative simplicity, ease of control and its ability to recover
of valuable metals (Habashi, 2005; Doyle, 2005; Nosier and Sallam,
2000). However, the consumption of sacrificial metals and the redox
potentials of sacrificial metals limit the application of this process
(Park, 2008). In the applied recovery process, the more reactive metal
(in the present case, metallic zinc powder) is oxidized and rhodium is
reduced, as this latter metal is much nobler than zinc. This process
results in the production of rhodium powder.
The standard reduction potentials of Rh and Zn are given as
follows:
RhðaqÞ + 3e → Rh∘ðsÞ
3+ −
E = + 0:758 V ð1Þ

ZnðaqÞ + 2e → Zn∘ðsÞ
⁎ Tel.: +90 533 7230576(mobile). 2+ −
E-mail address: serdaraktash@yahoo.com. E = −0:762 V ð2Þ

0304-386X/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.hydromet.2010.12.005
72 S. Aktas / Hydrometallurgy 106 (2011) 71–75

100
The potential difference is calculated to be 1.52 V (Park, 2008).
The overall reaction is expressed in Eq. (3):

Rh2 ðSO4 Þ3ðaqÞ + 3Zn∘ðsÞ 2Rh∘ðsÞ + 3 ZnSO4ðaqÞ

80
→ ð3Þ

Rh Recovery (%)
(Safarzadeh et al., 2007). 60
The objectives of this work were 1) to recover the rhodium
incorporated in waste rinsing water via cementation with zinc
powder and 2) to highlight the dissolution behavior of the sacrificing 40
metal (zinc) and 3) to observe the pH variation during the
cementation process.
20

2. Materials and methods

Used rinsing water that was procured from a rhodium-plating
workshop (Hasar, S., Turkey) was employed in this work.
All of the chemicals used in this study were of analytical grade. The
optimal cementation parameters were established by examining the
following factors: time, temperature, amount of zinc powder
(b150 μm, Aldrich), absence or presence of shaking and solution pH.
The rhodium content (Co) of the waste solution was determined to be
144.8 ± 0.1 ppm using a Perkin Elmer AAnalyst 800 Atomic Absorp-
tion Spectrophotometer. Solution pH was measured to be 1.99 using a
WTW pH 315i pH meter. For each experiment, 20 mL of waste rinsing
water was employed to cement the rhodium out of the solution using
various amounts of zinc powder. The experiments were conducted
inside a falcon tube with a volume of 50 mL that was placed in a
temperature-controlled shaking bath to ensure uniform heat convec-
tion at the surface of the falcon tube. The zinc content of the treated
solution was measured using a Titroline Easy Titrator by means of
0.01 M EDTA titration solution.
Solid/liquid separation was performed following each cementation
experiment. For the analyses, the filtered solutions were introduced
into the instrument at an appropriate dilution when necessary. The
recovery (%) of this cementation process was calculated from the
percentage of the cemented rhodium using the following equation:
Recoveryð%Þ = ½ðCo −Ct Þ = Co  × 100 ð4Þ
where Co is the initial rhodium concentration (144.8 ± 0.1 ppm) and
Ct is the concentration at the end of the experiment.
To investigate the cementation behavior of the rhodium from the
waste rinsing water, a kinetic study was performed. After the
cementation reaction, excess zinc was digested in 2.0 M HCl (pH =
−0.3) to clean the product thoroughly. The morphology of the
rhodium produced was investigated using a JEOL JSM-5800 LV
scanning microscope (SEM). The oxygen and hydrogen contents of
the samples were measured with a NOH-2000 analyzer.
3. Results and discussion
The process outlined in this paper could be used to recover almost
all of the rhodium present in waste rinsing water. In the following
section, the process parameters were examined in detail.
0
0 10 20 30 40 50 60 70 80 90 100
Amount of Zn (mg)
Fig. 1. The variation in rhodium recovery (%) with different quantities of zinc (25 °C,
200 rpm, 1 h, 20 cm3 of 144.8 ppm Rh3+).
in the solution increases, which results in higher cementation (%)
(Farahmand et al., 2009). Similar observations were also made in the
study by (Aktas, 2010) where silver conversion (%) increased with
increasing quantities of zinc.
Approximately 2.75 mg zinc is stoichiometrically adequate to
cement all the rhodium out of a 20-mL solution containing 2.896 mg
rhodium. Interestingly, even 10 times the stoichiometric amount was
not enough to recover all of the rhodium, which can be attributed to
the fact that zinc is consumed by the free acid in the acidic medium
rather than being subjected to the cementation reaction with rhodium
ions. It is also worth mentioning that the rhodium sulfate used in the
plating was in the complex form rather than in the form of simple
rhodium sulfate (Belyaev et al., 2007a,b). This complex is very stable
(Forrester and Ayres, 1959; Mellor, 1936; Armstrong and Choppin,
1965), which is why much more than the stoichiometric amount of
zinc powder is necessary to disrupt this rhodium complex. Fig. 2
shows the variation in solution pH with increasing amounts of zinc
powder.
As shown in Fig. 2, solution pH increases dramatically with
increasing amounts of zinc powder, which confirms that zinc
preferentially reacts with free sulfuric acid in the medium rather
than cementing rhodium out of the solution. However, above a certain
amount of zinc powder (e.g., 50 mg), there is almost no change in
solution pH; this result indicates that free acid is nearly neutralized by
zinc powder.
7.0
6.5
6.0
5.5
5.0
4.5
4.0
pH

3.5
3.1. Cementation of rhodium incorporated in waste rinsing water by zinc 3.0
powder 2.5
2.0
Fig. 1 shows that the rhodium recovery (%) increased with 1.5
increasing amounts of zinc powder, which is in agreement with 1.0
studies that investigated cementation efficiency with regard to the 0.5
quantity of the cementator (Aktas, 2008; Aktas et al., 2010). The 0.0
0 10 20 30 40 50 60 70 80
recovery was almost complete when N60 mg of zinc powder was
Amount of Zn (mg)
used. By increasing the amount of the cementator, the surface area of
zinc powder per rhodium ion increases. Hence, the likelihood of Fig. 2. The variation in solution pH with different quantities of zinc (25 °C, 200 rpm, 1 h,
interactions between metallic zinc atoms with rhodium ions present 20 cm3 of 144.8 ppm Rh3+).
 S. Aktas / Hydrometallurgy 106 (2011) 71–75 73

44 100
40 90
36 80 20 mg Zn
30 mg Zn
Dissolved Zn (mg)

32
70 40 mg Zn

Rh Recovery (%)
28 50 mg Zn
60
24
50
20
16 40

12 30

8 20
4 10
0 0
0 10 20 30 40 50 60 70 80
0 10 20 30 40 50 60 70
Amount of Zn (mg) Time (min)
Fig. 3. The levels of dissolved zinc (mg) with different quantities of zinc added to the
Fig. 4. The variation in rhodium recovery (%) over time (25 °C, 200 rpm, 20 cm3 of
solution (25 °C, 200 rpm, 1 h, 20 cm3 of 144.8 ppm Rh3+).
144.8 ppm Rh3+).

6.5
Fig. 3 shows the dependence of dissolved zinc on the amount of
zinc powder added to the solution. Table 1 shows the zinc balance in 6.0
the cementation reaction. 5.5
As shown in Table 1, appreciable amount of zinc was consumed by 5.0
free acid, resulting in the increment in solution pH. After 40 mg of zinc 4.5
addition, the dissolved zinc quantity levels off. 4.0
As shown in Fig. 3, the amount of dissolved zinc increased up to 3.5
pH

40 mg, which was also confirmed by the variation in solution pH with 3.0
the amount of zinc. However, above 40 mg of zinc powder, there was 2.5
almost no change in the amount of the dissolved zinc in the solution 2.0
due to the fact that nearly all of the free acid is neutralized with zinc 1.5 20 mg Zn
powder (Abdel-Aal, 2000; Nagib and Inoue, 2000). 30 mg Zn
1.0 40 mg Zn
In order to observe the effect of time on rhodium recovery, 50 mg Zn
0.5
experiments were carried out at various time intervals. Figs. 4, 5 and 6
0.0
show Rh recovery (%), pH variation and dissolved zinc (mg) over time. 0 10 20 30 40 50 60 70
These three figures similarly show that zinc preferentially reacts Time (min)
with free acid, resulting in the increment in solution pH. Moreover,
30 min was enough to cement rhodium out of the solution. It is also Fig. 5. The variation in solution pH over time (25 °C, 200 rpm, 20 cm3 of 144.8 ppm Rh3+).
apparent from Fig. 6 that 20 mg and 30 mg of zinc were consumed
within the first 10 min of the reaction, which indicates that zinc has a After the effect of shaking was observed, it was attempted to
great affinity for acidic solutions and that this is an exothermic investigate the effect of temperature alone on rhodium recovery.
reaction (Huggare and Ojanen, 1973). However, this is negligible Thus, experiments were conducted without shaking. Some authors
because the experiments were carried out in a temperature- have suggested that temperature is the most influential parameter on
controlled shaking bath. cementation (Blaser and O'Keefe, 1983). The effect of temperature on
Fig. 7 displays the effect of shaking on the recovery of rhodium. the recovery of rhodium is displayed in Fig. 8.
As shown in Fig. 7, shaking was an important parameter affecting
the cementation of rhodium from waste rinsing water. Without
shaking, a recovery of 9% was obtained after 10 min, although a 45
recovery of 37% was achieved using shaking for the same duration.
40
This finding indicates that rhodium cementation is affected by
diffusion-controlled kinetic factors (Habashi, 1976). 35
Zn Dissolved (mg)

30

Table 1 25
Zinc balance in the cementation reaction.
20
Zinc balance⁎
15
Added Used for Rh Consumed by Unreacted Solution
quantity (mg) cementation (mg) acid (mg) zinc (mg) pH 10 20 mg Zn
30 mg Zn
20 0.62 19.38 0.00 2.42 40 mg Zn
5 50 mg Zn
30 1.62 28.38 0.00 2.81
40 2.52 36.43 1.05 4.76 0
50 2.71 36.28 11.01 6.03 0 10 20 30 40 50 60 70
60 2.74 36.26 21.00 6.04
Time(min)
70 2.74 36.27 30.99 6.20
⁎Conditions: 25 °C, 200 rpm, 1 h, 20 cm3 of 144.8 ppm Rh3+. Fig. 6. The variation in dissolved zinc in the solution over time (25 °C, 200 rpm, 20 cm3
Error: Rh ± 0.07%, Zn ± 0.05%, pH ± 0.14%. of 144.8 ppm Rh3+).
74 S. Aktas / Hydrometallurgy 106 (2011) 71–75

100 2.5
25°C
35°C
80 2.0 45°C
55°C
65°C
Rh Recovery (%)

60 1.5

-ln(1-α)
40 1.0

20 0.5
No Shaking
200 rpm
0 0.0
0 10 20 30 40 50 60 70 0 15 30 45 60 75
Time (min) Time(min)

Fig. 7. The variation in rhodium recovery (%) with over time with and without shaking Fig. 9. The plot of −ln(1 − α) vs. time for the rhodium cementation by zinc powder.
(25 °C, 40 mg zinc, 20 cm3 of 144.8 ppm Rh3+).

As shown in Fig. 8, temperature had an important role in the
recovery of rhodium from waste rinsing water even though no shaking
was used. Temperature weakens the rhodium complex, increasing the
cementation efficiency as the reaction temperature increased. It is also
worth mentioning that the plating process is generally conducted at
approximately 60 °C because high temperatures facilitate the plating
process, weakening the rhodium complex. For instance, a recovery of
39% was observed after 60 min using 40 mg zinc powder at room
temperature. However, under the same conditions but at a temperature
of 65 °C, a recovery of 89% was achieved, which proves that the process
is under chemical control (Nelson, 1998). The increment in the recovery
(%) may be attributed to the increased temperature at which the oxide
film is removed from the deposit structure, thus increasing the
cementation efficiency (Dönmez et al., 1999; Farahmand et al., 2009).
After showing that temperature played an important role in the
cementation reaction, as found in a previous study (Aktas, 2010), it
was attempted to determine the rate constant (k) of rhodium
cementation within a temperature range of 298–338 K. After demon-
strating that shaking is a significant parameter in the cementation
reaction, shaking was not used in the kinetics study in order to
emphasize the effect of temperature. For this purpose, −ln (1− α) was
plotted over time (Dickinson and Heal, 1999; Markus et al., 2004), as
shown in Fig. 9.
Fig. 10 shows the Arrhenius plot of ln k vs. 103/T for rhodium
cementation. α, k and T denote cementation efficiency, rate constant,
temperature (K) respectively. At a temperature range between 25 and
65 °C, the activation energy for rhodium cementation was calculated
to be 30 kJ/mol. Taking into account that shaking was not used, this
result indicates that the cementation process is mainly governed by a
chemically-controlled process (Habashi, 1976).
3.1.1. Characterization of the obtained powder
Following the production of metallic rhodium powder, the powder
was washed with fresh 2.0 M HCl (pH = −0.3), distilled water, and
then acetone and subsequently dried under vacuum at 80 °C for 1 h.
To determine the purity of the produced powder, the powder was
dissolved in fused sodium bisulfate (NaHSO4) at approximately 600 °C
to allow complete dissolution (Khar'kova et al., 2001). The sample was
found to contain 99.27% ± 0.1 rhodium. Zinc analysis was then carried
out and the zinc content of the sample was found to be 0.65% ± 0.01.
Hydrogen content was measured to be 0.078% ± 0.001, although
oxygen was not detected. According to the SEM images shown in
Fig. 11, a porous powder was obtained and the particles were
nanosized and had a typical structure obtained via cementation.
4. Conclusion
In the present work, it was attempted to recover rhodium from
rhodium-containing waste rinsing water that is used to clean rhodium
plated items following the plating process. It was demonstrated that
more than 99% of the rhodium metal in waste rinsing water could be
recovered using only high quantities of zinc powder. This is possible

100 -3.2

-3.4 y = - (3.606 * X) + 7.394

80
-3.6
Rh Recovery (%)

-3.8
60
ln(k)

-4.0

40 -4.2

25°C
-4.4
35°C
20 45°C
55°C -4.6
65°C
0 -4.8
0 15 30 45 60 75 2.9 3.0 3.1 3.2 3.3 3.4
Time (min) 103/T (K-1)

Fig. 8. The variation in rhodium recovery (%) over time at various temperatures. (40 mg Fig. 10. The Arrhenius plot of ln (k) vs. 1000/T for the rhodium cementation by zinc
zinc, no shaking, 20 cm3 of 144.8 ppm Rh3+). powder.
 S. Aktas / Hydrometallurgy 106 (2011) 71–75
Fig. 11. SEM image of the rhodium powder obtained via cementation by zinc powder
(10,000×).
because most of the zinc powder was consumed by free acid in the
medium and rhodium is in its complex form. Shaking and temper-
ature were shown to be important parameters in the cementation
reaction, which is in accordance with the scientific literature. The
activation energy of rhodium cementation by metallic zinc powder
was calculated to be 30 kJ/mol. Using this method, a fine rhodium
powder with a purity of 99.27% ± 0.1 was produced. The zinc and
hydrogen contents of the powder were found to be 0.65% ± 0.01 and
0.078% ± 0.001, respectively, yet oxygen was not detected. Although
this impure powder can be directly sold, it needs further purification
prior to being used for the preparation of rhodium sulfate plating
solution because the zinc content of the powder decreases reflectivity
of rhodium deposits extremely. It needs to be re-dissolved and
selectively precipitated by formic acid, hydrazine hydrate or hydra-
zine sulfate (information by Aktas, S., unpublished results), which is
beyond the scope of the present study. The proposed process avoids
environmental problems and allows for the non-hazardous hydro-
metallurgical recovery of valuable rhodium from rhodium-containing
waste rinsing water.
Acknowledgements
The author wishes to thank TUBITAK for the financial support.
Special thanks are due to Güntaç Zorlu (MSc student) for his
invaluable discussions and Mr. Tayfun Aktas for making possible the
analysis conducted outside the university. Grateful acknowledgment
is also due to Tony Goetz & Zonen, Antwerpen, Belgium for invaluable
support.
75
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