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Hydrometallurgy 106 (2011) 175178

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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

A novel purication method for copper sulfate using ethanol


Serdar Aktas
Istanbul Technical University, Institute of Science & Technology, Maslak, 34469, Istanbul, Turkey

a r t i c l e

i n f o

Article history:
Received 22 December 2010
Received in revised form 10 January 2011
Accepted 11 January 2011
Available online 22 January 2011
Keywords:
Purication
Sulfate precipitation method
Copper
Ethanol
Precipitation

a b s t r a c t
This work presents a method for the purication of technical-grade copper sulfate by precipitation with
ethanol. We demonstrate a selective separation to the desired purity level, leaving impurities in solution. The
effects of altering the volume ratio of ethanol to copper sulfate solution, the solution pH, and the initial
concentration of copper and acid type were investigated. In this sulfate-based solution, ethyl alcohol was
shown to remove water ligands from the copper(II) cations, leading to the precipitation of copper as copper
sulfate pentahydrate. The developed method allows for the utmost purication, and the product can be used
in various applications where highly pure compounds are required. The applied method was proven to be
simple, straightforward and environmentally friendly.
2011 Elsevier B.V. All rights reserved.

1. Introduction
Copper sulfate has many applications, including the preparation of
Bordeaux and Burgundy mixtures, copper electrolysis, the control of
fungal diseases, and the correction of copper deciency in soils and in
animals (Courtade et al., 1999; Andras et al., 2009). Several chemical
tests utilize copper sulfate; for example, it is used in Fehling's solution
and Benedict's solution to test for reducing sugars, which reduce the
soluble blue copper(II) sulfate to insoluble red copper(I) oxide.
Copper(II) sulfate is also used in the Biuret reagent to test for proteins
and in the blood test for anemia (Wiberg et al., 1995; Shaffer and
Hartmann, 1921).
Copper sulfate can be produced by the action of sulfuric acid on a
variety of copper(II) compounds; for example, copper is oxidized to
copper(II) oxide with the addition of hydrogen peroxide to the acid,
and subsequently converted to copper sulfate (Atwood and Curtis,
1994; Davenport et al., 2002). It may also be prepared by electrolyzing
sulfuric acid using copper cathodes or by the electrolysis of an Epsom
salt solution at moderate voltage with a copper anode. The latter
reaction produces hydrogen gas, copper sulfate solution, and
magnesium hydroxide precipitate (Casas et al., 2000):
MgSO4aq 2 H2 O Cus H2g MgOH2s CuSO4aq

Another method of producing copper sulfate is to place metallic


copper in a solution of nitric acid, sulfuric acid and water. In this
method, nitric acid acts as an oxidizing agent, allowing copper to be
converted to copper oxide (Atwood and Curtis, 1994).
Tel.: +90 5337230576.
E-mail address: serdaraktash@yahoo.com.
0304-386X/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.hydromet.2011.01.001

Ethanol or ethyl alcohol, with the formula C2H5OH, is the second


member of the aliphatic alcohol series. Except for alcoholic beverages,
nearly all the ethanol used industrially is a mixture of 95% ethanol and
5% water (known simply as 95% alcohol); it is prepared by distilling
the solution that results from the fermentation of sugars (Ethanol,
2010; Myers, 2007).
C6 H12 O6 2CH3 CH2 OH 2CO2

Most of the ethanol used in industry is made not by alcoholic


fermentation but by an addition reaction between ethene and steam
(Ethanol, 2010).
C2 H4 H2 OC2 H5 OH

Ethyl alcohol has vast applications in the manufacturing of


alcoholic drinks (e.g., vodka), ethanal (acetaldehyde) and ethanoic
(acetic) acid, and fuel (e.g., gasohol). It is also used as a solvent for
paint, varnish and drugs; as uid in thermometers; and in preserving
biological specimens (Myers, 2007). However, its precipitating
properties have not been extensively investigated. The sulfate
precipitation method using ethanol can be used to purify metal
sulfates depending on their concentration in the solution (Aktas and
Acma, 2002; Aktas et al., 2006). This method can also be applied to
many other mixed compounds in solution by ensuring a selective
precipitation. The objective of this work was to precipitate copper
sulfate selectively, thus allowing impurities to remain in the solution,
and to purify this precipitated compound thoroughly with repeated
precipitations to yield an analytical-grade product.

176

S. Aktas / Hydrometallurgy 106 (2011) 175178

Table 1
The composition of the copper sulfate used in the study.
Components

Cu

Zn

Fe

Ag

Mg

SO4

Water of crystallization and moisture

Others

24.201

0.0911

0.0256

0.0011

0.0079

37.320

38.110

0.243

employed for analytical purposes. In the following section, various


experimental parameters are examined.

2. Materials and methods


2.1. Experimental procedures
Technical-grade copper sulfate pentahydrate (24.201% Cu) was
procured from a copper sulfate plant, Metal-Kim, in Istanbul, Turkey.
The composition of this sulfate is shown in Table 1.
The optimal precipitation parameters were determined by evaluating
the effects of the following factors: initial copper concentration, ethanol/
solution volume ratio, solution pH and acid type. For each experiment,
25 mL of copper sulfate solution was employed to precipitate copper
sulfate using various amounts of pure ethanol (12.5100 mL). The
experiments were conducted in a beaker for 15 min at an agitation rate of
300 rpm at room temperature, unless noted otherwise.
2.2. Analysis
Solid/liquid separation was performed following each precipitation
experiment. Atomic absorption spectrophotometer (Perkin Elmer
AAnalyst 800 AAS) was used to measure the concentrations of the
impurities present in the solution. Copper content was determined
using 0.1 M EDTA as an indicator (Murexide) in a Titroline Easy Titrator
for verication. Electrolytic measurements were also made using a
platinum anode and a platinum cathode designed specically for copper
electrolysis.
The efciency of this precipitation method was calculated as the
percentage of precipitated copper using the following equation:

Efficiency% = Co Ct x100 = Co

where Co is the initial copper concentration and Ct is the copper


concentration at the end of the experiment.
3. Results and discussion
The method outlined in this paper can be used to precipitate
copper sulfate with high efciency and to remove impurities from
copper sulfate so that the new copper sulfate pentahydrate can be

3.1. Effect of concentration on copper sulfate precipitation


Fig. 1 shows the variation of copper sulfate precipitation (%) with
changing copper concentration. As shown here, copper sulfate
precipitation increased with increasing copper concentration in the
solution. Therefore, it is important to increase copper concentration in
the solution if a higher degree of precipitation is desired. This result is
in agreement with a study by Aktas et al. (2006) in which cobalt
sulfate was precipitated using the same method. At a Cu concentration
of 1.28 g/L, no precipitation was observed, although precipitation
increased dramatically above 5 g/L Cu.
Ethanol precipitates sulfate compounds from the solution due to
the fact that ethanol behaves as a water-removing or dehydrating
agent when it is added to sulfate containing solutions (Aktas et al.,
2006). Ethanol is capable of precipitating metal sulfates from acidic
solutions (Aktas and Acma, 2002; Aktas et al., 2006), but it does not
precipitate metal sulfates at low concentration, as evident in Fig. 1.
This property of ethanol allowed the selective separation of copper
sulfate from other impurities. The optimum conditions for maximizing
copper sulfate precipitation and minimizing other sulfate precipitation
were then investigated.
The presence of ethanol lowers the thermodynamic activity of
water and makes it less available as a ligand for Cu2+ and SO2
4 . With
fewer water ligands, these two ions form direct bonds more easily,
and they precipitate as copper sulfate pentahydrate when a
substantial amount of ethanol is added to the solution (Aktas et al.,
2006).

3.2. Effect of solution pH on copper sulfate precipitation


Fig. 2 shows the effect on copper sulfate precipitation of varying
pH. As previously explained, ethanol acts as a dehydrating or waterremoving agent; it withdraws water, resulting in the precipitation of
metal sulfates. However, this effect becomes weaker at lower pH
values due to the gradual appearance of HSO
4 , which interferes with
100

CuSO4 Precipitation Efficiency, %

CuSO4 Precipitation Efficiency, %

100
90
80
70
60
50
40
30
20
10
0
0

10

15

20

25

30

35

40

45

50

55

60

Copper Concentration, g/L


Fig. 1. The variation of copper sulfate precipitation (%) with changing copper concentration
(ethanol/solution vol. ratio= 1, room temp., 300 rpm, pH ~3.5).

95
90
85
80
75
70
65
60
55
50
20
0
-1

Solution pH
Fig. 2. The variation of copper sulfate precipitation (%) with changing pH (ethanol/solution
vol. ratio= 1, initial Cu con.= 25.58 g/L, room temp., 300 rpm).

S. Aktas / Hydrometallurgy 106 (2011) 175178

177

CuSO4 Precipitation Efficiency, %

100
95
90
85
80
75
70
65
60
55
5
0
0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

Ethanol/Solution Volume Ratio


Fig. 3. The variation of copper sulfate precipitation (%) with changing ethanol/solution
volume ratios (initial Cu con. = 25.58 g/L, room temp., 300 rpm, pH = 3.76).

the formation of the CuSO4 bond, preventing the precipitation to a


certain degree and resulting in poorer efciencies (Aktas et al., 2006).
3.3. Effect of ethanol/solution volume ratio on copper sulfate precipitation
Fig. 3 shows the effect on copper sulfate precipitation of changing the
ethanol/solution volume ratio. It is apparent from the gure that copper
sulfate precipitation increased with increasing ethanol/solution volume
ratio. For a concentration of 25.58 g/L copper in a volume ratio of 0.5, a
precipitation of 68% was achieved; with a volume ratio of 2.0, a
precipitation of 97% was achieved. From this observation, we concluded
that a higher ethanol/solution volume ratio leads to greater precipitation.
3.4. Effects of various acids on copper sulfate precipitation
To investigate the effect of acid type on copper sulfate precipitation,
nitric acid, hydrochloric acid, and hydrobromic acid were employed. It
was observed that addition of HNO3, HCl, and HBr all had detrimental
effects on the precipitation. Almost no precipitate was observed after
these acids were added to the copper sulfate solution along with a
substantial amount of ethanol. From this observation, we concluded that
this applied process is only applicable to sulfate-containing solutions.
Classical techniques for salt crystallization rely on simultaneous
heating, water evaporation and crystal formation (nucleation). With
ethanol precipitation, no temperature shift is needed, and the process is
rapid and easy to implement. It is suggested that some of the impurities
are carried away with copper sulfate during sulfate precipitation by
ethanol. However, when the copper sulfate obtained was dissolved in
water and reprecipitated by this method several times, the level of

Fig. 5. Thermal gravimetric analysis of the nal product.

impurities was decreased to an appropriate level for analytical


applications. Thus, the proposed method ensures a thorough purication and selective precipitation.
3.5. Characterization of the obtained powder
Following the production of copper sulfate pentahydrate, it was
washed with fresh alcohol and subsequently dried under a vacuum at
45 C for 2 h. Fig. 4 displays the XRD pattern of the nal product. Fig. 5
displays TGA analysis of the nal product. As can be seen from the
pertinent gures, the product contains 5 mol of crystal water. To
determine the purity of the product, it was rst dissolved in 1 M sulfuric
acid solution at room temperature to allow complete dissolution. Along
with titration method, electrolysis was also conducted to determine the
copper content of the obtained powder. The copper content was
determined to be 25.45%. Table 2 shows the impurity levels at each
precipitation step. Table 3 displays a comparison of the nal product
produced in this work with commercially available products (ATA Chem
Ltd., 2010; Merck Data Sheet).
As shown in the table, the nal product contained lower amounts
of impurities than other commercially available products. It is also
worth mentioning that the product produced in this work contained no
acid at all, whereas other commercially available products invariably
contain small amounts of free acid.
4. Conclusions
In the present work, a novel precipitation method was developed
to selectively precipitate copper sulfate, leaving impurities in solution.
It was demonstrated that the obtained copper sulfate is of analytical
grade.
It is suggested that the concentration of metal sulfate should be near
saturation in water if a higher degree of precipitation is desired. For

Fig. 4. XRD pattern of the nal product.

178

S. Aktas / Hydrometallurgy 106 (2011) 175178

Table 2
Impurity level (ppm) in each precipitation step.
1

Impurities

Precipitation

Precipitation

Precipitation

Precipitation

Zn
Fe
Ag
Mg

575
87
6
55

218
29
4
25

91
3
1
11

59
n.d.a
n.d.
n.d.

Acknowledgments

Not detected.

Table 3
Impurity levels (ppm) in the nal product obtained in this work and other commercially
available products.
Impurities

Final product

Merck

ATA Chem Ltd.

Zn
Fe
Ag
Mg

59
n.d.a
n.d.
n.d.

b 300
b 30

300
100

It is possible to recover the ethanol by distillation using a rotary


evaporator or classical distillation units. However, in the present work, the
distillation of ethanol was not performed. Regarding disposal of the
solution, a sodium hydroxide can be used to precipitate metal hydroxides.
However, in industrial applications, Lewatite TP 207 resins are employed
to adsorb copper (II) ions selectively.

The author wishes to thank TUBITAK for their nancial support.


Special thanks are due to Mr. Tayfun Aktas for making possible the
analysis conducted in a private laboratory outside the university.
Grateful acknowledgment is also due to Prof. D. Fray at the University of
Cambridge for valuable discussions. Special thanks are also due to MSc.
Eng. Hasan Harman at Metal-Kim for the provision of copper sulfate.

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Not detected.

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