Article

pubs.acs.org/IECR

Solid−Liquid Equilibrium and Copper Sulfate Crystallization Process

Design from a Sulfuric-Acid−Seawater System in the Temperature
Range from 293.15 to 333.15 K
Francisca J. Justel, María E. Taboada, and Yecid P. Jiménez*
Department of Chemical and Mineral Process Engineering, University of Antofagasta, Av. Angamos 601, Antofagasta 124000, Chile

ABSTRACT: The objective of this work is to determine experimentally the

solubilities and the water activities for aqueous solutions of copper sulfate in
seawater at different temperatures and to use this information to represent the
solid−liquid equilibrium of a copper-sulfate−sulfuric-acid−seawater system. In
a previous work, the experimental solubility data of copper sulfate in acidic
seawater from 293.15 to 318.15 K were obtained experimentally; in this study,
these data were complemented by measuring solubilities at 323.15 and 333.15
K. The thermodynamic representation of the phase equilibrium is based on a
simple methodology reported in the literature with some modifications, where
the Pitzer model and a Born-type equation were used for modeling the copper
sulfate and sulfuric acid effects, respectively, and the seawater was considered as
a solvent. The amounts of copper sulfate precipitated and the optimum yield as
a function of the sulfuric acid concentration were estimated, giving relevant
information for the drowning-out crystallization process design of copper sulfate using seawater.

1. INTRODUCTION K were presented. Miller et al.8 presented thermodynamic and

Copper mining is the most significant economic activity in the
north of Chile. However, due to the arid conditions in this zone
along with water scarcity, mining industries have required
innovative solutions for the optimization of water consumption
and have started to use seawater in their productive processes.1
Copper sulfate pentahydrate is the most important industrial
compound of copper, with a wide variety of commercial
uses;2−4 it can be crystallized from an acidic solution from
copper leaching by the addition of greater amounts of sulfuric
acid, which generates supersaturation in the aqueous
dissolution of the salt.5 In Chile, some small and medium-
sized mining companies crystallize copper sulfate from
hydrometallurgical processes using freshwater. However, it
would be interesting to know the effect of seawater on the
crystallization and on the thermodynamic behavior of copper
sulfate pentahydrate. This information will be useful in the
process design to produce copper sulfate pentahydrate crystals
obtained from leaching solutions using seawater by means of
the addition of sulfuric acid.
Thermodynamic properties of copper sulfate (water
activities, activity, and osmotic coefficients) have been reported
in the literature by several authors: Wetmore and Gordon6
reported the activity coefficients of copper sulfate at different
molalities (up to 1 m) and different temperatures (288.15,
298.15, 308.15, and 318.15 K). Downes and Pitzer7 reported
the activity and osmotic coefficients of copper sulfate in
freshwater at molalities from 0.1 to 2.0 and at 298.15 K. In this
article, the Pitzer equations for 2−2 electrolytes for the
representation of the osmotic and activity coefficients for a salt
and the Pitzer parameters for copper sulfate solutions at 298.15
transport data (diffusion coefficients, electrical conductances,
and osmotic coefficients) for aqueous CuSO4 solutions at
298.15 K from low concentrations to near saturation, where the
osmotic coefficients for CuSO4 at concentrations from 0.00458
to 0.10355 m were reported. Apelbat9 reported the water
activities and osmotic coefficients of saturated solutions of
copper sulfate in freshwater at six different temperatures (from
283.15 to 308.15 K). Later, Gendouzi et al.10 reported the
water activities, osmotic coefficients, and activity coefficients
values of copper sulfate in freshwater at 298.15 K at different
molalities (from 0.2 to 1.4 m). Furthermore, the Pitzer
parameters for copper sulfate at 298.15 K were also reported.
Yang et al.11 reported the water activities and osmotic
coefficients of the binary systems MSO4 + H2O (M = Mn,
Co, Ni, Cu, and Zn) at 323.15 K from isopiestic measurements.
For copper sulfate, the values reported are in the range of
concentrations of 0.1289 to 2.0560 m.
In a previous work,12 solubility, density, and viscosity values
for saturated solutions of a copper-sulfate−sulfuric-acid−
seawater system at four different temperatures (from 293.15
to 318.15 K) were reported.
The objective of the present work is to determine the
saturation concentrations and water activities of copper sulfate
in seawater at different concentrations and temperatures (from
293.15 to 323.15 K). All this information was used to represent
Received: December 21, 2016
Revised: March 3, 2017
Accepted: March 24, 2017
Published: March 24, 2017

© XXXX American Chemical Society A DOI: 10.1021/acs.iecr.6b04925

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the solid−liquid equilibrium of the copper-sulfate−sulfuric-
acid−seawater system by the model proposed in this work,
which is based on a variation of the methodology of Kan et
al.13,14
Kan’s methodology uses the Pitzer model to quantify the
effect of a salt, whereas a similar equation to the Born model is
used to quantify the cosolvent effect. The present work
proposes a variation of this method where the Pitzer model is
used to represent the copper sulfate effect and the Born model
is used to represent the sulfuric acid effect, instead of a
cosolvent. Moreover, it is important to mention that in the
Pitzer model, seawater is the solvent and the seawater ions are
not considered separately.
Additionally, the amounts of precipitated salt and the
maximum yield from the CuSO4−H2SO4−seawater system at
different temperatures in function of the sulfuric acid
concentration were predicted. This information will be useful
in the process design to obtain copper sulfate pentahydrate
crystals using seawater by applying a simple methodology.
2. EXPERIMENTAL SECTION
2.1. Materials. All reagents employed in this research were
of analytical grade and supplied by Merck: copper sulfate
pentahydrate, 99%; absolute sulfuric acid, 95−97%, and
distilled deionized water (0.054 μS/cm).
Solutions were prepared using synthetic seawater, which was
prepared according to ASTM International:15 NaCl, 99%;
MgCl2, 99−101%; Na2SO4, 99−100.5%; CaCl2·2H2O, 99−
102%; KCl, 99.5%; NaHCO3, 99.7%; KBr, 99.5%; H3BO3,
99.5−100.5%; SrCl2·6H2O, 99−103%; NaF, 99.5%. The
chemical composition of the synthetic seawater is shown in
Table 1.
Table 1. Chemical Composition of Synthetic Seawater
Obtained from the Literature15
compound concentration (g/cm3) × 10−2
NaCl 2.4530
MgCl2 0.5200
Na2SO4 0.4090
CaCl2 0.1160
KCl 0.0695
NaHCO3 0.0201
KBr 0.0101
H3BO3 0.0027
SrCl2 0.0025
NaF 0.0003
Table 2 shows the density of synthetic seawater at six
different temperatures measured in triplicate using a Mettler
Toledo DE-50 vibrating tube densimeter with a precision of ±5
× 10−5 g/cm3.
2.2. Apparatus and Procedures. 2.2.1. Solubility Meas-
urements for the CuSO4−H2SO4−Seawater System at 323.15
and 333.15 K. Justel et al.12 reported density, viscosity, and
solubility data for saturated solutions of copper-sulfate−
Table 2. Synthetic Seawater Densities (g/cm3) at Different Temperaturesa
temperature (K) 293.15 298.15
density (g/cm3) 1.02464 1.02338
a
Standard uncertainty u for seawater densities is u(ρ) = 0.00005 g/cm3
B DOI: 10.1021/acs.iecr.6b04925
Article
sulfuric-acid−seawater at four different temperatures (from
293.15 to 318.15 K). Here, solubilities and densities at 323.15
and 333.15 K were measured in triplicate. Density was
measured using a Mettler Toledo DE-50 vibrating tube
densimeter with precision of ±5 × 10−5 g/cm3, and solubilities
were analyzed by the method of wet residues. The method-
ology utilized for the determination of the solubility is
described below.
The methodology for the equilibrium time determination has
been reported previously.12,16 For the CuSO4−H2SO4−sea-
water system, the equilibrium time for different temperatures
was determined by Justel et al.,12 where acidic seawater was
prepared by adding sulfuric acid to seawater until it reached pH
2. The pH was measured using an Accumet pH meter model 50
with a measurement range from −2 to 20 between 268.15 and
378.15 K and a precision of ±0.002. The masses of the copper
sulfate pentahydrate in the solution (acidic seawater) were
measured using an analytical balance (Mettler Toledo Co.,
model AX204, with a precision of 0.07 mg), and an excess of
copper sulfate pentahydrate was added to ensure that the
solution was saturated. Several saturated solutions in closed
glass flasks were immersed in a rotary water bath and
mechanically shaken. Every hour, the rotation was stopped,
and the solution density was measured. The equilibrium time
was determined when the solutions obtained at different times
reached constant densities.
Then, ten solutions (CuSO4−acid−seawater) at different
acid concentrations were prepared and stirred at 323.15 and
333.15 K in a rotary water bath during the equilibrium time.
The rotation was then stopped, and the solutions were
decanted. In the thermostatic bath, using a syringe filter,
solutions (without solid) were obtained for each equilibrium
point. The copper(II) concentration was measured in triplicate
by atomic absorption, and the CuSO4 solubility was obtained
by stoichiometry; density was measured in triplicate for each
solution. Solids were kept for further analysis.
2.2.2. X-ray Diffraction and Thermogravimetric Analysis
of Copper Sulfate Crystals. To analyze the composition of the
crystals obtained in seawater medium at different temperatures,
the same procedure as described above was used, and crystals
obtained at working temperatures of 293.15, 308.15, and
323.15 K were recovered. The crystals remaining after
decantation were dried and analyzed by powder X-ray
diffraction (XRD) using an automatic, computerized X-ray
diffractometer (Siemens Co., model D5000), Cu Kα radiation
with a wavelength of 1.5406 Å, and a voltage of 40 kV.
To confirm the XRD results, crystals obtained at 308.15 K
(intermediate temperature) were subjected to thermogravi-
metric analysis (TGA). Thermal assays were conducted with a
Mettler Toledo thermogravimetric analyzer TGA/DSC1,
STARe system. The crucibles used in the TGA instrument
were made of platinum and were hermetically sealed. The test
was conducted in a flowing inert nitrogen atmosphere (50 mL/
min) at a heating rate of 283.15 K/min. The equipment was
calibrated with indium, and the sample mass was 10 mg. The
308.15 318.15 323.15 333.15
1.01982 1.01586 1.01362 1.01180
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Table 3. Solubilities from 293.15 to 318.15 K Obtained in a Previous Work12 and Solubilities and Densities at 323.15 and
333.15 K Obtained in the Present Work for Saturated Solutions of Copper Sulfate in Acidic Seawater at Different Acid
Concentrationsa
(a) Solubilities from 293.15 to 318.15 K obtained in previous work12
T = 293.15 K T = 298.15 K T = 308.15 K T = 318.15 K

mH2SO4 mCuSO4 mH2SO4 mCuSO4 mH2SO4 mCuSO4 mH2SO4 mCuSO4

0.0000 1.3252 0.0000 1.3946 0.0000 1.6401 0.0000 1.9517
0.0460 1.3119 0.0454 1.3869 0.0461 1.6391 0.0445 1.9404
0.0958 1.3040 0.0913 1.3756 0.0933 1.6204 0.0899 1.9288
0.1943 1.2699 0.1851 1.3495 0.1885 1.5907 0.1819 1.9054
0.3013 1.2350 0.2868 1.3200 0.2918 1.5514 0.2815 1.8800
0.5136 1.1848 0.4902 1.2603 0.4960 1.5116 0.4843 1.8283
0.7940 1.0980 0.7547 1.1987 0.7651 1.4682 0.7416 1.7628
1.0948 1.0238 1.0385 1.1432 1.0508 1.4061 1.0251 1.6906
1.4221 0.9563 1.3531 1.0732 1.3731 1.3406 1.3445 1.6092
1.7690 0.8738 1.6776 1.0043 1.6873 1.3126 1.6506 1.5313
2.5546 0.7051 2.4184 0.8401 2.4278 1.2099 2.3824 1.3449
(b) Solubilities and Densities at 323.15 and 333.15 K Obtained in the Present Work
T = 323.15 K T = 333 K

mH2SO4 mCuSO4 ρ (g/cm ) 3

mH2SO4 mCuSO4 ρ (g/cm3)
0.0000 2.0746 1.30330 0.0000 2.4675 1.34400
0.0439 2.0657 1.30419 0.0419 2.4585 1.34420
0.0883 2.0568 1.30286 0.0847 2.4492 1.34378
0.1794 2.0384 1.30092 0.1717 2.4304 1.33843
0.2780 2.0185 1.29873 0.2658 2.4101 1.33682
0.4741 1.9789 1.29731 0.4541 2.3694 1.33508
0.7307 1.9271 1.29634 0.6992 2.3164 1.33350
1.0096 1.8709 1.29816 0.9649 2.2590 1.33097
1.3058 1.8111 1.30040 1.2558 2.1961 1.33481
1.6192 1.7478 1.30622 1.5536 2.1318 1.33684
2.3129 1.6079 1.31380 2.2288 1.9859 1.34757
a
Standard uncertainties u for molalities of H2SO4 and CuSO4 and densities of the saturated solutions are u(mH2SO4) = 0.0002 mol/kg H2O and
u(mCuSO4) = 0.0003 mol/kg H2O, and u(ρ) = 0.00005 g/cm3, respectively.

temperature range used in the experiment was from 298.15 to
573.15 K.
2.2.3. Water Activity Measurements of CuSO4 in Seawater
at Different Temperatures. Water activities were measured
using a Novasina Corp. model AW-Center 500 electronic
hydrometer. The hydrometer was calibrated before making
each set of measurements by using standard salt solutions
supplied by the manufacturer. This instrument works in the
temperature range from 273.15 to 323.15 K, so the measure-
ments of the activities of copper-sulfate−seawater solutions
were performed in duplicate from 293.15 to 323.15 K. At each
temperature, solutions at six different concentrations of copper
sulfate were measured.
With the objective of improving the accuracy, calibration
curves using sodium sulfate aqueous solutions were developed
at each working temperature (293.15, 298.15, 308.15, 318.15,
and 323.15 K). For each temperature, at least five sodium
sulfate solutions were prepared at different molalities, and the
obtained data were compared and fitted to the values reported
by Holmes and Mesmer,17 obtaining calibration curves at each
temperature. Using these calibration curves for the water
activities, we determined the Pitzer parameters β(0), β(1), β(2),
and C(⌀) for copper sulfate in synthetic seawater from 293.15 to
323.15 K.
It is important to mention that in the present work, the
solutions were prepared using synthetic seawater (Table 1)
elaborated under ASTM International standards,15 which
makes reproducible all the parameters determined in the
present work.
3. THERMODYNAMIC FRAMEWORK
According to Gendouzi et al.,10 using the experimental data of
the water activities as a function of molality, it is possible to
determine the osmotic coefficients (⌀) for each solution using
eq 1:
⌀ = −(1000/(vmM ))ln a w (1)
where v is the number of ions released by dissociation, m the
molality, M the molar mass, and aw the water activity.
On the other hand, a simple method based on a variation of
Kan’s methodology13,14 to correlate copper sulfate solubilities
in acidic seawater is proposed.
Accordingly, the activity coefficients due to the copper sulfate
effect γS±(CuSO4) were determined by the Pitzer model,18
where for 2:2 electrolytes, the mean activity ionic coefficients
are given by the following expression:
ln γ± = 4f γ + mBγ + m2C γ (2)
where
f γ = −A⌀[I1/2/(1 + bI1/2) + 2/b ln(1 + bI1/2)] (3)

C DOI: 10.1021/acs.iecr.6b04925
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Figure 1. Solubility of saturated solutions of CuSO4−H2SO4−seawater: ■ = 293.15 K; ◆ = 298.15 K; ▲ = 308.15 K; ● = 318.15 K; × = 323.15 K;
* = 333.15 K; solid line, correlated data; dashed line, data predicted by the methodology proposed in this work.
Bγ = 2β (0) + (2β (1)/α12I )[1 − (1 + α1I1/2 − 1/2α12I )
−α1I1/2 (2) 2
exp ] + (2β /α2 I )
1/2 2 −α2I1/2
[1 − (1 + α2I − 1/2α2 I ) exp ] (4)
C γ = 3/2C ⌀
In these equations, m and I correspond to the molality and
ionic strength, respectively. The symbols β(0), β(1), β(2), and C⌀
are solute specific parameters, and the parameters α1, α2, and b
are constant, with values of 1.4, 12, and 1.2 kg1/2·mol−1/2,
respectively.
In eq 3, the function fγ includes the Debye−Hückel term
(A⌀) represented by the following expression:19
A⌀ = 1/3 2πdN0 [e 2 /4πE0εkT ]3/2
where d corresponds to the density of seawater (kg/m3), N0 to
the Avogadro number (6.022045 × 1023), K to the Boltzmann
constant (1.38066 × 10−23), e to the electron charge (1.6022 ×
10−19), E0 to the permittivity of vacuum (8.85418 × 10−12), ε to
the dielectric constant of seawater, and T to the temperature in
K. The values of the dielectric constant (ε) of seawater at
different temperatures were obtained by the method of
Hernández-Walls using the equations reported by Stogryn.20
Here A⌀ is calculated considering the seawater as solvent.
The solubility product (Ksp) of a hydrated salt is a value
obtained from the solubility (concentration), the water activity,
and activity coefficient values of copper sulfate in seawater
(without acid). These last two were calculated using the Pitzer
model through the eqs 1 and 2, respectively. The Ksp values at
different temperatures were determined by the following
expression:21
CuSO4 ·5H 2O
K sp = (mCuSO4 )2 (γ±S(CuSO4 ))2 (a w )5
On the other hand, the sulfuric acid effect, is γN± (CuSO4)
represented by an empirical equation similar to the Born
expression of the type:
Article
2
γ±N(CuSO4 ) = 10(a + b / T(K) + cI )xH2SO4 + dxH2SO4 (8)
where a, b, c, and d are fitting parameters and xH2SO4 and I
represent the mole fraction of sulfuric acid in the H2O−H2SO4
mixture and the ionic strength, respectively.
(5) From eq 7, the copper sulfate saturation molality in the
ternary CuSO4−H2SO4−seawater system (mT) is obtained by:
m T = [(K spCuSO4 ·5H2O)B /((γ±S(CuSO4 )2 (γ±N(CuSO4 )2 a w 5)T ]1/2
(9)
where the subscripts B and T represent the binary (CuSO4−
H2O) and ternary (CuSO4−H2SO4−H2O) systems, respec-
tively.
Experimental data of the solubilities of the copper-sulfate−
sulfuric-acid−seawater system at five different temperatures
(6) were correlated, minimizing the following objective function:
OF = ∑ (mT,exptl − mT,calcd /mT,exptl)2 (10)
where the subscripts exptl and calcd are the experimental and
calculated saturation concentrations, respectively.
4. RESULTS AND DISCUSSION
4.1. Solubilities of Copper Sulfate in Acidic Seawater
at Different Temperatures. The experimental solubility data
of copper sulfate in seawater at six different temperatures (from
293.15 to 333.15 K) and experimental density values at 323.15
and 333.15 K are shown in Table 3a,b.
The experimental solubility data (in mol/kg H2O) of copper
sulfate in seawater at four different temperatures (from 293.15
to 318.15 K) obtained in a previous work12 are shown in Table
3a. Solubility and density values at 323.15 and 333.15 K
obtained in the present work are presented in Table 3b.
(7) The experimental and calculated solubility data (expressed as
the molality of CuSO4 for different molalities of H2SO4) from
293.15 to 333.15 K are shown in Figure 1, where a big effect of
sulfuric acid on the reduction of the copper sulfate solubility is
observed. According to Cisternas,22 this behavior is attributed
D DOI: 10.1021/acs.iecr.6b04925
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Figure 2. XRD patterns of copper sulfate samples obtained at three different temperatures: (a) 293.15 K, (b) 308.15 K, and (c) 323.15 K. Black and
red lines correspond to the standard patterns and samples, respectively.

E DOI: 10.1021/acs.iecr.6b04925
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Figure 3. Thermal decomposition curve of copper sulfate pentahydrate crystals obtained from a CuSO4−H2SO4−seawater solution at 308.15 K.
to the common ion effect, which causes the reduction in
solubility. For the studied system, copper sulfate and sulfuric
acid share the SO42− ion.
4.2. Solids Analysis: X-ray Diffraction and Thermog-
ravimetric Analysis. XRD and TGA were used to analyze the
composition of the crystals obtained at different temperatures
using sulfuric acid and seawater.
Figure 2 shows the XRD patterns of samples obtained at
three different temperatures (293.15, 308.15, and 323.15 K).
At the three different temperatures (293.15, 308.15, and
323.15 K), the results showed that the obtained salt is 99.9%
copper sulfate pentahydrate.
To validate the XRD results, the crystals obtained at 308.15
K were analyzed using TGA. The results of mass loss as a
function of time are shown in Figure 3.
From Figure 3, it is evident that when copper sulfate
pentahydrate is heated (from 298.15 to 573.15 K), it loses its
water of crystallization in two steps at different temperatures.
Additionally, Figure 3 shows that the total dehydration is
35.98%, where the water loss is 28.62% in the first step,
corresponding to the loss of four water molecules, and 7.36% in
the second step, corresponding to the loss of one water
molecule. These results allowed us to validate the sample
composition, confirming that it corresponds to copper sulfate
pentahydrate.
4.3. Water Activities of the Copper-Sulfate−Seawater
System at Different Temperatures. The water activities of
copper sulfate in seawater in the temperature range from
293.15 to 323.15 K were measured in order to validate the
Pitzer model used to represent the solid−liquid equilibrium of
the copper-sulfate−sulfuric-acid−seawater system later. These
water activity values with their respective absolute average
deviations (AAD) are presented in Table 4.
On the other hand, the effect of seawater on the water
activities of copper sulfate solutions is represented in Figure 4,
where the experimental results of the CuSO4−seawater system
from this work (Table 4) were compared with water activity
values in freshwater reported by Guendouzi et al.10 and Yang et
al.11 at 298.15 and 323.15 K, respectively. The comparison
F DOI: 10.1021/acs.iecr.6b04925
Article
between the copper sulfate water activities in both media at two
different temperatures is shown in Figure 4.
From Figure 4, it is possible to observe that in both systems
(freshwater and seawater) at 298.15 and 323.15 K, the water
activity values decrease with increases in the solution
concentration. Moreover, the activity values in seawater are
lower than those in freshwater; this behavior is due to the
increment in the number of water molecules associated with the
different ions in the solution.23 On the other hand, with regard
to the temperature effect in both systems (Table 4 and Figure
4), the activity values are slightly higher at 323.15 K; these
results agree with those of Guendouzi and Dinane,23 who
reported that the water activities are highly affected by the
solute concentration but slightly influenced by the temperature.
4.4. Determination of the Pitzer Parameters β(0), β(1),
β(2), and C⌀ for Copper Sulfate in Seawater at Different
Temperatures. Regarding the Pitzer ion-interaction parame-
ters, Ning et al.24 reported that ion interaction parameters for a
single salt at different temperatures could be expressed using
the following equation based on the works of Marliacy et al.25
and Hovey et al.:26
P(T ) = P0 + P1(1/T − 1/298.15) + P2 ln T /298.15
(11)
⌀
where P represents β , β , β , and C ; T is the temperature
(0) (1) (2)
in Kelvin; and P0, P1, and P2 are fitting parameters.
Using the experimental water activity data of copper sulfate
in seawater (cf. Table 4) and eq 11, we were able to establish
the values of P0, P1, and P2 for the determination of the CuSO4
Pitzer parameters in seawater in the temperature range from
293.15 to 323.15 K. These values are presented in Table 5.
Here, the seawater with all its constituent salts was
considered as a solvent. On the other hand, the low AAD
values of the water activities (Table 4) demonstrated the
reliability of eq 1124 for the determination of the Pitzer
parameters of the copper sulfate−seawater system in the
temperature range from 293.15 to 323.15 K.
4.5. Solubility Products of Copper Sulfate Pentahy-
drate in Seawater at Different Temperatures. Table 6
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Table 4. Experimental and Calculated Water Activities (aw)

at Different Molalities of CuSO4 in Seawater and at Five
Different Temperaturesa
m (mol/kg H2O) aexptl
w acalcd
w AAD (×10−3)
T= 293.15 K
0.8615 0.9842 0.9848 0.222
0.9598 0.9822 0.9824
1.0422 0.9806 0.9804
1.1260 0.9787 0.9782
1.2114 0.9764 0.9758
1.3017 0.9738 0.9733
T= 298.15 K
0.8617 0.9845 0.9849 0.218
0.9604 0.9826 0.9826
1.0426 0.9809 0.9806
1.1244 0.9790 0.9784
Figure 4. Comparison between the experimental and literature data of
1.2124 0.9768 0.9761
water activities of CuSO4 in seawater and freshwater at (◆) 298.15
1.4046 0.9711 0.9705 and (●) 323.15 K: solid line, CuSO4−freshwater;10,11 dashed line,
T= 308.15 K CuSO4−seawater [present work].
0.8613 0.9848 0.9853 0.249
1.0413 0.9815 0.9811 Table 5. Pitzer Parameters of Copper Sulfate in Seawater
1.2123 0.9773 0.9767 within the Temperature Range of 293.15 to 323.15 K.
1.3085 0.9748 0.9741
1.4049 0.9720 0.9713 parameters β(0) β(1) β(2) C⌀
1.6072 0.9652 0.9653 P0 0.5750 2.9831 0 −0.0721
T= 318.15 K P1 −0.0008 −0.0010 0 0.0004
1.0418 0.9816 0.9815 0.341 P2 0.2463 0.3079 0 −0.1326
1.2127 0.9777 0.9771
1.4050 0.9727 0.9718 Table 6. Solubility Products and Activity Coefficient Values
1.6075 0.9665 0.9658 at Different Temperatures and Copper Sulfate
1.8043 0.9596 0.9597 Concentrations
2.0002 0.9516 0.9534 4·5H2O
T (K) m (mol/kg H2O) γS±(CuSO4) KCuSO
sp
T= 323.15 K
1.0509 0.9818 0.9814 0.374 293.15 1.3252 0.0317 0.0015
1.2126 0.9782 0.9774 298.15 1.3946 0.0304 0.0016
1.4044 0.9732 0.9722 308.15 1.6401 0.0276 0.0017
1.6079 0.9672 0.9664 318.15 1.9517 0.0255 0.0019
1.8041 0.9607 0.9605 323.15 2.0746 0.0245 0.0020
1.9998 0.9531 0.9545 333.15 2.4675 0.0226a 0.0023a
4·5H2O
a
AAD = |(aexptl
w − acalcd
w )/n|, where n is the number of experimental
a
Predicted values for γS±(CuSO4) and KCuSO
sp at 333.15 K.
points. The standard uncertainties u for the adjusted water activities
and molalities of copper sulfate are u(aw) = 0.0006 and u(mCuSO4) =
which have a direct effect on the solubilities and water activities
0.0001 mol/kg H2O, respectively.
used for the calculations.
4.6. Representation of the Solid−Liquid Equilibrium.
shows the solubility product and activity coefficient values of 4.6.1. Experimental and Calculated Solubility Isotherms of
copper sulfate pentahydrate in seawater from 293.15 to 333.15 the CuSO4−H2SO4−Seawater System at Different Temper-
K. These values were calculated by eq 7, where the solubility atures. Considering the seawater as a solvent, the values of A⌀
values and water activities of copper sulfate in seawater in the for copper sulfate in seawater at temperatures from 293.15 to
absence of acid were utilized for the calculations. 333.15 K were calculated using eq 6 and are shown in Table 7.
It is important to mention that due to the measurement On the other hand, regarding the sulfuric acid effect, the
range of the hydrometer used to determine water activities, it parameter values of the Born-type empirical equation (eq 8) for
was not possible to realize measurements over 323.15 K. Thus, the CuSO4−H2SO4−seawater system were obtained. These are
CuSO4·5H2O
the values for γ±S (CuSO4) and Ksp at 333.15 K valid in the temperature range from 293.15 to 323.15 K and are
correspond to predicted values, where the Pitzer parameters presented in Table 8.
used for these calculations were determined using the values Figure 1 shows the correlation of the solubility data of the
from Table 5. copper-sulfate−sulfuric-acid−seawater system from 293.15 to
Christov27 reported the solubility product of copper sulfate 323.15 K and also includes the predicted solubilities of copper
pentahydrate in freshwater at 298.15 K, obtaining a value of sulfate in acid seawater at 333.15 K using the parameter values
0.0026. Accordingly, there is a difference of 0.0010 between the from Tables 5 and 8.
solubility product obtained in the present work (Table 6) and A good agreement between the experimental and correlated
that reported in the literature;27 this small difference between values for the CuSO4−H2SO4−seawater system at the five
Ksp values is mainly due to the presence of salts in the seawater, temperatures (from 293.15 to 323.15 K) was obtained, with an
G DOI: 10.1021/acs.iecr.6b04925
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Industrial & Engineering Chemistry Research Article

Table 7. A⌀ Values for Copper Sulfate in Seawater Media at Different Temperatures

T (K) 293.15 298.15 308.15 318.15 323.15 333.15
A⌀ 0.49377 0.49726 0.50464 0.51191 0.51354 0.5195

Table 8. Parameter Values of the Born-Type Empirical

Equation (Eq 8)
a 5.1564
b 0.0191
c −0.4248
d 0.1947

AAD of 0.0062 mol/kg. On the other hand, predicted data at

333.15 K have a deviation with respect to the experimental data
of 0.0053 mol/kg, allowing the reproducibility of the model
proposed in the present work to be verified.
The approach that has been given here considers the studied
system as a ternary one, where seawater was taken as a solvent,
instead of considering the seawater ions individually; moreover,
the sulfuric acid effect was considered separately by means of
the Born-type equation. Despite this consideration, the average
deviation obtained in the present work indicates that the
proposed method is a successful tool to represent the solubility
of copper sulfate in a complex medium such as seawater and
could be used by the mining industry.
4.7. Predictions of Precipitated Amounts and Yield of
Copper Sulfate. As shown above, sulfuric acid has a significant
effect on the reduction of copper sulfate solubility, being a good
agent for its crystallization. For this reason, the quantification of
the copper sulfate precipitated at different percentages of
sulfuric acid can provide relevant information for the isothermal
crystallization process design.
According to Jiménez et al.,14 this prediction can be
performed starting from an initial equilibrium condition
where the copper sulfate is saturated in seawater and no
copper sulfate precipitates. Then, if any amount of sulfuric acid
is added to the system, the precipitation is produced and a new
equilibrium condition is established, where the copper sulfate is
present in lower quantity and is saturated again but is now in a
new seawater−sulfuric-acid medium. If this new concentration
is substituted into eq 7, the following expression is obtained
and can be used to predict these precipitated amounts:
X = 2m0 − [4m0 2 − 4(m0 2 − K spCuSO4 ·5H2O
/(γ±S(CuSO4 ))2 (γ±N(CuSO4 ))2 a w 5)]/2 (12)
where m0 is the copper sulfate molality in the initial saturated
solution (without acid) and X is the precipitated amount (in
mol/kg) obtained when the sulfuric acid is added to the system.
This amount can also be expressed in grams per liter,
considering the molar mass of copper sulfate and the density
of seawater (Table 2).
This method was applied to different sulfuric acid
concentrations (wt %) and temperatures. The results of the
predictions (in grams of CuSO4·5H2O per liter of saturated
solution) at 298.15 and 323.15 K for the CuSO4−H2SO4−
seawater system are presented in Figure 5.
From Figure 5, it is readily apparent that in both cases the
precipitation is highly affected by the acid concentration, where,
as the sulfuric acid concentration is increased, a greater amount
of copper sulfate is precipitated. Similar results were obtained at
the other temperatures.
Figure 5. Predicted amounts of copper sulfate pentahydrate
precipitated versus sulfuric acid weight percent at two different
temperatures: (◆) 298.15 and (×) 323.15 K.
Also, it is possible to observe that the precipitated amounts
are not highly affected by the temperature, with similar
amounts of copper sulfate pentahydrate being obtained in
both cases when sulfuric acid is added to the system. This is
because, in the temperature range from 293.15 to 333.15 K, the
solubility curves of the CuSO4−H2SO4−seawater system (cf.
Figure 1) have similar slopes, which causes the precipitated
amounts to be similar at the different temperatures.
On the other hand, based on the work of Jiménez et al.,14
once the values of X have been determined, it is possible to
calculate the percentage of sulfuric acid that produces the
maximum precipitate. This amount is defined as the yield (Y).
The prediction of the amount of acid that produces the
maximum yield (Y) can be calculated by the following
expression:14
Y = XM(100 − s)(1 − w)10−5 (13)
where s is the CuSO4 solubility expressed as weight percent,
and M and w represent the molecular weight of copper sulfate
and the mass fraction of sulfuric acid (free of salt), respectively.
This estimation has been performed for the CuSO4−
H2SO4−seawater system using the copper sulfate and sulfuric
acid concentrations from Table 3 (as a weight percent and mass
fraction, respectively) in the temperature range from 293.15 to
333.15 K. Table 9 shows the results of the optimum values Y,
with their respective sulfuric acid concentrations, obtained at
each temperature.
Table 9. Optimum Values of w and Y for the CuSO4−
H2SO4−Seawater System at the Six Different Temperatures
T (K) H2SO4 (wt %) yield (%)
293.15 18.1037 11.419
298.15 16.9197 10.523
308.15 16.4071 9.181
318.15 15.7963 10.402
323.15 14.9704 8.858
333.15 14.0057 8.102

H DOI: 10.1021/acs.iecr.6b04925
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Industrial & Engineering Chemistry Research
From Table 9, it can be noted that independently of the
temperature, the yield reaches a maximum value at the highest
concentration of sulfuric acid used at each temperature. Also, it
is important to mention that the higher value of Y obtained at
293.15 K is attributed to the higher acid concentration used for
the calculations.
As can be seen in Figure 5 and Table 9, with the range of
sulfuric acid concentrations used for the calculations, it was not
possible to achieve a maximum precipitated amount (X) and
yield (Y), so it is possible that the optimum acid concentration
necessary to reach maximum values of X and Y is higher.
However, our calculations of Y are based on the sulfuric acid
values normally used by the mining industry (over 100 g/L
H2SO4).5
On the other hand, despite the high copper concentrations
present in the initial solutions (Table 3), high yields were not
obtained (Table 9). So it is proposed that a continuous
crystallization process with recirculation would help to obtain
higher values of Y.
4.8. Conceptual Design of the Copper Sulfate
Crystallization Process by Means of the Addition of
Sulfuric Acid Using the Phase Diagram. The conventional
methodology used to make the graph of yield versus the sulfuric
acid weight percent is through a solubility diagram (graph
form). In the present work, this calculation has been carried out
at 298.15 and 323.15 K (Figure 6), and these results were
compared to those obtained analytically using eq 12.
Figure 6. Solubility diagram of CuSO4−H2SO4−seawater system at
298.15 K (◆) and 323.15 K (×).
The solution compositions used for the calculations were
obtained from Figure 6, which shows the solubility diagram
(expressed as the mass fraction) of the studied system at 298.15
and 323.15 K, where the conceptual process design was
realized. F1 and F2 correspond to the input currents of pure
sulfuric acid and saturated aqueous solution of copper sulfate,
respectively. These flows (F1 and F2) are subsequently mixed
and separated into copper sulfate pentahydrate crystals (F3)
and saturated solution (F4) at the outlet of the crystallizer.
Calculations were realized considering the crystallization
process as isothermal and F2 as 100 g/s, while the mass flows
F1, F3, and F4 were obtained from a material balance (Figure 7).
The compositions were also read directly from the solubility
diagram (Figure 6).
Figure 7 shows the flow sheet of the isothermal copper
sulfate crystallization process, where the input and output
I DOI: 10.1021/acs.iecr.6b04925
Article
Figure 7. Process flow sheet of the copper sulfate crystallization
process using sulfuric acid.
currents were also represented in Figure 6. Flow compositions
are given in Table 10.
Figure 8 shows the precipitated amounts of copper sulfate
pentahydrate at 298.15 and 323.15 K using the analytic and
graph forms. In both cases, the same acid concentration values
from Table 3 were used, and the results are expressed in grams
of CuSO4·5H2O per liter of saturated solution versus sulfuric
acid weight percent.
It is observed that at both temperatures, the amounts of
copper sulfate precipitated increase as the acid concentration
increases. On the other hand, it is possible to note that the
results obtained using the analytical and graph methods are
similar, with mean deviations of 2.67% and 3.54% at 298.15 and
323.15 K, respectively. This indicates that the analytical
methodology proposed in the present work is suitable for the
design of the isothermal copper sulfate crystallization process
using seawater by means of the addition of sulfuric acid. Similar
results were obtained at other temperatures (293.15, 308.15,
318.15, and 333.15 K).
The main contribution of the present work is that a simple
methodology has been proposed to correlate the CuSO4−
H2SO4−seawater system, which also allows the prediction of
the sulfuric acid concentration that maximizes the copper
sulfate precipitation. This approach could be very useful in the
crystallization process design and for the mining industry,
because only a few solubility data are needed to know the
optimal amount of sulfuric acid to obtain the maximum yield.
In the future, the next step is to realize crystallization
experiments with seawater by adding sulfuric acid to validate
the model proposed in the present work.
5. CONCLUSIONS
A simple methodology, based on a variation of Kan’s method,
has been applied to represent the solid−liquid equilibrium of
the copper-sulfate−sulfuric-acid−seawater system at different
temperatures and considering the seawater as a solvent,
obtaining an AAD of 0.0062 mol/kg. Also, a simple analytical
procedure has been applied to construct yield-versus-concen-
tration diagrams, which can be used to estimate the sulfuric acid
concentration that maximizes the copper sulfate precipitation.
From the methodology proposed in the present work, it has
been possible to obtain valuable information that could be
useful in the design of the copper sulfate crystallization process
by means of the addition of sulfuric acid. So in the future, it
would be interesting to prove the reproducibility of the model
Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
Industrial & Engineering Chemistry Research Article

Table 10. Compositions of the Input and Output Currents at 298.15 and 323.15 Ka
currents F1 F2 F3 F4
compositions (w) X1 X2 X1 X2 X1 X2 X1 X2
T = 298.15 K 0 1 0.1770 0 0.639 0 0.0956 0.1691
T = 323.15 K 0 1 0.2428 0 0.639 0 0.1735 0.1497
a
X1 and X2 correspond to the mass fractions of copper sulfate and sulfuric acid, respectively.

ionic transport coefficients lij for aqueous CuSO4 at 25 °C. J. Solution

Figure 8. Amount of CuSO4·5H2O precipitated versus sulfuric acid
weight percent. Solid and dashed lines represent the analytical method
while the symbols ◆ and × represent the graph method at 298.15 and
323.15 K, respectively
through experimental tests, to validate the model, and to apply
it in the mining industry.
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(9) Apelblat, A. The vapour pressures of saturated aqueous solutions
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sulfate, and manganese (II) dichloride, at temperatures from 283 to
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■
(15) D-98, A. Standard Practice for the Preparation of Substitute Ocean
Water; ASTM International: West Conshohocken, PA, 2008.
AUTHOR INFORMATION (16) Alavia, W.; Lovera, J. A.; Cortez, B. A.; Graber, T. f. A. Solubility,
Corresponding Author density, refractive index, viscosity, and electrical conductivity of boric
*E-mail: yecid.jimenez@uantof.cl. acid+ lithium sulfate+ water system at (293.15, 298.15, 303.15, 308.15
ORCID and 313.15) K. J. Chem. Eng. Data 2013, 58 (6), 1668−1674.
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Yecid P. Jiménez: 0000-0001-6451-4615
of the alkali metal sulfates. J. Solution Chem. 1986, 15 (6), 495−517.
Notes (18) Pitzer, K. S.; Mayorga, G. Thermodynamics of electrolytes. III.
The authors declare no competing financial interest.

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ACKNOWLEDGMENTS (19) Fernandez, D.; Goodwin, A.; Lemmon, E. W.; Levelt Sengers, J.
Funding for this research was provided by CONICYT M. H.; Williams, R. A formulation for the static permittivity of water
(Fondecyt Project 1140169 and Grant 21130894). and steam at temperatures from 238 to 873 K at pressures up to 1200

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K DOI: 10.1021/acs.iecr.6b04925
Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX