Thermodynamic model for acidic Fe(II) sulphate from solubility data

P.M. Kobylin
a,n
, H. Sippola
a,b
, P.A. Taskinen
a
a
Department of Materials Science and Engineering, Aalto University, FI-00076 Aalto, Finland
b
FCG Finnish Consulting Group Oy, Osmontie 34, FI-00601 Helsinki, Finland
a r t i c l e i n f o
Article history:
Received 1 March 2012
Received in revised form
28 June 2012
Accepted 28 June 2012
Available online 31 July 2012
Keywords:
Ferrous sulphate
Solubility
Ferrous sulphate hydrates
Pitzer model
Sulphuric acid
CALPHAD method
a b s t r a c t
Acidic ferrous sulphate solutions are generated in a large scale in the hydro- and pyrometallurgical
industries. They are also produced in the steel industry and titanium dioxide production. Acid mine
drainage has long been a signicant environmental problem in the coal and metal sulphide mining. The
demand of recycling and reuse of materials has increased signicantly especially in EU. Dumping and
land lling a neutralised deposit is not an option anymore. Thus, efcient techniques of recycling and
reuse of sulphuric acid and/or metal sulphates from the side streams are needed.
When developing alternative solutions, a better understanding of the thermodynamic behaviour of
the FeSO
4
H
2
SO
4
H
2
O system is needed. In the present study a thermodynamic model of this system
has been developed, in order to yield a thermodynamically consistent set of values for the solubility of
iron sulphate in a wide temperature and concentration range. The current model presents the
experimental data available with a good accuracy and consistently up to 100 1C, and sulphuric acid
concentrations up to 10 mol/kg. The model also predicts well the solubility measurements available in
dilute sulphuric acid solutions at 160220 1C.
& 2012 Elsevier Ltd. All rights reserved.
1. Introduction
The waterferrous sulphatesulphuric acid system has been
studied due to its key importance in many hydrometallurgical
applications, which typically operate at temperatures between 50
and 300 1C. Hydrometallurgical processes such as stainless steel
pickling acid regeneration, lateritic nickel hydrometallurgy, titania
manufacturing and zinc leaching as well as acid mine drainage from
tailings ponds need internally consistent thermodynamic databases
to improve, develop and understand deeper the systems and
phenomena in the aqueous process solutions and environments.
In aqueous sulphuric acid solutions, ferrous sulphate forms
hydrates with 1, 4, 5, 6 and 7 molecules of crystalline water, with
the chemical names szomolnokite, rozenite, siderotil, ferrohex-
ahydrite and melanterite, respectively [1]. Thermodynamics of
the H
2
OFeSO
4
H
2
SO
4
system have been modelled earlier by
Reardon and Beckie [2], Sippola [3] and Kobylin [4], Kobylin
et al. [5] and Przepiera [6] using the Pitzer model. Those models
have also been reviewed critically in this work.
Reardon and Beckie [2] assessed the FeSO
4
-H
2
SO
4
H
2
O sys-
tem using Harvies modication of the Pitzer model for describing
activity coefcients over a temperature range from 10 to 60 1C in
the ternary system and from 10 to 90 1C for the binary FeSO
4

H
2
O. The solubility data in H
2
O were used to generate the
temperature dependent equations for the solubility products
(K
sp
) for melanterite and szomolnokite, which were used with
the ternary solubility data to generate Pitzer parameters for the
FeSO
4
H
2
SO
4
H
2
O system. Reardon and Beckie did an iterative
regression analysis on the ternary system with the concentration
limit of the experimental data 6 mol/kg of H
2
SO
4
. They used the
sulphuric acid second dissociation constant K
2
from Pitzer et al.
[7] and a different ternary Pitzer interaction parameter c(H

Fe
2
HSO
4

) than the other authors. This model is limited in

concentration and temperature range, and extrapolations using
the model fail.
Sippola [3] assessed the FeSO
4
H
2
SO
4
H
2
O system, using the
same Pitzer model version as Reardon and Beckie [2]. Instead of
using the solubility products he used the D
f
H1
298.15
, S1
298.15
and C
p
(T)
data. Heat capacity data for melanterite were taken from Lyon and
Giauque [8], at 260.8307.67 K. Sippola estimated the heat capacity
data of the rozenite and szomolnokite from MgSO
4
H
2
O(s) and
MgSO
4
4H
2
O(s) using the relation C
p
(FeSO
4
nH
2
O)C
p
(FeSO
4
)
C
p
(MgSO
4
nH
2
O)C
p
(MgSO
4
), where n is 1 for monohydrate and
4 for tetrahydrate. He was able to reproduce the solubility of FeSO
4
in
H
2
O and up to 6.1 mol/kg of sulphuric acid over a temperature range
of 0100 1C. Sippola used c(Fe
2
HSO
4

SO
4
2
) ternary Pitzer para-
meter in his assessment. The parameters of Sippola have been listed
in Kobylin et al. [5]. Sippolas [3] model is extrapolating well also
outside that concentration and temperature range but his binary
Contents lists available at SciVerse ScienceDirect
journal homepage: www.elsevier.com/locate/calphad
CALPHAD: Computer Coupling of Phase Diagrams and
Thermochemistry
0364-5916/$ - see front matter & 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.calphad.2012.06.011
n
Corresponding author. Tel.: 358 50 3251489; fax: 358 94 7022798.
E-mail addresses: petri.kobylin@aalto. (P.M. Kobylin),
hannu.sippola@aalto. (H. Sippola), pekka.taskinen@aalto. (P.A. Taskinen).
CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 38 (2012) 185193
FeSO
4
H
2
O system is not able to reproduce enthalpy and heat
capacity of solution data.
Kobylin [4] and Kobylin et al. [5] assessed the H
2
OFeSO
4

H
2
SO
4
and H
2
OFe
2
(SO
4
)
3
H
2
SO
4
systems at 0100 1C and 25 1C,
respectively, using the original Pitzer model [1315], excluding
unsymmetrical mixing terms and following the same procedure
as in Sippola [3], and adopting the solubility data (up to 10 mol/kg
of sulphuric acid) only in the parameter optimisation. This model
presents well FeSO
4
H
2
O(s) solubility data but is lacking accuracy
for FeSO
4
7H
2
O at lower temperatures. As in Sippolas model,
Kobylin et al. set of Pitzer parameters in the binary FeSO
4
H
2
O
system is not able to reproduce enthalpy and heat capacity of
solution data.
Przepiera [6] assessed the H
2
OFeSO
4
H
2
SO
4
system at 0100 1C
and up to 30 mol/kg of sulphuric acid using the same Pitzer model
version as Reardon and Beckie [2] and Sippola [3]. Przerpiera
included both enthalpy of solution and solubility data in his
assessment, but the paper is lacking some thermodynamic data
and that is why Przepiera results are not recalculated in this work.
Przepiera [6] tabulated solubility data at 0, 25, 50, 80 and 100 1C
which are included in Figs. 15 for comparison up to 10 mol/kg of
H
2
SO
4
. The concentration range of Przepiera [6] seems to be too
high for the Pitzer model, 30 mol/kg of sulphuric acid.
The new improved thermodynamic models of the binary
systems FeSO
4
H
2
O and H
2
SO
4
H
2
O have been published in
separate papers [9,10] by authors. In the FeSO
4
H
2
O study [9]
melanterite and szomolnokite were found to be stable phases with
the peritectic transition temperature at 56.5 1C. Adding sulphuric
acid to the system will decrease this temperature due to lowering
of the activity of water so that there is a peritectic point with
0.0
0.2
0.4
0.6
0.8
1.0
1.2
0 2 4 6 8 10
Molality of H
2
SO
4
/ molkg
-1
M
o
l
a
l
i
t
y

o
f

F
e
S
O
4


/

m
o
l

k
g
-
1FeSO
4
7H
2
O
FeSO
4
H
2
O
Fig. 1. The assessed and experimental solubility data on the system H
2
OFeSO
4
H
2
SO
4
at 0 1C. this work; (- - -) Sippola [3]: extrapolated outside the H
2
SO
4
concentration range of the original work; (- - -) Reardon and Beckie [2]: extrapolated outside the temperature and H
2
SO
4
concentration range of the original work; (....)
Kobylin et al. [5]; ( ) Przepiera [6]; (&) Belopolskii and Urusov [23]; () Bullough et al. [24]; (J) Kobe and Fredrickson [25]; (D) Cameron [20]: data was not included in
the assessment. Transition compositions are shown as larger symbols; open and close symbols refer to FeSO
4
7H
2
O(s) and FeSO
4
H
2
O(s), respectively.
0.0
0.5
1.0
1.5
2.0
2.5
0 2 4 6 8 10
Molality of H
2
SO
4
/ molkg
-1
M
o
l
a
l
i
t
y

o
f

F
e
S
O
4


/

m
o
l

k
g

-
1
FeSO
4
7H
2
O
FeSO
4
H
2
O
Fig. 2. The assessed and experimental solubility data on the system H
2
OFeSO
4
H
2
SO
4
at 25 1C. this work; (- - -) Sippola [3]: extrapolated outside the H
2
SO
4
concentration range of the original work; (- - -) Reardon and Beckie [2]: extrapolated outside the H
2
SO
4
concentration range of the original work; (y) Kobylin et al.
[5]; ( ) Przepiera [6]; (&) Belopolskii et al. [22]; (D) Cameron [20]: data was not included in the assesssmet; () Bullough et al. [24]. Transition compositions are shown
as larger symbols; open and close symbols refer to FeSO
4
7H
2
O(s) and FeSO
4
H
2
O(s), respectively.
P.M. Kobylin et al. / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 38 (2012) 185193 186
0.0
0.5
1.0
1.5
2.0
2.5
3.0
0 2 4 6 8 10
Molality of H
2
SO
4
/ molkg
-1
M
o
l
a
l
i
t
y

o
f

F
e
S
O
4

/

m
o
l

k
g
-
1
FeSO
4
H
2
O
Fig. 4. The assessed and experimental solubility data on the system H
2
OFeSO
4
H
2
SO
4
at 80 1C. this work; (- - -) Sippola [3]: extrapolated outside the H
2
SO
4
concentration range of the original work; (- - -) Reardon and Beckie [2]: extrapolated outside the temperature and H
2
SO
4
concentration range of the original work; (y)
Kobylin et al. [5]; ( ) Przepiera [6]; (~) Bullough et al. [24].
0.0
0.5
1.0
1.5
2.0
2.5
0 2 4 6 8 10
Molality of H
2
SO
4
/ molkg
-1
M
o
l
a
l
i
t
y

o
f

F
e
S
O
4

/

m
o
l

k
g
-
1
FeSO
4
H
2
O
Fig. 5. The assessed and experimental solubility data on the system H
2
OFeSO
4
H
2
SO
4
at 100 1C. this work; (- - -) Sippola [3]: extrapolated outside the H
2
SO
4
concentration range of the original work; (- - -) Reardon and Beckie [2]: extrapolated outside the temperature and H
2
SO
4
concentration range of the original work; (y)
Kobylin et al. [5]; ( ) Przepiera [6]; (~) Bullough et al. [24]; (K) Kobe and Fredrickson [25]: data was not included in the assessment.
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
0 2 4 6 8 10
Molality of H
2
SO
4
/ molkg
-1
M
o
l
a
l
i
t
y

o
f

F
e
S
O
4

/

m
o
l

k
g
-
1
FeSO
4
7H
2
O
FeSO
4
H
2
O
Fig. 3. The assessed and experimental solubility data on the system H
2
OFeSO
4
H
2
SO
4
at 50 1C. this work; (- - -) Sippola [3]: extrapolated outside the H
2
SO
4
concentration
range of the original work; (- - -) Reardon and Beckie [2]: extrapolated outside the H
2
SO
4
concentration range of the original work; (y) Kobylin et al. [5]; ( ) Przepiera [6];
(&) Belopolskii and Shpunt [21]. Transition compositions are shown as larger symbols; open and close symbols refer to FeSO
4
7H
2
O(s) and FeSO
4
H
2
O(s), respectively.
P.M. Kobylin et al. / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 38 (2012) 185193 187
different compositions in each temperature from 055 1C. The
FeSO
4
H
2
O system was successfully assessed from 2 to 220 1C
frompure water up to solubility limit of ferrous sulphate 3.58 mol/kg.
The H
2
SO
4
H
2
O system has been assessed by Sippola [10] with
the experimental EMF cell and osmotic coefcient data only, and
it is valid up to 6.1 mol/kg and over a temperature interval of
055 1C. Sippola [10] found out that four different K
2
equations
for the dissociation of HSO
4

are equally suitable for presenting

the H
2
SO
4
H
2
O system. The equation of Matsushima and Okuwaki
[11] was chosen since it has been found out to be able to describe
the H
2
SO
4
FeSO
4
H
2
O system up to 100 1C [3].
The aim of this study is to compile and reassess critically the
experimental solubility observations of the FeSO
4
H
2
OH
2
SO
4
sys-
tem at 0100 1C and H
2
SO
4
concentration range up to 10 mol/kg
and test the thermodynamic description for the system up to 220 1C
to validate our previous FeSO
4
H
2
O and H
2
SO
4
H
2
O binary models
[9,10] with this ternary system. All experimental data used in the
modelling were taken from the literature. The resulting thermo-
dynamic model was obtained using the thermodynamic equilibrium
calculation programMTDATA
s
(www.mtdata-software.com), which
uses global Gibbs energy minimisation routine and includes the
Pitzer activity coefcient model for the excess Gibbs energy of the
aqueous solutions. The CALPHAD (CALculation of PHAse Diagrams)
method [12] was used in the modelling, to ensure internal consis-
tency of the thermodynamic database.
2. Modelling the aqueous solutions
The Pitzer model is one of the most used activity coefcient
models for aqueous solutions. The original approach assumes that
the aqueous solution consists only of ions, and no ion complexes
are formed. Details of the Pitzer model used are available in
[1315]. Later, Harvie and Weare [16] and Harvie et al. [17]
included unsymmetrical electrostatic mixing terms in their mod-
ication of the Pitzer model, which has been shown to improve
the t in multicomponent systems. The values for the internal
constant parameters Harvies modication of the Pitzer equation
used in this work are shown in Table 1. All the necessary Pitzer
model equations, variables and parameters have been explained
in our previous paper [9].
2.1. Thermodynamic functions
The consistent concentration unit in aqueous solutions is
molality of FeSO
4
and H
2
SO
4
(mol/kg of water), which is used
throughout this paper. The temperature dependency equation in
MTDATA
s
for heat capacity of a species has the following form:
C
p
AB
T
K

C
T
K

2
D
T
K

2
, 1
and thus Gibbs energy has a temperature-dependent form
GT A
G
B
G
T
K

C
G
T
K

ln
T
K

D
G
T
K

2
E
G
T
K

3
F
G
T
K

1
2
The general temperature dependency available in MTDATA
s
for the Pitzer equation parameter (p) is
p A
Pitz
B
Pitz
T
K

C
Pitz
T
K

ln
T
K

D
Pitz
T
K

2
E
Pitz
T
K

3
F
Pitz
T
K

1
3
3. Experimental observations
3.1. Solubility data
Solubility measurements have been made at temperatures
ranging from 0 to 220 1C [1831]. The solubilities measured until
1958 have been reviewed by Linke and Seidell [32]. Hasegawa
et al. [31] have measured the solubilities at 160220 1C. Accord-
ing to Hasegawa et al., FeSO
4
H
2
O is the stable phase at those
temperatures.
The peritectic point, which means the condition at which the
phase transition from melanterite (FeSO
4
7H
2
O(s)) to szomolno-
kite (FeSO
4
H
2
O(s)) is in equilibrium with the aqueous sulphuric
acid phase, has been determined experimentally at 0, 25, 27, 40,
45 and 50 1C [20,21,24,25].
3.2. Enthalpy and heat capacity data
Przepiera et al. [33] measured enthalpies of solution at 25 1C as
a function of H
2
SO
4
additions up to 2 mol/kg. Bhattacharyya and
Bhattacharyya [34] measured enthalpy and heat capacity of H
2
O
FeSO
4
H
2
SO
4
solution at a temperature range of 060 1C. Agde
and Holtmann [35] determined the heat capacity of solution of
H
2
OFeSO
4
H
2
SO
4
from 2545 1C. No enthalpy and heat capacity
data were used for the ternary model in this work because the
enthalpy data have not been taken into account in the modelling
of the binary H
2
SO
4
H
2
O system [10].
3.3. Density of solution
K onigsberger et al. [36] measured densities of the H
2
OFeSO
4

H
2
SO
4
system using high-precision vibrating-tube densimetry
up to 10 mol/kg of H
2
SO
4
at 25 1C. This data were connected to
thermodynamic functions through pressure dependency of the
Gibbs energy function and partial molal volume.
3.4. Raman spectroscopy measurements
Sobron et al. [37] measured H
2
OFeSO
4
H
2
SO
4
solutions with
Raman spectroscopy at 01.65 mol/kg of FeSO
4
. Concentrations of
sulphate, bisulphate and hydrogen ions have been determined in
that work.
4. Parameter optimisation
Evaluation of the thermodynamic properties of the aqueous
phase as well as the condensed ferrous sulphate hydrates was
carried out using the MTDATA
s
assessment module, version 4.81
and MTDATA Studio 5.03, using Harvies modication of the Pitzer
equation [16,17]. The assessment module minimises the weighted
sum of squares of errors between the measured and tted values,
according to Eq. (4). Thus, the objective function (OF) to be
minimised in the parameter optimisation can be written as
OF
X
n
i 1
W
i
C
i
E
i
U
i

2
4
Table 1
Internal parameters (b1.2) of the Pitzer model used in this work.
Parameter 11, 12, 13 and 14 electrolyte 22 electrolyte
a
1
(kg/mol)
1/2
2.0 1.4
a
2
(kg/mol)
1/2
12
P.M. Kobylin et al. / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 38 (2012) 185193 188
where
n is the number of properties (data items) to be reproduced,
C
i
and E
i
are the calculated and experimental values of
property i,
U
i
is the uncertainty associated with value E
i
and
W
i
is the weight assigned to property (data item) i.
4.1. Experimental phase equilibrium data used in the optimisation
The experimental solubility data used in the optimisation at a
temperature range of 0100 1C are shown in Table 2. The H
2
SO
4
concentration upper limit was 10 mol/kg. Details of the experi-
mental data used have been added as supplemental material
including uncertainties of each experiment. In the earlier works
less data were used. Peritectic points and solubility measure-
ments at higher temperatures were used in the validation of the
Pitzer parameters used in this work.
All weights for experimental data were set to 1, with the
exception of rejected values, where 0 was used.
4.2. Thermodynamic data used in the optimisation
The simplied HelgesonKirkhamFlowers (HKF) model
[38,39] was used for the ions (except HSO
4

); see Appendix 1.
Thermodynamic data for HSO
4

were calculated from SO

4
2
data
and the sulphuric acid second dissociation (HSO
4

SO
4
2
H

)
constant K
2
value of Matsushima and Okuwaki [11], from the
equation
log
10
K
2
T,K 577:214246:01 log
10
T
12717
T
0:283133 T
1:37566 10
4
T
2
5
C
p
function of the H
2
O was tted to experimental data from
the literature; see details in Kobylin et al. [9].
The thermodynamic values D
f
H1
298.15
, S1
298.15
and C
p
for ions
and C
p
for FeSO
4
7H
2
O(s), FeSO
4
4H
2
O(s) and FeSO
4
H
2
O(s)
were taken from Sippola [3]. D
f
H1
298.15
, S1
298.15
of FeSO
4
7H
2
O(s),
FeSO
4
4H
2
O(s) and FeSO
4
H
2
O(s) at 25 1C were optimised with
the H
2
OFeSO
4
binary system [9]. The gas phase was assumed to
be ideal.
5. Results and discussion
The temperature dependencies of the Pitzer parameters b
(0)
,
b
(1)
and C
f
for the Fe
2
HSO
4

binary interaction and c for Fe

2

HSO
4

SO
4
2
ternary interaction were optimised in this work
following Sippola [3] with a temperature dependency of A
Pitz

F
Pitz
/T. Reardon and Beckie [2] used a different set of parameters
in their model. The assessed Pitzer parameters (A
Pitz
and F
Pitz
) are
shown in Table 3. The interaction parameters used for H
2
SO
4
H
2
O
Table 3
Assessed Pitzer parameters used in this work. FeSO
4
H
2
O binary parameters from
[9] were used.
A
Pitz
F
Pitz
b
(0)
0.75865 96.8922 Fe
2
(aq)HSO
4

(aq) this work

b
(1)
14.45279 5787.6144 Fe
2
(aq)HSO
4

(aq) this work

C
F
0.00000 3.2097 Fe
2
(aq)HSO
4

(aq) this work

b
(0)
0.04083 20.4876 H

(aq)SO
4
2
(aq) [10]
a
C
F
0.18522 42.794 H

(aq)SO
4
2
(aq) [10]
a
b
(0)
0.02808 54.141 H

(aq)HSO
4

(aq) [10]
a
b
(1)
0.00516 147.759 H

(aq)HSO
4

(aq) [10]
a
c 0.25247 71.407 Fe
2
(aq)HSO
4

(aq)SO
4
2
(aq) this work
a
Okuwaki set A from reference [10] was used in this work.
0.0
0.2
0.4
0.6
0.8
1.0
1.2
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Fig. 6. The calculated solubility data on the system H
2
OFeSO
4
H
2
SO
4
at 140 1C. The predictive feature of the model is demonstrated as no experimental data was used at
this temperature. this work: extrapolated outside the temperature range of the original work; (- - -) Sippola [3]: extrapolated outside the temperature range of the
original work; (- - -) Reardon and Beckie [2]: extrapolated outside the temperature range of the original work; (y) Kobylin et al. [5]: extrapolated outside the
temperature range of the original work; ( ) Bruhn et al. [40] and (~) Hasegawa et al. [31].
Table 2
The experimental data used in the assessment of the H
2
OFeSO
4
H
2
SO
4
ternary
system. H
2
SO
4
cut-off limit was 10 mol/kg.
Experiment Temperature 1C Data points
Solubility of melanterite 055 109/120
a
[2126]
Solubility of szomolnokite 0100 110/153
b
[2125,28]
a
Excluded values: Bullough et al. [24] metastable solubilities at 045 1C
(7 points); Belopolskii et al. [22] values at 45 1C (4 points).
b
Excluded values: Bullough et al. [24] metastable solubilities at 045 1C
(5 point), 7.88 and 9.45 mol/kg of H
2
SO
4
at 25 1C (2 points); Kobe et al. [25] at
100 1C (4 points). In addition Bullough et al. [24] values were the only values
included at 60 1C (32 points were excluded from other authors [21,25,28]).
P.M. Kobylin et al. / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 38 (2012) 185193 189
binary from [10] are also shown in Table 3 and FeSO
4
H
2
O binary
parameters are published in [9].
5.1. Solubility data
The solubility of FeSO
4
in aqueous sulphuric acid solutions was
calculated from 0 to 220 1C, using the optimised properties of this
work from 0 to 100 1C. Calculated solubilities, higher than 100 1C,
are extrapolated. Figs. 18 show the solubility results together
with the experimental points (some of the experimental points
have not been included in assessment; see gure captions for
more details) at 0, 25, 50, 80, 100, 140, 160 and 220 1C, respec-
tively. Data from the earlier thermodynamic modelling studies
[2,3,5,6] have been superimposed in the gures. Model extrapola-
tions of Reardon and Beckie [2] (at 0 1C, above 60 1C and
concentrations higher than 6 mol/kg of H
2
SO
4
), Sippola [3] (above
6.1 mol/kg and 100 1C) and Kobylin et al. [5] (above 100 1C) are
also shown.
From Fig. 1 we can see that Reardon and Beckie [2] set of Pitzer
parameters cannot extrapolate solubilities at higher than 3.5 mol/kg
acid concentrations at 0 1C, and our set of Pitzer parameters is not
able to properly model the chosen data at low acid concentrations
0.0
0.2
0.4
0.6
0.8
1.0
1.2
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Molality of H
2
SO
4
/ molkg
-1
M
o
l
a
l
i
t
y

o
f

F
e
S
O
4

/

m
o
l

k
g
-
1
FeSO
4
H
2
O
Fig. 7. The calculated and experimental solubility data on the system H
2
OFeSO
4
H
2
SO
4
at 160 1C. this work: extrapolated outside the temperature range of the original
work; (- - -) Sippola [3]: extrapolated outside the temperature range of the original work; (- - -) Reardon and Beckie [2]: extrapolated outside the temperature range
of the original work; (y) Kobylin et al. [5]: extrapolated outside the temperature range of the original work and (~) Hasegawa et al. [31].
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Molality of H
2
SO
4
/ molkg
-1
M
o
l
a
l
i
t
y

o
f

F
e
S
O
4

/

m
o
l

k
g
-
1
FeSO
4
H
2
O
Fig. 8. The calculated and experimental solubility data on the system H
2
OFeSO
4
H
2
SO
4
at 220 1C. this work: extrapolated outside the temperature range of the original
work; (- - -) Sippola [3]: extrapolated outside the temperature range of the original work; (- - -) Reardon and Beckie [2]: extrapolated outside the temperature range
of the original work; (y) Kobylin et al. [5]: extrapolated outside the temperature range of the original work and (~) Hasegawa et al. [31].
Table 4
Values of the objective functions of the current set of experimental data. Columns
35 show the calculated objective functions (OF) using thermodynamic data of
other assessments and the experimental data used in this work.
This work [3] [2] [45]
Experiment OF OF OF OF
Solubility of melanterite 050 1C 0.54 0.42 76.32
a
4.73
Solubility of szomolnokite 0100 1C 0.71 1.12 8979.48
b
6.66
Total t 0.63 0.77 4548.23 5.70
a
Value extrapolated outside the temperature range of the original work at 0
and 5 1C.
b
Value extrapolated outside the temperature and concentration range of the
original work.
P.M. Kobylin et al. / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 38 (2012) 185193 190
(0.13 mol/kg H
2
SO
4
). Kobylin et al. [5] set of Pitzer parameters
have problems in modelling the solubility of melanterite at 0
50 1C temperatures and low acid concentrations (see Figs. 13). As
can be seen in Figs. 4 and 5, the Reardon and Beckie model cannot
predict the solubilities at temperatures higher than 60 1C, while
Kobylin et al. [5], Sippola [3] and this work calculate well the
solubilities at 80 and 100 1C. An interesting feature of slight
increase of solubility with increasing sulphuric acid concentration
from 0.5 to 2 mol/kg of H
2
SO
4
can be seen in Fig. 5. Przepiera [6]
set of Pitzer parameters do not really follow experimental mea-
surements and only give rough estimates of the solubility data at
temperatures other than 25 1C. This maybe due to the fact that the
data is optimised up to 30 mol/kg of H
2
SO
4
.
The objective functions of the four models have been com-
pared (see Table 4). As can be seen from the table there is not
much difference between the OF value of Sippola [3] model and
that of this work (0.77 and 0.63, respectively). OF which is
calculated using Kobylin et al. [5] Pitzer parameters is also
reasonably good while the Reardon and Beckie [2] model, which
has been referred in many publications, cannot be used outside its
concentration (06 mol/kg) and temperature (1060 1C) range
which can be seen also from the large OF value.
The solubilities have also been calculated at 140 1C where
ternary solubility data are not available (see Fig. 6). As can be seen
the binary solubility is best calculated using this work while the
values of Sippola [3], Reardon and Beckie [2] and Kobylin et al. [5]
deviate from that value. Solubility measurements by Hasegawa
Table 5
Comparison of the calculated and measured peritectic points (transition of FeSO
4
7H
2
O(s) to FeSO
4
H
2
O(s)) at 0,25 and 50 1C in the system FeSO
4
H
2
SO
4
H
2
O.
t0 1C t25 1C t50 1C
m(H
2
SO
4
) m(FeSO
4
) m(H
2
SO
4
) m(FeSO
4
) m(H
2
SO
4
) m(FeSO
4
)
mol/kg mol/kg mol/kg mol/kg mol/kg mol/kg
7.78 0.38 5.28 1.13 1.31 2.93 This
work
7.20 0.08 5.18 1.09 1.31 2.78 [2]
8.06 0.30 5.26 1.13 0.96 2.97 [3]
8.21 0.31 5.19 1.17 0.97 3.10 [4,5]
6.79 0.38 4.60 1.14 [20]
1.38 2.85 [21]
a
7.81 0.32 5.13 1.15 [24]
7.37 0.41 [25]
a
According to Belopolskii and Shpunt [21] this phase transition point is
between FeSO
4
4 H
2
O(s) and FeSO
4
H
2
O(s).
0
50
100
150
200
250
300
0 50 100 150 200 250
Temperature / C
M
a
s
s

o
f

F
e
S
O
4

d
i
s
s
o
l
v
e
d

/

g
FeSO
4
7H
2
O
FeSO
4
H
2
O
All FeSO
4
0
50
100
150
200
250
300
0 50 100 150 200 250
Temperature / C
M
a
s
s

o
f

F
e
S
O
4

d
i
s
s
o
l
v
e
d

/

g
FeSO
4
7H
2
O
FeSO
4
H
2
O
All FeSO
4
Fig. 9. (a and b) Amount of FeSO4 dissolved when temperature is increased in FeSO
4
H
2
O (a) and FeSO
4
H
2
SO
4
H
2
O (b) systems. this work; (- - -) Sippola [3]; (- - -)
Reardon and Beckie [2]; (y) Kobylin et al. [5]. Initial concentrations are 250 g of FeSO
4
per kg of H
2
O in both systems and H
2
SO
4
addition is 300 g in the ternary system.
P.M. Kobylin et al. / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 38 (2012) 185193 191
et al. [31] at 160220 1C have been used for validation of the
models and this work, Sippola [3] and Kobylin et al. [5] and are
reproducing the measurements quite well up to the highest
sulphuric acid and ferrous sulphate concentrations of 0.5 and
0.58 mol/kg, respectively, while Reardon and Beckie fail in the
extrapolations (see Figs. 7 and 8).
The peritectic point, FeSO
4
7H
2
O(s)FeSO
4
H
2
O(s) transition,
was calculated using the model and compared to literature
measurements to further validate different Pitzer models (see
Table 5). There is deviation in the molality of H
2
SO
4
at peritectic
points in the literature at 0 1C. According to Cameron [20],
molalities of H
2
SO
4
and FeSO
4
are 6.79 and 0.38 mol/kg, while
Bullough et al. [24] have 7.81 and 0.32 mol/kg, respectively. Our
calculated point 7.78 and 0.38 is between the measured values,
while Sippola [3] has molalities of 8.06 and 0.3 mol/kg that are
outside the measured values. The model of Reardon and Beckie
gives too low FeSO
4
concentration of 0.08 mol/kg as also seen in
Fig. 1. All model results are rather close to Bullough et al. [24] 5.13
and 1.15 mol/kg value at 25 1C while Cameron measured smaller
acid concentration 4.6 mol/kg. This work and Reardon and Beckie
values at 50 1C are close to the experimental value by Belopolskii
and Shpunt [21] while Kobylin et al. [5] and Sippola [3] models
calculate little lower acid concentrations and higher FeSO
4
concentrations.
5.2. Example on how to use the model
Here it is demonstrated how this thermodynamic model can
be used in predicting the behaviour of process solution. For
example if there is process solution with 250 g FeSO
4
and
1000 g of water and system is heated the dissolution of FeSO
4
in the solution is changed according to Fig. 9a (binary system) and
b if 300 g of H
2
SO
4
is added to the solution (ternary system). Also
shown are results of other models. As can be seen the behaviour
of the solutions is different when acid is added. An interesting
feature is observed at temperatures higher than 100 1C where due
to domination of bisulphate ion addition of sulphuric acid will
increase solubility of FeSO
4
.
6. Conclusions
In this work, the earlier models were carefully compared for
the solubility data. The current model presents the experimental
data available with a good accuracy and consistently up to 100 1C,
and sulphuric acid concentrations up to 10 mol/kg. The model
also predicts the solubilities between 100 and 160 1C, where
experimental data are not available. The solubility measurements
available in dilute solutions only by Hasegawa et al. [31] at 160
220 1C, which were used for validation of this model, have been
reproduced well up to the highest sulphuric acid and ferrous
sulphate concentrations of 0.5 and 0.58 mol/kg, respectively. The
model has limitations at temperatures higher than 100 1C due to
lack of experimental data.
Due to the lack of experimental data, the heat capacity of
crystalline FeSO
4
H
2
O(s) should be measured on a wide tem-
perature interval, preferably from 0 to 500 K. More solubility
measurements of FeSO
4
in sulphuric acid solution at higher
temperatures, above 100 1C, are also needed to ensure the correct
saturation line. There is also a need to make water activity and
vapour pressure measurements at moderate to high temperatures
to improve the current model in the areas of industrial processes.
A new evaluation of the D
f
G1
298.15
, S1
298.15
, D
f
H1
298.15
and C
p
values of Fe
2
ion is also needed.
Acknowledgements
The authors would like to acknowledge the nancial support
provided by Technology Industries of Finland Centennial Foundation.
Appendix A. Thermodynamic properties of ions
Enthalpy of formation and standard entropy of ions were taken
from the literature (see Table A.1). The heat capacities of the ions
were estimated using a simplied HKF model. According to the
HKF model; see Table A.2. [9,42]
Appendix B. Supplementary material
Supplementary data associated with this article can be found
in the online version at http://dx.doi.org/10.1016/j.calphad.2012.
06.011.
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SO
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Ion D
f
H1
298.15
/J mol
1
S1
298.15
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K
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H

(aq) 0.0 0.00 By denition

OH

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Fe
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(aq) data
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SO
4
2
ion.
Ion T
max,
K A B C10
3
D10
5
OH

(aq) 343.15 21245.30 84.1929 93.5145 4083.14

448.15 5250.28 20.4720 23.0421 985.66
Fe
2
(aq) 328.15 14279.40 57.8948 65.9339 2588.70
413.15 1363.44 6.4203 8.5393 165.15
448.15 3170.88 5.6005 0.0000 1585.87
SO
4
2
(aq) 328.15 46200.60 186.8004 211.9290 8546.29
403.15 1080.77 0.7188 3.9917 676.58
448.15 5857.78 10.7722 0.0000 2907.89
HSO
4

(aq) 328.15 48246.05 197.6415 227.7310 8546.29

403.15 3126.22 11.5599 11.8103 676.58
448.15 7903.23 21.6133 15.8020 2907.89
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SO
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