Fluid Phase Equilibria 396 (2015) 43–49

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Fluid Phase Equilibria

j o u r n a l h o m e p a g e : w w w . e l s e v i e r . c o m / l o c a t e / fl u i d

Properties of fluoride in wet phosphoric acid processes: Fluorosilicic

acid in an aqueous solution of H2SiF6–H20 at temperatures ranging
from 298.15 K to 353.15 K
Mohamed El Guendouzi * , Ahmed Rifai, Mourad Skafi
Laboratoire de Chimie Physique, URAC17, Faculty of Sciences Ben M'Sik, University of Hassan II – Casablanca, B.P. 7955, Casablanca, Morocco

A R T I C L E I N F O A B S T R A C T

Article history: The properties of fluoride in wet phosphoric acid processes were of interest us to understand the
Received 10 February 2015 processes and roles that fluorosilicic acid plays in phosphoric acid solutions. The literature data indicate
Received in revised form 2 March 2015 that some deficiencies exist in the thermodynamic properties of hexafluorosilicic acid aqueous solutions.
Accepted 8 March 2015
In this investigation, the water activity and osmotic coefficients of H2SiF6(aq) were determined in the
Available online 11 March 2015
temperature range from T = 298.15 to 353.15 K. The measurements of the water activity were performed
at molalities from 0.10 to 3.00 mol kg
1 of H2SiF6(aq) using the hygrometric method. The modelling
Keywords:
approach based on the Pitzer model was developed to determine the thermodynamic properties. From
Fluorosilicic acid
Water activity
these measurements, the ion interaction parameters in binary solution were evaluated at different
Osmotic coefficient temperatures ranging from 298.15 K to 353.15 K and were used to predict the solute activity coefficients.
Ion interaction parameters The development of a model for solution behaviour was also employed to determine the excess molal
Excess thermodynamic properties Gibbs energy, enthalpy, entropy and heat capacity of the H2SiF6 aqueous solution within the temperature
range from 298.15 K to 353.15 K.
ã 2015 Elsevier B.V. All rights reserved.

1. Introduction solution is distributed between the phosphoric acid and the

The production of phosphoric acid is directly related to world
phosphate fertilizer consumption, which continues to increase [1].
Phosphoric acid for use in fertilizer applications is mainly
produced by wet processes. In these processes, phosphate ore is
digested by a mixture of sulphuric and phosphoric acids and large
amounts of hydrated calcium sulphate are precipitated as a
by-product. The phosphate ore is mainly fluoroapatite
(Ca10(PO4)6F2), with some additional compounds, such as calcite,
quarts, and clay.
Fluoroapatite contains approximately 4% fluoride [2]. During its
digestion by phosphoric acid, fluoride is released as hydrogen
fluoride, which reacts with the silica present in the ore or added as
clay, to form a fluorosilicic acid solution in the phosphoric acid.
Some of the fluorosilicic acid precipitates during the production
process with sodium or potassium ions or as more complex
compounds [3]. The remaining fluorosilicic acid in the phosphoric
acid partly decomposes as SiF4 and HF. The residual fluoride in
* Corresponding author.
E-mail addresses: elguendouzi@yahoo.fr, m.elguendouzi@gmail.com
(M.E. Guendouzi).
by-product during its precipitation [4].
During the formation of the acid and fluorosilicate, as its
concentration increases, solid-based compounds, such as Na2SiF6,
K2SiF6, CaSiF6, and MgSiF6, are formed in turn by inducing the
problem of fouling. Reactors, pumps, and pipes are clogged by the
solids, which causes disruptions in the production chain. The
elimination of these contaminants is performed either by cleaning
or by changing the reactors [5,6].
The valuation and resolution of some of the problems
encountered in the industrial production of phosphoric acid
are of interest to us, such as dirt and derivatives that allow better
production yields of phosphoric acid and the valuation of the
derivatives. The knowledge of the physical–chemical properties
of compounds and their mixing allows a better understanding of
the mechanisms governing such complex thermodynamic equi-
libria.
The presence of fluoride in phosphoric acid not only makes this
acid more corrosive, but it also makes it unsuitable for fertilizer
applications if the concentration is too high. Fluoride also causes
precipitation of the compounds as chuckrovite. The removal of
fluoride from the phosphoric acid is an industrial need, and control
of the concentration of the fluoride to be released into the air is
critical for the protection of the environment [4].

http://dx.doi.org/10.1016/j.fluid.2015.03.014
0378-3812/ ã 2015 Elsevier B.V. All rights reserved.
44 M.E. Guendouzi et al. / Fluid Phase Equilibria 396 (2015) 43–49

Moreover, phosphate fertilizer plants produce a particular 2. Methods and materials

type of effluent, characterised by its aggressiveness and its
composition. This effluent is highly acidic and contains high
amounts of both fluoride and phosphate [7,8], in addition to
variable contents of other species, mainly sodium, calcium,
chloride and sulphate. The presence of fluoride at acidic pH
makes this wastewater aggressive towards skin, laboratory
glassware and various metallic materials [9]. The fluoride
present in such wastewater is commonly of two forms:
hydrofluoric acid (HF) and hexafluorosilicic acid (H2SiF6)
[3,4,10]. During the acidulation of phosphate rock (fluorapatite
containing 3–4% fluoride and 3–5% SiO2) to produce phosphoric
acid or superphosphates (single and triple), fluoride is released
as hydrofluoric acid, which in turn reacts with silica, forming
the volatile gas silicon tetrafluoride (SiF4) and hydrosoluble
hexafluorosilicic acid (H2SiF6). Both HF and H2SiF6 are partially
carried in the wastewater from gaseous waste scrubbing and
phosphogypsum transportation, which are performed during
the processing of phosphate rock. The thermodynamic proper-
ties of fluorosilicic acid and/or the by-products generated
during production are important, especially if the conditions of
the study are similar to that of the production.
Hexafluorosilicic acid and its sodium salts are the most
commonly used compounds for drinking water supply fluoridation
[11–13]. The pH of a water supply may be adjusted by various
hydroxides to neutralize the hexafluorosilicate anion in potable
water supplies. Upon dilution, the hexafluorosilicate anion releases
fluoride ion and dissociates, producing soluble aquo-hydroxo and
oxosilicates. Their speciation is complicated, with a number of
polymeric species observed.
The literature indicates that some deficiencies exist in our
understanding of the speciation of hexafluorosilicic acid. The
experimental thermodynamic data of the fluorosilicic acid
aqueous solution are not available in the literature. Moreover,
few studies have been performed for these electrolyte solutions in
this field at different temperatures [14]. The main objectives of this
study are: (1) determination of the water activity and osmotic
coefficients of the binary solution of H2SiF6–H2O within the
temperature range from T = 298.15 to 353.15 K on the basis of
hygrometric measurements; (2) development of a thermodynamic
model for the solution behaviour at different temperatures ranging
from 298.15 to 353.15 K; and (3) evaluation of excess thermody-
namic functions of the aqueous solution H2SiF6 (aq).
The water activity was determined using the hygrometric
method, which has been previously described [15]. The apparatus
used in this study solution is based on the measurement of the
relative humidity over an aqueous solution containing non-volatile
electrolytes. For the water activity measurements of these
electrolytes at different temperatures ranging from 298.15 to
353.15 K, the apparatus was modified and adapted to these
conditions at elevated temperatures (relatively) from 298.15 to
353.15 K [16]. The apparatus used is a hygrometer, in which a
droplet of salt solution is maintained on a thin thread. The droplets
of a reference solution of NaCl(aq) are deposited on the spider-thin
thread by pulverization. This thread is kept tense over a perspex
support, which is fixed to a cup containing the selected solution to
be studied. The cup is then placed in a thermostatted box. The
apparatus was held at a constant temperature, and at standard
pressure P. The temperature was controlled to within 0.1 K. The
diameter measurement of the previously calibrated droplet allows
for the determination of the water activity of aqueous solutions.
The droplet diameter was measured by a microscope with an
ocular equipped with a micrometric screw. The relative humidity
was equivalent to the water activity aw in our experiments. The
uncertainty in the water activity depends on the accuracy of the
diameter measurements and is therefore less than 0.02 per cent
for aw > 0.97, 0.05 per cent for 0.97 > aw > 0.95, 0.09 per cent for
0.95 > aw > 0.90 and 0.2 per cent for aw < 0.90.
The reference solutions of NaCl were prepared from crystalline
material (extrapur-grade chemicals, mass fraction > 0.99) and
deionized distilled water. The studied solutions were prepared
by the dissolution of H2SiF6 at 34%, analytical grade compounds
Riedel de-Haën (Sigma–Aldrich) and deionized distilled water
(conductivity <5 mS m
1) at 298.15 K. The purity of H2SiF6 at 34% is
99.98%; the density is d20 = 1.30 and the molar mass is 144.09 g
mol
1. The molality is prepared at the considered value and its
uncertainty is 0.01 mol kg
1.
3. Results and discussion
3.1. Water activity and the osmotic coefficient
Binary aqueous solutions of fluorosilicic acid were studied using
the hygrometric method in the temperature range from 298.15 to

Table 1
Water activities, osmotic and activity coefficients of the binary aqueous solutions of fluorosilicic acid H2SiF6–H2O as function of molality m at temperatures from 298.15 to
353.15 K, at standard pressure P.

T (K) 298.15 313.15 333.15 353.15

m/ aw f g aw f g aw f g aw f g
mol kg
1
0.10 0.9947 0.983 0.714 0.9949 0.946 0.518 0.9956 0.816 0.472 0.9964 0.667 0.250
0.20 0.9888 1.042 0.766 0.9894 0.986 0.584 0.9910 0.836 0.425 0.9945 0.510 0.175
0.50 0.9688 1.173 0.959 0.9706 1.104 0.785 0.9744 0.960 0.433 0.9806 0.725 0.132
0.80 0.9453 1.301 1.213 0.9481 1.233 0.927 0.9527 1.121 0.517 0.9588 0.972 0.143
1.00 0.9275 1.393 1.434 0.9307 1.329 1.074 0.9354 1.236 0.603 0.9413 1.118 0.163
1.20 0.9072 1.502 1.698 0.9119 1.422 1.415 0.9166 1.343 0.723 0.9229 1.237 0.188
1.50 0.8750 1.647 2.266 0.8798 1.580 1.867 0.8829 1.536 0.949 0.8897 1.442 0.252
1.80 0.8385 1.811 3.046 0.8430 1.756 2.700 0.8449 1.733 1.282 0.8535 1.628 0.340
2.00 0.8122 1.924 3.738 0.8169 1.871 3.350 0.8189 1.848 1.579 0.8256 1.773 0.420
2.20 0.7861 2.024 4.591 0.7893 1.990 4.025 0.7908 1.974 1.949 0.7971 1.907 0.519
2.50 0.7411 2.218 6.360 0.7449 2.180 5.233 0.7464 2.165 2.711 0.7501 2.128 0.729
2.80 0.7018 2.340 8.848 0.6983 2.373 6.766 0.7000 2.357 3.791 0.7028 2.331 1.025
3.00 0.6644 2.522 11.067 0.6668 2.500 7.833 0.6683 2.486 4.756 0.6717 2.454 1.291

Expanded uncertainty of temperature is 0.1 K; molality uncertainty is 0.01 mol kg
1. The uncertainty is less than 0.02% for aw > 0.97, 0.05% for 0.97 > aw > 0.95, 0.09% for
0.95 > aw > 0.90 and 0.2% for 0.90 > aw. Uncertainty of osmotic coefficient f is estimated to be, at most 0.005. (N = 13) number of experimental data points (each point is the
average of 8–10 series of experiments).
 M.E. Guendouzi et al. / Fluid Phase Equilibria 396 (2015) 43–49 45
[(Fig._1)TD$IG] [(Fig._2)TD$IG]

Fig. 1. Water activities aw of H2SiF6–H2O, as function of molality m at temperatures

ranging from 298.15 to 353.15 K; , 298.15 K; ^, 313.15 K; &, 333.15 K; +, 353.15 K.

353.15 K. The measurement of the water activities of H2SiF6(aq)

was performed at molalities from 0.10 to 3.00 mol kg
1 and from Fig. 2. Osmotic coefficient f of H2SiF6(aq), as a function square root of the ionic
298.15 to 353.15 K. The experimental data are presented in Table 1 strength I1/2 in the temperature range from 298.15 to 353.15 K; , 298.15 K; ^,
and Fig. 1. According to Fig. 1, the behaviour of the water activity 313.15 K; &, 333.15 K; +, 353.15 K.

depends on the molality and temperature and decreases with

The osmotic coefficient data sets are determined directly from
increasing concentration. This behaviour is due to the reduction of
the hygrometric measurements and used in Eq. (1) (with
the vapour partial pressure of water relative to pure water, which
1-2 charge type) of the fluorosilicic acid solutions in the
causes an increase in the number of molecules of free water from
temperature range from 298.15 to 353.15 K (see Table 1 and Fig. 2).
the liquid state to the vapour state. The water activity increases as
the temperature increases from 298.15 to 353.15 K as follows
3.2. Binary parameters and activity coefficient
aw 353.15 K > aw333.15 K > aw313.15 K > aw298.15 K.
In the solution, increasing molality causes a deviation from
The ion interaction model [17] has been successful in describing
ideality. The water molecules under the influence of ion–dipole
the osmotic coefficient results. The osmotic coefficients of
interactions are divided into two types. Bound water molecules
1-2 electrolyte solutions are given by Eqs. (3–6)
are directly subjected to the electric fields of ions, and free

 " #
water molecules are not affected by these fields. Therefore, 2na nc ðna nc Þ3=2 f
when the concentration increases, the number of free water f ¼ 1 þ jZa Zc jf f þ mBf þ 2m2 C ; (3)
n n
molecules decreases and the proportion of water molecules
f
passing to the vapour state reduces along with the correspond- where f is the long-range electrostatic term, defined as
ing water activity.
Using the obtained experimental results of the water activity, f
Af I1=2
f ¼ : (4)
the osmotic coefficients of the water were evaluated by Eq. (1), ð1 þ 1:2I1=2 Þ

1000
f¼
vi mi lnaw : (1) f
Mw Si The second virial coefficient BMX is given by
where ni is the number of ions released by dissociation, mi is the
BfMX ¼ b
ð0Þ ð1Þ
þb expð
aI1=2 Þwitha ¼ 2 (5)
molality of solute I, and Mw is the molar mass of water.
Generally, the release of fluoride, as a chemical gas in the form
of SiF4 and HF, can be absorbed in water to give a fluorosilicic acid Af is the Debye–Hückel coefficient (defined as a dimensionless
solution [1,4]. The activities of the volatile SiF4 and HF compounds quantity) for the osmotic coefficient and b(0), b(1), and Cf are the
in the liquid phase are both assumed to be negligible compared to ion interaction parameters, which are functions of the temperature
the activity of SiF62
at a molar F/Si ratio of six, which has to be and pressure. For the single-electrolyte solution of anion “a” and
maintained in the liquid phase if a release maximal fluoride is cation “c”, Za and Zc are the charge numbers of the anion and cation,
pursued. The fluoride is therefore assumed to only be present as respectively, and na and nc are the total number of anions and
SiF62
in the liquid phase. Fluorosilicic acid is a strong acid and is cations per mole of the electrolyte produced by dissociation of one
assumed to be completely dissociated into SiF62
and H+ in pure molecule, respectively.
water [1]. Thus, except under very acidic conditions, the dominant The ionic strength I is given by the usual definition.
form in solution is the hexafluorosilicate ion. Therefore, the
X
1
equilibrium reaction is generally considered to be similar to the I¼ mi z2i (6)
2 i
form given in Eq. (2). From the equilibrium, the system was
considered a 1-2 charge type.
The corresponding values of the ion parameters b(0), b(0) and Cf
H2 SiF6 ðaqÞ ! 2Hþ ðaqÞ þ SiF2

6 ðaqÞ (2) of the pure electrolytes H2SiF6 (aq) were obtained from Pitzer's
46 M.E. Guendouzi et al. / Fluid Phase Equilibria 396 (2015) 43–49

Table 2
Ion interaction parameters b(0), b(1), C(f) of the binary system H2SiF6–H2O in the temperature range from 298.15 to 353.15 K.

T (K) b(0) b(1) C(f) sf Af

(kg mol
1) (kg mol
1) (kg2 mol
2)
298.15 0.4981  0.0029 4.027  0.066
0.00006  0.000005 0.0034 0.3930
313.15 0.4837  0.0022 3.313  0.037 0.00124  0.00001 0.0031 0.4023
333.15 0.4986  0.0031 0.302  0.069 0.00003  0.000001 0.0019 0.4190
353.15 0.5089  0.0027
4.443  0.018 0.00001  0.000003 0.0027 0.4384

Expanded uncertainty of temperature is 0.1 K. The uncertainty of parameters is calculated for each temperature.
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
s f ¼ Sðfobs N
1

fth Þ2
N is number of experimental data points.

expressions by the fits of the experimental osmotic coefficients. H2SiF6(aq) as a function of the ionic strength I1/2 and within
The uncertainty of the parameters is calculated for each tempera- the temperature range from 298.15 to 353.15 K are shown in
ture, and the standard deviation of the fit s (f) is also given in Fig. 3.
Table 2. At the same temperature, Fig. 3 shows that the activity
Eqs. (7–10) give the expressions for the activity coefficients coefficients increase slightly at a dilute-moderate concentration
g as and increase greatly in concentrated solutions of H2SiF6. At the

 " # same concentration, with increasing temperature from 298.15 K
g 2na nc 2ðna nc Þ3=2
lng ¼ jZ a Z c jf þ mBg þ m2 C g ; (7) to 353.15 K, the activity coefficients decrease in the following
n n order: g 353.15 K < g 333.15 K < g 313.15 K < g 298.15 K.
where the long-range electrostatic term, fg , is given by
" # 3.3. Excess heat capacity, enthalpy, entropy and Gibbs energy
g I1=2
f ¼
Af (8)
ð1 þ 1:2I1=2 Þ þ ð2=1:2Þlnð1 þ 1:2I1=2 Þ 3.3.1. Approach theory
The thermodynamic properties of aqueous solutions at
g different temperatures are of major importance in many
BMX is defined as.
geochemical and industrial processes [18]. In addition to the
!
2b
ð1Þ j   k osmotic and activity coefficients and excess Gibbs energy, there is
g ð0Þ
BMX ¼ b þ 1
exp
a2 I1=2 1 þ a2 I1=2 (9) significant interest in the excess enthalpy and heat capacity of
a
2 I 1=2
fluorosilicic acid aqueous solutions. Nevertheless, these excess
g f thermodynamic functions of H2SiF6(aq) are not available in the
and C MX is related to C MX by
literature.
g 3 f In this section, the excess molar enthalpy, entropy, Gibbs
C MX ¼ C MX (10)
2 energy, and heat capacity of H2SiF6 aqueous solutions were
evaluated in the temperature range from 298.15 to 353.15 K. The
Using ion interaction parameters b(0), b(1) and Cf, the determination of these thermodynamic functions allows effec-
solute activity coefficients are calculated by Eq. (7) and given in tive interaction of the solute in aqueous solutions. In the
Table 1. The predicted solute activity coefficients g of construction of the temperature-variation model, the binary
parameters for H2SiF6(aq) are evaluated as a function of the
temperature. The osmotic and activity coefficients can be used
[(Fig._3)TD$IG] to represent the apparent molar properties of solutions
depending on the temperature and pressure, such as the
enthalpy and heat capacity. The determination of the apparent
10.00
magnitudes requires the calculation of the first and second
partial derivatives of the ion interaction parameters b(0), b(1)
and Cf of the fluorosilicic acid solution. Temperature depen-
8.00 dence for the binary ion interaction parameters is built into the
model to predict the ion parameters BL and CL of the apparent
γ
molar enthalpy and BJ and CJ of the apparent molar heat
6.00
capacity. Second, the calculated ion parameters are used in
semi-empirical Eqs. (11–26) to evaluate the excess enthalpy,
4.00 Gibbs energy, entropy and heat capacity.
Differentiation of the Gibbs energy, osmotic and activity
coefficient equations with respect to temperature and pressure
2.00 can be used to derive the equations needed to represent the
apparent molar properties of solutions. The equations are
given by:
0.00
0.00 0.50 1.00 1.50 2.00 2.50 3.00

0  . 1
-1 1/2
{ I(mol.kg ) }

2@
@ Gex
Fig. 3. Activity coefficient g of H2SiF6(aq), as a function square root of the ionic 
L ¼ H
H ¼
T T A (11)
strength I1/2 at temperatures ranging from 298.15 to 353.15 K; , 298.15 K; ^, @T
P;m
313.15 K; &, 333.15 K; +, 353.15 K.
 M.E. Guendouzi et al. / Fluid Phase Equilibria 396 (2015) 43–49 47

Table 3
i
Least squares estimated coefficients bj of H2SiF6–H2O within the temperature range from 298.15 to 353.15 K.

Ion interaction parameters i

b1
i
b2
i
b3
i
b4
b (0)

11.82  0.09 6.06  0.001
7.82  0.08 0.88  0.002
b(1)
12.79  0.16 45.35  0.16
113.86  2.81
12.57  0.03
(f)
C 1.37  0.03
0.69  0.003 0.91  0.03
0.09  0.0004

Values of uncertainties were evaluated using error propagation.

Table 4
ð0ÞL ð1ÞL ð0ÞJ ð1ÞJ
Calculated parameters bMX ,bMX , C LMX , bMX , bMX and C JMX of H2SiF6–H2O at temperatures ranging from 298.15 to 353.15 K.

T (K) bð0ÞL
MX bð1ÞL
MX
C LMX bð0ÞJ
MX bð1ÞJ
MX
C JMX
298.15 0.0129  0.00001
0.2113  0.0007
0.00138  0.00002
0.00015  0.00009
0.0024  0.0013 0.00002  0.00001
313.15 0.0107  0.0001
0.2468  0.0018
0.00112  0.00003
0.00015  0.00007
0.0024  0.0008 0.00002  0.000003
333.15 0.0077  0.0001
0.2938  0.0029
0.00077  0.00005
0.00015  0.00004
0.0023  0.0005 0.00002  0.000003
353.15 0.0046  0.0001
0.3406  0.0040
0.00041  0.00006
0.00015  0.00003
0.0023  0.0003 0.00002  0.000001

Expanded uncertainty of temperature is 0.1 K. Values of uncertainties were evaluated using error propagation.


 ! !
@H  @L @2 bð0Þ 2 @bMX
ð0Þ
Cp ¼ ¼ Cp þ (12) andb
ð0ÞJ
¼ MX
þ (20)
@T P;m @T P;m
MX
@T 2 T @T
P P
The relative apparent molar enthalpy Lf is

   ! !
AL
Lf ¼ njZ M Z X j @2 bð1Þ ð1Þ
1
ln 1 þ bI2 2 @bMX
2:4
h i bð1ÞJ
MX ¼
MX
þ (21)
@T 2 T @T

2nM nX RT 2 mBLMX þ m2 ðnM Z M ÞC LMX (13) P P

!

h i @2 CMX 2 @C MX
bð0ÞL ð1ÞL
MX þ 2bMX 1
ð1 þ aI
1=2
Þexpð
aI1=2 Þ C JMX ¼ þ (22)
whereBLMX ¼ (14) @T 2 T @T P
P
ða2 IÞ
The excess Gibbs energy Gex, enthalpy Hex, entropy Sex, and the heat
capacity, C ex
P of the solution are determined by Eqs. (23–26):
" #
ð0ÞL @bð0Þ Gex ¼ nmRTð1
f þ l ng Þ;
withbMX ¼ MX
(15) (23)
@T P

Hex ¼ mLf ; (24)

" ð1Þ
#
@b
bð1ÞL
MX ¼
MX
(16)
@T P
Hex
Gex
Sex ¼ ¼ mLf
nmRTð1
f þ l ng Þ; (25)
T
f
½@C MX =@TP
C LMX ¼ (17) 
ð2jZ M Z X j1=2 Þ C ex
P ¼ mðC p;f
C p;f Þ: (26)
b(0), b(1) and Cf are the ion interaction parameters. AL is the
Debye–Hückel constant for the apparent molar enthalpy. The
apparent molar heat capacity, CP,f is also defined by
3.3.2. Evaluation of the ion parameters as a function of temperature

  
 AJ The ion interaction parameters b(0), b(1) and Cf calculated
C P;f ¼ C P;2 þ njZ M Z X j ln 1 þ bI1=2
h 2b i within the temperature range from 298.15 to 353.15 K are

2nM nX RT 2 mBJMX þ m2 ðnM Z M ÞC JMX (18) expressed by Eqs. (27) and (28) [19]:
f ð1; TÞ ð1Þ f ð2; TÞ f ð3; TÞ
andC f ¼

C P;2 is the standard of molar heat capacity of the solute and bð0Þ ¼ ;b ¼ (27)
m0 m0 m20
AJ is the Debye–Hückel constant for the apparent molar heat
capacity,

2
ðT
T r Þ

5 i T
T r
! f ði; TÞ ¼ b1 þ 10
2 b2
i i

 þ 10 b
@ BMX
2
2 @BMX T0 !
3
T0 !3
BJMX ¼ þ 0 2
@T 2 T @T P b
i
3 i T 6 i T0
P h i þ 102 4
þ 10 b5 þ 10 b6 (28)
bð0ÞJ ð1ÞJ
þ 2bMX 1
ð1 þ aI1=2 Þexpð
aI1=2 Þ T
225 T T
225
MX
¼ (19)
ða2 IÞ m0 = 1 mol kg
1, T0 = 1 K and Tr = 298.15 K
48 M.E. Guendouzi et al. / Fluid Phase Equilibria 396 (2015) 43–49
[(Fig._4)TD$IG]
20 700

600
0

500
G (kJ mol ) -20

H (kJ mol )
-1

-1
400

-40

ex
ex

300

-60
200

-80
100

-100 0
0,00 0,50 1,00 1,50 2,00 2,50 3,00 3,50 0,00 0,50 1,00 1,50 2,00 2,50 3,00 3,50
-1 -1
m ( mol kg ) m ( mol kg )

10.000

1.500

Cp (J. K (mol kg) )

-1
8.000
S (J. K (mol kg) )
-1

1.000 6.000
-1
-1

ex
ex

4.000

500

2.000

0 0
0,00 0,50 1,00 1,50 2,00 2,50 3,00 0,00 0,50 1,00 1,50 2,00 2,50 3,00
-1 -1
m ( mol kg ) m ( mol kg )

Fig. 4. Excess Gibbs energy G , enthalpy H , entropy Sex and heat capacity C ex
ex ex
P of H2SiF6–H2O as a function of molality m within the temperature range from 298.15
to 353.15 K; , 298.15 K; ^, 313.15 K; &, 333.15 K; +, 353.15 K.

The coefficients b (i, j) are estimated by means of the least 4. Conclusion

squares method (Table 3). Thus, the first and second derivatives
of the virial parameters are used to evaluate the ion interaction In this investigation, binary aqueous solutions of fluorosilicic
parameters b(0)L, b(1)L, CL, b(0)J, b(1)J and CJ that are designed, acid were studied at different temperatures ranging from
respectively, for the apparent molar enthalpy and heat T = 298.15 to 353.15 K. The water activities were measured at
capacity (Table 4). The uncertainties of the values are also molalities from 0.10 to 3.00 mol kg
1 of H2SiF6–H2O using the
estimated using error propagation theory and are given in hygrometric method. From these measurements, the osmotic
Tables 3 and 4. coefficients were determined in the temperature range.
In constructing the model of the H2SiF6–H2O system within the
3.3.3. Evaluation of the excess heat capacity, enthalpy, Gibbs energy temperature range from 298.15 to 353.15 K, single electrolyte
and entropy parameters (b(0), b(1) and Cf) were adjusted to fit the obtained
The ion parameters b(0)L, b(1)L, CL, b(0)J, b(1)Jand CJ of the osmotic coefficients data. The standard for the 1-2 type of
apparent molar enthalpy Lf and heat capacity CP,f for H2SiF6(aq) in electrolytes approach with three b(0), b(1), and Cf single electrolyte
the temperature range from 298.15 to 353.15 K were evaluated ion interaction parameters shows very good agreement with the
(Table 4). They can be employed (Tables 2–4) using Eqs. (11–26) to osmotic coefficients data. Using these parameters in binary
calculate the excess Gibbs energy Gex, enthalpy Hex, entropy Sex and aqueous solutions, the solute activity coefficients were calculated
heat capacity C exP . The excess thermodynamic properties are at temperatures from 298.15 to 353.15 K.
plotted against the molality in Fig. 4. Based on the figure, Hex, A model based on Pitzer ion interaction was also developed to
Sex and C exP increase with the increase of the molality. This calculate the excess thermodynamic properties using the ion
behaviour is more pronounced in concentrated solutions. These parameters BL and CL of the apparent molar enthalpy and BJ and CJ
excess thermodynamic functions become more important at of the apparent molar heat capacity. These parameters were used
elevated temperature. However, the excess Gibbs energy increases to determine the excess Gibbs energy, enthalpy, entropy and heat
slightly with increased molality at first (m = 1 mol kg
1) and then capacity of aqueous solutions of fluorosilicic acid within the
decreases with further increases in the molality. temperature range from 298.15 to 353.15 K.
 M.E. Guendouzi et al. / Fluid Phase Equilibria 396 (2015) 43–49
The thermodynamic properties are of fundamental impor-
tance in understanding and predicting the behaviour of
complex aqueous systems. Construction of the relevant and
consistent thermodynamic database of electrolyte aqueous
systems has important applications in industry. The extension
of the proposed data helps in understanding the role of
fluorosilicic acid in the wet production process of phosphoric
acid.
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