Thermodynamic Modeling of the

Solubility of Alkali and Earth Alkali

Borates
Kaj Thomsen, Associate Professor
CERE, Center for Energy Resources Engineering
Department of Chemical and Biochemical Engineering
Technical University of Denmark

24-07-2012 Thermodynamic Modeling of the Solubility of
Alkali and Earth Alkali Borates
2 DTU Chemical Engineering,
Technical University of Denmark
Importance of borates
Metabolizing effects useful for controlling insects and bacteria
Bleaching effects useful in laundry detergents
Buffering effects widely used for controlling pH
Dispersing effects useful in paints, adhesives and cosmetics
Vitrifying effects modify the structure of glass, facilitate the
production of LCD screens
Inhibiting effects forms a coating that protect metals from corrosion
Flame-Proofing effects useful as a flame retardant
Neutron-Absorbing effects useful in connection with certain
hospital equipment and nuclear containment shields
Micro nutrient for plants
Glazing on ceramics
Largest single use worldwide is as an ingredient in fiberglass
24-07-2012 Thermodynamic Modeling of the Solubility of
Alkali and Earth Alkali Borates
3 DTU Chemical Engineering,
Technical University of Denmark
Complexity of borates
The chemical formulae for borates are often written in terms of the
amounts of oxides:
Na
2
O B
2
O
3
H
2
O Formula 1 Formula 2
1 1 1 Na
2
OB
2
O
3
H
2
O NaBO
2
H
2
O
1 1 4 Na
2
OB
2
O
3
4H
2
O NaBO
2
2H
2
O
1 1 8 Na
2
OB
2
O
3
8H
2
O NaBO
2
4H
2
O
1 2 Na
2
O2B
2
O
3
Na
2
B
4
O
7
1 2 4 Na
2
O2B
2
O
3
4H
2
O Na
2
B
4
O
7
4H
2
O
1 2 10 Na
2
O2B
2
O
3
10H
2
O Na
2
B
4
O
7
10H
2
O
1 5 10 Na
2
O5B
2
O
3
10H
2
O NaB
5
O
8
5H
2
O
2 1 1 2Na
2
OB
2
O
3
H
2
O NaBO
2
NaOH
2 5 7 2Na
2
O5B
2
O
3
7H
2
O Na
4
B
10
O
17
7H
2
O
2 9 11 2Na
2
O9B
2
O
3
11H
2
O Na
4
B
18
O
29
11H
2
O
24-07-2012 Thermodynamic Modeling of the Solubility of
Alkali and Earth Alkali Borates
4 DTU Chemical Engineering,
Technical University of Denmark
Complexity of borates
In this work, all borate species were expressed in terms of:
H
3
BO
3
(aq), Boric acid
B
4
O
7
2-
, Tetraborate ion
BO
2
-
, Metaborate ion
B
2
O
3
is considered to be a dehydrated form of Boric acid:
2H
3
BO
3
(aq) B
2
O
3
+ 3H
2
O
B
5
O
8
-
is formed when pH is raised:
5H
3
BO
3
(aq) + OH
-
B
5
O
8
-
+ 8H
2
O
Tetraborate, B
4
O
7
2-
+is formed at slightly higher pH:
4H
3
BO
3
(aq) + 2OH
-
= B
4
O
7
2-
+ 7H
2
O
Metaborate, BO
2
-
is formed when pH is increased more:
H
3
BO
3
(aq) +OH
-
BO
2
-
+ 2H
2
O

24-07-2012 Thermodynamic Modeling of the Solubility of
Alkali and Earth Alkali Borates
5 DTU Chemical Engineering,
Technical University of Denmark
Extended UNIQUAC model
Not a new model but new parameters
Original parameters were limited in terms of temperature,
concentration, and pH
Thermodynamic model for solutions containing electrolytes
Debye-Hckel term for electrostatic interactions
UNIQUAC term for short range interactions
Soave-Redlich-Kwong term for gas phase fugacities
The model is used for calculation of
Speciation equilibrium
Solid-liquid equilibrium
Vapor liquid equilibrium
Liquid-liquid equilibrium
Thermal properties
24-07-2012 Thermodynamic Modeling of the Solubility of
Alkali and Earth Alkali Borates
6 DTU Chemical Engineering,
Technical University of Denmark
Extended UNIQUAC model
Relative permittivity for pure water is used for all solutions
The effect of other species on the chemical potentials in the
solution is accounted for by interaction parameters
The hydrogen ion is given fixed parameters, including interaction
parameters with all other species
The hydrogen ion is considered an anchor for the parameters
The properties of all other species are determined relative to
those of the hydrogen ion
The temperature dependence of chemical potentials is determined by
the Gibbs-Helmholtz equation:


0
0
2
/
ln
at constant pressure
d G RT
d K H
dT dT RT

24-07-2012 Thermodynamic Modeling of the Solubility of
Alkali and Earth Alkali Borates
7 DTU Chemical Engineering,
Technical University of Denmark
Model parameters and standard
state properties
Volume and surface area parameters for each species
6 parameters
A binary interaction parameter for each pair of species
26 interaction parameters were used
5 of these have linear temperature dependency
Values of the Gibbs energy of formation for ions is usually found in the
NIST tables
Values not found in the NIST tables were determined during
parameter estimation:
Enthalpy of formation of the tetraborate ion, B
4
O
7
2-

Gibbs energy of formation for 22 solid phases
Enthalpy of formation for 20 solid phases

24-07-2012 Thermodynamic Modeling of the Solubility of
Alkali and Earth Alkali Borates
8 DTU Chemical Engineering,
Technical University of Denmark
Determination of parameters
The adjustable parameters were determined using a modified
Marquard routine from Harwell subroutine library and a Nelder-
Mead simplex routine
Parameter determination:
1. Core system consisting of H
+
, Li
+
,Na
+
, K
+
, Mg
2+
, Ca
2+
, OH
-
, Cl
-
, HCl,
NO
3
-
, HNO
3
, SO
4
2-
, HSO
4
-
based on ca. 27000 experimental data
points distributed on 23 binary and 87 ternary systems.
2. 3000 experimental data for borates in the above systems except
HNO
3
were used for
Determining the 6+26 model parameters for the borate
species
Determining the 43 standard state properties for the
various solid phases and the tetraborate ion

24-07-2012 Thermodynamic Modeling of the Solubility of
Alkali and Earth Alkali Borates
9 DTU Chemical Engineering,
Technical University of Denmark
Online experimental data bank - free
Data bank for electrolyte solutions at http://www.cere.dtu.dk/Expertise/
Over 150,000 experimental data on electronic form
More than 350 solute species
Types of data include:
Activity/osmotic coefficient
Enthalpy of mixing
Heat capacity
Degree of dissociation
Gas solubility
Enthalpy of absorption/evaporation
Density
Salt solubility (Solid-liquid equilibrium)
Liquid-liquid equilibrium
Vapor-liquid equilibrium
24-07-2012 Thermodynamic Modeling of the Solubility of
Alkali and Earth Alkali Borates
10 DTU Chemical Engineering,
Technical University of Denmark
-5
15
35
55
75
95
115
0 5 10 15 20 25 30
T
e
m
p
e
r
a
t
u
r
e

C

Weight percent Na
2
B
4
O
7

Horn and Van Wagener (1905)
Teeple (1929)
Blasdale and Slansky (1939)
Nies and Hulbert (1967)
Platford (1971)
Extended UNIQUAC model

Na
2
B
4
O
7
10H
2
O
Borax
Na
2
B
4
O
7
4H
2
O
Kernite
24-07-2012 Thermodynamic Modeling of the Solubility of
Alkali and Earth Alkali Borates
11 DTU Chemical Engineering,
Technical University of Denmark
0%
1%
2%
3%
4%
5%
6%
0% 10% 20% 30% 40%
w
t

%

H
3
B
O
3

wt % MgCl2
Extended UNIQUAC
Gode (1969)
H
3
BO
3
MgCl
2
6H
2
O

25C
24-07-2012 Thermodynamic Modeling of the Solubility of
Alkali and Earth Alkali Borates
12 DTU Chemical Engineering,
Technical University of Denmark
0
10
20
30
40
50
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
m
o
l

H
2
O
/
(
m
o
l

N
a
2
O
+
B
2
O
3
)

Na
2
O/(Na
2
O+B
2
O
3
) molar ratio
Extended UNIQUAC
Nies and Hulbert (1967)
Sborgi and Mecacci (1916)
60C
H
3
BO
3
Sassolite
NaB
5
O
8
5H
2
O
Sborgite
Na
2
B
4
O
7
10H
2
O
Borax
NaBO
2
4H
2
O
NaBO
2
H
2
O
NaOHH
2
O
Na
4
B
10
O
17
7H
2
O
Excurrite
2Na
2
OB
2
O
3
H
2
O
NaBO
2
2H
2
O
24-07-2012 Thermodynamic Modeling of the Solubility of
Alkali and Earth Alkali Borates
13 DTU Chemical Engineering,
Technical University of Denmark
0
10
20
30
40
50
60
70
80
0 0.2 0.4 0.6 0.8 1
H
2
O
/
(
K
2
O
+
B
2
O
3
)

m
o
l

b
a
s
i
s

K
2
O/(K
2
O+B
2
O
3
) mol basis
Carpeni (1955)
Extended UNIQUAC
45C
H
3
BO
3
KB
5
O
8
4H
2
O

K
2
B
4
O
7
4H
2
O

KBO
2
H
2
O
KOHH
2
O

24-07-2012 Thermodynamic Modeling of the Solubility of
Alkali and Earth Alkali Borates
14 DTU Chemical Engineering,
Technical University of Denmark
0
50
100
150
200
250
300
350
400
450
500
0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0.18 0.2
H
2
O
/
(
M
g
O
+
B
2
O
3

m
o
l

b
a
s
i
s
)

MgO/(MgO+B
2
O
3
) mol basis
D'Ans and Behrent (1957)
Extended UNIQUAC
83C
H
3
BO
3
MgO3B
2
O
3
7.5H
2
O

MgB
2
O
4
3H
2
O

24-07-2012 Thermodynamic Modeling of the Solubility of
Alkali and Earth Alkali Borates
15 DTU Chemical Engineering,
Technical University of Denmark
0
500
1000
1500
2000
2500
0 0.2 0.4 0.6 0.8 1
H
2
O
/
(
C
a
O
+
B
2
O
3
)

m
o
l

b
a
s
i
s

CaO/(CaO+B
2
O
3
) mol basis
Sborgi (1913)
Extended UNIQUAC
30C
Ca(OH)
2
CaB
2
O
4
6H
2
O
2CaO3B
2
O
3
13H
2
O
Inyoite
CaO3B
2
O
3
4H
2
O
H
3
BO
3
24-07-2012 Thermodynamic Modeling of the Solubility of
Alkali and Earth Alkali Borates
16 DTU Chemical Engineering,
Technical University of Denmark
0
0.5
1
1.5
2
2.5
3
3.5
0 10 20 30 40 50
L
i
2
B
4
O
7

LiCl
T= 25.0C
Extended UNIQUAC model
Lepeshkov et al. (1963)
Skvortsov et al. (1981)
Li
2
B
4
O
7
3H
2
O
LiClH
2
O
24-07-2012 Thermodynamic Modeling of the Solubility of
Alkali and Earth Alkali Borates
17 DTU Chemical Engineering,
Technical University of Denmark
0.00
0.10
0.20
0.30
0.40
0.50
0.60
0.70
0.80
0.90
1.00
0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00
L
i
+







C
a
t
i
o
n

C
h
a
r
g
e

f
r
a
c
t
i
o
n




K
+








SO
4
2-
Anion charge fraction B
4
O
7
2-
T= 14.9C
Sang et al. (2004)
Sang et al. (2006) -metastable
Zeng et al. (2005)
Zeng et al. (2007)
Extended UNIQUAC model
Li
2
SO
4
K
2
SO
4
K
2
SO
4
Li
2
SO
4
H
2
O

K
2
B
4
O
7
4H
2
O
Li
2
B
4
O
7
3H
2
O
24-07-2012 Thermodynamic Modeling of the Solubility of
Alkali and Earth Alkali Borates
18 DTU Chemical Engineering,
Technical University of Denmark
Conclusion
The complex system of alkali and earth alkali borates could be
modeled using a relatively simple model with only a few parameters
The system was modeled considering only three aqueous species
H
3
BO
3
(aq), B
4
O
7
2-
, BO
2
-

Can the modeling be improved by including B
5
O
8
-
?
Most of the model parameters were not temperature dependent
Many experimental solubility data are conflicting better solubility
data are needed!
Meta stability is an issue in this system
Thank you very much for your
attention
24-07-2012 Thermodynamic Modeling of the Solubility of
Alkali and Earth Alkali Borates
20 DTU Chemical Engineering,
Technical University of Denmark
Model implementation
The model is implemented in a dynamic link library (DLL-file)
Multi-phase flash algorithm
The program can be called from programs that have a Visual Basic
interface such as Microsoft Excel
Simulations can be carried out directly in Excel
The excel sheet can be used as an interface to Aspen Plus

The model can be implemented as a user model in Aspen Plus