1

Thermodynamic modeling of
some properties of electrolyte
solutions
Kaj Thomsen
IVC-SEP, Department of Chemical
Engineering, Technical University of
Denmark, DK-2800 Lyngby, Denmark.
E-mail: kth@kt.dtu.dk
3
Models for electrolytes
Long range interactions
Debye-Hckel electrostatic term
Short range interactions
Pitzer virial expansion in molality
Electrolyte NRTL
UNIQUAC
Gas phase fugacity
PR or SRK equation of state
4
Extended UNIQUAC
Excess gibbs energy function
Debye-Hckel term
UNIQUAC term
Activity coefficients and thermal
properties are derived by standard
methods known from classical
thermodynamics
5
Standard states
Water is the solvent
Ions, non-electrolytes and gases are
treated equally as solutes in water
0
1
ln( ); 1
w
x w w w w w
RT x

= +
* * *
0
ln( ); 1
i
i
i i i i i
x
RT x

= +

6
Gibbs energy of transfer
Kamps, A.P-S., Ind. & Eng. Chem. Res., 44(2005)201-225
7
Relative permittivity
Relative permittivity of aqueous solutions
0
10
20
30
40
50
60
70
80
90
0 10 20 30 40 50 60 70 80 90 100
Mass % solute
R
e
l
a
t
i
v
e

p
e
r
m
i
t
t
i
v
i
t
y



.
NaCl, Hasted et al, 1948
Ethanol, kerlf, 1932
8
Conventional and Mixed solvent
approach
* *
ln ln
"Mixed solvent" approach:
ln ln
i i i i
ideal excess
Mixed solvent Mixed solvent
i i i i
ideal excess
RT x RT
RT x RT


= + +
= + +
In the Mixed solvent approach, the standard state chemical
potential is a function of the solvent composition
9
Model parameters
Standard UNIQUAC parameters
Volume parameter for each species
Surface area parameter for each species

Interaction energy parameter for each
pair of species
Temperature dependence of interaction
energy parameter
Number of parameters:
eUNIQUAC ~ eNRTL << Pitzer
10
Databank
Over 100,000 experimental data on
electronic form
Activity/osmotic coefficient
Enthalpy of mixing
Heat capacity
Degree of dissociation
Gas solubility
Density
Salt solubility (Solid-liquid equilibrium)
Liquid-liquid equilibrium
Vapor-liquid equilibrium
11
Parameter estimation
Critical review of data
Non-linear least squares optimization
Differences between experimental and
calculated values are minimized
The calculation of the difference
depends on the type of data
All data of same type weighted equally
12
Anchoring of parameters
No binary solution of one ion in
water
Parameters of ions are relative to
each other
The hydrogen ion is used as anchor
Parameters for the hydrogen ion are
given fixed values

13
Thermal properties
Excess enthalpy is calculated from the
temperature derivatives of activity
coefficients.
By using thermal properties in the
parameter estimation a better
temperature dependency of activity
coefficients is achieved
Clear distinction between temperature
dependency and concentration
dependency
14
Parameters
H
+
, Na
+
, K
+
, NH
4
+
, Ca
2+
, Mg
2+
, Mn
2+
, Fe
2+
,
Co
2+
, Ni
2+
, Cu
2+
, Zn
2+
, Ba
2+
, Sr
2+

F
-
, Cl
-
, Br
-
, NO
3
-
, SO
4
2-
, HSO
4
-
, OH
-
, CO
3
2-
,
HCO
3
-
, S
2
O
8
2-
, SO
3
2-
, HSO
3
-
, HPO
4
-
, H
2
PO
4
-
H
2
O, CO
2
, NH
3
, SO
2
, HNO
3
, H
3
PO
4
,
C
12
H
22
O
11
, CH
3
OH, C
2
H
5
OH, n-C
3
H
7
OH, i-
C
3
H
7
OH, n-C
4
H
9
OH, i-C
4
H
9
OH, s-C
4
H
9
OH,
t-C
4
H
9
OH
15
Equilibrium calculations
Speciation equilibrium
+
Solid-liquid equilibrium
Vapor-liquid equilibrium
Liquid-liquid equilibrium

16
Speciation equilibria
NH
3
(aq)+H
2
O NH
4
+
(aq)+OH
-
(aq)
Equilibrium condition:
-
3 2
4
- -
3 2
4 4
3 2
* * * 0 * *
*
- -
- ln
NH H O
NH OH
NH H O
NH OH NH OH
NH H O
a a
RT a a


+
+ +
+ = +
+
=
17
Solid-liquid equilibrium
At equilibrium, the chemical potential
of the pure crystalline salt(hydrate)
equals the sum of the chemical
potentials of the salts components in
solution
It is required that other salts are not
supersaturated.
18
Vapor-liquid equilibrium
Equality of chemical potential in gas
phase and in liquid phase (Gamma-phi
method)
Gas phase fugacities are calculated
with the Soave-Redlich-Kwong
equation of state
( )
2 2
2 2 2 2 2 2
( ) ( )
0, * *
0

ln ln
CO g CO aq
ig
CO CO CO CO CO CO
P
RT y RT x
P


=
| |
+ = +
|
\ .
19
Liquid-liquid equilibrium
Here the activity product of salts rather
than the activities of the individual ions
ions are compared



=
+ = +
=
I II
* * I * * II
* I * II
ln( ) ln( )
( ) ( )
i i
i i i i i i
i i i i
RT x RT x
x x
Equilibrium between component i in
phase I and phase II
20
Standard state properties
The numerical values of standard state
chemical potentials are needed before
equilibrium calculations can be made
Such values for most solutes and many
salts have been published by NIST
Those not found are fitted to experimental
data
Temperature dependence calculated with
classical thermodynamic method
21
-20
-10
0
10
20
30
40
50
60
70
80
90
0 10 20 30 40 50 60 70 80 90 100
T
e
m
p
e
r
a
t
u
r
e

C


Extended UNIQUAC model
Experimental data
--
Mass percent Mn(NO
3
)
2
I
c
e
M
n
(
N
O
3
)
2

6
H
2
O
M
n
(
N
O
3
)
2

4
H
2
O
M
n
(
N
O
3
)
2

2
H
2
O
M
n
(
N
O
3
)
2

H
2
O
22
0
20
40
60
80
100
120
0 0.05 0.1 0.15 0.2
Mass percent Ca(OH)
2
T
e
m
p
e
r
a
t
u
r
e

C
Calculated
Experimental
Ca(OH)
2
23
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
-40 -30 -20 -10 0 10 20 30 40 50 60 70 80 90 100 110
s
a
l
t

f
r
a
c
t
i
o
n
Extended UNIQUAC model
Experimental data
Temperature, C
K
2
C
O
3
N
a
2
C
O
3




Na
2
CO
3
K
2
CO
3
NaKCO
3
6H
2
O
Na
2
CO
3
Na
2
CO
3
H
2
O
Na
2
CO
3
7H
2
O
Na
2
CO
3
10H
2
O Ice
K
2
CO
3
H
2
O
24
100
90
80
70
60
50
40
30
20
10
0 100
90
80
70
60
50
40
30
20
10
0
0
1
0
2
0
3
0
4
0
5
0
6
0
7
0
8
0
9
0
1
0
0
0 10 20 30 40 50 60 70 80 90 100
Experimental
data, various
sources
Extended
UNIQUAC,
Equilibrium lines
and tie lines
K
2
CO
3
Na
2
CO
3
H
2
O(l)
T= 75.0C
Na
2
CO
3
H
2
O
Na
2
CO
3
K
2
CO
3
K
2
CO
3
H
2
O
25
0
10
20
30
40
50
60
70
80
90
0 2 4 6 8 10
CO
2
mol kg
-1
C
O
2

p
a
r
t
i
a
l

p
r
e
s
s
u
r
e
,

b
a
r
Extended UNIQUAC model
Experimental data
__
80C
12 molal NH
3
9 molal NH
3
2 molal
NH
3
6.8 molal NH
3
4.1 m
1 m
0.6 m
5.9 molal NH
3
26
100
90
80
70
60
50
40
30
20
10
0
0
10
20
30
40
50
60
70
80
90
100
0
1
0
2
0
3
0
4
0
5
0
6
0
7
0
8
0
9
0
1
0
0
0 10 20 30 40 50 60 70 80 90 100
Thompson and Vener (1948)
Armstrong and Eyre (1910)
Gerardin (1865)
Schiff (1861)
Extended UNIQUAC model
Series2
Series3
Series4
C
2
H
5
OH
KNO
3
H
2
O
15C
25C
50C
75C
27
100
90
80
70
60
50
40
30
20
10
0 100
90
80
70
60
50
40
30
20
10
0
0
.
0
0
1
0
.
0
0
2
0
.
0
0
3
0
.
0
0
4
0
.
0
0
5
0
.
0
0
6
0
.
0
0
7
0
.
0
0
8
0
.
0
0
9
0
.
0
0
1
0
0
.
0
0
0 10 20 30 40 50 60 70 80 90 100
Iino et al. (1971)
Do & Park (1974)
Extended UNIQUAC
Series2
Series3
Series4
Series7
iso-propanol
K
2
CO
3
H
2
O
30 C
28
xy - diagram for iso-propanol - water, 1 bar
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x iso-propanol
y

i
s
o
-
p
r
o
p
a
n
o
l
Extended UNIQUAC model
Marzal et al. (1996)
Saturation with K2CO3
29
Integral heat of dilution to infinite dilution
-3000
-2000
-1000
0
1000
2000
3000
4000
0 2 4 6
Molality of KCl
J mol
-1
Ext. UNIQUAC
Experimental, 12.5C
Experimental, 25C
Experimental, 40C
Experimental, 60C
Experimental, 80C
30
Apparent molal heat capacity
-200
-150
-100
-50
0
50
0 0.5 1 1.5 2 2.5 3
Molality of NaOH
J mol
-1
K
-1
Ext. UNIQUAC
Experimental, 10C
Experimental, 25C
Experimental, 40C
Experimental, 100C
31
Pressure dependency
No pressure dependency in activity
coefficient model
High pressure applications
Scale formation in oil production
equipment and reservoirs
Scale formation in equipment used for
producing geothermal energy
32
What is scale formation?
33
Pressure dependency
Solubility product:


Activity coefficients:
0
0
2
0 0
ln ln ( ) ( )
2
dis P
dis
P P
V
K K P P P P
RT RT
k
A
A
= +
0
0
,
* * 2
, , 0 0
ln ln ( ) ( )
2
ex
ex
i P
i
i P i P
V
P P P P
RT RT
k
= +
34
Equilibrium expression
The resulting equation for
equilibrium is:


Alfa and beta have physical
meanings.
We treat them as adjustable
parameters
( )
0 0
2
0 0 ,
ln ( ) ( ) ln
P i i i P
i
K P P P P x o | v + + =

35
BaSO
4
solubility at 500 bar
1.00E-06
6.00E-06
1.10E-05
1.60E-05
2.10E-05
2.60E-05
3.10E-05
3.60E-05
4.10E-05
4.60E-05
0 50 100 150 200 250 300
T (
o
C)
B
a
S
O
4

(
m
)
Extended UNIQUAC model
Blount (1977)
Lyashchenko and Churagulov (1981)
Garca A.V.,
Thomsen K.,
Stenby E.H.,
Geothermics
34(2005)61-
97
36
SrSO
4
solubility isotherms
0.0E+00
2.0E-04
4.0E-04
6.0E-04
8.0E-04
1.0E-03
1.2E-03
1.4E-03
0 100 200 300 400 500 600 700
P (bar)
S
r
S
O
4

(
m
)
Extended UNIQUAC model
Howell et al. (1992)
25 C
100 C
200 C
37
CaCO
3
solubility at 30 bar CO
2
0.000
0.005
0.010
0.015
0.020
0.025
0.030
0 50 100 150 200
T (
o
C)
C
a
C
O
3

(
m
)
Extended UNIQUAC model
Segnit et al. (1962)
Miller (1952)
Garca A.V.,
Thomsen K.,
Stenby E.H.,
Geothermics
35(2006)239-
284

38
Inconsistent data
0.000
0.001
0.002
0.003
0.004
0.005
0.006
0.007
0.008
0.009
0.010
0 1 2 3 4 5 6
NaCl (m)
S
r
S
O
4

(
m
)
Howell et al. (1992)
Brower and Renault (1971)
Vetter et al. (1983)
Lucchesi and Whitney (1962)
Mller (1960)
39
Experimental setup
40
Measurements
Analysis for Ba performed by ICP-MS
(Inductively Coupled Plasma Mass
Spectrometry)
Three different labs measured three
different Ba contents in the same
sample!
We did not get any good data yet!

41
Corrosion in wet gas pipelines
In another project, the Extended
UNIQUAC model is being applied for
describing and preventing corrosion
Equilibrium calculations to be
combined with electrochemical and
transport aspects

PhD student Philip Fosboel
42
Where do we find corrosion?
GAS Line
16
CO
2

H
2
O
Natural gas

CO
2

H
2
O
NaOH
MEG

43
CO
2
Corrosion
pH is lowered by dissolved CO
2
.

2 2 3
2
2
2
2 2 3 2
( ) ( ) ( ) ( )
Half cell reactions:
2 2
2
The sum of reactions:
( ) 2 ( ) 2 ( ) ( ) 2 ( ) ( )
CO aq H O l HCO aq H aq
H e H
Fe Fe e
Fe s CO aq H O l Fe aq HCO aq H g
+
+
+
+
+ +
+
+
+ + + +
44
CO
2
corrosion
If pH is high enough, a protective
layer of FeCO
3
is formed
Gas composition
1.6 mol % CO
2
0.1 mol % H
2
O
Balance light alkanes
Temperature 10 to 50C
Pressure 60 to 70 bar
45
CO
2
corrosion
Inhibitors:
NaOH
Mono ethylene glycol (MEG)
Liquid phase:
27 to 0.5 wt % NaOH in water
95 - 30 wt % MEG
How much CO
2
can dissolve in this
solution?
46
CO
2
corrosion
If sufficient data are available, the system
can be modelled
No data for solubility of CO
2
in H
2
O MEG
mixture published
Few data for solubility of Na
2
CO
3
and NaHCO
3

in H
2
O MEG mixture
Highly non ideal solution
High ionic strength (up to 10 molal)
Mixed solvent solution
Speciation equilibria
47
CO
2
NaOH - H
2
O MEG
measurements
New measurements are required
The solubility of Na
2
CO
3
and NaHCO
3
is
being measured by titration
The total Na
+
content can be determined
The carbonate/bicarbonate ratio is not
determined
Solvent composition changes during
precipitation of hydrates
Na
2
CO
3
10H
2
O
Na
2
CO
3
7H
2
O
Na
2
CO
3
H
2
O
Na
2
CO
3
NaHCO
3
2H
2
O
48
CO
2
NaOH - H
2
O MEG
measurements
Equilibration
Automated accurate titration
10 < TC < 50
0 < wt % MEG < 100
Saturated solutions
49
CO
2
NaOH - H
2
O MEG
NaHCO
3
solubility
determined by
titration of saturated
solution
Two salt transition
points marked by
sudden density
change of saturated
solution
Solubility of salts can
be determined if
amount of precipitate
is known. Raw data
are used for
parameter estimation
100
90
80
70
60
50
40
30
20
10
0
0
10
20
30
40
50
60
70
80
90
100 Solid phase
Saturated
Start
0
1
0
2
0
3
0
4
0
5
0
6
0
7
0
8
0
9
0
1
0
0
0 10 20 30 40 50 60 70 80 90 100
Solubility isotherm
Tie-lines
Experiment
NaHCO
3
Na
2
CO
3
H
2
O+MEG
Na
2
CO
3
NaHCO
3
2H
2
O
Na
2
CO
3
10H
2
O
50
CO
2
NaOH - H
2
O MEG
Preliminary results
calculated with
Extended UNIQUAC
model based on
model parameters
determined from
literature data.
(Grtner et al. J.
Chem. Eng. Data,
49(2004)116-125)
0
5
10
15
20
25
0 20 40 60 80 100
wt% saltfree MEG
g
/
1
0
0
g

s
o
l
v
e
n
t
model 25C
model 50C
model 80C
experimental 25C
experimental 50C
experimental 80C
0
5
10
15
20
25
0 20 40 60 80 100
wt% saltfree MEG
g
/
1
0
0
g

s
o
l
v
e
n
t
model 25C
model 50C
model 80C
experimental 25C
experimental 50C
experimental 80C
51
CO
2
corrosion
When parameters in the model are
determined, we can
Combine this thermodynamic model with a
diffusion model to determine corrosion rate
Calculate speciation equilibria in the mixed
solvent solution
Calculate the saturation index of the protective
coating of FeCO
3
Determine the optimal amount of NaOH to add
to the solution to avoid corrosion
Determine the optimal amount of MEG to add
to avoid gas hydrate formation
52
Equation of state for electrolytes
Current activity coefficient models
are good but not perfect
No pressure dependency
No density calculation
Decreasing accuracy with increasing
number of components
Practical to use same equation of
state for all components
PhD student Yi Lin
53
Comparative study of four EOS
Short range interactions:
Soave-Redlich-Kwong
Peng-Robinson
Wertheim association term for water
Long range electrostatic interactions:
Mean spherical approximation (MSA)
Implicit and explicit version
Simpel Debye-Hckel term
Born term
54
Myers, Sandler and Wood (MSW)
electrolyte EOS
Myers et al., Ind. Eng. Chem. Res.
41(2002)3282-3297
A
R
= AA
PR
+ AA
Born
+ AA
MSA
Short range term : PR EOS
Long range terms: Explicit MSA, Born
We use ion specific parameters.
AA
PR
:
AA
Born
, AA
MSA
:

, ,
i i ij
a b k
i
o
55
Modified MSW electrolyte EOS
We replace the explicit MSA term with the
implicit MSA term
A
R
= AA
PR
+ AA
Born
+ AA
imMSA
Short range term : PR EOS
Long range terms: Implicit MSA, Born
Ion specific parameters.
AA
PR
:
AA
Born
, AA
imMSA
:

, ,
i i ij
a b k
i
o
56
Electrolyte CPA EOS
We replace the Peng-Robinson term with
the Soave-Redlich-Kwong + Wertheim
term
A
R
= AA
SRK
+ AA
W
+ AA
Born
+ AA
imMSA
Short range term : SRK + Association
Long range terms: Implicit MSA, Born
Ion specific parameters.
AA
SRK
:
AA
Born
, AA
imMSA
:

, ,
i i ij
a b k
i
o
57
Approximation
An approximation introduced by Myers, Sandler
and Wood (Ind. Eng. Chem. Res. 41(2002)3282-
3297) is implemented for the three EOS
mentioned.
The density of water is needed for calculating the
relative permittivity of water from the relation of
Uematsu and Franck





2 2 2
2 2
/
( , ) ( , , )
H O H O H O
r H O r H O
n M V
T T V n

c c
~

58
SRK + DH EOS

Short range term : SRK
Long range terms: Debye-Hckel
Ion specific parameters.
The Debye-Hckel parameter A is a
function of temperature only
Debye-Hckel term with no
contribution to volume

, ,
i i ij
a b k
ln ln ln
SRK DH SRK DH
i i i

+
= +
59
Test system at 298.15 K
H
2
O-(Na
+
, Ca
2+
, H
+
)-(Cl
-
, SO
4
2-
, OH
-
)
1300 experimental data points used
Osmotic/activity coefficient
Solid-liquid equilibrium data
Apparent molar volume

0
*
,
ex ex
w w S S w w
S S
S S
nM n M n M n M
M M
n n

+
= +
60
Results
0 1 2 3 4 5 6 7
0.85
0.90
0.95
1.00
1.05
1.10
1.15
1.20
1.25
1.30
1.35
NaCl
O
s
m
o
t
i
c

C
o
e
f
f
i
c
i
e
n
t
Molality (mol/kg)
Experimental data
MSW EOS
mMSW EOS
eCPA EOS
SRK+DH
0 1 2 3 4 5 6 7 8 9 10
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
CaCl
2
O
s
m
o
t
i
c

C
o
e
f
f
i
c
i
e
n
t
Molality (mol/kg)
Experimental data
MSW EOS
mMSW EOS
eCPA EOS
SRK+DH
Lin Y., Thomsen K., and de Hemptinne J-C., submitted to AIChE Journal
61
Results
0 1 2 3 4 5 6 7
0.0
0.5
1.0
1.5
2.0
NaCl
Na
2
SO
4
Na
2
SO
4
10H
2
O
N
a
2
S
O
4

M
o
l
a
l
i
t
y

(
m
o
l
/
k
g
)
NaCl Molality (mol/kg)
Experimental Data
MSW EOS
mMSW EOS
eCPA EOS
SRK+DH
0.000 0.002 0.004 0.006 0.008 0.010 0.012 0.014 0.016
0.000
0.005
0.010
0.015
0.020
0.025
Ca(OH)
2
CaSO
4
2H
2
O

C
a
(
O
H
)
2

M
o
l
a
l
i
t
y

(
m
o
l
/
k
g
)
CaSO
4
Molality (mol/kg)
Experimental Data
MSW EOS
mMSW EOS
eCPA EOS
SRK+DH
62
Results
0 1 2 3 4 5 6 7
12
14
16
18
20
22
24
A
p
p
a
r
e
n
t

M
o
l
a
r

V
o
l
u
m
e
Molality (mol/kg)
Experimental data
MSW EOS
mMSW EOS
eCPA EOS
SRK+DH
HCl
0 1 2 3 4 5 6 7 8
0.75
0.80
0.85
0.90
0.95
1.00
1.05
1.10
1.15
HCl
D
e
n
s
i
t
y

(
g
/
c
m
3
)
Molality (mol/kg)
Experimental data
MSW EOS
mMSW EOS
eCPA EOS
SRK+DH
0 1 2 3 4 5 6
-5
0
5
A
p
p
a
r
e
n
t

M
o
l
a
r

V
o
l
u
m
e
Molality (mol/kg)
Experimental data
MSW EOS
mMSW EOS
eCPA EOS
NaOH
0 1 2 3 4 5 6
0.75
0.80
0.85
0.90
0.95
1.00
1.05
1.10
1.15
1.20
1.25
NaOH
D
e
n
s
i
t
y

(
g
/
c
m
3
)
Molality (mol/kg)
Experimental data
MSW EOS
mMSW EOS
eCPA EOS
63
Temperature dependence
Usually the a parameter in cubic EOS is
temperature dependent
We chose to let the ion size parameter be
temperature dependent too
Seven different temperature dependence
functions were tested
The best was:



( ) ( )
( )
0 1 2
0 1
2
( )
( )
298.15 298.15
298.15
a T a a a
T
T T
T o o o
= + +
= +

64
Results

0 0.5 1 1.5 2 2.5 3 3.5 4
0
20
40
60
80
100
120
Molality (mol/kg)
T
e
m
p
e
r
a
t
u
r
e

o
C
Exp data
MSW EOS
mMSW EOS
CPA EOS
SRK+DH EOS
Ice
Na
2
SO
4
.
10H
2
O
Na
2
SO
4

0 1 2 3 4 5 6
0
1
2
3
4
5
6
7
8
-40
o
C
-25
o
C
-20
o
C
-20
o
C, y + 0.5
-10
o
C
-10
o
C, y + 1.5
0
o
C
0
o
C, y + 2.5
NaCl Molality (mol/kg)
C
a
C
l
2

M
o
l
a
l
i
t
y


(
m
o
l
/
k
g
)

)

Exp data
MSW EOS
mMSW EOS
CPA EOS
N
aC
l
.
2H
2
O
Ice
-25
o
C
C
a
2
C
l

.
6
H
2
O
65
Temperature dependence
The thermal properties (heat of mixing,
heat capacity) of electrolyte solutions
could not be well correlated by any of the
EOS
The same is the case for the apparent
molar volume of these solutions
Alternative to be tested:
Use temperature dependent interaction
parameters in the EOS as it is done in the
activity coefficient model
66
Results
5
7
9
11
13
15
17
19
21
23
25
0 1 2 3 4 5 6
NaCl molality
A
p
p
a
r
e
n
t

m
o
l
a
r

v
o
l
u
m
e

c
m
3
/
m
o
l
MSW, 100 C
mMSW, 100 C
CPA, 100 C
Experimental, 100 C
Experimental, 25 C
MSW, 25 C
mMSW, 25 C
CPA, 25 C
67
Conclusions
Activity coefficient models like the
Extended UNIQUAC model is
currently the only way to model
properties of electrolyte solutions
Electrolyte EOS based on cubic EOS
need more developement before
they can be used as engineering
equations