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Abstract
Donnan equilibrium based models can be used to predict ion-exchange related phenomena within many application fields. In this paper, a
method for doing Donnan equilibrium calculations using Gibbs energy minimization is presented. With this approach, it is possible to solve
Donnan equilibrium systems with complex solution or multiphase chemistry using Gibbs energy minimizing programs.
D 2005 Elsevier B.V. All rights reserved.
Keywords: Donnan equilibrium; Ion-exchange; Gibbs energy minimization
1. Introduction
Donnan equilibrium based models have been used to model
ion exchange phenomena in industrial pulp and papermaking
processes [1], in basic research of polyelectrolytes [2] and
membrane equilibrium with ionic drugs [3]. In some of these
situations, the overall chemistry of the system can be quite
complex with multiple components and phases and non-ideal
interactions in solutions. As advanced computer programs and
databases have been developed for solving multi-component
and multi-phase equilibria problems, it has been the purpose of
this work to show how a general purpose Gibbs energy
minimizing program can be used for equilibrium calculations
in systems where the Donnan equilibrium applies.
2. Theory
2.1. Donnan equilibrium
Electrochemical systems consisting of two parts where one or
more charged species are restricted to one part of the system by a
semi-permeable membrane were first investigated by Donnan in
early 20th century [4]. It has been later shown that the same basic
relations can also often be applied to model systems where the
confinement of some ionic species is caused, not by a membrane,
but by chemical bonding to a macromolecular structure. The
* Corresponding author. Tel.: +358 9 456 6332; fax: +358 20 722 7026.
E-mail address: Risto.Pajarre@vtt.fi (R. Pajarre).
0167-7322/$ - see front matter D 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.molliq.2005.11.016
0
l4W
i li W RT lnai W zi FwW
Aqueous solution
CaCO3
H2O
H+
OH
N2
O2
Na+
CO2
HCO
3
CO23
Ca2 +
CaCO3
2
1
1
Na
Ca
e
1
1
2
i1
1
1
2
3
3
59
1
1
1
1
2
2
1
3
Table 2
The chemical system of Table 1 divided to two volumes with an added ion (Anion
a ) that cannot be transferred from the second sub-volume to the first one
(1) Solution volume
CaCO3
H2O
H+
OH
Na+
CO2
HCO
3
CO2
3
Ca2+
H2O
H+
OH
Na+
CO2
HCO
3
CO2
3
Ca2+
Anion
a
CaCO3
2
1
1
Na
Ca
solvent2
Aniona
1
1
1
1
2
2
1
1
1
2
1
1
1
2
3
3
1
1
1
1
1
charge2
1
1
1
1
2
3
3
e
1
1
1
1
1
1
1
2
2
1
1
2
2
1
z
p
a2i
i
charge
i
2
exp i
9
RT
a1i
that can be further simplified when the standard states are equal
to
z p
p
zi
a2i
i charge2
charge2
exp
:
10
exp
RT
RT
a1i
Comparing Eqs. (3) and (10), we can note the equality
11
F w1 w2 pcharge2
l0s
RT lna2s
12
l1s
psolvent2
13
Ca/mmol/dm3
60
0.4
0.3
0.2
0.1
0
0
10
12
pH
[Ca]s
[Ca]s measured
CaCO3
61
1
0.9
0.8
0.7
0.6
0.5
4. Conclusion
0.4
0.3
0.2
0.1
0
2
10
12
pH
Na
Na (exp)
Ca
K (exp)
Ca (exp)
Mg
Mg (exp)
Fig. 2. Calculated and experimental ratio between the metal amounts in solution
and the total metal content of the pulp as function of pH in a suspension treated
with EDTA. Experimental values and chemical inputs for the model based on
Ref. [10].