Journal o f Radioanalyticai Chemistry, Vol.

31 (]976) 335-36 i

THE COMPLEX FORMATION-PARTITION

AND PARTITION-ASSOCIATION
MODELS OF SOLVENT EXTRACTION OF IONS
S. SIEKIERSKI
Department o f Radiochemistry, Institute o f Nuclear Research, Warsaw (Poland)
Two models of the extraction process have been proposed. In the first model it is
assumed that the partitioning neutral species is at first formed in the aqueous phase and then
transferred into the organic phase. The second model is based on the assumption that equivalent
amount~ of cations and anions are at first transferred from the aqueous into the organic phase
and then associated to form a neutral molecule. The role of the solubility parameter in
extraction and the relation between the solubility of liquid organic substances in water and
the partition of complexes have been discussed. The extraction of simple complexes and
complexes with organic ligands has been discussed using the first model. Partition coefficients
have been calculated theoretically and compared with experimental values in some very simple
cases. The extraction of ion pairs has been discussed using the partition-association model
and the concept of single-ion partition coefficients.

Introduction

Solvent extraction is at present one of the separation methods most

f r e q u e n t l y u s e d on b o t h l a b o r a t o r y

and industrial scales.

It has found par-

t i c u l a r l y e x t e n s i v e a p p l i c a t i o n in t h e s e p a r a t i o n of r a d i o a c t i v e m a t e r i a l s .
For instance,

the reprocessing

r n a i n l y on s o l v e n t e x t r a c t i o n .
of extraction chromatography,
radioelements

e.g.

of n u c l e a r f u e l s i s a t t h e m o m e n t b a s e d
Solvent extraction,

particularly

in t h e f o r m

i s a l s o w i d e l y u s e d in t r a c e s e p a r a t i o n s

transurantum

elements and fission products.

of

At the

s a m e t i m e e x t r a c t i o n c a n a l s o b e a p p l i e d to t h e s t u d y of s o m e b a s i c p r o b l e m s in p h y s i c a l i n o r g a n i c c h e m i s t r y ,

such as complex formation or the

interaction of ions and complexes with molecules

of water and organic

solvents.

Z Radioanal Chem. 31 (1976J

335

S. SIEKIERSKI:THE COMPLEXFORMATION-PARTITION
Because of the g r e a t p r a c t i c a l i m por t ance of solvent extraction, and
because of its many interesting fundamental applications much work has
been devoted to the elucidation of its p h y s i c o - c h e m i e a l p r i n c i p l e s . In spite
of this, t h e r e a r e still many unsolved p r o b l e m s which d e s e r v e both t h e o r e t i c a l and ex p er i m ent al studies. P a r t i c u l a r l y , one of the m o s t important
p r o b l e m s - the prediction of extraction behaviour - is f a r from being solved,
even f o r v e r y simple extraction s y s t e m s .
This p ap er Is aimed at the discussion of some p h y s i c o - c h e m i c a l aspects
of solvent extraction of ions. F i r s t of all, aspects of solvent extraction will
be d i s c u s s e d which r e f e r to the interactions of e x t r a c t e d species with the
m o l e c u l e s of w a t e r and organic solvents. Two models o r two approaches
to the d e s c r i p t i o n of extraction p r o c e s s e s a r e p r e s e n t e d . It is believed
that these models point out to the n~ost c h a r a c t e r i s t i c stages of the e x t r a c tion p r o c e s s and facilitate the calculation o r the semiquantitative e s t i m a tion of extraction coefficients from m o r e basic data, at l e a s t in som e
simple c a s e s .
B ef o r e proceeding to the discussion som e r e m a r k s concerning the
terminology should be m a d e . In this p a p e r the t e r m extraction will denote
the o v er all p r o c e s s of t r a n s f e r r i n g a species, e . g . an ion, from the aqueous
into the organic p h a s e . In the c o u r s e of this p r o c e s s the ion can be dehydrated, solvated and can a s s o c i a t e with c o u n t e r - i o n s , so that the species
which ultimately appears in the organic phase may considerably differ from
that existing initially in the aqueous phas e . The t e r m partition will denote
the t r a n s f e r f r o m the aqueous to the organic phase (or distribution
between) of essentially the s a m e species, with only sm al l changes in
composition and s t r u c t u r e o c c u r r i n g in the c o u r s e of the t r a n s f e r
p r o c e s s . Accordingly, the e x t r a c t i o n coefficient, E, (identical wtth the

336

J. Radioanal. Chem. 31 (1976,)

S. SIEKIERSKI:THE COMPLEXFORMATION-PARTITION
distribution ratio) is defined as the ratio of the analytical concentrations of
the Ion in question in each phase, and the partition coefficient, P , a s the
ratio of concentrations of essentially the same species.

The complex formation - partition and partition - association models of extraction

Since in the extraction p r o c e s s many interactions between various

chemical species are involved, extraction s y s t e m s can be classified in a
number of ways according to different principles. There are three main
methods of classifying the extraction s y s t e m s involving ions. The f i r s t
classification is based on the nature of the extractable species, e . g . simple
inorganic molecules, metal chelates, solvated salts, ion pairs etc. The
second classification is based on the solvent type or extractant used, e . g .
inert solvents, basic solvents, acidic extractants e t c . , and the third is
according to the mechanism of the extraction reaction e . g . simple physical
distribution, distribution involving solvation etc. Each of these c l a s s i f i c a tions has its m e r i t s , since each is pointing to a particular feature of the
extraction p r o c e s s . However, t h e i r value as guidelines to the understanding
of the essential stages of the extraction process and to predicting of e x t r a c tion coefficients is r a t h e r limited r
/

Inspection of many extraction s y s t e m s shows that in the majority of

cases each solvent extraction p r o c e s s can be imagined as being composed
of two c h a r a c t e r i s t i c stages: partition between two immiscible liquid phases
and

association or complex formation in either phase. The partition stage

Is, of course, always present, the association stage is absent with simple
inorganic molecules and ion pairs at extreme dilution. Since thermodynamic
functions describing the extraction equilibrium are Independent of the
course of the extraction reaction, the sequence of the stages (partition,
association) ts i r r e l e v a n t from the thermodynamic point of view. Each

1. Radioanal. Chem. 31 {1976]

2~

337

S. SIEKIERSKi: THE COMPLEX FORMATION-PARTITION

e x t r a c t i o n p r o c e s s can t h e r e f o r e be d e s c r i b e d In t e r m s of one of the two
d i f f e r e n t m o d e l s . In both m o d e l s the e x t r a c t i o n p r o c e s s Is s p l i t into two
s t a g e s but in a d i f f e r e n t w a y . A c c o r d i n g to the f i r s t m o d e l which can be
c a l l e d the c o m p l e x f o r m a t i o n - p a r t i t i o n m o d e l the s p e c i e s which finally
a p p e a r s in the o r g a n i c p h a s e Is a s s u m e d to be f o r m e d in the aqueous p h a s e
and then t r a n s f e r r e d to the o r g a n i c p h a s e . I t u n d e r g o e s only s m a l l c h a n g e s
In s t r u c t u r e

and c o m p o s i t i o n in the c o u r s e of the t r a n s f e r p r o c e s s . By

s u c h s m a l l c h a n g e s a r e m e a n t the ones a c c o m p a n i e d by f r e e e n e r g y c h a n g e s
of s e v e r a l h u n d r e d s of e a l / m o l e . The f i r s t m o d e l can b e d e s c r i b e d s c h e m a t l c a l l y by the following equations:

Me

Z+

aq

MeA

+ zA

aq
~

z, aq

MeA

(I)

z, aq

MeA

(2)

z, o r g

( f o r the s a k e of s i m p l i c i t y only anions with c h a r g e

z = -1 a r e c o n s i d e r e d ) .

In m a n y c a s e s the m o l e c u l e MA h a s to b e s o l v a t e d b e f o r e t r a n s f e r
Z

to the o r g a n i c p h a s e . Eqs (1) and (2) r e a d then a s follows:

Me

Z+

aq

+ zA

aq

+ YBaq

MeA B
z y, aq

--

MeA B
z y, aq

MeA B
z y, o r g

(3)

(4)

T h e s p e c i e s MeA

and MeA B can be p a r t i a l l y h y d r a t e d in the o r g a n i c

z
z y
p h a s e . Since m o l e c u l e s B a r e initially p r e s e n t only In the o r g a n i c p h a s e
t h e i r d i s t r i b u t i o n m u s t a l s o be t a k e n into a c c o u n t . The s a m e Is t r u e f o r
the A - ions which, tn the f o r m of acid HA (Inorganic o r o r g a n i c ) , a l s o
d i s t r i b u t e b e t w e e n the two p h a s e s . T h e s e e q u i l i b r i a , including the d l s s o c t a tlou and a s s o c i a t i o n of the HA acid, althought i m p o r t a n t f o r the o v e r a l l

338

J. Radioanal. Chem. 31 {1976)

S. SIEKIERSKI:THE COMPLEXFORMATION-PARTITION
extraction p r o c e s s , a r e not c h a r a c t e r i s t i c of the extraction of the c o n s i d e red cation and can be d i s c u s s e d as independent extraction p r o c e s s e s .
According to the second model which can be called the partition association model,

ions forming the ext ract ed salt are, at f i r s t , t r a n s -

f e r r e d into the organic phase and then eventually associated to f o r m a

n e u tr al molecule o r an ion p a i r . In the c o u r s e of the t r a n s f e r p r o c e s s
ions a r e completely o r partially dehydr a t e d. The m o l e c u l e s MeA z o r the
ions Me 2+ and A - a r e solvated in the organic phase. This model can be
s ch ematically r e p r e s e n t e d by the following equations:
Z+

Me

aq

+ zA

Z+

Me

org

aq

+ zA

org

Z+

Me

org

~ MeA

+ zA

org

(5)

(6)

z, org

It should be noted that, in general, both models do not d e s c r i b e the

r e a l c o u r s e of the extraction p r o c e s s . In the m a j o r i t y of cases the species
which finally appears in the organic phase is f o r m e d at the boundary phase,
so that complex formation, dehydration and solvation p r o c e e d s i m u l t a n e ously with the t r a n s f e r p r o c e s s . The fact that the two models proposed
a r e f a r f r o m r e a l i t y does not impair t h e i r u s e f u l n e s s . Both a r e c o r r e c t
f r o m the th er m odyna m i c point of view, since t herm odynam i c functions of
the o v er all p r o c e s s do not depend on the method of dividing the p r o c e s s into
s tag es . They provide a simple des c r i pt i on and understanding of basic i n t e r actions which d e t e r m i n e the magnitude of the extraction coefficients. Basing
o n t h e s e models attempts can be m ade to calculate o r at least to e s t i m a t e
partition coefficients o r even extraction coefficients f o r some si m pl e
system s.
The choice between the two models depends mostly on p r a c t i c a l reasons.
It s e e m s that the f i r s t model can be m os t profitably applied to extraction of

Z Radioanal. Chem. 31 f1976)

339

S. SIEKIERSKI:THE COMPLEXFORMATION-PARTITION
cations of high charge, z = +3 or +4. Such cations readily form strong
complexes with a v a r i e t y of ligands. The formation constants for some of
such complexes can in some cases be determined, so that the f r e e energy
of formation in the aqueous phase of the uncharged species can be calculated at l e a s t in principle. If the coordination number of the cation is either
low (n=3 or 4) or high (n=6), but in the l a t t e r case a complex with a
polidentat e ligand is formed, the neutral complex might be an unhydrated
species and its f r e e energy of partition between the organic and aqueous
phases can be, at least semiquantitatively, estimated. F o r such an e s t i m a tion the knowledge of the interactions between large, neutral, hydrophobic
molecules and water molecules is of p r i m a r y importance.
The second model is p a r t i c u l a r l y suitable for the description of e x t r a c tion of ions of low charge, z =+_1, and l a r g e r a d i u s . For such ions the
electrostatic part of the free energy of t r a n s f e r of the dissociated ion pair
can be, m o r e or less a c c u r a t e l y , calculated. In o r d e r to calculate the total
f r e e energy of t r a n s f e r of a dissociated ion-pair, the s t r u c t u r e - m a k i n g
properties of large ions in water have to be taken into account in addition
to the electrostatic t e r m . The problem of increasing the s t r u c t u r e of
liquid water by ions is essentially the s a m e as that encountered in t h e case
of large neutral molecules. The second t e r m , the f r e e energy of a s s o c i a tion of ions in the organic phase can be calculated in the case of ion pairs
using the equations of Bjerrum or F u o s s .
According to the two models proposed above, the overall extraction
p r o c e s s consists of two types of partial processes:
(1) the association of ions in either aqueous or organic phase, resulting
in the formation of an electrically neutral species;
(2) the partition between the organic and aqueous phase of either ions
or neutral m o l e c u l e s . Both partial p r o c e s s e s influence extraction and the

340

.L Radioanai. Chem. 31 H976]

S. SIEKIERSKI:THE COMPLEXFORMATION-PARTITION
share of each of them in the overall reaction depends on the system studied.
In this paper only the second type of p r o c e s s e s which is specific for e x t r a c tion will be d i s c u s s e d .
As stated above the calculation of partition coefficients r e q u i r e s the
knowledge of the interaction of large, neutral and hydrophobic molecules or
large hydrophobic, low-charged ions with water molecules. Such a knowledge can be gained from the solubility of organic substances in w a t e r .

Solubility of shnple organic substancesin water

In many practically important extraction s y s t e m s the species which
finally appears in the organic phase is an tmcharged complex with a hydrophobic surface formed by organic ligands attached to the central ion. The
partition of such a complex should closely r e s e m b l e that of a big organic
molecule. The partition of liquid organic substances between w a t e r and a
solvent is, in turn, closely related to their solubility in w a t e r . Solubility
in water can be treated as the partition of substance between water and its
own liquid phase. There exists a simple relationship between the standard
f r e e energy of partition,

AG~

and the standard free energy of solubil-

t-"

ity in water,

AG:ol, H20:

AGpart = - AG:ol, H2O + AGtransf, 2

(7)

o
w h e r e zlGtra~asf,
2 is the f r e e energy of t r a n s f e r of the partitioning liquid
substance (denoted by index 2) from pure liquid to a standard state in
solution taken as mole fraction unity. In the c a s e when the partitioned
substance is a solid, the f r e e energy t e r m s in the right hand part of

J. Radionnal. Cke'n. 31 {1976)

341

S. SIEKIERSKI:THE COMPLEXFORMATION-PARTITION
Eq. (7) r e f e r to the supercooled liquid, In that case Eq. (7) can be written
alternatively:
o

dGpart
where

AG~

= - AGsol, H20 +

H20 and

AG~

AG~

org

(8)

org denote the solubilities of the solid in

water and organic solvent, respectively. Both f r e e energy t e r m s contain

the f r e e energy of fusion which cancels because of the opposite sign.
From the two free energy t e r m s which determine partition, the first,
AG~

tt20 , is the m o r e important one and will be discussed in this

chapter in m o r e detail. The discussion will be limited to molecules which

do not possess acidic or basic functional groups capable of reacting specifically with w a t e r . It is well known that the solubility of homologous h y d r o carbons in w a t e r d e c r e a s e s with the number of carbon atoms. For instance,
the solubility of n-butane in water is 6.14 rag/100 g, whereas that of
n-octane is only 0. 066 rag/100 g. M c A u 1 i f f e I has shown that for each
group of hydrocarbons (paraffins, cycloparaffins, olefines, acetylenes,
a r o m a t i c hydrocarbons) there exists a linear dependence of the logarithm
of solubility, lg S, on the m o l a r volume, V 2, of the dissolved substance.
L i n d e n b e r g 2 has postulated a single linear dependence of lg S on V 2
for all hydrocarbons, including many substituted hydrocarbons. Although
the relation formulated by Mc A u l i f f e
L i n d en be r g ,

are m o r e exact than that of

the l a t t e r relation should be p r e f e r r e d for the prediction

of partition behaviour. The ligands attached to the central ion frequently

contain both aUphatic and aromatic radicals and sometimes also halogen
atoms, so that a relation between lg S and V 2 which takes into account
different hydrocarbons s e e m s to be m o r e suitable. It also enables to cover
a l a r ~ e r range of solubilities and m o l a r v o l u m e s . In Fig. 1 tue plot of

LIG~ ' H20 = -RT In x s

342

Z RadioanaL Chem. 31 (1976}

S. SIEKIERSKI:THE COMPLEX FORMATION-PARTITION

i
12-

E
"~ 11

8--

o/

7--

6--

54

3
2

100

F i g . 1.

200

R e l a t i o n b e t w e e n the s t a n d a r d f r e e e n e r g y of s o l u b i l i t y in w a t e r
and m o l a r v o l t t m e

of the s o l u t e

vs. V 2 has been presented for compounds listed in Table 1 (xs denotes the
solubility in mole fractions). It can be seen in Fig.1 that the linear dependence holds quite well, including compounds such as nitromethane. The
straight line equation established by the least squares method is:
AG:ol, H 2 0 = 56 V 2

J. Radioanal. Chem. 31 (1976J

cal/mole

(9)

343

S. SIEKIERSKI:THE COMPLEXFORMATION-PARTITION
Table 1
F r e e energy of solubility tn water, m o l a r volume
and solubility p a r a m e t e r of some organic compounds
No.

1
2
3
4
5
6
7
8
9
19
I1
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29

344

Compound

Nitrom ethane
Methyl bromide
Carbon disulfide
Methyl iodide
Ethyl br om i de
1, 2--Dlchloroethane
Ethyl iodide
Chloroform
1, 1 -D lchloroethane
1, 2-D tbromoethane
Bromoform
Benzene
Cyclopentane
Carbon t e t r a c h l o r i d e
1, 1, 1 - T r l c h l o r o ethane
n-Butane
Chlorobenzene
Toluene
Cyclohexane
o-D lehlorobenzene
n - P entane
o-Xylene
Ethylbenzene
Neopentane
n-Hexane
n-Heptane
a- O ct ane
iso-Octane
n-Decane

V2

~}2

54
57
61
63
76
79
81
81
85
87
88
89
95
97
100
101
102
107
109
113
116
121
122
122
132
147
164
166
197

12.6
9.4
10.0
9.9
8.9
9.8
9. 4
9.3
9.1
10.4
10.5
9.15
8.10
8.6
8.5
6, 7
9.5
8.9
8.2
10.0
7.05
9. 0
8.80
6.25
7.30
7.45
7.55
6.85
7.75

AG:ol, H20

3450
3550
4330
3760
3860
3820
4550
4050
4150
4550
4980
4610
5990
5520
5130
5900
4830
5420
6720
6470
6840
6170
6230
6715
7780
8560
9520
8750
11730

J. Radioanal. Chem. 31 (1976)

S. S I E K I E R S K I :

THE COMPLEX

FORMATION-PARTITION

r13

o
m

o,I
I

@,1
I

o,,1
I

c,,1
I

~
I

P-~
I

0,I

L"=

c~

0
e~
o

o
m
o
o
I

o
@1

o
m

F...=I

O
O
e~

o
m

L~

r.D

L~

(30

O~

~'~

I.~

9q4
cq

t~

o:i
q)

~o

t~

C0
it

o
C.)

J. Radioonai. C h e m . 31 ( 1 9 7 6 )

it

~3

(D

it

=,

345

S. SIEKIERSKI:THE COMPLEXFORMATION-PARTITION
It is interesting to note that Eq. (9) holds f o r m o l a r volumes up to about
200. That is f or m o l a r volumes m o r e than 10 times g r e a t e r than the m o l a r
volume of w a t e r . It means that l~elation (9) includes the t e r m which
accounts for mixing of molecules of unequal v o l u m e s .
Since the m o l a r volume of the CH2 group is about 16 cm 3, it follows
fr o m Eq. (9) that the addition of the CH2 group to a hydrocarbon molecule
r e s u l t s in the i n c r e a s e of

AG:ol, aq by about 900 c a l / m o l e .

The enthalpies and entropies of solubility of hydrocarbons in w at er

a r e known only in few c a s e s . Some of them a r e p r e s e n t e d in Table 2.
It follows from these data that enthalpies of solution of hydrocarbons in
w a t e r a r e close to zero, so that a l a r g e negative entropy is almost excl usively r es p o n s i bl e for the low and d e c r e a s i n g solubility in w at er with inc r e a s i n g V 2. Since halogen substituted hydrocarbons show the sam e d e pendence of lg x v s . V 2 it may be assumed that also t hei r solubility is
s
d e t e r m i n e d by the entropy f a c t o r .
The low solubility of hydrocarbons in water and the entropy c h a r a c t e r
of this p r o c e s s is a r e s u l t of the s t r u c t u r e - m a k i n g behaviour of h y d r o 3
c a r b o n s . According to F r a n k and E v a n s
organic molecules dissolved
in water i n c r e a s e the n u m b e r of t e t r a c o o r d i n a t e d w a t e r m o l e c u l e s . The
formation of a c l u s t e r of t e t r a c o o r d i n a t e d w at er molecules around the
dissolved h y d r o car bon o r h y d r o c a r b o n - l i k e molecule is equivalent to the
i n c r e a s e in the " i c e - l i k n e s s " of w a t e r . This i n c r e a s e is accompanied by
a substantial d e c r e a s e in entropy because w at er molecules which form the
c l u s t e r lose t h e i r t r a ns l at i onal m~d rotational d e g r e e s of f r e e d o m . The f o r m a tion of wnter c l u s t e r s is also c h a r a c t e r i s t i c of big organic cations 4
Since partition is a r e v e r s e p r o c e s s to the solubility in water, it
should also be mainly an entropy p r o c e s s , accompanied by a

substantial

i n c r e a s e in e n t r o p y . This should also be t r u e for the partition of complexes

346

J. RadioanaL Chem. 31 (1976)

S. SIEKIERSKI: THE COMPLEXFORMATION-PARTITION

of metal ions with hydrophobic ligands.5 Of course, the thermodynamic

c h a r a c t e r i s t i c s of the extraction p r o c e s s might be quite different since
extraction includes complex formation stage which can be mainly enthalpic.
Solubility parameter and its role in extraction
When the partitioned substance and the solvent differ appreciably in
their internal p r e s s u r e s the term

AGtransf, 2 in Eq. (7) may become

comparable with the term representing the solubility in water and has to be
taken into account. This can be done quantitatively provided the partitioning
(liquid) substance and the solvent form a r e g u l a r solution. The theory of
6-12
regular solutions has been applied by s e v e r a l authors
to extraction
problems, and has proved to be quite useful. An excellent review of the
application of the solubility p a r a m e t e r concept to extraction has recently
been given by I r v i n g .13 Certain conditions have to be fulfilled by the
two liquids to form a regular solution. In practice however, many solutions
although not r e g u l a r can be d e s c r i b e d by equations of the theory of regular
14
solutions with a sufficient degree of a c c u r a c y .
The theory of regular
o
solutions provides the following expression for AGtransf ' 2
o
AGtransf,

where V 2 is the m o l a r volume

= V 2 ( 5 1 - (~2)2
of the solute and

(10)

5 2 and ~ 1 a r e the

solubility p a r a m e t e r s of the diluted solute and solvent, r e s p e c t i v e l y . The

standard free energy of partition between water and organic solvent can be
now e x p r e s s e d in the following way:

or

AGpart = - 5 6 V 2 + V 2 ( ( ~ 1 - (~2)2

(11)

AGpart = V 2 [-56

(12)

I. Radioanal. Chem. 31 (1976)

((~1 - ~ 2 )2]

347

S. SIEKIERSKI:THE COMPLEXFORMATION-PARTITION
The sign of the free energy of partition depends on the relative magnitudes of the two t e r m s in b r a c k e t s . The solubility p a r a m e t e r of the p a r t i tioning substance,

6 2' probably r a r e l y exceeds

12. When heptane is

used as a solvent ( 6 1 = 7.45) the term ( 6 1 - 6 2 )2 is equal to about 20.

F o r other commonly used solvents, such as CC14, CHC13 and benzene,
this term is even smailer, since their solubility p a r a m e t e r s are higher.
In the majority of cases, therefore, the sum
- 5 6 + ( 6 1 - 62 )2
is negative, so that partition should increase with the m o l a r volume of
the partitioning s p e c i e s . As has been explained previously the term -56 V 2
is probably mainly entropic, whereas the term
V2( 61 - 62 )2
is purely enthalpic. Since in general
(6 1 -

62)2~56

the partition of a hydrophobic molecule between an organic solvent and

water should be mainly determined by the favourable entropy term resulting
from the d e c r e a s e in the number of water c l u s t e r s .
The solubility p a r a m e t e r has also been used in o r d e r to d e s c r i b e
mixtures between water and organic liquids. Such mixtures are certainly
not regular but formally one can write the following expression for the
standard free energy of solubility of an organic liquid in water:
O

AGsol ' H 2 0 = V 2 ( 6H20 - 62 )2

In this equation

(13)

~ H20 is an empirical p a r a m e t e r . The solubility

p a r a m e t e r of water, determined from the heat of vaporisation is equal to

23.8, The determination of the solubility p a r a m e t e r of water from the
348

J. RadioanaL Chem. 31 (1976)

S. SIEKIERSKI: THE COMPLEX FORMATION-PARTITION

2
o

20 -

o
/

19--

18-

17--

16

--

~ 1 7 6 ~176
o

15

14
I

"I

10

11

12

,.-

13
52

Fig. 2. Relation between the solubility p a r a m e t e r of water and the

solubility p a r a m e t e r of the solute
solubility of water in hydrocarbons gives a value between 22 and 24. In
o r d e r to get consistency between theoretical calculations and experiments
on the partition of some fl -diketones between water and organic solvents
the solubility p a r a m e t e r of water was assumed to be equal to 16.3.10
However, the empirical value of the solubility p a r a m e t e r of water can not
be constant, but must change with the solubility p a r a m e t e r of the dissolved
species. This follows from the comparison of Eq. (13) with the empirical
relation

AGsol, H20 = 56 V 2.
The difference (~ H2O - ~2 )2 must be equal to 56, and since 6 2 is different
for different substances
pendence of

must also change appropriately. The d e H20

~ H2 O on the solubility p a r a m e t e r of the dissolved substance

is shown in Fig. 2. The solubility p a r a m e t e r of water has been calculated

J. RadioanaL Chem. 31 (1976)

23

349

S. SIEKIERSKI:THE COMPLEXFORMATION-PARTITION

from Eq. (13) using the values of the f r e e energy of solubility, m o l a r

volume and solubility p a r a m e t e r listed in Table 1. The relation between
H2O and

~2 can be approximated by a straight line conforming to the

following relation:
~H20 =

62+7.5

(14)

Taking into account this relation, Eq. (13) can be presented in the
following form:
o
AGsol, H2O = V 2 9 7 . 5 2 = 56V 2

(15)

which is, of course, identical with Eq. (9).

Nevertheless, Eq. (9) should be p r e f e r r e d to Eq. (13) since the f o r m e r
r e q u i r e s only the knowledge of V , whereas the latter also r
The main difficulty in applying the concept of the solubility p a r a m e t e r
to the extractlon of ions is due to the fact that solubility p a r a m e t e r s and
molar volumes of the partitioning species are not known with sufficient
a c c u r a c y . This problem and some examples of the applications of the
concept of the solubility p a r a m e t e r to extraction will be discussed in m o r e
details in the next paragraph.
The complex formation - partition model. Calculation of partition coefficients of simple
molecules and complexes

In this model it is assumed that the complex of the extracted cation is

formed in the aqueous phase; the complex is then t r a n s f e r r e d into the
organic phase. Because of the role played by the complex formation stage
in the overall extraction p r o c e s s , the extraction coefficient should increase
with the stability constant of the complex. Because of the partition stage,
extraction should also increase with the m o l a r volume and h y d r o p h o b i c
c h a r a c t e r of the complex and with decreasing polarity. The increase of the
350

J. Radioanai. Chem. 31 (1976}

S. SIEKIERSKI. THE COMPLEX FORMATION-PARTITION

extraction coefficient with the molar volume

of the complex results from

the application of Eq. (11) to the partition of complexes. However, the

problem arises whether Eq. (11), which has been established for simple
organic molecules, can be applied to complexes. It certainly can not, in
cases when the ligand possesses electron-donor atoms in addition to those
engaged in bond formation with the cation (as is the case with HDBP,
HDEI-IP, T B P and similar extractants). Are such atoms absent, as is the
case e.g. with

fl-diketones, Eq. (11) can probably be applied. The only

objection is that the validity of Eq. (11) has been established for molar
volumes not exceeding 200, whereas the molar volumes of many complexes
are

greater. However an extension of Eq. (11) to higher molar volumes

seems to be justified in view of the fact that it probably contains the term
accounting for the mixing of molecules of unequal volumes. There are two
ways of transforming the cation to be extracted into a complex possessing
the required properties (high molar volume, hydrophobic character).
According to the first, the charge of the cation is neutralized by inorganic
anions, whereas the molar volume of the complex is increased by association with solvent molecules containing electron donor atoms. Association
with solvent molecules also removes the rest of hydrating water molecules
and renders the complex highly hydrophobic. According to the second way,
both the charge and hydrating water molecules are removed by a polidentate
organic anion, which at the same time renders the complex hydrophobic
and increases its molar volume.
Besides the relation between the partition coefficient and the properties

of the partitioning complex other features of the extraction process

can also be predicted, basing on the complex form ationopartition model.

These are: the influence of the diluent (inert solvent) on the extraction

J. RadioanaL Chem. 31 [1976/

23*

351

S. SIEKIERSKI:THE COMPLEXFORMATION-PARTITION
coefficient, the origin of the d i f f e r e n c e s in the extractability of s i m i l a r
and d i s s i m i l a r cations (ha the same system) and s e v e r a l o t h e r s .
Quantitative evaluation of extraction coefficients, is at the moment,
impossible on the basis of the complex f o r m a t i o n - p a r t i t i o n m odel . This
is mainly due to the fact that the stability constants of partitioning c o m plexes (particularly with organic ligands) are, in general, unknown and can
not be calculated from m o r e basic data. T h e r e are, however, two eases
when the extraction coefficient is equal to the partition coefficient and can
be t h e r e f o r e calculated at l e a s t in p r i n c i p l e . The f i r s t case is r e p r e s e n t e d
by the extraction of simple inorganic m o l e c u l e s like OsO4, the second by
s y s t e m s in which the e x t r a c t e d cation exists in the aqueous phase only in
the form of the complex, identical with that which is t r a n s f e r r e d into the
organic phase (identical, at l e a s t with r e s p e c t to the n u m b e r of ligands
attached). Such s y s t e m s can be exemplified by the extraction of metal ions
with some /~-diketones at high pH.
C o n t r a r y to extraction coefficients, a semiquantitative evaluation of
partition coefficients s e e m s to be p o s s i b l e . In principle, t h e r e a r e two
methods which can be used. The f i r s t is based on the application of E q . ( l l ) .
The application of this equation r e q u i r e s the knowledge of the solubility
p a r a m e t e r and m o l a r vol um e of the partitioning com pl ex. In the case of
simple complexes like GeC14 both r e q u i r e d values cart be found in the
l i t e r a t u r e o r easily calculated. The situation is m o r e difficult in the case
of complexes with organic ligands. T h e r e a r e however r e a s o n s to assum e
that the m o l a r volume of a c h e l a t e - t y p e complex is somewhat l ess than
9 of the ligand,10, 12 where n is the number of
n - t i m e s the m o l a r volume
ligands attached to the c e n t r a l ion, and that the solubility p a r a m e t e r of a
c h e l a t e - t y p e complex does not di f f er much from that of the ligand. 10' 12
In general, one should expect the solubility p a r a m e t e r of a c h e l a t e - t y p e

352

Jr. Radioanal. Chem. 31 (1976)

S. SIEKIERSKI:THE L-X)MPLEXFORMATION-FARrlTION
complex to be less than that of the ligand. The r e a s o n is that polar groups
which essentially contribute to the solubility para_m.eter of the f r e e ligand
a r e inactive in the bonded ligand. On the ot her hand it is probable that the
solubility p a r a m e t e r of a complex is equal to that of the d i m e r i z e d ligand 15
The approach based on Eq. (11) is limited to only few special c a s e s .
A condition of applying this equation is that the complex does not interact
with water molecules by hydrogen bonding. This is possible only if the
ligand r e m o v e s all w a t e r molecules from the hydration sphere of the cation
and if all e l e c t r o n - d o n o r atoms p r e s e n t in the Iigands a r e engaged in bonding with the c e n t r a l

cation. E x t r a c t i o n of some metal ionst with f l - d i k e -

tones can probably s e r v e as an example.

The second method is based on the assumption that the free energy of
partition of the complex is pr opor t i onal to that of the ligand, so that:

Ig Pcompl = n' Ig Plig + A

(I 6)

wh er e n' is slightly less than n, which is the num ber of llgand m ol ecul es
attached to the c e n t r a l cation. The existence of such a relation was confirmed e x p e r i m e n t a l l y . 10 Relation (16) can be deri ved from Eq.(11) p r o vided the solubility p a r a m e t e r of the complex is equal to that of the ligand,
and m o l a r volume of the complex is less than n - t i m e s that of the li,~and.
Relation (16) holds, however, also in the case when the complex f o r m s
hydrogen bonds with w at er m o l e c u l e s . If the num ber of hydrogen bonds is
the s ame in both f r e e and bonded ligand that can be t rue f o r the d i m e r i z e d
form of the ligand, one has approximately:
lg P c o m p l -- n' lg Plig

(17)

wh er e Plig denotes the partition coefficient of the d i m e r i z e d ligand.

J. Radioanai. Chem. 31 (1976)

353

S. SIEKIERSKI, THE COMPLEX FORMATION-PARTITION

If the p a r t i t i o n coefficient is c a l c u l a t e d with s o m e d e g r e e of confidence

by e i t h e r method, the evaluation of the c o n c e n t r a t i o n of the p a r t i t i o n i n g
c o m p l e x in the aqueous phase can be m a d e . If also the ltgand c o n c e n t r a t i o n
in the aqueous p h a s e is known, the stability constant of the c o m p l e x can be
e v a l u a t e d . Such an Indirect method of a p p r o x i m a t e evaluation of stability
c o n s t a n t s can be of s o m e v a l u e in few special c a s e s .
In the following, e x a m p l e s of applying Eqs (11) o r (17) to the c a l c u l a tion of p a r t i t i o n c o e f f i c i e n t s will be p r e s e n t e d along with e x a m p l e s of
calculating the c o n c e n t r a t i o n of c o m p l e x e s In the aqueous p h a s e .

Extraction

of OsO 4

V 2 = 58 and

~2 = 1 2 . 6 . A c c o r d i n g to E q . ( l l ) the s t a n d a r d f r e e e n e r g y

of p a r t i t i o n between c a r b o n t e t r a c h l o r i d e and w a t e r should be:

AG:art=-56.58+

58 ( 8 . 6 - 1 2 . 6 ) 2 = - 3 2 5 0 + 9 2 8 = - 2 3 2 2 c a l / m o l e

and the p a r t i t i o n coefficient (defined as a r a t i o of m o l e f r a c t i o n s ) P

= 50.
x
The e x p e r i m e n t a l v a l u e is 69.6~61 so that the a g r e e m e n t Is v e r y s a t i s f a c t o r y .

Extraction

of 1

V 2 = 59 and

62 = 1 4 . 1 . The s t a n d a r d f r e e e n e r g y of p a r t i t i o n between

w a t e r and CC14 a c c o r d i n g to Eq. (11) is:

-3304 + 1875 = -1429 c a l / m o l e ,

and

= 11.

Since the e x p e r i m e n t a l v a l u e is 48517 the t h e o r y fails c o m p l e t e l y in

this c a s e . However, it should be taken into account that E q . ( l l ) is only valid
f o r s u b s t a n c e s for which the enthalpy of solubility in w a t e r ts m u c h l e s s
i m p o r t a n t than the entropy t e r m . This is not the c a s e with Iodine since the
enthalpy of d i s s o l v i n g the s u p e r c o o l e d liquid iodine tn w a t e r (at 25 ~

354

is

J. Radioanal. Chem. 31 (1976)

S. SIEKIERSKI: THE COMPLEX FORMATION-PARTITION

about 2410 c a l / m o l e . Let us assume that in the case of iodine the f i r s t

term in Eq. (11) r e p r e s e n t s only the entropy contribution to the free energy
of solubility in w a t e r . The free energy of solubility in water of liquid s u p e r cooled iodine is then
3304 + 2410 = 5714
and the free energy of partition between water and CC14,
AG ~
= - 5714 + 1875 = -3839.
part
For P

one gets 630, in good agreement with the experimental value.

The agreement however could be obtained only with additional assumptions

and additional thermodynamic data.

Extraction

of GeC14

A sufficiently accurate stability constant of the GeC14 complex at high

HC1 concentrations is not known, so that the concentration of GeC14 in the
aqueous phase containing a known amount of HC1 can not be calculated.
As the r e s u l t a comparison between theoretical predictions and experimental results on the partition of GeC14 is not possible.
From the measured distribution ratio of germanium, Dx, and from the
theoretically calculated partition coefficient of the GeC14 complex between
CC14 and water the percentage content of the GeC14 species in the aqueous
phase can be calculated. The extraction coefficient of germanium into CC14
from 7.30M HC1 is 36.2, 8 and from 12.1M HC1 is 318018 (concentrations
expressed in mole fractions). The standard free energy of partition of
GeC14 between CC14 and water is, according to Eq. (11),
Gpart
~
= -56 9 115 + 1 1 5 . ( 8 . 6 - 8.1) 2 ---6411 c a l / m o l e ,
and

J. Radioanal. Chem. 31 (1976J

= 48000.
355

S. SIEKIERSK1,THE COMPLEXFORMATION-PARTITION
The percentage content of GeC14 should be
3620

100 Dx/P x - 4800------0-0.075% at 7.30M HCI,

and

318000
48000

6.6%

at

12.1M H C 1 .

These seem to be reasonable values. The approach exemplified by

the extraction of GeC14 can also be applied to other s i m i l a r cases e . g .
extraction of the halogcnides of As, Sb, and Sn.

Extraction

of complexes

with

organic

ligands

To the authors knowledge the only attempt to compare calculated with

experimental partition coefficients of complexes containing organic ligands
19
wasmadeby Allard,
Johnsson
and R y d b e r g .
The extraction of
zinc and copper acetylacetonates was studied. Instead of directly comparing
experimental with calculated partition coefficients the m o l a r volume and
the solubility p a r a m e t e r of the complex were calculated from the experimental extraction coefficients (at high pH), assuming

b H2O = 17.5.

The calculated solubility p a r a m e t e r s of the complexes were found to be

substantially g r e a t e r than the solubility p a r a m e t e r of the ligand, contrary
to what one would expect, and molar volumes s m a l l e r than twice the molar
volume of the ligand.
The difference between the expected and experimental value of the
solubility p a r a m e t e r of the complex is probably caused by the hydration of
the partitioning complex.
The application of Eq. (17) to the calculation of the partition coefficient
of the complex can be discussed on the example of extraction of the e u r o pium ion with HDBP. Since the composition of the complex with respect to

356

J. Radioanal. Chem. 31 (1976)

S. SIEKIERSKI,THE COMPLEXFORMATION-PARTITION
the ligand is EuIH(DBP)2]3 Eq.(17) can be applied. As explained p r e viously it is v e r y probable that the d i m e r i z e d ligand, as well f r e e as bonded,
i n ter acts with w a t e r and solvent m ol e c ul e s in the sam e way. The partition
coefficient of the I-IDBP d i m e r in the system 0.1M HNO 3 - CC14 is 1450~ 0
so that the f r e e energy of partition is -4320 c a l / m o l e . This value is much
l es s negative than that calculated from Eq. (11). Assuming V(DBP)2= 420
and

(~(DBP)2 = 9.3 (an e x p e r i m e n t a l value) one gets from E q . ( l l ) the f r e e

energy of partition of d i m e r equal to -23730 c a l / m o l e . The di fference is

m o s t probably caused by the hydration of the d t m e r in the aqueous phase.
It follows from Eq. (17) assuming n = 3, that the partition coefficient of the
Eu[H(DBP)2] 3 complex should be about 3.109. This seem s to be a r e a s o n able value when one takes into account the v e r y high m o l a r volume of the
complex that p r o m o t e s extraction, and hydration of the complex that is a
hindering f a c t o r . It should be noted that the experi m ent al l y d e t e r m i n e d
solubility p a r a m e t e r of the complex is equal to that of the d i m e r . 15 This
may be co n s id e r ed as e x p e r i m e n t a l evidence f o r the thesis that the d i m e r i z e d ligand i n t e r a c t s with both w a t e r and solvent m ol ecul es in the same
way, i r r e s p e c t i v e whether it is f r e e o r bonded to the cation.

The partition - association model. Single ion partition coefficients

According to this model equivalent amounts of cations and anions are

at f i r s t t r a n s f e r r e d f r om the aqueous to the organic phase, and then a s s o ciated to f o r m neutral m o l e c u l e s . In principle, this model can be applied
to any extraction s y s t e m , even to extraction of highly charged cations with
organic e x t r a c t a n t s . However, quantitative o r semiquantltative predictions
can be made only in the cas e of extraction of simple ion p a i r s . In such an
ion p a i r at least one of the ions (most frequently the cation) is highly h y d r o J.. Radioanal. Chem. 31 {1976}

357

S. SIEKIERSKI, THE COMPLEX FORMATION-PARTITION

phobic and has a large r a d i u s . In a qualitative way this model can be

applied to m o r e complicated s y s t e m s where either the cation or the anion
of the partitioning ion pair is a complex ion. The following equilibria must
be then taken into account:
MeZ+ + n X- ,
aq
aq
MeX z-n + (n-z) R +
n, aq
aq

MeX z-n
n, aq

~ MeX z-n + (n-z)B +

n, org
org

(I 8)

(19)

+
where R denotes the big, hydrophobic cation.
Usually, in the organic phase the association of the ions takes place.
Since almost every highly charged cation can be t r a n s f o r m e d into a complex
anion the partition - association model is of g r e a t practical importance.
Before discussing the quantitative possibilities of this model the
concept of the single ion partition coefficient must be introduced. The single
ion partition coefficient (called also single ion solvent activity coefficient
or individual extraction constant) can be defined in the following way:

- R T l r t P i = AGpart, i = AG:olv, i -

where d

art, i'

AG: olv, i and

AGhydr, i

(20)

A G~ydr, i are free energies of partition,

solvation and hydration of the ion, r e s p e c t i v e l y . Single ion partition coefficient, like any other thermodynamic property concerning individual ions
can not be determined experimentally without some extrathermodynamic
assumptions. These assumptions have been reviewed in detail by P a r k e r
21
and A l e x a n d e r
and will not be discussed in this paper.
As it has been previously shown by the autho 2 2 there also exists a
possibility of a s e m i e m p i r i c a l calculation of single ion partition coeffi358

Z Radioanat Chem. 31 {!976)

S. SIEKIERSKI, THE COMPLEX FORMATION-PARTITION

cients. For this purpose it is assumed that the free energy of the t r a n s f e r
of each ion, A G:art,~ i can be divided into two independent terms: the
electrostatic t e r m ,

' elzlG~

i and a neutral term,

~ G ; a r t , i"

AG;art, i = el AGpart, i + n AGP art, i

(21)

It was proposed that the electrostatic part of the free energy change
can be calculated from the Born equation using the crystallographic radius
of the ion and the macroscopic dielectric constant of both water and organic
solvent. In o r d e r to calculate the neutral term it was assumed that this
term for an ion is equal to that of an isoelectronic molecule (atom). The
details of the calculation depend on the ion under consideration. In the
case of big organic cations like tetrabutylaxnmonium cation the neutral
term is calculated by means of Eq. (11) assuming that the molar volume
and solubility p a r a m e t e r of the ion are equal to those of the isoelectrontc
molecule which in this case is tetrabutylmethane. In the case of the iodide
ion the neutral term is set equal to that of xenon. The f r e e energy of
partition of xenon is assumed to be equal to the ratio of solubilities in the
organic solvent and water. The neutral term for the perchlorate anion can
be calculated by extrapolating the approximately linear r e l a t i o n between
the free energy of partition and m o l a r volume, which relation is observed
in the case of noble g a s e s .
The agreement between the calculated and experimentally observed
free energy of partition of completely dissociated NBut4I between water
and chloroform was found to be very g o o d"2"
f However, this agreement
might only be fortuitous because of the cancellation of e r r o r s made in the
calculation of the separate t e r m s and because specific interactions between
CHC13 and iodide ions (postulated by some authors) were not taken into

J. Radioanal. Chem. 31 (1976]

359

S. SIEKIERSKI,THE COMPLEXFORMATION-PARTITION

a c c o u n t . R e c e n t r e s u l t 2 3 on the p a r t i t i o n of N-ProP4CIO4, NBut4CIO 4 and

NAm4CIO 4 between w a t e r and c h l o r o b e n z e n e o r o--dichlorobenzene show
that the e x p e r i m e n t a l l y o b s e r v e d p a r t i t i o n c o e f f i c i e n t s of t h e s e s a l t s a r e
by about 3 o r d e r s of magnitude l o w e r than the c a l c u l a t e d o n e s . On the
o t h e r hand the change in the p a r t i t i o n c o e f f i c i e n t with the s i z e of the cation
is n e a r to that c a l c u l a t e d t h e o r e t i c a l l y .
It is hoped that it has been shown in this p a p e r that the two p r o p o s e d
m o d e l s of solvent e x t r a c t i o n a r e useful f o r a quantitative u n d e r s t a n d i n g of
the r o l e of m a n y f a c t o r s which influence the e x t r a c t i o n of ions. On the o t h e r
hand the application of t h e s e m o d e l s to quantitative p r e d i c t i o n of e x t r a c t i o n
b e h a v i o u r is l i m i t e d to only v e r y few s i m p l e c a s e s . The r e a s o n s e e m s to
be not the l i m i t e d c h a r a c t e r of the m o d e l s but r a t h e r the l a c k of i n f o r m a t i o n
on the c o m p o s i t i o n , s t r u c t u r e and m o d e s of i n t e r a c t i o n of the s p e c i e s
a p p e a r i n g in each p a r t i c u l a r e x t r a c t i o n s y s t e m .

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