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Discussion of the
Physicochemical Effects of
Modifiers on the Extraction
Properties of Hydroxyoximes.
A Review
Ana M. Sastre
a
& Jan Szymanowski
b
a
Department of Chemical Engineering ,
Universitat Politcnica de Catalunya, E.T.S.E.I.B. ,
Barcelona, Spain
b
Institute of Chemical Technology and
Engineering , Poznan University of Technology , Pl.
SklodowskiejCurie, 260965, Poznan, Poland
Published online: 24 Aug 2007.
To cite this article: Ana M. Sastre & Jan Szymanowski (2004) Discussion of the
Physicochemical Effects of Modifiers on the Extraction Properties of Hydroxyoximes.
A Review, Solvent Extraction and Ion Exchange, 22:5, 737-759, DOI: 10.1081/
SEI-200035610
To link to this article: http://dx.doi.org/10.1081/SEI-200035610
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Discussion of the Physicochemical Effects of
Modiers on the Extraction Properties of
Hydroxyoximes. A Review
Ana M. Sastre
1
and Jan Szymanowski
2,
*
1
Department of Chemical Engineering, Universitat Polite`cnica de
Catalunya, E.T.S.E.I.B., Barcelona, Spain
2
Institute of Chemical Technology and Engineering, Poznan University
of Technology, Poznan, Poland
ABSTRACT
The physicochemical aspects of hydroxyoxime modication with various
modiers containing oxygen atoms are discussed. This kind of modication
is unique to hydroxyoxime reagents, which form weak intramolecular and
intermolecular hydrogen bonds. These bonds can easily be destroyed not
only by modier molecules (alcohols, alkylphenols, and esters) but also
by solvating diluents. Alcohols are stronger modiers than alkylphenols.
The drawback of these modiers is their strong self-association, which is
eliminated in esters and sterically hindered alcohols. The extraction proper-
ties of strong hydroxyoxime extractants can also be modied by adding
737
DOI: 10.1081/SEI-200035610 0736-6299 (Print); 1532-2262 (Online)
Copyright #2004 by Marcel Dekker, Inc. www.dekker.com
*
Correspondence: Jan Szymanowski, Institute of Chemical Technology and Engineer-
ing, Poznan University of Technology, Pl. Sklodowskiej-Curie, 260-965 Poznan,
Poland; E-mail: jan.szymanowski@put.poznan.pl.
SOLVENT EXTRACTION AND ION EXCHANGE
Vol. 22, No. 5, pp. 737759, 2004
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weak reagents (hydroxyoximes or b-diketones), which form co-associates
with strong extractants. The use of sterically hindered esters seem rational
for two reasons: they inhibit hydroxyoxime adsorption at the hydrocarbon/
water interface with oximino group penetrating the aqueous layers; and they
show negligible adsorption. Due to these phenomena, hydroxyoxime
extractants are more stable, and a retardation of the extraction is not
observed in the presence of hindered esters. There is currently no general
explanation of the chemistry of modication. Many published works
focus only on the interactions of modiers with extractants, neglecting
the interactions with metal complexes. In order to achieve a substantial pro-
gress in our understanding of the phenomenon of modication, interactions
between complexes and modiers must be studied and explained.
Key Words: Hydroxyoximes; Extractants; Dimerization; Modier.
INTRODUCTION
Modiers are often used in extraction systems for two reasons. Firstly, they
are used to increase the solubility of extractants and their complexes and to
avoid third-phase formation. Secondly, they are used to modify extraction prop-
erties, i.e., metal extraction and stripping abilities. The rst application is
usually found in systems containing various amines.
[16]
However, addition
of modiers is not unique to the routine extraction of metals. For instance, modi-
ers are also added to increase the polarity of supercritical CO
2
in supercritical
uid extraction [e.g., to increase the extraction of mercury(II) with sodium
diethyldithiocarbamate].
[7]
Polar modiers dissolved in supercritical carbon
dioxide improve the extraction of Hg(II). The improvement in extraction ef-
ciency depends on the polarity and acidity of the modier. Extraction improves
in the following order: none , hexane , toluene , dichloroethane ,
methanol , acetic acid. Although the effect is the opposite of that observed
in solvent extraction, the analogy can be seen clearly. The second application
is found in connection with hydroxyoximes (Structure 1) and the formation of
tailored blends where extraction and stripping properties are adjusted to the
aqueous feed [i.e., acidity and concentration of copper(II)] in such a way that
the maximum of the metal transfer is achieved in extractionstripping cycle.
Sastre and Szymanowski 738
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The technical aspects of these kinds of blends were recently discussed by
Kordosky and received very positively.
[810]
The blends included: ACORGA
5100 and 5050 fromthe rst generation of reagents, modied with nonylphenol
and hydrophobic alcohols; M 5640 and M 5774 modied with hydrophobic
esters; LIX 622 modied with tridecanol; and LIX 664N modied with esters
(Table 1). The study also included LIX 984N and LIX 973, which are mixtures
of aldoxime and ketoxime. The problem of industrial application of tailored
blends is still actual. It is easier and cheaper to optimize the composition of
the blend than to invent and produce a reagent with a new active substance.
Future developments will involve new and improved synergistic mixtures of
old reagents, rather than manufacturing new extractants.
The aim of this work is to discuss the physicochemical aspects of modify-
ing the extraction abilities of hydroxyoximes by adding modiers which form
hydrogen bonding with the hydroxyl and oximino groups of these extractants.
SELF-ASSOCIATION OF EXTRACTANTS
A characteristic feature of some extractants is their self-association,
especially the formation of cyclic dimers. Acidic extractants, e.g., monofunc-
tional organic acids, form stable dimers with dimerization constants in the
order 10
4
or even higher.
[1116]
Such a high value in the dimerization constant
is the result of the presence of strongly polarized groups (C55O or P55O in
carboxylic or phosphorus organic acids, respectively). These groups are
strong hydrogen-bond acceptors (i.e., strong electron donors) and form hydro-
gen bonds with acid hydroxyl group.
Hydroxyoximes contain a hydroxyl group which is less acidic
(pK
a
8.99.9) than the hydroxyl group found in the classical acidic extrac-
tants.
[17,18]
Actually, higher values, up to pK
a
12 are reported in the original
literature because they were determined in water dioxane mixtures. The
acidity of the phenolic hydroxyl group depends on hydroxyoxime structure
and changes as follows: 2-hydroxy-5-alkylbenzaldehyde oxime (active
substance in ACORGA reagents and LIX 860) . 2-hydroxy-5-alkylacetophe-
none oxime (active substance in LIX 84) . 2-hydroxy-5-alkylbenzophenone
oxime (active substance in LIX 65 and LIX 64N). Actually, the last two hydro-
xyoximes form two different isomers (E and Z, or anti and syn) that show a
different acidity of the phenolic group. The reagents are not currently pro-
duced and the problem of their isomerization and the association of
Z-isomer will not be discussed.
The most important issue is that the oximino group (55NOH) is a weak
proton acceptor.
[17,18]
Due to steric limitations, only the nitrogen atom can
form hydrogen bonds with the undissociated hydroxyl group of the same
Physicochemical Effects of Modiers 739
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Sastre and Szymanowski 740

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hydroxyoxime molecule (intramolecular bond, see Structure 1) or of the
second hydroxyoxime molecule (intermolecular bond) with the formation of
dimer (see Structure 2). The formation of intramolecular hydrogen bond
between the hydrogen atom of the oximino group and the oxygen of phenolic
group (see Structure 3) is only possible after a dissociation of the hydroxyl
group. For example, this could occur during contact with an alkaline
aqueous phase at pH . 11. These kinds of conditions are not encountered
in industrial copper extraction processes with hydroxyoxime reagents.
The IR spectra of hydroxyoximes depend on the diluent, and are signi-
cantly different in non-solvating (aliphatic hydrocarbons) and solvating
(aromatic hydrocarbons) diluents.
[19]
In practical terms, the non-solvating
diluents are not used alone. Aromatics are, to some extent, present in com-
mercial solvents to improve the solubility of hydroxyoxime copper com-
plexes. The IR spectra of alkyl derivatives of salicyl aldoximes, of
2-hydroxyacetophenone and 2-hydroxybenzophenone oximes (the active
substances present in commercial reagents) are similar in aliphatic hydrocar-
bons. They show a sharp band at 3580 cm
21
and a broad band at 3420 cm
21
.
This is characteristic of the monomeric and associated NOH group.
[20]
A
further broad band is observed at 3220 cm
21
. This is characteristic of the
phenolic hydroxyl group which is bound to the oxime nitrogen atom in
both the monomeric and the associated forms (Structures 1 and 2). Often,
these two bands are not separated and show-up as one broad band
between 3200 and 3400 cm
21
. The ratio of the integrated monomeric and
associated densities decreases with an increase in hydroxyoxime concen-
tration. This indicates a shift of the equilibrium towards associated
species. These three bands disappear in solvating diluents, such as toluene,
Physicochemical Effects of Modiers 741
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and there is a sharp band at 3510 cm
21
, which is characteristic in hydroxy-
oxime solvates.
[19]
Molecules of aromatic hydrocarbons carrying p electrons
behave as electron donors, and intermolecular p complexes are formed. The
dissociation of these solvate complexes is an additional barrier that must be
overcome when hydroxyoxime complexes with metals are formed. Thus,
hydroxyoximes behave as different species in aliphatic and aromatic hydro-
carbons. This is reected in extraction ability,
[1719,21]
interfacial adsorp-
tion,
[19,2226]
and kinetics.
[17,18,27]
The rates of copper extraction using
ACORGA P 50 and DEHPA decrease with an increasing tendency for the
diluent to interact with the extractant. There is, for example, an increase
in dipole moment, solubility, and the extractant distribution ratio. The rst
two parameters can be considered to be indicators of extractant polarity,
while the distribution ratio is representative of the extractant molecules
ability to be transferred to the aqueous phase. The uxes for copper(II)
extraction with P 50 decrease in the following order of diluents: heptane
methylcyclohexane . toluene . decaline . isopropylether octanol. The
results obtained with the use of decaline deviate from the expected. This
is due to the low quality of the diluent, which may contain some interfering
impurities.
The disappearance of monomeric species and the formation of solvates
decreases the extraction abilities and inhibits kinetics. In mixed diluents,
monomeric and associated species that are characteristic in octane and solv-
ates for toluene are in equilibrium. Their distribution depends on the
content of aromatics.
[19]
For systems with a toluene content of up to 5%,
the interface seems to have an aliphatic character. When the toluene
content is up to 20%, the interface is still not fully aromatic. However,
the interface is more aromatic than the bulk of the organic phase. Linear
solvation energy relationships based on the application of Kamlet and
Taft model enable the estimation of the effects of aromatics on the inter-
facial activity of hydroxyoximes, including surface tension and surface
excess.
[22]
The dimerization constants are in the range 110 in aromatic diluents,
but are signicantly higher (20120) in aliphatic hydrocarbons.
[17,18,20]
These large differences in the dimerization constants can be due to the
difference in water content of among the dried solvents. It is important to
note that the IR spectra were taken using dried solvents. Thus, water mol-
ecules compete during hydrogen bonding, hindering the formation of
weak hydroxyoxime associates. This hydration of extractant molecules has
been conrmed by molecular modeling.
[28,29]
However, in actual extraction
systems, the dimerization constants and degrees of isomerization are signi-
cantly lower in comparison with the values estimated in dried solvents.
[30]
The phenomenon is especially important in compounds that form weak
Sastre and Szymanowski 742
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hydrogen bonds (hydroxyoximes, for example). This effect is probably
smaller in association with acidic extractants, which form very stable
dimers.
On modeling extraction equilibria, Piotrowicz et al.
[31]
reports that the
dimerization of hydroxyoximes can be neglected in wet extraction systems.
The average value of the hydroxyoxime dimerization constant in kerosene
is only 1.7. Bogacki,
[32,33]
who models an extractionstripping system for
copper extraction with 2-hydroxy-5-nonylbenzaldehyde oxime and
2-hydroxy-5-nonylbenzophenone oxime reports the same phenomenon.
When using the Pitzer treatment
[34]
and calculating the activity coefcients
in the aqueous phase, a strong deviation from ideality is observed.
[31]
However, the estimated dimerization constants are small, statistically equal
to zero (0.6 + 0.2 or 20.7 + 3.3). Tanaka
[35]
also neglects the dimerization
of hydroxyoximes. However, he uses the modied reagent ACORGA P5100
to extract copper(II) from HCl and HNO
3
solutions. The activities are calcu-
lated according to the Bromley and the Pitzer models. The model agrees with
the experimental extraction data very well. The computed association
constants are, again, near zero and equal to 0.8 and 1.2 for the hydroxyoxime
dimerization and hydroxyoxime co-association with nonylphenol, respect-
ively. Recently, two works were published
[36,37]
in which the extraction equi-
librium with hydroxyoximes was modeled, neglecting the dimerization
constants. The differences observed are explained by strong deviations from
ideality in the aqueous acidic sulfate phase.
Actually, it is impossible to prove that the dimerization disappears in
wet solvents. It is more justied to assume that the equilibrium constant is
small and the dimerization still occurs, decreasing the content of monomeric
forms.
CO-ASSOCIATION OF HYDROXYOXIMES AND
MODIFIERS HAVING HYDROXYL GROUP
Hydroxyoximes with a55NOH group can form co-associates with various
alkylphenols, alcohols, ethers, ketones, and esters. Alkylphenols, alcohols,
and esters are, in practice, exploited in modern hydroxyoxime blends. The
formation of co-associates between different hydroxyoximes is also possible
and is currently exploited.
A hydroxyoxime molecule with intramolecular hydrogen bonding
(Structure 1) has two oxygen atoms. Each oxygen atom has two free elec-
tron pairs and one mobile hydrogen atom that is able to participate in
hydrogen bonds. Thus, theoretically, up to ve molecules (alcohols or alkyl-
phenols) can be bound into hydroxyoxime associates. Four of the molecules
Physicochemical Effects of Modiers 743
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would act as hydrogen-bond donors to the oxygen atoms of the hydroxy-
oxime, and one molecule would act as an hydrogen-bond acceptor for the
hydrogen from the oximino group. The nitrogen atom from the oximino
group also acts as an hydrogen-bond acceptor. Although the nitrogen
atom may bind an alcohol molecule, the formation of an intramolecular
bond with the hydrogen from the phenolic hydroxyl group seems more
probable.
A modier molecule may approach a hydroxyoxime molecule at various
sites, giving associates of somewhat different energies. Molecular modeling,
carried out for isolated molecules of hydroxyoxime and a modier, suggests
the formation of associates containing only one or two modier mol-
ecules.
[38,39]
The formation of 1 : 1 and 1 : 2 hydroxyoximealcohol associates
is also deduced by Freiser
[40]
from the modeling of copper extractions with
2-hydroxy-5-alkylbenzaldehyde oximes.
It is impossible to specically locate the modier molecule in associ-
ates. This is because the differences between the PM3 formation heats
computed for the various associates are small (only a few kJ/mol). Different
associates are, therefore, probably present in an equilibrium mixture.
However, some peculiarities are observed when bulky branched alcohol
molecules are considered. The steric effect is evident and a modier mole-
cule with a highly branched alkyl chain in the close proximity to the
hydroxyl group is shifted to the hydroxyoxime group in modier extractant
associate. The band that is characteristic of the hydroxyoxime monomer
rapidly disappears in the IR spectrum after introducing a modier to a
hydroxyoxime solution in a hydrocarbon. Instead, a broad and intense
band appears which is characteristic in hydroxyoxime associates with modi-
er molecule(s). Similar changes are observed in the IR spectra when
alcohol is added to pyridinecarboxamide. This demonstrates the formation
of an intermolecular hydrogen bonded amide and alcohol co-associate.
[41]
Polar solvents that have a proton acceptor group (e.g., alcohols), even break
carboxylic acids dimers and form intermolecular H-bond complexes.
[42]
Aliphatic alcohols show a greater electron density on the oxygen atom
than alkylphenols, and they form associates with hydroxyoxime molecules
more easily. This effect is manifested in the reduced amount of alcohol
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needed to obtain the same modication of hydroxyoxime extraction/
stripping abilities as when using nonylphenol. Actually, half the amount
of tridecanol is needed to obtain the same effect as when using nonylphenol,
when it is added to 2-hydroxy-5-nonylbenzaldehyde oxime (P 50 reagent).
[43,44]
Alcohols also behave differently to alkylphenols in terms of self-
association. Alkylphenols form linear associates (see Structure 4) with the
association constants in the range 5080 Lmol
21
.
[45,46]
Alcohols form differ-
ent species such as linear dimers, trimers, and tetramers (Structure 5). The
cyclic tetramer (Structure 6) is probably dominant for linear and slightly
branched alcohols.
[47]
Tetramer content increases with alcohol concentration. It also increases as
temperature decreases. At 258C, tetramers of decanol are the predominant
species in decane when the alcohol concentration is greater than 4%.
However, the associationof an alcohol depends uponits structure, anddecreases
with increased branching of the alkyl chain near the hydroxyl group. For
example, the monomer is the dominant species at a 10% solution of 4-propyl-
heptan-4-ol in decane at 258C.
[48]
Highly branched alcohols should be used
even with smaller amounts for hydroxyoxime modication, because they
could be used exclusively for hydrogen-bond formation with hydroxyoximes.
Physicochemical Effects of Modiers 745
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When considering the effect of the modier on the extraction of copper,
the following equilibria should be taken into account:
Cu
2
w
2HL
o
OCuL
2o
2H

w
2
2HL
o
OHL
2o
3
HL
o
nROH OHLnROH
o
4
mROH
o
OROH
mo
5
where HL stands for hydroxyoxime; subscripts o and w denote the organic and
aqueous phase respectively; n is equal to 1 or 2; and m varies from 1 to 4. Is n
equal to 4 for alcohols used in commercial blends? Only extractant producers
can answer this question, as only they know the composition and structures of
the modiers added. Reaction (3) consumes monomeric hydroxyoxime mole-
cules, thus shifting reaction (2) to the left decreasing the extraction abilities of
the hydroxyoximes. This effect would be negative for weak extractants such
as 2-hydroxy-5-nonylbenzophenone oxime (LIX 65N and LIX 64N from the
rst generation of hydroxyoximes produced by General Mills). The effect
would be positive for hydroxyoximes which form strong and stable complexes
such as 2-hydroxy-5-nonyl(or dodecyl)benzaldehyde oxime (ACORGA P 50
and LIX 860), and also for 2-hydroxy-5-nonylacetophenone oxime (LIX 84).
A decrease in extraction ability is compensated by an increase in stripping
ability.
[43,44]
As a result, more copper is transferred from an aqueous feed to
the hydrocarbon phase and, after that, to an aqueous strip phase in modied
strong hydroxyoximes. The optimization of technological processes concern-
ing reagents with different extraction abilities were rst modeled and dis-
cussed by Tanaka
[49]
and then developed for modied extractants by
Bogacki.
[50]
Their studies showed that tailored modied reagents can mean
an increased production of copper, or that the process can be carried out in
a smaller plant.
A computer simulation of a steady-state countercurrent multistage extrac-
tionstripping process shows that there is a value of the extraction equilibrium
constant that yields the maximum metal recovery when the other operational
parameters are constant.
[49]
The extraction is insufcient for a low extraction
constant. The stripping is excellent, but the total transfer of metal from the
aqueous feed to the strip is low. The extraction is excellent for a high extrac-
tion constant but the stripping is inefcient. As a result, the overall transfer is
also low.
The association phenomena (extractant association, modier association,
and extractant-modier co-association) change the optimum strength of
extractant which is needed to obtain an optimum metal transfer rate.
[50]
This
optimum transfer from the feed to the loaded electrolyte is obtained when an
appropriate combination of the equilibrium constants of extraction, association
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and co-association is found. Extractant association and co-association have a
negative effect in weak extractants and a positive effect in strong extractants.
The co-association of the modier with the extractant changes the optimum
strength of the extractant (or the extraction equilibrium constant) for both the
multistage countercurrent and the crosscurrent processes.
CO-ASSOCIATION OF METAL COMPLEXES
AND MODIFIERS
An association of the modiers with the extracted hydroxyoximecopper
complex (Structure 7) should also be considered.
The importance of this phenomenon can be deduced from the work of
Moyer et al.
[51]
. This work shows the relationship between the modiers
hydrogen-bond donor strength and the cesium extraction with calix[4]arene-
bis-(tert-octylbenzo-crown-6) and suggests the solvation of the complex via
hydrogen-bond interactions. The importance of hydrogen bonding in both
the extractant and the complex is also observed during the extraction of
alkali metal nitrates with crown ethers in octanol.
[52]
As a result, the effect
of an alcohol modication on extraction efciency cannot be predicted. For
instance, the extraction abilities of benzo-crowns increase when changing
the diluent from 1,2-dichloroethane to octanol, but the extraction ability of
the dicyclohexano-crowns decreases. The same phenomenon is observed
when alcohol is added to pyridenecarboxamides dissolved in toluene and
the mixture is used for the extraction of copper from chloride solutions.
[41]
Depending on the experimental conditions, extraction can increase or decrease
slightly in the presence of alcohol. Addition of decanol (20% vol/vol)
improves the extraction of copper(II) from concentrated chloride solutions
with dipentyl pyridine-3,5-dicarboxylate.
[53]
This indicates that the associ-
ation of the alcohol with the complex has a stronger positive effect than the
co-association with the extractant. This effect becomes dominant when
there is a very high alcohol content (50100% vol/vol). In this situation,
the efciency of copper(II) extraction decreases. An improved extraction of
Physicochemical Effects of Modiers 747
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cadmium(II) is observed with 3,5-diisopropylsalicylic acid in the presence of
thiols. This is explained by the incorporation of the thiol molecules in the
extracted complexes.
[54]
Further conrmation of the complex solvation is
shown by Gloe et al.,
[55]
who demonstrated that the extraction of U(VI) and
V(V) with pyrazolone derivatives depends on the presence of alcohol. The
addition of dodecanol results in an enhancement of the extraction of vana-
dium(V) at high HCl concentrations, but reduces the extraction of U(VI)
due to a change in the extraction mechanism. Alcohol molecules incorporate
into the extracted complexes. There is some analogy between solvation and
hydration of metal complexes with ligands containing oxygen atoms. The
uranyl-isoxazolonate is stabilized by both inner- and outer-sphere hydration
in the aqueous phase (Structure 8).
[56]
The introduction of an electrolyte
enhances the extraction due to dehydration of the complex.
The problem of inner- and outer-sphere hydration was broadly discussed
in the works of Narbutt,
[5760]
however, rather for hydrophilic extractants.
The hydrophilic properties of ligand oxygens result in outer-sphere hydration
of the complex and affect the partition coefcient of the complex. The outer-
sphere hydration depends on the coordination mode and on the distribution of
the electron density in the complex because the molecular structure may affect
the access of water molecules to oxygen atoms in the ligands, while electron
density on oxygen atoms, which depends on the central metal ion, may affect
the strength of hydrogen bonds to water molecules. Two water molecules can
form hydrogen bonds with ligand oxygens in the square-planar b-diketonates,
compared with four in the tetrahedral b-diketonates.
[60]
Chloroform and halophenols (Lewis acids) form outer-sphere solvates
with metal acetylacetonates by means of hydrogen bonding to donor oxygen
atoms
[57,61]
which enhances the extraction of metal complexes to the
organic phase. Each acetoacetonate ligand binds one molecule of halophenols
or chloroform.
An increase in the hydrophobic character of the extracted metal complex is
observed in the synergistic extraction of mixed complexes (adducts formed
Sastre and Szymanowski 748
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when the additional ligand has a pair of unbonded electrons at the nitrogen or
oxygen atom). Three different mechanisms are postulated.
[62]
The rst one
involves the opening of one or more chelate rings and occupation by the
adduct molecule(s) of the vacated metal coordination site(s). In the second
mechanism, the metal ion is not coordinately saturated by the ligand and,
hence, it retains residual water in the coordination sphere, which can be replaced
by adduct molecules. The third mechanisminvolves the expansion of the coordi-
nation sphere of the metal ion to allowbonding of the adduct molecules. Tributyl
phosphate, trialkylphosphine oxides, trialkylamines and also pyridinecarboxy-
late esters are used to form adducts and increase the extraction.
[62,63]
Electron spin resonance studies of hydroxyoxime complexes with
copper(II) show the formation of ve-coordinated square pyramidal species
containing one additional molecule of pyridine or ammonia (Structure 9).
[6466]
A pseudo-octahedral adduct of bis(2-hydroxybenzaldehyde oxime) nickel(II)
with two pyridine molecules occupying trans axial positions (Structure 10)
was isolated by Basolo and Matoush.
[67]
However, there are no more data
available.
Why, then, do hydroxyoximes behave differently to other extractants?
This phenomenon has not been studied. However, one can deduce that modi-
er molecules solvate both hydroxyoxime and its copper complex. The hydro-
gen bonds in the complex may be broken by modier molecules, leading to a
decreased stability of the complex. However, this kind of associate of the
complex with modier molecules becomes somewhat more hydrophobic
and is thus transferred more easily to the hydrocarbon phase. The effect
cannot be signicant because both the hydroxyoxime and complex are very
hydrophobic. Although the modeling shows that the solvation of hydroxyox-
ime molecules is a crucial factor as to the extraction abilities of hydroxyoxime
extractants, it is also probable that the effect is caused by a decreased complex
stability due to the breaking of hydrogen bonds in the vemember rings of
the complex (see Structure 7). Further studies on the phenomenon are
needed. Actually, the literature upon that problem is very scarce and poor.
Physicochemical Effects of Modiers 749
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CO-ASSOCIATION OF HYDROXYOXIMES WITH
ESTERS AND OTHER EXTRACTANTS
Both Cytec and Cognis use esters for the modication of hydroxyoxime
extractants.
[810,68,69]
These esters have two oxygen atoms in the carboxylic
group and can act only as electron donors. They form a hydrogen bond with
the hydrogen atom of the oximino group. The steric features and high polarity
of the carbonyl group favor the formation of the hydrogen bond with the
oxygen atomof the C55Ogroup.
[39]
The 1 : 1 associate with a well-dened struc-
ture is formed. The effect of both hydrocarbon chain length branching and the
position of a long alkyl chain on the predicted stability of the associate is small.
Both companies claim that these new blends (M 5640, M 5774, and LIX
664N) provided a better extraction performance and more hydroxyoxime
stability than the previous blends containing alcohols. Although this information
is not supported by independent research, the behavior seems possible. Esters
that form a hydrogen bond with the oximino group block the terminal hydroxyl
group (55NOH
. . .
O55C(OR
0
)R and change the symmetry and the hydrophilic
lipophilic balance of the modied molecules. The presence of this kind of associ-
ate must indicate a decrease in the ability to adsorb at the hydrocarbon/water
interfaces, thus decreasing or even eliminating the penetration of the oximino
group into the aqueous layers near the interface. As a result, a contact of the
associate with the aqueous phase is limited, and the possibility of hydrolysis
and other reactions unfolding is diminished. The problemof interfacial behavior
and kinetics was reviewed comprehensively in the literature.
[70,71]
Hydroxyoximes with weak extraction abilities (2-hydroxy-5-nonylbenzo-
phenone oximes that were present previously in LIX 65N and LIX 64N) can
modify the extraction abilities of salicyl aldoximes (2-hydroxy-5-alkylbenzal-
dehyde oximes) and 2-hydroxy-5-alkylacetophenone oximes. LIX 864, LIX
865, LIX 973, and LIX 984 are appropriate examples among commercial
extractants. They contain no additional, nonchelating modiers, but their
extraction properties are better than expected according to the additive
rule.
[72,73]
They maintain strong extraction abilities, and stripping is markedly
improved. The formation of mixed associates is conrmed by the molecular
modeling, which demonstrates the formation of 1 : 1 and 1 : 2 co-associates.
b-Diketones (LIX 54) can also be used for the modication of hydroxy-
oximes.
[74]
LIX 54 works as a modier of LIX 84 by the formation of 1 : 1
and 2 : 1 co-associates. The extraction ability of LIX 84 is decreased slightly,
but stripping is improved. A 1.6 M H
2
SO
4
can strip 9698% of the copper(II)
in a loaded LIX 54 and LIX 84-LIX 54 mixture (1 : 1). However, this kind of
modication is not practically exploited in commercial blends.
The addition of modiers improves stripping and increases the transfer of
copper(II) during the extraction and stripping cycle. The ratio of active oxime
Sastre and Szymanowski 750
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to modier can be altered so as to control the extractive strength of the blend.
This means that the extractant can be tailored in order to meet the specic
needs of a leach solution.
[73]
DRAWBACKS OF MODIFICATION
Alcohols and alkylphenols exhibit some surface activity and adsorb at the
hydrocarbon/water interfaces.
[2325,75,76]
When used in the mixtures with
extractants, they compete for the adsorption area at the interface. The inter-
facial population of the extractant molecules is therefore decreased,
[77]
and
they act in the same way as aromatic diluents.
[78]
The same phenomenon is
observed in other extractants, e.g., dinonylnaphthalene sulfonic acid, bis(2-
ethylhexyl)phosphoric acid, decylpyridine-carboxylates, and HOSTAREX
A327 and their blends with alcohols and alkylphenols.
[7984]
This adsorption
of modiers results in a decreased rate of extraction.
[8386]
Fortunately, this
retardation in the classical dispersive extraction process is not very large,
because the interface is dynamic and quickly regenerated. The problem may
become considerable in the future, when membrane processes with stable
interfaces in the pores of bers or ceramics will be used. Then, a considerable
decrease in mass transfer with modied extractants would be observed. It
would thus be necessary to return to the previous generation of unmodied
extractants. However, the benets of using esters as modiers can still be pos-
tulated. Although such studies of interfacial activity and kinetics of extraction
in ester have not been described in the literature, one can predict that they do
not adsorb at the hydrocarbon/water interfaces or that their surface activity is
low. As a result, they cannot accumulate at the interface and retard extraction
in this way.
A decrease in mass transfer in the presence of alcohols and alkylphe-
nols is not a general phenomenon. When using dibutyldithiophosphoric acid
for the extraction of nickel from acidic sulfate solution, it is observed that
the stripping is facilitated and accelerated in the presence of octanol.
[87,88]
This could be due to a different chemistry in the Cu(II) and Ni(II) com-
plexation. An exchange of water molecules in nickel(II) complexation is
slower than it is with copper(II). The extraction is slow and kinetic
equations are usually different from than those derived for copper(II).
[70,71]
Both the rate and the efciency of gallium(III) extraction from alkaline
solutions with 5-alkanoyl-8-hydroxyquinoline are increased when either
2-hexanone as a modier or hexadecyltrimethylammonium chloride
(CTAB) as a surfactant is added to the extraction system.
[89]
The reason
for the positive modication observed in the presence of the modier
cannot be predicted, but the effect of CTAB is probably connected to the
Physicochemical Effects of Modiers 751
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formation of reverse micelles and microemulsions, as reported by Bauer
[90]
and reviewed by Paatero.
[91]
The effect cannot be attributed to the adsorp-
tion of CTAB molecules at the hydrocarbon/water interface because, due to
electrostatic repulsion, a retardation of extraction would be observed.
[92,93]
Hydroxyoximes modied with alkylphenol cannot be used for the extrac-
tion of copper from ammoniacal solutions because they co-transfer too much
ammonia. Nonylphenol has a deleterious effect on certain construction
materials such as natural rubber.
CONCLUSIONS
This physicochemical discussion of hydroxyoxime modication with
various modiers containing oxygen atoms shows that this kind of modi-
cation is unique to hydroxyoxime reagents, which form weak intramolecular
and intermolecular hydrogen bonds. They can easily be destroyed, not only by
modier molecules (alcohols, alkylphenols, and esters), but also by solvating
diluents and the water present in actual extraction systems. Alcohols are
stronger modiers than alkylphenols. The drawback of these modiers is
their strong self-association, which is eliminated in esters and sterically hin-
dered alcohols. The extraction properties of strong hydroxyoxime extractants
can be also modied by an addition of weak reagents (hydroxyoximes or
b-diketones), which form co-associates with strong extractants. The use of
sterically hindered esters seems promising due to two reasons: they inhibit
hydroxyoxime adsorption at the hydrocarbon/water interface with the
oximino group penetrating the aqueous layers and show little to no adsorp-
tion. Due to these phenomena, hydroxyoxime extractants are more stable,
and a retardation of the extraction is not observed in the presence of hindered
esters. The chemistry of modication is not well explained because the works
published in the past focused solely on the interactions of modiers with
extractants, neglecting their interactions with metal complexes. In order to
achieve considerable progress in understanding the modication phenom-
enon, interactions between complexes and modiers must be studied.
ACKNOWLEDGMENTS
This work was supported by the V Comision Mixta Hispano-Polaca.
Ministerio de Asuntos Exteriores. One author (J.S.) would like to thank DS
032/044, Poznan, Poland for his support.
Sastre and Szymanowski 752
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Received January 7, 2004
Accepted April 30, 2004
Physicochemical Effects of Modiers 759
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