Hydrometallurgy 72 (2004) 139 – 148

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Infrared spectroscopy of metal carboxylates

II. Analysis of Fe(III), Ni and Zn carboxylate solutions
E.G. Palacios a,*, G. Juárez-López a, A.J. Monhemius b
a
Departamento de Ingenierı́a Metalúrgica, ESIQIE, Instituto Politécnico Nacional, A.P. 75-616, 07738 México, Distrito Federal, Mexico
b
Imperial College of Science, Technology and Medicine, RSM, Prince Consort Road, London SW7 2BP, UK
Received 29 May 2002; received in revised form 13 March 2003; accepted 8 June 2003

Abstract

The metal carboxylate complexes present in the organic solutions used in the hydrolytic stripping process strongly affect the
nature of the solid precipitated; in some cases, the product is a mixed oxide while in others, a mixture of single-metal oxides is
obtained. Infrared (IR) spectroscopy is a useful tool for determining the speciation of metal loaded organic phases. In the
previous work, relationships of the form [V-10] = aAmM + bAmD were obtained for the estimation of the free Versatic acid present
in metal carboxylate solutions at given specific temperatures. In this work, infrared spectroscopy has been used for the
speciation of single-metal Versatic 10k solutions containing Fe(III), Zn and Ni at temperatures between 20 and 200 jC.
It was found that iron and zinc predominantly form complexes with bidentate structures at all the concentration levels tested,
while the nickel complexes contain bidentate ligands at low concentrations and both monodentate and bidentate ligands at high
concentrations. The evidence found in this work supports the existence of a binuclear ferric Versatic complex, [Fe(OH)V2]2,
with chelating Versatic groups forming an octahedron around each of the iron atoms. An oxo-centred structure, containing only
bridging carboxylate groups, is proposed for the zinc Versatic complex, which is believed to be present in the organic medium
as Zn4O(V)6.
D 2003 Elsevier B.V. All rights reserved.

Keywords: Infrared spectroscopy; Metal carboxylate; Versatic complex

1. Introduction when carboxylate solutions containing several metals

are used, in certain cases the product is a mixed
Infrared (IR) spectroscopy is a reliable technique oxide while in others, a mixture of metal oxides is
for the characterization of metal carboxylate species obtained. As a first step in the characterization of
present in organic solutions such as that used in the metal carboxylate species by IR spectroscopy, rela-
hydrolytic stripping process. The chemical nature of tionships between the total concentration of the
the carboxylate species strongly affects the compo- carboxylic acid and the absorbance of the character-
sition of the solid products obtained by that process; istic dimer and monomer bands were obtained at
several temperatures (Palacios and Monhemius,
2001). In order to characterize the mixed-metal
* Corresponding author. Versatic solutions containing Fe(III), Zn and Ni,

0304-386X/$ - see front matter D 2003 Elsevier B.V. All rights reserved.
doi:10.1016/S0304-386X(03)00137-3
140 E.G. Palacios et al. / Hydrometallurgy 72 (2004) 139–148

which are used in studies aiming to produce Ni,Zn- atoms; the molecule possesses a C2 rotation axis of
Fe2O4, the speciation of the single-metal Versatic symmetry (Dresseyn, 1992), i.e. rotation around the
solutions is a necessary step, given that the structure C – R axis by 180j yields a molecular configuration
and chemical composition of the single-metal species indistinguishable from the original one. The carbox-
will determine the nature and number of complex ylate group also retains C2 symmetry when acting as a
species formed in the Fe(III)/Zn/Ni Versatic solu- bridging group or as a bidentate chelating; thus, from
tions. In this work, an IR spectroscopy study of the the point of view of symmetry, the CO2 frequencies of
single-metal Versatic solutions at several concentra- such structures could not be expected to be too
tions and temperatures is reported. The bands different from those observed in the free ion spectrum.
appearing in the region between 1800 and 1400 The derivatives with unidentate carboxylate ligands
cm
1 were analysed in all the spectra. have a lower symmetry (Cs) (Mehrotra and Bohra,
1983), and therefore could be expected to show
similarity to the spectra of the undissociated carbox-
2. Antecedents ylic acids.
The most useful characteristic bands of metal
Four distinct patterns of behaviour have been carboxylates are a strong asymmetric CO2 stretching
established for the carboxylate ligand on the basis of vibration (i.e. mCOasym) and a somewhat weaker
actual structural determinations (crystallographic symmetric CO2 stretching vibration (i.e. mCOsym);
methods), as shown in Fig. 1 (Mehrotra and Bohra, the bands corresponding to the coordinated modes
1983; Dresseyn, 1992). Ionic, bidentate chelating and (structures II, III and IV) are situated at different
bidentate bridging structures (types I, III and IV, frequencies relative to values for the free carboxylate
respectively) show certain resemblance to each other ion (structure I), usually taken as those of the sodium
in their IR spectra; however, all three differ markedly or potassium salts (Dresseyn, 1992). The frequencies
from those of the carboxylates of the type II (uniden- of the bands are highly sensitive to the structure of the
tate carboxylate ligands). In ionic carboxylates, the carboxylate group, the nature of the solvent, the nature
metal atom is associated equally with the two oxygen of the ligand and the identity of the metal ion (Colthup
et al., 1990); therefore, the separation of the bands
(i.e. Dm = COasym
COsym) is also indicative of the
structure of a given carboxylate.
Ionic carboxylates exhibit two bands (mCOasym and
mCOsym) in their IR spectra; the first band appears as a
very strong and generally broad band while the
second band is less intense (Mehrotra and Bohra,
1983; Colthup et al., 1990). The versatate anion,
formed by reaction of KBr with Versatic 10, shows
its corresponding asymmetric and symmetric CO2
stretching vibration bands at 1530 and 1470 cm
1,
respectively (Palacios-Beas, 1994). In all the three
coordination structures, there is a drastic change in the
intensity of both symmetric and asymmetric modes in
comparison with ionic carboxylates: the asymmetric
stretching becomes more intense than the symmetric
one (Mehrotra and Bohra, 1983; Crabtree and Rice,
1974).
In comparison with its corresponding free ion, a
Fig. 1. Structure of metal carboxylates according to the type of
metal – ligand interaction. (I) Ionic or uncoordinated form, (II) large splitting of the CO2 stretching frequencies
unidentate coordination, (III) bidentate chelating coordination, (IV) (Dm) is often an indication of monodentate coor-
bidentate bridging coordination. dination in a metal carboxylate; the asymmetric
 E.G. Palacios et al. / Hydrometallurgy 72 (2004) 139–148 141

stretching frequency increases and the symmetric (Mehrotra and Bohra, 1983; Dresseyn, 1992; Crab-
one decreases, due to the breakdown in equality tree and Rice, 1974); this hypothesis is founded on
of the carbonyl group (Mehrotra and Bohra, 1983; the premise that in chelating acetates, the O –C – O
Colthup et al., 1990). These frequencies then corre- angle will be smaller than in bridging acetates, thus
spond approximately to mCMO and mC –O, respec- leading to a decrease in the mCOasym and an increase
tively, and, as mentioned above, their frequencies in the mCOsym frequencies.
will be similar to the corresponding undissociated On the other hand, the major difference in the IR
acid. In several cases, however, the situation is spectra between monodentate (type II) and bidentate
complicated by the occurrence of hydrogen bonding bridging (type IV) groups is that the COasym is
between the noncoordinated oxygen atom of a generally smaller for the latter (Mehrotra and Bohra,
unidentate carboxylate ligand and a solvent mole- 1983; Crabtree and Rice, 1974).
cule, leading to a reduction in the CO2 asymmetric Thus, a general trend for both stretching frequen-
stretching frequency (Dresseyn, 1992; Nakamoto, cies and/or band separation values can be outlined
1986). Thus, in solutions in which several types as: uncoordinated acid>unidentate coordination>bi-
of metal – ligand bondings can occur, a change from dentate (bridging>chelating) coordination>free car-
bidentate (both types III and IV), or ionic, to boxylate ion.
unidentate structures will be observed as a disap- Due to the low dielectric constant of Versatic 10 in
pearance of the COsym band (Cassellato et al., Escaid 110 solutions, it has been assumed that ionic
1978). interactions do not occur in metal Versatic carboxy-
The distinction between the structural forms I, III lates (Doyle, 1983; Stefanakis and Monhemius, 1985;
and IV are not as unambiguously defined, since Doyle-Garner and Monhemius, 1985; Stefanakis,
chelation and bridging should not alter the bond 1983), then only spectral bands due to unidentate
orders (Dresseyn, 1992); although attachment of a and bidentate coordination are expected. Features of
heavy atom to each oxygen may cause some shifting the IR spectra of iron, nickel and zinc carboxylate
of the frequencies, such changes are relatively small solutions, both in Versatic 10 and Neo-decanoic acid
(Mehrotra and Bohra, 1983). Thus, in order to (tertiary C10 monocarboxylic acid), have been de-
establish bidentate coordination or to distinguish scribed in the literature (Doyle, 1983; Stefanakis and
between both configurations, additional information Monhemius, 1985; Doyle-Garner and Monhemius,
about the system under study is required. Neverthe- 1985; Stefanakis, 1983; Doyle et al., 1988; Teixeira,
less, it has been suggested that Dm is generally 1982); the main results from these studies are sum-
smaller in chelating than in bridging compounds marised in Table 1.

Table 1
Asymmetric stretching bands in some single metal carboxylate solutions
System mCoasym (cm
1) Me – O bonding assigned Comments Reference
Zn/ND 1675, 1582 not assigned 25 jC Doyle et al., 1988
Ni/V-10 1665, 1590 not assigned, type II Ni/HV z, Doyle, 1983; Doyle-Garner and
25 and 165 jC Monhemius, 1985
Ni/ND 1665, 1597 not assigned, type II 25 jC Doyle et al., 1988
Fe(III)/V-10 1600, 1575 type II, type IV Fe/HV z, 25 jC Stefanakis and Monhemius, 1985;
Stefanakis, 1983
Fe(III)/V-10 1575 type III Fe/HV z, Doyle, 1983; Doyle-Garner and
25 and 165 jC Monhemius, 1985
Fe(III)/V-10 1570 – 1575 bidentate Fe/HV z# , Teixeira, 1982
(type III or IV) 25 – 155 jC
Fe(III)/ND 1575 type III 25 jC Doyle et al., 1988
Escaid 110 was used as diluent in the Versatic solutions and kerosene in the Neo-decanoic solutions.
z and #: high and low molar ratios, respectively.
142 E.G. Palacios et al. / Hydrometallurgy 72 (2004) 139–148

3. Experimental methods ratios in each solution (i.e. [V]coord/[Me]) were then

calculated.
The metal carboxylate solutions were prepared
by exchange extraction (Fe(III)), solvent extraction
(Ni) and direct dissolution (Zn) in 33% (v/v) Ver- 4. Results and discussion
satic 10 in Escaid 110 solutions (Palacios-Beas,
1994); the experimental conditions are listed in 4.1. Zn Versatic 10 solutions
Table 2. In all cases, the respective metals were
quantitatively stripped with 1:1 hydrochloric acid The spectra at room temperature of zinc Versatic
from the organic phase in order that chemical solutions at several metal concentrations are shown in
analysis by atomic absorption (Perkin-Elmer spectro- Fig. 2; as can be seen, a strong band appears at 1584
photometer 1100 B) could be performed on aqueous cm
1 and a medium intensity band is observed at
solutions. Once prepared, the solutions were diluted 1416 cm
1; the intensity and frequency of the bands
with Escaid 110 as required for the recording of indicate that they correspond to mCOasym and mCOsym
the spectra. vibrations, respectively. The former is shifted to 1589
The vibrational spectra of the iron, nickel and zinc cm
1 and the latter becomes weaker as the concen-
carboxylate solutions, containing various metal con- tration of zinc decreases from 0.090 to 0.016 M.
centrations, were obtained at 20, 75, 150 and 200 jC. At low concentrations (0.016 – 0.004 M), mCOasym
The experimental methods for the recording of the remains constant at 1589 cm
1 and the intensity of
spectra are described elsewhere (Palacios and Mon- the 1416 cm
1 continues its decrease. Bands at 1675
hemius, 2001). The experimental conditions were and 1582 cm
1 have been observed in Neo-decanoic
selected to cover the range of both metal concentra- acid solutions at 25 jC, without being assigned
tion and temperature that are of interest for the (Doyle et al., 1988). The absorptivity of the mCOasym
hydrolytic stripping process. band is slightly affected by temperature (Fig. 3),
The bands appearing in the region between 1800 showing only a small decrease in intensity with
and 1400 cm
1 were analysed in all the spectra. increasing temperature. As with increasing concentra-
Using the appropriate equations (Palacios and Mon- tion, the effect of increasing temperature is to cause
hemius, 2001), the free Versatic acid (i.e. [V-10]free) only a slight shift in the zinc carboxylate characteristic
present in a number of metal carboxylate solutions band, showing that the structure of the species is not
was estimated; the concentration of Versatate groups affected by temperature. The CMO stretching band
coordinated with each metal (i.e. [V]coord=[V-10]0
corresponding to the dimeric free acid, mCMOD,
[V-10]free), and the Versatate groups to metal molar appears at around 1700 cm
1 in all the spectra in

Table 2
Experimental conditions for the preparation of metal carboxylate solutions
Solution Preparation method Experimental conditions
Ferric carboxylate (1) Direct dissolution of CaO magnetic stirring, T = 50 jC
(2) Exchange extraction from manual shaking, Ca/Fe (mol/mol) = 1.5, Aq/Org (v/v) = 2
ferric chloride aqueous solutions
(3) Ca2 + scrubbing magnetic stirring, Aq/Org (v/v) = 3, pH = 3.3 (0.5 M HCl)
(4) Cl
removal manual shaking, H2O/Org (v/v) = 2 (3 contacts)
(5) Raffinate and entrained H2O removal filtering through glass-fiber paper and silicon-coated paper
Nickel carboxylate (1) Solvent extraction from nickel magnetic stirring, Aq/Org (v/v) = 0.6,
sulphate aqueous solutions pH = 6.8 (1.0 M NaOH)
(2) Na+ removal H2O/Org (v/v) = 2 (2 contacts)
(3) Entrained H2O removal filtering through silicon-coated paper
Zinc carboxylate (1) Direct dissolution of ZnO magnetic stirring, T = 50 jC
(2) Entrained H2O removal filtering through silicon-coated paper
 E.G. Palacios et al. / Hydrometallurgy 72 (2004) 139–148 143

Fig. 2. IR spectra of zinc Versatic solutions at several metal concentrations. T = 20 jC, [V-10]0 = 0.1732 M, [Zn] (M) = (1) 0.004, (2) 0.008, (3)
0.016, (4) 0.090.

Figs. 2 and 3, and the monomeric free acid band, band (5 cm
1); this and the decreasing intensity of the
mCMOM, is observed at 1748 cm
1 in all the high band are more likely to be caused by the dilution of
temperature spectra (Fig. 3); the inflection appearing the absorbing species.
at around 1603 cm
1 is due to the solvent (Palacios The measured absorbance of both the monomer
and Monhemius, 2001). and the dimer peaks corresponding to the free
The presence of the mCOsym band indicates that the Versatic acid are presented in Table 3; in the same
carboxylate group is associated to the metal as a table, the calculated values for the concentration of
bidentate ligand, either chelating or bridging. A both free Versatic acid and Versatate groups coordi-
change in metal –ligand bonding cannot be inferred nated with the metal, and the acid to metal molar
from such a small shift in the position of the mCOasym ratio, are also shown. As can be seen, the calculated

Fig. 3. IR spectra of zinc Versatic solutions at several temperatures. [V-10]0 = 0.1732 M, [Zn] = 0.090 M, T (jC) = (1) 20, (2) 75, (3) 150, (4) 200.
144 E.G. Palacios et al. / Hydrometallurgy 72 (2004) 139–148

Table 3
Free and coordinated acid in zinc Versatic solutions at several concentrations and temperatures
[Zn], [V-10]0, T, AmM AmD [V-10]free, [V]coord  102, [V]coord/[Zn]
(M) (M) (jC) (abs. units) (abs. units) (M) (M)
0.004 0.173 20 – 1.341 0.167 0.61 1.52
0.008 0.173 20 – 1.322 0.165 0.85 1.06
0.016 0.173 20 – 1.228 0.153 2.02 1.26
0.016 0.173 20 – 1.213 0.151 2.21 1.38
0.018 0.035 20 – 0.070 0.009 2.60 1.44
0.090 0.173 20 – 0.299 0.037 13.60 1.51
0.090 0.173 150 0.105 0.077 0.041 13.22 1.47
0.018 0.035 150 0.048 0.010 0.013 2.17 1.21
0.090 0.173 200 0.126 0.022 0.037 13.60 1.51
0.018 0.035 200 0.043 – 0.010 2.51 1.40

values for the acid to zinc molar ratio, [V]coord/[Zn], 4.2. Ni Versatic 10 solutions
in the solutions fall in a narrow range (1 – 1.5), even
in the highly diluted samples, which is in agreement The spectra of nickel Versatic solutions at several
with the observations made earlier, i.e. that the metal concentrations and temperatures are shown in
structure of the zinc complex is not affected by Figs. 5 and 6, respectively. As can be seen in Fig. 5, two
changes in either concentration or temperature. Two strong bands appear at 1665 and 1595 cm
1 in the
basic types of complexes form in both zinc formate more concentrated solution; as the concentration of
and zinc acetate solutions (Mehrotra and Bohra, nickel decreases, the band at 1665 cm
1 tends to
1983; Oldham, 1968), namely Zn4O(O2CR)6 and disappear and the band at 1595 cm
1 is weakened
Zn(O2CR)2, with mCOasym bands appearing at 1600 and shifted to 1603 cm
1. The intensity and frequency
and 1550 cm
1, respectively. In the former, there are of the bands indicate that both correspond to mCOasym
four, tetrahedrally arranged, zinc atoms surrounding vibrations. A very weak band, appearing at 1405 cm
1
a central oxygen atom; the tetrahedron around each in the less concentrated solutions, is due to the dimeric
zinc atom is completed by three oxygen atoms from yOH vibration of the free acid (Palacios and Monhe-
bridging carboxylate groups. The [O2CR] to [Zn] mius, 2001). Temperature affects the absorptivity of
molar ratio for this species can be calculated as 1.5. the carboxylate groups associated with nickel, as
The latter contains only chelating ligands, with evidenced by the broadening and decreasing intensity
[O2CR]/[Zn] = 2, and the distorted octahedral stereo-
chemistry around the metal is completed by two
solvating water molecules. The data calculated here
would tend to suggest that a complex with a struc-
ture similar to the oxygen-centred formate/acetate
complexes is present in the zinc Versatic solutions,
considering that, within experimental error, [V]coord/
[Zn] = 1.5. The frequency of the mCOasym band
observed in the spectra is also in agreement with a
zinc Versatate complex with bridging ligand groups.
Additionally, since the solutions were prepared by
direct dissolution of ZnO in the organic medium, the
formation of the oxygen-centred complex would be
favoured. The proposed structure is presented in Fig.
4. As can be seen, a complex with such a structure
will present steric hindrance when reacting with any
other metal carboxylate species. Fig. 4. Structure proposed for the zinc/Versatic 10 complex.
 E.G. Palacios et al. / Hydrometallurgy 72 (2004) 139–148 145

Fig. 5. IR spectra of nickel Versatic solutions at several metal concentrations. T = 20 jC, [V-10]0 = 0.1732 M, [Ni] (M) = (1) 0.002, (2) 0.004, (3)
0.008, (4) 0.0325.

of both mCOasym bands as temperature is increased (Fig. 1665 cm
1 is overlapped with the band corresponding
6); however, both bands appear at the same frequency to the free dimeric acid; this introduced a large error in
in all cases, which suggests that the metal – ligand the estimation of the concentration of free Versatic acid
bondings are not affected by temperature. The mCMOD and therefore in the values calculated for the [V]coord/
band appears at 1698 cm
1 in all the spectra at 20 jC [Ni] ratio, making any discussion about the composi-
and it is shifted to 1700 cm
1 at higher temperatures; tion of the species meaningless.
the mCMOM band is observed at 1748 cm
1 in all the As in the case of the zinc solutions, the shift in the
high temperature spectra. As can be seen, the band at position (8 cm
1) of the mCOasym band is likely

Fig. 6. IR spectra of nickel Versatic solutions at several temperatures. [V-10]0 = 0.1732 M, [Ni] = 0.040 M, T (jC) = (1) 20, (2) 75, (3) 150,
(4) 200.
146 E.G. Palacios et al. / Hydrometallurgy 72 (2004) 139–148

caused by the dilution of the absorbing species. decreases with the increasing atomic weight of the
Similar mCOasym bands have been observed in nickel central atom (Rao, 1963); then, if Ni and Zn Versatic
Versatic solutions at high loadings, both in Versatic 10 complexes possess the same type of carboxylate
(Doyle, 1983; Doyle-Garner and Monhemius, 1985) ligand, their characteristic asymmetric frequencies
and in Neo-decanoic acid (Doyle et al., 1988); in would be expected to decrease from nickel to zinc,
either case, the higher frequency band was not which is the trend observed in the present study
assigned, while the lower frequency one (i.e. 1595 (mCOasym for Ni>mCOasym for Zn); thus, the trend
cm
1) was assigned to unidentate coordination; that suggests that the band at 1595 cm
1 should be due
assignation implies that the former band corresponds to bidentate bridging coordination.
to solvating acid. A frequency of 1685 cm
1 has been
reported for Versatic acid solvating iron(III) (Stefana- 4.3. Fe(III) Versatic 10 solutions
kis and Monhemius, 1985; Stefanakis, 1983); thus,
the band at 1665 cm
1 emerges at too low a frequen- In the 0.038 M ferric Versatic solution shown in
cy to be due to solvating acid; additionally, solvation Fig. 7, a strong band at 1575 cm
1 and a weak band
is more likely to occur in the less concentrated at 1416 cm
1 (mCOasym and mCOsym, respectively)
solutions, in which more free acid is available. Since can be observed. Although the absorptivity of the
the band is stronger in the highly loaded solution and carboxylate groups associated with the metal is slight-
is not present at lower loadings, it is more likely due ly affected by temperature (Fig. 8), it can be said that
to monodentate coordination. Thus, according to the temperature does not affect the structure of the ferric
trend in the position of the bands outlined in the carboxylate, as can be seen in the same figure, in
previous section, the band at 1595 cm
1 should be which only a slight shift in the mCOasym band towards
due to bidentate coordination (either chelating or lower frequencies is observed. The mCMOD band
bridging), with its corresponding mCOsym band being appears at 1702 cm
1 at 20 jC and it is shifted to
overshadowed by the strong bands corresponding to 1700 cm
1 at higher temperatures, while the mCMOM
skeleton vibrations of both acid and solvent, which band is observed at 1748 cm
1 in all the high
appear in the low frequency carboxylate region (1460 temperature spectra.
and 1380 cm
1) (Palacios and Monhemius, 2001). In The band at 1575 cm
1 has been observed in both
general, the characteristic frequency of a given group Versatic 10 and Neo-decanoic acid solutions which

Fig. 7. IR spectrum of a 0.038 M iron Versatic solution. T = 20 jC, [V-10]0 = 0.1732 M.

 E.G. Palacios et al. / Hydrometallurgy 72 (2004) 139–148 147

Fig. 8. IR spectra of iron Versatic solutions at several temperatures. [V-10]0 = 0.1732 M, [Fe] = 0.038 M, T (jC) = (1) 20, (2) 75, (3) 150, (4) 200.

contained a wide range of iron(III) concentrations ferric complexes have been reported to form in acetate
(Doyle, 1983; Stefanakis and Monhemius, 1985; and formate solutions (Mehrotra and Bohra, 1983;
Doyle-Garner and Monhemius, 1985; Doyle et al., Stefanakis and Monhemius, 1985). X-ray structural
1988; Teixeira, 1982). The predominance of bidentate analysis has shown that the trinuclear Fe(III) acetate
bridging over bidentate chelating has been suggested complex, Fe3(H2O)3O(O2CCH3)6+, contains six bridg-
on the basis of the presence of both mCOasym and ing carboxylate ligands and a central bridging oxygen
mCOsym bands (Stefanakis and Monhemius, 1985; (Blake and Fraser, 1975). As can be seen, in both types
Stefanakis, 1983), although a bidentate chelating struc- of complexes mentioned above [V]coord/[Fe] = 2. How-
ture would also satisfy the data, since the presence of ever, the frequency of the mCOasym band for the ferric
the lower frequency one is characteristic of both types solutions suggests that a bidentate chelating species is
of structure. A value of [V]coord/[Fe] = 2 can be taken present, given that mCOasym for Ni>mCOasym for
as constant (see Table 4) in all the solutions analysed. Zn>mCOasym for Fe(III); then, a frequency higher that
It has been claimed (Doyle, 1988) that, in freshly 1595 cm
1 would be expected for a mCOasym band
prepared iron(III) Versatic solutions, as in the present corresponding to a bridging bidentate ligand for
case, the predominant species is the dimeric complex iron(III). Therefore, the results suggest that the di-
(Fe(OH)V2)2, in which the Versatate groups are che- meric complex (Fe(OH)V2)2 is the species present in
lating the metal atoms. On the other hand, trinuclear the iron(III) Versatic solutions.

Table 4
Free and coordinated acid in iron(III) Versatic solutions at several concentrations and temperatures
[Fe], [V-10]0, T, AmM AmD [V-10]free, [V]coord, [V]coord/[Fe]
(M) (M) (jC) (abs. units) (abs. units) (M) (M)
0.015 0.069 20 – 0.279 0.035 0.035 2.27
0.038 0.173 20 – 0.723 0.090 0.083 2.19
0.015 0.069 150 0.105 0.070 0.039 0.030 1.97
0.038 0.173 150 0.184 0.250 0.098 0.075 1.97
0.015 0.069 200 0.129 0.021 0.037 0.032 2.09
0.038 0.173 200 0.256 0.100 0.099 0.074 1.96
148 E.G. Palacios et al. / Hydrometallurgy 72 (2004) 139–148

5. Conclusions Crabtree, H.E., Rice, N.M., 1974. A spectrophotometric study of

the organic phase complexes in the extraction of cobalt (II) with
carboxylic acids. Proc. ISEC ’74, vol. 1. London, UK.
Infrared spectroscopic data have been used for Doyle, F.M., 1983. Hydrolytic stripping of mixed metal carboxy-
determining the speciation of single-metal carboxylate lates. PhD thesis, University of London, London, UK.
solutions containing Fe(III), Ni and Zn at several Doyle, F.M., 1988. The physical chemistry of the precipitation
concentrations and temperatures. It was found that stripping process for removing iron (III) from carboxylate
solutions with dilute sulphuric acid. Hydrometallurgy 20,
iron(III) and zinc predominantly form complexes with
65 – 85.
bidentate structures at all the concentration levels Doyle-Garner, F.M., Monhemius, A.J., 1985. Mixed iron – nickel
tested, while the nickel complexes contain bidentate complexes in Versatic 10 solutions. Hydrometallurgy 13,
ligands at low concentrations and both monodentate 317 – 326.
and bidentate ligands at high concentrations. The Doyle, F.M., Pouillon, D., Villegas, E.A., 1988. Solvent extraction
evidence found in this work supports the existence of of metals with carboxylic acids—coextraction of base metals
with Fe(III) and characterization of selected carboxylate com-
a binuclear ferric carboxylate complex, [Fe(OH)V2]2, plexes. Hydrometallurgy 19, 289 – 308.
with chelating Versatic groups forming an octahedron Dresseyn, H.O., 1992. Vibrational analysis of acid derivatives. In:
around each of the iron atoms. An oxo-centred struc- Patai, S. (Ed.), The Chemistry of Acid Derivatives. The Chem-
ture, containing only bridging carboxylate groups, is istry of Functional Groups, Supplement B, vol. 2. Wiley, Chi-
proposed for the zinc Versatic complex, which is chester, UK, pp. 271 – 304.
Mehrotra, R.C., Bohra, R., 1983. Metal Carboxylates. Academic
believed to be present in the organic medium as Press, London, UK.
Zn4O(V)6. Nakamoto, K., 1986. Infrared and Raman Spectra of Inorganic and
Coordination Compounds, 4th ed. Wiley, New York, USA.
Oldham, C., 1968. Complexes of simple carboxylic acids. Prog.
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Acknowledgements
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