Aug 2014 Oct. 2014, Vol. 4, No. 4; 3156-3181.

E- ISSN: 2249 1929

Journal of Chemical, Biological and Physical Sciences

An International Peer Review E-3 Journal of Sciences
Available online at www.jcbsc.org

Section A: Chemical Sciences

CODEN (USA): JCBPAT Review Article

Synergism in Solvent Extraction and Solvent Extraction

Kinetics
Roshni Sarkar (Sain), Sumon Ray and Sukalyan Basu*

Department of Chemistry, the University of Burdwan, Burdwan-713104, India

Received: 15 September 2014; Revised: 04 October 2014; Accepted: 14 October 2014

Abstract: Extraction methods of different metal ions viz, Au(III), Fe(III), Co(II),
Cr(III), Ni(II) and U(VI) by synergistic extraction technique using different
extractants in different extracting conditions has been reviewed. Among the
parameters controlling synergism, the effect of diluents is highlighted and it has been
explained with the help of Hildebrands Regular Solution Theory Kinetics of these
synergistic extractions will enrich us about mechanistic step ladder of this ingrained
separation technique which will be supportive to our scientific society in future
progress in the field of extraction techniques.
Keywords: organophosphorous, thenoyltrifluoroacetone, organophilicity, hexa
co-ordinated

INTRODUCTION

The phenomenon in which two extractants when present together, extracted species, mostly metal ions
with greater efficiency than that corresponding to their additive action is called synergism. Rather
much effort has been devoted to synergistic extractions over the past two decades since the very
nature of synergism offers interesting research possibilities of both the chemistry of these extractants
and their potential application.
The large enhancement of metal extraction has been widely investigated from the theoretical,
analytical as well as from the applied point of view. The first careful studies of this phenomenon was
carried out by Blake et al in 1958, who found that U(VI) is extracted synergistically by a mixture of
dialkyl- phosphoric acid and a neutral organophosphorous reagent. Later on, extensive works have
been carried out on the synergic extraction of di, tri and tetravalent metal ions with different
combination of reagents by two pioneer workers in this field e.g. H. Irving and T. V. Helay. The

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Synergism Roshni Sarkar et al.

increasing interest in this subject can be seen from large number of research papers and various
reviews published in different journals. It will not be out of mention that opposite phenomenon i.e.
reduction in extraction efficiency in presence of mixed extractants is termed as antagonism.
When speaking about mixed extractants, the most common system appears to be an extraction of
metal cation MZ+ by a mixture of acidic extractant (HA) and a basic (S) reagent. Combined action of
two becomes very pronounced especially in those cases where co-ordination capacity of MAZ chelate
is not fully saturated by ligand A. Then the basic reagent (S) brings about the formation of adduct
MAZSX which is extracted to a greater efficiency than the parent chelate. On the other hand,
antagonistic extraction results when HA and S combine among themselves, reduces the formation of
MAZ. The most versatile and popular method of separation is solvent extraction and the reason behind
its popularity is the applicability in a wide range of concentration of extracting species i.e., from
macro level to micro level. The method is used [1-11] for the preparation, purification, enrichment and
separation of the components of interest from other interfering species. Depending on the polarity of
the solvent, the like extracted species extract into the like extracting solvents.
Uncharged metal complexes may be formed either by chelation [12] or ion association. Chelating
extractants simultaneously fulfil the co-ordination number and charge of the metal ions. Both of these
two are essential criteria for the transfer of a charged hydrated metal ion into nonpolar organic solvent
e.g. 1-Phenyl-3-methyl-4-benzoyl-5-pyrazolone (HP)[13], 3-Phenyl-4-Benzoyl-5-isoxazolon (HPBI)
[14]
, 1-benzoyl acetone[15], thenoyltrifluoroacetone (HTTA)[16], 2-hydroxy-5-nonylbenzophenone
oxime[17] tetrabutylmalonamide[18] are only few examples of such wide number of chelating
extractants which are recently explored. Extractions by solvation have also been reported [19-20] by
many authors.
Usually long chain alkyl or aryl amines in acid media extract anionic metal complexes through ion
pair formation. Alkyl or aryl group is responsible for organophilicity while positive charge of nitrogen
favors ion pair formation [21-22]. For instance, the 31.1 kJ mol1 is required to transfer an acetate anion
into nitrobenzene,[23] while the energy required to transfer a chloride anion from an aqueous phase to
nitrobenzene is 43.8 kJ mol1[24]. The interesting extraction of Fe (III) acetyl acetone in presence of
TOPO was studied by Aggett [25]. It was recognized [26] that the species extracted was an ion pair
[Fe(acac)2(TOPO)2]+CIO4-1 .

SYNERGISM

Synergistic extraction: Synergism can be defined as cooperation of two extractant molecules to

transfer metal ions from aqueous medium to organic phase in order to satisfy both the solvation and
co-ordination sites of the cation and neutralizes charge, while another less sterically demanding
extractant or synergist may serve to replace water or to occupy open co-ordination sites. In this way
two extractants cooperate to increase the extraction, which is greater than the sum values obtained
with each extractant operating independently e.g., D12 >> D1 + D2.
The synergist should have to fulfil the following conditions:
(i) It should have capability of displacing water molecules from the metal complex
rendering it less hydrophilic.
(ii) It should form less stable complex than the primary ligand.
(iii) It should favour the maximum co-ordination number of the metal.
Synergism reaction may be of various types, e.g.,

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Synergism Roshni Sarkar et al.

(i) Synergist co-ordinates with metal ion due to complete dissociation of the ligand.
(ii) Interaction between the synergist and coordinated ligand molecule.
(iii) Co-ordination of the synergist to the metal ion is such that it occupies the empty coordination
sites made available as a result of dissociation of one end of the ligand.
The phenomenon of enhancement of extraction efficiency for Pr (III) and Nd (III) was first observed
by Cuninghume et. al. [27] in the year of 1954 and the term synergism was first used by Blake et. al.[28]
in the year 1958. The extent of synergism is determined by synergistic coefficient (S.C) for the
combination of two extractants defined by Taube and Siekerski [29] and by Irving [30] as,
S.C = log [Dmix/(DI + DII)], where Dmix, DI and DII denote the distribution ratios of a metal ion with
mixture of extractants, extractant I and extractant II, respectively in binary liquid system. The extent
of synergism is given by
D = Dmix (DI + DII).
Thus, when S.C and D values are positive then it is said that synergism occurs. If both are negative
i.e. extraction decreased due to combination of some reagents, the phenomenon is known as
antagonism [31].
The synergistic extractions can be carried out with the any of the following combinations of the
extractants.
(i) Acidic and neutral extractants
(ii) Two acidic extractants
(iii) Two neutral extractants
(iv) Anionic and neutral extractants
(v) Cationic and anionic extractants and
(vi) Two anionic extractants.
(i) Acidic and neutral extractants: The acidic extractants may be -diketone, carboxylic acids,
sulfonic acids etc. which may behave as chelating extractants. The neutral donors include ketones,
amides, ethers, alcohols, sulphoxides, organo phosphorous, esters, etc. Extent of extraction increases
with these combinations [32-34]. The synergistic extraction obtained from the studies of effects of TBP
on the separation and extraction of some metals in MSO4/TBP/D2EHPAkerosene systems, where M
is a divalent metal ion such as Zn, Cd, Co, Ni, Cu and Mn [35].
(ii) Two acidic extractants: Comparatively lesser number of synergistic extractions has been
reported with the combination of two acidic extractants like two -diketones or two organic acids.
Synergism is observed in the extraction of Ni (II) with the mixture of Lix 860 and HDEHP [36].
(iii) Two neutral extractants: The enhancement of extraction can be produced by the combination of
two neutral extractants, e.g. extraction of Lu(III) by B2EHSO & DOSO or TOPO in benzene [37-38].
(iv) Anionic and neutral extractants: The mixture of amine salts which act as anionic extractants
and neutral organo phosphorous extractants may results in synergism. Enhancement is obtained in the
extraction of cobalt [39-40].
(v) Cationic and anionic extractants: The mixture of anionic, like amines and cationic extractants
may give rise to synergism [41-42].

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Synergism Roshni Sarkar et al.

(vi) Two anionic extractants: The mixture of two anionic extractants e.g. mixture of two amines may
results synergism [43].
(vii) Chelating agent and crown ether: Synergistic extraction of Nd (III), Tb (III) & Lu (III) with a
mixture of picrolinic acid & benzo crown-5 in CHCl3 have been reported [44].
(viii) Synergism in RTIL: Extractions of alkali & alkaline earth cations by crown ether into room
temperature ionic liquid (RTIL) have been carried out [45] and synergistic effects in the facilitated
transfer of metal ions in to RTIL is observed. This results minimum amount of disposable waste.
(ix) Miscellaneous combination : The enhancement of extraction efficiency was observed when
extraction of copper(II) was carried out with bidentate mono-schiff base extractants(HL), namely, N-
salicylideneaniline (SA), N-(2-hydroxy- 1-naphthalidene)aniline (HNA), N-salicylidene-1-
naphthylamine (SN), and N- (2-hydroxy-1-naphthalidene)-1-naphthylamine (HNN), from a weakly
acidic sulphate media into chloroform in the presence of acyclic polyether non-ionic surfactant[46].
Again, when lanthanides (III) were extracted with HTTA and Cu(Saltn) [Saltn = N N
disalicylidenetrimethylenediamine] a large synergistic effect was observed into chloroform[47] due to
formation of binuclear complexs.
(x) Self-adducts: If the system does not contain any donor molecule B, the water of hydration may be
replaced by undissociated HA (assuming the ligand A to be a dissociation product of HA), at least at
high HA concentrations; the MAz(HA)x complexes are refered to as self-adducts. Such type of
extraction was first noted by Dyrssen [48] during the extraction of Sr2+ with 8-hydroxyquinoline in
CHCl3 and species was identified as Sr(A)2 2HA. Recently, Y. Boukraa at. el have reported this type
of extraction on the transition divalent metal ( like Cu(II), Co(II) and Ni(II)) by Schiff base
salicylideneaniline (SAN) in chloroform from aqueous sulfate medium [49-50].
Pathways of synergism: The phenomenon of synergistic extraction of mixed ligand complexes has
been explained in terms of the enhancement of hydrophobic character of extracted complex [51]. At
first the metal ion is coordinated by the ligand and if the coordination number of the metal ion is not
fulfilled then water molecules enter into inner sphere. Later the water molecules are replaced by the
addition of donor. In other cases, an expansion of the coordination sphere of the metal ion takes place
in order to allow bonding with the donor molecules. Alternatively, the second ligand or donor is
attached to the metal-chelate complex via hydrogen bonding with the water molecules of metal-
chelate complex, e.g,
M(L)2(H2O)2 + (donor) = M(L)2(donor)(H2O) + H2O (Replacement of water from inner sphere)

M(L)2(H2O)2 + (donor) = M(L)2 ( H2O)2(donor) (Expansion of co-ordination shell of metal e.g, rare
earths)

M(L)2(H2O)2 + (donor) = M(L)2(HOHdonor) (Hydrogen bonding)

Assuming the metal ion is hexa co-ordinated in simple aqua complex ML2 (H2O)2 , where L=
bidentate ligand. Formula and structures may vary from system to system but basic idea of
incorporation of donor into ternary adduct is same and can take place either of the alternate pathways.
Parameters controlling the exact mechanism will be discussed in appropriate place.

PARAMETERS CONTROLLING SYNERGISM

(a) Role of bases or synergists: The structure of base and availability of electron density from its
donor centre has an important role in deciding the extent of synergic effect. It is obvious that the

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Synergism Roshni Sarkar et al.

stability constant of ternary adducts formed by metal complex and synergist base is highly influenced
by the electron density on the donor molecule. In an interesting study [53] effects of several alkyl and
aryl amine donors on the extraction of Co (TTA)2 chelate into CHCl3 were reported . Benzyl 2 amine
(BA) , Dibenzyl and Tribenzyl amine (DBA and TBA) are the representatives of aryl amines while
alkyl amines like, Tri-n-octyl amine (TOA), Tri allyl amine (TAA) , Tri propyl amine (TPA) , Tri
butyl amine (TBA) , Tri dodecyl amine (TDA), were used. Results reflect that the inductive and steric
effects of substituents attached to nitrogen atom determine the position of unshared electron pair at the
coordinatively active nitrogen atom. It is obvious that benzyl group with (-I) effect lowers the basic
nature of amine while presence of alkyl groups (+I) increases basic character of amine. Thus
Co(TTA)2TOA is more stable than Co(TTA)2TBA (log = 4.01 and 2.93 respectively). Again,
presence of conjugated double bond in TTA reduces its basicity and subsequently Co(TTA)2TPA >
Co(TTA)2TAA. The effect of chain length can be demonstrated by the fact that a linear increase in
stability constant with chain length is observed. Again, the inductive contribution of the different
substituents is shown by linear decrease of stability constants with increase in Taft constant for long
chain allyl amine where steric differences are not very significant.
On the other hand, phosphine oxides form a closely related series of synergists in which there are
similarities in basic moiety and differences in substituents which imparts steric influences on the
available lone pair of oxygen atom of phosphine oxides. Thus, tri-octyl phosphine oxide or tri-butyl
phosphine oxide behave as stronger bases than tri-phenyl phosphine oxide (TOPO> TBPO > TPPO).
Thus stability constant for ternary adducts of uranyl-dipyridyl chelate [54] during extraction into
CHCl3 follows the above sequence (log = 1.50, 1.43, 1.39 respectively, being the stability
constant). Again organic phase adduct formation constant (log Ks) of uranium-HPBI chelate [ 55] in
toluene with a series of long chain alkyl amide shows a linear variation of logKs with logKH of
amides.
Because of the increasingly polar nature of the phosphoryl group the solubility of neutral
organophosphorus compounds in water decreases in the following order: Phosphine oxides >
Phosphinates > Phosphonates > Phosphates. The order of basicity is the same as above. Thus the
trialkyl phosphine oxides are the most basic of this class of solvating extractants. Recently there has
been an increased interest in the potential applications of organophosphorus acid extractant, the
general formula RP(=O)(OR')2 in industrial processes as wel as the partitioning-transmutation nuclear
fuel cycle. The specificity of the chelating agent containing the phosphonic group is due to its
stereochemistry which is quite different from that of the carboxylic group. The phosphonate ion is
nearly tetrahedral (a distorted tetrahedron) with the symmetry axis of third order. The carboxylate ion
is planar and has a plane of symmetry. The valence angles and bonds lengths are different. -Bonding
between the oxygen and phosphorus atoms is considerably weaker than that between the oxygen and
carbon atoms in the carboxylic group. Polarizability of P=O bonds in the phosphoryl group is higher
than that of C=O bonds in the carboxylic group. That is why in phosphonic compounds the induction
effect plays a role on the one hand, and they have great nucleophilicity of the phosphonic group on the
other hand. Due to the stereochemistry of these complexones having two hydroxyls capable of
coordination, an a priori assumption was that stability of their chelates might be increased by
formation of additional cycles and that the complexones should be very selective to cations of
increased coordination capacity and of high electrostatic properties.
Various neutral organo phosphorus extractants, such as tributylphosphate (TBP) [56-58] and
trialkylphosphine oxide [59-61] have also been widely employed in separation chemistry. Acidic organo
phosphorus compounds, namely, di-2-ethylhexylphosphoric acid,[62-64] 2-ethylhexylphosphonic acid
mono-2-ethylhexyl ester[65-66] have been employed for the extraction and separation of different

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metal from acidic solution. Particularly organo phosphorus acid compounds have been widely
studied with respect to cobalt-nickel separation in weakly acidic sulphate media [67-68]. Cobalt and
nickel separation increased when the extractant was changed from phosphoric to phosphonic and
phosphinic acid based derivatives [phosphoric < phosphonic < phosphinic acids][69-71].Thio-substituted
organophosphorous acids have always attracted considerable attention from solvent extraction
specialists. Interest in these reagents has grown recently due to the entrance of Cyanex 301 with
bis(2,4,4-trimethylpentyl) dithiophosphinic acid (HR) as the active component, differs from other
thioorganophosphorous acids (e.g., from dialkyldithiophosphorous acids), as it has excellent thermal
and hydrolytic stability with regard to contact with sulfuric acid. Particular interest in this reagent is
explained also by the fact that Cyanex 301 is a key element of the hydrometallurgical technology for
the treatment of transition metals [72-74].
Structure and basicity of the donors control the stability of donors which determine the fate of
synergism. Structure of some donor molecules are given below, eg., tri-octyl phosphine oxide(TOPO),
tri-butyl phosphine oxide (TBPO), tri-phenyl phosphine oxide (TPPO), tri-butyl phosphate (TBP),
dimethyl solfoxide (DMSO) , crown ether (18C6 and 15C5) and pyridine.
.

Trioctylphosphine oxide (TOPO)

Tributylphosphine oxide (TBPO)

Triphenylphosphine oxide (TPPO)

Tributyl phosphate (TBP)

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Synergism Roshni Sarkar et al.

18-crown-6

15-crown-5

Dimethyl solfoxide (DMSO)

Pyridine

(b) Role of ligand: The phemenon of enhanced extraction or synergistic extraction popularly known,
has attracted considerable attention of analytical scientists due to possibilities of metal extraction from
relatively more acidic and complexing media. Apart from the applicability of the synergistic systems
to metal ion separation in analytical chemistry, there is a great deal of scope to understand the nature
of bonding in these complexes. Some of them are dependent on the nature of the principal ligand
often on synergists.
It is well-known that the pKa values of beta-ketones play a significant role in the binary extraction
system [75]. A reciprocal relation between the acid dissociation constants of the beta-diketones and the
two phase extraction constant indicate major role played by the acid strength of chelating agent in this
process. Thus, pyrazolones and isooxazolones which have relatively lower pKa values as compared to
the HTTA or HPMBP, can extract metal ions from acid solutions [76 ]. Low pKa value of HPBI is due
to the presence of heterocyclic isooxazolone group which enhances the dissociation of the beta-
diketone anions. The presence of phenyl group, on the other hand, imparts the desired partitioning
behaviour of the ligand.
Structures

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But when the benzoyl group is replaced by acetyl group in HPBI moiety, above linear correlation with
tetravalent cations like Pu4+ and Th4+ was not observed. The deviation from linearity was predicted on
the basis of electronic factors. Overall extraction behaviour of HPBI were more than HPAI since
acetyl group having +I effect reduces the acidity of hydrogen atom thus making the enolic form of
HPAI less predominant. But for HPBI, phenolic group with I effect makes -H atom more acidic.

[Correlation of binary extraction constant with pKa of beta diketones.]

Structure of ligand also plays an important role in the synergistic extraction because saturation of
coordination number, ultimate structure of the adduct, stability of the adduct are all dependend on the
structure of the ligand. Some examples of ligands which satisfy all these criteria are Carboxlic Acids
(R3CCOOH), Versatic Acid 10 [78], Didodecylnapthaenesulfonic Acid (HDDNS) [79], 2-
ethylhexylphosphonic acid mono 2-ethylhexyl ester (EHEHPA, PC 88A) [80], Bis(2,4,4
trimethylpentyl) phosphinic acid (Cyanex 272) [81], Di-2-ethylhexyl phosphoric acid (D2EHPA)[82].
The pictorial views of some commonly used ligands are,

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Synergism Roshni Sarkar et al.

(c) Temperature: Solvent extraction process or synergistic solvent extraction process is temperature
dependent because the process is dependent on chemical potential. Chemical potential is symbolized
by , a quantity first described by J. W. Gibbs. In simplest terms it is analogous to electric potential
and gravitational potential utilizing the same idea of force fields as being cause of things moving, be
they charges, masses or in this case chemicals. Chemical potential is the driving force for the transfer
of solute from one phase to other.
= 0 + RTln a
Where and 0 are the chemical potential at the experimental and standard state and is the activity of
the species. As is dependent on T, thus extraction process also depends on temperature.
On the other hand Gibbs free energy for a particular system is
G = -RTlnK K= equilibrium constant.
So, (0 -) = change in chemical potential = G
So it is clear that there is a close relation between spontaneity, change in chemical potential and
temperature [83]. The thermodynamic quantities like enthalpy change (H0 ) and entropy change (S0)
are important factors for explaining the exact extraction mechanism of the metal ion. The change in
enthalpy (H0) and entropy (S0 ) of liquid-liquid distribution of metal ions have been predominantly
obtained using the vant Hoff relationship [84-86]. On the other hand, the determination of the enthalpy
change of metal extraction reactions is also possible by calorimetric data [87-91]. The exact mechanism
of the reaction can be determined by using the thermodynamic data. The process is either through the
expansion of co-ordination number of transition metal [92-95], lanthanides [96] and actinides [97-98] or by
replacement of the co-ordinated water molecules of transition metals [99] lanthanides [100] and actinides
[101-102]
, as previously mentioned.
The thermodynamic parameters like enthalpy of formation (Hof), entropy of formation (S0f) and
free energy changes (G0 f) were calculated by the use of GibbsHelmholtz equation

o H f S o f
log K
2.303RT 2.303 R

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The enthalpy of formation (Ho f) and entropy of formation (S0f) of the extraction processes were
calculated from the slopes and intercepts of the plot of logK against 1/T.
When the water molecules of hydrated metal complex are replaced by the presence of synergist donor,
then enthalpy change (H0) and entropy change (S0) would be positive. In this case the hydration
zone of inner-sphere complexes is disrupted extensively and the net entropy and enthalpy changes are
usually positive. For inner-sphere complexes the entropy term is favoured (with respect to the
thermodynamic conditions of the reaction, i.e., positive (S0) is obtained). Liberation of larger
number of molecules leads to enhancement of entropy term. On the other hand enthalpy term is
disfavoured i.e., positive (H0) is simultaneously obtained for the same reaction due to breaking of
M-H2O bond [101].
M(L)2(H2O)2 + (donor) = M(L)2(donor)(H2O) + H2O
When the adduct formation is done through expansion of co-ordinates number of metal, the enthalpy
change (H0) would be negative and entropy change (S0) would be much negative. In this case
adducts are formed via outer-sphere complexes. For outer-sphere complexes the enthalpy term is
favoured and the entropy term is disfavoured, i.e., negative (H0) and negative (S0) are
simultaneously obtained. In outer-sphere complexes the hydration sphere is less disrupted. The net
entropy changes are negative owing to the complexation with decrease in randomness without a
compensatory disruption of the hydration spheres [103]
M(L)2(H2O)2 + (donor) = M(L)2 ( H2O)2(donor)
When adduct complex are formed by H-bond via one of the coordinated water molecules then the
entropy change would be largely negative. But in this case the enthalpy change would be
approximately similar to the energy of the hydrogen bond (~ -1.5 to -2.5 kcal/mole)
M(L)2(H2O)2 + (donor) = M(L)2(HOHdonor) (H2O)
In all these examples formula of hydrated metal complex has been arbitrarily assumed to be
ML2(H2O)2, of course it may be of differently one. Such a mechanistic pathway for ternary adduct
formation reaction was proposed by Marcus and Kertes [104]. Depending upon the relative values of
thermodynamic quantities course of synergistic extraction can be assigned. A series of extractions of
Zr(IV) complexes under varying media and different extractants were reported by A.A. Abdel-Fattah
et. al. [105] showing the possibilities of both inner-sphere and outer-sphere complexes for the same
metal depending upon the nature of extractant e.g., Amberlite LA-2, TBP, HDEHP etc.
On the other hand, extraction of Np(IV) by[106] the combination of HPBI and TOPO revealed that the
mixed extraction is highly enthalpy favoured (H = 46.65 KJ mol-1), a characteristic of hard Np4+
cation. But the steric crowding around the small metal ion (0.98A0) by four isooxazolone moiety leads
to very high negative entropy change and is highly unfavourable (S = -159.4 J/K/mol). However S
values for both binary and ternary extractions (-12.8, -22.5 KJ mol-1) are in favour of spontaneous
nature of extractions.
Antagonistic Extraction: In some cases addition of donor decreases the extraction efficiency, known
as antagonism or antisynergism. There are several examples of antagonistic extractions in the field of
extraction chemistry. The synergistic extraction behaviour of Pd2+, [107] one of the main radioactive
fission products in the reprocessing process, from HNO3 solutions with a 4-arayl derivative of 1-
phenyl-3-methyl-pyrazolone-5-one (PMP), a weakly acidic chelating extractant 1-phenyl-3-methyl-4-
(2-methoxybenzoyl)-pyrazolone-5-one (HPMMBP), and a trialkylamine of high molecular weight, tri-
iso-octylamine (TiOA), has been studied. An antagonistic extraction effect was observed in the
extraction system under the given conditions. To understand this phenomenon, a preliminary

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investigation was performed to explain the mechanism of this reaction. According to the theory of the
corresponding solutions (TCS), the association between HPMMBP and TiOA is presented and
discussed in the organic phase. An associated species HPMMBPTiOA formed through hydrogen
bonding in a CHCl3 medium might be the main reason why an antagonistic extraction effect occurred.
The association constant between HPMMBP and TiOA was calculated to be 0.212 0.03.
Liquidliquid extraction of cesium (spiked with 137Cs isotope)[108] with 18-crown-6 in nitrobenzene
solvent is diminished in presence of various phosphine oxides, namely, tri-n-octylphosphine oxide
(TOPO), tri-n-butylphosphine oxide (TBPO), and triphenylphosphine oxide (TPPO). Formation of an
electron donoracceptor complex between the crown ether and phosphine oxides is assumed, making
the crown ether less available for cesium extraction. The formation constants of the complexes were
determined by UVVIS spectrophotometry, utilizing Benesi-Hildebrand equation [109-115]. This
technique is complementary to fluorescence spectroscopy, in that fluorescence deals with transitions
from the excited state to the ground state, while absorption measures transitions from the ground state
to the excited state.[109]
d. Diluent effect in synergistic extraction: In synergistic extraction, as mentioned before,
thermodynamic equilibrium K0s,m for the adduct formation reaction,
MAx(org) + ms = (MAx.ms)org MAx = metalchelate s = donor
is given by
K0s,m = aMax. ms / aMAx . as m
= (XMAx. ms / XMAx . Xsm). (MAx. ms / MAx.sm)
= Ks . Fy - -(1)
X = molar fraction, = activity co-efficient
Where, Fy = (MAx. ms / MAx.sm) and KS= (XMAx. ms / XMAx . Xsm).
Where, a and represent activity and activity coefficient respectively. In these set of equations,
MAx.ms, MAx and S represent ternary chelate donor adduct of metal, metal chelate and pure donor
respectively. If a pure liquid is chosen as standard, the value of K0s,m may be considered to be
independent on the solvent. Under this condition, plot of logKs against logFY is expected to give
straight line with slope -1. Activity coefficients may be determined from Hildebrands regular
solution theory.
Now, activity in a solution consisting of component A and B is given by,
Now, RTln aA = RT [ ln A + B ( 1- VA/VB) + VAB2 (A B)2 ]
(from equation 9) , for dilute solution B ~ 1, then,
log A = log VA/VB + 1/ 2.3 ( 1- VA/VB) + VA / 2.3RT(A B)2 --(2)
If the solubility parameters and molar volumes are known, values can be determined
and the equation is,
log ( MAx. ms / MAx.s m) = A2org - 2BOrg +m log Vorg +
log (Vorg.VMAx.ms / VMAx.Vs m )+ C m/2.3 --(3)
Where,
A = 1/2.303 (VMAx.ms - VMAx mVs ) -- (4)

3166 J. Chem. Bio. Phy. Sci. Sec. A, Aug. 2014 Oct. 2014; Vol.4, No.4; 3156-3181.
Synergism Roshni Sarkar et al.

B = 1/2.3RT (VMAx.ms.MAx.ms VMAx.MAx- mVss ) -- (5)

C = 1/2.3RT (VMAx.ms.2MAx.ms VMAx.2MAx- mVs2s) - (6)
Putting V and values we get A, B, C (Vorg and org are dependent on diluents).
Since, VMAx.ms = VMAx + mVs
As we approximate that the molar volume of the adduct is nearly equal to the sum of the molar
volumes of chelate and of TOPO, we get A=0 from equation (4). Consequently Ks can be expressed
by a linear function of org so that logKs = 2B org + constant , where second term in R.H.S is
constant , collected together all terms independent on diluent. The adduct formation constant depends
only on org , diluent solubility parameter.
Again values of chelate can be calculated assuming M = HA and VM = nVHA as described
previously. The value of s and Vs was used for calculation of s. The molar volume of adduct VMS =
VM + VS and the approximate solubility parameter of adduct was determined from,
K0S,m = KS1 (MS1/ M1 S1 ) = KS2 (MS2/ M2 S2) --(7)
for two different solvent systems.
Rearranging,
MS = 2.3RT / VMS(1 2) [log KS1/KS2 + log V1/V2] + (VMM +VSS)/VMS --(8)
Thus MS of adduct can be calculated for a solvent pair with | 1 2| 0.5, in order to overcome the
uncertainities in measurement of solubility parameters.
As all numerical values of V and are known, so the final equation is,
logFY = -2BOrg + log Vorg.VMAx.ms / VMAx.Vsm + C m/2.3 --(9)
The calculation of logFY from each of the solvent system using above set of equations and a plot of
logFY against experimentally determined values of logKS is expected to result straight line, showing
the applicability of regular solution theory in the case of synergistic extractions.
Thus the role of solvent as medium can be generally elucidated from the activity co-efficient
evaluated with the aid of the solubility parameter concept.

A brief review of some of the metal ion is shown in tabular form.

Metal Extraction System Reference

[116]
Au(III) The synergic extraction of gold from cyanide solutions has been
studied using a mixture of Primene JMT (primary aminesRNH2)
and Cyanex 925 (bis2,4,4,trimethylpentylactyPhosphine
oxidesR3PO) in xylene
The mechanism of synergistic extraction of gold in HC1 media [117]

was researched with tri-n-octyl amine(TOA) and tri-noctyl

phospine oxide(TOPO)

The synergistic extraction of gold with TOA and TOPO in [118]

sulfuric acid media or thiourea-containing H2SO4 media

[119]
Synergistic extraction of Au(III) with Thiosemicarbazone
derivative of 2-OH napthaldehyde in presence of amine donor
and phosphine donor in methyl isobutyl ketone
Gold extraction from thiosulphate solutions using mixed amines [120]

3167 J. Chem. Bio. Phy. Sci. Sec. A, Aug. 2014 Oct. 2014; Vol.4, No.4; 3156-3181.
Synergism Roshni Sarkar et al.

Metal Extraction System Reference

[121]
Fe(III) The extraction of iron(III) from chloride solutions at macrolevel
concentration by different solvents such as tri-n-butyl phosphate
(TBP), di(2-ethylhexyl) phosphoric acid (D2EHPA), and their
mixture in various proportions has been investigated at different
acid concentrations

[122]
The synergistic extraction and improvement in the stripping of
iron(III) in sulfate solutions by a mixture of tertiary amine and 2-
ethylhexyl 2-ethylhexyl phosphonic acid.

[123]
Solvent extraction of iron (III) from hydrochloric acid solutions
using N,N-dimethyl-N,N-diphenylmalonamide and N,N-
dimethyl-N,N-diphenyltetradecylmalonamide

[124]
The use of synergistic solvent extraction mixtures based on
alkylated derivatives of 8-hydroxy quinoline and D2EHPA for
selective removal of iron(III) from the strong sulfuric acid
solution was described by Demopoulos and Gefvert

Metal Extraction System Reference

Co(II) Synergistic extraction of Co(II) with 8-hydroxyquinoline [125]

(Hq)/decanoic acid [(HR)2 ] solution mixtures was carried out in

benzene and chloroform.
Synergistic extraction of Co(II) with resacetophenone oxime in [126]

the presence of heterocyclic nitrogen and organophosphorus

compounds into cyclohexanone solvent
1-Phenyl-3-methyl-4-benzoylpyrazol-5-one (HPMBP) with 3,4- [127]

Dimethylanilin or 4-Methylaniline from sulphate medium to

toluene
The effect of the organic Lewis bases (TOPO, TBP, TBPO as [128]

oxygen containing bases, quinoline, isoquinoline lepidine

acridine as nitrogen containing bases) acting as a synergist on
the extraction of Co(II) with benzoyltrifluoroacetone from
perchlorate medium to benzene.
Mechanism of the synergistic extraction of octahedral Co(II) [129]

from nitrate medium by 8-hydroxyquinoline-dibenzo-18-C-6

chloroform mixture
Thermodynamics study on the synergistic extraction of Co(II) [130]

with Acetylacetone and Trioctyl-phosphine oxide in benzene

solvent from nitrate medium.
Co(II) The temperature effect on the extraction of Co(II) from a 0.1M [131]

ionic strength acetate buffer by acetylacetone, and a mixture of

acetylacetone and pyridine or triethylame into xylene solvent.
Enthalpy and entropy variations in the synergic extraction of [132]

cobalt(II) by thenoyltrifluoroacetone and tertiary amine ligands

into nitrobenzene

3168 J. Chem. Bio. Phy. Sci. Sec. A, Aug. 2014 Oct. 2014; Vol.4, No.4; 3156-3181.
Synergism Roshni Sarkar et al.

Metal Extraction System Reference

Cr(III) [133]

Simultaneous and Synergistic Extraction of Cationic and

Anionic Cr-compounds by a Mixed Solvent Extraction System
and a Novel Contained Liquid Membrane Device

Radiochemical solvent extraction of Cr(III) using51Cr tracer by [134]

8-hydroxyquinoline and acetylacetone as mixed ligands in

chloroform
Extraction of chromium(III) from a model spent tanning bath of [135]

the leather industry has been investigated using ammoniated and

non-ammoniated di(2-ethylhexyl)phosphoric acid (D2EHPA)
and bis(2,4,4-trimethylpentyl)phosphinic acid (Cyanex 272)

The equilibria of extraction of Ni(II) from 1.0Mnitrate medium by mixtures of LIX 860 [136]

and bis-(2-ethylhexyl)phosphoric acid (HDEHP) dissolved in toluene

Ni(II) [ 137]
Synergic extraction of Ni(II) by mixtures of 5,8-diethyl-7 hydroxydodecan-6-oxime and
n-dodecanoic acid in toluene
[138]
Synergistic extraction of Ni(II) by mixtures of LIX 63 and bis-(2-ethylhexyl)phosphoric
or di-n-octylphosphinic acids in toluene
The synergistic extraction of nickel and cobalt from acidic aqueous solutions has been [139]

observed with a mixture of di(2-ethylhexyl phosphoric acid and 5-dodecylsalicylaldoxime

Separation of nickel and copper by solvent extraction using di-2 ethylhexylphosphoric [140]

acid-based synergistic mixture

Solvent extraction of nickel and cobalt with synergistic systems consisting of carboxylic [141]

acid and aliphatic hydroxyoxime

The extraction of uranium from aqueous phosphoric acid medium using 2-ethyl hexyl [142]

hydrogen 2-ethyl hexyl phosphonate (PC88A) and octyl (phenyl)-N,N-

U(VI) diisobutylcarbamoylmethylphosphine oxide (CMPO) individually as well as their
synergistic mixture in different diluents
[143]
The influence of temperature in the range 15 to 75 C on the extraction of thorium(IV)
and uranium(VI) from nitric acid solutions into ligroine solutions of 2ethylhexyl
phenylphosphonic acid (HEHP), micellar dinonyl naphthalene suIphonic acid
(HDNNS) extractants and mixture of the two extractants
The extraction behavior of uranyl ion from dilute nitric acid medium employing 1-phenyl- [144]

3-methyl-4-benzoyl-5-pyrazolone (HPMBP)/2-thenoyltrifluoroacetone (HTTA) in

toluene and their mixture with several structurally modified monoamides viz. di-2-
ethylhexyl acetamide (D2EHAA), di-2-ethylhexyl propanamide (D2EHPrA), di-2-
ethylhexyl isobutyramide (D2EHiBA), and di-2-ethylhexyl pivalamide (D2EHPvA) was
investigated
Synergistic solvent extraction studies of uranium(VI) using a combination of naphthenic [145]

acid and various neutral donors into benzene

U(VI) [146]
The synergistic extraction of uranium(VI) from aqueous nitric acid solution with mixtures
of bis(hexylsulfinyl)ethane (BHxSE) and petroleum sulfoxides (PSO) in 1,1,2,2-
tetrachloroethane
Extraction of uranium(VI) with a binary mixture of LIX-860 and Versatic-10 in kerosene [147]

at equilibrium pH 4.6
Synergistic extraction of hexavalent uranium and plutonium as well as trivalent [148]

americium was studied in HNO3 with thenoyl, trifluoro-acetone (HTTA)/1-phenyl, 3-

methyl, 4-benzoyl pyrazolone-5 (HPMBP) in combination with neutral donors viz.
DPSO, TBP, TOPO (mono-functional) and DBDECMP, DHDECMP, CMPO (bi-
functional) with wide basicity range using benzene as diluent
[149]
The extraction of uranium(VI) from nitric acid medium is investigated using 2-ethylhexyl
phosphonic acid-mono-2-ethylhexyl ester (PC88A in dimeric form, H2A 2) as extractant
either alone or in combination with neutral extractants such as tri-n-butyl phosphate
(TBP), trioctyl phosphine oxide (TOPO), and dioctyl sulfoxide (DOSO)

3169 J. Chem. Bio. Phy. Sci. Sec. A, Aug. 2014 Oct. 2014; Vol.4, No.4; 3156-3181.
Synergism Roshni Sarkar et al.

Separation of copper from aqueous sulfate solutions by mixtures of Cyanex 301 [150]

and LIX 984N

Equilibrium Studies on the Synergic Liquid-Liquid Extraction Process of [151]

Copper(II) from Sulphate Media with Mixtures of some Bidentate Mono-Schiff

Bases and Acyclic Polyether Non-ionic Surfactant in Chloroform
Cu(II) Synergistic extraction of copper(II) and other divalent metals with 3-phenyl- 4- [152]

acylisoxazol-5-ones and 1-phenyl-3-methyl-4-acylpyrazol-5-ones in the

presence of TOPO) in toluene
Synergistic extraction of some divalent metal cations (Cu(II) Co(II) with 3- [153]

phenyl-4-benzoylisoxazolone-5-one and P=O donor ligands in chloroform

Synergistic extraction of copper(II), zinc(II) and cadmium(II) with [154]

monothiothenoyltrifluoroacetone and 1, 10-phenothroline

Thermodynamic study on adduct formation of Copper(II) diketone with [155]

heterocyclic bases
Yasunobu Ohmiya and Tatsuya Sekine studied the extraction behaviour of
Ag(I) silver from aqueous sodium nitrate medium with 2-thenoyltrifluoroacetone [156]

(HTTA) and 4- isopropyltropolone (HIPT) in the absence and presence of

tetrabutylammonium ions (TBA+), into chloroform solvent
The synergistic extraction of silver from nitrate medium into chloroform in
presence of some p-donor and n-donor [157]

Vesna Gasperov observed the synergistic extraction of Ag(I) from nitrate

medium using a mixture of with 1,4,8,11-tetrabenzyl-1,4,8,11-
tetraazacyclodecane and lipophilic organic carboxylic acid via the formation of [158]

Hostguest assemblies between those ligands as well as metal ion into

chloroform
Synergistic effect of trioctylphosphine oxide and dibenzo-18-crown-6 on the
extraction of silver (I) as picrate [159]

Extraction of silver from water into nitrobenzene using sodium

[160]
dicarbollylcobaltate in the presence of valinomycin
[161]
Design of ion-exchange resigns selective of Cesium (I) synergistic effect of
Cs(I) macrocycle in phenolic resins
[162]
The extraction rubidium and cesium picrates has been studied with mixture of
crown ether and tributyl phosphate (TBP) or trioctyl phosphine oxide (TOPO)
in benzene

E. Kinetics of synergistic solvent extraction: The rate of complex formation of chromium(III) with
acetylacetone in aqueous perchlorate solutions was determined by a solvent extraction method in 4-
methyl-2-pentanone and 4-methyl-2-pentanol. The rate of complex formation in the organic solvents
was also studied by a spectrophotometric method. On the basis of the results that the rate of complex
formation was nearly the same in these three media, a mechanism for the extraction of the metal ions
in aqueous perchlorate solutions with acetylacetone into these polar organic solvents was proposed
[163].

The rate of extraction of iron(III) in acid aqueous perchlorate solutions with acetylacetone,
benzoylacetone, trifluoroacetylacetone, benzoyltrifluoroacetone, 2-thenoyltrifluoroacetone and
hexafluoroacetylacetone into carbon tetrachloride has been studied at 25C. The rate was found to be

(Where HA is a -diketone)
When the acidity was not very high, and the rate constants were calculated by assuming either that the
reaction was controlled by the association of (i) hydrated Fe3+ with a -diketonate anion, or (ii)
hydrated FeOH2+ with an enol form of -diketone molecule. It was concluded that the reaction (ii)

3170 J. Chem. Bio. Phy. Sci. Sec. A, Aug. 2014 Oct. 2014; Vol.4, No.4; 3156-3181.
Synergism Roshni Sarkar et al.

was, in general, more acceptable although it could not explain previously reported observations on the
rate of iron(III) extraction with 2-thenoyltrifluoroacetone[164].
The effects of temperature and contact time on lipid extraction from sunflower collets were
investigated in a batch extractor with hexane as solvent. The total removed material varied in quantity
and composition due to changes in temperature and contact time. Higher temperatures enhanced oil
extraction as well as increased the tocopherol and phospholipid contents of the oil. The kinetic data
for triglycerols, phospholipid and tocopherols extraction were interpreted by using an equation that
considers extraction as the sum of two components: diffusion and washing. Effective diffusion
coefficients for oil, tocopherols and phospholipid at different temperatures were determined. Control
of temperature and contact time are essential to obtain good quality oil and reduce refining costs.
Extraction at 60 C and short contact times (30 min) obtained high oil yield (98%) accompanied by
significant tocopherol extraction (>99%) and reduced phospholipid extraction (66%)[165].
Kinetics of the mass transfer processes involved in uranium recovery from wet process phosphoric
acid (WPA) by solvent extraction employing synergistic extractants has been studied. In the present
investigation results on the kinetics of separation of entrained solvent by diluent washing and uranium
mass transfer behaviour have been discussed. Kinetic studies for the entrained solvent separation by
diluent (petrofin) wash for D2EHPA/WPA system showed significant dependence of the rate constant
value on the variables such as phase ratio, temperature and agitator speed. Kinetic studies on the mass
transfer of U(VI) from phosphoric acid with 1.5 M D2EHPA+ 0.2 M TBP have been carried out using
a constant interfacial area cell (Lewis cell). The effect of stirring speed, interfacial area, acidity of
aqueous phase, extractant concentration in organic phase and temperature on the extraction rate
constant indicate that both chemical reaction and diffusion, control the rate of uranium extraction
from phosphoric acid to extractant phase. The activation energy for uranium mass transfer is found to
be 18.1 kJ/mole. Experimental results showed that the rate of extraction has an inverse first order
dependence on phosphoric acid concentration whereas the dependence of the rate constant on
D2EHPA+TBP concentration was found to be greater than first order (1.5) [166].
The rate of extraction of V(IV) from aqueous sulphuric acid solutions (0.5 mol dm3sulphate and 0.25
mol dm3 acetate buffer) with HDEHP [HDEHP H2A2 bis-(2-ethyl hexyl) phosphoric acid] in
benzene and the back extraction of V(IV) from V(IV)-DEHP chelate in the benzene phase to aqueous
sulphoric acid phase (0.5 mol dm3sulphate and 0.25 mol dm3sulphate and 0.25 mol dm3 acetate)
have been studied under various conditions. The rate expression for forward extraction can be written
at (30 1)C as:

-dCAV/dt = - 2.484 [H2A2](0)0.5[H+]-1 (1+2.09 [Ac-]) (1+1.175 [SO42-])- (1+1.44 [NO3-])

and the backward extraction rate expression can be written as:

-dC0V/dt = 10-0.6387(Cv0) [H2A2](0) -0.5[H+] (1+ [NO3-])-1 (1+0.5 [Ac-])-1

In absence of the sulphate, acetate and nitrate ions, the formation of the 1:1 complex (VO2+ + A
VOA+) is the rate determining step in the forward extraction, whereas, the liberation of a DEHP (A)
anion from the monomeric complex (VOA2 VOA+ + A) is the rate determining step in the
backward extraction. The rate data is comparable with the equilibrium data [167].
Metal extraction pH isotherms and extraction and stripping kinetics have been determined with
Versatic 10 acid and LIX 63 and modifier TBP in an attempt to develop synergistic SX systems for
the separation, purification and recovery of nickel and cobalt from leach solutions.

3171 J. Chem. Bio. Phy. Sci. Sec. A, Aug. 2014 Oct. 2014; Vol.4, No.4; 3156-3181.
Synergism Roshni Sarkar et al.

The combination of LIX 63 with Versatic 10 acid resulted in significant synergistic shifts for nickel,
cobalt, copper, zinc, and manganese and antagonistic shifts for calcium and magnesium. With the 0.5
M Versatic 10 acid/0.35 M LIX 63 system, the pH50 values of nickel, cobalt, copper, zinc and
manganese compared to Versatic 10 acid alone were found to be 2.79, 3.50, > 2.0, 1.99 and 1.17 pH
units, respectively. The pH50(MnNi) and pH50(MnCo) values were found to be 1.96 pH and 2.53 pH
units, respectively, indicating easy separation of nickel and cobalt from manganese, calcium and
magnesium. The extraction and stripping kinetics of cobalt, copper, zinc, and manganese were fast
and the extraction and stripping kinetics of nickel were slow with the Versatic 10 acid/LIX 63
synergistic system. The nickel stripping kinetics increased with the addition of TBP. Within 2 min,
the stripping efficiency of nickel increased from 18% with no TBP to 91% with 0.5 M TBP addition.
The addition of TBP to the Versatic 10 acid/LIX 63 system also improved the nickel extraction
kinetics.
It is proposed that in the Versatic 10 acid/LIX 63 synergistic system, LIX 63 plays the role of an
extractant and Versatic 10 acid a synergist for nickel while LIX 63 plays the role of a synergist and
Versatic 10 acid an extractant for cobalt [168].
The rate of nickel extraction by hydroxyoxime/carboxylic acid mixturesis first order with respect to
nickel, hydroxyoxime and carboxylic acid concentrations and inverse first order with respect to the
hydrogen ion concentration. The rate dependencies for the reverse reaction are the reciprocal of the
extraction reaction. Although it has not proved possible from these data to derive an unambiguous
kinetic scheme, the study has highlighted the importance of the interfacial properties of the metal
chelate solvent extraction systems [169].
Organophosphorus reagents are well known in solvent extraction. Commercial operations for the
separation of cobalt from nickel have been successfully carried out using organophosphoric, -
phosphonic, and -phosphinic acid extractants. Two new reagents in this class are the mono and dithio
analogs of the commercial dialkylphosphinic acid, Cyanex 272. The replacement of oxygen by sulfur
in these reagents enables extraction to be carried out at much lower pH.
Characterization of Cyanex 272, Cyanex 302 (bis-(2,4,4-trimethylpentyl)-thiophosphinic acid), and
Cyanex 301 (bis-(2,4,4-trimethylpentyl)-dithiophosphinic acid) has been undertaken. A comparison of
the solvent extraction behavior of metallurgically important first-row transition metal ions from acidic
sulfate solution by these reagents is reported. Distribution coefficients shift to lower pH with
increasing sulfur substitution and decreasing pKa of the extractant, the greatest effect being observed
for nickel. Stoichiometry of the extraction reactions, and the nature of the metal complexes formed
have been determined using slope analysis techniques and spectroscopic measurements [K8 [170]
In the present review, dealing with the kinetics of solvent extraction of metal species, we will consider
biphasic systems consisting of:
1. An aqueous electrolyte solution containing a metal cation which, according to the nature and
composition of the electrolyte, can exist either as a free (hydrated) ion or as neutral, positively or
negatively charged complex species
2. An organic phase which is a solution, in a water-immiscible organic diluent, of an organic molecule
called extractant; only organic diluent not exhibiting appreciable extraction properties by themselves
will be considered; the extractant will instead be a molecule capable of reacting with the aqueous
metal species, transferring them into the organic phase; this reactivity is conferred to the extractant by
the presence of a functional group which has binding properties with respect to the metal species; the
only purpose of the diluent will then be that of dissolving the extractant and possibly to improve its
physical properties[171].
3172 J. Chem. Bio. Phy. Sci. Sec. A, Aug. 2014 Oct. 2014; Vol.4, No.4; 3156-3181.
Synergism Roshni Sarkar et al.

Nickel extraction kinetics with the synergistic solvent extraction (SSX) system of LIX63/Versatic 10
is known to be slow. The presence of TBP improved the extraction rate. A study of the nickel
extraction kinetics with the SSX system has been carried out using an improved Lewis cell in order to
identify the kinetic role of each component.[172]

CONCLUSION

Adopting Hildebrands regular solution theory and from the supplied values of solubility parameters
and experimentally determined values of same quantity lead to same result indicating that,
(1) The regular solution theory is applied in present sets of system.
(2) The validity of the equation connecting distribution ratio in molar fraction with solubility
parameter of diluents in case of -diketonates studied here.
(3) Adduct formation takes place in organic media and as such, diluents or media plays an important
role in deciding the extent of synergism.
Beside diluents, metal ligand combination might direct the possibilities of ternary adduct formation or
not. Thus Au(III) forms outer sphere complex with both of two ligands in presence of TOPO.
Corresponding values of thermodynamic parameters (H0, S0)are in favour of no-bond breaking of
metal chelates when donor is added to it and this is equally applicable for all solvents taken up for
present investigation. But for Fe(III), it is seen that TTA behaves similar with Au(III) complexes but
BZAC complex of Fe(III) form innersphere adduct with TOPO . The endothermic nature of extraction
process with positive values of S0 in case of Fe(III)-BZAC-TOPO extraction is clearly indicative of
replacement of water molecules from innersphere by donor. The IR data also support these fact. Again
the same behavior is shown by all the diluents used to study the corresponding of Fe(III)-BZAC-
TOPO adduct.
The differential behavior of two ligands for a particular metal ion is also shown in case of Co(II)-HA-
TOPO adduct extraction. Here, although TTA extraction is enhanced by the addition of TOPO with
overall outersphere complex formation, BZAC extraction of Co(II) is diminished by the addition of
TOPO. Formation of (BZAC,TOPO) electron donor acceptor complex is hypothesized with
corresponding value of formation constant obtained through spectrophotometric measurement. Again,
all the diluents have similar trend of antisynergic effect on much extraction. Thus role of ligand, as
discussed in chapter 1, is also found to have important consequences on mixed extraction
system.Perhaps electronic effect of the -diketone moiety is responsible for different behavior of two
different ligands.
But such a conclusion is not valid for all the metals and we reported that for Cr(III) extraction by both
of the two ligands are reduced by the addition of TOPO with each of the two solvents. Corresponding
values of formation constants of EDA complexes are appreciably high explaining why the ligand
becomes increasing less available for metal extra action thus leading to antagonistic extraction.
Thus, it is revealed that effects of mixed extractants vary widely from system and a single theory or
single mechanism is not sufficient to offer explanation of all sorts of combination e.g. metal, ligand,
donor, diluents etc. In our present work, we have restricted our study on only one donor to avoid
further complexity.
An interesting observation among the three metal chelate extractions e.g. Co(II), Au(III) & Fe(III)
may be cited. Thus for binary extraction (MA3/ MA2), Co(II) &Fe(III) extract best in ethyl acetate and
n-butanol respectively is with either of two ligands. But Au(III) chelate is best extracted into n-

3173 J. Chem. Bio. Phy. Sci. Sec. A, Aug. 2014 Oct. 2014; Vol.4, No.4; 3156-3181.
Synergism Roshni Sarkar et al.

butanol (BZAC) and ethyl acetate (TTA). On the other hand, for ternary adduct formation with
TOPO, e.g. Co(II)-TTA-TOPO, extracts in ethyl acetate is most while Fe(III)-TTA-TOPO in n-
butanol and Au(III)-TTA-TOPO in chloroform. When the ligand is replaced by BZAC, Fe(III) adduct
extracts most in n-butanol but Au(III) adduct in CCl4 and Co(II) does not form ternary adduct with
BZAC-TOPO under present condition of experiment. Thus, for Au(III) binary and ternary complexes
undergo best extraction in two different solvents for two different ligands although mechanism is
same in both cases. On the contrary, extraction pathways of Fe(III) complexes are different for
different ligands but they do extract in same solvent in most.
So it may be concluded that mixed extraction systems offer very interesting features and needs further
investigation to elucidate the actual reason of differential behavior of the systems under conditions.
Diluent effects have been analysed by the evaluation of solubility parameter of metal chelates and
have been corrected with extraction parameters as much as practicable. So far other variables are
concerned, we have been successful to point out the differences, although detail explanation needs
through investigation. Even for diluents variation, we could correlate with the solvents we used but
are not aware whether the same is valid for other unexplored system.
Finally, we quote few lines of Dr R.L. Scot (taken from R.L.Scot, Ann. Rev, Phy.Chem, 431, 1943)
who describe the regular solution theory in a clear optimistic view. We can extrapolate these lines to
our overall investigation presented in this dissertation too.
In short, the solubility parameter equations offer a useful approach to a very wide area of solutions,
like a small-scale map for a very broad long-distance air view of a subcontinent. It is able to make
numerical predictions about all areas, these are unlikely to prove highly accurate. When a small area
is examined carefully, they are equally unlikely to prove completely absurd. A real serious failure of
basic assumptions and attracts serious attentions.
A. Abbreviations
acac Acetyl acetone
BA Benzyl amine
BDSO Butyldodecylsulfoxide
B2EHSO Bis (2-ethylhexyl)sulphoxide
BHxSE Bis (hexylsulfinyl) ethane
bipy 2,2' bipyridine
bta Benzoyltrifluoroacetone
BZAC Benzoyl acetone
B15C5 Benzo-l5-crown-5-ether
B18C6 Benzo-18-crown-6-ether
CE Crown ether
CMPO Octyl (phenyl)(N,Ndiisobutylcarbamoylmethyl) Phosphine oxide
Cyanex- 272 Bis(2,4,4 trimethylpentyl) phosphinic acid
C18C6 Cyclohexano-18-crown-6
15C5 l5-crown-5-ether

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Synergism Roshni Sarkar et al.

18C6 18-crown-6-ether
DBA Dibenzyl amine
DB15C5 Dibenzo-15-crown-5-ether
DBSO Dibenzoylsulphoxide
DC18C6 Dicyclohexano-18-crown-6-ether
DDA n-dodecylamine
D2EHPA Di-2-ethylhexyl phosphoric acid
D2EHPrA Di-2-ethylhexyl propanamide
D2EHiBA Di-2-ethylhexyl isobutyramide
D2EHPvA Di-2-ethylhexyl pivalamide
DMSO Dimethyl solfoxide
DOSO Dioctyl sulfoxide
EHEHPA 2-ethylhexylphosphonic acid mono 2-ethylhexyl Ester, PC 88A
HDDNS Didodecylnapthaenesulfonic Acid
HEHP 2ethylhexyl phenylphosphonic acid
HIPT 4- isopropyltropolone
HPA Picrolonic acid
HNA N-(2-hydroxy- 1-naphthalidene) aniline
HNN N- (2-hydroxy-1-naphthalidene)-1-naphthylamine
HPAI 3-phenyl- 4-Acetyl-5-isoxazolon
HPBI 3-phenyl- 4-Benzoyl-5-isoxazolon
HPMAP 1-phenyl-3-methyl-4-acetyl-5-pyrazolone
HPMBP 1-Phenyl-3-methyl-4-benzoyl-5-pyrazolone
HPMDP 1-Phenyl-3-Methyl-4-Decanoyl-5-Pyrazolone
HPMSP 1-phenyl-3-methyl-4-stearoyl-5-hydroxypyrazole
Hq 8-hydroxyquinoline
HTTA 2- thenoyltrifluoroacetone
PSO Petroleum sulfoxides
SA N-salicylideneaniline
SAN Salicylideneaniline
Saltn N N disalicylidenetrimethylenediamine
SNN Salicylidene-1-naphthylamine
TAA Tri allyl amine
TBA Tribenzyl amine

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Synergism Roshni Sarkar et al.

TBP Tri butyl phosphate

TBPO Tri butyl phosphine oxide
TDA Tri dodecyl amine
TFA Tri fluoroacety lacetone
TIBPS Triisobutylphosphine sulphide
TOA Tri-n-octyl amine
TOPO Tri-n-octyl phosphine oxide
TPA Tri propyl amine
TPPO Tri-phenyl phosphine oxide
TTA Theonyl tri-fluoro acetone

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Date of Publication: 2011-10-03 Conference: ISEC 2011 - 19th International Solvent
Extraction Conference, Santiago, Chile, 3-7 October 2011 Pages: 7p Publication
Type: Conference Paper

* Corresponding author: Sukalyan Basu;

Department of Chemistry, the University of Burdwan,
Burdwan-713104, India
E-mail: [email protected]

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