International Journal of Mineral Processing 167 (2017) 86–94

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International Journal of Mineral Processing

journal homepage: www.elsevier.com/locate/ijminpro

An extension of Free's extraction isotherm for the solvent extraction of

cations using acidic extractants
V. Agarwal, M.S. Safarzadeh ⁎, J. Galvin
Department of Materials and Metallurgical Engineering, South Dakota School of Mines and Technology, 501 East Saint Joseph Street, Rapid City, SD 57701-3995, United States

a r t i c l e i n f o a b s t r a c t

Article history: A simple theoretical model has been developed for the solvent extraction of cations with different oxidation
Received 2 April 2017 states varying from +1 to +4 using acidic extractants. The basic assumption behind this theoretical model is
Received in revised form 11 August 2017 that the cationic species (Mn+) will exist in ionic form and not form any complexes in the aqueous phase. A direct
Accepted 21 August 2017
relationship between the concentration of metal ions in the aqueous phase and that in the organic phase was de-
Available online 23 August 2017
veloped for trivalent and tetravalent cationic species. Using this model, the distribution isotherms were plotted
Keywords:
for a given set of conditions. The effect of pH and equilibrium constant on the distribution isotherms were repre-
Solvent extraction sented in three-dimensional form for trivalent and tetravalent cationic species. Consistent with expectations, the
Model results suggest that with increasing pH and an increasing equilibrium constant one finds an enhancement of the
Equilibrium extraction of cationic species for a given set of conditions. The calculations were performed in the pH range of 1
Oxidation state through 3 because for higher pH values, the pH shift accompanying the extraction is significant and thereby af-
Distribution isotherm fects the mass balance equations. A comparison of the distribution isotherms shows that the total metal ion con-
centration to extractant concentration ratio determines the distribution behavior of metal ions with different
valency. At low total metal ion concentration to extractant concentration ratio, the distribution coefficient was
higher for higher oxidation state cations under similar experimental conditions, and this trend started to reverse
when the total metal ion concentration to extractant concentration ratio was increased.
© 2017 Elsevier B.V. All rights reserved.

1. Introduction course, activity coefficients need to be evaluated for more accurate

results.
The general equilibrium equation for solvent extraction of cationic The distribution coefficient (D) is the ratio at equilibrium of the con-
species using organophosphorus extractants can be expressed as fol- centration of metal in the organic phase (CMRn) divided by the concen-
lows (Rydberg, 2004; Free, 2013): tration of metal in the aqueous phase (CMn+). This is given by Eq. (3).

Mnþ þ n RH⇄MRn þ nHþ ð1Þ CMRn

D¼ ð3Þ
CMnþ
n+
where M represents the cation, RH represents the organophosphorus
extractant before deprotonation, and MRn represents the metal com- Substituting Eq. (3) into Eq. (2) gives:
plex formed because of the extraction reaction. The bar line over a sym-
bol represents the species in the organic phase. From Eq. (1), the CHþ n
concentration-based equilibrium constant can be written as: K conc ¼ D ð4Þ
CRH n

CMRn  CHþ n
K conc ¼ ð2Þ The logarithmic form of Eq. (4) is as follows:
CMnþ  CRH n

logD ¼ logK conc þ n log½RH þ npH ð5Þ

where Kconc represents the equilibrium constant, which is equal to Keq
when the activity coefficients are equal to one. For practical purposes,
this concentration-based equilibrium constant is generally used. Of
⁎ Corresponding author.
E-mail address: sadegh.safarzadeh@sdsmt.edu (M.S. Safarzadeh).
where pH refers to the equilibrium pH of the aqueous solution. Eq. (5) can
be utilized to solve for logKconc by plotting logD versus (log[RH]+pH), as
the y-intercept of the graph will be equal to logKconc and the slope n will
give the stoichiometry of the extraction reaction.

http://dx.doi.org/10.1016/j.minpro.2017.08.005
0301-7516/© 2017 Elsevier B.V. All rights reserved.
 V. Agarwal et al. / International Journal of Mineral Processing 167 (2017) 86–94 87

The efficiency of the solvent extraction is expressed in terms of per- Although many researchers have tried to develop mathematical
cent extraction (%E), which is the ratio of the concentration of metal models using solvent extraction experimental data for various metal-
loaded into the organic phase at equilibrium divided by the total, or ini- extractant systems (Thakur et al., 1993; Alguacil, 1999; Mishra et al.,
tial, metal concentration in the aqueous phase, finally multiplied by 100. 2000; Belova et al., 2015; Lyon et al., 2017), there is no data available
Eq. (6) represents a simple way to calculate %E, where [Mn+]initial is the on further deriving mass balance equations to get a direct relationship
initial metal concentration in the aqueous solution and [Mn+]equilibrium between metal ion concentration in the organic and aqueous phases
is the equilibrium metal concentration remaining in the raffinate. for tricharged and tetracharged species using acidic extractants. For
neutral extractants, a chemical model was developed to predict the con-

nþ 
 ! centration of distributed species and was used to explain the solvent ex-
M initial − Mnþ equilibrium
%E ¼
nþ   100 ð6Þ traction of thorium nitrate with tri-n-butyl phosphate (TBP) by fitting
M initial
the model with experimental data (Čomor et al., 1997).
Professor Michael L. Free (Free, 2013) of the University of Utah de-
Another way to calculate the fraction of metal extracted is to use Eq. veloped a theoretical model for monocharged and bicharged cations
(7), as follows: and plotted distribution isotherms for both. In this paper, similar models
for tricharged and tetracharged cations are developed and comparison
of the developed models for different cationic species was studied
CMRn  Vorg
E¼ ð7Þ under similar conditions. Most of the elements in lanthanide series are
CMRn  Vorg þ CMnþ  Vaq
tricharged, whereas the elements in actinide series are tetracharged.
Therefore, extension of Free's isotherm is required and prediction of dis-
where Vorg and Vaq are the volumes of the organic and aqueous phases, tribution isotherms using these developed models would be useful to
respectively. find out optimized extraction and separation conditions.

2. Development of a theoretical model

Distribution isotherms are constructed using CMRn against CMn+ extraction data, based on which the relationship between concentration of metal
in the organic phase and that in the aqueous phase can be established. A molar mass balance for the total organic extractant concentration can be
written as follows:

CRtot ¼ nCMRn þ CRH ð8Þ

where CRtot is the total number of moles of extractant used in the reaction.
Based on Eqs. (2) and (8), it is possible to derive a relationship between the equilibrium concentration of metal in the organic phase and that in the
aqueous phase for different oxidation states of the dissolved cations as detailed below.

2.1. Monocharged cations (M+)

Substituting n = 1 in Eqs. (1), (2) and (8), the typical equation for solvent extraction can be written as:

Mþ þ RH⇄MR þ Hþ ð9Þ

CMR CHþ
K conc ¼ ð10Þ
CMþ CRH
CRtot ¼ CMR þ CRH ð11Þ

By combining Eqs. (10) and (11), CMR can be calculated as follows:

CRtot
CMR ¼ ð12Þ
CHþ
1þ
ðK conc CMþ Þ

Fig. 1 shows the typical distribution isotherm for monocharged species based on Eq. (12).

2.2. Bicharged cations (M2+)

For n = 2, the typical equations for solvent extraction are written as follows:

M2þ þ 2RH⇄MR2 þ 2Hþ ð13Þ

CMR2 CHþ 2
K conc ¼ ð14Þ
CM2þ CRH 2

CRtot ¼ 2CMR2 þ CRH ð15Þ

88 V. Agarwal et al. / International Journal of Mineral Processing 167 (2017) 86–94

Fig. 1. Representative distribution isotherm for monocharged cationic species (n = +1) using Eq. (12), with pH = 2, total extractant concentration = 30 mM, and equilibrium constant =
0.03 at 298 K.

After substituting Eq. (15) into Eq. (14) and rearranging the resulting equation, a quadratic Eq. (16) is obtained:
! !!
4K conc CM2þ 2 4K conc CM2þ CRtot K conc CM2þ CRtot 2
2
CMR2 − 1 þ 2
CMR2 þ ¼0 ð16Þ
CHþ CHþ CHþ 2

The explicit roots for Eq. (16) are given by

vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
!2
u
CHþ 2 u C þ2
4K conc CRtot þ  t −4K conc CRtot − H −16K conc 2 CRtot 2
CM2þ CM2þ
CMR2 ¼ ð17Þ
8K conc

Fig. 2 shows a typical distribution isotherm for bicharged cationic species based on Eq. (17). It should be noted that only the root with negative sign
was used as the meaningful root for solvent extraction equilibrium.

2.3. Tricharged (M3+) cations

The simplest solvent extraction scenario using acidic extractants for tricharged cations can be written as follows:

M3þ þ 3RH⇄MR3 þ 3Hþ ð18Þ

Fig. 2. Distribution isotherm for bicharged species (n = +2) using Eq. (17) with pH = 2, total organic concentration =30 mM, and equilibrium constant = 0.03 at 298 K.
 V. Agarwal et al. / International Journal of Mineral Processing 167 (2017) 86–94 89

CMR3 CHþ 3
K conc ¼ ð19Þ
CM3þ CRH 3

CRtot ¼ 3CMR3 þ CRH ð20Þ

Rearranging Eq. (20) and substituting CRH from Eq. (19):

K conc CM3þ CRH 3

CMR3 ¼ ð21Þ
CHþ 3

 3
K conc CM3þ CRtot −3CMR3
CMR3 ¼ ð22Þ
CHþ 3

 
K conc CM3þ CRtot 3 −9CRtot 2 CMR3 þ 27CRtot CMR3 2 −27CMR3 3
CMR3 ¼ ð23Þ
CHþ 3

After several variable substitutions (see Appendix for details), it may be shown that Eq. (23) can be written as follows:

ffi vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
u
u ! v u
ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
!2 !3ffi u u ! v u
ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
!2 !3ffi
u −CRtot CHþ 3 u C C 3
C 3 u −C C 3 u C C 3
C 3
CR
CMR3
3
¼t þ t R tot H þ
þ H þ 3
þt
R tot H þ
− t R tot H þ
þ H þ
þ tot ð24Þ
162K conc CM3þ 162K conc CM3þ 81K conc CM3þ 162K conc CM3þ 162K conc CM3þ 81K conc CM3þ 3

Eq. (24) shows the extraction equilibrium for tricharged cationic species. A representative distribution isotherm for a tricharged metal ion is
shown in Fig. 3.
With the help of Eq. (24) it is also possible to see the effect of pH on distribution isotherms. Fig. 4 shows how the distribution isotherm for
tricharged metal cations changes with pH variation at a fixed equilibrium constant of 0.03 and total concentration of extractant in the organic
phase of 30 mM. With an increase in pH or a decrease in hydrogen ion concentration, the concentration of metal in the organic phase increases,
i.e., the extraction efficiency is increased.
Similarly, Fig. 5 shows the effect of varying the equilibrium constant on the distribution isotherm of tricharged cations at a constant pH of 3 and
total organic extractant concentration of 30 mM. It can be clearly seen from Fig. 5 that the increase in equilibrium constant improves the extraction of
cations.

2.4. Tetracharged cations (M4+)

The simplest solvent extraction scenario with acidic extractants for tetracharged cations can be written as follows:

M4þ þ 4RH⇄MR4 þ 4Hþ ð25Þ

Fig. 3. Distribution isotherm from Eq. (24) for a tricharged cationic metal species (n = +3) with pH = 2, total organic concentration = 30 mM, and an equilibrium constant = 0.03 at
298 K.
90 V. Agarwal et al. / International Journal of Mineral Processing 167 (2017) 86–94

Fig. 4. Three-dimensional plot illustrating the variations of the concentration of metal in the organic phase, the concentration of metal in the aqueous phase with varying concentration of
hydrogen ions for tricharged cations at fixed equilibrium constant (0.03) and fixed total extractant concentration (30 mM) in the organic phase.

CMR4 CHþ 4
K conc ¼ ð26Þ
CM4þ CRH 4

CRtot ¼ 4CMR4 þ CRH ð27Þ

Substituting Eq. (27) into Eq. (26) and expanding:

 4
K conc CM4þ CRtot −4CMR4
CMR4 ¼ ð28Þ
CHþ 4

Expanding the right side:

 
K conc CM4þ CRtot 4 −16CRtot 3 CMR4 þ 96CRtot 2 CMR4 2 −256CRtot CMR4 3 þ 256CMR4 4
CMR4 ¼ ð29Þ
CHþ 4

Fig. 5. Three-dimensional plot illustrating the concentration of metal in the organic phase, concentration of metal in the aqueous phase with changing equilibrium constant for tricharged
cations at fixed pH of 3 and total extractant concentration of 30 mM.
 V. Agarwal et al. / International Journal of Mineral Processing 167 (2017) 86–94 91

This equation has four roots only one of which (Eq. (30)) is relevant to solvent extraction process. See Appendix for the details of this derivation.

1
CMR4 ¼ C Rtot
4 vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
u sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi

!
u p ffiffiffi p ffiffiffi 3
pffiffiffi
u 2
3
u 3 6 8C Rtot 6 Z−
3
3 1024ðC Rtot Þ3 Z þ 27 þ 9 Z
1 u
þ u − sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi


ffi

ð
48 uu qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
pffiffiffi
t Z
3
3 1024ðC Rtot Þ3 Z þ 27 þ 9 Z

0 vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi 1
u sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi

!
B uu p ffiffiffi p ffiffiffi 3
2 pffiffiffi C
B u 3 6 8C Rtot 6 Z−
3 3
3 1024ðC Rtot Þ3 Z þ 27 þ 9 Z C
B u 3 ffiffiffi
p C
B u sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
2 C
B 8u− q ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi

6 C Rtot Z C
B u p ffiffiffi C
B t 3
ð Þ 3
þ þ C
B Z 3 1024 C Rtot Z 27 9 Z C
B C
B vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi C
B u s ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi ! C
1 pffiffiffi B u
B u p ffiffiffi p ffiffiffi 3
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
p ffiffiffi


C
C
− 3 B u 3 3 6 8C Rtot 3 6 Z− 2 3 s ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi C
48 B u ð
3 1024 C Rtot Z þ 27 þ 9 Z Þ 3 q ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi

C
B u p ffiffiffi 2 pffiffiffi C
B −u− sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi

3
6 3 1024 ð C Þ 3
Z þ 27 þ 9 Z C ð30Þ
B u p ffiffiffi
Rtot
C
B t 3 3 C
B Z 3 1024ðC Rtot Þ Z þ 27 þ 9 Z C
B C
B sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi C
B q ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi

C
B p ffiffiffi C
@ þ36 3 3 1024ðC Þ Z þ 27 þ 9 Z 3 A
Rtot

ð ÞÞ
−1 1=2
vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
u sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi

ffi !
u pffiffiffi pffiffiffi pffiffiffi
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi u


ffiu 3 1024ðC Rtot Þ3 Z þ 27 þ 9 Z
3=2
pffiffiffiqffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi 3 3 6 8C Rtot 3 6 Z−
u
3 1024ðC Rtot Þ3 Z þ 27 þ 9 Z u
3
Z u− sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi

ffi
u pffiffiffi
t Z
3
3 1024ðC Rtot Þ3 Z þ 27 þ 9 Z

K conc CM4þ
where z ¼
CHþ 4
Eq. (30) shows the extraction equilibrium equation for tetracharged cationic species. Based on Eq. (30), distribution isotherm for tetravalent
metal ions is shown in Fig. 6.
Fig. 7 shows how the distribution isotherm for tetracharged metal ions changes with pH at a constant equilibrium constant of 0.03 and a total
extractant concentration in the organic phase of 30 mM. With increasing pH, the concentration of metal in the organic phase will increase.
Similarly, Fig. 8 shows the effect of varying the equilibrium constant on the distribution isotherm for tetracharged metal cations at constant pH of 3
and total organic extractant concentration of 30 mM. It is clear from Fig. 8 that increasing the equilibrium constant improves the extraction of cations.
Fig. 9a and b summarize the differences of the distribution isotherms for the four different oxidation states of cationic metal species. It can be
observed from Fig. 9a that, after reaching a characteristic concentration of total metal ion concentration, an increase in oxidation state from n = +1

Fig. 6. Distribution isotherm from Eq. (30) for tetracharged cationic species (n = + 4), where pH = 2, total extractant concentration in the organic phase = 30 mM, and equilibrium
constant = 0.03 at 298 K.
92 V. Agarwal et al. / International Journal of Mineral Processing 167 (2017) 86–94

Fig. 7. Three-dimensional plot illustrating the concentration of metal in the organic phase and the concentration of metal in the aqueous phase with changing pH for tetracharged metal
ions at fixed equilibrium constant (0.03) and fixed concentration of extractant (30 mM).

to n = +4 results in a decrease in extraction at constant pH and organic extractant concentration. In this case this concentration is ~0.11 M at pH of 2 and
organic extractant concentration and equilibrium constant at 30 mM and 0.03; respectively. Of course, by changing pH and organic extractant concen-
tration this characteristic concentration will change. This behavior can also relate to the metal to extractant concentration ratio. It can be seen from
Fig. 9b that at lowest total metal ion concentration of 0.002 M, when metal ion to extractant concentration ratio is also lowest, increasing the oxidation
state from n = +1 to +4 results in increased extraction. The possible reason for this behavior could be when there is enough extractant molecules avail-
able to react with all metal ions, then due to high charge density, cations with higher oxidation number extract better than cations with low charge den-
sity. But when metal ion concentration to extractant ratio increases, then due to limited availability of extractant molecules, cations with lower oxidation
number extract better since according to Eq. (1), cations with low oxidation number require less number of extractant molecules to react with.

3. Conclusions the effects of pH and equilibrium constant are illustrated in three-dimen-

A theoretical model for solvent extraction of differently charged cat-
ionic species using acidic extractants at given set of conditions (constant
pH, equilibrium constant and total organic concentration) was further de-
veloped using the mass balance equation introduced by Free (Free, 2013).
A mathematical relationship between concentration of metal ions in the
aqueous phase and that in the organic phase was developed for each cat-
ionic species of different charge, which helps in predicting the behavior of
particular cationic species at a given set of conditions. This model helps in
further understanding of the solvent extraction of metal ions with differ-
ent oxidation states using acidic extractants, but holds true only for the
simplest scenario, where metal ions exist in simple cationic form in the
aqueous phase. For cationic metal complexes, modified models are re-
quired. Based on the explicit algebraic expressions for the isotherms,
sional form for n = +3 and n = +4. It was shown that increasing both
pH and equilibrium constant favors the extraction reaction. It was also
found that increasing the oxidation state of species from +1 to +4 results
in decrease in extraction above a certain characteristic concentration of
metal ion in the aqueous phase under equal experimental conditions
and this characteristic concentration is not independent, and correspond-
ingly results in an increase in extraction efficiency when the extractant
concentration greatly exceeds the metal concentration.
Acknowledgements
This study was sponsored by ARL and was accomplished under Co-
operative Agreement Number W911NF-16-10-2-0025. The authors
would like to thank Profs. J. Kellar, W. Cross, J. Bendler and D. Boyles
for useful discussions.

Appendix A.

A.1. Details of solution to Eq. (23)

Defining the following symbols:

K conc CM3þ
z¼
CHþ 3

a ¼ CM3þ ; b ¼ CRH ; c ¼ CMR3 ; d ¼ CHþ ; e ¼ CRtot

and substituting in Eq. (23), it follows that:

c ¼ ze2 −9e2 cz þ 27ec2 z−27c3 z ð31Þ

Fig. 8. Three-dimensional plot illustrating the concentration of metal in the organic phase,
concentration of metal in the aqueous phase and equilibrium constant for tetracharged  
metal ions at fixed pH of 3 and total extractant concentration of 30 mM. 27zc3 −27ezc2 þ 1 þ 9ze2 c−ze3 ¼ 0 ð32Þ
 V. Agarwal et al. / International Journal of Mineral Processing 167 (2017) 86–94 93

Fig. 11. Comparison of calculated and experimental values of distribution coefficients

(initial pH =2, initial [Dy(III)] = 0.25 mM, O/A = 1:1).

Eq. (32) is a cubic equation in c, which can be written in the follow-

ing form (Carruccio, 1964):

pc3 þ qc2 þ rc þ s ¼ 0 ð33Þ

where p = 27z ; q = − 27ez ; r= (1+ 9ze2) ; s = − ze3.

First, we define a variable ‘f ’:

2

3r q
− 2
p p
f¼ ð34Þ
3

Substituting the variables p, q and r in Eq. (34), we obtain:

 ! !
3 1 þ 9e2 z ð−27ezÞ2
−
27z ð27zÞ2
f¼ ð35Þ
3
Fig. 9. (a) Distribution isotherms for different cationic species and (b) enlarged view of
distribution isotherms at lower total concentration of cationic species at fixed equilibrium
constant (0.03) and fixed concentration of extractant (30 mM).
1
f¼ ð36Þ
27z
Next, we define another variable ‘g’:
3

2q 9qr 27s
3
− 2
þ
p p p
g¼ ð37Þ
27

After substituting the variables p, q, r and s into Eq. (37), we obtain:

e
g¼ ð38Þ
81z

Then we define ‘h’:

3
g2 f
h¼ þ ð39Þ
4 27

After substituting the variables f and g from Eqs. (36) and (38) into
Eq. (39), we obtain:

 e 2

1 3
Fig. 10. Plot of log D − 3pH versus log [PC88A] ([Dy(III)] = 0.25 mM, initial pH = 2, h¼ þ ð40Þ
O/A = 1:1). 162z 81z
94 V. Agarwal et al. / International Journal of Mineral Processing 167 (2017) 86–94

As concentration cannot be negative, h, which is related to concen- A.3. Verification of model for a tricharged (M3+) metal ion
tration and equilibrium constant, is always positive. Hence, there is
only one real root available for Eq. (32). To verify the given model with experiments, solvent extraction data
At this stage, variables R, S, T, and U are defined for convenience. for dysprosium with acidic extractant PC88A from hydrochloric acid so-
lution is taken into consideration. Concentration of PC88A is varied from
g 
R¼− þh
1=2
ð41Þ 1 mM to 5 mM at constant initial dysprosium concentration of 0.25 mM.
2 Initial pH was kept constant at 2, and all experiments were carried out at
S ¼ R1=3 ð42Þ room temperature and aqueous to organic volume ratio of 1:1. The plot
g 
1=2 between logD-3pH vs. log [PC88A] was used to find the equilibrium
T¼− −h ð43Þ
2 constant. The result can be seen in Fig. 10. The slope and equilibrium
constant values were found to be equal to 2.98 and 11.74, respectively.
U ¼ T1=3 ð44Þ Substituting equilibrium constant value K = 11.74 in Eq. (24), theo-
retical distribution coefficient values were calculated at different con-
It follows that centrations of PC88A at constant pH of 2. Fig. 11 shows that the plot
between model-predicted versus experimental distribution coefficients

q is a straight line with slope of 0.85 and regression coefficient of 0.979,

c ¼ ðS þ UÞ− ð45Þ
3p which shows that model derived in Eq. (24) predicts the solvent extrac-
tion behavior well when compared to experimental results.
After substituting variables p, q, S and U in Eq. (45), the final root is
obtained which is shown in Eq. (24). References
Alguacil, F.J., 1999. Modeling Au (CN) 2− extraction by mixtures of primene JMT and cyanex
A.2. Details of derivation of Eq. (30) 925 reagents. AICHE J. 45, 2136–2141.
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metals, uranium, and thorium from nitrate solutions by binary extractants. Theor.
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z¼ Čomor, J.J., Kopečni, M.M., Petković, D.M., 1997. Solvent extraction of thorium nitrate with
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rare earth elements using solvent extraction: predicting separation performance
using laboratory equilibrium data. Ind. Eng. Chem. Res.
Mishra, S.L., Singh, H., Gupta, C.K., 2000. Simultaneous purification of dysprosium and ter-
After substitution in Eq. (29), it follows that:
bium from dysprosium concentrate using 2-ethyl hexyl phosphonic acid mono-2-
ethyl hexyl ester as an extractant. Hydrometallurgy 56, 33–40.
c ¼ ze4 −16e3 cz þ 96e2 c2 z−256ec3 z þ 256c4 z ð46Þ Pratt, O., 1866. New and Easy Method of Solution of the Cubic and Biquadratic Equations:
Embracing Several New Formulas, Greatly Simplifying this Department of Mathemat-
  ical Science. Longmans, Green, Reader, and Dyer, pp. 71–84.
256zc4 −256ezc3 þ 96e2 zc2 − 1 þ 16ze3 c þ ze4 ¼ 0 ð47Þ Rydberg, J., 2004. Solvent Extraction Principles and Practice, Revised and Expanded. CRC
Press.
Thakur, N.V., Jayawant, D.V., Iyer, N.S., Koppiker, K.S., 1993. Separation of neodymium
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physically relevant for the solvent extraction process (Pratt, 1866) and 99–108.
the obtained root is shown in Eq. (30).