Hydrometallurgy 133 (2013) 1522

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Hydrometallurgy
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Some additional aspects of gold(III) extraction by dibutyl carbitol

Igor V. Mironov
Institute of Inorganic Chemistry, Siberian Branch of RAS, Lavrentjev ave 3, Novosibirsk, Russia
Novosibirsk State University, Pirogova 2, Novosibirsk, Russia

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

Article history: From changes of volumes of the aqueous and organic phases it was found that the extraction of HAuCl4 from
Received 25 April 2012 hydrochloric medium by dibutyl carbitol (DBC) involves co-extraction of about 6 mol of water per one mole of
Received in revised form 19 October 2012 gold(III). The changes of phase volumes are equal to Vorg =0.17 nAu, Vaq =0.20 nAu, where nAu is the number
Accepted 12 November 2012
of moles of gold(III) extracted. Distribution coefcients have been obtained for CAu org =1061.25 M, CHCl =1 M
Available online 20 November 2012
and for some other conditions. The electro-conductivity of extracts and solutions of HAuCl43.3H2O in dry DBC has
Keywords:
been measured. In the organic phase the contribution of the ionic subsystem increases with the concentration of
Gold(III) complexes gold(III) and at high CAu org exceeds 50%. A set of species in the organic phase H+, AuCl4, HAuCl4, (HAuCl4)2,
HAuCl4 H(AuCl4)2, and H2(AuCl4)+ containing molecules of DBC and water, is sufcient to adequately explain the exper-
Dibutyl carbitol imental data on distribution and electro-conductivity of extracts. However, it is necessary to take into account
Equilibrium in the organic phase medium effects, which were simulated using simple models by Born and Debye. It has been shown that for this
Medium effect system the method based on the correspondence of the organic phases (equality of CAu org) gives satisfactory
results in recalculating data from 1 M to other CHCl.
2012 Elsevier B.V. All rights reserved.

1. Introduction
It is well known that gold(III) may be readily extracted into oxygen-
containing organic solvents from aqueous solutions of hydrochloric acid,
and these processes are widely used for the recovery and purication of
gold. Many extractants and techniques have been proposed, but current-
ly the most frequently employed is the method with the use of dibutyl
carbitol (DBC, dibutyl ether of diethylene glycol, butyl diglyme, butex,
C4H9OC2H4OC2H4OC4H9). The process as a whole has high selec-
tivity towards the separation gold from other elements, especially of
platinum group metals (Feather et al., 1997; Kyriakakis, 2005; Morris
and Khan, 1968). Variations of the method differ in the concentration
of HCl and in a choice of reducing and other agents (Jung et al., 2009;
Morris and Khan, 1968; Rimmer, 1974; Zhu and Gu, 2006). With excep-
tion of a relatively high price, DBC as extractant has a number of attrac-
tive properties, as low solubility in water, low vapor pressure, low
toxicity, resistance to oxidizing agents including nitric acid. The extrac-
tion process is fast, and equilibrium distribution can be reached within
2 min after mixing (Feather et al., 1997; Morris and Khan, 1968). Despite
the prevalence of using DBC for the extraction of gold(III), available
quantitative data on this process is limited. In the pioneering work by
Morris and Khan (Morris and Khan, 1968) the distribution coefcients
D=CAu org/CAu aq have been determined only for three relatively low
concentrations of gold and several concentrations of HCl. Though behav-
ior of D (CAu and CHCl) was not simple, the nature of processes was not
Tel.: +7 383 316 56 32.
E-mail address: imir@niic.nsc.ru.
discussed. In another work (Javanshir et al., 2011) this extraction was
studied for CAu =5104 M and CHCl =2 M. When gradual adding alkali
into the solution and measuring D at different pH, it has been found that
the coefcients for H+ and AuCl4 in the equation of extraction are equal
to 0.5 and 1, i.e. per one anion AuCl4 only 0.5 H+ ion passes from one
phase to another. That is implausible for heterogeneous processes but
no explanations were offered.
The object of this work was to study the extraction of HAuCl4 into
the DBC for wider range of concentrations of gold(III) and to give
explanations of taking place processes.
2. Materials and techniques
Initial concentrated solutions of HAuCl4 (CAu =0.72 M) were pre-
pared by dissolving metallic gold (99.9) in aqua regia followed by several
evaporations with addition of HCl and then of water. Solid crystalline
hydrate was obtained by evaporating portion of the concentrated solution
on a water bath with further crystallization and additional drying over
concentrated H2SO4. Analysis of the product has shown that it corre-
sponds to HAuCl43.3H2O. Diethylene glycol dibutyl ether was obtained
from Aldrich, 99+%. Before use, the DBC was washed twice in a sepa-
rating funnel by a solution of Na2CO3 (5%), water, 3 M HCl and then
again by water several times, until the mixture began to separate quickly,
giving two absolutely transparent colorless phases. Most experiments
0 6
were carried out at CHCl aq =1 M, CAu aq =210 1.7 M, t=25 C.
Some measurements were done also at other temperatures (20, 35 and
45 C), CHCl aq and dilutions of DBC by CCl4. Extraction was performed
in test tubes with ground stoppers, using DBC saturated by water.

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16 I.V. Mironov / Hydrometallurgy 133 (2013) 1522
Volumes of phases were equal to 110 ml, their ratio was varied.
After adding all components and shaking the test tube by hand for
2 min, it was placed into a thermostated waterbath for 30 min.
During this period the tube was taken out 23 times and shaken again.
After phase separation the concentration of AuCl4 in the aqueous
phase (CAu aq) was determined. The content of gold(III) in the organic
phase was calculated considering changes of phase volumes after extrac-
tion, CAu org =CAu aq /[r(10.20CAu aq)+0.17CAu aq] where CAu aq =
0 0 0
CAu aqCAu aq; r=Vorg/Vaq. In some cases, the organic phase was also an-
alyzed for gold(III).
Solutions of HAuCl4 in dry DBC were prepared by dissolving
weighed amounts of solid HAuCl43.3H2O. The dissolution occurs
quickly until at least CAu b 1 M. The DBC for dehydration was heated for
0.5 h at 130140 C and then additionally dried with CaCl2. According
to the IR spectra, the residual water content was 0.0050.01 M.
The gold(III) concentration CAu aq was determined from the
absorption spectra, = 5600 cm1 M1 at = 31,800 cm1 or =
40,900 cm1 M1 at = 44,200 cm1, using a Specord spectropho-
tometer. The aqueous phase was slightly diluted by water before being
placed in the cell to prevent the turbidity of the solution due to the iso-
lation of the dissolved DBC when the conditions changed, primarily the
temperature. Very low concentrations of gold were determined by
atomic absorption with electro-thermal atomization (MGA-915),
where = 242.8 nm. The IR spectra (absorbance) of water were
recorded using a single-beam Fourier spectrophotometer Scimitar FTS
2000 with a quartz cell of l = 1 mm. The anhydrous DBC was used as a
reference solution.
Fischer titration is impossible in the presence of gold(III). Therefore,
the quantity of water co-extracted with gold(III) was evaluated using
the change of the volume of the aqueous phase. Due to the wetting of
the tube wall, the direct measurements of V in a narrow graded tube
have an error of not less than 0.03 ml. Therefore, we also used a method
based on the change of the concentration of the component that was
not extracted. For this component, C1/C2 = V2/V1 = 1 + V/V1, where
C1, V1 and C2, V2 refer to the aqueous solution before and after extrac-
tion. To subtract the contribution due to the dissolution of DBC in
water, the V could be corrected with the help of the known solubility
of DBC (2.7 g/l) (Nikolotova and Kartashova, 1976). HCl or a special
additive of Cr3+ was used as the components. They do not pass into
the organic phase, whereas HAuCl4 is almost totally extracted. The
solutions for these experiments were prepared by controlling the
weight. The change of CHCl was determined by gravimetric titration
with NaOH, using a microsyringe with a drop size of 12 mg and
methyl-red as the indicator. The following masses were measured:
HCl (ms1) and the same acid used for extraction (m2), the added solu-
tion of HAuCl4 (m3), the sample of the aqueous phase after extraction
(ms2), and the alkali used for the titration of ms1 and ms2 (ma1 and
ma2). The ratio Cl HCl/C2 HCl = (ma1/ms1)(ms2/ma2)(1/2)m2/(m2 + m3)
where 1 and 2 are the densities of the aqueous phases before and
after extraction. Chromium(III) chloride complexes are weak and
inert. The change of CCr can be determined from the absorbance at
16,700 cm1. The error of these determinations of V is approximately
3 times lower than the error for direct measurements in a test tube.
However, at high CAu an appreciable amount of gold(III) remains in
the aqueous phase. When it is titrated together with HCl, it forms
hydroxo-complexes of Au(OH)iCl4, and thus xing the endpoint is dif-
cult. In the case of chromium(III), the intense absorption of AuCl4 can
distort the band of Cr 3+.
The conductivity measurements of the solutions and extracts were
conducted at 25 C (Radelkis OK 102/1) in a thermostated cell with a
water jacket. The cell constant was determined from measurements in
0.1 M NaCl, where =106.7 cm2 1 eq1 (Robinson and Stokes,
2002). Because they are separated from the aqueous phase, the extracts
are unstable systems, and small changes in the conditions (e.g., temper-
ature) can cause supersaturation and the isolation of micro-droplets of
the aqueous solution that in turn can affect the results of the conductivity
measurements. Therefore, prior to measurements, 5% dry DBC was
added to the extracts to prevent the separation, but the addition of
DBC should not signicantly affect the equilibrium in the organic
phase. The value of AuCl4 =60.30.9 cm2 1 eq1 in the aqueous
solution (CAu =0.01 M) was determined from the data of the titration
of HAuCl4 with NaOH by considering the equilibrium AuCl4 +H2O=
AuCl3OH +H+ +Cl, lg K=6.13 (Mironov and Tsvelodub, 2000)
and values of Na+
=47.4, H+
=340, and Cl
=70.5 (Dobos, 1975).
The densities of the aqueous and organic phases were measured
by hydrostatic weighing of a standard body or by using a pycnometer
(V 1 cm 3).
The viscosity of the extractant was measured with the help of a
glass capillary viscosimeter (d = 0.76 mm). For dry DBC and DBC sat-
urated by water, the values practically coincided: at 20 C = 2.33 cp
and at 25 C = 2.06 (2.12 (Pal and Sharma, 1998)). Due to the small
volumes involved, the viscosity of the gold-containing organic phases
was measured using a vibration viscometer Reotekhnika. The
change was approximated as log(/ 0) 0.85CAu org.
The solubility of water in DBC from 1 M HCl is equal to 11.51 g/l,
which was obtained by gravimetric titration and agrees with the
known values of 10.7 or 10.4 (Nikolotova and Kartashova, 1976) for
the DBC/H2O system.
The distribution coefcient of HCl in the DBC/1 M HCl system was
determined via pH after back-extraction into 0.1 M NaCl with the use
of a glass electrode calibrated in the same medium, and the result was
logDHCl = 3.9. The extract of HCl is not electro-conductive. For
perchloric acid, logDHClO4 = 0.89 and 0.36 for concentrations in
DBC of 0.34 and 0.75 M, respectively.
The analysis of the data was performed using the weighted least
squares method. In addition, the program to calculate the equilibrium
composition for the given total concentrations and constants was
used. The double standard deviations are given as the errors.
3. Results
3.1. The densities and the changes of the volumes
The densities of the extracts and solutions of HAuCl4 in the aqueous
phase and DBC are presented in Table 1. The density of the aqueous
solutions of HAuCl4 depends linearly on the concentration of gold(III),
which indicates the constancy of the molar volume of the solvent. In
the Root equation = 0 + aCAu + bCAu 3/2
, the parameters are a = 251
2 and b 0. For the organic phase, a = 301 4 for the extracts and
solutions. After the extraction from the aqueous phase, its volume
decreases, and the volume of the organic phase increases. However,
these changes are different: Vorg = aVaq and a = 0.85 0.07.
This simple relation between Vorg and Vaq is valid only when
the partial molar volumes and the hydration number are constant.
The dependence of Vaq/Vorg upon CAu org is shown in Fig. 1. In the range
of CAu org studied, the dependence is approximately linear: Vaq/Vorg =A
CAu org, A=0.2010.014. Because the product CAu orgVorg =nAu is
equal to the total amount of gold(III), which transitions from the
Table 1
The densities of the solutions and extracts of HAuCl4a, t = 20 C.
Phaseb CAu, M , g/dm3 Phaseb CAu, M , g/dm3
A 1.33 1331 C 0.25 962
1.93 1481 0.53 1044
3.15 1796 0.78 1118
4.59 2146 0.89 1156
B 1.21 1317 D 0.54 1043
0.57 1159 0.92 1162
a
0 (g/dm3): 998 (aq), 1016 (1 HCl), 883 (dry DBC), 884 (DBC sat. with H2O).
b
A aqueous solutions of HAuCl4; B aqueous solutions of HAuCl4 in 1 M HCl; C
extracts of HAuCl4 in DBC; and D solutions of HAuCl43.3H2O in dry DBC.
 I.V. Mironov / Hydrometallurgy 133 (2013) 1522 17

aqueous phase into the organic phase, the initial volumes are related to
0 0
the equilibrium ones as Vaq =Vaq0.20 nAu and Vorg =Vorg +0.17 nAu.

3.2. The distribution coefcients

The dependence of the distribution coefcient D upon CAu org is

shown in Fig. 2. It has qualitatively the same form as the dependences
for other oxygen-containing extractants and metal ions (Afanas'eva
and Mironov, 2000; Peschevitskii et al., 1992; Zolotov, 1963). With
increasing concentration, the D(CAu org) increases and then decreases
0
sharply. Some of the data for HCl = 1 M is also presented in Table 2.
The values of D for other CHCl could be obtained from Tables 4 to 6.
0
For high CAu , the changes of the volumes mentioned above have to
be considered.
Of particular interest is the determination of D at very low CAu
(b10 5 M). For example, in the work (Morris and Khan, 1968) the
value of D = 8.3 has been obtained for CAu = 6 10 7 M, which is
much lower than for slightly higher CAu. In our experiments, we also
obtained values of D that were too low several times. However, the Fig. 2. Dependence of the distribution coefcients (D) of HAuCl4 upon CAu org (M) at
slope of logCAu org from logCAu aq for CAu = 10 510 3 M is close to 0
CHCl = 1 M, t = 25 C; and data from Morris and Khan (1968).
1, which is evidence of the simplest principal equilibrium of extrac-
tion. A more detailed study (Table 3) showed that the observed
value of D depends on the ratio of the volumes of the phases for
equally low CAu 0 0
. With decreasing r = Vorg 0
/Vaq, the distribution coef- high hS = 89. In the work (Javanshir et al., 2011), the value of hS =
cient increases and reaches the normal values that are characteristic 5.4 (diluent of kerosene, CAu org = 5 10 4 and CHCl = 2 M) has been
for higher CAu. In addition, the content of gold in the aqueous phase obtained using the same method, and this value is also too high. It
increases with time, and the process is accelerated in light. Given is difcult to imagine that such a number of large molecules of DBC
these facts, it follows that the reason for the sharp decrease of D at may be bonded with one hydrated ion H +. High values of hS have
very low CAu is not the features of extraction but an additional process also been found for some other extractants, e.g., methyl isobutyl
that is signicant in this range. Most likely, this process is the reduc- ketone. It is likely that the decrease of D is caused not only by a decreas-
tion of gold(III) to gold(0), though the presence of gold(I) in the form ing concentration of the extractant at the dilution. The concentration
of AuCl2 is also possible. The reducing agent can be any uncontrolled of water in the organic phase can also be of great importance. At higher
micro-impurity in the extractant. The photosensitivity of very diluted CAu org the inuence of the dilution is lower. Another way to determine
gold(III) solutions is well known. The methods of analysis do not dis- the solvation numbers is based upon the saturation of the extractant at
tinguish the valence state at low concentrations, and the reduction of high CAu org (Peschevitskii et al., 1992; Sergievsky, 1984) and often leads
10% gold(III) will inevitably lead to a decrease of the experimental D to lower values of hS. It is clear that the solvation number can be variable
by a factor of approximately ten. in general and decrease with increasing CAu org, remaining lower than
The distribution coefcients decrease rapidly with increasing tem- CS/CAu org. According to the data for high CAu org (Table 4), it follows
perature: logD/logT = 0.029 0.006 grad 1 for CAu org = (12) that the values of hS b 3 can also occur in this system. Thus, the problem
10 4 M in the interval of t = 2045 C. However, considering the of determining the solvation numbers and their changes remains
complex nature of the equilibrium in the organic phase, this estimate unsolved and requires additional research.
cannot be extended to higher concentrations.
The dilution of DBC by inert solvent CCl4 leads to a decrease of D,
3.3. Absorption spectra and conductivity
especially at low CAu org = 10 510 3 M. A formal estimation of the
solvation number hS = (lgD/lgCDBC)CAu gives an unrealistically
In comparison with the results for the aqueous solution, in the UV
absorption spectra of the extracts, the principal band of HAuCl4 is
shifted to the red side from 0 = 31,800 cm 1 to 30,700 cm 1 with-
out changes in its shape or intensity. This result is also observed at
relatively high CAu org where polymeric species exist in the system.
Similar shifts for other solvents have been observed in the works of
(Afanas'eva and Mironov, 2000; Peschevitskii et al., 1992), and they
are caused by medium effects (polarization). Thus, the changes in

Table 2
0 0
Distribution coefcients of HAuCl4 for various CAu (M), CHCl = 1 M, t = 25 C.
0 0
logCAu r logCAu aq logD logCAu r logCAu aq logD

3.77 1 5.78 2.00 0.09 1.4 2.87 2.59

2.83 1 4.89 2.05 0.80 0.2 2.38 2.21
2.13 0.8 4.28 2.24 0.09 1 2.42 2.26
1.79 1 4.08 2.28 0.22 2 2.36 2.23
1.79 0.33 3.82 2.50 0.63 0.2 1.59 1.55
1.79 0.2 3.70 2.63 0.51 0.2 1.13 1.16
0.80 1.2 3.59 2.69 0.33 0.2 0.61 0.67
Fig. 1. The dependence of Vaq/Vorg upon CAu org. The linear regression for all data has a
0.33 2.4 3.36 2.70 0.21 0.2 0.38 0.48
slope of 0.201 0.014.
18 I.V. Mironov / Hydrometallurgy 133 (2013) 1522

Table 3
Observed values of D at low CAu a, t = 25 C and CHCl = 1 M.
0
CAu, 106 r CAu aq, 107 logD 0
CAu , 106 r CAu aq, 107 logD

18.5 1 2.9 1.8 1.09 0.5 1.3 1.2

1.79 1 3.5 0.6 1.81 0.2 1.2 1.8
1.81 0.5 2.7 1.1 0.72 0.2 1.2b 1.4
1.45 0.5 2.5 1.0 0.72 0.08 1.5 1.7
a
Method atomic absorption, measurements in 25 min after extraction.
b
2.5 107 M after 1.5 h.

the coordination sphere of the complex ion AuCl4 do not occur, as in

other cases of the hydrationsolvation mechanism of extraction
(Zolotov, 1963). For this mechanism, it is assumed that the ionic asso-
ciate {H +(H2O)hwShsAuCl4} is formed in the organic phase from the
solvated and hydrated H + ion and from the complex anion as the
counter ion, which is the principal particle.
The IR absorption spectra of water in DBC, in a solution of
HAuCl43.3H2O in dry DBC and in other organic media are shown in
Fig. 3. In the DBC, the spectrum is a typical doublet in which the
long-wave band is distorted in the presence of HAuCl4 due to the inu-
ence of hydrogen bonds. The short-wave band may be used for the eval-
uation of the concentration of free water (Mironov and Troshin, 2010).
The extracts and the solutions of HAuCl4 in DBC are electro-
conductive (Fig. 4). When CAu org >102 M, the conductivity increases
more rapidly than CAu org and, at 0.1 M, reaches approximately 5% of the
conductivity of the aqueous NaCl solution of the same concentration.
Given the large size of the ions, the presence of polymeric species and
the high viscosity of DBC, one can conclude that the fraction of ionic
forms in the organic phase is several times higher than this value.
From a practical point of view, a high conductivity implies that one
can attempt to use electrochemical techniques instead of the chemical
reduction of gold (III) in the organic phase.
Thus, a quantitative description of the system, in addition to poly-
merization, requires the consideration of other factors, such as the
presence of neutral and ionic subsystems, medium effects (activity
coefcients) and the inuence of water.
4. Discussion
4.1. Co-extraction of water
Fig. 3. IR molar absorptivity of water in several media: DBC; tri-n-butyl phosphate
(TBP, 0.6 M in CCl4) (Mironov and Troshin, 2010); acetonitrile (AN); solution of
HAuCl43.3H2O in dry DBC ( = A/(3.3CAu orgl), CAu org = 0.0234 M).
Vaq/Vorg from CAu org (Fig. 1) with the slope A V aq


V Au hw V w 0:201  0:014 M1 enables us to consider it constant

as a rst approximation: hw*=(0.2010.089)/0.018=6.2(0.9). The
volume increase of the organic phase Vorg is lower than Vaq. Because
a molecule of HAuCl4 passes together with hw* molecules of water to the
organic phase, one can show that the total molar volume is equal to


V org V Au hw V w org 0:170 M1 and decreases compared with
the aqueous phase by approximately 0.030 M 1 using the same rela-
tion and densities of the extracts (Table 1). Therefore, the ratio
V org =V aq V org =V aq 0:85, which coincides with the value
obtained from the direct measurements of Vaq and Vorg. The
total concentration of water in the organic phase is equal to C w
 
C w 0 h C w 0 V org C Auorg , where Cw
 0
w = 0.6 M is the solubility of
water in the pure extractant. However, for this system, the addend
C w 0 V org 0:1 is much less than hw*. Therefore, as a good approxima-
0
tion, we can use the relation Cw = Cw + hw*CAu org. For ideal solutions,
the concentration of free water in the organic phase [H2O]org remains

The volume decrease of the aqueous phase after extraction is caused

by the removal of HAuCl4 and water to the organic phase,


V aq V Au hw V w nAu , where nAu is the number of moles of gold,


V w and V Au are the partial molar volumes of water and HAuCl4, respec-
tively, and hw is the total hydration number indicating how many
moles of water are co-extracted with one mole of gold(III). According to
the data on the density of aqueous solutions (Table 1) and the relation
 
V Au d=dC Au =C Au d=dC Au , it follows that V Au
HAuCl4

0:089 M 1 because d/dCAu =251 and V w 0:018 M 1 . In general,

the total hydration number hw* may depend on CAu org, but the linearity

Table 4
Data for CAu org > 0.9 M.
0 0
CAu CHCl r CAu org logD CS/CAu org

0.62 2.3 0.2 1.40 0.64 2.2

0.58 2.9 0.25 1.36 0.86 2.3
0.62 1 0.2 1.25 0.49 2.6
0.52 3.8 0.33 1.21 1.81 2.7
0.46 1 0.2 1.16 0.68 2.9
Fig. 4. The change of the ion concentration in the organic phase with the growth of the
0.31 1 0.2 1.06 1.17 3.2
total concentration, Z = 103 / (0) (M), for the extracts of HAuCl4 (with the addition
0.46 4.6 0.4 0.97 2.84 3.5
of 5% dry DBC), solutions of HAuCl43.3H2O in dry DBC, and extracts of HClO4 in DBC.
0.23 1 0.2 0.91 1.56 3.8
The solid lines correspond to the calculations for the extracts and the solutions.
 I.V. Mironov / Hydrometallurgy 133 (2013) 1522
constant and equal to Cw0
. However, due to medium effects, it typically
varies. In this case, hw* can be not equal to the number of water
molecules (hw) bonded with H+ and AuCl4, and [H2O]org =
0
Cw + (hw* hw)CAu org.
4.2. The electro-conductivity
The extracts and solutions of HAuCl4 in DBC have a signicant
electrical conductivity (Fig. 4), which is also observed for TBP, methyl
isobutyl ketone, and diethyl ether. The interpretation of data on elec-
trical conductivity (EC) requires an estimate of the ionic conductivity
. If the formation of only single-charged ions is assumed, which is
typical, then = +i+i + jj in the general case, where
+i = [K +i] / Z and i = [A i] / Z are the fractions of the cation K +i
and anion A j in the sum of the concentrations of cations or anions:
Z = [K +i] = [A i]. However, there are no substances with known
degree of dissociation in DBC. For example, extracts of perchloric
acid often have a high degree of transformation into ionic forms
(Nikolotova and Kartashova, 1976), but their EC in DBC are several
times lower than that for HAuCl4 at the same concentration (Fig. 4).
The salt Et4NBr does not show EC at all, even at C=0.1 M. Therefore, to
estimate , we used the Walden rule. It is likely that associates of the
type H+(H2O)hwShs have a large size and that their ionic mobility is low.
The data for large cations as NR4+ in other solvents (Evans and Matesich,
1973) show that for them the product + is in the range 2025. The
anion AuCl4 in aqueous solution has =60 cm2 1 eq1, which cor-
responds to =54. On this basis, for the extracts and solutions of
HAuCl4 in DBC, the value =77 was accepted and used for all species
in further evaluations. This assumption means that these evaluations
are semi-quantitative. However, the known data on + and for
other ions in aqueous and organic media (Dobos, 1975) indicate that
changing the set of species is unlikely to change the product by greater
than a factor of 1.5. At the same time, the total increase of the conductivity
is greater than 104 times. The measurements of EC for high CAu org, where
most of the gold(III) exists in ionic forms, are in agreement with this
assumption. Thus, Z103 /, where is the specic conductivity. For
low CAu org the value of =+ + =37; for higher Cau org it has to be
corrected with the help of the viscosity.
4.3. Equilibrium, medium effect and ionic subsystem
In aqueous solutions, HAuCl4 is a strong electrolyte and fully dis-
sociates into H + and AuCl4. When [H +][Cl ] > 10 4, the hydrolysis
of AuCl4 can be neglected (Mironov and Tsvelodub, 2000). In the
hydrationsolvation mechanism of extraction, the coordination
sphere of the complex anion does not change, which is evidenced
by the spectra and the results of chemical analysis, which show that
the ratio of nCl/nAu = 4 in the organic phase. Because the extraction
of HCl is negligible, the minimal set of equilibria including the forma-
tion of polymeric and charged species can be represented as
H aq A aq HAorg ; K 0 1 cules associated with one H + ion. For low values of n or for
nHAorg HAnorg ; K n 2 When logCAu org = 3.20, the slope is = 0.85, and therefore
H org A org HAorg ; K 11 3
H org iHAorg HHAi org ; i 4 log(+ 1 1) = 6.18 0.15, (+ 1 + 1) = (1.9 1.0) 10 3. Because
A org jHAorg HAj A org ; j : 5 trostatic interactions, one can assume that log+ 1 = log 1 = 3.1, as
For brevity, the constant fragment AuCl4 is denoted as A. Among
the equilibria (Eqs. (1)(5)), only the rst one (Eq. (1)) is heteroge-
neous (of extraction), and all others belong to the organic phase.
The molecules of water and extractant S are omitted; for example,
19
(HA)n = (H +A )n Sx (H2O)y. For CAu org b 0.05 M, the extractant and
water are present in a large excess, and the stoichiometry of the spe-
cies with respect to them cannot be determined. At this stage, the
concentration [S] is included in the constants.
According to the data on (Fig. 4), it follows that the fraction of
ion species in the CAu org does not exceed 2% for CAu org b 3 10 3 M.
In this eld, the dependence of logCAu org upon logCAu aq is almost
linear with a slope of 1.13 0.08. Thus, the simplest equilibrium
(Eq. (1)) is a basic one, and the form HA is dominant in the organic
phase. A small slope deviation from Eq. (1) is caused by the growing
inuence of the polymerization. In the range of CAu org = 0.010.1 M,
the slope is already close to Eq. (2), i.e., dimeric species are formed in
the system. The fraction of the ionic subsystem increases simulta-
neously, and, for CAu org = 0.1 M, the fraction is approximately 10%.
The data analysis for the model D = K0CH aq + 2 K02K2 CAu aqCH 2
aq leads
2
to the following estimates: logK0 =1.890.06 and log(K0K2)=5.86
0.07. This model corresponds to the approximation that CAu org =
[HA]org +2[(HA)2]org. Therefore, the constant of the dimerization 2
HAorg =(HA)2 org is equal to logK2 =2.1. The model adequately ts the
extraction isotherm for CHCl aq =1 M and CAu org b 0.1. Adding ions in
the form of CAu org [HA]org +2[(HA)2]org +103/ has a slight effect
on the values of constants, logK0 =1.870.08, log(K02K2)=5.810.10,
because the contribution of the ionic subsystem to CAu org is still small in
this eld.
The dependence of log upon logCAu org (Fig. 4) consists of two parts
with very different slopes, CAu org b 3 103 and CAu org > 102 M. The
rst part relates to systems with the dominating monomeric form of
HA. Within the range of logCAu org =3.72.5, the slope =dlog/dlog
[HA] changes from 0.6 to 1.2. When considering the processes separately,
this change does not correspond to equilibrium (3) with =0.5 nor to
reactions 2HAorg =H+org +A(HA)org or 2HAorg =Aorg +H(HA)+org
for which =1. Because the ionic strength is low (I=Z), the activity
coefcients do not have much effect. Therefore, an intermediate value
of the slope is connected with the simultaneous implementation of
several equilibria, both Eq. (3) and the formation of dimeric ions
(Eqs. 4 and 5). The expression for Z can be written as Z=
[H +] + [H(HA)i +] = [A ] + [A(HA)j ] = [H +](1 + + i[HA] i) =
[A ](1 + j[HA] j). Therefore,
  
2 1 i j
Z HAK 11 1 Sbi HA 1 Sbj HA ; 6
where K11, j and + i are the constants of Eqs. (3)(55). However,
Z 10 3 / and Eq. (6) can be used to estimate some constants or
their combinations. For low CAu, the concentration [HA] CAu org;
in other cases, it can be calculated as [HA] = K0CAu aqCH aq. If the
change of the medium can be neglected, then the equation for the
slope can be written as = (1 + n+ + n) / 2, where n+ and n are
the analogues of the formation function (the mean ligand number
and the Bjerrum function). For example, n+ = (i+ i[HA] i) /
(1 + + i[HA] i), and it is equal to the average number of HA mole-
one-stage equilibrium, n = , where is a fraction of the complex.
+ 2 + 2 = 0.7, where + 2 and 2 are the fractions of H(HA) +
and A(HA) in Z. Thus, the contribution of these dimeric species in
ionic subsystem is already signicant at low CAu. The data analysis
using Eq. (6) leads to the following estimates: logK11 = 7.08 0.15,
the formation of ions H +A H + and A H +A is caused by elec-
it was done for triple ions by Fuoss and Krauss (Robinson and Stokes,
2002). The possible systematic error in logK11 is connected to an
accepted value of and is equal to 2log(/true).
For CAu org > 10 2 M, the slope dlog/dlogCAu org increases rapidly
and reaches 1.71.8, i.e., ionic forms H(HA) +, (HA)A and possibly
20 I.V. Mironov / Hydrometallurgy 133 (2013) 1522
more complex ions, dominate over simple H + and A . However,
this growth is caused not only by the increasing concentration of
HA but also by another, not less objective, factor: the medium effect
in the organic phase. In the general case, the change of the constant
can be represented as
logK R1 R2 ;
where R1 is the primary medium effect reecting changes of a solvent
and the corresponding interactions and R2 is the secondary effect
associated with changes in the ionic surroundings and in ionic
strength. For the DBC/HAuCl4 aq system studied, the primary effect
R1 is caused mainly by the co-extraction of water and leads in partic-
ular to the increase of the polarity and the dielectric constant of the
medium. Both effects (R1 and R2) are comparable in magnitude and
act in one direction, reducing the activity coefcients of the ions.
Most signicantly, they affect the equilibrium (3), for which
z 2 = 2. The concentration constant K11 decreases in accordance
with the relation K11 = K11a y 2, where y is mean molar activity coef-
cient and K11a is a thermodynamic constant, as expressed in terms of
activities. Because for equilibria (4, 5) z 2 = 0, the effect on the for-
mation of ions H(HA) + and (HA)A is much lower. Therefore, it has
been assumed that changes of the medium inuence only the equilib-
rium (3). For the estimations, the simplest models were used, that is,
the equations by Born (R1) and Debye (R2)
 

1=2 1=2
log K 11 2 log y 243=RB 1=e0 1=e2 A I = 1 BaI 8 form. On the other hand, as shown above, approximately six water mol-
with the parameters (t = 25 C): A = 355 3/2, B = 2.91 1/2, RB =
2(1/RX + 1/RH) 1 = 5 (A); a = 2RB, and ionic strength I = 10 3/ = Z.
The dielectric constant of dry DBC is equal to 5.02 at t = 35 C
(Sengwa, 1994), and recalculation to 25 C (Kotera et al., 1962)
gives DBC = 5.13. After the addition of water, it increases approxi-
mately proportionally to the volume fraction x: = DBC xDBC + w
xw, where w = 78.5, xw = 1 xDBC 0.018 (0.6 + hwCAu org). Both
the initial (0.6 M) and co-extracted (hwCAu org) water are considered,
and thus, for extracts, 0 = 5.94. The accepted values of the averaged
radius RB* and the parameter of the closest approach a roughly corre-
spond to large sizes of AuCl4 and the solvated associate of H +. We
did not carefully select the parameters for the model (8) to t exper-
imental data on as accurately as possible. In our opinion, it does not
make sense, considering all accepted assumptions and imperfection
of the models for R1 and R2. However, more perfect models as a
rule contain unknown parameters that have to be determined from
the same experimental data. The main objective was to clarify wheth-
er there are other signicant factors affecting the equilibrium in the
system and whether it is necessary to extend the set of species.
The interpretation of data for high CAu org requires the consider-
ation of the binding of the extractant molecules to the solvate com-
plex with the H +, which is the main factor leading to the sharp
decrease of D in the eld of high CAu org. With the participation of
water and extractant the equilibrium (1) can be written as

H aq A aq hS S hw H2 O HA  hS S  hw H2 O; K 0 ;
where K0* = K0 [S] hs and [S] is the concentration of free DBC ([S]0 =
4.0 M). All calculations were performed with hS = 3 for each H + ion
in the composition of any particle, e.g., H +3S, HA3S, (HA)26S and
so on, i.e., [S] = CS 3CAu org.
The calculations were performed with the constants logK0 = 1.87,
logK2 =2.1, log+1 = log1 = 3.1, which were obtained as described
above, and with hw* = 6.2 and hS = 3. For the extracts the standard
0
state is water saturated DBC with w = 0.6 M and logK11a = 7.2; for
the solutions in dry DBC, as it follows from Eq. (8), logK11a = 8.5.
These constants were used for the evaluations of the equilibrium con-
centrations of all species in the organic phase for various CAu org. The
change of K11 caused by the variations of Cw and the ionic strength I
was estimated using the Eq. (8). For every CAu, the calculation was
performed simultaneously with the renement of K11 and I. As an initial
approximation, the value of I = 0 was used. The evaluated distribution
coefcients and the electrical conductivities are shown in Figs. 2 and 4.
As the data presented show, the agreement with experiment is bet-
7 ter than might be expected. For the extracts, the average deviation
|logZcalc logZexp| is equal to 0.04, and the maximal deviation is
0.15 at CAu org = 0.7 M. In addition, for high CAu org the fraction of
ion species exceeds 50%, and the overall decrease of logK11 due to R1
and R2 is approximately 4 units. For the solutions of HAuCl43.3H2O in
dry DBC, the deviations from logZexp are higher (up to 0.4), though
the total change is similar to the experimental change. The main differ-
ence between these solutions and the extracts is the content of water.
The water has two independent inuences. It changes the medium in
particular by increasing the dielectric constant. In addition to this
eld-effect inuence, it can also act as a reagent and is included in
the solvation sphere, supplementing or replacing molecules of the
extractant. In this case, the constants of equilibria (2)(55) may be con-
ditional (effective) and depend on the concentration of free water.
However, the entrance of water molecules into the solvate does not
change the charge of the ions and does not inuence the molar conduc-
tivity considerably. Therefore, in this study, these processes cannot be
identied. According to the IR spectrum of water in the solution of
HAuCl43.3H2O in dry DBC (Fig. 3), it follows that the hydration number
is hw 2.4 in this solution and that some of the water is present in free
ecules are co-extracted with one molecule of HAuCl4. The addition of
water into the solution of HAuCl43.3H2O in dry DBC increases the con-
ductivity, though not very sharply. Our calculation shows that a part of
this change may be caused by a shift of the equilibrium due to the
medium effect (Fig. 4).
4.4. The recalculation to other concentrations of HCl
The results presented here are mainly attributed to CHCl = 1 M but
also other concentrations of hydrochloric acid are used in practice. In
this system, if the only equilibrium (1) exists, then the distribution
coefcient is proportional to CH aq and depends on the medium effects
in the aqueous phase. However, this dependence is observed only
for low CAu org. For higher gold(III) concentrations D also depends on
CAu org due to the complexity of the equilibria (1)(5) and the medium
effects in the organic phase. To recalculate D, one can use the correspon-
dence of solutions. In this system, the extraction of hydrochloric acid is
negligible, and thus the medium and the position of all equilibria in the
organic phase are mainly determined by the total concentration of
gold(III) CAu org. The activity of water is the second factor and may be
signicant for high CHCl. Therefore, if the CAu org are equal in different
systems, then the concentrations of all species are also equal, including
[HA]org and [S]org. Conversely, the equality of [HA]org for different sys-
tems implies the equality of their CAu org and [S]org. Given the medium
effect in the aqueous phase on the equilibrium (9), one can show that
[HA]org = K0aCHaqCAu aq[S] hsorgyaq
2 hw
aw , where yaq and aw are the mean
9 molar activity coefcient of HAuCl4 in the aqueous phase and the activ-
ity of water, respectively. Therefore, the concentration CAu org should be
a single-valued function of F=CH aq CAu aq yaq 2 hw
aw , which allows us to
obtain a unied extraction isotherm. The activity coefcients of HAuCl4
in solutions of HCl up to I =5 M obtained with liquid membranes are
given in (Mironov and Tsvelodub, 1999). They can be approximated by
the DebyeHuckel equation: logytraq =0.509I1/2/(1+1.4I1/2)+0.11I.
The water activity in solutions of HCl is approximately equal to
3/2 2
logaw 0.016CH aq +0.006CH aq0.0057CH aq, and the empirical
value of hw =3. The unied isotherm of extraction is shown in Fig. 5,
which includes all data. In addition, for two systems with different aque-
ous phases but with equal concentrations of CAu org and CAu org 1 the
2 hw 2 hw
following equality holds: D/(CH aqyaq aw )=D1 /(CH aq1yaq1 aw1 ). The
 I.V. Mironov / Hydrometallurgy 133 (2013) 1522 21

Table 6
Inuence of sodium chloride, Iaq = 1 M, CAu org = 0.2 M, and t = 25 C.

CHCl CNaCl log D log(D1/CH aq)

1 0 2.7 2.7
0.3 0.7 2.5 2.2
0.1 0.9 2.1 1.7

of 4 instead of 89. At the same time, in the absence of salt, the inu-
ence of CH aq is normal, as follows from the data in Table 5. A similar
behavior in presence of sodium salts was observed for the extraction
by TBP (Peschevitskii et al., 1992) and was explained by additional
extraction of the ion pair of {Na +AuCl4}. Such possibilities have
been noted already in previous work (Zolotov, 1963). This additional
process is likely the reason that the unusual coefcient 0.5 is obtained
for H + in the equation of extraction in the work (Javanshir et al.,
2 hw 2011).
Fig. 5. Unied extraction isotherm, t=25 C, F=CH aqCAu aqyaq aw . All data are included
both for 1 M and for other CHCl. The solid line corresponds to the calculations for 1 M Another important point relates to the extraction of other ele-
HCl described above. For 1 M HCl logF=logCAu aq0.25. ments by DBC and to the purication of gold. Because of its practical
Literature data from Javanshir et al. (2011) and Morris and Khan (1968) importance, this problem has been studied in detail (Jung et al.,
2009; Kyriakakis, 2005; Morris and Khan, 1968; Rimmer, 1974). We
consider only one example related to the inuence of the acidity
comparison of the experimental distribution coefcients (Dexp) obtained and the concentration of chloride. The growth of CHCl increases D
for various CHCl with the calculated values using this relation (Dcalc) is and improves the recovery of gold from the aqueous phase. However
given in Table 5. For the calculations, the data obtained in this work for the increase of the distribution coefcients for impurities may be
CHCl =1 M were used as D1. The differences are greater for systems much greater. Thus, iron(III) for DBC has logDFe = 2.5 at CHCl =
with high CAu org; in other cases deviations are comparable with experi- 1 M. Therefore, for low concentrations of gold(III), the separation fac-
mental errors (Fig. 2), although the overall change of D is almost 3 orders tor logAu/Fe = log(DAu/DFe) = 4.4, which is 0.51 higher than for the
of magnitude. other typical extractants, such as TBP, methyl isobutyl ketone,
chlorex, etc. However, due to low stability of FeCl4, the extraction
4.5. Inuence of NaCl of iron(III) depends sharply on CHCl. At CHCl = 3 M, logDFe 0 and
logAu/Fe = 2.6; at CHCl = 6 M, logDFe = 2.6 and logAu/Fe = 0.61.
The addition of sodium chloride inuences the distribution appre- Thus, at least with respect to iron(III), DBC at low CHCl is able to pro-
ciably compared with what can be expected considering only CHCl vide good separation, but this advantage disappears at high CHCl.
(Table 6). The observed change of D is less than that in the absence
of NaCl. Even when the possible variation of the activity coefcients 5. Conclusions
logyaq 0.03 for substitution of HCl by NaCl at Iaq = 1 M is consid-
ered, the change of CHCl from 1 to 0.1 M reduces D by only a factor For the extraction of HAuCl4 from hydrochloric medium by DBC,
about 6 water molecules are co-extracted per one molecule of HAuCl4.
The measurements of the electrical conductivity of the extracts and
Table 5
solutions of HAuCl43.3H2O in dry DBC show that the contribution of
Comparison of the experimental D with the values calculated from the data for CHCl =
1 M a and t = 25 C.
the ionic subsystem to CAu org increases with the concentration of
gold(III) and exceeds 50% at high CAu org. The set of species H+, AuCl4,
0
N CHCl logCAu org logCH aq logD1 f logDexp logDcalc HAuCl4, (HAuCl4)2, H(AuCl4)2 and H2(AuCl4)+, which also contain
1 0 0.74 1.91 2.72 0.16 1.16 0.97 0.19 the molecules of the extractant and water, is sufcient to adequately
2 0 0.08 1.13 2 0.06 1.05 0.93 0.12 t the experimental data on the distribution and the electrical conduc-
3 0.1 3.57 1 1.95 0.04 0.96 1.00 0.04
tivity of extracts. However, in addition to the equilibrium constants, it is
4 0.5 3.51 0.3 1.95 0.02 1.57 1.62 0.06
5 2 2.5 0.3 2.12 0.09 2.36 2.51 0.15 necessary to consider the medium effect. This effect consists of two
6 2.3 0.16 0.39 0 0.14 0.64 0.53 0.11 parts: the inuence of water in the organic phase and the inuence of
7 3 2.49 0.48 2.12 0.19 2.68 2.79 0.11 the ionic subsystem.
8 3.8 0.09 0.63 0.6 0.29 1.81 1.52 0.29
9 4 2.79 0.6 2.05 0.27 3.08 2.92 0.16
10 4.6 0 0.7 1.5 0.34 2.84 2.53 0.31 Acknowledgments
11 5.6 0.16 0.78 2.22 0.37 3.20 3.37 0.17
12 6 1.80 0.78 2.32 0.37 3.28 3.47 0.19
13 6 2.80 0.78 2.05 0.37 3.28 3.20 0.08
The author expresses the appreciation to Troshin V. V., Mironova
14 2 2.49 0.3 1.94 0.09 2.07 2.33 0.26 G. N., Gavriljuk E. I., Natorkhina K. I. for help in the preliminary
15 3 2.49 0.48 1.94 0.19 2.47 2.61 0.14 experiments.
16 4 2.49 0.6 1.94 0.27 3.03 2.81 0.22
17 2 1.42 0.3 2.67 0.09 2.95 3.08 0.13
18 3 1.42 0.48 2.67 0.19 3.26 3.34 0.08 References
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