Chemical Engineering and Processing 99 (2016) 183–191

Contents lists available at ScienceDirect

Chemical Engineering and Processing:

Process Intensification
journal homepage: www.elsevier.com/locate/cep

Removal of chromium(VI) from aqueous solutions using a novel hybrid

liquid membrane—electrodialysis process
T. Zh. Sadyrbaeva*
Riga Technical University, Institute of Inorganic Chemistry, Miera str. 34, Salaspils LV-2169, Latvia

A R T I C L E I N F O A B S T R A C T

Article history: Chromium(VI) is one of the most toxic metals, and the removal of this metal ion from effluents and waste
Received 31 October 2014 waters is a problem of great significance. A novel hybrid process of electrodialysis and liquid membrane
Received in revised form 29 May 2015 extraction is proposed for chromium(VI) removal from aqueous solutions. Transport through bulk liquid
Accepted 6 July 2015
membranes was found to be effective for chromium(VI) anions removal from chloride acidic solutions
Available online 26 July 2015
during galvanostatic electrodialysis. Solutions of tri-n-octylamine with admixtures of di(2-ethylhexyl)
phosphoric acid in 1,2-dichloroethane were used as the liquid membranes. Effects of current density,
Keywords:
chromium(VI) and hydrochloric acid concentration in the feed solution, carrier and admixture
Chromium(VI)
Electrodialysis
concentration in the liquid membrane were studied, and optimal conditions were determined. It is
Liquid membrane demonstrated that a practically complete removal of chromium(VI) from the feed solution is achieved
Hybride process during 1.0–4.0 h of electrodialysis. A maximal stripping degree of
90% is obtained under the optimal
Tri-n-octylamine conditions. A possibility of effective single-stage removal of chromium(VI) into dilute solutions of
Di(2-ethylhexyl)phosphoric acid hydrochloric, sulphuric, perchloric, phosphoric acids and water is demonstrated.
ã 2015 Elsevier B.V. All rights reserved.

1. Introduction
Chromium finds extensive use in industry due to its magnetic
properties, hardness and resistance to corrosion. Chromium is an
important alloying material for steel; it is used for surface coating
and in refractory materials. Chromium compounds are used for the
preservation of wood, in leather tanning, in the manufacturing of
synthetic rubies, as industrial catalysts and as yellow, red, green
pigments in paints, glassmaking and in ceramics [1]. Chromium
(VI) is one of the most dangerous carcinogenic and mutagenic
heavy metals, it is toxic for humans, animals, plants and micro-
organisms [2]. Chromium(VI) is commonly used in various
industrial processes, therefore, the removal of this metal ion from
effluents and waste waters is a problem of great significance.
Chromium(VI) exists in aqueous solutions as various anionic
species, and solvent extraction with anion exchange extractants
can be applied to remove chromium(VI) from aqueous solutions
[3]. The liquid membrane is a layer of an organic solvent separating
two aqueous solutions. Addition of mobile carrier species into the
membrane increases the membrane’s solute permeability and
selectivity by carrier-facilitated transport. The main advantages of
the liquid membranes, if compared with the traditional solvent
* Tel.: +371 67944711; Fax: +371 67800779.
E-mail address: sadyrbaeva@hotmail.com (T. Z. Sadyrbaeva).
extraction, are the relatively small volume of the organic phase,
simultaneous extraction and back extraction within single
technological stage, higher extraction degrees of target com-
pounds from dilute solutions, more effective separation of
elements with similar properties, easy scale-up, low capital and
operating costs [4–6]. The liquid membrane technology has great
potential for the removal of heavy metals from aqueous dilute
solutions.
The liquid membranes can be classified into different types:
bulk, emulsion, supported, hollow fiber liquid membranes. Bulk
liquid membranes consist of an aqueous feed and stripping phases,
separated by a water-immiscible liquid membrane (thickness
0.1 cm). They demonstrate stable transport properties. During
recent years the application of different liquid membrane
technologies to remove chromium(VI) has been widely studied.
Tertiary amines and quaternary ammonium salts were used as the
ion carriers in the liquid membranes. The gradient of OH ions
concentration acts usually as the driving force for the transporta-
tion of chromium(VI) ions in these systems. The mechanism of
transfer is the facilitated coupled counterion transport, with metal
anions and hydroxyl ions passing in opposite directions. The
transport of chromium(VI) through the tri-n-octylamine (TOA)-
based bulk liquid membrane was studied in [7]. Tri-n-octylamine
[8], tertiary amine Alamine 336 [9] and quaternary ammonium salt
Aliquat 336 [10] were applied for the chromium(VI) elimination in
supported liquid membrane processes. The applications of

http://dx.doi.org/10.1016/j.cep.2015.07.011
0255-2701/ ã 2015 Elsevier B.V. All rights reserved.
184 T.Z. Sadyrbaeva / Chemical Engineering and Processing 99 (2016) 183–191

properties for different pHs. A hybrid technique of electrodialysis

Nomenclature
and ion exchange was used to concentrate chromate ions from
chrome plating rinse water [25]. The removal of chromium from
c Concentration (mol L1)
tannery and metal-finishing effluents by electrodialysis through
E Extraction degree (%)
solid synthesized membranes was studied in [26].
S Stripping degree (%)
Electrodialysis with liquid membranes combines carrier-
J Molar flux (mol m2 s1)
mediated transport and electrodialysis. The electric field gradient
V Volume (L)
is a driving force of the membrane extraction process during
S Surface area of the liquid membrane (m2)
electrodialysis. Liquid membranes provide greater selectivity and
t Time (s)
permeability than the solid ion-exchange membranes used in
F Faraday’s constant (96485 C mol1)
conventional electrodialysis. If compared with the traditional
I Current (A)
liquid membranes, application of a direct electric field significantly
i Current density (mA cm2)
intensifies the transport of ions through the liquid membranes and
D Diffusion coefficient (m2 s1)
facilitates the stripping of metals from the organic phase [27,28]. A
R Universal gas constant (8.31 J mol1 K1)
first study on the electrodialysis of liquid membranes had been
T Absolute temperature (K)
conducted by Purin [29,30] who concentrated rhenium from
z Charge of the ion
industrial solutions. Bustero et al. [31] studied electroassisted
h Current efficiency (%) solvent extraction for the separation of Ni(II), Cu(II) and Cd(II) ions
using supported liquid membranes. Di(2-ethylhexyl) phosphoric
Abbreviations
acid (D2EHPA) was used to extract copper from a copper, nickel and
TOA, R3N Tri-n-octylamine
iron sulphate solutions by the liquid membranes at electrodialysis
D2EHPA, HA Di(2-ethylhexyl)phosphoric acid
[32]. Electromembrane potentiostatic microextraction through
supported liquid membranes was introduced some years ago [33]
Subscripts
as a sample preparation technique for chromatography, electro-
f Feed solution
phoresis and mass spectrometry. This technique was used to
s Strip solution
remove lead ions from various biological fluids [34] as well as to
aq Aqueous solution
extract Ni(II), Mn(II), Cd(II), Cu(II), Co(II) and Zn(II) cations [35].
org Organic solution
However, electromembrane extraction method is associated with
some drawbacks [36]. The voltages above 300 V cause bubble
formation at the electrodes, instability problems, punctuation of
emulsion liquid membranes for chromium(VI) separation and the liquid membrane and sparking.
concentration using Alamine 336 [11,12], tri-n-octylamine [13,14] Galvanostatic electrodialysis through bulk liquid membranes
and Aliquat 336 [15,16] as mobile carriers have been reported. The containing D2EHPA was used by the author previously to separate
elimination of chromium(VI) by polymer inclusion membranes copper(II) from palladium(II) and platinum(IV) extracted from
containing tri-n-octylamine and Aliquat 336 was investigated in binary hydrochloric mixtures [37]. It has been demonstrated that
[17,18]. Comparative chromium(VI) transport studies of bulk, the D2EHPA-based liquid membranes ensure an effective extrac-
supported and polymer inclusion membranes with tertiary amines tion of manganese(II) from sulphuric acid solutions as well as silver
and Aliquat 336 were carried out in [19]. However, practical (I) transport from nitric acid solutions accompanied by electrode-
importance of the liquid membranes is not sufficiently high at position of metal during electrodialysis [38,39]. Effective electro-
present. A common problem for the supported liquid membranes dialytic separation of palladium(II) and platinum(IV) extracted
is the loss of the membrane solvent and carrier. The emulsion from hydrochloric mixtures using liquid membranes containing
liquid membrane process is much more complex than that of bulk organic derivatives of thiourea has been achieved [40]. The aim of
liquid membrane. The slow transport of metals is a disadvantage of the present work is to study the membrane extraction of
polymeric liquid membranes. Therefore, development of new chromium(VI) from hydrochloric acid solutions by bulk liquid
membrane extraction processes for chromium(VI) removal is of membranes containing tri-n-octylamine with admixtures of di(2-
important environmental and economic interest. ethylhexyl) phosphoric acid during galvanostatic electrodialysis
The electrodialysis process is promising for wastewater and to find optimal conditions for chromium(VI) transfer into
treatment. The applications of electrodialysis with solid ion acidic stripping solution.
exchange membranes for chromium ions removal have been
described in several papers. The simultaneous recovery of Cr(III)
and Cr(VI) through charged ion exchange membranes by using
three detachable cells was studied in [20]. Electro-electrodialysis
process, which combines electrolysis and electrodialysis, was used
4 6 7
for chromic acid recovery, removal of metallic impurities and static − +
rinse water purification in one step [21]. A two-step separation-
concentration process using a cation exchange membrane modi-
fied by electrodeposition of polyethylenimine is proposed to
recover Cr(III) from aqueous solutions [22]. The application of
electrodialysis pilot plant to remove Cr(VI) from the simulated
mixture and to produce good quality drinking water was
investigated in [23]. The two-stage electrodialysis system was
proposed to recover chromate from a low pH electroplating 1 2 3 5 3 2 1
wastewater [24]. This process was designed to concentrate HCrO4–
in the first stage, but to separate the monovalent ions from Fig. 1. Electrodialysis cell with a liquid membrane. (1: platinum electrode; 2:
CrO42–in the second stage based on their monovalent/ divalent sulphuric acid solution; 3: solid cation exchange membrane; 4: feed solution; 5:
cellophane film; 6: liquid membrane; 7: strip solution).
 T.Z. Sadyrbaeva / Chemical Engineering and Processing 99 (2016) 183–191 185

2. Materials and methods where cf is the concentration of chromium(VI) in the feed solution,
cf,0 is the initial concentration of Cr(VI) in the feed solution
2.1. Instrumentation (mol L1). The stripping degree of chromium(VI) is defined as:
 
cs
The experiments were carried out in a five-compartment S¼  100%; ð2Þ
cf;0
cylindrical Teflon electrodialysis cell (Fig. 1). The cell had the length
of 10 cm and a diameter of 3 cm. The liquid membrane (volume where cs is the concentration of chromium(VI) in the strip solution
2.5 cm3, thickness 0.3 cm, surface area 7.1 cm2) was separated from (mol L1).
the aqueous solutions by two vertical cellophane films (Khimvo- The average chromium(VI) flux into the strip solution was
lokno, Russia). The films had a thickness of 20–30 mm and a surface determined as equal to:
area of pores of 1 103 cm2 per 1 cm2. It has been demonstrated  
earlier that electrodialysis influences the structure of the cello- cs V s
J¼ ; ð3Þ
phane film. The number of pores and their diameter significantly St
increase after electrodialysis [41]. These films serve as an aqueous where Vs is the volume of the strip solution (L), S is the surface area
phase continuation and allow creating a reproducible hydrody- of the liquid membrane (m2), t is the time (s).
namic situation at the interface, however they provide an The average current efficiency h for chromium(VI) transfer was
additional diffusional resistance [27]. calculated as:
The electrode solutions (volume 17 cm3) containing 0.15 mol L1
cs  V s  F
sulphuric acid were separated by the solid cation exchange h¼  100%; ð4Þ
membranes MK-40 (Shchekinoazot, Russia) from the feed and strip It
solutions (volume 13 cm3). The MK-40 is a sulfonic polystyrene where F is the Faraday’s constant (96,485 C mol1), I is the current
divinylbenzene cation exchange membrane. The cellophane films (A).
and the solid membranes were soaked in water for more than 24 h
before use. The direct electric current was supplied to the plane 3. Results and discussion
platinum electrodes (w  h: 1.5 2.4 cm). Potentiostat P-5848
(Russia) was used as a current source. All experiments were 3.1. Transport mechanism
performed under galvanostatic mode. Voltage was measured by a
digital voltmeter. The concentration of chromium(VI) in the aqueous Chromium(VI) can exist in aqueous solutions in different
solutions was determined spectrophotometrically by characteristic anionic forms (HCrO4–, CrO42–, Cr2O72–, HCr2O7–) depending on the
absorption peak for [Cr2O7]2 ions [42]. The absorption of metal ions pH value of the solution and on the concentration of chromium(VI).
was measured at 442 nm. UV–vis spectrophotometer SF-46 (LOMO, The main equilibriums for the Cr(VI) ions are presented in [43]:
Russia) was used for the analysis of chromium(VI) ions. The Cr(VI)
Cr2O72– + H2O $ 2HCrO4– K1 = 10–2.2 (5)
concentration in the organic phase was calculated from mass
balance. The solutionpH was measured bya digital pH-meter (Adwa,
Hungary). The experiments were carried out at room temperature
(18–20  C). The solutions were not agitated. HCrO4– $ CrO42– + H+ K2 = 10–5.9 (6)

2.2. Reagents
The solutions of TOA (pure grade) with or without the
admixtures of D2EHPA (technical grade, contents of the main
substance
63%) in 1,2-dichloroethane were used as the liquid
membranes. They contained usually 0.1–0.2 mol L1 TOA and
0.19 mol L1 D2EHPA (10 vol.%). The membrane solutions were
prepared by dissolving an exactly weighed amount of TOA and
known volume of D2EHPA into a given volume of 1,2-dichloroeth-
ane. It should be noted that the application of an electric field
imposes specific demands on organic solvents, such as sufficient
electric conductivity and low solubility in water. 1,2-dichloroeth-
ane satisfies these criteria. It is a relatively polar solvent (e = 10.42),
which reduces the association of compounds in the organic phase.
The feed solutions were prepared by dissolving K2Cr2O7 (analyti-
cally pure grade) in the hydrochloric acid of appropriate
concentration, as a rule, 0.1 mol L1 HCl. The initial concentration
of K2Cr2O7 was usually 0.01 mol L1. The stripping solutions were
prepared by diluting HCl with distilled water. The concentration of
HCl in the strip solutions was usually 0.1 mol L1. All chemicals
were of reagent quality and were used without further purification.
H2CrO4 $ HCrO4– + H+ K3 = 4.1 (7)
The following general equilibrium is realized in chromium(VI)
solutions [18]:
Cr2O72– + H2O $ 2HCrO4– $ 2H+ + 2CrO42– (8)
From the equilibriums (5)–(7) results that CrO42–anions dominate
in a basic or weakly acidic media, while Cr2O72–and HCrO4– ions
coexist in acidic solutions, the anions’ ratio depending on the total
Cr(VI) concentration. As the initial concentration of chromium(VI)
in the feed solution was usually 0.02 mol L1 in 0.1 mol L1 HCl, we
can suggest that Cr2O72–and HCrO4– anions coexist in comparable
amounts in this study. For simplicity, we will only consider
Cr2O72–fraction.
Chromium(VI) ions are extracted by TOA due to the interfacial
anion exchange mechanism. Amine first reacts with hydrochloric
acid to form tri-n-octylammonium chloride:
H+(aq) + Cl(aq) + R3N(org) $ R3NH+Cl(org) (9)
The extraction of chromium(VI) by TOA can be described by the
following equation:

2.3. Calculations Cr2O72–(aq) + 2R3NH+Cl(org) $ (R3NH)2Cr2O7(org) + 2Cl(aq) (10)

The extracted complex can partially dissociate in 1,2-dichloro-
The extraction degree of chromium(VI) into the liquid ethane:
membrane is expressed as:
  (R3NH)2Cr2O7(org) $ 2R3NH+(org) + Cr2O72–(org) (11)
1  cf
E¼  100%; ð1Þ
cf;0
186 T.Z. Sadyrbaeva / Chemical Engineering and Processing 99 (2016) 183–191
In the presence of D2EHPA in the organic phase, an ion pair is
formed, which consists of an organic cation and an organic anion
[44]:
R3N(org) + HA(org) $ R3NH+ A(org) (12)
Chromium(VI) ions are extracted by TOA in the presence of
D2EHPA due to the following mechanism:
Cr2O72(aq) + 2R3NH+ A(org) $ (R3NH)2Cr2O7(org) + 2A(org) (13)
The flux of the ions through the liquid membrane under
electrodialysis conditions can be described by the Nernst–Planck
equation [45]:
 
dc zcFd’
J ¼ D þ ð14Þ
dx RT dx
where dc/dx is concentration gradient across the membrane, df/
dx is electric field gradient.
The first term of the Nernst–Planck equation is the Fick’s first
law, it describes a diffusional flux produced by the concentration
gradient, and the second term is a migrational flux driven by an
electric field.
The transport process schematically is illustrated in Fig. 2.
Cr2O72–anions are transferred by diffusion and electromigration
from the bulk of the solution to the interface feed solution/liquid
membrane and interact with the carrier forming the ion pair
(Reactions (10) and (13)). The transported compound
(R3NH)2Cr2O7 diffuses across the organic layer and dissociates at
the polarized 1,2-dichloroethane/water interface (reactions re-
verse 10, 13). The carrier’s molecules return back according to their
concentration gradient. Cr2O72–anions, appearing in the organic
phase due to the partial dissociation of the extracted complexes,
are transported through the liquid membrane by electromigration.
Chloride ions from the feed solution interact with the carrier due to
the interfacial anion exchange mechanism and permeate across
the membrane into the strip solution in the same direction as
chromium(VI) anions. Thus, the mechanism of membrane extrac-
tion is a facilitated chromium–chloride cotransport.
In the presence of cation exchange carrier D2EHPA, hydrogen
ions from the strip hydrochloric acid solution interact with the
carrier at the interface liquid membrane/strip solution according to
Reaction (15) and are transferred across the liquid membrane into
the feed solution in the direction opposite to Cr2O72–transport:
Fig. 2. Scheme of the membrane extraction during electrodialysis.
H+(aq) + R3NH+ A(org) $ HA(org) + R3NH+(org) (15)
At the interface feed solution/liquid membrane the Reaction
(15) goes from right to left.
Hydrogen ions are transferred from the feed solution across the
solid cation exchange membrane into the cathode compartment
and permeate from anode compartment into the strip solution
owing to the electroneutrality condition. Redox reactions occur-
ring at the electrodes are coupled to transmembrane ion transport.
Hydrogen evolution occurs at the cathode, and oxygen evolution
occurs at the platinum anode in the sulphuric acid solution:
2H+ + 2e ! H2" (16)
2H2O ! O2" + 4H+ + 4e (17)
3.2. Effect of the current density
It was found out in the preliminary experiments that the
extraction degree of chromium(VI) from the feed solution into the
liquid membrane containing 0.1 mol L1 TOA and 0.19 mol L1
(10 vol.%) D2EHPA was about 25% within 2 h without electric field
application, and the transfer of chromium(VI) anions into the strip
solution of 0.1 mol L1 HCl was not practically observed. The
imposition of an electric field makes it possible to intensify the
chromium(VI) extraction from the feed solution and to transfer
Cr2O72–anions through the liquid membranes. The increase of the
current density results in an increase of the chromium(VI) anions
transport rate (Table 1). A practically complete (>99 %) removal of
the metal from the feed solution by the liquid membranes
containing individual TOA solution in 1,2-dichloroethane as well as
TOA with admixtures of D2EHPA can be achieved during 1–4 h of
electrodialysis depending on the current density. At high current
densities the duration of electrodialysis reduces, however the
extraction degree and the stripping degree are somewhat less than
the values obtained at moderate current densities. A maximum Cr
(VI) stripping degree of 89% is achieved at a current density of
10.6 mA cm2.
The chromium(VI) transport rate depends on the acidity of the
feed hydrochloric solution and on the composition of the liquid
membrane. The highest chromium(VI) flux was achieved in the
system with 0.01 mol L1 HCl in the feed solution (Fig. 3, line 1).
 T.Z. Sadyrbaeva / Chemical Engineering and Processing 99 (2016) 183–191 187

Table 1
Effect of the current density on the Cr(VI) extraction degree E, stripping degree S and flux J for various HCl, D2EHPA and TOA concentrations in the system.a

i (mA cm2) t (min) cHCl (mol L1) Liquid membrane E (%) S (%) JCr (mmol m2 s1)
1
cTOA cD2EHPA (mol L )
(mol L1)
0 120 0.1 0.1 0.19 25.7 0 0
4.2 173 0.01 0.2 0.19 99.8 85 30
6.4 109 0.01 0.2 0.19 99.7 84 46
8.5 86 0.01 0.2 0.19 99.4 86 60
10.6 73 0.01 0.2 0.19 99.0 84 70
12.7 53 0.01 0.2 0.19 98.4 80 90
4.2 216 0.1 0.2 0 99.6 70 20
6.4 157 0.1 0.2 0 99.3 72 28
8.5 122 0.1 0.2 0 99.2 67 34
10.6 109 0.1 0.2 0 98.9 65 36
12.7 90 0.1 0.2 0 98.7 66 44
14.9 79 0.1 0.2 0 98.6 60 47
6.4 235 0.1 0.1 0.19 100.0 85 22
8.5 159 0.1 0.1 0.19 99.8 80 30
10.6 168 0.1 0.1 0.19 99.6 89 32
12.7 132 0.1 0.1 0.19 99.2 85 38
14.9 122 0.1 0.1 0.19 99.3 83 40
a
cK2Cr2O7 = 0.01 mol L1; strip solution: 0.1 mol L1 HCl.

The transport rate is directly proportional to the current density up
to 12.7 mA cm2. An increase in HCl content in the feed solution
from 0.01 to 0.1 mol L1 leads to a decrease in metal transport rate
(Fig. 3, curves 2 and 3). It is presumed to occur due to the chloride
ions transfer intensification through the liquid membrane,
resulting in the current efficiency decrease for chromium(VI).
When individual TOA solutions are used as the liquid membranes
(curve 2), the chromium(VI) flux is somewhat higher if compared
with the TOA-D2EHPA mixture with the same HCl concentration
(curve 3), and the flux is proportional to the current density up to
8.5 mA cm2. However, the flux becomes almost constant at high
(>12 mA cm2) current densities, probably, due to the water
accumulation in the liquid membrane.
The duration of galvanostatic electrodialysis is limited, as a rule,
by an abrupt increase of voltage within 1.0–4 h of electrodialysis
depending on the current density, acidity of the feed solution and
the composition of the liquid membrane (Fig. 4). It was found out
that the decrease of the electrical conductivity of the membrane
system corresponded to the nearly complete (99%) extraction of
chromium(VI) from the feed solution (Table 1). The voltage
increase is attributed to the desalination of the feed solution as a
result of the chromium(VI) anions and chloride ions extraction into
the liquid membrane and to the hydrogen ions and K+ cations
transfer through the solid cation exchange membrane into the
cathode compartment. Thus, the shape of the voltage—time
diagram can be used to evaluate the removal completeness. The
electrical conductivity of the system is determined, as a rule, by the
Ohmic resistance of the organic layer. The chromium(VI) anions
and chloride ions transport across the interface during electrodi-
alysis leads to a reduction of the Cr2O72–and Cl concentration at
the surface of the liquid membrane. The resistance of the feed
solution / liquid membrane interface gradually increases and
exceeds the Ohmic resistance of the organic layer. A limiting
current arises, and the voltage on the membrane sharply increases.
At the same current density, the desalination of the feed
solution and the rise in voltage occur earlier in case of low
hydrochloric acid concentration in the feed solution (Fig. 4, curve
1). Electrodialysis in a system containing individual TOA solutions
in the liquid membrane is characterized by a relatively high initial
voltage (Fig. 4, curves 2 and 5). During the chromium(VI) transport,
the voltage decrease in the beginning of the process is followed by
a sharp increase of voltage. The initial voltage decrease is
determined by the rise of the total concentration of ions in the
liquid membrane due to the extraction of hydrochloric acid and
chromium(VI) ions by the carrier. The final voltage increase is
determined by the desalination of the feed solution.
The kinetics of the chromium(VI) transport through the liquid
membranes containing 0.1 mol L1 TOA and 0.19 mol L1 (10 vol. %)
D2EHPA at a current density of 10.6 mA cm2 is shown in Fig. 5.
Practically a complete extraction of metal ions from the feed
1 2 3 4 5 6
200

10
1
Flux 10 5, mol m -2 s-1

150
Voltage, V

6 100
2
3
4
50
2

0 0
0 4 8 12 16 0 60 120 180 240
Current density, mA cm-2 Time, min

Fig. 3. Dependence of the chromium(VI) flux into the strip solution on the current Fig. 4. Change in voltage during electrodialysis for various membrane systems (i
density for various membrane systems (cG?A (mol L1) = 0.2 (1, 2); 0.1 (3); cD2EHPA (mA cm2) = 6.4 (3, 5, 6); 12.7 (1, 2, 4); cG?A (mol L1) = 0.1 (4, 6); 0.2 (1, 2, 3, 5);
(mol L1) = 0.19 (1, 3); 0 (2); cHCl (mol L1) = 0.01 (1); 0.1 (2, 3)). cD2EHPA (mol L1) = 0.19 (1, 3, 4, 6); 0 (2, 5); cHCl (mol L1) = 0.01 (1, 3); 0.1 (2, 4, 5, 6)).
188 T.Z. Sadyrbaeva / Chemical Engineering and Processing 99 (2016) 183–191

solution is achieved within 170 min of electrodialysis, about 90% of Table 2

Change in pH during electrodialysis.a
chromium (VI) is accumulated in the strip solution and
10% of the
metal remains in the organic phase under these conditions. The t (min) Feed solution Strip solution Catholyte Anolyte
concentration of chromium(VI) anions in the strip solution is 0 1.1 1.0 0.9 0.9
directly proportional to the process duration, whereas the metal 155 3.4 0.8 1.0 0.9
content in the liquid membrane reaches its maximum value within a
i = 10.6 mA cm–2; cK2Cr2O7 = 0.01 mol L–1; cTOA = 0.1 mol L–1; cD2EHPA = 0.19 mol L–
2 h of electrodialysis (Fig. 5, curve 2). This time corresponds to the 1
; strip solution: 0.1 mol L–1 HCl.
beginning of the sharp rise in voltage in the system.
The transfer of chromium(VI) through the liquid membrane is
accompanied by a significant rise in pH values of the feed and
100
cathodic solution (Table 2). Hydrogen ions are transported from
the feed solution into the catholyte where they participate in the

Flux 10 5, mol m-2 s-1

electrode Reaction (16). The data in Table 2 show noticeable 75
decrease of pH value in the strip solution during electrodialysis as a

E, S, %
result of hydrogen ions transport from the anolyte into the strip
50
solution through the solid cation exchange membrane. 1

2
3.3. Effect of the concentration variation 25
3

3.3.1. Feed solution parameters

0
The effect of the composition of aqueous solutions and liquid
0 0.025 0.05 0.075 0.1
membranes on the chromium(VI) anions transport rate was
studied at a current density of 10.6 mA cm2 and an electrodialysis K2Cr2O7 concentration, mol L-1
duration of 100 min. The increase of K2Cr2O7 initial concentration
Fig. 6. Dependence of the chromium(VI) extraction degree (1), stripping degree (2)
in the feed solution from 4.3  103 to 0.1 mol L1 was found to and flux into the strip solution (3) on the K2Cr2O7 initial concentration
increase the metal transport rate into the strip solution, while the (i = 10.6 mA cm2; t = 100 min; cTOA = 0.2 mol L1; cD2EHPA = 0.19 mol L1).
extraction and stripping degrees decreased (Fig. 6). The current
efficiency for the Cr2O72 transport was found to increase with the
metal initial concentration rise. The highest current efficiency of 1
17% was obtained in case of the maximal (0.1 mol L1) K2Cr2O7 120
concentration in the feed solution. The current is transferred
through the liquid membranes mainly by chloride ions from the 90
Voltage, V

feed solution and by hydrogen ions from the strip solution.

The increase of K2Cr2O7 concentration in the feed solution from
60
0.01 to 0.1 mol L1 leads to some rise of the electrical conductivity
of the membrane system and influences the shape of the voltage-
time diagrams (Fig. 7, curves 2 and 3). Electric breakdown, i.e., a 30 2
stepwise decrease of voltage during galvanostatic electrodialysis 3
caused by the water accumulation in the organic phase, occurs in 4
0
the membrane system with high Cr(VI) initial concentration (Fig. 7,
curve 3). Water is transferred into the organic phase in the 0 25 50 75 100
Time, min
hydration—solvation shells of ions and by electroosmosis [46]. The
accumulation of water negatively affects the transport of ions Fig. 7. Change in voltage during electrodialysis for various Cr(VI) and HCl
through the liquid membranes. concentrations in the feed solution (i = 10.6 mA cm2; cTOA = 0.2 mol L1; cD2EHPA =
The acidity of the feed solution was found to influence the 0.19 mol L1; cK2Cr2O7 (mol L1) = 0.01 (1, 2, 4); 0.1 (3); cHCl (mol L1) = 0.01 (1); 0.1 (2,
3); 1.0 (4)).
chromium(VI) extraction efficiency. The increase of the hydro-
chloric acid concentration in the feed solution from 0.05 to
0.5 mol L1 results in a significant decrease of the Cr(VI) transport
rate as well as of the extraction and stripping degrees (Fig. 8). The
increase of the hydrochloric acid concentration leads to a rise of the
100 chloride ion flux through the liquid membrane, resulting in the
1
3 current efficiency decrease for chromium(VI) anions. The optimal
acidity of the feed K2Cr2O7 solution was found to be 0.05 mol L1
75
Cr content, %

HCl. More than 90% of chromium(VI) is extracted from the feed

solution and a sufficiently high stripping degree of 80% is achieved
50 within 100 min of electrodialysis in this system.
The change in hydrochloric acid concentration in the feed
25 solution influences the curves of chronopotentiograms (Fig. 7). A
2 sharp voltage increase occurs within 75 min of electrodialysis in a
membrane system containing 0.01 mol L1 hydrochloric acid
0
(Fig. 7, curve 1). It is determined by the desalination of the feed
0 60 120 180 solution. At higher hydrochloric acid concentrations the initial
Time, min gradual rise in voltage changes to some voltage decrease, or the
continuous decrease of voltage is observed (curves 2–4). The
Fig. 5. Kinetics of chromium(VI) removal from the feed solution (1), accumulation
in the liquid membrane (2) and in the strip solution (3) (i = 10.6 mA cm2;
voltage decrease is determined by the water accumulation in the
cK2Cr2O7 = 0.01 mol L1; cHCl = 0.1 mol L1; cTOA = 0.1 mol L1; cD2EHPA = 0.19 mol L1). organic phase.
 T.Z. Sadyrbaeva / Chemical Engineering and Processing 99 (2016) 183–191 189

200

150

Voltage, V
1
2
100
3
50 4

5
0
0 20 40 60 80 100
Time, min

Fig. 8. Dependence of the chromium(VI) extraction degree (1), stripping degree (2) Fig. 9. Change in voltage during electrodialysis for various TOA and D2EHPA
and flux into the strip solution (3) on the HCl concentration in the feed solution concentrations in the liquid membrane (i = 10.6 mA cm2; cHCl = 0.1 mol L1; cTOA
(i = 10.6 mA cm2; t = 100 min; cTOA = 0.2 mol L1; cD2EHPA = 0.19 mol L1). (mol L1) = 0.05 (1); 0.2 (2, 3); 0.4 (4, 5); cD2EHPA (mol L1) = 0 (2); 0.19 (1, 4, 5); 0.77
(3)).

3.3.2. Liquid membrane parameters

The effect of the TOA and D2EHPA concentrations in the liquid
membranes on the chromium(VI) anions transport into the strip
hydrochloric acid solution is illustrated in Table 3. The increase of
the TOA concentration in the liquid membrane from 0.05 to
0.3 mol L1, with the D2EHPA concentration being constant, leads
to some increase of the chromium(VI) extraction degree into the
organic phase and transport rate into the strip solution.
The electrical conductivity of the membrane system is
determined usually by the composition of the liquid membrane.
The increase of the TOA concentration in the organic phase leads to
a rise of the electrical conductivity and to a decrease of the initial
voltage of galvanostatic electrodialysis (Fig. 9, curves 1 and 5). It
should be noted that the storage time of the liquid membrane
solution can influence the kinetics of the chromium(VI) transport.
A sharp voltage increase occurs within an hour of electroialysis,
and practically complete (99 %) removal of chromium(VI) from
the feed solution is achieved at a current density of 10.6 mA cm2
when 0.4 mol L1 TOA solution is used immediately after
preparation (Fig. 9, curve 4). The Cr(VI) extraction degree reduces
(80 %), the voltage changes insignificantly during electrodialysis,
and the initial voltage in this system is somewhat lower when the
liquid membrane is used after one day storage (Fig. 9, curve 5). The
negative effect of the storage time on the transport properties
of the liquid membranes can be caused by the formation of
quaternary ammonium salt in the organic phase as a result of the
TOA interaction with 1,2-dichloroethane [47]:
R3N + CH2Cl  CH2Cl ! [R3NCH = CH2]+Cl + HCl.
The liquid membranes were used in the experiments usually
within 2 days after preparation.
The electrodialysis in a system containing individual TOA
solution is characterized by a rather high initial voltage (Fig. 9,
curve 2). The increase of the D2EHPA concentration in the organic
phase up to 0.77 mol L1 (40 vol.%), with the TOA concentration
being constant, significantly reduces the voltage of galvanostatic
electrodialysis (Fig. 9, curve 3), however leads to some reduction of
the chromium(VI) extraction and stripping degrees and of the flux
(Table 3). It is presumed to occur due to the hydrogen ions transfer
intensification from the strip solution through the liquid mem-
brane resulting in the current efficiency decrease for Cr2O72–ions.
Liquid membranes containing TOA with an admixture of 0.19 mol
L1 (10 vol.%) D2EHPA were commonly used in the experiments.
3.4. Effect of the stripping solution
The influence of the strip solution composition on the
chromium(VI) extraction rate is illustrated in Table 3. In contrast
to traditional membrane extraction, the nature of mineral acid in
the strip solution usually does not exert a considerable influence
on the electrodialytic transport of metals. It was found out that the
transfer of chromium(VI) ions proceeded with an approximately
equal rate into 0.1 mol L1 solutions of phosphoric, sulphuric,
perchloric and hydrochloric acids, while the maximal chromium
(VI) transport rate as well as extraction and stripping degree were
achieved in a system containing distilled water as the strip
solution. It should be mentioned that the electrodialysis in this
system is characterized by significantly higher initial voltage if
(18) compared with the acidic strip solutions.
The obtained results allow to conclude that the electrodialysis
through the liquid membranes represents a promising alternative
to the conventional techniques for the removal of chromium(VI)

Table 3
Effect of the D2EHPA and TOA concentration in the liquid membrane and of the stripping solution composition on the Cr(VI) transport.a

cTOA (mol L–1) cD2EHPA (mol L–1) Strip solution (c = 0.1 mol L–1) E (%) S (%) JCr (mmol m–2 s–1)
0.05 0.19 HCl 64 49 30
0.1 0.19 HCl 66 46 28
0.2 0.19 HCl 74 55 34
0.3 0.19 HCl 80 55 34
0.4 0.19 HCl 79 55 34
0.2 0 HCl 93 64 40
0.2 0.1 HCl 77 60 36
0.2 0.39 HCl 66 46 28
0.2 0.77 HCl 62 47 28
0.1 0.19 H2O 74 73 44
0.1 0.19 H3PO4 70 55 34
0.1 0.19 H2SO4 71 49 30
0.1 0.19 HClO4 70 48 30
a
cK2Cr2O7 = 0.01 mol L–1; i = 10.6 mA cm–2; t = 100 min.
190 T.Z. Sadyrbaeva / Chemical Engineering and Processing 99 (2016) 183–191
ions from dilute solutions. The electrodialysis has some advantages
compared with the supported and emulsion liquid membranes.
The electric field significantly intensifies the transport of ions
through the organic layer and facilitates the stripping of the metal
from the liquid membrane. The pH gradient between the feed and
the strip solutions is not necessary during electrodialysis. The
nature of acid in the strip solution does not exert significant
influence on the electrodialytic transport of chromium(VI) through
the liquid membranes. The bulk liquid membranes are more stable
than the supported liquid membranes as the solvent evaporation
and the loss of organic solvent and carrier from the support are
eliminated. The electrodialysis through the liquid membranes
includes a relatively small volume of the organic phase and ensures
simultaneous extraction and back extraction in single technologi-
cal step. With respect to the conventional electrodialysis, the liquid
membranes offer the advantage of higher fluxes, since diffusion in
liquids is faster than in the solid ion exchange membranes.
4. Conclusions
The liquid membranes containing individual tri-n-octylamine
solutions or tri-n-octylamine with admixtures of di(2-ethylhexyl)
phosphoric acid in 1,2-dichloroethane ensure the effective single-
stage extraction of chromium(VI) from HCl solutions into dilute
solutions of hydrochloric, sulphuric, perchloric, phosphoric acids
and water during galvanostatic electrodialysis. As a rule, the
chromium(VI) transport rate increases as the current density,
K2Cr2O7 initial concentration in the feed solution and the TOA
concentration in the organic phase increase. The increase of the
feed solution acidity and D2EHPA concentration in the liquid
membrane exert some negative influence on the chromium(VI)
flux. The type of acid in the strip solution insignificantly affects the
metal transport rate. The maximal chromium(VI) flux is achieved
in a system containing distilled water as the strip solution. By
varying the ratio of the current, time and concentrations of the
components, the practically complete (>99.5 %) removal of
chromium(VI) from the feed solution and a maximal stripping
degree of
90% are achieved in the studied systems.
Acknowledgements
Financial support of this work from the Latvian Council of
Science through Grant No. 09.1551 is gratefully acknowledged. The
author would like also to thank Mrs. S.V. Shchanitsina for her
language help.
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