ISSN 0036-0244, Russian Journal of Physical Chemistry A, 2022, Vol. 96, No. 3, pp. 550–555. © Pleiades Publishing, Ltd.

, 2022.

CHEMICAL KINETICS
AND CATALYSIS

Kinetic Study on Removal of Cr(III) Heavy Metal

by Using Amino Oxime Molecule
M. Yunus Pamukoğlua, Bülent Dedeb,*, and M. Çağrı Karabuğaa
a Süleyman Demirel University, Faculty of Engineering, Department of Environmental Engineering, Isparta, 32260 Turkey
b
Süleyman Demirel University, Faculty of Arts and Sciences, Department of Chemistry, Isparta, 32260 Turkey
* e-mail: bulentdede@sdu.edu.tr
Received November 30, 2020; revised January 21, 2021; accepted January 22, 2021

Abstract—The use of Cr(III) heavy metals in the leather industry is quite common and therefore the leather
industry has high concentrations of Cr(III) heavy metals in wastewater. In this study, it was aimed to remove
the chromium ions from the wastewater of leather industry by means of the amino oxime ligand, which is
selective for heavy metal ions and allows reuse of the complex formation. These studies were supported by the
kinetic experiments. Pseudo-first and second order kinetics was used for correlation of complex formation
data and rate constants were determined. In almost all conditions, experimental data were found to be better
suited to second-order complex formation kinetics. The highest rate constants were found to be 0.432 min–1
and 0.0312 (mg g–1)–1 min–1 for the first and second order kinetics, respectively, at the highest concentration
of amino oxime tested (3 g L–1).

Keywords: heavy metal, amino oxime, wastewater, Cr(III) ion, leather industry, kinetics
DOI: 10.1134/S0036024422030293

INTRODUCTION in incineration and disposal facilities that are limited

One of the methods widely used in the removal of
chromium heavy metals from wastewater in recent
years is adsorption. Numerous researches were carried
out on the use of industrial wastes such as hazelnuts,
almonds, rice husks, fruit nuts and agricultural resi-
dues in chrome removal by adsorption method [1–5].
Some of these studies were directed towards the direct
use of these residues. However, in recent years studies
to increase the adsorption capacity, activated carbon
production and utilization were investigated by using
various activation methods from such wastes. In some
of the studies, commercial active carbons were
restructured with acids or bases to investigate adsorp-
tion yield [6].
The leather industry has high concentrations of
Cr(III) heavy metal ions in wastewater [7]. In this con-
text, Cr(III) heavy metal in wastewater has been also
released in significant amounts. Such wastewater is
covered by hazardous and harmful materials [8–10].
In addition, biological wastewater treatment processes
are problematic due to the toxic nature of this heavy
metal [11]. Waste sludges formed in wastewater treat-
ment plants containing heavy metals such as Cr(III) in
the input wastewater are also classified as hazardous
and harmful wastes. The disposal of such sludges is
either incineration or the most commonly used incin-
eration processes. These sludges need to be eliminated
in developing countries. This creates very serious costs
for businesses. At the same time, the use of Cr(III) in
leather industry enterprises also brings significant
operating costs. Many adsorbents were used such as
wood shavings, lawn waste, biomass, etc. in the
removal of heavy metals [12, 13]. As a result of the use
of such adsorbents, both the physical and chemical
retention of heavy metals has not been effective
enough and their reuse is also limited.
The most important advantage in heavy metal
removal by complex formation from wastewaters using
chemical ligands is that only heavy metals are retained.
The recovery and use of the retained heavy metal is
therefore also effective. Removal of heavy metal ions
with ligand complex formation is accomplished by
forming complexes or complex compounds with metal
ions of the functional groups in the ligand [14–16].
The benefits of the ligands in heavy metal complex
formation are:
• the ease of controlling the number of functional
groups,
• the ability to use many functional groups specific
to the adsorptive metal, which is the enhancing effect
of metal complex formation,
• complex formation of the metal quickly and
selectively,

550
 KINETIC STUDY ON REMOVAL OF Cr(III) HEAVY METAL
• they must have adequate complex formation
capacities,
• high physical and chemical stability to adsorp-
tion environment,
• high stability to chemical substances such as
acids and bases used in desorption processes,
• they must be renewable [17].
Considering these advantages, the use of the ligand
is very important in terms of removing and recovering
the α contaminating heavy metals from the aqueous
environment. For this purpose, in this study, the
removal of Cr(III) heavy metals from the wastewater
of leather industry was studied with amino oxime
ligand. One of the main aims of the work is to carry out
the kinetic studies with the aim of revealing the com-
plex formation mechanisms precisely. The complex
formation rates of amino oximes used as chemical
ligands were determined on this scale.
EXPERIMENTAL
Amino Oxime Handling
In this study, the removal of Cr(III) heavy metal
from the wastewater of the leather industry was studied
with the amino oxime ligand. The structure of the
amino oxime ligand is shown in Fig. 1 [18].
Numerous studies have been carried out on the use
of ligands in metal removal by complex formation
[19–21]. In these investigations ligands were found to
be effective in heavy metals removal.
Batch Shaker Experiments
Shaker experiments were carried out at 150 rpm
using a circular motion stirrer and water containing
10 mL of Cr(III) ions and a 10 mL volume of the
amino oxime concentration were added to the tubes in
a volume of 50 mL. Amino oxime was prepared to pro-
vide the desired concentration in chloroform in order
to achieve full solubility. The reasons for giving the
amino oxime in liquid phase rather than solid are to
minimize the effects of the particle size, to provide
better dispersion in the solution and thus to better
interactivity, to recover and reuse the amino oxime. As
the chloroform was not mixed with water, it was clas-
O The Cr(III) heavy metal ion precipitates in hydroxyl
N OH
(CH2)n
NH OH
Cl
Fig. 1. Structure of the amino oxime ligand.
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A
551
sified as chloroform in the lower phase, Cr(III) ions in
the middle by the amino oxime and Cr(III) ions in the
upper phase as the liquid solution at the end of the
experiment. In this respect, the separation by means of
a separation hopper can be easily carried out at the end
of the experiment.
In the kinetic studies, the effects of pH, tempera-
ture, amino oxime concentration and Cr(III) ion con-
centrations were examined. In isotherm studies,
Cr(III) ion concentrations were changed under opti-
mum environmental conditions (pH, rpm, tempera-
ture, amino oxime concentration). The tubes were
shaken for 120 min at 25°C and samples were taken at
specific time intervals. A control tube containing only
100 mg Cr(III) L–1 solution without amino oxime was
simultaneously shaken to determine the amount of
Cr(III) ion removal without amino oxime.
Analytical Methods
Cr(III) heavy metal ion analysis was done by Per-
kin Elmer brand Nexion 300 model ICP-MS. pH
measurements were made with Hach sensION + pH1
brand pH meter and centrifuges were performed with
Nuve NF400 device. Each analysis was repeated at
least three times and values were obtained with a devi-
ation of 5%.
RESULTS AND DISCUSSION
Kinetics of the Complex Formation
of Cr(III) Ion with Amino Oxime
In this experimental set, kinetic studies on the
removal of Cr(III) ions by amino oxime of operating
parameters such as pH, temperature, Cr(III) ion, and
amino oxime concentration were investigated.
Pseudo-first and second order kinetics were applied
for the purpose of verifying the amount of complex
formed material in equilibrium and determining the
rate constants. Pseudo grade 2 kinetics were found to
be more appropriate in assessing kinetic data calcu-
lated for almost all operating parameters.
Effects of Initial pH
pH is an important parameter in terms of binding
of metal ions to the complex formation and at the
same time in terms of the solubility of metal ions [22].
form above pH 5. Therefore, the concentrations of
amino oxime and Cr(III) ions were constantly main-
tained at 1 g L–1 and 100 mg L–1, respectively, and the
pH was changed from 3 to 6 in the removal of the
heavy metal with CrO3. During the complex formation
experiments the pH changes were neglected (±0.2 pH
value).
Kinetic constants for the pseudo-first and second
degree models at different pH values were calculated
Vol. 96 No. 3 2022
552 YUNUS PAMUKOĞLU et al.

0 1.2
ln(1  qt/qe) 1 1.0
2 0.8
3 0.6

t/qt
1
4 2 0.4
3
5 4 0.2
(a) (b)
6 0
0 2 4 6 8 10 0 2 4 6 8 10
Time, min Time, min

Fig. 2. (a) Variation of ln(1 – qt/qe) values with time at different pH with respect to pseudo-first order kinetics; (b) variation of
t/qt values with time at different pH with respect to pseudo-second order kinetics; pH: (1) 3, (2) 4, (3) 5, (4) 6.

0 0.18
0.15
1
0.12
ln(1  qt/qe)

2 1 0.09
t/qt
2
3 3 0.06
4
5 0.03
4 (a) (b)
0
0 2 4 6 8 10 0 2 4 6 8 10
Time, min Time, min

Fig. 3. (a) Variation of ln(1 – qt/qe) values with time at different temperature with respect to pseudo-first order kinetics; (b) vari-
ation of t/qt values with time at different temperature ((1) 30, (2) 35, (3) 40, (4) 45, (5) 50°C) with respect to pseudo-second order
kinetics.

from the slope and cutoff points of the plotted lines Effects of Temperature
(Fig. 2). The kinetic constants obtained from the pH 6
line are not only due to the removal of amino oxides, Batch experiments were carried out on a shaker at
but also from the precipitation of Cr(III) heavy metal different concentrations of 1 g L–1 of amino oxime and
ions. When the validation of the experimental data was 100 mg L–1 of Cr(III) ions at different temperatures
examined, it was found that the pseudo second degree between 30 and 50°C and at a solution pH of 5. The
kinetic model (R2 = 0.98–0.99) was more suitable kinetic constants for pseudo first and second order
than the first order kinetic model (R2 = 0.86–0.99). models at different temperature values given in Fig. 3
are found from the slope and cut points of the plotted
The pH changes of the first and second order rate lines. When we look at the correlation constants, it is
constants (k1 and k2) are given in Table 1. As a result seen that the pseudo second degree kinetic model
of the increase of the solution pH, the kinetic con-
stants in both modes increased with pH as a result of
Table 1. Variations in the pH of the first and second order
the easier binding of the Cr(III) ions to the negatively rate constants
charged binding sites on the surface of the complex
pH 3 4 5 6
formation due to their low (H+) ion concentrations.
The first and second order rate constants were k1, min–1 0.226 0.315 0.362 0.457
0.362 min–1 and 0.0023 (mg g–1)–1 min–1 at pH 5, R2 0.86 0.99 0.93 0.99
respectively, but these values decreased by
k2, (mg g–1)–1 min–1 0.0019 0.0021 0.0023 0.0054
0.226 min–1 and 0.0019 (mg g–1)–1 min–1 at pH 3,
respectively. R2 0.98 0.99 0.98 0.99

RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A Vol. 96 No. 3 2022

 KINETIC STUDY ON REMOVAL OF Cr(III) HEAVY METAL 553

Table 2. Variations in the first and second rate constants with the temperature
T, °C 30 35 40 45 50

k1, min–1 0.368 0.384 0.399 0.405 0.415

R2 0.94 0.96 0.98 0.97 0.98
k2, (mg g ) –1 –1
min –1
0.00234 0.00372 0.00523 0.00544 0.00626
R2 0.99 0.99 0.99 0.99 0.99

Table 3. Variations of the first and second order rate constants with Cr(III) ion concentrations
[Cr(III)], mg L–1 25 50 100 150 200 250 300

k1, min–1 0.543 0.485 0.401 0.392 0.387 0.381 0.379

R2 0.94 0.98 0.95 0.98 0.98 0.98 0.98
k2, (mg g ) –1 –1
min –1
0.0065 0.0042 0.0036 0.0031 0.0029 0.0028 0.0027
R2 0.98 0.96 0.98 0.97 0.99 0.97 0.98

(R2 = 0.99) is more suitable than the first order kinetic
model (R2 = 0.94–0.98).
The temperature changes of the pseudo-first and
second order rate constants (k1 and k2) are given in
Table 2. At higher temperatures, the kinetic constants
for both models increased due to the higher tempera-
ture (higher energy levels) due to the higher communi-
cation frequency between the complex formation and
the Cr(III) ion. As a result of the increase in solution
pH, the kinetic constants in both modes increased
with pH as a result of the easier binding of Cr(III) ions
to the negatively charged binding sites on the surface
of the complex formation due to their low (H+) ion
concentrations. The first and second order rate con-
stants are 0.388 min–1 and 0.00234 (mg g–1)–1 min–1
and 0.00626 mg g–1, respectively, with the temperature
rising from 30 to 50°C, it increased to 1 min–1. It is
clear that kinetic constants are very sensitive and
effective for both the first and second order models,
depending on the energy levels of both the complex
formation and the contaminant.
Effects of Cr(III) Ion Concentration
The concentration of Cr(III) ions was varied
between 25 and 300 mg L–1, with the concentration of
amino oxime being fixed at 1 g L–1, pH 5, and 25°C in
this experimental set. Kinetic constants for pseudo-
first and second order models at different Cr(III) ion
concentrations were found from the slope and cut
points of the plotted lines (Fig. 4). From the correla-
tion constants, it was found that the pseudo second
order kinetic model (R2 = 0.97–0.99) is more suitable
than the first order kinetic model (R2 = 0.94–0.98).
Variations of the first and second order rate con-
stants (k1 and k2) with Cr(III) ion concentrations are
given in Table 3. Since the concentration of the com-

0 0.12
1 0.10
0.08
ln(1  qt/qe)

2
1
2 0.06
t/qt

3
3
4 4 0.04
5
5 6 0.02
(a) 7 (b)
6 0
0 2 4 6 8 10 0 2 4 6 8 10
Time, min Time, min

Fig. 4. (a) Variation of ln(1 – qt /qe) values with time at different Cr(III) ion concentration ((1) 25, (2) 50, (3) 100, (4) 150, (5) 200,
(6) 250, (7) 300 mg L–1) with respect to pseudo-first order kinetics; (b) variation of t/qt values with time at different Cr(III) ion
concentration with respect to pseudo-second order kinetics.

RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A Vol. 96 No. 3 2022

554 YUNUS PAMUKOĞLU et al.

0 0.4
1
0.3
1
ln(1  qt/qe)

2
2
3

t/qt
3 0.2
4
4 5
6 0.1
5 7
(a) (b)
6 0
0 2 4 6 8 10 0 2 4 6 8 10
Time, min Time, min

Fig. 5. (a) Variation of ln(1 – qt/qe) values with time at different amino oxime concentration with respect to pseudo-first order
kinetics; (b) variation of t/qt values with time at different amino oxime concentration ((1) 0.25, (2) 0.5, (3) 1.0, (4) 1.5, (5) 2.0,
(6) 2.5, (7) 3 g L–1) with respect to pseudo-second order kinetics.

plex formation at high Cr(III) concentrations and there-
fore the binding points are constant, the pseudo first and
second order kinetic constants are reduced as the initial
Cr(III) ion concentration increases and there is compe-
tition between the Cr(III) ions (blocking effect). The first
and second order rate constants decreased from
0.543 min–1 and 0.0065 (mg g–1)–1 min–1 to 0.379 min–1
and 0.0027 (mg g–1)–1 min–1 when the Cr(III) ion
concentration increased from 25 to 300 mg L–1,
respectively.
The Effects of Amino Oxime Concentration
The initial concentration of Cr(III) ion was kept
constant at pH 5 and 25°C with 100 mg L–1 respec-
tively, and the amino oxime concentrations were var-
ied between 0.25 and 3.0 g L–1. The data obtained for
different concentrations of amino oxime concentra-
tors were linearized, and pseudo-first and second
order kinetic model constants were calculated from
the cut-off point and slope (Fig. 5). The kinetically
modified pseudo-second order kinetic model (R2 =
0.96–0.99), confirming the interaction of the complex
formation and the contaminant, assessed the data
more reliably than the pseudo-first order kinetic
model (R2 = 0.89–0.95).
Amino oxime concentrations of the first and sec-
ond rate constants (k1 and k2) are shown in Table 4.
The first and second order rate constants increased
from 0.532 min and 0.0005 (mg g–1)–1 min–1 to
0.394 min and 0.0312 (mg g–1)–1 min–1 when the
amino oxime concentration increased from 0.25 to
0.25 g L–1, respectively.
CONCLUSIONS
In this study, kinetic studies were carried out to
determine the rate of complex formation of Cr(III)
heavy metals in leather wastewaters in aqueous solu-
tion removal using amino oxime chemical compound.
The effects of operating parameters such as pH, tem-
perature, Cr(III) ion and amino oxime concentrations
were investigated in determining the kinetics of com-
plex formation with amino oxime and Cr(III) ions.
Kinetic studies have been carried out with the aim
of determining the velocities of the complex formation
process. The results are listed below as item cursors:
• pseudo-first and second degree kinetics were
applied for the purpose of verifying the amount of
adsorbed material in equilibrium and determining the
rate constants;
• pseudo-second order kinetics were found to be
more appropriate in evaluating the kinetic data calcu-
lated for almost all operating parameters.

Table 4. Variations of the first and second order rate constants with amino oxime concentrations (C)
C, g L–1 0.25 0.50 1.0 1.5 2.0 2.5 3.0

k1, min–1 0.294 0.302 0.319 0.331 0.341 0.362 0.432

R2 0.89 0.95 0.93 0.95 0.94 0.95 0.89
k2, (mg g–1)–1 min–1 0.0005 0.0011 0.0021 0.0081 0.0142 0.0187 0.0312
R2 0.96 0.97 0.98 0.97 0.98 0.98 0.99

RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A Vol. 96 No. 3 2022

 KINETIC STUDY ON REMOVAL OF Cr(III) HEAVY METAL
ACKNOWLEDGMENTS
The authors are grateful for the financial support pro-
vided by Süleyman Demirel University Research Founda-
tion Unit under project number of 2875-YL-11.
CONFLICT OF INTEREST
The authors declare that they have no conflicts of interest.
REFERENCES
1. S. Datta, B. K. Mahapatra, J. N. Bhakta, et al., in
Wastewater Management through Aquaculture (Springer,
Singapore, 2018), p. 207.
2. P. S. Keng, S. L. Lee, S. T. Ha, et al., Environ. Chem.
Lett. 12, 15 (2014).
3. B. König, J. Janker, T. Reinhardt, et al., J. Clean. Prod.
180, 232 (2018).
4. M. R. Prasanthi, M. Jayasravanthi, and R. V. Nadh,
Korean J. Chem. Eng. 33, 2374 (2016).
5. B. Zhao, X. Xu, S. Xu, et al., Bioresour. Technol. 243,
375 (2017).
6. B. Şen, F. Atasoy, and N. Aydın, Akad. Bilişim, 10
(2010).
7. X. Dang and Z. Shan, Environ. Chem. Lett. 16, 427
(2018).
8. R. P. Bartelme, B. O. Oyserman, J. E. Blom, et al.,
Front. Microbiol. 9, 8 (2018).
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A
555
9. Z. Guo, D. Dong, X. Hua, et al., Environ. Chem. Lett.
13, 111 (2015).
10. Q. Xu, Y. Wang, L. Jin, et al., J. Hazard. Mater. 339, 91
(2017).
11. P. C. Nagajyoti, K. D. Lee, and T. V. M. Sreekanth,
Environ. Chem. Lett. 8, 199 (2010).
12. Q. Li, J. Zhai, W. Zhang, et al., J. Hazard. Mater. 141,
163 (2007).
13. M. Y. Pamukoglu and F. Kargi, Process Biochem. 41,
1047 (2006).
14. P. K. Jal, S. Patel, and B. K. Mishra, Talanta 62, 1005
(2004).
15. S. Moradinasab and M. Behzad, Desalin. Water
Treatm. 57, 4028 (2016).
16. R. Nouri, E. Tahmasebi, and A. Morsali, Mater. Chem.
Phys. 198, 310 (2017).
17. J. Čežiková, J. Kozler, L. Madronová, et al., React.
Funct. Polym. 47, 111 (2001).
18. F. Karipcin, B. Dede, and M. Cengiz, Russ. J. Inorg.
Chem. 55, 530 (2010).
19. A. C. Gonçalves, H. Nacke, D. Schwantes, et al., Envi-
ron. Sci. Pollut. Res. 24, 21778 (2017).
20. A. Denizli, B. Garipcan, A. Karabakan, et al., Sep. Pu-
rif. Technol. 30, 3 (2003).
21. M. Y. Pamukoglu and F. Kargi, J. Hazard. Mater. 138,
479 (2006).
22. M. Y. Pamukoglu and F. Kargi, Enzyme Microbiol.
Tech. 42, 76 (2007).
Vol. 96 No. 3 2022