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Procedia Environmental Sciences 16 (2012) 646 – 655

The 7th International Conference on Waste Management and Technology

Kinetic and equilibrium studies of chromium (III) removal


from aqueous solution by IRN-77 cation-exchange resin
Huai Lia, Jianzheng Lia,*, Zifang Chib, Weishi Kec
a
State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology, Harbin 150090, PR China
b
School of Environment, Tsinghua University, Beijing 100084, PR China
c
Fujian-Bailin Environmental Technology Co. Ltd., Quanzhou 362271, Fujian Province, PR China

Abstract

The kinetic and thermodynamic characteristics of adsorption of Cr (III) on IRN77 cation-exchange resin was
investigated in the present study. Cr (III) sorption on cation-exchange resin IRN77 was studied as a function of time
and temperature. The temperature was found to have a positive effect on film and particle diffusion processes. The
activation energy was calculated using Arrhenius equation based on the rate constants and indicated that the
activation energy of the particle diffusion process was higher than that of the film diffusion process. The film
diffusion equation was well-fitted with a correlation coefficient over 0.99. The results showed that the film diffusion
process was the rate-limiting step during Cr (III) sorption process. After the rate constants of adsorption isotherm of
Cr (III) obtained from the Langmuir equation, the thermodynamic parameters ǻSș, ǻHș and ǻGș were further
calculated using the Eyring equation. The ǻSș and ǻHș were found to be -128.07 J/mol·K and 42.98 kJ/mol,
respectively. The ǻGș at temperature 298K, 313K and 328K were 81.14, 83.07 and 84.99 kJ/mol, respectively. The
thermodynamic characteristics revealed that the mechanism of Cr (III) sorption was endothermic and the entropy-
driving ion exchange.

© 2012 The Authors. Published by Elsevier B.V.


© 2012 Selection and/or peer-review under responsibility of Basel Convention Coordinating Centre for Asia and the Pacific
Selection and/or
and National peer-review
Center underManagement,
of Solid Waste responsibilityMinistry
of BaselofConvention Coordinating
Environmental Protection Centre for Asia and the Pacific
of China.
and National Center of Solid Waste Management, Ministry of Environmental Protection of China.

Keywords: Chromium(III); Ion-exchange; Langmuir model; Kinetics study; Film diffusion

1. Introduction

Heavy metal contamination exists in the aqueous waste streams discharged from various industries,
such as plating facilities, mining operations, nuclear power plants and tanneries. Some metals associated
with these activities are cadmium, chromium, cobalt, lead and mercury. Heavy metals are not

* Corresponding author. Tel./fax: +86-0451-86283761.


E-mail address: ljz6677@163.com.

1878-0296 © 2012 Selection and/or peer-review under responsibility of Basel Convention Coordinating Centre for Asia and the Pacific and National
Center of Solid Waste Management, Ministry of Environmental Protection of China
doi:10.1016/j.proenv.2012.10.089
Huai Li et al. / Procedia Environmental Sciences 16 (2012) 646 – 655 647

biodegradable and tend to accumulate in living organisms, causing various diseases and disorders [1-3].
Chromium exists in various wastes and a common metal contamination [4]. It has two stable oxidation
states, Cr (III) and Cr (VI), in environment. Cr (III) is considered as an essential trace element playing an
important role in the metabolism of glucose, lipid and protein, whereas Cr (VI) is reported to be toxic to
the biological systems [5-7]. Thus, Cr (VI) removal has been investigated extensively. However, Cr (III)
removal has attracted an increasing interest in view of its oxidation to harmful Cr (VI) in the presence of
oxidants in nature media such as soil and water [8, 9].
The separation techniques commonly used for the removal of Cr (III) from aqueous solutions are
solvent extraction, ion exchange, co-precipitation, membrane processes and sorption [9]. Organic ion
exchange resins are found more suitable for the removal of toxic metal cations because of their faster
kinetics, ease of regeneration and high exchange capacity [10]. Though, a number of monovalent and
divalent metal cations have been reported for the exchange removal from aqueous solutions [11-13], a few
studies have focus on exchange removal of trivalent metal cations like Cr3+, Al3+, Fe3+, etc. [14,15].
Macrosporous strong cation Amberlyst-15 (H+) and macroporous weak acid exchanger Amberlite IRC-50
(Na) have been reported to remove Cr (III) from aqueous solutions and proved a strong affinity for metal
cations [4, 16]. A cation exchange resin IRN77 was introduced for the exchange removal of Cr (III) from
aqueous solutions, and the kinetic and thermodynamic characteristics of the adsorption process was
investigated in the present study.

2. Material and methods

All of the analytical grade reagents were used without further purification. Their solutions were
prepared in Pyrex glass vessels using doubly distilled water. The physical properties and specifications of
the cation-exchange resin IRN77 (M/s Rohm and Haas, SA, France) were illustrated in Table 1.

Table 1. Characteristics of IRN77 cation-exchange resin.

Number Characteristics Values


Physical characteristics
1 Physical form Uniform particle size spherical beads
2 Shipping weight 800 g/l
3 Harmonic mean size 650 ± 50 ȝm
4 Uniformity coefficient <1.2
5 Particle size <0.300mm,0.2%maximum;>1.180mm,2.0%maximum
6 Whole beads 95% minimum
7 Breaking weight (average) >350 g per bead
Chemical characteristics
8 Matrix Polystyrene DVB gel
9 Functional groups Sulphonic acid
10 Ionic form as shipped H+
11 Total exchange capacity >1.9 equiv. lí1 (H+ form)
12 Moisture holding capacity 49-55% (H+ form)
13 Ionic conversion 99% minimum H+
648 Huai Li et al. / Procedia Environmental Sciences 16 (2012) 646 – 655

To obtain the adsorption isotherm, 0.4 g of commercially prepared IRN77 cation-exchange resin was
added into a Pyrex glass vessel containing 100 mL of CrCl3·6H2O solution with a certain concentration,
and then stirred for 240 minutes with a rate of 120 r/min. The chromium solution with a concentration of
50,150,250 and 500 mg/L was tested at a desired temperature of 298, 313 and 328K in a shaker bath
(SHZ-82, Jintan Shunhua, China), separately. After absorption for 240 minutes, about 0.5 mL solution
was sampled from each adsorption system for detecting the chromium content by an inductively coupled
plasma atomic emission spectrophotometry (IRIS/AP, Thermo Jarrel Ash, USA).
An infinite bath method was used to study the kinetics of sorption of Cr (III) in adsorption systems, all
of which contained the same 0.4 g IRN77 resin and 100 mL Cr(III) solution with a concentration of 250
mg/L. The adsorption systems were put in a shaker bath (SHZ-82, Jintan Shunhua, China) and the
kinetics was investigated at temperature 298, 313 and 328K, respectively, with a stirring rate of 120 r/min.
About 0.5 mL solution was sampled from each adsorption system at different time intervals for detecting
the chromium content.

3. Results and discussions

3.1. Kinetics studies

The adsorption process of Cr (III) on IRN77 resin was tested at temperature 298, 313 and 328K,
respectively, in 100 mL Cr(III) solution systems. The results (Fig.1) showed that the rate of chromium
sorption increased following the raise in temperature. The equilibrium achieved after adsorption for 120,
90 and 60 min at 298 K, 313 and 328 K, respectively.

70
60
50
X(mg/g)

40 298K
30 313K
20 328K
10
0
0 50 100 150 200 250 300
Time(min)

Fig.1. Amount of chromium adsorbed as a function of time for IRN77 at different temperatures.

The ion exchange kinetics is generally thought to follow five stages: (1) Diffusion of Cr (III) through
the solution onto the adsorbent particles; (2) Diffusion of Cr(III) through the adsorbent particles; (3)
Chemical exchange between H+ and Cr (III) in the interior of the particles; (4) Diffusion of the displaced
cation H+ through the solution away from the adsorbent particles (reverse of the step 1); (5) Diffusion of
the displaced cation H+ out of the interior of the exchanger (reverse of step 2). The kinetics of the
chromium sorption on IRN77 cation-exchange resin can be described with the help of two types of
Huai Li et al. / Procedia Environmental Sciences 16 (2012) 646 – 655 649

equations, film diffusion and particle diffusion equations. The expression for the film diffusion equation
is given below [17],

-ln(1- F)= ku t (1)

where F is the ratio of amount adsorbed after time t to the amount adsorbed at equilibrium and ku is the
rate constant. According to Eq. (1), when the kinetic data obtained for a series of F values were plotted
against t, a straight line was obtained having a slope equal to rate constant as shown in Fig.2. Similarly
for particle diffusion equation, the Bt values could be calculated by using the equations given below [16,
18, 19]:

Bt = -2.30258 ln(1- F) - 0.49770 (2)


1
Bt = 6.28318 - 3.2899F - 6.28318(1- 1.0470F) 2 (3)

where B is equal to D±2/r2, D being the particle diffusion coefficient and r its radius. Eq. (2) was used
for values of F˚0.85 and Eq. (3) for values of F˘0.85. The Bt values calculated from Eqs. (2) and (3)
were plotted against t and straight lines were obtained again. The values of rate constants B were
calculated from the slopes in Fig.3. The values of ku and B obtained from film and particle diffusion
equations at different temperatures were presented in Table 2.

5
y = 0.0748x + 0.0578 298K
4 2
R = 0.9977 313K
328K
-ln(1-F)

3 y = 0.061x + 0.0421
2
2 R = 0.9992
y = 0.0423x + 0.0962
1 2
R = 0.9955
0
0 10 20 30 40 50 60 70
Time(min)

Fig.2. Film diffusion plots for IRN77 at different temperatures.


650 Huai Li et al. / Procedia Environmental Sciences 16 (2012) 646 – 655

12
y = 0.1819x - 1.0266 298K
10 2
R = 0.9599 313K
8 y = 0.1469x - 1.2186 328K
2
6 R = 0.9032
Bt

4
y = 0.0921x - 0.9068
2 2
R = 0.8174
0
0 10 20 30 40 50 60 70
Time(min)

Fig.3. Particle diffusion plots for IRN77 at different temperatures.

Table 2. Values for film and particle diffusion process on IRN77 cation-exchange resin.

Activation energy,
Temperature (K) Rate constants k (miní1) R2
Ea (kJ•mol-1)

Film diffusion Particle Film Particle Film Particle


(ku) Diffusion (B) diffusion diffusion diffusion diffusion
298 0.0423 0.0921 0.9955 0.8174
313 0.061 0.1469 0.9992 0.9032 15.5 18.5
328 0.0748 0.1819 0.9977 0.9599

The activation energy (Ea) for the film and particle diffusional processes can be calculated using
Arrhenius equation as,

Ea
ln k = ln A- (4)
RT

where k=film diffusion (ku) or particle diffusion rate constant (B), A is Arrhenius factor, T is absolute
temperature and R is the molar gas constant.
The plots of ln k versus 1/T according to Eq. (4) for film and particle diffusion processes were shown
in Fig.4 where two straight lines were obtained with a slope and intercept equal to Ea/RT and ln A,
respectively. The rise in temperature caused a slight increase in the value of the rate constant (k) for the
ion exchange of Cr (III) ions tested in this study. The values of activation energy for both diffusion
processes were also given in Table 2. It could be seen from Table 2 that film diffusion equation was well-
fitted with relatively high R2 values and low activation energy as compared to particle diffusion equation.
This indicated that film diffusion process was the rate-limiting step during Cr (III) sorption. Alguacil et al.
[17] proposed that chromium adsorption by Amberlite IR-120 resin was film-diffusion controlled.
Rengaraj et al. [20] also assumed that the removal of chromium by ion exchange resins followed film
Huai Li et al. / Procedia Environmental Sciences 16 (2012) 646 – 655 651

diffusion process. Mustafa et al. [21] observed that the sorption process of chromium was controlled by
both the film and particle diffusions. Sheckel and Sparks [22] have also reported that activation energy
below 42 kJ/mol indicated diffusion-controlled processes.
1/T(1/K)
0.003 0.0031 0.0032 0.0033 0.0034
-0.5
-1 lnku lnB
ln(Rate constant)

-1.5 y = -2228.9x + 5.1296


2
R = 0.9666
-2
-2.5
-3 y = -1864.2x + 3.1143
2
R = 0.9819
-3.5

Fig. 4. Arrhenius plots for the chromium removal by IRN77 cation-exchange resin.

3.2. Equilibrium studies

The adsorption equilibrium of Cr (III) on IRN77 resin was studied using a concentration of 50,150,250
and 500 mg/L at temperature 298, 313 and 328K, respectively. The results (Fig.5) indicated that Cr (III)
sorption on IRN77 resin increased with increase in temperature and initial concentration. The best
sorption capacity of the exchanger IRN77 was found to be 1.3 mmol/g at 328K, which was found to be
much higher than 0.39 mmol/g for Lewetit S 100 and 0.29 mmol/g for Chelex-100 observed by Gode and
Pehlivan[23].

80

60
X(mg/g)

298K
40
313K
20 328K

0
0 50 100 150 200 250 300
Ce(mg/L)
Fig.5. Chromium(III) sorption isotherm on IRN77 cation-exchange resin at different temperatures.
652 Huai Li et al. / Procedia Environmental Sciences 16 (2012) 646 – 655

The Langmuir equation was applied to the present data to determine the maximum exchange capacity
at different temperatures. As was evident from Fig.6, the experimental data fitted to the linear form of the
Langmuir equation expressed in the form,

Ce 1 C
= + e (5)
X Kb X m X m

where Ce is the equilibrium concentration of metal ions in the solution, X is the amount of metal ions
sorbed per unit weight of the resin, Xm is the maximum sorption, Kb is the binding constant, computed
from the slope and intercept of the lines in Fig.6. It could be seen from table 3, there was not an increase
of Xm values for Cr (III) with increase in temperature, indicating that the exchange capacity of resin did
not increase with increase in temperature. The Kb values were found to increase with increase in
temperature, indicating the greater interaction of the metal with the resin.

0.1 y = 0.2693x + 0.01


2 y = 0.1125x + 0.0101
0.08 R = 0.9828 2
R = 0.9863
1/X(g/mg)

0.06
y = 0.0497x + 0.0099
0.04 2
R = 0.9038
0.02
298K 313K 328K
0
0 0.2 0.4 0.6 0.8 1 1.2 1.4
1/Ce(L/mg)

Fig.6. Langmuir plots for chromium(III) sorption on IRN77 cation-exchange resin at different temperatures.

Table 3. Calculated maximum adsorption capacity (Xm) and binding energy constants (Kb) at different temperatures.

Temperature (K) Xm (mg•g-1) Kb (L•mg-1) R2


298 100 0.037 0.9828
313 99 0.09 0.9863
328 101 0.199 0.9038
Huai Li et al. / Procedia Environmental Sciences 16 (2012) 646 – 655 653

The standard enthalpy, entropy and free energy changes for Cr (III) ion removal can be estimated by
using the well known Eyring equation,

T
k K B 'S T 'H
ln ln   (6)
T h R RT

where R is the molar gas constant, T is the absolute temperature, k is the rate constant, KB is the
Boltzmann constant and h is the Planck constant.
The standard free energy change (ǻGș) of the process can be calculated by the equation,

'GT 'H T  T 'S T (7)

The plots of ln k/T versus temperature according to Eq. (6, 7) gave a straight line with slope and
intercept equal to ǻHș/R and ǻSș/R + ln(KB/h), respectively, as shown in Fig.7. The values of ǻSș, ǻHș
and ǻGș thus calculated were given in Table 4. The ǻSș and ǻHș were found to be -128.07 J/mol·K and
42.98 kJ/mol, respectively. The positive ǻHș value indicated that the Cr (III) exchange required
considerable energy while the negative ǻSș values showed that the movement of the Cr (III) ions in the
exchanger was more restricted as compared to the outgoing ions. Therefore, the positive value of ǻHș and
the negative value of the ǻSș were related to the mutual changes in hydration/dehydration of the ions in
the exchanger and aqueous solutions, which indicated that the mechanism of sorption on IRN77 was
entropy-driving ion exchange and dependent upon the ionic radii and charge of counter-ion initially
present inside the resin. El-Naggar et al. [24, 25] have also reported the negative ǻSș values of activation
for the exchange of Cs+, Co2+ and Eu3+ with H+ on amorphous zirconium silicate as cation exchanger.
Similar positive values of ǻHș and ǻGș and negative values of ǻSș were also reported by Mustafa et al.
[26] for Cr (III) sorption on macroporous strong acid exchanger Amberlyst.15. Their ǻGș values for
exchange were found to be 74.3-90.52 kJ/mol, which were very close to the values reported in the present
investigation.

Table 4. Gibbs free energy, enthalpy and entropy changes for Cr(III) sorption on IRN77 cation-exchange resin.

Temperature (K) ǻGș (kJ•mol-1) ǻHș (kJ•mol-1) ǻSș (J•mol-1•K-1)


298 81.14
313 83.07 42.98 -128.07
328 84.99
654 Huai Li et al. / Procedia Environmental Sciences 16 (2012) 646 – 655

1/T(1/K)
0.003 0.0031 0.0032 0.0033 0.0034
-5

-6
y = -5169.8x + 8.3571
-7
ln(k/T)

2
R =1
-8

-9

-10

Fig.7. Plot of ln(k/T) versus 1/T for the sorption of Cr(III) onto IRN77 cation-exchange resin.

4. Conclusions

According to the experimental results, it may be concluded that IRN77 cation-exchange resin had fast
kinetics and high exchange capacity towards the Cr (III) ions in aqueous solutions. The temperature was
found to have a positive effect on both the film and particle diffusional processes. Film diffusion equation
was well-fitted with relatively high R2 values and low activation energy as compared to particle diffusion
equation, and it was apparent that the adsorption rate was controlled by the film diffusion process. The
ǻSș value was found to be negative while both the ǻGș and ǻHș were positive. The thermodynamic
parameters of activation revealed that the mechanism of Cr (III) sorption was endothermic and the
entropy-driving ion exchange.

Acknowledgements

This work was financially supported by State Key Laboratory of Urban Water Resource and
Environment, Harbin Institute of Technology (Grant No. 2010DX06) and Harbin Science and
Technology Bureau (Grant No. 2009RFXXS004).

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