ECS Transactions, 64 (32) 13-23 (2015)

10.1149/06432.0013ecst ©The Electrochemical Society

Kinetic and Thermodynamic Study of Mercury (II) Adsorption on Ca-Bentonite

I. Robles, L. Godínez and E. Bustos*

Centro de Investigación y Desarrollo Tecnológico en Electroquímica, S. C. Parque

Tecnológico Querétaro, Sanfandila, Pedro Escobedo, Querétaro, 76703, Mexico.

The adsorption of Hg (II) from aqueous solution into Ca-bentonite

was studied using a batch technique under controlled condition of
temperature and constant pressure. Adsorption percentage was
determined as a function of shaking time and temperature to study
the adsorption thermodynamics and kinetics of Hg (II) on Ca-
bentonite. The results showed that the adsorption behavior of Hg
(II) on Ca-bentonite was strongly dependent on time and
temperature. The adsorption isotherms were simulated by the
Langmuir, Freundlich, Temkin, Dubinin-Radushkevich and Flory-
Huggins models. The results of kinetics studies show that the
adsorption reaction is second order with respect to the metal cation
solution concentration. The thermodynamic parameters (∆Hº, ∆Sº
and ∆Gº) were determined at four different temperatures. The
results of thermodynamic investigation indicates the adsorption
reaction ∆G° (Hgads < Hgsol), with a bond energy ∆H° of -40.57
KJ·mol-1 and a low energy ∆S° minor of cero.

Introduction

Mercury (Hg°) is a metal which at room temperature is presented as odorless liquid,

when their temperature increases above 313 K, toxic and corrosive gases are produced,
and according to its chemical species, these are easily transported in water, air and soil
(1-4).

Soil is an important receptor of mercury, the concentration of the metal increases with
increasing concentration in the atmosphere. Deposited mercury may be retained,
mobilized and volatilized by various processes in soil. The presence of mercury in soils,
like other metals, is associated with organic matter and minerals. Mercury deposited in
soils is mainly in its oxidized form Hg2+ (5).

Within the classification of minerals that are present in soils include the silicate clays,
pyrite and quartz, which have the ability due to its composition, to act as adsorbents of
metal ions or may be carried out in exchange of ions from clay. Mercury has a high
affinity for soil minerals, so it might expect low mobility of this metal. However, the
amount of mercury adsorbed on the mineral surfaces of the soil depends on the soil pH,
cation exchange capacity and the specific surface of soil particles (6). Adsorption is the
accumulation of material in two dimensions in a water/solid and its understanding is
based on intramolecular interactions between it and the solid phase solute, in this process
clays act as good adsorbent materials (6-9).

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 ECS Transactions, 64 (32) 13-23 (2015)

Adsorption kinetics depends on the interaction adsorbent-adsorbate and system

conditions. The solute adsorption rate determines the residence time required to carry out
the adsorption reaction, which can be analyzed by a kinetic analysis. To distinguish the
kinetic equation based on the solution concentration and the adsorption capacity of the
solid Equation 1 is used.

Log(qm-qt) = Log(qm)-kt/2.30 [1]

Where qm and qt (mg•g-1) is the adsorption capacities at equilibrium and with respect to
time, respectively. K (min-1) is the rate constant of pseudo-first order. On the other hand,
the expression of pseudo-second rate order can be expressed by Equation 2,

dqt/dt = k(qe-qt)2 [2]

Where k is the rate constant of adsorption (g•mg-1•min-1), qe is the amount of solute

adsorbed at equilibrium (mg•g-1), and qt is the amount of solute adsorbed on the surface
of the sorbent at any time (mg•g-1).

There is a way to calculate the reaction order by the Equation 3 (10-12).

Log r = Log k+ nLog CHg [3]

The value of the slope (n) the reaction order and the rate constant of the value of the
intercept (k) , which can be corroborated by Equation 4, where the slope of the graph
confirms the value of the rate constant.

r = k[Hg]n [4]

Typically the mathematical correlation is an important role to the modeling process,

where physicochemical parameters are taken with the corresponding thermodynamic
considerations [9]. The models corresponding to two parameters can be evaluated directly
because a laboratory study of adsorption on an adsorbent material over time is set (10,
13-23). Once the amount of mercury adsorbed known from the model that best fits the
adsorption of mercury, one can calculate the equilibrium constant as Equation 5 shows:

Keq = [Hg2+]sol/[Hg2+]ads [5]

Additionally, the standard free energy ∆G ° (kcal•mol-1) can be calculated from the
following Equation 6:

∆G0 = -RT Ln Keq [6]

Where R is the ideal gas constant equal to 8.314 J (mol•K-1), and T is the absolute
temperature given in K. The apparent heat or reaction enthalpy, ∆H°, is assumed to be
constant for a covered area, and it can be estimated using Equation 7 where D is a
constant.

Ln Keq = - ∆H0/R (1/T) +D [7]

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 ECS Transactions, 64 (32) 13-23 (2015)

The above equation is represented by a straight line, for most processes and for most
reactions, with a slope of (-∆H°·R-1). For an exothermic process, the slope is positive
(∆H° < 0), and will be negative if the process is endothermic (∆H° > 0). The D can be
calculated by the intersection of the line in the y - axis. The entropy of a system ∆S° is
calculated using Equation 8 (8-10, 15).

∆G0 = ∆H0 -T ∆S0 [8]

The adsorption of Hg (II) on Clay happens across three main mechanisms of interaction,
as the follow equations show (8).

Mechanism 1:
Ca-bentonite + Hg2+sol↔ Hg–bentonite + Ca2+sol [9]

Mechanism 2:
Ca-bentonite + 2HgOH+sol↔ 2HgOH+–bentonite + Ca2+sol [10]

Mechanism 3:
Ca-bentonite + 2H+sol↔ 2H+–bentonite + Hg2+sol [11]

Ca-bentonite represents the Ca clay, Co means initial concentration, and Cdes is the
desorbed mercury concentration. Some reports show the formation of different mercury
compounds as mechanisms indicate (6). Using the last mechanism, adsorption isotherms
were performed to analyze the adsorption of mercury on calcium bentonite.

The interest of this study was to determine the thermodynamic and kinetic parameters of
the adsorption of mercury on calcium bentonite clay as a representative soil samples
contaminated with this metal. Adsorption tests were conducted and with the data obtained,
two parameters were obtained constructing adsorption isotherms and subsequently
performing thermodynamic study at three different temperatures. The thermodynamic
and kinetic results were used to obtain a model of the interaction of mercury on Ca-
betonite that is the same exchangeable 2+ cation.

Material and Methods

Calcium Bentonite from Lodbent was used to analyze the kinetic and thermodynamic
behavior of mercury adsorption; for this purpose Ca-Bentonite was exposed to a solution
of mercuric chloride (HgCl2) from Merck. Kinetics and thermodynamic study was carried
out at temperatures of 278, 283, 293 and 303 K.

The amount of mercury in solution was determined using the electrochemical technique
of Anodic Stripping Voltammetry (ASV), the difference between mercury in solution and
initial mercury concentration was taken as the adsorbed mercury by the clay. Stripping
methods include a variety of electrochemical methods have in common a characteristic
initial stage. In all these procedures, the analyte is first deposited on an electrode, usually
from a stirred solution, this stage is equivalent to an electrochemical pre-concentration,
analyte concentration at the electrode surface is much higher than within dissolution.
After a while, accurately measured, electrolysis is interrupted, the stirring is stopped and
the analyte deposited by any of the voltammetric procedures are determined. During this

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 ECS Transactions, 64 (32) 13-23 (2015)

second stage of analysis, the analyte is re-dissolved or released from the electrode, hence
the name of these methods. In the anodic stripping, the electrode acts as a cathode during
the deposition stage and as an anode during the stripping step, the analyte is oxidized
back to its original shape. A negative potential is applied to promote the fixation of
mercury into the surface of the working electrode, after a rest period a stripping is
promoted with a sweep potential to quantify the current response that is proportional to
the amount of mercury present in solution. To determine mercury concentration in
solution a Basi Epsilon potenciostate and a three electrodes cell were used, as working
electrode (WE) a glassy carbon electrode was used, as reference electrode (RE) Ag|AgCl
was used, and as counter electrode (CE) a Pt wire was used. Mercury concentration in
solution was measured, in this way the amount of mercury adsorbed on the clay is known
(23, 24).

Results and discussion

Adsorption kinetics

Mercury adsorption kinetic was analyzed, for this purpose the concentration of mercury
remaining in solution was analyzed after the equilibrium time, using the technique of
VRA, the difference between the amount of added and adsorbed mercury concentration is
known. Figure 1 shows the behavior obtained, equations (1) to (4) were used to calculate
the order of the reaction kinetics.

Figure 1. Adsorption kinetic of mercury (II) on calcium bentonite over the time.

Figure 2A and 2B show the kinetic data fit to pseudo first and pseudo-second order
kinetics. Fitting kinetic data obey to adsorption pseudo-second kinetic order.

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 ECS Transactions, 64 (32) 13-23 (2015)

Figure 2. Adsorption kinetics fitting of (A) pseudo-first, and (B) pseudo-second order
over time.

The theoretical calculation of the constant rate given by the Equation 3 is shown in
Figure 3. The order of reaction obtained by Equation 3 and Figure 3 indicated a reaction
order of 2.75, and a rate constant of 0.0061 obtained from the logarithm of the origin “y”.
Equation 4 and Figure 4 can corroborate the value of 0.0064 which was obtained from the
slope given in Figure 4.

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 ECS Transactions, 64 (32) 13-23 (2015)

Figure 3. Graph of Log r vs. Log [Hg] to calculate the reaction order.

Figure 4. Graph of r vs. Hgn to calculate the rate constant

Batch adsorption tests of mercury at temperatures of 278, 283, 293 and 303 K were
conducted after equilibrium adsorption time (24 h, given from Figure 1). Figure 5 shows
the amount of mercury in solution at equilibrium time analyzed at different temperatures.
The results were fitted for adsorption isotherm models that are shown in Table 1. As can
be seen in Table 1 Freundlich isotherm model showed the best fit of experimental results
by the lateral interaction between mercury and bentonite as it was reported before (25).
The values of the slope (m), intercept (b) and some additional parameters obtained from
each adsorption isotherm model are shown in Table 1.

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 ECS Transactions, 64 (32) 13-23 (2015)

Figure 5. Graph of [Hg]adsorbed vs. Co to obtain the equilibrium concentration in solution

depending on temperature.

Thermodynamic Adsorption Process

To calculate the equilibrium constant, the next equation was used: K= [Hg]ads/[Hg]sol.
From equations 6 to 8 the values of the thermodynamic parameters were obtained, which
are shown in Table 2 adding the calculated standard conditions at 298 K. The
thermodynamic values obtained for ∆G indicate that the adsorption process was favored
to mercury over Ca-bentonite than in solution, as |Hg|ads < |Hg|sol. The ∆H value (-
40.577 KJ·mol-1) and the value of ∆S (-42.273 KJ·mol-1) show that the interaction
mercury – Ca - bentonite is carried out at low energy.

Thermodynamic study of mercury adsorption on Ca-Bentonite indicates that mercury is

not directly moved to bentonite by the value of the energy of mercury adsorption (∆H = -
47 KJ·mol-1), but an excess of the pollutant promotes a mercury adsorption on the clay,
this information is indicted by the value of ∆G. Finally ∆S indicate that the adsorption
needs low energy to absorb mercury. As can be seen in Table 3, there is no enough
information about thermodynamics of mercury reported before this paper.

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 ECS Transactions, 64 (32) 13-23 (2015)

TABLE I. Isotherm models fitting data.

Parameters obtained from Parameters obtained
Theoretical Model R2
T/K m from b
of Isotherm (linear fitting)
(slope) (intercept)

278 Qo = 1.520 mg g-1 B = 0.035 L mg-1 0.680

-1 -1
283 Qo = 0.622 mg g B = 0.030 L mg 0.022
Langmuir -1 -1
293 Qo = 0.285 mg g B = 0.028 L mg 0.610
303 Qo = 0.161 mg g-1 B = 0.152 L mg-1 0.795
-1
278 n = 0.89 KF = 0.025 mg g 0.983
-1
283 n = 0.79 KF = 0.010 mg g 0.991
Freundlich -1
293 n = 0.77 KF = 0.005 mg g 0.987
303 n = 0.72 KF = 0.003 mg g-1 0.982
-1 -1
278 bT = 7634.22 g mg AT = 0.590 L g 0.921
-1 -1
283 bT = 7500.23 g mg AT = 0.026 L g 0.906
Temkin -1 -1
293 bT = 6329.78 g mg AT = 0.014 L g 0.967
303 bT = 5828.08 g mg-1 AT = 0.013 L g-1 0.931
-2 -1
278 BD = 2.009 x 10-6 mol2 J q0 = 0.195 mg g 0.788
-2 -1
Dubinin- 283 BD = 2.279 x 10-5 mol2 J q0 = 1.646 mg g 0.815
Radushkevich -2 -1
293 BD = 5.073 x 10-5 mol2 J q0 = 0.356 mg g 0.965
303 BD = 1.780 x 10-5 mol2 J-2 q0 = 2.171 mg g-1 0.924
-1
278 nFH = 2.659 KFH = 3.09 x 10-4 L g 0.557
-1
283 nFH = 1.301 KFH = 3.40 x 10-2 L g 0.066
Flory-Huggins -1
293 nFH = 1.515 KFH = 2.30 x 10-2 L g 0.605
303 nFH = 3.871 KFH = 4.10 x 10-2 L g-1 0.750
Note: Q0 is maximum monolayer coverage capacities, B the Langmuir isotherm constant,
n represents the adsorption intensity, KF the Freundlich isotherm constant related to
adsorption capacity, bT means Tempkin isotherm constant, AT is Tempkin isotherm
equilibrium binding constant, B0 is Dubinin–Radushkevich isotherm constant, q0
represents theoretical isotherm saturation capacity, nFH means Flory–Huggins isotherm
model exponent, and KFH the Flory–Huggins isotherm equilibrium constant (Foo and
Hameed, 2010; Kennedy and Murthy, 2010).

TABLE II. Calculation of Thermodynamic parameters.

∆G°° ∆H°° ∆S°°

Conditions T (K)
(KJ•mol-1) (KJ•mol-1) (KJ•mol-1)
278 - 1.238 - 40.577 - 39.339
Experimental 283 - 0.299 - 40.577 - 40.278
293 0.984 - 40.577 - 41.561
303 2.381 - 40.577 - 42.958
Standard conditions (calculated) 298 1.696 - 40.577 - 42.273

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 ECS Transactions, 64 (32) 13-23 (2015)

TABLE III. Thermodynamic comparison of metal adsorption on different adsorbent matrixes.

Metal (II) Adsorbent matrix Thermodynamic parameters Reference
Activation energies: 4.9, 8.2 and 9.1
Hg, Cd, Pb Demineralized coal kJ mol-1 Hg (II), Cd (II) and Pb (II), Eligwe et al., 1999
respectfully.
∆G = 6.19
Ea = - 969 KJ
Ni y Pb Bentonite Okoye et al., 2012
∆H = - 1511 J
∆S = - 25 J
∆S = 59.29 J•mol-1 K-1 Akapomie et al.,
Cd Nsu clay
∆H = 16.93 KJ•mol-1 2012
Cu, Zn y Cd Calcined hydrocalcite Ea = 21.96 a 27.05 KJ•mol-1 Anirudha and
∆H° (Cu, 25°C) =19.02 KJ•mol-1 Suchithra, 2010
∆S° (Cu, 25°C) = - 74.58 J•mol-1
∆G° (Cu, 25°C) = - 3.52 KJ•mol-1
Pb Agbani clay ∆H° = 14.37 KJ•mol-1 Dawodu, 2012
∆S° = 62.75 J•mol-1 K-1
Mn Natural clay ∆H°= 0.1157 KJ•mol-1 Eba et al., 2010
∆S°= 342.56 KJ•mol-1
∆G°= -105.39 KJ•mol-1
Pb, Zn y Cu Kaolinite - Shahmohammadi-
Kalalagh et al.,
2011
Hg Soil - Yin et al., 1997
Different Kaolinite (Pb(II)) - Ho and McKay,
metals Biomass Cu y Pb (II) 1999
(review) Kaolinite (Hg(II))
Soil (Hg(II))
Hg 2- mercapto benzimidasol Endothermic process Manohar et al.,
Clay ∆H°= 20 a 30 KJ•mol-1 2002
Cu Bentonite - Qunaibit et al.,
2005
Cu Ca-kaolinite Adsorption (exothermic), desorption Doula, 2000
(endothermic)
∆G° = 0.06 a 0.39 Kcal•mol-1
∆H° = 20 a 200 Kcal•mol-1
∆S° = - 0.009 a - 0.04 Kcal•mol-1
grad-1
Pb Activated carbon - Machida et al.,
2004

Conclusions

The kinetic and thermodynamic study allowed us to know the behavior of the adsorption
of mercury. The behavior of the adsorption kinetics fits a second-order model, the data
were fitted to the Freundlich isotherm, and these results are consistent with reports in the
literature for the adsorption of mercury in various matrices as carbon by the lateral
interactions of mercury over adsorbent material. The results of the thermodynamic study
indicate that the adsorption process is favored as |Hg|ads< |Hg|sol. This means that the
adsorption of mercury in calcium bentonite is favored by an excess of mercury in solution.
Therefore, the energy of the adsorption process is -40.57 KJ•mol-1. The mercury is
adsorbed onto the calcium bentonite a form stable bond, the calcium in the bentonite is
displaced by the mercury present in solution promoting by the kinetic process too.

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Acknowledgements.

Authors thank Consejo Nacional de Ciencia y Tecnología de los Estados Unidos

Mexicanos (CONACYT) for the financial support, bilateral project Mexico - Hungary
and L’Oreal – United Nations Educational, Scientific and Cultural
Organization (UNESCO) – Academia Mexicana de Ciencias (AMC). I. Robles is grateful
to CONACyT for her scholarship.

References

1. F. A. Cotton and G. Wilkinson, Advanced Inorganic Chemistry, A Comprehensive

Text, Sixth ed. Wiley & Sons (1999).
2. N. N. Greenwood and A. Earnshaw, Chemistry of the Elements, Second Ed.
Butterworth – Heinemann (1997).
3. A. F. Holleman and E. Wiberg, Inorganic Chemistry, Academic Press. U.S.A.
(2001).
4. C. E. Housecraft and A. G. Sharpe, Química Inorgánica, Second ed. Pearson
Prentice Hall. U. S. A. (2006)
5. T. Volke, J. A. Velasco and D. A. De la Rosa, Suelos Contaminados por Metales
y Metaloides, SEMARNAT, México (2005).
6. F. M. M. Morel, Annu. Rev. Ecol. Syst., 29, 543 (1998).
7. S. Müller, K. U. Totsche and K. Knabner, European J. Soil Sci., 58, 918 (2007).
8. M. Doula, A. Ioannou and A. Dimirkou, Adsorption, 6, 325 (2000).
9. D. A. Skoog, Fundamentos de Química Analítica, Editorial Reverté, Barcelona
(1997).
10. J. U. Kennedy and Z. V. P. Murthy, Appl. Clay Sci., 50, 409 (2010).
11. E. A. Kim, Y. Masue - Slowey, S. Fendorf and R. G. Luthy, Chemosphere, 86,
648 – 654 (2012).
12. K. Y. Foo and B. H. Hameed, Chem. Engin. J,. 156, 2 (2010).
13. C. Hinz, Geoderma, 99, 225 (2001).
14. M. Toor and B. Jin, Chem. Engin. J., 187, 79 (2012).
15. G. P. Jeppu and T. P. J. Clement, Contam. Hidrol., 129, 46 (2012).
16. F. A. Dawodu, G. K. Akpomie and P. C. N. Ejikeme, Res. J. Engineering Sci., 1
(6), 9 (2012).
17. F. A. Dawodu, G. K. Akpomie and I. C. Ogbu, Intern. J. Multidisciplinary Sci.
Engin., 3 (9), 9 (2012).
18. D. Wankasi and T. Tarawou, J. Appl. Sci. Environ. Manag., 12 (4), 87 (2008).
19. Y. S. Ho, J. F. Porter and G. Mckay, Water, Air, Soil Poll., 141, 1 (2002).
20. Y. S. Ho and G. McKay, Process Biochem., 34, 451 (1999).
21. A. U. Itodo and H. U. Itodo, Life Sci. J., 7 (4), 31 (2010).
22. M. Horsfall and A. I. Spiff, Acta Chim. Slov., 52, 174 (2005).
23. R. G. Compton and C. E. Banks, Understanding Voltammetry, World Scientific
Publishing Co., United States (2007).
24. A. J. Bard and L. R. Faulkner, Electrochemical Methods, Fundamentals and
Applications, John Wiley and Sons, United States (1980).
25. I. Robles, M. G. García, S. Solís, G. Hernández, Y. Bandala, E. Juaristi and E.
Bustos, Int. J. Electrochem. Sci., 7, 2276 (2012).
26. G. K. Akpomie, M. A. Abuh, C. I. Ogbu, A. C. Agulanna and I. O. Ekpe, JETEAS,
3 (2), 254 (2012).

22
Downloaded on 2016-04-04 to IP 170.140.26.180 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).
 ECS Transactions, 64 (32) 13-23 (2015)

27. M. H. Al-Qunaibit, W. K. Mekhemer and A. A. Zaghloul, J. Colloid Interface Sci.,

283, 316 (2005).
28. T. S. Anirudhan and P. S. Suchithra, Indian J. Chem. Technol., 17, 247 (2010).
29. H. B. Bradl, J. Colloid Interface Sci., 277, 1 (2004).
30. F. Eba, S. Gueu, A. Eya’A-Mvongbote, J. A. Ondo, B. K. Yao, N. J. Ndong and B.
R. Kouya, Intern. J. Engin. Sci. Technol., 2 (10), 5001 (2010).
31. C. A. Eligwe, N. B. Okolue, C. O. Nwambu and C. I. A. Nwoko, Chem. Eng.
Technol., 22, 45 (1999).
32. M. Machida, Y. Kikuchi, M. Aikawa and H. Tatsumoto, Colloids Surf. A:
Physicochem. Eng. Aspects, 240, 179 (2004).
33. D. M. Manohar, K. A. Krishnan and T. S. Anirudhan, Water Res., 36, 1609
(2002).
34. I. P. Okoye, C. Obi and S. E. Otolo, J. Applied Technol. Environ. Sanitation, 2 (3),
145 (2012).
35. S. Shahmohammadi - Kalalagh, H. Babazadeh, A. H. Nazemi and M. Manshouri,
J. Env. Sci., 9 (2), 243 (2011).
36. Y. Yin, H. E. Allen and C. P. Huang, Environ. Sci. Technol., 31, 496 (1997).

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