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Removal of manganese from water by electrocoagulation: Adsorption,

kinetics and thermodynamic studies

Article in The Canadian Journal of Chemical Engineering · March 2013

DOI: 10.1002/cjce.21709

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Removal of Manganese from Water by
Electrocoagulation: Adsorption, Kinetics
and Thermodynamic Studies
Pandian Ganesan, Jothinathan Lakshmi, Ganapathy Sozhan
and Subramanyan Vasudevan*
CSIR-Central Electrochemical Research Institute, Karaikudi 630 006, Tamil Nadu, India

The present study provides an electrocoagulation process for the removal of manganese (Mn) from water using magnesium as anode and galvanised
iron as cathode. The various operating parameters like effect of initial pH, current density, electrode configuration, inter-electrode distance,
coexisting ions and temperature on the removal efficiency of Mn were studied. The results showed that the maximum removal efficiency of 97.2%
at a pH of 7.0 was achieved at a current density 0.05 A/dm2 with an energy consumption of 1.151 kWhr/m3 . Thermodynamic parameters, including
the Gibbs free energy, enthalpy and entropy, indicated that the Mn adsorption of water on magnesium hydroxides was feasible, spontaneous
and endothermic. The experimental data were fitted with several adsorption isotherm models to describe the electrocoagulation process. The
adsorption of Mn preferably fitting the Langmuir adsorption isotherm suggests monolayer coverage of adsorbed molecules. In addition, the
adsorption kinetic studies showed that the electrocoagulation process was best described using the second-order kinetic model at the various
current densities.

Keywords: electrocoagulation, manganese removal, adsorption kinetics, isotherms

INTRODUCTION and adsorption (Friberg, 1983; Gupta et al., 1997b; Nogawa

et al., 2004; Sekar et al., 2004; Youssef et al., 2004; Gupta et al.,

M
anganese (Mn) is the second most abundant metal in
2006a, 2008, 2009; Ali and Gupta, 2007; Ali and Gupta, 2008;
nature (Dabeka et al., 2002). It is an essential metal for
Bedow et al., 2008; Gupta and Rastogi, 2008a; Gupta and Suhas,
the human system and many enzymes are activated by
2009; Vasudevan et al., 2010). Physical methods like ion exchange,
Mn. Mn has a variety of applications in ceramics, primary cells
reverse osmosis and electrodialysis have proven to be either too
(dry battery) and electrical coils. Mn is also used in alloying ele-
expensive or inefficient to remove Mn from water. At present,
ment of many alloys. It is present in the atmosphere as suspended
chemical treatments are not used due to disadvantages like high
particulates resulting from industrial emission, soil erosion, vol-
costs of maintenance, problems of sludge handling and its dis-
canic emissions and the burning of MMT-containing petrol (WHO,
posal and neutralisation of effluent (Melnik et al., 1999; Mollah
2004). The Mn contaminant in ground water affects the intelligent
et al., 2001; Mouedhen et al., 2008). Recent research has demon-
quotient (IQ) of children (Dabeka et al., 2002). The neuro-
strated that electrocoagulation offers an attractive alternative to
toxic disease like Parkinsonism is caused by the Mn over intake
above-mentioned traditional methods for treating water (Mollah
(Erikson et al., 2007). The prolonged over intake is potentially
et al., 2001). In this process, anodic dissolution of metal electrode
affect the central nervous system and lungs. These Mn contam-
takes place with the evolution of hydrogen gas at the cathode
inants in the ground water cause a disease, called manganism
and also causes diseases of disturbed speech called prognosis,
also cause bronchitis and pneumonia (USEPA report). The World ∗ Author to whom correspondence may be addressed.
Health Organisation (WHO) prescribed the permissible limit for E-mail address: vasudevan65@gmail.com
the Mn in the ground water is 0.05 mg/L (WHO, 2004). Can. J. Chem. Eng. 91:448–458, 2013
The common methods for removing toxic metals from water © 2012 Canadian Society for Chemical Engineering
DOI 10.1002/cjce.21709
include electrodialysis, chemical coagulation, reverse osmosis, Published online 4 June 2012 in Wiley Online Library
co-precipitation, complexation, solvent extraction, ion exchange (wileyonlinelibrary.com).

| 448 | THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING | | VOLUME 91, MARCH 2013 |
(Mouedhen et al., 2008). Electrochemically generated metallic
ions from the anode can undergo hydrolysis to produce a series
of activated intermediated that are able to destabilise and adsorb
(Gupta et al., 1997a, 2006b, 2007; Gupta and Rastogi, 2008b) the
finely dispersed particles present in the water to be treated. The
adsorbed/destabilised particles then aggregate to form flocks as
outlined below:
(i) When iron/aluminum is used as the electrode, the reactions
are as follows:

At the cathode: 2 H2 O + 2 e− → H2 (g) + 2 OH− (1)

At the anode (Iron): 4 Fe + 10 H2 O + O2 → Fe(OH)3 ↓ + 4 H2

(2)

At the anode (Aluminum): Al3+ (aq) + 3 H2 O → Al(OH)3 ↓

+ 3 H+ (3)

(ii) In the present study, magnesium is used as anode and the

reactions are as follows:
At the cathode: 2 H2 O + 2 e− → H2 (g) + 2 OH− (4)
At the anode: Mg → Mg2+ + 2 e− (5)
In the solution: Mg2+ (aq) + 2 H2 O → Mg(OH)2 ↓ +2 H+ (6)
The advantages of electrocoagulaton include high particulate
removal efficiency, a compact treatment facility, relatively low cost
and the possibility of complete automation. This method is char-
acterised by reduced sludge production, a minimum requirement
of chemicals and ease of operation (Agrawal and Sahu, 2006).
Besides, the main disadvantage in case of aluminum electrode is
the residual aluminum (The USEPA guidelines suggest maximum
contamination is 0.05–0.2 mg/L) present in the treated water due
to cathodic dissolution. This will lead to health problems like can-
cer. There is no such health problem in the case of magnesium
electrode, because the USEPA guidelines suggest that the max-
imum contamination level of magnesium in water is 30 mg/L.
Although, there are numerous reports dealt with electrocoagula-
tion as a means of removal of many pollutants from water and
wastewater, but there are few studies on the removal of Mn by
electrocoagulation method.
This study presents the results of the laboratory scale studies on
the removal of Mn using magnesium and stainless steel as anode
and cathode respectively by electrocoagulation process. To opti-
mise the maximum removal efficiency of Mn, different reaction
conditions like effect of current density, co-existing ions, effect of
temperature and pH were studied. In doing so, the equilibrium
adsorption behaviour is analysed by fitting the isotherm models
of Langmuir and Freundlich. Adsorption kinetics of electrocoag-
ulants is analysed using first- and second-order kinetic models.
Activation energy was evaluated to study the nature of adsorption.
EXPERIMENTAL SECTIONS
Experimental Apparatus and Procedures
Figure 1 shows the electrolytic cell consisted of a 1.0-L Plexiglas
vessel that was fitted with a polycarbonate cell cover with slots to
Figure 1. Laboratory scale cell assembly, (1) DC power supply, (2) pH
meter, (3) electrochemical cell, (4) cathodes, (5) anode, (6) electrolyte,
(7) outer jacket, (8) thermostat, (9) inlet for thermostatic water, (10)
outlet for thermostatic water, (11) PVC cover, (12) pH sensor and (13)
magnetic stirrer.
introduce the anode, cathode, pH sensor, a thermometer and elec-
trolytes. Magnesium sheet (Alfa Aesar, Lancashire, UK) of surface
area (0.017 m2 ) acted as the anode. The cathodes were stainless
steel (commercial grade) sheets of the same size as the anode
is placed at an inter-electrode distance of 0.005 m. The temper-
ature of the electrolyte was controlled to the desired value with
a variation of ±2 K by adjusting the rate of flow of thermostati-
cally controlled water through an external glass-cooling spiral. A
regulated direct current (DC) was supplied from a rectifier (10 A,
0–25 V; Aplab model).
Manganese nitrate (Mn(NO3 )2 ; MERCK, Darmstadt, Germany,
AR Grade) was dissolved in distilled water for the required con-
centration. In all the experiments 2 mg/L of Mn was used. The
solution of 0.90 L was used for each experiment as the elec-
trolyte. The pH of the electrolyte was adjusted, if required, with
HCl (MERCK; AR Grade) or NaOH (MERCK; AR Grade) solutions
before adsorption experiments. To study the effect of co-existing
ions, in the removal of Mn, sodium salts (Analar Grade) of phos-
phate (5–50 mg/L), silicate (5–15 mg/L), carbonate (5–250 mg/L)
and arsenic (0.2–5 mg/L) was added to the electrolyte.
Analytical Methods
The concentration of Mn was determined using UV–Visible spec-
trophotometer with manganese kits (Pharo 300; MERCK). The
SEM and EDAX of Mn-adsorbed magnesium hydroxide coagu-
lant were analysed with a scanning electron microscope (SEM)
made by Hitachi (Chiyoda-ku, Tokyo, Japan; model s-3000h). The
Fourier transform infrared spectrum of magnesium hydroxide was
obtained using Nexus 670 FT-IR spectrometer made by Thermo
Electron Corporation (Waltham, MA). The XRD for magnesium
hydroxide coagulant was analysed by X-ray diffractmeter made
by JEOL X-ray diffractmeter (Type—JEOL, Tachikawa, Tokyo,
Japan). The concentration of carbonate, silicate, arsenic and phos-
phate were determined using UV–Visible spectrophotometer with
respective standard ion kits supplied by MERCK (Pharo 300).

| VOLUME 91, MARCH 2013 | | THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING | 449 |
THEORY
Adsorption Kinetic Modelling
The amount of generated coagulant (metal hydroxides) can be sto-
ichiometrically determined according to Faraday’s law. Since the
amount of coagulant can be estimated for a given time, the pollu-
tant removal can be modelled using an adsorption phenomenon.
In order to investigate the mechanisms of the adsorption process,
two different kinetic models, the first- and second-order Lagergren
models were applied to describe the kinetics of the Mn adsorp-
tion onto magnesium hydroxides. The best-fit model was selected
according to the linear regression correlation coefficient values,
R2 (Johnson, 1990).
First-Order Lagergren Model
The first-order Lagergren model is one of the most widely used
expressions describing the adsorption of solute from a solution.
The first-order Lagergren model is generally expressed as follows:
dqt
= k1 (qe − qt ) (7)
dt
where qe (mg/g) and qt (mg/g) are the amounts of Mn adsorbed
on the adsorbent at equilibrium and at any time t (min), respec-
tively, and k1 (min−1 ) is the rate constant of the first-order model.
The integrated form of the above equation with the boundary
conditions t = 0 to >0 (q = 0 to >0) is rearranged to obtain the
following time-dependence function:
k1 t
log(qe − qt ) = log(qe ) − (8)
2.303
The first-order model considers the rate of occupation of the
adsorption sites proportional to the number of unoccupied sites.
Second-Order Lagergren Model
The Lagergren second-order kinetic model is expressed as
(Izanloo and Nassir, 2005):
dqt
= k2 (qe − qt )2 (9)
dt
where k2 is the rate constant of second-order adsorption. The inte-
grated form of Equation (9) with the boundary condition t = 0 to
>0 (q = 0 to >0) is:
equilibrium curves. In this study, two adsorption isotherms, viz.,
Langmuir and Freundlich were applied to establish the relation-
ship between the amounts of Mn adsorbed onto the magnesium
hydroxides and its equilibrium concentration in the electrolyte
containing Mn ions (Hamadi et al., 2001).
Freundlich Isotherm
The Freundlich adsorption isotherm model includes considera-
tions of surface heterogeneity and exponential distribution of the
active sites and their energies. The isotherm is adopted to describe
reversible adsorption and is not restricted to monolayer formation.
This isotherm typically fits the experimental data over a wide
range of concentrations. The linearised and logarithmic expres-
sion of the Freundlich model is (Agrawal and Sahu, 2006):
log qe = log kf + n log Ce (12)
where kf (mg/g) and n (dimensionless) are constants that account
for all factors affecting the adsorption process, such as the adsorp-
tion capacity and intensity. The Freundlich constants kf and n are
determined from the intercept and slope, respectively, of the linear
plot of log qe versus log Ce .
Langmuir Isotherm
The Langmuir isotherm model was developed to represent
chemisorption at a set of well-defined localised adsorption sites
with the same adsorption energy, independent of the surface cov-
erage and with no interaction between adsorbed molecules. This
model assumes a monolayer deposition on a surface with a finite
number of identical sites. The Langmuir equation is valid for a
homogeneous surface. The linearised form of Langmuir adsorp-
tion isotherm model is (Sohn and Kim, 2005; Demiral et al., 2008):
Ce 1 Ce
= + (13)
qe qm b Qm
where qe (mg/g) is the amount adsorbed at equilibrium, Ce
(mg/L) is the equilibrium concentration, qm is the Langmuir con-
stant representing maximum monolayer adsorption capacity and
b is the Langmuir constant related to energy of adsorption.
The essential characteristics of the Langmuir isotherm can be
expressed as the dimensionless constant RL (Oguz, 2004):
RL =
1
(14)
1+bCo

1 1 where RL is the equilibrium constant it indicates the type of

= + k2 t (10)
qe − qt qe adsorption, b is the Langmuir constant and Co is the various con-
centration of Mn solution. The RL values between 0 and 1 indicate
Equation (10) can be rearranged and linearised as: the favourable adsorption.

t 1 t Effect of Temperature on Thermodynamic

= + (11)
qt k2 qe2 qe
where qe and qt are the amount of Mn adsorbed on Mg(OH)2
(mg/g) at equilibrium and at time t (min), respectively, and k2 is
the rate constant for the second-order kinetic model.
Adsorption Isotherms
The pollutants are generally adsorbed at the surface of the metal
hydroxides generated during the electrocoagulation process. In
order to identify the mechanism of the adsorption process, it is
important to establish the most appropriate correlation for the
Adsorption Parameters
To understand the effect of temperature on adsorption process,
thermodynamic parameters should be determined at various tem-
peratures. The energy of activation for adsorption of Mn can
be determined by the second-order rate constant is expressed in
Arrhenius form (Yang and Al-Duri, 2001):
log k2 = log k0 − 2.303 E/RT (15)
where ko is the constant of the equation (g/mg min), E is the
energy of activation (J/mol), R is the gas constant (8.314 J/mol K)

| 450 | THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING | | VOLUME 91, MARCH 2013 |
and T is the temperature (K). The free energy change is obtained
using the following relationship:

G = −RT ln Kc (16)

where
G is the free energy (kJ/mol), Kc is the equilibrium con-

stant, R is the universal gas constant and T is the temperature
(K). The relationship between
G,
H and
S can be expressed
by the following equation:

G =
H − T
S (17)

Combining Equations (16) and (17) leads to:

S
H
ln Kc = − (18)
R RT

Enhancement of adsorption capacity of electrocoagulant (mag- Figure 2. Effect of inter-electrode distance on removal efficiency and
nesium hydroxide) at higher temperatures may be attributed to energy consumption of manganese. Conditions—concentration: 2 mg/L;
the enlargement of pore size and or activation of the adsorbent pH of the electrolyte: 7.0; temperature: 305 K.
surface.

Pore Diffusion Coefficient (D)
The diffusion coefficient (D) for intraparticle transport of Mn
species into the adsorbent particles has been calculated at different
temperature by:
r02
t1/2 = 0.03 × (19)
D tial pH was kept in neutral, all the aluminum produced at the
where t½ is the time of half adsorption (s), ro is the radius of the
adsorbent particle (cm) and D is the diffusion coefficient (cm2 /s;
Golder et al., 2006).
RESULTS AND DISCUSSION
Effect of Inter-Electrode Distance
To determine the effect various inter-electrode distances between
anode and cathode were kept at different spacing of 0.003, 0.005,
0.007, 0.009 and 0.011 m using 2 mg/L Mn containing solutions
at a current density of 0.05 A/dm2 . The results of inter-electrode
distance on removal efficiency and energy consumption are pre-
sented in Figure 2. While decreasing the inter-electrode distance
shows decrease in energy consumption and increase in removal
efficiency. Lower distance between anodes and cathodes require
low electrical energy for motion of ions. This is due to shorter
travel path that reduce the resistance of motion of ions and the
situation is reverse for the case of large distance between each
electrode. In maintaining the inter-electrode distance of 0.003 m
was practically difficult. So, further experiments were carried out
at inter-electrode distance of 0.005 m. Inter-electrode spacing of
0.005 m had the low energy consumption and removal efficiency.
removal efficiency for the removal of Mn is 97.2% at pH 7 and the
minimum efficiency is 82.4% at pH 3. The decrease of removal
efficiency at more acidic and alkaline pH was observed by many
investigators and was attributed to an amphoteric behaviour of
Al(OH)3 which leads to soluble Al3+ cations (at acidic pH) and
to monomeric anions Al(OH)4− (at alkaline pH). When the ini-
anode formed polymeric species (Al13 O4 (OH)7+24 ) and precipitated
Al(OH)3 leading to more removal efficiency. In the present study,
the electrolyte pH was maintained in neutral, so the formation
of Mg(OH)2 is more predominant (like aluminium), leading to
greater removal efficiency.
Effect of Electrode Configurations
The percentage removal of Mn from Mg(OH)2 along with the
experimental conditions utilised at various current densities from
0.025 to 0.2 A/dm2 were analysed for monopolar and bipolar con-
figuration with concentration 2 mg/L. The data were presented in
Table 1. From Table 1, it was observed that, for a given current
densities, the removal efficiency of bipolar electrolytic cell was
slightly higher than the monopolar electrode configurations. And
the energy consumption was higher for monopolar electrode than
the bipolar electrode.
Table 1. Effect of electrode configuration at various current densities
with concentration 2 mg/L
Monopolar electrodes Bipolar electrodes

Effect of Electrolyte pH Current Removal Energy Removal Energy

density efficiency consumption efficiency consumption
It is believed that the initial pH is an important operating fac- (A/dm2 ) (%) kWhr/kL) (%) (kWhr/kL)
tor influencing the performance of electrochemical process. To
explain this effect, a series of experiments were carried out using 0.025 84.8 1.056 85.0 0.994
2 mg/L of Mn containing solutions, by adjusting the initial pH 0.05 97.2 1.151 97.3 1.002
in the interval from 3 to 11. The removal efficiency of Mn was 0.10 98.5 1.224 98.6 1.121
increased with increasing the pH up to 7. When the pH is above 0.15 98.6 1.298 98.7 1.186
7, removal efficiency was decreased. It is found that the maximum 0.20 98.8 1.365 99.0 1.239

| VOLUME 91, MARCH 2013 | | THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING | 451 |
Figure 3. Effect of time on the amount of manganese-adsorbed qe at Figure 4. Second-order kinetic model plot of different current density of
various current density. Conditions—concentration: 2 mg/L; pH of the manganese. Conditions—concentration: 2 mg/L; temperature: 305 K; pH
electrolyte: 7.0; temperature: 305 K. of the electrolyte: 7.

Effect of Current Density Kinetic Modelling

Among the various operating variables, current density is an
important factor which strongly influences the performance of
electrocoagulation. The amount of Mn removal depends upon the
quantity of adsorbent [Mg(OH)2 ] generated, which is related to the
time and current density (Mohammad et al., 2004). The amount
of adsorbent [Mg(OH)2 ] was determined from the using Faraday
law. With the increase in current density the amount of magne-
sium hydroxide generation also increases. To investigate the effect
of current density on the Mn removal, a series of experiments
were carried out by solutions containing a constant pollutants
loading of 2 mg/L, at a pH 7.0, with current density being var-
ied from 0.025 to 0.2 A/dm2 . Figure 3 shows the plot between
amounts of Mn adsorbed with respect to time at different current
densities. From the figure it was well seen that the uptake of Mn
(mg/g) increased with increase in current density and remained
nearly constant after equilibrium time. The equilibrium time was
found to be 45 min for all concentration studied. After 45 min the
amount of Mn adsorbed (qe ) increased from1.115 to 1.981 mg/g as
the current density increased from 0.025 to 0.2 mg/L. The figure
also shows that the adsorption is the rapid in the initial stages
and remains almost constant with the progress of the adsorp-
tion. The plots are single, smooth and continuous curves leading
to saturation, suggesting the possible monolayer coverage to Mn
on the surface of the adsorbent (Jiang et al., 2002; Malkoc and
Nuhoglu, 2007; Vasudevan et al., 2008; Vasudevan and Lakshmi,
2011; Vasudevan et al., 2011a,b,c).
In the present study, kinetic models, namely, first- and second-
order models were tested with the Mn concentration of 2 mg/L at
various current densities from 0.025 to 0.2 A/dm2 .
First-Order Lagergren Model
The experimental data were analysed initially with first-order
Lagergren model. The plot of log (qe − qt ) versus t should give
the linear relationship, from which k1 and qe can be determined
by the slope and intercept respectively from Equation (8). The
computed results are presented in Table 2. The results show that
the theoretical qe (cal) value does not agree to the experimental
qe (exp) values at all current densities studied with poor correla-
tion coefficient. So, further the experimental data were fitted with
second-order Lagergren model.
Second-Order Lagergren Model
The kinetic data were fitted to the second-order Lagergren model
using Equation (11). The equilibrium adsorption capacity, qe (cal)
and k2 were determined from the slope and intercept of plot of
t/qt versus t (Figure 4) and are compiled in Table 2. The plots
were found to be linear with good correlation coefficients. The
theoretical qe (cal) values agree well to the experimental qe (exp)
values at all current density studied. This implies that the second-
order model is in good agreement with experimental data and can
be used to favourably explain the Mn adsorption on Mg(OH)2 .

Table 2. Comparison of experimental and calculated qe values at different current densities for first- and second-order adsorption kinetics of
manganese with concentration 2 mg/L at 305 K

First-order adsorption Second-order adsorption

Current density (A/dm2 ) qe (exp) qe (Cal) k1 × 104 (min/mg) R2 qe (cal) k2 × 104 (min/mg) R2

0.025 1.115 25.33 −0.0066 0.7664 1.099 0.0961 0.9985

0.05 1.456 26.67 −0.0075 0.7856 1.367 0.0845 0.9989
0.1 1.704 27.82 −0.0081 0.8024 1.691 0.0714 0.9996
0.15 1.894 28.64 −0.0086 0.7645 1.808 0.0641 0.9956
0.2 1.981 29.01 −0.0091 0.7981 1.944 0.0523 0.9997

| 452 | THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING | | VOLUME 91, MARCH 2013 |
 Table 2 depicts the computed results obtained from first- and
second-order models. From the results, it is observed that the
correlation coefficients for the first-order kinetic model were rel-
atively lower than those obtained for the second-order kinetic
model for the different current densities. These results indicate
that the second-order kinetic model can be applied suitably to
predict the Mn adsorption process onto magnesium hydroxides.

ISOTHERM MODELLING
Freundlich Isotherm
In testing the isotherm, the Mn concentration used was
0.5–2.5 mg/L with various current densities from 0.025 to
0.2 A/dm2 and at an initial pH 7. The adsorption data are plotted
as log qe versus log Ce by Equation (12) should result in a straight
line with slope n and intercept kf . The intercept and the slope
are indicators of adsorption capacity and adsorption intensity,
respectively. The value of n falling in the range of 1–10 indicates
favourable sorption. The kf and n values were listed in Table 3 for
each concentration and current density. It has been reported that
values of n lying between 0 and 10 indicate favourable adsorption.
From the analysis of the results it is found that the Freundlich
plots fit satisfactorily with the experimental data obtained in the
present study.
Langmuir Isotherm
Langmuir isotherm was tested from Equation (13). The plots of
1/qe as a function of 1/Ce for the adsorption of Mn on Mg(OH)2 are
shown in Figure 5. The plots were found linear with good correla-
tion coefficients (>0.99) indicating the applicability of Langmuir
model in the present study. The values of monolayer capacity (qm )
and Langmuir constant (b) is given in Table 3. The values of qm
calculated by the Langmuir isotherm were all close to experimen-
tal values at given experimental conditions. These facts suggest
that Mn is adsorbed in the form of monolayer coverage on the
surface of the adsorbent.
The applicability of the two isotherm equations was compared
using the correlation coefficient (R2 ). The correlation coefficient
values of Freundlich and Langmuir isotherm models are presented
in Table 3. The values of correlation coefficient (R2 ) are found to
be >0.9 for both isotherms. However, based on the R2 values, the
Langmuir isotherm model provided a better fit compared to Fre-
undlich isotherm model. This suggests the adsorption of Mn by
magnesium hydroxides is apparently with monolayer coverage of
adsorbed molecules. The dimensionless constant RL were calcu-
Table 3. Constant parameters and correlation coefficient for different
adsorption isotherm models for manganese adsorption at
0.5–2.5 mg/L at various current densities of 0.025–0.2 A/dm2
Current density (A/dm2 )
Figure 5. Langmuir plot (1/qe vs. 1/Ce ) for adsorption of manganese.
Conditions—pH of the electrolyte: 7.0; current density:
0.025–0.2 A/dm2 ; temperature: 303 K; concentration: 0.5–2.5 mg/L.
lated from Equation (14). The RL values were found to be between
0 and 1 for all the concentration of Mn studied.
Thermodynamic Parameters
Figure 6 shows that the rate constants vary with temperature
according to Equation (15). The activation energy (0.665 kJ/mol)
is calculated from the slope of the fitted equation. The free energy
change is obtained from Equation (16). The Kc and
G values are
presented in Table 4. From the Table, it is found that the nega-
tive value of
G indicates the spontaneous nature of adsorption.
The enthalpy change (
H = 3.063 kJ/mol) and entropy change
(
S = 0.6975 J/mol K) were obtained from the slope and inter-
cept of the van’t Hoff linear plots of ln kc versus 1/T (Figure 7,
Equation 17). Positive value of enthalpy change (
H) indicates
that the adsorption process is endothermic in nature, and the
negative value of change in internal energy (
G) show the spon-
taneous adsorption of Mn on the adsorbent. Positive values of
entropy change show the increased randomness of the solution
interface during the adsorption of Mn on the adsorbent (Table 4).
Enhancement of adsorption capacity of electrocoagulant (magne-
sium hydroxide) at higher temperatures may be attributed to the
enlargement of pore size and/or activation of the adsorbent sur-
face. Using Lagergren rate equation, second-order rate constants
and correlation coefficient were calculated for different tempera-
tures (305–343 K). The calculated ‘‘qe ’’ values obtained from the
second-order kinetics agrees with the experimental ‘‘qe ’’ values
better than the first-order kinetics model, indicating adsorption
following second-order kinetics. Table 5 depicts the computed
results obtained from first- and second-order kinetic models.

Isotherm Parameters 0.025 0.05 0.1 0.15 0.2

Freundlich kf (mg/g) 1.7125 1.5959 1.4321 1.3782 1.2566 Table 4. Thermodynamics parameters for adsorption of manganese
n (L/mg) 1.0026 1.0065 1.1061 1.0996 1.0664
R2 0.9885 0.9856 0.9823 0.9881 0.9876 Temperature (K) Kc
G◦ (J/mol)
H◦ (kJ/mol)
S◦ (J/mol K)
Langmuir qm (mg/g) 1.7361 2.2261 2.8616 2.9465 3.0155
b (L/mg) 5.1892 4.9912 4.8321 4.5641 4.3981 323 17.085 −222.32 3.063 0.6975
R2 0.9995 0.9999 0.9989 0.9991 0.9988 333 18.122 −229.21
RL 0.5646 0.6125 0.5946 0.6864 0.6355 343 19.098 −236.17

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 Table 5. Comparison between the experimental and calculated qe values for the manganese concentration of 2 mg/L with 0.05 A/dm2 in first- and
second-order adsorption kinetics

First-order adsorption Second-order adsorption

Concentration (mg/L) qe (exp) qe (Cal) k1 × 104 (min/mg) R2 qe (Cal) k2 × 104 (min/mg) R2

323 3.9031 24.33 −0.0061 0.8002 3.8641 0.0661 0.9963

333 4.0078 28.34 −0.0068 0.7661 3.9914 0.0665 0.9991
343 4.2155 29.61 −0.0071 0.6844 4.0022 0.0671 0.9994

Effect of Competing Ions

Carbonate
Effect of carbonate on Mn removal was evaluated by increasing
the carbonate concentration from 0 to 250 mg/L in the electrolyte.
The removal efficiencies are 97.2%, 95.3%, 72.8%, 50.7%, 38%
and 19% for the carbonate concentration of 0, 2, 5, 65, 150
and 250 mg/L, respectively. From the results, it is found that the
removal efficiency of the Mn is not much affected by the pres-
ence of carbonate below 2 mg/L. Significant reduction in removal
efficiency was observed above 2 mg/L of carbonate concentration
is due to the passivation of anode resulting the hindering of the
dissolution process of anode.

Figure 6. Plot of log k2 and 1/T. Conditions—pH of 7.0; current density:
0.025–0.2 A/dm2 ; concentration: 0.5–2.5 mg/L.
Pore Diffusion Coefficient (D)
For all chemisorptions system the diffusivity coefficient should be
10−5 to 10−13 cm2 /s. In the present study, D is found to be in the
range of 10−10 cm2 /s. The D values for various temperatures and
different initial concentrations of Mn are presented in Table 6.
Phosphate
The concentration of phosphate ion was increased from 0 to
50 mg/L, the contaminant range of phosphate in the ground water.
The removal efficiency for Mn was 97.2%, 96.3%, 64.7%, 41.5%
and 36.2% for 0, 2, 5, 25 and 50 mg/L of phosphate ion, respec-
tively. There is a negligible change in removal efficiency of Mn
below 2 mg/L of phosphate in the water was observed. At higher
concentrations (at and above 2 mg/L) of phosphate, the removal
efficiency decreases drastically. This is due to the preferential
adsorption of phosphate over Mn as the concentration of phos-
phate increases.
Arsenic
The concentration of arsenic was gradually increased from 0 to
5 mg/L. From the results it is found that the removal efficiency
of Mn was decreased by increasing the concentration of arsenic.
The removal efficiencies are 97.2%, 95.7%, 83.5%, 73.6% and
54.6% for 0, 0.2, 0.5, 2.5 and 5.0 mg/L of arsenic, respectively.

Table 6. Pore diffusion coefficients for the adsorption of manganese

at temperature 305 K

Pore diffusion constant D × 10−9 (cm2 /s)

Concentration (mg/L)
0.5 1.5229
1.0 1.1221
1.5 0.7847
2.0 0.5123
2.5 0.4838
Temperature (K)
323 2.5528
Figure 7. Plot of ln Kc and 1/T. Conditions: pH of the electrolyte: 7.0; 333 2.6318
current density of 0.025–0.2 A/dm2 ; concentration: 2 mg/L. 343 2.7109

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This is due to the preferential adsorption of arsenic over Mn as
the concentration of arsenic increases. So, when arsenic ions are
present in the water to be treated arsenic ions compete greatly
with Mn ions for the binding sites.

Silicate
From the results it is found that no significant change in Mn
removal was observed, when the silicate concentration was
increased from 0 to 2 mg/L. The respective efficiencies for 0, 2, 5,
10 and 15 mg/L of silicate are 97.2%, 87.2%, 82.4%, 59.6% and
51.8%. In addition to preferential adsorption, silicate can interact
with magnesium hydroxide to form soluble and highly dispersed
colloids that are not removed by normal filtration.

SURFACE MORPHOLOGY
Characterisation of the Cathode Surface
To investigate the possibility of direct deposition of Mn on the
cathode surface, the EDAX analysis was carried out on the cathode
surface. The results showed that the amount of deposited Mn on
cathode surface is very low. The reason for this phenomenon may
be due to the hydrogen evolution from aqueous solutions will Figure 8. SEM image of the anode after treatment.
compete with metal deposition on the cathode surface. Hence, the
direct cathodic deposition has insignificant effect on the removal
of Mn ions from aqueous solution.
hydroxides. The formation of a large number of dents may be
Characterisation of the Anode Surface attributed to the anode material consumption at active sites due to
A SEM image of magnesium electrode after electrocoagulation of the generation of oxygen at its surface. The elemental constituent
Mn electrolyte was obtained (Figure 8). The electrode surface is of Mn-adsorbed magnesium hydroxide was shown in Figure 9. It
found to be rough, with a number of dents of ca. 10 um. These shows that the presence of Mn, Mg and O appears in the spectrum.
dents are formed around the nucleus of the active sites where EDAX analysis provides direct evidence that Mn is adsorbed on
the electrode dissolution results in the production of magnesium magnesium hydroxide.

Figure 9. EDAX curve of the manganese-adsorbed anode plate.

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 The following conclusions were drawn based on the presented
information:

(1) The optimal removal efficiency of 97.2% was achieved at a

current density 0.05 A/dm2 and at pH 7.0 using magnesium
as anode and stainless steel as cathode.
(2) The first- and second-order model was applied to identify the
kinetics of Mn adsorption onto magnesium hydroxides. The
kinetic results showed that the Mn adsorption on magnesium
hydroxides was best described using the second-order kinetic
model at the various current densities studied.
(3) The electrocoagulation process was modelled using adsorp-
tion isotherm models, viz., Langmuir and Freundlich. The
Mn adsorption was best fitted by the Langmuir adsorption
isotherm, and the results were in good agreement with the
experimental data.
(4) The thermodynamic parameters like
G,
H and
S were
determined. Their values indicated that the adsorption pro-
cess was favourable, spontaneous and endothermic in nature.
Figure 10. FT-IR spectrum of manganese-adsorbed magnesium As the temperature increased from 223 to 343 K,
G became
hydroxide. less negative, indicating a stronger driving force, resulting in a
greater adsorption capacity at higher temperatures. The posi-
tive value of
H confirmed that the process was endothermic.
The positive value of
S suggested that the increased random-
ness of the Mn adsorption from the water containing Mn onto
magnesium hydroxides.
(5) From the surface characterisation studies, it is confirmed that
the magnesium hydroxide generated in the cell-adsorbed Mn
present in the water than direct cathodic deposition.

NOMENCLATURE
R2 regression correlation coefficient values
qt the amount of manganese adsorbate adsorbed on adsorbent
at any time (mg/g)
qe the amount of manganese adsorbate adsorbed on adsorbent
at equilibrium time (mg/g)
t time (min)
k1 the rate constant of first-order model (min)
k2 the rate constant of second-order model (L/g min)
Figure 11. XRD spectrum of manganese-adsorbed electrocoagulant. kf adsorption capacity of the Frendlich isotherm (mg/g)
n adsorption intensity of the Frendlich isotherm
Ce the non-retained manganese (mg/L)
MATERIAL CHARACTERISATION Co different concentrations of manganese (mg/L)
qm the maximum monolayer adsorption capacity (mg/g)
FT-IR and XRD Studies b energy of Langmuir adsorption
Figure 10 presents the FT-IR spectrum of Mn–magnesium hydrox- RL Langmuir equilibrium constant
ide. The sharp and strong peak at 3694.57 cm−1 is due to the (O–H) ko thermodynamical Arrhenius constant (g/mg min)
stretching vibration in the Mg(OH)2 structures. The 1476.6 cm−1 E energy of activation (J/mol)
peak indicates the bent vibration of H–O–H. A broad absorption R gas constant which is 8.314 (J/mol K)
band at 3696.4 cm−1 implies the transformation from free pro- T Temperature (K)
tons into a proton conductive state in brucite. The strong peak at
G Gibbs free energy for adsorption (kJ/mol)
439.2 cm−1 is assigned to the Mg–O stretching vibration (Golder et Kc equilibrium constant of adsorption process
al., 2006; Vasudevan et al., 2010). The spectrum data are in good
H enthalpy of the adsorption (J/mol)
agreement with the reported data (Golder et al., 2006). Mg–Mn
S entropy of the adsorption (J/mol)
is observed in –OH stretching region. The Figure 11 shows the X- t½ half time of adsorption (min)
ray diffraction of Mn-adsorbed magnesium hydroxide. From the D diffusion coeffficient (cm2 /s)
figure it is found that electrocoagulation by product showed the r0 radius of the particle (cm)
well crystalline phase of magnesium hydroxide.
ACKNOWLEDGEMENTS
CONCLUSIONS The authors wish to express their gratitude to the Director, Cen-
The results indicate that the electrocoagulation is a promis- tral Electrochemical Research Institute, Karaikudi to publish this
ing technology for the removal of Mn from drinking water. article.

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REFERENCES
Agrawal, A. and K. K. Sahu, ‘‘Kinetics and Isotherm Studies of
Cadmium Adsorption Manganese Nodule Residue,’’ J.
Hazard. Mater. 137, 915–924 (2006).
Ali, I. and V. K. Gupta, ‘‘Advances in Water Treatment by
Adsorption Technology,’’ Nat. Protoc. 1, 2661–2667 (2007).
Ali, I. and V. K. Gupta, ‘‘Removal of Endosulfan and
Methoxychlor From Water on Carbon Slurry,’’ Environ. Sci.
Technol. 42, 766–770 (2008).
Bedow, K., I. Bekri-Abbes and E. Srasra, ‘‘Removal of Cadmium
(II) From Aqueous Using Pure Smectitic and Lewtite S100 the
Effects of Time and Metal Concentration,’’ Desalination 223,
269–273 (2008).
Dabeka, R. W., H. B. Conacher, J. F. Lawrence, W. H. Newsome,
A. McKenzie and H. P. Wagner, ‘‘Survey of Bottled Drinking
Waters Sold in Canada for Chlorate, Bromide, Bromate, Lead,
Cadmium and Other Trace Elements,’’ Food Addit. Contam.
19, 721–732 (2002).
Demiral, H., I. Demiral, F. Tumsek and B. Karacbacakoglu,
‘‘Adsorption of Chromium (VI) from Aqueous Solution by
Activated Carbon Derived from Olive Baggase and
Applicability of Different Adsorption Models,’’ Chem. Eng. J.
144, 188 (2008).
Drinking Water Advisory Health Advisory for Manganese. U.S.
Environmental Protection Agency Office of Water, Health and
Ecological Division, Washington. www.epa.gov/safewater
Erikson, K. M., K. Thompson, J. Aschner and M. Aschne,
‘‘Manganese Neurotoxicity A: Focus on Neonate,’’
Pharmacol. Ther. 113, 369–377 (2007).
Friberg, L., ‘‘Cadmium,’’ Annu. Rev. Publ. Health 4, 367–388
(1983).
Golder, A. K., A. N. Samantha and S. Ray, ‘‘Removal of
Phosphate From Aqueous Solutions Using Calcinated Metal
Hydroxides Sludge Waste Generated From
Electrocoagulation,’’ Sep. Purif. Technol. 52, 102–109
(2006).
Gupta, V. K., I. Ali and V. K. Saini, ‘‘Adsorption Studies on the
Removal of Vertigo Blue 49 and Orange DNA13 From
Aqueous Solutions Using Carbon Slurry Developed From a
Waste Material,’’ J. Colloid Interface Sci. 315, 87–93 (1997a).
Gupta, V. K., P. J. M. Carrott, M. M. L. Ribeiro Carrott and A.
Suhas, ‘‘Low Cost Adsorbents: Growing Approach to
Wastewater Treatment—A Review,’’ Crit. Rev. Environ. Sci.
Technol. 39, 783–842 (2009).
Gupta, V. K., R. Jain and S. Varshney, ‘‘Removal of Reactofix
Golden Yellow 3RFN From Aqueous Solution Using Wheat
Husk—An Agricultural Waste,’’ J. Hazard. Mater. 142,
443–448 (2007).
Gupta, V. K., A. Mittal, V. Gajbe and J. Mittal, ‘‘Removal and
Recovery of the Hazardous azo Dye Acid Orange 7 Through
Adsorption Over Waste Materials: Bottom Ash and De-Oiled
Soya,’’ Ind. Eng. Chem. Res. 45, 1446–1453 (2006b).
Gupta, V. K., A. Mittal, R. Jain, M. Mathur and S. Sikarwar,
‘‘Adsorption of Safranin-T From Wastewater Using Waste
Materials—Activated Carbon and Activated Rice Husk,’’ J.
Colloid Interface Sci. 303, 80–86 (2006a).
Gupta, V. K., A. Mittal, L. Kurup and J. Mittal, ‘‘Adsorption of
Basic Fuchsin Using Waste Materials—Bottom Ash and
De-Oiled Soya as Adsorbents,’’ J. Colloid Interface Sci. 319,
30–39 (2008).
Gupta, V. K. and A. Rastogi, ‘‘Biosorption of Lead From Aqueous
Solutions by Non-Living Algal Biomass Oedogonium sp. and
| VOLUME 91, MARCH 2013 | |
Nostoc sp.—A Comparative Study,’’ Coll. Surf. B 64, 170–178
(2008a).
Gupta, V. K. and A. Rastogi, ‘‘Sorption and Desorption Studies of
Chromium (VI) From Nonviable Cyanobacterium Nostoc
muscorum Biomass,’’ J. Hazard. Mater. 154, 347–354
(2008b).
Gupta, V. K., A. Rastogi, M. K. Dwivedi and D. Mohan, ‘‘Process
Development for the Removal of Zinc and Cadmium From
Wastewater Using Slag—A Blast Furnace Waste Material,’’
Sep. Sci. Technol. 32, 2883–2912 (1997b).
Gupta, V. K. and A. Suhas, ‘‘Application of Low Cost Adsorbents
for Dye Removal—A Review,’’ J. Environ. Manage. 90,
2313–2342 (2009).
Hamadi, N. K., X. D. Chen, M. Mohammed, G. Q. Farid and M.
G. Q. Lu, ‘‘Adsorption Kinetics for Removal of Chromium(VI)
From Aqueous Solution by Adsorbents Derived From Used
Tyres and Sawdust,’’ Chem. Eng. J. 84, 95–105 (2001).
Izanloo, H. and S. Nassir, ‘‘Cadmium Removal From Aqueous
Solution by Ground Pine Cone,’’ Iran J. Environ. Health. Sci.
Eng. 2, 33–42 (2005).
Jiang, J. Q., N. Graham, C. Andre, G. H. Kelsall and N. Brandon,
‘‘Laboratory Study on Electro-Coagulation-Flotation for Water
Treatment,’’ Water Res. 36, 4064–4078 (2002).
Johnson, B. B., ‘‘Effect of pH, Temperature and Concentration on
Adsorption of Cadmium on Goethite,’’ Environ. Sci. Technol.
24, 112–118 (1990).
Malkoc, E. and Y. Nuhoglu, ‘‘Potential of Tea Factory Waste for
Chromium (VI) Removal From Aqueous Solutions:
Thermodynamic and Kinetic Studies,’’ Sep. Purif. Technol.
54, 291–298 (2007).
Melnik, L., O. Vysotskaja and B. Kornilovich, ‘‘Boron Behaviour
During Desalination of Sea and Underground Water by
Electro Dialysis,’’ Desalination 124, 125–130 (1999).
Mohammad, Y., A. Mollah, P. Morkovsky, A. Jewel, G. Gomes,
K. Mehmet, J. Parge and D. L. Cock, ‘‘Fundamendal, Present
and Future Perspectives of Electrocoagulation,’’ J. Hazard.
Mater. 114, 199–210 (2004).
Mollah, A., R. Schennach, J. R. Parga and D. L. Cocke,
‘‘Electrocoagulation (EC)—Science and Applications,’’ J.
Hazard. Mater. 84, 29–41 (2001).
Mouedhen, G., M. Feki, M. De Petris Wery and H. F. Ayedi,
‘‘Behaviour of Aluminum Electrodes in Electrocoagulation,’’
J. Hazard. Mater. 150, 124–135 (2008).
Nogawa, K., E. Kobayashi, Y. Okubo and Y. Suwazono,
‘‘Environmental Cadmium Exposure, Adverse Effects and
Preventive Measure in Japan,’’ BioMetals 17, 581–590 (2004).
Oguz, E., ‘‘Adsorption Characteristics and Kinetics of Cr(VI) on
Thuja orantalis,’’ Colloids Surf. A 252, 121–128 (2004).
Sekar, M., V. Sakthi and S. Rengaraj, ‘‘Kinetics and Equilibrium
Adsorption Study of Lead (II) Onto Activated Carbon
Prepared From Cocounut Shell,’’ J. Colloid. Interface Sci. 279,
307–313 (2004).
Sohn, S. and D. Kim, ‘‘Modification of Langumuir Isotherm in
Solution Systems—Definition and Utilisation of Concentration
Dependent Factor,’’ Chemosphere 58, 115–123 (2005).
Vasudevan, S. and J. Lakshmi, ‘‘Effects of Alternating and Direct
Current in Electrocoagulation Process on the Removal of
Cadmium From Water—A Novel Approach,’’ Sep. Purif.
Technol. 80, 643–651 (2011).
Vasudevan, S., J. Lakshmi and M. Packiyam,
‘‘Electrocoagulation Studies on Removal of Cadmium Using
Magnesium Electrode,’’ J. Appl. Electrochem. 40, 2023–2032
(2010).
THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING | 457 |
Vasudevan, S., J. Lakshmi and G. Sozhan, ‘‘Effects of
Alternating and Direct Current in Electrocoagulation Process
on the Removal of Cadmium From Water,’’ J. Hazard. Mater.
192, 26–34 (2011a).
Vasudevan, S., J. Lakshmi and G. Sozhan, ‘‘Studies on the
Al–Zn–In—Alloy as Anode Material for the Removal of
Chromium From Drinking Water in Electrolcoagulation
Process,’’ Desalination 275, 260–268 (2011b).
Vasudevan, S., G. Sozhan, S. Ravichandran, J. Jeyaraj and S. M.
Sheela, ‘‘Studies on Removal of Phosphate From Drinking
Water by Electrocoagulation Process,’’ Ind. Eng. Chem. Res.
47, 2018–2023 (2008).
Vasudevan, S., B. Suresh Kannan, J. Lakshmi, S. Mohanraj and
G. Sozhan, ‘‘Effects of Alternating and Direct Current in
Electrocoagulation Process on the Removal of Fluoride From
Water,’’ J. Chem. Technol. Biotechnol. 86, 428–436 (2011c).
WHO., ‘‘Manganese in drinking water,’’ Background document
for development of WHO guidelines for drinking water
quality report (2004).
Yang, X. Y. and B. Al-Duri, ‘‘Application of Branched Pore
Diffusion in the Adsorption of Reactive Dyes on Activated
Carbon,’’ Chem. Eng. J. 83, 15–23 (2001).
Youssef, A. M., T. E. Nabarawuy and S. E. Samra, ‘‘Sorption
Properties Chemically Activated Carbons 1. Sorption of
Cadmium(II) Ions,’’ Colloids Surf. Physicochem. Eng.
Aspects 235, 153–163 (2004).

Manuscript received December 2, 2011; revised manuscript

received February 4, 2012; accepted for publication February 8,
2012.

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