20320140501003

International Journal of Civil Engineering and Technology (IJCIET), ISSN 0976 – 6308
INTERNATIONAL JOURNAL OF CIVIL ENGINEERING AND
(Print), ISSN 0976 – 6316(Online) Volume 5, Issue 1, January (2014), © IAEME

TECHNOLOGY (IJCIET)

ISSN 0976 – 6308 (Print)
ISSN 0976 – 6316(Online)
Volume 5, Issue 1, January (2014), pp. 21-34
© IAEME: www.iaeme.com/ijciet.asp
Journal Impact Factor (2013): 5.3277 (Calculated by GISI)
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IJCIET
©IAEME

REMOVAL OF THE BLUE METHYLENE DYE FROM AN AQUEOUS
SOLUTION BY USING POWDERED CORN COB
Rasha Salah Mahdi
Department of Environmental Engineering, College of Engineering, University of Babylon

ABSTRACT
This study deals with removal of dyes from industrial water by using the corn cob powder.
The adsorption isotherm of the alkaline methylene blue was examined by using Langmuir and
Freundlich isotherms. It also investigates the contact time and acidic effect on the adsorption surface
and records the change that each effect caused when other factors were constant. Results revealed
that the adsorption of methylene blue is gradually increased with an increase in adsorbent dosage
when using concentrations ranging from 0.25-1.5 g, and then the adsorption becomes gradually
constant at 1g. The nature of the adsorbate substance was also examined. It was found that the
adsorbatedose (qe) is increased with the increase of the residual concentration (ce). As for the effect
of the contact time, it was found that the adsorbatedose (qe) decreases with an increase of the
residual concentration. The capacity of adsorption is also affected by the PH. It was found that the
adsorbent has an acidic property following the order PH: 7> 10 > 2. From the adsorption isotherm of
methylene blue, it can be found that it is closer to the Freundlich adsorption Equation than
Langmuir’s, where RF=0.976, while RL=0.77.
Keywords: Adsorption, Blue Methylene, Corn Cob, Powder, Aqueous Solution.
INTRODUCTION
Environment pollution is one of the most serious problems currently facing mankind. Human
beings even make this issue more serious with their different activities, making things life-threaten.
Pollution of environment has close relation with population expansion all around the world. Human
beings want to get rid and avoid unnecessary colors, flavors, and smell or keep them at least in
reasonable limits from health and psychological aspects. Has water purification process achieved this
demand?

21

Sources of fresh water has recently witnessed deterioration with the production of new
pollutants due to technological advancement, and because of leakage of minerals such as iron and
magnesium into fresh water, as well as insecticides which lead to different communicative diseases.
There are many types of pollution: chemical, organic, thermal, and radioactive. World Health
Organizations (WHO) reports indicate that most communicative diseases in developing countries are
due to water pollution. Researchers have conducted different methods for the treatment of industrial
waters such as sedimentation, coagulation, filtration, and sterilization. The process of adsorption on
solid sublimed surfaces is one of the common methods used to purify polluted water. Many research
methods have been conducted on sublimed surfaces such as ash, wood, cellulose, active carbon, and
silica, as well as the remains of wheat residue, eggshell and others(1).
USING NATURAL MATERIALS IN TREATING INDUSTRIAL WATER
It is well-known that residues of industrial water resulting from texture and tannery plants
contain dyes ranging from 10-50 mg/L, and large amount of surface-active material, in addition to
dissolved salts and high PH. There are also traces of transitional metals such as Cu, Cr, and Ni which
cause considerable damage to the environment. Many countries conduct researches to treat industrial
water, especially water coming out of texture and tannery plants with aim of removing dyes from
these residues before reaching mainstream river. For this reason, physical and chemical methods
were used. Some were conducted by direct sedimentation or separation of dye pollutants, or by using
adsorption on active carbon or similar materials. Some researchers indicated the possibility of
separating dyes from residues of texture solutions using Aluminum Sulfate as a coagulant (PH=1-8),
with a success not exceeding 50%. Away from traditional methods, the Advanced Oxidation Process
(AOPs) which rely on generating very active reagents such as hydroxyl group which oxidize organic
pollutants of all different kind in high speed(3).
In this research, we will not use chemical substances to treat industrial water; it will use
natural substances such as corn cob as an adsorbent of dyes. We use the corn cob because it is locally
available and of low cost; besides, it is eco-friendly. The purpose of using this substance is to
improve quality of industrial water resulting from some industries.
ADSORPTION
This method is used to remove organic pollutants of very low concentration, toxic
compounds and dyes which are not easily removed from industrial water. These substances can be
removed to large extent by using the process of adsorption on surfaces of many substances of high
sublimity such as the activated carbon, Aluminum Oxide, animal coal, and others.
Adsorption can be defined as the “adhesion of atoms, ion, or molecules of a gas or liquid on solid
surface. Two types of adsorption can be distinguished(5): polar adsorption such as alumina and
calcite, where the polarity of the solute affects fixation density. The second type is the non-polar
adsorption such as coal where the size and shape of molecules and the surface affect the adsorption
process.
The substance undergoing adsorption is referred to as “adsorbate” such as phenols, ammonia,
dyes, etc (pollutants); whereas the surface on which the adsorption takes place is called the
“adsorbent” such as the activated carbon. The adsorption process involves contacts between the
surfaces of liquid and solid phases with each other, where the liquid phase is either purified or
containing one or more dissolved substances.
The adsorption process is accompanied by decrease in free energy ( G) of the surface; this
implies that the adsorption process is spontaneous. It is also accompanied by decrease in entropy
( S) because the molecules undergoing adsorption become restricted due to its adhesion to the
22

surface, hence losing some degree of freedom. The decrease in free energy and entropy lead to
decrease in enthalpy H, according the following relationship:
G= H-T S
FACTORS AFFECTING ADSORPTION
1- The Nature of adsorbent
Adsorption is affected by the nature of an adsorbent and polar groups existed on the surface.
It is also affected by surface area and size and distribution of surface areas in terms of homogeneity
and alignment. Further, it is affected by surface polarity and predominant charge. For example, the
amount of adsorption on (ᾳ- Alumina) is greater compared with that on Silica or Kaolin; the reason
behind that is that the surface of Alumina is positively charged while the Kaolin and Silica are
negatively charged.
2- Nature of adsorbate
The overlap between the adsorbent and particles of the adsorbate is affected by the nature of
the adsorbate in terms of size, shape, and polarity, as well as by the existence of active groups,
solubility, and molecular weight. This difference may lead to what referred as the “selective
adsorption” (selection of one component rather than the other). The insecticide “Baraqut” has high
selection ability on mud compared with other insecticides. This can be explained by the fact that the
Baraqut has high polarity, producing organic cations which have high tendency to adhere to mud
surfaces which have negative charges.
3- Temperature
Generally, the adsorption process is exothermic; consequently, the amount of adsorbate
decreases with the increase of temperature at the point of equilibrium. Temperature increases the
energy of adsorbate molecules and results in the separation of molecules from the surface of
adsorbent surface to return to the solution.
4- The effect of PH
The effect of solution PH varies in the adsorption process with the difference of the
adsorption system. The changes in the PH lead to increase of adsorbate solubility in the solution,
resulting in decreased adsorption. This is in contrary to changes that lead to decreased solubility of
adsorbate molecules. Additionally, if the surface of an adsorbent has different charge than that of the
adsorbate particles, the adsorption is increased on surfaces containing charged and polarized sites;
the opposite is true if the charges of the surface and adsorbate particles are the same.
MATERIAL AND TOOLS
Material
1- Powdered corn cobs: it is used as a natural element for the adsorption process after being dried.
Corn cobs are the corns after removing grains from them as seen in figure 1. The corn cobs are
known for their low digestion coefficient due to increased lignin content of the wall of the cell
which is connected to the cellulose and hemi-cellulose with strong bonds. This strong bonding
makes it hard to microorganisms existing in the animal tripe to break these bonds, resulting in
less benefiting from these nutrients. Corn cobs are is lingo-cellulose residues which have proved
to have the potential of removing Aluminum ions from aqueous solutions just as a natural
23

adsorbent does. Corn cobs even have better advantage in this respect since they are available in
Iraq (constitute 20% of the corn) and do not cost much.

Figure (1): corn cobs
2- Methylene blue: it is an alkaline dye with a molecular weight of 373.9*10-3. It is easily adsorbed
at a wave length of 664.(4) It has the following chemical structure(2) (figure 2):

Figure (2): structure of Methylene blue
3- Sodium Chloride or Sulfuric Acid to neutralize the solution
4- Distilled water to dilute the dye
5- Filter papers
Tools and Methodology
1- Absorbability was recorded using a device (UV-spectrophotometer)
2- Scale(Denver instrument)
3- PH measurement device
4- Lab Tech 250 rpm vibrator(shaker)
5- Volumetric flask
6- Sieve
Methodology
Methylene blue solutions were prepared by dissolving 0.1gm of it in one liter of distilled
water to prepare six solutions of the methylene blue dye of 100ppm concentration. The following
weights of corn cobs were placed in these solutions: (0.25, 0. 5, 0.75, 1, 1.25 and 1,5) gm. These
were placed in a vibrator for two hours. Then solutions were filtered using filter papers. Later
absorbability was measured for each sample after the adsorption process. Absorbability was then
projected on a curve to find the concentration. The following linear equation was also used for the
curve using UV device:

24

Y =7.9377X + 0.0141 …………………………. (1)
Where:
(Y)is the concentration at the equilibrium point for the adsorbate (ce) (mg/L)
(X) is the absorbability
To obtain adsorption isotherm, six diluted solutions of the dye were prepared having concentrations
from 10 -100 ppm in 100ml volumetric flasks. They were put in contact with (1)gm of corn cobs and
then put in the device for two hours at a speed of 250rpm. The absorbability of each sample was
measured by the UV device to calculate the dose of the adsorbate, as follows:
(C0 – Ce) Vsol
qe= ---------------------………………………(2)
M
Where:
qe = dose of the adsorbate mg(dye)/g (dose)
Co = the initial concentration of the adsorbate mg/L
Ce= the concentration at equilibrium mg/L
Vsol= total volume of the adsorbate solution (L)
M=Weight of the adsorbent (gm)
From the 100 ppm concentrations, solutions from changing the media were prepared ranging from
PH=2 to PH=11. When the contact time was examined, six flasks of one concentration (100mg/l)
were taken. These flasks were put in the vibrator device. The first flask was drawn after 20 minutes.
It was then filtered by filter paper and placed in the UV device and the absorbability was measured.
The same process was used with other flasks. This action has been after every twenty minutes to the
extent of 120 minutes.
RESULTS AND DISCUSSION
In this study, the following factors were investigated:
1- The effect of the weight of the adsorbent surface
To study this effect on the capacity of adsorbate methylene blue dye on the surface of corn
cob, different weights of adsorbent were experienced, as illustrated in the figures( 3, 4, 5,6,7). These
weights were( 0.25, 0.5, 0.75, 1, 1.25, and 1.5 gm). The rest of factors were constant. It was found
that the capacity of adsorption of the dye is affected by the weight of the surface. When the weight of
the adsorbent is increased, the dose of adsorbate in increased, then it starts to be constant at the
weight 1gm, then it decreases at the weight 1.25 gm, then it starts to rise at 1.5gm. The effect of
changing concentrations on the value of PH is changing, starting with gradual decrease with
increased concentrations.

Figure (3): shows solutions before adding corn cobs
25


Figure (4): shows solutions after adding corn cobs
6.00

C( g )
e m /L

5.00

4.00

3.00

2.00
0.00

0.40

0.80

1.20

1.60

Dose of adsorbent (g)

Figure (5): shows the relations between different weight of corn cobs and the concentration at
equilibrium

98.00

R m v l( )
e oa %

97.00

96.00

95.00

94.00
0.00

0.40

0.80

1.20

1.60

Dose of adsorbent(g)

Figure (6): shows efficiency of the removal of the dye by using different doses of corn cobs

26

0.04

q e ( mg / g )

0.03

0.02

0.01

0.00
2.00

3.00

4.00

5.00

6.00

Ce(mg/L )

Figure (7): shows the relation between dose of adsorbent and concentration at equilibrium

2- Nature of adsorbate
To study the nature of the adsorbate, the dye concentrations where changed from 10-100
ppm, keeping other factors constant. These concentrations were placed in 100ml bottles. Then, they
were place in contact with 1gm of corn cobs and place in a device for two hours at a speed rate of
250rpm. It was found that the dose of adsorbate (qe) is increased with the increase of reside
concentration (ce). In order to find the adsorption isotherm, these concentrations were prepared from
the dye as illustrated in the figures of adsorption isotherm (8, 9, and 10).
3.50

C ( mg / L )
e

3.00

2.50

2.00

1.50

1.00
0.00

20.00

40.00

60.00

80.00

100.00

Co ( m g / L )

Figure (8): shows the relationship between the initial concentration of the methylene dye and
the concentration at equilibrium

27

10.00

q e ( mg / g )

8.00

6.00

4.00

2.00

0.00
0.00

20.00

40.00

60.00

80.00

100.00

Co ( m g / L )

Figure (9): shows the relationship between the initial concentration of the methylene dye and
the dose of the adsorbate
10.00

q e ( mg / g )

8.00

6.00

4.00

2.00

0.00
1.00

1.50

2.00

2.50

3.00

3.50

Ce(mg/L)

Figure (10): shows the relationship between the concentration at equilibrium and
adsorbatedose
3- Contact time
The contact time affects the adsorption capacity of methylene blue on corn cobs surface to
reach a state equilibrium. It was noted that it takes 60-120 minutes for the equilibrium to take place,
and the dose of the adsorbate decreases with the increase of the residue concentration (Ce). This
means that an hour is enough for the equilibrium to take placeand explain the interaction mechanical
to migration and the movement of dye molecules from the solution to the surface by impact of
distribution and dispersion forces to reach a state of equilibrium at the time in question, as shown in
the figure (11,12, 13).
28

9.90

qe(m / g)
g

9.89

9.88

9.87

9.86

9.85
1.25

1.30

1.35

1.40

1.45

1.50

Ce ( m g / L )

Figure (11): shows the relation between the residue concentration and the adsorbate on the
surface of the corn cobs affected by the contact time
1.50

C (mg / L )
e

1.45

1.40

1.35

1.30

1.25
20.00

40.00

60.00

80.00

100.00

120.00

Time ( minute )

Figure (12): shows the relationship between the contact time and the residue concentration on
the surface of the corn cobs
9.90

q e (m g / L )

9.89

9.88

9.87

9.86

9.85
20.00

40.00

60.00

80.00

100.00

120.00

Time ( minute )

Figure (13): shows the effect of contact time on methylene blue adsorption on the surface of
corn cobs

29

4-The PH effect
The study showed the effect of the PH in the adsorption of the methylene blue at a different
PH (2, 4, 6, 8, 10, and 11). The results revealed that the PH has different effect, as shown in figures
(14, 15). The dose of the adsorption of methylene blue increased when the solution was nearing
equilibrium, and it decreases when the solution become alkaline (PH = 10 and 11). It slightly
decreases when the PH = 2. This can be explained as follows: the surface used has neutral charges,
and the methylene blue in a neutral medium has a positive charge. Additionally, the active group is
the CH3- group. All these factors contribute to forming Vanderforces and electrostatic attraction
forces, forcing the methylene to adhere to the surface more than staying in its aqueous solution.
2.00

C (mg / L)
e

1.80

1.60

1.40

1.20
2.00

4.00

6.00

8.00

10.00

12.00

pH

Figure (14): shows the effect of PH on methylene blue adsorption on the surface of corn cobs
9.88

qe(m
g/g)

9.86

9.84

9.82

9.80
1.20

1.40

1.60

1.80

2.00

Ce(mg/L)

Figure (15): shows the relationship between the residue concentration and the adsorbate on the
corn cob surface due to acidity

30

DETERMINATION OF ADSORPTION ISOTHERMS
Figure (16) shows the adsorption isotherm of the dye from its aqueous solutions on the corn
cob surface. It can be deduced that these isotherms to the overlap of the adsorbate with the adsorbent
through different types of forces. In nature, the dyes are organic compounds containing electron
donating and electron drawing groups which affect the quantity of adsorption. The negative and
positive charges are distributed on the surface, leading to the formation of different physical forces
such as the hydrogen bond, electrostatic forces, and dipolar induction forces(1). The methylene blue
adsorption data were processed in the light of the logarithmic equations of Freundlich and
Langmuir(6):
Log qe = log Kf + 1/n log ce …………………………….. (3)
When drawing qe against ce, we get straight line having the slope 1/n which is a measure of
the intensity of adsorption. The intersection logK is a measure of adsorption capacity as in table (1)
and figure (16). The equation of Langmuir is:
Ce/ qe = 1/KI + (a/k). ce ………………………………….. (4)
This is the linear formula for Langmuir where a and k are constant of Langmuir which can be
obtained by drawing ce/qe against ce to get a straight line having the slope a/k and the intersection
1/kas in figure (17). Table 2 shows the values of constants studied in the equations of Freundlich and
Langmuir where (Kf) is the adsorption capacity,( n) is the adsorption coefficient, (kI) the adsorption
capacity, and (a) is the energy of adsorption. Correlation coefficients R2 were also determined to
describe the adsorption isotherm. It was noted that R2 for Freundlich equation is more than R2 for
Langmuir equation. The qe of Freundlich and Langmuir for the adsorption of methylene blue versus
qe calculated from equation (2) are illustrated in Table 3 and figure 18..
Linear, Y=B*X+A
Equation:
Y = 2.88781 * X + -0.43568
Number of data points used = 6
Average X = 0.3475
Average Y = 0.567833
Regression sum of squares = 0.790825
Residual sum of squares = 0.0187697
Coef of determination, R-squared = 0.976816
Residual mean square, sigma-hat-sq'd = 0.00469243

1.20

Lg e
o (q )

0.80

0.40

0.00

-0.40
0.10

0.20

0.30

0.40

0.50

0.60

Log(Ce)

Figure (16): shows the straight lines of Freundlich for the adsorption of methylene blue on the
surface of the corn cobs
31

Linear, Y=B*X+A
Equation:
Y = -0.645037 * X + 2.21341
Number of data points used = 6
Average X = 2.31833
Average Y = 0.718
Regression sum of squares = 1.00044
Residual sum of squares = 0.296343
Coef of determination, R-squared = 0.771478
Residual mean square, sigma-hat-sq'd = 0.0740857

2.00

Fit 1: Linear, Y=B*X+A

1.60

C /q (g )
e e /L

1.20

0.80

0.40

0.00
1.00

1.50

2.00

2.50

3.00

3.50

Ce (mg/L)

Figure (17): shows the straight lines of Langmuir for the adsorption of methylene blue on the
surface of the corn cobs
20.00

qe(mg/g)
16.00

qe Experimental
qe Langmuir isotherm
qe Freundich isotherm

qe g/g)
(m

12.00

8.00

4.00

0.00
1.00

1.50

2.00

2.50

3.00

3.50

Ce(mg/l)

Figure (18): shows the qe of Freundlich and Langmuir for the adsorption of methylene blue
versusqe calculated

32

Table 1: shows the adsorption of methylene blue on the surface of corn cobs.
Langmuir equation

Freundlich equation

Co

Ce

Qe

Ce/qe

mg/
L

mg/L

mg/g

g/L

10

1.42

0.858

20

1.69

40

Co

Ce

Qe

Log qe

Logce

mg/L

mg/L

g/mg

mg/g

mg/L

1.66

10

1.42

0.858

-0.067

0.1523

1.831

0.93

20

1.69

1.831

0.263

0.228

2.1

3.79

0.554

40

2.1

3.79

0.579

0.322

60

2.7

5.73

0.471

60

2.7

5.73

0.758

0.431

80

2.8

7.72

0.363

80

2.8

7.72

0.888

0.447

100

3.2

9.68

0.33

100

3.2

9.68

0.986

0.505

Table 2: shows constant values of Freundlich and Langmuir of the used dye
Dyes

Freundlish con.

Langmuir con.

݊
metheylene blue

Log Kf

ܴ ଶ .F

A

K.L

ܴ ଶ .L

0.35

-0.44

0.976

-0.29

0.45

0.77

Table 3: show the dose of adsorbateqe mg/g.
Co

Ce

(qe)
Experimental

(qe)
Langmuir
equation

(qe)
Freundlich
equation

mg/L

mg/L

mg/g

mg/g

mg/g

10

1.42

0.858

1.08

0.99

20

1.69

1.831

1.49

1.64

40

2.1

3.79

2.417

3.07

60

2.7

5.73

5.59

6.35

80

2.8

7.72

6.7

7.06

100

3.2

9.68

2.0

10.38

33

CONCLUSIONS AND RECOMMENDATIONS
Conclusions
1- The adsorption of the used dye (methylene blue) on the surface of corn cobs follows the
adsorption equation of Freundlich equation more than Langmuir equation
2- The study shows that the PH has different effect on the adsorption capacity of the methylene
blue. The dose of adsorption increased with the solution was nearing equilibrium and
decreased when the solution is alkaline.
3- Contact time has an effect on adsorption capacity of methylene blue. It was noted that the
time of equilibrium ranged from 60 to 120 minutes.
Recommendations
1- This study sheds the light on using low-cost adsorbents of high adsorption capacity for the
removal of dyes from their solutions
2- Methylene blue was used in coloring these surfaces by means of adsorption on surfaces. This
means that other dyes can be used.
3- The study of the desorption process to examine the constancy of dyes on the used surface.
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