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ISSN: 0970-020 X

ORIENTAL JOURNAL OF CHEMISTRY CODEN: OJCHEG


An International Open Free Access, Peer Reviewed Research Journal
2015, Vol. 31, No. (2):
Pg. 643-651
www.orientjchem.org

Adsorption Behavior of Methyl Orange onto


Wheat Bran : Role of Surface and pH
ATEF S. ALZAYDIEN*

* Department of Chemistry, Mutah University, P. O. Box 7, Jordan


*Corresponding author E-mail : [email protected]

http://dx.doi.org/10.13005/ojc/310205

(Received: March 30, 2015; Accepted: May 11, 2015)

ABSTRACT

This paper deals with the application of wheat bran (WB), an agricultural by-product, for the
adsorption of methyl orange (MO) from aqueous solution. The characteristics of WS surface, such as
surface functional groups, zero of point charge and conductivity were obtained. The removal of MO
onto WB from aqueous solution was investigated by using parameters, such as pH, temperature,
adsorbent dose and contact time. A spectrophotometer technique was used for measuring the extent
of adsorption. The extent of dye removal decreased with increasing adsorbent dosage and also increased
with increasing contact time and temperature. The results revealed that the sorption capacity increases
from 12.34 to 19.85 mg/g when the temperature increased from 25 to 55 éþC. This suggests that the
sorption of MO dye onto WB is endothermic and activated process indicating that the higher temperature
is more favorable for the dye sorption. Optimum pH value for dye adsorption was determined to be 4.0.
strong pH-dependence of MO adsorption onto WB together with FTIR results indicate to possible
involvement of physical forces such as hydrogen bonding, Vander Waals and covalent chemical
bonds in the adsorption process. In addition, the adsorption data of MO by WB were applied to
Lagergren,s pseudo first-order, pseudo second-order and the rate constants of first-order adsorption
(k1 = 1.34x102 min-1) the rate constants of second-order adsorption (k2 = 2.93x10-3 g/mg min) were
calculated, respectively. The results indicate that WB could be employed as a low-cost alternative to
other adsorbents in the removal of MO from aqueous solution.

Key words : Adsorption, WB, MO, Surface, PH, Temperature, Rate.

INTRODUCTION of which are difficult to biodegrade due to their


centupled structure and synthetic origin 3. The
Synthetic dyes are widely used for textile presence of very low concentrations of dyes in
dyeing , paper printing ,leather dyeing , color effluent is high visible and undesirable. Colored
photography and as additives in petroleum agents interfere with the transmission of light
products1. They exhibit a wide range of different through water and hinder photosynthesis. Most of
chemical structures, primarily based on substituted these dyes are harmful, when they are in contact
aromatic and heterocyclic groups2. There are more with living tissues for along time4. Physico–chemical
than 100,000 dyes available commercially, most or chemical treatment of such wastewater is
644 ALZAYDIEN, Orient. J. Chem., Vol. 31(2), 643-651 (2015)

however possible. Many invesligators have studied lead to intestinal cancer13.


different techniques for removal of colored dye from
wastewater ,e.g., Chemical coagulation, Adsorption may be classified as physical
nanofiltration, and adsorption onto different or chemical depending on the nature of forces
materials5. involved. When adsorption occurs without any
chemical reaction , it is generally termed as” physical
Although commercial activated carbon is adsorption “ . It is brought about as a result of Vander
a preferred adsorbent for color removal, its use is Waals forces. If the adsorbate undergoes chemical
restricted due to high cost. In the country where interaction with the adsorbent, the phenomenon is
economy plays a very big role, there is a need to reffered to as “chemical adsorption “ . It is involved a
search for low-cost affective sorbents. It well know sharing of electrons between the adsorbate
that natural materials, waste materials from industry molecules and surface of the adsorbent14. This
and a agriculture and biosorbents can be obtained chemistry may include complexation involving
and employed as inexpensive sorbents. recently, ligand exchange, covalent bonding ,hydrogen
an extensive list of sorbent literature for dye removal bonding and our understating may even be
has been complied by Crini and Banat et al.,4,6. stretched to include steric or orientation effects15.
The equilibrium adsorption isotherm is fundamental
Wheat is one of cereals used for the in adsorption, and is important in the design of
preparation of bread and other bakery products ,and adsorption system. This rate controls the residence
wheat bran is the by –product of wheat bread time of adsorbate uptake at the solid – solution
production industry. WB is a rich source of dietary interface 16. The adsorption of dyes is mainly
fibers and contains carbohydrates, proteins, starch, depedent on the dyes properties and Structure, and
sugar and celluloses7. There has also been some to an equal extent on the surface chemistry of the
research into the use of WB as an adsorbent . adsorbent .The role of Texture and surface
Farajzadeh and Monjig7 reported the adsorption of functional groups of sorbent must be explored
heavy metals by WB . Butut and Baysal studied the and highlighted in any adsorption process.
removal of pb(II) using WB as low cost sorbent8,9. Investigations describing the adsorption of dyes on
Cicek et.al. used WB to remove reactive dyes. solids rarely explain the role of the surface chemistry
Hamdaoui and Chua showed the suitability of WB and to some extent on the effect of Various operating
for cationic dye MB adsorption10. Ozer and Dorsum parameters influencing the adsorption process17,18.
prepared Activated carbon from WB dehydration11.
Dyes are classified into three broad categories (a) The aim of present study was to examine
anionic : direct, acid and reactive dye; (b) cationic: optimum adsorption conditions such as pH, sorbent
all basic dyes and (d) nonionic : dispersed9. Methyl dose, contact time and temperature of cost–effective
Orange is a water soluble azo dye, which is a widely sorbent . The surface characteristics of the adsorbent
used in the textile, printing, paper manufacturing , were determined versus point of zero charge, FTIR
pharmaceutical , food industries and also in analysis of the surface functional groups, pH and
research laboratories. In the Analytical Chemistry conductivity measurements. The adsorption kinetic
laboratories it is mainly used as an acid base properties were also explored.
indicator due to its ability to function as weak acid
as the aqueous solution of the dye has a pH value MATERIALS AND METHODS
a proximately 6.5 (5g/l , H2O, 20°C)12.
Reagents and apparatus
A dyes are well known carcinogenic All chemicals used in this study were of
organic substances. Like many other dyes of its analytical reagent grade. Doubly distilled water was
class Methyl orange on inadvertently entering the used in solution preparation. The pH pf solution was
body through ingestion, metabolites into aromatic measured using pH-meter (315i/SET). The
amines by intestinal microorganisms. Reductive absorbance of dye solution was measured using
enzymes in the liver can also catalyze the azo an UV-VIS spectrophotometer (spectronic 20D+).
Linkage to produce aromatic amines and can even The conductivity measurements were done using a
ALZAYDIEN, Orient. J. Chem., Vol. 31(2), 643-651 (2015) 645

conductivity meter. The FTIR spectra were recorded measuring absorbance of different predetermined
using spectrophotometer (Mattson 500, UK ). A concentrations of the samples at 2ûmax = 506 nm.
mechanical shaker (Labortechnik mbH, Germany) Final concentration of dye in experimental solution
with a constant temperature water bath was used was calculated from the linear regression equation
for all the adsorption experiments for agitating the ( Absorbance= 0.0337*concentration (mg/l) +0.025)
samples for a desired contact time. of the calibration curve. The synthetic dye sample
calibrated in order to find out various absorbencies
Adsorbent preparation at various concentrations. The calibrated results are
WB used in this study was purchased from very effective to identify the respective color removal
local flour mills (Mutah, Jordan). capacities of the WB adsorbent. Fig.1 shows the
graphical representation of the calibration of MO.
The material was washed several times
with distilled water to remove all dirt particles. The Equilibrium adsorption studies
washed WB was then dried in a hot oven at 70°C Experiments were conducted using a
for 8 h to constant weight . The sorbent material batch procedure. 100 ml aqueous solution of MO
was screened through 5.6 mm sieve and used as with predetermined initial concentration (20-100
such without any pretreatment. mg/l) was taken in different 250 ml stoppered
Erlenmeyer flasks. Powdered WB (0.5 g) was added
Adsorbent characterization to each flask. The flasks were agitated (160 rpm) at
Determination of pH point of zero-charge 25±1 éþC for 240 min, which is expected to be the
The pH point of zero-charge (pHZPC ) of time required to reach equilibrium. At the end of
WB was carried out as described elsewhere agitation sorbent was separated by filtration through
(Onyango et al., 2004) : 50 ml of 0.01M NaCl filter paper. The first part of filtrate was discharged
solutions were placed in different closed to avoid effects of dye adsorption on the filter paper.
Erlenmeyer flasks and corked. The pH of each The residual concentration of the dye in the
solution in each flask was adjusted to initial (pHi) supernatant was estimated spectrophotometrically.
values 2, 4, 6, 8, 10 and 12 by adding 0.1M HCl or The same experiment was repeated at two different
0.1M NaOH solutions. Then 0.5 g of WB was added temperatures (40°C and 60°C). The effect of pH on
and agitated in a shaker for 1 h and allowed to stay sorption studies was investigated in the pH ranges
for 24 h to reach equilibrium at ambient temperature. of 2-10.
At the end of 24 h contact period, the final pH values
(pHf) were measured. The pHZPC was determined A series of experiments were also
from the plot of pHf versus pHi. conducted for different sorbent doses varying
between 0.5-2.0 g per 100 ml dye solution. Blank
FTIR analysis containing no dye were conducted at similar
The surface functional groups on free and conditions as control. The influence of operating
dye loaded WB were examined using Fourier parameters were studied by varying one parameter
transform infrared (FTIR) spectroscopy. Discs were an keeping other constant. Stirring speed of shaker
prepared by first mixing 1 mg of powdered WB with was kept constant thus ensuring equal mixing.
100 mg of KBr in an agate mortar, then pressing the
resulting mixture under 10 tons/cm2 for 5 min. The Adsorption kinetics
spectra were recorded between 4000 and 400 cm- The above experiment was repeated with
1
using a Mattson 5000 spctrophotometer, UK. 100 mg/l MO solution at 25±1°C and concentration
of dye in the solution was determined at different
Preparation of MO solutions time intervals. Each data point obtained from
The characteristics of MO dye are given in individual flask and therefore no correction was
Table.1. Stock solution of MO (1g/L) was prepared necessary due to withdrawal of sampling volume.
in doubly distilled water and desired concentrations
of the dye were obtained by diluting the same with Calculations
water. Calibration curve of MO was prepared by The amount of dye adsorbed per unit
646 ALZAYDIEN, Orient. J. Chem., Vol. 31(2), 643-651 (2015)

weight of adsorbent (Qe, mg MO/g WB) was the initial and the final pH values (pHi and pHf,
calculated as respectively). pHf readings for the determination of
pHZPC were plotted as a function of pHi in Fig. 2. The
Qe = (C0-Ce) *V/S ...(1) pH f value of the plateau observed in Fig. 2
corresponds to the pH at which there is no net OH-
Where C0 and Ce, the concentrations of or H+ adsorption. At this pH, the difference between
MO dye (mg/l) in aqueous phase, respectively before the initial and the final [H+] or [OH-] is zero. This pH
and after adsorption; V is the volume of dye solution was determined to be 6.3 and taken as the pHZPC of
(ml); S is the weight of WB (g). the WB. The recorded FTIR spectra of free and dye
loaded WB are depicted in Fig. 3a and Fig.3b. The
RESULTS AND DISCUSSION FT-IR analysis of the WB showed the presence of
the following groups . C=O(1649.24cm -1 ), -
Adsorbent characterization OH(3423.86cm-1),C=C(1675 cm-1), C- O(1080.21cm-
1
The pHZPC of WB used in the present study ), N-H(1155.43 cm-1),and NH2(3400-3500 cm-1). The
was previously measured by batch equilibrium intense peak at a frequency level of 3423,86 cm-
1
method. At the end of 24 h contact period, the amount represents a mino group(-NH2) stretching vibration
of H+ or OH- ions adsorbed by WB was calculated band. The -NH2 bands are superimposed on the
from the difference between the initial and the final side of hydroxyl (-OH) group at 3500-3300cm-1. The
concentrations of H+ or OH- ions, determined from strong peak at around 1650 cm-1 is caused by the

Table 1: The characteristics of MO dyea

Chemical name p-dimethylamonoazobenzenesulphonate

Chemical formula C14H14N3NaO3S

Chemical structure

Molecular weight 327.34 g/mol


Type of dye Acidic azo dye
 max 506 nm

a
The data were obtained from Aldrich-Sigma chemical databases
website : http://www.sigmaaldrich.com/catalog/product/sigma/c3886?lang=en&region=JO

C=O stretching band of carbonyl groups. The peak disappeared. These changes confirmed the
at 1155.43 cm-1 can be assigned to bending modes participation of WB surface functional groups
of-CH3 and some aromatic compounds. The strong (C=O1– NH21- OH and –OCH3) in the adsorption
C-O band at 1080.21 cm-1is due to –OCH3 group. reaction. Based on FTIR spectroscopy we
The peak at 1026.19 is characteristic of C-O group suggested that the interaction of MO and WB occurs
of primary hydroxyl stretching that may be attributed between active surface sites of WB and SO-3 –N
to cellulose structure of WB. In spectrum of MO- =N- group on MO .
loaded WB( figure 1b) the frequencies of free WB
are shifted e.g.- NH2 group appears at 3435.44 cm- Effect of pH on dye adsorption
1
C=O group appears at 1635.74 cm -1 and In general, initial pH value may enhance
characteristic C=O frequency appears at 1024.27. or depress the uptake of solute. pH of adsorption
The peaks at 1155.43 cm -1 and 1080.21 cm -1 medium influences not only the surface charge of
ALZAYDIEN, Orient. J. Chem., Vol. 31(2), 643-651 (2015) 647

adsorbent, the degree of ionization of the material affected by the pH value of the solution and acidic
present in the solution and the dissociation of pH was favourable for the adsorption of the dye.
functional groups on the active sites of the adsorbent, Similar result was also obtained fro the adsorption
but also the solution dye chemistry20. The study of MO onto activated alumina at an initial pH 4.021.
evaluated the effect of pH on the adsorption of MO In order to understand the role of pH on the sorption
by WB over a wide range of pH (2.0-10.0). The process, the surface charge of WB was determined
influence of pH on adsorption of the dye is shown by measuring the pHZPC. The effect of pH can be
in Fig. 4. Adsorption of MO by WB had been found described on the basis of the influence of pH on the
to be dependent on pH of the solution, which zero point of charge (pHZPC), which is the point at
increased with the decrease in pH. From Fig. 4, it which the net charge of sorbent surface is zero.
can be seen that the amount of dye adsorbed on According to Al-Degs et al., pHZPC can be used as
the WB is high for pH between 2 and 6.3 and the
8
best color removal 16.48 mg of dye per gram of WB
was achieved at pH 4.0.The adsorbed amount of
dye was lower at strongly acidic (2.0-3.0) and was 7

much lower at alkaline (8.0-10.0) conditions.


Therefore, the results clearly indicate that the 6

sorption of MO dye onto WB was significantly


5
0.8
Final pH

0.7
4

0.6

0.5 3
Absorbance

0.4

2
y = 0.0337x + 0.0251
0.3
R2 = 0.9989

0.2
1

0.1

0 0
0 5 10 15 20 25
0 2 4 6 8 10 12
Concentration (mg/l)
Initial pH

Fig. 1: Calibration curve of MO dye Fig. 2: Plot for determination


of the pHzpc of WB

Fig. 3(a-b): FTIR spectra of free and dye loaded WB


648 ALZAYDIEN, Orient. J. Chem., Vol. 31(2), 643-651 (2015)

index for the ability to become either positively or water (150 ml. pH 5.9. electric conductivity 1.7 µS
negatively charged, This ability is controlled by the cm-1for 90 min), an increase in the pH and electric
pH of the surrounding solution. When pH of solution conductivity of water to 7.4 and 173 ¼S cm-1,
< pHZPC, the sorbent will react as positive surface respectively, was observed. The increase of pH can
and as negative surface when pH of solution > pHZPC be interpreted by a possible fixation of H+ by the
22
. From other side, the observed pH dependence negative groups present on the WB surface and as
can be also related to the dye chemistry. MO is an a result the proton concentration decreases when
acidic dye contains negatively charged sulfonated the initial pH increases, and then the dye molecules
group (-SO3-Na+). Higher adsorption of the dye at have more chance to react with the active sites on
lower pH is probably due to increase in electrostatic the surface of WB because of a lower proton
attraction between negatively charged dye molecule competition10. However, at pH 6.3 where surface
and positively charged WB surface. From other side, charge of WB is neutral, adsorption of dye in this pH
when WB (1 g) was stirred (160 rpm) with bidistilled range may be attributed to physical forces only. At
25
18

16
Amou nt of MO adsorb ed, Qe ( mg/g) 20
14
Amount of MO adsorbed, Qe (mg/g)

12

15
10

10
6

2 5

0
0 2 4 6 8 10 12
pH 0
0 10 20 30 40 50 60
Temperature (C)

Fig. 4: Effect of pH on adsorption of MO onto WB Fig. 5: Effect of temperature


on adsorption of MO onto WB
14

12
Amount of MO adsorbed, Qe (mg/g)

10

16

8 14
Amount of MO adsorbed, Qe (mg /g)

12

6 10

4 6

2 2

0
0 20 40 60 80 100 120 140 160 180
0 Time (min)

0 5 10 15 20 25
Adsorbent dose (g/l)

Fig. 6: Effect of sorbent dose on Fig. 7: Effect of contact time


adsorption of MO onto WB on adsorption of MO onto WB
ALZAYDIEN, Orient. J. Chem., Vol. 31(2), 643-651 (2015) 649

pH above 6.3, surface charge of WB is negative Effect of temperature on dye adsorption


which hinders the adsorption by electrostatic forces Temperature has a vital effect on
of repulsion between negatively charged MO adsorption process as it can increase or decrease
molecule and WB surface. Also lower adsorption of the amount of adsorption. To study the effect of
MO at alkaline pH is due to the presence of excess temperature , sorption experiments of MO by WB
OH - ions competing with dye anions for the were performed at four different temperatures, i.e.,
adsorption sites. At alkaline pH significant 25, 35, 45, and 55 éþC and the obtained results are
adsorption of the MO dye adsorption still occurred. presented in Fig. 5. The results in Fig. 5 revealed
It can be explained by formation of covalent bonding that the sorption capacity increases from 12.34 to
between surface –OH group of WB and negatively 19.85 mg/g when the temperature increased from
charged dye molecules. This can be suggested that 25 to 55 éþC. This suggests that the sorption of MO
the second mechanism, i.e., chemisorption might dye onto WB is endothermic and activated process
be operative23. Thus, strong pH-dependence of MO indicating that the higher temperature is more
adsorption onto WB together with FTIR results favorable for the dye sorption. The increase in dye
indicate to possible involvement of physical forces adsorption with rise in temperature may be a result
such as hydrogen bonding, Vander Waals and of increase in the mobility of MO molecules with
covalent chemical bonds in the adsorption process. temperature. Increasing temperature is known to
increase the rate of diffusion of the adsorbed
1.2
molecules across the external boundary layer and
the internal pores of the adsorbent particles, owing
1
to the decrease in the viscosity of the solution24.
0.8 y = -0.0058x + 0.9744 Furthermore increasing temperature may produce
R2 = 0.9723
a swelling effect within the internal structure of the
log (Qe-Qt)

0.6
WB enabling large dye molecules to penetrate
0.4 further25. Similar results has been reported by Cicek
0.2
et.al for the sorption of reactive dyes onto WB3.

0
0 20 40 60 80 100 120 140 Effect of WB dose on dye adsorption
Time (min)
To optimize the WB dose for MO
Fig. 8: Pseudo-first order adsorption adsorption from its aqueous solution. Adsorption
kinetics of MO onto WB was carried out with different sorbent dosages. The
dose of WB was varied from 0.5 to 2.0 g per 100 ml
dye solution at concentration 100 mg/l, pH 4.0 and
12 temperature 25±1 [C. The amount of MO dye
adsorbed by different masses of WB is presented
10 in Fig. 6. It was observed that the adsorbed amount
of MO dye per unit weight of WB decreased from
8 12.94 to 6.38 mg/g by increasing the sorbent dose
t/Qt, (min g/mg)

from 0.5 to 2.0 g. The decrease in adsorption amount


6 y = 0.0659x + 1.4824 (Qe, mg/g) may be due to the splitting effect of flux
2
R = 0.9821
(concentration gradient) between adsorbate and
4 adsorbent with increasing adsorbent dose causing
in amount of dye onto unit weight of adsorbent3.
2 Another reason may be due to the particle
interactive behavior, such as aggregation, resulted
0 from high adsorbent dose. Such aggregation would
0 20 40 60 80 100 120 140 160
Time (min)
lead to decrease in diffusional path length24. In
addition, the adsorption sites remain unsaturated
during the sorption process in these conditions.
Fig. 9: Pseudo-second order
adsorption kinetics of MO onto WB
650 ALZAYDIEN, Orient. J. Chem., Vol. 31(2), 643-651 (2015)

Adsorption kinetics dye concentration. Fig. 9 shows the (t/Qt) versus t


Effect of contact time plot of the second order kinetics with correlation
The plot of Qt versus time, where Qt is the coefficient (R2 >0.98). The slope of the plot gives the
amount of MO dye sorbed at time t per unit weight of value Qe and from intercept k2 can be calculated.
WB is shown in Fig. 7. In this plot, it is apparent that The values of Qe and k2 were determined to be
the extent of dye adsorption increased rapidly in 15.17 mg/g and 2.93x10-3 g/mg min, respectively. It
the initial stages and became slower in the later is clear from the nature of fit and correlation
stages until the attainment of equilibrium. As the coefficients that adsorption of MO dye on WB is
surface adsorption sites become exhausted, the represented well by both first order and pseudo
uptake rate is controlled by the rate at which the second order kinetic models. This suggests that the
dye molecules are transported from the exterior to sorption of MO dye onto WB surface is presumably
the interior sites of the adsorbent particles. a chemisorption process involving exchange or
Equilibrium time for the adsorption of MO on WB sharing of electrons mainly between dye anions
was found to be 150 min and the equilibrium and surface functional groups of the WB28. Pseudo
adsorption capacity Qe was found to be 14.3 mg/g. second order kinetics was observed earlier by Ho
and MacKay for adsorption of dyes BB69 and AB25
Rate of adsorption on peat (k2 = 5.79x10-3 g/mg min and 1.84x10-3 g/
The adsorption rate shows how much mg min, respectively) and on wood (k2 = 3.43x10-3
adsorbate can be adsorbed from the liquid phase g/mg min and 3.21×10-3 g/mg min, respectively)26,27.
onto the adsorbent within a unit time. The kinetics of Due to different nature of the adsorbent used in the
adsorption of MO dye onto WB was described by present work from those described above. A direct
using first order and pseudo second order model. comparison of the values of k2 is not possible, but
The Lagergren,s equation for first-order kinetics is the values may be described to be in the same order.
given as follows26.
CONCLUSIONS
log(Qe-Qt) = log Qe – (k1/2.303)t ...(2)
In this study, the ability of WB to bind MO
The expression for pseudo second order dye was investigated. The results indicates thar the
rate equation is given as27. adsorption capacity of WB was considerably
affected by its surface functional groups and surface
t/Qt = 1/k2Qe2 + t/Qe ...(3) charge as well as by pH and temperature of medium.
strong pH-dependence of MO adsorption onto WB
where Qe and Q t are the amount of MO dye together with FTIR results indicate to possible
adsorbed (mg/g) at equilibrium and at any time t; involvement of physical forces such as hydrogen
k1(min-1) and k2 (g/mg min) are the rate constants. bonding, Vander Waals and covalent chemical
Plot of log(Qe-Qt) versus t gives a straight line with bonds in the adsorption process. Adsorbed amount
correlation coefficient (R2 >0.97) for the first order of MO dye decreases with increasing pH but when
adsorption kinetics and is shown in Fig. 8 for the temperature increased adsorption capacity is
initial dye concentration of 100 mg/l. The value of increased within study range, this indicates that the
first order rate constant k1 is obtained from the slope adsorption process is endothermic. The kinetics of
of the curve is equal to 1.34x10-2 min-1. This means MO adsorption onto WB followed pseudo – first and
that in case of strict surface adsorption, a variation second -order rate expressions. It can be concluded
in rate should be proportional to the first power of that the WB is an efficient adsorbent for the removal
of MO dye from aqueous solution.

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