Well Reviewed PDF

Journal of Purity, Utility Reaction and Environment Vol.1 No.
4, June 2012, 170-199
Langmuir model application on solid- Article Info

liquid adsorption using agricultural
Received:10th May 2012
wastes: Environmental application Accepted: 20th May 2012
Published online: 1st June 2012
review
Dalia Khalid Mahmoud1,∗, Mohamad Amran Mohd

Salleh1,2, Wan Azlina Wan Abdul Karim1
1
Department of Chemical and Environmental Engineering,
Faculty of Engineering, Universiti Putra Malaysia, 43300 UPM
Serdang, Selangor, Malaysia
2
Green Engineering and Sustainable Technology Laboratory,
Institute of Advanced Technology, Universiti Putra Malaysia,
43300 UPM Serdang, Selangor, Malaysia
almusaferdalia@yahoo.com
ISSN: 2232-1179 © 2012 Design for Scientific Renaissance All rights reserved
ABSTRACT
Langmuir isotherm is a model that used intensely at adsorption studies to make comparison between the
adsorption capacities of different adsorbents in order to evaluate the efficiency of these adsorbents.
Langmuir model is concept of the monomolecular adsorption on homogeneous surfaces. Adsorption has
been proved to be a promising technique at wastewater treatment. Recently many researchers have proved
the capability of agricultural solid wastes as alternative adsorbents instead of commercial activated carbon
to remove different classes of pollutants such as dyes, phenols and metals. This review presents the use of
agricultural solid wastes as adsorbents to remove different pollutants and the effect of treatment on their
efficiency. Adsorbent efficiency related to the physical and chemical properties of adsorbent.
Keywords: Adsorption, Langmuir model, Agricultural wastes, Review
1. Introduction
The day-to-day human activities and industrial revolution have influenced the flow and
storage of water and the quality of available fresh water (Mohan et al., 2007). Industries have a
Journal of Purity, Utility Reaction and Environment Vol.1 No.4, June 2012, 170-199
large potential to cause lake, streams and river pollution. The nature of pollution varies from
industry to industry and also from plant to plant (Mohan et al., 2008).
Among all physicochemical methods, adsorption is known to be a promising technique due
to the ease of operation, comparable low cost of application, high-quality of the treated effluents
especially for well-designed sorption processes (Eren and Afsin, 2007; Qadeer, 2007).
Activated carbon is widely used as an adsorbent, but it is expensive and therefore not
economical for wastewater treatment (Chandra et al., 2007), thus researchers interested to
investigate the using of adsorbents based on the agricultural wastes to remove different types of
pollutant, such as using of pomelo peel for adsorption of methylene blue dye (Hameed et al,
2008a), banana stalk for adsorption of methylene blue dye (Hameed et al, 2008b), Lemon peel
for adsorption of malachite green dye (Kumar, 2007), sugarcane bagasse for adsorption of ions
Cu(II), Cd(II) and Pb(II) (Gurgel and Gil, 2009) and palm seed for adsorption of phenol
(Rengaraj et al., 2002).
2. Adsorption technology
Adsorption is the method for separation of mixtures on a laboratory and industrial scale
where it is a surface phenomenon that can be defined as the increase in concentration of a
particular component at the interface between two phases.
Adsorption is very important process due to its technological, environmental and biological
importance. Furthermore the practical applications of adsorption process in industry and
environmental protection are important. Adsorption is a method for separation of mixtures that
based on the change in concentration of components at the interface. The development of
adsorption at surface science is considered as physical science that representing an
interdisciplinary area between chemistry, physics, biology and engineering. Adsorption process
systems can be as: liquid-gas, liquid-liquid, solid-liquid and solid-gas.
Physical adsorption can happened due to the universal van der Waals interactions, while
chemical adsorption or chemisorption can occur when there will be a character of a chemical
process.
The practical applications of adsorption can be at separation and purification of liquid and
gas mixtures, bulk chemicals, drying gases and liquids before loading them into industrial
systems, removal of impurities from liquid and gas media, recovery of chemicals from industrial
and vent gases and water purification. Activated carbon is the most widespread uses of for
liquid-phase adsorption in water treatment and has increased throughout the world. (Dabrowski,
2001; Noll et al., 1992). Adsorption process also used in many industrial wastewaters that
contain substances difficult to remove via conventionally secondary treatment, toxic or
hazardous, volatile and cannot be transferred to the atmosphere, substances have the potential for
creating noxious vapors or odors or for imparting color to the wastewater and substances present
is very small concentrations that make their removal via other methods difficult (Armenante.,
NJIT).
171
The change in the concentration of a pollutant (adsorbate) in the surface layer of the material
(adsorbent) in comparison with the bulk phase with respect to unit surface area is termed
adsorption. The term ‘‘biosorption’’ is given to adsorption processes, which use biomaterials as
adsorbents (or biosorbents). The assessment of a solid-liquid adsorption system is usually based
on two types of investigations: batch adsorption tests and dynamic continuous-flow adsorption
studies. When studying adsorption from solutions on materials it is convenient to differentiate
between ‘‘adsorption from dilute solution’’ and ‘‘adsorption from binary and multicomponent
mixtures covering the entire mole fraction scale’’. Batch studies use the fact that the adsorption
phenomenon at the solid/liquid interface leads to a change in the concentration of the solution.
Adsorption isotherms are constructed by measuring the concentration of adsorbate in the medium
before and after adsorption, at a fixed temperature (Crini and Badot, 2008).
3 Adsorption isotherm using Langmuir model
Adsorption is technique suitable for the removal of low concentrations of pollutants from
large volumes of process effluents, potable water, wastewater and aqueous solutions. Adsorption
equilibrium information is important to understand of how much adsorbate can be
accommodated by a solid adsorbent. Adsorption isotherm describes how pollutants interact with
adsorbent materials with relate to adsorption properties and equilibrium data. Mathematical
description of equilibrium adsorption capacity is necessary for efficient prediction of adsorption
parameters and quantitative comparison of adsorption behavior for different adsorbent systems.
For solid–liquid adsorption system, adsorption isotherm is important model in description of
adsorption behavior. At equilibrium, a saturation point is reached where no further adsorption
can occur. Typically, the mathematical correlation, which constitutes an important role towards
the modeling analysis, operational design and applicable practice of the adsorption systems, is
usually depicted by graphically expressing the solid-phase against its residual concentration. The
adsorption isotherm is representing the relationship between the mass of adsorbate adsorbed per
unit weight of adsorbent and the liquid-phase equilibrium concentration of adsorbate.
Giles et al. (1974), proposed a general modeling of sorption isotherms, in which four
particular cases are used as the four main shapes of isotherm commonly observed (Fig. 1).
172
Fig. 1. The four main types of isotherms (Giles et al., 1974).
At the ‘‘C’’ isotherm (Fig. 1a), the curve is a line of zero-origin which means that the ratio
between the concentration of the compound remaining in solution (C) and adsorbed on the solid
(Q) is the same at any concentration. The ‘‘C’’ isotherm is often used for a narrow range of
concentration or very low concentrations rather than an accurate description. At the ‘‘L’’
isotherm (Fig. 1b), the ratio between the concentration of the compound remaining in solution
(C) and adsorbed on the solid (Q) decreases when the solute concentration increases, providing a
concave curve suggesting a progressive saturation of the solid.
At the ‘‘H’’ isotherm (Fig. 1c), the initial slope is very high because the compound exhibits
sometimes such a high affinity for the solid (Toth, 1995). At the ‘‘S’’ isotherm (Fig. 1d), the
curve is sigmoidal and thus has got a point of inflection. This type of isotherm is always the
result of at least two opposite mechanisms.
Irving Langmuir was awarded the Nobel Prize in 1932 for his investigations concerning
surface chemistry. The Langmuir model (Langmuir, 1918) is probably the most popular one due
to its simplicity and its good agreement with experimental data (Crini & Badot, 2008; Hamdaoui
and Naffrechoux, 2007; Limousin et al., 2007).
Langmuir model is clear concept of the monomolecular adsorption on energetically
homogeneous surfaces. The statement proposed by Langmuir was applied to chemical adsorption
and with some restrictions to physical adsorption and the constant parameters of the Langmuir
equation have a strictly defined physical meaning. The Langmuir equation and the method of
solid surface area determination based on it can be applied to systems in which the adsorption
process is not complicated by formation of a multilayer (Dabrowski, 2001; Noll et al., 1992).
173
Most of adsorption isotherm equations were proposed as modification of the classical

Langmuir equation (Rudzinski and Plazinski, 2007). The Langmuir isotherm gives the following
hypotheses (Gimbert et al., 2008):
 Monolayer adsorption (the adsorbed layer is one molecule thick).
 Adsorption takes place at specific homogeneous sites within the adsorbent.
 Once a dye occupies a site, no further adsorption can take place at that site.
 Adsorption energy is constant and does not depend on the degree of occupation of an
adsorbent’s active centers.
 The strength of the intermolecular attractive forces is believed to fall off rapidly with
distance.
 The adsorbent has a finite capacity for the adsorbate (at equilibrium, a saturation point is
reached where no further adsorption can occur).
 All sites are identical and energetically equivalent.
 The adsorbent is structurally homogeneous.
 There is no interaction between molecules adsorbed on neighboring sites.
Langmuir adsorption isotherm plays an important role in the determination of the maximum
capacity of adsorbent. Langmuir’s isotherm describing the adsorption of adsorbate (A) onto the
surface of the adsorbant (S), where the chemical reaction for monolayer adsorption can be
represented as follows (CHEM 331L):
A+S AS (1)
Where AS represents a solute molecule bound to a surface site on S. The equilibrium

constant K for this reaction is given by:
K= (2)
[A] denotes the concentration of A, while the other two terms [S] and [AS] are two-
dimensional analogs of concentration and are expressed in units such as mol/cm2. The principle
of chemical equilibrium holds with these terms. The complete form of the Langmuir isotherm
considers (Eq. 2) in terms of surface coverage q which is defined as the fraction of the adsorption
sites to which a solute molecule has become attached. An expression for the fraction of the
surface with unattached sites is therefore (1 - q). Given these definitions, we can rewrite the term
[AS]/[S] as:
= (3)
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Now we express [A] as C and rewrite equation 2 as:
K= (4)
Rearranging, we can obtain the final form of the Langmuir adsorption isotherm:
= (5)
Where =
The Langmuir isotherm model (Langmuir, 1918) assumes that the adsorption occur at
homogeneous sites at adsorbent surface, and saturation happen when the dye molecule fill the
site where no more adsorption can occur at that site. According to the above equations Langmuir
isotherm can represent by the following equation:
q max K L C e
qe  (6)
1  K L Ce
qe - Amount of adsorbate adsorbed at equilibrium (mg/g)

qmax Maximum monolayer adsorption capacity of the adsorbent (mg/g)
Ce---- Equilibrium concentration of adsorbate (mg/L)
KL Langmuir adsorption constant related to the free energy adsorption (L/mg)
Since the estimation of the adsorption isotherms parameters interference by the method of
linearization [Hamdaoui, 2006], therefore five forms of Langmuir isotherm equation used to
determine the constants KL and qmax. Equation 2 can be linearized in to the following five forms
of Langmuir isotherm equations (Hamdaoui and Naffrechoux, 2007):
Ce  1
 Ce (7) (7)
qe qmax K L qmax
175
1 1 1
  (8)
qe qmax K Lq
max Ce
qe
qe   q
max
(9)
K L Ce
qe
 K q  K q (10)
Ce L e L max
1 KLq
 max
 KL (11)
Ce qe
The constants values can be evaluated from the intercept and the slop of the linear plot of
experimental data of (Ce/qe) versus Ce or (1/qe) versus (1/ Ce) or qe versus (qe / Ce), (qe / Ce)
versus qe , (1/ Ce) versus(1/qe).
Although non-linear method provides a better result, but the linear least-square method is still
preferred in favor of its simplicity and convenience. (Febrianto et al., 2009). It is clear that
transformations of non-linear model to linear forms implicitly alter their error structure and may
also violate the error variance and normality assumptions of standard least-squares method
(Kinniburgh, 1986; Ho and Wang, 2004). Equations 7 and 8 are the most frequently used by
several researchers because of the minimized deviations from the fitted equation resulting in the
best error distribution (Hamdaoui and Naffrechoux, 2007).
The essential feature of the Langmuir isotherm can be expressed by means of RL, a
dimensionless constant referred to as separation factor or equilibrium parameter RL which is
calculated using the following equation (Hall et al., 1966):
1
RL  ------- -------------- (12)
1 K LC

KL ---- Langmuir adsorption constant related to the free energy adsorption (L/mg)
Cο---- The highest initial adsorbate concentration (mg/L)
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The value of separation factor RL indicates the adsorption process as given:

Unfavorable (RL >1)
Linear (RL =1)
Favorable (0< RL <1)
Irreversible (RL = 0)
Most of adsorption studies are using the same theories for the adsorption isotherms, which
depend on the comparison between the adsorption capacities of different adsorbents in order to
evaluate the efficiency of these adsorbents (Foo and Hameed, 2010).
4 Agricultural solid wastes
Agricultural “green energy” production is the principal contributor in economic development

of a developing country. Its economy development is based on agricultural production and most
people live in the rural areas. Implementation of integrated community development programs is
therefore very necessary. It is believed that integrated community development contributes to
push up socio-economic development of the country (Demirbas et al., 2006).
Agricultural by-products usually are composed of lignin and cellulose as major constituents and
may also include other polar functional groups of lignin, which includes alcohols, aldehydes,
ketones, carboxylic, phenolic and ether groups (Pagnanelli et al., 2003).
There have been many attempts to find inexpensive and easily available adsorbents to
remove the pollutants. According to the physico-chemical characteristics and low cost of the
agricultural solid wastes, they may be good potential adsorbents (Rafatullah et al., 2010).
Agricultural solid wastes used as adsorbents to remove many types of pollutants, such as dyes,
metals and phenol compounds. Agricultural productions are available in large quantities around
the world; thus big amount of wastes rejected (Mohd Salleh et al., 2011a). Table 1 shows
agricultural production (Ton/year) in some countries (FAO, 2009).
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Table 1 Agricultural production in some countries (Ton/year) (FAO, 2009)
Products Malaysia Indonesia India Mexico Nigeria Philippines
Coconut 459640 21565700 10148000 1004710 236700 15667600
Oil palm 84842000 86000000 - 292499 8500000 516115
Coir 23400 - 507400 - - -
Rice,paddy 2510000 64398900 133700000 263028 3402590 16266400
Sugar cane 700000 26500000 285029000 49492700 1412070 22932800
Agricultural wastes are lignocellulosic materials that consist of three main structural
components which are lignin, cellulose and hemicelluloses. These components contribute mass
and have high molecular weights. Lignocellulosic materials also contain extractive structural
components which have a smaller molecular size (Demirbas, 2009). Agricultural and industrial
sectors dispose of large amounts of untreated waste, which may pollute the land as a result
damage the ecosystem. On the other hand, improper treatment of these wastes causes similar
problems. Therefore legislative control of pollutants should be enacted to prevent or to minimize
the transfer of hazardous material to other areas (Mannan and Ganapathy, 2004). Thus, within
the last few years many ideas have been introduced in order to properly dispose of these wastes,
such as intensive use as adsorbents for pollutant removal especially for dye removal where it
showed high adsorption capacity (Noeline et al., 2005). Agricultural wastes are better than other
adsorbents because the agricultural wastes are usually used without or with a minimum of
processing (washing, drying, grinding) and thus reduce production costs by using a cheap raw
material and eliminating energy costs associated with thermal treatment (Franca et al., 2009).
Researchers also used carbon derived from different agricultural solid wastes to be used as
adsorbents and used different activation treatments in order to improve their physical, chemical
and morphological characteristics. Physical activation involves carbonization of material then
activation at elevated temperature in the presence of suitable oxidizing gases such as air, carbon
dioxide, steam or their mixtures, while the chemical activation involve mixing the precursor with
chemical activating agents such as acid, basic solutions, as dehydrating agents and oxidants.
Steam activation involve heating at moderate temperatures (500-700 °C) under a flow of pure
steam, or heated at (700–800 °C) under a flow of just steam (Ioannidou and Zabaniotou, 2007).
178
5 Dyes removal
Synthetic dyes are an important class of organic compounds and are often found in the
environment as a result of their wide industrial use (Crini and Badot, 2008). Many industries are
involved with water pollution, such as textile companies, food processing companies, dye
manufacturers, electroplating factories, paper and pulp mills usually discharge coulored
wastewaters, where it is aesthetically undesirable and may reduce sunlight penetration.
Furthermore dyes have complex structure and synthetic origin therefore these dyes are difficult
to decolorize (Kuo et al., 2008; Demirbas et al., 2008). The total dye consumption of the textile
industry worldwide is in excess of 107 kg/year and 1000 tonnes/year or more of these dyes are
discharged into waste streams by the textile industry worldwide (Marc, 1996). Dyes can affect
aquatic plants because they reduce sunlight transmission through water. Also dyes may impart
toxicity to aquatic life and may be mutagenic, carcinogenic and may cause severe damage to
human beings, such as dysfunction of the kidneys, reproductive system, liver, brain and central
nervous system (Kadirvelu et al., 2003; Dinçer et al., 2007; Shen et al., 2009).
In the dye molecules there are two important components: chromophores which are
responsible for producing the color and auxochromes which enhance the affinity of the dye
toward the fibers (Gupta and Suhas, 2009). Generally, the dyes used in the textile industry are
basic dyes, acid dyes, reactive dyes, direct dyes, azo dyes, mordant dyes, vat dyes, disperse dyes
and sulfur dyes (Demirbas, 2009).
There is higher consumption of synthetic dyes over natural dyes for most types of industrial
applications, due to the low production cost and brighter colors of synthetic dyes, furthermore
better resistance towards environmental factors and easy-to-apply factor (Ngah et al., 2011).
Many researchers had studied the adsorption of Methylene blue dye since it is an important basic
dye and widely used in the textile industry. Acute exposure to Methylene blue may cause
jaundice, quadriplegia, increased heart rate, cyanosis, shock, vomiting, heinz body formation and
tissue necrosis in humans (Vadivelan and Kumar, 2005). Fig.2 shows the chemical structures of
different classes of dyes. Different adsorbents derived from agricultural solid wastes have been
used for dye removal from wastewater and many studies of dye adsorption by agricultural solid
wastes have been published. Table 3 lists previous studies of the adsorption of dyes using
adsorbents based on agricultural solid wastes.
Adsorption capability of adsorbent usually related by the physical and chemical properties of
adsorbent such as BET surface area and functional groups. The carboxyl and hydroxyl groups
are the major functional groups in the adsorption of cationic dyes. Carboxyl group bearing
negative charge inhibited the adsorption of anionic dyes, while hydroxyl group is important
functional group in the adsorption of anionic dyes (Gong et al., 2005).
Cazetta et al., (2011) activated the coconut shell carbon using NaOH at three NaOH:char
ratio of 1:1 (AC-1), 2:1 (AC-2) and 3:1 (AC-3). They found that the surface area were 783, 1842
and 2825 (m2/ g) while the carboxylic groups were 0.37, 0.62 and 0.75 (mmol/g) for (AC-1),
179
(AC-2) and (AC-3) respectively. Therefore the adsorption capacity of AC-3 for adsorption of
Methylene blue was high (916 mg/g).
Wu and Tseng, (2008), studied the adsorption of basic brown1 (BB1) using fir wood char
that treated with NaOH solution (4 NaOH/char weight ratio). They found that the surface area of
activated fir wood char was 2406 m2/g and its adsorption capacity was 2226 g/kg, which
consider high value comparing with other studies.
Wang and Zhu, (2007), studied the adsorption of Methylene blue and Rhodamine B using
commercial activated carbon (Calgon, USA) as original form with BET surface area 972 m2/g
and another form that treated with HCl at BET surface area1015 m2/g. For the adsorption of
Methylene blue, the adsorption shows an order of AC > AC-HCl, while for the adsorption of
Rhodamine B, the adsorption order was AC-HCl > AC. The difference in adsorption capacity
depends on the surface chemistry, where, there are two parallel adsorption mechanisms in the
adsorption, the first involving electrostatic interactions between dye molecules and carbon
surface groups and the second involving dispersive interactions between dye molecules and
carbon surface layers. For adsorption of Methylene blue cationic dye, the electrostatic
interactions between dye molecules and carbon surface groups could play a role but the
predominant effect is the interaction between the delocalised π -electron of the carbon surface
and the free electrons of the dye molecule (aromatic rings and –N=N– or –N=C–C=C– bonds).
Therefore, a carbon with the highest acidity shows a lower adsorption for methylene blue dye
[Pereira et al., 2003]. The basic original carbons exhibited higher adsorption to cationic
Methylene blue dye suggesting that dispersive interaction plays a dominant role in the adsorption
mechanism.
Batzias et al., (2009) studied the adsorption of Methylene blue onto fine grinded wheat straw
where they found that BET surface area was 3.1 (m2/ g) corresponding to adsorption capacity of
2.23 mg/g. After acid treatment, the BET surface area (m2/ g) increased from 3.1 to 9, thus the
adsorption capacity increased from 2.23 to 16.21(mg/ g).
Tseng, (2007) studied the activation of plum kernels by NaOH and he found that the BET
surface area increased from 1478 to 1887 (m2/ g) when the NaOH/char ratio increased from 2 to
4, thus adsorption capacity for Basic brown 1 increased from 1453 to 1845 mg/g.
Foo and Hameed, (2011) used activated carbon prepared from date stones char (DSAC) for
adsorption of Methylene blue. The BET surface area, Langmuir surface area and total pore
volume were 856 m2/g, 1276 m2/g and 0.4680 cm3/g, respectively (compared with 66 m2/g, 99
m2/g and 0.0385cm3/g for char without activation). The adsorption capacity of DSAC was
316.11 mg/g. The FTIR spectrum of char revealed the peaks at 3233, 2361, 1992, 1424 and 1054
cm−1, corresponds to the presence of –OH (hydroxyl), alkynes, –COOH (carboxylic acids), OH,
and C–O–C (esters, ether or phenol) functional groups. Meanwhile, the surface chemistry of
DSAC illustrated intensive peaks, at 3233, 1424 and 1054 cm−1, corresponds to the presence of–
OH (hydroxyl), –OH bending vibrations, and C–O–C (esters, ether or phenol) derivatives.
180
Tan, et al., (2008) used acid treated oil palm shell carbon to remove Methylene blue dye.
Activated carbon was prepared by immersing the original activated carbon in 5% hydrochloric
acid (HCl) and left for 4 h. The sample was then filtered, rinsed and dried in an oven. After
activation, the surface chemistry of the activated carbon underwent some changes and the bands
displayed by the FTIR spectra were: 3572 cm−1 (O–H stretching vibrations in carboxylic acid),
2278 cm−1 (C C stretching vibrations), 1236 cm−1 (C–O–C stretching vibrations in ether) and 664
cm−1(C–Cl stretching vibrations in chloro). That is why the adsorption capacity increased from
243.90 to 303.03 (mg/g) for oil palm shell-based and HCl-treated oil palm shell-based,
respectively.
181
Acid blue 92
Amido Black 10B
Methylene blue
Fig. 2. Chemical structures of different dyes
182
Table 2 previous studies of adsorption of dyes using adsorbents based on agricultural solid
wastes.
Adsorbents Dyes qmax References
.(mg/g)
Kenaf fibre char Methylene blue 18.18 Dalia et al., 2012
Mixture of Agricultural Solid Wastes Methylene blue 93.458 Mohd Salleh et al., 2011b
Cashew nut shell Congo red 5.184 Kumar et al., (2010)
Waste apricot Malachite green 116.27 Başar (2006)
Waste apricot Crystal violet 57.80 Başar (2006)
Wheat bran Malachite green 66.57 Wang et al., (2008)
Yellow passion fruit waste Methylene blue 44.70 Pavan et al., (2008)
Apricot stone activated carbon Astrazon yellow 209.64 Demirbas et al., (2008)
Sunflower oil cake Methylene blue 10.21- Karagöz et al., (2008)
16.43
Almond shell activated carbon at750 °C Methylene blue 1.33 Aygün et al., 2003
Banana pith Acid brilliant 4.42 Namasivayam et al., (1998)
blue
Peanut hull Sunset yellow 13.99 Gong et al., (2005)
Hazelnut shell carbon at 750 °C Methylene blue 8.82 Aygün et al., (2003)
Coir pith carbon Methylene blue 5.87 Kavitha and Namasivayam, (2007)
Activated date pits at 500 °C Methylene blue 12.94 Banat et al., (2003)
Corncob hull char immersed in KOH Methylene blue 5.53 Wu et al., (2011)
Coconut coir pith Direct Red 12B 76.3 Sureshkumar and Namasivayam ,
(2008)
Waste apricot activated carbon Methylene blue 102.04 [Basar, 2006
Rice husk Indigo carmine 29.2799 Lakshmi et al., (2009)
neem sawdust malachite green 4.35 Khattri and Singh, (2009)
Acid treated wood-shaving bottom ash Red Reactive 29.9 Leechart et al., (2009)
Thespesia populnea pods activated Orange G dye 9.129 Arulkumar et al., (2011)
carbon
Coconut bunch Methylene blue 70.92 Hameed et al., (2008c)
Coconut coir pith Direct Red 12B 76.3 Sureshkumar and Namasivayam
,(2008)
Treated Coconut male flowers carbons Crystal violet 60.42 Senthilkumaar et al., (2006)
Jute fiber Eosin yellow 31.489 Porkodi and Kumar,( 2007)
Banana pith Acid brilliant 4.42 Namasivayam et al., (1998)
blue
Peanut hull Sunset yellow 13.99 Gong et al., (2005)
Polygonum orientale Linn activated Malachite green 476 Wang et al., (2010)
carbon
Mild acid hydrolyzed wheat straw Methylene Blue 16.21 Batzias et al., (2009)
Husk of the mango seed carbon Acid blue 80 9.2 Dávila-Jiménez et al., (2009)
Oil palm empty fruit bunch Methylene blue 50.76 Rebitanim et al., (2012)
Petai (Parkia speciosa) seed Methylene blue 91.74- Ahmad et al., (2011)
100.03
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6 Phenols removal
Phenols are natural components of many substances like wine, smoked foods and tea.
Phenols are present in animal wastes and decomposing organic material. Phenols can be
generated from the industrial sources of contaminants such as oil refineries, coal gasification
sites and petrochemical units. Phenols also released from the combustion of tobacco and fossil
fuels. Furthermore, phenols are introduced into surface water from industrial effluents such as
those from the coal tar, gasoline, plastic, rubber proofing, disinfectant, pharmaceutical and steel
industries and domestic wastewaters, agricultural run-off and chemical spills. In the refinery and
lubricant production, phenols used as an extracting solvent. Due to their germicidal and local
anesthetic properties, phenols used at preparation of shaving soaps and creams. Phenols also
used as a reagent in chemical analysis and as a primary petrochemical intermediate. Phenols are
biodegradable and at high concentrations can be toxic and mutagenic. Fig.3 shows phenol and
phenol derivatives that commonly found in industrial wastewaters. Table 3 shows molecular
weight of phenol compounds. Phenol is rapidly absorbed through the skin and can cause skin and
eye burns upon contact. Comas, convulsions, cyanosis and death can result from overexposure to
it. Phenols can cause unpleasant taste and odor of drinking water also can cause negative effects
on different biological processes internally, phenol affects the liver, kidneys, lungs and vascular
system (Ahmaruzzaman, 2008; Dąbrowski, 2005; Busca et al., 2008; Lin and Juang, 2009).
Therefore, it is important to remove these compounds from the effluents before it disposed into
the wastewaters. Table 4 lists previous studies of the adsorption of phenols using adsorbents
based on agricultural solid wastes.
Aygün et al., (2003), studied the adsorption of phenol using carbon obtained from several
agricultural wastes (almond shell, hazelnut shell, walnut shell and apricot stone). Although some
properties like surface area and carbon content of all activated carbons are not very much
different from each other, phenol adsorption capacities differ. The BET surface area of hazelnut
shell carbon and apricot stone carbon were 793 and 783 (m2/ g), and their adsorption capacities
for phenol were 145 and 126 (mg/g), that are higher than other adsorbents. Oxygen containing
surface functional groups strongly influence adsorption capacity of for phenolic compounds.
There are no acidic groups on hazelnut shell carbon and apricot stone carbon, that is why the
adsorption capacity of phenol was high on these adsorbents.
Tseng et al., (2003) studied the adsorption of acid blue 264, basic blue 69 and phenol onto
activated carbon prepared from pinewood. Physical activation of pinewood was done under
steam at 900 °C. They found that pinewood activated carbon have high adsorption capacities for
these three adsorbates. The adsorption capacities for the adsorption of acid blue 264, basic blue
69 and phenol were 1176, 1119 and 240.6 g/ kg at high surface area of adsorbent (902 m2/ g).
184
Fig. 3 Phenol and phenol derivatives (C6) commonly found in industrial wastewaters or fractions
isolated from vegetal sources. Representative examples are indicated under the general chemical
structures (Soto et al., 2011).
185
Table 3 Molecular weight of phenol compounds (Liu, et al 2010)
Phenol compounds Molecular weight

(g/mol)
Phenol 94.1
2-chlorophenol (2-CP) 128.6
4-chlorophenol (4-CP) 128.6
DICHLORO PHENOL 163

(DCP)
Trichlorophenylmethyliodosalicyl (TCP) 197.4
4-Nitrophenol (4-NP) 139.1
dinitrophenol (DNP) 184
186
Table 4 previous studies of the adsorption of phenols using adsorbents based on agricultural solid
wastes.
Adsorbents Pollutants qmax. References
(mg/g)
Commercial activated Phenol 49.72 Özkaya, (2006)
carbon
Granular activated carbon 2-chlorophenol 303.03 Hamdaoui and Naffrechoux, (2007)
(GAC) 4-chlorophenol 322.58
2,4-dichlorophenol 370.37
2,4,6-trichlorophenol 526.32
Coconut husk activated 2,4,6-trichlorophenol 716.10 Hameed et al., (2008d)
carbon
Coconut shell activated Phenol 205.8 Mohd Din et al., (2009)
carbon
Coconut fibers Phenol 12.23 Phan et al., (2006)
Activated coconut fibers 74.63
jute fibers 19.49
Activated jute fibers 181.81
beet pulp carbon Phenol 90.61 Dursun et al., (2005)
Wood particleboard wastes Phenol 500 Girods et al., (2009)
activated carbons
Carbon-rich black gram Phenol 109.92 Srihari and Das, (2008)
husk
Black cherry Phenol 133.33 Arana et al., (2010)
Stones activated carbon
Oil palm empty fruit bunch 2,4-dichlorophenol 232.56 Shaarani and Hameed, (2010)
activated carbon
Punica granatum 2,4-dichlorophenol 65.7 BhatnagarMinocha, (2009)
(pomegranate) peel
Carbonized Corncobs Phenol 37 El-Hendawy, (2005)
o-nitrophenol 13
m-nitrophenol 20
Pnitrophenols 23
Almond shells Pentachlorophenol 9.6 Estevinho et al., (2008)
Charred saw-dust p-nitrophenol 147 Dutta et al., (2001)
NaOH-Modified Palm Oil 4-nitrophenol 500 AL-Aoh et al., (2012)

Fuel Ash
187
7 Metals removal
Heavy metals are a general collective term applying to the group of metals and metalloids
with an atomic density greater than 6 g cm-3(O’Connell et al., 2008). The metals of major
environmental concern today are arsenic, cadmium, chromium, cobalt, copper, lead, manganese,
mercury, nickel and zinc (Bhattacharyya and Gupta, 2008). Toxic metal ions in water represent
serious public health problem where the heavy metal ions are not degradable and cannot be
destroyed therefore they persistent environmental contaminants and can be harmful to aquatic
life. Furthermore these metals may have a potentially damaging effect on human physiology and
other biological systems when the tolerance levels are exceeded. The heavy metal ions are stable
and persistent environmental contaminants since they cannot be degraded and destroyed. The
presence of copper, zinc, cadmium, lead, mercury, iron, nickel and others metals, has a
potentially damaging effect on human physiology and other biological systems when the
tolerance levels are exceeded (Demirbas, 2008; Demirbas et al., 2005). The chemical functional
groups such as carboxylic and phenolic groups are responsible for binding between the metal ion
and lignocellulosic adsorbents by a surface complexation mechanism (Pagnanelli et al., 2003).
Although the maximum adsorption capacities of metal adsorption by agricultural adsorbents
are not high compare to dyes and phenols removal, but still good choice as adsorbents for metal
removal. Table 5 lists previous studies of the adsorption of metals using adsorbents based on
agricultural solid wastes.
Camire and Clydesdale (1981), studied the effect of heat treatment on the binding of calcium,
magnesium, zinc, iron to wheat bran, and they conclude that the lignin and pectin have a high
metal binding capability. They found that the pH had a significant effect on the binding of
metals by lignin and wheat bran and the boiling had a significant effect on the binding of metals
by cellulose, lignin, and wheat bran.
Agarwal et al., (2006), studied adsorption of chromium (VI) by Tamarindus indica seeds.
They found that the particle size of sorbents has a significant effect on Cr (VI) sorption. The
larger sorbent size showed lesser Cr (VI) removal as compared to the smaller sorbent size. This
may be due to that the surface area available for adsorption decreases with the increase of
particle size, providing less active surface sites for adsorption of sorbate. The reduction in Cr
(VI) removal capacity with increase in sorbent size gives an idea about the porosity of sorbent,
where if the sorbent is highly porous then it would not have significant effect on Cr (VI)
removal.
Adsorption of lead (II) using activated carbon prepared from coconut shell has been studied
by Sekar et al., (2004). The Surface area of the adsorbent was found to be 265.96 (m2 g−1) with
maximum adsorption capacity of 26.50 (mg/g).
A study of Cr (VI) removal from synthetic wastewater using coconut shell charcoal was
done by Babel and Kurniawan, (2004), and they found that the surface area of the adsorbent was
found to be low (5–10 m2 g−1) with adsorption capacity of 10.88 (mg/g).
188
Ho and McKay, (2000), studied the kinetics of sorption of divalent metal ions onto sphagnum
moss peat and they found that the chemical bonding among divalent metal ions and polar
functional groups on peat, such as aldehydes, ketones, acids, and phenolics are responsible for
the cation-exchange capacity of the peat.
Table 5 previous studies of the adsorption of metals using adsorbents based on agricultural solid
wastes.
Adsorbents Metals qmax. (mg/g) References
Coconut shell activated carbon Pb 26.50 Sekar et al., (2004)
Treated green coconut (Cocos Pb+2 54.62 Sousa et al., (2010)
nucifera) shells Ni+2 16.34
Cd+2 37.78
Zn+2 17.08
Cu+2 41.36
Ethanol treated Agricultural Ni+2 2.5 Zhang and Ismail, (2012)
Wastes (peat soil, cow dung and
digested paddy husk)
Green coconut shell powder Cd+2 285.7 Pino et al., (2006)
Coconut shell charcoal oxidized Cr(VI) 10.88 Babel and Kurniawan, (2004)
with nitric acid
Coconut coir pith Cr(VI) 201.47 Suksabye et al., (2008)
Modified coconut coir pith Cr(VI) 76.3 Namasivayam and Sureshkumar(2008)
Modified coir pith Ni(II) 38.9 Ewecharoen et al., (2008)
Apricot stone activated carbon Ni(II) 27.21 Kobya et al., (2005)
Co 30.07
Cd(II) 33.57
Pb(II) 22.85
Cu(II) 24.21
Cr(III) 29.47
Palm Tree Leaves Zn(II), 14.60 Al-Rub, (2006)
Wool Cr(VI) 41.15 Dakiky et al., (2002)
Tea waste Cu(II) 48.00 Amarasinghe and Williams, (2007)
Tamarindus indica seeds Cr(VI) 0.098 Agarwal et al., (2006)
Rose waste biomass Pb(II) 151.51 Javed et al., (2007)
Tea factory waste Ni(II) 15.26 Malkoc and Nuhoglu (2005)
Rice bran Zn(II) 14.17 Wang et al., (2006)
Orange peels Cd(II) 123.65 Schiewer and Patil, (2008)
Olive pits Cd(II) 9.39 Salem and Allia, (2008)
Commercial activated carbon Zn(II) 19.9 Ramos et al., (2002)
Raw activated carbon Cr(VI) 7.614 Liu et al., (2007)
Oxidized in boiling HNO3 13.74
NaOH and NaCl 13.89
Activated carbon CN 47.62 Behnamfard and Salarirad, (2009)
189
8 Conclusion
During the last few years many articles concerning the adsorption of pollutants by
agricultural solid wastes have been published. This article is an attempt to highlight the use of
Langmuir adsorption isotherm to determine the maximum capacity of adsorbents and effect of
the physical and chemical properties on to adsorption capacity of adsorbent. Furthermore, to
highlight the effect of different activations on the adsorbents, thus improve their physical,
chemical and morphological characteristics. Previous studies showed that the activation with
acidic or basic solutions can increase the BET surface area and carboxylic groups. The more acid
or basic ratio (acid or basic- adsorbent), the more increase in BET surface area, thus increasing
adsorption capacity. The carboxyl and hydroxyl group are major functional groups in the
adsorption of cationic dyes.
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Journal of Purity, Utility Reaction and Environment Vol.1 No.

4, June 2012, 170-199

Langmuir model application on solid- Article Info

Dalia Khalid Mahmoud1,∗, Mohamad Amran Mohd

Keywords: Adsorption, Langmuir model, Agricultural wastes, Review

3 Adsorption isotherm using Langmuir model

Fig. 1. The four main types of isotherms (Giles et al., 1974).

Most of adsorption isotherm equations were proposed as modification of the classical

Where AS represents a solute molecule bound to a surface site on S. The equilibrium

Now we express [A] as C and rewrite equation 2 as:

qe - Amount of adsorbate adsorbed at equilibrium (mg/g)

The value of separation factor RL indicates the adsorption process as given:

4 Agricultural solid wastes

Agricultural “green energy” production is the principal contributor in economic development

Table 1 Agricultural production in some countries (Ton/year) (FAO, 2009)

Products Malaysia Indonesia India Mexico Nigeria Philippines

Coconut 459640 21565700 10148000 1004710 236700 15667600

Oil palm 84842000 86000000 - 292499 8500000 516115

Coir 23400 - 507400 - - -

Rice,paddy 2510000 64398900 133700000 263028 3402590 16266400

Sugar cane 700000 26500000 285029000 49492700 1412070 22932800

Amido Black 10B

Fig. 2. Chemical structures of different dyes

Table 3 Molecular weight of phenol compounds (Liu, et al 2010)

Phenol compounds Molecular weight

2-chlorophenol (2-CP) 128.6

4-chlorophenol (4-CP) 128.6

DICHLORO PHENOL 163

Trichlorophenylmethyliodosalicyl (TCP) 197.4

4-Nitrophenol (4-NP) 139.1

dinitrophenol (DNP) 184

NaOH-Modified Palm Oil 4-nitrophenol 500 AL-Aoh et al., (2012)

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