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Journal of Environmental Chemical Engineering 2 (2014) 398–414

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Journal of Environmental Chemical Engineering


journal homepage: www.elsevier.com/locate/jece

Review

Relevance of isotherm models in biosorption of pollutants by agricultural


byproducts
S. Rangabhashiyam, N. Anu, M.S. Giri Nandagopal, N. Selvaraju *
Department of Chemical Engineering, National Institute of Technology Calicut, Kozhikode 673601, Kerala, India

ARTICLEINFO AB STR ACT

Article history: Industries generating wastewater with elevated concentrations of pollutants (e.g. metals, dyes, phenolic
Received 1 October 2013 compounds, anions, etc.) need specialized atreatment systems. Adsorption is one of the most extensively
Accepted 13 January 2014 applied techniques for the removal of pollutants from the industrial effluents. The prominent and
emerging trend of subjecting biosorbent in the adsorption technology is mainly because of their natural
Keywords: existence, abundance, renewable, biodegradable and economic features. The adsorption isotherm
Adsorption equations used to describe the experimental data and the thermodynamic assumptions of the models
Isotherms often provide some insight into the sorption mechanism, the surface properties and affinity of the
Biosorbents
biosorbent. This paper presents a state of the art on the review of adsorption isotherm models in an
Wastewater treatment
exhaustive manner on the basis of two, three, four and five parameters respectively. Focuses on the
Pollutants
various sources of agricultural byproducts as biosorbents and describes on the potential applications of
different adsorption isotherm models for the evaluation of the wastewater pollutants biosorption. It is
evident from the literature survey that various adsorption isotherm models have been considered under
study by the researchers but mostly two and three parameter isotherm model were best fitted the
equilibrium data. This paper reviews the adsorption isotherm models on the basis of parameters that can
be applied for exploring a novel biosorbents.
© 2014 Elsevier Ltd. All rights reserved.

Contents

Introduction ...................................................................................................................................................................................................................... 400


Biosorption and the characteristic features of the biosorbents .................................................................................................................................. 400
Adsorption isotherm models ...........................................................................................................................................................................................401
Two parameter isotherms .....................................................................................................................................................................................401
The Langmuir Isotherm model .............................................................................................................................................................. 401
The Freundlich isotherm model ............................................................................................................................................................ 402
The Temkin isotherm model................................................................................................................................................................402
The Dubinin–Radushkevich isotherm model ....................................................................................................................................... 402
The Flory–Huggins isotherm model ..................................................................................................................................................... 403
The Elovich isotherm model................................................................................................................................................................403
The Fowler–Guggenheim isotherm model ........................................................................................................................................... 403
The Kiselev isotherm model ................................................................................................................................................................403
The Hill–de Boer model ........................................................................................................................................................................ 403
The Jovanovic isotherm model ............................................................................................................................................................. 403
The Halsey isotherm model .................................................................................................................................................................403
The Harkin–Jura isotherm model .......................................................................................................................................................... 403
Three parameter isotherms ...................................................................................................................................................................................404
The Redlich–Peterson isotherm model ................................................................................................................................................. 404
The Hill isotherm model ......................................................................................................................................................................404
The Toth isotherm model .....................................................................................................................................................................404
The Jossens isotherm model ................................................................................................................................................................404

* Corresponding author. Tel.: +91 495 2285409; fax: +91 495 2287250.
E-mail addresses: selvaraju@nitc.ac.in, selvaraju.n@gmail.com (N. Selvaraju).

2213-3437/$ – see front matter © 2014 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.jece.2014.01.014
S. Rangabhashiyam et al. / Journal of Environmental Chemical Engineering 2 (2014) 398–414 399

The Fritz–Schlunder isotherm model ................................................................................................................................................... 404


The Sips isotherm model ..................................................................................................................................................................... 404
The Koble–Corrigan isotherm model ................................................................................................................................................... 404
The Khan isotherm model ................................................................................................................................................................... 404
The Radke–Prausnitz isotherm model .................................................................................................................................................. 404
The Frumkin isotherm model ............................................................................................................................................................... 405
The Liu isotherm model [87] ................................................................................................................................................................ 405
Four parameter isotherms .................................................................................................................................................................................... 405
The Weber–van Vliet isotherm model ................................................................................................................................................. 405
The Fritz–Schlunder isotherm model ................................................................................................................................................... 405
The Baudu isotherm model ................................................................................................................................................................. 405
Five parameter isotherms ..................................................................................................................................................................................... 405
The Fritz–Schlunder isotherm model ................................................................................................................................................... 405
BET isotherm ......................................................................................................................................................................................................... 405
Adsorption isotherm models in the assessment of biosorbents for different pollutants .......................................................................................... 405
Adsorption isotherm model significance in the biosorbent evaluation for metal removal .......................................................................... 405
Adsorption isotherm model significance in the biosorbent evaluation for dye removal ............................................................................. 407
Adsorption isotherm model significance in the biosorbent evaluation for phenolic removal ..................................................................... 408
Adsorption isotherm model significance in the biosorbent evaluation for anio ns removal ........................................................................ 409
The selection of isotherm model for the adsorption studies [231]............................................................................................................................. 410
Error function ......................................................................................................................................................................................................... 410
Average relative error .......................................................................................................................................................................... 410
Sum of squares of the error ................................................................................................................................................................. 410
Determination coefficient .................................................................................................................................................................... 410
Adjusted determination coefficient ..................................................................................................................................................... 410
Error function [179,236] ........................................................................................................................................................................ 410
Conclusion ......................................................................................................................................................................................................................... 411
Acknowledgements .......................................................................................................................................................................................................... 411
References .......................................................................................................................................................................................................................... 411

Nomenclature
qm Elovich maximum adsorption capacity
(mg/g)
Ce equilibrium concentration of adsorbate
KFG Fowler–Guggenheim equilibrium constant
(mg/L)
(L/mg)
qe adsorbate adsorbed per gram of the
uFG, uK, uH fractional coverage
adsorbent at equilibrium (mg/g)
W interaction energy between adsorbed
Q0 monolayer coverage capacity (mg/g)
molecules (kJ/mol)
KL Langmuir isotherm constant (L/mg)
K1K Kiselev equilibrium constant (L/mg)
RL separation factor or equilibrium parameter
kn constant of complex formation between
C0 adsorbate initial concentration (mg/L)
adsorbed molecules
Kf Freundlich isotherm constant
K1H Hill–de Boer constant (L/mg)
ðmg1—ð1=nÞ L1=n g—1Þ
K2 energetic constant of the interaction
n adsorption intensity
between adsorbed molecules (J/mol)
AT Temkin isotherm equilibrium binding
Kj Jovanovic isotherm constant (L/mg)
constant (L/mg)
KH Halsey isotherm constant
bT Temkin isotherm constant
nH Halsey equation exponents Harkins–
R universal gas constant (8.314 J/mol K)
AH Jura isotherm parameter Harkins–Jura
T absolute temperature (K)
B2 isotherm constant
B heat of sorption constant (J/mol) Dubinin–
KRP Redlich–Peterson model isotherm constant
K Radushkevich isotherm constant related to
(L/g)
the adsorption energy (mol2/kJ2) theoretical
aRP Redlich–Peterson model constant (mg/L)—g
Qm isotherm saturation capacity (mg/g)
g Redlich–Peterson model exponent
Polanyi potential
q sH Hill isotherm maximum uptake saturation
e mean free energy (kJ/mol)
(mg/L)
E Flory–Huggins equilibrium constant (L/mg)
KD Hill constant
KFH model exponent
nH Hill cooperativity coefficient of the binding
nFH Gibbs free energy (kJ/mol)
interaction
DG8 degree of surface coverage of adsorbent
KT Toth equilibrium constant
u surface
TT Toth model exponent
Elovich equilibrium constant (L/mg)
H, F, p parameters of the Jossens equation
KE
400 S. Rangabhashiyam et al. / Journal of Environmental Chemical Engineering 2 (2014) 398–414

large industrial scale application. Therefore cost-effective materi-


qmFS Fritz–Schlunder maximum adsorption als are needed [8]. Biosorption subjecting agricultural byproducts
capacity (mg/g) acts as the economic and pragmatic method for the removal of
KFS Fritz–Schlunder equilibrium constant (L/mg) different pollutants like heavy metals [9,10], COD [11,12], phenol
mFS Fritz–Schlunder model exponent [13,14], and dyes [15–17]. A general modelling of the sorption
q ms isotherms under 4 particular cases (C, L, H and S isotherm
Sips maximum adsorption capacity (mg/g)
respectively) with 4 main shapes of isotherm were commonly
KS Sips equilibrium constant ðL=mgÞms
observed [18]. The adsorption isotherm does not provide
mS Sips model exponent automatically any information about the reactions involved in
a Koble–Corrigan parameter(Ln mg1—n/g) the adsorption phenomenon. Therefore, mechanistic interpreta-
b Koble–Corrigan parameter(L/mg)n tions must be carefully verified for the appropriate measurements
bK Khan isotherm model constant and interpretations of isotherm data [19]. In order to investigate
qs theoretical isotherm saturation capacity novel adsorbents in the ideal adsorption system, it is essential to
(mg/g) introduce the most appropriate adsorption equilibrium correlation
nK Khan model exponent Radke– [20], which is important for reliable prediction of adsorption
qmRPI, qmRPII, Prausnitz maximum adsorption parameters and for the quantitative comparison of adsorbent
qmRPIII behaviour under different adsorbent systems or different experi-
capacities (mg/g)
mental conditions [21,22]. With this perception, equilibrium
KRPI, KRPII, Radke–Prausnitz equilibrium constants
relationships also known as the adsorption isotherms describes
KRPIII
how pollutants interact with the adsorbent materials, critical for
mRPI, mRPII, Radke–Prausnitz models exponents optimization of the adsorption mechanism pathways, expression
mRPIII of the surface properties and capacities of adsorbents and effective
f interaction coefficient of the Frumkin design of the adsorption systems [23,24].
equation
KFF equilibrium constant of Frumkin equation Biosorption and the characteristic features of the biosorbents
Kg Liu equilibrium constant (L/mg)
nL dimensionless exponent of the Liu equation Biosorption is a potential alternative technique for the removal
P1, P2, P3, P4 parameters of Weber–van Vliet equation of organic pollutants like metals, dyes and phenolics from
wastewaters. Agricultural byproducts of various origins serve as
A, B Fritz–Schlunder parameters
the biosorbents are known to bind with the pollutants [25,26]. Use
a, b Fritz–Schlunder equation exponents
of agricultural, botanical residues in biosorption process suggests
qm0 Baudu maximum adsorption capacity (mg/g)
the following importance over other unitary operations. (1) The
b0 equilibrium constant materials are usually highly economical. (2) There is no need of
x, y Baudu parameters costly growth media and maintenance of aseptic conditions. (3)
qmFS5 Fritz–Schlunder maximum adsorption The process is independent of physiological constraints of living
capacity (mg/g) cells. (4) Reversible process, the biosorbent can be subjected for the
K1, K2, m1, m2 Fritz–Schlunder parameters further recycle. (5) The formation of chemical or biological sludge
CBET BET adsorption isotherm relating to the is minimized [27].
energy of surface interaction (L/mg) The biomass source of agricultural byproducts includes wood,
adsorbate monolayer saturation short rotation woody crops, agricultural wastes, short rotation
Cs
herbaceous species, wood wastes, bagasse, sawdust, biosolids,
concentration (mg/L)
grass, etc. [28]. Most of the organic materials are produced from
the sources of plants, trees and crops. The two major carbohydrates
having significant value are cellulose and hemicelluloses [29].
Cellulose, a remarkable pure organic polymer comprised exclu-
Introduction sively of the units of anhydroglucose and bound together through
giant straight chain molecule [30]. These anhydroglucose units are
The global increase in water pollution has augmented bound together by b-(1,4)-glycosidic linkages. Through intramo-
awareness among the public and more attention has been focused lecular and intermolecular hydrogen bonds between OH groups
to combat the problem [1]. The major cause of water pollution is within the same cellulose chain and the surrounding cellulose
the industrial activities [2]. Conventional methods used for the chains, the chains tend to be arranged parallel and form a
removal of wastewater pollutants include chemical precipitation, crystalline super molecular structure [31]. Cellulose is insoluble in
ion exchange, filtration, reverse osmosis, electrochemical treat- most of the solvents and has a low accessibility to acid and
ment, electrodialysis and adsorption on activated carbon. In enzymatic hydrolysis. Hemicelluloses consist of different mono-
comparison of all the methods, adsorption plays as the most saccharide units and the polymer chains have short branches and
versatile and widely used method for the removal of pollutants are amorphous in nature, which makes it partially soluble or
because of its cost effectiveness, simplicity of design and operation swellable in water. Hemicellulose occurs as much shorter molecule
and high removal capacity [3,4]. Adsorption has been revealed as chains in comparison with cellulose [32]. Xylose is the most
the most promising and widely used method for the removal of important sugar component in the hemicelluloses. In hardwood
both inorganic and organic pollutants from contaminated water xylan, the xylose units act as the backbone linked by means of b-
[5]. Activated carbon with the properties of higher surface area, (1,4)-glycosidic bonds and branched by a-(1,2)-glycosidic bonds
good adsorption capacity and fast kinetics is used for the with 4-omethylglucuronic acid groups [31]. In case of the softwood
adsorption of pollutants from contaminated water. The use of xylan, the acetyl groups fewer distributed in the backbone chain
activated carbon in adsorption process is based on the surface and has additional branches composed of arabino furanose units
chemistry and pore structure of porous carbons [6,7]. Activated linked by means of a-(1,3)-glycosidic bonds. Hemicelluloses are
carbon is expensive and this setback, limits its employment on a highly soluble in alkali gets easily hydrolyzed [33–35]. Lignins are
S. Rangabhashiyam et al. / Journal of Environmental Chemical Engineering 2 (2014) 398–414 401

Fig. 1. The chemical structure of major organic compounds of agricultural byproduct.

polymers of aromatic compounds provides structural strength, of the two, three, four and five parameter adsorption isotherm are
sealing of water conducting system that links roots with leaves, represented in Fig. 2, those isotherm models can be subjected for
and protect plants against degradation [36]. Lignin a macromole- the investigation of novel biosorbents for the removal of
cule consists of alkylphenols and has a complex three-dimensional wastewater pollutants.
structure. Lignin is covalently linked with xylans in the case of
hardwoods and with galactoglucomannans in softwoods [37]. The Two parameter isotherms
basic chemical phenylpropane units of lignin are bonded together
through a set of linkages in such a way to form a very complex The Langmuir Isotherm model
matrix. This matrix comprises of various functional groups like This model describes quantitatively about the formation of a
hydroxyl, methoxyl and carbonyl imparts a high polarity to the monolayer adsorbate on the outer surface of the adsorbent and after
lignin macromolecule [31,38]. The basic chemical structures of that no further adsorption takes place. The Langmuir represents the
cellulose, hemicelluloses, xylose and lignin were shown in Fig. 1. equilibrium distribution of adsorbate between the solid and liquid
A biosorption process performed through several modes. The phases [45]. The Langmuir adsorption isotherm the most widely
batch and continuous modes of operation are the often employed used isothermforthe biosportion of pollutantsfroma liquidsolution
modes in order to conduct laboratory scale biosorption processes. based on the following hypotheses. (1) Monolayer adsorption. (2)
In most of the industrial applications the continuous mode of Adsorption takes place at specific homogeneous sites on the
operations are employed but for the evaluation of fundamental adsorbent. (3) Once a pollutant occupies in a site; no further
information’s like biosorbent efficiency, optimum experimental adsorption can take place in that site. (4) Adsorption energy is
conditions, biosorption rate and possibility of biosorbent regener- constant and does not depend on the degree of occupation of an
ation batch experiments are deployed [26]. adsorbent’s active centres. (5) The strength of the intermolecular
attractive forces is believed to fall off rapidly with distance. (6) The
Adsorption isotherm models adsorbent has a finite capacity for the pollutant. (7) All sites are
identical and energetically equivalent. (8) The adsorbent is
Adsorption isotherm indicates the graphical representation of structurally homogeneous. (9) There is no interaction between
the relationship between the amount adsorbed by a unit weight of molecules adsorbed on neighbouring sites [41]. Based upon these
adsorbent and the amount of adsorbate remaining in a test assumptions, Langmuir represented the following equation:
medium at a constant temperature under equilibrium condition. It
gives the information about the distribution of adsorbable solute Q 0K L Ce
qe ¼ (1)
between the liquid and solid phases at various equilibrium 1 þ KLCe
concentrations. The data under the study of adsorption isotherm where Ce is the equilibrium concentration of adsorbate (mg/L), qe
are to be specific for each system and the determination of denotes the adsorbate adsorbed per gram of the adsorbent at
isotherm are to be carried out for every application [39]. The equilibrium (mg/g), Q0 represents the monolayer coverage
different types of the equilibrium isotherm models (Langmuir, capacity (mg/g) and KL is the Langmuir isotherm constant (L/mg).
Freundlich, Temkin, Dubinin–Radushkevich, Flory–Huggins, Elo- The essential features of the Langmuir isotherm may be expressed
vich, Fowler–Guggenheim, Kiselev, Hill–de Boer, Jovanovic, Halsey, in terms of equilibrium parameter RL, a dimensionless constant,
Harkin–Jura, Redlich–Peterson, Hill, Toth, Jossens, Fritz–Schlunder, referred to as separation factor or equilibrium parameter
Sips, Koble–Corrigan, Khan, Radke–Prausnitz, Frumkin, Liu, We- [46]:
ber–van Vliet, Baudu) have been put together on the basis of three
fundamental approaches [38,40]. Kinetic consideration [41], 1
RL ¼ (2)
thermodynamics [42,43] and potential theory [44]. The availability 1 þ KLC0
402 S. Rangabhashiyam et al. / Journal of Environmental Chemical Engineering 2 (2014) 398–414

Adsorption isotherm models

1450 parameter isotherm


Two Three parameter isotherm Four parameter isotherm Five parameter isotherm

1452
1. Redlich–Peterson 1. Weber–van Vliet 1. Fritz–Schlunder
1. Langmuir
1453 2. Hill
2. Freundlich 2. Fritz–Schlunder
3. Toth 3. Baudu
3.1454
Temkin
4. Jossens
4. Dubinin–Radushkevich
5. Fritz–Schlunder
1455
5.Flory–Huggins
6. Sips
6. Elovich
7. Koble–Corrigan
7.1456
Fowler–Guggenheim
8. Khan
8.Kiselev
1457 9. Radke–Prausnitz Explore novel biosorbents
9. Hill–de Boer
10. Frumkin
10. Jovanovic
1458
11.Liu
11. Halsey
1459
12. Harkin-Jura

Fig. 2. The significance of adsorption isotherm models in exploring novel biosorbents.

where C0 is the adsorbate initial concentration (mg/L), KL is the where


constant related to the energy of adsorption (Langmuir constant).
RL value indicates the adsorption nature of unfavourable if RL > 1, RT
B¼ bT (5)
linear if RL = 1, favourable if 0 < RL < 1 and irreversible if RL = 0.

The Freundlich isotherm model where AT is the Temkin isotherm equilibrium binding constant
The Freundlich equilibrium isotherm equation is an empirical (L/mg), bT is the Temkin isotherm constant R is the universal gas
equation used for the description of multilayer adsorption with constant (8.314 J/mol K), T is the temperature (K), B is the constant
interaction between adsorbed molecules: related to heat of sorption (J/mol) [52]. The Temkin equation better
holds for the prediction of gas phase equilibria. Nevertheless, in
1=n
qe ¼ K f Ce (3) case of liquid phase adsorption particularly of heavy metals using
biosorbent, this model fall-short in representing the equilibrium
where Kf is the Freundlich isotherm constant ðmg1—ð1=nÞ L1=n g—1Þ, n
data. In comparison with the gas phase adsorption, the liquid phase
represents the adsorption intensity, Ce indicates the equilibrium
is a more complex phenomenon since the adsorbed molecules do
concentration of adsorbate (mg/L), qe is the amount of adsorbate
not necessarily organized in a tightly packed structure with
adsorbed per gram of the adsorbent at equilibrium (mg/g).
identical orientation. The solvent molecules and micelles forma-
The model is applicable to the adsorption on heterogeneous
tion from adsorbed molecules add to the complexity of liquid
surfaces by a uniform energy distribution and reversible adsorp-
phase adsorption. Many factors such as pH, adsorbate solubility in
tion. The Freundlich equation implies that adsorption energy
the solvent, temperature and surface chemistry of the adsorbent
exponentially decreases on the finishing point of adsorptional
influence the adsorption from liquid phase. The Temkin equation is
centres of an adsorbent [47]. The Freundlich constants are
often not suitable for representation of experimental data of the
empirical constants depends on many environmental factors.
liquid phase adsorption in complex systems, since the derivation
The value of 1/n ranges between 0 and 1 indicates the degree of
for the Temkin equation are based of simple assumption and the
non-linearity between solution concentration and adsorption [48].
complex phenomenon in liquid phase adsorption are not taken
If the value of 1/n is equal to 1, the adsorption is linear [49]. Henry’s
into account [53].
isotherm or one parameter isotherm is applicable for linear
adsorption under the condition when n = 1 in Eq. (3).
The Dubinin–Radushkevich isotherm model
The Dubinin–Radushkevich isotherm can be applied for the
The Temkin isotherm model
estimation of apparent free energy and the characteristics of
Temkin equation, the early model proposed to depict adsorp-
adsorption [44,54,55]. The Dubinin–Radushkevich equation de-
tion of hydrogen on platinum electrodes within acidic solutions.
fined by the following equation [56,57]:
The derivation of the Temkin isotherm based on the assumption
that the decline of the heat of sorption as a function of temperature
qe ¼ Q m expð—K e2Þ (6)
is linear rather than logarithmic, as implied in the Freundlich
equation [50,51]. The model is given by the following equation:
where K is the Dubinin–Radushkevich isotherm constant related to
RT the adsorption energy (mol2/kJ2), Qm is the theoretical isotherm
qe ¼ lnðATCe Þ (4)
B saturation capacity (mg/g), e is the Polanyi potential, calculated
S. Rangabhashiyam et al. / Journal of Environmental Chemical Engineering 2 (2014) 398–414 403

from Eq. (7): interaction among adsorbed molecules is repulsive (i.e. W is


. Σ negative), the heat of adsorption shows a decrease with loading. In
1
e ¼ RT ln 1 þ (7) the case of no interaction between adsorbed molecules (i.e. W = 0),
Ce Fowler–Guggenheim equation will reduce to the Langmuir
where R is the gas constant (8.314 J/mol K) and T is the equation.
temperature (K). The mean free energy E (kJ/mol) of sorption
can be found by using K values represented in Eq. (8). The Kiselev isotherm model
The adsorption isotherm [64] in localized monomolecular layer
1 expressed by the equation
E ¼ pffi ffiffiffiffiffi (8)
2K

The Dubinin–Radushkevich isotherm model is a tempera-


uK (13)
k1 C e ¼
K
ð1 — uK Þð1 þ knuK Þ
ture dependent, when the adsorption data at different tem-
peratures plotted as a function of logarithm of amount adsorbed where k1K is the Kiselev equilibrium constant (L/mg), and kn is the
versus the square of potential energy, all suitable data will lie constant of complex formation between adsorbed molecules.
on the same curve, referred to as the characteristic curve [58–
60]. The Hill–de Boer model
This model [65,66] describes the mobile adsorption and lateral
The Flory–Huggins isotherm model interaction among adsorbed molecules
. Σ
Flory–Huggins isotherm model [61] derives the degree of uH uH K u
K C ¼ exp — 2 H (14)
surface coverage characteristics of adsorbate onto adsorbent,
1 — uH 1 — uH
1H e
express the feasibility and spontaneous nature of an adsorption RT
process. u indicates the degree of surface coverage of adsorbent where K1H is the Hill–de Boer constant (L/mg), K2 is the energetic
surface, KFH and nFH are the Flory–Huggins equilibrium constant constant of the interaction between adsorbed molecules (J/mol).
(L/mg) and model exponent. The equilibrium constant KFH used to
A positive K2 value indicates the attraction between adsorbed
calculate the spontaneity of Gibbs free energy ( DG8). The equation species and a negative value means repulsion. The apparent
of the Flory–Huggins isotherm is as follows: affinity is increased with loading when there exist the attraction
u nFH
between adsorbed species and it is decreased with loading when
¼ KFHð1 — uÞ (9) there is repulsion among the adsorbed species. When there is no
C0
interaction between adsorbed molecules (i.e. K2 = 0), the Hill–de
The degree of surface coverage of adsorbent surface calculated Boer equation will be reduced to the Volmer equation.
using the following equation:
Ce The Jovanovic isotherm model
u ¼1— (10) An adsorption surface assumption considered in this model [67]
C0
is similar to that considered by Langmuir. It corresponds to another
approximation for monolayer localized adsorption without lateral
The Elovich isotherm model interactions. This model is similar to that of Langmuir model,
The equation defining the Elovich model based on the kinetic except that the allowance is made in the former for the surface
principle with the assumption of adsorption sites increase binding vibrations of an adsorbed species. This model shown by
exponentially with adsorption, which implies a multilayer using the following nonlinear relationship
adsorption [62]. The model is expressed by the relation:
. Σ qe ¼ qmð1 — eK jC e Þ (15)
qe q
¼ K EC eexp — e (11)
where Kj is the Jovanovic isotherm constant (L/mg), qm is the
qm qm
maximum adsorption capacity in Jovanovic model (mg/g).
where KE represents the Elovich equilibrium constant (L/mg), qm is
the Elovich maximum adsorption capacity (mg/g). The Halsey isotherm model
Adsorption isotherm equation of this model [68] given as
The Fowler–Guggenheim isotherm model follows:
For the derivation of this isotherm equation, takes in account of
. Σ
the lateral interaction of the adsorbed molecules [63]. The model ln K H — ln C e
qe ¼ exp (16)
has the following explicit form: nH
. Σ
u FG 2uFG W
K C ¼ exp (12) where KH represents the Halsey isotherm constant, nH represents
1 — uFG
FG e
RT the Halsey equation exponents.
Eq. (18) is appropriate for the multilayer adsorption and the
where KFG is the Fowler–Guggenheim equilibrium constant (L/mg),
fitting of the experimental data to this equation confirms to the
uFG is the fractional coverage, W is the interaction energy between
heteroporous nature of the adsorbent.
adsorbed molecules (kJ/mol).
Fowler–Guggenheim equation is the simplest equations with
The Harkin–Jura isotherm model
the consent to the lateral interaction. The heat of adsorption varies
The adsorption isotherm equation of this model [69] expressed
linearly with loading. If the interaction between the adsorbed
as follows:
molecules is attractive (i.e. W is positive), the heat of adsorption
will increase with loading. This is because of the increased . Σ1=2
AH
interaction between adsorbed molecules as the loading increases. qe ¼ (17)
B2 — log Ce
This means that if the measured heat of adsorption shows an
increase with respect to loading, it indicates the positive lateral where AH is the Harkins–Jura isotherm parameter, B2 is the
interaction between adsorbed molecules. Conversely, if the Harkins–Jura isotherm constant.
404 S. Rangabhashiyam et al. / Journal of Environmental Chemical Engineering 2 (2014) 398–414

Three parameter isotherms The Fritz–Schlunder isotherm model


The Fritz–Schlunder [80] equation has been represented in the
The Redlich–Peterson isotherm model following form:
Redlich and Peterson included the features of both the qmFS KFSCe
q¼ (24)
e
Langmuir and Freundlich isotherms into a single equation 1 þ qm CemFS
presented as follows:
where qmFS is the Fritz–Schlunder maximum adsorption capacity
KR PCe (mg/g), KFS is the Fritz–Schlunder equilibrium constant (L/mg), and
qe ¼ g (18) mFS is the Fritz–Schlunder model exponent.
1 þ aRPCe

where KRP is the Redlich–Peterson model isotherm constant (L/g), The Sips isotherm model
aRP is the Redlich–Peterson model constant (mg/L)—g; g is the By identifying the problem of continuing increase in the
Redlich–Peterson model exponent, should be 0 < g ≤ 1. When g = 1 adsorbed amount with an increase in concentration in the
the Redlich–Peterson equation becomes the Langmuir equation: Freundlich equation, Sips [81] proposed an equation similar in
form to the Freundlich equation, but it has a finite limit when the
KRPCe concentration is sufficiently high:
q¼ (19)
e 1 þ aRPCe q K C ms
ms S e
qe ¼ ms (25)
1þK C s e
where g = zero it becomes the Henry’s law [70].
where qms is the Sips maximum adsorption capacity (mg/g), KS is
KR PCe the Sips equilibrium constant ðL=mgÞms , and mS is the Sips model
qe ¼ (20)
1 þ aRP exponent, limited from 0 to 1. At the low adsorbate concentrations
the Sips isotherm model effectively reduces to the Freundlich
isotherm and thus does not obey Henry’s law. And at high
The Hill isotherm model
adsorbate concentrations, this model predicts a monolayer
Hill equation [71], from the non-ideal competitive adsorption
sorption capacity characteristic of the Langmuir isotherm [22].
[72] model, and postulated to explain about the binding of
different species onto homogeneous substrates. The model
The Koble–Corrigan isotherm model
assumes that adsorption process as a cooperative phenomenon,
Koble–Corrigan model [82] is the three-parameter empirical
with the ligand binding ability at one site on the macromolecule,
model based on the combination of both the Langmuir and
may influence the different binding sites on the same macromole-
Freundlich isotherm equations representing in one non-linear
cule [73].
equation of the equilibrium adsorption data. The model is
q C nH commonly expressed by Eq. (26):
qe ¼ sH e (21)
KD þ Cne H aCen
qe ¼ (26)
1 þ bCen
where qsH is the Hill isotherm maximum uptake saturation (mg/L),
KD is the Hill constant, nH is the Hill cooperativity coefficient of the where a (Lnmg1—n/g), b (L/mg)n and n are the Koble–Corrigan
binding interaction. parameters.
This model is generally applied for heterogeneous sorbent
The Toth isotherm model surface [83].
Toth [74] modified the Langmuir equation in order to reduce
the error between experimental data and predicted values of The Khan isotherm model
equilibrium adsorption data. The significance of the equation is This model [84] suggests a generalized isotherm for the bi-solute
best suited to multilayer adsorption, which is a special type of adsorption from dilute aqueous solution. The correlation repre-
Langmuir isotherm and has very restrictive validity [75]. The Toth sented in Eq. (27) has a unique characteristic by covering both
correlation is given for the application to liquid–solid adsorption extremes of the Langmuir and Freundlich isotherm. The generalized
generally presented as [76–78]. equation for pure component adsorption isotherms as follows:

KT Ce q sb K C e
qe ¼ (27)
q e¼ (22) ð1 þ b KC eÞnK
TT 1=TT
½AT þ C e ]
where bK is the Khan isotherm model constant, qs is the theoretical
where KT is the Toth equilibrium constant, and TT is the Toth model isotherm saturation capacity (mg/g), nK is the Khan model exponent.
exponent. When nK is equal to unity, Eq. (27) reduces to the Langmuir
isotherm. This equation at large value of Ce reduces to the
The Jossens isotherm model Freundlich isotherm.
This model is based on a distribution of the energy of
interactions adsorbate–adsorbent on adsorption sites [79]. The The Radke–Prausnitz isotherm model
model assumes that the activated carbon surface is heterogeneous, The three isotherms [85] of this model can be represented as
with respect to the interactions which it engages with the qm KRPICe
adsorbate: qe ¼ RPI
m (28)
ð1 þ KRPICeÞ RPI
q qm KRPIICe
¼ e expðFq pÞ (23)
Ce H e qe ¼ RPII
m (29)
1 þ KRPIICe RPII
where H, F and p represent the parameters of the Jossens equation. m
qmRPIII KRPIIICe RPIII
H and F depend only on temperature. Eq. (23) can be reduced to qe ¼ m (30)
Henry’s law at low capacities. 1 þ KRPIICe RPIII—1
S. Rangabhashiyam et al. / Journal of Environmental Chemical Engineering 2 (2014) 398–414 405

where qmRPI, qmRPII and qmRPIII are the Radke–Prausnitz maximum Graphical study of ln KL = f(ln Ce) and ln Q0 = f(ln Ce) gives access to
adsorption capacities (mg/g), KRPI, KRPII and KRPIII are the Radke– b0, qm0, x, and y.
Prausnitz equilibrium constants, and mRPI, mRPII and mRPIII are the This model gives the transformed the Langmuir equation as
Radke–Prausnitz models exponents. expressed in Eq. (38)
ð1þxþyÞ
The Frumkin isotherm model qm0 b0 C e with ð1 þ x þ yÞ and ð1 þ xÞ < 1 (38)
qe¼
This is the three-parameter isotherm model [86,87] depicted in 1 þ b0 C eð1þxÞ
Eq. (31)
qm0 is the Baudu maximum adsorption capacity (mg/g), b0 is the
. Σ — fu
KFFCe u exp¼ (31) equilibrium constant, and x and y are the Baudu parameters.
1—u For lower surface coverage, Eq. (38) reduces to the Freundlich
equation, i.e.
where f is the interaction coefficient of the Frumkin equation, KFF
ð1þxþyÞ
indicates the equilibrium constant of Frumkin equation. qm0 b0 C e
qe ¼ (39)
1 þ b0
The Liu isotherm model [87]

Five parameter isotherms


nL
Qe ¼ Q max · K gC e (32)
1 þ KgCe nL The Fritz–Schlunder isotherm model
This model represents a broad field of equilibrium data through
where Qe is the adsorption capacity (mg/g), Qmax is the maximum the five-parameter empirical expression [80].
adsorption capacity of the adsorbent (mg/g), Kg is the Liu
q K1Cm1
equilibrium constant (L/mg), Ce is the adsorbate concentration q e 1¼þmKFS5 e with m and m ≤ 1 (40)
at the equilibrium (mg/L), n is the dimensionless exponent of the Cm2 1 2
L 2e
Liu equation.
where qmFS5 is the Fritz–Schlunder maximum adsorption capacity
(mg/g) and K1, K2, m1, and m2 are the Fritz–Schlunder parameters.
Four parameter isotherms
BET isotherm
The Weber–van Vliet isotherm model
Weber and van Vliet [88] proposed an empirical relation with
Brunauer et al. [90] developed an equation for the multilayer
four parameters isotherm models in order to describe the
adsorption and the expression has been represented as follows:
equilibrium data
qsCBET C e (41)
ð P3 þP Þ q¼
e
e s e BET e s
P2 q e
Ce ¼ P1q 4
(33) ðC — C Þ½1 þ ðC — 1ÞðC =C Þ]
where P1, P2, P3 and P4 are the isotherm parameters of Weber–van In which CBET, BET adsorption isotherm relating to the energy of
Vliet equation. surface interaction (L/mg), Cs, adsorbate monolayer saturation
concentration (mg/L)
The Fritz–Schlunder isotherm model
Four-parameter equation of another form of Langmuir– Adsorption isotherm models in the assessment of biosorbents
Freundlich type developed empirically by Fritz and Schlunder for different pollutants
[80]. The equation of this model expressed as follows:
ACa A functional expression for quantity of adsorption with
q¼ e
with a and b ≤ 1 (34) concentration of solute at a constant temperature. Adsorption
1 þ BCeb
e
properties and equilibrium data are commonly known as
where A and B are the Fritz–Schlunder parameters, and a and b are adsorption isotherms. The adsorption isotherms show the
the Fritz–Schlunder equation exponents. pollutants interaction with adsorbent materials and are thus
At high liquid-phase concentrations of the adsorbate, Eq. (34) critical in optimizing for the use of biosorbents [91,92]. In order to
reduces to the Freundlich equation as shown in Eq. (35) optimize the design of an adsorption system to remove pollutant
from wastewater, it is important to establish the most appropriate
A
q e¼ e Ca—b (35) correlation for the equilibrium curve. An accurate mathematical
B description of equilibrium adsorption capacity is indispensable for
where A/B and (a — b) present the parameters Kf and 1/n of the reliable prediction of adsorption parameters and quantitative
Freundlich model. comparison of adsorption behaviour for different adsorbent
For a = b = 1, Eq. (34) reduces to the Langmuir equation, with systems [22,49,92].
KL = B is the Langmuir adsorption constant (L/mg) related to the
energy of adsorption and A = KLQ0. Adsorption isotherm model significance in the biosorbent evaluation
for metal removal
The Baudu isotherm model
The calculation of the Langmuir coefficients, KL and Q0, carried out Special concern over the heavy metal remediation is due to the
through the measurement of tangents at the different equilibrium recalcitrant and persistency nature of heavy metals in the
concentrations. Shows that they are not constants in a broad environment. The distributions of cellulosic agricultural waste
concentration range [89]. Their variations written as follows: materials act as the copious source for significant metal biosorp-
tion. The agricultural waste biomass consists of functional groups
KL ¼ b0Cxe (36) like phenolic, amido, amino, acetamido, alcoholic, carbonyl,
sulphydryl groups, etc. have affinity towards heavy metal ions
Q 0 ¼ qm0Cey (37) in order to form metal complexes or chelates [93]. The design and
406 S. Rangabhashiyam et al. / Journal of Environmental Chemical Engineering 2 (2014) 398–414

analysis of biosorption process entails relevant biosorption comparison with the unmodified orange peel, the biosorption
equilibrium. At the equilibrium condition, a certain relationship capacity increased for modified biomass by 4.2-, 4.6- and 16.5-fold
exists between adsorbate and adsorbent. Their equilibrium for Pb2+, Cd2+ and Ni2+, respectively [102]. Pecan nutshell (Carya
concentrations are a function of temperature. Initially several illinoensis) used for the removal of Cu(II), Mn(II) and Pb(II) from
adsorption isotherm models used for gas phase adsorption and aqueous solutions. The effects such as, pH, biosorbent dosage was
then those isotherm models were readily adopted to show considered in the study. Fractionary order kinetic model was
relationship adsorption equilibrium in heavy metals biosorption observed as the best fitted kinetic model. The equilibrium data
[94]. Biosorption has mainly been considered for heavy metal were fitted to Langmuir, Freundlich, Redlich–Peterson and Sips
removal in order to detoxify metal-bearing effluents. The process isotherm models. Sips isotherm model best fitted the equilibrium
features a high heavy metal selectivity and cost-effectiveness for data. The maximum biosorption capacities of pecan nutshell were
low metal concentrations as compared with ion exchange resins. found as 85.9, 98.0 and 195.9 mg/g for Cu(II), Mn(II) and Pb(II)
There is also no hazardous sludge by-product generation in both respectively [103].
processes and biosorbents can also be easily regenerated for Chemically modified orange peel subjected for the adsorption
multiple reuses [95]. of environmentally problematic metal ions namely Cd2+, Cu2+ and
Pinhao (Araucaria angustifolia) waste and pinhao loaded with Pb2+ from aqueous solutions. And the comparison made with the
Congo red were investigated for the Cu(II) removal from aqueous original orange peel. The metals uptake by chemically modified
solutions. After optimizing the batch adsorption system through orange peel shows rapid and the equilibrium time attained within
statistical design of experiments, the adsorption equilibrium 30 min at constant temperature and pH. The mechanism of metal
data fitted to the Langmuir and Freundlich models. The adsorption by chemically modified orange peel gave good fits for
maximum adsorption capacity of pinhao waste and pinhao Freundlich and Langmuir models in comparison to the Dubinin–
loaded with Congo red for Cu(II) removal was found as 32.2 mg/g Radushkevich isotherm model. The modified biosorption data
and 68.6 mg/g respectively [96]. The evaluation of the feasibility perfectly fits the Langmuir and Freundlich adsorption isotherms
of sugarcane bagasse carried out for the adsorption of nickel from models with determination coefficient > 0.95 for all the metal ions
aqueous solution. The biosorption data were fitted to Langmuir, Cd2+, Cu2+ and Pb2+ [104]. A lignocellulosic material extracted from
Freundlich and Sips isotherm models. The Langmuir model rice husk (Oryza sativa) modified by iron coating through
shows better representation of data, with determination coeffi- hydrolization of ferric nitrate while adding an alkaline solution
cient greater than 0.99 [97]. The sugar cane bagasse subjected as drop wise into the batch type reactor. The parameters studied
a selective solid phase extractor for Fe(III). Batch experiments includes pH, As(V) concentrations, contact times, ionic strength
were carried out at the pH range 1.0–4.0, initial concentration of and adsorbent amounts. Maximum percentage removal of As(V)
metal ion (10–100 mmol), weight of biosorbent (25, 50, 75, 100, ions 94% occurs at pH 4.0. The Langmuir model fitted the
125 and 150 mg) and shaking time (10, 30, 45, 60, 90, 120 and equilibrium data better than Freundlich model and confirms the
150 min). The equilibrium data better fits with Langmuir model surface homogeneity of adsorbent [105]. The adsorption of Cu(II)
in comparison with the Freundlich model [98]. The yellow by carbons prepared from rice husk through pyrolysis and steam
passion fruit shell (Passiflora edulis Sims. f. flavicarpa Degener) activation were investigated. The Cu(II) adsorption on the rice husk
was reported as an biosorbent for the removal Cr(III) and Pb(II) carried out with an optimum pH value of 5.0 and an equilibrium
from aqueous solutions in batch studies. The effects of contact time of 24 h. The Langmuir isotherm model fits better the
time and pH were considered in the biosorption study. The experimental data in comparison with the Freundlich isotherm,
biosorption kinetics followed the pseudo second order. The Dubinin–Radushkevitch isotherm. The values of E obtained in D–R
maximum removal capacity of yellow passion fruit shell were model found to be greater than 14 kJ/mol, indicating the
85.1 and 151.6 mg/g for Cr(III) and Pb(II) respectively. The adsorption process as chemical ion-exchange process [106]. The
Langmuir isotherm model suitably fitted for both the metallic magnitude of E between 8 and 16 kJ/mol corresponds to a chemical
ions [99]. ion-exchange process while the value of E < 8 kJ/mol represents as
The capacity of Polyaniline coated on saw dust as synthetic physical nature process [107]. Coir pith chemically modified by
adsorbent investigated for the removal of Cd(II) ions from aqueous grafting with acrylic acid for the removal of Cr(VI). The maximum
solutions by means of batch operation. The optimum pH for Cr(VI) removal (99.99 T 0.07%) attained under the following
adsorption of Cd(II) found to be 6. Adsorption was rapid and conditions: 1.3% (w/v) dosage of acrylic acid-grafted coir pith, pH
occurred within 20 min for a cadmium concentration range of 10– of 2, contact time of 22 h, temperature of 30 8C, particle size of
40 mg/L. The equilibrium adsorption data for Cd(II) were better <150 mm and an initial Cr(VI) of 1171 mg/l. The adsorption isotherm
fitted to the Freundlich isotherm model in comparison with the of 2 M acrylic acid-grafted coir pith shows a good fit with the
Langmuir adsorption isotherm model [100]. Rubber wood (Hevea Langmuir isotherm in comparison with the Freundlich isotherm
brasiliensis) saw dust modified by the chemical treatment of [108].
phosphoric acid and sodium hydroxide with different impregna- The garden grass was subjected for the biosorption of copper(II)
tion ratios in order to improve adsorption capacity for the removal from water. Copper adsorption depends on important parameters
of copper. The effects of variables like solution pH, temperature, like the pH, initial copper concentrations, contact time, adsorbent
adsorbent dose, initial copper concentration, on the removal of doses, temperature and particle sizes. The equilibrium data were
copper ions have been studied. Adsorption equilibrium data were well fitted by the Langmuir, Sips and Redlich–Peterson isotherm
fitted to the adsorption isotherm models like Langmuir, Freundlich models. The maximum biosorption of 58.34 mg/g was obtained for
Dubinin–Radushkevich and Temkin. The equilibrium data were 1 g dose [109]. Rice husk evaluated was evaluated for the
best represented by the Langmuir and Freundlich isotherms [101]. biosorption of U(VI). Biosorbent used in the form of native, SDS-
Grafted copolymerization-modified orange peel used for the treated and immobilized. The adsorption study parameters
biosorption of Pb2+, Cd2+ and Ni2+ ions from aqueous solution. investigated were pH, biosorbent dosage, contact time, initial
Langmuir and Freundlich isotherm models were applied to U(VI) concentration and temperature. Maximum biosorption
describe the biosorption. Langmuir model fits the equilibrium capacity for native (29.56 mg/g) and immobilized biomass
data better than the Freundlich isotherm. The maximum adsorp- (17.59 mg/g) followed with SDS-treated biomass showed maxi-
tion capacities found through the Langmuir equation, for Pb2+, Cd2+ mum removal of 28.08 mg/g. The Langmuir sorption isotherm
and Ni2+ ions were 476.1, 293.3 and 162.6 mg/g respectively. In model best fitted best with the U(IV) biosorption equilibrium data
S. Rangabhashiyam et al. / Journal of Environmental Chemical Engineering 2 (2014) 398–414 407

Table 1
Applicable isotherm models in the metal biosorption.

Biosorbent Metal ion Equilibrium model Reference

Coconut copra meal Cd(II) Freundlich [112]


Carpinus betulus tree leaves Cd(II) Sips [113]
Chestnut shell Cd(II), Cu(II) Sips [114]
Pb(II), Zn(II)
Wheat bran Cu(II) Langmuir [115]
Coffee wastes Cr(VI) Sips [116]
Golden Shower Leaves Ni(II) Freundlich [117]
Grapefruits peels Cd(II) Freundlich [118]
Litter of poplar forests Cu(II) Freundlich [119]
Wheat shell Cu(II) Freundlich [120]
Rice shell Cu(II) Freundlich [120]
Maize husk Pb(II), Zn(II) Freundlich [121]
Cedar sawdust Cu(II) Freundlich [122]
Coir pith Cr(VI) Freundlich [123]
Almond shell Cu(II) Sips [124]
Sugar beet pulp Pb(II), Cd(II) Freundlich [125]
Mango peel waste Cd(II) Langmuir [126]
Peanut hull Cu(II), Pb(II) Langmuir [126]
Pomelo peel Cd(II) Langmuir [127]
Orange peel Cu(II) Langmuir [128]
Tamarind fruit shell U(VI) Sips [129]
Coconut shell, Neem leaves, hyacinth roots, Cu(II) Freundlich and Halsey [130]
rice straw, rice bran, rice husk
Modified Rice Husk Zn(II) Langmuir [131]
Palm oil fruit shells Cu(II) Sips, Redlich–Peterson, Toth, [132]
Radke–Prausnitz, Hill
Ficus carica Cr(VI) Langmuir [133]
Opuntia ficus indica Cd(II),Pb(II) Langmuir [134]
Bamboo leaf powder Hg(II) Freundlich and Temkin [135]

[110]. The single and binary biosorption of copper and lead ions Langmuir isotherm and isotherm data of Acid Blue 7 follows
from aqueous solution carried out using rice straw. The modified Freundlich isotherm models [142]. The potential of lotus leaf for
extended-Langmuir model with incorporation of solute’s selectiv- the removal of methylene blue from aqueous solution was
ity factor gave good correlation results against binary adsorption investigated. The experiments performed under various conditions
data [111]. The biosorbents and the best fitted adsorption isotherm like solution pH, salt ionic strength, temperature, contact time,
model are shown in Table 1. adsorbent dose and initial methylene blue concentration. In order
to describe the adsorption behaviour, isotherm models like the
Adsorption isotherm model significance in the biosorbent evaluation Langmuir, Freundlich and Koble–Corrigan were employed. In
for dye removal comparison, the equilibrium data were perfectly represented by
Koble–Corrigan isotherm [143]. The study carried out by using
Dye decolourization now becomes the foremost difficulty for the palm kernel fibre for the removal of methylene blue and crystal
treatment plants of various industries like textiles, rubber, paper, violet from aqueous solutions. Adsorption studies parameters
plastics, leather, cosmetic, food, etc. yearly 10–15% of the synthetic includes the different initial dye concentrations (20, 40, 80 and
textile dyes used is lost to waste streams and of about 20% of these 160 mg/L), contact time, pH (1.0–11.0) and sorbent doses (0.4, 2.0,
losses enter the environment through effluent generated the 4.0 and 8.0 g/L). Adsorption data were modelled using Langmuir,
treatment plant [136]. The effluent generated is the most important Freundlich and Temkin adsorption isotherms. Equilibrium data of
threatening factor to the environment because it affects the biotic the biosorption process fitted very well to the Freundlich model
and the abiotic systems [137]. Biosorption represents a powerful (determination coefficient = 0.997 and 0.991 for methylene blue
technique for the dye removal. Biosorption process involves solid and crystal violet, respectively) [144]. Activated and non-activated
living or non-living biosorbent attracts a component to its surface carbonaceous materials of Brazilian pine-fruit-shell (A. angustifo-
from the aqueous solution and form an attachment through a lia) were tested for the removal of Procion Red MX 3B dye from
physical or chemical bond, thereby removing the component from aqueous solutions. Procion Red MX 3B dye uptake was higher at
the liquid phase [138,139]. Agricultural byproducts hold significant the pH range of 2–3 for non-activated carbonaceous adsorbent and
potential for the removal of the toxic dye substances from the 2–7 for activated carbonaceous adsorbent. For the adsorption
effluent discharging into the water bodies [140]. equilibrium data, the Ferror values of the Sips isotherm model were
Rhodamine 6G removal from aqueous solutions carried out by at least 4.0 lower than the values of Langmuir, Freundlich and
almond shell (Prunus dulcis) in a batch technique. The investigation Redlich–Peterson isotherm models [145]. The activated carbon
carried out with the consideration of parameters like pH, contact from bamboo culms wastes were employed for the removal of
time, Rhodamine 6G concentration, almond shell concentration, Disperse Red 167. The adsorption isotherm data were fitted to nine
temperature etc. The biosorption pattern of Rhodamine 6G onto non-linear adsorption isotherm models. The Akaike Information
almond shell well fits with both the Langmuir and Freundlich Criterion analysis was confirmed as the best statistical tool for
isotherm models. Through the Langmuir model equations biosorp- analyzing the data obtained. Temkin isotherm equation best
tion capacity of almond shell found to be as 32.6 mg/g [141]. The described the adsorption isotherm data [146]. The Brazilian pine
adsorption of Acid Black 26, Acid Green 25 and Acid Blue 7 fruit shell (A. angustifolia) was tested as biosorbent for the removal
investigated on Pine Cone. Equilibrium isotherms were analyzed of non-hydrolyzed reactive red 194 and hydrolyzed reactive red
using Langmuir, Freundlich and Tempkin adsorption models. The 194 dyes from aqueous solutions. Chemical treatments of Brazilian
isotherm data of Acid Black 26 and Acid Green 25 follows the pine fruit shell, with chromium, with acid and with acid followed
408 S. Rangabhashiyam et al. / Journal of Environmental Chemical Engineering 2 (2014) 398–414

by chromium were carried out in the study. The adsorption data and Halsey isotherm equations respectively. The highest values of
were fitted to Langmuir, Freundlich, Sips and Redlich–Peterson determination coefficient (0.997) were obtained with Langmuir
isotherm models. For non-hydrolyzed reactive red 194 reactive dye isotherm model [155].
the equilibrium data were best fitted to the Sips isotherm using Meranti (Philippine mahogany) sawdust showed strong scav-
raw and acid treated biosorbent and Redlich–Peterson isotherm enging behaviour towards methylene blue through adsorption
using chromium treated pine fruit shell and acid followed by from aqueous solution. To analyze the equilibrium data, the
chromium treated biosorbents. In the case of hydrolyzed reactive isotherm models like Langmuir, Freundlich and Temkin isotherms
red 194 reactive dye, the equilibrium data were best fitted to the were used at different temperatures. The experimental data fits
Sips isotherm using raw, acid treated biosorbent and acid followed well with the Langmuir adsorption isotherm, representing the
by chromium treated biosorbents and the Redlich–Peterson mono layer adsorption of the dye. The monolayer sorption capacity
isotherm model for chromium treated biosorbents [147]. Brazilian of meranti sawdust for methylene blue found to be 120.48, 117.64,
pine fruit shells (A. angustifolia) in raw form and as activated 149.25 and 158.73 mg/g at 30, 40, 50 and 60 8C respectively [156].
carbon were used for the biosorption of remazol black B from The study examine the potential use of activated carbon prepared
aqueous effluents. The fractionary-order kinetic model best fitted from the epicarp of Ricinus communis for the removal of malachite
the experimental data. Adsorption data of both forms of the green dye from simulated wastewater. As the amount of the
biosorbent better fitted the Sips isotherm equation [148]. adsorbent increased, the percentage of dye removal increased
The adsorption of crystal violet dye by grapefruit peel subjected consequently. Dye adsorption occurs at the optimum pH of 7.0. The
as the potential adsorbent in the remediation of dye contaminated experimental data were analyzed by using isotherm models of
wastewaters. The equilibrium process is well described by the Langmuir, Freundlich, Tempkin and Dubinin–Radushkevich iso-
Langmuir isotherm model than the Freundlich isotherm model. therm models. Adsorption behaviour is well described by a
The maximum adsorption capacity found as 254.16 mg/g [149]. monolayer Langmuir-type isotherm. The maximum removal of MG
The study carried out on the adsorption of Crystal Violet and was obtained at pH 7 as 99.04% for adsorbent dose of 1 g 50 m/L
Rhodamine B by Acacia nilotica leaves. The effect of solution pH, and 25 mg/L initial dye concentration at room temperature [157].
agitation time and initial dye concentration was evaluated. The The wheat straw has been modified by etherification to prepare a
applicability of Langmuir, Freundlich, Dubinin–Radushkevich, and kind of quaternary ammonium straw adsorbents. The adsorption
Temkin equations was examined. The Langmuir isotherm shows behaviours of the modified straw for methyl orange and acid green
the best fit with the experimental data and the maximum 25 were studied in both batch and column systems. The maximal
monolayer capacity found as 33 mg/g for Crystal Violet and methyl orange and acid green 25 uptakes were more than 300 and
37 mg/g for Rhodamine B respectively [150]. Pine cone studied for 950 mg/g. The Mechanism studies using equilibrium data through
its potential application as an adsorbent in raw form and Langmuir model, Freundlich model, Sips model, Dubinin–Radush-
hydrochloric acid modified form to remove anionic dye Congo kevich model indicates that the adsorption process as monolayer
red from aqueous solution. The Congo red adsorption of both form chemical adsorption, therefore well described by the Langmuir
of the biosobent increased with initial dye concentration, isotherm model [158]. Single-dye equilibrium data fitted well with
temperature, contact time, but decreased with increase of solution the Langmuir–Freundlich model and the maximum biosorption
pH and amount of adsorbent of the system. Equilibrium data were capacities were 0.68 mmol/g for methylene blue and 0.50 mmol/g
best represented by Freundlich isotherm model among Langmuir for rhodamine B. Competitive dynamic biosorption demonstrated
and Freundlich adsorption isotherm models. Freundlich constant the preference of the modified cone chips for biosorbing methylene
‘n’ indicates favourable adsorption [151]. The potential of garlic blue [159]. Table 2 shows the valid adsorption isotherm model for
peel evaluated in a batch process for the remove methylene blue the biosorbents in dye sequestration.
from aqueous solution. Experiments were carried out in account of
the parameters like contact time, initial concentration (25– Adsorption isotherm model significance in the biosorbent evaluation
200 mg/L), pH (4–12) and temperature (303, 313 and 323 K). for phenolic removal
Adsorption isotherms assessed through Langmuir, Freundlich, and
Temkin isotherms. The data fits well with the Freundlich isotherm. Phenol is the major organic water pollutants since of its toxicity
The maximum monolayer adsorption capacities found to be 82.64, effects even at low concentrations. The presence of phenol in
123.45, and 142.86 mg/g at 303, 313, and 323 K, respectively [152]. natural waters forms substituted compounds during disinfection
A chemically modified adsorbent prepared from kenaf fibre char and oxidation processes [188]. The thousands of known phenolic
by HCl treatment, which increased the BET surface area in turn compounds distributed in a high molecular diversity and are
increased the Methylene blue adsorption. The highest percentage categorized on the basis of carbon atoms and structure [189–191].
removal of Methylene blue dye found to be 95 wt% at a Even at low concentrations of phenol, act as an impediment to the
concentration of 50 mg/L. The equilibrium data analyzed using use or reuse of water. A phenol gives an unpleasant taste, odour to
the Langmuir, Freundlich and Temkin isotherm models and best drinking water and exerts negative effects on different biological
represented by the Langmuir isotherm model [153]. Olive pomace processes. Most of the phenolic compounds are suspected to the
evaluated for the removal of reactive textile dye, RR198. The causative agents for human carcinogens [192]. The all-pervading
highest dye biosorption capacity occurs at pH 2 and the nature of phenols, their toxicity effects even in trace level and the
equilibrium time was 40 min with a biosorbent concentration of stricter environmental regulations compulsorily made in develop-
3.0 g/L. The equilibrium data were analyzed by Langmuir, ing processes for the phenols removal from wastewaters [193].
Freundlich and Dubinin–Radushkevich isotherm models and the Phenolic removal through adsorption is regarded as a good option
isotherm studies indicate that the data fits better with the since it offers several advantages like (a) non-selectivity in
Langmuir isotherm model [154]. Bagasse pith modified through micropollutants removal at low concentration, (b) efficiency in
chemical activating agent H 3PO4 or KOH followed by carbonization the operational time, (c) convenient handling, (d) economical,
at 500 8C for the removal of Rhodamine-B. The adsorption ability of availability and reusability, (e) no Sludge formation and (f) being
Bagasse pith activated by H 3PO4 is higher than that of the Bagasse eco-friendly [194,195].
pith activated by KOH by approximately 10 folds (198.6 and Carrot dross was subjected to activated carbon preparation,
21.5 mg/g, respectively). The adsorption was analyzed by using magnetized and used for the p-nitrophenol removal from aqueous
isotherm models of Langmuir, Freundlich, Temkin, Harkins–Jura, solution. Batch sorption studies carried out at different pH values,
S. Rangabhashiyam et al. / Journal of Environmental Chemical Engineering 2 (2014) 398–414 409

Table 2
Applicable isotherm models in the dye biosorption.

Biosorbent Dye Equilibrium model Reference

Rice husk Indigo carmine Freundlich, Redlich-Peterson [160]


Rice husk a-Picoline Radke–Prausnitz [161]
Wheat straw Methylene blue Langmuir [162]
Yellow passion fruit Methylene blue Sips [163]
Barley straw Acid blue 40 Langmuir [164]
Pine fruit shell Methylene blue Sips [165]
Cupuassu shell Reactive Red 194, Direct Blue 53 Sips [166]
Wood shaving Egacid orange Langmuir–Freundlich [167]
Canola stalks Acid Orange 7, Remazol Black 5 Langmuir [168]
Jujuba seeds Congo red Langmuir [169]
Coir pith Acid Yellow 99 Langmuir–Freundlich [170]
Olive-waste cakes Lanaset Grey G Langmuir [171]
Sesame hull Methylene blue Langmuir [172]
Pyracantha coccinea berries Methylene blue Langmuir [173]
Olive-waste cakes BlackDycem TTO Langmuir [174]
Swede rape straw Methylene blue Langmuir [175]
Jatropha curcas pods Remazol Brilliant Blue R Langmuir [6]
Cypress cone chips Methylene blue, Rhodamine B Langmuir–Freundlich [159]
Aminoethanethiol modified cellulose Reactive red dye RB Langmuir [176]
Wheat straw Methylene blue Langmuir [177]
Sugarcane bagasse Brilliant Red 2BE Sips [178]
Jatropha curcas shell Reactive Red 120 Liu [179]
Oil palm empty fruit bunch Phenol red Freundlich [180]
Oil palm empty fruit bunch Methylene blue Langmuir [180]
Pine cone Acid Red 114, Acid Yellow 117 Temkin [181]
Pine cone Acid Black 80, Acid Black 1, Acid Blue 113 Langmuir [181]
Pinefruit shell Reactive orange 16 Sips [182]
Pine cone Methyl orange Jovanovic [183]
Cashew nut shell Congo red Redlich–Peterson, Toth Koble–Corrigan model, Sips [184]
Mangifera indica seeds Victazol Orange 3R Liu [185]
Mustard husk Alizarin Red S Freundlich [186]
Cocoa pod husk Methylene blue Freundlich [187]

solid/liquid ratios, contact times and pollutant initial concentra- out on granular activated carbon. The effect of parameters like pH,
tions in the presence and absence of ultrasonic irradiation. The temperature, adsorbent dose and contact time were evaluated.
magnetic activated carbons of carrot dross in the ultrasound Phenol removal takes place at an optimum pH 8, temperature 30 8C
presence fit well the Freundlich isotherm. But in contrast, activated and adsorbent dose of 30 g/L, 79.9% of 200 mg/L phenol. Four
carbon in the presence of ultrasonic irradiation fit well with the multicomponent isotherms were applied to the experimental data
Langmuir model [196]. The adsorption potential of thermally conducted at an initial concentration range of 100–1000 mg/L.
activated carbon from maize cob used for the removal of 2,4- Single component isotherms viz. Langmuir and Freundlich were
dichlorophenol from aqueous solutions. Study carried out to applied to determine the multicomponent isotherm parameters. It
analyze the effects of contact time, 2,4-dichlorophenol initial was found that phenol adsorption followed extended Langmuir
concentration, pH and temperature. Langmuir isotherm fitted well isotherm while cyanide adsorption followed extended Freundlich
with experimental data. The adsorption capacity of maize cob isotherm in multicomponent system. The monolayer adsorption
carbon found as 17.94 mg/g for the particle size of 250–500 mm capacity of GAC was found to be 269.7 and 1.95 mg/g for phenol and
[197]. The adsorption of five phenolic compounds like phenol, 2- cyanide, respectively as calculated by extended Langmuir isotherm
chlorophenol, 4-chlorophenol, 2,4-dichlorophenol, and 2,4,6-tri- [201]. Isotherms for adsorption of 2,4-dinitrophenol from water and
chlorophenol onto granular activated carbon were subjected under basal salt medium onto date seeds and activated carbon were
study through the adsorption equilibrium isotherm. For determin- determined. The experimental data fits the Freundlich isotherm.
ing the best fit isotherm, the equilibrium data analyzed through 0.5 g of date seeds, with a 125 mL salt medium, act the suitable
thirteen adsorption isotherm models. The experimental data fits adsorbent for the removal of 2,4-dinitrophenol [202]. Table 3 shows
the adsorption isotherm models in the order of Baudu > Langmuir– the best fitted adsorption isotherm model for the phenolic removal
Freundlich > Sips > Fritz–Schlunder > Toth > Fritz–Schlunder > using biosorbents.
Redlich–Peterson [198]. The adsorption tests carried out for the
adsorption of five phenolic compounds like phenol, 2-chlorophe- Adsorption isotherm model significance in the biosorbent evaluation
nol, 4-chlorophenol, 2,4-dichlorophenol and 2,4,6-trichlorophe- for anions removal
nol on granular activated carbon using the seven adsorption
equilibrium isotherm models (Langmuir, Freundlich, Elovich, Inorganic anions are the main category of aquatic pollutants
Temkin, Fowler–Guggenheim, Kiselev, and Hill–de Boer). Experi- found in above the normal concentrations in the drinking water
mental data obtained reveals that the adsorption isotherm models sources. The pollutants removal from drinking water supplies is a
fits the data in the order of Fowler–Guggenheim > Hill–de Boer > rising issue [216,217]. Increased nitrate concentrations in water
Temkin > Freundlich > Kiselev > Langmuir isotherms [199]. causes severe health hazard due to reduction of nitrate to nitrite in
The potential of Dalbergia sissoo sawdust charred at 673 K the gastrointestinal human tract. Nitrite causes methemoglobine-
evaluated for the removal of phenol from aqueous solution. The mia. Nitrate and nitrite have the potential to form carcinogenic N-
experimental data for removal from single-contaminant water fits nitroso compounds. At high concentrations of Sulfate causes
well on the Langmuir adsorption model, showing maximum phenol catharsis, dehydration and gastrointestinal irritation [218].
uptake capacity of 344.83 mg phenol/g sawdust at 45 8C [200]. The Excess fluoride intake causes various diseases such as
co-adsorption of phenol and cyanide from binary solution carried osteoporosis, cancer, infertility, brain damage, arthritis, brittle
S. Rangabhashiyam et al. / Journal of Environmental Chemical Engineering 2 (2014) 398–414 411

Table 3
Applicable isotherm models in the phenol biosorption.

Biosorbent Phenolic pollutants Equilibrium model Reference

Mansonia sawdust 4-Nitrophenol Langmuir [203]


Rice husk p-Chlorophenol, p-Nitrophenol Redlich–Peterson [204]
Coconut husk 2,4,6-Trichlorophenol Langmuir [205]
Coconut shell Phenol Freundlich [206]
Banana peel Phenolic compounds Freundlich, Langmuir [207]
Palm seed coat o-Cresol Freundlich [208]
Palm pith 2,4-Dichlorophenol Tempkin [209]
Coconut shell Parachlorophenol, 2,4,6-trichlorophenol Freundlich [210]
Avocado kernel seeds Phenol Langmuir [211]
Olive pomace Phenols Freundlich, Langmuir [212]
Almond shell residues Pentachlorophenol Freundlich [213]
Coconut shell a-Picoline, b-picoline, and g-picoline Langmuir [214]
Coir pith 2-chlorophenol Freundlich [215]

Table 4
Applicable isotherm models in the anion biosorption.

Biosorbent Anions Equilibrium model Reference

Orange waste Phosphorus Langmuir [222]


Sugarcane bagasse Nitrate Langmuir [223]
Rice hull Nitrate Langmuir [223]
Coir pith Sulfate Langmuir, Freundlich [224]
Coir pith Thiocyanate Langmuir, Freundlich and Dubinin–Radushkevich [225]
Wheat straw Nitrate Freundlich [226]
Mustard straw Nitrate Langmuir [227]
Beet residue Nitrate Langmuir [228]
Orange juice residue Fluoride Langmuir [229]
Coconut shell fibres Nitrate, sulfate and phosphate Langmuir, Sips, and Redlich–Peterson [230]

bones, Alzheimer syndrome and thyroid disorder [219,220]. Sum of squares of the error
Phosphate direct discharge into surface waters perturbs the
aquatic organisms and affects water quality by depletion of the X
p ðqe calc — qe meas Þ2 (44)
dissolved oxygen level. Depletion of the oxygen level leads to
; ; i
eutrophication in the confined water bodies [220]. Vanadium holds i¼1
harmful effects on the circulatory system and disturbs the plants
This is the most widely used common error function but the
metabolism leads to chlorosis and limited growth [221]. Table 4
major drawback is that the isotherm parameters derived using this
illustrates the suitable adsorption isotherm model for the anions
error function will provide a better fit as the magnitude of the
removal using biosorbents.
errors and therefore the sum of squares of the error increases –
biasing the fit towards data obtained at the at higher end of the
The selection of isotherm model for the adsorption studies
liquid-phase concentration ranges [235].
[231]

Determination coefficient
The Akaike information criterion is used for the selection of
The determination coefficient (R2) is calculated using the
appropriate model under the situation of when data fitted by more
following equation [179,236]:
than one model [232,233]. The general representation of the !
Pn P
Akaike information criterion is represented as follows: ðq — q̄i exp Þ2 — n ðqi exp — qi model Þ2
2 i i exp
; ; i ; ;
R ¼ Pn (45)
AIC ¼ 2k — 2 lnðLÞ (42) ðqi exp
;
— q̄i exp
;
Þ2
i

where k is the number of parameters in the model and L is the where qe,a,meas is the average of qe,meas. determination coefficient is
maximum value of the likelihood function for the model. used to check the validity of the kinetic and isotherm models used
in describing the experimental data.
Error function
Adjusted determination coefficient
Average relative error A measure of the variability of the linear model is explained by
the adjusted linear coefficient of determination ðR2 Þ [179,236]
Ad j
" #
represented in Eq. (46)
100 X ðqe;cal — qe;meas Þ
p
. Σ
R
i
n—p
n (43) 2
qe;meas (46)
i¼1 Ad j n—1
¼ 1 — ð1 — R2Þ·

Average relative error function attempts to reduce the


fractional error distribution across the entire concentration range Error function [179,236]
[234].
Where qe,calc is the calculated adsorbate concentration at vffiffiffiffiffiffiffiffiffi ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi ffi
equilibrium(mg/g), qe,meas measured adsorbate concentration at u. 1 Σ X n
2
equilibrium (mg/g), n is the number of data points and p is the Ferror ¼ t · ðqi;exp — qi;modelÞ (47)
n—p
number of parameter of the isotherm equation. i
410 n — p 2 (2014) 398–414
S. Rangabhashiyam et al. / Journal of Environmental Chemical Engineering
i
S. Rangabhashiyam et al. / Journal of Environmental Chemical Engineering 2 (2014) 398–414 411

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