See

discussions, stats, and author profiles for this publication at: https://www.researchgate.net/publication/311614551

Comments on "Characterization and

adsorption capacity of raw pomegranate peel
biosorbent for copper...

Article in Journal of Cleaner Production · December 2017

DOI: 10.1016/j.jclepro.2016.12.066

CITATIONS READS

0 1,739

1 author:

Hai Tran
Chung Yuan Christian University
13 PUBLICATIONS 15 CITATIONS

SEE PROFILE

Some of the authors of this publication are also working on these related projects:

I am a PhD student (the four year) at Chung Yuan Christian University in Taiwan. Nice too meet you.
View project

All content following this page was uploaded by Hai Tran on 01 January 2017.

The user has requested enhancement of the downloaded file. All in-text references underlined in blue are added to the original document
and are linked to publications on ResearchGate, letting you access and read them immediately.
 Journal of Cleaner Production xxx (2017) xxx-xxx

Contents lists available at ScienceDirect

Journal of Cleaner Production

F
journal homepage: www.elsevier.com

OO
Letter to the editor

Comments on “Characterization and adsorption capacity of raw pomegranate peel

biosorbent for copper removal”
Hai Nguyen Tran

PR
Department of Environmental Engineering, Chung Yuan Christian University, Chungli 320, Taiwan

ARTICLE INFO ABSTRACT

Article history: This article aims to discuss (1) misapplications of the “iodine number” to determine the surface area of an adsor-

ED
Available online xxx bent, (2) inconsistency discussions about FTIR, (3) incorrect assumptions regarding pKa of surface oxygen functionali-
ties, (4) invalid discussions on adsorption mechanisms, (5) inaccurate calculations on the adsorption energy of the Du-
binin–Radushkevich equation, (6) incorrect expressions for the kinetic models (i.e., intra-particle diffusion and Elovich)
and inconsistent data points in experimental data and model fitting, (7) mistakes in calculating the thermodynamic para-
meters, and (8) other miscellaneous errors. The author hopes that this work will contribute to avoiding the propagation of
incorrect information in the scientific community in the field of adsorption studies.
© 2016 Published by Elsevier Ltd.
CT
A recent paper by Ben Ali et al. (2016) entitled characterization Therefore, the iodine number cannot be applied for the determina-
and adsorption capacity of raw pomegranate peel biosorbent for cop- tion of porosity of any biosorbent. Moreover, it is impossible to ob-
per removal, contained several inaccurate calculations, incorrect ex- tain the extremely high iodine number reported for PGP (602 mg/g) as
perimental data interpretations, and inappropriate conclusions. My de- shown in Table 3 in the Ben Ali's paper. In my opinion,the high iodine
tailed comments are as follows: number for PGP can be attributed to the high sulfur content (0.89%)
as shown in Table 3 and a prolonged contact time (>30 s). Accord-
RE

1. Surface area of biosorbent determined by the iodine number
(Section 3.1)
The authors used the “iodine number” to determine the surface area
of a biosorbent without any treatment (pomegranate peel; PGP) and
concluded that “the specific surface area obtained is equal to 598.78
m2/g. Iodine number is generally used as an approximation for surface
R
ing to the ASTM (D4607-14 2014), after transferring activated car-
bon (g) into hydrochloric acid solution (5 wt %), the mixture should
be boiled gently for 30 s to remove any sulfur that may interfere with
the test results. Therefore, it is clear that the iodine number is greatly
affected by the presence of high sulfur content. Notably, the contact
time between activated carbon and iodine solution (0.1 N) has a strong

area and microporosity of active carbons with good precision”. There impact on the determined iodine number. The contact time recom-
are two serious misconceptions in this work that need to be discussed. mended by the ASTM was approximately 30 s, while the contact time
First, the iodine number of activated carbon (AC) is often deter- used by Ben Ali et al. was approximately 4 min. Recently, Tran et al.,
CO

mined following the internal method, ASTM (D4607-14 2014). Ac-
cording to the ASTM standard, the iodine number (mg/g; amount of
iodine adsorbed (mg) by 1.0 g of AC) is a relative indicator of poros-
ity in AC. Iodine molecules (≈0.27 nm) can be adsorbed into micro-
pores (pore width > 1 nm) of porous materials. However, the iodine
number does not necessarily provide a measure of the carbon's ability
to absorb other species. Although the iodine number may be used to
UN
(2017b) prepared activated carbons from golden shower through dif-
ferent chemical activation methods with K2CO3 (GSAC, GSBAC, and
GSHAC). Their results indicated that the iodine numbers (mg/g) of the
prepared activated carbons at a contact time of 30 s were significantly
lower than those at 5 min; GSAC (2,604 mg/g < 2,883 mg/g), GSBAC
(1,568 mg/g < 2,296 mg/g), GSHAC (2,695 mg/g < 4,842 mg/g).
Second, the textural properties of an adsorbent (i.e., specific sur-

approximate the surface area for several types of AC, it must be re-
alized that the relationship between surface area and iodine number
cannot be generalizedas it varies with changes in carbon raw mater-
ial, processing conditions, and pore volume distribution. Biosorbents
that have not undergone any treatments or activations have never been
defined as porous materials; thus, the porosity of a biosorbent is neg-
ligible.
Email address: Trannguyenhai2512@gmail.com (T.H.N.T. Hai)
face area, total pore volume, and micropore volume) can be obtained
from conventional analysis of nitrogen adsorption-desorption
isotherms, which are measured at 77 K using a sorptometer (i.e.,
Micromeritics ASAP 2020). The Brunauer–Emmett–Teller (BET)
method is widely employed to compute the specific surface area of an
adsorbent (SBET) (Marsh and Reinoso, 2006). Therefore, it is impossi-
ble to measure the surface area of an adsorbent using the iodine num-
ber method. This mistaken assumption will lead to incorrect result,
such as the extremely high surface area of PGP (598 m2/g; see Table
3 in the Ben Ali's paper). The BET surface areas of various biosor-
bents are approximately 40 m2/g for yellow passion-fruit shell, 20

http://dx.doi.org/10.1016/j.jclepro.2016.12.066
0959-6526/© 2016 Published by Elsevier Ltd.
2 Journal of Cleaner Production xxx (2017) xxx-xxx
m2/g for orange peel, 8.17 m2/g for wheat straw, 8.13 m2/g for Sargas-
sum, 4.01 m2/g for Moringa oleifera lamarck seed powder, 1.31 m2/g
Spirogyra species, 1.21 m2/g for waste pomace from an olive oil fac-
tory, 0.76 m2/g for soy meal shells, 0.48 m2/g for rubber tree leaves,
and 0.48 m2/g for rice bran (Farooq et al., 2010; Tran et al., 2016).
In summary, any discussions and conclusions regarding the surface
area of PGP made by Ben Ali and coworkers are not valid, as they are
inconsistent with the ASTM definitions and fundamental understand-
ing of the porosities of materials.
2. The analysis results of FTIR in Section 3.1
The authors provided an inconsistency information. For example,
in page 3811, they reported that “the band at 1607.21 cm−1 is assigned
to the stretching vibration bond of (C O) and (C C)”. This infor-
mation was inconsistent with with the information presented in Table
2 that the peak at 1607.21 cm−1 belongs to (C C) or (C N) defor-
mation N H of amines or amides. Similarly, the authors explained
that “the peaks at 1322.65 cm−1 and 1029.18 cm−1 are assigned to
(C O) groups of carboxylic acid, alcoholic, phenolic, ether and es-
ter groups”, which was also inconsistent with the information pre-
sented in Table 2: the peaks at 1322.65/748.7 cm−1 corresponding to C
H aliphatic: ( CH3) or ( CH2). Thus, the discussions related to
FTIR in the Ben Ali's paper demonstrated a great confusion and am-
ED
biguity.
3. Effect of pH solution in Section 3.2.1
The authors reported that the effect of pH on the interaction of cop-
per with the surface functional groups has been explained as follows:
CT
R OH2+ ↔ R OH + H+ (1)
R OH ↔ R O− + H+ (2)
R O− + Cu2+ ↔ R OCu+ (3)
O− + Cu(OH)+ ↔ R
RE
R OCu(OH) (4)
+ data points in experimental data and model fitting (Section 3.4)
“where R represents the surface adsorbent; R OH2 , R OH and
R O− represent protonated, neutral, and ionized surface hydroxyl
functional groups; R OCu+ and R OCu(OH) are formation of the
bonding complexes.”
R
The authors explained that, “the effect of pH could be also ex-
plained by considering the point of zero charge of the adsorbent
(pHpzc). The adsorbent surface is positively charged for pH < 4.7
CO
and it becomes negatively charged at pH value above 4.7. There-
fore, for pH values < 4.7, the adsorption is unfavorable because of
repulsive electrostatic interactions between metal ions and positively
charged functional groups. The maximum adsorption of Cu(II) oc-
curs at pH above pHpzc value when the adsorbent surface is nega-
tively highly charged”. However, the important role of the pKa values
of carboxylic groups ( COOH; pKa 1.7–4.7) and hydroxyl groups (
UN
OH; pKa 9.5–13) was ignored (Volesky, 2007). As a result, Equa-
tions (1)–(4) indicates a misunderstanding of the surface chemistry
of the adsorbent. Fig. 5 in the Ben Ali's paper demonstrates that the
experiment on pH dependence of Cu(II) adsorption process was con-
ducted at the solutions pH from 2.0 to 6.0. Therefore, dissociation
of the OH groups into O- did not occur at these solutions pH
values. Instead, the COOH groups dissociated, forming negatively
charged carboxylate groups ( COO‒) (Tran et al., 2016). These er
rors make their conclusions invalid.
4. Invalid discussions regarding the effect of temperature in Sec-
tion 3.2.4
As aforementioned, biosorbent often exhibits poor surface area and
F
low total pore volume. It means that the contributions of pore filling
in adsorption mechanism seem negligible. In this case, the adsorption
process of heavy metal by biosorbent might involve electrostatic at-
OO
traction (known as out-sphere complexation), non-electrostatic attrac-
tion (known as inner-sphere complexation), or cation exchange be-
tween Cu2+ ions in the solution with cations (Ca2+, Mg2+, K+, or Na+)
available on the biosorbent's surface (Iqbal et al., 2009; Tran et al.,
2016). Therefore, it is not valid when the authors try to interpret that
“the temperature increasing may leads to some changes of the pore
size that becomes larger, and to a relative increase in the diffusion
of the copper ions due to the solution viscosity decreasing, which im-
PR
proves their exposure to the adsorption on the sites difficult to access”.
Notably, in Section 3.2.1, the authors concluded that “the maximum
adsorption of Cu(II) occurs at pH above pHpzc value when the adsor-
bent surface is negatively highly charged”. This means that the elec-
trostatic attraction plays a primary role in the adsorption process of
Cu2+ ions onto pomegranate peel.
5. Inaccurate calculation regarding the adsorption energy in Sec-
tion 3.3.4
The authors concluded that “the obtained value of E in this work
varies from 32.596 kJ/mol to 40.572 kJ/mol for studied temperature
which is higher than the adsorption energy values previously enu-
merated”. However, these adsorption energy (E) values might be not
calculated correctly. Assuming the β values at 303 K (β = 1.93E-08
mol2/kJ2), 313 K (2.99E-08 mol2/kJ2), 323 K (2.00E-08 mol2/kJ2),
and 333 K (2.35E-08 mol2/kJ2) in Table 4 is correction, the recalcu-
lated adsorption energy (E) values are 5,090 kJ/mol at 303 K, 4,089
kJ/mol at 313 K, 5,000 kJ/mol at 323 K, 4,613 kJ/mol at 333 K. Thus,
the E values in this study ranged from 4,089 to 5,091 kJ/mol, which
is impossible for a biosorption process of heavy metal.
6. Incorrect expression for the kinetic models and inconsistent
Ben Ali et al. (2016) expressed the intra-particle diffusion model
(Eq. (5)) and the Elovich model (Eq. (6)) as follows:
(5)
(6)
However, the expression of Equation (5) and Equation (6) are not
correct. Incorrect Equation (5) might result from an oversight of miss-
ing typos; therefore, it should be expressed correctly as Eq (7).
(7)
An empirical equation was firstly proposed by Roginsky and
Zeldovich (1934) for the adsorption of carbon monoxide onto
manganese dioxide. However, this equation is now generally known
as the Elovich equation, which has been extensively applied to
chemisorption data (McLintock, 1967). The equation can be de-
scribed mathematically as follows:
 Journal of Cleaner Production xxx (2017) xxx-xxx
(8)
where qe and qt are the amounts of adsorbate uptake per mass of ad-
sorbent at equilibrium and at any time t (min); α (mg/g × min) is the
initial rate constant because of dqt/dt → α when qt → 0; and β (mg/g)
is the desorption constant during any one experiment.
By applying the boundary conditions of qt = 0 at t = 0, the inte-
grated form of Equation (8) will become Equation (9) (nonlinear).
(9)
To simplify the Elovich equation (Chien and Clayton, 1980), as-
sumed αβt >>1. Thus a linear form (Eq. (10)) will be obtained:
(10)
A plot of qt versus ln(t) should give a linear relationship with a
ED
slope of (1/β) and intercept of (1/β)ln(αβ). However, errors in the pre-
sentation of the nonlinear form of the Elovich model are common in
the literature. These mistakes can be identified in the previous pa-
pers (Ho and McKay, 1998; Lin and Wang, 2009; Alagumuthu et al.,
2010).
CT
(11)
(12)
RE
Therefore, any discussions related to the Elovich model in the Ben
Ali's paper will be not valid, and the re-calculation of the Elovich pa-
rameters is strongly recommended. Gupta et al. (2005) have suggested
that authors should read the original article before quoting it, rather
than citing from abstracts or cross-references.
Another important problem was the inconsistency error about the
data points between experiment and model. Clearly, the number of
R
experiment points in the adsorption kinetics (i.e., Figs. 7 and 8) was
overwhelmingly higher than that of points in Fig. 11.
The difference regarding the number of data points between the
CO
experiment and the model fitting should be avoided. For example,
Azizian (2008) made critical comments about a paper published by
Karadag et al. (2007), as follows: there are six experimental data
points in adsorption kinetics (the plots of qt versus t), but only five
experimental data points were used for fitting of the experimental
data to the pseudo-second-order model (plot of t/qt versus t). This
omission resulted in inaccurate calculations and questionable conclu-
UN
sions. The R2 values of pseudo-second-order model were very high
(0.992–1.000), but the difference between the experimental (qe,exp)
and calculated (qe,cal) values was more than 100% (for example
qe,exp = 6.720 mg/g and qe,cal = 15.526 mg/g). Clearly, the qe values
calculated from the experimental data and model were significantly
different, but Karadag et al. (2007) concluded that “The pseudo-sec-
ond-order kinetic model agrees very well with the dynamic behavior
for the adsorption of dyes RR239 and RB5 onto CTAB-zeolite under
several different dye concentrations, temperatures, and pH values”;
the validity of this conclusion is very questionable. In addition, Lima
3
et al. (2015) observed a change in kinetic parameters when five ex-
perimental points were deleted to achieve a good R2 value . They con-
cluded that the strategy of deleting some points to improve R2 causes
serious errors in the values of qe and k1 in the pseudo-first-order equa-
tion or k2 in the pseudo-first-order equation.
F
7. Mistake in calculating thermodynamic parameters (Section
3.5)
OO
The authors made misconceptions regarding the fundamental of the
adsorption thermodynamics. First, to estimate the thermodynamic pa-
rameters, the authors used three equations as follows:
(13)
(14)
PR
(15)
“where Cs and CL are the equilibrium concentration of copper in a liq-
uid (mg/L) and in a solid phase respectively, KL is Langmuir constant,
R is a gas constant, and T is a temperature (K)”.
I would like to highlight that the Langmuir constant KL has never
been calculated or expressed as Equation (15). In their study, Ben
Ali and coworkers applied the partition constant for calculation of the
thermodynamic parameters, not the Langmuir constant. In addition, a
recent comment on the inappropriate application of the partition con-
stant for calculating the thermodynamic parameters has been reported
by Hai (2016).
The thermodynamic equilibrium constant (or partition constant)
with changes in temperatures was originally published by Biggar and
Cheung (1973). The equilibrium constant can be defined as follows:
(16)
where as is the activity of the adsorbate adsorbed onto adsorbent; ae is
the activity of adsorbate in the solution at equilibrium; γs is the activity
coefficient of the adsorbate adsorbed onto adsorbent; γe is the activity
coefficient of adsorbate in the solution at equilibrium; Cs is the con-
centration of adsorbate adsorbed onto adsorbent at equilibrium (mg/
L); and Ce is the concentration of adsorbate in the solution at equilib-
rium (mg/L). The Cs is defined by the mass balance of adsorbate that
disappeared from the solution, which should appear on the adsorbent.
When the concentration of adsorbate in the solution approaches
zero, which results in Cs → 0 and Ce → 0, the activity of coefficient
γ approaches unity at low concentrations , and equation (16) can be
written as:
(17)
Kp values can be obtained plotting ln(Cs/Ce) against Cs and extrap-
olating Cs to zero. If a straight line fits the data with a high determi-
nation coefficient value (R2) and its intersection with the vertical axis
provides the value of Kp, the partition coefficient will be in unison
with the equilibrium constant (KC). The ΔGo value can be directly cal-
culated using Eq. (18), while the values of ΔHo and ΔSo are deter
4 Journal of Cleaner Production xxx (2017) xxx-xxx
mined from the slope and intercept, respectively, of Equation (20).
(18)
The relationship of ΔGo to ΔHo and ΔSo is described as:
(19)
The well-known van't Hoff equation is obtained by substituting Eq.
(18) into Eq. (19).
(20)
Second, the results of the adsorption kinetics (Fig. 8) and the ad-
sorption isotherms (Fig. 10 and Table 4) indicated that the adsorption
process of copper was strongly dependent on the operation tempera-
tures from 303 K to 333 K. It might be incorrect when the authors
only studied the effects of two temperatures (i.e., 303 and 313K) on
the changes of the Gibbs energy change (ΔG°), the enthalpy change
ED
(ΔH°), and the entropy change (ΔS°). Correspondingly, any discus-
sions and conclusions as regard to the adsorption thermodynamics in
the Ben Ali's paper should be approached with caution. According
to the high R2 values of the Langmuir model in Table 4, I suggest
that the authors should apply the Langmuir constant KL for calculat-
ing the thermodynamic parameters. However, the unit problem in the
thermodynamic calculation of adsorption using the Langmuir equation
CT
should be considered carefully (Milonjić, 2007, 2009; Zhou and Zhou,
2014; Tran et al., 2016; Tran et al., 2017a).
Recently, Tran et al. (2016) compared the thermodynamic parame-
ters of cadmium adsorption onto orange peel calculated from various
methods. They concluded that (1) the values of the equilibrium con-
stant (KC) were strongly dependent on the applied constants, such as
RE
Langmuir, Freundlich, Henry, and partition, (2) the thermodynamic
parameters (i.e., ΔG°, ΔH°, and ΔS°) calculated from the constants of
Langmuir, Freundlich, Henry and partition had the same sign; how-
ever, the magnitude of these parameters varied greatly according to
the applied constants, (3) the adsorption equilibrium data play a vital
role in determining the constants (i.e., Langmuir, Freundlich, Henry,
and partition) that are most appropriate to correctly calculate the ther-
R
modynamic parameters. Furthermore, the correlation coefficient (R2)
of van't Hoff equation is also another determining factor in selecting
the optimal derivation for KC. In their study, the thermodynamic para-
CO
meters of the biosorption process of cadmium onto orange peel were
appropriately calculated based on both the Langmuir and Freundlich
constant.
8. Other miscellaneous errors
8.1. The data of the surface oxygen functional groups (i.e., car-
boxylic and phenolic) are presented in Fig. 2; therefore, it is
UN
redundant when these data are presented again in Table 3. Fur-
thermore, the authors determined the oxygen-containing func-
tional groups on the biosorbent’ surface by Boehm titration.
Unfortunately, the authors did not use any method for CO2
expulsion, which can lead to incorrect titration results . The
acidic groups and basic sites on the adsorbent's surfaces can
be determined using Boehm titration by following the stan-
dardization protocol proposed by Goertzen et al. (2010). They
recommended that “the titration should be performed imme-
diately after degassing for 2 h with N2 or Ar, and degassing
should continue during the titration”.
8.2. It is very confusing when the authors wrote “The Langmuir
isotherm defines also a dimensionless separation parameter
(RL > 1). (RL > 1) is defined as” in Section 3.3.1. Furthermore,
the authors reported the equation of the dimensionless separa-
tion parameter without any citation. The essential characteris-
tics of the Langmuir isotherm model, which can be expressed
F
in terms of a dimensionless constant separation factor RL, were
originally proposed by Hall et al. (1966).
OO
8.3. In Section 2.3, the authors mentioned that “adsorption
isotherm experiments were carried out at different tempera-
tures (303, 313, 323 and 333 K) by shaking 0.25 g of PGP ad-
sorbent with 100 mL sample of Cu(II) solution of different ini-
tial concentrations that vary from 10 to 60 mg/L at pH of 5.8”.
However, in the captions of Fig. 9 (the linear isotherms) and
Fig. 10 (the adsorption isotherms), they provided a contrary
information as follows: “mPGP = 3 g/L, particle size ≤ 630 μ
PR
m, agitation speed = 200 rpm, T = 303 K, contact time = 2 h,
pH = 5.8, CCu(II) = 10–100 mg/L, VCu(II)100 mL”. Clearly, there
is an inconsistency error in the solid/liquid ratio and initial
Cu(II) concentration.
8.4. Fig. 7 in the Ben Ali's paper shows the effect of the contact
time and the initial ion concentration on the equilibrium ad-
sorption capacity of Cu(II) on PGP adsorbent. Therefore, the
symbol used in y-axis (Fig. 7) needs to be changed from qe
(mg/g) into qt (mg/g). The amount of adsorbate adsorbed at
equilibrium was defined as qe, while the amount of adsor-
bate adsorbed at time t was defined as qt.
8.5. There are not any available supporting data for the conclu-
sions that, “the same observations are noticed when metal
concentration increasing. Yet, the FTIR spectra of PGP before
and after copper Cu(II) adsorption shows either shift, reduc-
tion or appearance in absorption peaks”. Clearly, Fig. 12 in
the Ben Ali's paper presents “the FTIR spectra of pomegran-
ate peel: (a) before copper adsorption, (b) after copper ad-
sorption for particles size 800 ≤ d < 630 μm and (c) for par-
ticles size 630 ≤ d < 500 μm”, which means no any data for
the metal concentration increasing. This arbitrary makes their
conclusions invalid.
8.6. The word “A spectrum range 375–7800 cm−1 to observe dif-
ferent functional groups” in Section 2.1.6 should be restated
by the word “a spectrum range 650–400 cm−1” to obtain a
good accordance with Fig. 3 and Fig. 12.
8.7. The thermo-gravimetric graph (Fig. 4 in the Ben Ali's paper)
indicates a contrary result compared to the literature. The au-
thors pointed out that, “the DTA curves are characterized by
first endothermic peaks and mass loss about 2% due to water
evaporation for temperature between 343 and 433 K. Two en-
dothermic peaks are observed at 378 K and 443 K data have
revealed a weight loss of about 10.5% for temperature do-
main 523 K-643 K”. This means that the total mass loss is ap-
proximately 13%. The thermo-gravimetric graph in the Ben
Ali's paper demonstrates dissimilar information to the litera-
ture (see Fig. 1a in this study). Taking the thermo-gravimet-
ric graph of golden shower (a lignocellulose material) as a
typical example (Fig. 1c in this study), the weight loss tem-
perature (Tmax) at 56.2 °C was assigned to the vaporization
of moisture (≈4.11%). Meanwhile, the thermal decomposition
peaks at Tmax of 307 °C, 332 °C, and 451 °C were attributed to
the thermal degradation of hemicellulose (19.37%), cellulose
(38.95%), and lignin (37.57%) in golden shower, respectively
(Tran et al., 2017b).
8.8. In my opinion, it is necessary to re-check two experimental
points at Ce approximately 40 mg/g and 60 mg/g in Fig. 10
(adsorption isotherm at 313 K). The adsorption isotherm at
 Journal of Cleaner Production xxx (2017) xxx-xxx
ED
Fig. 1. Thermo-gravimetric analysis for (a) pomegranate peel (in the Ben Ali's paper), (b) orange peel (Chen and Chen, 2009), (c) golden shower (Tran et al., 2017b), and (d) Jat-
ropha curcasfruit shell (Tongpoothorn et al., 2011).
313 K demonstrated a dissimilar tendency to the others at 303
K, 323 K, and 333 K. Moreover, the parameters of the Lang-
muir and Freundlich equations (Table 4 in the Ben Ali's pa-
CT
per) might be inaccurately calculated. In essential, the KF
values and qm values should indicate the same order. Clearly,
the KF values followed the order: 4.471 at 303 K > 3.439 at
313 K and 323 K > 2.877 at 333 K, while the qm values were
30.12 mg/g at 313 K > 21.367 mg/g at 323 K > 21.276 mg/g
at 333K > 20.492 mg/g at 303 (Table 4). Therefore, all discus-
sions and conclusions readings to the adsorption isotherms in
RE
the Ben Ali's paper should be approached cautiously.
It should be clarified that my comments will not bring Ben Ali and
colleagues into discredit because the comments are aimed at avoiding
undesirable mistakes and the propagation of incorrect information in
the scientific literature.
R
References
Alagumuthu, G., Veeraputhiran, V., Rajan, M., 2010. Comments on “Fluoride removal
CO
from water using activated and MnO2-coated Tamarind Fruit (Tamarindus indica)
shell: batch and column studies”. J. Hazard. Mater. 183 (1–3), 956–957.
Azizian, S., 2008. Comments on “Adsorption equilibrium and kinetics of reactive
black 5 and reactive red 239 in aqueous solution onto surfactant-modified zeolite”
(Karadag, D.; Turan, M.; Akgul, E.; Tok, S.; Faki, A. J. Chem. Eng. Data 2007,
52, 1615−1620). J. Chem. Eng. Data 53 (1), 322–323.
Ben Ali, S., I. Jaouali, S. Souissi-Najar and A. Ouederni, . Characterization and ad-
sorption capacity of raw pomegranate peel biosorbent for copper removal.
J. Clean. Prod. 142, Part 4: 3809-3821. ( http://dx.doi.org/10.1016/j.jclepro.2016.
UN
10.081).
Biggar, J.W., Cheung, M.W., 1973. Adsorption of picloram (4-amino-3,5,6-trichlorop-
icolinic acid) on panoche, ephrata, and palouse soils: a thermodynamic approach to
the adsorption mechanism. Soil Sci. Soc. Am. J. 37 (6).
Chen, Baoliang, Chen, Zaiming, 2009. Sorption of naphthalene and 1-naphthol by
biochars of orange peels with different pyrolytic temperatures. Chemos-
phere 76 (1), 127–133.
Chien, S.H., Clayton, W.R., 1980. Application of Elovich equation to the kinetics of
phosphate release and sorption in soils. Soil Sci. Soc. Am. J. 44 (2), 265–268.
D4607,
2014 D4607–14, Standard Test Method for Determination of Iodine Number of Ac-
tivated Carbon, American Society for Testing and Materials, Philadelphia,
U.S.A, 2014.
5
F
OO
PR
Farooq, U., Kozinski, J.A., Khan, M.A., Athar, M., 2010. Biosorption of heavy metal
ions using wheat based biosorbents–a review of the recent literature. Bioresour.
Technol. 101 (14), 5043–5053.
Freundlich, H., 1906. Over the adsorption in solution. J. Phys. Chem. 57 (385471),
1100–1107.
Goertzen, S.L., Thériault, K.D., Oickle, A.M., Tarasuk, A.C., Andreas, H.A., 2010.
Standardization of the Boehm titration. Part I. CO2 expulsion and endpoint deter-
mination. Carbon 48 (4), 1252–1261.
Gupta, P., Yadav, M., Mohta, A., Choudhury, P., 2005. References in Indian pedi-
atrics: authors need to be accurate. Indian Pediatr. 42, 140–145.
Hai, T. N., 2017. Comments on “Effect of temperature on the adsorption of methylene
blue dye onto sulfuric acid-treated orange peel” Chem. Eng. Commun. 204(1):
134-139. (A http://dx.doi.org/10.1080/00986445.2016.1245185/).
Hall, K.R., Eagleton, L.C., Acrivos, A., Vermeulen, T., 1966. Pore- and solid-diffusion
kinetics in fixed-bed adsorption under constant-pattern conditions. Ind. Eng.
Chem. Fundam. 5 (2), 212–223.
Ho, Y.S., McKay, G., 1998. A comparison of chemisorption kinetic models applied to
pollutant removal on various sorbents. Process Saf. Environ. Prot. 76 (4), 332–340.
Iqbal, M., Saeed, A., Zafar, S.I., 2009. FTIR spectrophotometry, kinetics and adsorp-
tion isotherms modeling, ion exchange, and EDX analysis for understanding the
mechanism of Cd2+ and Pb2+ removal by mango peel waste. J. Hazard.
Mater. 164 (1), 161–171.
Karadag, D., Turan, M., Akgul, E., Tok, S., Faki, A., 2007. Adsorption equilibrium
and kinetics of reactive black 5 and reactive red 239 in aqueous solution onto sur-
factant-modified zeolite. J. Chem. Eng. Data 52 (5), 1615–1620.
Lima, É.C., Adebayo, M.A., Machado, F.M., 2015. Kinetic and Equilibrium Models of
Adsorption. Carbon Nanomaterials as Adsorbents for Environmental and Biologi-
cal Applications. Springer, 33–69.
Lin, J.X., Wang, L., 2009. Comment on “Adsorption of supranol yellow 4 GL from
aqueous solution by surfactant-treated aluminum/chromium-intercalated ben-
tonite”. J. Hazard. Mater. 172 (1), 516–517.
Marsh, H., Reinoso, F.R., 2006. Activated Carbon. Elsevier.
McLintock, I., 1967. The Elovich equation in chemisorption kinetics. Na-
ture 216, 1204–1205.
Milonjić, S.K., 2007. A consideration of the correct calculation of thermodynamic pa-
rameters of adsorption. J. Serb. Chem. Soc. 72 (12), 1363–1367.
Milonjić, S.K., 2009. Comments on “removal of uranium (VI) from aqueous solution
by adsorption of hematite”, by X. Shuibo, Z. Chun, Z. Xinghuo, Y. Jing, Z. Xiao-
jian, W. Jingsong. J. Environ. Radioact. 100 (10), 921–922.
Roginsky, S., Zeldovich, Y.B., 1934. The catalytic oxidation of carbon monoxide on
manganese dioxide. Acta Phys. Chem. USSR 1, 554.
Tongpoothorn, W., Sriuttha, M., Homchan, P., Chanthai, S., Ruangviriyachai, C.,
2011. Preparation of activated carbon derived from Jatropha curcas fruit shell by
simple thermo-chemical activation and characterization of their physico-chemical
properties. Chem. Eng. Res. Des. 89 (3), 335–340.
6 Journal of Cleaner Production xxx (2017) xxx-xxx

Tran, H.N., You, S.-J., Chao, H.-P.. Thermodynamic parameters of cadmium adsorp-
tion onto orange peel calculated from various methods: a comparison study. J. En-
viron. Chem. Eng. 4 (3), 2016, 2671–2682.
Tran, H. N., S.-J. You and H.-P. Chao. Fast and efficient adsorption of methylene
green 5 on activated carbon prepared from new chemical activation method, J. En-
viron. Manage. 188, 2017b, 322-336.Tran, H. N., S.-J. You and H.-P. Chao,
2017b. Activated carbons from golden shower upon different chemical activation
methods: synthesis and characterizations. adsorption science and technology
(DOI: 10.1177/0263617416684837).
Volesky, B., 2007. Biosorption and me. Water Res. 41 (18), 4017–4029.
Zhou, X., Zhou, X., 2014. The unit problem in the thermodynamic calculation of ad-
sorption using the Langmuir equation. Chem. Eng. Commun. 201 (11),
1459–1467.

F
OO
PR
ED
CT
R RE
CO
UN

View publication stats