Journal of Molecular Liquids 334 (2021) 116542

Contents lists available at ScienceDirect

Journal of Molecular Liquids

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

Comments on ‘‘Reasonable calculation of the thermodynamic

parameters from adsorption equilibrium constant, Journal of Molecular
Liquids 322 (2021) 114980.”
Eder C. Lima a,⇑, Farooq Sher b, Mohammad Reza Saeb c, Mohamed Abatal d, Moaaz K. Seliem e
a
Institute of Chemistry, Federal University of Rio Grande do Sul (UFRGS), Av. Bento Goncalves 9500, Postal Box 15003, ZIP 91501-970, Porto Alegre, RS, Brazil
b
School of Mechanical, Aerospace and Automotive Engineering, Faculty of Engineering, Environmental and Computing, Coventry University, Coventry CV1 5FB, United Kingdom
c
Center of Excellence in Electrochemistry, School of Chemistry, College of Science, University of Tehran, Tehran, Iran
d
Facultad de Ingeniería, Universidad Autónoma del Carmen, Ciudad del Carmen, Campeche, Mexico
e
Faculty of Earth Science, Beni-Suef University, 62511, Egypt

a r t i c l e i n f o a b s t r a c t

Article history: The determination of thermodynamics parameters of adsorption is a controversial issue in the adsorption
Received 25 March 2021 field. The correct way of obtaining the adsorption thermodynamic parameters’ values involves obtaining
Revised 28 April 2021 adsorption isotherms at least four different temperatures. However, this correct procedure demands
Accepted 18 May 2021
much experimental work, and some researcher wants to take a shortcut to obtain faster results, indepen-
Available online 21 May 2021
dently if these results have or not physical meaning. However, in the paper Journal of Molecular Liquids
322 (2021) 114980, the authors want to turn official the incorrect way of obtaining confident results of
Keywords:
thermodynamic parameters. Practically, every definition written in the paper is biased, with several not
Adsorption
The thermodynamic equilibrium constant
funded definitions that would lead to the Adsorption Field’s trivialization. This comment will correct the
Thermodynamic parameters misinformation published to avoid the propagation of error throughout the literature.
van’t Hoff equation Ó 2021 Elsevier B.V. All rights reserved.

Comments to the Editor DH0 1 DS0

The correct information about Science should be spread and
used for the development of knowledge. Errors committed in the
Adsorption Field are so constant and severe that they threaten
adsorption authors’ credibility [1].
Recently Chen et al. [2] published a paper concerning ‘‘Reason-
able calculation of the thermodynamic parameters from adsorption
equilibrium constant.” However, this manuscript has so many flaws
of concepts that need some clarification.
First of all, the arrow utilized for equilibrium should be a double
semi-arrow
. The arrow utilized by these authors is a single full arrow
(⟷) stands for resonance [3,4]. Therefore equation (2) should be:
S þ A
S  A
Usually, the symbol for a standard is °; however, the symbol h is
recommended by IUPAC [3]. Considering that the symbol ° is
spreadly used, we will employ it for defining DG° for free standard
Gibb’s free energy, DH° standard changes in enthalpy, and DS° for
standard changes in entropy [4,5]. The linearized van’t Hoff equa-
tion should be written as:
⇑ Corresponding author.
E-mail address: profederlima@gmail.com (E.C. Lima).
LnðK e0 Þ ¼ : þ ð2Þ
R T R
Adsorption is a mass transfer phenomenon where chemical
substances (ions, molecules, particles) are removed from fluid
phases (liquids or gases) and transferred to the surface of a solid
or a liquid. From the Engineering perspective, adsorption is a mass
transfer-based unit operation, where dissolved ions or molecules
are transferred from a fluid to a solid phase [6]. The authors
wrongly used the term ‘‘adsorption-reaction” throughout the text.
A chemical reaction would consist of reactants forming products
that could be quietly different from the reactants.
a Aþb B!c Cþd D ð3Þ
ð1Þ
where a, b, c, and d are stoichiometric coefficients, and A and B are
the reactants and C, and D the chemical reaction products.
Most of the adsorption process is physical adsorption and not
chemisorption. The last process would occur when the adsorption
enthalpy changes are 200 kJ mol1 [7]—contradicting several
adsorption papers that consider changes in enthalpy of 40 kJ mol1
or even lower. Some authors confound hydrogen bonding, p-p
interaction, n-p interaction (acceptor and donor electron interac-
tion), electrostatic attraction as chemical sorption [2,8]. However,
the energies for those interactions are <80 kJ mol1 [7], therefore,

https://doi.org/10.1016/j.molliq.2021.116542
0167-7322/Ó 2021 Elsevier B.V. All rights reserved.
E.C. Lima, F. Sher, Mohammad Reza Saeb et al. Journal of Molecular Liquids 334 (2021) 116542

the term ‘‘adsorption reaction” should be banned from the vocabu- qe

KL ¼ ð13Þ
lary of Adsorption Experts, and the term covalent adsorption and ðQ max  qe Þ:C Adsorbate
non-covalent adsorption should be included. Introducing Eq. (13) onto Eq. (11), it leads to
The correct thermodynamic equilibrium constant (K 0e ) is shown
in Eq. (4) [10,11]: K L :C 0Adsorbate
K oe ¼ ð14Þ
h cAdsorbate
K e ¼ :C 0 ð4Þ
ð1  hÞ:C e :c In this equation, KL is the Langmuir equilibrium constant
where h means surface coverage of the adsorbent, Ce is the equilib- expressed in L mol1; by definition, C 0Adsorbate =1 mol L-1 and cAdsorbate
rium adsorbate concentration, C° is the standard concentration of is dimensionless.
the adsorbate (by definition, it is 1 mol L-1), and c is the activity Although this equation was deduced using the Langmuir iso-
coefficient of the adsorbate (dimensionless). therm model, any equilibrium constant with the unit of L mol1
Considering the chemical equilibrium of adsorption of an adsor- could be used, such as Liu, Sips, Redlich-Peterson, Toth, and others
bate by one adsorbent as given below [9,12]: [9,12].
Therefore, this equation could be written as Eq. (15):
adsorption
AdsorbentðsÞ þ AdsorbateðaqÞ
Adsorbent  AdsorbateðsÞ ð5Þ
desorption K g :C 0Adsorbate
K oe ¼ ð15Þ
The equilibrium constant could be given as [9]:
cAdsorbate
aAdsorbentAdsorbate where Kg is any equilibrium constant obtained from different iso-
K oe ¼ ð6Þ
aAdsorbent :aAdsorbate therm models (Langmuir, Liu, Langmuir-Freundlich, Sips) expressed
in L mol1.
where aAdsorbent-Adsorbate is the activity of Adsorbent-Adsorbate(s),
Eq. (15) should be used when the concentrations are expressed
aAdsorbent is the activity of Adsorbent(s), and aAdsorbate is the activity
in mol L-1 and sorption capacities are expressed in mol kg1.
of the adsorbate solution (aq).
Notwithstanding, many authors use the concentration in mg L-1,
Activity by definition is [9,12]:
sorption capacities in mg g1, which will lead to the isotherm K
C expressed in L mg1. However, to apply the thermodynamic equi-
a ¼ :c ð7Þ
C0 librium constant, it is recommended to use the expression below
[9,12]:
where a is the activity, C is the concentration of the specie (mol L-1),
C° is the standard concentration of the specie, which by definition is ð1000:Kg:molecular weight of adsorbate: ½adsorbate Þ
K 0e ¼ ð16Þ
1 mol L-1, and c is dimensionless. Considering Eq. (7), the activity of c
any specie is dimensionless. This is the reason that the thermody-
Considering the units of Eq. (16) [9,12]:
namic equilibrium constant (K 0e ) is dimensionless. Many authors
1
try to use any mathematical strategy to arrive at a dimensionless 1000 mg g 1 :L mg 1 :g mol : 1 mol L1
equilibrium constant [12]. Nevertheless, the thermodynamic equi- K 0e ¼
dimensionless
librium constant is dimensionless because the activity (a) is without
¼ dimensionless ð17Þ
dimension.
Considering Eq. (8): Note that the thermodynamic equilibrium constant is dimen-
aAdsorbentAdsorbate h sionless; however, it should be clear to the reader that Ke° is
¼ ð8Þ dimensionless because the activities described in Eqs. (6) and (7)
aAdsorbent 1h
are dimensionless. Therefore, the Adsorption Scholars should not
The activity of Adsorbent-Adsorbate(s) corresponds to the cov- try to make any expression in a dimensionless ‘‘equilibrium con-
erage surface (h) of the adsorbent, and the activity of Adsorbent(s) stant” because it does not have physical meaning, as already
corresponds to the 1 minus the coverage surface [9]. reported [9,12].
The thermodynamic equilibrium constant could be given as: Continuing with evaluating the errors committed in the paper
  of Chen et al., [2], Eq. (8) of the original paper is entirely wrong
aAdsorbentAdsorbate h C 0Adsorbate
K oe ¼ ¼ : ð9Þ (see Fig. 1).
aAdsorbent :aAdsorbate 1  h C Adsorbate: cAdsorbate The equation described in Fig. 1 is totally wrong because q° does
Considering that [13,14]: not exist. The standard conditions expressed by using the
symbols ° or h could not be arbitrarily assumed for any variable.
qe
h¼ ð10Þ The q° would be the initial standard initial concentration (C o0 )
Q max
minus the standard equilibrium concentration (C 0e ) multiplied by
Eq. (10) becomes Eq. (11): the standard volume (V°) and divided by standard mass (m°), as
 
qe represented in Fig. 2.
Q max C 0Adsorbate Although Chen et al. [2] did not mention the equation of Fig. 2
K oe ¼ :
1  Q max C Adsorbate: cAdsorbate
qe
(definition for q°) in the original manuscript, the q° would mean
the equation described in Fig. 2.
qe C 0Adsorbate If C 00 and C 0e were 1 mol L-1, the value of q° would be zero, which
¼ : ð11Þ
Q max  qe C Adsorbate: cAdsorbate
implies that K 0d would be an undetermined value or a value tending
Considering the Langmuir equilibrium model: to the infinite, using the concept of function limit. Therefore, the
authors’ strategy of transforming a Kd (expressed in L kg1) into a
Q max  K L  C Adsorbate
qe ¼ ð12Þ unidimensional expression is incorrect.
1 þ K L  C Adsorbate Therefore, any section of the paper reported by Chen et al. [2]
Isolating KL that use the q° and K 0d do not make sense and should not be used
for obtaining correct values of the thermodynamic parameters of
2
E.C. Lima, F. Sher, Mohammad Reza Saeb et al.
Fig 1. The wrong expression of K0d , that is Eq. (8) of Ref. [2].
Fig 2. The wrong expression of q0e .
adsorption using linearized or nonlinear van’t Hoff equation [15].
For obtaining accurate values of DG°, DH°, and DS° of adsorption,
please use Eq (15) (when working with concentrations expressed
in mol L-1, sorption capacities in mol kg1) or Eq (16) (when work-
ing with concentrations expressed in mg L-1, and sorption capaci-
ties in mg g1).
In order to make clear that Kd or K 0d , do not leave to accurate
results for the estimation of the adsorption thermodynamic
parameters using van’t Hoff plot; and that these parameters values
should be obtained from the application of van’t Hoff equation
using equilibrium constants that were attained from the isotherm
fitting at least from four different temperatures, we will explore
the determination of the thermodynamic parameters of adsorption
using K 0d and the thermodynamic K 0e (Eq. (15)) using data of
adsorption of the Acid Red 1 (AR-1) dye onto the APTES-Tannin
hybrid (1.5 g L-1) at pH 2 at different temperatures [16].
Table S1 present the numeric data of the values of sorption
capacity at equilibrium (qe) and the respective concentration at
equilibrium (Ce) after the adsorption of AR-1 dye onto APTES-
Tannin (1.5 g L-1) at 25°, 30°, 35°, 40°, 45°, and 50 °C [16]. The third
column corresponds to the values of K d ¼ Cqee , which were inserted
for obtaining the values of K 0d (see Fig. 1). Fig S1 present all the iso-
therm of adsorption of AR-1 dye onto adsorbent at 25°, 30°, 35°,
40°, 45°, and 50 °C [16]. In order to keep all units in SI standards,
the concentrations were expressed in mol L-1, sorption capacities
in mol kg1, values of equilibrium constant obtained from isotherm
were expressed in L mol1, and values of Kd were expressed in L
kg1. This study aims to compare the use of equation (15) (K 0e ) to
Equation (18) given below for obtaining the thermodynamic
parameters of adsorption.
qe
q0 C0
K 0d ¼ Ce
¼ Kd:
q0
C0
Journal of Molecular Liquids 334 (2021) 116542
Fig S2 shows plots of Kd versus Ce for temperatures ranging
from 25° to 50 °C. As shown in Fig S2 and the values of Kd reported
in Table S1, all Kd values are different for each experimental point.
Therefore, Kd is not a unique value.
Fig. 3 shows how the values of Table S2 were obtained at 298 K.
For obtaining K 0e it was necessary to obtain six isotherms at six dif-
ferent temperatures (298–323 K). After, the equilibrium data were
fitted using the nonlinear Liu isotherm model [16]. For each iso-
therm, it was obtained a different value of Kg is displayed in
Table S2.
On the other hand, the Kd values were obtained by fitting the
data of Kd versus Ce to exponential decay equations. It is possible
to infer that the plots of Fig S2 were suitably fitted using exponen-
tial decay equations, which could be checked by the high values of
R2 and R2adj displayed directly in Fig S2. All values of Kd are different
for each experimental point, which means that the term constant
could not be used for the ratio Cqee : Even if the highest point is deleted
(see Fig. 3B), it is observed that it is impossible to obtain a unique
value of Kd. In this sense, Kd values result from interpolation in the
curves of Fig S2, when Ce = 0 [12].
Fig. 4 summarizes all the results and calculations made in
Tables S1 and S2, Figs. S1 and S2, where the linearized van’t Hoff
plot was used using the equilibrium constant depicted in Eq. (15)
(Fig. 4A and 4B) and the van’t Hoff plot using the equilibrium con-
stant depicted in Eq. (18) (Fig. 4C, 4D, and 4E). A perfect linearized
plot of the van’t Hoff equation was obtained, using values of equi-
librium constant obtained from the adsorption isotherm at six dif-
ferent temperatures (298–323 K). Also, using the nonlinearized
van’t Hoff equation (Fig. 4B), as already reported [15], the differ-
ences of DH° and DS° of adsorption were in the decimal places
(see Fig. 4A and 4B) comparing the differences of linear and nonlin-
ear van‘t Hoff plots. On the other hand, when the van’t Hoff plot
was used utilizing the values of K 0d (see Table S2 and Fig S2), it
was not possible to obtain an accurate plot using the six tempera-
tures (see Fig. 4C). The R2 and R2adj obtained were only 0.3049 and
0.1312, indicating that the values of LnK 0d versus 1/T is not a linear
function.
However, as it was already described [9], when thermodynamic
data are obtained using just three experimental temperatures, it is
still possible to obtain suitable linearization of van’t Hoff equation
using K 0d (R2 0.9922 Fig. 4D, and 0.9684 Fig. 4E). Therefore, authors
using just three experimental temperatures could obtain values of
DH° and DS° that just seeing the values, it is impossible to infer
that the results are meaningless, and erroneous conclusions about
the mechanism of adsorption could be formulated.
Let us discuss the values of DH° of adsorption of AR-1 anionic
dye onto positively charged APTES-Tannin hybrid adsorbent at
pH 2 [16]. The values of DH° obtained in Fig. 4A and 4B were
24.25 and 24.02 kJ mol1 (exothermic process), respectively,
that is compatible with physical adsorption. On the other hand,
the DH° values obtained from Fig. 4D and 4E were + 71.55 (en-
dothermic) and 135.45 kJ mol1 (exothermic). Observe that in
Fig. 4D, the R2 value was 0.9922, but a positive value of enthalpy
(endothermic) was obtained, and it is expected that the adsorption
process was exothermic (see Fig. 4A and 4B). Concerning Fig. 4E,
some authors could wrongly attribute that the adsorption process
is chemisorption since DH° value is > 80 kJ mol1. Therefore, using
only three temperatures in the van’t Hoff plots, wrong conclusions
could be drawn from the thermodynamic studies, mainly if Kd is
utilized.
For the adsorption of AR-1 dye onto the adsorbent, it should be
stated that the values of DH° obtained from the equilibrium con-
stants obtained from nonlinearized isotherm fitting lead to values
ð18Þ of about 24 kJ mol1, that is compatible with physical adsorption,
such as electrostatic attraction, as earlier reported [16].
3
E.C. Lima, F. Sher, Mohammad Reza Saeb et al. Journal of Molecular Liquids 334 (2021) 116542

Fig 3. A- Isotherm of adsorption of AR-1 dye onto APTES-Tannin (1.5 g L-1) at 25 °C. B- Kd versus Ce at 25 °C. C- - Kd versus Ce at 25 °C after deleting the first point.

Fig 4. van’t Hoff plots to determine the DH° and DS° of adsorption for removing AR-1 dye onto APTES-Tannin hybrid adsorbent. A- Linearized van’t Hoff plot using the
equilibrium constant described in Eq. (15). B- Nonlinear van’t Hoff plot using the equilibrium constant described in Eq. (15). C- Linearized van’t Hoff plot using the equilibrium
constant described in Eq. (18). D- Linearized van’t Hoff plot using the equilibrium constant described in Eq. (15), using three experimental temperatures (curve 1). E-
Linearized van’t Hoff plot using the equilibrium constant described in Eq. (15), using three experimental temperatures (curve 2).

Based on the results depicted in this current manuscript, the
authors recommend to:
Perform isotherm at least four different temperatures;
Use nonlinear fitting to obtain more accurate results of the
isotherm;
If the authors use concentrations expressed in mg L-1 and sorp-
tion capacities in mg g1, use Eq. (16) for obtaining K 0e , that should
be furtherly employed in the van’t Hoff equation to better estimate
the values of DH°, DS°, and DG° of adsorption.
If the author use concentration expressed in mol L-1, sorption
capacities in mol kg1, use Eq. (15) for calculating K 0e , and furtherly
obtain the thermodynamic parameters of adsorption.
The authors reinforce that the ratio Cqee is not an equilibrium
constant since, for each concentration of adsorbate, a different
value of this ratio will be obtained (see Table S1, Fig S2), and
also, an erroneous conclusion could be drawn from the thermo-
dynamic parameters obtained using this ratio Cqee in the van’t Hoff
equation.

4
E.C. Lima, F. Sher, Mohammad Reza Saeb et al.
The authors should clarify that the main criticism of this letter
is limited to Eq. (8) of the previous publication (Eq. (18) of this
comment).
CRediT authorship contribution statement
Eder C. Lima: Original draft, Visualization. Farooq Sher: Revis-
ing & editing. Mohammad Reza Saeb: Revising & editing.
Mohamed Abatal: Revising & editing. Moaaz K. Seliem: Revising
& editing.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgements
The authors thank CAPES, FAPERGS, and CNPq for sponsorship.
Appendix A. Supplementary material
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.molliq.2021.116542.
References
[1] C. Tien, Remarks on adsorption manuscripts received and declined: An
editorial, Sep. Purif. Technol. 54 (2007) 277–278.
[2] T. Chen, T. Da, Y. Ma, Reasonable calculation of the thermodynamic parameters
from adsorption equilibrium constant, J. Mol. Liq. 322 (2021), https://doi.org/
10.1016/j.molliq.2020.114980 114980.
[3] T. Renner, Quantities, Units, and Symbols in Physical Chemistry, Royal Society
of Chemistry, 2007.
Journal of Molecular Liquids 334 (2021) 116542
[4] P. Atkins, J. de Paula, Physical Chemistry, ninth ed., W. H. Freeman and
Company, New York, 2010.
[5] I.N. Levine, Physical Chemistry, sixth ed., Mc Graw Hill, New York, 2009.
[6] G.L. Dotto, G. McKay, Current scenario and challenges in adsorption for water
treatment, J. Environ. Chem. Eng. 8 (2020), https://doi.org/10.1016/
j.jece.2020.103988 103988.
[7] R. Chang, J.W. Thoman-Jr, Chapter 17- Intermolecular forces, in: Physical
Chemistry for Chemical Sciences, University Science Books, 2014, pp. 779–808.
[8] T.E. Payne, V. Brendler, M. Ochsc, et al., Guidelines for thermodynamic sorption
modelling in the context of radioactive waste disposal, Environ. Modell. Softw.
42 (2013) 143–156.
[9] E.C. Lima, A. Hosseini-Bandegharaei, I. Anastopoulos, Response to ‘‘Some
remarks on a critical review of the estimation of the thermodynamic
parameters on adsorption equilibria. Wrong use of equilibrium constant in
the van’t Hoff equation for calculation of thermodynamic parameters of
adsorption - Journal of Molecular Liquids 273 (2019) 425–434”, J. Mol. Liq. 280
(2019) 298–300.
[10] S. Salvestrini, V. Leone, P. Iovino, S. Canzano, S. Capasso, Considerations about
the correct evaluation of sorption thermodynamic parameters from
equilibrium isotherms, J. Chem. Thermod. 68 (2014) 310–316.
[11] H.N. Tran, S.J. You, A. Hosseini-Bandegharaei, H.-P. Chao, Mistakes, and
inconsistencies regarding adsorption of contaminants from aqueous
solutions: a critical review, Water Res. 120 (2017) 88–116.
[12] E.C. Lima, A. Hosseini-Bandegharaei, J.C. Moreno-Piraján, I. Anastopoulos, A
critical review of the estimation of the thermodynamic parameters on
adsorption equilibria. Wrong use of equilibrium constant in the Van’t Hoof
equation for calculation of thermodynamic parameters of adsorption, J. Mol.
Liq. 273 (2019) 425–434.
[13] Y. Liu, Is the free energy change of adsorption correctly calculated?, J. Chem.
Eng. Data 54 (2009) 1981–1985.
[14] A. Fenti, P. Iovino, S. Salvestrini, Some remarks on ‘‘A critical review of the
estimation of the thermodynamic parameters on adsorption equilibria. Wrong
use of equilibrium constant in the Van’t Hoof equation for calculation of
thermodynamic parameters of adsorption” - Journal of Molecular Liquids 273
(2019) 425–434,”, J. Mol. Liq. 276 (2019) 529–530.
[15] E.C. Lima, A.A. Gomes, H.N. Tran, Comparison of the nonlinear and linear forms
of the van’t Hoff equation for calculation of adsorption thermodynamic
parameters (DS° and DH°), J. Mol. Liq. 311 (2020), https://doi.org/10.1016/
j.molliq.2020.113315 113315.
[16] A.J.B. Leite, E.C. Lima, G.S. dos Reis, P.S. Thue, C. Saucier, F.S. Rodembusch, S.L.P.
Dias, C.S. Umpierres, G.L. Dotto, Hybrid adsorbents of tannin and APTES (3-
aminopropyltriethoxysilane) and their application for the highly efficient
removal of acid red 1 dye from aqueous solutions, J. Environ. Chem. Eng. 5
(2017) 4307–4318.