Water Research 120 (2017) 88e116

Contents lists available at ScienceDirect

Water Research
journal homepage: www.elsevier.com/locate/watres

Review

Mistakes and inconsistencies regarding adsorption of contaminants

from aqueous solutions: A critical review
Hai Nguyen Tran a, b, *, Sheng-Jie You b, Ahmad Hosseini-Bandegharaei c, d,
Huan-Ping Chao b, *
a
Department of Civil Engineering, Chung Yuan Christian University, Chungli 320, Taiwan
b
Department of Environmental Engineering, Chung Yuan Christian University, Chungli 320, Taiwan
c
Wastewater Division, Faculty of Health, Sabzevar University of Medical Sciences, PO Box 319, Sabzevar, Iran
d
Department of Engineering, Kashmar Branch, Islamic Azad University, PO Box 161, Kashmar, Iran

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

Article history: In recent years, adsorption science and technology for water and wastewater treatment has attracted
Received 29 October 2016 substantial attention from the scientific community. However, the number of publications containing
Received in revised form inconsistent concepts is increasing. Many publications either reiterate previously discussed mistakes or
29 March 2017
create new mistakes. The inconsistencies are reflected by the increasing publication of certain types of
Accepted 6 April 2017
Available online 18 April 2017
article in this field, including “short communications”, “discussions”, “critical reviews”, “comments”, “letters
to the editor”, and “correspondence (comment/rebuttal)”. This article aims to discuss (1) the inaccurate use
of technical terms, (2) the problem associated with quantities for measuring adsorption performance, (3)
Keywords:
Adsorption
the important roles of the adsorbate and adsorbent pKa, (4) mistakes related to the study of adsorption
Mistake kinetics, isotherms, and thermodynamics, (5) several problems related to adsorption mechanisms, (6)
Comment inconsistent data points in experimental data and model fitting, (7) mistakes in measuring the specific
Inconsistency surface area of an adsorbent, and (8) other mistakes found in the literature. Furthermore, correct ex-
Critical review pressions and original citations of the relevant models (i.e., adsorption kinetics and isotherms) are
Water treatment provided. The authors hope that this work will be helpful for readers, researchers, reviewers, and editors
who are interested in the field of adsorption studies.
© 2017 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
2. Technical terms used in the study of adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
3. Quantities for measuring adsorption performance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
4. Incorrect assumptions regarding pKa . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
5. Adsorption kinetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
5.1. The important role of initial contact time . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
5.2. Adsorption equilibrium time for porous materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
5.3. Pseudo-first-order (PFO) equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
5.3.1. Derivation of the PFO equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
5.3.2. Problems in the application of the PFO equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
5.4. Pseudo-second-order (PSO) equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
5.4.1. Derivation of the PSO equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
5.4.2. Problems in the application of the PSO equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
5.5. Elovich equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96

* Corresponding authors. Department of Environmental Engineering, Chung

Yuan Christian University, Chungli 320, Taiwan.
E-mail addresses: trannguyenhai2512@gmail.com (H.N. Tran), hpchao@cycu.
edu.tw (H.-P. Chao).

http://dx.doi.org/10.1016/j.watres.2017.04.014
0043-1354/© 2017 Elsevier Ltd. All rights reserved.
 H.N. Tran et al. / Water Research 120 (2017) 88e116 89

5.5.1. Derivation of the Elovich equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96

5.5.2. Incorrect expression of the Elovich equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
5.6. Intra-particle diffusion equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
6. Adsorption isotherms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
6.1. Adsorption equilibrium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
6.2. Langmuir equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
6.2.1. Derivation of the Langmuir equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
6.2.2. Derivation of the separation factor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
6.2.3. Mistakes concerning the Langmuir model and the separation factor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100
6.3. Freundlich equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100
6.3.1. Derivation of the Freundlich equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100
6.3.2. Mistakes concerning the Freundlich equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100
6.4. RedlichePeterson equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
6.4.1. Derivation of the RedlichePeterson equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
6.4.2. Mistakes concerning the RedlichePeterson equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
6.5. DubinineRadushkevich equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
6.5.1. Derivation of the DubinineRadushkevich equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
6.5.2. Mistakes concerning the DubinineRadushkevich equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102
7. Adsorption thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102
7.1. Principles of adsorption thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102
7.2. Equilibrium constant derived from the Langmuir constant (KL) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102
7.3. Equilibrium constant derived from the Freundlich constant (KF) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
7.4. Equilibrium constant derived from the partition coefficient (Kp) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
7.5. Equilibrium constant derived from the distribution coefficient (Kd) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
8. Others mistakes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
8.1. Inconsistent data points in experimental data and model fitting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
8.2. Oxidation state of chromium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
8.3. Incorrect labels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
8.4. BET specific surface area of an adsorbent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
8.5. Maximum absorption wavelength in dye adsorption studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
8.6. Cp-cation and p-p interactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
8.6.1. Cp-cation interactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
8.6.2. p-p interactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
8.7. Other miscellaneous errors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110
9. Nonlinear-optimization technique . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
10. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112

1. Introduction related to the adsorption of contaminants in aqueous solutions

reveals that some less obvious inconsistencies and mistakes have
Nowadays, the number of publications in international scientific unavoidably slipped the attention of authors and were repeated in
journals has increasingly become a standard for the assessment of subsequent publications.
scientists (Geckeis and Rabung, 2004). As the number of scientific The observation of these inconsistencies and mistakes, regard-
publications increase, mistakes and misconceptions enter scientific less of their origin, along with comments and open discussions can
literature and some can also be repeated in subsequent publica- prevent their propagation in scientific knowledge transfer. There-
tions. Once errors and mistakes enter the literature, it is difficult to fore, the presentation of a comprehensive review on common
eradicate them. The entrance of mistakes in scientific publications, mistakes in adsorption studies, besides introducing the most cor-
as well as their propagation, can result from the subjectivity of the rect approaches to use and giving a source of up-to-date literature
authors and/or objective reasons. on this issue, seems to be valuable to both readers and researchers
A typical study on the adsorption of organic and inorganic in this field.
contaminants comprises several sections, such as the effects of The main purpose of this review is to identify mistakes in past
solution pH and ionic strength, studies of adsorption kinetics, iso- publications and prevent the propagation of such mistakes in
therms, thermodynamics, desorption, and regeneration. Adsorp- future scientific literature. Herein, we present some common
tion processes can be conducted using either batch or column mistakes in various aspects of adsorption studies and analyze the
techniques. It has been found that many scientific articles in the reasons for their entrance into the literature. This was accom-
field of adsorption science and technology contain several mistakes plished by discussing the published papers in the field of adsorp-
and misconceptions including the use of technical terms, applica- tion of contaminants from aqueous solutions, commonly including
tion of quantities, determining the roles of some constants like pKa, “comments on”, “reply for comments”, “response to”, “authors'
performing kinetic studies and modeling kinetic adsorption data, response to comments on”, “comments on the authors” response to
finding a suitable isotherm model to fit equilibrium data, calcu- comments on”, “comments on comment on”, “in reaction to”, “critical
lating thermodynamic parameters, correct interpretation of review”, and “a note on the comments” published works. In addition
adsorption mechanisms, and measuring the specific surface area of to our comprehensive review on the mistakes existing in publica-
an adsorbent. Moreover, a survey of the scientific publications tions, some correct approaches are suggested where necessary to
90 H.N. Tran et al. / Water Research 120 (2017) 88e116
avoid the propagation of such mistakes in the future scientific
literature. This paper primarily focuses on three basic constituents
of adsorption theory: adsorption equilibria, kinetics, and
thermodynamics.
2. Technical terms used in the study of adsorption
Adsorption processes have their own vernacular. Therefore,
correctly understandings the technical terms used in adsorption
technology can prevent the introduction of several unexpected
ambiguities and discrepancies. Some basic adsorption terms are
summarized in Fig. 1.
To some extent, a thorough understanding of the properties of
adsorbents might prevent common mistakes made in interpreting
adsorption processes and adsorption mechanisms. Numerous
techniques can be used to characterize an adsorbent (Fig. 2). More
information on the basic properties of adsorbents (i.e., biosorbent,
biochar, hydrochar, and activated carbons) and the relations be-
tween these properties has been published in our recent work
(Tran et al., 2017c).
The appropriate use of technical words regarding the bio-
sorption mechanism of heavy metals has been highlighted by
Robalds et al. (2016). To avoid reader confusion, they recommended
that “surface precipitation” be used instead of “microprecipitation”
(also written as “micro-precipitation”). Similarly, it is necessary to
distinguish between “chelation”, “complexation”, and “coordina-
tion”. The word “complexation” includes two meanings: “chelation”
and/or “coordination”. For example, the incorrect sentence “in
another sense, it can also be defined as a collective term for a number
of passive accumulation processes which in any particular case may
include ion exchange, coordination, complexation, chelation, adsorp-
tion and microprecipitation” should be revised as “biosorption may
include ion exchange, complexation (including coordination and/or
Fig. 1. Some basic terms used in adsorption science and technology.
chelation), physisorption, or microprecipitation” (Robalds et al.,
2016). In addition, the use of the term “electrostatic adsorption”
may cause misunderstanding and confusion; therefore, depending
on the intended meaning, the appropriate terms (i.e., “electrostatic
attraction”, “electrostatic force”, or “electrostatic interaction”)
are recommended. Notably, the authors also suggested a new
classification system for the (bio)sorption mechanisms of heavy
metals (Fig. 3).
The electrical state of an adsorbent's surface in solution is usu-
ally characterized by either the point of zero charge (PZC) or the
isoelectric point (IEP). Many authors have complained about the
misuse of the terms IEP and PZC outside their normal meanings
(Somasundaran, 1968; Kosmulski, 2009). The PZC is defined as the
solution conditions under which the surface charge density equals
zero. Potentiometric titration, or related methods, is used to
determine the PZC by finding the point at which the apparent
surface charge density in the presence of an inert electrolyte is not
dependent on ionic strength (Fig. 4a). The IEP occurs when the
electrokinetic (z) potential at the shear plane equals zero; z is
determined from measuring electrokinetic (electrophoresis and
streaming potential) and electroacoustic phenomena (Fig. 4b)
(Kosmulski, 2009). IEP values clearly represent only the external
surface charge of particles in solution, whereas the PZC varies in
response to the net total (external and internal) surface charge of
the adsorbent (as the characteristic of amphoteric surfaces).
Therefore, the difference between the PZC and IEP values for a
porous carbon system can be interpreted as a measure of the sur-
face charge distribution. A difference (PZC
IEP) of greater than
zero indicates that the external particle surface is more negatively
charged than the internal particle surface, and a difference of close
to zero corresponds to a more homogeneous distribution of surface
charge. The PZC is only equal to the IEP in the absence of specific or
counter ions. This means that equality between the PZC and IEP
 H.N. Tran et al. / Water Research 120 (2017) 88e116
Fig. 2. Basic properties of an adsorbent determined by various common techniques.
Fig. 3. Schematic illustration of a new classification system for metal (bio)sorption
mechanisms (Adapted from Robalds et al., 2016. Copyright (2016), with permission
from Elsevier).
exists only if no specific adsorption of counter ions from the solu-
tion occurs (Radovic, 1999; Onjia and Milonji
c, 2002).
3. Quantities for measuring adsorption performance
In the field of adsorption, adsorption performance can be
expressed as the amount of adsorbate adsorbed at equilibrium or
91
the percentage of removed adsorbate. The amount of adsorbate
adsorbed at equilibrium (qe; mg/g) is often calculated using the
material balance of an adsorption system; the adsorbate, which has
disappeared from the solution, must be in the adsorbent (Volesky,
2007).
ðCo
Ce Þ
qe ¼ V (1)
m
where C0 (mg/L) and Ce (mg/L) are the initial and equilibrium
adsorbate concentration in solution, respectively; m (g) is the dried
mass of used adsorbent; V (L) is the volume of the adsorbate so-
lution; and m/V (g/L) is defined as a solid/liquid ratio.
Depending on the purpose of the study, the parameter qe may be
expressed in different units as follows: (1) mg/g for evaluating
practical and engineering processes, (2) mmol/g or meq/g for
examining the stoichiometry of a process and for studying func-
tional groups and metal-binding mechanisms, and (3) mmol/g for
comparing the selective adsorption performance of various adsor-
bates (Volesky, 2007). Of these units, mg/g (milligrams of adsorbate
adsorbed per gram of dried adsorbent) is used most commonly for
qe in adsorption studies.
In addition to qe, the adsorption performance can also be
expressed as the percentage of removed adsorbate (%removal) from
solution. However, the unit of %removal needs to be used cautiously,
as it is very approximate and can cause misleading conclusions
about relative adsorption performance. This unit is only appro-
priate for the purpose of crude measurements and perhaps for
quick and very approximate screening of adsorbent materials
(Kratochvil and Volesky, 1998; Hai, 2017).
92 H.N. Tran et al. / Water Research 120 (2017) 88e116
Fig. 4. A typical example of difference between (a) point of zero charge (PZC) and (b)
isoelectric point (IEP) glucose-derived spherical biochar prepared at 800  C (Data
unpublished).
ðCo
Ce Þ
%removal ¼  100 (2)
Co
To some extent, the use of %removal in the study of adsorption
equilibria can cause incorrect observations and, as a result, inac-
curate conclusions (a detailed discussion is provided in Section 6.1).
4. Incorrect assumptions regarding pKa
A mistake regarding the fundamentals of chemistry was com-
mented on by Rayne (2013). The commented paper reported the
adsorption of n-perfluorooctanesulfonamide (PFOSA) onto multi-
walled carbon nanotubes with differing oxygen content. However,
PFOSA was mistakenly assumed to be an “organic base”, resulting in
the following invalid interpretation: “for PFOSA (pKa ¼ 6.52), when
pH < pKa, protonation occurs on the amino group, and the decreased
protonation leads to the increased adsorption, but when pH > pKa,
PFOSA exists as neutral molecule in water.” In fact, PFOSA is an acid
and, thus, is a neutral compound below its pKa value (estimated at
between 6.0 and 7.0) and a dissociated anion at pH > pKa (Rayne,
2013).
Recently, the effect of pH on the interaction of copper with the
surface functional groups of raw pomegranate-peel biosorbent was
reported as follows:
ReOHþ
2 4 ReOH þ H
þ
(3)
ReOH 4 ReO
þ Hþ (4)
ReO
þ Cu2þ 4 ReOCuþ (5)
ReO
þ Cu(OH)þ 4 ReOCu(OH) (6)
where eR represents the surface adsorbent; ReOHþ 2 , ReOH, and
ReO
represent protonated, neutral, and ionized surface hydroxyl
functional groups, respectively; and ReOCuþ and ReOCu(OH) are
the formed bonding complexes.
The authors (Ben Ali et al., 2016) explained that, “the effect of pH
could be also explained by considering the point of zero charge of the
adsorbent (pHpzc). The adsorbent surface is positively charged for
pH < 4.7 and it becomes negatively charged at pH value above 4.7.
Therefore, 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) occurs
at pH above pHpzc value when the adsorbent surface is negatively
highly charged.” However, the important role of the pKa values of
carboxylic acid groups (eCOOH; pKa 1.7e4.7) and hydroxyl groups
(eOH; pKa 9.5e13) was ignored (Volesky, 2007). Correspondingly,
Eqs. (3)e(6) indicate a misunderstanding of the surface chemistry
of the adsorbent. The authors investigated the effect of solution pH
on the adsorption process of Cu(II) in solutions with pH values from
2.0 to 6.0. Therefore, dissociation of the eOH groups to eO
did not
occur at these solutions pH values. Instead, the eCOOH groups
dissociated, forming negatively charged carboxylate groups
(eCOO‒) in the aforementioned pH range, and were the dominant
groups that interacted with copper ions (Tran, 2017).
Moreover, Bui and Choi (2010) made a critical comment that
Oleszczuk et al. (2010) mistyped the properties of two pharma-
ceuticals: oxytetracycline (logKow ¼ 2.45; pKa ¼ 7) and carbamaz-
epine (logKow ¼
1.22; pKa ¼ 3.27, 7.32, and 9.11). The correct
expression should be oxytetracycline (Sw ¼ 121 mg/L ;
logKow ¼
1.22; pKa ¼ 3.27, 7.32, and 9.11; density ¼ 1.63 g/cm3)
and carbamazepine (Sw ¼ 112 mg/L; logKow ¼ 2.45; pKa ¼ 7;
density ¼ 1.15 g/cm3). Bui and Choi (2010) also emphasized that the
pKa value of carbamazepine reported by Oleszczuk et al. (2010) is
still debated. Carbamazepine (CBZ) is commonly characterized with
two pKa values: pKa1 (¼ 1 or 2.3) for the equilibrium RCONHþ 3 #
RCONH2 þ Hþ and pKa2 (¼ 13.9) for the equilibrium RCONH2 #
RCONH
þ Hþ. The misreporting of the CBZ pKa can cause inac-
curate conclusions. For example, Oleszczuk et al. (2010) suggested
that an electrostatic interaction occurred between CBZ and multi-
walled carbon nanotubes (MWCNT) at pH < 7.0 because they
opined that CBZ existed in its cationic form at pH < 7.0 (pKa ¼ 7.0).
However, CBZ with pKa1 < 2.3 and pKa2  13.9 actually exists
entirely as a neutral species in the pH range of 1.9e11.9, as calcu-
lated using ACDLab. As a result, the electrostatic interaction was
ruled out as a contributing interaction in the CBZ-adsorption
mechanisms (Bui and Choi, 2010).
5. Adsorption kinetics
5.1. The important role of initial contact time
In the study of adsorption kinetics, Azizian proposed that by the
observation of breaking point or deviating from linearity at initial
regions of t/qt versus t plots, means presence of at least two
different sites for adsorption Azizian (2006) or contribution of
diffusion on the rate of adsorption (Haerifar and Azizian, 2013) and
therefore fitting with the PSO model should be avoided. Adsorption
kinetics data in the initial contact time periods play an important
 H.N. Tran et al. / Water Research 120 (2017) 88e116
role in performing accurate modeling and drawing valid
conclusions.
Depending on the affinity between the adsorbent and adsor-
bate, the initial adsorption rate may be very fast. For the adsorption
of heavy metals, Tran et al. (2015) investigated the adsorption of
Cd2þ onto orange-peel-generated biochars, and found that equi-
librium can be reached rapidly in kinetic experiments with a
removal rate of 80.6e96.9% (within 1 min). An analogous perfor-
mance was reported by Guo et al. (2015), with approximately
70.0e96.6% of the total Cd2þ in solution removed within the first
minute of contact. Additionally, Müller et al. (2012) noted that
approximately 90% of Zn(II) adsorption onto Lewatit S1468 occurs
within 1 min, and this adsorption process reached equilibrium in
approximately 5 min.
For the adsorption of organic contaminants, kinetic studies
indicated that the adsorption equilibrium of cationic methylene
green 5 was quickly established, with a low activation energy
required for adsorption (Ea; 3.30e27.8 kJ/mol), and activated car-
bons removed 50e73% of the dye from solution within 1 min (Tran
et al., 2017d, 2017b). Similarly, Canzano et al. (2012) noted that the
adsorption process of anionic Congo-red dye onto raw and acid-
treated pine cone powder reached equilibrium in the first few
minutes (<5 min), during which no measurements were carried
out.
As time goes on, the amount of adsorbate uptake per mass of
adsorbent at any time t (qt) approaches that of at equilibrium (qe)
and, therefore, plotting the kinetic data is bound to produce a
straight line, independent of the real kinetic order followed by the
system. In other words, equilibrium data does not describe the way
by which the system reaches equilibrium. As a result, the use of
data recorded over a significant time interval after the attainment
of equilibrium, or very close to equilibrium, is likely to lead to
erroneous conclusions regarding adsorption kinetics.
5.2. Adsorption equilibrium time for porous materials
The adsorption processes for inorganic and organic contami-
nants onto porous adsorbents (i.e., activated carbon, biochar, acti-
vated carbon spheres, zeolite, and macroreticular resin) can take
longer (i.e., several days or weeks) to approach true equilibrium
than nonporous adsorbents (i.e., biosorbent and hydrochar). This
difference is attributed to the different adsorption mechanisms of
these adsorbents. Pore filling is the most common adsorption
mechanism for porous adsorbents, along with several other in-
teractions (i.e., electrostatic attraction, hydrogen bonding, surface
precipitation, p-p interaction, n-p interaction, and cation ex-
change) that depend on the characteristics of the porous adsor-
bents and adsorbates. Many studies have opted for a 24 h
equilibrating time for isotherm adsorption experiments, without
providing evidence that adsorption in their system attained true
equilibrium within the appropriate timeframe.
Therefore, it is necessary to provide the specified timeframe in
which the adsorption process approaches a true equilibrium.
Fig. 5aec represent the influence of contact time on the adsorption
processes of various contaminants onto porous adsorbents (Hung
and Lin, 2006; Masson et al., 2016; Kim et al., 2016). Clearly, the
amount of contaminants adsorbed onto the porous adsorbents
continued to increase after 24 h. For example, Kim et al. (2016)
speculated on the process of methyl violet (MV) adsorption onto
synthesized granular mesoporous carbon (GMC) and commercial
granular activated carbon (GAC). The results of their kinetic study
demonstrated that MV adsorption reached an equilibrium state
within 20 d for GMC-polyvinyl alcohol and 26 d for GMC-
carboxymethyl cellulose, while adsorption onto GAC had not
reached equilibrium even after 75 d. Furthermore, a phenomenon
93
involving desorption from the adsorbent surface after reaching
adsorption equilibrium (Fig. 5d) has been reported in the literature
(Sharma et al., 2013; Halder et al., 2016). Therefore, studies of the
adsorption kinetics play an important role in identifying the
required equilibration time and the optimal contact time and for an
adsorption process.
In aqueous-phase adsorption, two kinetic reaction models (i.e.,
pseudo-first-order and pseudo-second-order equations), the Elo-
vich or RoginskyeZeldovich model, and the intraparticle diffusion
model have been widely applied to mathematically describe the
intrinsic kinetic adsorption constant. Furthermore, most mistakes
found and discussed in the literature correspond to the use of ki-
netic models. Therefore, the following Sections (5.3e5.6) include a
thorough discussion of these models.
5.3. Pseudo-first-order (PFO) equation
5.3.1. Derivation of the PFO equation
Recently, Ho published a series of critical papers (Ho and McKay,
1998b; Ho, 2005, 2014a, 2015, 2016e) discussing two main points.
First, Ho (Ho and McKay, 1998b) claimed to offer the correct
reference style for citing Lagergren's paper, with the original
translated from “Lagergren, S. (1898), Zur theorie der sogenannten
adsorption gelo€ster stoffe. Kungliga Svenska Vetenskapsakademiens
Handlingar, Band 24, No. 4, 1e39” into English as “Lagergren, S.,
About the theory of so-called adsorption of soluble substances, Kun-
gliga Svenska Vetenskapsakademiens. Handlingar, Band 24, No. 4,
1898, pp. 1e39.” Second, Ho stated that Lagergren's first-order rate
equation has been called pseudo-first-order since 1998 (Ho, 2005)
in order to distinguish kinetic equations based on the adsorption
capacity of solids from those based on the concentration of a so-
lution. However, the responses of many authors (Ozacar, € 2005;
Kumar, 2006d; Utomo et al., 2010) state that Lagergren's first-
order rate expression had been referred to as a pseudo-first-order
equation before Ho's publication in 1998. For example, in 1990,
Sharma et al. (1990) studied the removal of Ni(II) from an aquatic
environment by wollastonite. In the section on adsorption kinetics,
they stated: “the adsorption of Ni (II) on wollastonite follows the first
order adsorption rate expression of Lagergren (1898).”
The great contributions of Ho toward correcting the citation
style format for the PFO equation cannot be denied. However, the
PFO equation was not originally proposed or initially expressed by
Ho. In the scientific community, the authors who first propose a
theoretical model should always be given credit for their contri-
butions via correct citation (Vasanth Kumar and Rattanaphani,
2007; Wu, 2009; Utomo et al., 2010). Therefore, the original work
by Lagergren (1898), who first presented the first-order-rate
equation for the adsorption of oxalic acid and malonic acid onto
charcoal, should be cited. The PFO equation can be expressed
correctly in nonlinear (Eq. (7)) and linear forms (Eq. (8) or Eq. (9)).


qt ¼ qe 1
e
k1 t (7)
k
logðqe
qt Þ ¼
1 t þ logðqe Þ (8)
2:303
lnðqe
qt Þ ¼
k1 t þ lnðqe Þ (9)
where qe and qt are the amounts of adsorbate uptake per mass of
adsorbent at equilibrium and at any time t (min), respectively; and
k1 (1/min) is the rate constant of the PFO equation.
5.3.2. Problems in the application of the PFO equation
It cannot be denied that the PFO equation is widely applied in
94 H.N. Tran et al. / Water Research 120 (2017) 88e116

Fig. 5. Effect of contact time on the adsorption process of (a) methyl violet onto granulated mesoporous carbon (GMC) and granular activated carbon (GAC) (Reprinted from Kim
et al. 2016. Copyright (2016), with permission from Elsevier); (b) methyl tert-butyl ether onto carbonaceous resin (Ambersorb 563) (Reprinted from Hung and Lin 2006. Copyright
(2006), with permission from Elsevier); (c) ibuprofen (IBP), carbamazepine (CBZ), ofloxacin (OFX), bisphenol-A (BPA), diclofenac (DFN), mecoprop (MCP), pentachlorophenol (PCP),
benzotriazol (BZT), and caffeine (CAF) onto activated carbon cloths (resin phenolic precursor) (Reprinted from Masson et al. 2016. Copyright (2016) with permission from Elsevier);
and (d) methyl blue onto graphene oxide (Reprinted with permission from Sharma et al. 2013. Copyright (2013) American Chemical Society).

adsorption kinetics. However, several problems related to the

application of the PFO equation have been discussed in the litera- k1 t
logðqe
qt Þ ¼ logðqe Þ (13)
ture. First, many incorrect expressions for its linear forms have been 2:303
published. Various incorrect forms are shown in Eq. (10)
(Alagumuthu et al., 2010), Eq. (11) (Fu et al., 2007; Jing et al., Ci k t
log ¼ 1 (14)
2014; Nekouei and Nekouei, 2017), Eq. (12) (Ho 2014a, 2014e; Ct 2:303
Jing et al., 2014; Ho 2016a, 2016b, 2016c, 2016d, 2016e, 2017), Eq.
 
(13) (Ho, 2015), Eqs. (14) and (15) (Jing et al., 2014), Eq. (16) (Kumar, C
Ct k t
2006a), and Eq. (17) (Kumar and Porkodi, 2007b), which should be log 1
i ¼ 1 (15)
Ci
Ce 2:303
avoided in future studies. As a result of these incorrect expressions,
recalculation of the PFO equation parameters was necessary to
qe k1
obtain the correct parameters (Wu et al., 2017). log ¼ (16)
qe
qt 2:303t

logðqe Þ
k1 k1
logðqe
qt Þ ¼ t (10) logðqe
qt Þ ¼ logðqe Þ
(17)
2:303 2:303

where Ci (mg/L), Ct (mg/L), and Ce (mg/L) are the concentrations of

logðqe Þ
k1 adsorbate at the initial time (t ¼ 0), any time t, and equilibrium,
logðqe
qt Þ ¼ (11) respectively.
2:303t
The second problem is the two unknown parameters (qe and k1).
Furthermore, in most cases, the PFO equation is only appropriate
1 k 1 for the initial 20e30 min of contact time, not for the whole range
¼ 1 þ (12) (Ho and McKay, 1998a). Thus, plots of Eq. (8) or Eq. (9) are only
qt qe t qe
linear over approximately the first 30 min; beyond this initial
period, the experimental and theoretical data will not fit
 H.N. Tran et al. / Water Research 120 (2017) 88e116 95

adequately (McKay et al., 1999). Another important problem is the F
avere, 2006; Kumar and Guha, 2006; Vasanth Kumar and
selection of an appropriate qe value. Notably, the adjusted qe value Rattanaphani, 2007) to clarify the correct citation of the PSO
cannot be lower than the maximum measured value of qt. This is equation. Thus, the nonlinear form of the PSO equation for solid-
because mathematical errors associated with taking the logarithm liquid adsorption systems was not originally reported by Ho
of a negative number will occur when using Eq. (8) or Eq. (9) (1995) or first applied by Ho et al. (1996), but initially proposed
(Plazinski et al., 2009). Finally, the qe value calculated using the by Blanchard et al. (1984).
PFO equation is not equal to the qe value obtained from experi- In the literature, the PSO equation can be correctly expressed in
ments, which further indicates the inability of the PFO equation to four linear forms (Eqs. (23)e(26)), and the initial adsorption rate (h)
fit kinetic adsorption data (Febrianto et al., 2009). The presence of a can be described by Eq. (29).
boundary layer or external resistance controlling the beginning of Expression for the linear form (Type 1) with a plot of t/qt versus
the sorption process was argued to be responsible for this t:
discrepancy (McKay et al., 1999).  
Therefore, two methods have been recommended to obtain an t 1 1
¼ tþ (23)
accurate estimation of the kinetic parameters in the PFO equation: qt qe k2 q2e
(1) a trial and error process to obtain the optimal qe value (Ho and
McKay, 1998a), or (2) application of a nonlinear optimization Expression of the linear form (Type 2) with a plot of 1/qt versus
1/t:
technique. A simple guide to using the nonlinear method is intro-
duced in Section 9.  
1 1 1 1
¼ þ (24)
qt k2 q2e t qe
5.4. Pseudo-second-order (PSO) equation
Expression of the linear form (Type 3) with a plot of qt versus qt/
5.4.1. Derivation of the PSO equation t:
In 1984, Blanchard et al. (1984) initially proposed a second-  
order rate equation for the removal of heavy metals from water 1 qt
qt ¼
þ qe (25)
using natural zeolites, as follows: k2 qe t
Expression of the linear form (Type 4) with a plot of qt/t versus
dn
¼ Kðno
nÞ2 (18) qt:
dt
Integration of Eq. (18) gives: qt
¼
ðk2 qe Þqt þ k2 q2e (26)
t
1

a ¼ Kt (19) The initial adsorption rate (h) was proposed by Ho et al. (1996).
no
n First, Eq. (22) can be rearranged to:
After rearranging, Eq. (19) becomes:
1
qt ¼ (27)
Ktno þ ano
1 1 þ qte
n¼ (20) k2 q2e
Kt þ a
Subsequently, when t approaches 0, Eqs. (23) and (27) can be
where n is the amount of M2þ fixed or the amount of NHþ 4 released expressed as Eq. (28). Setting h ¼ qt/t, the initial adsorption rate (h;
at each instant; no is an exchange capacity; and K is a rate constant. mg/g  min) can then be determined by Eq. (29).
Plotting 1/(n0
n) as a function of time (t) must produce a
straight line, the slope of which gives the rate constant K and the t 1 qt
intercept leads to the exchange capacity. Considering the boundary ¼ 4 ¼ k2 q2e (28)
qt k2 q2e t
condition of n ¼ 0 for t ¼ 0, it follows that a ¼ 1/n, and Eq. (20) can
be rearranged to:
h ¼ k2 q2e (29)
n2
þ Kt
no ¼ (21) Clearly, only the linear form (Type 1, Eq. (23)) might have been
1 þ Knt reported by Ho et al. (1996) for the adsorption of dyes from waste
If qt ¼ no, qe ¼ n, and k2 ¼ K, Eq. (21) becomes: €
streams by peat (Ozacar, 2005; Kumar, 2006d; Kumar and F
avere,
2006; Wu, 2009). Kumar and Fa
vere (2006) hypothesized that, in
q2e k2 t adsorption research, the Langmuir equation (Langmuir, 1918) has
qt ¼ (22)
1 þ k2 qe t been the most widely used isotherm to describe adsorption pro-
cesses under equilibrium conditions. In the literature, four linear
where qe (mg/g) and qt (mg/g) are the amount of adsorbate types of the Langmuir isotherm have been reported. Irrespective of
adsorbed at equilibrium and at any t (min), respectively; and k2 (g/ the linear expression reported, these equations have been widely
mg  min) is the rate constant of the PSO equation. called the Langmuir isotherm. It is not correct to claim that the
The nonlinear form of the PSO equation (Eq. (22)) has been Langmuir model was derived or proposed by other authors who
applied elsewhere (Ho, 1995; Ho et al., 1996). Recently, a series of transformed the original Langmuir expression into a new linear
comments made by Ho implied that the derivation and first expression (Kumar and Guha, 2006). In scientific literature, the
application of the PSO equation belongs to his work. Any applica- names of scientists (i.e., Langmuir or Freundlich) have always been
tion of the PSO equation in the field of adsorption studies without presented, even after modification of their equations (Arica, 2003).
citation of the original work or with a misquotation (i.e., the cita- Similarly, Utomo et al. (2010) suggested that it might not be
tion of a secondary reference) might suffer from his comments. necessary to cite papers that deal with mathematical modification
However, in reaction to Ho's comments, a series of notes were and different mathematical expressions of the models (i.e., PFO and
published by other scholars (Kumar, 2006c, 2006d; Kumar and PSO, and Langmuir). However, from the scientific point of view, the
96 H.N. Tran et al. / Water Research 120 (2017) 88e116

authors who first proposed a theoretical model should be credited analysis, Boehm titration, and solution calorimetry), and (2) having
because of their great contributions to the advancement of science. a good sense of the chemical nature of the adsorbate and adsorbent,
Therefore, the original work by Blanchard et al. (1984) should be adsorbent's surface, and chemical or physical interactions between
€
cited for the expression of the PSO equation (Ozacar, 2005; Kumar, the adsorbent and adsorbate (Volesky, 2007; Lima et al., 2015,
2006d; Kumar and Fa
vere, 2006; Azizian, 2007; Plazinski et al., 2016). The use of analytical techniques together with adsorptive
2009; Wu, 2009; Utomo et al., 2010). thermodynamic data (i.e., changes in enthalpy and entropy) and
activation and adsorption energies, are necessary to confirm
whether the adsorption of contaminants in aqueous solution is a
5.4.2. Problems in the application of the PSO equation chemical or physical process (Lima et al., 2015; Tran et al., 2016).
First, many incorrect expressions of the linear form of PSO Finally, in most cases, experimental data for adsorption kinetics
equation are found in the literature, as shown in Eq. (30) (Fu et al., are well fitted by the linear form of the PSO equation. However,
2007; Kumar and Porkodi, 2007b), Eq. (31) (Ho, 2014f), Eqs. (32) caution should be taken in drawing conclusions based on fitting to
and (33) (Ho, 2014g), Eq. (34) (Ho, 2013), Eq. (35) (Lin and Wang, the linear form of the PSO equation. For example, Fig. 6 presents a
2009), Eq. (36) (Ho, 2014c), Eq. (37) (Ho, 2014d), Eq. (38) (Ho, plot of t/qt versus t. Clearly, the R2 values for the linear form of the
2014b), and Eq. (39) (Ho, 2015). PSO equation are very high (R2 > 0.99); however, the corresponding
R2 values for the nonlinear form of the PSO equation are signifi-
t 1 1
¼ þ (30) cantly lower (R2 ¼ 0.53e0.68). This finding means that the
qt k2 q2e qe t
adsorption process of methylene green 5 (MG5) onto synthesized
activated carbon and commercial activated carbon (porous mate-
t 1 1 rials) is not adequately described by the PSO equation. In fact, Tran
¼ þ (31)
qt 2k2 qe et al. (2017d) concluded that the process of MG5 adsorption onto
these porous materials involved p-p interactions and pore filling,
t 1 t and was not related to chemical adsorption. Obviously, the
¼ þ (32)
qt k2 qe qe nonlinear method can be applied to obtain kinetic model param-
eters that are more accurate than those obtained using the linear
  method.
t 1 2 1
¼ q þ t (33)
qt k2 e qe

t 1 1
¼ þ t (34)
qt k2
q2e qe
5.5. Elovich equation
 
t 1 1 5.5.1. Derivation of the Elovich equation
¼  t (35)
qt k2 q2e qe An empirical equation was firstly proposed by Roginsky and
Zeldovich (1934) for the adsorption of carbon monoxide onto
t 1 t manganese dioxide. However, this equation is now generally
¼ k q2 þ (36)
qt 2 2 e qe known as the Elovich equation and has been extensively applied to
chemisorption data (McLintock, 1967). This equation can be
expressed mathematically as follows:
1 1 1
¼ þ (37)
qt k2 q2e qe

t 1 1
¼ þ (38)
qt k2 q2e qe

t k t t
¼ 2 þ (39)
qt k2 q2e qe
Second, based on the best fit of kinetic experimental data using
the PSO model, many authors have drawn controversial conclu-
sions. For example, “the adsorption process is the chemisorption,
which involve valence forces through sharing electrons between
adsorbate and adsorbent”, “the best fit of experimental kinetic data in
pseudo-second-order kinetics suggests the chemisorption, which may
involve valency forces through sharing of electrons between dye anion
and adsorbent”, and other similar conclusions. The problem with
such conclusions has been discussed by several researchers (Kumar,
2006a; Lima et al., 2015; Lima et al., 2016), who claimed that
adsorption mechanisms cannot be directly assigned based on
observing simple kinetic experiments or by fitting kinetic models
(i.e., the PFO and PSO models).
Adsorption mechanisms can only be established by (1) using Fig. 6. Fits of kinetic adsorption data to the linear pseudo-second-order equation [the
study of methylene green 5 adsorption onto commercial activated carbon (CAC) and
several analytical techniques (i.e., FTIR, SEM, nitrogen adsorption- synthesized activated carbons prepared from golden shower through different
desorption isotherms, Raman spectroscopy, TGA/DTA, DSC, 29Si chemical activation methods (GSAC, GSBAC, GSHAC, and GSHBAC)] (Adapetd from Tran
and 13C solid-state NMR, XRD, XPS, pHPZC, pHIEP, CHN element et al., 2017d. Copyright (2017), with permission from Elsevier).
 H.N. Tran et al. / Water Research 120 (2017) 88e116
dqt
¼ a expð
bqt Þ (40)
dt
where qe and qt are the amounts of adsorbate uptake per mass of
adsorbent at equilibrium and at any time t (min), respectively; a
(mg/g  min) is the initial rate constant because dqt/dt / a when qt
/ 0; and b (mg/g) is the desorption constant during any one
experiment.
By applying the boundary conditions of qt ¼ 0 at t ¼ 0, the in-
tegrated form of Eq. (40) will become Eq. (41) (nonlinear).
1 diffusion of the adsorbate molecules from the exterior of the
qt ¼ lnð1 þ abtÞ (41)
b
To simplify the Elovich equation, Chien and Clayton (1980)
assumed abt [ 1. Thus, a linear form (Eq. (42)) can be obtained:
1 1
qt ¼ lnðt Þ þ lnðabÞ (42)
b b
and a plot of qt versus lnt should give a linear relationship with a
slope of (1/b) and an intercept of (1/b)ln(ab).
5.5.2. Incorrect expression of the Elovich equation
Errors in the presentation of the nonlinear form of the Elovich
model are common in the literature. These incorrect equations
(Eqs. (43)e(45)) can be found in several previous papers (Ho and
McKay, 1998a; Lin and Wang, 2009; Alagumuthu et al., 2010; Ben
Ali et al., 2016).
qt ¼ lnðt Þ þ b lnðabÞ (43)
1 suggestion that metal-ion adsorption is pH dependent (Volesky,
qt ¼ lnðt Þ þ b lnðabÞ (44)
b 2003, 2007; Tien, 2007; Tien, 2008). However, the pH effect has
qt ¼ b lnðt Þ þ b lnðabÞ (45)
5.6. Intra-particle diffusion equation
The linearized transformation of the intra-particle diffusion
model (Weber and Morris, 1963) is presented as follows:
pffiffi
qt ¼ kp t þ C (46)
where kp (mg/g  min1/2) is the rate constant of the intra-particle
diffusion model and C (mg/g) is a constant associated with the
thickness of the boundary layer, where a higher value of C corre-
sponds to a greater effect on the limiting boundary layer.
Generally, although the PSO model can adequately describe
adsorption kinetic experimental data, this model does not reveal
the adsorption mechanisms. Similarly, the Elovich equation seems
to describe various reaction mechanisms, such as bulk diffusion and
surface diffusion. In contrast, the intra-particle diffusion model can
be useful for identifying the reaction pathways and adsorption
mechanisms and predicting the rate-controlling step. In a solid-
liquid sorption process, adsorbate transfer is often characterized
by film diffusion (also known as external diffusion), surface diffu-
sion, and pore diffusion, or combined surface and pore diffusion. In
short, if a plot of qt against t0.5 is linear and passes through the
origin, the adsorption is entirely governed by intra-particle diffu-
sion. In contrast, if the intra-particle diffusion plot gives multiple
linear regions, then the adsorption process is controlled by a
multistep mechanism.
97
Four steps associated with transport processes during adsorp-
tion by porous adsorbents were originally proposed in reference
(Walter, 1984). The first stage is transport in the solution phase
(known as “bulk transport”; occurs quickly), which can occur
instantaneously after the adsorbent is transferred into the adsor-
bate solution; therefore, it does not control engineering design. In
most cases, this stage occurs too rapidly and its contribution is
considered negligible. The second stage is “film diffusion” (occurs
slowly). In this stage, the adsorbate molecules are transported from
the bulk liquid phase to the adsorbent's external surface through a
hydrodynamic boundary layer or film. The third stage involves
adsorbent into the pores of the adsorbent, along pore-wall surfaces,
or both (known as “intraparticle diffusion”; occurs slowly). The last
stage, adsorptive attachment, often occurs very quickly; therefore,
it is also not significant for design. These four steps are summarized
in Fig. 7 (Weber and Smith, 1987).
6. Adsorption isotherms
6.1. Adsorption equilibrium
Milonji
c (2009a) and Milonji
c (2010) suggested that the amount
of adsorbate adsorbed onto an adsorbent depended on the equi-
librium concentrations of metal ions, equilibrium solution pH, and
temperature. An adsorption isotherm should be given as the
equilibrium adsorbed amounts versus the equilibrium ion con-
centrations for a constant equilibrium solution pH and tempera-
ture. Thus, environmental parameters in the sorption system
(especially solution pH) must be carefully controlled at the given
value over the entire contact period until the sorption equilibrium
is reached. These comments were in good agreement with the
invariably been examined in terms of the initial pH of the aqueous
solution. Not a single case has reported data demonstrating the
changes in the solution pH during the course of an adsorption
experiment.
In the scientific literature, adsorption equilibrium studies in
batch experiments have been conducted in different ways as fol-
lows: (1) solution pH values were not mentioned in the manuscript,
(2) initial pH values were neither measured nor adjusted and final
pH values were measured, (3) initial and final pH values were
measured, (4) initial pH values were adjusted and final pH values
were not mentioned, (5) initial pH values were adjusted and final
pH values were measured, (6) initial and final pH values were
adjusted, (7) pH was controlled several times during the course of
the reaction, (8) a constant pH was maintained throughout the
equilibration time by adding acidic or alkaline solutions, and (9)
experiments were conducted at a constant pH using a buffered
solution (Smiciklas et al., 2009).
Kumar (2006a) recommended that presenting a plot of qe versus
Ce for the complete adsorption isotherm in an adsorption study
plays a key role in identifying the regions (e.g., Henry, Freundlich,
Langmuir, and BET) in which the experimental data relating to
adsorption equilibrium are actually located. In contrast, plots of the
Freundlich, Langmuir, or other adsorption isotherm models do not
help to identify these regions. Fig. 8a and b provide typical com-
plete adsorption isotherms that should be presented in the inves-
tigation of liquid-phase adsorption. Vasanth Kumar and Sivanesan
(2006) also recommended that using equilibrium data covering
the complete isotherm was the best way to obtain the parameters
in isotherm expressions; equilibrium data with a partial isotherm
was not sufficient, instead equilibrium data that covers the com-
plete isotherm was required.
98 H.N. Tran et al. / Water Research 120 (2017) 88e116
Fig. 7. Transport processes during adsorption by a porous adsorbent (Adapted with permission from Weber and Smith, 1987. Copyright (1987) American Chemical Society).
Furthermore, an inconsistent definition of the adsorption
isotherm plot in the literature was recognized by Li and Pan (2007);
the plot of qe against Ce/Wo (with Wo being a liquid/solid ratio) is
invisible with the traditional definition of the complete adsorption
isotherm (the plot of qe versus Ce).
Recently, Senthil Kumar et al. (2014) presented a plot of %
removal versus C0 in an adsorption equilibrium study instead of
presenting the complete adsorption isotherm as shown in Fig. 8a.
However, Hai (2017) made a critical note that it is clear that at every
initial concentration of methylene blue (MB; 50, 100, 150, 200,
250 mg/L), the removal percentage of MB by sulfuric acid-treated
orange peel (STOP) at 30  C was always overwhelmingly higher
than the corresponding values at 40, 50, and 60  C. This result
revealed that increasing the temperature from 30 to 60  C resulted
in a decrease in the adsorption capacity (qe) of MB dye onto STOP
(Fig. 8a). However, the maximum adsorption capacities of STOP
from the Langmuir model (Qomax) exhibited the following order:
60  C (83.333 mg/g) > 50  C (71.428 mg/g) > 40  C (62.5 mg/
g) > 30  C (50 mg/g). This logic problem might be caused by the
adsorption process of MB onto STOP not reaching equilibrium at the
different temperatures (see adsorption isotherms in Fig. 8a) owing
to the low initial MB concentrations (50e250 mg/L) used at a high
solid/liquid ratio of 4.0 g/L (Hai, 2017). Therefore, in adsorption
equilibrium studies, presenting plots of %removal versus Co, %
removal versus Ce, or qe versus Co should be avoided, and a plot of qe
versus Ce for the complete adsorption isotherm must be presented.
Fig. 8b provides a typical example of the comparison of
adsorption performance under the same operating conditions (i.e.,
temperature and solution pH). Clearly, “adsorbent B” exhibits a
higher affinity than “adsorbent A” at low initial adsorbate con-
centrations (Co) and low equilibrium adsorbate concentrations (Ce),
whereas the opposite order (“adsorbent A” > “adsorbent B”) was
found at higher Co and Ce values (Volesky, 2007).
It was recently identified that many researchers have made
questionable conclusions when studying the effects of agitation
rate or shaking speed on the adsorption capacity (qe) or maximum
adsorption capacity (Qomax) of an adsorbent toward an adsorbate.
For example, Chu et al. (2005) concluded that the adsorption ca-
pacity of vitamin E onto silica varies as a function of the agitation
rate (120e180 rpm). The Qomax values exhibited the following or-
der: 43.71 mg/g at 180 rpm > 24.20 mg/g at 160 rpm > 24.20 mg/g
at 140 rpm > 17.62 mg/g at 120 rpm. However, Choong and Chuah
(2005) made a critical remark that the agitation rate only impacts
on the speed at which a system reaches equilibrium, but not on the
equilibrium itself. This means that when the adsorption process
obtains a true equilibrium (sufficient contact time between adsor-
bent and adsorbate), the Qomax values at different agitation rates
will be insignificantly different. This is because the decrease of the
boundary layer resistance a higher agitation rate will facilitate the
transport of the adsorbate to the adsorbent.
Although adsorption isotherms can insignificantly contribute to
elucidating adsorption mechanisms, they are less helpful in this
regard than data on adsorption kinetics and thermodynamics
(Volesky, 2003; Tien, 2007, 2008). However, collecting adsorption
isotherms is a useful strategy to both describe the relationship
between the adsorbate concentration in solution (liquid phase) and
the adsorbent (solid phase) at a constant temperature and design
adsorption systems (Tran et al., 2016).
A wide variety of models of adsorption isotherms have been
applied in the literature. These models can be classified as follows:
(1) irreversible isotherms and one-parameter isotherms (i.e., Henry
isotherm); (2) two-parameter isotherms (i.e., Langmuir, Freundlich,
DubinineRadushkevich, Temkin, FloryeHuggins, and Hill); (3)
three-parameter isotherms (i.e., RedlichePeterson, Sips, Toth,
KobleeCorrigan, Khan, FritzeSchluender, VietheSladek, and Rad-
keePrausnitz); and (4) more than three-parameter isotherms (i.e.,
Weberevan Vliet, FritzeSchlunder, and Baudu) (Kumar and
Porkodi, 2006; Hamdaoui and Naffrechoux, 2007; Foo and
 H.N. Tran et al. / Water Research 120 (2017) 88e116 99

 
1 1 1 1
¼ o K
þ o (49)
qe Qmax L Ce Qmax

EadieeHoffsiee linearization of the Langmuir model (Type 3):

 

1 qe o
qe ¼ þ Qmax (50)
KL Ce
Scatchard linearization of the Langmuir model (Type 4):

qe o
¼
KL qe þ Qmax KL (51)
Ce

where Qomax (mg/g) is the maximum saturated monolayer

Fig. 8. (a) Non-equilibrium adsorption isotherms of methylene blue onto sulfuric acid-
treated orange peel at various temperatures (Adapted from Hai (2017). Copyright
(2017) Taylor and Francis), and (b) comparison of adsorption isotherm curves: adsor-
bent B performs better (higher qe at q10) than adsorbent A at lower equilibrium con-
centrations (e.g., Ce ¼ 10 mg/L) (Adapted from Volesky 2007. Copyright (2007), with
permission from Elsevier).
Hameed, 2010). Of these, the Langmuir and Freundlich models are
the most commonly used, followed by the DubinineRadushkevich
and RedlichePeterson models, because of the usefulness of their
model parameters, their simplicity, and their easy interpretability.
adsorption capacity of an adsorbent, Ce (mg/L) is the adsorbate
concentration at equilibrium, qe (mg/g) is the amount of adsorbate
uptake at equilibrium, and KL (L/mg) is a constant related to the
affinity between an adsorbent and adsorbate. For a good adsorbent,
a high theoretical adsorption capacity Qomax and a steep initial
sorption isotherm slope (i.e., high KL) are generally desirable
(Kratochvil and Volesky, 1998; Wang, 2009).
The limitations of using the four linear forms of the Langmuir
model have been highlighted by Bolster and Hornberger (2007).
The transformation of data for linearization can result in modifi-
cations of error structure, introduction of error into the indepen-
dent variable, and alteration of the weight placed on each data
point, which often leads to differences in the fitted parameter
values between linear and nonlinear versions of the Langmuir
model. For the Type 1 linearization, because Ce and Ce/qe are not
independent, the correlation between Ce and Ce/qe is over-
estimated, i.e., this equation may provide good fits to data that do
not conform to the Langmuir model. For the Type 2 linearization,
transformation leads to clustering of data points near the origin and
is extremely sensitive to variability at low values of qe (high values
of 1/qe). For the Type 3 linearization, the abscissa is not error free,
and qe/Ce and qe are not independent. Thus, the correlation between
qe/Ce and qe is underestimated, i.e., this equation may provide poor
fits to data that do conform to the Langmuir model. Finally, the
variables qe and qe/Ce are also not independent in the Type 4 line-
arization. In this case, the correlation between qe and qe/Ce is
underestimated, i.e., this equation may provide a poor fit to data
that do conform to the Langmuir model.

6.2. Langmuir equation

6.2.1. Derivation of the Langmuir equation

6.2.2. Derivation of the separation factor
The theoretical Langmuir equation (Langmuir, 1918), which was
If the experimental data are adequately described by the Lang-
originally applied to the adsorption of gases on a solid surface, was
muir model, it is essential to calculate the separation factor. Hall
developed using the following assumptions: (1) a fixed number of
et al. (1966) originally proposed that the essential characteristics
accessible sites are available on the adsorbent surface and all active
of the Langmuir isotherm model can be expressed in terms of a
sites have the same energy; (2) adsorption is reversible; (3) once an
dimensionless constant called the separation factor or equilibrium
adsorbate occupies a site, no further adsorption can occur on that
parameter RL, which is defined as follows:
site; and (4) there is no interaction between adsorbate species. The
nonlinear form of the Langmuir model is described in Eq. (47) and
its four linearized forms are shown in Eqs. (48)e(51). Table 1
Relationship between isotherm parameters and isotherm shapes.
o K C
Qmax L e
qe ¼ (47) Freundlich exponent Separation factor Isotherm shapes Remarks
1 þ KL Ce
n ¼0 RL ¼0 Irreversible Horizontal
HaneseWoolf linearization of the Langmuir model (Type 1): n <1 RL <1 Favorable Concave
n ¼1 RL ¼1 Linear Linear
 
Ce 1 1 n >1 RL >1 Unfavorable Convex
¼ o
Ce þ o K
(48)
qe Qmax Qmax L Note: Information was adapted from Worch (2012). Copyright (2012), with
permission from De Gruyter. RL and n were calculated from Equations (52) and (56),
LineweavereBurk linearization of the Langmuir model (Type 2): respectively.
100 H.N. Tran et al. / Water Research 120 (2017) 88e116

1 1
RL ¼ (52) RL ¼ (55)
1 þ KL Co 1 þ KL Qmax
o C
o

where RL is a constant separation factor (dimensionless) of the
solid-liquid adsorption system, KL is the Langmuir equilibrium
constant, and Co (mg/L) is the initial adsorbate concentration.
Notably, the isotherm shape can be predicted using the sepa-
ration factor (RL) (Weber and Chakravorti, 1974) and the Freundlich
exponent n (Worch, 2012). Table 1 summarizes the various
isotherm shapes.
6.2.3. Mistakes concerning the Langmuir model and the separation
factor
Wang et al. (2014) published a corrigendum because of a
misapplication of the nonlinear form of the Langmuir equation (Eq.
(53)). A similar mistake in presenting the nonlinear form of the
Langmuir equation (Eq. (54)) was observed by Kumar and Porkodi
(2007b).
Ce Ce K
¼ o þ oL
qe Qmax Qmax
Ce 1 1
¼ o
þ o
qe KL Qmax Qmax Ce
Furthermore, an unexpected typographical error was made in
reference (Egirani, 2004). As a result, the sentence “a plot of Ce/qe
versus Ce should indicate a straight line of slope 1/KLQomax and an
intercept of 1/Qomax” was corrected to “a plot of Ce/qe versus Ce should
indicate a straight line of slope 1/Qomax and an intercept of 1/KLQomax”
by Ho (2004a).
The incorrect expression and inaccurate calculation of RL were
recognized and discussed by Kumar (2006a, 2006b). First, the
separation factor RL is not a Langmuir constant, and is only
employed for isotherms that obey the Langmuir model. Second, RL
values will vary with the initial adsorbate concentration, irre-
spective of the shape of the isotherm, and RL values at different
initial adsorbate concentrations cannot be calculated directly from
the Langmuir isotherm, but can be calculated from the Langmuir
equilibrium constant KL. These misunderstandings and mistakes
are summarized in Table 2.
Furthermore, a mistake related to the definition of RL compared
with the original definition was stated by Fu et al. (2007). The
incorrect presentation is shown in Eq. (55).
Recently, Hai (2017) commented that “the authors' conclusion
about separation factor (RL) was not valid. It is noted that there is no
information or value of RL mentioned in the paper's results and dis-
cussion. It is impossible for the authors to conclude that the values of RL
were found to be between 0 and 1, indicating the favorable adsorption
of MB dye onto STOP.”
Clearly, the separation factor is related to the Langmuir equation
in the adsorption isotherm. Nevertheless, Goswami et al. (2016)
recently described an incorrect relationship between the separa-
tion factor and adsorption kinetic models (i.e., PFO, PSO, and intra-
particle diffusion) at different initial cadmium concentrations. This
is a fundamental misunderstanding that should be avoided.
6.3. Freundlich equation
6.3.1. Derivation of the Freundlich equation
The Freundlich equation is one of the earliest empirical equa-
(53)
tions used to describe equilibrium data and adsorption character-
istics for a heterogeneous surface (Freundlich, 1906). Unlike the
Langmuir equation, the Freundlich isotherm can describe neither
(54) the (arithmetic) linearity range at very low concentrations nor the
saturation effect at very high concentrations. Hence, the Freundlich
isotherm does not describe the saturation behavior of an adsorbent
(Wang, 2009). The nonlinear and linear forms of the Freundlich
equation can be expressed as shown in Eqs. (56) and (57),
respectively.
qe ¼ KF Cen (56)
log qe ¼ n log Ce þ log KF (57)
where qe (mg/g) is the amount of adsorbate uptake at equilibrium,
Ce (mg/L) is the adsorbate concentration at equilibrium, KF (mg/g)/
(mg/L)n is the Freundlich constant, and n (dimensionless) is the
Freundlich intensity parameter, which indicates the magnitude of
the adsorption driving force or the surface heterogeneity.
6.3.2. Mistakes concerning the Freundlich equation
Several investigators have identified an incorrect expression
(Eq. (58)) of the linear form of the Freundlich equation (Kumar and
Porkodi, 2007b; Alagumuthu et al., 2010).

1
Table 2 log qe ¼ þ log KF (58)
Mistakes in the presentation and calculation of the separation factor (RL).
n log Ce

Typical examples Remakes Furthermore, several discussions that are inconsistent with the
original concepts of the Freundlich theory have been identified in
Langmuir parameters The RL is not the Langmuir constant,
so it is mistake for presentation. the literature (Lu, 2008; Hai, 2017). Hai (2017) commented that the
Qomax KL RL exponent n of the Freundlich equation must be dimensionless.
Orange peel 54.5 0.101 0.01e0.17 Therefore, the original authors incorrectly reported the units of the
OP Biochar 115 0.019 0.08e0.57 exponent n (g/L); and there is no validation for the statement of the
Langmuir RL The RL values must be calculated at
significance of the n value for the adsorption of MB dye onto STOP is
parameters different range of initial adsorbate
concentration, so it is mistake for as follows: when n ¼ 1 the adsorption is linear, when n < 1 the
Qomax KL
calculation. adsorption is a chemical process, and when n > 1 the adsorption is a
Orange peel 54.5 0.101 0.17 physical process. According to the Freundlich theory, the adsorp-
OP Biochar 115 0.019 0.57 tion isotherm becomes linear when n ¼ 1, favorable when n < 1, and
Langmuir RL Correction presentation and
unfavorable when n > 1. Similarly, Harsha et al. (2015) also made a
parameters calculation.
basic mistake when they reported the units of the exponent n as g/
Qomax KL
L.
Orange peel 54.5 0.101 0.01e0.17 Lu (2008) highlighted that in many cases KF is not the maximum
OP Biochar 115 0.019 0.08e0.57 adsorption capacity and the KF value is only equal to the maximum
Data were modified from our previous publication (Tran et al., 2015). adsorption capacity when n approaches infinity. Although KF is not
 H.N. Tran et al. / Water Research 120 (2017) 88e116 101

defined as the maximum adsorption capacity (Qomax), KF values and
Qomax values should be of the same order. Such a mistake has been
discussed by Tran (2017), where the reported KF values for the
adsorption of Cu2þ onto raw pomegranate peel biosorbent followed
the order: 4.471 at 303 K > 3.439 at 313 and 323 K > 2.877 at 333 K,
while the Qomax values were 30.12 mg/g at 313 K > 21.367 mg/g at
323 K > 21.276 mg/g at 333 K > 20.492 mg/g at 303 K. This mistake
might be attributable to a miscalculation.
Notably, Kumar (2006a) highlighted that values for the expo-
nent n (Eq. (59)) in the range of 0e10 suggest favorable adsorption.
If the experimental equilibrium data do not lie in the Henry region,
then the linear regression method will just check the hypothesis
instead of verifying the theory behind the Freundlich model;
therefore, it is not possible in practice to obtain n > 10 (Kumar,
2006a). A corresponding error was also found in a published pa-
per (Huang et al., 2014), in which the n values reported for the
removal of aniline and Cr(VI)/aniline þ Cr(VI) by an activated car-
bon/chitosan composite were 10.20 and 11.34, respectively.
1=n
qe ¼ KF Ce
6.4. RedlichePeterson equation
6.4.1. Derivation of the RedlichePeterson equation
A three-parameter RedlichePeterson isotherm was proposed
upon considering the limitations of the Freundlich and Langmuir
isotherms (Redlich and Peterson, 1959). This model incorporates
the features of the Freundlich and Langmuir models and might be
applicable for demonstrating adsorption equilibrium over a wide
range of adsorbate concentrations. The nonlinear form of this
empirical model is given as follows:
KRP Ce
qe ¼ g (60)
1 þ aRP Ce
where KRP (L/g) and aRP (mg/L)
g are the RedlichePeterson con-
stants and g (dimensionless) is an exponent whose value must lie
between 0 and 1.
Eq. (60) becomes a linear isotherm (Henry's law equation) at
low surface coverage (g ¼ 0), reduces to the Langmuir isotherm
when g ¼ 1, and transforms into the Freundlich isotherm when KRP
and aKP [ 1 and g ¼ 1. Therefore, if the g value is outside the range
of 0e1, the data is not adequately explained by the RedlichePerson
equation. Accurate calculation of g can be helpful in expatiation of
where the isotherm presentations, neither in the Freundlich or
Langmuir (Vasanth Kumar and Sivanesan, 2006).
6.4.2. Mistakes concerning the RedlichePeterson equation
A series of comments related to mistakes in calculating the
exponent g have been reported elsewhere (Inbaraj, 2006; Kumar
and Porkodi, 2007a; Kumar et al., 2007; Kumar et al., 2007;
Kumar and Porkodi, 2008). These mistakes involved values of the
exponent g that were outside the range of 0e1 (Table 3). It is not
easy to predict the parameters of the RedlichePeterson equation
because there are three unknown parameters. Although a new
linear form of the RedlichePeterson equation was published by Wu
et al. (2010), the nonlinear form might be more appropriate for
accurately calculating the parameters of adsorption models with
more than two unknown parameters, such as the RedlichePeterson
model.
6.5. DubinineRadushkevich equation
6.5.1. Derivation of the DubinineRadushkevich equation
The DubinineRadushkevich equation was developed to account
for the effect of the porous structure of an adsorbent (Dubinin and
Radushkevich, 1947), and is expressed as follows:
(59)
qe ¼ qDR e
KRD ε
2
(61)
The linear form of the DubinineRadushkevich equation is:
ln qe ¼
KDR ε2 þ ln qDR (62)
 
1
ε ¼ RT ln 1 þ (63)
Ce
By inserting Eq. (63) into Eq. (62), Eq. (64) can be obtained:
 
1
ln qe ¼
KDR R2 T 2 ln2 1 þ þ ln qDR (64)
Ce
The parameters qDR and KDR in Eq. (64) can be obtained as fol-
lows: (1) a plot of lnqe against ln2(1 þ 1/Ce) has a slope ¼
KDRR2T2
and an intercept ¼ lnqRD, and the E value can be obtained using Eq.
(65), and (2) a plot of lnqe against R2T2ln2(1 þ 1/Ce) has a
slope ¼
KDR and an intercept ¼ lnqRD, and the E value can be
obtained using Eq. (66). Notably, the E values obtained from Eqs.
(65) and (66) are the same (Tran et al., 2016).
1 RT
E ¼ pffiffiffiffiffiffiffiffiffiffiffi ¼ pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi (65)
2KDR
2slope
1 1
E ¼ pffiffiffiffiffiffiffiffiffiffiffi ¼ pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi (66)
2KDR
2slope
where qRD (mg/g) is the adsorption capacity, KRD (mol2/kJ2) is a
constant related to the sorption energy, 3 is the Polanyi potential, E
(kJ/mol) is the mean adsorption energy, R is the gas constant, T is
the temperature in Kelvin, and qe and Ce are obtained from Eq. (1).

Table 3
Incorrect values of the exponent g in the RedlichePeterson equation.

Adsorbent Adsorbate g Reference

Sawdust Reactive black 1.10 Inbaraj (2006)

Sawdust Reactive red 1.04 Inbaraj (2006)
Anilinepropylsilica xerogel Congo red 2.91 Kumar and Porkodi (2008)
Xad-4 resin 4-chlorophenol at 303 K 1.07 Kumar and Porkodi (2007a)
Xad-4 resin 4-chlorophenol at 318 K 1.19 Kumar and Porkodi (2007a)
Tectona grandis Cu2þ
0.35 Vasanth Kumar et al. (2007)
Syzygium cumini Pb2þ
1.23 Kumar et al. (2007)
Activated carbon/chitoshan composite Aniline/aniline þ Cr(VI) 1.04 Huang et al. (2014)
Activated carbon/chitoshan composite Cr(VI)/aniline þ Cr(VI) 1.04 Huang et al. (2014)
Activated carbon/chitoshan composite Cr(VI) 1.02 Huang et al. (2014)
102 H.N. Tran et al. / Water Research 120 (2017) 88e116
6.5.2. Mistakes concerning the DubinineRadushkevich equation
Some authors have highlighted erroneous expressions of the
DubinineRadushkevich equation (Cavas, 2008; Fu et al., 2008).
These erroneous forms are shown in Eqs. (67)e(70).
Incorrect nonlinear form of the DubinineRadushkevich
equation:
 tively; therefore, the equilibrium constant KC in Eq. (71) must be
qe ¼ qDR expð
KDR ðRTðln 1 þ 1=Ce Þ2
Incorrect linear form of the DubinineRadushkevich equation:
 
1 with the assumption of the International Union of Pure and Applied
ln qe ¼
2KDR RT ln 1 þ þ ln qDR
Ce
Incorrect expressions for the Polanyi potential (3 ):
ε ¼ RTe1=Ce
 
1
ε ¼ RT ln
Ce
Additionally, the magnitude of E may give useful information
about the type of adsorption process (physical or chemical) (Fu
et al., 2008; Tran et al., 2016). Fu et al. (2008) commented that
the E values for the removal of phenolic compounds by organo-
philic bentonite can be categorized as corresponding to ion ex-
change (E ¼ 8e16 kJ/mol), whereas the original authors made an
inconsistent conclusion that the adsorption of two phenolic com-
pounds could be regarded as physical adsorption.
Recently, Tran (2017) made the following comment on the
conclusions of the original paper: “the obtained value of E in this
work varies from 32.596 kJ/mol to 40.572 kJ/mol for studied temper-
ature which is higher than the adsorption energy values previously
enumerated.” However, these adsorption energy (E) values might
not have been calculated correctly. Assuming the b values at 303 K
(b ¼ 1.93  10
8 mol2/kJ2), 313 K (2.99  10
8), 323 K (2.00  10
8),
and 333 K (2.35  10
8) reported by these authors are correct, the
recalculated 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, and 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 heavy-metal biosorption process.
7. Adsorption thermodynamics
7.1. Principles of adsorption thermodynamics
Thermodynamic studies are an indispensable component of
predicting adsorption mechanisms (e.g., physical and chemical).
The key distinctions between physical and chemical adsorption
were summarized in detail in a recent report (Tran et al., 2016). The
thermodynamic parameters can be computed according to the laws
of thermodynamics using the following equations:
DG ¼
RT ln KC
The relationship between DG and DH and DS is described as
follows:
DG ¼ DH 
T DS
The well-known van't Hoff equation is obtained by substituting
Eq. (71) into Eq. (72)

DH 1 DS
ln KC ¼  þ
R T R
where R is the universal gas constant (8.3144 J/(mol  K)) and T is
the absolute temperature in Kelvin.
The Gibbs energy change (DG ) is directly calculated from Eq.
(71), whereas the enthalpy change (DH ) and entropy change (DS )
are determined from the slope and intercept, respectively, of a plot
of lnKC versus 1/T (Eq. (73)). The common units of DG , the gas
constant, and temperature are J/mol, J/(mol  K), and K, respec-
(67) dimensionless (Milonji
c, 2007, 2009b; Canzano et al., 2012;
Dawood and Sen, 2012; Zhou et al., 2012; Zhou and Zhou, 2014;
Tran et al., 2016; Ghosal and Gupta, 2017; Hai, 2017; Rahmani-
Sani et al., 2017; Zhou, 2017). This discussion is in accordance
(68)
Chemistry.
Eq. (72) describes the relationship of DG with DH and DS , and
it is useful for checking the logic of calculated values for these
(69) thermodynamic parameters. Unfortunately, associated mistakes
have been found in the literature. Fu et al. (2008) substituted the
values of DH and DS into Eq. (72) to obtain DG , but the obtained
(70) DG values were significantly different from the DG values ob-
tained using Eq. (71). Fu et al. (2008) highlighted that this mistake
might result from incorrect application of the method for calcu-
lating the equilibrium constant.
Clearly, accurate estimation of thermodynamic parameters is
directly dependent on accurate determination of the equilibrium
constant between two phases (KC; dimensionless). In the literature,
the thermodynamic parameters can be calculated from KC values
derived from adsorption-isotherm constants (i.e., Langmuir,
Freundlich, Frumkin, FloryeHuggins, and Henry) or the partition
coefficient (Liu, 2009; Doke and Khan, 2013; Tran et al., 2016).
However, to obtain an appropriate calculation method, several
factors need to be considered thoroughly. First, the equilibrium
constant (KC) must be dimensionless. Second, the linear regression
coefficient (R2) of the van't Hoff equation must be high. Third, the
concentration of adsorbate used in the adsorption equilibrium
study (adsorption isotherm) are low or high. In addition, the tem-
peratures used for calculating the thermodynamic parameters
must have units of Kelvin (K), not degrees Celsius ( C). The incorrect
use of temperature units led to the publication of an erratum by Ho
(2004a), with accurate recalculations.
As the equilibrium constant KC can be derived using a number of
approaches, considerable variation in the thermodynamic param-
eters can be obtained; therefore, the most appropriate approach
should be determined. Here, we thoroughly discuss the derivation
of the equilibrium constant KC from adsorption isotherms (i.e.,
Langmuir, Freundlich, and Henry constants) and the partition co-
efficient because of their popularity in the literature.
7.2. Equilibrium constant derived from the Langmuir constant (KL)
The Langmuir equation was initially derived from a kinetic study
and then subsequently from a thermodynamic study. The deriva-
(71) tion of the Langmuir equation from the thermodynamic perspec-
tive can be described as follows (Crittenden et al., 2012; Tran et al.,
2016). The relationship between vacant surface sites on the surface
of an adsorbent (Sv; mmol/m2), adsorbate species in solution (A;
(72) mmol), and adsorbate species bound to surface sites (SA; mmol/m2)
can be described by the following reaction:
SV þ A#SA (74)
On the basis of the Langmuir expression, it is assumed that the
(73) reaction has a constant Gibbs energy change (DG ; J/mol) for all
sites, so the thermodynamic equilibrium constant (KC; dimen-
sionless) can be expressed as:
 H.N. Tran et al. / Water Research 120 (2017) 88e116 103

DG
DH 1 DS

DG ¼
RT ln KC ⇔KC ¼ e RT (75) lnð55:5  1; 000  KL Þ ¼  þ (81)
R T R
Another Langmuir assumption is that each site is capable of
binding at most one adsorbate molecule (monolayer). According to where the factor 55.5 is the number of moles of pure water per liter
the equilibrium condition, the thermodynamic equilibrium con- (1,000 g/L divided by 18 g/mol) and the term 55.5  1,000  KL is
stant may be written as: dimensionless.
In the case of KL with units expressed in L/mg, Milonji
c (2007
and 2009b) stated that KL could be obtained as a dimensionless
SA
DG
KC ¼ ¼ e RT (76) parameter by multiplying KL by 106 (Eq. (82)). However, Zhou and
SV ½A
Zhou (2014) recommended that KC could be obtained as a dimen-
sionless parameter by multiplying KL by the molecular weight of
where [A] is the concentration of adsorbate A in solution at equi-
the adsorbate (Mw; g/mol), by 1,000, and then by 55.5 (Eq. (85)).
librium (mg/L), R is the universal gas constant (8.314 J/mol  K), and
T is absolute temperature K (273 þ  C).
KC ¼ 106 KL (82)
The critical problem with Eq. (76) is that there are two unknown
parameters (i.e., SV and [A]). However, this problem can be solved if

the total sites available or monolayer coverage (ST; mol/m2) are DG ¼
RT ln 106 KL (83)
fixed:


DH 1 DS
SA K ½AST ln 106 KL ¼  þ (84)
ST ¼ SV þ SA ¼ þ SA⇔SA ¼ C (77) R T R
KC ½A 1 þ KC ½A
where the factor 106 is the solution density (assuming the density
The expression of SA in units of mmol/m2 is not useful in mass
of pure water is 1.0 g/mL) and the term 106  K is dimensionless.
balance, and units of mass of adsorbate adsorbed per unit mass of
adsorbent (qe; mg/g) are much more useful. The mass loading (qe)
KC ¼ Mw  55:5  1; 000  KL (85)
can be obtained in units of mg/g (Eq. (1)) by multiplying both sides
of Eq. (71) by the surface area (SBET; m2/g) of the adsorbent and the
molecular weight of the adsorbate (Mw; g/mol). Thus, Eq. (77)
DG ¼
RT lnðMw  55:5  1; 000  KL Þ (86)
becomes:

DH 1 D S
lnðMw  55:5  1; 000  KL Þ ¼  þ (87)
KC ½AST SBET Mw Q o K Ce R T R
SA:SBET $Mw ¼ ⇔qe ¼ max L (78)
1 þ KC ½A 1 þ KL Ce
where the factor 55.5 is the number of moles of pure water per liter
and the term Mw  55.5  1,000  KL is dimensionless.
where qe (mg/g) ¼ SA  SBET  Mw is described by Eq. (1); Ce (mg/
In a recent paper, Tran et al. (2016) applied Eqs. (79)e(87) to
L) ¼ [A] is the concentration of adsorbate in solution at equilibrium;
compare thermodynamic parameters calculated from the Langmuir
Qomax (mg/g) ¼ ST  SBET  Mw is the maximum monolayer
constants derived from four linear forms of the Langmuir model.
adsorptive capacity of the adsorbent when the surface sites are
They concluded that (1) both the recommendations of Milonji
c
saturated with adsorbate; the relationship between KL and KC is
(2007 and 2009b) and Zhou and Zhou (2014) provide the same
described in the following discussion.
methods for calculating the thermodynamic parameters, and (2)
However, the main problem is that the Langmuir constant KL is
there is some deviation between these methods for the results from
dimensional with common units of L/mmol or L/mg, while the
Types 1, 3, and 4; only Type 2 produces identical results.
equilibrium constant KC is dimensionless (without units). Thus, the
direct application of KL (L/mmol or L/mg) in the calculation of
thermodynamic parameters produces incorrect results, as dis- 7.3. Equilibrium constant derived from the Freundlich constant (KF)
cussed by many authors (Milonji
c, 2007, 2009b; Canzano et al.,
2012; Dawood and Sen, 2012; Zhou et al., 2012; Zhou and Zhou, The Freundlich equation is consistent with the thermodynamics
2014; Anastopoulos and Kyzas, 2016; Tran et al., 2016; Ghosal and of heterogeneous adsorption (Crittenden et al., 2012). The
Gupta, 2017; Hai, 2017; Rahmani-Sani et al., 2017). To solve this Freundlich constant KF can be obtained as a dimensionless value
unit problem, several methods have been recommended (Milonji
c, using Eq. (88) (Ghosal and Gupta, 2015; Tran et al., 2016).
2007; Zhou and Zhou, 2014; Tran et al., 2016). Depending on the  
units of KL, the equilibrium constant KC can easily be obtained as a   1
1n
KF r 106
dimensionless constant. KC ¼ (88)
When an adsorption study is conducted in aqueous solution and 1000 r
KL has units of L/mmol, KC can be easily obtained as a dimensionless  1
0
parameter by multiplying KL by 55.5 and then by 1,000 (Eq. (79)).  6  1
1n
This method was originally proposed by Milonji
c (2007) and then B KF r 10 C
DG ¼
RT lnB
@1000
C
A (89)
developed by Zhou and Zhou (2014) and Tran et al. (2016). The r
values of the parameters DG , DH , and DS can be calculated using
the following equations:
0  1

 1
1n
KC ¼ 55:5  1; 000  KL (79) B KF r 106 C
DH  1 DS
lnB
@1000
C¼
A x þ (90)
r R T R
DG ¼
RT lnð55:5  1; 000  KL Þ (80)
where r is the density of pure water (assumed as ~1.0 g/mL).
104 H.N. Tran et al. / Water Research 120 (2017) 88e116

It is noted that the units of KF rely on the units used for the Table 4
liquid-phase concentration (C) and solid-phase concentration (q). Comparison of incorrect and correct thermodynamic parameters for methylene blue
adsorption onto sulfuric acid-treated orange peel.
Units of mg/L or mmol/L for C and mg/g or mmol/g for q are used
most frequently to demonstrate adsorption from water solutions. Incorrect thermodynamic parameters reported by Senthil Kumar et al. (2014)
The differing units of KF can be reciprocally converted using Eq. (91) Co (mg/L) DH (kJ/mol) DS (J/mol/K)a DG (kJ/mol)
(Worch, 2012).
30  C 40  C 50  C 60  C

53.7
137
12.5
10.4
8.87
8.49

KF ¼ KF0 ðMw Þ1
1=n (91) 50
100
37.4
90.3
10.1
9.15
8.04
7.46
150
32.9
79.4
8.86
8.19
7.27
6.52
where the units of the Freundlich constant KF are (mg/g)/(mg/L)1/n, 200
27.5
64.2
8.03
7.54
6.64
6.19
with Co and Ce (mg/L) and qe (mg/g); the units of KF0 are (mmol/g)/ 250
23.7
54.4
7.29
6.61
6.17
5.64
(mmol/L)1/n, with Co and Ce (mmol/L) and qe (mmol/g); and Mw is Co (mg/L) KC values
the molecular weight of the adsorbate. The exponent 1/n is not
30  C 40  C 50  C 60  C
affected by the units of the liquid-phase concentration (C) and
solid-phase concentration (q). 50 142 54.9 27.2 21.5
100 54.8 33.6 19.9 14.8
Based on a comparison of the thermodynamic parameters 150 33.7 23.3 14.9 10.5
calculated from the Freundlich constant (dimensionless) and 200 24.2 18.1 11.9 9.35
Langmuir constant (dimensionless), Tran et al. (2016) concluded 250 18.1 12.7 9.97 7.66
that the signs and magnitudes of DG , DH , and DS calculated from Correct thermodynamic parameters suggested by Hai (2017)
KF were consistent with those calculated from KL. Of course, the
Temperature KC DG (kJ/ DH (kJ/ DS (J/mol  van't Hoff
experimental data in the adsorption isotherms must be fitted well (K) mol) mol) K) equation
by the Langmuir and Freundlich models, and the R2 value of the
303 5.25
4.18 13.65
31.39 y ¼ 1642e3.78
van't Hoff equation must be higher than 0.90 (Tran et al., 2016). It is
313 4.33
3.81 R2 ¼ 0.978
also evident that, to some extent, the application of KF to estimate 323 3.54
3.40
the thermodynamic parameters should be approached with 333 3.27
3.28
caution. a
The unit of J/mol/K was expressed as the original paper; the correction unit
might be J/(mol  K).

7.4. Equilibrium constant derived from the partition coefficient (Kp)

Changes in the thermodynamic partition coefficient with

changes in temperature were first reported by Biggar and Cheung
(1973). The equilibrium constant can be defined as follows:
as g Cs
Kp ¼ ¼ s
ae ge Ce
where as is the activity of the adsorbate adsorbed onto the adsor-
bent, ae is the activity of the adsorbate in solution at equilibrium, gs
is the activity coefficient of the adsorbate adsorbed onto the
adsorbent, ge is the activity coefficient of the adsorbate in solution
at equilibrium, Cs is the concentration of adsorbate adsorbed onto
the adsorbent at equilibrium (mg/L), and Ce is the concentration of
adsorbate in solution at equilibrium (mg/L). Cs is defined by the
mass balance of adsorbate that disappears 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
g approaches unity, and Eq. (92) can be written as:
Cs as
Lim ¼ ¼ Kp
Cs/0 Ce ae
In this method, Kp values can be obtained plotting ln(Cs/Ce) versus
Cs and extrapolating Cs to zero. If a straight line fits the data with a
high regression coefficient (R2) and its intersection with the vertical
axis provides the value of Kp, the partition coefficient will be in
unison with the equilibrium constant. The DG value can be directly
calculated using Eq. (71), while the values of DH and DS are
determined from the slope and intercept, respectively, of Eq. (73).
This method has been widely applied in the literature. A sum-
mary of the applications of this method can found in the critical
review in reference (Doke and Khan, 2013). However, incorrect
applications of Biggar and Cheung's definition have also been
identified in the literature. In a typical experiment, Senthil Kumar
et al. (2014) made a mistake in the application of Kp during
calculation of the thermodynamic parameters for the adsorption of
MB onto STOP (Table 4). Hai (2017) highlighted that it is impossible
to obtain an equilibrium constant, Gibbs energy change (DG ),
enthalpy change (DH ), and entropy change (DS ) for the adsorp-
(92)
tion process at every initial MB concentration, as shown in Table 4.
Assuming that the experimental data reported by Senthil Kumar
et al. (2014) are correct, Hai (2017) recalculated the thermody-
namic parameters based on the method of Biggar and Cheung
(1973), and the corrected thermodynamic parameters are also lis-
ted in Table 4. Likewise, Lima et al. (2015) also determined the value
of the adsorption equilibrium constant (KC) from the value of the
best fit nonlinear isotherm equilibrium model instead of using the
equilibrium constant (Kp) calculated from the initial and equilib-
rium concentrations of the adsorbate.
Importantly, according to the United States Environmental
Protection Agency (USEPA, 1999), the partition coefficient is only
appropriate for calculating the thermodynamic parameters if the
initial used adsorbate concentration is low. Analogous conclusions
can be found in the literature (Liu, 2009; Salvestrini et al., 2014;
Lima et al., 2015; Tran et al., 2016; Hai, 2017). It has been high-
(93)
lighted that the partition coefficient is only equal to the thermo-
dynamic equilibrium constant when the adsorbed concentrations
in the solutions are very low (infinite dilution). In this situation, the
partition coefficient can be used to calculate the thermodynamic
parameters. Recently, Tran et al. (2016), who compared the ther-
modynamic parameters calculated from the Langmuir constant and
the partition coefficient, concluded that although the signs of the
calculated DG , DH , and DS parameters were the same, the
partition coefficient might not be appropriate for calculating the
thermodynamic parameters owing to the low regression coefficient
of the van't Hoff equation (R2 ¼ 0.53).
 H.N. Tran et al. / Water Research 120 (2017) 88e116
7.5. Equilibrium constant derived from the distribution coefficient
(Kd)
In 1987, Khan and Singh (1987) proposed a method for calcu-
lating thermodynamic parameters (Eq. (94)) based on the method
of Biggar and Cheung (1973). The distribution coefficient (Kd) can
be defined as follows:
qe
Kd ¼ (94)
Ce
In this method, Kd values are obtained by plotting ln(qe/Ce)
against Ce and extrapolating to zero Ce. If a straight line fits the data
with a high regression coefficient (R2), then its intersection with the
vertical axis provides the value of Kd. Fundamentally, Eq. (94) can
be derived from the Freundlich and Langmuir equations. If n ¼ 1,
the Freundlich equation (Eq. (56)) will become Henry's equation for
a linearized isotherm (Eq. (95)), and the Freundlich constant (KF)
will be equal to the Henry constant (KH). For very low concentra-
tions of adsorbate (KL and Ce ≪ 1), the Langmuir equation (Eq. (47))
will become Henry's equation (Eq. (95)), and the Henry constant
(KH) will become QomaxKL. The Henry constant (KH) is also referred
to as the distribution coefficient (Kd).
qe ¼ KH Ce (95)
This method has been widely applied to calculating thermody-
namic parameters in the literature. Unfortunately, the units of Kd in
Eq. (94) are L/g as Ce has units of mg/L and qe has units of mg/g.
Therefore, it is impossible to directly employ Kd as the equilibrium
constant for the calculation of DG , DH , and DS . This problem
associated with the units has been discussed by several scientists
(Patrickios and Yamasaki, 1997; Milonji
c, 2007; Canzano et al.,
2012; Dawood and Sen, 2012; Tran et al., 2016; Zhou, 2017).
Canzano, Iovino et al. (2012) suggested that the partition coefficient
Kd (L/g) could be converted to KC (dimensionless) by multiplying Kd
by a factor of 1,000, as originally proposed by Milonji
c (2007 and
2009b).
Similar to the partition coefficient, the distribution coefficient
may be appropriate for estimating the thermodynamic parameters
when the initial concentration of the adsorbate is very low
(Salvestrini et al., 2014; Tran et al., 2016). Tran et al. (2016)
concluded that the signs of DG , DH , and DS estimated from the
distribution coefficient and the Langmuir constant are the same.
However, the units of Kd (L/g) are different from those of KL (L/mg),
and the adsorption equilibrium data do not fit Henry's adsorption
isotherm. As a result, application of the distribution coefficient was
not appropriate for calculating the thermodynamic parameters in
their study; the low regression coefficient of the van't Hoff equation
(R2 ¼ 0.42) is further evidence of the inappropriateness of this
approach.
In summary, to determine accurate thermodynamic parameters,
several points should be thoroughly considered. First, the equilib-
rium constant (KC) must be dimensionless. Second, if the concen-
trations of adsorbate used to obtain the adsorption isotherm are
very low (infinite dilution), the partition (Kp) or distribution co-
efficients (Kd) are appropriate for calculation of the thermodynamic
parameters; otherwise, the Langmuir (KL) or Freundlich (KF) con-
stant models may be more appropriate. Third, the plot of lnKC
against 1/T corresponding to the van't Hoff equation must be linear
with a high regression coefficient (R2). Additionally, it is necessary
to consider whether the adsorption process can reach equilibrium
and consideration of the adsorption isotherm shapes and the
adsorption model fit are also recommended. Thus, presentation of
the complete adsorption isotherm (plot of qe versus Ce) is strongly
recommended. Finally, the determined thermodynamic
105
parameters must have a logical relationship with the relevant
experimental data. For example, the adsorption capacity of adsor-
bate onto an adsorbent (i.e., qe or Qomax) increased with increasing
temperature, which means that the enthalpy change must be
positive (þDH ).
Notably, numerous recent studies have reported methods of
calculating thermodynamic parameters from the partition coeffi-
cient (Kp) or distribution coefficient (Kd) that differed from the
traditional concepts defined in Sections 7.4 and 7.5, respectively. A
typical mistake is present in the work of Nekouei et al. (2016). They
studied the adsorption thermodynamics at only one initial adsor-
bate concentration and different temperatures instead of using a
range of adsorbate concentrations (i.e., from 100 mg/L to 1,000 mg/
L) and different temperatures (i.e., 10  C, 20  C, 30  C, and 50  C).
This mistake led to invalid conclusions regarding the adsorption
thermodynamics.
8. Others mistakes
8.1. Inconsistent data points in experimental data and model fitting
Significant differences between the number of data points in an
experiment and those used for model fitting should be avoided. For
example, Azizian (2008a) made the following critical comments
about the paper of Karadag et al. (2007): there were six experi-
mental data points regarding the adsorption kinetics (plots of qt
versus t), but only five experimental data points were used for
fitting of the experimental data to the PSO model (plot of t/qt versus
t). This omission resulted in inaccurate calculations and question-
able conclusions. The R2 values of the PSO model were very high
(0.992e1.000), but the difference between the experimental (qe,exp)
and calculated (qe,cal) values was more than 100% (for example
qe,exp ¼ 6.720 mg/g and qe,cal ¼ 15.526 mg/g). Clearly, the qe values
calculated from the experimental data and the model were signif-
icantly different, but the authors (Karadag et al., 2007) concluded
that “The pseudo-second-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.
Lima et al. (2015) observed a change in kinetic parameters when
five experimental points were deleted to achieve a good R2 value.
They concluded that the strategy of deleting some data points to
improve the R2 value caused serious errors in the values of qe and k1
in the PFO equation or k2 in the PSO equation.
Azizian (2008a,b) pointed out that in reference (Karadag et al.,
2007), a comparison was made between the results of fitting four
experimental equilibrium data points to the Langmuir model and
fitting five experimental equilibrium data points to the Freundlich
model. Therefore, it is impossible for the authors (Karadag et al.,
2007) to conclude that “the Freundlich model exhibited a slightly
better fit than the Langmuir model.” To compare the fits of two
different models, the same experimental data (including the same
number of experimental data points) should be used (Azizian,
2008a). Likewise, Harsha et al. (2015) examined adsorption iso-
therms using seven experimental data points. However, in the plots
for calculating the Langmuir, Freundlich, and Dubi-
nineRadushkevich models, only three experimental points were
used. It is impossible to obtain the Langmuir, Freundlich, and
DubinineRadushkevich parameters from only three experimental
points. A similar mistake was found in reference (Goswami et al.,
2016).
8.2. Oxidation state of chromium
Many investigators (Aoyama, 2003; Park et al., 2006a, 2006b,
106 H.N. Tran et al. / Water Research 120 (2017) 88e116
2006c) have commented that mistakes in analyzing chromium
species in aqueous solution have resulted in the incorrect eluci-
dation of hexavalent chromium adsorption, attributing Cr(VI)
removal from an aqueous solution to “anionic adsorption”. Gener-
ally, when Cr(VI) comes into contact with organic substances or
reducing agents, especially in an acidic medium, it is easily or
spontaneously reduced to Cr(III), as Cr(VI) has a high redox po-
tential (above þ1.3 V under standard conditions). Therefore, there
is a strong possibility that the mechanism of Cr(VI) removal by
biomaterials or biomaterial-based activated carbon is not “anionic
adsorption” but “adsorption-coupled reduction”. Various authors
(Aoyama, 2003; Park et al., 2006a, 2006b, 2006c) also suggested
that in Cr(VI) adsorption studies, it is necessary to analyze both the
Cr(VI) and total Cr in aqueous solution, as well as determining the
oxidation state of chromium bound to the biomaterial or activated
carbon.
The authors (Aoyama, 2003; Park et al., 2006a, 2006b, 2006c)
pointed out that in most papers, only Cr(VI) in aqueous solutions
was analyzed by the standard colorimetrical method; the pink
colored complex formed from between 1,5-diphenycarbazide and
Cr(VI) in an acidic solution can be spectrophotometrically analyzed
at 540 nm. Similarly, the total Cr in aqueous solutions has been
analyzed using atomic absorption spectroscopy (AAS) or induc-
tively coupled plasma-atomic emission spectroscopy (ICP-AES),
which cannot distinguish Cr(VI) from the total Cr. Additionally,
Aoyama (2003) underlined that the total Cr present in a solution
can be determined by oxidizing any Cr(III) formed with KMnO4,
followed by the same procedures described for the determination
of Cr(VI). The adsorption density can be calculated from the dif-
ference between the initial concentration of Cr(VI) and the final
concentration of total Cr. In contrast, the Cr(III) concentration is
calculated from the difference between the final total Cr and final
Cr(VI) concentrations.
Several techniques have been applied in the literature to
ascertain the oxidation state of chromium on an adsorbent, such as
X-ray photoelectron spectroscopy (XPS) and X-ray absorption
spectroscopy (XAS). For example, Dambies et al. (2001) investi-
gated the characterization of Cr(VI) interactions with chitosan us-
ing XPS. On the basis of their XPS data, they concluded that Cr(VI)
was entirely reduced to Cr(III) on glutaraldehyde crosslinked beads,
while only 60% of Cr(VI) was found in its reduced form on raw
beads. Additionally, Cr(VI) binding and reduction to Cr(III) by
agricultural byproducts of Avena monida (oat) biomass was char-
acterized by Gardea-Torresdey et al. (2000). Their XAS studies
further corroborated that, although Cr(VI) could bind to oat
biomass, it was easily reduced to Cr(III) by positively charged
functional groups, and Cr(III) was subsequently adsorbed by avail-
able carboxyl groups.
A study on using fermentation waste for detoxification of Cr(VI)
contaminated aqueous solutions was published by Park et al.
(2008). In this study, the colorimetric method was used in combi-
nation with excess potassium permanganate to analyze both the
Cr(VI) and total Cr in aqueous solution, and XPS was used to
ascertain the oxidation state of the chromium bound on the
biomass. Park et al. (2008) concluded that the mechanism of Cr(VI)
removal by the fermentation waste involved reduction of Cr(VI) to
Cr(III) (redox reaction). As a result, kinetic and equilibrium models
based on the “reduction” mechanism were used to describe the
behavior of Cr(VI) and total Cr in aqueous solution.
Two main mechanisms for removal of Cr(VI) from aqueous so-
lution by nonliving biomass were proposed by Park et al. (2005). In
the first mechanism (direct reduction), Cr(VI) was directly reduced
to Cr(III) in the aqueous phase by contact with electron-donor
groups of the biomass, i.e., groups with lower reduction poten-
tials than that of Cr(VI) (þ1.3 V). However, the second mechanism
comprised three steps: (1) binding of anionic Cr(VI) ion species to
positively charged groups on the biomass surface, (2) reduction of
Cr(VI) to Cr(III) by adjacent electron-donor groups, and (3) release
of the Cr(III) ions into the aqueous phase, owing to electronic
repulsion between the positively charged groups and the Cr(III)
ions, or complexation of Cr(III) with adjacent groups capable of
binding chromium. If there are a small number of electron-donor
groups in the biomass or a low concentration of protons in the
aqueous phase, chromium bound on the biomass can remain in the
hexavalent state. Therefore, the extent to which mechanisms I and
II operate depends on the nature of the biosorption system,
including solution pH, temperature, functional groups on the
biomass, and biomass and Cr(VI) concentrations (Park et al., 2006a,
2006b). These two main mechanisms are summarized in Fig. 9.
8.3. Incorrect labels
Incorrect labeling of compounds should also be avoided. A
publication entitled “Selenite adsorption and desorption in main
Chinese soils with their characteristics and physicochemical proper-
ties” included such a mistake, as pointed out by Goldberg (2016).
The purpose of this work was to study the adsorption of Se(IV)
(selenite), not Se(VI) (selenate); however, the paper reported that
the authors prepared Se solutions using Na2SeO4 (hexavalent
Se(VI)). This mistake was explained by the incorrect labeling of
Na2SeO3 as Na2SeO4 in the Materials and Methods section.
Similarly, the author of the paper entitled “Adsorption sequence
of toxic inorganic anions on a soil” prepared solutions from
Na2HAsO4$7H2O as As(V) species. However, they mislabeled
Na2HAsO4$7H2O as NaAsO2, a trivalent As(III) species (Goldberg,
2009).
8.4. BET specific surface area of an adsorbent
Using the BrunauereEmmetteTeller (BET) surface area of
pahokee peat (0.88 m2/g) and assuming that the atrazine molecule
is a sphere with a radius (r) of 4.16  10
10 m, Borisover and Graber
(1997) estimated the maximum adsorption capacity of pahokee
peat for atrazine. First, the cross-section area (A) of atrazine can be
obtained as 3.14  (4.16  10
10)2 ¼ 54.4  10
20 m2; subsequently,
the surface covered by 1 mol of atrazine (MA) can be calculated as
(54.4  10
20 m2)  (6.023  1023/mol) ¼ 3.3  105 m2/mol. Sec-
ond, the maximum possible concentration of atrazine on the sur-
face area (Qomax,covered; maximum adsorption capacity) was
obtained by dividing the BET surface area (0.88 m2/g) by the surface
covered by 1 mol of atrazine (3.3  105 m2/mol) to give
2.7  10
6 mol/g. Finally, Qomax,covered was converted into weight
units using (2.7  10
6 mol/g)  (215.7 g/mol) to give 582 mg/g. This
value (582 mg/g) is substantially higher than the maximum
adsorption capacity obtained from the Langmuir equation (161 mg/
g). Although these calculations are correct, these inconsistent
values might originate from a misunderstanding by the authors
(Borisover and Graber, 1997) who state that “N2 BET measured
external surface area”, and thus attributed the value of 582 mg/g to
the maximal possible atrazine concentration on the external sur-
face of pahokee peat.
According to the 2011 guide for the accelerated surface area and
porosimetry (ASAP) system, the definition of the BET specific sur-
face area (m2/g) includes both the t-Plot external surface area (m2/
g) and the t-Plot micropore area (m2/g). Table 5 gives a typical
example of correct and incorrect use of the Micromeritics report
(experimental data measured using a Micromeritics ASAP 2020
sorptometer at 77 K). Although there were no problems found in
the N2 adsorption/desorption isotherms, the report results for BET
analysis of the prepared activated carbon in Table 5 contain
 H.N. Tran et al. / Water Research 120 (2017) 88e116 107

Fig. 9. Proposed mechanisms for Cr(VI) biosorption by nonliving biomass (Adapted from Park et al., 2005. Copyright (2005), with permission from Elsevier).

Table 5 Biosorbents that have not undergone any treatment have never
A typical example of correct and incorrect use of a Micromeritics report. been defined as porous materials; thus, the porosity of a biosorbent
Incorrect data Correct data is negligible.
Therefore, the iodine number cannot be applied for the deter-
Prepared activated carbon Prepared Biochar
mination of porosity for any biosorbent. Moreover, it is impossible
BET surface area 613 536 to obtain the very high iodine number reported for PGP (602 mg/g).
Langmuir surface area 1684 660
Micropore area NA 348
The high iodine number for PGP can be attributed to the high sulfur
External surface area 698 188 content (0.89%) and prolonged contact time (>30 s) (Tran, 2017).
According to the ASTM (D4607-14 2014), after transferring acti-
Note: NA means that the micropore area is not reported because either the micro-
pore volume is negative or the calculation of external surface area is larger than the vated carbon (g) into hydrochloric acid solution (5 wt%), the
total surface area (BET surface area). The unit is m2/g. Data are not published. 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 high sulfur contents. Notably,
the contact time between activated carbon and iodine solution
discrepancies, as the BET specific surface area value is less than the
(0.1 N) strongly impacts the determined iodine number. The con-
external surface area. This error resulted from calculation of the
tact time recommended by the ASTM was approximately 30 s,
specific surface area (SBET) in the range 0.38 < p/p0 < 0.57, instead of
while the contact time used by Ben Ali et al. was approximately
0.05 < p/p0 < 0.3.
4 min. Recently, Tran et al. (2017c) prepared activated carbons from
Recently, Ben Ali et al. (2016) used the “iodine number” to
golden shower using different chemical activation methods with
determine the surface area of a biosorbent without any treatment
K2CO3 (GSAC, GSBAC, and GSHAC). Their results indicated that the
(pomegranate peel; PGP) and concluded that “the specific surface
iodine numbers (mg/g) of the prepared activated carbons at a
area obtained is equal to 598.78 m2/g. Iodine number is generally used
contact time of 30 s were significantly lower than those at 5 min;
as an approximation for surface area and microporosity of active
GSAC (2,604 mg/g < 2,883 mg/g), GSBAC (1,568 mg/g < 2,296 mg/
carbons with good precision”. Tran (2017) commented that there are
g), GSHAC (2,695 mg/g < 4,842 mg/g).
two serious misconceptions in this work that need to be discussed.
Second, the textural properties of an adsorbent (i.e., specific
First, the iodine number of activated carbon is often determined
surface area, total pore volume, and micropore volume) can be
following the internal method, ASTM D4607-14 (D4607-14, 2014).
obtained from conventional analysis of nitrogen adsorption-
According to the ASTM, the iodine number (mg/g; amount of iodine
desorption isotherms, which are measured at 77 K using a sorp-
adsorbed (mg) by 1.0 g of activated carbon) is a relative indicator of
tometer (e.g., Micromeritics ASAP 2020). The BET method is widely
porosity in activated carbon. Iodine molecules (z0.27 nm) can be
employed to compute specific surface area (SBET) (Marsh and
adsorbed into the micropores (pore width > 1 nm) of porous ma-
Reinoso, 2006). Therefore, it is impossible to measure the surface
terials. However, the iodine number does not necessarily provide a
area of an adsorbent using the iodine number method. This
measure of the ability of activated carbon to adsorb other species.
mistaken assumption will lead to incorrect result, such as the
Although the iodine number may be used to approximate the
extremely high surface area of PGP (598.78 m2/g). The BET surface
surface area for several types of activated carbon, it must be real-
areas of various biosorbents are approximately 40 m2/g for yellow
ized that the relationship between surface area and iodine number
passion-fruit shell, 20 m2/g for orange peel, 8.17 m2/g for wheat
cannot be generalized, as it varies with changes in the raw carbon
straw, 8.13 m2/g for sargassum, 4.01 m2/g for Moringa oleifera
material, processing conditions, and pore volume distribution.
108 H.N. Tran et al. / Water Research 120 (2017) 88e116
Fig. 10. (a) Chemical structure of Congo Red and (b) UVevis spectra of Congo Red
solutions at different solution pH values (Adapted from Zhou et al., 2011. Copyright
(2011), with permission from Elsevier).
lamarck seed powder, 1.31 m2/g Spirogyra species, 1.21 m2/g for
waste pomace from an olive oil factory, 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). Thus, the discussions and
conclusions regarding the surface area of PGP made by Ben Ali et al.
(2016) are not valid, as they are inconsistent with the ASTM defi-
nitions and fundamental understanding of the porosities of
materials.
8.5. Maximum absorption wavelength in dye adsorption studies
A comment on the method of using the maximum absorption
wavelength (lmax) to calculate Congo red (CR) solution concentra-
tions was published by Zhou et al. (2011). They pointed out that CR
is very sensitive to pH and changes from red to blue owing to a p-p*
transition of the azo group following protonation (Fig. 10a). At
lower pH values, CR is protonated and cationic CR shows two
tautomeric forms: ammonium rich variety and azonium variety.
Therefore, the maximum absorption wavelength used to calculate
the concentration of CR in solution is strongly dependent on the
solution pH (both initial and final) (Fig. 10b); for example, lmax was
576 nm at pH 2.18e3.16, 567 nm at pH 3.86, and 496 nm at
pH  4.71.
Tien (2007) and Tien (2008) highlighted that commercial dyes
are often mixtures of active ingredients and filler materials are
often not recognized. Therefore, the possibility that experiments
may involve bi-solute adsorption is often not considered.
8.6. Cp-cation and p-p interactions
8.6.1. Cp-cation interactions
Recently, Morosanu et al. (2016) investigated the biosorption of
lead ions onto rapeseed biomass that was used as a biosorbent
without any treatments. On the basis of FTIR measurements before
and after adsorption, they concluded that the disappearance of the
peak at 1710 cm
1, which is characteristic of C]O stretching,
indicated surface complexion through Cp-cation interactions.
Similarly, Medellin-Castillo et al. (2017) examined the biosorption
of Pb2þ and Cd2þ onto a biosorbent derived from industrial chili
seeds. They also found changes in the intensity of the absorbance
peak at 1657 cm
1 in heavy-metal-loaded chili seeds, suggesting
that the adsorption of Cd2þ and Pb2þ involved p-cation interactions
between the aromatic rings of the lignin and the Cd2þ and Pb2þ
cations in the solution.
In general, Cp-cation interactions are attributed to electrostatic
interactions between the aromatic rings of basic carbonaceous
materials (i.e., biochar, carbon foam, carbon nanotubes, activated
carbon, and graphene) and metallic cations. For example, Tran et al.
(2015) used orange-peel-derived biochar, which was produced
through a carbonization process under limited-oxygen conditions
(also known as pyrolysis) at a high temperature (>400  C). Biochar
is known as a carbon-enriched porous material, similar to activated
carbon. Thus, biochar also possesses a graphite structure (C]C
bonds; p-electrons). As a result, Cp-cation interactions played a
primary role in the adsorption of heavy metals onto biochar.
Analogous conclusions were reached by other scholars
(Swiatkowski et al., 2004; Uchimiya et al., 2010; Rivera-Utrilla and
S
anchez-Polo, 2011).
The contribution of Cp-cation interactions to the mechanism of
heavy-metal adsorption onto carbonaceous material cannot be
denied. However, unlike biochar and activated carbon, biosorbents
(commonly derived from lignocellulose materials) do not possess a
graphite structure. In addition, although hydrochar prepared
through hydrothermal carbonization (i.e., 150e250  C controlled
temperature for 2e72 h at a specific pressure) exhibits an aromatic
carbon network, its properties are similar to those of biosorbents
(Tran et al., 2017c). Therefore, the presence of Cp-cation in-
teractions in heavy-metal adsorption onto biosorbents and hydro-
char is still controversial and needs to be further investigated.
Bui and Choi (2010) considered the role of cation-p bonding
between the protonated amino group of oxytetracycline (OTC) and
the graphene p electrons of multiwalled carbon nanotubes
(MWCNTs). Essentially, the cation-p bonding is dominated by the
electrostatic forces between the cation and the permanent quad-
rupole of the p-electron-rich aromatic structure and cation-
induced polarization (Ji et al., 2009). Like p-p interactions,
cation-p bonding would be suppressed with increasing pH. This is
because at a higher pH, deprotonation of the charged amino group
and protonation of the enol groups will be enhanced and so the
electron-acceptor ability of the oxytetracycline molecule is weaker
(Ji et al., 2009). Bui and Choi (2010) opined that Oleszczuk et al.
(2010) ignored the important roles of Ca2þ in the solution; for
example, Ca2þ possibly forms a complex with OTC in the solution or
Ca2þ can act as a cation bridge between the negatively charged OTC
and the negative charges of the MWCNTs. Therefore, Bui and Choi
(2010) suggested that Ca2þ may simultaneously bind with the
negatively charged OTC and interact either with the negative
charges or the graphene p electrons of the MWCNTs via cation-p
bonding. As pH is increased, both MWCNTs and OTC become more
negatively charged and, consequently, probably interact more
strongly with Ca2þ, leading to lower desorption of OTC. This hy-
pothesis could be further verified by studying the desorption of OTC
in the presence of NaCl, instead of CaCl2.
 H.N. Tran et al. / Water Research 120 (2017) 88e116
Fig. 11. An example of a graphene layer and proposed mechanisms of methylene adsorption green 5 onto biochar, synthesized activated carbon, and commercial activated charcoal
(Adapetd from Tran et al., 2017 b,d. Copyright (2017), with permission from Elsevier).
8.6.2. p-p interactions
p-p interactions (also known as p-p electron donor-acceptor
interactions) between the p-electrons in a carbonaceous adsor-
bent and the p-electron in the aromatic ring of an adsorbate were
initially proposed by Coughlin and Ezra (1968). In short, the addi-
tion of electron-withdrawing groups (i.e., oxygen-containing and
nitrogen-containing functional groups) at the edges of the indi-
vidual graphene layers within a carbonaceous solid causes a
considerable drop in the p-electron density. Positive holes are
consequently created in the conduction p-band of the individual
graphene layers, and the interactions between the p-electrons of a
carbonaceous adsorbent and the p-electrons of the adsorbate ar-
omatic rings become weaker.
Recently, Tran et al. (2017b, 2017d) investigated the mechanisms
of methylene green 5 (MG5) adsorption by commercial activated
charcoal, synthesized activated carbons, and prepared biochars.
They proposed that the primary mechanisms in MG5 adsorption
were p-p interactions and pore filling, while hydrogen bonding and
n-p interactions were minor contributors (Fig. 11). To identify the
existence of p-p interactions, they used two pieces of experimental
evidence. First, FTIR analysis showed that a peak corresponding to
the skeletal vibration of aromatic C]C bonds decreased in intensity
and upshifted after MG5 adsorption. Secondly, oxygenation of the
surface of the carbonaceous solids (i.e., biochar and activated car-
bon) through a hydrothermal process with acrylic acid resulted in a
decrease in MG5 adsorption and indicated the importance of p-p
interactions to the adsorption process.
As discussed in Section 8.6.1, hydrochar also possesses an
109
aromatic carbon network; therefore, p-p interactions might be
expected between the p-electrons of the aromatic C]C bonds in
hydrochar and the p-electrons of an adsorbate. However, a recent
study (Tran et al., 2017e) demonstrated that oxygenation of a
hydrochar surface through a hydrothermal process with acrylic
acid contributed to increasing MG5 adsorption and indicated the
negligible role of p-p interaction in the adsorption process. FTIR
analysis demonstrated that the aromatic C]C peak did not signif-
icantly decrease in intensity or shift toward higher/lower wave-
numbers after adsorption, which further confirms the insignificant
contribution of p-p interactions. Electrostatic attraction played a
major role in the adsorption mechanism of MG5 onto hydrochar,
while hydrogen bonding and n-p interactions were minor con-
tributors. The primary adsorption mechanisms of MG5 onto
hydrochar were similar to those on biosorbents, but dissimilar to
biochar and activated carbon (i.e., p-p interaction and pore filling).
An identical result was obtained in the investigation of phenol,
MG5, and acid read 1 adsorption onto a commercial glucose-
derived spherical hydrochar functionalized with triethylenetetr-
amine (Tran et al., 2017a). Therefore, it can be concluded that the
addition of oxygen- and nitrogen-containing functional groups
(electron-withdrawing groups) on the surface of hydrochar does
not cause a considerable drop in the p-electron density, but this
process provides abundant adsorption sites on the hydrochar
surface.
Jiang et al. (2009) and Chen et al. (2009) argued over the pri-
mary adsorption mechanisms of hydroxyl- and amino-substituted
aromatics on carbon nanotubes and graphite (CNTs/graphite).
110 H.N. Tran et al. / Water Research 120 (2017) 88e116
Chen et al. (2009) proposed that p-p interactions played a major
role in the adsorption mechanism. However, Jiang et al. (2009)
remarked that the experiments of Chen et al. (2009) were insuffi-
cient to support the presence of p-p electron-donor
acceptor
(EDA) interactions between hydroxyl-substituted aromatics and
CNTs/graphite. According to Jiang et al. (2009), phenolic com-
pounds were not appropriate candidates to assess the presence of
p-p EDA interactions between p-electron-donating aromatics and
CNTs because of the significant effects of oxygen. Therefore, the
oxygen effect should be considered in more detail in order to gain
in-depth insights into the adsorption mechanisms of environ-
mentally relevant phenolic compounds onto carbonaceous
materials.
8.7. Other miscellaneous errors
Azizian (2007) commented that the theoretical development of
empirical PFO and PSO kinetic adsorption models using a more
general rate theory was first reported by Azizian (2004), not by
Rudzinski and Plazinski (2007). Furthermore, the idea that the PFO
model can only be derived theoretically at a nearly constant bulk
concentration was first proposed by Azizian (2004). In addition, the
conclusion that the PFO and PSO models are simplified forms of a
more general equation was proposed independently by Azizian
(2004) (who relied on the Langmuir kinetic model) and by
Rudzinski and Plazinski (2007) (who relied on the statistical rate
theory). Similarly, mistakes related to either no citation of the
original paper or incorrect citation were pointed out by Azizian
(2008b).
A series of mistakes related to incorrectly digitized data, typos,
inaccurate calculations, incorrect use of conditional equilibrium
constants, incorrect units, incorrect references, incorrect applica-
tion of modeling procedures, and other miscellaneous errors have
been highlighted by Gustafsson and Lumsdon (2014).
The distinction between heat of adsorption, adsorption energy,
and activation energy in adsorption was reported elsewhere
(Inglezakis and Zorpas, 2012). The authors concluded that it is
important to distinguish the differential enthalpy at zero coverage
(DHdo) from the differential enthalpy or isosteric heat (DHd) and the
standard heat of complete coverage or integral enthalpy (DH ),
which expresses the total heat generation for the adsorption and is
related to the thermodynamic equilibrium constant.
Li et al. (2010) pointed out that (1) although the cited documents
were solid and sound in their scientific aspects, the reviewers
seemed to fail to take full advantage of the intrinsically contained
information; (2) there were some critical errors in the main text;
and (3) the writing style of the paper was misleading and, to some
extent, lacked cautiousness. They focused on 11 comments and
concluded that the original paper's conclusions were not opti-
mistic. However, most of these comments were rejected by the
original authors (Mohan and Pittman, 2011).
Regarding the correct citation for determining pHPZC using the
batch equilibration method, Milonji
c (2009a) commented that this
method was originally proposed by Milonji
c et al. (1975). Further-
more, Milonji
c (2009a) noted that using correct and updated cita-
tions were very important for researchers to find relevant
information, pioneer ideas, and make progress in a particular
subject. Additionally, from a scientific point of view, it is always
necessary to give credit to the authors who first proposed a method
or theoretical model. Recently, Tran et al. (2017b) applied the “drift
method” to determine the pHPZC of commercial activated charcoal
(CAC). The effects of various operation conditions (i.e., different
degassing times with N2, background electrolytes, concentrations
of an electrolyte, solid/liquid ratios, and contact times) on the pHPZC
were investigated. The results demonstrated that the pHPZC
(9.81 ± 0.07) of CAC was insignificantly dependent on the operation
conditions.
Geckeis and Rabung (2004) pointed out that photon correlation
spectroscopy is a method for colloid size determination, not for
zeta-potential analysis. Methods that have been correctly applied
for zeta-potential analysis include electrophoretic light scattering
and laser Doppler velocimetry, and the units for the measured zeta
potentials are mV, not eV.
Lee (2017) considered the potential effects of flow velocity on
the concentration and distribution of triphenyltin chloride (TPT) on
nano zinc oxide (nZnO). The author remarked that TPT was possibly
re-suspended by the hydraulic flow that occurs during hydrant
flushing in a reactor because TPT can be loosely deposited on the
nZnO surface. As reported in the literature, the flow velocity in a
wastewater treatment system is one of the factors affecting the
removal efficiency for a tested pollutant. The distribution of TPT on
nZnO might vary during the adsorption process according to the
time of hydrant flushing; therefore, the process of TPT adsorption
onto nZnO might be affected by the operating conditions of a
reactor. However, the authors of the commented paper replied that
the application of nZnO for the removal of TPT from dockyard
wastewater was examined using a batch adsorption technique. As a
result, the effects of flow velocity on the adsorption process con-
ducted in the batch experiments were negligible compared to that
in pilot studies and/or column experiments.
Kamagate
et al. (2016) and Koma

rek et al. (2016) considered the
influence of Si species originating from the partial dissolution of
quartz on the competitive adsorption of Cd(II), Cr(VI), and Pb(II)
onto nanomaghemite- and nanomaghemite-coated quartz. They
recommended that to accurately assess the interfacial reaction
mechanisms occurring at the Fe-oxide/water interface in the
presence of Si-complex mineral assemblages or Fe-coated sand
systems, more attention should be paid to the possible release of
silicate from Si-bearing minerals and its subsequent adsorption on
reactive phases.
A critical paper entitled “comments on “zirconium-carbon
hybrid sorbent for removal of fluoride from water: oxalic acid
mediated Zr(IV) assembly and adsorption mechanism”” was pub-
lished by Zhao (2015). The authors of the original paper concluded
that the fluoride adsorption occurs on the surface sites of ZrOx-AC
(commercial activated carbon modified with Zr together with
oxalic acid) with eOH displacement and/or interacts with the
positive charge of zirconium to form eCOOH groups in the oxalate
acid; however, Zhao (2015) suggested that if the fluoride concen-
tration is high enough, it would completely desorb the oxalate acid
from the ZrOx-AC surface. According to the results of previous
experiments, Zhao (2015) suggested that it is necessary to further
consider or add the exchangeable role of chloride and oxalic acid in
the proposed fluoride-adsorption mechanism.
Fan et al. (2007) additionally discussed the mechanisms of
fluoride adsorption by calcined Mg-Al-CO3 layered double hy-
droxides (CLDH). Based on the experimental data published in the
original paper and analysis of other literature results, they
concluded that XRD measurements indicated that mixed Mg-Al
oxides, as well as partially restored LDH, was present in fluoride-
loaded CLDH after freeze-drying treatment. Furthermore, fluoride
can be effectively adsorbed onto MgO, demonstrating that fluoride
adsorption over the mixed oxide along with a memory effect ac-
counts for the effective removal of fluoride by CLDH.
An analytical article on the magnitude of estimated maximum
surface-area-normalized adsorption capacities (Qmax*) for the
adsorption of polycyclic aromatic hydrocarbons and poly-
chlorobiphenyls on soot and soot-like carbon materials was pub-
lished by Werner and Karapanagioti (2005). The original authors
(van Noort et al., 2005) used the Langmuir isotherm to extrapolate
 H.N. Tran et al. / Water Research 120 (2017) 88e116
Qmax* at the solubility limit from solid-water distribution co-
efficients (Ks) measured in the pg/L to ng/L range along with esti-
mated Langmuir affinities for adsorption (KL) on a carbonaceous
surface. After comparison with estimated surface-area-normalized
monolayer adsorption capacities (Qmono*) and with empirical
sorption data from the literature, Werner and Karapanagioti (2005)
concluded that “the Langmuir isotherm cannot be used to extrapolate
maximum sorption capacities (Qmax*) near the aqueous-sorbate
saturation limit from distribution coefficients measured at extremely
low aqueous-sorbate concentrations. Adsorption sites in carbon ma-
terials are not uniform and other processes, such as multilayer
adsorption, condensation in capillary pores, and absorption into the
polymeric matrix, may be relevant near the solubility limit”.
Müller et al. (2017) analyzed strong conflicts between the XPS
and XRD data and their interpretation by the original author in a
study on the synthesis of Yb doped CuFe2O4 nanoferrite adsorbents
(i.e., CuYb0.5Fe1.5O4) and the application of such adsorbents in the
Fig. 12. A simple guide to the nonlinear method of calculating the Langmuir parameters using (a) “Solver add-in” in Microsoft office Excel (RSS: residual sum of squares, TSS: total
sum of squares) and (b) Origin program.
111
removal of different pollutants (e.g. methyl orange, safranin, Cr3 þ,
and Pb2 þ). After a discussion, Müller et al. (2017) concluded that
because “any experimental study stands and falls on the reliability of
the investigated specimen the lack of any significance therefore holds
for this study as a whole”.
Interestingly, a series of recommendations and suggestions
were written by the editor of Carbon journal for improving
manuscript quality and avoiding mistakes (Thrower, 2007, 2008a,
2008b, 2010, 2011). The author focused on five main topics: titles
and abstracts, introduction and references, experimental, results
and discussion, and language.
9. Nonlinear-optimization technique
To calculate the parameters of kinetic and isotherm models
accurately in both batch and column experiments, application of
the nonlinear method instead of the linear method has been
112 H.N. Tran et al. / Water Research 120 (2017) 88e116
recommended by many researchers (Porter, 1985; Ho, 2004b; Ho
et al., 2005; Bolster and Hornberger, 2007; Han et al., 2007;
Kumar, 2007; El-Khaiary et al., 2010; Chowdhury and Das Saha,
2011; Lima et al., 2015; Tran et al., 2015, 2017d).
Furthermore, to identify the best-fit model, calculation of the
chi-squared (c2, Eq. (96)) value is recommended in addition to
calculating the coefficient of determination (R2, Eq. (97)) for the
nonlinear method. In the chi-squared test, the squares of the dif-
ferences between the experimental data and data calculated using
the models are divided by the corresponding data obtained and
then summed. If the data obtained using a model are similar to the
experimental data, c2 is close to zero. High c2 values indicate high
bias between the experiment and model. Therefore, analyzing the
data set using the chi-squared test is necessary to confirm the best-
fit isotherm for a given sorption system (Ho, 2004b; Ho et al., 2005;
Chowdhury and Das Saha, 2011; Lima et al., 2015; Tran et al., 2015,
2017b, 2017d, 2017e).

2
X qe;exp
qe;cal
c2 ¼ (96)
qe;cal
P
2
qe;exp
qe;cal
2
R ¼1
(97)
P
2
qe;exp
qe;mean
where qe,exp (mg/g) is the amount of adsorbate uptake at equilib-
rium obtained from Eq. (1), qe,cal (mg/g) is the amount of adsorbate
uptake achieved from the model using the Solver add-in, and
qe,mean (mg/g) is the mean of the qe,exp values.
Lima et al. (2015) confirmed that the use of nonlinear equilib-
rium and kinetic adsorption models gives values that are reliable
and statistically relevant for modeling the isotherm and kinetics of
adsorption. Moreover, they did not suggest using linearized equi-
librium and kinetic adsorption models, even in the cases of the
linearized Langmuir Type 1 and linearized PSO Type 1 equations
that provide R2 values close to unity. The linearization of equilib-
rium and kinetic adsorption models could make the parameters
determined from these models meaningless.
Owing to the wide application of the nonlinear method in the
study of adsorption processes, we provide here a short introduction
to the application of this method using the “Solver add-in” in
Microsoft Office Excel (2013 version). First, it is necessary to load
the Solver add-in in Microsoft Excel: File / Excel options / Add-
ins (select Excel Add-ins in Manage box) / select the Solver Add-in
check box. Second, all Ce and qe values obtained experimentally are
considered as input data, and the qe values from the Langmuir
equation are calculated based on two variables (Qomax and KL s 0).
Using the Solver Add-in (Fig. 12a), the Qomax, KL, and R2 values can
be obtained. Notably, other programs (i.e., Origin; Fig. 12b) also
provide similar results and can accurately calculate the parameters
of kinetic and isotherm models.
10. Conclusions
In scientific publications, the correct use of technical terms and
accurate calculations are essential. According to the viewpoints
discussed in this review, we put forward the following key con-
clusions and perspectives:
i. Adsorption performance should be expressed as qe (mg/g),
while the use of the unit of %removal should be avoided or
used cautiously.
ii. The use of accurate citations and correct mathematical ex-
pressions in original works is also recommended.
iii. Measurements of adsorption kinetics should be started at an
initial time of less than 2 min and finish when the adsorption
process reaches true equilibrium.
iv. A complete adsorption isotherm (plotting qe versus Ce)
should be presented when investigating liquid-phase
adsorption to identify the regions in which the experi-
mental data relating to adsorption equilibrium are actually
located.
v. Differences between the number of data points in an
experiment and those used for model fitting (i.e., the pseudo-
second-order or Langmuir models) should be avoided.
vi. For adsorption thermodynamics, the equilibrium constant
(KC) must be dimensionless. The optimal method for calcu-
lating thermodynamic parameters should be appropriately
selected according to the data from the adsorption equilib-
rium experiment. Notably, it is impossible to calculate ther-
modynamic parameters from an experiment using one initial
adsorbate concentration at different temperatures.
vii. To accurately estimate the parameters of adsorption kinetic
and isotherm models, the nonlinear optimization technique
should be applied to decrease the bias between the qe values
calculated from the experimental data and those estimated
from the models. The chi-squared (c2) test should be used
alongside the nonlinear determination coefficient (R2) to
obtain the best-fit models for adsorption kinetics and
isotherms.
viii. An in-depth understanding of the models applied to
adsorption kinetics and isotherms is necessary to avoid
misapplication of these models, as well as inaccurate dis-
cussions, calculations, and conclusions.
ix. More attention should be paid to various common mis-
understandings about fundamental adsorption and chemis-
try concepts. Understanding the unique properties of
adsorbents and target adsorbates can help avoid mistakes
made when explaining adsorption mechanisms.
Although the comments and recommendations of some authors
are not always correct, their observations and suggestions should
be acknowledged because of their great contributions in trans-
ferring scientific knowledge.
Acknowledgements
The first author would like to thank Chung Yuan Christian
University for the Distinguished International Graduate Students
(DIGS) scholarship to pursue his doctoral studies. The authors
gratefully acknowledge the editor and anonymous reviewers for
their invaluable insight and helpful suggestion.
References
Alagumuthu, G., Veeraputhiran, V., Rajan, M., 2010. Comments on “Fluoride removal
from water using activated and MnO2-coated Tamarind Fruit (Tamarindus
indica) shell: batch and column studies”. J. Hazard. Mater. 183 (1e3), 956e957.
Anastopoulos, I., Kyzas, G.Z., 2016. Are the thermodynamic parameters correctly
estimated in liquid-phase adsorption phenomena? J. Mol. Liq. 218, 174e185.
Aoyama, M., 2003. Comment on “Biosorption of chromium(VI) from aqueous so-
lution by cone biomass of Pinus sylvestris”. Bioresour. Technol. 89 (3), 317e318.
Arica, M.Y., 2003. In reaction to the comment by Dr. Y.-S. Ho on our publication
“Affinity dye-ligand poly(hydroxyethylmethacrylate/chitosan composite mem-
brane for adsorption lysozyme and kinetic properties, Biochemical Engineering
Journal 13(2003) 35e45. Biochem. Eng. J. 15 (1), 79e80.
Azizian, S., 2004. Kinetic models of sorption: a theoretical analysis. J. Colloid
Interface Sci. 276 (1), 47e52.
Azizian, S., 2006. A novel and simple method for finding the heterogeneity of ad-
sorbents on the basis of adsorption kinetic data. J. Colloid Interface Sci. 302 (1),
 H.N. Tran et al. / Water Research 120 (2017) 88e116
76e81.
Azizian, S., 2007. Comment on “Kinetics of solute adsorption at solid/solution in-
terfaces: a theoretical development of the empirical pseudo-first and pseudo-
second order kinetic rate equations, based on applying the statistical rate
theory of interfacial transport”. J. Phys. Chem. B 111 (1), 318.
Azizian, S., 2008a. 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), 322e323.
Azizian, S., 2008b. Comments on “Biosorption isotherms, kinetics and thermody-
namics” review. Sep. Purif. Technol. 63 (2), 249e250.
Ben Ali, S., Jaouali, I., Souissi-Najar, S., Ouederni, A., 2016. Characterization and
adsorption capacity of raw pomegranate peel biosorbent for copper removal.
J. Clean. Prod. 142, 3809e3821.
Biggar, J.W., Cheung, M.W., 1973. Adsorption of picloram (4-amino-3,5,6-
trichloropicolinic acid) on panoche, ephrata, and palouse soils: a thermody-
namic approach to the adsorption mechanism1. Soil Sci. Soc. Am. J. 37 (6).
Blanchard, G., Maunaye, M., Martin, G., 1984. Removal of heavy metals from waters
by means of natural zeolites. Water Res. 18 (12), 1501e1507.
Bolster, C.H., Hornberger, G.M., 2007. On the use of Linearized Langmuir equation.
Soil Sci. Soc. Am. J. 71 (6), 1796e1806.
Borisover, M.D., Graber, E.R., 1997. Comment on “Competitive sorption between
atrazine and other organic compounds in soils and model sorbents”. Environ.
Sci. Technol. 31 (5), 1577.
Bui, T.X., Choi, H., 2010. Comment on “Adsorption and desorption of oxytetracycline
and carbamazepine by multiwalled carbon nanotubes”. Environ. Sci. Technol.
44 (12), 4828.
Canzano, S., Iovino, P., Salvestrini, S., Capasso, S., 2012. Comment on “Removal of
anionic dye Congo red from aqueous solution by raw pine and acid-treated pine
cone powder as adsorbent: equilibrium, thermodynamic, kinetics, mechanism
and process design”. Water Res. 46 (13), 4314e4315.
Cavas, L., 2008. Comment on Equilibrium Sorption Isotherm Studies of Cd(II), Pb(II)
and Zn (II) Ions Detoxification from Waste Water Using Unmodified and EDTA-
modified Maize Husk.
Chen, W., Duan, L., Wang, L., Zhu, D., 2009. Response to comment on “Adsorption of
hydroxyl- and amino-substituted aromatics to carbon nanotubes”. Environ. Sci.
Technol. 43 (9), 3400e3401.
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), 265e268.
Choong, T.S.Y., Chuah, T.G., 2005. Comment on “Separation of vitamin E from palm
fatty acid distillate using silica: I. Equilibrium of batch adsorption by B.S. Chu
et al. [Journal of Food Engineering 62(2004) 97e103]”. J. Food Eng. 67 (3), 379.
Chowdhury, S., Das Saha, P., 2011. Comparative analysis of linear and nonlinear
methods of estimating the pseudo-second-order kinetic parameters for sorp-
tion of malachite green onto pretreated rice husk. Bioremed. J. 15 (4), 181e188.
Chu, B.S., Baharin, B.S., Man, Y.B.C., Quek, S.Y., 2005. Reply from the authors to the
comments by Choong and Chuah in a recent Letter to the Editor on “Separation
of vitamin E from palm fatty acid distillate using silica: I. Equilibrium of batch
adsorption by B.S. Chu et al. [Journal of Food Engineering 62(2004) 97e103]”.
J. Food Eng. 69 (1), 131e132.
Coughlin, R.W., Ezra, F.S., 1968. Role of surface acidity in the adsorption of organic
pollutants on the surface of carbon. Environ. Sci. Technol. 2 (4), 291e297.
Crittenden, J.C., Trussell, R.R., Hand, D.W., Howe, K.J., Tchobanoglous, G., 2012.
Adsorption. MWH's Water Treatment: Principles and Design, third ed. John
Wiley & Sons, Inc., pp. 1117e1262
D4607-14, A., 2014. Standard Test Method for Determination of Iodine Number of
Activated Carbon. American Society for Testing and Materials, Philadelphia,
U.S.A.
Dambies, L., Guimon, C., Yiacoumi, S., Guibal, E., 2001. Characterization of metal ion
interactions with chitosan by X-ray photoelectron spectroscopy. Colloids Surf. A
Physicochem. Eng. Asp. 177 (2e3), 203e214.
Dawood, S., Sen, T.K., 2012. Author's Responses to the comment by Canzano et al
and also corrigendum to “Removal of anionic dye Congo red from aqueous
solution by raw pine and acid-treated pine cone powder as adsorbent: equi-
librium, thermodynamic, kinetics, mechanism and process design” published in
Water Research, Vol. 46, pp. 1933e1946, 2012. Water Res. 46 (13), 4316e4317.
Doke, K.M., Khan, E.M., 2013. Adsorption thermodynamics to clean up wastewater;
critical review. Rev. Environ. Sci. Bio Technol. 12 (1), 25e44.
Dubinin, M., Radushkevich, L., 1947. Equation of the characteristic curve of activated
charcoal. Chem. Zentr. 1 (1), 875.
Egirani, D., 2004. Comments on: removal of copper ions from aqueous solution by
tree ferns. Water Res. 38 (20), 4535.
El-Khaiary, M.I., Malash, G.F., Ho, Y.-S., 2010. On the use of linearized pseudo-
second-order kinetic equations for modeling adsorption systems. Desalination
257 (1e3), 93e101.
Fan, J., Xu, Z., Zheng, S., 2007. Comment on “Factors influencing the removal of
fluoride from aqueous solution by calcined MgeAleCO3 layered double hy-
droxides”. J. Hazard. Mater. 139 (1), 175e177.
Farooq, U., Kozinski, J.A., Khan, M.A., Athar, M., 2010. Biosorption of heavy metal
ions using wheat based biosorbents e a review of the recent literature. Bio-
resour. Technol. 101 (14), 5043e5053.
Febrianto, J., Kosasih, A.N., Sunarso, J., Ju, Y.-H., Indraswati, N., Ismadji, S., 2009.
Equilibrium and kinetic studies in adsorption of heavy metals using biosorbent:
a summary of recent studies. J. Hazard. Mater. 162 (2e3), 616e645.
Foo, K.Y., Hameed, B.H., 2010. Insights into the modeling of adsorption isotherm
113
systems. Chem. Eng. J. 156 (1), 2e10.
Freundlich, H., 1906. Über die Adsorption in Lo €sungen. Z Phys. Chem. 57, 385e471.
Fu, L., Huang, X., Wang, J., 2007. Comment on “Removal of supranol yellow 4GL by
adsorption onto Cr-intercalated montmorillonite”. J. Hazard. Mater. 148 (3),
771e772.
Fu, L., Wang, J., Lu, H., Su, Y., Ren, A., 2008. Comment on “The removal of phenolic
compounds from aqueous solutions by organophilic bentonite”. J. Hazard.
Mater. 151 (2e3), 851e854.
Gardea-Torresdey, J.L., Tiemann, K.J., Armendariz, V., Bess-Oberto, L., Chianelli, R.R.,
Rios, J., Parsons, J.G., Gamez, G., 2000. Characterization of Cr(VI) binding and
reduction to Cr(III) by the agricultural byproducts of Avena monida (Oat)
biomass. J. Hazard. Mater. 80 (1e3), 175e188.
Geckeis, H., Rabung, T., 2004. Comment on the paper: X. Wang, Th. Rabung, H.
Geckeis, Effect of pH and humic acid on the adsorption of cesium onto g-Al2O3.
J. Radioanal. Nucl. Chem. 260 (2), 437e438.
Ghosal, P.S., Gupta, A.K., 2015. An insight into thermodynamics of adsorptive
removal of fluoride by calcined Ca-Al-(NO3) layered double hydroxide. RSC Adv.
5 (128), 105889e105900.
Ghosal, P.S., Gupta, A.K., 2017. Determination of thermodynamic parameters from
Langmuir isotherm constant-revisited. J. Mol. Liq. 225, 137e146.
Goldberg, S., 2009. Comments on “adsorption sequence of toxic inorganic anions on
a soil” by K. Saeki Bull Environ Contam Toxicol (2008) 81:508e512. Bull. En-
viron. Contam. Toxicol. 83 (1), 1e2.
Goldberg, S., 2016. A comment on “Selenite adsorption and desorption in main
Chinese soils with their characteristics and physicochemical properties. J Soils
Sediments 15(5):1150e1158(2015), doi:10.1007/s11368-015-1085-7. J. Soils
Sediments 16 (1), 324.
Goswami, R., Shim, J., Deka, S., Kumari, D., Kataki, R., Kumar, M., 2016. Character-
ization of cadmium removal from aqueous solution by biochar produced from
Ipomoea fistulosa at different pyrolytic temperatures. Ecol. Eng. 97, 444e451.
Guo, H., Zhang, S., Kou, Z., Zhai, S., Ma, W., Yang, Y., 2015. Removal of cadmium(II)
from aqueous solutions by chemically modified maize straw. Carbohydr. Polym.
115 (0), 177e185.
Gustafsson, J.P., Lumsdon, D.G., 2014. Comment on “Citrate adsorption can decrease
soluble phosphate concentration in soils: results of theoretical modelling” by
Marek Duputel, Nicolas Devau, Michel Brossard, Benoît Jaillard, Davey L. Jones,
Philippe Hinsinger and Fre
de
ric Ge
rard (2013). Appl. Geochem. 46, 85e89.
Haerifar, M., Azizian, S., 2013. Mixed surface reaction and diffusion-controlled ki-
netic model for aAdsorption at the solid/solution interface. J. Phys. Chem. C 117
(16), 8310e8317.
Hai, T.N., 2017. Comments on “Effect of temperature on the adsorption of methylene
blue dye onto sulfuric acidetreated orange peel”. Chem. Eng. Commun. 204 (1),
134e139.
Halder, G., Khan, A.A., Dhawane, S., 2016. Fluoride sorption onto a steam-activated
biochar derived from cocos nucifera shell. CLEAN Soil Air Water 44 (2),
124e133.
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), 212e223.
Hamdaoui, O., Naffrechoux, E., 2007. Modeling of adsorption isotherms of phenol
and chlorophenols onto granular activated carbon: Part II. Models with more
than two parameters. J. Hazard. Mater. 147 (1e2), 401e411.
Han, R., Wang, Y., Zou, W., Wang, Y., Shi, J., 2007. Comparison of linear and nonlinear
analysis in estimating the Thomas model parameters for methylene blue
adsorption onto natural zeolite in fixed-bed column. J. Hazard. Mater. 145 (1e2),
331e335.
Harsha, N., Krishna, K.V.S., Renuka, N.K., Shukla, S., 2015. Facile synthesis of
[gamma]-Fe2O3 nanoparticles integrated H2Ti3O7 nanotubes structure as a
magnetically recyclable dye-removal catalyst. RSC Adv. 5 (38), 30354e30362.
Ho, Y.-S., 1995. Adsorption of Heavy Metals from Waste Streams by Peat (Ph.D.
Thesis). The University of Birmingham, Birmingham, U.K.
Ho, Y.-S., 2004a. Erratum to “Removal of copper ions from aqueous solution by tree
fern”: [Water Res. 37(2003) 2323e2330]. Water Res. 38 (20), 4536e4537.
Ho, Y.-S., 2004b. Selection of optimum sorption isotherm. Carbon 42 (10),
2115e2116.
Ho, Y.-S., 2005. Comment on “Two-stage batch sorber design using second-order
kinetic model for the sorption of metal complex dyes onto pine sawdust” by
€
Ozacar, _
M. and Şengýl, I.A. Biochem. Eng. J. 23 (3), 291e292.
Ho, Y.-S., 2013. Comments on “Removal of zirconium(IV) from aqueous solution by
Coriolus versicolor: equilibrium and thermodynamic study”. Ecol. Eng. 58, 1e2.
Ho, Y.-S., 2014a. Comments on “Adsorption of 2-mercaptobenzothiazole from
aqueous solution by organo-bentonite” by P. Jing, M.H. Hou, P. Zhao, X.Y. Tang,
H.F. Wan. J. Environ. Sci. 26 (12), 2571e2572.
Ho, Y.-S., 2014b. Comment on “New Calix[4]arene appended amberlite XAD-4 resin
with versatile perchlorate removal efficiency”. J. Chem. Eng. Data 59 (6), 2131.
Ho, Y.-S., 2014c. Comments on “Adsorption characteristics and behaviors of gra-
phene oxide for Zn(II) removal from aqueous solution”. Appl. Surf. Sci. 301, 584.
Ho, Y.-S., 2014d. Comments on “Simultaneous adsorption of aniline and Cr(VI) Ion
by activated carbon/chitosan composite”. J. Appl. Polym. Sci. 131 (22) (n/a-n/a).
Ho, Y.-S., 2014e. Comments on the paper “Removal of Cu (II) by loofah fibers as a
natural and low-cost adsorbent from aqueous solutions”. J. Mol. Liq. 198, 322.
Ho, Y.-S., 2014f. The real pseudo-second-order rate equation. Ind. Crops Prod. 52, 17.
Ho, Y.-S., 2014g. Using of “pseudo-second-order model” in adsorption. Environ. Sci.
Pollut. Res. 21 (11), 7234e7235.
Ho, Y.-S., 2015. Comment on “Genetic characterization, nickel tolerance,
114 H.N. Tran et al. / Water Research 120 (2017) 88e116
biosorption, kinetics, and uptake mechanism of a bacterium isolated from
electroplating industrial effluent”. Can. J. Microbiol. 61 (11), 881e882.
Ho, Y.-S., 2016a. Comments on the paper ‘Synthesis and application of ion-
imprinted resin based on modified melamine-thiourea for selective removal
of Hg(II)’. Polym. Int. 65 (7), 845e846.
Ho, Y.-S., 2016b. Comments on the paper “Removal of aqueous Hg(II) and Cr(VI)
using phytic acid doped polyaniline/cellulose acetate composite membrane”.
J. Hazard. Mater. 311, 273e274.
Ho, Y.-S., 2016c. Comments on the paper “Simultaneous removal of mixed con-
taminants by organoclays d amoxicillin and Cu(II) from aqueous solution”.
Appl. Clay Sci. 126, 297e298.
Ho, Y.-S., 2016d. Comments on using of “pseudo-first-order model” [J. Taiwan Inst.
Chem. Eng. Vol. 59]. J. Taiwan Inst. Chem. Eng. 68, 136e137.
Ho, Y.-S., 2016e. Comments on using of “pseudo-first-order model” in adsorption
[Int. J. Biol. Macromol., vol. 81]. Int. J. Biol. Macromol. 88, 505e506.
Ho, Y.-S., 2017. Comments on the paper “Application of Mn/MCM-41 as an adsor-
bent to remove Methyl Blue from aqueous solution”. J. Colloid Interface Sci. 498,
461.
Ho, Y.-S., Chiu, W.-T., Wang, C.-C., 2005. Regression analysis for the sorption iso-
therms of basic dyes on sugarcane dust. Bioresour. Technol. 96 (11), 1285e1291.
Ho, Y.S., McKay, G., 1998a. A comparison of chemisorption kinetic models applied to
pollutant removal on various sorbents. Process Saf. Environ. Prot. 76 (4),
332e340.
Ho, Y.S., McKay, G., 1998b. Sorption of dye from aqueous solution by peat. Chem.
Eng. J. 70 (2), 115e124.
Ho, Y.S., Wase, D.A.J., Forster, C.F., 1996. Kinetic studies of competitive heavy metal
adsorption by sphagnum moss peat. Environ. Technol. 17 (1), 71e77.
Huang, R., Yang, B., Liu, Q., Liu, Y., 2014. Simultaneous adsorption of aniline and
Cr(VI) ion by activated carbon/chitosan composite. J. Appl. Polym. Sci. 131 (4) (n/
a-n/a).
Hung, H.-W., Lin, T.-F., 2006. Adsorption of MTBE from contaminated water by
carbonaceous resins and mordenite zeolite. J. Hazard. Mater. 135 (1e3),
210e217.
Inbaraj, B.S., 2006. Comment on “Adsorption of reactive dyes from a textile effluent
using sawdust as the adsorbent”. Ind. Eng. Chem. Res. 45 (21), 7362.
Inglezakis, V.J., Zorpas, A.A., 2012. Heat of adsorption, adsorption energy and acti-
vation energy in adsorption and ion exchange systems. Desalination Water
Treat. 39 (1e3), 149e157.
Ji, L., Chen, W., Duan, L., Zhu, D., 2009. Mechanisms for strong adsorption of
tetracycline to carbon nanotubes: a comparative study using activated carbon
and graphite as adsorbents. Environ. Sci. Technol. 43 (7), 2322e2327.
Jiang, J., Pang, S.-Y., Ma, J., 2009. Comment on “Adsorption of hydroxyl- and amino-
substituted aromatics to carbon nanotubes”. Environ. Sci. Technol. 43 (9),
3398e3399.
Jing, P., Hou, M., Zhao, P., Tang, X., Wan, H., 2014. Reply to comments on “Adsorption
of 2-mercaptobenzothiazole from aqueous solution by organo-bentonite” by
Yuhshan Ho. J. Environ. Sci. 26 (12), 2573e2574.
Kamagate
, M., Lützenkirchen, J., Huber, F., Hanna, K., 2016. Comment on
“Competitive adsorption of Cd(II), Cr(VI), and Pb(II) onto nanomaghemite: a
spectroscopic and modeling approach”. Environ. Sci. Technol. 50 (3),
1632e1633.
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
surfactant-modified zeolite. J. Chem. Eng. Data 52 (5), 1615e1620.
Khan, A.A., Singh, R.P., 1987. Adsorption thermodynamics of carbofuran on Sn (IV)
arsenosilicate in Hþ, Naþ and Ca2þ forms. Colloids Surf. 24 (1), 33e42.
Kom
arek, M., Koretsky, C.M., Stephen, K.J., Alessi, D.S., Chrastný, V., 2016. Response
to Comment on “Competitive adsorption of Cd(II), Cr(VI), and Pb(II) onto
nanomaghemite: a spectroscopic and modeling approach”. Environ. Sci. Tech-
nol. 50 (3), 1634e1635.
Kim, Y., Bae, J., Park, H., Suh, J.-K., You, Y.-W., Choi, H., 2016. Adsorption dynamics of
methyl violet onto granulated mesoporous carbon: facile synthesis and
adsorption kinetics. Water Res. 101, 187e194.
Kosmulski, M., 2009. Surface Charging and Points of Zero Charge. CRC Press.
Kratochvil, D., Volesky, B., 1998. Advances in the biosorption of heavy metals.
Trends Biotechnol. 16 (7), 291e300.
Kumar, K.V., 2006a. Comments on “Adsorption of acid dye onto organobentonite”.
J. Hazard. Mater. 137 (1), 638e639.
Kumar, K.V., 2006b. Comments on “Equilibrium studies for the adsorption of Acid
dye onto modified hectorite”. J. Hazard. Mater. 137 (2), 1252e1253.
Kumar, K.V., 2006c. A note on the comments by Dr. Y.S. Ho on “Nitrate removal from
aqueous solution by adsorption onto various materials”. J. Hazard. Mater. 136
(3), 995e996.
Kumar, K.V., 2006d. A note on the comments by Dr. Y.S. Ho on “Remediation of soil
contaminated with the heavy metal (Cd2þ)”. J. Hazard. Mater. 136 (3),
993e994.
Kumar, K.V., 2007. Optimum sorption isotherm by linear and non-linear methods
for malachite green onto lemon peel. Dyes Pigments 74 (3), 595e597.
Kumar, K.V., F
avere, V.T., 2006. Reply to Comments on ‘Chitosan functionalized with
2[-bis-(pyridylmethyl) aminomethyl]4-methyl-6-formyl-phenol: equilibrium
and kinetics of copper(II) adsorption’ by Yuh-Shan Ho: discussion on pseudo
second order kinetic expression. Polymer 47 (6), 1772e1773.
Kumar, K.V., Guha, B., 2006. Reply to the comments on “Study on biosorption of Cr
(VI) by Mucor hiemalis” by Y.-S. Ho, Biochem. Eng. J. 26(2005) 82e83. Biochem.
Eng. J. 30 (2), 222e223.
Kumar, K.V., Porkodi, K., 2006. Relation between some two- and three-parameter
isotherm models for the sorption of methylene blue onto lemon peel.
J. Hazard. Mater. 138 (3), 633e635.
Kumar, K.V., Porkodi, K., 2007a. Comments on “adsorption of 4-chlorophenol from
aqueous solutions by xad-4 resin: isotherm, kinetic, and thermodynamic
analysis”. J. Hazard. Mater. 143 (1e2), 598e599.
Kumar, K.V., Porkodi, K., 2007b. Comments on “Biosorption of nickel from pro-
tonated rice bran”. J. Hazard. Mater. 147 (1e2), 679.
Kumar, K.V., Porkodi, K., 2008. Comments on “removal of Congo red from aqueous
solution by anilinepropylsilica xerogel” by Pavan FA, Dias SLP, Lima EC, Ben-
venutti EV. Dyes and Pigments 2008;76:64e9. Dyes Pigments 77 (2), 481e482.
Kumar, K.V., Porkodi, K., Rocha, F., 2007. Comments on “Removal of lead from
aqueous solution using Syzygium cumini L.: equilibrium and kinetic studies”.
J. Hazard. Mater. 147 (1e2), 677e678.
Lagergren, S., 1898. About the theory of so-called adsorption of soluble substances.
K. Sven. Vetensk. Handl. 24 (4), 1e39.
Langmuir, I., 1918. The adsorption of gases on plane surfaces of glass, mica and
platinum. J. Am. Chem. Soc. 40 (9), 1361e1403.
Lee, D.-G., 2017. Comment on: Olushola S, Olalekan S, Folahan A, Leslie F and Ximba
BJ (2014) Application of nano zinc oxide (nZnO) for the removal of triphenyltin
chloride (TPT) from dockyard wastewater. Water SA (Online) 43 (1), 175.
Li, W., Pan, G., 2007. Comments on “Ion adsorption components in liquid/solid
systems”. J. Environ. Sci. 19 (6), 768.
Li, Z., Imaizumi, S., Katsumi, T., Tang, X., Chen, Y., 2010. Comment on JHM 142 (2007)
1e53 ‘Arsenic removal from waterewastewater using adsorbentsda critical
review’ by D Mohan and CU Pittman Jr. J. Hazard. Mater. 175 (1e3), 1116e1117.


Lima, E.C., Adebayo, M.A., Machado, F.M., 2015. Kinetic and Equilibrium Models of
Adsorption. In: Carbon Nanomaterials as Adsorbents for Environmental and
Biological Applications. Springer, pp. 33e69.
Lima, E.C., Cestari, A.R., Adebayo, M.A., 2016. Comments on the paper: a critical
review of the applicability of Avrami fractional kinetic equation in adsorption-
based water treatment studies. Desalination Water Treat. 57 (41), 19566e19571.
Lin, J.X., Wang, L., 2009. Comment on “Adsorption of Supranol Yellow 4 GL from
aqueous solution by surfactant-treated aluminum/chromium-intercalated
bentonite”. J. Hazard. Mater. 172 (1), 516e517.
Liu, Y., 2009. Is the free energy change of adsorption correctly calculated? J. Chem.
Eng. Data 54 (7), 1981e1985.
Lu, X., 2008. Comment on “Thermodynamic and isotherm studies of the biosorption
of Cu(II), Pb(II), and Zn(II) by leaves of saltbush (Atriplex canescens)”. J. Chem.
Thermodyn. 40 (4), 739e740.
Marsh, H., Reinoso, F.R., 2006. Activated Carbon. Elsevier.
Masson, S., Gineys, M., Delpeux-Ouldriane, S., Reinert, L., Guittonneau, S., Be
guin, F.,
Duclaux, L., 2016. Single, binary, and mixture adsorption of nine organic con-
taminants onto a microporous and a microporous/mesoporous activated carbon
cloth. Microporous Mesoporous Mater. 234, 24e34.
McKay, G., Ho, Y.S., Ng, J.C.Y., 1999. Biosorption of copper from waste waters: a
review. Sep. Purif. Rev. 28 (1), 87e125.
McLintock, I., 1967. The Elovich equation in chemisorption kinetics. Nature 216,
1204e1205.
Medellin-Castillo, N.A., Padilla-Ortega, E., Regules-Martínez, M.C., Leyva-Ramos, R.,
Ocampo-Pe
rez, R., Carranza-Alvarez, C., 2017. Single and competitive adsorption
of Cd(II) and Pb(II) ions from aqueous solutions onto industrial chili seeds
(Capsicum annuum) waste. Sustain. Environ. Res. 27 (2), 61e69.
Milonji
c, S.K., 2007. A consideration of the correct calculation of thermodynamic
parameters of adsorption. J. Serb. Chem. Soc. 72 (12), 1363e1367.
Milonji
c, S.K., 2009a. Comments on “Factors influencing the removal of divalent
cations by hydroxyapatite”. J. Hazard. Mater. 162 (2e3), 1588e1589.
Milonji
c, S.K., 2009b. Comments on “Removal of uranium (VI) from aqueous solu-
tion by adsorption of hematite”, by X. Shuibo, Z. Chun, Z. Xinghuo, Y. Jing, Z.
Xiaojian, W. Jingsong. J. Environ. Radioact. 100 (10), 921e922.
Milonji
c, S.K., 2010. Comments on the authors' response to the comments on
“Factors influencing the removal of divalent cations by hydroxyapatite”, by
Smiciklas et al. J. Hazard. Mater. 176 (1e3), 1126e1127.
Milonji
 si

c, S.K., Ruvarac, A.L., Su c, M.V., 1975. The heat of immersion of natural
magnetite in aqueous solutions. Thermochim. Acta 11 (3), 261e266.
Mohan, D., Pittman Jr., C.U., 2011. Reply to the comments on HAZMAT 142 (2007)
1e53 ‘Arsenic removal from water/wastewater using adsorbents e a critical
review’ by D. Mohan and C.U. Pittman Jr. made by Zhenze Li et al. [Hazmat 175
(2010) 1116e1117]. J. Hazard. Mater. 185 (2e3), 1614e1617.
Morosanu, I., Teodosiu, C., Paduraru, C., Ibanescu, D., Tofan, L., 2016. Biosorption of
lead ions from aqueous effluents by rapeseed biomass. New Biotechnol. http://
dx.doi.org/10.1016/j.nbt.2016.08.002.
Müller, G., Janoskov

r, T., Cakl, J., Jir

a, K., Bakala
, H., 2012. Removal of Zn(II)
ankova
from aqueous solutions using Lewatit S1468. Desalination Water Treat. 37
(1e3), 146e151.
Müller, F., Faidt, T., Grandthyll, S., Natter, H., 2017. Comment on “CuYb0.5Fe1.5O4
nanoferrite adsorbent structural, morphological and functionalization charac-
teristics for multiple pollutant removal by response surface methodology” by
M.A. Rehman et al., J. Mol. Liq. 224(2016) 1256e1265. J. Mol. Liq. 233, 52e54.
Nekouei, F., Nekouei, S., 2017. Comments on the paper “Adsorptive removal of
methylene blue by rhamnolipid-functionalized graphene oxide from waste-
water”. Water Res. 108, 462e463.
Nekouei, F., Kargarzadeh, H., Nekouei, S., Tyagi, I., Agarwal, S., Kumar Gupta, V.,
2016. Preparation of Nickel hydroxide nanoplates modified activated carbon for
Malachite Green removal from solutions: kinetic, thermodynamic, isotherm
 H.N. Tran et al. / Water Research 120 (2017) 88e116
and antibacterial studies. Process Saf. Environ. Prot. 102, 85e97.
Oleszczuk, P., Pan, B., Xing, B., 2010. Response to comment on “adsorption and
desorption of oxytetracycline and carbamazepine by multiwalled carbon
nanotubes”. Environ. Sci. Technol. 44 (12), 4829.
Onjia, A.E., Milonji
c, S.K., 2002. Influence of the background electrolyte on the point
of zero charge of chromium(III)-oxide. Mater. Sci. Forum 413, 87e92.
€
Ozacar, M., 2005. Response to comment on “Two-stage batch sorber design using
second-order kinetic model for the sorption of metal complex dyes onto pine
sawdust” by Dr. Y.-S. Ho, Biochem. Eng. J. 21(2004) 39e45. Biochem. Eng. J. 23
(3), 293.
Park, D., Yun, Y.-S., Kim, J.Y., Park, J.M., 2008. How to study Cr(VI) biosorption: use of
fermentation waste for detoxifying Cr(VI) in aqueous solution. Chem. Eng. J. 136
(2e3), 173e179.
Park, D., Yun, Y.-S., Park, J.M., 2005. Studies on hexavalent chromium biosorption by
chemically-treated biomass of Ecklonia sp. Chemosphere 60 (10), 1356e1364.
Park, D., Yun, Y.-S., Park, J.M., 2006a. Comment on “Chromate ion adsorption by
agricultural by-products modified with dimethyloldihydroxylethylene urea and
choline chloride” by Wartelle and Marshall. Water Res. 40 (7), 1501e1504.
Park, D., Yun, Y.-S., Park, J.M., 2006b. Comment on the removal mechanism of
hexavalent chromium by biomaterials or biomaterial-based activated carbons.
Ind. Eng. Chem. Res. 45 (7), 2405e2407.
Park, D., Yun, Y.-S., Park, J.M., 2006c. Mechanisms of the removal of hexavalent
chromium by biomaterials or biomaterial-based activated carbons. J. Hazard.
Mater. 137 (2), 1254e1257.
Patrickios, C.S., Yamasaki, E.N., 1997. A correction to the calculation of the Gibbs free
energy of adsorption for biomolecules in ion-exchange systems. Biophys. Chem.
69 (2e3), 219e220.
Plazinski, W., Rudzinski, W., Plazinska, A., 2009. Theoretical models of sorption
kinetics including a surface reaction mechanism: a review. Adv. Colloid Inter-
face Sci. 152 (1e2), 2e13.
Porter, W.R., 1985. Comment on: “Equilibrium adsorption of polycyclic aromatic
hydrocarbons from water onto activated carbon”. Environ. Sci. Technol. 19 (9),
869e870.
Radovic, L.R., 1999. Surface chemistry of activated carbon materials: state of the art
and implications for adsorption. Surfactant Sci. Ser. 78, 529e565.
Rahmani-Sani, A., Shan, R.-r., Yan, L.-g., Hosseini-Bandegharaei, A., 2017. Response
to “Letter to Editor: minor correction to the thermodynamic calculation using
the distribution constant by Shan et al. and Rahmani-Sani, et al.” J. Hazard.
Mater. 325 (5).
Rayne, S., 2013. Comment on “Adsorption of ionizable organic contaminants on
multi-walled carbon nanotubes with different oxygen contents [Li et al., J.
Hazard. Mater. 186(2011) 407e415]”. J. Hazard. Mater. 252e253, 1.
Redlich, O., Peterson, D.L., 1959. A useful adsorption isotherm. J. Phys. Chem. 63 (6),
1024.
Rivera-Utrilla, J., Sa
nchez-Polo, M., 2011. Adsorbent-adsorbate interactions in the
adsorption of organic and inorganic species on ozonized activated carbons: a
short review. Adsorption 17 (3), 611e620.
Robalds, A., Naja, G.M., Klavins, M., 2016. Highlighting inconsistencies regarding
metal biosorption. J. Hazard. Mater. 304, 553e556.
Roginsky, S., Zeldovich, Y.B., 1934. The catalytic oxidation of carbon monoxide on
manganese dioxide. Acta Phys. Chem. USSR 1, 554.
Rudzinski, W., Plazinski, W., 2007. Reply to “Comment on “kinetics of solute
adsorption at solid/solution Interfaces: a theoretical development of the
empirical pseudo-first and pseudo-second order kinetic rate equations, based
on applying the statistical rate theory of interfacial transport”. J. Phys. Chem. B
111 (1), 319.
Salvestrini, S., Leone, V., Iovino, P., Canzano, S., Capasso, S., 2014. Considerations
about the correct evaluation of sorption thermodynamic parameters from
equilibrium isotherms. J. Chem. Thermodyn. 68, 310e316.
Senthil Kumar, P., Fernando, P.S.A., Ahmed, R.T., Srinath, R., Priyadharshini, M.,
Vignesh, A.M., Thanjiappan, A., 2014. Effect of temperature on the adsorption of
methylene blue dye onto sulfuric acidetreated orange peel. Chem. Eng. Com-
mun. 201 (11), 1526e1547.
Sharma, P., Hussain, N., Borah, D.J., Das, M.R., 2013. Kinetics and adsorption behavior
of the methyl blue at the graphene oxide/reduced graphene oxide nano-
sheetewater interface: a comparative study. J. Chem. Eng. Data 58 (12),
3477e3488.
Sharma, Y.C., Gupta, G.S., Prasad, G., Rupainwar, D.C., 1990. Use of wollastonite in the
removal of Ni(II) from aqueous solutions. Water Air Soil Pollut. 49 (1), 69e79.
Smiciklas, I., Onjia, A., Rai cevi

c, S., Jana

ckovi

c, D., 2009. Authors' response to
comments on “Factors influencing the removal of divalent cations by hy-
droxyapatite”. J. Hazard. Mater. 168 (1), 560e562.
Somasundaran, P., 1968. Zeta potential of apatite in aqueous solutions and its
change during equilibration. J. Colloid Interface Sci. 27 (4), 659e666.
Swiatkowski, A., Pakula, M., Biniak, S., Walczyk, M., 2004. Influence of the surface
chemistry of modified activated carbon on its electrochemical behaviour in the
presence of lead(II) ions. Carbon 42 (15), 3057e3069.
Thrower, P., 2011. Writing a scientific paper V e language. Carbon 49 (15),
4957e4960.
Thrower, P.A., 2007. Writing a scientific paper: I. Titles and abstracts. Carbon 45 (11),
2143e2144.
Thrower, P.A., 2008a. Writing a scientific paper: II. Introduction and references.
Carbon 46 (2), 183e184.
Thrower, P.A., 2008b. Writing a scientific paper: III. Experimental. Carbon 46 (8),
1113e1114.
115
Thrower, P.A., 2010. Writing a scientific paper: IV. Results and discussion. Carbon 48
(10), 2675e2676.
Tien, C., 2007. Remarks on adsorption manuscripts received and declined: an
editorial. Sep. Purif. Technol. 54 (3), 277e278.
Tien, C., 2008. Remarks on adsorption manuscripts revised and declined: an
editorial. J. Hazard. Mater. 150 (1), 2e3.
Tran, H.N., 2017. Comments on “Characterization and adsorption capacity of raw
pomegranate peel biosorbent for copper removal”. J. Clean. Prod. 144, 553e558.
Tran, H.N., Huang, F.-C., Lee, C.-K., Chao, H.-P., 2017a. Activated carbon derived from
spherical hydrochar functionalized with Triethylenetetramine: synthesis,
characterizations, and adsorption application. Green Process. Synth. http://
dx.doi.org/10.1515/gps-2016-0178.
Tran, H.N., Wang, Y.-F., You, S.-J., Chao, H.-P., 2017b. Insights into the mechanism of
cationic dye adsorption on activated charcoal: the importance of p-p in-
teractions. Process Saf. Environ. Prot. 107, 168e180.
Tran, H.N., You, S.-J., Chao, H.-P., 2015. Effect of pyrolysis temperatures and times on
the adsorption of cadmium onto orange peel derived biochar. Waste Manag.
Res. 34 (2), 129e138.
Tran, H.N., You, S.-J., Chao, H.-P., 2016. Thermodynamic parameters of cadmium
adsorption onto orange peel calculated from various methods: a comparison
study. J. Environ. Chem. Eng. 4 (3), 2671e2682.
Tran, H.N., You, S.-J., Chao, H.-P., 2017c. Activated carbons from golden shower upon
different chemical activation methods: synthesis and characterizations.
Adsorpt. Sci. Technol. http://dx.doi.org/10.1177/0263617416684837.
Tran, H.N., You, S.-J., Chao, H.-P., 2017d. Fast and efficient adsorption of methylene
green 5 on activated carbon prepared from new chemical activation method.
J. Environ. Manag. 188, 322e336.
Tran, H.N., You, S.-J., Chao, H.-P., 2017e. Insight into adsorption mechanism of
cationic dye onto agricultural residues-derived hyrochars: negligible role of p-p
interaction. Korean J. Chem. Eng. http://dx.doi.org/10.1007/s11814-017-0056-7.
Uchimiya, M., Lima, I.M., Thomas Klasson, K., Chang, S., Wartelle, L.H., Rodgers, J.E.,
2010. Immobilization of heavy metal ions (CuII, CdII, NiII, and PbII) by Broiler
litter-derived biochars in water and soil. J. Agric. Food Chem. 58 (9),
5538e5544.
USEPA, 1999. Understanding Variation in Partition Coefficient, Kd, Values. United
States Office of Air and Radiation. EPA 402-R-99e004A. Environmental Pro-
tection Agency, Washington, USA, p. 1.
Utomo, R.P., Koswojo, R., Ju, Y.-H., Ayucitra, A., Soetaredjo, F.E., Sunarso, J.,
Ismadji, S., 2010. Reply to the comment on “Acid green 25 removal from
wastewater by organo-bentonite from Pacitan” by R. Koswojo, R. P. Utomo, Y.-H.
Ju, A. Ayucitra, F. E. Soetaredjo, J. Sunarso, S. Ismadji [Applied Clay Science
48(2010) 81e86]. Appl. Clay Sci. 50 (1), 165e166.
van Noort, P.C.M., Jonker, M.T.O., Koelmans, A.A., 2005. Response to comment on
“Modeling maximum adsorption capacities of soot and soot-like materials for
PAHs and PCBs”. Environ. Sci. Technol. 39 (1), 383e384.
Vasanth Kumar, K., Porkodi, K., Rocha, F., 2007. Comments on “Equilibrium and
kinetic studies for the biosorption system of copper(II) ion from aqueous so-
lution using Tectona grandis L.f. leaves powder”. J. Hazard. Mater. 146 (1e2),
428e429.
Vasanth Kumar, K., Rattanaphani, S., 2007. Reply to ‘Comments on “An adsorption
and kinetic study of lac dyeing on silk”’ by Yuh-Shan Ho: discussion on pseudo
second order kinetic expression. Dyes Pigments 75 (1), 253e254.
Vasanth Kumar, K., Sivanesan, S., 2006. Equilibrium data, isotherm parameters and
process design for partial and complete isotherm of methylene blue onto
activated carbon. J. Hazard. Mater. 134 (1e3), 237e244.
Volesky, B., 2003. Sorption and Biosorption. BV Sorbex.
Volesky, B., 2007. Biosorption and me. Water Res. 41 (18), 4017e4029.
Walter, W.J., 1984. Evolution of a technology. J. Environ. Eng. 110 (5), 899e917.
Wang, H., Yuan, X., Wu, Y., Huang, H., Zeng, G., Liu, Y., Wang, X., Lin, N., Qi, Y., 2014.
Corrigendum to “Adsorption characteristics and behaviors of graphene oxide
for Zn(II) removal from aqueous solution” [Appl. Surf. Sci. 279(2013) 432e440].
Appl. Surf. Sci. 301, 585.
Wang, L.K., 2009. Heavy Metals in the Environment. CRC Press, Boca Raton.
Weber, T.W., Chakravorti, R.K., 1974. Pore and solid diffusion models for fixed-bed
adsorbers. AIChE J. 20 (2), 228e238.
Weber, W.J., Morris, J.C., 1963. Kinetics of adsorption on carbon from solution.
J. Sanit. Eng. Div. 89 (2), 31e60.
Weber, W.J., Smith, E.H., 1987. Simulation and design models for adsorption pro-
cesses. Environ. Sci. Technol. 21 (11), 1040e1050.
Werner, D., Karapanagioti, H.K., 2005. Comment on “Modeling maximum adsorp-
tion capacities of soot and soot-like materials for PAHs and PCBs”. Environ. Sci.
Technol. 39 (1), 381e382.
Worch, E., 2012. Adsorption Technology in Water Treatment: Fundamentals, Pro-
cesses, and Modeling. Walter de Gruyter.
Wu, C.-H., 2009. Response to comment on “Adsorption of direct dyes from aqueous
solutions by carbon nanotubes: determination of equilibrium, kinetics and
thermodynamics parameter” by Dr. Ho. J. Colloid Interface Sci. 333 (1), 413e414.
Wu, F.-C., Liu, B.-L., Wu, K.-T., Tseng, R.-L., 2010. A new linear form analysis of
RedlichePeterson isotherm equation for the adsorptions of dyes. Chem. Eng. J.
162 (1), 21e27.
Wu, Z., Zhong, H., Yuan, X., Wang, H., Wang, L., Chen, X., Zeng, G., Wu, Y., 2017. Reply
for comment on “Adsorptive removal of methylene blue by rhamnolipid-
functionalized graphene oxide from wastewater”. Water Res. 108, 464e465.
Zhao, Y., 2015. Comment on “ZirconiumeCarbon hybrid sorbent for removal of
fluoride from water: oxalic acid mediated Zr(IV) assembly and adsorption
116 H.N. Tran et al. / Water Research 120 (2017) 88e116

mechanism”. Environ. Sci. Technol. 49 (19), 11982e11983. (Part B), 735e736.

Zhou, Q., Xie, C., Gong, W., Xu, N., Zhou, W., 2011. Comments on the method of using
maximum absorption wavelength to calculate Congo red solution concentration
published in J. Hazard. Mater. J. Hazard. Mater. 198, 381e382.
Zhou, X., 2017. Minor correction to the thermodynamic calculation using the dis-
tribution constant by Shan et al. and Rahmani-Sani, et al. J. Hazard. Mater. 323
Zhou, X., Liu, H., Hao, J., 2012. Letters to the editor. Adsorpt. Sci. Technol. 30 (7),
647e649.
Zhou, X., Zhou, X., 2014. The unit problem in the thermodynamic calculation of
adsorption using the Langmuir equation. Chem. Eng. Commun. 201 (11),
1459e1467.