Accepted Manuscript

A critical review of the estimation of the thermodynamic

parameters on adsorption equilibria. Wrong use of equilibrium
constant in the Van't Hoof equation for calculation of
thermodynamic parameters of adsorption

Eder C. Lima, Ahmad Hosseini-Bandegharaei, Juan Carlos

Moreno-Piraján, Ioannis Anastopoulos

PII: S0167-7322(18)34601-4
DOI: doi:10.1016/j.molliq.2018.10.048
Reference: MOLLIQ 9793
To appear in: Journal of Molecular Liquids
Received date: 5 September 2018
Revised date: 6 October 2018
Accepted date: 10 October 2018

Please cite this article as: Eder C. Lima, Ahmad Hosseini-Bandegharaei, Juan Carlos
Moreno-Piraján, Ioannis Anastopoulos , A critical review of the estimation of the
thermodynamic parameters on adsorption equilibria. Wrong use of equilibrium constant
in the Van't Hoof equation for calculation of thermodynamic parameters of adsorption.
Molliq (2018), doi:10.1016/j.molliq.2018.10.048

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 ACCEPTED MANUSCRIPT
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A critical review of the estimation of the thermodynamic parameters on

adsorption equilibria. Wrong use of equilibrium constant in the Van’t

Hoof equation for calculation of thermodynamic parameters of

adsorption.

Eder C. Limaa*, Ahmad Hosseini-Bandegharaeib,c*, Juan Carlos Moreno-Pirajánd, Ioannis

Anastopoulose,

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a-
Laboratory of Environmental Technology and Analytical Chemistry (Latama), Institute of

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Chemistry, Federal University of Rio Grande do Sul (UFRGS), Av. Bento Gonçalves 9500,

Postal Box 15003, 91501-970 Porto Alegre, RS, Brazil

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b-
Department of Environmental Health Engineering, Faculty of Health, Sabzevar University of

Medical Sciences, Sabzevar, Iran

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c-
Department of Engineering, Kashmar Branch, Islamic Azad University, PO Box 161,

Kashmar, Iran
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d-
Department of Chemistry, University of the Andes, Bogotá, Colombia
e-
Laboratory of Biochemical Engineering & Environmental Technology (LBEET), Department
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of Chemical Engineering, University of Patras, 26504 Patras, Greece

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Corresponding authors:

profederlima@qmail.com (E.C. Lima)

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ahoseinib@yahoo.com (Ahmad Hosseini-Bandegharaei)

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Abstract

In the adsorption literature, the Van´t Hoff equation is used in different manners without any

criteria about the concepts of physical-chemistry of equilibrium for calculation of

thermodynamic parameters of adsorption. Indeed, the equilibrium constant (K) should be

dimensionless for being used in the Van´t Hoff equation. However, this is not a simple

adjustment of units, as being spread in the literature, to become K dimensionless. In this

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paper, it will be calculated the equilibrium constants using numeric examples and show the

flaws of the thermodynamics calculations, when the value of K is wrongly calculated, and

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what are the expected results of the changes in enthalpy (H°) and changes in the entropy

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(S°) that are spread in the literature.
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Keywords: equilibrium constant, Van’t Hoof equation, thermodynamic parameters of

adsorption, isotherm models.

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1. Introduction
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It is spread in the literature different ways how to calculate changes in Gibb´s free
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energy (G), changes of enthalpy (H°), and changes in the entropy (S°) in the adsorption
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process using the Van´t Hoff equation´s, as depicted below.

The Van´t Hoof equation measures the changes in the equilibrium constant with
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variations of the temperature, as depicted on in Eq. 1 (Atkins and de Paula, 2010; Chang and

Thoman-Jr., 2014).

G0  RTLn(Ke) (1)

where R is the universal gas constant (8.314 J K-1 mol-1), T is the absolute temperature

(Kelvin), and Ke° is the thermodynamic equilibrium constant (Atkins and de Paula, 2010;

Chang and Thoman-Jr., 2014).

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Considering the 3rd principles of the Thermodynamics (eq. 2)

G 0  H 0  T .S 0 (2)

Combining the equations 1 and 2, it leads to eq 3.

-ΔH0 1 ΔS0 (3)

Ln(Ke0)= . +
R T R

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By constructing a plot of Ln(Ke°) versus 1/T, from the intercept is calculated the

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change in entropy (S°) and by the slope, it is possible to calculate the change in enthalpy

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(H°) (Atkins and de Paula, 2010; Chang and Thoman-Jr., 2014). The main point of

discussion of this paper is how the equilibrium constant (Ke°) is calculated (Lima et al., 2015).
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Several authors even do not comment on their papers distinctly, how this value was

calculated (Ali et al., 2014; Guo et al., 2017; Madan et al., 2016; Massoudinejad et al., 2018;
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Maity et al., 2018).

The correct way to calculate the equilibrium constant for adsorption system is to
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obtain isotherms of adsorption at different temperatures (Ali et al., 2012, 2015, 2016, 2017,

2018; Liu and Xu, 2007, 2008; Liu 2009,) and making the nonlinear fitting of the isotherms
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(Liu 2009; Lima et al., 2015). From the best-fitted model at the different temperatures, the

equilibrium constant is obtained one for each isotherm at a given temperature (Prola et al.,
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2013; Saucier et al., 2017). This equilibrium constant obtained in the isotherms (usually
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expressed in L mg-1) must become dimensionless for being applied in the Vant´Hoff equation

(Atkins and de Paula, 2010; Chang and Thoman-Jr., 2014).

In this sense, it is recommended to use Eq 4 below described for calculating the

thermodynamic parameters by the Vant´Hoff equation (Eq. 3).

(4)

(1000.Kg.molecular weight of adsorbate).[Adsorbate]°

K0e=
γ
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Where  is the coefficient of activity (dimensionless), [Adsorbate]° is the standard

concentration of the adsorbate (1 mol L-1) (Chang and Thoman-Jr., 2014) and K°e is the

thermodynamic equilibrium constant that is dimensionless. It is calculated by converting the

units of Kg (the best isotherm model fitted, such as K of the Liu equilibrium constant, or K of

the Sips isotherm model or KL, the Langmuir equilibrium constant), that are given initially in L

mg-1 into L mol-1 (Leechart et al., 2009; Liu and Xu, 2007; Liu and Liu, 2008; Liu 2009). This

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conversion is obtained by the multiplication of the value of K (L mg-1) by 1000, to convert

L mg-1 into L g-1 and subsequently making the multiplication of this result by the molecular

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weight of the adsorbate (g mol-1) multiplied by the unitary standard concentration of the

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adsorbate (1 mol L-1) and making the division by the activity coefficient (dimensionless)

(Levine, 2009; Chang and Thoman-Jr., 2014). For this calculation, it is considered that the
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adsorbate solution is very diluted to consider that the activity coefficient is unitary (Levine,

2009; Chang and Thoman-Jr., 2014). The parameter K°e becomes dimensionless after
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making these calculations.

The principles of chemical equilibrium described in the textbooks of General

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Chemistry (Chang, 2011) and Physical-Chemistry (Levine, 2009; Atkins and de Paula, 2010;

Chang and Thoman-Jr., 2014) should be considered for establishing the equilibrium of
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adsorption.

Considering the chemical equilibrium of an adsorbate by one adsorbent as give

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below:
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(5)

Adsorbent(s) + Adsorbate(aq) Adsorbent-Adsorbate(s)

The chemical potential (µ) for this equilibrium system could be considered as (Atkins and de

Paula, 2010; Chang and Thoman-Jr., 2014):

[Adsorbent-Adsorbate(s)] (6)
µAdsorbent-Adsorbate = µ°Adsorbent-Adsorbate + RT Ln
[Adsorbent-Adsorbate(s)]°
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[ Adsorbent ( s )] (7)
µAdsorbent = µ° Adsorbent + RTLn
[ Adsorbent ( s )]

[ Adsorbate ] (8)
µAdsorbate = µ°Adsorbate + RTLn
[ Adsorbate ]

Where µAdsorbent is the chemical potential of the adsorbent, µAdsorbate is the chemical potential of

the adsorbate, µAdsorbent-Adsorbate is the chemical potential of the Adsorbent-Adsorbate. The µ° is

the standard chemical potential. Being µ°Adsorbent the standard chemical potential of the

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adsorbent; µ°Adsorbate is the standard chemical potential of the adsorbate and µ°Adsorbent-Adsorbate

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is the standard chemical potential of the adsorbent-adsorbate.

The [Adsorbate]°, [Adsorbent(s)]° and [Adsorbent-Adsorbate(s)]° are the standard

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concentrations of the adsorbate, adsorbent and adsorbent-adsorbate, respectively, whose
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concentration by definition is 1 mol L-1 at standard conditions (Atkins and de Paula, 2010;

Chang and Thoman-Jr., 2014; Levine, 2009). The standard state of pure solids and liquids is
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defined as the state with the pressure of 1 bar and at one temperature of interest (usually

298K) (Levine, 2009).

The free Gibbs energy of the adsorption process will be given by the equation below:
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Gad= µAdsobent-Adsorbate- (µAdsorbent + µAdsorbate) (9)

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Substituting Eq 6-8 onto Eq 9, it gives:

Gad= µ°Adsorbent-Adsorbate –(µ°Adsorbent + µ°Adsorbate) + RT𝐿𝑛𝑄 (10)

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Where Q means:
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[ Adsorbent  Adsorbate( s )] (11)

[ Adsorbent  Adsorbate( s )]
Q
[ Adsorbent ( s )].[ Adsorbate ]
[ Adsorbent ( s )].[ Adsorbate ]

Being µ°Adsorbent-Adsorbate – (µ°Adsorbent + µ°Adsorbate) = G°ad, Eq 10 becomes:

Gad=G°ad + RTLnQ (12)

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By definition at the equilibrium Gad = 0, and Q becomes K (Atkins and de Paula, 2010;

Chang and Thoman-Jr., 2014; Levine, 2009):

G°ad=  RTLnK (13)

Moreover, considering all standard concentrations of 1 mol L-1, and the concentrations of

Adsorbent, Adsorbate, and Adsorbent-Adsorbate are also expressed in mol L-1, the

equilibrium constant will be dimensionless. (Levine, 2009; Chang and Thoman-Jr., 2014;

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Chang, 2011).

[ Adsorbent  Adsorbate( s )] (14)

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[ Adsorbent  Adsorbate( s )]
K
[ Adsorbent ( s )].[ Adsorbate ]

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[ Adsorbent ( s )].[ Adsorbate ] NU
The adsorption is a heterogeneous equilibrium (Chang, 2011; Chang and Thoman-Jr.,

2014) where the adsorbate is present in a fluidic phase (aqueous solution, or gas) and the
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adsorbent will be present in a solid phase. Usually, the concentration of the solid phase

{[Adsorbent] and [Adsorbent-Adsorbate]} is considered constant, because the number of

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moles of the solid phase divided by the volume of the solid phase is practically constant,

because the solid phases did not alter their volume during the process of the adsorption
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(Chang, 2011; Chang and Thoman-Jr., 2014). In this sense, Eq 14, becomes (Atkins and de
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Paula, 2010; Chang, 2011; Chang and Thoman-Jr., 2014):

[ Adsorbent ( s )] (15)
K.
[ Adsorbent ( s )]  [ Adsorbate ] 
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
[ Adsorbent  Adsorbate( s )] [ Adsorbate ]
[ Adsorbent  Adsorbate( s )] 

A constant K being multiplied and divided by a constant (the concentrations of adsorbent and

adsorbent-adsorbate) will originate a new constant (Ke), as (Chang and Thoman-Jr., 2014;

Chang, 2011; Atkins and de Paula, 2010; Levine, 2009):

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[Adsorbate]° (16)
Ke=
[Adsorbate]

Ke is the equilibrium constant of an ideal solution, whose numeric values is already

considered the concentration of the solid phases (Atkins and de Paula, 2010; Chang and

Thoman-Jr., 2014).

The adsorption of an adsorbate by a solid adsorbent is far away of an ideal solution

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(Abe et al., 1979), the equilibrium constant should be expressed regarding activity, instead of

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concentration (Chang and Thoman-Jr., 2014).

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The activity of the adsorbate is defined as (Levine, 2009; Chang and Thoman-Jr.,

2014):
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𝐴𝑐𝑡𝑖𝑣𝑖𝑡𝑦𝑎𝑑𝑠𝑜𝑟𝑏𝑎𝑡𝑒 = [𝐴𝑑𝑠𝑜𝑟𝑏𝑎𝑡𝑒].  (17)
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Where [Adsorbate] is the molar concentration of the adsorbate (mol L-1); and  is the

coefficient of activity of the adsorbate (dimensionless) (Chang and Thoman-Jr., 2014).

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Substituting Eq 17 onto 16, it becomes:

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[ Adsorbate ]  Ke (18)
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K°e= =
 .[ Adsorbate ] 
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Note Eq. 18 is the same Eq. 4 given above.

(1000.Kg.molecular weight of adsorbate. [adsorbate]°) [ Adsorbate ]  (19)

K0e= 
  .[ Adsorbate ]

(1000.Kg.molecular weight of adsorbate. [adsorbate]°) Ke (20)

  Ke
 
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Therefore, from the best isotherm model fitted at different temperatures (Thue et al.,

2016, 2018) it is possible to obtain the thermodynamic equilibrium equation that is

dimensionless, after some little arithmetic’s.

In a recent review article, Ghosal and Gupta, 2016, also support that the use of

Equation 20 given above. In that situation, the best isotherm model that was adjusted to the

equilibrium data was the Langmuir model. Therefore, the KL (mol L-1) was used in the Van't

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Hooff equation, in order to estimate the thermodynamic parameters.

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KL H 0 S 0 (21)
ln( )  

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e RT R
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Note that the equilibrium constant utilized in the Vant´Hoof equation used in equation

21, is the same as defined in equation 20 of this paper. Also, the use of equation 21 was
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already reported by Liu, 2009.

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2. Other equations of equilibrium constant used in the adsorption literature.

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In the adsorption literature, several expression of equilibrium constants is utilized

(Anastopoulos and Kyzas, 2016).

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The most common found equilibrium constants reported in the literature, are
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expressed in equations below:

qe (22)
Kd 
Ce

Kd is the distribution constant (L g-1), qe is the sorption capacity (mg g-1) at the equilibrium,

and Ce is the equilibrium concentration (mg L-1) (Fosso-Kankeu et al., 2017; Johir et al.,

2016; Guo et al., 2017; Lonappan et al., 2018). By using this equation Kd presents the unit of
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L g-1, considering that qe is expressed in mg g-1, and Ce is expressed in mg L-1. Some authors

make a strategy of becoming Kd dimensionless according to Eq. 23.

qe m (23)
Kd  .
Ce V
Where m is the mass of adsorbent (g) and V is the volume of adsorbate solution (L). By

using this equation, Kd becomes dimensionless (Khosravi et al., 2018; Tran et al., 2017;

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Wang et al., 2016).

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Another equilibrium constant that is usually employed is given below:

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Cs C 0  Ce (24)
KC  
Ce Ce NU
The KC equilibrium constant is dimensionless, Cs is the concentration is the solid phase

(mg L-1), Ce is the adsorbate equilibrium concentration in the supernatant phase (mg L-1), Co
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is the initial adsorbate concentration (mg L-1) (Fan and Zhang, 2018; Razak et al., 2018;

Konicki et al., 2018; Tran et al., 2017). Also, Kc is dimensionless.

Equations 22-24 do not lead to a correct value of the equilibrium constant, since
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these Kc and Kd described above are not an equilibrium constant, as spread in the literature
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(Abe et al., 1979, Anastopoulos and Kyzas, 2016; Tran et al., 2017). This will be shown in the

next sections.
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It should be made clear that K°e should be obtained by the manner depicted in Eq 20

and should not be obtained as earlier reported (Dotto et al., 2015; Anastopoulos and Kyzas,
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2016):

K0=1000.Kg. d (25)

Where Kg is also obtained from the isotherm, and its value is expressed in L mg-1, that is

multiplied by 1000 to be converted into L g-1. Subsequently, the value is multiplied by the

density of the aqueous solution (approximately 1000 g L-1; assuming the density of the

adsorbate solution is equal to the density of water). When the value of Kg (already in L g-1) it
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is multiplied by 1000 g L-1 of the density, the value of K° becomes dimensionless. However, it

should be born in mind, that this strategy is incorrect and do not follow the principles of

chemical equilibrium as made in Eq. 20. This is just a strategy of letting K dimensionless,

disregarding if the obtained equilibrium constant has physical meaning.

For comparison of different equilibrium constants obtained from equation 20, and

compared with the equations 23, 24 and 25, in the next section, these equilibrium constants

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will be utilized with numeric results, in order to check what is the best equilibrium constant

that should be used in the estimation of the thermodynamic parameters of adsorption. It is

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necessary to define what equation should be utilized for the correct obtention of

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thermodynamic parameters and not just a mathematical strategy of arriving at a

dimensionless equilibrium constant. The concepts of chemical equilibrium used in chemical

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reactions are also valid for the equilibrium of adsorption.
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3. Study of Case
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3.1 Defining the correct equilibrium constant for use in the Vant´Hoof equation.
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Recently Leite et al., 2017a published a paper using Avocado seed activated carbon

as an adsorbent for 3-aminophenol. It will be shown calculations of thermodynamic

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parameters using different the equilibrium constants described on Eq. 20, 23, 24, and 25. In
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Fig 1 and Table 1 is presented the experimental points of initial adsorbate concentration (Co),

the concentration at the equilibrium (Ce), sorption capacity at the equilibrium (qe). These are

the experimental data. Also, the next columns of Table 1 show the manipulated data that are

necessary to use the Eq. 23, and 24, for the temperature of 25°C (298 K). For all other

temperatures, these Tables are shown in the Supplementary Material. Fig 1 is presented as

the isotherm of adsorption of the 3-aminophenol adsorbate onto the AC. Each experimental

point was labeled from a to n. For the isotherm, it was used the nonlinear fitting of the data

(Lima et al., 2015). According with several reports in the literature (Alencar et al., 2012a,
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2012b; Prola et al., 2013; Saucier et al., 2017; Thue et al., 2016; Umpierres et al., 2018) the

thermodynamic parameters could be obtained by performing the isotherm of adsorption at

different temperatures. The isothermal data are fitted using a nonlinear fitting. The best

isotherm model for the temperature studied should be the model chosen to explain the

experimental data (see Fig 1A). The equilibrium constant is then obtained from the best-fitted

isotherm model obtained, usually the KL of Langmuir (Ali et al., 2012, 2015,2016,2017, 2018,

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Dirbaz and Roosta, 2018; Gupta and Singh, S, 2018; Shin and Kim, 2016; Tran et al., 2016;),

KS of Sips (Alencar et al., 2012b; Cardoso et al., 2011; Dotto et al., 2012) Kg of Liu (Alencar

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et al., 2012a; Leite et al., 2017a, 2017b; Thue et al., 2018).

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On the other hand, from the fourth to the eighth column are presented the

manipulated data that are used to obtain the “supposed equilibrium constant” given by Eq 23
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1
(Kd) and 24 (Kc). Also, there is a mathematical strategy for plotting 𝑣𝑒𝑟𝑠𝑢𝑠 𝐶𝑒 to linearize
𝐾𝑑

the “equilibrium constant” (Abe et al., 1979). As can be seen in the Table 1, none of the
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supposed values of equilibrium constants are equal in values for the fourteen experimental

points of the isotherm (see Fig 1b and 1d). Also, this information is confirmed in the Fig 1. As
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shown in the literature (Guo, et al., 2017; Madan et al., 2016; Fan and Zhang, 2018; Razak

(𝐶𝑜−𝐶𝑒 )
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et al., 2018), it is necessary to make graphs of 𝐿𝑛 ( 𝐶𝑒

) versus Ce (see Fig 1C). When Ce

trends to zero, the value of LnK is obtained. This would be the value of LnK obtained by
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these method spreadly reported in the literature. Similar behaviour was also accomplished at

30°, 35°, 40°, 45° and 50°C, whose data were presented on Supplementary Tables 1, 2, 3, 4,
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and 5, respectively.
𝑞 𝑚
For the plot 𝐾𝑑 = 𝐶𝑒 . 𝑉 versus Ce (see Fig 1D and 1E), the results were also plotted.
𝑒

Again, it is possible to see that the values reported for this “supposed equilibrium constant” is

𝑞 𝑚
not also a single value. Therefore, is necessary to obtain its value from the plot of Ln(𝐶𝑒 . 𝑉 )
𝑒

versus Ce, when 𝐶𝑒→0 . It also should be commented, that all the values of this equilibrium

constant are not a single value (see Table 2). At first seeing (see Fig 1D), it seems that if the
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points a and b are deleted, the points from c to n would be constants. However, this
1 𝐶 .𝑉
information is not true (see Fig 1E). The plot 𝐾𝑑
= 𝑞 𝑒.𝑚 is linear, therefore at infinite dilution,
𝑒

1
when 𝐶𝑒→0 , the value of the intercept of the graph would give the value of 𝐾𝑑
. Therefore,

1
𝑖𝑛𝑡𝑒𝑟𝑐𝑒𝑝𝑡
= 𝐾𝑑 (see Fig 1G). This mathematical strategy at the first analysis would lead the

reader to think that this is the best way to obtain Kd, since a linear approach is used to obtain

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the intercept (Abe et al, 1979).

Table 2 is presented the values of equilibrium constants obtained by the Kg (Liu

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equilibrium constant in L mg-1, L mol-1, and dimensionless after applying Eq 20), the

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(𝐶𝑜 −𝐶𝑒) 𝑞𝑒 𝑚
corresponding LnKe; the 𝐾𝑐 = (equation 24) and its Ln K, and 𝐾𝑑 = . . (equation
𝐶𝑒 𝐶𝑒 𝑉

1 𝐶𝑒 .𝑉
23) and its Ln Kd, and also Ln Kd, whose value of Kd was obtained from = 𝑣𝑒𝑟𝑠𝑢𝑠 𝐶𝑒
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𝐾𝑑 𝑞𝑒 .𝑚

1
(see Fig 1F). In Fig 2 is presented the plots of different LnK versus 𝑇. In Fig 2A is presented
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the plot based on the Liu isotherm, after it becoming dimensionless (Eq. 20). In Fig 2B is
(𝐶𝑜 −𝐶𝑒 )
show the equilibrium constant 𝐾 = ( 𝐶𝑒
) (Eq 24) and in Fig 2C it was considered the
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𝑞𝑒 𝑚
equilibrium constant 𝐾 = . (Eq 23), and in Fig 2D, the values of Kd were obtained by the
𝐶𝑒 𝑉
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1 𝐶𝑒 .𝑉
plot = 𝑣𝑒𝑟𝑠𝑢𝑠 𝐶𝑒 . The values of R²adj for the linear fitting of Fig 2 weres 0.9942,
𝐾𝑑 𝑞𝑒 .𝑚

0.5681, 0.3657, and -0.2468 for Fig 2A, 2B, 2C, and 2D, respectively, indicating that only the
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equilibrium constant that was based on the isotherm fitting presented a linear behaviour (Eq
1 𝐶 .𝑉
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20). The equations 23 and 24 as well as the modified eq 23 (𝐾 = 𝑞 𝑒.𝑚), presented poor
𝑑 𝑒

linearization’s, that is an indication that these three methodologies of obtaining the

equilibrium constant should not be applied for studying the thermodynamics of adsorption. It

should let clear on this paper, that several authors indeed do not observe this behaviour,

because their “supposed equilibrium constants” based on Eq 23 and 24, and modified Eq 23,

were obtained with just one concentration, instead of a set of concentrations (14 experiments

for each temperature). If indeed these authors used several concentrations, they would
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perceive that it is not possible to employ Eq 23 and 24 to obtain a constant value of

equilibrium constant. Therefore, in the author´s opinion, researchers in the adsorption area

are using Eq 23 and 24 in their adsorption works, because this leads to a lower number of

experiments to be carried out, as it is done with the linearization’s of the equilibrium and

kinetics of adsorption (El-Khaiary et al., 2010; El-Khaiary 2010; El-Khaiary and Malash, 2011;

Lima et al., 2015; Tien, 2007).

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Moreover, it is not only the linearity that should be evaluated, but also the values of

Gibb´s free energy should be considered (see Table 3). By using the equilibrium constant of

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Eq. 24, the values of ∆𝐺 are completely without physical meaning (values of G ranged from

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+8.144.10-3 to +1.602.10-2 kJ mol-1). It is not possible the values of ∆𝐺 be positive. If the

adsorption took place, values of ∆𝐺 always should be negative. This was obtained by using
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Eq. 20 (Liu equilibrium constant- G obtained ranged from -26.14 to

-26.25 kJ mol-1) and Eq. 23 (G ranged from -11.08 to -16.29 kJ mol-1) and modified Eq 23
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(G ranged from -8.562 to -9.751 kJ mol-1). However, it should be clear, that the linearity of

Fig 2C and 2D (by using the equilibrium constant of Eq. 23, and modified Eq 23), is not good
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at all. It is even worse than the linearity of Fig 2b (using equilibrium constant of Eq. 24). Also,
1 𝐶 .𝑉
the linearity of the 𝐾 = 𝑞 𝑒.𝑚 𝑣𝑒𝑟𝑠𝑢𝑠 𝐶𝑒 was the worse of all the plots show in Fig 2. Therefore,
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𝑑 𝑒

the strategy of linearization presented in Fig 1G, (Abe et al., 1979) did not generate results of
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Kd that followed a regular pattern with the increase of temperature.

Also continuing with the analysis of the thermodynamic parameters, the changes in
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enthalpy (ΔH) and entropy (ΔS) obtained by the fitting of the Liu isotherm presented values

that are compatible with the physical phenomena (see Table 4). The adsorption enthalpy

obtained by the plot of Fig 2A, using the values of the equilibrium constant obtained by the

Liu isotherm was -26.25 kJ mol-1, whose value is compatible with a physical adsorption of 3-

aminophenol onto the carbon surface of the activated carbon (Leite et al., 2017a; Sun and

Wang, 2010). The numeric values of changes in enthalpy and entropy based on equation
(𝐶𝑜 −𝐶𝑒 )
𝐾= 𝐶𝑒
, is close to a value with physical meaning, however, these results should not be
 ACCEPTED MANUSCRIPT
14

considered since the R²adj was only 0.3657. On the other hand, by using Eq 24, the values of

changes in enthalpy and entropy are lower than -0.1 kJ mol-1 and -0.3 J K-1 mol-1,

respectively. These values indeed are not compatible with enthalpies and entropies of

adsorption. For using the strategy of linearization (Fig 1G) the numeric value of entropy could

lead an erroneous observation that this parameter presents a physical meaning. On the other

hand, the value of the change in the enthalpy of only -0.7318 kJ mol-1 is completely

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senseless. Therefore, by analyzing Tables 1 to 4 and Fig 1 and 2, it could be stated that it is

necessary to obtain the isotherms of adsorption at several temperatures, preferably using

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nonlinear fitting, and for the best isotherm model obtain the equilibrium constant (Kisotherm).

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Then, this Kisotherm should have their value converted from L mg-1 into L mol-1, as

demonstrated in Eq 20 of this paper. After the equilibrium constant being dimensionless (Eq
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20), the Eq 3 could be used to obtain values of changes in enthalpy (ΔH) and changes in

entropy (ΔS) of adsorption.

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3.2 Other considerations that are not explored in the supposed equilibrium constants of Eq 5
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and 6.
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When Eq 20 is used for obtaining the Thermodynamic equilibrium constant, it is

assumed that the activity coefficient is unitary. The activity coefficient is unitary for diluted
CE

solutions. When Eq. 23 and 24 were applied, graphs of Ln K versus Ce were utilized
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considering 𝐶𝑒⟶0 . And making an extrapolation for Ce=0, the value of LnK was obtained.

However, this strategy is completely out of any Physical-Chemistry concept. According to the

sorption capacity Eq. 26

(𝐶0 − 𝐶𝑒 ) (26)
𝑞= .𝑉
𝑚

When Ce trends to zero, the sorption capacity would increase, in this situation, considering

an adsorbent with large sorption capacity, the adsorbent would become saturated. Also

thinking about before the adsorption process occurs, for saturating of an adsorbent with large
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15

sorption capacity, would require an adsorbate solution with high concentrations. Therefore,

for adsorbents with high sorption capacity for an adsorbate, in order to Ce trends to zero,

after the system attaining the equilibrium, it is initial concentration (C0) would be a high

concentration. When the concentration increases, the activity coefficient () would decrease

(Levine, 2009; Chang and Thoman-Jr., 2014). Therefore, the assumptions made for utilizing

Eq 23 and 24 would not be correct. This is one of the reasons that the plots of Fig 2B, 2C

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and 2D, did not linearize. Also, it should be concerned, that in Fig 2, six temperatures were

chosen, showing that the graphs were not well fitted.

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On the other hand, in the literature, authors usually show only three temperatures,

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that sometimes there are no criteria for how these temperatures were chosen. In order to

verify the effect of deleting some points to improve the R²adj values, in Fig 3 is presented with
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this strategy, that some authors could use (intentionally or not) to show appropriate fittings.

𝐶0− 𝐶𝑒 1
The plot 𝐿𝑛 ( ) 𝑣𝑒𝑟𝑠𝑢𝑠 is show in Fig 3a. It is observed for Fig 3a, if one point is
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𝐶𝑒 𝑇

deleted, there is a possibility of obtaining two straight lines, curve 1 and curve 2, that are

shown in Fig 3b and 3C, respectively. Observe that the R²adj with only three experimental
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points improved to 0.9752 and 0.8926, respectively for Fig 3B and 3C (see Table 5). These

values are better than the previous R²adj of Fig 3a (0.5681) (see Table 5). Calculating the ∆𝑆°
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and ∆𝐻° by the graph of Fig 3B, these values are -0.1154 J K-1 mol-1, -26.18 kJ mol-1,
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respectively. Although these values could seem compatible with the thermodynamic study, it

was carried out after disregarding 3 points. For Fig 3C, the values of the ∆𝑆° and ∆𝐻° were -
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0.1680 J K-1 mol-1, -41.74 kJ mol-1, respectively (see Table 5). Again, it should be reinforced

𝐶0− 𝐶𝑒 1
that using only three convenient temperatures, the plot 𝐿𝑛 ( ) 𝑣𝑒𝑟𝑠𝑢𝑠 could lead to
𝐶𝑒 𝑇

values that are compatible with the changes in enthalpy and entropy of adsorption, however,

it is clearly seen that these events occurred, after deleting three points of a total of six.

Therefore, it is not admissible to obtain thermodynamic parameters of adsorption just, using

three points (three temperatures) (see Table 5).

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16

By analogy of the calculations above described calculations of Fig 3E and 3F, were

done by deleting a set of three points of Fig 3D presents the following values for S° and H°

of -518.8 (Fig 3E) and -256.1 kJ K-1 mol-1 (Fig 3F) for changes in entropy and -179.0 (Fig 3E)

and -92.19 kJ mol-1 (Fig 3F) for changes in enthalpy. In continuation of this analysis, for Fig

3G, after deleting 3 experimental points, it is possible to obtain curve 1 and curve 2. Note

that curve 2 has the negative slope that would lead to endothermic adsorption that disagrees

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of all enthalpies presented on Table 4 and also in disagreement with all the plots of Fig 2 and

the plots of Fig 3A to 3F. For Fig 3H, the change of enthalpy (-37.90 kJ mol-1) and entropy (-

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89.30 J K-1 mol-1) and for Fig 3I the change of enthalpy (+15.91 kJ mol-1) and entropy (+82.37

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J K-1 mol-1) were obtained (see Table 5).

Now considering Eq 2, let us verify if the thermodynamic parameters obtained from

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Fig 3 presents physical meaning. Fig 3A to 3C (resulting from Eq 24), has no physical

meaning. G° values are all positive, that would mean that the adsorption did not take place.
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(𝐶𝑜 −𝐶𝑒 )
In this way the equation 𝐾 = could be ruled out.
𝐶𝑒

Fig 3D to 3F is the most dangerous to the scientific community because it could to

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lead to erroneous interpretation since all values of Gibb´s free energy are negative. Deleting
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three experimental points, the values of R²adj attain values of 0.9082 (Fig 3E), and 0.9912

(Fig 3F), and also the values of changes in enthalpy and changes in entropy are compatible
CE

(see Table 5). The only point that is questionable is the values of H° that are -179.0 (Fig 3E)

and -92.19 kJ mol-1 (Fig 3F), that would indicate chemical adsorption. However, the system in
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the study is 3-aminophenol being adsorbed onto activated carbon, where the probability of

occurring a chemical bond of the adsorbate with the solid surface of the adsorbent should be

ruled out since the principal mechanism of adsorption depends on the chemical nature of the

adsorbent and adsorbate. In this case, hydrogen bonds, - interactions, and other Wan der

Waals forces should take place (Liu et al., 2010, Leite et al., 2017a; Thue et al., 2016).

Therefore, all judgment about a process of adsorption should consider several factors, such

as the chemical characteristics of the adsorbent and adsorbate, results of other analytical
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17

techniques to prove the mechanism of interaction, and the mechanism of adsorption could

not only be established based on simple adjustment of Vant´ Hoff equation (Lima et al.,

2016).
1 𝐶 .𝑉
Fig 3G to 3I, show all the contradiction that the use of the plot 𝐾𝑑
= 𝑞 𝑒.𝑚 𝑣𝑒𝑟𝑠𝑢𝑠 𝐶𝑒
𝑒

could bring. After deleting 3 points, it is possible to obtain two set of curves with exothermic

(Fig 3 H) and endothermic (Fig 3I) behavior. Also, the values of G° are negative for Fig 3H

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and 3I, inducting the reader to errors. Therefore, papers reported in the literature using the

equations 23 and 24 with just three temperatures, could lead to erroneous results, that are

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spread in the adsorption papers reported in the literature. The fact of the results of the

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𝐶0 −𝐶𝑒
thermodynamic parameters obtained in Fig 3 prove that the equilibrium constants 𝐾 =
NU 𝐶𝑒

𝑞𝑒 𝑚
and 𝐾 = . should not be used for calculation of the changes in enthalpy and entropy of
𝐶𝑒 𝑉

adsorption, even if a good on a linear relationship of Ln K versus 1/T could occur by chance,
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as demonstrated (Fig 3).

ED

3.3 Different strategies for becoming equilibrium constant dimensionless, without considering

the physical-chemical concept of chemical equilibrium.

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Although some authors obtain the equilibrium constant from isotherms, they do not
CE

know how to proceed to become it dimensionless by Eq 20. Some authors multiply the value
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of Langmuir equilibrium constant, as (L mg-1) by 1000 and then by the molality of water (Tran

et al., 2016; Milonjić, 2007). Considering the amount of mol of water present in 1 kg and

considering the molecular weight of water 18.015 g mol-1, 1 kg of water will present 55.51

mol of water. Therefore, the molal concentration of water in an aqueous solution will be 55.51

mol kg-1 and considering that 1 kg of water will occupy a volume of 1 L, the molal

concentration of water in aqueous solution will be very close to 55.51 mol L-1 (molar

concentration of water). Transforming the Langmuir, Liu or Sips equilibrium constant (L mg-1)
 ACCEPTED MANUSCRIPT
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into L mol-1 and then multiplying it by 55.51 mol L-1, the K becomes dimensionless (Milonjić,

2007).

𝐾 = 55.51. 𝐾𝐿 . 1000. 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑎𝑑𝑠𝑜𝑟𝑏𝑎𝑡𝑒 (27)

Although authors sometimes do not transform the unit of KL

(L mg-1) into L mol-1 for using Eq. 27 (Tran et al., 2016). Moreover, also, authors forget to

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convert the unit L mg-1 into L mol-1 by using Eq 27. Also, it is widespread to use Eq 27, just to

become the equilibrium constant dimensionless (Anastopoulos and Kyzas, 2016; Dotto et

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al., 2012, 2017). Therefore, in Fig 4 and Table 6 is presented the correct Eq 20 applied to the

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system 3-aminophenol adsorbed onto avocado seed activated carbon, whose experimental

conditions were previously discussed in this paper (Fig 4A, Table 6).
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In comparison with the Liu equilibrium constant expressed in mg g-1, without using the

molecular weight of the adsorbate and converting it in L mol-1 (Fig 4B, Table 6). Using Eq 27,
MA

where the Liu equilibrium constant (L mg-1), is multiplied by the density of the aqueous

solution (assuming that the density of the solution is close to water being 1000 g L-1) (Fig 4C,
ED

Table 6). Using Eq 27, and not multiplying it by 1000 to convert L mg-1 into L g-1 (Fig 4D,

Table 6). Using Eq 27, where the Liu equilibrium constant (L mg-1) is firstly converted in L mol-
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1
and then multiplying it by the molal concentration of water (55.51 mol kg-1, that is

approximately 55.51 mol L-1) (Fig 4D, Table 6). Moreover, finally taking the Liu equilibrium
CE

constant (L mg-1) and multiplying it by the term 55.51 (Fig 4E, Table 6). Note that only Fig 4A,
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using equation 20, it was considered the principles of chemical equilibrium. Fig 4B, 4C, 4D,

4E and 4F are not correct, since authors use it indiscriminately without having a real notion,

what they are calculating. Fig 4B, 4D, and 4F are typical of authors that have no notion what

they are calculating since these equilibrium constants existing units. Fig 4C and 4E at least

authors are trying to let the equilibrium constant dimensionless, thinking that chemical

equilibrium is just a simple adjustment of units. All the thermodynamic parameters, G, H

and S were determined for all the cases of Fig 4. If someone that does not have notion

about the chemical equilibrium will not be able to differentiate among all these equations
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19

since all values of H for the five cases are the same (H° -26.14 kJ mol-1). This situation

was expected that would happen, since all the calculations made for Fig 4, there is no

variation at the slope of the curves obtained. Therefore, the error is just in the changes in

entropy (S) values. Of course, depending on how it is calculated, changes in the intercept of

the straight line will occur. This should be one of the reasons that about 95% of the papers

reported in the literature about the thermodynamics of adsorption are entirely out of any

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sense of chemical equilibrium. Just using Eq 20 that consider the activity coefficient and the

standard concentration of the pure adsorbate are considered. Even using Eq 20, it is

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necessary to assume that the activity coefficient is 1. The standard concentration of any

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chemical specie (molecule, ion) by definition is always 1 mol L-1 (Atkins and de Paula, 2010;

Chang and Thoman-Jr., 2014). However, the value of activity coefficient is unitary only for
NU
diluted solutions, that is not the case of the majority of the isotherms of adsorption, where

high concentrations of the adsorbate solution are necessary to saturate the adsorbent.
MA

Therefore, even using Eq 20, the Vant´Hoff equation should be used with care, as an

estimative of the values of enthalpy and entropy of adsorption, however more accurate
ED

results of changes of enthalpy of adsorption should be obtained using a commercial

adiabatic calorimeter. Therefore, the experiments of isotherms at different temperatures do

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not surpass experimental measurements of energy in a calorimeter.

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4. Conclusion.
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This work showed that accurate estimation of thermodynamic parameters for

adsorption systems needs a correct equilibrium thermodynamic constant (Ke°) to be used in

Van't Hoof equation. For this purpose, after deriving the correct thermodynamic equilibrium

constant from isothermal studies, considering the principles of chemical equilibrium,

information was provided about the most propagated wrong constants used as the

thermodynamic equilibrium constant in the literature (Kc and Kd). Then, using equilibrium data

of adsorption of 3-aminophenol onto Avocado seed activated carbon as a case study, the
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20

performances of the propagated wrong constants for calculation of thermodynamic

parameters were compared with that of the true thermodynamic equilibrium constant. The

results showed that applying the wrong approaches and constants propagated in the

literature for thermodynamic studies cause computing erroneous values for thermodynamic

parameters. Therefore, much emphasis was placed on the importance of using the correct

thermodynamic equilibrium constant introduced in the current study.

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Acknowledgments

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The authors thank the National Council for Scientific and Technological Development

(CNPq, Brazil) for financial support.

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and thermodynamic analysis of the adsorption of hydroxy-Al cations by montmorillonite.

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Table 1. Adsorption isotherms 3-aminophenol onto Avocado seed activated carbon at 25°C. Conditions: Adsorbent mass 30.0 mg, initial pH of

adsorbate solution 7.0, time of contact between the adsorbent and adsorbate 60 min (Leite et al., 2017a).

P T
Co (mg L-1)
Data measured
Ce (mg L-1) qe (mg g-1) 𝐾𝑐 =
𝐶0 −𝐶𝑒
𝐶𝑒
(Eq 23) 𝐿𝑛
𝐶0 − 𝐶𝑒
Data manipulated

𝐾𝑑 =
𝑞𝑒 𝑚

R I
. (Eq 22)
𝐶𝑒 𝑉
1
𝐾𝑑
𝐿𝑛 (
𝑞𝑒 𝑚
. )
𝐶𝑒 𝑉
0 0 0 - -
𝐶𝑒

S C - - -
A
B
211.2
281.4
0.4785
4.3062
140.5
184.7
0.9977
0.9847
-0.002268

N
-0.01542
U 440.4
64.35
0.002271
0.01554
6.088
4.164
C
D
364.7
405.4
29.45
52.97
223.5
235.0
0.9192
0.8693
M A
-0.08420
-0.1400
11.38
6.654
0.08785
0.1503
2.432
1.895
E
F
510.5
591.1
135.0
204.2
250.3
258.0
0.7354
0.6546
E D -0.3073
-0.4237
2.780
1.895
0.3597
0.5276
1.022
0.6394
G
H
668.1
769.5
271.5
370.5
264.4
266.0
E PT 0.5936
0.5185
-0.5215
-0.6568
1.461
1.077
0.6845
0.9286
0.3790
0.07408
I
J
861.4
999.4
453.6
590.3
C
271.9
272.8
C 0.4734
0.4094
-0.7478
-0.8931
0.8990
0.6932
1.112
1.443
-0.1064
-0.3664
K
L
1130.4
1298.0
712.7
880.9
A 278.4
278.1
0.3695
0.3214
-0.9956
-1.135
0.5860
0.4736
1.706
2.112
-0.5344
-0.7474
M 1486.8 1060 284.3 0.2869 -1.249 0.4022 2.486 -0.9107
N 1573.1 1151 281.6 0.2685 -1.315 0.3671 2.724 -1.002
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Table 2. Equilibrium constants based on Liu isotherm and after applying Eq 20 to become it dimensionless and using equations 23 and 24. The

adsorbent dosage utilized was 1.50 g L-1 (Leite et al., 2017).

T (K) K Liu (L mg-1) K Liu (L mol-1)* Ke (Liu) 𝐿𝑛𝐾𝑐 𝑞𝑒 𝑚 𝐿𝑛𝐾𝑑 LnKd***

𝐶0 − 𝐶𝑒 𝐾𝑑 = .
𝐾𝑐 = 𝐶𝑒 𝑉
dimensionless** 𝐿𝑛𝐾𝑒 𝐶𝑒 Fig 1C

P T Fig 1F Fig 1G

298 0.3576 3.902.104

Eq 20
3.902.104 10.57
Eq 24
0.9972 -3.287.10-3
R I Eq 23
623.3 6.435 3.456
303
308
0.2903
0.2593
3.168.104
2.830.104
3.168.104
2.830.104
10.36
10.25
0.9964
0.9963
S C
-3.749.10-3
-3.694.10-3
314.8
186.4
5.752
5.228
3.642
3.481
313
318
0.2186
0.1842
2.386.10
2.010.10
4

4
2.386.10
2.010.10
4

4
10.08
9.908
0.9959

N
0.9962
U -4.129.10
-3.950.10
-3

-3
524.0
265.6
6.261
5.582
3.778
3.688
323 0.1549 1.690.104
* 3- aminophenol 109.128 g mol-1.
1.690.104 9.735
M A
0.9940 -5.965.10-3 62.00 4.127 3.326

** after applying Eq. 7

E D
*** obtained by 1/Kd versus Ce
P T
C E
A C
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Table 3. The values of equilibrium constant and Gibb´s free energy.

𝐶0 − 𝐶𝑒 𝑞𝑒 𝑚 𝐶𝑒 𝑉 ΔG (kJ mol-1)
𝐾𝑐 = 𝐾𝑑 = . 𝐾𝑑 = .
T (K) Ke (Liu) ΔG (kJ mol-1) 𝐶𝑒 ΔG (kJ mol-1) 𝐶𝑒 𝑉 ΔG (kJ mol-1) 𝑞𝑒 𝑚
Fig 1A* Fig 1C* Fig 1F* Fig 1G*
298 3.902.10
3.168.104
4
-26.19 0.9967 + 8.144.10-3 623.3 -15.94

P T 31.68 -8.562
303
308 2.830.10 4
-26.11
-26.25
0.9963
0.9963
+ 9.444.10-3
+ 9.459.10 -3
314.8
186.4
R I
-14.49
-13.39
38.17
32.50
-9.175
-8.914
313
318
2.386.10
2.010.104
4
-26.23
-26.20
0.9959
0.9961
+ 1.074.10 -2

+ 1.044.10-2
524.0
265.6
S C -16.29
-14.76
43.75
39.97
-9.833
-9.751
323 1.690.104 -26.14 0.9941 + 1.602.10-2

N
62.00
U -11.08 27.83
* In Fig 1 is show how it is determined at 298K. For the other temperatures, similar graphs were plotted (not shown).
-8.932

M A
E D
P T
C E
A C
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Table 4. Values of changes in enthalpy (ΔH) and changes in entropy (ΔS) obtained by plots of Fig 2.
Ke (Liu) 𝐶0 − 𝐶𝑒 𝑞𝑒 𝑚 𝐶𝑒 𝑉
𝐾= 𝐾= . 𝐾𝑑 = .
𝐶𝑒 𝐶 𝑒 𝑉 𝑞𝑒 𝑚
-1
ΔS (J K mol )
-1
0.1346 -0.2447 -114.7 27.26

P T
I
-1
ΔH (kJ mol ) -26.14 -0.06528 -49.84 -0.7318
R²adj 0.9942
Fig 2a
0.5681
Fig 2b
0.3657
Fig 2c
C R
-0.2468
Fig 2d

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Table 5. Values of Gibbs´s free energy calculated from data of Fig 3.

Fig 3A Fig 3B Fig 3C Fig 3D Fig 3E Fig 3F Fig 3G Fig 3H Fig 3I
-1 -1
ΔS° (J K mol ) -0.2447 -0.1154 -0.1680 -114.7 -518.8 -256.1 27.26 -89.30 82.37
-1
ΔH° (kJ mol ) -0.06528 -0.02618 -0.04174 -49.94 -179.0 -92.19 -0.7318 -37.90 15.91

T
-1
ΔG° (kJ mol ) +0.007649 +0.008195 +0.008324 -15.76 -24.42 -15.89 -8.854 -11.29 -8.640
R²adj 0.5681 0.9752 0.8926 0.3657 0.9082 0.9912
I
-0.2468
P 0.7738 0.8611

C R
U S
A N
M
E D
P T
C E
A C
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Table 6. Equilibrium constants based on Liu isotherm and after applying Eq 20 to become it dimensionless, other equilibrium that was

transformed to dimensionless, disregarding the principle of chemical equilibrium.

- -
T (K) K Liu (L.mol K°e Kg Liu (L.mg 1000*Kg.d Kg.d 55.51.Kg.1000.molecular weight 55.51.Kg.molecular weight
1
)
1
) (g mg )
-1

P T (g mg )
-1

a b c d e

R I f

SC
4 4 5 6
298 3.902.10 3.902.10 0.3576 3.576.10 357.6 2.166.10 2166
4 4 5 6
303 3.168.10 3.168.10 0.2903 2.903.10 290.3 1.758.10 1758
308
313
2.830.10
2.386.10
4

4
2.830.10
2.386.10
4

4
0.2593
0.2186
2.593.10
2.186.10
5

5
259.3
218.6
N U
1.571.10
1.324.10
6

6
1571
1324
318
323
2.010.10
1.690.10
4

4
2.010.10
1.690.10
4

4
0.1842
0.1549
1.842.10
1.549.10
5

5
184.2

M
154.9
A 1.116.10
9.380.10
6

5
1116
938.0
a-
3- aminophenol 109.128 g mol . -1

E D
T
b-
after applying Eq. 20

c- 𝐿
𝑚𝑔
𝑥
1000𝑚𝑔
𝑔
𝑥1000
𝑔
𝐿
= 𝑑𝑖𝑚𝑒𝑛𝑠𝑖𝑜𝑛𝑙𝑒𝑠𝑠.
E P
d- 𝐿
𝑚𝑔
𝑥1000
𝑔
𝐿
=
𝑔
𝑚𝑔
.
C C
e-
55.51
𝑚𝑜𝑙 𝐿
.
𝐿 𝑚𝑔
𝑚𝑔 𝑔
. 1000 𝑔 . 𝑚𝑜𝑙 A
= 𝑑𝑖𝑚𝑒𝑛𝑠𝑖𝑜𝑛𝑙𝑒𝑠𝑠

f- 𝑚𝑜𝑙 𝐿 𝑔 𝑔
55.51 . . =
𝐿 𝑚𝑔 𝑚𝑜𝑙 𝑚𝑔
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Highlights
 Determination of thermodynamic parameters by using Van’t Hoof equation.
 The correct equilibrium constant for determination of thermodynamic parameters of
adsorption.
 Use of nonlinear equilibrium isotherms at several temperatures to obtain the K.

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Figure 1
Figure 2
Figure 3
Figure 4