Applied Thermal Engineering 229 (2023) 120581

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Applied Thermal Engineering

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

Selecting an optimum kinetic model for gas–solid adsorption based on

statistical approaches and a model selection criterion
Md. Matiar Rahman a, c, Abu Zar Shafiullah c, Mahua Jahan Rupa a, e,
Shamal Chandra Karmaker a, b, c, Shahadat Hosan a, b, Animesh Pal d, Bidyut Baran Saha a, b, *
a
International Institute for Carbon-Neutral Energy Research, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka 819-0395, Japan
b
Mechanical Engineering Department, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka 819-0395, Japan
c
Department of Statistics, University of Dhaka, Dhaka-1000, Bangladesh
d
Department of Nuclear Engineering, University of Dhaka, Dhaka-1000, Bangladesh
e
Department of Mathematics, University of Barishal, Barishal-8254, Bangladesh

A R T I C L E I N F O A B S T R A C T

Keywords: Adsorption heat transformation (AHT) techniques can help to safeguard the environment by reducing the use of
Adsorption fossil fuels. When constructing an adsorption-based dynamic heat pump system, analyzing the kinetic charac­
Bootstrap teristics of the adsorbate–adsorbent pair is important. The recently established time-adapted linear driving force
Information criteria
(LDF) and commonly used models such as LDF, modified LDF, and Fickian diffusion (FD) models are available in
Kinetic model
Statistical tool
the literature for analyzing the kinetic characteristics, making it challenging for researchers to select the opti­
Time-adapted LDF mum one for simulating the complete real system. This study applies a non-parametric statistical approach
known as bootstrapping for simulating the replica of experimental kinetics data for all studied pairs. The kinetics
models mentioned above are used to correlate the bootstrap samples. The estimated values of the statistical
parameters are compared, and the optimum kinetics model for gas–solid physical adsorption is proposed. The
parameters of the model are estimated using the generalized reduced gradient (GRG) non-linear optimization
method. For each bootstrap sample, the optimum model is selected based on the minimum values, which means
less information loss, of a set of information-based model selection criteria (ICs). The time-adapted LDF incurs
smaller values of IC compared to other kinetics models. The p-value of the proportion test for water adsorption
onto AQSOA-Z01, RD silica gel, and Al-Fum is very small, which is less than 0.01. So, the test is significant at a
1% level, which implies that time adapted LDF model is significantly optimum. This is the first time that a
rigorous statistical optimization technique has been used to identify the optimum kinetic model for gas–solid
adsorption. The current findings are critical for a comprehensive analysis of an adsorption system and its design.

isotherm and kinetic models can be used to explore the adsorption

1. Introduction
Adsorption heat transformation (AHT) systems, for instance, heating
and cooling, that can be powered by waste heat or renewable-resource
and operate at temperatures as low as 60 ◦ C, are attracting a lot of
attention from scientists as a means to reduce world electricity demand
[1]. It is also employed in the following applications: gas storage/cap­
ture [2], purification [3], gas separation [4], desalination [5], heavy
metal/liquid removal [6], and so on. The characteristics of the
adsorbate-adsorbent combinations determine the efficiency of adsorp­
tion systems. The most significant factors in choosing a pair are their
physical, chemical, and thermodynamic characteristics [7]. Adsorption
properties. The isotherm model identifies the equilibrium absorption
uptake at a particular temperature, while the kinetic model determines
the cycle time of the process. The kinetic model estimates the adsorption
or desorption cycle time required to complete processes by determining
the rate at which vapor diffuses into the pores or removes from the
pores. As a result, in order to simulate and develop a realistic adsorption
cooling system, an appropriate model for calculating adsorption kinetics
is required [8]. Several authors have estimated the kinetic parameters of
various working pairs utilized in the sorption process, and several ki­
netics models were employed to analyze the experimental data [9-19].
Table 1 shows the studied different kinetics models and their
characteristics.

* Corresponding author at: International Institute for Carbon-Neutral Energy Research, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka 819-0395, Japan.
E-mail address: saha.baran.bidyut.213@m.kyushu-u.ac.jp (B.B. Saha).

https://doi.org/10.1016/j.applthermaleng.2023.120581
Received 14 February 2022; Received in revised form 2 March 2023; Accepted 13 April 2023
Available online 18 April 2023
1359-4311/© 2023 Elsevier Ltd. All rights reserved.
Md.M. Rahman et al. Applied Thermal Engineering 229 (2023) 120581

transfer. The same author [36] developed mathematical models for a

Nomenclature batch process to forecast concentration distributions for an active in­
gredient’s (vancomycin) adsorption on a typical hydrophobic-molecule
a Fitting parameters of time-adapted LDF model (s− 2) adsorbent. A heuristic algorithm was used to estimate the kinetic pa­
b Fitting parameters of time-adapted LDF model (s− 1) rameters by maximizing the coefficient of determination.
c Fitting parameters of time-adapted LDF model (-) However, the LDF model [37,38] is the most extensively used for
Ds Diffusion coefficient [m2/s]. explaining gas–solid sorption dynamics. At constant pressure, the LDF
Ei Expected frequency model undertakes that the particle temperature of adsorbent is always
F0 Shape factor of the particle similar. Several researchers updated the LDF model based on the char­
H0 Null hypothesis acteristics of the adsorption pair. For example, Sultan et al. [25] intro­
H1 Alternative hypothesis duced a dimensionless power ‘m’ as a variable. The LDF model was used
n1 Number of data points [-] by Liaw et al. [39] to study the parabolic concentration curve of a
Oi Observed frequency spherical particle. Sircar and Hufton [40] investigated a relationship
p Number of parameters in the model [-] between the diffusion time constant and the total mass transfer coeffi­
RP Adsorbent particle radius [m] cient of the LDF model, removing the usual constraint between them.
Wcal Calculated uptake [kg/kg] Sircar and Hufton [28] studied at the interplay of the LDF and FD
Wexp Experimental uptake [kg/kg] models, but due to integrations, local adsorption aspects were over­
W(t) Instantaneous uptake [kg/kg] looked. Lagergreen’s pseudo-first-order model and Glueckauf’s LDF
w(∞) Equilibrium uptake [kg/kg] model were thoroughly explored by Rodrigues and Silva [41]. They
observed that both techniques were similar only in the limiting condi­
Greek Letters tion of infinite bath systems or zero adsorption. The final and initial fluid
α Level of significance phase concentrations, on the other hand, are practically similar. The LDF
χ2 Chi-square value of the overall test has some limitations; it sometimes overestimates experimental kinetics
θ fractional uptake (kg/kg) at a specific time and underestimates at the rest periods [42]. Both the
LDF and FD models are successful in predicting the long-time experi­
mental results, however, they fail to predict the adsorption’s beginning
phase of adsorption. The linearized FD model causes this occurrence; the
Pal et al. [26] examined both FD and LDF kinetic models for ethanol
interception would be (ln 6/π2), implying that there will always be a
vapor adsorption onto activated carbons made from waste palm trunk
constant value. The semi-infinite model, on the other hand, is good at
(WPT) and mangrove (M). Ibrahim et al. [24] studied FD model to
forecasting the beginning phase of adsorption. The semi-infinite kinetic
determine the adsorption kinetics of ethanol adsorption onto phenol
model is clearly imprecise in predicting the experimental data for the
resin-based adsorbents for a cooling system. The author employed two
AQSOA-Z01/water pair beyond 400 s and entirely fails to forecast the
types of KOH-treated adsorbents, KOH4-PR and KOH6-PR. Sultan et al.
behavior for the RD silica gel/water pair [33].
[25] examined FD, LDF, and semi-infinite kinetic model for water
Recently Rupa et al. [33] established a time-adapted LDF model for
adsorption onto polymer-based adsorbents. Vancomycin adsorption on
gas–solid adsorption. The time-adapted LDF model was compared to the
polymeric adsorbent was investigated by Blaz Likozar et al. [34]. Here,
other kinetic models for various types of adsorption pairs. They studied
vancomycin adsorption from broth supernatant, diluted broth, and the
AC/ethanol, AC/CO2, MOF/water, MOF/methanol, zeolite/adsorbate
whole broth was examined in terms of equilibrium and kinetics. The
(water and CO2), silica gel/water, aminated solid/CO2, immobilized
RSFK, the HSDM, and the BPM models were used to study it. The HSDM
polyethyleneimine-mesoporous silica/CO2 adsorption pair. As can be
provided the best response. Vancomycin adsorption was investigated by
seen from the above literature reviews, it is evident that many adsorp­
authors [35] using two different polymeric resins (Amberlite XAD16N
tions kinetic models have been suggested for specific pairs for gas–solid
and 1600 N). They developed a fixed-bed column model and verified it
adsorption, but there is no widely accepted model for the general
in a laboratory experiment. The consistency between the estimated and
gas–solid adsorption process. Researchers face difficulties in choosing
measured data was significantly improved by applying structural
the best kinetic model to describe their experimental findings. In almost
adsorption/desorption kinetics while accounting for the resin particle
all cases, to the best of our knowledge, the authors did not consider the
size distribution, as opposed to changing the impact of external mass
information loss of the fitted model, and they used only root mean

Table 1
Studied adsorption kinetics models and their characteristics [20].
Model name Mathematical expression Advantages Limitations Remarks Ref(s).
√̅̅̅̅̅̅̅
Semi-infinite 2A Ds t Best to calculate the initial phase Not suitable for high-pressure Only acceptable for semi-infinite medium for
[21,22]
model θ =
V π ( of adsorption ratios any particle shape
)
Fickian 6 Ds t Can predict long time region Inadequate for the initial Convenient for intra-particle diffusion
θ = 1 − 2 exp − F0 π2 2 [23-
diffusion π Rp kinetics data phase of adsorption
(FD) model 27]
)
Linear driving (
Ds t Easy to calculate, suitable for Under-predicts at the initial Often used model by the researchers
θ = 1 − exp − F0 2 [28-
force (LDF) Rp breakthrough curves stage and over-predicts at the
model saturated stage of dynamic 32]
adsorption data
Modified LDF ( ( )m ) Dimensionless parameter m has No physical significance of Very few works can be found in the literature
Ds t [25]
θ = 1 − exp − F0 been introduced to correlate the the parameter m has been utilizing this model
R2p
experimental precisely. reported
Time-adapted θ = To describe the transient Time dependency of a and b is Relatively new and gaining popularity as this
[33]
LDF model ( ( )(at2 +bt+c) ) behavior more accurately, two not well defined yet. model can predict the adsorption dynamics
Ds t
1 − exp − F0 time-dependent variables a and accurately both during the initial unsaturated
R2p
b are introduced. condition as well as during the later period
when the adsorbent is near its saturated
condition.

2
Md.M. Rahman et al. Applied Thermal Engineering 229 (2023) 120581

Table 2 square deviation (RMSD) error analysis in their investigations.

Adsorption pair, data sources, and surface properties of adsorbents. The major purpose of this investigation is to use a variety of statis­
SL. Adsorption pair Data sources Surface properties of tical approaches and a model selection criterion to determine the
No. adsorbent optimal kinetic model for gas adsorption on solids. This is the first time
1 AQSOA-Z01/water Teo et al. [48] PV: 0.071 cm3/g; BET-SA: that a rigorous statistical optimization technique has been used to
189.6 m2/g, and average identify the optimum kinetic model for gas–solid adsorption. Parameter
PS: 11.78 Å. effect adjustment and information loss are considered in this investi­
gation to find the optimal kinetics for gas–solid adsorption, which also
2 RD silica gel/water Sun et al. [7], Islam PV: 0.4 cm3/g; BET-SA:
et al. [49], Chua et al. 820 m2/g, and average PS:
makes it significant from the statistical analysis of the best-fitting model.
[50] 2.2 nm. A non-linear optimization method called generalized reduced gradient
(GRG) is employed to optimize the adsorption kinetic data. The root
3 Aluminum Teo et al. [51] PV: 0.926 cm3/g; BET-SA: mean square deviation (RMSD) is employed as an error evaluation
fumarate (Al- 792.26 m2/g, and average
function. As far as we are concerned, the RMSD distribution is unknown.
Fum)/water PS: 10.91 Å.
Therefore, we must use inferential methods using non-parametric ap­
4 AQSOA-Z02/water Teo et al. [48] PV: 0.27 cm3/g; BET-SA: proaches, such as the bootstrap technique, to determine the distribution
717.8 m2/g, and average of RMSD. In the bootstrap method, 10,000 resamples from the original
PS: 11.84 Å. sample are taken, giving us a distribution of RMSD. Then this informa­
5 M− AC/ethanol Pal et al. [26] PV: 2.18 cm3/g; BET-SA:
tion is used in model selection criteria to find an optimum kinetic model.
2924 m2/g; and average Thirteen gas–solid adsorption kinetic experimental data are taken from a
PS: 1.47 nm. published paper with the aim of finding the optimum kinetic model for
6 WPT-AC/ethanol Pal et al. [26] PV: 2.51 cm3/g; BET-SA: this investigation. Among them, nine pairs are chosen from cooling
2927 m2/g; and average
systems with different refrigerants, while the remaining four are from
PS: 1.68 nm.
7 MIL-101-GP/ Solovyeva et al. [52] PV: 1.61 cm3/g; BET-SA: CO2 capture and storage applications. At first, all kinetic models are
methanol 2550 m2/g; average PS: tried to analyze the experimental data, but only the most likely optimal
not available. models, i.e., FD, LDF, and time-adapted LDF models, are chosen for
8 MIL-101-T(5)/ Solovyeva et al. [52] PV: 1.61 cm3/g; BET-SA: further examination. Statistical techniques such as bootstrap sampling,
methanol 2870 m2/g; average PS:
overall, and pairwise proportion tests were employed to select the
not available.
9 MIL-101-T(10)/ Solovyeva et al. [52] PV: 1.43 cm3/g; BET-SA: suitable kinetic model. The selection rates were determined from n =
methanol 2610 m2/g; average PS: 10000 bootstrap samples, and the statistical tests for the significance of
not available. differences in selection rates further confirmed the optimal kinetic
10 Natural zeolite tuff Ammendola et al. PV: not available; BET-SA:
model.
/CO2 [53] 141 m2/g, and average PS
range: 2–7 Å.
11 CS-H2O/CO2 Alvarez et al. [54] PV: 0.53 cm3/g; BET-SA: 2. Kinetic models
998 m2/g; and average PS:
not availabe.
The vapor diffusion rate into the pores is measured by adsorption
12 CS-C2O/CO2 Alvarez et al. [54] PV: 0.48 cm3/g; BET-SA:
1045 m2/g; and average kinetics, which aids in calculating the cycle time required to complete
PS: not availabe. the desorption/adsorption processes. Therefore, when simulating and
13 Calgon BPL/CO2 Alvarez et al. [54] PV: 0.50 cm3/g; BET-SA: designing actual adsorption chillers, an accurate model to predict the
1129 m2/g; and average adsorption kinetics is essential [8]. Numerous authors have experi­
PS: not availabe.
mentally investigated the adsorption kinetics of various working pairs
utilized in the adsorption system, and a variety of kinetics models [9-
Note: PV: Pore volume; BET-SA: BET surface area; PS: Pore size. 11,14,19] have been used to fit those data. To characterize the kinetics
of different gasses adsorbing onto various adsorbents, various models

Table 3
Fitting parameters of a time-adapted LDF model for studied adsorption pairs.
Time-adapted LDF model LDF FD

Adsorption pairs Tads [◦ C] Ds/R2p [s¡1] a [s¡2] b [s¡1] c [-] Ds/R2p [s¡1] Ds/R2p [s¡1]

AQSOA-Z01/water 60 5.42E-05 1.02E-09 − 1.5E-05 1.01 6.0E-05 4.4E-06

RD silica gel/water 30 8.33E-04 7.02E-07 − 8.6E-05 0.6 0.26 6.64E-05
Aluminum fumarate/water 60 3.29E-03 1.10E-05 − 5.90E-04 1.01 3.97E-03 2.92E-04
Aluminum fumarate/water 25 5.12E-04 1.10E-05 − 5.90E-04 1.01 4.90E-04 4.20E-05
AQSOA-Z02/water 60 6.60E-05 5.72E-09 − 6.5E-05 1.15 8.00E-05 –
AQSOA-Z02/water 45 2.75E-05 5.72E-09 − 6.5E-05 1.15 2.84E-05 –
AQSOA-Z02/water 35 1.13E-05 5.72E-09 − 6.5E-05 1.15 1.12E-05 –
AQSOA-Z02/water 25 6.95E-06 5.72E-09 − 6.5E-05 1.15 6.8E-06 –
M− AC/ethanol 50 2.71E-04 1.1E-07 − 3.1E-05 0.75 2.21E-04 1.70E-05
M− AC/ethanol 70 3.33E-04 1.0E-07 − 3.0E-05 0.75 3.23E-04 2.50E-05
WPT-AC/ethanol 30 3.96E-04 2.21E-06 − 1.1E-03 0.82 3.85E-04 3.92E-04
WPT-AC/ethanol 50 6.82E-04 2.21E-06 − 1.0E-03 0.82 6.74E-04 6.71E-04
MIL-101-GP/methanol – 1.05E-03 5.01E-07 − 4.7E-04 0.89 1.07E-03 5.51E-05
MIL-101-T(5)/methanol – 6.51E-04 5.11E-07 − 4.7E-04 0.90 6.49E-04 3.36E-05
MIL-101-T(10)/methanol – 6.58E-04 5.12E-07 − 4.7E-04 0.90 5.63E-04 3.28E-05
Natural zeolite tuff /CO2 25 3.96E-02a 4.23E-03b − 1.21E-01a 1.5 4.55E-02a 1.85E-03a
CS-H2O/CO2 30 5.81E-02a 9.74E-04b − 5.02E-03a 0.9 6.92E-02a 6.01E-03a
CS-C2O/CO2 30 5.44E-02a 9.62E-04b − 5.10E-02a 1.4 7.34E-02a 3.17E-03a
Calgon BPL/CO2 30 5.80E-02a 9.72E-04b − 5.00E-02a 0.8 5.34E-02a 2.92E-03a

Note: a [Unit] = [min− 1

] and b [Unit] = [min− 2
].

3
Md.M. Rahman et al. Applied Thermal Engineering 229 (2023) 120581

Fig. 1. Adsorption kinetics of (a) AQSOA-Z01/water, (b) RD silica gel/water, and (c) Al-Fum/water pairs using RMSD errors.

4
Md.M. Rahman et al. Applied Thermal Engineering 229 (2023) 120581

Table 4
Results of all ICs, p-value of proportion tests for AQSOA-Z01/water, RD silica gel/water, Al-Fum/water, and AQSOA-Z02/water pairs of probable kinetic models
employing n = 10000 bootstrap samples.
AQSOA-Z01/water

Model Error mean AIC BIC AICc mAIC AIC3 CAIC ABIC

LDF 0.0745 –223.16 − 214.78 –222.43 − 199.16 − 219.16 − 210.78 − 227.36

FD 0.0838 − 218.08 − 211.79 − 217.65 − 206.08 − 215.08 − 208.79 − 221.23
Time-adapted LDF 0.0638 ¡234.48 ¡228.20 ¡234.06 –222.48 ¡231.48 ¡225.20 ¡237.64
Overall and pairwise tests P-value
Overall 2.0E-15 2.1E-14 2.2E-15 2.0E-13 2.1E-15 2.0E-14 2.1E-15
LDF vs time-adapted LDF 2.0E-04 2.1E-05 2.2E-03 1.4E-04 1.8E-04 1.9E-03 2.1E-04
FD vs time-adapted LDF 1.5E-08 2.1E-09 1.1E-08 2.0E-07 2.0E-08 1.7E-09 2.1E-11
RD silica gel/water
LDF 0.0745 –223.16 − 214.78 –222.43 − 199.16 − 219.16 − 210.78 − 227.36
FD 0.0838 − 218.08 − 211.79 − 217.65 − 206.08 − 215.08 − 208.79 − 221.23
Time-adapted LDF 0.0638 ¡234.48 ¡228.20 ¡234.06 –222.48 ¡231.48 ¡225.20 ¡237.64
Overall and pairwise tests P-value
Overall 2.5E-11 1.9E-12 2.8E-16 2.4E-12 1.8E-13 2.4E-12 2.3E-16
LDF vs time-adapted LDF 2.1E-05 2.5E-07 1.8E-04 1.9E-03 2.8E-05 2.9E-04 2.7E-03
FD vs time-adapted LDF 1.6E-09 1.6E-10 1.7E-07 2.8E-09 2.2E-06 1.4E-12 2.7E-13
Al-Fum/water
LDF 0.0745 –223.16 − 214.78 –222.43 − 199.16 − 219.16 − 210.78 − 227.36
FD 0.0838 − 218.08 − 211.79 − 217.65 − 206.08 − 215.08 − 208.79 − 221.23
Time-adapted LDF 0.0638 ¡234.48 ¡228.20 ¡234.06 –222.48 ¡231.48 ¡225.20 ¡237.64
Overall and pairwise tests P-value
Overall 2.2E-16 2.3E-13 2.7E-14 1.0E-15 1.9E-16 2.7E-12 2.8E-13
LDF vs time-adapted LDF 2.1E-05 2.5E-04 2.9E-04 1.3E-03 2.8E-03 2.9E-04 2.8E-05
FD vs time-adapted LDF 1.6E-07 2.5E-10 2.1E-07 2.1E-08 2.7E-09 1.0E-8 2.8E-12
AQSOA-Z02/water
LDF 3.11 22.35 25.36 23.56 24.65 27.65 28.51 24.61
Time-adapted LDF 0.98 4.23 19.50 6.35 27.31 6.24 18.50 2.81
Overall test P-value
LDF vs time-adapted LDF 2.2E-03 2.3E-04 2.2E-04 1.7E-04 1.9E-05 2.8E-04 2.7E-04

*Bold values represent the smallest ICs.

are available. The pseudo-first-order equation proposed by Lagergreen

[43] is said to be the initial model considering the adsorption rate
2.2. Fickian diffusion (FD) model
dependent on the adsorption capacity. However, the linear driving force
(LDF) and Fickian diffusion (FD) model is the most often used model for
The FD model can be employed to predict the adsorption kinetics of
characterizing the gas–solid adsorption dynamics. The next paragraphs
various adsorption pairs [44]. Assuming purely radial diffusion by a
explain the LDF, FD, and recently developed time-adapted LDF models.
spherical shape adsorbent particle, the diffusion equation can be
expressed as follows [21]-
2.1. Linear driving force (LDF) model
( ) ( )
dw 1 ∂ ∂w
The LDF is a widely used model to illustrate the interaction between = 2 r 2 Ds (5)
dt r ∂r ∂r
adsorbate and adsorbent during the adsorption process. Glueckauf and
Coates were the first to present this model’s approximation [37]. The For constant diffusivity (Ds ), equation (5) simplifies to
following equation can be used to determine the rate of adsorption of an (
dw
) ( 2
∂ w 2 ∂w
)
adsorption pair. = Ds + (6)
dt ∂r2 r ∂r
(dw/dt) = Ks av (w(∞) − w(t)) (1) where, w(r, t) represents the adsorbed phase concentration.
Although the diffusivity is concentration dependent, the assumption of a
where ksav is the overall mass transfer coefficient. w(t) represents instant
constant diffusivity is still an acceptable approximation provided that
uptake [kg/kg], w(∞) represents the saturation uptake [kg/kg]. This
the uptake curve is measured over a small differential change in
equation is originally proposed by Gleuckauf [27], where the shape
adsorbed phase concentration [21]. If the uptake of sorbate by the
factor (F0) is 15 for the spherical shape of an adsorbent particle with a
adsorbent is small relative to the total quantity of sorbate introduced
homogeneous structure.
into the system, the ambient sorbate concentration will remain essen­
F0 Ds tially constant following the initial step, change, and the appropriate
Ks av = (2)
R2p initial and boundary conditions are;
( )
Rp denotes adsorbent particle radius [m], and Ds signifies the diffu­ ∂w
w(r, 0) = w(initial), w(r, t) = w(∞), =0
sion coefficient [m2/s]. Then, the equation (1) can be written as follows- ∂r r=0
F0 D s After simplifying equation (6), it can be expressed by the familiar
(dw/dt) = (w(∞) − w(t)) (3)
R2p expression-
( )
After simplifying equation (3), the fractional uptake (θ) can be pre­ w(t) − w(initial) 6 ∑∞
1 2 2 Ds t
θ= = 1− 2 exp − F n π (7)
sented as follows- w(∞) − w(initial) π n=1 n2 0
R2p
( )
w(t) − w(initial) Ds t
θ= = 1 − exp − F0 2 (4) where Rp is the adsorbent particle radius and w(t) is the average con­
w(∞) − w(initial) Rp
centration through the adsorbent particle, defined by-

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Md.M. Rahman et al. Applied Thermal Engineering 229 (2023) 120581

Fig. 2. Selection rate of (a) AQSOA-Z01/water, (b) RD silica gel/water, and (c) Al-Fum/water pairs using RMSD errors.

6
Md.M. Rahman et al. Applied Thermal Engineering 229 (2023) 120581

Fig. 3. Adsorption kinetics of (a) M− AC/ethanol pair for 50 ◦ C; and (b) WPT-AC/ethanol pair for 30 ◦ C using RMSD errors.

∫
3 r
the uptake at short times [42]. Based on this error, Rupa et al. [33]
w(t) = wr2 dr
r3 0 proposed to modify the LDF with a time-based correction factor equation
(at2 + bt + c) to the LDF model. As a result, the time-adapted LDF Model
The equation (7) gives faster convergence over the long time period,
[33] is presented, and it can be stated as-
whereas the higher terms of this summation go to zero; consequently,
⎛ ( )(at2 +bt+c) ⎞
the FD model can be presented as follows [21]-
w(t) − w(initial) Ds t
( ) θ= = 1 − exp⎝ − F0 ⎠ (9)
6 Ds t w(∞) − w(initial) R2p
θ = 1 − 2 exp − F0 π 2 2 (8)
π Rp
Here a, b, and c represent fitting parameters. The unit of a is s− 2 or
min− 2, the unit of b is s− 1 or min− 1, and c is a unit less. The correction
factor is chosen to be a quadratic function because the quadratic func­
2.3. Time-adapted LDF model
tion helps to find out the curves which are in a parabola or U-shape and
varies the curve in width or steepness. The values of a, b, and c are fixed
When the adsorbent particle’s temperature is uniform, and the heat
for the same working pair. These values are specified after fitting the
transfer rate is ignored, the LDF equation is commonly employed [45]. It
experimental data with various configurations (thickness and sizes of
has a wide range of applications to describe sorption kinetics at non-
adsorbents), different measurement methods (LTJ and LPJ), and
equilibrium conditions and aids in understanding the fundamental
different adsorption temperatures and pressures.
concept of the adsorption process that ranges from transient to cyclic
steady-state [3346,47]. However, the LDF model has several flaws; it
sometimes overestimates the uptake at long times and underestimates

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Md.M. Rahman et al. Applied Thermal Engineering 229 (2023) 120581

Fig. 4. Selection rate of (a) M− AC/ethanol, and (b) WPT-AC/ethanol adsorption pairs using RMSD errors.

Table 5
Results of all ICs, p-value of proportion tests for M− AC/ethanol, and WPT-AC/ethanol pairs of probable kinetic models employing n = 10000 bootstrap samples.
M¡AC/ethanol

Model Error mean AIC BIC AICc mAIC AIC3 CAIC ABIC

LDF 0.061 − 3055.93 − 3051.72 − 3055.92 − 3055.93 − 3054.93 − 3050.72 − 3054.90

FD 0.116 − 2737.14 − 2732.93 − 2737.13 − 2737.14 − 2736.14 − 2731.93 − 2736.11
Time-adapted LDF 0.015 – ¡3728.90 ¡3745.65 ¡3721.73 ¡3741.73 ¡3724.90 ¡3741.60
Overall and pairwise tests P-value 3745.73
Overall 1.8E-12 1.8E-13 1.2E-13 1.5E-14 3.1E-11 1.0E-13 1.6E-14
LDF vs time-adapted LDF 2.2E-03 2.6E-04 1.2E-07 1.9E-06 1.7E-07 1.4E-08 2.7E-05
FD vs time-adapted LDF 2.5E-07 1.1E-12 1.5E-11 1.6E-10 1.4E-9 1.4E-09 2.1E-12
WPT-AC/ethanol
LDF 0.061 − 1952.2 − 1948.37 − 1952.19 − 1952.2 − 1951.2 − 1947.37 − 1951.55
FD 0.127 − 1704.34 − 1700.51 − 1704.33 − 1704.34 − 1703.34 − 1699.51 − 1703.69
Time-adapted LDF 0.023 – ¡2260.58 ¡2275.76 ¡2251.88 ¡2271.88 ¡2256.58 ¡2273.27
Overall and pairwise tests P-value 2275.88
Overall 1.96E-13 2.35E-12 1.61E-14 1.5E-16 2.1E-15 1.5E-14 1.9E-13
LDF vs time-adapted LDF 2.6E-04 2.4E-07 1.7E-09 2.8E-08 1.9E-08 1.3E-07 2.7E-10
FD vs time-adapted LDF 1.8E-06 1.8E-11 1.4E-13 1.6E-15 1.4E-12 1.8E-08 2.6E-13

*Bold values represent the smallest ICs.

8
Md.M. Rahman et al.
Fig. 5. Adsorption kinetics of (a) MIL-101-GP/methanol and (b) MIL-101-T(5)/methanol pairs using RMSD errors.
2.4. Experimental data
In this study, experimental data extracted from thirteen widely used
gas–solid adsorption pairs are analyzed to find the best-fitted kinetic
model for each pair. Among them, nine pairs (SL. No 1–9 of Table 2) are
chosen from cooling systems with different refrigerants, while the
remaining four are from CO2 capture and storage applications. The
adsorption pair, data sources, and surface properties of adsorbents are
all listed in Table 2.
3. Statistical tools
The statistical techniques used to choose the optimum kinetic model
(s) for gas–solid physical adsorption are described in this section. A set of
model selection criteria outlined in Section 3.2 are used to compare
these models. The residual sum of squares (RSS) for the candidate
models, i.e., the sum of the squared discrepancies between the observed
and estimated outcome (Y = uptake), is required for computing the
9
Applied Thermal Engineering 229 (2023) 120581
model selection criteria. Original experimental data, however, allow
computing a single measurement of RSS, and this, in turn, computes a
single value of the information criteria for each model. Multiple esti­
mates of RSS and IC can be obtained by replicating the experiment. Since
the actual experiment was not replicated due to time and cost con­
straints, a simulation-based approach, i.e., bootstrapping (Section 3.3),
was applied to generate samples from the existing data. Bootstrap
samples allow to estimate the RSS of a given model multiple times under
the same experimental setup. This enables us to compare the informa­
tion loss of the candidate models from each bootstrap sample. Since the
experiment was operated under regulated conditions, the outcome and
simulated data were expected to signify the true outcome under the
treatment combinations. An empirical approximation of the rate at
which a model is preferred over alternative models is provided by the
percentage of samples where a specific model meets the minimal value
of a selection criterion. The probability of each model is compared
independently based on each criterion, and tests are conducted to find
evidence that specific model(s) have a higher selection rate (more likely
Md.M. Rahman et al. Applied Thermal Engineering 229 (2023) 120581

Table 6
Results of all ICs, p-value of proportion tests for MIL-101-GP/methanol, MIL-101-T (5)/methanol, MIL-101-T(10)/methanol pairs of probable kinetic models
employing n = 10000 bootstrap samples.
MIL-101-GP/methanol

Model Error mean AIC BIC AICc mAIC AIC3 CAIC ABIC

LDF 0.039 − 2299.45 − 2297.22 − 2299.39 − 2299.45 − 2298.45 − 2296.22 − 2300.37

FD 0.130 − 1702.28 − 1700.05 − 1702.22 − 1702.28 − 1701.28 − 1699.05 − 1703.20
Time-adapted LDF 0.035 – ¡2338.19 ¡2346.50 –2323.12 ¡2343.12 ¡2334.19 ¡2350.79
Overall and pairwise tests P-value 2347.12
Overall 2.8E-15 2.1E-13 1.9E-13 1.8E-15 3.2E-11 1.8E-16 1.9E-14
LDF vs time-adapted LDF 2.1E-04 2.8E-04 1.5E-05 2.9E-06 3.7E-06 2.4E-09 1.7E-08
FD vs time-adapted LDF 1.9E-08 1.1E-11 1.5E-13 1.6E-11 1.4E-12 1.4E-11 2.1E-12
MIL-101-T (5)/methanol
LDF 0.643 1.85 4.04 1.91 1.85 2.85 5.04 0.89
FD 0.149 − 1634.62 − 1632.43 − 1634.56 − 1634.62 − 1633.62 − 1631.43 − 1635.58
Time-adapted LDF 0.033 – ¡2367.55 ¡2375.65 ¡2352.31 ¡2372.31 ¡2363.55 ¡2380.14
Overall and pairwise tests P-value 2376.31
Overall 1.7E-14 2.3E-15 1.7E-15 2.5E-16 2.9E-15 3.7E-14 1.9E-16
LDF vs time-adapted LDF 2.6E-05 1.4E-04 1.7E-06 2.8E-05 2.9E-05 2.3E-06 2.2E-09
FD vs time-adapted LDF 2.8E-08 2.8E-09 2.6E-11 2.4E-12 2.6E-11 2.8E-12 2.9E-12
MIL-101-T (10)/methanol
LDF 0.069 − 268.68 − 266.48 − 268.62 − 268.68 − 267.68 − 265.48 − 269.63
FD 0.1334 − 224.51 –222.31 − 224.45 − 224.51 –223.51 − 221.31 − 225.46
Time-adapted LDF 0.039 ¡292.09 ¡300.27 ¡276.91 ¡296.91 ¡288.09 ¡304.69
Overall and pairwise tests P-value ¡300.91
Overall 2.9E-15 2.3E-16 2.8E-14 2.5E-15 1.8E-16 1.7E-14 2.6E-15
LDF vs time-adapted LDF 2.1E-05 2.1E-06 1.8E-05 2.2E-06 1.5E-08 2.3E-05 2.8E-09
FD vs time-adapted LDF 2.7E-10 3.6E-11 2.5E-12 2.4E-13 2.8E-10 2.6E-09 2.6E-12

*Bold values represent the smallest ICs.

to be optimal) than others. The overall proportion test, as well as pair­

wise comparisons, are covered in Section 3.4.
3.1. Root mean square deviation (RMSD)
The error evaluation function RMSD is also commonly used [55], and
its mathematical form is-
√̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
√∑
√n ( )2
√ W − Wcal i
√i=1 exp
RMSD = (10)
n
Here, Wexp and Wcal measure the experimental and projected/
calculated (using model) uptake, respectively. n presents the total
number of observations. If the difference between the experimental and
projected values is large, the square offers a large value in this error
evaluation function. RMSD primarily advises against using models that
produce substantial errors on a regular basis. It is based on the normal
distribution, which is used to fit ordinary least square regression models.
3.2. Information based criterion
In general, the penalized-likelihood information criteria (IC), − 2l + f
(n, p), contains a goodness of fit term (-2l) and a penalty function, f(n, p)
[56-58]. Here, n is the number of observations, and p indicates the
number of parameters in the kinetic model. The purpose of these criteria
is to find the (optimal) model that best defines the data relationship.
These criteria are founded on the idea that the best model is one that
sacrifices the least amount of information when estimating the true
relationship. Thus, the information-based model selection criteria aim to
select the model which incurs the minimum discrepancy with the un­
derlying model relative to all other models examined in the study. The
following equation shows the list of IC’s used for selecting the optimal
kinetic models in this study.
AIC : − 2l + 2p
BIC : − 2l + pln(n)
AICc : − 2l + 2p(n/(n − p − 1))
AIC3 : − 2l + 3p (11)
mAIC : − 2l + 2p2
CAIC : − 2l + p(ln(n) + 1)
ABIC : − 2l + pln((n + 2)/24)
Where 2l = − n(log2π + log(error) − logn + 1)
3.3. Bootstrap approach
Efron and Tibshirani (1993) [59] proposed the bootstrap sampling
method for performing data-driven (non-parametric) statistical analysis
[60]. This method assumes that data (experimental) represent the un­
derlying population. The bootstapping sampling gives a sampling dis­
tribution of the estimates like proportion and average. Using the same
condition of replacement sampling method, the repeated samples are
drawn randomly from the original sample taking with same size of
sample in each repeated sample. Therefore, each repeated sample gives
an estimated value of the certain parameter (like adsorption uptake) so
that sampling distribution of the estimate is observed. Hence, the RMSD,
standard errors (SE), and confidence intervals (CI) of the parameter
(adsorption uptake) are easily estimated using the sampling distribu­
tion. These estimates are usually used for testing a parameter or
comparing models.
3.4. Proportion tests
For each candidate model, the bootstrap samples give 10,000 esti­
mates of each IC. At each bootstrap sample, the IC values of the candi­
date models are compared, and the smallest IC value is treated as
minimum IC value. For each sample, only one minimum IC value is
observed. The proportion of bootstrap samples when a model achieves
the minimum value of an IC estimates the selection rate of the model by
the specific IC, i.e.,
Here, i represents the candiadate model: LDF, FD, and time-adapted
LDF. Given information criterion, the selection rate of a specific model

10
Md.M. Rahman et al. Applied Thermal Engineering 229 (2023) 120581

Fig. 6. Selection rate of (a) MIL-101-GP/methanol, and (b) MIL-101-T(5)/methanol, adsorption pairs using RMSD.

estimates the expected probability or likelihood that the criterion will
declare the model to be the best kinetic model. Since the proportions
obtained from bootstrap approximations of the true selection probabil­
ities of the candidate models, a statistical test is conducted to examine
the equality of the likelihoods. Here the null hypothesis is,
pairwise comparisons, respectively. Thus, the selection of a single or set
of optimum models is validated separately for each criterion considered
in this study.
3.4.1. Overall proportion tests

Number of bootstrap samples with minimum value of IC for model i

Selection rate for model i =
Number of bootstrap samples (10000)

H0; The three kinetic models are equally likely based on the IC’s vs.
H1; At least two models have different selection probabilities for the
IC’s.
In case we find evidence against H0, a multiple comparison test
further examines the pairs of models that have unequal selection rates.
The chi-square test and t-tests are used to conduct the overall and
The Chi-squared (χ 2) test [61] is an overall test which can be used to
examine whether a kinetic model is selected by chance, i.e., each of the
three kinetic models are equally likely to be selected by a given IC. The
test procedure can be described using the following example. Let us say a
gambler wants to see if the six numbers on a six-sided dice are equally
likely to show on top when the dice is rolled. The gambler conducts an
experiment by rolling the dice a large number of times (say 10000) and

11
Md.M. Rahman et al. Applied Thermal Engineering 229 (2023) 120581

Fig. 7. Adsorption kinetics of (a) Zeolite tuff/CO2, (b) CS-CO2/CO2, and (c) Calgon BPL/CO2 pairs using RMSD errors.

observing the frequency Oi of i (i = 1,2,…,6) out of the 10,000 trials. The using the test–statistic is, χ 2 =
∑6 (Oi − Ei )2
where Oi denotes observed
i=1 Ei
proportion, Oi/10000 estimates the true probability (Pi) that the number
frequency and Ei = (1/6)*10000 estimates the expected frequency of i
i appears on top of the dice. The null hypothesis H0: P1 = P2 = …….. = P6.
under H0. The test statistic follows χ 2 distribution with five degrees of
Against the alternatives H1: At least two are not equal, can be tested
freedom (df.). If the p-value is small (<0.05), the null hypothesis H0 is

12
Md.M. Rahman et al. Applied Thermal Engineering 229 (2023) 120581

Table 7
Optimal kinetic model using model selection criteria for n = 10000 bootstrap samples for zeolite tuff/CO2, CS-H2O/CO2, CS-CO2/CO2, and Calgon BPL/CO2 pairs using
RMSD errors.
Natural zeolite tuff/CO2

Model Error mean AIC BIC AICc mAIC AIC3 CAIC ABIC

LDF 0.0881 − 159.72 − 157.879 − 159.64 − 159.729 − 158.729 − 156.879 − 161.015

FD 0.1541 − 133.48 − 131.635 − 133.397 − 133.486 − 132.486 − 130.635 − 134.772
Time-adapted LDF 0.04339 ¡179.621 ¡186.069 ¡163.022 ¡183.022 ¡175.621 ¡192.166
Overall and pairwise tests P-value ¡187.02
Overall 2.4E-15 2.8E-16 2.4E-14 1.5E-16 2.5E-12 1.3E-16 2.1E-15
LDF vs time-adapted LFD 1.9E-03 1.6E-04 2.4E-04 1.9E-05 1.9E-04 2.1E-07 1.7E-08
FD vs time-adapted LFD 2.6E-07 1.5E-08 1.8E-11 2.8E-11 1.6E-09 1.2E-11 1.9E-10
CS-H2O/CO2
LDF 0.039 − 40.80 − 40.16 − 40.46 − 40.80 − 39.80 − 39.16 − 43.20
FD 0.098 − 27.72 − 27.08 − 27.38 − 27.72 − 26.72 − 26.08 − 30.12
Time-adapted LDF 0.005 ¡61.07 ¡59.18 ¡39.62 ¡59.62 ¡57.07 ¡73.24
Overall and pairwise tests P-value ¡63.62
Overall 2.3E-12 1.9E-13 3.1E-16 3.2E-15 2.7E-15 1.9E-13 1.8E-15
LDF vs time-adapted LDF 1.8E-05 1.9E-04 1.7E-04 2.4E-05 2.9E-04 2.3E-07 2.7E-08
FD vs time-adapted LDF 2.1E-07 2.3E-10 1.6E-13 1.4E-11 2.4E-13 2.4E-10 1.8E-12
CS-CO2/CO2
LDF 0.050 − 37.03 − 36.39 − 36.70 − 37.03 − 36.03 − 35.39 − 39.44
FD 0.132 –23.52 –22.88 –23.18 –23.52 –22.52 − 21.88 − 25.92
Time-adapted LDF 0.013 ¡49.80 ¡47.25 ¡45.36 ¡25.80 ¡45.80 ¡43.25 ¡59.43
Overall and pairwise tests P-value
Overall 1.5E-16 2.6E-15 1.9E-13 1.2E-15 1.7E-15 1.3E-13 2.2E-15
LDF vs time-adapted LDF 2.1E-07 2.1E-08 1.8E-06 2.2E-09 1.5E-04 2.3E-06 2.8E-10
FD vs time-adapted LDF 1.8E-11 1.2E-12 1.5E-11 1.4E-12 1.8E-10 2.4E-11 2.1E-10
Calgon BPL/CO2
LDF 0.032 − 43.36 − 42.72 − 43.03 ¡43.36 − 42.36 − 41.72 − 45.77
FD 0.117 − 25.24 − 24.60 − 24.91 − 25.24 − 24.24 –23.60 − 27.65
Time-adapted LDF 0.014 ¡46.54 ¡44.65 − 25.10 ¡45.10 ¡42.54 ¡58.72
Overall and pairwise tests P-value ¡49.10
Overall 1.8E-14 1.9E-15 1.8E-16 1.7E-14 1.8E-15 1.9E-15 2.5E-16
LDF vs time-adapted LDF 1.1E-08 2.1E-05 3.8E-07 3.2E-09 1.5E-08 4.3E-04 1.8E-06
FD vs time-adapted LDF 1.7E-12 1.6E-13 1.5E-12 2.5E-12 2.6E-11 2.4E-13 2.4E-12

*Bold values represent the smallest ICs.

rejected in favor of H1. In this study, we have three candidate models to
test the selection probabilities for different IC. Using the bootstrap
samples, the errors are obtained separately for the candidate models, ICs
are computed, and the models with the minimum value of each IC are
recorded for each sample. Thus, given IC, the 10,000 bootstrap samples
provide Oi and Ei = (1/3)*10000 for the ith model (i = 1,2,3). Finally, the
p-value is obtained using the observed value of the test statistic and χ 2
distribution with 2 df. A small p-value (<0.05) provides sufficient evi­
dence that the three kinetic models are not equally probable to be
preferred by the given IC. This means at least one model may have a
higher chance of being chosen than other candidates to be selected by
the criteria using the experimental data. In this study, the overall test is
performed independently for each criterion to investigate if the specific
model(s) are selected to be the optimum by most of the criteria.
3.4.2. Pairwise test: Multiple comparisons
If the overall proportion test suggests that the selection probabilities
of the three kinetic models are unequal, it is required to identify the pair
(s) of models with different selection probabilities for the given IC. This
is accomplished by a multiple comparisons test [61], which compares
the selection probabilities of all the 3C2 = 3 pairs of models under
investigation. For instance, the null hypothesis that two models (1 & 2)
are equally probable, i.e., achieve minimum IC value, is given by H0: P1
= P2, which is tested against the alternative hypothesis H1: They are not
̂p 1 − ̂p 2
equal. The test statistic is given by- Z = √̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
where ̂
̂p (1− ̂p )(1/n1 +1/n2 )
indicates pooled sample proportion, n1 and n2 (10000) denote the size of
the bootstrap samples. A small p-value gives evidence against the
equality of selection probabilities of the two models, implying that one
model is more likely than the others. Thus, the multiple comparisons test
validates the selection of the best model based on the selection rates that
are significantly higher than others. As the study considers seven
different IC’s, the overall and pairwise comparison tests are performed
independently for each criterion.
4. Results and discussion
The GRG non-linear optimization technique was used to fit the
experimental adsorption kinetic data of thirteen gas–solid adsorption
pairs shown in Table 2. Table 3 presents the fitting parameters of the
studied kinetic models for different pairs using GRG non-linear optimi­
zation methods.
All kinetic models were fitted to the experimental data, but only the
probable optimum models, i.e., FD, LDF, and time-adapted LDF models,
are selected for further examination. Here, it can be said that only these
three kinetic models fit comparatively better than other models.
Therefore, these three models were picked for statistical analysis. In this
study, the RMSD error is calculated for each model. This section ex­
amines statistical approaches like overall and pairwise proportion tests
and selection probabilities using 10,000 bootstrap samples.
4.1. Water adsorption
Teo et al. [48] studied the water adsorption on AQSOA-Z01 and
AQSOA-Z02 at different temperatures. They evaluated adsorption
isotherm models for characterization. Sun et al. [7] addressed the
p = xn11 +x
2
+n2
thermodynamics of water adsorption kinetics onto RD silica gel. Teo
et al. [51] also focused on the kinetics of water adsorption onto
Aluminium Fumarate. Fig. 1 depicts fractional adsorption uptake at
various times for three possible optimum kinetic model fittings of water
adsorption onto AQSOA-Z01, RD silica gel, and aluminium fumarate
adsorbents. The kinetic model fittings of the AQSOA-Z02 adsorbent are
presented in SF1 in the supplementary file.
For four water adsorption pairs, Table 4 shows the RMSD error

13
Md.M. Rahman et al. Applied Thermal Engineering 229 (2023) 120581

Fig. 8. Selection rate of (a) Natural zeolite tuff/CO2, (b) CS-CO2/CO2, and (c) Calgon BPL/CO2 adsorption pairs using RMSD.

means (10000 bootstrap sample) and the values of information criteria
(IC’s) of three possible optimum kinetic models. It also includes the p-
value for both the overall and pairwise proportion tests. It is found that
the values of all IC’s for the time-adapted LDF model are small and
associated with other possible models when considering the RMSD error
mean for all four pairs. This means that, when all IC is considered, the
information loss of the time-adapted LDF model is lower than that of the
other two models. As a result, the time-adapted LDF model has a smaller
amount of information loss than other models for these three studied
water adsorption pairs. Table 4 shows the p-values of proportion tests for

14
Md.M. Rahman et al.
the equality of the minimum IC’s. It demonstrates that the p-value for
these pairs is very low, close to zero, and less than 0.01. As a result, at a
1% level of significance, both tests are highly significant. It claims that
when compared to other possible models, the time-adapted LDF model
has much-reduced information loss than other models, hence selected as
the optimal model by each selection criterion. Fig. 2 illustrates a bar
diagram showing the selection probability that was constructed using
10,000 bootstrap samples. The selection rate of the possible kinetic
models for three adsorption pairs was graphically depicted. The selec­
tion rate graph for AQSOA-Z02/water pair has been presented in SF2 in
the supplementary files. When all criteria are considered, it is clear that
the time-adapted LDF model has the highest selection rate/probability
among the three kinetic models. According to AIC, the time-adapted LDF
model has an estimated selection probability of 75 percent for AQSOA-
Z01/water pair, 78 percent for RD silica gel/water pair, 65 percent for
Al-Fum/water pair. As a result, the time-adapted LDF model is the op­
timum kinetic model.
4.2. Ethanol adsorption
Pal et al. [26] studied ethanol vapor adsorption uptake and kinetics
onto biomass-based activated carbon. The author developed two ad­
sorbents: M− AC, which was prepared from mangroves, and WPT-AC,
which was prepared using waste palm trunks. The experimental ki­
netic data are extracted from this published article [26]. Fig. 3(a) and (b)
show the kinetic model fittings for ethanol vapor adsorption onto
M− AC/ethanol at 50 ◦ C and WPT-AC/ethanol at 30 ◦ C, respectively. The
kinetic model fittings for M− AC/ethanol at 70 ◦ C and WPT-AC/ethanol
at 50 ◦ C are also presented in SF3 in the supplementary file (see Fig. 4).
Table 5 displays the RMSD error means (10000 bootstrap sample)
and the values of IC’s of the possible kinetic models for two ethanol
adsorption pairs. Also, it presents the p-value of the overall and pairwise
proportion tests. It is found that all of the values of ICs for the time-
adapted LDF model are minimal when compared to LDF and FD
models for M− AC/ethanol and WPT-AC/ethanol adsorption pairs. As a
result, for these two ethanol adsorption pairs, the time-adapted LDF
model has less information loss than LDF models. It demonstrates that
the p-value of overall and pairwise proportion tests for these pairs is very
low, close to zero, and less than 0.01. It claims that when compared to
other possible models, the time-adapted LDF model has much-reduced
information loss than other candidates, hence selected as the optimal
model by each selection criterion. The selection rate of the possible ki­
netic models for (a) M− AC/ethanol, and (b) WPT-AC/ethanol pairs have
been presented in Fig. 5. It is found that the time-adapted LDF model has
the highest selection rate/probability among the three kinetic models.
So, it can be stated that the time-adapted LDF model is an optimum
kinetic model.
4.3. Methanol adsorption
We extended our work to MIL-101(Cr) [52], a porous crystalline
solid that belongs to a family of porous crystalline solids. The large
pressure jump (LPJ) method was used to measure the dynamics of
methanol sorption onto MIL-101(Cr). Fig. 5 shows the experimental
methanol uptakes onto MIL-101-GP and MIL-101-T (5), as well as the
three most likely optimum kinetics models. The kinetic model fittings of
MIL-101-T (10)/methanol pairs are presented in SF4 in the supple­
mentary file. Table 6 presents the IC values and statistical test results for
methanol adsorption. It is found that the values of IC’s for the time-
adapted LDF model are minimal when compared to LDF and FD
models for all pairs. So, for these adsorption pairs, the time-adapted LDF
model has less information loss than LDF and FD models. Both test re­
sults in Table 6 confirm that the time-adapted LDF model is significantly
better than the other two models. The selection rate of these three
15
Applied Thermal Engineering 229 (2023) 120581
models for two methanol adsorption pairs is graphically depicted in
Fig. 6. The selection rate diagram is presented in SF5 in the supple­
mentary documents. When all criteria are considered, the time-adapted
LDF model clearly has the highest selection rate among the three kinetic
models.
4.4. CO2 adsorption
Ammendola et al. [53] studied CO2 adsorption onto natural zeolite
tuff at 25 ◦ C. Further to our research, we investigated CO2 adsorption
[54] in the context of its capture and storage (CCS). Two AC’s made from
biomass, namely, CS-H2O and CS-CO2; and Calgon BPL (bituminous
coal-based) are used. Fig. 7 shows the kinetic model fittings for CO2
adsorption onto natural zeolite tuff, CS-CO2, and Calgon BPL are pre­
sented at various times. The kinetic model fittings for CS-H2O/CO2 are
presented in SF6 in supplementary documents.
Table 7 presents the IC values and statistical test results for CO2
adsorption. The values of IC’s for the time-adapted LDF model are
minimal when compared to LDF and FD models for all CO2 adsorption
pairs presented in Table 7. As a result, for these adsorption pairs, the
time-adapted LDF model has less information loss than LDF models.
Overall and pairwise proportion test confirms that the time-adapted LDF
model is significantly more optimum than the other two models. The
selection rate depicted in Fig. 8 demonstrates that the time-adapted LDF
model obviously has the highest selection rate among the three kinetic
models. The selection rate diagram for CS-H2O/CO2 pair is presented in
SF7 in the supplementary file.
5. Conclusions
For a gas–solid adsorption system, the equilibrium fractional
adsorption uptake of thirteen pairs has been modeled using popularly
used kinetic models employing generalized reduced gradient (GRG)
non-linear optimization techniques considering RMSD error evaluation
function. The findings of this investigation demonstrate which kinetic
model is most suited for a gas–solid adsorption process. The present
study indicates that the time-adapted LDF model is the best suitable than
conventional LDF and FD models for gas–solid adsorption systems in
terms of information losses based on a comprehensive assessment of IC’s
employing bootstrap error means. The time-adapted LDF model is
significantly optimum from a statistical standpoint, as evidenced by the
small p-values (close to zero) for two proportion tests subsequent to
adsorption pairs, and the identified optimal model could also be perti­
nent for other pairs for the gas–solid adsorption process. According to
AIC, it is found that the time-adapted LDF model has an estimated se­
lection probability of 75% for AQSOA-Z01/water pair, 78% for RD silica
gel/water pair, 65% for Al-Fum/water pair, whereas for all of these pairs
LDF model shows 23%, 7.5%, and 32%, respectively. Finally, among all
possible kinetic models, selection probability based on bootstrapping
confirms that the time-adapted LDF model has the highest selection rate.
This study will help the researcher in the adsorption field in their
rigorous investigation of adsorption kinetic analysis as well as adsorp­
tion characteristics.
CRediT authorship contribution statement
Md. Matiar Rahman: Conceptualization, Formal analysis, Method­
ology, Writing – original draft. Abu Zar Shafiullah: Conceptualization,
Formal analysis, Methodology. Mahua Jahan Rupa: Conceptualization,
Formal analysis. Shamal Chandra Karmaker: Conceptualization,
Methodology. Shahadat Hosan: Formal analysis, Methodology. Ani­
mesh Pal: Formal analysis, Writing – original draft. Bidyut Baran Saha:
Conceptualization, Methodology, Writing – review & editing,
Supervision.
Md.M. Rahman et al.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
Data will be made available on request.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.applthermaleng.2023.120581.
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