Journal of Environmental Chemical Engineering 8 (2020) 103702

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Journal of Environmental Chemical Engineering

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Removal of Cr (VI) from an aqueous solution using an activated carbon T

obtained from teakwood sawdust: Kinetics, equilibrium, and density
functional theory calculations.
Anyi Ramireza, Raúl Ocampob,*, Stephanie Giraldoa, Erika Padillab, Elizabeth Flóreza,*,
Nancy Acelasa,*
a
Group of Materials with Impact (Mat&mpac), Department of Basic Sciences, University of Medellín, Medellín, Colombia
b
Department of Chemical Sciences, Autonomous University San Luis Potosí (UASLP), San Luis Potosí, Mexico

ARTICLE INFO ABSTRACT

Keywords: Because of its acute toxicity and high mobility, the hexavalent chromium [Cr (VI)] found in wastewater is a risk
Hexavalent chromium to the environment. In this study, activated carbon was produced from teakwood sawdust, which was chemically
Adsorption modified using ZnCl2 (AT) as an efficient adsorbent for Cr (VI) removal from aqueous systems. Batch experi-
Kinetics ments were conducted to identify kinetic, diffusional, and equilibrium parameters. In addition, to better un-
Biomass
derstand the adsorption process, computer calculations were conducted based on the density functional theory
Computational simulation
(DFT). A maximum adsorption capacity of 72.46 mg g−1 was achieved by adapting experimental data to the
Langmuir isotherm model. Intraparticle diffusion was further identified through a three-dimensional diffusion
model, which revealed that it was ruled by intraparticular diffusion based on surface diffusion, with surface
diffusion coefficient (Ds) values ranging from 1.29 × 10−10 to 0.78 × 10−10 cm2 s−1. Finally, computational
chemistry calculations and an FTIR analysis determined that oxygenated functional groups, lactone, semi-
quinone, phenols, and carboxylic acids were involved in the process of Cr (VI) adsorption on AT. Moreover, the
main adsorption mechanisms were found to be complexation, electrostatic interaction, and reduction of Cr (VI)
to Cr (III).

1. Introduction
Chromium (Cr) is a widely used metal in metallurgical and chemical
industries, whose waste contaminates the surface and groundwater [1].
In water, Cr is stable as trivalent chromium, Cr (III), and hexavalent
chromium, Cr (VI). The latter specie is more toxic and produces carci-
nogenic effects owing to its high mobility in water and soil [2]. The
Environmental Protection Agency sets a maximum allowable limit of
0.1 mg L−1 for Cr in potable water. In contrast, in Colombia, the max-
imum allowable limit for Cr in drinking water is 0.05 mg L−1 [3] and
that for wastewater discharges is 0.5 mg L−1 [4].
There are various technologies that have proved efficient in the
removal or reduction of Cr (VI) from aqueous solutions, but the most
prominent ones include i) chemical methods [5,6]; ii) electrochemical
methods [7,8]; iii) photocatalytic methods [9,10]; iv) biological
methods [11,12]; and v) adsorptive methods.
From these methods, adsorption process using activated carbon has
become significantly more important due to its great efficiency and
lower costs when biomass are used as precursor. Enniya et al. [13]
investigated the elimination of Cr (VI) with activated carbon prepared
from apple peels at different pH and temperature obtaining a maximum
adsorption capacity of 36.01 mg g−1 at pH = 2. Besides the adsorption
process was endothermic and the adsorption kinetics were interpreted
with the pseudo-second order kinetic model. Yang et al. [14] studied
the kinetics, equilibrium and thermodynamics of Cr (VI) adsorption
onto activated carbon prepared from longan seed. The results revealed
that at pH = 3 and T = 318.2 K is maximized the adsorption capacity.
Additionally, it was corroborated that with a stirring speed higher than
170 rpm the effects of external mass transfer are discarded.
Mohan and Pittman [1] demonstrated that the adsorption of Cr (VI)
is influenced by i) the type of raw materials and activating agents used;
(ii) chemical and textural characteristics of activated carbons; and (iii)
the solution pH, since it affects the distribution of Cr species in the
solution and influences the behavior of functional groups existing on
adsorbent material surfaces.
From above, the literature suggests a variety of Cr (VI) adsorption

⁎
Corresponding authors.
E-mail addresses: raul.ocampo@uaslp.mx (R. Ocampo), elflorez@udem.edu.co (E. Flórez), nyacelas@udem.edu.co (N. Acelas).

https://doi.org/10.1016/j.jece.2020.103702
Received 5 November 2019; Received in revised form 10 January 2020; Accepted 14 January 2020
Available online 15 January 2020
2213-3437/ © 2020 Elsevier Ltd. All rights reserved.
A. Ramirez, et al.
mechanisms on activated carbon such as: i) reducing Cr (VI) to Cr (III),
ii) electrostatic attractions, and iii) ion exchange [15,16]. In an attempt
to clarify these aspects, Valentín-Reyes et al. [16] modified the acti-
vated carbon surface with several chemical and thermal treatments for
the removal of Cr (VI). The results evidenced that acid functional
groups of the activated carbon had an important effect on the hex-
avalent chromium removal and an anionic/reduction coupled adsorp-
tion mechanism was proposed. However, to explain the adsorption
mechanism present in Cr (VI) removal, it is important to understand the
surface functional groups, porosity development, surface area, and
pHPZC, along with the adsorption rate and adsorption capacity of the
adsorbent, which depend on the pH level, temperature, and ionic
strength of the solution. Thus far, few studies have focused on meti-
culously interpreting adsorption rates and detailing the complexation
mechanism of Cr (VI) and Cr (III) with the oxygenated functional
groups from the carbonaceous matrix. Computational chemistry based
on DFT calculations has been found to be an efficient tool, specifically
regarding this last item, as this tool can characterize interactions be-
tween cations or anions and oxygenated groups existing in carbonac-
eous matrices [17–19]. Note that the authors have not found compu-
tational studies describing HCrO4− and Cr3+ interactions with
oxygenated carbonaceous materials.
This paper seeks to study Cr (VI) adsorption equilibrium on an ac-
tivated carbon produced from teakwood sawdust. Teak wood is used by
both paper and furniture industry, since it is a light wood, easy to work
and offers high durability, so that every year a huge amount of teak tree
sawdust is extracted from commodity production. The Food and
Agriculture Organization of the United Nations (FAO) [20], reported
that, after processing, only 28 % of the original tree becomes sawn
timber and, the remainder 72 % being residues. It makes sawdust as a
potential precursor for the production of cost-effective activated
carbon. We investigate the effect of various important parameters on
the adsorption, such as, pH levels, contact time, adsorbent amount, and
initial Cr (VI) concentrations on the adsorption capacity. The interac-
tions between the adsorbent surface with Cr (VI) and Cr (III) are con-
firmed through a computational study. The controlling diffusional
mechanism is achieved by applying diffusion models that consider ex-
ternal mass transport, intraparticle diffusion, and adsorption on an
active site.
2. Experimental methodology
2.1. Preparation and characterization of materials
For the purposes of this study, the authors used teakwood sawdust
as a raw material from the Sena Calatrava of Itagüí (Antioquia). The
sawdust (sample T) was passed through a sieve with size of < 850 μm.
Subsequently, it was washed with distilled water, and dried for 12 h at
105 °C. This unmodified adsorbent is designated as T.
The sample T was chemically modified and pyrolized by using the
previously reported methodology [21]. Briefly, sample T was im-
pregnated with a 3 mol L−1 solution of ZnCl2 (T:ZnCl2 ratio of 1:4). The
mixture was left in contact for 24 h and then pirolized in a chamber
furnace for 30 min at 550 °C with a heating rate of 10 °C min−1. Next,
the sample obtained was washed for 3 h with 2 mol L−1 HCl, and then
with distilled water until reaching a pH level between 6 and 7. Finally,
the material obtained was ground and sieved a particle size ranging
from 0.074 to 0.15 mm, and labeled as AT. The yield of activated
carbon was 56 %.
A thermogravimetric analysis (TGA Q500, TA Instruments) was
applied to characterize the raw materials, to ascertain their moisture
content, volatile material (VM), fixed carbon (FC), and ash. Using the
ASTM D-5373-08 method (CHNSO TrueSpec® Micro, LECO), a basic
analysis was conducted. The surface area of the AT sample was calcu-
lated through the Brunauer, Emmett and Teller (BET) method, applied
to N2 adsorption data at 77 K obtained at P/P0 < 0.35 with an ASAP
2
Journal of Environmental Chemical Engineering 8 (2020) 103702
2020 Micrometrics equipment. The zero charge point pH (pHPZC), de-
fined as the condition under which the surface charge density of a so-
lution is equal to zero [22], was calculated using the solids addition
method [23]. The active functional groups were determined by Fourier-
transform infrared spectroscopy (FTIR) (with a spectrum two - Perki-
nElmer with UATR) for a range within 4000–450 cm−1. The acid and
basic groups were quantified by applying the acid–base titration
method, proposed by Boehm based on Goertzen et al.’s [24] metho-
dology, which applies the principle that oxygenated groups on coal
surfaces have different acidity levels and can be neutralized by bases at
different strengths.
2.2. Equilibrium and adsorption rate experiments
Batch experiments were conducted to determine the adsorption rate
and equilibrium of Cr (VI) on AT. By adding a K2Cr2O7 mass of 14.145 g
to a 1 L volume, a 5000 mg L−1 Cr (VI) solution was prepared, from
which synthetic Cr (VI) solutions were produced at different initial
concentrations (35, 50, 100, 170, 250, and 290 mg L−1). Next, 500 mL
of each solution, at pH 2 and 0.5 g of AT, was brought in contact with a
three-layer glass reactor placed in a constant-temperature bath at 25 °C.
The reactor was stirred at 200 rpm with a turbine propeller operated by
a rotor. Samples were taken at 30, 60, 120, 180, 300, 420, 1380, 1740,
2640, 3120, 4080, and 4320 min, until reaching equilibrium. For all
experiments, the total subtracted volume was guaranteed to not exceed
5 % of the total volume. The pH levels of the solutions were measured
regularly and held constant by adding drops of a 0.1 mol L−1 HCl so-
lution. The Cr (VI) concentration of each sample was measured twice,
based on the 1,5-diphenylcarbazide method [25] using a Shimadzu UV
1900 UV/VIS spectrophotometer at 542-nm wavelength. The reported
values were the averages of both readings.
The equilibrium point is defined as the time period in which no
significant concentration variations (< 2 %) were found for three
consecutive samples. In this study, the time required to reach equili-
brium was determined to be 72 h.
Experiments at different pH were similarly conducted, but the pH
level of the solution was adjusted to 2, 4, 6, 8, and 10 by using 0.1 mol
L−1 NaOH and 0.1 mol L−1 HCl solutions. The removal percentage of
Cr (VI) was estimated based on Eq. (1) and the adsorption capacity of Cr
(VI) was calculated using Eq. (2).
CA0 CA
%R= ×100
CA0 (1)
(CA0 CA )
qt = ×V
(2)
w
−1
where %R is the removal percentage of Cr (VI), CA0 (mg L ) is the
initial Cr (VI) concentration of the solution, CA (mg L−1) is the Cr (VI)
concentration at time t, qt (mg g−1) is the amount of Cr (VI) adsorbed at
time t, V (L) is the volume of the solution, and w (g) is the mass of the
adsorbent material.
2.3. Interpretation of adsorption kinetics based on kinetic and diffusional
models
The pseudo first-order (PFO) [26] and pseudo second-order (PSO)
[27] kinetic models, as well as diffusional models, were applied to as-
sess the mass transfer mechanism that controls the Cr (VI) adsorption
rate on AT. In the kinetic models, it is assumed that the overall rate of
adsorption is controlled by the adsorption rate of the solute on the
surface of the adsorbent, and the intraparticle diffusion and external
mass transport can be neglected. Moreover, it is considered that the
adsorption rate of a solute on the surface can be represented in the same
manner as the rate of a chemical reaction (chemisorption). The pseudo
first-order and pseudo second-order kinetic models have been ex-
tensively applied for describing the adsorption rate of several
A. Ramirez, et al.
Table 1
Equation of kinetic and diffusional models.
Nonlinear form
Pseudo First-Order qt = q e (1-e k1t) (3)
Pseudo Second-Order qe2k2t (5)
qt =
1+q ek2t
where k1 (min−1) is the pseudo first-order rate constant; qt and qe are the amounts of Cr (VI) adsorbed in time t (min) and in the equilibrium, respectively (mg g−1); and
k2 (g mg−1 min−1) is the pseudo second-order rate constant.
Diffusional model
dC
V A = mSkL (CA CAP |Bp s )
dt
t=0 CA = CA0 CAP =0 (9)
q = f(CAP) (11)
CAP : concentration of Cr (VI) within the particle (mg L ); CAP |Bp-s : concentration of Cr (VI) at the external surface of the particle (r = R) (mg L−1); Dep : pore volume
−1
diffusion coefficient (cm2 s−1); Ds : surface diffusion coefficient (cm2 s−1); kL : external mass transfer coefficient in liquid phase (cm s−1); m: mass of adsorbent (g); np-
s: unit normal vector on the surface at r = R; q: mass of adsorbed Cr (VI) predicted with the adsorption isotherm (mg g−1); S : external surface area per mass of
adsorbent (cm2 g−1), S = 3/R p ; V : volume of the solution (mL).
adsorbate-adsorbent systems [28–30]. Both models are represented in
linear and nonlinear forms in Eqs. (3)–(6) (Table 1).
The linear shape constants of PFO and PSO models were calculated
from the intercept and the graph slope of each model as follows. For the
PFO model, a Log (qe-qt) graph was developed as a function of time (t),
from which the values of qe and k1 were calculated. In addition, for the
PSO model, qe and k2 were calculated by plotting t/qt against t. To
calculate nonlinear shape constants of the kinetic models, the least
squares model derived from the Rosenbrock–Newton optimization al-
gorithm was applied through the Statistical software.
The experimental adsorption rate data were also interpreted
through a diffusional model, which considered external mass trans-
portation, intraparticle diffusion, and adsorption on the active site. This
model was developed by performing material balances in the solution
and inside particles, assuming that the particles were spherical and
isotropic and that external mass transportation could be modeled using
the external mass transfer coefficient, kL. On the other hand, inside the
particle, pore volume and surface diffusion mechanism were assumed.
Given these considerations, the general diffusion model is described by
Eqs. (7)–(10) (Table 1).
Eq. (7) represents the variation in Cr(VI) concentration in the so-
lution, and Eq. (8) denotes the evolution of Cr(VI) inside the particle.
The initial and boundary conditions (Eqs. (9)–(10)) indicate that, at the
beginning (t = 0), there was no Cr(VI) inside the particle pores and a
continuity of the mass flux at the external surface of the particle
(r = R).
The rate of adsorption on an active site is assumed to be in-
stantaneous; thus, local equilibrium existed between the Cr(VI) con-
centration in the solution inside the pore solution (CAP = CAe) and the
Cr(VI) mass adsorbed on the pore surface. This equilibrium is re-
presented by an adsorption isotherm, which is the mathematical rela-
tion between q and CAP (Eq. (11)).
The model represented by Eqs. (7)–(10) is the general diffusional
model (PVSDM), which can be simplified considering that the in-
traparticle diffusion can be controlled by either pore volume diffusion
model (PVDM) (Dep ≠ 0, Ds = 0) or the surface diffusion model (SDM)
(Dep = 0, Ds ≠ 0).
2.4. Computational simulation - DFT studies
In this study, quantum chemistry calculations were performed to
simulate HCrO4− and Cr3+ adsorption in carbonaceous materials, since
both ions were detected experimentally. All calculations were per-
formed with the Gaussian 09 software package [31] using the DFT-
B3LYP method and a 6–31+g (d, p) basis set. Geometry optimization
Journal of Environmental Chemical Engineering 8 (2020) 103702
Linear form
Log(q e qt ) =Logq e
k1
t (4)
2.303
t
=
1
+
t (6)
qt k2q e2 qe
(7) CAP q
+ p = (Dep CAP + Ds p q) (8)
p t t
np s (Dep CAP + Ds p q) = kL (CA CAP |Bp s) (10)
CA (12)
d
-V CA0
kL =
mS dt
t 0
calculations and vibrational frequency analysis were conducted by
taking into account the solvent effect, which considers long-range im-
plicit hydration by applying the integral equation formalism variant of
the polarized continuum model (IEFPCM). This model is based on a
“supermolecule” approach, which contemplates the water effects by
assuming that the species are surrounded by an H2O layer and a di-
electric continuum, based on the use of their dielectric constant [32].
IEFPCM is therefore used to estimate the total free energy in a solution
when non-electrostatic terms are included [33].
The local minimum potential energy values for each structure were
confirmed since imaginary frequencies did not occur. The interactions
of the anions with diverse carbonaceous surfaces were quantified after
Wiberg indexes were calculated with the NBO 6 package [34].
Simulations of carbonaceous surfaces were conducted based on the
proposals from Liu et al. [35]. The structure exhibits five benzene rings
merged at the top with unsaturated carbon atoms (for active sites) and
altered with a range of oxygen-containing functional groups, such as
carboxylic, lactone, semiquinone, and phenol groups, as shown in
Fig. 1.
The adsorption energy (Eads) produced by HCrO4− and Cr3+ on
carbonaceous surfaces was estimated as specified in Eq. (13):
Eads = E(Cr3+ or HCrO-4 )-surface - (E(Cr3+or HCrO-4) + Esurface) (13)
where E(Cr3+ or HCrO-4 )-surface is the total energy of the complex (HCrO4 or
Cr3+) and the carbonaceous surface. E(Cr3+or HCrO-4) is the total energy of
the HCrO4 or Cr3+ monomers, and Esurface is the total energy of the
oxygenated carbonaceous model.
3. Results and discussion
3.1. Characterization of the materials
Table 2 shows the physicochemical and textural properties of the
materials, where the contents of VM, FC, and ash are within the range
for different types of wood [21]. After a basic analysis, T was found to
be mostly composed of carbon (47.20 %). Therefore, it is an appropriate
raw material for obtaining activated carbon. From the N2 adsorption
isotherm the SBET surface area, pore diameter and pore volume for AT
were 999.65 m2 g−1, 2.55 nm and 0.63 cm3 g−1, respectively. There-
fore, this adsorbent can be classified as a porous activated carbon.
Table 3 records the pHPZC and the amount of acidic and basic groups
on the surface of AT. The pHPZC value of 6.30 indicates that if the pH
values are below 6.30, surfaces with positive charges can exist to pro-
mote HCrO4− adsorption by electrostatic attraction. If the pH values
are greater than 6.30, surfaces are negatively charged and OH−
3
A. Ramirez, et al.
Fig. 1. Oxygenated carbonaceous models.
competes with CrO42−, which could decrease the adsorption capacity of
AT to remove Cr (VI). A greater number of acid groups compared to the
basic groups were also noticed, and the carboxylic acids were found to
be up to 2.45 and 4.68 times more prevalent than lactones and phenols,
respectively.
FTIR analysis corresponding to T and AT samples are presented in
Fig. 2. Bands of around 3336 and 3200 cm−1 correspond to glucose
alcohol (CeOH) and the hydroxyl group (eOH) of the carboxylic acid
from the material cellulose [38]. The stretch in band 2916 cm−1 is
consistent with the long linear aliphatic chain (eCH2 and eCH3)
[38,39]. The intensity of these bands for AT decreases with T, which is
attributed to the degradation of hemicellulose and other components in
the wood cell wall as it has free hydroxyl and can absorb moisture [40].
The peak of the 1734 cm-1 band is consistent with carboxylic groups of
hemicelluloses (C]O) [39]. The bands at approximately 1235 and
1030 cm−1 correspond to groups of carboxylic acids or esters owing to
CeO stretches, and the stretching at 557 cm−1 corresponds to aromatic
groups (CeH). These bands exist in T, but almost fade away or dis-
appear completely in AT. A possible cause of this is high temperatures
Table 2
Chemical properties of teakwood sawdust.
Materials Moisture (%) Proximate analysis (Wt%)a
VM FC
T 5.02 83.92 15.67
MV: volatile material; CF: fixed carbon; N: nitrogen; C: carbon; H: hydrogen; O: oxygen; dp: pore size.
a
Dry basis.
b
Obtained by difference.
4
Journal of Environmental Chemical Engineering 8 (2020) 103702
that degrade the functional groups and transform them into CO and
CO2. Thus, hydrophilic radicals decrease with the development of the
aromatic structure [15]. The 1692 and 1582 cm−1 bands that become
steeper in AT are consistent with carboxylic groups (C]O) and aro-
matic rings (C]C), respectively [41]. The 1419 and 1366 cm−1 bands
correspond to stretches of the aromatic group (CeC) and alkane group
(CeH), respectively. The small band at 765 cm−1 pertains to the aro-
matic groups (CeH), which means that there is a greater condensation
of the material structure [42].
3.2. Adsorption experiments
The effect of pH on the removal efficiency of Cr (VI) using AT is
shown in Fig. 3. The figure shows that the percentage of chromium
removal is related to the pH level. When pH increases from 2 to 10,
adsorption decreases. At a pH level of 2, the highest percentage of Cr
(VI) removal is achieved (100 %). An explanation for this might be the
distribution of Cr species for different pH values [43] and surface
charges of AT. Under acidic pH conditions, HCrO4− ions predominate
Elemental analysis (Wt%)
Ash N C H Ob
0.41 0.12 47.20 5.70 46.98
A. Ramirez, et al. Journal of Environmental Chemical Engineering 8 (2020) 103702

Table 3
Chemical characteristics of AT.
Materials Carboxylic group (mmol g−1) Lactone group (mmol g−1) Phenol group (mmol g−1) Total acid sites (mmol g−1) Total basic sites (mmol g−1) pH (PZC)

AT 1.225 0.500 0.262 1.987 0.112 6.30

adsorption process, a preliminary experiment was conducted. The fol-

lowing adsorption conditions were evaluated: 100 mL of solution at
100 mg L−1 of Cr (VI) solution, a pH level of 2 with 0.1 g of T and AT, at
25 °C, with a stirring speed of 100 rpm and a contact time of 3 h (See
Fig. 2, Data in Brief). The removal percentages obtained for Cr (VI)
were 5 % for T and 40 % for AT. These results indicate that the acti-
vation process has a positive effect on Cr (VI) adsorption, with a re-
moval rate that is 8 times higher for AT than it is for T. This is due to
both porosity generation and functional groups formation on the ad-
sorbent surface (AT). With the aim to reach a removal percentage of Cr
(VI) less than 50 % a concentration of 100 mg L−1 for Cr (VI) was used.

3.3. Adsorption rate and equilibrium

In general, the interpretation of experimental data improves when

Fig. 2. FTIR spectra for T and AT materials.
and the AT surface is positively charged (pHPZC < 6.4), thus generating
an electrostatic attraction that favors Cr (VI) adsorption.
By increasing the pH level, the HCrO4− species gradually becomes
CrO42- and the protonation degree of the AT surface is weakened in the
presence of OH- ions, causing an electrostatic repulsion between AT and
the anion, which decreases its adsorption capacity. Therefore, all the
experiments were carried out at pH 2.
To assess the effect of biomass activation (T) on the Cr (VI)
using the PSO kinetic model (non-linear and linear), with correlation
coefficients R2 > 0.93, and values of qe quite close to the experimen-
tally determined values (qe exp) (Table S1). These results indicate that
chemisorption is the limiting process in the Cr (VI) adsorption rate for
AT. Similar results have been obtained previously, where the best fit for
experimental data corresponded to PSO kinetic models [28–30].
Table 4 shows the operating conditions used to obtain the con-
centration decay curves for the Cr adsorption on AT sample, and Fig. 4
displays the experimental data obtained for Exp. 1–4. This figure clearly
indicates that the experimental data evidenced a high concentration
drop at short times, and it slowly decreased until the equilibrium was
reached after approximately 4500 min. This behavior indicates that, for
short times, external mass transport dominates the overall adsorption

Fig. 3. a: Effect of pH level on the adsorption of Cr (VI) on AT; b: relative distribution in water of Cr (VI) species as a function of pH level and Cr (VI) concentration.
[Cr (VI) concentration: 20 mg L−1; pH = 2; adsorbent amount = 0.1 g of T and AT; Temperature =25 °C; stirring speed = 100 rpm; contact time = 3 h].

Table 4
Experimental conditions and mass transfer parameters corresponding to Cr (VI) adsorption on AT at 25 °C at a pH level = 2.
Exp. No. CA0 (mg L−1) qe (mg g−1) kL×104 (cm s−1) Dep (cm2 s−1) Ds (cm2 s−1)

1 35.7 33.6 2.6 1.037 × 10−6 1.29 × 10 −10

2 52.9 44.9 1.8 2.07 × 10 −7 0.79 × 10 −10

3 98.6 51.1 1.1 1.04 × 10 −7 1.11 × 10 −10

4 171.5 64.4 0.46 3.47 × 10 −8 0.78 × 10 −10

5 246.7 57.3 1.14 3.11 × 10 −8 1.14 × 10 −10

6 288.0 71.4 1.08 2.14 × 10 −8 1.16 × 10 −10

5
A. Ramirez, et al.
Fig. 4. Cr concentration reduction curves on AT. The dotted lines correspond to
the forecast calculated with PVDM.
rates, while for long times, adsorption rate could be governed by in-
traparticle diffusion. To respond to this hypothesis, the general diffu-
sion model, as denoted in Eqs. (7)–(10) (Table 1), was solved numeri-
cally by considering Dep→∞ and Ds→∞, which suggests that there are
no concentration gradients within the particle and that the exclusive
controlling stage is the external mass transportation (MTEM). Hence, it
is necessary to exclusively calculate the mass external transportation
coefficient, kL, to find a numerical solution for the model. In fact, this
value can be calculated from experimental data based on the procedure
proposed by Furusawa and Smith [44], which determines the initial
slope of the experimental data based on Eq. (12), as denoted in Table 1.
The obtained kL values, which range from 0.46 × 10− 4 to
2.6 × 10−4 cm s−1, are listed in Table 4. Fig. 5 shows the experimental
data, as an example, for Exp. 3 and forecast results based on the MTEM
model. It is evident that the model can only predict experimental data
for very short periods, but cannot interpret the curve inflection asso-
ciated with intraparticle diffusion. Furthermore, the model predicts that
equilibrium is reached after approximately 500 min, while, experi-
mentally, it is reached at 4500 min. This means that the model predicts
an adsorption rate that is nine times faster than the values calculated
Fig. 5. Concentration decay curve for the adsorption of Cr (VI) on AT for Exp. 3.
The dotted line corresponds to prediction of the general diffusion model with
Dep→∞ and Ds→∞.
6
Journal of Environmental Chemical Engineering 8 (2020) 103702
experimentally. This identical procedure was also executed for the re-
maining five experiments and a quite similar behavior was observed for
MTEM, which evidences that the external mass transport is not the
controlling stage of the overall adsorption rate.
Experimental data were interpreted based on previous results by
applying the general diffusion model. First, it was assumed that in-
traparticular diffusion is controlled by pore volume diffusion, where
Ds = 0. Therefore, to calculate the model results, only kL and Dep values
were required. Table 4 provides the values of kL. Meanwhile, the value
of Dep was calculated by fitting the model to experimental data and
minimizing the following objective function:
t end
error= (CAexp –CAnum )2dt (14)
t = 0 min
The numerical solution was determined with a commercial software
based on finite-element subroutines. We ensured that numerical solu-
tions were independent and consistent with the grid mesh employed.
Other numerical aspects employed were set by the default software
configuration.
Fig. 4 presents the prediction of the PVDM model to the experi-
mental data, while Table 4 records the optimal values of Dep. It is re-
markable in the figure that the model satisfactorily predicts the ex-
perimental data, however, it can be observed that the values of Dep
increased exponentially by augmenting the mass adsorbed at equili-
brium, which lacks of physical meaning, since Dep is a function of the
textural properties of the material (porosity and tortuosity) and not of
the adsorbed mass as shown in Eq. (15), therefore its value should re-
main almost constant with the operating conditions of the system.
DAB p
Dep =
(15)
where DAB: molecular diffusion coefficient at infinite dilution (cm s ) 2 −1
and : tortuosity factor.
Moreover, considering that the value of Cr (III) ionic diffusivity is
DCr3+ = 1.22 × 10−5 cm2 s−1 [45] and that the εp value for AT sample
is 0.60, the tortuosity factor values can be estimated using Eq. (15),
which yields values of 7 ≤ τ ≤ 342. This demonstrates that Dep values
are not physically significant, thus indicating that Cr intraparticular
diffusion of pores is not controlled by pore volume diffusion.
Surface diffusion refers to the movement of adsorbate molecules
along the pore surface of AT, and its driving force is the surface con-
centration gradient, q [46]. To confirm its influence, experimental data
were interpreted through the MDS model, assuming Dep = 0. The Ds
optimal values were calculated similarly as the Dep values for PVDM
Fig. 6. Concentration decay curves of Cr (VI) on AT. The dotted lines corre-
spond to the SDM model prediction.
A. Ramirez, et al.
Fig. 7. Evolution of intraparticular profiles, CAP and flux direction, for Exp. 1 at periods of (a) 1, (b) 5, (c) 10, (d) 20, and (e) 40 h.
and the prediction of MDS model is depicted in Fig. 6 for Exp. 1–4,
while the optimal values of Ds are reported in Table 4.
It is remarkable in this figure that the MDS model matches quite
well the experimental data for short times as well as long times.
Furthermore, contrary to the Dep values, the Ds values vary only from
1.29 × 10−10 to 0.78 × 10−10 cm2 s−1, which is due to the variations
of q in each experiment, evidencing that the overall adsorption rate of
Cr on AT carbon is better predicted when applying a surface diffusion
model.
Fig. 7 shows the evolution and direction of the concentration gra-
dients of Cr within the particle at times of 1, 5, 10, 20 and 40 h. It is
evident as time increases the Cr ions diffuse toward the center of the
particle, and after a long period, intraparticular concentration gradients
disappear after reaching equilibrium.
Finally, in Fig. 8, the evolution of the surface flux magnitude, NAS
(mass transport due to surface diffusion, mg cm−2 min−1), is estimated
through Eq. (16) for Exp. 1 as a function of position and time. Here, the
maximum values of NAS are found near the external surface of the
particle, at shorter periods, because at these positions, the greatest
gradients of q occur. Over time, the external part starts to saturate,
7
Journal of Environmental Chemical Engineering 8 (2020) 103702
leading to a gradual decrease in NAS. Therefore, at longer periods, the
highest values of NAS shift towards the q gradient, in other words, to-
ward the particle center.
NAS = Ds q (16)
p
3.4. Adsorption isotherms
Langmuir [47], Freundlich [48], and Temkin [49] isothermal
models were applied to model the equilibrium data of Cr (VI) adsorp-
tion onto AT. These models are mathematically represented by Eqs.
(17)–(19) (Table 5), respectively.
It is feasible to calculate different equilibrium constants, as defined
in isotherms from the intercept and the slope of the graph of each
model: when plotting Ce/qe based on Ce, KL and q (Langmuir constants)
can be calculated. When plotting Log qe against Log Ce, KF and 1/n
(Freundlich constants) are estimated. By plotting qe against Ln Ce, KT
and b (Temkin constants) are calculated. If the values are within the
0.1 < 1/n < 1 range of the Freundlich constant, there is a favorable
adsorption process. In addition, the b < 8 kJ mol−1 values (the Temkin
A. Ramirez, et al. Journal of Environmental Chemical Engineering 8 (2020) 103702

Fig. 8. Evolution of NAS as a function of the position and time for Exp. 1. (a) 1, (b) 5, (c) 10, (d) 20, and (e) 40 h.

Table 5
Isotherm models employed to interpret the adsorption equilibrium of Cr over
AT.
Langmuir Ce
=
1
+
Ce (17)
qe qm KL qm
Freundlich Logq e =LogKF +
1
LogCe (18)
n
Temkin qe =
RT
LnKT +
RT
LnCe (19)
b b
Separation factor RL=
1 (20)
1+ KL CA0

Ce and qe represent the Cr (VI) concentration at equilibrium (mg L−1) and the
amount of Cr (VI) adsorbed at equilibrium (mg g−1), respectively. qm (mg g−1)
is the maximum adsorption capacity; KL (L g−1) is the Langmuir constant; KF
(mg g−1) is the multilayer adsorption capacity and 1/n is a constant linked to
the adsorption intensity; b (kJ mol−1) is a constant related to adsorption heat;
KT (L g−1) is the Temkin constant; T (K) is the temperature; R (0.008314 kJ
mol−1 K−1) is the gas constant; RL: separation factor (dimensionless).

constant) demonstrate the existence of physical interactions, through

which adsorbate–adsorbent interactions similar to the Van Der Waals
interaction [15] can be estimated.
In Fig. 9, Cr (VI) adsorption isotherms for the Langmuir, Freundlich, Fig. 9. Cr (VI) adsorption isotherms on AT (solution volume 500 mL, adsorbent
and Temkin models are denoted. Here, concave isotherms are observed, dose 0.5 g, temperature 25 °C, stirring speed 200 rpm, and contact time 72 h).
thus evidencing a good level of Cr (VI) adsorption on AT and a good fit
for the experimental data from the three models, which aligns with the

8
A. Ramirez, et al. Journal of Environmental Chemical Engineering 8 (2020) 103702

Table 6
Langmuir, Freundlich, and Temkin isotherm parameters.
Langmuir Freundlich Temkin

−1 −1 2 −1 2
qm (mg g ) KL (L mg ) R RL KF (mg g ) 1/n R KT (L g−1) b (kJ mol−1) R2

72.46 0.121 0.9918 0.028–0.188 34.79 0.125 0.9568 180.9 0.388 0.9158

correlation coefficients obtained from Table 6 (R2 > 0.91).
The good fit of the experimental data to the Langmuir model allows
for the determination of the maximum adsorption capacity
(72.46 mg g−1) and indicates that, at equilibrium, adsorption corre-
sponds to the monolayer, with a homogeneous surface with a fixed
number of active sites with the same Cr (VI) affinity. Nevertheless, a
good fit of the experimental data to the Freundlich model is observed,
which accounts for the interactions on multilayer heterogeneous sur-
faces, which have different affinities and interaction energies between
active sites of the surface and the pollutant. This model helps in pre-
dicting a favorable adsorption process, as 1/n < 1 [50]. Furthermore,
adjustment to the Temkin model shows that the Cr (VI) adsorption heat
on a layer decreases linearly with the surface coverage due to interac-
tions between AT and Cr (VI), where adsorption is characterized by a
uniform distribution of bond energies. Additionally, a value of
b = 0.388 kJ mol-1 reveals that there is a weak physical Van der Waals
interaction. Hence, there are several interactions between Cr (VI) and
AT and a combination of adsorption mechanisms.
In addition, according to Eq. (20) (Table 5), the separation factor RL
(dimensionless) can be determined, which helps to predict whether the
adsorption process is irreversible (RL = 0), favorable (RL < 1), linear
(RL = 1), or unfavorable (RL > 1) [51]. As denoted in Table 6, RL values
range from 0.028 to 0.188, which means that the Cr (VI) adsorption
process, using AT as an adsorbent material, is favorable [51]. These
results match some literature reports for Cr (VI) adsorption. For ex-
ample, Cherdchoo et al. [52] used coffee and tea waste to adsorb Cr (VI)
and found RL to range between 0.031 and 0.082. Therefore, their ad-
sorption conditions are optimal for Cr (VI) adsorption.
3.5. Comparison with other adsorbents
Table 7 exhibits the maximum adsorption capacity (qm) of Cr (VI) by
AT, compared to the capacity of other adsorbents described in the
scientific literature. It can be observed that materials treated with ZnCl2
evidence better adsorption capacities than those treated with other
treatments, and that the AT capacity obtained in this study is com-
parable to those reported previously. This proves that the activated
carbon produced in this study by chemical activation with ZnCl2 (AT)
has great potential as a Cr (VI) adsorbent on aqueous solutions.
3.6. Computational results
3.6.1. Adsorption modes and establishment of basal-state multiplicity
Zhao et al. [55] found that, through molecular modeling, the
interaction of CrO2-4 and a carbonaceous surface is produced with two
adsorption modes: a) ion complexation with the surface and b) for-
mation of H bonds among OeH oxygenated groups on the surface and O
atoms of CrO2-4 . Based on these results, for interactions between HCrO4
and the carboxylic and phenolic groups, two interaction modes were
modeled (Fig. 10): a) interaction with H from the functional group and
b) interaction with the carbonaceous surface. For lactone and semi-
quinone groups, only interaction with the carbonaceous surface was
studied (Fig. 10). For Cr3+, only one mode of adsorption was assessed:
interaction with a carbon from the carbon surface close to the func-
tional group (Fig. 10).
To determine the multiplicity of the fundamental state, optimiza-
tions were applied to several spin (M) multiplicities for each structure
(Fig. 11). For complexes (carbonaceous surface - HCrO4 ), the interac-
tion basal states with lactone, phenol (a and b), and carboxylic-a
functional groups were found to be two. Regarding interaction with the
semiquinone functional group, the basal state was 1, and for carboxylic-
b, it was 4. For Cr3+ adsorption, the basal state exhibited 5, 6, 7, and 5
multiplicities for the lactone, semiquinone, phenol, and carboxylic
functional groups, respectively. Based on these results, this study fo-
cused on electronic basal state structures for each case.
3.6.2. Characteristics of the most stable structures
In Table 8, Gibbs electronic and free adsorption energies are pre-
sented, along with geometric parameters and the Wiberg index for the
most stable structures produced in the interaction between HCrO4 and
the oxygenated carbonaceous surface. Based on the geometric data
obtained from the table, we conclude that there is an average distance
of 1.32 Å between the O atom of the anion (HCrO4 ) and the C atom of
the carbonaceous surface for structures containing lactone, semi-
quinone, and carboxylic-b. For the structure with phenol-b, the distance
was smaller (1.24 Å). For phenol-a and carboxylic structures, the dis-
tance between the O atoms of HCrO4 and the H atom of the functional
group was approximately 1.65 Å. In addition, the Wiberg index was
calculated to determine the interaction degree between the anion and
the carbonaceous surface. Although there were interactions in all cases,
it was found that, for the anion adsorption mode on the carbonaceous
surface, the value was approximately 10 times greater than that for
modes where the anion interacts with the H atom from the functional
group. In fact, only the phenol-b structure exhibited greater differences.
In all cases, the interaction between the anion and the different oxy-
genated groups was thermodynamically favorable. The carbonaceous
surface interaction was more favorable for phenol and carboxylic
functional groups than for the OeH group of the functional group,

Table 7
Comparison of maximum adsorption capacities.
Precursor material Treatment pH qm (mg g−1) References

AT Chemical activation with ZnCl2 2.0 72.46 This study

Eucalyptus globulus bark Pyrolysis 2.0 21.30 [53]
Apple peels Chemical activation with H3PO4 2.0 36.10 [13]
Rubber wood (Hevea brasiliensis) None 2.0 4.87 [28]
Sterculia guttata shell Chemical activation with ZnCl2 2.0 90.90 [54]
Bael fruit shell (Aegle marmelos strap) Chemical activation with H3PO4 2.0 17.27 [39]
Activated charcoal None 4.0 12.87 [36]
Activated alumina None 2.0 7.44 [36]
Nutshell Chemical activation with ZnCl2 2.0 43.45 [30]

9
A. Ramirez, et al.
Fig. 10. Optimized structures of the most stable configurations for Cr3+ and HCrO4 .
where chemisorption and physisorption, respectively, occurred. The
electronic adsorption energy trend was phenol-b > semiquinone >
carboxylic-b > lactone > phenol-a > carboxylic-a.
The sign of Gibbs free energy was used to determine the spontaneity
of adsorption processes [56–58]. If there are negative values, this
means that the process occurs spontaneously. Considering this, we can
conclude that the adsorption process of HCrO4 on carbonaceous sites is
10
Journal of Environmental Chemical Engineering 8 (2020) 103702
spontaneous. However, the adsorption by the H atom of the phenol and
carboxylic OeH functional groups is not spontaneous.
Table 9 lists the parameters applied for the characterization of the
most stable adsorption configurations of Cr3+. Distances between Cr3+
and the surface carbon do not fluctuate based on the functional group,
as can be noticed, and are approximately 2.07, while the Wiberg in-
dexes range between 0.51 and 0.68. Note that, in all cases, the
A. Ramirez, et al. Journal of Environmental Chemical Engineering 8 (2020) 103702

Fig. 11. Spin multiplicity (M) for the optimization of I) Cr 3+and II) HCrO4 relative to the most stable structure in each case.

Table 8 Table 10
Adsorption electronic (Eads) and Gibbs free (Gads) energies in (kcal mol−1), Vibrational frequencies predicted of the most stable configurations for each ion
geometrical parameters in Å, and Wiberg index of the most stable configura- (Cr3+and HCrO4 ) adsorbed.
tions for HCrO4 adsorbed.
Vibrational mode *Wavenumbers (cm−1)
Structure Eads Gads Distances Wiberg index
Before After
d(Csur_O) d((O-H)suf_O) (Csur_O) ((O-H)sur_O)
Cr3+ HCrO4−
Lactone −60.52 −35.36 1.32 1.16
Semiquinone −93.70 −59.00 1.32 1.17 C]O stretching:
Phenol-a −11.80 9.97 1.64 0.11 Lactone 1719 1576 1733
Phenol-b −94.70 −66.30 1.24 1.62 Semiquinone 1610 1282 1635
Carboxylic-a −8.10 13.30 1.66 0.10 Carboxylic-b 1641 1502 1709
Carboxylic-b −64.45 −37.50 1.33 1.13
OeH stretching:
Phenol-b 3635 3583 3782
Carboxylic-b 3609 3552 3760

interaction of Cr3+ with an O atom of the functional group was char-

* A scale factor of 0.9614 [60] was used to convert the harmonic vibrational
acterized by distances ranging from 1.88 to 2.09 and Wiberg indexes frequencies (ω) to the fundamentals frequencies (ν) observed experimentally.
ranged from 0.08 to 0.48. Furthermore, the data include that, in all
cases, the adsorption process is thermodynamically favorable and is a
spontaneous process fostered by the existing functional groups.
Table 10 denotes the calculated vibrational frequencies for C]O
stretching and OeH stretching before and after the adsorption process
for the lactone, semiquinone, carboxylic-b, phenol-b, and carboxylic
functional groups, respectively. A shift of these bands is noticed in both
species, which has been proven experimentally, and accounts for the
complexation mechanism between the anion and surface functional
groups [59].

3.7. Description of the adsorption process

The Cr (VI) adsorption process on AT was analyzed using FTIR

spectroscopy, computational chemistry calculations, and the diffusional
model. Fig. 12 denotes the AT FTIR spectra before and after the ad- Fig. 12. FTIR spectra of AT before and after the adsorption process. AT: acti-
sorption process. As it can be observed, for the Cr (VI) adsorbed on AT, vated teak before adsorption; AT-Cr (VI): activated teak after adsorption of Cr
an increase in band intensity for the eOH group is evidenced at ap- (VI).
proximately 3330 cm−1, which explains the formation of a H bond for
the OH group of the phenol or group carboxylic acid, and their inter-
action with an O atom of the HCrO4- species. The fact that signal

Table 9
Adsorption electronic and Gibbs free energies (kcal mol−1), geometrical parameters (Å), and Wiberg index of the most stable configurations of Cr3+ adsorbed.
Structure Eads Gads Distances Wiberg index

d(Cr_Csur) d(Cr_Osur) (Cr_Csur) (Cr_Osur)

Lactone −142.81 −121.26 2.09 1.98 0.68 0.32

Semiquinone −150.90 −130.72 2.07 1.90 0.61 0.48
Phenol −151.42 −132.12 2.08 2.22 0.51 0.08
Carboxylic −146.69 −123.81 2.06 1.88 0.71 0.36

11
A. Ramirez, et al. Journal of Environmental Chemical Engineering 8 (2020) 103702

Table 11 According to computational and experimental results, Fig. 13 shows

Cr (VI) and Cr (III) concentrations in solutions after equilibrium in the Cr ad- a proposal for the adsorption reactions during the removal of Cr (VI) on
sorption process. activated carbon. The most favorable adsorption (Eads) modes were
CA0 (mg L−1) Cr total (mg L−1) Cr (VI) (mg L−1) Cr (III) (mg L−1) represented.

35.7 7.40 0.00 7.40 4. Conclusions

52.9 16.09 7.95 8.14
98.6 59.45 47.50 11.95
intensity shifts and decreases at 1692 cm−1 denotes the interaction
between Cr (VI) and the carbonyl group in lactones, semiquinones, and
carboxylic acids. However, interactions with semiquinones
(e93.70 kcal mol−1) and carboxylic acids (e64.45 kcal mol−1) are fa-
vored due to their greater adsorption energy. Nevertheless, the dis-
placement and decreasing intensity recorded at 1235 cm−1 corresponds
to the interaction with the phenol.
Such results match the band straps found in simulated frequencies
calculated by computational chemistry, which shows that Cr (VI) is
adsorbed on the AT surface by complexation and hydrogen bridge in-
teractions [55]. Another mechanism proposed to remove Cr (VI) from
aqueous solutions using adsorbent materials is the reduction of Cr (VI)
to Cr (III) principally by interaction with oxygenated functional groups
and the subsequent adsorption of Cr (III) through complexation [59].
To corroborate this mechanism, in this study, a total chromium analysis
was conducted for the solution after reaching adsorption equilibrium,
thus verifying the presence of Cr3+ (Table 11). Nevertheless, the
computational results indicate thermodynamic favorability for adsorp-
tion of this species on AT.
The results demonstrate that activated carbon made from teakwood
waste exhibited high adsorption capacity toward Cr (VI) in an aqueous
solution, attaining an adsorption capacity of 72.46 mg g−1.
Furthermore, when increasing the pH level of the solution, this ad-
sorption capacity gradually decreased because of the existence of re-
pelling electrostatic attractions. The diffusion model corroborated that
the Cr (VI) adsorption rate is not ruled by external mass transportation,
but by intraparticular diffusion based on surface diffusion. The Ds va-
lues identified fluctuated from 1.29 × 10−10 to 0.78 × 10−10 cm2 s−1.
Based on the computational chemistry calculations and FTIR analysis, it
can be stated that the main mechanisms that exist in the Cr (VI) ad-
sorption process on AT are i) complexation, ii) electrostatic interac-
tions, and iii) reduction of Cr (VI) to Cr (III). In such cases, oxygenated
functional groups such as lactone, semiquinone, phenols, and car-
boxylic acids are mainly responsible for these processes.
CRediT authorship contribution statement
Anyi Ramirez: Conceptualization, Methodology, Investigation,
Software, Formal analysis, Data curation, Writing - original draft,
Visualization. Raúl Ocampo: Conceptualization, Software, Validation,
Writing - review & editing. Stephanie Giraldo: Methodology,

Fig. 13. Adsorption reactions during the removal of Cr (VI) on activated carbon.

12
A. Ramirez, et al.
Investigation. Erika Padilla: Software, Validation. Elizabeth Flórez:
Conceptualization, Software, Validation, Writing - review & editing,
Funding acquisition. Nancy Acelas: Conceptualization, Methodology,
Validation, Writing - review & editing, Visualization, Supervision,
Funding acquisition.
Declaration of Competing Interest
None.
Acknowledgments
The authors are grateful to Colciencias for financing the project
120677757983, CT-648-2018. A Ramirez thanks to Universidad
Autónoma San Luis Potosí for allowing the research internship.
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