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Modelling studies for remediation of Cr (VI) from wastewater by activated Mangifera

indica bark

Deepak Pathania, Arush Sharma, A.K. Srivastava

PII: S2666-0865(20)30037-0
DOI: https://doi.org/10.1016/j.crgsc.2020.100034
Reference: CRGSC 100034

To appear in: Current Research in Green and Sustainable Chemistry

Received Date: 29 June 2020

Revised Date: 4 September 2020
Accepted Date: 12 October 2020

Please cite this article as: D. Pathania, A. Sharma, A.K. Srivastava, Modelling studies for remediation of
Cr (VI) from wastewater by activated Mangifera indica bark, Current Research in Green and Sustainable
Chemistry, https://doi.org/10.1016/j.crgsc.2020.100034.

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Modelling studies for remediation of Cr (VI) from wastewater by activated
Mangifera indica bark

Deepak Pathaniaa* Arush Sharmab and A.K. Srivastavac

a*
Department of Environmental Sciences, Central University of Jammu, Bagla (Rahya Suchani),
Samba, J&K – 181143
b
Department of Chemistry, Baddi University of Emerging Sciences and Technology (BUEST),
Solan, Himachal Predesh, India-173205
c
Faculty of Engineering & Technology, Veer Bahadur Singh Purvanchal University, Jaunpur

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(UP)-222003, India

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Graphical Abstract

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Modelling studies for remediation of Cr (VI) from wastewater by activated
Mangifera indica bark

Deepak Pathaniaa* Arush Sharmab and A.K. Srivastavac

a*
Department of Environmental Sciences, Central University of Jammu, Bagla (Rahya Suchani),
Samba, J&K – 181143
b
School of Sciences, Baddi University of Emerging Sciences and Technology (BUEST), Solan,

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Himachal Predesh, India-173205
c

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Faculty of Engineering & Technology, Veer Bahadur Singh Purvanchal University, Jaunpur
(UP)-222003, India

Abstract -p
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Activated bark prepared from Mangifera indica was used for the removal of Cr(VI) from
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aqueous solution. Activated bark (AB) was characterized by some instrumental techniques such
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as Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and

thermal analysis (TGA). The effect of different adsorption parameters such as metal ion
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concentration, adsorbent dosage, contact time, pH, and the temperature was optimized.
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Langmuir, Freundlich, and Tempkin's isotherms were studied for the interpretation of

experimental data. Langmuir model was found to be best fitted with a maximum adsorption

capacity of 78.96 mg/g. The kinetic study was described by pseudo-first-order kinetics and

Elovich model. Kinetic study indicates that physio-adsorption play major role in Cr(VI) removal

from water system. The thermodynamic parameters such as energy change (ΔG°), enthalpy

change (ΔH°) and entropy change (ΔS°) were found to be spontaneous, feasible, and

endothermic nature.
Keywords: Bark, Activation, Cr(VI), Adsorption, Isotherm, Kinetics, Thermodynamics

Running title: Removal of Cr (VI) from wastewater by activated Mangifera indica

bark

No. of words (Abstract): 129

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No. of words (Text): 5108

No. of tables: 3
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No. of figure: 5
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Corresponding authors:
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Deepak Pathania, Department of Environmental Sciences, Central University of Jammu, Bagla

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(Rahya Suchani), Samba, J&K – 181143, E-mail: dpathania74@gmail.com; Tel:

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+919805440648

1.Introduction

Recently, natural water resources are polluted by different contaminates due to industrialization

and urbanization. Industrial effluent containing varieties of toxic organic and inorganic pollutants

are generally released into the aquatic system. The main sources of these pollutants into the

water system are mining, metallurgical, chemical manufacturing, tannery, battery manufacturing

industries, fossil fuel, chemical industries, etc (1-2). Inorganic pollutants are also known as

heavy metals due to their high atomic weight and high density. Heavy metals are quite dangerous
and poisonous even at low concentrations. Heavy metals enter into the water system from

different sources such as coal, natural gas, metal plating industries, leather industries, pulp, and

paper mill, etc. Heavy metals possess a stern detrimental effect on human health (3-4). Heavy

metals are not biodegradable and potentially hazardous to living beings hence their

concentrations required to be reduced to acceptable limits before release into water bodies.

Chromium exists in the environment primarily in two oxidation states such as trivalent

chromium, Cr(III), and hexavalent chromium, Cr(VI). The toxicity of chromium varies greatly

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with its compounds, oxidation state, and solubility in water (5). Cr(III) is considered an essential

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dietary element to humans and mammals while chromium(VI) is highly toxic, mutagenic, and
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carcinogenic (6). However, in the presence of oxidizing impurities, the less toxic trivalent
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chromium can be easily oxidized to hexavalent chromium. Chromium inters into the water
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bodies from effluents of various industries such as paints, electroplating, metal finishing, and
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leather tanning (7-8). Cr(VI) compounds are carcinogenic and long term exposure causes nausea,

ulceration, skin sensitization, and kidney damage (9-10). The permissible level permitted of
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hexavalent chromium in wastewater and drinking water is 0.1 mg/L and 0.05 mg/L, respectively
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(11). To reduce the environmental risk of Cr (VI), wastewater should be before discharged into

aquatic systems. Therefore, considerable attention has been paid for the effective removal of

chromium at low concentrations form contaminated water.

Several methods have been used for the removal of heavy metals from aqueous solutions such as

chemical precipitation, chemical oxidation and reduction, ion exchange, filtration, and

electrochemical treatment (12-16). However, these methods have some disadvantages as

incomplete removal of metals, high energy requirements, the requirement of expensive

equipment, generation of toxic sludge or waste, etc. (17). This has motivated the development of
alternative low-cost techniques for the removal of heavy metals from wastewater. Adsorption is

extensively used for the removal of heavy metals from the aqueous solution because it is a more

efficient, cost-effective, cleaner, and easy controlled process (18). However, reasonable

operation cost for the use of low-cost adsorbents has drawn interest in the use of the adsorption

process for the removal of heavy metals. Many agriculture byproducts like sawdust, rice husk,

nut and walnut shells, eucalyptus bark, and wheat bran have been explored as potential

adsorbents for the removal of Cr(VI) from wastewater (19-23). The bark is usually considered as

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waste material in timber processing, and its disposal is a major challenge due to high volumes.

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The bark is either left in the forest after tree felling or used as a fuel. Large amounts of bark are
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found in pulp mills, primary wood processing mills, and small-sized wood processing units.
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About 68.1% of chromium was removed from synthetic solution using Acacia Nilotica bark as an
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adsorbent (24). It comprises electron-rich functional groups which are active sites for heavy
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metals. Due to abundance, renewable and low-cost barks are used as appearing as excellent

alternatives to activated carbon for industrial applications. Moreover, barks show good
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adsorption capacity metals even at low concentrations (below 100 ppm) and their reductive
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ability is important for removal of chromium (VI) from water (25-26).

The biosorption process involves s mechanisms such as ion exchange, chelation, adsorption, and

diffusion (27). The ion-exchange or complex formation mechanisms have been used to explain

metal-binding onto barks (28). The functional groups such as hydroxyl and carboxyl groups on

the bark lose the associated proton and behave as an acid, while other groups, such as carbonyl,

behave as a base due to electronegative oxygen atom. The carboxylic acid groups are majorly

involved in metal adsorption by biomass, followed by hydroxyl group, aromatic rings, and amine

group (29).
The disadvantages associated with the use of bark for the removal of heavy metals due to the

reason that the natural organic complexation agents such as tannins, soluble enough to be

released significant concentrations and stabilize contaminants in solution rather remove them

(30). Therefore, several modification techniques have been studied to reduce organic

components of natural adsorbent and increased adsorption capacity (31).

In this study, we extensively studied the modification of a natural adsorbent (pine bark) with

NaOH reagent for Cd removal which was intended to benefit the NaOH destroying effect on

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organic components in barks.

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This paper reports the activated bark of Mangifera indica based adsorbent for the removal of
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Cr(VI) from the water system. It has been characterized by different techniques such as Fourier-
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transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and
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thermogravimetric analysis (TGA). The effect of different parameters such as concentration, pH,
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contact time, temperature, and adsorbent dose for the removal of Cr(VI) was explained. The

adsorption data were analyzed using various equilibrium isotherms models like Langmuir and
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Freundlich isotherms. The kinetics, thermodynamics models were also performed to determine
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the possible mechanism of adsorption.

2. Materials and methods

2.1. Materials
Potassium dichromate (K2Cr2O7), sodium hydroxide (NaOH), hydrochloric acid (HCl), sodium

hypochlorite (NaClO), diphenylcarbazide and nitric acid (HNO3) were purchased from Sigma

Aldrich Pvt. Ltd. India. The stock solution of metal ion (1000 mg/L) was prepared by dissolving

the required amount of metal nitrate in double-distilled water. All glasswares were cleaned and
rinsed with deionized water and dried in an oven at 50 to 55 °C before use. The working

solutions were prepared from the stock solution using double distilled water.

2.2. Collection of bark

The bark of mango (Mangifera indica L.) was collected from the Central University of Jammu,
India where it is available in abundance. It was washed firstly with tap water followed by
distilled water to remove the impurities. Then, it was dried for seven days in a shaded
atmosphere. The collected material was washed, dried, and powdered. The powder and finally
dried in an air oven at 60-65ºC for 12 h. It was stored in an airtight plastic container for further

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use.

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2.3. Activation of powered bark

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In this, 25 g of powdered bark of Mangifera Indica was soaked in 200 mL of 0.5M HCl at room

temperature for 6 hrs with shaking. Now, the mixture was filtered and washed with distilled
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water several times until the pH of the filtrate reached neutral. The power was dried in an oven at
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60 ℃ to constant weight. After drying, the material was sieved (60–200 mesh screens) and stored
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in a desiccator until use. The obtained mass was donated as activated bark (AB).
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2.4. Batch adsorption studies

The adsorption of Cr(VI) from the aqueous system was studied using batch adsorption
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experiment. Typically, 50 mg/L adsorbent (activated bark) was taken into the 100 mL aqueous

solutions of Cr(VI) in 250 mL of Erlenmeyer flasks. Mixtures were stirrer on a magnetic stirrer

for definite contact time. The pH of the adsorbate phase was adjusted by adding a few drops of

0.1N HNO3 or 0.1N NaOH. At a predetermined time, flasks were withdrawn and centrifuged at

5500 rpm for 10 min to remove the adsorbent particles from the aqueous phase. The samples

were filtered using Whatman no 41 filter paper and the filtrate was analyzed for residual Cr (VI)

concentration with UV-Visible spectrophotometer using 1,5-diphenylcarbazide at λmax of 540

nm (32). The adsorption experiment was carried out at different Cr(VI) concentration, pH,
reaction times, reaction temperatures, and different adsorbent doses. The adsorption capacity; qe

(mg/g) of adsorbent was determined equation as mentioned below:

= (1)

Where, Ci and Ce are initial and equilibrium concentrations (mg/L), respectively, qe (mgg-1) is the

equilibrium adsorption capacity, V is the volume of solution (mL) and M is the mass of

adsorbent (g). The percentage removal of Cr(VI) was calculated using the following equation:

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(2)

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Where Ci and Ce (mg/L) are initial and final concentrations of Cr(VI) before and after adsorption.
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The quantity of Cr(VI) adsorbed at time t, qt (mg/g) was calculated as follow:
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(3)
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Where, Co and Ct (mg/L) are the Cr(VI) concentrations at initial and at time t, respectively.
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2.5. Characterization techniques

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The concentrations of Cr(VI) in aqueous phase using a double beam UV-visible (UV-Vis)
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spectrophotometer. pH measurements were done using a Systonic pH meter. Fourier transform

infrared (FTIR) spectra of materials before were recorded by KBr pallet using Perkin Elmer-

Spectrum RX-IFTIR spectrophotometer in the range between 4000cm-1 and 350 cm-1.

The morphology of samples was studied over scanning electron microscope (SEM) using JEOL-

JSM-7001F instrument. SEM scans the surface of sample with high energy beam of electrons.

These electrons interact with atoms to produce the signals and signals contain essential

information such as topographical and chemical compositions. The accelerated electrons in SEM

have kinetic energy. This energy is dissipated as a variety of signals. These signals possess
secondary and back scattered electrons that produces microscopic SEM images that is used for

surface imaging.

TGA of samples was carried out using Perkin Elmer TGA-7 system. Thermogravimetric

analyzer continuously measures mass and temperature of a sample is changed over time. Mass,

temperature and time are considered as base measurements in TG analysis. Thermogravimetric

analyzer consists of a precision balance with a sample holder present inside furnace with a

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programmable temperature controller. Thermograms were recorded in the temperature range of

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50-800°C at the heating rate of 10°C/min under nitrogen atmosphere.

2.6. Adsorption modeling

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The equilibrium distribution of Cr(VI) between the aqueous phase and adsorbent was determined
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in terms of adsorption isotherms. Langmuir, Freundlich, and Tempkin isotherm models are most

usually used models to analyze the equilibrium of Cr(VI) adsorption by activated bark.
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2.6.1. Langmuir isotherm

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The Langmuir isotherm model assumed that all adsorption sites are identical and each site
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occupies one molecule of adsorbate. If adsorption occurs on one site, no more adsorption occurs

on that particular site. Hence, adsorption is limited to the monolayer. The adsorptive forces are

similar to the forces involve in chemical interaction (33). Langmuir equation is represented as

follow:

(4)

Linearized Langmuir equation is given as below:

(5)
Where Qmax (mg/g) is maximum monolayer capacity of adsorbent, kL (L/mg) is adsorption

energy. The values of Qmax and kL are determined from the slope and intercept of plot Ce vs.

Ce/qe, respectively. The dimensionless factor (RL) was used to determine the feasibility of the

adsorption process. RL values were computed from the following equation (34):

(6)

It was observed that if RL> 1; unfavorable, RL = 1; linear, 0 <RL< 1; favorable, RL = 0 ;

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irreversible.

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2.6.2. Freundlich isotherm

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The Freundlich model applies to non-ideal adsorption equilibrium on heterogeneous surfaces and

multi-layer adsorption. It suggests that the binding sites are not equivalent and independent. This
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model indicates an infinite contribute of unreacted adsorption sites, that the stronger binding sites
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are occupied first. The binding strength decreases with the increase of the degree of site
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occupation. The reduction of affinity between solute and adsorbent during surface coverage
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occurs (35). The Freundlich isotherm expression is the following:

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(7)

Where, Kf (L/mg) and 1/n are empirical constants linked to adsorption capacity and intensity,

respectively. A plot of log qe against log Ce gives the value of Kf and n from intercept and slope,

respectively.

2.6.3. Tempkin isotherm

Tempkin model indicates that heat of adsorption for all molecules decreased linearly rather than

logarithmic due to indirect interaction between adsorbate-adsorbent molecules. It show the

uniform distribution of binding energy on the active sites of adsorbates. Tempkin isotherm can

be written as follow (36):

 (8)

Where T is the absolute temperature (K), R is the universal gas constant (8.314 J/K/mol) and

fitting plot between qe and ln Ce calculates the values of Bi and KT.

2.7. Kinetic modeling

The kinetics of Cr(VI) adsorption was analyzed by pseudo-first-order, pseudo-second-order,

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intra-particle diffusion, and Elovich models. It was used to determine the behavior of metal ions

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adsorption and steps that control the rate of adsorption.

2.7.1. Pseudo-first-order model -p

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The pseudo-first-order model conjectures that the rate of adsorption is proportional to the
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number of free active sites on the surface of the adsorbent. It predicts the adsorption kinetics of

the metal ions. This model is based on the mass transfer of adsorbate molecules to sorption sites.
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The pseudo-first-order kinetic model can be articulated from the following equation (37):
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(9)

Where, qe and qt (mg/g) are the quantity of Cr(VI) adsorbed at equilibrium and time t (min),

respectively and k1 (min−1) is the first-order rate constant. The value of k1and qe is calculated

from slope and intercept of plot log ( ) versus t.

2.7.2. Pseudo-second-order model

In the pseudo-second-order kinetic model, the adsorption rate is controlled by chemical sorption

and proportional to the second power of available active sites. It describes the chemisorptions
involving valence forces through the exchange of electrons between the adsorbent and adsorbate.

The pseudo-second-order model is expressed by the following equation (38):

(10)

Where, qe and qt are the sorption capacity at equilibrium and time t, respectively (mg/g), k2 is the

second-order rate constant (g/mg/min). The value of qe and k2 can be calculated from the slope

and intercept of plot of t/qt versus t.

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2.7.3. Elovich model

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The Elovich model is widely useful for chemical adsorption on an energetically heterogeneous

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solid surface. The linearized Elovich equation may be presented as follow (39):
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(11)
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Where, Elovich coefficients α and β represents the initial sorption rate (mgg−1h−2) and desorption

constant (g mg−1 h-2), respectively. Elovich constants are determined from the slope and intercept
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of plot qt versus lnt.

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2.8. Thermodynamics modeling

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The nature of adsorption was determined by a thermodynamic parameters such as Arrhenius

activation energy (Ea) free energy change (∆G°), enthalpy change (∆H°), and entropy change

(∆S°). These thermodynamic parameters can be determined by the following equations:

k = Ae-Ea/RT (12)

Where Ea is activation energy (J mol-1), k is adsorption rate constant, which was determined from

kinetics modeling of Cr(VI) at different temperatures. A is frequency factor, R is a molar

constant of gases (8.314 J mol-1 K-1) and T is absolute solution temperature (K).

(13)
 (14)

KD = (15)

Where, KD is distribution coefficient, qe (mg/g) represents is absorption capacity of adsorbent, Ce

(mg/L) is equilibrium concentrations of adsorbate, T (K) is temperature and R is gas constant

(8.314 J/mol/K-1). ΔS0 and ΔH0 are obtained from the slope and intercept of the vant Hoff’s plot

of ln KD versus 1/T.

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3. Results and discussion

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3.1. Characterization

FTIR, TGA and SEM study

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The FTIR spectrum of activated carbon was shown in Fig. 1(a). The absorption band appeared
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near about 3392 cm-1 corresponds to -OH stretching vibration (40). The absorption peaks

appeared at 2914 cm-1, 1608 cm-1 and 1015 cm-1 were correspond to C-H stretching vibration of
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-CH2 group, C=O stretching vibration of carbonyl functionality, and C-O- vibration,
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respectively.
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The initial very small weight loss was observed up to 250oC, which may be due to the

dehydration and volatilization. Further weight loss was due to the complete oxidation of the

compound. Fig. 1(b) shows the thermogravimetric analysis of activated carbon.

The surface anatomy and microstructure of AC are shown in Fig. 2(a-b). Highly elongated and

heterogeneous textures with small cavities were observed in the activated carbon. The porous

structure of AC affords a good probability for the adsorption of pollutants from the water system.

3.2. Adsorption study

3.2.1. Effect initial metal concentrations

The effect of initial metal concentration on adsorption was examined in the concentration range

of 100 to 500 mg/L as shown in Fig. 3(a). The percentage of adsorption uptake decreased from

74.08% to 41.29 % with an increase in the concentration of metal ions. The initial increase in

percentage adsorption may be due to the low number of pollutant molecules on the adsorption

sites. At lower concentrations, there were many vacant adsorption pores on the surface of

activated bark. These active pores are essential for the adsorption of Cr(V1). In other words, all

Cr(V1 molecules at lower concentrations interact with active binding sites and boost the

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maximum adsorption. While at higher concentrations, these sites get saturated and lesser

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adsorption occurred. This may be due to the increase in the number of competent Cr(V1) ions for

the binding sites onto activated carbon (41).

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3.2.2. Effect of adsorbent dose
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The effect of adsorbent dosage has been carried out by changing the amount from 20 to 120
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mg/L. The results of the sorbent dosage on adsorption were shown in Fig. 3(b). It has been

observed that the adsorption percentage increased with an increase in the adsorbent dosage. It
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may be due to the presence of greater adsorbent sites as well as a higher specific surface area
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with numerous functional groups on activated carbon. This helps in the easier penetration of

Cr(V1) ions into the adsorption sites (42). The maximum adsorption of 87.89% has occurred at

120 mg/L of adsorbent dosage.

3.2.3. Effect of contact time

The effect of contact time on the adsorption of Cr(V1) has been carried at the optimized initial

metal concentration (20 mg/L) and adsorbent dosage (120 mg). Fig. 3(c) shows that the

adsorption of Cr(V1) enhanced with the contact time The initial rapid adsorption was due to the

copious binding sites on the surface of activated carbon and percentage uptake increased from
31.89% to 89.9% with contact time varied from 20−120 min. The result inferred that adsorption

was fast during the initial stages and then slow down toward the equilibrium. It was due to the

accessibility of numerous vacant sites during the initial stage, hence a large amount of adsorbate

gathered on the adsorbent surface and after that, other vacant sorbent sites are difficult to adsorb

due to repulsive forces between the adsorbate molecules (43-45).

3.2.4. Effect of pH

The effect of pH for the removal of Cr(V1) using AB has been investigated in the range from

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2.0 to 10.0 as shown in Fig. 3(d). The maximum percentage adsorption of 77.06% has recorded

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at 2.0 pH. It was evident from Fig. 3(d) that percentage adsorption using AB was dropped from
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77.06 % at pH 2.0 to 22.05% at pH of 10.0. Cr(V1) generally exist in different forms depending
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on the pH of solutions. In the pH range of 2.0-6.0, Cr(V1) mainly found in HCrO-4, H2CrO-4 and
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CrO2-4, but HCrO-4 dominates. Hence, greater adsorption uptake under acidic pH was due to the

electrostatic attraction between HCrO-4 and positively charge adsorbent surface. The lesser
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adsorption of Cr(V1) in the pH range of 6.0 and 10.0 may be due to competition between anionic
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species such as CrO2-4 and OH- ions for the same adsorption sites on the adsorbent surface (46).
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3.2.5. Effect of temperature

The effect of temperature on the adsorption of Cr(V1) was shown in Fig. 4(a). It has been

observed that percentage adsorption increased with the temperature. This is referred to be

endothermic adsorption of. Cr(V1) ions. The increase in the adsorption capacity of activated

carbon may be due to the enhanced pore structure and greater activation of the adsorbent surface

with the rising temperature. Additionally, a rise in temperature enhanced the movability of

Cr(V1) ions and reduce the swelling effect of the adsorbent. Hence, Cr(V1) ions easily

transferred into the adsorbent surface (47).

3.3. Isotherm study

The isotherm parameters obtained from the Langmuir plot were shown in Table 1. The

maximum adsorption capacity (qm) for the adsorption of Cr(V1) was found to be 78.96 mg/g. It

was apparent from Fig. 4(b) that Langmuir isotherm is more applicable with a higher value of

regression coefficient, R2 approximately 0.99. This intimate the possible monolayer adsorption

of Cr(V1) on the surface of activated carbon. RL values were found to be 0.515-0.079.

The values of the Freundlich parameter were (KF, n and regression coefficient) shown in Table 1.

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The value of n > 1 exhibits (3.07) the heterogeneous adsorption of Cr(V1) onto activated carbon.

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The adsorption behavior of Cr(V1) ions does not obey the Freundlich isotherm.
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The Tempkin constants such as B1 and KT have been calculated from the linear plot of qe vs.
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lnCe. It was inferred from Fig. 4(d) that Tempkin isotherm does not show a higher value of the
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regression coefficient. The isotherm constants and correlation coefficient values (R2) have been
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given in Table 1.

3.4. Kinetic study

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The values of qe and k1 were obtained from the intercept and slope of a plot log(qe− qt) vs. t (Fig.
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5a). The regression coefficient, qe and k1 were provided in Table 2. According to Table 2 and Fig.

5(a), the greater R2 undoubtedly confirmed that Cr(V1) adsorption kinetics closely follow the

pseudo-first-order model. Thus, it revealed that physio-adsorption plays an important role in the

adsorption of Cr(V1). The Elovich constants were computed from the plots of qt vs. ln t (Fig. 5c).

The Elovich model provides a higher correlation coefficient value of 0.97.

3.5. Thermodynamic study

The thermodynamic parameters for Cr(V1) adsorption onto activated carbon were given in Table

3. The positive value of ∆H0 (112.47 KJ mol-1) indicates that the adsorption of Cr(V1) from the

water system was endothermic. The calculated value of free energy change (∆G°) was negative
(−4.78 KJ mol-1) at 30°C, indicating spontaneous adsorption (Fig. 5d). Further, positive value of

entropy change (∆S°) indicates that randomness occurred at the solid-liquid interface during the

adsorption of adsorbate molecules onto adsorbent. It was because, before adsorption, the

adsorbate ions in the aqueous phase are deeply solvated and well ordered. This order has

vanished when the Cr(V1) ions were adsorbed onto activated carbon surfaces due to the free

movement of solvated water molecules (48).

4. Conclusions

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This study shows that prepared porous activated carbon (AB) is an efficient adsorbent for the

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removal of notorious Cr(V1) from an aqueous phase. The activated carbon was characterized by

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Fourier transform infrared spectroscopy (FTIR), Thermogravimetric analysis (TGA) and
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scanning electron microscopy (SEM) to explore the composition thermal stability and surface
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structure of activated carbon. The maximum adsorption capacity of Cr(V1) was found to be

78.96 mg/g. The adsorption of Cr(V1) ions onto activated carbon well agreed with Langmuir
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model R2 (0.99) and it shows the monolayer adsorption. The adsorption kinetics confirmed the
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pseudo-first-order model which indicates that physio-adsorption plays a vital role in the
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adsorption process. The thermodynamic parameter indicates the spontaneous, feasible, and

endothermic nature of the adsorption process. Thus, the results imply that activated carbon (AB)

prepared from Mangifera indica bark is a technically viable, extremely competent, and economic

material for the removal of Cr(V1) from the water system.

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Table 1. Isotherm parameters for Cr(VI) removal onactivated bark (AB)

Isotherm Plot Parameters

Langmuir qm (mg/g) KL (L/mg) RL R2

78.96 0.146 0.515-0.079 0.99

Freundlich n Kf (L/mg) R2
3.07 14.96 0.87

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Tempkin B1 KT (L/mg) R2

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14.67 5.67 0.88

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Table. 2. Kinetic parameters for the adsorption of Cr(VI) of onto activated bark (AB)

Kinetic models Plot parameters

Psuedo-first-order K1 (min-1) qe (mg g-1) R2

0.0046 3.08 0.99
-1 -1 -1
Psuedo-second-order K2 (g mg min ) qe (mg g ) R2

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0.00095 54.20 0.93

Elovich α (mg g-1 h-2) β (g mg-1 h-2) R2

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18.67 2.89 0.978
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Table 3. Thermodynamic functions for Cr(VI) adsorption on activated bark (AB)

T (K) ∆G0 (KJ/mol) ∆H0 (KJ/mol) ∆S0 (J/molk)

303 − 4.78 112.47 212.07

308 − 5.33
313 − 6.15

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318 − 6.91
323 − 7.47

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328 − 7.93

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Fig. 1. (a) FTIR spectra of AB, (b) Thermal stability curve of AB.
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Fig. 2.SEM images of AB at different magnifications.
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Fig. 3. Effect of (a) initialmetal concentration (b) adsorbent amount (c) contact time (d) pH for
Cr(V1) adsorption onto AB [metal concentration 100 mg L-1, adsorbent dosage 0.12 g, contact
time 120 min, pH 2.0, temperature 30 °C].
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Fig.4. Effect of (a) temperature(b) Langmuir isotherm, (c) Freundlich isotherm (d) Tempkin
isotherm for adsorption of Cr(V1) onto AB.
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Fig.5. (a) Pseudo-first-order (b) Pseudo-second-order (c) Elovich model (d) Van't Hoff plot for
adsorption quantity of Cr(V1)onto AB for computing thermodynamic parameters.
 Highlights

• Activated bark prepared from Mangifera indica was used for the removal of Cr(VI) from

aqueous solution.

• Activated bark was characterized by techniques such as Fourier transform infrared

spectroscopy (FTIR), scanning electron microscopy (SEM), and thermal analysis (TGA).

• The effect of different adsorption parameters such as metal ion concentration, adsorbent

dosage, contact time, pH, and the temperature was optimized. Langmuir, Freundlich, and

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Tempkin's isotherms were studied to investigate the adsorption capacity.

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• Langmuir model was found to be best fitted with a maximum adsorption capacity of
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78.96 mg/g. The adsorption of Cr(V1) ions onto activated carbon was found to be agreed
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with Langmuir model R2 (0.99) with monolayer adsorption.
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• The adsorption kinetics confirmed the pseudo-first-order model which indicates that
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physio-adsorption plays a vital role in the adsorption process.

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Declaration of interests

√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.

☐The authors declare the following financial interests/personal relationships which may be considered
as potential competing interests:

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 Credit author statement

Authors contributions to the paper titled “Modelling studies for remediation of Cr (VI) from

wastewater by activated Mangifera indica bark are as follow:

Dr. Deepak Pathania has done Conceptualization; Data curation; Formal analysis; Funding

acquisition; Investigation; Methodology; Project administration; Resources;

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Dr Arush Sharma has performed: Software; Supervision; Validation; Visualization;

Roles/Writing - original draft; Writing. -p

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Dr A.K. Srivastava has attempted review & editing.
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