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Adsorption Studies of Pb2+, Cu2+ and Cr3+ from Aqueous Solution Using Azadirachta Indica (Neem) Seed Husk and Adansonia Digitata (Baobab) Seeds

Received: 12 June 2024     Accepted: 10 July 2024     Published: 27 August 2024
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Abstract

The adsorption of Pb2+, Cu2+ and Cr3+ from aqueous solution using Neem seed husk (NSH) and baobab seed (BS) were studied through the use of batch adsorption system. The adsorbents were prepared by drying at 120°C for 24hours and were characterized using FT-IR, XRD, and SEM analysis. The FTIR spectroscopy revealed the presence of O-H, N-H, C-H, C=C, C=O, and C-O stretching; XRD revealed the particle sizes as 44.51nm for NSH and 42.61nm while the morphology of the NSH and BS were revealed by SEM to be porous for NSH and BS. Various parameters such as, initial metal ion concentration, adsorbent dosage, contact time, Temperature and pH of metal ion solution were investigated in a batch-adsorption System. The adsorption uptake was found to increase with increase in adsorbent dose, contact time and temperature but decreases with the initial concentration. The uptake of the metal ions increases and reaches optimum at pH of 4-6. The maximum adsorption capacity was found to be Pb-NSH (15.267mg/g) and Cu-NSH (19.46mg/g). Adsorption of Cu2+onto NSH fitted Langmuir isotherm model with (R2 > 0.93) while Adsorption of Pb-NSH Fitted Freundlich isotherm Model with (R2> 0.99). Kinetic data fitted pseudo-second-order model (R2 > 0.98) which was more suitable in explaining the adsorption rate. Thermodynamic data showed that Gibb’s free energy (ΔG°) values for all metal ions were negative indicating feasibility and favorability of adsorption. Positive enthalpy change (ΔH°) and Entropy change (ΔS°) values indicate endothermic processes and increase in randomness.

Published in Science Journal of Chemistry (Volume 12, Issue 4)
DOI 10.11648/j.sjc.20241204.12
Page(s) 73-85
Creative Commons

This is an Open Access article, distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution and reproduction in any medium or format, provided the original work is properly cited.

Copyright

Copyright © The Author(s), 2024. Published by Science Publishing Group

Keywords

Adsorption Studies, Aqueous Solution, Azadirachta Indica (Neem) Seed Husk, Adansonia Digitata (Baobab) Seeds

1. Introduction
Heavy metals are generally referred to those metals which possess a specific density of more than 5 g/cm3 and adversely affect the environment and living organisms . These are group of pollutants, which are non-bio-degradable in living organisms. . They constitute a very heterogeneous group of elements widely varied in their chemical properties and biological functions The most common heavy metal contaminants are copper, iron, zinc, lead, cadmium, arsenic, manganese, cobalt, chromium, mercury and nickel .
Although it is acknowledged that, heavy metals have many adverse health effects and last for a long period of time, heavy metal exposure continues and is increasing in many parts of the world. Heavy metals are significant environmental pollutants and their toxicity is a problem of increasing significance for environmental reasons Heavy metals enter the surroundings by natural means and through human activities. Various sources of heavy metals include soil erosion, weathering, leaching and volcanic eruption. Anthropogenic source of heavy metals which result from human activities such as mining, agricultural activities, fossil fuel combustion, refineries, textile and paper industries e.t.c. .
This accumulation of the heavy metals is harmful to the environment because these metals generally accumulated in their most stable oxidation states, i.e., As3+, Pb2+, Hg2+, Cd2+, Cu2+and Cr3+ which further react with body bio-molecules to generate extremely stable bio-toxic compounds which are very difficult to dissociate .
The release of heavy metals into the natural environment has resulted in various environmental challenges due to their non-biodegradable and persistent characteristics . The toxicity of heavy metals in humans may result in damage to various physiological systems, such as the central nervous, cardiovascular, and gastrointestinal systems, as well as the lungs, kidneys, liver, endocrine glands, and bones, which may increase the prevalence of degenerative illnesses and cancers .
Various methods have been developed for the removal of heavy metals from water, including chemical precipitation, electro dialysis, ultrafiltration, ion exchange, reverse osmosis, phytoremediation, membrane separation, aerobic and anaerobic degradation, chemical oxidation, coagulation, and flocculation. Some of these methods have been shown to be effective, however they have some limitations such as excess amount of chemical usage, accumulation of concentrated sludge that has serious disposal problems, formation of toxic compounds during the process, high cost, and incomplete removal of certain ions and takes long time for heavy metal removal. The adsorption technique, which is based on the transfer of pollutants from the solution to the solid phase, is known as one of the efficient and general wastewater treatment method .
The major advantages of adsorption over these conventional treatment methods are low cost, high efficiency, minimization of chemicals, no additional nutrient requirement, and reuse of adsorbent for further metal uptake and possibility of metal recovery .
Lowcost adsorbent such as rice husk, maize cob, banana peels, orange peels, wheat shell, water hyacinth, hazelnuts shells, orange peel pith, sunflower, coconut husk, groundnut husk, coconut shell, palm fibres, are used for removal of heavy metals from industrial waste water.
This research, explore the potential of Neem seed husk for possible use as adsorbent for removal of Pb2+, and Cu2+ ions from waste water.
Aim
The aim of this work is to determine the potentials of Azadirachta indica (Neem) seed husk, and Adansonia Digitata (Baobab) husk for the removal of Pb2+, Cu2+ and Cr3+ ions from aqueous solution for possible use as an adsorbent for heavy metals removal from the environment.
Objectives
The objectives of the study are:
i. To characterize the adsorbents using FTIR, SEM and XRD.
ii. To study the effect of initial concentration, adsorbent dose, time, temperature and pH on adsorption of Pb2+, Cu2+ and Cr3+ions.
iii. To study and understand the adsorption equilibrium isotherms for Pb2+, Cu2+, and Cr3+ ions removal by Neem seed husk, Baobab seeds and Mahogany leaves.
iv. To study and understand the kinetics of the adsorption process and the thermodynamic parameters for removal of Cu2+, Pb2+ and Cr3+ ions.
2. Materials and Methods
2.1. Reagents
All reagents used were of analytical grade. These include: Pb(NO3)2, CuSO4, Cr(NO3)3, NaOH, and HNO3
2.2. Preparation of Stock Solutions
1000g/L Stock solutions of Pb(NO3)2, CuSO4 and Cr(NO3)3 were prepared according to standard procedures by dissolving 1.5980g, 2.5117g and 4.5775g each in 1L of deionize water. Serial dilution method from the stock solution to obtain different concentration by using the formula below, equation (1).
C1V1=C2V2(1)
Where
C1 is the concentration of stock solution, V1 is the volume of the stock solution, C2 is the concentration of the dilute solution and V2 is the volume of the dilute solution.
2.3. Sample Collection and Preparation
Neem Seed Husks samples and Baobab seeds were collected within Gombe State University Area. The samples were prepared by using slightly modified method of . The samples were washed with ordinary water thoroughly and with distill water in order to remove impurities and debris present. The sample was dried in oven at about 120C for 24 hrs. These dried samples were then crushed to a fine powder and sieved with 150mm mesh size sieve. The prepared adsorbents were kept in an airtight bottle awaiting subsequent experiments.
2.4. Sample Characterization
Neem Seed Husk and Baobab Seeds samples were characterized using X-ray diffraction analysis (XRD), Scan Electron Microscopy (SEM) and FT-IR spectroscopy.
2.5. The Batch Adsorption Experiment
Batch adsorption experiment was carried out in order to study the effect of change in initial metal concentration of metal ions, adsorbent dose, contact time, temperature and pH on the adsorption of the Pb2+, Cu2+ and Cr3+. The effect of each parameter was studied by keeping others parameters constant. The solutions were then filtered and the filtrates were subjected to AAS analysis.
i. Effect of Initial Metal Concentration
The effect of initial metal concentration on adsorption of Pb2+, Cu2+ and Cr3+ ions was determine at different concentration of 50, 100, 150, 200, and 250mg/L at room temperature (~25°C). 0.5 g of adsorbents was added 50ml the metal ion solution in each conical flask. The solutions were shaken for 30min at 150rpm. The solutions were filtered using Whatman filter paper and the filtrates were analyzed with AAS.
ii. Effect of Adsorbent Dose
Effect of adsorbent dose on Pb2+, Cu2+ and Cr3+ ions were determined at different amounts of dosage ranging from 0.2, 0.4, 0.6, 0.8, 1.0 and 1.2g. For each experiment, an accurate quantity of the adsorbents were added to 50 mL of metal ions solution at 100mg/L, at 25°C in 250 ml conical flasks. The solutions were shaken at 150 rpm for 30minutes. The solutions were filtered with Whatman filter paper and the filtrates were analyzed using AAS.
iii. Effect of Contact Time
The effect of contact time on the adsorption process of Pb2+, Cu2+ and Cr3+ was studied at the following time intervals 10, 20, 30, 40 and 60mins at optimum concentration of 100mg/L for the metal ions, adsorbent dose of 0.5g at temperature of 25°C. 50 ml of the metal ions were transferred into 250ml conical flasks. The solutions were shaken at 150 rpm at different time intervals. The solutions were filtered using Whatman filter paper and filtrate was analyzed with AAS.
iv. Effect of Temperature
The effect of temperature on the adsorption process of Pb2+, Cu2+ and Cr3+ ions were examined at the following temperatures 25, 30, 35, 40 and 60°C. Then 50ml of 100mg/L metal ions solutions were transferred into 250ml conical flasks, 0.5g of the adsorbents were added in to the flasks. The solutions were shaken at 150 rpm for different temperatures. The filtrates were then filtered and analyzed using AAS.
v. Effect of pH
The effect of pH on the process of adsorption Pb2+, Cu2+ and Cr3+ ions by the adsorbents was determined at different pH value of 2, 3, 4, 5, and 7 and optimum concentrations of metal ions of at room temperature (~25°C). The pH was adjusted using 0.1M HNO3 and 0.1M NaOH. 50ml of 100mg/L solutions of metal ions were transferred into 250ml conical flasks, 0.5 g of absorbents samples were added and the solutions were shaken for 30 min at 150rpm. The solutions were filtered whatman No1 filter paper and the filtrate was analyzed with AAS.
2.6. Data Evaluation
The data obtained by AAS was carried out to analyze the amount Pb2+, Cu2+ and Cr3+ ions adsorbed. The equations 2 and 3 were used to calculate the amount of metal ions adsorbed per unit mass of the adsorbent and percentage removal of metal ions.
qe=C0-CeVM(2)
%R=C0-CeC0 ×100(3)
Where
𝑞𝑒 is the amount of ions adsorbed (mg/g) at equilibrium, C0 is the adsorbate initial concentration (mg/l) and Ce is adsorbate final concentration (mg/l) at equilibrium, V is the solution volume (l) and M is the adsorbent dosage (g).
2.7. Adsorption Equilibrium Studies
The experimental data was modeled using Freundlich and Langmuir isotherms (equations 4 and 5) separately to determine maximum adsorption capacity and adsorption mechanism. The model with the highest R2 value best fitted the adsorption data.
I Langmuir Isotherm
The Langmuir isotherm model equation is expressed as:
1qe=1qmax+1qmaxKL 1Ce(4)
Where
qe is the equilibrium dye concentration on the adsorbent (mg g-1);
Ce is the equilibrium dye concentration in solution (mg L-1);
qmax is the monolayer capacity of the adsorbent (mg g-1);
KL is the Langmuir constant.
The value of KL and qmax are determined from the slope and intercept of the plot of 1/qe against 1/Ce.
The essential characteristics of the Langmuir isotherm can be expressed in terms of a dimensionless constant separation factor RL that is given by equation 5,
RL=11+KLc0(5)
Where
C0 (mg/L) is the highest initial concentration of adsorbate. The value of RL indicates the shape of the isotherm to be either unfavorable (RL>1), linear (RL = 1), favorable (0< RL< 1), or irreversible (RL =0) (Olgun and Atar, 2012).
II Freundlich Isotherm
The Freundlich isotherm model equation is expressed as in equation 6:
Lnqe= LnKF + 1nLnCe(6)
Where
KF (mg/g) and n are the Freundlich constants related to adsorption capacity and intensity, respectively. A linear plot of Lnqe against Ln Ce gives KF and n values.
2.8. Adsorption Kinetics Studies
In order to obtain a suitable rate equation and investigate the controlling mechanism of adsorption process, two main types of adsorption kinetic models, pseudo-first order and pseudo-second order models were considered.
I The Pseudo First-Order Kinetic Model
The first-order rate expression is given in equation 7:
Ln(qe−qt)=Lnqe−k1t(7)
where
qt (mg/g) is the amount of the metal ion absorbed at time t. The value of k1 is the pseudo-first-order rate constant and can be obtained from the slope of the plot of ln(qe−qt) versus t.
II The Pseudo Second-Order Kinetic Model
The pseudo second-order rate expression is given in equation 8:
tqt=1K2qe2+ 1qet(8)
where
qe is the maximum adsorption capacity (mg g-1), qt is the amount of metal ion adsorbed at time t (mg g-1) and k2 is the pseudo-second order kinetic rate constant (g mg-1 min-1).
2.9. Thermodynamic Parameters of Adsorption
Thermodynamic parameters for the adsorption process, such as Gibbs-free energy (∆G°), change in enthalpy and (∆H°) change in entropy (∆S°) were obtained from the experiments carried out at different temperatures in equations 9 - 10.
The free energy change G, enthalpy changes H and entropy changes S are determined using fallowing equations 9 - 10.
= -RTlnKd(9)
= -TS(10)
Where
Kd is the distribution coefficient of the adsorbate, (Kd = Ce/ qe), R is the universal gas constant (8.314 J K-1 mol-1), T is the absolute temperature (K). The plot of ln Kd as a function of 1/T yields a straight line from which H and S are obtained.
3. Result and Discussion
3.1. FTIR Analysis
Figure 1. FTIR Spectra of NSH.
FTIR analysis was carried out to identify functional groups present on the surface of NSH. The FT-IR spectrum shows a peak around 3422 cm-1 indicate the presence of O-H and N-H groups. Peak around 2924 cm- 1 indicate presence of C-H stretch of alkane. The peak around 1616 cm-1 and 1456cm-1 in the spectra depict mainly C=C stretch bands of alkene. Peak around 1034 cm-1 is attributed to C-O bending band. The results obtained are in agreement with the works reported by .
Figure 2. Shows the FTIR result for BS.
The FT-IR results for Baobab seed is shown in Figure 2. Peaks at 3563cm-1 represent O-H stretch due to alcohol and phenols and also free hydroxyl group. The peak at 1653 cm-1 indicate C=O and C=C while that of 1124cm-1 represents C-O. Similar results were reported by .
3.2. Sem Analysis
Figure 3. Shows the SEM result for NSH.
Figure 4. Shows the SEM result for BS.
Figures 3 and 4 show the SEM image of NSH and BS. The images showed an irregular and well developed porous structure indicating relatively high surface area. The porous nature of NSH makes it an efficient adsorbent.
3.3. XRD Result
Figure 5. Shows XRD Spectra of NSH.
Figure 6. Shows XRD image of BS.
XRD analysis was carried out using Cu-Kα radiation, λ = 1.54059 A ° at 25°C. Figures 5 and 6 show the patterns for NSH, and BS with peaks at 2θ = 21.96 and 22.48° respectively. The average crystal size was calculated to be 44.51 and 42.61nm for NSH and BS.
3.4. The Effect of Initial Concentration
The effect of initial metal ion concentration on percentage removal of Pb2+, Cu2+ and Cr3+ ions was investigated at different initial concentrations (50, 100, 150, 200 and 250 mg/l) metal ions and keeping the other parameters constant. The results are shown in Figures 7 and 8. The percentage removal of the metal ions decreases with the increase in the concentrations of the metal ions. This is because, at lower concentration, the number of metal ions is low when compared to the available adsorbent active sites; therefore, adsorption is more frequent. When the metal ion concentration is increased, more ions are crowded on the surface of the adsorbents and the active sites are quickly occupied by them. This result in the saturation of the adsorption sites which decreases the rate of adsorption at higher concentration .
Figure 7. Effect of Initial Concentration the percentage removal of Pb2+, Cu2+ and Cr3+ by NSH.
Figure 8. Effect of Initial Concentration on the percentage removal of Pb2+, Cu2+ and Cr3+ by BS.
3.5. The Effect of Adsorbent Dosage
The effect of adsorbent dosage on the adsorption of Pb2+, Cu2+ and Cr3+was investigated from range 0.2-1.2g while other parameters were kept constant. The plots of percentage removal against adsorbent dosage are presented in figures 9 and 10. It is clear from the results that an increase in the adsorbent dosage led to a corresponding increase of the percentage removal of Pb2+, Cu2+ and Cr3+ adsorbed. This is because as the amount of adsorbent is increased the number of available adsorptions sites increased which directly increases the rate of adsorption .
Figure 9. Effect of adsorbent dose on the percentage removal of Pb2+, Cu2+ and Cr3+ by NSH.
Figure 10. Effect of adsorbent dose on the percentage removal of Pb2+, Cu2+ and Cr3+ by BS.
Figure 11. Effect of contact time on the percentage removal of Pb2+, Cu2+ and Cr3+ by NSH.
Figure 12. Effect of contact time on the percentage removal of Pb2+, Cu2+ and Cr3+ by BS.
3.6. Effect of Contact Time
The effect of contact time on the adsorption of Pb2+, Cu2+ and Cr3+ by the adsorbents was studied using time interval from 10-60 minutes, while other parameters were kept contact. The results were shown in figures 11 and 12. It is clear that the percentage removal of the metal ions increased with increasing the contact time to a point where it reached equilibrium at 40 minutes, beyond which, there was almost no further increase in the adsorption. At initial stages, there are available adsorbent surface sites that rapidly adsorb metal ions. At equilibration time, active sites are exhausted limiting the number of metal ions that can be adsorbed . Completion of adsorption occurs when equilibration time is achieved at a specific time of adsorption .
3.7. The Effect of Temperature
The effect of temperature on adsorption Pb2+, Cu2+ and Cr3+ ions onto the adsorbents was carried out at five different temperatures ranging from 25°C to 60°C while other parameters were kept contact. The results in Figures 13 and 14 show that the percentage removal of metal ions increases with rise in temperature indicating the endothermic nature of the process and was further explained by evaluation of thermodynamic parameters. A similar trend was also observed by .
Figure 13. Effect of Temperature on the percentage removal of Pb2+, Cu2+ and Cr3+ by NSH.
Figure 14. Effect of Temperature on the percentage removal of Pb2+, Cu2+ and Cr3+ by BS
Figure 15. Effect of pH on the percentage removal of Pb2+, Cu2+ and Cr3+ by NSH.
Figure 16. Effect of pH on the percentage removal of Pb2+, Cu2+ and Cr3+ by BS.
3.8. Effect of pH
The pH solution is one of the most important factors affecting the adsorption of metal ions. The acidity of the medium affects the competition of the hydrogen ions and the metal ions for the active sites on the adsorbent surface . The effect of pH on the adsorption of the Pb2+, Cu2+ and Cr3+ ions onto the adsorbents was studied by changing pH values within the range 2–7 for the metal ion solution. The results are presented in Figure 7. The results showed that the adsorption of metal ions increased from within the pH range 2–5. An appreciable decrease in adsorption was observed after pH 5, which continued till pH 7. A similar result was observed by . At lower pH the adsorption of metal ions was low due to competitions between protons and metal ions for the available sites . As the pH increased from 2-5, there were fewer protonated active sites leaving more negatively charged active sites. The decrease in adsorption at pH> 5 could be attributed to the formation of insoluble hydroxyl complexes.
3.9. Adsorption Isotherms
The equilibrium of the adsorption of Pb2+, Cu2+ and Cr3+ on to NSH and BS is established when the concentration of metal ions in bulk solution is in dynamic balance with that on the liquid-adsorbent interface. The relationships between the concentrations of adsorbed metal and metal in solution at a given temperature are known as adsorption isotherms. Langmuir and Freunlich isotherm model were used to describe the equilibrium data. The Langmuir isotherm constant KL and qmax were calculated from the slope and intercept of the plot between 1/qe and 1/Ce. While the Freundlich constants KF and 1/n where obtained from the slope and intercept of a plot of logqe against log Ce. The values of Langmuir parameters (qmax, KL and RL) and Freundlich parameters (KF and 1/n) together with the correlation coefficients (R2) for both models are presented in Tables 1 and 2.
Table 1. Isotherm models for adsorption of Pb2+, Cu2+ and Cr2+ ions onto NSH.

Isotherm Model

Adsorbates

Pb2+

Cu2+

Cr3+

Langmuir

qmax

15.267

19.46

14.75

KL

0.152

0.0498

0.253

RL

0.294

0.167

0.038

R2

0.9512

0.9921

0.9400

Freundlich

KF

3.0549

1.867

3.769

1/n

0.7192

0.381

0.547

R2

0.9912

0.9261

0.9922

The results in the table 1: showed that the Langmuir isotherm model best fitted the adsorption of Cu2+ onto NSH due to higher correlation coefficient R2 value 0.9921 as compared with the Freundlich Isotherm model (0.9261). This indicate a monolayer adsorption which mostly due to the formation of a fixed number of local sites on the surface of the adsorbent . The Freundlich adsorption model fitted well for the adsorption of Pb2+ and Cr3+ ions with R2 value 0.9912 and 0.9922 respectively. The Freundlich model assumes that the adsorption occurs on a heterogeneous surface with non-identical sites with different distributions of heat of adsorption over the surface, and the adsorption sites are distributed exponentially with respect to the heat of adsorption . The maximum adsorption capacity (qmax) of adsorption for Pb2+, Cu2+ and Cr3+ onto NSH was observed to be 15.267mg/g, 19.46mg/g and 14.75 mg/g respectively. It was observed that the value of RL in the range 0–1 confirms favourable adsorption processes.
Table 2. Isotherm models for adsorption of Pb2+, Cu2+ and Cr3+ions onto BS.

Isotherm Model

Metal ions

Pb2+

Cu2+

Cr3+

Langmuir

qmax

30.864

16.155

12.048

KL

0.048

0.134

0.2304

RL

0.116

0.067

0.0416

R2

0.9789

0.977

0.9770

Freundlich

KF

3.0549

3.138

3.8415

1/n

0.7192

0.398

0.2618

R2

0.9512

0.9235

0.9512

Table 2: shows different values for Langmuir and Freundlich adsorption isotherms. The Langmuir isotherm fitted the experimental data very well for the adsorption Pb2+, Cu2+ and Cr3+ on to BS with R2 value 0.9789, 0.9770 and 0.9770 respectively which is greater than the R2 for Freundlich Isotherm. This confirmed the monolayer coverage of Pb2+, Cu2+ and Cr3+ onto BS and also the homogeneous distribution of active sites on the adsorbent, since the Langmuir equation assumes that the surface is homogeneous. This is consistent with the result obtained by .
The RL and 1/n values less than 1 also confirm favorable adsorption of the metal ions onto BS. The maximum adsorption capacity for adsorption for Pb2+, Cu2+ and Cr3+ onto BS was observed to be 30.864mg/g and 16.155mg/g and 12.048 mg/g respectively.
4. Kinetic Studies
In investigating the adsorption kinetic process of the metal ions in solutions, the experimental data obtained were tested with pseudo-first-order and pseudo-second-order kinetic models to identify the controlling mechanism. The linear graph of pseudo-first order was plotted from ln (qe-qt) against t (mins), and the graph of pseudo-second order was plotted from t/qt against t (min). The qcal, K1, K2, and R2 were obtained from the plots and are presented with the qexp in tables 3 and 4.
Table 3. Kinetics of Pb2+, Cu2+ and Cr3+ ions adsorption on NSH.

Kinetic Model

Parameters

Adsorbates

Pb2+

Cu2+

Cr3+

Pseudo-First order

q exp (mg/g)

8.524

8.917

8.7660

K1 (min-1)

0.0438

0.0246

1.7615

q cal (mg/g)

4.772

36.509

0.8270

R2

0.9021

0.9856

0.9908

Pseudo-Second order

K2 (min-1)

0.0164

1.0299

1.5893

qcal (mg/g)

8.945

8.7873

8.4817

R2

0.9895

0.9939

0.9942

Table 4. Kinetics parameters of Pb2+, Cu2+ and Cr3+ ions adsorption on BS.

Kinetic Model

Parameters

Adsorbates

Pb2+

Cu2+

Cr3+

Pseudo-First order

q exp (mg/g)

8.455

8.930

7.366

K1 (min-1)

0.0345

0.0303

0.7841

q cal (mg/g)

2.8519

19.638

0.9036

R2

0.9372

0.9923

0.9947

Pseudo-Second order

K2 (min-1)

0.0277

1.6466

2.4172

qcal (mg/g)

8.606

9.0009

7.5529

R2

0.9984

0.9970

0.9994

From tables 2 and 3, the experimental data processed using the pseudo-first-order kinetic model gave a low correlation coefficient, R2 values for the adsorption of Pb2+, Cu2+ and Cr3+ ions by NSH, BS and ML. Therefore, the adsorption of Pb2+, Cu2+ and Cr3+ onto NSH and BS cannot be adequately described by the pseudo-first-order model. The wide variance between the experimental adsorption capacity (qexp) and calculated adsorption capacity (qcal) values also support this assertion. The pseudo-second order model fit well for the adsorption of the Pb2+, Cu2+ and Cr3+ onto NSH and BS due to higher R2 values as well as the relative agreement between qcal and qexp. The pseudo-second-order model assumes that the rate is proportional to the square of the number of remaining free surface sites . This result trend is in consistent with .
5. Thermodynamic Studies
Table 5. Thermodynamic parameters for adsorption of Pb2+, Cu2+ and Cr3+ ions onto NSH.

Model

Metal ion

Pb2+

Cu2+

Cr3+

ΔG° (KJ.mol-1)

25

-0.4665

-0.9655

-0.0153

30

-0.8994

-2.0486

-0.32143

35

-1.2289

-2.9288

-0.59872

40

-2.1354

-3.9544

-0.97635

60

-2.7753

-4.7526

-1.02944

ΔH° (KJ.mol-1)

+18.8528

+29.8389

+8.7131

ΔS° (KJ.mol-1.K-1)

+0.05487

+0.08717

+0.02962

Table 6. Thermodynamic parameters for adsorption of Pb2+, Cu2+ and Cr3+ ions onto BS.

Model

Metal ion

Pb2+

Cu2+

Cr3+

ΔG° (KJ.mol-1)

25

-0.05396

-0.233

-0.19854

30

-0.5959

-0.51166

-0.66506

35

-0.84665

-1.05825

-1.12888

40

-1.19037

-1.43191

-1.27545

60

-1.61301

-1.91713

-1.72442

ΔH° (KJ.mol-1)

+11.8832

+13.90683

+11.6133

ΔS° (KJ.mol-1.K-1)

+0.040584

+0.04757

+0.04016

The values of the thermodynamic parameters for the adsorption of Pb2+ and Cu2+ onto NSH and BS are given in Tables 5 and 6. These results showed negative values of ∆G° which indicate spontaneous processes. The values of ∆G° become more negative with increasing temperature, which shows that adsorptions are more favourable at high temperatures. The positive values of enthalpy indicate endothermic process. The positive values of the entropy (∆S) indicate an increase in the degree of randomness. Similar findings were obtained by .
6. Conclusion
This study presents a simple, cost-effective, and efficient adsorption process for removing heavy metals from wastewater and the environment. The parameters of initial concentration, temperature, contact time, dosage and pH affected the removal of the three metal ions. The maximum adsorption capacity was found to be for Pb2+, Cu2+ and Cr3+ onto NSH was observed to be 15.267mg/g, 19.46mg/g and 14.75 mg/g respectively. Also the maximum adsorption capacity Pb2+, Cu2+ and Cr3+ onto BS was observed to be 30.864mg/g and 16.155mg/g and 12.048 mg/g respectively. The equilibrium data were well-fitted with the Langmuir isotherm model for adsorption of Cu2+ while the Freundlich isotherm model best fitted the adsorption of Pb2+. The kinetics study of the adsorption of three metal ions fitted pseudo-second-order model compared to the pseudo-first-order. Thermodynamic parameters, change in the free energy (ΔG°), the enthalpy (ΔH°), and the entropy (ΔS°), show that the overall adsorption processes were spontaneous, endothermic in nature, and proceeds with increase in randomness as the value of entropy is positive. Based on this study NSH and BS could be used as a natural adsorbent to remove Pb2+, Cu2+ and Cr3+ from wastewater and environment due to their high removal efficiencies.
Conflicts of Interest
The authors declare no Conflicts of Interest.
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    Yahaya, N. P., Saad, Y. A., Abubakar, A. (2024). Adsorption Studies of Pb2+, Cu2+ and Cr3+ from Aqueous Solution Using Azadirachta Indica (Neem) Seed Husk and Adansonia Digitata (Baobab) Seeds. Science Journal of Chemistry, 12(4), 73-85. https://doi.org/10.11648/j.sjc.20241204.12

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    Yahaya, N. P.; Saad, Y. A.; Abubakar, A. Adsorption Studies of Pb2+, Cu2+ and Cr3+ from Aqueous Solution Using Azadirachta Indica (Neem) Seed Husk and Adansonia Digitata (Baobab) Seeds. Sci. J. Chem. 2024, 12(4), 73-85. doi: 10.11648/j.sjc.20241204.12

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    AMA Style

    Yahaya NP, Saad YA, Abubakar A. Adsorption Studies of Pb2+, Cu2+ and Cr3+ from Aqueous Solution Using Azadirachta Indica (Neem) Seed Husk and Adansonia Digitata (Baobab) Seeds. Sci J Chem. 2024;12(4):73-85. doi: 10.11648/j.sjc.20241204.12

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  • @article{10.11648/j.sjc.20241204.12,
      author = {Nasiru Pindiga Yahaya and Yahaya Aliyu Saad and Adamu Abubakar},
      title = {Adsorption Studies of Pb2+, Cu2+ and Cr3+ from Aqueous Solution Using Azadirachta Indica (Neem) Seed Husk and Adansonia Digitata (Baobab) Seeds
    },
      journal = {Science Journal of Chemistry},
      volume = {12},
      number = {4},
      pages = {73-85},
      doi = {10.11648/j.sjc.20241204.12},
      url = {https://doi.org/10.11648/j.sjc.20241204.12},
      eprint = {https://article.sciencepublishinggroup.com/pdf/10.11648.j.sjc.20241204.12},
      abstract = {The adsorption of Pb2+, Cu2+ and Cr3+ from aqueous solution using Neem seed husk (NSH) and baobab seed (BS) were studied through the use of batch adsorption system. The adsorbents were prepared by drying at 120°C for 24hours and were characterized using FT-IR, XRD, and SEM analysis. The FTIR spectroscopy revealed the presence of O-H, N-H, C-H, C=C, C=O, and C-O stretching; XRD revealed the particle sizes as 44.51nm for NSH and 42.61nm while the morphology of the NSH and BS were revealed by SEM to be porous for NSH and BS. Various parameters such as, initial metal ion concentration, adsorbent dosage, contact time, Temperature and pH of metal ion solution were investigated in a batch-adsorption System. The adsorption uptake was found to increase with increase in adsorbent dose, contact time and temperature but decreases with the initial concentration. The uptake of the metal ions increases and reaches optimum at pH of 4-6. The maximum adsorption capacity was found to be Pb-NSH (15.267mg/g) and Cu-NSH (19.46mg/g). Adsorption of Cu2+onto NSH fitted Langmuir isotherm model with (R2 > 0.93) while Adsorption of Pb-NSH Fitted Freundlich isotherm Model with (R2> 0.99). Kinetic data fitted pseudo-second-order model (R2 > 0.98) which was more suitable in explaining the adsorption rate. Thermodynamic data showed that Gibb’s free energy (ΔG°) values for all metal ions were negative indicating feasibility and favorability of adsorption. Positive enthalpy change (ΔH°) and Entropy change (ΔS°) values indicate endothermic processes and increase in randomness.
    },
     year = {2024}
    }
    

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  • TY  - JOUR
    T1  - Adsorption Studies of Pb2+, Cu2+ and Cr3+ from Aqueous Solution Using Azadirachta Indica (Neem) Seed Husk and Adansonia Digitata (Baobab) Seeds
    
    AU  - Nasiru Pindiga Yahaya
    AU  - Yahaya Aliyu Saad
    AU  - Adamu Abubakar
    Y1  - 2024/08/27
    PY  - 2024
    N1  - https://doi.org/10.11648/j.sjc.20241204.12
    DO  - 10.11648/j.sjc.20241204.12
    T2  - Science Journal of Chemistry
    JF  - Science Journal of Chemistry
    JO  - Science Journal of Chemistry
    SP  - 73
    EP  - 85
    PB  - Science Publishing Group
    SN  - 2330-099X
    UR  - https://doi.org/10.11648/j.sjc.20241204.12
    AB  - The adsorption of Pb2+, Cu2+ and Cr3+ from aqueous solution using Neem seed husk (NSH) and baobab seed (BS) were studied through the use of batch adsorption system. The adsorbents were prepared by drying at 120°C for 24hours and were characterized using FT-IR, XRD, and SEM analysis. The FTIR spectroscopy revealed the presence of O-H, N-H, C-H, C=C, C=O, and C-O stretching; XRD revealed the particle sizes as 44.51nm for NSH and 42.61nm while the morphology of the NSH and BS were revealed by SEM to be porous for NSH and BS. Various parameters such as, initial metal ion concentration, adsorbent dosage, contact time, Temperature and pH of metal ion solution were investigated in a batch-adsorption System. The adsorption uptake was found to increase with increase in adsorbent dose, contact time and temperature but decreases with the initial concentration. The uptake of the metal ions increases and reaches optimum at pH of 4-6. The maximum adsorption capacity was found to be Pb-NSH (15.267mg/g) and Cu-NSH (19.46mg/g). Adsorption of Cu2+onto NSH fitted Langmuir isotherm model with (R2 > 0.93) while Adsorption of Pb-NSH Fitted Freundlich isotherm Model with (R2> 0.99). Kinetic data fitted pseudo-second-order model (R2 > 0.98) which was more suitable in explaining the adsorption rate. Thermodynamic data showed that Gibb’s free energy (ΔG°) values for all metal ions were negative indicating feasibility and favorability of adsorption. Positive enthalpy change (ΔH°) and Entropy change (ΔS°) values indicate endothermic processes and increase in randomness.
    
    VL  - 12
    IS  - 4
    ER  - 

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Author Information
  • Department of Chemistry, Faculty of Science, Gombe State University Gombe, Gombe, Nigeria

  • Department of Chemistry, Faculty of Science, Gombe State University Gombe, Gombe, Nigeria

  • Department of Chemistry, Faculty of Science, Gombe State University Gombe, Gombe, Nigeria

  • Abstract
  • Keywords
  • Document Sections

    1. 1. Introduction
    2. 2. Materials and Methods
    3. 3. Result and Discussion
    4. 4. Kinetic Studies
    5. 5. Thermodynamic Studies
    6. 6. Conclusion
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