THERMODYNAMIC STUDIES ON BIOSORPTION OF ZINC USING PALM SHELL ACTIVATED CARBON

KAYATHRE A/P RAVEENDRAN

A project report submitted in partial fulfilment of the requirements for the award of Bachelor of Engineering (Hons.) Chemical Engineering

Faculty of Engineering and Science Universiti Tunku Abdul Rahman

April 2012

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DECLARATION

I hereby declare that this project report is based on my original work except for citations and quotations which have been duly acknowledged. I also declare that it has not been previously and concurrently submitted for any other degree or award at UTAR or other institutions.

Signature :

_________________________

Name

Kayathre A/P Raveendran

ID No.

08 UEB 03125 13th April 2012

Date

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APPROVAL FOR SUBMISSION

I certify that this project report entitled THERMODYNAMIC STUDIES ON BIOSORPTION OF ZINC USING PALM SHELL ACTIVATED CARBON was prepared by KAYATHRE A/P RAVEENDRAN has met the required standard for submission in partial fulfilment of the requirements for the award of Bachelor of Engineering (Hons.) Chemical Engineering at University Tunku Abdul Rahman.

Approved by,

Signature : _________________________

Supervisor : Dr. Gulnaziya Issabayeva

Date

: _________________________

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The copyright of this report belongs to the author under the terms of the copyright Act 1987 as qualified by Intellectual Property Policy of University Tunku Abdul Rahman. Due acknowledgement shall always be made of the use of any material contained in, or derived from, this report.

2012, Kayathre a/p Raveendran. All right reserved.

Specially dedicated to my beloved grandmother, late Madam Alamaloo, mother, S.Chitra Devi and my beloved father S.Raveendran.

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ACKNOWLEDGEMENTS

I would like to thank everyone who had contributed to the successful completion of this project. I would like to express my gratitude to my research supervisor, Dr. Gulnaziya Issabayeva for his invaluable advice, guidance and his enormous patience throughout the development of the research.

In addition, I would also like to express my gratitude to my loving parents especially my mom who is always on my side, riding along with me on my ups and downs as well as giving me the encouragement to pursue my dreams and friends who had helped and given me encouragement throughout my research.

To my dear friends, Thilaga Laxmy Kannan, Vitya Kalaiselvam, Sumithra Shanmugam, Yushshendrra Shrii Kumar, Parameswari Subramaniam and all close members in Faculty of Engineering & Science, UTAR thanks for making my stayed in UTAR so colourful and enjoyable, the memory of your friendships will forever stay inside my heart.

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THERMODYNAMIC STUDIES ON BIOSORPTION OF ZINC() USING PALM SHELL ACTIVATED CARBON

ABSTRACT

Toxic heavy metals in air, soil, and water are global problems that are growing threat to humankind. The heavy metals, which include copper (Cu), zinc (Zn), lead (Pb), mercury (Hg), nickel (Ni), cobalt (Co), and chromium (Cr), are common trace constituents in the earth crust. Heavy metals are major toxicants found in industrial wastewaters. Thus, the removal of heavy metals from wastewater is necessary before any unpleasant things occur. A conventional method for removing metals from industrial effluents includes chemical precipitation, coagulation, solvent extraction, electrolysis, membrane separation, ion exchange and adsorption. Most of these methods are high capital and regeneration costs of the materials. Therefore, there is currently a need for new, innovative and cost effective methods for the removal of toxic substances from wastewaters. Bio-sorption is an effective and adaptable method and can be easily adopted in low cost to remove heavy metals from large amount of industrial wastewaters. Biosorption is a physicochemical process that occurs naturally in certain biomass which allows it to passively concentrate and bind contaminants (heavy metals) onto the biosorbent cellular structure. This project is focused more on the phenomenon of biosorption in particular, on the biosorption of zinc, where this entire assessment is about the thermodynamics studies on biosorption of zinc by different type of biosorbent materials covering the effect of different temperatures, effect of pH on biosorption capacity, and particle size of biosorbent and initial concentration of zinc aqueous solution. At the same time, the thermodynamics parameters such as change in standard free energy ( ( and entropy ( will be determine using several equations. , enthalpy

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TABLE OF CONTENTS

DECLARATION APPROVAL FOR SUBMISSION ACKNOWLEDGEMENTS ABSTRACT TABLE OF CONTENTS LIST OF TABLES LIST OF FIGURES LIST OF SYMBOLS/ABBREVIATIONS LIST OF APPENDICES

ii iii vi vii viii x xi xii xiii

CHAPTER

INTRODUCTION 1.1 1.2 Background Aims and Objectives

1 1 2

LITERATURE REVIEW 2.1 2.2 2.3 2.4 2.5 Background Effect of agitation speed and contact time Effect of pH on the biosorption capacity Temperature Effect Initial concentration of Zinc

3 3 4 5 6 6

METHODOLOGY 3.1 Preparation of Biosorbents

10 10

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3.2

Preparation of stock solution, Zn(NO3)2 and blank solution, NaNO3 10 11 11 11 12 12 13 14 Biosorption Experiments 3.3.1 3.3.2 Batch Experiment Analytical Experiment

3.3

3.4

Adsorption Equilibrium Models 3.4.1 3.4.2 Langmuir Isotherm Freundlich Isotherm

3.5

Biosorption Thermodynamics

RESULTS AND DISCUSSION 4.1 4.2 4.3 The Effect of initial zinc ion concentration The Effect of Temperature Adsorption Equilibrium Models 4.3.1 4.3.2 4.4 Langmuir Isotherm Freundlich Isotherm

15 15 17 19 20 23

Thermodynamics properties for biosorption of Zinc() by original PSAC 26

4.5

Comparison of biosorption of Zinc(II) with different Adsorbents Reported in Literature 29 Comparison of pH changes for biosorption of Zinc() with different adsorbent were revised 30

4.6

CONCLUSION AND RECOMMENDATIONS 5.1 5.2 Conclusion Recommendations

31 31 32

REFERENCE

33

APPENDICES

36

LIST OF TABLES

TABLE

TITLE

PAGE

Table 2.1: The Langmuir Isotherm parameters for Biosorption of Zinc () with different biosorbents. Table 2.2: The Freundlich Isotherm parameters for Biosorption of Zinc () with different biosorbents Table 4.1: Sorption Capacity at different temperatures and initial concentration Table 4.2: Freundlich and Langmuir model parameters for biosorption of zinc (11) with original PSAC Table 4.3: Values of 1/T and ln b for the Gibbs Energy Graph Table 4.4: Gibbs Energy for Biosorption of Zinc () ions on original PSAC Table 4.5: The thermodynamics parameters for the entire Biosoprtion of Zinc () ions on original PSAC Table 4.6: Zinc() adsorption capacities (qm) of agricultural waste materials Table 4.7: The biosorption of Zinc() in different pH with different biosorbents

16

18 26

27

28

29

30

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LIST OF FIGURES

FIGURE

TITLE

PAGE

Figure 4.1: The Sorption Capacity for biosorption of Zinc () ions on PSAC at different temperatures Figure 4.2: The Adsorption capacity of Zinc () ions during the biosorption process by PSAC Figure 4.3: Langmuir isotherm for biosorption of Zinc () ions on original PSAC at T = 30C Figure 4.4: Langmuir isotherm for biosorption of Zinc () ions on original PSAC at T= 40C Figure 4.5: Langmuir isotherm for biosorption of Zinc () ions on original PSAC at T = 50C Figure 4.6: Langmuir isotherm for biosorption of Zinc () ions on original PSAC at T= 60C Figure 4.7: Freundlich isotherm for biosorption of Zinc () ions on original PSAC at T= 30 C Figure 4.8: Freundlich isotherm for biosorption of Zinc () ions on original PSAC at T= 40 C Figure 4.9: Freundlich isotherm for biosorption of Zinc () ions on original PSAC at T= 50 C Figure 4.10: Freundlich isotherm for biosorption of Zinc () ions on original PSAC at T= 60 C Figure 4.11:Thermodynamics parameters (The Gibbs Energy) for biosorption of Zinc () ions on original PSAC

16

17

20

21

21

22

23

24

24

25

26

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LIST OF SYMBOLS/ABBREVIATIONS

b/K Ci Ce Ceq KF M n q qmax R2 RL R T V

ratio of adsorption, L/mg initial concentration of zinc ions, mg/L final concentration of zinc ions, mg/L equilibrium concentration of metal , mg/L Freundlich constant of adsorption capacity, mg/g mass of biosorbent, g Freundlich constant of adsorption intensity metal uptake, mg/g maximum metal uptake, mg/g correlation coefficient dimensionless equilibrium parameter for Langmuir Isotherm gas constant, J/(mol.K) temperature, K solution volume, mL standard free energy, kJ/mol enthalpy, kJ/mol entropy, kJ/mol.K

PSAC rpm

palm shell activated carbon revolution per minute

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LIST OF APPENDICES

APPENDIX A Figure A1.1

TITLE Graphs/Tables Percentage uptake of biosorption of Zinc () ions on original PSAC The qe graph for biosorption of Zinc () ions on original PSAC Thermodynamic parameter for biosorption of Zinc () ions on original Percentage uptake of biosorption of Zinc () ions on original PSAC The qe graph for biosorption of Zinc () ions on original PSAC Thermodynamic parameter for biosorption of Zinc () ions on original Percentage uptake of biosorption of Zinc () ions on original The qe graph for biosorption of Zinc () ions on original PSAC Thermodynamic parameter for biosorption of Zinc () ions on original PSAC(T = 50 C)

PAGE 36

36

Figure A1.2

37

Figure A1.3

37

Figure A1.4

38

Figure A1.5

38

Figure A1.6

39

Figure A1.7

40

Figure A1.8

40

Figure A1.9

41

Figure A1.10 Percentage uptake of Zinc () ions on original PSAC (T = 60 C) Figure A1.11 The qe graph for biosorption of Zinc () ions on original PSAC Figure A1.12 Thermodynamic parameter for biosorption of Zinc () ions on PSAC

42

42

43

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Figure A1.13 Calibration graph for biosorption Zinc () ions on original PSAC Table A2.1 The Calibration table for the biosorption of Zinc () ions on PSAC Sorption Capacity for different temperatures as initial concentration varies Adsorption capacity for different Temperature as initial concentration varies Calculations for thermodynamic parameters

43

44

Table A2.2

44

Table A2.3

45 46

CHAPTER 1

1 INTRODUCTION

1.1

Background

Toxic heavy metals in air, soil, and water are global problems that are growing threat to humankind. The heavy metals, which include copper (Cu), zinc (Zn), lead (Pb), mercury (Hg), nickel (Ni), cobalt (Co), and chromium (Cr), are common trace constituents in the earth crust. The metals concentrations in the ambient environment have increased significantly since the Industrial Revolution. Heavy metals are major toxicants found in industrial wastewaters. The increment of population throughout nation, leads to a rapid industrialization. Therefore, it increases the effluents and domestic wastewaters into the aquatic ecosystem. High usage of heavy metals in industrial activities has caused the discharge of them in wastewater. The discharge of metallic ions in industrial wastage is of great concern because their presence and accumulation have a toxic effect on living species. Industrial wastewater containing metal ions such as nickel, lead, copper, zinc and aluminum are common because the metals are used in a large number of industries such as electroplating, batteries manufacturing, mining, metal finishing, brewery, and pharmaceutical. Heavy metal toxicity can result in damaged or reduced mental and central nervous function, lower energy levels, and damage to blood composition, lungs, kidneys, liver, and other vital organs (International Occupational Safety and Health Information Centre, 1999). Thus, the removal of heavy metals from wastewater is necessary before any unpleasant things occur.

One of the gears that help to achieve the removal of heavy metal is by using activated carbon. A conventional method for removing metals from industrial effluents includes chemical precipitation, coagulation, solvent extraction, electrolysis, membrane separation, ion exchange and adsorption. Most of these methods are at high capital and regeneration costs of the materials. Therefore, there is currently a need for new, innovative and cost effective methods for the removal of toxic substances from wastewaters. Bio-sorption is an effective and adaptable method and can be easily adopted in low cost to remove heavy metals from large amount of industrial wastewaters.

1.2

Aims and Objectives

General Objective The general objective of this experiment is about the thermodynamics studies on biosorption of zinc by original Palm Shell activated carbon.

Specific Objectives The specific objectives for this experiment are to investigate: 1. 2. The biosorption of zinc using palm shell activated carbon. The effect of biosorption of zinc using palm shell activated carbon at four different temperature. (30 3. , 40 50 and 60 )

The effect of biosorption of zinc using palm shell activated carbon at different range of initial concentration of zinc.

4.

The thermodynamics parameters such as change in standard free energy ( , enthalpy ( and entropy ( for the biosorption of zinc using

palm shell activated carbon.

CHAPTER 2

2 LITERATURE REVIEW

2.1

Background

This entire review is about the thermodynamics studies on biosorption of zinc by different type of biosorbent materials covering the effect of different temperatures, effect of pH on biosorption capacity, biosorption time, and particle size of biosorbent and initial concentration of zinc aqueous solution. Also the review encloses the effects of different condition for biosorption and some methodological aspects. This chapter is focused more on the phenomenon of biosorption in particular, on the biosorption of zinc. Heavy metals are common in industrial application such as manufacturing of pesticides, batteries, alloys, electroplating metal parts, textile dyes, and steel. Zinc is one of the most crucial metals often found in effluents discharged from manufacturing industries. Elimination of heavy metal by biosorption plays an important part in wastewater treatment. Biosorption is a physicochemical process that occurs naturally in certain biomass which allows it to passively concentrate and bind contaminants onto the biosorbent cellular structure. The scientists and engineers hope, this remedy will provide an economical alternative for removing toxic heavy metals from industrial wastewater. The adsorbing biomass, or biosorbents, can remove harmful metals like: arsenic, lead, cadmium, cobalt, chromium, zinc and uranium. Biosorption can be used as an environmentally friendly filtering technique. There is no uncertainty that the world could benefit from more

precise filtering of harmful pollutants created by industrial processes. Biosorption uses biomass raw materials which are either abundant or wastes from other industrial operations. The metal-sorbing performances of certain types of biomass depend on the type of biomass, the mixture in the solution, the type of biomass preparation, and the chemico-physical environment. These studies enclose the biosorption of heavy metal zinc using maize leaf, egg shell powder, chicken feather, fungal biomass, wheat based biosorbent, rice husk, and activated carbon (Jonathan Fabrito & Aline Nathasiah,2009).The effect of different operating parameters such as initial concentration of zinc and adsorbent, temperature, particle size, effect of pH on the biosorption capacity, effect of agitation speed, contact time and mass on the uptake of zinc ions by biosorbents are enfold in this review. In addition, the biosorption equilibrium thermodynamic parameters for the removal of zinc using those biosorbents as mentioned above are enlighten in this review as well.

2.2

Effect of agitation speed and contact time

The agitation speed is required to enhance the chemical reaction by the biosorbent with the zinc ions. As the agitation speed increases, the movement of the biosorbent and the zinc ions increases as well, where it ensures the biosorbent and the zinc ions collide together. Hence, the zinc ions will bind on the cellular structure of the biosorbents. It is obvious that the removal efficiency of zinc ions increases extensively at agitation speed between 100 rpm and 350 rpm (Shuguang Lua et al., 2007). In addition, contact time also plays a part for the removal efficiency of zinc ions, where as the contact time increases the highest removal of zinc ions is achieved. The contact time for each biosorbent to absorb the metal ions is depends on the nature of the biosorbents. It is clearly illustrated by P.King et al., where the optimum time for the removal of zinc using biomass Azaclirachta Indica bark is at 45 minutes. Further time increases, there are no significant change is observed. So for this biosorbents the optimum time of 45 minute has been chosen for effective removal of zinc ions. Similarly, Jin-Ho Joo et.al permits that highest biosorption of zinc ions

was observed at after 30 minutes using bacteria biomass as the biosorbents. This short time required for biosorption in accordance with the results given by other authors showed that the maximum absorption of zinc was reached after 30 minutes. Overall, at the beginning of the biosorbent is added to the metal solution, the reaction will be very prompt within the first 5 minutes of contact. This is due to the high initial concentration at the initial stage, where the binding site on the biosorbent cellular structure is still empty.

2.3

Effect of pH on the biosorption capacity

It is acknowledged that biosorption of heavy metal ions by biosorbents depends on the pH solution. The pH medium influences the solubility of metal ions and the concentration of counter ions. In addition, the pH affects the speciation of metal ions in solution and the metal binding sites on biosorbent surface. The both carboxyl and hydrogen ions presence in the solution, depends on the pH value. As the pH value increases, the amount of carboxyl ions presence will be increases as well and vice versa for the amount of hydrogen ions. Since zinc ions are positively charged, it is preferable that the surface of the biosorbent will have higher negative charge density. On the other hand, at lower pH values zinc removal was inhibited, perhaps as a result of the competition of between hydrogen ions and zinc ions on the sorption sites. Therefore, the efficiency of biosorption of zinc ions can be observed at pH above 4 (Sibel Tunali and Tamer Akar, 2005). Similar results were also reported in literature for different biomass system. (Y.Prasanna Kumar et al.)

2.4

Temperature Effect

The temperature parameter is found to be an important tool for the sorption of zinc ions dealing with the thermodynamics of the biosorption process. It is promptly correlates to the kinetic energy of the zinc ions. Apart from that, an increase or decrease in temperature will cause a change in the amount of zinc being absorbed by the biosorbents. Temperature changes will affect a number of factors which are important in heavy metal ion biosorption(T.Kutsal et al.). Some of the factors include: i. ii. the stability of the metal ion species initially placed in solution; the stability of micro organism-metal complex depending on the biosorption sites; iii. iv. the effect of temperature on the micro organism cell wall configuration; the ionization of chemical moieties on the cell wall The temperature has two major effects on the adsorption process. One is that increasing the temperature will increase the rate of adsorbate diffusion across the external boundary layer and in the internal pores of the adsorbate particles because liquid viscosity decreases as temperature increase and the other one is that it effects the equilibrium capacity of the adsorbate depending on whether the process is exothermic and endothermic (Al-Qodah).

2.5

Initial concentration of Zinc

The initial zinc concentration is one of the key to determine the efficiency in removal of zinc ions. As the zinc concentration is increased, the uptake of zinc ions increases as well for certain level only. An increase in the concentration of zinc ions would cause more hydrogen ions to be released, hence causing the pH value to decrease. This would consistently lead to decrease in biosorption efficiency at high zinc ions concentration. The higher concentration of zinc ions makes the biosorption capacity reached a saturation value, where it doesnt give any further changes with initial zinc ions concentration. The review that done, for this part were found to be comparable with many of the reported literature. (Shuguang Lua et al., 2007).

2.1.5

Effect of biosorbent particle size

The size of the biosorbent will influence the biosorption capacity. As the particle size increases, the surface area is reduced and, therefore the binding area is reduced as well. So, it will results in lower value of biosorption as the particle size increases (M. Tukaram Bai et al. 2010). Hence, a smaller biosorbent particle size with a larger surface area is more preferable.

2.1.6

Biosorption Isotherm

The equilibrium of the biosorption process is often described by fitting the experimental points with models (Gadd, et al. 1988) usually used for the representation of isotherm adsorption equilibrium. The Langmuir isotherms equation is valid for monolayer sorption onto surface containing finite number of identical sorption sites which is described by the following equation (2.1) where q is milligrams of metal accumulated per gram of the biosorbent material; Ceq is the metal residual concentration in solution; qmax is the maximum specific uptake corresponding to the site saturation and b is the ratio of adsorption and desorption rates. This is a theoretical model for monolayer adsorption. Another empirical model for monolayer adsorption is the Freundlich Isotherm, which is represented by the following equation (2.2) where KF (mg g1) and n are the Freundlich constants related to adsorption capacity and adsorption intensity, respectively. The adsorption capacities of the adsorbents for the biosorption of Zn (II) have been compared with those of other adsorbents reported in literature and the values of adsorption capacities have been presented in Table 2.1 and Table 2.2. The values reported in the form of monolayer adsorption capacity. The experimental data of the present investigations are comparable with the reported values. In this literature reviews studies, it is clearly shown that the Langmuir Isotherm fits the best compared to the Freundlich Isotherm.

Table 2.1: The Langmuir Isotherm parameters for Biosorption of Zinc () with different biosorbents. Biosorbents b (L/mg) P.simplicissimum Clarified Sludge Activated alumina Neem Bark 0.047 13.29 0.9923 Bhattacharya et al. 0.025 0.299 0.102 Langmuir Isotherm qmax (mg/g) R2 77.52 15.53 13.69 0.992 0.9971 0.9932 Reference Ting Fan et al.2007 Bhattacharya et al. Bhattacharya et al.

Table 2.2: The Freundlich Isotherm parameters for Biosorption of Zinc () with different biosorbents Biosorbents Kf (mg/g) P.simplicissimum Clarified Sludge Activated alumina Neem bark 8.248 3.16 1.34 0.687 Freundlich Isotherm n R2 0.4 0.705 0.701 0.755 0.887 0.9964 0.9923 0.9913 Reference

Ting Fan et al. 2007 Bhattacharya et al. Bhattacharya et al. Bhattacharya et al.

2.1.7

Thermodynamics of Biosorption

The recent study of biosorption of Zinc (II) Ions by Calymperes erosum were carried out by N.A. Adesola Babarinde with the authors working mates .Thermodynamic parameters were obtained by varying temperature conditions over the range of 2137 C by keeping other variables constant. The values of the thermodynamic parameters such as enthalpy energy H, Gibbs energy, G and entropy energy S describes the biosorption of zinc ions by Calymperes erosum. The biosorption process can be regarded as a heterogeneous and reversible process at equilibrium. The biosorption of zinc ions with different biosorbent will give negative value for Gibbs energy at various temperatures and the negative value indicates the biosorption is a feasible process (Ting Fan et al. 2007).

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CHAPTER 3

3 METHODOLOGY

3.1

Preparation of Biosorbents

Palm shell activated carbon (PSAC) was provided by Bravo Green Sdn. Bhd. a manufacturer of the material located in Kuching, Sarawak, Malaysia. The material is obtained using steam in the physical activation process. Oil-palm shells of various size fractions, namely 1.0-2.0, 2.0-2.8 and 2.8-4.0 mm were used for the preparation of activated carbons. Detailed preparation procedures can be found elsewhere. The mass of palm shell activated carbon was measured in the range of 0.2495 mg to 0.2505 mg.

3.2

Preparation of stock solution, Zn(NO3)2 and blank solution, NaNO3

Stock solutions of zinc concentration 6539 mg/L was prepared by dissolving 14.87 g of Zn (NO3)2 in 500 mL of blank solution. The blank solution, NaNO3 was prepared by dissolving 63.75 g of NaNO3 in 5 L deionised water. The solution of zinc nitrate was prepared using standard flasks. The range of concentration of the prepared metal solutions varied between 10 and 200 mg/L. The solutions were prepared by diluting the zinc stock solution, which were obtained by dissolving in blank solution. The pH of the solutions was adjusted with 0.1M HCI and 0.1M NaOH.

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3.3

Biosorption Experiments

3.3.1

Batch Experiment

Batch biosorption equilibrium experiments were conducted in 250 mL conical flasks at a constant agitation speed that is 220 rpm. The experiments were carried out at four different temperatures, that were 30 and 60 , 40 50

for twelve sets readings of zinc concentration. The experiments were

carried out in duplicate, where the total number of samples will be collected are there hundred sixty samples. The first run of experiment will be using the palm shell activated carbon. Around 10 mL of samples solution is being transferred into the test tube. The conical flasks that contain the sample are being placed inside the orbital shaker overnight. After 24 hrs, the samples were filtrated, and collected in a test tube for further analytical experiments lines.

3.3.2

Analytical Experiment

The mixture samples of the zinc ions and original PSAC were before batch experiment and after batch experiment were collected in a test tube. The measurement of the initial and equilibrium metal ions concentrations was carried out using ICP-OES (Optima 7000DV, Perkin Elmer).The amount of metal absorbed by palm shell activated carbon was calculated from the differences between metal quantity added to the biomass and metal content of the supernatant using the following equation: Equilibrium sorption capacity, (mg/g)

(3.1)

Where

is the metal uptake (mg/g),

and

are the initial and final metal

concentrations in the solution (mg/L), respectively, V the solution volume (mL) and M is the mass of biosorbent (g).

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3.4

Adsorption Equilibrium Models

3.4.1

Langmuir Isotherm

The relationship between the PSAC and the zinc ions was quantified by fitting the obtained sorption values to the Langmuir isotherm. In this case, the following form of the Langmuir equation is applied in Equation 3.2

(3.2) Where qm is the maximum sorption uptake per unit mass of adsorbent in mg/g, Ce is the equilibrium concentration of heavy metal ions in mg/L and b is the Langmuir constant of sorption and desorption rate. To get the equilibrium data, initial zinc

(II) concentration were varied while the adsorbent mass in each sample was kept constant.

If the metal ions are taken up independently on a single type of binding site in such a way that the uptake of the first metal ion does not affect the sorption of the next ion, then the sorption process would follow the Langmuir adsorption isotherm. (Mubashir Hussain Nasir et. al, 2007) A further analysis of the Langmuir equation can be made on the basis of a dimensionless equilibrium parameter, RL (L.K. Koopal et. al 1994) also known as the separation factor, given by (3.3) The value of RL lies between 0 and 1 for a favorable adsorption, while RL > 1 represents an unfavorable adsorption, and RL = 1 represents the linear adsorption, while the adsorption operation is irreversible if RL =0.

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3.4.2

Freundlich Isotherm

The Freundlich isotherm equation describes the biosorption of zinc ions from liquid to solid surface (PSAC) and assumes that the stronger binding sites are occupied first and that the binding strength decreases with the increasing degree of site occupation. The Freundlich isotherm assumes a heterogeneous surface with a non-uniform distribution of heat of adsorption over the surface. This isotherm can be described as equation 3.4.

(3.4)

where = equilibrium metal uptake, mg/g KF = Freundlich constant of adsorption capacity, mg/g Ce = final concentration of zinc ions, mg/L n = Freundlich constant of adsorption intensity

Equation 3.5 can be transformed into a linear equation form as follows: (3.5)

Where, KF and n are physical constants of Freundlich adsorption isotherm. Also, KF and n are indicators of adsorption capacity and adsorption intensity, respectively. The slope and intercept of linear Freundlich equation are equal to n and ln KF, respectively. If the n value is in the range of 0 < n < 1, it indicates a favorable adsorption (M.Tukaram Bai et al, 2010).

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3.5

Biosorption Thermodynamics

The thermodynamics studies were carried out by conducting batch biosorption experiments with different initial zinc concentrations and temperature. Samples were taken at constant periods and analyzed for their zinc concentration. The values of the thermodynamic parameters such as H, G and S describing zinc ions biosorption by PSAC, were calculated using the thermodynamic equations described below. The biosorption process can be regarded as a heterogeneous and reversible process at equilibrium.

The thermodynamic parameter such as the Gibbs free energy change indicates the degree of spontaneity of a process. A higher and negative value indicates a more energetically favorable process. Therefore, it can be used to evaluate the thermodynamic feasibility of the adsorption of zinc ions on PSAC. The Gibbs free energy change of the sorption reaction is given by equation 3.6 and 3.7.

(3.6)
S H R RT

ln K

(3.7)

where = standard free energy, kJ/mol = enthalpy, kJ/mol T = temperature, K = entropy, kJ/mol.K K = equilibrium constant from Langmuir isotherm

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CHAPTER 4

4 RESULTS AND DISCUSSION

4.1

The Effect of initial zinc ion concentration

The effect of initial zinc ion concentration on biosorption was studied at temperature 30 C, 40 C, 50C and 60 C at pH 5 with a constant agitation speed of 220 rpm. Figure 4.1 shows that all the curves have the same pattern for the initial zinc ion concentration against the adsorption percentage, where the adsorption percentage declined as the initial zinc ion concentration increased. The figure 4.1 and 4.2 shows that the metal uptake increases and the percentage adsorption of zinc decreases with increase in metal ion concentration at different range of temperature.

The increment of metal uptake was tabulated in table 4.1 at different range of temperature and initial concentration of zinc ions. However, the percentage adsorption of zinc ions on PSAC was decreased from 73.1 % to 36.12 % (temperature 30 C). Though an increase in metal uptake was observed, the decrease in percentage adsorption may be attributed to lack of sufficient surface area to accommodate much more metal ions available in the solution. The percentage adsorption at higher concentration levels shows a decreasing trend whereas the equilibrium uptake of zinc displays an opposite trend.

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At lower concentrations, all zinc ions present in solution could interact with the binding sites and thus the percentage adsorption was higher than those at higher zinc ion concentrations. At higher concentrations, lower adsorption yield is due to the saturation of adsorption sites. As a result, the purification yield can be increased by diluting the aqueous solutions containing high metal ion concentrations.

Figure 4.1: The Sorption Capacity for biosorption of Zinc () ions on PSAC at different temperatures

Table 4.1: Sorption Capacity at different temperatures and initial concentration Varies qe , mg g-1 Ci, mg/L 10 20 30 40 50 70 90 120 150 30 3.248 5.654 7.884 10.560 11.632 17.484 20.272 25.188 27.088 Temperature, C 40 50 1.062 1.237 3.837 3.849 4.606 3.996 4.812 3.988 5.217 4.940 5.940 5.664 6.532 5.864 6.776 6.184 8.204 5.520 60 3.712 6.033 7.568 9.336 9.520 10.632 12.216 11.812 15.120

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Figure 4.2: The Adsorption capacity of Zinc () ions during the biosorption process by PSAC

4.2

The Effect of Temperature

Temperature is found to be an important parameter for the sorption of zinc ions dealing with the thermodynamics of the biosorption process. The studies on biosorption of Zinc with PSAC were carried out with four different temperatures which were 30 C, 40 C, 50 C and 60 C. It is directly related to the kinetic energy of the zinc ions. Temperature changes will affect a number of factors which are important in heavy metal ion biosorption. Some of the factors include: (Sag, Y. and T. Kutsal, 2000.)

a. The stability of the metal ion species initially placed in solution. b. The stability of micro organism-metal complex depending on the biosorption sites; c. The effect of temperature on the microorganism cell wall configuration; d. The ionization of chemical moieties on the cell wall.

18

The both figure 4.1 and 4.2 at the pre shows the relationship of temperature with adsorption percentage and the sorption capacity based on the initial zinc ions metal concentration. Based on the Figure 4.1 it can be seen that for the adsorption of zinc ions initially the uptake capacity increases in a linear way with rising equilibrium concentration. Uptake capacity is eventually limited by the fixed number of uptake active sites on the adsorbent and a resulting plateau can be observed. This plateau would represent the maximum uptake capacity of the adsorbent for zinc ions at different temperature values. From the below table 4.2 it was found that qmax for zinc ions are 52.083, 8.503, 7.032 and 13.00 mgg1 at temperature values of 303, 313, 323 and 333 K, respectively.

Table 4.2: Freundlich and Langmuir model parameters for biosorption of zinc (11) with original PSAC Temperature (K) b (L/mg) Langmuir Isotherm qmax (mg/g) 303 313 323 333 0.0163 0.118 0.137 0.220 52.083 8.503 7.032 13.000 0.9576 0.229 -0.847 0.9775 0.074 -0.735 0.9513 0.033 -0.578 0.9635 0.021-0.263 1.153 1.093 1.041 1.574 0.7075 0.4898 0.5438 0.0307 0.9739 0.8759 0.8009 0.9652 R2 RL Freundlich Isotherm Kf (mg/g) n R2

The initial zinc concentration may provide a driving force to overcome all mass transfer resistances between the adsorbent and the adsorption medium. Hence higher sorption capacities were obtained at higher initial concentrations of zinc point up by T.Fan (2001). Figure 4.1 shows that the uptake capacity of zinc ions increases as the temperature increases.

The entire experimental results for organic reaction of biosorption indicated that adsorption of zinc ions was endothermic (29.72 kJ/mol). The increment in temperature may lead to a swelling effect within the internal structure of adsorbent enabling metal ions to penetrate further (Ozer, 2001). The rise in temperature would also cause a rise in kinetic energy of sorbent particles.

19

First, the collision frequency between sorbent and sorbate would increase, this results in the enhanced sorption on to the surface of the sorbent. Second, at high temperature due to bond rupture of functional groups on adsorbent surface there may be an increase in number of active sorption sites, which may also lead to enhance sorption with the rise in temperature (E.Malkoc et al., 2005)

4.3

Adsorption Equilibrium Models

The biosorption of Zn (II) was investigated as a function of concentration at different temperatures in the range of 10 200 mgL using 0.2495 mg to 0.2505 mg of adsorbent, 250 mL of adsorbate solution, and 24 hours shaking time at a shaking speed of 220 rpm. The results indicated that the uptake of metal ions was above 60% at low adsorbate concentrations (1090 mgL1) and 6 % 59 % at high concentrations (100200 mgL1). The equilibrium data for the adsorption of Zn(II) on original Palm shell activated carbon (PSAC) was tested with two adsorption isotherm models (Langmuir, and Freundlich, isotherm) among which two models were found to be suitable for the Zn(II) adsorption. The Langmuir isotherm model applied to the estimation of maximum adsorption capacity corresponding to complete monolayer coverage on the PSAC surface. The equilibrium models are extensively used to investigate the amounts of zinc ions absorbed by a certain PSAC. The distribution of zinc ions between solution and PSAC is a measure of the position of equilibrium and can be expressed by one or more isotherms. The equilibrium distribution is important in determining the maximum biosorption capacity. The Langmuir isotherm model was chosen to estimate the maximum adsorption capacity corresponding to complete monolayer coverage on the biomass surface. The Freundlich model was chosen to estimate the adsorption intensity of the biosorbent towards the biomass.

20

4.3.1

Langmuir Isotherm

The isotherm represents the equilibrium relationship between the metal uptake by the adsorbent and the final metal concentration in the aqueous phase, showing the adsorption capacity of the adsorbent. The pH value of 5.0 was chosen as the experimental condition for the determination of adsorption isotherms. All the datas were fitted into Langmuir isotherm for all the four different temperature. The Figure 4.3, Figure 4.4, Figure 4.5 and Figure 4.6 were generated from the Langmuir isotherm respectively. The best-fit equilibrium model was determined based on the linear regression correlation coefficient R2.

Figure 4.3: Langmuir isotherm for biosorption of Zinc () ions on original PSAC at T = 30C

21

Figure 4.4: Langmuir isotherm for biosorption of Zinc () ions on original PSAC at T= 40C

Figure 4.5: Langmuir isotherm for biosorption of Zinc () ions on original PSAC at T = 50C

22

Figure 4.6: Langmuir isotherm for biosorption of Zinc () ions on original PSAC at T= 60C

Here we consider Langmuir model with its main assumptions: (Leszek Czepirksi et al.) a. Adsorption only takes place only at specific localized sites on the surface and the saturation coverage corresponds to complete occupancy of these sites. b. Each site can accommodate one and only one molecular or atom. c. The surface is energetically homogeneous, and there is no interaction between neighboring and adsorbed molecules or atoms. d. There are no phase transitions.

The RL values calculated were between 0.229 and 0.847 (Table 4.2) indicating highly favorable biosorption of Zn (II) on PSAC for temperature 303 K. Overall, the entire inorganic reactions for different temperature is favorable and by referring to the RL values in table 4.2, the biosorption of Zn (II) at temperature 333 K gives the lowest range of RL, (0.021-0.263). This is due to the high temperature, where the low range of RL value probably caused by a change in the texture of the PSAC and a loss in the sorption capacity due to material deterioration. (Volesky, 2003)

23

The validity of Langmuir isotherm suggests that adsorption is a monolayer process and adsorption of all species requires equal activation energy. As Table 4.2 shows, b increases with increasing of temperature, indicating that adsorption of zinc ions onto PSAC surfaces increases with temperature. The results also implied that the affinity of the binding sites increased with temperature. (Moradi et al. ,2011) page.

4.3.2

Freundlich Isotherm

The results of present study indicates that the Freundlich model does not fit the experimental data since the R2 values were 0.9739, 0.8759, 0.8009 and 0.9652, respectively, for 303, 313, 323 and 333 K. Below are the figure 4.7, figure 4.8, figure 4.9 and figure 4.10 shows has the n value in the range of 0 < n < 1 for the biosorption of zinc ions using original PSAC. Thus, the adsorptions for different temperature with the variations of initial concentration of zinc are favorable.

Figure 4.7: Freundlich isotherm for biosorption of Zinc () ions on original PSAC at T= 30 C

24

Figure 4.8: Freundlich isotherm for biosorption of Zinc () ions on original PSAC at T= 40 C

Figure 4.9: Freundlich isotherm for biosorption of Zinc () ions on original PSAC at T= 50 C

25

Figure 4.10: Freundlich isotherm for biosorption of Zinc () ions on original PSAC at T= 60 C

Freundlich isotherm does not describe the saturation behavior of adsorbents. Regarding the coefficients of Freundlich model, KF increased with temperature, revealing that adsorption capacity increased with temperature. Like KF, n increased with temperature as well. Since all n values obtained from the isotherms exceeded unity, the zinc ions were favorably adsorbed onto PSAC surfaces. The highest values of n were 0.7075 at 303K.These data indicate favorable adsorption. Refer to table 4.2.

For all cases, the Langmuir equation fits the experimental data better than the Freundlich equation. This isotherm does not predict any saturation of the adsorbent by the sorbate. Instead, infinite surface coverage is predicted, indicating multilayer sorption on the surface.

26

4.4

Thermodynamics properties for biosorption of Zinc() by original PSAC

In the present study, thermodynamic parameters were obtained by varying temperature conditions over the range 303-333 K and varying initial concentrations by keeping other variables constant. Thermodynamic parameters were calculated to confirm the adsorption nature of the present study. The thermodynamic constants, free energy change G, enthalpy change, H and entropy change, S were calculated to evaluate the thermodynamic feasibility of the process and to confirm the nature of the biosorption process. Those parameters were evaluated using the equation 3.6 and 3.7.

Table 4.3: Values of 1/T and ln b for the Gibbs Energy Graph T (C) 30 40 50 60 Temperature (K) 303 313 323 333 1/T 0.0033 0.0032 0.0031 0.0030 K 0.8493 0.9999 0.9656 2.8547 ln K -0.1633 -0.0001 -0.0350 1.0490

Figure 4.11:Thermodynamics parameters (The Gibbs Energy) for biosorption of Zinc () ions on original PSAC

27 The thermodynamic parameters of enthalpy energy, H and entropy energy, S were obtained from the slope and intercept of vant Hoff plot of ln K against 1/T (Fig. 4.11 and table 4.3). The negative G values for Zn (II) at various temperatures approved the adsorption processes were spontaneous, and the values of G (Table 4.4) decreased with an increase in temperature, indicated that the spontaneous nature of adsorption of Zn (II) were inversely proportional to the temperature. Enhancement of adsorption capacity at higher temperatures may be attributed to the enlargement of pore size and activation of the PSAC surface.

The biosorption process at temperature 303 K gives a positive value of Gibbs energy of 0.8314 kJ/mol tabulated at table 4.4. The author thinks that the positive value of Gibbs energy was because the process was non-spontaneous enough to give a negative value of Gibbs energy. Table 4.4: Gibbs Energy for Biosorption of Zinc () ions on original PSAC Temperature (K) 303 313 323 333 G (kJ/mol) 0.8314 -0.12 -1.08 -2.03 Process Non feasible feasible feasible feasible

Based from Figure 4.11, the enthalpy and entropy were evaluated by multiplying the gas constant, R referring to the equation 3.7. Therefore, the values of the entropy and enthalpy were 95.34 J/mol.K and 29.72 kJ/mol. The positive value of enthalpy energy H, 29.72 kJ/mol illuminated the endothermic nature of zinc ions biosorption.

The thermodynamic parameters for the biosorption of zinc ions using original PSAC were tabularize in table 4.5. The positive value of entropy energy S, 0.095 kJ/mol.K suggested the increase randomness at the solid or solution interface during the biosorption of zinc ions on PSAC.

28

As the temperature increases, the Gibbs free energy decreases with more negative values, which it indicates the degree of spontaneity of the biosorption process, and the more negative values reflect a more energetically favorable biosorption process of zinc ions onto original PSAC. In addition, from the table 4.5 below, the Langmuir constant, b (L/mg) is proportional to the temperature, which eventually gives a negative declining value of Gibbs energy. Since Gibbs energy related to the spontaneous of the biosorption process, thus at higher temperature of 333 K the degree of spontaneity was higher due to the kinetic movement of the PSAC and zinc ions increases as well. Table 4.5: The thermodynamics parameters for the entire Biosoprtion of Zinc () ions on original PSAC Temperature, K 303 313 323 333 R2 H (kJ/mol) S (kJ/mol) G (kJ/mol) 0.8314 0.6627 29.72 0.095 -0.12 -1.08 -2.03

b (L/mg) 0.0163 0.1180 0.1370 0.2200

29

4.5

Comparison of biosorption of Zinc(II) with different Adsorbents Reported in Literature

The adsorption capacities of the adsorbents for the biosorption of Zinc(II) have been compared with those of other adsorbents reported in literature and the values of adsorption capacities have been presented in Table 4.6. The values reported in the form of monolayer adsorption capacity. The experimental data of the present investigations are comparable with the reported values. From the Table 4.6, it is observed that palm shell activated carbon gives the highest adsorption capacity compared to the other biosorbents. Another thing, the author thinks that the high adsorption capacity for PSAC was due to the parameter of pH and agitation speed of 220 rpm during the biosorption of zinc ions. Table 4.6: Zinc() adsorption capacities (qm) of agricultural waste materials Biosorbent PSAC Sugar beet pulp Almond husk activated carbon Bengal gram husk Cassava waste Peanut hulls Coir Fibers Pecan Shell carbon Banana peel Barlew straw Orange peel Cocoa shell qm, mg/g 52.08 35.60 35.34 33.81 11.06 9.00 8.60 7.38 5.80 5.30 5.25 2.92 Equilibrium Model Freudlich,Langmuir Freudlich Freudlich,Langmuir Freudlich,Langmuir Freundlich Freundlich Freundlich Reference Present Study Pehlivan et al.,2006 Hasar et al. Saeed et al. Abia et al. Brown at al. Shukla et al. Bansode et al Annadurai et al. Larsen & Schierup Annadurai et al. Meunier et al.

30

4.6

Comparison of pH changes for biosorption of Zinc() with different adsorbent were revised

The biosorption of Zinc() ions with PSAC was carried out under pH 5. Based, on the literature review studies, it was observed that the optimum pH range were 4 to 6 to achieve the maximum sorption capacity. The Table 4.9 indicates the optimum pH for biosorption of Zinc() ions using different biosorbents. It is well known that the pH value of the medium affects the solubility of Zinc ions and the concentration of the counter ions, on the functional groups of the PSAC cell walls. A PSAC presents a high content of ionizable groups (carboxyl groups) on the cell wall polysaccharides, which makes it very liable to the influence of the pH value. As shown in Table 4.7 the uptake of free ionic zinc depends on pH. The biosorption of metallic zinc ion was observed to increase with increase in pH up to a value of 6.

These functional groups from PSAC carry negative charges that allow the functional cell wall components to be potential binding sites for cations (P.Yin et al, 1999). Since high proton concentration at lower pH, zinc ions uptake was decreased because of the positive charge density on metal binding sites. Namely hydrogen ions effectively compete with zinc ions to bind the sites. The negative charge density on the PSAC surface increases with increasing in pH due to deprotonation of the metal binding sites. Table 4.7: The biosorption of Zinc() in different pH with different biosorbents Biosorbent Syzygium cumini L. A.indica bark PSAC Tectona grandis Activated carbon Sargassum sp. qmax ( mg/g) 35.84 33.49 52.08 16.42 31.11 24.35 pH 6.0 6.0 5.0 5.0 4.5 4.5 Reference N.Rakesh (2006) King et al. Present study Prasanna Kumar Mohan et al. Erteves et al.

31

CHAPTER 5

5 CONCLUSION AND RECOMMENDATIONS

5.1

Conclusion

The current study shows that the biomass of original Palm Shell Activated Carbon was used as effective biosorbents for the biosorption of Zn (II) from aqueous solution. The specific objectives of this study had been accomplished by carrying out the experiment according to the methodology, and then the thermodynamics parameters were evaluated based on the tabulated datas. The initial concentrations of zinc affect the sorption capacity of PSAC. The sorption capacity is relative to the initial concentration. The highest sorption capacity was achieved at temperature 303 K. Zinc biosorption by original PSAC was fitted well with the Langmuir and Freundlich adsorption isotherms equations in the studied metal concentration range. The thermodynamic parameters include H, G and S. Those parameters were strongly affected by the temperature and initial concentration of zinc ions. The effect of temperature clearly observed during the computation of Gibbs free energy, where the temperature is proportional to the Gibbs energy. The positive value of H (29.72 kJ/mol) indicates an endothermic process. Hence S (0.095 kJ/mol) has to be positive value as well.

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5.2

Recommendations

The entire studies of thermodynamics properties for biosorption of zinc metal using original palm shell activated carbon was successfully accomplished. As a conclusion, the highest adsorption capacity (73.1 % ) for biosorption of zinc metal using original PSAC was achieved at temperature 303 K with the initial concentration of 10 mg/L. For this present study, the Gibbs energy obtained at temperature 303 K is a positive value, where the reaction is not spontaneous. So, for further studies in future, it is recommended to decrease the initial concentration of zinc metal, to attain an adsorption capacity of above 90% or even up to 100 % and to carry out at the same temperature again. In addition, other parameters can be adjusted to obtain a higher adsorption capacity.

Since, this study of using original PSAC manage to obtain adsorption capacity of 73.1%, it is a good option to replace the original PSAC with the biomodified PSAC in future studies, so that the sorption capacity of zinc can be increase. Furthermore, base on the literature review studies and present work, at pH range of 5 to 6 the biosoprtion of zinc will be at the optimum stage. Hence, it is another alternative way to increase the sorption capacity of zinc by increasing the pH value to 5.5 or 6.

33

REFERENCE

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Jin-Ho Joo 1, S. H.-E. (2010). Comparative study of biosorption of Zn by Pseudomonas aeruginosa. International Biodeterioration & Biodegradation 64 , 734-741. Jonathan Fabriato and Aline Nathasiah (2009). Equilibrium and kinetic studies in adsorption of heavy metals using biosorbent:. Journal of Hazardous Materials 162 , 616645 K.S. Rao1, M. M. (2010). Review on cadmium removal from aqueous solutions. International Journal of Engineering, Science and Technolog Vol 2 , 81-103. M.Tukaram Bai, K.. (September,2010). Equilibrium, kinetics and Thermodynamic studies on biosorption of copper and zinc from mixed solution by Erythitina variegata orientalis leaf powder. Indian Journal of Chemical Technology , 346-355. Mubashir Hussain Nasir, R. N. (2007). Efficacy of modified distillation sludge of rose (Rosa centifolia) petals. Journal of Hazardous Materials 147 , 10061014. N. A. Adesola Babarinde, O. O. (November, 2007). Isotherm and thermodynamic studies of the biosorption of Copper ions by Erythrodontium barteri. International Journal of Physical Sciences Vol. 2 , 300-304. N. Gamze Turan, S. E. (2011). Adsorption of copper and zinc ions on illite: Determination of the optimal conditions. Applied Clay Science 52 , 392-399. N.A. Adesola Babarinde, P. J. (May-June 2008 ). Isotherm and Thermodynamic Studies of the Biosorption of Zinc (II). The Pacific Journal of Science and Technology , 196202. P. King. (2008). Biosorption of zinc from aqueous solution using Azadirachta. Journal of Hazardous Materials 152 , 324329. P.Venkateswarlu, G. V. (September 9, 2008). Biosorption of Zn(II) from an aqueous solution by Erythrina variegata orientalis leaf powder. International Journal of Physical Sciences Vol. 3 , 197-204. Ramiro J.E. Martinsa, R. P. (2004). Cadmium(II) and zinc(II) adsorption by the aquatic. Water Research 38 , 693-699. Salem M. Hamza Hanan, F. A. (2010). Optimization of Cadmium, Zinc and Copper biosorption in an aqueous solution by Saccharomyces cerevisiae. Journal of American Science , 6-12. Shuguang Lua, S. W. (2007). Effective removal of zinc ions from aqueous. Journal of Hazardous Materials 149 , 208217. Sisca O. Lesmanaa, N. F. (2009). Studies on potential applications of biomass for the separation of heavy metals. Biochemical Engineering Journal 44 , 1941. Tarun Kumar Naiya, P. C. (2009). Saw dust and neem bark as low-cost natural biosorbent for adsorptive. Chemical Engineering Journal 148 , 68-79.

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Thomas Anish Johnson, N. J. (September,2008). Agricultural and agro processing wastes as low cost asdorbents for metal removal from wastewater. Journal of Scientific & Industrial Research , 647-658. Y. Prasanna Kumar, P. K. (2006). Comparison for adsorption modelling of copper and zinc from aqueous. Journal of Hazardous Materials B137 , 12461251. Yun Zhanga, Y. L.-q.-j.-y.-F. (2010). Characterization and adsorption mechanism of Zn2+ removal by PVA/EDTA resin. Journal of Hazardous Materials 178 , 1046 1054.

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APPENDICES

APPENDIX A1: Graphs

Temperature 30 C

Figure B1.1: Percentage uptake of biosorption of Zinc () ions on original PSAC (T = 30 C)

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Figure C1.2: The qe graph for biosorption of Zinc () ions on original PSAC (T = 30 C)

Figure D1.3: Thermodynamic parameter for biosorption of Zinc () ions on original PSAC (T = 30 C)

38

Parameter: Temperature 40 C

Figure E1.4: Percentage uptake of biosorption of Zinc () ions on original PSAC (T = 40 C)

Figure F1.5: The qe graph for biosorption of Zinc () ions on original PSAC (T = 40 C)

39

Figure G1.6: Thermodynamic parameter for biosorption of Zinc () ions on original PSAC(T = 40 C)

40

Parameter: Temperature 50 C

Figure H1.7: Percentage uptake of biosorption of Zinc () ions on original PSAC(T = 50 C)

Figure I1.8: The qe graph for biosorption of Zinc () ions on original PSAC (T = 50 C)

41

Figure J1.9: Thermodynamic parameter for biosorption of Zinc () ions on original PSAC(T = 50 C)

42

Parameter: Temperature 60 C

Figure K1.10: Percentage uptake of Zinc () ions on original PSAC (T = 60 C)

Figure L1.11: The qe graph for biosorption of Zinc () ions on original PSAC (T = 60 C)

43

Figure M1.12: Thermodynamic parameter for biosorption of Zinc () ions on PSAC (T = 60 C)

1400000 Corrected intensity 1200000 1000000 800000 600000 400000 200000 0 0 200000 400000 600000 800000 1000000 1200000 1400000 Net intensity R = 1

Figure N1.13: Calibration graph for biosorption Zinc () ions on original PSAC (T = 60 C)

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APPENDIX O2: Tables

Table P2.1: The Calibration table for the biosorption of Zinc () ions on PSAC

Solution Blank solution Standard 1:10ppm Standard 3:50ppm Standard 3:100ppm Standard 3:150ppm Standard 3:200ppm

Net intensity 59.9 59327.6 288304.8 594518.7 914531.3 1238441.2

Corrected intensity 59.9 59267.7 288244.9 594458.8 914471.4 1238381.2

Table Q2.2: Sorption Capacity for different temperatures as initial concentration varies qe , mg g-1 Temperature, C 40 1.062 3.837 4.606 4.812 5.217 5.940 6.532 6.776 8.204

Ci, mg/L 10 20 30 40 50 70 90 120 150 30 3.248 5.654 7.884 10.560 11.632 17.484 20.272 25.188 27.088

50 1.237 3.849 3.996 3.988 4.940 5.664 5.864 6.184 5.520

60 3.712 6.033 7.568 9.336 9.520 10.632 12.216 11.812 15.120

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Table R2.3: Adsorption capacity for different Temperature as initial concentration varies Concentration,ppm 10 20 30 40 50 70 90 120 150 170 30 73.1 65.89 63.23 59.57 59.33 62.35 54.56 48.89 46.54 46.39 Adsorption % Temperature,C 40 66.94 60.45 58.42 56.59 56.07 40.1 26.63 26.45 26.22 23.75

50 57.15 63 59.28 53.15 52.23 42.92 31.93 26.62 9.24 8.73

60 72.89 64.05 56.33 53 43.64 35.95 31.23 21.38 14.74 15.74

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APPENDIX S: Calculations for thermodynamic parameters

Sample Calculation

Temperature 303 K

1.

Langmuir Isotherm

From the Figure 4.3 the equation obtain from the graph is Compare the above equation with equation 4.1:

From the comparison we can evaluate the b and qm value.

Gradient from the figure 4.3,

Then evaluate the b value,

Next, evaluate the dimensionless equilibrium parameter, RL from equation 4.2

Co b

= 11.259 mg/L = 0.0163 L/mg

47

2.

Freundlich Isotherm

From the Figure 4.3 the equation obtain from the graph is Compare the above equation with equation 4.4

From the comparison of the two equations, need to evaluate the KF and n value. Freundlich constant of adsorption intensity, n Freundlich constant of adsorption capacity, KF = = 0.7075

so, KF = 1.153 mg/g

Thermodynamics Parameter The parameter consists of Gibbs energy, entropy and enthalpy. The Figure 4.11 was used to evaluate the above parameters. Figure 4.11 was plotted according to the equation 4.6 :

This equation was obtained from the figure 4.11 Thus, we can evaluate the entropy and enthalpy. Using gas constant, R = 8.314 J/mol.K

Hence from the above value, the Gibbs energy can be evaluated using following equation :