STABILITY OF CYPERMETHRIN AGAINST A PREPARED HIGH...

STABILITY OF CYPERMETHRIN AGAINST A PREPARED HIGH

SURFACE AREA MAGNESIUM OXIDE

HANIS BINTI MOHD YUSOFF

UNIVERSITI TEKNOLOGI MALAYSIA

STABILITY OF CYPERMETHRIN AGAINST A PREPARED HIGH

SURFACE AREA MAGNESIUM OXIDE

HANIS BINTI MOHD YUSOFF

A thesis submitted in fulfilment of the

requirements for the award of the degree of

Master of Science (Chemistry)

Faculty of Science

Universiti Teknologi Malaysia

JUNE 2006

iii

Dedicated to my beloved father Hj Mohd Yusoff bin Hussin,

Mother Hjh Wan Bidah binti Wan Sulaiman,

family and friends.

iv

ACKNOWLEDGEMENT

First of all, in a humble way I wish to give all the Praise to Allah, the

Almighty God for giving me the strength and the time to complete this work.

I would like to take this opportunity to express my sincere thanks to my

supervisor Assoc. Prof. Dr Abdul Rahim bin Yacob for believing in me. I am also

grateful with his patience, endless efforts in guiding and imparting his vast

knowledge to me. Writing this thesis is a remarkable accomplishment, thanks to the

ever constant advice from my supervisor.

At the same time, I would also like to thank all lab assistants from the

Department of Chemistry for their help and advice with the handling of the

equipment in the laboratories. To all my colleagues, thank you for your help and

support. I am also grateful to the Department of Chemistry, Faculty of Science

Universiti Teknologi Malaysia for all the facilities and financial support.

Lastly, I would like to acknowledge my family, whose patience love enabled

me to complete this research.

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ABSTRACT

High surface area magnesium oxide was prepared by various methods of preparation using modified dehydration technique. Commercial magnesium oxide was first transformed into its hydroxide. The magnesium hydroxide was heated under high vacuum at different temperatures of 200, 400, 600 and 800 degree Celsius and high surface area magnesium oxide was obtained. The activated magnesium oxide sample was labeled as dehydrated magnesium oxide. The same magnesium hydroxide was also calcined at various temperatures and was labeled as dehydrated and calcined magnesium oxide. Finally, the third magnesium oxide sample was labeled as magnesium oxide sol gel, produced by synthesis of Mg turnings to form sol gel solution and was dried using autoclave which will convert to its magnesium hydroxide sol gel. Again, activation using high vacuum will convert magnesium hydroxide sol gel into its high surface area magnesium oxide. To characterize the resulting magnesium oxide samples, several spectroscopic techniques were used which includes Fourier Transform Infra-Red, X-Ray Diffraction, Nuclear Magnetic Resonance and Electron Spin Resonance. For better understanding of the magnesium oxide surface area and morphology, Nitrogen Gas Adsorption and Scanning Electron Microscope, was used. Pyrethrin is the most effective insecticide. However it is not harmful to mammals or humans. Synthetic pyrethroid that is cypermethrin later was developed. Since cypermethrin was sprayed towards furnitures, floors, walls at home and at the agriculture field, thus their stability towards these matrices is important. In this study, the stability of cypermethrin under variously prepared high surface area magnesium oxide effect was studied using Fourier Transform Infra-Red spectroscopy and Gas Chromatography with Electron Capture Detector. For comparison, inert matrix of activated carbon was used.

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ABSTRAK

Magnesium oksida berluas permukaan tinggi telah disediakan dengan menggunakan pelbagai kaedah. Langkah pertama adalah dengan menukarkan magnesium oksida komersil kepada magnesium hidroksida dan telah melalui penggunaan vakum berkuasa tinggi dengan pemanasan pada pelbagai suhu 200, 400, 600 dan 800 darjah celsius, telah menghasilkan magnesium oksida berluas permukaan tinggi. Sampel ini dilabel sebagai magnesium oksida terhidrat. Magnesium hidroksida yang sama, turut dipanaskan secara pengkalsinan pada pelbagai suhu dan dilabel sebagai magnesium hidroksida terhidrat dan kalsin. Akhir sekali, sampel magnesium oksida yang ketiga dikenali sebagai sol gel magnesium oksida kerana teknik penyediakan adalah sedikit berbeza iaitu melibatkan sintesis yang menukarkan pita magnesium menjadi cecair sol gel dan dikeringkan dengan menggunakan ‛autoclave’ menukarkan ia kepada serbuk sol gel magnesium hidroksida. Pemanasan menggunakan vakum pada pelbagai suhu telah menukarkannya kepada magnesium oksida berluas permukaan tinggi. Bagi pencirian ke atas sampel magnesium oksida yang telah disediakan, beberapa kaedah spektroskopi telah digunakan iaitu Spektoskopi Inframerah, Pembelauan Sinar-X, Resonans Magnet Nukleus dan Resonans Spin Elektron. Bagi mengetahui lebih lanjut tentang permukaan sampel magnesium oksida yang diperolehi, penjerapan Gas Nitrogen dan Mikroskop Imbasan Elektron telah dijalankan. Pyrethrin merupakan racun serangga yang sangat berkesan. Walau bagaimanapun ia tidak merbahaya kepada mamalia mahupun manusia. Kemudian, pyrethroid sintetik iaitu cypermethrin telah dihasilkan. Memandangkan penggunaan cypermethrin adalah meliputi penyemburan di sofa, lantai, dinding rumah dan juga dalam bidang pertanian, maka kestabilan terhadap pelbagai matrik adalah amat penting. Dalam kajian ini, kestabilan cypermethrin di dalam pelbagai jenis magnesium oksida berluas permukaan tinggi dikaji dengan menggunakan Spektrokopi Inframerah and juga Kromatografi Gas dengan Pengesan Penangkap Elektron. Sebagai perbandingan, arang teraktif juga telah turut digunakan.

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TABLE OF CONTENTS

CHAPTER TITLE PAGE

DECLARATION ii

ACKNOWLEDGEMENT iv

ABSTRACT v

TABLE OF CONTENTS vii

LIST OF TABLES x

LIST OF FIGURES xi

LIST OF SYMBOLS xv

LIST OF APPENDICES xvi

1 INTRODUCTION

1.1 Background of research 1

1.1.1 Metal Oxide 1

1.1.2 Insecticides 1

1.1.3 Problem Statement 2

1.2 Objectives of Reasearch 2

1.3 Scope of Research 3

2 LITERATURE REVIEW

2.1 Magnesium Oxide 5

2.2 Insecticide 7

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2.2.1 Pyrethrin and Cypermethrin 7

3 EXPERIMENTAL

3.1 Sample Preparation 13

3.1.1 Activated Carbon 13

3.1.2 Cypermethrin 13

3.1.3 Converting Commercial MgO to Mg(OH)2 14

3.1.4 Dehydrated Magnesium Oxide (D-MgO) 15

3.1.5 Dehydrated and Calcined Magnesium Oxide

(DC-MgO) 15

3.1.6 Magnesium Oxide Sol Gel (SG-MgO) 15

3.2 Activation using Vacuum line system 16

3.3 Characterization 17

3.3.1 Fourier Transform Infrared Spectroscopy

(FTIR) 17

3.3.2 Scanning Electron Microscopy (SEM) 18

3.3.3 Nitrogen Gas Adsorption (NA) 19

3.3.3.1 Physisorption Isotherms 19

3.3.3.2 The-Brunauer-Emmet-Teller (BET) 21

3.3.3.3 Hysteresis Loop and Pore Clasification 22

3.3.4 X-Ray Diffraction (XRD) 26

3.3.5 Nuclear Magnetic Resonance (NMR) 29

3.3.6 Electron Spin Resonance (ESR) 32

3.4 Gas Chromatography 36

3.4.1 Stability Study of Cypermethrin 39

4 RESULTS AND DISSCUSSION

4.0 Introduction 41

4.1 Characterizations 41

4.1.1 Fourier Transform Inrfa-Red (FTIR) 41

4.1.2 Surface Morphology 49

4.1.3 X-Ray Diffraction (XRD) 54

ix

4.1.4 Surface Study using Nitrogen Gas

Adsorption (NA) 64

4.1.5 Electron Spin Resonance ESR 72

4.1.5.1 Fs+ Colour Centre 77

4.1.6 Nuclear Magnetic Resonance 79

4.2 Application in Cypermethrin 81

4.2.1 Fourier Transform Infra-Red (FTIR) 81

4.2.2 Gas Chromatography with Electron Capture

Detector Analysis 90

5 CONCLUSION AND RECOMMENDATIONS

5.1 Conclusion 101

5.2 Recommendations 102

REFERENCES 104

APPENDICES 112

x

LIST OF TABLES

TABLE NO. TITLE PAGE

3.1 Classifications of pores according to their width 23

3.2 Types of detectors and its selectivity 38

3.3 Operation Parameters for GC-ECD 40

4.1 FTIR peaks assignment 43

4.2 XRD peaks assignment for CM-MgO 55

4.3 XRD peaks assignment for D-Mg(OH)2 and SG-Mg(OH)2 58

4.4 XRD peaks assignment for D-MgO 400, DC-MgO 600 and

SG-MgO 400 60

4.5 XRD peaks assignment for D-MgO 600, DC-MgO 600 and

SG-MgO 600 63

4.6 Nitrogen Gas Adsorption-Desorption Analysis 70

4.7 Intensity ratio obtain from 1H MAS NMR spectra 79

4.8 Percentage of cypermethrin incubated with MgOs and AC 98

xi

LIST OF FIGURES

FIGURE NO. TITLE PAGE

1.1 Schematic layout of research scope 3

2.1 The expected pores and cavities in metal oxide 6

2.2 Molecular structures of compounds in pyrethrum 8

2.3 Molecule structures of resmethrin and cypermethrin 10

2.4 Cypermethrin isomers 11

3.1 Schematic layout of converting MgO to Mg(OH)2 14

3.2 Schematic diagram of rotary pump system 16

3.3 Types of BET isotherms 20

3.4 The hyteresis shapes of BET isotherm 23

3.5 Common model of pores (a) slit shape pore, (b) cylindrical shaped

pore and (c) pores between connected solid spheres 24

3.6 Types of pores 24

3.7 Simplified X-Ray Diffractometer 26

3.8 Pictorial view of Bragg’s law 27

3.9 Schematic layout of typical NMR spectrometer 30

3.10 Energy levels for a nucleus with spin quantum number ½ 31

3.11 The schematic diagram of an ESR spectrometer 33

3.12 Zeeman energy levels of an electron in an applied magnetic field 34

3.13 ESR sample cell 35

3.14 Schematic diagram of gas chromatography 37

3.15 Schematic diagram of injection port 37

3.16 Schematic diagram of ECD detector 39

4.1 FTIR spectrum of commercial magnesium oxide (CM-MgO) 42

xii

4.2 FTIR spectra of D-Mg(OH)2 and SG-MG(OH)2 43

4.3 FTIR spectra of D-MgO after activation under vacuum at

various temperatures; 200 oC, 400 oC, 600 oC and 800 oC. 45

4.4 FTIR spectra of DC-MgO after calcinations at various

temperatures; 200 oC, 400 oC, 600 oC and 800 oC. 46

4.5 FTIR spectra of SG-MgO after activation under vacuum

at various temperatures; 200 oC, 400 oC, 600 oC and 800 oC. 48

4.6 Type of bonding, Type A represent unassociated hydroxyl bond

and Type B stretching vibration of adsorbed water molecules 49

4.7 SEM micrographs of D-Mg(OH)2 and SG-Mg(OH)2 with

magnification of 1000X. 50

4.8 SEM micrographs of D-Mg 200, D-MgO 400, D-MgO 600 and

D-MgO 800 with magnification of 1000X. 51

4.9 SEM micrographs of DC-Mg 200, DC-MgO 400, DC-MgO 600

and DC-MgO 800 with magnification of 1000X. 52

4.10 SEM micrographs of SG-Mg 200, SG-MgO 400, SG-MgO 600

and SG-MgO 800 with magnification of 1000X. 53

4.11 XRD diffractogram of CM-MgO 55

4.12 XRD diffractograms of D-MgO activated under vacuum at

400 oC and 600 oC respectively 57

4.13 XRD diffractograms of D-MgO 400, DC-MgO 400 and

SG-MgO 400 59

4.14 XRD diffractograms of D-MgO 600, DC-MgO 600 and

SG-MgO 600 62

4.15 Adsorption-desorption isotherm plot of CM-MgO 64

4.16 Adsorption-desorption isotherms plot of D-MgO 400, D-MgO

600 and D-MgO 800. 66

4.17 Pore size distribution of D-MgO 400 and D-MgO 800 67

4.18 Adsorption-desorption isotherms plot of DC-MgO 400, DC-MgO

600 and DC-MgO 800. 68

4.19 Adsorption-desorption isotherms plot of SG-MgO 400,

SG-MgO 600 and SG-MgO 800. 69

4.20 Graph of BET surface area versus temperature for D-MgO,

DC-MgO and SG-MgO heated at various temperatures. 71

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4.21 ESR spectra of D-MgO 600 73

4.22 ESR spectra of DC-MgO 600 74

4.23 ESR spectra of SG-MgO 600 76

4.24 Schematic diagram of trapped electron on MgO 77

4.25 SG-MgO 600 shows (a) before UV-irradiation and (b) after

UV-irradiation, the formation of surface FS + (H) colour centre. 78

4.26 1H MAS NMR spectra of D-Mg(OH)2, before and after activation

using vacuum at temperature 400 oC, 600 oC and 800 oC 80

4.27 FTIR spectra of blank cypermthrin incubated at 46 ± 2 oC. 83

4.28 FTIR spectra of CM-MgO with cypermthrin incubated at 46 ± 2 oC 84

4.29 FTIR spectra of D-MgO activated under vacuum at 600 oC with

cypermthrin incubated at 46 ± 2 oC. 85

4.30 FTIR spectra of DC-MgO calcined at 600 oC with cypermthrin

incubated at 46 ± 2 oC. 86

4.31 FTIR spectra of SG-MgO activated under vacuum at 600 oC with

cypermthrin incubated at 46 ± 2 oC. 87

4.32 FTIR spectra of activated carbon, (AC) with cypermthrin

incubated at 46 ± 2 oC. 88

4.33 Two major pathways for cypermethrin’s degradation 89

4.34 GC-ECD chromatograms of blank cypermethrin monitored in an

incubator at 46 ± 2 oC. 90

4.35 A plot of peak height against incubation time for blank

cypermethrin incubated at 46 ± 2 oC. 91

4.36 GC-ECD chromatograms of cypermethrin incubated with

CM-MgO monitored in an incubator at 46 ± 2 oC. 92

4.37 A plot of peak height against incubation time for cypermethrin

incubated with CM-MgO at 46 ± 2 oC. 92


D-MgO monitored in an incubator at 46 ± 2 oC 93


incubated with D-MgO at 46 ± 2 oC. 94


DC-MgO monitored in an incubator at 46 ± 2 oC. 95

xiv

4.41 A plot of peak height against incubation time for

cypermethrin incubated with DC-MgO at 46 ± 2 oC. 96


SG-MgO monitored in an incubator at 46 ± 2 oC. 97


incubated with SG-MgO at 46 ± 2 oC. 98


SG-MgO monitored in an incubator at 46 ± 2 oC. 99


incubated with SG-MgO at 46 ± 2 oC. 100

xv

LIST OF SYMBOLS/ABBREVIATIONS

λ - Wavelength 2θ - Bragg Angle

FTIR - Fourier-Transformed Infrared

KBr - Potassium Bromide

XRD - X-ray Diffraction

Cu Kα - X-ray diffraction from Copper K energy levels

PDF - Powder Diffraction File

FWHM - Full Width Half Maximum

SEM - Scanning Electron Microscopy

EDX - Energy Dispersive X-Ray Analysis

BET - Brunnauer, Emmett and Teller

IUPAC - International Union of Pure and Applied Chemistry

NA - Nitrogen Adsorption

ESR - Electron Spin Resonance

NMR - Nuclear Magnetic Resonance

GC-ECD/FID - Gas Chromatography with Electron Capture Detector / Flame

Ionization Detector

MgO - Magnesium Oxide

D-MgO - Dehydrated MgO

DC-MgO - Calcine MgO

SG-MgO - Sol Gel MgO

H2 - Hydrogen

OH - Hydroxyl

P/Po - Relative pressure; obtained by forming the ratio of the

equilibrium pressure and vapour pressure Po of the adsorbate

at the temperature where the isotherm is measured

xvi

LIST OF APPENDICES

APPENDIX TITLE PAGE

A1 PDF Reference for Magnesium Oxide (MgO) 112

A2 PDF Reference for Magnesium Hydroxide (Mg(OH)2) 113

B1 EDAX analysis for D-Mg(OH)2 114

B2 EDAX analysis for SG-Mg(OH)2 115

B3 EDAX analysis for D-MgO 600 116

B4 EDAX analysis for DC-MgO 600 117

B5 EDAX analysis for SG-MgO 600 118

C1 ESR spectrum in full width 119

C2 Peak height calculation using internal standard

From ESR spectrum 120

D Percentage of decrease in GC-ECD data 121

CHAPTER 1

INTRODUCTION

1.1 Background of Research

1.1.1 Metal Oxide

Magnesium is one of the elements in Group 2, also known as alkaline earth

metal. The main minerals in which magnesium is found are carnellite, magnesite and

dolomite. Magnesium is the eight most abundance elements in the earth’s crust.

According to Knozinger et al. (1993) and Webb et al. (2003), magnesium oxide,

MgO exhibits a simple rock salt structure with minimal surface defect and may easily

be produced as high surface area material and also an excellent model compound for

the study of absorption phenomena.

1.1.2 Insecticides

One of the oldest insecticides that have been discovered is pyrethrum

(Garfield. E, 1990). Pyrethrins insecticides are derived from pyrethrum flowers, such

as chrysanthemums. The aromatic flower heads are powdered or extracted with

solvents. The resultant substance or product is contact poisons and nerve toxins for

2

insects (Hitmi et al. 1998 and Garfield, 1990). Pyrethrins boost several distinctions of

advantages such as-low mammalian toxicity, high toxicity to a broad spectrum of

insects at very low dosages and minor environmental impact (Chen and Wang, 1996,

Pedigo, 1989). Commercial uses ranges from household to industrial insect control

(Elliott, 1977).

Pyrethrins are however expensive and not stable especially when exposed to

sunlight, thus; synthetic pyrethrin also known as synthetic pyrethroid have been

introduced such as allethrin, cypermethrin, fenvalerate and permethrin (Elliott, 1977

and Pedigo, 1989).

1.1.3 Problem Statement

Cypermethrin is a type of insecticide which originated from a flower, since

the insecticide was sprayed towards tree trunks (garden) or on the floors and walls

(house), thus; their stability studies, with respect to times towards these matrices inert

and ionic, can open up a new dimensions in synthetic pyrethrins study of nontoxic

insecticides and pesticides. If this stability is understood, the effectiveness of these

new improved insecticides, which are not harmful to human are a major

breakthrough in agriculture sector and human consumption. This application was to

discover the ability of prepared high surface area MgO

1.2 Objectives of the Research

The objectives of this research are to investigate the potential of MgO as a

reaction medium as well as matrix in pesticide. This could be further divided into

three:

3

1) To synthesize dehydrated MgO, sol gel MgO and to prepare calcined

MgO.

2) To characterize all three types of MgO

3) To apply synthesized and prepared MgO in the stability study of

cypermethrin.

1.3 Scope of the Research

The scope of the research is to prepare and characterize three types of high

surface area MgO that has been identified as dehydrated method MgO (D-MgO),

open calcinations MgO (DC-MgO) and sol gel method MgO (SG-MgO). All these

three types of MgO were applied as a matrix in the stability study of cypermethrin.

Figure 1.1 Schematic layout of research scope

Sample Preparation

Spectroscopy Study

Stability of Cypermethrin

Surface and Morphology

Study

FTIR XRD ESR NMR

NA SEM

FTIR GC-ECD

D-MgO DC-MgO SG-MgO

4

Resulting MgO samples were characterized using spectroscopy instruments

which includes Fourier Transform Infra-Red (FTIR), X-Ray Diffraction (XRD),

Electron Spin Resonance (ESR) and Nuclear Magnetic Resonance. To have better

understanding on the surface and morphological properties, Nitrogen Gas Adsorption

(NA) and Scanning Electron Microscopes (SEM) were used. In stability of

cypermethrin, samples were analyzed using Fourier ransform Infra-Red (FTIR) and

Gas Chromatography with Electron Capture Detector (GC-ECD).

104

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