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UNIVERSITI PUTRA MALAYSIA
ENZYMATIC SYNTHESIS, CHARACTERIZATION AND ANALYTICAL APPLICATIONS OF FATTY HYDRAZIDES FROM PALM OIL
SHARIFAH MOHAMAD
FS 2008 34
ENZYMATIC SYNTHESIS, CHARACTERIZATION AND ANALYTICAL APPLICATIONS OF FATTY HYDRAZIDES FROM PALM OIL
By
SHARIFAH MOHAMAD
Thesis Submitted to the School of Graduate Studies, Universiti Putra Malayisa, in Fulfilment of the Requirements for the Degree of Doctor of Philosophy
May 2008
Abstract of thesis presented to the Senate of Universiti Putra Malaysia in fulfilment of the requirement for the degree of Doctor of Philosophy
ENZYMATIC SYNTHESIS, CHARACTERIZATION AND ANALYTICAL
APPLICATIONS OF FATTY HYDRAZIDES FROM PALM OIL
By
SHARIFAH MOHAMAD
May 2008
Chair: Professor Dato’ Wan Md. Zin Wan Yunus, PhD
Faculty: Faculty of Science
Hydrazides with the general formula R-CO-NHNH2, have received a lot of attention due
to their applications in biological, organic synthesis and analytical chemistry fields. The
preparation of fatty hydrazides from palm oil has been developed in this research. Fatty
hydrazides (FH) and fatty phenyl hydrazides (FPH) were successfully synthesized from
palm oil as a raw material by one-step lipase catalyzed reaction. FTIR and CHN
elemental analyses were carried out to determine the presence of the hydrazides in the
products. The method offers several advantages such as renewable and abundant of raw
materials, simple reaction procedure and high yield of products.
The application of the products as a reagent was carried out based on the ability of the
FH and FPH to form complexes with some metal ions. FH was successfully used as an
extractant for extraction and separation of copper(II). The separation of Cu(II) is
ii
possible from other metal ions such as Co(II), Cr(VI), Ni(II), Zn(II) and Fe(III) at pH
5.5-6.5. A preconcentration method was proposed for the determination of Cu(II) in
water samples. It was shown that the extraction from aqueous phase containing Cu(II)
with organic phase containing FH and then stripping the organic phase with 2 M of HCl
solution give a solution of Cu(II) 10 fold in concentrations.
FH was also successfully used as an extractant for extraction and separation of Mo(VI).
This metal successfully separated from other metal ions such as Ni(II), Co(II), Al(III),
Fe(III) and Mn(II). Quantitative stripping of Mo(VI) ion from the organic phase can be
carried out using 2 M ammonium hydroxide. This proposed method was applied for the
recovery of Mo(VI) from synthetic mixture and the results showed that more than 90%
recovery of Mo(VI) is achieved and the metal ion solution is free from the impurities.
FH and FPH were also evaluated as an extractant for extraction and separation of
gold(III) from chloride media. This metal was extracted quantitatively from hydrochloric
media at 0.001-0.1 M into the organic phase. Gold(III) was successfully separated from
Cu(II), Ni(II), Zn(II), Co(II) and Fe(III) by using FH or FPH. Quantitative stripping of
gold(III) from the organic phase can be carried out using 2.0 M thiourea in 1.0 M HCl
solution. The extraction and separation of gold(III) by FH or FPH was applied to
separate and recover pure gold(III) from synthetic mixtures.
iii
FPH synthesized from palm olein was also successfully used as a new reagent for the
determination of V(V) by spetrophotometric method. The method is based on the
colored complex of vanadium(V)-FPH. The metal ion forms dark brown colored
complex which has an absorption maximum at 405 nm. Beer’s law is valid over the
concentration range of 0.2-20 mg/L and the limit of detection of this method is
0.01 mg/L. The characteristics of this developed method are simple, good selectivity,
high sensitivity and rapid.
iv
Abstrak tesis yang dikemukakan kepada Senat Universiti Putra Malaysia sebagai memenuhi keperluan untuk ijazah Doktor Falsafah
SINTESIS BERENZIM, PENCIRIAN DAN PENGGUNAAN ANALISIS HIDRAZIDA LEMAK DARIPADA MINYAK KELAPA SAWIT
Oleh
SHARIFAH MOHAMAD
Mei 2008
Pengerusi: Professor Dato’ Wan Md Zin Wan Yunus, PhD
Fakulti: Fakulti Sains
Hidrazida dengan formula umumnya R-CO-NHNH2, mendapat banyak perhatian kerana
pengunaannya dalam bidang biologi, sintesis organik dan kimia analisis. Penyediaan
hidrazida lemak daripada minyak kelapa sawit telah dimajukan di dalam penyelidikan
ini. Hidrazida lemak (FH) dan hidrazida fenil lemak (FPH) telah berjaya disintesiskan
daripada minyak kelapa sawit sebagai bahan asas dengan tindakbalas satu peringkat
menggunakan enzim lipase sebagai mangkin. Analisis FTIR dan analisis unsur CHN
telah dijalankan untuk menentukan kehadiran kumpulan hidrazida di dalam produk.
Kaedah ini mempunyai beberapa kelebihan seperti bahan asas yang berterusan dan amat
banyak, prosedur tindak balas yang mudah dan hasil produk yang tinggi.
v
Penggunaan produk sebagai reagen telah dijalankan berasaskan kebolehan FH dan FPH
membentuk kompleks dengan beberapa ion logam. FH telah berjaya digunakan sebagai
pengekstrak untuk pengekstrakan dan pemisahan kuprum(II). Pemisahan kuprum(II)
adalah mungkin dari ion logam yang lain seperti Co(II), Cr(VI), Ni(II), Zn(II) dan
Fe(III) pada pH 5.5-6.5. Kaedah pra-pemekatan dicadangkan untuk penentuan Cu(II) di
dalam sampel air. Ini telah ditunjukkan dengan pengekstrakan fasa akueus yang
mengandungi Cu(II) dengan fasa organik yang mengandungi FH dan penanggalan
daripada fasa organik dengan larutan 2 M HCl memberikan pemekatan larutan Cu(II)
sebanyak 10 kali ganda.
FH juga telah berjaya digunakan sebagai pengekstrak untuk pengekstrakan dan
pemisahan Mo(VI). Logam ini telah berjaya dipisahkan dari ion logam seperti Ni(II),
Co(II), Al(III), Fe(III) dan Mn(II). Penanggalan kuantitatif bagi ion Mo(VI) dari fasa
organik boleh dijalankan dengan menggunakan larutan 2 M ammonia. Kaedah ini
diaplikasi untuk perolehan semula Mo(VI) dari campuran sintetik dan keputusan
menunjukkan lebih dari 90% perolehan semula Mo(VI) telah dicapai and larutan ion
logam tersebut bebas dari ketidaktulenan.
FH dan FPH telah berjaya digunakan sebagai pengekstrak untuk pengekstrakan dan
pemisahan emas(III) dari medium klorida. Logam tersebut telah diekstrak secara
kuantitatif dari medium hidroklorik pada 0.001-0.1 M ke dalam fasa organik. Emas(III)
telah berjaya dipisahkan dari Cu(II), Ni(II), Zn(II), Co(II) dan Fe(III) dengan
mengunakan FH atau FPH. Penanggalan kuantitatif bagi emas(III) dari fasa organik
boleh dijalankan dengan menggunakan larutan 2.0 M thiourea di dalam larutan HCl
vi
1.0 M. Pengekstrakan dan pemisahan emas(III) dengan FH atau FPH telah digunakan
untuk pisah dan peroleh semula emas(III) tulen dari campuran sintetik.
FPH disintesis dari olein minyak sawit telah berjaya digunakan sebagai reagen baru
dalam penentuan V(V) dengan kaedah spektrofotometrik. Kaedah ini beasaskan warna
bagi kompleks vanadium(V)-FPH. Ion logam tersebut membentuk kompleks berwarna
perang kehitaman dengan penyerapan maksimum pada 405 nm. Hukum Beer adalah sah
di dalam julat kepekatan 0.2-20 mg/L dan had pengesanan bagi kaedah ini adalah
0.01 mg/L. Ciri kaedah yang dimajukan ini adalah mudah, keselektifan yang bagus,
kesensitifan yang tinggi dan cepat.
vii
ACKNOWLEDGEMENTS
In the name of Allah, Most Gracious, Most Merciful. Praise be to Allah, the Cherisher
and Sustainer of the worlds. May the blessings and peace of Allah be upon our prophet
Muhammad ibn Abdullah (peace be upon him), upon his families and upon his
companions.
I wish to express my gratitude to my supervisor, Prof. Dato’ Dr Wan Md Zin Wan
Yunus. This thesis would not have been realized without his support, encouragement,
guidance and supervision throughout this work. I am also grateful to Prof Dr Md Jelas
Haron and Assoc. Prof Dr Mohamad Zaki Abd Rahman for their capacities as members
of Supervisory Committee. Thank you for the comments and suggestions. To the staff of
Chemistry Department thank you for their help and co-operation. A word of thanks is
also to Prof Dr Mhd Radzi Abas, University of Malaya for his advice and discussions.
My sincere thanks are to all my friends for the needed chats we had every day during our
lunch breaks, which took my mind off work. This thesis may not be completed without
your help and friendship, you are all great friends.
And to my family, thank you for supporting me throughout my long education. And
special thanks with heart full of love to my beloved sister, Sheela for her love,
encouragement, patience, understanding and moral support.
viii
I certify that an Examination Committee has met on date of viva voce to conduct the final examination of Sharifah Mohamad on her Doctor of Philosophy thesis entitled “Enzymatic Synthesis Characterization and Analytical Application of Fatty Hydrazides from Palm Oil” in accordance with Universiti Pertanian Malaysia (Higher Degree) Act 1980 and Universiti Pertanian Malaysia (Higher Degree) Regulations 1981. The Committee recommends that the student be awarded the Doctor of Philosophy. Members of the Examination Committee were as follows: Chairman, PhD Professor Department of Chemistry Faculty of Science Universiti Putra Malaysia (Chairman) Examiner 1, PhD Associate Professor Department of Chemistry Faculty of Science Universiti Putra Malaysia (Internal Examiner) Examiner 2, PhD Department of Chemistry Faculty of Science Universiti Putra Malaysia (Internal Examiner) External Examiner, PhD Professor Department of Chemistry Faculty of Science University Kebangsaan Malaysia (External Examiner) HASANAH MOHD. GHAZALI, PhD Professor and Deputy Dean School of Graduate Studies
Universiti Putra Malaysia
Date:
ix
This thesis was submitted to the Senate of Universiti Putra Malaysia and has been accepted as fulfilment for the requirement for the degree of Doctor of Philosophy. The members of the Supervisory Committee were as follows: Wan Md. Zin Wan Yunus, PhD Professor Department of Chemistry Faculty of Science Universiti Putra Malaysia (Chairman)
Md. Jelas Haron, PhD Professor Department of Chemistry Faculty of Science Universiti Putra Malaysia (Member)
Mohamad Zaki Abd Rahman, PhD Associate Professor Department of Chemistry Faculty of Science Universiti Putra Malaysia (Member)
AINI IDERIS, PhD Professor and Dean School of Graduate Studies Universiti Putra Malaysia Date: 10 July 2008
x
DECLARATION
I declare that the thesis is my original work expert for quotations and citations which have been duly acknowledgment. I also declare that it has not been previously, and is not concurrently, submitted for any other degree at Universiti Putra Malaysia or at any other degree at Universiti Putra Malaysia or at any other institution. SHARIFAH MOHAMAD
Date: 18 June 2008
xi
LIST OF TABLES
Table
2.1
2.2
2.3
2.4
3.1
3.2
3.3
3.4
3.5
4.1
4.2
4.3
4.4
4.5
4.6
4.7
4.8
4.9
Physical and chemical properties of palm oil and palm kernel olein Fatty acid composition (%) in palm oil and palm kernel olein Review of some extractants for copper separation and preconcentration Review of some spectrophotometric reagents for determination of V(V) Composition of synthetic mixture solutions containing Mo(VI) Composition of synthetic mixture solutions containing gold(III) Experimental conditions for determination PPH-vanadium(V) ratio (Job’s method) Experimental conditions for determination PPH-vanadium(V) ratio (slope ratio method) Composition of synthetic mixture solutions containing V(V) Optimum conditions of hydrazinolysis of palm oils Percentage of conversion of various fraction of palm oil to fatty hydrazide The elemental analysis data of FH Spectral assignments of palm olein, fatty hydrazide and palmityl hydrazide Optimum conditions of hydrazinolysis of palm oils Percentage of conversion of various fraction of palm oil to fatty phenyl hydrazide The elemental analysis data of FPH Spectral assignments of palm olein, fatty phenyl hydrazide and palmityl phenyl hydrazide Separation factor of separation of Cu(II) from other metal ions
Page
23
25
32
42
61
65
68
68
69
78
78
81
82
90
90
92
94
107
xii
4.10
4.11
4.12
4.13
4.14
4.15
4.16
4.17
4.18
4.19
4.20
4.21
4.22
4.23
4.24
4.25
4.26
4.27
4.28
Effect of foreign ions (500 mg/L) on the extractant of Cu(II) ion (10 mg/L) from the aqueous phase Effect of stripping agents on recovery of Cu(II) The application of the preconcentration procedure on water samples (n=5) Percentage of extraction of Mo(VI) in the presence of Ni(II), Co(II), Al(III), Mn(II) or Fe(III) from HCl solutions Effect of anions on extraction of Mo(VI) Stripping agent efficiency Effect of alkaline solutions concentration on stripping of Mo(VI) Recovery of pure molybdenum(VI) from synthetic mixture Binary separation of gold(III) from base metals by FH Binary separation of gold(III) from base metals by FPH Effect of the presence of chloride salts on the extraction of gold(III) by FH and FPH Stripping agent efficiency Recovery of gold(III) from synthetic mixture solutions by using FH Recovery of gold(III) from synthetic mixture solutions by using FPH The effect of foreign ions on the determination of 1 mg/L of vanadium(V) Molar absorptivity, specific absorptivity and Sandell sensitivity for FPH and PPH Limit of detection of vanadium(V) using FPH and PPH Determination of vanadium(V) in some synthetic mixture solutions Recovery of vanadium(V) in water samples
108
110
110
119
120
122
122
123
133
134
136
139
140
141
147
154
155
156
157
xiii
LIST OF FIGURES
Figure
2.1
2.2
4.1
4.2
4.3
4.4
4.5
4.6
4.7
4.8
4.9
4.10
4.11
4.12
4.13
4.14
4.15
4.16
4.17
Biotransformation of an ester in organic solvents World production and uses of oils and fats (1998, in million tones) Effect of temperature on hydrazinolysis of FH by various lipases Effect of various solvent on hydrazinolysis of FH Effect of reaction period on hydrazinolysis of FH Effect of catalyst loading on hydrazinolysis of FH Effect of mole ratio of hydrazine hydrate on hydrazinolysis of FH Possible reaction for the biosynthesis of FH in the presence of water FTIR spectra of (a): Palm olein (b) FH from palm olein FTIR spectra of (a): Palmityl hydrazide (PH) (b) FH from palm olein Effect of temperature on hydrazinolysis of FPH by various lipases Effect of solvent on hydrazinolysis of FPH Effect of reaction period on hydrazinolysis of FPH Effect of catalyst loading on hydrazinolysis of FPH Effect of mole ratio of phenylhydrazine on hydrazinolysis of FPH Possible reaction for the biosynthesis of FPH in anhydrous medium FTIR spectra of (a) Palm Olein, and (b) FPH from palm olein
FTIR spectra of (a) Palmityl phenyl hydrazide (PPH) and (b) FPH from palm olein 1H NMR spectra of FPH from palm olein
Page
13
20
71
73
74
76
77
80
83
83
85
86
87
88
89
91
94
95
96
xiv
4.18
4.19
4.20
4.21
4.22
4.23
4.24
4.25
4.26
4.27
4.28
4.29
4.30
4.31
4.32
4.33
4.34
4.35
4.36
4.37
4.38
4.39
1H NMR spectra of palmityl phenyl hydrazide (PPH)
Effect of pH on extraction of Cu(II) by FH and FPH Effect of pH on extraction of Ni(II) by FH and FPH Effect of pH on extraction of Zn(II) by FH and FPH Effect of pH on extraction of Co(II) by FH and FPH Effect of pH on extraction of Fe(III) by FH and FPH Effect of pH on extraction of Mn(II) by FH and FPH Distribution ratio for Cu(II), Ni(II), Zn(II), Co(II), Mn(II) and Fe(III) with FH Distribution ratio for Cu(II), Ni(II), Zn(II), Co(II), Mn(II) and Fe(III) with FPH
Effect of solvent on the extraction of copper(II) by FH Effect of pH on the extraction of Cu(II) Effect of shaking period on the extraction of Cu(II) Plot of log D vs log [FH] Effect of the A/O ratio on the extraction of Cu(II) with FH in toluene Extraction of molybdenum(VI) using FH and FPH Effect of solvent on the extraction of Mo(VI) Effect of shaking period on the extraction of Mo(VI) Effect of HCl concentration on the extraction of Mo(VI) Effect of the concentration of FH on the extraction of Mo(VI) Effect of HCl concentration on the extraction of metal ions by FH Extraction of gold(III) by using FH and FPH Effect of solvent on the extraction of gold(III)
96
98
98
99
99
100
100
101
101
103
104
105
106
109
112
113
114
116
117
118
125
126
xv
4.40
4.41
4.42
4.43
4.44
4.45
4.46
4.47
4.48
4.49
4.50
4.51
4.52
4.53
4.54
4.55
4.56
4.57
4.58
Effect of shaking period on the extraction of gold(III) ion
Effect of HCl concentration on the extraction of gold(III) by using FH and FPH Effect of the concentration of FH on the extraction of gold(III) Effect of the concentration of FPH on the extraction of gold(III) Effect of HCl concentration on the extraction of metal ions by FH Effect of HCl concentration on the extraction of metal ions by FPH Effect of anions on the extraction of gold(III) by FH Effect of anions on the extraction of gold(III) by FPH Absorption spectra (a) absorption spectra of FPH (b) absorption spectra of FPH-V(V) complex Effect of solvent on the absorbance of V(V)-FPH system Effect of acid on the absorbance of V(V)-FPH system Effect of nitric acid concentration on the absorbance of V(V)-FPH system Effect of FPH concentration on the absorbance of V(V)-FPH system Absorption spectra of FPH-V(V), FPH-Fe(III) and FPH-Cr(VI) complex V(V) complex stoichiometry determination with PPH at 405 nm (Job’s method) V(V) complex stoichiometry determination with PPH at 405 nm (Slope ratio method) Response curve of FPH towards different concentration of V(V) Response curve of PPH towards different concentration of V(V) Calibration curve of complex FPH-vanadium(V)
127
129
130
130
131
132
137
138
142
143
144
144
145
148
149
150
151
151
153
xvi
4.59
4.60
Calibration curve of complex PPH-vanadium(V) Reproducibility study in FPH response towards V(V)
153
155
xvii
xviii
LIST OF ABBREVIATIONS
DAGs
DBC
DEHPA
FAAS
FFAs
FH
FPH
FTIR
ICP-AES
MAGs
NMR
PH
PPH
TAG
TAGS
TBP
TBPO
diacylglycerols di-butylcarbitol di-2-ethylhexylphosphoric acid flame atomic absorption spectroscopy free fatty acids fatty hydrazide fatty phenyl hydrazide fourier transforms infrared spectroscopy inductively coupled plasma-atomic emission spectroscopy monoacylglycerols nuclear magnetic resonance palmityl hydrazide palmityl phenyl hydrazide triacylglycerol triacylglycerols tributyl phosphate tributyl phosphine oxide
TABLE OF CONTENTS
Page ABSTRACT ABSTRAK ACKNOWLEDGEMENTS APPROVAL DECLARATION LIST OF TABLES LIST OF FIGURES LIST OF ABBREVIATIONS
ii v
vii ix xi xii xiv
xviii
CHAPTER 1
2
INTRODUCTION 1.1 Background of study 1.1.1 Hydrazide 1.1.2 Application of hydrazide in analytical chemistry 1.2 Objectives of study LITERATURE REVIEW 2.1 Synthesis of hydrazide 2.2 Lipases 2.2.1 Lipase-catalyzed synthesis of carboxylic amides 2.2.2 Lipases in fat and oleochemical industry 2.3 Fats and oils as oleochemical raw materials 2.3.1 Palm oils 2.3.2 Characteristics of palm oil 2.3.3 Chemical composition of palm oil 2.3.4 Current status of the palm oil industry 2.4 Organic reagent for analytical application 2.5 Solvent extraction 2.5.1 Preconcentration and separation of copper(II) by solvent extraction 2.5.2 Recovery and purification of molybdenum(VI) by solvent extraction 2.5.3 Recovery and purification of gold by solvent extraction 2.6 Spectrophotometric method 2.6.1 Spectrophotometric method for determination of vanadium
1 1 1 4 6
8 8 11 14 16 19 20 21 23 25 27 28 30
32
34 37 39
3
MATERIALS AND METHODS 3.1 Materials and equipments 3.1.1 Materials and equipments for synthesis of FH and FPH 3.1.2 Materials and equipments for application studies 3.2 Synthesis of FH 3.2.1 General procedure for enzymatic synthesis of FH 3.2.2 Separation and purification of FH 3.3 Optimization study of FH synthesis 3.3.1 Screening of lipase 3.3.2 Effect of solvent 3.3.3 Effect of reaction period 3.3.4 Effect of catalyst loading 3.3.5 Effect of mole ratio of hydrazine 3.4 Synthesis of fatty phenylhydrazide (FPH) 3.4.1 General procedure for enzymatic synthesis of FPH 3.4.2 Separation and purification of FPH 3.5 Optimization study of FPH synthesis 3.5.1 Screening of lipase 3.5.2 Effect of solvent 3.5.3 Effect of reaction period 3.5.4 Effect of catalyst loading 3.5.5 Effect of mole ratio of phenyl hydrazine 3.6 Characterization of FH and FPH 3.6.1 Elemental analysis 3.6.2 Fourier Transform Infrared (FTIR) spectroscopy 3.6.3 1H Nuclear Magnetic Resonance (NMR) 3.7 Metal ion extraction by solvent extraction 3.7.1 Effect of pH on metal ion extraction by using FH and FPH 3.8 Preconcentration and separation of copper(II) ion by using FH 3.8.1 Effect of solvent on extraction of copper(II) ion 3.8.2 Effect of pH on the extraction of copper(II) ion 3.8.3 Effect of shaking period 3.8.4 Effect of FH concentration on the extraction of copper(II) ion 3.8.5 Separation of copper(II) from other metal ions 3.8.6 Effect of foreign ions on extraction of copper(II) ion 3.8.7 Effect of aqueous to organic phase ratio 3.8.8 Effect of different acids of various concentration stripping of copper(II) from organic phase 3.8.9 Preconcentration of copper(II) ion from water samples using optimum conditions of extraction and stripping 3.9 Extraction and separation of molybdenum(VI) using FH 3.9.1 Effect of solvent on the extraction of molybdenum (VI) ion
44 44 44 45 48 48 48 48 48 49 49 49 50 50 50 50 51 51 51 51 52 52 52 52 53 53 53 53
54
54 55 55 55
56 56 56 57
57
58 58
4
3.9.2 Effect of HCl concentration on the extraction of molybdenum(VI) ion 3.9.3 Effect of shaking period 3.9.4 Effect of FH concentration 3.9.5 Separation of molybdenum(VI) from associated metals 3.9.6 Effect of anions on the extraction of molybdenum(VI) 3.9.7 Stripping study 3.9.8 Recovery of molybdenum(VI) from synthetic solutions 3.10 Extraction and separation of gold(III) using FH and FPH 3.10.1 Effect of solvent on the extraction of gold(III) 3.10.2 Effect of HCl concentration on the extraction of gold(III) ion 3.10.3 Effect of shaking period 3.10.4 Effect of extractant concentration 3.10.5 Separation of gold(III) from associated metals 3.10.6 Effect of the presence of chloride salts on the extraction of gold(III) 3.10.7 Effect of anions on the extraction of gold(III) 3.10.8 Stripping agent studies 3.10.9 Recovery of gold(III) from synthetic solutions 3.11 Spectrophotometric studies for determination of vanadium (V) using FPH 3.11.1 Absorption of spectra 3.11.2 Effect solvent 3.11.3 Effect of acidity 3.11.4 Effect of concentration of FPH 3.11.5 Effect of foreign ions 3.11.6 Determination of molar ratio of FPH-vanadium(V) complexes 3.11.7 Dynamic range and sensitivity 3.11.8 Reproducibility of the method 3.11.9 Determination of vanadium(V) from synthetic solutions and water samples RESULTS AND DISCUSSION 4.1 Optimization of FH synthesis 4.1.1 Effect of various lipases on the biosynthesis of FH 4.1.2 Effect of solvent on biosynthesis of FH 4.1.3 Effect of reaction period on biosynthesis of FH 4.1.4 Effect of catalyst loading on biosynthesis of FH 4.1.5 Effect of mole ratio of hydrazine hydrate on biosynthesis of FH 4.1.6 Hydrazinolysis of various products of palm oil 4.1.7 Proposed reaction involved in the biosynthesis of FH
58
59 59 59
60 60 61 62 62 62
62 63 63 63
64 64 65 65
65 66 66 66 67 67
68 69 69
70 70 70 72 74 75 76
77 79
4.2 Characterization of FH 4.2.1 Elemental analysis of FH 4.2.2 FTIR spectra of FH 4.3 Optimization of FPH synthesis 4.3.1 Effect of various lipases on the biosynthesis of FPH 4.3.2 Effect of solvent on biosynthesis of FPH 4.3.3 Effect of reaction period on biosynthesis of FPH 4.3.4 Effect of catalyst loading on biosynthesis of FPH 4.3.5 Effect of mole ratio of phenylhydrazine on biosynthesis of FPH 4.3.6 Hydrazinolysis of various products of palm oil 4.3.7 Proposed reaction involved in biosynthesis of FPH 4.4 Characterization of FPH 4.4.1 Elemental analysis of FPH 4.4.2 FTIR spectra of FPH 4.4.3 1H NMR of FPH 4.5 Solvent extraction of metals by FH and FPH 4.5.1 Effect of pH on various metal ion extraction 4.6 Preconcentration and separation of copper(II) by FH 4.6.1 Effect of solvent on the extraction of Cu(II) 4.6.2 Effect of pH on the extraction of Cu(II) 4.6.3 Effect of shaking period on the extraction of Cu(II) 4.6.4 Effect of FH concentration on the extraction of Cu(II) 4.6.5 Separation of Cu(II) from other metals 4.6.6 Effect of foreign ions on the extraction of Cu(II) 4.6.7 Effect of aqueous to organic phase ratio 4.6.8 Effect of stripping agent for preconcentration of Cu 4.6.9 Preconcentration of Cu in water samples 4.7 Extraction and separation of molybdenum(VI) using FH 4.7.1 Extraction of molybdenum(VI) ion by using FH and FPH 4.7.2 Effect of solvent on the extraction of molybdenum(VI) 4.7.3 Effect of shaking period 4.7.4 Effect of HCl concentration on the extraction of molybdenum(VI) 4.7.5 Effect of FH concentration on the extraction of molybdenum(VI) 4.7.6 HCl concentration effect on extraction of various metal ions 4.7.7 Separation of molybdenum(VI) from associated metals 4.7.8 Effect of anions on the extraction of molybdenum(VI) 4.7.9 Stripping agent studies 4.7.10 Recovery of molybdenum(VI) from synthetic solutions
80 80 81 84 84 85 87 88 89
90 91 92 92 93 95 97 97 102 102 103 105 105 106 107 108 109 110 111 112
113 114 114
116
117
118 119 121 123
5
4.8 Extraction and separation of gold(III) using FH and FPH 4.8.1 Extraction of gold(III) ion by using FH and FPH 4.8.2 Effect of solvent on the extraction of gold(III) 4.8.3 Effect of shaking period on gold(III) extraction 4.8.4 Effect of HCl concentration on the extraction of gold(III) 4.8.5 Effect of FH concentration on the extraction of gold(III) 4.8.6 HCl concentration effect on extraction of various metal ions 4.8.7 Separation of gold(III) from associated metals 4.8.8 Effect of the presence of chloride salts on the extraction of gold(III) 4.8.9 Effect anions on the extraction of gold(III) 4.8.10 Stripping agent studies 4.8.11 Recovery of gold(III) from synthetic solutions 4.9 Spectrophotometric studies for determination of vanadium (V) using FPH 4.9.1 Absorption spectra 4.9.2 Effect of solvent 4.9.3 Effect of acidity 4.9.4 Effect of concentration of FPH 4.9.5 Effect of foreign ions 4.9.6 Molar ratio of PPH-vanadium(V) complex 4.9.7 Dynamic range and sensitivity 4.9.8 Limit of detection (LOD) 4.9.9 Reproducibility of the method 4.9.10 Determination of vanadium in synthetic solutions 4.9.11 Application: Analysis of vanadium in spiked water samples CONCLUSIONS 5.1 Recommendations for further studies
124 125 126 126 127
129
131
132 134
136 138 139 141
142 143 143 145 146 148 150 154 155 156 156
158 160
REFERENCES APPENDICES BIODATA OF THE STUDENT LIST OF PUBLICATIONS
162 180 182 183
CHAPTER I
INTRODUCTION
1.1 Background of study
1.1.1 Hydrazide
Hydrazides with the general formula RCONHNH2 have been thoroughly studied as
ligands with non-bonded lone pair of electrons on the nitrogen of amino group and
oxygen of the carbonyl group. It may coordinate with many metal ions monodentate or
multidentate (Gudasi et al., 2007; Becher et al., 2006; Zhang et al., 2006). The
molecular structure of chelate-forming reagents must contain at least two donor atoms
capable of bonding to the same metal atom. The complex formation with hydrazide
ligands in aqueous solution demonstrated clearly that two atoms (O, N) bonding modes
of the ligands are accessible to metal ions (Bontchev et al., 1981; Ahmed and Chaudhuri,
1971).
The formation of metal complexes plays an important role in the enhancement of their
biological activity (Singh et al., 2000). In recent years, hydrazides have received a lot of
attention due to their biological activity as tuberculostatic (Yadav et al., 2005),
antibacterial agent (Malhotra et al., 1992), antitumor agent (Dodoff et al., 1994) and
anticancer agent (Zhang et al., 2004). In addition, hydrazides have received considerable
attention in analytical chemistry chelating reagents for metal extraction and
determination (Jal et al., 2001; Ahmed and Banoo, 1999; Liu et al., 1999).