DEGRADATION OF ACETAMINOPHEN BY USING SULFATE RADICAL

By

MUHAMMAD YASIR KHAN

(Regd. No. 2013-CHE-114)

Session 2016-2018

Department of Chemistry
Faculty of Basic and Applied Sciences
University of the Poonch Rawalakot
Azad Jammu and Kashmir
DEGRADATION OF ACETAMINOPHEN BY USING SULFATE RADICAL

By

MUHAMMAD YASIR KHAN

(Regd. No. 2013-CHE-114)

A thesis submitted in partial fulfillment of the requirements for the degree of

M. Phil

in

Chemistry

Session 2016-2018

Department of Chemistry

Faculty of Basic and Applied Sciences

University of the Poonch Rawalakot

Azad Jammu and Kashmir

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 CERTIFICATION

It is certified that the contents and form of thesis entitled “Degradation of

Acetaminophen by using sulfate radical” submitted by Mr. Muhammad Yasir khan

(2013-CHE-114), dated ___________________ have been found satisfactory for the

award of degree of Master of Philosophy in Chemistry.

SUPERVISORY COMMITTEE

i. Supervisor Dr. FaizaRehman ------------------

Assistant Professor in Chemistry

ii. Co-Supervisor Dr. MurtazaSayed -----------------

Assistant Professor in NCEPC, UOP

iii. Member Dr. ShabnamShahida -----------------

Assistant Professor in Chemistry

iv. Member Dr. Qamar Din

-----------------Assistant Professor in Mathematics

v. External Examiner --------------

Incharge
Department of Chemistry

Dean Director
Faculty of Basic and Applied Sciences Advanced Studies and Semester Affairs

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 DEDICATION

This thesis is dedicated to my beloved parents, brothers

and sisters

CONTENTS

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 LIST OF TABLES VIII

LIST OF FIGURES IX

LIST OF ABBREVIATIONS XI

ACKNOWLEDGEMENT XIII

Abstract XV

1. INTRODUCTION 1

1.1 Pharmaceuticals as environmental pollutants 1

1.2 Acetaminophen as organic pollutant 6

1.3 Persulfate radical 9

1.4 Action of Persulfate radical 10

2. REVIEW OF LITERATURE 19

3. MATERIAL AND METHODS 26

3.1 UV-Visible Spectrophotometer 26

3.2 Actinometry 26

3.3 pH meter 27

3.4 Fourier Transformer Infrared Spectroscopy (FTIR) 28

3.5 Total Organic Carbon (TOC) Analysis 28

3.6 High Performance Liquid Chromatography-Mass Spectrometry

HPLC-MS 29

3.7 Reagents used 30

3.7.1 Chemicals 30

3.7.2 Standard solution of ACTP 30

3.7.3 Dilute solutions preparations 30

3.7.4 Preparations of stock solutions of oxidants 30

3.7.5 Preparation of stock solution of Catalyst 31

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 3.7.6 Preparation of stock solutions of cations and anions 32

3.7.7 Preparation of solutions of NaOH and HCl 32

4. RESULTS AND DISCUSSION 33

4.1 Concentration selection of ACTP 33

4.2 Degradation of ACTP under UV-C Light 33

4.3 Effect of initial concentration of different oxidants 33

4.3.1 UV/H2O2/Co2+ 33

4.3.2UV/PS/Co2+ 37

4.3.3 UV/PMS/Co2+ 37

4.4 Effect of initial concentration of catalyst 40

4.4.1 UV/H2O2/Co2+ 40

4.4.2 UV/PS/Co2+ 40

4.4.3 UV/PMS/Co2+ 43

4.5 Pollutant concentration study 43

4.5.1 UV/ACTP/H2O2/Co2+ 43

4.5.2 UV/ACTP/PS/Co2+ 46

4.5.3 UV/ACTP/PMS/Co2+ 46

4.6 Effect of different Anions on the degradation of ACTP 49

4.6.1 UV/ACTP/H2O2/Co2+/Anions 49

4.6.2 UV/ACTP/PS/Co2+/Anions 49

4.6.3 UV/ACTP/PMS/Co2+/Anions 49

4.7 Effect of different Cations on the degradation of ACTP 53

4.7.1 UV/ACTP/H2O2/Co2+/Cations 53

4.7.2 UV/ACTP/PS/Co2+/Cations 53

4.7.3 UV/ACTP/PMS/Co2+/Cations 56

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 4.8 Effect of pH on the degradation of ACTP 56

4.8.1 UV/H2O2/Co2+ 56

4.8.2 UV/PS/Co2+ 56

4.8.3 UV/PMS/Co2+ 59

4.9 Kinetic study 62

4.9.1 Kinetic study of UV/H2O2/Co2+, UV/PS/Co2+, UV/PS/Co2+ and

UV/PMS/Co2+ 62

4.10 FTIR analysis 62

4.10.1 FTIR analysis of ACTP degradation by using UV/H2O2/Co2+,

UV/PS/Co2+ and UV/PMS/Co2+ processes 62

4.11 TOC Analysis 62

4.11.1 TOC analysis of degradation of ACTP by using H2O2/Co2+,

PS/Co2+ and PMS/Co2+ processes under UV-C irradiation 62

4.12 Proposed degradation pathways of ACTP 68

SUMMARY 70

5. LITERATURE CITED 71

List of Tables

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Table No. Title Page

4.1 FTIR analysis of functional groups of photo degraded 64

byproducts of ACTP by using UV/H2O2/Co2+ process

4.2 FTIR analysis of functional groups of photo degraded 65

byproducts of ACTP by using UV/PS/Co2+ process

4.3 FTIR analysis of functional groups of photo degraded 66

byproducts of ACTP by using UV/PMS/Co2+ process

4.4 TOC removal by using UV/H2O2/Co2+, UV/PS/Co2+ and 67

UV/PMS/Co2+ processes

List of Figures

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Figure No. Title Page

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1.1 Structure of ACTP 1
3.1 Specord 210 UV-Visible Spectrophotometer 26
3.2 GL-58 UV-C hand lamp 27
3.3 Inolab 7110 pH meter 28
3.4 Alpha FTIR spectrometer 28
3.5 Skalar TOC Analyzer 29
3.6 Agilent 1100 series HPLC-MS 30
4.1 Calibration curve and concentration selection for ACTP 34
4.2 Photo degradation of ACTP by using UV-C irradiation 35
Effect of different concentration of H2O2 on the degradation
4.3 36
of ACTP in the presence of Co2+ catalyst

Effect of different concentration of PS on the degradation

4.4 38
of ACTP in the presence of Co2+ catalyst

Effect of different concentration of PMS on the degradation

4.5 39
of ACTP in the presence of Co2+ catalyst

Effect of different concentration of Co2+ on the degradation

4.6 41
of ACTP at fixed concentration of H2O2 and ACTP

Effect of different concentration of Co2+ on the degradation

4.7 42
of ACTP at fixed concentration of PS and ACTP

Effect of different concentration of Co2+ on the degradation

4.8 44
of ACTP at fixed concentration of PMS and ACTP
Degradation by using different concentrations of ACTP in
4.9 45
the presence of Co2+ catalyst with H2O2
Degradation by using different initial concentration of
4.10 47
ACTP in the presence of Co2+ catalyst with PS

Degradation by using different initial concentration of

4.11 48
ACTP in the presence of Co2+ catalyst with PMS

Effect of different anions on the degradation of ACTP in

4.12 50
the presence of Co2+ catalyst with H2O2

Effect of different anions on the degradation of ACTP in

4.13 51
the presence of Co2+ catalyst with PS

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 Effect of different anions on the degradation of ACTP in
4.14 52
the presence of Co2+ catalyst with PMS

Effect of different cations on the degradation of ACTP in

4.15 54
the presence of Co2+ catalyst with H2O2

Effect of different cations on the degradation of ACTP in

4.16 55
the presence of Co2+ catalyst with PS

Effect of different cations on the degradation of ACTP in

4.17 57
the presence of Co2+ catalyst with PMS

Effect of different pH on degradation of ACTP with H2O2 in

4.18 58
the presence of catalyst

Effect of different pH on degradation of ACTP with PS in

4.19 60
the presence of Co2+ catalyst

Effect of different pH on degradation of ACTP with PMS in

4.20 61
the presence of Co2+ catalyst

Pseudo first order kinetics for photo degradation of ACTP

4.21 63
by UV/H2O2/Co2+, UV/PS/Co2+ and UV/PMS/Co2+ reactions

4.22 Proposed degradation pathway for ACTP 69

List of Abbreviations

ACTP Acetaminophen

STP Standard Temperature and

Pressure

Eₒ Redox Potential

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 TOC Total Organic Carbon

PMS Peroxymonosulfate

PS Persulfate

SO4.- Sulfate Radical

H2O2 Hydrogen Peroxide

·
OH Hydroxyl Radical

EDTA Ethylenediamminetetraacetic
acid

HSO5- Peroxomonosulfate

H2S82- Peroxodisulfate

IM Endomethasine

DEET N,N-diethyl-toluamide

CYN Cylindrospermopsin

K2S2O8 Potassium persulfate

G-Value Chemical yield

TiO2 Titanium Dioxide

RVC Reticulated Vitreous Carbon

COD Chemical Oxygen Demand

HPLC High Performance Liquid

Chromatography

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 CO32- Carbonate Ion

Co2+ Cobalt catalyst

ACKNOWLEDGEMENT

First of all, I give thanks to Allah for his showers of blessings throughout my

research work to complete the research successfully.

I would never express my gratitude enough to my supervisor Dr. Faiza Rehman

for giving me the opportunity to do research and providing guidance during this

research. It was a great honor to do work and study under her guidance. She

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generously gave her time to offer me valueable comments toward improving my

work.

My co-supervisor Dr. Murtaza Sayed for his excellent guidance and supervision

in last few years, I would like thank you for your endless patience and co-operation

in my research work. For being a wonderful human being, I really felt honored and

blessed to have you as a co-supervisor and I hope that your future students realize

how lucky they are.

I am highly indebted to my HOD Dr. Naveed Iqbal, Dr. Syed Mubashir Sabir,

Dr. Khizar Hussain Shah, Dr. Shabnum Shahida, Dr Khuram Liaqat, and all

other teachers who helped me during research.

I thank my fellow labmates Waqas Ahmed and Nazish Parveen for their

stimulating discussion, their unstinted support, timely motivation, sympathetic

attitude and unfailing help during my research work.

With a special mention to Sikandar Hayyat, Hafiz Azhar Hussain, Yasir

Inayat, Raja Khalid, Asad Naseer, Qadeer Afsar, Azhar khan, Manazar,

Sajid ur Rehman, Absar Khan, Ali Raza, Sikandar, Sajid Hussain, Syed

Khurram zakir, Qadir Arif, Toseer Afsar, Saghir Anjum and my class fellows

for their limitless cooperation during the whole studies and research.

I am thankful to Usman Khan (Lab. Assistant) and Mumtaz Ali for their cooperation.

Finally, last but not least, I am very thankful to my beautiful family, my parents, my
brothers, my sisters, my Grandmother and my cousins who supported me spiritually,
financially and morally throughout of my life especially my Father M. Azim Khan and
uncle M. Tufail Khan.

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 Muhammad Yasir Khan

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