DETERMINATION OF INORGANIC ANIONS IN CHEMICAL IGNITION

MOLOTOV COCKTAIL USING ION CHROMATOGRAPHY

WAN NUR SYAHIRAH BINTI WAN MOHAMMAD

UNIVERSITI TEKNOLOGI MALAYSIA

DETERMINATION OF INORGANIC ANIONS IN CHEMICAL IGNITION

MOLOTOV COCKTAIL USING ION CHROMATOGRAPHY

WAN NUR SYAHIRAH BINTI WAN MOHAMMAD

A dissertation submitted in partial fulfillment of the requirements for the award of

the degree of Master of Science (Forensic Science)

Faculty of Science

Universiti Teknologi Malaysia

JANUARY 2014

iii

To my beloved mother and father, family, friends and myself.

To my supervisors for their advices, supports and encouragements.

iv

ACKNOWLEDGEMENT

Special thanks go to my main supervisor, Assoc. Prof. Dr. Mohd Shahru bin

Bahari, for his help during the course of this research. Without his time and patience

much of this work could not have been accomplished.

I am also thankful to my co-supervisor, ACP Tang Ngat Ngoh and Tuan

Azlimin bin Mat Noor for their suggestions and advices. Without their continued

support and interest, this dissertation would not have been completed yet.

Special thanks to Tuan Khalib, Tuan Eva Suffian, Tuan Suffian and En.

Mohd Fattah from Fire Rescue Department Malaysia for their assistance in petrol

bom explosion. A sincere appreciation goes to laboratory assistants of the Chemistry

Department, Universiti Teknologi Malaysia (UTM), particularly Madam Mariam

Hasan, Mr. Mat Yasin Sirin, Mr. Mohd Nazri Zainal and Madam Siti Rafezah Mat

Emin for their help and guidance. A million thanks to my entire fellow friends for

their knowledge, encouragement and help throughout the research. Special thanks to

Ministry of Higher Education for funding my post-graduate study via MyBrain 15

scholarship.

Last but not least, I wish to express my sincere appreciation to my beloved

family for their continuous support, advices and motivation for me to complete my

research. Thank you so much.

v

ABSTRACT

The Chemical Ignition Molotov Cocktail (CIMC) is one of the improvised

incendiary devices (IIDs) that have been used recently in acts of terrorism. It is in the

interest of the Police and Fire Department to gather information on the compositions

and types of device employed by the determining the inorganic ions present in

CIMCs residues, namely sulphate (SO42-

), chlorate (ClO3-), perchlorate (ClO4

-), and

chloride (Cl-). In simulated ground experiments, these improvised CIMCs using

petrol, kerosene and diesel as accelerants were thrown against a brick wall which

initiated the fire as a consequence of the exothermic reaction produced by the

combination of the concentrated sulfuric acid and potassium chlorate. Ion

Chromatography (IC) was employed to determine the ionic composition of the

CIMCs residues in order to identify the chemical reagents used for the device. The

targeted anions were separated within 56 minutes using NaHCO3-Na2CO3 as the

eluent. In this study, results from samples of CIMCs showed that sulfate, chlorate,

and chloride were detected in most samples. However, perchlorate could not be

detected since not all potassium chlorate reacted with sulfuric acid when the bottle

broke. Concentration of sulfate ion was higher than the other anions. It was also

noted that petrol gave the most powerful explosion on the CIMCs devices as

compared to kerosene and diesel. Combustible material such as sugar was also found

to give more destructive power on these devices as reflected by the more powerful

combustion.

vi

ABSTRAK

Bom petrol pencucuhan kimia (CIMCs) adalah salah satu daripada peranti

pembakar yang diubahsuai (IIDs) dan telah digunakan dalam tindakan pengganas

kebelakangan ini. Ia adalah satu keperluan bagi Jabatan polis untuk mengumpul

maklumat tentang komposisi dan jenis peranti yang digunakan bagi menentukan ion-

ion tak organik yang hadir dalam sisa-sisa CIMCs iaitu sulfat (SO42-

), klorat (ClO3-),

perklorat (ClO4-), dan klorida (Cl

-). Bagi eksperimen simulasi, CIMCs yang

menggunakan petrol, diesel dan minyak tanah sebagai bahan pembakar dilontarkan

ke dinding batu-bata seterusnya menghasilkan nyalaan api akibat daripada tindak

balas eksotermik yang dihasilkan oleh gabungan asid sulfurik pekat dan kalium

klorat. Ion kromatografi (IC) digunakan untuk menentukan komposisi ionik sisa-sisa

CIMCs untuk mengenalpasti reagen kimia yang digunakan dalam peranti tersebut.

Anion yang terpilih telah dipisahkan dalam masa 53 minit menggunakan NaHCO3-

Na2CO3 sebagai eluen. Dalam kajian ini, hasil daripada sampel CIMC menunjukkan

sulfat, klorat dan klorida dikesan dalam kebanyakan sampel. Walau bagaimanapun,

perklorat tidak dapat dikesan kerana tidak semua klorat kalium bertindak balas

dengan asid sulfurik apabila botol itu pecah. Kepekatan ion sulfat adalah lebih tinggi

daripada anion lain. Ia juga menyatakan bahawa petrol memberikan letupan paling

kuat pada peranti CIMCs berbanding dengan minyak tanah dan diesel. Bahan mudah

terbakar seperti gula juga didapati memberi kuasa yang lebih membinasakan dalam

peranti ini berdasarkan oleh pembakaran yang lebih berkuasa.

vii

TABLE OF CONTENT

CHAPTER TITLE PAGE

DECLARATION

DEDICATION

ACKNOWLEDGEMENT

ABSTRACT

ABSTRAK

TABLE OF CONTENTS

LIST OF TABLES

LIST OF FIGURES

LIST OF ABBREVIATIONS

ii

iii

iv

v

vi

vii

x

xi

xiii

I

INTRODUCTION

1

1.1 Background of Study

1.2 Statement of Problem

1.3 Objectives

1.4 Scope of Study

1.5 Significance of Study

1

2

3

3

4

II LITERATURE REVIEW 5

2.1 Arson

2.2 Improvised Incendiary Devices

2.3 Molotov Cocktail

2.3.1 The Classic Molotov Cocktail

2.3.2 The Chemical Ignition Molotov

Cocktail

5

6

7

8

11

viii

2.4 Accelerant

2.3.1 Petrol

2.3.2 Kerosene

2.3.4 Diesel

2.5 Chemical Analysis of Incendiary Devices

2.6 Analysis of Inorganic Ions

2.7 Ion Chromatography

2.7.1 Ion Chromatography Components

10

11

11

11

12

12

12

13

III

EXPERIMENTAL

15

3.1 Introduction

3.2 Chemicals and Materials

3.3 Apparatus

3.4 Instrumentation

3.5 Methodology Diagram

3.6 Procedure

3.6.1 Preparation of Eluent

3.6.2 Preparation of Suppressor

3.7 Chemical Ignition Molotov Cocktail

Sample Preparation

3.8 Ground Experiment

3.9 Extraction

3.10 Ion Chromatography Analysis

15

15

16

16

17

17

18

18

18

19

20

20

IV RESULTS AND DISCUSSIONS 21

4.1 Selection of Target Analytes

4.2 Ground Experiment of CIMC

4.3 Separation of Inorganic Anions

4.4 Calibration Graph and Limits of

Detection

4.5 Reproducibility

4.6 Analysis of CIMC Residue Samples

21

21

26

27

28

29

ix

4.6.1 Comparison of CIMC Residue

Samples with Different

Accellerant

4.6.2 Comparison of CIMC Residue

Samples With and Without

Sugar

4.6.3 Concentration of CIMC Residue

Samples

4.7 Limitations of the Research

32

32

34

37

V CONCLUSIONS AND RECOMMENDATIONS 38

5.1 Conclusions

5.2 Recommendations

38

39

REFERENCES 40

APPENDICES 44

x

LIST OF TABLES

TABLE NO. TITLE PAGE

3.1 CIMCs samples used in this study 19

4.1 Limit of detection (LOD) and correlation coefficient

(r2) of each anions.

28

4.2 Relative standard deviation of retention time and peak

area for each anions within day and day-to-day.

29

4.3 The concentration value of target anions in petrol-

CIMCs samples.

35

4.4 The concentration value of target anions in diesel-

CIMCs samples.

36

4.5 The concentration value of target anions in kerosene-

CIMCs samples.

37

xi

LIST OF FIGURES

FIGURES NO. TITLE PAGE

2.1 Example of classic Molotov Cocktails 8

2.2 Example of Chemical Ignition Molotov Cocktails

(CIMCs)

9

2.3 Schematic diagram of suppressed ion

chromatography.

14

2.4 Schematic diagram of non-suppressed ion

chromatography.

14

3.1 The steps in determining anions in Chemical Ignition

Molotov Cocktails (CIMCs)

17

3.2 (a) Sample preparation of CIMCs and (b) CIMCs

sample bottle

18

3.2 CIMCs simulation 20

4.1 The fire produced by different accelerant (a) Petrol (b)

Diesel and (c) Kerosene.

23

4.2 The difference size of flame between CIMCs sample

(a) without and (b) with sugar.

24

4.3 Separation of standard anions (5 mg/L) on Metrosep

A Supp 5 column.

26

4.4 Calibration graph of standard anions ranged 1 to 5

mg/L.

28

4.5 IC chromatogram of three different types of CIMCs

with sugar.

30

xii

4.6 IC chromatogram of three different types of CIMCs

without sugar.

30

4.6 (a) IC chromatogram from Figure 4.6 but with smaller

scale as Figure 4.5 to compare the intensity of ion

peaks.

30

4.7 IC chromatogram of petrol-CIMCs (a) without sugar

and (b) with sugar.

33

4.8 IC chromatogram of diesel-CIMCs (a) without sugar

and (b) with sugar.

33

4.9 IC chromatogram of kerosene-CIMCs (a) without

sugar and (b) with sugar.

34

4.10 The concentration graph of target anions in petrol-

CIMCs samples.

35

4.11 The concentration graph of target anions in diesel-

CIMCs samples.

36

4.12 The concentration graph of target anions in kerosene-

CIMCs samples.

37

xiii

LIST OF ABBREVIATIONS

DDW - Distilled deionised water

CE - Capillary Electrophoresis

CIMCs - Chemical Ignition Molotov Cocktails

FRDM - Fire and Rescue Department of Malaysia

IC - Ion chromatography

IED - Improvised explosive devices

IID - Improvised incendiary devices

ND - Not detected

RMP - Royal Malaysia Police

RSD - Relative standard deviation

SD - Standard deviation

xiv

LIST OF APPENDICES

APPENDIX TITLE PAGE

A Abstract for INPALMS 2013 44

CHAPTER 1

INTRODUCTION

1.1 Background of Study

Improvised incendiary devices (IIDs) are weapons which designed to start

fires or destroy properties using fire. The devices have become the popular device

used and become a current trend as an act of vengeance. There are a quite number of

cases where IIDs are used as weapon in acts of violent, riot and others. These kinds

of devices have the potential to create a devastating impact resulting in severe

fatalities (Martin-Albera et al., 2012).

One example of an IID is a Molotov cocktail which has been used recently. It

is also known as petrol bomb. They are very simple and easy to be constructed,

inexpensive and common weapon to use. It is used by arsonist with its primary

purpose to set off fire (Ahmad et al., 2011). Molotov cocktail is another incendiary

device where mechanical explosions occurs when the bottle with a burning wick is

thrown and upon impact, the bottle will break and allows the accelerant to spread and

splatter (Bordie, 1973).

These days the petrol bomb has been improved by using chemical reagents to

initiate the ignition of the flammable liquid. These devices are called the Chemical

Ignition Molotov Cocktail (CIMCs) which are also known as chemical fire bottles.

Cases involving arson have highlighted the interest of forensic scientists in

the characterization of the composition of the incendiary devices. For inorganic

2

explosive devices, it is possible to assume the original devices composition from the

inorganic found from the residue (Martin-Albera et al., 2012). However, this has

never been reported before with incendiary devices (Martin-Albera et al., 2012). The

determination of inorganic ions from the evidence has the potential for revealing the

type of weapon and/or its ignition system.

The inorganic ions that are normally analyzed are sulphate, confirming the

presence of sulfuric acid, chlorate, as a marker on the employment of potassium

chlorate and chloride, which could be produced from the chemical reduction of

chlorate salts and is also sometimes employs as a marker (Martin-Albera et al.,

2012).

In order to analyze the evidence and acquire some information from it, the

forensic scientists need to use several techniques for its identification. In this study,

ion chromatography will be used to determine the ionic content of Chemical Ignition

Molotov Cocktails (CIMCs) from the residues collected from the simulation used of

the CIMCs.

1.2 Statement of Problem

Lately, the number of cases where incendiary devices were used as an act of

retaliation has increased. These kind of incendiary devices like Molotov Cocktails

were commonly used during riot and from protestors against from police, and they

are also being used to attack houses, to burn the house or to threaten the occupants.

This device will cause severe damages to whatever is directly or indirectly targeted.

CIMCs used by criminal are normally based on inorganic salts and/or

peroxides since these kinds of chemical are readily available, low cost and can be

purchased legally (Johns et al., 2008). The major ingredients normally are fuels and

oxidizers (Johns et al., 2008). The most common fuels are petrol, kerosene and

gasoline, while chlorate and perchlorate are the most common oxidizers used.

3

In arson investigation, the chemical analysis will be carried out on the

collected fire debris resulting from the fire. In chemical analysis, the chemist will

deal with extraction, isolation and analysis of the target compound that could be used

to accelerate the fire (Ahmad et al., 2012). The search for evidence of any accelerant

used at the crime scene is a difficult task because the accelerants are volatile and

evaporate quickly. However, in the case of incendiary devices, the accelerant is not

only the components as it also contains some chemical reagents to make the reaction

more exothermic and result in stronger combustion.

Therefore, the original composition and other characteristics from inorganic

ions in the incendiary residues and it also could be determine to ascertain the type of

weapon and ignition system used.

1.3 Objectives

The objectives of this study are:

i. To detect the presence of anions in CIMCs, and

ii. To identify the type of ignition system

1.4 Scope of Study

This study is focused on the analysis of the composition by determining the

anionic content of the Chemical Ignition Molotov Cocktails (CIMCs).

4

1.5 Significance of Study

This study will help the Royal Malaysian Police (RMP), Fire and Rescue

Department Malaysia (FDRM) or Chemistry Department of Malaysia in the

identification of the type of improvised incendiary devices that had been used by the

criminals. Analysis of this device will offer important information regarding the

materials that been used in making it. This will eventually establish a link between

the device and its perpetrators.

40

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