The Science of Arson and The Science of Arson and ExplosivesExplosives

Chapter 11Chapter 11

Fire• Made of heat and light (photons)

• It is produced when an energy-containing compound combines with oxygen and gets oxidized.

• Oxygen gets reduced and becomes water.

• This is called combustion.

CH4 + 2O2 CO2 + 2H2O + Energy / Heat / Light

Methane contains energy in the form of electrons in the hydrogen atoms

Oxygen loves to grab electrons, so it grabs

the electron-containing hydrogens from carbon

Carbon combines with leftover oxygen

atoms to form carbon dioxide

The oxygen atoms that did grab the electron-containing hydrogens,

become water

The breaking of the bonds in methane, releases energy,

heat and light

Methane gets oxidized to carbon

dioxide

Oxygen gets reduced to water

More about combustionMore about combustion• The heat released in the reaction is called the The heat released in the reaction is called the

“Heat of Combustion”“Heat of Combustion”

• Since the reaction released energy, it is called Since the reaction released energy, it is called an exergonic or exothermic reactionan exergonic or exothermic reaction

• Some reactions require an input of energy – Some reactions require an input of energy – those are called endergonic or endothermic those are called endergonic or endothermic reaction – however, we are not concerned with reaction – however, we are not concerned with those since arson and explosions are mostly those since arson and explosions are mostly exothermic reactions.exothermic reactions.

Not all combustion leads to a fire

4Fe + 3O2 2Fe2O3

No fire was produced, but iron is oxidized and oxygen is reduced.

Iron Oxygen Iron Oxide a.k.a. rust

Energy

• Energy is the capacity of doing work.

• When chemical bonds form or break, the energy released can be used to do work.

• What kind of work?– Driving a car or other machines– Pushing bullets out of a cartridge– Fireworks– Exploding mountains, old buildings, etc.

How can we put this energy to use?

• If the rate of combustion is controlled and the speed of the reaction is slow (like the combustion of gasoline in the engine of a car), then one can perform prolonged work – the car keeps driving.

• If the rate of the combustion is fast, it produces a “burst” or explosion of energy. One cannot do prolonged work with one explosion of energy. But one can use the explosion to perform a one-time job (demolition, for example)

The Energy Barrier• Although Methane, gasoline and other

compounds pack huge amount of energy, they do not combust automatically when exposed to oxygen (thank goodness for that!)

• That is because there is an energy barrier or threshold that has to be crossed first.

• That threshold can be crossed with the help of high temperature – such as a spark, a match, etc.

Low vs. High Energy BarriersLow vs. High Energy Barriers

• Iron and oxygen can combine and form rust Iron and oxygen can combine and form rust without the addition of heat because they have a without the addition of heat because they have a low energy barrier to cross.low energy barrier to cross.

• They can used the energy in the surrounding They can used the energy in the surrounding area to cross the barrier.area to cross the barrier.

• Methane and oxygen have a considerably higher Methane and oxygen have a considerably higher one to cross – therefore the surrounding energy one to cross – therefore the surrounding energy is not sufficient. One has to use heat.is not sufficient. One has to use heat.

Ignition Temperature

• The amount of heat required to “push” the combustion reaction over the energy barrier is known as the ignition temperature.

• Once the combustion starts, enough heat is created to keep the reaction going.

• For example: You need to use a match (extra heat) to light the methane gas on fire. But once that ignition occurs, the material keeps burning.

Liquid and Solid Fuels

• So far we discussed methane – a gas. Its molecules mix with the molecules of oxygen when the ignition temperature is reached.

Question: What about liquids and solid fuels? How do oxygen molecules combine freely with them if they are not in the gaseous state?

Answer

• Both liquids and solids must first be converted into gas molecules, so that oxygen molecules can combine with them to produce fire.

• Liquid fuels have to turn to vapor or gas first. The lowest temperature at which this happens is called the Flash PointFlash Point of the liquid.

• Once the Flash Point is reached, a light or spark can cause the gas/vapor to reach the ignition point and combustion to occur.

Solid Fuels• Wood for example, cannot generate a vapor

easily.

• It has to first be exposed to enough heat to breakdown some of the solid organic material into gases that are combustible.

• The chemical breakdown of solids into gas is known as pyrolysis.

Glowing Combustion

• If there is not enough heat to pyrolyze the solid fuel to produce flames, the solid fuel does not combust through-and-through, only on the surface.

• This produces a glowing effect – Examples: embers, burning cigarette, etc.

Spontaneous Combustion• Natural heat-producing process occurring in a

poorly ventilated area.• Very rare, but when it does occur, it is in fuel cans

or other ignitable substances.• Almost never in human bodies (more of a belief,

right now).

Quite the Hottie!

Arson

• By definition, it is a man made fire that was started in order to destroy persons or property.

• Usually started with an accelerant.

• An accelerant is a fuel with a low flash point, that is used to speed-up the combustion process. (Gasoline, turpentine, alcohol, etc.)

Fire InvestigationFire Investigation• Locate origin of fireLocate origin of fire

– Fire moves upwards, so source will be at the lowest Fire moves upwards, so source will be at the lowest pointpoint

– The area will show the most intense burn damage The area will show the most intense burn damage

• Isolate and protect origin site for further investigationsIsolate and protect origin site for further investigations

• Look for signs of tampering or use of accelerants – Use Look for signs of tampering or use of accelerants – Use hydrocarbon vapor detecting apparatus or “Sniffers”hydrocarbon vapor detecting apparatus or “Sniffers”

• Dogs can be used as well to sniff-out accelerant Dogs can be used as well to sniff-out accelerant residuesresidues

Hydrocarbon Detector or Sniffer

Gas Chromatography, Mass Spectroscopy

• Analysis of materials collected at a suspected arson site is done using GC-MS.

• The chromatogram is compared to known petroleum standards.

• One such standard is called the “gasoline standard”

• But first, the debris has to be prepped.

Headspace vapor

• The debris is placed in an airtight container and the container is heated.

• If the debris contains any volatiles or hydrocarbons (from accelerants), the vapors will rise to the top of the container.

• This risen vapor or headspace is removed with a syringe and injected into a GC.

This is a Gasoline Standard Gas Chromatograph

This is a Gas Chromatograph from suspicious fire debris

Introduction to ExplosivesIntroduction to Explosives

• Most bombing incidents involve Most bombing incidents involve homemade explosive deviceshomemade explosive devices

• There are a great many types of There are a great many types of explosives and explosive devicesexplosives and explosive devices

• Lab must determine type of explosives Lab must determine type of explosives and, if possible, reconstruct the explosive and, if possible, reconstruct the explosive devicedevice

ExplosivesExplosives

• An explosive is a material that undergoes rapid An explosive is a material that undergoes rapid exothermic oxidation reaction (combustion), exothermic oxidation reaction (combustion), producing immense quantities of gas.producing immense quantities of gas.

• The build-up of gas pressure in a confined The build-up of gas pressure in a confined space is the actual “Explosion”. The space is the actual “Explosion”. The damage is damage is caused by rapidly escaping gases and caused by rapidly escaping gases and confinement.confinement.

• The ignition of an explosive is called DetonationThe ignition of an explosive is called Detonation

Explosives

• Combustion (or decomposition) of explosives occurs so rapidly, that there isn’t enough time for the oxygen in the surrounding atmosphere to combine with the fuel.

• Therefore, many explosives must have their own source of oxygen – or oxidizing agents

Types of Explosives

• Low explosives• Combustion is relatively slow -1000 meters per

second• The speed of explosion is called the speed of speed of

deflagrationdeflagration• Crucial element is physical mixture of oxygen and fuel• Examples are black and smokeless powders

• Black powder is mixture of potassium nitrate, charcoal and sulphur

• Smokeless powder is nitrocellulose and perhaps nitro-glycerine

Black Powder (Low Explosive)• Black powder contains:

– 75% Potassium Nitrate (KNO3)– 15% Charcoal (C)– 10% Sulfur (S)

The KNO3 is the oxidizing agent. – When heat is applied to the powder, the

oxygen from KNO3 is liberated. – It combines with the carbon (fuel) and sulfur (for

stable combustion).– The combustion of charcoal and sulfur produces 2

gases – CO2 and N2.– The buildup of gases in the cartridge, propels the

bullet forward in bullet cartridges.

Black Powder Reaction

3C + S + 2KNO3 3CO2 + N2 + K2S + heatCarbon in charcoal

is fuel

Sulfur stabilizes

combustion

Saltpeter is the

oxidizing agent

Carbon dioxide gas

Nitrogen gas Potassium Sulfide solid

Smokeless Powder• Used as propellant in firearms and other weapons.

• There are 3 types:– Single-base – contains nitrocellulose– Double-base – contains nitrocellulose and nitroglycerine– Triple-base – contains nitrocellulose, nitroglycerine and

nitroguanidine

• Produce very little smoke when burned, unlike black powder.

• The reason that they are smokeless is that the combustion products are mainly gaseous, compared to around 55% solid products for black powder (potassium carbonate, potassium sulfate residues).

Types of Explosives part deux• High explosives – they detonate (explode) rather

than deflagrate (burn)• Combustion can range from 1000 mps to 10,000 mps• Oxygen usually contained in fuel molecule

• Two types Initiating (or primary explosives)Initiating (or primary explosives)

• Sensitive, will detonate readily when subjected to heat or shock.

• Used to detonate other explosives in explosive train (a triggering sequence that ends up in a detonation of explosives)

• Includes Nitroglycerine Noninitiating (Secondary or base explosives) Noninitiating (Secondary or base explosives)

• relatively insensitive, to heat, friction or shock, need special detonators such as low explosives.

• Includes Dynamite, TNT or PETN

• ANFOs or (Ammonium Nitrate Fuel Oil) (These are actually tertiary)

Nitroglycerin (Initiating or primary high explosive)Nitroglycerin (Initiating or primary high explosive)

• In its pure form, it is a contact explosive (physical shock can cause it to explode) and degrades over time to even more unstable forms.

• This makes it highly dangerous to transport or use.

• In this undiluted form, it is one of the most powerful high explosives, comparable to the newer military explosives

• Believe it or not, it is also used as heart medication – it is a vasodilator.

How does it work?

• The explosive power of nitroglycerin is derived from detonation: energy from the initial decomposition causes a pressure gradient that detonates the surrounding fuel.

DynamiteDynamite

• A creation of Alfred Nobel (he also dabbled in A creation of Alfred Nobel (he also dabbled in pure nitroglycerine and its explosive qualities)pure nitroglycerine and its explosive qualities)

• He liked the “oomph” of nitroglycerine, but not its He liked the “oomph” of nitroglycerine, but not its sensitivity. sensitivity.

• He discovered that kieselguhr or diatomaceous He discovered that kieselguhr or diatomaceous earth would absorb the nitroglycerine, but not earth would absorb the nitroglycerine, but not reduce its explosive force.reduce its explosive force.

Alfred Nobel, Sweden

Diatoms

Ingredients of Dynamite• Original dynamite consisted of three

parts nitroglycerin, one part diatomaceous earth and a small admixture of sodium carbonate.

• This mixture was formed into short sticks and wrapped in paper, with a “fuse” or a cord with a core of powder, that will transport the fire to the cylinder.

• Today, ammonium nitrate based dynamite is made and the fuse has been replaced with electronic detonators called blasting caps.blasting caps.

Electric Blasting Caps (Detonators)

Dynamite Today

High Explosives Acronyms

• TNT = Trinitro Toluene

• PETN = PentaErythritol TetraNitrate, also known as pentrite. PETN is also used as a vasodilator, similar to nitroglycerin. Used as medicine for heart diseases.

• RDX = Cyclotrimethylenetrinitramine

• HMX or Octagon = Cyclotetramethylene-tetranitramine (related to RDX)

TNT (Non-initiating or secondary high explosive)TNT (Non-initiating or secondary high explosive)

• Trinitro Toluene

• Most used by the military

• Used in grenades, bombs, shells, or even alone.

PETN

• PETN and TNT used together to make small-caliber projectiles

• Commercially used (mining, demolition, etc.)

• PETN is used in detonation cords or Primacords. These cords are used to create a series of explosions.

PETN primacords attached to demolition explosives.

Ammonium Nitrate Based Explosives

• They are:

• Water gels

• Emulsions

• ANFOs (Ammonium Nitrate Fuel Oil)

Water GelsWater Gels

• Consistency of gel or toothpasteConsistency of gel or toothpaste• Water-resistant, so good for explosions in or Water-resistant, so good for explosions in or

under bodies of water and wet conditionsunder bodies of water and wet conditions• Contains:Contains:

– Oxidizers : a mixture of ammonium nitrate and Oxidizers : a mixture of ammonium nitrate and sodium nitrate, gelled together with a carbohydrate sodium nitrate, gelled together with a carbohydrate like guar gum (food thickener and emulsifier)like guar gum (food thickener and emulsifier)

– The fuel : is usually a combustible substance such as The fuel : is usually a combustible substance such as aluminumaluminum

Emulsion ExplosivesEmulsion Explosives

• Have 2 distinct phasesHave 2 distinct phases– An oil phaseAn oil phase– A water phaseA water phase

• These emulsions containThese emulsions contain– An ammonium nitrate solution (oxidizer) An ammonium nitrate solution (oxidizer)

surrounded bysurrounded by– A hydrocarbon (fuel)A hydrocarbon (fuel)– An emulsifier such as glass, resin or ceramic An emulsifier such as glass, resin or ceramic

microspheres to make the explosive less microspheres to make the explosive less sensitivesensitive

ANFO• Ammonium nitrate (oxidizer) or urea

nitrate, soaked in a highly combustible hydrocarbon (fuel) – usually a fuel oil.

• Easy to make, safe to handle

• Ammonium nitrate is found in fertilizers, so ANFOs are a favorite type of homemade bombs.

ANFOs in trucks

Dupont is a leading manufacturer of industrial and commercial ANFO

Homemade Explosives

• Molotov Cocktails

• TATP (Triacetone triperoxide) – a favorite amongst Middle Eastern Terrorists.

Molotov cocktail• In its simplest form, a Molotov cocktail is a glass bottle

containing petrol fuel usually with a source of ignition such as a burning, fuel soaked, rag wick held in place by the bottle's stopper.

• In action the fuse is lit and the bottle hurled at a target such as a vehicle or fortification. When the bottle smashes on impact, the ensuing cloud of petrol droplets and vapor is ignited, causing an immediate fireball followed by a raging fire as the remainder of the fuel is consumed.

• Other flammable liquids such as wood alcohol and turpentine have been used in place of petrol.

• Thickening agents such as motor oil have been added to the fuel, analogously to the use of napalm, to help the burning liquid adhere to the target and create clouds of thick choking smoke.

http://upload.wikimedia.org/wikipedia/commons/5/55/Molotov_cocktail_flam.jpg

1, 2, and 3 step Explosive Trains

Analysis of Explosives

• Microscopy

• Thin layer chromatography

• Visualise with Greiss reagents

• Infrared spectrophotometry

• Detonator fragments

The Role of Forensic Science in the Investigation of Major Acts of Terrorism

Introduction

• A major terrorist act can generate huge amounts of evidence that can help in the investigation

• Different acts call for different strategies• This talk will examine three major terrorist

acts in the US during the past 10 years with emphasis on the forensic science aspects:• World Trade Center Bombing• Murrah building in Oklahoma City bombing• World Trade Center destruction

The World Trade Center Bombing

The Scenario

• Urea nitrate bomb put into truck and driven into underground WTC garage and parked at 4th level down

• Subsequent explosion did extensive damage to several levels of the garage and less damage to other levels

• Although goal was to topple WTC, little structural damage was done

• Some loss of life

Goals of Investigation

•Identify victims•Identify explosive•Recover bomb and timing

device•Determine method of

delivery

Evidence Sought

• Investigators had to remove large quantities of concrete, steel and cars to get to bomb seat

• Bomb seat contained most of the important evidence

• Bomb parts; timer, casing, etc.• Explosive residue• Parts of truck that contained

explosive

Areas of Forensic Science

• Explosives• Engineering• Questioned documents• Fingerprints• Pathology• DNA

The Murrah Building, Oklahoma City

The Scenario

• ANFO explosive and timer packed into a rented truck, which was then parked outside Murrah building

• Explosive confined to closed space such as truck is much more powerful

• Resulting explosion caused severe damage to building and loss of more than 100 lives

Goals of Investigation

•Identify victims•Identify explosive•Find timer and bomb parts•Determine method of

delivery

Evidence Sought

• Easier to find than in WTC because bomb seat outside building

• Explosive residues• Bomb parts• Bodies and body parts; cadaver

dogs, flies• Personal effects; helps in

identification of human remains

Areas of Forensic Science

• Anthropology• DNA and serology• Pathology• Entomology• Explosives• Trace evidence• Engineering• Questioned documents• Fingerprints

WTC Destruction

The Scenario

• Large airplanes, loaded with fuel, crash into WTC buildings

• Raging fires ignite everything in building above crash sites.

• Metal supports melt from heat• Building collapses due to inability to

support its own weight after structural damage

• Thousands of people killed

Goals of Investigation

• Cause known, no need to determine how destruction occurred

• Recover and identify bodies, parts of bodies and charred remains

• Recover personal effects that might help identify victims or perpetrators

• Evidence that might determine how hijackings occurred.

Evidence Sought

• Bodies and body parts; cadaver dogs, flies

• Charred remains• Personal effects• Trace evidence such as charred

papers• Weapons such as knives• Constraining devices such as wire

Areas of Forensic Science

• Anthropology• DNA and serology• Odontology• Pathology• Entomology• Trace evidence• Questioned documents• Fingerprints• Tools and toolmarks

THE ENDTHE END