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Arson and Combustion. Role of the forensic scientist. Establish a modus operandi and a suspect to which the physical evidence can be linked. In practice, at an Arson scene…….. detect and identify relevant chemical materials collected. Reconstruct and identify igniters or
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Role of the forensic scientist. • Establish a modus operandi and a suspect to which the physical evidence can be linked. • In practice, at an Arson scene…….. • detect and identify relevant chemical materials collected. • Reconstruct and identify igniters or detonating mechanisms.
Chemical reaction of fire. • Oxidation (or combustion) ∆T CH4 + 2O2 CO2 + 2H20 reactants products • But, methane mixed with oxygen does NOT produce fire!………….Why?
Oxidation of iron • Not all oxidations produce heat or flames. • Rust is oxidized iron!
Additional energy must be added to “get the process going”. • Energy can take many forms: Heat, electrical, mechanical, nuclear, light, chemical etc.
Chemical Energy • Chemical reactions involve the making and breaking of chemical bonds. • To break bonds…….absorb energy • To form bonds……create energy
Chemical reactions • The quantity of heat energy in a chemical reaction comes from the breaking and forming of chemical bonds.
EXOTHERMIC: when energy is given off or liberated in a reaction • ENDOTHERMIC: if a reaction requires more energy than it will liberate.
Heat of Combustion • If more energy is liberated than is required to break the different bonds….excess energy. • Excess energy is given off as heat and is called the heat of combustion. Source: www.repp.org/repp_pubs/articles/envImp/Table4
Ignition Temperature • “Energy barrier” for methane + oxygen to react is high, so a HIGH temperature is required to “jump start” this reaction.
Common igniters • Most common igniter is a lighted match BUT, Must consider other potential ignition sources eg. Electrical discharges, sparks, chemicals etc. Must also consider the rate or speed of the reaction.
Physical state & temperature of the fire. • Fuel will react ONLY when in the gaseous state. • The vapor burns when it mixes with oxygen and combusts as a flame.
Flash point • Lowest temperature at which a liquid gives off sufficient vapor to form a mixture with air that will support combustion. • (solid fuel’s are more complex….chemical breakdown process is called pyrolysis)
What is “spontaneous combustion”? • Result of a natural heat-producing process in a poorly ventilated area or container. • So, do we always need air (containing oxygen) for combustion/oxidation reactions to occur?
Summary • 3 requirements for combustion 1. Fuel 2. Available oxygen 3. Heat to initiate combustion with sufficient heat to sustain the reaction.
Searching the Fire Scene • Necessity for immediate investigation takes precedence over the requirement to obtain a search warrant. • Focus on finding the origin of the fire, then, • are they separate or connected? • Locate containers that held the accelerant • Evidence of signs of breaking and entering
Identifying the Accelerant. Field Detection • Portable vapor detector (“sniffer”) • Trained “sniffer” dogs.
Collection and Preservation of Arson Evidence 1.Collect 2-3 quarts of ash and soot debris 2. Package in airtight container. 3. Controls from similar but uncontaminated areas at the fire scene.
Vapor concentration • Increases the sensitivity 100 fold over the “headspace” conventional technique.
Analysis of Flammable residues. • G.C is the most sensitive and reliable method. (If we have a mixture we must use GC-MS.)
Explosives • Undergo RAPID, EXOTHERMIC oxidation reactions and produce large quantities of gas. • Explosives MUST have their own source of oxygen.
Explosives need extra oxygen! • The hot cigar! • If excess oxygen is made available (by soaking the cigar in liquid oxygen) the flame will burn hotter and longer. • This is the principle underlying explosive mixtures.
Explosive mixtures contain oxidizing agents to provide extra oxygen eg. potassium nitrate or potassium chlorate. Explosives using potassium chlorate. OR • Have oxygen and fuel components combined in one molecule
Fireworks are mini-explosions! • Potassium chlorate, icing sugar (the “fuel”) and a metal nitrate (NaNO3, Sr(NO3)2, Ba(NO3)2) are the ingredients for basic fireworks. • The color of the flames is dependent on the metal nitrate added (Bengal lights experiment).
Types of Explosives An explosion occurs at a rapid rate but the speed of decomposition varies greatly allowing classification. • high (high speed) ….speed of detonation • low (low speed) explosives …..speed of deflagration (burning)
Low explosives Usually black powder and smokeless powder. Very accessible to the public Ingredients: Fuel + oxidizing agent (eg. Potassium chlorate) Safety fuse – black powder wrapped in fabric or plastic casing.
Two Categories of High Explosives 1. Primary Explosives • very sensitive to heat shock or friction -> violent detonation • Used as primers eg. lead azide, lead styphnate
2. Secondary Explosives • majority of explosives for military or commercial use • Burn rather than detonate in open air • Booster + main charge
Commercial high (secondary) explosives Most commercial explosives are ammonium nitrate based Booster: Usually PETN Main charge: Water gel, emulsion and ANFO explosives.
Military high (secondary) explosives Booster: • RDX: most common and very powerful. • PETN: detonating cord (primacord) used in TNT mixtures for small caliber projectiles (eg. grenades) Main charge: • TNT: used alone or in combination for shells, bombs, grenades, demolition explosives etc. • Dynamite or binary explosives
Collection and Analysis of Explosives 1. Look for the presence of a crater 2. Wear PPE to avoid contamination 3. Systematically search the area - wire-mesh screens for sifting through debris - EGIS system
Final analysis back at the Lab! • Microscopic examination • Rinse explosives in solvent • TLC • HPLC GC-MS