Week 4

Chemistry of Explosives
Explosion – is a violent bursting or expansion
caused by the release of mechanical,
chemical or nuclear energy from a confined
area. This is a phenomenon resulting from a
sudden release of energy and this happens so
rapidly that a local accumulation of energy
occurs at the site of explosion moving
outward in various ways.
Types of Explosion
1. Mechanical Explosion – It is a sudden breaking
apart, shattering or bursting into pieces by
internal pressure; as that of gas or stream
boiler, also known as pressure explosion.
2. Chemical explosion – a source of explosion
wherein the source of this energy comes from
explosive such as gunpowder.
3. Nuclear explosion – an explosion due to
nuclear fusion and fission of particles.
Chemistry of Explosives
Explosives – any chemical compound or
mixture that under the influence of heat,
pressure, friction or shock, undergoes a
sudden chemical change or decomposition. It
is also a material that is capable of rapid
conversion from either a solid or liquid to a gas
with resultant heat, pressure and loud noise.
When exploded always accompanied with the
liberation of heat and almost with the
formation of gas.
Why do law enforcers need to know about
explosives?
• They often encounter explosives which are
found at the construction sites or those buried
underground.
• Law enforcers encounter explosives at the
crime scene.
• Law enforcers should know some lands may
contain toxic chemicals and explosives
ordinance.
Classification of Explosives
According to the Velocity of reaction involved
The speed of chemical reaction or detonation
of the explosive determines the classification
of explosive as a) low; b) primary and
initiating; and c) high explosives
A. Low explosives
These are the low burning and used mainly
as propellants like black and smokeless
powder. The rate of decomposition is
 relatively slow process and the wave produce is less than the
speed of sound. These are used for launching rockets,
projectiles from guns and missile systems.

B. Primary and initiating explosive

This kind of explosive is extremely sensitive to
detonation by heat, shock, friction and impact. It detonates
without burning, like lead azide and mercury fuminate. This is
use primarily to start an explosion.

C. High explosive
High explosives are materials that are characterized
by a very high rate of reaction, high pressure
development and the presence of a
detonation wave.

Mechanism of Explosion
An explosion produces a very rapid growing
shockwaves moving outward as it transform
into a more stable substances. It is
accompanied by a loud and sharp report as it
liberates great amount of energy in the form
of heat, light and other form of gases.
Effect of Explosion: Chain reaction causes the
decomposition and rearrangement of
molecules with a greater release of energy.
1. Explosive strength – The magnitude of an
explosion can be established based on the
amount of energy that is released.
2. Damage mechanism
A. Brisance – the direct measure of energy
transmission from explosion to the target.
 This is the most severe because of its
shattering action. Brisance is directly
proportional to the speed of decomposition of
explosives. Explosives with high shattering
power are termed high explosives. The
brisance effect of deflagrating material is
relatively small.
B. Sensitivity – is the effort required to initiate
explosive decomposition. The lesser the effort
required, the more sensitive is the explosive.
C. Shock Wave - the damage produced depend
on the location of explosion.

1. Earth shock – wave produced when an

explosive detonates underground producing
earthquake.

2. Water shock – wave produced when an

ordinance is detonated underwater.
Safety procedures when responding to an
explosive incident:
a. Do not use two-way radios, radar, or
television transmitting device within 500 ft.
This includes mobile data terminals and
cellular phones. Electromagnetic radiation
(EMR) given off by these devices can
detonate the item.
b. Notify proper authorities, (BFP, Police
department, EOD, etc.)
c. Clear and control the area. The size and type of
explosive, terrain, shielding and other factors
will determine the area to be controlled.
d. Stage emergency medical service (EMS), fire
and police units outside the control point.
e. Do not proceed to the suspected explosive. It
may have motion sensitive or acoustic fuses
that function when disturbed or senses target.
Use binoculars to observe the area.
f. Reduce potential effect of blast and flying
shrapnel by opening doors and windows and
by placing emergency vehicles in the path of
the blast wave to act as shield.
Gunpowder/gunpowder residue
Gunshot residue
– is defined as the traces of material that
remain after the use of a firearm using
gunpowder ammunition. The major sources
of these materials are the primer, propellant
and associated stabilizers and plasticizers that
are used in ammunition, as well as any
decomposition products of these materials
formed during detonation.
Component of Gunshot residue
A. Primer or lead residue
Primers are devices used to initiate the
propellant in ammunition, and may consist of
a single component or a mixture of various
inorganic or organic materials.
Residue from these materials are most likely to deposit on
the thumb and the dorsal portion of the firing hand of the
shooter, since these areas are in closest proximity to the
gases escaping from the breech of the gun during
discharge.
But individual who handle or came into contact with the
weapon without firing may have primer residues
deposited on their palm portion of the hand. The intensity
of these residues is not the same for the one who fired a
gun to the one who only holds a fired weapon.
B. Propellants Components
- Contain up to 23 organic compounds (FBI study)
- Nitrocellulose (NC) is virtually present along with the
nitrate and nitrogen containing compound such as
diphenylamine (DPA), used as stabilizer in the
powder.
Types of powder used in the ammunition of small
firearms:
1. Black powder – this consist of a mixture of
 carbon (charcoal), sulfur, and potassium nitrate.
The trick in making a suitable ballistic propellant was on
the correct ratio of the three chemicals. Although
many combinations have been used, the best formula
for small arms application is 75% potassium nitrate,
15% charcoal, and 10% sulfur. This recipe makes the
propellant we know today as black powder. Blasting
powders often used a different ratio of components.
Smokeless powder – since the discovery of
nitrocellulose in 1845, by treating cellulose
(wood fiber or raw cotton) with sulfuric acid,
and nitroglycerine by Alfred Novel evolves the
use of smokeless powders. Its’ clean
combustion was due to the nitration process
adding additional oxygen that made burning
very efficient.
Mechanism of Gun Action
In order for a bullet to be released and to attain
its maximum efficiency, the shell of
ammunition must contain appreciable
amount of primer and low explosives
(propellants).
Mechanism
Combustion of chemical components of a bullet
produces a sudden liberation of large amount
of gases capable of bursting the container,
which produces the effect of explosion.
Enclosure increases the rate of reaction due to
the increase in temperature caused by the heat
of reaction being confined by the container.
Burning rate – is the rate at which energy is released
during burning. Slow burning powders release their
energy (in the form of pressure) more slowly than the
fast burning powders. Fast burning powders are
commonly used for light loads with light bullets.
Detection of Gunshot Residue
Firearm discharge can deposit residues to a person at
close proximity, so the interpretations as to who fired
the weapon should be made with caution. (Thorton
1986)
Hand and body parts close to the fired weapon
may have residue consistent with having fired
the weapon. If there is no presence of
gunpowder residue, it does not mean that you
do not fire a weapon. The amount of residue
deposited decreases with increasing fire range.
Distance Determination – gunpowder examination of
clothing for possible gunshot range determination.
The size and density of the pattern of gunpowder
residue found on the clothing are the main factors
considered in determining the approximate
distance of the shooter to the victim. As the
distance to the victim increases, the size of pattern
expands while density decreases and vice-versa.
 
Importance of Distance determination

• In connection of self-defence pleas

• In the distinction between the murder and suicide. It is often
possible to state of considerable certainty the distance of
the gun from the target by the study of patterns and residues
left on the target. Not only the type of gun, but the condition
and type of ammunition will affect this pattern.
• In ascertaining the gunshot range, the examiner should note
and observe the entrance and exit hole; and Powder residue
pattern.
Entrance and exit Hole
• Bullet wipe residue. Entrance hole contains gunpowder
residue
• The diameter of entrance hole is smaller than the exit hole.
• The exit hole is frayed outward while entrance hole is inward.
• Gaping hole (deep and wide open) where the fabric is badly
torn
 Other Entrance hole characteristics
• Angled bullet entrance hole has elongated holes.
• Contact fires have uneven margins other distance fires
typically have an even margin
• Blackened area surrounding the hole. The presence of
partially burned powder residues around the entrance hole.
• Grazing bullet hole (several small holes created from a folded
garment).
Blackened area surrounding the hole. The presence of
partially burned powder residues around the entrance
hole.
Grazing bullet hole (several small holes created from a
folded garment).
Bullet hole examination may yield presence for lead and
copper

Classification of gunshot distance

Burning (direct) - the principal damage due to flame and

muzzle blast is more visible than to the penetration of
bullet.
• Singeing (1 to 2 inches) –slight burning
• Smudging - produced when the gun is held from
about 2 inches to the maximum of 8 inches. The
smoke and soot from the burned pores will be
deposited around the hole of the entrance producing
a dirty appearance and a blackening of area around
the bullet hole. This observation is more pronounced
when the ammunition used is black powder. The size
of the smudge depends on the following:
– Caliber of the gun
– Type of powder used
– Length of the barrel of the gun.
• Tattooing (8 to 18 inches) - (black coarsely
peppered pattern). Individual specks of
tattooing around the hole are visible by the
naked eye. The area of blackening around the
perforation will be found to diminish in size as
the muzzle of the gun is held further away
from the target. Blackening around the hole
will completely disappear. A few individual
specks of tattooing will be visible with the
naked eye.
The size of the area of powder tattooing will also
depend on
– Caliber of the gun
– Powder charge
– Distance of firing
• Wounds inflicted at a distance of more than
36 inches. Powder tattooing is seldom present
and the nitrates present will not be sufficient
for GSR.
THREE ZONES OF DISTANCES FROM WHICH A FIREARM WAS
DISCHARGED
1. Those in which the muzzle of the gun was held directly in
contact with the body or practically so.
• Characteristic patterns observed are as follows:
– Gaping hole where fabric is badly torn;
– Smudging
– Singeing of the fibers at the entrance;
– And tattooing.

Presence of partially burned powdered residues around the

entrance hole that may be embedded in the fabric. This
could present originally but may have become dislodged by
rough handling of the specimen or may have been blown
into the wound or may have been washed by bleeding.
2. Those in which the muzzle of the gun was held 2
inches to 36 inches away.

 Held from 2 inches to 8 inches (maximum), the smoke and soot

from the burned powder will be deposited around the hole of
entrance producing a dirty grimy appearance (covered with
soot, dirt adhering or embedded on the surface). More
pronounced when the ammunition used contains black powder.
Smudging around the perforation will be found to diminish in
size as the muzzle of the gun is held a distance of eight inches
and all the blackening around the hole completely disappear and
few individual specks of tattooing will be visible with the naked
eye. The size of the smudge depends upon the caliber of the gun,
type of powder used, length of the barrel, distance of the
muzzle of the gun was held .
This observation is helpful in determining whether the
wound was due to suicide or murder. If the gun was
discharged from a position in which the victim could not
easily have held himself, it intends to indicate a murder.
The size of the area of powder tattooing will also depend
on the caliber, powder charge and the distance of firing.
3. Those in which the muzzle of the gun was held beyond
36 inches.
Held from 8 inches to 36 inches. Tattooing is visible.
The partially burned and unburned powder particles will
be driven into the surface around the gunshot hole
producing a black coarsely peppered pattern called
tattooing.
Laboratory Examination Conducted
Color test
• Harrison-Gilroy – test for the presence of lead, antimony and
barium
• Sodium Rhodizonate test/ Griess Test – test for the presence of
nitrates.
 Gunshot residue test results can be divided into three categories:
Those where a pattern of residues is found on the evidence
garment and the questioned firearm and ammunition are
recovered.
Those where a pattern of residues is found on the evidence
garment and the firearm and ammunition are not recovered.
Those where only trace amounts or no residues are found on the
evidence garment
Collection, Preservation and Transit of Specimen
Collection of gunshot residue
• Clothing removed from the victim should be carefully and
cautiously handled to prevent powder residues to dislodge
from the garment. Do not wad the garment.
• Clothing heavily smeared with blood should be dried in shed
before packing
• Secure the area to be tested between two layers of heavy
cardboard fastened together tightly to prevent the specimen
from becoming postlude in the transit.
• Gun recovered from the scene of the crime and ammunition
available should be preserved.
• Pack it loosely for shipment. Each specimen should be
wrapped and mark
 
C. Firearm examination/ Examination of the
probable time the gun has been fired
• Lucas Test - a characteristic smell that
decreases in intensity with lapse of time and is
observable immediately after firing. Sometimes
after several weeks some slight smell remains.
• Hydrogen Sulfide – another product of
combusting gunpowder and is present in the
gaseous state that can be detected by means of
a lead acetate paper.
If the breech of the gun is kept close, this persists
between 2 to 3 hours after firing. The greater part
disappears about 4 to 5 hours but frequently, a
trace is remained for sometimes linger, the longest
period is up to 10 hours.
• Rusting – as a rule does not commence for several
days. No rust can be detected inside the barrel if
the gun was not fired. But if the gun was fired, iron
salts will be soon oxidized resulting in a formation
of rust. Rust formation is affected by humidity of
the air so that in the preparation of the result, the
factor must always be considered.
• Nitrite – presence of NO2 is determined by the
addition of diphenylamine reagent. If the colour
becomes blue, nitrites are present and we may say
that the firearm could have been fired recently.
• Presence of nitrates – diminishes after a lapse of
time. Can be detected by swabbing a portion of
residue in a barrel and mixed it with
diphenylamine reagent. If the colour becomes
yellow green, nitrates are present and we may say
that that the firearm could have been fired but not
recently.
Paraffin Examination

While the residue was deposited on the target in the

barrel of the gun, some of these unburned and partially
burned particles may escape around the breech of the gun
and implanted on the exposed surface of the hand of the
person firing a gun.

The test was designed to demonstrate the presence of

nitrates on the hands. Particularly in pores resulting from
firing of gun, due to the manner in which the powder
residue maybe blown out around the edge of the revolver
cylinder through imperfect fitting parts of the gun.
Different names of this test
1. Lunge’s test
2. Diphenylamine test
3. Dermal nitrate test
4. Gonzales test (the one who improved the
test)
Paraffin examination is non- specific but it can
be used as a corroborative evidence to
support the allegation or intended to support
the testimony of eyewitness.
Factors affecting the result of paraffin examination

1. Type of caliber of ammunition. A hand firing a

revolver is more likely to give a positive result for
gunpowder nitrates as compared to a hand firing
a pistol. In automatic pistol the chamber is an
integral part of the barrel whereas in revolver the
chamber is located in the cylinder and separated
from the barrel with air space. Thus leakage of
powder in revolver are more likely to occur.
2. Length of the barrel. A weapon with shorter
barrel will deposit residue over a larger area in
the hand of the firer. Distance of firing and
type of ammunition do not affect this factor. A
2 inches barrel will deposit residues over a
larger area than a weapon having a 5 inches
barrel even though they are fired at the same
distance and with the same type of
ammunition.
3. Age of gun/ efficiency of mechanism.
Complete combustion or the conversion of all
nitrates into its end product (carbon
monoxide, carbon dioxide, nitrogen gas,
oxygen and hydroxides) is more likely to occur
in a new weapon compared to an old one.
Leakage of gunpowder is more likely happen
in an old weapon where the breech
mechanism is no longer tightly fired.
4. Direction of firing. More powder residues
will be obtained when the gun is fired upward
than downward. Gunpowder residues have
weight and naturally fall down because of
gravity. Firing vertically, slightly greater than
firing horizontally from the same distance.
When gun is fired downward or vertically all
the residues will fall on the target, but when
fired horizontally some of the residues are
likely to fall short of the target.
5. Wind velocity and direction. In high velocity
(strong wind), the powder residues will be
blown in the direction of the wind. If there is
no wind or the wind direction is away from
the body, the probability of depositing nitrates
in the hands of the firer will be lessen.
6. Humidity/ percentage moisture in air.
Humidity lessens extent of combustion
yielding more gunpowder nitrates.
7. Use of gloves and when 72 hours has elapsed
(3 days).
True Positive vs False Positive
• True Positive- Blue specks with tailing appearance
because the particles are embedded into hands with
force
• Substances giving false positive result: there is
smudges or conglomeration of blue specks
• Fertilizers
• Explosives
• Tobacco
• Urine
• Certain cosmetics
• Food samples
• Cigarettes