FORENSIC CHEMISTRY AND TOXICOLOGY

Glass and Glass Fractures

Glass: In the technical sense, glass is an inorganic product of fusion which has been cooled to a
rigid condition without crystallizing. Many glasses contain silica as their main component and glass
former.

In the scientific sense the term glass is often extended to all amorphous solids (and melts that
easily form amorphous solids), including plastics, resins, or other silica-free amorphous solids. In
addition, besides traditional melting techniques, any other means of preparation are considered,
such as ion implantation, and the sol-gel method. However, glass science commonly includes only
inorganic amorphous solids, while plastics and similar organics are covered by polymer science,
biology and further scientific disciplines.

Glass plays an essential role in various scientific fields and in industry. The optical and physical
properties of glass make it suitable for applications such as flat glass, container glass, optics and
optoelectronics material, laboratory equipment, thermal insulator (glass wool), reinforcement fiber
(glass-reinforced plastic, glass fiber reinforced concrete), and art.

The term glass developed in the late Roman Empire. It was in the Roman glassmaking center at
Trier, Germany, that the late-Latin term glesum originated, probably from a Germanic word for a
transparent, lustrous substance.

1. Two kinds of glass fractures

Two kinds of glass fractures:

Radial fractures -is a primary
fractures that resemble the spokes
of a wheel radiating outward from
the point of impact. Radial cracks
are fractures extending outward
from the point of impact.
Concentric fractures- are secondary fractures having the
appearance of circles around the point of impact connecting
one radiating crack to the other, thus forming triangular
pieces of glass. Concentric cracks are fractures forming in
an approximately circular pattern around the point of
impact. They are usually in straight segments that terminate
in an existing radial crack

Definition of terms:

1. Cone or crater (Hertzian cone) is a funnel-shaped area of damage caused by a high-velocity

impact.

2. Hackle is a line on the crack surface running parallel to the local direction of crack spreading.

3. Ream is an imperfection; nonhomogeneous layers of flat glass.4

4. Wallner lines (ridges) are rib-shaped marks with a wave-like pattern. Wallner lines are called rib
marks or ridges to describe their shape and are almost always concave in the direction from which
the crack was propagating.

 The Breaking of glass:

            When a force pushes on one side of a pane glass, the elasticity of glass permits it to bend in
the direction of the forced applied. Once the elastic limit is exceeded, the glass begins to crack.
Radial cracks are first commencing on the same side of the glass opposite to the destructive force.
Concentric cracks occur afterwards, starting on the same side as the force.

 Derivations from the study of fractures:

1.Point of Impact :The front of the glass can be determined due to the accumulation of dust and
dirt on the glass
2.Direction of impact :A bullet will make a clear cut hole in the side of the entrance rather than
on the exit side If fired perpendicularly, it will give a crater of uniform flaking. If shot is fired at
an angle from the right, the left side of the glass will give more flaking and vice versa.
Depression will be produced on the exit side of the glass due to the rebound of the glass. Radial
fractures can be felt on the exit side and concentric fractures on the entrance side.
3 .Cause of fractures

 Thermal Fractures  due to heat does not exhibit a definite pattern of radial and concentric
fractures but are characteristically wavy. They show little stress lines whereas fractures due to
mechanical means show a definite pattern of radial and concentric fractures
4.Determination of the sequence of multiple bullet holes

The radial fractures from the second bullet hole always terminate into the fractures from the first
bullet hole, the radial fractures from a third bullet terminate into the radial fractures from the
second bullet, and so forth.
  5. Determining the direction from which a bullet was fired: Compare the size of the entrance
hole to the size of the exit hole

  a. Exit holes: always larger, regardless of the type of material that was shot a larger piece of
glass is knocked out of the surface where the bullet is leaving because glass is elastic and bows
outward when struck.

  b. Entrance holes: bullet makes a very small hole when it enters glass always blows back in the
direction of the impact because of its elasticity, glass snaps back violently after being stressed
and can blow shattered glass back several meters and most of the shattered glass lands on the
impacted side of the glass, instead of by the exit hole.

Gunpowder Determination and Explosives

In the investigation of crimes involving the use of firearms, law enforcement officers need an
understanding to gunpowder, their burning characteristics and the way in which their burning rates
may be change in order to determine the following:

1.Whether the suspect/victim fired the firearms.

2.Whether the firearms were fired or not

3.The approximate distance of the firer to its target

1. Gunpowder
In more recent times, the general term “gunpowder” is replaced by the term “propellant”, which is
the primary propulsive force in a cartridge which when exploded will cause the bullet to be driven
forward towards the gun muzzles.

In a shooting case there are two types of gunshot residue that occur during the discharge of a
firearm

Primer gunshot residue (GSR) Gunshot residue (GSR)

 - comprised of fused particles of the -is principally composed of burnt and unburnt particles
elements lead, barium and antimony.  from the explosive primer, the propellant, as well as
components from the bullet , the cartridge case and
- identification of GSR can only the firearm  used.
associate a subject with a firearm. 
 -there are authors who use other definitions, such as
- analysis is conducted by scanning cartridge discharge residue (CDR) or firearm discharge
electron microscopy coupled with residue (FDR).
energy dispersive spectroscopy
(SEM/EDS - is the residue that gets deposited on the hands of the
shooter after the bullet has been fired.

It may or may not have some burnt, unburnt or semi-burnt

particles
 

Powder gunshot residue Modified Walker test( Griess test

-is pattern evidence that originates from the -is performed by first treating a piece of
muzzle of a firearm and is deposited on the desensitized photographic paper with a
target.  chemical mixture of sulfanilic acid in distilled
water and alpha-naphthol in methanol
-this residue pattern can be comprised of un-
burnt and partially burnt gun powder, -the resulting reaction will appear as orange
particulate metals and nitrites.  specks on the piece photographic paper

 -Pattern comparison and chemical testing can

assist in determining muzzle to target distance. 
Gunpowder range determination Factors to consider in determining the
approximate distance of the firer to its victim:
-gunshot residue can travel out from the gun to
distances of 3–5 feet (0.9–1.5 meters) or even 1. Size
farther.
2. Density
-at the farthest distance, only a few trace
particles may be present. 3. Pattern of gunpowder

-this information can be useful in determining if  

someone was near a gun while it was
discharged. - As the distance to the victim increases the size
of the pattern increases while the density
- GSR can match the residue left on clothes to decreases and vice versa.
match a specific gun
 

Paraffin test Interpretation of the result

chemical test is also known as 1. Characteristics of the specks; small,

minute blue specks.
-dermal nitrate  
2. Distribution of the specks: more than
-diphenylamine test. two(2) specks should be present for
positive results for the presence of
-lunge’s or gonzales test gunpowder.

-detects two polyatomic ions (nitrites and nitrates) that 3. Location of the specks; mostly found
originate from gunpowder or primer on the dorsal portion of the thumb and
index finger.
-positive test produces blue flecks in the paraffin in
response to deposits on the hands of the shooter
Presence or absence of gunpowder residues may Substances that will give a false positive
depend on several factors: reaction:

1. Types and caliber of the firearms Urine

2. Length of the barrel of the firearms Tobacco/cigarettes

3. Distance of the gun muzzle of the gun to the target Detergents

4. Humidity Cosmetics

5. Wind Velocity Explosives        

6. Direction of firing Fertilizers

7. Nature of the materials into which the gun was fired Firecrackers                 

8. Use of gloves Food samples

9. When 72 hours or three(3) days had lapse Matches

2. Test for Primer components (powder residue)

A. Harrison & Gilroy test

It was developed by Harrison and Gilroy to determine just three elements.

Procedure:

The hands of the subject are swab moistened with dilute hydrochloric acid.

The swab is dried and treated with triphenymethylarsonium iodide.

it is dried again then treated with sodium rhodosinate and finally dilute hydrochloric acid was
added.

Results:

1. If antimony is present on the swab, the first reagent ( triphenymethylarsonium iodide)-

    would give a orange color.

2. If lead and barium is present, the second reagent (sodium rhodizonate) would give a

    red color.

3. If lead is present the addition of dilute hydrochloric acid turn the spots purple.

Limitations:

            The test is not sensitive enough and may give misleading results.
B. Neuron Activation Analysis (NAA)

            It used in the qualitative analysis of major, trace and rare elements. The principle
involved in neuron activation analysis consists of first radiating a sample with neurons in a
nuclear reactor to produce specific radionuclides. After the irradiation, the characteristics
gamma rays emitted by the decaying nucleotides are quantitatively measured by gamma
spectroscopy, where the gamma rays detected at a particular energy are indicative of a specific
radio nucleotides presence. It detects barium, antimony but not lead. To collect samples for it,
use cotton swabs with plastic handles dip in a mild hydrochloric or nitric acid solution and wipe
the hands with the swabs where the residue is expected to be present.
C. Flameless Atomic Absorption spectrophotomerty (FAAS)

            It detects antimony, lead, barium and copper. It is capable of measuring the amounts of
various elements present. The sampling method is similar to that of NAA system except that 5%
nitric acid solution must be used.
D. Scanning Electron Microscopy (SEM)

            Scanning electron microscopy with energy dispersive analysis (SEM-NEDA) has
become an excellent method for detection of gunshot residue. It is considered the most reliable
test but requires the use of scanning electron microscope, a very expensive piece of equipment.
Samples are taken from the hand with tape.it looks for the distinctive shape of gunpowder and
then X-rays the particles to determine the elements present.

3. EXPLOSIVES
EXPLOSIVES:

Any explosive material has the following characteristics:

            It is chemically or otherwise energetically unstable. The initiation produces a sudden

expansion of the material accompanied by large changes in pressure (and typically also a loud flash
or loud noise) which is called explosion.

Classification of explosions as to the source of energy:

1. Mechanical explosion- cause by expansion of gasses producing high pressures beyond the
capacity of the container. It involves the use of machines or tools or produced by machine.
Examples:  machine use by arm forces particularly mechanical weapons.
2. Electrical explosion-associated with the energy of electricity to create explosions
3. Nuclear Explosion-involving the use of atomic nuclei or nuclear transformation. Most
industrialized and powerful countries create nuclear weapons and use it to distract other
countries, because once this nucleonic proper explode it creates another form of nucleus and
causes harmful effects towards living matter.
4. Atomic explosion-which the energy is associated with atoms, or consisting of atoms,
5. Chemical explosion-called a chemical reaction. It is a change in which a substance is
transformed into chemically different substance
 

Classification of explosives:

            The speed of the chemical reaction or detonation of the explosive determines the
classification of explosives:

1. Low explosives:

             Low explosives burn through deflagration rather than a detonation wave, are usually a
mixture, are ignited by heat and require confinement to create an explosion. They are use primarily
as propellants; they undergo auto combustion at rates that vary from few centimeters per second
to approximately 400 meters per second

A. Black Powder

            Black powder, the oldest explosives, this is an explosive substance that consists of carbon
material (charcoal is common, nitrate and sulfur. All such powders are extremely flammable, they
are design to intend to burn rapidly and vigorously when ignited. Oxygen from air is not necessary
for the combustion of smokeless powder since they contain built in oxygen to burn completely
even in a close space such as the chambers of a firearm.

Compositions: Modifications were introduced in order to lower

the rate of burning:
1. Potassium nitrate (KNO3) + charcoal +
sulfur 1. Addition of silicate dust and graphite

2. Sodium nitrate (NaNO3) + charcoal + 2. Addition of resin

sulfur
3. Substitution of pitch or cuprene for charcoal,
3. Potassium nitrate (KNO3) + charcoal + mixing black powder with nitrocellulose dissolves
sulfurless black powder in solvent
 

B. Smokeless powder:

            Smokeless powder is the most widely used propellants is based with nitrocellulose, It
contains stabilizers, plasticizers and coating and sometimes a burning modifiers.

Preparations:

Single base: compose of either Double base: compose of both Triple base: compose of both
cellulose nitrate or cellulose nitrate o& cellulose nitrate &
nitroglycerine nitroglycerine nitroglycerine and
nitroquanidine
 

2. High explosives:

            High explosives consist of molecules with many high-energy bonds. The shock wave breaks
an apart the molecular bonds between the atoms of the material at a rate approximately equal to
the speed of sound traveling through that substance. Because high explosives are generally solids
or liquids, this speed can be much greater than the speed of sound in air.

High explosives are conventionally subdivided into two classes and differentiated by sensitivity:

A. Primary-extremely sensitive to shock, friction and heat, they will burn rapidly or detonate if
ignited
B. Secondary- relatively insensitive to shock, friction and heat. They may burn when ignited in
small, unconfined quantities, detonation occurs otherwise.
 

Common High explosives:

  Chemical name Characteristics Uses

explosives
TNT Trinitrotoluene Light yellow, Military explosives, known second
brown or light oldest explosives
gray
Bombs, projectiles, grenades,
demolition charges, propellant
composition
RDX Triazacyclohexane White, maybe Detonating cord, blasting caps, base
dyed pink charge, projectile, bomb filler
Hexogen, cyclonite ingredients
HMX Tetranitro-tetrazacyclo- white Mixed with TNT to form explosives
octane, octagon, filler for high blast weapons, military
applications as buster charges for
Homocylonite artillery shells, components of solid
fuel rocket propellants
NG Nitroglycerine, glyceryl Colorless, Industrial explosives, main
nitrate odorless, oily components in many dynamites and an
liquid, pale ingredient in multi base propellants
yellow color
PETH Penta or ten, pentrit White crystalline, Detonating cord, blasting caps, booster
sometimes dyed charges, priming composition
green
AN Ammonium nitrate White, maybe Ingredients of explosives mixtures,
 dyed & presence dynamites and fertilizers
of other colors
EGDN Ethylene glycol Transparent Mixture with nitroglycerine for low
dinitrate, nitroglycol colorless, liquid freezing dynamite
glycoldinitrate explosives
NC Nitrocellulose,guncotton Transparent Blasting explosives, smokeless
, colorless, liquid powder, propellants
explosives
cellulose, nitrate, nitro
cotton
 

3 Primary or initiating explosives:

      These explosives are less powerful than secondary explosives but are easier to detonate (most
will detonate with a hot spark but detonate better with a blasting cap.) These explosives are often
used in the blasting caps. Most fall under the category of nitrates, peroxides, nitrides, sulfides,
chlorates and acetylides.

      These are compounds which are highly sensitive to mechanical shock, friction and heat and are
readily ignitable to direct contact with flame or electrical shock.

Explosives Chemical name Characteristics Uses

1. Mercury HG(ONC)2 White to gray or  
fulminate light brown
Mercuric It is thermally unstable and very sensitive
fulminate to impact and friction. It reacts with metals
in a moist atmosphere. Beings a mercury
derivative, it is a toxic compound.
2. Lead azide PB(N3)2 White to buff to It has a good stability to heat and storage.
gray It is less sensitive to impact, but more
sensitive to fiction. It is easily ignited. It is
compatible with most explosives and
priming mixture ingredients.
3. Silver azide AGNO3   It requires less energy for initiation than
lead azide and fires with shorter time
delay. It may be used in smaller quantities
as an initiator. All azides are toxic due to
the evolution of hydrazoic acid.
4. Diazo DDNP Green, yellow, It is sparingly spluble in water, non-
Nitrophenol brown crystalline hygroscopic and less sensitive that other
powder primary explosives to impact, friction or
electrostatic energy. It is used as an
initiator in industrial blasting caps.
5. Tetrazene Tetracene Pale yellow It decomposes in boiling water. It ignites
crystalline readily and is slightly more sensitive to
explosive impact than mercury fulminate. Its main
use is for the sensitization of priming
composition.
6. Lead Lead It is thermally stable, non-corrosive and non-hygroscopic. It is
styphnate Trinitrosorcinate very sensitive to flame and to electrostatic discharge. It is
therefore used sensitize lead azide and to initiate burning in
primer compositions. The addition of graphite enhances its
electrical conductivity in system designed for electrical
initiation. 
 

Industrial Explosive
Ammonium nitrate-fuel oil explosives (ANFO)-These mixtures are made of porous prills of AN
(about 94%) soaked in fuel oil (6%). In some cases, aluminum is added to increase the explosive
strength. These explosives are inexpensive and safe to handle, but low in explosive strength and
detonation velocity. They cannot be used in the presence of water

Water Explosives Slurries and water gels Explosive’s emulsions

-explosives do not contain -explosives are made of -sensitized by air bubbles,

NG and are based on a aqueous solution of AN and introduced by means of hollow
solution of nitrates, sodium or calcium nitrate, glass or plastic bubbles.
containing 10-15% of water. gelled by the addition of
They are inexpensive and guar gum or cross-linking -neither gelled nor cross-linked
safe to produce and handle. agents. their storage time is limited.
They are unstable and
deteriorate during aging. –high detonation velocity
compensates for low explosive
strength of the constituents.
Stabilizers: -chemical compounds that are added to explosives to control the rate, characteristics
and type of reaction that ensues following the detonation. They may also be used to maintain the
chemical stability of the explosive while in storage
 

Stabilizers in explosives

1. Diphenylamine (DPA)- used in single base propellants. Since it is incompatible with

nitroglycerin, it cannot be used in double-base and triple base propellants composition
2. Dinitrotoluene (DNT)-Used as stabilizers in single base propellants. Also used as a ballistic
modifier (homogenizer) for single base propellants
3. Ethyl Centralite-used as a stabilizer, gelatinizer and waterproofing agent. It can be used in
relatively large proportions (up to 8%) of the propellant composition
4. Methyl Centralite-used as a stabilizer for multi base propellant and as a burning rate modifier.
5. 2-Nitrodiphenyamine-used for double base and triple base propellants which use
nitroglycerine as gelatinizing agent for the nitrocellulose.
6. N-methly-P-Nitroaniline (MNA)-used as a stabilizer in the manufacturer of solid fuel
propellants
7. Silica (Sio2)-occurs commonly in nature as sandstone, silica sand or quartzite. It is the
starting material for production of silicate glasses and ceramics. Silica is one of the most
abundant oxide materials in the earth’s crust. It can exist in an amorphous form (vitreous silica)
or in a variety of crystalline forms. Often it will occur as a non-crystalline oxidation product on
the surface of silicon or silicon compounds. It is used in numerous types of explosives due to
inherent stability.