CRI 023 – FORENSIC CHEMISTRY

In the investigation of crimes involving the use

of firearms, three most important problems may
arise.
(1) The first and probably of primary importance is
the problem of determining whether or not a
person has fired a gun with bare hands within a
pertinent period of time.
(2) The other is the means of determining the
probable gunshot range i.e., the distance the
firearm held from the body of the victim at the
time of discharged.
(3) A third problem may come up when the time of
firing of the gun becomes an issue.
1. Black Powder – because of its inherent
defects modern ammunition plants
abandoned the use of this.
It is possibly the oldest known explosive.
It is consists of an intimate mixture of charcoal
– 15%, sulfur – 10% and potassium or sodium
nitrate – 75%. When exploded in open space
the following reaction occurs:
2KNO3 + 3C + S  3CO2 + K2S + N2
This reaction holds true if the
composition of the powder is uniform, pure
and no other side reactions take place. Slight
difference in composition cannot be avoided
as well as side reactions cannot be controlled.
2. Smokeless powder – is the most widely
used propellant. It can be either be a single
based propellant or double propellant.
It is consists of cellulose nitrate or glyceryl
nitrate combined with cellulose nitrate and
some stabilizers. Among the stabilizers used
are nitrates, bichromates and oxalates. Some of
the organic stabilizers are nitrobenzene,
graphite and Vaseline. Stabilizers are added to
reduce side reactions. These combine with
products of decomposition and may have a
negative or positive catalytic effect. When
exploded the following reactions occur:
C12H1404(NO3)6  9 CO + 3N2 + 7H2O + 3CO2
(Cellulose nitrate)
4C3H3(NO3)3  12CO2 + 10H2O + 6N2 + O2
(Glyceryl nitrate)
 It will be notice that nitrates are
present in both gun powders so that one
will expect to find nitrates (NO3) in the
following:
1. Residue of the barrel of the gun
2. In or around the wound
3. On the clothing of the person fired
upon at close range
4. On the exposed surfaced of the
hand
a. Type and caliber of the ammunition –
different types of ammunition fired in the
same weapon and from the same distance
may give different pattern.
b. Length of the barrel of the gun – a
weapon with 2 inches barrel will deposit
residues over a larger area than a weapon
having a five inches barrel even though
they are fired at the same distance and
with the same type of ammunition.
c. Distance of the muzzle of the gun from
the target.
d. Humidity – affects the spend with which
powder burns. Powder having lesser
amount of moisture will burn more rapidly
and completely within a given time yielding
greater amount of residue.
e.Wind velocity and direction – in high winds
the residue will be blown in the directions of
the wind yielding a scattered pattern.
f. Direction of firing – firing vertically, slightly
greater than firing horizontally from the same
distance. Power residues have weight.When
gun is fired downward or vertically all of the
residence will fall on the target, but when
fired horizontally some of the residues are
likely to fall short of the target.
 The burned residues are partially
burned particles may escape around the
breech of the gun and implanted on the
exposed surface of the hand firing the gun
and the presence of this particles serves as
a basis for the diphenylamine-paraffin test
(DPA-Paraffin Test).
 At the instance of discharge there is a
certain amount of gases and mixture of
burned residues and partially burned
particles that escape from the breech of
the gun. These particles strike the exposed
surface of the hand holding the weapon
and became implanted into the skin.
Diphenylamine Test
- a test to determine whether a person fired a
gun or not with bare hands.
Procedures:
a. Paraffin Test - the taking of the cast to extact
the nitrates embedded or implanted in the
skin.
b. Diphenylamine Test – the chemical aspect of
the test. It determines the presence and
distribution of nitrates.
Reagent:
Diphenylamine reagent (0.5 gram
diphenylamine crystals dissolved in 100
ml of sulfuric acid and 20 ml of water).

Visible Result:
Deep blue specks that develop when
nitrates comes in contact with
diphenylamine reagent.
1. The test is not specific for nitrates since the role of
nitrate is simply oxidizing agent. The test cannot
determine the source of nitrate.
2. There are other substances which contain nitrate
oxidizing agents that are not in the ordinary
course of life like fertilizers, explosives, tobacco,
firecrackers, urine, cosmetics and detergents.
3. In general persons do not have nitrates or other
oxidants on their hands as a matter of common
occurrence.
4. Hands contaminated with nitrates from other
sources than gunpowder or any oxidant one will
expect to find either a smear blue color or
conglomeration of blue specks located at the
different places of the hand both dolsar and
palmar aspects.
1. It is possible that the gunpowder
particles may have been blown on the
hand directly from the barrel of the gun
being fired by another person.
2. An attempt to shield the body by raising
the hand would in some instances result
in the implanting of powder particles
on the hand of a person close to one
firing a gun.
1. Use of automatic pistol
2. Direction of the wind
3. Wind velocity
4. Excessive precipitation
5. Use of gloves
6. Knowledge of chemicals that will remove
the nitrates
7. Washing of hands
 In cases involving shooting incidents
where paraffin test is required, the person
suspected to have fired a gun should be
subjected to diphenylamine-paraffin test
immediately and in no case should it be
postponed seventy-two (72) hours after
shooting. It is possible to detect nitrates as
late as three days even though the hands
have been washed. In our country the
period is reduced to two days only due to
excessive perspiration.
 The clothing of the victim with bullet
perforation should be submitted for
possible gunshot range.