MODULE 4

GUNPOWDER AND
EXPLOSIVES

OVERVIEW
This module will provide information on gunpowder and its residue, explosives,
explosive ingredients and explosion incident.

OBJECTIVES
 To be able to gain knowledge about gunpowder, its residue and examination
 To be able to know the different types of explosives, explosive ingredients and explosion
incident

SCOPE
1. Gunpowder
2. Gunpowder residue
3. Explosive and explosive ingredients
4. Explosion incident

ACTIVITY
  Online / On-site quiz

GUNPOWDER

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 Gunpowder (black powder) is a mixture of sulfur (S), carbon (C in the form of charcoal)
and potassium nitrate (KNO3 or saltpeter). It is the earliest known chemical explosive. The sulfur
and carbon act as fuels while the potassium nitrate is an oxidizer.

2KNO3 + S + 3C → K2S + N2 + 3CO2

10KNO3 + 3S + 8C → 2K2CO3 + 3K2SO4 + 6CO2 + 5N2

Aluminum (Al) is added to enhance the burning property. When this powder is burned,
combustion reaction takes place:

4KNO3 + O2 + S + C → CO2 + SO2 + 2K2O + 4NO2

It is classified as a low explosive because it does not detonate but deflagrates (burns
quickly) and does not burn as a single reaction.

Those made with less-expensive and more plentiful NaNO 3 instead of KNO3 (in
appropriate proportions) works well too. However, it is more hygroscopic. Gunpowder made
with NaNO3 must be kept sealed to remain stable.

I. COMPONENTS

The current standard composition through proportions by weight depends on the purpose
of the powder.

Purpose of the Powder KNO3 C S

gunpowder 75% 15% 10%
blasting powder 70% 14% 16%
blasting powder made of NaNO3 40% 30% 30%
French war powder (1879) 75% 12.5% 12.5%
English war powder (1879) 75% 15% 10%
British Congreve rockets 62.4% 23.2% 14.4%
British Mark VII gunpowder 65% 20% 15%
Brown gunpowder 79% 18% 3%

Other formulation that is base on its use are:

 rocketry - uses a slower burn rate because it need to accelerate the projectile for a much
longer time
 weapons - needs a higher burn rate to accelerate the projectile in a much shorter distance
 cannons - uses lower burn rate powders because most would burst with higher burn rate
powders

Other forms of gunpowder are:

 sulfur-free powders - sulfur was removed to prevent corrosion and to decrease the ignition
temperature thereby increasing the rate of combustion, having 70.5 parts of saltpeter and
29.5 parts of charcoal

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 6KNO3 + C7H4O → 3K2CO3 + 4CO2 + 2H2O + 3N2
 smokeless powders - mixture consists of nitrocellulose or glycerol nitrate combined with
some stabilizers having different burning properties that can generate higher pressures and
may rupture older weapons designed for blackpowder, with ranging color from brownish tan
to yellow to white

II. GUNPOWDER RESIDUE

Gunpowder residue are components of the bullet, elements from cartridge cases and gun
barrel where the bullet passes. When a firearm is discharged, unburned and partially burned
particles of gunpowder in addition to smoke are propelled out of the barrel along with the bullet
toward the target. If the muzzle of the weapon is sufficiently close, these products are deposited
onto the target.
 primer - flame produced when a low explosive containing the following explodes and is the
basis for examination:
a) initiating explosive - mercury fulminate
b) oxidizing agent - potassium chlorate or barium nitrate
c) fuel - antimony sulfide

A. PURPOSE OF GUNPOWDER RESIDUE EXAMINATION

Both hands of the suspect and the victim, the firearms and clothing must be examined to
determine the presence of gunpowder residues. Gunshot residue examination helps the
investigator to determine:
 whether a person has discharged a firearm or not
 whether a firearm was discharged or not
 possible gunshot range or the distance of the shooter to the victim

B. DISTANCE DETERMINATION

The distribution of gunpowder particles and other discharge residues around the bullet
hole permits a distance determination. This can establish the proximity of the people involved in
the shooting incident.
 distance determination - an assessment of the distance from which a handgun or rifle was
fired

C. POWDER RESIDUES ON GARMENTS

When garments or other evidence relevant to a shooting are received in the crime
laboratory, the surfaces of all items are first examined microscopically for gunpowder residue.
The clothing of a firearms victim must not be cutted or teared in the area of the holes to prevent
damage or disruption on powder residues deposited around it. These particles may be identifiable
by their characteristic colors, sizes and shapes. In other situations, the analyst must use chemical
tests.

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 nitrites - one type of chemical product resulting from the incomplete combustion of
smokeless (nitrocellulose) powder
 Griess test - method for locating powder residues by transferring particles embedded on the
target surface to chemically treated gelatin-coated photographic paper
 sodium rhodizonate - second chemical test performed to detect any trace of lead residue
around the bullet hole followed by a series of oversprays of acid solutions giving a color
reaction turning lead particles pink then blue-violet

D. PRIMER RESIDUES ON THE HANDS

The firing of a weapon not only propels residues toward the target but also the shooter.
Traces of these residues are often deposited on the firing hand of the shooter and their detection
can provide an information whether an individual has fired a weapon recently.
 Detection of primer residues or dermal nitrate test - determination of powder residues on the
hands using chemical tests that could detect unburned gunpowder or nitrates by applying hot
paraffin wax and after drying, it will be tested with diphenylamine. A blue color indicates a
positive reacton for nitrates.
 Tests for primer residues - determination whether a person has fired or handled a weapon or
has been near a discharged firearm is made by measuring the presence and amount of barium
and antimony on the suspect’s hands.

E. FACTORS AFFECTING THE PRESENCE OF GUNPOWDER RESIDUES

The factors that can affect the amount and distribution of gunshot residue (GSR) on skin
and clothing include:
 firing distance
 length and diameter of the firearm barrel
 characteristics of the gunpowder
 angle between the firearm barrel and target
 characteristics of the cartridge
 the environment (moisture, wind, heat)
 type of clothing
 intermediate targets
 characteristics of the target (tissue type, putrefaction, blood marks)
 use of gloves

F. COMPONENTS OF GUNPOWDER RESIDUE

1. Primer or lead residue

Primer elements may be easier to detect in residues because they do not get as hot as that
of powder.
 Major primer elemental composition: lead (Pb), barium (Ba) and antimony (Sb)
 Trace element: aluminum (Al), sulfur (S), tin (Sn), calcium (Ca), potassium (K), chlorine
(Cl) and silicon (Si)

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 Inorganic compound: mercury fulminates (present in most ammunition manufactured in
Eastern Europe and used in Middle East)

In addition, these residues gradually adhere to the discharged bullets. Thus, primer
residue can be found in targets or wounds at considerable distance from the muzzle up to 200
meters.

2. Gunpowder residue
 contains up to 23 organic compounds
 nitrocellulose is virtually always present along with nitrate and nitrogen
containing compound such as diphenylamine or DPA (stabilizer in powder)

3. Composition of cartridge case, bullet coating and metal jacket

 cartridge and primer cases: brass (7:3 copper-zinc)
 bullet cores: lead, barium, antimony and few iron alloy
 bullet jackets: brass (9:1 copper-zinc) and some are iron, aluminum or nickel
alloy

EXPLOSIVES
The ready accessibility of potentially explosive chemicals and other explosive substances
has provided any person or organization a lethal weapon bent on but not limited to, revenge,
destruction of commercial operations or just plain mischief. These incidents typically involve
homemade explosives and incendiary devices base on the imagination and ingenuity of the
bomber.
 explosives - compounds that are unstable and break down with the sudden release of large
amounts of energy

An explosive consists of an explosive material or mixture, a container and an ignition

source.

I. EXPLOSION

Explosion or bomb investigation requires close cooperation among a group of highly

specialized individuals trained and experienced in bomb disposal, bomb-site investigation,
forensic analysis and criminal investigation. The criminalist must detect and identify explosive
chemicals recovered from the crime scene as well as identify the detonating mechanisms.
 explosion - the sudden conversion of chemical or mechanical energy into kinetic energy
caused by combustion with the release of heat, light and mechanical shock with the rapid
expansion of gases
 explosion limit, flammability limit - the highest or lowest concentration of a flammable gas
or vapor in air that will explode or burn readily when ignited and is usually expressed as a
volume percent of gas or vapor in air

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 A. CHEMISTRY OF EXPLOSIONS

The distinguishing characteristic of an explosion is the rapid rate of the reaction. The
sudden build-up of expanding gas pressure at the origin of the explosion produces the violent
physical disruption of the surrounding environment.

Explosives must have its own source of oxygen because they undergo a rapid exothermic
oxidation reaction producing large quantities of gases. Detonation occurs so rapidly that oxygen
in the air cannot participate in the reaction.
 oxidizing agent - substance that supplies oxygen to a chemical reaction

Oxygen-containing potassium nitrate acts as an oxidizing agent for the charcoal and
sulfur fuels. As heat is applied to blackpowder, oxygen is liberated from potassium nitrate and
simultaneously combines with charcoal and sulfur to produce heat and gases (symbolized by ↑),
as represented in the following chemical equation:

2KNO3 + S + 3C → K2S + N2↑ + 3CO2↑

Some explosives have their oxygen and fuel components combined within one molecule.
For example, the chemical structure of nitroglycerin, the major constituent of dynamite,
combines carbon, hydrogen, nitrogen and oxygen:

When nitroglycerin detonates, large quantities of

energy are released as the molecules decomposes, and the
oxygen recombines to produce large volumes of carbon
dioxide, nitrogen and water.

B. TYPES OF EXPLOSIVES

Explosives are classified as high and low explosives base on the speed of its
decomposition.
 deflagration (burning) - the speed of decomposition in low explosive characterized by very
rapid oxidation reaction producing heat, light and a subsonic or low-intensity pressure wave
that can disrupt the surroundings
 detonation - an extremely rapid oxidation reaction creating a violent disruptive effect and an
intense supersonic or high-speed shock wave breaking the chemical bonds within the
explosive charge of high explosive leading to a new instantaneous build-up of heat and gases
1. Low explosives - decomposes relatively slow with a velocity of detonation less than
1,000 m/s that produces a propelling or throwing action
a. blackpowder - a relatively stable mixture of potassium nitrate or sodium nitrate
with charcoal and sulfur. Unconfined, it merely burns. It is commonly used in
safety fuses carrying a flame to an explosive charge. When confined, it
becomes lethal.

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  safety fuse - a cord containing black powder wrapped in a fabric or plastic
casing used to carry a flame at a uniform rate to an explosive charge that
allows a person adequate time to leave the site before explosion
b. smokeless powder - the safest and most powerful low explosive
 single-base powder - consists of nitrated cotton or nitrocellulose
 double-base powder - nitroglycerin mixed with nitrocellulose
 triple-base powder - nitrocellulose + nitroglycerin + nitroguanidine
c. chlorate mixtures - an oxidizing agent mixed with fuels such as carbon, sulfur,
starch, phosphorus and magnesium filings wherein it may also be ignited by the
heat generated from a chemical reaction
d. gas-air mixtures - created when a considerable quantity of natural gases capes
into a confined area and mixes with a sufficient amount or air which when
ignited, results in simultaneous combustion and sudden production of large
volumes of gases and heat
 mixtures of air and a gaseous fuel explode or burn only within a limited
concentration range
 rich mixtures - mixtures at or near the upper concentration limit explode
with some gas remains unconsumed because there is not enough oxygen to
complete the combustion
As air rushes back into the origin of the explosion, it combines
with the residual hot gas, producing a fire that is characterized by a
whoosh sound and is often more destructive than the explosion preceding
it.
 lean mixtures - mixtures near the lower end of the limit generally causes an
explosion without causing accompanying damage due to fire

2. High explosives - an explosive with a velocity of detonation greater than 1,000 m/s
to 8,500 m/s producing a smashing or shattering effect and is classified based on
their sensitivity to heat, shock or friction
a. primary explosives (primers) - are ultrasensitive to heat, shock or friction,
under normal conditions detonate violently instead of burning and is used to
detonate other explosives through a chain reaction, the major ingredients of
blasting caps and rarely used as the main charge of a homemade bomb
 blasting caps - small explosive devices used to detonate larger explosives
 examples: mercury fulminate (Hg(CNO)2), silver fulminate (AgCNO), lead
azide (Pb(N3)2), lead styphnate (PbC6HN3O8), diazodinitrophenol (C6H2N4O5)
and silver azide (AgN3)
b. secondary explosives - more stable and relatively insensitive to heat, shock or
friction and normally burn rather than detonate when small quantities are
ingnited in open air and comprises mostly of high explosives
 dynamite - created in 1867 by Swedish chemist Alfred Nobel, searching
for a method to desensitize nitroglycerin, found that when kieselguhr, a
variety of diatomaceous earth absorbing a large portion of nitroglycerin, it
became less sensitive but still retained its explosive force and later decided
to use wood pulp as an absorbent instead because kieselguhr is a heat-
absorbing material

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 straight dynamite series - pulp dynamite used when a quick shattering is
desired which includes sodium nitrate (oxidizing agent) and a small
percentage of calcium carbonate (stabilizer) and is rated by strength
(determined by the weight percentage of nitroglycerin in the formula)
 ammonium nitrate - mixture of oxygen-rich ammonium nitrate with a fuel
to form a low-cost and very stable explosive
 water gels - have a consistency resembling set gelatin or gel-type
toothpaste characterized by water-resistant nature and are employed for all
types of blasting under wet conditions based on formulations of
ammonium nitrate and sodium nitrate gelled with a natural polysaccharide
and a combustible material is mixed into the gel to serve as fuel
 emulsion - consist of two distinct phases, an oil phase and a water phase
wherein a droplet of a supersaturated solution of ammonium nitrates is
surrounded by a hydrocarbon serving as a fuel or a typical emusion
consists of water, one or more inorganic nitrate oxidizers, oil and
emulsifying agents
 microspheres or microballoons - micron-sized glass, resin or ceramic
spheres emulsion content that controls the explosive’s sensitivity and
detonation velocity
 ANFO (ammonium nitrate fuel oil) - ammonium nitrate soaked in fuel oil
 TATP (triacetone triperoxide) - a friction and impact sensitive improvised
homemade explosive prepared by reacting the common ingredients of
acetone and hydrogen peroxide in the presence of an acid catalyst which
when confined in a container is extremely potent
 RDX (cyclotrimethylenetrinitramine) - the most popular and powerful
military explosive in the form of a pliable plastic of doughlike consistency
and is a content of composition C-4
 TNT (trinitrotoluene) - stable to friction and impact, does not react with
water or metals but can be converted to unstable compounds by treatment
with base
 Tetryl (tetrile nitramine, trinitrophenylmethylnitramine, 2,4,6-
trinitrophenyl-N-methylnitramine) - an off-white to yellow solid
commonly used as a booster explosive because it tolerates compression
well or used to make detonators that can be ignited by flame, friction, and
shock wherein in large quantities, it may detonate rather than burn
 military dynamite - composed of RDX and TNT
 PETN (pentaerythritol tetranitrate or penthrite) - used as explosive core in
a detonating cord
 detonating cord (primacord) - a cordlike explosive containing a core of
high-explosive material used to connect a series of explosive charges so
that they will detonate simultaneously
 detonators - initiates explosion with bombs made of high explosives
usually blasting caps composed of copper or aluminum cases filled with
lead azide as an initiating charge and PETN or RDX as a detonating charge
 blasting caps - initiated by means of a burning safety fuse or by an
electrical current

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 C. INCENDIARY WEAPONS

Incendiary weapons (IEDs or improvised explosive devices) - made of the following:

1. flammable material - include common household chemicals
2. container - include light bulbs, propane and butane cylinders, plastic pipes, bottles and cans
3. ignition source - include matches, gas lighters, fireworks, roadway flares and electrical
components and devices and may be paired with timing devices, sensors, radio-operated
remote control or a cellphone

Examples of IEDs:
 pipe bomb - consists of blackpowder, the pipe’s seam will split and its face plates on the
capped ends will be pushed out
 Molotov cocktail - consists of a glass bottle containing flammable liquid and a rag as a wick
 blackpowder rolled in paper with a string lead

D. DETECTION, COLLECTION AND ANALYSIS

Undetonated residues of the explosive remaining at the site of the explosion should be
collected.

The most obvious characteristic of a high or contained low explosive is the presence of a
crater at the origin of the blast. Once it has been located, all loose soil and other debris must
immediately be removed from the interior of the hole and preserve for laboratory analysis. Other
good sources of explosive residues are objects located near the origin of detonation.

All materials collected for examination must be placed in airtight sealed containers and
labeled with pertinent information. Plastic bags should not be used to store evidence because
some explosive residues can actually escape and sharp-edged ojects may pierce its sides.

Materials for examination are examined chemically or microscopically to detect

unconsumed explosive particles. The recovered debris is thoroughly rinsed with acetone. Others
are to be rinsed with water.

1. Color test for explosives

Reagent
Substance
Griess Diphenylamine Alcoholic KOH
chlorate no color blue no color
nitrate pink to red blue no color
nitrocellulose pink blue-black no color
nitroglycerin pink to red blue no color
PETN pink to red blue no color
RDX pink to red blue no color
TNT no color no color red
tetryl pink to red blue red-violet

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 Griess test - test for nitrites published in 1858 by Peter Griess
 diphenylamine test - test for oxidizing ions, especially nitrates, nitrites, chlorates and ferric
ions
 alcoholic KOH - in addition, 2,4-dinitrotoluene results in a yellow color
 aniline hydrochloride test - test for chlorates and chlorites, prepared using aniline acidified
with hydrochloric acid and activated potassium chlorate showing blue color
 Nessler’s reagent (mercuric iodide solution) - the solution is a faint yellow in color used to
detect the presence of ammonium ions showing orange-yellow/brown precipitate
 anthrone test - test for carbohydrates including sugars and starches like those in
nitrocellulose showing blue-green color
 Reinsch test - test for inorganic explosive residue containing bismuth, thallium, antimony
and tin

Reagent
Substance Additional test
Barium chloride Silver nitrate
sulfate ions white precipitate
chloride ions white precipitate
re-dissolved with
carbonates white precipitate white precipitate
acetic acid
concentrated
sulfates and other off-white to yellow off-white to yellow ammonium hydroxide
halide ions precipitate precipitate will re-dissolve halide
precipitates

However, non-explosive materials containing nitrites and nitrates will also yield a
presumptive positive result. Therefor, all color tests must be confirmed with instrumental
chemical tests.

2. Microcrystalline test for explosives

 Cropen test - used to indicate the presence of chlorates and perchorates forming
insoluble crystals
a. perchlorates form blue needle crystals, some with a purplish tinge that may grow
singly or in blundles and exhibit blunt or split ends
b. chlorate crystals form blue rosettes or single crystals, some of which have a slight
purplish tinge
 the chlorate needles are smaller and thinner than those of perchlorates and are slower to
develop
 high concentration leads to small crystal formation
 impurities may lead to unusual and distorted crystal formation
 reference standard is used to verify the positive result
 old reagents may not produce the expected crystals

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 REFERENCES
Elkins, Kelly M., 2019. Introduction to Forensic Chemistry. CRC Press. FL, USA

Fisher, Barry A. J., Tilstone, William J., Woytowicz, Catherine., 2009. Introduction to
Criminalistics. Elsevier Academic Press. MA, USA

Houck, Max M., Siegel, Jay A., 2010. Fundamentals of Forensic Science. Second Edition.
Elsevier. MA, USA

Saferstein, Richard. 2013. Forensic Science. Pearson Education, Inc. New Jersey, USA

https://en.wikipedia.org/wiki/Gunpowder

https://webpath.med.utah.edu/TUTORIAL/GUNS/GUNINJ.html

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