GUNPOWDER

AND
EXPLOSIVES

Compiled by:
Dr. Jun Cariňo Corpuz
RMT.,RN.,MACT.,US-RN.,PH.D.
DOH Certified Drug Analyst
 Importance :
It determines…
a. Person has fired a gun or not.
b. Probable gunshot range.
c. Time of firing of a gun.
 Classification of Gunpowder
1. Blackpowder
a. Composition:
- 75% KNO3
- 15% Carbon
- 10% Sulfur
 b. Chemical Reaction
KNO3 + C + S = CO2 + K2S + N2
2. Smokeless Powder
a. Single Based
- Nitrocellulose or Nitroglycerine
b. Double Based
- Nitrocellulose and Nitroglycerine
Bouble Base Ballistite Cordite Axite Amberite
Components

√ √ √
Nitrocellulose √

Nitroglycerine √ √ √ √

Vaseline √ √ √

Ba(NO3)2 √ √

KNO3 √ √

Wood
√
Chemical Reactions:(Smokeless)

a. Cellulose Nitrate
- C12H14O4(NO3)= CO+N2+H2O+CO2
b. Glycerol Nitrate
- C3H5O3(NO3) = CO2+H2O+N2+O2
•Explosion of 1 grain:
- 800-900 cc gas:
a. CO2 d. H2
b. N2
c. Unburnt powder (NO3)
•Less flame and less powder
residue than blackpowder
3. Semi-Smokelss Powder
- Mixture of:
a. 80 L of blackpowder
b. 20 L of smokeless
powder
 Stabilizers
- Chemicals that prevent side
reactions during firing
- Produce positive & negative
catalytic effects
Active Component of Gunpowder
is NO3
Kinds of Stabilizers:
Organic Inorganic

Nitrobenzene Nitrates

Graphite Dichromates

Vaseline Oxalates
Distance of the Gun from the
Victim’s Body When Fired
•Not more than 24 inches
a. Expelled particles embedded in
skin
b. More gunpowder at the upper
portion of wound entrance
c. Less gunpowder in smokeless
 Determination Whether a
Person has Fired a Gun

•Dorsum of hand is examined

•Gunpowder at the dorsum of the
hand may infer that a person has
fired a gun
Basis of the Tests:
- When a gun is discharged forms
two types of residues:
a. Metallic Elements
- From the primer not blown
towards the target
- Moves backward to the
shooter
Indications of Primer on the Palm:
- Defensive Movements
1. Grabs weapon at time of
discharge
2. Suicide
(steady barrel at the time of
discharge)
b. Gunpowder Residue:
- Partially and completely burnt
particles
1. Barrel of the gun
2. Inside and around the wound
3. Hand that fired a gun
4. Clothes in close range
 Factors Affecting Gunpower
Residues

1. Type & Caliber of Ammunition

- Manufacturer
- Different ammunition,
different pattern
2. Length of Barrel
- 2 inch barrel deposits residues
over a larger area than 5 inch
barrel
3. Humidity
- Scattered pattern in high
winds
4. Direction of Firing
- Vertical firing over a target is
slightly greater than
horizontal firing
- Vertical downward gun
powder falls short at the
target
 Procedure in Determining
Presence of Gunpowder
1. Gross Examination
- Non-conclusive
- Use of hand lens
- Check for fine black powder
particles:
- Entrance of gunshot
- Dorsum of hand
2. Microscopic Examination
- Fine particles magnified
- No characteristic shape, color
or consistency of gunpowder
3. Chemical Tests
a. Paraffin Test
- Diphenylamine Test
- Dermal Nitrate Test
- Lunge Test/ Gonzales Test
Principle: Nitrates in the
gunpowder residue (NO3)
reacts with the diphenylamine
Positive Result:
- A deep blue specks developed
when NO3 comes in contact with
diphenylamine reagent
H2SO4
- Cause pores of the skin to open
and exude particles of
gunpowder residue
False Positive Results:
a. Firecrackers e. Detergents
b. Explosives f. Cosmetics
c. Fertilizers g. Tobacco
d. Urine h. Oxidizing
Agents
False Positive Result:
•Chlorates, dichromates, iodates,
bromates, permanganates, higher
metal oxides etc
•Because of its unreliability, the
paraffin test has been abandoned
by forensic scientists.
False Negative Results
a. Use of automatic pistol
- Almost completely enclosed
b. Direction & Wind Velocity
b. On Clothings (Colored Ones)
Walker’s Test
1. C-Acid, H-Acid test
- Uses photographic paper
treated with either:
* C-Acid (2-naphthalamine-
4,8-disulfonic acid)
 *H- Acid (1-amino-8-naphthol-
3,6-disulfonic acid)
* Sulfonic Acid swabbed with
alpha naphthalamine in ethyl
alcohol
Positive Result:
- Dark orange brown spot on the
prepared paper
c. Griess Reagent
Principle:
-Nitrite in acid solution
reacts with a primary aromatic
amine forming diazonium salt
1. Alpha-naphthylamine
2. Sulfanilic acid in acetic acid
•Sulfanilic acid reacts with nitrous
acid to yield a diazonium ion
which then couples with alpha-
naphthylamine to produce a red
azo dye.
•Specific for nitrite, not specific for
gunshot residues
•Alpha-naphthylamine a powerful
carcinogen
•N-(1-naphthyl)ethylenediamine is
a suitable replacement agent
Tests for Primer Components:
1. Harrison & Gilroy Test
- Test for Primer components
- Sb.,Ba.,Pb.
- Swab moistened with 0.1M
HCl gathers residues
Principle:
1. Red Color with sodium
rhodisonate (Pb.,Ba.)
2. Addition of 1.5 M HCl:
- Blue-Violet Color (Pb)
- Bright Pink (Ba)
* Lacks sensitivity
2. Neutron Activation Analysis
(NAA)
- More specific to detect
nuclear reactor to detect
radiation
Principle:
- Ba and Sb converted to isotopes
by neutron bombardment
3. Flameles Atomic Absorption
Spectrophotometry (FAAS)
Principle:
- High temperature vaporizes
metalic elements
- Detected through Absorption
Spectrophotometry
4. Scanning Electron Microscope
w/ X-Ray Analyzer
- Adhesive to gather any particles
- Analyzed through Scanning
Electron Microscopy
- X-Ray Analyzer confirms their
presence
5. HPLC
a. Analyze pre-cleaned handswab
extracts obtained from hands
after firing a revolver
b. Pendant Mercury Drop
Electrode (PMDE) Detector
- Detect down to 1 ng/swab of
nitroglycerine.
6. Fluorimetric Detection
•One of the most sensitive
•Selective modes of detection
•Organic constituents of gunshot
residues identified by molecular
luminescence.
7. Supercritical Fluid
Chromatography(SFC)
•The mobile phase is a
supercritical fluid such as CO2,
N2O, NH3, or SF6.
•Solvation power for SF and
higher separation efficiency in
SFC
8. Capillary Electrophoresis
•Provide rapid, high-resolution
separations of complex mixtures
• In CE separation is carried out
by:
a. Electrophoresis
b. Electroosmosis
 Gunpowder Residue Test
(GPR)

Principle:
- Diphenhydramine reagent is
swabbed to the barrel and
chambers.
- A deep blue color
Gunshot Range Determination
(GSR)
Principle:
- When a gun is discharged,
gunpowder residue deposited
on the clothing of the victim.
- Distance of victim increases,the
size of the pattern also increases
- Sizes of pattern increases while
density decreases
Explosives

- Substances capable of exerting

an intense pressure on its
surrounding
- Due to sudden increase in
volume of substances
Increase Volume due: Extreme…
a. Physical Changes
b. Chemical Changes
c. Nuclear Changes
Change is accompanies by intense:
a. Heat
b. Flame
Definition of Terms:
a. Explosion
- Act of exploding, rapid
combustion, decomposition of gas
with violent increase of pressure
b. Detonation
- A violent explosion resulting from
instant decomposition of unstable
compound(TNT).
Classification of Explosions
A. Mechanical
- Explosion due to expansion of
gas
- Producing high pressure
beyond the capacity of the
container
B. Atomic
- Explosion due to atomic or
nuclear
C. Chemical
- Explosion due to rapid
transformation of unstable
substances
- Formation of heat
Classification of Explosives
- Based on speed of chemical rxn.
(Detonation)
A. Low Explosives
- Slow burning
- Used as propellants(50 cm/s)
- Shattering effect not intense
- Controllable explosion
Examples:
1. Smokeless Powder
- Nitrocellulose
a. Nitroglycerine
- Modern pistol
- Riffle cartridges
2. Blackpowder
- Mixture of potassium
nitrate, charcoal and
sulfur
a. Homemade bomb
3. Bottles of gasses
B. High Explosives
- High rate of decomposition
- Instense shattering effect
- Initiated by shock
- Speed of detonation at
3000-8000 m/sec
- Uncontrollable explosion
- Product of explosion same
direction as detonation wave
- Examples:
1. Trinitrotoluene (TNT)
a. First made by Germany
b. Mostly for military
explosives
c. Safe explosive
d. It will burn but not explode
if set on fire
e. Preparations:
Amonal: Mxture of
- TNT - Aluminum
- NH4NO3 - Carbon
Amatal: Mixtures of
- TNT
- NH4NO3
2. Readily Detonating Explosives
(RDE)
Nitro-glycerine: Mixture of
a. HNO3 c. H2SO4
b. Glycerine
- Oily yellow liquid
- Slightest shake cause
explosion
- Modified form (safer)
a. Dynamite g. Umsax
b. Gelignite
c. Gelatine
d. Plaster Gelatine
e. Ajax
f. Supergel
 Heating with Sulfuric acid
and Hg

Yields NO2
Brownish gas with irritating odor
3. Plastic Explosives
- Military explosive
- Like putty or molding clay
“Plasticutiers”
- Men who used plastic
explosives
4. Nitrocellulose
- Nitration of cotton or
cellulose
5. Picric Acid and Picrates
- Nitration of phenol
- Homemade bombs
- Explosion leaves yellow stain
on objects arounf
C. Primary / Initiating Explosives
- Sensitive to detonation by:
1. Heat 3. Friction
2. Shock 4. Impact
- Detonate w/o burning
- Examples:
1. Lead Azide
2. Mercury Fulminate
Criteria Needed in Chem.Rxn.:
1. Chemical Instability
- Provided by excessive N2
2. Oxygen
- Provided by oxides
3. Fuel
- C, H2 provide fuel
- Converted to oxides
Analysis of Explosives
A. Friction Test
- Explosive materials are
rubbed against rough subs.
- Use of Stone Slabs
- If material ignites(fire), it „s
an explosive
B. Impact Test
- Done with hammer
- Tests sensitivity of material
C. Flame Test
- Violent burning in a piece of
paper
D. Thin Layer Chromatography
•Simplest and most widely used
•Detect nitrocellulose on the upper
surface of a firer‟s hand.
•Cotton swabs moistened with
ether
•Extracted with acetone and
centrifuged.
Result:
- TLC using Griess reagent spray
to detect the nitrocellulose.
- Alpha-naphthylamine to
produce a red azo dye.
E. Gas Liquid Chromatography
- Separation of complex mixtures
a. Flame-ionization,
b. Electron-capture
c. Thermal Energy Analysis (TEA)
- Very selective detector for
explosives
F. Color Reaction/Wet Method
G. IR Spectrophotometer
H. Solubility Tests:
Carbon di Water
Sulfide

Black Powder Soluble Soluble

 Water Alcohols Acetone
and other
Esters
Guncotton Insolu- Slightly Soluble
ble Soluble
J. Heating with H2SO4 and Hg
1. Nitroglycerine
- Brownish gas w/irritating
odor
2. TNT
- Light brown color
K. Picrate/Picric Acid - Yellow
 Handling & Disposition
of Bomb
1. Handled only by qualified
experts
2. Upon discovery of suspected
bombs:
a. Take precautions
b. Clear & secure area
c. Do not move or touch
anything connected with it
d. Notify Proper Authorities:
- Fire Department
- Rescue Squad
- Medical Group
e. Remove flammable
materials near the area
f. Shut off :
- Power
- Fuel
- Electric current
 Ways of Starting
An Explosion
Black Powder
a. Simple Fuse
b. Detonators
- Cap like the primer of
cartridge
 - Exploded by:
- Fuse
- Electricity
- Impact
Dynamite:
- Exploded by Blasting Cap
Safety or Time Fuse
- Slow burning fuse
- Sets off a black powder
charge
- Made from black powder
wrapped with fabric
- Orange, black, white or green
- 15 meters length
Electric Blasting Cap
- For explosives that can not
be exploded by a flame
- eg. : Dynamite
: High Explosives
- Copper-filled tubes
 Firing Trains
• For safety in handling
• Consist of:
a. Fuse
b. Primer or Detonator
c. Main Charge
 Collection and
Preservation of Explosive
Evidence
Importance:
a. Show the kind of bomb
b. Show kind of trigger device
c. Nature of explosives

• Done by explosive experts

• Photographs are taken
Look for:
a. Fragments
b. Bits of wood (clock)
c. Cardboard
d. Parts of clock
 Methods of
Specimen Collection
a. Sift the soil through a
screen
b. Note odor & strange
chemicals
c. Carbon blackening
d. Liquid to glass bottle
 Tear Gas
• Very fine powder dispursed in
the form of dust
• Diluted with inert compounds:
a. Magnesium Oxide
b. Fuller’s Earth
• Fired from a cartridge or
exploded
Kinds of Tear Gas
a. Chloroacetophenone (C)
- 2-chloroacetophenone,
alpha-chloroacetophenone
- Phenacyl Chloride
- White to tan crystalline
solid
b. Phenylchloromethyketone
- Helpless gas or Chemical
mace
- Liquid, intense burning
- Penetrates skin
- Attacks nerve endings