Explosives and Explosions

The Chemistry of High

Energy Organic Compounds
What is an Explosion?

Rapid burning of a material

resulting in a sudden build-up
and release of heat and gas
pressure.
Explosions Which Rely
on Oxygen from the Air
• Combustion of gasoline in the
engine of your car.

• How easy is it to make gasoline

explode?
Hexanes: Among the many hydrocarbons
found in gasoline, they are representative of
the volatility and explosivity of gasoline.
 Hexanes burn rapidly in air to
form carbon dioxide and water.

2 C6H14 + 19 O2 12 CO2 + 14 H2O

Hexanes will not explode in a closed container

and neither will gasoline.
•Too much fuel
•Not enough oxygen

The gas tank on your car is not an explosion

hazard.
•Vapor phase concentration of hydrocarbons is
above upper explosive limit (UEL) of 8%.
 Ethanol also burns in air.

CH3CH2OH + 3 O2 2 CO2 + 14 H2O

Ethanol is highly explosive in a closed

container

• optimum balance of fuel and oxygen in the vapor

•Vapor phase concentration of ethanol at room

temperature falls between the LEL and UEL.
What about other types of
hydrocarbon fuels and fuel tanks?

• Diesel and Jet fuel tanks have a

higher risk of explosion than
automobile fuel tanks.

• TWA Flight 800 exploded in mid air in

1996, probably due to a vapor phase
fuel tank explosion.
Surprisingly, explosivity of jet
airplane fuel tanks is not well
studied or understood.

“The July 17, 1996, crash of TWA flight 800, a Boeing 747 airplane, was
blamed on a fuel-air explosion within the center wing tank, with the
ignition source still unidentified. As a consequence of the accident, the
Federal Aviation Administration (FAA) is evaluating improved safety
requirements for the fuel tanks on commercial aircraft. One technique,
recommended by the National Transportation Safety Board (NTSB), is to
maintain sufficient fuel in the center wing tanks of transport aircraft to
limit the liquid fuel temperature rise and evaporation, thus keeping the
vapor fuel/air ratio below the explosive limit. Initial attempts to determine
the benefit of additional fuel in the center tank were frustrated by the
lack of an acceptable method for determining the explosive hazard in the
tank under varying conditions.”

- FAA final report, TWA Flight 800 crash investigation.

How can we make explosives
without the limitation of needing
oxygen from the air?

• Make the “oxygen” (oxidizing agent)

part of the chemical structure.

• Example: Nitrocellulose used in gun

powder.
Cellulose (cotton) burns
slowly in air.

H OH

H H OH
O
O
HO O
H H
OH HO O
H H H OH
H
H OH O

H
H HO O

Cellulose H OH O

H
major component of cotton
Nitrocellulose (gun cotton)
burns very rapidly even
without air.
NO2

H O
NO2
H H O
O
O
O
O H H
O
O O NO2
O2N H H H O
O2 N O2N H
H O O

H
O2N H O O
O2N

Nitrocellulose H
H
O O
"gun cotton" O2N H

major component of modern gun powder and fireworks

High Explosives Burn at
Supersonic Speeds

Conflagration: rapid burning with a flame

front traveling through the material at
1 m/sec to 300 m/sec.

Detonation: “instantaneous” burning with

flame front traveling through the material
at 1000 m/sec to 3000 m/sec resulting in a
supersonic shock wave.
Primary and Secondary
High Explosives

• Primary High Explosives

- detonate very easily
- minimal activation energy.

• Secondary High Explosives

- do not detonate easily
- high activation energy
Early Examples of Primary
High Explosives
CH2OH CH2ONO2
HNO3
CHOH CHONO2
H2SO4
CH2OH CH2ONO2

Glycerine Nitroglycerine

CH2OH CH2ONO2
HNO3
HOH2C C CH2OH O2NOH2C C CH2ONO2
H2SO4
CH2OH CH2ONO2

Pentaerythritol Pentaerythritoltetranitrate
(PETN)
Nitroglycerine

• Nitroglycerine detonates by rapidly rearranging to a collection

of small stable gas molecules releasing a huge quantity of heat
and pressure.

CH2ONO2
12 CO2 + 10 H2O +
Detonation
4 CHONO2
6 N2 + O2
CH2ONO2

• Pure Nitroglycerine is way too “sensitive” to be a useful

explosive. It was the invention of dynamite by Alfred Nobel that
converted nitroglycerine into a useful commercial and military
explosive by mixing nitroglycerine with clay (diatomaceous
earth) and forming the mixture into dynamite sticks.
Nitrogen triiodide

• NI3 also detonates by rearrangement to a

collection of small stable gas molecules.

2 NI3 N2 + 3 I2
Secondary High Explosives

• Compounds which are not easily

(accidentally) detonated but which
can be detonated intentionally to
cause very high energy explosions.

• Secondary explosives require a small

amount of a primary explosive to set
them off.
Examples of Secondary
High Explosives
CH3
OH

O2N NO2
O2N NO2

NO2
NO2

TNT Picric Acid

NO2
O2N NO2
N N N
O2N
N

N N
NO2
N
NO2

O2N
RDX
HMX
Predicting the Products of
Organic High Explosive Reactions
• Carbon combines with oxygen to form CO to maximum extent
possible.

• Hydrogen combines with any additional oxygen to form H2O to

maximum extent possible.

• CO combines with any additional oxygen to form CO2.

• Nitrogen forms N2.

• Excess oxygen forms O2.

• Excess hydrogen forms H2.

Oxygen Balance: A useful
concept for evaluating high
explosives.

Oavail - Oneeded
%OB = --------------------------- (100)
mass of comp.
Oxygen Balance of Some
Representative High Explosives

Explosive %OB
TNT -74

RDX -43

Nitroglycerine +7.0

Ammonium Nitrate +20

Mixing Explosives to Achieve
Optimum %OB

Amatols = mixtures of ammonium

nitrate and TNT

ANFO = mixtures of ammonium

nitrate and fuel oil
ANFO – A crude “low tech” high
explosive that has been used by
terrorists with devastating results.

Sterling Hall Bombing Here at UW:

“…. In the early morning hours of August 24, 1970, the New
Years Gang loaded about 2,000 pounds of ammonium nitrate
soaked in aviation fuel into a stolen Ford. The group parked the
van below the Army Mathematics Research Center, in a driveway
of Sterling Hall. At 3:42 A.M. the bomb exploded. It was powerful
enough to knock out windows six blocks away, and police found
pieces of the Ford van on top of an eight-story building
nearby….”

- www.sit.wisc.edu/~psohandbook
Organic Peroxides – A very different
and less predictable class of
potentially explosive compounds.
O O

O O
H3C O H H O H

Perxyacetic Acid Peroxyformic Acid

O
O
O
O

O
Diethylperoxide
Dibenzoylperoxide
O
O H

n-octyldiperoxysuccinic acid O

H
Acetone Peroxide

• Formed from acid catalyzed reaction of acetone

with hydrogen peroxide.

• Formed as a mixture of dimer and trimer

structures.
H3C CH3
H3C CH3

O O
O O
O O

O O
CH3
H3C
O O
H3C CH3
H3C CH3

Dimer Trimer
Acetone Peroxide

• Extremely dangerous and unpredictable in

it’s detonation behavior.

• Has been used by terrorists.

- easily prepared from common chemicals
which are not regulated.
- not detected by bomb-sniffing dogs.