Unit IV Explosives Chemistry:

Introduction and assessment of explosives, Oxygen balance,

Explosive Power Index, Heat and Temperature of Explosion,
Pressure of explosion, Mechanism of Ignition and hot spot
formation.

Thermal decomposition, physical and chemical aspects of combustion,

Deflagration and Detonation,
Analysis of low and high explosives by different instrumental
techniques,
Quality control, Proficiency Testing, Interpretation and Significance of
Results.
Case studies

Chemical Warfare Agents: Classification, physical and biochemical

properties, toxic effects, detection by Biosensors and various
instrumental techniques
 What are essential features of Explosive
1.
 What are Explosives & Explosives chemicals
NM, DNT, TNT, TATB
NC, EGDN, NG, PETN

RDX, HMX

SA, LA,
AA
MF, SF

TATP,
HMTD
Napalm, Magnesium, White P etc.
Fission of Uranium
 Appendix
Short form used Name of the explosives
TATB Triamino trinitro benzene
TNT Trinitro toluene
NM Nitro methane
NC Nitro Cellulose
NG Nitro Glycerine
EGDN Ethylene glycol dinitrate
RDX Research and Dept. Explosive
HMX High Melting Explosives
PETN Penta erythritol tetranitrate
TATP Triacetonetriperoxide
HMTD Hexamethylenetriacetonediperoxide
MF Mercury Fulminate
SF Silver Fulminate
LA Lead azide
SA Silver azide
ANFO Ammonium nitrate fuel oil
 Classification of Explosivs
 On the basis of speed or VoD:
 Low explosives (less than the speed of sound, deflagration (1,300 ft/s)
 High explosives (Supersonic speed, deflagration (9,800–29,500 ft/s)
 On the basis of sensitivity and use of explosives:
 Primary high explosives (initiatory) More sensitive than
PETN
 Secondary high explosives, TNT and RDX
 Tertiary explosives, also called blasting agents
 On the basis of application of explosives:
 Military explosives
 Industrial explosives
 On the basis of chemical structure of explosives:
 Nitro compounds (C-NO2 group)
 Nitrate ester (C-O-NO2 group)
 Nitramines (C-N-NO group)
 AS S E S S M E N T O F E X P LO S I V E S
 With the advent of various modeling techniques, m u c h
information concerning any given explosive can be obtained by
theoretically calculating its properties.
 This information is valuable but indicative as calculations
predict performance, which an explosive may have under ideal
conditions.
 In practise, s uc h perfection is never achieved and it is a matter
of practical importance to assess their properties experimentally
under conditions more appropriate to their use.
 S u c h an assessment is usually made by a series of tests chosen
to determine the performance of explosives under various
conditions.
 While these tests are of considerable value, it must be
remembered that no laboratory test or series of tests can predict
precisely the performance of explosives which may be used for
widely varying purposes.
 The ultimate test for all explosives is their performance in the
field.
 The experimental assessment of the following properties, which
are considered to be of utmost importance from the point of view
of their application, are given in the follows
1) Compatibility and stability.
2) Sensitivity to heat, impact, friction, spark and shock.
3)Velocity of detonation.
4) Detonation pressure.
5) Explosive power or strength.
1. Strength Test :
This strength of the detonator is evaluated by Lead Plate Test and Sand Bomb Test.
These tests are indirect measure of the ability of detonators to initiate high
explosives. In Lead Plate Test, a square 3cm X 3cm lead plate is used.
The hole made in the lead plate by the detonator will determine the strength of
detonator.

In Sand Bomb test, a preselected sand is subjected to the firing of the detonator.
The amount of sand crushed in the firing will determine the strength of the detonator.
2. Series Firing :
This test is a measure of the firing ability of Electric Detonators, when connected in
series and
minimum firing current of 1.2 amperes DC is applied.
All Electric Detonators are subjected to this test.
3. Firing Impulse Test :
This test is related to the fuse head and is a measure of the energy required to setoff a
fusehead.
It is expressed in milliwatt seconds per ohm. Higher the impulse level the greater is
the insensitivity of the fusehead for firing currents and resisitant to leakage currents.
4. “No fire” current test :
This test is a measure of the ability of the detonators for not getting initiated when
the prescribed level of current is passed through if for a specified time.
It is a measure of safety against stray currents, which can initiate accidentally the
5. Under water pressure Test :
This test measures the ability of the detonators to get initiated even after exposure to water
pressure.
This will specify whether the detonators can be used in watery boreholes and or
for underwater blasting applications.

This test is done on all types of detonators.

6. Buxton Test :
This test measures the fitness of the detonator for use in gassy mines.
This test is carried out in special steel chambers in an atmosphere of 9% methane
–air
mixture.

This test applies to detonators required for use in underground gassy mines.
Instantaneous Copper Electric Detonators and Super coal delay detonators are subjected
to this test to evaluate their safety in gassy underground mines.

7. Continuity of Electrical Circuit of the detonators :

This test is being carried out to ensure the reliability of the fusehead. Eqach fusehead is
tested for its continuity before crimping, during crimping and after crimping to the detonator
shell.
This is a routine test done to ensure continuity of electrical circuit for large hook-up
of detonators.
 Oxygen Balance:
• The concentration of oxygen within an explosive or oxidizer is
represented by a term known as ‘ oxygen balance ’ (OB represented by
Ω
) which is an important parameter for identifying their potential as
an explosive or oxidizer.

• It is the propration of oxygen present with in structure of molecule of

the explosive.The oxygen balance indicates the amount of
molecularly bound oxygen that remains after complete
decomposition or, alternatively, the amount of oxygen that is missing
to ensure complete decomposition.

• Oxygen balance may be defined as the amount of oxygen remaining after

the oxidation of hydrogen, carbon and metals (like Mg, Al etc.) to
produce H2O, CO2 , MgO, Al2O3 etc.
• In other words, OB is an expression that is used to indicate the degree to
which an explosive can be oxidized
• It can be calculated and compared with the amount of oxygen
required for complete oxidation of the fuel elements (i.e. C and H)
• It may be negative, positive or zero oxygen balance.if the amount
of oxygen present in the explosive molecule is insufficient for
complete combustion then it results negative oxygen balance.
Exp: TNT, RDX, HMX etc

• if the amount of oxygen present in the explosive molecule is in

high propertion than required for complete combustion then it
results positive oxygen balance. Exp: NG & NH4NO3

• if the amount of oxygen present in the explosive molecule is just

sufficient for complete combustion then it results zero oxygen
balance. But Explosive are rarly perfactly balance.Exp: EGDN

• If oxygen balance is negative then there is not enough oxygen for

CO2 to be formed and CO will be liberated which is toxic.
• It doesnot provide information on the energy changes during
explosion.
The procedure for calculating oxygen balance in terms of 100 grams of the
explosive material is to determine the number of moles of oxygen that are excess or
deficient for 100 grams of the compound.

X = number of atoms of carbon,

Y = number of atoms of hydrogen,
Z = number of atoms of oxygen, and
M = number of atoms of metal (metallic oxide produced).

In the case of TNT (C6H2(NO2)3CH3),

Molecular weight = 227.1
X = 7 (number of carbon atoms)
Y = 5 (number of hydrogen atoms)
Z = 6 (number of oxygen atoms)

Therefore,

OB% = −73.97% for TNT

In the case of Ammonium Nitrate,
NH4NO3
Molecular weight = 80.043
X = 0 (number of carbon atoms)
Y = 4 (number of hydrogen
atoms) Z = 3 (number of oxygen
atoms) M = 0

Therefore,

OB% = +20
Oxygen balance and power
sensitivity, brisance, and strength are properties resulting from a complex
explosive chemical reaction, a simple relationship such as oxygen balance cannot
be depended upon to yield universally consistent results.

When using oxygen balance to predict properties of one explosive relative

to another, it is to be expected that one with an oxygen balance closer to zero will
be the more brisant, powerful, and sensitive; however, many exceptions to this
rule do exist.

One area in which oxygen balance can be applied is in the processing of

mixtures of
explosives.
The family of explosives called amatols are mixtures of ammonium nitrate
and TNT.

Ammonium nitrate has an oxygen balance of +20% and TNT has an

oxygen balance of −74%, so it would appear that the mixture yielding an oxygen
balance of zero would also result in the best explosive properties.
Explosive Power & Power
Index: power refers to the destructive energy released by an explosive
Explosive
material upon detonation.
It is typically measured by the amount of pressure, heat, and damage
generated by the explosion.

Explosive power is the ability to produce a maximum amount of force in a

very short period of time
Explosive Power or Strength
The power or strength of an explosive is a measure of its ability to do useful
work.

This is also termed the potential of an explosive and is the total quantity of
heat given off by an explosive at constant volume
The volume of gas (V) and heat of explosion (Q) can be calculated
independently

Explosive power is the product of volume of gas liberated

(V) and the heat of explosion (Q).
Mathematically,
• If the value of explosive power of explosive is compared with explosive
power
of standard explosive then it is called explosive Power Index.

• In order to calculate the power index of an explosive, its explosive power (as
calculated above), is compared with the explosive power of a standard
explosive (usually picric acid) that is

Explosive Power Index = QxV

(Q x V) piciric acid

• The Explosive Power Index of secondary high explosives

are much higher than those of primary high explosives
HEAT AND TEMPERATURE OF EXPLOSION
 What is Heat of Explosion:
• The heat liberated by the explosion will raise the temperature
of
the gases liberated, which in turn cause them to expand (as
properational to Temperature).

• When an explosive is initiated either to burning or detonation,

its energy is released in the form of heat.

• The liberation of heat under adiabatic conditions is called the

‘heat of explosion,’ denoted by the letter Q.
• The heat of explosion provides information about the work
capacity of the explosive, where the effective propellants and
secondary explosives generally have high values of Q.
• For propellants burning in the chamber of a gun, and secondary
explosives in detonating devices, the heat of explosion is
conventionally expressed in terms of constant volume conditions
Q,.
• For rocket propellants burning in the combustion chamber of a
rocket motor under conditions of free expansion to the
atmosphere, it is conventional to employ constant pressure
conditions.

• In this case, the heat of explosion is expressed as Qp,.

 TEMPERATURE O F C H E M I C A L EXPLOSION:

 What is Temperature of Explosion:

The temperature of explosion is the maximum temperature
that the explosion products can attain under adiabatic
conditions. fast and,
 initially,
When the an gases do notdetonates
explosive have time to
theexpand to any
reaction is great extent.
extremely
 The heat liberated by the explosion will raise the temperature of the
gases, which will in turn cause them to expand and work on the
surroundings to give a 'lift and heave effect’.
 The effect of this heat energy on the gas can be used to calculate the
temperature of explosion.
Pressure of Explosion
• It is the maximum static pressure achieved
when a given mass of explosive is burnt in a close vessel of fixed
volume.
• The pressure attained is so high that the ideal gas laws are not sufficiently
accurate and thus it can be expressed as,
Pe(Vi-a)=nRTe
 M EC H A N IS M O F IGNITION AND HOT SPOT FORMATION

 Ignition occurs when part of a combustible material s u ch as an explosive

is heated to or above its ignition temperature.
 The ignition temperature is the minimum temperature required for the
process of initiation to be self-sustaining.
 Explosive materials are ignited by the action of an external stimulus
which effectively inputs energy into the explosive and raises its
temperature.
 The external stimulus can be friction, percussion, electrical impulse,
heat, etc. Once stimulated the rise in temperature of the explosive
causes a sequence of pre-ignition reactions to commence.
 These involve transitions in the crystalline structure, liquid phases
changing into gaseous phases, and thermal decomposition of one or
more of the ingredients.
 These reactions then lead to a self-sustaining combustion of
the
material, i.e. ignition.
 As the temperature rises, the rate of the heat produced increases
exponentially whereas the rate of heat lost is linear.
 Ignition occurs at the temperature where the rate of heat generated is
greater than the rate of heat lost.
 The above figure presents a simple model in defining the ignition temperature of
an explosive material Tign.

 Tign is the temperature at which the heat generated in the composition is greater
than the heat lost to the surroundings, or more accurately, Tign should equal
'ignition temperature - initial temperature’.

 As discussed above, ignition generally results in deflagration of the explosive

material, but if the material is confined or is in large quantities deflagration
can develop into detonation.
 It is generally accepted that the initiation of explosives is a thermal process.
 Mechanical or electrical energy from the stimulus is converted into heat by a
variety of mechanisms.
 The heat is concentrated in small regions forming hotspots.
 Hotspots The formation of hotspots depends upon the energy input and the
physical properties of the explosive composition.
 The diameter of the hotspots is in the region of 0.1-10 um and their duration
is about 10-5-10-3 s with temperatures greater than 900 0C.
 Ignition and its Mechanism :
• When a combustible material is heated above its ignition temp. the
material undergoes self sustaining comustion reaction. This
process is called ignition.
• Explosive material are Ignited by the action of external stimulus
(heat, friction, percusion, electrical etc.) rises the temp. of the
material, which causes a sequence of pre-ignition reactions.
These reactions then lead to a self sustaining combustion of the
material called ignition.
• As the temp. rises the rate of the heat produced increases
exponentially and the rate of heat lost is linear.
• Ignition occurs at that temp. where the rate of the heat
produced
is greater than that of heat lost.
• Ignition results in deflagaration of the explosive material but if the
material is confined or is in large quantity deflagaration
can develop into detonation.
 Hotspots : In general the initiation of explosive is a thermal process.
The mechanical or electrical energy from the stimulus is conveted
into heat.
 The heat is concentrated in small regions called hotspots.
• The formation of hotspots depends upon the energy input and the
physical properties of the explosive material.
• The dia of of the hotspots is in the region 0.1-10 micrometer and their
duration is about 10-5 to 10-3 sec with temp. more than 900 0C.
 THERMAL DECOMPOSITION
 Thermal decomposition, or th ermolysis, a chemical
is decomposition caused by heat.
 The decomposition temperature of a substance is the temperature at
which the substance chemically decomposes. Examples:
 The reaction is usually endothermic as heat is required to
break chemical bonds in the compound undergoing decomposition.
 If decomposition is sufficiently exothermic a positive feedback loop is
created producing thermal runaway and possibly an explosion or other
chemical reaction.
Examples:
 Calcium carbonate (limestone or chalk) decomposes into calcium
oxide and carbon dioxide when heated.
The chemical reaction is as follows:
CaCO3 → CaO + CO2
 The reaction is used to make quick lime, which is an industrially
important product.

 Another example of thermal decomposition is

2Pb(NO 3 ) 2 → 2PbO + O 2 + 4NO 2 .
All explosive material undergo thermal decomposition at a temperature far
below the temperature at which they explode.
During thermal decomposition, strong exothermic reaction takes place
which generate a lot of heat.
Some of this is lost to the surroundings and the remaining will be used to
raise the
temperature of explosive even further.
When the rate of heat generated is more than that of heat lost, a
spontaneous decomposition will occur.
The rate of decomposition with rise in temperature follows a curve path as
shown in
figure
 From this figure it is found that, the
rate of decomposition rises very
slowly at temperature below 100 0C
and then it steepens as the temp.
approaches the ignition temp. of
explosive.

The effect of temperature on the rate

of decomposition of explosive
In thermal decomposition, the
chemical energy generated by the
decomposition of
explosive will give information on
 PHYSICAL AND CHEMICAL ASPECTS OF COMBUSTION,
Deflagration Detonation
 The main energetic reactions to consider for explosives are:
• Combustion
• Deflagration
• Detonation
 Combustion:
• Combustion is a chemical reaction which takes place between a
sustance (combustibl) and oxygen.
• It is very fast and highly exothermic and is usually accompanied
by a flame.
• Combustion is a complex process involving
many steps depending on the properties of combustible
substance.

• At low temp. oxidation of combustible substance takes place

without any flame
but when temp. is raised the rate of oxidation is increased.

• If the temperature of reactants is raised above the ignition temp, the heat
generated is more than the heat lost to surroundings and thus flame will be
  The physical and chemical aspects of combustion are the reactants, products,
and the change in enthalpy during the combustion reaction.
 The reactants are the fuel and the oxidizer.
 The products are water vapor, carbon dioxide, and heat.
 The change in enthalpy is the energy released during the combustion reaction.
 The flame is the visible part of the combustion reaction.
Complete Combustion
 In complete combustion, the reactant burns in oxygen and produces a limited number of
products. When a hydrocarbon burns in oxygen, the reaction will primarily yield carbon
dioxide and water.
 When elements are burned, the products are primarily the most common oxides. Carbon
will yield carbon dioxide, sulfur will yield sulfur dioxide, and iron will yield iron(III)
oxide.
 Nitrogen is not considered to be a combustible substance when oxygen is the oxidant.
Still, small amounts of various nitrogen oxides (commonly designated NOx species) form
when the air is the oxidative.
 Combustion is not necessarily favorable to the maximum degree of oxidation, and it can
be temperature-dependent.
 For example, sulfur trioxide is not produced quantitatively by the combustion of sulfur.
NOx species appear in significant amounts above about 2,800 °F (1,540 °C), and more is
produced at higher temperatures.
The amount of NOx is also a function of oxygen excess.
InComplete Combustion
 Incomplete combustion is the incomplete burning of a
 This
fuel. produces a range of pollutants, including carbon
hydrocarbons,
monoxide, and nitrogen oxides.
 Incomplete combustion can be caused by a lack of oxygen, by the fuel
not
being distributed evenly, or by the fuel not being hot enough.
 Incomplete combustion can produce a range of pollutants, including:
1. Carbon monoxide – a poisonous gas that can cause headaches, dizziness,
and nausea
2. Hydrocarbons – a group of pollutants that includes methane, benzene,
and
toluene
3. Nitrogen oxides – a group of pollutants that includes nitrogen dioxide
and nitric oxide
Incomplete Combustion
 Incomplete combustion is a type of combustion in which not all of the fuel is burned.
 This can result from a lack of oxygen, a problem with the fuel itself, or a problem with
the combustion process.
 Incomplete combustion can produce harmful emissions, including carbon monoxide, which
can be dangerous to breathe.

In the Combustion Process, the Flames Can be Classified as:

 There are three types of flames: premixed, diffusion, and vortex.

 Premixed flames occur when the fuel and oxidizer are mixed in the correct
ratio before ignition.
 This type of flame is very stable and produces little soot.
 Diffusion flames occur when the fuel and oxidizer are mixed after ignition.
 This type of flame is less stable and produces more soot than premixed flames.

 Vortex flames occur when the fuel and oxidizer are mixed in a swirling motion.
 This type of flame is the most unstable and produces the most soot.
 Physical Aspects of Combustion
 The physical aspects of combustion are the changes in state that
occur when a fuel is burned. The three most common phases are
solid, liquid, and gas.
Solid
 When a fuel is in its solid phase, the atoms are all close together
and the molecules are held together by chemical bonds.
 When heat is applied, the atoms and m olecules vibrate
faster
and the bonds break. This causes the solid to change into a liquid.

Liquid
 In the liquid phase, the atom s and m olecules are still
close together, but they are not held together by chemical bonds.
 When heat is applied, the atoms and molecules move faster and
the liquid expands.
Gas
 In the gas phase, the atoms and molecu les are spread out
and there are no chemical bonds holding them together.
 When heat is applied, the atoms and molecules move faster and
Chemical Aspects of Combustion
 The chemical aspects of com bu stion involve the release
of
energy from the chemical reaction of a fuel with oxygen.
 The combustion process can be divided into three stages:

 The ignition stage, in which the fuel and oxygen

molecules collide and start the reaction.
 The propagation stage, in which the reaction spreads through
the fuel mixture.
 The termination stage, in which the reaction ends and
the
products are released
 The overall process of combustion is exothermic, meaning that
it releases energy in the form of heat.
 The heat produced by combu stion can be used to
 Deflagaration:
• When a small amount of substance (deflagarating explosive) in an
unconfined codition suddenly ignites by flame, spark, friction or heat
then it burns violently than ordianary combustion.
This is called deflagaration.
• It accompanies with a flame or spark or a hissing or cracking
noise.
• Mechanism: On initiation of deflagarating explosive, local and
finite hotspots are developed in three ways:
i) Either through friction between the solid particulates
ii) By compression of voids or bubble in the liquid
 By plastic flow of material
This in turn produces heat and volatile
intermediates which then undergo highly exothermic reactions
in the gaseous phase and hence produces enough
energy and heat to initiate decomposition.
The rate of deflagaration increases with increasing degree of
confinement
Deflagrations are thermal processes that proceed radially outward in all
directions through the available fuel away from the ignition source.
As the volume of the reaction zone expands with every passing moment, the
larger surface area contacts more fuel, like the surface of an inflating balloon.
The reaction starts small and gathers energy with time.
This process occurs at speeds depending largely on the chemistry of the fuel
--from 1 to 10 meters per second in gasoline vapors mixed with air to

hundreds of meters per second in black powder or nitrocellulose propellants.

These speeds are less than the speed of sound in the fuel

Deflagrations, then, are thermally initiated reactions propagating at subsonic

speeds through materials like:
mixtures of natural gas and air,
LP gases and air, or gasoline vapors and
air; black powder or nitrocellulose (single-base) propellants
or rocket fuels.
The pressures developed by deflagrating explosions are dependent on the fuels
involved,
their geometry, and the strength (failure pressure) of a confining vessel or
structure (if any).

Pressures can range from 0.1psi to approximately 100psi for gasoline:air

mixtures
to several thousand psi for propellants.
Times of development are on the order of thousandths of a second to a half-
second or more.
Maximum temperatures are on the order of 1000-2000 degrees Celsius (2000-
4000 degrees Fahrenheit).
 Detonation:
• The process in which explosive substances on initiation can
undergo decomposition via. the passage of shockwave rather
than thermal mechanism is called detonation.
• The speed at which the shock wave propagate through
the
material of explosive is called velocity of detonation (VOD)
• The velocity of shock wave in solid or liquid explosives
ranges between 1500 and 9000 m/sec.
• The detonation can be achieved either by burning to
detonation or by initial shock.
• Burning to detonation can takes place when explosive
substance is confined in a container and ignited from one
end.
• Explosives can also be detonated when they are subjected to
a high velocity shock wave.
Detonation is chemically an oxidation reaction; it does not involve a combination
with oxygen.
It involves only special chemically unstable molecules that, when energized,
instatneously splits into many small pieces that then recombine into
different chemical products releasing very large amounts of heat as they do
so.
High explosives are defined as materials intended to function by detonantion, such
as TNT, nitroglycerine, C4, picric acid, and dynamite.
The reaction speeds are higher than the speed of sound in the material (i.e.,
supersonic).
Since most explosives are roughly the same density, a reaction speed of 1000
m/s (3100 feet per second) is set as the minimum speed that distinguishes
detonations from deflagrations.
Due to the supersonic reaction speed, a shock wave develops in the explosive
(like the sonic boom from supersonic aircraft) that triggers the propagating
reaction.
Detonation speeds are on the order of 1000-10000 m/s so times of development
are on the order of millionths of a second.
Temperatures produced can be 3000-5000 degrees Celsius and pressures can be
from
It should be noted that a few materials can transition from deflagration to
detonation depending on their geometry (long, straight galleries or pipes), starting
temperature, and manner of initiation.
Double-base smokeless powders (containing nitroglycerine), perchlorate-based
flashpowders, hydrogen/air mixtures and acetylene (pure or with air) can
detonate under some conditions.
The effects of detonations are very different from those of deflagrations.
Deflagrations tend to push, shove, and heave, often with very limited shattering
and little production of secondary missiles (fragmentation).
Building components may have time to move in response to the pressure as
it builds up and vent it.
The maximum pressures developed by deflagrations are often limited by the
failure pressure of the surrounding structure.
Detonations, on the other hand, tend to shatter, pulverize and splinter
nearby materials with fragments propelled away at a very high speeds.
There is no time to move and relieve pressure so damage tends to be much
more localized (seated) in the vicinity of the explosive charge (and its initiator)
than a deflagration whose damage is more generalized.
Damage from a deflagration tends to be more severe away from the ignition
point,
as the reaction energy grows with the expanding reaction (flame) front.

It is for this reason that identification of an ignition source and mechanism for
a deflagration may be more difficult than for a detonation.
Deflagaration to Detonation of
explosives
 Kinetics of explosive reaction:
• Kinetics is the study of rate of change of chemical reaction.
• Explosive reactions are instantaneous and the rate of reaction depend
on the temperature, pressure and concentration of the reactants.
• In explosive reaction, the energy is first supplied from the initiator to
raise the temp. of explosive for ignition with the formation of hotspot.
If the enegy generated by the hot spots is greater than the activtion
energy, the reaction will proceed with formation of products and relese
energy.
• Thus activation energy represents
an amount of energy required by
the starting material and conver it
to a reactive with higher excited
state.
• Activation energy
measures the ease with which
an explosive material will
initiate. Larger the activation
energy more difficult it will be to
initiate the explosive material.
• The rate of reaction is determined by the magnitude of activation
energy and the temp. at which the reaction takes place. When temp.
of the sytem is increased an exponentially greater no. of molecules
will possess the necessary activation energy and the rate of
reaction also incraeses exponentially as given in fig.
• The rate of reaction can be described by using rate-temp.
relationship i.e by Arrehinius equation,
k = A e -E/RT
• Primary explosives have low values for the activation energy so it
takes less energy to initiate the same and thus they are more
sensitive to external stimulus i.e. impact, friction etc. where as
secondary explosives have high values of activation energy and
colission factor, therefore more difficult to initiate and less
sensitive to external stimulus.
• The common methods of investigating kinetics of explosive
reactions are Differemntial thermal analysis, Thermogravimetric
analysis and differential scanning calorimetry.
 KIN E T ICS O F E X P LO S I V E REAC T ION S
 Kinetics is the study of the rate of change of chemical reactions.
 These reactions can be very fast, i.e. instantaneous reactions
s u c h as detonation, those requiring a few minutes, i.e. dissolving
sugar in water, and those requiring several weeks, i.e. the rusting
of iron.
 In explosive reactions the rate is very fast and is dependent on
the temperature and pressure of the reaction, and on the
concentration of the reactants.
 When an exothermic reaction occurs, the free energy of the
reactants is higher than the free energy of the products.
However, energy is often needed to start the reaction.
 This supply of energy is known as the Activation Energy (E a ). It is
the energy needed to break bonds in the reactants and to allow
the less stable intermediates, or transition state, of the reaction
to form. Only when this barrier has been breached, can the
reaction proceed via the downhill pathway, which can be seen on
the diagram below.
 In an explosive reaction, ignition involves giving the explosive material the
activation energy to start deflagration.
 Energy can be given in various forms depending on which type of stimulus is used.
 Friction, impact and heat initiation may provide thermal, potential or kinetic energy
to
the system while electrical impulses would supply electrical energy.
 Once the reaction has started, deflagration can then provide heat energy to the system
to allow the rest of the explosive to react.
ANALYSIS OF LOW AND HIGH
EXPLOSIVES BY DIFFERENT
INSTRUMENTAL
TECHNIQUES
Explosive Residue
Analysis
 Extraction & Identification of Explosives

Extract/Extraction Solvent (s) Purpose/ Techniques/Instruments

of blast residues used Detection used
of
explosives
analyte
Thin Layer Chromatography
• Petroleum Ether: Ethyl Acetate
[50:50]
• Cyclohexane: Acetone [60:40]
• Trichloroethylene: Acetone [4:1]
• Silica Gel G (Stationary phase)
•Visualizers :
Ethylene diamine &
UV light

• RDX Rf value -
52
& 57 respectively
Gas Chromatography
Supercritical Fluid Chromatography
Quantitative method for the analysis of RDX, TNT and PETN
Method selection and optimisation With the combination of the high resolution of a
capillary column and the high sensitivity of a mass spectrometer, gas
chromatography- mass spectrometry (GC-MS) has become a common instrumental
technique for the identification of explosives in most forensic laboratories
worldwide. Therefore, GC- MS was chosen as the first technique to be evaluated.
A set of solutions of RDX, TNT and PETN were prepared by dilution of the
certified explosive standards in ethyl acetate, covering the range 2 – 15 ppm.
The analytical parameters of the Perkin Elmer Autosystem XL gas chromatograph
and TurboMass Upgrade mass spectrometer were optimised and the established
quantitative method applied in both full-scan and selected ion monitoring (SIM)
modes using musk tibertine as an internal standard. It was found that the relationship
between the instrumental response and the concentration of each target compound
was non-linear. This resulted from the considerable difference in the mass between
the chosen target ion from explosive compounds and the ion from the internal
standard. Also, there were no other suitable ions to be chosen as a target ion for
quantitative analysis. In addition, and more importantly, a high variation was
observed in the signal for the same set of calibration solutions analysed at the
beginning and at the end of the same sequence (especially in the case of PETN
at low concentrations). This was possibly due to the configuration of the instrument
in that a sample can experience high temperatures in the sample carousel while
waiting for analysis (as the carousel on this instrument is located directly on top of
the oven). As a consequence of these observations, GC-MS was determined to be
unsuitable as a quantitative method for this study.
High performance liquid chromatography (HPLC) was the next technique considered. There
are no high temperature compartments, such as the injection port in a GC-MS, and no
requirement of high temperature for the separation, which makes the technique more
compatible given the inherent thermal instability of explosives. Initially, there was an attempt
to develop a method that was able to analyse RDX, TNT and PETN using the same
chromatographic conditions by optimising the composition of the mobile phase and the
column temperature; however, it was difficult to obtain a good separation of all three
explosives while ensuring that the analysis time was not too long. A gradient elution was not
an option as it would generate a higher background in the analysis of PETN, which required
low-wavelength detection. Consequently, a separate method for each explosive was developed
and the analyses were carried out under different chromatographic conditions. The criteria for
development of the final method for each explosive included the sensitivity of detection for
each target compounds, the analysis time, and the possibility of applying the same internal
standard. The full details of the final chromatographic conditions for each organic explosive
are provided in Table 2.1.
Instrumentation The analyses were performed on an Agilent 1120 high performance
liquid chromatography system comprising a quaternary pump, vacuum degasser, standard
autosampler, thermostatted column compartment and a diode array detector. Instrumental
control, data acquisition and analysis were accomplished using EZChrom Elite
Chromatography Data System software version 3.3.2
Methanol/water was chosen as the mobile phase for chromatographic analysis due to a
worldwide shortage of acetonitrile at the time of performing this research. An isocratic run at
a flow rate of 1 mL/min on a 4.6 × 150 mm Zorbax Eclipse XDB-C18 analytical column
with particle size of 5 μm was applied for each separation of all three high explosives. The
full conditions for the analysis of each explosive are provided in Table 2.1.
Results
Examples of chromatograms obtained utilising the procedure outlined are shown in Figures 2-1
to 2-3.
 QUALITY CON T ROL
 It is defined as the operational technique and activities that are used
to fulfill the requirements of the quality. It is the process of detecting
the errors.
 Quality control is used to verify that deliverables are of acceptable
quality and that they are complete and correct. Examples of quality
control activities include inspection, deliverable peer reviews and the
testing process.
 Quality control is about adherence to requirements.

 Quality assurance activities are determined before production work

begins and these activities are performed while the product is being
developed.
 In contrast, Quality control activities are performed after the product
is developed.
 PROF I C I E N C Y TESTING

PROFICIENCY TESTING
 Proficiency testing determines the performance of individual laboratories for specific
tests or measurements and is used to monitor laboratories’ continuing performance.
 Proficiency testing is also called interlaboratory comparison. As this term implies,
proficiency testing compares the measuring results obtained by different laboratories.
 In a proficiency test one or more artifacts are sent around between a number of
participating laboratories. Each laboratory measures the artifacts (e.g. a ring gage or a
set of gage blocks) according to a given set of instructions and reports its results to the
administrator.
 NABL provide accreditation to Proficiency Testing Provider as per ISO/IEC
17043:2010 “Conformity assessment- General requirements for Proficiency testing”
and NABL is signatory to APAC MRA for this program.
 This International Standard specifies general requirements for the competence of
providers of proficiency testing schemes and for the development and operation of
proficiency testing schemes.
 International standard ISO/IEC 13528:2015 is complementary to ISO/IEC 17043
providing detailed guidance on the use of statistical methods in proficiency testing.
Case Study
INTRODUCTION TO C H E M I C A L WARFARE AGE NTS
 INTRODUCTION TO C H E M I C A L WARFARE AGE NTS
 It is imperative for the modern soldier to be able to understand
the hazard of chemical weapons and the protective measures
required to be able to survive in s u c h an environment to be able
to continue fighting effectively.
 The capability to wage chemical warfare is well within the means
of several nations that cannot afford a nuclear armory and this
poses a serious threat.
CLASSIFICATION O F C H E M I C A L WARFARE AGE NTS
 Types of C h emical Agents C h emical agents are
classified according to the following criteria: -
(a) Military use and Effects on the body
(b) Duration of effectiveness.
Duration of Effectiveness:
 The duration of effectiveness, that is the time for which the effects lasts,
depends on many factors s u c h as:
(a) The physical characteristics of the agent.
(b) The amount of agent delivered and its physical state.
(c) The weapon system used.
(d) The weather in the target area at the time of the attack
and afterwards.
 Types of Chemical Agents Based on Effectiveness Have you seen dew
on grass or leaves in the morning?
 The dew is water droplet, which forms on leaves due to condensation
in the atmosphere.
 Consider the dew drops as chemical agents. Then some
chemicals
disappear quickly like the dewdrop.
 These agents are called non-persistent agents. Other chemical
agents remain in the atmosphere and on the objects where it was
sprayed.
 These agents are called persistent agents.
 From the point of view of duration of effect the agents m ay
be
classified as follows: -
(a) Non-Persistent Agents: These agents disperse rapidly after
release and present an immediate short duration hazard e.g. G
agents (Nerve Agent), Hydrogen Cyanide (Blood Agent) etc.
(b) Persistent Agent: These agents continue to present a hazard for
a considerable period after delivery by remaining a liquid
contact hazard and by continuing to produce vapour by the
evaporation of the liquid e.g. V agents (Nerve Agents), Sulphur
Mustard (Blister Agent).
Effects on the Body
 The third method of classification is to group agents by their
action and effect on the body. S u c h groups are as follows:
(a)Killer Agents: These agents are used to kill h u m an s and are
deadly/ fatal. These are further classified as:-
(i)Nerve Agent: These interfere with the nervous system and
thus disrupt essential body functions like breathing, muscular
control and vision. E . g . , TABUN (GA), SARIN (GB), S O M A N (GD) and
V agents.
(ii)Blister Agents: These agents cause inflammation,
blistering of the skin and superficial destruction of contaminated
internal tissue, e.g., the lining of the breathing passage. Although
classified as killers, blister agents do not cause death except in
extreme cases. Examples are Mustard G a s (HD), Nitrogen, Mustard
(HN 1 to HN 3) and Lewisite (L).
(iii)Blood Agents: These prevent body tissue from using the
oxygen in the blood. E . g . , Hydrogen Cyanide (AC), Cyanogen
Chloride (CK) and Arsine (SA).
(iv)Choking Agents: These attack the breathing passage and
lungs. E . g . , Phosgene(CG), Di-phosgene (DP) and Chloropicrin (PS).
(b) Incapacitating Agents: These agents cause temporary
incapacitation of individuals. They affect the normal h u m a n body
functioning for a short duration.
They are further classified as:-

(i) Nose (Vomiting) Agents: These cause irritation in the nose and
throat, which can lead to vomiting.
(ii) Mental Incapacitates: These cau se temporary m ental
disturbances, usually preceded or accom panied by
physical effects.
(iii) Physical Incapacitates: These cause temporary effects s uc h as
fainting or paralysis, unaccompanied by mental effects.

(c) Riot Control Agents: Agents selected and approved for use
when giving aid to the civil power and in similar operations. These
are mostly the incapacitating agents s u c h as C S . These are also
referred to as 'tear' agents. These cause irritation of the eyes, flow
of tears and a stinging sensation.
PHYSICAL AND BIOCH E MICA L P ROP E RT IE S O F
C H E M I C A L WARFARE AG E NTS
TOX I C E F F E C T S DETECTION BY B I O S E N S O R S AND VARIOUS
INSTRUMENTAL T EC H NIQ U E S