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ROLE OF CHEMISTRY IN FORENSIC

SCIENCE Seminar
Chem. 591

Presented by:
Charu Maini
L-2013-BS-43-IM
1
CONTENTS
Forensic science – An Introduction

Role of chemistry

Mixtures

Date rape drugs as homogeneous mixtures

Cocaine as heterogeneous mixture

Fingerprint development

Gunshot residue analysis

Chemical reactions in forensic science

Death investigation
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Forensic science – An Introduction
• The word forensic comes from the Latin word forensis
meaning “of the forum”
• Today forensic science deals with the application of
science to legal matters and, in particular, to crime solving.

3
An interdisciplinary field

BIOLOGY GEOLOGY

FORENIC
SCIENCE

PSYCOLOG PHYSICS
Y

CHEMISTRY
4
Role of chemistry
Applying the principles and laws that are taught in
traditional chemistry to find the chemistry of
evidence

5
Mixtures
A mixture is two or more pure substances that are
physically confined but not chemically bonded together

Two subclasses:
• Homogenous
mixture
• Heterogeneous
mixture
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Homogenous Heterogeneous
mixture mixture
One in which substances One in which
that compose it are so composition varies
evenly distributed that a from one region of a
sample from any one part sample to another. e.g.
of the mixture will be sand and water
chemically identical to a
sample from any other
part. e.g. Sugar in water

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But why talking about mixtures in forensic
chemistry

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Mixtures in drug assisted crimes

DATE
RAPE
DRUGS
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Date rape drugs
Date rape drug refers to any drug that can be used
to assist in the commission of a sexual assault
and can be dissolved in a person’s drink to form a
homogeneous solution.
Drugs may be added to a food or drink without the
victim’s knowledge and may have:
• Sedative
• Hypnotic
• Dissociative and/or
• Amnesiac effects
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Rohypnol (The forget pill) - A dangerous date rape
drug

• Rohypnol’s effects vary depending on the dosage, but


they range from sedation to stage-4 coma.
• It takes 20-30 minutes before its sedative effects
begin, and the effects can last from 8-24 hours.
• As well as being a strong sedative, it also causes
short-term memory loss.

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Other known date rape drugs
• GHB, also known as
gamma-hydroxybutyric
acid
• Benzodiazepines (such
as flunitrazepam, also
known as Rohypnol or
“roofies”)
• A vetenarian anaesthesia
like ketamine
• An American 1997 study
showed that alcohol is
also considered here. 12
Forensic Analysis of Date Rape Drugs

Detected through a urine sample test, but rohypnol can also be


detected through a blood test.

GHB, Ketamine and Benzodiazepines like flunitrazepam can be


analyzed by UV spectrometry at 314 nm.

Testing kits that detect Date rape drugs are commercially


available under the name of “the drink detective”.

In toxicology, routine test are performed on drug of forensic


interest such as spot tests, IR, NMR, Thin layer
Chromatography, Immunoassay, GC-MS, LC-MS, HPLC, etc.
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An innovative approach
Four chemistry students
from North Carolina
University, all
undergraduates, Ankesh
Madan, Stephen Gray,
Tasso Von Windheim, and
Tyler Confrey-Maloney
have been successful in
introducing a nail varnish,
that indicates the presence of
date rape drugs, by changing
color after being dipped in
the drink.
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An interesting fact
Vitreous
humor
• Vitreous humor is
sampled
postmortem to
determine whether
alcohol is present !!

15
Denatured alcohol
The U.S. government places high taxes on ethanol for
human consumption, but for industrial purposes or
for scientific research it is exempted from this tax.

To make sure that the ethanol being sold for the


latter purposes, the suppliers mix a small amount of
methanol into the ethanol.

Methanol can make a person desperately


sick, can cause permanent blindness, and is
potentially lethal.
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Cocaine
Cocaine is a naturally occurring
alkaloid and powerful nervous system
stimulant derived from the coca plant
(Erythroxylum coca)

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Chemical forms of cocaine

Powder Crack Cocaine


Cocaine
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Cocaine and the impurities
• Cocaine sold on the illegal drug market are usually
heterogeneous mixtures.
• Drug dealers boost their profits by mixing cocaine with
fillers to increase the sample size.

• Forensic drug chemists have


found some fillers –
including sugar, baking soda,
talcum powder and even tang
breakfast drink powder!
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Analysis of cocaine
For cocaine containing exhibits,
combinations of testing methods such as:
• Scott’s color test
• TLC
• FTIR
• Ultraviolet Spectrophotometry
• GC coupled with FID and/or MS and
• HPLC
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An interesting case
Police officers were once chasing a crack dealer when the
suspect entered a fast–food restaurant. The drug dealer
threw his entire inventory of drugs into the deep fryer. The
crack cocaine was not recovered by the police at that time.
But after sometime, forensic
chemists were successful in
recovering the crack cocaine from
oil by exploiting the concept of
solubility and the acid-base
properties of organic compounds
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Solving the problem..
Knowledge of the
principles of
chemistry allows a
forensic scientist to
use the pH of a
solvent like a
switch.

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Extraction of acidic and basic organic compounds

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Marijuana
Marijuana is a mind-alerting drug, produced by the
Cannabis sativa plant. THC (Tetrahydrocannabinol)
is the main chemical ingredient in it.

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Fingerprint development
There are three types of fingerprints:
latent, plastic, and negative.
Latent fingerprints are produced by
touching a surface and leaving behind
fingerprint residue in the pattern of the
ridges.
Fingerprints typically not requiring
development include plastic
fingerprints made into soft surfaces.
Negative fingerprints are created as
the skin ridges of a finger remove
transferable material from a surface
leaving behind a pattern of the ridges.

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Fingerprint development techniques
1. Ninhydrin Reaction

Ninhydrin reacts with α-


amino acids and produce
a purple-colored product
called, Rhuemann’s
purple

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2. Silver Nitrate Reaction
When silver nitrate reacts with
any soluble chloride salt, the
insoluble silver chloride is
produced.

The silver chloride produced is a


white solid that does not offer
much contrast for fingerprint
development.

However, as the silver chloride remains


exposed to ultraviolet light, it
decomposes producing silver and
chlorine gas which produces a purple-
black product.

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3. Superglue Fuming

Superglue fumes, compose of


cyanoacrylate monomers, selectively
polymerize on fingerprint residue.

The polymerization process is


typically initiated by negatively
charged water-soluble species,
which are found in fingerprint
residue.

This allows for the


white–gray polymer.
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Gunshot Residue analysis

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Gunshot residue tests
The tests for the gunshots residue
includes:
• Paraffin Test
• Harrison-Gilroy Test
• Atomic absorption spectroscopy
(AAS)
• Scanning Electron Microscopy
(SEM)
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Limitations
The residues can be removed by
washing the hands.

It can associate an individual with a


firearm but not successful in identifying
that person as the shooter.
It is also possible, but very unlikely,
that residue would be deposited on
hands by other means. 31
Paraffin Test
• This test is used to detect the presence of nitrate residues.
• These substances are residues from smokeless powder, the
propellant used in modern cartridges.
• Paraffin test starts with removing the residues from the hands.
After removal, the cast is tested with a reagent (diphenylamine).
Dark blue spots indicates the presence of nitrate residues.

Principal problem :
• Nonspecificity - the
test detects nitrate
residues, but the
source of residues
cannot be
determined.

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Scanning Electron Microscopy
• SEM uses a high-energy electron beam to produce magnification significantly
greater than an optical microscope.
• This increased magnification permits the identification of gunshot particles by
their characteristic morphology.
• In addition, scanning with an electron beam causes the emission of X rays.
Since each element produces characteristic X rays, an elemental analysis of
the substances is also possible. Barium, antimony, and lead are the elements
that are indicative of a firearm discharge.

• Cigarette lighter flint


mimic GSR in
morphology
• Cost of the instruments
Disadvantages:• Time-consuming nature
• Variation between
laboratories in
determining the number
of particles.
33
Chemical reactions in forensic science
Combination
reaction

Combustion Decomposition
reaction reaction

Simple
Precipitation
displacement
reaction
reaction
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Synthesis reaction or combination reaction

Synthesis reaction occurs when two compounds react together to form a single
product.

A+B C

For example, calcium oxide was often used in graves, as it would help reduce the
odors, and it reacts with water to form calcium hydroxide. This helps speed up the
breakdown of tissue.

35
Decomposition reaction
Decomposition reaction consists of a single reactant compound that breaks
down to form smaller compounds.

C A+B

For example, the explosive decomposition of TNT (Trinitrotoluene)

36
Single displacement reaction
Single displacement reaction is a class of redox reactions involving the
replacement of part of a compound with a more active metal element.

A + BC AB + C

For example, reaction of a metal with an acid

Acid + metal salt + hydrogen gas

37
Serial number restoration

This particular type The hydrogen bubbles


of redox reaction is tend to form faster on
The acid reacts with
used to restore the steel that was
iron in the steel to
serial numbers that compressed beneath
produce Fe2+ ions the serial numbers as
have been altered
and hydrogen gas. compared with the
on guns or vehicle
parts. rest of the surface.

38
Combustion reaction
• The combustion reactions are distinguished by the presence of oxygen gas reacting
with an organic compound to produce carbon dioxide and water.
• Arsonists use the combustion of flammable organic compounds such as kerosene,
gasoline, or lighter fluid to fuel the fires they set.
• One of the components of gasoline is octane, which reacts with oxygen gas in
combustion reaction.

39
Backdraft or smoke explosion
• A hidden danger lurks in the fire triangle!!
• When fire heats a poorly ventilated room, the air
in the room can fill with flammable compounds
created from the incomplete combustion of fuels.
• Only two of three ingredients for fire are present.
• Once the oxygen gas rushes in, such an excess of
heated fuel ready to react causes an explosion
known as backdraft. 40
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Precipitation reaction
Precipitation reactions can be distinguished by the formation of a solid
compound from two aqueous reactants.

AB + CD AD + CB

For example, Formation of AgCl to develop fingerprints located on rough


surfaces.

42
Saponification reaction
Saponification is a process by which triglycerides are
reacted with sodium or potassium hydroxide to produce
glycerol and a fatty acid salt, called 'soap'.

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Adipocere or grave wax

When a human body, which in the


average person contains 10 to 30%
body fat, is disposed off in alkaline
soil, the normal decomposition
process does not occur.
• Instead, the saponification reaction
occurs and the body is converted
into a waxy, soaplike substance
called adipocere or grave wax.

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Death investigations

Use of soil samples

Use of insects

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Soil evidence
The density of a substance is its mass per unit volume.

Density = Mass/Volume

Density is typically expressed


in units of grams per milliliter,
or kilograms per liter.

It is a physical property
of a substance that does
not change with amount.
Soil is a complex mixture of
many substances, each
substance will have its own
unique density.
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Density gradient method
• A tall cylinder contains a
solution that has a high density
at the bottom and low density
at the top.
• When the soil sample is
introduced, the particles begin
to sink down through the
lighter density liquid until they
reach a place where the density
of the liquid matches the
density of the particles.
• The result is that the soil forms
bands throughout the cylinder.

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The use of insects
• Live samples are raised in a
temperature-controlled chamber
until the insects reach adulthood.
• The total amount of heat to get to a
specific growth stage is the same
whether it happens quickly at high
temperatures or slowly at cold
temperatures.
• The amount of heat needed for a
species to develop is measured in
units called Accumulated degree
hours (ADH) that simply express
the number of hours the insect
spends developing times the
temperature of each hour. 48
A body was discovered on November 12 at 1
P.M. and was found to have larva of the blow
fly species Phormia regina. In a laboratory, it
was determined that this species requires 16
hrs at 27˚C to develop from the egg stage to
the larva stage, Given that the average
temperature on November 12 was 15˚C and
on November 11 was 17˚C. when did the blow
fly first arrive at the scene?

49
Conclusions
• Chemistry is an integral part of forensic science as
chemists have made a number of important contributions
to forensic sciences over past 2 centuries.
• Forensic scientist must understand chemistry principles,
concepts and techniques. They, therefore, look at matter
from the chemist’s point of view to glean greater
information about a substance, person, or crime, for a
variety of reasons.
• Thanks to the chemistry of crime scene investigations,
more guilty people get caught and more innocent people
are freed.
• It is definitely one of the most important advances when
it comes to criminal justice and as our technology and
knowledge increase, it will only become more reliable.50
REFERENCES
•Collins D(2007) Forensic Chemistry Pp 1- 29. Thomson Brooks,
Idaho.
•Barar M (2015) The Role of Chemistry in processing crime scenes.
Int J Medpharm Res 2 (1): 10-16.
•Johll M E (2009) Investigating Chemistry Pp 93-270. W H
Freeman and company publishers, Newyork, USA.
•Halamek J and Katz E (2016) Forensic Science : A
multidisciplinary approach Pp- 1-4. Wiley-VCH GmBH & Co
KGaA.
•Bell S (2012) Forensic Chemistry Pp 70-98. Prentice Hall,
Newyork. 51

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