2. Forensic Chemistry
Definition
• Forensic chemistry involves the application of
chemical principles and techniques to analyze
evidence in criminal investigations.
• It involves the identification, analysis, and
interpretation of substances found at crime scenes,
which can include drugs, toxins, explosives,
biological materials, and other chemical
compounds.
• The main goal is to provide scientific evidence
that can be used in court to support investigations
and legal proceedings.
3. Cont’d
Role
• Collection and Preservation of Evidence: Forensic chemists
are involved in ensuring that chemical evidence is properly
collected, handled, and preserved to avoid contamination and
maintain the integrity of the sample.
• Analysis and Identification: Forensic chemists perform
rigorous chemical analyses to identify substances and
determine their significance in a criminal case.
• Providing Expert Testimony: Forensic chemists may be
called to testify in court as expert witnesses, explaining their
findings and the methods used to arrive at their conclusions.
• Maintaining Chain of Custody: A crucial aspect of forensic
chemistry is maintaining the chain of custody, which ensures
that evidence is tracked from collection through analysis to
presentation in court, preventing tampering or contamination.
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5. Periodic Trends
Atomic Radius
• Refers to the distance from the nucleus of an atom to the
outermost electron shell. It is a measure of the size of an
atom and is typically expressed in picometers (pm) or
angstroms (Å), where 1 Å = 100 pm.
Trends
• Down a Group: Atomic radius increases
• Across a Period: Atomic radius decreases
Factors affecting Atomic radius
• Number of electron shells: electron shells increases down
a group, causing atomic size/radius to increase
• Nuclear charge (Number of protons): Across a period
(form left to right) the number of protons in the nucleus
increases, which results in a greater positive charge causing
a decrease in atomic radius because electrons are pulled
closer to the nucleus
• Shielding effect: repulsion of outer electrons by inner
6. Cont’d
Ionization Energy
• Refers to the amount of energy required to remove an electron from
a neutral atom or molecule in its gas phase. it provides insight into
how tightly an atom holds onto its electrons, which in turn
influences the atom's reactivity and chemical behavior.
Trends
• Across a period: Ionization energy increases
• Down a group: Ionization energy decreases
Factors affecting Ionization Energy
• Atomic radius: Smaller atoms have higher ionization energy whiles
larger atoms have lower ionization energy
• Nuclear charge: Higher nuclear charge/more protons increases
ionization energy because the nucleus has a stronger attractive force
on the electrons
• Shielding effect: Atoms with more electron shells experience more
shielding, hence lower ionization energy
• Electron configuration: Atoms with a more stable electron
configuration (such as a full outer shell, like noble gases) require
more energy to remove an electron
7. Cont’d
Electron Affinity
• Refers to the amount of energy released when an electron is added
to a neutral atom in its gas phase to form a negatively charged ion.
It represents the atom's ability to accept an electron, and it provides
insight into the atom's tendency to gain electrons and form anions.
It is typically expressed in kilojoules per mole (kJ/mol).
Trends
• Across a period: Electron affinity increases (more negative)
• Down a group: Electron affinity decreases (less negative)
Factors influencing Electron Affinity
• Atomic size: Smaller atoms generally have more negative electron
affinities whiles larger atoms have less negative electron affinities
• Nuclear charge: Atoms with a higher nuclear charge (more
protons) tend to have more negative electron affinities because the
increased positive charge attracts the added electron more strongly
• Electron configuration: Atoms that are close to having a full
valence shell (like halogens) generally have a high, negative
electron affinity because gaining an electron brings them closer to a
stable configuration
8. Bonding & Hybridization
.
Bonding
• Refers to the interaction between atoms or ions that
holds them together in a stable configuration
• The type of bonding that occurs between atoms
depends on their electronegativity, atomic size, and
other factors.
• There are three main types of bonding:
Ionic - the bond formed by the complete transfer of
valence electron to attain stability. OR the electrostatic
interaction between a metal and a non metal
Properties
• High melting and boiling points
• Generally soluble in water but insoluble in organic
solvents
• Conducts electricity in an electrolyte
9. Cont’d
Covalent - Covalent bonds are formed when two atoms
share one or more pairs of electrons. This usually occurs
between non-metal atoms.
Types
• Single bond: One pair of electrons is shared between
two atoms
• Double bond: Two pairs of electrons are shared
between two atoms
• Triple bond: Three pairs of electrons are shared
between two atoms
Properties
• Low melting and boiling points compared to ionic
compounds
• Do not conduct electricity in the solid or liquid phase
• Often soluble in organic solvents and insoluble in water
• Can exist as gases, liquids, or solids
10. Cont’d
Hydrogen bonding – Occurs when a hydrogen atom is
covalently bonded to a highly electronegative atom
(Oxygen, Nitrogen, or Fluorine), and this hydrogen atom is
attracted to a lone pair of electrons on another
electronegative atom (usually Oxygen, Nitrogen, or
Fluorine) in a neighboring molecule or the same molecule..
Properties
• Hydrogen bonding contributes to the high boiling and
melting points of substances like water
• It plays a key role in biological molecules, such as the
structure of DNA and proteins.
11. Cont’d
Hybridization - is defined as the process of combining two atomic
orbitals to create a new type of hybridized orbitals.
The formation of hybrid orbitals with completely different energies,
shapes, and so on is frequently the outcome of this intermixing.
Hybridization Orbitals
Involved
Geometry Bond Angles Examples
sp 1 s + 1 p Linear 180° BeCl₂
sp² 1 s + 2 p Trigonal
planar
120° C₂H₄
(Ethene)
sp³ 1 s + 3 p Tetrahedral 109.5° CH₄
(Methane)
sp³d 1 s + 3 p + 1 d Trigonal
bipyramidal
90° and 120° PCl₅
sp³d² 1 s + 3 p + 2 d Octahedral 90° SF₆
12. Electronic Transition
Electronic transition refers to the
movement of an electron between different
energy levels or orbitals in an atom or
molecule, typically caused by the absorption
or emission of electromagnetic radiation.
Types
Absorption: In absorption, an electron in
an atom or molecule absorbs energy from an
external source (like light) and moves to a
higher energy state or orbital.
Emission: In emission, an electron
transitions from a higher energy state to a
lower energy state, releasing energy in the
form of electromagnetic radiation (such as
light).
13. Polarity
Polarity refers to the distribution of electrical charge over the
atoms in a molecule. It arises due to differences in the
electronegativity of atoms that form a bond.
Consequences of Polarity
• Solubility - Polar molecules dissolve in polar solvents due to
the attraction between their dipoles whiles nonpolar molecules
dissolve in nonpolar solvents
• Boiling & Melting points - Polar molecules generally have
higher boiling and melting points than nonpolar molecules
because the dipole-dipole interactions or hydrogen bonds
between polar molecules require more energy to break.
• Reactivity - polar molecules are more likely to participate in
reactions with other polar molecules, while nonpolar molecules
tend to react with nonpolar substances.
• Separation – Separation techniques like TLC, Solvent
extraction and Electrophoresis take advantage of differences in
the polarity of compounds to achieve separation.
14. pH & Buffers
pH is a measure of the acidity or basicity of a solution. It indicates
the concentration of hydrogen ions [H ] or [H O ] in the solution
⁺ ₃ ⁺
and is expressed on a scale from 0 to 14
The pH is mathematically related to the concentration of hydrogen
ions as:
pH = −log[H ], where [H
⁺ ] is the concentration of hydrogen
⁺
ions in moles per liter
A Buffer is a solution that resists changes in pH when small
amounts of an acid or a base are added.
Buffers are typically made up of a weak acid and its conjugate base
(or a weak base and its conjugate acid)
Examples of buffer systems
• Acetic Acid / Acetate Buffer: Made from acetic acid
(CH COOH) and its conjugate base acetate (CH COO ).
₃ ₃ ⁻
• Carbonic Acid / Bicarbonate Buffer: Involves carbonic acid
(H CO ) and bicarbonate (HCO ). This is the primary buffering
₂ ₃ ₃⁻
system in human blood and helps regulate blood pH
15. Solutions & their Importance
A solution is a homogeneous mixture of two or more substances,
where one substance (the solute) dissolves in another (the solvent).
Solutions in chemistry can be categorized in a number of ways:
Based on the amount of solute
• Saturated: A solution that cannot dissolve any more solute at a
given temperature
• Unsaturated: A solution that can dissolve more solute at a given
temperature
• Supersaturated: A solution that contains more solute than it can
dissolve at a given temperature, and the excess solute will crystallize
if the temperature is lowered
Based on tonicity
• Isotonic: A solution with the same concentration of dissolved
solutes as the submerged object
• Hypotonic: A solution with a lower concentration of dissolved
solutes than the submerged object
• Hypertonic: A solution with a higher concentration of dissolved
solutes than the submerged object.
16. Cont’d
Based on the state of matter of the solute and solvent
• Solid – Solid: Examples include alloys like brass and bronze
• Solid – liquid: Examples include solutions of sugar or salt in water
• Solid – gas: Examples include substances like iodine or camphor
sublimating into the air
• Liquid – solid: Examples include hydrated salts or mercury in
amalgamated zinc
• Liquid – liquid: Examples include hand sanitizer
• Gas – gas: Examples include air
• Gas – solid: Examples include hydrogen gas and platinum
• True solution - Is a homogeneous mixture in which the solute is
completely dissolved in the solvent at the molecular or ionic level.
• Colloidal solution - Is a type of heterogeneous mixture in which one
substance is finely distributed within another substance.
• A suspension - Is a type of heterogeneous mixture in which solid particles
are dispersed throughout a liquid or gas but are large enough that they will
17. dd
Basics of mole concept
.
Mole is a unit used to measure the amount of substance.
One mole contains 6.022 × 10²³ (Avogadro’s number) elemental
entities, such as atoms, molecules, ions, or other particles
Avogadro’s Number is the number of particles in one mole of any
substance: 6.022 × 10²³ particles/mol
Molar mass is the mass of one mole of a substance. It is typically
measured in grams per mole (g/mol).
For elements, the molar mass is numerically equal to the atomic
mass. For compounds, the molar mass is the sum of the atomic
masses of all elements in the compound.
Atomic mass/mass number is associated with the number of protons
and neutrons in the nucleus of an atom
Atomic number is the number of protons in the nucleus of an atom
18. Cont’d
Example:
The molar mass of water (H O)
₂ is:
(2 × atomic mass of H) + (atomic mass of O) = 2(1.008 g/mol) + 15.999
g/mol = 18.015 g/mol
To find the number of moles (n) in a given sample, you use the formula:
n = m
M
Where;
n = number of moles
m = mass of the sample (in grams)
M = molar mass of the substance (in grams per mole)
The number of particles (atoms, molecules, ions) in a sample can be
determined by multiplying the number of moles by Avogadro's number:
Number of particles = n × NA
Where;
n = number of moles
NA = 6.022 × 10²³ = Avogadro’s number
21. Forensic chemical analysis
Determining the composition of substances involves qualitative
analysis (to identify the components) and quantitative analysis
(to measure the amount of these components)
Some common methods used in forensic chemistry for both
qualitative and quantitative analysis are:
Qualitative Analysis Methods
These methods are used to identify the chemical nature,
composition, or characteristics of substances.
• Spectroscopic methods eg..; UV-Vis, IR, Raman
• Chromatographic methods eg..; TLC, GC, HPLC
• Microscopic and Elemental Analysis eg..; SEM, TEM, XRD,
EDX
• Wet Chemical Tests (Spot Tests) eg..; precipitation test for
ions, color tests (Scott test for cocaine, Kastle-Meyer for blood)
22. Cont’d
Quantitative Analysis Methods
These methods measure the exact amounts or concentrations of
substances in a sample.
• Gravimetric Analysis - measures the mass of a substance
after isolation
• Titrimetric Analysis eg..; acid-base titration, redox titration
• Spectroscopic Quantification eg..; UV-Vis, AAS, Flame
photometry
• Chromatographic Quantification eg..; GC, HPLC
• Mass Spectrometry – measures concentration based on
mass-to-charge ratio
• Electrochemical methods eg..; Potentiometry, voltammetry
23. Bribe Trap Cases
A bribe trap case involves setting up a covert operation to catch an individual in
the act of accepting a bribe. Law enforcement agencies use scientifically
validated techniques, including the application of phenolphthalein powder, to
gather irrefutable evidence.
Phenolphthalein acts as an indicator that reveals the presence of currency
involved in a bribe through a visual chemical reaction. When treated currency is
exposed to a basic medium (e.g., sodium carbonate solution), it produces a vivid
bright pink color, confirming the transfer of money.
Examination of phenolphthalein
• Spot test - few drops of a basic solution, and a pink color confirms presence
of phenolphthalein
• TLC – develop plate in appropriate solvent, visualize by iodine fumes
treatment of the developed plate and compare with standards.
• UV-Vis Spectroscopy – In methanol, absorption peak of 277nm is observed
and in aldehyde-free alcohol absorption peaks of 225 and 285nm were
observed
• HPLC – retention time is recorded and compared to standard.
26. Analysis of Petroleum Products
Parameter Description
Density & Specific Gravity Mass per unit volume
Color Visual spectrum
Flash point Lowest temperature at which vapors ignite
Boiling point Determines fuel volatility
Cetane number (Diesel) Measures combustion quality of diesel
Octane number (Petrol) Anti-knock quality of gasoline
Viscosity Resistance to flow
27. Parameter/Property Petrol/Gasoline Diesel Kerosene
Density 710 – 770 kg/m³ at 15°C 820 – 870 kg/m³ at 15°C 0.78 – 0.82 g/cm³ at 15°C
Color (Varies from place
to place due to dye added)
Orange (dye - Phenyl azo
2- naphthol)
Yellow Colorless
Flash point < -21°C 35°C to 40°C 37°C to 65°C
Boiling point 25 to 75°C 250 to 350°C 190 to 250°C
TLC Solvent System
(Hexane: Toluene: Acetic
Acid [ 50 : 50 : 2])
Pink or Orange color (Rf
Value 0.49 & 0.51)
Violet Blue color spot (Rf
around 0.4)
Filter Paper Test (Place
two drops of fuel on a
filter paper)
Vanish without leaving
any trace behind
Leave patches Leave patches
Ultra Violet Lamp Chloranil spray reagent:
brick red
Green/Yellow Blue
Cetane number 5 – 20 40 – 55 NA
Octane number 90 – 92 15 – 25 NA