Chapter 1.

Forensic Instrumentation

FORENSIC INSTRUMENTATION/ANALYTICAL CHEMISTRY

- Deals with the methods for determining the chemical composition of samples
(evidences) of matter as applied to forensic problems.
a. Qualitative Method
- Yields information about the identity of atomic or molecular species or the
functional groups in the sample.
b. Quantitative Method
- Provides numerical information as to the relative amount of one or more
components of the sample..

Importance of the Study of Forensic Instrumentation

a. Develop an understanding of those instrumental tools and their application to
solve important analytical problems;
b. Familiarize with the fundamental principles of operation of modern analytical
instrumentation;
c. Appropriate choices and efficient use of measurement tools;
d. Understanding the advantages and limitations of various tools;
e. Knowledge of measurement principles is necessary for calibration,
standardization and validation of instrumental method.

Classification of Methods Used in Forensic Instrumentation

a. Classical Methods
- In the early years of chemistry, most analyses were carried out by separating
the components of interest (the analytes) in a sample by precipitation, extraction
or distillation.
- For qualitative analyses, the separated components were then treated with
reagents that yield products that could be recognized by their colors, their boiling
and melting points, their solubilities in a series of solvents, their odors, their
optical activities or their refractive indexes.
- For quantitative analyses, the amount of analytes is determined by gravimetric
or by volumetric measurements.
- In gravimetric measurements, the mass of the analyte or some compound
produced from the analyte is determined.
- In volumetric, also called titrimetric procedures, the volume or mass of a
standard reagent required to react completely with the analyte is measured.
- The methods for separating and determining analytes are still used in many
laboratories. The extent of their general application is, however, decreasing with
the advent of instrumental methods to supplant theim.

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Chapter 1.Forensic Instrumentation

b. Instrumental Methods
- Early in the 12th century, scientists began to exploit phenomenon other than
those used for clinical century, scientists began to exploit phenomenon other
than those used for classical methods for solving analytical problems.
- Measurements of such analyte physical properties as conductivity, electrode
potential, light absorption or emission, mass to charge ration, and fluorescence
began to be used for quantitative analysis.
- Highly efficient chromatographic and electrophoretic techniques began to
replace distillation, extraction, and precipitation for the separation of the
components of complex mixtures prior to qualitative or quantitative determination.

Types of Instrumental Methods:

Most of the characteristic properties used for instrumental analysis require a
source of energy to stimulate a measurable response from the analyte.
Characteristics
Emission of Radiation
Absorption of radiation
Scattering of radiation
Refraction of radiation
Diffraction of radiation
Rotation of radiation
Electrical potential
Electrical charge
Electrical current
Electrical resistance
Mass
Mass-to-charge ratio
Rate of reaction
Thermal characteristics
Radioactivity
Instrumental Methods
Emission spectroscopy (X-ray, UV, visible, electron,
Auger), fluorescence, phosphorescence and
luminescence (X-ray, UV and visible)
Spectrophotometry and photometry (X-ray, UV,
Visible, IR), photoacoustic spectroscopy; nuclear
magnetic resonance and electron spin resonance
spectroscopy
Turbidimetry, nephelometry, Raman spectroscopy
Refractometry, interfetometry
X-ray and electron diffraction methods
Polarimetry, optical rotary dispersion, circular
dichroism
Potentiometry; chromopotentiometry
Coulometry
Amperometry, polarography
Conductometry
Gravimetry (Quartz crystal microbalance)
Mass spectrometry
Kinetic methods
Thermal gravimetry and titrimetry, differential
scanning calorimetry; differential thermal analyses,
thermal conductometric methods
Activation and isotope dilution methods

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Chapter 1.Forensic Instrumentation

The second column are based on the various physical and chemical properties.
Some instrumental techniques are more sensitive than the classical techniques, but
others are not. Gravimetric or volumetric approach may suffer less interference.

Instruments for Analysis

An instrument for chemical analysis converts information about the physical or
chemical characteristics of the analyte to information that can be manipulated and
interpreted by a human. Thus, an analytical instrument can be viewed as a
communication device between the system under study and the investigator.
To retrieve the desired information from the analyte, it is necessary to provide a
stimulus, which is usually in the form of electromagnetic, electrical, mechanical, or
nuclear energy. The stimulus elicits a response from the system under study whose
nature and magnitude are governed by the fundamental laws of chemistry and physics.

RESPONSE
STIMULUS SYSTEM Numerical
UNDER
STUDY Graphical

a. Data Domains
The measurement process is aided by a wide variety of devices that convert
information from one form to another. Maybe broadly classified into:
1. Nonelectrical Domain - Among these characteristics are the length, density,
chemical composition, intensity of light, pressured.
2. Electrical Domain - The modes of encoding information as electrical quantities:
a. Analog domain signal – information is encoded as the magnitude of one of
the electrical quantities like voltage, current, charge or power.
b. Time domain information – information is stored as the time relationship of
signal fluctuations rather than in amplitudes of the signal.
c. Digital domain - data are encoded in a two level scheme. It my be
represented by the state of a light bulb, a toggle switch or a logic-level
b. Detectors, Transducers, and Sensors
The term detectors, transuder and sensor are often used synonymously, but in
fact the terms have somewhat different meanings. The most general of the three terms,
detectors, refers to a mechanical, electrical or chemical device that identifies, records,
or indicates a change in one of the variables in its environment such as pressure,
temperature, electrical charge, electromagnetic radiation, nuclear radiation, particulates
or molecules.

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Chapter 1.Forensic Instrumentation

The term transuder refers specifically to those devices that convert information in
nonelectrical domains and the converse. It include photoiodides, photomultipliers and
those that produce current.
The term, sensor pertains to the class of analytical devices that are capable of
monitoring specific chemical species continuously and reversibly like glass electrodes
and other ion selective electrodes.
Generally, instruments for chemical analysis comprise just a few basic
components:
Instrument Energy Analytical Information Input Data Signal
source information Sorter Transuder Domain of Processor
(stimulus) Transduced Readout
Information
Photometer Tungsten Attenuated Filter Photoiodide Electrical Amplitude
lamp light beam Current Digitizer
LED
display
Atomic Inductively UV or Visible Monochroma- Photomultiplier Electrical Amplifier
Emission coupled radiations tor Current Difitizer
Spectromete plasma Digital
display
Amplitudes
Charge Digital
Coulometerr Direct required to Cell potential Electrode Time timer
current reduce or Amplitudes
source oxidize Digital
analyte timer

pH Meter Sample/ Hydrogen Glass Glass – Electrical Amplitude

Glass Ion electrode Calomel Voltage Digitizer
Electrode Activity electrode Digital
display
Mass Ion Source Mass-to- Mass Electron Electrical Amplitude
Spectrometer charge ratio Analyzer multiplier Current Digitizer
Digital
display
Computer
system
Gas Flame Ion Chromato- Biased Electrical Electro-
Chromato- concentraton Graphic Electrode current Meter
graph with Vs. time Column Computer
flame System
ionization Digitizer

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Chapter 1.Forensic Instrumentation

- The current form the phototransuder is then passed through a resistor R1 which
according to Ohm’s law produces a voltage (V) that is proportional to the intensity of the
fluorescence.
- Finally, V is measured by the digital voltmeter to provide a readout proportional to the
concentration of the substance in the sample.

Informati Intensity Electrical

voltage
on flow of current
analyte

readout

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