Lecturers : Prof NC Hintsho-Mbita

Email : [email protected]
Office No. : 2012 N- block
Ext. : 2205

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 INTRODUCTION
• Analytical chemistry is the branch of chemistry dealing
with the separation, identification, and quantification of
the chemical components of natural and artificial
materials.

• The basic knowledge of analytical chemistry is applied

when detecting the presence and determining the
quantities of chemical compounds, such as:
– heavy metals during water purification or
– arsenic in tissue samples.

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 Introduction to Analytical Chemistry
Analytical chemistry deals with separating, identifying, and
quantifying the relative amounts of substances in samples of
matter.
• Analyte is the component of the sample that is determined.
• Analytical chemistry is applied to all aspects of life, it covers
all fields of sciences.
• Examples : Rock analysis, Water analysis, Medicine, Food
analysis, Environment, Biochemistry, Forensic, Archeology,
Space science, etc.

.
 Types of Analysis
Qualitative analysis :
 What is present?
 reveals the chemical identity of the species in the sample.

• Quantitative analysis :
 How much is present ?
 determines the relative amount of species or analytes, in
numerical terms.
 In order to perform quantitative analysis, typically one needs
to complete qualitative analysis. One needs to know what it is
and then select the means to determine the amount.
 Analytical Methods

• Analytical methods are often classified as either being

classical or instrumental.

• Classical: qualitatively separated components were treated

with reagents that yielded products that could be recognized
by their : color, boiling point, melting point, odors, optical
activities, solubility.
• Quantitative gravimetric measurements and titrimetric
measurements.
 Analytical Methods
• Instrumental analysis (Our focus in this section)
 An instrument for chemical analysis converts information
stored in 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.
 Analytical Methods
1)Gravimetric method: determines the mass of the analyte or some
compound chemically related to it.
2) Volumetric method: the volume of a solution containing sufficient reagent
to react completely with the analyte is measured.

3)Instrumental methods: use an instrumental technique to assay the amount

of sample.
• Spectroscopic method: based on measurement of the interaction
between electromagnetic radiation and analyte atoms or molecules or
on the production of such radiation by analytes.
• Electroanalytical method: based upon the measurement of electrical
properties such as potential, current, resistance, and quantity of
electrical charge.
 Separation method:
 Analytical Methods
Some of the common spectroscopic techniques
• Atomic absorption spectroscopy
• Ultraviolet-Visible spectroscopy ( Absorbance/Concentration)
• X-Ray Flourescence Spectroscopy
• Fourier Transform infrared spectroscopy
• Laser Raman Spectroscopy
 SPECTROCHEMICAL METHODS

• After studying this topic the student should be able

to :
– Define each spectroscopic method
– Describe each spectroscopic method principles
– Explain major components of each spectroscopic
method and their functions
– Explain factors affecting function of each
spectroscopic method
– Describe advantages & disadvantages of each
spectroscopic method
– Data analysis
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 INTRODUCTION TO
SPECTROCHEMICAL METHODS

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 Introduction
• Spectroscopy and spectrography
– The measurement of radiation intensity as a function
of wavelength.
• Often used to describe experimental spectroscopic
methods

– Spectral measurement devices

• spectrometers,
• spectrophotometers,
• spectrographs or
• spectral analyzers..

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 Introduction
– Spectroscopic studies were central to the development
of: Quantum mechanics

– Spectroscopy is used in PHYSICS and CHEMISTRY

because atoms and molecules have unique spectra.

– As a result, these spectra can be used to detect,

identify and quantify information about the atoms and
molecules present in the analyte.

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 Introduction
• Spectrochemical methods
– Absorption or emission of light by the analyte
• More than half or all analytical instrumental
methods involve these processes

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 Introduction
– Spectrochemical analysis
• Degree involves analysis of light absorbed or the
primary light emitted
–Related to the quantity of analyte present in the
sample
–Critical qualitative and quantitative
measurements!

• Atomic spectroscopy
–Spectral differences between atoms for
elemental composition
• Molecular spectroscopy for electronic and
vibrational absorption
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 Spectroscopy
• Interaction of Radiation with matter as a function of
wavelength

• The study of molecular or atomic structure of a substance

by observation of its interaction with electromagnetic
radiation

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 Spectroscopy
• The basic principle shared by all spectroscopic
techniques

response

response
sample
detector

• The response is usually recorded as a function of

radiation wavelength.
• A plot of the response as a function of wavelength is
referred to as a spectrum.
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 Regions of the electromagnetic spectrum
• Most of us are aware of many different ways of
transmitting energy and these phenomena come together
in one physical entity called the ELECTROMAGNETIC
SPECTRUM

• The difference between these sources of radiation is the

amount of energy they radiate.

• The radiation from these and other sources covers a

range of energies

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 Regions of the electromagnetic spectrum

• Classes of electromagnetic radiation:

– Gamma radiation
– X-ray radiation
– Ultraviolet and Visible radiations
– Infrared radiation
– Terahertz radiation
– Microwave radiation
– Radio waves

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 The electromagnetic spectrum

Change of Change of Change of electron Change of nuclear

orientation configuration distribution configuration

NMR= 10 m - 100cm wavelength

ESR = 100 cm - 1cm wavelength Change of spin
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 Radiation Energy
• The strength of the radiation energy will interact with the
molecules in different ways:

– High energy sources produce breaking of bonds

• X-Ray,
• γ Rays, …

– Medium energy sources excite electrons

• UV Spectroscopy
• VISIBLE Spectroscopy

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 Radiation Energy
– Low energy sources produce vibrations in chemical
bonds

• Near-infrared
• Mid-infrared
• Far-infrared Energies

– Very low energy sources produce rotation of the

chemical bonds

• Microwaves and
• Radio waves

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 The particle nature of radiation energy
• Electromagnetic Spectrum: E = hv

– UV, visible, and infrared regions

• Radiation are transformed in a waveform

–Nanometer and micrometer units used for

wavelength

–Relationship
»Long wavelength = low energy
»Short wavelength = high energy
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The particle nature of radiation energy

• Infrared region
–Have short Wavelengths or high wavenumber
–Their energy is higher than radio or television
–Harmless
»Remotes for TVs, VCRs, etc

• Dangerous radiations: UV, x-rays, and gamma

rays
–Very short wavelengths
–Very high energy

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 Effect of energy on a molecule
ELECTROMAGNETIC SPECTRUM
ENERGY
1.2 x105 1.2 x107 12000 310 150 0.12 0.0012
( kJ/mol)

Electronic excitation
e-

FREQUENCY
(Hz) 1020 1018 1016 1014 1012 108

visible
Cosmic γ x Ultra Radio
Infrared Microwave
rays rays rays violet waves
WAVELENGTH
(m) 10-12 10-11 10-9 10-6 10-3 10-1

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 Interaction of light with matter

LIGHT MATTER INTERACTIONS

SCATTERING ABSORPTION

Elastic, PHOTOLUMINESCENCE
Inelastic

Fluorescence Phosphorescence
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 Interaction of light with matter
• Interaction in spectroscopy
involve transition between
energy levels of chemical
species
• Interactions: reflection,
refraction, elastic scattering,
interference and diffraction
are related to the bulk
properties of materials
• Interactions depends strongly
on the energy of the radiation
used and the mode of
detection
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 Spectroscopic measurements
• There are several ways to use a spectrometer:
– Substance Detection & Concentration
• Absorption Methods
–It refers to spectroscopic techniques that
measure the absorption of radiation, as a
function of frequency or wavelength, due to
its interaction with a sample.

–The sample absorbs energy, i.e., photons,

from the radiating field.

–The intensity of the absorption varies as a

function of frequency, and this variation is
the absorption spectrum. 27
 Spectroscopic measurements
• There are several ways to use a spectrometer:
– Substance Detection & Concentration
• Absorption Methods
Incident light
S2

E2=hv2

Absorbance
sample
S1

E1=hv1

Transmitted light S0 λ1 λ2
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 Spectroscopic measurements
• There are several ways to use a spectrometer:
– Substance Detection & Concentration
• Emission Spectroscopy
–It is a type of electromagnetic spectroscopy
which analyses fluorescence from a sample.

–It involves using a beam of light that excites

the electrons in molecules of certain
compounds and causes them to emit light of a
lower energy.

–At low concentrations the fluorescence

intensity will generally be proportional to the
concentration of the fluorophore. 29
 Spectroscopic measurements
• There are several ways to use a spectrometer:
– Substance Detection & Concentration
• Photoluminescence Spectroscopy
–The emission of photons is measured after
absorption.

–Light source, self-emission which means the

electrons transferred to the lowest level
spontaneously

–A fluorescence excitation spectrum provides

information about the absorption spectrum of
the excited fluorescent molecule in the excited
state. 30
 Spectroscopic measurements
• There are several ways to use a spectrometer:
– Chemical Identification
• IR Spectroscopy
–It is a powerful analytical tool for determining
the structure of both inorganic and organic
compounds

–All substances vaporize molecules that can be

detected with their own specific spectral
signature while being exposed to an
appropriate light.

–Vibrating ⇔ Energy ⇔ Frequency

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 Spectroscopic measurements
• There are several ways to use a spectrometer:
– Chemical Identification
• Atomic Spectroscopy
–It is used for determination of elemental
composition by its electromagnetic or electron
beam.

–It is closely related to other forms of

spectroscopy.

–It can be divided by atomization source or by

the type of spectroscopy used.
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 Tutorial Questions
1. Why do analytical chemists employ spectrochemical methods?
(3 marks)

2. In electromagnetic radiation, x-rays region is regarded as

dangerous radiation whereas infrared region known as a
harmless radiation. Explain, why is x-ray radiation harmful?
(3 marks)

3. Explain and give a conceptual diagram to demonstrate

absorption and emission processes in spectroscopic
measurements. (5 marks)

4. Define these terms: luminescence, photoluminescence,

chemiluminescence and bioluminescence. (4 marks)
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