Spectrochemical

Methods of
Analysis

UV-VIS

NMR

AAS

CHM580
ICP-OES

FTIR

Fakulti Sains Gunaan

Shah Alam

Why do we need an instrumental

analysis course?
Scientists involve in chemical analysis
samples of interest (analytes) usually ask
these QUESTIONS
What is this sample composed of?
How much of each component is
present?

Why do we need an instrumental

analysis course?
Chemical analysis relies on
accurate measurements
careful interpretation of results

Classification of Instrumental
Methods
Chemical and Physical Properties Used in Instrumental Methods
Characteristic Properties

Instrumental Methods

Emission of radiation

Emission (ICP-OES) and

Fluorescence spectroscopy

Absorption of radiation

Atomic Absorption
Spectroscopy(AAS), UV-vis, IR, NMR
spectroscopy

Scattering of radiation

Raman spectroscopy

Mass-to-charge ratio

MS

Definitions
Spectrometer/Spectrophotometer
An instrument
Spectroscopy
The use of the spectrometer
Spectrometry
The measurement of a spectrum
Spectrum
Output of the instrument (further definition)

Spectrometric methods
A group of techniques that relies on the
interaction of electromagnetic radiation and
matter
There are many types methods based on either
molecular or atomic interactions

What is light?
Visible light
the form of light which we can see
a form of energy made up of waves known
as electromagnetic radiation
What we perceive as light is actually only
a very small part of the electromagnetic
spectrum.

Electromagnetic spectrum and

the uses in everyday life
How do we make use of the varied
properties of light?
There are thousands of applications.
Here are a few examples:
Radio waves - Television, radio, cellphones,
satellites
Microwaves - Satellites and microwave
ovens
Infra-Red - Toaster ovens, broilers, Nightvision, F.L.I.R. (forward looking infra-red)
Ultra-violet - Sunbeds, night club lighting
X-rays - Medical imaging, material science

Electromagnetic radiation
Represented as electric and magnetic
fields that undergo in-phase, sinusoidal
oscillations at right angles to each other
and to the direction of propagation

Properties of electromagnetic
radiation
Dual properties
Wave
Particle

Wave characteristics
Amplitude
Wavelength
Frequency

Wave characteristics

Amplitude, A is the length of the electric

vector at a maximum in the wave

Wave characteristics
Wavelength () is the distance between two
equivalent points on successive waves, and it can
be measured with a base unit
of meters (m) (such as km, cm, m, angstroms ())
Frequency () is the number of cycles of a wave to
pass some point in a second.
The basic unit of frequency is cycles per second
(s-1), or Hertz (Hz)

Velocity of radiation
Wavelength and frequency are
related by the velocity of
radiation (c), a fundamental
constant

Velocity of radiation
In vacuum, c
Is independent of wavelength
Is at its maximum
2.99792 x 108 m s-1

Velocity of radiation
In medium containing matter
Propagation of radiation is slowed by the
interaction of EMR with bound electrons in
matter

Frequency
and
wavelength

Wavenumber,
1
Reciprocal of wavelength of radiation,

-1
Unit of cm
The wavelength must be measured in cm

Prefixes
atto
femto
pico
nano
micro
milli
centi
deci
kilo
mega
giga
tera

a
f
p
n

m
c
d
k
M
G
T

10-18
10-15
10-12
10-9
10-6
10-3
10-2
10-1
103
106
109
1012

1 = 10-10 m = 10-8 cm
1 nm = 10-9 m = 10-7 cm
1m = 10-6 m = 10-4 cm

Electromagnetic radiation

Electromagnetic radiation

The electromagnetic spectrum

Quantum-mechanical properties of
radiation
Planck's theory was based on the idea that
black bodies emit light (and other
electromagnetic radiation) as a stream of
discrete particles called

photons or quanta

Energy states of chemical species

Postulates of quantum theory
atoms, ions and molecules can exist only
in certain discrete states
change their state
they absorb or emit energy exactly
equal to the energy difference between
the states

Energy states of chemical species

when species absorb or emit radiation,
the or of the radiation is related to
the energy difference
where
h is Planck's constant
is the wavelength
is the frequency
c is the speed of light.

hc
E E1 E0 h

Energy of a given EMR

c
E h h hc

Atom

Atomic orbitals

Orbital shapes representing boundary surfaces enclosing regions

of space where electrons are most likely to be found in the first
three shells.

Molecules and compounds

A molecule is a group of two or more atoms
in a definite arrangement held together by
chemical bonds. Examples; H2, H2O
A compound is a molecule that contains at
least two different elements
Examples: H2O, NaCl
All compounds are molecules but not all
molecules are compounds

Molecules

3D

3D

2D

Atomic and molecular orbitals

Atomic orbitals

Molecular orbitals

Interaction of radiation and matter

Spectroscopists use the interaction of
radiation with matter
To obtain information about MATTER
Sample is stimulated by applying ENERGY
which can be in the form of
Heat
Electrical energy
RADIATION
Chemical reaction

Overall process of an
instrumental measurement

Interaction of radiation with matter

Interaction of radiation and matter

Initially, the matter (molecules, atoms or ions)
is in its ground state
Lowest energy state
Some analyte species undergoes a
TRANSITION to an excited state
Higher energy level

Interaction of radiation and matter

We obtain information about the sample by
measuring EMR
Emitted
Absorbed as a result of
Scattered excitation

Method of interactions
Absorption
Radiation is absorbed by an atom, molecule
or ion taking it to a higher energy state

Emission
The release of photon by an atom, molecule
or ion, taking it to a lower energy state

Scattering
an excitation to a virtual state lower in energy
than a real electronic transition

Three General Types of Spectra

Continuous spectrum

Emission line spectrum

Absorption line spectrum

The absorption process

Electronic transition
Changes in the distribution of outer
electrons about atoms or molecules

Molecular
*
Atomic

Atomic absorption
With atoms, the simplest
case, it is still a relatively
complex absorption
process.

Even for hydrogen atom,

the line spectrum is
complex due to major
electronic transitions and
the sublevels s, p, d, f

Quantitative absorption methods

Measurements of two beams, Po and P
Passes through the medium that contains
the analyte, Po
Part of the radiation has been absorbed by
the matter, P
Two terms related to the ratio of P and Po
Transmittance
Absorbance

Beers Law
A beam of monochromatic radiation of radiant power P0
is directed at a solution
The solution contains a sample
Absorption takes place
The beam of radiation leaving the solution has radiant
power P

P
Po
b

Transmittance, T

T=

P
P0

% Transmittance, %T = 100 T =

x 100%

Absorbance, A

P
P0

A = - log T = - log

P
P0

Absorbance vs. %Transmittance

T 10

Beers Law
Absorbance is linearly related to the
concentration of the absorbing species c
and the pathlength l of the absorbing
medium

A = lc
c has the units of g L-1
l has the unit of length, cm
, absorptivity, has the units of L g-1 cm-1

Beers Law
When c is in mole/L or M, b in cm,
the proportionality constant is
called molar absorptivity
has the units of L mol-1 cm-1

A = lc

Emission of EMR
Atoms, molecules and ions can be excited
via a number of processes
When they relax, they release excess
energy
In some cases, the relaxation causes the
emission of EMR
The type of EMR emission is often the
characteristic of the species

Emission of EMR
Energy

Emission of EMR
Continuous spectra
Produced by many solids that are
heated until they glow
Radiation is emitted over a wide
energy range
Maximum is a function of the
temperature of the materials

Spectra in the visible region

Visible region
Continuous
Emission
or
Bright line
Absorption
or
Dark line

Emission of EMR
Type of spectra
Atomic species line spectra
relatively narrow lines but still complex
Several major electronic transition and sublevels

Emission
The intensity of the radiation is directly
proportional to the concentration of
species being measured

I=kc
where
I is the intensity of light
k is the proportionality constant
c is the concentration

Instrumental methods
Characteristic properties

Spectrometers

Emission of radiation

ICP-OES
Fluorescence

Absorption of radiation

UV-vis
FTIR
NMR
AAS (flame and GF)

Scattering of radiation

Raman

Mass-to-charge ratio

Mass

Common spectroscopic methods

based on EMR
Types of spectroscopy

Wavelength
range

Type of quantum
transition

Gamma-ray emission

0.005 1.4

Nuclear

X-ray (A, E, F, D)

0.1 100

Inner electron

Vacuum UV absorption

10 180 nm

Bonding electrons

UV-vis (A, E, F)

180 780 nm

Bonding electrons

IR absorption and Raman

scattering

0.78 300 m

Rotation/vibration of
molecules

Microwave absorption

0.75 375 mm

Rotation of molecules

Electron spin resonance

3 cm

Spin of electrons in a
magnetic field

Nuclear magnetic resonance

0.6 10 m

Spin of nuclei in a
magnetic field