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Spectrochemical

Methods of
Analysis
CHM580
Fakulty of Applied Sciences
UiTM
FTIR
AAS
UV-VIS
ICP-OES
NMR
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

CHM 580
In this course, you will appreciate
The methods and instruments used to
make measurements
The principles behind these
measurements

SPECTROSCOPY


Classification of Instrumental
Methods
Characteristic Properties Instrumental Methods
Emission of radiation Emission (ICP-OES) and
Fluorescence spectroscopy
Absorption of radiation AA, UV-vis, IR, NMR spectroscopy
Scattering of radiation Raman spectroscopy
Mass-to-charge ratio MS
Chemical and Physical Properties Used in Instrumental Methods
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 type of methods that are
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, Night-
vision, 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 (v) 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 10
8
m s
-1
c
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,
Reciprocal of wavelength of radiation,
Unit of cm
-1

The wavelength must be measured in cm

1
v
Prefixes
atto a 10
-18
femto f 10
-15

pico p 10
-12

nano n 10
-9

micro 10
-6

milli m 10
-3

centi c 10
-2

deci d 10
-1

kilo k 10
3

mega M 10
6

giga G 10
9

tera T 10
12

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 v or of the radiation is related to
the energy difference

v
hc
h E E E = = = A
0 1
where
h is Planck's constant
is the wavelength
v is the frequency
c is the speed of light.
Energy of a given EMR
hc
c
h h E
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; H
2
, H
2
O

A compound is a molecule that contains at
least two different elements
Examples: H
2
O, 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
Scattered

as a result of 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
t t*
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, P
o
and P
Passes through the medium that contains
the analyte, P
o
Part of the radiation has been absorbed by
the matter, P
Two terms related to the ratio of P and P
o
Transmittance
Absorbance

Beers Law
A beam of monochromatic radiation of radiant power P
0
is directed at a solution
The solution contains a sample
Absorption takes place
The beam of radiation leaving the solution has radiant
power P
b
P
o
P
Transmittance, T

T =


% Transmittance, %T = 100 T = x 100%

Absorbance, A

A = - log T = - log
0
P
P
0
P
P
0
P
P
Absorbance vs. %Transmittance
A
10 T

=
Beers Law
Absorbance is linearly related to the
concentration of the absorbing species c
and the pathlength b of the absorbing
medium
A = abc
c has the units of g L
-1
b has the unit of length, cm
a, 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 c
called molar absorptivity
has the units of L mol
-1
cm
-1

A = bc
Q & A
A compound of formula
weight 280 adsorbed
85% of the radiation in a
2.5 cm cell at a
concentration of 15 ug
mL
-1.
Calculate its molar
absorptivity at the
wavelength
A= 0.839
= A/bc
= 0.839/2.5 x Molar?
=0.3356 x 5.36 x 10
-5
M
=1.8 x 10
-5
(unit?)

The SI units for are
m
2
/mol, but in practice,
they are usually taken as
M
1
cm
1
or L mol
1
cm
1
.
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
Continuous

Emission
or
Bright line
Absorption
or
Dark line
Visible region
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 = k c
where
I is the intensity of light
k is the proportionality constant
c is the concentration
Instrumental methods
Characteristic properties Spectrometers
Emission of radiation


Absorption of radiation




Scattering of radiation

Mass-to-charge ratio
ICP-OES
Fluorescence

UV-vis
FTIR
NMR
AAS (flame and GF)

Raman

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