• CHAPTER 1:

• AN INTRODUCTION TO
SPECTROSCOPIC METHODS OF ANALYSIS
www.tinyurl.com/skoogpia7
CONTENT
1.1 Properties of Electromagnetic Radiation
1.2 The Electromagnetic Spectrum
1.3 Spectroscopic Measurements
1.3.1 Radiation Absorption
❑Transmittance
❑Absorbance
1.3.2 Beer’s Law
❑Theory and application
❑Limitations to the applicability of
Beer’s Law
CONTENT
1.3.3 Absorption Spectra
❑Atomic absorption
❑Molecular absorption
1.3.4 Emission of Electromagnetic
❑Line spectrum
❑Band spectrum
❑Continuum spectrum
Why Do We Need
An Instrumental Analysis Course?
Scientists involve in analysis samples of interest
(analytes) usually ask these QUESTIONS:

❑What is this sample composed of? (Qualitative

analysis)
❑How much of each component is present?
(Quantitative analysis)

Scientific analysis relies on:

❑Accurate measurements
❑Careful interpretation of results
WHAT IS SPECTROSCOPY ?
• Spectroscopy is a study of the interactions
of radiation with matter (samples in the
form of atom ion or molecules)

• Spectroscopy deals with the absorption,

emission, scattering, etc. of electromagnetic
radiation by matter.
1.1 Electromagnetic Radiations
(EMR)
• EMR is type of energy readily in the forms of:
• light
• radiant heat.

• E.g:
• Gamma rays
• X-rays
• Ultraviolet
• Microwave
• radio-frequency
Electromagnetic Radiations (EMR)
 Common spectroscopic
methods based on EMR
Types of spectroscopy Wavelength range Type of quantum
transition
Gamma-ray emission 0.005 – 1.4 Å Nuclear
X-ray (A, E, F, D) 0.1 – 100 Å Inner electron
Vacuum UV absorption (VAC-UV) 10 – 180 nm Bonding electrons
UV-Vis (A, E, F) 180 – 780 nm Bonding electrons
IR absorption and 0.78 – 300 m Rotation/vibration of
Raman scattering molecules
Microwave absorption 0.75 – 375 mm Rotation of molecules
Electron spin resonance (ESR) 3 cm Spin of electrons in a
magnetic field
Nuclear magnetic resonance 0.6 – 10 m Spin of nuclei in a
(NMR) magnetic field
Various type of interaction of EMR with matter
LEARNING CHECK…
• Name any four (4) electromagnetic radiations in the
order of increasing energy (2m - Mar 2014)
• Arrange the following four electromagnetic spectral
regions in the order of increasing energy (2m - Mar
2013)
Visible Ultraviolet Infrared Microwave
Electromagnetic Spectrum And The Uses
In Everyday Life
How do we make use of the varies
properties of light?

There are thousands of applications.

Here are a few examples:

Radio waves - Television, radio, cell-phones,

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
Properties Of Electromagnetic
Radiation
• Dual properties of EMR:
• Wave properties

• Particles properties
1. Wave Characteristics

1. Amplitude (A)
2. Wavelength (λ)
3. Frequency (ν)
 Wave Properties

• Amplitude (A) - is the length of the electric

vector at a maximum in the wave.

• Wavelength (λ) - is the distance between two

equivalent points on successive waves, and it can
be measured with a base unit of meters (such as
m, km, cm, m and angstroms Å)
 Wave Properties
• Frequency () - number of cycles of a wave to
pass some point in a second. The SI unit of
frequency is cycles per second (s-1) or Hertz (Hz)
Frequency (ν) and Wavelength (λ)
Frequency (ν) and
wavelength (λ)
are related by the velocity of radiation (c),
which is a fundamental constant
( 3.0 x 108 m/s @ 3.0 x 1010 cm/s)
𝑐
𝜈=
𝜆 − −1
−1 𝑐 (𝑚𝑠 1 @ 𝑐𝑚𝑠 )
𝜈(𝑠 ) =
𝜆(𝑚@𝑐𝑚)
 
Wavenumber,
❑Wave number is reciprocal of wavelength of
radiation.
❑Wave number is much favored because of its
direct proportional to energy.
❑Unit - cm-1.
❑Wavelength must be measured in cm.

1
=

 2. Particle properties
(Quantum-mechanical Properties Of Radiation)

Planck's theory was based on the idea that

black bodies emit light (and other EMR)
as a stream of discrete particles
called photons or quanta
Important postulates of quantum theory:

1. Atoms, ions and molecules can exist only in certain

discrete states, characterized by definite amount of
energy. When a species change of state, it absorbs
or emits energy exactly equal to the energy
difference between the states.
Important postulates of quantum theory:

2. When atoms, ions and molecules absorb or emit

radiation in making the transition from one energy
state to another, the frequency () or the
wavelength () of the radiation is related to the
energy difference (ΔE) between the state by the
equation:

hc
E = E1 − E0 = h =

h is Planck's constant
λ is the wavelength
 is the frequency
c is the speed of light
 Energy of a given EMR

1 c
E = h = h = hc  = hc
 

Energy (E) is proportional to :

❖Planck’s constant (h) 6.625x10–34 J•s
❖Frequency (ν)
❖Wavelength (λ)
❖Speed of light ( c ) 2.998 × 108 m/s
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 103
mega M 106
giga G 109
tera T 1012
Frequency wavelength and energy

✦ Blue light

✦ Red light
LEARNING CHECK…
1. Calculate the wavelength (in nm) of an
electromagnetic radiation at 8 x 1014 s-1.(2m -
Mar 2016) (Answer: 375 nm)
c 1
E = h = h = hc  = hc
 
LEARNING CHECK…
2. A molecular absorption band occurs at a wavenumber of 812
cm-1. Calculate : (Mar 2013)
a) The wavelength (in meters) of this radiation. (2m)
b) The energy (in Joules) of this radiation. (2m)

c 1
E = h = h = hc  = hc
 
 = 1/ 
Solution:
1
a) ;λ= =1.23 x10-3 cm x 10-2 = 1.23 x 10-5 m
812
6.6 𝑥 10−34 𝑥 3 𝑥 108 𝑚𝑠 −1
b) E = hc/λ =
1.23 𝑥 10−5 𝑚
= 1.62 x10-20 J
LEARNING CHECK…
3. If the wavelength used in a spectroscopic instrument is 560 nm (Sep
2015):
a) Calculate the frequency in Hz. (3m)
b) Determine the energy (in Joules) of this radiation. (2m)

c 1
E = h = h = hc  = hc
 

Solution:
3.00×108 𝑚𝑠 −1
a) ν = c/λ = −9 = 5.36 x 1014 s-1
560×10 𝑚
b) E = hν = 6.63 𝑥 10−34 𝐽𝑠 𝑥 5.36 𝑥 1014 𝑥 𝑠 −1
= 3.55 𝑥 10−19 J
Some Terminologies
Spectroscopy
❑The science that deals with the interactions of
various types of radiation with matter.

Spectrometry/spectrometric methods
❑The measurement of the intensity of radiation with
a photoelectric transducer/detector or other type of
electronic device.
Some Terminologies
Spectrum
❑Output of the instrument
❑Adsorption spectrum – the spectrum of EM
radiation that has passed through a medium that
absorbed radiation of certain wavelength.

Spectrometer
❑An instrument for spectrometric analysis.

Spectrophotometer
❑A spectrometer equipped with a photo-transducer.
1.2 THE ELECTROMAGNETIC
SPECTRUM
✦ electromagnetic
spectrum
encompasses
an enormous
range of
wavelengths
and frequencies
(and thus
energies).
THE ELECTROMAGNETIC SPECTRUM
1.3 SPECTROSCOPIC MEASUREMENTS

❑1.3.1 Radiation absorption

❑1.3.2 Beer’s Law
❑1.3.3 Absorption spectra
❑1.3.4 Emission of EMR
Overall process of an instrumental
measurement
Interaction of radiation and matter

• Initially, the matter (molecules, atoms or ions)

predominantly is in its ground state (lowest energy
level).
• The stimulus causes 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 excitation
❑Scattered
Type 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.
Interaction of radiation with matter
 Type of spectroscopy
Type of Stimulus Process Measurement
spectroscopy
Absorption External Incident radiation is Amount of light of light
EMR source absorbed absorbed as a function
of wavelength
Emission Heat The radiant power A plot of the emitted
Electrical emitted as the analyte radiation as a function
energy return to the ground of frequency or
state wavelength
Scattering External Incident radiation is The intensity of the
EMR source scattered, the elastically scattered
interaction of the radiation.
incoming radiation with The inelastic scattering
the sample may be to produce a vibrational
elastic or inelastic. spectrum
Instrumental methods
Characteristic properties Spectrometers
Absorption of radiation UV-vis
FTIR
AAS (Flame and GF)
NMR

Emission of radiation ICP-OES

Fluorescence

Scattering of radiation Raman

Mass-to-charge ratio Mass

1.3.1 RADIATION ABSORPTION
Measurements of two beams, Po and P
• Po (Power /Incidents light) - Passes through the
medium that contains the analyte.
• P (transmitted light) - Part of the radiation has been
absorbed by the matter
Two terms related to the ratio of P and Po
• Transmittance
• Absorbance

P
Po
b
 Transmittance
• Transmittance (T) - The ratio of the intensity of the
transmitted light (P) to the intensity if the incident light
(Po).
• It is a fraction of the incident light which pass through a
sample.

P
Transmittance, T : T=
P0
P
% Transmittance : 100
P0
 Absorbance
• Absorbance - A logarithmic measure of the amount of light
absorbed (at a particular wavelength) as the light passes
through a sample or substance.
• Absorption takes place when a beam of monochromatic
radiation of radiant power P0 (incident light) is directed at a
solution contains a sample. The beam of radiation leaving the
solution has radiant power P (transmitted light)

Absorbance, A
P
A = - log T = - log P0 P
Po

b
Absorbance vs. %Transmittance

−A
T = 10
1.3.2 BEER’S 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
 Calibration curves
Plot of absorbance vs. concentration

Non ideal
Absorbance
Deviations of Beer’s Law
• Non ideal calibration curve is caused by:
1. Ideal deviation(Concentration of sample is too
high)
2. Instrumental deviation-Illumination is not
monochromic.
3. Chemical deviation.

4. Determine two causes of deviation in Beer’s Law.

(2m – Mar 2016)
Beer’s Law

A = bc
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
LEARNING CHECK…
1. A 30 x10-3 g sample of a compound with a
molecular weight of 317.17 gmol-1 was dissolved
with the solvent in a 250 mL volumetric flask. The
absorbance of this solution at 238 nm was 0.524
in a 1.00 cm cuvette. Calculate the molar
absorptivity of this compound. (3m - Mar 2016)
(Answer: ε = 1.38 x 103 L mol-1 cm-1)
LEARNING CHECK…

1. A solution containing Fe(SCN)2+ complex which is formed

between iron(III) and KSCN has a molar absorptivity of 7.35 x
10 3 Lmol-1 cm-1 at 580 nm. (Mar 2015)

a) Determine the absorbance of a 2.5 x 10-5 M solution of the

complex at 580 nm in a 1.00 cm cell. (2m)
b) Calculate the percent transmittance of the solution describe in
(a). (2m)
c) Calculate the absorbance of a solution in a 2.00 cm cell in
which the concentration of the complex is twice of that in (a).
(2m)
d) Calculate the frequency of the radiation if a particular
electromagnetic radiation has a wavelength of 862 nm. (2m)
e) Calculate the energy (in Joules) of this radiation. (2m)
LEARNING CHECK…
2. A copper(II) sulfate solution of unknown
concentration is placed in a colorimeter and
absorbance reading of 0.46 is recorded. Using the
same 1.0 cm cell, a 0.05 M solution of copper(II)
sulfate gives an absorbance reading of 0.34. What
is the concentration of the unknown solution?
(3m – Sept 2013)
3. Sketch and label correctly an ideal Beer’s Law
plot. (2m - Sep 2013)
• KMnO4 λ max = 525 nm
• 2.468 x 10-7 mol-1 L cm-1
1.3.3 THE SPECTRA
Continuous spectrum
Spectra in the visible region
Visible region

Continuous

Emission
or
Bright line

Absorption
or
Dark line
Types of spectra
✦ Line spectra (atomic absorption)-
consists of a series of sharp lines with
widths.

✦ Band spectra (molecular absorption) -

consist of a series of closely spaced
lines that are not fully resolved by the
instrument used to obtain the
spectrum.

✦ Continuous spectra (molecular

absorption) – consist of broad band.
Some typical UV absorption spectra
The absorption spectra
Electronic transition
• Changes in the distribution of outer electrons about
atoms or molecules
Molecular
→ *
Atomic
1.3.4 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
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
Emission of EMR

Type of spectra
Atomic species – line spectra
relatively narrow lines but still complex
• Several major electronic transition and sublevels
REFERENCES
• Skoog et. al., 2004. Fundamental of Analytical
Chemistry, 8th ed. Thomson Brooks/Cole. USA
• Skoog et. al., 2007. Principles of Instrumental
Analysis, 6th ed. Thomson Brooks/Cole. USA
• Higson, S.P.J., 2006. Analytical chemistry,
Oxford University Press. New York.
• CHM580 notes.