CET2BAT-Analyt Chem 3

The Electromagnetic Spectrum

Lecture 2
24 July 2019
 Electromagnetic Spectrum
Properties of Light:
• Light is described in terms of particles and
waves.
Wave Properties
• Light waves consist of perpendicular
oscillating electric and magnetic fields as
shown in the diagram on the next slide
Diagram: Light waves consisting of perpendicular
oscillating electric and magnetic fields
·Frequency (ν) is the number of complete oscillations that the
wave makes. Unit of frequency is Hertz (Hz).
1 Hz = one oscillation per second (s-1).
·Wavelength (λ) is the crest-to-crest distance between waves.
A frequency of 106 Hz is called Megahertz (MHz)

·Relationship between frequency and wavelength

νλ=c (1)
Where; c = 2.998 x 108 m/s speed of light in a vacuum.
Speed of light in media other than vacuum is given by c / n
c= speed in vacuum and n= refractive index of that medium.
n = ci /vi
ci =speed of radiation in vacuum to that in the substance
vi = speed of radiation in the substance (medium)
Behaviour of Light as Particles (Photons)-
Quantum theory
·According to quantum theory light is made up of particles called
photons. Each photon carries a definite amount of energy (E)
as shown by the following relationship
E=h ν (2)
E =energy in Joule (J); ν is frequency in s-1 and h= planck's
constant, 6.626x10-34 J.s
Combining the two equations (1) and (2)
E= h ν = = h ū c (3)

1/ λ = ū, wave number in m-1 or cm-1

SI Units: E=J h= J.s; c = ms-1 λ = m

ū = m-1; ν = Hz or ν = s-1
 Electromagnetic radiation spectrum: Different regions

Regions Cosmic rays Gamma rays X-ray Ultra- V Infrared Micro-wave Radio-
violet frequen
Energy (J) >1.2x1011 1.2x1010 1.2x107 3.1x105 5
i 1.2x10 to 1.5x10
5
1.2x102 to <1.2
to 1.2x1011 to 1.2x1010 to 1.2x107 1.2x105
Absorptio Very high Nuclear Bond Transition s Molecular Rotations Electron Nuclear
n/ energy transitions/ breaking/ of valency & vibrations spin spin
Reactions rays decay ionization electrons transitions transitio
(NMR)
Frequency 5x1019 5x1016 1015 i 1011 107
Hz or (s-1) >1021 to 5x1021 to 5x1019 to 5x 1016 to 5 x1014 to 1011 <107
Waveleng <10-12 10-12 to 10-11 10-11 to 10-8 10-8 to b 10-6 to 10-3 10-3 to 10-1 >-10-1
th(m) 6.5x10-6

l
e
 Visible radiation spectrum
The visible spectrum spans the wavelength range 380-780nm
(1nm = 10-9m) commonly indicated as 400-800nm.

Violet Indigo Blue Green Yellow Orange Red ?? Purple ??

<400 430 450 500 550 600 650 680 740 800
Refer to page 513 D.C. Harris Quantitative analysis, 5th Edition

Wavelength = Energy =
0.4 x10-6 to 0.8x10-6 m 1.5x105 to 3.1x105J/mol

Frequency =
5 x1014 to 5x1016 Hz
Colours of visible Light:

Wavelengh of colour absorbed colour abserved Wavelength

maximum Range

absorbance

380-420 Violet Green- Yellow 520-550

420-440 Violet -Blue Yellow 550-5580

(Indigo)

440-470 Blue Orange 580-620

470-500 Blue-Green Red 620-680

500-520 Green Purple 680-780

520-550 Yellow-Green Violet 380-420

550-580 Yellow Violet-Blue 420-440

580-620 Orange Blue 440-470

620-680 Red Blue-Green 470-500

680-780 Purple (reddish- Green 500-520

purple) Magenta
 Absorption and Emission of light
Absorption of light increases the energy of a molecule.
Emission of light decreases its energy.
·When a molecule absorbs a photon, an electron is
promoted to an excited state of molecular orbitals.
·If a molecule emits a photon, the energy of the molecule is
lowered. An electron jumps from high-energy molecular
orbital to a lower energy molecular state.
·The lowest state of a molecule is called the ground state.
 Different types of Analytical spectroscopic Techniques

1) Radio Frequency (RF)-NMR Techniques

(Energy <0.1 J/mol; ν = 10-600 MHz; λ = 50cm to 30m)
•This region includes Nuclear Magnetic Resonance (NMR)
techniques.
•Absorption of RF radiation results in changes in the
orientation of spinning nuclei in a magnetic field.
•RF techniques are used for structural analysis of organic
compounds. Examples: 1H, 2H and 13C nuclei.

•All nuclei are assigned a Spin Quantum Number or

Angular momentum, I.
I can be zero, half or integral = 0, ½,-½,1,-1,-2, 2, etc.

•The nucleus also possesses dipole moment, μ.

•Energy changes are associated with orientation of the
nuclear axis in space relative to an external magnetic field.

•Only those nuclei with non-zero I values can give rise to

NMR spectrum.
•As the nucleus carries a charge, spinning about its own
axis produces a magnetic moment or dipole, μ along the
nucleus axis (μ = charges x distance between them).

•The amount of energy that a nucleus absorbs is

determined by I and μ values.

•Instruments used to record NMR spectrum are called

NMR instruments.
2) Microwave techniques
(Energy 1.2- 120J/mol; ν = 5x107-1011 Hz; λ = >10-3 -10-1 m)

·The energy changes involve absorption of radiation of

wavelength λ =10-3 -10-1m or frequency, ν = 5x107-1011 Hz.

·Absorption of microwave radiation stimulates rotational

motion of molecules.

·Instruments used are called microwave radiation

spectrometers.
3) Infra Red (IR) Radiation Technique:
(E= 120- 1.5x105J/mol; ν = 1011-5x1014 Hz; λ =10-6 -10-3 m)
·IR technique is used for the identification and structural analysis of
mainly organic compounds and selected metal oxides.

·Infrared radiation causes the vibration of the molecules e.g, O 2 , CO,

CO2.
·Instruments for IR measurements are called IR-spectrophotometers.

·Example - stretching vibrations and bending of bond angle)- e.g C=O

in different compounds can be identified using the wavenumber (⊽) of
the carbonyl group, C=O e.g
·Ketones C=O stretches at 1710-1720cm-1
·Carboxylic acid C=O stretches at 1750-1770cm-1:
Molecular
o-Quinone C=O stretches at 1680-1700cm-1 .
Vibrations
4) Visible Light Spectrophotometry:
(E= 1.5x105 - 3.1x105J; ν = 5x1014-1015 Hz; λ = 400-800 nm).
•Instruments used for analysis in the visible region are called
colorimeters or visible light spectrophotometers.

·The visible radiation causes electrons to be promoted from ground

state to higher energy levels of molecular orbitals.

5) Ultra-Violet Radiation Spectrophotometry

(E= 3.5x105-1.2x107 J; ν = 5x1015-5x1016 Hz; λ = 10-8 -6.510-6 m).
·The radiation cause electrons to be promoted from ground state to
higher energy states of molecular orbitals.
(Energy is higher than in Visible light)
·UV Instruments are called UV- spectrophotometers.
·Most modern UV-Spectrophotometers do measurements in both
Visible and UV- regions i.e UV-Visible spectrophometers.
6) X-ray Radiation:
(E= 1.2x107-1.2x1010 J/mol; ν = 5x1017-5x1019 Hz; λ = 10-11 -10-8 m).
·Transitions of inner shell electrons.
·The radiation breaks chemical bonds and ionizes molecules.
·Example: Medical X-rays to analyse defects in body tissues.
·Instruments used are called X-ray spectrometers.

7)Gamma or γ-ray techniques

(Energy 3.5x1010-1.2x1011 J; ν = 5x1019-5x1020 Hz; λ = 10-12 -10-11 m).
·The radiation involves electron transitions within the inner shells of an
atom such as nuclear reaction used in radio-chemical methods.

·Application of this technique is in biochemistry and medicine.

Assessment of pollution by radio-nucleus.

·Instruments used are called Gamma or γ-Ray Spectrometers.

8) Cosmic rays:
(E= >1.2x1011 J; ν = >5x1020 Hz; λ = <10-12 m).
·These are very high energy radiation.
·Highly destructive to matter.
·Involve Nuclear Transitions.
·Not very common are of little use for analytical
purposes.
CALCULATIONS ON PHOTON ENERGIES
Question
(i) By how many Kilojoules (KJ) per mole is the energy of oxygen (O 2) increased
when it absorbs ultraviolet radiation with a wavelength of 147nm?
(ii) By how much is the energy of carbon dioxide (CO2) increased when it absorbs
infrared radiation with a wavenumber of 2300cm-1 .
Answer
i) Oxygen molecule absorbing UV radiation
For 1 molecule
ΔE= hυ =h c/λ λ = 147nm c = 2.988 x 108m.s-1 h = 6.626x10 -34 J.s
= (6.626 x 10-34 J.s) x (2.998x108 m/s) / [(147nm)(10-9 m/nm)]
= 1.35 x 10 -18 J/molecule.
For 1 mole of molecules
ΔE = (1.35 x 10 -18 J/molecule) (6.022x10 23 molecule / mol)
= (812970J/mol) (KJ/10 3 J = 813KJ/mol

•Therefore, 813 KJ per mol of oxygen molecules is the energy

required to break the O=O bond of oxygen molecule (O2 ) when UV
light at λ = 147nm is absorbed.
ii) Carbon dioxide molecule absorbing Infrared radiation
For one molecule
ΔE= hυ =h c (1/λ)=h c ⊽ (1/ λ =⊽= 2300cm -1)
= (6.626x10 -34J.s) (2.998x108m/s) x(2300cm-1) (100cm/m)
= 4.568892 x 10-20 J/molecule.
= 4.57 x 10-20 J/molecule
For one mole of carbon dioxide
ΔE=(4.568892x10-20 J/molecule) (6.022x10 23 molecules/mol) (KJ/103J)
= (27.51386786KJ/mol)
= 27.51KJ/mol
·This implies that infrared absorption increases the amplitude of the
vibrations of the carbon dioxide, CO2 molecule.
DETECTORS FOR DIFFERENT REGIONS OF
ELECTROMAGNETIC REGIONS
Detector-the beam emerging from the sample with radiant power P is
compared to the radiant power, Po emerging from the reference
solution. The simplest detector employed in the visible region is a
photovoltaic cell. Current is produced when radiation falls on a layer
on a layer of a semiconductor material, e.g selenium, sandwiched
between two metal electrodes, is proportional to the power of the
incident radiation and can be monitored by a galvanometer.
i) Another device used as a detector is photoelectric cell or vacuum
phototube. Electrons dislodged when radiation strikes the surface
of a sensitive photocathode are collected by an anode and
constitute a current that is proportional to the radiation intensity.
An example of a high sensitivity detector in the UV-Vis region is a
photomultiplier tube that contains up to 16 electrodes (dynodes).
The latter is very important in signal amplification and makes the
detector to have highly sensitive frequency.
. Other detectors
i) Diode array detectors which consists of integrated circuit
(IC) chips incorporating up to 100-200 pairs of photodiodes
and capacitors. Each photodiode has dimensions of about
0.05 x 0.5mm and is sensitive to radiation over a wide range
of wavelengths e.g 200-800nm.
ii) For IR instruments, thermal detectors and photon detectors
can be used. Thermal detectors depend on heating of IR
radiation producing a temperature sensitive response.
Photon detectors are more sensitive and have a more rapid
response. They are semiconductor materials made of
substances such as mercury, cadmium, telluride (MCT)
which at liquid nitrogen or helium temperatures, generate a
voltage according to the energies of the incident photons of
infrared radiation.
i) Radiations such as X-rays, and γ-rays
outside the UV-Vis and IR regions, cannot be
detected by the conventional photoelectric
detectors.
ii) X-rays and γ-rays are detected by gas
ionization or solid state ionization.

iii) For radiowave and microwave regions, the

radiation is essentially monochromatic, and
detection is by radio-receiver tuned to the
source
VISIBLE AND ULTRAVIOLET
SPECTROPHOTOMETERS (λ = 10-8 - 10-6 m)
·Spectrophotometers specifically for absorption in visible
region are called colorimeters
·Usually the sample is in liquid form and is contained in a
cuvette (mostly ~ path length=1.00cm).
·The cuvette is made of fused silica. The cuvets are sold in
pairs for both sample & reference/blank solutions.
·Glass cuvettes are only restricted for use with colorimeters
but are unsuitable for UV- instruments because glass absorbs
in the UV-region.
See Figure 19.5 page 518-Quantitaive
Analysis 5th Edn by
Harris for different designs of cuvettes.
INFRARED SPECTROPHOTOMETERS (λ = 10-6 - 10-3
m; ⊽=10-10,000cm-1 )
·The sample holders are commonly known as cells,
constructed of NaCl or KBr. Mainly, solid samples are
analyzed.
·The solid sample is first ground to a fine powder and then
mixed with mineral oil called Nujol (liquid paraffin C 10H22)
to form a dispersion or a mixture known as mull. The mull is
pressed between KBr plates as the sample holder during
absorbance measurements.
·Liquid samples can also be used either in solution form or
neat. The liquid sample is sandwiched between two plates of
KBr or NaCl. Solvents commonly used to dissolve the
sample are carbon tetrachloride, chloroform and carbon
disulfide.
 Class Activity 2

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