CHM260

CHAPTER 1

The study of the interaction between

ELECTROMAGNETIC (EM) RADIATION
and MATTER

covers

ATOMIC
SPECTROSCOPY

MOLECULAR
SPECTROSCOPY

(atomic absorption)

(molecular absorption)
3

What is Electromagnetic Radiation?

is a form of energy that has both Wave and
Particle Properties.
It is produced by oscillating electric and magnetic
disturbance, or by the movement of electrically
charged particles traveling through a vacuum or
matter.
For example: Ultraviolet, visible, infrared,
microwave, radio wave.

EM radiation is conveniently modeled as waves

consisting of perpendicularly oscillating electric and
magnetic fields, as shown below.

Direction of
propagation

At 90 to the direction of propagation is an oscillation in

the ELECTRIC FIELD.
At 90 to the direction of propagation and 90 from the
electric field oscillation (orthagonal) is the MAGNETIC
FIELD oscillation.

Period (p)
the time required for one cycle to pass a fixed point in
space.
Frequency (V @ f )
the number of cycles which pass a fixed point in space per
second. Unit in Hz or s-1
Amplitude (A)
The maximum length of the electric vector in the wave
(Maximum height of a wave).
Wavelength ()
The distance between two identical adjacent points in a
wave (usually maxima or minima).

 Wavenumber

()

The number of waves per cm in units of cm-1.

Radiant

Power ( P )

The amount of energy reaching a given area per second.

Unit in watts (W)
Intensity

(I)

The radiant power per unit solid angle.

Speed of light = Wavelength x Frequency

c = V

Where as
is the wavelength of the waves
V is the frequency of the waves
c is the speed of light

c = 3.00 x 108 m/s = 3.00 x 1010 cm/s

9

800 nm

Infrared radiation
V = 3.75 x 1014 s-1

Ultraviolet radiation
V = 7.50 x 1014 s-1

Wavelength is inversely proportional to frequency

1/V

The Higher the Frequency the Shorter the Wavelength and

vv.

10

EMR is viewed as a stream of discrete particles of

energy called photons.
We can relate the energy, E of photon to its
wavelength, frequency and wavenumber by

hc
E = hV =
= hc

h = Plancks constant
h = 6.63 x 10-34 J.s

11

hc
E = hV = hc =

Therefore wavenumber,

= 1/ = V/c

Unit of wavenumber is cm-1

What is the energy of a 500 nm photon?

V
V
E

= c/
= (3 x 108 m s-1)/(5.0 x 10-7 m)
= 6 x 1014 s-1 @ Hz
= hV
= (6.626 x 10-34 Js)(6 x 1014 s-1)
= 4 x 10-19 J

13

14

15

16

17

Spectral Properties, Application and Interactions of

Electromagnetic Radiation
Wave
Number V

Energy

Wavelength

Frequency

Type
Radiation

Kcal/mol
9.4 x 107

9.4 x 103

9.4 x 101

eV
4.9 x 106

4.9 x 102

4.9 x 100

cm-1

cm

Hz

3.3 x 1010

3 x 10-11

1021

3.3 x 106

3.3 x 104

3 x 10-7

3 x 10-5

Gamma
ray

1017

X-ray

1015

Ultra
violet

Type
spectroscopy

Gamma ray
emission

Electronic
(inner shell)

UV absorption

Electronic
(outer shell)

IR absorption

9.4 x 10-1

4.9 x 10-2

3.3 x 102

3 x 10-3

1013

Infrared

9.4 x 10-3

4.9 x 10-4

3.3 x 100

3 x 10-1

1011

Microwave

Microwave
absorption

Radio

Nuclear
magnetic
resonance

4.9 x 10-8

3.3 x 10-4

3 x 103

107

wave

Nuclear

X-ray
absorption,
emission

Visible

9.4 x 10-7

Type
Quantum Transition

Molecular
vibration Molecular
rotation

Magnetically
induced spin
states

Region

Wavelength Range

UV

180 380 nm

Visible

380 780 nm

Near-IR

780 2500 nm

Mid-IR

2500 50000 nm

Region

Unit

Definition (m)

X-ray

Angstrom unit,

10-10 m

Ultraviolet/visible

Nanometer, nm

10-9 m

Infrared

Micrometer, m

10-6 m

19

Spectral Distribution of Radiant Energy

Wave Number (cycles/cm)

X-Ray

UV
200nm

Visible
400nm

IR
800nm

Wavelength (nm)

Microwave

Douglas A. Skoog, et al. Principles of Instrumental Analysis, Thomson, 2007

21

Longest wavelength EM waves

Uses:

TV broadcasting
AM and FM broadcast radio
Avalanche beacons
Heart rate monitors
Cell phone communication

Wavelengths from 1 mm- 1 m

Uses:

Microwave ovens
Bluetooth headsets
Broadband Wireless Internet
Radar
GPS

Wavelengths in between microwaves and

visible light
Uses:
Night vision goggles
Remote controls
Heat-seeking missiles

Only type of EM wave able to be detected by

the human eye
Violet is the highest frequency light
Red light is the lowest frequency light

Shorter wavelengths than visible light

Uses:

Black lights
Sterilizing medical equipment
Water disinfection
Security images on money

Tiny wavelength, high

energy waves
Uses:

Medical imaging
Airport security
Inspecting industrial welds

Smallest wavelengths, highest energy EM

waves
Uses
Food irradiation
Cancer treatment
Treating wood flooring

Interactions of radiation with matter is to obtain the

information about a sample.
The sample is stimulated by applying energy in the
form of heat, electrical energy, light, particles, or a
chemical reaction.
The analyte is predominately in its lowest-energy or
ground state. The stimulus then causes some
analyte species to undergo a transition to a higherenergy or excited state.

In emission the analyte is stimulated by the

application of heat, electrical energy, or a chemical
reaction.
The energy required for the transition for analyte
from a lower energy state to a higher energy state is
directly related to the frequency of electromagnetic
radiation that causes the transition.
Information about the analyte can be obtained by: measuring the electromagnetic radiation emitted as
it returns to the ground state
or by measuring the amount of electromagnetic
radiation absorbed as a result of excitation.

Process involved in emission and chemiluminescence

spectroscopy

Absorption methods

Photoluminescence method
(Fluorescence and phosphorescence)

33

Absorption: A transition from a lower level to a higher level with transfer of

energy from the radiation field to an absorber, atom, molecule, or solid.
Emission: A transition from a higher level to a lower level with transfer of
energy from the emitter to the radiation field. If no radiation is emitted, the
transition from higher to lower energy levels is called nonradiative decay.

1.3.1 Radiation Absorption

This process transfers energy to the molecule and results in a
decrease in the intensity of the incident electromagnetic
radiation.
Absorption of the radiation thus attenuates the beam in
accordance with the absorption law.
Transmittance
Transmittance (T) is defined as the amount of light passing through the
sample solution (P) divided by the amount of incident radiation (Po).

Absorbance

Absorbance, A of solution is related to the transmittance in

logarithmic manner.
As the absorbance increases, transmittance decreases.

where I is the light intensity after it passes through the sample

and I o is the initial light intensity. The relation between A and T is:
A = -log T = - log (I / I o ).
36

The Beer-Lambert law (or Beer's law) is the

linear relationship between absorbance and
concentration of an absorbing species.

The amount of radiation absorbed may be measured in a number

of ways:
Transmittance, T = P / P0
% Transmittance, %T = 100 T
Absorbance,
The last equation, A = 2 - log10 %T , is worth
remembering because it allows you to easily calculate
A = log10 P0 / P
absorbance from percentage transmittance data.

A = log10 1 / T
A = log10 100 / %T
A = 2 - log10 %T

The relationship between absorbance and transmittance

is illustrated in the following diagram:
So, if all the light passes
through a solution without
any
absorption,
then
absorbance is zero, and
percent transmittance is
100%. If all the light is
absorbed, then percent
transmittance is zero, and
absorption is infinite.

A = ebc tells us that absorbance depends on the total quantity of the absorbing
compound in the light path through the cuvette. If we plot absorbance against
concentration, we get a straight line passing through the origin (0,0)

Note that the Law is not obeyed at high

concentrations. This deviation from the Law is not
dealt with here.

39

slit

cuvette

source
detector

A = -logT = log(P0/P) = ebc

T = Psolution/Psolvent = P/P0
Works for monochromatic light
Compound x has a unique e at different
wavelengths

A = bc
A is absorbance (no units, since A =
log10 P0 / P )
is the molar absorbtivity with units of L
mol-1 cm-1
b is the path length of the sample - that
is, the path length of the cuvette in which
the sample is contained. In cm
c is the concentration of the compound in
solution, expressed in mol L-1

Beers law also applies to solutions containing

more than one kind of absorbing substance.
Provided that there are no interactions among
the various species.
The total absorbance for a multicomponent
system is the sum of the individual
absorbances. In other words,
Atotal = A1 + A2 + An
= 1bc1 + 2bc2 + + nbcn
where the subscripts refer to absorbing
componets 1, 2, , n.

The linearity of the Beer-Lambert law is limited by chemical

and instrumental factors. Causes of nonlinearity include:

deviations in absorptivity coefficients at high concentrations (>0.01M)

due to electrostatic interactions between molecules in close
proximity.
scattering of light due to particulates in the sample.
fluoresecence or phosphorescence of the sample.
changes in refractive index at high analyte concentration.
shifts in chemical equilibria as a function of concentration.
non-monochromatic radiation, deviations can be minimized by using
a relatively flat part of the absorption spectrum such as the maximum
of an absorption band.
stray light = radiation from the instrument that is outside the nominal
wavelength band chosen for the determination.
43

Limits to Beers Law

There are few exception to the linear relationship
between absorbance and path length at a fixed
concentration. We frequently observe deviations
from
the
direct
proportionality
between
absorbance and concentration where b is a
constant. Some of these deviations, called real
deviations, are fundamental and represent real
limitations to the law. Others occur as a
consequence of the manner in which the
absorbance measurements are made or as a
result of chemical changes associated with
concentration changes. These deviations are
called instrumental deviations and chemical
deviation respectively.

Limitations (deviations) of Beers

Law

High concentration (close proximity of

molecules affects absorption)
Analyte dissociation to product with different
absorption
characteristics
(e.g.,
pHdependent indicators)

Polychromatic radiation (i.e., light of more

than one )

p'

P"0
Ameas log
P' P"
0

Where P and P are powers for and ,

respectively

Negative
deviation
=
lower
absorbance than predicted because
higher transmittance
Higher T because molecules dont
absorb one as well as other

 Stray

radiation

p'

Ps
A' log
P' Ps
0

Ps = power from stray radiation

Extra light hits detector
higher T; lower A

Absorption spectra

An absorption spectrum is a plot of absorbance

versus wavelength.
Absorbance could also be plotted against wave
number or frequency.
Occasionally, plots with log A as the ordinate
are used. A plot of molar absorptivity as a
function of wavelength is independent of
concentration.

Typical absorption spectra of potassium permanganate

at five different concentrations

51

52

A 7.25 x 10-5 solution of potassium

permanganate has a transmittance of 44.1%
when measured in a 2.10 cm cell at
wavelength of 525nm. Calculate
a) The absorbance of this solution
b) The molar absorptivity of KMnO4

53

a)
b)

A = -log T = -log 0.441 = 0.355

= A/bc
= 0.3554/(2.10 x 7.25 x 10-5mol L-1)
= 2.33 x 103 L mol-1cm-1

54

55

Electrons bound to
atoms have discrete
energies (i.e. not all
energies are allowed).
Thus, only photons of
certain energy can
interact with the
electrons in a given
atom.
Transitions between
electronic levels of the
electrons produce line
spectra.

56

Consider hydrogen, the

simplest atom.
Hydrogen has a specific
line spectrum.
Each atom has its
own specific line
spectrum (atomic
fingerprint).

57

For an electromagnetic radiation, at the

give wvlgth of 562 nm
i) calculate the frequency in Hz
Ii) Name the EMR at the given wvlgth
Iii) Determine the energy in (joules) of
this radiation

58

A spectroscopy experiment was

conducted using a 1.0 cm cuvette. The
molar absorptivity of MnO4- is 2.3 x 103
M-1cm-1.
i)
Calculate the conc of permanganate
solution which would give an
absorbance 0.8
ii)
Calculate the % transmittance of
solution in (i)
iii) Solution (i) is diluted to half of its
original conc. Calculate the
transmittance of the diluted solution
59

Partial energy level diagram

for sodium.
Involve excitation from ground
state to higher state.
Occurs by absorption of
photon of radiation
Transitions between two
different orbitals are termed
electronic transition.
Atomic absorption is measured
at a single wavelength using a
very narrow, nearly
monochromatic source.
60

The energy of photon that can promote electrons

to excite/jump to a higher energy level depends
on the energy difference between the electronic
levels.

61

Each atom has a specific set of energy levels, and

thus a unique set of photon wavelengths with which
it can interact.

62

Absorption and emission

for the sodium atom in the
gas phase.
The diagram illustrate the
transitions (excitation and
emission) of electrons
between different energy
levels in sodium atom.

Etransition = E1 - E0 = hv = hc/

63

The energy, E, associated with the molecular bands:

Etotal = Eelectronic + Evibrational + Erotational

In general, a molecule may absorb energy in 3 ways:

1. By raising an electron (or electrons) to a higher
energy level. (electronic)
2. By increasing the vibration of the constituent
nuclei. (vibrational)
3. By increasing the rotation of the molecule about
the axis. (rotational)

hn

En

En

hn

Eo

hn

Eo

Absorption

Emission

Rotational
absorption

Vibrational
absorption

67

Absorption spectrum
A plot of the absorbance as a function of
wavelength or frequency.
Emission spectrum
A plot of the relative power of the emitted
radiation as a function of wavelength or
frequency.

68

Absorption Spectrum of Na

The two peaks arise from the promotion of

a 3s electron to the two 3p states

69

Electronic Transition

Vibrational Transition
Superimposed on the
Electronic Transition

Absorption Band
A series of closely
shaped peaks

70

In solvents the rotational

and vibrational
transitions are highly
restricted resulting in
broad band
absorption spectra.

71

Three types of
spectra:
Lines
Bands
Continuum
spectra
Emission spectrum of a brine sample
72

Emission
X*

X + h

Excitation needs energy!

Particle bombardment (e-)
Electrical currents (V)
Fluorescence
Heat

73

 Made up of a series of sharp, welldefined peaks.

Caused by excitation of individual
atoms.
Atomic transitions are usually very
discrete changes of electrons from one
quantum state to another energy level
(shells, spins, etc).
Only electronic transition is quantized
No vibrational or rotational transition.

Individual atoms, well separated, in a gas phase

74

 Encountered in spectral
sources when gaseous
radicals or small molecules
are present.
Molecular transition
consists of 3 processes:
i) Rotational transition
ii) Vibrational transition
iii) Electronic transition
E = Eelectronic + Evibrational +
E rotational

Band spectra is produced

due to vibrational and
rotational transitions.

Small molecules and radicals

75

Continuum spectra: A beam of light that contains a

broad, smooth distribution of photon wavelengths.
Produced when solid are heated to incandescence.
Blackbody Radiation (Thermal Radiation)

Line spectra

Band spectra

Continuum spectra