Chapter 11:

Introduction to Spectroscopy
• Spectroscopy is the study of the interaction of
light or electromagnetic radiation with matter.

• Interaction of light involves either absorption,

emission, or scattering of electromagnetic
radiation by the system.
• EM radiation is conveniently modeled as waves consisting of
perpendicularly oscillating electric and magnetic fields, as shown
below.

o At 90° to the direction of propagation is an oscillation in the

ELECTRIC FIELD.

o At 90° to the direction of propagation and 90° from the electric

field oscillation (orthagonal) is the MAGNETIC FIELD oscillation.
y

x
z Electric Field

Magnetic Field

Direction of
propagation
 Wave Parameters
 Period (p) – the time required for one cycle to pass a fixed point in space.

 Frequency (V) – the number of cycles which pass a fixed point in space per
second.

 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.

 Relationship Between These Variables

Speed of light = Wavelength x Frequency

• c = V
•  = c/V
• V = c/

For Electromagnetic Waves the Speed (c) is a Constant

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

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 Interaction of electromagnetic radiation with matter
 The interaction of radiation with matter can cause redirection of the
radiation and/or transitions between the energy levels of the atoms
or molecules.

1. A transition from a lower level to a higher level with transfer of

energy from the radiation field to the atom or molecule is called
absorption.

2. A transition from a higher level to a lower level is called emission

if energy is transferred to the radiation field, or nonradiative decay
if no radiation is emitted.

3. Redirection of light due to its interaction with matter is called

scattering, and may or may not occur with transfer of energy, i.e.,
the scattered radiation has a slightly different or the same
wavelength. 7
 Types of spectra
1. Absorption spectrum
2.Emission spectrum

• 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.
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 UV-Visible Absorption Spectroscopy
Absorption of UV and visible light by a molecule causes
electronic excitation

• Violet:   400 - 420 nm

• Indigo:   420 - 440 nm

• Blue:   440 - 490 nm
• Green:   490 - 570 nm
• Yellow:   570 - 585 nm
• Orange:  585 - 620 nm
• Red:   620 - 780 nm
 Electromagnetic Spectrum
Type of Frequency Wavelength
Type of Transition
Radiation Range (Hz) Range
gamma-rays 1020-1024 <1 pm nuclear
X-rays 1017-1020 1 nm-1 pm inner electron
ultraviolet 1015-1017 400 nm-1 nm outer electron

visible 4-7.5x1014 750-400 nm outer electron

2.5 µm-750 outer electron molecular

near-infrared 1x1014-4x1014
nm vibrations
infrared 1013-1014 25 µm-2.5 µm molecular vibrations
molecular rotations,
microwaves 3x1011-1013 1 mm-25 µm
electron spin flips*
radio waves <3x1011 >1 mm nuclear spin flips*
 Absorption laws
Beer-Lambert Law (Beer's law)

Consider a beam of light with an (initial) radiant intensity I0

The light passes through a solution of concentration, c

The path length is b
The intensity of the light after passage through the solution is I
Transmittance is given by the equation:
T = I/Io
where I is the intensity of the light after it has gone
through the sample & Io is the initial light intensity.

Absorbance is related to the %T:

A = -log T = -log(I/ Io)
 Absorbance
Beer-Lambert Law (a.k.a. Beer's law) - The fraction of the
incident light absorbed by a solution at a given wavelength is related
to
a. thickness of the absorbing layer (path length) and
b. concentration of the absorbing species

The linear relationship between absorbance and concentration of an

absorbing species.
A = ebc
A is the absorbance
“e” is molar absorptivity in L/[(mole)(cm)]
“b” is the path length in cm
“c” is the concentration of the analyte
(sample) in mol/L
 “e” or molar absorptivity (1/M.cm)

It is sometimes called “extinction coefficient”

A wavelength dependent constant for the species being analyzed
“” is also used in some texts for “a”.

“b” or path length (cm)

The diameter of the cuvette or sample holder which is the distance

the light travels through the absorbing sample.
Becomes a constant when the same cuvette is used for all samples

“c” or concentration (M or mol/L)

Generally the main use of Beer’s Law is to determine the

concentration of various solutions
 Components of Optical Instruments
General Designs of Optical Instruments:

Spectroscopic instruments that were developed for use in the visible region
are optical instruments.

Optical spectroscopic methods are based upon six phenomena namely,

(1) Absorption
(2) Emission
(3) Fluorescence
(4) Scattering
(5) Phosphorescence and
(6) Chemiluminescene

Although the instruments for measuring each differ somewhat in

configuration, most of their basic components are remarkably similar.
 Five Basic Optical Instrument Components
1) Source - A stable source of radiant energy at the desired wavelength (or 
range).
2) Sample Holder - A transparent container used to hold the sample (cells,
cuvettes, etc.).

3) Wavelength Selector - A device that isolates a restricted region of the EM

spectrum used for measurement (monochromators, prisms, & filters).

4) Photoelectric Transducer - (Detector) Converts the radiant energy into a

useable signal (usually electrical).

5) Signal Processor & Readout - Amplifies or attenuates the transduced signal

and sends it to a readout device such as a meter, digital readout, chart recorder,
computer, etc.

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 COMPONENTS OF THE SPECTROMETER

Absorption (UV-Vis)

b
Po P
Light Wavelength
sample detector readout
source Selector

4
 Atomic Absorption Spectroscopy (AAS)

BASIC PRINCIPLE

ATOMIC ABSORPTION SPECTROSCOPY (AAS)

is an analytical technique that measures the concentrations of
elements.

It makes use of the absorption of light by these elements in

order to measure their concentration.

The technique uses basically the principle that free atoms (gas)
generated in an atomizer can absorb radiation at specific frequency.
Atomic Absorption Spectroscopy (AAS)

- Atomic absorption spectroscopy quantifies the absorption of

ground state atoms in the gaseous state .

- The atoms absorb ultraviolet or visible light and make

transitions to higher electronic energy levels . The analyte
concentration is determined from the amount of absorption.

- Concentration measurements are usually determined from a

working curve after calibrating the instrument with standards of
known concentration.

- Atomic absorption is a very common technique for detecting

metals and metalloids in environmental samples.
 Atomic Emission Spectroscopy (AES)
Atomic emission spectroscopy is also an analytical technique that is
used to measure the concentrations of elements in samples.

It uses quantitative measurement of the emission from excited atoms

to determine analyte concentration.

The analyte atoms are promoted to a higher energy level by the

sufficient energy that is provided by the high temperature of the
atomization sources.

The excited atoms decay back to lower levels by emitting light.

Emissions are passed through monochromators or filters prior to

detection by photomultiplier tubes.

In atomic Emission the sample is atomized and the analyte atoms are
excited to higher energy levels all in the atomizer.
 INFRARED SPECTROSCOPY

A molecule may absorb light energy in three

ways:
[1] Increasing the rotation of molecule around its axis
(rotational)
when molecule absorb F-IR irradiation.
[2] Increasing the vibration of constituent nuclei (vibrational)

when molecule
[3] Raising absorb
an electron to a IR irradiation.
higher energy level (transitional
energy)
when molecule absorb visible and UV light.
E total = E transitional + E vibrational + E rotational
 Infrared radiations

Region Wavelength Wave number, 

range,  (cm─1)
(µm)
Near 0.78 ─ 2.5 12,800 ─ 4000
Middle 2.5 ─ 50 4000 ─ 200
Far 50 ─ 1000 400 ─ 10
Most used 2.5 ─ 15 4000 ─ 670

Wavenumber ( ) is the reciprocal of the wavelength () in

cm
 = number of waves per centimeter = 1/ 
The region of 2.5 – 15 µm correspond to 4000 – 666 cm ─1
Advantage of wave number : direct proportion to the energy;
4000 cm ─1 is highest energy and 666 cm─1 is the lowest
energy.
 Instrumentation

1. Radiation source 2. Monochromator

3. Solvents, sample cells, samples 4. Readout / Recorder

Schematic diagram of a double beam double-grating infrared

spectrophotometer