Electronic Radiation

► The sun produces a full spectrum of

electromagnetic radiation
Two Components of EM Radiation
► Electrical field (E): varies in magnitude in a
direction perpendicular to the direction of
propagation

► Magnetic field (M): at right angle to the electrical

field, is propagated with the electrical field
Components of EM Radiation
 Three Properties of EM Energy
► Wavelength (l)
► Frequency (n)
► Amplitude
 Wavelength (l)
► The distance from one wave crest to the next
► Measurement units: micrometer (mm)
1m = 1,000 mm, 1mm = 1,000microm

l
 Frequency (n)
► The number of crests passing a fixed point
in a given period of time
► Measure units: hertz (cycle per second)

n
 Amplitude
► The height of each peak
► Measured as watts per square meter (energy
level)
 Speed of EM
► The speed of EM
► c= 300,000km/second,
► c = nl
l and n are inversely related
 Electromagnetic Spectrum
► Spectrum of electromagnetic radiation
► Major divisions of EM spectrum
 Major Divisions of EM Spectrum
► Ultraviolet spectrum: 0.3 - 0.38microm
► Visible spectrum:
- blue 0.4 - 0.5microm
- green 0.5 - 0.6microm
- red 0.6 - 0.72microm
► 1m = 1,000mm = 1,000,000 micrometer
Major Divisions of EM Spectrum
► Infrared spectrum:
- near infrared: 0.72 - 1.3microm
- mid infrared: 1.30 - 3.0microm
- far infrared: 7.00 - 15microm,
► Microwave spectrum: 1mm - 1m
 The Dual Nature of Light (Newton)
► Light is formed by a stream of quanta (photons)
that travels in straight line. The size of each
quantum is directly proportional to the frequency
of the energy's radiation
Q = hn
► The quantum model best explains the
photoelectric effect

► (Photon: tiny, particle-like bundles of radiation)

 The Dual Nature of Light
► EM energy propagates as a series of waves

► The wave model best explains the refraction and

diffraction
 INFRARED
SPECTROSCOPY
THE ELECTROMAGNETIC SPECTRUM
high Frequency (n) low
high Energy low

X-RAY ULTRAVIOLET INFRARED MICRO- RADIO FREQUENCY

WAVE

Nuclear
Vibrational
Ultraviolet Visible magnetic
infrared
resonance
2.5 mm 15 mm 1m 5m
200 nm 400 nm 800 nm
BLUE RED

short Wavelength (l) long

Types of Energy Transitions in Each Region
of the Electromagnetic Spectrum

REGION ENERGY TRANSITIONS

X-ray Bond-breaking
UV/Visible Electronic
Infrared Vibrational
Microwave Rotational
Radio Frequency Nuclear and
(NMR) Electronic Spin
 Simplified Infrared Spectrophotometer
NaCl
focusing plates
mirror
Detection Electronics
and Computer

Determines Frequencies
of Infrared Absorbed and
Infrared
plots them on a chart
Source

Infrared
Sample Spectrum

intensity of
Absorption absorption
“peaks”
frequency
(decreasing)
DIPOLE MOMENTS
 DIPOLE MOMENTS
Only bonds which have significant dipole moments will
absorb infrared radiation.

Bonds which do not absorb infrared include:

• Symmetrically substituted alkenes and alkynes

R R
R C C R
R R
• Many types of C-C Bonds

• Symmetric diatomic molecules

H-H Cl-Cl
 STRONG ABSORBERS

The carbonyl group is one O

- d
of the strongest absorbers d+
C

Also O-H and C-O bonds O H C O

infrared beam
C C
+ + d+
O
O
- - d-
 RAMAN SPECTROSCOPY

Another kind of vibrational spectroscopy that

can detect symmetric bonds.

Infrared spectroscopy and Raman spectroscopy

complement each other.
 RAMAN SPECTROSCOPY
In this technique the molecule is irradiated with
strong ultraviolet light at the same time that the
infrared spectrum is determined.

Ultraviolet light promotes electrons from bonding

orbitals into antibonding orbitals. This causes
formation of a dipole in groups that were formerly
IR inactive and they will absorb infrared radiation.

p* d+ . d- induced
dipole

R C..C R
hn
R C C R
.
UV
p p* absorbs IR
no dipole transition
symmetric
….. we will not talk further about this technique
 HARMONIC OSCILLATOR

MATHEMATICAL DESCRIPTION
OF THE
VIBRATION IN A BOND

…. assumes a bond is like a spring

 force
HOOKE’S LAW
constant
compress

K stretch

Dx

x0 x1
restoring
force = -F = K(Dx)

Molecule
as a
Hooke’s
m1 m2
Law
device
K
THE EQUATION OF A
n= frequency
in cm-1
SIMPLE HARMONIC
OSCILLATOR

c = velocity of light

( 3 x 1010 cm/sec )

1 K
n = 2 pc m
K= force constant
in dynes/cm

where

m1 m2 C C > C C > C C
m = multiple bonds have higher K’s
m1 + m2
m = atomic masses
This equation describes the
vibrations of a bond. m = reduced mass
 larger K,
higher frequency

1 K
n = 2pc m larger atom masses,
lower frequency

constants increasing K

= > C=C > C-C

C=C
2150 1650 1200

increasing m
C-H > C-C > C-O > C-Cl > C-Br
3000 1200 1100 750 650
THE UNIT USED ON AN IR SPECTRUM IS
WAVENUMBERS ( n )
n = wavenumbers (cm ) -1

1
n = l(cm) l = wavelength (cm)

c = speed of light
n = frequency = nc c = 3 x 1010 cm/sec

or

1 c cm/sec 1
n =( ) c = =
l l cm sec

wavenumbers are directly proportional to frequency

Typical Infrared Absorption Regions
(stretching vibrations)

WAVELENGTH (mm)
2.5 4 5 5.5 6.1 6.5 15.4

O-H C-H C N C=O C=N C-Cl

Very C-O
N-H C C few C=C
C-N
X=C=Y bands C-C
(C,O,N,S) N=O N=O *

4000 2500 2000 1800 1650 1550 650

FREQUENCY (cm-1)
* nitro has
two bands
 Definition of Infrared
Spectroscopy
► The absorption of light, as it passes through a
medium, varies linearly with the distance the light
travels and with concentration of the absorbing
medium.
► Where a is the absorbance, the Greek lower-case
letter epsilon is a characteristic constant for each
material at a given wavelength (known as the
extinction coefficient or absorption coefficient), c is
concentration, and l is the length of the light path,
the absorption of light may be expressed by the
simple equation
► a= epsilon x c x l.
 Infrared Spectroscopy
► Infrared spectroscopy is the measurement of the
wavelength and intensity of the absorption of mid-infrared
light by a sample. Mid-infrared is energetic enough to
excite molecular vibrations to higher energy levels.

► The wavelength of infrared absorption bands is

characteristic of specific types of chemical bonds, and
infrared spectroscopy finds its greatest utility for
identification of organic and organometallic molecules.
 Theory of Infrared Absorption
Spectroscopy
► For a molecule to absorb IR, the vibrations or rotations
within a molecule must cause a net change in the dipole
moment of the molecule. The alternating electrical field of
the radiation interacts with fluctuations in the dipole
moment of the molecule.

► If the frequency of the radiation matches the vibrational

frequency of the molecule then radiation will be absorbed,
causing a change in the amplitude of molecular vibration.
Stretching and Bending
Stretching Vibrations
Bending Vibrations
 Infrared Instruments
► An infrared spectrophotometer is an instrument that
passes infrared light through an organic molecule and
produces a spectrum that contains a plot of the amount of
light transmitted on the vertical axis against the
wavelength of infrared radiation on the horizontal axis.
► In infrared spectra the absorption peaks point downward
because the vertical axis is the percentage transmittance of
the radiation through the sample.

► Significance
► Since all bonds in an organic molecule interact with
infrared radiation, IR spectra provide a considerable
amount of structural data.
 KETONE
4-Methyl-2-pentanone
C-H < 3000, C=O @ 1715 cm-1

100
100
%

T 80
80
R
A
N 60
S 60
M
I 40
T 40
T
A
N 20 CH3 O
20
C
E
0
CH3 CH CH2 C CH3
0

3500 3000 2500 2000 1500 1000 500

WAVELENGTH (cm-1)

AN INFRARED SPECTRUM