Electromagnetic Radiation

Spectroscopy
Spectroscopy deals with the interaction of electromagnetic radiation (EMR) with matter.

For example the absorption of visible light by a solution

The amount of light absorbed depends on the colour or wavelength of the light and the concentration of the solution Spectroscopy can be used to identify compounds by studying the absorbance versus wavelength plots (spectrum)

Spectroscopy can be used to analyse the concentration of a solution by measuring the amount of light absorbed
There are other types of interactions of EMR with matter e.g. fluorescence, scattering, photo-electron emission
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Interactions of EMR with Matter

Absorption no re-emission energy dissipated as heat
Absorption/Re-emission if the same wavelength is
emitted then it is called light scattering

Absorption/Re-emission if different wavelength

then it is called fluorescence or phosphorescence

Reflection from Surfaces mirror, special geometry Photoemission of Electrons EMR detectors
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Types of Electromagnetic Radiation (EMR) 1. Visible light colours (VIBGYOR) 2. Infrared radiated heat 3. Ultraviolet sunburn 4. X-rays - medicine 5. g-rays cancer therapy
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Dual Nature of EMR

Electromagnetic radiation has properties that can be described in terms either: 1. A wave train consisting of oscillating electric and magnetic fields travelling through space
e.g. interference patterns, diffraction

2. A stream of particles (photons)

e.g. absorption and emission spectroscopy photoemission of electrons from metals5

EMR as a Wave

(a)

(b)

EMR as a Wave

(a)

EMR as a Wave

(b)

Wavelength and Wavenumber

Wavelength (l in m) is the distance travelled during a complete oscillation of the wave

Wavenumber (n in m-1) is the reciprocal of wavelength

- =1/l n

EMR can be Described by a Sine Wave

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Period and Frequency

Period (T in s) is the time for a complete oscillation Frequency (n in s-1 or Hertz i.e. Hz) is the number of oscillations per second

n = 1/T
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Velocity of EMR

The velocity of EMR (c in m s-1) in a given medium is constant irrespective of the wavelength or frequency

In vacuum
And

c = 3.00 x 108 m s-1

c = l/T = ln
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Effect of Medium on EMR

Air

Water

Air

Frequency remains constant

Velocity decreases with refractive index

Wavelength decreases with RI
since during one oscillation the wave travels a shorter distance in water than in air
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Einsteins Interpretation of the Photoelectric Effect

EMR can eject electrons from certain materials but only if the frequency is above a given threshold

Einstein argued that this must mean EMR consists of a stream of particles (now called photons) and the energy of a photon depends on the frequency of the EMR For electrons to be emitted the photon energy must exceed the work required for the electron to escape from the material
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EMR as a Particle
EMR consists of a stream of particles called photons The energy of a photon (E in J photon-1 or J mol-1) is

E = hn
Or

(J photon-1 ) (J mol-1 )

E = hn N 0

Planks constant h = 6.63x10-34 J s Avagadros number N0 = 6.02x1023 mol-1

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Intensity of EMR
Intensity is the energy transmitted through unit area at right angles to the beam per second It is the energy per photon (Ephoton ) times the number of photons passing unit area per second (N)

I = Ephoton x N
=hnN

Units J m-2 s-1

Unit Area

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The type of EMR depends on wavelength, frequency, energy,etc

n
n n n
3x1012 3x1014 Hz 100 mm 800 nm
3x1014 6x1014 Hz 800 nm 400 nm 6x1014 3x1016 Hz 800 nm 10 nm 3x1016 3x1018 Hz 10 nm 100 pm
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Infrared -

Visible light -

l
l l

Ultraviolet -

X-rays -

Absorption or emission of specific types of EMR cause changes in different kinds of atomic or molecular energy

1. Microwave - molecular rotation

2. Infrared molecular vibration

3. Visible light outer shell electrons 4. Ultraviolet outer valence electrons

5. X-rays inner shell electrons

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The type of EMR depends on wavelength, frequency, energy,etc Absorption or emission of specific types of EMR cause changes in different kinds of atomic or molecular energy

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The EMR Spectrum

Electronic excitation Bond breaking and ionization Vibration Rotation

Cosmic rays

Visible

g-rays

X-rays

UV

Infrared

Microw ave

Visible Spectrum

400

500

600

700

Wavelength (nm)

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Radio

10 20

10 18

10 16

10 14

10 12

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Energy is Quantized
The energy of atoms and molecules is quantized. They can only exist in allowed energy states or levels

Electronic energy levels in a H atom 1s 2s 2p 3s 3p 3d The lowest energy state has the single electron in the 1s orbital 1s1
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Absorption and Emission of EMR

When EMR is absorbed or emitted by matter it does so in whole photons only (NOT fractions) Absorption involves promotion from a lower energy state to a higher one Emission results in a jump from a higher energy level to a lower energy level
E2

DE = hn
E1 E2

DE = hn
E1

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