Reviewer for Atomic Spectroscopy

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Atomic Spectroscopy

Reviewer for Atomic Spectroscopy

© All Rights Reserved

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An Introduction of

Spectrometric Methods

Properties of

Electromagnetic Radiation

Electromagnetic Radiation

energy radiated in the form of a WAVE caused

by an electric field interacting with a magnetic

field

result of the acceleration of a charged particle

does not require a material medium and can

travel through a vacuum

Properties of

Electromagnetic Radiation

v i = i

where

vi => velocity

=> frequency

i => wavelength

Properties of

Electromagnetic Radiation

in vacuum, velocity is independent of

frequency,

maximum value

c = = 2.998 X 108 m/s

Properties of

Electromagnetic Radiation

"Representation of a beam of monochromatic, plane polarized radiation.

The arrows represent the electrical vectors."

Properties of

Electromagnetic Radiation

"Effect of change of medium on a monochromatic beam of radiation."

Properties of

Electromagnetic Radiation

"Regions of the electromagnetic spectrum"

Properties of

Electromagnetic Radiation

"Common Spectroscopic Methods Based on electromagnetic Radiation"

Properties of

Electromagnetic Radiation

Wave Equation

for a single wave

y = A sin (2t + )

Properties of

Electromagnetic Radiation

for n waves of same frequency

superimposed of phase angle

y = A1 sin (2t + 1)

+ A2 sin (2t + 2)

+ A3 sin (2t + 3)

+

+ An sin (2t + n)

Properties of

Electromagnetic Radiation

"Superposition of sinusoidal waves: (a) same frequency, small

difference in phase (b) same frequency, large difference in phase

(c) difference frequencies, starting in phase.

Properties of

Electromagnetic Radiation

for n waves of different frequencies

superimposed of phase angle

y = A1 sin (2t + 1)

+ A2 sin (2t + 2)

+ A3 sin (2t + 3)

+

+ An sin (nt + n)

Properties of

Electromagnetic Radiation

"Superposition of sine waves

to form a square wave:

(a) combination of three sine

waves, and (b) combination of

three, as in (a), and nine sine

waves."

Diffraction

"Propagation of waves

through a slit: (a) xy >

(b) xy ."

Diffraction

"Diffraction of

monochromatic

radiation by slits."

Diffraction

= CF = BC sin

n = CF = BC sin

DE = OD sin

Diffraction

BC DE

BC DE

n = ---------- = -----------OD

OE

where

BC => slit spacing

DE => band spacing

EXAMPLE:

Suppose that the screen in the figure

shown is 2.00 m from the plane of the

slits and that the slit spacing is 0.300

mm. What is the wavelength of

radiation if the fourth band is located

15.4 mm from the central band?

figure shown is 2.00 m from the plane of the

slits and that the slit spacing is 0.300 mm. What

is the wavelength of radiation if the fourth band

is located 15.4 mm from the central band?

BC DE

BC DE

n=4

n = ------------ = -----------OD

OE

___

OE

=

2.00

m

___

BC

___ = 0.300 mm

DE = 15.4 mm

EXAMPLE:

Suppose that the screen in the figure is 2.00 m from the

plane of the slits and that the slit spacing is 0.300 mm.

What is the wavelength of radiation if the fourth band is

located 15.4 mm from the central band?

n=4

OE = 2.00 m

___

___

BC = 0.300 mm

DE = 15.4 mm

= ---------------------------4 (2 * 1000)mm

= 5.78 X 10-4 mm or 578 nm

Transmission of Radiation

Transmission

rate at which radiation passes through a

transparent material is less than through a

vacuum

depends upon the kinds and concentrations of

atoms, ions, and molecules in the medium

radiation must interact with material

interaction must not undergo permanent energy

transfer

Transmission of Radiation

Transmission

ni = c/vi

where

ni => refractive index, measure

of interaction

c => speed of light in vacuum

vi => speed of light in medium

Transmission of Radiation

Dispersion

variation in refractive index of a substance with

wavelength or frequency

Refraction of Radiation

Snells Law

sin

n2

v1

sin

n1

v2

Reflection of Radiation

reflection always occurs when radiation

passes from one medium to another

reflection greatest when two materials have

the greatest difference on their refractive

indices

Scattering of Radiation

Types of Scattering

Rayleigh Scattering

scattering involving molecules which are

considerably smaller than the wavelength of

radiation

blue sky results from greater scattering of shorter

wavelength visible light

Scattering of Radiation

Types of Scattering

Scattering by Large Molecules

can be measured

a function of the size and shape of molecule

Scattering of Radiation

Types of Scattering

Raman Scattering

part of the radiation undergoes quantized frequency

changes

Quantum-Mechanical

Properties of Radiation

E = h = hc/

Emission of Radiation

Line spectra

Band spectra

Continuum spectra

Line spectra

Emission spectrum

of a brine obtained

with an oxy-hydrogen

flame

Line spectra

X-ray emission

spectrum of

Molybdenum

metal

Band spectra

Energy-level

diagram for (a) a

sodium atom

showing the source

of a line spectrum

and (b) a simple

molecule showing

the source of a band

spectrum.

Continuum spectra

Blackbody radiation curves

Absorption of Radiation

energy of exciting photon must equal

energy difference between ground state

and 1 excited state for absorption to

occur

Absorption of Radiation

"Some typical

ultraviolet

absorption

spectra."

Atomic Absorption

absorption occurs with only a few welldefined frequencies

electronic excitation

Molecular Absorption

E = Eelectronic + Evibrational + Erotational

Molecular Absorption

diagram for a

fluorescent organic

molecule."

Emission of Radiation

radiation resulting from the relaxation to

lower energy states of excited particles

T = P/Po

where

T => transmittance

P => power of transmitted

radiation

Po => power of incident

radiation

%T = (P/Po)*100

where %T => percent transmittance

A = - log10T = - log10 (P/Po)

where

A => absorbance

Absorption Methods,

Beers Law

A = abc = bc

where a => absorptivity

b => path length

c => concentration

=> molar absorptivity

Spectroscopic Methods

Major classes of spectroscopic methods

Absorption Methods

Attenuation of a beam of radiation by an absorbing species

Absorption Methods

Single-beam photometer for absorption

measurements in the visible region.

Absorption Methods

Readout for an inexpensive photometer.

absorbance scale is exponential

thus, read transmittance, then calculate absorbance

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