Atomic Spectroscopy

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

OE => distance from screen to plane of slits

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?

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?
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

(0.300 mm)(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

"Partial energy level

diagram for a
fluorescent organic
molecule."

Emission of Radiation
radiation resulting from the relaxation to
lower energy states of excited particles

Absorption Methods, Transmittance

T = P/Po
where

T => transmittance
P => power of transmitted
radiation
Po => power of incident
radiation
%T = (P/Po)*100
where %T => percent transmittance

Absorption Methods, Absorbance

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.

transmittance scale is linear

absorbance scale is exponential
thus, read transmittance, then calculate absorbance