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Lesson 1. Introduction

Analytical chemistry is the science that identifies the components of a sample

(qualitative analysis) and which determines the relative amounts of each of
1. Fundamentals of spectroscopy. them (quantitative analysis). Usually, requires a prior separation of the analyte
of interest.

Classical methods: wet chemistry (titration, gravimetry and systematic

2. The electromagnetic radiation. qualitative analysis)

3. Wave properties of radiation. Instrumental Methods: exploit the physical properties of the analyte to
obtain both qualitative and quantitative information

4. Quantum mechanical aspects of radiation. Spectroscopy: studies the interaction of the electrical field
component of electromagnetic radiation with matter by means of
phenomena such as absorption, emission and scattering of light
5. Atomic and molecular spectroscopy.

Some spectrometric modes Electromagnetic spectrum and its regions

Electromagnetic spectrum and its regions Interaction of radiant energy with matter

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Interaction of radiant energy with matter Light: electromagnetic radiation

Light has a dual nature:

• Corpuscular (photons)
• Wavelike (waves)

Light: discrete energy levels The light and its interaction with matter: discrete energy levels

The principle of energy quantization implies that only certain

discrete values of energy are possible.

Electromagnetic wave Electromagnetic wave

Power, P, is the energy -expressed in watts- that reaches a given area per
unit of time
Intensity, I, is the radiation power per unit solid angle

Frequency: number of cycles per unit time. It depends on the emission source and remains invariant,
regardless of the medium it travels through.
cicles
 [ ] [ ] hertz [ ] s 1
s
Period: time spent in a complete cycle. T = 1/ [=] s

Wavelength, i: distance between two successive maxima or minima.

h ·c
Velocity of propagation: vi =  · i v and  are a function of the medium they traverse E  h ·   h ·c ·  h, Planck’s constant = 6,63·10-34 J s

1 1
Wavenumber: # of waves per cm.  [ ] cm 1 ;     K ·
i vi
In a beam, P is directly proportional to the # of photons per second.
In a vacuum, the speed of radiation becomes independent of wavelength and reaches its maximum
value. c =  ·  = 3,00·108 ms-1

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Superposition of waves Constructive and destructive interferences

The amplitude of the resulting wave depends on the phase out between the
individual waves
When the two waves are in phase,  =0,
a maximum constructive figure of
interference is obtained

When  = 180, a maximum

destructive interference is
produced.

Superposition of waves Transmission of light through a dense medium

The shortening of the wave is a function of the nature and

concentration of the matter.

Refraction c
ni 
index vi
Animations courtesy of Dr. Dan Russell, Kettering University

Refractive dispersing curve Scattering of light

Lenses, n  const.

vi = f (i)

ni = f (i)
Prisms

Rayleigh

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Scattering of light Polarization

Electromagnetic radiation is said to be depolarized when both the magnetic

and electric vectors reach the same magnitude in all directions.
Most of dispersed photons keep the
frequency of the source (Rayleigh
dispersion); the frequency of a
very small fraction of photons
(aprox. 1 in 107) has changed
(Raman dispersion). Light becomes plane-polarized when it propagates in a single plane through
space.

Polarized light Refraction of radiation: Snell’s law

Abrupt change in direction of the beam as a consequence of a

difference in velocity of radiation in the two media.
E = Eocost E = Eoe-t = Eocost + Eo sin t

c
sen θ1 n2 v 2 v1  1 1
    
sen θ 2 n1 c v 2  2  2
v1

Plane-polarized light Circular-polarized light When medium 1 is vacuum, n1 = 1

nvacuum = 1,00027 · nair

n1 sen θ1  n2 sen θ 2

Reflection of radiation Reflection of radiation

If the surface roughness is less than the wavelength, then an

actual reflection takes place, for which the law of reflection is
obeyed (angle of incidence = angle of reflection). Usually only a
portion of the incident beam is reflected, because the other
penetrates the medium and is refracted.

Fermat’s rule:
Pathlength L from A to B is: radiation always travels If the roughness of the boundary surface is comparable to the
the shortest way wavelength of the incident beam, a diffusion is obtained (diffuse
(shorter time). reflection).

Since medium remains unchanged, velocity is identical, and the minimum time-consuming
route should be the one with shortest distance, what can be easily calculated by making
If the beam angle exceeds a certain limit, the
the derivative zero.
so-called total reflection takes place.

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Reflection of radiation Propagation of waves through slits: Difraction

Difraction: every parallel beam of radiation is bent as it passes by a

For a beam that enters an interface at sharp barrier or through a narrow opening.
Ir right angles, the fraction reflected
(reflectance) is given by:

Ii
(n2  n1 )2 Ir
ρ and,in general, ρ
(n2  n1 )2 Ii

The total reflective loss will be the sum of the losses occurring at each
of the interfaces. The more interfaces present, the higher the beam
intensity loss.
For the air (n=1) to glass (n=1,5) interface a 4% loss is calculated ( =
0,04; 4%)

See Skoog, page 142 Difraction is a consequence of interference as shown by Young in 1800.
Example 6-2

Propagation of monochromatic radiation waves through slits Coherent radiation

 
BCF  DOE Radiation emitted by a source in which all elemental waves show a constant phase
relationship along time and space. (IUPAC, 1997)

CBF  θ
Laser light is:
Monochromatic (unique wavelength)
λ  CF  BC sen θ
Coherent (in phase)
Directional (very narrow diverging cone)
m λ  BC sen θ

A tungsten filament lamp is:

m: orden of interference
Chromatic

DE  OD sen θ Incoherent
Non-directional

BC DE BC DE
mλ  A monocromatic source:
OD OE
Coherent
See Skoog, page 139
Example 6-1 Non-directional

Simplified energy levels diagram Atoms as absorbing species: atomic (line) spectrum

E
E = E electr + E vibr + E rot

The two absorbing peaks surge

from the 3s electron promotion to
the 3p states.

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Atoms as absorbing species: atomic (line) spectrum Molecules as absorbing species: band spectrum

The two absorbing peaks surge

from the 3s electron promotion to
the 3p states.

Absorption bands

Absorption spectra and resolution Radiative and non-radiative relaxation

Atomic and molecular spectra Black body emission: continuum of radiation vs. discrete lines by XR source

1
λ máx  (Wien)
T

W(B ν )  T 4 (Stefan)

W  V 4 (in VIS )

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