Chapt.6 Spectrochemical Anal.

NTLP

CHAPTER 6

SPECTROCHEMICAL METHODS

Contents
 6.1. General principle of spectrochemical
methods
 6.2. Ultraviolet-visible spectroscopy
 6.3. Atomic absorption spectroscopy
 6.4. Application of spectroscopic methods to
food analysis

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Chapt.6 Spectrochemical Anal. NTLP

6.1. General principles of

spectrochemical methods
 Introduction
 Properties of Electromagnetic Radiation
 Interaction of Radiation and Matter
 Absorption of Radiation
 Principles of Spectroscopy
 Instruments for Chemical Spectrometry

Electromagnetic Spectrum

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Chapt.6 Spectrochemical Anal. NTLP

Wave Properties of Electromagnetic Radiation

Wave Properties of Electromagnetic Radiation

 The wavelength, , is the linear distance between

successive maxima or minima of a wave, depends on
the medium.
 The wavenumber, n (cm-1)= 1/.
 The refractive index, h = c/v.

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Chapt.6 Spectrochemical Anal. NTLP

Particle Properties of Electromagnetic Radiation

 In many radiation/matter interactions, it is useful to
emphasize the particle nature of light as a stream of
photons or quanta. We relate the energy of a single
photon to its wavelength, frequency, and wave number
by

C
E  hf  h


E: eV, kcal/mol (= 4.34.10-2 eV)

h (Planck constant) = 6.622.10-34 J.s = 6.59 eV.s

Energy levels diagram of a molecule

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Chapt.6 Spectrochemical Anal. NTLP

Principles of Spectrochemical Methods

 Spectrochemical methods have provided perhaps the
most widely used tools for the elucidation of
 molecular structure
 qualitative determination
 quantitative determination
of both inorganic and organic compounds.
 the excitation of atoms and molecules by photons.
 Ultraviolet-visible spectroscopy (UV-Vis)
 Atomic absorption spectroscopy (AAS)

 .

Absorption methods

(a), radiation of incident radiant power P0 can be absorbed by the

analyte, resulting in a transmitted beam of lower radiant power P.
(b), for absorption to occur the energy of the incident beam must
correspond to one of the energy differences.
(c), the resulting absorption spectrum.

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Chapt.6 Spectrochemical Anal. NTLP

Energy level

Absorbance (A)

A  - logT
 - log %T  log100
 2 - log %T

Attenuation of a beam of monochromatic radiation by an absorbing solution.

 The larger arrow on the incident beam signifies a higher radiant power P0 than that
transmitted by the solution P.
 The path length of the absorbing solution is b and the concentration is CM.
 Interactions between the photons and absorbing particles decrease the radiant
power of the beam from P0 to P.
 The transmittance, T, of the solution is the fraction of incident radiation transmitted by
the solution, is often expressed as the percent transmittance.

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Chapt.6 Spectrochemical Anal. NTLP

Measuring Transmittance and

Absorbance

Reflection and scattering losses with a solution contained in a

typical glass cell. Losses by reflection can occur at all the boundaries
that separate the different materials. In this example, the light passes
through the following boundaries, called interfaces: air-glass, glass-
solution, solution-glass, and glass-air.

Terms Used in Absorption Spectrometry

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Chapt.6 Spectrochemical Anal. NTLP

Absorption Spectra
 An absorption spectrum is a plot of
absorbance (A) versus wavelength ()

Typical absorption spectra of

KMNO4 at five different
concentrations.
The numbers adjacent to the
curves indicate concentration
of manganese in ppm, and the
absorbing species is
permanganate ion, MnO42. The
cell path length b is 1.00 cm.
A plot of absorbance at the
peak wavelength at 525 nm
versus concentration of
permanganate is linear and
thus the absorber obeys
Beer’s law.

Beer-Lambert law

A   .b.C
A = the absorbance and C = concentration
b = path length (cm)
- Molar absorptivity (L/mol.cm)
 - absorptivity coefficient (L/g.cm)
 depends on the transition probability ( of the radiation)
and the nature of the absorbing species; temperature.

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Chapt.6 Spectrochemical Anal. NTLP

Example
 A 7.25 x 10-5 M solution of potassium
permanganate has a transmittance of 44.1%
when measured in a 2.10-cm cell at a
wavelength of 525 nm. Calculate
(a) the absorbance of this solution
(b) the molar absorptivity of KMnO4.

Applying Beer’s law to Mixtures

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Chapt.6 Spectrochemical Anal. NTLP

Components of various instruments used in optical spectroscopy

Detector

Table 25-2 p700

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Chapt.6 Spectrochemical Anal. NTLP

Cell chamber

Application to Food Analysis

1. Ultraviolet-visible spectroscopy (UV-Vis)

2. Atomic Absorption Spectroscopy (AAS)

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