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14 views34 pages

ch24 Better

Uploaded by

Jaser Yamin
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Chapter 24

Introduction to Spectrochemical Methods


Interaction of Radiation and Matter
• Physical interaction:
(without changing the energy level of chemical species)
 Reflection (反射)
 Refraction (折射) Absorption
 Elastic scattering (散射) Emission

 Interference (干涉)
 Diffraction (繞射)

• The most interesting types of interaction in spectroscopy:


 Transitions between different energy levels of chemical species
 Absorption and Emission
Spectroscopy
 Spectroscopic analytical methods are based on measuring the amount of
radiation produced (emission) or absorbed (absorption) by molecular
or atomic species of interest.

 γ‐ray, X‐ray, ultraviolet (UV), visible (VIS), infrared (IR), microwave, and
radio‐frequency (RF).

 Spectrochemical methods are the most widely used tools for the
elucidation of molecular structure as well as the quantitative and
qualitative determination of both inorganic and organic compounds.
Properties of Electromagnetic Radiation

 Electromagnetic radiation is a form of energy that is transmitted through


space at enormous velocities.

 Electromagnetic radiation can be described as a wave with properties of


wavelength, frequency, velocity, and amplitude.
Properties of Electromagnetic Radiation
 The amplitude of an electromagnetic wave is a vector quantity that provides a
measure of the electric or magnetic field strength at a maximum in the wave.

 The period of an electromagnetic wave is the time in seconds for successive


maxima or minima to pass a point in space.

 The frequency of an electromagnetic wave is the number of oscillations that


occur in 1s. The unit of frequency is the hertz (Hz), which corresponds to one
cycle per second, that is, 1 Hz = 1 s‐1.

 The product of the frequency in waves per unit time and the wavelength in
distance per wave is the velocity v of the wave in distance per unit time (cm s‐1
or m s‐1).
v = 

 In a vacuum, light travels at its maximum velocity .

c =  = 2.99792  108 m s‐1 = 2.99792  1010 cm s‐1


Properties of Electromagnetic Radiation

 The frequency of a beam of electromagnetic radiation does not


change as it passes through different media.
Properties of Electromagnetic Radiation
 The wavenumber,  , is another way to describe electromagnetic
radiation.

 It is defined as the number of waves per centimeter and is equal to


1/ (units of cm‐1).

 The wavenumber in cm‐1 is most often used to describe radiation in


the infrared region (2.5 ‐ 15 μm = 4000 ‐ 667 cm‐1).
The Particle Nature of Light: Photons
The energy of a single photon is related to its wavelength, frequency, and
wavenumber

E = h = hc/ = hc

where h is Planck’s constant (6.63  10‐34 Js).


Electromagnetic Spectrum

Optical methods
Spectroscopic Measurement

Relaxation

Spectroscopic
measurement

Stimulus:
 Heat
 Electrical energy
 Light
 Particles
 Chemical reaction
Emission or Chemiluminescence Process
 Emission spectroscopy: Stimulated by heat or electrical energy

 Chemiluminescence spectroscopy: Excite by chemical reaction

Radiant Spectrum
 Information of identity
 Information of concentration
Absorption Method
Reflection
Atomic absorption spectroscopy

Scattering

Photoluminescence Method

Fluorescence and phosphorescence


spectroscopy
Radiation Absorption
 The transmittance T of the solution is the fraction of incident radiation
transmitted by the solution. Transmittance is often expressed as a
percentage and called the percent transmittance.

T = P/P0

 The absorbance, A, of a solution is related to the transmittance in a


logarithmic manner.

P P0
A   log T   log  log
P0 P
Calculation of Absorbance from Transmittance

P P0
A   log T   log  log
P0 P
Measurement of Transmittance
 Transmittance and absorbance usually cannot be measured because
the solution to be studied must be held in a container (cell or cuvette).

 Reflection and scattering losses can occur at the cell walls.

 A = log P0/P  log Psolvent/Psolution


Beer’s Law
 For monochromatic radiation, absorbance is directly proportional to the
concentration of the absorbing species, c, and to the path length, b, of
the absorbing medium:

A = log(P0/P) = abc

a is a proportionality constant called the absorptivity.

 Concentration expressed in moles per liter and b in cm, gives the


proportionality constant, called the molar absorptivity,  (L mol‐1 cm‐1).

A = bc

 Atotal = A1 + A2 + …+ An = 1bc1 + 2bc2 + …+ nbcn


where the subscripts refer to absorbing components 1, 2, . . . , n.
Absorption Spectra (Absorbance vs. Wavelength)

Typical UV/VIS Spectrum Typical IR Spectrum

KMnO4
Why is a Red Solution Red ?
Atomic Absorption
 The major atomic absorption transitions occur when the single outer electron
of sodium is excited from its room temperature or ground state 3s orbital to the
3p, 4p, and 5p orbitals.

 These excitations are brought on by absorption of photons of radiation whose


energies exactly match the differences in energies between the excited states
and the 3s ground state. Na

 Transitions between two different orbitals are


termed electronic transitions.

Electronic transition
Molecular Absorption
 The total energy E associated with a molecule is

Eoverall = Eelectronic + Evibrational + Erotational

 Eelectronic is the energy associated with the electrons in the various outer
orbitals of the molecule.

 Evibrational is the energy of the molecule as a whole due to interatomic


vibrations.

 Erotational accounts for the energy associated with rotation of the


molecule about its center of gravity.

 Vibrational and rotational transitions occur with polyatomic species


because only this type of species has vibrational and rotational states
with different energies.
Electronic, Vibrational, and Rotational Transitions

 E electronic  10Evibrational  100E rotational


Vibrational Transition

Vibration
(energy level)
(Ev>Er)
Effect of Solvent on the Absorbance Peaks

Inter‐molecular
interactions
Limits to Beer's Law

 Real Limitations to Beer's Law


 in relatively concentrated solution (0.01 M) of the analyte or in
concentrated electrolyte solutions
 Non‐linearity due to intermolecular interactions

 Chemical Deviation
 The absorbing species participates in a concentration‐dependent
equilibrium such as a dissociation or association reaction.

 Instrumental Deviation
 Polychromatic radiation, stray light, mismatched cell
Chemical deviations
Instrumental Deviation: Polychromatic Radiation
Instrumental Deviation: Polychromatic Radiation
Instrumental Deviation: Stray Light
Emission of Electromagnetic Radiation
 (1) bombardment with electrons; (2) heating in a plasma, flame, or an electric
arc; or (3) irradiation with a beam of light.
Line Spectrum

 The line spectrum consists of a


series of sharp, well‐defined
spectral lines caused by excitation
of individual atoms that are well
separated, as in a gas.

 0.1 – 0.01 Å
Continuum Spectrum: Blackbody Radiation

 A spectral continuum of radiation


is produced when solids such as
carbon and tungsten are heated to
incandescence.
Emission By Fluorescence and Phosphorescence

10-15 s

10-9 ~ 10-6 s

10-5 s

 Nonradiative relaxation  Resonance fluorescence (λ1 = λ2)


Temperature ↑  Stokes shift (λ1 < λ2)

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