Electromagnetic Radiation

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Electromagnetic Radiation

Electromagnetic Radiation

Energy

Common Spectroscopic Methods Based on Electromagnetic Radiation

Electromagnetic Radiation
All of these, known collectively as the electromagnetic spectrum, are fundamentally similar in that they move at 186,000 miles per second (the speed of light in a vacuum). The only difference between them is their wavelength, which is related to the amount of energy the waves carry. The shorter the wavelength of the radiation, the higher the energy.
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Properties of Electromagnetic Radiation

v i = n li
where vi => velocity n => frequency li => wavelength

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Properties of Electromagnetic Radiation

in vacuum, velocity is independent of frequency, maximum value
c = nl = 2.998 X 108 m/s

energy = E = hn = hc/l

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Spectroscopy
Spectroscopy is the use of the absorption, emission, or scattering of electromagnetic radiation by matter to qualitatively or quantitatively study the matter or to study physical processes. The matter can be atoms, molecules, atomic or molecular ions, or solids. The interaction of radiation with matter can cause redirection of the radiation and/or transitions between the energy levels of the atoms or molecules.

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Absorption
Matter can capture electromagnetic radiation and convert the energy of a photon to internal energy. This process is called absorption. Energy is transferred from the radiation field to the absorbing species. We describe the energy change of the absorber as a transition or an excitation from a lower energy level to a higher energy level. Since the energy levels of matter are quantized, only light of energy that can cause transitions from one level to another will be absorbed.
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Absorption
The type of excitation depends on the wavelength of the light. Electrons are promoted to higher orbitals by ultraviolet or visible light, vibrations are excited by infrared light, and rotations are excited by microwaves. Absorption spectroscopy is one way to study the energy levels of the atoms, molecules, and solids. An absorption spectrum is the absorption of light as a function of wavelength. The spectrum of an atom or molecule depends on its energy-level structure, making absorption spectra useful for identifying compounds.
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Wave Parameters

Wave Parameters

Wave Parameters

Wave Parameters

Superposition of Waves The principle of superposition states that when two or more waves traverse the same space, a disturbance occurs that is the sum of the disturbances caused by the individual waves. This can cause constructive and destructive interference.

Superposition of sine waves to form a square wave: (a) combination of three sine waves, (b) combination of three, as in (a), and nine sine waves

Diffraction - a consequence of interference

Absorption
Measuring the concentration of an absorbing species in a sample is accomplished by applying the Beer-Lambert Law. A = abc,
where A = is the measured absorbance a = absorptivity b = path length c = analyte concentration

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Absorption
Experimental measurements are usually made in terms of transmittance (T), which is defined as:

where P is the power of light after it passes through the sample and Po is the initial light power. The relation between A and T is:

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Absorption
The figure below shows the case of absorption of light through an optical filter and includes other processes that decreases the transmittance such as surface reflectance and scattering.

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Energy States of Chemical Species

Atoms, ions, and molecules can exist only in certain discrete states, characterized by definite amounts of energy. When a species changes it state, it absorbs or emits an amount of energy exactly equal to the energy difference between the two states When atoms, ions, or molecules absorb or emit radiation in making the transition from one energy state to a second, the frequency is related to the difference in energy states by the equation E1 E0 = hn = hc/l where E1 is the energy of the higher state and E0 the energy of the lower state. The terms c and h are the speed of light and the Planck constant, respectively.

Energy States of Chemical Species

For atoms or ions in the elemental state, the energy of any given state arises from the motion of the electrons around the positively charged nucleus.
As a consequence, the various energy states are called electronic states.

In addition to having electronic states, molecules also have quantized vibration states that are associated with the interatomic vibrations and quantized rotational states that arise from the rotation of molecules around their centers of gravity

Molecular Absorption
Etotal = Eelectronic + Evibrational + Erotational The lowest energy state of an atom or molecule is its ground state Higher energy states are termed excited states

Emission
Atoms, molecules, or solids that are excited to high energy levels can decay to lower levels by emitting radiation (emission or luminescence) or through nonradiative processes .

Emission of Radiation
Line spectra
atoms

Band spectra
molecules

Continuum spectra
Produced when solids are heated to incandescence, black body radiation.

Emission

Jablonski Diagram
Relaxation mechanism for excited state molecules

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Jablonski Diagram

Molecular Fluorescence
Transitions between molecular electronic energy levels:

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Scattering (Raman)
When electromagnetic radiation passes through matter, most of the radiation continues in its original direction but a small fraction is scattered in other directions. Light that is scattered at the same wavelength as the incoming light is called Rayleigh scattering. Light that is scattered due to vibrations in molecules is called Raman scattering.

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Chapter 7

Components of
Optical Instruments

Components of Optical Instruments

Source Wavelength Selector Sample Detector Signal Processor Readout

A stable source of radiant energy A transparent container for holding the sample A device that isolates a restricted region of the spectrum for measurement (wavelength selector) A radiation detector which converts radiant energy to a usable signal (usually electrical) A signal processor and readout (for most modern instruments this is a computer)

Components of Optical Instruments

Source Wavelength Selector Sample Detector Signal Processor Readout

Emission Flame Photometer Flame Atomic Absorption Spectrometer Absorption Spectrometer Fluorescence and/or Scattering Spectrometer

Components of Optical Instruments

Emission Flame Photometer
Source Wavelength Selector Detector Signal Processor Readout

Sample

Components of Optical Instruments

Flame Atomic Absorption Spectrometer
Source Wavelength Selector Detector Signal Processor Readout

Sample

Components of Optical Instruments

Absorption Spectrometer
Source Sample Wavelength Selector Detector Signal Processor Readout

Components of Optical Instruments

Fluorescence and/or Scattering Spectrometer
Sample Wavelength Selector 0-90o Detector Signal Processor Readout

Source

Components of Optical Instruments Fig. 7-2 a, pg. 145 Construction materials

Components of Optical Instruments Fig. 7-2b, pg. 145 wavelength selectors

Components of Optical Instruments

Fig. 7-3, pg. 146 (a) Sources and for spectroscopic instruments.

Components of Optical Instruments

Fig. 7-3, pg. 146 (b) Detectors for spectroscopic instruments.

Sources
UV-Visible-Near IR Region H2 - D2
160 - 375 nm, must use Quartz windows and cuvettes

Xe arc lamps
250 - 600 nm, max I at 500 nm

W filament
320 - 2500 nm, needs close V control

Sources
IR Region Nernst glower - rare earth oxides globar - silicon carbide rod incandescent wire - nichrome wire

Sources
Line Sources metal vapor - Hg and Na hollow cathode - 65 elements

Wavelength Selection
Filters interference filters interference wedges absorption filters

Wavelength Selection
Monochromators Components entrance slit collimating element (lens or mirror) prism or grating as dispersing element focusing element (lens or mirror) exit slit

Wavelength Selection
Fig. 7-17, pg. 158 Dispersion for three types of monochromators. The points A and B on the scale in (c) correspond to the points shown in Figure 6-11.

Grating Monochromator
Fig. 7-19, pg. 160 Mechanism of diffraction from an echellettetype grating."

Gratings vs. Prisms

Advantages Gratings
dispersion nearly constant w/ wavelength simpler monochromator better dispersion for same size

Gratings vs. Prisms

Advantages Prisms
cheaper in the past

Gratings vs. Prisms

Disadvantages Gratings
stray radiation higher order spectra

Gratings vs. Prisms

Disadvantages Prisms
larger may be unstable to atmosphere of lab

Monochromator Slits
Construction of slits

Monochromator Slits
Fig. 7-22, pg. 165 Illumination of an exit slit by monochromatic radiation l2 at various monochromator settings. Exit and entrance slits are identical.

Monochromator Slits
Fig. 7-23, pg. 166 The effect of the slit width on spectra. The entrance slit is illuminated with l1, l2, and l3 only. Entrance and exit slits are identical. Plots on the right show changes in emitted power as the setting of monochromator is varied.

Sample Containers
Ultra-Violet
quartz

Visible
quartz glass

Infrared
NaCl AgCl KBr

Radiation Transducers
Properties of Ideal Transducers
High sensitivity High signal to noise ratio Constant response over a considerable range of wavelengths Fast response time Zero output in the absence of illumination The electrical signal produced would t=be directly proportional to the radiant power

Spectral response of some typical photoemissive surfaces

Fig. 7-28, pg. 170

Types of Radiation Detection

UV-Visible
Photon Detectors Vacuum Phototubes Photomultiplier Tubes Photodiodes Linear Photodiode arrays Charge-Transfer

Infrared
Heat Detectors

Types of Radiation Detection

Photovoltaic or Barrier-Layer Cell
Consist of flat copper or iron electrode which is deposited on a layer of semiconducting material such as selenium The outer surface of the of the semiconductor is coated with a thin transparent metallic film of silver or gold which serves as the collector electrode

Fig. 7-26, pg. 169

Schematic of a typical barrierlayer cell.

Types of Radiation Detection

Photovoltaic or Barrier-Layer Cell
When radiation of sufficient energy reaches the semiconducting material bonds are broken, resulting in the liberated ions migrating thru the circuit creating a current.

Fig. 7-26, pg. 169 Schematic of a typical barrierlayer cell.

Types of Radiation Detection

Photovoltaic or Barrier-Layer Cell
Advantages
No external power source needed Rugged Low cost

Disadvantages
Only useful for high levels of illumination
In other words, it suffers from lack of sensitivity at low levels

It suffers from fatigue

Good for routine analysis

Types of Radiation Detection

Vacuum Phototubes Fig.7-27, pg. 170 A phototube and accessory circuit. The photocurrent induced by the radiation causes a potential drop across R, which is then amplified to drive a meter or recorder.

Types of Radiation Detection

Photomultiplier Tubes Fig. 7-29, pg. 171 Photomultiplier tube: (a) cross section of the tube (b) electrical circuit. For the measurement of low radiant power intense light can irreversibly damage the photoelectric surface

Types of Radiation Detection

Photodiodes Fig. 7-30, pg. 172 (a)Schematic of a silicon diode. (b)Formation of depletion layer, which prevents flow of electricity under reverse bias. More sensitive than phototubes but less sensitive than photomultiplier tubes

Types of Radiation Detection

Photodiodes Fig. 7-31, pg. 173 A reverse-biased linear diode-array detector: (a) cross section and (b) top view.

Types of Radiation Detection

Photodiode arrays sensitivity less than photomultiplier tube but has then multi channel advantage

Types of Radiation Detection

Charge-Injection Device Fig. 7-33, pg. 174 Cross section of a CTD detector in the charge integration mode. The positive hole produced by the photo hn is collected under the negative electrode.

Types of Radiation Detection

Charge-Transfer Fig. 7-34, pg. 175
Duty cycle of a chargetransfer device: (a.) production and storage of charge (b.) first charge measurement (c.) second charge measurement after charge transfer (d.) reinjection of charge into the semiconductor.

Types of Radiation Detection

Heat Detectors covered in detail in Chapter 16
Fourier Transform also covered in detail in Chapter 16