Chapter 12 Atomic X-Ray Spectroscopy

is based on measurement of emission, X-ray spectroscopy, like optical spectroscopy, is based on measurement of emission, absorption, scattering, fluorescence, and diffraction of electromagnetic radiation. X-ray fluorescence and X-ray absorption methods are widely used for the qualitative and quantitative determination of all elements in the periodic table having atomic numbers greater than that of sodium. With special equipment, elements with atomic numbers in the range of 5 to 10 can also be determined.

12A FUNDAMENTAL PRINCIPLES

X-Rays are short wavelength electromagnetic radiation produced by the deceleration of high-energy electrons or by electronic transitions of electrons in the inner orbitals of atoms.

12A-1 Emission of X-Rays

For analytical purposes, X-rays are obtained in four ways: 1 For analytical purposes, X-rays are obtained in four ways: 1. by bombardment of a metal with a beam of high-energy electrons, 2. by exposure of a substance to a primary beam of X-rays in order to generate a secondary beam of X-ray fluorescence, 3. by use of a radioactive source whose decay process results in X-ray emission, 4. from a synchrotron radiation source.

Continuum Spectra from Electron Beam Sources

V: accelerating voltage e: charge on electron Ee = E’e + h At o, E’e = 0 h0 = hc/o = Ve V: accelerating voltage e: charge on electron l0 = 12,398/V Duane-Hunt Law Independent of material Related to acceleration voltage  E l0 FIGURE 12-1 Distribution of continuum radiation from an X-ray tube with a tungsten target. The numbers above the curves indicate the accelerating voltages.

FIGURE 12-2 Line spectrum for an X-ray with a molybdenum target. From electron transitions involving inner shells Atomic number >23 2 line series K and L E K> EL Atomic number < 23 K only A minimum acceleration voltage is required for FIGURE 12-2 Line spectrum for an X-ray with a molybdenum target. A minimum acceleration voltage required for each element increases with atomic number

Line Spectra from Electron Beam Sources

FIGURE 12-4 Partial energy level diagram showing common transitions producing X-rays. The most intense lines are indicated by the wider arrows.

Line Spectra from Fluorescent Sources Spectra from Radioactive Sources X-Radiation is often a product of radioactive decay processes.

TABLE 12-2 Common Radio isotopic Sources for X-ray Spectroscopy

12A-2 Absorption Spectra When a beam of X-rays is passed through a thin layer of matter, its intensity or power is generally diminished as a consequence of absorption and scattering. The absorption spectrum of an element, like its emission spectrum, is simple and consists of a few well-defined absorption peaks.

The Absorption Process The Mass Absorption Coefficient

X-ray absorption spectra for lead and silver. Ln P0/P = μX μ is the linear absorption coefficient is characteristic of the Element and # of atoms in the path of the beam. X is sample thickness Ln P0/P = μMηX η is density of the sample μM is mass absorption coefficient FIGURE 12-5 X-ray absorption spectra for lead and silver.

12A-3 X-ray Fluorescence

12A-4 Diffraction of X-rays

Bragg's Law

12B INSTRUMENT COMPONENTS

12B-1 Sources

The X-ray Tube Radioisotopes Secondary Fluorescent Sources

Determining the energy of the X-Ray 100KV! Controlling the intensity of X-Ray

12B-2 Filters for X-rays

12B-3 X-ray Monochromators

FIGURE 12-9 An X-ray monochromator and detector. Note that the angle of the detector with respect to the beam (2ө) is twice that of the crystal face. For absorption analysis, the source is an X-ray tube and the sample is located in the beam as shown. For emission measurements, the sample becomes a source of X-ray fluorescence as shown in the insert.

12B-4 X-ray Transducers and Signal Processors

Photon Counting Gas-Filled Transducers The Geiger Tube

Proportional Counters Ionization Chambers Scintillation Counters Semiconductor Transducers

FIGURE 12-12 Vertical cross section of a lithium-drifted silicon detector for X-rays and radiation from radioactive sources.

Distribution of Pulse-Heights from X-ray Transducers

12B-5 Signal Processors

Pulse-Height Selectors Pulse-Height Analyzers Scalers and Counters

12C X-RAY FLUORESCENCE METHODS

12C-1 Instruments

Wavelength-Dispersive Instruments Energy-Dispersive Instruments

FIGURE 12-14 Energy-dispersive X-ray fluorescence spectrometer FIGURE 12-14 Energy-dispersive X-ray fluorescence spectrometer. Excitation by X-rays from (a) an X-ray tube and (b) a radioactive substance

FIGURE 12-15

Semi quantitative Analysis 12C-2 Qualitative and Semi quantitative Analysis

FIGURE 12-16 X-Ray fluorescence spectrum for a genuine bank note recorded with a wave- length dispersive spectrometer.

FIGURE 12-17 Spectrum of an iron sample obtained with an energy-dispersive instrument with a Rh anode X-ray tube source. The numbers above the peaks are energies in keV. (Reprinted with permission from J. A. Cooper, Amer. Lab., 1976,8 (11),44. Copyright 1976 by International Scientific Communications, Inc.)

12C-3 Quantitative Analysis

Calibration Against Standards Use of Internal Standards Matrix Effects Calibration Against Standards Use of Internal Standards Dilution of Samples and Standards

Some Quantitative Applications of X-ray Fluorescence Advantages and Disadvantages of X-ray Fluorescence Methods

12D X-RAY ABSORPTION METHODS

12E X-RAY DIFFRACTION METHODS

12E-1 Identification of Crystalline Compounds

Automatic Diffractometers Photographic Recording

FIGURE 12-18 Schematic of (a) a Debye- Scherrer powder camera; (b) the film strip after development. D2, D1 and T indicate positions of the film in the camera.

12E-2 Interpretation of Diffraction Patterns

12F THE ELECTRON MICROPROBE