Instrumental Chemistry

Chapter 12
Atomic X-Ray Spectrometry

Brief Summary
X-ray spectroscopy is a form of
optical spectroscopy that utilizes
emission, absorption, scattering,
fluorescence, and diffraction of Xray radiation

About X-Rays
X-rays are short-wavelength (hence, high frequency, and
hence, relatively high energy) electromagnetic radiation.
Two ways to produce X-rays:
1) Deceleration of high-energy electrons
2) Electronic transitions involving inner-orbital (e.g. d or f) electrons
The wavelength range of X-Rays is from about 10-5 to
100
Conventional X-Ray spectroscopy islargelyconfinedto
theregionofabout0.1to25

For Analytical Purposes, X-rays

are Generated in Three Ways:
1) Bombardment of metal target with
high-energy electron beam
2) Exposure of target material to
primary X-ray beam to create a secondary
beam of X-ray fluorescence
3) Use of radioactive materials whose
decay patterns include X-ray
emission

Schematic of an X-ray tube

Energy-level iagram showing common

transitions producing X-rays

Energy-Level Diagram Showing

Common Transitions Producing X-rays

Common X-Ray Transitions

Partialenergylevel

diagramshowing
commontransitions
leadingtoX
radiation.
Themostintenselines
areindicatedbythe
widestarrows

Wavelengths/forIntenseXray
EmissionLines
Note that all possible electronic transitions
are not of equal probability, i.e., the nature of
a spectrum depends on specific selection
rules, so that the complexity of a spectrum is
not as great as might be expected from first
consideration of an energy level diagram.

Wavelengths/forIntenseXray
Thefactthatthewavelengthofalineof

giventypedecreasesastheatomicnumber
oftheelementincreasesisratherimportant
inthatitmeansthatanXrayfromagiven
elementmustbeabletocauseinnershell
ionizationand,hence,emissionofradiation
oflowerenergyfromanylighterelement.

Characteristics and Identification

Of Wavelengths
Identification and measurement of concentration

of elements based on the fact that primaryemission x-rays emitted by an element excited by
an electron beam have a wavelength characteristic
of that element and an intensity related to its
concentration. It may be performed by an electron
probe microanalyzer, an electron microscope
microanalyzer, or by an electron microscope, or
scanning electron microscope, fitted with an x-ray
spectrometer.

Electron Beam Sources

In electron beam sources, X-rays are
produced by heating a cathode to produce
high-energy electrons; these electrons are
energetic enough to ionize off the cathode
and race towards a metal anode (the target)
where, upon collision, X-rays are given off
from the target material in response to the
colliding electrons.

The Duane-Hunt law

The maximum photon energy corresponds
to total stopping of the electron and is given
by:
hvo = (hc)/o = Ve
vo is the maximum frequency
V = accelerating voltage
e = electron charge

ContinuumSpectrafrom
ElectronBeamSources
In an X-ray tube, electrons produced at a heated cathode
are accelerated toward a metal anode by a potential as great
as 100kV; upon collision, part of the energy of the electron
beam is converted into X-Rays. Under some conditions
only a continuum spectrum is results. The continuum XRay spectrum is characterized by a well-defined, short
wavelength limit, which is dependent upon the accelerating
voltage but independent of the target material. The
continuum radiation from an electron beam source results
from collisions between the electrons of the beam and the
atoms of the target material.

LineSpectrafromElectronBeam
Sources
Bombardment of a molybdenum target produces intense emission

lines. The emission behavior of molybdenum is typical of all elements

having atomic numbers greater than 23, that is, the X-Ray line spectra
are similar when compared with ultraviolet emission and consist of
two series of lines.
Line spectra are composed of distinct lines of color, or in the case of
our graphs, sharp peaks of large intensity at a particular wavelength.
Line spectra are characteristic of elements and compounds when
excited (energized) under certain conditions. These spectra helped
develop the current atomic theories. Line spectra thus provide a
fingerprint unique to each element, and as with continuous spectra,
the combination of the prominent lines in the spectrum produce the
observe light color.

Line Spectra from Electron Beam

Sources

X-ray Fluorescence
Since X-rays are rather energetic,
excitation of sample electrons will
give rise to fluorescence as the
sample electrons are excited and
return to their ground states in a
series of electronic transitions.

Bragg Equation
sin = (n)/2d
= angle of incidence
= wavelength
d = interplane distance of crystal

Diffraction of X-rays by a crystal

XrayMonochromatorandDetector

References
http://www.anachem.umu.se/jumpstation.ht
m
http://userwww.service.emory.edu/~kmurra
y/mslist.html
http://www.chemcenter/org
http://www.sciencemag.org