Atomic X-Ray

Dr Francis Mani
Spectrometry
Dr Francis Mani
(Notes are from Skoog et al. unless advised)

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OUTLINE OF LECTURE
WEEK 4 SESSION 1

• X-ray fundamentals
• Emission of X-rays
• Continuum vs Line Spectra
• Duane-Hunt Law
• Emission Lines & Interpretation
• Absorption Spectra

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Fundamental Principles
• X-Rays are short wavelength electromagnetic
radiation produced by deceleration of high-energy
electrons or by electronic transitions of electrons in
the inner orbitals of atoms.
• The λ range of X-rays: 10-5 Å – 100 Å
• Conventional X-Ray spectroscopy: 0.1 Å – 25 Å

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Emission of X-rays
• X-rays are obtained in four ways, from:
• Bombardment of a metal target with a beam of high
energy electrons;
• Exposure of a substance to a beam of X-rays in order
to generate a secondary bean of X-ray fluorescence;
• Decay of a radioactive source; and
• A synchrotron radiation source
• X-ray sources often produce continuum and line
spectra 4
 Continuum Spectra from Electron
Beam Sources
• In an X-ray tube, electrons are
produced at a heated cathode
and aimed at a target anode.
• The potentials required to
achieve this generation can go
as high as 100 kV.
• Upon collision, part of the
energy of the electron beam
is converted to X-rays.
• Under some conditions, only
a continuum results. 5
Continuum Spectra from Electron
Beam Sources
• This continuum spectrum is dependent upon the
acceleration voltage but not on the target material.
• This continuum radiation results from collisions between
the electrons of the beam and the atoms of the target
material.
• At each collision, an electron in the beam is decelerated
and a photon of X-ray energy is produced.
• This photon’s energy = change in the electron’s KE (before
and after collision).
• The maximum photon energy generated corresponds to 6
the instantaneous deceleration of the electron to zero KE.
 Conditions for Continuum
Spectra

• Also called bremsstrahlung, "braking radiation“.

• Produced by the deceleration of incident-beam particles.
• Incident electrons are slowed to varying degrees by the
strong electromagnetic field of the atomic nuclei.
• When all KE converted into a photon (no further
movement) - highest possible energy in the continuum.

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The Duane-Hunt Law
• For such an event,

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The Duane-Hunt Law simplified
• Upon substituting numerical values for the constants,
and rearrangement,

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Line Spectra from Electron Beam
Sources
• As shown, bombardment of a
Mo target produces intense
emission lines at ~0.63 & 0.71
Å.
• Such line spectra result from Line
Continuum
electronic transitions that Spectra
Spectra
involve the innermost atomic
orbitals.
• The short wavelength K series
result from the removal of an
electron from those orbitals
closest to the nucleus. 10
 TheMichaelJ.DrakeElectronMicroprobeLaboratory
UniversityofArizona

• K-lines: associated with K-shell transitions

• L-lines: associated with L-shell transitions etc.

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Interpreting emission lines
• , ,  lines all represent discrete magnitudes of emissions
• Thus K represents transitions

Shell Line Transition Energy level difference (jumps)

K  L to K 1
K  M to K 2
K  N to K 3
L  M to L 1
L  N to L 2
L  O to L 3
M  N to M 1
M  O to M 2
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M  P to M 3
Line Spectra from Fluorescent
Sources – Radioactive Sources
• A convenient way of producing a line spectrum is by
irradiating the element or one of its compounds with the
continuum radiation from an X-ray tube.
• The best-known example of an artificial radioactive
isotope:

• The resulting Mn Kα line at about 2.1 Å has proved to be a

useful source for both fluorescence and absorption 13
methods.
RECAP OF LECTURE

• X-ray fundamentals
• Emission of X-rays
• Continuum vs Line Spectra
• Duane-Hunt Law
• Emission Lines & Interpretation

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Week 4 Session 2
• Absorption Process
• Absorption Spectra
• Mass Absorption Coefficient
• XRF

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The Absorption Process
• Absorption of an X-ray quantum causes ejection of
one of the innermost electrons from the atom.
• Consequently an excited ion results.
• In this process, the entire energy of the hv of the
radiation is partitioned between the KE of the
electron and the potential energy of the excited ion.
• The highest probability for absorption arises when
the energy of the quantum exactly matches the
energy required to move the electron just to the
periphery of the atom (meaning the KE of the 16
electron approaches zero).
 APPLICATION: The Absorption
Spectrum for Pb
• Four peaks observed starting a 0.14 Å.
• The energy at this wavelength just matches the energy
required to eject the highest energy K electron of the
element.
• Do not confuse lowest
energy shell K with highest
energy required to eject K
electron! 

• Beyond this wavelength, the

E is insufficient to remove 17
any further K electrons.
The Absorption Spectrum for Pb
• The additional peaks beyond 0.14 Å correspond to the removal of an
electron from the L energy levels of lead.
• Three sets of L levels exist, thus three peaks are observed. Another set
of peaks corresponding to ejection of M electrons are located at still
longer wavelengths.
• Note also the K absorption edge for Ag is at longer wavelength than that
for Pb, reflecting the lower atomic number for Ag.

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The Mass Absorption Coefficient
• Beer’s Law applies to X-radiation, thus we may write

Po
ln  x
P

Here,
x is the sample thickness in cm
P and Po are powers of the transmitted and incident beams
μ is the linear absorption coefficient (characteristic of the element
and as well as the number of atoms in the path of the beam) 19
The Mass Absorption Coefficient
• A more convenient form of Beer’s Law is

Po
ln = μM ρx Eq. 3
P

Here,
ρ is sample density
μM is the mass absorption coefficient (independent of
the physical and chemical state of the element) with
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units of cm2/g.
The Mass Absorption Coefficient
• Thus the mass absorption coefficient for bromine has the same
value in gaseous HBr as in solid sodium bromate.
• Mass absorption coefficients are additive functions of the weight
fractions of elements contained in a sample. Thus,

• Here, μM is the mass absorption coefficient of a sample containing

the weight fractions WA, WB and WC of elements A, B and C.
• The terms μA, μB and μC are the respective mass absorption
coefficients for each of the elements. 21
Applications of X-ray Absorption
• Detection of broken bones in medicine
• Define the shapes of arteries and capillaries
(injection of strongly absorbing cesium iodide)
• Detection of impurities in sample
• Detection of levels of liquids in a container without
opening it.

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X-ray Fluorescence
• X-rays absorption by an atom can have sufficient energy to
actually eject an electron from an innermost orbital.
• This leaves a vacancy in the innermost orbital.
• An electron from the higher orbitals fills the vacancy.
• Excess energy is expended as a photon (E = energy
difference of the two orbitals involved.
• Thus, the material emits radiation, which has energy
characteristic of the atoms present. This release of energy
is termed fluorescence.
• Note abs < emis. Why?
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X-ray Fluorescence
• When fluorescence is to be initiated through
excitation from an X-ray tube, it must be ensured
that
• E involved is sufficiently high for the
corresponding absorption;
• Then, it’s a matter of using Equation 2 and the
appropriate wavelength of radiation to determine
the minimum voltage that must be applied.

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Worked Example
• What would be the minimum operating acceleration
voltage to bring about fluorescence involving K lines
in Ag?
Solution
First find out what is the wavelength of
radiation involved in generating the K line in
Ag?
Lit. suggests it’s 0.485 Å.

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Behera et al. 2010 26
X-ray Fluorescence Methods
• Excitation usually achieved using a beam of X-rays from an
XRT or a radioactive source.
• Samples being irradiated emit their own characteristic
fluorescence X-rays.
• Exploiting this fact, XRF is one of the most widely used of all
analytical methods for the qualitative identification of
elements having atomic numbers grater than of oxygen (>8).
• Often also used for semi-quantitative or quantitative
elemental analysis as well.
• A particular advantage is the non-destructive nature of the
technique. 27
XRF Spectrum

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XRF Spectra Interpretation
• Peak identification is done by comparison with
tables of emission lines of elements.

• Qualitative information from the spectrum can be

converted to quantitative information by studying
the peak heights.

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Applications of XRF

• Rapid determination of all but the light elements in;

• manufacturing industries
• liquid samples
• atmospheric samples
• rock and soil samples
• Advantages - non-destructive of samples
• Disadvantage - very costly

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X-Ray Diffraction (XRD)
• When x-rays are scattered by the ordered environment
in a crystal, interference (both constructive and
destructive) takes place among the scattered rays
because the distances between the scattering centers
are of the same order of magnitude as the wavelength
of the radiation. Diffraction is the result.
• The requirements for X-ray diffraction are:
1) The spacing between layers of atom must be
roughly the same as the wavelengths of the
radiation
2) The scattering centers must be spatially distributed 31
in a highly regular way.
Bragg’s law
• When an x-ray beam strikes a crystal surface at some
angle θ, a portion is scattered by the layer of atoms at
the surface. The unscattered portion of the beam
penetrates to the second layer of atoms where again a
fraction is scattered and the remainder passes on to
the third layer.
• W.L. Bragg treated the diffraction of x-rays by
crystals a shown below:

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 Analysing Crystal
• Layers of ions or
molecules arranged in
a well ordered system
• x-ray radiations falling
on the crystal are
parallel waves I.e.
waves AX and BG are
in phase with each
other
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• For waves to immerge as a beam, XD and HE must
be in phase with each other
• If out of phase, waves will be destroyed.
• Lower wave travel extra distance GYH compare to
the upper wave.
• Only when the GYH is a whole number will the wave
HE remain in phase with XE

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• Relationship between x-ray wavelength, inter-planer
distance and angle of diffraction can be deduced.
• From  GXY, sin  = GY/d  GY = dsin 
• From  YXH, sin  = YH/d  YH = dsin 
•  path difference (GY + YH) = 2dsin 

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• Now the two reflected rays, XD and YE will
constructively interfere when the path difference is
equal to the wavelength () or a multiple of it.
• the condition for x-ray diffraction is 2dsin = n 
• Only x-rays of a particular wavelength are diffracted
by the crystal

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APPLICATIONS OF XRD
• Structural determination
• phase analysis
• solid solution analysis
• detection of particle analysis
• detection of preferred orientation and order/disorder

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