X-Ray Spectrometry

X-ray Fluoresces (XRF)

X- ray Absorption (XAS

X-ray Diffraction (XRD)

For CH301 Lecture @ The University of the South Pacific

D.Rohindra 2019
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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Generation 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

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Instrument Components
• X-Ray Source
• device for restricting wavelength range
• sample holder
• radiation detector
• signal processor

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EQUIPMENT

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 X-ray Absorption Spectroscopy
and
X-Ray Fluorescence Spectroscopy
These are inner shell spectroscopies.

Inner shell means that an x-ray

interacts primarily with a deep-
core electron rather than with a
valence electron.

XRS
XAS
X-Ray Absorption
• If the wavelength of an x-ray is short enough, it will excite an
atom that is in its path (i.e. atom will absorb the x-ray)
• x-ray emitted from a particular element will be absorbed by
elements with lower atomic number
• The relationship is expressed as follows:

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 • Continuous spectra (white radiation)–
X-ray Spectra range of X-ray wavelengths generated by
the absorption (stopping) of electrons by
the target
• Characteristic X-rays – particular
wavelengths created by dislodgement of
inner shell electrons of the target metal;
x-rays generated when outer shell
K electrons collapse into vacant inner shells
K
• K peaks created by collapse from L to K
X shell;
K peaks created by collapse from M to K
shell
When light hits an electron, the
electron jumps to a higher energy
level, then drops back to its original,
shell, emitting light
 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
M  P to M 3

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 I =Io exp(-Ax)
where x = sample thickness
P = transmitted beam
Po= incident beam
A = linear absorption coefficient

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• more convenient form

I =Io exp(-ρx)

• where m= mass absorption coefficient

(cm2/g)
 = density of the sample

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ABSORPTION SPECTRUM

Ag
Pb

13
• simple and has few broad but well define peaks
characteristics of elements
• Peaks: arise as a result of complete ejection of electron from
K or L shells etc. Here the probability of absorption is
greatest because the energy of the x-rays is exactly equal to
the energy required to expel the electrons
• Mass absorption coefficient: Beer’s law applies to other
types of electromagnetic radiation.

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•  (mass absorption coefficient) of a sample is
determined by the mass absorption coefficient of all
elements comprising the sample and their weight
fractions. Thus,
• m = WAA + WBB + WCC + …
m : mass absorption coefficient of sample
WA, WB, WC, : wt fraction of elements A,
B, + C
A, B, C : mass absorption coefficient
for A, B, C,

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 Example
• The mass absorption coefficient for Ni,
measured with the Cu K line, is 42.2 cm2/g.
Calculate the thickness of the nickel foil that
was found to transmit 36.1% of the incident
power of a beam of Cu K radiation. Assume
the density of Ni is 8.9 g/cm3

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• Use

• Direct absorption methods: limited to the analysis of samples

containing a single heavy element in a matrix of lighter
elements. Reason can be seen from previous equation.
m = WAA + WBB + WCC + …

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• Condition under which m will reflect the
concentration of one element only, eg. A is when
WAA is much larger than WBB & WCC etc.

• Examination of equation above indicates this will

only occur if the atomic weight, A and atomic no. Z
is significantly larger than all of the rest. Example,
Sulfur in hydrocarbon or lead in gasoline.

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Example see Skoog et al., p296
• A solution of I2 in ethanol had a density of
0.794g/cm3. A 1.50 cm layer was found to transmit
27.3% of the radiation from a Mo K source. Mass
absorption coefficients for I,C,H, and O are 39.2,
0.70. 0.00, and 1.50, respectively.

(a) calculate the percent of I2 present,

neglecting absorption by the alcohol
(b) correct the results in part (a) for the
presence of alcohol

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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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The vegetable garden
When this house was sold, there was a wooden deck off the dining room.
This was replaced with a paving stone patio and converted the adjacent
plot of ground into a vegetable garden.
Wood preservative
The wood used to make the deck was treated with the wood preservative
chromated copper arsentate (CCA), which is chromium-bearing analogue of
copper orthoarsente, Cu3(AsO4)24H2O.

CCA-treated wood is known to leach all three elements into surrounding soils.

I had some questions:

• How much As is in the soil? Is it higher near the patio than else where in the
garden?
(Use XRF)

• What chemical species is the As in the soil? (Use XAS)

 XRF Spectra
Soil samples taken from near the deck and 5 meters away

Clear enhancement of both As and Cr in the soil but near the deck. As is enhanced roughly 2 fold.
XAS spectra.

As can exist in two forms .

Prepare standards of As5+ and As3+

X-ray Diffraction Technique
X-ray Crystallography Methods
Single-Crystal: Laue Method

Several directions simultaneously fulfill Bragg equations

Good for symmetry, but poor for analysis because distorted

Fig 7.39 of Klein (2002) Manual of Mineral

Science, John Wiley and Sons
X-Ray Diffraction
• Crystals characterize by well
defined and symmetrically
arranged planes
• shape depend on the process of
crystallization but angle between
planes remain the same
• shape and size of crystals are
define by six parameters

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Diffraction of X-rays from crystals
A  D

B
E
 X 

 
d
G H
 
Y
d

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Scattering of the X-rays
• X-ray beam is scattered as it strikes X on a crystal surface at
some angle 
• Unscattered part of the x-ray beam penetrate to second layer
Q and scattered on interaction with atoms
• The scattered x-ray beams is reflected from the plane at
some angle 

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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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• If the distance GY + YH = n, then the scattered radiation
will be in phase at XH and the crystal appear to reflect the
x-radiation.

• In other words constructive waves are reflected.

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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.
• Diffraction of x-rays
• The spacing between layer of atoms must be
roughly the same as  of the radiation
• The scattering centers must be spatially
distributed in a highly regular way

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Sir William Henry Bragg:
•William Henry and William Lawrence Bragg Bragg’s law
(father and son) found a simple interpretation
of von Laue’s experiment.
• They assume that each crystal plane reflects
radiation as a mirror and analyze this situation for
cases of constructive and destructive interference.

Noble
prize
1915!

Conditions for reflection: 2d sin  n  

The most important thing in science is not so much to obtain
new facts as to discover new ways of thinking about them.
 Derivation of Bragg’s law
x
sin( )  θ
d hkl
 x  d hkl sin( )
θ
dhkl
θ x

Path difference Δ= 2x => phase shift

Constructive interference if Δ=nλ
This gives the criterion for constructive interference:

   2dhkl sin( )  n
Bragg’s law tells you at which angle θB to expect maximum
diffracted intensity for a particular family of crystal planes.
For large crystals, all other angles give zero intensity.
 The powder diffractometers typically use
the Bragg-Brentano geometry

Detector
X-ray
tube

w  2

• The incident angle, w, is defined between the X-ray source and the sample.
• The diffracted angle, 2, is defined between the incident beam and the detector angle.
• The incident angle w is always ½ of the detector angle 2 .
• In a :2 instrument (e.g. Rigaku RU300), the tube is fixed, the sample rotates at  °/min
and the detector rotates at 2 °/min.
• In a : instrument (e.g. PANalytical X’Pert Pro), the sample is fixed and the tube rotates
at a rate - °/min and the detector rotates at a rate of  °/min.
A single crystal specimen in a Bragg-Brentano diffractometer
would produce only one family of peaks in the diffraction
pattern.

2

At 20.6 °2, Bragg’s law The (110) planes would diffract at 29.3 The (200) planes are parallel to the (100)
fulfilled for the (100) planes, °2; however, they are not properly planes. Therefore, they also diffract for this
producing a diffraction peak. aligned to produce a diffraction peak crystal. Since d200 is ½ d100, they appear at
(the perpendicular to those planes does 42 °2.
not bisect the incident and diffracted
beams). Only background is observed.
 A polycrystalline sample should contain thousands of
crystallites. Therefore, all possible diffraction peaks should be
observed.

2 2 2

• For every set of planes, there will be a small percentage of crystallites that are properly
oriented to diffract (the plane perpendicular bisects the incident and diffracted beams).
• Basic assumptions of powder diffraction are that for every set of planes there is an equal
number of crystallites that will diffract and that there is a statistically relevant number of
crystallites, not just one or two.
 Example: Diffraction Patterns
• Each peak represents the solution to Bragg’s law for known radiation
wavelength ( = 0.154nm)
• The unique relationship between such patterns and crystal structures
provide a powerful tool for identification of the phase composition of
powders and polycrystalline materials.
 Basis and Bravais Structure Factor Terms
Np Nb
F  e 2  igrn
m
f e 2  igrm
 FBR FBA
n1 m1
The following simple table giving the integer values of FBR for the different types of centering
translations. Keep in mind that these are valid for any crystal system.

Centering type Missing Reflections Possible Reflections Bravais Term FBR for
(FBR = 0) (FBR ° 0) possible reflections
P (primitive) None All 1
I (body-centered) (h + k + l) odd (h + k + l) even 2
A (base-centered on A (k + l) odd (k + l) even 2
face)
B (base-centered on B (h + l) odd (h + l) even 2
face)
C (base-centered on C (h + k) odd (h + k) even 2
face)
F (face-centered) hkl mixed hkl unmixed 4
The Seven Crystal Systems
System Axes Angles
Cubic a=b=c ===90

Tetragonal abc ===90

Orthorhombic abc ===90

Monoclinic abc ==90

Hexagonal a=bc ==90, =120

Rhombohedral a=b=c 90

Triclinic abc 90

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BRAVAIS LATTICES

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Millers Indices
A short hand notation to describe certain crystallographic directions and planes in a material.

Lattice directions are in direct space and are denoted by [ ] brackets.

A negative number is represented by a bar over the number.

It represents the direction of the planes on the three axes.

The values are given as reciprocals

https://www.youtube.com/watch?v=-40Qi-Ve1dQ
Different sets of planes

https://www.youtube.com/watch?v=pMTA_wiY784
Powder Diffraction Plots
θ = arcsin (nλ / 2d)

λ(Cu) = 1.54Å
d - Qtz [101] = 3.342
θ = 13.32° ; 2θ = 26.64°

Quartz
 Interpreting X-ray data
 We will use the data obtained to
 identify the mineral
 determine the dimensions of the unit cell.
 Calculating Miller Indices from X-ray diffraction Pattern
Please visit this link to view how miller Indices are calculated.

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