Chapter 5: X-Ray Related Techniques

Problem 5.1: The typical Jablonski diagram (i.e., Figure 7.3; also see the “Compare and Contrast—Optical
Absorption versus Photoelectric Absorption”) shows electronic transitions for the valence shell of an atom or
molecule. Using Figure 7.3 as a style guide, construct an energy diagram in the style of a Jablonski diagram for
an XRF Kα emission. As you construct your Jablonski diagram, make sure you consider the differences in
atomic versus molecular transitions.

Problem 5.2: Why is it quantum mechanically impossible to observe a characteristic L β emission for
magnesium? A diagram similar to Figure 10.1 might be helpful in answering this question.

L indicates that the electron hole was generated in the n = 2 quantum shell and indicates that an electron fell
from two shells above. Two shells above would be n = 4. Magnesium does not have any n = 4 electrons.

Problem 5.3: In the orbital diagrams depicted, an ejected electron “hole” is designated with a “⊕” and the
arrow represents a higher n-value electron cascading into that hole. Label each transition (i.e., K α, Lβ, and so
on).

K K K L M
Problem 5.4: Compare and contrast photoelectric absorption of source radiation with molecular UV-vis and IR
absorption of source radiation. In what ways are they similar? How are they different?

This is an open ended question and instructors will need to adjust their expectations
accordingly. Students should mention that photoelectric absorption involves an electron being
ejected from an inner core quantum shell and molecular UV-vis absorption involves bonding
electrons and results in the electron being promoted to a higher quantum shell. IR absorption
involves changes in vibrational quantum states. In photoelectric and UV-vis absorption, the
relaxation event involves an electron “falling” into a lower quantum state. The main difference
is that the vacancy in the lower quantum state for photoelectric events is the result of a lost
electron while in UV-vis events, the vacancy in the lower quantum state is the result of an
electron being promoted out of that state to a higher energy state. IR relaxation events involve
vibrational quantum states rather than electronic quantum states, however the existence of
vibrational states requires the existence of bonds. IR and molecular UV-vis events are the
result of quantum states that exist within the valence shells of the molecules. Additionally, for
IR and UV-vis events, the energy of the absorbed photon must exactly match the energy
difference between the two quantum states involved. In photoelectric absorption, the energy
of the absorbed photon must exceed the threshold energy needed to eject the electron. Any
excess photon energy is carried away by the ejected electron as kinetic energy.

Problem 5.5: In what ways does the variable  in Equation 5.3 resemble the variable  in Equation 6.5? How is
 different from ?

is the molar absorptivity of an atom or molecule and represents a species specific constant that governs the
absorptivity of a species. must be determined experimentally. In a similar manner the variable 
represents the atom specific constant that governs the absorptivity of x-rays by an atom. However in an
atom, x-rays are absorb by inner core electrons which typically are not affected by the bonding environment
of the atom. As a result, tends to track atomic electron density which roughly tracks atom number as

4
μ∝Z

Problem 5.6: Use Equation 5.5 and Example 5.1 to determine the minimum wavelength, the maximum
frequency and the energy in units of joules for the bremsstrahlung radiation generated by a X-ray tube with a
voltage gradient of
(a) 25 kV (b) 50 kV (c) 100 kV

a)
hc 1240 pm 1240 pm
λ min = = = =49.6 pm=49.6 X 10−12 m
eV kV 25.00 kV
 m
2.99 X 1 0 8
c s 18
ν max= = =6.03 X 1 0 Hz
λ 49.6 X 1 0 m
−12

E=h ν= ( 6.626 X 10 Js )( 6.03 X 1 0 s )=4.00 X 10 J

−34 18 −1 −15

b) Part “b” is worked in the exact same way as part “a” with appropriate substitutions made
at the highlighted points in each equation.
c) Part “c” is worked in the exact same way as part “a” with appropriate substitutions made
at the highlighted points in each equation.

Problem 5.7: What voltage would you need to apply to the X-ray tube of an XRF spectrometer in order to
induce a Kα emission from the following:
(a) Fe (d) Ru (g) Co
(b) Cu (e) Zn (h) Sn
(c) Ti (f) Ni (i) Ca

See Examples 5.1 & 5.2 on pages 308 & 309 for a worked out example of this type of problem.

Problem 5.8: Given a crystal lattice distance of d = 2.35Å, use Bragg’s Law to calculate the (n = 1) angle
required for the constructive interference of a  = 1.54 Å X-ray beam.

Bragg’s Law states

nλ=2 dsinθ Eq. 5.6

n = integer
wavelength of incident X-ray
d = the distance between the planes in the atomic lattice
 = the incident angle between the X-rays and the plane of reflection.

Substitution yields

( 1 ) 1.54 Å=2 ( 2.35 Å ) sinθ

θ=si n
−1
( 1 ( 1.54 Å )
2 ( 2.354 Å ))=19.1°
Problem 5.9: For an X-ray beam of 2.01 Å experiencing constructive interference incident on a crystal surface
at an angle of 45 degrees, determine the crystal lattice distance “d,” assuming first-order (n = 1) Bragg
diffraction.

Substitution into Bragg’s equation yields,

1 ( 2.01 Å )=2 dsin 45°

Solving for d yields,

1(2.01 Å )
d= =1.421 Å
2sin 45°

Problem 5.10: It is customary to report XRF in units of eV. However, in Chapter 6, on UV-vis spectroscopy,
we reported absorption wavelengths in units of nanometers. For comparative purposes, convert the range of 5
to 20 eV into units of nanometers. Compare the resolution of a typical XRF spectrometer to that of a UV-vis
spectrometer in the context of the bandwidth of the X-ray and UV-vis regions of the electromagnetic spectrum.

We will use the Duane-Hunt law to convert eV to .

m
(4.136 X 1 0−15 eV ∙ s)(2.99 X 1 08)
hc s −7
λ 5 eV = = =2.47 X 1 0 m=247 nm
eV 5 eV

−15 8 m
( 4.136 X 1 0 eV ∙ s)(2.99 X 10 )
hc s
λ 20eV = = =6.183 X 10−8 m=61.8 nm
eV 20 eV

A typical UV-vis spectrometer’s bandwidth is limited by the optics employed in its construction. Typical UV-vis
spectrometers can operate from ~190 nm to ~900 nm for a spectral range of ~710 nm. We need to remind
ourselves that the tern UV-vis spectrum is a bit of a misnomer since the visible range of the EM spectrum ends at
700 nm. And although the UV-vis portion of the EM spectrum extends down to ~10 nm, the typical UV-vis
spectrometer’s optics limit its use to approximately ~190 nm.

As we have shown in this problem, a typical WDXRF can operate from ~61nm  ~247 nm for a spectral range of
186 nm, however it is important to recognize that we are utilizing two different regions of the EM spectrum when
we do an XRF analysis. The x-rays induce ionization of a core electron and the result is a fluorescence in the UV-vis
region of the EM spectrum. Although the x-ray region of the EM spectrum can be thought of as extending from 1 X
10-8m (10 nm) to 1 X 10-11m (0.01 nm) for a spectral range of ~1000 nm, we are limited by the source materials
used to generate x-rays and the optics used to capture the UV-vis fluorescence.
Problem 5.11: In Problem 10.10, we converted the spectral resolution of WDXRF spectrometers from eV to
nm. For comparative purposes, convert the spectral range of a typical EDXRF (100–300 eV) into nanometers.

We will use the Duane-Hunt law to convert eV to .

−15 8 m
( 4.136 X 10 eV ∙ s )(2.99 X 1 0 )
hc s −8
λ 100eV = = =1.2366 X 1 0 m=12.4 nm
eV 100 eV

m
(4.136 X 10−15 eV ∙ s )(2.99 X 1 08 )
hc s
λ 300eV = = =4.122 X 10−9 m=4.12 nm
eV 300 eV

In problem 5.10 we saw the spectral range of a typical WDXRF is ~186 nm. Here we see the
spectral range of a typical EDXRF is 8.25 nm.

Problem 5.12: Consider this scenario. You are writing a business plan in order to open a commercial laboratory
that will conduct routine agricultural microanalysis of soil for the nutrients Ca, Mg, Cu, and Zn. You will need
to be able to quantify these elements in the ppm range. The going rate for an analysis of this type in your area
of the country is $60 per element per analysis. Your anticipated overhead will be $1500 per month, which does
not include a loan payment plan for the instrument. Use the Internet to research commercially available XRF
spectrometers and complete the business plan. Justify (in your business plan) your choice of XRF spectrometer
and include in your final business plan the 5-year loan payments (5% APR) for your XRF. Do not forget to
include your salary. How many analyses per week will you need to conduct in order for your business to
succeed? Make sure you justify your choice of XRF spectrometer against the number of analyses per week you
will be conducting.

This is an open ended question and the answers will vary considerably based upon changing market forces and
assumptions made by the student. Students should recognize that the routine analysis of the nutrients Ca, Mg,
Cu, and Zn in soil does not require the use of a high-end WDXRF spectrometer and the business plan would be
better served by the lower cost and higher throughput of a bench quality EDXRF spectrometer.

With these assumptions in place, a thumbnail sketch of a business plan might contain the following analysis.

Initial cost of EDXRF = $60,000

A five year loan with a 4.5% interest rate would yield a loan payment of ~$1,119/mo

Annual salary of owner = $84,000/year  $7,000/mo

Monthly Operating Expenses

Instrument Loan Payments = &1,119
Overhead = $1,500
Salary = $7,000
Total = $9,619
If you analyzed each soil sample for all four elements, then each soil sample would generate 4 x
$60 = $240. In order to meet your monthly cash flow obligations, you would need to analyze
$9,616/mo ÷ $240/sample = 40 samples/mo

A more sophisticated business plan might also include additional equipment and supply
purchases, marketing expenses and depreciation schedules for the instrument and other lab
equipment.

Problem 10.13: Compare and contrast the physical quantum events involved in XRF, XPS, and AS techniques.
How are they similar? How are they different?

This question is essentially answered by the Venn diagram in the “Compare and Contrast”
profile on p. 328

Problem 5.14: Determine the Bragg angle () needed to obtain first-order (n = 1) constructive interference for
an X-ray of wavelength 10 Å, given the interstitial distance (d) between lattice points in the diffraction crystal,
for the following:
(a) 12 Å (c) 32 Å (e) 6.8 Å
-4
(b) 7.5 nm (d) 6 × 10 mm (f) 300 pm
a) Bragg’s Law states

nλ=2 dsinθ Eq. 5.6

n = integer
wavelength of incident X-ray
d = the distance between the planes in the atomic lattice
 = the incident angle between the X-rays and the plane of reflection.

Substitution yields

( 1 ) 10 Å=2 ( 12 Å ) sinθ

θ=si n−1
( )
1 ( 10 Å )
2 ( 12 Å )
=24.63 °
The answer to parts (b)  (f) are obtained by substitution the various d-values into the Bragg equation. Care
must be taken for parts (b), (d) & (f) to convert the d-value to angstroms.
Problem 5.15: Determine the Bragg angle () needed to obtain first-order (n = 1) constructive interference for
a 200 eV X-ray, given the interstitial distance (d) between lattice points in the diffraction crystal for the
following:
(a) 12 Å (c) 6 × 10-4 mm (e) 6.8 Å
(b) 7.5 nm (d) 32 Å (f) 300 pm

This is a tricky question. In order for a crystal to function as a diffraction grating for x-rays, the
wavelength of the x-ray must be able to “fit” between the interstitial distances within the
crystal. In other words, you must satisfy the requirement of n ≤ 2d.

Using the Duane-Hunt law to convert 200 eV into a wavelength we obtain,

−15 8 m
( 4.136 X 10 eV ∙ s )(2.99 X 1 0 )
hc s −9
λ 200eV = = =6.1833 X 1 0 m=61.833 Å
eV 200 eV

For all of the interstitial distances found in parts (a) (f) where 2d < n, the crystal would be
unsuited for the purposes of Bragg diffraction. This eliminates parts (a), (b), (e) and (f).

Then we can use the Bragg law to find  for parts (c) and (d). Care must be taken when using
Bragg’s law to match the units of the incident x-ray to the interstitial distance between
reflection planes.

nλ=2 dsinθ Eq. 5.6

θ=si n
−1
( 2nλd )
(c) θ=si n
−1
{ (1)(61.833 Å)
( 2 ) ( 60 Å ) }
=31°

(d) θ=si n
−1
{ (1)(61.833 Å)
( 2 ) ( 32 Å )}=75 °

Problem 5.16: Determine the Bragg angle () needed to obtain first-order (n = 1) constructive interference for
an X-ray with a frequency of 3 × 10 18 Hz, given the interstitial distance (d) between lattice points in the
diffraction crystal for the following:
(a) 12 Å (c) 6.8 Å (e) 6 × 10-4 mm
(b) 7.5 nm (d) 300 pm (f) 32 Å

Using the relationship of

 c
λ= =
( 2.99 X 1 08
m
s )
=9.967 X 1 0−11 m=0.9967 Å
ν 18 −1
3 X 10 s

Solving the Bragg equation for ,

(a) θ=si n
−1
( 2nλd )=si n {(1)(0.9967
−1
(2)(12 Å) }
Å)
=2.38°

Parts (b)  (f) are determined by making appropriate substitutions into the Bragg equation.

Problem 5.17: Label each of the following Miller index points within the given crystal lattice. The origin is
indicated by a black dot.

(a) [−1−10] (d) [100] (g) [212]

(b) [−111] (e) [111] (h) [0–12]
(c) [210] (f) [302] (i) [2–21]

The miller points are labeled in this

diagram. The miller point for part (i) is
technically outside of this diagram
however it is shown here.
Problem 5.18: There are nine labeled points in the given crystal lattice. Provide the proper Miller index for
each of these points. The origin is indicated by a black dot.

1: [123]
2: [213]
3: [312]
4: [322]
5: [001]
6: [300]
7: [011]
8: [221]
9: [110]

Problem 5.19: Sketch a unit cell similar to the one depicted in Figure 5.29 and shade and label the following
planes:
(a) (010) (c) (100) (e) (001)
(b) (110) (d) (101) (f) (011)
(a) Invalid plane index. Does not (c) Invalid plane index. Does not (e) Invalid plane index. Does not
define a plane define a plane define a plane

(b) (d) (f)