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Lab Manual PDF
Lab Manual PDF
Lab Manual PDF
7
Background
Normally one would use a microscope to view small objects. For a microscope, light is
scattered by an object and collected using lenses, which in turn magnifies the image of the
object. The limit of the microscope is intrinsic to the nature of the electromagnetic radiation
that is used to probe the object. If we use white light we cannot look at objects smaller
than the wavelength of light, which is about 10 -6 m. Since the atom has dimensions of
about 10-10 m we cannot image an atom with a photon of white light. X-rays, on the other
hand, have a wavelength of about 10 -10 m and are suitable for imaging objects at the
atomic scale.
X-rays are electromagnetic radiation of wavelength about 1 Å (10-10m) which is about the
same size as an atom. They occur in that portion of the electromagnetic spectrum between
gamma rays and the ultraviolet. The discovery of X-rays in 1895 enabled scientists to probe
crystalline structure at the atomic level. X-ray diffraction has been employed in two main
areas: for the fingerprint characterization of crystalline materials and the determination of
their structure. Each crystalline solid has its unique characteristic X-ray powder pattern,
which may be used as a "fingerprint" for its identification. Once the material has been
identified, X-ray crystallography may be used to determine its structure, i.e. how the atoms
pack together in the crystalline state and what the inter-atomic distance and angle are etc.
X-ray diffraction is one of the most important characterization tools used in solid-state
chemistry and materials science.
We can determine the size and the shape of the unit cell for any compound most easily
using the diffraction of x-rays.
Diffraction of X-rays
Given that two parallel rays will strike a grating at an angle theta where the grating
separation is given as d then :
A'
θ
B'
θ d
2d
A
B
θ
C
Γ
sin θ =
2d
θ 2d 2d sin θ = Γ
Γ = AC − A' B '
given A' B ' = AB then Γ = AC − AB = BC
Γ = BC = λ ( path difference)
Γ
2d sin θ = λ
X-ray Sources
point focus
anode (top view)
sealed tube
The primary beam is used for Single crystal work
experimentation. requires a point focus,
while powder work
cathode primary beam employs the line focus
e-
rotating anode
main beam
cathode
evacuated
-
e chamber
50kV
anode
metal filter
White Radiation
Electron reaccelerate when “Bremsstrahlung”
entering the metal and "bend" or breaking radiation
their trajectory path. Loss of
momentum results in generation
of X-rays.
http://xray.tamu.edu/safety_training.php
The following appendix is available for your information and not necessary
reading.
Bibliography
"Procedures Manual for Use of Radioisotopes and Radiation
Producing Devices", Office of Radiological Safety, Texas A & M
University
Learning Experiences
• Materials Analysis
• Qualitative Analysis
• Bragg's Law
In this lab you will measure the x-ray powder diffraction pattern from silicon. Your TA
will give you the sample to be measured and show you how to set up the D8 x-ray
diffractometer.
You should measure all the values of 2theta from the chart, and after converting them into
d values calculate the repeat distance in your unit cell. In your lab notebook list all the
2theta values with their corresponding values of n and d.
INSTRUMENTATION
The X-ray diffraction experiment requires an X-ray source, the sample under investigation
and a detector to pick up the diffracted X-rays. Figure 1 is a schematic diagram of a powder
X-ray diffractometer.
R1 R2 Receiving Slit
θ θ
R1 = R2
Sample
PROCEDURE
**Do not open the enclosure while the alarm red light is on.
1. Obtain a sample from your instructor and place it into the sample holder.
2. Place sample holder in the sample positioner.
3. Record the values of the fixed slits.
4. Close the DOORS. The green ready light should be the only LED displayed
5. Run the COMMANDER program.
6. For RAW-file name type ijkSILICON wher ijk are YOUR initials
7. Add a title under sample identification.
8. Set the instrument at optimum setting as follows
14. Use the ZOOM key to zoom out the plot (if necessary).
15. Keep this information for Laboratory 3.
(You can cut and paste the results from the peak list to the notepad)
16. Find Silicon in the ICCD data base.
reference
peaks
appear in
red
CHECK
ONLY
THE *
toggle all
unwanted
red all
wanted
green
23. Print
the results
and be sure
you have
written
down the
peak
positions.
Laboratory 3. Indexing Powder Patterns
Learning Experiences
In this lab you will manually index the powder pattern for Silicon. An example of how to
index powder patterns is presented. The mathematics are introduced and the step by step
procedure is presented. You will need a calculator and a pencil.
For the peak positions of Silicon use the values that you determined in Laboratory 2.
or ask your Laboratory assistant for the values.
----------------------------------------------------------------------
2d sin θ = nλ
nλ
sin θ =
2d
λ2
sin θ =
2
4d 2
d* can be determined as :
1 (h 2 + k 2 + l 2 )
=
d2 a2 Let X = λ2/4a2 and M = h2+k2+l2
λ 2
sin 2 θ = (h 2 + k 2 + l 2 ) Now create a table for M values given h,k and l are integers
2
4a
sin 2 θ λ2
=
( h 2 + k 2 + l 2 ) 4a 2
Largest common sin2θ/M value(s) (X) are (see bold values above)
From Table 2 we see that 0.0362 is the result for sin2θ/M3 : M3 is the result for h =1, k =1
and l =1. Completing the table for the first 4 peaks we now can assign these peaks with
h,k,l values
Table 3. M = h2 + k2 + l2
h k l M
1 1 1 3
2 0 0 4
2 2 0 8
3 1 1 11
Or we can solve Bragg’s equation for each observed peak. For example for
2θ = 38.52 : sin2θ/0.0362 = 3.005652 or 3.00. From table 1 we see that M=3
is equivalent to h=1, k=1 and l =1. Therefore the peak at 38.52 is assigned as
the (1,1,1) reflection. Table 4 summarizes the results for all peaks and assigns
their h,k,l values.
Table 4
2θ sin2θ/0.0362 M h,k,l
38.52 3.005652 3 1,1,1
44.76 4.004662 4 2,0,0
65.14 8.005491 8 2,2,0
78.26 11.00178 11 3,1,1
82.47 12.00214 12 2,2,2
99.11 15.99904 16 4,0,0
112.03 18.99298 19 3,3,1
116.6 19.99667 20 4,2,0
137.47 23.99066 24 4,2,2
Laboratory Particle: Index the following.
First Task. Fill in Table 1
e.g. for n=1 h=1,k=0,l=0 will afford M1 = 1
From your peak list from Laboratory 2 fill in this table. For example a peak at 26o 2θ will afford θ = 13o
sin2(13) = 0.0506 sin2(13)/M1 = 0.0506/1 = 0.0506 sin2(13)/M2 = 0.0506/2 = 0.0253
Complete this table for your peaks. (or you may generate a spread sheet in EXCEL to do the same thing)
# 2θ Θ sin2θ/M1 sin2θ/M2 sin2θ/M3 sin2θ/M4 sin2θ/M5 sin2θ/M6 sin2θ/M8 sin2θ/M9 sin2θ/M10 sin2θ/M11 sin2θ/M12 sin2θ/M14 sin2θ/M15 sin2θ/M16
1
2
3
4
5
6
7
8
9
10
sin2θ/M17 sin2θ/M18 sin2θ/M19 sin2θ/M20 sin2θ/M21 sin2θ/M22 sin2θ/M23 sin2θ/M24 sin2θ/M25 sin2θ/M26 sin2θ/M27 sin2θ/M28 sin2θ/M29 sin2θ/M30
Largest common sin2θ value from Table 2 (value of X) = _________
Remember X = λ2/4a2
Calculate unit cell a given λ = 1.54056Å _________
Now complete Table 3 from the given information assign the h,k,l value for each peak.
Learning Experiences
"PowderX: Windows-95 based program for powder X-ray diffraction data processing",
C. Dong, J. Appl. Cryst. (1999), 32, 838-838
In this lab you will index a powder pattern from a known and unknown sample. You will
need to use the computers in the X-ray Laboratory. Bring a calculator, your notebook and
a pencil.
1. Peak Picking
- Generation of a list of dhkl and their intensities
2. Peak Indexing with the program TREOR
- Choice of unit cell parameters based on the number of
reflections indexed and the figure of merit.
3. Indexing and Cell parameters refinement
1. Peak Picking. Begin the program POWDERX and load the Ascorbic
Acid data.
Point to OK
Example of the Table of peak
positions from the peak Pick
routine
Step 2. Indexing unit cell with the program TREOR
Let the program run and examine (print) the output for later study.
(point to file and then print)
Summary of TEROR output
Scroll down the TEROR listing file and find : THIS MAY BE THE
SOLUTION
This is a good sign that you have successfully indexed the cell
The main rule is that if all the first twenty lines are indexed and the De
Wolff figure of merit M(20) [J. Appl. Cryst. (1972). 5, 243] is greater
than 9, then the indexing problem is in principle solved.
Comments
a. If the De Wolff figure of merit M(20) is less than 10 or more
than one line is un-indexed within the 20 first observed lines,
the solution is probably meaningless.
c. Observe that the De Wolff figure of merits are derived from the assumption
that no systematic extinctions occur and all lines are indexed.
Warning. a high figure of merit has no meaning unless the lines are indexed.
Notice all of the peaks (save the one near 13.48o ) are labeled. You did
not select the 13.48 peak at the peak picking stage so it is not labeled
now. Add this peak with the TASK/ADD remove peak command and
type finish. For the wavelength box point to OK Goto to
INDEXING/DHKL and recalculate the PEAK MATCH. Now when
you ZOOM you will see the peak labeled.
CAUTION : Care must be taken when manually picking the peak. You
could be off and assign the peak as 100 which would be WRONG!
Finally Point to the REFINE CELL button and you will refine the cell.