Bragg's Law

Table of Content
Introduction
1.
2.

Braggs Law
References
The structures of crystals and molecules are often being identified using x-ray diffraction studies, which are
explained by Braggs Law. The law explains the relationship between an x-ray light shooting into and its reflection
off from crystal surface.

Introduction
Braggs Law was introduced by Sir W.H. Bragg and his son Sir W.L. Bragg. The law states that when the x-ray is
incident onto a crystalsurface, its angle of incidence, , will reflect back with a same angle of scattering, . And,
when the path difference, d is equal to a whole number, n, of wavelength, a constructive interference will occur.
Consider a single crystal with aligned planes of lattice points separated by a distance d. Monochromatic X-rays A,
B, and C are incident upon the crystal at an angle . They reflect off atoms X, Y, or Z.

The path difference between the ray reflected at atom X and the ray reflected at atom Y can be seen to be 2YX.
From the Law of Sines we can express this distance YX in terms of the lattice distance and the X-ray incident
angle:
If the path difference is equal to an integer multiple of the wavelength, then X-rays A and B (and by extension C)
will arrive at atom X in the same phase. In other words, given the following conditions:
then the scattered radiation will undergo constructive interference and thus the crystal will appear to have
reflected the X-radiation. If, however, this condition is not satisfied, then destructive interference will occur.

Braggs Law
n=2dsin
where,

 = the wavelength of the x-ray

d = the spacing of the crystal layers (path difference)
= the incident angle (the angle between incident ray and the scatter plane)
n = an integer

The principle of Braggs law is applied in the construction of instruments such as Bragg spectrometer, which is
often used to study the structure of crystals and molecules.

References
1.
2.

Bragg, W.L. The Crystalline State: Volume I. New York: The Macmillan Company, 1934.
McQuarrie, Donald A. Physical Chemistry: A molecular Approach. Sausalito: University Science Books,
1997.

Powder X-ray Diffraction

Table of Contents
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2.
3.
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2.
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2.
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7.

Introduction
Bragg's Law
Instrumentation
X-ray Tubes
X-ray Detectors
Gas-Filled Transducers
Scintillation Counters
Semiconductor Transducers
References
Outside Links
Problems
Contributors

When an X-ray is shined on a crystal, it diffracts in a pattern characteristic of the structure. In powder X-ray
diffraction, the diffraction pattern is obtained from a powder of the material, rather than an individual crystal.
Powder diffraction is often easier and more convenient than single crystal diffraction since it does not require
individual crystals be made. Powder X-ray diffraction (XRD) also obtains a diffraction pattern for the bulk material
of a crystalline solid, rather than of a single crystal, which doesn't necessarily represent the overall material. A
diffraction pattern plots intensity against the angle of the detector, 2.

Introduction
Since most materials have unique diffraction patterns, compounds can be identified by using a database of
diffraction patterns. The purity of a sample can also be determined from its diffraction pattern, as well as the
composition of any impurities present. A diffraction pattern can also be used to determine and refine the lattice
parameters of a crystal structure. A theoretical structure can also be refined using a method known as Rietveld
refinement. The particle size of the powder can also be determined by using the Scherrer formula, which relates
the particle size to the peak width. The Scherrer fomula is

with

is the x-ray wavelength,

BM is the observed peak width,
BS is the peak width of a crystalline standard, and
is the angle of diffraction.

To the left is an example XRD pattern for Ba24Ge100. The x axis is 2 and the y axis is the intensity.

Bragg's Law
X-rays are partially scattered by atoms when they strike the surface of a crystal. The part of the X-ray that is not
scattered passes through to the next layer of atoms, where again part of the X-ray is scattered and part passes
through to the next layer. This causes an overall diffraction pattern, similar to how a grating diffracts a beam of
light. In order for an X-ray to diffract the sample must be crystalline and the spacing between atom layers must be
close to the radiation wavelength. If beams diffracted by two different layers are in phase, constructive
interference occurs and the diffraction pattern shows a peak, however if they are out of phase,
destructive interference occurs appear and there is no peak. Diffraction peaks only occur if

sin=n
2d
where

is the

angle of
incidence
of the Xray,
n is an

integer,
is the

wavelength, and
d is the spacing between atom layers.
Since a highly regular structure is needed for diffraction to occur, only crystalline solids will diffract; amorphous
materials will not show up in a diffraction pattern.

Instrumentation
A powder X-ray diffractometer consists of an X-ray source (usually an X-ray tube), a sample stage, a detector
and a way to vary angle . The X-ray is focused on the sample at some angle , while the detector opposite the
source reads the intensity of the X-ray it receives at 2 away from the source path. The incident angle is than
increased over time while the detector angle
always remains 2 above the source path.

X-ray Tubes
While other sources such as radioisotopes and
secondary fluorescence exist, the most
common source of X-rays is an X-ray tube. The tube is evacuated and contains a copper block with a metal
target anode, and a tungsten filament cathode with a high voltage between them. The filament is heated by a
separate circuit, and the large potential difference between the cathode and anode fires electrons at the metal
target. The accelerated electrons knock core electrons out of the metal, and electrons in the outer orbitals drop
down to fill the vacancies, emitting X-rays. The X-rays exit the tube through a beryllium window. Due to massive
amounts of heat being produced in this process, the copper block must usually be water cooled

X-ray Detectors
While older machines used film as a detector, most modern equipment
uses transducers that produce an electrical signal when exposed to
radiation. These detectors are often used as photon counters, so
intensities are determined by the number of counts in a certain amount of
time.

Gas-Filled Transducers
A gas-filled transducer consists of a metal chamber filled with an inert
gas, with the walls of the chamber as a cathode and a long anode in the
center of the chamber. As an X-ray enters the chamber, its energy ionizes many molecules of the gas. The free
electrons then migrate towards the anode and the cations towards the cathode, with some recombining before
they reach the electrodes. The electrons that reach the anode cause current to flow, which can be detected. The
sensitivity and dead time (when the transducer will not respond to radiation) both depend on the voltage the
transducer is operated at. At high voltage, the transducer will be very sensitive but have a long dead time, and at
low voltage the transducer will have a short dead time but low sensitivity.

Scintillation Counters
In a scintillation counter, a phosphor is placed in front of a photomultiplier tube. When X-rays strike the phosphor,
it produces flashes of light, which are detected by the photomultiplier tube.

Semiconductor Transducers
A semiconductor transducer has a gold coated p-type semiconductor layered on a lithium containing
semiconductor intrinsic zone, followed by an n-type semiconductor on the other side of the intrinsic zone. The
semiconductor is usually composed of silicon; germanium is used if the radiation wavelength is very short. The
n-type semiconductor is coated by an aluminum contact, which is connected to a preamplifier. The entire crystal
has a voltage applied across it. When an X-ray strikes the crystal, it elevates many electrons in the
semiconductor into the conduction band, which causes a pulse of current.

References
1.
2.

Dann, S.E. Reactions and Characterization of SOLIDS. Royal Society of Chemistry, USA (2002).
Skoog, D.A.; Holler, F.J.; Crouch, S.R. Principles of Instrumental Analysis. Sixth Edition, Thomson
Brooks/Cole, USA (2007).

Outside Links

http://en.wikipedia.org/wiki/Powder_diffraction

Problems
Copper emits radiation at 1.5418. If a diffraction pattern taken with a copper X-ray tube source shows a peak at
40, what is the corresponding d spacing? (Hint: Don't forget that diffraction patterns are plotted in 2, not .)

Contributors

Jason Grebenkemper