Dr.

Anand A Mahajan

X – RAY

X – Ray spectroscopy, like optical spectroscopy is based upon measurement of absorption,

emission, fluorescence, scattering and diffraction of electromagnetic radiation. X – ray
absorbance and X – ray fluorescence are widely used for the qualitative and quantitative
determinations of all elements in the periodic table having atomic numbers greater than that of
sodium. With special equipment, elements with atomic numbers in the range of 5 to 10 can also
be determined.

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
wavelength range of X – ray is from about 10-5 Ǻ to 100 Ǻ. However, conventional X – ray
spectroscopy is confined to the region of about 0.1 Ǻ to 25 Ǻ (1 Ǻ = 0.1 nm = 10-10 m).

INSTRUMENTATION

X-ray spectrometer consists of following parts

1.0 X-ray sources.

2.0 Filters for X-rays.
3.0 X-ray monochromators.
4.0 X-ray transducers and signal processors

1.0 X-ray sources:

For analytical purposes, X – rays are obtained in four ways:

1) By bombardment of metal target with a beam of high-energy electrons.

2) By exposure of substance to a primary beam of X – rays in order to generate a secondary

beam of X – ray fluorescence.

3) By use of radioactive source whose decay processes results in X – ray emission.

4) From synchrotron radiation source.

Here we will consider only first three sources since they are widely use. X – ray sources, like
ultraviolet and visible emitters often produce both continuum and line spectra; both types have
importance in analysis. Continuum radiation is also called white radiation or Bremsstrahlung
radiations. Bremsstrahlung means radiations that arise from retardation by particles; such
radiations are generally continuous in nature.

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1) By bombardment of metal target with a beam of high-energy electrons (X-ray tube)

The most common source of X-ray used for analytical work is produced by X-ray tube
(sometime it is called as Coolidge tube). It consists of evacuated tube in which tungsten filament
acts as cathode and heavy block of copper as anode as shown in following figure. Other metals
such as tungsten, chromium, copper, molybdenum, rhodium, scandium, silver, iron and cobalt.
Separate circuits are used to heat the filament and to accelerate the electrons to the target. The
circuit which is used to heat the filament control intensity of emitted X-rays while accelerating
potential determines their energy, or wavelength.

The production of X-ray by electron bombardment is highly inefficient processes. Less than 1%
of the electrical power is converted to radiant power, the remaining being dissipated as heat. Due
to this water cooling of anode is required. However modern instruments do not require anode
cooling because these can be operated at significantly lower intensity than earlier instrument due
to high sensitivity of modern X-ray transducers.

Figure 1.0: Schematic diagram of X-ray tube (W represents cooling water).

A) Generation of continuum spectra from electron beam source

In an X-ray tube, when a potential of 100 kV is applied the electrons produced at a heated
cathode get accelerated towards a metal anode. Upon collision with anode part of energy of
electron beam gets converted to X-rays. Depending upon certain conditions it leads to formation
of either continuum spectra (figure 1.1) or a line spectrum (figure 1.2) superimposed on the
continuum spectra.

The continuum X-ray spectrum shown in both the figures is characterized by a well defined,
short wavelength limit (λ0), which is dependent upon the accelerating voltage V but independent
of target material. Thus, λ0 for the spectrum produced with a molybdenum target at 35 kV (figure
1.2) is identical to λ0 for a tungsten target at the same voltage (figure 1.1).

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Figure 1.1: Distribution of continuum Figure 1.2 Line spectra of an X-ray with
radiation from an X-ray tube with a molybdenum target.
Tungsten target. The numbers above
the curve indicates the accelerating
voltage.

The continuum radiation from an electron beam source results from collisions between the
electrons of the beam and the atoms of the target material. At each collision, the electron is
decelerated and a photon of X-ray energy is produced. The energy of the photon is equal to the
difference in kinetic energies of the electron before and after the collision. Generally, the
electrons in the beam are decelerated in a series of collisions; the resulting loss of kinetic energy
differs from collision to collision. Thus, the energies of the emitted X-ray photons vary
continuously over a considerable range.

The maximum photon energy generated corresponds to the instantaneous deceleration of the
electron to zero kinetic energy. For such an event we may write

Where, Ve is the product of the accelerating voltage and the charge on electron is the kinetic
energy of all of the electrons in the beam; h is the Plank constant; and c is the velocity of light.
The quantity v0 is the maximum frequency of radiation that can be produced at voltage V, while
λ0 is the low wavelength limit of the radiation.

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B) Generation of line spectra from electron beam source

As shown in figure 1.2, bombardment of a molybdenum target produces intense emission lines at
about 0.63 and 0.71 Ǻ. X-ray line spectra are remarkably simple when compared with ultraviolet
emission and consists of two series of lines. The shorter wavelength group is called the K series
and the longer wavelength group is called L series. First characteristic spectra is that elements
with atomic number smaller than 23 produce only a k series lines (Na, K) while elements having
atomic number greater than 23 (Cr, Rb, Cs, W, U) produce both K and L series lines.

X-ray line spectra result from electronic transitions that involve the innermost atomic orbitals.
The short wavelength K series is produced when the high energy electrons from the cathode
removes electrons from those orbitals nearest to the nucleus of the target atom, which then emit
quanta of X-radiation as electrons from outer orbitals undergo transitions to the vacant orbital.
As shown in figure 1.3 the line in the K series arise from electronic transitions between higher
energy levels and the K shell. The L series of line results when an electron is lost from the
second principal quantum level either as consequence of ejection by an electron from the cathode
or from the transition of an L electron to the K level that accompanies the production of a
quantum of K radiation. It is important to appreciate that the energy scale in the figure 1.3 is
logarithmic. Thus, the energy difference between the L and K level is significantly larger than
the M and L levels. The K line therefore appears at shorter wavelengths. It is also important to
note that the energy difference between the transitions labeled α1 and α2 as well as β1 and β2 are so
small that only single lines are observed figure 1.2. The energy diagram in figure 1.3 is
applicable to any element with sufficient electrons to permit the number of transitions shown.
The difference in the energies between the levels increases regularly with atomic number
because of the increasing charge on the nucleus, therefore radiations of the K series appears at
shorter wavelengths for the heavier elements. Moreover, minimum voltage is required to excite
the spectra of these elements.

It is important to note that for lightest elements, the wavelength of characteristic X-ray lines are
independent of the physical and chemical state of the element because the transitions responsible
for these lines involve electrons that take no part in bonding. Thus, the position of the Kα lines
for the molybdenum is the same regardless of whether the target is the pure metal, its sulfide or
its oxide.

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Figure 1.3: Partial energy-level diagram showing common transitions producing X-rays.

2) By exposure of substance to a primary beam of X – rays in order to generate a secondary

beam of X – ray fluorescence (line spectra from fluorescence source)

This is another way of producing line spectrum. Here, element is irradiated with continuum
irradiation from X-ray tube, absorption of X-rays leads to formation of electronically excited ion
which return to its ground state by transitions involving electrons from higher energy levels.
Example: Lead goes to excited ionic state with vacant K shell when it absorbs radiation of
wavelengths shorter than 0.14 Ǻ (figure 1.4). After a brief period the ion returns to ground its
ground state via series of electronic transitions characterized by emission of X-radiation
(fluorescence) of wavelengths identical to those that result from excitation produced by electron
bombardment.

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Figure 1.4: X-ray absorption spectra for lead and silver.

The wavelengths of fluorescence lines are always somewhat greater than the wavelength of the
corresponding absorption edge, however, because absorption requires a complete removal of the
electron (that is. ionization), whereas emission involves transitions of an electron from a higher
energy level within the ion. For example, the K absorption edge for silver occurs at 0.485 Ǻ, but
the K emission lines for the element have wavelengths at 0.497 and 0.559 Ǻ. When fluorescence
is to be excited by radiation from an X-ray tube, the operating voltage must be sufficiently great
so that the cutoff wavelength λ0 (Equation 12-2) is shorter than the absorption edge of the
element whose spectrum is to be excited.

Figure 1.5: Diagram showing production of X-rays by primary X-ray beams.

Example: an X-ray tube with a tungsten target could be used to excite the Kα and Kβ lines of
molybdenum, the resulting fluorescence spectrum would then be similar to the spectrum in figure
1.2 except that the continuum would be absent.

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3) By use of radioactive source whose decay processes results in X – ray emission.

X-radiation is often a product of radioactive decay processes. Gamma rays, which are
indistinguishable from X-rays, are produced in intranuclear reactions. Many α and β emission
processes leave a nucleus in an excited state; the nucleus then releases one or more quanta of
gamma rays as it returns to its ground state. It is important to note that γ rays except for their
source are indistinguishable from X-rays of the same energy. Thus γ rays are produced by
nuclear relaxation, while X-rays derive from electronic relaxations. The γ ray emission spectrum
is characteristic for each nucleus and is thus useful for identifying radioisotopes.

Electron capture or K capture also produces X-radiation. This process involves capture of a K
electron (less commonly, an L or an M electron) by the nucleus and formation of an element of
the next lower atomic number. As a result of K capture, electronic transitions to the vacated
orbital occur, and we observe the X-ray line spectrum of the newly formed element. The half-
lives of K-capture processes range from a few minutes to several thousand years. Artificially
produced radioactive isotopes provide a very simple source of mono energetic radiation for
certain analytical applications. The best-known example is iron-55, which undergoes a K-capture
reaction with a half) life of 2.6 years:
55
Fe Mn + hv
54

The resulting manganese Ka line at about 2.1 A has proved to be a useful source for both
fluorescence and absorption methods.

Examples:
125
53I, 210 82Pb

2.0 Filters for X-rays

In many applications, it is desirable to use an X-ray beam with a narrow wavelength range. As in
the visible region, both filters and monochromators are used for this purpose. Figure 2.1
illustrates a common technique for producing a relatively monochromatic beam by use of a filter.
Here, the Kβ line and most of the continuum emitted from a molybdenum target is removed by a
zirconium tiller having a thickness of about 0.01 cm. The pure Kα line is then available for
analytical purposes. Several other target-filter combinations of this type have been developed,
each of which serves to isolate one of the intense lines of a target element. Monochromatic
radiation produced in this way is widely used in X-ray diffraction studies. The choice of
wavelengths available by this technique is limited by the relatively small number of target-filter
combinations that are available. Filtering the continuum from an X-ray tube is also feasible with
thin strips of metal.

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Figure 2.1: Use of filter to produce monochromatic radiation.

3.0 X-ray monochromators

The monochromator consists of a pair of beam collimators, which serve the same purpose as the
slits in an optical instrument, and a dispersing element. The latter is a single crystal mounted on a
goniometer, or rotatable table that permits variation and precise determination of the angle θ
between the crystal face and the collimated incident beam. From equation (nλ = 2d sin θ), it is
evident that, for any given angular setting of the goniometer, only a few wavelengths are
diffracted (λ, λ/2, λ/3... λ/n, where λ=2d sin θ). To produce a spectrum it is necessary that the exit
beam collimator and the detector be mounted on a second table that rotates at twice the rate of
the first: that is, as the crystal rotates through an angle θ, the detector must simultaneously move
through an angle 2θ. Clearly, the interplanar spacing d for the crystal must be known precisely
(nλ = 2d sin θ). Many modern X-ray monochromators have computer-controlled motors to drive
the crystal and the detector independently without a gear-based mechanical connection. These
units are capable of scanning at very rapid rates (ca. 2400min). Some instruments feature slew-
scan operation, in which the monochromator can be slewed to the wavelength region of interest
(ca. 14000min) and then slowly scanned over analyte peaks. The collimators for X-ray
monochromators ordinarily consist of a series of closely spaced metal plates or tubes that absorb
all but the parallel beams of radiation. X-radiation longer than about 2 Ǻ is absorbed by
constituents of the atmosphere. Therefore, provision is usually made for a continuous flow of
helium through the sample compartment and monochromator when longer wavelengths are
required. Alternatively, these areas can be evacuated by pumping.

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Figure 3.0: An X-ray monochromator and detector

5.0 X-ray transducers and signal processors

Modern instruments are generally equipped with transducers that convert radiant energy into an
electrical signal. Following three types of transducers are used in equipments

5.1 Gas-filled transducers.

5.2 Scintillation counters.

5.3 Semiconductor transducers.

Before considering the function of each of these devices, it is worthwhile to discuss photon
counting, a signal-processing method that is often used with X-ray transducers as well as
detectors used to measure radiation from radioactive sources.

Photon counting

In this mode of operation, individual pulses of charge are produced from each quanta of
radiation. These charges are then absorbed by the transducer, and are counted. The power of the

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beam is then recorded digitally as the number of counts per unit of time. Photon counting
requires rapid response times for the transducer and signal processor so that the arrival of
individual photons may be accurately transduced and recorded. In addition, the technique is
applicable only to beams of relatively low intensity. As the beam intensity increases, photon
pulses begin to overlap and only a steady-state current, which represents an average number of
pulses per second, can be measured. If the response time of the transducer is long, pulse overlap
occurs at relatively low photon intensities. As its response time becomes shorter, the transducer
is more capable of detecting individual photons without pulse overlap. For weak sources of
radiation, photon counting generally provides more accurate intensity data than are obtainable by
measuring average currents. Separation of the signal from noise can then be achieved with a
electronic device called pulse-height discriminator. Photon counting is used in X-ray work
because the power of available sources is often low. In addition, photon counting permits spectra
to be acquired without using a monochromator.

5.1 Gas-filled transducers

When X-radiation passes through an inert gas such as argon, xenon, or krypton, interactions of
X-rays leads to production of a large number of positive gaseous ions and electrons (ion pairs)
for each X-ray quantum. A typical gas-filled transducer is shown schematically in figure 5.1.1.
Radiation enters the chamber through a transparent window of mica, beryllium, aluminum, or
Mylar. Each photon of X-radiation that interacts with an atom of argon causes it to lose one of its
outer electrons. This photoelectron has a large kinetic energy, which is equal to the difference
between the X-ray photon energy and the binding energy of the electron in the argon atom. The
photoelectron then loses this excess kinetic energy by ionizing several hundred additional atoms
of the gas. Under the influence of an applied voltage, the mobile electrons migrate toward the
central wire anode and the slower-moving cations migrate toward the cylindrical metal cathode.
Figure 5.1.2 shows the effect of applied voltage on the number of electrons that reach the anode
of a gas filled transducer for each entering X-ray photon. The diagram indicates three
characteristic voltage regions. At voltages less than V1, the accelerating force on the ion pairs is
low, and the rate the positive and negative species separate is insufficient to prevent partial
recombination. As a result, the number of electrons reaching the anode is smaller than the
number produced initially by the incoming radiation.

In the ionization chamber region between V1and V2 the number of electrons reaching the anode
is reasonably constant and represents the total number formed by a single photon.

In the proportional counter region between V3 and V4 the number of electrons increases rapidly
with applied voltage. This increase is the result of secondary ion-pair production caused by
collisions between the accelerated electrons and gas molecules which lead to amplification of the
ion current.

In the Geiger range V5 to V6, amplification of the electrical pulse is enormous but is limited by
the positive space charge created as the faster-moving electrons migrate away from the slower
positive ions. Because of this effect, the number of electrons reaching the anode is independent
of the type and energy of incoming radiation and is governed instead by the geometry and gas
pressure of the tube. Figure 5.1.2 also illustrates that a larger number of electrons is produced by

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the more energetic 0.6 Ǻ radiation than the longer-wavelength 5 Ǻ X-rays. Thus, the size of the
pulse (the pulse height) is greater for high-frequency X-rays than for low-frequency X-rays.

Figure 5.1.1 Cross section of gas-filled transducer.

Figure 5.1.2 Gas amplification for various types of gas filled detector.

5.2 Scintillation counters

The most widely used modern scintillation detector consists of a transparent crystal of sodium
iodide that has been activated by the introduction of 0.2% thallium iodide. Often, the crystal is
shaped as a cylinder that is 3 to 4 inch. in each dimension; one of the plane surfaces then faces
the cathode of a photomultiplier tube. As the incoming radiation passes through the crystal, its
energy is first lost to the scintillator; this energy is subsequently released in the form of photons
of fluorescence radiation. Several thousand photons with a wavelength of about 400 nm are
produced by each primary particle or photon over a period of about 0.25 µs, which is the dead
time. The dead time of a scintillation counter is thus significantly smaller than the dead time of a
gas-filled detector. The flashes of light produced in the scintillator crystal are transmitted to the

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photocathode of a photomultiplier tube and are in turn converted to electrical pulses that can be
amplified and counted. An important characteristic of scintillators is that the number of photons
produced in each flash is proportional to the energy of the incoming radiation.

In addition to sodium iodide crystals, a number of organic scintillators such as stilbene,

anthracene, and terphenyl have been used. In crystalline form, these compounds have decay
times of 0.01 and 0.1 µs. Organic liquid scintillators have also been developed and are used to
advantage because they exhibit less self absorption of radiation than do solids. An example of a
liquid scintillator is a solution p-terphenyl in toluene.

Figure 5.2.1 Schematic diagram of scintillation counter.

5.3 Semiconductor transducers

These devices are sometimes called lithium-drifted silicon detectors, Si (Li), or lithium-drifted
germanium detectors, Ge (Li).

Figure 5.3.1 illustrates one form of a lithium-drifted detector. There are three layers in the
crystal: a p-type semiconducting layer that faces the X-ray source, a central intrinsic zone, and
an n-type layer. The outer surface of the p-type layer is coated with a thin layer of gold for
electrical contact; often, it is also covered with a thin beryllium window that is transparent to
X-rays. The signal output is taken from an aluminum layer that coats the n-type silicon: this
output is fed into a preamplifier with a gain of about 10.

A lithium-drifted detector is formed by vapor depositing lithium on the surface of a p-doped

silicon crystal. When the crystal is heated to 400°C to 500°C, the lithium diffuses into the
crystal. Because lithium easily loses electrons, its presence converts the p-type region to an
n-type region. While still at an elevated temperature, a dc voltage applied across the crystal
causes withdrawal of the electrons from the lithium layer and holes from the p-type layer.
Current across the pn junction causes migration, or drifting, of lithium ions into the p layer and
formation of the intrinsic layer, where the lithium ions replace the holes lost by conduction.
When the crystal cools, this central layer has a high resistance relative to the other layers because
the lithium ions in this medium are less mobile than the holes they displaced.

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The intrinsic layer of a silicon detector functions in a way that is analogous to argon in the gas-
filled transducer. Initially, absorption of a photon results in formation of a highly energetic
photoelectron, which then loses its kinetic energy by elevating several thousand electrons in the
silicon which results in marked increase in conductivity. When a voltage is applied across the
crystal, a current pulse accompanies the absorption of each photon. As in proportional detectors,
the size of the pulse is directly proportional to the energy of the absorbed photons.

As shown in figure 5.3.1, the detector and preamplifier of a lithium-drifted detector must be
thermostatted at the temperature of liquid nitrogen (77 K) to decrease electronic noise to a
tolerable level. The original Si (Li) detectors had to be cooled at all times because at room
temperature the lithium atoms would diffuse throughout the silicon, thereby degrading the
performance of the detector. Modern Si (Li) detectors need to be cooled only during use.
Germanium is used in place of silicon to give Lithium drifted detectors particularly useful for
detection of radiation shorter in wavelength than 0.3 Ǻ. These detectors must be cooled at all
times. Germanium detectors that do not require lithium drifting have been produced from very
pure germanium. These detectors, called intrinsic germanium detectors.

Figure 5.3.1 Schematic diagram of semiconductor transducer.

6.0 Diffraction of X-rays

Like- other types of electromagnetic radiation, when X-radiation passes through a sample of
matter. The electric vector of the radiation interacts with the electrons in the atoms of the matter
to produce scattering. Scattering of X-rays leads to formation of constructive and destructive
interferences because the distances between the scattering centers are of the same order.

Bragg's Law

When an X-ray beam strikes a crystal surface at some angle θ, part of the beam is scattered by
the layer of atoms at the surface. The unscattered part of the beam penetrates to the second layer

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of atoms where again a fraction of beam gets scattered, and the remaining passes on to the third
layer (figure 6.1), and so on. The cumulative effect of this scattering from the regularly spaced
centers of the crystal. Diffraction of the beam occurs much in the same wave as visible radiation
is diffracted by a reflection grating. The requirements for X-ray diffraction are as follows.

(1) The spacing between layers of atoms must be roughly the same as the wavelength of the
radiation and
(2) The scattering centers must be spatially distributed in a highly regular way.

Diffraction of X-rays by crystals is shown in figure 6.1. Here, a narrow beam of radiation strikes
the crystal surface at angle θ; scattering occurs as a result of interaction of the radiation with
atoms located at O. P, and R.

Figure 6.1 Diffraction of X-rays by a crystal.

If the distance

AP + PC = nλ Equ. 1

Where, n is an integer, the scattered radiation will be in phase at OCD, and the crystal will
appear to reflect the X-radiation.

But,

Sin θ = AP / OP Sin θ = PC/OP

Sin θ + Sin θ = AP + PC / OP

2 Sin θ = AP + PC /d Since, OP = d

Where, d is the interplanar distance of the crystal. Thus, the conditions for constructive
interference of the beam at angle θ are

2 d Sin θ = AP + PC

2 d Sin θ = nλ Equ. 2 Since, AP + PC = nλ Equ. 1

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Equation 2 is the fundamentally important Bragg equation. Note that X-rays appear to be
reflected from the crystal only if the angle of incidence satisfies the condition

Sin θ = nλ/2d

At all other angles, destructive interference occurs.

6.1 X – Ray Diffraction Methods

X-ray diffraction has provided a wealth of important information to science and industry.

1.0 X-ray diffraction studies provide information about arrangement and the spacing of atoms
in crystalline materials.
2.0 X-ray diffraction is one of the most important methods for determining the structures of
complex natural products such as steroids, vitamins, and antibiotics.
3.0 X-ray diffraction also provides a convenient and practical means for the qualitative
identification of crystalline compounds.
4.0 The X-ray powder diffraction method is the only analytical method that is capable of
providing qualitative and quantitative information about the compounds present in a
solid sample. For example the powder method can determine the percentage KBr and NaCl
in a solid mixture of these two compounds. Other analytical methods reveal only the
percentage K+. Na+, Br-, and Cl- in the sample."

Identification of crystalline compounds

Sample Preparation

For analytical studies, the crystalline sample is ground to a fine homogeneous powder so that
every small crystallite are oriented in every possible direction; thus, when an X-ray beam passes
through the material, a significant number of the particles are oriented in such ways as to fulfill
the Bragg condition for reflection from every possible interplanar spacing. Samples are usually
placed in a sample holder that uses a depression or cavity to mount the sample. These mounts are
commonly made of aluminum, bronze, Bakelite, glass, or Lucite. Alternatively, a specimen may
be mixed with a suitable noncrystalline binder and molded into an appropriate shape.

Automatic Diffractometers

Diffraction patterns are generally obtained with automated instruments similar in design to that
shown in Figure 6.1.1. In this instrument, the source is an X-ray tube with suitable filters. The
powdered sample, however, replaces the single crystal on its mount. In some instances, the
sample holder may be rotated to increase the randomness of the orientation of the crystals.

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Photographic Recording

The classical photographic method for recording powder diffraction patterns is still used,
particularly when the amount of sample is small. The most common instrument for this purpose
is the Debye-Scherrer powder camera, which is shown schematically in Figure 12-17a. Here,
the beam from an X-ray tube is filtered to produce a nearly monochromatic beam (often the
copper or molybdenum Kα line), which is collimated by passage through a narrow tube. Several
other target-filter combinations have been developed to isolate one of the intense lines of the
target material. The undiffracted radiation T then passes out of the camera via a narrow exit tube
as shown in Figure 6.1.1. The camera itself is cylindrical and equipped to hold a strip of film
around its inside wall. The inside diameter of the cylinder usually is 5.73 or 11.46 cm, so that
each lineal millimeter of film is equivalent to 10 or 0.50 in θ, respectively. The sample is held in
the center of the beam by an adjustable mount. Figure 12-17b shows the appearance of the
exposed and developed film; each set of lines (D1, D2 and so forth) represents diffraction from
one set of crystal planes. The Bragg angle θ for each line is easily evaluated from the geometry
of the camera.

Figure 6.1.1 A Schematic diagram of Debye-Scherrer powder camera B The film strip after
development.

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Interpretation of diffraction pattern

The identification of a species from its powder diffraction pattern is based on the position of the
lines (in terms of θ or 2θ) and their relative intensities. The diffraction angle 2θ is determined by
the spacing between a particular set of planes: with the aid of the Bragg equation. This distance d
is calculated from the known wavelength of the source and the measured angle. Line intensities
depend on the number and kind of atomic reflection centers in each set of planes. Crystals are
identified empirically. A powder diffraction database is maintained by the International Centre
for Diffraction Data, Newtown Square, Pennsylvania. As of 2005, this file contained powder
diffraction patterns for more than 477,000 reference materials. Because the file is so large, the
powder data file has been broken down into sub files that contain listings for inorganics,
organics, minerals, metals, alloys, forensic materials, and others. The sub-databases are available
on CD-ROM, and software is available for searching the databases using any combination of
several search criteria. Each record in the database contains a wealth of information regarding
the substances and materials, including name, formula (if appropriate), composition, color, line
strengths, melting point, mineral classification, density, and a lots of other characteristics of the
materials as well as bibliographic information. A variety of presentation modes are available so
that graphs and other important images may be viewed and printed.

If the sample contains two or more crystalline compounds, identification becomes more
complex. Here, various combinations of the more intense lines are used until a match can be
found. Computer searching and matching of data greatly facilitates this task.

One very important application is the determination of the percentage crystallinity of materials.
In the pharmaceutical area, the degree of crystallinity can influence the long-term stability of a
formulation as well as its bioactivity due to this X-ray diffraction methods are being increasingly
applied to pharmaceuticals.

7.0 Applications of X-ray spectroscopy

X-ray Crystallography

1.0 It determines the arrangement of atoms within a crystal (slats, metals, minerals and
semiconductors). From angles and intensities of these diffracted beams, a
crystallographer can produce a three-dimensional picture of the density of electrons within
the crystal. From this electron density, the mean positions of the atoms in the crystal can be
determined, as well as their chemical bonds, their order and various other information can be
deduced.
2.0 The method is also useful in determining structure of many biological molecules, including
vitamins, drugs, proteins and nucleic acids such as DNA.
3.0 X-ray crystallography is still the chief method for characterizing the atomic structure of new
materials and in discerning materials that appear similar by other experiments.

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X-ray powder diffraction

01 Identification of Polymorph - Vitamins are another group of materials commonly tested

with XRD. The wrong polymorph of a vitamin is usually inert and provides no benefit to the
consumer. For example, the B vitamin pantothenic acid has two polymorphs, one of which is
inert. Using XRD it is possible to identify each component, and whether the correct
polymorph is present to ensure proper potency.

02 Qualitative Identification of Mixture (Phase identification) - Two mixtures, 50% cocaine /

50% maltose and 10% cocaine / 90% maltose, show the qualitative differences in the XRD
pattern as the components are varied. Qualitative identification is based on the presence of
the unique diffraction lines for each substance. In addition, a quantitative determination can
be made for each component by measuring its peak intensity and comparing it to the
intensities measured from one or more samples of known concentration.

03 Active Pharmaceutical Agents (APIs) Characterization -Polymorphic forms of a drug

substance can have different chemical and physical properties, including melting point,
chemical reactivity, apparent solubility, dissolution rate, optical and mechanical properties,
vapour pressure, and density. These properties can have a direct effect on the ability to
process and/or manufacture the drug substance and the drug product, as well as on drug
product stability, dissolution, and bioavailability. Thus, polymorphism can affect the quality,
safety, and efficacy of the drug product.

04 Re-crystallization of amorphous material - XRPD can also be used to monitor re-

crystallization of amorphous materials. Following figure shows the monitoring of re-
crystallization of amorphous felodipine by XRPD over a 7 day period. The top pattern is pure
amorphous felodipine; the remaining patterns were collected on the same sample stored
under ambient conditions (250C and 50% RH) after a period of 2, 3, 5, and 7 days,
respectively. Pattern Collected after 2 days is approximately 5%crystalline, followed by 11%
after 3 days and 45% after 5 days. After 7 days the sample is almost completely crystalline.

Figure 7.1 Re-crystallization of amorphous felodipine monitored by XRPD.

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 Dr. Anand A Mahajan

Reference: Douglas A. S., Holler F. J., Nieman T. A., Principals of Instrumental Analysis, 5th
edition, page 272.

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