X-ray spectroscopy is a technique that involves the detection and measurement of photons, or

particles of light, within the X-ray segment i.e., 0.01 – 10 nm of the electromagnetic spectrum.
By analyzing the emitted X-rays during electronic transitions in atoms, X-ray spectroscopy
identifies and quantifies specific elements present in a sample. This analytical tool finds
widespread use in scientific research, aiding investigations in materials science, chemistry, and
geology.
Principle of X-Ray Spectroscopy:
X-ray spectroscopy, or, X-ray Fluorescence (XRF), operates on the fundamental principles of
atomic behavior when subjected to radiation. When materials are exposed to high-energy,
short-wavelength radiation like X-rays, they undergo ionization. Particularly, the excitation of
an electron from an atom's inner shell occurs when energized by a photon, propelling it to a
higher energy level. As the electron returns to a lower energy state, the previously gained
energy is released as a photon, characterized by a specific wavelength indicative of the element.
The emitted X-rays during electronic transitions to inner shell states in atoms, particularly those
with modest atomic numbers, possess characteristic energies linked to the atomic number. Each
element thus exhibits a distinctive X-ray spectrum, providing a powerful means to identify and
analyze the elemental composition of materials.

Instrumentation of X-Ray Spectroscopy:

A. X-ray generating equipment (X-ray tube):

X-rays are generated by an X-ray tube, a vacuum tube utilizing

high voltage to accelerate electrons released by a hot cathode.

High-velocity electrons collide with a metal target (anode),

producing X-rays.

B. Collimators:

Collimators narrow a beam of particles or waves, aligning their

directions of motion.

Achieved through closely spaced, parallel metal plates or small-diameter tubes (0.5 or
less).
C. Monochromators:

Monochromator crystals partially polarize an unpolarized X-ray beam.

The primary goal is to separate and transmit a narrow portion of the optical signal
from a wider range of wavelengths.

Types include Metallic Filter Type and Diffraction Grating Type.

1. Metallic Filter Type: Utilizes a metallic filter to selectively absorb or attenuate X-rays
based on their energy. The filter allows only a narrow range of X-ray energies to pass
through. It selectively transmits the desired wavelength while attenuating others.
Simple design and operation. Cost-effective.
2. Diffraction Grating Type: Relies on the diffraction phenomenon to separate and
transmit specific wavelengths. X-rays incident on a crystal lattice (grating) undergo
diffraction. Diffraction patterns result in the separation of X-rays into distinct
wavelengths. Offers precise control over the selected wavelength. Enables high-
resolution spectral analysis. Suitable for a wide range of wavelengths.

D. X-ray Detectors:

1. Solid-State Detectors:

Utilize semiconductor materials where radiation produces electron-hole pairs.

Under the influence of an electric field, electrons and holes are collected, and the
charge is measured as a pulse.

2. Scintillation Detectors:

Comprise a scintillator and a device like a Photomultiplier Tube (PMT) converting light
into an electrical signal.

The PMT includes a photocathode, dynodes, and an anode.

Electrons emitted from the photocathode undergo multiple stages of amplification

through dynodes before reaching the anode.

Amplification is adjustable by varying the applied voltage to the PMT

3. Gas-filled Detector:
Consists of a volume of gas between two electrodes with an applied electrical potential
difference (voltage).
Ionizing radiation generates ion pairs in the gas.
Positive ions (cations) are attracted to the negative electrode (cathode), and electrons or anions
are attracted to the positive electrode (anode).
In most detectors, the cathode is the container wall, and the anode is a wire inside the container.
4. Geiger-Mueller Counter:
GM counters must contain gases with specific properties.
Involves the electrical collection of ions produced by ionizing radiation.
When the gas amplification factor reaches 10^8, the size of the output pulse becomes constant,
independent of the initial energy deposit.
Operates in the Geiger-Mueller region, behaving like a spark plug with a single large discharge.
Exhibits energy dependence in the Geiger-Mueller region.
Large dead times (100-300μs) result.

Applications of X-Ray Spectroscopy

1. X-ray spectrometry is used in a wide range of applications, including

2. Research in igneous, sedimentary, and metamorphic petrology
3. Soil surveys
4. Mining (e.g., measuring the grade of ore)
5. Cement production
6. Ceramic and glass manufacturing
7. Metallurgy (e.g., quality control)
8. Environmental studies (e.g., analyses of particulate matter on air filters)
9. Petroleum industry (e.g., sulfur content of crude oils and petroleum products)
10. Field analysis in geological and environmental studies (using portable,
hand-held XRF spectrometers)
Advantages of X-Ray Spectroscopy

1. X-ray spectroscopy is an excellent method to determine the structure of a

compound.
2. In the event when other spectral methods fail to reveal a compound’s
identity, X-ray spectroscopy is the method of choice for structural
determination where the other parameters such as bond lengths and bond
angles are also determined.
Limitations of X-Ray Spectroscopy

1. The technique requires the availability of a compound as a single crystal.

 2. Most chemists find this process very tedious, time consuming and it requires
a skillful hand.
PRODUCTION OF X RAYS

X-rays are produced through the interaction of high-energy electrons with matter. The
two primary mechanisms for generating X-rays are bremsstrahlung radiation and
characteristic radiation.

Bremsstrahlung Radiation:

In this process, high-speed electrons are subjected to the electric field of atomic nuclei.

The electrons experience deceleration or deflection, and this abrupt change in velocity
results in the emission of X-rays.

The term "bremsstrahlung" is German for "braking radiation," reflecting the

deceleration of electrons.

Bremsstrahlung X-rays form a continuous spectrum, covering a range of energies.

Characteristic Radiation:

Characteristic X-rays are produced when inner-shell electrons are ejected from atoms,
leaving vacancies in those inner electron shells.

Outer-shell electrons then transition to fill these inner-shell vacancies, releasing energy
in the form of X-rays.

The energies of these characteristic X-rays are specific to the elements involved,
providing a unique spectral fingerprint for each element.

X-ray Tubes:

X-rays are commonly generated using X-ray tubes. An X-ray tube consists of a cathode
and an anode within a vacuum or low-pressure gas.

The cathode emits electrons when heated, and these electrons are accelerated toward
the anode by a high voltage.

The high-speed electrons interact with the anode, producing X-rays through both
bremsstrahlung and characteristic radiation.

Feature Characteristic X-rays Continuous X-rays

Production Produced during inner-shell electron Emitted when high-speed electrons
Mechanism transitions. are decelerated.
Nature of the
Spectrum Sharp, discrete lines. Smooth, continuous spectrum.
 Feature Characteristic X-rays Continuous X-rays
Well-defined, characteristic of Continuous range of energies, no
Energy Levels emitting element. specific lines.
Originates from transitions within Arises from electron acceleration and
Origin of Emission electron shells. deceleration.
Used for elemental analysis and Primarily applied in medical imaging
Application identification. (radiography).

MOSELEY’S LAW

The law states that the square root of the frequency of characteristic X-rays emitted by an
element is directly proportional to its atomic number (Z). Mathematically, it can be expressed
as:

Here:
represents the square root of the frequency of the emitted X-rays.
is the atomic number of the element.
Moseley's Law helped to resolve some inconsistencies in the arrangement of elements in the
periodic table. Prior to Moseley's work, elements were primarily ordered by their atomic
weights. However, this led to certain anomalies where elements with similar chemical
properties were not grouped together.
Moseley's Law justified the reorganization of the periodic table based on the atomic number,
which is the number of protons in an atom's nucleus. This reordering accurately reflects the
periodic trends in elemental properties and provides a clearer understanding of the relationships
between different elements. The law played a crucial role in the development of modern
quantum mechanics and contributed to the establishment of a more accurate and systematic
periodic table.

BRAGG'S LAW
Bragg's Law is a fundamental principle in X-ray crystallography that describes the conditions
for constructive interference of X-rays scattered by crystal planes. It was formulated by the
father-and-son scientists Sir William Henry Bragg and Sir William Lawrence Bragg in 1913.
Bragg's Law is a key component of the technique used to determine the atomic and molecular
structure of crystals. The law is expressed mathematically as:

Here's a breakdown of the terms in Bragg's Law:

• d: The spacing between adjacent crystal planes.
• θ: The angle of incidence of the X-ray beam with respect to the crystal lattice.
• n: An integer representing the order of the diffraction (e.g., 1 for the first order, 2 for
the second order).
• λ: The wavelength of the incident X-rays.
The law explains that when X-rays strike a crystal lattice, they interact with the regularly spaced
atomic planes. Constructive interference occurs when the path difference between X-rays
scattered from adjacent planes is a whole number of wavelengths. This results in the
reinforcement of the scattered waves and the formation of a distinct diffraction pattern.
Key points about Bragg's Law:
Constructive Interference: Bragg's Law describes the conditions under which X-rays
reinforce each other, leading to observable diffraction patterns.
Determination of Crystal Structure: The diffraction pattern generated by Bragg's Law
provides information about the arrangement of atoms in the crystal, allowing for the
determination of its structure.
Unit Cell Parameters: By analyzing the diffraction pattern, researchers can deduce the
crystal's unit cell parameters, symmetry, and the three-dimensional electron density
distribution.
Wavelength and Resolution: The choice of X-ray wavelength is crucial, as shorter
wavelengths provide higher resolution and can reveal finer details in the crystal structure.

Compton Effect:
The Compton Effect is a fundamental concept in quantum mechanics and wave-particle duality,
and it played a crucial role in confirming the particle-like nature of photons. Arthur Compton
conducted experiments in the early 20th century that showed that X-rays could be scattered by
electrons, and the scattered X-rays had a different wavelength than the incident X-rays.
Here are key points about the Compton Effect:
Scattering of X-rays: When X-rays are directed at a target material, some of the X-rays undergo
scattering when they interact with electrons in the target.
Wavelength Shift: Compton observed that the scattered X-rays had a longer wavelength than
the incident X-rays. This shift in wavelength is now known as the Compton shift.
Quantum Nature of Photons: The Compton Effect provided strong evidence for the particle
nature of photons. The shift in wavelength could be explained by treating X-rays as particles
(photons) colliding with electrons.
Mathematical Formulation: The Compton shift (change in wavelength) is given by the
equation:

where:

• Δλ is the change in wavelength.

• h is the Planck constant.
• me is the electron mass.
• c is the speed of light.
• θ is the scattering angle.
Experimental Confirmation: Compton's experiments were crucial in confirming the quantized
nature of electromagnetic radiation and provided support for the emerging theory of quantum
mechanics.
The Compton Effect has broad implications in fields such as physics and chemistry, and it has
contributed to our understanding of the dual nature of particles and waves in the realm of
quantum mechanics.