Lec# 03 Ionization and Types

Ionization &
types of Ionization
LEC # 03
Ionization by Electron Collision
• Ionization by electron impact is most important process in the
breakdown of gases.
• Ionization by electron collision is process in which energetic electron

(energy equal or greater than ionization potential) strike at other
electron of neutral atom/molecule, ejecting it from its atom.
• In this process, an electron from the analyte molecule (A) is expelled

during the collision process to convert the molecule/atom to a
positive ion with an odd number of electrons.
• Here slow moving electrons will not produce ionization until moving
electrons density is significantly high.
• Very fast moving electrons are also poor ionizer due to less chances of
collision with other electrons.
• Mass spectrometry is best example to understand electronic ionization.
• The electrons produced inside the chamber of mass spectrometer

utilizes the beam of energetic electrons to produce fragmentation of
molecules and (or) ions. (MS is utilized to know the mass-to-charge
ratio of the ions.
• https://www.youtube.com/watch?v=22dr-3XDNmQ
• In 1886, Eugen Goldstein (discoverer of proton) observed rays in gas
discharges under low pressure that traveled away from the anode and
through channels in a perforated cathode, opposite to the direction of
negatively charged cathode rays (which travel from cathode to anode).
Goldstein called these positively charged anode rays "Kanalstrahlen"; the
standard translation of this term into English is "canal rays".
• *Mass spectrometry is playing a significant role in organometallic

chemistry. One of the most important applications of mass spectrometry
is the determination of the molecular mass and elemental composition
of metal compounds, and the identification of their structure.
Electron collision with atoms and ionization
Electrons can also initiate a beta decay to ionize or excite the electrons, a process that depends on:
1.The energy of the incident electron, which is given by its kinetic energy.
2.The energy of the electrons moving around the atom.
Figure 1. When an electron or a photon impacts an atom, part of their kinetic injects energy into the
electrons orbiting around the atom. This moves them to another orbit. If the energy is high enough, it
ejects the electrons from the atom. Source: Manuel R. Camacho, StudySmarter.
Photons vs electron
Photons and electrons are both fundamental particles, the former of electromagnetic waves and the latter of atoms. Together,
they are can cause the flow of electricity. However, they are different in many aspects:
Electron Photon
It is matter. It is energy.
It has mass. It has no mass.
It carries a negative It doesn’t carry any
charge. charge.
The speed of an electron

can be zero or anything
under the speed of light. It Photon travels at the
https://byjus.com/physics/electrons-and-photons/ is impossible for an speed of light.
electron to achieve the
speed of light.
Photoionization
Electrons of lower energy than the ionization energy eVi, may on
collision excite the gas atoms to higher states.
The excited atom radiates a quantum of energy of photon hγ which in

turn may ionize another atom whose ionization potential energy is
equal to or less than the photon energy. The process is known as
photoionization.
• For ionization to occur or the photon wavelength

being the velocity of light and h Planck’s constant.
https://www.youtube.com/watch?v=xIFQaOX-Xl4
A photoionization detector or PID is a type
of gas detector which uses photoionization.
Conventional photoionization detectors (PIDs) The structure of the conventional photoionization detector (PID)
is shown in Fig. 1, and consists of an ionization chamber that includes a UV source and two capturing
electrodes.
Hereby, the one-photon ionization based on the photoelectric effect is used by the PID for detecting the
analytes. During ionization, the complete energy of the photon (hv) is transferred to the gas atom (B) as
inelastic impact, whereupon the gas atom (B +) is ionized by extracting an electron (e −; Eiceman and Karpas,
2013).
Ionization
B + hv −−−−−→ (B +) + (e − )
In case of gas ionization by a photon, the provided photon energy has to be larger than the ionization potential
(IP) of the atom or molecule (hv > IP).
Thermal ionization
The term thermal ionization, in general, applies to the ionizing actions
of molecular collisions, radiation and electron collisions occurring in
gases at high temperature.
If a gas is heated to sufficiently high temperature many of the gas

atoms or molecules acquire sufficiently high velocity to cause ionization
on collision with other atoms or molecules. Thermal ionization is the
principal source of ionization in flames and high-pressure arcs.
Mass spectrometry uses thermal ionization
A mass spectrometer produces

charged particles (ions) from
the chemical substances that
are to be analyzed. The mass
spectrometer then uses electric
and magnetic fields to measure
the mass ("weight") of the
charged particles.
Fluorescent lamps work by ionizing mercury vapour in a glass tube. This causes
electrons in the gas to emit photons at UV frequencies. The UV light is converted into
standard visible light using a phosphor coating on the inside of the tube.
Ionization by interaction of metastables.
In certain elements the lifetime in some of the excited electronic states
extends to seconds. These states are known as metastable states and
the atoms in these states are simply referred to as metastables
represented by Am.
Metastables have a relatively high potential energy and are therefore
able to ionize neutral atoms.
If Vm, the energy of a metastable Am, exceeds Vi, the ionization of
another atom B, then on collision ionization may result according to the
reaction.
• Metastable state, in physics and chemistry, particular excited state of an
atom, nucleus, or other system that has a longer lifetime than the ordinary
excited states and that generally has a shorter lifetime than the lowest,
often stable, energy state, called the ground state.
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Ionization &

• Ionization by electron collision is process in which energetic electron

• In this process, an electron from the analyte molecule (A) is expelled

• Mass spectrometry is best example to understand electronic ionization.

• The electrons produced inside the chamber of mass spectrometer

• *Mass spectrometry is playing a significant role in organometallic

The speed of an electron

The excited atom radiates a quantum of energy of photon hγ which in

• For ionization to occur or the photon wavelength

If a gas is heated to sufﬁciently high temperature many of the gas

A mass spectrometer produces

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