NUCLEAR MAGNETIC

RESONANCE SPECTROSCOPY
 Introduction
• Nuclear magnetic resonance (NMR) spectroscopy is a non-
destructive technique for mapping molecular structures and
learning how molecules function and relate to each other.
• The study of absorption of radio frequency (rf) radiation by
nuclei in a magnetic field is called nuclear magnetic
resonance.
• For a particular nucleus an NMR absorption spectrum may
consist of one to several groups of absorption lines in the rf
region of the electromagnetic spectrum.
• They indicate the chemical nature of the nucleus and the
spatial positions of neighboring nuclei.
 Introduction
• NMR spectroscopy uses rf radiation to induce transitions
between different nuclear spin states of samples in a
magnetic field.
• NMR spectroscopy can be used for quantitative
measurements, but it is most useful for determining the
structure of molecules along with IR spectroscopy and mass
spectrometry.
• The utility of NMR spectroscopy for structural
characterization arises because different atoms in a
molecule experience slightly different magnetic fields and
therefore, transitions at slightly different resonance
frequencies in an NMR spectrum.
 PRINCIPLE OF NMR
• Elementary particles such as electrons or a
nucleus are known to behave as if they rotate
about an axis and thus have the property of
spin.
• The angular momentum associated with the
spin of the particle would be an integral or a
half-integral multiple of h/2π, where h is
Planck’s constant.
 Principle of NMR
• The maximum spin component for a particular
particle is its spin quantum number I. Subatomic
particles (electrons, protons and neutrons) can be
imagined as spinning on their axes.
• In many atoms (such as 12C) these spins are
paired against each other, such that the nucleus of
the atom has Nuclear Magnetic Resonance
Spectrometer 245 no overall spin. However, in
some atoms (such as 1H and 13C) the nucleus
does possess an overall spin.
 Principle of NMR
The rules for determining the net spin of a nucleus are as
follows:
(i) If the number of neutrons and the number of protons are
even, the spin would be zero.
Nuclei of this type do not give rise to an NMR signal.
Neither do they interfere with an NMR signal from other
nuclei. Examples are C12, 016.
(ii) Nuclei having either the number of protons or the
number of neutrons as odd have half integral spin.
Examples are H1 B11, p31, etc.
(iii) Nuclei which have both the number of neutrons and the
number of protons as odd would have integral spin. For
example, H2 and N14.
 Nuclear Energy Levels
• Since a nucleus possesses a charge, its spin gives
rise to a magnetic field that is analogous to the
field produced when an electric current is passed
through a coil of wire.
• The resulting magnetic dipole or nuclear
magnetic moment m is oriented along the axis of
spin and has a value that is characteristic for each
kind of particle.
 Nuclear Energy Levels
• When spinning nucleus is placed in a strong uniform magnetic
field (H) , the field exerts a torque upon the nuclear magnet.
• This would make the nucleus to assume a definite orientation
with respect to the external field. The torque is a vector with its
direction at right angles to the plane of μ and H.
• This results in a rotation of the nuclear axis around the direction
of the external field. This is called precessional motion.
• Each orientation of the nucleus corresponds to a different
energy level or state. The interrelation between particle spin
and magnetic moment leads to a set of observable magnetic
quantum states given by the following formula:
Nuclear Energy Levels
 Nuclear Energy Levels
• The overall spin, I, is important. Quantum mechanics tell
us that a nucleus of spin I will have 2I + 1 possible
orientations. A nucleus with spin 1/2 will have 2 possible
orientations.
• In the absence of an external magnetic field, these
orientations are of equal energy. If a magnetic field is
applied, then the energy levels split. Each level is given a
magnetic quantum number, m.
• The spin number for both the electron and proton is 1/2.
Thus each has two spin states, corresponding to I = 1/2
and I = −1/2. The spin number of a nucleus is related to
the relative number of protons and neutrons it contains.
 Resonance Condition
• When an alternating rf field, superimposed over
the stationary magnetic field, rotates at exactly the
frequency of an energy level, the nuclei will be
provided enough energy to undergo a transition
from a lower energy level to a higher-energy level.
• In general, the energy difference between states is
given by

Ho- Magnetic field strength in Gauss

μ- Magnetic moment
I- Net Spin
β- Constant
 Resonance Condition
• The frequency ν of the radiation that will effect
transitions between energy levels can be determined
from the Planck’s equation as given below:
 Resonance condition
• The frequency of the resonance absorption can be
adjusted by varying the value of the applied magnetic
field. Difficulties in construction of large magnets limit
the field to approximately 23,000 gauss. In that case
 Resonance condition
• Therefore, proton will precess 95 million times
per second in a fixed field of 23,000 gauss. The
frequency 95 MHz lies in the rf range of the
electro-magnetic spectrum.
 Chemical Shift
• It is the phenomenon that occurs in which a specification,
that is, a carbon or hydrogen atom, in a given molecule
resonates at a slightly different frequency based on its local
chemical environment.
• In other words, the difference between the field necessary
for resonance in the sample and in some arbitrarily chosen
reference compound is called the chemical shift. For
protons, it is usual to refer spectra to tetramethyl silane
(TMSi) with extrapolation to infinite dilution in an inert
solvent such as CCI4.
• TMSi gives sharp resonance line at the high field end of the
range of observed proton shifts and therefore, it does not
obscure any other proton lines arising from the sample.
 Chemical Shift
• Chemical is expressed as:

•where Hsample and HTMSi are the positions of the

absorption peaks for the sample and reference material
respectively in Hz and H1 is the rf of the signal used. The
chemical shift ‘δ units’ is expressed in parts per million
(ppm).
•NMR takes advantage of the phenomenon of the
chemical shift so it allows a chemist to obtain a picture of
not only how many particular atoms are in a molecule,
but also an idea of how the atoms are joined together in
the molecule.
 Types of NMR Spectrometers
Continuous Wave (CW) NMR Spectroscopy:
•A CW-NMR spectrometer consists of a control
console, magnet, and two orthogonal coils of wire
that serve as antennas for rf radiation.
•One coil is attached to an rf generator and serves
as a transmitter.
•The other coil is the rf pick-up coil and is attached
to the detection electronics.
 Types of NMR Spectrometers
Fourier Transform NMR Spectrometer:
• FTNMR spectrometers use a pulse of rf radiation causes
nuclei in a magnetic field to flip into the higher-energy
alignment. Due to the Heisenberg uncertainty principle,
the frequency width of the rf pulse (typically 1–10 ms) is
wide enough to simultaneously excite nuclei in all local
environments.
• All of the nuclei will re-emit rf radiation at their respective
resonance frequencies, creating an interference pattern in
the resulting rf emission versus time, known as a free
induction decay (FID).
• The frequencies are extracted from the FID by a Fourier
transform of the time-based data.
Block diagram of CW NMR Spectrometer
 Block diagram of CW NMR Spectrometer

Key parts are:

• A magnet, which produces magnetic field in the range
10,000–25,000 gauss.
• Radio frequency transmitting system
• The signal amplifier and detector
• A display device, which may be a recorder or an oscilloscope
• A non-magnetic sample holder, which holds the sample
• Computer workstation which stores and processes the NMR
data using complex software to generate spectrum for the
same
 Magnetic field
• The magnet used in these instruments may be
permanent magnet or electromagnet. Alternately,
the magnetic field may be produced from super-
conducting solenoids.
• A permanent magnet is less expensive, but it does
not allow the observation of the resonance of
different nuclei and of a given nucleus, at two
different field strengths.
• Therefore, either electromagnet or superconducting
magnets are generally used.
 Magnetic Field
• Important requirement of the magnet is that, it should
be stable and homogeneous.
• In electromagnets, stability of the magnetic field is
achieved by continuously compensating for small rapid
fluctuations in magnetic field with coils wound around
the pole faces and by controlling the temperature of the
magnet to minimize thermal fluctuations.
• Inhomogeneity is compensated also with small magnetic
fields, produced by passing DC current through small
electrical coils located on the faces of the magnet, and
spinning the sample to effectively average out field
gradients in the direction perpendicular to the spin axis.
 Magnetic field
• The magnet is placed in a thermostated oven
and is surrounded by heavy thermal insulation.
Special magnetic and rf shielding minimizes the
effects of environmental perturbations, which
can disrupt NMR operation.
• For the study of NMR, there are great
advantages in working at the highest possible
applied magnetic field strength, especially for
the resonances of nuclei other than hydrogen
and fluorine.
 Magnetic field
• Super-conducting magnets are operated at the
temperature of liquid helium which is 4.2 K at
standard pressure and for the highest available
fields even at 2 K.
• The magnet coils are constructed using
niobium alloy wires embedded in a copper wire
which allows the winding of a solenoid. The
niobium alloys used become super-conducting
at low temperatures unlike copper.
 Magnetic field
• A typical super-conducting solenoid is 26 cm long, with
a 3 cm bore and outside diameter 8.36cm.
• It is wound with Nb-Zr 25% wire and produces a field of
5T (1 T = 10,000 gauss) with a current of about 20 A.
• Permanent magnets can yield maximum magnetic
fields, approximately 14,000 gauss, whereas
electromagnets can produce fields up to about 24,000
gauss. Super-conducting solenoids have been used to
give approximately 70,000 gauss.
Radio Frequency Transmitter
 Radio Frequency Transmitter
• The rf transmitter is a 60 MHz crystal controlled oscillator. The
rf signal is fed into a pair of coils mounted at right angles to the
path of the field.
• The coil that transmits the rf field is made in two halves, to
allow insertion of the sample holder. The two halves are placed
in the magnetic gap. For high-resolution work, the transmitted
frequency must be highly constant to about 1 part in 10 8.
• The oscillator is of low power, generally of less than 1 W. The
basic oscillator is usually crystal controlled, at a fundamental
frequency of 15 MHz.
• It is followed by a buffer doubler, the frequency being doubled
by tuning the variable inductance to the second (30 MHz). It is
further connected to another buffer doubler, with the
connector inductance, tuned to 60 MHz.
 Signal Amplifier and Detector
• The rf signal produced by the resonating nuclei is
detected by means of a coil that surrounds the sample
holder.
• This coil consists of a few turns of wire and is placed at
right angles to the source coil and the stationary field
to minimize pick up from these fields.
• The signal results from the absorption of energy from
the receiver coil, when nuclear transitions are induced
and the voltage across the receiver coil drops.
• This voltage change is quite small and must be
amplified in an rf amplifier before it can be displayed.
Signal Amplifier and Detector
 Signal Amplifier and Detector
• After impedance matching in a transformer T1, the input rf
signal is amplified in a three-stage low noise cascade
amplifier.
• The output of the last rf stage is applied to the AGC
(automatic gain control) and spectrum detectors.
• The AGC voltage is fed back to the previous stage through
an AGC amplifier, which is kept cut-off due to a delaying
bias, until a predetermined signal level is reached.
• This delayed AGC allows maximum gain on weak signals
and prevents overdriving on strong signals.
 Fourier Transform NMR Spectrometer
• The limitations of CW spectrometers are low
sensitivity and long analysis time.
• In pulsed NMR spectrometers, a single pulse of rf
energy is used to simultaneously activate all
nuclei.
• The excited nuclei returning to the lower energy
level generate an FID signal that contains in a
time domain all the information obtained in a
frequency domain
 FTNMR
(Principle)
 FTNMR
(Free Induction Decay Signal)
FTNMR
FTNMR Block diagram
 FTNMR
• It uses a super-conducting (cryogenic) solenoid as the
source of the magnetic field.
• Introduction of FT-pulsed NMR spectrometer has made
the acquisition of spectra routine and has also allowed
proton spectra to be obtained in much less time, and
with smaller amounts of specimen as compared to CW
techniques.
• This data is digitized and a computer performs a Fast
Fourier Transform to convert it from an FID signal as a
function of time (time domain) to a plot of intensity as
a function of frequency (frequency domain).
 FTNMR
• This ‘spectrum’ has one peak for each resonant frequency in
the sample.
• The real advantage of the pulsed- FT method is that, because
the data is recorded so rapidly, the process of pulse excitation
and recording the FID can be repeated many times, each time
adding the FID data to a sum stored in the computer.
• The signal intensity increases in direct proportion to the
number of repeats or ‘transients’, but the random noise
tends to cancel because it can be either negative or positive,
resulting in a noise level proportional to the square root of
the number of transients.
Electron Spin Resonance (ESR) Spectroscopy

• Electron spin resonance involves detecting a physical

phenomenon of absorption of electromagnetic
radiation in the microwave region by paramagnetic
species that are subjected to an external magnetic field.
• It is the study of magnetic dipoles of electronic origin by
applying, usually, fixed microwave frequencies to a
sample residing in a varying magnetic field.
• Also known as electron paramagnetic resonance (EPR)
spectroscopy, it is a valuable research and analytical
tool in Chemistry, Physics, Biology and Medicine.
 ESR Spectroscopy
• The phenomenon of electron spin resonance is based on
the fact that an electron possesses a spin, and associated
with the spin, there is a magnetic moment, the value of
which is called the Bohr magneton.
• The atoms, ions or molecules having an odd number of
electrons exhibit characteristic magnetic properties,
which arise from the spinning or orbiting action of the
unpaired electrons about the nucleus.
• When a strong magnetic field is applied to the unpaired
spins of an electron, the electrons will be split into two
groups. In one group, the electron dipoles or magnetic
moments of the electrons are aligned either parallel or
anti-parallel to the direction of the external magnetic
field.
 ESR Spectroscopy
• The electrons will precess about the axis of the magnetic
field at a frequency proportional to both the applied
magnetic field and the electron magnetic moment.
• If a second, weaker radiofrequency alternating magnetic
field, having the frequency of precession of the electron is
applied at right angles to the fixed magnetic field, resonance
occurs.
• At resonance, the absorption of energy from the rotating
field causes the spin of the electrons to flip from the lower
energy level to the higher level.
• The two levels are separated by
ESR Spectroscopy
 ESR Spectroscopy
• For a free electron, the frequency of absorption is given by

(μ= 9.28474x10-28J/G, h=6.626x10-34 J-s)

• In a field of 3,400 gauss, the precession frequency is
approximately 9,500 MHz.
• In actual practice, the radio frequency (rf) is in the
microwave region and is held at a certain constant value,
and the magnetic field strength is varied to obtain
conditions where resonance occurs.
• The incident radiation is absorbed by the electrons in the
lower energy level and they jump into higher energy state.
 ESR Spectroscopy
• In general, if n1, the population of the ground
state, exceeds n2 the population of the excited
state, a net absorption of microwave radiation
takes place. The signal would be proportional
to the population difference (n1−n2).
• By the Boltzmann distribution law, the
population ratio in the two states is given by
 ESR Spectroscopy
• For routine investigations with the ESR
spectrometer, it is a general practice to employ
an X-band frequency (8.5–10 GHz).
Basic ESR Spectrometer
 Basic ESR Spectrometer
• Microwaves are generated by the klystron tube and the
power level adjusted with the attenuator.
• The circulator routes the microwaves entering from the
klystron towards the Cavity where the sample is mounted.
• A majority of EPR spectrometers operate at approximately
9.5 GHz. The radiation may be incident on the sample
continuously or pulsed.
• The sample is placed in a resonant cavity which admits
microwaves through an iris. The cavity is located in the
middle of an electromagnet and helps to amplify the
weak signals from the sample.
 Basic ESR Spectrometer
• Numerous types of solid-state diodes are sensitive to
microwave energy and absorption lines can be detected
when the separation of the energy levels is equal or
very close to the frequency of the incident microwave
photons.
• A wave meter is put in between the oscillator and
attenuator to know the frequency of microwaves
produced by klystron oscillator.
• The wave meter is usually calibrated in frequency unit
(megahertz) instead of wavelength. Waveguide is a
hollow, rectangular brass tube. It is used to convey the
wave radiation to the sample and crystal.
 Basic ESR Spectrometer
• The power propagated down the waveguide may
be continuously decreased by inserting a piece of
resistive material into the waveguide. The piece is
called variable attenuator and used in varying the
power of the sample from the full power of
klystron to one attenuated by a force 100 or more.
• Isolators are used to prevent the reflection of
microwave power back into the radiation source.
It is a strip of ferrite material which allows
microwaves in one direction only. It also stabilizes
the frequency of the klystron.
 Basic ESR Spectrometer
• Microwaves reflected back from the cavity are
routed to the diode detector, and any power
reflected from the diode is absorbed completely
by the load.
• The diode thus produces a current proportional to
the microwave power reflected from the cavity.
• Thus, in principle, the absorption of microwaves
by the sample is detected by noting a decrease in
current in the micro-ammeter.
 Basic ESR Spectrometer
Klystron Tube:
There are three electrodes:
(i) a heated cathode from which electrons are emitted
(ii) an anode to collect the electrons
(iii) a highly negative reflector electrode which sends those electrons
which pass through a hole in the anode back to the anode.
 Basic ESR Spectrometer
Cavity:
• The sample is mounted in the microwave cavity.
• The cavity is a rectangular metal box, exactly one
wavelength in length.
• An X-band cavity has dimensions of about 1 × 2 ×
3 cm.
 Basic ESR Spectrometer
• Since the cavity length is not adjustable but it must be
exactly one wavelength, the spectrometer must be
tuned such that the klystron frequency is equal to the
cavity resonant frequency.
• The tune-up procedure usually includes observing the
klystron power mode.
• That is, the klystron reflector voltage is swept, and
the diode current is plotted on an oscilloscope or
other device.
• When the klystron frequency is close to the cavity
resonant frequency much less power is reflected from
the cavity to the diode, resulting in a dip in the power
mode.
 Basic ESR Spectrometer
• The cavity dip is centered on the power mode
using the coarse mechanical frequency
adjustment with the reflector voltage used to
fine tune the frequency.
 Components of ESR Spectrometer
• The sample is irradiated by microwave energy from the klystron in
the microwave bridge. A klystron normally operated at 9.5 GHz,
generates a microwave field.
• The magnetic field at the sample is modulated at 100 kHz. The
klystron output passes through an isolator, a power leveller and a
directional coupler.
• The field is applied to the resonant cavity, which is connected to
one arm of the microwave bridge.
• During the magnetic field scan, when field intensity reaches the
value required to induce electron spin resonance in the sample, a
change occurs in the amount of microwave energy absorbed by
the sample.
• This causes a change in the microwave energy reflected from the
cavity. The reflected microwave energy, which is modulated at the
field modulation frequency, is directed to the detector crystal.
ESR Spectrometer
 Mass Spectrometers
• In a mass spectrometer, the sample to be analyzed is first
bombarded with an electron beam to produce ionic fragments of the
original molecule.
• These ions are then sorted out by accelerating them through electric
and magnetic fields, according to their mass-to-charge (m/e) ratio.
• A record of the numbers of different kinds of ions is called the mass
spectrum.
• The uniqueness of the molecular fragmentation is the basis for
identification of different molecules in a complex mixture, as no two
molecules will be fragmented and ionized in exactly the same
manner.
• Very small sample sizes, which may be of the order of a few tenths of
a milligram, are generally sufficient as long as the material is able to
exist in the gaseous state at the temperature and pressure existing in
the ion source.
 Mass Spectrometers
Applications:
• Direct determination of the molecular weight
• The placement of functional groups into certain
areas of the molecules.
• Their interconnection and investigation of reaction
mechanism.
Advantages :
• The main advantage of mass spectrometry over
other spectroscopic techniques is its sensitivity. It
is possible on some instruments to obtain full mass
spectra with 1 ng of material in about a second.
 Mass Spectrometers
Advantages:
• A significant advantage of mass spectra is its suitability for
data storage and library retrieval, since the positions
(masses) of the peaks in the spectrum of a given compound
are fixed.
• Another asset of mass spectrometry is its capability in
handling complex mixtures.
• Impurities of masses different than the one being analyzed
do not interfere with the results.
 Mass Spectrometers
Principle:
• The procedure for analyzing a substance by mass spectrometry starts
by converting the substance into a gaseous state by chemical means.
• The gas is introduced into the highly evacuated spectrometer tube,
where it is ionized by means of an electron beam. The positive ions
thus formed are deflected and focused by means of suitable magnetic
and electric fields.
• For a given accelerating voltage, only positive ions of a specific mass
pass through a slit and reach the collecting plate.
• The ion currents thus produced are measured by using a sensitive
electrometer tube.
• By varying the accelerating voltage, ions from other mass species may
be collected, and the ion currents measured in such cases would be
proportional to the amount of the given mass species present.
 Mass Spectrometers
Principle:
 Mass Spectrometers
Principle:
• The molecules in the gas sample (A) to be analyzed are bombarded
with electrons to produce ions (B).
• These ions are accelerated in a high vacuum into a magnetic field
(C), which deflects them into circular paths (D).
• Since the deflection for light ions is greater than that for heavy
ions, the ion stream separates into beams of different molecular
weight.
• A suitably placed slit (F) allows a beam of a selected molecular
weight to pass through to a collection electrode (E).
• As the accelerating voltage on the ion source is gradually reduced,
ion beams of successively greater mass pass through the slit.
• When these ions fall on the collector electrodes, they produce
minute electric currents, which after suitable amplification, may be
measured. Their amplitude will indicate the number of ions in each
beam.
 Mass Spectrometers
Example:
• Let us take water (H2O) as an example to illustrate
the principle of mass spectrometry. A water molecule
consists of two hydrogen (H) atoms and one oxygen
(O) atom. The total mass of a water molecule is the
sum of the mass of two hydrogens (approximately 1
atomic mass unit per hydrogen) and one oxygen
(approximately 16 atomic mass units per oxygen).
• Let us suppose that we put some water vapour into
the mass spectrometer.
 Mass Spectrometers
• Some of the collisions between the water
molecules and the electrons will be so hard that
the water molecules will be broken into smaller
pieces, or ‘fragments’. For water, the only
possible fragments will be [OH]+, O+ and H+.
 Mass Spectrometers
• A trained mass spectrometrist can interpret the
masses and relative abundances of the ions in a
mass spectrum and determine the structure and
elemental composition of the molecule.
• Computer programs, such as those that search
libraries of mass spectra for the best match, can
also be used to interpret a mass spectrum.
 Types of Mass Spectrometers
1. Magnetic Defection Mass Spectrometer:
(600 Sector Mass Spectrometer)
 Magnetic Deflection Mass Spectrometer
• The heated tungsten filament produces an electron beam,
which passes between plates A and B. A difference in electrical
potential between A and B pulls ions out of the beam, so that
they pass through the slit in B into the region between B and C.
• The potential difference between B and C is adjustable from 0
up to several thousand volts. The ion beam then enters the
space between two trapezoid shaped magnet poles, where it is
deflected through an angle of 60, 90, 120 or 180.
• When ions of mass m and charge e pass through an accelerating
electric field, they would attain a velocity v, which can be
expressed in terms of the accelerating voltage V as follows:
 Magnetic Defection Mass Spectrometer
• If the ions next enter a magnetic field of constant intensity
h, which is applied at right angles to their direction of
motion, the ions would be diverted into circular orbits.
• From physics, it is known that when acceleration is applied
perpendicular to the direction of ion motion, the objects
velocity remains constant, but the object travels in a
circular path.
• Equating the centripetal and the centrifugal forces results
in the following formula:
 Time of Flight Mass Spectrometer
• In a time-of-flight mass spectrometer, ions of different m/e
ratio are separated by the difference in time they take to
travel over an identical path from the ion source to the
collector. This requires that the starting time (the time at
which the ions leave the ion source) is well defined.
• Therefore, ions are either formed by a pulsed ionisation
method (which is usually matrix assisted laser desorption
ionisation) or various kinds of rapid electric field switching are
used as a ‘gate’ to release the ions from the ion source in a
very short time.
• In the pulsed mass spectrometer, in which ion packets of a
few micro-seconds duration are emitted at intervals of a few
milliseconds from a voltage source.
 Time of Flight Mass Spectrometer
• The ions traverse an evacuated tube called the drift tube
to reach the detector. The detector is sensitized for a brief
instant to register their arrival.
• Since ions of different masses arrive at the detector at
different times, the accurate measurement of the time
between activating the source and sensitizing the
detector gives information concerning the mass of the
ions.
• The signal from the ions reaching the detector is amplified
and applied to the vertical deflection plates of an
oscilloscope.
• The horizontal axis deflection of the oscilloscope
commences as the ion packets start out. This produces a
mass spectrum on the screen of the oscilloscope.
 Time of Flight Mass Spectrometer
The essential parts of a time-of-flight instrument are:
• An electron gun for the production of ions.
• A grid system for accelerating ions to uniform
velocities in a pulsed mode.
• An evacuated tube, called the drift tube.
• An ion detector and suitable electronic circuitry for
translating the time-dependent arrival of ions of
different velocities into a time base that is related
to mass number.
Time of Flight Mass Spectrometer
 Time of Flight Mass Spectrometer
• If L is the length of the drift tube in
centimetres and t is transit time in micro-
seconds, for singly charged ions of mass m and
constant energy Ve, then

•If the detector is sensitised for a period Dt at time t,

the resolution Dm/m, for constant energy, is given by
 Time of Flight Mass Spectrometer
• The time resolution will increase with increased drift
tube length and will decrease with increasing
accelerating voltage.
• The current produced by the ions arriving at the
collector may have a very short duration, which
necessitates the use of a wide-band amplifier.
• Specially designed magnetic electron multiplier is
used for this purpose.
• This multiplier uses a strip of semiconducting material
for the multiplying surface instead of dynodes.
• A gain of 107 is attained with a dark current of only 3
× 10−21A.
 Time of Flight Mass Spectrometer
• The ions leaving the ion source of a time-of-flight mass spectrometer have
neither exactly the same starting times nor exactly the same kinetic
energies.
• Various time-of-flight mass spectrometer designs have been developed to
compensate for these differences.
• One such design makes use of a device known as Reflectron. The
‘Reflectron’ is an ion optic device in which ions in a time-of-flight mass
spectrometer pass through a ‘mirror’ (reflection) and their flight is
reversed.
• The linear reflection allows ions with greater kinetic energies to penetrate
deeper into the Reflectron than ions with smaller kinetic energies.
• The ions that penetrate deeper will take longer to return to the detector. If
a packet of ions of a green m/e ratio contains ions with varying kinetic
energies, then the Reflectron will decrease the spread in the ion flight
times, and therefore improve the resolution of the time-of-flight mass
spectrometer.
 Time of Flight Mass Spectrometer
Reflectron: