UNIT-IV: NMR and Mass Spectrometry

Chemical shift, Factors influencing chemical shifts: electronegativity and electrostatic effects;
Mechanism of shielding and deshielding. Spin systems: First order and second order coupling of AB
systems, Simplification of complex spectra. Spin-spin interactions: Homonuclear coupling
interactions - AX, AX2, AB types. Vicinal, germinal and longrange coupling-spin decoupling.
Nuclear Overhauser effect (NOE), Factors influencing coupling constants and Relative intensities.
13CNMR and structural correlations, Satellites. Brief introduction to 2D NMR – COSY, NOESY.
Introduction to 31P, 19F NMR. Mass Spectrometry: Ionization techniques- Electron ionization (EI),
chemical ionization (CI), desorption ionization (FAB/MALDI), electrospray ionization (ESI),
isotope abundance, molecular ion, fragmentation processes of organic molecules, deduction of
structure through mass spectral fragmentation, high resolution. Effect of isotopes on the appearance
of mass spectrum.
Chemical shift
• An NMR spectrum is a plot of the radio frequency applied against absorption.
• A signal in the spectrum is referred to as a resonance.
• The frequency of a signal is known as its chemical shift, d

• The most commonly used scale for measuring chemical shifts is the  (delta)
scale.
• Most chemical shifts have  values between 0 and 10. A small  value indicates a
small downfield shift while a large  value represents a large downfield shift. An
NMR signal from a particular proton appears at a different field than the signal
from TMS. The chemical shift ( ) is defined as

• It is often convenient to describe the relative positions of the resonances in an NMR spectrum.
For example, a peak at a chemical shift, δ, of 10 ppm is said to
be downfield or deshielded with respect to a peak at 5 ppm, or if you prefer, the peak at 5
 ppm is upfield or shielded with respect to the peak at 10 ppm.
(i) The reference compound is the same for both, tetramethysilane (Si(CH3)4). The
position of the TMS signal is taken at  = 0.0ppm
(ii) Its resonance is sharp and intense since all the twelve protons are equivalent and
absorb at exactly the same applied field.
• For example, at 60 MHz the shift ofthe protons in CH3Br is 162 Hz while at 100 MHz,
the shift is 270 Hz from TMS. However, both of these correspond to the same value of
= 2.70 ppm

Factors influencing chemical shifts: electronegativity and electrostatic effects

• Electrons around the nucleus create a magnetic field that opposes the applied field.
This reduces the field experienced at the nucleus.
• Since the induced field opposes the applied field the electrons are said to be
diamagnetic and the effect on the nucleus is referred to as diamagnetic shielding.
• Since the field experienced by the nucleus defines the energy difference between
the different spin states, the frequency and hence the chemical shift δ will change
depending on the electron density around the nucleus.
• Electronegative groups decrease the electron density around the nucleus, and there
is less shielding (i.e. deshielding) so the chemical shift increases.
• Increasing the number of electronegative substituents increases the deshielding of
protons and increases the chemical shift.
 Compound,
CH3F CH3OH CH3Cl CH3Br CH3I CH4 (CH3)4Si
CH3X

X F O Cl Br I H Si

Electronegativity
4.0 3.5 3.1 2.8 2.5 2.1 1.8
of X

Chemical
4.26 3.4 3.05 2.68 2.16 0.23 0
shift, δ / ppm

Mechanism of shielding and deshielding

Shielding:
• The greater the electron density all around the nucleus, the bigger the opposing magnetic
field to the electrons, and hence the greater the shielding.
• Because the proton is subjected to a reduced external magnetic field B0, it requires a lower
frequency to establish resonance, causing the chemical shift to shift upfield (lower ppm).
Example of shielding :
• Shielding occurs in nuclear fission when electrons farthest from the center of the atom are

drawn away.
Deshielding:
• When the electron density around a nucleus falls, the opposing magnetic field B0 gets
smaller, and the nucleus feels more of the external magnetic field.
Example of De - shielding:
• The chemical shift of CH4 protons and CH3Cl protons, can be taken into account here. The
chlorine atom is an electronegative atom that attracts electron density and causes the
hydrogen nucleus to be deshielded. As a result, the movement will be toward greater ppm.
Because the hydrogen nucleus in CH4 is protected, the peak appears on the lower ppm side.
 • In a molecule, all the protons may not be in the same electronic environment. When a
molecule is placed in an external magnetic field, the valence electrons around protons are
made to circulate.
• This circulation generates a local diamagnetic current and produces a counter magnetic
field which opposes the applied magnetic field. The field experienced by the proton is
thus diminished and the proton is said to be shielded.
• This effect is called diamagnetic shielding or diamagnetic anisotropy.

Spin systems: First order and second order coupling of AB systems

• In a given molecule, protons with the same environment absorb at the same applied
field and exhibit same chemical shift.
• A set of protons with same environment are said to be equivalent.

• On the other hand, protons with different environments absorb at different applied
fields with different chemical shifts are said to be non-equivalent.

• AB system : A system containing two protons, say HA and HB which couple with
each other but do not couple with any other proton and their chemical shift (δA─δB)
values difference is comparable to the coupling constant JAB.

• In AB system, both the nuclei are strongly coupled and are designated by adjacent
letters A and B in the alphabet.
 • In such systems the doublets are distorted i.e. they are not 1:1. The inner lines
become larger and the outer lines smaller.
First-order coupling: In NMR spectroscopy, spin-spin coupling in which the energy differences
between the spin states are equal. Results in first-order splitting. First order coupling Jab=Jac

• First-order splitting results. The n+1 rule is obeyed. A triplet is observed.

• Second order Coupling : In NMR spectroscopy, spin-spin coupling in which the energy
differences between the nuclear spin states are not equal.

• The n+1 rule is not obeyed; complex splitting patterns (non-first-order splitting) often result.

• Non-first-order splitting results. The n+1 rule is not obeyed. A doublet of doublets is observed
Spin-spin interactions: Homonuclear coupling interactions - AX, AX2, AB types.

• AX System A system having two protons, say HA and HB with their chemical shift (δA─δB)
values difference much larger to the coupling constant JAB.
 • This system shows two distinct doublets with all the four lines of equal intensity.

• The example of AX system is dichloroacetaldehyde (Cl2CHCHO).

AX2, A2X system

• In this system, two magnetically equivalent protons are coupled to the third proton which
has chemical shift value widely different from the other two protons.

• For such system, NMR spectrum shows a proper doublet (1:1) and a triplet (1:2:1).

• Examples are Cl2CHCH2Cl, Cl2CHCHClCHCl2.

AB System A system containing two protons, say HA and HB which couple with each other but do
not couple with any other proton and their chemical shift (δA─δB) values difference is comparable
to the coupling constant JAB. In AB system, both the nuclei are strongly coupled and are designated
by adjacent letters A and B in the alphabet. In such systems the doublets are distorted i.e. they are
not 1:1. The inner lines become larger and the outer lines smaller.
Vicinal, germinal and long range coupling Factors influencing coupling constants and Relative
intensities
• The splitting pattern of a given nucleus (or set of equivalent nuclei) can be predicted by
the n+1 rule, where n is the number of neighboring spin-coupled nuclei with the same (or
very similar) Js.
• If there are 2 neighboring, spin-coupled, nuclei the observed signal is a triplet ( 2+1=3 ); if
there are three spin-coupled neighbors the signal is a quartet ( 3+1=4 ). In all cases the
central line(s) of the splitting pattern are stronger than those on the periphery.
• The intensity ratio of these lines is given by the numbers in Pascal's triangle. Thus a doublet
has 1:1 or equal intensities, a triplet has an intensity ratio of 1:2:1, a quartet 1:3:3:1 etc.
•
The Coupling Constant (J)
• The separation between two adjacent peaks in a multiplet in NMR spectrum of a
molecule is called coupling constant ( J).
• The coupling constant is a measure of how strongly a proton is affected by the
spin states of its neighboring protons.
• The spacing between the adjacent peaks of a multiplet is measured on the same
scale as the chemical shift, and the coupling constant (J) is always expressed in
Hertz (Hz).
• The value of coupling constant remains the same irrespective of the strengths
of the applied magnetic field.
• In the NMR spectrum of ethyl iodide (CH3CH2I), the methyl protons give rise to
a triplet centred at 1.83 ppm, and the methylene protons give a quartet centred at
3.20 ppm, the coupling constant between methyl and methylene protons is 7.5
Hz.

Factors Affecting The Values Of Coupling Constant (J)

(i) Geminal coupling : In the case of protons attached to the same carbon but having
different chemical environments in a saturated compound, the value of J depends
H
upon the bond angle ( ) .
• When the bond angle is 105º, J is approximately —
25
H
 Hz.
• When the bond angle is widened upto 125º, the value of J increases to zero.
• If the bond angle is larger than 125º, a small positive value of J is observed.
Following characteristics of the geminal coupling constant (Jgem.) are worthnoting :

(i) Vicinal coupling : For vicinal protons, the value of coupling constant varies with the dihedral
angle. When the dihedral angle is 0º or 180º, the coupling constant is found to be maximum.
It is slightly negative when dihedral angle is 90º.
 In case of cyclopentanes, where the
dihedral angle for cis protons is 0º, Jvic is found to be 8 Hz whereas for trans protons
where the dihedral angle is 90º, Jvic is observed to be nearly equal to zero.

Long range coupling :

• Generally, no coupling is observed if the distance between the two absorbing nuclei is
more than three covalent bonds apart.
• However, in unsaturated compounds, appreciable coupling is observed with the high
resolution spectrometers even if the concerned nuclei are more than three covalent
bonds apart.
• This is called long range coupling. In 2, 4-dichlorobenzaldehyde, long range coupling
occurs between the aldehydic proton and a ring proton

SPIN DECOUPLING

• The effect of spin-spin coupling can be removed by a technique called "decoupling“.

• The effect of decoupling is to mask the presence of a particular proton group,

 • e.g. the He protons in the Ethylbenzene figure.

• A spectrum is acquired as if the He protons were absent!

• This is achieved by transmitting a decoupling pulse sequence at the He resonance

frequency fe and thereby permanently changing the spin orientation of these protons. For
the spectrum illustrated in the Ethylbenzene Spectrum figure the decoupling frequency
would be 1.25 ppm above the TMS peak.

• Decoupling pulses tend to be longer and of lower power than excitation pulses.

• The Decoupling Experiment figure below is a representation of a decoupling experiment,

while the Ethylbenzene Spectrum with Homodecoupling figure shows the decoupled
spectrum. The CH2 quartet has now become a singlet.

• the quartet collapsing to a singlet.

• The signal from the CH3 group at 1.25 ppm is missing from the decoupled spectrum,
because the decoupling pulses effectively removes the effects of the presence of the CH3
protons.
Nuclear Overhauser effect (NOE)

• The nuclear Overhauser effect ( NOE) is the transfer of nuclear spin polarization from one
population of spin-active nuclei (e.g. 1 H, 13 C, 15 N etc.) to another via cross-relaxation.

• The Nuclear Overhauser effect(NOE) is a “through space” effect that can be observed by
irradiating a peak corresponding to a particular proton in the sample with lower power
radiation than is used for decoupling.

• This effect is popularly known as the NOE effect in abbreviated form.

 • If HA and HB are two protons close in space within molecules then irradiating the peak of
proton HA will enhance the peak of the Proton HB. This effect is simply known as the
Nuclear Overhauser effect.

• The signal enhancement in NOE is due to dipolar interaction(cross-polarization) in which

the polarization of the spin states in one nucleus(proton) causes the polarization of the spin
states in another nucleus.

• Due to the interaction of spin dipoles in an excited state, energy transfer takes place. This
causes an enhancement in the signal in the NOE effect.
13CNMR AND STRUCTURAL CORRELATIONS
• The study of carbon nuclei through nuclear magnetic resonance spectroscopy is an
important technique for determining the structures of organic molecules.
• Using it together with proton NMR (PMR) and infrared spectroscopy, organic chemists
can often determine the complete structure of an unknown compound.
• 13C-NMR spectra can be used to determine the number of non- equivalent carbon atoms
and to identify the types of carbon atoms that may be present in a compound.
• Thus, 13C-NMR provides direct information about the carbon skeleton of a molecule.
• • 13C isotope has a natural abundance of 1.108% (of all C atoms) • Magnetogyric ratio γ
for 13C is approximately four times small • As a result, a 13C nucleus is about 400 times
less sensitive than an 1H nucleus NMR spectroscopy 13C - 13C coupling is no
• • Chemical shifts measured with respect to tetramethylsilane, (CH3)4Si (i.e., TMS •
Chemical shift range is normally 0 to 220 ppm 13 as in 1H NMR • Similar factors affect
the chemical shifts in C 13 • C spectra are normally broadband proton decoupled, removed
 between C and H, so peaks appear as single lines
• • Number of peaks indicates the number of distinct types of C
Satellites
• Carbon satellites in spectroscopy, are small peaks that can be seen shouldering the main
peaks in the nuclear magnetic resonance (NMR) spectrum.
• These peaks can occur in the NMR spectrum of any NMR active atom (e.g. 19F or 31P
NMR) where those atoms adjoin a carbon atom
• Carbon satellites are most often encountered in proton NMR.
• In the example of proton NMR, these peaks are not the result of proton-proton coupling,
but result from the coupling of 1H atoms to an adjoining 13C atom.
• These small peaks are known as carbon satellites as they are small and appear around the
main 1H peak i.e. satellite (around) to them.
Brief introduction to 2D NMR – COSY, NOESY
• Two-dimensional nuclear magnetic resonance spectroscopy (2D NMR) is a set of nuclear
magnetic resonance spectroscopy (NMR) methods which give data plotted in a space
defined by two frequency axes rather than one.
• Types of 2D NMR include correlation spectroscopy (COSY), J-spectroscopy, exchange
spectroscopy (EXSY), and nuclear Overhauser effect spectroscopy (NOESY).
• Two-dimensional NMR spectra provide more information about a molecule than one-
dimensional NMR spectra and are especially useful in determining the structure of a
molecule, particularly for molecules that are too complicated to work with using one-
dimensional NMR.
Correlation Spectroscopy (COSY)
• The most basic form of 2D NMR is the 2D COSY (pulse sequence shown below)
experiment, a homonuclear experiment with a pulse sequence.
• It consists of a 90o RF pusle followed by an evolution time and an additional 90o pulse.
The resulting oscillating magnetization (symbolized by decaying the sinusoidal curve) is
then acquired during t2 .
 • For example, in COSY of 1-propanol (CH3CH2CH2OH), the peak marked A
indicates a coupling interaction between the H at 1.5 ppm and the H at 3.6
ppm. This corresponds to the coupling of the CH2 group and the adjacent H
on the CH2OH group.
• Similarly, the peak marked B indicates a coupling interaction between the H
at 0.7 ppm and the H at 1.3 ppm. This corresponds to the coupling of the CH2
and the CH3 in the 1-propanol .
• There are a second set of equivalent peaks, also marked A and B on the other
side of the diagonal.

NOESY
 • The NOESY (Nuclear Overhauser Enhancement SpectroscopY) spectrum allows users to
trace out the spatial relationships in the molecule.

• The Nuclear Overhauser Effect (NOE) arises from dipole-dipole interactions due to
proximity between active nuclei, giving information about the spatial environment when
active spins are close in space (< 5 Å).

• In the case where NOE is experimentally observed, information related to relative

stereochemical, and molecule assignment is obtained.

• Vanillin has an aromatic ring with three substituents and using NOESY spectroscopy it is
possible to assign the aromatic substitution in the ring.

NOESY for very large molecules and These spectra are used to locate protons that are close
together in space.
Introduction to 31P, 19F NMR
• 19F has magnetically active nucleus with nuclear spin quantum number, I=1/ 2.
• Except for the appropriate radiofrequency source, no major modification is required in the
instrument for recording 19F NMR spectrum of a compound.
• 19F chemical shifts are measured taking CFCl3 as reference.
• The range of chemical shift covered by fluorine containing compound is 0 to 200 ppm
compared to 0 to 10 ppm in case of 1H NMR.
• Moreover, signals corresponding to 19F resonances are well separated on the spectrum.
• Obviously, the value of coupling constants (J) in 19F NMR signals have large values.
• . J values for (i) geminal C F F F—F coupling ranges form 43 to 370 Hz. (ii) vicinal F—
C—C—F F—F coupling ranges from 0 to 39 Hz. (iii) cis configuration C = C F F F—F
coupling ranges from 0 to 58Hz, while trans C = C F F F—F coupling ranges from 106 to
148 Hz.
• The coupling between 1H and 19F is also very strong.
• Geminal H—F coupling constant ranges from 42 to 80 Hz while vicinal H—F coupling
constant ranges from 1.3 to 29 Hz.
 • For cis H—F coupling, J = 0 to 22 Hz while for trans H-F coupling, J=11 to 52 Hz. Fluorine
substituted to benzene ring also couple with the benzene ring protons.
• For ortho H-F, coupling constant ranges from 7.4 to 11.8 Hz, for meta H-F coupling, J
value ranges from 4. 3 to 8.0 Hz and for para H-F coupling, J value ranges from 0.2 to 2.7
Hz.
31
P NMR SPECTROSCOPY
• 31
P nucleus is magnetic with nuclear spin quantum number , I=1/ 2.
• Its natural abundance is 100%.
• For P-H coupling, multiplicity rules are same as for H-H coupling.
• Coupling constants (JP-H) are quite large, around 200-700 Hz. JCPH lies in the range 0.5
to 20 Hz.
• Coupling is effective through at least four bonds.
• There are no rules for predicting 31P chemical shifts.
• Let us consider the spectra of compounds such as Ph3P, H3PO4 and (C2H5O) POCl
• . Here, phosphorus atoms differ widely with respect to valence state and groups attached
to them, yet every compound has a distinct chemical shift and provides useful information
even in the absence of predictive rules.
• 13P NMR spectroscopy can be used in investigating the mechanism of reactions.
• In Wittig reaction, an aldehyde or ketone is treated, an with a phosphorane (a phosphorus
ylide) to produce an olefin. 1
• 3P NMR spectra showed that oxaposphetanes are the intermediate species instead of
betaine since the spectra of reaction mixture at low temperatures are in agreement with
oxaphosphetane and not with tetracoordinated phosphorus species as in the case of a
betaine .
• The proton decoupled 31P spectra of triphenyl phosphine, Ph3P gives a singlet.
Mass Spectrometry
• Mass spectrometry is based on identifying molecules based on their molecular weight and
weights of fragments formed from the molecules as measured by using electric and
magnetic fields to measure masses of ions generated in the gas phase.
• It is a powerful analytical technique that can used for identification and quantification of
 the compounds in a mixture with the help of separation techniques such as gas
chromatography (GC) and liquid chromatography(LC).
• Mass spectrometry is one of the most sensitive techniques that can be used for
identification of compounds.
Ionization techniques
Electron ionization (EI) –
• EI is done by volatilizing a sample directly in the source that is contained in a vacuum
system directly attached to the analyzer.
• The gas phase molecules are bombarded by a beam of electrons formed by heating a
filament bias at a negative voltage compared to the source.
• The bias voltage is most commonly at -70 volts.
• The electron beam ejects an ion from the gas phase molecule producing a radical ion. This
technique is considered a hard ionization technique, because it causes the ion to fragment.

• EI is also the method that is most commonly used for GC-MS.

Chemical Ionization (CI)

• In chemical ionization, the sample is introduced to a chamber filled with excess reagent
gas (such as methane).
• The reagent gas is ionized by electrons, forming a plasma with species such as CH5+, which
react with the sample to form the pseudomolecular ion [M+H]+.
 • Because CI does not involve radical reactions, fragmentation of the sample is generally
much lower than that of EI.
• CI can also be operated in negative mode (to generate anions) by using different reagent
gases.
• For example, a mixture of CH4 and NO2 will generate hydroxide ions, which can abstract
protons to yield the [M-H]- species.

Desorption ionization
Fast Atom Bombardment (FAB) –
• FAB is a technique that was popular because it was the first technique that allowed
ionization of non-volatile compounds that could be done simply.
• It was done by bombarding a sample in a vacuum with a beam of atoms, typically Ar or
Xe, accelerated to Kilovolt energies.
• The sample was typically mixed in a matrix.
• The two most common matrixes were glycerol and 3 Nitro-benzoic acid.
• The matrix allowed the sample to refresh itself. The ions formed by FAB were adducts to
the molecule, where the adducts could be protons, sodium ions, potassium ions or
ammonium ions.
• A variation of FAB was replacement of the atom beam with a beam of ions, typically
cesium ions, which was called secondary ion mass spectrometry (SIMS). SIMS spectra
were typically identical to FAB spectra and the terms became interchangeable.
Matrix Assisted Laser Desorption Ionization (MALDI)-
• MALDI is a method of ionization in which the sample is bombarded with a laser.
• The sample is typically mixed with a matrix that absorbs the laser radiation and transfer a
proton to the sample.
• Some small mass samples can be ionized without matrix, but this is typically called laser
desorption.
• The laser is always pulsed, and typically in a vacuum.
• In addition, MALDI mostly forms singularly charged ions. This means MALDI is mostly
performed on specially built time-of-flight instruments.
• One major application of MALDI besides simple analysis is imaging mass spectrometry.
Electrospray Ionization (ESI)
• Electrospray ionization mass spectrometry is a desorption ionization method.
• Desorption ionization methods can be performed on solid or liquid samples, and allows
for the sample to be nonvolatile or thermally unstable.
• Electrospray ionization is a soft ionization technique that is typically used to determine
the molecular weights of proteins, peptides, and other biological macromolecules.
• Soft ionization is a useful technique when considering biological molecules of large
molecular mass, such as the aformetioned, because this process does not fragment the
macromolecules into smaller charged particles, rather it turns the macromolecule being
ionized into small droplets.
• These droplets will then be further desolvated into even smaller droplets, which creates
molecules with attached protons.
• These protonated and desolvated molecular ions will then be passed through the mass
analyzer to the detector, and the mass of the sample can be determined.
• As the droplets shrink due to evaporation, the charge density increases until a coulombic
explosion occurs, producing daughter droplets that repeat the process until individualized
sample ions are generated (see figure below).
 • One of the limitations of is the requirement that the sample be soluble. ESI is best applied
to charged, polar, or basic compounds.

Isotope Abundance
• When interpreting mass spectra it is important to remember that the relative atomic mass
or atomic weight of an element is a weighted average of the naturally occurring isotopes.
• Mass spectrometers separate these isotopes and they are each observed at their respective
mass to charge ratio.
• The relative abundance used to determine the relative atomic mass is determined using
mass spectrometry.
• it also provides useful information for identifying the elements in an ion.
• Chlorine is an excellent example of how isotope distributions are useful for interpretation.
• The molecular weight of chlorine is 35.45u.
• This is calculated from the natural abundance
of 35Cl(75%)35Cl(75%) and 37Cl(25%)37Cl(25%).
• For CH3Cl the molecular ion is 12C1H335Clat 50 m/z .
• The natural abundance of these two isotopes is observed in the mass spectrum as two peaks
separated by 2 m/z with a relative intensity of 3:1
• . The mass spectrum of chlorobenzene C6H5Cl clearly shows the chlorine isotope
distribution at 112 m/z and 114 m/z .
• These peaks correspond to the molecular ion - the molecular ion has the most abundant
isotope for each element - at 112 m/z (6x12 + 5x1 + 35) and the
 • 37Cl isotope peak at 114 m/z (6x12 + 5x1 + 37) and the relative intensity is determined by
the natural abundance of the 37Cl isotope.
• The other major peak in this spectrum at 77 m/z corresponds to the loss of chlorine from
the molecular ion or the 37Cl isotope peak to give C6H5+ (112 - 35 = 77 OR 114 - 37 =
77).
Molecular Ion
• In a mass spectrometer, molecules are broken down into charged pieces known as ions,
which are then sorted based on their masses.
• The vertical axis shows the highest content of ions.
• A mass spectrum is a chart that contains the masses of the pieces as well as a measurement
of their relative abundance.
• The most intense point in a spectrum is referred to as the “Base Peak,” and its intensity is
set to 100%.
• This ion is the most common in the ionisation chamber and the most stable, making it
valuable for identifying the molecule.
• The release of one electron from an electrically neutral molecule results in the formation of a
molecular ion
• The electron bombardment with energy 10-15 eV usually removes one electron from the
molecule of the organic compound in the vapour phase.
• It results in the formation of molecular ion (). The highest occupied orbital of aromatic
system and non bonding electron orbitals on oxygen and nitrogen atoms readily lose one
electron.
• An electron from double bond (2- electron) or triple bond (4- electron) is usually lost.
In alkanes, the ionization of C—C sigma bonds is easier than that of C—H bonds.
• The mass of the parent ion gives the molecular mass of the sample. I
Fragmentation Processes of Organic Molecules
The relative abundance of the fragment ions formed depends upon the following factors:
1. Stability of ions
2. Stability of radical lost
(1) Simple cleavage
• Fragmentation of odd electron molecular ion M+. may occur through homolytic or
heterolytic cleavage of single bond.
A. Homolytic cleavage:
• Odd electron ions have an unpaired electron which is capable of new bond formation.
• The energy released by bond formation can help offset the energy required for the
cleavage of some other bond in the molecules.

(ii) Heterolytic cleavage

• Cleavage of the C-X (x= O, N, S, Cl) bond is more difficult than that of the C-C bond.
• In such a cleavage the positive charge is carried by the carbon atom and not by a
heteroatom. eg. Fragmentation of alkyl halide.
(iii) Hydrogen transfer
• These processes are very common in mass spectroscopy, which involves the transfer of
hydrogen atoms from one part of the molecule to another part.
• E.g., an even-numbered fragment mass from an even-numbered molecular ion mass
indicates a rearrangement of hydrogen has accompanied the fragmentation process.

• From hydrogen rearrangement, we can distinguish between cis and trans isomer as well
as ortho-substituted compounds from meta and para-substituted compounds.
B. γ -hydrogen transfer (Mc-Lafferty rearrangement)
• This arrangement involves the cleavage of the β-bond followed by the γ-Hydrogen
transfer. The mechanism involves the six-membered transition state.
• This rearrangement eliminates neutral molecules from aldehydes, ketones, amines, and
unsaturated compounds.
• To undergo the Mc-Lafferty rearrangement reaction, a molecule must possess
appropriately located heteroatoms (e.g., oxygen), a π system, and an abstractable
hydrogen atom at γ position to the C=O system.

MC-Lafferty rearrangement reaction

Effect of isotopes on the appearance of mass spectrum.
• Since the majority of elements have two or more isotopes, the ratio of these isotopes can
be a powerful tool in deriving the composition of unknown samples.
• some isotopes are so prominent that they can easily be observed with a quadrupole mass
spectrophotometer with unit resolution.
• Chlorine, bromine, and sulfur can all be identified by their isotopic rations.

Element M+ M+1 M+2

hydrogen 1H 100.0%
carbon 12C 98.9% 13C 1.1%
nitrogen 14N 99.6% 15N 0.4%
oxygen 16O 99.8% 18O 0.2%
sulfur 32S 95.0% 33S 0.8% 34S 4.2%
chlorine 35Cl 75.5% 37Cl 24.5 %
bromine 79Br 50.5% 81Br 49.5%
iodine 127I 100.0%

• Compounds can also contain any combination of multiple chlorine and bromine atoms.
These samples will produce distinct peaks due to the various combinations of the isotopes.
A compound containing two bromines will have a M+2 peak twice the size of the M+ peak
and a M+4 peak the same size as the M+ peak