Mass Spectrometry

Mass Spectrometry
 The technique is used to determine the atomic weight of elements,
number of isotopes and their natural abundance.
 Molecular masses of molecules and their molecular formula how?

A beam of high-energy electrons breaks the molecule making their

fragments. The masses of the fragments and their relative
abundance reveal information about the structure of the molecule.
 It does not involve the absorption or emission of light.

 MS is a graph of relative abundance vs m/z

Mass Spectrometer
 How do we achieve this?

Persuade the molecule to enter the gas phase is really difficult. So we

produce ions from the element/molecule that enter the gas phase.

Ions thus formed are separated on the basis of their m/z ratio
 Some Basic Terms
•Molecular ion - The ion obtained by the loss of one
electron from the molecule (m+)
•Base peak - The most intense peak in the MS, assigned
100% intensity
•Radical cation - positively charged species with an odd
number of electrons
•Fragment ions - Lighter cations (and radical cations)
formed by the decomposition of the molecular ion.  These
often correspond to stable carbocations.
•m/z - mass to charge ratio.
 ELECTRON IMPACT
H H
H-C:H + e H-C H + 2e CH4
H H
RADICAL CATION
H
H H
H-C
H H-C + + H
H
BOND-BREAKING RADICAL
CATION
H
H-C + H+
H
ONLY CATIONS ARE CARRIED TO DETECTOR
Typical Mass Spectrum
100%
43 base peak given 100%
abundance

NOTE: 114-71 = 43
58
NOTE: 43 = mass of radical
50%
71
114
molecular ion

m/e
Isotope peaks - P+1,
P+2, etc
 Electron Impact Ionization
A high-energy electron can dislodge an electron
from a bond, creating a radical cation (a
positive ion with an unpaired e-).
H H
H C C H
H H
H H H H
e- + H C C H H C C+ H
H H H H

H H
H C+ C H
=>
H H
 Separation of Ions
• Only the cations are deflected by the magnetic
field.
• Amount of deflection depends on m/z smaller the
m/z ratio higher will be the deflection and vice
versa.
• The detector signal intensity is proportional to the
number of ions hitting it.
• By varying the magnetic field, ions of all masses
are collected and counted. =>
 High Resolution MS
• Masses measured to 1 part in 20,000.
• A molecule with mass of 44 could be C3H8,
C2H4O, CO2, or CN2H4.
• If a more exact mass is 44.029, pick the
correct structure from the table:
C3H8 C2H4O CO2 CN2H4
44.06260 44.02620 43.98983 44.03740
=>
 Mass Spectra of Alkanes
More stable carbocations will be more abundant.

=>
 Mass Spectra of Alkenes
Resonance-stabilized cations favored.

=>
Molecules with
Heteroatoms
Isotopic Abundance

81
Br

=>
Mass Spectrum with Sulfur

=>
Mass Spectrum with Chlorine

=>
Mass Spectrum with Bromine

=>
 The GC-MS a hyphenated technique

A mixture of compounds is separated

by gas chromatography, then identified
by mass spectrometry.

=>