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Mass Spectrometry: - Introduction
Mass Spectrometry: - Introduction
Mass Spectrometry: - Introduction
Mass Spectrometry
• Introduction
• Ionization
• Separation
• Fragmentation
• Isotope Effects
• High Resolution
Ions with a
large mass
Recorder
Ions with a
small mass
Sample molecules
Ionisation area
Electrometer
Sample leak
tube
Instrumental Analysis in Molecular Chemistry
3
Department of Organic Chemistry, IMM, Radboud University Nijmegen
Volatilization
Ionization (1)
Fragmentation possibilities:
.
a) Loss of radical M+ → A+ + B
.
i.e. an odd electron (OE) ion gives
an even electron ion (EE) + a radical
. .
b) Loss of neutral fragment, even-electron molecule M+ → C+ + D
i.e. OE ion gives other OE ion
Massaspectrometrie
Depending O +.
on the energy OH
Benzoic acid
of the electron C7H6O2, Mr 122
70 eV is C6H5 (77)
standard ! HC CH
(26)
+
C4H3 (51)
Instrumental Analysis in Molecular Chemistry
10
Department of Organic Chemistry, IMM, Radboud University Nijmegen
Drawbacks of EI (1)
a) No molecular ion observed for molecules that are prone
to fragmentation. See the example of a branched alkane
Drawbacks of EI (2)
c) Thermal lability:
decomposition prior to
ionization, or
fragmentation after
ionization, because of the
temperatures required
for vaporization.
The possibility of
fragmentation depends
on the energy
transferred with the
protonation, i.e.
on the strength of the acid
produced from the
reaction gas.
Instrumental Analysis in Molecular Chemistry
13
Department of Organic Chemistry, IMM, Radboud University Nijmegen
. .
CH4+ CH3+ + H
. .
CH4+ CH5+ + CH3
. .
O - + CH4 OH- + CH3
source
Acceleration in electric field:
To ½.m.v2 = z.e.V
vacum m = mass of ion
pump v = velocity
z = charge
e = unit charge (electron)
V = potential of electrostatic field
Magnet
Bending by Lorentz force
in magnet (centripetal force)
FL = B.z.e.v
With the detector slit at a distance 2r from the source slit, V can be
varied with a fixed B so that ions with a certain m/z reach the detector.
Resolution
Resolution
defined
as (M/ΔM)10%
Isotope Effects
Spectrum of HCl
Atom weights:
H: 1; Cl: 35,5
Expected (naively):
M+. at 36,5
Cl+ fragment at 35,5
Observed:
Strong peaks at 36 and 38
Weak at 35 and 37
Reason: Cl occurs as
a mixture of isotopes
35Cl and 37Cl in
approx. 3 : 1 ratio
Instrumental Analysis in Molecular Chemistry
24
Department of Organic Chemistry, IMM, Radboud University Nijmegen
For 3 Br atoms, a = b = 1 : 1
(a + b)3 = a3 + 3a2b + 3ab2 + b3 = 1 + 3 + 3 + 1
i.e. 4 peaks with intensity ratio 1 : 3 : 3 : 1
(a + b)n (c + d)m
Summary
In conventional MS techniques, small (apolar, < MW 1000;
polar, < MW 300) molecules are volatilized, ionized, and the ions
separated by a magnet.