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David Smith
Emeritus Professor of Chemistry
University of Nebraska
Lincoln, NE 68588 USA
Course Topics
Overview
Electron Impact Ionization and Fragmentation
Chemical Ionization
Fast Atom Bombardment Ionization
Chemical Derivatives
Elemental Composition
Analyses of Natural Products: Acetogenins
Electrospray Ionization; LCMS;
Matrix Assisted Laser Desorption Ionization
Collision Induced Fragmentation; CID MS/MS
Quantitation
Chemical Ionization
Similar to EI (Electron Ionization)
Use to analyze same types of compounds (must be volatile)
Use same sample inlets (solids probe or GC)
Requires only minor changes to the ion source
Different from EI
Gives less fragmentation, charge-induced fragmentation only
Greatly simplified spectra
Use to determine/verify MW
Determine the number of labile hydrogens
Can selectively ionize amines
-500 V
Sample
plus
reagent
gas
Analyzer pressure
~10-6Torr
0V
Trap
+20 V
-500 V
Analyzer pressure
~10-6Torr
0V
Trap
+20 V
Formed by EI
Formed by EI
MH+ + R
MH+
Proton Affinity = -H
CH3CH2CH2CH2OH2+ + CH4
base 1
base 2
PT Proton Transfer
Proton Affinity
kcal/mol
CH4
127
C2H6
142
C2H4
153
iC4H8
195
CH3Br
163
CH3OH
183
C2H5OH
189
CH3OCH3
191
CH3COCH3
195
CH3CO2H
189
NH3
203
C2H5SC2H5
204
HCON(CH3)2
211
Aniline
208
NH(CH3)2
219
N(CH3)3
223
Methane PT
NH4+ Adduct
Isobutane PT
Ammonia PT
PA > 203
PA > 127
PA > 184
PA > 195
Citronellol
CI Isobutane
Formed by PT
EI and CI of Ephedrine
EI spectrum is very simple, but does not give the MW
58
58
MH+ - H2O
HA PT
EI
CI
Together, these three
peaks show that
MW = 165
134
MH+
i-C4H10
CH4
134
MH+
139
M(D4)D+
ND3
m = 5 4 exchangeable H
151
m =17
MNH4+
159
m = 8
MW + 2
MW + 22
ND3
ROD/RND2/RND/RSD
MND4+
CH3CH2CH2NH2
MW + 4
MW + 24
CH3CH2NHCH3
MW + 3
MW + 23
(CH3)3N
MW + 2
MW + 22
CH4
369
MH+-18
369
MH+-18
385
M-H+
385
M-H+
369
NH3
386
MNH4+-H2O-NH3
MDND4+-D2O-ND3
MNH4+-H2O
404
MNH4+
MDND4+-D2O
MND4+
369
ND3
389
409