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Survey of Mass Spectrometry

David Smith
Emeritus Professor of Chemistry
University of Nebraska
Lincoln, NE 68588 USA

Former Director of the Nebraska


Center for Mass Spectrometry

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

Chemical Ionization (CI)


Emission filament
where White Hot
wire emits electrons

Small apertures are


required to achieve high
pressure

-500 V
Sample
plus
reagent
gas

Analyzer pressure
~10-6Torr

0V
Trap
+20 V

Reagent gas pressure 0.5 Torr

EI: Ions drift from electron beam


to exit aperture with no collisions
CI: Reagent ions formed by EI

Chemical Ionization (CI)


Small apertures are
required to achieve high
pressure

Ions undergo thousands


of collisions with reagent
gas

-500 V

Analyzer pressure
~10-6Torr

0V
Trap
+20 V

Reagent gas pressure 0.5 Torr

Methane Chemical Ionization

Ions formed by EI of methane

Reagent gas pressure is sufficiently high


in the ionization chamber that each ion
undergoes 100-1000 collisions before
exiting.

Isobutane Chemical Ionization

Formed by EI

Less energetic, less fragmentation than methane CI

Ammonia Chemical Ionization

Formed by EI

Less energetic, less fragmentation than isobutane CI


Selectively ionizes compounds that contain N

Chemical Ionization Reactions


Proton Transfer (PT)
RH+ (Reagent ion) + M (Sample)
Proton Affinity (PA): H+ + M

MH+ + R
MH+

Proton Affinity = -H

Excitation energy of MH+ = PA (M) PA (R)


Excitation energy in MH+ facilitates fragmentation
CH5+ + CH3CH2CH2CH2OH

CH3CH2CH2CH2OH2+ + CH4

base 1

base 2

PT is an acid/base reaction. The stronger base keeps the proton.


Proton transfer occurs only when PA (M) > PA (R)

Chemical Ionization Reactions (Cont)


Hydride Abstraction (HA)

HA occurs most often with long chain saturated hydrocarbons

Adduct Formation (A)

The adduct likely dissociates if the excitation energy is not removed


by a third molecule
Higher source pressure and lower source temperature
favor formation of adducts

Chemical Ionization Reactions (Cont)

PT Proton Transfer

HA Hydride Abstraction A Adduct

Predict Reactions From Proton Affinities


Compound

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

Use CI to Simplify Spectra


EI

Citronellol

CI Isobutane
Formed by PT

Change reagent gas to CH4? To NH3?

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

CI of Aspartic Acid MW 133


134
MH+

134
MH+

i-C4H10

CH4

134
MH+

Using ND3 as the reagent


gas allows one to determine
the number of exchangeable H
NH3

139
M(D4)D+

ND3

m = 5 4 exchangeable H
151
m =17
MNH4+

159
m = 8

Use ND3 to Determine the Number of Exchangeable H


Mass shift due to charging:
M + ND4+ MD+
MND4+

MW + 2
MW + 22

Mass shift due to exchangeable H:


ROH/RNH2/RNH/RSH

ND3

ROD/RND2/RND/RSD

Consider 3 structures for C3H9N


MD+

MND4+

CH3CH2CH2NH2

MW + 4

MW + 24

CH3CH2NHCH3

MW + 3

MW + 23

(CH3)3N

MW + 2

MW + 22

Ammonium Adducts May Lose Water


Ammonium adducts (M + 18) of some compounds may
lose water (M + 18 18) to give what appears as M+.
The exact mass of the apparent M+. is not consistent with
the elemental composition of the unknown.

Same Nominal Masses


Different Exact Masses

Chemical Ionization of Cholesterol MW 386


i-C4H10

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

New Terms And Concepts


Compare CI to EI; Source modifications required to increase pressure
Why is high reagent gas pressure required?
Reagent gas; Common gases; Reagent ions; Common reactions
Proton transfer; Hydride abstraction; Adduct formation
Proton Affinity; How does it relate to ion excitation energy and fragmentation
Use proton affinity to predict PT or A in ammonia CI
Use ammonia CI to determine the number of exchangeable H
Explain apparent M+ in ammonia CI spectra

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