Lecture 2:

Ionization Techniques – Part I

CU- Boulder
CHEM 5181
Mass Spectrometry & Chromatography
MS
Prof. Jose-Luis Jimenez Interpretation
Fall 2006 Lectures

High Vacuum
Sample Ion Mass
Detector Recorder
Inlet Source Analyzer
2

Ionization Methods Brainstorming

• What are the desirable characteristics of an
ionization method?

3
 Ionization Methods Characteristics

From Lambert

Ionization Techniques (that we will discuss)

• Electron Ionization (EI)
• Chemical Ionization (CI)
• Electrospray (ESI) / Nanospray
• Desorption Techniques
– Fast Atom Bombardment (FAB)
– Matrix-Assisted Laser Desorption/Ionization (MALDI)
– DESI
• Ionization for Elemental Analysis
– Thermal Ionization Source
– Spark Source
– Glow Discharge
– Inductively-Coupled Plasma (ICP)
5
 From Schewdt

Effect of Ionization Techniques

• Same molecule analyzed by 4 techniques

• Information is complementary, use >1 technique if possible
• Goal for today: understand why this happens
6

Electron Ionization Source Scheme

Extraction
Plate
-300 V

Ground
0V
+

Electron
Emission
Filament
-70 V Electron Collector
7
 Electron Ionization Source

From
Watson 8

EI Notes 1
• Hot filament giving off electrons
– “Thermoionic effect”
– W or Re filament
• Accelerated by a potential difference towards and
anode
• Interact with the gaseous molecules in their path
– Do not “impact” them
ions formed
• Ionization Efficiency IE =
molecules present
• What characteristic of the electron can we change
to try to improve the results of ionization?
9
 Electron Interaction Cross Sections (SF6)

http://www.eeel.nist.gov/811/refdata/ 10

Electron Interaction Cross Sections (CF4)

http://physics.nist.gov/Divisions/Div842/Icamdata/PDF/1Databases/christo.pdf
http://www.eeel.nist.gov/811/refdata/ 11
 The Concept of Cross Section
• Electrons are coming perpendicular to page

Physical Scattering 70 eV 15 eV
Cross Cross Ionization Ionization
Section Section Cross Cross
Section Section

12

Time Scales of Ionization

• What happens to the molecule when an electron
goes by?
– 70 eV electron => 5 x 106 m/s
– Molecule = 10 A = 1 nm
• Transit time = 2 x 10-16 s
• Molecular vibrations > 10-12 s
• Electronic time scale ~ 10-16 s
e • Frank-Condon principle: nuclei remain frozen in position

+
molec + +
frag1 frag2 frag1
“PSD”

1016 s e e >10-12 s 10-5 s Log(t) 13

 EI Notes 3
• What electron energy would be most interactive with the
molecule?
• Each electron is associated with a wave
• λ = h / (mv)
• 2.7 A for 20 eV, 1.4 A for 70 eV
• Wave is “dispersed” into many frequencies. If one of them has
an energy hv corresponding to an electronic transition in
molecule, energy transfer leads to excited electronic state
– 10 to 20 eV are transferred to the molecule. Only 10 eV are needed to
ionize, so rest of the energy can lead to fragmentation
• Ionization potential: energy it would take to eject the weakest
bound electron from the molecule
• At very high energies the wavelength becomes too small, and
the molecules become “transparent” to the electron. In other
words: not enough time to interact + transfer energy 14

Ionization Efficiency vs. Electron Energy 1

From
Watson

15
Ionization Efficiency vs. Electron Energy 2
From
Hoffmann

16

“Soft” and “Hard” Events 1

From
Lambert

17
 “Soft” and “Hard” Events 2
From
Lambert

18

Fragmentation notes
• Fragmentation depends on:
– Internal energy deposition on the ion
• Shapes of the potential energy hypersurfaces
• Energy of the interacting electrons
– Molecular structure resists fragmentation
• Chemical nature of the analyte
• Is fragmentation good or bad?

19
 EI: Fragmentation vs. Electron Energy
From
Hoffmann

20

EI Fragmentation vs. Molecular Structure

From
Lambert

21
 Breakdown Curve for 1-propanol
• This information CH3-CH2-CH2OH
can be precisely
determined using
electrons of a
single energy, and
scanning the
energy
• This is what is
different between
molecules (prev.
slide)
From
Lambert
22

Breakdown
Curve
&
Internal
Energy
Distribution
Chemical
of Molecular Ionization
Ions I

From
Lambert
23
 Breakdown
Curve
&
Internal
Energy
Distribution
of Molecular
Ions II

From
Lambert
24

Breakdown
Curve
+
Internal
Energy
Distribution
of Molec.
Ions III
From
Lambert
25
 Internal Energy Distribution after EI
From
Lambert

26

Reproducibility: 4 Spectra of 1-Propanol in NIST

31 Contributor: NIST 31
100 31
Mass Spectrometry
100
Contributor: also from
100 Again noteNIST
that it doesn’t
Data Center, 1990.
correspond to 70 eVs
50
OH 50
of internal energy OH

29 29
42 42
59 59
15 15 45
45
0
0
10 20 30 OH40 50 60 70
50 10 20
(m ainlib) 1-Propanol
30 40 50 60 70
(m ainlib) 1-Propanol

31 31
100 Contributor: Chemical 100 Contributor: From
Concepts Japan AIST/NIMC
Database

29
42
50 OH 50
59 OH

15 45
0 27 59
10 20 42 29 30 59 40 50 27 60 42 70
33 45 57
(m 0ainlib)
10
1-Propanol
20 30 40 50 60 70
0
10 20 30 40 50 60 70
(replib) 1-Propanol (replib) 1-Propanol
27
 Electron Ionization Notes
• Big advantage: high reproducibility of the
fragmentation because
– Purely physical (not chemical) process
– Fragmentation involves only gas-phase
unimolecular reactions
• However all MS are far less reproducible
than those based in the interaction of
electromagnetic radiation with matter (IR,
NMR)
– MS depend on distribution of electron energies,
time allowed for fragmentation
28

Advantages + Disadvantages of EI

From Lambert
29
 Appendix:
Filament Emission and Failure
Characteristics

30

Filament Emission Characteristics I

The Mass Spec

Handbook of Service.
Published by Scientific
Instrument Services, Inc.
http://www.sisweb.com/

31
Filament Emission Characteristics II

MS Handbook
Of Service

32

Filament Burnout Patterns

MS Handbook
Of Service

33