2.1.

ION SOURCES 17

TA B LE 2.1. Overview of the Ion Generation Methods Described in this Chapter

Method Acronym Category Ion type Applicationsa
Gas discharge – Discharge Atomic ions First ionization
mechanism to be used
in MS
Thermal ionization TI Ionization by heating Atomic ions Isotope ratio, Trace
analysis; Solid samples
Spark source SS Discharge Atomic ions Trace analysis in solid
samples
Glow discharge GD Plasma source Atomic ions Trace analysis
Inductively coupled ICP Plasma source Atomic ions Isotope ratio; Trace
plasma analysis
Electron ionization EI Electron induced Volatile Smaller molecules;
ionization molecular GC-MS; Extensive
ions libraries
Chemical ionization CI Electron induced Volatile GC-MS
ionization molecular
ions
Atmospheric pressure APCI Electron induced Nonvolatile Smaller molecules;
chemical ionization ionization molecular LC-MS
ions
Photoionization PI Photoionization Volatile Smaller molecules;
molecular GC-MS
ions
Multiphoton MPI Photoionization Atomic and Resonance-enhanced
ionization molecular MPI is highly
ions selective; Trace
analysis
Atmospheric pressure APPI Photoionization Nonvolatile LC-MS; Nonpolar
photoionization molecular compounds
ions
Field ionization FI Ionization by strong Volatile Molecular compounds
electric field molecular
ions
Field desorption FD Desorption/ionization Nonvolatile First soft method; Large
by strong electric molecular molecules
field ions
Thermospray TSI Spray Nonvolatile LC-MS
ionization molecular
ions
Electrospray ESI Spray Nonvolatile Soft method, LC-MS;
ionization molecular Large molecules
ions
(Continued)
18 A MASS SPECTROMETER’S BUILDING BLOCKS

TA B LE 2 . 1. Continued
Method Acronym Category Ion type Applicationsa
Desorption DESI Spray Nonvolatile Direct, preparation-free
electrospray molecular analysis of samples
ionization ions
Direct analysis in real DART Discharge Nonvolatile Direct, preparation-free
time molecular analysis of samples
ions
Secondary ion (mass SIMS Particle induced Nonvolatile Semiconductors;
spectrometry) desorption/ molecular Surface analysis;
ionization ions Imaging
Fast atom FAB Particle induced Nonvolatile Soft method; Large
bombardment desorption/ molecular molecules
ionization ions
Plasma desorption PD Particle induced Nonvolatile Soft method; Large
desorption/ molecular molecules
ionization ions
Laser desorption/ LDI Photon induced Nonvolatile Isotope ratio; Trace
ionization desorption/ atomic and analysis
ionization molecular
ions
Matrix-assisted laser MALDI Photon induced Nonvolatile Soft method; Large
desorption/ desorption/ molecular molecules
ionization ionization ions
Atmospheric pressure AP- Photon induced Nonvolatile Soft method; Large
matrix-assisted laser MALDI desorption/ molecular molecules
desorption/ ionization ions
ionization
a
The “applications” column does not cover all applications, but some examples.

Figure 2.1. Schematic of a thermal ionization (TI) source. Each filament consists of two pins
connected by a wire.
 TA B LE 2.2. A Rough Comparison of Some Features of the Mass Analyzers
Analyzer TOF Sector Q filter QIT Orbitrap FTICR Accelerator
Resolution Low –high Very high Low –medium Low –high Very high Highest Very high
Mass accuracy High Very high Low Low –medium Very high Very high Very high
a
m/z range Very high Medium Low Low –medium Low Medium Very low
Sensitivity High High High High Medium Medium High
Dynamic Medium Very high High Low –medium Medium Medium Very high
range
Quantification Medium –good Very good Good –very Poor Medium Medium Very good
good
Speed Fast Slow Medium –fast Medium –fast Slow –medium Slow – medium Slow
Ion-source Pulsed/ Continuous Continuous Pulsed/ Pulsed/ Pulsed/ Continuous
continuous continuous continuous continuous
Handling Easy –medium Medium – Easy Easy Medium Demanding Very
demanding demanding
a
There is presently only one instrument type available, and its maximum m/z is set to 4000 Th.

39
 2 Carbon Isotopic Patterns 501

Pt continued 192 191.961035 2.311

194 193.962664 97.443
195 194.964774 100
196 195.964935 74.610
198 197.967876 21.172
Au Gold 79 197 196.966552 100 196.966552
Hg Mercury 80 196 195.965815 0.50 200.59
198 197.966752 33.39
199 198.968262 56.50
200 199.968309 77.36
201 200.970285 44.14
202 201.970626 100
204 203.973476 23.00
Tl Thallium 81 203 202.972329 41.892 204.3833
205 204.974412 100
Pb Lead 82 204 203.973029 2.7 207.2
206 205.974449 46.0
207 206.975881 42.2
208 207.976636 100
Bi Bismuth 83 209 208.980383 100 208.980383
Th Thorium* 90 232 232.038050 100 232.038050
U Uranium* 92 234 234.040946 0.0055 238.0289
235 235.043923 0.73
238 238.050783 100

2 Carbon Isotopic Patterns

Read out the PM+1/PM ratio from a mass spectrum to calculate the approximate
number of carbon atoms. Provided no other element contributing to M+1 is pres-
ent, an M+1 intensity of 15 %, for example, indicates the presence of 14 carbons.
(For the risk of overestimation due to autoprotonation cf. Chap. 7.2.1)

Fig. A.1. Calculated isotopic patterns for carbon. Note the steadily expanding width of the
pattern as X+2, X+3, X+4,... become visible. At about C90 the X+1 peak reaches the same
intensity as the X peak. At higher carbon number it becomes the base peak of the pattern.
502 Appendix

Table A.2. Calculated isotopic distributions for carbon

Number of X+1 X+2 X+3 X+4 X+5

Carbons
1 1.1 0.00
2 2.2 0.01
3 3.3 0.04
4 4.3 0.06
5 5.4 0.10
6 6.5 0.16
7 7.6 0.23
8 8.7 0.33
9 9.7 0.42
10 10.8 0.5
12 13.0 0.8
15 16.1 1.1
20 21.6 2.2 0.1
25 27.0 3.5 0.2
30 32.3 5.0 0.5
40 43.2 9.0 1.3 0.1
50 54.1 14.5 2.5 0.2 0.1
60 65.0 20.6 4.2 0.6 0.2
90 97.2 46.8 14.9 3.5 0.6
120a 100.0 64.4 27.3 8.6 2.2
a
The X peak has an abundance of 77.0 % in that case.

3 Silicon and Sulfur Isotopic Patterns

Fig. A.2. Isotopic patterns for silicon and sulfur. The peak at zero position corresponds to
the monoisotopic ion at m/z X. The isotopic peaks are then located at m/z = X+1, 2, 3, ...
 5 Characteristic Ions 503

4 Chlorine and Bromine Isotopic Patterns

For halogens the

isotopic peaks
are separated by
2 u.

Fig. A.3. Calculated isotopic patterns for combinations of bromine and chlorine. The peak
shown at zero position corresponds to the monoisotopic ion at m/z X. The isotopic peaks
are then located at m/z = X+2, 4, 6, ... The numerical value of X is given by the mass num-
ber of the monoisotopic combination, e.g., 70 u for Cl2.

5 Characteristic Ions

Remember that care should be taken when using tables of characteristic ions and
neutral losses, because the values listet represent only a minor fraction of the
fragmentations possible. There is a substantial risk of getting fixed on a certain
fragment or structure too early.
504 Appendix

Table A.3. Characteristic ion series and neutral losses

Ion Series m/z and [M–X]+ Ions Remarks

carbenium ions 15, 29, 43, 57, 71, 85, 99, 113, any alkyl group
127, 141, ...
acylium ions 29, 43, 57, 71, 85, 99, 113, 127, aliphatic aldehydes, ketones, car-
141, 155, ... boxylic acids and their derivatives
immonium ions 30, 44, 58, 72, 86, 100, 114, 128, aliphatic amines
142, 156, ...
oxonium ions 31, 45, 59, 73, 87, 101, 115, 129, aliphatic alcohols and ethers
143, 157, ...
sulfonium ions 47, 61, 75, 89, 103, 117, 131, aliphatic thiols and thioethers
145, 159, ...
from benzyl 39, 51, 65, 77, 91 phenylalkanes
from benzoyl 51, 77, 105 aromatic aldehydes, ketones, car-
boxylic acids and derivatives
[M–16]+, [M–30]+, [M–46]+• nitroarenes
45, 60, 73, carboxylic acids
[M–17]+, [M–45]+
59, 74, 87, methyl carboxylates
[M–31]+, [M–59]+
73, 88, 101, ethyl carboxylates
[M–45]+, [M–73]+
44 McL of aldehydes
58 McL of methyl ketones
60 McL of carboxylic acids
59 McL of carboxylic acid amides
74 McL of methyl carboxylates
88 McL of ethyl carboxylates
[M–20]+• fluorine compounds
35, [M–35]+, [M–36]+• chlorine compounds (plus Cl iso-
topic pattern)
79, [M–79]+, [M–80]+• bromine compounds (plus Br iso-
topic pattern)
127, [M–127]+, [M–128]+• iodine compounds
[M–15]+ loss of methyl
[M–17]+• loss of ammonia from amines,
[M–17]+ loss of OH• from (tert.) alcohols
[M–18]+• loss of water from alcohols
[M–27]+• loss of HCN from heterocycles or
HNC from aromatic amines
[M–28]+• loss of CO, C2H4 or N2
[M–44]+• loss of carbon dioxide
[M–91]+ loss of benzyl

6 Frequent Impurities
Table A.4. Recognition of frequent impurities
m/z
18, 28, 32, 40, 44
149, 167, 279
149, 177, 222
73, 147, 207, 281, 355, 429
27, 29, 41, 43, 55, 57, 69, 71, 83, 85,
97, 99, 109, 111, 113,
125, 127, ..., up to m/z 500
32, 64, 96, 128, 160, 192, 224, 256
51, 69, 119, 131, 169, 181, 219, 231,
243, 281, 317, 331, ...
6 Frequent Impurities 505
Source
residual air
phthalic acid esters (plasticizers)
diethyl phthalate (plasticizers)
silicon grease or GC column bleed
(Six isotopic pattern)
hydrocarbons from grease or from
suspensions in paraffin
sulfur (Sx isotopic pattern)
background from PFK