Mass Spectrometry

The concept of mass spectrometry

The mass spectrometer analyses the masses of cations.
A compound is ionised, the ions are separated on the
basis of their mass/charge ratio, and the number of ions
representing each mass/charge unit (m/z) is recorded
as a spectrum
It is routine to couple a mass spectrometer to some form of
chromatographic instrument, such as a gas chromatograph
(GC-MS) or a liquid chromatograph (LC-MS).

 When the electron beam ionizes the molecule, the

species that is formed is called a radical cation, and
symbolized as M+.
The radical cation M+ is called the molecular ion or
parent ion.
The mass of M+ represents the molecular weight of M.
Because M is unstable, it decomposes to form
fragments of radicals and cations that have a lower
molecular weight than M+.

 Molecular Ion
Molecular ion (M): A radical cation formed by removal of
a single electron from a parent molecule in a mass
spectrometer = MW.
For our purposes, it does not matter which electron is
lost; radical cation character is delocalized throughout
the molecule; therefore, we write the molecular formula
of the parent molecule in brackets with:
A plus sign to show that it is a cation.

M+

A dot to show that it has an odd number of electrons.

Partial MS of octane (C8H18, M = 114)

14 (CH2)
29 (CH3CH2)

57

85
71

M+
114

The parent peak or molecular ion

-

C8H18

e
70 eV

[C8H18] + 2 e
+
(M )

The largest or most abundant peak is called the base peak

and is assigned an intensity of 100%, other peaks are
then fractions of that.
The relative abundance of all other ions is reported
as a % of abundance of the base peak.
14 (CH2)
29 (CH3CH2)

57

85
71

M+
114

114(M+,40), 85(80), 71(60), 57(100) etc.

Masses are usually rounded off to whole numbers

assuming:
H = 1, C = 12, N = 14, O = 16, F = 19 etc.

[C8H18]

fragmentation

-CH
CH
(29)
3
2
(M , 114)
+

-CH3CH2CH2 (29+14)
Molecular ion (parent peak)

[C6H13]

Daughter
ions

(85)
[C5H11]
(71)
7

Whats in a Mass Spectrum?

Mass spectrum: A plot of the relative abundance of ions versus

their mass-to-charge ratio (m/z).

Molecule

Intensity (% of Base Peak)

e-

High Energy
Electron

CH2OH+

M - (H2O and CH2=CH2)

1-Pentanol - MW 88

M - (H2O and CH3)

CH3(CH2)3 CH2OH

M - H2O

Molecular Ion Peak

M+ - 1

20

30

40

2e-

Molecular
Ion
(Radical Cation)

Base Peak
100
90
80
70
60
50
40
30
20
10
0

+
M

50

60

70

m/z

80

90

WAYS TO PRODUCE IONS

Electron impact (EI) - vapor of sample is bombarded with
.+
electrons:
M+e
2e + M
fragments
Chemical ionization (CI) - sample M collides with reagent
ions present in excess
e.g.

CH4.+

CH4 + e
M + CH5

CH5+
+

CH4 + MH

Fast Atom/Ion Bombardment (FAB)

Laser Desorption & Matrix-Assisted Laser Desorption
(MALDI) - hit the sample with a laser beam
Electrospray Ionization (ESI) - a stream of solution
6
passes through a strong electric field (10 V/m)

Ionization Methods
1. Electron Ionization (EI)
most common ionization technique, limited to relatively
low MW compounds (<600 amu)
2. Chemical Ionization (CI)
ionization with very little fragmentation, still for low
MW compounds (<800 amu)
3. Desorption Ionization (DI)
for higher MW or very labile compounds
4. Spray ionization (SI)
for LC-MS, biomolecules, etc.

note: amu, atomic mass units

1 amu = 1 dalton (Da)

Electron Ionization (EI)

vaporized sample is bombarded with high energy

electrons (typically 70 eV)
hard ionization method leads to significant
fragmentation
ionization is efficient but non-selective

Electron Ionization
Advantages
inexpensive, versatile and reproducible
fragmentation gives structural information
large databases if EI spectra exist and are
searchable
Disadvantages
fragmentation at expense of molecular ion
sample must be relatively volatile

Chemical Ionization (CI)

Vaporized sample reacts with pre-ionized reagent gas via
proton transfer, charge exchange, electron capture,
adduct formation, etc.
Common CI reagents:
methane, ammonia, isobutane, hydrogen, methanol
soft ionization gives little fragmentation
selective ionization-only exothermic or thermoneutral
ion-molecule reactions will occur
choice of reagent allows tuning of ionization

The Index of Hydrogen Deficiency (or IHD) is also known as

"units of unsaturation".
The index of hydrogen deficiency is a count of how many molecules
of H2 need to be added to a structure in order to obtain the
corresponding saturated, acyclic species.
Hence, the IHD is the sum of the number of rings, the number of
double bonds and twice the number of triple bonds.

CnHmXxNyOz
Index = (n) - (m/2) - (x/2) + (y/2) +1

How To Determine Molecular Formulas and

Molecular Weights Using Mass Spectrometry
Isotopic Peaks & the Molecular Ion

15

The presence of isotopes of carbon, hydrogen,+and

nitrogen in a compound gives rise to a small M + 1
peak.

The presence of oxygen, sulfur, chlorine, or bromine

+
in a compound gives rise to an M + 2 peak

M + 1 Elements:

C, H, N

M + 2 Elements:

O, S, Br, Cl
16

Is M odd or even?
According to the nitrogen rule, if it is even, then the
compound must contain an even number of nitrogen
atoms (zero is an even number)

For our unknown, M is even. The compound must

have an even number of nitrogen atoms
+
M +2

The relative abundance of the

peak indicates the
presence (or absence) of S (4.4%), Cl (33%), or Br (98%)
+
For our unknown M +2 = 0.3%; thus, we can assume
that S, Cl, and Br are absent

The molecular formula can now be established by

determining the number of hydrogen atoms and adding the
appropriate number of oxygen atoms, if necessary
17

Since M is m/z 72
molecular weight = 72
+

As determined using the relative abundance of M

+1 peak, number of carbons present is 4

Using the nitrogen rule, this unknown must have

an even number of N. Since M.W. = 72, and there
are 4 C present, (12 x 4 = 48), adding 2 N will be
greater than the M.W. of the unknown. Thus, this
unknown contains zero N

18

For a molecule composed of C and H only

H = 72 (4 x 12) = 24
but C4H24 is impossible

For a molecule composed of C, H and O

H = 72 (4 x 12) 16 = 8
and thus our unknown has the molecular formula
C4H8O

19

1.BM vs formula
2.Index ??
3.Fragment ions and fragment lost

C8H8O2

23

Terima kasih

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