6.

Mass Spectrometry
Pendahuluan

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Contoh Spektrum MS Benzamida dan
Pemenggalan

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 12.1 Mass Spectrometry of Small
Molecules:Magnetic-Sector Instruments
Bonds in cation radicals
begin to break (fragment)

Sample
vaporized and
subjected to
bombardment
by electrons
that remove an
electron
creating a Mass to charge (m/z)
cation radical ratio is measured
Molecular ion (M+)
shows molecular weight

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Spektra Massa

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Penentuan Rumus Molekul

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Dari tabel
Rumus Molekul M+1 M+2

C7H10N4

C8H8NO2

C8H10N2O

C8H12N3

C9H10O2 9,96 0,84

C9H12NO

C9H14N2

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Tugas 1

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Tugas 2

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 The Mass Spectrum
 Plot mass of ions (m/z) (x-axis) versus the intensity of the signal
(roughly corresponding to the number of ions) (y-axis)
 Tallest peak is base peak (100%)
 Other peaks listed as the % of that peak
 Peak that corresponds to the unfragmented radical cation is
parent peak or molecular ion (M+)

H H H
Propane H C C C H
MW = M+ = 44 H H H

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 12.2 Interpreting Mass Spectra
 Molecular weight from the mass of the molecular ion
 Double-focusing instruments provide high-resolution
“exact mass”
 0.0001 atomic mass units – distinguishing specific
atoms
 Example MW “72” is ambiguous: C5H12 and C4H8O but:
 C H 72.0939 amu exact mass C H O 72.0575 amu
5 12 4 8
exact mass
 Result from fractional mass differences of atoms 16O =
15.99491, 12C = 12.0000, 1H = 1.00783
 Instruments include computation of formulas for each
peak
 If parent ion not present due to electron bombardment causing
breakdown, “softer” methods such as chemical ionization are used

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 M+ peak Example:
 Possible formulas can be determined from the mass. (M+)

Predict possible molecular formulas containing C, H, and

maybe O if :
M+ = 86 M+ = 156

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 M+ peak Example:
 Possible formulas can be predicted from the mass. (M+)

Predict possible molecular formulas containing C, H, and

maybe O if :
M+ = 86 M+ = 156
C6H14 C11H24 C10H4O2
C5H10O C12H12 C9H16O2
C4H6O2 C11H8O C8H12O3
C3H2O3 C10H20O C7H8O4
C6H4O5

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 M+ peak :
 Peaks above the molecular weight appear as a result
of naturally occurring heavier isotopes in the sample
 (M+1) from 1.1% 13C in nature
 (M and M+2) in 75.8%/24.2% ratio = 35Cl and 37Cl
 (M and M+2) in 50.7%/49.3% ratio = 79Br and 81Br

H H H
Propane
H C C C H
MW = M+ = 44
H H H

M+1 = 45
From 1.1% 13C

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 Click on image to enlarge

M+ peak: Halides
M+ and M+2 in
75.8%:24.2% CH3Cl
(~ 3:1) ratio
= 35Cl and 37Cl

M+ and M+2 in Br
50.7%:49.3%
(~ 1:1) ratio
= 79Br and 81Br

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 Mass-Spec Fragmentation Patterns
 Molecular ions break into characteristic fragments that can be
identifed
 Serves as a “fingerprint” for comparison with known materials in
analysis (used in forensics)
 Positive charge goes to fragments that best can stabilize it

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Mass-Spec Fragmentation Patterns

M -15 = 57

CH3=15

MW=72;
M+ peak not seen
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 Mass Spec: Fragmentation of Hexane
Hexane (m/z = 86 for parent) has peaks at
m/z = 71, 57, 43, 29

71=Loss of CH3 (15)

57=Loss of CH3CH2 (29)

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 CH3

Learning Check:
MW=98 MW=98
Identify the following MS as that of methylcyclohexane or ethylcyclopentane.

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 CH3

Solution:
MW=98 MW=98
Identify the following MS as that of methylcyclohexane or ethylcyclopentane.

98-69=29 loss of (CH3CH2)

98-83=15 (loss of CH3)

M+ =98

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 CH3

Learning Check:
MW=98 MW=98
Identify the following MS as that of methylcyclohexane or ethylcyclopentane.

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 CH3

Solution:
MW=98 MW=98
Identify the following MS as that of methylcyclohexane or ethylcyclopentane.

98-83=15 (loss of CH3)

M+ =98

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12.3 Mass Spec: Common Functional Groups
Alcohols:
 Alcohols undergo -cleavage (at bond next to the C-OH)
as well as loss of H-OH (18) to give C=C

Loss of 18

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Mass Spec: Alcohols
CH3
CH
H3C

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 Mass Spec: Amines
 Nitrogen Rule: Amines with odd # of N’s have Odd M+
 Amines undergo -cleavage, generating radicals

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 Mass Spec: Carbonyl Compounds
 A C-H that is three atoms away leads to an internal transfer of a
proton to the C=O, called the McLafferty rearrangement

Loss of 28

• Carbonyl compounds can also undergo  cleavage

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12.4 Mass Spectrometry in Biological
Chemistry: Time-of-Flight (TOF) Instruments
 Most biochemical analyses by MS use:
 electrospray ionization (ESI)
 Matrix-assisted laser desorption ionization (MALDI)
• Linked to a time-of-flight mass analyzer

MALDI-TOF MS of chicken
eg-white lysozyme

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12.5 Spectroscopy and the
Electromagnetic Spectrum
 Radiant energy is proportional to its frequency (cycles/s = Hz)
as a wave (Amplitude is its height)
 Different types are classified by frequency or wavelength ranges

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 Electromagnetic Spectrum

High frequency (u) Low frequency (u)

Short wavelength (l) Long wavelength (l)
= High energy = Low energy

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 Learning Check:
42. Propose a structure for the following unknown hydrocarbon:

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 Solution:
42. Propose a structure for the following unknown hydrocarbon:
70-55 =15
C5H10
loss of CH3

M=70

=C-H -C-H
-C=C-

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