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Mass Spectrometer
1
Spektrometer massa
amplifier
Komponen dasar MS
1. Sistem injeksi sampel
2. Sumber pengionan
3. Analisator/pemisah massa
4. Sistem pompa vakum
5. Detektor
6. Penguat sinyal
7. Pencetak spektra
2
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+)
3
3-methyl-6-i-PropylCyclohex-2-ene-1-one
MW = 152
4
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:
C5H12 72.0939 amu exact mass C4H8O 72.0575 amu
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
5
Molecular formula in
Molecular ion:
general
Fragmentation ions:
Even Mass : From even mass M+
comes from rearrangement or 2 bond breaking
Odd Mass : From even mass M+
comes from single bond breaking
6
Molecular formula: RULE of 13
After establishing the basic formula with only Carbon/hydrogen,
Other element can be introduced by substracting the proper hydrocarbon
value
14N => CH2 16O => CH4
19F => CH7 1 H12 => C
28Si => C2H4 127I => C10H7
31P => C2H7 79Br => C6H7
32S 35Cl => C2H11
=> C2H8
Nitrogen
rule
7
Nitrogen rule NH2
OH
8
Isotope Abundance patterns for some
atoms
Can be diagnostic
for some isotopes
Isotope
peaks
9
Interpreting Mass-Spectral
Fragmentation Patterns
The way molecular ions break down can
produce characteristic fragments that help in
identification
Serves as a fingerprint for comparison with
known materials in analysis (used in forensics)
Positive charge goes to fragments that best can
stabilize it
Fragmentation process
There are 3 type of fragmentations:
1) Cleavage of s bond
+.
---- C C ---- ---- C + +
. C ----
At heteroatom
+.
---- C Z ---- ---- C + +
. Z ----
a to heteroatom
+.
---- C - C Z ---- C=Z + + ---- C .
+.
---- C - C Z ---- Z+. + ---- C = C
10
Fragmentation process
2) Cleavage of 2 s bond (rearrangements)
+.
---- HC C Z ---- ---- C=C + + HZ
McLafferty
H H
Z +. Z +. CH2
CH2
Z R Z R
Fragmentation process
Fragmentation rules in MS
11
2. Intensity of M.+ decrease with
Increasing M.W. (fatty acid is an
exception)
3. Cleavage is favored at branching
reflecting the Increased stability of
the ion
Stability order: CH3+ < R-CH2+ < R2-CH+
< R3-C+
R
R CH
R
12
Branched alkanes
H3C H3C H3C
CH3
H3C
CH3
H3C
MW=170
13
Illustration of first 3 rules
(Branched alkane with Smaller MW)
43 Molecular ion smaller than
linear alkane
Cleavage at branching is
favored
Hexane
14
Mass Spectral Fragmentation of
Hexane
Hexane (m/z = 86 for parent) has peaks at m/z =
71, 57, 43, 29
Rule 3 Alkanes
15
Fragmentation in different isomers
16
Fragmentation rules in MS
4. Aromatic Rings, Double bond,
Cyclic structures stabilize M.+
5. Double bond favor Allylic Cleavage
Resonance Stabilized Cation
-R
.
+ +
H2C CH CH2 R H2C CH CH2
H2C CH CH+2
17
Cycloalkane
ring has
stable M.+
Fragmentation rules in MS
6. a) Saturated Rings lose a Alkyl Chain
(case of branching)
R
+. +
-R.
18
Retro Diels-alder
+. +.
Fragmentation rules in MS
7. Aromatic Compounds Cleave in b
Resonance Stabilized Tropylium
+
CH2 CH2
R
C
-R. CH
+
+
CH
Tropylium ion +
m/z 91
19
Tropylium ion
+
Fragmentation rules in MS
8. C-C Next to Heteroatom cleave leaving the
charge on the Heteroatom
+
x - [RCH2] H2C Y R
R CH2 CH2 Y R
+
H2C Y R
R2 R1 R1 R1
- [R2 ] C C
+
C
larger
+ O
O O
x
20
Fragmentation rules in MS
x
x
- CH2=CH2
x
O CH2 O CH2
C
C CH2 C CH2 Y CH2
Y CH2 Y CH2
Ion Stabilized
Y H, R, OH, NR2
by resonance
Alkenes
Most intense peaks are often:
m/z 41, 55, 83
-Et
CH2 + CH CH Et +CH
2 CH CH CH2 CH CH +
-29
Me Et Me Et Me Et
M+ = 112 m/z = 83
21
Alkenes
Aromatic
compound
22
Mass Spectral Cleavage
Reactions of Alcohols
Alcohols undergo a-cleavage (at the bond next
to the C-OH) as well as loss of H-OH to give
C=C
Hydroxy compounds
R1
R1 R1 +
- R3
x
+ C O H
R2 C O H C O H
R2 R2
R3 If R1=H m/z 45, 59, 73
H H CHR
+ CHR
CHR OH
x
CHR OH (H2O)
+ +
CHR CHR CHR CHR
CHR CHR
CHR CHR CHR CHR
CHR CHR M (H2O)
H
CHR
x
OH - H2O CHR
- CHR=CHR
CHR CHR CHR
CHR M (H2O) (C1=C2) Alkene
23
Alcohols
24
Phenol
+
O x
O
R -CO
1) - R C5H5
m/z 93 m/z 65
Cleavage in b of aromatic ring
O O
2) - CH2=CH2 x
H
H
H
Rearrangement m/z 94
O
H
x
25
B
Aliphatic Ether
Cleavage of C-C next ot Oxygen
Loss of biggest fragment
+
CH3 CH2 OCH2 CH2 CH2 CH3 CH3 CH2 O+ =CH2
m/z 45
Ether
Rearrangement
B
m/z 73
26
Fragmentation of Ketones and
Aldehydes
A C-H that is three atoms away leads to an
internal transfer of a proton to the C=O, called
the McLafferty rearrangement
Carbonyl compounds can also undergo a
cleavage
27
Ionization
Techniques
Electron Impact (EI)
Under these conditions, very energetic Ions are produced
=> Fragmentation M.+ is often weak
e.g. ROH often loose H2O
.
Intensity of M + Depends on the stability of the Ion
Most Stable
Ketones
Aromatic
Amines
Conjugated Alkenes
Ester
Cyclic compounds
Ether
Sulfides
Acid ~ Amides ~ Aldehydes
Short Linear Alkanes
Mercaptans
Least Stable
M.+ is often absent in: { Alcohols,
Nitriles, Nitrates, Nitro
28
Other Ionization Techniques
Under EI (Electron Impact), the molecular ion may be weak or absent
In such case, the best solution is to run CI Chemical Ionization
Which result in intense M+1 ion with little fragmentation
CI Chemical Ionization
Vaporized Sample is introduced with excess gas (usually methane)
The gas is ionized producing Primary ions that react with excess gas
to produce secondary ions
CH .+ + CH CH + + CH .
4 4 5 3
CH3+ + CH4 C2H5+ + H2
Secondary ions react with sample M:
CH5+ + M [M+H]+ + CH4
C2H5+ + M [M+H]+ + C2H4
Less energy than CI => less fragment
Comparing
different
techniques
29
Classification according to method of separating charged
particule
1. Magnetic Field Deflection
1. Magnetic Field only: Mass 12-500 in seconds
2. Double Focussing: High resolution to 4 decimals
r = 60,000
2. Quadrupole Mass Spectrometer
1. Quadrupole Mass Filter: Mass Scanning by varying RF & DC
Frequencies
2. Quadrupole Ion Storage (Ion Trap)
- Compact
-Inexpensive
-Very Sensitive
-GC/MS
3. Time of Flight
- Need Fast Electronic (10-7 s)
- Used With Sophisticated Ionization Methods
(FAB, Laser Desorption .)
4. FT-ICR (Fourier Transform Ion Cyclotron
Resonance)
- Very High Precision most expensive
5. MS/MS (Tandem Mass Spectro.)
-Specific Ions are Separated in First MS
- Pass one at a time in a collision chamber
- Second MS produce Daughter Ions
30
Comparing Mass Spectrum of a compound in different
type of mass spectrometers
Magnetic sector Quadrupole
Time of Flight
105
MW = 164
Hard method
Relatively GC or to
Electron Impact versatile
small liquid/solid 1,000
(EI) provides
volatile probe Daltons
structure info
Relatively GC or to Soft method
Chemical
small liquid/solid 1,000 molecular ion
Ionization (CI)
volatile probe Daltons peak [M+H]+
Liquid Soft method
Peptides to
Electrospray Chromatograp ions often
Proteins 200,000
(ESI) hy multiply
nonvolatile Daltons
or syringe charged
Carbohydrates Soft method
Fast Atom Sample mixed to
Organometallics but harder
Bombardment in viscous 6,000
Peptides than ESI or
(FAB) matrix Daltons
nonvolatile MALDI
Matrix Assisted
Peptides Sample mixed to Soft method
Laser
Proteins in solid 500,000 very high
Desorption
Nucleotides matrix Daltons mass
(MALDI)
31
Linked Systems:
32
Mass Spectroscopy C5H12O
MW = 88.15
33
Mass Spectroscopy C9H10 O
MW = 134.18
34
Tentukan struktur senyawa dari data berikut :
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