Identification of organic compounds

by spectroscopy

Mass Spectrometry
 Mass Spectrometry
Simplest form of mass spectrometer performs 4 essential functions: (under
vacuum 10-6 mm Hg)

It subjects vaporized molecules to bombardment by

a stream of high-energy electrons, converting these
molecules to ions
These ions are then accelerated in an electric field
The accelerated ions are then separated according to
their mass-to-charge ratio in a magnetic or electric
field
The ions that have a particular mass-to-charge ratio are
then detected by a device that counts the number of
ions striking it
 Mass Spectrometry
Atomic and molecular weight are expressed in
Atomic Mass Unit (amu).
(amu)

The amu is based on a relative scale in which

12
C is assigned exactly 12 amu.
amu Also called dalton

Each isotope has specific exact mass. MS is interested in exact mass up

to 3-4 figures after decimal point (high resolution HR).
HR

Chemical atomic weight is the average weight taking into account the
mass of each isotope and their natural abundance.
Components of a mass spectrometer
 MS : Ionization
1. Gas Phase:
1. Electron ionization (EI)
EI
2. Chemical ionization (CI)
CI
3. Field Ionization (FI)
FI
2. Desorption
1. Field Desorption (FD)
FD
2. Fast Atom Bombardment (FAB)
FAB
3. Secondary Ion Mass Spectrometry (SIMS)
SIMS
4. Laser Desorption (LD)
LD
5. Plasma Desorption (PD)
PD
6. Thermal Desorption
7. Thermospray ionization (TS)
TS
8. Electrospray (ES)
ES
 Mass analyzers: Magnetic sector
In Magnetic Field (H) an ion
of charge z and mass m
experiences centripal force
Hzv (where v is the velocity
of the ion). At the same time,
any particle moving on a
circle of radius r experiences
centrifugal force of mv2/r
When these two forces are
equal the ion travel on a circle
and
Hzv = mv2/r
m/z = Hr/v

We could measure v, the velocity of the ion to determine the mass

but this is very difficult experimentally
 Mass Spectrometer
If a molecule absorb an electron (creating a Negative Ion), It will
be absorbed by the repeller plate
The repeller plate (Positively charged) directs the ions through a
series of accelerating plates
Kinetic Energy : 1 mv = eV
2

2
In Magnetic Field (H) ions describe a curved Path (r -> curvature)
r = mv m = H2 r2
eH e 2v
Ions with reater m/e have larger curve
Instruments has fixed curve => only particules with correct m/e can reach
detector
Magnetic field is varied to detect all ions
 Components of MS: Mass Analyzers

Dispersion of the ions is based on mass-to-charge ratio

Mass
Analyzer There are several type of mass analyzers.

1. Magnetic sector
2. Electrostatic and Magnetic sector
3. Quadrupole MS filter
4. Ion trap analyzers
5. TOF Time-of-Flight
6. FT-MS
 Components of MS: Detector, Vacuum
Convert the beam of ions in an electrical signal that can
Detector be processed, stored, displayed and recorded in many
ways.

Electron Multiplier (most commonly used)

Other: Faraday cup

Photographic plates
Scintillation type

Vacuum MS require the high vacuum is maintained in all

System spectrometer components (except signal processing)
 Amplifying signal

Continuous Dynode electron multiplier

Provide high gain and nanosecond response time.

 Mass Spectrum
Ionization:
CH3OH + e- CH3OH+ + 2e-
m/z 32
Molecular ion
Fragmentation:
[CH3OH]+ [CH2OH] + + H
m/z 31

CH3+ + HO CHO+ + H2
m/z 15 m/z 29
B Base Peak 100%

Tabular presentation
Bar graph presentation
 B+
Benzamide: EI
M+

77 44

- NH2
C NH2 C6H5C=O + - CO C6H5+
O
m/z 105 m/z 77
105
3-methyl-6-i-PropylCyclohex-2-ene-1-one

MW = 152

Isotopic cluster M, M+1, M+2

 Natural Abundance of a few elements
Isotope Atomic weight Mass % Abundance
1
H 1.008 1.00783 99.99
2
H 2.01410 0.016

12
C 12.011 12.0000 (std) 98.89
13
C 13.00336 1.11

14
N 14.0067 14.0031 99.64
15
N 15.0001 0.36

16
O 15.9994 15.9949 99.76
17
O 16.9991 0.04
18
O 17.9992 0.20
 Natural Abundance of a few elements
Isotope Atomic weight Mass % Abundance

F
19
18.998 18.9984 100.0

28
Si 28.0855 27.9769 92.17
29
Si 28.9765 4.71
30
Si 29.9738 3.12

32
S 32.066 31.9721 99.64
33
S 32.9715 0.76
34
S 33.9679 4.20

35
Cl 35.4527 34.9689 75.77
37
Cl 36.9659 24.23
 Natural Abundance of a few elements
Isotope Atomic weight Mass % Abundance

P
31
30.9738 30.9738 100.0

79
Br 79.9094 78.9183 50.52
81
Br 80.9163 49.48

126
I 126.9045 126.9045 100.00

The Atomic weight: Average atomic weight of all isotopes with their
natural abundances

Atomic weight Br: [% 79Br x 78.9183] + [% 81Br x 80.9163]

[50.52 x 78.9183] + [49.48 x 80.9163] = 79.9094
Natural Abundance of a few elements
Molecular formula M+ (molecular ion) m/z
M mass of the most abundant isotope
e.g C7H7NO : 7 x 12C = 84
7 x 1H = 7
1 x 14N = 14
1 x 16O = 16
m/z 121
Isotope peaks: (% respect to M)
M+1 due to (13C) or 15N (17O) or 2H are negligeable)

%(M+1) = (1.1 * #C) + (.38 * #N) = 8.08 %

%(M+2) = (1.1 * #C)2/200 + (.2 * #O) = 0.5%

For C, H, N,O, F, P composition

 Molecular formula in general
Molecular ion:
Even Mass : can contain C, H, O , halogen, even # N

Odd Mass : can contain C, H, O , halogen, odd # N

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

even Mass : from Odd Mass M+

comes from single bond breaking
 Molecular formula: RULE of 13
Consider CH unit 13 amu
If we divide the mass by 13 we can establish easily possible formula:

Example: Molecular ion => 152

152 / 13 = # carbons = 11
Mass = 12 * 11 = 132 therefore H = 152 132 = 20

Basic formula C11 H20

If Oxygen is present : mass = 16 remove CH4
If Nitrogen is present : mass = 14 remove CH2
If one oxygen : C11 H20 CH4 + O = C10 H16 O
If second oxygen : C10 H16 O CH4 + O = C9 H12 O2
If third oxygen : C9 H12 O2 CH4 + O = C8 H8 O3
 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
16
O => CH4
14
N => CH2
19
F => CH7 1
H12 => C
Si
28
=> C2H4
P
31
=> C2H7
S
32
=> C2H8
Cl
35
=> C2H11
Br
79
=> C6H7
127
I => C10H7
 Nitrogen rule

Molecular ion => 26 Molecular ion => 27 odd!

26 / 13 = # carbons = 2 27 / 13 = # carbons = 2
Mass = 12 * 2 = 24 therefore H = 2 Basic formula C2 H3
Basic formula C2 H2 One Nitrogen C2 H3 - CH2 + N
H C C H H C N
 Nitrogen rule
OH NH2

Molecular ion => 100 Molecular ion => 99 odd!

100 / 13 = # carbons = 7 Basic formula C7 H16
Mass = 12 * 7 = 84 therefore H = 16
1 Nitrogen: C7 H16 CH2 + N
Basic formula C7 H16
C6 H14 N
1 Oxygen: C7 H16 - CH4 + O
C6 H12 O
Calculating M+1 and M+2
 Isotope peaks
Usually [M+2] peak is very small

Except for:

M M+1 M+2

Sulfur : 32
S : 100 S : 4.4
34

Silicon : 28
Si: 100 Si: 5.2
29
Si : 3.35
30

Chlorine : 35
Cl : 100 Cl : 32.5
37

Bromine : Br : 100
79 81
Br : 98
 Isotope peaks : CH3Br

[12CH379Br]+
[12CH381Br]+

M-H
[13CH379Br]+
[12CH279Br]+
[12CH281Br]+
[13CH381Br]+
 Bromine
79
Br 81Br

79
Br 81Br

2 intense peaks for the molecular ion, spaced by 2 daltons.

Br and 81Br
79
 Chlorine

35
Cl (P= .75)
37
Cl (P= .25)
Ratio 3:1

Probability : [M+] / [M + 2] = 0.75 / 0.25 = 3 / 1

100 : 33
 Calculation of isotope pattern: 2 Cl
C2H235Cl2
1 Cl C2H235Cl 37Cl
C2H237Cl 35Cl

C2H2 37Cl2

2 Cl
P (2 35Cl) = (0.75 )2 = 0.563

P (35Cl 37Cl) + P (37Cl 35Cl ) = (0.75 ) (0.25 ) + (0.25 ) (0.75 ) = 0.375

P (2 37Cl) = (0.25 )2 = 0.063

[M+] / [M + 2] / [M + 4] = 100 / 66 / 11
 Calculation of isotope pattern: ClBr
35
Cl => .75 Cl => .25
37

79
Br => 51% Br => 49%
81

[RClBr]+ can exist as 4 isotopic forms:

35
Cl 79Br M 0.75 x 0.51 = 38%

Cl 81Br
35
M+2 0.75 x 0.49 = 37%
50%
37
Cl 79Br M+2 0.25 x 0.51 = 13%

37
Cl 81Br M+4 0.25 x 0.49 = 12%

At very high resolution, the 2 (M + 2)

2 peaks can be distinguished
(separated by 0.001 Dalton)
Dalton
Chlorine and
Bromine

The Molecular ion

M+ is always the
lowest mass peak in
the ion cluster
(regardless of its
relative intensity)
 Isotopic abundances for Carbon containing compounds

M+ => p(M) = p(n 12C) = (0.989)n

The probability of finding 1 13C among n carbons is:

[M+1]+ => p(M+1) = p(n -1) 12C + 1 13C = n p[n-1] 12C x p(13C)

= n(0.989)n-1 (0.011)

Relative ratio: [M+1]+ / [M+ ] = n(0.989)n-1 (0.011) / (0.989)n

= n (0.011) / (0.989)
= n (0.0111)

In percentage: n x 1.1 %
 Isotopic abundances for Carbon containing compounds
When comparing calculated abundances with observed intensities:
intensities
We see that the ratio is not identical:
identical due to experimental error
The relative abundance of the larger peaks are reproducible to 10%
For smaller peaks, relative intensity is larger

Generally speaking, The size of the [M+1]+ ion can be used to figure out
the number of carbons in a molecule

For example, if molecular ion is observed at m/z 118

and the ion at m/z 119 has an intensity of about 9%

There are probably 8 carbons (1.1% x 8 = 8.8% )

 Isotopic abundances for Carbon containing compounds
Due to the relatively large error on peak intensity ( 10%)
10% determination
of the number of carbons is sometime ambiguous
For example: [M+1]+ => intensity 22.5 2.3%
Range covers 20.2 to 24.8 => 20 2 carbons
 Isotopic abundances for other common nuclei

For 15N: [M+1]+ / [M]+ => n x 0.36%

For 33S: [M+1]+ / [M]+ => n x 0.80%

For 18O: [M+2]+ / [M]+ => n x 0.20%

For 34S: [M+2]+ / [M]+ => n x 4.42%

Calculating Peak Intensities from Isotopic abundances
Isotopic abundances for Silicon

Often observed is TMS compounds

M+2 larger than usual

Often observed either from GC column

Or septum
 Isotopic abundances for Sulfur

SO+

M+2
M+2

For 18O: [M+2]+ / [M]+ => n x 0.20%

For 34S: [M+2]+ / [M]+ => n x 4.42%

[M+2]+ = 4.42 + (2 x 0.20) = 4.82%

 isotope pattern: 2 Cl (example)

When there are many carbons, isotopic pattern for 13C adds up to
chlorine pattern
 Steps in the Identification of Unknown
Identify Molecular ion M.+
Determine Molecular Formula (odd / even mass)
Analyze heteroatom (M+1 and M+2 )
S, Si, Cl, Br, .
Use rule of 13 to determine # Carbons (M+1 and M+2 )
Compare with 13C-NMR (# carbons)
carbons with APT experiment (J-
MOD) ( # protons)
protons
Compare with proton NMR ( # protons)
protons
Identify base peak (note if even / odd)
odd
One or two bond fragmentation
Test your conclusions: in lab make derivatives (TMS or Na or
K complexes mass shift)
 Solving problems in MS
Try to identify the Molecular Ion or decide if it is present (most
critical step in solving a structure)
Check if [M+1]+ ion is too large to accommodate reasonable number of
carbons. (the [M+1]+ ion might be the very small M+ instead!)
Determine the first loss from proposed molecular ion. Some loss are
impossible (e.g 12, 14, 23 daltons)
Does the spectrum appear dirty? (lots of small peaks even at high mass)
If GC of the comopund Is available, compare retention time
Is the molecular weight even or odd?
An odd mass can be associated with an odd number of Nitrogen
An even mass means no Nitrogen or an even number of Nitrogen
This Rule is applicable only to Molecular ion and to odd-electron ions
Examine ion cluster for isotopic natural abundance (look for
special heteroatom pattern). Try to calculate number of carbons
 Solving problems in MS
From the overall appearance: is it a fragile compound?
Is it likely to be aromatic or aliphatic?
Look in the low mass ions. Do you see any clues of the family of
compounds that you might be dealing with?
Make a list of suggested losses from the molecular ion and try to
make a pattellsrn from them.
Look for intense odd-electron ions in the spectrum: this is almost
impossible in compounds containing Nitrogen! These provides
clues for rearrangements (retro Diels Alder, McLafferty)
Speculate on the structure using all that information

Index of Hydrogen deficiency

CxHyNzOn Index = x y + z +1
 Neutral losses and Ion series
M-1 H M-30 NO (Nitro compounds),
H2 CO (anisoles)
M-15 CH3
M-16 O (rare) , NH2 M-31 CH3O
M-17 OH , NH3 (rare) M-32 CH3OH
M-18 H2O
M-35 Cl
M-19 F
M-36 HCl
M-20 HF (very rare)
M-42 CH2=C=O, CH2=CH-CH3
M-26 HCCH , CN
M-43 CH3CO , C3H7
M-27 HCN
M-44 CO2
M-28 H2C=CH2 , CO
M-29 CH3CH2 , HCO M-45 CH3CH2O , CO2H
 Neutral losses and Ion series
Figuring out which peak is molecular ion can be supported by
identifying what fragment is lost.

There can be sometimes 2 consecutive loss:

In steroid, M-33 is often observed: comes from the loss of Me and H2O

The ions loss are only useful from molecular ion

There is no fragment in organic compounds between M-1 and M-15

Loss of M-14 is never observed!

Other gaps in mass loss are: between 21-25,

21-25 33-34,
33-34 37-41
Ions in these areas should be viewed suspiciously:
suspiciously either compound is
not pure or postulated molecular ion is wrong
 Neutral losses and Ion series
Among the losses: most common are
Loss of H, CH3 , H2O (from some oxygenated compounds),
HCCH (from aromatic compounds),
HCN (from aromatic compounds containing Nitrogen),
CO and CH2=CH2 (both at 28! Difficult to tell which one is lost)
Ethyl radical (29)
Methoxy radical (31)
Cl and HCl (35, 36)
Acetyl (43) accompanied by m/z 43 prominent and propyl (43) radical
Resolution
Exact Masses
of isotopes
 Mass Defects
By definition the atomic weight of 12C is 12.0000 Daltons
All other elements are determined relative to 12C
Their difference to nearest integral is called Mass Defect

Light element has small

positive mass defect

Vast majority of elements

have substantial negative
mass defect
 Mass Defects
The Mass Defect of a C23H35O2Si is shown
here on a low resolution MS (+/- 0.1)

Mass defect for H : 1.008-1.000 = .008

Mass defect for O : 15.995-16.000 = -.005
Mass defect for Si : 27.977 -28.000 = -.003

(35 x 0.008) + (2 x -.005) + (-.003) = .27

Mass defect for organic compounds is

mainly due to Hydrogen due to their large
number
 Mass Defects
Mass defect brings the maximum of the
C23H35O2Si peak not at 371 but at 371.25
If the Mass spectrometer measure the
mass with a resolution of 1,
1 the sensitivity
is reduced.

Greatest application of Mass Defect is

surely very high resolution, which provide
mass with .001 to .0001 accuracy
 High resolution:
Exact Mass can provide Molecular Formula
With sufficient accuracy, unique molecular formula can be determine

e.g. Distinguish CO,

CO N2, CH2N and C2H4 (all having m/z 28)
28

CO 12
C 12.0000 N2 14
N 14.0031
16
O 15.9949 14
N 14.0031
27.9949 28.0062

CH2N 12
C 12.0000 C2H4 12
C x2 24.0000
1
H x2 2.0156 1
H x4 4.0312
14
N 14.0031 28.0312
28.0187
 Exact Mass can provide Molecular Formula
Consider the following 2 formulas which have m/z 287:
287

C15H10NO3Cl C14H8N2O3Cl

Mass Defect of C15H10NO3Cl:

(10 x .0078) + (.0031) + (3 x -.0051 ) + (-.0311 ) = .0347

Mass Defect of C14H8N2O3Cl:

(8 x .0078) + (2 x .0031) + (3 x -.0051 ) + (-.0311 ) = .0202

With sufficiently high resolution MS, it is possible to propose a unique

empirical formula for an ion.
 Nitrogen rule
M+ even even # of N 0, 2, 4,
M+ odd odd # of N 1, 3, 5,

Index of Hydrogen deficiency

Index = C H/2 X/2 + N/2 + 1

e.g. C7H7NO Index = 7 - 3.5 + 1 = 5

Hydrogen deficiency can be unsaturation (multiple bonds)

or cyclic structure

R-CN
I=2
I=1 (1 DB + cycle) I=4 (3 DB + cycle)
 Index of hydrogen deficiency : General

Index = IV (I/2) + (III/2) +1

IV any tetravalent atom (e.g. C, Si..)

I any monovalent atom (e.g. H, D,Cl, Br, F )

III any trivalent atom (e.g. N, P, )

II any divalent atom (e.g. S, O,).
These count for 0 in the formula

Higher valences uses valence shells lewis octet rule

CH3
+ + O
CH3-S-CH3 CH3-N CH3-P+-CH3 phosphine
O-
O- O-
I=0 I=1 I=0
Fragmentation in different isomers

Molecular ion almost absent

 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
Alcohols,
M.+ is often absent in:
M is often absent in: { Nitriles, Nitrates, Nitro, Nitriles
 Other Ionization Techniques
Under EI (Electron Impact),
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 gaz is ionized producing Primary ions that react with excess gaz
to produce secondary ions

CH4.+ + CH4 CH5+ + CH3.

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
 Chemical Ionization techniques
In Electron Impact (EI) and chemical ionization,
vaporization of the Sample is a prerequisite.
prerequisite

Therefore: the study of non-volatile or thermally fragile compound is not

possible with these techniques.

Several methods have been developed to go around these limitation

(methods that enable ions to be obtained from liquid/solid)

1- Field Desorption:
Desorption ions are desorbed by strong electric field
In this and other techniques,, the aim is to transfer energy to the Sample,
causing transfer of molecules/ions to gas phase
2- SIMS : other source of energy is a beam of ions (Secondary Ion
Mass Spectroscopy): Typically Argon (FAB)
FAB

Field Desorption methods give a high concentration of Molecular ion

=> Particularly useful for identification of unknown
 Fast Atom Bombardment (FAB)
The sample is dissolved in a liquid matrix such as glycerol,
glycerol thioglycerol,
thioglycerol
m-nitrobenzyl alcohol,
alcohol or diethanolamine and a small amount (about 1
microliter) is placed on a target.
The target is bombarded with a fast atom beam (for example, 6 keV
xenon atoms)
atoms that desorb molecular-like ions and fragments from the
analyte.
e- Xe+Xe
Xe

Xe+ Is accelerated to ~6-10 keV, and pass through Xe

Xe + Xe+ Xe (Xenon with Kinetic energy) FAB

Cluster ions from the liquid matrix are also desorbed and produce a
chemical background that varies with the matrix used.
used
 FAB: Benefits

Sample introduction can be through direct insertion

probe or LC/MS (continuous-flow FAB).

Benefits
rapid, simple
relatively tolerant of variations in sampling
good for a large variety of compounds
Useful fragentation pattern
strong ion currents -- good for high-resolution measurements
 FAB: Limitations
Limitations
high chemical background defines detection limits
may be difficult to distinguish low-molecular-weight compounds
from chemical background
analyte must be soluble in the liquid matrix
no good for multiply charged compounds with more than 2 charges
requires a high concentration of the organic liquid matrix (typically
80 to 95% glycerol) which limits sensitivity
Mass range
Moderate Typically ~300 Da to about 6000 Da.
Da
Comparing
different
techniques
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

Quadrupole Mass Spectrometer

Quadrupole Mass Filter: Mass Scanning by varying RF & DC Frequencies
Quadrupole Ion Storage (Ion Trap)
- Compact
-Inexpensive
-Very Sensitive
-GC/MS
Classification according to method of separating charged particule
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

-used for large molecule and resolution of mixture

 Time-of-Flight analyzer (TOF)
In TOF instruments, positive ions are produced periodically using
brief pulses of electrons,
electrons
secondary ions or
laser generated photons

These pulses have typically a frequency of 10-50 kHz and lifetime

0.25s

The ions produced are then accelerated by electric field pulse (103-104 V)
that has the same frequency as ionization pulse but lags behind.
behind

The accelerated ions then pass into a field-free drift tube (about 1 m
long)
 Time-of-Flight analyzer (TOF)

MALDI ionization, Time-of-flight Mass Spectrometer

Tandem-MS
 Comparing Mass Spectrum of a compound in
different type of mass spectrometers
Magnetic sector Quadrupole

Time of Flight

105
MW = 164
 Organometallic compounds in MS
It is often possible to determine molecular weight of a compound by MS
For example: Manganese carbonyl => m/z 390
As Mn => 55 and C=O => 28 Mn2(CO)
CO 10
PEt3
Cl Cl
Another example: Iridium complex Cl Ir P
Cl
OC
NMR and IR can give a lot of information but without PEt3

MS it is very difficult to show the presence of Cl

With MS, It is easy to show that 4 Chlorine are present
Molecular ion is usually present with Laser desorption. However, ions produced
That way comes from condensed phase (solid/liquid) and structure in these phase
Might be very different from the one in gaz phase.
With FAB most intense cation peak is the protonation ion (M+1) peak.
Anion (M-1) can also be formed.
 Isotope Abundance patterns for some
atoms and group of atoms

Can be diagnostic
for some isotopes
 Calculation of isotope pattern
Abundances can be calculated by multiplying the abundances of the
Constituent isotopes
e.g. 185Re => 37% Re => 63%
187

Br => 51%
79 81
Br => 49%

[ReBr]+ can exist as 4 isotopic forms:

185
Re79Br 264 m/z 0.37 x 0.51 = 19%

185
Re81Br 266 m/z 0.37 x 0.49 = 18.1%
50.2%
Re79Br
187
266 m/z 0.63 x 0.51 = 32.1%

Re81Br
187
268 m/z 0.63 x 0.49 = 30.9%
 Metastable ions

Some ions have so short lifetimes that they dissociate while moving through
the spectrometer.

An ion of mass m1 is accelerated after initial ionization

But a different ion m2 (daughter ion)
ion passes the magnetic analyzer
The resulting peak is neither m1 or m2 but appear at m* (metastable)
m* = (m2)
m2 2/m1

These metastable ions are formed during 10 -5 s

(time spent between electrostatic and magnetic
analyzer) are quite broad but provide direct
information about ion reactions
Platinum
 Tungsten

Index MS-fragmentation