MS Chapter

Spectroscopy
Beauchamp
Basics of Mass Spectroscopy

The roots of mass spectroscopy (MS) trace back to the early part of the 20th century. In 1911
J.J. Thomson used a primitive form of MS to prove the existence of isotopes with neon-20 and neon22. Current, easy-to-use, table-top instruments of today are a very recent luxury. In less than a day,
you could be running samples on a mass spectrometer. However, it would take you longer to learn
the many intricacies of MS, something we cannot pursue in a book such as this. We will mainly look
at electron impact mass spectrometry (EI) and briefly mention chemical ionization (CI) as they
pertain to determining an organic structure.
The technique of MS only requires very small amounts of sample (g-ng) for high quality data.
For that reason, it is the preferred method to evaluate product structures in combinatorial chemistry,
forensic laboratories and with complicated biological samples. Generally, in these situations, you
have some indication of the structure(s) possible. MS can be coupled to separation techniques such
as gas chromatography (GC) and high pressure liquid chromatography (HPLC) to make a
combination technique (GC-MS and LC-MS). GC can separate components in relatively volatile
mixtures and HPLC can separate components in relatively less volatile mixtures. There are also
options for direct inlet of solid samples and sampling methods for high molecular weight
biomolecules and polymers. But, these are beyond the scope of this book.
MS is different from the other spectroscopies (UV-Vis, IR, NMR) in that absorption or emission
of electromagnetic radiation is not used. Rather, the sample (molecule) is ionized by some method
(often a high energy electron beam = electron impact = EI). An electron is knocked out of a bonding
molecular orbital (MO), forming a radical cation. Dications and anions can also be formed, but we
will not consider these possibilities.
R
high
energy
e-
EI mass spec
R
2 e-
radical cation
The cations formed are accelerated in a high voltage field, focused and separated by mass to
charge ratio (m/z or m/e) using a magnetic and/or electric fields. A detector indicates the intensity of
each mass signal and the mass data (x axis) are plotted against this intensity (y axis) to produce a
spectrum similar to that shown below. It is also possible that this same data can be printed in a
tabulated, numerical form (shown in the side box).
The most useful information from the MS is the molecular weight (the M+ peak), which can
indicate what the formula is. The formula provides the degree of unsaturation, which gives important
clues to the possible structures (rings and pi bonds). Fragment peaks that are detected provide hints
as to the nature of the carbon skeleton, heteroatoms and functional groups present.
The most abundant peak (largest) in the mass spectrum is called the base peak. It is assigned a
value of 100% and all other detectable masses are indicated as a percent of the base peak. The
molecular weight peak is called the mass peak or molecular ion peak or parent peak and
symbolized with an M. Since this peak is a radical cation, it often also has a + or + . (plus sign and a
dot) superscript as well. We will use M+. There is often ambiguity in the other fragment peaks
because of high energy rearrangements that are possible. It is usually very difficult to assign a
structure to a completely unknown molecule based solely on mass spectroscopy. But a mass
spectrum can help provide a very important piece of the puzzle, the molecular weight.
y:\files\classes\Spectroscopy Book home\1 Spectroscopy Workbook, latest MS full chapter.doc
Spectroscopy
Beauchamp
base peak = largest peak in MS spectrum = 100% peak, other peaks are reported as a
percent of this peak
molecular ion = M = M+ = M+ = parent peak
Only specific isotopic masses are found in the molecular formula. We do
not see average masses that are listed in the periodic table. Also present
will be M+1, M+2, etc. peaks due to other isotopes. On low resolution MS
these peaks can help decide what the molecular formula is.
In the MS example below, some of the peaks are very logical (57, 85 and 91 are logical) and
some are less so (39, 41, 42, 51 and 55). It is also true that peaks that are logical are sometimes
small or completely missing (119). Many of the other peaks will be explainable with certain
assumptions about fragmentations discussed later in this chapter. .
91
Tabulated Data
Mass
27
28
29
39
41
42
43
50
51
55
57
58
60
63
65
77
85
86
89
90
91
92
176
177
percent
6
2
24
7
26
1
1
1
3
3
99
5
1
3
11
2
100 (base)
6
2
2
36
6
7 = M+
1
85 119
57
1-phenyl-2-hexanone
C12H16O , MW = 176
57
100
85 = base peak
Many smaller
peaks are not
shown, but listed
in data table to
the left.
75
percent
relative 50
intensity
91
29 41
25
27
65
58
39
M+
peak
176
86 92
0
0
25
50
75
100
m
mass
charge = e
125
150
175
200
Spectroscopy
Beauchamp
Typical MS Instrument Features.
The moving charged cations (R-H+) can be made to curve in their direction of flight in a
magnetic or electric field. The amount of curvature is determined by the mass (m) of the ions as
shown in the following equations (assuming the charge, e, is constant = +1). The magnetic field (B)
and/or accelerator plate voltage (V) can be altered to cause each possible mass to impact the detector.
The charged masses must survive about 10-6 to 10-5 seconds to make this journey to the detector.
Often there is some rational feature to explain each peaks special stability that allows it to last long
enough to reach the detector, where it becomes part of the data we examine. We will look at some of
these features later in this discussion. We will not discuss other possibilities, such as metastable ions
or +2 and negatively charged ions. Our main goal in this book is interpretation.
m
e
=
=
B2r2
2V
mV
e
1
B
m = mass
e = charge (usually +1)
B = size of magnetic field
r = radius of curvature
V = voltage on accelerator plate
Besides just seeing a positively charged mass at the detector, we must resolve it from nearby
mass values. MS instruments can be either low resolution (LRMS) or high resolution (HRMS). Low
resolution MS instruments can generally resolve single amu values as high as about 2000 amus (e.g.
they can distinguish 300 amu from 301 amu). An atomic mass unit is defined as 1/12 the mass of a
neutral carbon-12 atom (12C = 12.0000, by definition). High resolution MS instruments can resolve
masses as close as the fourth decimal place (XXX.XXXX). With such accuracy, an exact molecular
formula can be determined by a computer. A molecular formula can also be obtained from LRMS,
Spectroscopy
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through a slightly more involved procedure. HRMS instruments tend to be more expensive and less
common.
Exact Masses
We need to be precise in our calculation of possible masses for each collection of atoms because
the atoms in any cation hitting the detector are specific isotopes. The atomic weights listed in the
periodic table are average weights based on the abundance and mass of all of the naturally occurring
isotopes of each element. For example, the atomic weight of bromine in the periodic table is 79.9,
even though there is no bromine isotope with a mass of 80. The 79.9 atomic weight is a result of an
approximate 50/50 mixture of two stable isotopes of mass 78.9 and 80.9. Because of this
complication, we will require data on the exact masses and the relative abundance of the common
isotopes that we expect to encounter. Those most useful to us in organic chemistry and biochemistry
are listed below.
Element
hydrogen
Average
Atomic Weight
1.00797
Nuclides
1
H
2
H (D)
carbon
12.01115
12
nitrogen
14.0067
14
oxygen
15.9994
16
fluorine
Exact Mass
1.00783
2.01410
Relative Abundance*
100.0
0.015
C
C
12.00000
13.00336
100.0
1.11
N
N
14.00307
15.00011
100.0
0.37
O
O
18
O
15.9949
16.9991
17.9992
100.0
0.04
0.20
18.9984
19
18.9984
100.0
silicon
28.086
28
Si
Si
30
Si
27.9769
28.9765
29.9738
100.0
5.06
3.36
phosphorous
30.974
31
30.9738
100.0
sulfur
32.064
32
S
S
34
S
31.9721
32.9715
33.9679
100.0
0.79
4.43
chlorine
35,453
35
Cl
Cl
34.9689
36.9659
100.0
31.98
bromine
79.909
79
Br
Br
78.9183
80.9163
100.0
97.3
13
15
17
29
33
37
81
127
iodine
126.904
I
126.9045
100.0
*The most abundant nuclide is assigned 100% and the others assigned a fractional percent of that value.
Coincidently, in the examples listed in the table above with more than one isotope, the lowest mass isotope is
the 100% isotope.
Spectroscopy
Beauchamp
Obtaining a molecular formula from a HRMS is relatively straight forward Each possible
molecular mass is unique when calculated to 3-4 decimal places and computers can do the
calculations for us. Try the problems below. Unfortunately, here you have to do the calculations
yourself.
Problem 1 - A low-resolution mass spectrum of 1,10-phenanthroline showed the molecular weight to
be 180. This molecular weight is correct for the molecular formulas C14H12, C13H8O and C12H8N2. A
high-resolution mass spectrum provided a molecular weight of 180.0688. Which of the possible
molecular formulas is the correct one? What is the degree of unsaturation in 1,10-phenanthroline?
Problem 2 Isopalhinine A, a natural product was found by low-resolution mass spectrometry to
have a molecular weight of 291. Possible molecular formulas include C15H17NO5, C16H21NNO4, and
C17H25NO3. High-resolution mass spectrometry indicated that the precise molecular weight was
291.1472. What is the correct molecular formula of isopalhinine? What is the degree of
unsaturation?
To obtain a molecular formula from a LRMS requires more sophistication. Various possible
formulas can be generated using the molecular ion peak and the rule of 13. The first possible formula
assumes that only carbon and hydrogen are present. The molecular mass (M+) is divided by 13
generating an integer (n) and a remainder (r). The number 13 represents the mass of one carbon atom
and one hydrogen atom. The CH formula becomes CnHn+r. All molecular hydrocarbons have even
mass molecular weights.
M
=
13
n + r
Each of these masses = 13 amu = C + H

(We assume there are "n" of them if
the unknown was a hydrocarbon.
This is our starting point formula.)
These are left over hydrogen atoms = r
M = molecular weight
n = number of CH units = quotient
r = left over hydrogens = remainder
Possible hydrocarbon molecular formula = CnHn+r (as a hydrocarbon always an even mass)
The degree of unsaturation can be calculated for this formula and possible rings and/or pi bonds
can be considered (discussed in the introduction, p 10). If oxygen and/or nitrogen (and other
elements) are present, the C/H numbers in the molecular formula must be changed by an amount
equal to the new elements isotopic mass. It is assumed, when substituting atoms, that the major
isotope is used in all cases (always the lowest mass isotope, for us), H=1, C=12, N=14, O=16, S=32,
Cl=35, Br=79. Since oxygen weighs 16, we can subtract CH4 (= 16) from the formula and substitute
in the oxygen atom. If two oxygen atoms were present, we would subtract 2x(CH4) = C2H8 and so
forth. Nitrogen-14 would substitute for CH2 and n nitrogen atoms would substitute for (CH2)x(n). If
we did not have enough hydrogen atoms for some reason (it happens), we could take away one
carbon atom and add in 12 hydrogen atoms, or if there were too many hydrogens, you could do it the
other way around and add one carbon and take away 12 hydrogen atoms.
Information concerning the possible number of nitrogen atoms in the molecular formula is also
available in the molecular mass. If the molecular mass is an even number, then the number of
Spectroscopy
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nitrogen atoms has to be zero or an even number (= 0, 2, 4......). If the molecular mass is an odd
number, then the number of nitrogen atoms has to be odd (= 1, 3, 5.....). Remember, each nitrogen
atom in the formula adds an extra bonding position.
CnH2n+2Ox
C = even mass
H = even mass
O = even mass
MW = even mass
CnH2n+3N1
(N is odd)
C = even mass
H = odd mass
O = even mass
MW = odd mass
CnH2n+4N2
(N is even)
C = even mass
H = even mass
O = even mass
MW = even mass
Problem 3 - An unknown compound produces a molecular weight of 108. What are all possible
formulas having only carbon and hydrogen or having carbon, hydrogen and an oxygen atom (two
oxygen atoms) or having carbon hydrogen and nitrogen (what is the minimum of nitrogen atoms that
would have to be present)? What is the degree of unsaturation for each of these possibilities? Is it
possible that the formula has only a single nitrogen? If so what would the formula be? If not, why
not? What if the molecular weight was 107? (Same questions.)
To choose among the various formulas generated from the rule of 13, we can consider the other
possible isotopes present and their relative abundances to calculate the size of the peaks just one mass
unit (M+1) and two mass units (M+2) larger than the molecular ion peak (M+). For each possible
formula, percents of the M+1 and M+2 peaks versus the M+ peak are calculated. In this calculation
the M+ peak is assumed to be 100% for comparisons with M+1 and M+2, regardless of the base
peak. These calculated values are compared to the experimental values to determine the most likely
formula. The reason for this is that the relative sizes of the M+1 and M+2 peaks are determined by
the number and isotopic abundance of the elements present. The presence of either chlorine, bromine
or sulfur significantly changes the M+2 peak. If there are multiple halogens (Cl and Br), the M+2,
M+4, M+6 and beyond can be calculated and compared to the experimental mass spectrum. This
approach only works if the M+ peak is large enough so that M+1 and M+2 are significant. If the M+
peak is too small, we cant tell what the relative fractions of M+1 and M+2 are. Lets take a look at
how one could calculate the relative size of these peaks (M+1 and M+2).
Sample calculation using M+, M+1, M+2 peaks to identify the molecular formula by LRMS
We will assume an actual formula that is C4H10O. However, we will pretend we dont know
this. How could the M+1 and M+2 lead us to the correct formula? The molecular mass of C4H10O is
74 and that would produce our molecular ion peak, M+. We would have an extra amu in the mass if
we had a different isotope one amu higher. We could do this 4 ways with carbon (because there are
four 13C atoms) 10 ways with hydrogen (2H = D) and 1 way with oxygen (17O). The probabilities for
these possibilities are shown below for the M+1 peak. If we add all of these together we can see the
total probability for getting an M+1 peak relative to 1.0000 for getting the M+ peak. Using a similar
strategy we can estimate the probability for getting an M+2 peak, which will be considerably lower
since we have to get two 13C or two 2H or one 13C and one 2H. The main contribution to the M+2
peak is the 18O isotope. Taken together, these three peaks would predict the indicated distribution for
M+, M+1 and M+2 for this collection of atoms (C4H10O).
Spectroscopy
Beauchamp
molecular ion peak = M+ = 4x(12C) + 10x(1H) + 1x(16O) = 74 amu

as a fraction = 1.000
as a percent = 100%
Whatever the size of this peak,

it is assumed to be 100% for
comparison with the M+1 and
M+2 peaks.
M+1 peak - arises from different possibilities of one additional amu = 75 amu
one 13C =
1.11
101.11
(4 ways) = 0.0439
one 2H =
0.015
100.015
(10 ways) = 0.0015
0.04
101.24
(1 ways) = 0.0004
one
16
O=
13
12
C
C + 13C
2
D
H + 2D
17
16
O
O + 17O+ 18O
sum of possibilities = (0.0439) + (0.0015) + (0.0004) = 0.0458

M+1 peak as a percent of M+ peak = (0.0458)x(100%) = 4.58%
M+2 peak - arises from different possibilities of two additional amu = 76 amu
two 13C =
1.11
101.11
two 2H =
0.015
100.015
4x3
2x1
"mini" probability theory

There are 4 ways of picking
the first carbon and 3 ways of
picking the second carbon
(=4x3) and since all carbon
is the same, we can't tell what
carbon was picked first and
second, so we divide by two
facorial (2x1).
= (0.0439)2(6 ways) = 0.0007
10 x 9
2 x 1 = (2.25x10-8)(45 ways)
= 1 x 10-6 = 0.000001 = too small to consider

one 18O =
0.20
101.24
13
one
C and one H =
(1 ways) = 0.0020
1.11
101.11
100%
0.015
(4 ways) x 100.015
(10 ways)
= 1 x 10-6 = 0.000065 = 0.0001

4.58%
sum of possibilities = (0.0007) + (0.0020) + (0.0001) = 0.0028

M+2 peak as a percent of M+ peak = (0.0028)x(100%) = 0.28%
M+
M+1
0.28%
M+2
To find a possible molecular formula using the M+1 and M+2 peaks, we first find the correct molecular weight
for our molecule (in this case mass = 74). Then we look through the M+1 and M+2 values for two values that
match our mass spec data. In this case we see that C4H10O is a very close match and it becomes our best guess.
M+ = molecular ion peak
(formulas)
74
CH2H2O2
CH4N3O
CH6N4
C2H2O3
C2H4NO2
C2H6NO
C3H6O2
C3H10N2
C4H10O
Exact Mass (M+1)

74.0117
74.0355
74.0594
74.0004
74.0242
74.0480
74.0368
74.0845
74.0003
1.95
2.33
2.70
2.31
2.69
3.06
3.42
4.17
4.52
(M+2)
0.41
0.22
0.03
0.62
0.42
0.23
0.44
0.07
0.28
M+ = molecular ion peak

(formulas)
75
CH2H2O2
CH4N3O
CH6N4
C2H2O3
etc.
Exact Mass (M+1)

74.9956
75.0320
75.0798
75.0684
1.60
2.70
3.45
3.81
(M+2)
0.61
0.43
0.05
0.25
Data tables exist with many values

already calculated for comparisons.
Here is our compound.
Since the molecular weight is even, the number of nitrogens atoms must be even (0,2,4...).
Any formulas with an odd number of nitrogen atoms must be part of a fragment.
Spectroscopy
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Problem 4
a. Calculate the relative intensities (as a percent) of M+, M+1 and M+2 for propene
(CH3-CH=CH2) and diazomethane (CH2=N=N). Can these two formulas (C3H6 vs CH2N2) be
distinguished on the basis of their M+1 and M+2 peaks? Calculate the exact mass (four decimal
places) for both of these formulas. Can they be distinguished on the basis of exact mass? Helpful
data are on page 4.
b. Both CHO+ and C2H5+ have fragment masses of approximately 29, yet CHO+ has a M+1 peak of
1.13% and M+2 peak of 0.20%, whereas C2H5+ has a M+1 peak of 2.24% and M+2 peak of
0.01%. High resolution mass spec shows CHO+ to have a different fragment mass than C2H5+.
Explain these observations and show all of your work. Helpful data are on page 4.
Chlorine, bromine and sulfur, when present, have very characteristic M+2 peaks (32.6% for Cl,
96.9% for Br and 4.4% for S). If multiple Cls and/or Brs are present M+2, M+4 and beyond are
indicative of the number and type of halogen(s) present. The various patterns are available in many
references. However, you can calculate these values yourself, as was done above for the M+1 and
M+2 peaks above.
one Cl comparison of M+ peak (35Cl) to M+2 peak (37Cl)
M+ peak relative size
probability of
100%
100
Cl =
(1 way) = 0.758
100 + 32
35
(assigned a referenced value of 100%)

32%
M+2 peak relative size

probability of
37
Cl =
32
(1 way) = 0.242
100 + 32
0.242
0.758
percent of M+ peak =
(100%) = 32%
M+
M+1
M+2
one Br comparison of M+ peak (79Br) to M+2 peak (81Br)

probability of
100%
97%
100
Br =
(1 way) = 0.508
100 + 97
79

probability of
81
Br =
97
(1 way) = 0.492
100 + 97
0.492
0.508
(100%) = 97%
M+
M+1
M+2
Spectroscopy
Beauchamp
one S comparison of M+ peak to M+1 to M+2 peak

probability of
100
100 + 0.79 + 4.43 (1 way) = 0.950
32
S=
100%

probability of
33
S=
0.79
100 + 0.79 + 4.43 (1 way) = 0.008
0.008
0.950
(100%) = 0.8%

probability of
34
S=
4.4%
0.8%
M+
M+2
M+1
4.43
100 + 0.79 + 4.43 (1 way) = 0.042
0.042
0.950
(100%) = 4.4%
one Br and one Cl comparison of M+ peak to M+2 and M+4 peaks

probability of 79Br = 0.508 (from above) probability of 35Cl = 0.758 (from above)
(probability of 79Br)(probability of 35Cl) = (0.508) (0.758)(1 way) = 0.385
probability of 81Br = 0.492 (from above) probability of 37Cl = 0.242 (from above)
(probability of 79Br)(probability of 37Cl)(1 way) = (0.508) (0.242)(1) = 0.123
total = 0.496
percent of M+ peak = (0.496/0.373)x100% = 129%
129%
100%
31%
M+
M+2
M+4
two Cl comparison of M+ peak to M+2 peak to M+4 peaks

probability of two 35Cl = (0.758)2 (1 way) = 0.602
100%
61%

probability of 37Cl = 0.242 (from above)
(probability of 35Cl)(probability of 37Cl)(2 ways) = (0.758) (0.242)(2) = 0.367
(probability of 37Cl)(probability of 37Cl)(1 way) = (0.242)2(1) = 0.059
10%
M+
M+2
M+4
Spectroscopy
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10
Problem 5 - Calculate the relative intensities (as a percent) of M+, M+2 and M+4 for Br2. Use the
probabilities from above.
Problem 6 - Calculate the relative intensities (as a percent) of M+, M+2, M+4 and M+6 for BrCl2 and
Br2Cl. Hint: All of the data you need to perform these calculations are in the examples above. Use
the probabilities from above.
Energetics of Fragmentation of simple hydrocarbon patterns
Bonds are broken in fragmentations, forming radicals and/or cations. The energy costs for
radicals and cations of common hydrocarbon patterns are worked out in the tables that follow. We
first assume a C-H bond is homolytically broken (each atom gets one electron, no charge is formed).
Next, we take away the cost of making the hydrogen atom (the same for every C-H bond) to find out
what the cost is for forming only the carbon free radical. Lower energy possibilities are favored over
higher energy possibilities. A few problems are provided just below the following tables to illustrate
these points.
A similar diagram is constructed to estimate the energy costs of forming carbocations. We start out the
same, but in this diagram we include the ionization potential of the carbon free radical, a value that can be
measured experimentally. We again take away the energy to make the hydrogen free radical and also take
away the energy change when the hydrogen atom attracts the extra electron (electron affinity) to become a
hydride. What remains is an estimate of the energy to make only the carbocation. This is a considerably larger
amount of energy than to make the carbon free radical (because we are stealing away an electron).
Spectroscopy
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11
General Energy Cycle for Carbocations - relative energy to form carbocations (all energy values in kcal/mole)
e-
heterolytic
bond energy
H
Hf o(H ) = -52 heat of formatio of hydrogen
atom, common to all cycles
H
ionization
potential of R
H
R
R-H
Compound
H-H
H3C-H
CH3CH2-H
(CH3)2CH-H
(CH3)3C-H
CH2=CHCH2-H
C6H5CH2-H
Radical
H (hydrogen carbocation)
(methyl carbocation)
H3C
CH3CH2 (primary carbocationl)
(CH3)2CH (secondary carbocation)
(tertiary carbocation)
(CH3)3C
(allylcarbocation)
CH2=CHCH2
(benzyl carbocation)
C6H5CH2
Hf o(H electron af finity) = -17
Hf o(R ) = + value
(see table)
H
homolytic
bond
energy
Energy to f orm
carbocation
Hf
o(H
Hf o(R ) = [BE+IP-EA- Hf o(H )]

)
= energy to make R
(104) + (313) - (17) - (52) = +348
(105) + (227) - (17) - (52) = +263
(BE)
I.P. E.A.(H)
104
105
98
95
92
86
313
227
193
169
154
186
-17
-17
-17
-17
-52
-52
-52
-52
-17
-17
-52
-52
(98) + (193) - (17) - (52) = +222

(95) + (169) - (17) - (52) = +195
(92) + (154) - (17) - (52) = +177
(86) + (186) - (17) - (52) = +203
88
165
-17
-52
(88) + (165) - (17) - (52) = +184
Common arguments for relative stabilities of free radicals and carbocations are inductive
effects/hyperconjugation and resonance. Inductive effects and hyperconjugation argue that switching
out a hydrogen for a carbon group allows greater electron donation to the electron deficient carbon
atom (free radical or carbocation) because of increased pairs of electrons polarized towards the
electron deficient centers. Carbocations are much more electron deficient than free radicals and
benefit much more from this effect. The resonance argument states that an adjacent pi bond or lone
pair can spread electron density through parallel p orbitals, thus reducing the energy to form a cation
or free radical.
Spectroscopy
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12
The differences in relative carbocation stabilities parallel the trend seen in free radicals, but are greatly
enhanced versus the free radical stabilities.
One could also make a steric argument for tertiary being the most stable free radical or
carbocation. The geometry changes from 109o (sp3) bond angles to 120o bond angles (sp2). The
ground state of a tertiary C-H bond would start at higher potential energy from crowding, which
would be relieved somewhat when the fourth group is removed, providing, perhaps, part of the
advantage in the tertiary reaction over secondary over primary over methyl when forming tertiary free
radicals and carbocations.
R
C
R
R
more crowded as sp3 center = higher

potential energy starting point
with 3-4 larger groups around
tetrahedral carbon
Breaking a bond is a large

uphill energy transformation,
but less so with a sterically
crowded starting point, so Ea
is a little smaller than expected.
R
C
less crowded as sp2with 3 groups

around trigonal planar carbon
is slightly more stable than it
would be if groups were smaller
Spectroscopy
Beauchamp
13
Problem 7 Consider the possible fragmentation of 2-methylbutane (isopentane). There are 3 types
of C-C bonds that could break (b,d,f) and 4 types of C-H bonds that could break (a,c,e,g). Only
consider breaking the C-C bonds (b,d,f) and the tertiary C-H bond (c). Each bond could break in two
ways: either atom could be a cation and either atom could be a free radical. Calculate the energy cost
for each possibility (each bonded atom as a radical and each atom as a cation). For each possibility
what are the masses that would be observed at the detector (we only see cations)? This problem will
require eight calculations for the four bonds considered.
CH3
H2C
a
H
d H f
CH2
C
c
e
g
H
H
H
CH3
high energy
electron beam
H2C
a
H
2-methylbutane
(isopentane)
d H f
CH2
C
c
e
g
H
H
H
Possible
fragmentations?
Energy to rupture bonds
(eight calculations).
radical cation
b
Actual Mass Spectrum tabulated and graphical.

mass percent
15
2
26
4
27 43
28
6
29 60
30
1
37
1
38
3
39 30
40
5
41 88
42 95
43 100 = base
44
7
50
2
51
3
53
4
55 10
56 40
57 95
58
6
71
5
72 16 = M+
Peaks 15, 29, 43, 57 and 72 are logical. In our discussions of

fragmentation we will see how many of the other peaks are explainable.
75 eV
43 = base peak
41,42
57
100
isopentane
C5H12
75
CH3
43
15
CH 29 CH3
H3C
C
H2
MW = 72
57
29
percent
relative 50
intensity
39
25
Many smaller
peaks not shown.
M+
peak
72
0
0
25
50
mass
m
=
charge
e
75
100
Spectroscopy
Beauchamp
14
Problem 8 Consider the possible fragmentation of 2,2,4-trimethylpentane. There are four types of
C-C bonds that could break (a, b, d, f) and 4 types of C-H bonds that could break (a, c, e, g). Only
consider breaking the C-C bonds (a, b, c, d). Each bond could break in two ways: either atom could
be a cation and either atom could be a free radical. Calculate the energy cost for each possibility
(each bonded atom as a radical and each atom as a cation). For each possibility what are the masses
that would be observed at the detector? This problem will require eight calculations for the four
bonds considered (we only see cations).
CH3
H3C a C
b
H2
C
CH3
H
C
CH3
CH3
high energy
electron beam
H2 H
CH3
H3C a C
C
C
c
b
d
CH3
CH3
2,2,4-trimethylpentane
a
27
5
29
8
39
5
40
1
41 21
42
1
43 18
53
1
55
3
56 33
57 100 = base
58
4
99
6
114
0 = M+ (missing)
CH3
Energy to rupture bonds

(eight calculations).
radical cation
a

mass percent
Possible
fragmentations?
Spectroscopy
Beauchamp
15
Problem 9 - Predict reasonable fragmentation patterns for n-octane and where the major ion peaks
should appear. Rationalize your predictions on the basis of energetics. The mass spectrum is
provided for comparison. Some of the less logical peaks will become explainable after our
discussions on fragmentation. Is there a logical peak that is missing?
mass percent
27 20
28
4
29 27
39 12
40
2
41 44
42 15
43 100 = base
44
3
53
2
55 11
56 18
57 34
69
2
70 12
71 20
84
7
85 26
86
2
114
6 = M+
percent
relative
intensity 75 eV
base
peak
43
100
octane
C8H18
Many smaller
peaks not shown.
75
H2
C
H3C
H2
C
C
H2
H2
C
C
H2
CH3
C
H2
50
41
29
25
57
M+
peak
114
85
71
0
0
25
50
mass
m
=
charge
Z
75
100
120
Spectroscopy
Beauchamp
16
Special patterns of fragmentation from organic functional groups

Alkanes - Key Points (see examples above)
1. Lower mass alkyl branch fragments (2-6 Cs, masses = 29, 43, 57, 71, 85) are more intense than
higher mass fragments (6). The loss of the smaller branch as the cation more commonly reaches
the detector.
2. The major carbocations that form follow carbocation stabilities (R+ = 3o > 2o > 1o > Me). It is
also quite possible that less stable carbocations rearrange to more stable carbocations before they
reach the detector. We cant tell by only observing the mass since they have the same number.
less stable
primary carbocation
proposed
fragmentation
more stable
tertiary carbocation
probable
rearrangement
R
C4H9
mass = 57
can't tell which
C4H9
mass = 57
3. Linear alkanes more often have observable molecular ion peaks, while increased branching
weakens the molecular ion peak. Fragmentation is more common at branch points. Loss of a
methyl from a straight chain is considerably weaker than loss of a methyl at a branch point.
M+ = 114 (6%)
base peak = 43
(M - 15) = 99 peak (0%)
M+ = 114 (3%)
base peak = 43
(M - 15) = 99 peak (1%)
M+ = 114 (0%)
base peak = 57
(M - 15) = 99 peak99 peak (6%)
4. Linear fragments often differ by 14 amu (different size branches split off between carbons in different
molecules, CH2 = 14). Take another look at problem 9, just above.
5. There are often clusters of peaks around main peaks. Very large fragment peaks will have a
trailing M+1 peak due to 13C isotopes (about 1% for every carbon present). A rough guide for
any large peak is that it will have M+1 peak that is about 1% its size for every carbon in the
fragment due to 1% 13C isotopes at each carbon. For example, if a fragment mass had an 80%
value in a five carbon fragment, the next mass peak would be expected to be 0.05x80% 4% size
based on 13C isotopes. If there were 10 carbons, the next mass peak would be expected to have
0.10x80% 8% size just based on the 13C isotopes (in addition to any real fragments that might
come at that value.
Spectroscopy
Beauchamp
17
6. Cycloalkanes tend to have stronger molecular ion peaks (two bonds have to break) and their
fragment patterns are more complicated to interpret (and we wont try to interpret every
possibility). Alkene fragmentation peaks are often subfeatures of the fragmentation pattern. Loss
of CH2CH2 (= 28) is common, if present.
M+ = 112 (59%)
M-28 = 84 (39%)
M+ = 114 (6%)
M-28 = 86 (2%)
7. Two masses that seem to show up in nearly every mass spectrum are 39 and 41. These may arise
from resonance stabilized carbocations formed by rearrangements in the high energy electron
beam. Look for peaks that extend those patterns by units of 14 (insertion of a CH2),. which are
also commonly observed masses.
8. Even masses of 30, 44, 58, 72, etc. on occasion can be due to radical-cation alkanes that form
from high energy rearrangements. Some of these masses form from other fragmentations too.
But if there is no other logical reason to see one of these masses, this could be a possible
explanation.
Common alkane fragmentations occur at branch points; more branches lead to more stable
carbocations. However, skeletons can rearrange in almost any conceivable way possible to form
more stable carbocations (e.g. 3o R+ > 2o R+ > 1o R+ > H3C+). Also, alkanes can lose H2 or R-H to
form alkenes, so we have to consider possible alkene rearrangements for alkanes too (see our next
functional group). Smaller masses tend to be more prominent than larger masses in the mass
spectrum. Perhaps they dont have as many options for falling apart as the larger fragments do.
Also, when larger fragments fall apart, they make smaller fragments.
Spectroscopy
Beauchamp
18
M+ = 114
C8H18
71
57
57
99
43
85
29
C6H13
C8H18
15
M+ = 114
octane - all alkane f ragments

are observed, except 99.
99
C6H13
C5H11
C4H9
C3H7
85
71
57
43
not observed
in octane
Only cations reach detector, so only the part with positive charge is observed at the detector. A positive charge
is written on all f ragments to indicate that either part could retain the positive charge (in a rearranged stable form).
Of ten you can see the mass of both cations of a possible fragmentation. It is usef ul to look f or both fragment
masses in the mass spectrum. Peaks related to alkene fragmentations are discussed in the next f unctional group.
The typical appearance of a mass spectrum is shown below. Data is also often presented as shown
to the right. The intensity of the peaks tends to decrease as the fragment masses get larger. Larger
f ragments are less likely to survive the 10-5 second trip to the detector.
Mostly peaks greater than 4%

of the base peak are shown.
43 = base
MW = 114
41
57
27 29
28
20
30
39
40
42
71
56
55
50
85
M+ = 114
70
60
70
80
90
100
110
120
C2H5
29
C1H3
15
actual peaks
in octane
mass
%
15.0
1
26.0
1
27.0
20
28.0
4
29.0
27
39.0
12
40.0
2
41.0
44
42.0
15
43.0 100
44.0
3
51.0
1
53.0
2
54.0
1
55.0
11
56.0
18
57.0
34
58.0
2
69.0
2
70.0
12
71.0
20
72.0
1
84.0
7
85.0
26
86.0
2
99.0 none
114.0
6
115.0
1
alkane
peaks
base
M+
Spectroscopy
Beauchamp
19
3,4-dimethylhexane - has branches

possible alkyl
fragments
15 / 99
actual peaks
in 3,4-dimethylhexane
mass %
27.0 10
28.0
1
alkane
H
58 (4%)
29.0 26
29 / 85
peaks
elimination reaction similar to
39.0
7
-H2O in alcohols to form alkene
40.0
1
43 / 71
41.0 43
42.0
2
57 / 57
MW = 114
43.0 58
Loss of hydrogen (H-H) or an alkane (R-H) fragment
44.0
2
generates alkenes so alkene fragmentation patterns are
51.0
1
also observed from alkane structures (see on next page).
the base
53.0
2
peak is
55.0
8
not expected
56.0 100
(-RH)
(-H2)
57.0 81
58.0
4
56 (100%)
69.0
3
alkenes
70.0
1
The base peak (56) is likely from an alkene, C4H8.
(see the next functional group)
71.0
1
Remarkably, it is the major peak in the spectrum!
84.0
7
85.0 41
56 = base
86.0
3
99.0 none
57
114.0
2
M+
115.0 0.2
43
27
20
29
30
84
55
39
40
MW = 114
85
41
50
60
70
80
M+ = 114
90
100
110
120
130
It is very common to see alkene fragments in the mass spectra of alkanes, though it is very
surprising to see one as the base peak, as is the case here. In the next functional group, we will
compare fragmentations of alkenes and alkanes.
Alkenes - Key Points
1. A pi electron is likely to be ionized first from the HOMO of the alkene as the least tightly held electrons.
Alkenes often produce stronger molecular ion peaks than alkanes because of this.
R
octane, MW =114 (M+ = 6%)
e-
Remaining sigma bond

holds skeleton together.
oct-1-ene, MW =112 (M+ = 20%)
2. The double bond can migrate through the skeleton (this makes it difficult to distinguish among positional
isomers sharing a common skeleton).
These alkenes all look similar.
Spectroscopy
Beauchamp
20
3. Allylic cleavage is common due to resonance stabilization of cation fragment. The mass can vary
depending on the groups attached to the allylic part. Look for peaks that extend this pattern by units
of 14 (insertion of CH2 x1, x2, ).

R
R' ionization
R'
fragmentation
R'
free radical
is sucked away
resonance stabilized carbocation

mass = 41 (R = H)
55 (R = CH3)
69 (R= CH2CH3)
83 (R = C3H7)
etc.
4. McLafferty-like rearrangements are possible (similar to carbonyl pi bonds). Again, bond migration is
possible. Also look for some of these fragment peaks in alkane mass spectra that have lost H2.
McLafferty-like rearrangement
H
CH2
fragmentation
It is possible to see the cation charge on either

fragment. Both fragments will be even unless
an odd number of nitrogen atoms is present.
R
R
H
C
H2C
C
R
C
H2
CH2
mass = 42 (R = H)
56 (R = CH3)
70 (R= CH2CH3)
84 (R = C3H7)
even mass
28 (R = H)
42 (1 extra C)
56 (2 extra C)
70 (3 extra C)
5. Cyclohexenes often undergo retro Diels-Alder reactions.
R2
R1
R2
fragmentation is a
retro-Diels-Alder reaction
R1
diene
dienophile
Only cations reach the detector. Either fragment could be positive,

but usually the diene would be the more stable cation. Both
fragments will be even unless an odd number of nitrogen atoms is present.
Spectroscopy
Beauchamp
21
Alkenes Fragmentation Patterns (Many of those below can also be found in octane, an alkane.)
Only cations reach detector, so only the part with positive charge is seen at the detector. A positive charge is
written on both fragments to indicate that either could retain the positive charge (in a rearranged stable form).
Often you can see both as cations from different fragmentations. The following peaks are explained by
common alkene fragmentations (data on the right). Many of them are found in fragment peaks of octane, an
alkane (see data on the following page). A pi bond can migrate through the skeleton to almost any conceivable
position, leading to almost any variation conceivable.
McLafferty rearrangements
allylic fragmentations
H
OR
OR
112 (0%)
112 (0%)
42 (15%)
41 (44%)
70 (12%)
H
OR
112 (0%)
56 (18%)
112 (0%)
56 (18%)
H
OR
112 (0%)
70 (12%)
42 (15%)
112 (0%)
112 (0%)
71 (20%)
mass %
26.0
1
27.0
20
28.0
4
29.0
27
39.0
12
OR
40.0
2
44
57 (34%) 41.0
42.0
15
43.0 100
55 (11%)
44.0
3
53.0
2
55.0
11
56.0
18
57.0
34
OR
58.0
2
69.0
2
12
43 (100%) 70.0
69 (2%)
71.0
20
72.0
1
84.0
7
85.0
26
86.0
2
CH3
114.0
6
OR
15 (0%)
97 (0%)
H
OR
112 (0%)
84 (7%)
OR
28 (4%)
actual peaks
from octane
112 (0%)
83 (0%)
29 (27%)
Spectroscopy
Beauchamp
22
Similar fragmentation patterns for C8H16 alkenes. Notice that octane (an alkane) has many of these same fragments.
B
A
octane
B
1-octene
1
15.0
1 15.0
1
26.0
1 26.0
27.0 20 27.0 25
5
28.0
4 28.0
29.0 27 29.0 35
30.0
- 30.0
1
32.0
- 32.0
1
38.0
- 38.0
39.0 12 39.0 28
5
40.0
2 40.0
41.0 44 41.0 82
42.0 15 42.0 66
43.0 100 43.0 100
3
44.0
3 44.0
50.0
- 50.0
2
51.0
1 51.0
1
52.0
- 52.0
8
53.0
2 53.0
9
54.0
1 54.0
55.0 11 55.0 99
56.0 18 56.0 87
57.0 34 57.0 19
58.0
2 58.0
59.0
- 59.0
63.0
- 63.0
1
65.0
- 65.0
66.0
- 66.0
6
67.0
- 67.0
7
68.0
- 68.0
69.0
2 69.0 44
70.0 12 70.0 86
71.0 20 71.0 12
72.0
1 72.0
77.0
- 77.0
79.0
- 79.0
1
81.0
- 81.0
6
82.0
- 82.0
83.0
- 83.0 34
84.0
7 84.0 22
2
85.0 26 85.0
86.0
2 86.0
4
97.0
- 97.0
112.0
- 112.0 20
2
113.0
- 113.0
114.0
115.0
1
E
D
C
F
H
G
trans-2-octene cis-2-octene trans-3-octene cis-3-octene cis-4-octene trans-4-octene
15.0
1
26.0
1
27.0 18
28.0
4
29.0 33
30.0
1
32.0
38.0
1
39.0 19
40.0
3
41.0 64
42.0 34
43.0 11
44.0
50.0
1
51.0
2
52.0
1
53.0
8
54.0
9
55.0 100
56.0 52
57.0 21
58.0
1
59.0
63.0
65.0
1
66.0
67.0
5
68.0
4
69.0 29
70.0 43
71.0
4
72.0
77.0
79.0
81.0
1
82.0
2
83.0 16
84.0
7
85.0
86.0
97.0
2
112.0 28
113.0
3
15.0
1
15.0
26.0
1
26.0
27.0 25 not available 27.0
28.0
4
28.0
29.0 45
29.0
30.0
1
30.0
32.0
32.0
38.0
1
38.0
39.0 22
39.0
40.0
4
40.0
41.0 81
41.0
42.0 44
42.0
43.0 15
43.0
44.0
1
44.0
50.0
1
50.0
51.0
2
51.0
52.0
1
52.0
53.0
8
53.0
54.0
8
54.0
55.0 100
55.0
56.0 63
56.0
57.0 25
57.0
58.0
1
58.0
59.0
59.0
63.0
63.0
65.0
1
65.0
66.0
66.0
67.0
6
67.0
68.0
5
68.0
69.0 34
69.0
70.0 56
70.0
71.0
6
71.0
72.0
72.0
77.0
77.0
79.0
79.0
81.0
1
81.0
82.0
3
82.0
83.0 22
83.0
84.0 10
84.0
85.0
1
85.0
86.0
86.0
97.0
2
97.0
112.0 36
112.0
113.0
3
113.0
2
2
25
4
19
2
26
5
100
38
18
1
2
4
2
11
8
95
54
16
1
1
1
2
1
10
7
47
48
6
2
2
3
2
24
7
2
2
36
3
15.0
1
26.0
2
27.0 23
28.0
3
29.0 17
30.0
32.0
38.0
2
39.0 24
40.0
4
41.0 93
42.0 29
43.0 15
44.0
50.0
2
51.0
3
52.0
2
53.0
9
54.0 9.2
55.0 100
56.0 46
57.0 14
58.0
59.0
63.0
1
65.0
2
66.0
1
67.0
9
68.0
5
69.0 36
70.0 44
71.0
5
72.0
77.0
1
79.0
2
81.0
2
82.0
2
83.0 24
84.0
7
85.0
1
86.0
97.0
2
112.0 36
113.0
3
alkyl branch fragments = 15, 29, 43, 57, 71, 85, 99

allylic fragments = 27, 41, 55, 69, 83, 97
McLafferty fragments = 28, 42, 56, 70, 84, 98
15.0
1
26.0
1
27.0 16
28.0
2
29.0 14
30.0
32.0
38.0
1
39.0 16
40.0
2
41.0 78
42.0 25
43.0 12
44.0
50.0
1
51.0
2
52.0
1
53.0
6
54.0
7
55.0 100
56.0 43
57.0 12
58.0
59.0
63.0
65.0
2
66.0
67.0
8
68.0
4
69.0 32
70.0 42
71.0
4
72.0
77.0
1
79.0
1
81.0
2
82.0
2
83.0 29
84.0
7
85.0
86.0
97.0
1
112.0 33
113.0
3
Spectroscopy
Beauchamp
23
Another Alkene Example (C7 alkene)

alkenes (1-heptene, 2-heptene, 3-heptene, all of them look similar because the pi bond can migrate through the skeleton)
This example starts with hept-1-ene
A pi bond can migrate
through the skeleton to
almost any conceivable
position.
H
C7H14 = 98 (14%)
42 (55%)
56 (100%)
C7H14 = 98 (14%)
56 (100%)
42 (55%)
C7H14 = 98 (14%)
70 (44%)
alkyl branches
15 (1%)
29 (56%)
43 (16%)
57 (31%)
71 (3%)
85 (0%)
28 (5%)
allylic
fragments
27 (26%)
41 (97%)
55 (68%)
69 (31%)
83 (4%)
41 (97%)
57 (31%)
all peaks > 1%

15.0
1
18.0
1
26.0
2
27.0 26
28.0
5
29.0 56
30.0
1
43 (16%)
38.0
2
39.0 30
C7H14 = 98 (14%)
55 (68%)
40.0
5
41.0 97
42.0 55
43.0 16
50.0
2
51.0
2
52.0
1
53.0
6
54.0
8
55.0 68
69 (31%)
29 (56%)
C7H14 = 98 (14%)
56.0 100
57.0 31
58.0
1
67.0
2
68.0
4
69.0 31
CH3 = 15 (1%)
70.0 44
71.0
2
83.0
4
98.0 14
83 (31%)
C7H14 = 98 (14%)
C7H14 = 98 (14%)
McLafferty
fragments
28 (5%)
42 (55%)
56 (100%)
70 (44%)
Spectroscopy
Beauchamp
24
Alkynes - Key Points

1. Terminal alkynes have weak or missing M+ peaks (they often lose radical hydrogen), though M-1
can be very strong.
H
H H
H
M+
(M-1)+
2. The triple bond can migrate through the skeleton (this makes it difficult to distinguish among positional
isomers sharing a common skeleton).
These alkynes all look similar.
3. All alkynes give a reasonably strong m/e = 39 peak from propargylic cleavage (resonance is OK,
but more electronegative sp carbocation resonance form reduces contribution). This mass can
also be explained by rearrangement to from a very stable aromatic cyclypropenyl carbocation. If
you look at a lot of mass spectra, this mass always shows up, even if no alkyne is present. Look
for peaks that extend this pattern by units of 14 (insertion of CH2 x1, x2, ).
Only cations reach the detector. Mass 39 is in every EI mass spectrum.
This could be because the cation is really an aromatic carbocation.
R'
C
C
fragmentation
CH
H
resonance
C
H
R'
also
works
for
C
C
R
C
H
radical cation
mass = 39 (R = H)
53 (R = CH3)
67 (R= CH2CH3)
4. Small peaks at M=26 are probably ethyne (acetylene).

H
C
C
M = 26
H
5.
McLafferty-like rearrangements are possible (similar to the alkene above and a carbonyl pi bond)
R
H
C
R
H
C
R
fragmentation
C
H
C
H
radical cation
even mass
on one or the other.
H
40 (R = H)
28 (R = H)
54 (R = CH3)
42 (R = CH3)
68 (R= CH2CH3)
56 (R= CH2CH3)
82 (R= C3H7)
70 (R= C3H7)
Either fragment can be observed and both show an even mass.
Spectroscopy
Beauchamp
25
Example peaks from hept-1-yne:

alkynes (1-heptyne, 2-heptyne, 3-heptyne, all of them look similar because the pi bonds can migrate through the skeleton)
A pi bond can migrate
through the skeleton to
almost any conceivable
H
position.
C7H12 = 96 (1%)
40 (12%)
C7H12 = 96 (1%)
56 (26%)
39 (30%)
57 (28%)
43 (4%)
C7H12 = 96 (1%)
54 (35%)
42 (8%)
C7H12 = 96 (1%)
53 (18%)
15 (0.5%)
29 (46%)
43 (4%)
57 (28%)
71 (0.2%)
85 (0%)
C7H12 = 96 (1%)
68 (30%)
C7H12 = 96 (1%)
28 (4%)
67 (44%)
29 (46%)
CH3
15 (0.5%)
81 (100%)
C7H12 = 96 (1%)
%
1
18
4
46
1
1
3
30
mass
40.0
41.0
42.0
43.0
45.0
50.0
51.0
52.0
%
12
71
8
4
1
3
6
3
mass
53.0
54.0
55.0
56.0
57.0
58.0
63.0
65.0
%
18
35
51
26
28
1
2
7
mass
66.0
67.0
68.0
69.0
70.0
77.0
79.0
80.0
%
3
44
30
2
2
3
11
1
mass
C7H12
M+ = 96
1-heptyne
mass
26.0
27.0
28.0
29.0
30.0
37.0
38.0
39.0
C7H12
M+ = 96
2-heptyne
mass
15.0
18.0
26.0
27.0
28.0
29.0
37.0
38.0
%
1
2
3
40
7
9
2
4
mass
39.0
40.0
41.0
42.0
43.0
50.0
51.0
52.0
%
51
8
68
7
26
6
12
9
mass
53.0
54.0
55.0
56.0
57.0
62.0
63.0
65.0
%
47
82
22
8
1
2
3
10
mass
66.0
67.0
68.0
69.0
77.0
78.0
79.0
80.0
%
6
43
42
4
5
1
14
3
mass
%
81.0 100
82.0
8
91.0
1
95.0
5
96.0 18
97.0
2
C7H12
M+ = 96
3-heptyne
mass
15.0
18.0
26.0
27.0
28.0
29.0
37.0
38.0
%
2
1
3
23
1
14
2
4
mass
39.0
40.0
41.0
42.0
43.0
50.0
51.0
52.0
%
43
12
84
10
3
6
12
7
mass
53.0
54.0
55.0
56.0
61.0
62.0
63.0
64.0
%
49
25
26
5
1
3
5
1
mass
%
65.0 21
66.0 11
67.0 100
68.0 29
69.0
2
74.0
1
77.0
9
78.0
2
81.0 100
82.0
7
95.0
9
96.0
1
mass
79.0
80.0
81.0
82.0
91.0
93.0
95.0
96.0
97.0
%
32
4
93
6
2
1
7
70
6
Spectroscopy
Beauchamp
26
Benzenoid Structures - Key Points

1. Generally, aromatics compounds show a strong M+ peak.
2. A side chain alkyl branch (RCH2-) can fragment at the benzylic position, which is proposed to
rearrange to the tropylium ion showing a m/e = 91 peak. Analogous rearrangements are possible
in more substituted benzenoid compounds producing different, but predictable, masses.
R
R
CH2 fragmentation
R'
R'
radical cation
CH2
rearrangement
lots of
R'
resonance
tropylium ion,
an aromatic cation
(lots of resonance)
R' = mass
H
91
CH3 105
C2H5 119
HO 107
H2N 106
Only cations reach the detector. This mass is 91 (if

R = H) and even though it is a very stable cation, it
rearranges to a more stable 'tropylium' carbocation.
Any branches or heteroatoms would change the '91'
mass.
3. Isomeric benzenes are difficult to distinguish among, as a group. Even though the structures are
different, the mass spectra of the compounds are pretty much alike due to high energy
rearrangements.
These isomers have similar

looking mass spectra.
4. McLafferty-like rearrangements are possible, if a simple alkyl chain of three more carbons is
present (oxygen can also be in the branch) and a hydrogen atom is on the gama atom. This
fragmentation produces an even mass of m/e = 92 for an unsubstituted carbon chain. Substituted
rings will have different masses depending on the additional atoms. Remember that part of the 92
peak is C-13 isotopes in the 91 peak (about 7x0.01 = 0.07).
R
H
C
C
H
R
H
or
can be on either fragment

H
Even mass, if there is not an

odd number of nitrogen atoms.
C
R = mass H
H
92
CH3 106
C2H5 120
HO 108
H2N 107
Both have even masses,

if there is not an odd
number of nitrogen atoms.
H
H
R = mass
H
28
42
CH3
56
C2H5
C3H7
70
Spectroscopy
Beauchamp
C
C
27
or
can be on either fragment

H
H
28.0 = 1%
94.0 = 100%
M+ = 122 (35%)
Examples:
benzylic fragmentations
H
C11H16 = 148 (27%)
56 (0.4%)
92 (74%)
15 (0.2%)
29 (6%)
43 (1%)
57 (4%)
71 (0%)
85 (0.2%)
105 (11%)
43 (1%)
105 (11%)
bridging phenyl group
C12H18
M+ = 162
hexylbenzene
C12H18
M+ = 162
1-t-butyl-3-ethylbenzene
C10H14
M+ = 135
p-propyltoluene
57 (4%)
91 (100%)
mass
27.0
29.0
39.0
41.0
42.0
43.0
50.0
51.0
%
5
6
6
8
1
17
1
3
mass
52.0
55.0
56.0
63.0
65.0
71.0
77.0
78.0
%
1
4
1
2
9
2
5
6
mass
27.0
29.0
39.0
41.0
51.0
53.0
57.0
63.0
%
1
2
2
6
2
1
1
1
mass
64.0
65.0
66.0
77.0
78.0
79.0
89.0
91.0
%
2
4
1
4
2
6
1
14
mass
27.0
39.0
41.0
51.0
53.0
63.0
65.0
77.0
%
2
3
2
2
1
1
2
6
mass
%
78.0
2
79.0
5
91.0
6
92.0
2
103.0
3
104.0
2
105.0 100
106.0
9
mass
%
79.0
4
82.0
1
83.0
2
89.0
1
91.0 100
92.0 95 *
93.0
8
103.0
2
65 (9%)
77 (4%)
mass
%
mass
%
163.0
5
104.0
3
105.0 11
106.0
2
115.0
1
117.0
1
119.0
3
133.0
5
162.0 33
* Only about 7% is due to 13C isotopes.
mass
mass
%
162.0
119.0 21
163.0
120.0
2
128.0
2
129.0
1
131.0
3
133.0
1
147.0 100
148.0 12
Notice that "91" is not logical, but it shows up.
mass
92.0
103.0
104.0
105.0
107.0
115.0
116.0
117.0
%
1
2
1
4
2
5
2
4
mass
%
115.0
1
117.0
1
119.0
1
134.0 23
135.0 2.6
mass
mass
%
21
3
Spectroscopy
Beauchamp
28
Halogenated Compounds - Key Points

1. Fluorine (mass = 19) and iodine (mass = 127) have only one naturally occurring isotope, loss of
either of these masses is informative (M-19, M-127). Fluorine compounds tend to show weak
M+ peaks (or none at all). When iodine is lost, there can be a big hole (= 127) in the middle of
the mass spectrum.
2. Chlorine has two isotopes (35 and 37) which occur in a 3:1 ratio; this is easily observed when
there is a molecular ion and in any fragments that retain the chlorine. An M-35 peak is
informative, and M-36 corresponds to loss of HCl.
3. Bromine has two isotopes (79 and 81) which occur in a 1:1 ratio; this is easily observed when
there is a molecular ion and in any fragments that retain the bromine. An M-79 peak is
informative, and M-80 corresponds to loss of HBr.
4. Loss of X is common (see above) and loss of HX can occur with fluorine (M-20), chlorine
(M-36), bromine (M-80).
5. Loss of an alkyl radical and formation of a five atom ring or three atom ring is possible with
chains of C5 and longer with bridging chlorine, bromine or iodine (also true for sulfur).
X
X
fragmentation
Cations reach the detector,

will see this mass.
R
Free radicals are sucked
away by the vacuum pump.
X = mass
Cl
91
Br
135
I
183
X
fragmentation
R

will see this mass.
X = mass
Cl
63
Br
107
I
155
R
Spectroscopy
Beauchamp
29
Examples
Cl
1-chlorhexane
C6H13Cl = 120
alkyl branches
15 (1%)
29 (32%)
43 (72%)
57 (15%)
71 (3%)
85 (0.7%)
Cl
Cl
84 (4%), minus HCl
91 (100%)
63 (5%)
other alkene fragments

allylic
McLafferty
27 (27%)
28 (5%)
41 (59%)
42 (45%)
63 (81%)
56 (56%)
70 (3%)
84 (1%)
91.0 100
93.0 32
Br
1-bromorhexane
C6H13Br = 165
I
1-iodohexane
C6H13I = 212
I
1-iodopropane
C3H7I = 170
I
2-iodopropane
C3H7I = 170
alkyl branches
15 (1%)
29 (21%)
43 (66%)
57 (100%)
71 (3%)
85 (18%)
alkyl branches
15 (1%)
29 (15%)
43 (100%)
57 (11%)
71 (0%)
85 (50%)
alkyl branches
15 (2%) (1%)
29 (0%) (0%)
43 (100%) (100%)
57 (0%) (0%)
71 (0%) (0%)
85 (0%) (0%)
Almost identical
mass spectra.
35
Cl and 37Cl
mass %
mass
15.0
26.0
27.0
28.0
29.0
39.0
40.0
41.0
42.0
43.0
44.0
49.0
53.0
54.0
55.0 81
56.0 56
57.0 15
63.0
5
65.0
2
67.0
3
69.0 22
70.0
2
71.0
3
84.0
4
91.0 100
92.0
4
93.0 32
94.0
1
mass
Br
Br
84 (4%), minus HBr
135 (8%)

107 (1%)
allylic
McLafferty
27 (16%)
28 (3%)
41 (42%)
42 (10%)
63 (0%)
56 (5%)
70 (3%)
84 (1%)
91.0 100
93.0 32
35
Cl and 37Cl
91.0 100
93.0 32
35
Cl and 37Cl
I
84 (4%), minus HI
183 (0%)
107 (2%)

allylic
McLafferty
27 (14%)
28 (3%)
41 (25%)
42 (3%)
63 (0%)
56 (2%)
70 (0%)
84 (0%)
15.0
1
26.0
1
27.0 16
28.0
3
29.0 21
39.0 11
40.0
2
41.0 42
42.0 10
43.0 66
44.0
2
53.0
2
54.0
1
55.0
6
56.0
5
57.0 100
mass
I
1
2
27
5
32
17
3
59
45
72
2
3
4
4
mass
58.0 4.9
69.0
.5
70.0
3
71.0
3
81.0
1
83.0 1.5
84.0
1
85.0 18
86.0
1
99.0 14
100.0
1
107.0
1
109.0
1
135.0
8
137.0
8
mass %
27.0 14
28.0
3
29.0 15
39.0
7
40.0
1
41.0 25
42.0
3
43.0 100
44.0
3
53.0
1
55.0
6
56.0
2
57.0 11
85.0 50
86.0
3
155.0
2
212.0
4
1-iodopropane 2-iodopropane
mass %
mass %
I
not possible
I
155 (0%)
42, minus HI
allylic
McLafferty
28 (3%) (2%) 27 (32%) (28%)
42 (3%) (4%) 41 (37%) (36%)
56 (0%) (0%) 63 (0%) (0%)
70 (0%) (0%)
84 (0%) (0%)
I = 127.0 (5%)
HI = 128.0 (1%)
(6%)
(2%)
15.0
2
26.0
2
27.0 32
28.0
2
38.0
2
39.0 11
40.0
2
41.0 37
42.0
3
43.0 100
44.0
3
127.0
5
128.0
1
170.0 24
15.0
1
26.0
1
27.0 28
28.0
2
38.0
2
39.0 12
40.0
2
41.0 36
42.0
4
43.0 100
44.0
3
127.0
6
128.0
2
170.0 24
Spectroscopy
Beauchamp
30
Alcohols - Key Points

1. Alcohols generally have weak M+ peaks. Tertiary alcohols often do not have an M+ peak.
However, if you had an IR, you would know an alcohol was present from the OH and CO bands.
Additional evidence would be present in the proton and carbon 13 NMR spectra, if available.
2. Loss of water (M-18) is common; more so with straight chains and less so with branched
alcohols.
H
M-18
O
H
fragmentation
R'
R'
This can lead to alkene fragmentations.

OH
OH
OH
linear
15.0
3
26.0
3
27.0 33
28.0 12
29.0 16
31.0 83
39.0 11
40.0
4
41.0 66
42.0 32
43.0 59
45.0
7
53.0
1
55.0 14
56.0 100
57.0
6
59.0 0.3
74.0 0.6
OH
has branch
has branch
has branch
15.0
2
26.0
2
27.0 10
28.0 52
29.0
6
31.0 17
39.0
3
40.0
1
41.0 12
42.0
1
43.0
9
45.0 100
53.0
1
55.0
2
56.0
2
57.0
2
59.0 20
74.0 0.2
15.0
3
26.0
1
27.0
4
28.0
1
29.0
6
31.0 27
39.0
6
40.0
1
41.0 21
42.0
1
43.0
9
45.0
1
53.0
1
55.0
2
56.0
3
57.0
8
59.0 100
74.0
0
15.0
2
26.0
2
27.0 23
28.0 12
29.0
8
31.0 40
39.0 14
40.0
3
41.0 57
42.0 59
43.0 100
45.0
4
53.0
1
55.0
6
56.0
5
57.0
3
59.0
6
74.0 13
H2C=OH
(M-29) = C2H5
(M-18) = H2O
(M-15) = CH3
M+ peak
The base peak is bolded in each example.
3. Alpha cleavage is common because a resonance stabilized carbocation can form three possible
ways in tertiary alcohols where R1 R2 R3. (two ways with 2o alcohols). Often all are
observed, when present.
R1
H
C
R3
radical cation
R1
R2
fragmentation
C
R3
R2
R2
R3
"X" lone pair electrons fill in loss of electrons at carbocation site. This is a common
fragmentation pattern for any atom that has a lone pair of electrons (oxygen = alcohol,
ether, ester; nitrogen = amine, amide; sulfur and halogens). Loss of R1, R2 or R3 is
possible.
Spectroscopy
Beauchamp
31
4. Cyclic alcohols tend to show stronger M+ peaks than linear chains.

OH
M+ = 72 (1%)
M-18 = 54 (1%)
M-28 = 44 (100%)
base peak = 44 (100%)
OH
M+ = 86 (9%)
M-18 = 68 (7%)
M-28 = 58 (14%)
base peak = 57 (100%)
OH
M+ = 100 (3%)
M-18 = 82 (46%)
M-28 = 72 (7%)
base peak = 57 (100%)
OH
M+ = 114 (2%)
M-18 = 96 (23%)
M-28 = 86 (4%)
base peak = 57 (100%)
OH
M+ = 102 (0%)
M-18 = 84 (9%)
base peak = 56 (100%)
M+ = 88 (0%)
M-18 = 70 (51%)
base peak = 42 (100%)
M+ = 74 (0.6%)
M-18 = 56 (100%)
base peak = 56 (100%)
OH
OH
OH
M+ = 116 (0%)
M-18 = 98 (6%)
base peak = 70 (100%)
5. When oxygen is present in any molecule, it is likely that mass 31 will be present.
H
Mass = 31 is almost always present when oxygen is present, especially in alcohols.
Example
OH
H
C7H16O
(-H2O)
98 (4%), minus H2O

allylic
McLafferty
27 (5%)
28 (0%)
41 (10%)
42 (4%)
55 (15%)
56 (7%)
69 (3%)
70 (5%)
84 (0%)
loss of water
from either side
M+ = 116
See alkene fragmentations earlier. The

pi bond can move around the carbon
skeleton, which can also rearrange.
98
OH
a
a
b
C7H16O
M+ = 116
C5H11
CH3
71
15
alkyl branches
15 (1%)
29 (5%)
43 (8%)
57 (4%)
71 (1%)
85 (0%)
O
45
CH
HC
CH3
101
Many types of skeletal rearrangements are possible using a such high energy electron beam.
The "31" fragment does not make sense at a 2o or 3o ROH, but is often observed (in ethers too).
H
O
CH2
31
not logical,
but observed
actual peaks
mass
27.0
29.0
31.0
39.0
41.0
42.0
43.0
44.0
45.0
46.0
55.0
56.0
57.0
69.0
70.0
83.0
98.0
101.0
%
5
5
2
3
10
4
8
7
100
2
15
7
4
3
5
9
4
4
Spectroscopy
Beauchamp
32
Ethers - Key Points

1. Ethers tend to have stronger M+ peaks than alcohols, but still can lose ROH the way that alcohols
lose H2O.
R
R = mass
H
18
32
CH3
46
C2H5
C3H7
60
O
R
fragmentation
R'
R'
from either side
2. Alpha cleavage is common from either side and further loss of the carbonyl fragment is possible.
R1
R'
R1
fragmentation
R2
R'
R3
R'
R2
R2
R3
R3
possible.
radical cation
3. Loss of an oxygen carbon branch is also possible (from either side).

R1
R1
R'
fragmentation
R2
R'
R3
R3
We only see the cations. The fragmentation

could potentially occur from either side.
radical cation
56 (24%), minus ROH

28 (4%), minus ROH
a
O
b
H
(-ROH)
OH2
M+ = 102 (4%)
46 (0%)
H
56 (24%)
loss of alcohol b
from either side
74 (0%)
C6H14O
87 (2%)
M+ = 102 (4%)
59 (100%)
CH3
43 (6%)
O
O
73 (8%)
H2C
f
O
29 (27%)
H2
C
O
allylic
27 (12%)
41 (26%)
55 (6%)
69 (0%)
d
CH3
15 (1%)
C6H14O M+ = 102 (4%)
McLafferty
28 (4%)
42 (3%)
56 (24%)
70 (0%)
84 (0%)
HO
28 (4%)
R2
45 (10%)
57 (31%)
CH2
31 (57%)
not logical,
but observed
mass
15.0
18.0
26.0
27.0
28.0
29.0
31.0
39.0
41.0
42.0
43.0
44.0
45.0
47.0
55.0
56.0
57.0
58.0
59.0
60.0
73.0
87.0
101.0
102.0
1
3
1
12
4
27
57
5
26
3
6
1
10
1
6
24
31
1
100
3
8
2
1
4
Spectroscopy
Beauchamp
33
Thiols and Thioethers - Key Points

1. The M+2 peak with a single sulfur adds an extra 4.4% to this peak relative to the M+ peak (in
addition to other M+2 contributions). Other than chlorine and bromine, this is the most
significant M+2 contributor to common organic molecules.
2. Loss of H2S (M-34) is possible for thiols and RSH for sulfides (loss of CH3SH = (M-48)).
R
M - (RSH mass)
fragmentation
H
R'
R = mass
H
34
48
CH3
C2H5
62
76
C3H7
R'
This can lead to alkene fragmentations.
3. Alpha cleavage is possible because a resonance stabilized carbocation can form three possible
ways. Often all are observed, when present.
R1
R
R1
fragmentation
R2
R3
R2
R2
R3
R3
possible.
radical cation
4. If a side chain has five or more atoms then cleavage is possible with ring formation (see the
halogens). Beta () cleavage is also reasonable.
R
S
fragmentation

will see this mass.
R = mass
H
89
103
CH3
C2H5 117
R
fragmentation

R
S

will see this mass.
R = mass
H
61
75
CH3
C2H5 89
R
Spectroscopy
Beauchamp
34
Example
SH
1-hexanethiol
C6H14S = 118
120 (5.3%)
S
butyl ethyl sulfide
C6H14S = 118
120 (4.8%)
alkyl branches
15 (1%)
29 (15%)
43 (48%)
57 (7%)
71 (0%)
85 (2%)
84 (16%), minus H2S

61 (10%)
89 (3%)

allylic
McLafferty
27 (16%)
28 (4%)
41 (35%)
42 (32%)
55 (35%)
56 (100%)
69 (25%)
70 (2%)
83 (1%)
84 (16%)
mass
15.0
26.0
S
56 (68%), minus H2S
27.0
28.0
29.0
allylic
61 (38%) McLafferty
34.0
27 (36%) 35.0
28 (9%)
41 (49%) 39.0
CH3 42 (4%)
55 (17%) 40.0
56 (68%)
H2S = 34 (1%)
69 (0%) 41.0
S
70 (0%)
83 (0%) 42.0
84 (0%)
43.0
45.0
75 (100%)
46.0
47.0
S
48.0
S
53.0
(M-29) = 89 (25%)
(M-57) = 89 (38%)
54.0
alkyl branches
15 (1%)
S
29 (50%)
43 (4%)
57 (0%)
71 (0%)
89 (25%)
85 (0%)
1 55.0 35
16 56.0 100
4 57.0
7
15 59.0
2
2 60.0
2
9 61.0 10
2 62.0
1
35 69.0 25
32 70.0
2
48 83.0
1
2 84.0 16
4 85.0
2
2 89.0
3
15 118.0 30
1 119.0
2
2 120.0 1.6
3
mass
%
1
3
36
9
50
1
9
11
2
49
4
4
12
12
48
6
2
1
2. Loss of CO with extensive rearrangement is common.

R
R1
R
fragmentation
loss of carbon
monoxide...?
R =
H
CH3
C2H5
radical cation
mass
65
79
93
3. A hydroxy tropylium ion with no other substituents has a m/e = 107.

R
OH
R'
R1
H
fragmentation
O
radical cation
Lots of
resonance.
55.0 17
56.0 68
57.0 17
58.0
3
59.0
6
60.0
6
61.0 38
62.0 47
63.0 20
75.0 100
76.0
8
77.0
5
89.0 25
90.0
3
103.0
2
118.0 56.4 = M+
119.0
4
120.0 2.7 = M+2
1. Phenols tend to have intense M+ peaks. (See below = 100% and 36%.)
OH
Phenols - Key Points
mass
mass
26.0
27.0
28.0
29.0
35.0
39.0
40.0
41.0
42.0
43.0
44.0
45.0
46.0
47.0
48.0
53.0
54.0
R =
CH3
C2H5
etc.
mass
107
121
Spectroscopy
Beauchamp
35
Examples
mass %
OH
alkyl branches
15 (0%)
29 (0.8%)
43 (0.4%)
57 (0%)
71 (0%)
85 (0%)
phenol
C6H60 = 94 (100%)
M+1 = (7%)
OH
p-ethylphenol
27
41
55
69
83
C6H60 = 122 (36%)

M+1 = (3%)
(3%)
(1%)
(3%)
(0%)
(0%)
39 (14%)
65 (17%)
alkyl branches
15 (0.4%)
29 (0.4%)
43 (0.4%)
57 (0%)
71 (0%)
85 (0%)
27.0
37.0
38.0
39.0
40.0
47.0
50.0
51.0
53.0
55.0
61.0
OH
R=H
65 (3%)
R=CH3 79 (2%)
R=C2H5 93 (1%)
107 (100%)
OH
allylic R
mass %
27.0
38.0
39.0
41.0
50.0
51.0
52.0
53.0
55.0
62.0
63.0
39 (6%)
2
2
4
14
9
4
3
3
2
7
1
3
1
6
1
3
5
3
2
3
1
2
mass %
62.0
2
63.0
4
64.0
1
65.0 17
66.0 23
67.0
2
74.0
1
93.0
2
94.0 100
95.0
7
mass
65.0
3
77.0 13
78.0
3
79.0
2
91.0
4
94.0
1
103.0
2
107.0 100
108.0
8
121.0
3
122.0 36
123.0
3
121 (3%)
Amines - Key Points

1. Amines often have weak or absent M+ peaks. An odd number of nitrogen atoms produces an odd
molecular ion peak.
H2
C
H3C
H2
C
H
N
CnH2n+2+NOm
H3C
H
Molecules made with an odd number of
nitrogen atoms have odd molecular masses
because they have an odd number of hydrogens.
CnH2n+2Om
Molecules made with C, H, S, O, halogens

and an even number of nitrogen
atoms have even molecular masses.
2. Alpha cleavage is usually a major fragmentation pattern in a manner similar to alcohols and
ethers.
R1
R1
R'
R"
R3
radical cation
R2
fragmentation
R'
R"
R3
R2
R'
R"
R3
resonance
R2
all R = H
one CH3
C2H5
etc.
The fragment mass depends on what is present in the "R" groups. If all
R groups are "H" (H2N=CH2 ) then the mass will be 30, which shows up
in almost every amine compound examined, even tertiary amines.
mass
30
44
58
Spectroscopy
Beauchamp
36
3. Loss of a branch at nitrogen is also possible in a manner similar to alcohols and ethers.
R1
R1
R'
R"
R3
fragmentation
R2
R'
radical cation
R"
R3
R2
The fragment mass depends on what is present in the

"R" groups and which fragment retains the cation charge.
4. Aromatic amines generally show intense M+ peaks.
NH2
R1
odd mass
R'
H
1. fragmentation
2. rearrangement
Lots of
resonance.
N
H
radical cation
odd mass
R'
R' =
H
CH3
C2H5
etc.
mass
106
120
134
even mass
Examples
b
H
N
H
loss of amine
from either side
N
H
56
56
n-isobutyl-sec-butylamine
M+ = 129 (1%)
C8H19N
d
(-ROH)
56 (6%), minus RNH2

McLafferty
allylic
28 (8%)
27 (7%)
42 (4%)
41 (18%)
56 (6%)
55 (7%)
70 (2%)
69 (0%)
84 (2%)
C2H5
N
H
29 (18%)
d
n-isobutyl-sec-butylamine
M+ = 129 (1%)
100 (18%)
N
H
CH3
15 (1%)
114 (8%)
e
NH2
86 (66%)
N
H
C3H7
43 (2%)
30 (100%)
CH2
not logical, but observed
and is even the base peak
alkyl branches
29
43
57
71
85
(18%)
(2%)
(24%)
(0%)
(0%)
mass
%
15.0
1
18.0
2
27.0
7
28.0
8
29.0 18
30.0 100
31.0
1
39.0
5
41.0 18
42.0
4
43.0
2
44.0 53
45.0
1
55.0
7
56.0
6
57.0 24
58.0 20
70.0
2
72.0
6
84.0
2
86.0 66
87.0
4
100.0 67
101.0
5
114.0
8
128.0
1
129.0
1
Spectroscopy
Beauchamp
37
a
N
H
b
H
(-ROH)
H2N
28 (5%)
73 (0%)
CH3
N
H
15 (1%)
M+ = 101 (9%)
butylethylamine
86 (2%)
H2
C
N
H2C
58 (100%) H
mass
15.0
18.0
27.0
28.0
29.0
30.0
39.0
41.0
42.0
43.0
44.0
56.0
57.0
58.0
59.0
86.0
100.0
101.0
N
H
C6H15N
See alkene
fragmentations above.
56 (3%)
M+ = 101 (9%) H
butylethylamine
NH2
45 (0%)
43 (2%)
CH3
N
H
C6H15N M+ = 101 (9%)
butylethylamine
HN
NH2
72 (0%)
29 (8%)
CH2
NH4
18 (1%)
%
1
1
5
5
8
33
2
4
3
2
10
3
3
100
4
2
2
9
30 (33%)
NH
57 (3%)
44 (10%)
Carbonyl Compounds (aldehydes, ketones, esters, acids, amides, acid chlorides) - Key Points
1. M+ peaks are often observable (though they can be weak or absent). Several examples are
provided below.
2. Alpha cleavage is possible from either side. Usually the more stable cation forms in greater
amount. It is best to look for both possibilities.
O
R1
R2
R1
C
R1
R2
radical cation
R1 or R2 can be lost from
aldehydes, ketones, acids,
esters, amides, acid chlorides,
etc.
R2
An oxygen lone pair paritally fills in the loss of electrons at the

carbocation site via resonance. This is a common fragmentation
pattern for any carbonyl compound and can occur from either
side, though some are more common than others.
Spectroscopy
Beauchamp
38
3. Alpha cleavage can be followed by loss of CO (another -28). That would leave the side branches
as observable peaks, plus any further fragment branches from those peaks.
R1
R1
R2
O
loss of
R2
R1
R2
Subsequent loss of CO is possible

after fragmentation, so not only
can you see loss of an branch you
can also see the mass of an branch.
4. McLafferty rearrangements are common with at least three carbons in a side chain. Cleavage occurs
between C and C.
R
H
O
R1
Positive charge can be on

either fragment, which
typically has an even mass.
R
R
C
R1
= alpha position
= beta position
= gamma position
R R
radical cation
R R
R
C
R
R
This is another common fragmentation pattern for carbonyl compounds (and other pi systems as well: alkenes, alkynes, aromatics,
nitriles, etc.). If the pi bond has at least 3 additional nonhydrogen atoms attached and a hydrogen on the "gamma" atom, the branch
can curve around to a comfortable 6 atom arrangement and the pi bond can pick up a hydrgen atom and cut off a fragment between
the C and C positions. The positive charge can be seen on either fragment and usually the fragments have an even mass (unless
there is an odd number of nitrogen atoms). The mass of either fragment depends on what "R"s are.
The bottom line is there are several ways that carbonyl (C=O) functionality can fall apart. It is
best to look for all possibilities. See the last example in this example list below (ketone).
Carbonyl Examples
Carboxylic Acids
Loss of side chain, then CO (?)
H
17 (0.4%)
O
a
OH
HO
C6H12O2 = 116 (0%)
b
HO
45 (100%)
McLafferty
H
O
HO
HO
C6H12O2 = 116 (0%)
hexanoic acid
60 (100%)
McLafferty
56 (8%)
28 (4%)
42 (7%)
70 (3%)
mass %
18.0
2
26.0
2
O
27.0 17
28.0
4
C
29.0 14
99 (0.8%)
71 (2%)
30.0
1
28 (5%)*
31.0
2
alkyl branches 39.0 10
40.0
2
15 (0.9%)
41.0 26
29 (14%)
42.0
7
71 (2%)
43 (14%)
43.0 14
57 (12%)
45.0
9
71 (2%)
53.0
1
*28 could also be ethene
85 (0.4%)
55.0 10
99 (0.8%)
56.0
8
alkenes
57.0 12
58.0
6
allylic
59.0
3
60.0 100
O
61.0
9
HO
69.0
3
41 (26%)
70.0
3
55 (10%)
71.0
2
73.0 44
69 (3%)
(M-29) = 87 (11%)
74.0
7
83 (1%)
83.0
1
87.0 11
Spectroscopy
Beauchamp
39
Esters
mass
CH3O
C7H14O2 = 130 (0.4%)
McLafferty
H
O
CH3O
C7H14O2 = 130 (0.4%)
methyl hexanoate
15.0 10
18.0
1
26.0
1
O
27.0 11
H3CO
O
a
28.0
2
29.0 12
31 (2%)
C
31.0
2
71 (10%)
39.0
7
99 (19%)
28 (2%)*
40.0
1
alkyl branches 41.0 17
42.0
6
O
15 (10%)
43.0 31
29
(12%)
44.0
2
b
43 (31%)
45.0
2
57 (4%)
71 (10%)
CH3O
53.0
1
71 (10%)
59 (15%)
55.0
9
85 (0.1%)
56.0
2
99 (19%)
57.0
4
alkenes
59.0 15
69.0
2
McLafferty
H
O
70.0
3
allylic
CH3O
O
71.0 10
73.0
1
74.0 100
75.0
5
56 (2%)
H3CO
41 (17%)
87.0 32
55 (9%)
(M-29) = 101 (8%)
88.0
4
74 (100%)
28 (2%)
69 (2%)
99.0 19
42 (6%)
83 (0%)
100.0
1
70 (3%)
101.0
8
Aldehyde

H
1 (?)
a
OH
99 (0.4%)
C6H12O = 100 (0.4%)
b
H
hexanal
29 (33%)
alkenes
McLafferty
McLafferty
H
O
allylic
H
56 (82%)
H
C6H12O = 100 (0.4%)
hexanal
71 (7%)
28 (8%)*
alkyl branches
15 (2%)
29 (33%)
43 (55%)
57 (38%)
71 (7%)
71 (7%)
85 (0.3%)
*28 could also be ethene 99 (0.4%)
44 (100%)
28 (8%)
42 (11%)
70 (0%)
41 (69%)
55 (15%)
69 (1%)
83 (1%)
(M-29) = 71 (7%)
mass
%
15.0
2
18.0
1
26.0
3
27.0 34
28.0
8
29.0 33
30.0
2
31.0
2
38.0
2
39.0 20
40.0
4
41.0 69
42.0 11
43.0 55
44.0 100
45.0 20
50.0
1
51.0
1
53.0
3
54.0
2
55.0 15
56.0 82
57.0 38
58.0
9
60.0
4
67.0
8
69.0
1
71.0
7
72.0 17
73.0
2
81.0
1
82.0 13
83.0
1
Spectroscopy
Beauchamp
40
Ketone
O
mass
15 (4%)
H
O
CH3
C
28 (2%)*
99 (4%)
b
O
C7H14O = 114 (10%)
2-heptanone
71 (14%)
43 (100%)
71 (14%)
alkyl branches
15 (4%)
29 (9%)
43 (100%)
57 (2%)
71 (14%)
85 (3%)
99 (4%)
alkenes
McLafferty
H
McLafferty
allylic
O
56 (2%)
C7H14O = 114 (10%)
58 (91%)
41 (12%)
55 (5%)
69 (0%)
83 (0%)
28 (2%)
42 (3%)
70 (0%)
2-heptanone
(M-29) = 85 (3%)
15.0
4
18.0
2
27.0
9
28.0
2
29.0
9
39.0
7
40.0
1
41.0 12
42.0
3
43.0 100
44.0
2
45.0
1
53.0
1
55.0
5
56.0
2
57.0
2
58.0 91
59.0 15
71.0 14
72.0
4
85.0
3
99.0
4
113.0
2
114.0 10
115.0
1
Amide
NH4
18 (2%)=NH4
a
a
99 (1%)
98 (0.2%)
O
b
O
H2N
C6H13NO = 115 (0.6%)
b
H2N
hexanamide
44 (29%)
71 (2%)
C
28 (2%)*
71 (2%)
alkyl branches
15 (0%)
29 (8%)
43 (26%)
18 could be
57 (2%)
NH4 or H2O
71 (2%)
85 (0%)
*28 could also be ethene 99 (1%)
alkenes
McLafferty
H
H2N
H2N
C6H13NO = 115 (0.6%)

hexanamide
McLafferty
59 (100%)
allylic
H2N
56 (0%)
28 (2%)
42 (4%)
70 (0%)
41 (12%)
55 (4%)
69 (0%)
83 (0%)
(M-29) = 86 (9%)
mass
18.0
2
27.0
9
28.0
2
29.0
8
39.0
6
41.0 12
42.0
4
43.0 26
44.0 28
45.0
1
55.0
4
57.0
2
59.0 100
60.0
3
71.0
2
72.0 19
73.0
4
86.0
9
99.0
1
Spectroscopy
Beauchamp
41
Full example for 2-methyl-4-heptanone

2-methylheptan-4-one
O
27.0
28.0
29.0
39.0
40.0
41.0
42.0
43.0
44.0
53.0
55.0
56.0

57 = base
C8H16O
MW = 128
43
71
41
58
57.0 100
58.0
27
59.0
1
69.0
2
70.0
1
71.0
70
72.0
3
85.0
72
86.0
11
113.0
6
128.0
23
129.0
2
17
2
17
11
2
36
5
73
3
1
2
1
M+ = 128
27 29
39
28
20
30
86
42
50
40
H
O
2 McLafferty
possibilities
a
C8H16O = 128 (23%)
70
60
100
90
a = only see the fragment that

retains the positive charge
H
O
b = only see the fragment that

H
O
42 (5%)
c
c = only see the fragment that

Lose
CO
Lose
right
branch
C
28 (2%)
57 (100%)
C8H16O = 128 (23%)
43 (73%)
71 (70%)
d = only see the fragment that

O
Lose
CO
C
C8H16O = 128 (23%)
28 (2%)
100 (0.4%)
86 (11%)
130
120
110
100
a and b
Lose
left
branch
80
113
85 (72%)
C
43 (73%)
57 (100%)
28 (2%)
reasonable
mass peaks
128
100
86
85
71
57
43
42
28
Spectroscopy
Beauchamp
42
Nitriles - Key Points

1. Usually have weak M+ peaks. An odd number of nitrogen atoms produces an odd molecular ion
peak.
H2
C
H3 C
Compare.
CnH2n-2+N
C
N
H2
C
CnH2n-2
H3C
C3H5N
MW = 55
Nitriles made with an odd number of

nitrogen atoms have odd molecular masses
because they have an odd number of hydrogens.
C4H6
CH MW = 54
Alkynes made with C and H

have even molecular masses.
2. With side chains of three carbons or longer McLafferty rearrangements are possible.
H
H
N
C
fragmentation
C
CH
odd
mass
HN
...or...
C
CH
odd
mass
even
mass
C
R
mass = 28 (all H)
mass = 41 (R = H)
42 (1R = CH3)
55 (R = CH3)
56 (1R= CH2CH3)
69 (R= CH2CH3)
70 (1R = C3H7)
83 (R = C3H7)
Nitrile McLafferty can cut off a fragment between the C and C positions. Either fragment
can be observed (if the cation) and the one with the nitrogen atom will show an odd mass.
radical cation
3. Alpha cleavage is possible.

N
R
odd
mass
C
C
radical cation
fragmentation
odd
mass
The detector sees cations.
even
mass
C
C
Radicals are pumped away.
Spectroscopy
Beauchamp
43
Example
mass
Loss of side chain, then CN (?)
H
N
a
hexanenitrile
C
26 (5%)
71 (1%)
C6H11N = 97 (0.8%)
perhaps...?
H
NH
b
54 (82%)
55 (42%)
56 (4%)
43 (32%)
42 (14%)
41 (100%)
McLafferty
hexanenitrile
CH
or
HCNH
allylic
N
56 (4%)
C6H11N = 97 (0.8%)
H2C
alkenes
McLafferty
N
27 (33%)
H
NH
alkyl branches
15 (2%)
29 (43%)
43 (32%)
57 (28%)
71 (1%)
85 (0%)
41 (100%)
28 (9%)
42 (14%)
70 (4%)
41 (100%)
55 (42%)
69 (23%)
83 (1%)
15.0
2
26.0
4
27.0 33
28.0
9
29.0 43
30.0 1.6
37.0
1
38.0
3
39.0 22
40.0
5
41.0 100
42.0 14
43.0 28
50.0
1
51.0
2
52.0
3
53.0
4
54.0 82
55.0 42
56.0
4
57.0 32
58.0
1
66.0
1
67.0
1
68.0 30
69.0 23
70.0
4
71.0
1
82.0 24
83.0
1
96.0 12
97.0
1
similar masses
These are some of the more common organic functional group fragmentation patterns in EI mass
spectroscopy. Most of the examples presented here are very simple monofunctional compounds.
When more functional groups are present, more complexity is expected and it gets increasingly difficult
to make definitive conclusions on the basis of mass spectroscopy. Even with simple monofunctional
group compounds, we have seen that functional groups can change through rearrangements possible
due to the high energy of ionization (e.g. alkanes alkenes). If you specialize in other specific
patterns of functionality in your work, you will become familiar with useful mass spectral features of
those groups. For us, the molecular weight is the primary information we seek from a mass spectrum,
assisting us toward our main goal of determining organic structures from the available spectra.
A one page summary sheet showing many of the fragmentation patterns above is provided on the
next page, and the following page shows common fragments and their extended variations. These two
pages will explain most of what you will encounter as a burgeoning mass spectroscopist.
Spectroscopy
Beauchamp
44
Common fragmentation patterns in mass spectroscopy (only cations are observed)

1.
Fragment a branch next to a pi bond ( cleavage)

R
C
radical cation
pi bond of an alkene,
alkyne or aromatic
2.
R
C
Characteristic carbocation stability also applies.

C
3o R
Pi electrons partially fill in loss of electrons at carbocation

site via resonance. This is a common fragmentation
pattern for alkenes, alkynes and aromatics.
> 2o R > 1o R > CH3
We only see the cationic fragments. The

radical fragments are lost to the vacuum.
Fragment a branch next to an atom with a lone pair of electrons

R
X
X lone pair partially fills in loss of electrons at carbocation site via resonance. This is a common
fragmentation pattern for any atom that has a lone pair of electrons (oxygen = alcohol, ether, ester;
nitrogen = amine, amide; sulfur = thiol, sulfide, etc.) Alcohols often lose water (M-18), ethers can
lose ROH, primary amines can lose ammonia (M-17), etc.
radical cation
adjacent lone pair ofan
oxygen or nitrogen atom
3.
Fragment a branch next to a carbonyl (C=O) bondand possible subsequent loss of carbon monoxide, CO
loss of
a
R1
b
R1
R1
O
O
R2
R1
R1 or R2 can be lost
from aldehydes, ketones,
acids, esters, amides...etc.
4.
R2
loss of
O
R2
R2
O
An oxygen lone pair partially fills in the loss of electrons

at the carbocation site via resonance. This is a common
fragmentation pattern for any carbonyl compound and
can occur from either side, though some are more common
than others.
Subsequent loss of CO is possible after

fragmentation, so not only can you
see loss of an a branch, you can also
see the mass of an branch.
McLafferty Rearrangement
H
H
O
C
R1
C
C
radical cation
C
R1
cation fragment
OR
cation fragment
The positive charge can be on

either fragment, which typically
have even masses (unless an odd
number of N is present).
= alpha position
= beta position
= gama position
This is another common fragmentation pattern for carbonyl compounds (and other pi systems as well: alkenes, aromatics, alkynes, nitriles,
etc). If the pi bond has at least 3 additional nonhydrogen atoms attached and a hydrogen on the "gama" atom, the branch can curve around
to a comfortable 6 atom arrangement and the pi bond can pick up a hydrogen atom and cut off a fragment between the C and C positions.
The positive charge can be seen on either fragment and usually the fragments have an even mass (unless there is an odd number of nitrogen
atoms in the observed fragment).
Knowing these few fragmentation patterns will allow you to make many useful predictions and interpretations in mass spectroscopy. Also loss
of small molecules is common, producing an even mass if no nitrogen is present: H2O = 18, H2S = 34, CH3OH = 32, C2H5OH = 46, NH3 = 17,
CH3CO2H = 62, HF = 20, HCl = 36/38, HBr = 80/82, etc. This can even include loss of an alkane equivalent (R branch plus H, 16, 30, 44, etc.)
to leave behind an alkene cation that can also generate alkene fragments, which is shown later in the notes (McLafferty & allylic). Certain
atoms generate characteristic M+2 peak patterns: 35Cl/37Cl = 75/25 ration, 79Br/81Br = 50/50 ratio, 32S/34S = 95/5 ratio. Any peak 1 amu larger
than the one in front of it shows about 1% of the front peak for every carbon atom in the formula (e.g. C6 = M+ / M+1 ratio of 100% / 6%).
Spectroscopy
Beauchamp
45
A sampling of common and/or miscellaneous peaks that are often seen, (even when they don't make sense). Whatever the
initial mass is, a series of masses increased by increments of 14 (CH2)n reveals additional "logical" fragment masses. Remember,
we only see the cationic fragments.
R
CH3 = 15
CH3CH2 = 29
C3H7 = 43
C4H9 = 57
C5H11 = 71
C6H13 = 85
mass = 39 (R = H)
53 (R = CH3)
67 (R= CH2CH3)
also works for
CH2
R
C
H
mass = 41 (R = H)
55 (R = CH3)
69 (R= CH2CH3)
83 (R=C3H7)
H2N
mass = 65 (R = H)
79 (R = CH3)
93 (R= CH2CH3)
mass = 91 (R = H)
105 (R = CH3)
119 (R= CH2CH3)
C
H2
mass = 29 (R = H)
43 (R = CH3)
mass = 42 (R = H)
57 (R= CH2CH3)
H
56 (R = CH3)
mass = 27
RO
C
O
71 (R = C3H7)
mass = 77
70 (R= CH2CH3)
85 (R = C4H9)
mass = 45 (R = H)
84 (R=C3H7)
99 (R = C5H11)
59 (R = CH3)
105 (R = C6H5)
73 (R = CH2CH3)
45
(R= OH)
87 (R = C3H7)
Loss of small molecules via elimination reactions.
59 (R= OCH3)
44 (R= NH2)
HCl
HBr
H2O H2S CH3OH C2H5OH NH3 CH3CO2H
HF
80 (50%)
36 (75%)
34
mass = 18
32
46
17
20
62
82 (50%)
38 (25%)
mass = 44
McLafferty Rearrangement Possibilities

O
Notice!
even masses
(without N)
R2
R1
McLafferty
R1
variable mass,
CH2
44 (R = H)
58 (R = CH3)
mass =
72 (R = CH2CH3)
86 (R = C3H7)
60 (R = OH)
74 (R = OCH3)
59 (R = NH2)
78 (R = Cl)
HC
R2
C
R
C
H2
CH2
(can sometimes see this

fragment if it retains the
cation charge)
mass = 28 (R = H)
42 (R = CH3)
56 (R= CH2CH3)
70 (R = C3H7)
84 (R = C4H9)
Similar Patterns - positive charge is written on both fragments to show that either fragment might be seen at the detector
H
CH2
R2
R1
R2
R1
mass = 42 (R = H)
56 (R = CH3)
70 (R= CH2CH3)
84 (R = C3H7)
R1
R2
R
R1
mass = 92 (R = H)
106 (R = CH3)
120 (R= CH2CH3)
134 (R = C3H7)
H
C
C
R2
C
H2
C
H2
H2C
CH2
R2
R1
C
H2
R1
C
H2
R2
R2
R1
CH2
mass = 40 (R = H)
54 (R = CH3)
68 (R= CH2CH3)
82 (R = C3H7)
R2
CH2
R1
mass = 41 (R = H)
55 (R = CH3)
69 (R= CH2CH3)
83 (R = C3H7)
Spectroscopy
Beauchamp
46
Very Brief Description of Various Mass Spec Techniques There are other techniques others besides those
mentioned below. If you need practical knowledge of the theory and instrumentation of these experimental
techniques, you will need to consult specialty references or textbooks.
1.
In electron impact (EI), vaporized sample is bombarded with a very high energy beam of
electrons at about 70 eV (1600 kcal/mole) knocking an electron out of a bonding orbital,
forming a radical cation. EI is relatively inexpensive and additional information can be obtained
from fragmentation patterns. However fragmentation can prevent seeing the molecular ion peak
(parent peak), which may necessitate using another approach, such as CI (next).
2.
Chemical ionization (CI) introduces a reagent gas in the source at higher concentration and the
gas is ionized by electrons at 500 eV. The reagent gas acts as a strong acid to protonate a basic
site in the molecule of interest (at much lower energy to minimize fragmentation). This adds
some mass to the sample, such as +1 (proton) or +(mass of gas). The protonated reagent gas can
also abstract a proton (forming M-1). Generally, one can see the molecular mass peak (+1)
much more clearly using CI. However, the sample must be vaporized and thermally stable
which limits many biological samples or high molecular weight samples. If EI-MS does not
produce an M+ peak, we will provide a hypothetical CI mass peak (and always assume it
represents M+1). If we have access to a proton and 13C NMR we can use those spectra to
provide a proton and carbon count. Both IR and 13C can provide information about the
functional groups that are present which will give us a clue about how many oxygen and
nitrogen atoms are present. If any larger than expected M+2 peaks show up (molecular ion or in
a fragment) we might gain information about chlorine, bromine or sulfur. Using such a
combination approach could also lead us to a molecular formula.
3.
In fast atom bombardment (FAB), a solution of the sample in a matrix of low volatility is
bombarded with neutral fast heavy atoms (Xe, Ar at 7 kev). It is a good method for molecules
up to 20 KDa (biological molecules), and one can sequence some proteins. However the matrix
usually produces background peaks at nearly every mass. One can usually see ions at M+1 or
M-1.
4.
In electrospray (ES), a solution of the sample is sprayed at atmospheric pressure through a 2-5
kV potential and the resulting droplets are electrostatically charged. There is no matrix
background, multicharged species, molecules up to 200 kDa can be analyzed. However the
method is susceptible to contamination of ions in the mist solution and nonpolar molecules are
not detected.
5.
In matrix assisted laser desorption ionization (MALDI), ions are accelerated to an energy of 3kV
for mass analysis. A matrix absorbs energy produced by a laser and there is minimal
fragmentation with better resolution than ES and FAB, especially at high mass.
6.
In field desorption (FD), a sample is deposited directly onto anode where a high electric field
produces desorption and ionization. There are very few fragmentations and is a preferred
method for synthetic polymers. However samples may begin to decompose before inserted to
the direct inlet. It is not good for high sensitivity and biological samples and has poor
reproducibility.
Spectroscopy
Beauchamp
Mass Spec Problem Set
47
Name ___________________________________
1. If the molecular ion peak is 142, what molecular formula does the rule of 13 predict if the structure is a
hydrocarbon? What formula is predicted if there is one oxygen atom? Two oxygen atoms? Two nitrogen
atoms? What is the degree of unsaturation for each possibility above (4 calculations)? Draw one
structure for each possibility. What if the molecular ion peak is 143 (same questions)?
2. Both CHO+ and C2H5+ have fragment masses of approximately 29, yet CHO+ has a M+1 peak of 1.13%
and M+2 peak of 0.20%, whereas C2H5+ has a M+1 peak of 2.24% and M+2 peak of 0.01%. High
resolution mass spec shows CHO+ to have a different fragment mass than C2H5+. Explain these
observations and show all of your work. Helpful data follow.
Element
H
H
C
C
O
O
O
Average
Atomic Mass
1.00797
12.01115
15.9994
Nuclide
(Relative Abundance) Mass
1
H (100)
1.00783
2
H (0.016)
2.01410
12
C (100)
12.00000
13
C (1.08)
13.00336
16
O (100)
15.9949
17
O (0.04)
16.9991
18
O (0.20)
17.9992
3. What relative abundance would the characteristic M (let M be 100%), M+2, M+4, M+6 mass peaks have
for: (a) tribromo, Br3 substituted alkane, (b) trichloro, Cl3, substituted alkane and (c) bromodichloro,
BrCl2 substituted alkane? Show your work. You can use these approximate probabilities (P):
P35Cl = 0.75,
P37Cl = 0.25,
P79Br = 0.50,
P81Br = 0.50
4. Radical cations of the following molecules (e- + M M.+ + 2e-) will fragment to yield the indicated
masses as major peaks. The molecular ion peak is given under each structure. The base peak is listed as
100%. Other values listed represent some relatively stable possibilities (hence higher relative abundance),
or common fragmentations (expected), even if in low amount. For the fragments with arrows pointing at
them, show what the fragment is and how it could form from the parent ion. This may be as easy as
drawing a line between two atoms of a bond, or it may require drawing curved arrows to show how
electrons move (e.g. McLafferty). Explain why each fragment is reasonable. This may involve drawing
resonance structures or indicating special substitution patterns (3o R+ > 2oR+ > 1oR+ > CH3+). If a
fragment has an even mass and there is a pi bond, think McLafferty (unless an odd number of nitrogen
atoms are present). Even masses can also be formed by elimination of a small molecule such as loss of
water from an alcohol or loss of an alcohol from an ether or a retro-Diels-Alder reaction, etc. Make sure
you show this.
Peaks with arrows are expected from the functional group shown. Most of the other peaks should be
explainable using the examples in the prior discussions. See how many you can explain.
Spectroscopy
Beauchamp
a.
CH3
H 3C
CH3
C
H 3C
C
H2
M+ = 86
m/e
% base
27.0
29.0
41.0
42.0
43.0
55.0
56.0
57.0
71.0
72.0
86.0
17.2
33.6
49.1
5.6
100.0
11.3
28.0
98.3
76.7
4.5
<1.0
c.
M+ = 84
48
b.
H2
C
H2
C
H 3C
H2
C
C
H2
C
H2
CH3
C
H2
M+ = 114
Is there a logical peak that is missing?
m/e
% base
27.0
41.0
42.0
43.0
56.0
69.0
84.0
10.0
49.5
24.7
11.2
100.0
35.4
17.5
d.
M+ = 84
You might have to
move the C=C around.
% base
27.0
41.0
42.0
43.0
56.0
69.0
84.0
20.8
68.2
31.4
100.0
49.8
16.9
11.7
f.
m/e
CH3
C
H2
M+ = 120
Use a bridging ring to make 105.
m/e
% base
65.0
77.0
91.0
92.0
105.0
120.0
7.2
2.7
100.0
10.8
3.8
25.9
27.0
29.0
41.0
42.0
43.0
55.0
56.0
57.0
70.0
71.0
85.0
114.0
20.1
27.4
43.8
15.3
100.0
11.4
18.4
33.5
12.1
20.4
26.5
6.0
% base
27.0
32.9
29.0
24.4
H2
C
39.0
54.9
C
40.0
61.2
H3C
C
H2
41.0
22.7
42.0
22.3
M+ = 68
53.0
44.0
67.0 100.0
68.0
15.3
Don't remove the sp C-H, there is a better
spot to lose an H atom (resonance).
CH
g.
H2
C
% base
No easy explanation for

56, but if ring opens and
forms alkene, McLafferty
might work.
e.
m/e
m/e
H2
C
H3C
H2
C
C
H2
OH
M+ = 74
56 is an even mass, but not
McLafferty. A small molecule
might help explain it.
m/e
% base
27.0
29.0
31.0
41.0
42.0
43.0
55.0
56.0
57.0
74.0
32.7
16.1
83.4
65.6
31.6
59.3
14.1
100.0
5.9
<1.0
Spectroscopy
Beauchamp
h.
OH
CH3
CH
H3C
C
H2
M+ = 74
Peak 31 is harder to
explain, but common.
j.
m/e
% base
27.0
28.0
29.0
31.0
41.0
43.0
45.0
56.0
59.0
74.0
9.8
51.5
6.0
16.8
11.7
9.2
100.0
1.5
20.5
<1.0
H 3C
C
H2
NH2
M+ = 73
Peak 30 dominates. Think of a
small molecule elimination for
peak 56.
l.
O
H2
C
C
H
C
H2
CH3
M+ = 72
29 is different than C2H5+
44 is an even mass, so...
n.
m/e
H2
C
C
C
H2
CH3
M+ = 88
An even mass strikes again
at 60 and 45 is not common,
but expected here.
p.
27.0
23.0
28.0
7.9
O
CH3
29.0
34.9
H 3C
C
C
31.0 100.0
H2
H2
42.0
4.1
43.0
39.8
M+ = 88
59.0
98.3
73.0
3.3
88.0
25.7
28 and 42 are even, but not McLafferty. Think like "g", but
"organic" water. 31 requires some drastic rearrangements.
m/e
% base
27.0
29.0
30.0
43.0
56.0
73.0
3.5
2.1
100.0
1.2
1.2
7.3
m/e
% base
27.0
29.0
41.0
43.0
44.0
57.0
72.0
73.5
54.8
69.1
75.3
100.0
23.3
53.6
m/e
% base
27.0
29.0
41.0
43.0
45.0
60.0
73.0
88.0
13.6
8.1
16.3
14.1
9.9
100.0
32.5
2.6
m/e
H2
C
C
C
H2
CH3
M+ = 69
Normally 41 would be even,
but there is nitrogen present.
27.0
29.0
40.0
41.0
42.0
54.0
69.0
% base
H2
C
% base
28.6
66.3
3.8
100.0
4.0
1.2
0.2
H2
C
C
H 3C
CH3
C
H2
C
H2
M+ = 100
43 is different than C3H7+
m.
H3C
H2
C
C
H2
CH3
M = 102
74 is an even mass.
% base
27.0
29.0
43.0
57.0
58.0
85.0
100.0
8.2
14.8
100.0
15.8
49.8
6.4
8.0
H2
C
C
H2
CH3
M+ = 87
Normally 59 would be even,
but there is nitrogen present.
q.
M+ = 136
Two famous names goes with 68.
% base
27.0
47.0
29.0
9.2
41.0
45.3
43.0 100.0
59.0
22.2
71.0
49.9
74.0
64.2
87.0
16.4
102.0
1.4
m/e
O
C
H 2N
m/e
m/e
o.
HO
i.
k.
H2
C
H2
C
49
27.0
29.0
41.0
43.0
44.0
59.0
71.0
72.0
87.0
% base
26.6
26.1
53.4
32.2
66.3
100.0
8.0
19.2
2.9
m/e
% base
27.0
41.0
68.0
91.0
92.0
95.0
121.0
136.0
9.3
19.3
100.0
12.7
18.8
7.6
19.5
22.6
Spectroscopy
Beauchamp
50
Problem 11 On the following pages are 22 compounds (these are lettered A-V) from the 22 functional
groups numbered below. Try to match each spectrum (A-V) to the class of functional group numbered 1-22,
and then try to solve the exact structure of each compound. These are simple monofunctional group
compounds. Explain the major peaks that helped decide on your structure. Why are these peaks formed in
preference to others (what is the reason for their special stability)?
Classes of compounds
1. alkane
2. branched alkane
3. cycloalkane
4. alkene
5. alkyne
6. aromatic
7. fluorinated alkane
8. chlorinated alkane
9. brominated alkane
10. iodinated alkane
11. alcohol
12. ether
13. phenol
14. aldehyde
15. ketone
16. ester
17. acid
18. amine
19. amide
20. acid chloride
21. sulfide
22. thiol
A few hints are given with some of the spectra to help you match structures with the functional groups
mentioned above. The mass of each peak is listed with its percent of the base peak. The IR spectra should also
give you some functional group hints. Remember, not every wave number is interpretable.
Major peaks
answer (remove) oct-1-yne
Sample A
mass percent
Mass Spec - Only larger and/or significant peaks are shown.

Hint: No N or O. Explain peaks at 67, 53 and 39. Peak 54 associated with McLafferty.
26
28
29
39
40
41
42
43
50
51
52
53
54
55
65
67
68
81
82 =
%T
100
725
1375
1385
2120
50
1470
3310
2960-2850
650
0
4000
3500
3000
2500
2000
1500
= wavenumber = cm-1
1000
100%
500
3
5
6
36
25
64
16
49
6
8
4
15
27
3
5
100 (base)
6
10
M+
67 = base peak
75%
41
43
50%
39
25%
40
42
54
53
81
M+ peak = 82
(very small)
0%
20
30
40
50
60
70
m/e
80
90
100
110
Spectroscopy
Beauchamp
51
Sample B
Major peaks
1-methylcyclohexene (remove)
MW = 96
mass percent

Hint: Strong M+ peak, easily lost branch explains 81 and two famous names are associated with 68.
27
29
39
40
41
53
54
55
65
67
68
77
79
81
82
95
96
97
%T
100
1685
1375
1385
50
838
1470
2960-2850
0
4000
3500
3000
2500
2000
1500
= wavenumber = cm-1
500
1000
100%
6
4
12
4
11
13
16
28
4
42
36
5
11
100 (base)
7
8
41 = M+
4
81 = base peak
75%
50%
67
55
25%
39 41
53
M+ = 96
68
54
79
0%
20
30
50
40
60
m
e
70
90
80
4-methyl-1-bromopentane
MW = 164 (remove in book)
Sample C
%T
100
1385
1470
640 560
1250
2960-2850
0
4000
3500
3000
100%
2500
2000
1500
= wavenumber = cm-1
1000
110
Major peaks
Major peaks
mass percent
mass percent
85.0
15.0
1
86.0
27.0 13
107.0
28.0
1
109.0
29.0
8
149.0
38.0
1
151.0
39.0 11
164.0
40.0
2
166.0
41.0 44
42.0 42
43.0 100 (base)
44.0
3
53.0
2
55.0
5
56.0 12
57.0
9
69.0 31
70.0
2
83.0
1
84.0
2
Hint: (M+2) is helpful, as are 151/149, 109/107. Explain 85, 57 and 43.
50
100
500
59
4
3
2
3
3
2 = M+
2 = M+2
43 = base peak
75%
85
41
42
50%
69
56
57
25%
107
109
149
151
164 = M+
166 = M+2
0%
20
40
60
80
100
m
e
120
140
160
180
200
Spectroscopy
Beauchamp
52
p-thiomethyltoluene
Sample D

Hint: (M+2) is helpful. There is no major peak at 91 for a reason, but 105 will substitute.
100
3050
1375
1385
3550
1520 1440
2960-2850
820
0
4000
2500
3000
3500
2000
1500
= wavenumber = cm-1
500
1000
100%
Major peaks
mass percent
mass percent
106.0 10
27.0
3
135.0
2
39.0
4
137.0
2
45.0
6
138.0 15.5 = M+
50.0
2
139.0
2
51.0
4
140.0 0.9 = M+2 (5.8%)
52.0
1
53.0
2
63.0
2
65.0
3
68.0
2
77.0 11
78.0
4
79.0 11
89.0
1
91.0
5
93.0
1
103.0
8
104.0
6
105.0 100 (base)
%T
50
Major peaks
105 = base peak
75%
50%
25%
138 = M+
77 79
140 = M+2
0%
20
40
80
60
100
120
m
e
140
butoxybenzene
Sample E

Hint: McLafferty can explain 94, though there is no carbonyl group, but there is an xygen. 107 is
small, but more like what you would expect for this functional group. Regular peaks at 29 and 57.
%T The IR peak at 1220 is important.
100
3040
1380
50
1600 1500
2960-2850
1250
760 690
0
4000
2500
3000
3500
2000
1500
= wavenumber = cm-1
100%
500
1000
160
180
Major peaks
Major peaks
mass percent
mass percent
200
27.0
4.1
29.0 11.2
39.0
7.1
40.0
1.4
41.0
8.3
50.0
1.2
51.0
4.4
55.0
1.5
56.0
1.1
57.0
3.9
63.0
1.1
65.0
5.3
66.0
5.5
77.0
7.4
94.0 100.0 (base)
95.0
7.0
107.0
1.6
150.0 18.4 = M+
151.0
2.1
94 = base peak
75%
50%
25%
29
41
57
150 = M+
69
77
107
0%
20
40
60
80
100
m
e
120
140
160
180
200
Spectroscopy
Beauchamp
53
propylbenzene
Sample F
%T
100
3030
1610
1500
1450
2960-2850
740 700
0
4000
2500
3000
3500
2000
1500
= wavenumber = cm-1
100%
500
1000
Major peaks
mass percent
mass percent
27.0
2
39.0
4
41.0
2
50.0
1
51.0
4
63.0
2
65.0
7
77.0
3
78.0
6
79.0
1
89.0
1
91.0 100 (base)
92.0 12
103.0
1
105.0
4
120.0 26 = M+
121.0
3
Hint: The big base peak is a big clue.
50
Major peaks
91 = base peak
75%
50%
120 = M+
25%
0%
20
65
41
29
40
103
105
78
80
60
100
Sample G
140
octan-3-one
%T
120
m
e
Hint: There are a lot of peaks that could be explained, both large and small.
Try 100, 86, 85, 71, 57, 43 and 29. McLafferty might help on some of these.
100
3420
50
1460 1410
1380
2960-2850
1720
0
4000
3500
3000
2500
2000
1500
= wavenumber = cm-1
1000
500
160
180
200
Major peaks
Major peaks
mass percent
mass percent
15.0
1
18.0
1
26.0
2
27.0 21
28.0
4
29.0 58
30.0
1
39.0
8
40.0
1
41.0 17
42.0
4
43.0 100 (base)
44.0
4
53.0
2
55.0
9
56.0
3
57.0 92
58.0
5
71.0 52
72.0
73.0
81.0
85.0
86.0
99.0
100.0
128.0
129.0
67
8
1
10
3
52
4
12 = M+
1
43 = base peak
57
72
29
99
71
50%
25%
128 = M+
85
0%
20
40
60
80
100
m
e
120
140
160
180
200
Spectroscopy
Beauchamp
54
2-ethylhexanal
Sample H
%T
Hint: There are a lot of peaks that could be explained, both large and small. Try 100, 72,
57, 43 and 29. McLafferty might help on some of these.
100
3420
2810
2700
50
1460 1340
2960-2850
1730
0
3500
4000
2500
3000
100%
2000
1500
= wavenumber = cm-1
500
1000
Major peaks
Major peaks
mass percent
mass percent
27.0
28.0
29.0
39.0
40.0
41.0
42.0
43.0
44.0
53.0
54.0
55.0
56.0
57.0
58.0
67.0
68.0
69.0
70.0
15
1
24
9
1
34
4
40
2
2
3
11
4
82
4
2
1
2
1
71.0
5
72.0 100 (base)
73.0
5
81.0
1
82.0
3
85.0
3
100.0
1
128.0
1 = M+
72 = base peak
57
75%
50%
41 43
25%
27
15
29
55
128 = M+
0%
20
40
60
80
100
m
e
120
140
pentylamine
Sample I
Hint: Notice the odd mass peak and the really big peak at 30. Though small 29 and 43 are obvious.
%T
100
3370
3290
50
1610
1470 1380
820
2960-2850
160
180
200
Major peaks
Major peaks
mass percent
mass percent
18.0
2
27.0
3
28.0 33
29.0
2
30.0 100 (base)
31.0
2
39.0
2
41.0
3
42.0
2
43.0
1
44.0
2
45.0
3
87.0
4 = M+
0
4000
3500
3000
2500
2000
1500
= wavenumber = cm-1
1000
500
30 = base peak
50%
27
25%
87 = M+
0%
20
40
60
80
100
m
e
120
140
160
180
200
Spectroscopy
Beauchamp
55
Sample J
heptane
Hint: Look how regular the peaks are. What is lost in each fragment100, 85, 71, 57, 43, 29?
%T
100
1380
50
720
1470
2960-2850
0
4000
3500
2500
3000
2000
1500
= wavenumber = cm-1
500
1000
Major peaks
Major peaks
mass percent
mass percent
72.0
15.0
1
85.0
26.0
1
100.0
27.0 18
28.0
3
29.0 31
39.0 11
40.0
2
41.0 45
42.0 20
43.0 100 (base)
44.0
3
53.0
1
55.0 10
56.0 25
57.0 47
58.0
2
70.0 18
71.0 46
2
2
11 = M+
43 = base peak
57
50%
29
99
41
42
71
56
25%
70
0%
20
40
72
85
80
60
100 = M+
100
Sample K
m
e
120
140
2-ethylpentane
Hint: You can barely see the M+ peak because? 43 is big and 71, 57 and 29 are all there too.
%T
100
770
1380
50
1460
890
2960-2850
0
4000
3500
3000
2500
2000
1500
= wavenumber = cm-1
1000
160
Major peaks
mass percent
27.0 10
29.0 14
39.0
6
41.0 16
42.0
7
43.0 100 (base)
44.0
4
53.0
1
55.0 15
56.0
4
57.0
4
70.0 48
71.0 51
72.0
3
100.0
2 = M+
180
200
Major peaks
mass percent
500
43 = base peak
41
42
50%
25%
27
29
55
0%
20
70 71
40
57
60
100 = M+
72
80
m
e
100
120
140
160
180
200
Spectroscopy
Beauchamp
56
Sample L
dipropylsulfide
Hint: The (M+2) at 120 is helpful, as are 103, 89, 43 and 29. Why is 89 so big and 103 so small?
%T
100
1380
50
1470
2960-2850
0
4000
2500
2000
1500
= wavenumber = cm-1
3000
3500
43 = base peak
61
27
75
29
120 = M+2 (4.8%)
103
40
60
80
100
m
e
Sample M
120
Hint: Look at that big hole in the middlethen there's 85, 57, 43, 29.
%T
100
1370
1420
50
2960-2850
3500
3000
2500
1460
1500
2000
= wavenumber = cm-1
1000
160
140
1-iodohexane
0
4000
mass percent
15.0
2
27.0 25
29.0
6
39.0 16
41.0
2
42.0 65
43.0 100 (base)
47.0 47
61.0 35
75.0 13
76.0 50
89.0 92
103.0
4
118.0 63 = M+
119.0
5
120.0
3 = M+2 (4.8%)
76
47
20
mass percent
118 = M+
50%
0%
Major peaks
89
42
25%
500
1000
Major peaks
500
180
Major peaks
Major peaks
mass percent
mass percent
200
27.0 14
28.0
4
29.0 15
39.0
7
40.0
1
41.0 25
42.0
3
43.0 100 (base)
44.0
3
53.0
1
55.0
6
56.0
2
57.0 11
85.0 50
86.0
3
155.0
2
212.0
4 = M+
43 = base peak
85
50%
25%
29
57
86
20
40
60
80
m
e
212 = M+
155
0%
100
120
140
160
180
200
Spectroscopy
Beauchamp
57
Sample N
%T
Major peaks
mass percent
hexan-1-ol
Hint: If you look hard there is a tiny peak at 102 (=M+)and then a gap of 18. Some
familiar peaks at 57, 43 and 29 are helpful. There's a special reason that 31 is therewhy?
100
1380
660
50
3320
2960-2850
1470
1060
0
4000
2500
3000
3500
2000
1500
= wavenumber = cm-1
1000
500
Major peaks
mass percent
15.0
1
18.0
3
27.0 15
28.0
3
29.0 20
31.0 24
39.0
8
41.0 36
42.0 43
43.0 59
45.0
3
53.0
2
55.0 49
56.0 100
57.0
7
69.0 25
70.0
3
71.0
2
73.0
1
83.0
2
84.0
102.0
9
0 M+ (missing)
160
180
200
56 = base peak
43
50%
25%
27
15
0%
55
42
41
31
29
69
70
71
20
40
84
80
60
M+ = 102
is missing
100
m
e
Sample O
%T
120
140
Major peaks
mass percent
hexanoic acid (remove in book)

MW = 144
Hint: 144 is tiny, but important. (M-56) is big for a reason (McLafferty). Other helpful
peaks are 73, 71, 57, 56, 45, 43, 29.
100
3300-2500
1380
50
1460
2864
2925
1710
0
4000
3500
2500
3000
1230
2000
1500
= wavenumber = cm-1
73
940
1000
500
15.0
18.0
29.0
31.0
39.0
41.0
42.0
43.0
45.0
53.0
55.0
56.0
57.0
59.0
60.0
69.0
70.0
71.0
88 = base peak
1
4
22
1
10
32
5
20
7
2
17
5
38
3
2
6
4
1
Major peaks
mass percent
73.0 92
74.0
5
87.0 21
88.0 100 (base)
89.0
5
101.0 18
115.0 11
116.0 14
144.0 0.5 = M+
M+ = 102
is missing
50%
25%
29
31
0%
20
41 43
45
40
55
56
57
87
70
71
60
101
115
116
144 = M+
80
m
e
100
120
140
160
180
200
Spectroscopy
Beauchamp
58
propyl pentanoate
Sample P
%T

.
Hint:
McLafferty can occur two ways, at 116 and 88. Other useful peaks are at 57, 43, 29
and 45 is there for a reason. By the way, the M+ peak is missing at 144
100
1380
50
1460
2850-2960
1740
0
3000
3500
4000
1250
2500
1090
1180
2000
1500
= wavenumber = cm-1
500
1000
Major peaks
Major peaks
mass percent
mass percent
15.0
2
86.0
6
27.0 24
87.0
3
28.0
8
102.0 10
29.0 29
103.0 60
31.0
4
104.0
4
39.0 10
115.0
4
41.0 38
M+ = 144
42.0 19
is missing
43.0 40
55.0
7
56.0
5
57.0 57
59.0
7
60.0 34
61.0 29
73.0 19
84.0
1
85.0 100 (base)
85 = base peak
57
50%
27
25%
40 43
41
29
15
103
60
61
73
104
31
0%
20
40
80
60
100
m
e
Sample Q
%T
115
M+ = 144
is missing
120
160
140
heptanamide

.Hint: Has an odd M+ peak at 143. McLafferty can explain the base peak at 59 and other
familiar peaks are 43 and 29. The peak at 44 can be explained too.
Major peaks
mass percent
100
640
1460
50
3190
3360
1380
2850-2960
1650
0
3500
4000
3000
2500
2000
720
1630
1500
1000
500
= wavenumber = cm-1
180
200
Major peaks
mass percent
18.0
2
73.0
27.0
5
82.0
28.0
2
83.0
29.0
7
84.0
39.0
4
86.0
41.0 13
96.0
42.0
4
97.0
43.0 16
100.0
44.0 19
114.0
53.0
1
143.0
54.0
1
55.0
8
56.0
2
57.0 10
59.0 100 (base)
60.0
7
69.0
2
72.0 34
6
2
2
1
10
1
1
6
5
6 = M+
59 = base peak
50%
72
25%
0%
18
20
29
43
4144
42
40
55
57
100
60
80
m
e
100
M+ = 143
120
140
160
180
200
Spectroscopy
Beauchamp
59
Sample R
%T
1-octene (remove in book)

MW = 112
.Hint: Some important peaks are M+ at 112 and 41 has a special reason as does 56
(McLafferty-like, but there is no oxygen). Other familiar peaks are at 71, 57, 43 and 29.
100
1380
1640
3080
50
990
1470
910
2850-2960
0
4000
3000
3500
2500
2000
1500
= wavenumber = cm-1
43 = base peak
55
41
56
42
50%
29
27
25%
69
53
0%
20
83
84
85
71
80
60
100
m
e
Sample S
%T
120
140
p-ethylphenol

.Hint: The M+ peak is solid at 122and look at that peak at 107 (think "91" plus a really
good something extra). That's almost all there is.
100
3020
50
1620
3330
2850-2960
3500
3000
1450
1510
0
4000
2500
15.0
1
27.0 25
28.0
5
29.0 35
39.0 28
41.0 82
42.0 66
43.0 100 (base)
53.0
8
55.0 99
56.0 87
57.0 19
69.0 44
70.0 86
71.0 12
83.0 34
84.0 22
85.0
2
112.0 20 = M+
M+ = 112
57
40
Major peaks
mass percent
70
39
15
500
1000
Major peaks
mass percent
1240
2000
1500
= wavenumber = cm-1
830
500
1000
180
160
Major peaks
mass percent
27.0
38.0
39.0
41.0
50.0
51.0
52.0
53.0
55.0
62.0
63.0
65.0
77.0
78.0
79.0
91.0
94.0
3
1
6
1
2
4
2
2
2
1
2
3
13
3
2
4
1
200
Major peaks
mass percent
103.0
2
107.0 100 (base)
108.0
8
121.0
3
122.0 36 = M+
123.0
3
107 = base peak
50%
M+ = 122
25%
77
27
0%
20
39
40
60
108
91
65
55
80
m
e
100
121
120
140
160
180
200
Spectroscopy
Beauchamp
60
1-chloropentane
Sample T
%T

.
Hint:
The M+ peak barely shows at 106 (and 108 is 1/3 its size). 70 is really big because
it lost a small molecule of (36)? 71, 57, 43 and 29 are old familiar friends.
100
50
1350
660
750
1470
2850-2960
0
4000
3500
2500
3000
2000
1500
= wavenumber = cm-1
27
39
57
20
40
M+ = 106
M+2 = 108
91
93
15
80
60
100
m
e
Sample U
%T
120
140
benzylfluoride

.Hint: M+ is big, but M-1 is bigger and that's unusual. However, it has lots of stabilization.
There is a halogen present, but M+2 is not important. What does 91 remind you of?
100
1510
50
3080-3030
1470 1380
2850-2960
980
0
4000
3500
15.0
1
27.0 27
28.0
6
29.0 38
39.0 19
41.0 70
42.0 100 (base)
43.0 39
53.0
3
55.0 93
56.0
6
57.0 22
63.0
5
69.0
3
70.0 95
71.0
6
91.0
3
93.0 0.9
106.0 1.0 = M+
108.0 0.3 = M+2
43
29
25%
0%
Major peaks
mass percent
70
42 = base peak
55
50%
500
1000
Major peaks
mass percent
3000
2500
2000
1500
= wavenumber = cm-1
740
1000
700
500
160
Major peaks
mass percent
27.0
2
28.0
2
31.0
1
39.0
8
44.0
1
45.0
2
50.0
5
51.0
8
57.0
5
62.0
3
63.0
6
65.0
4
77.0
2
81.0
2
83.0 12
89.0
4
180
200
Major peaks
mass percent
91.0
8
92.0
1
107.0
2
108.0
1
109.0 100 (base)
110.0 55 = M+
111.0
4
109 = base peak
110 = M+
50%
25%
27
44
29 31 39 45 51 57
0%
20
40
60
65
77
83
80
91
m
e
100
120
140
160
180
200
Spectroscopy
Beauchamp
61
Sample V
%T
benzoyl choride
(remove in book)
MW = 134.6

.
Hint: Peaks at 105 and 106 have M+2 about 1/3 their size. There is a really helpful
band in the IR spectrum. There are the usual peaks at 29, 43, 57 and 71.
100
50
1380
1470
2860-2960
0
3500
4000
3000
1130
960
1800
2500
2000
1500
= wavenumber = cm-1
55 = base peak
41 43
42
580 440
730
500
1000
Major peaks
mass percent
Major peaks
mass percent
80.0 11
15.0
4
91.0 12
27.0 59
92.0
1
29.0 44
39.0 36
98.0 24
99.0 84
41.0 84
105.0
6
42.0 43
106.0
6
43.0 97
107.0
2 = mass+2
53.0
5
2 = mass+2
55.0 100 (base) 108.0
56.0 27
57.0 45
134.0 0 M+
60.0 13
(missing)
65.0
2
69.0 10
70.0 23
71.0 40
77.0
4
78.0 34
99
27
50%
29
56
57
39
25%
15
53
0%
20
40
60
65
60
71
70
69
78
91
80
80
m
e
105
106
107
108
100
134.0 0 M+
(missing)
120
140
180
160
200
What Happens When There is More Than One Functional Group?

We have mostly looked at monofunctional groups to learn the main clues provided by each functional
group toward our goal of determining organic structures. What if more than one functional group is present?
We can pit two strongly stabilizing groups against one another and see what happens. Both benzyl (91 mass)
and methyliminium (30 mass) carbocations are strongly stabilized and generate easily recognizable MS peaks.
We have seen both individually earlier, but we will repeat them below for comparison.
M+ = 120
mass = 91
(M-29)
27.0
2
39.0
4
41.0
2
50.0
1
51.0
4
CH2 63.0
2
65.0
7
77.0
3
78.0
6
79.0
1
89.0
1
91.0 100
92.0 11
103.0
1
105.0
4
120.0 26
H
H2C
base
peak
NH2
H2N
M+ = 59
mass = 30
(M-29)
15.0
1
18.0
3
26.0
1
27.0
4
28.0
8
29.0
2
30.0 100.0
31.0
2
39.0
2
41.0
5
42.0
3
43.0
2
44.0
1
56.0
1
58.0
2
59.0
9
base
peak
Spectroscopy
Beauchamp
62
One way we could pit these two groups against one another would be to look at the mass spectrum of
benzyl amine. Do we lose the amine group, NH2, or do we lose the phenyl group, C6H5? Not surprisingly, we
dont lose either. Instead they work together to make an even more stable carbocation with mass of 106 (M-1).
H H
27.0
28.0
29.0
30.0
32.0
38.0
39.0
41.0
50.0
51.0
52.0
52.5
53.0
62.0
63.0
65.0
H
NH2
CH2
NH2
H2C
M+ = 107
mass = 106 (100%)

(M-29)
both
stabilizing
groups
mass = 91 (15%)
(M-16)
NH2
mass = 30 (27%)
(M-77)
benzyl
carbocation
(tropylium ion)
imminium
ion
2
11
5
27
1
2
6
1
6
11
4
2
3
1
3
5
74.0
2
75.0
1
76.0
2
77.0 19
78.0 12
79.0 35
80.0
3
89.0
4
90.0
2
91.0 15
92.0
2
103.0
2
104.0
5
105.0
1
106.0 100
107.0 60
Another way to compare these two groups would be to look at the spectrum of 2-phenylethylamine
(phenethylamine). Do we lose benzyl or do we lose methylimminium? Here we find the methylimminium
group is the preferred method of fragmentation, but the benzyl carbocation is still observable. As molecules
get more complicated, so will their mass spectra. We will not emphasize such examples because there are
other methods much more helpful to our goal of determining organic structures, namely 1H and 13C NMR
spectroscopy.
H
CH2
NH2
H2C
NH2
NH2
H
mass = 30 (15%)
M+ = 121
(M-29)
benzyl
carbocation
(tropylium ion)
mass = 30 (100%)
mass = 120 (1%)

(M-1)
(M-91)
imminium
ion
28.0
2
30.0 100
31.0
1
39.0
3
50.0
1
51.0
3
63.0
2
65.0
6
77.0
2
89.0
1
91.0 15
92.0
6
103.0
2
120.0
1
121.0
6
base
peak
Problem Discuss the MS of the following compounds. How do they compare to those in the examples
above?
27.0
2
39.0
4
41.0
2
50.0
1
51.0
4
63.0
2
65.0
7
77.0
3
78.0
6
79.0
1
89.0
1
91.0 100
92.0 11
103.0
1
105.0
4
120.0 26
M+ = 120
OH
M+ = 108
18.0
26.0
27.0
28.0
29.0
31.0
37.0
38.0
39.0
40.0
41.0
43.0
49.0
1
1
6
2
4
3
2
3
11
1
1
1
1
50.0
51.0
52.0
53.0
53.5
54.0
61.0
62.0
63.0
64.0
65.0
74.0
75.0
HO
base
peak
10
21
6
6
2
1
1
3
6
2
7
3
2
M+ = 60
76.0
2
77.0 49
78.0 11
79.0 100
80.0 10
89.0
6
90.0
9
91.0 17
92.0
2
105.0
4
107.0 68
108.0 99
109.0
8
base
peak
(very
unusual)
15.0
1
26.0
2
27.0 10
28.0
4
29.0
7
30.0
2
31.0 100
32.0
2
33.0
1
39.0
4
41.0
7
42.0 12
43.0
2
45.0
2
57.0
1
59.0 16
60.0 10
OH
M+ = 122
27.0
31.0
38.0
39.0
41.0
50.0
51.0
52.0
62.0
63.0
64.0
65.0
66.0
base
peak
1
4
1
8
1
3
6
2
1
4
1
15
1
74.0
1
77.0
5
78.0
4
79.0
1
89.0
3
90.0
1
91.0 100
92.0 60
93.0
4
103.0
4
104.0
4
122.0 30
123.0
3
base
peak
base
peak
Spectroscopy
Beauchamp
63
Problem Major peaks in mass spectra representing most organic groups are provided below. Explain as many peaks
as seems reasonable. There is plenty of opportunity to practice your new mass spec skills.
Alkanes (Also look for alkene fragments too.)
%
19
3
31
11
2
45
20
100
mass
44.0
53.0
55.0
56.0
57.0
58.0
70.0
71.0
%
3
2
10
25
48
2
18
46
mass
72.0
85.0
100.0
%
3
2
11
mass
mass
C7H16
M+ = 100
heptane
mass
27.0
28.0
29.0
39.0
40.0
41.0
42.0
43.0
%
11
15
8
1
31
35
100
3
mass
53.0
55.0
56.0
57.0
58.0
69.0
70.0
71.0
%
1
5
21
29
1
1
2
2
mass
84.0
85.0
86.0
100.0
%
5
37
3
3
mass
mass
C7H16
M+ = 100
2-methylhexane
mass
27.0
29.0
39.0
40.0
41.0
42.0
43.0
44.0
%
12.8
24.7
9.1
1.5
36.7
9.2
100.0
3.5
mass
53.0
55.0
56.0
57.0
58.0
69.0
70.0
71.0
%
1.8
15.0
39.3
52.8
2.3
2.0
46.5
58.3
mass
72.0
84.0
85.0
100.0
%
3.1
1.1
5.7
4.0
mass
mass
C7H16
M+ = 100
3-methylhexane
mass
27.0
29.0
39.0
40.0
41.0
42.0
43.0
44.0
mass
%
27.0
9.9
29.0
14.3
39.0
6.4
41.0
16.1
42.0
6.8
43.0 100.0
44.0
3.5
53.0
1.4
mass
55.0
56.0
57.0
70.0
71.0
72.0
100.0
%
14.9
3.6
4.5
48.4
50.6
2.8
1.7
mass
mass
mass
mass
%
27.0
14.8
28.0
1.3
29.0
27.0
39.0
10.8
40.0
2.0
41.0
52.5
42.0
26.0
43.0 100.0
mass
44.0
53.0
55.0
56.0
57.0
58.0
69.0
70.0
%
3.4
2.2
9.8
99.8
76.2
3.3
1.9
10.8
mass
71.0
72.0
84.0
85.0
100.0
%
38.2
2.2
1.0
12.6
3.0
mass
mass
mass
%
27.0
9.3
29.0
11.5
39.0
6.4
41.0
15.7
42.0
2.7
43.0 100.0
44.0
3.4
53.0
1.8
mass
55.0
56.0
57.0
69.0
70.0
71.0
72.0
85.0
%
11.2
1.3
6.1
1.4
18.0
69.7
4.1
19.3
mass
86.0
100.0
%
1.3
0.0
mass
mass
C7H16
M+ = 100
3-ethylpentane
C7H16
M+ = 100
2,3-dimethylpentane
C7H16
M+ = 100
3,3-dimethylpentane
Spectroscopy
Beauchamp
C7H16
M+ = 100
2,4-dimethylpentane
mass
15.0
27.0
29.0
39.0
40.0
41.0
42.0
43.0
%
1.0
10.6
14.0
7.6
1.4
33.5
23.9
100.0
C7H16
M+ = 100
2,2,3-trimethylbutane
mass
15.0
27.0
29.0
39.0
40.0
41.0
42.0
43.0
C6H14
M+ = 86
hexane
mass
15.0
26.0
27.0
28.0
29.0
30.0
38.0
39.0
64
%
3.3
1.0
3.2
35.3
71.7
3.2
2.4
1.1
mass
85.0
86.0
100.0
%
18.5
1.3
0.0
mass
mass
%
1.5
8.4
15.6
9.3
1.6
42.1
2.7
62.6
mass
%
44.0
2.1
53.0
1.6
55.0
5.1
56.0
58.3
57.0 100.0
58.0
4.6
59.0
2.8
69.0
2.4
mass
83.0
85.0
86.0
100.0
%
1.0
34.4
2.3
0.0
mass
mass
%
1.3
1.7
22.7
4.7
42.5
1.0
1.2
14.8
mass
40.0
41.0
42.0
43.0
44.0
51.0
53.0
54.0
%
3.1
72.5
42.4
80.9
2.8
1.2
2.2
1.2
mass
%
55.0
12.1
56.0
70.5
57.0 100.0
58.0
4.7
69.0
8.5
70.0
2.6
71.0
11.0
84.0
3.2
mass
86.0
%
10.0
mass
mass
%
27.0
12.6
28.0
1.3
29.0
11.3
39.0
9.6
40.0
1.5
41.0
29.5
42.0
52.6
43.0 100.0
mass
44.0
53.0
55.0
56.0
57.0
69.0
70.0
71.0
%
3.2
1.2
6.7
9.4
17.0
1.3
10.2
39.5
mass
72.0
78.0
85.0
86.0
%
2.2
1.0
1.5
6.1
mass
mass
%
1.0
13.3
2.2
39.1
9.2
1.2
53.4
3.6
mass
%
43.0
25.4
53.0
1.8
55.0
6.7
56.0
76.7
57.0 100.0
58.0
4.5
70.0
1.6
71.0
5.7
mass
86.0
%
3.0
mass
mass
C6H14
M+ = 86
3-methylpentane
mass
26.0
27.0
28.0
29.0
39.0
40.0
41.0
42.0
%
1.6
1.1
17.2
2.6
33.6
1.0
13.6
1.8
mass
%
41.0
49.1
42.0
5.6
43.0 100.0
44.0
3.1
51.0
1.1
53.0
2.5
55.0
11.3
56.0
28.0
mass
57.0
58.0
70.0
71.0
72.0
86.0
%
98.3
4.7
3.3
76.7
4.5
0.1
mass
mass
C6H14
M+ = 86
2,2-dimethylbutane
mass
15.0
26.0
27.0
28.0
29.0
38.0
39.0
40.0
mass
15.0
27.0
28.0
29.0
39.0
40.0
41.0
42.0
%
1.4
13.7
1.9
7.5
9.0
1.5
27.4
87.0
mass
%
43.0 100.0
44.0
3.5
53.0
1.4
55.0
5.2
56.0
1.5
57.0
2.3
71.0
19.2
72.0
1.1
mass
86.0
%
3.6
mass
mass
C6H14
M+ = 86
2-methylpentane
C6H14
M+ = 86
2,3-dimethylbutane
mass
44.0
53.0
55.0
56.0
57.0
58.0
69.0
71.0
Spectroscopy
Beauchamp
65
Alkenes & Cycloalkanes

%
1.1
1.2
2.0
25.7
4.9
55.9
1.2
1.8
mass
39.0
40.0
41.0
42.0
43.0
50.0
51.0
52.0
%
30.5
4.9
96.8
54.9
15.9
1.5
2.3
1.0
mass
%
53.0
6.5
54.0
7.6
55.0
67.6
56.0 100.0
57.0
30.7
58.0
1.3
67.0
2.3
68.0
3.6
mass
69.0
70.0
71.0
83.0
98.0
99.0
%
31.1
44.2
2.5
4.2
13.8
1.1
mass
C7H14
M+ = 98
1-heptene
mass
15.0
18.0
26.0
27.0
28.0
29.0
30.0
38.0
%
1.4
2.2
26.3
3.7
22.0
2.1
27.6
4.8
mass
41.0
42.0
43.0
50.0
51.0
52.0
53.0
54.0
%
74.3
19.3
20.5
1.8
3.1
1.4
9.9
11.6
mass
%
55.0 100.0
56.0
90.4
57.0
9.9
65.0
1.3
67.0
5.0
68.0
3.6
69.0
48.1
70.0
16.9
mass
71.0
81.0
83.0
98.0
99.0
%
1.1
1.2
4.2
43.4
3.6
mass
C7H14
M+ = 98
trans-2-heptene
mass
15.0
26.0
27.0
28.0
29.0
38.0
39.0
40.0
%
13.5
3.1
12.8
1.1
18.4
3.7
95.3
23.7
mass
43.0
50.0
51.0
52.0
53.0
54.0
55.0
56.0
%
18.0
1.2
2.4
1.0
7.7
8.3
82.5
98.8
mass
%
57.0
14.2
65.0
1.8
67.0
8.5
68.0
5.2
69.0 100.0
70.0
28.3
71.0
1.6
77.0
1.0
mass
79.0
81.0
83.0
97.0
98.0
99.0
%
1.3
1.7
8.3
2.0
80.2
6.1
mass
C7H14
M+ = 98
trans-3-heptene
mass
27.0
28.0
29.0
38.0
39.0
40.0
41.0
42.0
%
1.4
1.7
24.8
4.9
23.4
1.6
23.0
4.3
mass
41.0
42.0
43.0
44.0
45.0
50.0
51.0
52.0
%
87.8
22.8
27.5
1.0
1.1
1.5
2.4
1.0
mass
%
53.0
7.6
54.0
9.7
55.0
79.3
56.0 100.0
57.0
18.4
65.0
1.0
67.0
4.0
68.0
3.6
mass
69.0
70.0
71.0
81.0
83.0
98.0
99.0
%
49.4
17.6
2.6
1.2
4.5
43.3
3.9
mass
C7H14
M+ = 98
cis-2-heptene
mass
15.0
26.0
27.0
28.0
29.0
38.0
39.0
40.0
%
11.7
3.1
8.9
10.5
2.9
46.6
5.6
11.5
mass
%
53.0
3.2
54.0
1.6
55.0
17.7
56.0 100.0
57.0
10.5
67.0
1.5
69.0
9.9
70.0
12.4
mass
83.0
98.0
%
1.1
3.1
mass
mass
C7H14
M+ = 98
2-methy l-1-hexene
mass
27.0
28.0
29.0
39.0
40.0
41.0
42.0
43.0
%
1.4
1.1
15.5
3.3
12.2
1.5
18.9
3.4
mass
41.0
42.0
43.0
50.0
51.0
52.0
53.0
54.0
%
82.1
6.1
8.2
1.7
3.2
1.4
8.2
2.2
mass
55.0
56.0
57.0
65.0
67.0
68.0
69.0
70.0
%
69
19
2
2
7
3
100
13
mass
72.0
73.0
77.0
79.0
81.0
83.0
84.0
85.0
%
1.2
1.0
1.0
1.4
2.5
14.9
1.1
1.5
mass
98.0
99.0
%
35.9
3.2
C7H14
M+ = 98
3-methy l-3-hexene
mass
15.0
26.0
27.0
28.0
29.0
38.0
39.0
40.0
C7H14
M+ = 98
2,3-dimethy l-2-pentene
mass
15.0
18.0
27.0
28.0
29.0
31.0
38.0
39.0
%
2.2
1.0
14.1
2.3
12.8
1.3
1.1
17.9
mass
40.0
41.0
42.0
43.0
50.0
51.0
52.0
53.0
%
3.4
65.3
5.1
18.9
1.3
2.5
1.2
7.6
mass
%
54.0
2.3
55.0 100.0
56.0
13.7
57.0
4.6
58.0
1.8
59.0
8.9
65.0
1.7
67.0
7.3
mass
68.0
69.0
70.0
71.0
72.0
73.0
79.0
81.0
%
1.6
21.1
4.5
1.0
5.2
3.5
1.5
4.2
mass
83.0
84.0
85.0
98.0
99.0
%
82.9
5.7
4.8
37.8
4.1
Spectroscopy
Beauchamp
66
C7H14
M+ = 98
cycloheptane
mass
15.0
26.0
27.0
28.0
29.0
38.0
39.0
40.0
%
1.7
2.4
23.2
4.8
23.9
2.2
30.9
6.2
mass
41.0
42.0
43.0
50.0
51.0
52.0
53.0
54.0
%
77.6
75.4
14.1
1.6
2.9
1.3
8.5
18.4
mass
%
55.0
96.8
56.0 100.0
57.0
17.9
63.0
1.0
65.0
2.0
66.0
1.7
67.0
13.2
68.0
27.2
mass
%
69.0
61.7
70.0
85.7
71.0
5.1
77.0
1.1
79.0
1.5
81.0
7.5
82.0
4.6
83.0
48.6
mass
84.0
91.0
92.0
95.0
96.0
97.0
98.0
99.0
%
3.7
2.0
1.4
1.1
3.4
1.7
62.9
5.0
%
1.0
12.9
3.2
11.1
1.0
15.6
2.9
41.1
mass
42.0
43.0
51.0
53.0
54.0
55.0
56.0
57.0
%
28.6
6.9
1.9
4.6
4.5
76.3
28.5
5.0
mass
%
67.0
4.5
68.0
9.3
69.0
22.5
70.0
21.8
71.0
1.4
81.0
1.4
82.0
14.5
83.0 100.0
mass
84.0
97.0
98.0
99.0
%
7.0
2.8
36.9
3.1
mass
C7H14
M+ = 98
methylcyclohexane
mass
26.0
27.0
28.0
29.0
38.0
39.0
40.0
41.0
%
1.0
1.4
13.7
2.6
12.5
1.2
18.6
3.5
mass
41.0
42.0
43.0
50.0
51.0
53.0
54.0
55.0
%
63.7
41.3
7.0
1.0
1.7
5.1
5.3
47.9
mass
56.0
57.0
65.0
67.0
68.0
69.0
70.0
71.0
%
44.7
7.4
1.2
10.0
66.4
100.0
56.1
3.2
mass
%
83.0
8.2
98.0
12.3
99.0
1.0
mass
C7H14
M+ = 98
ethylcyclopentane
mass
15.0
26.0
27.0
28.0
29.0
38.0
39.0
40.0
mass
27.0
28.0
29.0
38.0
39.0
40.0
41.0
42.0
%
9.6
2.3
8.3
1.1
18.0
3.0
48.6
2.7
mass
%
43.0
17.4
51.0
1.6
53.0
3.9
55.0 100.0
56.0
11.2
57.0
2.0
65.0
1.1
67.0
3.7
mass
69.0
81.0
83.0
84.0
98.0
99.0
%
2.4
1.4
88.4
6.0
18.4
1.4
mass
mass
mass
15.0
18.0
26.0
27.0
28.0
29.0
31.0
39.0
%
1.3
3.2
1.2
20.2
4.6
27.2
25.6
11.3
mass
40.0
41.0
42.0
43.0
44.0
45.0
53.0
54.0
mass
%
55.0 65.7
56.0 95.5
57.0 23.4
67.0
1.8
68.0 13.3
69.0 51.6
70.0 100.0
71.0
6.3
mass
73.0
83.0
98.0
116.0
%
2.0
7.4
5.6
0.0
mass
mass
27.0
29.0
31.0
39.0
41.0
42.0
43.0
44.0
%
5.1
5.4
1.5
3.2
10.0
3.6
8.1
6.9
mass
%
45.0 100.0
46.0
2.3
55.0
14.9
56.0
6.8
57.0
3.5
69.0
2.7
70.0
4.8
83.0
8.9
mass
98.0
101.0
116.0
%
4.0
3.7
0.0
mass
mass
mass
27.0
28.0
29.0
30.0
31.0
39.0
41.0
42.0
%
9.8
2.1
11.1
1.1
22.1
5.3
34.9
2.9
mass
43.0
44.0
45.0
53.0
55.0
56.0
57.0
58.0
mass
%
59.0 100.0
60.0
3.3
69.0
70.2
70.0
5.4
73.0
1.0
86.0
2.7
87.0
31.3
88.0
1.8
mass
98.0
116.0
%
2.9
0.0
mass
C7H14
M+ = 98
1,1,2,2-tet ramethylcyclopropane
Alcohols and ethers
C7H16O
M+ = 116
1-heptanol
OH
C7H16O
M+ = 116
2-heptanol
OH
C7H16O
M+ = 116
3-heptanol
OH
%
2.4
62.6
48.5
66.7
2.7
3.6
2.5
5.6
%
11.4
2.9
8.1
1.1
8.0
5.8
8.1
8.0
Spectroscopy
Beauchamp
67
mass
18.0
19.0
27.0
28.0
29.0
31.0
39.0
41.0
%
1.1
1.1
9.8
1.1
6.9
11.1
5.4
13.1
mass
%
42.0
2.5
43.0
33.4
44.0
5.4
45.0
4.6
53.0
1.2
55.0 100.0
56.0
9.2
57.0
4.4
mass
69.0
70.0
71.0
72.0
73.0
74.0
98.0
116.0
%
4.0
1.3
3.2
6.3
71.4
3.4
2.0
0.0
mass
mass
%
1.7
8.5
1.5
13.9
6.1
4.2
24.9
1.5
mass
43.0
45.0
46.0
53.0
55.0
56.0
57.0
59.0
mass
%
67.0
1.2
69.0
28.1
70.0
2.7
83.0
1.6
87.0 100.0
88.0
5.4
98.0
2.8
116.0
0.0
mass
mass
3-ethy l-3-pentanol
mass
18.0
27.0
28.0
29.0
31.0
39.0
41.0
42.0
%
2.0
5.9
1.9
8.2
1.8
5.2
4.5
14.1
mass
%
42.0
13.1
43.0
13.3
45.0 100.0
46.0
2.4
47.0
1.3
54.0
1.3
55.0
16.4
56.0
53.7
mass
57.0
69.0
70.0
83.0
84.0
85.0
116.0
%
3.4
13.2
2.4
1.3
19.4
1.8
0.0
mass
mass
C7H16O
M+ = 116
1-methoxyhexane
mass
15.0
27.0
28.0
29.0
31.0
33.0
39.0
41.0
mass
15.0
18.0
26.0
27.0
28.0
29.0
30.0
31.0
%
1.3
1.4
1.0
11.9
2.8
12.0
1.1
5.4
mass
39.0
40.0
41.0
42.0
43.0
44.0
45.0
51.0
mass
%
53.0
4.8
54.0
15.9
55.0
23.1
56.0
4.4
57.0 100.0
58.0
9.1
66.0
2.0
67.0
19.8
mass
68.0
69.0
70.0
71.0
72.0
81.0
82.0
83.0
%
38.6
4.0
13.0
14.9
6.3
34.2
2.5
1.4
mass
85.0
86.0
95.0
96.0
97.0
113.0
114.0
%
5.6
4.1
2.9
22.6
2.0
1.1
2.1
%
10.7
11.8
3.1
34.1
12.6
1.7
1.0
2.0
mass
81.0
82.0
83.0
85.0
86.0
95.0
96.0
97.0
%
47.2
3.7
2.2
3.8
3.1
6.0
35.0
3.1
mass
71.0
79.0
81.0
82.0
83.0
95.0
96.0
114.0
%
1.9
1.5
23.9
2.2
7.5
3.0
4.0
0.0
OH
C7H16O
M+ = 116
4-heptanol
OH
C7H16O
M+ = 116
OH
C7H14O
M+ = 114
cycloheptanol
OH
C7H14O
M+ = 114
4-methylcyclohexanol
OH
C7H14O
M+ = 114
2-cyclopentylethanol
O
C7H14O
M+ = 114
3-butoxypropene
mass
15.0
18.0
26.0
27.0
28.0
29.0
30.0
31.0
%
1.5
2.4
1.1
13.5
3.7
19.8
1.7
5.7
mass
18.0
27.0
28.0
29.0
31.0
39.0
40.0
41.0
mass
39.0
40.0
41.0
42.0
43.0
44.0
45.0
51.0
%
1.3
10.6
2.5
8.4
11.0
13.4
3.8
40.7
mass
15.0
18.0
26.0
27.0
28.0
29.0
30.0
31.0
%
1.4
1.3
1.8
9.9
4.0
24.7
3.2
3.2
%
12.5
73.7
1.7
1.9
8.2
2.3
11.2
2.5
%
12.7
2.8
25.0
14.8
10.3
22.5
5.3
1.1
%
12.7
2.6
34.8
9.9
7.8
17.0
3.3
1.5
mass
42.0
43.0
44.0
45.0
51.0
53.0
54.0
55.0
mass
53.0
54.0
55.0
56.0
57.0
58.0
59.0
65.0
%
5.5
7.7
31.1
12.0
100.0
52.8
2.7
1.0
mass
%
56.0
7.0
57.0
7.3
58.0
1.0
65.0
1.2
66.0
7.6
67.0
99.6
68.0 100.0
69.0
15.4
%
9.6
4.8
5.8
2.4
1.2
7.5
12.3
36.9
mass
38.0
39.0
40.0
41.0
42.0
43.0
44.0
55.0
mass
67.0
68.0
69.0
70.0
71.0
73.0
77.0
79.0
%
1.1
13.4
3.0
100.0
7.6
16.0
1.9
10.4
mass
56.0
57.0
58.0
59.0
71.0
72.0
73.0
85.0
%
13.3
42.9
72.2
3.8
10.7
1.8
2.8
1.9
mass
114.0
mass
113.0
114.0
mass
%
0.0
mass
%
1.4
2.8
Spectroscopy
Beauchamp
C8H18O
M+ = 130
di-sec-butyl ether
O
C8H18O
M+ = 130
di-isobutyl ether
Amines
68
mass
15.0
27.0
28.0
29.0
31.0
39.0
41.0
42.0
%
1.2
8.0
2.0
23.8
2.9
5.2
28.8
1.7
mass
%
43.0
4.7
44.0
1.3
45.0 100.0
46.0
2.2
53.0
1.0
55.0
8.3
56.0
6.8
57.0
84.5
mass
58.0
59.0
60.0
73.0
83.0
97.0
101.0
102.0
%
3.8
29.5
1.0
5.4
9.7
1.1
39.1
2.6
mass
112.0
115.0
130.0
%
1.0
1.0
0.2
mass
mass
27.0
29.0
31.0
39.0
41.0
42.0
43.0
45.0
%
4.0
12.4
1.0
4.2
19.3
2.2
3.6
2.0
mass
%
55.0
2.0
56.0
4.7
57.0 100.0
58.0
4.6
59.0
1.7
73.0
1.0
87.0
8.2
130.0
2.6
mass
mass
mass
Spectroscopy
Beauchamp
69
Haloalkanes
Cl
C3H7Cl
M+ = 78.5
(78 & 80)
mass
%
15.0
1.3
18.0
1.3
26.0
3.9
27.0
31.9
28.0
12.9
29.0
40.6
36.0
1.2
37.0
2.3
1-chloropropane
Cl
C3H7Cl
M+ = 78.5
(78 & 80)
2-chloropropane
Cl
C3H7Cl
M+ = 92.6
(78 & 80)
1-chlorobutane
mass
15.0
26.0
27.0
36.0
37.0
38.0
39.0
40.0
mass
18.0
26.0
27.0
28.0
29.0
38.0
39.0
40.0
%
1.7
2.4
29.3
1.2
1.5
2.4
8.5
2.1
%
1.4
3.7
26.3
15.0
16.7
1.4
10.0
2.2
mass
38.0
39.0
40.0
41.0
42.0
43.0
49.0
51.0
%
4.7
1.4
2.7
0.8
mass
mass
mass
mass
mass
78.0
80.0
9.0
3.1
mass
55.0
56.0
57.0
62.0
63.0
65.0
%
7.5
100.0
5.8
1.3
4.8
1.4
mass
mass
%
3.1
11.4
3.1
23.2
100.0
13.7
4.2
1.3
mass
63.0
65.0
78.0
80.0
mass
%
41.0
21.8
42.0
6.6
43.0 100.0
44.0
3.6
62.0
1.8
63.0
17.0
65.0
5.7
mass
41.0
42.0
43.0
44.0
49.0
51.0
53.0
%
57.5
5.0
36.6
1.1
2.8
1.1
1.2
Spectroscopy
Beauchamp
Cl
C3H7Cl
M+ = 92.6
(90 & 92)
2-chloro-2-methylpropane
Cl
C6H13Cl
M+ = 120.6
(120 & 122)
1-chlorohexane
Br
C3H7Br
M+ = 123
(122 & 124)
1-bromohexane
Br
C3H7Br
M+ = 123
(122 & 124)
mass
15.0
26.0
27.0
28.0
29.0
36.0
37.0
38.0
%
1.9
1.9
10.4
1.4
22.3
3.1
1.4
2.6
mass
39.0
40.0
41.0
42.0
49.0
51.0
53.0
%
17.9
2.6
66.8
3.2
2.2
1.3
1.3
mass
55.0
56.0
57.0
58.0
76.0
77.0
79.0
%
3.9
8.1
100.0
4.3
3.1
38.3
12.2
mass
mass
mass
15.0
18.0
26.0
27.0
28.0
29.0
31.0
38.0
%
1.3
3.2
2.2
27.0
5.0
32.0
1.4
1.2
mass
39.0
40.0
41.0
42.0
43.0
44.0
49.0
51.0
%
16.7
2.9
59.0
44.7
72.0
2.5
3.0
1.4
mass
53.0
54.0
55.0
56.0
57.0
62.0
63.0
65.0
3.7
3.9
81.1
56.5
14.7
1.2
4.7
1.5
mass
67.0
69.0
70.0
71.0
82.0
83.0
84.0
%
2.7
22.1
2.1
2.8
1.2
1.3
4.2
mass
91.0
93.0
%
100.0
32.0
mass
mass
107.0
109.0
122.0
124.0
%
1.5
1.2
8.6
8.3
mass
1.6
2.4
25.6
1.6
4.0
1.2
2.2
9.0
%
2.1
31.0
7.7
100.0
3.5
1.1
1.0
mass
15.0
26.0
27.0
28.0
29.0
37.0
38.0
39.0
mass
40.0
41.0
42.0
43.0
44.0
93.0
95.0
mass
15.0
26.0
27.0
28.0
37.0
38.0
39.0
40.0
%
1.4
2.2
27.4
1.1
1.2
2.1
9.9
1.9
mass
41.0
42.0
43.0
44.0
107.0
109.0
122.0
124.0
%
31.9
4.0
100.0
3.6
1.1
1.0
5.9
5.7
mass
mass
mass
mass
15.0
26.0
27.0
28.0
29.0
38.0
39.0
40.0
%
1.5
5.7
29.4
13.3
40.9
2.0
14.8
2.2
mass
41.0
42.0
43.0
50.0
51.0
53.0
55.0
56.0
%
64.5
3.2
3.9
1.6
1.4
1.5
7.2
16.4
mass
%
57.0 100.0
58.0
4.6
79.0
1.0
81.0
1.0
93.0
1.4
95.0
1.3
107.0
3.7
109.0
3.6
mass
136.0
138.0
%
7.9
7.8
mass
mass
15.0
26.0
27.0
28.0
29.0
38.0
39.0
40.0
%
1.4
3.9
18.6
5.3
40.9
1.8
14.3
1.7
mass
41.0
42.0
50.0
51.0
53.0
55.0
56.0
57.0
%
53.2
2.9
1.6
1.5
1.6
4.9
8.0
100.0
mass
58.0
107.0
109.0
136.0
138.0
mass
mass
2-bromohexane
Br
C4H9Br
M+ = 137
(136 & 138)
70
1-bromobutane
Br
C4H9Br
M+ = 137
(136 & 138)
2-bromobutane
%
4.4
1.2
1.0
0.6
0.6
Spectroscopy
Beauchamp
Br
C6H13Br
M+ = 165.1
(164 & 166)
1-bromohexane
I
C3H7I
M+ = 170.0
1-iodopropane
I
C3H7I
M+ = 170.0
2-iodopropane
I
C5H11I
M+ = 198.0
1-iodopentane
71
%
66.4
2.2
2.4
1.3
25.7
14.6
100.0
4.9
mass
69.0
70.0
71.0
81.0
83.0
84.0
85.0
86.0
%
7.5
3.2
2.8
1.0
1.5
1.2
18.2
1.3
mass
99.0
100.0
107.0
109.0
135.0
137.0
%
14.5
1.2
1.2
1.0
8.3
8.0
mass
164.0
166.0
%
0.4
0.4
%
1.7
1.7
31.7
1.7
1.5
10.7
2.0
36.8
mass
%
42.0
3.3
43.0 100.0
44.0
3.3
127.0
4.9
128.0
1.2
170.0
23.3
mass
mass
mass
mass
15.0
26.0
27.0
28.0
38.0
39.0
40.0
41.0
%
1.1
1.4
27.7
1.6
1.6
11.5
2.0
35.8
mass
%
42.0
3.6
43.0 100.0
44.0
3.4
127.0
5.8
128.0
1.7
170.0
24.3
mass
mass
mass
26.0
27.0
28.0
29.0
39.0
40.0
41.0
42.0
%
1.2
18.8
2.5
23.1
10.6
2.0
30.1
8.3
mass
43.0
44.0
53.0
55.0
71.0
72.0
127.0
128.0
mass
mass
26.0
27.0
28.0
29.0
39.0
40.0
41.0
42.0
%
1.2
16.5
2.7
20.7
10.8
1.9
41.8
10.3
mass
15.0
26.0
27.0
28.0
38.0
39.0
40.0
41.0
mass
43.0
44.0
53.0
54.0
55.0
56.0
57.0
58.0
%
100.0
3.4
1.3
9.9
73.2
4.3
2.1
0.6
I+ = 127
HI+ = 128
mass
I+ = 127
HI+ = 128
mass
141.0
155.0
198.0
%
1.2
2.3
9.5
mass
I+ = 127
HI+ = 128
Spectroscopy
Beauchamp
72
Aldehydes and ketones

mass
%
14.0
2.0
15.0
4.7
18.0
5.2
25.0
2.4
26.0
16.4
27.0
59.0
28.0
90.8
29.0 100.0
H
C3H6O
M+ = 58
propanal
O
C3H6O
M+ = 58
propanone
O
C 4 H8O
M+ = 72
butanal
mass
58.0
59.0
%
85.0
12.1
mass
mass
%
3.1
mass
mass
mass
14.0
15.0
26.0
27.0
28.0
29.0
37.0
38.0
%
2.9
23.1
3.5
5.7
1.2
3.1
1.8
2.2
mass
%
39.0
4.2
40.0
1.0
41.0
2.0
42.0
9.1
43.0 100.0
44.0
3.4
57.0
1.7
58.0
63.8
mass
59.0
mass
14.0
15.0
18.0
26.0
27.0
28.0
29.0
30.0
%
1.7
5.9
1.2
8.2
73.5
19.6
54.8
1.2
mass
31.0
32.0
37.0
38.0
39.0
40.0
41.0
42.0
mass
%
43.0
75.3
44.0 100.0
45.0
3.2
50.0
1.1
53.0
1.1
54.0
2.3
55.0
1.5
57.0
23.3
mass
60.0
71.0
72.0
73.0
%
2.7
5.4
53.6
2.7
mass
%
2.6
1.3
3.1
5.3
27.3
3.5
69.1
9.4
mass
%
38.0
5.7
39.0
28.7
40.0
3.9
41.0
86.7
42.0
14.0
43.0 100.0
44.0
7.4
45.0
1.1
mass
50.0
53.0
55.0
56.0
57.0
71.0
72.0
73.0
%
1.0
1.5
3.3
1.8
6.9
4.4
92.3
5.9
mass
mass
mass
%
14.0
1.2
15.0
6.6
18.0
1.3
26.0
2.6
27.0
8.9
28.0
1.3
29.0
18.8
39.0
1.6
mass
%
41.0
1.1
42.0
4.1
43.0 100.0
44.0
2.6
57.0
8.0
72.0
22.1
73.0
1.0
mass
mass
mass
%
3.9
3.4
28.2
10.5
52.3
2.2
1.9
1.3
mass
%
39.0
12.3
40.0
2.2
41.0
41.0
42.0
11.1
43.0
18.7
44.0 100.0
45.0
12.2
53.0
1.6
mass
55.0
56.0
57.0
58.0
59.0
60.0
67.0
68.0
%
4.4
2.2
19.8
31.4
1.3
2.9
1.1
1.0
mass
71.0
73.0
85.0
86.0
%
1.8
1.1
1.2
1.1
mass
mass
15.0
26.0
27.0
28.0
29.0
30.0
31.0
38.0
%
4.2
2.8
41.9
4.0
46.3
1.0
1.3
2.3
mass
38.0
39.0
40.0
41.0
42.0
43.0
44.0
45.0
mass
50.0
51.0
53.0
55.0
56.0
57.0
58.0
59.0
%
2.5
2.4
5.7
6.2
3.6
37.0
81.4
3.1
mass
60.0
67.0
68.0
69.0
71.0
72.0
85.0
86.0
%
2.7
1.9
2.3
2.6
36.0
1.7
2.8
11.7
mass
87.0
%
1.2
mass
15.0
26.0
27.0
28.0
29.0
30.0
31.0
37.0
C 4 H8 O
M+ = 72
pentanal
O
C4H8O
M+ = 72
butanone
O
C5H10O
M+ = 86
pentanal
O
3-methylbutanal
%
7.8
5.6
2.4
2.3
4.0
1.7
1.7
7.3
mass
%
15.0
2.4
26.0
5.6
27.0
54.9
28.0
13.1
29.0
31.5
31.0
1.5
37.0
3.4
C5H10O
M+ = 86
mass
30.0
31.0
37.0
38.0
39.0
40.0
56.0
57.0
%
5.0
38.7
5.7
89.8
24.6
93.4
100.0
19.6
Spectroscopy
Beauchamp
H
C5H10O
M+ = 86
3-methylbutanal
O
H
C5H10O
M+ = 86
2,2-dimethylpropanal
O
C5H10O
M+ = 86
2-pentanone
O
C5H10O
M+ = 86
3-pentanone
O
C5H10O
M+ = 86
3-methyl-2-butanone
H
C6H12O
M+ = 100
hexanal
H
C6H12O
M+ = 100
2-methylpentanal
73
mass
%
15.0
2.3
18.0
2.3
26.0
4.5
27.0
31.1
28.0
9.4
29.0 100.0
30.0
4.0
31.0
1.7
mass
37.0
38.0
39.0
40.0
41.0
42.0
43.0
44.0
%
1.1
1.9
18.4
2.7
92.4
5.8
11.9
3.8
mass
45.0
50.0
51.0
53.0
55.0
56.0
57.0
58.0
%
3.0
1.4
1.5
3.6
9.4
7.8
95.8
60.0
mass
59.0
67.0
69.0
70.0
71.0
73.0
74.0
85.0
%
2.7
1.1
1.3
2.3
4.9
1.8
11.1
1.8
mass
86.0
87.0
%
6.3
3.2
mass
15.0
18.0
26.0
27.0
28.0
29.0
30.0
32.0
%
2.3
3.0
1.7
16.4
3.2
51.5
1.1
1.0
mass
37.0
38.0
39.0
40.0
41.0
42.0
43.0
50.0
%
1.1
2.5
19.4
2.6
83.5
8.8
26.6
1.2
mass
%
51.0
1.3
53.0
2.1
55.0
5.5
56.0
2.8
57.0 100.0
58.0
5.2
59.0
1.5
71.0
1.6
mass
86.0
87.0
%
18.1
3.1
mass
mass
15.0
26.0
27.0
28.0
29.0
38.0
39.0
41.0
%
4.8
1.3
10.5
1.3
1.9
1.2
6.3
11.9
mass
%
42.0
4.0
43.0 100.0
44.0
2.3
58.0
10.3
71.0
11.0
86.0
20.2
87.0
1.2
mass
mass
mass
mass
26.0
27.0
28.0
29.0
30.0
39.0
41.0
42.0
%
2.5
12.4
4.3
59.4
1.4
1.8
2.0
1.8
mass
%
43.0
1.6
55.0
1.3
56.0
3.7
57.0 100.0
58.0
3.4
86.0
21.2
87.0
1.2
mass
mass
mass
mass
14.0
15.0
26.0
27.0
28.0
29.0
37.0
38.0
%
1.6
9.8
3.1
19.3
3.1
3.5
1.4
2.9
mass
%
39.0
16.3
40.0
2.1
41.0
26.2
42.0
4.9
43.0 100.0
44.0
2.4
45.0
1.3
50.0
1.3
mass
51.0
57.0
71.0
86.0
87.0
%
1.1
3.7
6.9
22.6
1.0
mass
mass
mass
15.0
18.0
26.0
27.0
28.0
29.0
30.0
31.0
%
2.2
1.0
2.7
33.9
8.1
33.0
1.6
1.8
mass
%
38.0
1.9
39.0
20.1
40.0
3.8
41.0
69.1
42.0
10.8
43.0
55.1
44.0 100.0
45.0
19.5
mass
50.0
51.0
53.0
54.0
55.0
56.0
57.0
58.0
%
1.0
1.3
2.9
2.3
15.3
82.0
38.1
9.0
mass
60.0
67.0
69.0
71.0
72.0
73.0
81.0
82.0
%
3.6
8.1
1.4
6.7
16.7
1.8
1.2
12.8
mass
83.0
100.0
%
1.0
0.4
mass
15.0
18.0
26.0
27.0
28.0
29.0
30.0
38.0
%
1.0
1.0
1.5
17.6
2.1
21.4
2.5
1.0
mass
%
39.0
11.4
40.0
1.9
41.0
27.2
42.0
5.2
43.0 100.0
44.0
3.4
53.0
1.9
55.0
10.3
mass
56.0
57.0
58.0
59.0
67.0
69.0
70.0
71.0
%
1.7
12.1
90.1
3.4
1.3
1.3
1.2
15.3
mass
72.0
74.0
100.0
%
1.0
1.7
2.0
mass
Spectroscopy
Beauchamp
H
C6H12O
M+ = 100
2-ethylbutanal
O
C6H12O
M+ = 100
2-hexanone
O
C6H12O
M+ = 100
3-hexanone
O
C6H12O
M+ = 100
4-methyl-2-pentanone
O
C6H12O
M+ = 100
3-methyl-2-pentanone
H
C7H14O
M+ = 114
heptanal
O
H
C7H14O
M+ = 114
2,3-dimethylpentanal
mass
26.0
27.0
28.0
29.0
39.0
40.0
41.0
42.0
%
1.2
14.9
2.0
22.2
10.9
1.3
27.5
4.9
mass
15.0
18.0
26.0
27.0
28.0
29.0
39.0
41.0
mass
15.0
18.0
26.0
27.0
28.0
29.0
30.0
32.0
3.6
1.9
1.1
8.2
2.0
14.8
5.6
14.1
%
2.4
1.8
2.9
27.6
7.5
53.0
1.1
1.6
74
%
100.0
5.5
2.7
1.6
12.6
2.9
15.3
3.8
mass
59.0
67.0
69.0
70.0
71.0
72.0
73.0
82.0
%
1.2
2.6
1.7
2.9
34.2
48.1
3.1
4.9
mass
88.0
100.0
%
1.5
3.1
mass
mass
%
42.0
3.1
43.0 100.0
44.0
2.4
55.0
1.4
57.0
15.8
58.0
49.8
59.0
3.1
71.0
5.4
mass
85.0
100.0
%
6.4
8.0
mass
mass
mass
%
38.0
1.0
39.0
7.9
40.0
1.2
41.0
20.3
42.0
3.6
43.0 100.0
44.0
3.4
53.0
1.0
mass
55.0
56.0
57.0
58.0
71.0
72.0
85.0
100.0
%
2.4
1.8
84.9
3.1
54.0
6.1
2.9
28.6
mass
101.0
%
2.0
mass
mass
43.0
44.0
53.0
54.0
55.0
56.0
57.0
58.0
mass
15.0
27.0
28.0
29.0
31.0
39.0
40.0
41.0
%
5.1
7.2
1.7
11.0
1.1
8.3
1.3
19.2
mass
%
42.0
3.1
43.0 100.0
44.0
2.6
55.0
1.4
56.0
1.4
57.0
24.9
58.0
42.6
59.0
3.5
mass
67.0
72.0
85.0
86.0
100.0
101.0
%
1.9
1.3
17.7
1.0
19.0
1.4
mass
mass
mass
15.0
26.0
27.0
28.0
29.0
39.0
41.0
42.0
%
2.9
1.0
8.0
2.2
33.6
7.1
41.8
4.0
mass
43.0
44.0
45.0
53.0
55.0
56.0
57.0
58.0
mass
67.0
71.0
72.0
73.0
85.0
100.0
101.0
%
1.6
2.4
50.7
2.2
8.3
17.6
2.4
mass
mass
mass
15.0
26.0
27.0
28.0
29.0
30.0
31.0
38.0
%
2.0
2.1
30.7
7.4
40.2
1.5
1.9
1.2
mass
%
39.0 19.2
40.0
3.3
41.0 66.7
42.0 53.0
43.0 84.0
44.0 100.0
45.0 21.9
51.0
1.5
mass
53.0
54.0
55.0
56.0
57.0
58.0
59.0
60.0
%
4.0
7.6
58.6
9.7
46.5
6.4
1.0
1.1
mass
67.0
68.0
69.0
70.0
71.0
72.0
74.0
81.0
%
8.8
17.5
7.1
93.7
23.7
8.5
2.0
19.2
mass
82.0
83.0
84.0
85.0
86.0
87.0
95.0
96.0
mass
27.0
28.0
29.0
30.0
39.0
40.0
41.0
42.0
%
9.8
3.4
25.0
2.7
6.9
1.2
31.1
1.9
mass
%
43.0 70.9
44.0
2.4
45.0
1.2
53.0
1.9
55.0
7.2
56.0
7.9
57.0 31.8
58.0 100.0
mass
59.0
69.0
70.0
74.0
85.0
91.0
97.0
%
4.3
1.5
1.5
2.5
9.9
1.3
1.5
mass
mass
%
100.0
4.4
2.5
1.6
5.1
23.5
67.9
3.3
% mass
2.2 97.0
3.2 114.0
1.2
4.1
15.4
1.3
2.2
14.4
%
mass
%
2.1
1.5
Spectroscopy
Beauchamp
C7H14O
M+ = 114
2-heptanone
O
C7H14O
M+ = 114
3-heptanone
O
C7H14O
M+ = 114
4-heptanone
O
C7H14O
M+ = 114
5-methyl-3-hexanone
O
C7H14O
M+ = 114
5-methyl-2-hexanone
O
C9H18O
M+ = 142
4-nonanone
75
mass
15.0
18.0
27.0
28.0
29.0
39.0
40.0
41.0
%
4.2
1.5
8.9
2.0
8.7
6.7
1.0
11.6
mass
%
42.0
3.0
43.0 100.0
44.0
2.4
45.0
1.4
53.0
1.0
55.0
5.1
56.0
1.5
57.0
1.6
mass
58.0
59.0
71.0
72.0
85.0
99.0
113.0
114.0
%
90.6
14.8
14.0
3.9
3.3
4.1
1.7
9.5
mass
115.0
%
1.0
mass
mass
15.0
26.0
27.0
28.0
29.0
30.0
39.0
40.0
%
1.2
2.5
22.8
8.2
79.1
1.8
8.8
1.0
mass
%
41.0 33.7
42.0
2.8
43.0 15.2
53.0
1.5
55.0
3.6
56.0
2.8
57.0 100.0
58.0
4.4
mass
59.0
71.0
72.0
73.0
85.0
86.0
114.0
115.0
%
1.2
5.6
32.9
2.0
43.3
2.6
14.0
1.1
mass
mass
mass
15.0
26.0
27.0
28.0
29.0
39.0
40.0
41.0
%
1.5
1.0
15.9
1.1
2.9
6.3
1.0
17.5
mass
%
42.0
2.6
43.0 100.0
44.0
3.5
55.0
2.2
57.0
1.4
58.0
6.7
70.0
1.2
71.0
84.7
mass
72.0
86.0
99.0
114.0
115.0
%
3.8
1.4
2.0
14.4
1.2
mass
mass
mass
15.0
26.0
27.0
28.0
29.0
30.0
39.0
40.0
%
1.4
1.3
13.3
2.6
44.8
1.0
8.0
1.2
mass
41.0
42.0
43.0
53.0
55.0
56.0
57.0
58.0
%
25.7
3.0
15.1
1.0
1.6
1.7
100.0
5.0
mass
69.0
71.0
72.0
73.0
85.0
86.0
99.0
114.0
%
1.2
1.5
14.0
1.0
41.3
2.8
4.3
20.4
mass
115.0
%
1.5
mass
mass
15.0
18.0
27.0
28.0
29.0
39.0
40.0
41.0
%
4.6
1.0
9.3
1.6
7.1
7.0
1.0
13.3
mass
%
42.0
2.1
43.0 100.0
44.0
2.4
53.0
1.3
55.0
4.1
56.0
3.8
57.0
14.8
58.0
50.2
mass
59.0
71.0
72.0
81.0
85.0
86.0
99.0
114.0
%
12.4
9.6
1.2
4.8
1.4
1.2
2.3
4.3
mass
mass
mass
15.0
27.0
28.0
29.0
39.0
40.0
41.0
42.0
%
1.1
16.0
1.7
11.5
7.0
1.4
18.7
4.2
mass
%
43.0 100.0
44.0
3.8
53.0
1.2
55.0
5.5
57.0
2.5
58.0
34.4
59.0
1.5
70.0
1.5
mass
71.0
72.0
86.0
87.0
99.0
100.0
142.0
%
59.5
3.4
15.3
2.5
34.3
3.4
5.2
mass
mass
Spectroscopy
Beauchamp
76
Esters
C8H16O2
M+ = 144
ethyl hexanoate
mass
15.0
26.0
27.0
28.0
29.0
30.0
31.0
39.0
%
1.9
1.8
22.3
4.0
49.8
1.4
1.5
8.7
mass
40.0
41.0
42.0
43.0
44.0
45.0
53.0
55.0
%
1.7
22.3
10.1
61.0
2.2
17.4
1.3
12.4
mass
56.0
57.0
59.0
60.0
61.0
69.0
70.0
71.0
%
2.6
2.5
1.0
38.9
23.6
5.5
22.9
26.1
mass
%
72.0
1.5
73.0 23.3
74.0
4.1
83.0
1.3
87.0
6.8
88.0 100.0
89.0
5.8
97.0
2.0
mass
98.0
99.0
100.0
101.0
102.0
115.0
116.0
117.0
144.0
%
1.3
51.9
3.5
25.8
3.6
8.0
1.0
5.0
1.6
Spectroscopy
Beauchamp
C8H16O2 O
M+ = 144
isopropyl 2-methylbutanoate
mass
15.0
26.0
27.0
28.0
29.0
31.0
38.0
39.0
%
1.0
1.1
13.0
5.7
15.7
1.0
1.3
12.0
77
mass
40.0
41.0
42.0
43.0
44.0
45.0
53.0
55.0
%
2.7
43.4
9.6
100.0
3.3
5.0
1.0
4.2
mass
56.0
57.0
58.0
59.0
69.0
73.0
74.0
85.0
%
12.4
92.6
4.1
10.0
1.4
2.6
19.5
66.8
Carboxylic acids
mass
86.0
87.0
102.0
103.0
104.0
116.0
117.0
129.0
%
3.7
11.0
10.5
32.0
1.8
21.3
1.4
5.0
mass
144.0
%
0.6
Spectroscopy
Beauchamp
OH
C8H16O2
M+ = 144
2,2-dimethylhexanoic acid
Alkynes
Acid chlorides
Nitriles
Anhydrides
Amides
mass
18.0
27.0
28.0
29.0
31.0
39.0
40.0
41.0
%
1.5
8.9
1.0
11.9
1.1
8.4
1.4
27.3
78
mass
%
42.0
3.4
43.0
25.2
44.0
1.1
45.0
2.5
53.0
2.2
55.0
11.5
56.0
4.1
57.0 100.0
mass
58.0
59.0
60.0
69.0
70.0
71.0
73.0
74.0
%
4.4
5.5
1.0
3.3
3.8
1.2
19.2
1.3
mass
83.0
87.0
88.0
89.0
99.0
100.0
101.0
115.0
%
2.8
7.3
67.9
3.1
28.5
2.2
6.2
2.0
mass
144.0
%
0.1
Spectroscopy
Beauchamp
79
Amides
hexanamide
27.0
29.0
39.0
41.0
43.0
44.0
59.0
72.0
86.0
N,N-diethylethanamide N-ethylpropanamide N-butylpropanamide
8.7
8.4
5.5
11.6
25.8
28.5
100.0
18.7
9.3
15.0
6.5
27.0
6.4
28.0
5.6
29.0
8.3
30.0 19.0
42.0
6.6
43.0 27.6
44.0 32.9
58.0 100.0
72.0 15.1
100.0
5.9
115.0 33.5
27.0 25.1
28.0 10.4
29.0 100.0
30.0 69.7
42.0
5.4
44.0 72.0
46.0
9.1
56.0
8.6
57.0 63.2
72.0 62.1
86.0
9.6
100.0
5.4
101.0 92.6
102.0
5.6
27.0 12.3
28.0
6.9
29.0 40.0
30.0 100.0
41.0 12.6
44.0 30.5
57.0 51.6
58.0
7.2
74.0 11.1
86.0 22.8
87.0 25.0
100.0 14.5
129.0 13.2
M+ = 115
M+ = 115
NH2
N
H
heptanenitrile
1-heptyne
2-heptyne
27.0 20.6
28.0
6.7
29.0 22.5
39.0 17.8
41.0 87.3
42.0 12.0
43.0 60.2
54.0 55.3
55.0 50.2
56.0
8.2
57.0 11.2
68.0 23.1
69.0 14.7
71.0
5.2
82.0 100.0
83.0 59.4
96.0 14.3
110.0
7.8
111.0 0.7
3-heptyne
27.0
29.0
39.0
40.0
41.0
42.0
51.0
53.0
54.0
55.0
56.0
57.0
65.0
67.0
68.0
79.0
81.0
82.0
95.0
96.0
27.0
28.0
29.0
39.0
40.0
41.0
42.0
43.0
50.0
51.0
52.0
53.0
54.0
55.0
56.0
65.0
66.0
67.0
68.0
77.0
79.0
81.0
82.0
95.0
96.0
27.0
29.0
39.0
40.0
41.0
42.0
50.0
51.0
52.0
53.0
54.0
55.0
56.0
63.0
65.0
66.0
67.0
68.0
77.0
79.0
81.0
82.0
95.0
96.0
18.4
45.7
29.8
11.7
70.6
8.0
5.9
17.9
35.4
51.0
26.1
28.4
7.1
44.0
30.2
10.6
100.0
7.3
9.4
1.0
39.9
6.7
8.6
50.8
7.6
67.6
7.2
25.6
6.3
11.5
8.6
46.9
81.8
22.3
8.2
9.9
5.5
43.3
42.5
5.3
13.8
100.0
7.6
5.3
18.0
M+ = 101
O
M+ = 129
N
H
23.3
13.9
43.1
11.5
83.6
10.5
6.3
11.7
7.3
48.8
24.6
26.5
5.0
5.2
21.3
11.1
100.0
29.2
9.2
32.4
92.6
6.4
6.9
69.6
C
N
M+ = 111
M+ = 96
M+ = 96
M+ = 96
Spectroscopy
Beauchamp
80
Aromatics
hexylbenzene m-diisopropylbenzene p-diisopropylbenzene
27.0
5.2
29.0
5.6
39.0
5.5
41.0
7.6
43.0 16.6
65.0
8.8
78.0
6.4
91.0 100.0
92.0 95.1
93.0
7.7
105.0 11.2
133.0
5.4
162.0 33.2
27.0
39.0
41.0
43.0
65.0
66.0
77.0
79.0
91.0
105.0
119.0
133.0
147.0
148.0
162.0
6.0
5.4
13.1
33.4
5.2
5.2
7.2
5.6
25.7
30.2
41.8
6.5
100.0
14.4
36.4
41.0
43.0
77.0
91.0
105.0
117.0
119.0
131.0
147.0
148.0
162.0
9.3
19.2
5.5
19.2
21.8
7.5
30.8
5.0
100.0
12.4
33.1
M+ = 162
M+ = 162
M+ = 162

MS Chapter

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MS Chapter

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Spectroscopy

Basics of Mass Spectroscopy

y:\files\classes\Spectroscopy Book home\1 Spectroscopy Workbook, latest MS full chapter.doc

Typical MS Instrument Features.

Each of these masses = 13 amu = C + H

molecular ion peak = M+ = 4x(12C) + 10x(1H) + 1x(16O) = 74 amu

Whatever the size of this peak,

(10 ways) = 0.0015

sum of possibilities = (0.0439) + (0.0015) + (0.0004) = 0.0458

"mini" probability theory

= (0.0439)2(6 ways) = 0.0007

= 1 x 10-6 = 0.000001 = too small to consider

= 1 x 10-6 = 0.000065 = 0.0001

sum of possibilities = (0.0007) + (0.0020) + (0.0001) = 0.0028

Exact Mass (M+1)

M+ = molecular ion peak

Exact Mass (M+1)

Data tables exist with many values

Here is our compound.

y:\files\classes\Spectroscopy Book home\1 Spectroscopy Workbook, latest MS full chapter.doc

(assigned a referenced value of 100%)

M+2 peak relative size

one Br comparison of M+ peak (79Br) to M+2 peak (81Br)

(assigned a referenced value of 100%)

one S comparison of M+ peak to M+1 to M+2 peak

(assigned a referenced value of 100%)

M+2 peak relative size

one Br and one Cl comparison of M+ peak to M+2 and M+4 peaks

two Cl comparison of M+ peak to M+2 peak to M+4 peaks

M+2 peak relative size

y:\files\classes\Spectroscopy Book home\1 Spectroscopy Workbook, latest MS full chapter.doc

Hf o(H electron af finity) = -17

Hf o(R ) = [BE+IP-EA- Hf o(H )]

(98) + (193) - (17) - (52) = +222

(88) + (165) - (17) - (52) = +184

y:\files\classes\Spectroscopy Book home\1 Spectroscopy Workbook, latest MS full chapter.doc

more crowded as sp3 center = higher

Breaking a bond is a large

less crowded as sp2with 3 groups

Actual Mass Spectrum tabulated and graphical.

Peaks 15, 29, 43, 57 and 72 are logical. In our discussions of

y:\files\classes\Spectroscopy Book home\1 Spectroscopy Workbook, latest MS full chapter.doc

Energy to rupture bonds

Actual Mass Spectrum tabulated and graphical.

y:\files\classes\Spectroscopy Book home\1 Spectroscopy Workbook, latest MS full chapter.doc

Special patterns of fragmentation from organic functional groups

can't tell which

y:\files\classes\Spectroscopy Book home\1 Spectroscopy Workbook, latest MS full chapter.doc

octane - all alkane f ragments

Mostly peaks greater than 4%

3,4-dimethylhexane - has branches

octane, MW =114 (M+ = 6%)

Remaining sigma bond

oct-1-ene, MW =112 (M+ = 20%)

These alkenes all look similar.

y:\files\classes\Spectroscopy Book home\1 Spectroscopy Workbook, latest MS full chapter.doc

of 14 (insertion of CH2 x1, x2, ).

resonance stabilized carbocation

It is possible to see the cation charge on either

5. Cyclohexenes often undergo retro Diels-Alder reactions.

Only cations reach the detector. Either fragment could be positive,

y:\files\classes\Spectroscopy Book home\1 Spectroscopy Workbook, latest MS full chapter.doc

alkyl branch fragments = 15, 29, 43, 57, 71, 85, 99

Another Alkene Example (C7 alkene)