Basics of Mass Spectroscopy: R H E-High Energy R H Radical Cation 2 e - EI Mass Spec

Spectroscopy Beauchamp 1
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 neon-
22. 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.
high EI mass spec
R H + energy R H + 2 e-
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

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. .
Tabulated Data 91 57
85 119
Mass percent
O 1-phenyl-2-hexanone
27 6 C12H16O , MW = 176
28 2
29 24
39 7 57 85 = base peak
100
41 26 Many smaller
42 1 peaks are not
43 1 shown, but listed
50 1 in data table to
51 3 75 the left.
55 3
57 99
58 5 percent
60 1 relative 50
63 3 intensity
65 11 91
77 2
85 100 (base) 29 41
86 6 25 M+
89 2 65 peak
90 2 27 176
91 36 39 58 86 92
92 6 0
176 7 = M+
177 1 0 25 50 75 100 125 150 175 200
mass m
charge = e
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 peak’s 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 B2r2 m = mass
e = 2V e = charge (usually +1)
B = size of magnetic field
r = radius of curvature

mV 1 V = voltage on accelerator plate
r = e B
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 amu’s (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,
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.
Average
Element Atomic Weight Nuclides Exact Mass Relative Abundance*
1
hydrogen 1.00797 H 1.00783 100.0
2
H (D) 2.01410 0.015
12
carbon 12.01115 C 12.00000 100.0
13
C 13.00336 1.11
14
nitrogen 14.0067 N 14.00307 100.0
15
N 15.00011 0.37
16
oxygen 15.9994 O 15.9949 100.0
17
O 16.9991 0.04
18
O 17.9992 0.20
19
fluorine 18.9984 F 18.9984 100.0
28
silicon 28.086 Si 27.9769 100.0
29
Si 28.9765 5.06
30
Si 29.9738 3.36
31
phosphorous 30.974 P 30.9738 100.0
32
sulfur 32.064 S 31.9721 100.0
33
S 32.9715 0.79
34
S 33.9679 4.43
35
chlorine 35,453 Cl 34.9689 100.0
37
Cl 36.9659 31.98
79
bromine 79.909 Br 78.9183 100.0
81
Br 80.9163 97.3
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.
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.
Each of these masses = 13 amu = C + H
H H H H H H (We assume there are "n" of them if
the unknown was a hydrocarbon.
H C C C C C C H This is our starting point formula.)
H H H H H H These are left over hydrogen atoms = r
M M = molecular weight
= n + r n = number of CH units = quotient
13
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 element’s 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
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.
C C C C O C C C C N N C C C C N
CnH2n+2Ox CnH2n+3N1 CnH2n+4N2

(N is odd) (N is even)
C = even mass C = even mass C = even mass
H = even mass H = odd mass H = even mass
O = even mass O = even mass O = even mass
MW = even mass MW = odd 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 can’t tell what the relative fractions of M+1 and M+2 are. Let’s 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 don’t 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).
molecular ion peak = M+ = 4x(12C) + 10x(1H) + 1x(16O) = 74 amu Whatever the size of this peak,
as a fraction = 1.000 it is assumed to be 100% for
as a percent = 100% comparison with the M+1 and
M+2 peaks.
M+1 peak - arises from different possibilities of one additional amu = 75 amu
1.11 13
C
one 13C = 101.11 (4 ways) = 0.0439 12
C + 13C
2
0.015 D
one 2H = 100.015 (10 ways) = 0.0015 1
H + 2D
17
0.04 O
16 (1 ways) = 0.0004
one O= 101.24 16
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 "mini" probability theory
2
1.11 4x3 There are 4 ways of picking
two 13C = 101.11 = (0.0439)2(6 ways) = 0.0007
2x1 the first carbon and 3 ways of
2 picking the second carbon
0.015 10 x 9 (=4x3) and since all carbon
two 2H = 100.015 2 x 1 = (2.25x10-8)(45 ways) is the same, we can't tell what
carbon was picked first and
= 1 x 10-6 = 0.000001 = too small to consider second, so we divide by two
0.20 facorial (2x1).
one 18O = 101.24 (1 ways) = 0.0020
100%
13 2 1.11 0.015
one C and one H = (4 ways) x 100.015 (10 ways)
101.11
= 1 x 10-6 = 0.000065 = 0.0001
4.58%
sum of possibilities = (0.0007) + (0.0020) + (0.0001) = 0.0028 0.28%
M+2 peak as a percent of M+ peak = (0.0028)x(100%) = 0.28%
M+ M+1 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 Exact Mass (M+1) (M+2) M+ = molecular ion peak Exact Mass (M+1) (M+2)
(formulas) (formulas)
74 75
CH2H2O2 74.0117 1.95 0.41 CH2H2O2 74.9956 1.60 0.61
CH4N3O 74.0355 2.33 0.22 CH4N3O 75.0320 2.70 0.43
CH6N4 74.0594 2.70 0.03 CH6N4 75.0798 3.45 0.05
C2H2O3 74.0004 2.31 0.62 C2H2O3 75.0684 3.81 0.25
C2H4NO2 74.0242 2.69 0.42
C2H6NO 74.0480 3.06 0.23 Data tables exist with many values
etc. already calculated for comparisons.
C3H6O2 74.0368 3.42 0.44
C3H10N2 74.0845 4.17 0.07
C4H10O 74.0003 4.52 0.28 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.

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 Cl’s and/or Br’s 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 100%

probability of 35
Cl = 100 (1 way) = 0.758
100 + 32
(assigned a referenced value of 100%)
32%
M+2 peak relative size
probability of 37
Cl = 32 (1 way) = 0.242
100 + 32
percent of M+ peak = 0.242 (100%) = 32%

0.758 M+ M+1 M+2
one Br – comparison of M+ peak (79Br) to M+2 peak (81Br)
M+ peak relative size 100% 97%

probability of 79
Br = 100 (1 way) = 0.508
100 + 97
probability of 81
Br = 97 (1 way) = 0.492
100 + 97
percent of M+ peak = 0.492 (100%) = 97%

0.508 M+ M+1 M+2
one S – comparison of M+ peak to M+1 to M+2 peak
M+ peak relative size

probability of 32
S= 100
100 + 0.79 + 4.43 (1 way) = 0.950 100%
probability of 33
S= 0.79
100 + 0.79 + 4.43 (1 way) = 0.008
percent of M+ peak = 0.008 (100%) = 0.8% 4.4%

0.950 0.8%
M+2 peak relative size M+ M+2

M+1
probability of 34
S= 4.43
100 + 0.79 + 4.43 (1 way) = 0.042
percent of M+ peak = 0.042 (100%) = 4.4%

0.950
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) = 0.385 129%
M+2 peak relative size 100%
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 31%
percent of M+ peak = (0.496/0.373)x100% = 129%
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%
M+2 peak relative size 61%
probability of 37Cl = 0.242 (from above)
(probability of 35Cl)(probability of 37Cl)(2 ways) = (0.758) (0.242)(2) = 0.367
10%
(probability of 37Cl)(probability of 37Cl)(1 way) = (0.242)2(1) = 0.059
percent of M+ peak = (0.059/0.602)x100% = 10% M+ M+2 M+4

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).
General Energy Cycle for Carbocations - relative energy to form carbocations (all energy values in kcal/mole)
R e- H
heterolytic
bond energy Hf o(H ) = -52 heat of formatio of hydrogen
C H C H atom, common to all cycles
ionization Hf o(H electron af finity) = -17

potential of R H
R H Hf o(R ) = + value
(see table)
homolytic
bond Energy to f orm
energy carbocation
R-H
Hf o(R ) = [BE+IP-EA- Hf o(H )]

(BE) Hf o(H )
Compound Radical I.P. E.A.(H) = energy to make R
H-H H (hydrogen carbocation) 104 313 -17 -52 (104) + (313) - (17) - (52) = +348
H3C-H H3C (methyl carbocation) 105 227 -17 -52 (105) + (227) - (17) - (52) = +263
CH3CH2-H CH3CH2 (primary carbocationl) 98 193 -17 -52 (98) + (193) - (17) - (52) = +222
(CH3)2CH-H (CH3)2CH (secondary carbocation) 95 169 -17 -52 (95) + (169) - (17) - (52) = +195
(CH3)3C-H (CH3)3C (tertiary carbocation) 92 154 -17 -52 (92) + (154) - (17) - (52) = +177
CH2=CHCH2-H CH2=CHCH2 (allylcarbocation) 86 186 -17 -52 (86) + (186) - (17) - (52) = +203
C6H5CH2-H C6H5CH2 (benzyl carbocation) 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.

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
Breaking a bond is a large
uphill energy transformation, R
C
R but less so with a sterically R
R C R
R crowded starting point, so Ea
is a little smaller than expected. R
more crowded as sp3 center = higher less crowded as sp2with 3 groups

potential energy starting point around trigonal planar carbon
with 3-4 larger groups around is slightly more stable than it
tetrahedral carbon would be if groups were smaller
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
CH3
b d H f high energy
H2C C CH2 electron beam b d H f Possible
a c e g H2C C CH2
a c e fragmentations?
g
H H H H
H H H H
2-methylbutane Energy to rupture bonds
(isopentane) radical cation (eight calculations).
b b c c d d f f
Actual Mass Spectrum – tabulated and graphical.

mass percent Peaks 15, 29, 43, 57 and 72 are logical. In our discussions of
15 2 fragmentation we will see how many of the other peaks are explainable.
26 4
27 43 75 eV
28 6 43 = base peak
100
29 60 41,42 57 Many smaller
isopentane
30 1 peaks not shown.
37 1 C5H12
38 3 75 CH3
39 30
40 5 57
43
29
41 88 percent
15 CH 29 CH3
42 95 relative 50 H3C C
H2
43 100 = base intensity
MW = 72
44 7
50 2 39
51 3 25 M+
53 4 peak
55 10 72
56 40
57 95 0
58 6 0
50 100
25 75
71 5 mass m
72 16 = M+ =
charge e

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 CH3
H2 high energy
H H2 H
H3C a C C C CH3 electron beam Possible
b c d H3C a C C C CH3
b c d fragmentations?
CH3 CH3 CH3 CH3
Energy to rupture bonds
2,2,4-trimethylpentane radical cation (eight calculations).
a a b b c c d d
Actual Mass Spectrum tabulated and graphical.
mass percent
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)
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?
Actual Mass Spectrum tabulated and graphical.

mass percent percent
base
relative
27 20 intensity 75 eV peak
28 4 100
43
29 27 octane Many smaller
39 12 C8H18 peaks not shown.
40 2
41 44 75 H2 H2 H2
42 15 C C C CH3
43 100 = base H3C C C C
44 3 H2 H2 H2
53 2 50
55 11 41
56 18
57 34 29 57
25 71 85 M+
69 2 peak
70 12 114
71 20
84 7 0
85 26 0
86 2 50 75 100 120
25
mass m
114 6 = M+ charge =
Z

Special patterns of fragmentation from organic functional groups
Alkanes - Key Points (see examples above)
1. Lower mass alkyl branch fragments (2-6 C’s, 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 can’t tell by only observing the mass since they have the same number.
less stable more stable

primary carbocation tertiary carbocation
proposed probable
fragmentation rearrangement
R R
C4H9 C4H9
mass = 57 can't tell which 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%) M+ = 114 (3%) M+ = 114 (0%)

base peak = 43 base peak = 43 base peak = 57
(M - 15) = 99 peak (0%) (M - 15) = 99 peak (1%) (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.
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 won’t 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+ = 114 (6%)

M-28 = 84 (39%) 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 don’t have as many options for falling apart as the larger fragments do.
Also, when larger fragments fall apart, they make smaller fragments.

M+ = 114
C8H18
71 99 C8H18 C6H13 C6H13 C5H11 C4H9 C3H7 C2H5 C1H3
57 43 15
57
29 M+ = 114 99 85 71 57 43 29 15
85
actual peaks
octane - all alkane f ragments not observed in octane
are observed, except 99. in octane mass %
alkane
15.0 1
peaks
26.0 1
Only cations reach detector, so only the part with positive charge is observed at the detector. A positive charge 27.0 20
is written on all f ragments to indicate that either part could retain the positive charge (in a rearranged stable form). 28.0 4
Of ten you can see the mass of both cations of a possible fragmentation. It is usef ul to look f or both fragment 29.0 27
masses in the mass spectrum. Peaks related to alkene fragmentations are discussed in the next f unctional group. 39.0 12
40.0 2
41.0 44
42.0 15
The typical appearance of a mass spectrum is shown below. Data is also often presented as shown 43.0 100 base
to the right. The intensity of the peaks tends to decrease as the fragment masses get larger. Larger 44.0 3
f ragments are less likely to survive the 10-5 second trip to the detector. 51.0 1
53.0 2
54.0 1
55.0 11
56.0 18
Mostly peaks greater than 4%
43 = base 57.0 34
of the base peak are shown.
58.0 2
69.0 2
70.0 12
41 MW = 114 71.0 20
72.0 1
57 84.0 7
27 29 71 85
42 56 85.0 26
39 55 70 M+ = 114
28 86.0 2
99.0 none
120 114.0 6 M+
20 30 40 50 60 70 80 90 100 110
115.0 1
3,4-dimethylhexane - has branches actual peaks

possible alkyl in 3,4-dimethylhexane
fragments mass %
15 / 99 27.0 10
28.0 1 alkane
29 / 85 H 58 (4%) 29.0 26
elimination reaction similar to peaks
39.0 7
43 / 71 -H2O in alcohols to form alkene 40.0 1
41.0 43
MW = 114 57 / 57 42.0 2
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). 53.0 2 the base
55.0 8 peak is
56.0 100 not expected
(-H2) (-RH) 57.0 81
56 (100%) 58.0 4
alkenes 69.0 3
(see the next functional group) The base peak (56) is likely from an alkene, C4H8. 70.0 1
71.0 1
Remarkably, it is the major peak in the spectrum! 84.0 7
85.0 41
56 = base Mostly peaks greater than 4% 86.0 3
of the base peak are shown. 99.0 none
57 114.0 2 M+
43 115.0 0.2
41 85 MW = 114
29 55 84
27 39 M+ = 114
20 30 40 50 60 70 80 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.
Remaining sigma bond

R R + e-
holds skeleton together.
octane, MW =114 (M+ = 6%) 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.

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 R R
R' ionization R' fragmentation
R'
free radical
resonance stabilized carbocation is sucked away
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 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 H
CH2 C H2C C
fragmentation
C C C
R C R CH2 R R
H2
mass = 42 (R = H) 28 (R = H)
even mass 56 (R = CH3) 42 (1 extra C)
70 (R= CH2CH3) 56 (2 extra C)
84 (R = C3H7) 70 (3 extra C)
5. Cyclohexenes often undergo retro Diels-Alder reactions.
R2
R2
fragmentation is a
retro-Diels-Alder reaction
R1
diene dienophile
R1
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.
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
actual peaks
112 (0%) 112 (0%) 71 (20%) from octane
70 (12%) 41 (44%) mass %
42 (15%)
26.0 1
27.0 20
H 28.0 4
29.0 27
39.0 12
OR 40.0 2
OR
57 (34%) 41.0 44
112 (0%) 42.0 15
112 (0%) 43.0 100
56 (18%) 56 (18%) 55 (11%) 44.0 3
53.0 2
55.0 11
H 56.0 18
OR 57.0 34
OR 58.0 2
69.0 2
112 (0%) 69 (2%) 43 (100%) 70.0 12
112 (0%) 70 (12%) 42 (15%) 71.0 20
72.0 1
84.0 7
85.0 26
86.0 2
CH3
OR 114.0 6
112 (0%) 15 (0%)

97 (0%)
OR
OR
112 (0%) 112 (0%)
84 (7%)
28 (4%) 83 (0%) 29 (27%)

Similar fragmentation patterns for C8H16 alkenes. Notice that octane (an alkane) has many of these same fragments.
A C E G
D F H
B
A B C D E F G H
octane 1-octene trans-2-octene cis-2-octene trans-3-octene cis-3-octene cis-4-octene trans-4-octene
15.0 1 15.0 1 15.0 1 15.0 1 15.0 2 15.0 1 15.0 1
26.0 1 26.0 1 26.0 1 26.0 1 26.0 2 26.0 2 26.0 1
27.0 20 27.0 25 27.0 18 27.0 25 not available 27.0 25 27.0 23 27.0 16
28.0 4 28.0 5 28.0 4 28.0 4 28.0 4 28.0 3 28.0 2
29.0 27 29.0 35 29.0 33 29.0 45 29.0 19 29.0 17 29.0 14
30.0 - 30.0 - 30.0 1 30.0 1 30.0 - 30.0 - 30.0 -
32.0 - 32.0 1 32.0 - 32.0 - 32.0 - 32.0 - 32.0 -
38.0 - 38.0 1 38.0 1 38.0 1 38.0 2 38.0 2 38.0 1
39.0 12 39.0 28 39.0 19 39.0 22 39.0 26 39.0 24 39.0 16
40.0 2 40.0 5 40.0 3 40.0 4 40.0 5 40.0 4 40.0 2
41.0 44 41.0 82 41.0 64 41.0 81 41.0 100 41.0 93 41.0 78
42.0 15 42.0 66 42.0 34 42.0 44 42.0 38 42.0 29 42.0 25
43.0 100 43.0 100 43.0 11 43.0 15 43.0 18 43.0 15 43.0 12
44.0 3 44.0 3 44.0 - 44.0 1 44.0 1 44.0 - 44.0 -
50.0 - 50.0 - 50.0 1 50.0 1 50.0 2 50.0 2 50.0 1
51.0 1 51.0 2 51.0 2 51.0 2 51.0 4 51.0 3 51.0 2
52.0 - 52.0 1 52.0 1 52.0 1 52.0 2 52.0 2 52.0 1
53.0 2 53.0 8 53.0 8 53.0 8 53.0 11 53.0 9 53.0 6
54.0 1 54.0 9 54.0 9 54.0 8 54.0 8 54.0 9.2 54.0 7
55.0 11 55.0 99 55.0 100 55.0 100 55.0 95 55.0 100 55.0 100
56.0 18 56.0 87 56.0 52 56.0 63 56.0 54 56.0 46 56.0 43
57.0 34 57.0 19 57.0 21 57.0 25 57.0 16 57.0 14 57.0 12
58.0 2 58.0 - 58.0 1 58.0 1 58.0 1 58.0 - 58.0 -
59.0 - 59.0 - 59.0 - 59.0 - 59.0 1 59.0 - 59.0 -
63.0 - 63.0 - 63.0 - 63.0 - 63.0 1 63.0 1 63.0 -
65.0 - 65.0 1 65.0 1 65.0 1 65.0 2 65.0 2 65.0 2
66.0 - 66.0 - 66.0 - 66.0 - 66.0 1 66.0 1 66.0 -
67.0 - 67.0 6 67.0 5 67.0 6 67.0 10 67.0 9 67.0 8
68.0 - 68.0 7 68.0 4 68.0 5 68.0 7 68.0 5 68.0 4
69.0 2 69.0 44 69.0 29 69.0 34 69.0 47 69.0 36 69.0 32
70.0 12 70.0 86 70.0 43 70.0 56 70.0 48 70.0 44 70.0 42
71.0 20 71.0 12 71.0 4 71.0 6 71.0 6 71.0 5 71.0 4
72.0 1 72.0 - 72.0 - 72.0 - 72.0 - 72.0 - 72.0 -
77.0 - 77.0 - 77.0 - 77.0 - 77.0 2 77.0 1 77.0 1
79.0 - 79.0 - 79.0 - 79.0 - 79.0 2 79.0 2 79.0 1
81.0 - 81.0 1 81.0 1 81.0 1 81.0 3 81.0 2 81.0 2
82.0 - 82.0 6 82.0 2 82.0 3 82.0 2 82.0 2 82.0 2
83.0 - 83.0 34 83.0 16 83.0 22 83.0 24 83.0 24 83.0 29
84.0 7 84.0 22 84.0 7 84.0 10 84.0 7 84.0 7 84.0 7
85.0 26 85.0 2 85.0 - 85.0 1 85.0 2 85.0 1 85.0 -
86.0 2 86.0 - 86.0 - 86.0 - 86.0 - 86.0 - 86.0 -
97.0 - 97.0 4 97.0 2 97.0 2 97.0 2 97.0 2 97.0 1
112.0 - 112.0 20 112.0 28 112.0 36 112.0 36 112.0 36 112.0 33
113.0 - 113.0 2 113.0 3 113.0 3 113.0 3 113.0 3 113.0 3
114.0 -
115.0 1 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
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
McLafferty rearrangements through the skeleton to allylic fragmentations
almost any conceivable
H position.
C7H14 = 98 (14%) 57 (31%)

42 (55%) 56 (100%) C7H14 = 98 (14%) 41 (97%) all peaks > 1%
15.0 1
18.0 1
H 26.0 2
27.0 26
28.0 5
29.0 56
43 (16%) 30.0 1
42 (55%) 38.0 2
C7H14 = 98 (14%) 56 (100%) C7H14 = 98 (14%) 55 (68%) 39.0 30
40.0 5
41.0 97
42.0 55
43.0 16
H 50.0 2
51.0 2
52.0 1
53.0 6
54.0 8
70 (44%) 28 (5%) 69 (31%) 55.0 68
C7H14 = 98 (14%) C7H14 = 98 (14%) 29 (56%) 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
C7H14 = 98 (14%) 83 (31%)
alkyl branches allylic McLafferty

15 (1%) fragments
29 (56%) fragments
27 (26%) 28 (5%)
43 (16%) 41 (97%)
57 (31%) 42 (55%)
55 (68%) 56 (100%)
71 (3%) 69 (31%)
85 (0%) 70 (44%)
83 (4%)

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
R H R
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.

R' This could be because the cation is really an aromatic carbocation.
H
C H H
R C C C also
fragmentation resonance
CH R C R C works R
C for
H C
R' 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 on one or the other.
R C H
H R
C C
R
fragmentation C H C
H H
H
40 (R = H) 28 (R = H)
radical cation 54 (R = CH3) 42 (R = CH3)
even mass 68 (R= CH2CH3) 56 (R= CH2CH3)
82 (R= C3H7) 70 (R= C3H7)
Either fragment can be observed and both show an even mass.
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)
McLafferty rearrangements A pi bond can migrate
through the skeleton to allylic fragmentations
almost any conceivable
H position.
C7H12 = 96 (1%) 57 (28%)

40 (12%) 56 (26%) C7H12 = 96 (1%) 39 (30%)
43 (4%)
42 (8%) C7H12 = 96 (1%) 53 (18%)
C7H12 = 96 (1%) 54 (35%)
15 (0.5%)
29 (46%)
H 43 (4%)
57 (28%)
71 (0.2%)
85 (0%)
68 (30%) 67 (44%) 29 (46%)

28 (4%) C7H12 = 96 (1%)
C7H12 = 96 (1%)
CH3
15 (0.5%)
C7H12 = 96 (1%) 81 (100%)
mass % mass % mass % mass % mass %

26.0 1 40.0 12 53.0 18 66.0 3 81.0 100
27.0 18 41.0 71 54.0 35 67.0 44 82.0 7
28.0 4 42.0 8 55.0 51 68.0 30 95.0 9
29.0 46 43.0 4 56.0 26 69.0 2 96.0 1
C7H12 30.0 1 45.0 1 57.0 28 70.0 2
M+ = 96 37.0 1 50.0 3 58.0 1 77.0 3
38.0 3 51.0 6 63.0 2 79.0 11
1-heptyne 39.0 30 65.0 7 80.0 1
52.0 3
15.0 1 39.0 51 53.0 47 66.0 6 81.0 100
18.0 2 40.0 8 54.0 82 67.0 43 82.0 8
26.0 3 41.0 68 55.0 22 68.0 42 91.0 1
27.0 40 42.0 7 56.0 8 69.0 4 95.0 5
C7H12 28.0 7 43.0 26 57.0 1 77.0 5 96.0 18
29.0 9 50.0 6 62.0 2 78.0 1 97.0 2
M+ = 96
37.0 2 51.0 12 63.0 3 79.0 14
2-heptyne 38.0 4 52.0 9 65.0 10 80.0 3
mass %
mass % mass % mass % mass % 79.0 32
15.0 2 39.0 43 53.0 49 65.0 21 80.0 4
18.0 1 40.0 12 54.0 25 66.0 11 81.0 93
26.0 3 41.0 84 55.0 26 67.0 100 82.0 6
27.0 23 42.0 10 56.0 5 68.0 29 91.0 2
C7H12 28.0 1 43.0 3 61.0 1 69.0 2 93.0 1
29.0 14 50.0 6 62.0 3 74.0 1 95.0 7
M+ = 96 51.0 12 63.0 5
37.0 2 77.0 9 96.0 70
3-heptyne 38.0 4 52.0 7 64.0 1 78.0 2 97.0 6

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
R' CH2 fragmentation R' CH2 lots of rearrangement

resonance R'
radical cation tropylium ion,

Only cations reach the detector. This mass is 91 (if an aromatic cation
R = H) and even though it is a very stable cation, it (lots of resonance)
rearranges to a more stable 'tropylium' carbocation.
Any branches or heteroatoms would change the '91' R' = mass
mass. H 91
CH3 105
C2H5 119
HO 107
H2N 106
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 R H R
R
H
H H H
C or C
can be on either fragment
C C
H H
C C
H H
H R = mass H Both have even masses,
H H if there is not an odd
H 92 number of nitrogen atoms. R = mass
Even mass, if there is not an CH3 106 H 28
odd number of nitrogen atoms. C2H5 120 CH3 42
HO 108 C2H5 56
H2N 107 C3H7 70
H H H
H
H H H
C or C
can be on either fragment
C C
H H
O O
H H
M+ = 122 (35%) 94.0 = 100% 28.0 = 1%
Examples:
McLafferty rearrangements benzylic fragmentations
H
H
H
57 (4%)
C11H16 = 148 (27%) 92 (74%) 56 (0.4%) 91 (100%)
15 (0.2%)
29 (6%)
43 (1%)
57 (4%) 65 (9%)
43 (1%) 71 (0%) 77 (4%)
85 (0.2%)
105 (11%) 105 (11%)
bridging phenyl group

27.0 5 52.0 1 79.0 4 104.0 3 163.0 5
29.0 6 55.0 4 82.0 1 105.0 11
39.0 6 56.0 1 83.0 2 106.0 2
41.0 8 63.0 2 89.0 1 115.0 1
C12H18 42.0 1 65.0 9 91.0 100 117.0 1
M+ = 162 43.0 17 71.0 2 92.0 95 * 119.0 3
hexylbenzene 50.0 1 77.0 5 93.0 8 133.0 5
51.0 3 78.0 6 103.0 2 162.0 33
* Only about 7% is due to 13C isotopes.
27.0 1 64.0 2 92.0 1 119.0 21 162.0 21
29.0 2 65.0 4 103.0 2 120.0 2 163.0 3
39.0 2 66.0 1 104.0 1 128.0 2
41.0 6 77.0 4 105.0 4 129.0 1
C12H18 51.0 2 78.0 2 107.0 2 131.0 3
M+ = 162 53.0 1 79.0 6 115.0 5 133.0 1
57.0 1 89.0 1 116.0 2 147.0 100
1-t-butyl-3-ethylbenzene 63.0 1 91.0 14 117.0 4 148.0 12
Notice that "91" is not logical, but it shows up.
27.0 2 78.0 2 115.0 1
39.0 3 79.0 5 117.0 1
41.0 2 91.0 6 119.0 1
51.0 2 92.0 2 134.0 23
C10H14 53.0 1 103.0 3 135.0 2.6
M+ = 135 63.0 1 104.0 2
p-propyltoluene 65.0 2 105.0 100
77.0 6 106.0 9

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
R  R
fragmentation  

Free radicals are sucked
  away by the vacuum pump.
 
Cations reach the detector,
will see this mass.
X = mass
Cl 91
Br 135
I 183
X
X R
fragmentation
R Cations reach the detector, Free radicals are sucked

will see this mass. away by the vacuum pump.
X = mass
Cl 63
Br 107
I 155
Examples
mass % mass %
alkyl branches
Cl 15 (1%) Cl Cl 15.0 1 55.0 81
29 (32%) 26.0 2 56.0 56
1-chlorhexane 43 (72%) 84 (4%), minus HCl 27.0 27 57.0 15
C6H13Cl = 120 57 (15%) other alkene fragments 28.0 5 63.0 5
71 (3%) 63 (5%) 29.0 32 65.0 2
91 (100%) McLafferty allylic
85 (0.7%) 39.0 17 67.0 3
28 (5%) 27 (27%) 40.0 3 69.0 22
42 (45%) 41 (59%) 41.0 59 70.0 2
56 (56%) 63 (81%) 42.0 45 71.0 3
70 (3%) 43.0 72 84.0 4
84 (1%) 44.0 2 91.0 100
49.0 3 92.0 4
91.0 100 53.0 4 93.0 32
35
93.0 32 Cl and 37Cl 54.0 4 94.0 1
alkyl branches mass % mass %
Br 15 (1%) Br Br
29 (21%) 15.0 1 58.0 4.9
1-bromorhexane 43 (66%) 84 (4%), minus HBr 26.0 1 69.0 .5
C6H13Br = 165 57 (100%) 27.0 16 70.0 3
107 (1%) other alkene fragments 28.0 3 71.0 3
71 (3%) 135 (8%) McLafferty allylic
85 (18%) 29.0 21 81.0 1
28 (3%) 27 (16%) 39.0 11 83.0 1.5
42 (10%) 41 (42%) 40.0 2 84.0 1
56 (5%) 63 (0%) 41.0 42 85.0 18
70 (3%) 42.0 10 86.0 1
84 (1%) 43.0 66 99.0 14
44.0 2 100.0 1
91.0 100 53.0 2 107.0 1
35
93.0 32 Cl and 37Cl 54.0 1 109.0 1
55.0 6 135.0 8
91.0 100 56.0 5 137.0 8
35
93.0 32 Cl and 37Cl 57.0 100
alkyl branches mass % mass %

I 15 (1%) I I 27.0 14
29 (15%) 28.0 3
1-iodohexane 43 (100%) 84 (4%), minus HI
29.0 15
C6H13I = 212 57 (11%) 107 (2%) other alkene fragments 39.0 7
71 (0%) 183 (0%) McLafferty allylic 40.0 1
85 (50%) 41.0 25
28 (3%) 27 (14%)
42 (3%) 41 (25%) 42.0 3
56 (2%) 63 (0%) 43.0 100
70 (0%) 44.0 3
84 (0%) 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 alkyl branches
I 15.0 2 15.0 1
15 (2%) (1%) 26.0 2
29 (0%) (0%) 42, minus HI 26.0 1
1-iodopropane 27.0 32 27.0 28
43 (100%) (100%) other alkene fragments 28.0 2
C3H7I = 170 57 (0%) (0%) 28.0 2
not possible McLafferty allylic 38.0 2 38.0 2
71 (0%) (0%) 39.0 11 39.0 12
85 (0%) (0%) 28 (3%) (2%) 27 (32%) (28%)
42 (3%) (4%) 41 (37%) (36%) 40.0 2 40.0 2
I 41.0 37
56 (0%) (0%) 63 (0%) (0%) 41.0 36
70 (0%) (0%) 42.0 3 42.0 4
I 84 (0%) (0%) 43.0 100 43.0 100
Almost identical 155 (0%) 44.0 3 44.0 3
2-iodopropane mass spectra. 127.0 5 127.0 6
C3H7I = 170 I = 127.0 (5%) (6%) 128.0 1 128.0 2
HI = 128.0 (1%) (2%) 170.0 24 170.0 24

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
O M-18
fragmentation H H
H R' O
R'
This can lead to alkene fragmentations.
OH
OH
OH OH
linear has branch has branch has branch

15.0 3 15.0 2 15.0 3 15.0 2
26.0 3 26.0 2 26.0 1 26.0 2
27.0 33 27.0 10 27.0 4 27.0 23
28.0 12 28.0 52 28.0 1 28.0 12
29.0 16 29.0 6 29.0 6 29.0 8
31.0 83 31.0 17 31.0 27 31.0 40 H2C=OH
39.0 11 39.0 3 39.0 6 39.0 14
40.0 4 40.0 1 40.0 1 40.0 3
41.0 66 41.0 12 41.0 21 41.0 57
42.0 32 42.0 1 42.0 1 42.0 59
43.0 59 43.0 9 43.0 9 43.0 100
45.0 7 45.0 100 45.0 1 45.0 4 (M-29) = C2H5
53.0 1 53.0 1 53.0 1 53.0 1
55.0 14 55.0 2 55.0 2 55.0 6
56.0 100 56.0 2 56.0 3 56.0 5 (M-18) = H2O
57.0 6 57.0 2 57.0 8 57.0 3
59.0 0.3 59.0 20 59.0 100 59.0 6 (M-15) = CH3
74.0 0.6 74.0 0.2 74.0 0 74.0 13 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 R1
H O C R2 fragmentation H O C R2
H O C R2
R3 R3 R3
"X" lone pair electrons fill in loss of electrons at carbocation site. This is a common
radical cation
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.
4. Cyclic alcohols tend to show stronger M+ peaks than linear chains.

OH
OH OH
OH
M+ = 72 (1%) M+ = 86 (9%) M+ = 100 (3%) M+ = 114 (2%)

M-18 = 54 (1%) M-18 = 68 (7%) M-18 = 82 (46%) M-18 = 96 (23%)
M-28 = 44 (100%) M-28 = 58 (14%) M-28 = 72 (7%) M-28 = 86 (4%)
base peak = 44 (100%) base peak = 57 (100%) base peak = 57 (100%) base peak = 57 (100%)
OH OH OH OH
M+ = 74 (0.6%) M+ = 88 (0%) M+ = 102 (0%) M+ = 116 (0%)

M-18 = 56 (100%) M-18 = 70 (51%) M-18 = 84 (9%) M-18 = 98 (6%)
base peak = 56 (100%) base peak = 42 (100%) base peak = 56 (100%) base peak = 70 (100%)
5. When oxygen is present in any molecule, it is likely that mass 31 will be present.
H O C H H O C H
H H
Mass = 31 is almost always present when oxygen is present, especially in alcohols.
Example
OH
H (-H2O)
98 (4%), minus H2O
loss of water other alkene fragments
C7H16O M+ = 116 from either side McLafferty allylic
28 (0%) 27 (5%)
42 (4%) 41 (10%)
See alkene fragmentations earlier. The 56 (7%) 55 (15%)
pi bond can move around the carbon 70 (5%) 69 (3%)
skeleton, which can also rearrange. 84 (0%)
OH 98
alkyl branches actual peaks
a b a 15 (1%)
29 (5%) mass %
b CH3 43 (8%) 27.0 5
C5H11 71 57 (4%) 29.0 5
C7H16O M+ = 116 71 (1%) 31.0 2
15 85 (0%) 39.0 3
H H 41.0 10
O 42.0 4
O H 43.0 8
45 O 44.0 7
HC CH 45.0 100
CH3 46.0 2
101 CH2 55.0 15
31 56.0 7
Many types of skeletal rearrangements are possible using a such high energy electron beam. not logical, 57.0 4
The "31" fragment does not make sense at a 2o or 3o ROH, but is often observed (in ethers too). but observed 69.0 3
70.0 5
83.0 9
98.0 4
101.0 4

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
O R = mass
H 18
fragmentation H R CH3 32
H R' O C2H5 46
R'
C3H7 60
from either side
2. Alpha cleavage is common from either side and further loss of the carbonyl fragment is possible.
R1 R1
R' O C R2 fragmentation R' O C R2

R' O C R2
R3 R3 R3
radical cation
possible.
3. Loss of an oxygen carbon branch is also possible (from either side).
R1 R1
R' O C R2 fragmentation C R2
R' O
R3 R3
We only see the cations. The fragmentation
radical cation could potentially occur from either side.
56 (24%), minus ROH

a 28 (4%), minus ROH
(-ROH) mass %
O OH2 other alkene fragments
b a 46 (0%) 15.0 1
56 (24%) McLafferty allylic 18.0 3
H H loss of alcohol b 26.0 1
M+ = 102 (4%) 28 (4%) 27 (12%)
from either side HO 42 (3%) 41 (26%) 27.0 12
56 (24%) 55 (6%) 28.0 4
28 (4%) 74 (0%) 70 (0%) 69 (0%) 29.0 27
84 (0%) 31.0 57
39.0 5
d H2 41.0 26
c d c 42.0 3
C
CH3 O 43.0 6
H2C CH3
O O 44.0 1
15 (1%) 87 (2%) 43 (6%) 45.0 10
C6H14O M+ = 102 (4%) 59 (100%) 47.0 1
55.0 6
56.0 24
f H 57.0 31
e f e 58.0 1
O
59.0 100
O O O 60.0 3
CH2 73.0 8
73 (8%) 45 (10%) 57 (31%)
29 (27%) 31 (57%) 87.0 2
C6H14O M+ = 102 (4%)
101.0 1
not logical, 102.0 4
but observed
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)
S R = mass
H 34
fragmentation R H CH3 48
H R' S C2H5 62
R' C3H7 76
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 R1
R S C R2 fragmentation R S C R2
R S C R2
R3 R3 R3
radical cation
possible.
4. If a side chain has five or more atoms then  cleavage is possible with ring formation (see the
halogens). Beta (β) cleavage is also reasonable.
R R
S S
R  R
fragmentation  

Free radicals are sucked
  away by the vacuum pump.
 
Cations reach the detector,
will see this mass.
R = mass
H 89
CH3 103
C2H5 117
R
S R
S R
fragmentation
   
R Cations reach the detector, Free radicals are sucked
will see this mass. away by the vacuum pump.
R = mass
H 61
CH3 75
C2H5 89

Example
H H mass %
alkyl branches mass %
SH 15 (1%) S S 26.0 1 55.0 35
29 (15%) 27.0 16 56.0 100
1-hexanethiol 43 (48%) 84 (16%), minus H2S
28.0 4 57.0 7
C6H14S = 118 57 (7%) other alkene fragments 29.0 15 59.0
71 (0%) 61 (10%) 2
120 (5.3%) 89 (3%) McLafferty allylic 35.0 2 60.0 2
85 (2%) 39.0 9 61.0 10
28 (4%) 27 (16%)
42 (32%) 41 (35%) 40.0 2 62.0 1
56 (100%) 55 (35%) 41.0 35 69.0 25
70 (2%) 69 (25%) 42.0 32 70.0 2
84 (16%) 83 (1%) 43.0 48 83.0 1
44.0 2 84.0 16
45.0 4 85.0 2
46.0 2 89.0 3
47.0 15 118.0 30
48.0 1 119.0 2
53.0 2 120.0 1.6
54.0 3
mass % mass %
H H
alkyl branches 15.0 1 55.0 17
S 15 (1%) S 26.0 3 56.0 68
S
29 (50%) 56 (68%), minus H2S 27.0 36 57.0 17
butyl ethyl sulfide 43 (4%)
other alkene fragments 28.0 9 58.0 3
C6H14S = 118 57 (0%) 29.0 50 59.0 6
120 (4.8%) 71 (0%) 89 (25%) 61 (38%) McLafferty allylic 34.0 1 60.0 6
85 (0%) 28 (9%) 27 (36%) 35.0 9 61.0 38
CH3 42 (4%) 41 (49%) 39.0 11 62.0 47
H2S = 34 (1%) 56 (68%) 55 (17%) 40.0 2 63.0 20
S 70 (0%) 69 (0%) 41.0 49 75.0 100
84 (0%) 83 (0%) 42.0 4 76.0 8
43.0 4 77.0 5
45.0 12 89.0 25
75 (100%) 46.0 12 90.0 3
47.0 48 103.0 2
S S 48.0 6 118.0 56.4 = M+
(M-57) = 89 (38%) (M-29) = 89 (25%) 53.0 2 119.0 4
54.0 1 120.0 2.7 = M+2
Phenols - Key Points
1. Phenols tend to have intense M+ peaks. (See below = 100% and 36%.)
2. Loss of CO with extensive rearrangement is common.

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

R R1
OH R'
H R = mass
fragmentation CH3 107
O Lots of
resonance. C2H5 121
etc.
radical cation
Examples
mass % mass %
OH alkyl branches
15 (0%) 27.0 2 62.0 2
29 (0.8%) 37.0 2 63.0 4
43 (0.4%) 38.0 4 64.0 1
57 (0%) 39.0 14 65.0 17
71 (0%) 65 (17%) 39 (14%) 40.0 9 66.0 23
phenol 85 (0%) 47.0 4 67.0 2
C6H60 = 94 (100%) 50.0 3 74.0 1
M+1 = (7%) 51.0 3 93.0 2
53.0 2 94.0 100
55.0 7 95.0 7
61.0 1
alkyl branches
OH 15 (0.4%) R OH mass % mass %
29 (0.4%)
43 (0.4%) 27.0 3 65.0 3
57 (0%) 38.0 1 77.0 13
71 (0%) R=H 65 (3%) 39 (6%) 39.0 6 78.0 3
85 (0%) 41.0 1 79.0 2
p-ethylphenol R=CH3 79 (2%)
50.0 3 91.0 4
27 (3%) R=C2H5 93 (1%) 94.0 1
C6H60 = 122 (36%) 107 (100%) 51.0 5
41 (1%) 52.0 3 103.0 2
M+1 = (3%) OH 107.0 100
55 (3%) allylic R 53.0 2
69 (0%) 55.0 3 108.0 8
83 (0%) 62.0 1 121.0 3
63.0 2 122.0 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 H H2
H3C N C H
CnH2n+2+NOm CnH2n+2Om
H3C O
H
Molecules made with an odd number of Molecules made with C, H, S, O, halogens
nitrogen atoms have odd molecular masses and an even number of nitrogen
because they have an odd number of hydrogens. atoms have even molecular masses.
2. Alpha cleavage is usually a major fragmentation pattern in a manner similar to alcohols and
ethers.
R1 R1 mass
all R = H 30
fragmentation R' N C R2 R' N C R2
R' N C R2 one CH3 44
resonance
C2H5 58
R" R3 R" R3 etc.
R" R3
The fragment mass depends on what is present in the "R" groups. If all
radical cation R groups are "H" (H2N=CH2 ) then the mass will be 30, which shows up
in almost every amine compound examined, even tertiary amines.

3. Loss of a branch at nitrogen is also possible in a manner similar to alcohols and ethers.
R1 R1
R' N C R2 fragmentation R' N C R2
R" R3 R" R3
radical cation 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.
R1
odd mass
NH2 R'
H R' = mass
1. fragmentation Lots of H 106
R N
2. rearrangement resonance. CH3 120
C2H5 134
H etc.
R' radical cation
odd mass even mass
Examples
mass %
56 (6%), minus RNH2 15.0 1
a b other alkene fragments 18.0 2
(-ROH) McLafferty 27.0 7
N allylic 28.0 8
b a 28 (8%) 27 (7%) 29.0 18
H H H 42 (4%) 41 (18%) 30.0 100
loss of amine 56 (6%)
from either side 56 56 55 (7%) 31.0 1
n-isobutyl-sec-butylamine 70 (2%) 69 (0%) 39.0 5
M+ = 129 (1%) 84 (2%) 41.0 18
C8H19N 42.0 4
43.0 2
d c 44.0 53
e C2H5 45.0 1
c N 55.0 7
H
56.0 6
N 29 (18%) 57.0 24
H 100 (18%)
58.0 20
70.0 2
d 72.0 6
n-isobutyl-sec-butylamine CH3 N 84.0 2
H 86.0 66
M+ = 129 (1%)
15 (1%) 114 (8%) 87.0 4
100.0 67
e 101.0 5
114.0 8
NH2 alkyl branches 128.0 1
30 (100%) 129.0 1
C3H7 29 (18%)
N CH2 43 (2%)
H 57 (24%)
86 (66%) 43 (2%) not logical, but observed 71 (0%)
and is even the base peak 85 (0%)
NH2
N (-ROH) 45 (0%) 56 (3%) See alkene
b H a
fragmentations above.
b
H M+ = 101 (9%) H
H2N
butylethylamine 28 (5%) 73 (0%)
mass %
c 15.0 1
d c
18.0 1
N CH3 27.0 5
H N 28.0 5
15 (1%) H
C6H15N M+ = 101 (9%) 86 (2%) 29.0 8
30.0 33
butylethylamine d 39.0 2
H2
C 41.0 4
N 42.0 3
H2C CH3 43.0 2
58 (100%) H 43 (2%)
44.0 10
e 56.0 3
e f 57.0 3
58.0 100
N HN 59.0 4
H 72 (0%) NH2 86.0 2
29 (8%) NH4
C6H15N M+ = 101 (9%) 100.0 2
f CH2 18 (1%) 101.0 9
butylethylamine
30 (33%)
NH
44 (10%) 57 (3%)
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 C O R1 C O
C
R1 R2
O C R2 O C R2
radical cation
R1 or R2 can be lost from
An oxygen lone pair paritally fills in the loss of electrons at the
aldehydes, ketones, acids, carbocation site via resonance. This is a common fragmentation
esters, amides, acid chlorides, pattern for any carbonyl compound and can occur from either
etc. side, though some are more common than others.

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 C O R1 C O R1
loss of Subsequent loss of CO is possible
after  fragmentation, so not only
can you see loss of an  branch you
C O can also see the mass of an  branch.
O C R2 O C R2 R2
4. McLafferty rearrangements are common with at least three carbons in a side chain. Cleavage occurs
between Cα and Cβ.
R
H H
O C Positive charge can be on R
R O either fragment, which
typically has an even mass. C
C C R R
C
R1 C
R R1 C = alpha position C R
 = beta position
R R  = gamma position R
radical cation 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
mass %
Loss of side chain, then CO (?) O 18.0 2
OH O 26.0 2
a 27.0 17
H
28.0 4
O 17 (0.4%) C 29.0 14
a 99 (0.8%) 71 (2%)
b 30.0 1
28 (5%)* 31.0 2
HO alkyl branches 39.0 10
O 15 (0.9%) 40.0 2
C6H12O2 = 116 (0%) b 29 (14%) 41.0 26
71 (2%) 43 (14%) 42.0 7
HO 57 (12%) 43.0 14
45 (100%) 71 (2%) 45.0 9
*28 could also be ethene 85 (0.4%) 53.0 1
99 (0.8%) 55.0 10
McLafferty alkenes 56.0 8
H 57.0 12
H McLafferty 58.0 6
O O allylic
59.0 3
O 60.0 100
HO 61.0 9
HO 69.0 3
HO 56 (8%) 41 (26%) 70.0 3
60 (100%) 55 (10%) 71.0 2
C6H12O2 = 116 (0%) 28 (4%) 69 (3%) 73.0 44
42 (7%) (M-29) = 87 (11%)
hexanoic acid 83 (1%) 74.0 7
70 (3%) 83.0 1
87.0 11
Esters
mass %
Loss of side chain, then CO (?) 15.0 10
18.0 1
26.0 1
H3CO O O 27.0 11
a 28.0 2
O 29.0 12
a b 31 (2%) C 31.0 2
99 (19%) 28 (2%)* 71 (10%) 39.0 7
40.0 1
CH3O
alkyl branches 41.0 17
O 42.0 6
15 (10%) 43.0 31
C7H14O2 = 130 (0.4%) 29 (12%)
b 44.0 2
43 (31%) 45.0 2
CH3O 71 (10%) 57 (4%) 53.0 1
59 (15%) 71 (10%) 55.0 9
99 (19%) 57.0 4
McLafferty alkenes
59.0 15
H 69.0 2
H McLafferty
O allylic O 70.0 3
O CH3O 71.0 10
73.0 1
74.0 100
CH3O 75.0 5
H3CO 56 (2%) 41 (17%) 87.0 32
55 (9%) (M-29) = 101 (8%) 88.0 4
74 (100%) 28 (2%) 69 (2%)
C7H14O2 = 130 (0.4%) 42 (6%) 99.0 19
83 (0%) 100.0 1
methyl hexanoate 70 (3%)
101.0 8
Aldehyde
mass %
15.0 2
18.0 1
Loss of side chain, then CO (?) 26.0 3
27.0 34
H O O 28.0 8
a
29.0 33
C 30.0 2
1 (?) 31.0 2
99 (0.4%) 71 (7%)
OH 28 (8%)* 38.0 2
a b 39.0 20
alkyl branches 40.0 4
O 15 (2%) 41.0 69
H 29 (33%) 42.0 11
b 43 (55%) 43.0 55
C6H12O = 100 (0.4%) 57 (38%) 44.0 100
H 71 (7%) 71 (7%) 45.0 20
hexanal 29 (33%) 85 (0.3%) 50.0 1
53.0 3
54.0 2
alkenes 55.0 15
McLafferty 56.0 82
McLafferty 57.0 38
H allylic 58.0 9
H
O O 60.0 4
O H 67.0 8
69.0 1
56 (82%) 41 (69%) 71.0 7
H 72.0 17
55 (15%)
C6H12O = 100 (0.4%) 44 (100%) 28 (8%) 69 (1%) (M-29) = 71 (7%) 73.0 2
42 (11%) 83 (1%) 81.0 1
hexanal 70 (0%) 82.0 13
83.0 1

Ketone
Loss of side chain, then CO (?) O
CH3 O
a mass %
15 (4%) C 15.0 4
H 99 (4%) 28 (2%)* 71 (14%) 18.0 2
O 27.0 9
a b alkyl branches 28.0 2
15 (4%) 29.0 9
O 29 (9%) 39.0 7
43 (100%) 40.0 1
C7H14O = 114 (10%) b 57 (2%) 41.0 12
2-heptanone 71 (14%) 42.0 3
71 (14%) 85 (3%) 43.0 100
43 (100%) 99 (4%) 44.0 2
*28 could also be ethene 45.0 1
53.0 1
McLafferty alkenes 55.0 5
McLafferty 56.0 2
H H allylic 57.0 2
O O O 58.0 91
59.0 15
71.0 14
56 (2%) 41 (12%) 72.0 4
55 (5%) 85.0 3
C7H14O = 114 (10%) 58 (91%) 28 (2%) (M-29) = 85 (3%) 99.0 4
69 (0%)
42 (3%) 83 (0%) 113.0 2
2-heptanone 114.0 10
70 (0%)
115.0 1
Amide
Loss of side chain, then CO (?)
NH4 O
O
a 18 (2%)=NH4
99 (1%) C
O 98 (0.2%) 28 (2%)* 71 (2%)
a b alkyl branches
15 (0%) mass %
H2N O 29 (8%) 18.0 2
18 could be 43 (26%) 27.0 9
b 57 (2%) 28.0 2
C6H13NO = 115 (0.6%) NH4 or H2O
H2N 71 (2%) 29.0 8
hexanamide 71 (2%) 85 (0%)
44 (29%) 39.0 6
*28 could also be ethene 99 (1%) 41.0 12
42.0 4
alkenes 43.0 26
McLafferty
H McLafferty 44.0 28
H 45.0 1
allylic
O O O 55.0 4
H2N 57.0 2
59.0 100
H2N 56 (0%) 60.0 3
H2N 41 (12%) 71.0 2
28 (2%) 55 (4%) (M-29) = 86 (9%) 72.0 19
C6H13NO = 115 (0.6%) 59 (100%) 42 (4%) 69 (0%) 73.0 4
70 (0%) 83 (0%) 86.0 9
hexanamide
99.0 1
Full example for 2-methyl-4-heptanone
2-methylheptan-4-one Mostly peaks greater than 5% 27.0 17 57.0 100

O of the base peak are shown. 28.0 2 58.0 27
29.0 17 59.0 1
39.0 11 69.0 2
40.0 2 70.0 1
57 = base 71.0 70
41.0 36
C8H16O 43 42.0 5 72.0 3
71
MW = 128 43.0 73 85.0 72
44.0 3 86.0 11
53.0 1 113.0 6
55.0 2 128.0 23
41 58 56.0 1 129.0 2
27 29 M+ = 128
39 86 113
28 42 100
20 30 50 60 70 80 90 100 110 120 130

40
a = only see the fragment that b = only see the fragment that
H H retains the positive charge retains the positive charge
O 2 McLafferty a H b H
possibilities O O
b a and b
a 28 (2%)
C8H16O = 128 (23%) 42 (5%) 86 (11%) 100 (0.4%)
c = only see the fragment that

Lose c retains the positive charge
O left Lose
c branch CO
O O
C C
28 (2%) 43 (73%)
C8H16O = 128 (23%) 57 (100%) 71 (70%)
reasonable
mass peaks
d = only see the fragment that 128
d retains the positive charge 100
Lose
86
O d right Lose
branch 85
O CO O 71
C C 57
43
85 (72%) 57 (100%) 28 (2%) 42
C8H16O = 128 (23%) 43 (73%) 28

Nitriles - Key Points

1. Usually have weak M+ peaks. An odd number of nitrogen atoms produces an odd molecular ion
peak.
H2 Compare.
CnH2n-2+N H2 CnH2n-2
C C
H3 C C H3C C
C3H5N C4H6
N CH MW = 54
MW = 55
Nitriles made with an odd number of Alkynes made with C and H
nitrogen atoms have odd molecular masses have even molecular masses.
because they have an odd number of hydrogens.
2. With side chains of three carbons or longer McLafferty rearrangements are possible.
H R R
H HN
N C C
...or...
fragmentation C
C odd CH C
CH even
mass mass R R
odd
mass R
R
mass = 41 (R = H) mass = 28 (all H)
radical cation 55 (R = CH3) 42 (1R = CH3)
69 (R= CH2CH3) 56 (1R= CH2CH3)
83 (R = C3H7) 70 (1R = 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.
3. Alpha cleavage is possible.
N
R C N
C even C
fragmentation odd
odd mass R mass C
mass
radical cation The detector sees cations. Radicals are pumped away.
Example
mass %
15.0 2
Loss of side chain, then CN (?) alkyl branches 26.0 4
N 27.0 33
H 15 (2%)
29 (43%) 28.0 9
N a C 29.0 43
43 (32%)
a 57 (28%) 30.0 1.6
hexanenitrile 26 (5%) 71 (1%) 37.0 1
71 (1%) 85 (0%) 38.0 3
39.0 22
C6H11N = 97 (0.8%)
40.0 5
perhaps...? 41.0 100
H 27 (33%)
H 42.0 14
NH H2C CH 43.0 28
NH 50.0 1
b 43 (32%) 54 (82%) or 51.0 2
42 (14%) 55 (42%) 52.0 3
41 (100%) 56 (4%) HCNH
b 53.0 4
54.0 82
55.0 42
alkenes 56.0 4
McLafferty 57.0 32
McLafferty 58.0 1
H H allylic 66.0 1
N N 67.0 1
68.0 30
69.0 23
56 (4%) 41 (100%) 70.0 4
55 (42%) 71.0 1
28 (9%) 69 (23%) 82.0 24
C6H11N = 97 (0.8%) 41 (100%)
42 (14%) 83 (1%) 83.0 1
70 (4%) 96.0 12
hexanenitrile 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.

Common fragmentation patterns in mass spectroscopy (only cations are observed)

1. Fragment a branch next to a pi bond (α cleavage)
R R Characteristic carbocation stability also applies.

C C C C C C C C C
3o R > 2o R > 1o R > CH3
radical cation Pi electrons partially fill in loss of electrons at carbocation

pi bond of an alkene, site via resonance. This is a common fragmentation We only see the cationic fragments. The
alkyne or aromatic pattern for alkenes, alkynes and aromatics. radical fragments are lost to the vacuum.
2. Fragment a branch next to an atom with a lone pair of electrons
R
X C X C R
X C
radical cation 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;
adjacent lone pair ofan nitrogen = amine, amide; sulfur = thiol, sulfide, etc.) Alcohols often lose water (M-18), ethers can
oxygen or nitrogen atom lose ROH, primary amines can lose ammonia (M-17), etc.
3. Fragment a branch next to a carbonyl (C=O) bond…and possible subsequent loss of carbon monoxide, CO
loss of
a
R1 C O R1 C O R1
O C
O
b a
loss of
C b R2
R1 R2 O C R2 O C R2
R1 or R2 can be lost O C
from aldehydes, ketones, An oxygen lone pair partially fills in the loss of electrons Subsequent loss of CO is possible after
acids, esters, amides...etc. at the carbocation site via resonance. This is a common  fragmentation, so not only can you
fragmentation pattern for any carbonyl compound and see loss of an a branch, you can also
can occur from either side, though some are more common see the mass of an  branch.
than others.
4. McLafferty Rearrangement
H H The positive charge can be on
O C O
C either fragment, which typically
have even masses (unless an odd
C C C
C
number of N is present).
R1 C R1 C
 = alpha position
 = beta position
cation fragment OR cation fragment  = gama position
radical cation
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%).
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 R
CH3 = 15 C
R R
CH3CH2 = 29 H
C3H7 = 43 mass = 39 (R = H)
C4H9 = 57 53 (R = CH3) mass = 41 (R = H)
67 (R= CH2CH3) 55 (R = CH3) mass = 65 (R = H) mass = 91 (R = H)
C5H11 = 71
C6H13 = 85 also works for 69 (R= CH2CH3) 79 (R = CH3) 105 (R = CH3)
83 (R=C3H7) 93 (R= CH2CH3) 119 (R= CH2CH3)
R CH2
H R
H2N C O O C R
H C
mass = 29 (R = H)
H2
mass = 44
43 (R = CH3)
mass = 42 (R = H)
H 57 (R= CH2CH3)
mass = 27 56 (R = CH3) 71 (R = C3H7)
mass = 77 RO C O
70 (R= CH2CH3) 85 (R = C4H9)
mass = 45 (R = H) 84 (R=C3H7)
59 (R = CH3) 99 (R = C5H11)
73 (R = CH2CH3) 105 (R = C6H5)
87 (R = C3H7) 45 (R= OH)
Loss of small molecules via elimination reactions. 59 (R= OCH3)
HCl HBr 44 (R= NH2)
H2O H2S CH3OH C2H5OH NH3 CH3CO2H HF
36 (75%) 80 (50%)
mass = 18 34 32 46 17 62 20 38 (25%) 82 (50%)
McLafferty Rearrangement Possibilities
H R
H Notice! O HC
O R2 even masses McLafferty R2
(without N) = CH2
C
R1 R1
R CH2 mass = 28 (R = H)
R C variable mass,
H2 44 (R = H) 60 (R = OH) 42 (R = CH3)
58 (R = CH3) 74 (R = OCH3) (can sometimes see this 56 (R= CH2CH3)
mass = fragment if it retains the 70 (R = C3H7)
72 (R = CH2CH3) 59 (R = NH2)
86 (R = C3H7) 78 (R = Cl) cation charge) 84 (R = C4H9)
Similar Patterns - positive charge is written on both fragments to show that either fragment might be seen at the detector
H H
H
CH2 R2 H H
R2
C R2 N R2
R1
R1 R1
R C R1
H2 C C
H2 C H2
H2
H H
H2C R2 H H H
H C R2 N R2
R2
C R1 R
R CH2 C R1 C R1
R1
CH2 CH2
mass = 42 (R = H) mass = 92 (R = H) mass = 40 (R = H) mass = 41 (R = H)

56 (R = CH3) 106 (R = CH3) 54 (R = CH3) 55 (R = CH3)
70 (R= CH2CH3) 120 (R= CH2CH3) 68 (R= CH2CH3) 69 (R= CH2CH3)
84 (R = C3H7) 134 (R = C3H7) 82 (R = C3H7) 83 (R = C3H7)

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.
Mass Spec Problem Set 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.
Average Nuclide
Element Atomic Mass (Relative Abundance) Mass
1
H 1.00797 H (100) 1.00783
2
H H (0.016) 2.01410
12
C 12.01115 C (100) 12.00000
13
C C (1.08) 13.00336
16
O 15.9994 O (100) 15.9949
17
O O (0.04) 16.9991
18
O 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.

m/e % base
m/e % base b.
a. H2 H2 H2 27.0 20.1
27.0 17.2 C C C CH3 29.0 27.4
CH3 29.0 33.6 H 3C C C C 41.0 43.8
H 3C 41.0 49.1 H2 H2 H2 42.0 15.3
42.0 5.6 43.0 100.0
C CH3
43.0 100.0 M+ = 114 55.0 11.4
H 3C C
H2
55.0 11.3 56.0 18.4
56.0 28.0 57.0 33.5
M+ = 86 57.0 98.3 Is there a logical peak that is missing? 70.0 12.1
71.0 76.7 71.0 20.4
72.0 4.5 85.0 26.5
86.0 <1.0 114.0 6.0
c. m/e % base
27.0 10.0
41.0 49.5 H
42.0 24.7 No easy explanation for
? 56, but if ring opens and
43.0 11.2
56.0 100.0 forms alkene, McLafferty
M+ = 84 69.0 35.4 might work.
84.0 17.5
d. e. m/e % base
m/e % base 27.0 32.9
H2 29.0 24.4 CH
27.0 20.8 C C 39.0 54.9
41.0 68.2 H3C C 40.0 61.2
42.0 31.4 H2 41.0 22.7
M+ = 84 43.0 100.0 42.0 22.3
56.0 49.8 M+ = 68 53.0 44.0
69.0 16.9 67.0 100.0
You might have to 84.0 11.7 68.0 15.3
move the C=C around. Don't remove the sp C-H, there is a better
spot to lose an H atom (resonance).
f. g. m/e % base
H2
H2 H2 27.0 32.7
C CH3
m/e % base C C 29.0 16.1
C
H2 H3C C OH 31.0 83.4
65.0 7.2 H2 41.0 65.6
77.0 2.7 42.0 31.6
M+ = 120 91.0 100.0 M+ = 74 43.0 59.3
92.0 10.8 56 is an even mass, but not 55.0 14.1
105.0 3.8 McLafferty. A small molecule 56.0 100.0
Use a bridging ring to make 105. 120.0 25.9 might help explain it. 57.0 5.9
74.0 <1.0
h. m/e % base i. m/e % base

OH
27.0 9.8 27.0 23.0
H2 28.0 7.9
CH CH3 28.0 51.5 C O CH3
29.0 6.0 29.0 34.9
H3C C 31.0 16.8
H 3C C
H2
C
H2 31.0 100.0
H2
41.0 11.7 42.0 4.1
M+ = 74 43.0 9.2 M+ = 88 43.0 39.8
45.0 100.0 59.0 98.3
56.0 1.5 73.0 3.3
Peak 31 is harder to 88.0 25.7
explain, but common. 59.0 20.5
74.0 <1.0 28 and 42 are even, but not McLafferty. Think like "g", but
"organic" water. 31 requires some drastic rearrangements.
j. k. O
H2 H2 m/e % base
C C H2
m/e % base C C CH3 27.0 8.2
H 3C C NH2
H2 29.0 14.8
27.0 3.5 H 3C C C
43.0 100.0
29.0 2.1 H2 H2
M+ = 73 57.0 15.8
30.0 100.0 M+ = 100 58.0 49.8
Peak 30 dominates. Think of a 43.0 1.2
85.0 6.4
small molecule elimination for 56.0 1.2 100.0 8.0
73.0 7.3 43 is different than C3H7+
peak 56.
l. O m. m/e % base
m/e % base O
H2
H2
27.0 47.0
C C 27.0 73.5 H3C C C 29.0 9.2
H C CH3 29.0 54.8 41.0 45.3
41.0 69.1 O C CH3
H2
H2 43.0 100.0
43.0 75.3 + 59.0 22.2
M+ = 72 44.0 100.0
M = 102
71.0 49.9
57.0 23.3 74.0 64.2
29 is different than C2H5+ 72.0 53.6 74 is an even mass. 87.0 16.4
44 is an even mass, so... 102.0 1.4
n. o. O m/e % base
O
m/e % base
H2 27.0 26.6
H2
C C 27.0 13.6 C C 29.0 26.1
29.0 8.1 H 2N C CH3 41.0 53.4
HO C CH3
H2 41.0 16.3 H2 43.0 32.2
43.0 14.1 44.0 66.3
M+ = 88 45.0 9.9 M+ = 87 59.0 100.0
60.0 100.0 71.0 8.0
An even mass strikes again 73.0 32.5 72.0 19.2
at 60 and 45 is not common, Normally 59 would be even,
88.0 2.6 but there is nitrogen present. 87.0 2.9
but expected here.
p. q.
m/e % base m/e % base
N
H2
C C 27.0 28.6 27.0 9.3
C CH3 29.0 66.3 41.0 19.3
H2 40.0 3.8 68.0 100.0
41.0 100.0 91.0 12.7
M+ = 69
42.0 4.0 92.0 18.8
Normally 41 would be even, 54.0 1.2 M+ = 136 95.0 7.6
but there is nitrogen present. 69.0 0.2 121.0 19.5
Two famous names goes with 68. 136.0 22.6

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.
Sample A answer (remove) oct-1-yne Major peaks

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 3
28 5
%T 29 6
39 36
100 40 25
41 64
725 42 16
2120 1375 43 49
1385 50 6
50 51 8
3310 1470 52 4
53 15
54 27
2960-2850 650 55 3
0 65 5
3500 3000 2500 2000 1500 1000 500 67 100 (base)
4000 68 6
 = wavenumber = cm-1 81 10
82 = M+
100% 67 = base peak
75% 41
50% 43
39
40 54 M+ peak = 82
42
25% 53 (very small)
81
0%
20 30 40 50 60 70 80 90 100 110
m/e
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 6
29 4
%T 39 12
40 4
100 41 11
53 13
54 16
1685 1375 55 28
1385 838 65 4
50 67 42
1470 68 36
77 5
79 11
2960-2850 81 100 (base)
0 82 7
3500 3000 2500 2000 1500 1000 500 95 8
4000 96 41 = M+
 = wavenumber = cm-1 97 4
100% 81 = base peak
75%
50%
67 M+ = 96
55 68
25%
39 41 54
53 79
0%
20 30 40 50 60 70 80 90 100 110
m
e
Major peaks Major peaks
Sample C 4-methyl-1-bromopentane
mass percent mass percent
MW = 164 (remove in book)
Mass Spec - Only larger and/or significant peaks are shown. 85.0 59
15.0 1
Hint: (M+2) is helpful, as are 151/149, 109/107. Explain 85, 57 and 43. 27.0 13 86.0 4
28.0 1 107.0 3
%T 29.0 8 109.0 2
38.0 1 149.0 3
100 39.0 11 151.0 3
40.0 2 164.0 2 = M+
41.0 44 166.0 2 = M+2
42.0 42
1385 43.0 100 (base)
50 44.0 3
1470 1250 640 560
53.0 2
55.0 5
2960-2850 56.0 12
57.0 9
0 69.0 31
4000 3500 3000 2500 2000 1500 1000 500 70.0 2
83.0 1
 = wavenumber = cm-1 84.0 2
100% 43 = base peak
75%
85
41
50% 42
69
25% 56 107
57 149 164 = M+
109 151 166 = M+2
0%
20 40 60 80 100 120 140 160 180 200
m
e

Sample D p-thiomethyltoluene Major peaks Major peaks

MW = 138 (remove in book) mass percent
Mass Spec - Only larger and/or significant peaks are shown. mass percent
27.0 3 106.0 10
Hint: (M+2) is helpful. There is no major peak at 91 for a reason, but 105 will substitute. 135.0 2
39.0 4
%T 45.0 6 137.0 2
50.0 2 138.0 15.5 = M+
100 51.0 4 139.0 2
52.0 1 140.0 0.9 = M+2 (5.8%)
3050 53.0 2
1375 63.0 2
3550 1385 65.0 3
50 68.0 2
1520 1440 77.0 11
78.0 4
79.0 11
2960-2850 820 89.0 1
0 91.0 5
3500 3000 2500 2000 1000 500 93.0 1
4000 1500 103.0 8
105.0 100 (base)
100%
105 = base peak
75%
50%
25% 138 = M+
77 79
140 = M+2
0%
20 40 60 80 100 120 140 160 180 200
m
e
Sample E butoxybenzene Major peaks Major peaks

Mass Spec - Only larger and/or significant peaks are shown. MW = 150 (remove in book) mass percent mass percent
Hint: McLafferty can explain 94, though there is no carbonyl group, but there is an xygen. 107 is 27.0 4.1
small, but more like what you would expect for this functional group. Regular peaks at 29 and 57. 29.0 11.2
%T The IR peak at 1220 is important. 39.0 7.1
40.0 1.4
100 41.0 8.3
50.0 1.2
3040 51.0 4.4
55.0 1.5
1380 56.0 1.1
50 57.0 3.9
63.0 1.1
65.0 5.3
2960-2850 1600 1500 1250 760 690 66.0 5.5
77.0 7.4
0 94.0 100.0 (base)
4000 3500 3000 2500 2000 1500 1000 500 95.0 7.0
 = wavenumber = cm-1 107.0 1.6
150.0 18.4 = M+
151.0 2.1
100% 94 = base peak
75%
50%
25% 150 = M+
29 41 57 69 77 107
0%
20 40 60 80 100 120 140 160 180 200
m
e
Sample F propylbenzene Major peaks Major peaks

Hint: The big base peak is a big clue. 27.0 2
39.0 4
%T 41.0 2
50.0 1
100 51.0 4
63.0 2
65.0 7
3030
1610 77.0 3
50 78.0 6
1500 79.0 1
89.0 1
91.0 100 (base)
2960-2850 1450 740 700 92.0 12
0 103.0 1
3500 3000 2500 2000 1000 500 105.0 4
4000 1500 120.0 26 = M+
100% 91 = base peak
75%
50%
120 = M+
25%
41 65 103
29 78 105
0%
20 40 60 80 100 120 140 160 180 200
m
e
Sample G Major peaks Major peaks

octan-3-one
Hint: There are a lot of peaks that could be explained, both large and small. 15.0 1 72.0 67
Try 100, 86, 85, 71, 57, 43 and 29. McLafferty might help on some of these. 18.0 1 73.0 8
%T 26.0 2 81.0 1
27.0 21 85.0 10
100 28.0 4 86.0 3
29.0 58 99.0 52
3420 30.0 1 100.0 4
39.0 8 128.0 12 = M+
40.0 1 129.0 1
50 41.0 17
1460 1410
1380 42.0 4
43.0 100 (base)
44.0 4
2960-2850 1720 53.0 2
0 55.0 9
3500 3000 2500 2000 1500 1000 500 56.0 3
4000 57.0 92
71.0 52
43 = base peak
57
72
29 99
71
50%
25%
85 128 = M+
0%
20 40 60 80 100 120 140 160 180 200
m
e


Sample H 2-ethylhexanal
Hint: There are a lot of peaks that could be explained, both large and small. Try 100, 72, 27.0 15 71.0 5
57, 43 and 29. McLafferty might help on some of these. 28.0 1 72.0 100 (base)
%T 29.0 24 73.0 5
39.0 9 81.0 1
100 40.0 1 82.0 3
41.0 34 85.0 3
3420 2810 42.0 4 100.0 1
2700 43.0 40 128.0 1 = M+
44.0 2
50 53.0 2
1460 1340
54.0 3
55.0 11
56.0 4
2960-2850 1730 57.0 82
0 58.0 4
3500 3000 2500 2000 1500 1000 500 67.0 2
4000 68.0 1
70.0 1
100% 72 = base peak
57
75%
50%
41 43
25% 27 29
15 55
128 = M+
0%
20 40 60 80 100 120 140 160 180 200
m
e

Sample I pentylamine
18.0 2
Hint: Notice the odd mass peak and the really big peak at 30. Though small 29 and 43 are obvious. 27.0 3
%T 28.0 33
29.0 2
100 30.0 100 (base)
31.0 2
39.0 2
3370 41.0 3
3290 1610 42.0 2
50 43.0 1
1470 1380 44.0 2
820 45.0 3
87.0 4 = M+
2960-2850
0
4000 3500 3000 2500 2000 1500 1000 500
 = wavenumber = cm-1
30 = base peak
50%
27
25%
87 = M+
0%
20 40 60 80 100 120 140 160 180 200
m
e
Sample J Major peaks Major peaks

heptane
Hint: Look how regular the peaks are. What is lost in each fragment…100, 85, 71, 57, 43, 29? 15.0 1 72.0 2
26.0 1 85.0 2
%T 27.0 18 100.0 11 = M+
28.0 3
100 29.0 31
39.0 11
40.0 2
41.0 45
1380 42.0 20
50 720
1470
43.0 100 (base)
44.0 3
53.0 1
55.0 10
2960-2850 56.0 25
0 57.0 47
3500 3000 2500 2000 1500 1000 500 58.0 2
4000 70.0 18
43 = base peak
57
99
41
50% 42
29 71
56
25%
70 100 = M+
72 85
0%
20 40 60 80 100 120 140 160 180 200
m
e
Sample K Major peaks Major peaks

2-ethylpentane
27.0 10
Hint: You can barely see the M+ peak because…? 43 is big and 71, 57 and 29 are all there too. 29.0 14
%T 39.0 6
41.0 16
100 42.0 7
43.0 100 (base)
44.0 4
53.0 1
1380 770 55.0 15
50 56.0 4
1460 890 57.0 4
70.0 48
71.0 51
2960-2850 72.0 3
0 100.0 2 = M+
4000 3500 3000 2500 2000 1500 1000 500
43 = base peak
41
50% 42 70 71
25%
29 55
27 100 = M+
57 72
0%
20 40 60 80 100 120 140 160 180 200
m
e

Sample L Major peaks Major peaks

dipropylsulfide
15.0 2
Hint: The (M+2) at 120 is helpful, as are 103, 89, 43 and 29. Why is 89 so big and 103 so small? 27.0 25
%T 29.0 6
39.0 16
100 41.0 2
42.0 65
43.0 100 (base)
47.0 47
1380 61.0 35
50 75.0 13
76.0 50
89.0 92
103.0 4
2960-2850 1470 118.0 63 = M+
0 119.0 5
4000 3500 3000 2500 2000 1500 1000 500 120.0 3 = M+2 (4.8%)
43 = base peak 89
42 118 = M+
47 76
50%
61
27
25% 75
29 103 120 = M+2 (4.8%)
0%
20 40 60 80 100 120 140 160 180 200
m
e
Sample M Major peaks Major peaks

1-iodohexane
Hint: Look at that big hole in the middle…then there's 85, 57, 43, 29. 27.0 14
28.0 4
%T 29.0 15
39.0 7
100 40.0 1
41.0 25
42.0 3
1370 43.0 100 (base)
1420 44.0 3
50 53.0 1
55.0 6
56.0 2
57.0 11
2960-2850 1460 85.0 50
0 86.0 3
4000 3500 3000 2500 2000 1500 1000 500 155.0 2
212.0 4 = M+
43 = base peak
85
50%
25% 29
57 86 212 = M+
155
0%
20 40 60 80 100 120 140 160 180 200
m
e
Sample N Major peaks Major peaks

hexan-1-ol mass percent mass percent
Mass Spec - Only larger and/or significant peaks are shown. MW = 102 (remove in book)
15.0 1 84.0 9
Hint: If you look hard there is a tiny peak at 102 (=M+)…and then a gap of 18. Some 18.0 3 102.0 0 M+ (missing)
familiar peaks at 57, 43 and 29 are helpful. There's a special reason that 31 is there…why? 27.0 15
%T 28.0 3
29.0 20
100 31.0 24
39.0 8
41.0 36
1380 42.0 43
660
50 43.0 59
45.0 3
3320 53.0 2
55.0 49
2960-2850 1470 1060 56.0 100
57.0 7
0 69.0 25
4000 3500 3000 2500 2000 1500 1000 500 70.0 3
73.0 1
83.0 2
56 = base peak
43
55
50%
42
31 41 69
25% 29
27 70 84 M+ = 102
15 71 is missing
0%
20 40 60 80 m 100 120 140 160 180 200
e
Sample O Major peaks Major peaks

hexanoic acid (remove in book) mass percent mass percent
Mass Spec - Only larger and/or significant peaks are shown. MW = 144
15.0 1 73.0 92
Hint: 144 is tiny, but important. (M-56) is big for a reason (McLafferty). Other helpful 18.0 4 74.0 5
peaks are 73, 71, 57, 56, 45, 43, 29. 29.0 22 87.0 21
%T 31.0 1 88.0 100 (base)
39.0 10 89.0 5
100 41.0 32 101.0 18
42.0 5 115.0 11
3300-2500 43.0 20 116.0 14
45.0 7 144.0 0.5 = M+
50 1380 53.0 2
55.0 17
1460 56.0 5
57.0 38
2864 59.0 3
2925 1710 1230 940 60.0 2
0 69.0 6
4000 3500 3000 2500 2000 1500 1000 500 70.0 4
73 88 = base peak M+ = 102

is missing
50%
57
41 43 55 115
25% 56 87 101
29 70 116
45
31 71 144 = M+
0%
20 40 60 80 m 100 120 140 160 180 200
e

Sample P propyl pentanoate Major peaks Major peaks

MW = 144 (remove in book) mass percent mass percent
15.0 2 86.0 6
.
Hint: McLafferty can occur two ways, at 116 and 88. Other useful peaks are at 57, 43, 29 27.0 24 87.0 3
and 45 is there for a reason. By the way, the M+ peak is missing at 144 28.0 8 102.0 10
%T 29.0 29 103.0 60
31.0 4 104.0 4
100 39.0 10 115.0 4
41.0 38
42.0 19 M+ = 144
43.0 40 is missing
1380 55.0 7
50 56.0 5
1460 1250 1090 57.0 57
59.0 7
60.0 34
2850-2960 1740 1180 61.0 29
0 73.0 19
4000 3500 3000 2500 2000 1500 1000 500 84.0 1
 = wavenumber = cm-1 85.0 100 (base)
85 = base peak
103
57
60
50% 61
40 43
29 41
27 73
25%
104 115 M+ = 144
15 31 is missing
0%
20 40 60 80 m 100 120 140 160 180 200
e
Sample Q Major peaks Major peaks

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

1-octene (remove in book) mass percent mass percent
Mass Spec - Only larger and/or significant peaks are shown. MW = 112
15.0 1
.Hint: Some important peaks are M+ at 112 and 41 has a special reason as does 56 27.0 25
(McLafferty-like, but there is no oxygen). Other familiar peaks are at 71, 57, 43 and 29. 28.0 5
%T 29.0 35
39.0 28
100 41.0 82
42.0 66
43.0 100 (base)
53.0 8
3080 1640 1380 990 55.0 99
50 56.0 87
1470 910 57.0 19
69.0 44
70.0 86
2850-2960
71.0 12
0 83.0 34
4000 3500 3000 2500 2000 1500 1000 500 84.0 22
112.0 20 = M+
43 = base peak
55
41 70
42 56
50%
69
29 83
27 39 M+ = 112
25% 57 84
53 71
15 85
0%
20 40 60 80 m 100 120 140 160 180 200
e
Sample S Major peaks Major peaks

p-ethylphenol mass percent mass percent
27.0 3 103.0 2
.Hint: The M+ peak is solid at 122…and look at that peak at 107 (think "91" plus a really 38.0 1 107.0 100 (base)
good something extra). That's almost all there is. 39.0 6 108.0 8
%T 41.0 1 121.0 3
50.0 2 122.0 36 = M+
100 51.0 4 123.0 3
52.0 2
53.0 2
55.0 2
3020 62.0 1
50 63.0 2
3330 1620 1450 65.0 3
77.0 13
78.0 3
2850-2960 1510 1240 830 79.0 2
0 91.0 4
4000 3500 3000 2500 2000 1500 1000 500 94.0 1
107 = base peak
50%
M+ = 122
25% 77
39 108
27 55 65 91 121
0%
20 40 60 80 m 100 120 140 160 180 200
e

Sample T 1-chloropentane Major peaks Major peaks

MW = 106 (remove in book) mass percent mass percent
15.0 1
.
Hint: The M+ peak barely shows at 106 (and 108 is 1/3 its size). 70 is really big because 27.0 27
it lost a small molecule of… (36)? 71, 57, 43 and 29 are old familiar friends. 28.0 6
%T 29.0 38
100 39.0 19
41.0 70
42.0 100 (base)
43.0 39
53.0 3
50 55.0 93
56.0 6
1350
57.0 22
63.0 5
2850-2960 1470 750 660 69.0 3
70.0 95
0 71.0 6
4000 3500 3000 2500 2000 1500 1000 500 91.0 3
 = wavenumber = cm-1 93.0 0.9
106.0 1.0 = M+
108.0 0.3 = M+2
42 = base peak 70
55
50%
29 43
27
25% 39 57 91 M+ = 106
15 93 M+2 = 108
0%
20 40 60 80 m 100 120 140 160 180 200
e
Sample U Major peaks Major peaks

benzylfluoride mass percent mass percent
27.0 2 91.0 8
.Hint: M+ is big, but M-1 is bigger and that's unusual. However, it has lots of stabilization. 28.0 2 92.0 1
There is a halogen present, but M+2 is not important. What does 91 remind you of? 31.0 1 107.0 2
%T 39.0 8 108.0 1
44.0 1 109.0 100 (base)
100 45.0 2 110.0 55 = M+
50.0 5 111.0 4
51.0 8
1510 57.0 5
50 62.0 3
3080-3030 63.0 6
1470 1380 65.0 4
2850-2960 77.0 2
740 700 81.0 2
980 83.0 12
0 89.0 4
4000 3500 3000 2500 2000 1500 1000 500
109 = base peak
110 = M+
50%
25% 27 44 83
29 31 39 45 51 57 65 77
91
0%
20 40 60 80 m 100 120 140 160 180 200
e
Sample V Major peaks Major peaks

benzoyl choride mass percent mass percent
Mass Spec - Only larger and/or significant peaks are shown. (remove in book)
MW = 134.6
15.0 4 80.0 11
. 27.0 59 91.0 12
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. 29.0 44 92.0 1
%T 39.0 36 98.0 24
41.0 84 99.0 84
100 42.0 43 105.0 6
43.0 97 106.0 6
53.0 5 107.0 2 = mass+2
55.0 100 (base) 108.0 2 = mass+2
56.0 27
50 1380
57.0 45 134.0 0 M+
1470 1130 580 440 60.0 13 (missing)
65.0 2
69.0 10
2860-2960 1800 960 730 70.0 23
0 71.0 40
4000 3500 3000 2500 2000 1500 1000 500 77.0 4
41 43 55 = base peak
42 99
27
50%
29 39 56 71 78
57 105
70 106
25% 60 107
69 80 91 108 134.0 0 M+
15 53 65 (missing)
0%
20 40 60 80 m 100 120 140 160 180 200
e
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.
27.0 2 15.0 1
39.0 4 18.0 3
41.0 2 26.0 1
H 50.0 1 27.0 4
51.0 4 28.0 8
CH2 63.0 2 29.0 2
65.0 7 H 30.0 100.0 base
77.0 3 NH2 31.0 2 peak
78.0 6 H2C 39.0 2
79.0 1 H2N 41.0 5
89.0 1 base 42.0 3
mass = 91 91.0 100 peak M+ = 59 mass = 30 43.0 2
M+ = 120 92.0 11 44.0 1
(M-29) 103.0 1 (M-29)
56.0 1
105.0 4 58.0 2
120.0 26 59.0 9

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
don’t lose either. Instead they work together to make an even more stable carbocation with mass of 106 (M-1).
27.0 2 74.0 2
H H H 28.0 11 75.0 1
29.0 5 76.0 2
CH2 30.0 27 77.0 19
NH2 32.0 1 78.0 12
NH2 38.0 2
NH2 79.0 35
H2C 39.0 6 80.0 3
41.0 1 89.0 4
50.0 6 90.0 2
M+ = 107 51.0 11 91.0 15
mass = 106 (100%) mass = 91 (15%) mass = 30 (27%) 52.0 4 92.0 2
(M-29) (M-16) 52.5 2 103.0 2
(M-77)
both 53.0 3 104.0 5
benzyl 62.0 1
stabilizing carbocation 105.0 1 base
imminium 63.0 3 106.0 100
groups (tropylium ion) ion peak
65.0 5 107.0 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.
28.0 2
H 30.0 100 base
H 31.0 1 peak
CH2 39.0 3
NH2 50.0 1
NH2 NH2 51.0 3
H2C 63.0 2
H 65.0 6
mass = 30 (100%) H 77.0 2
mass = 30 (15%) 89.0 1
M+ = 121 91.0 15
(M-29) (M-91) mass = 120 (1%) 92.0 6
benzyl imminium (M-1) 103.0 2
carbocation ion 120.0 1
(tropylium ion) 121.0 6
Problem – Discuss the MS of the following compounds. How do they compare to those in the examples
above?
15.0 1
27.0 2 26.0 2
39.0 4 27.0 10
41.0 2 28.0 4
50.0 1 29.0 7
51.0 4 30.0 2
63.0 2 31.0 100 base
65.0 7 32.0 2 peak
77.0 3 33.0 1
78.0 6 HO 39.0 4
79.0 1 41.0 7
89.0 1 base 42.0 12
91.0 100 peak M+ = 60 43.0 2
M+ = 120 92.0 11 45.0 2
103.0 1 57.0 1
105.0 4 59.0 16
120.0 26 60.0 10
18.0 1 50.0 10 76.0 2 27.0 1 74.0 1
26.0 1 51.0 21 77.0 49 31.0 4 77.0 5
27.0 6 52.0 6 78.0 11 base 38.0 1 78.0 4
28.0 2 53.0 6 79.0 100 peak 39.0 8 79.0 1
OH 29.0 4 53.5 2 80.0 10 OH
(very 41.0 1 89.0 3
31.0 3 54.0 1 89.0 6 unusual) 50.0 3 90.0 1
37.0 2 61.0 1 90.0 9 51.0 6 91.0 100 base
38.0 3 62.0 3 91.0 17 52.0 2 92.0 60 peak
39.0 11 63.0 6 92.0 2 62.0 1 93.0 4
M+ = 108 40.0 1 64.0 2 105.0 4 63.0 4 103.0 4
41.0 1 65.0 7 107.0 68 M+ = 122 64.0 1 104.0 4
43.0 1 74.0 3 108.0 99 65.0 15 122.0 30
49.0 1 75.0 2 109.0 8 66.0 1 123.0 3
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.)

27.0 19 44.0 3 72.0 3
28.0 3 53.0 2 85.0 2
29.0 31 55.0 10 100.0 11
39.0 11 56.0 25
C7H16 40.0 2 57.0 48
M+ = 100 41.0 45 58.0 2
42.0 20 70.0 18
heptane 43.0 100 71.0 46
27.0 11 53.0 1 84.0 5
29.0 15 55.0 5 85.0 37
39.0 8 56.0 21 86.0 3
40.0 1 57.0 29 100.0 3
41.0 31 58.0 1
C7H16 42.0 35 69.0 1
M+ = 100 43.0 100 70.0 2
2-methylhexane 44.0 3 71.0 2
27.0 12.8 53.0 1.8 72.0 3.1
29.0 24.7 55.0 15.0 84.0 1.1
39.0 9.1 56.0 39.3 85.0 5.7
40.0 1.5 57.0 52.8 100.0 4.0
C7H16 41.0 36.7 58.0 2.3
42.0 9.2 69.0 2.0
M+ = 100 43.0 100.0 70.0 46.5
3-methylhexane 44.0 3.5 71.0 58.3
27.0 9.9 55.0 14.9
29.0 14.3 56.0 3.6
39.0 6.4 57.0 4.5
41.0 16.1 70.0 48.4
C7H16 42.0 6.8 71.0 50.6
43.0 100.0 72.0 2.8
M+ = 100 44.0 3.5 100.0 1.7
3-ethylpentane 53.0 1.4
27.0 14.8 44.0 3.4 71.0 38.2
28.0 1.3 53.0 2.2 72.0 2.2
29.0 27.0 55.0 9.8 84.0 1.0
39.0 10.8 56.0 99.8 85.0 12.6
C7H16 40.0 2.0 57.0 76.2 100.0 3.0
M+ = 100 41.0 52.5 58.0 3.3
42.0 26.0 69.0 1.9
2,3-dimethylpentane 43.0 100.0 70.0 10.8
27.0 9.3 55.0 11.2 86.0 1.3
29.0 11.5 56.0 1.3 100.0 0.0
39.0 6.4 57.0 6.1
41.0 15.7 69.0 1.4
C7H16 42.0 2.7 70.0 18.0
M+ = 100 43.0 100.0 71.0 69.7
44.0 3.4 72.0 4.1


15.0 1.0 44.0 3.3 85.0 18.5
27.0 10.6 53.0 1.0 86.0 1.3
29.0 14.0 55.0 3.2 100.0 0.0
39.0 7.6 56.0 35.3
C7H16 40.0 1.4 57.0 71.7
M+ = 100 41.0 33.5 58.0 3.2
42.0 23.9 69.0 2.4
15.0 1.5 44.0 2.1 83.0 1.0
27.0 8.4 53.0 1.6 85.0 34.4
29.0 15.6 55.0 5.1 86.0 2.3
39.0 9.3 56.0 58.3 100.0 0.0
C7H16 40.0 1.6 57.0 100.0
M+ = 100 41.0 42.1 58.0 4.6
42.0 2.7 59.0 2.8
2,2,3-trimethylbutane 43.0 62.6 69.0 2.4
15.0 1.3 40.0 3.1 55.0 12.1 86.0 10.0
26.0 1.7 41.0 72.5 56.0 70.5
27.0 22.7 42.0 42.4 57.0 100.0
28.0 4.7 43.0 80.9 58.0 4.7
29.0 42.5 44.0 2.8 69.0 8.5
C6H14 30.0 1.0 51.0 1.2 70.0 2.6
M+ = 86 38.0 1.2 53.0 2.2 71.0 11.0
hexane 39.0 14.8 54.0 1.2 84.0 3.2
27.0 12.6 44.0 3.2 72.0 2.2
28.0 1.3 53.0 1.2 78.0 1.0
29.0 11.3 55.0 6.7 85.0 1.5
39.0 9.6 56.0 9.4 86.0 6.1
40.0 1.5 57.0 17.0
C6H14 41.0 29.5 69.0 1.3
M+ = 86 42.0 52.6 70.0 10.2
2-methylpentane 43.0 100.0 71.0 39.5
26.0 1.0 43.0 25.4 86.0 3.0
27.0 13.3 53.0 1.8
28.0 2.2 55.0 6.7
29.0 39.1 56.0 76.7
39.0 9.2 57.0 100.0
C6H14 40.0 1.2 58.0 4.5
M+ = 86 41.0 53.4 70.0 1.6
3-methylpentane 42.0 3.6 71.0 5.7
15.0 1.6 41.0 49.1 57.0 98.3
26.0 1.1 42.0 5.6 58.0 4.7
27.0 17.2 43.0 100.0 70.0 3.3
28.0 2.6 44.0 3.1 71.0 76.7
29.0 33.6 51.0 1.1 72.0 4.5
C6H14 38.0 1.0 53.0 2.5 86.0 0.1
M+ = 86 39.0 13.6 55.0 11.3
2,2-dimethylbutane 40.0 1.8 56.0 28.0
15.0 1.4 43.0 100.0 86.0 3.6
27.0 13.7 44.0 3.5
28.0 1.9 53.0 1.4
29.0 7.5 55.0 5.2
C6H14 39.0 9.0 56.0 1.5
M+ = 86 40.0 1.5 57.0 2.3
41.0 27.4 71.0 19.2
2,3-dimethylbutane 42.0 87.0 72.0 1.1
Alkenes & Cycloalkanes

15.0 1.1 39.0 30.5 53.0 6.5 69.0 31.1
18.0 1.2 40.0 4.9 54.0 7.6 70.0 44.2
26.0 2.0 41.0 96.8 55.0 67.6 71.0 2.5
27.0 25.7 42.0 54.9 56.0 100.0 83.0 4.2
C7H14 28.0 4.9 43.0 15.9 57.0 30.7 98.0 13.8
29.0 55.9 50.0 1.5 58.0 1.3 99.0 1.1
M+ = 98
30.0 1.2 51.0 2.3 67.0 2.3
1-heptene 38.0 1.8 52.0 1.0 68.0 3.6
15.0 1.4 41.0 74.3 55.0 100.0 71.0 1.1
26.0 2.2 42.0 19.3 56.0 90.4 81.0 1.2
27.0 26.3 43.0 20.5 57.0 9.9 83.0 4.2
28.0 3.7 50.0 1.8 65.0 1.3 98.0 43.4
C7H14 29.0 22.0 51.0 3.1 67.0 5.0 99.0 3.6
38.0 2.1 52.0 1.4 68.0 3.6
M+ = 98 69.0 48.1
39.0 27.6 53.0 9.9
trans-2-heptene 40.0 4.8 54.0 11.6 70.0 16.9
27.0 13.5 43.0 18.0 57.0 14.2 79.0 1.3
28.0 3.1 50.0 1.2 65.0 1.8 81.0 1.7
29.0 12.8 51.0 2.4 67.0 8.5 83.0 8.3
38.0 1.1 52.0 1.0 68.0 5.2 97.0 2.0
C7H14 39.0 18.4 53.0 7.7 69.0 100.0 98.0 80.2
M+ = 98 40.0 3.7 54.0 8.3 70.0 28.3 99.0 6.1
41.0 95.3 55.0 82.5 71.0 1.6
trans-3-heptene 42.0 23.7 56.0 98.8 77.0 1.0
15.0 1.4 41.0 87.8 53.0 7.6 69.0 49.4
26.0 1.7 42.0 22.8 54.0 9.7 70.0 17.6
27.0 24.8 43.0 27.5 55.0 79.3 71.0 2.6
28.0 4.9 44.0 1.0 56.0 100.0 81.0 1.2
C7H14 29.0 23.4 45.0 1.1 57.0 18.4 83.0 4.5
38.0 1.6 50.0 1.5 65.0 1.0 98.0 43.3
M+ = 98 67.0 4.0 99.0 3.9
39.0 23.0 51.0 2.4
cis-2-heptene 40.0 4.3 52.0 1.0 68.0 3.6
27.0 11.7 53.0 3.2 83.0 1.1
28.0 3.1 54.0 1.6 98.0 3.1
29.0 8.9 55.0 17.7
39.0 10.5 56.0 100.0
C7H14 40.0 2.9 57.0 10.5
M+ = 98 41.0 46.6 67.0 1.5
42.0 5.6 69.0 9.9
2-methy l-1-hexene 43.0 11.5 70.0 12.4
15.0 1.4 41.0 82.1 55.0 69 72.0 1.2 98.0 35.9
26.0 1.1 42.0 6.1 56.0 19 73.0 1.0 99.0 3.2
27.0 15.5 43.0 8.2 57.0 2 77.0 1.0
28.0 3.3 50.0 1.7 65.0 2 79.0 1.4
C7H14 29.0 12.2 51.0 3.2 67.0 7 81.0 2.5
38.0 1.5 52.0 1.4 68.0 3 83.0 14.9
M+ = 98 39.0 18.9 53.0 8.2 69.0 100 84.0 1.1
3-methy l-3-hexene 40.0 3.4 54.0 2.2 70.0 13 85.0 1.5
15.0 2.2 40.0 3.4 54.0 2.3 68.0 1.6 83.0 82.9
18.0 1.0 41.0 65.3 55.0 100.0 69.0 21.1 84.0 5.7
27.0 14.1 42.0 5.1 56.0 13.7 70.0 4.5 85.0 4.8
28.0 2.3 43.0 18.9 57.0 4.6 71.0 1.0 98.0 37.8
C7H14 29.0 12.8 50.0 1.3 58.0 1.8 72.0 5.2 99.0 4.1
31.0 1.3 51.0 2.5 59.0 8.9 73.0 3.5
M+ = 98 38.0 1.1 52.0 1.2 65.0 1.7 79.0 1.5
2,3-dimethy l-2-pentene 39.0 17.9 53.0 7.6 67.0 7.3 81.0 4.2


15.0 1.7 41.0 77.6 55.0 96.8 69.0 61.7 84.0 3.7
26.0 2.4 42.0 75.4 56.0 100.0 70.0 85.7 91.0 2.0
27.0 23.2 43.0 14.1 57.0 17.9 71.0 5.1 92.0 1.4
28.0 4.8 50.0 1.6 63.0 1.0 77.0 1.1 95.0 1.1
29.0 23.9 51.0 2.9 65.0 2.0 79.0 1.5 96.0 3.4
C7H14 38.0 2.2 52.0 1.3 66.0 1.7 81.0 7.5 97.0 1.7
M+ = 98 39.0 30.9 53.0 8.5 67.0 13.2 82.0 4.6 98.0 62.9
cycloheptane 40.0 6.2 54.0 18.4 68.0 27.2 83.0 48.6 99.0 5.0
26.0 1.0 42.0 28.6 67.0 4.5 84.0 7.0
27.0 12.9 43.0 6.9 68.0 9.3 97.0 2.8
28.0 3.2 51.0 1.9 69.0 22.5 98.0 36.9
29.0 11.1 53.0 4.6 70.0 21.8 99.0 3.1
38.0 1.0 54.0 4.5 71.0 1.4
C7H14 39.0 15.6 55.0 76.3 81.0 1.4
M+ = 98 40.0 2.9 56.0 28.5 82.0 14.5
methylcyclohexane 41.0 41.1 57.0 5.0 83.0 100.0
15.0 1.0 41.0 63.7 56.0 44.7 83.0 8.2
26.0 1.4 42.0 41.3 57.0 7.4 98.0 12.3
27.0 13.7 43.0 7.0 65.0 1.2 99.0 1.0
28.0 2.6 50.0 1.0 67.0 10.0
29.0 12.5 51.0 1.7 68.0 66.4
C7H14 38.0 1.2 53.0 5.1 69.0 100.0
M+ = 98 39.0 18.6 54.0 5.3 70.0 56.1
ethylcyclopentane 40.0 3.5 55.0 47.9 71.0 3.2
27.0 9.6 43.0 17.4 69.0 2.4
28.0 2.3 51.0 1.6 81.0 1.4
29.0 8.3 53.0 3.9 83.0 88.4
38.0 1.1 55.0 100.0 84.0 6.0
39.0 18.0 56.0 11.2 98.0 18.4
C7H14 40.0 3.0 57.0 2.0 99.0 1.4
M+ = 98 41.0 48.6 65.0 1.1
1,1,2,2-tet ramethylcyclopropane 42.0 2.7 67.0 3.7
Alcohols and ethers

15.0 1.3 40.0 2.4 55.0 65.7 73.0 2.0
18.0 3.2 41.0 62.6 56.0 95.5 83.0 7.4
26.0 1.2 42.0 48.5 57.0 23.4 98.0 5.6
27.0 20.2 43.0 66.7 67.0 1.8 116.0 0.0
OH 28.0 4.6 44.0 2.7 68.0 13.3
C7H16O 29.0 27.2 45.0 3.6 69.0 51.6
M+ = 116 31.0 25.6 53.0 2.5 70.0 100.0
1-heptanol 39.0 11.3 54.0 5.6 71.0 6.3
OH mass % mass % mass % mass % mass %
27.0 5.1 45.0 100.0 98.0 4.0
29.0 5.4 46.0 2.3 101.0 3.7
31.0 1.5 55.0 14.9 116.0 0.0
39.0 3.2 56.0 6.8
41.0 10.0 57.0 3.5
C7H16O 42.0 3.6 69.0 2.7
M+ = 116 43.0 8.1 70.0 4.8
2-heptanol 44.0 6.9 83.0 8.9
27.0 9.8 43.0 11.4 59.0 100.0 98.0 2.9
28.0 2.1 44.0 2.9 60.0 3.3 116.0 0.0
29.0 11.1 45.0 8.1 69.0 70.2
OH 30.0 1.1 53.0 1.1 70.0 5.4
31.0 22.1 55.0 8.0 73.0 1.0
C7H16O 39.0 5.3 56.0 5.8 86.0 2.7
M+ = 116 41.0 34.9 57.0 8.1 87.0 31.3
3-heptanol 42.0 2.9 58.0 8.0 88.0 1.8

18.0 1.1 42.0 2.5 69.0 4.0
19.0 1.1 43.0 33.4 70.0 1.3
27.0 9.8 44.0 5.4 71.0 3.2
28.0 1.1 45.0 4.6 72.0 6.3
29.0 6.9 53.0 1.2 73.0 71.4
C7H16O 31.0 11.1 55.0 100.0 74.0 3.4
M+ = 116 39.0 5.4 56.0 9.2 98.0 2.0
4-heptanol 41.0 13.1 57.0 4.4 116.0 0.0
18.0 1.7 43.0 12.5 67.0 1.2
27.0 8.5 45.0 73.7 69.0 28.1
28.0 1.5 46.0 1.7 70.0 2.7
C7H16O 29.0 13.9 53.0 1.9 83.0 1.6
31.0 6.1 55.0 8.2 87.0 100.0
M+ = 116 39.0 4.2 88.0 5.4
56.0 2.3
41.0 24.9 57.0 11.2 98.0 2.8
3-ethy l-3-pentanol 42.0 1.5 59.0 2.5 116.0 0.0
15.0 2.0 42.0 13.1 57.0 3.4
27.0 5.9 43.0 13.3 69.0 13.2
28.0 1.9 45.0 100.0 70.0 2.4
O 29.0 8.2 46.0 2.4 83.0 1.3
31.0 1.8 47.0 1.3 84.0 19.4
C7H16O 33.0 5.2 54.0 1.3 85.0 1.8
M+ = 116 39.0 4.5 55.0 16.4 116.0 0.0
1-methoxyhexane 41.0 14.1 56.0 53.7
15.0 1.3 39.0 12.7 53.0 4.8 68.0 38.6 85.0 5.6
18.0 1.4 40.0 2.8 54.0 15.9 69.0 4.0 86.0 4.1
26.0 1.0 41.0 25.0 55.0 23.1 70.0 13.0 95.0 2.9
27.0 11.9 42.0 14.8 56.0 4.4 71.0 14.9 96.0 22.6
C7H14O 28.0 2.8 43.0 10.3 57.0 100.0 72.0 6.3 97.0 2.0
29.0 12.0 44.0 22.5 58.0 9.1 81.0 34.2 113.0 1.1
M+ = 114 30.0 1.1 45.0 5.3 66.0 2.0 82.0 2.5 114.0 2.1
cycloheptanol 31.0 5.4 51.0 1.1 67.0 19.8 83.0 1.4
OH mass % mass % mass % mass % mass % mass %

15.0 1.5 39.0 12.7 53.0 5.5 67.0 10.7 81.0 47.2 113.0 1.4
18.0 2.4 40.0 2.6 54.0 7.7 68.0 11.8 82.0 3.7 114.0 2.8
26.0 1.1 41.0 34.8 55.0 31.1 69.0 3.1 83.0 2.2
27.0 13.5 42.0 9.9 56.0 12.0 70.0 34.1 85.0 3.8
C7H14O 28.0 3.7 43.0 7.8 57.0 100.0 71.0 12.6 86.0 3.1
M+ = 114 29.0 19.8 44.0 17.0 58.0 52.8 73.0 1.7 95.0 6.0
30.0 1.7 45.0 3.3 59.0 2.7 77.0 1.0 96.0 35.0
4-methylcyclohexanol 31.0 5.7 51.0 1.5 65.0 1.0 79.0 2.0 97.0 3.1

18.0 1.3 42.0 9.6 56.0 7.0 71.0 1.9
27.0 10.6 43.0 4.8 57.0 7.3 79.0 1.5
28.0 2.5 44.0 5.8 58.0 1.0 81.0 23.9
29.0 8.4 45.0 2.4 65.0 1.2 82.0 2.2
31.0 11.0 51.0 1.2 66.0 7.6 83.0 7.5
C7H14O 39.0 13.4 53.0 7.5 67.0 99.6 95.0 3.0
M+ = 114 40.0 3.8 54.0 12.3 96.0 4.0
68.0 100.0
2-cyclopentylethanol 41.0 40.7 55.0 36.9 69.0 15.4 114.0 0.0
O 15.0 1.4 38.0 1.1 56.0 13.3 114.0 0.0
18.0 1.3 39.0 13.4 57.0 42.9
26.0 1.8 40.0 3.0 58.0 72.2
27.0 9.9 41.0 100.0 59.0 3.8
C7H14O 28.0 4.0 42.0 7.6 71.0 10.7
M+ = 114 29.0 24.7 43.0 16.0 72.0 1.8
30.0 3.2 44.0 1.9 73.0 2.8
3-butoxypropene 31.0 3.2 55.0 10.4 85.0 1.9


O 15.0 1.2 43.0 4.7 58.0 3.8 112.0 1.0
27.0 8.0 44.0 1.3 59.0 29.5 115.0 1.0
28.0 2.0 45.0 100.0 60.0 1.0 130.0 0.2
29.0 23.8 46.0 2.2 73.0 5.4
C8H18O 31.0 2.9 53.0 1.0 83.0 9.7
39.0 5.2 55.0 8.3 97.0 1.1
M+ = 130 41.0 28.8 56.0 6.8 101.0 39.1
di-sec-butyl ether 42.0 1.7 57.0 84.5 102.0 2.6
27.0 4.0 55.0 2.0
29.0 12.4 56.0 4.7
O 31.0 1.0 57.0 100.0
39.0 4.2 58.0 4.6
C8H18O 41.0 19.3 59.0 1.7
42.0 2.2 73.0 1.0
M+ = 130 43.0 3.6 87.0 8.2
di-isobutyl ether 45.0 2.0 130.0 2.6
Amines
Haloalkanes

15.0 1.3 38.0 3.1 63.0 4.7
18.0 1.3 39.0 11.4 65.0 1.4
26.0 3.9 40.0 3.1 78.0 2.7
Cl 27.0 31.9 41.0 23.2 80.0 0.8
C3H7Cl 28.0 12.9 42.0 100.0
M+ = 78.5 29.0 40.6 43.0 13.7
36.0 1.2 49.0 4.2
(78 & 80) 37.0 2.3 51.0 1.3
1-chloropropane
15.0 1.7 41.0 21.8 78.0 9.0
26.0 2.4 42.0 6.6 80.0 3.1
27.0 29.3 43.0 100.0
Cl 36.0 1.2 44.0 3.6
C3H7Cl 37.0 1.5 62.0 1.8
M+ = 78.5 38.0 2.4 63.0 17.0
(78 & 80) 39.0 8.5 65.0 5.7
40.0 2.1
2-chloropropane
18.0 1.4 41.0 57.5 55.0 7.5
26.0 3.7 42.0 5.0 56.0 100.0
27.0 26.3 43.0 36.6 57.0 5.8
Cl 28.0 15.0 44.0 1.1 62.0 1.3
C3H7Cl 29.0 16.7 49.0 2.8 63.0 4.8
M+ = 92.6 38.0 1.4 51.0 1.1 65.0 1.4
(78 & 80) 39.0 10.0 53.0 1.2
40.0 2.2
1-chlorobutane


15.0 1.9 39.0 17.9 55.0 3.9
26.0 1.9 40.0 2.6 56.0 8.1
27.0 10.4 41.0 66.8 57.0 100.0
Cl 42.0 3.2 58.0 4.3
28.0 1.4
C3H7Cl 29.0 22.3 49.0 2.2 76.0 3.1
M+ = 92.6 36.0 3.1 51.0 1.3 77.0 38.3
37.0 1.4 53.0 1.3 79.0 12.2
(90 & 92)
38.0 2.6
2-chloro-2-methylpropane
15.0 1.3 39.0 16.7 53.0 3.7 67.0 2.7 91.0 100.0
18.0 3.2 40.0 2.9 54.0 3.9 69.0 22.1 93.0 32.0
Cl 26.0 2.2 41.0 59.0 70.0 2.1
55.0 81.1
27.0 27.0 42.0 44.7 56.0 56.5 71.0 2.8
C6H13Cl 28.0 5.0 43.0 72.0 57.0 14.7 82.0 1.2
M+ = 120.6 29.0 32.0 44.0 2.5 62.0 1.2 83.0 1.3
(120 & 122) 31.0 1.4 49.0 3.0 63.0 4.7 84.0 4.2
38.0 1.2 51.0 1.4 65.0 1.5
1-chlorohexane

15.0 1.6 40.0 2.1 107.0 1.5
26.0 2.4 41.0 31.0 109.0 1.2
Br 27.0 25.6 42.0 7.7 122.0 8.6
28.0 1.6 43.0 100.0 124.0 8.3
C3H7Br 29.0 4.0 44.0 3.5
M+ = 123 37.0 1.2 93.0 1.1
38.0 2.2 95.0 1.0
(122 & 124)
39.0 9.0
1-bromohexane
15.0 1.4 41.0 31.9
26.0 2.2 42.0 4.0
27.0 27.4 43.0 100.0
Br 28.0 1.1 44.0 3.6
C3H7Br 37.0 1.2 107.0 1.1
38.0 2.1 109.0 1.0
M+ = 123 39.0 9.9 122.0 5.9
(122 & 124) 40.0 1.9 124.0 5.7
2-bromohexane
15.0 1.5 41.0 64.5 57.0 100.0 136.0 7.9
26.0 5.7 42.0 3.2 58.0 4.6 138.0 7.8
Br 27.0 29.4 43.0 3.9 79.0 1.0
28.0 13.3 50.0 1.6 81.0 1.0
C4H9Br 29.0 40.9 51.0 1.4 93.0 1.4
M+ = 137 38.0 2.0 53.0 1.5 95.0 1.3
(136 & 138) 39.0 14.8 55.0 7.2 107.0 3.7
40.0 2.2 56.0 16.4 109.0 3.6
1-bromobutane
15.0 1.4 41.0 53.2 58.0 4.4
26.0 3.9 42.0 2.9 107.0 1.2
27.0 18.6 50.0 1.6 109.0 1.0
Br 51.0 1.5
28.0 5.3 136.0 0.6
C4H9Br 29.0 40.9 53.0 1.6 138.0 0.6
M+ = 137 38.0 1.8 55.0 4.9
(136 & 138) 39.0 14.3 56.0 8.0
40.0 1.7 57.0 100.0
2-bromobutane

26.0 1.2 43.0 66.4 69.0 7.5 99.0 14.5 164.0 0.4
27.0 16.5 44.0 2.2 70.0 3.2 100.0 1.2 166.0 0.4
28.0 2.7 53.0 2.4 71.0 2.8 107.0 1.2
Br 109.0 1.0
29.0 20.7 54.0 1.3 81.0 1.0
39.0 10.8 55.0 25.7 83.0 1.5 135.0 8.3
C6H13Br 137.0 8.0
M+ = 165.1 40.0 1.9 56.0 14.6 84.0 1.2
41.0 41.8 57.0 100.0 85.0 18.2
(164 & 166) 42.0 10.3 58.0 4.9 86.0 1.3
1-bromohexane
15.0 1.7 42.0 3.3
26.0 1.7 43.0 100.0 I+ = 127
27.0 31.7 44.0 3.3
I
28.0 1.7 127.0 4.9
38.0 1.5 128.0 1.2 HI+ = 128
C3H7I 39.0 10.7 170.0 23.3
M+ = 170.0 40.0 2.0
41.0 36.8
1-iodopropane
15.0 1.1 42.0 3.6
26.0 1.4 43.0 100.0
44.0 3.4 I+ = 127
27.0 27.7
28.0 1.6 127.0 5.8
I 38.0 1.6 128.0 1.7 HI+ = 128
C3H7I 39.0 11.5 170.0 24.3
M+ = 170.0 40.0 2.0
41.0 35.8
2-iodopropane
26.0 1.2 43.0 100.0 141.0 1.2
27.0 18.8 44.0 3.4 155.0 2.3
28.0 2.5 53.0 1.3 198.0 9.5 I+ = 127
I 29.0 23.1 55.0 9.9
39.0 10.6 71.0 73.2
C5H11I 40.0 2.0 72.0 4.3 HI+ = 128
M+ = 198.0 41.0 30.1 127.0 2.1
42.0 8.3 128.0 0.6
1-iodopentane

Aldehydes and ketones

O mass % mass % mass % mass % mass %
14.0 2.0 30.0 7.8 58.0 85.0
15.0 4.7 31.0 5.6 59.0 12.1
18.0 5.2 37.0 2.4
H 25.0 2.4 38.0 2.3
C3H6O 26.0 16.4 39.0 4.0
M+ = 58 27.0 59.0 40.0 1.7
28.0 90.8 56.0 1.7
propanal 29.0 100.0 57.0 7.3
O
14.0 2.9 39.0 4.2 59.0 3.1
15.0 23.1 40.0 1.0
26.0 3.5 41.0 2.0
27.0 5.7 42.0 9.1
C3H6O 28.0 1.2 43.0 100.0
M+ = 58 29.0 3.1 44.0 3.4
propanone 37.0 1.8 57.0 1.7
38.0 2.2 58.0 63.8
O
14.0 1.7 31.0 2.6 43.0 75.3 60.0 2.7
15.0 5.9 32.0 1.3 44.0 100.0 71.0 5.4
18.0 1.2 37.0 3.1 45.0 3.2 72.0 53.6
H 26.0 8.2 38.0 5.3 50.0 1.1 73.0 2.7
C 4 H8O 27.0 73.5 39.0 27.3 53.0 1.1
M+ = 72 28.0 19.6 40.0 3.5 54.0 2.3
29.0 54.8 41.0 69.1 55.0 1.5
butanal 30.0 1.2 42.0 9.4 57.0 23.3
15.0 2.4 38.0 5.7 50.0 1.0
26.0 5.6 39.0 28.7 53.0 1.5
H 27.0 54.9 40.0 3.9 55.0 3.3
28.0 13.1 41.0 86.7 56.0 1.8
C 4 H8 O 29.0 31.5 42.0 14.0 57.0 6.9
M+ = 72 31.0 1.5 43.0 100.0 71.0 4.4
37.0 3.4 44.0 7.4 72.0 92.3
pentanal 45.0 1.1 73.0 5.9
O
14.0 1.2 41.0 1.1
15.0 6.6 42.0 4.1
18.0 1.3 43.0 100.0
26.0 2.6 44.0 2.6
C4H8O 27.0 8.9 57.0 8.0
28.0 1.3 72.0 22.1
M+ = 72 29.0 18.8 73.0 1.0
butanone 39.0 1.6

15.0 3.9 39.0 12.3 55.0 4.4 71.0 1.8
26.0 3.4 40.0 2.2 56.0 2.2 73.0 1.1
27.0 28.2 41.0 41.0 57.0 19.8 85.0 1.2
H 28.0 10.5 42.0 11.1 58.0 31.4 86.0 1.1
C5H10O 29.0 52.3 43.0 18.7 59.0 1.3
M+ = 86 30.0 2.2 44.0 100.0 60.0 2.9
31.0 1.9 45.0 12.2 67.0 1.1
pentanal 38.0 1.3 53.0 1.6 68.0 1.0

15.0 4.2 38.0 5.0 50.0 2.5 60.0 2.7 87.0 1.2
26.0 2.8 39.0 38.7 51.0 2.4 67.0 1.9
27.0 41.9 40.0 5.7 53.0 5.7 68.0 2.3
H 28.0 4.0 41.0 89.8 55.0 6.2 69.0 2.6
C5H10O 29.0 46.3 42.0 24.6 56.0 3.6 71.0 36.0
M+ = 86 30.0 1.0 43.0 93.4 57.0 37.0 72.0 1.7
31.0 1.3 44.0 100.0 58.0 81.4 85.0 2.8
3-methylbutanal 37.0 2.3 45.0 19.6 59.0 3.1 86.0 11.7

15.0 2.3 37.0 1.1 45.0 3.0 59.0 2.7 86.0 6.3
18.0 2.3 38.0 1.9 50.0 1.4 67.0 1.1 87.0 3.2
H 26.0 4.5 39.0 18.4 51.0 1.5 69.0 1.3
27.0 31.1 40.0 2.7 53.0 3.6 70.0 2.3
C5H10O 28.0 9.4 41.0 92.4 55.0 9.4 71.0 4.9
M+ = 86 29.0 100.0 42.0 5.8 56.0 7.8 73.0 1.8
30.0 4.0 43.0 11.9 57.0 95.8 74.0 11.1
3-methylbutanal 31.0 1.7 44.0 3.8 58.0 60.0 85.0 1.8

15.0 2.3 37.0 1.1 51.0 1.3 86.0 18.1
18.0 3.0 38.0 2.5 53.0 2.1 87.0 3.1
26.0 1.7 39.0 19.4 55.0 5.5
H 27.0 16.4 40.0 2.6 56.0 2.8
C5H10O 28.0 3.2 41.0 83.5 57.0 100.0
M+ = 86 29.0 51.5 42.0 8.8 58.0 5.2
30.0 1.1 43.0 26.6 59.0 1.5
2,2-dimethylpropanal 32.0 1.0 50.0 1.2 71.0 1.6

15.0 4.8 42.0 4.0
26.0 1.3 43.0 100.0
27.0 10.5 44.0 2.3
28.0 1.3 58.0 10.3
C5H10O 29.0 1.9 71.0 11.0
M+ = 86 38.0 1.2 86.0 20.2
39.0 6.3 87.0 1.2
2-pentanone
41.0 11.9
O
26.0 2.5 43.0 1.6
27.0 12.4 55.0 1.3
28.0 4.3 56.0 3.7
29.0 59.4 57.0 100.0
C5H10O 30.0 1.4 58.0 3.4
M+ = 86 39.0 1.8 86.0 21.2
41.0 2.0 87.0 1.2
3-pentanone
42.0 1.8
14.0 1.6 39.0 16.3 51.0 1.1
15.0 9.8 40.0 2.1 57.0 3.7
26.0 3.1 41.0 26.2 71.0 6.9
27.0 19.3 42.0 4.9 86.0 22.6
C5H10O 28.0 3.1 43.0 100.0 87.0 1.0
M+ = 86 29.0 3.5 44.0 2.4
37.0 1.4 45.0 1.3
3-methyl-2-butanone 38.0 2.9 50.0 1.3
15.0 2.2 38.0 1.9 50.0 1.0 60.0 3.6 83.0 1.0
18.0 1.0 39.0 20.1 51.0 1.3 67.0 8.1 100.0 0.4
H 26.0 2.7 40.0 3.8 53.0 2.9 69.0 1.4
27.0 33.9 41.0 69.1 54.0 2.3 71.0 6.7
C6H12O 28.0 8.1 42.0 10.8 55.0 15.3 72.0 16.7
29.0 33.0 43.0 55.1 56.0 82.0 73.0 1.8
M+ = 100 81.0 1.2
30.0 1.6 44.0 100.0 57.0 38.1
hexanal 31.0 1.8 45.0 19.5 58.0 9.0 82.0 12.8
15.0 1.0 39.0 11.4 56.0 1.7 72.0 1.0
18.0 1.0 40.0 1.9 57.0 12.1 74.0 1.7
H 26.0 1.5 41.0 27.2 58.0 90.1 100.0 2.0
27.0 17.6 42.0 5.2 59.0 3.4
C6H12O 28.0 2.1 43.0 100.0 67.0 1.3
M+ = 100 29.0 21.4 44.0 3.4 69.0 1.3
30.0 2.5 53.0 1.9 70.0 1.2
2-methylpentanal 38.0 1.0 55.0 10.3 71.0 15.3


26.0 1.2 43.0 100.0 59.0 1.2 88.0 1.5
27.0 14.9 44.0 5.5 67.0 2.6 100.0 3.1
H 28.0 2.0 53.0 2.7 69.0 1.7
29.0 22.2 54.0 1.6 70.0 2.9
C6H12O 39.0 10.9 55.0 12.6 71.0 34.2
M+ = 100 40.0 1.3 56.0 2.9 72.0 48.1
41.0 27.5 57.0 15.3 73.0 3.1
2-ethylbutanal 42.0 4.9 58.0 3.8 82.0 4.9
15.0 3.6 42.0 3.1 85.0 6.4
18.0 1.9 43.0 100.0 100.0 8.0
26.0 1.1 44.0 2.4
27.0 8.2 55.0 1.4
C6H12O 28.0 2.0 57.0 15.8
M+ = 100 29.0 14.8 58.0 49.8
2-hexanone 39.0 5.6 59.0 3.1
41.0 14.1 71.0 5.4

15.0 2.4 38.0 1.0 55.0 2.4 101.0 2.0
18.0 1.8 39.0 7.9 56.0 1.8
26.0 2.9 40.0 1.2 57.0 84.9
27.0 27.6 41.0 20.3 58.0 3.1
C6H12O 28.0 7.5 42.0 3.6 71.0 54.0
M+ = 100 29.0 53.0 43.0 100.0 72.0 6.1
3-hexanone 30.0 1.1 44.0 3.4 85.0 2.9
32.0 1.6 53.0 1.0 100.0 28.6
15.0 5.1 42.0 3.1 67.0 1.9
27.0 7.2 43.0 100.0 72.0 1.3
28.0 1.7 44.0 2.6 85.0 17.7
29.0 11.0 55.0 1.4 86.0 1.0
C6H12O 31.0 1.1 56.0 1.4 100.0 19.0
M+ = 100 39.0 8.3 57.0 24.9 101.0 1.4
40.0 1.3 58.0 42.6
4-methyl-2-pentanone 41.0 19.2 59.0 3.5
15.0 2.9 43.0 100.0 67.0 1.6
26.0 1.0 44.0 4.4 71.0 2.4
27.0 8.0 45.0 2.5 72.0 50.7
28.0 2.2 53.0 1.6 73.0 2.2
C6H12O 29.0 33.6 55.0 5.1 85.0 8.3
M+ = 100 39.0 7.1 56.0 23.5 100.0 17.6
41.0 41.8 57.0 67.9 101.0 2.4
3-methyl-2-pentanone 42.0 4.0 58.0 3.3
O mass % mass % mass % mass % mass % mass %

15.0 2.0 39.0 19.2 53.0 4.0 67.0 8.8 82.0 2.2 97.0 2.1
26.0 2.1 40.0 3.3 54.0 7.6 68.0 17.5 83.0 3.2 114.0 1.5
27.0 30.7 41.0 66.7 55.0 58.6 69.0 7.1 84.0 1.2
H 28.0 7.4 42.0 53.0 56.0 9.7 70.0 93.7 85.0 4.1
C7H14O 29.0 40.2 43.0 84.0 57.0 46.5 71.0 23.7 86.0 15.4
M+ = 114 30.0 1.5 44.0 100.0 58.0 6.4 72.0 8.5 87.0 1.3
31.0 1.9 45.0 21.9 59.0 1.0 74.0 2.0 95.0 2.2
heptanal 38.0 1.2 51.0 1.5 60.0 1.1 81.0 19.2 96.0 14.4
O mass % mass % mass % mass % mass % mass %
27.0 9.8 43.0 70.9 59.0 4.3
28.0 3.4 44.0 2.4 69.0 1.5
H 29.0 25.0 45.0 1.2 70.0 1.5
30.0 2.7 53.0 1.9 74.0 2.5
C7H14O 39.0 6.9 55.0 7.2 85.0 9.9
M+ = 114 40.0 1.2 56.0 7.9 91.0 1.3
41.0 31.1 57.0 31.8 97.0 1.5
2,3-dimethylpentanal 42.0 1.9 58.0 100.0

15.0 4.2 42.0 3.0 58.0 90.6 115.0 1.0
18.0 1.5 43.0 100.0 59.0 14.8
27.0 8.9 44.0 2.4 71.0 14.0
28.0 2.0 45.0 1.4 72.0 3.9
C7H14O 29.0 8.7 53.0 1.0 85.0 3.3
M+ = 114 39.0 6.7 55.0 5.1 99.0 4.1
40.0 1.0 56.0 1.5 113.0 1.7
2-heptanone 41.0 11.6 57.0 1.6 114.0 9.5

15.0 1.2 41.0 33.7 59.0 1.2
26.0 2.5 42.0 2.8 71.0 5.6
27.0 22.8 43.0 15.2 72.0 32.9
28.0 8.2 53.0 1.5 73.0 2.0
C7H14O 29.0 79.1 55.0 3.6 85.0 43.3
M+ = 114 30.0 1.8 56.0 2.8 86.0 2.6
39.0 8.8 57.0 100.0 114.0 14.0
3-heptanone 40.0 1.0 58.0 4.4 115.0 1.1

O
15.0 1.5 42.0 2.6 72.0 3.8
26.0 1.0 43.0 100.0 86.0 1.4
27.0 15.9 44.0 3.5 99.0 2.0
28.0 1.1 55.0 2.2 114.0 14.4
C7H14O 29.0 2.9 57.0 1.4 115.0 1.2
M+ = 114 39.0 6.3 58.0 6.7
40.0 1.0 70.0 1.2
4-heptanone 41.0 17.5 71.0 84.7

15.0 1.4 41.0 25.7 69.0 1.2 115.0 1.5
26.0 1.3 42.0 3.0 71.0 1.5
27.0 13.3 43.0 15.1 72.0 14.0
28.0 2.6 53.0 1.0 73.0 1.0
C7H14O 29.0 44.8 55.0 1.6 85.0 41.3
30.0 1.0 56.0 1.7 86.0 2.8
M+ = 114 99.0 4.3
39.0 8.0 57.0 100.0
5-methyl-3-hexanone 40.0 1.2 58.0 5.0 114.0 20.4

15.0 4.6 42.0 2.1 59.0 12.4
18.0 1.0 43.0 100.0 71.0 9.6
27.0 9.3 44.0 2.4 72.0 1.2
28.0 1.6 53.0 1.3 81.0 4.8
C7H14O 29.0 7.1 55.0 4.1 85.0 1.4
M+ = 114 39.0 7.0 56.0 3.8 86.0 1.2
40.0 1.0 57.0 14.8 99.0 2.3
5-methyl-2-hexanone 41.0 13.3 58.0 50.2 114.0 4.3

15.0 1.1 43.0 100.0 71.0 59.5
27.0 16.0 44.0 3.8 72.0 3.4
28.0 1.7 53.0 1.2 86.0 15.3
29.0 11.5 55.0 5.5 87.0 2.5
39.0 7.0 57.0 2.5 99.0 34.3
C9H18O 40.0 1.4 58.0 34.4 100.0 3.4
M+ = 142 41.0 18.7 59.0 1.5 142.0 5.2
4-nonanone 42.0 4.2 70.0 1.5

Esters

O 15.0 1.9 40.0 1.7 56.0 2.6 72.0 1.5 98.0 1.3
26.0 1.8 41.0 22.3 57.0 2.5 73.0 23.3 99.0 51.9
27.0 22.3 42.0 10.1 59.0 1.0 74.0 4.1 100.0 3.5
O 28.0 4.0 43.0 61.0 60.0 38.9 83.0 1.3 101.0 25.8
C8H16O2 29.0 49.8 44.0 2.2 61.0 23.6 87.0 6.8 102.0 3.6
M+ = 144 30.0 1.4 45.0 17.4 69.0 5.5 88.0 100.0 115.0 8.0
31.0 1.5 53.0 1.3 70.0 22.9 89.0 5.8 116.0 1.0
ethyl hexanoate
39.0 8.7 55.0 12.4 71.0 26.1 97.0 2.0 117.0 5.0
144.0 1.6

15.0 1.0 40.0 2.7 56.0 12.4 86.0 3.7 144.0 0.6
O 26.0 1.1 41.0 43.4 57.0 92.6 87.0 11.0
27.0 13.0 42.0 9.6 58.0 4.1 102.0 10.5
28.0 5.7 43.0 100.0 59.0 10.0 103.0 32.0
29.0 15.7 44.0 3.3 69.0 1.4 104.0 1.8
C8H16O2 O
31.0 1.0 45.0 5.0 73.0 2.6 116.0 21.3
M+ = 144 53.0 1.0 74.0 19.5 117.0 1.4
38.0 1.3
isopropyl 2-methylbutanoate 39.0 12.0 55.0 4.2 85.0 66.8 129.0 5.0
Carboxylic acids


O 42.0 3.4 83.0 2.8
18.0 1.5 58.0 4.4 144.0 0.1
27.0 8.9 43.0 25.2 59.0 5.5 87.0 7.3
28.0 1.0 44.0 1.1 60.0 1.0 88.0 67.9
OH 29.0 11.9 45.0 2.5 69.0 3.3 89.0 3.1
C8H16O2 31.0 1.1 53.0 2.2 70.0 3.8 99.0 28.5
39.0 8.4 55.0 11.5 71.0 1.2 100.0 2.2
M+ = 144
40.0 1.4 56.0 4.1 73.0 19.2 101.0 6.2
2,2-dimethylhexanoic acid 41.0 27.3 57.0 100.0 74.0 1.3 115.0 2.0
Alkynes
Acid chlorides
Nitriles
Anhydrides
Amides
Amides
hexanamide N,N-diethylethanamide N-ethylpropanamide N-butylpropanamide

27.0 8.7 15.0 6.5
27.0 6.4 27.0 25.1
29.0 8.4 28.0 10.4 27.0 12.3
39.0 5.5 28.0 5.6 28.0 6.9
29.0 8.3 29.0 100.0
41.0 11.6 30.0 69.7 29.0 40.0
43.0 25.8 30.0 19.0 30.0 100.0
42.0 6.6 42.0 5.4
44.0 28.5 44.0 72.0 41.0 12.6
59.0 100.0 43.0 27.6 44.0 30.5
44.0 32.9 46.0 9.1
72.0 18.7 56.0 8.6 57.0 51.6
86.0 9.3 58.0 100.0 58.0 7.2
72.0 15.1 57.0 63.2
72.0 62.1 74.0 11.1
100.0 5.9 86.0 22.8
115.0 33.5 86.0 9.6
100.0 5.4 87.0 25.0
101.0 92.6 100.0 14.5
102.0 5.6 129.0 13.2
O
O M+ = 115
M+ = 115
O O
M+ = 101 M+ = 129
N
NH2
N N
H H
heptanenitrile 1-heptyne 2-heptyne 3-heptyne

27.0 20.6 27.0 18.4 27.0 39.9 27.0 23.3
28.0 6.7 29.0 45.7 28.0 6.7 29.0 13.9
29.0 22.5 39.0 29.8 29.0 8.6 39.0 43.1
39.0 17.8 40.0 11.7 39.0 50.8 40.0 11.5
41.0 87.3 41.0 70.6 40.0 7.6 41.0 83.6
42.0 12.0 42.0 8.0 41.0 67.6 42.0 10.5
43.0 60.2 51.0 5.9 42.0 7.2 50.0 6.3
54.0 55.3 53.0 17.9 43.0 25.6 51.0 11.7
55.0 50.2 54.0 35.4 50.0 6.3 52.0 7.3
56.0 8.2 55.0 51.0 51.0 11.5 53.0 48.8
57.0 11.2 56.0 26.1 52.0 8.6 54.0 24.6
68.0 23.1 57.0 28.4 53.0 46.9 55.0 26.5
69.0 14.7 65.0 7.1 54.0 81.8 56.0 5.0
71.0 5.2 67.0 44.0 55.0 22.3 63.0 5.2
82.0 100.0 68.0 30.2 56.0 8.2 65.0 21.3
83.0 59.4 79.0 10.6 65.0 9.9 66.0 11.1
96.0 14.3 81.0 100.0 66.0 5.5 67.0 100.0
110.0 7.8 82.0 7.3 67.0 43.3 68.0 29.2
111.0 0.7 95.0 9.4 68.0 42.5 77.0 9.2
96.0 1.0 77.0 5.3 79.0 32.4
79.0 13.8 81.0 92.6
81.0 100.0 82.0 6.4
82.0 7.6 95.0 6.9
95.0 5.3 96.0 69.6
96.0 18.0
C
N
M+ = 111 M+ = 96 M+ = 96 M+ = 96

Aromatics
hexylbenzene m-diisopropylbenzene p-diisopropylbenzene

27.0 6.0
27.0 5.2 39.0 5.4
29.0 5.6 41.0 9.3
41.0 13.1 43.0 19.2
39.0 5.5 43.0 33.4
41.0 7.6 77.0 5.5
65.0 5.2 91.0 19.2
43.0 16.6 66.0 5.2
65.0 8.8 105.0 21.8
77.0 7.2 117.0 7.5
78.0 6.4 79.0 5.6
91.0 100.0 119.0 30.8
91.0 25.7 131.0 5.0
92.0 95.1 105.0 30.2
93.0 7.7 147.0 100.0
119.0 41.8 148.0 12.4
105.0 11.2 133.0 6.5
133.0 5.4 162.0 33.1
147.0 100.0
162.0 33.2 148.0 14.4
162.0 36.4
M+ = 162
M+ = 162
M+ = 162

Basics of Mass Spectroscopy: R H E-High Energy R H Radical Cation 2 e - EI Mass Spec

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Basics of Mass Spectroscopy: R H E-High Energy R H Radical Cation 2 e - EI Mass Spec

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Spectroscopy Beauchamp 1

Basics of Mass Spectroscopy

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

molecular ion = M = M+ = M+ = parent peak

Typical MS Instrument Features.

H H H H H H These are left over hydrogen atoms = r

CnH2n+2Ox CnH2n+3N1 CnH2n+4N2

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%

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

one Cl – comparison of M+ peak (35Cl) to M+2 peak (37Cl)

M+ peak relative size 100%

percent of M+ peak = 0.242 (100%) = 32%

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

M+ peak relative size 100% 97%

percent of M+ peak = 0.492 (100%) = 97%

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

M+ peak relative size

percent of M+ peak = 0.008 (100%) = 0.8% 4.4%

M+2 peak relative size M+ M+2

percent of M+ peak = 0.042 (100%) = 4.4%

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

M+ peak relative size

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

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

ionization Hf o(H electron af finity) = -17

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

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

more crowded as sp3 center = higher less crowded as sp2with 3 groups

Actual Mass Spectrum – tabulated and graphical.

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

Actual Mass Spectrum tabulated and graphical.

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

Alkanes - Key Points (see examples above)

less stable more stable

M+ = 114 (6%) M+ = 114 (3%) M+ = 114 (0%)

M+ = 112 (59%) M+ = 114 (6%)

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

3,4-dimethylhexane - has branches actual peaks

20 30 40 50 60 70 80 90 100 110 120 130

Alkenes - Key Points

Remaining sigma bond

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

McLafferty-like rearrangement It is possible to see the cation charge on either

5. Cyclohexenes often undergo retro Diels-Alder reactions.

McLafferty rearrangements allylic fragmentations

112 (0%) 15 (0%)

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

Another Alkene Example (C7 alkene)

This example starts with hept-1-ene

C7H14 = 98 (14%) 57 (31%)

alkyl branches allylic McLafferty

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

Alkynes - Key Points

These alkynes all look similar.

Only cations reach the detector. Mass 39 is in every EI mass spectrum.

4. Small peaks at M=26 are probably ethyne (acetylene).

Example peaks from hept-1-yne:

C7H12 = 96 (1%) 57 (28%)