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Table of Common Fragment Ions

m/z Ions m/z Ions


15 CH3 63 C5H3 a
16 O 65 C5H5 a
17 OH 67 C5H7
18 H2O 69 C5H9
19 F 70 C5H10
26 CN 71 C5H11, C3H7-C=O
27 C2H3 72 C2H5-CO-CH2+Hb
28 C2H4, CO, N2 73 C3H7OCH2,C2H5O-C=O
C3H7CHOH, C2H5OCHCH3
29 C2H5, CHO 74 CH2-COOCH3+Hb
30 CH2NH2, NO 75 C2H5O-C=O+2Hb, C2H5COO+2Hb
31 CH2OH, OCH3 77 C6H5 a
32 O2 78 C6H5+Hab
33 SH 79 C6H5+2Hab, Br (also 81)
34 H2S 81 C6H9
35, 37 Cl 82 C6H10, CCl2 (also 84&86)
36,38 HCl 83 C6H11, CHCl2 (also 85&87)
39 C3H3a 84 C6H12
40 CH2CN, Ar 85 C6H13, C4H9-C=O
41 C3H5, CH2CN+Hb 86 C3H7-CO-CH2+Hb
42 C3H6 87 Homologs of 59 & 73
43 C3H7, CH3C=O 88 CH2-COOC2H5+Hb
44 CH2CHO+Hb, CO2 89 C3H7-O-C=O+2Hb, C3H7COO+2Hb
CH3CH-NH2
45 CH3CHOH, CH2OCH3, 90 C6H5-CH
CH2CH2OH, COOH
46 NO2 91 C6H5-CH2, C6H5-CH+Hb
47 CH2SH, CH3S 92 C6H5-CH2+Hb
48 CH3S+Hb 93 C7H9, CH2Br (also 95)
49, 51 CH2Cl 94 C6H5O+H
50 C4H2 a 97 C7H13
51 C4H3 a 99 Homologs of 71 & 85
52 C4H4 a 100 Homolog of 72 & 86
53 C4H5 101 Homologs of 59, 73, & 87
54 CH2CH2CN, 102 Homolog of 74 & 88
CH3CH-CN
55 C4H7 103 Homolog of 75 & 89
56 C4H8 105 C6H5C=O,C6H5-CH2CH2
57 C4H9, C2H5-C=O 107 C6H5-CH2O
58 CH3-CO-CH2+Hb 108 C6H5-CH2O+Hb
59 C2H5OCH2, CH3O-C=O 119 C6H5-C(CH3)2
C2H5CHOH, CH3O-CHCH3
60 CH2-COOH+Hb 127 I
61 CH3COO+2Hb, CH3OCO+2Hb
a
Good diagnostic for benzene ring compounds
b
The “+H” notation means that the ion was formed by a rearrangement that involved the
transfer of a hydrogen atom from some other part of the molecule. For example:
H H
C O O
+
C
C CH3 H2C CH3
H2

You will notice that most of these “+H” entries have even mass values. The
rearrangement shown above produces an ion with m/z=58.

Those ions identified with a “+2H” arise from a double rearrangement. One example,
producing an ion of m/z=61 from an ester, is shown below.

R
H
H H
C O
C O C C
CH2R CH2R =
C H
C C H
O CH3
O CH3 O
O

H3C

H
R
H H
O
C C
+ O

C.
m/z=61
H3C