第二十章质谱分析一、饱合烃
alkanes
二、芳烃的
aromatic hydrocarbons
三、醇和酚
alcohols and phenols
四,醚
ethers
五,醛、酮
aldehydes and ketones
六,其他化合物
other compounds
第四节质谱图与结构解析
（电子轰击质谱 — EIMS ）
mass spectrometry,MS
mass spectrograph and
structure determination
1.直链烷烃
1 6
1 5
m / z
m e t h a n e
M = 1 6
一、饱合烃的质谱图 alkanes
m / z
1 5
2 9
4 3
5 7
8 5
9 9 1 1 3 1 4 2
7 1
1 0
0
8 0
9 0
1 0 0
6 0
5 0
3 0
2 0
4 0
7 0
0 2 0 4 0 6 0 8 0 1 0 0 1 2 0 1 4 0 1 6 0 1 8 0 2 0 0
%
O
F
B
A
S
E
P
E
A
K
1 0 3 0 5 0 7 0 9 0 1 1 0 1 3 0 1 5 0 1 7 0 1 9 0 2 1 0 2 2 0 2 3 0
C 2
C 3 C 4
C 5
C 6
C 7
m / z = 2 9
m / z = 4 3 m / z = 5 7
m / z = 7 1
m / z = 8 5
9 9
1 1 3 1 2 7 1 4 1 1 5 5 1 6 9 1 8 3
1 9 7
C 8 C
9 C 1 0
C 1 1 C 1 2 C 1 3 C 1 4
C 1 6
C H 3 ( C H 2 ) 1 4 C H 3
M
m / z = 2 2 6
n - H e x a d e c a n e
M W 2 2 6
m / z
1 5
2 9
4 3
5 7
8 5
9 9 1 1 3 1 4 2
7 1
正癸烷
分子离子,C1(100%),C10(6%),C16(小 ),C45(0)
有 m/z,29,43,57,71,……C nH2n+1 系列峰 (σ— 断裂 )
有 m/z,27,41,55,69,……C nH2n-1 系列峰
C2H5+（ m/z =29） → C 2H3+（ m/z =27） +H2
有 m/z,28,42,56,70,……C nH2n系列峰 (四圆环重排 )
2.支链烷烃
2 0 4 0 6 0 8 0 1 0 0 1 2 0 1 4 0 1 6 0 1 8 0 2 0 01 0 3 0 5 0 7 0 9 0 1 1 0 1 3 0 1 5 0 1 7 0 1 9 0 2 1 0 2 2 0 2 3 0
1 0
0
8 0
9 0
1 0 0
6 0
5 0
3 0
2 0
4 0
7 0
0
%
O
F
B
A
S
E
P
E
A
K
C
3
m / z = 4 3
C
4
m / z = 5 7
C
5
m / z = 7 1
C
8
m / z = 8 5C 6
m / z = 9 9
C
7
1 1 3
C
9
C
1 0
C
1 2 C 1 6M 1 5
M
5 - M e t h y l p e n t a d e c a n e
C H
3
( C H
2
)
3
C H ( C H
2
)
9
C H
3
C H
3
8 5
1 6 9 1 4 1
5 7
3.环烷烃
M = 8 4
C y c l o h e x a n e
8 4 ( M )
5 6 ( C
4
H
8
+
)
4 1 ( C
3
H
5
+
)
1 0
0
8 0
9 0
1 0 0
6 0
5 0
3 0
2 0
4 0
7 0
%
O
F
B
A
S
E
P
E
A
K
0 2 0 4 0 6 0 8 0 1 0 01 0 3 0 5 0 7 0 9 0 1 1 00
M = 9 8
9 8 ( M )
1 0
0
8 0
9 0
1 0 0
6 0
5 0
3 0
2 0
4 0
7 0
%
O
F
B
A
S
E
P
E
A
K
0 2 0 4 0 6 0 8 0 1 0 01 0 3 0 5 0 7 0 9 0 1 1 0
8 3
6 9
5 5
4 1
2 9
M e t h y l C y c l o h e x a n e
C H 3
m / z = 9 8 m / z = 8 3
8 4 ( M )
0 2 0 4 0 6 0 8 0 1 0 01 0 3 0 5 0 7 0 9 0 1 1 0
6 9
5 5
4 1
2 7
1 0
0
8 0
9 0
1 0 0
6 0
5 0
3 0
2 0
4 0
7 0
%
O
F
B
A
S
E
P
E
A
K
C H CH
3
C
C H
3
C H
2
C H
3
C H CH
3
C
C H
3
C H CH
3
C
C H
3
C H
2
C H
3
C H
2
C H
3
m / z = 6 9
m / z = 5 5
1 3 4 ( M )
1 0
0
8 0
9 0
1 0 0
6 0
5 0
3 0
2 0
4 0
7 0
%
O
F
B
A
S
E
P
E
A
K
0 2 0 4 0 6 0 8 0 1 0 01 0 3 0 5 0 7 0 9 0 1 1 0
9 1
7 7
9 2
5 13 9
1 2 0 1 3 0 1 4 0
6 5
C H
2
C H
2
C H
2
C H
3
二、芳烃的质谱图
aromatic hydrocarbons
C H
2
C H
2
C H
2
C H
3
C H
2
m / z = 9 1
m / z = 9 1
m / z = 6 5m / z = 3 9
m / z = 1 3 4
H C C H
H C C H
C H
2
C H
2
C H
3
H
2
C
C H
2
C H
H
C H
3
C H
2
H
H
m / z = 9 2
C H
2
H C
C H
3
C H
2
C H
2
C H
2
C H
3
m / z = 7 7m / z = 1 3 4
m / z = 5 1
H C C H
C
4
H
9
R 2 C
R 1
R 3
O H
- R 3
R 2
C
R 1
O H
m / z,3 1,5 9,7 3,
R H C
H
C H 2
O H
R H C
C H 2
O H
H
- H 2 O
R H C C H
2
R H C C H
2
( C H 2 ) n ( C H
2 ) n
( C H 2 ) n ( C H 2 ) n
o r
三、醇和酚的质谱图
alcohols and phenols
R H C
H
C H
2
C H
2
C H
2
O +
H
H
2
C C H
2
- H
2
O
M - ( A l k e n e + H
2
O )
M - 4 6
H
2
C C H R
-
R H C
H
H C
C H
2
C H
2
O +
H
C H
3
H
2
C
H
C
- H
2
O
- C H
3
H
2
C C H R
M - 6 0
H
C C H 2H 2 C
C H H
H 2
CR
H 2 C C H 2-
C H 2
C H
H 2
CR
M - 7 6
1 0
0
8 0
9 0
1 0 0
6 0
5 0
3 0
2 0
4 0
7 0
%
O
F
B
A
S
E
P
E
A
K
C H
2
O H
M - ( H
2
O a n d C H
2
C H
2
)
M - ( H
2
O a n d C H
3
)
M - H
2
O
M - 1
1 - P e n T a n o l M W 8 8
C H
3
( C H
2
)
3
C H
2
O H
3 1
4 0 6 0 8 0 1 0 0 1 2 0 1 4 01 0
3 0
5 0 7 0 9 0 1 1 0 1 3 0 1 5 00
2 0
1 0
0
8 0
9 0
1 0 0
6 0
5 0
3 0
2 0
4 0
7 0
2 0 4 0 6 0 8 0 1 0 0 1 2 0 1 4 0
%
O
F
B
A
S
E
P
E
A
K
1 0 3 0 5 0 7 0 9 0 1 1 0 1 3 0 1 5 0
M - ( H
2
O a n d C H
3
)
M - H
2
O
M - C H
3
M - 1
M
2 - P e n T a n o l M W 8 8
O H
C H
3
( C H
2
)
2
C H
3
H
C
4 5
4 5
M - ( H
2
O a n d
C H
2
C H
2
)
0
1 0
0
8 0
9 0
1 0 0
6 0
5 0
3 0
2 0
4 0
7 0
2 0 4 0 6 0 8 0 1 0 0 1 2 0 1 4 0
%
O
F
B
A
S
E
P
E
A
K
1 0 3 0 5 0 7 0 9 0 1 1 0 1 3 0 1 5 0
M - ( H
2
O a n d
C H
2
C H
2
)
M - ( H
2
O a n d C H
3
)
M - C H
3
M - H
2
O
O H
C H
3
C H
2
C H
3
C
5 9
C H
3
2 - M e t h y l - 2 - b u t a n o l M W 8 8
0
5 9
C H
2
O H
H
O H
-
m / z = 1 0 8
m / z = 1 0 7
- C O
HH
- H
2
HH
H
H
H
m / z = 7 9 m / z = 7 7
H
2
C
C
H
2
H
O H
C H
2
C H
2
H
2
O-
H
2
C
O
H
O H
C H
2
O
H
2
O-
O H
m / z = 9 4
O
H
H
H
H
- C O
H
- C H O
m / z = 6 6
m / z = 6 5
C H 2 C H 3
O H
C H 2
O H
- C H 3
m / z 1 0 7 ( 1 0 0 % )
C H C H 3
O H
m / z 1 2 1 ( 3,5 % )- H
1 0
0
8 0
9 0
1 0 0
6 0
5 0
3 0
2 0
4 0
7 0
0 2 0 4 0 6 0 8 0 1 0 0 1 2 0 1 4 0
%
O
F
B
A
S
E
P
E
A
K
1 0 3 0 5 0 7 0 9 0 1 1 0 1 3 0 1 5 0
o - E t h y l p h e n o l
1 2 2 ( M )
M - C H
3
MM - H
2
O
C
6
H
5
1 0
0
8 0
9 0
1 0 0
6 0
5 0
3 0
2 0
4 0
7 0
0 2 0 4 0 6 0 8 0 1 0 0 1 2 0 1 4 0
%
O
F
B
A
S
E
P
E
A
K
1 0 3 0 5 0 7 0 9 0 1 1 0 1 3 0 1 5 0
C H
3
C H
2
5 7
M - C H
3
C H
2
M - C H
3
M
E t h y l s e c - b u t y l e t h e r
M W 1 0 2
7 3 2 9
8 7
5 7
H
3
C C
H
O H
C H
3
C H
2
H
C
C H
3
O C H
2
C H
3
4 5
2 9
7 3
8 7
1 0 2
四,醚的质谱图
ethers
0 2 0 4 0 6 0 8 0 1 0 0
1 2 0 1 4 0 1 6 0 1 8 0 2 0 05 0 7 0 9 0 1 1 0 1 3 0 1 5 0 1 7 0 1 9 0
2 1 0 2 2 0 2 3 0
1 0
0
8 0
9 0
1 0 0
6 0
5 0
3 0
2 0
4 0
7 0
0
%
O
F
B
A
S
E
P
E
A
K
C
6
H
5
C l C
M M + 1
M + 2
M + 3
M + 4
p - C h l o r o b e n z o p h e n o n e
2 1 6 ( M ) 1 0 0,0
2 1 7 ( M + 1 ) 1 9,2 8
2 1 8 ( M + 2 ) 3 3,9 9
2 1 9 ( M + 3 ) 6,2 1
2 2 0 ( M + 4 ) 0,9 8
O
C O
C l
1 0 3 0
C l C
O
五,醛、酮的质谱图
aldehydes and ketones
5 5
M
0 2 0 4 0 6 0 8 0 1 0 01 0 3 0 5 0 7 0 9 0
4 2
2 7
6 9
1 0
8 0
9 0
1 0 0
6 0
5 0
3 0
2 0
4 0
7 0
%
O
F
B
A
S
E
P
E
A
K
0
9 8
O
1 0
0
8 0
9 0
1 0 0
6 0
5 0
3 0
2 0
4 0
7 0
%
O
F
B
A
S
E
P
E
A
K
5 7
M - C H
2
C H
2
M - H
2
O
M
M W 1 4 2
4 0 6 0 8 0 1 0 0 1 2 0 1 4 01 0 3 0 5 0 7 0 9 0 1 1 0 1 3 0 1 5 00 2 0
M - 1
M - 4 4
M - 4 3
C H
3
( C H
2
)
7
C H O
4 4
O
C h
3
( C H
2
)
4
C O ( s m a l l ) 9 9
C H
3
( C H
2
)
4
7 1
C H
3
( C H )
3
5 7
C H
3
( C H
2
)
2
4 3
C H
3
C H
2
2 9
C H
3
C H
2
C H
2
C H
2
C H
2
C O H
4 5 C O
2
H
5 9 ( s m a l l ) C H
2
C O
2
H
7 3 ( C H
2
)
2
C O
2
H
8 7 ( C H
2
)
3
C O
2
H
1 0
0
8 0
9 0
1 0 0
6 0
5 0
3 0
2 0
4 0
7 0
0 2 0 4 0 6 0 8 0 1 0 0 1 2 0 1 4 0
%
O
F
B
A
S
E
P
E
A
K
1 0 3 0 5 0 7 0 9 0 1 1 0 1 3 0 1 5 0
F i g u r e 2,1 4,M e t h y l O c a t a n o a t e
C O C H
3
O
C H
2
C H
2
O C H
3
O
1 2 1 [ M - 3 1 ]
M
M + 1
M + 2
M e t h y l o c t a n o a t e
C H
3
( C H
2
)
6
C O O C H
3
1 5 8 ( M )
1 5 9 ( M + 1 )
1 6 0 ( M + 2 )
1 6 0
8 7
5 9
7 4
C
O H
O C H
3H
2
C
六,其他化合物的质谱图
other compounds
1 2 9 ( M )
1 0
0
8 0
9 0
1 0 0
6 0
5 0
3 0
2 0
4 0
7 0
%
O
F
B
A
S
E
P
E
A
K
0 2 0 4 0 6 0 8 0 1 0 01 0 3 0 5 0 7 0 9 0 1 1 0
8 6
1 1 4
4 4
2 9
1 2 0 1 3 0 1 4 0
5 8
C H N C H
2
C H
3
C H
2
C H
2
C H
3
C H
3
C H
3
M = 8 5
N
8 5 ( M )
1 0
0
8 0
9 0
1 0 0
6 0
5 0
3 0
2 0
4 0
7 0
%
O
F
B
A
S
E
P
E
A
K
0 2 0 4 0 6 0 8 0 1 0 01 0 3 0 5 0 7 0 9 0 1 1 00
H
8 5
5 7
5 6
4 44 2
2 9
M = 1 1 3
1 0
0
8 0
9 0
1 0 0
6 0
5 0
3 0
2 0
4 0
7 0
%
O
F
B
A
S
E
P
E
A
K
N H
8 4
5 6
4 1
2 7
C H
2
H
3
C
7 0
1 1 3 ( M )
2 0 4 0 6 0 8 0 1 0 01 0 3 0 5 0 7 0 9 0
1 1 0
0
1 2 00
5 4
M
4 1
2 7
6 7
1 0
8 0
9 0
1 0 0
6 0
5 0
3 0
2 0
4 0
7 0
%
O
F
B
A
S
E
P
E
A
K
0
8 2
3 9
2 0 4 0 6 0 8 0 1 0 01 0 3 0 5 0 7 0 9 00
结构未知（ C6H12O，酮）
解析：
1,100，分子离子峰
2,85，失去 CH3（ 15） 的产物
3,57,丰度最大,稳定结构失去 CO(28)后的产物内容选择：
第一节 基本原理与质谱仪
basic principle and mass spectrometer
第二节 离子峰的主要类型
main kinds of ion peaks
第三节 有机分子裂解类型
cleavage types of organic compounds
第四节 质谱图与结构解析
mass spectrograph and structure determination
第五节 色谱 -质谱联用仪
hyphenated methods of GC-MS
结束
alkanes
二、芳烃的
aromatic hydrocarbons
三、醇和酚
alcohols and phenols
四,醚
ethers
五,醛、酮
aldehydes and ketones
六,其他化合物
other compounds
第四节质谱图与结构解析
（电子轰击质谱 — EIMS ）
mass spectrometry,MS
mass spectrograph and
structure determination
1.直链烷烃
1 6
1 5
m / z
m e t h a n e
M = 1 6
一、饱合烃的质谱图 alkanes
m / z
1 5
2 9
4 3
5 7
8 5
9 9 1 1 3 1 4 2
7 1
1 0
0
8 0
9 0
1 0 0
6 0
5 0
3 0
2 0
4 0
7 0
0 2 0 4 0 6 0 8 0 1 0 0 1 2 0 1 4 0 1 6 0 1 8 0 2 0 0
%
O
F
B
A
S
E
P
E
A
K
1 0 3 0 5 0 7 0 9 0 1 1 0 1 3 0 1 5 0 1 7 0 1 9 0 2 1 0 2 2 0 2 3 0
C 2
C 3 C 4
C 5
C 6
C 7
m / z = 2 9
m / z = 4 3 m / z = 5 7
m / z = 7 1
m / z = 8 5
9 9
1 1 3 1 2 7 1 4 1 1 5 5 1 6 9 1 8 3
1 9 7
C 8 C
9 C 1 0
C 1 1 C 1 2 C 1 3 C 1 4
C 1 6
C H 3 ( C H 2 ) 1 4 C H 3
M
m / z = 2 2 6
n - H e x a d e c a n e
M W 2 2 6
m / z
1 5
2 9
4 3
5 7
8 5
9 9 1 1 3 1 4 2
7 1
正癸烷
分子离子,C1(100%),C10(6%),C16(小 ),C45(0)
有 m/z,29,43,57,71,……C nH2n+1 系列峰 (σ— 断裂 )
有 m/z,27,41,55,69,……C nH2n-1 系列峰
C2H5+（ m/z =29） → C 2H3+（ m/z =27） +H2
有 m/z,28,42,56,70,……C nH2n系列峰 (四圆环重排 )
2.支链烷烃
2 0 4 0 6 0 8 0 1 0 0 1 2 0 1 4 0 1 6 0 1 8 0 2 0 01 0 3 0 5 0 7 0 9 0 1 1 0 1 3 0 1 5 0 1 7 0 1 9 0 2 1 0 2 2 0 2 3 0
1 0
0
8 0
9 0
1 0 0
6 0
5 0
3 0
2 0
4 0
7 0
0
%
O
F
B
A
S
E
P
E
A
K
C
3
m / z = 4 3
C
4
m / z = 5 7
C
5
m / z = 7 1
C
8
m / z = 8 5C 6
m / z = 9 9
C
7
1 1 3
C
9
C
1 0
C
1 2 C 1 6M 1 5
M
5 - M e t h y l p e n t a d e c a n e
C H
3
( C H
2
)
3
C H ( C H
2
)
9
C H
3
C H
3
8 5
1 6 9 1 4 1
5 7
3.环烷烃
M = 8 4
C y c l o h e x a n e
8 4 ( M )
5 6 ( C
4
H
8
+
)
4 1 ( C
3
H
5
+
)
1 0
0
8 0
9 0
1 0 0
6 0
5 0
3 0
2 0
4 0
7 0
%
O
F
B
A
S
E
P
E
A
K
0 2 0 4 0 6 0 8 0 1 0 01 0 3 0 5 0 7 0 9 0 1 1 00
M = 9 8
9 8 ( M )
1 0
0
8 0
9 0
1 0 0
6 0
5 0
3 0
2 0
4 0
7 0
%
O
F
B
A
S
E
P
E
A
K
0 2 0 4 0 6 0 8 0 1 0 01 0 3 0 5 0 7 0 9 0 1 1 0
8 3
6 9
5 5
4 1
2 9
M e t h y l C y c l o h e x a n e
C H 3
m / z = 9 8 m / z = 8 3
8 4 ( M )
0 2 0 4 0 6 0 8 0 1 0 01 0 3 0 5 0 7 0 9 0 1 1 0
6 9
5 5
4 1
2 7
1 0
0
8 0
9 0
1 0 0
6 0
5 0
3 0
2 0
4 0
7 0
%
O
F
B
A
S
E
P
E
A
K
C H CH
3
C
C H
3
C H
2
C H
3
C H CH
3
C
C H
3
C H CH
3
C
C H
3
C H
2
C H
3
C H
2
C H
3
m / z = 6 9
m / z = 5 5
1 3 4 ( M )
1 0
0
8 0
9 0
1 0 0
6 0
5 0
3 0
2 0
4 0
7 0
%
O
F
B
A
S
E
P
E
A
K
0 2 0 4 0 6 0 8 0 1 0 01 0 3 0 5 0 7 0 9 0 1 1 0
9 1
7 7
9 2
5 13 9
1 2 0 1 3 0 1 4 0
6 5
C H
2
C H
2
C H
2
C H
3
二、芳烃的质谱图
aromatic hydrocarbons
C H
2
C H
2
C H
2
C H
3
C H
2
m / z = 9 1
m / z = 9 1
m / z = 6 5m / z = 3 9
m / z = 1 3 4
H C C H
H C C H
C H
2
C H
2
C H
3
H
2
C
C H
2
C H
H
C H
3
C H
2
H
H
m / z = 9 2
C H
2
H C
C H
3
C H
2
C H
2
C H
2
C H
3
m / z = 7 7m / z = 1 3 4
m / z = 5 1
H C C H
C
4
H
9
R 2 C
R 1
R 3
O H
- R 3
R 2
C
R 1
O H
m / z,3 1,5 9,7 3,
R H C
H
C H 2
O H
R H C
C H 2
O H
H
- H 2 O
R H C C H
2
R H C C H
2
( C H 2 ) n ( C H
2 ) n
( C H 2 ) n ( C H 2 ) n
o r
三、醇和酚的质谱图
alcohols and phenols
R H C
H
C H
2
C H
2
C H
2
O +
H
H
2
C C H
2
- H
2
O
M - ( A l k e n e + H
2
O )
M - 4 6
H
2
C C H R
-
R H C
H
H C
C H
2
C H
2
O +
H
C H
3
H
2
C
H
C
- H
2
O
- C H
3
H
2
C C H R
M - 6 0
H
C C H 2H 2 C
C H H
H 2
CR
H 2 C C H 2-
C H 2
C H
H 2
CR
M - 7 6
1 0
0
8 0
9 0
1 0 0
6 0
5 0
3 0
2 0
4 0
7 0
%
O
F
B
A
S
E
P
E
A
K
C H
2
O H
M - ( H
2
O a n d C H
2
C H
2
)
M - ( H
2
O a n d C H
3
)
M - H
2
O
M - 1
1 - P e n T a n o l M W 8 8
C H
3
( C H
2
)
3
C H
2
O H
3 1
4 0 6 0 8 0 1 0 0 1 2 0 1 4 01 0
3 0
5 0 7 0 9 0 1 1 0 1 3 0 1 5 00
2 0
1 0
0
8 0
9 0
1 0 0
6 0
5 0
3 0
2 0
4 0
7 0
2 0 4 0 6 0 8 0 1 0 0 1 2 0 1 4 0
%
O
F
B
A
S
E
P
E
A
K
1 0 3 0 5 0 7 0 9 0 1 1 0 1 3 0 1 5 0
M - ( H
2
O a n d C H
3
)
M - H
2
O
M - C H
3
M - 1
M
2 - P e n T a n o l M W 8 8
O H
C H
3
( C H
2
)
2
C H
3
H
C
4 5
4 5
M - ( H
2
O a n d
C H
2
C H
2
)
0
1 0
0
8 0
9 0
1 0 0
6 0
5 0
3 0
2 0
4 0
7 0
2 0 4 0 6 0 8 0 1 0 0 1 2 0 1 4 0
%
O
F
B
A
S
E
P
E
A
K
1 0 3 0 5 0 7 0 9 0 1 1 0 1 3 0 1 5 0
M - ( H
2
O a n d
C H
2
C H
2
)
M - ( H
2
O a n d C H
3
)
M - C H
3
M - H
2
O
O H
C H
3
C H
2
C H
3
C
5 9
C H
3
2 - M e t h y l - 2 - b u t a n o l M W 8 8
0
5 9
C H
2
O H
H
O H
-
m / z = 1 0 8
m / z = 1 0 7
- C O
HH
- H
2
HH
H
H
H
m / z = 7 9 m / z = 7 7
H
2
C
C
H
2
H
O H
C H
2
C H
2
H
2
O-
H
2
C
O
H
O H
C H
2
O
H
2
O-
O H
m / z = 9 4
O
H
H
H
H
- C O
H
- C H O
m / z = 6 6
m / z = 6 5
C H 2 C H 3
O H
C H 2
O H
- C H 3
m / z 1 0 7 ( 1 0 0 % )
C H C H 3
O H
m / z 1 2 1 ( 3,5 % )- H
1 0
0
8 0
9 0
1 0 0
6 0
5 0
3 0
2 0
4 0
7 0
0 2 0 4 0 6 0 8 0 1 0 0 1 2 0 1 4 0
%
O
F
B
A
S
E
P
E
A
K
1 0 3 0 5 0 7 0 9 0 1 1 0 1 3 0 1 5 0
o - E t h y l p h e n o l
1 2 2 ( M )
M - C H
3
MM - H
2
O
C
6
H
5
1 0
0
8 0
9 0
1 0 0
6 0
5 0
3 0
2 0
4 0
7 0
0 2 0 4 0 6 0 8 0 1 0 0 1 2 0 1 4 0
%
O
F
B
A
S
E
P
E
A
K
1 0 3 0 5 0 7 0 9 0 1 1 0 1 3 0 1 5 0
C H
3
C H
2
5 7
M - C H
3
C H
2
M - C H
3
M
E t h y l s e c - b u t y l e t h e r
M W 1 0 2
7 3 2 9
8 7
5 7
H
3
C C
H
O H
C H
3
C H
2
H
C
C H
3
O C H
2
C H
3
4 5
2 9
7 3
8 7
1 0 2
四,醚的质谱图
ethers
0 2 0 4 0 6 0 8 0 1 0 0
1 2 0 1 4 0 1 6 0 1 8 0 2 0 05 0 7 0 9 0 1 1 0 1 3 0 1 5 0 1 7 0 1 9 0
2 1 0 2 2 0 2 3 0
1 0
0
8 0
9 0
1 0 0
6 0
5 0
3 0
2 0
4 0
7 0
0
%
O
F
B
A
S
E
P
E
A
K
C
6
H
5
C l C
M M + 1
M + 2
M + 3
M + 4
p - C h l o r o b e n z o p h e n o n e
2 1 6 ( M ) 1 0 0,0
2 1 7 ( M + 1 ) 1 9,2 8
2 1 8 ( M + 2 ) 3 3,9 9
2 1 9 ( M + 3 ) 6,2 1
2 2 0 ( M + 4 ) 0,9 8
O
C O
C l
1 0 3 0
C l C
O
五,醛、酮的质谱图
aldehydes and ketones
5 5
M
0 2 0 4 0 6 0 8 0 1 0 01 0 3 0 5 0 7 0 9 0
4 2
2 7
6 9
1 0
8 0
9 0
1 0 0
6 0
5 0
3 0
2 0
4 0
7 0
%
O
F
B
A
S
E
P
E
A
K
0
9 8
O
1 0
0
8 0
9 0
1 0 0
6 0
5 0
3 0
2 0
4 0
7 0
%
O
F
B
A
S
E
P
E
A
K
5 7
M - C H
2
C H
2
M - H
2
O
M
M W 1 4 2
4 0 6 0 8 0 1 0 0 1 2 0 1 4 01 0 3 0 5 0 7 0 9 0 1 1 0 1 3 0 1 5 00 2 0
M - 1
M - 4 4
M - 4 3
C H
3
( C H
2
)
7
C H O
4 4
O
C h
3
( C H
2
)
4
C O ( s m a l l ) 9 9
C H
3
( C H
2
)
4
7 1
C H
3
( C H )
3
5 7
C H
3
( C H
2
)
2
4 3
C H
3
C H
2
2 9
C H
3
C H
2
C H
2
C H
2
C H
2
C O H
4 5 C O
2
H
5 9 ( s m a l l ) C H
2
C O
2
H
7 3 ( C H
2
)
2
C O
2
H
8 7 ( C H
2
)
3
C O
2
H
1 0
0
8 0
9 0
1 0 0
6 0
5 0
3 0
2 0
4 0
7 0
0 2 0 4 0 6 0 8 0 1 0 0 1 2 0 1 4 0
%
O
F
B
A
S
E
P
E
A
K
1 0 3 0 5 0 7 0 9 0 1 1 0 1 3 0 1 5 0
F i g u r e 2,1 4,M e t h y l O c a t a n o a t e
C O C H
3
O
C H
2
C H
2
O C H
3
O
1 2 1 [ M - 3 1 ]
M
M + 1
M + 2
M e t h y l o c t a n o a t e
C H
3
( C H
2
)
6
C O O C H
3
1 5 8 ( M )
1 5 9 ( M + 1 )
1 6 0 ( M + 2 )
1 6 0
8 7
5 9
7 4
C
O H
O C H
3H
2
C
六,其他化合物的质谱图
other compounds
1 2 9 ( M )
1 0
0
8 0
9 0
1 0 0
6 0
5 0
3 0
2 0
4 0
7 0
%
O
F
B
A
S
E
P
E
A
K
0 2 0 4 0 6 0 8 0 1 0 01 0 3 0 5 0 7 0 9 0 1 1 0
8 6
1 1 4
4 4
2 9
1 2 0 1 3 0 1 4 0
5 8
C H N C H
2
C H
3
C H
2
C H
2
C H
3
C H
3
C H
3
M = 8 5
N
8 5 ( M )
1 0
0
8 0
9 0
1 0 0
6 0
5 0
3 0
2 0
4 0
7 0
%
O
F
B
A
S
E
P
E
A
K
0 2 0 4 0 6 0 8 0 1 0 01 0 3 0 5 0 7 0 9 0 1 1 00
H
8 5
5 7
5 6
4 44 2
2 9
M = 1 1 3
1 0
0
8 0
9 0
1 0 0
6 0
5 0
3 0
2 0
4 0
7 0
%
O
F
B
A
S
E
P
E
A
K
N H
8 4
5 6
4 1
2 7
C H
2
H
3
C
7 0
1 1 3 ( M )
2 0 4 0 6 0 8 0 1 0 01 0 3 0 5 0 7 0 9 0
1 1 0
0
1 2 00
5 4
M
4 1
2 7
6 7
1 0
8 0
9 0
1 0 0
6 0
5 0
3 0
2 0
4 0
7 0
%
O
F
B
A
S
E
P
E
A
K
0
8 2
3 9
2 0 4 0 6 0 8 0 1 0 01 0 3 0 5 0 7 0 9 00
结构未知（ C6H12O，酮）
解析：
1,100，分子离子峰
2,85，失去 CH3（ 15） 的产物
3,57,丰度最大,稳定结构失去 CO(28)后的产物内容选择：
第一节 基本原理与质谱仪
basic principle and mass spectrometer
第二节 离子峰的主要类型
main kinds of ion peaks
第三节 有机分子裂解类型
cleavage types of organic compounds
第四节 质谱图与结构解析
mass spectrograph and structure determination
第五节 色谱 -质谱联用仪
hyphenated methods of GC-MS
结束
