分析化学第四章质谱

ytical

质量分析器（10-6Pa）

10-5Pa

ytical

(1/2)m(1/2)m2=eV==向心力；m2/R=H0eVRme质谱方程式：m/eH02R2改变加速电压V,可以使不同m/e的离子进入检测器。质谱分辨率=M/M

联用仪器（联用仪器（THEGC/MSPROCESSDCABGasDCABGasChromatographBACDMassSpectrometerABCD

联用仪器（THELC/MSPROCESS

..API-IonTrapInterface

M

同

12C+2H+1H×3=17 峰13C+2H+1H×3=18 峰

15H15H329CH27143CH25757CH24371CH29CH1571H357H3CHCHCHCHCHCHCHCHCHCH432915H3H3CCHCHCHCHCHCH CH CHCH CH CH CHCH CH CH CH

H3C

H3CCH

H3CC

有机分子的裂解

ytical下列方式形成各种类型离子（分子碎片 +e 2e BCD•+A

CD•+AB

B•+AA•+B+ D•+C

ABCD C•+D

15 29 43 7 71 H3 CH CH CH CH CH 71 57

43 29 1571H357 H3

CH2 CH2 CH2 CH2CH2 CH2 CH2

CHCH CH43 H3 CH CH29 H3 CH

CH2 CH2 CH3CH2 CH2 CH2 CH3

15 CH

CH CH CH CH CH 2 A2 CH2 CH2OR' CH2

A OH+ OR' 2 NR' 2 CH2SR'

SR'

A

CR'

CR'

H3CCH2CH2 C OH3CCH2CH

CH

CH3H OH

H3CCH2CH2 OHCHm/z=45(M-43

H3CCH2CH2 OHCH3m/z=87(M-

m/z=73(M-

43

O57 H3C29 71

CH2CH272 100( 20 3040

50 60 70 8090100O

m/ -[CH2CH2

CH2CH2-[H3CH2C] m/z=71(48%) CH2CH2CH3

4573457329275987102(M)20 30 40 50 60 70 80 90100110m/H3 H2 HC CH CHCHCHCH3CHCHHC CH CHCH m/z=73

H3 H2 HC CHm/z=87 CH

ytical CHCH CHCHC

CHCH

C

4357712943577129588586100128(

40 50 60

70 8090100110120130m/ O CH2CH2CH2

aromaticaromaticalcoholsandaldehydesandother

massmassspectrographand99

99%OFBASE

m/z=43C3C40C5MWC7113141155169183CC8 CC12 CM

0102030405060708090100110120130140150160170180190有m/z：29，43，57，71，……CnH2n+1系列峰(σ—断裂有m/z：27，41，55，69，……CnH2n-1 C2H+（m/z=29）→CH+（

系

5%OFBASE%OFBASE

系

10080706050403020100

56(C4H8+)41(C3H5+)

84(MCyclohexaneM=84 100110

%%OFBASE0

Methlco

ytical98(M 100

CHCH

CH CH

CH CHCHm/z=55

CH

CH100807060

CH 41

69

CH m/z=69

CH50 554030 2720100

84( 10 20 30 40 50 60 70 80 90 100110

%%OF BASEPEAK

AromaticAromatic

390

65 203040

60 90100110120130

CH2

CH2

CH2

R2 OHR3m/z:31,59,73,

R

OHHRHC

OHCH

RHC

OHCH

-H2RHC

CH(CH2)

or RHC CH(CH2)

HO+

RHC

CH2CH2

-H2CCH2-H

H2CCHCH

-(Alkene+H2O)HM-46HHO+

-H2CCCH

3HCCHRHC

HCCH2

CH

-H2O

M-60H

H

2 C

CH2OH

1-PenTanolMW88 M-(H2Oand 0 10203040

M-(H2Oand M-M-60 80

BASEBASE

2-PenTanol

(CH %%

2 M-(H2O 0

M-(H2OandM-H2OM-M-M0

1020304050607080 2-Methyl-2-butanol MW881008070

59M-(H2Oand

CH3CH3CH2 CH3OH CH2 CH2)

M-CH3 59504030201000

M-(H2OandCH3)M-H2O10203040 60 80

H-

H H

CCCC-CO COO

OOH--H

-

HHCH2CHOH

-CH

CHOHm/z107(100%)-H-Hm/z121(3.5%)

OH

%%OFBASE0

CH3M 10203040 6070

%%OFBASE

Ethylsec-butyletherMW102 M-

CH2

CH3 0

M- 871020

10203040 607080

O %%OFBASE

C 216(M) 0

C

219(M+3)M

10203040

60

BASEBASEPEAK%%OF0

O98010O98

60708090

10090806050403020100

57CH3(CH2)7CHOMW14244M-44M-43M-CH2CHM-H2

M-1

yticalCh3(CH2)4COCH3(CH2)CH3(CH) 57

(small)9971 CH3(CH2) 43 CH3CH 29CH CH CH

CH

CH

O OH45

59(small) 7387

CH2CO2H(CH2)2CO2(CH2)3CO2

BASEBASE

C

Methyloctanoate2 H2%%

O

0

10203040 6070 Figure2.14.Methyl

%%OFBASE

CH2CH2CH2 0

129(M 20 40