Mass Spectrometry - Examples

Mass Spectrometry - Examples

Following are examples of compounds listed by functional group, which demonstrate patterns which can be seen in mass spectra of compounds ionized by electron impact ionization. These examples do not provide information about the fragmentation mechanisms that cause these patterns. Additional information can be found in mass spectrometry reference books.

Scroll through this page, or use this list to move to select functional groups:


 

Alcohol:

An alcohol's molecular ion is small or non-existent. Cleavage of the C-C bond next to the oxygen usually occurs. A loss of H2O may occur as in the spectra below. An alcohol's molecular ion is small or non-existent. Cleavage of the C-C bond next to the oxygen usually occurs. A loss of H2O may occur as in the spectra below.

Mass Spec Spectra of Alcohol Example

3-Pentanol
C5H12O
MW = 88.15
Mass Spec Cleavage of Alcohol Example

 

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Aldehyde:

Cleavage of bonds next to the carboxyl group results in the loss of hydrogen (molecular ion less 1) or the loss of CHO (molecular ion less 29).

Mass spectra of an aldehyde

 

3-Phenyl-2-propenal
C9H8O
MW = 132.16
Mass spec cleavage of an aldehyde molecule

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Alkane:

Molecular ion peaks are present, possibly with low intensity.  The fragmentation pattern contains clusters of peaks 14 mass units apart (which represent loss of (CH2)nCH3).

Mass spectra of an alkane

 

Hexane
C6H14
MW = 86.18
Mass spec cleavage of alkane molecule

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Amide:

Primary amides show a base peak due to the McLafferty rearrangement.

Mass spectra of an amide

 

3-Methylbutyramide
C5H11NO
MW = 101.15
Mass spec cleavage of amide molecule

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Amine:

Molecular ion peak is an odd number.  Alpha-cleavage dominates aliphatic amines.

Mass spectrum of an amine

 

n-Butylamine
C4H11N
MW = 73.13
Mass spec cleavage of an amine

Another example is a secondary amine shown below.  Again, the molecular ion peak is an odd number.  The base peak is from the C-C cleavage adjacent to the C-N bond.

Mass spectrum of an amine

 

n-Methylbenzylamine
C8H11N
MW = 121.18
Mass spec cleavage of an amine

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Aromatic:

Molecular ion peaks are strong due to the stable structure.

Mass spectrum of an aromatic

 

Naphthalene
C10H8
MW = 128.17
Aromatic molecule

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Carboxylic Acid:

In short chain acids, peaks due to the loss of OH (molecular ion less 17) and COOH (molecular ion less 45) are prominent due to cleavage of bonds next to C=O.

Mass spectrum of a carboxylic acid

 

2-Butenoic acid
C4H6O2
MW = 86.09
Mass spec cleavage of a carboxylic acid

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Ester:

Fragments appear due to bond cleavage next to C=O (alkoxy group loss, -OR) and hydrogen rearrangements.

Mass spectrum of an ester

 

Ethyl acetate
C4H8O2
MW = 88.11
Mass spec cleavage of an ester

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Ether:

Fragmentation tends to occur alpha to the oxygen atom (C-C bond next to the oxygen).

Mass spectrum of ether

 

Ethyl methyl ether
C3H8O
MW = 60.10
Mass spec cleavage of ether

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Halide:

The presence of chlorine or bromine atoms is usually recognizable from isotopic peaks.

Mass spectrum of a halide

 

1-Bromopropane
C3H7Br
MW = 123.00
Mass spec cleavage of halide

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Ketone:

Major fragmentation peaks result from cleavage of the C-C bonds adjacent to the carbonyl.

Mass spectrum of a ketone

 

4-Heptanone
C7H14O
MW = 114.19
Mass spec cleavage of a ketone

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Written by Dr. Linda Breci (retired).

If you have comments or suggestions, email Dr. Michael Marty at mtmarty@arizona.edu.