Introduction to 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 (QUIZ! links you to a tutorial quiz for that functional group):
 

Alcohol     QUIZ! Amine     QUIZ! Ether     QUIZ!
Aldehyde     QUIZ! Aromatic Halide     QUIZ!
Alkane     QUIZ! Carboxylic Acid     QUIZ! Ketone     QUIZ!
Amide     QUIZ! Ester     QUIZ! Return to CONTENTS
 
 
 

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.




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).



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).


Amide

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


Amine

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

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.



Aromatic

Molecular ion peaks are strong due to the stable structure.


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.


Ester

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


Ether

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


Halide

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


Ketone

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


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