Mass spectra general description

Following the above general description of the McLafferty rearrangement, the peak at m/z 44 in the mass spectrum of butanal can be explained by C2H4 loss from the molecular ion. The process may either be formulated in a concerted manner (a) or as a stepwise process (b) ... 

This section deals with some general principles of tandem mass spectrometry and its applicability to quantitative analysis. The MS/MS acronym is used in this book as a general term for aU tandem mass spectrometry techniques. More detailed descriptions of how the principles are exploited in practice for the various instrumental types are given in later sections of this chapter. The general concept of tandem mass spectrometry in qualitative (structural) analysis is that additional chemical information, over and above that contained in a conventional onedimensional mass spectrum, can be obtained by examining the connectivity relationships among some or all of the ions in that mass spectrum. The connectivities arise as a result of the dissociation reactions that lead to the fragment ions in a mass spectrum, e.g. ... 

The most intense peaks in the El mass spectrum of methane are the molecular ion at m/z 16 and the fragment ion at m/z 15 (Fig. 6.1). Explicitly writing the electrons helps to understand the subsequent dissociations of to yield CHs", m/z 15, by H" loss (oi) or H by CH3 loss (02), respectively. In general, it is more convenient to write the molecular ion in one of the equivalent forms. The charge and radical state are then attached to the brackets (often abbreviated as 1) enclosing the molecule. (It is advised to review the rules of Chap. 1 for terminology in the description of mass spectra). 

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