Interpretationofmassspectra.ppt

Interpretation of Mass Spectra (I) Rings Plus Double Bonds Logic Neutral Loss Commonly observed neutral losses Molecular Ion Abundance Factors that Influence the Abundance: Stability Factors that Influence the Abundance: Stability Factors that Influence the Abundance: Stability Factors that Influence the Abundance: Stability Criteria for the Identification of the Molecular Ion 1. The molecular ion must be the ion of highest m/z in the mass spectrum (besides the corresponding isotopic peaks). 2. It has to be an odd-electron ion, M+?. 3. The peaks at the next lowest m/z must be explicable in terms of reasonable losses, i.e., of common radicals or molecules. Signals at M–5 to M–14 and at M–21 to M–25 point towards a different origin of the presumed M+?. 4. Fragment ions may not show isotopic patterns due to elements that are not present in the presumed molecular ion. 5. No fragment ion may contain a larger number of atoms of any particular element than the molecular ion does. Alkanes and Branched Alkanes High Branched Alkanes and Alkenes Cycloalkanes and Aromatics Alcohols and Ethers Ketones Acids and Esters Amines Amides and Mecaptans Common Fragment Ions Common Elemental compositions of Molecular ion Conclusion * Basic Theory Fragmentation mechanism EI fragmentation –C2 + –Mg+ –SO2 ++ –Li3H3 + – Any of the above Most mass spectra are not trivial to decipher due to: – interferences (Mg+ or C2+ on last page) – complexities of fragmentation – (exception: some elemental analysis cases) Instead, MS Interpretation is problem solving, ‘playing chess’, or ‘cracking a code’ – Use all available information in a logical and organized manner Our focus: EI spectra of “small” organic molecules The interpretation techniques are applicable to spectra obtained with other ionization techniques MS Interpretation Three steps: 1. Run the spectra you get against a database (if available) - Don’t stop h