Structural determination of zinc dithiophosphates in lubricating oils by gas chromatography–mass spectrometry with electron impact and electron-capture negative ion chemical ionization

Pentafluorobenzyl ester derivatives were used to identify zinc dialkyldithiophosphates and diaryldithiophosphates anti-wear engine oil additives by GC–electron impact ionization (EI) MS and GC–electron-capture negative ion chemical ionization (ECNCI) MS analysis. GC–EI-MS of the dialkyldithiophosphate–pentafluorobenzyl derivatives afforded characteristic fragment ions corresponding to the cleavage of one and two alkyl radicals. In most cases, information was only obtained on one alkyl chain. Additional and complete information was obtained with retention time indices using synthetic derivatives and with GC–ECNCI-MS analysis. ECNCI afforded characteristic dithiophosphate anions which allowed the determination of the total number of carbon atoms in the alkyl radicals. The diastereoisomer mixtures of 2-hydroxy-sec.-alkyl radicals were completely separated on GC analysis.