Analysis of Base Oil Fractions by ClMn(H2O)+ Chemical Ionization Combined with Laser-Induced Acoustic Desorption/Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

Abstract

Laser-induced acoustic desorption (LIAD), combined with chemical ionization with the ClMn(H(2)O)(+) ion, is demonstrated to facilitate the analysis of base oils by Fourier transform ion cyclotron resonance mass spectrometry. The LIAD/ClMn(H(2)O)(+) method produces only one product ion, [ClMn + M](+), for each component (M) in base oils, thus providing molecular weight (MW) information for the analytes. With the exception of one sample, no fragmentation was observed. The mass spectra indicate the presence of homologous series of ions differing in mass by multiples of 14 Da (i.e., CH(2)). All peaks in the spectra correspond to ions with even m/z values and hence are formed from hydrocarbons with no nitrogen atoms, in agreement with the compositional nature of base oils. The MW distributions measured for two groups of base oil samples cover the range 350-600 Da, which is in excellent agreement with the values determined by gas chromatography. Moreover, the hydrocarbon types (i.e., paraffin and cycloparaffins with different numbers of rings) present in each base oil sample can be determined based on the m/z values of the product ions. Finally, the results obtained by using LIAD/ClMn(H(2)O)(+) indicate that the efficiency of the technique (combined desorption and ionization efficiency) is similar for different hydrocarbon types and fairly uniform over a wide molecular weight range, thus allowing quantitative analysis of the base oils. Hence, the product ions' relative abundances were used to determine the percentage of each type of hydrocarbon in the base oil. In summary, three important parameters (MW distributions, hydrocarbon types, and their relative concentrations) can be obtained in a single experiment. This mass spectrometric technique therefore provides detailed molecular-level information for base oils, which cannot be obtained by other analytical methods.