Molecular features of sulfonic acids used for synthesis of overbased detergent additives

Overbased calcium sulfonates are used in many modern oil formulations to provide cleaning action and to neutralize the organic acids formed during combustion, preventing corrosion. The performance of detergents is related to their molecular structure, which is generally known only as a chemical category. In the present work, nuclear magnetic resonance (NMR) spectroscopy and electrospray ionization mass spectrometry are used to analyze the molecular structure of three alkyl‐benzene sulfonic acids in detail. Some important molecular features were obtained by elaborating the NMR signal intensities, such as the number and positions of alkyl substituents on the benzene ring, the distribution of alkyl chain lengths and the mole fraction of 1‐phenyl isomers (synthesized by alkylation of benzene with α‐olefin). Ion‐trap mass spectrometry is used to obtain the mass spectrometry/mass spectrometry (MS²) spectra of the principal molecular ions. By choosing suitable molecular ions, MS² spectra can ascertain the presence of different substituted benzene isomers within a mixture because the MS² spectra show specific fragments due to the number of alkyl substituents on the aromatic ring. Copyright © 2006 John Wiley & Sons, Ltd.