Standard Article

Lube Products. Molecular Characterization of Base Oils

Petroleum and Liquid Fossil Fuels Analysis

  1. Luciano Montanari

Published Online: 15 SEP 2006

DOI: 10.1002/9780470027318.a1824

Encyclopedia of Analytical Chemistry

Encyclopedia of Analytical Chemistry

How to Cite

Montanari, L. 2006. Lube Products. Molecular Characterization of Base Oils. Encyclopedia of Analytical Chemistry. .

Author Information

  1. San Donato Milanese, EniTecnologie S.p.A., Italy

Publication History

  1. Published Online: 15 SEP 2006


Base oils used in the formulation of lubricant products are a complex mixture of paraffinic (prevalently branched), aromatic and naphthenic (cycloparaffinic) molecules ranging in carbon number from 20 to 40+. Most automotive crankcase oils, accessory fluids, and many industrial lubricants contain in excess of 80% base oil in their “finished” formulation.

The compositional analysis of Lube base oils is usually obtained by a two-step procedure. The first step separates the aromatic and saturated fractions by column chromatography (American Society for Testing and Materials, ASTM D2549). The aromatic fraction is then further characterized by mass spectrometry (ASTM D3239) and the saturated subclasses of paraffins and cycloparaffins are measured by a different mass spectrometry method (ASTM D2786).

Recently the Lube base oils have been characterized at the molecular level by means of nuclear magnetic resonance (NMR) spectroscopy. The conventional NMR spectra have the problem of signal overlap due to the presence of a great number of isomers in the base oil composition.

To overcome the problem of signal overlap, some selected multiplet subspectral carbon-13 nuclear magnetic resonance (13C-NMR) analyses were developed and, in particular, gated spin echo (GASPE) and distortionless enhancement by polarization transfer (DEPT) have been applied to obtain quantitative CHn subspectra in petroleum fractions.

Usually the quantitative data obtained from GASPE have a better accuracy than those from DEPT and it will be shown how GASPE is applied to study the molecular characteristics of the aliphatic moieties of base oils of a different nature.

On the basis of the GASPE data and of the average molecular mass obtained via vapor pressure osmometry (VPO), the average number of branches and aliphatic rings can be calculated. Moreover, on the basis of GASPE, the distribution of side chain lengths and the positions of the methyl groups along the straight chain (methyls are the only groups for which the positions are directly obtained from NMR spectra) were obtained.

All these structural features are related to the finished lubricant's performance in both crankcase and industrial applications.