The method of dynamic microdistillation instrumented through DSC has been further elaborated and validated using distillate and residual base oils as model systems. The two major experimental factors of the method-sample mass and heating rate were varied to determine the optimal (standard) experimental conditions for better fraction resolution and thus more reliable quality assessment of petroleum products (lube oils). If these are increased, the fraction resolution ability of the method is reduced-the lighter fractions evaporate at temperatures close to those of the heavier ones, and generally all the fractions evaporate/oxidize at higher temperatures. Two major types of reactions in the heated sample were identified-the one occurring on the metal surface of the crucible leading to a polymer (lacquer) film formation and the other the oxidative cracking in the bulk of the sample leading to the formation of gaseous products. The extent of the lacquer film formation on the crucible metal surface can be reduced by increasing the heating rate and/or the sample mass, while their reduction results in better fraction resolution. (C) 2006 Elsevier B.V. All rights reserved.