Determination of the vaporization order of crude oils through the chemical analysis of crude oil residues burned on water.

To determine the vaporization order of (the components in) crude oils, the density, the viscosity and the chemical composition of a light and a heavy crude oil were studied as a function of the burning efficiency. An experimental series of small scale in-situ crude oil burns on water were conducted with the two crude oils. Chemical analyses of the burned residues showed that the components in crude oils vaporize in order of decreasing volatility and the depletion rate of components generally decreased with increasing molecular mass. Ultimately, this means that the burning efficiency of a crude oil burning on water can be related to fire dynamics principles, irrespective of its chemical and physical properties. The relative abundance of pyrogenic PAHs in the burned residues increased up to a maximum of 2600% for the light crude oil and 9100% for the heavy crude oil. Increased abundances of the pyrogenic PAHs were caused by the formation of the pyrogenic PAHs during the burning and not by an increase in concentration in the burned residues. Overall, the results provide relevant data for predicting the effectiveness of in-situ burning of crude oil as oil spill response method, both in terms of its burning efficiency and its environmental impact.

Chiral Control in Pentacoordinate Systems: The Case of Organosilicates.

Chirality at the central element of pentacoordinate systems can be controlled with two identical bidentate ligands. In such cases the topological Levi-Desargues graph for all the Berry pseudorotations (BPR, max. 20) reduces to interconnected inner and outer "circles" that represent the dynamic enantiomer pair. High enough barriers of the BPR crossovers between the two circles is all what is needed to ascertain chiral integrity. This is illustrated computationally and experimentally for the organosilicates 7 and 10 that carry besides a Me (a), Et (b), Ph (c), or F (d) group two bidentate 2-(phenyl)benzo[ b]-thiophene or 2-(phenyl)naphthyl ligands, respectively. The enantiomers of tetraorganosilane precursor 9 could be separated by column chromatography. Their chiral integrity persisted on forming the silicates. CD spectra are reported for 10c. Fluoro derivative 10d is shown to have its electronegative F substituent in an equatorial position, is stable toward hydrolysis, and its enantiomers do not racemize at ambient temperatures, while those of 10c racemize slowly.

Experimental Procedure for Laboratory Studies of In Situ Burning : Flammability and Burning Efficiency of Crude Oil.

A new method for the simultaneous study of the flammability and burning efficiency of fresh and weathered crude oil through two experimental laboratory setups is presented. The experiments are easily repeatable compared to operational scale experiments (pool diameter ≥2 m), while still featuring quite realistic in situ burning conditions of crude oil on water. Experimental conditions include a flowing water sub-layer that cools the oil slick and an external heat flux (up to 50 kW/m2) that simulates the higher heat feedback to the fuel surface in operational scale crude oil pool fires. These conditions enable a controlled laboratory study of the burning efficiency of crude oil pool fires that are equivalent to operational scale experiments. The method also provides quantitative data on the requirements for igniting crude oils in terms of the critical heat flux, ignition delay time as a function of the incident heat flux, the surface temperature upon ignition, and the thermal inertia. This type of data can be used to determine the required strength and duration of an ignition source to ignite a certain type of fresh or weathered crude oil. The main limitation of the method is that the cooling effect of the flowing water sub-layer on the burning crude oil as a function of the external heat flux has not been fully quantified. Experimental results clearly showed that the flowing water sub-layer does improve how representative this setup is of in situ burning conditions, but to what extent this representation is accurate is currently uncertain. The method nevertheless features the most realistic in situ burning laboratory conditions currently available for simultaneously studying the flammability and burning efficiency of crude oil on water.

Effectiveness of a chemical herder in association with in-situ burning of oil spills in ice-infested water.

The average herded slick thickness, surface distribution and burning efficiency of a light crude oil were studied in ice-infested water to determine the effectiveness of a chemical herder in facilitating the in-situ burning of oil. Experiments were performed in a small scale (1.0m2) and an intermediate scale (19m2) setup with open water and 3/10, 5/10 and 7/10 brash ice coverages. The herded slick thicknesses (3-8mm) were ignitable in each experiment. The presence of ice caused fracturing of the oil during the herding process, which reduced the size of the herded slicks and, as a consequence, their ignitability, which in turn decreased the burning efficiency. Burning efficiencies relative to the ignited fraction of the oil were in the expected range (42-86%). This shows that the herder will be an effective tool for in-situ burning of oil when the ignitability issues due to fracturing of the oil are resolved.