Molecular orientation of asphaltenes and PAH model compounds in Langmuir-Blodgett films using sum frequency generation spectroscopy.

Asphaltenes are an important class of compounds in crude oil whose surface activity is important for establishing reservoir rock wettability which impacts reservoir drainage. While many phenomenological interfacial studies with crude oils and asphaltenes have been reported, there is very little known about the molecular level interactions between asphaltenes and mineral surfaces. In this study, we analyze Langmuir-Blodgett films of asphaltenes and related model compounds with sum frequency generation (SFG) vibrational spectroscopy. In SFG, the polarization of the input (vis, IR) and output (SFG) beams can be varied, which allows the orientation of different functional groups at the interface to be determined. SFG clearly indicates that asphaltene polycyclic aromatic hydrocarbons (PAHs) are highly oriented in the plane of the interface and that the peripheral alkanes are transverse to the interface. In contrast, model compounds with oxygen functionality have PAHs oriented transverse to the interface. Computational quantum chemistry is used to support corresponding band assignments, enabling robust determination of functional group orientations.

Infrared contrast of crude-oil-covered water surfaces.

Infrared oil spill detection utilizes either temperature or emissivity contrast of native and oil-covered water surfaces. In particular, the thickness dependent radiance contrast due to thin film interference has been studied. Together with detection boundaries derived from the radiative transfer equation, we can explain historically observed daytime contrast reversal and our observations during nighttime, better contrast from thin oil slicks than from thick films, which to our knowledge has not been mentioned in the literature. These findings have important implications to long-wavelength infrared (LWIR) instrument design and data interpretation for crude oil spill detection.

Modeling of thickness dependent infrared radiance contrast of native and crude oil covered water surfaces.

We present a model for infrared radiance contrast of native and crude oil covered water surfaces. This model is based on the so called "direct" approach by treating individual volumetric elements as incoherent radiators. The total emitted radiation is calculated by the sum of individual contributions from the oil film and the underlying water, respectively. Therefore, different temperatures can be assigned to the oil film and water assuming quasi-static temperature distribution, enabling modeling of differential heating of the oil film during daytime. This model can be applied to remote sensing, particularly, to explain the historically observed thickness-dependent contrast in native and crude oil covered sea surfaces.

Diffusivity of asphaltene molecules by fluorescence correlation spectroscopy.

Using fluorescence correlation spectroscopy (FCS) we measure the translational diffusion coefficient of asphaltene molecules in toluene at extremely low concentrations (0.03-3.0 mg/L): where aggregation does not occur. We find that the translational diffusion coefficient of asphaltene molecules in toluene is about 0.35 x 10(-5) cm(2)/s at room temperature. This diffusion coefficient corresponds to a hydrodynamic radius of approximately 1 nm. These data confirm previously estimated size from rotational diffusion studied using fluorescence depolarization. The implication of this concurrence is that asphaltene molecular structures are monomeric, not polymeric.