High-Pressure Biodiesel Density: Experimental Measurements, Correlation, and Cubic-Plus-Association Equation of State (CPA EoS) Modeling

Density is one of the most important biodiesel properties, because engine injection systems (pumps and injectors) must deliver an amount of fuel precisely adjusted to provide a proper combustion while minimizing greenhouse gas emissions. The pressure influence in fuel density has become particularly important with the increased use of modern common rail systems, where pressures can reach 250 MPa. Nevertheless, besides its importance, little attention has been given to high-pressure biodiesel densities. In fact, there are almost no reports in the literature about experimental high-pressure biodiesel density data. To overcome this lack of information, in this work, new experimental measurements, from 283 to 333 K and from atmospheric pressure to 45 MPa, were performed for methyl laurate, methyl myristate, and methyl oleate, for methyl biodiesels from palm, soybean, and rapeseed oils, and for three binary and one ternary mixture of these oils. Following previous works, where the cubic-plus-association equation of state (CPA EoS) was shown to be the most appropriate model to be applied to biodiesel production and purification processes, the new high-pressure experimental data reported here were also successfully predicted with the CPA EoS, with a maximum deviation of 2.5%. A discussion about the most appropriate CPA pure compound parameters for fatty acid methyl esters is also presented

To Model Chemical Reactivity in Heterogeneous Emulsions, Think Homogeneous Microemulsions

Two important and unsolved problems in the food industry and also fundamental questions in colloid chemistry are how to measure molecular distributions, especially antioxidants (AOs), and how to model chemical reactivity, including AO efficiency in opaque emulsions. The key to understanding reactivity in organized surfactant media is that reaction mechanisms are consistent with a discrete structures–separate continuous regions duality. Aggregate structures in emulsions are determined by highly cooperative but weak organizing forces that allow reactants to diffuse at rates approaching their diffusion-controlled limit. Reactant distributions for slow thermal bimolecular reactions are in dynamic equilibrium, and their distributions are proportional to their relative solubilities in the oil, interfacial, and aqueous regions. Our chemical kinetic method is grounded in thermodynamics and combines a pseudophase model with methods for monitoring the reactions of AOs with a hydrophobic arenediazonium ion probe in opaque emulsions. We introduce (a) the logic and basic assumptions of the pseudophase model used to define the distributions of AOs among the oil, interfacial, and aqueous regions in microemulsions and emulsions and (b) the dye derivatization and linear sweep voltammetry methods for monitoring the rates of reaction in opaque emulsions. Our results show that this approach provides a unique, versatile, and robust method for obtaining quantitative estimates of AO partition coefficients or partition constants and distributions and interfacial rate constants in emulsions. The examples provided illustrate the effects of various emulsion properties on AO distributions such as oil hydrophobicity, emulsifier structure and HLB, temperature, droplet size, surfactant charge, and acidity on reactant distributions. Finally, we show that the chemical kinetic method provides a natural explanation for the cut-off effect, a maximum followed by a sharp reduction in AO efficiency with increasing alkyl chain length of a particular AO. We conclude with perspectives and prospects