Relaxation Dynamics of Ethanol and N-Butanol in Diesel Fuel Blends from Terahertz Spectroscopy

Abstract

Binary blends of ethanol-diesel, n-butanol-diesel, ethanol-biodiesel, and n-butanol-biodiesel have been analyzed with terahertz time-domain spectroscopy in a full range of concentrations and at room temperature. The real and imaginary parts of the complex dielectric constant of the blends were obtained from the spectra and fitted to the Debye model at low volume concentrations (up to 7.5% for ethanol in diesel and up to 20% for butanol in diesel, ethanol in biodiesel, and butanol in biodiesel blends), considering the number of relaxation processes recommended in the literature for each pure component (single for diesel, double for biodiesel, and triple for alcohols). The results indicate that the faster relaxation time in low alcohol mixtures is longer than in pure alcohols. This relaxation time increases as the alcohol content increases. The excess of the real and of imaginary parts of the dielectric constant were individually determined. The analysis of such excess and of its different contributions (volume, contrast, and interactions) suggests that the intermolecular interactions between the different components of the blends dominate the relaxation dynamics in each pseudo-binary system. Ethanol was found to move blends further away from ideal behavior than n-butanol. In fact, these latter blends showed the most ideal behavior, suggesting that the length of the alcohol carbon chain plays an important role. This information allows a possible link between the nonlinear behavior of the physicochemical properties of the blends (e.g., viscosity and surface tension) and the molecular interactions between their constituent molecules. This relation could have direct application for monitoring the fuel composition and quality in the vehicle control systems.