Characterization of wetting using topological principles.

HYPOTHESIS: Understanding wetting behavior is of great importance for natural systems and technological applications. The traditional concept of contact angle, a purely geometrical measure related to curvature, is often used for characterizing the wetting state of a system. It can be determined from Young's equation by applying equilibrium thermodynamics. However, whether contact angle is a representative measure of wetting for systems with significant complexity is unclear. Herein, we hypothesize that topological principles based on the Gauss-Bonnet theorem could yield a robust measure to characterize wetting. THEORY AND EXPERIMENTS: We introduce a macroscopic contact angle based on the deficit curvature of the fluid interfaces that are imposed by contacts with other immiscible phases. We perform sessile droplet simulations followed by multiphase experiments for porous sintered glass and Bentheimer sandstone to assess the sensitivity and robustness of the topological approach and compare the results to other traditional approaches. FINDINGS: We show that the presented topological principle is consistent with thermodynamics under the simplest conditions through a variational analysis. Furthermore, we elucidate that at sufficiently high image resolution the proposed topological approach and local contact angle measurements are comparable. While at lower resolutions, the proposed approach provides more accurate results being robust to resolution-based effects. Overall, the presented concepts open new pathways to characterize the wetting state of complex systems and theoretical developments to study multiphase systems.

Reduction of 1,2,3-trichloropropane (TCP): pathways and mechanisms from computational chemistry calculations.

The characteristic pathway for degradation of halogenated aliphatic compounds in groundwater or other environments with relatively anoxic and/or reducing conditions is reductive dechlorination. For 1,2-dihalocarbons, reductive dechlorination can include hydrogenolysis and dehydrohalogenation, the relative significance of which depends on various structural and energetic factors. To better understand how these factors influence the degradation rates and products of the lesser halogenated hydrocarbons (in contrast to the widely studied per-halogenated hydrocarbons, like trichloroethylene and carbon tetrachloride), density functional theory calculations were performed to compare all of the possible pathways for reduction and elimination of 1,2,3-trichloropropane (TCP). The results showed that free energies of each species and reaction step are similar for all levels of theory, although B3LYP differed from the others. In all cases, the reaction coordinate diagrams suggest that ß-elimination of TCP to allyl chloride followed by hydrogenolysis to propene is the thermodynamically favored pathway. This result is consistent with experimental results obtained using TCP, 1,2-dichloropropane, and 1,3-dichloropropane in batch experiments with zerovalent zinc (Zn0, ZVI) as a reductant.