Corrosion inhibition of magnesium alloy AZ31 in chloride-containing solutions by aqueous permanganate

In this work, corrosion of the AZ31 magnesium alloy was examined in 0.05 M NaCl solutions containing 0.01–0.150 mol/dm³ of potassium permanganate as a corrosion inhibitor. A set of electrochemical impedance spectroscopy, linear sweep voltammetry, and hydrogen evolution measurements revealed high inhibitor effectiveness at relatively high (0.150 mol/dm³) KMnO₄ concentrations. Based on data of energy-dispersive X-ray analysis, scanning electron microscopy, and Raman spectroscopy, a mechanism of the corrosion inhibition of AZ31 alloy by potassium permanganate in chloride-containing media was proposed.

     

Structure-transport analysis for particulate packings in trapezoidal microchip separation channels

This article investigates the efficiency of particulate beds confined in quadrilateral microchannels by analyzing the three-dimensional fluid flow velocity field and accompanying hydrodynamic dispersion with quantitative numerical simulation methods. Random-close packings of uniform, solid (impermeable), spherical particles of diameter d(p) were generated by a modified Jodrey-Tory algorithm in eighteen different conduits with quadratic, rectangular, or trapezoidal cross-section at an average bed porosity (interparticle void fraction) of epsilon = 0.48. Velocity fields were calculated by the lattice Boltzmann method, and axial hydrodynamic dispersion of an inert tracer was simulated at Péclet numbers Pe = u(av)d(p)/D(m) (where u(av) is the average fluid flow velocity through a packing and D(m) the bulk molecular diffusion coefficient) from Pe = 5 to Pe = 30 by a Lagrangian particle-tracking method. All conduits had a cross-sectional area of 100d(p)(2) and a length of 1200d(p), translating to around 10(5) particles per packing. We present lateral porosity distribution functions and analyze fluid flow profiles and velocity distribution functions with respect to the base angle and the aspect ratio of the lateral dimensions of the different conduits. We demonstrate significant differences between the top and bottom parts of trapezoidal packings in their lateral porosity and velocity distribution functions, and show that these differences increase with decreasing base angle and increasing base-aspect ratio of a trapezoidal conduit, i.e., with increasing deviation from regular rectangular geometry. Efficiencies are investigated in terms of the axial hydrodynamic dispersion coefficients as a function of the base angle and base-aspect ratio of the conduits. The presented data support the conclusion that the efficiency of particulate beds in trapezoidal microchannels strongly depends on the lateral dimensions of the conduit and that cross-sectional designs based on large side-aspect-ratio rectangles with limited deviations from orthogonality are favorable.     

Transition from creeping via viscous-inertial to turbulent flow in fixed beds

This review is concerned with the analysis of flow regimes in porous media, in particular, in fixed beds of spherical particles used as reactors in engineering applications, or as separation units in liquid chromatography. A transition from creeping via viscous-inertial to turbulent flow is discussed based on macro-scale transport behaviour with respect to the pressure drop-flow rate dependence, in particular, the deviation from Darcy's law, as well as direct microscopic data which reflect concomitant changes in the pore-level hydrodynamics. In contrast to the flow behaviour in straight pipes, the transition from laminar to turbulent flow in fixed particulate beds is not sharp, but proceeds gradually through a viscous-inertial flow regime. The onset of this steady, nonlinear regime and increasing role of inertial forces is macroscopically manifested in the failure of Darcy's law to describe flow through fixed beds at higher Reynolds numbers. While the physical reasons for this failure still are not completely understood, it is not caused by turbulence which occurs at Reynolds numbers about two orders of magnitude above those for which a deviation from Darcy's law is observed. Microscopic analysis shows that this steady, nonlinear flow regime is characterized by the development of an inertial core in the pore-level profile, i.e., at increasing Reynolds number velocity profiles in individual pores become flatter towards the center of the pores, while the velocity gradient increases close to the solid-liquid interface. Further, regions with local backflow and stationary eddies are demonstrated for the laminar flow regime in fixed beds. The onset of local fluctuations (end of laminar regime) is observed at superficial Reynolds numbers on the order of 100. Complementary analysis of hydrodynamic dispersion suggests that this unsteady flow accelerates lateral equilibration between different velocities in fixed beds which, in turn, reduces spreading in the longitudial (macroscopic flow) direction.     

Mechanochemistry-Amended Barbier Reaction as an Expedient Alternative to Grignard Synthesis**

Organomagnesium halides (Grignard reagents) are essential carbanionic building blocks widely used in carbon-carbon and carbon-heteroatom bond-forming reactions with various electrophiles. In the Barbier variant of the Grignard synthesis, the generation of air- and moisture-sensitive Grignard reagents occurs concurrently with their reaction with an electrophile. Although operationally simpler, the classic Barbier approach suffers from low yields due to multiple side reactions, thereby limiting the scope of its application. Here, we report a mechanochemical adaptation of the Mg-mediated Barbier reaction, which overcomes these limitations and facilitates the coupling of versatile organic halides (e.g., allylic, vinylic, aromatic, aliphatic) with a diverse range of electrophilic substrates (e.g., aromatic aldehydes, ketones, esters, amides, O-benzoyl hydroxylamine, chlorosilane, borate ester) to assemble C−C, C−N, C−Si, and C−B bonds. The mechanochemical approach has the advantage of being essentially solvent-free, operationally simple, immune to air, and surprisingly tolerant to water and some weak Brønsted acids. Notably, solid ammonium chloride was found to improve yields in the reactions of ketones. Mechanistic studies have clarified the role of mechanochemistry in the process, indicating the generation of transient organometallics facilitated by improved mass transfer and activation of the surface of magnesium metal.     

Dissecting Noncovalent Interactions in Carboxyl-Functionalized Ionic Liquids Exhibiting Double and Single Hydrogens Bonds Between Ions of Like Charge

We show that the carboxyl-functionalized ionic liquid 1-(carboxymethyl)pyridinium bis(trifluoromethylsulfonyl)imide [HOOC-CH₂-py][NTf₂] exhibits three types of hydrogen bonding: the expected single hydrogen bonds between cation and anion, and, surprisingly, single and double hydrogen bonds between the cations, despite the repulsive Coulomb forces between the ions of like charge. Combining X-ray crystallography, differential scanning calorimetry, IR spectroscopy, thermodynamic methods and DFT calculations allows the analysis and characterization of all types of hydrogen bonding present in the solid, liquid and gaseous states of the ionic liquid (IL). We find doubly hydrogen bonded cationic dimers (c⁺=c⁺) in the crystalline phase. With increasing temperature, this binding motif opens in the liquid and is replaced by (c⁺−c⁺−a⁻ species, with a remaining single cationic hydrogen bond and an additional hydrogen bond between cation and anion. We provide clear evidence that the IL evaporates as hydrogen-bonded ion pairs (c⁺−a⁻) into the gas phase. The measured transition enthalpies allow the noncovalent interactions to be dissected and the hydrogen bond strength between ions of like charge to be determined.     

Efficient implementation of periodic boundary conditions in Monte Carlo simulation

Determination of the shortest distances between particles is one of the most time-consuming parts of molecular simulation by the Monte Carlo method. In this work, we demonstrate that the use of signed-integer storage of coordinates in a scaled box allows one to skip multiple conditional statements in realization of periodic boundary conditions in cubic and rectangular boxes, which, in turn, increases the performance. Performance of the improved procedure was tested in NVT Monte Carlo simulations for liquid krypton and water. © 2018 Wiley Periodicals, Inc.     

Vaporization enthalpies of imidazolium based ionic liquids: dependence on alkyl chain length

Vaporization enthalpies of a series of ten 1-alkyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ionic liquids (ILs) [C(n) mim][NTf(2) ] with alkyl chain lengths of n=2, 3, 4, 6, 8, 10, 12, 14, 16, and 18 are determined by using a recently developed quartz crystal microbalance method. Due to the high sensitivity of the microbalance vapor studies can be extended to temperatures 60-100 K lower than those available with other methods. The results reveal a remarkably linear dependence of the vaporization enthalpies on the chain length at the reference temperature of 298 K.     

Thermodynamics of Aqueous Nitrilotriacetic Acid (NTA) Systems: Apparent and Partial Molar Heat Capacities and Volumes of Aqueous HNTA2−, NTA3−, MgNTA−, CoNTA−, NiNTA− and CuNTA− at 25 °C

Apparent molar heat capacities and volumes have been determined for aqueous Na₂HNTA, Na₃NTA, NaMgNTA, NaCoNTA, NaNiNTA and NaCuNTA at 25 °C. The experimental results have been analyzed in terms of Young’s rule with an extended Debye–Hückel equation to obtain standard partial molar heat capacities C _p ^o and volumes V ^o for the species HNTA²⁻(aq), NTA³⁻(aq), MgNTA⁻(aq), CoNTA⁻(aq), NiNTA⁻(aq) and CuNTA⁻(aq), at ionic strengths I = 0 and I = 0.1 mol⋅kg⁻¹. Values of C _p ^o and V ^o were combined with the literature data to estimate the stability constants of the NTA complexes at temperatures up to 100 °C.