13 Electrochemistry in Laboratory Flow Systems

Organic electrosynthesis in flow reactors is an area of increasing interest, with efficient mass transport and high electrode area to reactor volume present in many flow electrolysis cell designs facilitating higher rates of production with high selectivity. The controlled reaction environment available in flow cells also offers opportunities to develop new electrochemical processes. In this chapter, various types of electrochemical flow cells are reviewed in the context of laboratory synthesis, paying particular attention to how the different reactor environments impact upon the electrochemical processes, and the factors responsible for good cell performance. Coverage includes well-established plane-parallel-plate designs, reactors with small interelectrode gaps, extended-channel electrolysis cells, and highly sophisticated designs with rapidly rotating electrodes to enhance mass transport. In each case, illustrative electrosyntheses are presented.

Oscillations and Mass Draining that Lead to a Sympathetic Eruption of a Quiescent Filament

In this paper, we present a multiwavelength analysis to mass draining and oscillations in a large quiescent filament prior to its successful eruption on 2015 April 28. The eruption of a smaller filament that was parallel and in close, ∼350″ proximity was observed to induce longitudinal oscillations and enhance mass draining within the filament of interest. The longitudinal oscillation with an amplitude of ∼25 Mm and ∼23 km s−1 underwent no damping during its observable cycle. Subsequently the slightly enhanced draining may have excited a eruption behind the limb, leading to a feedback that further enhanced the draining and induced simultaneous oscillations within the filament of interest. We find significant damping for these simultaneous oscillations, where the transverse oscillations proceeded with the amplitudes of ∼15 Mm and ∼14 km s−1, while the longitudinal oscillations involved a larger displacement and velocity amplitude (∼57 Mm, ∼43 km s−1). The second grouping of oscillations lasted for ∼2 cycles and had a similar period of ∼2 hr. From this, the curvature radius and transverse magnetic field strength of the magnetic dips supporting the filaments can be estimated to be ∼355 Mm and ≥34 G. The mass draining within the filament of interest lasted for ∼14 hr. The apparent velocity grew from ∼35 to ∼85 km s−1, with the transition being coincident with the occurrence of the oscillations. We conclude that two filament eruptions are sympathetic, i.e., the eruption of the quiescent filament was triggered by the eruption of the nearby smaller filament.

Transport of solute and solvent driven by lubrication pressure through non-deformable permeable membranes

A discrete-forcing immersed boundary method with permeable membranes is developed to investigate the effect of lubrication on the permeations of solute and solvent through membrane. The permeation models are incorporated into the discretisation at the fluid cells including the membrane, and discretised equations for the pressure Poisson equation and convection–diffusion equation for the solute are represented with the discontinuities at the membrane. The validity of the proposed method is established by the convergence of the numerical results of the permeate fluxes (solute and solvent) to higher-order analytical models in a lubrication-dominated flow field. As a model of the mass exchange between inside and outside of a biological cell flowing in a capillary, a circular membrane is placed between parallel flat plates, and the effect of lubrication is investigated by varying the distance between the membrane and the walls. The pressure discontinuity near the wall is larger than that at the stagnation point, which is a highlighted effect of lubrication. In the case of a small gap, the solute transport is dominated by convection inside the circular membrane and by diffusion outside. Through the time variation of the concentration in the circular membrane, lubrication is shown to enhance mass transport from/to inside and outside the membrane.

The influence of acoustic power on chemical absorption of CO2 using Slow Kinetic Solvent

Ultrasonic Irradiation (UI) is an emerging technology that is used to assist the CO2 absorption process. Even for the slow kinetic solvents without using any chemical promoter, high-frequency UI might enhance mass transfer during the absorption process. For this purpose, it is essential to study the performance of a high-frequency ultrasonic-assisted absorption system under varied operating conditions. The ultrasonic power is considered as one of the main parameters during the absorption of CO2. Thus, in this paper, the influence of ultrasonic power is presented using Methyl diethanolamine (MDEA) as a chemical solvent. The ultrasonic power has been varied from 0 to 15.3 W. The results tend to show a significant absorption rate enhancement for higher ultrasonic power. Moreover, they prove that the high-frequency ultrasonic absorption system has high potential to be utilized to enhance the absorption using promoter-free MDEA.

Isotope Fractionation during Gas Chromatography Can Enhance Mass Spectrometry-Based Measures of 2H-Labeling of Small Molecules

Stable isotope tracers can be used to quantify the activity of metabolic pathways. Specifically, 2H-water is quite versatile, and its incorporation into various products can enable measurements of carbohydrate, lipid, protein and nucleic acid kinetics. However, since there are limits on how much 2H-water can be administered and since some metabolic processes may be slow, it is possible that one may be challenged with measuring small changes in isotopic enrichment. We demonstrate an advantage of the isotope fractionation that occurs during gas chromatography, namely, setting tightly bounded integration regions yields a powerful approach for determining isotope ratios. We determined how the degree of isotope fractionation, chromatographic peak width and mass spectrometer dwell time can increase the apparent isotope labeling. Relatively simple changes in the logic surrounding data acquisition and processing can enhance gas chromatography-mass spectrometry measures of low levels of 2H-labeling, this is especially useful when asymmetrical peaks are recorded at low signal:background. Although we have largely focused attention on alanine (which is of interest in studies of protein synthesis), it should be possible to extend the concepts to other analytes and/or hardware configurations.