Analysis and Review of Chemical Reactions and Transport Processes in Pulsed Electrical Discharge Plasma Formed Directly in Liquid Water

Electrical discharges formed directly in liquid water include three general cases where (a) streamer-like plasma channels form in, but do not span, the electrode gap, (b) spark discharges produce transient plasma channels that span the electrode gap, and (c) arc discharges form plasma channels with relatively longer life times. Other factors including the input energy (from <1?J/pulse to >1?kJ/pulse) as well as solution properties and the rates of energy delivery affect the nature of the discharge channels. An understanding of the formation of chemical species, including the highly reactive hydroxyl radical and more stable molecular species such as hydrogen and hydrogen peroxide, in such plasma requires determination of temporal and spatial variations of temperature, pressure, plasma volume, and electrical characteristics including current, voltage (electric field), and plasma conductivity. In spark and arc discharges analysis of the physical processes has focused on hydrodynamic and thermal characterization, while only a limited amount of work has connected these physical processes to chemical reactions. On the other hand, the most successful model of the chemical reactions in streamer-like discharges relies on simple assumptions concerning the temperature and pressure in the plasma channels, while analysis of the physical processes is more limited. This paper reviews the literature on the mathematical modeling of electrical discharges in liquid water spanning the range from streamer-like to spark and arc discharges, and compares the properties and processes in these electrical discharges to those in electron beam radiolysis and ultrasound.     

Chlorinated Organic Compound Removal by Gas Phase Pulsed Streamer Corona Electrical Discharge with Reticulated Vitreous Carbon Electrodes

Trichloroethylene (TCE) and vinyl chloride (VC) removal by gas phase pulsed corona discharge was investigated with attention to energy efficiency and byproduct identification. Approximately 50–95% removal of TCE and vinyl chloride was observed, depending on the energy density applied to the gas. Water vapor reduced TCE removal in some experiments. Evidence was found for post-corona reactions leading to removal of vinyl chloride downstream of the plasma discharge, while significant post-corona removal of TCE was not observed. Removal efficiencies of 100–900 g/kW-hr in the case of 1000 ppm feed of TCE, and of 2–24 g/kW-hr for a 100 ppm feed of vinyl chloride were found. In the TCE experiments, the formation of dichloroacetyl chloride was observed, while an unknown byproduct was found with vinyl chloride. The addition of a platinum-rhodium coated electrode was found to reduce the post-corona removal of vinyl chloride at low energy density.     

Electrical Conductance Studies in Aqueous Solutions with Aspartic Ions

Conductivity measurements of dilute aqueous solutions of DL-aspartic acid, potassium-DL-aspartate and magnesium-DL-aspartate were performed in the 288.15 to 323.15 K temperature range. The limiting molar conductances of aspartate anions, λ ⁰(HAsp⁻,T) and the dissociation constants of aspartic acid, K ₂(T) were derived by use of the Debye-Hückel equation for the activity coefficients and the Onsager, and Quint and Viallard conductivity equations.     

Electrical Conductance Studies in Aqueous Solutions with Glutamic Ions

Conductivity measurements in dilute aqueous solutions of L-glutamic acid, DL-glutamic acid, sodium-L-glutamate and magnesium-L-glutamate, were performed in the 288.15 to 323.15 K temperature range. The limiting molar conductivities of glutamic anions, λ ^o(HGlu⁻,T) and the dissociation constants of glutamic acid, K ₂(T) were derived by the use of the Debye–Hückel equation for the activity coefficients and the Onsager, and Quint and Viallard conductivity equations.     

Phenol Degradation Features in Aqueous Solutions upon Dielectric-Barrier Discharge Treatment

The formation kinetics and mechanism were studied for the intermediate and final products of degradation of aqueous phenol solutions in air and oxygen low-temperature dielectric-barrier discharge plasmas in a reactor with different geometric arrangements of electrodes. It was shown that the plasma-enhanced oxidation of phenol could be described in the general form by the well-known mechanism of enzymatic oxidation of toxic pollutants (-mechanism). The estimated effective rate constant of phenol degradation in an aqueous solution in an ₂ plasma in reactors with the parallel-plate and coaxial arrangement of electrodes was 2.2 × 10^–3 s^–1 and 5.8 × 10^–2 s^–1, respectively. It was found that the potential toxicity of solutions after treatment was 7.5 times lower than that of the untreated solutions.     

Electrical Conductance Studies in Aqueous Solutions with Ascorbate Ions

Conductivity measurements in dilute aqueous solutions of L-ascorbic acid, sodium-L-ascorbate, magnesium-L-ascorbate, calcium-L-ascorbate and ferrous-L-ascorbate were performed in the (288.15 to 323.15) K temperature range. The limiting molar conductances of the ascorbic anion, λ^∘(HAsc⁻, T), and the dissociation constants of ascorbic acid, K(T), were derived by the use of the Debye-Hückel equation for the activity coefficients and the Onsager and Quint and Viallard conductivity equations.     

Electrical Conductance and Volumetric Studies in Aqueous Solutions of DL-Pyroglutamic Acid

Conductivity measurements of DL-pyroglutamic acid and sodium pyroglutamate in dilute aqueous solutions were performed in the 288.15–323.15 K temperature range. The limiting molar conductances of pyroglutamate anion, λ^o(pGlu⁻, T) and the dissociation constants of pyroglutamic acid, K(T) were derived from the Onsager, and the Quint and Viallard conductivity equations. Densities of aqueous solutions with molalities lower than 0.5 mol-kg⁻¹ were determined at 5 K intervals from T = 288.15 K to 333.15 K. Densities served to evaluate the apparent molar volumes, V_2,φ(m, T), the cubic expansion coefficients, α (m,T) and the changes of the isobaric heat capacities with respect to pressure, (∂ C_P/∂ P)_T,m. They were correlated qualitatively with the changes in the structure of water when pyroglumatic acid is dissolved in it.     

Electrical Conductance and Volumetric Studies in Aqueous Solutions of Nicotinic Acid

Conductivity measurements of nicotinic acid and sodium nicotinate in dilute aqueous solutions were performed in the (288.15 to 323.15) K temperature range. The limiting equivalent conductances of the nicotinate anion, λ⁰(Nic⁻, T), and the dissociation constants of nicotinic acid, K(T), were derived by the use of the Onsager and the Quint and Viallard conductivity equations. Densities of aqueous solutions with molalities lower than 0.2 mol-kg⁻¹ were determined at 5 K temperature intervals, from T = (288.15 to 333.15) K. The measured densities were used to evaluate the apparent molar volumes, V_{2, φ}(m, T), the cubic expansion coefficients, α(m, T), and the changes of isobaric heat capacities with respect to pressure, (∂C_P/∂p)_{T, m}. They were qualitatively correlated with the changes in the structure of water when nicotinic acid is dissolved in it.     

Chemical and Physical Solutions for Hydrogen Storage

Hydrogen is a promising energy carrier in future energy systems. However, storage of hydrogen is a substantial challenge, especially for applications in vehicles with fuel cells that use proton‐exchange membranes (PEMs). Different methods for hydrogen storage are discussed, including high‐pressure and cryogenic‐liquid storage, adsorptive storage on high‐surface‐area adsorbents, chemical storage in metal hydrides and complex hydrides, and storage in boranes. For the latter chemical solutions, reversible options and hydrolytic release of hydrogen with off‐board regeneration are both possible. Reforming of liquid hydrogen‐containing compounds is also a possible means of hydrogen generation. The advantages and disadvantages of the different systems are compared.     

Raman Study of the Pulsed Discharge Effect on Molecular Relaxation in Aqueous Sodium Nitrate

The high-voltage pulsed electric discharge effect (HPED activation) on the Raman spectra of a saturated aqueous solution of sodium nitrate (NaNO₃/H₂O) in the region of the totally symmetric vibration ₁(A) of the NO _- ³ anion has been studied. The temperature dependences of the width and frequency of the corresponding spectral line are examined.     

Radiolytic Gas Formation in Dilute Oxalic Acid Aqueous Solutions

The radiolytic gas formation in aqueous oxalic acid solutions was studied. The concentrations of ₂ and ₂, the gas phase constituents, were measured. It was found that gas evolution is mainly due to the degradation of both oxalic acid and its radiolysis products.     

Production of SiC Nanoparticles in Carbon Network by Pulsed Electrical Discharges in Liquid Hexamethyldisilazane with Gaseous Bubbles

Plasma Chemistry and Plasma Processing - Discharges in liquid can efficiently produce nanoparticles via electrode erosion and (or) liquid decomposition. Although in-liquid spark discharges promote...     

Electrical Conductivity and Complexation of Sodium Borate in Trehalose and Sucrose Aqueous Solutions

The formation equilibrium constants for the esterification reaction between sucrose or trehalose and borate ion have been determined by measuring the pH changes produced when the corresponding sugar is added to sodium borate solutions. The speciation of the ternary sugar–borate–water system was calculated from this equilibrium information and used to separate the contribution of each ionic species to the electrical conductivity of the system. From the analysis of the results it is concluded that, in the viscosity region studied, the complex borate–trehalose and borate–sucrose ions obey Walden's rule, while the behavior of the smaller borate ion is not clear. The dramatic difference of the infinite dilution molar conductivity, and consequently of the hydrodynamic radius, of the trehalose– and sucrose–borate ester ions is ascribed to the formation of an intramolecular diester in aqueous trehalose.     

Characteristics of the Single-Gap Pseudospark Discharge Under Nanosecond Pulsed Voltages

In this paper, a single-gap pseudospark discharge chamber was built and tested with several electrode gap distances and pressures to explore the characteristics of the pseudospark under nanosecond pulsed voltages. Experimental results show that with the development of the discharge, anode plasma firstly forms near the anode, and then moves towards the cathode. The ionization initial voltage decreases with the increase of the electrode gap distance and pressure in our pseudospark discharge configuration. By analysing the emission spectra, it is concluded that the major emission spectra are composed of the second positive bands, and the electron energy of the plasma is in the level of several tens of electron volts. The mechanism of how the pressure and gap distance influence the characteristics has been discussed with the simulation of the collision ionization process using the Monte Carlo Collision method. Based on the simulation and experimental results, it is inferred that the breakdown voltages is decided by the ionization process of the electron with the neutral gas in the main gap, and a possible reason is put forward to explain the reason that U is a function of p ² d.     

凝聚液态水溶液中的化学反应

液态水是进行化学反应的最重要介质与溶剂之一,也是研究在凝聚(液)态中进行化学反应的主要对象。在不同的外界条件下(特别是极端条件下),液态水的组成、结构与性能会发生很大的变化,促使在其中进行的化学反应呈现不同的特点,因而形成了温和条件下、水热条件下(Hydrothermal condition)与超临界水热条件下(Supercritical water codition)三大类型反应的凝聚态化学。本文立足凝聚态,讨论了在温和(一般)条件下,液态水与水溶液的组成、结构与性能对发生于其中的化学反应(包括溶解与结晶反应、盐类复分解反应、酸碱反应、沉淀反应、成胶与晶化反应、水解反应、氧化-还原反应以及配位化学反应)的影响,包括对反应物存在状态与化学活性,化学反应的过程与机理,反应的中间与最后产物的组成、结构等造成的影响,以及产生的结果与规律等有关的反应化学。通过这些讨论我们提出应从凝聚态的角度看待发生于液态水溶液中的化学反应,并希望这种新视角对研究在其他类型液体(诸如有机溶剂、离子液体、分子熔体等)中进行的化学反应时有所帮助,同时能加强彼此间的交流、讨论与批判,协力为推动以液态为主要研究对象的凝聚态化学的研究与学科建设提供有益的基础。     

Characteristics of Aqueous Solutions of Methyl Cellulose-Polymethacrylamidoglucose Mixtures

The characteristics of dilute (0.1%) and moderately concentrated (2%) aqueous solutions of methyl cellulose, polymethacrylamidoglucose, and their blends, and also the composition of films based on them were studied by viscosimetry, rheology, and IR spectroscopy. The effect of the mixture composition on the conditions of gel formation in methyl cellulose solutions was studied.     

The CO2 Reforming of Natural Gas in a Pulsed Corona Discharge Reactor

The conversion of CO ₂ and (CH ₄+CO ₂ ) mixtures to CO, at room temperature and atmospheric pressure conditions, in pulsed corona discharges, was investigated. Conversion of pure CO ₂ was 16.8% at 10 cm ³ -min ^–1 flow rate, which corresponds to 75 mol-min ^–1 rate of conversion. The CO ₂ conversion was improved to 38% (85 mol-min ^–1 by feeding the reactor with CH ₄+CO ₂ gas mixture (1:1 ratio), simultaneously with CH ₄ conversion of 46% (102.7 mol-min ^–1 ) at 10 cm ³ -min ^–1 flow rate of feed gases and 9 W power conditions. Rate of CO production is increased from 110 to 180 mol-min ^–1 with the variation of feed gas (CH ₄+CO ₂ mixture, 1:1 ratio) flow rate from 10 to 40 cm ³ -min ^–1 at 9W, which corresponds to energy efficiency of 2.5 to 4.1%. Highest energy yield of 25 g/kWh for CH ₄ conversion, 29 g/kWh for CO ₂ conversion, and 33 g/kWh for CO production were achieved.     

Structural Characteristics of Hydrated Complexes of Aminoacids in Aqueous Solutions

Aqueous solutions of nine α-aminoacids were studied in a diluted range of concentrations (from 0. 01 m to 0.1 m) at 5°C, 15°C, 25°C, 35°C, and 45°C based on the model that uses molar adiabatic compressibility (β _s V _m ) as a measure of hydration of the solute. For the resulting hydrated complexes of aminoacids, structural characteristics have been determined. At increased concentrations of the acid, variation of its hydration number is the chief factor affecting the molar compressibility of the hydrated complex.Original Russian Text Copyright © 2004 by V. N. Afanasiev, E. Yu. Tyunina, and V. V. Ryabova__________Translated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 5, pp. 883–888, September–October, 2004.     

An Experimental Investigation of the Liquid Flow Induced by a Pulsed Electrical Discharge Plasma

In this work, particle image velocimetry has been used to visualize and quantify plasma-induced flow fields in liquid water. Experiments were performed in a rod-plane plasma reactor with a thin wire electrode suspended above the surface of the liquid in argon gas and a grounded plate immersed in the liquid. The velocity field has been quantified for two types of solutions: (1) aqueous NaCl solutions of varying solution conductivities and discharge frequencies and (2) aqueous NaCl solutions containing varying concentrations of the following four organic compounds: rhodamine B dye, caffeine, fluoxetine, and perfluorooctanoic acid. Results show that in neat water and aqueous caffeine solutions, the liquid is “pulled” along by the interaction of the gas molecules with the liquid molecules at the free surface and thus the direction of the liquid flow is in the direction of the gas phase flow (i.e., away from the discharge location). However, the flow was reversed (i.e., towards the discharge) for those solutions with strong surfactants such as perfluorooctanoic acid. The magnitude of the reversal depended on the initial concentration of the compound and for some compounds as time progressed the reversed flow pattern weakened and then reverted to a normal flow pattern. To determine the most likely cause of these flow reversals, a simple numerical model of the velocity field was developed to estimate relative contributions of various flow inducing mechanisms. The model indicates that in the presence of surfactants, Marangoni stresses are responsible for inducing the flow in the liquid.     

Color Characteristics of Aqueous Solutions of Synthetic Food Dyes

The color characteristics of aqueous solutions of synthetic food dyes Azo Rubine, tartrazine, Indigo Carmine, Ponceau 4R, Sunset Yellow, and Brilliant Blue were studied. A formula is proposed for determining the hue of dye solutions.