Quantification of the Ozone Dose Delivered into a Liquid by Indirect Plasma Treatments: Method and Calibration of the Pittsburgh Green Fluorescence Probe

Determination of the ozone dose delivered into liquids by plasma systems is of importance in many emerging plasma applications, such as plasma medicine. Quantification of this dose remains extremely challenging due to the complex physico-chemical processes encountered in the gas plasma, the plasma–liquid interface and the liquid itself. Chemical probes have the potential to address the limitation of more traditional plasma diagnostic techniques but most commercial chemical probes are not specific enough to be used in plasma applications. Here we report on the development of a method for the quantification of the ozone delivered into a liquid using Pittsburgh Green, a novel ozone-selective fluorescence probe. Entailed within this work is a method for the preparation of the probe solutions, the design of a calibration system and a normalized calibration curve correlating fluorescence intensity to actual ozone dose delivered to the liquid. This enables the quantitative comparison of ozone measurements performed with different spectrofluorometers and in different institutions.     

Hydrogen Peroxide Production in an Atmospheric Pressure RF Glow Discharge: Comparison of Models and Experiments

The production of \(\hbox {H}_2\hbox {O}_2\) in an atmospheric pressure RF glow discharge in helium-water vapor mixtures has been investigated as a function of plasma dissipated power, water concentration, gas flow (residence time) and power modulation of the plasma. \(\hbox {H}_2\hbox {O}_2\) concentrations up to 8 ppm in the gas phase and a maximum energy efficiency of 0.12 g/kWh are found. The experimental results are compared with a previously reported global chemical kinetics model and a one dimensional (1D) fluid model to investigate the chemical processes involved in \(\hbox {H}_2\hbox {O}_2\) production. An analytical balance of the main production and destruction mechanisms of \(\hbox {H}_2\hbox {O}_2\) is made which is refined by a comparison of the experimental data with a previously published global kinetic model and a 1D fluid model. In addition, the experiments are used to validate and refine the computational models. Accuracies of both model and experiment are discussed.     

(S,S)-(+)-Pseudoephedrine as chiral auxiliary in asymmetric conjugate addition and tandem conjugate addition/alpha-alkylation reactions

Organolithium reagents undergo highly regio- and diastereoselective 1,4-addition to (S,S)-(+)-pseudoephedrine enamides furnishing the corresponding beta-alkyl-substituted adducts in excellent yields and diastereoselectivities. In addition, the intermediate lithium enolates generated after the conjugate addition step undergo a highly diastereoselective alkylation reaction, furnishing alpha,beta-dialkyl-substituted amides in high yields. The obtained adducts have been converted into chiral nonracemic beta-alkyl- and alpha,beta-dialkyl-substituted carboxylic acids and gamma-alkyl- and beta,gamma-dialkyl-substituted alcohols using very simple and high-yielding procedures.     

Tandem asymmetric conjugate addition/alpha-alkylation using (S,S)-(+)-pseudoephedrine as chiral auxiliary

Alpha,beta-unsaturated amides derived from the chiral amino alcohol (S,S)-(+)-pseudoephedrine undergo a very clean and diastereoselective tandem conjugate addition/alpha-alkylation reaction. Excellent results have been achieved using a wide range of differently substituted conjugate acceptors, organolithium reagents, and alkyl halides. The chiral auxiliary could be easily removed from the obtained adducts by reduction, furnishing chiral nonracemic alpha,beta-branched alcohols in a very easy and efficient way. [reaction: see text]     

Excitation frequency effects on atmospheric-pressure helium RF microplasmas: plasma density,electron energy and plasma impedance

The effects of the driving RF frequency on the properties of low temperature atmospheric pressure helium microplasmas are discussed in light of simulation results of a 500 μm microdischarge driven at constant input power with a 10 MHz–2.45 GHz voltage source. The electron density is found to be a non-monotonic function of the driving frequency and agrees with experimental observations made in different frequency bands with different devices. The physics underpinning this non-monotonic behaviour are investigated and the increasing penetration of the electric field as frequency increases is identified as a key factor. Additionally, the relationship between the plasma impedance and the mean plasma density is studied, and the validity and accuracy of equations commonly used to infer the plasma density from experimental impedance measurements discussed. While this method can provide quantitative estimations, the accuracy suffers when the discharge operates in the γ-mode or when the displacement current across the bulk plasma is not negligible.     

Characterisation of a 3 nanosecond pulsed atmospheric pressure argon microplasma

This study details the generation and characterisation of a 3 nanosecond pulsed atmospheric pressure argon microdischarge, and provides a comparison with a comparable DC microplasma. There is a growing interest in short pulsed excitation of microplasmas as a gateway to access highly non-equilibrium discharge chemistry that is inaccessible using other excitation mechanisms. By combining time-resolved electrical and optical diagnostics the repetitive 3 nanosecond pulses considered in this study are shown to produce a highly transient plasma with a peak dissipated power above 160 kW and electron densities in excess of 10¹⁷ cm^-3. During the afterglow period electrons rapidly cool below the excitation threshold suggesting emission from excited argon neutrals should also diminish rapidly. However, argon emissions are observed for several microseconds after each applied pulse, far in excess of their radiative lifetimes. Potential repopulation mechanisms are considered and it is concluded that electron-ion recombination is the most likely repopulation process.     

Theory of free-electron optical absorption in n-GaAs

Free-electron optical absorption of Se-doped GaAs at room temperature is calculated and compared with existing experimental data. In addition to the standard features the theory takes into account a non-parabolic character of the conduction band, a short-range component of the Se donor potential and a plasmon generation in the presence of donors. Deformation potential constants for the conduction and the valence bands are calculated using the empirical pseudopotential method. A value of C = -15.7 eV is obtained for the conduction band and shown to agree with existing hydrostatic and uniaxial stress experiments. Assuming no impurity compensation and using no adjustable parameters we successfully describe the experimental free-electron absorption in GaAs as a function of photon wavelength for samples with various donor densities.     

Electron kinetics in radio-frequency atmospheric-pressure microplasmas

The kinetic study of three radio-frequency atmospheric-pressure helium microdischarges indicates that the electron energy probability function is far from equilibrium, and three electron groups with three distinct temperatures are identified. The relative population of electrons in different energy regions is strongly time modulated and differs significantly from values recently reported from fluid analyses. It is also shown that a flux of energetic electrons (epsilon>5 eV) that comprises up to 50% of the total electron flux can reach the electrodes. This energetic electron flux provides a new means of delivering energy to the electrodes and tuning the surface chemistry in atmospheric-pressure discharges. The three electron groups and the engineering of an energetic electron flux might open up a new paradigm in plasma-surface chemistry that has not been considered up until now.     

Electronic sputtering produced by fission fragments on condensed CO and CO2

Condensed CO and CO2 are bombarded by approximately 65 MeV 252Cf fission fragments and the desorbed ions are analyzed by time-of-flight mass spectrometry as a function of target temperature, in the ranges 25-33 K and 75-91 K, respectively. Absolute desorption yields are measured up to complete ice sublimation. The mass spectra of both ice targets reveal the emission of: (1) low mass ions, produced by direct Coulomb interaction of the highly charged projectiles and delta-electrons with CO and CO2, and (2) pronounced series of cluster ions. The basic ice cluster structures (CO)n and (CO2)n are present in the emitted cluster series such as (CO)nCO+, (CO2)nCO2+, or (CO2)nCO3-. In the case of CO ice, however, the intense production of the series Cn+, Cn-, and (CO)mCn+ shows that Cn is the main cluster structure, consequence of a higher concentration of free carbon atoms in the nuclear track plasma of CO ice than in that of CO2 ice. Ion cluster abundance is observed to decrease exponentially with cluster mass. The decay constant is k(n) congruent with 0.13, about the same for series based on (CO)n and (CO2)n, but a factor 3.3 higher for the Cn series. The Cn clusters are formed by gas-phase condensation, but the (CO)n and (CO2)n clusters are produced by fracturing of the highly excited solid around the nuclear track. A dramatic reduction of the ion desorption yield is observed near T = 29 K for CO and near T = 85 K for CO2, when fast sublimation occurs and ice thickness vanishes. Close to sublimation temperature, the decay constant of the (CO)2Cn+ series increases due to a decreasing formation probability of large Cn clusters.