The effect of CCl2F2 on ozone generation from oxygen

The production of ozone by negative corona discharge from O₂ + CCl₂F₂ (CFC12) mixtures is experimentally investigated at two pressures of gaseous mixture of 800 and 900 mbar in the CCl₂F₂ concentration range of (0–7)%. The efficiency of ozone generation is remarkably reduced with increasing content of CCl₂F₂ in the mixture with oxygen. The effect is more apparent at lower pressure of gaseous mixture. In order to identify the most likely process responsible for the inhibition of ozone production a discussion of the chemical kinetics of various processes is presented. This research was carried out with financial support from the Slovak Grant Agency for the project under the No. 1/5184/98 and the Action Austria-Slovakia project under the number 25s19.     

Relaxing Phenomena in Negative Corona Discharge: New Aspects

Two theories, explaining the time dependence of the negative corona discharge current in air, are confronted with new experimental results. The influence of the ozone concentration on the discharge current was experimentally confirmed in dry air and in mixtures of nitrogen with oxygen. Assuming that only the dissociative electron attachment to ozone molecule is a process being responsible for a reduction of the electron component in the total mean discharge current, the mean value of the electron attachment rate constant k = (3 - 5.5) × 10^?9 cm^?3 s^?1 was derived from the measured dependence of the discharge current on the ozone concentration. The calculated value of the rate constant k corresponds to the dissociative attachment of electron to ozone molecule via process e + O₃ → products (O^? or O^?₂ negative ions).     

Experimental investigations and modelling studies of ozone producing corona discharges

The ozone generation by negative corona discharge in coaxial cylindrical system of electrodes have been studied experimentally in Ar+O₂ and N₂+O₂ mixtures. Both in argon and nitrogen mixtures with oxygen the monotonous decrease in ozone concentration [O₃] was observed at decreasing oxygen content in mixtures and the constant input energy density η. The rate coefficients for the ozone generation and ozone decomposition were obtained by fitting experimentally measured data [O₃]=f(η) with Vasiljev-Eremin formula. The calculated rate coefficient for ozone generation in N₂+O₂ mixtures at low content of oxygen (below 20%) was found considerably higher than that in Ar+O₂ mixtures. Increase in the rate coefficients for ozone generation and decomposition was observed with decreasing content of oxygen in both mixtures. The experimental results are in qualitative agreement with the simple model incorporating five main chemical processes in mechanism of ozone generation. The research was partially supported by Slovak Grant Agency under project 1/765920 The UK EPSRC (Grant GM/98944) and NATO Joint Project PST CLG 976544.     

The dependence of ozone generation efficiency in silent discharge on a width of a discharge gap

The generation of ozone was studied experimentally in silent discharge on oxygen and air under the atmospheric pressure. The concentration of ozone was detected by means of UV absorption. It is shown that we must recount the charge (Q _T) transferred in outer circuit to the charge (Q _s) transferred in the discharge gap to establish the energetic load of ozone generation w[gO₃/Wh]. The width 0.8–1.1 mm of discharge gap was determined as optimal for ozone generation.     

Zur O2-Dissoziation in der Gleichstromglimmentladung. Teil I Bestimmung des Dissoziationsgrades mittels der O3-Bildung an gekühlten Oberflächen

The synthesis of ozone on the surface S cooled with liquid nitrogen O + O₂·S→O₃·S[1] was used to measure the concentration of atoms in a flow tube downstream of a d.c. discharge. The flow tube was constructed in the form of a U-tube. The ozone was deposited as a blue liquid film in the neighbourhood of the surface of the liquid nitrogen on the walls of the part of the U-tube, which was connected with the discharge tube. The oxygen atom decay in the U-tube was observed by measuring the production of ozone as the distance between the discharge tube (diameter: 5,2 cm) and the surface of the liquid nitrogen was varied. The decay is first order in atom concentration for the pressures p > 1 torr. But for the pressures below p = 1 torr near by the discharge tube we observed deviations from the law of decay In [O]₀/[O] = k·t for the currents of about i = 100 mA. This effect was attributed to the process From the extrapolation of an ozone production curve atom concentrations in the discharge have been obtained. The transition from the ?H”? form to the ?T”? form (striated, low average electric field) of the discharge [2] caused the dissociation to decrease rapidly. The highest dissociation (10%) was obtained in the ?H”? form at high currents (i = 120 mA) and low pressures (p = 0,60 torr). The yield of atomic oxygen per kilowatt hour of energy was measured as functions of pressure and gas flow rate for i = 100 mA and i = 50 mA.     

Effect of catalysts on dc corona discharge poisoning

The processes of ozone generation in non-thermal plasma produced by an electrical discharge in air at atmospheric pressure are burdened by the presence of nitrogen oxides, which on the one hand contribute to ozone generation and on the other hand are responsible for unpleasant discharge poisoning. The term discharge poisoning refers to the situation when the discharge ozone formation completely breaks down. Discharge poisoning can be affected by placing a catalyst in the discharge chamber. For the dc hollow needle to mesh corona discharge enhanced by the flow of air through the needle electrode we studied the effect of titanium dioxide TiO₂, ZSM-5 zeolite or Cu⁺⁺ZSM-5 zeolite on discharge poisoning by monitoring the ozone, nitrogen monoxide and nitrogen dioxide discharge production. We found that placing globules of any of these catalysts on the mesh decreases the energy density of the onset of discharge poisoning, and this energy density is smallest for a discharge with globules of a TiO₂ on the mesh.     

DasK-Röntgenemissionsspektrum des Chlors in freien Molekülen

TheKα andKβ spectra of chlorine in free molecules were studied using a special fluorescence X-ray tube and a high resolving curved crystal spectrograph with photoelectric registration. It was found that the wavelength shifts of ClKα₁ obtained for various gaseous compounds do not show the regularities observed with solid compounds of other 3rd period elements. — TheKβ spectrum consists of discrete lines the most intense of which result from transitions of the lonely pair electrons of the chlorine atoms. The spectra of HCl, Cl₂ and CH₃Cl can be explained using optical and betaspectroscopical data and MO calculations. The general structure of ClKβ of organic compounds seems to be determined by the hybridisation type of the carbon atoms bound to the chlorine atoms. Evidence is found for a contribution of molecular vibrational energy to the energies of the X-ray transitions.     

The submillimeter-wave spectrum of the chloromethyl radical, CH2Cl, in the ground vibronic state

We have extended the measurement of submillimeter wave transitions of CH₂Cl between 418 and 470 GHz for the two isotopic species of Cl. The radical was produced in a fast flow system by hydrogen abstraction of CH₃Cl by Cl atoms obtained from a 2450 MHz microwave discharge in Cl₂ diluted with helium. A global least-squares analysis including the previous and the newly observed transitions led to a more precise set of rotational, fine and hyperfine constants for the two isotopomers in their ground vibronic state. In addition, we have also observed CH₂Cl by the 248 nm photolysis of CH₂BrCl, leading to a single 1/e lifetime of 146 ms.     

Chemical oxygen-iodine laser with external production of iodine atoms in CH3I/Ar dc glow discharge

A cw chemical oxygen-iodine laser (COIL) operating in a subsonic mode with a high water content of ～15% and external production of iodine atoms in CH₃I/Ar dc glow discharge has been demonstrated. A straightforward comparison of COIL performance for two cases—conventional, when I₂ was injected in the singlet oxygen flow, and when iodine atoms produced externally together with other discharge products were injected—was made. In the latter case nearly four times increase in output power was observed, suggesting that the relaxation of the energy stored in the singlet oxygen slowed down substantially, when the laser operated using CH₃I/Ar discharge products instead of iodine molecules.     

Reaction Kinetics and Chemical Quasi-Equilibria of the Ozone Synthesis in Oxygen DC Discharges

The spatial distribution of ozone and of oxygen atoms was studied along the active and the passive zone of a dc discharge (positive column, pressure: p = (4 … 10) · 10² Pa, current: I = 2 … 50 mA, flow rate: F = 5 … 100 sccm) in flowing oxygen. The composition of the final output O₂/O₃-mixture is controlled by relaxation processes in the passive reactor zone. It is affected sensitively by the total number density and the gas temperature in the afterglow. Steady states meaning reversible chemical quasi-equilibria were observed and analysed extensively. Within a detailed kinetic model the formation of these equilibria can be explained quantitatively. The synthesis to ozone is controlled above all by the metastable O₂ (a¹Δg) species, which modify drastically the results for the basic mechanism, considering the O atoms in the ³P and ¹D states.     

含氧等离子体中臭氧形成过程数值模拟

利用数值模拟程序对不同条件下氧等离子体和大气等离子体中臭氧的形成过程进行数值模拟. 结果发现：臭氧的形成与游离态氧原子密切相关;臭氧的最大数密度与初始电子数密度有关;臭氧最大数密度持续的时间与脉冲放电大气等离子体中放电间隔时间选取相关,最佳的放电间隔是游离态氧原子达到最大的时间. 关键词： 等离子体 数值模拟 臭氧产生     

The quenching of Pb(6p 2 1 D 2) atoms in collisions with molecules

The collisions of metastable Pb(6p ^{2 1} D ₂) atoms with various molecules were studied by the diagnostics of radiation from a hollow cathode lamp and a laser on lead vapor. Experiments were performed for a gas flow of lead atoms with argon. The Pb(6p ^{2 1} D ₂) states were excited in a gas discharge in the presence of reagent gas molecules. The absolute rate constants for the quenching and chemical reactions of lead atoms in the ground and excited states were determined. The quantum efficiency of chemical reactions was close to one for the N₂O, CH₂Cl₂, SF₆, and CuBr molecules. Long-lived chemical compounds were formed in these reactions.     

Infrared absorption of iodomethylperoxy (syn-ICH2OO) radical generated upon photolysis of CH2I2 and O2 in solid para-H2

Irradiation of a para-hydrogen (p-H₂) matrix containing diiodomethane (CH₂I₂) and O₂ at 3.2 K with light at 280 ± 20 nm, followed by annealing of the matrix at 4.0 K, yielded infrared (IR) absorption lines at 2982.4, 1408.9, 1231.8, 1226.5/1225.6, 1085.6, 917.7, 841.6/841.1, 550.5, and 490.2 cm^?1 that are assigned to the syn-iodomethylperoxy (syn-ICH₂OO) radical. Further irradiation of the matrix at 365 nm diminished these features. Experiments with CH₂I₂ and ¹⁸O₂ yielded lines of syn-ICH₂¹⁸O¹⁸O at 1407.3, 1228.1/1227.7, 1217.7/1217.0, 1031.5, 899.9/899.4, 836.7/836.0, and 473.6 cm^?1. The assignments are based on the photolytic behaviour and comparisons of observed vibrational wavenumbers, IR intensities, and ¹⁸O-isotopic shifts with those predicted with the B3LYP/aug-cc-pVTZ-pp method. The observation is consistent with a mechanism that, upon photolysis of CH₂I₂ at 280 nm, CH₂I was formed and subsequently reacted with O₂ to yield syn-ICH₂OO. Compared with the gaseous reaction CH₂I + O₂ → CH₂OO + I at low pressure, observation of ICH₂OO in a p-H₂ matrix instead of CH₂OO in the gaseous phase indicates that the excess energy of internally excited ICH₂OO, produced upon reaction of CH₂I + O₂, was rapidly quenched in the matrix so that ICH₂OO became readily stabilised without further decomposition to form CH₂OO + I.     

Crucial role of the magnetic field in the evolution of life

The formation of a steady ozone layer in the earth’s atmosphere is the most significant event in the evolutionary cycle of the earth which, in turn, has been responsible for the development of life with an oxygen metabolism. In addition to protecting biological life from exposure to ultraviolet radiation the ozone layer has also been responsible for maintaining the water and oxygen balance in the atmosphere. It is argued that the magnetic field of the earth is really responsible for the formation of this steady ozone layer in the earth’s atmosphere. Because of the earth’s magnetic field and associated trapped charge particle belts and the magnetosphere, the earth’s atmosphere does not directly interact with the interplanetary space. Without such a shielding, the free oxygen atoms could have been depleted considerably causing a severe depletion in the ozone concentration to start with. The impact of charged particles from galactic and solar cosmic rays over the entire earth’s atmosphere and the consequent production of NO _x would have given rise to a major ozone sink, if earth were devoid of a magnetic field. The net result would have been the absence of a steady ozone layer and the absence of life with an oxygen metabolism, as in the case of the atmospheres of Venus and Mars, if the earth did not have a magnetic field.     

Investigation of the ozone formation process in a nanosecond microwave discharge in air and oxygen

Results are presented from an investigation of the dynamics of ozone formation in a freely localized discharge generated by a periodic train of 3-cm nanostructured microwave pulses in oxygen and air at a pressure p=3–30 Torr. Conditions for the efficient generation of ozone in air with the minimum production of nitrogen oxides are demonstrated experimentally. It is shown that when the microwave pulse repetition frequency is high, heating of the gas and the buildup of nitrogen oxides in the discharge in air reduce the ozone formation efficiency while under prolonged exposure the ozone formed initially is destroyed. The energy cost of forming ozone in oxygen and air is determined as a function of the microwave pulse length and repetition frequency and the gas pressure. The lowest energy cost of forming a single ozone molecule in these experiments is 16 eV per molecule for a discharge in air and 4 eV per molecule in oxygen. It was observed that circulating the gas through the discharge zone enhances th ozone formation efficiency. It is shown that there are optimal conditions for ozone formation as a function of the reduced electric field in the plasma. Zh. Tekh. Fiz. 67, 9–18 (March 1997)     

Geometric shielding corrections for total cross section calculations of electron scattering by CH4, C2H6, C2H3F3, C2H4, C2F4, C2Cl4 and C2Cl2F2 from 30–5000?eV

To quantify the changes in the geometric shielding effect in a molecule as the incident electron energy varies, an empirical fraction, which represents the total cross section contributions of shielded atoms in a molecule at different energies, is presented. Using this empirical fraction, the total cross sections for electron scattering by CH₄, C₂H₆, C₂H₃F₃, C₂H₄, C₂F₄, C₂Cl₄ and C₂Cl₂F₂ are calculated over a wide energy range from 30 to 5000 eV by the additivity rule model at the Hartree-Fock level. The quantitative total cross sections are compared with those obtained by experiment and other theories where available. Good agreement is attained above 100 eV.     

Energetic Characteristics of Oxygen Plasma

A low-temperature oxygen plasma is studied using the thermocouple, probe and spectral method in the range of 2–8 Torr pressure, 30–100 mA discharge currents, 0, 5, 10 m/s pumping velocity. The gas temperature, concentrations of electrons and oxygen atoms in the 3 p⁵P state, and the longitudinal electric field are measured. Radial distributions of gas temperature and electron concentration are obtained. Ranges of pressures and currents are found in which considerable increases in electric field, discharge voltage, temperatures of gas and electrons are observed at pumping switched on. An estimate of the rate constant of the steplike ionization through the O₂(a¹Δg) state is given. The concentration of atomic oxygen in the ground state and excitation constant of the triplet O(3p⁵P) by electron impact are obtained from the solution of the balance equations and our experimental data.     

Effect of ozone addition and ozonolysis reaction on the detonation properties of C2H4/O2/Ar mixtures

Ozone is one of the strongest oxidizers and can be used to enhance detonation. Detonation enhancement by ozone addition is usually attributed to the ozone decomposition reaction which produces reactive atomic oxygen and thereby accelerates the chain branching reaction. Recently, ozonolysis reaction has been found to be another mechanism to enhance combustion for unsaturated hydrocarbons at low temperatures. In this study, the effects of ozone addition and ozonolysis reaction on steady detonation structure and transient detonation initiation and propagation processes in C₂H₄/O₂/O₃/Ar mixtures are examined through simulations considering detailed chemistry. Specifically, the homogeneous ignition process, the ZND detonation structure, the transient direct detonation initiation, and pulsating instability of one-dimensional detonation propagation are investigated. It is found that the homogenous ignition process consists of two stages and the first stage is caused by ozonolysis reactions which consume O₃ and produces CH₂O as well as H and OH radicals. The ozonolysis reaction and ozone decomposition reaction can both reduce the induction length though they have little influence on the Chapman–Jouguet (CJ) detonation speed. The supercritical, critical and subcritical regimes for direct detonation initiation are identified by continuously decreasing the initiation energy or changing the amount of ozone addition. It is found that direct detonation initiation becomes easier at larger amount of ozone addition and/or larger reaction progress variable. This is interpreted based on the change of the induction length of the ZND detonation structure. Furthermore, it is demonstrated that the ozonolysis reaction can reduce pulsating instability and make the one-dimensional detonation propagation more stable. This is mainly due to the reduction in activation energy caused by ozone addition and/or ozonolysis reaction. This work shows that both ozone decomposition reaction and ozonolysis reaction can enhance detonation for unsaturated hydrocarbon fuels.     

约化场强对氮-氧混合气放电等离子体演化特性的影响

采用零维等离子体动力学模型,计算了不同约化场强条件下N₂/O₂放电等离子体的演化特性.结果表明,平均电子能量与约化场强有着近似的线性关系,在约化场强为100 Td时,平均电子能量约为2.6 eV、最大电子能量达35 eV;约化场强是影响电子能量函数分布的主要因素.气体放电过程结束后,振动激发态氮分子的粒子数浓度不再变化,电子激发态的氮分子、原子和氧原子的粒子数浓度达到一峰值后开始降低;放电结束后的氧原子通过复合反应生成臭氧.约化场强升高,由于低能电子减少的影响,振动激发态氮分子的粒子数浓度降低,当约化场强由50 Td增加75 Td,100 Td时,粒子数浓度由3.83×10¹¹ cm^-3降至1.98×10¹¹ cm^-3和1.77×10¹¹ cm^-3,其他粒子浓度则相应增大. 关键词： 等离子体 约化场强 粒子演化 数值模拟     

Atomic charges of Cl− ions confined in a model Escherichia coli ClC−Cl−/H+ ion exchanger: a density functional theory study

We present extensive semi-empirical and pseudo-potential density functional theory calculations dedicated to analyse the stability, charge density distribution and migration behaviour of Cl^? ions confined in model Escherichia coli (ec) ClC?Cl^?/H⁺ ion-exchangers. Following recent high-resolution crystal structure determination in these kinds of systems, we use a finite-cluster model approach and construct various chemically simplified pore structures made of a glutamate residue ?CH₂?CH₂?COO^? (E148) and its closets 15, 19, 23 and 26 amino acids into which the Cl^? ions will be confined. We reveal the sequence of molecular rearrangements induced on the E148 chain, which blocks the middle of the conduction pathway, leading to the pore opening. The ?CH₂?CH₂?COO^? fragment shows notable variations in its average charge density for small changes in the intra-cellular environment varying from ?0.4e to ?0.3e to ?0.1e in the presence of zero, one and two confined Cl^? ions, respectively, a result that reveals an interesting functionality of the E148 chain during Cl^? conduction. We also obtain complex fluctuations in the ionic charge of the confined Cl^? ions varying from ～?0.7e to ?0.2e, which deviate significantly from the value (?1e) usually used in classical simulations. By attaching a single H species to one of the oxygens of the glutamate group, we obtain that the ?CH₂?CH₂?COOH fragment has now a small effective charge of ～+0.25e. The energy barriers opposing the exit of the Cl^? ions from our considered ion-exchangers vary from 0.65 eV to 4.7 eV, the smallest values being obtained for model structures exhibiting a high degree of flexibility and having protonated E148 fragments. Our results reinforce previous findings and provide additional physical insight, at the atomic level, on the gating process. Finally, we underline the importance of using electronically polarisable force fields to describe the transport of anionic species through this kind of molecular constrictions.