Plasmas: reaction rates

The high density plasma reaction rate of BCI3 with anodized aluminum or high purity alumina at different flow is shown in Fig. 6. The high reaction rate occurs on chamber top window due to both high density plasma and gas flow. On the chamber wall, the reaction... 

In practical applications, gas-surface etching reactions are carried out in plasma reactors over the approximate pressure range 10 -1 Torr, and deposition reactions are carried out by molecular beam epitaxy (MBE) in ultrahigh vacuum (UHV below 10 Torr) or by chemical vapour deposition (CVD) in the approximate range 10 -10 Torr. These applied processes can be quite complex, and key individual reaction rate constants are needed as input for modelling and simulation studies—and ultimately for optimization—of the overall processes. 

Ton-molecule reactions are of great interest and importance in all areas of kinetics where ions are involved in the chemistry of the system. Astrophysics, aeronomy, plasmas, and radiation chemistry are examples of such systems in which ion chemistry plays a dominant role. Mass spectrometry provides the technique of choice for studying ion-neutral reactions, and the phenomena of ion-molecule reactions are of great intrinsic interest to mass spectrometry. However, equal emphasis is deservedly placed on measuring reaction rates for application to other systems. Furthermore, the energy dependence of ion-molecule reaction rates is of fundamental importance in assessing the validity of current theories of ion-molecule reaction rates. Both the practical problem of deducing rate parameters valid for other systems and the desire to provide input to theoretical studies of ion-molecule reactions have served as stimuli for the present work. 

An alternative pathway for activating the cascade has recently been demonstrated in which factor XII is absent from the reaction mixture [42-45]. Two different groups have isolated two different proteins, each of which seems to activate the HK-prekallikrein complex. One is heat-shock protein 90 [46] and the other is a prolylcarboxypeptidase [47]. Neither protein is a direct prekallikrein activator as is factor Xlla or factor Xllf because each activator requires HK to be complexed to the prekallikrein. In addition, the reaction is stoichiometric, thus the amount of prekallikrein converted to kallikrein equals the molar input of heat-shock protein 90 (or prolylcarboxypeptidase). These proteins can be shown to contribute to factor Xll-independent prekallikrein activation and antisera to each protein have been shown to inhibit the process. When whole endothelial cells are incubated with normal plasma or factor Xll-deficient plasma, the rate of activation of the deficient plasma is very much slower than that of the normal plasma, the latter being factor Xll-dependent [45]. Under normal circumstances (with factor XII present), formation of any kallikrein will lead to factor Xlla formation even if the process were initiated by one of these cell-derived factors. 

In general, the substrate temperature will remain unchanged, while pressure, power, and gas flow rates have to be adjusted so that the plasma chemistry is not affected significantly. Grill [117] conceptualizes plasma processing as two consecutive processes the formation of reactive species, and the mass transport of these species to surfaces to be processed. If the dissociation of precursor molecules can be described by a single electron collision process, the electron impact reaction rates depend only on the ratio of electric field to pressure, E/p, because the electron temperature is determined mainly by this ratio. 

Several compounds can be oxidized by peroxidases by a free radical mechanism. Among various substrates of peroxidases, L-tyrosine attracts a great interest as an important phenolic compound containing at 100 200 pmol 1 1 in plasma and cells, which can be involved in lipid and protein oxidation. In 1980, Ralston and Dunford [187] have shown that HRP Compound II oxidizes L-tyrosine and 3,5-diiodo-L-tyrosine with pH-dependent reaction rates. Ohtaki et al. [188] measured the rate constants for the reactions of hog thyroid peroxidase Compounds I and II with L-tyrosine (Table 22.1) and showed that Compound I was reduced directly to ferric enzyme. Thus, in this case the reaction of Compound I with L-tyrosine proceeds by two-electron mechanism. In subsequent work these authors have shown [189] that at physiological pH TPO catalyzed the two-electron oxidation not only L-tyrosine but also D-tyrosine, A -acetyltyrosinamide, and monoiodotyrosine, whereas diiodotyrosine was oxidized by a one-electron mechanism. 

In a hot plasma, the reaction rate per unit volume between particles of types i and... 

The thermal plasma is a source of high energy density with temperature of a few thousand degrees and high ultraviolet radiation. These result in fast reaction rates, high throughput in smaller reactors, heat generation independent of the chemical composition, avoidance of dioxins and furans... 

The rates and selectivities of these processes are frequently enhanced by the presence of plasmas, in which a high electric field in a gas causes ionization of molecules, and the reactions of these ions and the increased transport alters reaction rates. We will not consider these processes in this chapter. 

The Massachusetts Institute of Technology (MIT) has developed the tunable hybrid plasma (THP) system for the treatment of volatile organic compounds (VOCs) in gaseous waste streams. The reactor uses an electron beam to generate a plasma. The electron density of the plasma can be adjusted. This allows for the chemical reaction rates to be controlled as well as the intensity... 

As nonthermal plasma is a mixture of electrons, highly excited atoms and molecules, ions, radicals, photons, and so on, its chemistry is extremely complex, and highly selective products should not be expected via plasma chemistry. The basic reactions for controlling both the direction and reaction rate of plasma C02 utilization can be summarized as follows (here, A and B represent atoms, A2 and B2 molecules, e represents an electron, M is a temporary collision partner, and S represents a solid surface site. The excited species is indicated by an asterisk). 

This is a basic reaction for all C02-involved plasma reactions. Some primary investigations have been conducted for the C02 dissociation using corona discharge [8, 14—17]. Some types of C02 adsorbent, such as basic zeolite, can result in a much higher C02 dissociation rate under corona discharge [18],... 

A model system demonstrating the nutritional destruction of lysine in bovine plasma albumin (BPA) by reaction with either a dialdehyde (MA) or a keto-aldehyde (MGA) was studied in relation to reaction rates as affected by pH, temperature, reaction time and carbonyl concentration. The BPA was Fraction V obtained from Schwartz/Mann and had a molecular weight of 69 x 103 with sixty lysine residules/mole, an assayed content of 11.4%. It was dissolved in 0.0200 M phosphate-citrate buffer adjusted to the desired pH. Malonaldehyde was prepared by acid hydrolysis of its bis-(dimethyl acetal). An aqueous solution of pyruvic aldehyde was diluted with distilled water and phosphate-citrate buffer to give an MGA solution of the desired pH (16). 

On the other hand, the Boltzmann method of calculating the most probable distribution, used in the theoretical model, precludes an explicit consideration of actual values of transition probabilities (rate constants). This would only be possible if plasma reactions are considered as a multi-channel transport problem. However, the knowledge of a large number of various transition probabilities is necessary for such... 

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