STUDIES ON HYDROGEN–OXYGEN SYSTEMS IN THE ELECTRIC DISCHARGE: I. THE REACTIONS OF HYDROGEN ATOMS WITH HYDROGEN PEROXIDE

1966 ◽  
Vol 44 (8) ◽  
pp. 869-876 ◽  
Author(s):  
Norisuke H Ata ◽  
Paul A. Glguère

Hydrogen gas partly dissociated in an electrodeless discharge was mixed downstream with hydrogen peroxide vapor at low pressure (0.1 mm Hg) in a liquid nitrogen trap. The reaction products condensed readily on the wall as a clear, yellowish glass resembling that from dissociated water vapor and other related systems. A manometric study of the warming-up process has revealed four distinct steps. The first two, in which only traces of gas are given off, look like the recombination of trapped free radicals. The major evolution of oxygen upon crystallization of the glassy deposit at 160 °K is ascribed to the decomposition of hydrogen peroxide under the influence of some unidentified species generated in the electric discharge through hydrogen. Experimental evidence for this is presented. In any case the stoichiometry cannot be reconciled with the formation of a metastable intermediate, such as the hypothetical polyoxide H2O4.In the last step beginning around 215 °K more peroxide is decomposed during the eutectic melting of the solid. Qualitatively these phenomena are similar to those shown by the condensate from dissociated water vapor.

1968 ◽  
Vol 46 (16) ◽  
pp. 2649-2653 ◽  
Author(s):  
Kazimiera Herman ◽  
Paul A. Giguère

We have reinvestigated in detail the infrared spectra between 4000 and 600 cm−1 of the solid products formed by reacting liquid ozone at −190 °C with a stream of hydrogen gas dissociated in an electrodeless discharge. Extreme care was exercised to get "clean" spectra, free from any contaminants. All the spectra thus obtained showed very clearly the characteristic absorption bands of H2O2 at 2840 and 1430 cm−1, and the much weaker one at 880 cm−1; with deuterium atoms the former bands were shifted to 2100 and 1080 cm−1 respectively. Thus previous contentions that hydrogen peroxide is not one of the primary products of that reaction are disproved. The other infrared bands of H2O2 were not conspicuous, due either to their diffuse nature in the vitreous spectra or to extensive overlapping by the strong absorption of H2O, the other major component. Warming the material up to −110 °C caused some devitrification, but no significant change in the spectra. No new bands which could be assigned unambiguously to the hypothetical molecule H2O4 were observed.


1970 ◽  
Vol 48 (13) ◽  
pp. 2042-2046 ◽  
Author(s):  
Paul E. Brunet ◽  
Xavier Deglise ◽  
Paul A. Giguère

Surface effects in the reactions of dissociated hydrogen–oxygen systems and the products condensed therefrom have been investigated. Water vapor at about 0.1 Torr was streamed at high velocity through an electrodeless discharge confined in tubes of different materials or with various surface coatings. In all cases the products trapped in liquid nitrogen evolved oxygen gas on warming, but the relative amounts varied considerably from one type of surface to another. In some cases there was clear evidence that the walls of discharge tube were attacked by hydrogen atom bombardment. The decomposition, both thermal and electrical, of pure hydrogen peroxide vapor was studied likewise. The pyrolysis products gave off very little oxygen on warming. By contrast the products from electrical decomposition, even at low power level, evolved much oxygen, most of it above the melting point.It is concluded that there is always some decomposition of hydrogen peroxide in the trapped products. However, this does not seem sufficient to account for all the evolved oxygen; at least not in the case of dissociated water vapor.


2004 ◽  
Vol 842 ◽  
Author(s):  
T. Takasugi ◽  
Y. Hotta ◽  
S. Shibuya ◽  
Y. Kaneno ◽  
H. Inoue ◽  
...  

ABSTRACTThermomechanically processed TiAl-based intermetallic alloys with various alloy compositions and microstructures were tensile tested in various environmental media including air, water vapor and a mixture gas of 5vol.%H2+Ar as a function of temperature. All the TiAl-based intermetallic alloys showed reduced tensile fracture stress (or elongation) in air, water vapor and a mixture gas of 5vol.%H2+Ar not only at ambient temperature (RT∼600K) but also at high temperature mostly from 600K to 1000K (sometimes higher temperature than 1000K). The high-temperature environmental embrittlement of TiAl-based intermetallic alloy depended upon the microstructure. The possible species causing the high-temperature environmental embrittlement are hydrogen atoms decomposed from water vapor (H2O) or hydrogen gas (H2), similar to those causing the low-temperature environmental embrittlement.


2018 ◽  
Vol 18 (13) ◽  
pp. 9955-9973 ◽  
Author(s):  
Franziska Frank ◽  
Patrick Jöckel ◽  
Sergey Gromov ◽  
Martin Dameris

Abstract. An important driver of climate change is stratospheric water vapor (SWV), which in turn is influenced by the oxidation of atmospheric methane (CH4). In order to parameterize the production of water vapor (H2O) from CH4 oxidation, it is often assumed that the oxidation of one CH4 molecule yields exactly two molecules of H2O. However, this assumption is based on an early study, which also gives evidence that this is not true at all altitudes. In the current study, we re-evaluate this assumption with a comprehensive systematic analysis using a state-of-the-art chemistry–climate model (CCM), namely the ECHAM/MESSy Atmospheric Chemistry (EMAC) model, and present three approaches to investigate the yield of H2O and hydrogen gas (H2) from CH4 oxidation. We thereby make use of the Module Efficiently Calculating the Chemistry of the Atmosphere (MECCA) in a box model and global model configuration. Furthermore, we use the kinetic chemistry tagging technique (MECCA-TAG) to investigate the chemical pathways between CH4, H2O and H2, by being able to distinguish hydrogen atoms produced by CH4 from H2 from other sources.We apply three approaches, which all agree that assuming a yield of 2 overestimates the production of H2O in the lower stratosphere (calculated as 1.5–1.7). Additionally, transport and subsequent photochemical processing of longer-lived intermediates (mostly H2) raise the local yield values in the upper stratosphere and lower mesosphere above 2 (maximum  >  2.2). In the middle and upper mesosphere, the influence of loss and recycling of H2O increases, making it a crucial factor in the parameterization of the yield of H2O from CH4 oxidation. An additional sensitivity study with the Chemistry As A Boxmodel Application (CAABA) shows a dependence of the yield on the hydroxyl radical (OH) abundance. No significant temperature dependence is found. We focus representatively on the tropical zone between 23° S and 23° N. It is found in the global approach that presented results are mostly valid for midlatitudes as well. During the polar night, the method is not applicable.Our conclusions question the use of a constant yield of H2O from CH4 oxidation in climate modeling and encourage to apply comprehensive parameterizations that follow the vertical profiles of the H2O yield derived here and take the chemical H2O loss into account.


1953 ◽  
Vol 31 (3) ◽  
pp. 262-271 ◽  
Author(s):  
J. S. Batzold ◽  
C. Luner ◽  
C. A. Winkler

The products of the electrical discharge through hydrogen peroxide vapor were hydrogen peroxide, water, oxygen, and hydrogen, in amounts which depended upon the arrangement and temperature of the trap, reaction time, and surface to volume ratio of the reaction vessel. Water, hydrogen, and oxygen resulted from the gas phase reactions of the dissociated hydrogen peroxide, with hydrogen peroxide produced only in a trap cooled below −120 °C. Products trapped below −150 °C evolved oxygen on warming to room temperature. The decomposition products of the electrical discharge through hydrogen peroxide correspond closely with products obtainable both from a similar discharge through water vapor and from the interaction of hydrogen atoms with oxygen molecules in a cold trap. A mechanism which accounts for their correspondence is included. Water was the only product when molecular hydrogen peroxide was caused to react with hydrogen atoms, dissociated hydrogen peroxide vapor, or dissociated water vapor in the presence or absence of molecular hydrogen. A chain mechanism is postulated for these reactions.


Geophysics ◽  
1978 ◽  
Vol 43 (6) ◽  
pp. 1235-1249 ◽  
Author(s):  
J. D. Klein ◽  
R. T. Shuey

The impedance of the interface between an acidic electrolyte and monomineralic, polished electrodes of galena, graphite, and chalcopyrite has been investigated at current densities in the nonlinear range (up to [Formula: see text]). The potential across a single interface relative to a reference electrode was measured in response to a current sinusoid of low frequency, 0.002 Hz. Polarization curves, or linear plots of current density versus electrode potential, consisted of distorted Lissajous patterns. Onset of a new electrochemical reaction resulted in a decrease in impedance of the interface, and hence increase in slope of the polarization curve. For some reactions, the electrical characteristics were diagnostic of bulk mineral composition. Diagnostic reactions include (1) mineral dissolution and gas evolution reactions at extreme anodic and cathodic potentials, (2) reactions at intermediate potentials which involve reaction products from previous reactions. Response is thus dependent on previous reactions and therefore on sample history. Anodic reactions were generally independent of pH, and consisted primarily of mineral dissolution reactions. Potentials of cathodic reactions increased with increasing pH indicating the involvement of [Formula: see text] as demonstrated by the evolution of hydrogen gas and/or [Formula: see text] gas. The potentials of the main graphite reactions were larger in magnitude than any of the sulfide reaction potentials. Measurements with polymineralic electrodes indicate that current flows mainly through minerals with reactions at less extreme potentials and consequently reactions involving other minerals at higher potential do not occur. Due to its more extreme reaction potentials, graphite does not respond in the presence of sulfide minerals. It appears that nonlinear phenomena could be used for mineral discrimination in drill hole logging.


2001 ◽  
Vol 27 (8) ◽  
pp. 642-643 ◽  
Author(s):  
A. K. Shuaibov ◽  
L. L. Shimon ◽  
A. I. Dashchenko ◽  
I. V. Shevera

Catalysts ◽  
2018 ◽  
Vol 8 (12) ◽  
pp. 648 ◽  
Author(s):  
Haigang Hao ◽  
Tong Chang ◽  
Linxia Cui ◽  
Ruiqing Sun ◽  
Rui Gao

As a country that is poor in petroleum yet rich in coal, it is significant for China to develop direct coal liquefaction (DCL) technology to relieve the pressure from petroleum shortages to guarantee national energy security. To improve the efficiency of the direct coal liquefaction process, scientists and researchers have made great contributions to studying and developing highly efficient hydrogen donor (H-donor) solvents. Nevertheless, the details of hydrogen donation and the transfer pathways of H-donor solvents are still unclear. The present work examined hydrogen donation and transfer pathways using a model H-donor solvent, tetralin, by density functional theory (DFT) calculation. The reaction condition and state of the solvent (gas or liquid) were considered, and the specific elementary reaction routes for hydrogen donation and transfer were calculated. In the DCL process, the dominant hydrogen donation mechanism was the concerted mechanism. The sequence of tetralin donating hydrogen atoms was α-H (C1–H) > δ-H (C4–H) > β-H (C2–H) > γ-H (C3–H). Compared to methyl, it was relatively hard for benzyl to obtain the first hydrogen atom from tetralin, while it was relatively easy to obtain the second and third hydrogen atoms from tetralin. Comparatively, it was easier for coal radicals to capture hydrogen atoms from the H-donor solvent than to obtain hydrogen atoms from hydrogen gas.


Author(s):  
Derya Dispinar

It is well known that the reaction of liquid aluminum with the moisture in the environment results in two products: aluminum oxide and hydrogen gas that dissolves in aluminum. Both of these products are considered to be detrimental to the properties of aluminum alloys. Therefore, test equipment has been developed to check the levels of these defects in the melt. Many of these involve expensive and consumable tools. In addition, an experienced personnel may be required to interpret the results. Nonetheless, aluminum oxide is harmless as long as it remains on the surface. The problem begins when this oxide is entrained into the liquid aluminum such as turbulence during transfer or mold filling in a non-optimized design. This can only happen by folding of the oxide. During this action, rough surface of the oxides comes in contact to form no bonds. These defects are known as bifilms that have certain characteristics. First, they act as cracks in the cast parts since they are oxides. It is important to note that aluminum oxide has thin amorphous oxide (known as young oxides) and thick crystalline oxide (γ-Al2O3) that may be formed in a casting operation. Second, almost zero force is required to open these bifilms due to the unbonded folded oxide skins. Thus, these defects can easily form porosity by unravelling during solidification shrinkage. On the other hand, the formation of porosity by hydrogen is practically impossible. Theoretically, hydrogen has high solubility in the liquid but it has significantly low solubility in solid aluminum. Thus, it is suspected that hydrogen is rejected from the solidification front to form hydrogen gas and porosity. However, the hydrogen atom has the smallest atomic radii and high diffusibility. Therefore, segregation of hydrogen in front of the growing solid is difficult. In addition, the energy required for hydrogen atoms to segregate and form hydrogen gas molecule is around 30,000 atm. Under these conditions, porosity formation by hydrogen is not likely to be achieved. Hydrogen probably stays in a supersaturated state or diffuses homogeneously through the cast part. The effect of hydrogen can only be seen when it can diffuse into the unbonded gap between the bifilms to open them up to aid the unravelling of bifilms to form porosity. This phenomenon can be easily detected by a very simple test called reduced pressure test. When a sample is solidified under vacuum, the bifilms start to open up. Since all porosity is formed by bifilms, the cross section of the sample solidified under vacuum can be analyzed by means of image analysis software. The sum of maximum length of pores can be measured as an indication of melt quality. Since bifilms are the most detrimental defects, this value is called “bifilm index” given in millimetres, which makes this test the only test that can quantify aluminum melt quality in such detail including both the effects of bifilms and hydrogen together. Several Al-Si alloys were used at various conditions: degassing with lance, ceramic diffusers, and graphite rotary has been compared. Gravity sand casting, die casting, and low-pressure die casting methods were evaluated. The effect of grain refiners and modifiers was studied. And the evolution of the bifilm index has been presented.


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