Studying the process of ionization of hydrogen in conditions of its forced delivery to a porous nickel oxide electrode

The hydrogen ionization process is studied experimentally on an industrial sintered nickel oxide electrode in models of sealed nickel-metal hydride batteries. It is shown that the hydrogen ionization rates that are reached during overcharge by high current densities in conditions of forced gas delivery into the electrode pores (up to 40 mA cm^?2) exceed the self-discharge rate of a nickel-hydrogen battery by two orders of magnitude. Up to 70% of hydrogen delivered into the compact assembly block undergoes ionization during forced charge of models of sealed nickel-metal hydride batteries with a closed hydrogen cycle. Two independent methods (potentiostatic and manometric) are used to determine the relationship between rates of hydrogen ionization with the degree of the electrode filling with gas and perform estimation of the process intensity at a unit reaction surface. It is established that, in conditions of forced gas delivery, practically all the hydrogen oxidation current is generated at the surface of the nickel oxide electrode beneath thin films of an electrolyte solution at the rate of 4–5 mA cm^?2. It is shown that the hydrogen oxidation rate on a nickel oxide electrode filled in part by gas is independent of the electrode potential, probably because of a tangible contribution made by diffusion limitations to the overall hampering of the process.     

A study on the electrical conductivity of multi-walled carbon nanotube aqueous solution

The electrical conductivity was investigated for multi-walled carbon nanotubes (MWNTs) dissolved in chloroform and toluene, respectively. The electrical conductivity remarkably increased with increase in the content of MWNTs, which is in accordance with Archie's equation . Furthermore, a hypothesis of the electronic transport process was proposed to explain the difference between the solution and the solid compound. In addition, the temperature dependence of the electrical conductivity shows that log σ vs. 1/T exist in a good linear relationship. The activation energy of the electrical conductivity decreased with increase in concentration and an inflexion was observed at 60 °C in MWNT/toluene solution.     

Theoretical Study on the Reaction Mechanism between Dichlorocarbene and Armchair Single-walled Carbon Nanotubes

1 INTRODUCTION Carbon nanotubes have many potential applica- tions due to their unique structures and properties[1～4]. Physicists have been studying their electrical, me- chanical and other properties since their discove- ries[5, 6]. Recently, chemists are interested in carbon nanotubes because their properties can be altered by chemical functionalization[7～14], and these functiona- lized nanotubes can undergo further chemical trea- tment. So the potential application range of such na- …     

Non‐empirical calculations of NMR indirect carbon–carbon coupling constants. Part 4: Bicycloalkanes

A systematic study of the one‐bond and long‐range J(C,C), J(C,H) and J(H,H) in the series of nine bicycloalkanes was performed at the SOPPA level with special emphasis on the coupling transmission mechanisms at bridgeheads. Many unknown couplings were predicted with high reliability. Further refinement of SOPPA computational scheme adjusted for better performance was carried out using bicyclo[1.1.1]pentane as a benchmark to investigate the influence of geometry, basis set and electronic correlation. The calculations performed demonstrated that classical ab initio SOPPA applied with the locally dense Dunning's sets augmented with inner core s‐functions used for coupled carbons and Sauer's sets augmented with tight s‐functions used for coupled hydrogens performs perfectly well in reproducing experimental values of different types of coupling constants (the estimated reliability is ca 1–2 Hz) in relatively large organic molecules of up to 11 carbon atoms. Additive coupling increments were derived for J(C,C), J(C,H) and J(H,H) based on the calculated values of coupling constants within SOPPA in the model bicycloalkanes, in reasonably good agreement with the known values obtained earlier on pure empirical grounds. Most of the bridgehead couplings in all but one bicycloalkane appeared to be essentially additive within ca 2–3 Hz while bicyclo[1.1.1]pentane demonstrated dramatic non‐additivity of ?14.5 Hz for J(C,C), +16.6 Hz for J(H,H) and ?5.5 Hz for J(C,H), in line with previous findings. Non‐additivity effects in the latter compound established at the SOPPA level should be attributed to the through‐space non‐bonded interactions at bridgeheads due to the essential overlapping of the bridgehead rear lobes which provides an additional and effective non‐bonding coupling path for the bridgehead carbons and their protons in the bicyclopentane framework. Copyright © 2003 John Wiley & Sons, Ltd.     

Supercritical CO2 as a superior solvent for the cyclization of diallylmalonate catalyzed by palladium-containing zeolites

Palladium-containing zeolites catalyze the cycloisomerization of diethyl diallylmalonate to dimethylcyclopentenes. When the reaction is carried out in toluene, the performance of the palladium catalyst depends on the pore size of the zeolites. At 60 °C, palladium adsorbed on large pore size Beta zeolite (pore size ∼7.4 Å) is more active than medium pore size ZSM-5 (pore size ∼5.4 Å). This lower activity of ZSM-5 compared to Beta is attributable to the restricted diffusion of reagent and products through the ZSM-5 channels as compared to Beta zeolite. However, due to the gas-like diffusion characteristic of the supercritical state, the activity of ZSM-5 increases and becomes identical to that of Beta zeolite using supercritical CO₂ as medium.     

Lithium heptadecafluorooctanesulfonate catalyzed Mannich-type and aza-Diels-Alder reactions in supercritical carbon dioxide

The Mannich-type reaction of imines with (1-methoxy-2-methylpropenyloxy)trimethylsilane and aza-Diels-Alder reaction of imines with Danishefsky's diene can be carried out in scCO₂ in the presence of lithium heptadecafluorooctanesulfonate which offer a way to synthesize β-amino carbonyl compounds and nitrogen-containing six-membered ring compounds under environmentally benign conditions.     

Reversible nonlinear conduction in high‐density polyethylene/acetylene carbon black composites at various ambient temperatures

The reversible nonlinear conduction (RNC) in of high‐density polyethylene/acetylene carbon black composites with different degrees of crosslinking was studied above room temperature and below the melting point of high‐density polyethylene (HDPE). The experimental current density‐electric field strength curves can be overlapped onto a master curve, suggesting that the microscopic mechanisms for the appearance of RNC exist regardless of the ambient temperature and the crosslinking degree of the HDPE matrix. The relationship between the crossover current density and the linear conductivity can be explained in the framework of the dynamic random‐resistor‐network model. According to these results, two electron‐tunneling models are suggested to interpret the microscopic conduction behavior. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1212–1217, 2004     

Novel fixed‐site–carrier polyvinylamine membrane for carbon dioxide capture

Fixed‐site–carrier membranes were prepared for the facilitated transport of CO₂ by casting polyvinylamine (PVAm) on various supports, such as poly(ether sulfone) (PES), polyacrylonitrile (PAN), cellulose acetate (CA), and polysulfone (PSO). The cast PVAm on the support was crosslinked by various methods with glutaraldehyde, hydrochloric acid, sulfuric acid, and ammonium fluoride. Among the membranes tested, the PVAm cast on polysulfone and crosslinked by ammonium fluoride showed the highest selectivity of CO₂ over CH₄ (>1000). The permeance of CO₂ was then measured to be 0.014 m³ (STP)/(m² bar h) for a 20 μm thick membrane. The effect of the molecular weight of PVAm and feed pressure on the permeance was also investigated. The selectivity increased remarkably with increasing molecular weight and decreased slightly with increased pressure in the range of 1 to 4 bar. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4326–4336, 2004     

Radioactive Tracer Study of the Displacement of Iodine Adatoms from Platinized Platinum Electrode by Carbon Monoxide

Radioactive tracer studies confirm the earlier electrochemical results that carbon monoxide can virtually completely displace iodine adatoms. For the first time, it is found that iodine adatoms are not displaced by carbon monoxide when iodide anions are adsorbed in the presence of an upd silver monolayer. The possible reasons for the effect observed are discussed.     

Diffusion in poro‐plastic media

A model is developed for the flow of a slightly compressible fluid through a saturated inelastic porous medium. The initial‐boundary‐value problem is a system that consists of the diffusion equation for the fluid coupled to the momentum equation for the porous solid together with a constitutive law which includes a possibly hysteretic relation of elasto‐visco‐plastic type. The variational form of this problem in Hilbert space is a non‐linear evolution equation for which the existence and uniqueness of a global strong solution is proved by means of monotonicity methods. Various degenerate situations are permitted, such as incompressible fluid, negligible porosity, or a quasi‐static momentum equation. The essential sufficient conditions for the well‐posedness of the system consist of an ellipticity condition on the term for diffusion of fluid and either a viscous or a hardening assumption in the constitutive relation for the porous solid. Copyright © 2004 John Wiley & Sons, Ltd.