Influence of Na2S on the degradation kinetics of CCl4 in the presence of very pure iron

This paper presents the results of kinetic studies to investigate the effect of FeS film formation on the degradation rate of CCl(4) by 99.99% pure metallic iron. The film was formed by submersing metallic iron grains in an oxygen free HCO(3)(-)/CO(3)(2-) electrolyte solution. When the grains had reached a quasi steady-state value of the corrosion potential, Na(2)S((aq)) was injected. Upon injection, a microm thick poorly crystalline FeS film formed immediately on the iron surface. Over time, the iron became strongly corroded and both the FeS film and the metallic iron grains began to crack leading to exposure of bare metallic iron to the solution. The effect of the surface film on the degradation rate of CCl(4) was investigated following four periods of aging, 1, 10, 30, and 60 days. Relative to the controls, the 1-day sulfide-aged iron showed a substantial decrease in rate of degradation of CCl(4.) However, over time, the rate of degradation increased and surpassed the degradation rate obtained in the controls. It has been proposed that CCl(4) is reduced to HCCl(3) by metallic iron by electron transfer. The FeS film is substantially less conducting than the bulk iron metal or non-stoichiometric magnetite and from the results of this study, greatly decreases the rate of CCl(4) degradation relative to iron that has not been exposed to Na(2)S. However, continued aging of the FeS film results in breakdown and stress-induced cracking of the film, followed by dissolution and cracking of the iron itself. The cracking of the bulk iron is believed to be a consequence of hydrogen embrittlement, which is promoted by sulfide. The increase in CCl(4) degradation rate, as the FeS films age, suggests that the process of hydrogen cracking increases the surface area available for charge transfer.     

Numerical simulation of hydrogen–air detonation for damage assessment in realistic accident scenarios

An accidental hydrogen release within an equipment enclosure may result in the presence of detonable mixture in a confined environment. From a safety standpoint, it is then useful to assess the potential for damage. In that context, numerical simulation of the sequence of events subsequent to detonative ignition provides a useful tool, although with obvious limitations. This article describes the procedure, summarizes two case studies, and reviews the limitations. First, a hydrogen dispersion pattern is obtained from numerical simulation of dispersion, using a commercial package designed primarily for incompressible flow. This dispersion cloud is then used as the initial condition in an inviscid, compressible, reactive flow simulation. To force detonative ignition, a sufficiently large amount of energy is deposited in a small region that corresponds to the ignition location. Chemistry is modeled using a single step Arrhenius model. Because the wave thickness is small compared with the computational domain, a fine mesh is needed, limiting the practicality of the process to two-dimensional geometries. This is the most significant limitation; it is conservative. The two cases described in the paper include an electrolyzer, in which a small release occurs, leading potentially to some damage to the enclosure, and a reformer, in which the consequences are potentially more serious.     

Scale effects on hydrogen–air fast deflagrations and detonations in small obstructed channels

An experimental study of flame propagation, acceleration and transition to detonation in hydrogen–air mixture in 2-m-long rectangular cross-section channel filled with obstacles located at the bottom wall was performed. The initial conditions of the hydrogen–air mixture were 0.1 MPa and 293 K and stoichiometric composition (29.6% H₂ in air). The channel width was 0.11 m and blockage ratio was 0.5 in all experiments. The effect of channel geometrical scale on flame propagation was studied by using four channel heights H of 0.01, 0.02, 0.04, and 0.08 m. In each case, the obstacle height was equal to H/2 and the obstacle spacing was 2H.

The propagation of flame and pressure waves was monitored by four pressure transducers and four ion probes. The pairs of transducers and probes were placed at various locations along the channel in order to get information about the progress of the phenomena along the channel.

As a result of the experiments, the deflagration and detonation regimes and velocities of flame propagation in the obstructed channel were established.     

On the implementation of an International Curriculum on Hydrogen Safety Engineering into higher education

This paper describes the implementation of an International Curriculum on Hydrogen Safety Engineering into higher education. The curriculum is being developed as part of the educational and training activities of the European Network of Excellence Safety of Hydrogen as an Energy Carrier (HySafe) and has been implemented into a 1-year Postgraduate Certificate Course in Hydrogen Safety Engineering by the University of Ulster. The course is taught in the distance learning mode and comprises of two 30 CATS-point modules, namely, ‘Principles of Hydrogen Safety’ and ‘Applied Hydrogen Safety’. The first delivery of this course began in January 2007 and the second delivery will commence in September 2007.     

Variability of tropospheric hydroperoxides at a coastal surface site in Antarctica

The annual cycles of hydrogen peroxide (H₂O₂) and methylhydroperoxide (MHP) have been investigated at a remote site in Antarctica in order to study seasonal variations as well as chemical processes in the troposphere. The measurements have been performed from March 1997 to January 1998 and in February 1999 at the German Antarctic research station Neumayer which is located at 70°39′S, 8°15′W. The obtained time series for hydrogen peroxide and methylhydroperoxide in near-surface air represents the first all-year measurements in Antarctica and indicates clearly the occurrence of seasonal variations. During polar night mean values of 0.054±0.046 ppbv (range<0.03–0.11 ppbv) for hydrogen peroxide and 0.089±0.052 ppbv (range<0.05–0.14 ppbv) for methylhydroperoxide were detected. At the sunlit period higher Mixing ratios were found, 0.20±0.13 ppbv (range<0.03–0.91 ppbv) for hydrogen peroxide and 0.19±0.10 ppbv (range<0.05–0.89 ppbv) for methylhydroperoxide. Occasional long-range transport of air masses from mid-latitudes caused enhanced peroxide concentrations at polar night. During the period of stratospheric ozone depletion we observed peroxide mixing ratios comparable to typical winter levels.     

Effect of methylmercury on LPO levels, SH groups and activities of GSH-Px, SOD, XOD in liver of rats

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A “measurable” definition of sustainable development based on closed cycles of resources and its application to energy systems

Human society consumes resources that it is not able to reproduce. Human activities are still based on “open cycles,” starting from a condition of natural environmental balance and reaching an environmental imbalance. The challenging scope of scientific and technological research towards sustainability appears clear if it is based on this analysis: to find development systems based on “closed cycles” of resources. The challenging objective of realizing closed cycles leads to a definition of sustainability that indicates the path to sustainable development, as well as stating the general principle. It also provides a key to the qualitative measurement of sustainability. This means that the sustainability level of a system can be measured by measuring its capacity to avoid the consumption of resources. Zero consumption is a necessary condition for sustainability, and brings about as a side effect the highly desired “zero-waste” result. Materials entering the proposed endless scheme pass through the process of usefulness without losing their capacity to feed the system again after being used. Thus, the concept of “consumption” itself is replaced by one of “use” when resources are inserted into closed loops capable of feeding human development. The application of the closed cycle sustainability criterion particularly displays its feasibility, and a theoretical guiding role, in the energy sector. Energy vectors such as hydrogen and electricity enable the closure of the energy resources loop by effectively approaching the objective of “zero consumption” (and the side result of “zero waste”) through already demonstrated technological solutions.     

Reducing the risk level for pipelines transporting carbon dioxide and hydrogen by means of optimal safety valves spacing

In many countries where electricity generation is based on their natural resources of fossil fuels a need arises to implement new power engineering technologies that allow carbon dioxide capture. Simultaneously, efforts are made to find new energy carriers which, if fired, do not involve carbon dioxide emissions. Hydrogen is one of such fuels with this future potential which is now becoming increasingly popular. Obviously, this means that the two gases mentioned above – carbon dioxide and hydrogen – will be produced in large quantities in future, which in many cases will necessitate their transport over considerable distances. If a pipeline failure occurs, the transport of the gases may pose a serious hazard to people in the immediate vicinity of the leakage site. This paper presents an analysis of the possibility of reducing the level of risk related to pipelines transporting CO₂ and H₂ by means of safety valves. It is shown that for a 50 km long and a 0.4 m diameter pipeline transporting gas with the pressure of 15 MPa the individual risk level can be reduced from 1·10⁻⁴ to 6.5·10⁻⁷ for CO₂ and from 1·10⁻⁶ to 6·10⁻¹⁰ for H₂. The social risk can be diminished in similar proportions.     

有机过氧化物在生产、储运过程中的危险与可操作性分析

有机过氧化物的易燃、受热分解等特殊性质和生产、储运过程要求严格的低温条件与操作程序,使得有机过氧化物潜在的危险性很高。通过基于有机过氧化物危险特性及其在生产、储运过程中物质、能量与信息的分析,依据物-能量-信息的安全要素体系,应用危险与可操作分析方法,研究了有机过氧化物的安全理论,在某种程度上是延伸了HAZOP分析的内容。