We review the experimental and theoretical work which has been carried out on the dynamics of reactions of O(3P) with saturated hydrocarbons and related systems. We concentrate primarily on gas phase reactions, but also cover in less detail the more limited work on condensed phase and interfacial reactions. Although O(3P) + saturated alkane reactions are the primary focus, the dominant features of their dynamics are compared and contrasted with those of unsaturated alkanes, functionalised alkanes, and inorganic hydrides (including silanes, germanes, H2S, and hydrogen halides). The principal experimental techniques are reviewed. The experimentally determined quantities are identified, including excitation functions, OH rovibrational and fine-structure partitioning, the rather limited equivalent results for the organic radical co-product, and differential cross-sections. The dynamical conclusions that have been inferred are discussed and compared with the predictions of various levels of theory from semi-empirical models through to rigorous ab initio treatments. For many organic systems, most of the evidence points to OH being formed via a direct abstraction mechanism in which the O(3P) atom attacks along an isolated C–H bond. Outstanding problems with this basic interpretation and gaps in the current knowledge base are identified.
We present experimental rotational distributions for the reaction H + D2 --> HD(nu' = 3,j') + D at eight different collision energies between 1.49 and 1.85 eV. We combine a previous measurement of the state-resolved excitation function for this reaction [Ayers et al., J. Chem. Phys. 119, 4662 (2003)] with the current data to produce a map of the relative reactive cross section as a function of both collision energy and rotational quantum number (an E-j' plot). To compare with the experimental data, we also present E-j' plots resulting from both time-dependent and time-independent quantum mechanical calculations carried out on the BKMP2 surface. The two calculations agree well with each other, but they produce rotational distributions significantly colder than the experiment, with the difference being more pronounced at higher collision energies. Disagreement between theory and experiment might be regarded as surprising considering the simplicity of this system; potential causes of this discrepancy are discussed.
The importance of reactive trajectories straying far from the minimum energy path is demonstrated for the bimolecular reaction H + HBr --> H2(v', j') + Br at 53 kcal/mol collision energy. Product quantum state distributions are measured and calculated using the quasi-classical trajectory technique, and the calculations indicate that highly internally excited H2 products result from indirect reactive trajectories with bent transition states. A general argument is made suggesting that reaction products with internal energy exceeding a kinematic constraint can, in general, be attributed to reactive collisions straying far from the minimum energy path.
Energy Storage Technologies as Options to a Secure Energy SupplyThe current energy system is subject to a profound change: A system, designed to cater to energy needs by supplying fossil fuels is now expected to shift to integrate ever larger amounts of renewable energies to achieve overall a more sustainable energy supply. The challenges arising from this paradigm change are currently most obvious in the area of electric power supply. However, it affects the entire energy system, albeit with different effects. Within the energy system, various independent grids fulfill the function to transport and distribute energy or energy carriers in order to address spatially different energy supply and demand situations. Temporal variations are currently addressed by just-in-time production of the required energy form. However, renewable energy sources generally supply their energy independently from any specific energy demand. Their contribution to the overall energy system is expected to increase significantly. Energy storage technologies also represent an option to compensate for a temporal difference in energy supply and demand. Energy storage systems have the ability for a controlled take-up of a certain amount of energy, storing this energy within a storage media on a relevant timescale and a controlled redispatch of the energy after a certain time delay. Energy storage systems can also be constructed as process chains by combinations of unit operations, each covering different aspects of those functions. Large-scale mechanical storage options for electrical power are currently almost exclusively pumped hydro storage. These systems might be complemented in the future by compressed-air storage and maybe liquid-air facilities. There are several electrochemical storage technologies currently under investigation for their suitability as large scale electrical energy storage in various stages of research, development, and demonstration. Thermal energy storage technologies are based on a large variety of storage principles: Sensible heat, latent heat (based on phase transitions), adsorption/desorption processes or on chemical reactions. The latter can be a route to permanent and loss-free storage of heat. Chemical energy storage systems are based on the energy contained within the chemical bonds of the respective storage molecules. These storage molecules can act as energy carriers. Equally well, these compounds can enter various industrial value chains in energy-intensive industrial sectors and are therefore in direct economic competition with established (fossil) supply routes for these compounds. Water electrolysis, producing hydrogen and oxygen, is and will be the key technology for the foreseeable future. Hydrogen can be transformed by various processes to other energy carriers of interest. These transformations make the stored energy accessible by different sectors of the energy system and/or as raw materials for energy-intensive industrial processes. Some functions of energy storage systems can be taken over by ind...
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