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Thermochemical Cycle (thermochemical + cycle)
Selected AbstractsThermodynamic analysis of two-step solar water splitting with mixed iron oxidesINTERNATIONAL JOURNAL OF ENERGY RESEARCH, Issue 10 2009Martin Roeb Abstract A two-step thermochemical cycle for solar production of hydrogen from water has been developed and investigated. It is based on metal oxide redox pair systems, which can split water molecules by abstracting oxygen atoms and reversibly incorporating them into their lattice. After successful experimental demonstration of several cycles of alternating hydrogen and oxygen production, the present work describes a thermodynamic study aiming at the improvement of process conditions and at the evaluation of the theoretical potential of the process. In order to evaluate the maximum hydrogen production potential of a coating material, theoretical considerations based on thermodynamic laws and properties are useful and faster than actual tests. Through thermodynamic calculations it is possible to predict the theoretical maximum output of H2 from a specific redox-material under certain conditions. Calculations were focussed on the two mixed iron oxides nickel,iron-oxide and zinc,iron-oxide. In the simulation the amount of oxygen in the redox-material is calculated before and after the water-splitting step on the basis of laws of thermodynamics and available material properties for the chosen mixed iron oxides. For the simulation the commercial Software FactSage and available databases for the required material properties were used. The analysis showed that a maximum hydrogen yield is achieved if the reduction temperature is raised to the limits of the operation range, if the temperature for the water splitting is lowered below 800°C and if the partial pressure of oxygen during reduction is decreased to the lower limits of the operational range. The predicted effects of reduction temperature and partial pressure of oxygen could be confirmed in experimental studies. The increased hydrogen yield at lower splitting temperatures of about 800°C could not be confirmed in experimental results, where a higher splitting temperature led to a higher hydrogen yield. As a consequence it can be stated that kinetics must play an important role especially in the splitting step. Copyright © 2009 John Wiley & Sons, Ltd. [source] Determination of the electron affinities of ,- and ,-naphthyl radicals using the kinetic method with full entropy analysis.JOURNAL OF MASS SPECTROMETRY (INCORP BIOLOGICAL MASS SPECTROMETRY), Issue 6 2001H bond dissociation energies of naphthalene, The C Abstract The C , H bond dissociation energies for naphthalene were determined using a negative ion thermochemical cycle involving the gas-phase acidity (,Hacid) and electron affinity (EA) for both the ,- and ,-positions. The gas-phase acidity of the naphthalene ,- and ,-positions and the EAs of the ,- and ,-naphthyl radicals were measured in the gas phase in a flowing afterglow,triple quadrupole apparatus. A variation of the Cooks kinetic method was used to measure the EAs of the naphthyl radicals by collision-induced dissociation of the corresponding ,- and ,-naphthylsulfinate adducts formed by reactions in the flow tube portion of the instrument. Calibration references included both , and , radicals, and full entropy analysis was performed over a series of calibration curves measured at collision energies ranging from 3.5 to 8 eV (center-of-mass). The measured EAs are 33.0 ± 1.4 and 31.4 ± 1.0 kcal mol,1 (1 kcal = 4.184 kJ) for the ,- and ,-naphthyl radicals, respectively. The gas-phase acidities for naphthalene were measured by the DePuy silane cleavage method, which utilizes the relative abundances of aryldimethylsiloxides and trimethylsiloxide that result from competitive cleavages from a proposed pentacoordinate hydroxysiliconate intermediate. The measured acidities are 394.0 ± 5.0 and 397.6 ± 4.8 kcal mol,1 for the ,- and ,- positions, respectively. The C , H bond dissociation energies calculated from the thermochemical cycle are 113.4 ± 5.2 and 115.4 ± 4.9 kcal mol,1 for the ,- and ,-positions, respectively. These energies are, to within experimental error, indistinguishable and are approximately the same as the first bond dissociation energy for benzene. Copyright © 2001 John Wiley & Sons, Ltd. [source] A Radical-Anion Chain Mechanism Initiated by Dissociative Electron Transfer to a Bicyclic Endoperoxide: Insight into the Fragmentation Chemistry of Neutral Biradicals and Distonic Radical AnionsCHEMISTRY - A EUROPEAN JOURNAL, Issue 6 2008David Abstract The electron-transfer (ET) reduction of two diphenyl-substituted bicyclic endoperoxides was studied in N,N -dimethylformamide by heterogeneous electrochemical techniques. The study provides insight into the structural parameters that affect the reduction mechanism of the OO bond and dictate the reactivity of distonic radical anions, in addition to evaluating previously unknown thermochemical parameters. Notably, the standard reduction potentials and the bond dissociation energies (BDEs) were evaluated to be ,0.55±0.15,V and 20±3,kcal,mol,1, respectively, the last representing some of the lowest BDEs ever reported. The endoperoxides react by concerted dissociative electron transfer (DET) reduction of the OO bond yielding a distonic radical-anion intermediate. The reduction of 1,4-diphenyl-2,3-dioxabicyclo[2.2.2]oct-5-ene (1) results in the quantitative formation of 1,4-diphenylcyclohex-2-ene- cis -1,4-diol by an overall two-electron mechanism. In contrast, ET to 1,4-diphenyl-2,3-dioxabicyclo[2.2.2]octane (2) yields 1,4-diphenylcyclohexane- cis -1,4-diol as the major product; however, in competition with the second ET from the electrode, the distonic radical anion undergoes a ,-scission fragmentation yielding 1,4-diphenyl-1,4-butanedione radical anion and ethylene in a mechanism involving less than one electron. These observations are rationalized by an unprecedented catalytic radical-anion chain mechanism, the first ever reported for a bicyclic endoperoxide. The product ratios and the efficiency of the catalytic mechanism are dependent on the electrode potential and the concentration of weak non-nucleophilic acid. A thermochemical cycle for calculating the driving force for ,-scission fragmentation is presented, and provides insight into why the fragmentation chemistry of distonic radical anions is different from analogous neutral biradicals. [source] Crystal Structure, Lattice Energy, and Standard Molar Enthalpy of Formation of the Complex (C11H18NO)2CuCl4 (s)CHINESE JOURNAL OF CHEMISTRY, Issue 7 2010Wenyan Dan Abstract The complex (C11H18NO)2CuCl4 (s), which may be a potential effective drug, was synthesized. X-ray crystallography, elemental analysis, and chemical analysis were used to characterize the structure and composition of the complex. Lattice energy and ionic radius of the anion of the complex were derived from the crystal data of the title compound. In addition, a reasonable thermochemical cycle was designed, and standard molar enthalpies of dissolution for reactants and products of the synthesis reaction of the complex were measured by an isoperibol solution-reaction calorimeter. The enthalpy change of the reaction was calculated to be ,rH,m=(2.69±0.02) kJ·mol,1 from the data of the above standard molar enthalpies of dissolution. Finally, the standard molar enthalpy of formation of the title compound was determined to be ,rH,m[(C11 H18NO)2CuCl4, s]= , (1822.96±6.80) kJ·mol,1 in accordance with Hess law. [source] Experimental study on sulfur trioxide decomposition in a volumetric solar receiver,reactorINTERNATIONAL JOURNAL OF ENERGY RESEARCH, Issue 9 2009Adam Noglik Abstract Process conditions for the direct solar decomposition of sulfur trioxide have been investigated and optimized by using a receiver,reactor in a solar furnace. This decomposition reaction is a key step to couple concentrated solar radiation or solar high-temperature heat into promising sulfur-based thermochemical cycles for solar production of hydrogen from water. After proof-of-principle a modified design of the reactor was applied. A separated chamber for the evaporation of the sulfuric acid, which is the precursor of sulfur trioxide in the mentioned thermochemical cycles, a higher mass flow of reactants, an independent control and optimization of the decomposition reactor were possible. Higher mass flows of the reactants improve the reactor efficiency because energy losses are almost independent of the mass flow due to the predominant contribution of re-radiation losses. The influence of absorber temperature, mass flow, reactant initial concentration, acid concentration, and residence time on sulfur trioxide conversion and reactor efficiency has been investigated systematically. The experimental investigation was accompanied by energy balancing of the reactor for typical operational points. The absorber temperature turned out to be the most important parameter with respect to both conversion and efficiency. When the reactor was applied for solar sulfur trioxide decomposition only, reactor efficiencies of up to 40% were achieved at average absorber temperature well below 1000°C. High conversions almost up to the maximum achievable conversion determined by thermodynamic equilibrium were achieved. As the re-radiation of the absorber is the main contribution to energy losses of the reactor, a cavity design is predicted to be the preferable way to further raise the efficiency. Copyright © 2009 John Wiley & Sons, Ltd. [source] | ||||||||||