The performance of prototypes for the ALICE electromagnetic sampling calorimeter has been studied in test beam measurements at FNAL and CERN. A 4 × 4 array of final design modules showed an energy resolution of about 11% / p E(GeV) ⊕ 1.7 % with a uniformity of the response to electrons of 1% and a good linearity in the energy range from 10 to 100 GeV. The electromagnetic shower position resolution was found to be described by 1.5 mm ⊕ 5.3 mm / p E(GeV). For an electron identification efficiency of 90% a hadron rejection factor of > 600 was obtained.
Carboxylic acids react with sulfur trioxide to form carboxylic sulfuric anhydrides, RCOOSO 2 OH. In this article, new supersonic jet microwave spectra are presented for the anhydride derived from propiolic acid (HCCCOOH), and recent work on a series of carboxylic sulfuric anhydrides is reviewed. For the propiolic acid derivative, computed minimumenergy structures are reported for both the anhydride ( H C C C O O S O 2 O H ) a n d i t s p r e c u r s o r c o m p l e x (HCCCOOH−SO 3 ), and additional CCSD(T)/CBS(D-T)// M06-2X/6-311++G(3df,3pd) calculations indicate that, after zero-point energy corrections, the barrier to anhydride formation is effectively zero. These results are similar to those for other carboxylic sulfuric anhydrides studied and are consistent with their rapid production under supersonic jet conditions. Carboxylic sulfuric anhydrides, as a class, have not been widely characterized in the chemical literature and thus their study represents a new feature of the chemistry of sulfur oxides and oxyacids. As such, structural and energetic features of the carboxylic sulfuric anhydrides derived from formic, acetic, acrylic, trifluoroacetic, propiolic, pinic, and benzoic acids are compared. Computed vibrational frequencies are provided as Supporting Information and should be useful for possible future observation by infrared and/or Raman spectroscopy. Statistical thermodynamics is used to estimate the equilibrium constants for the formation reactions at a series of temperatures, and the results indicate values ranging from ∼10 4 atm −1 for formic acid at 288 K to over 10 11 atm −1 for benzoic acid at 217 K. We speculate that carboxylic sulfuric anhydrides could be active species in the Earth's atmosphere and atmospheric concentrations have, therefore, been estimated assuming an equilibrium state. These estimates are subject to significant uncertainties in the atmospheric SO 3 and carboxylic acid concentrations but may be as high as 10 7 molecules/cm 3 in some locations. Related calculations suggest that equilibrium anhydride concentrations may exceed those of the sulfuric acid precursors SO 3 −H 2 O and SO 3 −(H 2 O) 2 by several orders of magnitude. Kinetic modeling will ultimately be necessary to fully assess the role, if any, of carboxylic sulfuric anhydrides in atmospheric processes.
Electrochemical reprocessing of spent nuclear fuel may be an alternative to aqueous processing and is considered more attractive for fast reactor fuel cycles. Molten salt processing of the fuel may simplify the number of processing steps, but the nuclear industry worldwide has much less operational experience with this technology, including safeguards and security. As interest in electrochemical processing grows in the U.S. and other countries, it is important to understand how to address materials accountancy and security in this unique environment. For this work, a model of a commercial-scale electrochemical plant was developed in Matlab Simulink for design and analysis of integrated safeguards and security systems. The model tracks the mass flow rates of the fuel and salt through the various unit operations and simulates materials accountancy, process monitoring measurements, and physical protection. These measurements are then used to calculate inventory balances during normal operation and diversion scenarios. The model analysis enables one to identify various strategies and options for safeguarding nuclear material, contingent upon the feasibility of the measurement technology. This paper describes the model development, measurement options and strategies, and performance under diversion scenarios.4
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