{\rtf1\ansi\ansicpg1250\deff0\deflang1038\deflangfe1038\deftab708{\fonttbl{\f0\froman\fprq2\fcharset238{\*\fname Times New Roman;}Times New Roman CE;}} \viewkind4\uc1\pard\f0\fs24 Efficiency self-calibration of the HPGe detector for on-line assay of pebble bed reactor fuel \par }

Summary {\rtf1\ansi\ansicpg1250\deff0\deflang1038\deflangfe1038\deftab708{\fonttbl{\f0\froman\fprq2\fcharset238{\*\fname Times New Roman;}Times New Roman CE;}} \viewkind4\uc1\pard\f0\fs24 Multi-pass pebble bed reactors are loaded with spherical fuel pebbles that are circulated through the core until they reach a proposed burnup limit (~100,000 MWD/MTU). An HPGe detector can be used to assay the fuel on-line to ensure that the burnup limit is not breached. The potential exists for using a relative burnup indicator, which would allow the use of a relative self-calibrating approach for efficiency determination. The utilization of several fission products as built-in on-line relative calibration standards is explored using the computer codes ORIGEN2.1, MCNP4C, and SYNTH to produce simulated gamma-ray spectra of the fuel pebbles at various levels of burnup. \par }     

{\rtf1\ansi\ansicpg1250\deff0\deflang1038\deflangfe1038\deftab708{\fonttbl{\f0\froman\fprq2\fcharset238{\*\fname Times New Roman;}Times New Roman CE;}} \viewkind4\uc1\pard\f0\fs20 Calorimetric study of transition phenomena in molecular solids \par }

Summary {\rtf1\ansi\ansicpg1250\deff0\deflang1038\deflangfe1038\deftab708{\fonttbl{\f0\froman\fprq2\fcharset238{\*\fname Times New Roman;}Times New Roman CE;}} \viewkind4\uc1\pard\f0\fs20 Principle and technical development of low temperature calorimetry are described. Typical experimental results obtained by our group at Osaka University over the four decades are given. These include phase transitions in equilibrium crystals and glass transitions in non-equilibrium frozen-in disordered solids including crystals. It can be concluded that the glass transitions observed exclusively in liquids so far are just one example of transitions that must be of wide occurrence in solids arising from freezing of relevant degrees of freedom. Interplay between the phase and glass transitions in crystals is discussed in relation to useful dopant that may accelerate some molecular motions that had failed to maintain equilibrium at low temperatures. \par }     

{\rtf1\ansi\ansicpg1250\deff0\deflang1038\deflangfe1038\deftab708{\fonttbl{\f0\froman\fprq2\fcharset238{\*\fname Times New Roman;}Times New Roman CE;}} \viewkind4\uc1\pard\f0\fs24 Status of software for PGNAA bulk analysis by the Monte Carlo - Library Least-Squares (MCLLS) approach \par }

Summary {\rtf1\ansi\ansicpg1250\deff0\deflang1038\deflangfe1038\deftab708{\fonttbl{\f0\froman\fprq2\fcharset238{\*\fname Times New Roman;}Times New Roman CE;}} \viewkind4\uc1\pard\f0\fs24 The Center for Engineering Applications of Radioisotopes (CEAR) has been working for about ten years on the Monte Carlo - Library Least-Squares (MCLLS) approach for treating the nonlinear inverse analysis problem for PGNAA bulk analysis. This approach consists essentially of using Monte Carlo simulation to generate the libraries of all the elements to be analyzed plus any other required libraries. These libraries are then used in the linear Library Least-Squares (LLS) approach with unknown sample spectra to analyze for all elements in the sample. The other libraries include all sources of background which includes: (1) gamma-rays emitted by the neutron source, (2) prompt gamma-rays produced in the analyzer construction materials, (3) natural gamma-rays from K-40 and the uranium and thorium decay chains, and (4) prompt and decay gamma-rays produced in the NaI detector by neutron activation. A number of unforeseen problems have arisen in pursuing this approach including: (1) the neutron activation of the most common detector (NaI) used in bulk analysis PGNAA systems, (2) the nonlinearity of this detector, and (3) difficulties in obtaining detector response functions for this (and other) detectors. These problems have been addressed by CEAR recently and have either been solved or are almost solved at the present time. We have now finished the development of Monte Carlo simulation for all of the libraries except the prompt gamma-ray library from the activation of the NaI detector. We must first determine a treatment for the coincidence schemes for Na and particularly I to complete the Monte Carlo simulation of this last library. \par }     

{\rtf1\ansi\ansicpg1250\deff0\deflang1038\deflangfe1038\deftab708{\fonttbl{\f0\froman\fprq2\fcharset238{\*\fname Times New Roman;}Times New Roman CE;}} \viewkind4\uc1\pard\f0\fs24 Neutron activation analysis using Excel files and Canberra Genie-2000 \par }

Summary {\rtf1\ansi\ansicpg1250\deff0\deflang1038\deflangfe1038\deftab708{\fonttbl{\f0\froman\fprq2\fcharset238{\*\fname Times New Roman;}Times New Roman CE;}} \viewkind4\uc1\pard\f0\fs24 We have developed a method for analyzing neutron activated sample data by using Microsoft Excel as the analysis engine. A simple technique for inputting data is based on report files generated by Canberra’s Genie-2000 spectroscopy system but could be easily modified to support other vendors having report formats with consistent text placement. A batch program handles operating an automatic sample changer, acquiring the data, and analyzing the spectrum to create a report of the peak locations and net area. The entire report is then transferred to within an Excel spreadsheet as the source data for neutron activation analysis. Unique Excel templates have been designed, for example, to accommodate short-lived and long-lived isotopes. This process provides us with a largely integrated solution to NAA while providing the results in an industry standard spreadsheet format. This software is ideally suited for teaching and training purposes. \par }     

{\rtf1\ansi\ansicpg1250\deff0\deflang1038\deflangfe1038\deftab708{\fonttbl{\f0\froman\fprq2\fcharset238{\*\fname Times New Roman;}Times New Roman CE;}} \viewkind4\uc1\pard\f0\fs24 Automated analysis of off-line measured gamma-spectra using \scaps UniSampo\scaps0 gamma-ray spectrum analysis software including criterias for alarming systems \par }

Summary {\rtf1\ansi\ansicpg1250\deff0\deflang1038\deflangfe1038\deftab708{\fonttbl{\f0\froman\fprq2\fcharset238{\*\fname Times New Roman;}Times New Roman CE;}} \viewkind4\uc1\pard\lang2057\f0\fs24 In many laboratories the number of measured routine gamma-spectra can be significant and the labour work to review all the data is time consuming and expensive task. In many cases the routine sample does not normally contain radiation above a detectable level, and still the review of the spectra has to be performed. By introducing simple rules for emerging conditions, the review work can be significantly reduced. In one case the need to review the environmental measurement spectra was reduced to less than 1% compared to the original need, which in turn made the review personnel available for more useful functions. Using the \scaps UniSampo\scaps0 analysis system, the analysis results of spectra that are causing alarming conditions can be transmitted via e-mail to any address. Some systems are even equipped with the capability to forward these results to hand-portable telephones or pagers. This is a very practical solution for automated environmental monitoring, when the sample spectra are collected automatically and transmitted to central computer for further analysis. The paper describes how to set up an automatic analysis system, rules for the emerging conditions, technical solutions for an automated alarming system and a generic hypothesis test for the alarming system developed for \scaps UniSampo\scaps0 analysis software. \par }     

Excess molar heat capacities of ((<Emphasis Type="Italic">R</Emphasis>)-(+)-α-pinene+(<Emphasis Type="Italic">S</Emphasis>)-(-)- α-pinene) at temperatures between 293.15-308.15 K

Summary {\rtf1\ansi\ansicpg1250\deff0\deflang1038\deflangfe1038\deftab708{\fonttbl{\f0\froman\fprq2\fcharset238{\*\fname Times New Roman;}Times New Roman CE;}} \viewkind4\uc1\pard\f0\fs20 New explanations are given for two types of irregular thermogravimetric (TG) data. A TG relationship between mass and temperature is derived on the basis of migration behavior of bubbles generated in bulk of sample system, and superposed on that derived on the basis of kinetics of the 4\super th\nosupersub order event, which is superposed on the experimental TG data obtained from three reference papers. This suggests that these TG data are reflecting migration of bubbles. A dependence of TG behavior on heating rate, which is contrary to usual that, is shown and is explained in terms of event-rate determination by boiling. \par }     

{\rtf1\ansi\ansicpg1250\deff0\deflang1038\deflangfe1038\deftab708{\fonttbl{\f0\froman\fprq2\fcharset238{\*\fname Times New Roman;}Times New Roman CE;}} \viewkind4\uc1\pard\f0\fs20 A pseudo-isothermal kinetic analysis of the recrystallisation of nickel sulphide measured by non-isothermal DSC \par }

Summary A pseudo-isothermal method for the kinetic analysis was applied to the recrystallisation of to nickel sulphide based on the Ozawa model for non-isothermal crystallisation in the presence of pre-existing nuclei. The aim of the analysis was to determine the number of steps involved in the recrystallisation and, hence, determine the applicability of the kinetic equation based on a single step mechanism, as is commonly applied in the kinetic analysis of solid-state processes using thermal methods. The kinetic analysis yielded evidence of at least two processes indicating that physical and mechanistic significance should not be drawn from the use of a single step approximation of the rate equation.     

{\rtf1\ansi\ansicpg1250\deff0\deflang1038\deflangfe1038\deftab708{\fonttbl{\f0\froman\fprq2\fcharset238{\*\fname Times New Roman;}Times New Roman CE;}} \viewkind4\uc1\pard\f0\fs20 Processing of non-isothermal TG data \par }

Decomposition of dichlorodifluoromethane in thermal plasma was investigated theoretically by computing the equilibrium composition of the gas mixtures involving carbon, chlorine and fluorine in presence of argon (which is assumed to be the main plasma gas) and/or in addition of hydrogen and calcium together with hydrogen. The calculations were carried out for the temperature range between 500 and 6000 K and for the total pressure of the system of 1 bar. Use is made of the fact that a thermal plasma is a plasma in (local) thermal equilibrium, which makes possible the theoretical determination of its equilibrium composition at definite temperature by employing Gibbs free energy data for the compounds present in the system and assuming that the equilibrium of the system corresponds to its minimum energy state. The results of calculations show that toxic molecules and radicals can be, under convenient conditions (appropriate temperature and amount of added substances), converted into stable non-toxic species like CaF₂ and CaCl₂.     

{\rtf1\ansi\ansicpg1250\deff0\deflang1038\deflangfe1038\deftab708{\fonttbl{\f0\froman\fprq2\fcharset238{\*\fname Times New Roman;}Times New Roman CE;}} \viewkind4\uc1\pard\f0\fs24 Digital signal processing in prompt-gamma activation analysis \par }

Summary The International Data Centre of the Comprehensive Nuclear-Test-Ban Treaty Organisation receives atmospheric radioactivity data from the monitoring stations of the International Monitoring System. The Centre is a processing hub through which raw data and analysis results flow to Treaty Member States. Data are processed automatically upon receipt, and then interactively reviewed and screened for detection of CTBT-relevant radionuclides. Atmospheric back-tracking for source location is included in the IDC functions. This paper describes the role of the IDC in this verification effort, the types of radionuclide monitoring data received, the automatic and interactive processing, and the products distributed to Member States.     

{\rtf1\ansi\ansicpg1250\deff0\deflang1038\deflangfe1038\deftab708{\fonttbl{\f0\froman\fprq2\fcharset238{\*\fname Times New Roman;}Times New Roman CE;}} \viewkind4\uc1\pard\f0\fs20 Saturation determination of micellar systems using isothermal titration calorimetry \par }

A novel method for the determination of the point of micellar saturation has been developed. To exemplify the theory a model system was considered, this being the saturation of two aqueous micellar solvents with dimethyl phthalate ester (DMP). Upon addition of a hydrophobic compound to an aqueous micellar system partitioning will occur. On further addition, the inner hydrophobic regions will eventually be unable to accommodate any more DMP and, at this specific concentration, the micelle is saturated. With a comparatively large enthalpy change upon partitioning the point of saturation can be determined by a corresponding significant reduction in enthalpy change.     

The vinyloxonium cation, \documentclass{article}\pagestyle{empty}\begin{document}${\rm CH}_{\rm 2} = {\rm CH - }\mathop {\rm O}\limits^{\rm + } {\rm H}_{\rm 2}$\end{document}, a stable [C2H5O]+ species in the gas phase

The charge stripping mass spectra of [C₂H₅O]⁺ ions permit the clear identification of four distinct species: \documentclass{article}\pagestyle{empty}\begin{document}${\rm CH}_{\rm 3} - {\rm O - }\mathop {\rm C}\limits^{\rm + } {\rm H}_{\rm 2}$\end{document}, \documentclass{article}\pagestyle{empty}\begin{document}${\rm CH}_{\rm 3} - \mathop {\rm C}\limits^{\rm + } {\rm H - OH}$\end{document}, and \documentclass{article}\pagestyle{empty}\begin{document}${\rm CH}_{\rm 2} = {\rm CH - }\mathop {\rm O}\limits^{\rm + } {\rm H}_{\rm 2}$\end{document}. The latter, the vinyloxonium ion, has not been identified before. It is generated from ionized n-butanol and 1,3-propanediol. Its heat of formation is estimated to be 623±12 kJ mol^?1. The charge stripping method is more sensitive to these ion structures than conventional collisional activation, which focuses attention on singly charged fragment ions.     

Structure and formation of gaseous [C4H5O]+ ions. I—isomeric ions of the type C3H5\documentclass{article}\pagestyle{empty}\begin{document} $\mathop {\rm C}\limits^ + =\!= $\end{document}O

Characterization of [C₄H₅O]⁺ ions in the gas phase using their collisional activation spectra shows that the four C₃H₅\documentclass{article}\pagestyle{empty}\begin{document} $\mathop {\rm C}\limits^ + =\!= $\end{document}O isomers CH₂?C(CH₃)\documentclass{article}\pagestyle{empty}\begin{document} $\mathop {\rm C}\limits^ + =\!= $\end{document}O, CH₂?CHCH₂\documentclass{article}\pagestyle{empty}\begin{document} $\mathop {\rm C}\limits^ + =\!= $\end{document}O, CH₃CH?CH\documentclass{article}\pagestyle{empty}\begin{document} $\mathop {\rm C}\limits^ + =\!= $\end{document}O and ?? \documentclass{article}\pagestyle{empty}\begin{document} $\mathop {\rm C}\limits^ + =\!= $\end{document}O are stable for ≥ 10^?5 s. It is concluded further from the characteristic shapes for the unimolecular loss of CO from C₃H₅\documentclass{article}\pagestyle{empty}\begin{document} $\mathop {\rm C}\limits^ + =\!= $\end{document}O ions generated from a series of precursor molecules that the CH₂?CH(CH₃)\documentclass{article}\pagestyle{empty}\begin{document} $\mathop {\rm C}\limits^ + =\!= $\end{document}O- and CH₂?CHCH₂\documentclass{article}\pagestyle{empty}\begin{document} $\mathop {\rm C}\limits^ + =\!= $\end{document}O-type ions dissociate over different potential surfaces to yield [allyl]⁺ and [2-propenyl]⁺ [C₃H₅]⁺ product ions respectively. Cyclopropyl carbonyl-type ions lose CO with a large kinetic energy release, which points to ring opening in the transition state, whereas this loss from CH₃CH?CH\documentclass{article}\pagestyle{empty}\begin{document} $\mathop {\rm C}\limits^ + =\!= $\end{document}O-type ions is proposed to occur via a rate determining 1,2-H shift to yield 2-propenyl cations.     

Applications of NMR spectroscopy of chiral association complexes 5. Stereodynamics and diastereotopism in chiral 1,3-dienes \documentclass{article}\pagestyle{empty}\begin{document}${\rm HOCMe}_{\rm 2} \rlap{--} ({\rm CCl =\!= CCl\rlap{--})}_{\rm 2} {\rm X}$\end{document}

The barriers to partial rotation around the central single bond in chiral dienes \documentclass{article}\pagestyle{empty}\begin{document}${\rm HOCMe}_{\rm 2} \rlap{--} ({\rm CCl =\!= CCl\rlap{--})}_{\rm 2} {\rm X}$\end{document} have been determined by coalescence of either ¹H NMR signals (X = CH₂OCH₃) or ¹³C NMR signals (X = H). In the presence of the optically active shift reagent (+) ? Eu(hfbc)₃ all ¹H signals were split at temperatures where the interconversion of enantiomers is slow. The temperature dependence of these spectra also yielded free activation enthalpies for the enantiomerizations which were in agreement with the ones obtained without Eu(hfbc)₃. The assignment of the four methyl resonances appearing in the presence of (+) ? Eu(hfbc)₃ at low temperature was possible by gradually increasing the rate of enantiomerization or gradually replacing the optically active auxiliary compound by the racemic one.     

Multiplet structure of the K_{\alpha _{1, 2} } and K_{\beta _1 \beta '} lines in the X-ray spectra of iron compounds

The displacements in the intensity maxima and centers of gravity of the \(K_{\alpha _1 \alpha _{2^ - } } \) and \(K_{\beta _1 \beta '} \) lines in the x-ray spectra of iron compounds are determined. These values vary regularly with the effetive charge on the atom and with the number of unshared 3d electrons. The results are compared with theory.     

Stable γ-distonic oxonium ions: R\documentclass{article}\pagestyle{empty}\begin{document}$ \mathop {\rm O}\limits^ + $\end{document}HCHR′ĊH2CHR″ and their characteristic reaction

The γ-distonic radical ions R$ \mathop {\rm O}\limits^ + $CHR′CH₂?HR″ and their molecular ion counterparts R$ \mathop {\rm O}\limits^{{\rm + } \cdot } $CHR′CH₂CH₂R″ have been studied by isotopic labelling and collision-induced dissociation, applying a potential to the collision cell in order to separate activated from spontaneous decompositions. The stability of CH₃$ \mathop {\rm O}\limits^ + $HCH(CH₃)CH₂?HCH₃, C₂H₅$ \mathop {\rm O}\limits^ + $HCH(CH₃)CH₂?HCH₃, CH₃$ \mathop {\rm O}\limits^ + $HCH(CH₃)CH₂?H₂, CH₃$ \mathop {\rm O}\limits^ + $HCH₂CH₂?HCH₃ and C₂H₅$ \mathop {\rm O}\limits^ + $HCH₂CH₂?HCH₃, has been demonstrated and their characteristic decomposition, alcohol loss, identified. For all these γ-distonic ions, the 1,4-H abstraction leading to their molecular ion counterpart exhibits a primary isotope effect.     

Isolated Pd Sites on the Intermetallic PdGa(111) and PdGa($\bar 1$$\bar 1$$\bar 1$) Model Catalyst Surfaces

Scratching the surface: The high selectivity of PdGa catalysts towards the partial hydrogenation of acetylene was previously attributed to the separation of Pd atomic sites at the surfaces. The atomic structures of PdGa surfaces are determined by means of a combined experimental and computational approach, allowing investigation of the catalytic dissociation of hydrogen. The two opposite (111) and ${{\left( {\bar 1\bar 1\bar 1} \right)}}$ surfaces show a very different arrangement of catalytic centers.     

Mass spectrometry of transition-metal π-complexes. III—a study of an iron-coordinated tautomer of phenol

A study of the fragmentation of the \documentclass{article}\pagestyle{empty}\begin{document}$ \left[{\left({{\rm C}_{\rm 6} {\rm H}_{\rm 6} {\rm O}} \right){\rm Fe}} \right]_{}^{_.^ + } $\end{document} ion formed from two different precursors suggests that the ions adopt different structures over that part of the energy distribution giving rise to decomposition in the ion source.     

利用原位APXPS与STM研究H2在ZnO(10${\rm{\bar 1}}$0)表面的活化

Cu/ZnO/Al₂O₃是工业中最广泛使用的甲醇合成催化剂。然而该催化反应的活性位点和机理目前仍存争议。H₂作为反应物之一,研究其在ZnO表面的活化和解离对于弄清甲醇合成反应的催化机理具有重要的帮助。本工作利用近常压光电子能谱(APXPS)和扫描隧道显微镜(STM)原位研究了H₂在ZnO(10${\rm{\bar 1}}$0)表面上的活化和解离。APXPS结果表明：在0.3 mbar (1 mbar = 100 Pa)的H₂气氛中,室温下ZnO表面形成羟基(OH)吸附物种。STM实验发现通入H₂后ZnO表面发生了(1×1)到(2×1)的重构。上述结果和原子H在ZnO(10${\rm{\bar 1}}$0)表面的吸附结果一致。然而吸附H₂O可以导致同样的现象。因此,我们还开展了H₂O在ZnO(10${\rm{\bar 1}}$0)表面吸附的对比实验。结果表明：H₂气氛中ZnO表面发生0.3 eV的能带弯曲,而H₂O吸附实验中几乎观察不到能带弯曲发生。同时,热稳定性实验表明H₂气氛中ZnO表面的OH不同于H₂O解离吸附产生的OH,前者具有更高的脱附温度。因此,本工作的结果表明常温和常压下H₂在ZnO(10${\rm{\bar 1}}$0)表面发生解离吸附。这一结果和以往超高真空下未发现H₂在ZnO(10${\rm{\bar 1}}$0)表面上的解离不同,说明H₂的活化是一个压力依赖过程。     

Structures and formation of \documentclass{article}\pagestyle{empty}\begin{document}$ \left[{{\rm C}_{{\rm 4}} {\rm H}_{{\rm 8}} } \right]_{}^{_.^ + } $\end{document} ions

Several \documentclass{article}\pagestyle{empty}\begin{document}$ \left[{{\rm C}_{{\rm 4}} {\rm H}_{{\rm\ 8}} } \right]_{}^{_.^ + } $\end{document} ion isomers yield characteristic and distinguishable collisional activation spectra: \documentclass{article}\pagestyle{empty}\begin{document}$ \left[{{\rm 1-butene} } \right]_{}^{_.^ + } $\end{document} and/or \documentclass{article}\pagestyle{empty}\begin{document}$ \left[{{\rm 2-butene} } \right]_{}^{_.^ + } $\end{document} (a-b), \documentclass{article}\pagestyle{empty}\begin{document}$ \left[{{\rm isobutene} } \right]_{}^{_.^ + } $\end{document} (c) and [cyclobutane]⁺ (e), while the collisional activation spectrum of \documentclass{article}\pagestyle{empty}\begin{document}$ \left[{{\rm methylcyclopropane} } \right]_{}^{_.^ + } $\end{document} (d) could also arise from a combination of a-b and c. Although ready isomerization may occur for \documentclass{article}\pagestyle{empty}\begin{document}$ \left[{{\rm C}_{{\rm 4}} {\rm H}_{{\rm 8}} } \right]_{}^{_.^ + } $\end{document} ions of higher internal energy, such as d or e → a, b, and/or c, the isomeric product ions identified from many precursors are consistent with previously postulated rearrangement mechanisms. 1,4-Eliminations of HX occur in 1-alkanols and, in part, 1-buthanethiol and 1-bromobutane. The collisional activation data are consistent with a substantial proportion of 1,3-elimination in 1- and 2-chlorobutane, although 1,2-elimination may also occur in the latter, and the formation of the methylcycloprpane ion from n-butyl vinyl ether and from n-butyl formate. Surprisingly, cyclohexane yields the \documentclass{article}\pagestyle{empty}\begin{document}$ \left[{{\rm linear butene} } \right]_{}^{_.^ + } $\end{document} ions a-b, not \documentclass{article}\pagestyle{empty}\begin{document}$ \left[{{\rm cyclobutane} } \right]_{}^{_.^ + } $\end{document}, e.