A challenge to the Delta G~0 interpretation of hydrogen evolution

Platinum is a nearly perfect catalyst for the hydrogen evolution reaction, and its high activity has conventionally been explained by its close-to-thermoneutral hydrogen binding energy (G~0). However, many candidate non-precious metal catalysts bind hydrogen with similar strengths, but exhibit orders-of-magnitude lower activity for this reaction. In this study, we employ electronic structure methods that allow fully potential-dependent reaction barriers to be calculated, in order to develop a complete working picture of hydrogen evolution on platinum. Through the resulting ab initio microkinetic models, we assess the mechanistic origins of Pt's high activity. Surprisingly, we find that the G~0 hydrogen atoms are kinetically inert, and that the kinetically active hydrogen atoms have G's much weaker, similar to that of gold. These on-top hydrogens have particularly low barriers, which we compare to those of gold, explaining the high reaction rates, and the exponential variations in coverages can uniquely explain Pt's strong kinetic response to the applied potential. This explains the unique reactivity of Pt that is missed by conventional Sabatier analyses, and suggests true design criteria for non-precious alternatives

Split-screen single-camera stereoscopic PIV application to a turbulent confined swirling layer with free surface

An annular liquid wall jet, or vortex tube, generated by helical injection inside a tube is studied experimentally as a possible means of fusion reactor shielding. The hollow confined vortex/swirling layer exhibits simultaneously all the complexities of swirling turbulence, free surface, droplet formation, bubble entrapment; all posing challenging diagnostic issues. The construction of flow apparatus and the choice of working liquid and seeding particles facilitate unimpeded optical access to the flow field. A split-screen, single-camera stereoscopic particle image velocimetry (SPIV) scheme is employed for flow field characterization. Image calibration and free surface identification issues are discussed. The interference in measurements of laser beam reflection at the interface are identified and discussed. Selected velocity measurements and turbulence statistics are presented at Re_λ = 70 (Re = 3500 based on mean layer thickness)

Scaled and Dynamic Optimizations of Nudged Elastic Bands

We present a modified nudged elastic band routine that can reduce the number of force calls by more than 50% for bands with non-uniform convergence. The method, which we call "dyNEB", dynamically and selectively optimizes states based on the perpendicular forces and parallel spring forces acting on that region of the band. The convergence criteria are scaled to focus on the region of interest, i.e., the saddle point, while maintaining continuity of the band and avoiding truncation. We show that this method works well for solid state reaction barriers---non-electrochemical in general and electrochemical in particular---and that the number of force calls can be significantly reduced without loss of resolution at the saddle point

Subnational Government Bailouts in OECD Countries: Four Case Studies

We present four case studies of bailouts of subnational governments in Australia, Germany, Italy and Sweden. The case studies show that bailouts can occur in a diverse set of institutions shaping the relations between central and subnational governments. Surpisingly, there is little evidence in favor of the `too big to fail` argument explaining bailouts. In contrast, elements of political favoritism play some role in most cases. The cases also indicate the importance of properly designing principal-agent relationships in the decentralization of public finances. Constitutional mandates for uniform provision of public services and attempts by the central government to dominate subnational governments in matters of fiscal policy seem to be conducive to bailouts.

EXPRESSION OF A FUNCTIONAL CHIMERIC lg-MHC CLASS II PROTEIN

composed of the a- and ß-chains of the MHC class I1 I-E molecule fused to antibody V regions derived from anti-human CD4 mAb MT310. Expression vectors were constructed containing the functional, rearranged gene segments coding for the V region domains of the antibody H and L chains in place of the first domains of the complete structural genes of the I-E a- and ß-chains, respectively. Celltsr ansfected with both hybrid genes expressed a stable protein product on the cell surface. The chimeric molecule exhibited the idiotype of the antibody MT310 as shown by binding to the anti-idiotypic mAb 20-46. A protein of the anticipated molecular mass was immunoprecipitated witha nti-mouse IgG antiserum. Furthermore, human soluble CD4 did bind to thetr ansfected cell line, demonstrating that the chimeric protein possessed the binding capacity of the original mAb. Thus, the hybrid molecule retained: 1) the properties of a MHC class I1 protein with regardt o correct chain assembly and transport to the cell surface: as well as 2) the Ag binding capacity of the antibody genes used. Thgee neration of hybrid MHC class I1 molecules with highly specific, non-MHC-restricted bindingc apacities will be useful for studying MHC class 11-mediated effector functions such as selection of the T cell repertoire in thymus of transgenic mice

An overview of modeling methods for thermal mixing and stratification in large enclosures for reactor safety analysis

Thermal mixing and stratification phenomena play major roles in the safety of reactor systems with large enclosures, such as containment safety in current fleet of LWRs, long-term passive containment cooling in Gen III+ plants including AP-1000 and ESBWR, the cold and hot pool mixing in pool type sodium cooled fast reactor systems (SFR), and reactor cavity cooling system behavior in high temperature gas cooled reactors (HTGR), etc. Depending on the fidelity requirement and computational resources, 0-D steady state models (heat transfer correlations), 0-D lumped parameter based transient models, 1-D physical-based coarse grain models, and 3-D CFD models are available. Current major system analysis codes either have no models or only 0-D models for thermal stratification and mixing, which can only give highly approximate results for simple cases. While 3-D CFD methods can be used to analyze simple configurations, these methods require very fine grid resolution to resolve thin substructures such as jets and wall boundaries. Due to prohibitive computational expenses for long transients in very large volumes, 3-D CFD simulations remain impractical for system analyses. For mixing in stably stratified large enclosures, UC Berkeley developed 1-D models basing on Zuber’s hierarchical two-tiered scaling analysis (HTTSA) method where the ambient fluid volume is represented by 1-D transient partial differential equations and substructures such as free or wall jets are modeled with 1-D integral models. This allows very large reductions in computational effort compared to 3-D CFD modeling. This paper will present an overview on important thermal mixing and stratification phenomena in large enclosures for different reactors, major modeling methods and their advantages and limits, potential paths to improve simulation capability and reduce analysis uncertainty in this area for advanced reactor system analysis tools

EXPERIMENTAL INVESTIGATION OF MIXED CONVECTION HEAT TRANSFER CAUSED BY FORCED-JETS IN LARGE ENCLOSURE

ABSTRACT This research investigates experimentally mixed convection and heat transfer augmentation by forced jets in a large enclosure, at conditions simulating those of actual passive containment cooling systems and scales approaching those of actual containment buildings or compartments. The experiment was designed to measure the key parameters governing the heat transfer augmentation by forced jets and investigate the effects of geometric factors, including the jet diameter, jet injection orientation, interior structures, and enclosure aspect ratio. The tests cover a variety of injection modes leading to flow configurations of interest that contribute to reveal the nature of mixing and stratification phenomena in the containment under accident conditions of interest. By nondimensionalizing the governing equations, the heat transfer of mixed convection can be predicted to be controlled by jet Archimedes number and geometric factors. Using a combining rule for mixed convection and appropriate forced and natural convection models, the correlations of heat transfer augmentation by forced jets are developed and then tested by experimental data. The effects of jet diameter, injection orientation, interior structures, and enclosure aspect ratio on heat transfer augmentation are illustrated with analysis of experimental results

One-Dimensional Analysis of Thermal Stratification in AHTR and SFR Coolant Pools

Thermal stratification phenomena are very common in pool type reactor systems, such as the liquid-salt cooled Advanced High Temperature Reactor (AHTR) and liquid-metal cooled fast reactor systems such as the Sodium Fast Reactor (SFR). It is important to accurately predict the temperature and density distributions both for design optimation and accident analysis. Current major reactor system analysis codes such as RELAP5 (for LWR’s, and recently extended to analyze high temperature reactors), TRAC (for LWR’s), and SASSYS (for liquid metal fast reactors) only provide lumped-volume based models which can only give very approximate results and can only handle simple cases with one mixing source. While 2-D or 3-D CFD methods can be used to analyze simple configurations, these methods require very fine grid resolution to resolve thin substructures such as jets and wall boundaries, yet such fine grid resolution is difficult or impossible to provide for studying the reactor response to transients due to computational expense. Therefore, new methods are needed to support design optimization and safety analysis of Generation IV pool type reactor systems. Previous scaling has shown that stratified mixing processes in large stably stratified enclosures can be described using one-dimensional differential equations, with the vertical transport by free and wall jets modeled using standard integral techniques. This allows very large reductions in computational effort compared to three-dimensional numerical modeling of turbulent mixing in large enclosures. The BMIX++ (Berkeley mechanistic MIXing code in C++) code was originally developed at UC Berkeley to implement such ideas. This code solves mixing and heat transfer problems in stably stratified enclosures. The code uses a Lagrangian approach to solve 1-D transient governing equations for the ambient fluid and uses analytical or 1-D integral models to compute substructures. By including liquid salt properties, BMIX++ code is extended to analyze liquid salt pool systems in the current AHTR design, to provide an example of its application. Similar analysis is possible for liquid-metal cooled reactors. The current AHTR baseline design uses a large buffer salt tank to provide more thermal inertial and safety margin. Reactor vessel, intermediate heat exchangers, pool reactor auxiliary cooling system heat exchangers (PHX), and direct reactor auxiliary cooling system heat exchangers (DHX) are all immerged in the buffer salt pool. These structures provide major driving sources for vertical mixing and thermal stratification. Predication of the temperature distribution within the buffer salt tank directly affects the major safety systems design, such as the PHX and DHX, safety analysis results, and structure thermal stresses analysis. The BMIX++ code is used to predict mixing and thermal stratification in this pool system. This example shows the potential of 1-D analysis methods and BMIX++ to be included in system analysis codes for pool type of Gen-IV reactor systems