Void-induced dissolution in molecular dynamics simulations of NaCl and water

To gain a better understanding of the interaction of water and NaCl at the surface during dissolution, we have used molecular dynamics to simulate the interface with two equal-sized slabs of solid NaCl and liquid water in contact. The introduction of voids in the bulk of the salt, as well as steps or pits on the surface of the NaCl slab results in a qualitative change of system structure, as defined by radial distribution functions (RDFs). As an example, the characteristic Na-Na RDF for the system changes from regularly spaced narrow peaks (corresponding to an ordered crystalline structure), to a broad primary and smaller secondary peak (corresponding to a disordered structure). The change is observed at computationally short time scales of 100 ps, in contrast with a much longer time scale of 1 mus expected for complete mixing in the absence of defects. The void fraction (which combines both bulk and surface defects) required to trigger dissolution varies between 15%-20% at 300 K and 1 atm, and has distinct characteristics for the physical breakdown of the crystal lattice. The void fraction required decreases with temperature. Sensitivity studies show a strong dependence of the critical void fraction on the quantity and distribution of voids on the surface, with systems containing a balanced number of surface defects and a rough surface showing a maximum tendency to dissolve. There is a moderate dependence on temperature, with a 5% decrease in required void fraction with a 100 K increase in temperature, and a weak dependence on water potential model used, with the SPC, SPC/E, TIP4P, and RPOL models giving qualitatively identical results. The results were insensitive to the total quantity of water available for dissolution and the duration of the simulation.     

Ab initio simulation of carbon clustering on an Ni(111) surface: a model of the poisoning of nickel-based catalysts

In this work, we studied the poisoning of a nickel surface due to carbon. Performing ab initio simulations, within the framework of density functional theory, we computed the surface energy of the nickel (111) surface as a function of carbon coverage. On the basis of these results, we can assert that the stable state of the nickel/carbon surface is either a clean nickel surface or a fully carbon-covered nickel surface, which has a graphitic configuration. The relative stability of the two states depends on the temperature and partial pressure of the carbon gas. At fixed nominal carbon coverage, the most stable configurations are those forming carbon clusters. However, the nickel sites hosting these clusters change from hexagonal close packed/face centered cubic (hcp/fcc) sites to on-top sites when going toward larger clusters. This indicates that poisoning due to graphitic patches occurs on on-top sites.     

A first-principles investigation of LiNH(2) as a hydrogen-storage material: effects of substitutions of K and Mg for Li

Li-N-H compounds hold promise as novel hydrogen-storage materials with high gravimetric hydrogen densities. Because the dehydriding reaction caused by the decomposition of LiNH(2) requires a higher temperature than desired, much effort has been devoted to the destabilization of LiNH(2) to decrease the decomposition temperature. In particular, there has been recent experimental evidence for lowering the temperature by partial substitution of Li by Mg. However, the reason is not clear. In this study, we have employed density functional theory to investigate LiNH(2) and partially Li-substituted systems aiming to understand the effects of the substitution on the destabilization of the NH(2) species. K, a more electropositive element, and Mg, a more electronegative element, have been chosen as two probes to illustrate the effects. We have focused on the investigation of effects of substitutions on the N-H bond strength that is regarded as a qualitative indicator of the decomposition temperature. We have found that in both cases the N-H bonds are weakened, in particular, the Mg substitute appears to be more effective in the destabilization of the NH(2). The relative strength of the metal-N ionic bonding has been found to be a key factor to explain the effects of the substitutes. These have been discussed in detail in terms of Wannier function analyses.     

An Efficient and Rapid Chemoselective Synthesis of α-Aryl-N-methylnitrones Dry Media

Summary.  A simple, efficient, and eco-friendly procedure was developed for the condensation of N-methylhydroxylamine hydrochloride with benzaldehydes bearing electron-donating or electron-withdrawing substituents in the presence of powdered molecular sieves (3 ?) in a solventless system. α-Aryl-N-methylnitrones are obtained in excellent yields (80–100%); similar aromatic ketones do not react under these conditions, rendering the method chemoselective. Received March 26, 2001. Accepted (revised) May 7, 2001     

On linear vertex-arboricity of complementary graphs

The linear vertex-arboricity ρ(G) of a graph G is defined to be the minimum number of subsets into which the vertex set of G can be partitioned such that each subset induces a linear forest. In this paper, we give the sharp upper and lower bounds for the sum and product of linear vertex-arboricities of a graph and its complement. Specifically, we prove that for any graph G of order p. and for any graph G of order p = (2n + 1)², where n ? Z⁺, 2n + 2 ≦ ρ(G) + ρ(G ).     

Induced renal artery stenosis in rabbits: magnetic resonance imaging, angiography, and radionuclide determination of blood volume and blood flow

To investigate the ability of MRI to detect alterations due to renal ischemia, a rabbit renal artery stenosis (RAS) model was developed. Seven rabbits had RAS induced by surgically encircling the artery with a polyethylene band which had a lumen of 1 mm, 1 to 2 weeks prior to imaging. The stenosis was confirmed by angiography, and the rabbits were then imaged in a 1.4 T research MRI unit. T1 was calculated using four inversion recovery sequences with different inversion times. Renal blood flow, using 113Sn-microspheres, and regional water content by drying were then measured. The average T1 of the inner medulla was shorter for the ischemia (1574 msec) than for the contralateral kidney (1849 msec), while no change ws noted in the cortex. Ischemic kidneys had less distinct outer medullary zones on IR images with TI = 600 msec than did contralateral or control kidneys. Blood flow to both the cortex and medulla were markedly reduced in ischemic kidneys compared with contralateral kidneys (119.5 vs. 391 ml/min/100 gm for cortex and 19.8 vs. 50.8 ml/min/100 gm for medulla). Renal water and blood content were less affected. Our rabbit model of renal artery stenosis with MRI, radionuclide, and angiographic correlation has the potential to increase our understanding of MR imaging of the rabbit kidney.     

Minimal separating sets of maximum size

A connected graph G can be disconnected or reduced to a single vertex by removing an appropriate subset of the vertex set V(G), and can be disconnected by removing a suitable subset of the edge set E(G). Attention has usually been centered on separating sets having minimum cardinality, and parameters called the vertex connectivity and the edge connectivity defined. These classical concepts are generalized by using separating sets which are minimal. By considering the maximum as well as the minimum cardinality of such sets, one defines vertex and edge connectivity parameters. Sharp upper bounds are established for these numbers and their values computed for certain classes of graphs. An analogue of Whitney's theorem on connectivity is obtained. Parameters are also defined for minimal separating sets consisting of a mixture of vertices and edges, and these are shown to depend on the maximum and minimum values of the vertex and edge connectivity parameters.     

Novel ionic liquid supported on Fe3O4 nanoparticles as an efficient catalyst for the synthesis of new chromenes

An efficient procedure for the synthesis of new chromenes by the multicomponent reaction of aldehydes, 4‐hydroxycoumarin and 2‐hydroxynaphthalene‐1,4‐dione in the presence of an ionic liquid supported on Fe₃O₄ nanoparticles is described. The ionic liquid supported on Fe₃O₄ nanoparticles as a magnetic catalyst gives products in high yields. Significant features of this method are: short reaction times, excellent yields, green method and use of an effective catalyst that can be recovered and reused many times without loss of its catalytic activity.     

Kinetic modeling of the ethylbenzene/xylene isomerization reaction over HZSM-5 zeolites revisited

In this article, a binderless dealuminated HZSM-5 zeolite (Si/Al = 41.4) was used as a catalyst for the isomerization of a mixture of ethylbenzene and xylene. The experimental results indicated that at low residence times the catalyst is effective to isomerize the ethylbenzene into xylenes. A comprehensive kinetic model considering chemisorption, surface chemical reactions, and diffusional processes was developed for this reaction. The intrinsic activation energy (71.99 kJ mol⁻¹) for the surface reaction of ethylbenzene into m-xylene was calculated for the first time, and the corresponding intrinsic activation energies for o-xylene to m-xylene and m-xylene to p-xylene surface reactions were calculated to be 59.45 and 50.68 kJ mol⁻¹, respectively. Lower apparent values have been reported in the literature, and we rationalize that they correspond to multistep processes and intrinsically include a negative activation energy pertaining to chemisorption. The results also revealed that the ethylbenzene diffusion within the zeolite channels was four orders of magnitude smaller than p-xylene.