Experimental and computational studies of the thermal decomposition of halon 1211

Thermal pyrolysis of halon 1211 (CBrClF₂), diluted in nitrogen, in a tubular alumina reactor, has been studied over the temperature range of 773–1073 K at residence times from 0.3 to 2 s. At temperatures below 973 K, the major products were CCl₂F₂, CBr₂F₂, C₂Cl₂F₄, C₂BrClF₄, C₂F₄, and C₂Br₂F₄. Further increasing temperature resulted in the formation of CBrF₃, CClF₃, and many other species whose formation necessitated the rupture of C? F bonds. Coke formation was also observed on the surface of the reactor at high temperatures. A kinetic reaction scheme involving 16 species and 25 reaction steps was developed and applied to model the thermal pyrolysis of halon 1211 over the temperature range of 773–973 K. Sensitivity analysis suggests that the reaction CBrClF₂ + CClF₂→CCl₂F₂ + CBrF₂ constitutes the major pathway for the decomposition of halon 1211 under the conditions investigated. © 2005 Wiley Periodicals, Inc. Int J Chem Kinet 37: 134–146, 2005     

Search for improved host architectures: application of de novo structure-based design and high-throughput screening methods to identify optimal building blocks for multidentate ethers

This paper presents a computational approach to the deliberate design of improved host architectures. The approach, which involves the use of computer-aided design software, is illustrated by application to cation hosts containing multiple aliphatic ether oxygen binding sites. De novo molecule building software, HostDesigner, is interfaced with molecular mechanics software, GMMX, providing a tool for generating and screening millions of potential bidentate building block structures. Enhanced cation binding affinity can be achieved when highly organized building blocks are used to construct macrocyclic hosts.     

Free Convection Boundary Layer Flow from a Heated Upward Facing Horizontal Flat Plate Embedded in a Porous Medium Filled by a Nanofluid with Convective Boundary Condition

The steady laminar incompressible free convective flow of a nanofluid over a permeable upward facing horizontal plate located in porous medium taking into account the thermal convective boundary condition is studied numerically. The nanofluid model used involves the effect of Brownian motion and the thermophoresis. Using similarity transformations the continuity, the momentum, the energy, and the nanoparticle volume fraction equations are transformed into a set of coupled similarity equations, before being solved numerically, by an implicit finite difference numerical method. Our analysis reveals that for a true similarity solution, the convective heat transfer coefficient related with the hot fluid and the mass transfer velocity must be proportional to x ^−2/3, where x is the horizontal distance along the plate from the origin. Effects of the various parameters on the dimensionless longitudinal velocity, the temperature, the nanoparticle volume fraction, as well as on the rate of heat transfer and the rate of nanoparticle volume fraction have been presented graphically and discussed. It is found that Lewis number, the Brownian motion, and the convective heat transfer parameters increase the heat transfer rate whilst the thermophoresis decreases the heat transfer rate. It is also found that Lewis number and the convective heat transfer parameter enhance the nanoparticle volume fraction rate whilst the thermophoresis parameter decreases nanoparticle volume fraction rate. A very good agreement is found between numerical results of the present article for special case and published results. This close agreement supports the validity of our analysis and the accuracy of the numerical computations.     

Two new rare-class tetracyclic diterpenoids from Otostegia limbata

Two new tetracyclic diterpenoids trivially named as limbatenolide D (1) and limbatenolide E (2) have been isolated from Otostegia limbata. The structure elucidation of the compounds was based primarily on two-dimensional (2D) NMR techniques and on comparison with the literature data.     

The trajectory and stability of a spiralling liquid jet: Viscous theory

We examine a spiralling slender viscous jet emerging from a rapidly rotating orifice, extending Wallwork et al. [I.M. Wallwork, S.P. Decent, A.C. King, R.M.S.M. Schulkes, The trajectory and stability of a spiralling liquid jet. Part 1. Inviscid theory, J. Fluid Mech. 459 (2002) 43–65] by incorporating viscosity. The effects of viscosity on the trajectory of the jet and its linear instability are determined using a mixture of computational and asymptotic methods, and verified using experiments. A non-monotonic relationship between break-up length and rotation rate is demonstrated with the trend varying with viscosity. The sizes of the droplets produced by this instability are determined by considering the most unstable wave mode. It is also found that there is a non-monotonic relationship between droplet size and viscosity. Satellite droplet formation is also considered by analysing very short wavelength modes. The effects of long wavelength modes are examined, and a wave which propagates down the trajectory of the jet is identified for the highly viscous case. A comparison between theoretical and experimental results is made, with favourable agreement. In particular, a quantitative comparison is made between droplet sizes predicted from the theory with experimental observations, with encouraging agreement obtained. Four different types of break-up are identified in our experiments. The experimentally observed break-up mechanisms are discussed in light of our theory.     

1H-1,2,3-triazole,a promising precursor for chemical vapor deposition of hydrogenated carbon nitride

Well-crystallized hydrogenated carbon nitride thin films have been prepared by microwave plasma enhanced chemical vapor deposition (MWPECVD). 1H-1,2,3-triazole+N₂ and Si (1 0 0) were used as precursor and substrate, respectively. Substrate temperature during the deposition was recorded to be 850 °C. The synthesized samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and X-ray photo-electron spectroscopy (XPS) analyses. The plasma compositions were checked by optical emission spectroscopy (OES). XRD observation strongly suggests that the films contain polycrystalline carbon nitride with graphitic structure of (1 0 0), (0 0 2), (2 0 0) and (0 0 4). XPS peak quantification reveals that the atomic ratio of the materials C:N:O:Si is 32:41:18:9. X-ray photo-electron peak deconvolution shows that the most dominant peak of C (1s) and N (1s) narrow scans correspond to sp² hybrid structure of C₃N₄. These observations indicate that 1H-1,2,3-triazole favors the formation of hydrogenated carbon nitride with graphitic phase by CVD method and thus is in good agreement with XRD results. SEM of surface and OES of plasma also support the formation of polycrystalline carbon nitride films from 1H-1,2,3-triazole+N₂ by CVD.     

Submanifolds of generalized $$(k,\mu )$$-space-forms

In this paper, we have studied submanifolds especially, totally umbilical submanifolds of generalized \((k,\mu )\)-space-forms. We have found a necessary and sufficient condition for such submanifolds to be either invariant or anti-invariant. It is also shown that every totally umbilical submanifold of a generalized \((k,\mu )\)-space-form is a pseudo quasi-Einstein manifold.