Turbulent diffusion and mixing in interstellar dark clouds with adsorption onto grains

This paper reports the results of models of dark cloud chemistry incorporating a depth dependent density distribution with diffusive mixing and adsorption onto grains. The model is based on the approach taken by Xie et al. (1995), with the addition of grain accretion effects. Without diffusion, the central regions of the cloud freeze out in less than 10(7) years. Freeze-out time is dependent on density, so the diffuse outer region of the cloud remains abundant in gas for about an order of magnitude longer. We find that fairly small amounts of diffusive mixing can delay freeze-out at the centre of the model cloud for a time up to an order of magnitude greater than without diffusion, due to material diffusing inward from the edges of the cloud. The gas-phase lifetime of the cloud core can thus be increased by up to an order of magnitude or more by this process. We have run three different grain models with various diffusion coefficients to investigate the effects of changing the sticking parameters.

Light emission from gold and silver thin films in a scanning tunneling microscope: role of contamination and interpretation of grain structure in photon maps

Scanning tunnelling microscope (STM) tip-induced light emission from Au and Ag has been studied. Thin film samples similar to100nm thick were prepared by thermal evaporation at 0.5nm/s onto a room-temperature glass substrate to produce grains of 20-50nm in lateral dimension at the surface. Light emission from the samples in the STM was quasi-simultaneously recorded with the topography, at 1.8V tip bias and 3-40nA current, alternating pixel by pixel at the same bias. Typically, a surface scan range of 150 nm x 150 nm was surveyed. Au, W and PtIr tips were used.

Theoretical and experimental correlations of gas dissolution, diffusion, and thermodynamic properties in determination of gas permeability and selectivity in supported ionic liquid membranes

Supported ionic liquid membranes (SILMs) has the potential to be a new technological platform for gas/organic vapour separation because of the unique non-volatile nature and discriminating gas dissolution properties of room temperature ionic liquids (ILs). This work starts with an examination of gas dissolution and transport properties in bulk imidazulium cation based ionic liquids [C_nmim][NTf2] (n = 2.4, 6, 8.10) from simple gas H₂, N₂, to polar CO₂, and C₂H₆, leading to a further analysis of how gas dissolution and diffusion are influenced by molecular specific gas-SILMs interactions, reflected by differences in gas dissolution enthalpy and entropy. These effects were elucidated again during gas permeation studies by examining how changes in these properties and molecular specific interactions work together to cause deviations from conventional solution–diffusion theory and their impact on some remarkably contrasting gas perm-selectivity performance. The experimental perm-selectivity for all tested gases showed varied and contrasting deviation from the solution–diffusion, depending on specific gas-IL combinations. It transpires permeation for simpler non-polar gases (H₂, N₂) is diffusion controlled, but strong molecular specific gas-ILs interactions led to a different permeation and selectivity performance for C₂H₆ and CO₂. With exothermic dissolution enthalpy and large order disruptive entropy, C₂H₆ displayed the fastest permeation rate at increased gas phase pressure in spite of its smallest diffusivity among the tested gases. The C₂H₆ gas molecules “peg” on the side alkyl chain on the imidazulium cation at low concentration, and are well dispersed in the ionic liquids phase at high concentration. On the other hand strong CO₂-ILs affinity resulted in a more prolonged “residence time” for the gas molecule, typified by reversed CO₂/N₂ selectivity and slowest CO₂ transport despite CO₂ possess the highest solubility and comparable diffusivity in the ionic liquids. The unique transport and dissolution behaviour of CO₂ are further exploited by examining the residing state of CO₂ molecules in the ionic liquid phase, which leads to a hypothesis of a condensing and holding capacity of ILs towards CO₂, which provide an explanation to slower CO₂ transport through the SILMs. The pressure related exponential increase in permeations rate is also analysed which suggests a typical concentration dependent diffusion rate at high gas concentration under increased gas feed pressure. Finally the strong influence of discriminating and molecular specific gas-ILs interactions on gas perm-selectivity performance points to future specific design of ionic liquids for targeted gas separations.

Comparative study on transport properties for LiFAP and LiPF6 in alkyl-carbonates as electrolytes through conductivity, viscosity and NMR self-diffusion measurements

We present in this work a comparative study on density and transport properties, such as the conductivity (sigma), viscosity (eta) and self-diffusion coefficients (D), for electrolytes based on the lithium hexafluorophosphate, LiPF6; or on the lithium tris(pentafluoroethane)-trifluorophosphate, LiFAP dissolved in a binary mixture of ethylene carbonate (EC) and dimethylcarbonate (DMC) (50:50 wt%). For each electrolyte, the temperature dependence on transport properties over a temperature range from 10 to 80 degrees C and 20 to 70 degrees C for viscosity and conductivity, respectively, exhibits a non-Arrhenius behavior. However, this dependence is correctly correlated by using the Vogel-Tamman-Fulcher (VTF) type fitting equation. In each case, the best-fit parameters, such as the pseudo activation energy and ideal glass transition temperature were then extracted. The self-diffusion coefficients (D) of the Li+ cation and PF6- or FAP(-) anions species, in each studied electrolyte, were then independently determined by observing Li-3, F-19 and P-31 nuclei with the pulsed-gradient spin-echo (PGSE) NMR technique over the same temperature range from 20 to 80 degrees C. Results show that even if the diffusion of the lithium cation is quite similar in both electrolytes, the anions diffusion differs notably. In the case of the LiPF6-based electrolyte, for example at T approximate to 75 degrees C (high temperature), the self-diffusion coefficients of Li+ cations in solution (D (Li+)approximate to 5 x 10(-19) m(2) s(-1)) is 1.6 times smaller than that of PF6- anions (D (PF6-) = 8.5 x 10(-19) m(2) s(-1)), whereas in the case of the LiFAP-based electrolyte, FAP(-) anions diffuse at same rate as the Li+ cations (D (FAP(-)) = 5 x 10(-1) m(2) s(-1)). Based on these experimental results, the transport mobility of ions were then investigated through Stokes-Einstein and Nernst-Einstein equations to determine the transport number of lithium t(Li)(+), effective radius of solvated Li+ and of PF6- and FAP(-) anions, and the degree of dissociation of these lithium salts in the selected EC/DMC (50:50 wt%) mixture over a the temperature range from 20 to 80 degrees C. This study demonstrates the conflicting nature of the requirements and the advantage of the well-balanced properties as ionic mobility and dissociation constant of the selected electrolytes. (C) 2013 Elsevier Ltd. All rights reserved.

Electrooxidation of the iodides [C(4)mim]I, LiI, NaI, KI, RbI, and CsI in the room temperature ionic liquid [C(4)mim][NTf2]

The electrochemical oxidation of 1-butyl-3-methylimidazolium iodide, [C(4)mim]I, has been investigated by cyclic voltammetry at a platinum microelectrode at varying concentrations in the RTIL 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [C(4)mim][NTf2]. Two oxidation peaks were observed. The first peak is assigned to the oxidation of iodide to triiodide, in an overall two-electron process: 3I(-)- 2e(-) -> I-3(-). At higher potentials, the electrogenerated triiodide oxidizes to iodine, in an overall one-electron process: I-3(-) - e(-) -> 3/2I(2). An average diffusion coefficient, D, for I- of 1.55 x 10(-11) m(2) s(-1) was obtained. A digital simulation program was used to simulate the voltammetric response, and kinetic parameters were successfully extracted. The parameters deduced from the simulation include D for I-, I-3(-), and I-2 and K-eq,K-2, the equilibrium constant for the reaction of iodide and iodine to form triiodide. Values for these parameters are of the same order as those previously published for the oxidation of Br- in the same RTIL [Allen et al. J. Electroanal. Chem. 2005, 575, 311]. Next, the cyclic voltammetry of five different inorganic iodide salts was studied by dissolving small amounts of the solid in [C(4)mim][NTf2]. Similar oxidation peaks were observed, revealing diffusion coefficients of ca. 0.55, 1.14, 1.23, 1.44, and 1.33 x 10(-11) m(2) s(-1) and solubilities of 714, 246, 54, 83, and 36 mM for LiI, NaI, KI, RbI, and CsI, respectively. The slightly smaller diffusion coefficients for the XI salts (compared to [C(4)mim]I) may indicate that I- is ion-paired with Li+, Na+, K+, Rb+, and Cs+ in the RTIL medium.

An electrochemical study of PCl3 and POCl3 in the room temperature ionic liquid [C(4)mpyrr][N(Tf)(2)]

Voltammetric studies of PCl3 and POCl3 have not been reported in the literature to date, probably due to the instability of these molecules in conventional aprotic solvents giving unstable and irreproducible results. From a previous study [Amigues et al. Chem. Commun. 2005, 1-4], it was found that ionic liquids have the ability to offer a uniquely stable solution phase environment for the study of these phosphorus compounds. Consequently, the electrochemistry of PCl3 and POCl3 has been studied by cyclic voltammetry on a gold microelectrode in the ionic liquid [C(4)mpyrr][N(Tf)(2)] (1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl) imide). For both compounds, reduction and oxidation waves were observed and a tentative assignment of the waves is given. For PCl3, the reduction was thought to proceed via the following mechanism: PCl3 + e(-) h reversible arrow PCl3-, PCl3- reversible arrow Cl- + (PCl2)-Cl-center dot, (and) Cl- + PCl3 h PCl4-. For POCl3, the suggested reduction mechanism was analogous to that of PCl3: POCl3 + e(-) reversible arrow POCl3-, POCl3- reversible arrow Cl- + (POCl2)-O-center dot, and Cl- + POCl3 h POCl4-. In both cases (PCl2)-Cl-center dot and (POCl2)-O-center dot are likely to engage in further reactions. Potential step microdisk chronoamperometry was carried out on the reductive waves of PCl3 and POCl3 to measure diffusion coefficients and number of electrons transferred. It was found that the diffusion of PCl3 was unusually slow (3.1 x 10(-12) m(2) s(-1)): approximately 1 order of magnitude less than that for POCl3 (2.2 x 10(-11) m(2) s(-1)). For both PCl3 and POCl3, a

Troubled Geographies: A Spatial History of Religion and Society in Ireland

Ireland’s landscape is marked by fault lines of religious, ethnic, and political identity that have shaped its troubled history. Troubled Geographies maps this history by detailing the patterns of change in Ireland from 16th century attempts to “plant” areas of Ireland with loyal English Protestants to defend against threats posed by indigenous Catholics, through the violence of the latter part of the 20th century and the rise of the “Celtic Tiger.” The book is concerned with how a geography laid down in the 16th and 17th centuries led to an amalgam based on religious belief, ethnic/national identity, and political conviction that continues to shape the geographies of modern Ireland. Troubled Geographies shows how changes in religious affiliation, identity, and territoriality have impacted Irish society during this period. It explores the response of society in general and religion in particular to major cultural shocks such as the Famine and to long term processes such as urbanization.

Carbonation and pH in Mortars Manufactured with Supplementary Cementitious Materials

An investigation of carbonation in mortars and methods of measuring the degree of carbonation and pH change is presented. The mortars were manufactured using ordinary portland cement, pulverized fuel ash, ground granulated blast-furnace slag, metakaolin, and microsilica. The mortars were exposed to a carbon dioxide-rich environment 5% CO2 to accelerate carbonation. The resulting carbonation was measured using phenolphthalein indicator and thermogravimetric analysis. The pH of the pore fluid and a powdered sample, extracted from the mortar, was measured to give an accurate indication of the actual pH of the concrete. The pH of the extracted powder mortar sample was found to be similar to the pH of the pore fluid expressed from the mortars. The thermogravimetric analysis suggested two distinct regions of transport of CO2 within mortar, a surface region where convection was prevalent and a deeper region where diffusion was dominant. The use of microsilica has been shown to decrease the rate of carbonation, while pulverized fuel ash and ground granulated blast-furnace slag have a detrimental effect on carbonation. Metakaolin has little effect on carbonation.

The Diffusion of Risks in Public Private Partnership Contracts

Purpose The UK government argues that the benefits of public private partnership (PPP) in delivering public infrastructure stem from: transferring risks to the private sector within a structure in which financiers put their own capital at risk; and, the performance based payment mechanism, reinforced by the due diligence requirements imposed by the lenders financing the projects (HM Treasury, 2010). Prior studies of risk in PPPs have investigated ‘what’ risks are allocated and to ‘whom’, that is to the public or the private sector. The purpose of this study is to examine ‘how’ and ‘why’ PPP risks are diffused by their financiers. Design/methodology/approach This study focuses on the financial structure of PPPs and on their financiers. Empirical evidence comes from interviews conducted with equity and debt financiers. Findings The findings show that the financial structure of the deals generates risk aversion in both debt and equity financiers and that the need to attract affordable finance leads to risk diffusion through a network of companies using various means that include contractual mitigation through insurance, performance support guarantees, interest rate swaps and inflation hedges. Because of the complexity this process generates, both procurers and suppliers need expensive expert advice. The risk aversion and diffusion and the consequent need for advice add cost to the projects impacting on the government’s economic argument for risk transfer. Limitations and implications The empirical work covers the private finance initiative (PFI) type of PPP arrangements and therefore the risk diffusion mechanisms may not be generalisable to other forms of PPP, especially those that do not involve the use of high leverage or private finance. Moreover, the scope of this research is limited to exploring the diffusion of risk in the private sector. Further research is needed on how risk is diffused in other settings and on the value for money implication of risk diffusion in PPP contracts. Originality/value The expectation inherent in PPP is that the private sector will better manage those risks allocated to it and because private capital is at risk, financiers will perform due diligence with the ultimate outcome that only viable projects will proceed. This paper presents empirical evidence that raises questions about these expectations. Key words: public private partnership, risk management, diffusion, private finance initiative, financiers

Scattering theory of cooling and heating in optomechanical systems

We present a one-dimensional scattering theory which enables us to describe a wealth of effects arising from the coupling of the motional degree of freedom of scatterers to the electromagnetic field. Multiple scattering to all orders is taken into account. The theory is applied to describe the scheme of a Fabry-Perot resonator with one of its mirrors moving. The friction force, as well as the diffusion, acting on the moving mirror is derived. In the limit of a small reflection coefficient, the same model provides for the description of the mechanical effect of light on an atom moving in front of a mirror.

Transient distributions of composition and temperature in a gas-solid packed bed reactor by near-infrared tomography

Near-infrared diffuse tomography was used in order to observe dynamic behaviour of flowing gases by measuring the 3D distributions of composition and temperature in a weakly scattering packed bed reactor, subject to wall effects and non-isothermal conditions. The technique was applied to the vapour phase hydrogen isotopic exchange reaction in a hydrophobic packing of low aspect ratio made of platinum on styrene divinyl benzene sulphonate copolymer resin. The results of tomography revealed uneven temperature and composition maps of water and deuterated water vapours in the core-packed bed and in the vicinity of the wall owing to flow maldistribution. The dynamic lag between the near-wall water vapour and deuterated water vapour compositions were observed suggesting that the convective transfer which was significant near the wall at the start, owing to high porosity, was also effective at large conversions. (C) 2012 Elsevier B.V. All rights reserved.