Voltammetry of oxygen in the room-temperature ionic liquids 1-ethyl-3-methylimidazolium bis((trifluoromethyl)sulfonyl)imide and hexyltriethylammonium bis((trifluoromethyl)sulfonyl)imide: One-electron reduction to form superoxide. Steady-state and transient behavior in the same cyclic voltammogram resulting from widely different diffusion coefficients of oxygen and superoxide

The electrochemical reduction of oxygen in two different room-temperature ionic liquids, 1-ethyl-3-methylimidazolium bis((trifluoromethyl)sulfonyl)imide ([EMIM][N(Tf)(2)]) and hexyltriethylammonium bis((trifluoromethyl)sulfonyl)imide ([N-6222][N(Tf)(2)]) was investigated by cyclic voltammetry at a gold microdisk electrode. Chronoamperometric measurements were made to determine the diffusion coefficient, D, and concentration, c, of the electroactive oxygen dissolved in the ionic liquid by fitting experimental transients to the Aoki model. [Aoki, K.; et al. J. Electroanal. Chem. 1981, 122, 19]. A theory and simulation designed for cyclic voltammetry at microdisk electrodes was then employed to determine the diffusion coefficient of the electrogenerated superoxide species, O-2(.-), as well as compute theoretical voltammograms to confirm the values of D and c for neutral oxygen obtained from the transients. As expected, the diffusion coefficient of the superoxide species was found to be smaller than that of the oxygen in both ionic liquids. The diffusion coefficients of O-2 and O-2(.-) in [N-6222][N(Tf)(2)], however, differ by more than a factor of 30 (D-O2 = 1.48 x 10(-10) m(2) s(-1), DO2.- = 4.66 x 10(-12) m(2) s(-1)), whereas they fall within the same order of magnitude in [EMIM][N(Tf)(2)] (D-O2 = 7.3 x 10(-10) m(2) s(-1), DO2.- = 2.7 x 10(-10) m(2) s(-1)). This difference in [N-6222][N(Tf)(2)] causes pronounced asymmetry in the concentration distributions of oxygen and superoxide, resulting in significant differences in the heights of the forward and back peaks in the cyclic voltammograms for the reduction of oxygen. This observation is most likely a result of the higher viscosity of [N-6222][N(Tf)(2)] in comparison to [EMIM][N(Tf)(2)], due to the structural differences in cationic component.

Fundamentals of steady state, non-Newtonian rimming flow

Rimming flow on the inner surface of a horizontal rotating cylinder is investigated. Using a scale analysis, a theoretical description is obtained for steady-state non-Newtonian flow. Simple lubrication theory is applied since the Reynolds number is small and the liquid film is thin. Since the Deborah number is very small the flow is viscometric. The shear-thinning number, which characterizes the shear-thinning effect, may be small or large. A general constitutive law for this kind of flow requires only a single function relating shear stress and shear rate that corresponds to a generalized Newtonian liquid. For this case the run-off condition for rimming flow is derived. Provided the run-off condition is satisfied, the existence of a continuous steady-state solution is proved. The rheological models, which show Newtonian behavior at low shear rates with transition to power-law shear thinning at moderate shear rates, are considered. Numerical results are carried out for the Carreau and Ellis models, which exhibit Newtonian behavior near the free surface and power-law behavior near the wall of the rotating cylinder.

On the importance of steady-state isotopic techniques for the investigation of the mechanism of the reverse water-gas-shift reaction

The formation and reactivity of surface intermediates in the reverse water-gas-shift reaction on a Pt/CeO2 catalyst are critically dependent on the reaction conditions so that conclusionsregarding the reaction mechanism cannot be inferred using ex operando conditions.

Dynamical and steady-state requirements for effective entanglement transfer

Entanglement transfer processes from a continuous-variable (CV) to a qubit system have primary importance in quantum information processing due to some practical implications in the realization of a quantum network. A CV system can propagate entanglement while a qubit system is easy to manipulate. We study conditions to entangle two atomic qubits with a two-mode squeezed field driving two cavities containing the atoms.

Blood-derived dermal langerin+ dendritic cells survey the skin in the steady state.

Langerin is a C-type lectin receptor that recognizes glycosylated patterns on pathogens. Langerin is used to identify human and mouse epidermal Langerhans cells (LCs), as well as migratory LCs in the dermis and the skin draining lymph nodes (DLNs). Using a mouse model that allows conditional ablation of langerin(+) cells in vivo, together with congenic bone marrow chimeras and parabiotic mice as tools to differentiate LC- and blood-derived dendritic cells (DCs), we have revisited the origin of langerin(+) DCs in the skin DLNs. Our results show that in contrast to the current view, langerin(+)CD8(-) DCs in the skin DLNs do not derive exclusively from migratory LCs, but also include blood-borne langerin(+) DCs that transit through the dermis before reaching the DLN. The recruitment of circulating langerin(+) DCs to the skin is dependent on endothelial selectins and CCR2, whereas their recruitment to the skin DLNs requires CCR7 and is independent of CD62L. We also show that circulating langerin(+) DCs patrol the dermis in the steady state and migrate to the skin DLNs charged with skin antigens. We propose that this is an important and previously unappreciated element of immunosurveillance that needs to be taken into account in the design of novel vaccine strategies.

Extraction of electrode kinetic parameters from microdisc voltammetric data measured under transport conditions intermediate between steady-state convergent and transient linear diffusion as typically applies to room temperature ionic liquids

The extraction of electrode kinetic parameters for electrochemical couples in room-temperature ionic liquids (RTILs) is currently an area of considerable interest. Electrochemists typically measure electrode kinetics in the limits of either transient planar or steady-state convergent diffusion for which the voltammetic response is well understood. In this paper we develop a general method allowing the extraction of this kinetic data in the region where the diffusion is intermediate between the planar and convergent limits, such as is often encountered in RTILs using microelectrode voltammetry. A general working surface is derived, allowing the inference of Butler-Volmer standard electrochemical rate constants for the peak-to-peak potential separation in a cyclic voltammogram as a function of voltage scan rate. The method is applied to the case of the ferrocene/ferrocenium couple in [C(2)mim][N(Tf)(2)] and [C(4)mim][N(Tf)(2)].

On the complexity of the water-gas shift reaction mechanism over a Pt/CeO2 catalyst: Effect of the temperature on the reactivity of formate surface species studied by operando DRIFT during isotopic transient at chemical steady-state

The present report investigates the role of formate species as potential reaction intermediates for the WGS reaction (CO + H2O -> CO2 + H-2) over a Pt-CeO2 catalyst. A combination of operando techniques, i.e., in situ diffuse reflectance FT-IR (DRIFT) spectroscopy and mass spectrometry (MS) during steady-state isotopic transient kinetic analysis (SSITKA), was used to relate the exchange of the reaction product CO2 to that of surface formate species. The data presented here suggest that a switchover from a non-formate to a formate-based mechanism could take place over a very narrow temperature range (as low as 60 K) over our Pt-CeO2 catalyst. This observation clearly stresses the need to avoid extrapolating conclusions to the case of results obtained under even slightly different experimental conditions. The occurrence of a low-temperature mechanism, possibly redox or Mars van Krevelen-like, that deactivates above 473 K because of ceria over-reduction is suggested as a possible explanation for the switchover, similarly to the case of the CO-NO reaction over Cu, I'd and Rh-CeZrOx (see Kaspar and co-workers [1-3]). (c) 2006 Elsevier B.V. All rights reserved.

On the need to use steady-state or operando techniques to investigate reaction mechanisms: An in situ DRIFTS and SSITKA-based study example

The nature of the surface species formed at the surface of 2 wt.% Pt/CeO2 catalyst during the forward water-gas-shift (WGS, CO + H2O -> CO2 + H-2) and the reverse reaction (RWGS) were essentially identical. More, the surface concentration of formate, carbonate and carbonyl species was similar in each case. The presence of well-resolved IR bands allowed an unequivocal relative quantitative analysis of each species, avoiding the use of the carboxylate stretching region (1600-1200 cm(-1)). However, the quantitative analysis in the case of an isotopic study was complicated due to the overlapping of the various isotope bands, yet this problem could be overcome by integrating the high-wavenumber part of the bands. The reactivity of the surface species formed under RWGS conditions was followed under two different gaseous streams. Firstly, the reactivity of these intermediates were followed under an inert gas (i.e., At), in which case carbonates were essentially stable and less reactive than formates. Secondly, the reactivity of the same surface species was followed when switching to the corresponding C-13-labelled feed (i.e., (CO2)-C-13 + H-2), in which case carbonates were exchanged significantly faster than formates. While carbonates species have been reported as reaction intermediate under reaction conditions, the increased stability or surface poisoning by these carbonates in the absence of reaction mixture was highlighted. Ultimately, this work re-emphasises the need to use steady-state conditions if the true operando reactivity of the adsorbates and structure of the solid are to be determined. (c) 2005 Elsevier B.V. All rights reserved.

Negative apparent kinetic order in steady-state kinetics of the water-gas shift reaction over a Pt-CeO2 catalyst

The kinetics of the water-gas shift reaction Were Studied on a 0.2% Pt/CeO2 catalyst between 177 and 300 degrees C over a range of CO and steam pressures. A rate decrease with increasing partial pressure of CO was experimentally observed over this sample, confirming that a negative order in CO can occur under certain conditions at low temperatures. The apparent reaction order of CO measured at 197 degrees C was about -0.27. This value is significantly larger than that (i.e, -0.03) reported by Ribeiro and co-workers [A.A. Phatak, N. Koryabkina, S. Rai, J.L. Ratts, W. Ruettinger, R.J. Farrauto, G.E. Blau, W.N. Delgass, F.H. Ribeiro, Catal. Today 123 (2007) 224] at a similar temperature. A kinetic peculiarity was also evidenced, i.e. a maximum of the reaction rate as a function of the CO concentration or possibly a kinetic break, which is sometimes observed in the oxidation of simple molecules. These observations support the idea that competitive adsorption of CO and H2O play an essential role in the reaction mechanism. (C) 2008 Elsevier B.V. All rights reserved.

Steady-State and Transient Performance of Biodiesel-Fueled Compression-Ignition-Based Electrical Generation

This paper investigates the performance characteristics of rapeseed methyl ester, EN 14214 biodiesel, when used for electrical generation in compression ignition engines. The work was inspired by the need to replace fossil diesel fuel with a sustainable low carbon alternative while maintaining generator performance, power quality, and compliance with ISO 8528-5. A 50-kVA Perkins diesel engine generator was used to assess the impact of biodiesel with particular regard to gen-set fuel consumption, load acceptance, and associated standards. Tests were performed on the diesel gen-set for islanded and grid-connected modes of operation, hence both steady-state and transient performance were fully explored. Performance comparisons were made with conventional fossil diesel fuel, revealing minimal technical barriers for electrical generation from this sustainable, carbon benign fuel. Recommendations for improved transient performance are proposed and validated through tests.