The role of additional solvents in transition metal complex catalyzed asymmetric reductions in ionic liquid containing systems

When ionic liquids (ILs) are employed as solvents for transition metal complex (TMC) catalyzed reductions, a second solvent can be added to increase the efficiency of the catalytic cycle and the solubility of the reactant in the IL phase. Two industrially relevant asymmetric hydrogenations, the enantioselective reductions of methyl 2-acetamidoacrylate with Rh-EtDuPHOS and methyl acetoacetate with Ru-BINAP, were performed in different catalytic systems including 1-butyl-3-methylimidazolium hexafluorophosphate/ tetrafluoroborate as ILs. Product separation and TMC recycling was performed by extracting the product from the reaction mixture. This can be accomplished by cooling the system, by adding an excess of the second solvent or by adding a third solvent. A high solubility of the second solvent in the IL catalytic phase favors the reaction activity, but can induce leaching of the IL and TMC.     

Autoxidation of cyclohexane: conventional views challenged by theory and experiment.

In spite of its industrial importance, the detailed reaction mechanism of cyclohexane autoxidation by O2 is still insufficiently known. Based on quantum chemical potential energy surfaces, rate coefficients of the primary and secondary chain propagation steps involving the cyclohexylperoxyl (CyOO) radical were evaluated using multiconformer transition-state theory. Including tunneling and hindered-internal-rotation effects, the rate coefficient for hydrogen-atom abstraction from cyclohexane (CyH) by CyOO was calculated to be k(T)= 1.46 x 10(-11) x exp(-17.8 kcal mol(-1)/ RT) cm3s(-1) (300-600K), close to the experimental data. A "Franck-Rabinowitch cage" reaction between the nascent cyclohexylhydroperoxide (CyOOH) and cyclohexyl radical, products from CyOO + CyH, is put forward as an initially important cyclohexanol (CyOH) formation channel. alphaH abstraction by CyOO. from cyclohexanone was calculated to be only about five times faster than that from CyH, too slow to explain all the observed side products. The a-hydrogen (alphaH) abstractions from CyOH and CyOOH by CyOO. are predicted to be about 10 and 40 times faster, respectively, than the CyOO. +CyH reaction. The very fast CyOO.+CyOOH reaction proceeds through the unstable Cy-alphaH .OOH radical that decomposes spontaneously into the ketone (Q=O) plus the OH radical; the "hot" .OH is found to produce the bulk of the alcohol via a second, "activated cage" reaction analogous to that above. It is thus shown how the very reactive CyOOH intermediate is the predominant source of ketone and alcohol, while it also leads to some side products. The alpha-hydroxycyclohexylperoxyl radical formed during the moderately fast oxidation of CyOH is shown to decompose fast into HO2 + cyclohexanone in a rapidly equilibrated reaction, which constitutes a smaller, second ketone source. These two fast cyclohexanone forming routes avoid the need for unfavorable molecular routes hitherto invoked as ketone sources. The theoretical predictions are supported and complemented by experimental findings. The newly proposed scheme is also largely applicable to the oxidation of other hydrocarbons, such as toluene, xylene, and ethylbenzene.     

The glass transition of thin polymer films: some questions,and a possible answer

The European Physical Journal E - A simple and predictive model is put forward explaining the experimentally observed substantial shift of the glass transition temperature, T g, of sufficiently...     

Continuous quantum measurement and the emergence of classical chaos

We formulate the conditions under which the dynamics of a continuously measured quantum system becomes indistinguishable from that of the corresponding classical system. In particular, we demonstrate that even in a classically chaotic system the quantum state vector conditioned by the measurement remains localized and, under these conditions, follows a trajectory characterized by the classical Lyapunov exponent.     

Ionization equilibrium and radiative energy loss rates for C,N, and O ions in low-density plasmas

The results of calculations of the ionization equilibrium and radiative energy loss rates for C, N and O ions in low-density plasmas are presented for electron temperatures in the range 10⁴–10⁷ °K (～1–10³ eV). The ionization structure is determined using the steady-state corona model, in which electron impact ionization from the ground states is balanced by direct radiative and dielectronic recombination. Using an improved theory, detailed calculations are carried out for the dielectronic recombination rates in which account is taken of all radiative and autoionization processes involving a single-electron electricdipole transition of the recombining ion. The radiative energy loss processes considered are electron-impact excitation of resonance line emission, direct radiative recombination, dielectronic recombination, and electron-ion bremsstrahlung. For all three elements, resonance line emission resulting from 2s?2p transitions produces a broad maximum in the energy loss rate near 10⁵°K(～ 10 eV).     

Axisymmetric shock wave interaction with a cone: a benchmark test

Results of the benchmark test are presented of comparing numerical schemes solving shock wave of M_s = 2.38 in nitrogen and argon interacting with a 43∘ semi-apex angle cone and corresponding experiments. The benchmark test was announced in Shock Waves Vol. 12, No. 4, in which we tried to clarify the effects of viscosity and heat conductivity on shock reflection in conical flows. This paper summarizes results of ten numerical and two experimental applications. State of the art in studies regarding the shock/cone interaction is clarified. PACS 01.50.Kw, 47.15.Pn Communicated by K. Takayama     

The numerical and experimental simulation of hypervelocity flow around the HYFLEX vehicle forebody

Numerical and experimental techniques are used to model the flow and pressure distribution around the forebody of the HYFLEX hypersonic flight vehicle. We compare numerical simulation results with modified Newtonian theory and flight data to determine the accuracy of the computational fluid dynamics (CFD) technique used. The numerical simulations closely match the trends in flight data, and show that real gas effects have a small but significant influence on the nose pressure distribution. We also present pressure results from a scale-model tested in a shock tunnel, and compare them with simulation results. For the shock tunnel experiment, the model was placed such that part of the upper surface was in a region of the test flow where nonuniformities were significant, and it was shown that the numerical simulation could adequately capture these experimental flow features. The binary scaling parameter (describing the similarity in species dissociation between flight and model) was used to design the scale-model tests in the shock tunnel, and its effectiveness is discussed. We find that matching the flight Mach number in the shock tunnel experiment is not critical for reproducing flight pressure data, so long as flight velocity is matched, and binary scaling is maintained. Received 11 June 1998 / Accepted 1 September 1998     

Effect of boundary representation on viscous,separated flows in a discontinuous-Galerkin Navier–Stokes solver

The effect of curved-boundary representation on the physics of the separated flow over a NACA 65(1)-412 airfoil is thoroughly investigated. A method is presented to approximate curved boundaries with a high-order discontinuous-Galerkin spectral element method for the solution of the Navier–Stokes equations. Multiblock quadrilateral element meshes are constructed with the grid generation software GridPro. The boundary of a NACA 65(1)-412 airfoil, defined by a cubic natural spline, is piecewise-approximated by isoparametric polynomial interpolants that represent the edges of boundary-fitted elements. Direct numerical simulation of the airfoil is performed on a coarse mesh and fine mesh with polynomial orders ranging from four to twelve. The accuracy of the curve fitting is investigated by comparing the flows computed on curved-sided meshes with those given by straight-sided meshes. Straight-sided meshes yield irregular wakes, whereas curved-sided meshes produce a regular Karman street wake. Straight-sided meshes also produce lower lift and higher viscous drag as compared with curved-sided meshes. When the mesh is refined by reducing the sizes of the elements, the lift decrease and viscous drag increase are less pronounced. The differences in the aerodynamic performance between the straight-sided meshes and the curved-sided meshes are concluded to be the result of artificial surface roughness introduced by the piecewise-linear boundary approximation provided by the straight-sided meshes.     

Background oriented schlieren for flow visualisation in hypersonic impulse facilities

Experiments to demonstrate the use of the background-oriented schlieren (BOS) technique in hypersonic impulse facilities are reported. BOS uses a simple optical set-up consisting of a structured background pattern, an electronic camera with a high shutter speed and a high intensity light source. The visualization technique is demonstrated in a small reflected shock tunnel with a Mach 4 conical nozzle, nozzle supply pressure of 2.2 MPa and nozzle supply enthalpy of 1.8 MJ/kg. A 20° sharp circular cone and a model of the MUSES-C re-entry body were tested. Images captured were processed using PIV-style image analysis to visualize variations in the density field. The shock angle on the cone measured from the BOS images agreed with theoretical calculations to within 0.5°. Shock standoff distances could be measured from the BOS image for the re-entry body. Preliminary experiments are also reported in higher enthalpy facilities where flow luminosity can interfere with imaging of the background pattern. A version of this paper was presented at the 25th International Symposium on Shock Waves in Bangalore in July 2005.