Unraveling the mechanism of catalytic reactions through combined kinetic and thermodynamic analyses: Application to the condensation of ethanol

The combination of kinetic and thermodynamic analyses can provide an in-depth knowledge of the crucial steps of catalyzed reactions. Earlier examples are recalled to stress how a reaction mechanism can be supported or rejected based on trivial reactant and product concentration analyses. The method is then applied to the important reaction of alcohol condensation, the so-called Guerbet reaction, which enables converting ethanol, a renewable feedstock, into higher alcohols. Important conclusions regarding the design of ethanol condensation processes can be drawn, as the main reaction mechanism occurring at high temperatures (ca. 350–420 °C) appears to be different from that proposed at low temperatures (< 250 °C). In the former case, the pathway involving acetaldehyde is negligible, and therefore a multi-step process based on ethanol dehydrogenation followed by acetaldehyde self-aldolization would be irrelevant.     

Time delay as a key to apoptosis induction in the p53 network

A feedback mechanism that involves the proteins p53 and mdm2, induces cell death as a controlled response to severe DNA damage. A minimal model for this mechanism demonstrates that the response may be dynamic and connected with the time needed to translate the mdm2 protein. The response takes place if the dissociation constant k between p53 and mdm2 varies from its normal value. Although it is widely believed that it is an increase in k that triggers the response, we show that the experimental behaviour is better described by a decrease in the dissociation constant. The response is quite robust upon changes in the parameters of the system, as required by any control mechanism, except for few weak points, which could be connected with the onset of cancer. Received 8 May 2002 / Received in final form 9 July 2002 Published online 17 September 2002     

A thermodynamic approach with internal variables using Lagrange formalism. Part I: General framework

We present some reflections on the application of the Lagrangian formalism for continuous media locally uniform subjected to internal irreversible evolutions. The Lagrangian density, defined as the time derivative of a non-equilibrium thermodynamic potential, [Thermodynamics of Relaxation Processes using Internal variables within a Lagrange-formalism. P. Germain’s Anniversary Volume 2000. Contiuum Thermomechanics: the Art and Science of Modeling Matter’s Behaviour, 2000], contains all the symmetry properties of the system. The generalised Lagrange co-ordinates correspond to the state and internal variables of the time derivative of the generalised Gibbs potential. The latter being used within the framework of the De Donder’s method, must also account for the memory effect of the physical medium.This first part is devoted to the thermodynamic framework called the distribution of non-linear relaxations approach (DNLR) developed by C. Cunat on the basis of the generalised Gibbs’ relation.     

Thermodynamic study of sodium-iron oxides: Part II. Ternary phase diagram of the Na-Fe-O system

Studies on ternary phase diagrams of the Na-Fe-O system have been carried out from the thermodynamic point of view. Thermodynamic data of main ternary Na-Fe oxides Na₄FeO₃(s), Na₃FeO₃(s), Na₅FeO₄(s) and Na₈Fe₂O₇(s) have been assessed. A user database has been created by reviewing literature data together with recent DSC and vapor pressure measurements by the present authors. New ternary phase diagrams of the Na-Fe-O system have been constructed from room temperature to 1000 K. Stable conditions of the ternary oxides at 800 K were presented in predominance diagram as functions of oxygen pressure and sodium pressure.     

Noise-assisted mound coarsening in epitaxial growth

Two types of mechanisms are proposed for mound coarsening during unstable epitaxial growth: stochastic, due to deposition noise, and deterministic, due to mass currents driven by surface energy differences. Both yield the relation H=(RWL)² between the typical mound height W, mound size L, and the film thickness H. An analysis of simulations and experimental data shows that the parameter R saturates to a value which discriminates sharply between stochastic () and deterministic () coarsening. We derive a scaling relation between the coarsening exponent 1/z and the mound-height exponent which, for a saturated mound slope, yields . Received: 11 November 1997 / Revised in final form: 28 November 1997 / Accepted: 28 November 1997     

Chopped CW laser-induced optogalvanic effect in a neon hollow cathode discharge

A detailed model for the optogalvanic effect in a neon hollow cathode discharge irradiated by a chopped CW dye laser is presented. A rate equation formalism is used to calculate the evolution of the first and second electronic configuration populations coupled by the laser and of the electric charges number density. Processes as ambipolar-like electrons loss, electronic collisional coupling of level populations and electron emission by the cathode due to VUV radiation from the 1s ₂ resonant level are taken into account and further discussed.The transients and steady-state magnitude of the optogalvanic signal are calculated, compared with experimental data and related to population changes. We predict sign changes of the optogalvanic signal when the laser is tuned over transitions originating from the resonant level with respect to transitions involving the metastables states. The optogalvanic signal is shown to be basically determined by the laser-induced variations of the excited-state populations while changes in the electron temperature, due to laser energy transfer by collisions between electrons and excited atoms, play a negligible role.     

Controlling global stochasticity of Hamiltonian systems by nonlinear perturbation

A method of controlling global stochasticity in Hamiltonian systems by applying nonlinear perturbation is proposed. With the well-known standard map we demonstrate that this control method can convert global stochasticity into regular motion in a wide chaotic region for arbitrary initial condition, in which the control signal remains very weak after a few kicks. The system in which chaos has been controlled approximates to the original Hamiltonian system, and this approach appears robust against small external noise. The mechanism underlying this high control efficiency is intuitively explained. Received 15 January 2002 Published online 6 June 2002     

Teleportation of an Arbitrary Multipartite GHZ-Class State by One EPR Pair

We present a scheme for perfectly teleporting an arbitrary and unknown N-particle GHZ-class state from a sender to a receiver. We just need one quantum channel composed of two or three particles in the maximally entangled state. The sender performs one Bell-state measurement on two of her particles and N - 1 Hadamard operations and N - 1 yon Neumann measurements on the rest N - 1 particles. The receiver adopts one corresponding unitary transformation on his particles shared with the sender. After that, the receiver can obtain the original N-particle GHZ-class state by introducing N - 1 ancillary particles and carrying out N - 1 controlled-NOT operations. We also generalize the scheme to the case of controlled teleportation.     

Scheme for Robust Long-Distance Continuous Variable Quantum Key Distribution

It is shown that the configuration of phase coding for quantum key distribution with single photon can also be used for continuous variable quantum key distribution. Therefore the robust long-distance high-speed quantum key distribution can be achieved with current technology.