Direct observation of chemical oscillation at a water/nitrobenzene interface with a sodium-alkyl-sulfate system.

The oscillation of the interfacial tension and electrical potential at a water/nitrobenzene interface was observed with homologous anionic surfactant molecules, sodium-alkyl-sulfates. Concerning small molecules with a short hydrophobic carbon chain, the oscillation period and amplitude decreased with a decrease of the length of the alkyl chain. On the other hand, when surfactant molecules with a long hydrophobic carbon chain were used, no remarkable periodic oscillation occurred after the first oscillation. In all systems, an interfacial flow by Marangoni convection was observed when the oscillation took place. By monitoring the movement of carbon powder scattered on the liquid/liquid interface with a CCD camera, we could observe that the liquid/liquid interface expanded outward from the area on which the surfactant molecules adsorbed when the oscillation occurred. When the small molecule was used, the speed of expansion of the interface (flow speed) was small and shrinkage followed by expansion of the interface repeatedly occurred. However, when the large molecule was used, the flow speed was large and expansion occurred only one time. These results show that hydrodynamic factors and surface activities are important in chemical oscillation systems.     

New approaches to liquid interfaces through changes in the refractive index and nonlinear susceptibility utilizing ultrashort laser pulses.

Molecules in inhomogeneous liquid environments, such as air/liquid, liquid/liquid, solid/liquid interfaces interact with each other specifically, and sometimes form characteristic structures and emerge unique properties. Here, we introduce two newly developed spectroscopic techniques, the total-internal-reflection ultrafast transient lens method (TIR-UTL) and second harmonic generation-coherent vibrational spectroscopy (SHG-CVS), to investigate the characteristic behaviors of molecules in such inhomogeneous environments. TIR-UTL probes the refractive-index change with sub-picosecond resolution and provides information on ultrafast changes in the population, density, and thermal properties, such as temperature increase and energy transfer from the solute molecules to the surrounding solvent molecules. On the other hand, SHG-CVS probes nonlinear susceptibility changes at the interfacial areas, and is expected to provide spectroscopic information on the low-frequency vibrational modes that reflect the corrective motion of the molecules in such an inhomogeneous environment. These new approaches are based on pump-probe techniques utilizing (ultra) short laser pulses. They are expected to provide further information on inhomogeneous environments from the viewpoints of solute-solvent interactions, changes in the molecular orientation, and the corrective motion of molecules at liquid interfaces.     

Nonlinear Boundary Layers of the Boltzmann Equation: I. Existence

 We study the half-space problem of the nonlinear Boltzmann equation, assigning the Dirichlet data for outgoing particles at the boundary and a Maxwellian as the far field. We will show that the solvability of the problem changes with the Mach number ℳ^∞ of the far Maxwellian. If ℳ^∞<−1, there exists a unique smooth solution connecting the Dirichlet data and the far Maxwellian for any Dirichlet data sufficiently close to the far Maxwellian. Otherwise, such a solution exists only for the Dirichlet data satisfying certain admissible conditions. The set of admissible Dirichlet data forms a smooth manifold of codimension 1 for the case −1<ℳ^∞<0, 4 for 0<ℳ^∞<1 and 5 for ℳ^∞>1, respectively. We also show that the same is true for the linearized problem at the far Maxwellian, and the manifold is, then, a hyperplane. The proof is essentially based on the macro-micro or hydrodynamics-kinetic decomposition of solutions combined with an artificial damping term and a spatially exponential decay weight. Received: 20 April 2002 / Accepted: 4 December 2002 Published online: 21 March 2003 Communicated by H.-T. Yau