Kinetics and mechanism of a fast leuco-Methylene Blue oxidation by copper(II)-halide species in acidic aqueous media

The kinetics of a fast leuco-Methylene Blue (LMB) re-oxidation to Methylene Blue (MB) by copper(II)-halide (Cl-, Br-) complexes in acidic aqueous media has been studied spectrophotometrically using a stopped-flow technique. The reaction follows a simple first order rate expression under an excess of the copper(II) species (and H+(aq)), and the pseudo-first order rate constant (k'(obs)) is largely independent of the atmosphere used (air, oxygen, argon). The rate law, at constant Cl- (Br-) anion concentration, is given by the expression: (d[MB+])/dt = ((k(a)K[H+] + k(b))/(1 + K[H+])).[Cu-II][LMB] = k'(obs)[LMB], where K is the protonation constant, and k(a) and k(b) are the pseudo-second order rate constants for protonated and deprotonated forms of LMB, respectively The rate law was determined based on the observed k'(obs) vs. [Cu-II] and [H+] dependences. The rate dramatically increases with [Cl-] over the range: 0.1-1.5 M, reflecting the following reactivity order: Cu2+(aq)

The effects of multi-pulse irradiation on X-ray laser media

Multipulse irradiation with 100 ps pulses of stripe Germanium targets is shown to enhance by up to several orders-of-magnitude the output of Ne-like Ge lasing on the J = 0-1 line at 196 Angstrom compared to single pulse pumping. Various pre-pulse and multipulse configurations have been experimentally investigated for irradiances of approximate to 4 x 10(13) W/cm(2) with a 1.06 mu m wavelength pumping laser. The ionisation balance measured by a KeV crystal spectrometer (KAP crystal) has been found to not affect the X-ray laser output. Good agreement between the experimental results and a fluid code incorporating atomic physics, gain and X-ray beam ray tracing is obtained. The code results show that the enhanced X-ray laser output is produced by multipulse irradiation reducing the electron density gradients in the gain region and simultaneously increasing the gain region spatial size. These changes reduce the effect of refraction on the X-ray laser beam propagation.