Temperature (over) compensation in an oscillatory surface reaction

Biological rhythms are regulated by homeostatic mechanisms that assure that physiological clocks function reliably independent of temperature changes in the environment. Temperature compensation, the independence of the oscillatory period on temperature, is known to play a central role in many biological rhythms, but it is rather rare in chemical oscillators. We study the influence of temperature on the oscillatory dynamics during the catalytic oxidation of formic acid on a polycrystalline platinum electrode. The experiments are performed at five temperatures from 5 to 25 degrees C, and the oscillations are studied under galvanostatic control. Under oscillatory conditions, only non-Arrhenius behavior is observed. Overcompensation with temperature coefficient (q(10), defined as the ratio between the rate constants at temperature T + 10 degrees C and at T) < I is found in most cases, except that temperature compensation with q(10) approximate to I predominates at high applied currents. The behavior of the period and the amplitude result from a complex interplay between temperature and applied current or, equivalently, the distance from thermodynamic equilibrium. High, positive apparent activation energies were obtained under voltammetric, nonoscillatory conditions, which implies that the non-Arrhenius behavior observed under oscillatory conditions results from the interplay among reaction steps rather than, from a weak temperature dependence of the individual steps.

Thermo-optics parameters measurements in photorefractive sillenite Bi(12)SiO(20) crystals by thermal lens technique

The present work reports on the thermo-optical properties of photorefractive sillenite Bi(12)SiO(20) (BSO) crystals obtained by applying the Thermal Lens Spectrometry technique (TLS). This crystals presents one high photorefractive sensitivity in the region blue-green spectra, since the measurements were carried out at two pump beam wavelengths (514.5 nm and 750 nm) to study of the light-induced effects in this material (thermal and/or photorefractive). We determine thermo-optical parameters like thermal diffusivity (D), thermal conductivity (K) and temperature coefficient of the optical path length change (ds/dT) in sillenite crystals. These aspects, for what we know, not was studied in details up to now using the lens spectrometry technique and are very important against of the promising potentiality of applications these crystals in non linear optics, real time holography and optical processing data.

Thermal lens spectrometry in pyroelectric lithium niobate crystals

In this work, the light-induced lens effect due to thermal and/or photorefractive processes was studied in pyroelectric (undoped and Fe(2+)-doped) lithium niobate crystals (LiNbO(3)) using thermal lens spectrometry with a two-beam (pump-probe) mode-mismatched configuration. The measurements were carried out at two pump beam wavelengths (514.5 and 750 nm) to establish a full understanding of the present effects in this material (thermal and/or photorefractive). We present an easy-to-implement method to determine quantitative values of the pyroelectric coefficient (dPs/dT), its contribution to the thermal effect and other thermo-optical parameters like thermal diffusivity (D), thermal conductivity (K) and temperature coefficient of the optical path length change (ds/dT). These measurements were performed in LiNbO(3) and LiNbO(3): Fe (0.1 ppm Fe(2+)) crystals with c axis along the direction of laser propagation.