ALBERT

Notes: An experimental setup has been constructed for simultaneous measurements of the frequency, the absolute Q factor, and the amplitude of oscillation of a quartz crystal microbalance (QCM). The technical solution allows operation in vacuum, air, or liquid. The crystal is driven at its resonant frequency by an oscillator that can be intermittently disconnected causing the crystal oscillation amplitude to decay exponentially. From the recorded decay curve the absolute Q factor (calculated from the decay time constant), the frequency of the freely oscillating crystal, and the amplitude of oscillation are obtained. All measurements are fully automated. One electrode of the QCM in our setup was connected to true ground which makes possible simultaneous electrochemistry. The performance is illustrated by experiments in fluids of varying viscosity (gas and liquid) and by protein adsorption in situ. We found, in addition to the above results, that the amplitude of oscillation is not always directly proportional to the Q factor, as the commonly used theory states. This puts limitations on the customary use of the amplitude of oscillation as a measure of the Q factor. © 1995 American Institute of Physics.

Notes: An experimental setup is described that can simultaneously measure the absolute dissipation factor and the resonant frequency of a short-circuited quartz crystal microbalance. The crystal is driven at approximately its resonant frequency by a signal generator which is intermittently disconnected by a relay, causing the crystal oscillation amplitude to decay exponentially. The decay is measured using a ferrite toroid transformer. One of the crystal leads is fed through the center of the ferrite toroid and thereby acts as the primary winding of the transformer. The secondary winding of the transformer is connected to a digitizing oscilloscope which records the decay of the crystal oscillation. From the recorded decay curve, the absolute dissipation factor (calculated from the decay time constant) and the series resonant frequency of the freely oscillating crystal are obtained. Alternatively, the dissipation factor and resonant frequency can be measured for the crystal oscillating under open-circuit conditions, i.e., in the parallel mode. The measurements are automated. © 1996 American Institute of Physics.

Notes: The desorption of OH radicals from Pt(111) at high temperature, (approximately-greater-than)1000 K, during the water formation (H2+1/2 O2→H2O) and water decomposition reactions, respectively, was investigated using the laser-induced fluorescence technique. The results are compared with corresponding data from our laboratory for polycrystalline Pt. The OH desorption rate in H2+O2 at 1–100 mTorr total pressure has its maximum at 8%–9% relative H2 concentration for surface temperatures between 1100 and 1400 K. With H2 replaced by D2, the OD desorption rate maximizes at somewhat higher relative hydrogen content. The apparent activation energy for OH desorption increases from about 1.4 eV at low relative hydrogen concentration to about 2.0 eV at hydrogen contents of 25% or more. For the water decomposition reaction, the apparent activation energy for OH desorption was found to be 1.7±0.2 eV at 0.5 Torr and 1.9±0.2 eV at 1 Torr. These differences in apparent activation energies are primarily due to kinetic effects. The results are analyzed within a kinetic model previously developed by Hellsing et al. [J. Catal. 132, 210 (1991)], and are also compared with previous data for polycrystalline Pt. The kinetic model calculations give good overall agreement with the measured OH desorption rates as functions of temperature, H2/O2 mixture and H2O pressure, respectively. A nonuniqueness problem, with respect to the choice of kinetic parameters, is encountered in the simulation of the measured data; quite different sets of two of the kinetic constants, namely the activation energy for water formation (via OH+H→H2O) and the activation energy for OH desorption can reproduce the data as long as their difference is constant.This nonuniqueness problem, which is a consequence of the steady-state nature of the measurements, is analyzed and discussed in some detail, as are some apparent contradictions in the absolute values of reported kinetic constants in the literature. From this analysis two important conclusions are drawn. (i) The apparent contradictions in the literature about absolute values of activation energies for the water formation reaction and for OH-desorption may be less severe than believed or nonexistent. (ii) Coverage dependent activation energies must be considered and experimental exploration of such coverage dependencies are needed to create a firmer base for the kinetic modeling of the H2/O2 reaction on Pt. © 1995 American Institute of Physics.