Pamela A. Mosier-Boss

On the behavior of Pd deposited in the presence of evolving deuterium

This note reports on an alternative experimental approach to produce conditions favorable to the observation of this extraordinary behavior by exploiting the Pd/D codeposition

Charging of the Pd/nH system: Role of the interphase

The dynamics of transport of electrochemically generated deuterium across the electrode/electrolyte interphase was examined by slow scan (10 mV s−1) voltammetry. The investigation covers the potential range −1.2 to +0.4 V measured vs. an Ag/AgCl reference. It was found that a coupled, two-layer model of the interphase describes the observed behavior as a function of scan rate and electrolyte composition. The effect of chemisorbing species, e.g. CN− ions, as well as reactive species, e.g. SC(NH2)2, on the transport across the interphase is also discussed. Results are contrasted with those obtained for light water.

Further evidence of nuclear reactions in the Pd/D lattice: emission of charged particles

Almost two decades ago, Fleischmann and Pons reported excess enthalpy generation in the negatively polarized Pd/D-D2O system, which they attributed to nuclear reactions. In the months and years that followed, other manifestations of nuclear activities in this system were observed, viz. tritium and helium production and transmutation of elements. In this report, we present additional evidence, namely, the emission of highly energetic charged particles emitted from the Pd/D electrode when this system is placed in either an external electrostatic or magnetostatic field. The density of tracks registered by a CR-39 detector was found to be of a magnitude that provides undisputable evidence of their nuclear origin. The experiments were reproducible. A model based upon electron capture is proposed to explain the reaction products observed in the Pd/D-D2O system.

On the Behavior of the Pd/D System: Evidence for Tritium Production

Evidence for tritium production in the Pd/D system under cathodic polarization is presented. A comparison of the observed distribution and that calculated, based on the conservation of mass, leads to the conclusion that tritium is produced sporadically at an estimated rate of ∼10 3 to 10 4 atom/s. The results of several runs are interpreted by employing the concept of an electrode/ electrolyte interphase and the accepted kinetics of hydrogen evolution. Burstlike events followed by longer periods of inactivity yield poor reproducibility when distributions are averaged over the total time ofelectrolysis.

Deuterium uptake during PdD codeposition

Abstract The mode of deuterium uptake during PdD co-deposition has been explored using galvanostatic perturbation techniques. The resultant potential relaxation curves exhibit four distinct potential—time intervals where the relaxation process is controlled by the interaction between the transport of deuterium from the lattice to the surface to form adsorbed deuterium and the reduction of palladium from solution. These interactions are discussed in terms of the palladium + electrolyte interphase.

Absorption of deuterium in palladium rods: model vs. experiment

Abstract The electrochemical charging of Pd rods by deuterium involves a complex coupling of electrochemical, interfacial and transport processes. In order to predict the overpotential, surface coverage and bulk loading of the electrode during charging, a model has been developed that incorporates the essential features of these processes and involves variables such as the electrochemical rate constants, the bulk diffusion coefficient and the charging current. Features of the computed time dependence of the bulk loading are then compared with published experimental charging curves. New microscopic observations and X-ray diffraction data provide further evidence for the details of the charging process.

Feasibility studies for the detection of volatile organic compounds in the gas phase using microelectrode sensors

The use of microelectrode sensors to detect volatile organic compounds (VOCs) in air is demonstrated. In general, VOCs that oxidize easily to form protons gave a larger electrochemical response. The use of voltammetry for speciation and the effect of electrode size on the electrochemical response are discussed. We demonstrate that surface enhanced Raman spectroscopy (SERS) can be used to monitor the electrochemical reactions in situ and discuss its applicability in identifying the electroactive species.

Cyclic voltammetry of Pd+D codeposition

Abstract Processes associated with the Pd+D alloy codeposition are examined by cyclic voltammetry. The voltammograms cover the potential range: +0.3 to −1.3 V (measured against an Ag/AgCl/KCl (sat) reference) and indicate that the partial current due to the Pd 2+ ion reduction is diffusion limited at slow scan rates. Except for the significant increase in cathodic currents due to D 2 O reduction at ca. −0.25 V which occurs on a freshly generated Pd surface, the shapes of the voltammograms marginally differ from those recorded in the absence of Pd 2+ ions in the electrolyte phase. A discussion of the dynamics of the interphase is presented.

Comments on the analysis of tritium content in electrochemical cells

Abstract Expressions are given for the tritium distribution between gas and liquid phases arising from prolonged electrolysis of D2O on Pd electrodes saturated with absorbed deuterium. Errors associated with commonly employed experimental procedures and their interpretation using a simple model for the distribution between the gas and liquid phases are evaluated. With regard to tritium production, an unambiguous resolution requires a complete mass balance. Conclusions based on partial data, such as the measurement of the tritium content in a single cell component (e.g. electrode, electrolyte or “electrolytic” gas phase), may be misleading, particularly if production rates are either low or intermittent.

Raman and infrared spectroscopy of the AlCl3–SOCl2 system

The structural aspects of the AlCl3–SOCl2 system have been examined by vibrational spectroscopy. The SOCl2 molecule exhibits amphoteric character, i.e. it can act simultaneously as a donor through the oxygen atom and as an acceptor through the sulphur atom. The liquid state contains loosely bound, open-chain dimers/oligomers, (Cl2SO)n with n 2. The dissolution of Al2Cl6 in SOCl2 occurs dissociatively with the formation of Cl2SO → AlCl3 adducts. At higher AlCl3 concentrations, an increase in solution electrical conductivity is attributed to the reaction: 2Cl2SO → AlCl3⇌[Cl2Al(â†� OSCl2)2]++ AlCl–4