Solvation of ions—XX. The ferrocene—ferricinium couple and its role in the estimation of free energies of transfer of single ions

The ferrocene-ferricinium electrode (Pt/Foc, Fic⁺) was investigated in water, acetonitrile, ethanol, DMSO and DMF using single scan cyclic voltammetry and phase sensitive ac polarography. The oxidation-reduction is pseudo-reversible in all five solvents with an electrochemical rate constant of approximately 10⁻² cm/s. In all solvents a slow irreversible chemical step involving the ferricinium cation follows electron transfer, so that slow cyclic voltammetry or polarography rather than potentiometry is preferred if ferrocene is to be used as a reference electrode in non-aqueous solvents.

The Strehlow assumption, ΔG_tr(Foc) = ΔG_tr(Fic⁺ gives very different free energies of transfer of single ions from non-aqueous solvents to water when compared with the TATB assumption that ΔG_tr(Ph₄As⁺) = ΔG_tr(Ph₄B⁻). This discrepancy is likely to be because ferricinium is only a moderately large cation, so that ΔG_tr(Fic⁺) is less positive than ΔG_tr(Foc) for transfer to water. The discrepancy is not because of abnormal electrochemical behavior of the Pt/Foc, Fic⁺ electrode in water or other solvents. Values of E° vs nhe, H₂O in a variety of solvents based on the TATB assumption are presented.     

Mechanical properties and transition temperatures of copolymers of N-n-alkylacrylamides and vinylidene chloride

Mechanical and solution properties, melting transitions, torsional stiffness temperatures, T_f, and selected modulus-temperature curves are presented for copolymers of the N-n-alkylacrylamides with vinylidene chloride. Copolymers were prepared at 60°C across the range of compositions, using as comonomers N-n-butyl-, octyl-, dodecyl- and oleyl-acrylamide, which have amorphous side-chains, and N-n-octadecyl acrylamide and n-octadecyl acrylate whose side-chains are crystalline. The mechanical properties reflected the effect of the decline in backbone crystallinity and the simultaneous development of strong intermolecular interactions in the amorphous stage. Copolymers were stiff or showed brittle failure across the compositional range except when intermolecular forces were reduced (with n-octadrcyl acrylate) and side-chain crystallization eliminated (with N-oleylacrylamide). These systems and the n-dodecylacrylamide copolymers had yield strengths less than brittle strengths and substantial elongations. Backbone crystallinity was eliminated at about 15 mole % amide and side-chain crystallinity vanished at less than 10 mole % of the amide in the N-n-octadecylacrylamide series. No depression in side-chain melting point occurred with dilution by segments of vinylidene chloride. Over-all decline in the flex-temperature was the normal monotonic function of composition except that values increased in magnitude at high vinylidene chloride contents, the effect presumably being caused by the presence of crystallinity. An empirical equation was developed which permitted the calculation of T_f for any N-n-alkylacrylamide composition with any number of carbon atoms in the side-chain, above 3.     

Viscosity index. I. Evaluation of selected copolymers incorporating n-octadecyl acrylate as viscosity index improvers

Compositionally and structurally varied copolymers all containing n-octadecyl acrylate were prepared and evaluated as viscosity index improvers in a common base oil under conditions of low shear. Systems evaluated over a range of copolymer and blend composition were: copolymers of n-octadecyl acrylate with, respectively, methyl methacrylate, 2-ethylhexyl acrylate, and n-dodecyl acrylate; and homopolymers of poly(n-octadecyl acrylate), prepared with a wide range of molecular weights. Properties were compared with those of blends of commercial methacrylate copolymers (acryloids) which had been freed of their entraining liquid. Mixtures of base oil with copolymers of n-octadecyl acrylate and methyl methacrylate, compared at fixed SAE viscosities, were the most efficient of all blends studied. They had the smallest rate of change of viscosity with temperature (as measured by their ASTM slopes), particularly in the composition region of incipient polymer precipitation at room temperature. Efficiency of certain of these composition was somewhat greater than that of the acryloids. A parameter that related concentration and weight-average molecular weight was used to correlate all of the data for ASTM slope and viscosity. Empirical relations developed by using this parameter enabled rheological data to be estimated that agree within 6% of experimental values for the case of thermodynamically good base oil solvents. These data demonstrated the relatively small contributions of copolymer structure to viscosity index improvement.     

Interactive display of isosurfaces with global illumination

In many applications, volumetric data sets are examined by displaying isosurfaces, surfaces where the data, or some function of the data, takes on a given value. Interactive applications typically use local lighting models to render such surfaces. This work introduces a method to precompute or lazily compute global illumination to improve interactive isosurface renderings. The precompiled illumination resides in a separate volume and includes direct light, shadows, and intersections. Using this volume, interactive globally illuminated renderings of isosurfaces become feasible while still allowing dynamic manipulation of lighting, viewpoint and isovalue.     

Interconnect-based system-level energy and power prediction to guide architecture exploration

We present a novel technique to predict energy and power consumption in an electronic system, given its behavioral specification and library components. The early prediction gives circuit designers the freedom to make numerous high-level choices (such as die size, package type, and latency of the pipeline) with confidence that the final implementation will meet power and energy as well as cost and performance constraints. Our unique statistical estimation technique associates low-level, technology dependent physical and electrical parameters, with expected circuit resources and interconnect. Further correlations with switching activity yield accurate results consistent with implementations. All feasible designs are investigated using this technique and the designer may tradeoff between small size, high speed, low energy, and low power. The results for designs of two popular signal processing applications, predicted prior to synthesis, are within 10% accuracy of power estimates performed on synthesized layouts.     

Exploiting the Terahertz Band for Radionavigation

This paper demonstrates the feasibility of GPS-like ranging at terahertz (THz) frequencies. It is well established that GPS carrier signals are vulnerable to jamming via radio-frequency interference (RFI). As a result, there is a need for alternative radionavigation systems. THz signals offer a compelling option. Because of their high frequency (roughly ×100 higher than GPS), THz signals can be used to make highly precise range measurements. In addition, the large separation between the GPS and THz frequencies means that interference at GPS frequencies is very unlikely to impact the THz band. This paper lays the groundwork for a GPS-like ranging capability at THz frequencies. To this end, we identify key differences between THz hardware and GPS (radio frequency) hardware; we experimentally evaluate performance of a 0.30-THz system on a compact outdoor test range, and we introduce a measurement error model that highlights the distinctive role that multipath interference plays at THz frequencies.     

Myoelectric signal classification for phoneme-based speech recognition

Traditional acoustic speech recognition accuracies have been shown to deteriorate in highly noisy environments. A secondary information source is exploited using surface myoelectric signals (MES) collected from facial articulatory muscles during speech. Words are classified at the phoneme level using a hidden Markov model (HMM) classifier. Acoustic and MES data was collected while the words "zero" through "nine" were spoken. An acoustic expert classified the 18 formative phonemes in low noise levels [signal-to-noise ratio (SNR) of 17.5 dB] with an accuracy of 99%, but deteriorated to approximately 38% under simulations with SNR approaching 0 dB. A fused acoustic-myoelectric multiexpert system, without knowledge of SNR, improved on acoustic classification results at all noise levels. A multiexpert system, incorporating SNR information, obtained accuracies of 99% at low noise levels while maintaining accuracies above 94% during low SNR (0 dB) simulations. Results improve on previous full word MES speech recognition accuracies by almost 10%.