Tafel slopes from first principles

Tafel slopes for multistep electrochemical reactions are derived from first principles. The derivation takes place in two stages. First, Dirac’s perturbation theory is used to solve the Schrödinger equation. Second, current–voltage curves are obtained by integrating the single-state results over the full density of states in electrolyte solutions. Thermal equilibrium is assumed throughout. Somewhat surprisingly, it is found that the symmetry factor that appears in the Butler–Volmer equation is different from the symmetry factor that appears in electron transfer theory, and a conversion formula is given. Finally, the Tafel slopes are compiled in a convenient look-up table.     

X-ray investigation of the crystallization of chalcogenide glasses of the type (As2Se3)1−x:(Tl2Se)x

Amorphous and crystalline states of As₂Se₃, (As₂Se₃)₃ : Tl₂Se and As₂Se₃ : Tl₂Se have been studied using X-ray diffraction techniques. Structural changes arise during the process of annealing in the temperature range between their softening and melting points are reported and their rates investigated. The crystallization temperatures were found to be 105 ± 5 °C, 135 ± 5 °C and 180 ± 5 °C respectively. The unit cell parameters are identified for each of the three resulting crystalline phases, that for As₂Se₃ : Tl₂Se being orthorhombic while the other two are monoclinic.     

Bell clapper impact dynamics and the voicing of a carillon

The periodic re-voicing of the bell clappers of the Australian National Carillon in Canberra provided an opportunity for the study of the acoustic effects of this operation. After prolonged playing, the impact of the pear-shaped clapper on a bell produces a significant flat area on both the clapper and the inside surface of the bell. This deformation significantly decreases the duration of the impact event and has the effect of increasing the relative amplitude of higher modes in the bell sound, making it "brighter" or even "clangy." This effect is studied by comparing the spectral envelope of the sounds of several bells before and after voicing. Theoretical analysis shows that the clapper actually strikes the bell and remains in contact with the bell surface until it is ejected by a displacement pulse that has traveled around the complete circumference of the bell. The contact time, typically about 1 ms, is therefore much longer than the effective impact time, which is only a few tenths of a millisecond. Both the impact time and the contact time are reduced by the presence of a flat on the clapper.     

Rotational aerophones

Free rotational aerophones such as the bullroarer, which consists of a wooden slat whirled around on the end of a string, and which emits a loud pulsating roar, have been used in many ancient and traditional societies for ceremonial purposes. This article presents an experimental and theoretical investigation of this instrument. The aerodynamics of rotational behavior is elucidated, and relates slat rotation frequency to slat width and velocity through the air. Analysis shows that sound production is due to generation of an oscillating-rotating dipole across the slat, the role of the vortices shed by the slat being relatively minor. Apparent discrepancies between the behavior of a bullroarer slat and a slat mounted on an axle in a wind tunnel are shown to be due to viscous friction in the bearings of the wind-tunnel experiment.     

Synthesis and novel reactivity of halomethyldimethylsulfonium salts

Iodomethyl-, chloromethyl-, and fluoromethyldimethylsulfonium salts, 4b-d, have been synthesized and are observed to be highly reactive molecules that exhibit extraordinary diversity with respect to the nature of their reactivity, undergoing facile direct substitution (S(N)2) reactions, but also being highly susceptible to electron-transfer reactions. Cyclic voltametry experiments indicated that the iodomethyldimethylsulfonium compound, 4b, is a potent electron acceptor, even surpassing the reactivity of perfluoro-n-alkyl iodides in that capacity. The iodo- and chloromethyldimethylsulfonium salts, 4b,c, as well as the analogous iodomethyltrimethylammonium salt, 3a, are shown to be reactive SET acceptors.     

The determination of ethanol by alternating current tensammetry

A method for the determination of ethanol in vodka by phase-sensitive a.c. tensammetry is described; the only prior treatment of the sample is dilution with water and addition of KCl The positive wave of the tensammetric response was used. Ethanol concentrations in the range 2–10% can be determined with a relative imprecision of 0.5%. Other species having surfactant properties, such as the fusel oils found in most distilled liquors, interfere.     

CHEMILUMINESCENCE QUENCHING TERMS

Abstract— A methodology for the determination of chemiluminescence quenching terms is given. By using the oxidation of tetrakis(dimethylamino)ethylene as an example, it is shown how the nature and magnitude of the quenching terms help to elucidate the reaction mechanism, or how ignoring them can lead to false impressions. It is shown that chemiluminescence quenching effects need not be the same as those for photoluminescence of the same electronically excited species.