Heat capacities of copper(II) formate tetrahydrate and tetradeuterate: A comparative study of phase transitions in layer hydrate crystals

The heat capacities of copper(II) formate tetrahydrate and tetradeuterate have been measured from 12 to 300 K with an adiabatic calorimeter. They have sigmoidal temperature dependence except near the antiferroelectric-paraelectric transition temperatures, 235.78 ± 0.05 K and 245.64 ± 0.05 K, respectively. The corresponding enthalpy changes are 836.0 ± 1.0 J mol^?1 and 936.9 ± 0.5 J mor^?1. The entropy changes are 3.546 ± 0.005 JK^?1mol^?1 and 3.814 ± 0.002 JK^?1 mol^?1. The heat capacities are larger in the high temperature phase than in the low temperature phase, the difference amounting to 5.74 JK^?1 mol^?1 and 7.15 JK^?1 mol^?1 for the hydrate and the deuterate, respectively. The heat capacity anomaly is compared with those in tin(II) chloride dihydrate and potassium hexacyanoferrate trihydrate and discussed in relation to the structure of the hydrogen bond networks in these substances. The discussion is extended to include possible properties of the hydrogen bond frameworks in ices I_h and II.     

Waveguide holograms: A new approach to hologram integration

A new class of holography is proposed, in which (1) the evanescent part of a guided wave, or (2) the guided wave in a thin-film hologram is utilized as the reference wave and/or the illuminating one. The hologram was designated as “wave-guide hologram” and has advantages in the possibility of integration, wide field of view, and compactness and high reliability of the reconstructing system. The possibility of the waveguide hologram has been proved through reconstruction experiments with a guided wave of a waveguide hologram recorded with a plane reference wave.     

The stochastic Boltzmann equation and hydrodynamic fluctuations

Based on the assumption of a kinetic equation in space, a stochastic differential equation of the one-particle distribution is derived without the use of the linear approximation. It is just the Boltzmann equation with a Langevin-fluctuating force term. The result is the general form of the linearized Boltzmann equation with fluctuations found by Bixon and Zwanzig and by Fox and Uhlenbeck. It reduces to the general Landau-Lifshitz equations of fluid dynamics in the presence of fluctuations in a similar hydrodynamic approximation to that used by Chapman and Enskog with respect to the Boltzmann equation.This work received financial support from the Alexander von Humboldt Foundation.     

Heat capacity of a five-coordinated iron(III) complex with spin S = 32, bromobis(N,N-diethyldithiocarbamato)iron(III), between 0.4 and 300 K

Heat capacity measurements have been made for six kinds of specimens prepared by different methods. Among them, Sample A exhibited a A-type ferromagnetic pahse transition at 1.347 K and a Schottky-type anomaly due to the zero-field splitting around 9K. The total entropy and enthalpy were (11.05 ± 0.04) J K^?1mol^?1 and (97.0 ± 0.4) J mol^?1, respectively. Sample B exhibited a Sehottky-type anomaly around 0.4 K due to the ferro-magnetic dimeric coupling with $\text{J}{}_{\mathrm{D}}\text{k}\text{= + 0.30}\text{K}$ as well as the Schottky-type anomaly at 9K. The total magnetic entropy and enthalpy were (11.45 ± 0.03) JK^?1 mol^?1 and (93.8 ± 0.8) J mol^?1, respectively. The remaining samples are simple mixtures of the λ-type modification and the dimeric modification. Irrespective of the magnetic behavior at low temperatures, all the samples showed a non-magnetic first-order phase transition around 270 K. The heat capacity and entropy of this phase transition have been accounted for in terms of the Frenkel theory of heterophase fluctuation. Construction of an adiabatic-type calorimeter workable between 1.5 and 393 K has been also presented.     

Kinetic study of BH3 reduction of benzaldehydes: identification of effective reducing species

A kinetic study was carried out for the reaction of benzaldehyde and borane (BH₃) in tetrahydrofuran. The effect of BH₃ concentration on the rate constant showed that the reaction order with respect to BH₃ was 1.6. Substituent effects gave a linear Hammett plot with a ρ value of ?0.51. It was concluded that the reaction proceeds through a rate‐determining hydride‐transfer transition state with two BH₃ molecules, in which one molecule of BH₃ acts as a reducing agent and the other serves as a catalyst. Copyright © 2011 John Wiley & Sons, Ltd.     

Hydrogen bond lifetimes in supercritical methanol–water mixtures via MD simulation

Dynamical features of hydrogen bonds in methanol–water mixtures have been analysed in terms of lifetime in the wide range of conditions, including supercritical states, using a molecular dynamics simulation with flexible potential models. Hydrogen bond characteristics in methanol–water mixtures were investigated by considering the combination of molecular species and donor–acceptor of hydrogen-bonded molecules. The hydrogen bond lifetimes mainly depend on temperature, and those in supercritical condition were about 1/10th of that at ambient condition. Focusing on the composition dependence of the hydrogen bond lifetime, the unique behaviour of that resulting from hydration structure was observed. Moreover, the molecular combination, which showed the largest hydrogen bond lifetime, was different for ambient and high temperature and high pressure conditions. The relationship between hydrogen bond lifetime and molar volume was also calculated to discuss the hydrogen bond lifetime in terms of the collision frequency of molecules and the intermolecular distance.     

Echo-intensity compensation in echolocating bats (Pipistrellus abramus) during flight measured by a telemetry microphone

An onboard microphone (Telemike) was developed to examine changes in the basic characteristics of echolocation sounds of small frequency-modulated echolocating bats, Pipistrellus abramus. Using a dual high-speed video camera system, spatiotemporal observations of echolocation characteristics were conducted on bats during a landing flight task in the laboratory. The Telemike allowed us to observe emitted pulses and returning echoes to which the flying bats listened during flight, and the acoustic parameters could be precisely measured without traditional problems such as the directional properties of the recording microphone and the emitted pulse, or traveling loss of the sound in the air. Pulse intensity in bats intending to land exhibited a marked decrease by 30 dB within 2 m of the target wall, and the reduction rate was approximately 6.5 dB per halving of distance. The intensity of echoes returning from the target wall indicated a nearly constant intensity (-42.6 +/- 5.5 dB weaker than the pulse emitted in search phase) within a target distance of 2 m. These findings provide direct evidence that bats adjust pulse intensity to compensate for changes in echo intensity to maintain a constant intensity of the echo returned from the approaching target at an optimal range.     

Studies on vocal fold injection and changes in pitch associated with alcohol intake

The current study was carried out with particular emphasis on the association between phonetic function tests and alterations in the appearance of the hypopharyngeal and laryngeal mucosa, such as capillary dilatation, edema, and vocal fold injection after alcohol intake. The results demonstrated the occurrence of previously unrecognized pathophysiological changes associated with synchronous phonetic functions in the vocal pathway after alcohol intake. Serum ethanol and aldehyde concentration levels were evaluated hourly for 2.5 h after ingestion of alcohol. When an electronystagmogram showed the typical pattern of alcohol intake, the study was initiated. Occasionally, rhinography was performed on subjects complaining of a stuffy nose after alcohol intake.