Oscillatory kinetics and mechanism of the chromate catalyzed decomposition of hydrogen peroxide

Oscillatory change of pH occurs during the chromate-catalyzed decomposition of hydrogen peroxide in a weakly acidic medium at elevated temperature and at high initial concentration of hydrogen peroxide. In a closed system, there are only two or three periods, but sustained oscillation occurs in a CSTR. In a CSTR bistability is also found. In closed systems the temperature exhibits a great maximum (up to 15°C increase), in a CSTR sustained oscillation occurs at a constant stationary temperature.     

Transport properties of a side-chain liquid-crystalline polymer. Poly(4-acryloyloxy biphenyl)

The transport properties of a side-chain liquid-crystalline polymer forming a smectic A phase have been investigated using dichloromethane as a permeant. Samples differing in the isotropization enthaoly were analyzed. A. Correlation between this thermal parameter and sorption has been found, while the diffusion coefficient is substantially the same in all samples. The results obtained can be explained in terms of a biphasis model in which a disordered permeable phase is present within the liquid-crystalline phase, which is impermeable to the diffusant molecules.     

The Interference Slow Wave in a Poroacoustic Biot Layer

It is shown that in a poroacoustic Biot layer placed inside an elastic medium, for any parameters of the model an interference slow wave exists. For low frequencies, the wave has very weak attenuation and the polarization of it coincides with the direction of the layer. This is evidence for the possibility of mapping subtle collectors inside an elastic medium in crosshole measurements. Bibliography: 7 titles.     

Effect of Finite Spectral Width on the Modulational Instability of Langmuir Waves described by a Nonlinear Schrödinger Equation

By using the two-point space correlation function an equation for the power spectral density for a random Langmuir field has been derived. The dispersion relation for a monochromatic wave is regained for a delta spectrum. For a Gaussian spectrum, the maximum growth rate is less than that for a monochromatic wave. For a “meander spectrum”, the growth rate is increased with the width of the spectrum in the first stage then decreased for further increase of the width.     

Book reviews

Ohne Zusammenfassung

---

Book reviews

     

Deformation of doped NaCl crystals during uniaxial compression at temperatures of 4.2–293 K

The impurity weakening of crystalline NaCl:Mg and NaCl:Mn associated with purification of the matrix in a melt is demonstrated. This effect is manifested in a consistent change in the yield strength and mobility of dislocations. Its unusual temperature dependence is determined: in a number of cases weakening becomes greater as the temperature is lowered within the interval 293–4.2 K. A deviation in the elastic region of the stress-strain curves is observed to increase as the temperature is lowered. Plasticizing of crystalline NaCl is established: when the deformation temperature is lowered from 293 to 77 and 4.2 K the rate of rise in the yield strength of Cd²⁺ and Sr²⁺ doped samples is lower than that of undoped samples. An explanation for this fact is proposed. Fiz. Tverd. Tela (St. Petersburg) 39, 313–317 (February 1997) Deceased.     

Short-range order in miscible polymer blends: A monte carlo study

Local ordering in miscible binary polymer blends with strong attractive interactions between the two types of chains was investigated by computer simulation of allowable conformations on an incompressible cubic lattice. A tendency toward maximum ordering (in which chains pack in alternate parallel rows) is shown by the calculation of pair correlations and in “snapshots” of the mixtures. A specific directional interaction is not necessarily required for ordering. A comparison of these results with those recently obtained using mean-field theory is presented. The heat capacity of mixing was also calculated and found to be positive, with a value close to that reported experimentally.     

Determination of total oxygen in standard rocks by cyclic activation analysis using a 14 MeV neutron generator

Total oxygen, in fourteen rock standards and three ores, was determined with an experimental set up employing cyclic activation analysis using a 14 MeV neutron generator gamma-spectroscopy and NaI(T1) detectors.     

A model of the kinetics of macrocyclic BPA carbonate formation

Cyclic oligocarbonates are synthesized by two-phase interfacial reactions of aryl bischloroformates in the presence of an amine phase transfer catalyst and an alkali: nClOCOArOCOCl + 4nNaOH → (OArOCO)_n + 2nNaCl + nNa₂CO₃ + 2nH₂O. The organocarbonate product may be a macrocyclic oligomer or a linear chain polymer. A qualitative mechanism for this behavior has been proposed by Brunelle, Boden, and co-workers. Four steps are identifiable: activation of the aryl bischloroformate by the amine catalyst, hydrolysis of a portion of this intermediate at the aqueous/organic phase interface, oligomerization between activated and hydrolyzed moieties also at the interface, and chain terminating carbamate formation that leads to polymer. An important modification is made within the framework of the Brunelle and Boden mechanism. While the intramolecular cyclization reaction is formally second-order overall, it behaves as a first-order process. The kinetic constants for both this pseudo-first-order cyclization step and the corresponding second-order linearization step are simply related. It is speculated that the above relationship can be generalized for a whole class of pseudo-first- and second-order rate constants for similar macrocyclic reactions.