Kinetics of the reaction Cl + CH4 → CH3+ HCl from 200° to 500deg;K

The rate constant for the reaction \documentclass{article}\pagestyle{empty}\begin{document}${\rm Cl} + {\rm CH}_4 \mathop {\longrightarrow}\limits^1 {\rm CH}_3 + {\rm HCl}$\end{document} has been determined over the temperature range of 200°–500°K using a discharge flow system with resonance fluorescence detection of atomic chlorine under conditions of large excess CH₄. For 300° > T > 200°K the data are best fitted to the expression k₁ = (8.2 ± 0.6) × 10^?12 exp[?(1320 ± 20)/T] cm³/sec. Curvature is observed in the Arrhenius plot such that the effective activation energy increases from 2.6 kcal/mol at 200° < T < 300°K to 3.5 kcal/mol at 360° < T < 500°K. The data over the entire range may be fitted by the expression k₁ = 8.6×10^?18 T^2.11 exp[?795/T]. These results are compared with other experimental studies and with a semiempirical transition state calculation. Their atmospheric significance is discussed.     

The reaction of carboxylic acid hydrazides with formaldehyde

The hydrazides of benzoic, phenyacetic, and 3-phenylpropionic acids react with an acidic solution of formaldehyde to give 15 . Similar treatment of the corresponding methylhydrazides gave 16 . The ethers 15 can be cleaved to give, after methylation, 16 . Spectral data for 15 and 16 are presented.     

On the damped nonlinear evolution equation wtt = σ(w)xx − ywt

Initial boundary value problems for the damped nonlinear wave equation w_tt = σ(w)_xx ? yw_t arise in several areas of applied mathematics and, in particular, in studies of shearing flow in a nonlinear viscoelastic fluid; the problems of global existence and nonexistence of smooth solutions have been extensively studied in the strictly hyperbolic case σ′(δ) ? ε > 0, ?δ?R¹ as well as in the case where σ′(0) > 0 and the initial data are chosen so small that σ′(w) > 0 for as long as a smooth solution w(x, t) exists. In this paper the global nonexistence problem is studied for the cases σ′(0) = 0 and σ′(0) > 0 but σ′(δ) < 0 for ¦δ¦ sufficiently large and growth estimates which are valid on the maximal interval of existence of a sufficiently smooth solution are derived.     

Pronounced enhancement of the lower critical field and critical current deep in the superconducting state of PrOs4Sb12

We have observed an unexpected enhancement of the lower critical field H(c1)(T) and the critical current I(c)(T) deep in the superconducting state below T approximately 0.6 K (T/T(c) approximately 0.3) in the filled skutterudite heavy fermion superconductor PrOs(4)Sb(12). From a comparison of the behavior of H(c1)(T) with that of the heavy fermion superconductors U(1-x)Th(x)Be(13) and UPt(3), we speculate that the enhancement of H(c1)(T) and I(c)(T) in PrOs(4)Sb(12) reflects a transition into another superconducting phase that occurs below T/T(c) approximately 0.3. An examination of the literature reveals unexplained anomalies in other physical properties of PrOs(4)Sb(12) near T/T(c) approximately 0.3 that correlate with the features we have observed in H(c1)(T) and I(c)(T).     

Where is the shot noise of a quantum point contact?

Reznikov et al. [Phys. Rev. Lett. 75, 3340 (1995)]] have presented definitive observations of nonequilibrium noise in a quantum point contact. Especially puzzling is the "anomalous" peak structure of the excess noise measured at constant current; to date it remains unexplained. We show that their experiment directly reveals the deep link between conservation principles in the electron gas and its low-dimensional, mesoscopic behavior. The keys to that connection are gauge invariance and the compressibility sum rule. These are central not only to the experiment of Reznikov et al., but to the very nature of all mesoscopic transport.     

Crystal field potential of PrOs4Sb12: consequences for superconductivity

The results of inelastic neutron scattering provide a solution for the crystal field level scheme in PrOs4Sb12, in which the ground state in the cubic crystal field potential of T(h) symmetry is a Gamma(1) singlet. The conduction electron mass enhancement is consistent with inelastic exchange scattering, and we propose that inelastic quadrupolar, or aspherical Coulomb, scattering is responsible for enhancing the superconducting transition temperature. PrOs4Sb12 appears to be the first compound in which aspherical Coulomb scattering is strong enough to overcome magnetic pair breaking and increase T(c).     

The spatial logistic map as a simple prototype for spatiotemporal chaos

A spatial extension of the logistic map-termed spatial logistic map-is found to display the same basic universality classes as the commonly studied diffusively coupled logistic lattice despite being vastly simpler. By analyzing the escape rates and the Lyapunov spectra it is shown that the main attractors of the spatial logistic map are stable and hence that it is a good candidate for serving as a prototype for the class of coupled map lattices which it is a part of. The spatial logistic map is then employed to provide an analytical derivation for the recently discovered linear scaling of the wavelength under increasing coupling ranges.     

Laser induced time-dependent thermal lensing studies of vibrational relaxation: translational cooling in CH3F

Time-resolved measurements of the thermal lens effect have been made for CH₃F, CH₃CI and C₂H₄. This technique is compared to others used in the study of vibrational relaxation phenomena and is found to be applicable to the study of a wide variety of gaseous systems at relatively low pressures. Translational cooling has been observed in CH₃F and an approximate lower limit of 200 msec^-1 has been established for the rate of this cooling process, which corresponds to equilibration of the ν₃ and ν₆ states, in a mixture of 0.2 torr CH₃F and 10 torr Ar.     

Aromatic Polyhedral Hydroxyborates: Bridging Boron Oxides and Boron Hydrides

No explosion , but per-B-hydroxylation occurs if the icosahedral boron hydrides [closo-B₁₂H₁₂]²⁻ (see picture), [closo-CB₁₁H₁₂]⁻, or closo-1,12-(CH₂OH)₂-1,12-C₂B₁₀H₁₀ are refluxed in 30 % hydrogen peroxide. Thus, the three isoelectronic species [closo-B₁₂(OH)₁₂]²⁻, [closo-1-H-1-CB₁₁(OH)₁₁]⁻, and closo-1,12-H₂-1,12-C₂B₁₀(OH)₁₀ were obtained. ○=BH, ○=BOH.