Reactions of OH with butene isomers: measurements of the overall rates and a theoretical study

Reactions of hydroxyl (OH) radicals with 1-butene (k(1)), trans-2-butene (k(2)), and cis-2-butene (k(3)) were studied behind reflected shock waves over the temperature range 880-1341 K and at pressures near 2.2 atm. OH radicals were produced by shock-heating tert-butyl hydroperoxide, (CH(3))(3)-CO-OH, and monitored by narrow-line width ring dye laser absorption of the well-characterized R(1)(5) line of the OH A-X (0, 0) band near 306.7 nm. OH time histories were modeled using a comprehensive C(5) oxidation mechanism, and rate constants for the reaction of OH with butene isomers were extracted by matching modeled and measured OH concentration time histories. We present the first high-temperature measurement of OH + cis-2-butene and extend the temperature range of the only previous high-temperature study for both 1-butene and trans-2-butene. With the potential energy surface calculated using CCSD(T)/6-311++G(d,p)//QCISD/6-31G(d), the rate constants and branching fractions for the H-abstraction channels of the reaction of OH with 1-butene were calculated in the temperature range 300-1500 K. Corrections for variational and tunneling effects as well as hindered-rotation treatments were included. The calculations are in good agreement with current and previous experimental data and with a recent theoretical study.     

In search of a new class of stable nitroxide: synthesis and reactivity of a peri-substituted N,N-bissulfonylhydroxylamine

Acyclic bissulfonylnitroxides have never been isolated, and degrade through fragmentation. In an approach to stabilising a bissulfonylnitroxide radical, the cyclic, peri-substituted N,N-bissulfonylhydroxylamine, 2-hydroxynaphtho[1,8-de][1,3,2]dithiazine 1,1,3,3-tetraoxide (1), has been prepared by formal nitrogen insertion into the sulfur-sulfur bond of a sulfinylsulfone, naphtho[1,8-cd][1,2]dithiole 1,1,2-trioxide. The heterocyclic ring of 1 is shown to adopt a sofa conformation by X-ray crystallography, with a pseudo-axial hydroxyl group. N,N-Bissulfonylhydroxylamine 1 displays high thermal, photochemical and hydrolytic stability compared to acyclic systems. EPR analysis reveals formation of the corresponding bissulfonylnitroxide 2 upon oxidation of 1 with the Ce(IV) salts CAN and CTAN. Although 2 does not undergo fragmentation, it cannot be isolated, since hydrogen atom abstraction to reform 1 occurs in situ. The stability and reactivity of 1 and 2 are compared with the known cyclic benzo-fused N,N-bissulfonylhydroxylamine, N-hydroxy-O-benzenedisulfonimide (6), for which the X-ray data, and EPR of the corresponding nitroxide 10, are also reported for the first time.     

Reactions of coordinated hydroxymethylphosphines with NH-functional amines: the phosphorus lone pair is crucial for the phosphorus Mannich reaction

Non-coordinated hydroxymethylphosphines react readily with primary and secondary amines by the phosphorus Mannich reaction. To determine if this reactivity can be used to synthesize phosphine macrocycles, trans-Fe(DHMPE)(2)Cl(2) (DHMPE = 1,2-bis(dihydroxymethylphosphino)ethane) was prepared and reacted with various amines. However, no phosphorus Mannich reactivity was observed. In order to understand why no reactions occurred, the Mannich reactivity of the borane-coordinated hydroxymethylphosphines DHMPE·2BH(3) and Ph(2)PCH(2)OH·BH(3) was investigated. These borane-coordinated phosphines also did not undergo the phosphorus Mannich reaction. These results suggest that the lone pair of electrons on the phosphorus atom is essential for the phosphorus Mannich reaction to occur, and therefore it is not possible to use this reaction in a templated synthesis of phosphine macrocycles. It is speculated that the mechanism of the phosphorus Mannich reaction may involve a methylenephosphonium intermediate, analogous to an iminium in the standard Mannich reaction. X-ray crystal structures of trans-Fe(DHMPE)(2)Cl(2) and DHMPE·2BH(3) are also presented. Both crystal structures display an extended hydrogen-bonding network in the solid state.     

A new paradigm for the molecular basis of rubber elasticity

The molecular basis for rubber elasticity is arguably the oldest and one of the most important questions in the field of polymer physics. The theoretical investigation of rubber elasticity began in earnest almost a century ago with the development of analytic thermodynamic models, based on simple, highly-symmetric configurations of so-called Gaussian chains, i.e. polymer chains that obey Markov statistics. Numerous theories have been proposed over the past 90 years based on the ansatz that the elastic force for individual network chains arises from the entropy change associated with the distribution of end-to-end distances of a free polymer chain. There are serious conceptual objections to this assumption and others, such as the assumption that all network nodes undergo a simple volume-preserving linear motion and that all of the network chains have the same length. Recently, a new paradigm for elasticity in rubber networks has been proposed that is based on mechanisms that originate at the molecular level. Using conventional statistical mechanics analyses, Quantum Chemistry, and Molecular Dynamics simulations, the fundamental entropic and enthalpic chain extension forces for polyisoprene (natural rubber) have been determined, along with estimates for the basic force constants. Concurrently, the complex morphology of natural rubber networks (the joint probability density distributions that relate the chain end-to-end distance to its contour length) has also been captured in a numerical model (EPnet). When molecular chain forces are merged with the network structure in this model, it is possible to study the mechanical response to tensile and compressive strains of a representative volume element of a polymer network. As strain is imposed on a network, pathways of connected taut chains, that completely span the network along strain axis, emerge. Although these chains represent only a few percent of the total, they account for nearly all of the elastic stress at high strain. Here we provide a brief review of previous elasticity theories and their deficiencies, and present a new paradigm with an emphasis on experimental comparisons.     

Wavelength modulation diode laser absorption spectroscopy for high-pressure gas sensing

A general model for 1f-normalized wavelength modulation absorption spectroscopy with nf detection (i.e., WMS-nf) is presented that considers the performance of injection-current-tuned diode lasers and the reflective interference produced by other optical components on the line-of-sight (LOS) transmission intensity. This model explores the optimization of sensitive detection of optical absorption by species with structured spectra at elevated pressures. Predictions have been validated by comparison with measurements of the 1f-normalized WMS-nf (for n = 2–6) lineshape of the R(11) transition in the 1st overtone band of CO near 2.3 μm at four different pressures ranging from 5 to 20 atm, all at room temperature. The CO mole fractions measured by 1f-normalized WMS-2f, 3f, and 4f techniques agree with calibrated mixtures within 2.0 %. At conditions where absorption features are significantly broadened and large modulation depths are required, uncertainties in the WMS background signals due to reflective interference in the optical path can produce significant error in gas mole fraction measurements by 1f-normalized WMS-2f. However, such potential errors can be greatly reduced by using the higher harmonics, i.e., 1f-normalized WMS-nf with n > 2. In addition, less interference from pressure-broadened neighboring transitions has been observed for WMS with higher harmonics than for WMS-2f.     

Optimality and duality with generalized convexity

Hanson and Mond have given sets of necessary and sufficient conditions for optimality and duality in constrained optimization by introducing classes of generalized convex functions, called type I and type II functions. Recently, Bector defined univex functions, a new class of functions that unifies several concepts of generalized convexity. In this paper, optimality and duality results for several mathematical programs are obtained combining the concepts of type I and univex functions. Examples of functions satisfying these conditions are given.     

Zero temperature phase transitions in spin-ladders: Phase diagram and dynamical studies of Cu2(C5H12N2)2Cl4>

In a magnetic field, spin-ladders undergo two zero-temperature phase transitions at the critical fields H_c1 and H_c2. An experimental review of static and dynamical properties of spin-ladders close to these critical points is presented. The scaling functions, universal to all quantum critical points in one-dimension, are extracted from (a) the thermodynamic quantities (magnetization) and (b) the dynamical functions (NMR relaxation). A simple mapping of strongly coupled spin ladders in a magnetic field on the exactly solvable XXZ model enables to make detailed fits and gives an overall understanding of a broad class of quantum magnets in their gapless phase (between H_c1 and H_c2). In this phase, the low temperature divergence of the NMR relaxation demonstrates its Luttinger liquid nature as well as the novel quantum critical regime at higher temperature. The general behavior close these quantum critical points can be tied to known models of quantum magnetism. Received: 13 March 1998 / Received in final form and Accepted: 21 July 1998     

Measurement of aerosol size distribution functions by wavelength-multiplexed laser extinction

Previous work on the measurement of aerosol size distribution functions (SDFs) by laser extinction mainly relied on light sources from a relatively narrow wavelength range. This paper investigates the potential advantages of extending the extinction method to a general wavelength-multiplexed laser extinction (WMLE) concept by incorporating an arbitrary number of laser sources from a wider wavelength range. This extension improves the sensitivity of SDF measurements over wider aerosol diameter ranges and enables a stable algorithm to invert the extinction data to obtain SDFs. These advantages are illustrated by an example WMLE scheme employing wavelengths in the spectral range from 0.25 to 10μm to measure SDFs of water aerosols. Application of this approach to other aerosol systems is also considered. The WMLE scheme was found to provide stable determination of a variety of SDFs with Sauter mean diameters ranging from sub-micron to about 10μm. The sensitivity of such determinations was evaluated to reveal the optimum applicable range of the wavelengths employed. The analyses performed here provide theoretical background and motivation for practical applications of the WMLE concept.     

Laser-induced fluorescence study of a xenon Hall thruster

2 ⁰→6p[3/2]₂(³P₂-¹D₂) transition at 823.2 nm and the xenon-ion 5d[3]_7/2→6p[2]_5/2 ⁰(⁴D_7/2-⁴P_5/2) transition is used to measure plasma parameters in the plume of a laboratory-model xenon Hall thruster. The Hall discharge operates nominally at 62 V, 4.2 A, and 3.2 mg s^-1 xenon flow, with an overall thruster power of 320 W. A tunable semiconductor diode laser and an Ar⁺-pumped dye laser are used to probe the respective excited-state transitions. Axial velocity measurements are made at a number of axial and radial locations up to 4.5 cm downstream of the thruster-exit plane and under a variety of thruster operating conditions. Neutral velocities from 100 m s^-1 to 400 m s^-1 and ion velocities as high as 12 km s^-1 are calculated from measured Doppler shifts. The charge-exchange phenomenon evidently does not significantly affect the xenon neutrals. The spectral-line shapes of the ion indicate a spread in ion energies through a non-Maxwellian distribution of axial velocities. Neutral kinetic temperatures of 500 (±200) K are observed under standard operating conditions. Zeeman and Stark effects on the spectral-line shapes, from the thruster’s magnetic and electric fields, are not substantial. The measured line center of the ion transition is 16521.23 (±0.02) cm^-1. Received: 20 January 1997/Revised version: 12 May 1997