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1.
Conductance measurements for fifteen uni-univalent salts in 2-methylpyridine-N-oxide (2-MPO) were made over the concentration range of 2–120×10–4 mol-dm–3 at 55°C. All conductance data were evaluated by the Lee-Wheaton equation. The results indicate that all of the salts studied are slightly associated in 2-MPO, which is, nevertheless, a reasonably good ionizing solvent compared to other solvents having a similar value for the dielectric constant. The tetraalkylammonium halides are weaker electrolytes than the tetraphenylborate salts in 2-MPO. Ionic limiting molar conductances were obtained by using as a reference electrolyte tris(iso-pentyl)butylammonium tetraphenylborate. Anions appear to be poorly solvated in this solvent but certain cations, particularly Na+ and K+, show evidence of specific ion-solvent interaction.This study was presented, in part, at the 6th Central Regional Meeting of the American Chemical Society, Detroit, Michigan, April 1974. 相似文献
2.
The Xe nuclear magnetic resonance chemical shift differences that afford the discrimination between various biological environments are of current interest for biosensor applications and medical diagnostic purposes. In many such environments the Xe signal appears close to that in water. We calculate average Xe chemical shifts (relative to the free Xe atom) in solution in eleven liquids: water, isobutane, perfluoro-isobutane, n-butane, n-pentane, neopentane, perfluoroneopentane, n-hexane, n-octane, n-perfluorooctane, and perfluorooctyl bromide. The latter is a liquid used for intravenous Xe delivery. We calculate quantum mechanically the Xe shielding response in Xe-molecule van der Waals complexes, from which calculations we develop Xe (atomic site) interpolating functions that reproduce the ab initio Xe shielding response in the complex. By assuming additivity, these Xe-site shielding functions can be used to calculate the shielding for any configuration of such molecules around Xe. The averaging over configurations is done via molecular dynamics (MD). The simulations were carried out using a MD technique that one of us had developed previously for the simulation of Henry's constants of gases dissolved in liquids. It is based on separating a gaseous compartment in the MD system from the solvent using a semipermeable membrane that is permeable only to the gas molecules. We reproduce the experimental trends in the Xe chemical shifts in n-alkanes with increasing number of carbons and the large chemical shift difference between Xe in water and in perfluorooctyl bromide. We also reproduce the trend for a given solvent of decreasing Xe chemical shift with increasing temperature. We predict chemical shift differences between Xe in alkanes vs their perfluoro counterparts. 相似文献
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Reactions occurring within the high-pressure mass spectrometer source during argon-enhanced negative-ion mass Spectrometry (NIMS) of mono- and dichlorophenols result in the formation of adduct ions. The reactants for the formation of the adduct ions are derived solely from the chlorophenol. High-resolution accurate mass -measurements of the adducts and comparison of the argon NIMS of the phenols with the argon-enhanced NIMS of authentic chlorinated phenoxyphenol and dichlorodioxin suggest that gas-phase intermolecular and intramolecular nucleophilic substitutions are occurring. The products of the source reactions reflect the stability of the gas-phase species involved and may be compared with the photolysis and pyrolysis reaction products of chlorophenols, chlorinated phenoxyphenols and chlorophenates reported in the literature. 相似文献
6.
B A Finnin M A A O'Neill S Gaisford A E Beezer J Hadgraft P Sears 《Journal of Thermal Analysis and Calorimetry》2006,83(2):331-334
Isothermal
calorimetry is becoming indispensable as a tool for the study of a wide variety
of systems. As with all scientific instruments it is essential that robust
calibration routines be developed in order to validate the data obtained.
Chemical test reactions offer many advantages over (the traditionally used)
joule effect heating methods, not least because they have the potential to
validate instrument performance (i.e. they can be used to assess all aspects
of calorimeter operation). In this work the results of a validation exercise,
conducted by Thermal Hazard Technology as part of an installation routine,
using the base catalysed hydrolysis of methyl paraben are discussed. In the
case described, a systematic misreporting of the reported temperature of a
calorimeter was identified, caused by an upgrade to the calorimeter's
firmware, a discrepancy which may not have been noted using traditional electrical
calibration methods and one which highlights the importance of both manufacturers
and end-users adopting chemical test reactions into their test and validation
routines. 相似文献
7.
Hugh L. Huffman Jr. Robert J. Lemire Paul G. Sears 《Journal of solution chemistry》1983,12(8):563-571
The conductance behavior of twenty-five 1∶1 electrolytes has been investigated in 3-methyl-2-oxazolidone (3Me20x) at 25°C. Conductance data were analyzed by the Lee-Wheaton equation, and all salts studied were found to be only slightly associated. Ionic limiting equivalent conductances were obtained using tris(iso-pentyl)butylammonium tetraphenylborate as a reference electrolyte. The relative values of the ionic limiting molar conductance are generally similar to those for other dipolar aprotic solvents. However, the order $$\lambda _0 (i - Pent_3 BuN^ + ) > \lambda _0 (Pent_4 N^ + )and\lambda _0 (Br^ - ) > \lambda _0 (ClO_4^ - )$$ is opposite to that found previously in the similar solvent 3-tert-bytyl-2-oxazolidone. 相似文献
8.
The influence of the first-order crystalline transformation at about 60°C on the infrared bands of trans-1,4-polybutadiene yields microscopic information that supports the two-component microcrystalline model of a folded chain having loose and tight end loops at the lamellar surfaces. The temperature dependence of the band parameters of the 908-cm?1 vinyl band indicates that 1,2-(side vinyl) units are not easily taken into the crystalline component, thus forming long loops at the crystal surface that account for the micro-Brownian motion detected in the low-temperature phase. The results argue that infrared band parameters are excellent probes for details of the thermodynamics and morphology of polymers. 相似文献
9.
An investigation of the plastic phases of polycrystalline specimens of sulphur hexafluoride (SF6) and carbon tetrabromide (CBr4) by neutron elastic scattering and neutron diffraction experiments is reported. A theory of neutron diffraction in plastic crystals, which treats the Bragg scattering and the diffuse scattering from a unified point of view, is developed and applied in the interpretation of the neutron results. The Debye-Scherrer peaks are analysed, both by a cumulant expansion technique and a cubic harmonic analysis, to determine the crystal structures of the plastic phase which are found to be body-centred cubic (space group Im3m) for SF6 and face-centred cubic (space group Fm3m) for CBr4. The bond-orientation distribution function, f(Ω), has maxima in the <100> directions for SF6 and in the <110> directions for CBr4. Since, in both cases, f(Ω) is appreciably different from zero for all orientations, it is apparent that significant thermal reorientation takes place in both these crystals. The translational and librational displacements in CBr4 are exceptionally large and give rise to extensive diffuse scattering which is analysed on the basis of a simple Einstein model. The model predicts that the centre-of-mass thermal vibration and the orientational disorder give approximately equal contributions to the total diffuse scattering. The calculated scattering is in good agreement with experiment for all wave vector transfers outside the range 2 to 3 Å-1. Inside this range discrepancies occur which are interpreted as evidence for the existence of orientational short-range order in CBr4. 相似文献
10.