The position dependent 15N enrichment of nitrous oxide in the stratosphere.

The position dependent 15N fractionation of nitrous oxide (N2O), which cannot be obtained from mass spectrometric analysis on molecular N2O itself, can be determined with high precision using isotope ratio mass spectrometry on the NO+ fragment that is formed on electron impact in the source of an isotope ratio mass spectrometer. Laboratory UV photolysis experiments show that strong position dependent 15N fractionations occur in the photolysis of N2O in the stratosphere, its major atmospheric sink. Measurements on the isotopic composition of stratospheric N2O indeed confirm the presence of strong isotope enrichments, in particular the difference in the fractionation constants for 15N14NO and 14N15NO. The absolute magnitudes of the fractionation constants found in the stratosphere are much smaller, however, than those found in the lab experiments, demonstrating the importance of dynamical and also additional chemical processes like the reaction of N2O with O(1D).     

Nitrogen-15 NMR spectroscopy of proteins in solution

Experimental results from ¹⁵N NMR studies of selectively and uniformly labeled proteins with molecular weights ranging between 6000 and 155,000 Da in solution are described. These results demonstrate the resolution available in one- and two-dimensional ¹⁵N NMR spectra as well as the selection of particular ¹⁵N and ¹H resonances on the basis of the type of amino acid residue, the number of hydrogens bonded to a nitrogen, local dynamics, and amide hydrogen exchange kinetics.     

Infra-Red Spectra of the Nitrogen-15 Labelled Triphosphonitrilic Chloride

Although the vibrational spectra of triphosphonitrilic chloride, (PNCl₂)₃ (1), have been studied by numerous investigators^1–8, there is no general agreement about the frequency of completely inactive A₂ ring vibration. Besides, assignment of some overtones and combination bands is doubtful.     

The thermal conductivity of argon,carbon dioxide and nitrous oxide

The paper presents new, absolute measurements of the thermal conductivity of three gases: argon (Ar), carbon dioxide (CO₂) and nitrous oxide (N₂O). The measurements have been carried out with a transient hot-wire instrument in the temperature range 308 to 430 K and at pressures up to 11 MPa. For most of the range of thermodynamic states covered by the measurements it is estimated that the accuracy of the thermal conductivity data is one of ±0.3%. However, for carbon dioxide and nitrous oxide near their critical conditions the accuracy is degraded and the uncertainty may be as much as ±2%. The new experimental data for argon confirm the accuracy claimed for the thermal conductivity in the limit of zero-density.The thermal conductivity of the polyatomic gases in the limit of zero-density is used in conjunction with information on other transport cross-sections for the same systems, to extract a consistent set of cross-sections sensitive to the anisotropy of the intermolecular pair potential for use in the testing of proposed potential surfaces. Cross-sections for both of the available formulations of the thermal conductivity of a polyatomic gas due to Wang Chang and Uhlenbeck and Thijsse et al. are derived. For both gases it is shown that the Mason-Monchick approximation breaks down in either formulation. However, the effect of the failure on the formulation of Thijsse et al. is smaller and it is possible to represent the data with the aid of a single cross-section which has a very simple temperature dependence. The analysis also demonstrates that all available high-temperature thermal conductivity data for carbon dioxide are in substantial error.In the moderately dense gas the concept of a temperature-independent excess thermal conductivity is confirmed to a high degree of precision for carbon dioxide and argon when due allowance is made for the critical enhancement. A generalized correlation of the temperature dependence of the first density coefficient of thermal conductivity is broadly confirmed.     

Magnesium oxide nanocrystals via thermal decomposition of magnesium oxalate

The present work reports the synthesis of magnesium oxide (MgO) nanocrystals via a thermal decomposition route and the study of physicochemical properties of products. The MgO nanocrystals were prepared from magnesium oxalate powders as precursor. Transmission electron microscopy (TEM) analysis demonstrated MgO nanocrystals with an average diameter of about 20−25 nm. The products were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), selected area electronic diffraction (SAED), and Fourier transform infrared (FT-IR) spectroscopy. Optical absorption and photoluminescence emission properties of MgO nanocrystals were investigated.     

Spectroscopic determination of the nitrogen isotopic composition in the region of subnatural15N concentrations

Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 50, No. 3, pp. 407–412, March, 1989.     

Effect of isotopic composition on the linear thermal expansion coefficient of a germanium crystal lattice

Features of the thermal expansion coefficient α(T) of crystal lattices with different isotopic compositions have been analyzed. The case of germanium lattices has been studied in detail. Zh. éksp. Teor. Fiz. 114, 654–668 (August 1998)     

Flame propagation in gaseous nitrous oxide

The characteristics of the propagation of a nitrous oxide decomposition flame in a tube with an internal diameter of 70 mm were measured. It was demonstrated that the pattern of flame propagation and the extent of burnout are determined by the convective motion of the flame kernel because of a very slow burning of nitrous oxide. The laminar flame speed estimated from pressure oscillograms and calculated using thermal theory of flame propagation was found to be ～1 cm/s. The critical diameter of flame quenching in channels were measured to decrease from 10 to 4 mm as the pressure was increased from 15 to 20 atm. Because of the possibility of reignition of the fresh mixture behind the flame arrester by the outflowing combustion products, the channel should be significantly longer than 200 mm.     

Nitrogen-15 Fractionation in the Thermal Decomposition of Nitrous Oxide of Natural Isotopic Composition

Abstract

The ¹⁵N fractionation in the thermal decompostion of nitrous oxide (N₂O) of natural isotopic composition has been investigated in quartz reaction vessel in the temperature interval 888–1073K. The formulas relating the observed experimentally ¹⁵N fractionations with the primary ¹⁵N kinetic isotope effect, (k ¹⁴/k ¹⁵)_p for ¹⁴N¹⁵N¹⁶O, and secondary ¹⁵N kinetic isotope effect, (k ¹⁴/k ¹⁵)_s for ¹⁵N¹⁴N¹⁶O, have been derived. The experimentally estimated ¹⁵N kinetic isotope effects have been compared with the primary and secondary ¹⁵N kinetic isotope effects calculated with the absolute rate theory formulations applied to linear three atom molecules. A good agreement was found for the primary ¹⁵N kinetic isotope effect, (k ¹⁴/k ¹⁵)_p, in the temperature interval 888–1007K. But at 1073K the decompositions of N₂O, accompanied by NO (nitric oxide) formation proceed with a twice times smaller primary kinetic isotope effect, (k ¹⁴/k ¹⁵)_p of 1.0251 ± 0.0009, only, suggesting the nonlinear transition state structures with participation of the fourth external atom at high temperature decompositions of nitrous oxide. The nitrogen isotope effects determined in this study correlate well with nitrogen isotope fractionations observed in the natural biological, earth and atmospheric processes.     

Spinodal decomposition in solid isotopic helium mixtures

We report the first observations of spinodal decomposition in solid helium isotopic mixtures, using NMR measurements. The experiments were performed at a 3He concentration of 50% where the transition proceeds through the critical point. We used an initial pressure such that the system remained solid. Our observations indicate that the transition occurs by the mechanism of spinodal decomposition and we are able to study its evolution in real time.     

C-radiolabeling study of methanol decomposition on copper oxide modified mesoporous SBA-15 silica

¹¹C-radiolabeling technique is applied to investigate methanol decomposition on copper oxide modified SBA-15. Nitrogen physisorption, XRD, FTIR, UV-vis and TPR techniques are used for catalyst characterization. Selective adsorption coverage of the catalytic active sites with ¹¹C- and ¹²C-methanol molecules is carried out and the products of their conversion are followed. The mechanism of methyl formate, methylal and CO₂ formation from methanol is discussed.     

Sextic force field of nitrous oxide

The sextic force field in the curvilinear internal coordinates has been studied for the nitrous oxide molecule from the spectroscopic data of ¹⁴N₂¹⁶O, ¹⁴N¹⁵N¹⁶O, and ¹⁵N¹⁴N¹⁶O. The bands below 6600 cm⁻¹ have been used. The force constants in the internal coordinates are converted to those in dimensionless normal coordinates by two successive transformations. The vibration Hamiltonian matrix for each symmetry species of a given isotopic species has been constructed from the harmonic oscillator basis functions, and it is then diagonalized numerically to give the vibrational energy levels and the wavefunctions. The latter have been used for the evaluation of ratational constants. The least-squares refinement has been very successful in the present study, and it is shown that the general quartic force field supplemented by the quintic and sextic stretching diagonal force constants estimated from the Morse function, provided that the terms up to sextic are kept in the dimensionless normal coordinate space, well reproduces the spectroscopic constants such as the vibrational levels, rotational constants, l-type doubling constants, and centrifugal distortion constants. The spectroscopic constants of the isotopic molecules which are excluded from the refinement process are also in good agreement with the computed ones. The bond dissociation energies of the NN and NO bonds estimated from the present results have been critically examined.     

The structure and extinction of nonpremixed methane/nitrous oxide and ethane/nitrous oxide flames

Knowledge of combustion of hydrocarbon fuels with nitrogen-containing oxidizers is a first step in understanding key aspects of combustion of hypergolic and gun propellants. Here an experimental and kinetic-modeling study is carried out to elucidate aspects of nonpremixed combustion of methane (CH₄) and nitrous oxide (N₂O), and ethane (C₂H₆) and N₂O. Experiments are conducted, at a pressure of 1 atm, on flames stabilized between two opposing streams. One stream is a mixture of oxygen (O₂), nitrogen (N₂), and N₂O, and the other a mixture of CH₄ and N₂ or C₂H₆ and N₂. Critical conditions for extinction are measured. Kinetic-modeling studies are performed with the San Diego Mechanism. Experimental data and results of kinetic-modeling show that N₂O inhibits the flame by promoting extinction. Analysis of the flame structure shows that H radicals are produced in the overall chain-branching step 3H₂ + O₂ ? 2H₂O + 2H, in which molecular hydrogen is consumed. Hydrogen is also consumed in the overall step N₂O + H₂ ? N₂ + H₂O where stable products are formed. Inhibition of the flames by N₂O is attributed to competition between these two overall steps.     

Sulfur isotopic composition of mangroves

Abstract Sulfur isotope ratios of mangrove leaves of 19 species were compared to discuss the species-specific characteristics of sulfur uptake and assimilation. The members of Rhizophora and Bruguiera always show remarkable enrichments of the light isotope, giving negative δ(34)S values in most cases. The elaborated root systems of such species seem to be closely related to their sulfur absorbing systems as an adaptation to their anaerobic soil conditions.     

Evolution of isotopic composition of reprocessed uranium during the multiple recycling in light water reactors with natural uranium feed

A complex approach based on the consistent modeling of neutron-physics processes and processes of cascade separation of isotopes is applied for analyzing physical problems of the multiple usage of reprocessed uranium in the fuel cycle of light water reactors. A number of scenarios of multiple recycling of reprocessed uranium in light water reactors are considered. In the process, an excess absorption of neutrons by the ²³⁶U isotope is compensated by re-enrichment in the ²³⁵U isotope. Specific consumptions of natural uranium for re-enrichment of the reprocessed uranium depending on the content of the ²³²U isotope are obtained.