Force Constants and Bond Orders of Nitrogen Bonds

The force constants and the corresponding bond orders of nitrogen bonds have been calculated from the vibrational spectra (infrared and Raman spectra) of a great number of nitrogen compounds. Plotting the maximum bond order of stable nitrogen bonds against the sum of Pauling's electronegativities of the bonding partners (Σx) leads to one continuous curve for the N? X bonds where X represents elements of the first and the second short period of the periodic table. Furthermore, when the bonds formed between these elements are arranged in a coordinate system in such a way that the position of each bond is determined by the difference between the electronegativities of the bonding partners (Δx along the ordinate) and the sum of the electronegativities of the bonding partners (Σx along the abscissa), the bonding partners capable of forming multiple bonds all lie within a closed domain, where their position can be correlated with their polymerizability and other reactivities of the multiple bonds. Also discussed are the orders of bonds between nitrogen and some transition elements. In an appendix, the present methods used to calculate force constants and bond orders are surveyed.     

Dinitrogen-Transition Metal Complexes: Synthesis,Properties, and Significance

Compared to the large number of CO complexes, N₂ complexes are still rare. In certain cases they may be formed from N₂ gas and metal compounds under physiological conditions, and are therefore frequently considered as possible intermediates in N₂ assimilation. However, despite numerous attempts it has not yet been possible to reduce the N₂ ligand of a fully characterized N₂ complex to NH₃. This negative evidence recently prompted the discoverers of the first dinitrogen complex, the [Ru(NH₃)₅N₂]^2⊕ ion isolated in 1965, to express doubt whether such complexes really do play a part in the enzymatic reduction of N₂. The latest findings nevertheless incline toward a somewhat more optimistic view. Thus, the mild partial reduction of the N₂ ligand in metal complexes with inert gas configuration, hitherto considered nonreducible, justifies the hope that a suitable system permitting the catalytic reduction of molecular nitrogen under normal conditions will one day be found. Even apart from any technical potential, the N₂ complexes constitute an interesting chapter of modern inorganic chemistry.     

Symbiotic N2 Fixation and N Uptake of Yellow and White Lupines Influenced by Spontaneous Rhizobia Infection and Substrate

Abstract

By using soil as substrate, white and yellow lupines (Lupinus albus L., Lupinus luteus L.) assimilated higher N amounts than under quartz sand conditions. This was caused by spontaneous infection of lupines with wild Rhizobia strains and also by an additional N uptake from the soil. In yellow lupines without inoculation in non-sterile soil, only the additional N uptake played a role. Differences in P and K supply as the cause of different N acquisition from soil and quartz sand could be excluded. As compared with white lupines, yellow lupines inoculated with Rhizobia had a high N₂ fixation that exceeded the effect of spontaneous infections. This result as well as the positive effect of spontaneous infections with soil-borne Rhizobia on white lupines indicates insufficient effectiveness of the strains used for inoculation on this plant species.     

N2-broadening coefficients in the ν2 and ν4 bands of PH3

N₂-broadening coefficients are measured for 61 transitions of PH₃ in the ^QR branch of the ν₂ band and the ^PP, ^RP, ^SP, and ^PQ branches of the ν₄ band, using a tunable diode-laser spectrometer. The recorded lines with J values ranging from 1 to 16 and K from 0 to 11 are located between 1008 and 1106 cm⁻¹. The collisional widths are determined by fitting each spectral line with a Voigt profile, a Rautian profile, and a speed-dependent Rautian profile. The latter models provide larger broadening coefficients than the Voigt model. These coefficients have also been calculated on the basis of a semiclassical model of interacting linear molecules by considering an atom-atom Lennard-Jones potential in addition to the electrostatic contributions. The theoretical results are in good agreement with the experimental data and reproduce the J dependence of the broadenings, but their decrease at high J values is overestimated for the ^QR (J, K) transitions.     

Using the natural 15N abundance to assess the main nitrogen inputs into the sand dune area of the North-Western Negev desert (ISRAEL)

The variation of the natural ¹⁵N abundance is often used to evaluate the origin of nitrogen or the pathways of N input into ecosystems. We tried to use this approach to assess the main input pathways of nitrogen into the sand dune area of the north-western Negev Desert (Israel). The following two pathways are the main sources for nitrogen input into the system:

1. Biological fixation of atmospheric nitrogen by cyanobacteria present in biological crusts and by N₂-fixing vascular plants (e.g. the shrub Retama raetam);

2. Atmospheric input of nitrogen by wet deposition with rainfall, dry deposition of dust containing N compounds, and gaseous deposition.

Samples were taken from selected environmental compartments such as biological crusts, sand underneath these crusts (down to a depth of 90?cm), N₂-fixing and non-N₂-fixing plants, atmospheric bulk deposition as well as soil from arable land north of the sandy area in three field campaigns in March 1998, 1999 and 2000. The δ¹⁵N values measured were in the following ranges: grass ?2.5‰ to +1.5‰; R. reatam: +0.5‰ to +4.5‰; non-N₂-fixing shrubs +1‰ to +7‰; sand beneath the biological crusts +4‰ to +20‰ (soil depth 2–90?cm); and arable land to the north up to 10‰. Thus, the natural ¹⁵N abundance of the different N pools varies significantly. Accordingly, it should be feasible to assess different input pathways from the various ¹⁵N abundances of nitrogen. For example, the biological N fixation rates of the Fabaceae shrub R. reatam from the ¹⁵N abundances measured were calculated to be 46–86% of biomass N derived from the atmosphere. The biological crusts themselves generally show slight negative ¹⁵N values (?3‰ to ?0.5‰), which can be explained by biological N fixation. However, areas with a high share of lichens, which are unable to fix atmospheric nitrogen, show very negative values down to ?10‰. The atmospheric N bulk deposition, which amounts to 1.9–3.8?kg?N/ha?yr, has a ¹⁵N abundance between 4.4‰ and 11.6‰ and is likely to be caused by dust from the arable land to the north. Thus, it cannot be responsible for the very negative values of lichens measured either. There must be an additional N input from the atmosphere with negative δ¹⁵N values, e.g. gaseous N forms (NO _x , NH₃). To explain these conflicting findings, detailed information is still needed on the wet, particulate and gaseous atmospheric deposition of nitrogen.     

脉冲电晕放电脱除NO化学反应动力学过程

采用非接触的色散荧光发射光谱和时间分辨光谱方法,在大气压条件下,对脉冲电晕放电脱除NO的化学反应动力学过程进行了实验研究。在该研究中,首先利用色散荧光发射光谱方法,得到纯NO气体脉冲电晕放电中各活性粒子的色散荧光谱,并对其进行归属,确定了各活性粒子的灵敏指纹跃迁谱线;在此基础上,通过测量NO气体放电过程中所产生的N+,O,N₂及NO分子的灵敏指纹跃迁谱线的时间行为特性,研究脉冲电晕放电脱除NO的化学反应机理。实验结果表明：在脉冲电晕放电过程中,NO分子首先与高能电子发生非弹性电离碰撞,变成NO+离子,随后NO+离子发生解离反应,形成N+离子和O原子;N+离子在向阴极运动过程中与电子碰撞结合成激发态N原子,继而和其他激发态N原子结合成为激发态N₂;而O原子则应与其它O原子结合成为O₂。由此建立了大气压条件下纯NO气体脉冲电晕放电脱除NO的化学反应动力学模型。     

三氯化氮气体喷射自发分解实验研究

 在气体流动管中对三氯化氮气体喷射自发分解的现象进行了初步实验研究。在一根长80 cm，直径4 cm的圆柱形石英玻璃管中，用喷嘴向气体流动管内喷射NCl₃/He混合气体，观察到了NCl₃喷射分解时的红色火焰。测量了火焰光谱并进行了归属，认为该光谱是Cl₂(B→X)辐射跃迁。NCl­₃的喷射自发分解本质上是激波诱导发生的，即分子的动能转化为分子内能而引起的，生成的Cl原子及NCl₂自由基与NCl₃分子反应，从而得到持续燃烧火焰。实验结果表明了NCl₃自发分解反应可代替放电或燃烧作为Cl原子的来源。     

Interaction of indigo carmine dye with silica modified with humic acids at solid/liquid interface

Two distinct humic acids, one extracted from Brazilian peat soil, HA_PS, and another one obtained from commercial source, HA_FL, were attachment onto silica gel modified with aminopropyltrimethoxysilane, producing two material named SiHA_PS and SiHA_FL, respectively. The ability of these materials in removing indigo carmine dye from aqueous solution was followed through series of adsorption isotherms adjusted to modified Langmuir equation. The maximum number of moles adsorbed gave 6.82 ± 0.12 × 10⁻⁴ and 2.15 ± 0.17 × 10⁻⁴ mol g⁻¹ for SiHA_PS and SiHA_FL, respectively. Same interactions were calorimetrically followed and the thermodynamic data showed endothermic enthalpic values: 12.31 ± 0.55 and 24.69 ± 1.05 kJ mol⁻¹ for SiHA_PS and SiHA_FL surfaces, respectively. Gibbs free energies for two adsorption processes of indigo carmine dye presented negative values, reflecting dye/surface interactions must be accompanied by an increased in entropy values, which are 65 ± 3 and 98 ± 5 J mol⁻¹ K⁻¹ for SiHA_PS and SiHA_FL materials, respectively. The adsorption processes for both materials were spontaneous in nature although they presented an endothermic enthalpy for the interaction, resulting in an entropically favored process.     

泥炭中全氮的测定

采用连续流动化学分析仪（Continuous Flow Analyzer,CFA）,对泥炭中的全氮进行分析.方法有良好的线性关系（r=0.9999）,回收率为99％-105％,测试速度是比色法测试速度的15-20倍,操作简便、准确度好,对氮化学研究有一定意义.     

直流大气压电晕放电电子密度的光谱研究

利用自制针—板式放电装置,在大气中进行电晕放电实验。用发光区域照片光斑的大小,讨论了电晕层厚度与电源电压的关系。在相同针板间距下,电晕层厚度随着电压的升高而增大;在相同电压下,电晕层厚度随着针板间距的增大而减小。由于高能电子密度能够通过氮分子第二正带系337.1 nm的光谱强度大小反映,因此对氮分子第二正带系337.1 nm谱线的强度用发射光谱法进行了测量。实验结果发现在针尖附近高能电子密度最大,并且高能电子密度随电压的升高而增大;电压一定时,高能电子密度随针板间距的增大而减小。在针板间距和电源电压不变的情况下,高能电子密度随针尖曲率半径的减小而增大。