Raman spectral study of the constitution and equilibria of nitric acid and d-nitric acid

From relative integrated intensity measurements of the symmetric stretching vibration of nitrate ion in nitric acid solutions (both HNO ₃ /H ₂ O and DNO ₃ /D ₂ O), the mass law concentration quotients, Q were obtained as functions of concentration. By extrapolation the limiting dissociation constants were estimated to be 24.4 and 15 respectively at 25°C. It is shown that this constant refers to a process in which the ion pair H ₃ O⁺ NO ₃ ^– is in equilibrium with the dispersed, solvated H ₃ O⁺ and NO ₃ ^– ions.     

The synthesis of chiral functionalised morpholine N-oxides using a tandem Cope elimination/reverse-Cope elimination protocol

Hydroxylamine derivatives of (S)-prolinol have been generated using a Cope elimination. These undergo reverse-Cope elimination onto a pendant double bond to give morpholine N-oxides containing three contiguous chiral centres.     

Ester Elimination: A General Solvent Dependent Non-Hydrolytic Route to Metal and Mixed-Metal Oxides

Molecular routes to metal oxides has become an area of intensescientific interest due to the technological relevance of thesematerials. Molecular routes are proving important as a result ofthe possibility to control the physical and chemical propertiesof the final materials.We have chosen to study non-hydrolytic methods, namely esterelimination reactions between two prototypical molecularprecursors metal alkoxides, M(OR)_n, and metal carboxylates, M(O₂CR)_n, to synthesize metal oxides: This method allows for the synthesis of pure metal oxides bycomplete elimination of the organic supporting ligands withconcomitant formation of M-O-M bridges.Furthermore, incomplete esterelimination can lead to isolation of molecular clusters asintermediates which can also be used as building blocks for theformation of metal oxides with controlled microstructure.Here we report a series of reactions between Sn and Si alkoxidesand carboxylates designed to gain further insight into thefactors governing ester elimination reactions. By choosingcompounds with varying coordination environments and stericaccessibility we have devised a set of criteria which shouldallow for successful ester elimination between metal alkoxide andcarboxylate compounds. Furthermore we have also shown theability of ester elimination derived molecular clusters withspecific microstructure to be used in the synthesis of bulkmaterials retaining the structural attributes of the precursor cluster.     

Surface oxides on porous carbon

Wet oxidation of BPL porous carbon by H₂O₂ and HNO₃ changes the pore structure and also increases the concentration of surface oxides. KOH uptake is increased by oxidation and is seen to be dependent on KOH concentration and to a lesser extent on inert electrolyte concentration. Enthalpy of immersion measurements have allowed the estimation of the enthalpy of hydration of the surface oxides and the enthalpy of neutralization of the easily accessible acid oxides.     

LnSrNiO4-λ系列复合氧化物的物化性质与对NO分解的催化性能

用柠檬酸络合法合成了Ｋ２ＮｉＦ４结构的ＬｎＳｒＮｉＯ４－λ（Ｌｎ＝Ｌａ，Ｐｒ，Ｎｄ，Ｓｍ，Ｇｄ）系列稀土取代类钙钛石型复合氧化物催化剂，对该系列催化剂的固态物理、化学性质及其对ＮＯ分解的催化性能进行研究。结果表明，该系列复合氧化物催化剂对ＮＯ分解活性都很高，在此基础上对该系列复合氧化物中稀土元素对ＮＯ分解反应的取代效应进行了探讨。     

Heterogeneous Catalytic Partial Oxidation of C3-C4 Alkanes with Nitrogen Monoxide

The possibility of making products of partial oxidation, alcohols and acids in particular, by the reaction of C₃-C₄ alkanes with nitrogen monoxide over oxide and zeolite catalysts is demonstrated. The most effective catalysts are CeO₂ and Fe-TsVK. The dependence of the rate and selectivity of the process on the reaction conditions has been established.     

溶胶-凝胶-钴-邻菲啰啉修饰电极对一氧化氮的电催化氧化及其测定

报道了溶胶 凝胶 钴 邻菲口罗啉膜修饰电极的制备方法及其在一氧化氮(NO)检测中的应用,采用循环伏安法(CV)研究修饰电极的电化学特性,差示脉冲伏安法(DPV)对NO进行检测。该修饰电极对NO的电化学氧化具有很好的催化作用,使其氧化电位负移了210mV,氧化峰电流与NO浓度在5.6×10-8～2.8×10-5mol/L范围内呈良好的线性关系,相关系数r=0.999,检测限为1.4×10-8mol/L,且生物体内常见的干扰物质如抗坏血酸、NO2-和儿茶酚胺类神经递质的代谢物等不干扰测定。     

聚N,N-双水杨醛乙二胺合钴修饰超微电极的制备及其在一氧化氮测定中应用的研究

通过电化学聚合法制备了聚Ｎ，Ｎ－双水杨醛乙二胺合钴［ｐｏｌｙＣｏ（Ｓａｌｅｎ）］修饰超微电极，研究了该修饰电极的电催化性质及其在一氧化氮（ＮＯ）测定中的应用．实验结果表明，ｐｏｌｙＣｏ（Ｓａｌｅｎ）修饰超微电极对ＮＯ的测定有高的灵敏度，ＮＯ的浓度在２．０×１０－８～２．８×１０－６ｍｏｌ／Ｌ范围内，电流与浓度呈良好的线性关系，线性相关系数为０．９９９８，检出限为１．０×１０－８ｍｏｌ／Ｌ；该电极进一步修饰Ｎａｆｉｏｎ后，生物体中常见的物质如抗坏血酸、儿茶酚胺类神经递质的代谢物、ＮＯ的氧化产物ＮＯ－２等不干扰测定．本传感器可以满足ＮＯ在体分析的需要．     

Products of lithium interaction with nanostructured oxides SnO2-TiO2 and mechanism of charge-discharge of electrodes in a lithium-ion battery

Products of lithium interaction with thin-film nanostructured SnO₂-TiO₂ (ST) oxides are studied with the aid of x-ray diffraction analysis and Moessbauer spectroscopy on the ¹¹⁹Sn nuclei. Electrochemical properties of a series of the ST electrodes with different concentrations of TiO₂ varied from 0 to 20 mol % are also examined. It is concluded that the specific feature of the charge-discharge mechanism of the ST electrodes is a significant participation of oxygen in reversible reactions during insertion and extraction of lithium as compared with an alloying mechanism of operation of tin-containing anodes. The leading role in this is played by titanium oxide. Remaining stable towards reduction by lithium, it facilitates the holding of the neighboring layers of SnO₂ in a nanodisperse state and in an oxidized state. The effect of a decrease in the capacity degradation in modified TiO₂ electrodes, which is discovered in this work, is attributed to the hampering of the growth of nanocrystallites of β-Sn by interlayers of tin and titanium oxides mentioned above.     

Simple route to secondary amides of phosphorylacetic acids and their use for extraction and sorption of actinides from nitric acid solutions

An efficient method for the synthesis of secondary alkylamides of phosphorylacetic acids (APA) was proposed. The method involves amidation of ethyl phosphorylacetates with primary aliphatic amines. The scope of reaction was determined. Reactions with ethylenediamine and 1,4-diaminobutane yield the corresponding bisamides; in the case of 1,3-diaminopropane, N-(3-aminopropyl)diphenylphosphorylacetamide or N,N-propylenebis(diphenylphosphorylacetamide) was obtained, depending on the reaction conditions. The extraction of americium(III) complexes and the sorption of uranium(VI) by sorbents with physically sorbed APA from nitric acid solutions were studied. There is no correlation between the partition coefficient of americium(III) and the structure of APA; in the sorption of uranium(VI), the degree of extraction depends on the complexone structure.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2394–2402, November, 2004.