Potentials of gas chromatography in the determination of reaction products in the catalytic oxidation of ammonia to nitrogen(II) oxide

Peculiarities of the determination of nitrogen oxides and ammonia in the reaction products of ammonia oxidation are studied by gas chromatography. Particular attention was paid to the sampling problem. It is shown that in the course of the transportation of samples containing nitrogen(II) oxide and oxygen, the oxidation of nitrogen(II) oxide to nitrogen(IV) oxide takes place in the vapor phase. The conditions were found for suppressing or even eliminating the gas-phase reaction of NO oxidation to NO₂. A procedure for the gas-chromatographic analysis of the reaction products in the catalytic oxidation of ammonia is proposed using several samples and packed columns, including the determination of NO with respect to NO₂ formed in the gas-phase oxidation of NO.     

Boehmite formation mechanism in precipitate ageing

Phase composition of the products of Al(III) hydroxide ageing at 473 K is shown to be independent of pH. Under these conditions boehmite is always formed whose morphological structure is determined by both the phase composition of freshly precipitated Al(III) hydroxides and the pH of their ageing. A possibility for the formation of needlelike boehmite crystals whose width coincides with the value of b=12.3Å of its unit cell, has been shown.

---

Al(III) 473 pH, . Al(III), pH . , b=12,3 Å .

     

Distribution of copper- and nickel-containing modifier components in the pore space of HZSM-5 zeolite

The distribution of copper- and nickel-containing components in the pore space of HZSM-5 zeolite was quantitatively studied. It was found that the detailed distribution of a modifier in the micropore and mesopore volumes of the zeolite depends on both the chemical nature of the modifier and the conditions of supporting and the regime of M²⁺ polycondensation in the pore space of the zeolite. The experimental data on the low-temperature adsorption of nitrogen on Cu(n)ZSM-5 catalysts can be interpreted as the result of the partial filling of the zeolite micropore space (10 vol %) and the finest mesopores with D < 3 nm with the modifier. In the case of Ni(n)ZSM-5 catalysts, the penetration of the modifier into zeolite channels (micropores) in detectable amounts was not found, and it was arranged in mesopores on the surface of zeolite crystallites. The reason for differences between modifier distributions in the pore structure of the zeolite was explained from the standpoint of different structures of copper and nickel polyhydroxo complexes in impregnating solutions after polycondensation. It was found that, in the Cu(n)ZSM-5 and Ni(n)ZSM-5 catalysts, the modifier component contained copper and nickel only in a doubly charged state and mainly octahedral oxygen environments. In this case, three-dimensional nanoparticles or coarsely dispersed particles of CuO were not detected in the pore space of the support, whereas the presence of a small amount of sufficiently large NiO crystals with a coherent-scattering region of 80–100 nm was detected in Ni(n)ZSM-5, and these crystals occurred on the surface of zeolite crystals. It was found that the apparent density of a copper-or nickel-containing component arranged in the pore space of the zeolite was lower than the density of the bulk CuO and NiO phases by a factor of ～3 and 4, respectively, because of the size effect.     

The phase diagram of the superconducting state of superconductor-band-antiferromagnet superlattices

The formation of the superconducting phase in short-period proximity-effect layered superlattices of the superconductor-band-antiferromagnetic-metal (SC/AF) type is studied. The exact solution of the Usadel equations is used to discuss the possibility of formation in such structures of a ground state in which the order parameters of the adjacent superconducting layers have opposite signs (the “π-phase”). The dependence of the superconducting transition temperature and the upper critical field normal to the layers on the lattice period, the intensity of magnetic interaction in the antiferromagnetic layer, and the state of the interface between the layers is examined. It is found that there exists a nonlinear dependence of the conditions for the appearance of the superconducting state in a layered SC/AF system on the system’s parameters. Finally, the conditions for the appearance of the superconducting phase in proximity-effect superlattices consisting of a superconductor with nonmagnetic, ferromagnetic, and antiferromagnetic metals are compared. Zh. éksp. Teor. Fiz. 111, 547–561 (February 1997)