Nitrides thermodynamics

Grzegory I, Jun J, Bockowski M, Krukowski S, Wroblewski M, Lucznik B and Porowski S 1995 lll-V nitrides-thermodynamics and crystal growth at high N2 pressure J. Phys. Chem. Solids 56 639... 

This reaction is catalyzed by iron, and extensive research, including surface science experiments, has led to an understanding of many of the details (72). The adsorption of H2 on iron is fast, and the adsorption of N2 is slow and characterized by a substantial activation energy. N2 and H2 are both dis so datively adsorbed. Adsorption of N2 leads to reconstmction of the iron surface and formation of stmctures called iron nitrides that have depths of several atomic layers with compositions of approximately Fe N. There is a bulk compound Fe N, but it is thermodynamically unstable when the surface stmcture is stable. Adsorbed species such as the intermediates NH and NH2 have been identified spectroscopically. 

The third aspect, the stability range of solid electrolytes, is of special concern for alkaline-ion conductors since only a few compounds show thermodynamic stability with, e.g., elemental lithium. Designing solid electrolytes by considering thermodynamic stability did lead to very interesting compounds and the discovery of promising new solid electrolytes such as the lithium nitride halides [27]. However, since solid-state reactions may proceed very slowly at low temperature, metasta-... 

Wicks, C. E. and Block, F. E. "Thermodynamic Properties of 65 Elements - Their Oxides, Halides, Carbides, and Nitrides", Bureau of Mines, Bulletin 605, 1963. 

In many CVD reactions for the deposition of nitrides, ammonia (NH3) is used as a source of nitrogen, rather than nitrogen. This is preferable from a thermodynamic standpoint but may present a problem in that any NH3 — either unreacted or present in the regions of furnace where the temperature is below its dissociation temperature— tends to combine with the HCl effluent gas and forms NH4CI, which may clog the exhaust line. 

Nickel, K., Riedel, R., and Petzow, G., Thermodynamic and Experimental Study of High-Purity Aluminum Nitride Formation from Aluminum Chloride by Chemical Vapor Deposition, /. Amer. Ceram. Soc., 72(10) 1804-1810 (1989)... 

Nitridoborates of lanthanum and the lanthanides were obtained from reactions of lanthanide metal or lanthanide metal nitride with layer-like (a-)BN at elevated temperatures (3>1200°C). These reactions require elaborated techniques in the inert gas sample-handling and the use of efficient heating sources, such as induction heating. Only some compounds remain stable in this high-temperature segment, and the yields of such reactions are often limited due to the competing stability of binary phases, allowing only the most (thermodynamically) stable compounds to exist. 

Apparently thermodynamically unstable, because when the peroxodisulfuryl difluoride-boron nitride reaction mixture was heated to 40°C, detonations occurred. 

Considering other families of similar compounds, the contributions given by Guillermet and Frisk (1992), Guillermet and Grimvall (1991) (cohesive and thermodynamic properties, atomic average volumes, etc. of nitrides, borides, etc. of transition metals) are other examples of systematic descriptions of selected groups of phases and of the use of special interpolation and extrapolation procedures to predict specific properties. 

There are three anions that may loosely claim to be nitrides. Pentazolides (salts of cyclic N ) will all be explosive. Some azides (salts of N3) fall just short of being explosive but all are violently unstable. The true nitrides, nominal derivatives of N3-, are more various. In addition to some ionic structures, there are polymeric covalent examples, and some monomeric covalent ones, while most of those of transition metals are best considered as alloys. Several are endothermic and explosive, almost all are thermodynamically very unstable in air with respect to the oxide. Many are therefore pyrophoric if finely divided and also may react violently with water and, more particularly, acids, especially oxidising acids. A few are of considerable kinetic stability in these circumstances. There is no very clear classification of probable safety by position in the periodic table but polymeric and alloy structures are in general the more stable. Individual nitrides having entries ... 

Nitrides, Phosphides, and Arsenides. The phase diagram for the Cr-N system between 900 and 1350°C has been constructed and thermodynamic relationships in this system have been calculated. These latter studies indicated the extreme sensitivity of the kinetics of Cr-N reactions to oxygen impurity. ... 

In general, carbides, nitrides, and borides are manufactured in the vapor phase in order to form high-purity powders. This procedure is fundamentally different than a strict CVD process, since in powder synthesis reactors, deposition on seed particles may be desirable, but deposition on the reactor walls represents a loss of product material. As we will see, in CVD, heterogeneous deposition on a surface will be sought. Aside from this issue of deposition, many of the thermodynamic and kinetic considerations regarding gas phase reactions are similar. 

Block, Thermodynamic Properties of 65 Elements Their Oxides, Halides, Carbides and Nitrides , US BuMines Bull 608 (1963)... 

In general, the stable thermodynamic products of ordinary flames have little worth, but many of the uncommon flames have products of value. The chlorination of hydrocarbons may be carried out in a flame process which was recently announced (A4). A most fascinating example is the formation of boron nitride from the flame reaction between diborane and hydrazine, two compounds which are ordinarily thought of as fuels (B2, VI). The stabilization of this flame depends upon the proper preparation of the premixed gases, since a solid adduct between the reactants prevents flame stabilization if the preflame residence time is too great. 

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