Salt-like nitrides

The saltlike (or salinic) nitrides are composed of nitrogen and the most electropositive elements, i.e., the alkali metals, alkaline-earth metals, and the metals of Group III of the Periodic Table, including the lanthanide and actinide series. The difference in electronegativity between these elements and nitrogen is large and the atomic bonding is essentially ionic. They have the characteristics of a salt with a fixed composition. 

Although some of these saltlike nitrides have high melting points (for instance, thorium nitride 2820 C uranium nitride 2800°C plutonium nitride 2550 beryllium nitride 2200 C barium nitride 2200 C), they are sensitive to hydrolysis and react readily with water or moisture to give ammonia and the corresponding metal oxide or hydroxide. Consequently, they do not meet the refractory requirements as interpreted here. Some of these nitrides are useful industrial materials particularly as sintering additives for the production of silicon nitride, aluminum nitride, and cubic boron nitride (see Ch. 14). 

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Solid Electrolytes. Of the salt-like nitrides, only Li N has attracted technical interest. Lithium nitride has an uncommonly high ionic... 

Salt-like nitrides are exemplified by Li3N (mp 548°C, decomp) and M3N2 (M = Be, Mg, Ca, Sr, Ba). It is possible to write ionic formulations of these compounds using the species N though charge separation is... 

Saltlike carbides, 4 647, 648-650 Salt-like nitrides, 77 198-199 Salt mines, 22 799, 800 Salt-out, general separation heuristics for, 22 320... 

Nitrides can be sub-divided into ionic, covalent and interstitial types.An alternate general classification of nitrides, based on bonding classification, as ionic, covalent and metallic has also been applied. Ionic or salt-like nitrides are formed by electropositive elements such as Li, Mg, Ca, Sr, Ba, Cu, Zn, Cd and Hg and possess formulae which correspond to those expected on the basis of the combination of the metal ion with ions. A range of covalent nitrides are known and are exhibited by less electropositive elements such as B, S, P, C and Si. Interstitial nitrides are formed by some transition metals and refer to compounds which can be described in terms of the occupancy of interstitial sites in close packed metallic structures by nitrogen atoms. Oxygen can also be accommodated within these structures and a range of oxynitrides are known to... 

For the above reasons nitrogen forms many compounds of types not formed by other elements of this group, and for this reason we deal separately with the stereochemistry of this element. For example, the only compounds of N and P which are structurally similar are the molecules in which the elements are 3-covalent and the phosphonium and ammonium ions. There are no nitrogen analogues of the phosphorus pentahalides, and there is little resemblance between the oxygen compounds of the two elements. Monatomic ions of nitrogen and phosphorus are known only in the solid state, in the salt-like nitrides and phosphides of the more electropositive elements. The multiple-bonded azide ion, N3, is peculiar to nitrogen. 

Electron gain to form the nitride ion, N3-. This ion occurs only in the salt-like nitrides of the most electropositive elements, for example, Li3N. Many non-ionic nitrides exist and are discussed later in this Chapter. 

Nitrogen forms binary compounds with almost all elements of the periodic table and for many elements several stoichiometries are observed, e.g. MnN, Mn Ns, Mn3N2, MniN, Mn4N and Mn tN (9.2 < jc < 25.3). Nitrides are frequently classified into 4 groups salt-like , covalent, diamond-like and metallic (or interstitial ). The remarks on p. 64 concerning the limitations of such classifications are relevant here. The two main methods of preparation are by direct reaction of the metal with Ni or NH3 (often at high temperatures) and the thermal decomposition of metal amides, e.g. ... 

With hydrogen, the alkali metals form the mono-hydrides MeH, having salt-like properties and a partially ionic, Me H, NaCl-type structure. They are colourless crystalline solids having a fairly negative AH of formation. The mono-hydrides react with water. They may be prepared from hydrogen and the metal (heated at 700-800°C for Li, 350-400°C for the others) or through the reaction of hydrogen with the alkali mono-oxide, nitride, etc. 

As for hydrides, borides, and carbides, different types of nitrides are possible depending on the type of metallic element. The classifications of nitrides are similarly referred to as ionic (salt-like), covalent, and interstitial. However, it should be noted that there is a transition of bond types. Within the covalent classification, nitrides are known that have a diamond or graphite structure. Principally, these are the boron nitrides that were discussed in Chapter 8. 

Salt-like or ionic nitrides, in which N forms primarily ionic bonds to alkali metals, rare earth metals, and members of group IIIA. Although actinide nitrides are also included in this grouping, they may equally well be classified as metallic. Compounds in this group are readily hydrolyzed and must thus be protected from moisture. 

The last three, the NH2, NH , and N ions, are found in the salt-like amides, imides, and nitrides of the most electropositive metals, but with the exception of the amide ion the stereochemistry of nitrogen is based on N with no lone pairs and N with one lone pair. These two states of the nitrogen atom correspond to the classical trivalent and pentavalent states, now preferably regarded as oxidation rather than valence states. 

The interstitial structures comprise the compounds of certain metallic elements, notably the transition metals and those of the lanthanide and actinide series, with the four non-metallic elements hydrogen, boron, carbon and nitrogen. In chapter 8 we discussed the structures of a number of hydrides, borides, carbides and nitrides of the most electropositive metals, and these we found to be typical salt-like compounds with a definite composition and with physical properties entirely different from those of the constituent elements they are generally transparent to light and poor conductors of electricity. The systems now to be considered are strikingly different. They resemble... 

The Group II metal nitrides M3N2, are salt-like in character, but (BN) has a macromolecular structure and is refractory in nature. 

No, the editor didn t know what this name meant either.) It means salts of the triva-lent anions of Group V, restricted in [1] to arsenides, antimonides and bismuthides and prepared by reaction of sodium pnictides with anhydrous halides of transition and lanthanide metals. This violently exothermic reaction may initiate as low as 25°C. Avoidance of hydrated halides is cautioned since these are likely to react uncontrollably on mixing. Another paper includes a similar reaction of phosphides, initiated by grinding [2], Nitrides are reported made from the thermally initiated reaction of sodium azide with metal halides, a very large sealed ampoule is counselled to contain the nitrogen [3],... 

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