Interstitial hydrides

The interstitial carbides These are formed by the transition metals (e.g. titanium, iron) and have the general formula M, C. They are often non-stoichiometric—the carbon atoms can occupy some or all of the small spaces between the larger metal atoms, the arrangement of which remains essentially the same as in the pure metal (cf. the interstitial hydrides). 

The transition metal structures consist of close-packed (p. 26) arrays of relatively large atoms. Between these atoms, in the holes , small atoms, notably those of hydrogen, nitrogen and carbon, can be inserted, without very much distortion of the original metal structure. to give interstitial compounds (for example the hydrides, p. 113). 

The crystal stmeture and stoichiometry of these materials is determined from two contributions, geometric and electronic. The geometric factor is an empirical one (8) simple interstitial carbides, nitrides, borides, and hydrides are formed for small ratios of nonmetal to metal radii, eg, < 0.59. 

Other hydrides with interstitial or metallic properties are formed by V, Nb and Ta they are, however, very much less stable than the compounds we have been considering and have extensive ranges of composition. Chromium also forms a hydride, CrH, though this must be prepared electrolytically rather than by direct reaction of the metal with hydrogen. It has the anti-NiAs structure (p.. 555). Most other elements... 

Attempts to classify carbides according to structure or bond type meet the same difficulties as were encountered with hydrides (p. 64) and borides (p. 145) and for the same reasons. The general trends in properties of the three groups of compounds are, however, broadly similar, being most polar (ionic) for the electropositive metals, most covalent (molecular) for the electronegative non-metals and somewhat complex (interstitial) for the elements in the centre of the d block. There are also several elements with poorly characterized, unstable, or non-existent carbides, namely the later transition elements (Groups 11 and 12), the platinum metals, and the post transition-metal elements in Group 13. 

A number of metals have the ability to absorb hydrogen, which may be taken into solid solution or form a metallic hydride, and this absorption can provide an alternative reaction path to the desorption of H,. as gas. In the case of iron and iron alloys, both hydrogen adsorption and absorption occur simultaneously, and the latter thus gives rise to another equilibrium involving the transfer of H,<,s across the interface to form interstitial H atoms just beneath the surface ... 

There have been numerous studies with the objective of gaining an understanding of the factors that influence the stability, stoichiometry, and H-site occupation in hydride phases. Stability has been correlated with cell volume [7] or the size of the interstitial hole in the metal lattice [8] and the free energy of the a p phase conversion. This has been widely exploited to modulate hydride phase stability, as discussed in Sec. 7.2.2.1. 

Assuming the composition of the hydride to be expressed by PdjH2 (which corresponds to PdH0. 7) and bearing in mind the interstitial positioning of the hydrogen in the palladium lattice, the authors postulate the existence of the following equilibrium at the surface of the j8-hydride phase... 

Nevertheless it does not change the principle of the mechanism proposed by Scholten and Konvalinka, i.e. the ability to act catalytically of only the superficial palladium centers released from the vicinity of the interstitial hydrogen. Bearing in mind the dynamic character of the equilibrium in a palladium-hydrogen system as a whole is to regard such centers as being mobile in the surface layer of the hydride. 

The interstitial carbides are compounds formed by the direct reaction of a d-block metal and carbon at temperatures above 2000°C. In these compounds, the C atoms occupy the gaps between the metal atoms, as do the H atoms in metallic hydrides (see Fig. 14.9). Here, however, the C atoms pin the metal atoms together into a rigid structure, resulting in very hard substances with melting points often well above 3000°C. Tungsten carbide, WC, is used for the cutting surfaces of drills, and iron carbide, FesC, is an important component of steel. 

This means that 1 out of 42 hydride atoms is interstitial, cuid 1 out of 84 hydride-atom-sites is vacant. 

Interstitial Solid Solutions Interstitial solid solutions involve occupation of a site by introduced ions or atoms, which is normally empty in the crystal structure, and no ions or atoms are left out. Many metals form interstitial solid solutions in which small atoms (e.g., hydrogen, carbon, boron, nitrogen) enter empty interstitial sites within the host structure of the metal. Palladium metal is well known for its ability to absorb an enormous volume of hydrogen gas, and the product hydride is an interstitial sohd solution of formula PdH, 0 0.7, in which hydrogen atoms occupy... 

The interstitial hydrides of transition metals differ from the salt-like hydrides of the alkali and alkaline-earth metals MH and MH2, as can be seen from their densities. While the latter have higher densities than the metals, the transition metal hydrides have expanded metal lattices. Furthermore, the transition metal hydrides exhibit metallic luster and are semiconducting. Alkali metal hydrides have NaCl structure MgH2 has rutile structure. 

Although the formation of ionic hydrides is usually exothermic, the formation of interstitial hydrides may have positive enthalpy values. Physical characteristics of interstitial hydrides are determined by the fact that hydrogen atoms in interstitial positions cause some expansion of the lattice but contribute very little mass. Consequently, the interstitial hydrides always have lower densities than the metal itself, even though the crystal structure is normally the same. When interstitial positions contain hydrogen atoms, the flow of electrons in conduction bands within the metal is impeded, so the... 

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