Electron, atom ratio compound

Reference has already been made to the high melting point, boiling point and strength of transition metals, and this has been attributed to high valency electron-atom ratios. Transition metals quite readily form alloys with each other, and with non-transition metals in some of these alloys, definite intermetallic compounds appear (for example CuZn, CoZn3, Cu3,Sng, Ag5Al3) and in these the formulae correspond to certain definite electron-atom ratios. 

It should not be thought that the structure of every intermetallic compound can be treated so simply the discussion of such struetural features as the transfer of electrons between atoms, the occurrence of strained bonds, the significance of relative atomic sizes, and the electron-atom ratio (Hume-Rothery ratio) must, however, be postponed to later papers. 

Nonstoichiometric compounds are mixed-valence compounds with nonintegral electron/atom ratios. Electronic properties of these compounds depend crucially on the nature and magnitude of nonstoichiometry. Electronic conduction in many such compounds occurs by hopping between the cations of different valencies (e.g. Pr " " and Pr" " in Pri2022)- Nonstoichiometry with a wide range of compositions is more common in oxides, sulphides, and related materials where the bonding is not completely ionic. In ionic nonstoichiometric compounds, structural rearrangements... 

It is reasonable to assume that if the formation of the /Fphase type of abnormal valency intermetaliic compounds requires a certain definite electron atom ratio the other intermediate phases should also be based on similar ratios. Such is indeed the case, andwe may extend our discussion of the Hume-Rothery Rules by considering the other phases of the copper-zinc, copper-aluminium and copper-tin systems. We find, for example, that the y-phases occur near the compositions of 61 6 atomic per cent, zinc, 30-8 atomic per cent, aluminium and 20 5 atomic per cent, tin, respectively, which correspond to the compounds Cu5Zn8, Cu9A14 and Cu31Sn8 (Fig. 34). The y electron atom ratio is seen to be 21 13, as follows ... 

Structures of Abnormal Valency or Electron Intermetallic Compounds. We have seen how in many alloy systems the / -. y- and e-phases are based on electron compounds the formula of which differ very widely but which have in common electron atom ratios of 8 2, 21 18 and 7 4. The range of existence of the particular phases is really a range of solid solution in the compound concerned, and this tends to decrease, as it does in primary solid solution, with increase of valency of the second metal. The j3-, y- and -phases have, however, more in common than mere electron concentration, for they have, in addition, the same lattice structure, although the atomic arrangement is usually a purely random one. Thus, the 8 2 / -compound phase is normally body-centred cubic, although it may have a modified cubic structure known as the /3-manganese one the 21 18 y-compound phase, known as the y-brass structure,... 

To this point, our study of chemistry has been largely qualitative, involving very few calculations. However, chemistry is a quantitative science. Atoms of elements differ from one another not only in composition (number of protons, electrons, neutrons), but also in mass. Chemical formulas of compounds tell us not only the atom ratios in which elements are present but also the mass ratios. 

Colour centres are formed if a crystal of NaCl is heated in sodium vapour sodium is taken into the crystal, and the formula becomes Nai+/fl. The sodium atoms occupy cation sites, creating an equivalent number of anion vacancies they subsequently ionize to form a sodium cation with an electron trapped at the anion vacancy. The solid so formed is a non-stoichiometric compound because the ratio of the atomic components is no longer the simple integer that we have come to expect for well-characterized compounds. A careful analysis of many substances, particularly inorganic solids, demonstrates that it is common for the atomic ratios to be non-integral. Uranium dioxide, for instance, can range in composition from UOi 05 to UO2.25, certainly not the perfect UO2 that we might expect Many other examples exist, some of which we discuss in some detail. 

The Cu-Zn system (brass) is complex as shown in Figure 9.1. The a phase is a ccp solid solution of Zn in Cu. The (3-brass is body-centered cubic, the composition corresponding to CuZn. Each phase exists over a range of Cu/Zn ratios corresponding to a solid solution with Zn or Cu added to the compound. The y-brass, CupZns, has a complex cubic structure and e-brass, CuZn3, has an hep structure. Hume-Rothery found that many intermetallic compounds have structures similar to (3-, y-, and e-brass at the same electron-to-atom ratio as the corresponding brass compounds. Some examples of these so-called electron... 

Aromatic compounds have special characteristics of aromaticity, which include a low hydro-gen carbon atomic ratio, C-C bonds that are quite strong and of intermediate length between such bonds in alkanes and those in alkenes, tendency to undergo substitution reactions rather than the addition reactions characteristic of alkenes, and delocalization of n electrons over several carbon atoms. The last phenomenon adds substantial stability to aromatic compounds and is known as resonance stabilization. 

The circumstances under which intermetallics form were elucidated by the British metallurgist William Hume-Rothery (1899-1968) for compounds between the noble metals and the elements to their right in the periodic table (Hume-Rothery, 1934 Reynolds and Hume-Rothery, 1937). These are now applied to all intermetaUic compounds, in general. The converse to an intermetaUic, a solid solution, is only stable for certain valence-electron count per atom ratios, and with minimal differences in the atomic radii, electronegativities, and crystal structures (bonding preferences) of the pure components. For example, it is a mle-of-thumb that elements with atomic radii differing by more than 15 percent generally have very little solid phase miscibility. 

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