复旦大学无机化学IC09.pptVIP

2.1.2 Hydrides There are three types of hydrides, they are saline hydrides (or salt-like hydrides), metallic hydrides, and molecular hydrides. Most binary compounds of hydrogen fall into one of three types. The hydrogen compounds of the highly electropositive s-block metals are nonvolatile, electrically nonconducting, crystalline solids. These properties as well as their structures lead to their classification as saline hydrides. On the other hand, the d-block and f-block metals form hydrides that are often nonstoichiometric, electrically conducting solids, called metallic hydrides. Most of the p-block binary hydrogen compounds are volatile molecular compounds, and accordingly are classified as molecular hydrides. 1. The saline hydrides Alkali metal hydrides have rock-salt (NaCl) structure, and alkaline earth metal hydrides have crystal structures like those of some heavy metal halides. Compound Crystal structure LiH, NaH, RbH, CsH Rock-salt (NaCl) MgH2 Rutile CaH2, SrH2, BaH2 Distorted PbCl2 The ionic radius of H- of these compounds varies quite widely, from 1.26 ? in LiH to 1.54 ? in CsH. This wide variability reflects the loose control of the single charge of proton on its two surrounding electrons, resulting in high compressibility of H-. The saline hydrides are insoluble in common nonaqueous solvents. Electrolysis of the molten-salt solution produces hydrogen gas at the anode. thus providing chemical evidence for the existence of H-. The reaction of saline hydrides with water is dangerously vigorous:NaH (s) + H2O (l) → H2 (g) + NaOH (aq) The reaction between metal hydrides and water is employed in the laboratory to remove traces of water from solvents and inert gases such as nitrogen and argon: CaH2 (s) + 2H2O (l) → 2H2 (g) + Ca(OH)2 (s) Calcium hydride is preferred in this application because it is the cheapes