Friday, February 24, 2017

inorganic chemistry - What is the bonding type in hydrides of group 2 elements?


In one of my MCQ questions, there was a statement saying all group 2 elements form covalent hydroxides. I know it is incorrect. I know that BeHX2 is a covalent hydride. What about the rest? Are all of them metallic hydrides? Is it true that metallic hydrides produce the hydroxide and give off HX2 with water?



Answer



There is a quite extensive chapter about hydrogen and its compounds in Holleman and Wibereg's book "Inorganic Chemistry". As I only have the german version, I will briefly summarise what I read.


You are of course right, hydrogen forms salt-like structures with alkaline and earth alkaline elements, except for beryllium. Compounds like LiH, NaH, KH, RbH and CsH crystallise in a sodium chloride structure. Every cation is coordinated by six hydride ions and vice versa. The compounds CaHX2, SrHX2 and BaHX2 crystallise in a fluorite structure. The hydride ions are tetrahedrally coordinated by four earth alkaline cations. The cations are cubically coordinated by eight hydride ions. This β-structure is persistent at higher temperatures. Below 780 C (CaHX2), 855 C (SrHX2), and 598 C (BaHX2) it changes to the α-form, i.e. the lead dichloride structure. The magnesium compound exists in a rutile structure. Hydride ions are trigonally coordinated by magnesium ions. The cations are octahedrally coordinated by hydride ions.


However, according to the difference in the electronegativities, you would expect a predominant covalent character. The maximum is 1.3 for CaHX2 and the minimum 1.0 for MgHX2, which translates to a maximum 30% and minimum 18% ionic contribution. Maybe this is where the statement of the question originates from. Experimental findings rather support the more ionic nature of the compounds though, i.e. the found lattice energies were supported by calculations assuming a purely ionic structure.



The conclusion of this according to Holleman and Wiberg is that the elements are fused by ionic bonds with covalent contributions. The latter increases from CsH to LiH and from BaHX2 to MgHX2. The magnesium hydride is already borderline covalent.


The question about their reactivity towards water is mainly answered in the chapters for the elements itself. Magnesium reacts readily with water and releases hydrogen. Because of this it is sometimes used as a drying agent. MgHX2+2HX2OMg(OH)X2+HX2

The other elements react similar. The reaction is highly exothermic, the reaction of calcium hydride releases 228 kJ/mol. It is often used as a drying agent for gasses because of this feature. Strontium and Barium also react exothermic, i.e. they release 177 kJ/mol and 172 kJ/mol, respectively.


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