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The Main Group Elemental Hydrides

The chemogenesis story starts with the periodic table, simplified to the first 36 main group (s & p-block) elements, hydrogen to barium. The main group elements are then normalised to the corresponding main group elemental hydrides, a set that includes such well known species as: hydrogen, water, ammonia, methane, lithium hydride, xenon and hydrogen chloride. Patterns in structure and reaction behaviour are noted.


The First 36 Main Group Elements: Hydrogen to Barium

Initially we shall limit our initial discussions to s and p-block elements, to first 36 main group elements, hydrogen to barium:

However, as chemical substances in their standard state (100kPa pressure & 298K – 1.00atm & 25°C) the main group elements present as a diverse and complicated collection of substances:

As discussed previously in this web book – see the pages on the Classification of Matter and the Tetrahedron of Structure, Bonding & Material Type pages – elemental and binary substances exhibit four extreme material types [metallic, ionic, molecular & network covalent], however the elements present as just: metallic, molecular & network covalent (no pure element is ionic):


When this analysis is applied to the set of the first 36 main group elements we find:

16 elements are molecular, 15 are metallic, 5 are network covalent.

However, even this is a simplification because several elements have metallic and non-metallic allotropes that are intermediate between metallic and network, and are metalloid or semi-metallic in nature: C, Si, Ge, As, Sn, Sb & Te.

Thus, as a set, even the first 36 main group elements exhibit considerable complexity.



Normalisation

Data normalisation is a common procedure in science, here.

The question is:

Can the diversity associated with the elements in their standard state be removed? Is it possible to normalise the first 36 main group elements so that they can be meaningfully compared and contrasted with each other?

One way to normalise the elements is to examine the gas phase mono-atomic species, here. While this tells us much about the physics of atoms and atomic structure, it tells us little about the reaction chemistry of chemical elements as substances and reagents.

The approach taken by the chemogenesis analysis is to saturation bond each of the first 36 main group elements with a common bonding partner, and then to explore the chemistry of the resulting binary compounds. There are several candidate bonding partner elements, including:

to give the corresponding: hydrides, lithides, fluorides and oxides

By far the most interesting bonding partner is hydrogen. This gives rise the corresponding set of 36 main group elemental hydrides.


The Main Group Elemental Hydrides

The 36 of the main group elemental hydrides, H2 to BaH2, are all well known species with non-controversial structure and reaction chemistry. Indeed, the set includes such common chemical species as water, H2O, methane, CH4, ammonia, NH3, hydrogen sulfide, H2S, hydrogen, H2, and neon, Ne.

Of more importance – and crucial to the normalisation argument – is that all the main group elemental hydrides can be found in the gas phase where they are molecular.

This "gas phase & molecular" point is crucial for two reasons:

Some points to note:



Patterns In Reaction Chemistry Space

The main group elemental hydrides show patterns of reaction chemistry behaviour which correspond with the s-block and p-block construction of the periodic table in that they show real and rich periodicity.


The Main Group Elemental Hydrides as: Lewis Acids, Lewis Bases and Lewis Acid/Base Complexes

[For a revision of the difference between the "Lewis" and "Brønsted" definitions of acids and bases, look here, and for a discussion of frontier molecular orbitals, look here.]

In the original language of Lewis acid/base chemistry:

In the 1960s, with the development of frontier molecular orbital (FMO) theory, this can be modified to:

In the analysis presented here:

A Lewis acid's LUMO interacts with a Lewis base's HOMO to give a Lewis acid/base complex with a net bonding molecular orbital:

LUMO     +     HOMO   →      LUMO/HOMO     →    Bonding MO

There is a self-consistent colour scheme running through the Chemogenesis web book.


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The HSAB Principle The Five Hydrogen Probe Experiments

© Mark R. Leach 1999 –


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