Chemistry of the

Main Group
Elements
Prepared by: Kevin Nick S. Bandibas
The Main Group Elements
The Hydrogen Atom

• Discovered by Cavendish in 1766 and named by Lavoisier.

- hydro = water + genes = forming
• Most abundant element in the universe:
- 90% of all atoms
- ~3/4 of all mass
• The simplest possible system and the basis for all others.
• Elemental form is H2(g) and is rare in the atmosphere
The Hydrogen Atom
The Hydrogen Atom
Isotopes:
1. Protium
- the only isotope of hydrogen without a neutron
2. Deuterium
- obtained as D2O after prolonged electrolysis of natural water.
- D2O is concentrated during electrolysis (H2O electrolyzes
more rapidly)
- allows many chemical reaction mechanisms to be examined
since D-element bonds are more difficult to break than with H-
element bonds
The Hydrogen Atom

Isotopes:
3. Tritium
- beta particle emitter, t1/2 = 12.4 years

- produced naturally by cosmic rays of the upper

atmosphere
- produced commercially in a nuclear reactor
The Hydrogen Atom
Isotopes:
3. Tritium
- hydrogen isotope
used in “hydrogen
bombs”
- used in tracer
studies: movement of
underground water
- energy source for
tritium watches
The Hydrogen Atom
• Electron Configuration: 1s1
• 1 proton and 1 electron
• Only needs 2 electrons to fill up its
valence shell
• A non-metal
• A gas at room temperature
Where does Hydrogen belong?
Where does Hydrogen belong?

• Hydrogen and the Alkali Metals (Group 1A)

- outer electron configuration: ns1
- single valence electron
- common +1 oxidation state
Where does Hydrogen belong?
• Hydrogen and the Alkali Metals (Group 1A)
- forms cations (H+, Li+, Na+, K+, …)
- too high ionization potential for H:

- H+ requires stabilization in solution (NH4+, H3O+,…)

- H+ forms covalent compounds, alkali metal
compounds are mainly ionic.
Where does Hydrogen belong?

• Hydrogen and the Tetrel elements (Group 4A)

- half-filled valence orbitals
Hydrogen – 1s1 (filled 1 out of 2 max e-)
Group 4A = ns2 np2 (filled 4 out of 8 max e-)
Where does Hydrogen belong?

• Hydrogen and the Tetrel elements (Group 4A)

- similar in terms of:
* Ionization energy
* Electron affinity
* Electronegativity
* Bond energies
Where does Hydrogen belong?

• Hydrogen and the Halogens (Group 7A)

- exists as diatomic molecules
- needs only 1 electron to fill valence shell

• Hydrogen forms compounds with hydride (H-) ion,

negative (favorable) electron affinity
Where does Hydrogen belong?

• Unlike Halogens, Hydrogen:

- much lower electronegativity
- lacks 3 valence electron pairs
• Halides (F-, Br-, Cl-, I-) are common and stable
• Hydride (H-) ions are rare and reactive

NaH can ignite in air or in contact with water; NaCl is highly stable
Where does Hydrogen belong?

• Unlike typical halides, the overall enthalpy of formation

of the hydride ion is endothermic
Where does Hydrogen belong?

• H- requires a small and very electropositive element to

stabilize it in a crystal lattice.
• Radius of H- is highly variable:126 pm in LiH; 154 pm in CsH
• Hydrogen deserves its own location in the periodic table
• At very high pressures (>2 million atm) H becomes metallic!
- Group 1A
Reactions of Hydrogen

• Under normal conditions, H2 is relatively inactive

chemically but enters in many chemical reactions when
heated.
• H2 reacts with virtually all other elements (except noble
gases), often explosively.
Hydrogen Economy

• Hydrogen is an attractive fuel because of its high heat

of combustion and zero pollution
Hydrogen Economy

• Current hydrogen economy is impractical

• Generation of hydrogen is predominantly from fossil
fuels requiring large input of energy and release of
carbon dioxide
Synthesis of Hydrogen
• Laboratory Synthesis
- Active metal in acid

- hydrolysis of hydrides
- photochemical decomposition of water
Synthesis of Hydrogen

• Laboratory Synthesis
- electrolysis
Synthesis of Hydrogen

• Industrial Synthesis
- Bosch Process (water-gas shift reaction)
- Passing steam over coke (an impure form of
elemental carbon) at 1000°C produces a mixture of
carbon monoxide and hydrogen known as water gas
Synthesis of Hydrogen

• Industrial Synthesis
- Cracking of light hydrocarbons
Uses of Hydrogen

• Fuel of buses and cars in the 21st century

• Extract pure metals like copper from ore:
M+ + H2 → Cu + 2H+
when ΔG is negative
• Ammonia Production
Uses of Hydrogen
Compounds of Hydrogen

• Saline Hydrides
• Hydride Complexes
• Covalent Hydrides
• Macromolecular Hydrides
• Interstitial Hydrides
Compounds of Hydrogen

• Saline Hydrides
- Group 1 and 2 elements form saline hydrides by
direct combination.

- React with protic solvents to give H2.

- electrolysis of molten saline hydrides evolves H2 in

the anode
Compounds of Hydrogen

• Hydride Complexes
- MH4- complexes of Group 13 elements

- Stability decreases with increasing atomic number

of M and decreasing bond strength Explodes on contact
with water
Compounds of Hydrogen

• Covalent Hydrides
- covalent compounds with H having a formal
charge equal to +1
- strength of H-X bond tends to increase with
difference in electronegativity and decrease with mass of
X (X = nonmetal, Sn, As, Sb)
- Synthesis via Direct Combination
Compounds of Hydrogen

• Covalent Hydrides
- with less electronegative elements, metal salts of
the non-hydrogen element may be used:
Compounds of Hydrogen

• Covalent Hydrides
- LiAlH4 can also act as a hydrogenating agent
Compounds of Hydrogen
• Macromolecular Hydrides
- BeH2 and MgH2 have
similar reactivity to saline
hydrides, but they are more
covalent
- the solids contain infinite
chains of tetrahedrally
coordinated Be or Mg with H-
bridges
- The hydrogen bridges are
electron-deficient 3c-2e bonds
Compounds of Hydrogen

• Interstitial Hydrides
(Metallic Hydrides)
- H and H2 react with
most transition metals and
Lanthanide, MxHy – no fixed
geometry
- H and H2 occupy
interstitial holes in the
metallic structure
Hydrogen Bonding

• Occurs when an H in an H-X bond (X = N, O, F) is

attracted to another very electronegative atom.