Anhydrous Oxides

▪ Acidic Oxide: An oxide that, on dissolution in water, binds an H2O molecule and
releases a proton to the surrounding solvent:

▪ Basic Oxide: An oxide to which a proton is transferred when it dissolves in water:

▪ Metals form basic oxides and nonmetals form acidic oxides.

▪ Basic oxides are often ionic and acidic oxides are often covalent.

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 Anhydrous Oxides
▪ Amphoteric Oxide: An oxide that reacts with both acids and bases. Example: Al2O3

Amphoteric oxides in
all oxidation states

Acidic oxides in the

highest oxidation
state and ampho-
teric oxides in lower
oxidation states

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 Periodic Trends in Amphoteric Properties
▪ The character of the oxides of the elements across a row of the periodic table (s-
and p-blocks) changes from basic to acidic, consistent with a change from metallic to
non-metallic character of the element.

▪ Amphoteric oxides lie close to the so-called “diagonal line” or the borderline
between acidic and basic oxides.

▪ Amphoterism is observed for -

 lighter elements of Groups 2 and 13, as in BeO, Al2O3 and Ga2O3

 d-block elements in high oxidation states, such as MoO3 and V2O5

 heavier elements of Groups 14 and 15, such as SnO2 and Sb2O3

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 Lewis Acids and Bases
▪ Lewis Acid: A substance that acts as an electron pair acceptor.
▪ Lewis Base: A substance that acts as an electron pair donor.

Lewis acidity is much broader than Bronsted acidity. Why?

▪ All Bronsted acids are Lewis acids because a proton donor is also an electron pair
acceptor. Example: HCl is a Bronsted acid as well as a Lewis acid.

▪ All Bronsted bases are Lewis bases because a proton acceptor is also an electron
pair donor. Example: NH3 is a Bronsted base as well as a Lewis base.

▪ However, because the proton is not essential to the definition of a Lewis acid or
base, a wider range of substances can be classified as acids and bases in the Lewis
scheme than can be classified in the Bronsted scheme.

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 Examples of Lewis Acids
1) A molecule with an incomplete octet of valence electrons can complete its octet by
accepting an electron pair. Example: BF3, B(CH3)3

2) A metal cation can accept an electron pair supplied by the base in a coordination
compound. Example: Lone pairs of H2O donate to Co2+ cation to give [Co(OH2)6]2+.

3) A molecule or ion with a complete octet may be able to rearrange its valence
electrons and accept an additional electron pair. Example: CO2

4) A molecule or ion may be able to expand its valence shell (or simply be large
enough) to accept another electron pair.
2-

S 2F S

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 Group Characteristics of Lewis Acids
▪ Group 13 Lewis Acids:
▪ Order of Lewis acidity of boron trihalides BX3: BF3 < BCl3 < BBr3

BX3 and AlX3

▪ Explanation: A filled p-orbital on halogen atoms in BX3 molecule can form π- bonds
with the empty 2p orbital of B atom. These π bonds must be disrupted to make the
acceptor orbital available for complex formation. The π bond also favours the planar
structure of the molecule, which is converted into tetrahedral structure in the adduct.
The small F atom forms the strongest π bonds with the 2p orbital of B atom, since p–p
π bonding is strongest for Period 2 elements, due to the small atomic radii of these
elements and the significant overlap of their compact 2p orbitals. Thus, the BF3
molecule has the strongest bond to be broken when the amine forms an N–B bond.

pπ–pπ

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 Group Characteristics of Lewis Acids
▪ Group 14 Lewis Acids:

▪ Order of Lewis acidity of SiX4: SiI4 < SiBr4 < SiCl4 < SiF4
▪ Explanation: The order in this case is the reverse of that for BX3. π-conjugation from
the p-orbital of halogen atoms to the d-orbitals on the Si atoms is not as intense as in
the case of BX3. The electron-withdrawing power of the halogen atoms increases from
I to F. The F atom is SiF4 is the most electronegative halogen atom. The F atom makes
the Si atom in SiF4 most electron deficient so that the Si atom can make the strongest
bond with the incoming base.