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Structural Aspects of Brønsted Acids

▪ The largest class of acids in water consists of species that donate protons from an
–OH group attached to a central atom.

1) Aqua Acid: An acid in which the acidic proton is on a water molecule coordinated
to a central metal ion. Example: [Fe(H2O)6]3+

2) Hydroxo Acid: An acid in which the acidic proton is on a hydroxyl group without a
neighbouring oxo group (=O). Example: [Te(OH)6], [Si(OH)4]

3) Oxo Acid: An acid in which the acidic proton is on a hydroxyl group with an oxo (=O)
group attached to the same atom. Example: H2SO4, H2CrO4, HClO4

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Structural Aspects of Brønsted Acids
▪ The 3 classes of acids can be regarded as successive stages in the deprotonation of
an aqua acid:

▪ Example:

Positions in Periodic Table


▪ Aqua Acids: Found where central atoms are in low oxidation states.
Found with s- and d-block elements and elements on the left of the p-block.

▪ Hydroxo Acids: Found with central p-block elements.

▪ Oxo Acids: Found where the central atoms are in a high oxidation state.
Found with p-and d-block elements.

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Periodic Trends in Aqua Acid Strength

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Periodic Trends in Aqua Acid Strength

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Periodic Trends in Aqua Acid Strength
▪ Ionic Model: Applicable for s-block and early transition metals (e.g. Fe2+ and Cr3+)

▪ Trend: The strengths of aqua acids typically increase with increasing positive charge
of the central metal ion and with decreasing ionic radius.

▪ Explanation: In an ionic model, the metal cation is represented by a sphere of


radius r+ carrying z positive charges. When H2O coordinates to metal cation, charge
is withdrawn towards the metal center from O-H bond, leaving the H atoms more
positively charged. Because protons are more easily removed (due to repulsion)
from the vicinity of metal cations of high charge and small radius, the acidity should
increase with increasing z and with decreasing r+.

▪ Example: Acidity order: Fe(OH2)62+ < Fe(OH2)63+ < Al(OH2)63+

▪ Acid strength of Al(OH2)63+ is same as that of acetic acid, both having Ka = 1.8 × 10-5.

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Periodic Trends in Aqua Acid Strength
▪ Covalent Model: Applicable for the later d-block and p-block metals (e.g. Cu2+ and
Sn2+)

▪ Trend: The strengths of aqua acids are much greater than the ionic model predicts.

▪ Explanation: These metals repel the departing proton more strongly than is
predicted from the ionic model. The positive charge of the cation is not confined to
the central ion but is delocalized over the ligands and hence is closer to the departing
proton. The overlap between metal orbitals and the orbitals of an oxygen ligand
increases from left to right across a period. It also increases down a group, so aqua
ions of heavier d-block metals tend to be stronger acids.

▪ Example: Acidity order: Fe(OH2)62+ < Fe(OH2)63+ < Al(OH2)63+ ≈ Hg(OH2)2+.

▪ In Hg(OH2)2+, there is a large transfer of positive charge to oxygen as a result of


covalent bonding.