Strengths of Oxo Acids

Structure and pKa Values of Oxoacids

Cl

Cl

Cl

Se

As

p = number of nonprotonated O atoms

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 Strengths of Oxo Acids
▪ Mononuclear Oxo Acids: They are formed by the electronegative elements at the
upper right of the periodic table and by other elements in high oxidation states.

▪ Examples: H2CO3, HNO3, H3PO4 and H2SO4

▪ Substituted Oxo Acids: One or more –OH groups of an oxoacid may be replaced by
other groups to give a series of substituted oxoacids.

▪ Examples:

Fluorosulfuric Acid Trifluoromethanesulfonic Aminosulfuric Acid

Acid (Triflic Acid) (Sulfamic Acid)

Electron Withdrawing Substituents (-F, -CF3) Electron Donating

Substituent (-NH2)

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 Strengths of Oxo Acids
▪ Effect of Electron Withdrawing Substituents: Because F atom is highly
electronegative, it withdraws electron density from the central S atom and generates
a higher effective positive charge on S atom. As a result, fluorosulfuric acid and
trifluoromethanesulfuric acid are stronger than sulfuric acid.

▪ Effect of Electron Donating Substituents: The –NH2 group, which has lone pair
electrons on N atom, can donate electron density to S atom by π bonding. This transfer
of charge reduces the positive charge of the central atom and weakens the acid. As a
result, aminosulfuric acid is weaker than sulfuric acid.

Phosphoric acid Phosphorous acid Hypophosphorous acid

▪ In an oxoacid, for the H atom to be acidic, it must be attached to an O atom. The H
atom bonded directly to central atom (such as in P atom H3PO4) is not acidic because
P and H atoms have same electronegativity and P–H bond is nonpolar. Thus, H3PO4
possesses 3 acidic hydrogen atoms; H3PO3 acid, two; and H3PO2, only one.

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 Strengths of Oxo Acids
▪ Trend: For oxoacids (formula: HnYOm) that contain the same number of OH groups
and the same number of O atoms, acid strength increases as the electronegativity of Y
increases.
▪ Example: The acid strength of the hypohalous acids HOY (Y = Cl, Br, or I) increases as
the electronegativity of the halogen increases:

▪ Explanation: As the halogen becomes more electronegative, an increasing amount

of electron density shifts from the bond toward the halogen, thus weakening
the bond and increasing its polarity. As a result, the proton is more easily
transferred to a solvent water molecule, and so the acid strength increases.

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 Strengths of Oxo Acids
▪ Trend: For oxoacids (formula: HnYOm) that contain the same atom Y but different
numbers of O atoms, acid strength increases as the oxidation number of Y increases.
The oxidation number of Y increases, in turn, as the number of O atoms increases.
▪ Example:

Another Example: Acidity Order: H2SO3 < H2SO4

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 Strengths of Oxo Acids
▪ Explanation: As the number of O atoms in increases, an increasing amount of
electron density shifts from the Cl atom toward the more electronegative O atoms.
The amount of positive charge on the Cl atom therefore increases as its oxidation
number increases. The increased positive charge on the Cl atom attracts an increasing
amount of electron density from the bond, thus weakening the bond and increasing
its polarity. As a result, the proton is more easily transferred to a solvent water
molecule.

▪ Another factor that affects the acid strength of oxoacids is the relative stability
of the corresponding oxoanions. The ClOm- anion becomes more stable as the number
of O atoms increases in the series ClO- < ClO2- < ClO3- < ClO4- because a larger number
of electronegative O atoms can better accommodate the anion’s negative charge. In
other words, the number of resonance structures of the anion increases as the
number of O atoms increases. As the stability of the anion increases, the
corresponding acid has a greater tendency to dissociate.

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 Strengths of Oxo Acids
▪ Pauling’s Rules: Trends in acidity of oxoacids are systematized semiquantitatively.

▪ Rule 1: For the oxoacid OpY(OH)q, pKa ≈ 8 – 5p

p = number of oxo groups
q = number of hydroxyl groups

▪ Rule 2: The successive pKa values of polyprotic acids (those with q > 1), increase by
5 units for each successive proton transfer.

▪ Example: Sulfuric acid has p = 2 and q = 2

Predicted Experimental
pKa1 -2 -2.0
pKa2 +3 +1.9

▪ Comparison of theoretical values with experimental ones suggest that these rules
are only approximations.

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 Strengths of Oxo Acids
Comparison between Theoretical and Experimental pK Values (within Parenthesis)
Predicted pK Values Experimental pK Values
p=0 pKa = 8 HOCl (7.2); Si(OH)4 (10)
p=1 pKa1 = 3 H2CO3 (3.6)
pKa2 = 8 HClO2 (2.0)
pKa3 = 13 H3PO4 (2.1; 7.4; 12.7)
H3PO3 (1.8; 6.6)
H3PO2 (2.0)
p=2 pKa1 = -2 HNO3 (-1.4)
pKa2 = 3 H2SO4 (-2.0; +1.9)
pKa3 = 8 HClO3 (-1.0)
p=3 pKa = -7 HClO4 (-10)