Acids and Bases

▪ Definition: A Brønsted acid is a proton donor.

A Brønsted base is a proton acceptor.

▪ Examples: HF is a Brønsted acid. It can donate a proton to another molecule, such

as H2O, when it dissolves in water:

▪ NH3 is a Brønsted base. It can accept a proton from a proton donor such as H2O:

▪ These two examples show that water is an example of an amphiprotic substance,

a substance that can act as both a Brønsted acid and a Brønsted base.

▪ When an acid donates a proton to a water molecule, the latter is converted into a
hydronium ion, H3O+.

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 Proton Transfer Equilibria in Water
▪ Proton transfer between acids and bases is fast in both directions, so the following
dynamic equilibria give a more complete description of the behaviour of the acid HF
and the base NH3 in water than the forward reaction alone.

Conjugate Acids and Bases

▪ When a species donates a proton, it becomes the conjugate base; when a species
gains a proton, it becomes the conjugate acid.

▪ The species Base1 is called the conjugate base of Acid1, and Acid2 is the conjugate
acid of Base2.

▪ F– is the conjugate base of HF and H3O+ is the conjugate acid of H2O.

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 Strengths of Brønsted Acids and Bases
▪ Acidity Constant (Ka): Strength of a Brønsted acid is measured by its acidity constant.

▪ Basicity Constant (Kb): Strength of a Brønsted base is measured by its basicity constant.

▪ The stronger the base, the weaker is its conjugate acid.

▪ Ka for HF in Water:

▪ More generally:

▪ The experimental value of Ka for HF in water is 3.5 × 10–4, indicating that under
normal conditions only a very small fraction of HF molecules are deprotonated in
water.
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 Strengths of Brønsted Acids and Bases
▪ Kb for NH3 in Water:

▪ More generally:

▪ The experimental value of Kb for NH3 in water is 1.8 × 10–5, indicating that under
normal conditions only a very small fraction of NH3 molecules are protonated in water.

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 Autoprotolysis / Autoionization
▪ Definition: Because water is amphiprotic, a proton transfer equilibrium exists even
in the absence of added acids or bases. The proton transfer from one water molecule
to another is called autoprotolysis.

▪ Autoprotolysis Constant or Autoionization Constant (Kw) of Water:

▪ The experimental value of Kw is 1.00 × 10–14 at 25°C, indicating that only a very small
fraction of water molecules are present as ions in pure water.

▪ pH of pure water is 7.00, and [H3O+] = [OH–], then [H3O+] = 1.0 × 10–7 mol dm–3.

▪ Taking negative logarithms:

pKw = pH + pOH = 14

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 Relationship of Ka and Kb with Kw

[H3O+][A-]
▪ For a weak acid in water: Ka =
[HA]

[HA][OH-]
▪ For the conjugate base reaction: A- + H 2O HA + OH- Kb =
[A-]
[H3O+][A-] [HA][OH-]
▪ Ka x Kb = ×
[A-]
= [H3O+] [OH-] = Kw
[HA]

▪ Thus, for a conjugate acid-base pair: Ka × Kb = Kw

▪ Therefore, the larger the Ka, the smaller the Kb. That is, the stronger the acid, the
weaker the conjugate base.

▪ Taking negative logarithms: pKa + pKb = pKw Since pK = –log K