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Physical Chemistry

pKa

Definition and meaning of pKa in chemistry.

pKa is the negative base-10 logarithm of the acid ionization constant, Ka. It gives a convenient number for comparing acid strength: the lower the pKa, the stronger the acid.

In more detail

Acids differ in how completely they give up a proton in water. That tendency is measured by the acid ionization constant, Ka, which is large for strong acids and small for weak ones. Because Ka values span many orders of magnitude, chemists convert them to a simpler scale by taking pKa equal to the negative logarithm of Ka.

This turns awkward numbers like 1.8 times 10 to the minus 5 into an easy value of about 4.74. Because of the negative sign in the definition, the relationship between pKa and strength is inverted. A small Ka means a large pKa and a weak acid, while a large Ka means a small or even negative pKa and a strong acid.

Acetic acid has a pKa near 4.76 and is weak, while hydrochloric acid has a pKa below zero and is strong. A difference of one pKa unit represents a tenfold difference in the ionization constant. The pKa has a direct physical meaning tied to pH.

When the pH of a solution equals the pKa of an acid, exactly half of the acid is in its protonated form and half is in its deprotonated form. This is why the pKa marks the center of a buffer's most effective range and the midpoint of a titration curve.

The idea extends beyond acids. A base can be described by its pKb, and a conjugate acid-base pair follows the simple relationship pKa plus pKb equals 14 in water at 25 degrees Celsius. Chemists often list the pKa of the conjugate acid to compare base strength on a single scale.

Knowing pKa values helps predict the direction of proton-transfer reactions, since a proton tends to move from the stronger acid to form the weaker one.

Key facts

FieldPhysical Chemistry
DefinitionpKa = -log Ka
Meaninglower pKa = stronger acid
One unittenfold change in Ka
At pH = pKaacid is half ionized
Strong acidpKa below 0
RelationshippKa + pKb = 14 (water, 25 C)
Used inbuffers and titration curves
Example

Acetic acid has a Ka of about 1.8 times 10 to the minus 5, which gives a pKa of about 4.76. In a solution buffered at pH 4.76, half of the acetic acid exists as acetate ion and half remains as neutral acetic acid.

Frequently asked questions

Does a lower or higher pKa mean a stronger acid?

A lower pKa means a stronger acid. Because pKa is the negative log of Ka, a large Ka (strong acid) becomes a small pKa.

What happens when pH equals pKa?

The acid is exactly half ionized: half of it is in the protonated form and half is in the deprotonated form. This point is the center of a buffer's effective range.

How are pKa and pKb related?

For a conjugate acid-base pair in water at 25 degrees Celsius, pKa plus pKb equals 14. Knowing one lets you calculate the other.

Why use pKa instead of Ka?

Ka values range over many orders of magnitude and are awkward to compare. Taking the negative log compresses them into a simple scale that is easy to read and use.

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