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pH and pKa

Whether a molecule is holding its proton or has let it go depends on one comparison: pH versus pKa. That single rule also explains why an indicator changes color right where it does.

§1

Which form dominates.

Comparing the solution's pH to a species' pKa tells you which form predominates. When pH < pKa, the protonated (acid, HA) form dominates; when pH > pKa, the deprotonated (conjugate base, A⁻) form dominates.

At pH = pKa, the two forms are present in equal amounts.

An indicator is itself a weak acid whose protonated and deprotonated forms have different colors. It changes color as the pH crosses its pKa, which is exactly why an indicator signals the pH range around that pKa.

UNIT 8 TOPIC 8.7 • pH AND pKa pH VS pKa pH compared with pKa predicts the dominant form of a weak acid system. pKa − 2 pKa − 1 pH = pKa pKa + 1 pKa + 2 HA dominates equal amounts A⁻ dominates ← lower pH (more acidic) higher pH (more basic) → pH < pKa [HA] > [A⁻] HA (protonated form) dominates. pH = pKa [HA] = [A⁻] Equal amounts of HA and A⁻ present. pH > pKa [A⁻] > [HA] A⁻ (deprotonated form) dominates. pKa = −log Ka where Ka is the acid dissociation constant. CED ANCHOR pH = pKa + log [A⁻] / [HA] At pH = pKa the log term is 0, so [HA] = [A⁻]. AP Chemistry · Unit 8 · Acids and Bases
Fig. 8.7.1 Comparing pH to pKa tells you which form dominates: pH < pKa favors the protonated (acid, HA) form; pH > pKa favors the deprotonated (conjugate base, A⁻) form; at pH = pKa they are equal. Indicators change color by this same shift.
§2

Applying the comparison.

Compare pH to pKa, then name the form.

  1. Find the species' pKa. The pKa of the acid form.
  2. Compare it to the solution pH. Is the pH below, above, or equal to the pKa?
  3. Name the predominant form. pH < pKa → protonated (HA); pH > pKa → deprotonated (A⁻); equal at pH = pKa.
  4. Apply to indicators. An indicator's two colored forms predominate on either side of its pKa, so it changes color there.
§3

The pieces you'll meet.

One comparison, one predominant form.

pH vs pKa
pH vs pKa
The comparison that sets the predominant form.
below
pH < pKa
Protonated (acid, HA) form dominates.
above
pH > pKa
Deprotonated (conjugate base, A⁻) form dominates.
equal
pH = pKa
Equal amounts of both forms.
indicator
Indicator
A weak acid whose forms have different colors.
color change
Color change
Occurs as pH crosses the indicator's pKa.
§4

Worked example: predominant form and indicators.

Species. A weak acid HA has pKa = 5.

At pH 3. pH (3) < pKa (5), so the protonated HA form predominates.

At pH 7. pH (7) > pKa (5), so the deprotonated A⁻ form predominates.

Indicator. An indicator with pKa ≈ 5 would show its acid-form color below pH 5 and its base-form color above pH 5, changing color as the pH crosses 5.

§5

Mistakes that cost real points.

Pitfall · 01

"When pH is below the pKa, the deprotonated form dominates."

It is the reverse: when pH < pKa, the protonated (acid, HA) form dominates; the deprotonated (A⁻) form dominates when pH > pKa. Mixing up the direction misidentifies the predominant species.

Fix. Use: pH < pKa → protonated (HA); pH > pKa → deprotonated (A⁻).

Pitfall · 02

"An indicator changes color at pH 7."

An indicator changes color around its own pKa, not at pH 7. Different indicators have different pKa values and change color at different pH ranges — that is why the right indicator is chosen to match a titration's equivalence pH.

Fix. Match an indicator's color change to its pKa, not to pH 7.

Pitfall · 03

"At pH = pKa, the solution is neutral (pH 7)."

pH = pKa means the protonated and deprotonated forms are equal — it is not a statement that the pH is 7. A species with pKa = 4 has equal forms at pH 4, which is acidic, not neutral.

Fix. Read pH = pKa as equal amounts of the two forms, at whatever pH the pKa happens to be.

§6

Skill Check.

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