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Acid-base chemistry is one of the main tools for predicting how organic molecules react. In organic chemistry, an acid donates H+ and a base accepts H+, but the most useful question is often which side of an equilibrium is favored. The pKa scale lets you compare acids quantitatively, so you can decide whether a proton transfer is likely to happen.

This matters because many reaction mechanisms begin with protonation or deprotonation.

Key Facts

  • Lower pKa means stronger acid, and higher pKa means weaker acid.
  • Acid strength increases when the conjugate base is more stable.
  • For HA + B- ⇌ A- + HB, equilibrium favors the side with the weaker acid, which has the higher pKa.
  • Approximate pKa values: carboxylic acids 4 to 5, phenols about 10, alcohols about 16, alkynes about 25, alkanes about 50.
  • Resonance, electronegativity, induction, hybridization, and atom size can stabilize a conjugate base.
  • A useful estimate is ΔpKa = pKa(product acid) - pKa(reactant acid), and favorable proton transfer usually has ΔpKa > 0.

Vocabulary

pKa
pKa is a number that measures acid strength, with smaller values meaning the acid gives up H+ more easily.
Conjugate base
A conjugate base is the species left after an acid donates a proton.
Resonance stabilization
Resonance stabilization occurs when charge is spread over multiple atoms by delocalized electrons.
Inductive effect
The inductive effect is the pulling or pushing of electron density through sigma bonds by nearby atoms or groups.
Proton transfer
A proton transfer is an acid-base step in which H+ moves from an acid to a base.

Common Mistakes to Avoid

  • Comparing acids by the strength of the bond to hydrogen alone is wrong because acidity depends strongly on the stability of the conjugate base after H+ leaves.
  • Thinking a negative charge always means a strong base is wrong because a resonance-stabilized or electronegative atom can hold negative charge with low basicity.
  • Using pKa values backward is wrong because the stronger acid has the lower pKa, while equilibrium favors formation of the weaker acid with the higher pKa.
  • Ignoring solvent and functional group context is wrong because acid-base behavior can change when ions are stabilized differently or when nearby groups withdraw or donate electron density.

Practice Questions

  1. 1 Acetic acid has pKa 4.8 and ethanol has pKa 16. Will ethoxide deprotonate acetic acid? Calculate ΔpKa using ethanol as the product acid.
  2. 2 Phenol has pKa 10 and acetylene has pKa 25. Which conjugate base is stronger, phenoxide or acetylide, and by about how many pKa units do their conjugate acids differ?
  3. 3 Explain why a carboxylic acid is much more acidic than an alcohol even though both contain an O-H bond.