Predicting Acid

Strength
UCI Chem 51A
Dr. Link
Goals

After this lesson you should be able to:

Predict relative strength of acids or
bases using structure
Provide reasoning for acid or base
strength predictions
Acid Strength

We use pKa to measure acid strength.

We can correlate acid strength to base
strength.
What happens if we don’t have pKa
information?
 Golden Rule of Acid Strength
Anything that stabilizes the conjugate
base increases the strength of the acid!

H
H A + O +
H H O A
H H

Stabilize me!
Factors Affecting pKa

Element Effect
Inductive Effect
Resonance Effect
Hybridization Effect
Quick Question!
Choose the compound with the lowest pKa.

H2O CH4

HF NH3
Element Effect: Row
Across a row, acidity of H-A increases.
Electronegativity

C N O F
 Element Effect: Column
Acidity increases as size of conjugate base increases.

H"F,%pKa%=%3.2%%

H"Cl,%pKa%=%"7% increasing)
acidity)

H"Br,%pKa%=%"9%

H"I,%pKa%=%"10%

Spreading charge over larger volume stabilizes conjugate base

Another Quick Question!
Choose the most acidic compound.

CH3CH2OH ClCH2CH2OH

Cl2CHCH2OH F2CHCH2OH
 Inductive Effect
Inductive Effect: Electronegative atoms
stabilize the conjugate base by pulling electron
density toward themselves.
O
F
Inductive Effect: Anions
Inductive Effect Details
More electron-withdrawing groups = greater
inductive effect
Stronger electron-withdrawing groups =
greater inductive effect
Inductive effects decrease dramatically with
distance.
A Familiar Question
Choose the compound with the highest pKa.

OH
OH
+ NaOH
+ NaOH
Resonance Effect
Resonance Effect: Conjugate base is stabilized
by resonance (delocalization of charge)
One More Question!
Which contains the most acidic proton?
H H
CH3CH3$ H H
H H

Hybridization matters!
Hybridization Effect
Hybridization Effect: Increased percent
s-character of orbital containing lone
pair in conjugate base increases acidity
of corresponding acid.
Why?
S-orbitals closer to nucleus than p-
orbitals.
Priority of Effects

1.
2.
3.
Translating Acid and Base
Strength
Two ways to think about basicity:
Stronger acid has weaker conjugate base and
vice versa
F- Br -

Increased charge density on atom = more

likely to share e- = stronger base

NH3
 Basicity Examples
Choose the stronger base:

OH- NH2- CH3-

CH3CH2NH2 CCl3CH2NH2 CF3CH2NH2

Wrapping Up

Practice predicting relative acidities or

basicities based on structure.
Provide rationale for your choices!