Introductory Organic Chemistry I

CHEM 2020, Fall 2023

Dr. Hébert

Chapter 6
Acids and Bases

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Learning objectives
• Draw a curved arrow reaction mechanism for an acid–base reaction.

• Draw and interpret reaction coordinate diagrams for acid–base reactions.

• Rank the relative acidities of various acids or bases and rationalise the ranking in terms
of structural features.

• Identify the most acidic proton or basic site on a molecule.

• Compare, using pKa data, the relative strengths of both acids and their conjugate
bases, as well as the direction of an acid–base equilibrium.

• Qualitatively predict the direction of an acid–base equilibrium by comparison of the

structures of either the acid and conjugate acid or the base and conjugate base.

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The Brønsted–Lowry Definition

• Brønsted acids: any species that can DONATE protons (H+)

• Brønsted bases: any species that can ACCEPT protons (H+)

• When a base accepts a proton, it becomes a conjugate acid

• When an acid donates a proton, it becomes a conjugate base

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Examples of acid-base reactions

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Representations of acid-base reactions

H+ does not actually exist as a discrete species. It associates with the strongest
base in the system.

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Acid Strength
• Strength of a B-L acid is defined by the acid dissociation constant
Ka

conjugate base

• Strong acids have weak conjugate bases

• Weak acids have strong conjugate bases

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Acid Strength
• Ka values in organic chemistry span a large range: 1015 for the
strongest acids to 10-60 for the weakest acids known

Recall: pKa = -log(Ka)

pKa = -log(1015) = -15

pKa = -log(10-60) = 60

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Reaction Coordinate Diagrams

The position of an acid-

base equilibrium can
be predicted by
comparing acid or base
strengths.

Very strong acids have a

negative ∆G, and their
dissociation is
exothermic (Figure a) .

Most organic
acids are weak
and have positive
values of ∆G, and
their dissociation
is endothermic
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Reaction Coordinate Diagrams

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When using a pKa table, look
for the acid that most closely
resembles the group in
question.

There’s no need to memorize

exact pKa values, but it’s good
to have a general idea of
where difference classes of
acids lie on the scale.
Using pKa to measure base strength
The strength of a base can be quantified using the pKa of its
conjugate acid.

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Using pKa to measure base strength
Pay special attention to the different ionized forms of NH3.

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Predicting the Direction of Acid–Base Reactions
• pKa values are useful for predicting the equilibrium direction of a given
acid-base reaction
• Stronger acids readily give up their proton, whereas weaker acids
prefer to hold on to them
• Acid-base reactions always favour the formation of the weaker
conjugate acid (and base)

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In-class problem
Determine the direction of the following acid-base equilibria:

Remember:
stronger acids = smaller pKa values
weaker acids = larger pKa values

pKa: CH3CO2H 4.8, HCN 9.3, CH3CH2OH 16

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iClicker question
Determine the direction of the following acid-base equilibrium:

A. To the right C. Equal in both directions

B. To the left D. I don’t know

15 pKa: HOH 15.7 HCΞCH 25

Protonation at various pHs
The pKa of an acid can be used to predict the protonation state at a
particular pH.
Acids are primarily
• in protonated form when pH is less than pKa
• in deprotonated form when pH is greater than pKa

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Protonation at various pHs

If pH is very close to pKa value, a mixture of protonated

and deprotonated states is observed.

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What determines the strength of an acid?
• The strength of an acid can be determined by the stability of
the conjugate base
• The more stable the CB, the stronger the acid (and vice versa)
• To determine the strength of an acid, we look at how well the lone
pair/negative charge on the CB can be stabilized
• More stable CBs are also weaker bases

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Qualitative Estimates of Relative Acidities
• It is more important skill to be able to estimate the acidity of a
molecule (i.e., without using a pKa table)
• The acidity of an acid (HA) is impacted by the following factors:
1. Electronegativity
2. Atomic size
3. Induction
4. Hybridization
5. Resonance (charge delocalization)
These are not listed in order of importance, although
resonance has a very large impact on the acidity
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Electronegativity
• Higher electronegativity provides an increased ability to accommodate
negative charge.
• Thus, acidity increases across the same row in the periodic table

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Atomic Size
• Larger atomic size for anion spreads out electron density, making the
CB more stable
• Thus, acidity increases down the same column in the periodic table

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Induction
• Induction is a local change in the electron density due to electron-
withdrawing or electron-donating groups elsewhere in the molecule
• Electronegative atoms can stabilize the CB by withdrawing electron-
density through σ bonds.

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Induction
Strength of induction depends on
• electronegativity of atoms involved
• number of electronegative atoms involved
• proximity to charge (i.e., how many bonds away?)

Cl vs F:

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Induction

3 Cl vs 1 Cl:

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iClicker question

Rank the following molecules from the most acidic to the least acidic:

A) 1, 2, 3 D) 1, 3, 2

B) 3, 2, 1 E) I don’t know

C) 2, 3, 1
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Hybridization
• Atoms in organic molecules are generally in sp3, sp2, or sp hybridization
states.
• Since s orbitals are lower in energy than p, greater s character leads to
greater stability of the CB (electrons held closer to nucleus)

sp3
increasing
sp2 s character

sp

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Resonance (charge delocalization)
The ability to participate in resonance has a large impact on the acidity!

pKa ~ 16

pKa ~ 5

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Resonance (charge delocalization)
A proton can be removed from a carbon atom if
• a very strong base is present, and
• the resulting anion is stabilized

The anion generated when a

proton is removed adjacent to
carbonyl group is called an
enolate (more on this in Ch. 17).

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Positively Charged Acids
The CB of a positively charged acid is neutral. It may be easier in some
cases to compare the acid stabilities instead of the CBs.

Electronegativity:
• Higher electronegativity
destabilizes a positive
charge
• makes the acid less
stable and therefore
more acidic

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Positively Charged Acids
Atomic size:
• Large atoms form weaker bonds to protons when compared to smaller
atoms, thus making them less stable and more acidic

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Positively Charged Acids
Induction:
• Nearby electronegative atoms increase the effective positive charge on
an atom, resulting in destabilization.

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Positively Charged Acids
Induction:
• Alkyl groups stabilize positive charges by donating electron density.

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Positively Charged Acids
Resonance (charge delocalization):
• As with negative charges,
delocalization can stabilize
positive charges by spreading
the charge over a larger volume

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Qualitative Prediction of Acid-Base Equilibria
You can use the 5 factors we discussed to determine the position of a given
acid-base equilibrium (no pKa’s needed!)

e.g., Predict if the following acid-base reaction will favour reactants or

products.

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iClicker question
Predict if the following acid-base reaction will favour reactants or
products.

A) Reactants C) Equally favoured

B) Products D) I don’t know

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Ranking of Acidity
If asked to determine the most acidic proton in a molecule or to rank the
relative acidity of a group of molecules, follow these steps:

1) Classify acids by functional group type

2) Compare acids within a similar group by drawing their respective CBs

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Ranking of Acidity
3) Look for stabilizing factors, such as:
− Electronegativity
− Atomic size
− Inductive effects
− Hybridization
− Resonance (often the most impactful factor)

4) If comparing neutral acids, the strongest acid has the weakest (most
stable) conjugate base.
If comparing charged acids, the one that destabilizes the positive charge
more is more acidic.

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In-class problem
Identify the most acidic proton in the following molecules and rank their
relative acidity from most acidic to least acidic

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Acids and Bases: The Lewis Definition
• Lewis acids (LAs) are electron pair acceptors
• Lewis bases (LBs) are electron pair donors

In LA-LB reactions,
• The LA is the electrophile (lover of electrons)
• The LB is the nucleophile (lover of the positively charged nucleus)
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Comparing Brønsted & Lewis Acid-Base Reactions

Common Lewis acids: BF3, BBr3, AlCl3, FeCl3, ZnCl2, TiCl4, Hg(OAc)2

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