Organic Chemistry
Fourth Edition
David Klein
Chapter 3
Acids and Bases
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Copyright ©2021 John Wiley & Sons, Inc.
3.1 Bronsted-Lowry Acids and Bases
• Brønsted-Lowry definition
o Acids donate a proton
o Bases accept a proton
• Recall from General Chemistry this classic example:
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3.1 Conjugate Acids and Bases
• Brønsted-Lowry definition
o A conjugate acid results when a base accepts a proton
o A conjugate base results when an acid gives up a proton
• Label the acid, base, and the conjugates in the reaction
below
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3.2 Curved Arrows in Reactions /
Introduction
• The making and breaking of bonds involves electron movement.
• We use curved arrows to describe the flow of electron density.
• The are the same as curved arrows used to draw resonance structures,
but…
… here, the curved arrows are actually describing the physical movement
of electrons!!!
• Learning to draw mechanisms is one of the most valuable skills in
this class.
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3.2 Curved Arrows in Reactions / Single-
Step Example
• Consider a specific acid/base example
• The base “attacks” the acid, using a pair of electrons.
• The acid cannot lose its proton without the base taking it. All
acid/base reactions occur in one step.
• The mechanism shows two arrows indicating that two pairs of
electrons move simultaneously (one shows a bond breaking, the other
shows the bond being made).
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3.2 Curved Arrows in Reactions /
Multistep Example
• A multistep reaction mechanism is shown below.
• Which steps below are proton transfers?
• Before long, you will be drawing mechanisms like this one. For now,
just worry about correctly using curved arrows to show acid-base
reactions (that is proton transfers).
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SkillBuilder 3.1
Draw a mechanism for the following acid-base reaction. Label the
acid and base reactants, as well as the conjugate acid and conjugate
base.
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3.3 Quantifying Acidity / Introduction
• Recall from General Chemistry, how do “strong”
acids/bases differ from “weak” acids/bases?
• The strength of an acid or base is helpful to predict
how reactions will progress
o We will learn to do Quantitative strength analysis –
using pKa values to compare the strengths of acids.
o We will learn to do Qualitative strength analysis –
comparing the general stability of structures.
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3.3 Quantifying Acidity / Ka
• Quantitative strength analysis – using numerical data to compare
how strong acids are.
• Ka is the acid dissociation constant of an acid dissolved in water.
It is the measurement of an acid’s strength what water is the base.
• If the acid is strong, will Ka be bigger than 1, or smaller than 1?
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3.3 Quantifying Acidity / pKa
• Ka values range from 10 −50 to 1010 and so the size of these
numbers (very small or very big) are hard to work with.
• If you take the −log of the Ka, that will focus you on the
exponent of the Ka value, which ranges from −10 to 50.
• So, pKa values range from −10 to 50. Lower pKa = stronger
acid.
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3.3 Quantifying Acidity / Common
Compounds
Table 3.1 pK a values of common compounds
• There are more acids and pKa
values in Table 3.1 and the
inside cover of your textbook.
• Each pKa unit represents an
order of magnitude (or a power
of 10).
• For example, H2S O4 (pKa = −9)
is 100 times stronger acid than
HCl (pKa = −7).
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SkillBuilder 3.2
Acetic acid is the main constituent in vinegar solutions,
and acetone is a solvent often used in nail polish remover.
Using the pKa values in Table 3.1, identify which of these
two compounds is more acidic.
Copyright ©2021 John Wiley & Sons, Inc. 12
3.3 Quantifying Basicity
Table 3.1 pKa values of common compounds
You can also use pKa values to
compare the strengths of bases
because…
… the stronger an acid the
weaker its conjugate base.
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SkillBuilder 3.3
Using the pKa values in Table 3.1, identify which of the
following anions is a stronger base:
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3.3 Using pKa Values to Predict Equilibria
• With the relevant pKa values, you can predict which
direction an acid/base equilibrium will favor. Higher
pKa = weaker acid.
• This reaction demonstrates what is always true in an
acid-base reaction: equilibrium favors the weaker
acid and weaker base!!
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3.3 Using pKas to Analyze Equilibria
• Subtracting the pKa values, (50 − 15.7 ≈ 34) also tells you that
there will be ~1034 more products than reactants.
• It’s not really much of an equilibrium, and more like an
irreversible reaction.
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SkillBuilder 3.4
Using pKa values in Table 3.1, determine the position of
equilibrium for each of the following proton transfer
reactions:
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3.4 Qualifying Acidity / Introduction
• To determine the relative strength of two acids, without
knowing their pK a values, we compare the stability of
their conjugate bases.
• The stronger the acid, the more stable its conjugate
base!
• When an acid loses a proton, it forms the conjugate base,
which has a lone pair of electrons that resulted from the
loss of H+.
• To determine the stability of a conjugate base, we are
actually looking at the stability of the lone pair.
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3.4 Qualifying Acidity / ARIO
• The more effectively a conjugate base can stabilize its
negative charge (that is lone pair), the stronger the acid.
• Four main factors affect the stability of a negative charge:
o The type of atom that carries the charge.
o Resonance.
o Induction.
o The type of orbital where the charge resides.
• These factors can be remembered with the acronym, A R I O.
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3.4 Qualifying Acidity / Atom
• ARIO - The type of atom that carries the charge
In order to compare the acidity of the two compounds below
We need to draw and then analyze the stability of the negative
charge on the conjugate bases.
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3.4 Qualifying Acidity / Atom, Example
• ARIO - The type of atom that carries the charge
Here, we can determine whether an oxygen or a carbon will better
stabilize a negative charge.
1. When moving down a column, size is the most important factor. The
larger the atom, the more stable a negative charge will be.
2. For atoms in the same period, electronegativity is the most important
factor. Since C and O are in the same period, they are similar sizes. In
this case, the more electronegative atom will better stabilize the
negative charge.
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3.4 Qualifying Acidity / Atom, Carbon vs
Oxygen
• ARIO - The type of atom that carries the charge
The relative stability of the bases tells us the relative strength of the
acids.
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SkillBuilder 3.5
Compare the two protons that are shown in the following
compound. Which one is more acidic?
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3.4 Qualifying Acidity / Resonance
• ARIO - Resonance stabilizes a negative charge (that is
lone pair) by spreading it out across multiple atoms.
• Compare the acidity of the two compounds below by
comparing the stabilities of their conjugate bases.
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3.4 Qualifying Acidity / Resonance,
Example
• ARIO - Resonance
Now we know the relative
stability of the acids (which can
be confirmed by looking up their
pK a values).
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SkillBuilder 3.6
Compare the two protons shown in the following compound. Which
one is more acidic?
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3.4 Qualifying Acidity / Induction
• ARIO - Induction can also stabilize a formal negative charge by
spreading it out. How is induction different from resonance?
• Electron withdrawing atoms/groups inductively withdraw
electron density from their surroundings, thus stabilizing a
negative charge.
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3.4 Qualifying Acidity / Induction,
Examples
• More electron withdrawing groups = more stable conjugate base.
• The closer the electron withdrawing groups to the negative
charge = more stable the conjugate base.
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SkillBuilder 3.7
Identify which of the protons shown below is more acidic:
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3.4 Qualifying Acidity / Orbital
• ARIO - The type of orbital
also can affect the stability of
a formal negative charge.
• The closer electrons are held
to the nucleus, the more
stable they are.
• The shorter the atomic
orbital, the closer to the
nucleus.
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3.4 Qualifying Acidity / Orbital,
Introduction
• ARIO - The type of orbital also can affect the stability of a
formal negative charge.
• Consider the relative stability of the H’s indicated below:
• To predict which H is more acidic, we first have to draw the two
possible conjugate bases.
• Which carbanion is more stable?
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3.4 Qualifying Acidity / Orbital, Example
• ARIO - The type of orbital also can affect the stability of a
negative charge. The more s-character in the orbital, the more
stable the negative charge.
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3.4 Qualifying Acidity / Orbital, Practice
• Compare the acidity of the compounds below by
comparing the stabilities of their conjugate bases.
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SkillBuilder 3.8
Determine which of the protons identified below is more acidic:
Copyright ©2021 John Wiley & Sons, Inc. 34
3.4 Qualifying Acidity / Using ARIO
• When assessing the acidity of protons, we generally
use ARIO as the order of importance of these
stabilizing effects.
1. The type of atom that carries the charge.
2. Resonance.
3. Induction.
4. The type of orbital where the charge resides.
• It is typically helpful to use this order of priority when
comparing the stability of conjugate bases, but it isn’t
100% reliable: there are exceptions.
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3.4 Qualifying Acidity / Assessing ARIO
• Ethanol is more acidic than propylene. Therefore, the
conjugate base of ethanol must be more stable.
• The type of atom (O versus C) is consistent with this fact.
• But propylene’s conjugate base is resonance stabilized, which
would suggest it is more stable
• So, in this case, our order of priority (ARIO) is accurate.
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3.4 Qualifying Acidity / ARIO Sometimes
Fails
• ARIO is only a guideline of priority… it sometimes fails.
• In this example, we know equilibrium lies to the right because
we know the pKa values.
• If we had judged the conjugate base stability, we would’ve
concluded that negative charge on N is more stable than C, and
predicted equilibrium to lie to the left, and we would’ve been
wrong.
• Conclusion: for some acids, we simply need to know the pKa
values because they are exceptions to the ARIO priority rule.
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SkillBuilder 3.9
Predict which of the two protons identified below is more acidic and
explain why:
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SkillBuilder 3.9
Amphotericin B is a powerful antifungal agent used for intravenous
treatment of severe fungal infections. Without using a pKa table,
identify the most acidic proton in this compound.
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3.5 Assessing the Relative Acidity of
Cationic Acids
• To assess the acidity of cationic acids (HA+ vs. HB+), it is
often not necessary to compare their conjugate bases.
• Focus on charge stability: the stability of the positive
charges in the acids themselves
• For example, nitrogen can better stabilize a positive charge
(being less electronegative) compared to oxygen; NH4+ is
more stable than H3O+; H3O+ is more acidic.
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3.5 Assessing the Relative Acidity of
Cationic Acids
• What about the following acids (same atoms bearing the
positive charge)?
• Compare the conjugate bases: the weaker (more stable)
conjugate base gives the stronger acid.
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3.5 Assessing the Relative Acidity of
Cationic Acids
• The lone pair of the aryl amine is delocalized:
• This delocalized lone pair is less available to function as a
base—the aryl amin is weaker as a conjugate base.
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3.5 Assessing the Relative Acidity of
Cationic Acids
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SkillBuilder 3.10
Consider the structures for the following compounds:
Draw the conjugate acids of the compounds, and then
determine which of the two conjugate acids is more acidic.
Which is the stronger base, compound 1 or compound 2?
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3.6 Predicting Equilibrium Position
• Consider any acid base reaction:
• There are two distinct ways to predict which side is favored at
equilibrium.
1. The pKa values of H—A and H—B (the higher pKa will be
favored).
2. The relative stability of the bases, B− and A−.
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SkillBuilder 3.11
Predict the position of equilibrium for each of the following acid-
base reactions:
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SkillBuilder 3.12
Determine whether H2O would be a suitable reagent for protonating
the acetate ion.
Copyright ©2021 John Wiley & Sons, Inc. 47
3.7 Leveling Effect / Introduction
• Another important skill is to be able to choose an
appropriate solvent for an acid/base reaction.
• The solvent should be able to surround the reactants and
facilitate their collisions without itself reacting.
• Because water can act as an acid or a base, it has a leveling
effect on strong acids and bases.
o Acids stronger than H3O+ can not be used in water.
o Bases stronger than OH− can not be used in water.
• Why? – see the next few slides.
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3.7 Leveling Effect / Use of Water
• Appropriate use for water as a solvent – when the base is not
stronger than hydroxide:
• With water as the solvent, the CH3CO2− will react with the water,
but the equilibrium greatly favors the left side, so water is an
appropriate solvent.
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3.7 Leveling Effect / Strong Acids
• Because water can act as an acid or a base, it has a leveling
effect on strong acids and bases.
o Acids stronger than H3O+ cannot be used in water. For example,
water would react with sulfuric acid producing H3O+.
Virtually no sulfuric acid would remain if we wanted it to be
available to react with another reagent.
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3.7 Leveling Effect / Strong Bases
• Because water can act as an acid or a base, it has a leveling
effect on strong acids and bases.
o Bases stronger than OH− can not be used in water. For
example, we wouldn’t be able to perform the following acid-
base reaction in water.
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3.8 Solvating Effects / ARIO Is Insufficient
• Because they are so similar, ARIO can not be used to explain
the pKa difference comparing ethanol and tert-Butanol.
• As with all acids, the difference in acidity is due to the relative
stability of their conjugate bases.
• The ability of the solvent to stabilize conjugate bases comes into
play for this example.
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3.8 Solvating Effects / Sterics
• The solvent must form ion-dipole attractions to
stabilize the formal negative charge.
• If the tert-butoxide is sterically hindered, it won’t be as
well solvated as the ethoxide. That is why t-butanol is
not as acidic as ethanol.
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Conceptual Checkpoint
Predict which of the following compounds is more acidic:
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3.9 Counterions
• Counterions are also known as spectator ions.
• There are always present, because they are necessary to balance
the overall charge of a solution.
• Full reaction with counterion(s) included:
NaNH2 + H2O → NH3 + NaOH
• We often do not include the counterions when writing the rxn:
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3.10 Lewis Acids and Bases /
Definitions
• Lewis acid/base definition
o A Lewis acid accepts a pair of electrons
o A Lewis base donates a pair of electrons
• Acids under the Brønsted-Lowry definition are also acids
under the Lewis definition.
• Bases under the Brønsted-Lowry definition are also bases
under the Lewis definition.
• This reaction fits both definitions.
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3.10 Lewis Acids and Bases / Examples
• Lewis acid/base definition
o A Lewis acid accepts and shares a pair of electrons
o A Lewis base donates and shares a pair of electrons
• Some Lewis acid/base reactions can not be classified using the
Brønsted-Lowry definition.
• Explain how this reaction fits the Lewis definition but not the
Brønsted-Lowry definition.
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SkillBuilder 3.13
Identify the Lewis acid and the Lewis base in the reaction between
BH3 and THF.
Copyright ©2021 John Wiley & Sons, Inc. 58
