Organic Chemistry

Third Edition
David Klein

Chapter 3
Acids and Bases

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 3.1 Bronsted-Lowry Acids and Bases
• Brønsted-Lowry definition
– Acids donate a proton
– Bases accept a proton

• Recall from General Chemistry this classic example

conjugate conjugate
base acid

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 3.1 Conjugate Acids and Bases
• Brønsted-Lowry definition
– A conjugate acid results when a base accepts a proton
– 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
• 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
• 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
• 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 (i.e. proton transfers).

• Practice with SkillBuilder 3.1

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 3.3 Quantifying Acidity
• 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

– We will learn to do Quantitative strength analysis – using pKa

values to compare the strengths of acids

– We will learn to do Qualitative strength analysis – comparing

the general stability of structures.

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 3.3 Quantifying Acidity
• 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

• 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
• 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, H2SO4 (pKa = -9) is

100 times stronger acid than HCl
(pKa = -7)

• Practice with SkillBuilder 3.2

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 3.3 Quantifying Basicity

You can also use pKa

values to compare
the strengths of
bases because…

… The stronger an
acid the weaker its
conjugate base.

• Practice with SkillBuilder 3.3

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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

• Practice with SkillBuilder 3.4 and checkpoint 3.12

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 3.4 Qualifying Acidity
• to determine the relative strength of two acids, without knowing
their pKa values, we compare the stability of their conjugate
bases

• The stronger the acid, the more stable it’s conjugate base!

• When an acid loses a proton, it forms the conjugate base, which

has a lone pair of electrons that resulted from the lose 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
• The more effectively a conjugate base can stabilize its negative
charge (i.e. lone pair), the stronger the acid

• Four main factors affect the stability of a negative charge:

– The type of atom that carries the charge

– Resonance
– Induction
– The type of orbital where the charge resides

• These factors can be remembered with the acronym, ARIO

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 3.4 Qualifying Acidity
• 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
• 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

Less stable More stable

(1) The larger the atom, the more stable a negative charge will
be (size is the most important factor)

(2) 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
• ARIO - The type of atom that carries the charge
The relative stability of the bases tells us the relative strength of the
acids

More stable
Less stable

Less acidic MORE ACIDIC

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 3.4 Qualifying Acidity
• ARIO - Resonance stabilizes a negative charge (i.e. 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
• ARIO - Resonance

Compare the
stability of versus
these conjugate
bases

Now we know the relative

stability of the acids (which can
be confirmed by looking up
their pKa values)
Less acidic MORE ACIDIC
Practice with Skillbuilder 3.6
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 3.4 Qualifying Acidity
• 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.

less acidic more acidic

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 3.4 Qualifying Acidity
• More electron withdrawing groups = more stable conjugate base
• The closer the electron withdrawing groups to the negative
charge = more stable the conjugate base

• Practice with SkillBuilder 3.7

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 3.4 Qualifying Acidity
• ARIO - The type of orbital also can affect the stability of a formal
negative charge

• The closer electrons are held to the nucleus, the the more stable
they are.

• The shorter the atomic

orbital, the closer to the
nucleus.

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 3.4 Qualifying Acidity
• 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

versus

• Which carbanion is more stable?

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 3.4 Qualifying Acidity
• 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.

versus

Lone pair in a sp2 Lone pair in a sp

orbital, not as close orbital, closer to the
to the nucleus nucleus
LESS STABLE MORE STABLE

less acidic MORE ACIDIC

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 3.4 Qualifying Acidity
• Compare the acidity of the compounds below by comparing the
stabilities of their conjugate bases.

• Practice with SkillBuilder 3.8

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 3.4 Qualifying Acidity
• 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
• Ethanol is more acidic than propylene. Therefore, the conjugate
base of ethanol must be more stable.

pKa = 16 pKa = 43 More stable Less stable

• The type of atom (O vs. 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 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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 3.4 Qualifying Acidity
• Practice the Skill 3.23 – Predict which proton (red vs. blue) is
more acidic in each of these compounds.

• Keep practicing with the other examples in Practice the Skill 3.23

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 3.5 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-

See Skillbuilder 3.10

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 3.5 Choosing a Reagent
• Another important skill is to be able to choose an appropriate
reagent for a acid/base reaction
• Choose an acid from Table 3.1 that could effectively protonate
each of the following molecules
O

O O
O

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 3.6 Leveling Effect
• Another important skill is to be able to choose an appropriate
solvent for a 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

– Acids stronger than H3O+ can not be used in water.

– Bases stronger than OH- can not be used in water. WHY? – see
next few slides

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 3.6 Leveling Effect
• Appropriate use for water as a solvent – when the base is not
stronger than hydroxide:

pKa = 15.7 pKa=

4.75

• 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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 3.6 Leveling Effect
• Because water can act as an acid or a base, it has a leveling effect
on strong acids and bases

– Acids stronger than H3O+ cannot be used in water. For example,

water would react with sulfuric acid producing H3O+. Virtually
no sulfuric acid will remain if we wanted it to be available to
react with another reagent

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 3.6 Leveling Effect
• Because water can act as an acid or a base, it has a leveling effect
on strong acids and bases
– 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

+ + H
N N
H

– Which of the following solvents would be a better choice?

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 3.7 Solvating Effects
• 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 conjugates bases comes into
play for this example

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 3.7 Solvating Effects
• 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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 3.8 Counter Ions
• 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:

• We often do not include the counter ions when writing the rxn:

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 3.9 Lewis Acids and Bases
• Lewis acid/base definition
– A Lewis acid accepts a pair of electrons
– 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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 3.9 Lewis Acids and Bases
• Lewis acid/base definition
– A Lewis acid accepts and shares a pair of electrons
– 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

• Practice with SkillBuilder 3.12

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