Introduction to Acids and Bases

Chapter 3: Acids and Bases
Hello
1
Chapter 3: Acids and Bases
Topics:
• Introduction to Brønsted-Lowry Acids and Bases
• Flow of Electron Density: Curved-Arrow Notation
• Brønsted-Lowry
Hello Acidity: Quantitataive Perspective
• Brønsted-Lowry Acidity: Qualitative Perspective
• Position of Equilibrium and Choice of Reagents
• Leveling Effect
• Solvating Effects
• Counterions
• Lewis Acids and Bases
2
Chapter 3: Introduction
• 95% of the reaction covered in organic chemistry are ionic reactions.

• Ionic Reaction: A reaction where ions participate as reactants,
intermediates, or products.
• Most of theHello
time these ions are acting either as an acid or as a
base.
• We must learn how to deal with acids and bases in the context of
organic chemistry.
• We need to:
• Identify acids and bases
• Compare acid/base strengths in order to determine
reactivity and what reagents are needed for a reaction.
• Draw acid base reactions
3
Chapter 3: Introduction to Brønsted-Lowry
Acids and Bases
• Brønsted-‐Lowry definition
– Acids donate a proton
– Bases accept a proton
Hello
• Recall from General Chemistry this classic example
4
Chapter 3: Introduction to Brønsted-Lowry
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
– A conjugate acid-‐base
Hello pair d iffers by t he p resence o f a n H+.
• Label the acid, base, and the conjugates in the reaction below
5
Chapter 3 Flow of Electron Density: Curved-
Arrow Notation
Hello
Base Acid Conjugate Acid Conjugate Base
6
Arrow Notation
• The making and breaking of bonds involves electron movement
• We use curved arrows to describe the flow of electron density
Hello
• They 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
7
Arrow Notation
• Reaction Mechanism: Shows how a reaction occurs in terms of
the motion of electrons.
Hello
• In this case the base is abstracting a proton from the acid.
8
Arrow Notation
• Consider a specific acid/base example
Hello
• The base “attacks” the acid, using a pair of electrons.

• You need a pair of electrons to form a new bond!
• 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)
9
Arrow Notation
• A multistep reaction mechanism is shown below
• Which steps below are proton transfers?
Hello
step 1 step 2 step 3
• 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).
10
Arrow Notation
All of the following acid-‐base reactions are reactions that we will study in
greater detail in the chapters to follow. For each one, draw a mechanism,
then clearly label the acid, the base, the conjugate acid and conjugate base.
H
O O
1. +
OH + H
O
H
Hello
H
2. O
+
H
O
O
+
H
O
H
H H
O O
3.
H
N N
+ +
O
O
H O
4.
O + + O
OH H H
Arrow Notation
Answers
H
O O
1. + OH + H
O
H
Hello
Acid Base Conjugate Base Conjugate Acid
H
O H O
2. +
O
+
H
O
H
H H
Base Acid Conjugate Acid Conjugate Base

Arrow Notation
Answers
O O
H
H N
3.
N
+ +
Hello
O
O
H O
O + + O
OH H H
4.
Chapter 3 Brønsted-Lowry Acidity:
Quantitative Perspective
• Recall from General Chemistry, how do “strong” acids/bases differ

from “weak” acids/bases?
• The strength of an Hello

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.
14
QuanJfying Acidity
• Quantitative strength analysis – using numerical data to compare
how strong acids are.
Hello
• 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 greater than 1, or less than 1?
15
QuanJfying Acidity
• Ka values range from

Hello 10-‐50 to 1010 and 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
16
Chapter 3 Broasted-Lowry Acidity:
QuanJfying Acidity
• There are more acids and pKa
values in Table 3.1 and the inside
Hello 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)
17
Chapter 3 Broasted-Lowry Acidity:
Complete Table
Hello
18
For each pair of compounds below, identify the more acidic
compound:
O
H O O
a. b. H
H H H H
O
Hello
H H H
c. N
H C C H d. O
H Cl
H H H
H H H O H
O
e. H C C H H C C H f. O S O
H H H O
Answers: The one with the lowest pKa is the most acidic. Look up
the pKa values in the pKa table.
O
H O O
a. b. H
H H H H
O
Hello
pKa = 9.9 (more acidic) 15.7 (less acidic) pKa = 18 (less acidic) 15.7 (more acidic)
H H H
c. N
H C C H d. O
H Cl
H H H
pKa = 38 (less acidic) 25 (more acidic) pKa = −1.74 (less acidic) −7 (more acidic)
H H H O H
O
e. H C C H H C C H f. O S O
H H H O
pKa = 50 (less acidic) 25 (more acidic) pKa = −7.3 (less acidic) −9 (more acidic)
Using pKa values to compare bases.
You can also use pKa
values to compare the
Hello strengths of bases
because…
… The stronger an

acid the weaker its
conjugate base.
The higher the pKa (for the acid), the stronger the conjugate base
21
For each pair of compounds below, identify the more basic
compound:
a. H C C N b. O
H H O
Hello
O
c. O
H H d. OH O
H H
e. H C C H H C C f. Cl OH
H
Answer: The stronger conjugate base has the highest pKa for
the initial acid.
a. H C C N b. O
H H O
pKa(iniJal acid) = 25 Hello
38 (stronger base) 18 (stronger base) 16
O
c. O
H H d. OH O
pKa(iniJal acid) = −7.3 −1.74 (stronger base) 15.7 16 (stronger base)
H H
e. H C C H H C C f. Cl OH
H
pKa(iniJal acid) = 50 (stronger base) 25 −7 15.7(stronger base)
Using pKa values to compare acids and bases.
• Use the pH scale as your guide. Remember the lower the pH the
more acidic, the higher the pH the more basic. pKa works the same
Hello
way.
• For an acid: The lower the pKa = more acidic.

• Weaker conjugate base
• For a base: The higher the pKa (for the conjugate acid) = more basic.
• Stronger conjugate base
24
Another way to think about it.
• The lower the pKa:
• Stronger acids The conjugate base is weak since
• Weaker conjugate
Hello bases it can’t hold onto the H+ very well
• The higher the pKa:

• Weaker acids
• Stronger conjugate bases
The strength of the conjugate base determines the acidity of the
acid. If you have a strong conjugate base, it will not give up the H+
easily so therefore you will have a weak acid (high pKa)
25
Using pKa values to predict the posi4on of equilibrium
• With the relevant pKa values, you can predict which direction an
acid/base equilibrium will favor.
Hello
• This reaction demonstrates what is ALWAYS true in an acid-‐base
reaction: equilibrium favors the weaker acid and weaker base!!
Always Strong(er) ⟶ Weak(er)

26
Determine the position of equilibrium for each acid-‐base reaction below.
H
a.
O
+
OH ? O + H2O
Hello
O O
H
b. +
OH ? + H2O
H
c. + O +
H Cl
H H ? Cl
H
O
H
d. H C C H + NH2 ? H C C + NH3
Chapter 3 Brønsted-Lowry Acidity: Quantitative
Perspective
Answer: First determine the acid on each side, then look up the
pKa values, finally, the reaction shifts away from the stronger
acid (lower pKa) toward the weaker acid (higher pKa)
a. H + + H2O
O Hello OH O
Acid Acid
pKa = 16 Reac4on L ies
t o
t he
L eO
pKa = 15.7
Weaker Acid Stronger Acid
O O
H
b. + + H2O
OH
Acid Acid
pKa = 9.9 Reac4on L ies
t o
t he
R ight
pKa = 15.7
Stronger Acid Weaker Acid
Chapter 3 Brønsted-Lowry Acidity: Quantitative
Perspective
Answer: First determine the acid on each side, then look up the
pKa values, finally, the reaction shifts away from the stronger
acid (lower pKa) toward the weaker acid (higher pKa)
H
c. + O +
H Cl
Hello H H Cl O
H H
Acid Acid
pKa = −7 Reac4on L ies
t o
t he
R ight
pKa = −1.74
d. H C C H + NH2 H C C + NH3
Acid Acid
pKa = 25 pKa = 38
Reac4on Lies to the Right
Using pKa values to analyze equilibria
Hello
• 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
30
Qualitative Perspective
• 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!
Hello
• 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 or the concentration of
electron density. Both will play a role in this.
The less stable the lone pair, the more it “holds onto” the H+.
The more concentrated the electrons, 31 t he m ore it “ holds onto” t he H +.
• The more effectively a conjugate base can stabilize its negative

charge (i.e. lone pair), the stronger the acid
• Four main factors

Hello 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
32
will consider four factors: (1) the
Chapter 3 Brønsted-Lowry Acidity: atom bearing the charge, (2) reso
bitals. Qualitative Perspective
m •bears the
ARIO charge?
-‐ The type of The
atom first
that factor
carries involves comparing the atoms
the charge
arge in each conjugate base. For example, consider the structures o
In order to compare the acidity of the two compounds below
O
Hello H H
Butane Propanol
s the relative acidity of these two compounds, we must first deproto

We need to draw and then analyze the stability of the negative
drawcharge
the conjugate bases: bases
on the conjugate
⊝ ⊝
O
e these conjugate bases by looking at where the negative charge is loc

What are your thoughts?
ugate base, the negative charge is on a carbon atom. In the second co
33
is on an oxygen atom. To determine which of these is more stable,
H H
Chapter 3 Brønsted-Lowry Butane Acidity:
Propanol
the relative
• ARIO -‐ The acidity of these
type of atom twotcompounds,
that carries he charge we must first deproton
drawHere,
the wconjugate e can determine
bases: whether an oxygen or a carbon will better stabilize a
negative charge
⊝ ⊝
Less%stable% O More%stable%
Hello
these
(1)conjugate bases
The larger the atom, bythe
looking at where
more stable thecharge
a negative negativewill be charge is loca
(size is the
most important factor, more disperse charge)
gate base, the negative charge is on a carbon atom. In the second con
on (2)
an oxygen atom.
Since C and To
O are in determine
the same period, which
they are of these
similar is Imore
sizes. stable,
n this case, the w
ments are inethe
more same row
lectronegative or
atom win ill bthe same
etter column
stabilize of
the negative the periodic
charge (better ata t
−
holding onto the excess e )
• The valence electrons in oxygen experience a greater “effective nuclear
charge” so the electrons are held more tightly (lower in PE, or more stable)
In the same row In the same column
**I have no proof for this statement, but I sometimes think of it as the higher effective nuclear charge
(which is positive) helps push away that proton (even as it holds onto the valence electrons). The more
electronegative atoms “hold the electrons closer to the nucleus so the H+ also has to get closer to the
C N O F C N O F
nucleus and “feel” that effective nuclear charge. My statement sounds like it should be true, lol, but I have
no idea if it is! However it helps me out with the rationalizations. Also you may think about it like the bond
is becoming more and more ionic so it more easily dissociates.
P S Cl P S Cl
Chapter 3 Brønsted-Lowry Acidity:O
H H
Butane Propanol
• ARIO -‐ The type of atom that carries the charge
relative acidity
The relative of these
stability of the two compounds,
bases we must
tells us the relative firstof deprot
strength the
acidsconjugate bases:
w the
Hello⊝ ⊝
O More%stable%
Less%stable%
se conjugate bases by looking at where the negative charge is lo

base, the negative charge is on a carbon atom. In the second
an oxygen atom. To determine which of theseMORE%ACIDIC%
Less%acidic% is more stable
nts are in the same row or in the same column of the periodic
n the same row 35 In the same colu

Which is more acidic, H2O or H2S?
O S
H H Hello H H
Less$acidic$ MORE%ACIDIC%
O S
H H
Less$stable$ More%stable%
Oxygen is a smaller atom. Sulfur is a larger atom.

The charge is more concentrated Charge is spread out over a larger area
stronger base (less stable lone pair) weaker base (more stable lone pair)
36
Hello
Electronegativity Size
is more important is more important
(better at holding the electrons) (electrons are more disperse)
size is very similar so they both poor orbital overlap between
have similar orbital overlaps. the H and S or H and Cl
37
Determine which of the two protons are more acidic
H H H
N
HS
H C N
H Hello OH
O H H
H
O O N H
H H
Answers
H H H
N
HS
H C N
H Hello H
OH
O H
O-‐H. Oxygen is more N-‐H. Nitrogen is

S-‐H. Sulfur is larger
electronegaeve than more electronegaeve
than oxygen
nitrogen than carbon
H
O O N H
H H
O-‐H. Oxygen is more O-‐H. Oxygen is more

electronegaeve than carbon electronegaeve than nitrogen
• ARIO -‐ Resonance stabilizes a negative charge (i.e. lone pair) by
spreading it out across multiple atoms.
• Same idea as the size effect. The negative charge is delocalized
over a greater area. (Just like the size effect with atoms)
Hello
• Compare the acidity of the two compounds below by comparing
the stabilities of their conjugate bases.
40
O
⊝ ⊝
O O ⊝
Chapter 3 Brønsted-Lowry Acidity: O O
In both cases, the negative charge is on oxygen. Therefore, factor 1 d
ase, the charge is delocalized over both oxygen atoms. Such a negative charge will
an a• negative stable. But on
there is oxygen
a criticalatom:
difference between these two negative c
ARIO -‐ charge localized
Resonance one
has no resonance structures, while the second conjugate base does:
O
⊝
Compare the ⊝ O⊝ O
O versus& O
stability of these ⊝
Charge is localized O
Charge is delocalized O
conjugate bases Hello
(less stable) (more stable)
In this case, the charge is delocalized over both oxygen atoms. Such
this reason, compounds containing a C=O bond directly next to an OH are
stable than a negative charge localized on one oxygen atom:
idic, because their conjugate bases are resonance stabilized:
Now we know the relative O
stability of the Oacids (which +can O ⊝
⊝
O ⊝
–H O O
be confirmed by looking
H up their ⊝
R O Charge is localized
R
Charge is delocalize
O
pKa values)R O (less stable) (more stable)
A carboxylic acid
Resonance-stabilized
For this reason, compounds containing
Less&acidic&
conjugate base aMORE&ACIDIC&
C=O bond directl
mildly acidic, because their conjugate bases are resonance stabilized:
41 O O
–H+
• ARIO -‐ Resonance
O H H
Hello N
H
N N N H
H H H H
O H O
O H
H O
H H O H
• ARIO -‐ Resonance
Answers: The more acidic proton must be near a pi bond so the
resulting lone pair can delocalize. Resonance stabilization
O
Hello H N
H
N N H
N H
H H H H
O H O
O H
H O
H H O H
For both examples, both would result in resonance

stabilizaeon but the O is more electronegaeve than the C
• ARIO -‐ Induction can also stabilize a formal negative charge by
spreading it out. How is induction different from resonance?
• Electron withdrawing
Hello atoms/groups inductively withdraw electron
density from their surroundings, thus stabilizing a negative charge.
O
O
Cl
OH
OH Cl
Cl
Acetic Acid Trichloroacetic acid
less acidic more acidic

44
• ARIO -‐ Induction can also stabilize a formal negative charge by
spreading it out.
• More electron withdrawing groups = more stable conjugate base

Hello
• The closer the electron withdrawing groups to the negative
charge = more stable the conjugate base
• pKa of trifluoroacetic acid is -‐0.3

45
• ARIO -‐ Induction
O O O
Br O
OH
Hello OH OH
OH
Cl Cl Cl Br
F3C CF3 Br Br
OH OH
HO HO
F F
Answers: Look for electronegative atoms that are inductively
“pulling” electrons away from the O-‐H bond. This effectively
weakens the OH bond and makes the H+ more acidic and stabilizes
the resulting negative charge on the conjugate base.
HelloO O
O
Br O
OH OH OH
OH
Cl Cl Cl Br
Two Cl’s have a stronger

Br is closer to the OH bond
induc4ve effect than one Cl.
F3C CF3 Br Br
OH OH
HO HO
F F
This OH bond is closer to the two CF3 moie4es F is more electronega4ve than Br
Draw a constitutional isomer that is more acidic and less acidic
than the structure listed below.
Hello
O
Cl OH
Cl
Answers
O
Cl O
Hello
OH
Cl OH
Cl Cl
More acidic. Two nearby Cl’s Less acidic (by at least 10 pKa
have a greater induc4ve units). Both Cl’s are farther
affect than 1. away. Induc4ve effects are
significantly affected by
distance.
Rank the protons from most acidic to less acidic
O Cl Cl Br OH
OH
Hello OH
HO HO Cl
OH
F3C OH O
F
O OH F OH
• ARIO -‐ Induction Least acidic. Cl is less
Answers Same Acidity. These H’s
electronegaeve than
both Br or F
Most acidic. H is four are equivalent
bonds away from two F’s
Hello
O Cl Cl Br OH
OH
OH
HO
HO HO Cl
OH
O
F F
O OH F OH
Most acidic. H is the Most acidic. Closest to

Least acidic. H is five
closest to the Cl’s the most electronegaeve
bonds bonds away
element (fluorine).
from one Fluorine
H > H > H H > H = H H > H > H

• 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. Hello
• The shorter the

atomic orbital, the
closer to the
nucleus. electrons
3 sp : electrons
closest to
farthest from
nucleus
nucleus
52
• The shorter the

atomic orbital, the
closer to the
nucleus. (This Hello
answer may be
incomplete or
inaccurate)
**I honestly believe it has more to do with either hyper conjugation destabilizing the sp3 and
sp2 anions or the solvent being able to better stabilize the sp anion.
Hyperconjugation: There is simply more electron density. An sp orbital is not effected by
hyper-‐conjugation and therefore the electrons have more room to “roam” near the nucleus.
Solvent effects: For an sp anion, the entire back side of the molecule is free and more solvent
molecule can crowd around it thus better stabilizing the negative charge.
53
• 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:
Hello
• To predict which H is more acidic, we first have to draw the two
possible conjugate bases
versus
• Which carbanion is more stable?

• 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.
Hello
versus
Lone pair in a sp2 Lone pair in a sp

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

charge. The more s-‐character in the orbital, the more stable the
negative charge.
Hello
• Compare the acidity of the compounds below by comparing the
stabilities of their conjugate bases.
charge.
Hello
H H
H
Answers: Determine which conjugate base would have a lone pair in an orbital
that is closer to the nucleus.
2 3
Sp = closest to nucleus > sp > sp which is farthest from the nucleus
Least acidic. Lone pair HelloH H Most acidic. Lone pair

ends up in a sp3 ends up in a sp2
hybridized orbital which H hybridized orbital which
is farther from the is closer to the nucleus
nucleus
H
H
H
H
H
H
charge.
Identify the most acidic proton in each of the following compounds
Hello
charge.
Answers: Look at the hybridization of all the carbons containing protons. Any sp
2
hybridized carbons will have the most acidic protons followed by the sp hybridized
3
carbons. The hydrogens on the sp hybridized carbons will be the least acidic.
Hello
H
H
H H
Most acidic hydrogen.

Most acidic hydrogen
Most acidic hydrogen’s
charge.
What happens when you mix these two molecule together?
Hello
H H H H
+ H C C C C Li
H H H H
n-‐butyllithium
(n-‐BuLi)
charge.
The lone pair will find a way to become stabilized (higher energy to lower
energy). In this case the lone pair would rather be on an sp hybridized
carbon (vs the original s p
Hello
3 carbon) since the electrons will be closer to the
nucleus.
H Li
H H H H
+ H C C C C Li +
H H H H
• 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

Hello
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 (It is chemistry, there are always exceptions!)
• Ethanol is more acidic than propylene. Therefore, the conjugate base of
ethanol must be more stable.
Hello
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.
• 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
Hello
• 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.
• When assessing the acidity of protons, we generally use ARIO as the order of
importance of these stabilizing effects.
Identify the most acidic proton in each of the following compounds. Red vs Blue
OH O O O
H NH2
HO
Hello H H N
N O
H
N N
SH
H HO
H
H S
O H
HO N O
N
OH
O S O
H H
O H
Hydrogen on oxygen is more acidic Greater resonance stabiliza4on. O and is more
Answersthan a hydrogen on a carbon. Also The nega4ve is spread over 1 C and electronega4ve than
resonance stabiliza4on of the anion. 2 O’s instead of just 1 C and 1 O. N. Nega4ve is spread
over 2 O atoms instead
of 2 N atoms.
OH O O O
H NH2
HO
H H N
Nega4ve charge will spread out Hello

The nega4ve charge will spread S is larger than O.
over the carbon and nitrogen out over two nitrogen atoms Nega4ve charge spread
atoms. Resonance stabilized. instead of two carbon atoms. across the two S’s
instead of the two O’s.
N O
H
N N
SH
H HO
H
H S
The nega4ve is resonance The nega4ve is resonance

Excep4on! sp orbital on a carbon stabilized over 2 O atoms
is bemer at stabilizing a nega4ve stabilized over 3 O atoms instead
instead of 3 C atoms. of one C atom and one O atom.
charge than a nitrogen atom is.
O H
HO N O
N
OH
O S O
H H
O H
Identify the most acidic proton in Amphotericn B, a powerful antifungal drug used
to treat severe fungal infections.
OH
OH
O OH
HO O HelloOH
OH OH OH O O
OH
OH
O NH2
Amphotericn B
O
OH
Answer: The most acidic hydrogen is from the carboxylic acid moiety (COOH).
Carboxylic acids are often the most acidic functional groups since the anion is
resonance stabilized over two electronegative oxygen atoms.
OH
OH
O Hello OH
HO O OH OH OH OH O O
OH
OH
Amphotericn B O NH2
O
OH
What happens when you mix the following pairs of molecule together?
O Li
N
Hello
O
Li
Li H
O
Li H H
Answers O Li
H
O Li N
+
H N
The nega4ve would prefer to be resonance stabilized between the C and O than on the N
O
Hello O Li
H
Li +
The nega4ve would prefer to be resonance stabilized between the C and O than on just a C.
Li
Li H
N
N +
The nega4ve would prefer to be on the more electronega4ve nitrogen and not on the carbon.
+ O
O H
Li H H
The nega4ve would prefer to be on the more electronega4ve oxygen and not on the carbon.
What happens when you mix the following pairs of molecule together?
O N
H
Hello
O
O
H
pKa = 19.2 pKa of water = 15.7
O O
O
H

Answers
H
NO CHANGE! The nega4ve charge
O N would rather be on the more
H electronega4ve oxygen atom and
not on the less electronega4ve
nitrogen atom
Hello NO CHANGE! It seems like having the
O nega4ve spread over a C and an O
O would be bemer however, the pKa
H values tell us that water is a stronger
acid than acetone. HO-‐ is therefore a
pKa = 19.2 pKa of water = 15.7 weaker conjugate base and can NOT
deprotonate the hydrogen on the
carbon in acetone.
O O
O O
O
O
H H
H
H H H

In this case water is a weaker acid so its conjugate base is strong enough to deprotonate the hydrogen.
Now there is even more resonance stabiliza4on. The nega4ve is spread between 1 C and 2 O’s.
Chapter 3 Predicting Equilibrium Position
• Consider any acid base reaction:
• This equilibrium represents

Hello the competition between two bases
(A− and B−) for the H+.
• 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)
• Quantitative method by looking at a pKa table
2. The relative stability of the bases, B− and A−
• Qualitative method by using chemistry logic and ARIO.
Choosing a Reagent
• Another important skill is to be able to choose an appropriate
reagent for a acid/base reaction
Hello
• Choose an acid from Table 3.1 that could effectively protonate
each of the following molecules
O O
O
75
Hello
O O
O
Choosing a Reagent
Any acid with a pKa Any acid with a pKa
below 25 below 19.2
O
Hello
O O
O
Any acid with a pKa Any acid with a pKa
below 4.75 below −7.3
77
Predict the position of equilibrium for the following reactions.
O S O S
+ +
N
H
N ? N N
H
Hello
+ NH3 +
? NH2
OH O
+ + H2O
HO ?
78
Answers: Always strong to weak, make sure you know WHY!!!
O S O S
H + + H
N N N N
pKa = 15 (weaker acid) weaker base stronger base pKa = 13 (stronger acid)
Both cases are resonance stabilized but on the leo, the negaeve is on an N and S. On the right it is on an N
and O. The sulfur is much larger than the oxygen and is beper at spreading out the negaeve charge.
Hello than electronegaevity effects. Equilibrium lies to the leO.
Remember size effects is more important
+ NH3 + NH2
stronger base pKa = 38 (stronger acid) pKa ≈ 50 (weaker acid) weaker base
Carbon and nitrogen are in the same row (and have the same number of shells) so size effects are
negligible. The negaeve charge is more stabilized on the most electronegaeve atom (since these valence
electrons feel the greatest effeceve nuclear charge from the nucleus). Equilibrium lies to the right.
OH O
+ HO + H2O
pKa = 9.9 (stronger acid) stronger base weaker base pKa = 15.7 (weaker acid)
On the leo, the negaeve charge is just on an oxygen atom. On the right, the negaeve charge is resonance
stabilized. It is spread out over one oxygen atom and 3 carbon atoms. Equilibrium lies to the right.
The development of chemical sensors to detect harmful contaminants is a prevalent line
of research. Compound 1 below was explored as a possible sensor for the toxic cyanide
ion. Since compound 1 is not fluorescent and compound 3 is, this could prove to be a
usefully to detect the cyanide ion while out in the field.
a. Draw curved arrows showing the attack of the cyanide ion onto compound 1 to form
compound 2 through the formation of a new covalent C-‐C bond. Also, used curved
Hello proton transfer that converts 2 into 3.
arrows to show the intramolecular
b. Predict whether the equilibrium will favor compound 1, compound 2, or compound 3.
C N H N H N
O H
O C HO C
HO O O
HO O O O O O
1 2 3
80
Answers: Always weak (acids and bases) to strong (acids and bases), make sure
you know WHY!!!
C N H N H N
O H
O C HO C
H
HO O O
Hello O O O O O O
1 2 3
When comparing the difference between structures When comparing the difference between structures
1 and 2, the negaeve charge would rather be on the 2 and 3, structure 2 is not resonance stabilized and
more electronegaeve oxygen atom than on the less the negaeve charge is localized on one oxygen atom.
electronegaeve carbon atom. Structure 3 is resonance stabilized. The negaeve
Equilibrium lies to the right. charge is spread out over two different oxygen atoms
and 4 different carbon atoms. Structure 3 is the
most stable of the three structures. (Draw all the
resonance structures if you can!)
Equilibrium lies to the right.
81
For each of the following cases, identify whether the reagent shown is suitable to
accomplish the task described. Explain why or why not using quantitative analysis
(comparing pKa’s) and qualitative analysis (chemistry logic).
O O
N
a. To protonate using H2O d. To protonate using H2O
Hello
H
N
b. To protonate using e. To protonate using H2O
H H
c. To deprotonate C C using NH2 f. To deprotonate H C C H using NH2
H H
Yes, suitable reagent H
N H N
a. + O +
HO
H
stronger base pKa = 15.5 (stronger acid) pKa ≈ 38 (weaker acid) weaker base
The negaeve charge would rather be on the more electronegaeve atom, oxygen. Size affects don't maper
since they are both in the same shell. The stronger effeceve nuclear charge on oxygen holds the electrons
Hello
closer to the nucleus and stabilizes the charge.
H Yes, suitable reagent
N N
b. + +
stronger base pKa ≈ 38 (stronger acid) pKa ≈ 50 (weaker acid) weaker base
The negaeve charge would rather be on the more electronegaeve atom, nitrogen. Size affects don't maper
since they are both in the same shell. The stronger effeceve nuclear charge on nitrogen holds the electrons
No, not suitable reagent

H H H
c. C C +
NH2 C C + NH3
H H H H
pKa ≈ 44 (weaker acid) weaker base stronger base pKa = 38 (stronger acid)
The negaeve charge would rather be on the more electronegaeve atom, nitrogen. Even though the carbon is sp2 hybridized,
the NH3 is sell a stronger acid. The only case you have to memorize is that a hydrogen apached to an sp hybridized carbon is
more acidic than NH3.
O O H No, not suitable reagent O O
d. + O +
HO
H
weaker base pKa = 15.7 (weaker acid) pKa = 9.0 (stronger acid) stronger base
The negaeve charge on the leo is resonance stabilized and located on one carbon atom and two oxygen
atoms. This delocalizaeon is more stabilizing than if the negaeve charge was located on the oxygen alone (in
the hydroxide ion) Hello
Yes, suitable reagent
H
O
e. + +
HO
H
stronger base pKa = 15.7 (stronger acid) pKa ≈ 50 (weaker acid) weaker base
The negaeve charge would rather be on the more electronegaeve atom, oxygen. Size affects don't maper
since they are both in the same shell. The stronger effeceve nuclear charge on oxygen holds the electrons
Yes, suitable reagent
f. H C C H + H C C + NH3
NH2
pKa = 25 (stronger acid) stronger base weaker base pKa = 38 (weaker acid)
You will just need to memorize that a hydrogen on an sp hybridized carbon is more acidic than a hydrogen
located on a nitrogen.
You will learn about the following reactions in the chapters to come. Often times, the
products are anions and need to be protonated before you can isolate them. We call
this “working up the reaction”. Will water be a suitable proton source to protonate
these anionic products.
Hello
O
NaOH
O
a.
O ONa
Cl ONa
NaOH
b.
Heat
Answers: Compare the pKa’s of the two possible acids then determine
if protonation is possible.
O O O
NaOH O
a. H H
O Hello ONa OH
stronger base than OH−, pKa = 4.75 pKa = 15.7
protona4on will not occur (stronger acid) (weaker acid)
Cl ONa OH
NaOH O
b. Heat H H
stronger base than OH−,

pKa = 9.9 pKa = 15.7
protona4on will not occur
(stronger acid) (weaker acid)
Water will not protonate any of these anionic products. It’s pKa is too high.
Chapter 3 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 Hello
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. WHY? – see
next few slides
– Bases stronger than OH− can not be used in water. WHY? – see
next few slides
Appropriate use for water as a solvent: When the base is not
stronger than hydroxide, equilibrium lies to the left.
Hello
pKa = 15.7 pKa= 4.75

(weaker base) (weaker acid) (stronger acid) (stronger base)
• 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
– 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.
Hello
– Even though you add H2SO4, the strongest acid available is
now H3O+ with a pKa of −1.7.
– Bases stronger than OH– also can not be used in water.
O H H O
+ O + O
H
Hello
pKa = 15.7 pKa = 19.2
(stronger base) (weaker base)
(stronger acid) (weaker acid)
– The strongest base that will exist in solution is OH–. Any base
whose conjugate acid has a pKa greater than 15.7 will not exist in
solution. It instead will deprotonate water.
Water can not be used as a solvent in this reaction. Which of the
following solvents would be a better choice?
H
+ N + N
H
Hello
pKa = 40
pKa = 25
O O
O
OH H H
OH
Ethanol Hexane Tetrahydrofuran (THF) Acetic Acid Water
pKa = 16 pKa = 50 pKa around 48 pKa = 4.75 pKa = 15.7

Answers: Any acid with a pKa lower than 40 will be deprotonated by the nitrogen
anion. Similarly, any acid with a pKa lower than 25 will be deprotonated by the
product (the carbon anion)
H
+ N + N
H
Hello
pKa = 40
pKa = 25
O O
O
OH H H
OH
Ethanol Hexane Tetrahydrofuran (THF) Acetic Acid Water
pKa = 16 pKa = 50 pKa around 48 pKa = 4.75 pKa = 15.7
bad solvent Good solvent! Good solvent! bad solvent bad solvent
will be Can Not be Can Not be will be will be
deprotonanted deprotonated deprotonated deprotonanted deprotonanted
Any acid that has a pKa less than −1.74 will protonate
water.
The strongest acid possible in water is the H3O+ ion. If it is
any stronger than that, it will react with water to make
more H3O+.
H3O+
Hello
OH−
Any base who’s conjugate acid has a pKa

higher than 15.7 will deprotonate water.
The strongest base possible in water is the
hydroxide ion. Any stronger bases will
deprotonate water to make more OH−.
Chapter 3 Solvating Effects
• Because they are so similar, ARIO can not be used to explain the
pKa difference comparing ethanol and tert-‐Butanol
Hello
• 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
• 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.
Hello That is why t-‐butanol is not as acidic as
ethanol
Fun fact:
• The acidity of alcohols is reversed in gas phase. tert-‐Butoxide is
the most acidic, followed by ethanol, followed by methanol, with
water being the least acidic. Basically, think MO theory, t-‐butoxide
is more polarizable (its a large molecule) so the negative charge is
more spread out.
Hello Don't forget, molecular orbitals encompass the
entire molecule.
• Also, the pKa’s can change drastically based on the solvent used in
the reaction.
GP =
Chapter 3 Solvating Effects gas
phase
Hello
http://dx.doi.org/10.1002/poc.2946 f
Chapter 3 Counter Ions
• Counterions are also known as spectator ions.

• They are always present, because they are required in order to
balance the overall charge of a solution
Hello
• Full reaction. with counterion(s) included:
• We often do not include the counter ions when writing the rxn:
Chapter 3 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
Hello 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
• 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
Hello
Brønsted-‐Lowry definition
• Explain how this reaction fits the Lewis definition but not the
Brønsted-‐Lowry definition
Identify the Lewis acid and the Lewis base. H
H
H
B
H H O O
B +
H
Cl
Hello Cl Al
Cl
O O Cl
+
Al
Cl Cl
H H
O
O O
+ +
O H H
H H
Br Br
+ Br Br Br Al Br Br
Al
Br Br Br
H
Answers: Identify the electron donors and acceptors H H
B
H H O O
B +
H
Acid = electron acceptor Base = electron donor
Cl
Hello Cl Al
Cl
O O Cl
+
Al
Cl Cl
Base = electron donor Acid = electron acceptor
H H
O
O O
+ +
O H H
H H
Base = electron donor Acid = electron acceptor
Br Br
+ Br Br Br Al Br Br
Al
Br Br Br
Acid = electron acceptor Base = electron donor

Introduction to Acids and Bases

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Introduction to Acids and Bases

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Chapter 3: Acids and Bases

• 95% of the reaction covered in organic chemistry are ionic reactions.

… here, the curved arrows are actually describing the physical

• The base “attacks” the acid, using a pair of electrons.

step 1 step 2 step 3

Base Acid Conjugate Acid Conjugate Base

• Recall from General Chemistry, how do “strong” acids/bases differ

• The strength of an Hello

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

– We will learn to do Qualitative strength analysis – comparing

• Ka values range from

• Each pKa unit represents an order

• For example, H2SO4 (pKa = −9) is

… The stronger an

• For an acid: The lower the pKa = more acidic.

• The higher the pKa:

Always Strong(er) ⟶ Weak(er)

• To determine the stability of a conjugate base, we are actually

• The more effectively a conjugate base can stabilize its negative

• Four main factors

– The type of atom that carries the charge

s the relative acidity of these two compounds, we must first deproto

e these conjugate bases by looking at where the negative charge is loc

se conjugate bases by looking at where the negative charge is lo

n the same row 35 In the same colu

Oxygen is a smaller atom. Sulfur is a larger atom.

O-­‐H. Oxygen is more N-­‐H. Nitrogen is

O-­‐H. Oxygen is more O-­‐H. Oxygen is more

For both examples, both would result in resonance

Acetic Acid Trichloroacetic acid

less acidic more acidic

• More electron withdrawing groups = more stable conjugate base

• pKa of trifluoroacetic acid is -­‐0.3

Two Cl’s have a stronger

Most acidic. H is the Most acidic. Closest to

H > H > H H > H = H H > H > H

• The shorter the

• The shorter the

• Which carbanion is more stable?

Lone pair in a sp2 Lone pair in a sp

less acidic MORE ACIDIC

Least acidic. Lone pair HelloH H Most acidic. Lone pair

Most acidic hydrogen.

1. The type of atom that carries the charge

Nega4ve charge will spread out Hello

The nega4ve is resonance The nega4ve is resonance

pKa = 19.2 pKa of water = 15.7

pKa = 9.0 pKa of water = 15.7

pKa = 9.0 pKa of water = 15.7

• Consider any acid base reaction:

• This equilibrium represents

No, not suitable reagent

Yes, suitable reagent

stronger base than OH−,

pKa = 15.7 pKa= 4.75

Ethanol Hexane Tetrahydrofuran (THF) Acetic Acid Water

pKa = 16 pKa = 50 pKa around 48 pKa = 4.75 pKa = 15.7

Ethanol Hexane Tetrahydrofuran (THF) Acetic Acid Water

pKa = 16 pKa = 50 pKa around 48 pKa = 4.75 pKa = 15.7

Any base who’s conjugate acid has a pKa

• Counterions are also known as spectator ions.

• Lewis acid/base definition

O-‐H. Oxygen is more N-‐H. Nitrogen is

O-‐H. Oxygen is more O-‐H. Oxygen is more

• pKa of trifluoroacetic acid is -‐0.3