Reactions and their Mechanisms

-Cl on -CH3 has

Substitution been substituted
with an -OH

Br2 has been

Additions added to C2H2

HBr has been eliminated

or removed form C2H5Br
Eliminations

The carbon skeletal

system, C6H12, has been
Rearrangements
rearranged

Sec. 7 - Acid-base Reactions Forsey 1

 Homolysis and Heterolysis of Covalent Bonds
Heterolysis – Cleavage of sigma bond occurs so that
one fragment take away both electrons

Double headed arrow

shows the movement
of two electrons

Homolysis – Cleavage of sigma bond occurs so that each

fragment takes away one electron.

Single headed arrow

shows the movement
of one electrons

Sec. 7 - Acid-base Reactions Forsey 2

 Arrows are your thought process to solving reactions
(-ve goes to +ve)

Double headed arrow

shows the movement
of two electrons

Heterolysis requires that the bond be polarized which is due to the different
electronegativities between the atoms

Double headed
arrow shows the
movement of two
electrons

Often heterolysis is assisted by a molecule with an unshared pair of electrons

(a base) that can form a bond to on to the atoms. (-ve goes to +ve)

Sec. 7 - Acid-base Reactions Forsey 3

 Acid-Base Reactions

Bronsted-Lowry acid → substance that can donate a hydrogen ion (H+)

Bronsted-Lowry base → substance that can accept a hydrogen ion (H+)

CH3COOH + ¯OH CH3COO ¯ + H2O

acid baseconjugate base conjugate acid

Lewis acid → substance that can accept a pair of electrons

Lewis base → substance that can donate a pair of electrons

FeBr3 + Br2 FeBr4 ¯ + Br +

Lewis acid Lewis base Lewis base Lewis acid

Sec. 7 - Acid-base Reactions Forsey 4

 pH = -log[H+]
Review pOH = -log[OH]
kw = [H+][¯OH] = 1 x 10-14
Brønsted-Lowry pH + pOH = 14
acids and bases neutral solution → [H+] = [ ¯OH] = 1 x 10-7 pH = 7
acidic solution → [H+] > 1 x 10-7 pH range 0 to 7
basic solution → [H+] < 1 x 10-7 pH range 7 to 14

General formula for an acid HA; for a base B

HA H+ + A¯ B + H2O B+H + ¯OH
ka = [H+][A¯] kb = [¯OH][B+H]
[HA] [B]
taking the log of both sides
Henderson-Hasselbalch equations
pH = pka + log[A¯] pOH = pkb + log[B+H]
[HA] [B]
strong acid [H+] ↑ , ka ↑, pka ↓ strong base [¯OH] ↑ , kb ↑, pkb ↓
weak acid [H+] ↓ , ka ↓, pka ↑ weak base [¯OH] ↓ , kb ↓, pkb ↑
relationship between conjugate acid base pairs
ka x kb = kw =1 x 10-14
pka + pkb = 14

Sec. 7 - Acid-base Reactions Forsey 5

 Lewis Acids and Bases
Makes you think about the electrons and how bonds are formed

arrow show bond breaking

arrow show bond formation

gained two electrons

and becomes new bond
negatively charged

Sec. 7 - Acid-base Reactions Forsey 6

 Opposite Charges Attract and React

BF3 has substantial positive charge on the boron

NH3 has substantial negative charge localized at the lone pair

-ve goes to +ve

Sec. 7 - Acid-base Reactions Forsey 7

 The base donates its electrons that occupy the HOMO to the
LUMO of the acid to produce a new sigma bond

NH3 is sp3 hybridized.

BF3 is sp2 hybridized The HOMO (Highest
The LUMO (Lowest Occupied Molecular
Unoccupied Molecular Orbital) is shown to
Orbital) is shown to the the left and is where
right. Most of the the nonbonding lone
volume of the LUMO pair resides.
corresponds to the
empty p orbital

The van der Waals surface electron density is indicated by the mesh

Sec. 7 - Acid-base Reactions Forsey 8

Heterolysis of Bonds to Carbons: Carbanions and Carbocations

Reaction can occur to give a carbocation or carbanion depending on the nature of Z

Carbocations have only 6 valence electrons and a positive charge

Sec. 7 - Acid-base Reactions Forsey 9

Carbanions have 8 valence electrons and a negative charge

Organic chemistry terms for Lewis acids and bases

Electrophiles (“electron-loving” reagents ): seek electrons to obtain

a stable valence shell of electrons.
They are electron-deficient themselves e.g. carbocations.
Acid – accepts electrons
Nucleophiles (“nucleus-loving” reagents): seek a proton or some
other positively charged center.
They are electron-rich themselves e.g. carbanions
Base – donates electrons

Sec. 7 - Acid-base Reactions Forsey 10

A mechanisms shows the flow of
electrons that may occur to form
your product. The pathway is guided
by arrows. An arrow starts at a site
of higher electron density (a covalent
bond or unshared electron pair) and
points to a site of electron
deficiency.

In a few weeks you will have to

know and understand the
mechanism given to the right.
This is a SN1 reaction.

Sec. 7 - Acid-base Reactions Forsey 11

The first step to organic reactions is understanding acids and bases

Why do acids have different acidities? What makes a strong acid a

strong acid? An acid is strong if it’s conjugate base is stable. If the
base is not stable it is reactive and will react with a proton and shift
the equilibrium to the left in the following equilibrium.

HA A¯ + H+

Acidity increases with increasing anion stability

Hence the strength of an acid is inversely related to the strength of its

conjugate base. What makes the base stable? You must look at the
structure of the molecule. What is the hybridization of the atom? Is the
charge on an electronegative atom? Is the electronegative atom large so
that the charge is spread over a larger area? Can the charge be
delocalized throughout the molecule? All of these must be considered

Sec. 7 - Acid-base Reactions Forsey 12

1. What atom is the charge on?
Acidity increases with increasing anion stability HA A¯ + H+
The more electronegative an atom, the greater its ability to carry a negative
charge. Remember, electronegativity is the measure of an elements affinity for
an electron or its ability to accept an electron.
(CH3)3C-H (CH3)2N-H CH3O-H H-F

increasing electronegativity of the underlined atom;

increasing acid strength
increasing stability of anion

B C N O F
2.0 2.5 3.0 3.5 4.0
Al Si P S Cl
1.5 1.8 2.1 2.5 3.0
Ga Ge As Se Br
1.8 2.0 2.2 2.6 2.8
Te I
2.1 2.5

Sec. 7 - Acid-base Reactions Forsey 13

 1. What atom is the charge on? HA A¯ + H+
A larger anion can disperse the negative charge over a larger volume and thus
increases the stability of the conjugate base which is more important than
electronegativity when comparing elements down a column in the periodic
table.
H-F H-Cl H-Br H-I
conjugate
base
increasing size of halogen increasing acid strength
increasing stability of anion
decreasing electronegativity of halogen
B C N O F
2.0 2.5 3.0 3.5 4.0
Al Si P S Cl
1.5 1.8 2.1 2.5 3.0
Ga Ge As Se Br
1.8 2.0 2.2 2.6 2.8
Te I
2.1 2.5

Thus use electronegativity when comparing atoms in the same

row and size when comparing atoms in the same column
Sec. 7 - Acid-base Reactions Forsey 14
2. The proximity of an electronegative atom to an acidic atom can
help stabilize the conjugate base. (Induction)
HA A¯ + H+
Inductive effects: Electronegative atoms pull electron density through the sigma
bond from adjacent carbons making the carbon more positive. If the carbon is close
to the anion this carbon can then pull electron density from the region that has the
negative charge to make it more stable.
CH3CH2CH2COOH CH2ClCH2CH2COOH CH3CHClCH2COOH CH3CH2CHClCOOH

pka 4.83 4.52 4.05 2.86

increasing acidity
increasing anion stability

H3COH ClCH2CH2OH F3CCH2OH

pka 15.5 14.3 12.4

increasing acidity
increasing anion stability

Sec. 7 - Acid-base Reactions Forsey 15

 -½
δ− Cl O δ- Cl
δ+ δ+
δ- Cl
O -1
δ+
δ− Cl
Cl O -½ Cl
δ− δ-
The chlorines make the adjacent carbons electron poor. The carbon
can then pull electron density from the region that has the negative
charge, and this effect will stabilize the negative charge

How about these hydrogens This is destabilizing. The lone pairs on

Do the electronegative atoms the electronegative atom and the lone
help stabilize the conjugate base pair on the carbon repel each other.

O δ− O
+ H+

These protons are H

not very acidic F δ−
F
+ H+

H
Sec. 7 - Acid-base Reactions Forsey 16
 What effect do alkyl groups
Which compound is more acidic?
H3C O
H3C O
C C + H+
C C
H 3C O
H3C OH CH3
CH3

O O + H+
more acidic C C
H3C OH H3C O
more stable conjugate base

Alkyl and aryl groups are hyperconjugation H O sp2

electron donating through through C-H sigma
hyperconjugation or inductive bond. This is not sp3 C C sp 2

resonance. We will
effects which makes the
talk more about H
anion less stable. H O sp2
this later.
only one C-H σ
bond shown Resonance
Sec. 7 - Acid-base Reactions Forsey 17
3. Resonance Stabilization
Resonance helps stabilize the negative charge by delocalizing or sharing the negative
charge with more than one atom. For example which is more acidic methanol or acetic
acid? In methanol the charge on the conjugate base is localized on a single oxygen
whereas the conjugate base of acetic acid has the charge shared or delocalized over
two oxygens. The conjugate base of acetic acid is more stable thus the equilibrium is
shifted more to the right as compared to methanol making acetic acid more acidic.
But which is more acidic acetic acid or phenol

pka = 15.5 CH3OH CH3O ¯ + H+ No resonance

two resonance
O O structures helps
pka = 4.74 stabilize the negative
H3C C OH H3C C O ¯ + H+
charge and shifts the
equilibrium to the right
compared to CH3OH

Less acidic than acetic acid?

But doesn’t the phenoxide
pka = 9.92 OH O ¯ + H+ have more resonance
structure and should be more
stable than acetate ion
Sec. 7 - Acid-base Reactions Forsey 18
 CH3O ¯ + H+

O O O
O

+ H+

O O
+ H+
H3C C O H3C C O

Phenol has more resonance structures than acetic acid but acetic acid is more acidic, why?
Which atom is able to handle a negative charge better, carbon or oxygen?

Sec. 7 - Acid-base Reactions Forsey 19

 4. Hybridization
With increasing s character the lone pair of electrons are closer
to the nucleus thus stabilizing the conjugate base
(CH3)3CH CH2=CH2 HC≡CH

pka > 70 44 26

increasing acidity
increasing anion stability

Conjugate (CH3)3C¯ CH2=CH ¯ HC≡C ¯

base sp3 sp2 sp

C¯ C¯ C¯
sp3 sp2 sp

Sec. 7 - Acid-base Reactions Forsey 20

List the following compounds in order of decreasing acidity

CH4, NH3, CH3OH, HF B C N O F

2.0 2.5 3.0 3.5 4.0

Al Si P S Cl
¯
CH3 ¯
NH2 CH3O¯ F¯ 1.5 1.8 2.1 2.5 3.0

+ H+ + H+ + H+ + H+ Ga Ge As Se Br
1.8 2.0 2.2 2.6 2.8

Te I
2.1 2.5

Sec. 7 - Acid-base Reactions Forsey 21

 List the following compounds in order of decreasing acidity

a) HCl HBr HF HI
B C N O F
2.0 2.5 3.0 3.5 4.0
Al Si P S Cl
1.5 1.8 2.1 2.5 3.0
b) CH3CH3 H2C=CH2 HC≡CH Ga Ge As Se Br
1.8 2.0 2.2 2.6 2.8
Conjugate base: CH3CH2 ¯ H2C=CH ¯ HC≡C ¯ Te I
2.1 2.5
sp3 sp2 sp

OH OH
c) OH

> >

Two resonance structures with the negative charge on two electronegative atoms
(oxygen) is more stabilizing than 3 resonance structures with the negative charge on
carbons.

Sec. 7 - Acid-base Reactions Forsey 22

 O
O Cl O B C N O F
2.0 2.5 3.0 3.5 4.0
2) OH 3)
d) 1) OH OH Al Si P S Cl
Cl 1.5 1.8 2.1 2.5 3.0
Ga Ge As Se Br
1.8 2.0 2.2 2.6 2.8
Te I
2.1 2.5

e) 1) Cl OH 2) OH 3) CH3SH 4) CH3OH

Cl O

The electronegative chlorine is electron

withdrawing and pulls electron density from
the oxygen into the aromatic ring making the
conjugate base more

Sec. 7 - Acid-base Reactions Forsey 23

 Bases
The concept of base strength can sometimes be confusing to students. When
there is a negative charge on different atoms it is straightforward since we can
look at the electronegativity or hybridization of the atom to explain basicity.
For example place the following molecules in decreasing basicity.

a) CH3O¯, CH3NH¯, CH3CH2¯, F¯

b) I¯ , F¯ , Cl¯ , Br¯

c) CH2=CH¯ , CH3CH2¯ , HCC¯

Where does CH3NH¯ fit into the trend found in part c)

The sp3 nitrogen is a weaker base than an sp2

carbon because it is more electronegative. It is
also a weaker base than a sp2 carbon but not a
sp hybridized carbon because the change in
hybridization which gives the orbital more s
character has a greater stabilizing effect than
increasing electronegativity.
Sec. 7 - Acid-base Reactions Forsey 24
 Reactions from text Book

pKa+ pKb = 14
pKb = -24 pKb = -1.7

pKb = -24 pKb = -11

pKb = -24

Sec. 7 - Acid-base Reactions Forsey 25

Order the bases from strongest to weakest.
NH2 A) 1>2>3
H B) 1>3>2
N N
C) 3>2>1
D) 2>3>1

1 2 3 First put the electrons

H δ+ H on the nitrogen atoms
N
N Then think about the
N
H δ- δ- electrons. What is their
hybridization, are they
resonating?
δ-

Which electrons are most basic or available?

The sp3 nitrogen because it has more p character. Therefore 1 is the strongest base.

Now which electrons are more available? The electrons in structure 2 or 3?

What is the difference?

The electrons on the nitrogen in compound 3 are part of an aromatic system and are
thus very stable, whereas the electrons in compound 2 are in a sp2 hybridized orbital
sticking out from the aromatic system. The electrons in compound B are more basic,
less stable, more reactive and more available than 3. Answer: A
Sec. 7 - Acid-base Reactions Forsey 26
 We are always looking at an equilibrium and which way it is
shifted in a specific environment
HA A¯ + H+
∆G  = −RT ln K eq

∆G° = -ve value the reaction

favors the formation of products
and if smaller than – 13 kJ mol-1
the is said to go to completion
(>99% converted)
∆G° = +ve value the reaction
favors the reactants and the
formation of products is
unfavorable.

∆G° = ∆H° - T∆S°

Exothermic reaction ∆H ° is -ve

Endothermic reaction ∆H ° is +ve

∆S° is +ve - Change from a more ordered system to less a ordered system We will come back
to this when we
∆S° is -ve - Change from a less ordered system to a more ordered system look at reactions

Sec. 7 - Acid-base Reactions Forsey 27