CHAPTER 1

Structure Determines Properties

Sections 1.6, 1.10 – 1.15

CHAPTER 1.6
Structural Formulas of Organic Molecules
 WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 3

REVIEW & BEYOND: Representation of structure

• Lewis structures: include all valence electrons
bonding e-s: as pair of dots OR as a line
nonbonding e-s: as a pair of dots (lone pairs)

Full dot
structures

Nitric acid Carbonate Ion

Formic acid Formaldehyde Nitrogen

Simplified
structures

On Board…
WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 4

Important points to remember:

[Link] total # of valence electrons.
[Link] atoms of highest bonding capacity (lowest e neg.) in the
center and proceed outwards to lower atoms with lower bonding
capacity.
[Link] total # of needed electrons.
[Link] difference between left and needed  # π bonds.

• 1st row elements: MUST obey duet rule

• 2nd row elements: MUST obey octet rule
• 3rd row & below: can exceed octet

Formal charge =
# valence e-s – [# lone pair e-s + ½(# bonding e-s)]
 WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 5

Common Bond Numbers:

atoms with zero formal charge
one bond H F Cl Br I

two bonds O

three bonds N

four bonds C

How many lone pairs should each of these atoms have?

WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 6

Representation of Molecules:
Structural Formulas

Ball and Stick Formula Dot Formula Dash Formula

H H H H
C C HOCH2CH2CH3 HO
HO C H
H H Condensed Formula Bond-Line Formula
3-D Formula
Molecular formulas of propyl alcohol
All represent the same molecule!
 WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 7

Formula Representations
1. Kekulé structures (dash formula)
• All atoms and all bonds shown but not lone pairs
Example: 2-methylpropane

2. Condensed structures: formulas that show connectivity

• Atoms are shown but bonds are implied
CH3 CH (CH3)2
 WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 8

Formula Representations
3. Bond-line Formula
• Carbons and Hydrogens not shown
• Each vertex represents a C,
fill in Hs as needed (implied)
• Heteroatoms are always shown

4. 3-Dimensional representations
• (in plane)
• (into plane)
• (out of plane)
WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 9

• Kekulé structures: show all bonds but not lone pairs

• Condensed structures: formulas that show connectivity

Kekulé structure Condensed structures

 WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 10

Kekulé structure Condensed structures

Two or more identical groups considered bonded to the first atom on the left can be shown
(in parentheses) to the left of that atom, or hanging from the atom.
H H H H
H C N C C C H (CH3)2NCH2CH2CH3 or CH3NCH2CH2CH3
H H H H
H C H
CH3
H
An oxygen doubly bonded to a carbon can be shown hanging off the carbon or to the right of the carbon.
H O H H H O or CH3COCH2CH2CH3
H C C C C C H CH3CCH2CH2CH3 or CH3C(=O)CH2CH2CH3
H H H H

O H H H
H C C C C H
H H
H C H

H H O H

H C C C O H
H H
WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 11

Practice:
Redraw each of the following as dash formulas
a) c) (CH3)3CCH(Br)CH(CH2CH3)CH3

b)
WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 12

Practice:
Write a condensed structure (structural formula) for this:

Red = O
Grey = C
White = H
WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 13

Extra Practice:
Write a Bond-Line formula for this:
WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 14

Rules for drawing skeletal / line structures

Line structures provide feeling for molecule’s shape:

1. Bonds & angles shown:

chains = zigzags, rings = polygons
2. C & H atoms not shown:
vertices = C atoms, missing bonds = Hs
3. H-atoms bonded to heteroatoms always shown:
NH, OH, etc
•Lone pairs on heteroatoms optional but helpful
4. Formal charges are ALWAYS shown:
if not zero…
 WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 15

Rules for drawing skeletal / line structures

A full Lewis H
H
Its pure skeletal (line) structure:
structure: C C C H
H
H C C
H H
C C
H
H C H
H H

Two condensed representations: Hc Hd

H3C
CH3CH2CH2CHCHCH2CCH
Ha
CH3CH2CH2CH=CHCH2C≡CH A mixed-style
Hb
structure
WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 16

Constitution
• The order in which the atoms of a molecule are connected
is called its constitution or connectivity.

• The constitution of a molecule must be determined

(typically by experiment) in order to write a Lewis
structure.

• Usually C has 4 bonds, N has 3 bonds and O has 2

bonds.
 WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 17

Isomers
• Isomers = different molecules with same molecular formula
• Constitutional isomers: same molecular formula, different connectivity
(different atoms connected to each other)

Common motifs:
C4H10
(n-butane)

C5H12
(n-pentane)

For chains of ≥ 4 carbons: branched isomers also possible

WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 18

Other Examples of Constitutional Isomers

• Both compounds have the molecular formula CH3NO2

but the atoms are connected in a different order.
 WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 19

Practice:
Drawing isomers: start with straight chain, then try branches
Try C7H16:

7C:

6C:

5C:

4C:
SECTION 14.25
Molecular Formula as a Clue to Structure

***(skipping ahead)
WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 21

Molecular Formula

• One of the first pieces of information we try to obtain

when determining a molecular structure is the
molecular formula.

• Knowing the molecular formula helps reduce the

number of options for potential structures of an
unknown chemical species.
Alkane: single bonds CnH2n+2
Alkene: double bonds CnH2n
Alkyne: triple bonds CnH2n-2
Cyclo: ring CnH2n
WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 22

Molecular Formulas

• A substance with a molecular formula of C7H16 tells us

immediately that it is an alkane because it
corresponds to CnH2n+2.

• C7H14 lacks two hydrogens of an alkane, therefore

contains either a ring or a double bond.
WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 23

Molecular Formulas

C4H10 C5H12 C6H14

Saturated acyclic hydrocarbons have the

general molecular formula CnH2n+2
WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 24

Molecular Formulas
An alkene or cycloalkane has the general
molecular formula CnH2n

C6H12 C6H12

C6H14 Formula of saturated alkane with 6 carbons

C6H12
H2 Difference = 1 pair of hydrogen atoms
WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 25

Index of Hydrogen Deficiency

An alkene or cycloalkane has the general
molecular formula CnH2n

C6H12 C6H12

C6H14
C6H12
H2 Difference = 1 pair of hydrogen atoms

Index of hydrogen deficiency =1

WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 26

Index of Hydrogen Deficiency

C6H12 C6H12

Index of hydrogen deficiency =1

Every time we have a pi bond or a ring in the compound, the

index of hydrogen deficiency increases by 1
 WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 27

Index of Hydrogen Deficiency

• Indicates the relationship between molecular formulas,
multiple bonds and rings.

• It is expressed as:

Index of hydrogen deficiency =

1
(molecular formula of alkane – molecular formula of compound)
2

Index of hydrogen deficiency tells us the sum of rings plus

multiple bonds.
WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 28

Example: Index of Hydrogen deficiency

C7H14 C7H12
WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 29

Exercise
Determine the index of hydrogen deficiency for the
following molecules:
WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 30

Index of Hydrogen Deficiency

Oxygen has no effect

• CH3(CH2)5CH2OH (1-heptanol, C7H16O) has same

number of H atoms as heptane.

1
Index of hydrogen deficiency = (C7H16 – C7H 16O) = 0
2

No rings or double bonds

 WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 31

Index of Hydrogen Deficiency

Oxygen has no effect

1
Index of hydrogen deficiency = (C5H12 – C5H8O2) = 2
2

One ring plus one double bond

WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 32

Index of Hydrogen Deficiency

Treat a halogen as if it was hydrogen.

H Cl C3H5Cl
C C
Same index of hydrogen
H CH3 deficiency as for C3H6.
CHAPTER 1.10
Molecular Dipole Moments
WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 34

REVIEW: Electronegativity

Important: know relative electronegativities of nonmetals

COMMON ONES: F > O > N, Cl > Br > I, S, C > H
WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 35

Dipole Moment
A substance possesses a dipole moment if its centers of
positive and negative charge do not coincide.

+ + —
—

not polar polar

µ=exd
• µ = dipole moment
• e = amount of charge, esu (electrostatic units)
• d = distance between centers of charges (cm)
• expressed in Debye units (10-18 esu·cm)
 WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 36

Molecular Dipole Moments

δ+
δ‐ δ‐
O C O

In order to have a molecular dipole moment:

• molecule must have polar bonds

– necessary, but not sufficient

• need to know molecular shape

– individual bond dipoles can cancel each other out

WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 37

Molecular Dipole Moments

O C O

• Carbon dioxide has no dipole moment; µ = 0 D

• Individual bond dipoles cancel each other out.

WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 38

3-dimensional VECTOR SUM of bond dipoles yields

NET dipole moment of molecule
BF3: no lone CH2Cl2: no lone SF4: 1 lone
pairs on B pairs on C pair on S

Dipoles cancel out

Overall: no net dipole
NONPOLAR
POLAR POLAR
1. Determine structure & molecular geometry
• After determining geometry: ignore lone pairs
2. Determine which dipole components add vs. cancel
WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 39

Visualizing electron distribution in

molecules: Electrostatic Potential Maps

Pure covalent Polar covalent

bond (nonpolar) Ion pair
bond
H—H Li+ H-
H—F
Why is it useful to picture polarity?
• Electron-rich atoms or molecules are attracted to
electron-deficient atoms or molecules
 can predict physical & chemical properties!
 WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 40

Review: Dipole Moment of Molecules

The vector sum of magnitude and direction of individual bond dipole determines
overall dipole moment of a molecule

Net: NONPOLAR
symmetric
arrangement of
bond dipoles

Net: POLAR
asymmetry in
arrangement of
bond dipoles
WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 41

Judging polarity of organic molecules

1. Consider lone pairs as contributing δ - character

2. Treat C-H bonds as if they were totally nonpolar

(even though ∆χ = 0.4 and ∆ = 0.4)

WHY?
• Molecules are flexible:
 Free rotation occurs
about single bonds
 Exist in many different
“conformations”

THUS: on average…
dipoles

end up canceling out !

 WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 42

Identify the polar vs. nonpolar character of…

(label δ+/δ- in net polar regions of molecules only)
Draw Bond-Line or 3D structures to help with polarity:

(CH3)3CCH(OH)CH3

CH3N(CH3)2

CH3(CH2)14COOH
CHAPTER 1.11
Curved Arrows and Chemical Reactions
 WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 44

How to Use Curved Arrows in Illustrating Reactions

Curved Arrows
Reaction mechanisms: Show the direction of electron flow (High density
to low density)
Resonance: electrons don’t really “move” but we use them to show how
to get from one contributor to another

THE ANATOMY OF A CURVED ARROW VERY IMPORTANT!!!

Electrons End Up
Lone pair Tail Head Bond or
or π bond Atom

Never into Space!!!

WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 45

Curved Arrows
Consider the dissociation of H2CO3:
WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 46

Curved Arrows
• Consider the reaction shown below which shows the
combination of A+ and B-

A─B

• The arrow begins where the electrons were originally

and points to where they end up.
• Electrons flow from sites of higher electron density to
lower.
WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 47

Curved Arrows
• Many reactions involve both bond breaking and
formation. More than one arrow may be required.

• Electrons flow from electron-rich to electron-poor sites.

• Ex:
 WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 48

The Two Commandments of Arrow Pushing

1. Though shalt not break a single bond. Ex:

1. Though shalt not violate the octet rule (C’FON). Ex:

WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 49

Exercise
When a solution of NaSH in water is acidified, H2S is
produced. Complete the following equation and track
the flow of electrons via curved arrows. Is the net
charge the same on both sides of the reaction?

H
+
+ -
..
O H S H
..
..

..
H
CHAPTER 1.12
Acids and Bases:
The Arrhenius View
WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 51

Definitions: Acids and Bases

• Arrhenius
– An acid ionizes in water to give protons. A base
ionizes in water to give hydroxide ions.

• Brønsted-Lowry
– An acid is a proton donor. A base is a proton
acceptor.

• Lewis
– An acid is an electron pair acceptor. A base is
an electron pair donor.
WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 52

Arrhenius Acids and Bases

• An acid is a substance that ionizes to give
protons when dissolved in water.

H A H+ + A–

..
• A base is a substance that ionizes to give
hydroxide ions when dissolved in water.

.. –. ..
M OH
.. M+ + . OH
..
WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 53

Arrhenius Acids and Bases

• Strong acids dissociate completely in water.
Weak acids dissociate only partially.

H A H+ + A–

..
• Strong bases dissociate completely in water.
Weak bases dissociate only partially.

.. –. ..
M OH
.. M+ + . OH
..
 WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 54

Acid Strength is measured by pKa

H A H+ + A–

..
Strength of an acid is
[H+][A–]
measured by its acidity Ka =
constant, which is the [HA]
equilibrium constant Ka

pKa = – log10Ka

The smaller the value of the pKa , the stronger the acid.
CHAPTER 1.12
Acids and Bases:
The Brønsted-Lowry View

Brønsted-Lowry definition
An acid is a proton donor
A base is a proton acceptor
WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 56

A Brønsted Acid-Base Reaction

• When an acid reacts with a base, a proton is transferred
from the acid to the base.

+
B .. + H A B H + : .A–
base acid conjugate conjugate
acid base
WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 57

Proton Transfer from HBr to Water

• When water acts as a base, the acid transfers a proton to
water to form a hydronium ion.
WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 58

Equilibrium Constant for Proton Transfer

[H3O+][Br–]
Ka =
[HBr]

pKa = – log10 Ka
WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 59

Equilibrium Constant for Proton Transfer

[H3O+][Br–]
Ka =
[HBr]

• Takes the same form as for Arrhenius Ka, but H3O+

replaces H+. H3O+ and H+ are considered equivalent,
and there is no difference in Ka values for Arrhenius and
Brønsted acidity.
WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 60

Water as a Brønsted Acid

Ex:
WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 61

Exercise
• Write equation for proton transfer from hydrogen chloride to
trimethlylamine. Identify the acid, base, conjugate acid, and
conjugate base and use curved arrows to track electron
movement.
 WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 62

Dissociation Constants (pKa) of Acids

stronger
acid
Acid pKa Conj. Base
HI -10.4 I–
–
HBr -5.8 Br
H2SO4 –
-4.8 HSO4
–
HCl -3.9 Cl
weaker H3O+ -1.7 H2O
acid

Strong acids are stronger than hydronium ion.

The stronger the acid, the weaker the conjugate base.
WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 63

Dissociation Constants (pKa) of Acids

Acid pKa C on j. Ba se
H 3O + –1.7 H 2O
–
HF 3.5 F
CH3C O 2H –
4.6 CH 3CO 2
NH 4+ 9.2 NH3
–
H 2O 15 .7 HO

Weak acids are weaker than hydronium ion.

WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 64

Dissociation Constants (pKa) of Acids

A cid pKa C onj. Ba se
–
CH 3OH 15 .2 CH 3O
–
H 2O 15 .7 HO
–
CH 3CH 2O H ~ 16 CH CH O
3 2
(CH 3)2CH OH ~ 17 (CH ) CH O –
32
(CH 3)3C O H ~18 –
(CH 3) 3CO

Alcohols resemble water in acidity; their conjugate

bases are comparable to hydroxide ion in basicity.
WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 65

Dissociation Constants (pKa) of Acids

A cid pKa C on j. Ba se
–
NH 3 ~36 NH 2
–
(CH 3)2NH ~36 (CH 3)2N

Ammonia and amines are very weak acids;

their conjugate bases are very strong bases.
WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 66

Dissociation Constants (pKa) of Acids

Acid pK a C on j. Ba se
–
HC CH 26 HC C
H H
H H

H H 43 H –

H H H H
–
H2C CH2 45 H2C CH
–
CH3CH3 62 CH3CH2

Most hydrocarbons are extremely weak acids.

 WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 67

Table 1.8
From
Textbook
WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 68
WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 69

About pKa and pKb

• A separate “basicity constant” Kb is not necessary.

• Because of the conjugate relationships in the

Brønsted-Lowry approach, we can examine acid-base
reactions by relying exclusively on pKa values.
 WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 70

Example
Which is the stronger base, ammonia (left) or pyridine (right)?

N H

H N

• Recall that the stronger the acid, the weaker the

conjugate base.
• Therefore, the stronger base is the conjugate of the
weaker acid.
• Look up the pKa values of the conjugate acids of
ammonia and pyridine in Table 1.8.
WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 71

Example – Cont’d

Base

Conjugate
Acid

pKa of
Conjugate
Acid weaker acid stronger acid

Therefore, ammonia is a stronger base than pyridine

CHAPTER 1.13
How Structure Affects Acid Strength
WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 73

The Main Ways Structure Affects

Acid Strength

1. The strength of the bond to the atom from

which the proton is lost

2. The electronegativity of the atom from which

the proton is lost

3. Electron delocalization in the conjugate base

WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 74

Bond Strength
• Bond strength is the controlling factor when comparing
the acidity of hydrogen halides:

HF HCl HBr HI
pKa
3.1 -3.9 -5.8 -10.4

weakest acid strongest acid

strongest H—X bond weakest H—X bond
 WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 75

Bond Strength (Down a Period)

• When comparing two acids whose acidic Hydrogen is on a
different element from the same period, bond strength is
• inversely proportional to its relative acidity.

Decreasing bond
strength or Increasing
increasing Acidity
atomic radii.

Increasing Acidity Decreasing Bascicity

(Conjugate Base)
HF << HCl < HBr < HI
F- >> Cl- > Br- > I-
H2O < H2S < H2Se
HO- > HS- > HSe-
WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 76

Bond Strength

In looking at group 6A of the

periodic table we see this
generalization holds:
WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 77

The Main Ways Structure Affects

Acid Strength

1. The strength of the bond to the atom from

which the proton is lost

2. The electronegativity of the atom from which

the proton is lost

3. Electron delocalization in the conjugate base

 WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 78

Electronegativity (Across a Row)

• When comparing two acids whose acidic Hydrogen is on a
different element from the same row, the greater the
electronegativity, the greater the acidity of that hydrogen.
Increasing Acidity

H3C-H < H2N-H < HO-H < F-H

Decreasing Bascicity
Increasing bond (Conjugate Base)
electronegativity
H3C- > H2N- > HO- > F-
Increasing
Acidity
 WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 79

Electronegativity

CH4 NH3 H2O HF

pKa 60 36 15.7 3.1

weakest acid strongest acid

least electronegative most electronegative
WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 80

Electronegativity

• This equilibrium becomes more favorable as A becomes

better able to bear a negative charge.

• Another way of looking at it is that H becomes more

positive as the atom to which it is attached becomes more
electronegative (bond is more polarized).
WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 81

Bond Strength versus Electronegativity

• Bond strength is more important when comparing acids
in which the proton that is lost is bonded to atoms in the
same group of the periodic table.

• Electronegativity is more important when comparing

acids in which the proton that is lost is bonded to atoms
in the same row of the periodic table.
WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 82

Base Strength

Remember the inverse relationship between acidity

and basicity!
WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 83

Acidity of Alcohols
pKa

HO—H 15.7
In many acids the
acidic proton is
bonded to oxygen. CH3O—H 15.2

CH3CH2O—H 16
Alcohols (RO—H)
resemble water (HO (CH3)2CHO—H 17
—H) in their acidity.
(CH3)3CO—H 18
WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 84

Acidity of Alcohols
• Electronegative substituents can increase the acidity of
alcohols by drawing electrons away from the OH group.

CH3CH2OH CF3CH2OH
pKa 16 11.3
weaker stronger
WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 85

Inductive Effect
F H
δ+
F C C O H

F H
• The greater acidity of CF3CH2OH compared to CH3CH2OH
is an example of an inductive effect.

• Inductive effects arise through polarization of the electron

distribution in the bonds between atoms.

• A substituent induces a polarization in the bonds between it

and some remote site.
WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 86

Electrostatic Potential Maps

• The greater positive character of the proton of the OH
group of CF3CH2OH compared to CH3CH2OH is apparent
in the more blue color in its electrostatic potential map.

CH3CH2OH CF3CH2OH
WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 87

Another Example of the Inductive Effect

O O

H C H F C H
C O C O
H F
H F

pKa 4.7 0.50

weaker stronger
 WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 88

Inductive Effects
(Electron Withdrawing Groups) EWG
Electron withdrawing groups (EWG) stabilize the conjugate
base,
• The more electronegative the EWG is, the more acidic
the compound is.
• The further away the EWG is from the neg. charge of
the Conj. Base, the weaker an acid it is.

pKa = 4.76 3.15 2.86 2.81 2.66

The EWGs “pull” on the lone pair electrons and negative charge,
stabilizing the Conjugate Base
WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 89

The Main Ways Structure Affects

Acid Strength

1. The strength of the bond to the atom from which

the proton is lost

2. The electronegativity of the atom from which the

proton is lost

3. Electron delocalization in the conjugate base

WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 90

Electron Delocalization

• Ionization becomes more favorable if electron

delocalization increases in going from left to right in the
equation (A- ion is more stable).

• Resonance is a convenient way to show electron

delocalization.
WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 91

Nitric Acid
Ex:
WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 92

Nitric Acid Cont’d

Ex:
WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 93

Acetic Acid
Ex:
WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 94

Acetic Acid Cont’d

Ex:
WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 95

Conjugate Base and it’s Effect on Acidity

• The acidity of the parent acid increases as the
conjugate base stability increases.

• Factors that stabilize the conjugate base:

1. The electronegativity of the atom from which the

proton is lost

2. Electron delocalization in the conjugate base

CHAPTER 1.14
Acid-Base Equilibria
 WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 97

Generalization
• To determine the position of the equilibrium in any
proton transfer reaction, consider the acid strengths.

• The equilibrium in an acid-base reaction is favorable if

the stronger acid is on the left and the weaker acid is on
the right.

Stronger acid+ Stronger base Weaker acid+ Weaker base

WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 98

Example of a Strong Acid

pKa = -5.8 pKa = -1.7

stronger acid weaker acid

The equilibrium lies to the side of the weaker acid.

(To the right)
WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 99

Example of a Weak Acid

pKa = 4.7 pKa = -1.7

weaker acid stronger acid

The equilibrium lies to the side of the weaker acid.

(To the left)
WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 100

Summary
• A strong acid is one that is stronger than H3O+.
• A weak acid is one that is weaker than H3O+.

• A strong base is one that is stronger than HO–.

• A weak base is one that is weaker than HO–.

• The strongest acid present in significant quantities when a

strong acid is dissolved in water is H3O+.
• The strongest acid present in significant quantities when a
weak acid is dissolved in water is the weak acid itself.
WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 101

Predicting the Direction of

Acid-Base Reactions

Phenol Water
pKa = 10 pKa = 15.7

stronger acid weaker acid

• The equilibrium lies to the side of the weaker acid (to the
right). Phenol is converted to phenoxide ion by reaction
with NaOH.
WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 102

Predicting the Direction of

Acid-Base Reactions

Phenol Carbonic acid

pKa = 10 pKa = 6.4

weaker acid stronger acid

• The equilibrium lies to the side of the weaker acid (to the
left). Phenol is not converted to phenoxide ion by reaction
with NaHCO3.
 WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 103

Keq
The equilibrium constant Keq for an acid-base reaction is
given by the ratio for the Ka of the reactant acid to the Ka of the
product acid.

Ka of reactant acid 10-pKa of reactant acid

Keq = =
Ka of product acid 10-pKa of product acid

K > 1, then equilibrium lies to the right

K < 1, then equilibrium lies to the left
WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 104

Exercise

What is the equilibrium constant when fluoride ion is reacted

with acetic acid?

1. Start by writing out equation for acid-base reaction.

2. Compare pKa’s of the two acids
3. Which side does the equilibrium lie?
4. Calculate Keq
CHAPTER 1.15
Lewis Acids and Lewis Bases

Lewis Definition
An acid is an electron pair acceptor.
A base is an electron pair donor.
WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 106

Lewis Acid-Lewis Base Reactions

• Lewis acids and the Lewis bases may be
either neutral molecules or ions.

Lewis acid + Lewis base

–
A+ + :B A—B
–
A + : B – A—B

A—B +
A+ + :B
A + :B – A—B +
 WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 107

Example: Two Neutral Molecules

Lewis acid Lewis base

• Product is a stable [Link] is a liquid with a

boiling point of 126°C. Of the two reactants,
BF3 is a gas and H3CH2OCH2CH3 is a liquid with a
boiling point of 34°C.
WINTER 2024 ORGANIC CHEMISTRY TOPIC 1 Slide 108

Example: Ion + Neutral Molecule

Lewis base Lewis acid

• Reaction is classified as a substitution. But notice

how much it resembles a Brønsted acid-base reaction.

• Brønsted acid-base reactions are a subcategory of

Lewis acid-Lewis base reactions.