ORGANIC CHEMISTRY

CHM032 ORGANIC CHEMISTRY FOR TEACHERS

FELIPA GISELA dL. TENIDO

Department of Chemistry
College of Science and Mathematics
FGdLTenido Department of Chemistry , College of Science and Mathematics 2
 CHAPTER 1
Structure and Bonding ;
Acids and Bases

Fundamentals of Organic Chemistry

John McMurry , 7th ed

FGdLTenido Department of Chemistry , College of Science and Mathematics 3

Structure and Bonding ; Acids and Bases

Catalyzes a crucial
step in the body's
synthesis of
cholesterol.
Understanding how
this enzyme functions
has led to the
development of drugs
credited with saving
millions of lives. Enzyme HMG – CoA reductase
ribbon model
FGdLTenido Department of Chemistry , College of Science and Mathematics 4
Structure and Bonding ; Acids and Bases
Introduction

A scientific revolution is now taking

place - a revolution that will give us
safer and more effective medicines
cure our genetic diseases
increase our life spans
improve the quality of our lives.
FGdLTenido Department of Chemistry , College of Science and Mathematics 5
Structure and Bonding ; Acids and Bases
Introduction

The revolution is based in understanding

the structure and function of the
approximately
21,000 genes in the human body, but it
relies on
organic chemistry as the enabling science.

FGdLTenido Department of Chemistry , College of Science and Mathematics 6

Structure and Bonding ; Acids and Bases
Introduction
Organic Chemistry is all around us…
the reactions and interactions of organic molecules
allow us to
see, smell, fight, and feel
provide the molecules that
feed us,
treat our illnesses,
protect our crops,
clean our clothes
FGdLTenido Department of Chemistry , College of Science and Mathematics 7
Structure and Bonding ; Acids and Bases
History
In the late 1700s, the term organic chemistry, was used to
mean the chemistry of compounds found in living organisms.
Organic compounds were generally low-melting solids and were
usually more difficult to isolate, purify, and work with than
high-melting inorganic compounds.
By the mid-1800s, it was clear that there was no fundamental
difference between organic and inorganic compounds.
The only distinguishing characteristic of organic chemicals
is that all contain the element carbon.

Department of Chemistry , College of Science and Mathematics 8

Structure and Bonding ; Acids and Bases
What is organic chemistry?
Organic chemistry is the study of the compounds
of carbon.
includes biological molecules, drugs, solvents, dyes
does not include metal salts and materials
(inorganic)
does not include materials of large repeating
molecules without sequences

Department of Chemistry , College of Science and Mathematics 9

Structure and Bonding ; Acids and Bases
More than 99% of the presently known chemical
compounds contain carbon.
 what makes carbon special?
the electronic structure of carbon and
its consequent position in the Periodic
Table
as a group 4A element, carbon can share
four valence electrons and form four
strong covalent bonds
Department of Chemistry , College of Science and Mathematics 10
Structure and Bonding ; Acids and Bases

 what makes carbon special?

carbon atoms can bond to one another,
forming long chains and rings
carbon is able to form an immense
diversity of compounds from a simple
methane to the staggeringly complex
DNA, which can have more than 100
million carbons
Department of Chemistry , College of Science and Mathematics 11
Structure and Bonding ; Acids and Bases
the position of carbon in the periodic table

Department of Chemistry , College of Science and Mathematics 12

Structure and Bonding ; Acids and Bases
Other elements commonly found in organic compounds are shown in the colors typically used
to represent them.

Department of Chemistry , College of Science and Mathematics 13

 1.1 Atomic Structure
• Atom: (2 x 10-10 m)
• Nucleus (~ 10-14 to 10-15 m)
• protons (+)
• neutrons
• Electrons (-) 10-10 m

Department of Chemistry , College of Science and Mathematics 14

 1.1 Atomic Structure
A specific atom is described by its atomic
number (Z), which gives the number of protons
(or electrons) it contains, and its mass number
(A), which gives the total number of protons
plus neutrons in its nucleus.
All the atoms of a given element have the same
atomic number but they can have different
mass numbers depending on how many neutrons
they contain.
Department of Chemistry , College of Science and Mathematics 15
 1.1 Atomic Structure

Isotopes - atoms with the same atomic

number but different mass numbers
Atomic mass (atomic weight) – weighted
average mass units (amu) of an element’s
naturally occurring isotopes
e.g. 1.001 amu for hydrogen
12.011 amu for carbon

Department of Chemistry , College of Science and Mathematics 16

1.1 Atomic Structure : The Electrons
• the behavior of a specific electron in an atom
can be described by a mathematical expression
called a wave equation
(Quantum Mechanical Model of Atomic Structure)
• the same sort of expression used to describe
the motion of waves in a fluid
• The solution to a wave equation is a wave
function or orbital.

Department of Chemistry , College of Science and Mathematics 17

1.1 Atomic Structure : The Orbital

An orbital, Ψ, can be thought of

as defining a region of space
around the nucleus where the
electron can most likely be found.

Department of Chemistry , College of Science and Mathematics 18

1.1 Atomic Structure : Atomic Orbitals

Orbitals () : s, p, d, and f

s and p = most common among

organic and biological chemistry

Department of Chemistry , College of Science and Mathematics 19

1.1 Atomic Structure : Atomic Orbitals

an s orbital is spherical, with the

nucleus at its center
a p orbital is dumbbell-shaped and can
be oriented in space along any of three
mutually perpendicular directions,
arbitrarily denoted px , py , and pz
Department of Chemistry , College of Science and Mathematics 20
1.1 Atomic Structure : Atomic Orbitals

The two parts, or lobes, of a p

orbital have different algebraic
signs (+ and -) in the wave function
and are separated by a region of
zero electron density called a node.

Department of Chemistry , College of Science and Mathematics 21

1.1 Atomic Structure : Atomic Orbitals
s and p orbitals

Department of Chemistry , College of Science and Mathematics 22

1.1 Atomic Structure : Atomic Orbitals
s and p orbitals

Department of Chemistry , College of Science and Mathematics 23

1.1 Atomic Structure : Atomic Orbitals
Orbitals are organized into layers (or
electron shells) around the nucleus of
successively larger size and energy.
Electron shells contain different
numbers and kinds of orbitals.
Each orbital can accommodate a
maximum of 2 electrons.
Department of Chemistry , College of Science and Mathematics 24
1.1 Atomic Structure : Atomic Orbitals
the energy levels of electrons in an atom

Department of Chemistry , College of Science and Mathematics 25

1.2 Atomic Structure : Electron Configurations

The lowest-energy arrangement,

or ground-state electron
configuration, of an atom is a
listing of the orbitals that the
atom’s electrons occupy.

Department of Chemistry , College of Science and Mathematics 26

1.2 Atomic Structure : Electron Configurations

RULE 1 : Aufbau Principle

Electrons will fill the lower
energy levels before moving
to higher energy orbitals.

Department of Chemistry , College of Science and Mathematics 27

1.2 Atomic Structure : Electron Configurations

RULE 1 : Aufbau Principle

The orbitals of lowest energy are
filled first, according to the order

1s  2s  2p  3s  3p  4s  3d

Department of Chemistry , College of Science and Mathematics 28

1.2 Atomic Structure : Electron Configurations

RULE 2 : Pauli – Exclusion Principle

Only two electrons can occupy an
orbital, and they must be of opposite
spin.
This spin can have two orientations,
denoted as up  and down .
Department of Chemistry , College of Science and Mathematics 29
1.2 Atomic Structure : Electron Configurations

RULE 3 : Hund’s Rule

If two or more empty orbitals of
equal energy are available, one
electron occupies each with the spins
parallel until all orbitals are half-full.

Department of Chemistry , College of Science and Mathematics 30

1.2 Atomic Structure : Electron Configurations

Department of Chemistry , College of Science and Mathematics 31

1.3 Development of Chemical Bonding Theory
1858 : August Kekulé and Archibald Couper
independently proposed that, in all organic
compounds, carbon is tetravalent; i.e., it always
forms four bonds when it joins other elements
to form chemical compounds.
Kekulé further stated that carbon atoms can
bond to one another to form extended chains of
linked atoms and chains can double back on
themselves to form rings.
Department of Chemistry , College of Science and Mathematics 32
1.3 Development of Chemical Bonding Theory

1874 :
Jacobus van’t Hoff and Joseph Le Bel added a third
dimension to our ideas about organic compounds.
They proposed that the four bonds of carbon are not
oriented randomly but have specific spatial directions.
Van’t Hoff went even further and suggested that the
four atoms to which carbon is bonded sit at the
corners of a regular tetrahedron, with carbon in the
center.
Department of Chemistry , College of Science and Mathematics 33
1.3 Development of Chemical Bonding Theory
a representation of van’t Hoff’s tetrahedral carbon atom

Department of Chemistry , College of Science and Mathematics 34

1.3 Development of Chemical Bonding Theory
a representation of van’t Hoff’s conventions :
tetrahedral carbon atom
solid lines represent
bonds in the plane of
the page
heavy wedged line
represents a bond
coming out of the page
toward the viewer
dashed line represents
a bond receding back
behind the page away
from the viewer
Department of Chemistry , College of Science and Mathematics 35
 1.4 The Nature of Chemical Bonds
Why do atoms bond together?
results to more stable compound
lower in energy than the separate
atoms
energy is released and flows out of
the chemical system when a bond
forms
Department of Chemistry , College of Science and Mathematics 36
 1.4 The Nature of Chemical Bonds
How are bonds formed?
bonds are formed through the valence electrons of
the atoms involved
valence electrons – electrons in the outermost shell
when bonds are formed, the valence shell would
contain a total of 8 electrons (octet rule)
after the bond formation, the resulting electron
configuration of the atoms involved is isoelectronic
with any of the noble gases
Department of Chemistry , College of Science and Mathematics 37
1.4 The Nature of Chemical Bonds
types of chemical bonds
1. Ionic Bonds
• when metals bond to nonmetals, some
electrons from the metal atoms are
transferred to the nonmetal atoms
• metals have low ionization energy, relatively
easy to lose an electron
• nonmetals have high electron affinities,
relatively good to accept electrons
Department of Chemistry , College of Science and Mathematics 38
1.4 The Nature of Chemical Bonds
types of chemical bonds : ionic bonds
Examples:

Na + Cl  Na+ Cl–
Mg + 2 Br  Mg2+ 2Br–
Department of Chemistry , College of Science and Mathematics 39
 1.4 The Nature of Chemical Bonds
types of chemical bonds
2. Covalent Bonds
• nonmetals have relatively high ionization energies,
so it is difficult to remove electrons from them
• when nonmetals bond together, it is better in
terms of potential energy for the atoms to share
valence electrons
• potential energy is lowest when the electrons are
between the nuclei
• shared electrons hold the atoms together by
attracting nuclei of both atoms
Department of Chemistry , College of Science and Mathematics 40
 1.4 The Nature of Chemical Bonds
types of chemical bonds : covalent bonds
1916 G. N. Lewis proposed the shared-electron bond
shared-electron bond is called a covalent bond
The neutral group of atoms held together by covalent
bonds is called a molecule.
A simple way of indicating the covalent bonds in molecules
is to use the Lewis structures or the electron-dot
structures.
electron-dots indicate the number of valence electrons in
an atom
nonbonding electrons - lone-pair electrons
Department of Chemistry , College of Science and Mathematics 41
1.4 The Nature of Chemical Bonds
covalent bonds : Lewis structures

Department of Chemistry , College of Science and Mathematics 42

1.4 The Nature of Chemical Bonds
Lewis structures and Kekulé structures
Lewis structures : Electron-dot structures

Kekulé structures : Line-bond structures

Department of Chemistry , College of Science and Mathematics 43

 1.4 The Nature of Chemical Bonds
Number of Covalent Bonds
The number of covalent bonds an atom forms depends on
how many additional valence electrons it needs to reach a
noble-gas configuration.

Department of Chemistry , College of Science and Mathematics 44

 1.4 The Nature of Chemical Bonds
Lone-pair Electrons
Valence electrons not used for bonding are called lone-pair
electrons, or nonbonding electrons.
Example:
the nitrogen atom in ammonia (NH3), shares six valence
electrons in three covalent bonds and has its remaining two
valence electrons in a nonbonding lone pair

Department of Chemistry , College of Science and Mathematics 45

Exercises:
1. What are likely formulas for the following molecules?

2. Write both electron-dot and line-bond structures for

the following molecules, showing all nonbonded electrons:

3. Why can’t an organic molecule have the formula C2H7?

Department of Chemistry , College of Science and Mathematics 46

Exercises:
1. What are likely formulas for the following molecules?

Department of Chemistry , College of Science and Mathematics 47

Exercises:
2. Write both electron-dot and line-bond structures for
the following molecules, showing all nonbonded electrons:

Department of Chemistry , College of Science and Mathematics 48

Exercises:
3. Why can’t an organic molecule have the formula C2H7?

C2H7 has too many hydrogens for a

compound with two carbons.

Department of Chemistry , College of Science and Mathematics 49

1.5 Forming Covalent Bonds : Valence Bond Theory
How does electron sharing lead to bonding between atoms?
Valence bond theory
A covalent bond forms when two atoms approach each other
closely and a singly occupied orbital on one atom overlaps a singly
occupied orbital on the other atom.
Example: In the H2 molecule, the H - H bond results from the
overlap of two singly occupied hydrogen 1s orbitals.

Department of Chemistry , College of Science and Mathematics 50

1.5 Forming Covalent Bonds : Valence Bond Theory

• the electrons are now paired in the

overlapping orbitals
• the electrons are attracted to the nuclei of
both atoms, bonding the atoms together
Department of Chemistry , College of Science and Mathematics 51
1.5 Forming Covalent Bonds : Valence Bond Theory

During the bond-forming reaction, 436 kJ/mol

(104 kcal/mol) of energy is released.
2 H•  H2 + 436 kJ/mol 
the H2 molecule formed has 436 kJ/mol less
energy than the starting 2H• atoms
thus H2 is more stable than the 2H• atoms
new H-H bond has a bond strength of 436 kJ/mol
Department of Chemistry , College of Science and Mathematics 52
1.5 Forming Covalent Bonds : Valence Bond Theory

How close are the two nuclei in the H2 molecule?

The 2 nuclei in the H2 molecule must not be too

close nor too far apart.
if they are too close, they will repel each other
because both are positively charged
if they are too far apart, they won’t be able to
share the bonding electrons

Department of Chemistry , College of Science and Mathematics 53

1.5 Forming Covalent Bonds : Valence Bond Theory

How close are the two nuclei in the H2 molecule?

There is an optimum distance between

nuclei that leads to maximum stability
called the bond length.

In the H2 molecule, the bond length is 74 pm.

Department of Chemistry , College of Science and Mathematics 54

1.5 Forming Covalent Bonds : Valence Bond Theory
A plot of energy versus internuclear distance for two hydrogen atoms. The distance at the
minimum energy point is the bond length.

Every covalent bond has both a

characteristic bond strength
and bond length.

For the H2 molecule

bond strength of H – H
436 kJ/mol
bond length of H – H
74 pm

Department of Chemistry , College of Science and Mathematics 55

1.6 sp3 Hybrid Orbitals and the Structure of Methane

Carbon has four valence electrons (2s2 2p2) and

forms four bonds.
Because carbon uses two kinds of orbitals for
bonding, 2s and 2p, we might expect methane to
have two kinds of C-H bonds.
In fact, though, all four C-H bonds in methane
are identical and are spatially oriented toward
the corners of a regular tetrahedron.
Department of Chemistry , College of Science and Mathematics 56
1.6 sp3 Hybrid Orbitals and the Structure of Methane

in 1931 Linus Pauling proposed that an s orbital and

three p orbitals can combine, or hybridize, to form four
equivalent atomic orbitals with tetrahedral orientation
these tetrahedrally oriented orbitals are called sp3
hybrids
Note
the superscript 3 in the name sp3 tells how many of each
type of atomic orbital combine to form the hybrid, not
how many electrons occupy it

Department of Chemistry , College of Science and Mathematics 57

1.6 sp3 Hybrid Orbitals and the Structure of Methane

1s + 3p = 4 sp3

Department of Chemistry , College of Science and Mathematics 58

1.6 sp3 Hybrid Orbitals and the Structure of Methane
Four sp3 hybrid orbitals (green), oriented to the corners of a regular tetrahedron, are formed by
combination of an atomic s orbital (red) and three atomic p orbitals (red/blue).
The sp3 hybrids have two lobes and are unsymmetrical about the nucleus, giving them a directionality
and allowing them to form strong bonds when they overlap an orbital from another atom.

Department of Chemistry , College of Science and Mathematics 59

1.6 sp3 Hybrid Orbitals and the Structure of Methane
why does carbon forms four equivalent tetrahedral bonds?
When an s orbital hybridizes with three p orbitals, the
resultant sp3 hybrid orbitals are unsymmetrical about
the nucleus.
One of the two lobes is much larger than the other and
can therefore overlap better with another orbital when
it forms a bond.
As a result, sp3 hybrid orbitals form stronger bonds
than the unhybridized s or p orbitals.

Department of Chemistry , College of Science and Mathematics 60

1.6 sp3 Hybrid Orbitals and the Structure of Methane

The asymmetry of sp3 orbitals arises because the two

lobes of a p orbital have different algebraic signs,
+ and -.
Thus, when a p orbital hybridizes with an s orbital, the
positive p lobe adds to the s orbital but the negative
p lobe subtracts from the s orbital.
The resultant hybrid orbital is therefore
unsymmetrical about the nucleus and is strongly
oriented in one direction.

Department of Chemistry , College of Science and Mathematics 61

1.6 sp3 Hybrid Orbitals and the Structure of Methane
formation of sp3
hybrid orbitals

Department of Chemistry , College of Science and Mathematics 62

1.6 sp3 Hybrid Orbitals and the Structure of Methane
When each of the four identical sp3 hybrid orbitals
of a carbon atom overlaps with the 1s orbital of a
hydrogen atom, four identical C - H bonds are formed
and methane results.

Department of Chemistry , College of Science and Mathematics 63

1.6 sp3 Hybrid Orbitals and the Structure of Methane

Each C - H bond in methane has a strength of 439

kJ/mol (105 kcal/mol) and a length of 109 pm.
Because the four C – H bonds have a specific
geometry, we also can define a property called the
bond angle.
The angle formed by each H-C-H is 109.5°, the so-
called tetrahedral angle.

Department of Chemistry , College of Science and Mathematics 64

1.6 sp3 Hybrid Orbitals and the Structure of Methane

Department of Chemistry , College of Science and Mathematics 65

1.7 sp3 Hybrid Orbitals and the Structure of Ethane

The same kind of orbital hybridization that

accounts for the methane structure also
accounts for the bonding together of carbon
atoms into chains and rings to make possible
many millions of organic compounds.

Ethane, C2H6, is the simplest molecule containing

a carbon–carbon bond.

Department of Chemistry , College of Science and Mathematics 66

1.7 sp3 Hybrid Orbitals and the Structure of Ethane
Ethane, C2H6, is the simplest molecule containing a
carbon–carbon bond.

Department of Chemistry , College of Science and Mathematics 67

1.7 sp3 Hybrid Orbitals and the Structure of Ethane

For the ethane molecule, we can imagine

that the two carbon atoms bond to each
other by overlap of an sp3 hybrid orbital
from each carbon.
The remaining three sp3 hybrid orbitals of
each carbon overlap with the 1s orbitals of
three hydrogens to form the six C - H
bonds.
Department of Chemistry , College of Science and Mathematics 68
1.7 sp3 Hybrid Orbitals and the Structure of Ethane

Department of Chemistry , College of Science and Mathematics 69

1.7 sp3 Hybrid Orbitals and the Structure of Ethane

The C - H bonds in ethane are similar to

those in methane, although a bit weaker —
421 kJ/mol (101 kcal/mol) for ethane
versus 439 kJ/mol for methane.

The C - C bond is 154 pm long and has a

strength of 377 kJ/mol (90 kcal/mol).

Department of Chemistry , College of Science and Mathematics 70

1.7 sp3 Hybrid Orbitals and the Structure of Ethane

All the bond angles of ethane are near, although

not exactly at, the tetrahedral value of 109.5°.

Department of Chemistry , College of Science and Mathematics 71

1.7 sp3 Hybrid Orbitals and the Structure of Ethane

Department of Chemistry , College of Science and Mathematics 72

1.8 Other Kinds of Hybrid Orbitals : sp2 and sp
The bonds we’ve seen in methane and ethane are called
single bonds because they result from the sharing of one
electron pair between bonded atoms.
In some molecules carbon atoms can also form a double
bond by sharing two electron pairs between atoms or a
triple bond by sharing three electron pairs.
Ethylene, for instance, has the structure H2CCH2 and
contains a carbon– carbon double bond, while acetylene has
the structure HCCH and contains a carbon–carbon triple
bond.
Department of Chemistry , College of Science and Mathematics 73
1.8 Other Kinds of Hybrid Orbitals : sp2 and sp

Department of Chemistry , College of Science and Mathematics 74

1.8 Other Kinds of Hybrid Orbitals : sp2 and sp
formation of sp2
hybrid orbitals

Department of Chemistry , College of Science and Mathematics 75

1.8 Other Kinds of Hybrid Orbitals : sp2 and sp

The three equivalent sp2 hybrid orbitals (green) lie in a plane

at angles of 120° to one another, and a single unhybridized p
orbital (red/blue) is perpendicular to the sp2 plane.
Department of Chemistry , College of Science and Mathematics 76
 1.8 Other Kinds of Hybrid Orbitals : sp2 and sp

The structure of ethylene. Orbital overlap of two sp2-hybridized carbons forms a carbon–carbon
double bond. One part of the double bond results from σ (head-on) overlap of sp2 orbitals (green),
and the other part results from π (sideways) overlap of unhybridized p orbitals (red/blue). The π
bond has regions of electron density above and below a line drawn between nuclei.
Department of Chemistry , College of Science and Mathematics 77
1.8 Other Kinds of Hybrid Orbitals : sp2 and sp
Ethylene : C2H4 : 1 σ bond and 1 π bond

Department of Chemistry , College of Science and Mathematics 78

1.8 Other Kinds of Hybrid Orbitals : sp2 and sp
formation of sp hybrid orbitals

Department of Chemistry , College of Science and Mathematics 79

1.8 Other Kinds of Hybrid Orbitals : sp2 and sp
An sp-hybridized carbon atom.

The two sp hybrid orbitals (green) are oriented 180° away from each
other, perpendicular to the two remaining p orbitals (red/blue).
Department of Chemistry , College of Science and Mathematics 80
1.8 Other Kinds of Hybrid Orbitals : sp2 and sp

The
structure of
acetylene.
The two sp-
hybridized
carbon
atoms are
joined by
one sp–sp σ
bond and two
p–p π bonds.

Department of Chemistry , College of Science and Mathematics 81

1.8 Other Kinds of Hybrid Orbitals : sp2 and sp
Acetylene : C2H2 : 1 σ bond and 2 π bonds

Department of Chemistry , College of Science and Mathematics 82

Department of Chemistry , College of Science and Mathematics 83
 Hybridization and Geometry
The shape of organic molecules is determined by the hybridization of
the atoms.

Department of Chemistry , College of Science and Mathematics 84

 Strength of pi () and sigma () Bonds
Functional groups which contain  bonds are generally more
reactive as the  bond is weaker than the σ bond.

The  bond in an alkene or alkyne is around 210 to 230 kJ/mol,

while the σ bond is around 350 kJ/mol.
Department of Chemistry , College of Science and Mathematics 85
 Bond Strength

the greater the ‘s’ character of the carbon

orbitals, the shorter the bond length, because
the electrons are held closer to the nucleus

the shorter the bond length,

the stronger the bond
Department of Chemistry , College of Science and Mathematics 86
 1.9 Polar Covalent Bonds : Electronegativity

chemical bonds : ionic or covalent

the bond in sodium chloride is ionic
sodium transfers an electron to chlorine to give Na+ and
Cl ions which are held together in the solid by
electrostatic attractions between the unlike charges
the C - C bond in ethane is covalent
the two bonding electrons are shared equally by the
two equivalent carbon atoms, resulting in a symmetrical
electron distribution in the bond
Department of Chemistry , College of Science and Mathematics 87
 1.9 Polar Covalent Bonds : Electronegativity

Most bonds are neither fully ionic nor fully

covalent but are somewhere between the two
extremes.
Such bonds are called polar covalent bonds,
meaning that the bonding electrons are
attracted more strongly by one atom than the
other so that the electron distribution between
atoms is not symmetrical.
Department of Chemistry , College of Science and Mathematics 88
 1.9 Polar Covalent Bonds : Electronegativity
Covalent bond to Ionic bond

The continuum in bonding from covalent to ionic is a result of an unequal

distribution of bonding electrons between atoms. The symbol  (lowercase
Greek delta) means partial charge, either partial positive (+) for the
electron-poor atom or partial negative (–) for the electron-rich atom.
Department of Chemistry , College of Science and Mathematics 89
 1.9 Polar Covalent Bonds : Electronegativity
Types of Covalent Bond
nonpolar covalent bond
results from the combination of two nonmetallic atoms of the same
electronegativity
equal sharing of valence electrons

polar covalent bond

results from the combination of two nonmetallic atoms of different
electronegativity
unequal sharing of valence electrons
separation of charges
bonding electrons are attracted towards the
more electronegative atom
Department of Chemistry , College of Science and Mathematics 90
1.9 Polar Covalent Bonds : Electronegativity
Bond Polarity

bond polarity is due to differences in

electronegativity (EN)

electronegativity (EN) is the intrinsic

ability of an atom to attract the shared
electrons in a covalent bond

Department of Chemistry , College of Science and Mathematics 91

 Electronegativity Values of the Elements

Elements in orange are the most electronegative, those in peach are

medium, and those in green are the least electronegative.

Department of Chemistry , College of Science and Mathematics 92

 1.9 Polar Covalent Bonds : Electronegativity

a bond between atoms with similar

electronegativities is nonpolar covalent
a bond between atoms whose
electronegativities differ by less than 2
units is polar covalent
a bond between atoms whose
electronegativities differ by 2 units or
more is largely ionic
Department of Chemistry , College of Science and Mathematics 93
1.9 Polar Covalent Bonds : Electronegativity

EN = 0 0 < EN < 2.0 EN ≥ 2.0

Department of Chemistry , College of Science and Mathematics 94

 1.9 Polar Covalent Bonds : Electronegativity

A carbon–hydrogen bond is
relatively nonpolar because
carbon and hydrogen have
similar electronegativities.
ENcarbon = 2.5 ENhydrogen = 2.1

Department of Chemistry , College of Science and Mathematics 95

 1.9 Polar Covalent Bonds : Electronegativity
A bond between carbon and a more
electronegative element such as oxygen or
chlorine is polar covalent.
The electrons in such a bond are drawn away
from carbon toward the more electronegative
atom, leaving the carbon with a partial positive
charge, +, and leaving the more electronegative
atom with a partial negative charge, -.

Department of Chemistry , College of Science and Mathematics 96

1.9 Polar Covalent Bonds : Electronegativity

Department of Chemistry , College of Science and Mathematics 97

1.9 Polar Covalent Bonds : Electronegativity

A bond between carbon and a less

electronegative element is polarized
so that carbon bears a partial
negative charge (-) and the other
atom bears a partial positive charge
(+).
Department of Chemistry , College of Science and Mathematics 98
1.9 Polar Covalent Bonds : Electronegativity

Department of Chemistry , College of Science and Mathematics 99

1.9 Polar Covalent Bonds : Electronegativity
• Electrostatic potential maps
• Electron rich (red)
• Electron poor (blue)

Department of Chemistry , College of Science and Mathematics 100

1.9 Polar Covalent Bonds : Electronegativity

methanol, CH3OH, has a polar covalent C  O bond

Department of Chemistry , College of Science and Mathematics 101

1.9 Polar Covalent Bonds : Electronegativity

methyllithium, CH3Li, has a polar covalent C  Li bond

Department of Chemistry , College of Science and Mathematics 102
 1.9 Polar Covalent Bonds : Electronegativity

crossed arrow is used to indicate the direction of

bond polarity

electrons are displaced in the direction of the arrow

The tail of the arrow (which looks like a plus sign) is

electron-poor (+), and the head of the arrow is
electron-rich (–).

Department of Chemistry , College of Science and Mathematics 103

 1.9 Polar Covalent Bonds : Electronegativity
Electronegativity and Inductive Effect
An inductive effect is simply the shifting of
electrons in a σ bond in response to the
electronegativity of nearby atoms.
Metals, such as lithium and magnesium,
inductively donate electrons, whereas reactive
nonmetals, such as oxygen and nitrogen,
inductively withdraw electrons.
Department of Chemistry , College of Science and Mathematics 104
Electronegativity and Inductive Effect

Department of Chemistry , College of Science and Mathematics 105

 Predicting the Polarity of Bonds
Predict the extent and direction of
polarization of the O‒H bonds in H2O.

Which element in each of the following pairs

is more electronegative?
(a) Li or H (b) Be or Br (c) Cl or I
Department of Chemistry , College of Science and Mathematics 106
 Predicting the Polarity of Bonds
Predict the extent and direction of
polarization of the O‒H bonds in H2O.

Which element in each of the following pairs

is more electronegative?
(a) Li or H (b) Be or Br (c) Cl or I
Department of Chemistry , College of Science and Mathematics 107
 Predicting the Polarity of Bonds

Use the +/‒ convention to indicate the direction of

expected polarity for each of the bonds shown:
(a) H3C―Br (b) H3C―NH2 (c) H2N―H
(d) H3C―SH (e) H3C―MgBr (f) H3C―F

Order the bonds in the following compounds according

to their increasing ionic character:
CCl4 , MgCl2 , TiCl3 , Cl2O

Department of Chemistry , College of Science and Mathematics 108

 Predicting the Polarity of Bonds
Use the +/‒ convention to indicate the direction of
expected polarity for each of the bonds shown:
(a) H3C―Br (b) H3C―NH2 (c) H2N―H
C + , Br ‒ C + , N ‒ H + , N ‒
(d) H3C―SH (e) H3C―MgBr (f) H3C―F
C + , S ‒ Mg + , C ‒ C + , F ‒

Order the bonds in the following compounds according to

their increasing ionic character:
CCl4 , MgCl2 , TiCl3 , Cl2O
CCl4 and Cl2O < TiCl3 < MgCl2
Department of Chemistry , College of Science and Mathematics 109
1.10 Acids and Bases : The Bronsted-Lowry Definition

a Brønsted–Lowry acid is a substance that donates a

hydrogen ion (H+)
a Brønsted–Lowry base is a substance that accepts a
hydrogen ion (H+)

the conjugate base of the acid is the product that

results when the acid loses a proton
the conjugate acid of the base is the product that
results when the base gains a proton
Department of Chemistry , College of Science and Mathematics 110
1.10 Acids and Bases : The Bronsted-Lowry Definition

Donates/accepts a hydrogen ion (H+) or a proton

Conjugate A/B

Department of Chemistry , College of Science and Mathematics 111

1.10 Acids and Bases : The Bronsted-Lowry Definition

Department of Chemistry , College of Science and Mathematics 112

 Acid – Base Reactions
A strong acid yields a weak conjugate base,
and a weak acid yields a strong conjugate
base.
A strong acid is one that loses H+ easily, meaning
that its conjugate base holds the H+ weakly and is
therefore a weak base.
A weak acid is one that loses H+ with difficulty,
meaning that its conjugate base does hold the proton
tightly and is therefore a strong base.
Department of Chemistry , College of Science and Mathematics 113
 Acid – Base Reactions

example :
HCl is a strong acid means that Cl‒ does
not hold H+ tightly and is a weak base

water is a weak acid means that OH‒

holds H+ tightly and is a strong base

Department of Chemistry , College of Science and Mathematics 114

 Acid – Base Reactions
In an acid–base reaction, a proton always
goes from the stronger acid to the
stronger base.
an acid donates a proton to the conjugate
base of any acid with a larger pKa , and the
conjugate base of an acid removes a
proton from any acid with a smaller pKa
Department of Chemistry , College of Science and Mathematics 115
Acid – Base Reactions

Department of Chemistry , College of Science and Mathematics 116

 Acid – Base Reactions
in an acid–base reaction,
the product conjugate acid must be weaker and less reactive
than the starting acid and
the product conjugate base must be weaker and less reactive
than the starting base

Department of Chemistry , College of Science and Mathematics 117

 Predicting Acid – Base Reactions
Water has pKa = 15.74, and acetylene has pKa = 25. Which of the two is
more acidic? Will hydroxide ion react with acetylene?

Department of Chemistry , College of Science and Mathematics 118

 Predicting Acid – Base Reactions
Water has pKa = 15.74, and acetylene has pKa = 25. Which of the two is
more acidic? Will hydroxide ion react with acetylene?

water is a stronger acid than acetylene ; water loses a proton

more easily than acetylene, thus the HO‒ ion has less
affinity for a proton than the HC  C: ‒ ion.
In other words, the anion of acetylene is a stronger base than
hydroxide ion, and the reaction will not proceed as written.

Department of Chemistry , College of Science and Mathematics 119

 Predicting Acid – Base Reactions
Formic acid, HCO2H, has pKa = 3.75, and picric acid,
C6H3N3O7, has pKa = 0.38. Which is stronger, formic
acid or picric acid?

Amide ion, H2N―, is a stronger base than hydroxide

ion, HO― . Which is the stronger acid, H2N―H
(ammonia) or HO―H (water)?

Department of Chemistry , College of Science and Mathematics 120

 Predicting Acid – Base Reactions
Formic acid, HCO2H, has pKa = 3.75, and picric acid,
C6H3N3O7, has pKa = 0.38. Which is stronger, formic
acid or picric acid?
picric acid

Amide ion, H2N―, is a stronger base than hydroxide

ion, HO― . Which is the stronger acid, H2N―H
(ammonia) or HO―H (water)?
water
Department of Chemistry , College of Science and Mathematics 121
 Predicting Acid – Base Reactions
Given the following pKa values, which of the
following reactions is likely to take place?
HCN pKa = 9.31
CH3CO2H pKa = 4.76
CH3CH2OH pKa = 16.00

Department of Chemistry , College of Science and Mathematics 122

Predicting Acid – Base Reactions

Department of Chemistry , College of Science and Mathematics 123

 Predicting Acid – Base Reactions
Will the following reaction take place given
their pKa values ?

yes

Department of Chemistry , College of Science and Mathematics 124

 1.11 Organic Acids and Organic Bases
Organic Acids
characterized by the presence of a positively polarized H atom
two kinds :
1. those that lose a proton from O–H
e.g. methanol and acetic acid

Department of Chemistry , College of Science and Mathematics 125

 1.11 Organic Acids and Organic Bases
Organic Acids

those acids that

contain a hydrogen
atom bonded to an
electronegative
oxygen atom (O-H)

Department of Chemistry , College of Science and Mathematics 126

 1.11 Organic Acids and Organic Bases
Organic Acids

2. those that lose a proton from C–H, a carbon atom next to a

C=O double bond (O=C–C–H)
e.g. acetone

Department of Chemistry , College of Science and Mathematics 127

1.11 Organic Acids and Organic Bases
Organic Acids

those that
contain a
hydrogen atom
bonded to a
carbon atom
next to a C=O
double bond
(O=C-C-H)

Department of Chemistry , College of Science and Mathematics 128

 1.11 Organic Acids and Organic Bases
Organic Acids
Compounds called carboxylic acids, which contain the ‒CO2H grouping, are
particularly common.
They occur abundantly in all living organisms and are involved in almost all
metabolic pathways.
examples : acetic acid, pyruvic acid, and citric acid

Department of Chemistry , College of Science and Mathematics 129

1.11 Organic Acids and Organic Bases
Organic Bases

characterized by the
presence of an atom
with a lone pair of
electrons that can
bond to H+
N-containing
compounds are the
most common organic
bases
e.g. methylamine

Department of Chemistry , College of Science and Mathematics 130

 1.11 Organic Acids and Organic Bases
Organic Bases

oxygen-containing compounds can also act

as bases when reacting with a sufficiently
strong acid

some oxygen-containing compounds can

act as both acids and bases depending on
the circumstances

Department of Chemistry , College of Science and Mathematics 131

 1.11 Organic Acids and Organic Bases
Organic Bases
Methanol and acetone act as acids when they donate a proton but act as
bases when their oxygen atom accepts a proton.

Department of Chemistry , College of Science and Mathematics 132

 1.11 Organic Acids and Organic Bases

amino acids, so named because they are both amines

(‒NH2) and carboxylic acids (‒CO2H), are the building
blocks from which the proteins present in all living
organisms are made
Twenty different amino acids go into making up
proteins ; example - alanine
Interestingly, alanine and other amino acids exist
primarily in a doubly charged form called a zwitterion
rather than in the uncharged form.
Department of Chemistry , College of Science and Mathematics 133
 1.11 Organic Acids and Organic Bases
The zwitterion form arises because amino acids have both
acidic and basic sites within the same molecule and therefore
undergo an internal acid–base reaction.

Department of Chemistry , College of Science and Mathematics 134

 1.12 Acids and Bases : The Lewis Definition
a Lewis acid is a substance that accepts an electron pair
a Lewis base is a substance that donates an electron pair
the donated electron pair is shared between the acid and the base
in a covalent bond

Department of Chemistry , College of Science and Mathematics 135

 1.12 Acids and Bases : The Lewis Definition

The fact that a Lewis acid is able to accept an electron pair

means that it must have either a vacant, low-energy orbital
or a polar bond to hydrogen so that it can donate H+ (which
has an empty 1s orbital).
Thus, the Lewis definition of acidity includes many species in
addition to H+.
e.g. various metal cations, such as Mg2+, and metal
compounds, such as AlCl3 , are Lewis acids because they have
unfilled valence orbitals and can accept electron pairs from
Lewis bases

Department of Chemistry , College of Science and Mathematics 136

1.12 Acids and Bases : The Lewis Definition

Department of Chemistry , College of Science and Mathematics 137

 1.12 Acids and Bases : The Lewis Definition

The Lewis definition of a base - a

compound with a pair of nonbonding
electrons that it can use in bonding to
a Lewis acid - is similar to the
Brønsted–Lowry definition.
e.g. H2O and trimethylamine

Department of Chemistry , College of Science and Mathematics 138

 1.12 Acids and Bases : The Lewis Definition
H2O, with its two pairs of nonbonding electrons on
oxygen, acts as a Lewis base by donating an electron
pair to an H+ in forming the hydronium ion, H3O+

Department of Chemistry , College of Science and Mathematics 139

 1.12 Acids and Bases : The Lewis Definition
trimethylamine acts as a Lewis base by donating an
electron pair on its nitrogen atom to aluminum
chloride

Department of Chemistry , College of Science and Mathematics 140

 1.12 Acids and Bases : The Lewis Definition
• The Lewis definition of acidity includes metal cations, such as
Mg2+ : they accept a pair of electrons when they form a bond
to a base
• Group 3A elements, such as BF3 and AlCl3, are Lewis acids
because they have unfilled valence orbitals and can accept
electron pairs from Lewis bases
• Transition-metal compounds, such as TiCl4, FeCl3, ZnCl2, and
SnCl4, are Lewis acids
• Organic compounds that undergo addition reactions with
Lewis bases are called electrophiles and therefore Lewis
Acids
Department of Chemistry , College of Science and Mathematics 141
 1.12 Acids and Bases : The Lewis Definition

• Most oxygen- and nitrogen-containing

organic compounds are Lewis bases
because they have lone pairs of electrons
• Some compounds can act as both acids
and bases, depending on the reaction

Department of Chemistry , College of Science and Mathematics 142

1.12 Acids and Bases : The Lewis Definition

Department of Chemistry , College of Science and Mathematics 143

1.12 Acids and Bases : The Lewis Definition

the direction of
electron-pair
flow from the
electron-rich
Lewis base to
the electron-
poor Lewis acid
is shown using
curved arrows.

Department of Chemistry , College of Science and Mathematics 144

 1.12 Acids and Bases : The Lewis Definition

A curved arrow always means that a

pair of electrons moves from the
atom at the tail of the arrow to the
atom at the head of the arrow.

Department of Chemistry , College of Science and Mathematics 145

 Using Curved Arrows to Show Electron Flow
Using curved arrows, show how acetaldehyde, CH3CHO,
can act as a Lewis base in a reaction with a strong acid,
HA.

Department of Chemistry , College of Science and Mathematics 146

 Using Curved Arrows to Show Electron Flow
Using curved arrows, show how acetaldehyde, CH3CHO,
can act as a Lewis base in a reaction with a strong acid,
HA.

Department of Chemistry , College of Science and Mathematics 147

exercise

Department of Chemistry , College of Science and Mathematics 148

exercise

Answer
(a) Lewis acid and Lewis base (b) Lewis base
(c) Lewis acid (d) Lewis acid
(e) Lewis acid (f) Lewis base

Department of Chemistry , College of Science and Mathematics 149

 Summary and Key Words

Organic chemistry is the study

of carbon compounds.
Although a division into inorganic
and organic chemistry occurred
historically, there is no scientific
reason for the division.
Fundamentals of Organic Chemistry
John McMurry , 7th ed

FGdLTenido Department of Chemistry , College of Science and Mathematics 150

 Summary and Key Words

An atom is composed of a
positively charged nucleus
surrounded by negatively charged
electrons that occupy specific
regions of space called orbitals.

Fundamentals of Organic Chemistry

John McMurry , 7th ed

FGdLTenido Department of Chemistry , College of Science and Mathematics 151

 Summary and Key Words

Different orbitals have different

energy levels and shapes.
s orbitals are spherical
p orbitals are dumbbell-shaped

Fundamentals of Organic Chemistry

John McMurry , 7th ed

FGdLTenido Department of Chemistry , College of Science and Mathematics 152

 Summary and Key Words

There are two fundamental

kinds of chemical bonds:
ionic bonds
covalent bonds.

Fundamentals of Organic Chemistry

John McMurry , 7th ed

FGdLTenido Department of Chemistry , College of Science and Mathematics 153

 Summary and Key Words
The ionic bonds commonly found
in inorganic salts result from the
electrical attraction of unlike
charges.
The covalent bonds found in
organic molecules result from
the sharing of one or more
electron pairs between atoms.
Fundamentals of Organic Chemistry
John McMurry , 7th ed

FGdLTenido Department of Chemistry , College of Science and Mathematics 154

 Summary and Key Words

Electron sharing occurs when

two atoms approach and their
atomic orbitals overlap.

Fundamentals of Organic Chemistry

John McMurry , 7th ed

FGdLTenido Department of Chemistry , College of Science and Mathematics 155

 Summary and Key Words

Bonds formed by head-on

overlap of atomic orbitals are
called sigma (σ) bonds, and
bonds formed by sideways
overlap of p orbitals are called
pi (π) bonds.
Fundamentals of Organic Chemistry
John McMurry , 7th ed

FGdLTenido Department of Chemistry , College of Science and Mathematics 156

 Summary and Key Words

In the valence bond

description, carbon uses hybrid
orbitals to form bonds in
organic molecules.

Fundamentals of Organic Chemistry

John McMurry , 7th ed

FGdLTenido Department of Chemistry , College of Science and Mathematics 157

 Summary and Key Words

When forming only single bonds

with tetrahedral geometry,
carbon uses four equivalent sp3
hybrid orbitals.

Fundamentals of Organic Chemistry

John McMurry , 7th ed

FGdLTenido Department of Chemistry , College of Science and Mathematics 158

 Summary and Key Words

When forming double bonds,

carbon has three equivalent sp2
orbitals with planar geometry
and one unhybridized p orbital.

Fundamentals of Organic Chemistry

John McMurry , 7th ed

FGdLTenido Department of Chemistry , College of Science and Mathematics 159

 Summary and Key Words

When forming triple bonds,

carbon has two equivalent sp
orbitals with linear geometry
and two unhybridized p
orbitals.

Fundamentals of Organic Chemistry

John McMurry , 7th ed

FGdLTenido Department of Chemistry , College of Science and Mathematics 160

 Summary and Key Words

Organic molecules often have

polar covalent bonds because
of unsymmetrical electron
sharing caused by the
electronegativity of atoms.

Fundamentals of Organic Chemistry

John McMurry , 7th ed

FGdLTenido Department of Chemistry , College of Science and Mathematics 161

 Summary and Key Words

A carbon–oxygen bond is polar

because oxygen attracts the
bonding electrons more
strongly than carbon does.

Fundamentals of Organic Chemistry

John McMurry , 7th ed

FGdLTenido Department of Chemistry , College of Science and Mathematics 162

 Summary and Key Words

A carbon–metal bond is
polarized in the opposite sense
because carbon attracts
electrons more strongly than
metals do.

Fundamentals of Organic Chemistry

John McMurry , 7th ed

FGdLTenido Department of Chemistry , College of Science and Mathematics 163

 Summary and Key Words

A Brønsted–Lowry acid is a
substance that can donate a
proton (hydrogen ion, H+)

A Brønsted–Lowry base is a
substance that can accept a
proton.
Fundamentals of Organic Chemistry
John McMurry , 7th ed

FGdLTenido Department of Chemistry , College of Science and Mathematics 164

 Summary and Key Words

The strength of an acid is

given by its acidity constant,
Ka.

Fundamentals of Organic Chemistry

John McMurry , 7th ed

FGdLTenido Department of Chemistry , College of Science and Mathematics 165

 Summary and Key Words

A Lewis acid is a substance

that can accept an electron
pair.

Fundamentals of Organic Chemistry

John McMurry , 7th ed

FGdLTenido Department of Chemistry , College of Science and Mathematics 166

 Summary and Key Words

A Lewis base is a substance

that can donate an unshared
electron pair.

Most organic molecules that

contain oxygen and nitrogen
are Lewis bases.
Fundamentals of Organic Chemistry
John McMurry , 7th ed

FGdLTenido Department of Chemistry , College of Science and Mathematics 167

Summary and Key Words

E N D

Fundamentals of Organic Chemistry

John McMurry , 7th ed

FGdLTenido Department of Chemistry , College of Science and Mathematics 168

Thank You