ORGANIC CHEMISTRY

THEME 1
CHAPTER 1: STRUCTURE AND BONDING

Sefako MaKgatho Health Sciences University Dr RB Maseko

1
 1. ORGANIC vs INORGANIC CHEMISTRY
Organic Chemistry = chemistry of carbon containing
compounds (organic compounds)

• Includes chemistry of compounds from living organisms

• Includes chemistry of polymers (plastics)

• Includes synthesis of non-natural carbon compounds

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 Introduction to Organic Chemistry
Over 10 million compounds have been identified and about 1000
new ones are identified each day

•Organic chemicals affect virtually every facet of

our lives.

Examples of organic Compounds

carbohydrates, proteins, enzymes, vitamins, lipids, nucleic acids ,
synthetic polymers, synthetic fabrics, synthetic rubbers, plastics,
medicines, drugs, organic dyes and so on.

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Why the carbon atom is so special and forms millions of
compounds?

• Carbon has a stronger tendency to catenate since it is a smaller atom

and can form stronger covalent bonds with other carbons.

• Catenation is the ability of atoms of same element to bond covalently

among themselves and form long chains or rings.

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Examples of Organic Compounds

•Methane is the main •Ethanol is the alcohol

component of natural present in alcoholic
gas. beverages.

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 Examples of Organic Cmps

Amoxicillin (antibiotic) Fluoxetine

Generic Name: Prozac
(Antidepressant)

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Examples of Organic Compounds

AZT (azidodeoxythymide)
Generic :Zidovudine
Treats HIV, the virus that
causes AIDS

•Capsaicin is responsible
•for the spiciness of
• peppers, and is used
• for topical pain-relief
medicines.

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Examples of Organic Compounds
•Caffeine is the stimulant found in coffee, tea,
cola beverages, and chocolate.

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 Characteristics of Organic Compounds
Common Features
1. All organic compounds contain carbon atoms (always) and
contain hydrogen atoms (usually).

•Carbon always forms four covalent bonds.

•Hydrogen always forms one covalent bond.

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Characteristics of Organic Compounds
Common Features
2. Carbon forms single, double, and triple bonds to
other carbon atoms.

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Characteristics of Organic Compounds
Common Features
The most common multiple bond between carbon
and a heteroatom is a carbon–oxygen double bond.

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Characteristics of Organic Compounds
Common Features
3. Some compounds have chains of atoms and some
compounds have rings.

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Characteristics of Organic Compounds
Common Features
4. Organic compounds may also contain elements
other than carbon and hydrogen.

•Any atom that is not carbon or hydrogen is called

a heteroatom.
•The common heteroatoms (N, O, F, Cl, Br, and I)
also have nonbonding, lone pairs of e−, so that
each atom is surrounded by an octet of e−.

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Characteristics of Organic Compounds
Common Features
4. Organic compounds may also contain elements
other than carbon and hydrogen.

•Any atom that is not carbon or hydrogen is called

a heteroatom.
•The common heteroatoms (N, O, F, Cl, Br, and I)
also have nonbonding, lone pairs of e−, so that
each atom is surrounded by an octet of e−.

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 WHAT IS CARBON?

• Carbon is an element with atomic number (Z) = 6.

• Its ground state electronic configuration can be

represented as: 1s22s22p2 (or) 1s22s22px12py12pz0
• It is the first element in Group-14 (4a) of Long form of
Periodic table.

• It is a non metal.

• On Pauling's scale, its electronegativity value is around

2.5.

• It usually forms covalent bonds.

• Its valency is 4 since there are four electrons in the outer

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shell i.e., it can form four covalent bonds with other atoms.
 Structure and Bonding
Isotopes: A comparison of two isotopes of carbon

(Same number of protons)

(Different number of neutrons)

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 Structure and Bonding
The Periodic Table: A periodic table of the common elements
seen in organic chemistry

Most common atoms in organic Chemistry are are C, H, N & O.

Other common atoms are the halogens, P & S.

S orbitals P orbitals
Be

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 Structure and Bonding

Rules for sequentially adding electrons:

• Aufbau principle: orbitals fill in order of

increasing energy, lowest to highest.
• Pauli exclusion principle: only two electrons
are allowed to occupy each orbital and the spins
must be paired.
• Hund’s Rule: when filling orbitals of equal
energy (degenerate), one electron is added to
each orbital of equal energy until all have one
electron. The three 2p orbitals are degenerate.

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 Structure and Bonding
Atomic Orbitals:
• Four different kinds of orbitals for electrons, denoted s, p,
d, and f
• s and p orbitals most important in organic and biological
chemistry
• An s orbital has a sphere of electron density and is lower
in energy than the other orbitals of the same shell.
• A p orbital has a dumbbell shape and contains a node of
electron density at the nucleus. It is higher in energy
than an s orbital. There are three p orbitals in the same
shell.

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 Structure and Bonding
First row elments: Since there is only one orbital in the first shell,
and each orbital can hold a maximum of two electrons, there are two
elements in the first row, H and He. Rows represent the major
energy levels.

Second row elements: Each element in the second row of the periodic
table has four orbitals available to accept electrons: one 2s orbital,
and three 2p orbitals, therefore the second row elements are limited to
8 electrons.
Atomic orbitals of Carbon

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 Structure and Bonding
Second Row Elements: filling the 2nd major energy level.
• The second row of the periodic chart consists of eight
elements, obtained by adding electrons to the 2s and
three 2p orbitals.

(The electronic configuration of C = 1s22s22p2 )

S orbitals P orbitals
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Orbitals and Shells

• Orbitals are grouped in shells of increasing size and

energy
• Different shells contain different numbers and kinds of
orbitals
• Each orbital can be occupied by two electrons
• First shell contains one s orbital, denoted 1s, holds only
two electrons
• Second shell contains one s orbital (2s) and three p
orbitals (2p), eight electrons
• Third shell contains an s orbital (3s), three p orbitals (3p),
and five d orbitals (3d), 18 electrons

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Orbitals and Shells

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 Atomic Structure: Electron Configurations

Ground-state electron configuration (lowest energy

arrangement) of an atom lists orbitals occupied by its electrons.
• Aufbau Principle:
• orbitals fill in order of increasing energy from lowest
energy to highest energy: 1s  2s  2p  3s  3p
 4s  3d and so on

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 Electron Configuration of Atoms
The Ground-State Electron Configuration of Elements 1-18

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 Ionic Bonding – electron transfer
• An ionic bond generally occurs when an element on
the far left side of the periodic table combines with an
element on the far right side, ignoring noble gases.
• A positively charged cation formed from the element
on the left side attracts a negatively charged anion
formed from the element on the right side. An example
is sodium chloride, NaCl.

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How many covalent bonds will a particular atom form?
•Atoms with one, two, or three valence e− generally form one, two or
three bonds, respectively.

•Atoms with four or more valence electrons form enough bonds to give
an octet.

predicted
= 8 – number of valence e−
number of bonds

Make sure Number of bonds + Number of lone pairs = 4

Carbon atom: tetravalent

Nitrogen atoms: are trivalent

Oxygen atoms are divalent

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Halogen and hydrogen are monovalent
 Structure and Bonding
Summary: The usual number of bonds of common neutral atoms

Valence electrons are outer shell electrons used in bonding.

Valency is the combining capacity (number of bonds) to an

atom in producing a neutral structure.

Valence electrons 1 4 5 6 7

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 Covalent Bonding – electron sharing
Bonding in Molecular Hydrogen (H2):

• Hydrogen forms one covalent bond.

• When two hydrogen atoms are joined in a NONPOLAR
covalent bond, each has a filled valence shell of two
electrons. It is nonpolar due to equal sharing of e’s.

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 Structure and Bonding
Electronegativity and Bond Polarity:
Electronegativity is a measure of the attraction of an
atom for electrons in a bond.
Electronegativity values for some common elements:

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Polar and Nonpolar Covalent Bonds
• Although all covalent bonds involve sharing of
electrons, they differ widely in the degree of sharing

• We divide covalent bonds into

• nonpolar covalent bonds
• polar covalent bonds

D i fference in
El ectron eg ati vity
Betw een Bo nded Ato ms Typ e of Bond
Less than 0.5 N on pol ar cov alent
0.5 to 1.9 Pol ar co valent
Greater than 1.9 Io ns f orm
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 Electronegativity and Bond Polarity
Electronegativity values are used as a guideline to indicate
whether the electrons in a bond are equally shared or unequally
shared between two atoms.
When electrons are equally shared, the bond is nonpolar.
When differences in electronegativity result in unequal sharing
of electrons, the bond is polar, and is said to have a “separation
of charge” or a “dipole”.

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 Electronegativity and Bond Polarity
A carbon—carbon bond is nonpolar. The same is true
whenever two different atoms having similar electronegativities
are bonded together.
C—H bonds have very slight polarity and are considered to be
nonpolar because the electronegativity difference between C
(2.5) and H (2.2) is small.
Bonding between atoms of different electronegativity values
results in unequal sharing of electrons.

Example: In the C—O bond, the electrons are pulled away

from C (2.5) toward O (3.4), the element of higher
electronegativity. The bond is polar, or polar covalent. The
bond is said to have dipole; that is, separation of charge.
an example of a polar covalent bond is also that of H-Cl
the difference in electronegativity between Cl and H is 3.0 - 2.1 = 0.9

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 Electronegativity and Bond Polarity

d+ means the
indicated atom is
electron deficient.
d- means the
indicated atom is
electron rich.

The direction of polarity in a bond is indicated by an

arrow with the head of the arrow pointing towards the
more electronegative element.
The tail of the arrow, with a perpendicular line drawn
through it, is drawn at the less electronegative element.
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Polar Covalent Bonds
 Bond dipole moment (m):
• Is a measure of the polarity of a covalent bond
• Table below shows average bond dipole moments of
selected covalent bonds

Bond Bond Bond

Dipole Dipole D ipole
Bond (D ) Bond (D ) Bond (D)

H-C 0.3 C-F 1.4 C-O 0.7

H-N 1.3 C-Cl 1.5 C=O 2.3
H-O 1.5 C-Br 1.4 C-N 0.2
H-S 0.7 C-I 1.2 --
C=N 3.5

1-35
 SUMMARY
 Bonds between C and N, O or halogen (X) atoms are polar-
covalent, with the C partially positive (δ+) and the N, O or X
partially negative (δ−).

 Bonds between C and metal atoms such as Li and Mg are also

polar-covalent, with the C partially negative (δ−) and the metal
partially positive (δ+).

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 LEWIS STRUCTURES

Lewis structures are electron-dot structures

for molecules. They show the location of all
valence e−.

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 Lewis Structures
HOW TO Draw a Lewis Structure for molecules and ions
Determine the arrangement of atoms within a molecule Draw a
STEP 1 reasonable skeletal structure, using single bonds to join all the
atoms or by placing two electrons between any two atoms.
 Try to arrange the atoms to yield the most typical number
of bonds for each atom.

 Apply the following guidelines in deciding what element

belongs in the centre of your structure.

-Hydrogen and halogen atoms are never in the center.

-Oxygen atoms are rarely in the center.

-The element with the fewest atoms in the formula is often in the center.

-The atom that is capable of making the most bonds is often in the center

-Less electronegative atom becomes the central atom.

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 Lewis Structures
HOW TO Draw a Lewis Structure for molecules and ions

STEP 1
 Oxygen atoms rarely bond to other oxygen atoms.

 The molecular formula often reflects the molecular structure.

 Carbon atoms commonly bond to other carbon atoms.

H H
For CH4: H C H not H C H H
H

This H cannot form

two bonds.

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Lewis Structures
HOW TO Draw a Lewis Structure
•Also use the common bonding patterns forms
to arrange the atoms

H H H
For CH5N: H C N H not H C N H
H H H

Place four atoms Place three atoms

around C, since C around N, since N
generally forms generally forms
four bonds. three bonds.

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 Lewis Structures
HOW TO Draw a Lewis Structure

Step [2] Count the valence electrons for molecule or

polyatomic ion.
• For uncharged molecules, the total number of valence electrons is the sum
of the valence electrons of each atom.

• For polyatomic cations, the total number of valence electrons is the sum of
the valence electrons for each atom minus the charge.

• For polyatomic anions, the total number of valence electrons is the sum of
the valence electrons for each atom plus the charge

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Lewis Structures
HOW TO Draw a Lewis Structure

Step [2] Count the valence electrons.

•For main group elements, the number of valence
e− is equal to the group number.
•The sum gives the total number of e− that must
be used in the Lewis structure.

For CH3Cl: 1 C x 4e− = 4e−

3 H x 1e− = 3e−
1 Cl x 7e− = 7e−
14 total valence e−
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Lewis Structures
HOW TO Draw a Lewis Structure

Step [3] Arrange the electrons around the atoms.

•Place one bond (two e− / one pair of electrons)

between every two atoms.
•For main group elements (e.g group 2), give not
•more than 8 e−.
•For H, give no more than 2 e−.
•Use all remaining electrons to fill octets with lone
pairs, beginning with atoms on the periphery and then
the central atom.

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Lewis Structures
HOW TO Draw a Lewis Structure

For CH3Cl: H
4 bonds x 2e− = 8 e−
H C Cl
+ 3 lone pairs x 2e− = 6 e−
H 14 e−
e−
2 on 8e−
each H on Cl All valence e− have
been used.

•If all valence electrons are used and an atom still

does not have an octet, proceed to Step [4].

Step [4] Use multiple bonds to fill octets when

needed.
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Lewis Structures
Multiple Bonds

Example Draw the Lewis Structure for C2H4.

Step [1] Arrange the atoms.

H C C H
H H

Step [2] Count the valence e−.

2 C x 4 e− = 8 e−
4 H x 1 e− = 4 e−
12 e− total
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Lewis Structures
Multiple Bonds

Step [3] Add the bonds and lone pairs.

5 bonds x 2 e− = 10 e−
H C C H + 1 lone pair x 2 e− = 2 e−
H H 12 e−

C still does not All valence e− have

have an octet. been used.

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Lewis Structures
Multiple Bonds

Step [4] To give both C’s an octet, change one

lone pair into one bonding pair of
electrons between the two C atoms,
forming a double bond.

H–C–C–H H C C H
H H H H

Answer
Each C now has an octet.

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Exceptions to the Octet Rule
•Most of the common elements generally follow
the octet rule.
•H is a notable exception, because it needs only
2 e− in bonding.

Group 2a; beryllium

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Exceptions to the Octet Rule
 Molecules containing atoms of Group 3A elements, particularly
boron and aluminum

 Boron and Aluminium can have fewer than eight electrons but never more
6 electrons in the
:

:
: F: valence shells of boron : Cl :
and aluminum
: :

: :
:F B : Cl Al
:F: : Cl :
:

:
Boron trifluoride
Aluminum chloride

1-49
Exceptions to the Octet Rule
 Atoms of third-period (row) elements have empty
3d orbitals and may expand their valence shells
to contain more than 8 electrons
• phosphorus may have up to 10

:
: Cl : :O:
: : : :

: Cl : : : :
Cl :
:

: :

:
CH3 -P- CH3 P H- O-P- O-H

:
CH3 : Cl Cl : O-H

:
Trimethyl- Phosphorus Phosphoric
phosphine pentachloride acid
1-50
Exceptions to the Octet Rule
• sulfur, another third-period element, forms compounds
in which its valence shell contains 8, 10, or 12
electrons
: O: : O:
:

:
H-S- H CH 3 -S-CH 3 H-O- S-O-H
:

:
:
:O :

Hydrogen Dimethyl Sulfuric

sulfide sulfoxide acid

1-51
 Structure and Bonding
Formal Charge:: the charge on an atom in a molecule or a polyatomic ion

• By calculating formal charge, we determine how the number of

electrons around a particular atom compares to its number of
valence electrons. Formal charge is calculated as follows:

• The number of electrons “owned” by an atom is determined by its

number of bonds and lone pairs.
• An atom “owns” all of its unshared electrons and half of its shared
electrons.
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 Thus:
N umber of
Formal All One h alf of
= valence electrons un shared + all sh ared
charge in th e neutral,
un bonded atom electrons electrons

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 Structure and Bonding
In formal charge calculation, the number of electrons
“owned” by an atom is shown in these examples:
Example 1

Example 3

Example 2

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formal charge observed with Common
Bonding Patterns

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 Formal Charges

Formal charge = [group number ] – [nonbonding electrons ] – ½ [shared

electrons]
H3O+ NO+
6 – 2 – ½ (6) = +1 6 – 2 – ½ (6) = +1

+
H O H N O+
5 – 2 – ½ (6) = 0
H

• Formal charges are a way of keeping track of

electrons.
• They may or may not correspond to actual charges
in the molecule.

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 Solved Problem 1
Compute the formal charge (FC) on each atom in H3N – BH3.

Solution

• Example: Draw Lewis structures, and show which atom in each

bears the formal charge
- - 2-
(a) NH2 (b) HCO3 (c) CO3
+ - -
(d) CH3 NH3 (e) HCOO (f) CH3 COO
57
 Structure and Bonding
Isomers:
In drawing a Lewis structure for a molecule with several
atoms, sometimes more than one arrangement of atoms
is possible for a given molecular formula.
Example:

Both are valid Lewis structures and both molecules exist.

These two compounds are called isomers.
Isomers are different molecules having the same
molecular formula. Ethanol and dimethyl ether are
constitutional isomers.
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We can view certain molecules and polyatomic ions as if they were able to
resonate—to switch back and forth —between two or more different structures.

Each of these structures is called a resonance structure. The

hypothetical switching from one resonance structure to another is
called resonance.

Thus some molecules cannot be adequately represented by a single

Lewis structure.
For example, two valid Lewis structures can be drawn for the anion
(HCONH)¯.

One structure has a negatively charged N atom and a C=O double

bond; the other has a negatively charged O atom and a C=N double
bond.

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 Structure and Bonding
Resonance:

Resonance structures or
resonance forms.

A double headed arrow is used to separate the two resonance

structures. Only electrons are moved.

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 Structure and Bonding
Introduction to Resonance Theory:
Regarding the two resonance forms of (HCONH)¯ shown
below, it should be noted that:

• Neither resonance structure is an accurate representation

for (HCONH)¯. The true structure is a composite of both
resonance forms and is called a resonance hybrid.
• The hybrid shows characteristics of both structures.
• Resonance allows certain electron pairs to be delocalized
over two or more atoms, and this delocalization adds
stability.
• A molecule with two or more resonance forms is said to be
resonance stabilized. The more forms-THE MORE STABLE 61
 Structure and Bonding
Resonance Theory continued:
The following basic principles of resonance theory should
be kept in mind:

1. Resonance structures are not real. An individual

resonance structure does not accurately represent the
structure of a molecule or ion. Only the hybrid does.
2. Resonance structures are not in equilibrium with each
other. There is no movement of electrons from one form
to another. BUT WE TREAT THEM AS IF THEY DO!
3. Resonance structures are not isomers. Two isomers
differ in the arrangement of both atoms and electrons,
whereas resonance structures differ only in the
arrangement of electrons.
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 Structure and Bonding
Drawing Resonance Structures:
Rule [1]: Two resonance structures differ in the position of multiple
bonds and nonbonded electrons. The placement of atoms and
single bonds always stays the same.

Rule [2]: Two resonance structures must have the same number
of unpaired electrons.

63
 Structure and Bonding
Drawing Resonance Structures:
Rule [3]: Resonance structures must be valid Lewis structures.
Hydrogen must have two electrons and no second-row element
can have more than eight electrons.

64
 Structure and Bonding

Drawing Resonance Structures:

You must master the use of

curved arrows in order to
draw correct resonance
structures.

65
 Curved Arrows:
How to move arrows:

Organic chemists use a curved arrow formalism to show the

movement of a pair of electrons.
 Curved Arrows

Curved arrow notation

shows the movement
of an electron pair
Curved Arrows

.
The tail of the arrow always begins at the
electron pair, either in a bond or lone pair.
 Curved Arrows

Curved arrows are used in resonance

structures to “ push” either  electrons
or lone pairs from one area to another
area.
 Curved Arrows

Curved arrows are used in mechanisms

to “ push” either  electrons, lone
pairs, or  bond electrons from one area
to another area.
 Curved Arrows: concepts
1. (a) Unshared electron pairs (lone pairs) located on a given atom can only
move to an adjacent position to make a new pi bond to the next atom
(example 1). Adjacent positions means neighbouring atoms and/or
bonds.

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The electrons do not jump from one atom to another. The electrons stay
anchored to one atom.

In the first top example, the lone pair on oxygen forms a new bond with
the adjacent carbon atoms. However, the electrons are still part of the
octet on oxygen.

as electrons move around, different atoms may gain or lose their formal
charges. In each of the examples above, notice that the backside of the
arrow always points to a source of electrons (a lone pair or bond).

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(b) Electrons should flow toward a more electronegative atom or positive
charges and away from negative charges. The arrows are moving away
from negative charges and toward positive charges.
In the example below, the pi electrons from the C=O bond moved towards the
oxygen (more electronegative) to form a new lone pair.

(c) pi electrons can also move to an adjacent position to make new pi bond. Once
again, the octet rule must be observed:

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(d) Unless there is a positive charge on the next atom (carbon above), other
electrons will have to be displaced to preserve the octet rule. In resonance
structures these are almost always pi electrons, and almost never sigma
electrons.
HINT 1 : Multiple curved arrows
point will flow in the same
direction. This is because electrons
will flow. The arrows should not
point away from each other or point
toward each other.

HINT 2: Electrons should flow away from

negative charges.

Hint 3: Beware of exceeding the

octet rule, it will lead to invalid
Lewis structure

As the electrons from the carbon lone pair move towards the neighbouring
carbon to make a new pi bond, the pi electrons making up the C=O bond must
be displaced towards the oxygen to avoid ending up with five bonds to the
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central carbon.
Example (d) illustrates that one move we cannot make is to
move a lone pair on one atom to a lone pair on an adjacent
atom because then the electrons will be effectively hopping
from one atom to the next.

The example also suggests that electrons can be moved from

one atom to another atom but it takes multiple curved arrows
like in the examples below.

75
 Structure and Bonding
Resonance Structure Examples and movement of
arrows:

Equivalent structures:

Nonequivalent structures:

In the two examples above, a lone pair is located on

an atom directly bonded to a double bond.
76
 Structure and Bonding

Resonance Structure Examples:

In the above examples, an atom bearing a (+) charge

is bonded either to a double bond or an atom with a
lone pair.

77
 Structure and Bonding
Resonance Hybrids:
• A resonance hybrid is a composite of all possible
resonance structures. In the resonance hybrid, the
electron pairs drawn in different locations in
individual resonance forms are delocalized.
• When two resonance structures are different, the
hybrid looks more like the “better” resonance
structure. The “better” resonance structure is called
the major contributor to the hybrid, and all others are
minor contributors.
• The hybrid is a weighted average of the contributing
resonance structures.

78
To blend the resonance structures into a single resonance hybrid:

Step 1: Draw the skeletal structure, using solid lines for the bonds
that are found in all of the resonance structures.

Step 2: Where there is sometimes a bond and sometimes not,

draw a dotted line.

Step 3: Draw only those lone pairs that are found on every one of
the resonance structures. (Leave off the lone pairs that are on
one or more resonance structure but not on all of them.)

79
Resonance Hybrids
 Structure and Bonding
Resonance Hybrids:
A “better” resonance structure is one that has more bonds
and fewer charges.

81
Comparing Resonance Forms

Resonance forms can be compared using the following criteria,

beginning with the most important:

1. Has as many octets as possible.

2. Has as many bonds as possible.

1. Has the negative charge on the most electronegative atom.

2. Has as little charge separation as possible.

82
Resonance
 Preference 1: filled valence shells or where atoms have a
complete octet of electrons.
 structures in which all atoms have filled valence shells
contribute more than those with one or more unfilled
valence shells
+ •• +
CH 3 O C H CH 3 O C H
•• ••

H H
Greater contribution; Lesser contribution;
both carbon and oxygen have carbon has only 6 electrons
complete valence shells in its valence shell

1-83
Major and Minor Contributors

84 1-84
Resonance
 Preference 2: maximum number of covalent
bonds
• structures with a greater number of covalent bonds
contribute more than those with fewer covalent bonds

+ •• +
CH3 O
••
C H CH3 •O
•
C H

H H
Greater contribution Lesser contribution
(8 covalent bonds) (7 covalent bonds)

1-85
Resonance
 Preference 3: least separation of unlike charge
• structures with separation of unlike charges contribute
less than those with no charge separation
:

:
O: :O: -
CH3 - C- CH3 CH3 - C- CH3
Greater contribution Lesser contribution
(no separation of (separation of unlike
unlike charges) charges)

CH3 O N O CH3 O N O
MAJOR MINOR

1-86
Non-Equivalent Resonance

 Opposite charges should be on adjacent

atoms.

MAJOR MINOR

The most stable one is the one with the smallest

separation of oppositely charged atoms.

87 1-87
 Resonance
 Preference 4: negative charge on the more
electronegative atom
• structures that carry a negative charge on the more
electronegative atom contribute more than those with
the negative charge on the less electronegative atom

O O O
(1) C (2)
C C
H3 C CH3 H3 C CH3 H3 C CH3
(a) (b) (c)
Less er Greater S hould n ot
con trib ution contribu tion be d raw n

1-88
 Determining Molecular Shape
Molecular shape is influenced by bond
angle and bond length.

Right to left
within a period

Top to bottom
within a group
 Structure and Bonding

What is the trend in bond length shown here?

90
 Determining Molecular Shape

Recall the molecular shape is detm. by

applying the VSEPR rules.

Electron pairs repel each other and tend to be as far apart

as possible from each other

Non-bonding electron pairs tend to repel other electrons

more than bonding pairs do (i.e. they are “larger”)
 Valence Shell Electron Pair Repulsion
(VSEPR) Theory is used to predict the
geometry of a molecule

•To determine the shape around a given atom, first determine

how many groups surround the atom.

•A group is either an atom or a lone pair of electrons.

•Use the VSEPR theory to determine the shape.

•The most stable arrangement keeps the groups as far away

from each other as possible. 92
What is the molecular shape of C2H2 ?

Ethyne is linear
What is the molecular shape of CH2CH2?

Ethene is planar.
What is the molecular shape of CH4?

Methane is tetrahedral.
How do you represent the molecular
shape of CH4 on paper?
You must use solid lines, a dash, and
a wedge to show a 3D structure on
paper.
 A Central Atom with One Lone Pair

In ammonia (NH3), one of the four groups attached to the

central N atom is a lone pair.
The three H atoms and the lone pair point to the corners of a
tetrahedron.
The H-N-H bond angle of 107° is close to the theoretical
tetrahedral bond angle of 109.5°.
This shape is referred to as a trigonal pyramid.
 A Central Atom with two Lone Pairs

In water (H2O), two of the four groups attached to the central O atom
are lone pairs. The two H atoms and two lone pairs around O point
to the corners of a tetrahedron.
The H-O-H bond angle of 105° is close to the theoretical tetrahedral
bond angle of 109.5°. Water has a bent shape, because the two
groups around oxygen are lone pairs of electrons.
Common molecular shapes for a central atom with 2-6 bonded
atoms
No of atoms angle Geometry/shape Example

102
Molecular shapes when central atom has lone pairs

NOTE:
• Total number of Electron pairs =
total number of groups

• Number of bonding pairs = number

of atoms around central atom

103
Drawing Organic Structures
Converting a Lewis Structure to a Condensed
Structure
 Rules for Converting a Lewis Structure
to a Condensed Structure

1. Omit bond lines

2. Omit lone pairs
3. Use parentheses for repeating groups
Draw the condensed structure for 2-methyl
propane .
Examples of Condensed Structures
Examples of Condensed Structures
Condensed to Lewis-condensed hybrid
 Drawing Skeletal Structures

1. Omit all hydrogen atoms except for

functional groups H atoms

2. Show all C-C bonds as solid lines

3. End of a line is a terminal carbon.

4. Interior carbon atoms are bends in the line.

Skeletal Structures
 Practice Exercises

Change CH3CH2CH2CH3 into a skeletal

structure.
Skeletal Structures
Skeletal Structures
 Structure and Bonding
Examples of Skeletal Structures
Structure and Bonding
Hybridization
Hybrid Orbitals

• Hybridization of orbitals (L. Pauling)

• the combination of two or more atomic orbitals forms
a new set of atomic orbitals, called hybrid orbitals
• We deal with three types of hybrid orbitals
sp3 (one s orbital + three p orbitals)
sp2 (one s orbital + two p orbitals)
sp (one s orbital + one p orbital)
• Overlap of hybrid orbitals can form two types of bonds
depending on the geometry of overlap
bonds are formed by “direct” overlap
bonds are formed by “parallel” overlap
sp3 Hybrid Orbitals

• orbital overlap pictures of methane, ammonia, and water

Bonding in Ethylene
 Structure and Bonding
Summary of Covalent Bonding Seen in Carbon Compounds
(from Figure 1.15)

144
 Structure and Bonding
Bond Length and Bond Strength:
Note:
• As the percent s-character increases, a hybrid orbital holds
its electrons closer to the nucleus, and the bond becomes
shorter and stronger.
• Although sp3, sp2 and sp hybrid orbitals are similar in
shape, they are different in size.

145
Summary
So, what is hybridization?
Hybridization is a model used to explain how electrons can occupy the
positions needed to form the molecular shapes we see in organic molecules.

Hybridization is the “mixing "and “averaging "of 2s and 2p orbitals to produce

new orbitals of equal shape and energy.

hybridization requires energy, and will therefore only happen when energy can
be provided. The formation of stable bonds between carbon and other atoms
will release energy and will compensate for the energy required by
hybridization.

The driving force for hybridization is the formation of bonding orbitals with the
lowest energy geometry.

In each case the hybrid orbitals are directed as far as possible from one
another to minimize repulsion of bonding electron density as in the VSEPR
theory.(
147
 Structure and Bonding
Polarity of Molecules :
Use the following two-step procedure to determine if a
molecule has a net dipole:
1. Use electronegativity differences to identify all of the
polar bonds and the directions of the bond dipoles.
2. Determine the geometry around individual atoms by
counting groups, and decide if individual dipoles
cancel or reinforce each other in space.
Electrostatic potential plot of CH3Cl

148
 Structure and Bonding
Polarity of Molecules:
A polar molecule has either one polar bond, or two or more
bond dipoles that reinforce each other. An example is water:

A nonpolar molecule has either no polar bonds, or two or

more bond dipoles that cancel. An example is carbon dioxide:

149
Polar and Nonpolar Molecules
 these
molecules have polar bonds and are polar
molecules
direction O N direction
of dip ole of dip ole
H H H H
moment moment
H
Water Ammonia
m = 1.85D m = 1.47D

1-150
Polar and Nonpolar Molecules
 Molecular dipole moment (m): the vector sum of
the individual bond dipole moments in a
molecule
• reported in debyes (D)

direction O
of dip ole C
moment H H
Formaldehyde
m = 2.33 D

1-151
Polar and Nonpolar Molecules
 thesemolecules have polar bonds, but each has
a zero dipole moment

F Cl

O C O B F C
F Cl Cl
Cl
Carbon dioxide Boron trifluoride Carbon tetrachloride
m=0D m=0D m=0D

1-152