What is Organic Chemistry?

• Is the study of Carbon containing compounds

(except oxides of carbon, metal cyanides, cyanates,
carbonates and bicarbonates)

• Compounds of Carbon are central to life in this

planet
• Includes:
• DNA – contain all genetic information
• Proteins – catalyze all the reactions in our body
• Constitutes all essential compounds of our blood,
muscle and skin

• Organic compounds may also be synthesized in

the lab
1
 Properties of Organic vs. Inorganic
Compounds
Properties Organic Inorganic
Contains only C, H, O, N, All other elements in the
1. Composition
S, P, and Halogens periodic table
2. Abundance More than 18 Million Approx. 1.5 M
Molecular, complex Relatively simple
3. Structure
(covalent bonds) (ionic bonds)
4. Isomerism Exhibit isomerism None
Easily decomposes upon
5. Stability Relatively stable
exposure to heat/light
Low (some are liquids or High
6. Melting Point
gaseous at room temp.) (e.g. NaCl, mp 800oC)
7. Combustibility Burns easily Mostly incombustible
2
 Organic Chemistry
• Can bond with one another to form long
chains and rings

• Carbon has the remarkable ability to

bond in multiple ways

• Forms an immense diversity of

compounds

3
 Orbitals and Bonding: Methane
• Carbon has four valence electrons.
• In its ground state, carbon places two electrons in the 2s
orbital and one each in 2p orbitals.

4
 Divalent Carbon

• In this description, carbon should form only two bonds

because it has only two unpaired valence electrons.
• However, the resulting species, CH2, is very unstable
and cannot be isolated under typical laboratory
conditions.
• Note that in CH2, carbon would not have an octet of
electrons.

5
 Tetravalent Carbon
• Promotion of an electron from a 2s to a vacant 2p orbital
would form four unpaired electrons for bonding.
• This higher energy electron configuration is called an
electronically excited state.

• Carbon would form two different types of bonds: three with

2p orbitals and one with a 2s orbital.
• Experimental evidence points to carbon forming four
identical bonds in methane.
6
 Hybrid Orbitals
• To solve this dilemma, chemists have proposed that atoms
like carbon do not use pure s and pure p orbitals in forming
bonds.
• Instead, atoms use a set of new orbitals called hybrid
orbitals.
• Hybridization is the combination of two or more atomic
orbitals to form the same number of hybrid orbitals, each
having the same shape and energy.

7
 Shape and Orientation of sp3 Hybrid
Orbitals
• The mixing of a spherical 2s orbital and three dumbbell
shaped 2p orbitals together produces four hybrid orbitals,
each having one large lobe and one small lobe.

• The four hybrid orbitals are oriented toward the corners of a

tetrahedron and form four equivalent bonds.

8
 Bonding Using sp3 Hybrid Orbitals
Each bond in CH4 is formed by overlap of an sp3 hybrid
orbital of carbon with a 1s orbital of hydrogen.
These four bonds point to the corners of a tetrahedron.

©2020 McGraw-Hill Education.

Four Groups Around an Atom

10
 Drawing Three-Dimensional Structures
A solid line is used for a bond in the plane.
A wedge is used for a bond in front of the plane.
A dashed line is used for a bond behind the plane

©2020 McGraw-Hill Education.

 Equivalent Representations
for Methane
The molecule can be turned in many different ways,
generating equivalent representations.
All of the following are acceptable drawings for CH4.
Each drawing has two solid lines, one wedge, and
one dashed wedge.

©2020 McGraw-Hill Education.

 Wedges and Dashed Wedges
Note that wedges and dashed wedges are used for
groups that are really aligned one behind another.
It does not matter in the following two drawings
whether the wedge or dash is skewed to the left or
right.

©2020 McGraw-Hill Education.

 A Nonbonded Pair of Electrons is
Counted as a “Group”
In ammonia (NH3), one of the four groups attached
to the central N atom is a lone pair.
The group geometry is a tetrahedron.
The molecular shape is referred to as trigonal
pyramidal.

©2020 McGraw-Hill Education.

 The 3-D Structure of Water
In water (H2O), two of the four groups attached to
the central O atom are lone pairs.
The group geometry is a tetrahedron.
The molecular shape is referred to as bent.

©2020 McGraw-Hill Education.

 Varying Bond Angles
In both NH3 and H2O the
Methane (CH4) bond angle is smaller
than the theoretical
tetrahedral bond angle
because of repulsion of
the lone pairs of
Ammonia (NH3) electrons.
The bonded atoms are
compressed into a
smaller space with a
smaller bond angle.
Water (H2O)

©2020 McGraw-Hill Education.

 Hybrid orbitals of NH3 and H2O
Figure 1.9

©2020 McGraw-Hill Education.

Hybridization and Bonding in Ethane

18
 Ethane, CH3–CH3

• Making a model of ethane illustrates one additional

feature about its structure.
• Rotation occurs around the central C–C s bond.

19
 Other Hybridization Patterns
Figure 1.9

Figure 1.10
20
Ethylene (Ethene)

Each carbon is trigonal planar.

Each carbon is sp2 hybridized.

21
sp2 Hybrid Orbitals

22
Three Groups Around an Atom

23
 No Free Rotation in Ethylene

• Unlike the C–C bond in ethane, rotation about the C–C

double bond in ethylene is restricted.
• It can only occur if the p bond first breaks and then reforms, a
process that requires considerable energy.

24
sp Hybrid Orbitals

25
 Acetylene (Ethyne)

Each carbon atom has two unhybridized 2p orbitals that

are perpendicular to each other and to the sp hybrid
orbitals.

26
Two Groups Around an Atom

27
 Triple Bonds
• The side-by-side overlap of two 2p orbitals on one
carbon with two 2p orbitals on the other carbon
creates the second and third bonds of the triple bond.
• All triple bonds are composed of one sigma and two
p bonds.

28
 Summary of Bonding in
Acetylene
Figure 1.13

29
 Summary of Covalent Bonding
Figure 1.14

30
 Bond Length and Bond
Strength
• As the number of electrons between two nuclei
increases, bonds become shorter and stronger.
• Triple bonds are shorter and stronger than double
bonds, which are shorter and stronger than single
bonds.

31
 Carbon–Hydrogen Bonds
• The length and strength of C–H bonds vary depending
on the hybridization of the carbon atom.

32
Carbon-Hydrogen Bonds

33
 Percent s-Character

©2020 McGraw-Hill Education.

 Electronegativity
Electronegativity is a measure of an atom’s attraction for
electrons in a bond.

Electronegativity values for some common elements:

Figure 1.15

35
 Bond Polarity
• Electronegativity values are used 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.

36
 Nonpolar Bonds
• A carbon–carbon bond is nonpolar.

• C–H bonds are considered to be nonpolar because the

electronegativity difference between C and H is small.
• Whenever two different atoms having similar
electronegativities are bonded together, the bond is
nonpolar.

37
 Polar Bonds
• 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 a dipole; that is, separation of
charge.

38
 Depicting Polarity

• The d+ means the indicated atom is electron deficient.

• The 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 toward the
more electronegative element.
• The tail of the arrow is drawn at the less electronegative
element.
39
 Polarity of Molecules
Use the following procedure to determine if a molecule
has a net dipole:
• Use electronegativity differences to identify all of the polar
bonds and the directions of the bond dipoles.
• Determine the geometry around individual atoms by
counting groups, and decide if individual dipoles cancel or
reinforce each other in space.

Figure 1.16 Electrostatic potential plot of CH3Cl

40
 Polar Molecules
A polar molecule has either one polar bond, or two or
more bond dipoles that reinforce each other. An example
is water:

41
 Nonpolar Molecules
A nonpolar molecule has either no polar bonds, or two or
more bond dipoles that cancel. An example is carbon dioxide:

42
 Drawing Organic Molecules—
Condensed Structures
All atoms are drawn in, but the two-electron bond lines are
generally omitted.
Atoms are usually drawn next to the atoms to which they
are bonded.
Parentheses are used around similar groups bonded to the
same atom.
Lone pairs are omitted.

©2020 McGraw-Hill Education.

 Examples of Condensed Structures
Figure 1.3

©2020 McGraw-Hill Education.

 Condensed Structures with C=O
Figure 1.4

In these examples, the only way for all atoms to

have an octet is by having a carbon-oxygen double
bond.

©2020 McGraw-Hill Education.

 Skeletal Structures
Assume there is a carbon atom at the junction of
any two lines or at the end of any line.
Assume there are enough hydrogens around each
carbon to make it tetravalent.
Draw in all heteroatoms and the hydrogens directly
bonded to them.

©2020 McGraw-Hill Education.

Skeletal Structures

47
 Interpreting Skeletal Structures
Figure 1.5

©2020 McGraw-Hill Education.

 Skeletal Structures with Charged
Carbon Atoms
A charge on a carbon atom takes the place of one
hydrogen atom.
The charge determines the number of lone pairs.
Negatively charged carbon atoms have one lone pair
and positively charged carbon atoms have none.

©2020 McGraw-Hill Education.

 Lone Pairs on Heteroatoms
Skeletal structures often leave out lone pairs on
heteroatoms, but don’t forget about them.
Use the formal charge to determine the number of
lone pairs.

©2020 McGraw-Hill Education.

 Isomers
• Sometimes more than one arrangement of atoms (Lewis
structure) is possible for a given molecular formula.

• These two compounds are called isomers.

• Isomers are different molecules having the same
molecular formula. Ethanol and dimethyl ether are
constitutional isomers.
51
 Resonance
• Some molecules cannot be adequately represented by a
single Lewis structure. For example:

• These structures are called resonance structures or

resonance forms. A double-headed arrow is used to
separate the two resonance structures.
• Resonance structures are two Lewis structures having
the same placement of atoms but a different
arrangement of electrons.
52
 Resonance Forms

• 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.
53
 Basic Principles of Resonance Theory

• Resonance structures are not real. An individual resonance

structure does not accurately represent the structure of a
molecule or ion. Only the hybrid does.
• Resonance structures are not in equilibrium with each
other. There is no movement of electrons from one form to
another.
• 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.

54
 The Resonance Hybrid
• 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.

55
 Resonance Hybrids
A “better” resonance structure is the one that has more bonds
and fewer charges.

56