What is Organic Chemistry?
– Definition: Study of carbon-containing compounds.
– Importance: Basis of life, pharmaceuticals, polymers, fuels, etc.
• Organic chemistry is a sub discipline within chemistry
involving the scientific study of the structure, properties, and
reactions of organic compounds and organic materials, i.e.,
matter in its various forms that contain carbon atoms.
• The range of chemicals studied in organic chemistry includes
hydrocarbons (compounds containing only carbon and
hydrogen) as well as compounds based on carbon but also
containing other elements, especially oxygen, nitrogen, sulfur,
phosphorus (included in many biochemicals) and the halogens.
• Organic compounds form the basis of all earthly life and
constitute the majority of known chemicals. The bonding
patterns of carbon, with its valence of four—formal single,
double, and triple bonds, plus structures with delocalized
electrons—make the array of organic compounds structurally
diverse, and their range of applications enormous.
Atomic Structure and Bonding
• Content: in terms of organic chemistry
– Carbon: 4 valence electrons, forms 4 covalent bonds.
– Types of bonds: Single, double, triple.
• Atoms bond together because the compound that results is more stable and
lower in energy than the separate atoms. Energy—usually as heat—is always
released and flows out of the chemical system when a bond forms.
Conversely, energy is added to the chemical system when a bond breaks.
Making bonds always releases energy, and breaking bonds always absorbs
energy.
• Look at methane, CH4, the main constituent of natural gas, for example. The
bonding in methane is not ionic because it would take too much energy for
carbon (1s2 2s2 2p2) either to gain or lose four electrons to achieve a noble-
gas configuration.
• Valence electrons that are not used for bonding remain as dots in structures
and are called lone-pair electrons, or nonbonding electrons.
• The number of covalent bonds an atom forms depends on how many
additional valence electrons it needs to reach a noble-gas configuration.
Hydrogen has one valence electron (1s) and needs only one more to reach
the helium configuration (1s2), so it forms one bond. Carbon has four valence
electrons (2s2 2p2) and needs four more to reach the neon configuration
(2s2 2p6), so it forms four bonds. Nitrogen has five valence electrons
(2s2 2p3), needs three more, and forms three bonds; oxygen has six valence
electrons (2s2 2p4), needs two more, and forms two bonds; and the halogens
have seven valence electrons, need one more, and form one bond.
Introduction to the Hybridization
• Let’s start first by answering this question: Why do we need the
hybridization theory?
• Here is one answer to this. It is confirmed experimentally that the carbon
atom in methane (CH4) and other alkanes has a tetrahedral geometry. A
reminder that in tetrahedral geometry, all the angles are 109.5o and the
bonds have identical lengths. Remember also that covalent bonds form as
a result of orbital overlapping and sharing two electrons between the
atoms. So, in order to predict the valency and geometry of the carbon
atom, we are going to look at its electron configuration and the orbitals.
• C – 1s22s22p2
• The valence electrons are the ones in the 2s and 2p orbitals and these are
the ones that participate in bonding and chemical reactions.
• Hybridization is a theory that is used to explain certain molecular
geometries that would have not been possible otherwise.
sp³ Hybridization
Formation: 1 s + 3 p orbitals → 4 sp³ orbitals.
Geometry: Tetrahedral (109.5° bond angle).
Examples: Methane (CH₄), ethane (C₂H₆).
sp³ Hybridization
• Pay attention that the electron goes uphill as the p subshell is higher in energy
than the s subshell and this is not energetically favorable, but we will see how it
is compensated in the next step when orbitals are mixed (hybridized).
• So, in the next step, the s and p orbitals of the excited state carbon are hybridized
to form four identical in size, shape, and energy orbitals.
• The number of the hybrid orbitals is always the same as the number of
orbitals that are mixed. So, four orbitals (one 2s + three 2p) are mixed and the
result is four sp3 orbitals. These are hybrid orbitals and look somewhat like the s
and p orbitals. And again, we call them sp3 because they are formed from one s
orbital and three p orbitals.
• The formation of these degenerate hybrid orbitals compensates for the energy
uphill of the s-p transition as they have lower energy than the p orbitals.
• The four sp3-hybridized orbitals arrange in a tetrahedral geometry and make
bonds by overlapping with the s orbitals of four hydrogens: This explains the
symmetrical geometry of methane (CH 4) where all the bonds have the same
length and bond angle.
• All four C – H bonds in methane are single bonds that are formed by head-on
(or end on) overlapping of sp3 orbitals of the carbon and s orbital of each
hydrogen.
• The bonds that form by the head-on overlap of orbitals are called σ
(sigma) bonds because the electron density is concentrated on the axis
connecting the C and H atoms.
sp² Hybridization
Formation: 1 s + 2 p orbitals → 3 sp² orbitals + 1 unhybridized p orbital.
Geometry: Trigonal planar (120° bond angle).
Examples: Ethylene (C₂H₄), formaldehyde (CH₂O).
sp² Hybridization
• When the excited state carbon atom is formed, the sp3 hybridization is
not the only option of mixing the orbitals. The sp2 hybridization
occurs when the s orbital is mixed with only two p orbitals as
opposed to the three p orbitals in the sp3 hybridization. So, three
orbitals are mixed, and the outcome is three hybrid orbitals which are
called sp2 hybrid orbitals.
• The resulting 3 sp2 orbitals are then arranged in a trigonal planar
geometry (120o). An important difference here, compared to
the sp3 hybridization, is the left-out (unhybridized) p orbital that did
not participate in the hybridization. This orbital is placed at 90o to the
plane of the trigonal planar arrangement of the three sp2 orbitals:
• Carbon hybridization in Ethylene—C2H4
• Two sp2 hybridized carbon atoms can make a sigma bond by
overlapping one of the three sp2 orbitals and bond with two
hydrogens each and two hydrogens make sigma bonds with each
carbon by overlapping their s orbitals with the other two sp2 orbitals.
• This makes three bonds for each carbon and one p orbital left.
Remember, the standard valency of carbon is four and it likes
to have four bonds.
• This fourth bond is formed by the side-by-side overlap of the
two 2p orbitals on each carbon. This type of bonding by a
side-by-side overlap of the orbitals is called a π bond.
• So, the two carbons in ethylene, which is the first member of
the alkene family, are double-bonded. In each double bond,
there is one sigma and one π bond.
• Here are some key parameters about the sp2 hybridization and
double bonds that you need to know:
• * All the atoms on the double bond are in one plane.
• * The angle between atoms is 120 o.
• * The angle between the plane and p orbitals is 90 o.
sp Hybridization
– Formation: 1 s + 1 p orbital → 2 sp orbitals + 2 unhybridized p orbitals.
– Geometry: Linear (180° bond angle).
– Examples: Acetylene (C₂H₂), carbon dioxide (CO₂).
sp Hybridization
• In sp hybridization, the s orbital of the excited state carbon is
mixed with only one out of the three 2p orbitals. It is
called sp hybridization because two orbitals (one s and one p)
are mixed:
• The resulting two sp hybrid orbitals are then arranged in a
linear geometry (180o) and the two unhybridized 2p orbitals are
placed at 90o, in acetylene – C2H2. The two carbon atoms make
a sigma bond by overlapping the sp orbitals.
• One hydrogen bonds to each carbon atom by overlapping its s
orbital with the other sp orbital.
• The two p orbitals of each carbon overlap to make two π bonds.
• The key parameters of the sp hybridization and triple bond:
• * All the atoms have linear geometry.
• * The angle between atoms is 180o.
• * In a triple bond there is one σ (sigma) and two π (pi) bonds.
Localized Bonding
– Definition: Electrons are
shared between two specific
atoms.
– Examples:
• Single bonds in ethane (C₂H₆).
• Double bonds in ethylene
(C₂H₄).
• Triple bonds in acetylene
(C₂H₂).
– Properties: Fixed electron
density between two atoms.
• Localized bonding refers to sharing electron pairs between two atoms
in a molecule. It is a fundamental concept in chemistry that helps
explain the formation and stability of covalent bonds. In this context,
electrons are considered localized or confined to the region between
the bonded atoms. When two atoms come together to form a covalent
bond, they share electrons to achieve a more stable electron
configuration. The electrons involved in the bond are typically
derived from overlapping atomic orbitals. The most common example
is the sharing of electron pairs between nonmetal atoms.
• Example
• Let’s take the example of hydrogen chloride (HCl) to illustrate
localized bonding. Hydrogen has one valence electron, and chlorine
has seven. To attain a stable electron configuration, hydrogen needs
one more electron, while chlorine needs one electron to complete its
octet. When a hydrogen atom approaches a chlorine atom, their
atomic orbitals overlap, allowing the two electrons to be shared
between the atoms. This sharing forms a localized bond, where the
electron pair spends most of its time between the hydrogen and
chlorine nuclei.
Delocalized Bonding
• Definition: Electrons are shared across multiple atoms, not
confined to a single bond.
• Examples:
– Conjugated systems (e.g., 1,3-butadiene).
– Aromatic compounds (e.g., benzene).
• Properties: Increased stability, resonance, and unique reactivity.
• Delocalized bonding occurs when electrons are not confined to the
region between two specific atoms but are spread out over multiple
atoms or regions within a molecule. This phenomenon arises from
the concept of electron delocalization, wherein electrons have the
freedom to move through a larger portion of the molecule,
resulting in unique bonding properties and behaviors.
• Example
• One classic example of delocalized bonding is found in the
benzene molecule. Benzene consists of a ring of six carbon atoms,
with each carbon atom bonded to one hydrogen atom and one
adjacent carbon atom. The key feature of benzene lies in its
alternating double and single bonds between the carbon atoms.
However, these alternating bonds do not imply fixed positions for
the electrons involved. Instead, the π-electrons in the p-orbitals of
the carbon atoms undergo delocalization, freely moving throughout
the entire ring. This delocalized electron cloud gives rise to the
exceptional stability and aromatic properties exhibited by benzene.
