Chapter 02 ORGO

Chapter 2
Alkanes and Cycloalkanes:

Introduction to Hydrocarbons
Section 2.1
CLASSES OF
HYDROCARBONS
Compounds of Carbon and Hydrogen
• Hydrocarbons are compounds containing only carbon

and hydrogen
• Hydrocarbon compounds are classified according to their
sources
– Aliphatic hydrocarbons are derived from fats and oils and
contain mostly carbon-carbon single bonds
– Aromatic hydrocarbons are derived from essential oils and
contain single and double carbon-carbon bonds
The simplest hydrocarbon is methane (CH4).
Copyright © 2017 McGraw-Hill Education. All rights reserved. No reproduction or distribution without the prior written consent of McGraw-Hill Education.
Structural Classification of Hydrocarbons
• Hydrocarbons can also be classified according to their

structures
– Alkanes contain only C–C single bonds and C–H bonds
– Alkenes contain at least one C–C double bond
– Alkynes contain at least one C– triple bond
– Arenes contain a ring of alternating C–C and C=C bonds
Section 2.2
ELECTRON WAVES AND

CHEMICAL BONDS
Potential Energy of Covalent Bonds
• The energy of a covalent bond is influenced by electron-
electron and nucleus-nucleus repulsion (+) and electron-
nucleus attraction (–)
• At the equilibrium bonding distance, attractive and
repulsive forces are balanced and bond energy is at a
minimum
Interference of Electron Waves
• Quantum mechanics describes electrons using waves of
probability. These waves overlap or interfere as atoms
form covalent bonds
• Concepts of interference from physics are useful for
describing this process
Constructive interference Destructive interference
Section 2.3
BONDING IN H2: THE

VALENCE BOND MODEL
Valence Bond Model
Electron pair can be shared when half-filled

orbital of one atom overlaps in phase with
half-filled orbital of another.
9
Valence Bond Model
1s H H 1s
in-phase overlap of two half-filled

hydrogen 1s orbitals
H H
σ bond of H2
10
Valence Bond Model
σ Bond: orbitals overlap along

internuclear axis
Cross section of orbital perpendicular to
internuclear axis is circular.
H H
11
Head-on and Side-on Bonding
• The single bond in H2 and other organic molecules is a σ
bond with cylindrical symmetry about the bonding axis
• Multiple bonds derived from side-on overlap of 2p

orbitals are called π bonds
π bonds contain a node along the axis

connecting the bonding nuclei.
Valence Bond Model of H2
The 1s orbitals of two separated hydrogen atoms are far

apart. There is essentially no interaction. Each electron is
associated with a single proton.
13
As the hydrogen atoms approach each other, their 1s

orbitals begin to overlap and each electron begins to feel the
attractive force of both protons.
14
The hydrogen atoms are close enough so that appreciable

overlap of the two 1s orbitals occurs. The concentration of
electron density in the region between the two protons is
more readily apparent. 15
A molecule of H2. The two hydrogen 1s orbitals have been

replaced by a new orbital that encompasses both hydrogens
and contains both electrons.
16
Section 2.4
BONDING IN H2: THE

MOLECULAR ORBITAL MODEL
Principles of Molecular Orbital Theory
1. Just as electrons in atoms occupy atomic orbitals,
electrons in molecules occupy molecular orbitals
2. There are three types of molecular orbitals:
1. Antibonding orbitals (*): higher in energy than atomic
orbitals, with nodes between the bonding nuclei
2. Nonbonding orbitals: atomic orbitals not involved in
bonding
3. Bonding orbitals: lower in energy than atomic orbitals, with
significant density between the bonding nuclei
3. Atomic orbitals are added, subtracted, and scaled to
generate molecular orbitals
4. The number of molecular orbitals must equal the total
number of atomic orbitals in the atoms of the molecule
Like atomic orbitals, molecular orbitals have energy, shape, and
occupancy. MOs often have delocalized shapes.
Constructing Molecular Orbitals
• Molecular orbitals are weighted sums or linear
combinations of atomic orbitals
• For example, two 1s orbitals in hydrogen are added (in-
phase or constructive) and subtracted (out-of-phase or
distructive) to generate the MOs of H2
• Note how the shapes reflect constructive interference
(bonding) and destructive interference (antibonding)
Orbital Energy Diagram for H2
• An orbital energy diagram shows the atomic orbitals
that contribute to each MO, the relative energies of AOs
and MOs, and the occupancy of MOs
The antibonding MO (σ*) is

1s – 1s higher in energy than the
1sH AO.
The bonding MO (σ) is

lower in energy than the 1sH
AO.
1s + 1s Only the bonding AO is

occupied.
Section 2.5
INTRODUCTION TO ALKANES:
METHANE, ETHANE, AND
PROPANE
Alkanes
• Alkanes have the general formula CnH2n+2 and consist of
C–C and C–H bonds
• The simplest alkanes are methane, ethane, and
propane. Boiling point increases with molecular weight
• All three molecules have tetrahedral geometry at their

carbon atoms
Section 2.6
SP3 HYBRIDIZATION AND

BONDING IN METHANE
Alkanes: A Geometric Quandary
• Valence bond theory suggests that bonds are derived
from overlap of atomic orbitals. How can tetrahedral
geometry be explained by overlap of s orbitals and p
orbitals at 90º to one another?
• We make use of a mathematical device that explains the

observed geometry
• Hybridization: atomic orbitals on the same atom are
mixed to produce a new set of hybrid atomic orbitals
sp3 Hybridization
• To produce the four hybrid AOs on carbon needed for bonding in
CH4, one 2s orbital and three 2p orbitals are mixed
The resulting sp3 hybrids point to

the vertices of a tetrahedron.
Shape of sp3 hybrid orbitals
p + –
take the s orbital and place it on

top of the p orbital
s +
26
s+p + + –
reinforcement of electron wave in

regions where sign is the same
destructive interference in regions of
opposite sign
27
sp hybrid + –
orbital shown is sp hybrid

analogous procedure using three s orbitals
and one p orbital gives sp3 hybrid
shape of sp3 hybrid is similar
28
sp3 hybrid + –
The hybrid orbital is not symmetrical.

The higher probability of finding an electron on
one side of the nucleus than the other leads to
stronger bonds.
29
sp3 Hybridization
• The four C–H bonds in CH4 are formed from overlap of the sp3
hybrid AOs with 1s AOs on the hydrogens
This is a wedge-and-dash
drawing which is commonly
used to show the 3D
configuration of a molecule.
Section 2.7
BONDING IN ETHANE
Bonding in Ethane
• Both carbon atoms in ethane (H3CCH3) have four single
bonds, tetrahedral geometry, and sp3 hybridization
• The central C–C bond is derived from overlap of two sp3
hybrid AOs
The four σ bonds around each carbon

atom point to sp3 hybridization.
Section 2.8
SP2 HYBRIDIZATION AND

BONDING IN ETHYLENE
Structure and Hybridization of C2H4
• Ethylene (H2CCH2) contains a double bond and trigonal
planar geometry at each carbon atom
• The hybridization model can explain both the trigonal

planar geometry and the C–C double bond
• The carbon atoms are sp2 hybridized
sp2 Hybridization in Ethylene
• To form the three σ bonds at each carbon in ethylene, one 2s AO
and two 2p AOs are mixed to produce three sp2 hybrids
• The sp2 hybrids are two-dimensional, and one unhybridized 2p
orbital remains perpendicular to the plane of the hybrids
Forming the C–C σ and π Bonds
• sp2 hybrids on the carbons overlap
to form the C–C σ bond
• sp2 hybrids overlap with 1sH orbitals

to form the C–H bonds
• Unhybridized 2p orbitals on the

carbons overlap in a side-on manner
to form the C–C π bond
Section 2.9
SP HYBRIDIZATION AND
BONDING IN ACETYLENE
Structure and Hybridization in C2H2
• Acetylene (HCCH) contains a triple bond and linear
geometry at each carbon atom
• The hybridization model can explain both the linear

geometry and the C–C triple bond
• The carbon atoms are sp hybridized
sp Hybridization in Acetylene
• To form the two σ bonds at each carbon in acetylene, one 2s AO
and one 2p AO are mixed to produce two sp hybrids
• The sp hybrids are one-dimensional, and two unhybridized 2p
orbitals remain perpendicular to the axis of the hybrids
Forming the C–C σ and π Bonds
• sp hybrids on the carbons overlap
to form the C–C σ bond
• sp hybrids overlap with 1sH orbitals

to form the C–H bonds
• Unhybridized 2p orbitals on the

carbons overlap in a side-on manner
to form the C–C π bonds
• The two π bonds are perpendicular
to one another
Section 2.10
MOLECULAR ORBITALS AND

BONDING IN METHANE
Canonical MOs of CH4
• Thus far we have imagined bonds as arising from
localized overlap of orbitals
• In general, orbitals on multiple atoms can overlap to form
delocalized molecular orbitals
• Such canonical MOs describe electrons in molecules
well, but can be difficult to interpret
The canonical MOs of methane

include one low-energy orbital
derived from overlap of s orbitals
and three degenerate, higher-
energy orbitals derived from
overlap of s and p orbitals.
Section 2.11 (reading section)
ISOMERIC ALKANES: THE

BUTANES
Isomeric Alkanes
• Methane, ethane and propane have no constitutional
isomers
• Butane (C4H10) has two constitutional isomers
– Linear n-butane, CH3CH2CH2CH3
methylene
methyl carbon
carbon
– Branched isobutane or 2-methylpropane, (CH3)2CHCH3
methine
carbon
In both isomers, all carbons are sp3
hybridized and tetrahedral.
Section 2.12
HIGHER N-ALKANES
Higher n-Alkanes
• n-Pentane (C5H12) and n-hexane (C6H14) are linear
alkanes containing five and six carbons respectively
CH3(CH2)3CH3 CH3(CH2)4CH3
• Their structural formulas may also be written in

condensed form as CH3(CH2)nCH3
Section 2.13
THE C5H12 ISOMERS

Isomers of C5H12
• The compound C5H12 may include zero, one, or two
branched methyl groups. n-Pentane contains zero
methyl branches
• Isopentane contains one methyl branch on an n-butane

chain
• Neopentane contains two methyl branches from the

central carbon in n-propane
Counting and Naming Alkane Isomers
• There is not a general way to calculate the number of

isomers associated with a
molecular formula
• In simple cases, we can
enumerate possible isomers
by systematically moving
branches around and
changing their composition
• The IUPAC nomenclature
system is a rigorous and
and systematic method for
naming alkanes
Section 2.14
IUPAC NOMENCLATURE OF
UNBRANCHED ALKANES
Naming Linear Alkanes
• The IUPAC rules are used to name all organic compounds
• Alkanes are the foundation; we can think of organic compounds
as derivatives of alkanes
• Linear alkane chains are named using a prefix for the number of
carbons and the suffix –ane
The first ten prefixes

are worth memorizing.
Section 2.15
APPLYING THE IUPAC RULES:

THE NAMES OF THE C6H14
ISOMERS
Structural Isomers of C6H14
• There are five structural or constitutional isomers with
the molecular formula C6H14
• The linear isomer, CH3(CH2)4CH3, is simply called
hexane
n-hexane is not a correct IUPAC name!

• The other isomers contain branches—short chains of
carbons attached to a longer base or parent chain
• How do we name a compound with branches
systematically?
Naming Branched Alkanes
• Consider the structure at right.
1. Identify the longest continuous carbon chain
• Consider the structure at right. five carbons
methyl
2. Identify the substituents, branches attached to the
parent chain
1 2 3 4 5

methyl
parent chain
3. Number the carbons of the longest chain such that the
substituent at the first branching point gets the smallest
number possible
1 2 3 4 5

methyl
parent chain
3. Number the carbons of the longest chain such that the
substituent at the first branching point gets the smallest
number possible
4. Write the name of the compound
1. List substituents in alphabetical order, preceded by their
number location
2. Write the parent chain as an alkane at the end of the name
2-methylpentane
Section 2.16
ALKYL GROUPS
Beyond the Methyl Group
• What do we call substituents other than CH3?
• Other alkane substituents are known collectively as alkyl
groups
• The names of alkyl groups follow the IUPAC rules for
alkanes, but end in the suffix –yl
• Alkyl groups are classified by their substitution pattern at

the point of attachment
Naming Alkyl Groups
• Importantly, the parent chain of an alkyl substituent must
start from the point of attachment
NOT 2-propyl!
• Alkyl groups are often known by common names
Common Alkyl Groups
Section 2.17
IUPAC NAMES OF HIGHLY

BRANCHED ALKANES
Highly Branched Alkanes
• The IUPAC rules are flexible enough to apply to any
alkane. Consider 4-ethyloctane below
• When we add a methyl substituent to carbon 3…
• The name becomes 4-ethyl-3-methyloctane
Highly Branched Alkanes
• Multiple copies of a substituent are denoted using the
replicating prefixes di–, tri–, tetra–, etc.
4-ethyl-3,5-dimethyloctane
• These prefixes as well as italicized prefixes like sec- and

tert- are ignored when alphabetizing
• Complications may arise when numbering…
The “First Point of Difference” Rule
• The two numbering schemes below both ensure that the
substituent(s) at the first branching point have the
number “2”
• The blue scheme includes a second methyl group with

the number “2”; the next substitutent in the pink scheme
is a 3-methyl
• At the first point of difference, the blue scheme has the
smaller number (2-methyl versus 3-methyl
2,2,6,6,7-pentamethyloctane 2,3,3,7,7-pentamethyloctane
Section 2.18
CYCLOALKANE
NOMENCLATURE
Cycloalkanes: Cyclic Alkanes
• Cycloalkanes are cyclic alkanes with the general
formula CnH2n, where n > 2
• Found in a wide variety of organic compounds
• Parent cycloalkanes are named using the prefix cyclo–

• Substituents are named in the usual way
Where do we start numbering?

Numbering Cycloalkanes
• As for alkanes, we number cycloalkanes so that the
substituent at the first point of difference gets the lowest
number
• Typically, this means that the most substituted carbon is

C1
Cycloalkanes as Substituents
• Simple cycloalkanes bonded to longer alkyl chains are
treated as cycloalkyl substituents
Note that the cyclobutane ring is smaller

than the attached pentane chain.
Section 2.19
INTRODUCTION TO
FUNCTIONAL GROUPS
Introduction to Functional Groups
• Functional groups are structural units containing
heteroatoms or multiple bonds. A functional group can be
associated with its characteristic reactivities (function). It
is common to classify compounds according to their FG.
• We can imagine (and name) many organic compounds
as alkyl derivatives of functional groups
• Alkyl halides contain an alkyl group bound to a halogen
atom
• Alcohols contain an alkyl group bound to a hydroxyl

group
Section 2.20
SOURCES OF ALKANES AND

CYCLOALKANES
Alkanes from Petroleum
• Petroleum deposits are a very common source of
alkanes and other hydrocarbons
• Crude oil can be distilled over a range of temperatures to

separate it into pure compounds
Biological Sources
• Organic compounds, including alkanes, are commonly
found in biological organisms
– The linear pentacosane, CH3(CH2)23CH3, is present in the
waxy covering of many insects
– Hentriacontane, CH3(CH2)29CH3, is found in beeswax and
other natural waxes
• Biological compounds based on cycloalkanes are rare,
but do appear in some contexts
Section 2.21
PHYSICAL PROPERTIES OF
ALKANES AND CYCLOALKANES
van der Waals force/interaction
Attractive forces between neutral molecules are
referred to as van der Waals force. There are
generally three types:
1. dipole-dipole (including H-bonding)
2. Dipole/induced dipole
3. Induced dipole/induced dipole
Boiling point of a substance is solely determined
by its intermolecular force.
1. In the gaseous state, molecules essentially
experience zero intermolecular force as they
are far apart from each other.
2. In the liquid state, molecules are held together
by attractive intermolecular interaction.
Intermolecular Forces in Alkanes
• Alkanes consist of nonpolar C–C bonds and very weakly
polarized C–H bonds. Hence, they are nonpolar overall
• However, alkane molecules usually exhibit instantaneous
dipoles due to asymmetric distributions of electrons at
any point in time
• Instantaneous dipoles can induce a dipole in a nearby
molecule, resulting in attractive forces
• The instantaneous dipole–induced dipole force is called
a London dispersion force
Boiling Points
• Boiling points of alkanes increase with molecular weight
• Branched alkanes have lower boiling points than linear
alkanes
Branched alkanes have
smaller surface area than
isomeric linear alkanes.
van der Waals forces are

weaker in branched alkanes
as a result.
Melting Points
• Solid alkanes are typically soft and waxy substances
with relatively low melting points
• Molecules in the solid pack together closely
• Melting points points of alkanes also increase with
molecular weight
Branched alkanes have lower melting points than linear
alkanes
Solubility in Water
• Alkanes are nonpolar substances characterized by very
weak van der Waals interactions
• van der Waals interactions of alkanes with water cannot
overcome the strength of hydrogen bonds in water
• Hence, alkanes are not generally soluble in water
• The Hydrophobic Effect: alkane molecules cluster
together and exclude water molecules
Section 2.22
CHEMICAL PROPERTIES:
COMBUSTION OF ALKANES
Alkanes React with Oxygen
• Alkanes are highly reduced forms of organic compounds,
which contain only C–C and C–H bonds
• They react vigorously and exothermically with O2 gas in
combustion reactions to form CO2 and H2O
Heats of Combustion
Branching and Stability
• Intramolecular forces affect heats of combustion of isomeric
alkanes
• Branched isomers generally have less exothermic heats of
combustion, indicating greater stability
Attractive intramolecular
forces in the branched
isomer stabilize it relative
to n-octane.
Section 2.23
OXIDATION AND REDUCTION

IN ORGANIC CHEMISTRY
Calculating Oxidation Number
• The oxidation number of carbon is calculated by
assuming:
1. The overall oxidation number of a neutral compound is zero
2. Electronegative heteratoms have oxidation number –n,
where n is the number of bonds to carbon
3. Electropositive heteroatoms have oxidation number +n
4. Hydrogens have oxidation number +1
• In essence, subtract 1 for each bond to a nonmetal and
add 1 for each bond to hydrogen or a metal
Oxidation and Reduction at Carbon
• An oxidation reaction increases the oxidation number of
carbon by replacing a C–H bond with a C–X bond
C–H C–X
• A reduction reaction decreases the oxidation number of

carbon by replacing a C–X bond with a C–H bond
C–X C–H
Oxidation and Reduction at Carbon
• An oxidation reaction increases the oxidation number of
carbon by replacing a C–H bond with a C–X bond
• A reduction reaction decreases the oxidation number of

carbon by replacing a C–X bond with a C–H bond

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Chapter 02 ORGO

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Chapter 2

Alkanes and Cycloalkanes:

• Hydrocarbons are compounds containing only carbon

The simplest hydrocarbon is methane (CH4).

• Hydrocarbons can also be classified according to their

ELECTRON WAVES AND

BONDING IN H2: THE

Electron pair can be shared when half-filled

in-phase overlap of two half-filled

σ Bond: orbitals overlap along

• Multiple bonds derived from side-on overlap of 2p

π bonds contain a node along the axis

The 1s orbitals of two separated hydrogen atoms are far

As the hydrogen atoms approach each other, their 1s

The hydrogen atoms are close enough so that appreciable

A molecule of H2. The two hydrogen 1s orbitals have been

BONDING IN H2: THE

The antibonding MO (σ*) is

The bonding MO (σ) is

1s + 1s Only the bonding AO is

• All three molecules have tetrahedral geometry at their

SP3 HYBRIDIZATION AND

• We make use of a mathematical device that explains the

The resulting sp3 hybrids point to

take the s orbital and place it on

reinforcement of electron wave in

orbital shown is sp hybrid

The hybrid orbital is not symmetrical.

The four σ bonds around each carbon

SP2 HYBRIDIZATION AND

• The hybridization model can explain both the trigonal

• sp2 hybrids overlap with 1sH orbitals

• Unhybridized 2p orbitals on the

• The hybridization model can explain both the linear

• sp hybrids overlap with 1sH orbitals

• Unhybridized 2p orbitals on the

MOLECULAR ORBITALS AND

The canonical MOs of methane

ISOMERIC ALKANES: THE

– Branched isobutane or 2-methylpropane, (CH3)2CHCH3

• Their structural formulas may also be written in

THE C5H12 ISOMERS

• Isopentane contains one methyl branch on an n-butane

• Neopentane contains two methyl branches from the

• There is not a general way to calculate the number of

The first ten prefixes

APPLYING THE IUPAC RULES:

n-hexane is not a correct IUPAC name!

1. Identify the longest continuous carbon chain

1. Identify the longest continuous carbon chain

• Consider the structure at right. five carbons

• Consider the structure at right. five carbons

• Alkyl groups are classified by their substitution pattern at

• Alkyl groups are often known by common names

IUPAC NAMES OF HIGHLY

• When we add a methyl substituent to carbon 3…

• The name becomes 4-ethyl-3-methyloctane

• These prefixes as well as italicized prefixes like sec- and

• The blue scheme includes a second methyl group with

• Parent cycloalkanes are named using the prefix cyclo–

Where do we start numbering?

• Typically, this means that the most substituted carbon is

Note that the cyclobutane ring is smaller

• Alcohols contain an alkyl group bound to a hydroxyl