Ch. 4 Hydrocarbons

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MBMB 1212 : General Chemistry
Chapter 4
Hydrocarbons – Alkanes, alkenes and alkynes
September – December 2022
Forms of Carbon
• Diamond
• Graphite
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Forms of Carbon
• Buckminsterfullerene
“Bucky Balls”
Carbon nanotubes, can be thought of as a

rolled-up sheet of graphite capped on
either end by half of a buckyball.
Nanotubes have many potential
applications.
They can be spun into fibers that are
stronger and ligher than steel, and they
can also be made to carry electrical
currents more efficiently than metals
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• Buckyballs may be used to trap free radicals generated during an

allergic reaction and block the inflammation that results from an
allergic reaction
• The antioxidant properties of buckyballs may be able to fight the
deterioration of motor function due to multiple sclerosis
• Combining buckyballs, nanotubes, and polymers to produce
inexpensive solar cells that can be formed by simply painting a
surface
• Buckyballs may be used to store hydrogen, possibly as a fuel tank
for fuel cell powered cars
• Buckyballs may be able to reduce the growth of bacteria in pipes
and membranes in water systems
• Researchers are attempting to modify buckyballs to fit the
section of the HIV molecule that binds to proteins, possibly
inhibiting the spread of the virus
• Making bullet proof vests with inorganic (tungsten disulfide)
buckyballs
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Hydrocarbons
• Organic molecules are grouped into families
− Members of a family share common structural, physical, and
chemical characteristics
• There are four families that contain molecules made of

only carbon and hydrogen
• Hydrocarbons
− Alkanes
− Alkenes
− Alkynes
− Aromatic compounds
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Hydrocarbons
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Alkanes
• Alkanes are hydrocarbons that contain only
carbon-carbon single bonds
– Every carbon atom participates in 4 single bonds,
either to another carbon or to a hydrogen
– Every hydrogen atom is bonded to a carbon by a single
bond
Alkanes
– Alkanes in which the carbons are connected in a
straight chain are called normal alkanes
H H H H H H
H C C C C C C H n-hexane
H H H H H H
– Alkanes that are branched are called branched chain

alkanes
H
H C H
H H H H 2-methyl-pentane
H C C C C C H
H H H H H
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Properties of alkanes - Physical

• At room temperature:
– Small alkanes with 1–4 carbons are gasses
– Medium size alkanes with 5–12 carbons are liquids
– Large alkanes with 13–20 carbons are oils
– Extra large alkanes with 20–100 carbons are solids
like tar and wax
– Supersized alkanes called polymers can have
thousands or millions of carbon atoms in each
molecule
• What type of properties would you expect such
polymers to possess?
• Why? Consider London forces
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Properties of alkanes
Boiling points
The boiling points for alkanes isomers are shown to demonstrate that
branching decreases the surfaces area, weakens the intermolecular
forces, and lowers the boiling point
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Properties of alkanes
Solubility
Alkanes (both alkanes and cycloalkanes) are virtually insoluble in
water, but dissolve in organic solvents. However, liquid alkanes are
good solvents for many other non-ionic organic compounds
In most organic solvents, the primary forces of attraction between the

solvent molecules are Van der Waals - either dispersion forces or
dipole-dipole attractions. Therefore, when an alkane dissolves in an
organic solvent, the Van der Waals forces are broken and are replaced
by new Van der Waals forces between the substance and solvent
The two processes more or less cancel each other out energetically;
thus, there is no barrier to solubility
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Nomenclature of Alkanes
In the early nineteenth century, organic compounds were
often named at the whim of their discoverers. Here are just
a few examples
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Alkanes nomenclature - IUPAC
• In 1892, as the number of known molecules grew,

chemists decided that a SYSTEMATIC naming system
was needed
– IUPAC (International Union of Pure and Applied
Chemistry) system
• We can learn the IUPAC system instead of having to

memorize a common name for every molecule
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Naming alkanes- Finding the parent chain

The IUPAC system:
1. Find the parent chain, the longest consecutive chain
of carbons
Use Table 4.1 (next slide) to look up the prefix that

corresponds to the number of carbons in the parent
chain 14
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– If the parent chain has 9

carbons, the parent name
is nonane
– It would be smart to
memorize the names for
chains 1 to 12 carbons in
length
– Use Table 4.1 to look up
the prefix that
corresponds with the
number of carbons in the
parent chain
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– If there is more than one possible parent chain,

choose the one with the most substituents (side
chains) attached
• What is the parent name for this compound?
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– If the parent chain is cyclic (a ring of carbons), add

the prefix, “cyclo” to the beginning of the parent
name
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Naming alkanes- Identifying substituents
2. Identify and name substituents (side chains)
– Count the number of carbons in each side group, and

use the terms from Table 4.2 to name the substituents
– The terms in Table 4.2 are the same as those in Table
4.1, except they end in “yl” instead of “ane”
– Name the parent and substituents above
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– A ring can be either a parent chain or a substituent

depending on the number of carbons
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– Some substituents have complex branches
– How many carbons are in the highlighted

substituent above?
– Why is it improper to name it a PENTYL group?
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– Some branched substituents have COMMON names

that you may want to memorize, because they are
used more frequently than their IUPAC names
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Naming alkanes-
Numbering the parent chain
3. Number in sequence the consecutive carbons in the
parent chain and assign a locant to each substituent
– The number or LOCANT is used to communicate
where each substituent is attached to the parent
chain
• The molecules above are isomers, and they have the

same parent name. Their full name must
differ though, because they are not identical
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Naming alkanes-
• Guidelines to follow when numbering the
parent chain:
1. If ONE substituent is present, number the parent
chain so that the substituent has the lowest number
possible
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Naming alkanes-
2. When multiple substituents are present, number
the parent chain to give the first substituent the
lowest number possible
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Naming alkanes-
3. If there is a tie, then number the parent chain so
that the second locant gets the lowest number
possible
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Naming alkanes-
Assembling the entire name
4. To assemble the complete name, assign a locant to
each substituent, and list them before the parent
chain name in alphabetical order
5. A prefix is used (di, tri, terta, penta, etc.) if multiple
substituents are identical
6. Prefixes are NOT used for alphabetical purposes,
except for the prefix “iso”
• Name :
1,1,3-trimethylcyclohexane
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Naming alkanes- Summary

1. Identify the parent chain, the longest consecutive
chain of carbons
2. Identify and name substituents (side chains)
3. Number the parent chain and assign a locant (and
prefix if necessary) to each substituent
– Give the first substituent the lowest number
possible
4. List the numbered substituents before the parent
chain name in alphabetical order
– Ignore prefixes (except iso) when ordering
alphabetically
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Practice problems
• Name the following alkane
• Draw the bond-line representation for;

i. 1-tert-butyl-2-ethyl-4-methyl-3propylcyclohexane
ii.3-ethyl-2,2-dimethyl-hexane
iii.3-ethyl-2methyl-heptane
iv.4-ethyl-2,3-dimethylheptane (also give condensed
structural formula)
v.1-methyl-3-propylcyclohexane
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Naming alkanes- Bicyclic compounds

• There are many compounds with two fused rings
called bicyclic compounds
• To name a bicyclic compound, include the prefix

“bicyclo” in front of the normal name ending in -ane.
For example, the compounds below could both be
named, bicycloheptane
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• Both compounds consist of two rings and seven carbon atoms.

Yet, the compounds are clearly different, which means that the
name of the parent needs to contain more information.
• Specifically, it must indicate the way in which the rings are
constructed (the constitution of the compound). In order to do
this, we must identify the two bridgeheads. These are the two
carbon atoms where the rings are fused together
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There are three different paths connecting these two bridgeheads.
For each path, count the number of carbon atoms, excluding the
bridgeheads themselves. In the compound above, one path has two
carbon atoms, another path has two carbon atoms, and the third
(shortest path) has only one carbon atom. These three numbers,
ordered from largest to smallest, [2.2.1], are then placed in the
middle of the parent surrounded by brackets
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If a substituent is present, the parent must be numbered properly in
order to assign the correct locant to the substituent. To number the
parent, start at one of the bridgeheads and begin numbering along
the longest path, then go to the second longest path, and finally go
along the shortest path. For example, consider the following bicyclic
system:
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In this example, the methyl substituent did not get a low number. In
fact, it got the highest number possible because of its location.
Specifically, it is on the shortest path connecting the bridgeheads.
Regardless of the position of substituents, the parent must be
numbered beginning with the longest path first. The only choice is
which bridgehead will be counted as C1; for example:
We must start numbering at the

bridgehead that gives the
substituent the lowest possible
number.
6-methylbicyclo[3.2.1]octane
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Skill builder
1. Name each of the following compounds:
2. Draw a bond-line structure for each of the following

compounds:
(a) 2,2,3,3-Tetramethylbicyclo[2.2.1]heptane
(b) 8,8-Diethylbicyclo[3.2.1]octane
(c) 3-Isopropylbicyclo[3.2.0]heptane
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Cis-trans isomerism
• When naming a disubstituted cycloalkane, use the

prefix cis when there are two groups on the same side
of the ring
• Use the prefix trans when two substituents are on
opposite sides of a ring
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Cis-trans isomerism
• These two structures are NOT constitutional

isomers. WHY?
• They are STEREOISOMERS
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Skill builder
• Draw the condensed structural formulas for the

following molecules:
i. 1-ethyl-2-methylcyclopentane
ii. 1,1-dimethylcyclobutane
iii. 1,1-dimethyl-2-propylcyclopropane
• Do any of these molecules have cis- and trans-

geometric isomers?
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Polycyclic systems
• There are many important structures that result when
more than one ring is fused together
• We already looked at bicycloalkanes. Here are a couple
more
• Camphor and camphene are fragrant natural

products isolated from evergreens
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Polycyclic systems
There are many biologically important steroids, all of

which involve fusing cycloalkanes as part of their structure
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Naming Drugs
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Naming Drugs
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Sources and uses of alkanes
• Petroleum, which literally means rock oil is the main

source of alkanes
• Petroleum is a mixture of hundreds of hydrocarbons,
mostly alkanes, with varying numbers of carbons and
varying degrees of branching
• The alkanes in petroleum with 5 to 12 carbons per
molecule are most valuable, and they can be separated
from the rest of the oil by distillation
– HOW does distillation work?
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• Table 4.5 shows the various components of petroleum
• The gasoline fraction of crude oil only makes up about

19%, which is not enough to meet demand
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• Gasoline is a mixture of straight, branched, and aromatic
hydrocarbons (5–12 carbons in size)
• Cracking is a process by which C-C bonds of larger alkanes
are broken, producing smaller alkanes suitable for gasoline.
Cracking can be achieved at high temperature (thermal
cracking) or with the aid of catalysts (catalytic cracking).
Cracking generally yields straight-chain alkanes. Although
suitable for gasoline, these alkanes tend to give rise to pre-
ignition, or knocking, in automobile engines
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• Reforming is a process involving many different types of reactions (such as
dehydrogenation and isomerization reactions) with the goal of converting
straight-chain alkanes into branched hydrocarbons and aromatic compounds
• Branched hydrocarbons and aromatic hydrocarbons show less of a tendency
for knocking. It is therefore desirable to convert some petroleum into branched
alkanes and aromatic compounds and then blend them with straight-chain
alkanes. The combination of cracking and reforming effectively increases the
gasoline yield from 19 to 47% for every barrel of crude oil. Gasoline is
therefore a sophisticated blend of straight-chain alkanes, branched alkanes,
and aromatic hydrocarbons
• The precise blend is dependent on a number of conditions. In colder climates,
for example, the blend must be appropriate for temperatures below zero
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Reactivity of alkanes - Halogenation

• General reaction
R-H + X2, heat or hv  R-X + HX
• Specific reactions
H2
light C
CH3CH3 Cl2 + HCl
+ H3C Cl
ethane ethylchloride
H2 light H2 H3C CH3

C C Cl
H3C CH3 + Cl2
H3C C
+ CH
H2
Cl
propane n-propylchloride isopropylchloride
45% 55%
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Reactivity of alkanes - Combustion
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Rotational Conformations of alkanes
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Newman projections
• We know that single bonds in molecules can rotate
– Different rotational states are called
CONFORMATIONS
• 3D rotational conformations are difficult to represent
on a 2D paper. It’s useful to make a molecular model to
help you visualize the structures
• Here are three ways to represent ethane
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Newman projections
• Look directly down the C–C single bond axis. This is
where it is especially helpful to have a model
– The front carbon should eclipse the single bond and
the carbon behind it
– Show the front carbon as a point and the back
carbon as a large circle behind it
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Rotational conformations
• What is the angle between H atoms on the same
carbon? In the Newman projection it looks like 120°
– Does the angle affect stability? WHY? Think about
VSEPR theory
• The angle between H atoms on
adjacent carbons is called a dihedral
or TORSIONAL angle. It is 60° in the
molecule to the right
• Would you expect VSEPR theory to be useful when
considering the stability of rotational
conformations? HOW?
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• If the ethane molecule were to rotate 60° about the
C–C bond, the Newman projection would show that
the H atoms on adjacent carbons eclipse one another
• Compare the stability of the eclipsed and staggered
conformations based on VSEPR theory
• What other conformations are possible?

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Consider a complete 360° rotation about the C–C bond
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• The difference in energy between the staggered and

eclipsed conformations is called TORSIONAL STRAIN
• With a difference of 12 kJ/mol in stability, at room
temperature, 99% of the molecules will be in the
staggered conformation
• How would the ratio change at a higher temperature?
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Rotational conformations - propane

The energy diagram of propane is very similar to that of ethane,
except that the torsional strain is 14 kJ/mol rather than 12 kJ/mol.
Once again, notice that all staggered conformations are degenerate,
as are all eclipsed conformations
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Rotational conformations - propane

We already assigned 4 kJ/mol to each pair of eclipsing H’s. If we know
that the torsional strain of propane is 14 kJ/mol, then it is reasonable
to assign 6 kJ/mol to the eclipsing of an H and a methyl group. This
calculation is illustrated below
The energy cost associated with a methyl group eclipsing a hydrogen

atom amounts to 6 kJ/mol
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Conformational analysis of butane
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Conformational analysis of butane is a bit more complex than the
conformational analysis of either ethane or propane. The three
highest energy conformations are the eclipsed conformations, while
the three lowest energy conformations are the staggered
conformations. In this way, the energy diagram above is similar to the
energy diagrams of ethane and propane. But in the case of butane,
notice that one eclipsed conformation (where dihedral angle = 0) is
higher in energy than the other two eclipsed conformations. In other
words, the three eclipsed conformations are not degenerate.
Similarly, one staggered conformation (where dihedral angle = 180) is
lower in energy than the other two staggered conformations. Clearly,
we need to compare the staggered conformations to each other, and
we need to compare the eclipsed conformations to each other
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Let’s begin with the three staggered conformations. The
conformation with a dihedral angle of 180° is called the anti
conformation, and it represents the lowest energy conformation of
butane. The other two staggered conformations are 3.8 kJ/mol higher
in energy than the anti conformation. Why? We can more easily see
the answer to this question by drawing Newman projections of all
three staggered conformations.
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In the anti conformation, the methyl groups achieve maximum separation from
each other. In the other two conformations, the methyl groups are closer to each
other. Their electron clouds are repelling each other (trying to occupy the same
region of space), causing an increase in energy of 3.8 kJ/mol. This unfavorable
interaction, called a gauche interaction, is a form of steric hindrance, and it is
different from the concept of torsional strain. The two conformations above that
exhibit this interaction are called gauche conformations, and they are degenerate
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Cycloalkanes
In the nineteenth century, chemists were aware of many
compounds containing five-membered rings and six-membered
rings, but no compounds with smaller rings were known. Many
unfruitful attempts to synthesize smaller or larger rings fueled
speculation regarding the feasibility of ever creating such
compounds. Toward the end of the nineteenth century Adolph von
Baeyer proposed a theory describing cycloalkanes in terms of angle
strain, the increase in energy associated with a bond angle that has
deviated from the preferred angle of 109.5°. Baeyer’s theory was
based on the angles found in geometric shapes.
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Cycloalkanes
Baeyer reasoned that five-membered rings should contain almost
no angle strain, while other rings would be strained (both smaller
rings and larger rings). He also reasoned that very large
cycloalkanes cannot exist, because the angle strain associated with
such large bond angles would be prohibitive
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Cycloalkanes
Evidence refuting Baeyer’s conclusions came from thermodynamic
experiments. Recall from earlier in this chapter that heats of
combustion can be used to compare isomeric compounds in terms
of their total energy. It is not fair to compare the heats of
combustion for rings of different sizes since heats of combustion
are expected to increase with each additional CH2 group. We can
more accurately compare rings of different sizes by dividing the
heat of combustion by the number of CH2 groups in the compound,
giving a heat of combustion per CH2 group. The following table
shows heats of combustion per CH2 group for various ring sizes.
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Cycloalkanes – Heats of combustion

The following table shows heats of combustion per CH2 group for
various ring sizes.
Baeyer’s conclusions did not hold because they were based on the incorrect
assumption that cycloalkanes are planar, like the geometric shapes shown earlier. In
reality, the bonds of a larger cycloalkane can position themselves three
dimensionally so as to achieve a conformation that minimizes the total energy of
the compound.
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Cyclopropane
The angle strain in cyclopropane is severe. Some of this strain can be
alleviated if the orbitals making up the bonds bend outward. Not all
of the angle strain is removed, however, because there is an increase
in energy associated with inefficient overlap of the orbitals. Although
some of the angle strain is reduced, cyclopropane still has significant
angle strain. In addition, cyclopropane also exhibits significant
torsional strain, which can best be seen in a Newman projection:
In summary, cyclopropane has two

main factors contributing to its high
energy: angle strain (from small bond
angles) and torsional strain (from
eclipsing H’s). This large amount of
strain makes three-membered rings
highly reactive and very susceptible
to ring-opening reactions.
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Cyclobutane
Cyclobutane has less angle strain than cyclopropane. However, it has
more torsional strain, because there are four sets of eclipsing H’s
rather than just three. To alleviate some of this additional torsional
strain, cyclobutane can adopt a slightly puckered conformation
without gaining too much angle strain:
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Cyclopentane
Cyclobutane has less angle strain than cyclopropane. However, it has
more torsional strain, because there are four sets of eclipsing H’s
rather than just three. To alleviate some of this additional torsional
strain, cyclobutane can adopt a slightly puckered conformation
without gaining too much angle strain:
In total, cyclopentane has much less total strain than cyclopropane

or cyclobutane. Nevertheless, cyclopentane does exhibit some
strain. This is in contrast with cyclohexane, which can adopt a
conformation that is nearly strain free.
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Conformations of cyclohexane
Cyclohexane can adopt many conformations, as we will soon see. For
now, we will explore two conformations: the chair conformation and
the boat conformation
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In both conformations, the bond angles are fairly close to 109.5°,
and therefore, both conformations possess very little angle strain.
The significant difference between them can be seen when
comparing torsional strain. The chair conformation has no torsional
strain. This can best be seen with a Newman. Notice that all H’s are
staggered. None are eclipsed.
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This is not the case in a boat conformation, which has two sources of
torsional strain. Many of the H’s are eclipsed, and the H’s on either
side of the ring experience steric interactions called flagpole
interactions, as shown in. The boat can alleviate some of this torsional
strain by twisting (very much the way cyclobutane puckers to alleviate
some of its torsional strain), giving a conformation called a twist boat
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The lowest energy conformations are the two chair conformations,
and therefore, cyclohexane will spend the majority of its time in a
chair conformation. Accordingly, the remainder of our treatment of
cyclohexane will focus on chair conformations.
When drawing a chair conformation, it is important to draw it
precisely. Make sure that you avoid drawing sloppy chairs, because it
will be difficult to draw the substituents correctly if the skeleton is
not precise.
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Drawing axial substituents

• Each carbon atom in a cyclohexane ring can bear two substituents.
One group is said to occupy an axial position, which is parallel to a
vertical axis passing through the center of the ring. The other
group is said to occupy an equatorial position, which is positioned
approximately along the equator of the ring . In order to draw a
substituted cyclohexane, we must first practice drawing all axial
and equatorial positions properly
• Begin at the right side of the V and draw a vertical line pointing
up. Then, go around the ring, drawing vertical lines, alternating in
direction (up, down, up, etc.):
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Drawing equatorial substituents

• We saw earlier that a properly drawn chair skeleton is composed
of three pairs of parallel lines:
Use these pairs of parallel lines to draw the equatorial positions. In

between each pair of red lines above, draw two equatorial groups
that are parallel to (but not directly touching) the red lines:
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Monosubstituted cyclohexane
Consider a ring containing only one substituent. Two possible chair
conformations can be drawn: The substituent can be in an axial
position or in an equatorial position. These two possibilities
represent two different conformations that are in equilibrium with
each other:
The term “ring flip” is used to describe the conversion of one chair
conformation into the other.
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Skill builder
• Draw both chair conformations of bromocyclohexane
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Comparing the stability of both chair conformations

When two chair conformations are in equilibrium, the lower energy
conformation will be favored. For example, consider the two chair
conformations of methylcyclohexane:
At room temperature, 95% of the molecules

will be in the chair conformation that has the
methyl group in an equatorial position. This
must therefore be the lower energy
conformation, but why? When the substituent
is in an axial position, there are steric
interactions with the other axial H’s on the
same side of the ring
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1,3-diaxial interactions
The substituent’s electron cloud is trying to occupy the same region
of space as the H’s that are highlighted, causing steric hindrance.
These interactions are called 1,3-diaxial interactions, where the
numbers “1,3” describe the distance between the substituent and
each of the H’s. When the chair conformation is drawn in a Newman
projection, it becomes clear that 1,3-diaxial interactions are nothing
more than gauche interactions. Compare the gauche interaction in
butane with one of the 1,3-diaxial interactions in methylcyclohexane
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The presence of 1,3-diaxial interactions causes the chair
conformation to be higher in energy when the substituent is in an
axial position. In contrast, when the substituent is in an equatorial
position, these 1,3-diaxial (gauche) interactions are absent
The exact equilibrium concentrations of the two chair conformations

will depend on the size of the substituent. Larger groups will
experience greater steric hindrance resulting from 1,3-diaxial
interactions, and the equilibrium will more strongly favor the
equatorial substituent
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Di-substituted cyclohexane
When drawing chair conformations of a compound that has two or
more substituents, there is an additional consideration. Specifically,
we must also consider the three-dimensional orientation, or
configuration, of each substituent. To illustrate this point, consider
the following compound:
Draw both chair conformations of the following compound
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Skill builder
Draw both conformations for each of the following compounds:
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Comparing the stability of chair conformations

We compare the stability of compounds bearing more than one
substituent. Consider the following example:
In the first conformation, both groups are equatorial. In the second

conformation, both groups are axial. In the previous section, we
saw that chair conformations will be lower in energy when
substituents are in equatorial positions (avoiding 1,3-diaxial
interactions). Therefore, the first chair will certainly be more stable.
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Comparing the stability of chair conformations

We compare the stability of compounds bearing more than one
substituent. Consider the following example:
In a situation like this, we must decide which

group exhibits a greater preference for being
equatorial: the chlorine atom or the ethyl
group. To do this, we use the numbers from
Table 4.8
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Skill builder
Draw the lowest energy conformation for each of the following
compounds:
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Worked out example

Draw the more stable chair conformation of the following
compound:
According to Table 4.8, the energy cost associated with an axial ethyl group is 8.0
kJ/mol. In the second conformation, two groups are in axial positions: a methyl group
and a chlorine. According to Table 4.8, the total energy cost is 7.6 kJ/mol + 2.0 kJ/mol =
9.6 kJ/mol. According to this calculation, the energy cost is lower for the first
conformation (with an axial ethyl group). The first conformation is therefore lower in
energy (more stable).
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Alkenes : Nomenclature and their properties
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Alkenes
Important alkenes:
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Alkenes
Important alkenes:
The bright red color of tomatoes is due to

lycopene—a polyene
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Alkenes
pheromones
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Sources of alkenes
• Alkenes are also important compounds in the chemical
industry
• 70 billion pounds of propylene (propene) and
200 billion pounds of ethylene (ethene) are both made
from cracking petroleum each year
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Sources of alkenes
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Alkenes-nomenclature
• Alkenes are named using the same procedure we used in
to name alkanes with minor modifications
1. Identify the parent chain, which should include the C=C (double
bond) functional group
2. Identify and name the substituents
3. Assign a locant (and prefix if necessary) to each substituent. Give
the C=C double bond the lowest number possible
4. List the numbered substituents before the parent name in
alphabetical order. Ignore prefixes (except iso) when ordering
alphabetically
5. The C=C double bond locant is placed either just before the parent
name, or just before the -ene suffix
100
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1. Identify the parent chain, which should include the
C=C double bond
– The name of the parent chain should end in -ene
rather than –ane
– The parent chain should include the C=C double

bond
101
3. Assign a locant (and prefix if necessary) to each
substituent. Give the C=C double bond the lowest
number possible
– The locant is ONE number, NOT two. Although the

double bond bridges carbons 2 and 3, the locant is
the lower of those two numbers
102
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name in alphabetical order. Ignore prefixes (except iso)
when ordering alphabetically
5. The C=C double bond locant is placed either just
before the parent name or just before the -ene suffix
103
Cis, trans-isomerism
• For the pi bond to remain intact, rotation around a
double bond is prohibited
• As a result, cis and trans structures are not identical
• What specific type of isomers are cis- and

trans- butene?
104
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Cis, trans-isomerism
105
E,Z - isomerism
• Cis and trans modifiers are strictly used to describe
C=C double bonds with identical groups on each
carbon. Where are the identical groups in trans-2-
pentene?
• For molecules with different groups attached to the

C=C double bond, the E/Z notation is used instead of
cis/trans notation
106
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E,Z - isomerism
• E :higher ranked substituents on opposite sides
• Z :higher ranked substituents on same side
higher lower higher higher
C C C C
lower higher lower lower

Entgegen Zusammen
E Z 107
The Cahn-Ingold-Prelog Rules

• The system that we use to assign E,Z was devised by
R. S. Cahn
Sir Christopher Ingold
Vladimir Prelog
• Their rules for ranking groups were devised in

connection with a different kind of stereochemistry
— one that we discussed in Chapter 3 — but have
been adapted to alkene stereochemistry
108
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The Cahn-Ingold-Prelog Rules

1. Higher atomic number outranks lower atomic number
Br > F Cl > H
higher Br Cl higher
C C
lower F H lower
109
Exercise
a) Name the following alkenes and indicate the isomerism
either cis-trans or E,Z
Cl
b) Draw the structure of 3,4-dibromo-2-methyl-2-pentene

110
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Physical and Chemical Properties of

alkenes
111
Physical properties of alkenes

Physical state
Alkenes exist naturally in all three states. The first three alkenes
(ethane, propene & butane) are gases, and the next fourteen
are liquids. Alkenes higher than these are all solids
Solubility
Alkenes are insoluble in water, but dissolve in organic solvents.
The reasons for this are exactly the same as for the alkanes
Density
Alkenes are lighter than water and are insoluble in water due to
their non-polar characteristics
112
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Physical properties of alkenes

Boiling points
The boiling points of alkenes depend on their molecular mass (chain
length). The bigger their molecular chain the higher the boiling points
Melting Points
Melting points of alkenes depends on the packaging of the
molecules. In cis isomers molecules are package in a U-bending
shape, therefore, will display a lower melting points to that of the
trans isomers 113
Slight polarity of alkene pi() bond

The degree of s orbital character in a sp2 carbon is larger
than in an sp3 carbon (alkane) which makes the sp2 carbon
a weak electron withdrawing group
114
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Slight polarity of alkene pi() bond

• A consequence of this dipole is that cis and trans isomeric
alkenes often have somewhat different physical
properties
cis-2-Butene has a higher boiling point (4°C) than trans-2-butene (1°C)
• In the cis isomer, the two Csp3—Csp2 bond dipoles reinforce

each other, yielding a small net molecular dipole. In the trans
isomer, they cancel out
115
Chemical Properties of Alkenes
• Alkenes are unsaturated compounds, which makes

them highly reactive. Most of these chemical reactions
occur at the Carbon-Carbon double bonds
• This makes alkenes far more reactive than alkanes
• A functional group is a characteristic group of

atoms/bonds that possess a predictable chemical
behavior
116
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Functional groups
Capsaicin (8-methyl-N-vanillyl-6-nonenamide) is the active component of chili peppers
117
Stability-heats of combustion
• The difference in stability can be quantified by

comparing the heats of combustion
• How does heat of combustion relate to

stability?
118
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Stability of cis,trans-isomers
• Because of steric strain, cis isomers are

generally less stable than trans
119
Stability-heats of combustion
120
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Stability-substitution across the double

bond
• Consider the following stability trend:
• What pattern do you see?
121
Some reactions of alkenes

Hydrogenation
Catalytic hydrogenation involves the addition of molecular
hydrogen (H2) across a double bond in the presence of a
metal catalyst such as nickel (Ni) or platinum (Pt); for
example
122
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123

Halogenation
Alkenes also readily undergo halogenation—the addition of halogens.
Indeed, the reaction with bromine (Br2) can be used to test for
alkenes. Bromine solutions are brownish red. When we add a Br2
solution to an alkene, the color of the solution disappears because
the alkene reacts with the bromine:
124
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Hydration
Another important addition reaction is that between an alkene and
water to form an alcohol. This reaction requires a catalyst—usually a
strong acid, such as sulfuric acid (H2SO4):
Used in the synthesis of alcohols

125
Skill builder
• Classify each of the following alkenes as mono-, di-, tri-, or
tetra-substituted:
• List the following molecules in order of increasing heats of

combustion
126
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Alkene reactions
127
Alkynes : Nomenclature and their properties
64
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129
130
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Alkynes
• Alkynes are molecules that incorporate a CC triple
bond
131
Alkynes
• Given the presence of two pi bonds and their associated

electron density, alkynes are similar to alkenes in their
ability to act as a nucleophiles (nucleus loving)
• Converting pi bonds to sigma bonds generally makes a

molecule more stable
132
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Alkynes
• Alkynes contain a carbon—carbon triple bondthe and has a
general molecular formula CnH2n-2
• Terminal alkynes have the triple bond at the end of the carbon
chain so that a hydrogen atom is directly bonded to a carbon
atom of the triple bond.
• Internal alkynes have a carbon atom bonded to each carbon
atom of the triple bond
133
Uses of alkynes
• Acetylene is the simplest alkyne

– It is used in blow torches and as a precursor for the
synthesis of more complex alkynes
• More than 1000 different alkyne natural products have
been isolated
– One example is histrionicotoxin,
which can be isolated from South
American frogs, and is used on
poison-tipped arrows by South
American tribes
134
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Uses of alkynes
• An example of a synthetic alkyne is ethynylestradiol
• Ethynylestradiol is the active
ingredient in many birth control
pills
• The presence of the triple bond increases the potency

of the drug compared to the natural analog
• How do you think a CC triple bond affects the
molecule’s geometry? Its rigidity? Its intermolecular
attractions?
135
Physical properties of alkynes

• The first three alkynes are gases, and the next eight are
liquids. All alkynes higher than these eleven are solids
• Alkynes are slightly polar in nature (each C atom is sp
hybridized)
136
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Physical properties of alkynes
• The boiling point and melting point of alkynes increases as

their molecular structure grows bigger. The boiling point
increases with increase in their molecular mass
• Also, the boiling points of alkynes are slightly higher than

those of their corresponding alkenes, due to the one extra
bond at the carbon site
137
Nomenclature of alkynes
• Alkynes are named using the same procedure we used in
Chapter 4 to name alkanes with minor modifications:
1. Identify the parent chain, which should include the CC
triple bond
3. Assign a locant (and prefix if necessary) to each substituent,
giving the CC triple bond the lowest number possible
4. List the numbered substituents before the parent name in
alphabetical order. Ignore prefixes (except iso) when
ordering alphabetically
5. The CC triple bond locant is placed either just before the
parent name or just before the -yne suffix
138
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1. Identify the parent chain, which should include the

CC triple bond
139
3. Assign a locant (and prefix if necessary) to each

substituent. giving the CC triple bond the lowest
number possible
– The locant is ONE number, NOT two. Although the

triple bond bridges carbons 2 and 3, the locant is
the lower of those two numbers
140
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name in alphabetical order. Ignore prefixes (except
iso) when ordering alphabetically
5. The CC triple bond locant is placed either just
before the parent name or just before the -yne
suffix
141
Nomenclature of alkynes – worked examples
• When both double and triple bonds are present, the -

en suffix follows the parent chain directly and the -
yne suffix follows the -en suffix (notice that the e is
left off, -en instead of -ene)
• The location of the double bond(s) is(are) indicated

before the parent name as before, and the location of
the triple bond(s) is(are) indicated between the -en
and -yne suffixes
142
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• In addition to the IUPAC naming system, chemists

often use common names that are derived from the
common parent name acetylene
143
Using pKa Values to Compare Acidity

Consider the reaction between an acid HA, and water (acting as a
base)
• The reaction is said to have reached equilibrium when there is no

longer an observable change in the concentrations of reactants
and products
• The position of equilibrium is described by the term Keq, which is
defined in the following way
144
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• When an acid-base reaction is carried out in dilute aqueous
solution, the concentration of water is fairly constant (55.5M)
and can therefore be removed from the expression. This gives
us a new term, Ka:
• The value of Ka measures the strength of the acid. Very strong

acids can have a Ka on the order of 1010 (or 10,000,000,000), while
very weak acids can have a Ka on the order of 10-50 (or
0.00000000000000000000000000000000000000000000000001)
145

The values of Ka are often very small or very large numbers. To deal
with this, chemists often express pKa values, rather than Ka values,
where pKa is defined as
• When pKa is used as the measure of acidity, the values will

generally range from -10 to 50.
• An acid with a pKa of 10 is more acidic than an acid with a pKa of

16.
• Each unit represents an order of magnitude. An acid with a pKa of

10 is six orders of magnitude (one million times) more acidic than
an acid with a pKa of 16
146
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147
148
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Acidity of alkynes
• Terminal alkynes have a lower pKa than other

hydrocarbons
• Acetylene is 19 pKa units more acidic than ethylene

(1019 times stronger)
149
Acidity of alkynes
• Because acetylene (pKa=25) is still much weaker than
water (pKa=15.7), a strong base is needed to make it
react
– Explain why acetylene is a stronger acid than

ethylene which is stronger than ethane?
150
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Acidity of alkynes
151
Acidity of alkynes
• When carbon has more “s character,” the electrons are

closer to the nucleus - in effect, carbon with more s-
character is more electronegative - electrons are pulled
in toward the nucleus
∴ they are lower in energy and less available for reaction
152
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Acidity of alkynes
• Consider the equilibria below
• A base’s conjugate acid pKa must be greater than 25 for it

to be able to deprotonate a terminal alkyne
153
154
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Preparation of alkynes
• Alkynes are prepared by elimination reactions. A
strong base removes two equivalents of HX from a
vicinal or geminal dihalide to yield an alkyne through
two successive elimination reactions
155
Reactions of alkanes
Catalytic Hydrogenation
In the process, the alkyne consumes two equivalents of molecular
hydrogen:
Under these conditions, the cis alkene is difficult to isolate

because it is even more reactive toward further hydrogenation
than the starting alkyne
156
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Skill builder
1. The carbon-carbon triple bond of an alkyne is composed of;
A. 3  bonds
B. 3  bonds
C. 2  bonds and 1  bond
D. 1  bond and 2  bonds
2. Draw
i. hepta-3,6-dien-1-yne
ii. 5-phenyloct-2-yne
iii.5-ethyl-2,4,6-trimethyloctane
iv.3,3,6,6-tetraethyl-4-octyne
v. trans-1-chloro-2-butene
157
Skill builder
3. Name the following molecules using IUPAC
158
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Skill builder
4. The valence electron configurations of several atoms are shown
below. How many bonds can each atom make without
hybridization?
159
5. Methyl cyanoacrylate is the main ingredient in Super Glue. Using

its Lewis structure below, answer the questions below
N
d
C O H
c
H C C a C O C H
b
H H
i. Indicate the hybridization for each atom indicated by an

arrow
ii. For the bonds labelled a-d, identify the bond as either a
sigma () or pi () bond
iii. For the bonds you identified in ii above, what atomic
orbitals overlap to form the bond
160
80

Ch. 4 Hydrocarbons

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Ch. 4 Hydrocarbons

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10/13/2022

MBMB 1212 : General Chemistry

Hydrocarbons – Alkanes, alkenes and alkynes

September – December 2022

Carbon nanotubes, can be thought of as a

• Buckyballs may be used to trap free radicals generated during an

• There are four families that contain molecules made of

– Alkanes that are branched are called branched chain

Properties of alkanes - Physical

In most organic solvents, the primary forces of attraction between the

Alkanes nomenclature - IUPAC

• In 1892, as the number of known molecules grew,

• We can learn the IUPAC system instead of having to

Naming alkanes- Finding the parent chain

Use Table 4.1 (next slide) to look up the prefix that

Naming alkanes- Finding the parent chain

Naming alkanes- Finding the parent chain

– If the parent chain has 9

Naming alkanes- Finding the parent chain

– If there is more than one possible parent chain,

• What is the parent name for this compound?

Naming alkanes- Finding the parent chain

– If the parent chain is cyclic (a ring of carbons), add

Naming alkanes- Identifying substituents

2. Identify and name substituents (side chains)

– Count the number of carbons in each side group, and

Naming alkanes- Identifying substituents

Naming alkanes- Identifying substituents

– A ring can be either a parent chain or a substituent

Naming alkanes- Identifying substituents

– Some substituents have complex branches

– How many carbons are in the highlighted

Naming alkanes- Identifying substituents

– Some branched substituents have COMMON names

Naming alkanes- Identifying substituents

• The molecules above are isomers, and they have the

Naming alkanes- Summary

• Draw the bond-line representation for;

Naming alkanes- Bicyclic compounds

• To name a bicyclic compound, include the prefix

Naming alkanes- Bicyclic compounds

• Both compounds consist of two rings and seven carbon atoms.

Naming alkanes- Bicyclic compounds

Naming alkanes- Bicyclic compounds

Naming alkanes- Bicyclic compounds

We must start numbering at the

2. Draw a bond-line structure for each of the following

• When naming a disubstituted cycloalkane, use the

• These two structures are NOT constitutional

• They are STEREOISOMERS

• Draw the condensed structural formulas for the

• Do any of these molecules have cis- and trans-

• Camphor and camphene are fragrant natural

There are many biologically important steroids, all of

Sources and uses of alkanes

• Petroleum, which literally means rock oil is the main

Sources and uses of alkanes

• Table 4.5 shows the various components of petroleum

• The gasoline fraction of crude oil only makes up about

Sources and uses of alkanes

Sources and uses of alkanes

Reactivity of alkanes - Halogenation

H2 light H2 H3C CH3

Reactivity of alkanes - Combustion