Module 2 - Saturated Hydrocarbons

CHEM 40: Basic Organic Chemistry
Module 2: Saturated Hydrocarbons
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MODULE 2. SATURATED HYDROCARBONS
The simplest class of organic compounds is hydrocarbons, which consist entirely of

carbon and hydrogen. The four major classes of hydrocarbons are alkanes, alkenes, alkynes,
and the aromatic hydrocarbons, which usually contain rings of six carbon atoms that can be
drawn with alternating single and double bonds. Hydrocarbons that contain multiple bonds
(alkenes, alkynes, and aromatics) are unsaturated. Naturally occurring mixtures of many
different hydrocarbons include petroleum and natural gas, which furnish raw materials for the
chemical industry.
In this module, we will focus on saturated hydrocarbons, which contain only carbon–
hydrogen and carbon–carbon single bonds. Saturated hydrocarbons having open-chain
structures are called alkanes while those having cyclic structures are called cycloalkanes. In
the first part, you will learn about the general structure, physical and chemical properties, and
the laboratory as well as industrial preparation of alkanes and cycloalkanes. The second part of
discussion covers the complete combustion and free-radical halogenation of alkanes and
cycloalkanes. You will also learn how to recognize the different types of hydrogen and carbon
atoms present and predict the halogenation product of these compounds.
Objectives
At the end of this module, the students should be able to:
● write the structures and the IUPAC names of alkanes given their molecular
formula;
● name organic compounds based from their structural formulas;
● describe sources and uses of alkanes in particular the petrochemical industry;
● describe the laboratory and industrial preparation of alkanes;
● predict the physical and chemical properties and chemical reactivity from their
molecular structures;
● identify the organic starting material, organic product and/or necessary reagents
for chemical reactions of alkanes;
● understand the outcome of reactions based on the mechanism; and
● distinguish alkanes using simple chemical tests.
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This module is intended only for your personal use in connection with the course you are enrolled in. It
is not for distribution or sale. Permission should be obtained from the Organic Chemistry and Natural
Products Division for any use other than for what it is intended.
2.1. General Structure and Hybridization
Alkanes are organic compounds that have the general formula CnH2n+2 and can be
subdivided into the following two groups: the linear straight-chain alkanes and branched
alkanes. Cycloalkanes have the general formula CnH2n. These compounds consist entirely of
single-bonded carbon and hydrogen atoms and lack any other functional groups. Let us
consider the structure of methane, CH4.
Structure of methane.
The carbon atom in methane has sp3 hybrid orbital and is bonded to four hydrogen
atoms, forming a tetrahedral shape. Because of the sp3 hybridization, the bond angles in carbon
chains are close to 109.5°, and all bonds can thus have the same bond length and angle. Recall
that sp3 has 25% s and 75% p character and each hybrid involves a sigma (σ) bond.
Learning Activity
To learn more about the sp3 hybridization in alkanes and cycloalkanes, go through the
online resource entitled “sp³ Hybrid Orbitals and the Structure of Methane” by Chemistry
Libretexts.
2.2. Nomenclature
The systematic names of alkanes and other compounds were devised according to rules
set by the International Union of Pure and Applied Chemistry (IUPAC). IUPAC rules are
available for dealing with all functional groups and for unambiguously naming most organic
compounds. In the IUPAC system, the chemical name has three parts:
1. The parent tells how many carbon atoms are in the main chain and indicates the
overall size of the molecule.
2. The suffix identifies what functional groups are present in the main chain.
3. The prefix specifies the location of the functional groups and other substituents on
the main chain.
Prefix – Parent – Suffix

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Alkanes
Here are the steps in naming an alkane:
1. Use stems that signify the number of carbon atoms present in the molecule. The stems
signifying n C atoms are tabulated below:
Table 2-1. Stems signifying the number of carbon atoms.
# of C atoms Stem # of C atoms Stem

1 meth 11 undec
2 eth 12 dodec
3 prop 13 tridec
4 but 14 tetradec
5 pent 15 pentadec
6 hex 16 hexadec
7 hept 17 heptadec
8 oct 18 octadec
9 non 19 nonadec
10 dec 20 eicos
2. The stem is combined with an ending characteristic for a given functional group. The
characteristic ending for alkanes is “ane”. For example, a two-carbon chain is called
ethane while a three-carbon chain is called propane. The name for CH3(CH2)12CH3 is
tetradecane, formed by combining the stem, tetradec, signifying 14 C atoms and the
ending ane, indicating the class of the compound. Other members of the homologous
series of straight-chain alkanes, named systematically using a Greek (or Latin) prefix
that denotes the number of carbon atoms in the structure is presented below:
Table 2-2. The first ten straight-chain (continuous) alkanes.
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3. Identify the longest chain of carbon atoms in its structure. Complex alkanes are named
by using the longest continuous chain of C atoms as the basis of the name. If there is
no longest chain because two or more chains are the same longest length, then the
parent chain is defined as the one with the most branches.
Example 1:
Example 2:
The longest continuous chain or the parent chain of the C atoms in the structural
formula in example 2 contains 15 C atoms. The stem that signifies the number of C
atoms in the longest continuous chain is pentadec and the name for this chain is
pentadecane.
4. Add prefixes to the name of the longest chain to indicate the positions and names
of substituents. The longest chain of carbon atoms is numbered in such a way as to
produce the lowest number for the substituents.
a. If there are 2 substituents on the same C, assign them both the same number.
b. There must always be as many numbers in the name as there substituent.
All the groups attached to the chain of C atoms through which the line was drawn
are called substituents. Hydrocarbon substituents are named by adding “yl” to the stem,
which signifies the number of C atoms in those substituents. For example, “meth”, which
signifies 1 C atom, becomes methyl; “eth”, which signifies 2 C atoms becomes ethyl
and “alk”, the general stem for a hydrocarbon becomes alkyl.
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5. Multiple substituents are named individually. Arrange them in alphabetical order

and precede the name of each substituent by the position number (locant) and then
add the name of the parent chain. Numbers are separated from each other by commas
and from the words by hyphens (the general rule in punctuation is separate like things
with commas and unlike things with hyphens).
a. For same substituent occurring more than once, use prefixes di-, tri-, tetra-,
penta- Keep in mind that these prefixes indicating the number of substituents
are not considered in alphabetizing.
b. Prefixes indicating whether the carbon of the alkyl substituent directly attached
to the longest chain is s- or sec- (for secondary-) and t- or tert- (for tertiary)
are placed before the name of substituent. These prefixes are underlined or
italicized and are separated from the rest of the name by hyphens. These
structural prefixes are ignored in alphabetization.
Example: The alkyl group represented by the formula
is a tertiary alkyl group named as tert-pentyl or t-pentyl.
An alkyl group whose point of attachment is a carbon bound to only one

carbon is classified as a primary alkyl group (1°); one whose point of attachment
is a carbon bound to two other carbons is a secondary alkyl group (2°); and one
whose point of attachment is a carbon bound to three other carbons is a tertiary
alkyl group (3°).
Example: The alkyl group represented by the formula
is classified as a primary alkyl group, and its isomer
is classified as a secondary alkyl group. Another isomer
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is classified as a tertiary alkyl group.
b. The structural prefix “iso” (structural prefixes are used to distinguish among
the isomers) is restricted to compounds with single C branch at one end of
the parent chain.
c. The structural prefix “neo” is used for the isomers of with two methyl groups
attached to the second to the last carbon. Like “iso”, “neo” is not separated
from the alkane portion of the name. These prefixes are also considered in
alphabetization when they are treated as substituents.
There are 4 substituents in the Example 2, the names of the four substituents in
the foregoing formula are ethyl, isopropyl and two methyl groups.
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6. Naming alkane isomers:
Compounds that have the same molecular formula, but different structural
formula are called isomers. For example:
The first one shows a continuous chain of four carbons but the other shows a branched
chain of four carbon atoms. The two structural formulas represent two different
compounds with different physical and chemical properties.
a. Branched chain isomers may be named using prefixes. The structural prefix “iso”
signifies a single C branch at the end of the parent chain. Example: The structure
below can be named as isononane. The structure has a single branch at the end of
the parent chain and has a total of 9 C atoms.
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Example: The common name for the formula below is neohexane.
b. Isomers with more complex branching than that signified by the prefixes iso and neo
are not named by the use of structural prefixes. Names for these compounds are
based on the substituted parent chain.
Example: The IUPAC name for the compound represented by the structural formula
is not isooctane but 5-ethyl-2,3,3,6-tetramethyloctane.
7. When all the carbons of the group are in a continuous chain, the IUPAC name for the
alkyl group usually contains no structural prefix, although the structural prefix n-, “for
normal”, may be encountered in some books.
Example: The stem signifying five carbons in an alkyl group represented by the
formula CH3CH2CH2CH2CH2- is pentyl or n-pentyl.
IMPORTANT: Keep in mind that prefixes such as iso, neo, and cyclo are
considered in arranging the substituents in alphabetical order, whereas prefixes
indicating the number of substituents ( i.e. di, tri, tetra, penta) as well as prefixes
indicating the type of carbon (sec-, tert-) of the alkyl substituent directly attached
to the parent chain are not considered in alphabetization.
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SAQ 2-3. Nomenclature of Alkanes
Convert the chemical formulas to names and the names to chemical formulas. For naming, consider the use
of structural prefixes, if applicable.
1.
2.
3.
4.
5. 3-ethyl-2,2,4-trimethylhexane
6. 3,3-diethylpentane
7. 5-isopropyl-3-methyloctane
8. 4-methyl-4-propylheptane
Cycloalkanes
In cycloalkanes, the ends of a hydrocarbon chain are connected to form a ring of

covalently bonded carbon atoms. Cyclic hydrocarbons are named by attaching the
prefix cyclo– to the name of the alkane. The simplest cyclic alkanes
are cyclopropane (C3H6) a flammable gas that is also a powerful anesthetic,
and cyclobutane (C4H8). The most common way to draw the structures of cyclic alkanes
is to sketch a polygon with the same number of vertices as there are carbon atoms in
the ring; each vertex represents a CH2 unit.
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Table 2-3. Structures of the cycloalkanes that contain three to six carbon atoms.
For convenience, cycloalkanes are usually represented as geometric figures, such

as square for cyclobutane. Such figures symbolize a carbon at each corner and as
many hydrogens are necessary to complete a valence of 4 for that carbon.
a. Substituents on the ring are treated just as substituents on a chain. A

monosubstituted ring does not require a number to indicate the position of
substitution since all positions are equivalent.
Example: The name for the compound below is methylcyclohexane.
b. If there are two or more substituents, numbers should be used to indicate the
position of substitution. One of the substituents is always assigned the position
1, and the lower possible numbers are used for all the others. The
substituents are also arranged in alphabetical order. For example, the name
of
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is 4-ethyl-1-isopropyl-2-methylcyclohexane.
SAQ 2-4 . Nomenclature of Alkanes and Cycloalkanes
I. Give systematic IUPAC names for each of the following

structure IUPAC name
1.
2.
3.
4.
5.
II. Write a shorthand formula for each of the following compounds:

a) 1,4-Dichloropentane
b) 4-Isopropylheptane
c) 1,4-Dicyclopropylhexane
d) Cyclopentylcyclopentane
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2.1.5. Physical Properties
Physical state or phase (solid, liquid or gas) is the most obvious characteristic organic
compounds and one of the first observations that we would note in experimental work.
Temperatures at which transitions occur between phases (i.e. melting point and boiling points)
are more easily measured physical properties. Melting points and boiling points are useful in
identifying and isolating organic compounds.
Physical properties depend upon the following:

a) nature of the structural units (ions, molecules) of which substance is composed;
b) strength of the forces (interionic, intermolecular) between the structural units;
c) molecular size or weight; and
d) molecular shape.
Learning Outcomes
● correlate the physical properties of alkanes and cycloalkanes with their structures
● predict the relative boiling points of alkanes and cycloalkanes from their structures
Alkanes and cycloalkanes are structurally similar so that many of their properties can be
considered side by side. These compounds are not very reactive and have little biological
activity and are colorless and odorless non-polar compounds. As discussed in the previous
module, only two types of bonds are found in alkanes and cycloalkanes.
● A C-H bond (overlap of sp3 hybrid orbital of carbon and s orbital of hydrogen)
● A C-C bond (overlap of sp3 hybrid orbital of two carbon atoms)
●
The nature of these bond governs the physical as well as the chemical properties of
these compounds. Although there are some differences in properties between alkanes and
cycloalkanes, in this module we shall emphasize the similarities.
Melting point and boiling points are an indication of the strength of intermolecular forces
(IMFs). The relative weak London dispersion forces of alkanes result in gaseous substances for
short carbon chains, volatile liquids with densities around 0.7 g/mL for moderate carbon chains,
and solids for long carbon chains. The differences in the physical states occurs because there is
a direct relationship between the size and shape of molecules (influenced by the degree of
branching) and the strength of the IMFs.
The C-C bond is nonpolar, and the C-H bond is essentially nonpolar since there is a very
small electronegativity difference between carbon and hydrogen. Alkanes and cycloalkanes are
thus nonpolar molecules and the only type of intermolecular force present is intermolecular
forces Van der Waals forces, which is the weakest type of IMFs. Dispersion forces is due to
the attraction between temporary positive and negative charges arises from the movement of
electrons in nonpolar bonds.
The boiling points for the “straight chain” isomers and alkanes isomers are shown to
demonstrate that branching decreases the surfaces area, weakens the IMFs, and lowers the
boiling point.
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A. Boiling and Melting Points
Among organic compounds of similar molecular masses (molecular weights), alkanes have
the lowest boiling points because only the weak dispersion forces are present in the nonpolar
alkanes.The boiling point of a liquid is the temperature at which the vapor pressure of the liquid
equals the pressure of the atmosphere above it.
At room temperature and one atmospheric pressure, the first four members of the
unbranched alkanes are gases; the C5- C17 ae liquids; and unbranched alkanes with 18 carbon
atoms or more are solids.
For normal or unbranched alkanes, an increase in boiling point is observed as the molecular
mass (and molecular size) of the alkane increases.
Table 2-5. Boiling point of some normal or unbranched alkanes.

Name Structural Formula Boiling Point, °C
(1 atm)
Methane CH4 -162
Ethane CH3CH3 -88
Propane CH3CH2CH3 -42
Butane CH3CH2CH2CH3 0
Pentane CH3CH2CH2CH2CH3 36
Hexane CH3CH2CH2CH2CH2CH3 69
Heptane CH3CH2CH2CH2CH2CH2CH3 98
Octane CH3CH2CH2CH2CH2CH2CH2CH3 126
Nonane CH3CH2CH2CH2CH2CH2CH2CH2CH3 151
decane CH3CH2CH2CH2CH2CH2CH2CH2CH2CH3 174
Larger molecules would have greater surface contact between molecules and, thus, would
have greater dispersion forces than smaller molecules. This increase in intermolecular forces
would require more energy (a higher temperature) for the separation of molecules from one
another and for boiling to take place. Molecules that are generally longer, flatter, or cylindrical
have a greater surface area available for intermolecular interactions than more spherical
molecules, and consequently have greater attractive forces between them than the tangential
interactions between branched molecules.
The boiling points of the unbranched alkanes show a regular increase with increasing
molecular weight in the homologous series of straight-chain alkanes. Branching of the alkane
chain, however, lowers the boiling point. This is evident when comparing pentane, the
unbranched C5H12 hydrocarbon, with neopentane, the most highly branched C5H12 isomer (in
which one carbon bears four methyl groups). Pentane has a boiling point of 36 °C. Neopentane
has a boiling point of 9.5°C. The difference in their boiling points indicate that the attractive
forces between pentane molecules are stronger than between neopentane molecules.
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Table 2-6. Boiling point of the isomers of pentane.

Isomers of pentane Boiling point, °C
36
28
9.5
The normal isomer has an overall zigzag shape that allows two molecules to fit in and align
in a manner shown below. The shaded area depicts the area of the two molecules that are in
contact, through which Van der Waals forces occur.
Taking the other extreme, the most branched isomer has a compact and almost spherical
shape that allows two molecules to come in contact only over a small area. Chain branching
makes a molecule more compact, reducing its surface area and with it the strength of the
dispersion forces operating between it and adjacent molecules; this has the effect of lowering
the boiling point.
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Just like alkanes, the boiling points of cycloalkanes increase as the number of carbon atom
increases.
If branching occurs, symmetrical branching results in a higher boiling point and higher
melting point than unsymmetrical branching.
Example: Each alkane contain 6 carbons.
IMPORTANT!
Molecular shape has a big effect on melting point; the more symmetrical a molecule is, the
better it will pack or fit into the crystal lattice. All other factors being equal or comparable,
symmetrical compounds have higher melting points than unsymmetrical ones.
Table 2-7. Boiling point of some cycloalkanes.

Number of carbon atoms Name Boiling point, °C
3 cyclopropane -33
4 Cyclobutene 1.3
5 Cyclopentane 49
6 cyclohexane 81
7 cycloheptane 119
8 cyclooctane 149
Notice that cycloalkanes have higher boiling points than their open-chain counterparts. This
is largely due to the more rigid rings which allow closer packing of molecules resulting in
greater dispersion forces among the molecules.
The trends in melting points are not as regular as the trend in boiling points. This is because
melting points depend not only on the size of molecules but also on how well the molecule fits
in crystal lattice.
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SAQ 2-5 . Physical Properties

For each of the following group of compounds, determine which compound has the
higher melting point and boiling point. Explain your answer.
1.
pentane 2-methylbutane neopentane
2.
octane 2,2,3,3-tetramethylbutane
B. Solubility
Intermolecular forces are of primary importance in explaining the solubilities of

substances. Dissolution of a solid in a liquid is, in many respects, like the melting of a solid. The
orderly crystal structure of the solid is destroyed, and the result is the formation of the more
disorderly arrangement of the molecules (or ions) in solution. In the process of dissolving, too,
the molecules or ions must be separated from each other, and energy must be supplied for
both changes. The energy required to overcome lattice energies and intermolecular or interionic
attractions comes from the formation of new attractive forces between solute and solvent.
Being nonpolar molecules, alkanes and cycloalkanes do not dissolve in polar solvents like
water, but they dissolve in nonpolar solvents. Alkanes and cycloalkanes are almost totally
insoluble in water because of their very low polarity and their inability to form hydrogen bonds.
The liquid alkanes are themselves considered as nonpolar solvents and are soluble in one
another, and they generally dissolve in solvents of low polarity. Good solvents for them are
benzene, carbon tetrachloride, chloroform, and other hydrocarbons.
C. Density
The alkanes are the least dense of all groups of organic compounds. All alkanes and
cycloalkanes have densities considerably less than 1.00 g/mL, the density of water at 4 °C.
Consequently, petroleum (a mixture of hydrocarbons in alkanes) floats on water.
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2.1.6. Sources and Uses of Alkanes
The primary source of alkanes is petroleum, a complex mixture of organic compounds,

most of which are alkanes and aromatic hydrocarbons. The first step in refining petroleum is
distillation, a process that separates the petroleum into fractions based on the volatility of its
components. The fractions taken contain mixtures of alkanes of similar boiling points.
Table 2-8 . Typical Fractions Obtained by Distillation of Petroleum.
Petroleums differ considerably in composition depending on their source. However, a

representative petroleum on distillation yields the following fractions:
1. Gas fraction, boiling up to 40°, contains normal and branched alkanes from C1 to C5.
Natural gas is mainly methane and ethane. "Bottled" gas (liquefied petroleum gas) is
mainly propane and butane.
2. Gasoline contains mostly hydrocarbons from C6 to C10. Over 100 compounds have been
identified in gasoline, and these include continuous-chain and branched alkanes,
cycloalkanes, and alkylbenzenes (arenes). The branched alkanes make better gasoline
than their continuous-chain isomers because they give less "knock" in high-compression
gasoline engines.
3. Kerosene contains hydrocarbons from C11 to C12. Much of this fraction is utilized as jet
engine fuels or is "cracked" to simpler alkanes (and alkenes).
4. Light gas oil, C13 to C17, is utilized as diesel and furnace fuels.
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5. Heavy gas oil and light lubricating distillate, boiling point 305° to 405°, C18 to C25.
6. Lubricants, boiling point 405° to 515°, C26 to C38, familiarly encountered as paraffin and
petroleum jelly (Vaseline).
7. The distillation residues known as asphalts.
Sources and Uses of Alkanes
Mixtures of alkanes, fortunately, are perfectly suitable for uses as fuels, solvents, and
lubricants, the primary uses of petroleum. The highly branched compound 2,2,4-
trimethylpentane (called isooctane in the petroleum industry) burns very smoothly (without
knocking) in internal combustion engines and is used as one of the standards by which the
octane rating of gasolines is established (Solomons, 2011).
Structure of isooctane.
2.1.7. Reactions
a) Combustion
Reaction 2-1. Complete combustion of open-chain alkanes.
Reaction 2-2. Complete Combustion of cycloalkanes.
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When alkanes react with oxygen (e.g., in oil and gas furnaces and in internal combustion
engines) a complex series of reactions takes place, ultimately converting the alkane to carbon
dioxide and water. This reaction is accompanied with release of heat (known as heat of
combustion, H, which is the quantity of heat evolved when one mole of a compound
undergoes complete combustion). Combustion is a free radical reaction with a complex reaction
mechanism. Initially, energy is required to obtain the reactive species but once started, chain-
carrying steps proceed readily and exothermically. Complete combustion gives carbon dioxide
and water as products, and a large amount of heat is released. However, many combustion
processes, such as the burning of gasoline in an internal combustion engine, do not result in
complete combustion. Aside from carbon dioxide and water, incomplete combustion produces
carbon which is deposited as soot, and carbon monoxide (CO), a highly poisonous gas.
SAQ 2-6 . Combustion of Alkanes
A. Write a balanced combustion reaction for the following hydrocarbons.
d. butane
e. octane
b) Halogenation of Alkanes
Reaction 2-3
Alkane Alkyl halide
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Reactivity: F2 > Cl2 > Br2 > I2
Halogenation is the replacement of one or more hydrogen atoms in an organic compound

by a halogen (fluorine, chlorine, bromine or iodine). Unlike the complex transformations of
combustion, the halogenation of an alkane appears to be a simple substitution reaction in
which a C-H bond is broken, and a new C-X bond is formed. We shall confine our attention to
chlorine and bromine, since fluorine is so explosively reactive it is difficult to control, and iodine
is generally unreactive. These reactions are accompanied by the formation of hydrogen chloride
or hydrogen bromide. Consider the chlorination of methane as an example of this
reaction.
CH4 + Cl2 + energy → CH3Cl + HCl
One complication of this reaction is that all the hydrogen atoms of an alkane may
undergo substitution, resulting in a mixture of products. The relative amounts of the products
depend on the proportion of the two reactants used. In the case of methane, a large excess of
the hydrocarbon favors formation of methyl chloride as the chief product; whereas, an excess
of chlorine favors formation of chloroform and carbon tetrachloride.
CH4 + Cl2 + energy → CH3Cl + CH2Cl2 + CHCl3 + CCl4 + HCl
IMPORTANT!
For this lesson, we will focus only on the monohalogenation of alkanes.
Here are some of the key points to remember about halogenation reactions:
● exothermic
● initiated by energy input in the form of heat or light
● no reaction in the dark at room temperature
● oxygen slows down the reactiob
● occurs in the gas phase or non-polar solvent
o recall the bromine test in the laboratory
Let us see how substitution reaction takes place by studying the reaction mechanism.
Consider the reaction of methane with chlorine shown below as the model reaction:
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Steps in the mechanism:
1. Chain initiation step – starts the chain reaction; reactive species are produced
2. Chain propagation steps – result in the formation of the reaction products as well as
the reactive intermediates that propagate the chain; up to 5,000 cycles per halogen
atom
then (2), (3), (2), (3), (2), (3), ....... until the reactants are used up
3. Chain termination step – occurs after all the reactants have been used up; involves
all the possible combinations of free radical species produced in the course of the
reaction
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The reaction rates depend on the ease of hydrogen abstraction, which is parallel to the
stabilities of the alkyl free radicals formed in the chain propagation steps. The more stable the
free radical, the more easily it is formed. The kind of halogen also affects reaction rates: Cl –
more reactive; less selective Br – less reactive; more selective.
Stability of Free Radicals: 1° < 2° < 3°
To predict the halogenation products, you should be able to recognize the different
types of hydrogen atoms present. The type of hydrogen atom is determined by the type of
carbon atom to which it is attached.
Types of Carbon Atom
Types of Hydrogen atom
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Example: Consider the two structures below, hydrogen atoms are classified as
primary, secondary and tertiary.
SAQ 2-7 . Types of Hydrogen Atoms
In the following alkanes, identify the types of the encircled hydrogen atoms.
____________
a. ____________
b. ____________
c. ____________
d. ____________
e. ____________
f. ____________
____________
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Relative Proportions of Products
The relative proportion of chlorination products is determined by relative rates of

competing reactions.
Factors that determine rates:
1. probability factor
2. ease of abstraction of H atoms (based on the study of chlorination at room
temperature):
1° < 2° < 3°
Relative rates per H atom 1.0 : 3.8 : 5.0
When alkanes larger than ethane are halogenated, isomeric products are formed. For
example, chlorination of propane gives both 1-chloropropane and 2-chloropropane as mono-
chlorinated products.
Propane has 8 H atoms, 6 of them being structurally equivalent 1°, and the other two
being 2°. If all these H atoms were equally reactive, halogenation should give a 3:1 ratio of 1-
halopropane to 2-halopropane mono-halogenated products, reflecting the primary/secondary
numbers. This is not what we observe. Light-induced gas phase chlorination at 25 °C gives 45%
1-chloropropane and 55% 2-chloropropane. The results of bromination (light-induced at 25 °C)
are even more suprising, with 2-bromopropane accounting for 97% of the mono-bromo
product. These results suggest strongly that 2°-hydrogens are inherently more reactive than 1°-
hydrogens, by a factor of about 3:1.
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Light-induced chlorination of 2-methylpropane gave predominantly (64%) 2-chloro-2-

methylpropane, the substitution product of the sole 3°-hydrogen, despite the presence of nine
1º-hydrogens in the molecule. Surprisingly, bromination of 2-methylpropane gave
predominantly 2-chloro-2-methylpropane in > 99 % yield.
It should be clear from a review of the two steps that make up the free radical chain
reaction for halogenation that the first step (hydrogen abstraction) is the product
determining step. Once a carbon radical is formed, subsequent bonding to a halogen atom
(in the second step) can only occur at the radical site. Consequently, an understanding of the
preference for substitution at 2° and 3°-carbon atoms must come from an analysis of this first
step.
First Step: R3C-H + X• ——> R3C• + H-X

Second Step: R3C• + X2 ——> R3C-X + X•
Since the H-X product is common to all possible reactions, differences in reactivity can
only be attributed to differences in C-H bond dissociation energies (energy required to break a
bond homolytically).
R (in R–H) methyl ethyl iso- tert- phenyl benzyl allyl vinyl
propyl butyl
Bond Dissociation 103 98 95 93 110 85 88 112
Energy
(kcal/mole)
The covalent bond homolyses that define the bond dissociation energies listed above may are
described by the general equation:
R–H + energy ——> R• + H•
The difference in C-H bond dissociation energy reported for primary (1º), secondary (2º)
and tertiary (3º) sites agrees with the halogenation observations reported above, in that we
would expect weaker bonds to be broken more easily than are strong bonds. By this reasoning
we would expect benzylic and allylic sites to be exceptionally reactive in free radical
halogenation, as experiments have shown. The methyl group of toluene, C 6H5CH3, is readily
chlorinated or brominated in the presence of free radical initiators (usually peroxides), and
ethylbenzene is similarly chlorinated at the benzylic location exclusively. The hydrogens bonded
to the aromatic ring (referred to as phenyl hydrogens above) have relatively high bond
dissociation energies and are not substituted.
C6H5CH2CH3 + Cl2 ——> C6H5CHClCH3 + HCl
Since the hydrogen atom is common to all the cases cited here, we can attribute the
differences in bond dissociation energies to differences in the stability of the alkyl radicals (R·)
as the carbon substitution changes. This leads us to the conclusion that:
25
alkyl radical stability increases in the order:
phenyl < primary (1º) < secondary (2º) < tertiary (3º) < allyl ≈ benzyl
Because alkyl radicals are important intermediates in many reactions, this stability
relationship will prove to be very useful in future discussions. The enhanced stability of allyl and
benzyl radicals may be attributed to resonance stabilization. The poor stability of phenyl
radicals, C6H5•, may in turn be attributed to the different hybridization state of the carbon
bearing the unpaired electron (sp2 vs. sp3).
For example, 2,4-dimethylpentane will give a mixture of three isomeric products upon
halogenation. We can calculate the percent yield of each product by using the formula:
26
● product A
o results from substitution of any of the 12 equivalent 1º H atoms
o relative proportion of products = r
● product B
o relative proportion of products
● product C
Calculation on the percentage of each product:
percentage= x100
product A product B product C

Percentage= percentage= percentage=
of A of B of C
27
● product A
o relative proportion of products = r
● product B
● product C
product A product B product C

percentage= percentage= percentage=
of A of B of C
Keep in mind that these calculations for bromination of 2,4-dimethylpentane is to

illustrate that the tertiary alkyl bromide (product B) is the predominant product, which is
dependent on the stability of the free-radical intermediate formed. Thus, there is no need to
calculate the relative proportion of products for bromination reaction.
IMPORTANT
The major product of bromination is always the one coming from the most stable free radical
intermediate. Thus, there is no need to do calculations for predicting the major product of
bromination. In the case of chlorination, the major product formed depends on the
calculations of relative proportion of products as affected by probability factor and ease of
abstraction of H atoms (reactivity factor).
28
SAQ 2-8. Halogenation of Alkanes
1. Chlorination of 1,4-dimethylcyclohexane yields 3 isomeric products. Give their

structures and calculate their relative distribution in percent yield.
c) Ring Opening Reactions of Small Cycloalkanes
Reaction 2-3
Small rings may be prone to ring opening reactions due to angle strain and eclipsing
strain (bond orientation) are severe in small rings such as cyclopropane and cyclobutane.
29
Cycloalkane CH2 Units ΔH25º ΔH25º Ring Strain

(CH2)n n kcal/mole per CH2 Unit kcal/mole
Cyclopropane n=3 468.7 156.2 27.6
Cyclobutane n=4 614.3 153.6 26.4
Cyclopentane n=5 741.5 148.3 6.5
Cyclohexane n=6 882.1 147.0 0.0
Cycloheptane n=7 1035.4 147.9 6.3
Cyclooctane n=8 1186.0 148.2 9.6
Cyclononane n=9 1335.0 148.3 11.7
Cyclodecane n = 10 1481 148.1 11.0
CH3(CH2)mCH3 m = large — 147.0 0.0
Changes in chemical reactivity as a consequence of angle strain are dramatic in the case
of cyclopropane and are also evident for cyclobutane. Some examples are shown in the
following diagram. The cyclopropane reactions are additions, many of which are initiated by
electrophilic attack. The pyrolytic conversion of β-pinene to myrcene probably takes place by an
initial rupture of the 1:6 bond, giving an allylic 3º-diradical, followed immediately by breaking of
the 5:7 bond.
Reactions due to Ring Strain.
30
Supplementary Information
a. Go through the online resource entitled “Physical Properties of Alkanes” by

clicking the hyperlinked text.
b. Learn more about nomenclature by reading the online resource entitled “Naming
alkanes”. You can access the information by clicking the hyperlinked text.
c. Watch the following short video tutorials by Khan Academy. Click the hyperlinked
text to review the nomenclature process.
● Naming Simple Alkanes

● Common and systematic naming: iso-, sec-, and tert- prefixes
● Organic chemistry naming examples 2
● Naming a cycloalkane
● Alkane and cycloalkane nomenclature, I
● Alkane and cycloalkane nomenclature, II
● Alkane and cycloalkane nomenclature, III
d. Learn more about halogenation reaction by reading the online resource “Free
Radical Halogenation of Alkanes”. You can access the information by clicking the
hyperlinked text.
References:
McMurry,S. & McMurry, J. (2011). Fundamentals of organic chemistry, seventh edition,

John McMurry /Belmont, CA : Brooks/Cole.
Morrison, R. T., & Boyd, R. N. (1983). Organic chemistry. Boston: Allyn and Bacon.
Solomons, T. W. G., & Fryhle, C. B. (2008). Organic chemistry. Hoboken, NJ: John
Wiley.
31

Module 2 - Saturated Hydrocarbons

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Module 2 - Saturated Hydrocarbons

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CHEM 40: Basic Organic Chemistry

Module 2: Saturated Hydrocarbons

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MODULE 2. SATURATED HYDROCARBONS

The simplest class of organic compounds is hydrocarbons, which consist entirely of

At the end of this module, the students should be able to:

2.1. General Structure and Hybridization

Prefix – Parent – Suffix

Table 2-1. Stems signifying the number of carbon atoms.

# of C atoms Stem # of C atoms Stem

Table 2-2. The first ten straight-chain (continuous) alkanes.

5. Multiple substituents are named individually. Arrange them in alphabetical order

Example: The alkyl group represented by the formula

is a tertiary alkyl group named as tert-pentyl or t-pentyl.

An alkyl group whose point of attachment is a carbon bound to only one

Example: The alkyl group represented by the formula

is classified as a primary alkyl group, and its isomer

is classified as a secondary alkyl group. Another isomer

is classified as a tertiary alkyl group.

6. Naming alkane isomers:

Example: The common name for the formula below is neohexane.

SAQ 2-3. Nomenclature of Alkanes

In cycloalkanes, the ends of a hydrocarbon chain are connected to form a ring of

For convenience, cycloalkanes are usually represented as geometric figures, such

a. Substituents on the ring are treated just as substituents on a chain. A

Example: The name for the compound below is methylcyclohexane.

SAQ 2-4 . Nomenclature of Alkanes and Cycloalkanes

I. Give systematic IUPAC names for each of the following

II. Write a shorthand formula for each of the following compounds:

2.1.5. Physical Properties

Physical properties depend upon the following:

A. Boiling and Melting Points

Table 2-5. Boiling point of some normal or unbranched alkanes.

Table 2-6. Boiling point of the isomers of pentane.

Example: Each alkane contain 6 carbons.

Table 2-7. Boiling point of some cycloalkanes.

SAQ 2-5 . Physical Properties

pentane 2-methylbutane neopentane

Intermolecular forces are of primary importance in explaining the solubilities of

2.1.6. Sources and Uses of Alkanes

The primary source of alkanes is petroleum, a complex mixture of organic compounds,

Petroleums differ considerably in composition depending on their source. However, a

Sources and Uses of Alkanes

Reaction 2-1. Complete combustion of open-chain alkanes.

Reaction 2-2. Complete Combustion of cycloalkanes.

SAQ 2-6 . Combustion of Alkanes

A. Write a balanced combustion reaction for the following hydrocarbons.

Alkane Alkyl halide

Reactivity: F2 > Cl2 > Br2 > I2

Halogenation is the replacement of one or more hydrogen atoms in an organic compound

CH4 + Cl2 + energy → CH3Cl + HCl

CH4 + Cl2 + energy → CH3Cl + CH2Cl2 + CHCl3 + CCl4 + HCl

Steps in the mechanism:

Stability of Free Radicals: 1° < 2° < 3°

Types of Carbon Atom

Types of Hydrogen atom

SAQ 2-7 . Types of Hydrogen Atoms

Relative Proportions of Products

The relative proportion of chlorination products is determined by relative rates of

Light-induced chlorination of 2-methylpropane gave predominantly (64%) 2-chloro-2-

First Step: R3C-H + X• ——> R3C• + H-X

R–H + energy ——> R• + H•