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7
LEARNING OUTCOMES
By the end of this topic, you should be able to:
1. Classify hydrocarbons as alkanes, cycloalkanes, alkenes, alkadienes,
cycloalkenes, alkynes, and aromatic hydrocarbons;
2. Write chemical formulae of different classes of hydrocarbons based
on their general formulae and
3. Name chemical formulae according to IUPAC nomenclature;
3. Explain the concept of aromaticity; and
4. Name arenes correctly.
INTRODUCTION
This topic will explore hydrocarbons, a family of compounds that we encounter in
our daily lives, especially in our use of fossil fuels, perfumes, and plastics. Indeed,
modern life would not be what it is without hydrocarbons.
But first, what are hydrocarbons? Quite simply, they are chemical compounds
made up of only carbon and hydrogen atoms. For example, in methane, the
simplest of hydrocarbons, one carbon atom is attached to four hydrogen atoms.
In this topic, we will discuss not only the chemical and structural formulae of
hydrocarbons but also their IUPAC names, physical properties, and typical
reactions of alkanes, cycloalkanes, alkenes, alkadienes, cycloalkenes, alkynes, and
aromatic hydrocarbons.
7.1 HYDROCARBONS
Hydrocarbons contain carbon and hydrogen atoms only. Examples are shown in
Table 7.1:
Table 7.1: Hydrocarbons
Aromatic
Group Alkane Alkene Alkyne
Hydrocarbon
Example
For n 4, the carbon chains may be linear or branched. For example, refer to
Table 7.2:
Table 7.2: Examples of Carbon Chain
EXERCISE 7.1
Answers:
(a) The fourth alkane, n = 4
The chemical formula is C4H10 (from CnH2n+2; where n = 4)
The structural formula:
CH3-CH2CH2CH3 or CH3CHCH3
|
CH3
Rule 1: The base name corresponds to the number of carbon atoms in the main
chain. The main chain is a continuous chain (not necessarily written in a straight
line) containing the most number of carbon atoms. Example:
The main chain above has five carbon atoms. The alkane is a pentane.
Rule 2: Identify and name the substituent. Substituents are atoms (other than H) or
groups bonded to the main chain.
For alkanes, the substituents are the alkyl groups, general formula CnH2n+1 (n = 1,
2, 3 ). They are named from the corresponding alkanes by substituting the
ending ane with yl (refer to Table 7.4). In the example above, the alkyl is
methyl.
Rule 3: Indicate the location of the substituent on the main chain by a number.
Each substituent is given a number, which starts from the chain end that gives the
lowest number for the first substituent on the chain.
Example:
Name
Formula
Common IUPAC
CH3 methyl methyl
CH3CH2 (or C2H5) ethyl ethyl
CH3CH2CH2 propyl (or n propyl) propyl
isopropyl (methylethyl)
neopentyl (2,2-dimethylpropyl)
isohexyl (2-methylpentyl)
(3-methylpentyl)
IUPAC recommends common names for simple alkyls. The IUPAC name for an
alkyl group is obtained as follows:
EXERCISE 7.2
Write the IUPAC names for the following alkanes.
(a)
(b)
Answers
(a) Base name : Heptane (longest carbon chain)
Substituent : Methyl groups at C-3 and C-5.
IUPAC name : 3,5-dimethylheptane
(b) Base name : Decane (longest carbon chain)
Substituent : (3,3-dimethyl at C-3; ethyl at C-4.
IUPAC name : 4-ethyl-3,3-dimethyldecane
IUPAC Rules:
(a) Identify the longest continuous chain of carbon in the structure. This forms
the parent chain.
(b) If there are more than one of the same substituent, a prefix di (for two), tri
(for three), tetra (for four), penta (for five), hexa (for six), and so on, is used.
(c) Commas are used to separate numbers; hyphens are used to separate
numbers from words.
(d) Arrange the names of the substituents alphabetically, but do not consider the
prefixes n, sec , tert , di, and tri. Example:
(e) If there is more than one chain with the same number of carbon atoms, the
main chain is the one with the most substituents. Example:
or
Chain A Chain B
(f) If the number for the first substituent is the same from both ends of the
chain, choose the end that gives a lower number for the next substituent.
Example:
(g) If the locations of two different substituents are the same from both ends of
the main chain, the substituent to be named first is given a lower number.
Example:
EXERCISE 7.3
What is the IUPAC name of the following alkane?
Answer:
Base name : Decane
Substituent : Ethyl at C-5 and (1,2-dimethylpropyl) at C-6
IUPAC name : 5-ethyl-6-(1,2-dimethylpropyl)decane
The IUPAC names for cycloalkanes have prefix cyclo added to the name of
the corresponding alkane (same number of carbon atoms). Examples (refer to
Table 7.5):
Table 7.5: Examples of IUPAC Names for Cycloalkanes
Carbon
C3H6 C4H8 C5H10 C6H12
Number
Example
(a) If there is one alkyl group bonded to the cyclic carbon, the name of the alkyl
group is written as a prefix.
Example:
(b) If there are two or more alkyl groups, the alkyl group to be named first
(alphabetically) is numbered 1. The number starts from this alkyl group
either clockwise or anti-clockwise to give a lower number for the next alkyl
group.
Example:
(c) If the number of carbon atoms in the ring is less than in the linear chain, the
cycloalkane becomes the substituent and is named as cycloalkyl.
Example:
EXERCISE 7.4
What is the IUPAC name for the following cycloalkane?
Answer:
Base name: Cyclopropane
Substituent: Ethyl at C-1 and isopropyl at C-2
IUPAC name: 1-ethyl-2-isopropylcyclopropane
EXERCISE 7.5
Write the combustion equation for
(a) 2-methylpropane
(b) Methylcyclopropane
Answers:
(a) 2 CH3CH(CH3)CH3 + 13 O2 8 CO2 + 10 H2O
(b)
EXERCISE 7.6
Two of the products identified from the catalytic cracking of hexane are
ethane and butane. Name two probable products formed from
hydrocracking of hexane, and write the equation for the reaction.
Answer:
The two probable products are ethane and butane.
C H 3 C H 2 C H 2 C H 2 C H 2 C H 3 C H 3 C H 3 + C H 3 C H 2 C H 2 C H 3
Example
ethene 1,3-butadiene cyclopentene
EXERCISE 7.7
Answers:
(a) CH3CH=CH2
(b) CH2=C=CHCH3 or CH2=CHCH=CH2
(c)
For alkenes with four or more carbon atoms, the location of the double bond is
shown by a number. The numbering starts from the end of the main chain that
gives a lower number to the C=C bond. Examples:
Alkadienes are named by replacing the ending ene from the names of the
corresponding alkanes with diene. Examples:
Cycloalkenes are named by assigning the numbers 1 and 2 for the double bond.
However, the numbers are not written in the names. Examples:
EXERCISE 7.8
Write the structural formulas and IUPAC names for all the isomers with
the chemical formula C5H10.
Answer:
CH2=CHCH2CH2CH3 CH3CH=CHCH2CH3
Linear
1-pentene 2-pentene
Branches
2-methyl-1-butene 2-methyl-2-butene 3-methyl-1-butene
(a) Halogenation
Halogens (Cl2 or Br2) adds to the C=C of alkenes and cycloalkenes at room
temperature, in the dark and using inert solvents, such as, dichloromethane
(CH2Cl2) or tetrachloromethane (CCl4), to give vicinal-dihaloalkanes. This is
an example of an electrophilic addition reaction. For example:
EXERCISE 7.9
Answer:
(b) Oxidation
Description of oxidation is as follows:
Oxidative Cleavage of Alkenes
The cleavage of C=C by O3, in water in the presence of zinc forms
carbonyl compounds. The general reaction equation and example are:
Examples:
EXERCISE 7.10
Deduce the structural formula and give the IUPAC name of the alkene
that produces the following compound when reacted with hot
concentrated KMnO4.
Answer:
7.4 ALKYNES
Alkynes are unsaturated hydrocarbons with the functional group CC and
general formula CnH2n2 (n = 2, 3, 4 ). Their IUPAC names are similar to the
corresponding alkenes, by replacing ene with yne.
Examples:
cis-2-Butene is formed due to the syn-addition (same side of the triple bond).
Two moles of hydrogen gas add to one mole of an alkyne in the presence of
Pt, Pd, or Ni to form an alkane. For example:
Two moles of halogen add to one mole of alkyne in an inert solvent to form
tetrahaloalkane. For example:
Benzene (C6H6) 6 (n = 1)
Naphthalene (C10H8) 10 (n = 2)
Anthracene (C14H10) 14 (n = 3)
Note:
(a) There are two electrons for each double bond.
(b) Naphthalene and anthracene are examples of polycyclic aromatic
hydrocarbons.
EXERCISE 7.11
Answers:
(a) The hydrocarbon (cyclobutene) has two electrons, but it is not
aromatic because the bonds are not conjugated.
(b) The hydrocarbon (cyclooctatetraene) has conjugated double
bonds, but it is not aromatic because it has 8 electrons (Huckel
rule: 4n + 2).
(c) The hydrocarbon (tetracene) is aromatic because it is planar, has
conjugated double bonds, and 18 electrons (n = 4).
7.5.1 Benzene
Kekule suggested two structural formulas for benzene:
and
Kekules structures were replaced by one resonance structure, as shown below and
it explains the following observation.
(a) All CC bond lengths are equal (1.397 A). The bond length is intermediate
between CC (1.48 A) and C=C (1.34 A). Thus, benzene does not have
alternating single and double bonds.
(b) Benzene is unreactive towards electrophilic addition reactions (in contrast to
alkenes or alkynes).
Benzene is a planar hexagonal molecule with bond angles of 120o. Each carbon
atom is sp2 hybridised. There is one p orbital containing one electron in each
carbon atom. The six p orbitals overlap sideways to form delocalised electron
clouds above and below the plane. These electrons explain the reaction of
benzene with electrophiles.
Removing one hydrogen results in the phenyl group, C6H5, and this group is
present in many products, such as, in aspirin, polystyrene, perfumes, etc (see
Figure 7.1).
ACTIVITY 7.1
Note
(a) When there are two substituents in the ring, their positions are shown as 1,2-
(or ortho- or o-), 1,3- (or meta- or m-), or 1,4- (para- or p-).
(b) When there are more than two substituents in the ring, use numbers of the
lowest combination to show their positions.
(c) When benzene is the substituent (C6H5 or Ph), it is named phenyl.
(a) Nitration
ArH reacts with concentrated nitric acid (HNO3), in the presence of
concentrated sulphuric acid (H2SO4) as a catalyst, to form nitroarene
(ArNO2). Before the actual reaction takes place, the nitronium ion, NO2+ is
generated. The nitrating mixture generates the nitronium ion, NO2+, as
shown in the equation that follows:
(b) Sulphonation
ArH reacts with fuming sulphuric acid (H2SO4) to form arylsulphonic acid
(ArSO3H), which serves as important industrial chemicals. Fuming sulphuric
Copyright Open University Malaysia (OUM)
152 TOPIC 7 HYDROCARBONS
acid (H2SO4 enriched until SO3) under cold condition will produce HSO3+.
The sulphur atom carries a partial positive charge and attacks the benzene
ring.
Examples:
ACTIVITY 7.2
(a)
(b)
(a)
(b)
10. What are the structural formulae and IUPAC names of alkynes
with the chemical formula C5H8?
The general formula for alkanes is CnH2n+2, cycloalkanes and alkenes is CnH2n,
and alkadienes, cycloalkenes and alkynes is CnH2n - 2.
Hydrocarbons are aromatic if they are planar, cyclic and have (4n + 2)
electrons (The Huckel rule).
Alkadienes Cycloalkenes
Alkanes Hydrocarbons
Alkenes Nomenclature
Alkynes Reaction
Aromatic hydrocarbons The International Union of Pure and
Applied Chemistry (IUPAC)
Arenes
Cycloalkanes