THE UNIVERSITY OF ZAMBIA

SCHOOL OF NATURAL SCIENCES

CHEMISTRY DEPARTMENT
Dr. A. Kanyanta

CHE 2511 ALKANES LECTURE NOTES

01/07/20
Objectives
After completing this section, you should be able to
1. Understand physical properties of ALKANES
2. Give an example of a radical substitution reaction.
3. Identify the three steps (initiation, propagation and termination) that occur in a
typical radical substitution reaction.
4. Write out the steps involved in a simple radical substitution reaction, such as
the chlorination of methane.
5. Describe the different types of organic reactions
6. Explain why the halogenation of an alkane is not a particularly useful method
of preparing specific alkyl halides.
PHYSICAL PROPERTIES OF ALKANES
AND CYCLOALKANES
• Examining un-branched alkanes, each alkane
differs from preceding one by a -CH2-, these are
known as homologs

• At STP:
– the first FOUR members of the homologous series of
unbranched alkanes are gases
– C5-C17 (pentane to heptadecane) are liquids
– unbranched alkanes with 18 and more carbon atoms
are solids
 PHYSICAL PROPERTIES OF UNBRANCHED
ALKANES
C atoms Name Bp (˚C) Mp (˚C) Density
(g/mL)
1 Methane -161.5 -182
2 Ethane -88.6 -183
3 Propane -42.1 -188
4 Butane -0.5 -138
5 Pentane 36.1 -130 0.626
6 Hexane 68.7 -95 0.659
7 Heptane 98.4 -91 0.684
8 Octane 125.7 -57 0.703
9 Nonane 150.8 -54 0.718
10 Decane 174.1 -30 0.730
 PHYSICAL PROPERTIES OF UNBRANCHED
ALKANES

C atoms Name Bp (˚C) Mp (˚C) Density

(g/mL)
11 Undecane 195.9 -26 0.740
12 Dodecane 216.3 -10 0.749
13 Tridecane 235.4 -5.5 0.756
14 Tetradecane 253.5 6 0.756
15 Pentadecane 270.5 10 0.763
16 Hexadecane 287 18 0.773
17 Heptadecane 303 22 0.778
18 Octadecane 316.7 32 0.777
19 Nonadecane 330 32 0.777
20 Eicosane 343 36.8 0.789
 PHYSICAL PROPERTIES OF CYCLOALKANES

C atoms Name Bp (˚C) Mp (˚C) Density Refractive

(g/mL) index
3 Cyclopropane -33 -126.6

4 Cyclobutane 13 -90

5 Cyclopentane 49 -94 0.751 1.4260

6 Cyclohexane 81 6.5 0.779 1.4064

7 Cycloheptane 118.5 -12 0.811 1.4266

8 Cyclootane 149 13.5 0.834 1.4449

PREPARATION OF ALKANES

1. Hydrogenation of alkenes
2. Reduction of Alkyl Halides

a: Hydrolysis of Grignard reagent

b: Reduction by metal and acid
3. Coupling of alkyl groups with
organometallic compounds

R1

Li CuX R2X
R1 X R1 Li R1 CuLi R1 R2

1o, 2o, 3o Alkyllithium Lithium dialkylcopper (alkane)

R2 X
o
1 alkylhalide

Example CH2CH3
Li CuI Br CH2(CH2)5CH3
CH3CH2 Cl CH3CH2 Li CH3CH2 CuLi

Br CH2(CH2)5CH3 + CH3CH2CH2(CH2)5CH3
n-heptylbromide n-nonane
Types of Organic Chemical Reactions

(i) Addition Reactions

(ii) Elimination Reactions
(iii) Substitution Reactions
(iv) Rearrangement Reactions
(v) Reduction-Oxidation (Redox) Reactions

• How Organic Reactions Occur

Introduction to Organic Reaction Mechanisms
A Chemical Reaction
To the uninitiated or untutored, a chemical reaction must seem
like an act of magic.

• A chemist puts one or two reagents into a flask, waits for a

time, and then takes from the flask one or more completely
different compounds.

Some of the goals in this course:

• To try to understand how this chemical magic takes place.
Be able to explain how the products of reaction are formed.

• If, as is often the case, reaction takes place in more than one
step, to know what chemical species, called intermediates,
involved in each step along the way.
An Organic Chemical Reaction
Chemical reaction - A process in which one or more elements
or chemical compounds (the reactants) react to produce a
different substance or substances (the products).

• Although there millions of compounds, dozens of functional

groups, and endless number of reactions, there are only a few
fundamental ideas that underlie all organic reactions.

• Organic chemistry is a beautifully logical subject unified by a

few broad themes.

• When themes are understood, learning organic chemistry

becomes much easier and memorisation is minimised.

• Aim here to describe themes and clarify the patterns that

unify organic chemistry.
Kinds of Organic Reactions
Organic chemical reactions are organised broadly in two ways:
(a) By what kinds (types) of reactions occur, and
(b) By how these reactions occur.

(a) Types of Reactions

There are five general types of organic reactions:

(i) Additions,
(ii) Eliminations,
(iii) Substitutions,
(iv) Rearrangements, and
(v) Reduction-Oxidation (redox).
Addition reactions occur when two reactants add together
to form a single product with no atoms “left over”.

H H H H
C C + Br CCl4
Br H C C H
H H
Br Br
Ethe ne 1,2-Dibromoe thane
( a n a lke ne ) ( a n a lkyl ha lide )
An addition re action
Elimination reactions occur when a single reactant splits
into two products, often with formation of a small molecule such
as water or HBr.

They are, in a sense, the opposite of addition reactions.

H H H H
H C C H KOH C C
( -HBr)
H Br H H
Bromoe thane Ethe ne
( an alkly halide ) ( an alke ne )

An e limination re action ( De hydrohaloge nation)

Substitution reactions occur when two reactants exchange
parts to give two new products.

H
H
Light
H C H + Cl Cl H C Cl + H Cl
H H
Methane Chloromethane
(an alkane) (an alkyl halide)

A S ubs titution Re action

Rearrangement reactions occur when a single reactant
undergoes a re-organisation of bonds and atoms to yield an
isomeric product.

H3CH2C H Acid catalyst H3C H

H H H CH3
1-Butene 2-Butene
(an alkene) (an alkene)

A Rearrangement Reaction
Reduction-Oxidation reactions involve transfer of electrons
or change in oxidation number.
A decrease in the number of H atoms bonded to C and an
increase in the number of bonds to other atoms such as C, 0, N,
Cl, Br, F, and S signals oxidation.

H O H O
2- +
Cr2 O 7 / H
H C C H H C C OH
H H
Ethanal Ethanoic acid
(an aldehyde) (a carboxylic acid
A Re dox Re action
Practice1: Classify each of the following reactions as addition,
elimination, substitution, or re-arrangement:

(a) CH3Br + KOH CH3OH + KBr

Substitution

(b) CH3CH2Br H2C CH2 + HBr

Elimination

(c) H2C CH2 + H2 CH3CH3

Addition
 he a t
d) NH4 +( CNO) -
H2 N-C-NH2
Rearrangement O

( e ) 3CH3 CHO + 2MnO 4 - + OH- he a t 3CH3 COO - + 2MnO 2 + 2H2 O

Reduction-Oxidation

( f) CH3 CHClCHClCH3 + Zn CH3 CH=CHCH3 + ZnCl2

Elimination and Redox

 The need for a firm understanding of
structure, formal charges, and
electronegativity can hardly be emphasized
enough as you build a foundation of
knowledge for learning organic chemistry.
Practice2: Which element in each of the following pairs is more
electronegative?

(a) Li or H (b) B or Br (c) Cl or I (d) C or H

Problem: Use the δ+ / δ- convention to show the direction of
expected polarity for each of the bond indicated.

(a) H3C-Cl (b) H3C-NH2 (c) H2N-H

(d) H3C-SH (e) H3C-MgBr (f) H3C-F
In a tug of war the strongest team wins.
Relative ability of an atom to attract the pair of electrons
in a covalent bond is called its electronegativity.
Oxygen is more electronegative than hydrogen. It pulls
the shared pair of electrons towards itself.
Causes a partial negative charge on the oxygen atom
and a partial positive charge on the hydrogen atom.
Chlorine is more electronegative than carbon, so it gains
a partial negative charge.
Carbon gains a partial positive charge. When partial
charges are separated like this, a dipole forms.
Ionic bonding occurs when there are big differences in
electronegativity, usually between a metal and a non-metal.
Covalent bonding occurs when there are small differences
in electronegativity, usually between two non-metals.
Polar bonding lies between the two extremes. A bond
might be only slightly polar.
A bond might be covalent with a degree of ionic character.
It might be ionic with a degree of covalent character.
It might be ionic with a degree of covalent character.
Thus, most bonds are neither fully ionic nor fully covalent
but are somewhere between the two extremes, i.e., they are
polar covalent bonds, meaning that bonding electrons are
attracted more strongly by one atom than the other so the
electron distribution between atoms is not symmetrical.
Bond Breaking and Bond Making

Bond-Breaking

AB A + B Symmetrical bond-breaking (radical)

AB A + B Unsymmetrical bond-breaking (polar)

Bond-Making
A + B AB Symmetrical bond-making (radical)

A + B AB Unsymmetrical bond-making (polar)

How Organic Reactions Occur: Mechanisms
A reaction mechanism describes in detail exactly what takes
place at each stage of a chemical transformation – which
bonds are broken and in what order, which bonds are formed
and in what order.

A complete mechanism must also account for all reactants used

and all product formed.

All chemical reactions involve bond-breaking and bond-forming.

Fundamentally, there two ways in which a covalent 2e—bond

can break.
(i) Symmetrically (homolytic)
(ii) Unsymmetrically (heterolytic)
 REACTIONS OF ALKANES
• Alkanes as a class are characterized by a
general inertness to many chemical reagents
• The C-C and C-H bonds are very quite strong,
the do not break unless heated to very high
temperatures
• Due to the fact that C and H have nearly same
electronegativity, the C-H bond is slightly
polarized, as a result they are generally
unaffected by most bases
• No unshared pair of electrons to offer sites for
attack by acids
 REACTIONS OF ALKANES
1. Radical Reactions
•Radical reactions are not as common as polar reactions but
are nevertheless important in some industrial processes and
in numerous biological pathways.

•A radical is highly reactive because it contains an atom with

an odd number of electrons (usually 7) in its valence shell,
rather than a stable, noble gas octet.

•A radical can achieve a valence-shell octet in several ways.

Unpaired
electron
Unpaired
electron

Rad + AB Rad A + B
Reactant Substitution Product
radical Product radical

Unpaired
electron
Unpaired
electron
Rad
Rad + C C C C
Reactant Alkene Addition product
radical radical
• A example of an industrially useful radical reaction is the
chlorination of methane to yield chloromethane.

• This substitution reaction is the first step in the preparation of

the solvents dichloromethane (CH2Cl2) and chloroform (CHCl3).

H Light H
H C H + Cl Cl H C Cl + H Cl
H H
Chlorine
Methane Chloromethane
Like many radical reactions in the lab, methane chlorination
requires three kinds of steps: initiation, propagation, and
termination.

Initiation
Light
Cl Cl 2 Cl

Propagation

(a) Cl + H CH3 H Cl + CH3

(b) Cl Cl + CH3 Cl + Cl CH3

Termination
Occasionally, two radicals might collide and combine to form a
stable product.
When that happens, reaction cycle is broken and chain is ended.

Cl + Cl Cl Cl

Cl + Cl CH3 Possible termination

CH3 steps

H3C + H3C CH3

CH3
2. Combustion

3. Pyrolysis (Cracking)