Introduction Contents
Concepts: Alkanes
1. Hydrocarbons are certain organic compounds which contain Physical Properties
only two elements: Hydrogen and Carbon. Chemical Properties
Nomenclature
2. On the basis of structure, hydrocarbons are divided into Conformation
two main classes: aliphatic and aromatic. Drawing Chemical
3. Aliphatic hydrocarbons are further divided into families: Structures
alkanes, alkenes and alkynes and their cyclic analogs Cis-trans isomerism of
Alkanes
(cycloalkanes etc.)
Part I ALKANES
Concepts:
1. Alkanes have a general chemical formula of CnH2n+2.
2. Tetrahedral hybrid orbitals of Carbon are involved in bond formation.
3. The C H is sp3 s type and C C bonds are sp3 sp3 types
4. Alkanes are sometimes referred to as paraffins (L. parun affinis, meaning not enough affinity)
because alkanes have limited reactivity.
5. The most important property of alkanes is their almost lack of polarity. The electronegativity
difference between Carbon and Hydrogen is 0.4 (2.5 2.1) on the Pauling scale.
6. The only interactions between their molecules are the very weak London Dispersion forces.
1. The boiling point of alkanes is lower than most of any type of compound with the same
molecular weight.
2. In general, both boiling point and melting points of alkanes increase with increasing
molecular weight.
6. As branching in an alkane increases, the alkane molecule becomes more compact, and
its surface area decreases. As surface area decreases, London Dispersion forces act over
a smaller surface area. Hence, attraction between molecules decreases, and boiling point
decreases. Thus, the least branched isomer has the highest boiling point and the
most branched isomer has the lowest boiling point.
Note: Isomers refer to compound which have similar chemical formula but different
structural formula.
b. Solubility
1. Alkanes are non-polar, thus, they are not soluble in water.
3. Alkanes, however, are soluble in each other and in non-polar organic compounds such
as toluene and diethyl ether.
c. Density
1. All liquid and solid alkanes are less dense than water, thus, they float in water.
a. Combustion
1. Oxidation of Hydrocarbons, including alkanes and cycloalkanes, is the basis for their use
as energy sources for heat and fuel.
2. The heat liberated when an alkane is oxidized to Carbon dioxide and water is called it
heat of combustion.
Equations:
CH4 + 2O2 CO2 + 2H 2O + 212
kcal/mol
b. Halogenation
Equation:
CH4 + Cl2 heat or light
CH3Cl + HCl
Equations:
CH3Cl + Cl2 heat
CH2Cl2 + HCl
Additional Notes:
- Bromination takes place somewhat less readily than chlorination.
- Methane does not react with Iodine at all.
- With Fluorine, it reacts so vigorously that in the dark, the reaction is
controlled with great difficulty.
C. NOMENCLATURE OF ALKANES
1. Straight chain alkanes (Carbons are connected in a row) are also called as normal
alkanes, and are commonly indicated with letter n. Example: n-butane, n-pentane
2. Straight chain alkanes are named according to the number of Carbon atoms they
contain. With the exception of methane, ethane, propane and butane, the alkanes are
named based on GREEK numbers.
3. The suffix ane is added to each name to identify the molecule as an alkane.
Examples of Straight branched Alkanes
4. If an alkane has a terminal methyl branch (-CH3), the common name has a prefix iso-
5. If an alkane has a terminal dimethyl branch, it is identified with the prefix neo-
Example:
CH3
H3C-C- CH3 is named neopentane
CH3
6. If a Hydrogen is removed from an alkane, the partial structure that remains is called and
alkyl group.
7. The prefixes sec-(secondary), and tert-(tertiary) are used to refer to other Carbon atoms
attached to the branching Carbon atom. There are four possibilities:
H R R
R
H C R H C R R C R R C R
H H H
R
Primary Carbon Secondary Carbon Tertiary Carbon
Quaternary Carbon
Examples:
CH3
H3C - C- is named tert-butyl
CH3
2. Number the atoms in the main chain. Begin assigning numbers at the end
nearer the branch points.
3. Identify and number the substituents. Assign a number called a locant to each
substituent to specify its point of attachment to the parent chain. If there are two
substituents on the same number, assign them both the same number.
4. Write the name as a single word. Use hyphens to separate the numbers. If two
or more different side chains are present, cite them in alphabetical order. If two or
more identical side chains are present, use the appropriate multiplier prefixes (di-,
tri-, tetra- and so forth). Dont use prefixes for alphabetizing, though.
Additional Notes:
o The prefix iso- is considered a part of an alkyl group name while the
hyphenated and italicized prefixs sec-and tert- are not. Thus,
isopropyl and isobutyl are listed alphabetically under I while sec-
butyl and tert-butyl are listed under b.
2. Number the substituents and write the name. For substituted cycloalkanes, start at the
point of attachment and number around the ring. If two or more substituents are present,
begin numbering at the group that has alphabetical priority and proceed around the ring so
as to give the second substituent the lowest number.
D. CONFORMATION OF ALKANES
Conformations refers to the different arrangements of atoms that result from bond rotation.
Conformational isomers/Conformers refer to molecules that have different arrangements due
to bond rotation.
Kinds of Conformations
1. Sawhorse Representation views the C C bonds from an oblique angle
2. Newman Projection views the C C bond directly end-on and represent the two Carbon
atoms by a circle. Bonds attached to the front Carbon are represented in lines to a dot in the
center of a circle and bonds attached to the rear Carbon are represented by lines to the
edge of the circle.
3. At any give instant, alkanes have staggered conformation. It is more favored over
eclipsed conformation.
Rules:
1. Carbon atoms are not usually shown.
2. Hydrogen atoms bonded to Carbon are not shown.
3. All atoms other than Carbon and Hydrogen are shown.
2. Stereoisomers are classified as cis- isomers and trans-isomers (cis = L. on the same
side; trans = L. across)
b. Cyclohexane
i. Cyclohexane is not flat; it is puckered into a strain-free, three dimensional
shape called a chair conformation. All C-C-C bond angles are near 109 o, all C-H
bonds are staggered. It has 6 equatorial planes and 6 axial planes.