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CHM 257
CHAPTER 2
ALKANES
Hydrocarbons
Aliphatic Aromatic
hydrocarbons hydrocarbons
Saturated Unsaturated
-Only contain carbon-carbon -Molecule that contain multiple
single bonds (C-C). bonds such as double bond or
-Has no multiple bonds (double triple bonds.
or triple bonds). - Examples: Alkenes, alkynes,
- Has the maximum number of arenes
bonded hydrogen atoms.
- Examples: Alkanes,
cycloalkanes
Hydrocarbons
Saturated Unsaturated
H H
H C C H H C C H
alkenes alkynes
H H
H C C H
H H
benzene
• General formula:
CnH2n+2, where n = 1, 2, ….
- n = number of carbon atoms
H H H
H C H H C C H
H H H
no. of carbon = 1 no. of carbon = 2
name: Methane name: ethane
H H H H H H H H H H H H H
H C C C C C H H C C C C C C C C H
H H H H H H H H H H H H H
no. of carbon = 5 no. of carbon = 8
name: Pentane name: Octane
NOMENCLATURE OF BRANCHED CHAIN ALKANES
USING IUPAC RULES
RULE 1
Identify the longest carbon chain (not necessary straight)
and write parent name of the compound.
CH3-CH-CH2-CH3 CH3-CH-CH2-CH2-CH3
CH3 CH2-CH3
4 Carbon 6 Carbon
When a compound has two possible longest carbon chains,
select the chain/parent with more substituents.
CH3-CH-CH3
CH3-CH2-CH-CH2-CH2-CH2-CH3 WRONG
1 2 3 4 5 6 7
CH3-CH-CH3
2 1
CORRECT
CH3-CH2-CH-CH2-CH2-CH2-CH3
3 4 5 6 7
3-ethyl-2-methylheptane
RULE 2: NUMBERING THE MAIN CHAIN
To give the locations of the substituents, assign a number to each
carbon atom on the main chain.
Number the longest chain, beginning with the end of the chain
nearest a substituent.
Start the numbering from the end nearest a branch so the numbers
of the substituted carbons will be as low as possible.
1CH
7CH 3
3 3 2
5 6 CH3 CH CH2
CH3 CH CH2
4 5
3 CH CH CH2CH3
4CH CH CH2CH3
CH3 6CH CH3
CH3 2CH CH3 7CH
3
1CH
3 INCORRECT
CORRECT
The first branch at C2 The first branch at C3 (carbon
3-ethyl-2,4,5-trimethylheptane atom 3)
- When the numbering could begin with either of two alkyl groups or
other substituents, begin with the one that is alphabetically first.
- For example:
7 6 5 4 3 2 1 1 2 3 4 5 6 7
CH3 CH CH2 CH CH2 CH CH3 CH3 CH CH2 CH CH2 CH CH3
(INCORRECT) (CORRECT)
2-chloro-4,6-dimethylheptane
RULE 3: NAMING ALKYL GROUPS
• Give the location of each alkyl group by the number of the main chain
carbon atom to which it is attached.
• Alkyl groups are named by replacing the –ane suffix of the alkane name
with –yl. Methane becomes methyl; ethane becomes ethyl.
• The letter “R” is often used in formulas to represent any of the possible
alkyl groups.
NO2 Br
1 2 3 4 5
CH3 CH CH CH3 CH3
3-bromo-2-nitropentane
RULE 4: ORGANIZING MULTIPLE GROUPS
1 2 3 4 5 6
1 2 3
CH 3 CH 2 CH CH 2 CH 2 CH 3
CH 3
4
This is the longest continuous chain.
1 2 3 4 5 6
CH3 CH2 CH CH2 CH2 CH3
CH3
1 2 3 4 5 6
CH3 CH2 CH CH2 CH2 CH3
CH3
This is a methyl group.
1 2 3 4 5 6 7 8
methyl
ethyl
3-ethyl-4-methyloctane
Example 3
CH3 CH3
2 1
CH3CHCH2CHCHCH3
6 5 4 3
CH3
2,3,5-trimethylhexane
Exercises
• Give the IUPAC name of the following compounds:
i)
ii) CH3CH(Cl)CH(CH2CH3)CH2CH(CH3)CH3
Draw the structural formula for each of the
following compounds.
i) 5-isobutylnonane
ii) 4-chloro-3,3-diethyl-5-isopropyloctane
iii) 3-iodo-3-methylpentane
NOMENCLATURE OFALKANES
(COMMON NAMES / TRIVIAL NAMES)
Alkanes with molecular formula C4H10
CH3
H3C C CH3
CH3CH2CH2CH3
H
butane or n-butane ("normal" butane) isobutane meaning "isomer of butane"
Ø Insoluble in water:
- alkanes are non-polar and do not form hydrogen
bonds with water molecules.
- described as ‘hydrophobic’ (water hating).
2) Densities:
water
BOILING POINTS AND MELTING POINTS OF
ALKANES
BOILING POINTS OF ALKANES
Effect of relative molecular mass on boiling point.
• Hydrogenation of alkenes
• Reduction of alkyl halides
• Wurtz reaction
• Hydrolysis of Grignard reagent
Hydrogenation of alkenes
Pt / Pd / Ni
Example:
Ni
C2H4 + H2 C2H6
ethene ethane
Reduction of alkyl halides
• Alkyl halide react with zinc and aqueous acid to
produce an alkane.
R-X + Zn + HX R- H + ZnX2
• Examples:
• Equation:
2R-X + 2Na → 2NaX + R-R
dry ether
CH3I + 2Na + CH3CH2I CH3CH2CH3 + 2NaI + CH3CH2-CH2CH3 + CH3CH3
by-products
Examples:
dry ether
1. 2CH3CH2CH2Cl + 2Na CH3CH2CH2CH2CH2CH3
reflux + 2NaCl
2.
dry ether CH3CHCH2CH3
Br CH2CH2CH2CH3 CH3CHCH2CH3 2Na
CH2CH2CH2CH3
Br
2NaBr
Hydrolysis of Grignard reagent
(alkylmagnesium halide)
Example:
H+
Propylmagnesium Propane
chloride
UNREACTIVITY OF ALKANES
• Alkanes is chemically inert to most reagents.
• Combustion
• Halogenation
• Cracking and reforming of petroleum
REACTIONS OF ALKANES
• COMBUSTION
- Alkanes burn in a plentiful supply of air or oxygen to
produce water and CO2 only.
- for example:
C2H6 + 3 O2 → 2C + 3H2O
2
REACTIONS OF ALKANES
• HALOGENATION OF ALKANES
* Condition of reaction:
light or heat (high temperature) or ultraviolet
radiation (provides energy that is absorbed by
reactant molecules to produce free radicals).
Reaction of Organic Compounds
• Covalent bond cleavage
- during the organic reaction, chemical bonds have to be
broken in order that new compounds may be formed.
- the breaking of chemical bonds is called fission.
- When organic compounds react, their bonds can split up in
the following ways:
- Each atom retains one of the electrons
XY X Y present in the covalent bond.
- known as homolytic fission / homolytic
X
XYY X
X Y
Y cleavage
XY X Y
X
XYY X
X Y
Y - either X or Y retains both electrons
XY X Y - known as heterolytic fission / heterolytic
X cleavage
XYY X
X Y
Y
HOMOLYTIC FISSION (RADICAL
CLEAVAGE)
• Homolytic fission: two shared electrons of the
covalent bond are split equally between the two atoms
joined by the bond.
• Also known as homolysis.
• One electrons goes to X and the others goes to Y.
• The resulting species is called free radicals.
XY X Y
Free radicals
XY X Y
• Examples of free radicals:
i) hydrogen radical, H•
ii)chlorine radical, Cl•
iii)methyl radical, •CH3 or CH3•
iv)ethyl radical, •CH3CH2 or CH3CH2•
• Free radicals are reaction intermediates.
• They are very reactive and many may only exist for a
split second.
• The movement of a single electron in homolytic fission
is shown by a curved half-arrow.
C CI C CI
1) INITIATION STEP
- The chain is initiated (started) by UV light breaking a
chlorine molecule into free radicals. This process is called
photochemical homolytic fission/cleaveage.
hv
Cl Cl Cl Cl
H
Cl H C H HCl + CH3
H methyl radical
methane
- Methyl radical propagates a chain reaction as the
methyl free radical then reacts with another
chlorine molecule to form chloromethane and a
chlorine free radical.
Cl Cl Cl2
CH3 Cl CH3Cl
CH3 CH3 H3C CH3
(by product)
SUMMARY
uv light
CH4 + Cl2 CH3Cl + HCl
1) Initiation step:
hv
Cl Cl Cl Cl
2) Propagation steps:
H
Cl H C H HCl + CH3
H
CH3 Cl2 CH3Cl + Cl
3) Termination steps:
Cl Cl Cl2
CH3 Cl CH3Cl
CH3 CH3 H3C CH3
(by product)
- If a large excess of methane is used, CH3Cl is
obtained as the main organic product.
hv
Br Br Br Br initiation step
Br Br Br2
CH3CH2 Br CH3CH2Br termination step
Br CH3CH2CH2 Br2
CH3CH2CH2Br Br
1o alkyl radical 1-bromopropane
stability increases
The major product of halogenation of alkanes is the most
stable product which are:
i) Cracking:
v A process whereby a saturated hydrocarbon is
converted into an unsaturated hydrocarbon and
hydrogen.
v Ethane is cracked by heating in furnace at 800 to
900oC.
800-900oC
CH3CH3 thermal cracking H2C CH2 H2
ethane ethene
• Cracking is a process where large hydrocarbon
molecules (from crude oil) are broken down into
smaller and more volatile molecules.
catalyst catalyst
CH3CH2CH2CH2CH2CH3 -H2 -H2
• Example:
INDUSTRIAL SOURCE AND USES OF
ALIPHATIC HYDROCARBON
i) Natural gas
- consists of 90-95% methane, 5-10% ethane, and a
mixture of other relatively low boiling alkanes, which
are propane, butane and 2-methylpropane.
- Uses:
a) fuel for automobiles, aircraft and train.
b) provide most of the greases and lubricants
required for the machinery of highly
industrialized society.
c) petroleum with natural gas provides 90% of
organic raw materials for the synthesis and
manufacture of synthetic fibers, plastics,
detergents, drugs and dyes.
• Petroleum refining:
vi) Asphalt
- black, tarry residue remaining after removal of the
other volatile fractions
- C35 and above
Fractional distillation