Beruflich Dokumente
Kultur Dokumente
CYCLOALKANES
SITI HAJAR ANAZIAH MUHAMAD
C OURSE O UTCOME
Fossil Fuels:
Many alkanes occur in
nature, primarily in
natural gas and
petroleum.
Natural gas is com-posed
largely of methane, with
lesser amounts of ethane,
propane and butane.
Refining crude petroleum into usable fuel and other petroleum products.
(a) An oil refinery. At an oil refinery, crude petroleum is separated into
fractions of similar boiling point by the process of distillation.
(b) Schematic of a refinery tower. As crude petroleum is heated, the lowerboiling, more volatile components distill first, followed by fractions of
progressively higher boiling point.
size range
below 20
C1 to C4
20 to 60
C5 to C6
60 to 100
C6 to C7
40 to 200
C5 to C10
straight-run gasoline
175 to 325
C12 to C18
250 to 400
nonvolatile
liquids
nonvolatile
solids
mineral oil,
lubricating oil
paraffin w ax,
asphalt, tar
Petroleum Technologies
CH3CH2CH2CH2CH2CH3
hexane
acid catalyst
CH3CH2CH2CHCH3
CH3
+
CH3CH2CHCH2CH3
CH3
branched alkanes
Catalytic Reforming
silica-alumina
CH3CH2CH2CH2CH2CH2CH3
catalyst, 500oC
heptane
20 atm H2
CH3
+ 4H2
Petroleum Products
Daily consumption of petroleum in the United States is over 17
million barrels which amounts to close to one billion tons per year.
Of this total, approximately 43% goes into gasoline, another 25%
into fuel oil, and approximately 7.5% into jet fuel. Thus, about
75% of all the petroleum consumed is burned as a source of
energy. The remainder is used as "feedstock" for polymers (~4%)
and the chemical industry (~3%), and the many other products
used in our society such as oils, lubricants and asphalt.
Crude
Petroleum
Refining
straightchain
alkanes
of
different
sizes
branched alkanes
Cracking
Isomerization
Reforming
aromatics
Combustion
All hydrocarbons undergo combustion, the reaction with oxygen
that liberates energy. Thus, all hydrocarbons are potential "fuels",
materials that burn in oxygen releasing energy.
Heat of Combustion
The heat of combustion (Hcomb) is the amount of heat liberated
when one mole of material undergoes combustion at 1 atm pressure
to produce gaseous CO2 and liquid water.
CO2(g) + 2H2O(l)
CH4 + 2O2
methane
Hcomb = -882 kJ/mol (or -55.1 kJ/g)
For a gasoline-size hydrocarbon::
2C8H18 + 25O2
16CO2(g) + 18H2O(l)
Branched hydrocarbons were found to perform better than straightchain alkanes in the internal combustion engine. In 1927, an
arbitrary engineering performance standard was developed called
"the octane rating." The performance of the branched alkane
"isooctane" (actually 2,2,4-trimethylpentane) in a specific internal
combustion engine was given a rating of 100. Heptane, which
causes severe knocking, was given a rating of 0.
CH3 CH3
CH3CCH2CHCH3
CH3
"isooctane"
100
CH3CH2CH2CH2CH2CH2CH3
heptane
0
A fuel with a
performance equivalent
to a mixture of 75%
isooctane and 25%
heptane is given an
octane rating of 75.
Octane Boosters
It is common practice to add octane boosters to gasoline to
improve the performance of the fuel. Many years ago,
tetraethyllead, (C2H5)4Pb, was an important additive for this
purpose. It is now illegal to use "leaded" gasoline in an
automobile in the United States. Aromatics and "oxygenated
fuels" are blended into gasoline to raise the octane rating.
Some Octane Ratings of
Hydrocarbons and Additives
Octane Rating
heptane
0
1-pentene
91
2,2,4-trimethylpentane 100
benzene
106
methanol
107
ethanol
108
methyl t-butyl ether
116
toluene
118
P HYSICAL P ROPERTIES OF
A LKANES
14
Alkanes: Compounds with C-C single bonds and C-H bonds only (no
functional groups)
The formula for an alkane with no rings in it must be CnH2n+2 where the
number of Cs is n
A LKANE I SOMERS
C ONSTITUTIONAL I SOMERS
Isomers that differ in how their atoms are arranged in chains are called
constitutional isomers
C ONDENSED S TRUCTURES OF
A LKANES
A condensed structure does not show bonds but lists atoms, such as
CH3CH2CH2CH3 (butane)
CH3(CH2)2CH3 (butane)
Structural formulas
A LKYL G ROUPS
A LKYL G ROUPS
(C ONTINUED )
T YPES
OF
A LKYL G ROUPS
A LKYL G ROUPS
(C ONTINUED )
C YCLOALKANES
Cycloalkanes have molecular formula CnH2n and contain carbon atoms
arranged in a ring. Simple cycloalkanes are named by adding the prefix
cyclo- to the name of the acyclic alkane having the same number of
carbons.
N AMING A LKANES
Also note that if there are two chains of equal length, pick the
chain with more substituents. In the following example, two
different chains in the same alkane have seven C atoms. We
circle the longest continuous chain as shown in the diagram
on the left, since this results in the greater number of
substituents.
N AMING A LKANES
(C ONT..)
2. Number the atoms in the carbon chain to give the first substituent the
lowest number.
N AMING A LKANES
(C ONTINUED )
If the first substituent is the same distance from both ends, number the
chain to give the second substituent the lower number.
N AMING A LKANES
(C ONTINUED )
When numbering a carbon chain results in the same numbers from either
end of the chain, assign the lower number alphabetically to the first
substituent.
N AMING A LKANES
(C ONTINUED )
3. Name and number the substituents.
Name the substituents as alkyl groups.
Every carbon belongs to either the longest chain or a substituent, not
both.
Each substituent needs its own number
If two or more identical substituents are bonded to the longest chain, use
prefixes to indicate how many: di- for two groups, tri- for three groups,
tetra- for four groups, and so forth.
N AMING A LKANES
(C ONTINUED )
4. Combine substituent names and numbers + parent and
suffix.
Precede the name of the parent by the names of the substituents.
Alphabetize the names of the substituents, ignoring all prefixes except
iso, as in isopropyl and isobutyl.
Precede the name of each substituent by the number that indicates its
location.
Separate numbers by commas and separate numbers from letters by
hyphens. The name of an alkane is a single word, with no spaces after
hyphens and commas.
N AMING A LKANES
(C ONTINUED )
N AMING A LKANES
(C ONTINUED )
A)
B)
CYCLOALKANES
NAMING
Cycloalkanes are named by using similar rules, but the prefix cycloimmediately precedes the name of the parent.
CYCLOALKANES NAMING
(C ONT..)
2. Name and number the substituents. No number is needed to
indicate the location of a single substituent.
For rings with more than one substituent, begin numbering at one
substituent and proceed around the ring to give the second substituent the
lowest number.
CYCLOALKANES NAMING
(C ONT..)
With two different substituents, number the ring to assign the
lower number to the substituents alphabetically.
Note the special case of an alkane composed of both a ring and a long
chain. If the number of carbons in the ring is greater than or equal to the
number of carbons in the longest chain, the compound is named as a
cycloalkane.
CYCLOALKANES NAMING
(C ONT..)
CYCLOALKANES NAMING
(C ONT..)
CYCLOALKANES NAMING
(C ONT..)
NomenclatureCommon Names
Some organic compounds are identified using common names that do not
follow the IUPAC system of nomenclature. Many of these names were
given long ago before the IUPAC system was adopted, and are still widely
used. Additionally, some names are descriptive of shape and structure, like
those below:
REACTION OF ALKANES
Combustion of Alkanes
Alkanes undergo combustionthat is, they burn in the presence of
oxygen to form carbon dioxide and water.
REACTION OF ALKANES
(C ONT..)
Halogenation of Alkanes
250-400 o
C H + X2
Reactivity:-
or h
C X + HX
REACTION OF ALKANES
(C ONT..)
Polychlorination
CH3Cl + Cl2
CH2Cl2 + HCl
dichloromethane
methylene chloride
CH2Cl2 + Cl2
CHCl3 + HCl
trichloromethane
chloroform
CHCl3 + Cl2
CCl4 + HCl
tetrachloromethane
carbon tetrachloride
E. G:
C HLORINATION OF M ETHANE
45
T ERMINATION S TEPS
O VERALL R EACTION
O VERALL R EACTION
( CONT..)
54
CH 3CH 3
ethane
CH3CH2CH3
propane
CH 3
methyl radical
CH 3CH 2
ethyl radical
CH3CH2CH2
n-propyl radical
CH3CHCH 3
isopropyl radical
X2
X2
X2
X2
CH 3X
halomethane
CH3CH2X
haloethane
CH3CH2CH2X
1-halopropane
CH 3CHXCH 3
2-halopropane
S YNTHESIS
OF ALKANES AND
CYCLOALKANES
H2
CnH2n
H2/Ni
CnH2n+2
C2H5OH
25o, 50 atm
Pt, Pd or Ni
alkene
alkane
+ 2 H2
+ H2
Pt
Pd
(CH3)3CH
R Mg X
RMgX + HOH
R-H + Mg(OH)X
CH3CH2CH2MgBr + H2O
ii.
R-X
R-H
CH3CHBrCH2CH3
iii.
CH3CH2CH3 + Mg(OH)Br
CH3CH2CH2CH3
C9H19CH3
Na
R C C H
NH3
(CH3)2CHC C H
R C C Na+ + 1/2H2
a sodium
acetylide
NaNH 2
ether
(CH3)2CHC C
+ NH3
Na+
R C C- Na + + CH 3X
1. NaNH2
2. CH3Br
H2/Pt
R C CCH 3 + NaX
diethyl ether
2RLi + CuI
R2CuLi + R'X
1o alkyl or 2o
cycloalkyl halide
RLi + LiX
alkyllithium
R2CuLi + LiI
lithium
dialkylcuprate
a Gilman reagent
R-R' + RCu +LiX