Alkana

CnH2n+2
Dept Teknik Kimia FTUI

Hydrocarbons Hydrocarbons

Aliphatic Aliphatic

Aromatic Aromatic

Hydrocarbons Hydrocarbons

Aliphatic Aliphatic

Aromatic Aromatic

Alkana Alkana

Alkena Alkena

Alkuna Alkuna

Hydrocarbons Hydrocarbons
Alkanes are hydrocarbons in which all of the bonds are single bonds.

Aliphatic Aliphatic H Alkana Alkana

H C H
etana

H C H H

Hydrocarbons Hydrocarbons

Aliphatic Aliphatic

Alkenes are hydrocarbons that contain a carbon-carbon double bond.

H Alkena Alkena H C C
Etena

Hydrocarbons Hydrocarbons
Alkuna are hydrocarbons that contain a carboncarbon triple bond.

Aliphatic Aliphatic

HC

CH

Alkuna Alkuna

Asetilen

Hydrocarbons Hydrocarbons
The most common aromatic hydrocarbons are those that contain a benzene ring.

H H H H H H Aromatic Aromatic

Struktur alkana

tetrahedral about carbon all bond angles are approximately 109.5

Penggambaran Alkana
Ball-andstick model Line-angle formula Structural formula CH3 CH2 CH3 Propane CH 3 CH2 CH2 CH3 Butane CH 3 CH 2 CH 2 CH 2 CH 3 Pentane

Penamaan Alkana

Suffix -ana specifies an alkana Prefix tells the number of carbon atoms
Prefix Carbons meth1 eth2 prop3 but4 pent5 hex6 7 heptoct8 non9 dec10 Carbons Prefix undec11 dodec12 tridec13 tetradec14 pentadec15 hexadec16 heptadec17 octadec18 nonadec19 eicos20

Penamaan Alkana

Parent name: the longest carbon chain Substituent: a group bonded to the parent chain alkyl group: given the symbol RName Methane Ethane Alkyl group CH3 CH3 CH 2 Name Methyl group Ethyl group

Alkane CH4 CH3 CH 3

Penamaan Alkana

Each substituent is given a name and a number

CH3 CH3 CHCH3
1 2 3

2-Methylprop 2-metilpropana ane

If there is one substituent, number the chain from the end that gives it the lower number
4 5 3 2 2 1 3 4

CH3 CH3 CH2 CH2 CHCH3

2-Methylpen tane 2-metilpentana

(not 4-meth ylp entane)

Penamaan Alkana

If there are two or more identical substituents, number the chain from the end that gives the lower number to the substituent encountered first indicate the number of times the substituent appears by a prefix di-, tri-, tetra-, etc. use commas to separate position numbers

4 3

2 1

3 4

5 6

2,4-Dimethylhexan e (n ot 3,5-d imethylhexan e) 2,4-dimetilheksana

Penamaan Alkana

If there are two or more different substituents, list them in alphabetical order number from the end of the chain that gives the substituent encountered first the lower number
1 2 3 4 5 6 7 7 6 5 4 3 2 1

3-etil-5-metilheptana 3-Ethyl-5-methylh eptane

(n ot 3-methyl-5-ethylheptane)

Penamaan Alkana

The prefixes di-, tri-, tetra-, etc. are not included in alphabetization alphabetize the names of substituents first and then insert these prefixes

2 3

4-Ethyl-2,2-dimethylh exane 4-etil-2,2-dimetilheksana (not 2,2-dimethyl-4-eth ylh exane)

Physical Properties

Boiling points: increase with increasing number of carbons decrease with chain brainching Alkanes are non-polar, soluble in nonpolar or slightly polar solvents, insoluble in water Intermolecular forces are van der Waals forces Less dense than water

Chemical Properties

All alkanes burn in air to give CO2 and H2O Halogenation Pyrolysis (cracking): decomposition of a compound by the action of heat alone

Halogenation
(mekanisme radikal bebas) Alkanes can react with halogens to form alkyl halides via free radical substitution pathways.

A radical is

Halogenation
(mekanisme radikal bebas) Carbon radicals are formed by homolytic cleavage of covalent bonds using either: (1) Light ( h) (2) Heat () (3) Radical Initiators (ROOR i.e. peroxides)

Halogenation

Stage I Initiation
( f ormation of the halogen radicals)

The mechanism has three distinct stages.

Stage II Propagation
( f ormation of product and another halogen radical)

Stage III Termination

( multiple pathways to extinguish all radicals)

Halogenation
Initiation: The reaction begins with an initiation stage, which is the separation of the halogen (X2) into two radicals (atoms with a single unpaired electron) by the addition of uv light.

Halogenation
Propogation: The initiation stage, or the formation of the chlorine radicals, is immediately followed by the propogation stages--stages directly involved in the formation of the product.

In the last stage, the tertiary radical then reacts with another one of the chlorine molecules to form the product.

Halogenation
Termination: Side reactions that can stop the chain reaction are called termination stages.

Halogenation

excess halogen is used monohalogenation

The most important steps of radical halogenation are those that lead to product formationthe propagation steps

Radical ReactionsMechanism

Sources of Alkanes

Natural gas

90-95% methane gases (bp below 20C) naphthas, including gasoline (bp 20 - 200C) kerosene (bp 175 - 275C) fuel oil (bp 250 - 400C) lubricating oils (bp above 350C) asphalt (residue after distillation)

Petroleum

Coal Biomass ??????????

Cycloalkanes

General formula CnH2n

five- and six-membered rings are the most common to name, prefix the name of the corresponding open-chain alkane with cyclo-, and name each substituent on the ring if only one substituent, no need to give it a number if two substituents, number from the substituent of lower alphabetical order if three or more substituents, number to give them the lowest set of numbers and then list substituents in alphabetical order

Structure and nomenclature

Cycloalkanes

Line-angle drawings

each line represents a C-C bond each vertex and line ending represents a C
C C C C C C H2 C H2 C CH2 CH2 C8 H1 6 CH3 CH 3 CH CH

C C

Cycloalkanes

Example: name these cycloalkanes

(a)

(b)

(c)

(d)

Bicycloalkanes

Bicycloalkane: an alkane that contains two rings that share two carbons

Bicyclo[4.4.0]decane (Decalin)

Bicyclo[4.3.0]nonane (Hydrindane)

Bicyclo[2.2.1]heptane (Norbornane)

(camphor)

monoterpenes odorous components of plants

1,7,7-trimethylbicyclo [2.2.1]heptan-2-one

Bicycloalkanes

Nomenclature parent is the alkane of the same number of carbons as are in the rings number from a bridgehead, along longest bridge back to the bridgehead, then along the next longest bridge, etc. show the lengths of bridges in brackets, from longest to shortest
one C
1 6 7 5 4 3 2

bridgehead

two Cs

Bicyclo[2.2.1]h eptane

Isomers

relationships among isomers

Cis,Trans Isomerism (Geometric isomers)

Cis,trans isomers

stereoisomers that are the result of the presence of either a ring or a carbon-carbon double bond

Cis,Trans Isomers

1,2-Dimethylcyclopentane

H H H H H CH3 CH3 H H H H H

H H H HH 3 C H CH3 H

H3 C

CH3

H3 C

CH3

cis-1,2-D imeth ylcyclop entane

trans-1,2-D imethylcyclop entane

Cis,Trans Isomerism

1,4-Dimethylcyclohexane

H H3 C

CH3 H CH3

H H3 C

H CH3 CH3

H3 C t rans-1,4-D imethylcyclohexane

H3 C cis-1,4-D imethylcycloh exane

Cis,Trans Isomerism

trans-1,4-Dimethylcyclohexane

the diequatorial-methyl chair conformation is more stable by approximately 2 x (7.28) = 14.56 kJ/mol
CH3 H H CH3 (less stable) H (more stable) H H3 C CH3

Cis,Trans Isomerism

cis-1,4-Dimethylcyclohexane

H CH3 H CH3 H3 C

H conformation s are of equal s tability CH3

Cis,Trans Isomerism

The decalins

H A B H

H trans-Decalin

H A B H

H cis-Decalin

Conformations

Conformation: any three-dimensional arrangement of atoms in a molecule that results from rotation about a single bond Newman projection: a way to view a molecule by looking along a carbon-carbon single bond

Conformations

Staggered conformation: a conformation about a carbon-carbon single bond in which the atoms or groups on one carbon are as far apart as possible from the atoms or groups on an adjacent carbon
H H H H H H

Conformations

Eclipsed conformation: a conformation about a carbon-carbon single bond in which the atoms or groups of atoms on one carbon are as close as possible to the atoms or groups of atoms on an adjacent carbon
H
H

H H

HH

Conformations

Torsional strain also called eclipsed interaction strain strain that arises when nonbonded atoms separated by three bonds are forced from a staggered conformation to an eclipsed conformation the torsional strain between eclipsed and staggered ethane is approximately 12.6 kJ (3.0 kcal)/mol

+12.6 kJ/mol

Conformations

Dihedral angle (Q): the angle created by two intersecting (Q) planes

Conformations

Ethane as a function of dihedral angle

Conformations

conformations of butane as a function of dihedral angle

Anti Butane

Energy-minimized anti conformation

the C-C-C bond angle is 111.9 and all H-C-H bond angles are between 107.4 and 107.9

Eclipsed Butane

Cyclopropane

angle strain: the C-C-C bond angles are compressed from 109.5 to 60 torsional strain: there are 6 sets of eclipsed hydrogen interactions strain energy is about 116 kJ (27.7 kcal)/mol
H H

H H

Cyclobutane

puckering from planar cyclobutane reduces torsional strain but increases angle strain the conformation of minimum energy is a puckered butterfly conformation strain energy is about 110 kJ (26.3 kcal)/mol

Cyclopentane

puckering from planar cyclopentane reduces torsional strain, but increases angle stain the conformation of minimum energy is a puckered envelope conformation strain energy is about 42 kJ (6.5 kcal)/mol

Cyclohexane

Chair conformation: the most stable puckered conformation of a cyclohexane ring

all bond C-C-C bond angles are 110.9 all bonds on adjacent carbons are staggered

Cyclohexane

In a chair conformation, six H are equatorial and six are axial

Cyclohexane

For cyclohexane, there are two equivalent chair conformations

all C-H bonds equatorial in one chair are axial in the alternative chair, and vice versa

Cyclohexane

Boat conformation: a puckered conformation of a cyclohexane ring in which carbons 1 and 4 are bent toward each other

there are four sets of eclipsed C-H interactions and one flagpole interaction a boat conformation is less stable than a chair conformation by 27 kJ (6.5 kcal)/mol

Cyclohexane

Twist-boat conformation

approximately 41.8 kJ (5.5 kcal)/mol less stable than a chair conformation approximately 6.3 kJ (1.5 kcal)/mol more stable than a boat conformation

Cyclohexane

Methylcyclohexane

Equatorial and axial methyl conformations

CH3 +7.28 kJ/mol CH3