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Chapter 3: Alkanes and their Stereochemistry

Coverage: 1. Survey of Functional Groups 2. Alkane Isomers 3. Alkyl Groups 4. Nomenclature of Alkanes 5. Properties of Alkanes 6. Conformations of Ethane, Propane, Butane 7. Special Topic: Refining of Petroleum

Goals: 1. Be able to recognize and identify the functional group(s) in a molecule. 2. Be able to predict the hybridization of an atom in a functional group. 3. Know the definition of constitutional and stereoisomers and be able to apply definitions to alkanes. 4. Know the structures of alkyl groups up to 4 carbons. 5. Know the IUPAC system of nomenclature for naming alkanes. 6. Know trends in boiling points and melting points of alkanes, both branched and straight chain. 7. Know the meaning of gauche, anti, eclipsed, staggered in conformations. 8. Be able to draw Newman projections of ethane, propane, butane and others. 9. Know the sources of hydrocarbons, particularly petroleum refining.
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Classification of Organic Molecules Functional Groups


1. Hydrocarbons - molecules that possess only hydrogen and carbon a1. Alkanes noncyclic hydrocarbons with only C-C single bonds. Formula CnH2n+2 where n is an integer. Example: Butane CH3CH2CH2CH3 C4H10

a2. Cycloalkanes cyclic hydrocarbons with only C-C single bonds. Formula CnH2n where n is an integer. Example: Cyclobutane C4H8

b1. Alkenes noncyclic hydrocarbons with C=C double bonds. Formula CnH2n where n is an integer.
Example: 2-Butene CH3CH=CHCH3 C4H8
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b2. Cycloalkenes cyclic hydrocarbons with C=C double bonds. Formula CnH2n-2 where n is an integer. Example: Cyclobutene C 4 H6

c. Alkynes noncyclic hydrocarbons with C=C triple bonds. Formula CnH2n-2 where n is an integer. Example: Butyne CH3C=CCH3 C4H6

d. Aromatic Hydrocarbons benzene and its derivatives


H H C C C H C H C H C H

or

C6H6

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2. Compounds containing Oxygen


a. Alcohols R-OH

Functional Group OH hydroxyl group CH3OH methyl alcohol HOCH2CH2OH ethylene glycol (antifreeze)

b. Ethers

R-O-R

CH3CH2-O-CH2CH3 Diethylether c. Aldehydes and Ketones

O R-C-H

O R-C-R'
C=O carbonyl group
O
H O

Functional Group
O

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d.

Carboxylic Acids

O R-C-OH

O -COH Carboxyl Group


O

Functional Group
O CH3-C-OH

-CO2H

-COOH

H2O

H3O+

CH3CO-

Acetic Acid

e. Derivatives of Carboxylic Acids


O R-C-OR' O R-C-Cl O R-C-NH2

Ester

Acid Chloride

Amide

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3. Nitrogen-Containing Molecules
a. Amines R-NH2 -NH2 amino group
N N H

Functional Group
CH3NH2

Amines are Lewis and Bronsted bases because of the nonbonded pair of electrons

NH2 ..

HCl

NH3+ Cl

b. Amides (see above)

c. Nitriles

R C N
C N
Cyano Group
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Functional Group

Use of Wedges and Dashed Lines

H H C

H H

Solid Wedge indicates coming toward you Dashed Line indicates going away Narrow Line indicates in the plane of paper

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Single versus Double Bonds

H H C H C

H H
H

H H C C H

Ethane The carbon-carbon single bond in ethane freely rotates at room temperature.

H C H C

H C C

Ethylene

Pi bond broken

The carbon-carbon double bond in ethylene does not freely rotate at room temperature. Why not? Answer: The Pi bond would have to be broken. It will not break at room temperature
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Isomers different compounds with the same formula


a. Constitutional (Structural) Isomers isomers that differ in their bonding sequence
CH3 CH3CHCH2CH3\ vs CH3CH2CH2CH2CH3

C5H12
Cl C=C H H Br

C5H12

H C=C H

Br Cl

C2H2BrCl

C2H2BrCl

b. Stereoisomers isomers that differ in their spatial orientation


Cl C=C H H H Br Cl C=C Br H

C2H2BrCl Cis isomer

C2H2BrCl Trans isomer

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Alkyl Groups
R is the general symbol for an alkyl group. For example R-OH represents an alcohol where R is an alkyl group. R-Cl is an alkyl chloride.

Alkyl Groups know the following


-CH3 methyl -CH2CH3 ethyl -CH2CH2CH3 propyl -CH2CH2CH2CH3 butyl -CH2CHCH3 CH3 isobutyl -CHCH2CH3 sec-butyl CH3 CH3 -C CH3 CH3 tert-butyl

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Carbon Substitution
a. Primary carbon (1o) - carbon attached to one other carbon. R-CH3 1o

b. Secondary carbon (2o) - carbon attached to two other carbons. R-CH2-R 2o c. Tertiary carbon (3o) carbon attached to three other carbons 3o R-CH-R R d. Quaternary (4o) carbon attached to four other carbons.
R R

R C R
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4o

Alkane Nomenclature
1. Find the parent hydrocarbon a. Find the longest continuous chain of carbon atoms and name it accordingly. Number Carbons 1 2 3 4 5 6 7 8 9 10 Name methane ethane propane butane pentane hexane heptane octane nonane decane

Named as a hexane

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b. If two different chains of equal length are present, choose the one with the larger number of branch points.

Named as hexane with 2 substituents not hexane with 1 substituent 2. Number the atoms in the main chain

a. Begin at the end nearer the first branch point.


4 2 1 3 5 6

b. If there are branch points at equal distances away, begin at the end nearer the second branch point.
9 8 5 7 6 4 3 2 1

Named as a nonane with branch points at carbons 3, 4, 7.


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3. Identify and number the substituents.


9 8 5 7 6 4 3 2 1

3-ethyl 4-methyl 7-methyl

4. Write the name as a single word. a. Use prefixes such as mono, di, tri, tetra, etc. to indicate multiple substituents. b. List substituents alphabetically, ignoring prefixes. c. Use dashes to separate substitutents, use commas to separate numbers. The above example would have the name 3-ethyl-4,7-dimethylnonane
1

Name this alkane:

Answer: 5-sec-butyldecane
7 8 9 6

3 4 5

10

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Physical Properties of Alkanes


1. Combustion - Alkanes are inflammable, i.e. they burn.

CH4

2 O2

CO2

+ 2 H2O

2. Boiling and melting points a. Both bp and mp increase with increasing carbon number for straight-chain alkanes with formula CnH2n+2 Carbon Number C1 - C4 C5 C16 C17 C30 C30 C50 >C50 Physical State gases liquids oils and greases paraffin waxes plastics (polyethylene)

b. Branching tends to raise the melting point and lower the boiling point.

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b. Branching tends to lower the boiling point and raise the melting point

BP

60oC

58oC -135oC

50oC -98oC

MP -154oC Explanation:

MP Branching reduces the flexibility of the molecule which reduces the entropy term S in the equation Tmp = H/S. Since S is in the denominator, Tmp increases. BP Branching reduces surface area (more compact structure), and therefore London dispersion forces which control boiling point for these molecules. 3. Solubility alkanes are nonpolar molecules and therefore insoluble in water, which is polar. Alkanes are hydrophobic. 4. Densities alkanes are less dense than water, with densities near 0.7 g/mL. Therefore 3-16 they float on water, e.g. Exxon Valdez oil spill.

1. Conformation of Ethane
CH3CH3
H H H C2 C
1

H H H

Rotate 60o

H H C H C

H H H

Sawhorse

H H H

H H

H H

Newman projection
H H H

HH

Staggered Conformation Lower Energy More Stable

Eclipsed Conformation Higher Energy Less Stable

The staggered conformation is more stable by 3.0 kcal/mol


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Dihedral Angle the angle defined by the C-H bond on the front carbon and the C-H bond on the back carbon in a Newman projection.
H H
0 H 0 H

600
H H H

HH

H H

3.0 kcal/mol

0.0 kcal/mol

Eclipsed

Staggered

Eclipsed

Staggered

Eclipsed

Staggered

Eclipsed

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Why is the staggered conformation more stable than the eclipsed conformation? In the eclipsed conformation, the C-H bonds are closer, resulting in a repulsion of the electron clouds. This effect is referred to torsional strain. Torsional strain exists anytime C-H bonds are eclipsed.

1.0 kcal/mol

H H

H 1.0 kcal/mol H

Total Energy: 3.0 kcal/mol

HH

1.0 kcal/mol

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2. Conformations of Propane
H H H C
1

H H C
2

H H C1 C
2

Rotate

600

H H

CH3

CH3

H H H

Rotate 600

H CH3

More stable 0.0 kcal/mol 1.0 kcal/mole 1.0 kcal/mol

Less stable 3.3 kcal/mol The additional 0.3 kcal/mol energy is due to steric strain. Steric strain electronic repulsion that occurs when two atoms or groups are forced together. 3-20

1.3 kcal/mol

3. Conformations of Butane

H3C H H C
2

H H C
3

60o

H H3C C
2

H H C
3

CH3

CH3

CH3

60o
H CH3 H

H H

H CH3

Anti Conformation Staggered 180o dihedral


H H H
H H H H

HCH3

Eclipsed
H H H
H3C H

H H

H CH3

Anti
CH3
H3CCH3

H3C

Gauche Conformation Staggered 60o dihedral

CH3

HCH3

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There are two staggered conformations of different energy. There are two eclipsed conformations of different energy.

Remember, staggered conformations are more stable than eclipsed conformatiions Quicktime Movie

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Petroleum Refining

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1. The first step in petroleum refining is fractional distillation.

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2. Upstream processing of the distillates.


a. Catalytic hydrocracking produces small alkanes from large alkanes by adding hydrogen.
H2, heat Si-Al catalyst

b. Catalytic cracking produces small alkenes and alkanes by cracking in the absence of hydrogen.
heat Si-Al catalyst

c. Catalytic Reforming the alkanes and cycloalkanes are upgraded to higher octane number by conversion into aromatic compounds.
-H2 catalyst, heat -3H2 catalyst, heat

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Octane Number
Straight-chain hydrocarbons have low octane and make poor fuels. Octane Number = 0 heptane Branched Alkanes burn more slowly and reduce the knocking in the engine.

Octane Number = 100


2,2,4-trimethylpentane

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