CHAPTER 2

ALKANES: STRUCTURE AND NOMENCLATURE OF SIMPLE HYDROCARBONS

HYDROCARBON
 

Compound which composed by carbon & hydrogen 2 major classes of hydrocarbon which are saturated and unsaturated Saturated – alkanes - which all carbon-carbon bonds are single bonds Unsaturated alkenes – the molecules have at least one carbon-carbon double bonds alkynes – the molecules have at least one carbon-carbon triple bonds

MOLECULAR & STRUCTURAL FORMULA
Molecular Formula – the exact number each kind of atom in a compound  Structural Formula – is a graphical representation of the molecular structure showing how the atoms are arranged. There are three common representations: condensed, Lewis type and line-angle formulæ  Structural isomerism – form of isomerism in which molecules with the same molecular formula have atoms bonded together in different orders.  Three types of structural isomers: skeletal, positional, and functional isomers

Skeletal isomer - carbon skeleton are distinctly re-ordered to create different structures. Example: pentane C5H12

n-pentane neopentane/ methylpropane

isopentane/ 2-methylbutane 2,2-

REPRESENTATION OF STRUCTURAL FORMULA

POSITIONAL ISOMERISM
Positional Isomerism –a functional group changes position on the chain.  occurs when functional groups are in different positions on the same carbon chain.  Example:

FUNCTIONAL GROUP ISOMERISM
functional group isomerism a functional group splits up and becomes a different group.  Example: benzene and 1-hexene

IUPAC NOMENCLATURE
Continuous-chain hydrocarbon
Number of Carbons 1 2 3 4 5 6 7 8 9 10 11 12 Prefix Methane Ethane Propane Butane Pentane Hexane Heptane Octane Nonane Decane Undecane Dodecane Structure

CH4 CH3CH3 CH3CH2CH3 CH3(CH2)2CH3 CH3(CH2)3CH3 CH3(CH2)4CH3 CH3(CH2)5CH3 CH3(CH2)6CH3 CH3(CH2)7CH3 CH3(CH2)8CH3 CH3(CH2)9CH3 CH3(CH2)10CH3

Ring or cyclic, prefix cyclo is used to indicate the ring.

NOMENCLATURE OF THE BRANCHED ALKANES
According to IUPAC rules, there are steps in naming the organic compounds. 3) Find the longest chain in the molecule. For a cyclic compound, the ring is usually the base of the name regardless of the longest continuous chain. 4) Numbering the longest chain

3) Name the attached shorter chains (alkyl group). Give the location of each substituent by the number of the main-chain carbon to which it is attached.
CH3— methyl hexyl CH3CH2 — ethyl heptyl CH3CH2CH2 — propyl octyl CH3(CH2)2CH2 — butyl nonyl CH3CHCH3 3(CH2)3CH2 CH3CHCH2CH3 CH — pentyl C(CH3)3 decyl | | Isopropyl sec-butyl tert-butyl CH3(CH2)4CH2 — CH3(CH2)5CH2 — CH3(CH2)6CH2 — CH3(CH2)7CH2 — CH33(CH2)8CH2 2— CH CH(CH3)CH — | isobutyl

3) When 2 or more subst. are present, list them in alphabetical. When 2,3 or more same alkyl group are present, use prefix di, tri, tetra and so on (ignored in alphabetizing)

NOMENCLATURE FOR HALOGENATED HYDROCARBONS (ALKYL HALIDES)
Halogen :
   

Fluorine (F) - fluoro Chlorine (Cl) - chloro Bromine (Br) – bromo Iodin (I) - iodo

CORFORMATIONAL ISOMERISM

conformational isomerism is a form of stereoisomerism involving the phenomenon of molecules with the same structural formula existing as different conformational isomers or conformers due to atoms rotating about a bond. Stereoisomerism - the molecules have the same molecular formula and the same structural formula . However, the atoms have a different three dimensional arrangement in space which makes them non-superimposable Example: Ethane CH3CH3

Sawhorse diagram

Newman projection

If the hydrogen on the adjacent carbons are lined up with one another and as close together as possible results eclipsed conformation. This conformation is less stable. If the hydrogen on the adjacent carbons are far away results staggered conformation. This confirmation is more stable for ethane molecule. These conformation can be represented by either Sawhorse diagram or Newman projection.

Example: Butane
2 methyl groups are as far as possible – 180o

Sawhorse diagram

Newman projection

In the anti conformation (when the dihedral angle=180°) the potential energy is at its lowest, therefore the most stable. This is due to the methyl groups being the farthest away from each other in the molecule. When the dihedral angle=120° or 240°, (eclipsed conformation) in butane, the methyl groups align themselves with hydrogens on the same plane, resulting in the butane having a higher potential energy than the gauche conformations though still having a lower potential energy than the eclipsed conformation (dihedral angle=0° or 360°) When the dihedral angle=60° or 300°, (gauche conformation) in butane, the methyl groups are farther apart . When the dihedral angle=0° or 360°, (eclipsed conformation) in butane, the two methyl groups are in close proximity with the molecule, therefore the potential energy is at its highest.

CYCLOALKANESCONFORMATIONAL AND GEOMETRIC STRUCTURE

Cycloalkanes: saturated ring hydrocarbons

Each carbon atom in the ring has 4 bonded atoms, sp3 hybridized — shall have the angle of 109.5o But the internal angles for : cyclopropane= 60o, cyclobutane= 90o — angle strain, thus make them reactive. cyclopentane = 108o (slightly reactice). High cycloalkane, example:, cyclohexane -= 120o, , cycloheptane = 128o , the rings are large and have sufficient flexibility to twist, bend and pucker out of the plane until each carbon has stable tetrahedral angle. The Bayer Strain Theory

CONFORMATIONAL ISOMERISM IN CYCLOHEXANE

Two conformational isomers in cyclohexane; boat conformation and chair conformation Both conformations have sp3 hybridized for the carbon atoms. The two conformations are not equally stable, chair conformation is more stable.

Hydrogens:  6 axial hydrogens  6 equitorial hydrogens

CONFORMATIONAL ISOMERISM IN SUBSTITUTED CYCLOHEXANES

Example: methylcyclohexane

If there are two groups attached (axial position) to the ring,

If there are two groups attached (axialequitorial) to the ring,

HYDROCARBON: RELATION OF STRUCTURE AND PHYSICAL PROPERTIES
Solid, liquid and gaseous do not represent differences in structure of the individual molecules.  They represent variations in the ARRANGEMENT of the molecules  Solid – arranged very compactly and are relatively immobilized. Very maximum attractive forces.  Liquid – the molecules are mobile but the interaction between molecules are still exist.  Gas – molecular mobility is so great because no interaction between the molecules, theoretically independent of others.

A) MELTING POINT, BOILING POINT
AND MOLECULAR WEIGHT

Increase with increasing in molecular weight. - the plentiful of sites for intermolecular attractions solid liquid gasoeus - the heavier the substance, more energy is needed to break the intermolecules forces

B) MELTING POINT, BOILING POINT AND MOLECULAR STRUCTURE
•Boiling points for unbranched alkanes increase smoothly with the increasing number of atom carbon and molecular weight. Why??? * larger molecules have larger surface area, resulting in increased intermolecular Van de Walls attractions. CH3 CH3 H2 H2 H2 H2 H2 H3C C C C C CH3 H3C C C CH3 H3C C CH3 H CH3 Melting point (MP) : -160oC -130oC -17oC Boiling point (BP) : 36oC 28oC 9.5oC

•BP decrease with chain branching in hydrocarbons. Why???? * branching makes a molecule more compact and decreases the surface area *Small surface – few intermolecular attraction. •MP for highly branched are higher than longer straight chain

C) SOLUBILITY AND DENSITY
 Alkanes

are nonpolar – dissolve in nonpolar or weakly polar organic solvent  Alkanes – hydrophobic – do not dissolve in water  Hydrophobic nature make alkanes good lubricants and preservatives for metal – can avoid metal corrosion.  Alkanes have densities around 0.7g/mL compare with 1.0g/mL for water. So, the mixture of these two quickly separated into two layers