ALKANES Hydrocarbons General formula CnH2n+2 All C atoms are sp3-hybridized. All single bonds ( bonds).

ds). Saturated hydrocarbons HOMOLOGOUS SERIES Compounds that differ from each other in their molecular formulas by the unit CH2(methylene) unit. The boiling points of alkanes increases steadily with increase in molecular weight within a homologous series: C1 C4, gases; C5 C17, liquids; C18 and up, solids. The boiling points of different alkanes with the same MW increases as the chain length increases. Melting points of different alkanes with the same MW depend on the compactness of the molecular shape. Spherical molecules pack better in crystal lattices and will have higher melting points.

Methane, CH4 simplest hydrocarbon

H H H a 3-D representation C H H H Lewis structure H C H CH4 condensed formula

Ethane
H H C C H H H H C H C H CH3CH3 condensed formula

H H perspective drawing

H H Lewis strcuture

CONFORMATIONS OF A MOLECULE: Different arrangements in space of the atoms within the molecule due to rotations around single bonds.

NEWMAN PROJECTIONS View of a molecule down the axis of a C-C bond. The C atom toward the front is represented by a dot, and the C atom toward the rear by a circle. The atoms or groups of atoms on the C atoms are shown as being bonded to the dot or circle.

H H H H H H H

HH H H

H Staggered

Eclipsed

Propane

C3H8 CH3CH2CH3 Contains 2 different kinds of Cs: o Primary C (1 C) attached to only 1 other C o Secondary C (2 C) attached to 2 other Cs

Butane 2 possible structures for C4H10:

H H H H H C C C C H H H H H H H C H H H H C C C H H H H 2-methylpropane (or isobutane) n-butane

Tertiary (3o) carbon bonded to three other C atoms. Staggered Conformations of Butane: Anti conformation methyl groups are farthest from each other; most stable conformation of butane. Gauche conformation methyl groups are 60o apart; less stable than anti conformation by 0.9 kcal/mol. Line structures for organic compounds: A.k.a. skeletal structural formulas Each junction of 2 straight lines or the end of a straight line represents a C atom and the necessary number of H atoms to give the C atom 4 bonds. Functional groups are represented by their usual symbols. Alkanes may be: Acyclic hydrocarbons open-chain alkanes Cycloalkanes

Cycloalkanes: Hydrocarbons in which some or all of the C atoms form a ring. General formula: CnH2n. Named by adding the prefix cyclo- to the name of the alkane having the same number of C atoms as are in the ring.

Cyclopropane: Smallest cycloalkane. All three Cs define a plane. Internal bond angles of 60o; External C-C-H bond angle of 116o. H-C-H bond angle of 118o. All the bonds are eclipsed.

Contains bent bonds, i.e., the orbitals overlap at a slight angle bonds are weaker and more reactive than other alkane bonds. Has a lot of angle strain.

Cyclobutane: One of the atoms in the ring is bent out of plane of the other three by about 20o. Internal bond angle is 88o instead of 90o. This minimizes the eclipsing of H atoms on adjacent C atoms increases angle strain but decreases torsional strain. Has less angle strain than cyclopropane but more torsional strain because of its larger number of Hs.

Angle strain the strain introduced into a molecule when a bond angle is deformed from its ideal value. Torsional strain or eclipsing strain; the strain in a molecule caused by electron repulsion between eclipsed bonds.

Cyclopentane: Bond angles are close to the tetrahedral bond angle. Most stable conformation when one C is out of plane of the other 4 Cs envelop Cyclohexane: C6H12 Bond angles: 109o Exist in two conformations: Chair and boat Axial hydrogens in cyclohexane 3Hs are above the plane while the other 3 are below the plane. Equatorial hydrogens in cyclohexane lie roughly in the plane of the molecule
Axial H H H H H H H H H H H Equatorial H H H

Newman Projections of Chair and Boat Forms

Chair form
H H CH2 H H

Boat form H H

H H

HH
H H CH2 H H

H H

Methylcyclohexane
H H CH2 CH3 H H H CH2 H CH3

H H

CH2

H H

CH2

 The more stable conformation has the methyl group at the equatorial position. In general, the larger the substituent, the greater the repulsive interaction when it occupies an axial position. 1,2-Dimethylcyclohexane May be cis or trans Cis-1,2-dimethylcyclohexane has both methyls on the same side of the plane of the ring

H H H H

CH3 CH3 H H H H

CH3 CH3

In trans-1,2-dimethylcyclohexane, the 2 methyl groups are on opposite side of the plane of the ring.

H H H H

CH3 H H CH3 H H

H CH3

ISOMERS: Different compounds with the same molecular formula May be: 1. Structural or constitutional isomers differ in the way the atoms are bonded together. 2. Stereoisomers differ in the way the atoms are oriented in space but the attachment of atoms is the same Geometric Isomerism: Due to restricted rotation about a rigid structure such as a multiple bond or a ring structure. Examples: cis and trans isomers of alkenes and cycloalkanes. Stereoisomers can also be present in compounds with at least one chiral center. Chiral center carbon which is bonded to 4 different atoms or groups of atoms. Enantiomers compounds which are non-superimposable mirror images of each other Diastereomers non-superimposable compounds which are not mirror images For a molecule having n chiral centers, the maximum number of stereoisomers is 2n. Meso compound compound that has chiral centers but is superimposable on its mirror image. This happens because there is a symmetry plane within the molecule Example: Tartaric acid

CH3

COOH H H OH OH COOH

Reactions of Alkanes: 1. Combustion 2. Halogenation. Reaction with halogens at high temperatures or under the influence of light (h). Gives a mixture of products.

CH4

+ Cl2

CH3Cl + CH2Cl2

+ CHCl3 + CCl4 Intermediates unstable short-lived species Reactive intermediate free radicals. Free radical a highly reactive intermediate which has an unpaired electron and no charge Chain reaction type of reaction in which the product of one step is a reactant in the next step. Free radical chain reaction the reactive intermediate formed in different steps of the reaction are free radicals.

Steps in a chain reaction: 1. Initiation Step in which the first reactive intermediate is formed. In halogenation, homolytic cleavage of the halogen molecule is the initiation step.

.. : Cl ..
2.

.. Cl .. :

.. : Cl . ..

.. . Cl : ..

Propagation Consists of steps that are repeated many times to carry the reaction forward. A radical is present in the reactant side, and a radical is also formed as product.

H H C H H
H H C. H
3.

.. + . Cl .. :

H H C. H
H .. . Cl : ..

+ HCl

Cl2

H C Cl H

Termination Consists of steps that occur when two free radicals collide with each other and form a covalent bond, thereby stopping the chain of reactions.
H H C. H .. : Cl . .. H H C. H + + .. . Cl : .. H H C. H .. : Cl .. + .. . Cl : .. H H C Cl H .. : Cl .. H H H C C H H H

Stability of Free Radicals:

Most stable

3o > 2o > 1o > H3C .

Least stable