Alkanes

The alkanes (i.e. the paraffins) are the simplest homologous series of organic compounds of hydrogen and carbon, where all atoms are linked by single bonds. The general formula for the alkane series of hydrocarbons is CnH2n+2. The alkanes are said to be saturated because the maximum number of bonds are formed between each carbon atoms and its neighboring carbon and hydrogen atoms. The lack of any multiple bonds (i.e. double-bonds or triple-bonds) in the alkanes explain the relative chemical inertness of this series of hydrocarbons.
Methane Ethane Propane Butane Pentane Heptane Hexane Octane Nonane Decane CH4 C2H6 C3H8 C4H10 C5H12 C6H14 C7H16 C8H18 C9H20 C10H22 CH4 CH3CH3 CH3CH2CH3 CH3CH2CH2CH3 CH3CH2CH2CH2CH3 CH3CH2CH2CH2CH2CH3 CH3CH2CH2CH2CH2CH2CH3 CH3CH2CH2CH2CH2CH2CH2CH3 CH3CH2CH2CH2CH2CH2CH2CH2CH3 CH3CH2CH2CH2CH2CH2CH2CH2CH2CH3

The shapes of the alkanes shows that all bonds on the carbon atoms are identical and that the bond angles are close to 109 degrees. Thus, each carbon atom is at the center of a tetrahedral structure, with either carbon atoms or hydrogen atoms at the apices of the tetrahedron. All bonds between carbon atoms (i.e. C-C bonds), or between a carbon atom and hydrogen (i.e. C-H bonds), are s bonds (sigma bonds). These bonds are formed by the end-on overlap of sp3 hydride orbitals of the carbon atoms.

Alkanes Linear Structure

The alkane with the simplest structure is methane, CH4. Each succeeding member of the alkane series has a further methylene group, -CH2-, in the chain. The methane molecule consists of a central carbon atom, surrounded by four hydrogen atoms, with a tetrahedral shape. This tetrahedral structure of methane indicates that the geometry of the orbitals of the carbon in methane molecule, on which the geometry of the bonds depend, is significantly different from the structure of the orbitals in the carbon atom. This is due to hybridisation of four atomic orbitals in carbon atom to four identical molecular orbitals in methane molecule. These molecular orbitals are called SP3 Hybrid Orbitals. The single covalent bonds joining carbon to carbon and carbon to hydrogen in alkanes are sigma bonds formed by the end-on overlap of electron orbitals, so that each carbon atom is the center of a tetrahedron. There is free rotation about all bonds in alkanes.

Methane Ethane Propane Butane Pentane Heptane Hexane Octane Nonane Decane

CH4 C2H6 C3H8 C4H10 C5H12 C6H14 C7H16 C8H18 C9H20 C10H22

CH4 CH3CH3 CH3CH2CH3 CH3CH2CH2CH3 CH3CH2CH2CH2CH3 CH3CH2CH2CH2CH2CH3 CH3CH2CH2CH2CH2CH2CH3 CH3CH2CH2CH2CH2CH2CH2CH3 CH3CH2CH2CH2CH2CH2CH2CH2CH3 CH3CH2CH2CH2CH2CH2CH2CH2CH2CH3

Alkanes Physical Properties

Name ==== Methane Ethane Propane Butane Pentane Hexane Heptane State ===== Gas Gas Gas Gas Liquid Liquid Liquid Formula ======= CH4 C2H6 C3H8 C4H10 C5H12 C6H14 C7H16 MP degC BP degC Density(g/ml) ======= -183 -172 -190 -135 -130 - 95 - 91 ======= -162 -89 -45 -0.5 36 69 98 ======= 0.42 0.55 0.58 0.58 0.63 0.66 0.68

Alkanes Structural Isomerism

Structural isomerism results from the fact that for a given formula, the carbon and hydrogen atoms can be arranged in a number of different ways while retaining the normal combining power of each element. For example, in the case of butane, C4H20, the atoms can be arranged in two different ways, yielding n-butane and iso-butane. Because carbon has a valency of four, and because the carbon to carbon and the carbon to hydrogen covalent bonds are almost identical chemically, it is possible to arrange the linkages between the atoms in an alkane in many different ways. This leads to the concept of structural isomerism, where the isomers have identical formulae but different structural arrangements. Only one arrangement of the atoms within the molecule is possible for methane, CH4, ethane, CH3CH3, and propane, CH3CH2CH3. However, starting with butane, CH3CH2CH2CH3, alternative arrangements of the atoms is possible. The prefix n- (for normal) and iso- (for isomeric) is affixed to the name to distinguish between the isomers.

n-Butane Iso-Butane

C4H20 C4H20

CH3CH2CH2CH3 CH3CHCH3 CH3

The number of possible isomers increases rapidly as the number of carbons increases. Pentane has 3 isomers, and were known as
n-Pentane iso-Pentane CH3 C5H22 C5H22 CH3CH2CH2CH2CH3 (Structure I) CH3CHCH2CH3 (Structure II) neo-Pentane CH3 C5H22 CH3 CH3CCH3 (Structure III)

Structure I is an unbranched chain alkane. Structures II and III are branched chain alkanes. Because the number of structural isomers increases rapidly with increasing number of carbon atoms in a molecule, a systematic method of naming the organic compounds has been promulgated by the International Union of Pure and Applied Chemistry, IUPAC. In structure I, the longest continuous chain contains four carbon atoms and thus this compound is a pentane. In structure II, the longest continuous chain contains four carbon atoms and thus this compound is a butane. As this also has a methyl group attached to the second carbon atom; it is therefore called 2-Methylbutane. In structure III, the longest continuous chain contains three carbon atoms and thus this compound is a propane. As this also has two methyl group attached to the second carbon atom; it is therefore called 2,2-Dimethylpropane. Note that in this molecule, the central carbon atom is bonded to four carbon atoms, and the twelve hydrogen atoms are attached to the other four carbon atoms in the molecule.

Pentanes IUPAC Names

Old Name ======== Structure ========= IUPAC Name ==========

n-Pentane iso-Pentane

CH3CH2CH2CH2CH3 CH3CHCH2CH3 CH3 CH3 CH3CCH3 CH3

Pentane 2- methylbutane

neo-Pentane

2,2-dimethylpropane

5a. The ALKENE hydrocarbons series (unsaturated) Alkenes are hydrocarbons containing a carbon...carbon double bond (>C=C<) as well as single bonds. o Note that the name ends in ...ene eg , ethene, propene, butene etc. Alkenes have the general formula CnH2n where n = 2, 3, 4 etc. giving the formulae C2H4, C3H6, C4H8 etc. o The three formula quoted above match the three names above. o As with naming all organic molecule series eth.. means 2 carbon atoms in the chain, prop... means 3 and but.. means 4 etc. These are called unsaturated molecules because two atoms can join onto half of the double bond when it opens up. o The word unsaturation implies the fact that the carbon atoms are not bonded to the maximum number of atoms they can be. o ie 2 atoms can join onto the two atoms of the carbon-carbon double bond C=C + X-Y ==> X-C-C-Y though when studying and writing the structural/displayed formula equations, make sure each carbon atom forms a total of 4 bonds, not 2 or 3! The first three in the series are shown in the section below and are colourless smelly gases. They are extremely reactive and important compounds in the chemical industry and are converted into very useful compounds e.g. plastics and alcohols. o They are NOT found in crude oil and must be made by cracking - thermally breaking down certain fractions from crude oil. o See Cracking crude oil in the petrochemical industry processes o Advanced Level Notes on the Structure and Naming of Alkenes

Cracking demonstration!

You can demonstrate cracking in the laboratory by heating paraffin grease over an aluminium o oxide catalyst at 400-700 C, and collecting the smaller gaseous hydrocarbon molecules over water - easily shown to be flammable! o This experiment needs to be done as a teacher demonstration - most carefully! o Any hydrocarbon liquids collected in the bottle should decolourise bromine water the test for alkenes. Examples of alkene structure (1) is the molecular formula: a summary of the totals of each atoms of each element in one molecule (2) is are 'shorthand' versions of the full structural formula or displayed formula (3) (3) is called the full structural formula or displayed formula: o The displayed/structural formula shows how all the atoms are linked with the covalent bonds (the dashes -) ie the C-C bonds and the C-H atom bonds. o Note that carbon must form four bonds (C-C single bond or a C=C double bond) and hydrogen forms one bond (C-H). o It is the presence of the carbon = carbon double bond (C=C) which makes alkenes unsaturated hydrocarbon molecules.

(1)

, (2)

, (3)

ethene

the C=C is referred to as the 'double bond'

propene (1) , (2a) (1) , (2) , (2b) , (3) butene

5b. Three important reactions of alkenes

(1) Addition of bromine: A test to distinguish between ALKANE and ALKENE hydrocarbons

Hydrocarbons are colourless. Brominediss olved in water or trichloroethane solvent forms an orange (yellow/brown) solution. When bromine solution is added to both an alkane or an alkene the result is quite different. The alkane solution remains orange - no reaction.

However, the alkene decolourises the bromine as it forms a colourless dibromo-alkane compound - see equations below.

.... or

ethene + bromine ==> 1,2-dibromoethane colour of mixture changes from orange to colourless

Alkenes are unsaturated molecules, a toms can add to them via the C=C double bond, so a reaction occurs. Alkanes are saturated no double bond andatoms cannot add so no reaction.

.... or 2nd example of bromine addition to a double bond. The decolourisation of bromine is a simple and effective chemical test for an alkene - an unsaturated hydrocarbon.

propene + bromine ==> 1,2-dibromopropane (2) Alkenes can add hydrogen to form a saturated alkane molecule H2 propene + hydrogen ==> propane Alkenes will react with hydrogen gas over a nickel catalyst. The reaction process is used to makemargarine from vegetable oils.

(3) Addition of water to make alcohols

eg the alcohol ethanol can be

made by passingethene gas and water vapour over an o acid catalystat 300 C. This is an example of an addition reaction and ahydration reaction because it involves the addition of water to another molecule. see Alcohols, Ethanol, manufacture, reactions, biofuels & alternative fuels For (4) Polymer formation - Polymerisation See Part 7. Polymers-Plastics section and Part 11. More on addition polymers and condensation polymers 5c. More on ALKENES - unsaturated hydrocarbons - a quick summary These cannot be obtained directly from crude oil and must be made by cracking (see section 6 cracking notes). The unsaturated hydrocarbons form an homologous series called alkenes with a general formula CnH2n o Unsaturated means the molecule has a C=C double bond to which atoms or groups can add. Alkene examples: Names end in ...ene o ethene

+ H2O ==> ethene +water ===> ethanol

C2H4 or propene

or

C3H6 or butene

or

or

or The alkenes are more reactive than alkanes because of the presence of the carbon = carbon double bond. The alkenes readily undergo addition reactions in which one of the carbon = carbon double bonds breaks allowing each carbon atom to form a covalent bond with another atom such as hydrogen or bromine. Examples of addition reactions are: with hydrogen under pressure and in the presence of a nickel catalyst to form an alkane

+ H2 ==> ethene + hydrogen ==> ethane

+ H2 ==> propene + hydrogen ==> propane Alkenes react by 'addition' with bromine and decolourises the orange bromine water because the organic product is colourless, and this is a simple test to distinguish an alkene from an alkane. o see above equations for ethene and propene Vegetable oils contain unsaturated fats and can be hardened to form margarine by adding hydrogen on to some of the carbon=carbon double bonds using a nickel catalyst. The process is called hydrogenation, o and the change in an 'unsaturated' part of an oil molecule is o -CH=CH- + H2 ==> -CH2-CH2o so producing a 'saturated' section in the molecule. o The structure of 'fatty' saturated/unsaturated/hydrogenated-fats-oils and uses are described in section 14. Alkenes can add to themselves by addition polymerisation to form 'plastic' or polymeric materials.

o o For more details see section 7. Polymers-plastics notes Alkenes readily burn, just like alkanes, to give carbon dioxide and water. o e.g. ethene + oxygen ==> carbon dioxide + water o C2H4 + 3O2 ==> 2CO2 + 2H2O o However, they are NOT used as fuels for two reasons. 1. They are far too valuable for use to make plastics, anti-freeze and numerous other useful compounds. 2. They burn with a more smokey flame than alkanes due to less efficient and more polluting combustion. Alkenes are isomeric with cycloalkanes e.g. the molecular formula C6H12 can represent hexene or cyclohexane

o o

hexene CH3-CH2-CH2-CH2-CH=CH2 or cyclohexane and note that .... hexene is an unsaturated hydrocarbon with a double bond, the isomeric cyclohexane does not have a double bond and is a saturated hydrocarbon, so a simple bromine test could distinguish the two similar colourless liquids, because only the hexene would decolorize the bromine water test reagent.