1. AN INTRODUCTION TO THE CHEMISTRY OF ALKANES KNOCKHARDY PUBLISHING

2. CONTENTS Structure of alkanes Physical properties of alkanes Chemical properties of alkanes Breaking covalent bonds Chlorination via free radical substitution Cracking Revision check list THE CHEMISTRY OF ALKANES

3. Generalmembers of a homologous series general formula is C n H 2n+2 - for non-cyclic alkanes saturated hydrocarbons - all carbon-carbon bonding is single bonds are spaced tetrahedrally about carbon atoms. Isomerismthe first example of structural isomerism occurs with C 4 H 10 BUTANE 2-METHYLPROPANE Structural isomers have the SAME MOLECULAR FORMULA BUT DIFFERENT STRUCTURAL FORMULA They possess different physical properties such as boiling point, melting point and density ALKANES

4. HYBRIDISATION OF ORBITALS The electronic configuration of a carbon atom is 1s 2 2s 2 2p 2 1 1s 2 2s 2p

5. HYBRIDISATION OF ORBITALS The electronic configuration of a carbon atom is 1s 2 2s 2 2p 2 1 1s 2 2s 2p If you provide a bit of energy you can promote (lift) one of the s electrons into a p orbital. The configuration is now 1s 2 2s 1 2p 3 1 1s 2 2s 2p The process is favourable because the of arrangement of electrons; four unpaired and with less repulsion is more stable

6. HYBRIDISATION OF ORBITALS IN ALKANES The four orbitals (an s and three p’s) combine or HYBRIDISE to give four new orbitals. All four orbitals are equivalent. Because one s and three p orbitals are used, it is called sp 3 hybridisation 2s 2 2p 2 2s 1 2p 3 4 x sp 3

7. In ALKANES, the four sp 3 orbitals of carbon repel each other into a TETRAHEDRAL arrangement with bond angles of 109.5º. Each sp 3 orbital in carbon overlaps with the 1s orbital of a hydrogen atom to form a C-H bond. THE STRUCTURE OF ALKANES 109.5º

8. Alkanes - Nomenclature The names of alkanes are composed of two parts – (i) a prefix which comes from the number of carbon atoms in the longest straight chain in the molecule. Apart from the first four, which have trivial names, the number of carbons atoms is indicated by a prefix derived from the Greek numbering system. Prefix C atoms Alkane meth-1methane eth-2ethane prop-3propane but-4butane pent-5pentane hex-6hexane hept-7heptane oct-8octane non-9nonane dec- 10decane (ii) a suffix or ending which shows which type of organic compound it is. With alkanes this suffix is ___ane. Examples -ethane - octane -

9. CH 2 CH 3 CH 2 CH 3 CH 2 CH 3 CH 2 CH 3 CH 2 CH 3 I.U.P.A.C. NOMENCLATURE How long is a chain? Because organic molecules are three dimensional and paper is two dimensional it can confusing when comparing molecules. This is because... 1. It is too complicated to draw molecules with the correct bond angles 2. Single covalent bonds are free to rotate All the following written structures are of the same molecule - PENTANE C 5 H 12 A simple way to check is to run a finger along the chain and see how many carbon atoms can be covered without reversing direction or taking the finger off the page. In all the above there are... FIVE CARBON ATOMS IN A LINE.

10. CH 2 CH 3 CH 2 CH CH 3 CH 2 CH 3 CH CH 2 CH 3 I.U.P.A.C. NOMENCLATURE How long is the longest chain? Look at the structures and work out how many carbon atoms are in the longest chain. CH 3 CH CH 2 CH 3 CH CH 3 THE ANSWERS ARE ON THE NEXT SLIDE

11. CH2CH2 CH3CH3 CH2CH2 CH2CH2 CHCH CH3CH3 CH 3 CH2CH2 CH3CH3 CHCH CH2CH2 CH3CH3 I.U.P.A.C. NOMENCLATURE How long is the longest chain? Look at the structures and work out how many carbon atoms are in the longest chain. CH3CH3 CH 3 CHCH CH2CH2 CH2CH2 CH3CH3 CHCH LONGEST CHAIN = 5 LONGEST CHAIN = 6

12. CH2CH2 CH3CH3 CH2CH2 CH2CH2 CHCH CH3CH3 CH 3 CH2CH2 CH3CH3 CHCH CH2CH2 CH3CH3 I.U.P.A.C. NOMENCLATURE How long is the longest chain? Look at the structures and work out how many carbon atoms are in the longest chain. CH3CH3 CH 3 CHCH CH2CH2 CH2CH2 CH3CH3 CHCH LONGEST CHAIN = 5 LONGEST CHAIN = 6

13. NOMENCLATURE Ideally a naming system should tell you everything about a structure without ambiguity. There are two types of naming system commonly found in organic chemistry; Trivial :based on some property or historical aspect; the name tells you little about the structure Systematic :based on an agreed set of rules (I.U.P.A.C); exact structure can be found from the name (and vice-versa). HOMOLOGOUS SERIES trivial namesystematic name example(s) paraffin alkanemethane, butane olefin alkeneethene, butene fatty acid alkanoic (carboxylic) acidethanoic acid INDIVIDUAL COMPOUNDS trivial name derivation systematic name methanemethu = wine (Gk.)methane (CH 4 ) butanebutyrum = butter (Lat.)butane (C 4 H 10 ) acetic acidacetum = vinegar (Lat.)ethanoic acid (CH 3 COOH)

14. SIDE-CHAIN carbon based substituents are named before the chain name. they have the prefix -yl added to the basic stem (e.g. CH 3 is methyl). Number the principal chain from one end to give the lowest numbers. Side-chain names appear in alphabetical order butyl, ethyl, methyl, propyl Each side-chain is given its own number. If identical side-chains appear more than once, prefix with di, tri, tetra, penta, hexa Numbers are separated from names by a HYPHENe.g. 2-methylheptane Numbers are separated from numbers by a COMMAe.g. 2,3-dimethylbutane Alkyl radicals methylCH 3 - CH 3 ethylCH 3 - CH 2 - C 2 H 5 propylCH 3 - CH 2 - CH 2 - C 3 H 7 I.U.P.A.C. NOMENCLATURE

15. SIDE-CHAIN carbon based substituents are named before the chain name. they have the prefix -yl added to the basic stem (e.g. CH 3 is methyl). Number the principal chain from one end to give the lowest numbers. Side-chain names appear in alphabetical order butyl, ethyl, methyl, propyl Each side-chain is given its own number. If identical side-chains appear more than once, prefix with di, tri, tetra, penta, hexa Numbers are separated from names by a HYPHENe.g. 2-methylheptane Numbers are separated from numbers by a COMMAe.g. 2,3-dimethylbutane Alkyl radicals methylCH 3 - CH 3 ethylCH 3 - CH 2 - C 2 H 5 propylCH 3 - CH 2 - CH 2 - C 3 H 7 I.U.P.A.C. NOMENCLATURE

16. SIDE-CHAIN carbon based substituents are named before the chain name. they have the prefix -yl added to the basic stem (e.g. CH 3 is methyl). Number the principal chain from one end to give the lowest numbers. Side-chain names appear in alphabetical order butyl, ethyl, methyl, propyl Each side-chain is given its own number. If identical side-chains appear more than once, prefix with di, tri, tetra, penta, hexa Numbers are separated from names by a HYPHENe.g. 2-methylheptane Numbers are separated from numbers by a COMMAe.g. 2,3-dimethylbutane Example longest chain 8 (it is an octane) 3,4,5 are the numbers NOT 4,5,6 order is ethyl, methyl, propyl 3-ethyl-5-methyl-4-propyloctane Alkyl radicals methylCH 3 - CH 3 ethylCH 3 - CH 2 - C 2 H 5 propylCH 3 - CH 2 - CH 2 - C 3 H 7 CH 3 CH 2 CH 3 CH CH 2 CH 3 CH CH 2 CH 3 CH 2 CH 3 I.U.P.A.C. NOMENCLATURE

17. CH 2 CH 3 CH 2 CH CH 3 CH 2 CH 3 CH CH 2 CH 3 I.U.P.A.C. NOMENCLATURE Apply the rules and name these alkanes CH 3 CH CH 2 CH 3 CH CH 3 THE ANSWERS ARE ON THE NEXT SLIDE

18. CH 2 CH 3 CH 2 CH CH 3 CH 2 CH 3 CH CH 2 CH 3 I.U.P.A.C. NOMENCLATURE CH 3 CH CH 2 CH 3 CH CH 3 I.U.P.A.C. NOMENCLATURE Apply the rules and name these alkanes

19. CH 2 CH 3 CH 2 CH CH 3 CH2CH2 CH3CH3 CHCH CH2CH2 CH3CH3 I.U.P.A.C. NOMENCLATURE CH 3 CH CH 2 CH 3 CH CH 3 Longest chain = 5 so it is a pentane A CH 3, methyl, group is attached to the third carbon from one end... 3-methylpentane I.U.P.A.C. NOMENCLATURE Apply the rules and name these alkanes

20. CH2CH2 CH3CH3 CH2CH2 CH2CH2 CHCH CH3CH3 CH 3 CH 2 CH 3 CH CH 2 CH 3 I.U.P.A.C. NOMENCLATURE CH 3 CH CH 2 CH 3 CH CH 3 Longest chain = 5 so it is a pentane A CH 3, methyl, group is attached to the third carbon from one end... 3-methylpentane I.U.P.A.C. NOMENCLATURE Apply the rules and name these alkanes Longest chain = 6 so it is a hexane A CH 3, methyl, group is attached to the second carbon from one end... 2-methylhexane

21. CH 2 CH 3 CH 2 CH CH 3 CH 2 CH 3 CH CH 2 CH 3 I.U.P.A.C. NOMENCLATURE CH3CH3 CH 3 CHCH CH2CH2 CH2CH2 CH3CH3 CHCH Longest chain = 5 so it is a pentane A CH 3, methyl, group is attached to the third carbon from one end... 3-methylpentane I.U.P.A.C. NOMENCLATURE Apply the rules and name these alkanes Longest chain = 6 so it is a hexane A CH 3, methyl, group is attached to the second carbon from one end... 2-methylhexane Longest chain = 6 so it is a hexane CH 3, methyl, groups are attached to the third and fourth carbon atoms (whichever end you count from). 3,4-dimethylhexane

22. Boiling pointincreases as they get more carbon atoms in their formula more atoms = greater intermolecular Van der Waals’ forces greater intermolecular force = more energy to separate the molecules greater energy required = higher boiling point CH 4 (-161°C) C 2 H 6 (-88°C) C 3 H 8 (-42°C) C 4 H 10 (-0.5°C) difference gets less - mass increases by a smaller percentage straight chains molecules have greater interaction than branched “The greater the branching, the lower the boiling point” Melting pointgeneral increase with molecular mass the trend is not as regular as that for boiling point. Solubilityalkanes are non-polar so are immiscible with water they are soluble in most organic solvents. PHYSICAL PROPERTIES OF ALKANES

23. Introduction- fairly unreactive; (old family name, paraffin, meant little reactivity) - have relatively strong, almost NON-POLAR, SINGLE covalent bonds - they have no real sites that will encourage substances to attack them Combustion- make useful fuels - especially the lower members of the series - react with oxygen in an exothermic reaction complete CH 4 (g) + 2O 2 (g) ——> CO 2 (g) + 2H 2 O(l) combustion incomplete CH 4 (g) + 1½O 2 (g) ——> CO(g) + 2H 2 O(l) combustion the greater the number of carbon atoms, the more energy produced BUTthe greater the amount of oxygen needed for complete combustion. Handy tip When balancing equations involving complete combustion, remember... every carbon in the original hydrocarbon gives one carbon dioxide and every two hydrogen atoms gives a water molecule. Put the numbers into the equation, count up the O’s and H’s on the RHS of the equation then balance the oxygen molecules on the LHS. CHEMICAL PROPERTIES OF ALKANES

24. Processes involving combustion give rise to a variety of pollutants... power stationsSO 2 emissions produce acid rain internal combustion enginesCO, NOx and unburnt hydrocarbons Removal SO 2 react effluent gases with a suitable compound (e.g. CaO) CO and NOxpass exhaust gases through a catalytic converter Catalytic converters In the catalytic converter...CO is converted to CO 2 NOx are converted to N 2 Unburnt hydrocarbons are converted to CO 2 and H 2 O e.g.2NO + 2CO ———> N 2 + 2CO 2 catalysts are made of finely divided rare metals Rh, Pd, Pt leaded petrol must not pass through the catalyst as the lead deposits on the catalyst’s surface and “poisons” it, thus blocking sites for reactions to take place. POLLUTION

25. There are 3 ways to split the shared electron pair in an unsymmetrical covalent bond. UNEQUAL SPLITTING produces IONS known as HETEROLYSIS or HETEROLYTIC FISSION EQUAL SPLITTING produces RADICALS known as HOMOLYSIS or HOMOLYTIC FISSION If several bonds are present the weakest bond is usually broken first Energy to break bonds can come from a variety of energy sources - heat / light In the reaction between methane and chlorine either can be used, however... In the laboratory a source of UV light (or sunlight) is favoured. BREAKING COVALENT BONDS

26. TYPICAL PROPERTIES reactive species (atoms or groups) which possess an unpaired electron their reactivity is due to them wanting to pair up the single electron formed by homolytic fission (homolysis) of covalent bonds formed during the reaction between chlorine and methane formed during thermal cracking involved in the reactions taking place in the ozone layer FREE RADICALS

27. Reagentschlorine and methane ConditionsUV light or sunlight - heat is an alternative energy source Equation(s)CH 4 (g) + Cl 2 (g) ——> HCl(g) + CH 3 Cl(g) chloromethane CH 3 Cl(g) + Cl 2 (g) ——> HCl(g) + CH 2 Cl 2 (l) dichloromethane CH 2 Cl 2 (l) + Cl 2 (g) ——> HCl(g) + CHCl 3 (l) trichloromethane CHCl 3 (l) + Cl 2 (g) ——> HCl(g) + CCl 4 (l) tetrachloromethane Mixturesfree radicals are very reactive - they are trying to pair their electron with sufficient chlorine, every hydrogen will eventually be replaced. CHLORINATION OF METHANE

28. Reagentschlorine and methane ConditionsUV light or sunlight - heat is an alternative energy source Equation(s)CH 4 (g) + Cl 2 (g) ——> HCl(g) + CH 3 Cl(g) chloromethane CH 3 Cl(g) + Cl 2 (g) ——> HCl(g) + CH 2 Cl 2 (l) dichloromethane CH 2 Cl 2 (l) + Cl 2 (g) ——> HCl(g) + CHCl 3 (l) trichloromethane CHCl 3 (l) + Cl 2 (g) ——> HCl(g) + CCl 4 (l) tetrachloromethane Mixturesfree radicals are very reactive - they are trying to pair their electron with sufficient chlorine, every hydrogen will eventually be replaced. MechanismMechanisms portray what chemists think is going on in the reaction, whereas an equation tells you the ratio of products and reactants. Chlorination of methane proceeds via FREE RADICAL SUBSTITUTION because the methane is attacked by free radicals resulting in hydrogen atoms being substituted by chlorine atoms. The process is a chain reaction. In the propagation step, one radical is produced for each one used CHLORINATION OF METHANE

29. Initiation Cl 2 ——> 2Cl RADICALS CREATED The single dots represent UNPAIRED ELECTRONS During initiation, the WEAKEST BOND IS BROKEN as it requires less energy. There are three possible bonds in a mixture of alkanes and chlorine. 412 348 242 Average bond enthalpy kJ mol -1 The Cl-Cl bond is broken in preference to the others as it is the weakest and requires requires less energy to separate the atoms.

30. CHLORINATION OF METHANE Propagation Cl + CH 4 ——> CH 3 + HCl RADICALS USED and Cl 2 + CH 3 ——> CH 3 Cl + Cl then RE-GENERATED Free radicals are very reactive because they want to pair up their single electron. They do this by abstracting a hydrogen atom from methane; a methyl radical is formed The methyl radical is also very reactive and attacks a chlorine molecule A chlorine radical is produced and the whole process can start over again

31. CHLORINATION OF METHANE Termination Cl + Cl ——> Cl 2 RADICALS REMOVED Cl + CH 3 ——> CH 3 Cl CH 3 + CH 3——> C 2 H 6 Removing the reactive free radicals brings an end to the reaction. This is not very likely at the start of the reaction because of their low concentration.

32. CHLORINATION OF METHANE Initiation Cl 2 ——> 2Cl radicals created Propagation Cl + CH 4 ——> CH 3 + HClradicals used and Cl 2 + CH 3 ——> CH 3 Cl + Cl then re-generated Termination Cl + Cl ——> Cl 2 radicals removed Cl + CH 3 ——> CH 3 Cl CH 3 + CH 3——> C 2 H 6 OVERVIEW Summary Due to lack of reactivity, alkanes need a very reactive species to persuade them to react Free radicals need to be formed by homolytic fission of covalent bonds This is done by shining UV light on the mixture (heat could be used) Chlorine radicals are produced because the Cl-Cl bond is the weakest You only need one chlorine radical to start things off With excess chlorine you get further substitution and a mixture of chlorinated products

33. Initiation Propagation Termination CHLORINATION OF METHANE RADICALS PRODUCED RADICALS USED AND REGENERATED RADICALS REMOVED

34. Further propagationIf excess chlorine is present, further substitution takes place The equations show the propagation steps for the formation of... dichloromethane Cl + CH 3 Cl ——> CH 2 Cl + HCl Cl 2 + CH 2 Cl ——> CH 2 Cl 2 + Cl trichloromethane Cl + CH 2 Cl 2 ——> CHCl 2 + HCl Cl 2 + CHCl 2 ——> CHCl 3 + Cl tetrachloromethane Cl + CHCl 3 ——> CCl 3 + HCl Cl 2 + CCl 3 ——> CCl 4 + Cl Mixtures Because of the many possible reactions there will be a mixture of products. Individual haloalkanes can be separated by fractional distillation. CHLORINATION OF METHANE

35. Involves the breaking of C-C bonds in alkanes Converts heavy fractions into higher value products THERMALproceeds via a free radical mechanism CATALYTICproceeds via a carbocation (carbonium ion) mechanism CRACKING THERMAL HIGH PRESSURE... 7000 kPa HIGH TEMPERATURE... 400°C to 900°C FREE RADICAL MECHANISM HOMOLYTIC FISSION PRODUCES MOSTLY ALKENES... e.g. ETHENE for making polymers and ethanol PRODUCES HYDROGEN... used in the Haber Process and in margarine manufacture Bonds can be broken anywhere in the molecule by C-C bond fission or C-H bond fission

36. Involves the breaking of C-C bonds in alkanes Converts heavy fractions into higher value products THERMALproceeds via a free radical mechanism CATALYTICproceeds via a carbocation (carbonium ion) mechanism CRACKING CATALYTIC SLIGHT PRESSURE HIGH TEMPERATURE... 450°C ZEOLITE CATALYST CARBOCATION (IONIC) MECHANISM HETEROLYTIC FISSION PRODUCES BRANCHED AND CYCLIC ALKANES, AROMATIC HYDROCARBONS USED FOR MOTOR FUELS ZEOLITES are crystalline aluminosilicates; clay like substances

37. REVISION CHECK What should you be able to do? Recall and explain the physical properties of alkanes Recall the use of alkanes as fuels Recall and explain the different ways to break a covalent bond Write balanced equations representing combustion and chlorination Understand the conditions and mechanism of free radical substitution Recall the conditions and products from thermal and catalytic cracking CAN YOU DO ALL OF THESE? YES NO

38. In the past, most important organic chemicals were derived from coal. Nowadays, natural gas and crude petroleum provide an alternative source. the composition of crude petroleum varies according to its source it is a dark coloured, viscous liquid consists mostly of alkanes with up to 40 carbon atoms, plus water, sulphur and sand can be split up into fractions by fractional distillation distillation separates the compounds according to their boiling point at each level a mixture of compounds in a similar boiling range is taken off rough fractions can then be distilled further to obtain narrower boiling ranges some fractions are more important - usually the lower boiling point ones high boiling fractions may be broken down into useful lower boiling ones - CRACKING CONTENTS PETROCHEMICALS

39. Boiling C’s per Name of Use(s) range / °C molecule fraction < 25 1 - 4 LPG (LiquefiedCalor Gas Petroleum Gas)Camping Gas 40-100 4 - 12 GASOLINEPetrol 100-150 7 - 14 NAPHTHAPetrochemicals 150-200 11 - 15 KEROSINEAviation Fuel 220-350 15 - 19 GAS OILCentral Heating Fuel > 350 20 - 30 LUBRICATING OIL Lubrication Oil > 400 30 - 40 FUEL OILPower Station Fuel Ship Fuel > 400 40 - 50 WAX, GREASECandles Grease for bearings > 400 > 50 BITUMENRoad surfaces Roofing CONTENTS PETROCHEMICALS

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42. © 2003 JONATHAN HOPTON & KNOCKHARDY PUBLISHING THE THE END AN INTRODUCTION TO THE CHEMISTRY OF ALKANES