12ChF322 Alkanes

Alkanes
Candidates should be able to: (a) explain that a hydrocarbon is a compound of hydrogen and carbon only; (b) explain the use of crude oil as a source of hydrocarbons, separated as fractions with different boiling points by fractional distillation, which can be used as fuels or for processing into petrochemicals; (c) state that alkanes and cycloalkanes are saturated hydrocarbons; (d) state and explain the tetrahedral shape around each carbon atom in alkanes; (e) explain, in terms of van der Waals forces, the variations in the boiling points of alkanes with different carbon-chain length and branching; (f) describe the combustion of alkanes, leading to their use as fuels in industry, in the home and in transport; (g) explain, using equations, the incomplete combustion of alkanes in a limited supply of oxygen and outline the potential dangers arising from production of CO in the home and from car use; (h) describe the use of catalytic cracking to obtain more useful alkanes and alkenes; (i) explain that the petroleum industry processes straight-chain hydrocarbons into branched alkanes and cyclic hydrocarbons to promote efficient combustion; (j) contrast the value of fossil fuels for providing energy and raw materials with: (i) the problem of an over-reliance on nonrenewable fossil fuel reserves and the importance of developing renewable plantbased fuels, ie alcohols and biodiesel, (ii) increased CO2 levels from combustion of fossil fuels leading to global warming and climate change; (k) describe the substitution of alkanes using ultraviolet radiation, by Cl2 and by Br2, to form halogenoalkanes; (l) define the term radical as a species with an unpaired electron; (m) describe how homolytic fission leads to the mechanism of radical substitution in alkanes interms of initiation, propagation and termination reactions; (n) explain the limitations of radical substitution in synthesis, arising from further substitution with formation of a mixture of products.

Alkanes are SATURATED HYDROCARBONS (no double bonds, C and H atoms only). They are identified by having a ane name ending. The alkanes have similar chemistry to one another because they are a HOMOLOGOUS SERIES. Definition: Homologous Series: a series of organic compounds having the same functional groups, each successive member differing by CH2-

Any homologous series can be represented by a GENERAL FORMULA. In this case it is where n is the number of carbon atoms in the alkane.

CnH2n+2

The cycloalkanes are also saturated hydrocarbons, but having two less H atoms, and a ring rather than a chain structure. e.g. cyclohexane C6H12 hexane C6H14
H H H C H C C H H H C C H C H H H H Properties:

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

Physical

Low molecular weight alkanes (C1 to C4) are gases at room temperature A little heavier molecular weight alkanes (C5 C17) are liquids at room temperature Higher molecular weight alkanes (C18 and above) are solids at room temperature. Room temperature

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12ChF322 Alkanes Trend in melting and boiling points: As the number of carbons increases, the melting and boiling points get higher. We say that the volatility of the alkanes decreases with increasing number of carbons in the alkane molecule. [Volatility is the ease with which a substance turns into a vapour].
Temperature (K)
Variation of boiling and melting point of alkanes with chain length 650 600 550 500 450 400 350 300 250 200 150

Explanation: 100 The lack of polarity of alkane 50 molecules means that only weak 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 instantaneous dipole-inducedChain length (C-atoms) dipole forces (Van der Waals) forces are present between molecules so compared to many other substances the melting and boiling points are low. As the number of electrons in the molecule increases (with increasing number of atoms) the strength of the Van der Waals forces also increases. More energy is needed to separate the molecules, so melting and boiling points rise. Effect of branching: pentane 2-methylbutane 2,2-dimethylpropane boils at 309K boils at 301K boils at 283K

Explanation: As the molecule gets more ball shaped and less long and thin the molecules cant get so close together. There are fewer points of contact and so the intermolecular forces are weaker. The vapour is formed more easily, and so the boiling point gets lower. Solubility: The alkenes are insoluble in water (non-polar molecules don't dissolve well in polar solvents) but alkanes do dissolve in non-polar solvents e.g. other hydrocarbons. Shapes of molecules: The atoms in alkanes are held together by -molecular orbitals which lie along the axis of each bond, as shown here for an ethene molecule. The molecular orbitals can be considered as the overlap of two atomic orbitals. The two electrons in each -orbital attract both nuclei binding them together in a -bond.

Each C atom in an alkane has a tetrahedral arrangement of 4 around it, so it has: 109.5o bond angles free rotation about bonds which makes alkane chains are very flexible

bonds

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12ChF322 Alkanes

Check your understanding: i) List all the physical properties of pentane you can, based on the information so far in this section.

Chemical Properties:
General: alkanes are remarkably inert, showing no reaction with acids or alkalis for example. A reason for the inertness arises from their lack of polarity. As C and H have similar electronegativities, C-C and C-H bonds are non polar. Consequently alkanes are not attacked by most common chemical reagents. For some uses, the chemical inertness of the alkanes is their greatest asset. Compounds that are noncorrosive to metals (lubricating oils), harmless to our skin (vaseline), and safe in contact with foods (poly(ethene)), are enormously useful to us.

Reactions:
1: Combustion: When an excess of oxygen is available, alkanes combust completely giving carbon dioxide and water as the only products. Alkanes make excellent fuels for domestic, industrial and transport use because they react with oxygen exothermically (a fuel is defined as a source of useful energy). They have low toxicity and short chain alkanes are easily ignited. e.g. CH4 + 2O2 CO2 + 2H2O

Hc = -890 kJmol-1

When only limited oxygen is available, combustion is incomplete and carbon monoxide, or even carbon particles (soot) may be formed. The presence of carbon particles can be detected when hydrocarbons burn because the flame becomes yellow and smoky rather than pale blue. e.g. 2CH4 + 3O2 2CO + 4H2O or 2CH4 + 2 O2 CO + C + 4H2O

Dangers of incomplete combustion arise because CO binds permanently to haemoglobin, preventing O2 and CO2 transport. CO is therefore toxic, and is particularly dangerous because it is a colourless and odourless gas so hard for people to detect. Check your understanding: ii) Write a balanced symbol equation (including state symbols) for the complete combustion of hexane. iii) Write another equation to show combustion with a limited supply of oxygen, where equal volumes of carbon monoxide and carbon dioxide are produced. 2: Refinery processes in making useful products from crude oil i) Fractional distillation This first process is used to separate the crude oil into fractions of similar chain length, each of which has different applications. Fractional distillation is NOT A REACTION. It is just a physical process leading to separation. The molecules remain unchanged throughout. Fractional distillation makes use of the fact that each alkane will have a different boiling point (different strength Van der Waals forces due to length and shapes of molecules), and so when crude oil vapour is introduced into the bottom a tower which has a temperature gradient (hot at the bottom, cooler at the top) each alkane will condense at a different height in the tower from where the liquid can be collected and stored. Fraction Refinery Gases Gasoline Naphtha Kerosine Diesel Residue Length of chains 1-4 5-10 8-10 11-16 13-25 >25 Uses Bottled gases, LPG Petrol for cars Cracking, feedstock Jet fuel, heating oil Diesel fuel (cars, lorries), heating oil Fuel oil for power stations, waxes, bitumen

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12ChF322 Alkanes Reactions are then carried out in the refinery to make optimum use of these fractions. ii) Cracking The highest demand fractions are gasoline (C5 C10) which is used as petrol, and naphtha (C8 C10) which is used as a feedstock for chemical industries. There is a greater demand for these fractions than their proportion in crude oil, so it is usual to treat heavier fractions which are in less demand to create more gasoline and naphtha fraction this is cracking. The reaction uses high temperature and a catalyst usually either a mixture of silicon and aluminium oxides, or a zeolite. The reaction involves random breaking of C-C and C-H bonds and therefore leads to a wide variety of products. Chains can also be broken more than once. In general: long alkane short alkane + alkene e.g. C11H24 C6H14 + C5H10 e.g. C11H24 C7H16 + 2 C 2H 4

+
H H

+2

C C H H

Isomerisation and Reforming Modern engines require a higher proportion of branched-chain alkanes, cycloalkanes, or unsaturated hydrocarbon rings called arenes (e.g. benzene). These substances burn more smoothly than straightchain alkanes, which often pre-ignite leading problems called "knocking" or "pinking". In the refinery, two processes are used to increase the proportion of rings and branched chains by further chemical processing of the straight chains: iii) Isomerisation This simply rearranges an alkane into one of its isomers. Straight chain alkanes are converted into branched chain alkanes by passing their vapour over a hot platinum catalyst: e.g. heptane 2,2,3-trimethylbutane

The resulting mixture contains straight and branched chains which can be separated from one another using a molecular sieve a zeolite. This allows the straight chains through but the branched chains can't fit through the holes in the zeolite. iv) Reforming This reaction forms rings from chains, removing two hydrogen atoms in the process. Bimetallic catalysts (Pt/Re or Pt/Ir) are used:
e.g. hexane cyclohexane + hydrogen + H2

The process can continue to remove pairs of hydrogen atoms, creating double bonds in the ring. In the case of hexane, benzene can eventually be produced:
cyclohexane cyclohexene + hydrogen + H2

The overall equation can be represented as: hexane benzene + 4 H2 + 4 H2

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12ChF322 Alkanes Check your understanding: iv) Write an equation using skeletal formulae for the cracking of decane, in which heptane is produced. v) vi) vii) Write an equation using displayed formulae for one possible isomerisation of pentane. When octane is reformed, one of the possible products is ethylcyclohexane. Write a balanced equation to show this (use displayed or skeletal formulae). Ethylcyclohexane can be further reformed to produce ethylbenzene. Write a balanced equation for the conversion of ethylcyclohexane into ethylbenzene using skeletal formulae.

Alternatives to fossil fuels Crude oil and natural gas are fossil fuels, rich in hydrocarbons especially alkanes. Fuels made from crude oil or natural gas are NON-RENEWABLE because it takes millions of years for these substances to form. Over-reliance on non-renewable fossil fuel reserves is problematic because these fuels are finite and dwindling. It is therefore important to be developing renewable fuels and seeking other forms of renewable energy. Burning fossil fuels increases atmospheric CO2, leading to global warming and climate change due to the greenhouse effect. It is therefore necessary to be looking for more CARBON NEUTRAL fuels. Biofuels are produced from plant matter and waste animal matter. Examples include biodiesel (from extracted plant oils such as rapeseed or palm oil) and bioethanol (from fermentation of plant matter). Fuels from these sources are RENEWABLE because the plants can be grown regrown, and nearly CARBON NEUTRAL because the CO2 released when they are burnt was taken in by the plants from the atmosphere during photosynthesis. Biofuels are not completely carbon neutral because energy is needed for processing and transporting biofuels, and this produces CO2. Benefits and disadvantages of changing from diesel to biodiesel: saves crude oil, less risk of large scale pollution from exploitation of crude oil biodiesel is renewable, unlike diesel, and (more) carbon neutral land used for growing biofuel plants no longer available for growing food rainforests being cleared for growing biofuels 3: Substitution reaction of alkanes with halogens: Hydrogen atoms in an alkane can be SUBSTITUTED by halogen atoms. The mechanism involves the formation of FREE RADICALS, so it is referred to as a FREE RADICAL SUBSTITUTION mechanism. Conditions for the reaction: ULTRAVIOLET LIGHT is required (the amount present in sunlight is sufficient), so this is an example of a PHOTOCHEMICAL REACTION e.g. when chlorine is mixed with methane and exposed to sunlight, chloromethane is formed and hydrogen chloride gas is evolved: CH4(g) + Cl2(g) CH3Cl(g) + HCl(g) Mechanism of Free Radical Substitution: INITIATION STEP The energy of UV light is enough to break the Cl-Cl bond in the Cl2 molecule. Absorption of light energy to break a bond is called PHOTODISSOCIATION. The bond breaks homolytically, resulting in two Cl radicals being formed: uv Cl-Cl(g) Cl(g) + Cl(g) These react rapidly with other molecules or chemical species

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12ChF322 Alkanes PROPAGATION STEPS A chlorine radical reacts with methane to produce hydrogen chloride and a methyl radical Cl + H-CH3 Cl-H + CH3

The methyl radical is able to react with a chlorine molecule to produce chloromethane and a chlorine radical: Cl-Cl + CH3 CH3Cl + Cl

Regenerating the chlorine radical means the reaction can happen again and again - a chain reaction which needs no more UV to keep going. Measurements show these steps can occur some 10,000 times for one UV photon initiation. TERMINATION STEPS The reaction only stops when two radicals combine to form a new molecule. This removes radicals from the reaction mixture, stopping the chain reaction. There are several possibilities: Cl + Cl Cl + CH3 CH3 + CH3 Cl2 CH3Cl C2H6 so a small amount of ethane is also formed

Note: There is no reason why the reaction cant be followed by reaction of chloromethane with more chlorine in further photochemical chain reactions to produce CH2Cl2, CHCl3 and CCl4. It is important therefore to understand that this mechanism results in a mixture of products being formed, not just one pure product. Check your understanding: Bromine reacts with ethane to produce bromoethane when illuminated with uv light. viii) Show the initiation step in the mechanism for this reaction ix) Show the propagation steps in the mechanism for this reaction x) Show a termination step in which bromoethane is produced xi) Suggest two reasons why bromoethane is not the only organic product in this reaction

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12ChF322 Alkanes

Answers to Check Your Understanding questions:

i) List all the physical properties of pentane you can, based on the information given: - liquid at room temperature (but very close to its boiling point) - higher boiling point than similar isoelectronic alkanes - fairly volatile - insoluble in water - flexible chain, can flex into different conformations - 109.5 bond angles throughout ii) Write a balanced symbol equation (including state symbols) for the complete combustion of hexane: C6H14(l) + 9 O2(g) 6 CO2(g) + 7 H2O(l) - or quantities all x 2 iii) Write another equation to show combustion with a limited supply of oxygen, where equal volumes of carbon monoxide and carbon dioxide are produced: Equal volumes of CO and CO2 mean equal numbers of moles of each gas produced therefore three C atoms in each hexane make CO and the other three C atoms make CO2 C6H14(l) + 8O2(g) 3 CO(g) + 3 CO2(g) + 7 H2O(l) iv) Write an equation using skeletal formulae for the cracking of decane, in which heptane is produced: decane heptane + propene

v) Write an equation using displayed formulae for one possible isomerisation of pentane.
H H H H H H C C C C C H H H H H H
H

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

or methybutane as the product

vi) When octane is reformed, one of the possible products is ethylcyclohexane. Write a balanced equation to show this (use displayed or skeletal formulae).
H H H H H H H H H C C C C C C C C H H H H H H H H H

H H

or

C H H H C H + H C C H H C H C C H C H H HH

H2

+ H2

vii)

Ethylcyclohexane can be further reformed to produce ethylbenzene. Write a balanced equation for the conversion of ethylcyclohexane into ethylbenzene using skeletal formulae.

+ 3 H2

product can also be drawn as:

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12ChF322 Alkanes Bromine reacts with ethane to produce bromoethane when illuminated with uv light. viii) Show the initiation step in the mechanism for this reaction Br2 ix) uv Br + Br

Show the propagation steps in the mechanism for this reaction H3C-CH3 Br-Br + + Br CH2CH3 Br + + HBr

CH2CH3

CH3CH2Br

x)

Show a termination step in which bromoethane is produced CH3CH2 + Br CH3CH2Br

xi)

Suggest two reasons why bromoethane is not the only organic product in this reaction Ethyl radicals can combine to produce butane CH3CH2 + CH2CH3 CH3CH2CH2CH3 Bromoethane can itself react by the same mechanism to make dibromoethane uv CH3CH2Br + Br2 CH3CHBr2 + HBr also butane could react further to make bromobutane, and the dibromoethane could react further to make other halogenoalkanes.

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