1

6 Hydrocarbons : alkanes and alkenes

6.1 Types of hydrocarbons
Aliphatic hydrocarbons are straight-chain and branched hydrocarbons with no rings of carbon atoms e.g. alkanes and alkenes Alicyclic hydrocarbons are hydrocarbons with at least one ring of carbon atoms Arenes (aromatic hydrocarbons) are hydrocarbon with a ring or rings of carbon atoms in which there are delocalised electrons e.g. benzene, methylbenzene

6.2 Alkanes
hydrocarbons that make up most of crude oil / natural gas series of organic compounds with the formula CnH2n+2 saturated compounds single bonds between atoms in molecules Physical properties Alkanes are composed of simple molecules held together by weak intermolecular forces. As the molecules increase in size, the intermolecular forces increase, therefore the melting and boiling temperatures rise as the number of carbon atoms per molecule increase. C1 to C4 gases, C5 to C17 are liquid, C18+ are solids

6.3 Chemical reactions of the alkanes

bonds enthalpies of C-C and C-H bonds are high difficult to break the bonds are non-polar alkanes are very unreactive with ionic reagents in water e.g. acids / alkalis / oxidising agents important reactions of alkanes involving homolytic bond breaking and free radicals reactions combustion / halogenation / cracking Burning (combustion) common fuels consist mainly of alkanes alkane + oxygen (sufficient) carbon dioxide + water alkane + oxygen (insufficient) carbon dioxide + water (carbon monoxide + carbon soot) alkanes are kinetically stable in oxygen, but they are energetically unstable with respect to products of oxidation combustion of alkanes involves free-radical mechanism occurs rapidly in the gas phase this means that liquid and solid alkanes must vaporise before they burn and it explains why less volatile alkanes burn less easily used to generate energy cause of global warming + greenhouse effect

Adam Clarke www.brain-freeze.co.uk

2 Halogenation (reactions with chlorine and bromine) alkanes react with chlorine / bromine on heating or on exposure to UV light Hydrogen atoms in alkane molecules are replaced by halogen atoms substitution reaction A substitution reaction a reaction in which an atom or group of atoms is substituted by another atom or groups of atoms. any of the hydrogen atoms in an alkane may be replaced the reaction can continue until all the hydrogen atoms have been substituted by halogen atoms. as a consequence the product is a mixture of compounds Strong sunlight alkane + halogen react explosively Reaction involves breaking some bonds energy must be supplied / making - energy released Reaction requires sunlight molecules dont have enough energy for bonds to break when they collide The photons from UV light provide energy which is absorbed enough to cause homolytic fission of the halogen molecules into free radicals This is not enough for the homolytic fission of methane UV light starts the reaction by splitting halogen molecules into halogen atoms (free radicals) (INITIATION) The halogen atoms each with an unpaired electron are highly reactive They remove hydrogen atoms from alkane molecules to form hydrogen halogen and a new free radical The free radical now reacts with more halogen to form halogenoalkane and to generate another chlorine free radical The new halogen free radical can react with more alkane molecules and the last two reactions can be repeated until either all of alkane / halogen is used up such repeated reactions create a chain reaction (PROPAGATION) this stage ends when two free radicals combine this is (TERMINATION )stage of the reaction which is very exothermic . Initiation free radicals produced Propagation steps which form products and more free radicals Termination steps which remove free radicals by turning them into molecules

Adam Clarke www.brain-freeze.co.uk

6.4 Fuels from crude oil

Crude oil petroleum - provides energy needs / source of organic chemicals e.g. plastics/drugs it is a complex mixture of hydrocarbons most of which are alkanes crude oil has no uses in its raw form refineries should produce various oil products in the proportions required by industrial / domestic users. crude oil contains too much of the high boiling fractions with large molecules not enough of the low boiling fractions with the smaller molecules needed for fuels such as petrol in order to satisfy the demand for very different products, crude oil undergoes three main processes fractional distillation, cracking and reforming

Fractional distillation
first stage in refining crude oil furnace heats crude oil to 400oC it then flows into a fractionating tower containing around 40 trays pierced with small holes the column is hotter at the bottom and cooler at the top rising vapour condenses when it reaches the tray with liquid at a temperature just below its boiling temperature condensing vapour releases energy which heats the liquid on the tray and evaporates the more volatile compounds in the mixture on they tray with a series of trays the outcome is that hydrocarbons with small molecules and low boiling temperatures rise to the top of the column, while larger molecules stay at the bottom. Fractions are drawn off from the column at various levels. Some components of crude oil have boiling temperatures too high for them to vaporise at the furnace temperature and atmospheric pressure. lowering the pressure in a separate vacuum distillation column reduces the boiling temperatures of such hydrocarbons and this makes it possible to separate them. Fuel fractions Gasoline fraction (hydrocarbon 5-10C) > Petrol Kerosene/ Paraffin (hydrocarbons 10-16 C) > Jet fuel Diesel oil (hydrocarbon 14-20C) > Diesel engine fuel All these fuels have to be refined to remove sulphur compounds which would cause air pollution Blended carefully for engines to start reliably and run smoothly proportion of volatile hydrocarbons higher in winter to help cold-starting / lower in summer to prevent vapour forming too readily To ensure smooth combustion high-octane fuel is produced by increasing proportions of branched alkanes and arenes / blending-in oxygen compounds. cracking which makes smaller molecules and converts straight chain hydrocarbons to branched and cyclic hydrocarbons reforming which turns straight chain and cyclic alkanes into arenes such as benzene and methylbenzene. adding ethanol and ethers such as ETBE gasohol 90% gasoline / 10% ethanol

Adam Clarke www.brain-freeze.co.uk

Catalytic cracking
This converts heavier fractions (diesel oil and fuel oil) from fractional distillation of crude oil into more useful hydrocarbon fuels by breaking up large molecules into smaller ones. Cracking converts long-chain alkanes with 12+ C atoms into smaller more useful molecules in a mixture of branched alkanes, cycloalkanes, alkenes and branched alkenes. The catalyst is a synthetic sodium aluminium silicate belonging to a class of compounds called zeolites A zeolite is a 3D structure with silicon/oxygen atoms forming tunnels for small molecule to fit into cracking takes place on the surface of this catalyst at 500 oC synthetic zeolites make excellent catalysts because they can be developed with active sites to favour the shapes/sizes of the molecule which react to give the desired products. Catalytic cracking is a continuous process finely powdered catalyst becomes coated with carbon circulates through a regenerator where the carbon burns away in a stream of air.

Reforming
This converts straight-chain and cyclic alkanes into arenes (aromatic hydrocarbons) e.g. benzene Hydrogen is an important by-product it can be used in processes elsewhere in the refinery Catalyst precious metal platinum / rhodium supported on an inert material like aluminium oxide Temperature of 500 oC

6.5 Alternative fuels

Crops take In carbon dioxide from the air as they photosynthesise making sugars / vegetable oils that can be used to produce biofuels Carbon neutral - when the biofuels burn the carbon dioxide taken up is returned to the air this suggests that the use of biofuels should have no overall effect on the level of carbon dioxide in the atmosphere. This ignores the carbon dioxide released during the planting / harvesting / processing / manufacture of fertilisers. Bioethanol is manufactured fermenting carbohydrates such as starch and sugar in crops like sugar cane - Fermentation converts starch into glucose > ethanol + CO2 (catalysed by yeast enzymes) Biodiesel extracting / processing oils from crops e.g. rapeseed Sustainable lifestyle living within the means of the environment in order that the Earths natural resources are available for future generations

Adam Clarke www.brain-freeze.co.uk

6.6 Alkenes
produced during cracking of heavier fractions from crude oil reactivity of double bonds important starting points for synthesis of other chemicals Unsaturated compounds contain one/more double or triple bonds between atoms in their molecules. The term is often applied to alkenes and to describe unsaturated fats which C=C double bonds in their hydrocarbon chains. Names and structures number used to indicate position of double bond Physical properties melting / boiling temperatures increase as the number of carbon atoms increase (strength of intermolecular forces) ethane, propene , butene gases at room temperature Alkenes like other hydrocarbons dont mix/dissolve with water Double bond in alkenes Molecular orbitals result when atomic orbitals overlap forming bonds between atoms A sigma bond is a single covalent formed by a pair of electrons in an orbital in a molecule with the electron density concentrated between two nuclei. Free rotation is possible around single bonds Sigma bonds can form by overlap of two s orbitals, an s orbital and a p orbital or 2 p orbitals A pi bond is the bond found in molecules with double/triple bonds. The bonding electrons are in a pi orbital formed by the sideways overlap of two atomic p orbitals. In a pi bond the electron density is concentrated in two regions one above and the other below the plane of the molecule on either side of the line between the nuclei of the two atoms joined by the bond

6.7 Cis-trans isomerism

Double bond rotation would require breaking the pi bond and this requires more energy than the molecules possess at normal temperatures. Free rotation is not possible around carbon-carbon double bond in alkenes and this gives rise to cis and trans isomers. Alkenes have cis and trans isomers if there are two different groups on each carbon atom in the double bond. In a cis isomer similar groups are on the same side of the double bond trans similar groups on opposite sides The cis-trans isomers have different melting points, boiling temperatures and densities Cis and trans isomers are molecules with the same molecular formula, the same structural formula but different displayed formula.

Adam Clarke www.brain-freeze.co.uk

6 EZ naming system Used where there are four different groups on double bond 1) Look at atoms bonded to first carbon atom 2) the atom with the highest atomic number takes priority 3) If two atoms with the same atomic number but in different groups are attached to the first carbon atom, then the next bonded atom is taken into account. 4) This comes into account with the next carbon atom is the C=C bond. 5) If two groups of the highest priority on the same side of the double bond the isomer is named Z 6) If two groups of highest priority are on opposite sides of the double bond they are labelled E.

6.8 Chemical reactions of the alkenes

Addition reaction is a reaction in which two molecules add together to form a single product. Addition of hydrogen Hydrogen adds to C=C double bonds at room temperature Temperature room temperature (25OC) / 150oC Catalyst platinum, palladium / nickel process is known as catalytic hydrogenation + solid metal catalyst can be held in reaction vessel as reactions flow in and products out + no difficulty in separating catalyst / can be reused to save money during hydrogenation some double bonds are converted to c-c single bonds Addition of halogens Chlorine/Bromine add rapidly to alkenes at room temperature (products dichloroalkanes and dibromoalkanes) Flourine reacts explosively with small alkenes, such as ethane and propene Reaction with iodine is slow Addition of hydrogen halides Hyrogen halides react readily with alkenes at room temperature forming halogenoalkanes Hydrogen bromide (gaseous) + ethane bromoethane (at room temperature) The other hydrogen halides HCl and HI react in a similar way. Oxidation by potassium manganate Potassium manganate oxidises alkene the products depend on the conditions A dilute acidified solution of potassium manganate converts an alkene to a diol at room temperature. At the same time purple manganate ions MnO4 are reduced to very pale pink MN2+ ions and the purple colour disappears if there is excess alkene. The reaction with dilute acidified potassium manganate can be used to distinguish between unsaturated and saturated hydrocarbons.

Adam Clarke www.brain-freeze.co.uk

6.9 Electrophillic addition to alkenes

Most of the reactions of alkenes are electrophillic addition reactions. Electrophiles attach the electron-rich region of the double bond in alkenes and in particular the exposed pi bond. Electrophiles that add to alkenes include hydrogen bromide, bromine and water in the presence of H+ ions. The addition of hydrogen bromide to ethane Hydrogen bromide molecules are polar the H atom with its positive charge at one end of the molecule acts as an electrophiles. 1) HBr molecule approaches ethene molecule 2) The positive end of the HBr is attracted towards the electron-rich double bond 3) As the HBr molecule gets closer Heterolytic fission of the pi bond occurs electrons in it form a covalent bond to the hydrogen atom and at the same time Heterolytic fission of the HBr bond also occurs. 4) Electrons in the H-Br are taken over by the bromine atom, producing a Br- ion. Another product of the first stage is the highly reactive cation CH3CH2+. This is so reactive that it reacts immediately with the Br- in the second step to form bromoethane, CH3CH2Br. The addition of bromine to ethene Bromine molecules are not polar but they become polarised as they approach the electron-rich region of the double bond. Electrons in the double bond repel electrons in the bromine molecule and the positive end of the bromine molecule becomes electrophillic. Second step highly reactive cation CH3BrCH2 can be attacked by Br. In this case the product is 1,2-dibromoethane

The mechanisms for electrophillic additions as described are supported by experimental evidence. The rate of addition with hydrogen halides is in the order HCl > HBr> HI. This is the order of the strengths as acids, which supports the first step of the mechanism in which an H+ ion adds to the alkene. If HBr addition is carried out in the presence of NaCl then chloroethane is obtained in addition to CH3CH2Br / Br2 + NaCl CH2BrCH2Cl is obtained with CH2BrCH2Br

Adam Clarke www.brain-freeze.co.uk

Testing for alkenes and the C=C bond The reaction of bromine water with hydrocarbons is a useful test for alkenes and the C=C. Unsaturated hydrocarbons with a C=C bond such as ethene and cyclohexene quickly decolourise yellow/orange bromine water producing a colourless mixture. Saturated hydrocarbons such as ethane and cyclohexane have no reactions with bromine water and yellow/orange colour remains. When bromine is added to water some of it reacts with water to form a mixture of hydrobromic acid and bromic acid. Hydrobromic acid is a relatively strong acid which ionises immediately. In comparison bromic acid is a weak acid which remains un-ionised as polar HO-Br molecules. When bromine water is mixed with ethene H+ ions from the HBr react with the electron-rich region of the C=C bond forming an intermediate cation. This cation then reacts rapidly with Br and H2O in the bromine water to form a mixture of bromoethane and ethanol. In addition to these products unreacted bromine molecules react with ethene to form dibromoethane and the polarised HO-Br reacts with ethene to form 2-bromoethanol ethene + bromine water bromoethane + ethanol

6.10 Addition to unsymmetrical alkenes

When a molecule such as HBr or HCl adds to an unsymmetrical alkene such as propene there are two possible products, but much more of one product is usually produced. Reaction between hydrogen bromide and propene shows that much more 2-bromopropane than 1bromopropane is produced. This suggests that the hydrogen atom from HBr adds mainly to the carbon atom of the double bond which already has more hydrogen atoms attached to it. This pattern is called Markovnikovs rule The mechanism for electrophillic addition helps to account for the rule, where adding HBr to propene there are two possible cation intermediates. The cation with its positive charge in the middle of the carbon chain is slightly more stable than the cation with its charge at the end of the chain. The more stable cation has two alkyl groups pushing electrons towards the positively charged carbon atom. This helps to stabilise the ion by reducing its positive charge which is an example of an inductive effect. With effect more stable cation persists longer and is more likely to combine with Br ions forming the main product 2-bromopropane. Intermediates are atoms, molecules, ions or free-radicals which dont appear in the overall equation for a reaction but which are formed during one step of a reaction and then used up in the next. Inductive effect describes the way in which electrons are either pushed towards or pulled away from a carbon atom by the atoms of groups to which it is bonded. Alkyl groups have a small tendency to push electrons towards any carbon atom to which they are bonded. One of the consequences of this is that any carbon atom with a positive charge becomes more stable as more alkyl groups are attached to it.

Adam Clarke www.brain-freeze.co.uk

6.1 Addition polymers from alkenes

If the conditions are right, molecules of ethene will undergo addition reactions with each other to form polythene poly(ethene). Two types of polythene are made low density and high density. Addition polymerisation an addition reaction in which small molecules, called monomers, join together forming a giant molecule, called a polymer. Low density polythene is made by heating ethene at high pressures and high temperatures with special substances called initiators. These initiators are often peroxides which break apart to form free radicals that initiate (start) the reaction. The polyethene produced has very long chains with lots of branches. The branches prevent the molecules from packing closely and this results in low-density material.

High density polythene is made at relatively low pressure and low temperature with a special catalyst this produces extra long chains with little branching so the chains pack closer. Processes like these are called addition polymerisations during addition polymerisation small molecules like ethene known as monomers add to each other to form a giant molecule called a polymer. Polythene is by far the most important polymer at present after polythene the two most useful polymers are poly(propene) and poly(chloroethene) pvc. These are also manufactured by addition polymerisation Polythene polypropene and pvc are soft flexible and slightly elastic because of this they are often called plastics.

Adam Clarke www.brain-freeze.co.uk