Cracking

Short alkane chains from Fractional Distillation (used e.g. for petrol) are in much greater demand than long chains. This means that after fractionation, there are long chains left over when all the short chains have been sold. To make most efficient use of the crude oil, these long chains are cracked in the refinery. Cracking produces SHORTER CHAIN ALKANES plus molecules called ALKENES The shorter chain alkanes help satisfy the demand for short chain fractions to be used as fuels. Alkenes are important starting points for many products made in the chemical industry e.g. plastics, pharmaceuticals. Cracking is a THERMAL DECOMPOSITION reaction the long chains are heated until vapourised and the vapour is then passed over a hot catalyst. A catalytic cracking plant

What are alkenes ?

Recall that the alkanes are a family of hydrocarbons. The alkenes are also a family of hydrocarbons, but they have a double bond between two of the carbon atoms. This means that i) they are unsaturated ii) they have a general formula

CnH2n

Having a double bond means that alkenes are more reactive than alkanes which is why they are so useful as starting points for making other chemical compounds. Here are displayed formulae for some alkenes:

H C=C H
Ethene C2H4

H H

H H H | | C=CCH H | H
Propene C3H6

H H H H | | | C=CCCH H | | H H
Butene C4H8

Cracking reactions
The number of carbon and hydrogen atoms always has to add up to the same on both sides of the equation always check to make sure this is so ! e.g. octane hexane + ethene

C8H18
decane

C6H14
heptane

+
+

C2H4
propene

C10H22

C7H16

C3H6

Sometimes a chain may crack twice two alkenes will be formed e.g. decane propane + butene + propene

C10H22

C3H8

C4H8

C3H6

Hydrogen can also be made as a product of cracking e.g. hexane hexene + hydrogen

C6H14

C6H12

H2

Telling an alkane from an alkene

The test for a compound which contains one (or more) double bond between carbon atoms is to shake the compound with bromine water If the compound is unsaturated (contains a double bond) then the bromine water reacts with the alkene. The bromine water turns from orange to colourless. We say that the alkene decolourises bromine water. If the compound is saturated (no double bonds) the bromine water cant react with it, and the bromine water remains orange.

Testing an alkane and an alkene with bromine water

After adding bromine water and shaking

The alcohol (called ethanol) in both of these products has been produced by a chemical reaction (its the same alcohol we might find in wine, or beer). While the alcohol is the same, the reactions are very different. You will need to be able to compare the two routes by which ethanol is made.

Industrial ethanol made by the reaction of ethene with steam

Ethanol as an alternative fuel made by the fermentation of plant matter

Making ethanol from ethene

When heated and treated with a catalyst, ethene reacts with steam to produce ethanol. The equation for the reaction is:

H H | | C=C + | | H H

H-OH

H H | | HCCH | | H OH ethanol C2H5OH

ethene + water C2H4 + H2O

The ethene is obtained from cracking of long chain fractions from crude oil. It is therefore from a non-renewable source. The reaction goes at high temperature, so there are high energy costs The reaction can carry on as a continuous process, so large amounts of ethanol can be made relatively quickly this way.

Making ethanol by fermentation

Plant matter containing sugars (build up by the plant during photosynthesis) can be fermented using yeast. The yeast organisms convert the sugars into ethanol and carbon dioxide. sugars ethanol + carbon dioxide

C6H12O6 2 C2H5OH

2 CO2

The process uses plant matter which can be regrown continuously, so its from a renewable source The process does not require high temperatures low energy costs The yeast dies from ethanol poisoning, so the process has to be stopped and the ethanol extracted and purified before starting over again with fresh yeast. This is called a batch process. The reaction is slow. It takes a long time to make ethanol by this route compared to the industrial route.

Plastics are made from molecules which have extremely long chains of carbon atoms. We call these molecules polymers. They are made by linking together huge numbers of much smaller molecules to form the chain. Alkenes are suitable molecules to use for these polymerisation reactions. Common plastic materials such as polythene polypropylene PVC Perspex are all polymers made from alkenes

Manufacturing large polythene bags

A polymer molecule is made by reacting together many smaller molecules to link together into a chain. These smaller molecules which form the chain are called monomers. Polymers are named by taking the monomer name, putting it in brackets, and adding poly in front. e.g. The polymer made from ethene is called poly(ethene) known by the common name polythene Alkenes are one type of monomer which link together to form polymers. The reaction is called addition polymerisation, because the monomers add on to one another to form the chain, and no other product is formed. It would be impossible to draw the whole of a polymer molecule its too long ! Fortunately a polymer chain contains the same arrangement of atoms repeated over and over again. Instead we can draw a repeat unit, or a section of the polymer.

Products made from poly(ethene)

Look at these monomers, and see how the polymer repeat unit and structure are drawn using DISPLAYED FORMULAE: Monomer H H | | C=C | | H H ethene H H Repeat Unit H H | | CC | | H H Section (showing 3 repeats) H H H H H H | | | | | | -CCCCCC| | | | | | H H H H H H poly(ethene)

poly(ethene) H H

H C | / H C = C | | H H propene

H C | / H C C | | H H poly(propene)

H CH3 | | -C C | | H H

H CH3 | | C C | | H H

H CH3 | | CC| | H H

poly(propene)

Points to remember when drawing polymers: 1) The polymer is formed by breaking open the double bond and using it to join to monomer molecule either side. This means that every repeat unit is a section of the chain two carbon atoms long. 2) The double bond is broken when the polymer is made, leaving just single bonds. There are no double bonds in the repeat unit or section Balanced equations: Chains are different lengths, made from differing numbers of monomers. The best we can do is to say there were n monomers joined together to make the chain. The balanced equation therefore is written as: Cl H | | C=C | | H H Cl H | | CC | | H H n poly(chloroethene) (note where the n s are)

n monomers join together to form a polymer which is n repeats long

chloroethene

Advantages and disadvantages of

using products from crude oil as fuels or as raw materials
Fuels such as petrol and diesel are easy to transport, relatively safe to use,

Fossil fuels contain a little sulphur which, when burned, forms sulphur dioxide this causes acid rain. Crude oil is a non-renewable resource, taking millions of years to form it is a finite resource. Products from crude oil provide valuable starting points for chemicals such as life-saving drugs and high-tech polymers.

Alternative fuels are not yet sufficiently safe, cost effective or capable of meeting the massive energy needs of modern society, but fossil fuels are available in sufficient supply to meet current needs. The main gas implicated in Global Warming is carbon dioxide one of the products of burning fossil fuels.

The economies of the industrialised world are dependent on oil supplies. Rapid transport and available electrical power underpins our society.

At first when a new polymer was discovered, Scientists thought long and hard about what jobs these polymers could do. Some polymers, such as the adhesive on Post-It notes, were happy accidents ! Modern scientists understand polymers and how to make them very well. Now polymers are designed with specific properties to do well-defined jobs. There might be called Designer Polymers. Polymers designed for specific jobs include: Kevlar - designed for body armour - very strong but lightweight Lycra - sports-wear - very flexible but strong

Goretex - breathable fabric - lets sweat out but prevents rain getting in

Designer polymers have made an impact in medical applications too: Smart Materials are materials which change in response to changes around themselves. Shape memory polymers can change their shape in response to heat. Stitches which can pull the edges of a wound together at body-temperature are one example.

Hydrogels contain cross-links which trap water, making wound dressings which are moist and sterile possible, as well as being useful for soft contact lenses.

Remember ! Polymers are made from monomers such as alkenes Alkenes are made by cracking reactions, along with short chain alkanes the starting material is long-chain alkanes These long chain alkenes come from fractional distillation of crude oil Therefore polymers of this kind are from nonrenewable sources, and are using up our crude oil reserves. RECYCLING helps to reduce the rate at which crude oil is used up to make polymers. BUT recycling is labour intensive, and the different polymers all have to be sorted. Therefore recycling plastics is not very cost effective. Many people cant be bothered to save and sort plastic waste for recycling.

Many polymers are not bio-degradable. This means that they will not be broken down in nature by micro-organisms. This causes problems for disposal of waste polymers: - because they dont bio-degrade they can take up valuable landfill - they may give off toxic fumes when burnt - plastic waste is unsightly and can be dangerous to wildlife, if animals or birds swallow the plastic, or get trapped in waste objects - recycling takes a lot of effort to collect the waste - to recycle the plastics have to be sorted into different types, which is labour intensive and an unpleasant job - for these reasons recycled plastics can be more expensive than just making new polymers using products from crude oil

What are scientists doing to solve polymer disposal problems ? Designing polymers which are bio-degradable, or photo-degradable (broken down slowly by sunlight), or water-soluble.

Developing ways of burning plastic waste as a fuel but without the toxic emissions, e.g. by using scrubbers to remove these gases.