Unit 2 mod 1 chem.

Alkenes

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Alkenes (Module 1) a) state the general formula of alkenes b) know and identify the functional group in alkenes c) understand that alkenes are much more reactive than alkanes and explain why this is so d) appreciate that alkenes are not used as fuels but as building blocks to produce other chemicals e) describe the chemical reactions of alkenes (with conditions) i) combustion (include colour of flame) ii) halogenation iii) oxidation (hot and cold) iv) hydration v) hydrohalogenation vi) hydrogenation (include production of trans-fat which are harmful) and give equations for each chemical reaction f) state the name of the mechanism by which alkenes use and describe the mechanism using ethene and bromine as an example g) define Markovnikovs Rule and apply it to the prediction of products for the reaction of hydrogen halides and UNsymmetrical alkenes Alkenes are a family of hydrocarbons (compounds containing carbon and hydrogen only) containing ONE carbon-carbon double bond. They contain a multiple bond and thus are called UNSATURATED molecules. The first two are: ethene propene C2H4 C3H6

You can work out the formula of any of them using the general formula: CnH2n The functional group is the double bond C=C Reactivity of alkenes vs alkanes Alkenes have an electron rich centre i.e. partially negative region, the double bond or bond. Alkanes do not have either a partially positive or negative region. Therefore alkenes are susceptible to electrophilic attack but alkanes are NOT susceptible to either electrophile or nucleophile attack. Hence alkenes are more reactive than alkanes. Since alkenes are reactive compounds, they are NOT used as fuels like alkanes but as building blocks in the petro-chemical industry. Reactions of alkenes (using ethene as an example) 1. Combustion With oxygen or air to carbon dioxide and water (in excess oxygen) if oxygen is limited, carbon monoxide and water are the products e.g. C2H4 + 3O2 2CO2 + 2H2O alkenes burn with a smoky yellow flame

Unit 2 mod 1 chem. Alkenes

a) Hydrogenation

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2. Addition (all unsaturated compounds undergo addition reactions)

Ethene reacts with hydrogen in the presence of a finely divided nickel catalyst at a temperature of about 150C. Ethane is produced.

Some margarine is made by hydrogenating carbon-carbon double bonds in animal or vegetable fats and oils. You can recognise the presence of this in foods because the ingredients list will include words showing that it contains "hydrogenated vegetable oils" or "hydrogenated fats". If there are two or more carbon-carbon double bonds in each chain, then it is said to be polyunsaturated. However, there are possible health benefits in eating mono-unsaturated or polyunsaturated fats or oils rather than saturated ones - so you wouldn't want to remove all the carbon-carbon double bonds. One of the problems arises from the hydrogenation process. The double bonds in unsaturated fats and oils tend to have the groups around them arranged in the "cis" form. The relatively high temperatures used in the hydrogenation process tend to flip some of the carbon-carbon double bonds into the "trans" form. If these particular bonds aren't hydrogenated during the process, they will still be present in the final margarine in molecules of trans fats. The consumption of trans fats has been shown to increase cholesterol levels (particularly of the more harmful LDL form) - leading to an increased risk of heart disease. b) THE HALOGENATION OF ALKENES Ethene and chlorine / bromine In each case you get an addition reaction. For example, bromine adds to give 1,2-dibromoethane.

The reaction with bromine happens at room temperature. If you have a gaseous alkene like ethene, you can bubble it through either pure liquid bromine or a solution of bromine in an organic solvent like tetrachloromethane. The reddishbrown bromine is decolourised as it reacts with the alkene.

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Using bromine water as a test for the presence of a multiple bond If you shake an alkene with bromine water or bromine liquid (or bubble a gaseous alkene through bromine water), the solution becomes colourless. Alkenes decolourise bromine water.

c) ALKENES and HYDROGEN HALIDES

Addition to symmetrical alkenes All alkenes undergo addition reactions with the hydrogen halides. A hydrogen atom joins to one of the carbon atoms originally in the double bond, and a halogen atom to the other. For example, with ethene and hydrogen chloride, you get chloroethane: Conditions The alkenes react with gaseous hydrogen halides at room temperature. If the alkene is also a gas, you can simply mix the gases. If the alkene is a liquid, you can bubble the hydrogen halide through the liquid. Addition to unsymmetrical alkenes Orientation of addition If HCl adds to an unsymmetrical alkene like propene, there are two possible ways it could add. However, in practice, there is only one major product.

This is in line with Markovnikov's Rule which says: When a compound HX is added to an unsymmetrical alkene, the hydrogen becomes attached to the carbon with the greater number of hydrogen atoms attached to it already.

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In this case, the hydrogen becomes attached to the CH2 group, because the CH2 group has 2 hydrogen atoms and the CH group only has one hydrogen atom attached. d) Oxidation of alkenes Alkenes react with potassium manganate(VII) solution in the cold. Manganate(VII) ions are a strong oxidising agent, and in the first instance oxidise ethene to ethane-1,2-diol (old name: ethylene glycol). :

Oxidation of alkenes with hot concentrated acidified potassium manganate(VII) solution The formula below the general form of all alkenes. The R groups represent alkyl groups.

The hot conc. potassium manganate(VII) solution oxidises the alkene by breaking the carbon-carbon double bond and replacing it with two carbonoxygen double bonds. Two fragments are produced.

The products are known as carbonyl compounds because they contain the carbonyl group, C=O. Carbonyl compounds can also react with potassium manganate(VII), but how they react depends on what is attached to the carbonoxygen double bond. So we need to work through all the possible combinations. Carbonyl compounds which have two hydrocarbon groups attached to the carbonyl group are called ketones. Ketones aren't that easy to oxidise, and so there is no further action. If the groups attached either side of the original carbon-carbon double bond were the same, then you would end up with a single ketone. If they were different, then you would end up with a mixture of two. For example:

Unit 2 mod 1 chem. Alkenes

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Please note that if one of the R groups attached to the carbon atom is a hydrogen atom, then it would form the corresponding carboxylic acid. If both R groups are hydrogen atoms then it is further oxidised to carbon dioxide and water. This breakage of double bonds can be used to determine the position of double bonds in a molecule. e) Hydration In the lab, ethanol is produced by reacting ethene with concentrated sulphuric acid with concentrated sulphuric acid at 170 C. In industry, ethanol is manufactured by reacting ethene with steam. The reaction is reversible.

Only 5% of the ethene is converted into ethanol at each pass through the reactor. By removing the ethanol from the equilibrium mixture and recycling the ethene, it is possible to achieve an overall 95% conversion. A flow scheme for the industrial preparation looks like this:

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Alkenes react via the electrophilic addition mechanism Using ethene and bromine as an example:Note: The arrows show the movement of the electrons towards a positively charged region. In the first stage of the reaction, one of the bromine atoms becomes attached to both carbon atoms, with the positive charge being found on the bromine atom. A bromonium ion is formed.

The bromonium ion is then attacked from the back by a bromide ion formed in a nearby reaction.

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Worksheet 1 a)

Circle one functional group in the molecule above.

b) Draw the structural formula when retinol reacts with excess bromine in tetrachloromethane

c) Describe what would be observed in the reaction . d) Describe what would be observed if excess acidified potassium manganate VII was used instead of excess bromine. . e) Calculate the molar mass of retinol (H = 1, O = 16, C = 12)

Unit 2 mod 1 chem. Alkenes

f) Using just a portion of the retinol molecule

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i) Show the mechanism of the reaction of retinol and bromine.

ii) Show the structural formula of the product when retinol is reacted with hydrogen gas

iii) Show the structural formula of the product when retinol is reacted with steam

v) What volume of carbon dioxide would be produced if 1 mole of retinol was completely burnt in air? Remember 1 mole of any gas occupies 24 dm3 at rtp