F322 Alkenes

F322 Alkenes Notes

Candidates should be able to: (a) state that alkenes and cycloalkenes are unsaturated hydrocarbons; (b) describe the overlap of adjacent p-orbitals to form a -bond; (c) state and explain the trigonal planar shape around each carbon in the C=C of alkenes; (d) describe addition reactions of alkenes, ie by ethene and propene, with: (i) hydrogen in the presence of a suitable catalyst, ie Ni, to form alkanes, (ii) halogens to form dihalogenoalkanes, including the use of bromine to detect the presence of a double C=C bond as a test for unsaturation, (iii) hydrogen halides to form halogenoalkanes, (iv) steam in the presence of an acid catalyst to form alcohols; (e) define an electrophile as an electron pair acceptor; (f) describe how heterolytic fission leads to the mechanism of electrophilic addition in alkenes; (g) describe the addition polymerisation of alkenes; (h) deduce the repeat unit of an addition polymer obtained from a given monomer; (i) identify the monomer that would produce a given section of an addition polymer; (j) outline the use of alkenes in the industrial production of organic compounds: (i) the manufacture of margarine by catalytic hydrogenation of unsaturated vegetable oils using hydrogen and a nickel catalyst, (ii) the formation of a range of polymers using unsaturated monomer units based on the ethene molecule, ie H2C=CHCl, F2C=CF2; (k) outline the processing of waste polymers by: (i) separation into types (ie PTFE, etc.) and recycling, (ii) combustion for energy production, (iii) use as a feedstock for cracking in the production of plastics and other chemicals; (l) outline the role of chemists in minimizing environmental damage by: (i) removal of toxic waste products, ie removal of HCl formed during disposal by combustion of halogenated plastics (ie PVC), (ii) development of biodegradable and compostable polymers, ie from isoprene (2-methyl-1,3-butadiene), maize and starch.

General Akenes and cycloalkenes are UNSATURATED hydrocarbons. e.g. hex-1-ene , cyclohexene

The alkenes form a homologous series with general formula CnH2n. Each member of the series differs by a -CH2- unit. Benzene (C6H6) is an ARENE (rather than the alkene "cyclohexatriene" that you might expect), since the double bonds and single bonds are not alternating around the ring as the displayed formula would suggest, but all equivalent, with the double bond delocalised all around the ring. That's why we use the symbol: rather than:

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F322 Alkenes Bonding In addition to the sigma- bonds which hold carbon atoms to hydrogen atoms and to other carbon atoms (single bonds), in an alkene there is double bond >C=C< between two carbon atoms.

A double bond consists of a sigma bond between the two carbon atoms, formed by the overlap of the two s-orbitals, but also adjacent p-orbitals overlap to form a second bond between the two carbon atoms. This pi-bond is formed parallel to the sigma bond, and it is this bond that prevents rotation. Note also the symmetry at each carbon atom. The three bonds from each carbon are trigonal planar with approx 120 bond angle because they repel each other as far as possible. The pi-bond is above and below the plane of the three sigma bonds. Physical properties Because of the double bond having different bond angles (120) to the rest of the chain (109.5), alkenes can't pack as closely as the corresponding alkanes and therefore have correspondingly lower melting and boiling points. e.g. boiling points in Kelvin: ethene 169K propene 226K ethane propane 185K 231K

Like alkanes, the alkenes are insoluble in water (a polar solvent) but dissolve in non-polar solvents e.g. other hydrocarbons. Reactions of Alkenes Most alkene reactions involve breaking the pi-bond, which is weaker than the sigma- bond, leaving the sigma bond intact, and thereby attaching new species to the chain to form a saturated molecule. These are ADDITION reactions. Alkenes have an area of high electron density in the double bond. With lots of negative charge around here, species wanting to accept an electron pair (often positively charged species, but not always) are attracted here where they can attack the double bond. We call species which are electron pair acceptors ELECTROPHILES (electron loving). Thus these reactions are termed ELECTROPHILIC ADDITION reactions.

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F322 Alkenes i) reaction with hydrogen, H2

H

e.g.

C C H H

+ H2

H H H C C H H H

ethene

ethane

How it works: The double bond breaks leaving only a single bond. An H atom from the H2 is added to each of the carbons that had the double bond Reagents: Hydrogen Conditions: Nickel catalyst , 150C Use: Used in industry as hydrogenation (hardening) of polyunsaturated vegetable oils for margarines ii) reaction with halogens, Cl2, Br2, I2
H

e.g.

C C H H

+ Br2

H H H C C H Br Br

ethene

1,2-dibromoethane

Reagents: Bromine Conditions: mix at room temp Use: test for the presence of a C=C bromine loses its orange colour and is decolourised. Note: F2 is too powerful an oxidising agent and tends to ignite the hydrocarbon ! Chlorine and iodine produce similar addition products. iii) reaction with hydrogen halides, HF, HCl, HBr, HI

e.g.

C C H H

+ HCl

H H H C C H Cl H

ethene
Reagent: hydrogen chloride Conditions: mix gases at room temperature

chloroethane

Note that reactivity increases from HF to HI. HF will react with an alkene only under pressure.

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F322 Alkenes Note also that addition of a hydrogen halide to an unsymmetrical alkene can result in two possible isomeric products:

CH3CH=CH2 + HBr
H H H H C C C H H

CH3CHBrCH3
H H H H C C C H H Br H

or

CH3CH2CH2Br
H H H H C C C H Br H H

propene
iv) reaction with water (steam)

2-bromopropane

1-bromopropane

Where water is added to a molecule, we call this a HYDRATION reaction. The electrophilic addition of water to an alkene to form an alcohol is a HYDRATION. This is not to be confused with a hydrolysis, which is breaking a molecule up due to a reaction with water forming two products. As previously, with an unsymmetrical alkene two isomeric products are possible.

Reagent: water (steam) Conditions: an acid catalyst such as H3PO4 at 300C and 6MPa pressure This is the industrial route to alcohols not for drinking methylated spirits, industrial alcohol etc. Check your understanding: Write equations (displayed or skeletal formulae) and show the product(s) produced when: i) chlorine reacts with but-2-ene ii) hydrogen chloride reacts with but-2-ene iii) hydrogen iodide reacts with but-1-ene iv) steam (water) reacts with methylpropene v) pent-1-ene is burnt in excess oxygen

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F322 Alkenes Mechanism of electrophilic addition The steps by which a reaction takes place give chemists important information. In the case of electrophilic addition the reaction is initiated by the approach of a molecule with a dipole - either permanent, e.g. with HCl - or induced by the presence of the double bond e.g. with Br2 There are two steps. Step 1: Approach of electrophile and attraction of an electron pair from the pi-system to form a bond to the + end, and heterolytic fission of the bond in the electrophile. A curly arrow shows where the electron pair comes from and where is goes. The pair come FROM a bond or a lone pair on an atom, and goes TO an atom where the new bond is being formed. Step 2: The intermediate carbocation which is formed is very reactive and immediately reacts with the bromide ion forming a covalent bond

Note: when drawing mechanisms, there are marks for - relevant dipoles - lone pairs - curly arrows (showing the movement of a PAIR of electrons)

Check your understanding: vi) Draw the mechanism for the electrophilic addition of HCl to propene.

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F322 Alkenes Addition Polymerisation Alkenes can undergo addition reactions in which alkene molecules join to each other to form long chains often tens of thousands of carbon atoms long. While these are addition reactions, we ARE NOT REQUIRED TO KNOW THE MECHANISM. The individual alkene molecule is referred to as a monomer, and the resulting chain as a polymer. Note that (ignoring the ends of the chain) the empirical formula of the monomer and of the polymer are the same. We ignore the ends of the chain because they are insignificant compared with the length of the polymer chain. Often the end of the chain will be the molecule used as an initiator to start the reaction. Polymers are not always used as pure substances, they can be modified to give them the properties required for specific applications e.g. plasticisers can be added. These molecules sit between the polymer molecules, reducing the intermolecular forces and making the material more flexible. Plasticisers are usually liquids with high boiling points. Examples: But-1-ene and but-2-ene both react to form polymers. We may be required to draw the monomers, sections of the polymers, the repeat units, or write a balanced equation for the reactions:

H H

H H H C C C C H H H
but-1-ene

H H H

H H

H C C C C H H

but-2-ene

It may be helpful to re-draw the monomer molecules starting with the C=C and adding to each carbon the atoms/groups which are connected to it above and below:

H H C C H C2H5

H C

CH3 C

CH3 H

Drawing a section of a polymer, given a monomer: 1. Draw a chain of 6 carbon atoms leave the "connecting" bonds dangling 2. Find the first C of the double bond in the monomer transfer its side groups to the first carbon in your section 3. Transfer the side groups from the second C of the double bond to the second C of the chain 4. Repeat steps 2 and 3, alternating along the chain

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F322 Alkenes

H H C C

H H C C

H H C C

H C

CH3 H C C

CH3 H C C

CH3 C

H C2H5 H C2H5 H C2H5

CH3 H

CH3 H

CH3 H

Drawing a repeat unit: A repeat unit can be found by taking any two linked carbons in the polymer chain with their attached side groups:

H H C C H C2H5
n

H C

CH3 C
n

CH3 H

If starting with the monomer, simply draw the monomer then turn the double bond into a single bond and add connecting bonds to the two carbons which were originally doublebonded. Drawing the monomer from repeat unit or a section of chain: Take two adjacent carbons in the chain, plus their attached side groups. Remove the connecting bonds and add the double bond. For example, here's a repeat unit of poly(pent-2-ene), from which we can construct the monomer:

CH3 H C H C CH2 CH3

n

CH3 H C H C CH2 CH3

H H H

H H H H H

H C C C C C H

pent-2-ene

Writing a balanced equation: We don't know how many monomers form CH3 H the chain, so we use 'n' to be the number of monomers. This will produce a chain 'n' n C C repeat units long. Note the connecting H CH2 bonds sticking through the brackets, and don't forget the 'n' after the brackets to CH3 show the number of times the repeat unit repeats.

CH3 H C H C CH2 CH3

n

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F322 Alkenes Disposal of Waste Polymers Most polymers are non-biodegradable (not broken down by micro-organisms). Having strong covalent bonds which are mostly non-polar makes them resistant to chemical attack too. This makes polymer waste hard to dispose of. Being non-biodegradable makes it unsuitable for disposal in landfill sites (although that is where much polymer waste currently turns up) because more and more sites have to be found. One alternative is to separate the waste into different types, and recycle (sort, melt and remould). This labour intensive. Research chemists have a key role in reduce environmental damage and improve sustainability from disposal of polymers: Polymer waste can be burnt for energy generation Burning halogenated plastics (e.g. PTFE or PVC) can produce toxic gases, e.g. burning PVC can produce acidic gases e.g. HCl, dioxins, phosgene. Chemists have a role in minimising environmental damage by removing these toxic waste gases from the waste gases of combustion. Polymer waste can be cracked Used in cracking reactions (instead of fractions from finite crude oil), to produce feedstocks such as alkenes for plastics or chemicals. This technology is a current research area for industrial chemists. Photodegradable, biodegradable or compostable polymers Researchers are developing polymers that can be broken down more easily by light or micro-organisms, and can be made from naturally occurring raw materials rather than those based on finite crude oil. Many of these are already in use, e.g. for supermarket shopping bags. The starting materials include isoprene (2-methyl-1,3-butadiene) which is natural rubber, maize and starch. International co-operation is necessary to produce pollution levels (plastics): - all countries contribute towards pollution - waste plastics travel across boarders and seas - scientists can share ideas/warn governments of risk - world-wide legislation can be introduced Check your understanding: vii) Write a balanced equation for the addition polymerisation used to form polyethenol viii) Draw a section of the polymer formed by addition polymerisation of methylpropene

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F322 Alkenes

Answers to Check your Understanding questions:

Write equations (displayed or skeletal formulae) and show the product(s) produced when: i) chlorine reacts with but-2-ene
Cl

Cl2 +

Cl

ii)

hydrogen chloride reacts with but-2-ene HCl + but-2-ene is (only one product since Cl symmetrical)
I

iii)

hydrogen iodide reacts with but-1-ene HI + (two

I

OR products since but-1-ene is

unsymmetrical) iv) steam (water) reacts with methylpropene H2O(g) +

OH

OR

HO

(two products since methylpropene is unsymmetrical) v) pent-1-ene is burnt in excess oxygen + 7 O2 vi) 5 CO2 + 5 H2O

Draw the mechanism for the electrophilic addition of HCl to propene.

vii) Write a balanced equation for the addition polymerisation used to form polyethenol Page 9

F322 Alkenes

viii) Draw a section of the polymer formed by addition polymerisation of methypropene methypropene can be drawn as so the section of the polymer is

H CH3 C C H CH3

H CH3 H CH3 H CH3 C C C C C C H CH3 H CH3 H CH3

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