Topic 6c SLOP Booklet

Organic Chemistry: Alkenes

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Ethene, Propene etc. all belong to the same homologous series of compounds, the alkenes. All of these
organic compounds contain a highly reactive carbon – carbon double bond, and can be used as a
building block to prepare more complex organic molecules.

Large quantities of these alkenes are manufactured by cracking processes that we encountered when we
looked at alkanes. However in comparison to alkanes, whilst both hydrocarbons, alkenes are said to be
unsaturated.

Alkanes: Nomenclature and Overview

In this and future topics, you may see reference made to aliphatic hydrocarbons; this is a term used to
describe a specific type of hydrocarbons.

Aliphatic Hydrocarbons:- are those with branched or unbranched chains of carbon atoms, or rings of
carbon atoms that are not aromatic (do not contain delocalised electrons).

Systematic Name Structural Formula Displayed Formula Skeletal Formula

But-1-ene

CH3C(CH3)CHCH3

CH2CHCH2CHCH2

CH2C(CH3)CH2CH2CH2OH

C6H8 n/a

n/a

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 1. Why would you expect both alkenes and cycloalkenes to have similar reactions?
2. Which intermolecular forces are present in alkenes?
3. Propene and Butene are both gases at room temperature but pentane is a liquid, explain
this difference in state in terms of intermolecular forces.
4. State the state of ethene and hex-2-ene at room temperature.
5. Why does the position of the carbon-carbon double bond have a negligible effect on the
melting and boiling temperature of alkenes.
6. Define an isomer.
7. Draw the skeletal formula and name two differing isomers of pentene.
8. Explain which isomer you’ve drawn of pentene, including pentene, would have the lowest
boiling point, making reference to surface area of contact.
9. 10 cm3 of a hydrocarbon CaHb reacted with 50 cm3 of oxygen gas to produce 30 cm3 of
carbon dioxide and 40 cm3 of water vapour. Use the data to calculate to reacting moles in
the equation and suggest value for a and b.
10. Is the hydrocarbon calculated in Q9 an alkene?

The Nature of the C=C Double Bond in Alkenes

Covalent Bonds are formed from the overlap of orbitals. There are two types of bonds we have
been introduced to:- Sigma (σ) and Pi (π) bonds.

NOTE: NGoalby Chemrevise Sheet σ and π

For the following questions we will consider the structure of ethene.

11. Explain the difference between a sigma and a pi bond.

12. Draw a displayed formula diagram for ethene.
13. State the bond angle around the (H-C-H bond) in a molecule of ethene explain why.
14. Identify the number of sigma bonds present between the two carbon atoms.
15. Identify the number of pi bonds present between the two carbon atoms.
16. Identify the number of sigma bonds present between the carbon and hydrogen atoms.
17. Using Q14-16 explain the difference between a single bond and double bond in terms of
bonds present within them.
18. Explain why the bonds between the two carbon atoms are said to have a higher electron
density than the carbon – hydrogen bonds.

C-C (in ethane) C=C (in ethene) C≡C (in ethyne)

Bond Energy (kJ mol-1) 346 598 813
Bond Length (nm) 0.154 0.134 0.121
In a π bond, the two electrons of the π-bond are not situated in the same axis as the carbon
atoms (see diagram). This means “on average” they are not as close to the nuclei of the atoms as
the electrons situated in the σ-bond.

19. Which bond requires more energy to break, the σ-bond or the π-bond?
20. Why then, does the double bond in ethene require more energy to break than the single
bond in ethane?
21. Are alkenes saturated or unsaturated molecules?
22. Propene can react with hydrogen to form propane. Write the balanced symbol equation
for this reaction.
23. Which type of reactions do alkenes based on your answer to the above question.
24. If an alkene undergoes the type of reaction identified in Q23, what type of molecule does
in become? (see Q21)
25. Which bond must break to allow the reaction type identified in Q23?
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 E/Z Isomerism
Define an isomer

Bond Angle around Carbon in Ethene? Molecule Shape in Ethene?

Alkenes can exhibit a type of isomerism called E-Z stereoisomerism. E-Z isomers exists due to the
restricted rotation about the C=C bond.

Why do E-Z Stereoisomers Arise?

1.

2.

Z = Zusammen = Same Side | E = Entgegen = Opposite Sides

Z-but-2-ene E-but-2-ene

Skeletal Formula Skeletal Formula

But-1-ene, doesn’t exhibit E-Z Isomerism. 1,1-dichloroethene, doesn’t exhibit E-Z

Isomerism.

26. Explain why alkenes exhibit E/Z isomerism but alkanes do not.
27. Draw and name the E/Z Isomers of 1-2-dibromoethene.
28. Draw and name the E/Z Isomers of CH3CHCHCH2CH3.
29. Explain why 2-methylpropene does not exhibit E/Z Isomerism.
30. “Violet oil” is sometimes used in aromatherapy treatments for it’s
mild pain-killing properties. The oil has a strong “leafy” odour due
partly to the presence of compound A.
(a) Name the functional groups present in compound A.
(b) State the molecular formula of A.
(c) Compound A is one of a pair of E/Z Isomers. Draw a diagram to show the structure of
the other isomers and label it as E or Z.
31. Geraniol can exhibit E/Z isomerism due to the structure of
the molecule around the C=C bond nearest to the OH
group. One isomer is shown adjacent.
(a) Draw the skeletal formula of the other isomer.
(b) Explain why there are no E/Z isomers arising from the C=C bond at the other end of the
molecule.
NOTE: Chemsheets: E/Z Isomerism Sheet
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 Cis-Trans Isomerism
Organic molecules vary in their complexity, and not every molecule you encounter with a double bond will
have complex groups on either side of the carbon-carbon double bond.

Cis-trans isomerism arise in compounds containing the carbon-carbon double bond when there are just two
different groups on both carbon atoms of the double bonds. So rather than using E/Z Isomerism, previously
the terms cis and trans where used.

Cis = same side | Trans = opposite sides

Draw the displayed formula for 1,2-dichloroethene.

Draw the displayed formula for cis-1,2- Draw the displayed formula for trans-1,2-
dichloroethene. dichloroethene.

Draw the displayed formula for pent-2-ene.

Draw the displayed formula for cis-pent-2-ene Draw the displayed formula for trans-pent-2-ene

• How do we decide which groups have the higher priority?

• How do we decide which isomer is the cis and the trans isomer?
• This is where the cis-trans naming system breaks down, and why it’s neccesary to use the E/Z
naming system. It was specifically developed to deal with this occurane.

CIP Priority Rules

To understand which atoms we take priority and we must consider first to name E/Z Isomers we have an
established set of rules. At A-Level you only need to consider the first set of rules surrounding the CIP (Cahn-
Ingold-Prelog) Priority rules.

• The atom which has the higher atomic number is given the higher priority.
Draw the displayed formula for 2-bromo-1-chloro-
prop-1-ene.

Split the molecule down the middle, circle the

atoms/groups which have the higher atomic
number.
Draw E-2-bromo-1-chloro-prop-1-ene Draw Z-2-bromo-1-chloro-prop-1-ene

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 E/Z | Cis/Trans Isomerism Questions
32. Consider the following compounds:-

(a) Name each of the compounds shown above.

(b) State whether you would expect any of them to show cis-trans isomerism.
(c) For those molecules which show cis-trans isomerism. Draw the structures of the possible
isomers.
33. Compounds with double bonds between carbon atoms can exhibit stereoisomerism.
(a) Draw structures for the two stereoisomers of 1,2-dichloroethene.
(b) What features of the double bond allows for there to be stereoisomers?
(c) Why can the cis-trans prefixes be used for the stereoisomers of 1,2-dichloroethene?

Isomer Melting Point (oC) Boiling Point (oC)

Cis-1,2-dichloroethene -80 60
Trans-1,2-dichloroethene -50 48
The trans and cis isomers have differing melting and boiling points. Considering your
knowledge of structure and intermolecular forces, answer the following questions.

(d) Which intermolecular force is present in all molecules of the differing isomers?
(e) Which of the two isomers is polar?
(f) Which intermolecular force will arise in the isomer identified in part (d)?
(g) Explain the elevated boiling point in terms of energy and your answers to (d) – (f).
(h) Explain, in terms of points of contact, why the opposite is true when considering the
melting point of the differing isomers?
34. Addition reactions to alkenes can result in the formation of isomeric compounds.
Butene can react with HBr in an addition react to form two structural isomers.
(a) State the balanced symbol equation for this reaction, state symbols are not required.
(b) Name the homologous series the product belongs to.
(c) Why is the atom economy for this reaction 100%?
(d) Give the structures of these two structural isomers and name the type of isomerism
shown.
(e) Scientists prefer to form the family of products in this many, in comparison to the free
radical substitution mechanism. Explain why the free-radical substitution mechanism is
not used to form this family of compounds.
35. Consider the following molecules, add a prefix to state whether they are the E or Z isomer.

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 Reactions of Alkenes - Overview
Alkenes, unlike alkanes, are much more reactive with differing laboratory reagents. With alkanes we saw
that high temperatures/energy is needed to break the stable C-C bonds within alkanes.

Alkenes unlike alkanes are affected by polar reagents and oxidising agents such as potassium
manganate(VII). Nearly all the important reactions of alkenes are addition reactions. Due to this, the
product can often be predicted easily.

Combustion of Alkenes (Oxidation of Alkanes)

Complete Combustion % by mass of C in C2H4.

Alkenes will burn in air when heated, they burn to give CO2 and H2O.
C2H4 + 3O2(g) → 2CO2(g) + 2H2O(l) | ∆Hc = -1410 kJ mol-1

Alkenes burn with a smokier flame than that or an alkane with the same % by mass of C in C2H6.
number.
Why? Consider the percentage of carbon in each. Which is higher?
Addition of Hydrogen
Alkenes will react with hydrogen to produce alkanes.

The ADDITION of Hydrogen may be referred to as Reduction or Hydrogenation

C2H4(g) + H2(g) → C2H6(g)

Reagent: Hydrogen | Conditions: Nickel Catalyst | Temperature: 150oC | Product: Alkanes

Addition of Halogens
Alkenes will react with chlorine/bromine to produce dihaloalkanes.
C2H4(aq) + Br2(aq) → C2H4Br2(aq)

Reagent: Bromine (dissolved in organic solvent) | Temperature: Rm Temp | Product: Dihaloalkanes.

Colour Change: Orange → Colourless
NOTE: Reaction can be used as a test for the alkene functional group
Addition of Hydrogen Halides
Alkenes will react with Hydrogen Halides, excluding HF, to form a halogenoalkane.
C3H6(g) + HBr(aq) → C3H7Br(aq)

Reagent: HCl/HBr/HI | Temperature: Rm Temp | Product: Halogenoalkane

Addition of Steam
In industry, alkenes can be converted to alcohols.

The ADDITION of Water may be referred to as Hydration as water is added.

C2H4(g) + H2O(g) ⇋ CH3CH2OH(g)

Reagent: Steam | Conditions: Acid Catalyst (Conc. H3PO4(aq)) | Temperature: 300oC - 600oC |
Pressure: 70 atm | Product: Alcohols
NOTE: Reaction is reversible | Cannot be performed in the laboratory.
Oxidation by Potassium Manganate(VII)
Alkenes will be oxidised by acidified Potassium Manganate(VII) to form diols.
[O] this symbol represents the oxidising agent.

C2H4 + [O] + H2O → CH2(OH)CH2(OH)

Reagent: KMnO4(aq)/H+(aq) | Conditions: Acid Catalyst (Conc. H3PO4) | Temperature: Rm Temp

| Product: Diols (Molecules with two alcohol groups) | Colour Change: Purple → Colourless
NOTE: Reaction can be used as a test for the alkene functional group
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 Reaction of Alkenes – Questions

36. Predict the formula and name of the product of the reaction between:-
(a) Propene and Chlorine.
(b) But-2-ene and Hydrogen.
(c) Propene and Hydrogen.
37. Write the full symbol equation for the reaction between
(a) But-1-ene and Hydrogen Bromide.
(b) 2-methylbut-2-ene and Hydrogen Iodide.
(c) Propene and Hydrogen, over a Nickel Catalyst (ensure catalyst is shown).
(d) Excess Propene and KMnO4.
(e) State the expected colour change in reaction (d).
38. Use skeletal formulae to write an overall equation for the reaction of:
(a) Pent-2-ene with Bromine.
(b) But-2-ene with Hydrogen Bromide
(c) Hexa-1,4-diene with excess hydrogen.
(d) Cyclopentene with Hydrogen.
(e) Cyclohexa-1,3-diene with bromine.
39. Give the reagents and conditions needed to carry out each of the following reactions:
(a) Bromination of Alkenes
(b) Production of ethanol from ethene in industry.
(c) Laboratory hydrogenation of alkenes to alkanes.
(d) Explain why the reaction in (c) needs a catalyst.
(e) Explain why the catalyst is a fine powder.
40. This question is about the synthesis and reactions of
butane-1,4-diol. Butane-1,4-diol can be synthesised
from but-2-ene-1,4-diol, by reaction with a reagent,
B.
(a) Identify reagent B and state suitable conditions for this reaction.
(b) This reaction is best described as:-
A| Hydrolysis B| Oxidation C| Reduction D| Substitution
(c) Name one other commercially important product that can be manufactured by this
type of reaction with the alkene group?
(d) Identify whether the shown diagram of but-2-ene-1,4-diol is the E or Z isomer.
(e) Draw the other stereoisomer of but-2-ene-1,4-diol.
(f) Why can butane-1,4-diol not form E/Z isomers.
41. Consider the following compounds.

Structure CH3CH2CH2CHCHCH3 CH3CH2CH2CH2CHCH2 CH3CH2CH2CH2CH2CH3

Name
The answers to the following questions may be one or more than one of the compounds
featured above A-D.
(a) Which would decolourise bromine in the absence of sunlight?
(b) Which would react with chlorine, but only when heated or exposed to sunlight?
(c) Which would absorb 1 mole of hydrogen per mole of the compound in the presence of
a nickel catalyst?
(d) Which has E and Z isomers?
(e) Which are unsaturated?

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 Electrophilic Addition Mechanism
Alkenes undergo addition reactions because they are unsaturated hydrocarbons. The
unsaturated hydrocarbons contain a carbon-carbon double bond which has a high electron
density. This means there is a higher probability of electrons being present in this locations.

Due to their high electron density, this means that the alkene are susceptible to attack by
electrophiles.

What is an electrophile?

The addition reactions that alkenes undergo are described as being electrophilic addition
reactions. As the π bond is weaker than the σ bond, this means it is more likely to break, which
allows the carbon previously in a carbon-carbon double bond form a bond with another atom.
General Electrophilic Addition Mechanism

What is a carbocation? What do curly arrows show?

NOTE: Chemsheets Reactions of Alkenes 1

42. For the following reactions: Write the balanced equations, name of the organic product,
name of the mechanism and draw the mechanism for the reaction.
(a) But-2-ene and Br2(aq).
(b) Methyl-propene and Hydrogen Bromide
(c) But-1-ene and H2SO4.
(d) Propene and Water.
(e) Draw the two stereoisomers for the major organic product of (b).
(f) Name the two stereoisomers you have drawn.
(g) Explain why but-2-ene can exhibit E-Z isomerism.
(h) Can the cis-trans notation be used for the product of the reaction in (a).
(i) Ethene and Bromine and Water. (Major product is 2-bromoethanol)
(j) Explain why the major product in the reaction detailed in (e) not 1,2-dibromoethane.
43. SUse skeletal formulae to write an overall equation for the reaction of:-
(a) Pent-2-ene with Bromine.
(b) But-2-ene and Chlorine.
(c) Hexa-1,4-diene with excess hydrogen.
(d) Cyclohexa-1,3-diene with bromine.
(e) Cyclopentene with hydrogen.

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 Markovnikov’s Rule | Addition to Unsymmetrical Alkenes
When a molecule such as HCl adds to an unsymmetrical alkene, such as propene, there are actually two
possible products, whilst you might expect it to be just one. We can work out systematically which product
would form.

If you were to determine the product experimentally, you would notice that a much larger proportion of 2-
bromopropane would form rather than 1-bromopropane, but why?

This is all to do with the relative stability of the carbocation intermediates formed in the mechanism.

What is an intermediate?

What is a primary (1º) What is a secondary (2º) What is a tertiary (3º)

carbocation? carbocation? carbocation?

What do we describe alkyl groups as being? What does this mean?

Why is the order of stability: 1º < 2º < 3º

Example mechanism | Propene and HBr(aq)

44. For the following reactions: write the balanced equations, name of organic product and
draw the mechanism for the reactions.
(a) But-1-ene and HBr.
(b) Pent-1-ene and H2O(g)
(c) 2-methylpropene and HCl.
(d) Which of the carbonations in Q43 is the most stable? Explain why.
45. When pent-2-ene reacts with Hydrogen Bromide, a mixture of products is formed.
(a) Name the two different products that are formed.
(b) Draw the skeletal formulae of the carbocation intermediates that would form.
(c) State the conditions required for the above reaction.
(d) Explain the proportion (in %) of each product that forms.
(e) Why does the stated
percentages highlighted in (c)
form in this reaction?
46. An example of an alkene with six
carbon atoms is 2-methylpent-1-
ene. It reacts with chlorine by
means of an electrophilic addition
reaction. The diagram below shows a students attempt at drawing the mechanism for this
reaction. Identify the three errors in this student’s drawing of the mechanism.

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 Addition Polymerisation
Addition polymers are formed from unsaturated compounds under the right conditions, where
alkenes react with themselves. The conversion of substances from a single alkene monomer to a
polymer is called addition polymerisation.

Define a ‘Monomer’ Define a ‘Polymer’

What is Addition Polymerisation?

When naming addition polymers, we simply place the word “poly” followed by (name of the
unsaturated hydrocarbon) in brackets, even though the polymer formed is saturated “ene” is still
used as an ending.

Monomer Polymer Common Name

Ethene Poly(ethene)
Propene
Chloroethene Polyvinylchloride or PVC
Phenylethene PTFE or Teflon
Tetrachloroethene Polystyrene
NOTE: Chemsheets Addtion Polymers 1/2

47. Draw the displayed formula for the monomer chloroethene?

48. Draw a section of the polyvinylchloride polymer composed of four monomer units.
49. PVC is very resistant to water, acids and alkali’s. Look at the structure drawn in (b). Explain
why these properties arise.
50. Suggest two other properties polymers would have.

Polymer Waste
Edexcel Textbook: Pages 196 – 197
51. State 3 advantages of polymers over traditional materials.
52. Describe how we can reduce our use of polymers.
53. Why is the term recycling misused in the context of polymers?
54. Why is the recycling of polymers a difficult process?
55. State an advantage of incineration of polymers
56. Explain why incineration of polymers is problematic.
57. What is a biodegradable polymer?
58. What is a disadvantage of biodegradable polymers?
59. State a disadvantage of polymers.
60. How is the use of a polymer feedstock similar to cracking?
61. State 3 advantages of polymers over traditional materials
62. The halogenoalkane, chloroethene, is used to make the polymer poly(chloroethene).
(a) Draw the displayed formula of two repeating units of poly(chloroethene)
(b) Some polymers are disposed of by incineration. Ignoring any economic considerations,
explain why incineration is not suitable for the disposal of poly(chloroethene).
(c) Chloroethene has a boiling temperature of 260K and is known to be carcinogenic. Use
these facts to state one precaution that chemists should taken when using this
compound.

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