Alkenes

Alkenes & ethene

Occurs naturally in small quantity From crude oil product of cracking & catalytic reforming Raw materials polymers, detergents, solvents, etc. Unsaturated HC (has at least 1 C=C) For 1 C=C, less 2 H atoms General formula CnH2n Mp & bp increase with increase # of C

C=C
C-C ( bond) in ethane e cloud symmetrical about central axis of molecule Rotate about the axis 2 ends of ethane free to rotate C=C ( and bonds) in ethene bond above & below the plane of molecule Does not allow rotation around axis e density in bond covers large area around the nuclei of the C atoms C=C less than twice as strong as C-C (1 bond) in alkane Bond enthalpy for bond is 347, for bond is 265

C=C
Properties of molecules with C=C e rich positively polarised groups (electrophiles) more attracted to it bond provides e pair to form new bond with electrophile Geometric isomerism rotation around bond axis not possible

Naming & geometric isomerism

Geometric isomers = occur when components of molecules arranged on diff sides of molecule. Traditional way cis-trans isomerism Example:
H H3C H CH3
H H3C CH3 H

cis-but-2-ene

trans-but-2-ene

Diff physical props (mp, bp, density) Often same chemical reactivity

E-Z Isomerism
Current IUPAC system Works for all geometric isomers Groups attached around C=C are ranked Highest number, highest priority E = engegen = opposite Z = zussamen = together Reaction addition Energy to break bond is lower Heterolytic fission Can be attacked by electrophiles & oxidising agents
H H3C H CH3

Z-but-2-ene

H H3C

CH3 H

E-but-2-ene

E-Z Isomerism
1. Give correct E-Z nomenclature

Br I

F Cl
F < Cl < Br < I

Br I

Cl F

2. Find the mainisomers of pentene & give them correct E-Z nomenclature

Electrophiles & addition rxn

Electrophiles Electron deficient species Most common is H+ More attracted to C atom (has e pair)
Rxn of alkenes w H2 condition moderately high T (abt 200 C), Ni catalyst product - alkane
H H H

+
H

Ni
H2 H

H H

Electrophiles & addition rxn

Rxn w halogens decolourise Br2 (orange) product disubstituted halogenoalkane
H H H Br Br

+
H

Br Br

Ni

H H H

rate of reaction decrease down halogen group F > Cl > Br > I

Addition rxn mechanism

H-Br bond break, 2 e goes to Br

H H Br C H
+

Nucleophile

H Br Br

Br H

2 e in bond form bond with H atom

Carbocation (carbonium ion)

H H H H Br Br

Testing for alkenes

Bromine water (HBr) test for alkene Orange bromine water turn to colourless Major product:
H H H OH Br

+
H

Br Br

H2O

H H H

Br

Minor product:
H H H Br Br

+
H

Br Br

H2O

H H H

Rxns of alkenes with HX

Product monosubstituted haloalkane Rxn of HX with Symmetrical alkenes (ethene) 1 product Asymmetrical alkenes (propene) 2 products Asymmetrical alkene Markovnikovs rule: Major product form has H added to C with greater number of H

Rxns of symmetrical alkenes w HX

H H H H H H Br H H C
+

H Br H
-

H H H H H Br

Rxn of asymmetrical alkene w HX

Br H3C H H H H Br H3C C H
+ -

H H H H3C

Br

H H

Major product

H3C H

H H3C H H Br

H C
+

H H Br
-

H H

H3C H Br

Minor product

Rxn with KMnO4/H+

Addition & oxidation Product alkanediols Purple KMnO4 turn to colourless Can be used to differentiate btwn alkenes & alkanes
H H H H OH OH
KMnO4/dil. H 2SO4

H H H

Polymerisation
Very large molecule made fr monomers (smaller units) Synthesis Addition rxn btwn monomers with C=C or CC Ethene polyethene Propene polypropene Chloroethene polycholoroethene (polyvinylchloride, PVC)

H H

H H

H H

H H

H H

H H

H . H

H .

Polymerisation

LDPE
Highly branched Soft & malleable Low mp

HDPE
Few branched chains Rigid & dense High mp

Properties of polymer
Depend on their monomers, various properties Avg chain length
Tensile strength & mp when length until about 500 units

Branching

Branched chains cannot pack closely low tensile strength, mp & density Strong forces high mp Due to side groups
Hold chains together very rigid, hard, brittle, high mp

Intermolecular forces

Cross links

Polymer problems & solutions

Energy
Fr fossil fuels

Resources
Fossil fuel limited supply, costly

Disposal
Waste problem, toxic gases

Energy to make polymers fr the same source

Need for new resource

Endanger animals

C footprint of plastics
C footprint = a measure of impact fr human activities in terms of CO2 Purpose to try to reduce C footprint as much as possible Source of CO2 burning of fuels, waste plastics Solutions: Use renewable energy Reduce use of polymer products, reuse Recycle reduce diposal & demand to produce new ones Recycle thermoplastics PET carpets, textiles, waterproofing materials

How are plastics recycled?

Mechanical
Melted, shredded, turned into granules Sorting done by hand & expensive

Chemical
aka feedstock recycling Brkdown of waste to monomers burning, thermal cracking, & gasification Expensive use energy

Biodegradable polymers
Development of renewable resources biopolymers, bioplastics, green plastics Modified starch or cellulose (fr plants) Use CO2 during growth reduce C footprint Bacterial fermentation break down plant materials to monomers Broken down by microbes biodegradable Land use to grow plants for polymers decrease land to grow food crops

Energy recovery
Recovering some energy that was used into making polymers Example: burn waste polymer to generate electricity use incinerators at high T to prevent release of dioxin Pyrolysis break down polymer by heat in absence of O2 Syngas gasification involves brkdown of solid HC in limited O2
Product mainly mixture of H2 & CO

Most process are not efficient & expensive

Life cycle analysis

Use by industry quantify effect to environment Product examined fr extraction of raw materials to cost of recycling careful look at energy & material use & emission to environment to improve process & reduce impact to environment compare 2 diff polymers & decide which to be used based on their life cycle

End of alkenes