ALKANES

o GENERAL FORMULA: CnH2n+2 o ISOMERISM: All alkanes with 4 or more carbons show structural isomerism o CYCLO-ALKANES: lose two hydrogens

o BOILING POINTS: increase as chain lengths increase due to more Van der Waals dispersion forces holding the molecules together, needing more energy to break. With isomers, the more branched the chain, the lower the boiling point is: Van der Waals dispersion forces are smaller for shorter molecules, and only operate over very short distances between one molecule and its neighbours. o SOLUBILITY: Alkanes are insoluble in water (too much energy needed to break H-bonds in water), but dissolve in organic solvents (only breaking + forming new Van der Waals attractions). o

REACTIONS OF ALKANES:
REACTION WITH OXYGEN (COMBUSTION) Complete combustion (given sufficient oxygen) of any hydrocarbon burns with a blue flame and produces carbon dioxide and water. The hydrocarbons become harder to ignite as the molecules get bigger: bigger molecules have greater Van der Waals attractions which makes it more difficult for them to break away from their neighbours and turn to a gas. REACTION WITH HALOGENS (HALOGENATION) These are photochemical reactions, i.e. take place in the presence of (UV) light, and happen at room temperature. Free radical substitution reactions happen in which hydrogen atoms in the methane are replaced one at a time by chlorine atoms. The original mixture of a colourless and a green gas would produce steamy fumes of hydrogen chloride and a mist of organic liquids

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CRACKING Cracking is the name given to breaking up large hydrocarbon molecules into smaller and more useful bits such as alkenes. This is achieved by using high pressures and temperatures without a catalyst, or lower temperatures and pressures in the presence of a catalyst.

ALKENES
o GENERAL FORMULA: CnH2n o ISOMERISM: All alkenes with 4 or more carbons show structural isomerism: e.g. C4H8.

But, but-2-ene also has geometrical isomerism.

o BOILING POINTS: increase as chain lengths increase due to more Van der Waals dispersion forces holding the molecules together, needing more energy to break. o SOLUBILITY: Alkenes are also insoluble in water (non-polar and too much energy needed to break H-bonds in water), but dissolve in organic solvents (only breaking + forming new Van der Waals attractions). o

REACTIONS OF ALKENES:
The important reactions all centre around the double bond. Typically, the pi bond breaks and the electrons from it are used to join the two carbon atoms to other things. Alkenes undergo addition reactions. The pi bond is open to attack from electrophiles. REACTION WITH HYDROGEN Electrophilic addition Hydrogen adds to an alkene in the presence of a nickel catalyst (heterogeneous) at 150oC and high pressure.

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Hydrogenation can be used to make margarine.

REACTION WITH HALOGENS These are addition reactions. For example, bromine adds to give 1,2-dibromoethane. The reddish-brown bromine is decolourised as it reacts with the alkene.

Room temperature. Reaction speed: Cl2 > Br2 > I2. If you shake an alkene with bromine water (or bubble a gaseous alkene through bromine water), the solution becomes colourless. Alkenes decolourise bromine water.

REACTION WITH HYDROGEN HALIDES All alkenes undergo addition reactions with the hydrogen halides. Symmetrical alkenes: o A hydrogen atom joins to one of the carbon atoms originally in the double bond, and a halogen atom to the other. o e.g. o Conditions are room temperature o Reaction rates increase in the order HF - HCl - HBr - HI. The bond strength falls as you go from HF to HI, and the hydrogen-fluorine bond is particularly strong. o Reaction rates increase as the number of alkyl groups to increases on carbons at either end of the double bond. o This is because alkyl groups push electrons towards the double bond i.e. the pi bond, which attracts others more. Unsymmetrical alkenes: o There is no difference in terms of reaction conditions and factors affecting rate of reaction. o If HCl adds to an unsymmetrical alkene there are several possible ways it could add. But usually, there is only one major product. o Markovnikovs rule states that: When a compound HX is added to an unsymmetrical alkene, the hydrogen Do not quote in becomes attached to the carbon with the most exam hydrogens attached to it already. REACTION WITH POTASSIUM MANGANATE (VII) This is a hydroxylation reaction. Reaction occurs at room temperature. The product is ethan-1,2-diol. If the potassium manganate(VII) solution is acidified with dilute sulphuric acid, the purple solution becomes colourless.

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If the potassium manganate(VII) solution is made alkaline the purple solution first becomes dark green and then produces a dark brown precipitate. Manganate(VII) ions are a strong oxidising agent.

REACTION WITH conc. SULPHURIC ACID + WATER This is a hydrolysis reaction. Ethene is passed into concentrated sulphuric acid (170 C) to make ethyl hydrogensulphate, which is then passed through water. The water reacts with the ethyl hydrogensulphate to produce ethanol, which distils off.

HALOGENOALKANES
o GENERAL FORMULA: R-X where X is a halogen. o DIFFERENT TYPES: Halogenoalkanes fall into different classes depending on how the halogen atom is positioned on the chain of carbon atoms In a primary (1) halogenoalkane, the carbon with the halogen is only attached to one other alkyl group.

In a secondary (2) halogenoalkane, the carbon with the halogen attached is joined directly to two other alkyl groups

In a tertiary (3) halogenoalkane, the carbon atom holding the halogen is attached directly to three alkyl groups

o BOILING POINTS: The increase in boiling point as you go from a chloride to a bromide to an iodide (for a fixed number of carbon atoms) is because of the increase in number of electrons leading to larger dispersion forces (van der Waals). o SOLUBILITY: Not very soluble in water (too much energy required). Soluble in organic solvents. o REACTIVITY: The carbon-halogen bond has got to be broken. That gets easier as you go from fluoride to chloride to bromide to iodide, the compounds get more reactive in that order. o

REACTIONS OF HALOGENOALKANES:
REACTION WITH AQUEOUS KOH Nucleophilic substitution (hydrolysis) Product is an alcohol. Conditions: Heat under reflux in aqueous solution

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REACTION WITH ALCOHOLIC KOH Elimination Product is an alkene. Conditions: Heat under reflux with ethanol as a solvent

CH3CH2Br CH2CH2 + HBr

REACTION WITH ALCOHOLIC KCN Nucleophilic substitution. If a halogenoalkane is heated under reflux with a solution of potassium cyanide in ethanol, a -CN group replaces the halogen and a nitrile is produced.

This is an important reaction as it adds a carbon to the chain.

REACTION WITH EXCESS AMMONIA Nucleophilic substitution. The halogenoalkane is heated with a concentrated solution of ammonia in ethanol. The reaction is carried out in a sealed tube at high temperature and pressure. You couldn't heat this mixture under reflux, because the ammonia would simply escape up the condenser as a gas. Product is an amine. IDENTIFYING HALIDE GROUPS The halogenoalkane is warmed with sodium hydroxide solution in a mixture of ethanol (solvent) and water.

Acid is used to remove unwanted ions such as the OH-. The test is performed as described on page 22 of module 1

ALCOHOLS
o GENERAL FORMULA: R-OH where OH is a hydroxyl group. o DIFFERENT TYPES: Alcohols follow the same pattern as halogenoalkanes i.e. primary, secondary and tertiary. o BOILING POINT: Boiling point of alcohol is higher than alkane with same number of carbons. This is caused by hydrogen bonding between the slightly positive hydrogen atoms and lone pairs on oxygens in other molecules. Boiling point of alcohols increase as the number of carbons increases. This is

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because as molecules get larger, there are more electrons, hence greater dispersion forces (van der Waals forces) o SOLUBILITY: Small alcohols are soluble. As size increases, they become less soluble. o

REACTIONS OF ALCOHOLS:
REACTION WITH ACIDIFIED POTASSIUM DICHROMATE (VI) These are oxidation reactions. Potassium dichromate (VI) solution is acidified with sulphuric acid. It produces a colour change from orange to blue-green to show that the primary and secondary alcohols have undergone oxidation reactions. FOR PRIMARY ALCOHOLS: Conditions: dilute sulphuric acid and dichromate. Heat and distil.

C2H5OH + [O] CH3CHO + H2O

ALDEHYDE
Conditions: conc. sulphuric acid and dichromate. Heat under reflux.

C2H5OH + 2[O] CH3COOH + H2O

CARBOXYLIC ACID

FOR SECONDARY ALCOHOLS: Conditions: conc. sulphuric acid and dichromate. Heat under reflux. CH3CH(OH)CH3+[O]CH3COCH3+H2O

KETONE
FOR TERTIARY ALCOHOLS: o No reaction REACTION WITH DEHYDRATING AGENTS If ethanol vapour is passed over heated (300 C) aluminium oxide powder catalyst, the ethanol is cracked to give ethene and water vapour.

Ethanol is heated with an excess of concentrated sulphuric acid or concentrated phosphoric (V) acid (H3PO4) at a temperature of 170C. The gases produced are passed through sodium hydroxide solution to remove the carbon dioxide and sulphur dioxide produced from side reactions.

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REACTION WITH HALOGENATING AGENTS WITH PCl5 Phosphorus pentachloride at room temperature produces white steamy fumes of HCl. This is a test for the hydroxyl group. C2H5OH + PCl5 C2H5Cl + POCl3 + HCl

WITH HYDROGEN HALIDES HBr is made in situ from KBr and H2SO4 forms bromoalkanes during heating under reflux. NaBr can also be used instead of the HBr. KBR + H2SO4 HBr + KHSO4. C2H5OH + HBr C2H5Br + H2O With iodine: Iodoalkanes can be made in a reaction phosporus triiodide made in situ from iodine and red phosporus. 2P + 3I2 2PI3 3C2H5OH + PI3 ---> 3C2H5I +H3PO3 The relative reactivities of alcohols in halogenation are tertiary > secondary > primary alcohol.

Single and double bonds: o An alkene is much more reactive than an alkane because it has a double bond. A double bond is weaker that a single bond. o A single bond consists of 1 sigma bond. A double bond consists of a sigma and a pi bond. The pi bond is weaker because it is less under the control of the nuclei involved; hence the pi electrons are more easily accessible i.e. they are open to attack from an electrophile. o In a reaction, alkanes need to break sigma bonds, while alkenes only a pi bond. Hence, this requires less energy and therefore alkenes are more reactive. Bond polarity and enthalpy: o Some bonds like carbon-halogen are polar because there is a difference in E.N. values. This leaves the carbon slightly positive ( +) and open to nucleophilic attack. o A C-I bond is weaker than a C-Cl bond because it is longer due to the size of the halogen atom. Therefore an iodoalkane will react much faster.

Different types of formulae: o Empirical formula: formula which shows the simplest whole number ratio of elements in one molecule

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o Molecular formula: formula which shows the actual number of each element in one molecule o Structural formula: formula, which shows how individual atoms are bonded within the molecule. Theoretical yield + percentage yield: o The percentage yield is always lower than 100% because of side reactions and handling losses such as purification. o The theoretical yield is calculated using the balanced chemical equation. o Percentage yield = 100*actual yield/theoretical yield

Fuels: o Liquid fuels have the advantage of having higher densities than gaseous fuels. More energy may be stored in a liquid fuel than in the same volume of gaseous fuel. o It is easier and safer to pipe liquid fuels than gaseous fuels o The pollution of each fuel must be taken into account. o Example of some fuels and their advantages: Energy Energy Fuel State per per Handling Environment volume mass Hard to contain and pressure is needed to transfer it as a Only very liquid. Can lead to explosive hydrogen gas very low produces high risk. Expensive because must water come from electrolysis of water. methane gas very low high same as hydrogen Forms CO2 and H2O Forms CO2 and H2O Same as above but often produces CO. Can be made from sugar cane (renewable)

butane

liquid moderate (pressure)

high

easy to liquefy and use easy to handle. Easily ignited (i.e. volatile). Larger chains mean larger calorific value). easy to handle

octane

liquid

high

high

ethanol

liquid

moderate moderate

Polymers of simple alkenes: o All these reactions are addition polymerisations

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o An addition reaction is one in which two or more molecules join together to give a single product. During polymerisation of monomers, thousands of these join together to make polymers. Monomer Polymer Properties In LDPE, chains are arranged randomly, so vdW forces are less effective leading to a lower boiling point. This also makes it soft and flexible. Has many lengths of chainsno sharp melting point. In HDPE, chains are arranged less randomly so it is stronger and has a higher melting point +density PP, Resists tension and is tougher than polyethene, Water repellent, Low melting point and density PVC, is hard (because of dipoledipole attractions due to polarity of CCl bond. It is less flexible than polyethene. It is an electrical insulator. PTFE has a high melting point and resists chemical attack (does not corrode) because of strong C-F bond. It is also low-friction and non-stick. Uses Plastic bags, bottles, Flexible sheet material, Pipes, Washing up bowls Ropes, Carpets, Curtains, Crates Guttering Floor tiles, Packaging, Electrical wires, Clothing Cooking+ Garden utensils, Frying pans

Ethene CH2=CH2

Polyethene

Propene CH3CH=CH2

Chloroethene CHCl=CH2

Tetrafluoroethene CF2=CF2

Polymers and compounds of simple alkenes: o Polymers are not biodegradable because of strong C-Halogen bonds. Toxic gases are given off during combustion o DDT is a pesticide used to kill mosquitoes. The strong C-Cl bonds give DDT a long life, however it persists in the environment and builds up in the food chain threatening creatures at the top of the chain (bio-accumulation) o Can be used as refrigerants: CFC. It does not decompose quickly when discarded but does so in the upper atmosphere. The radicals it forms react with ozone. This increases UV radiation reaching the Earth's surface and a increases risks of skin cancers.

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