Introductory organic chemistry Homologous series A family of compounds with similar chemical properties due to the presence of the

same functional group but different number CH2 groups. Functional group An atom or group of atoms in a compound which is responsible for most of its reactions. It defines the characteristics of a particular compound.

Picture from AS chemistry module 3 support material (Collins)

Naming 1. In naming compounds the IUPAC (International Union of Pure and Applied Chemistry) rules are followed: a. Name the longest unbranched chain b. Name the substituent groups c. Give the position of the substituent group using the lowest possible number d. If there is more than one substituent group they are placed in alphabetical order e. For more than one of the same functional group use di-, tri-, tetra-. f. For aldehydes, carboxylic acids and nitriles the functional group comes at the end so this is carbon 1. g. Double bonds are numbered before substituent groups h. If there is more than one functional group then carboxylic acid takes priority over carbonyl which takes priority over alcohol. i. For unsaturated compounds use ene before other functional group suffixes.

Isomerism
Isomerism is the existence of different compounds with the same molecular formula but different structural formulae. There are 2 types of isomerism, Structural Isomerism and stereoisomerism, structural isomers have different structural formula stereoisomers have same structural formula but the 3D arrangement of the atoms is different- cis and trans isomers

Chain isomerism 1. The carbon chain is arranged differently, They have the same functional group and so have similar chemical properties but their physical properties will differ. 2. An example is butane and 2-methylpropane. Positional isomerism

1. The functional group is attached to a different carbon atom An example is propan-1-ol and propan-2-ol. Functional group isomerism 1. They contain different functional groups and so are members of different homologous series 2. An example would be an ether methoxymethane and an alcohol ethanol.

Cis-trans isomerism Molecules can rotate freely around the single c- bonds but not around the c-c double bond this leads to stereoisomerism 1. These may differ in physical and chemical properties. 2. The atoms or group of atoms about a double bond are arranged in the same plane. 3. There is no rotation about a double bond since too much energy would be needed to break the bond. 4. Rotation about a single () bond is possible 5. This brings about isomerism since atoms or groups of atoms can be placed on the same or opposite sides of a double bond. 6. An example is cis-butandioic acid and trans-butandioic acid.

7. This type of isomerism can also occur in ring compounds

Alkanes Chlorine/Bromine Type of reaction - homolytic substitution 1. 2. 3. 4. Bonds are broken with each of the bonded atoms taking one electron. This leaves the atoms with unpaired electrons These atoms are known as radicals They have no overall charge since the number of protons and electrons is the same. 5. They are very reactive since the unpaired electron readily pairs up. 6. Energy in the form of heat or ultraviolet light is needed to split the bond. 7. It is most common where the electrons are equally shared i.e. there is little difference in electronegativity. e.g. Cl2 2Cl.

8. The unpaired electron is shown as a dot. 9. A substitution reaction is where an atom or group of atoms in a compound is replaced by another atom or group of atoms. 10. In this case the halogen radical replaces one of the hydrogen atoms in the alkane. Reaction 1. 2. 3. 4. Bromine will react with hexane in the presence of sunlight. In the dark there is no reaction. The reaction taking place in the light is a photochemical reaction. Methane and chlorine will explode in the presence of sunlight.

u.v. CH4(g) + Cl2(g) CH3Cl(g) + HCl(g) H = -98kJ mol-1

5. The reaction can also take place at high temperature.

6. The type of reaction taking place is a free radical substitution reaction. 7. So for alkanes to react with chlorine or bromine energy is needed to first split the halogen molecule. This is usually in the form of ultraviolet light Oxygen 1. Alkanes will react with oxygen or the oxygen in air in a combustion reaction 2. This is the basis of combustion of fuels and is dealt with in more detail later 3. For complete combustion there must be an excess of oxygen 4. The larger the alkane the more oxygen needed for complete combustion 5. The products of complete combustion are carbon dioxide and water vapour 6. with insufficient oxygen combustion is incomplete and the products also include carbon and carbon monoxide 7. The reaction needs to overcome the activation energy and this may involve heating or for gaseous or very volatile alkanes a spark e.g. 2C4H10 + 13O2 8CO2(g) + 10H2O(l)

Alkenes
Structure and bonding 1. Alkenes are an example of a homologous series with the general formula CnH2n. 2. Their functional group is the carbon-carbon double bond >C=C< 3. This bond is described as unsaturated. The double bond 1. Alkenes react readily with bromine 2. However alkenes contain a double bond which would be expected to be stronger than single bonds and so less reactive. 3. The values for bond enthalpy show that it is stronger than a single bond. C C bond in ethane C = C bond in ethene

Bond enthalpy/kJ mol-1 Bond length/nm

346 0.154

598 0.134

4. The table shows that the carbon-carbon double bond is stronger than the single bond but not twice as strong. 5. This suggests that the bonds in the double bond are not identical.

1. The electron configuration of the carbon atom is 1s22s22p2. 2. This means that there are only 2 unpaired electrons. 3. The carbon is able to promote one of its 2s electrons into the 2p subshell. 4. The energy needed to do this is more than compensated for by the bonds that subsequently form. 5. This gives the electron configuration of: 1s22s12p3 6. In an alkene the 2s electron and two of the 2p electrons form three sp2 hybrid orbitals. 7. These orbitals are co-planar at 120o to each other. 8. One of the sp2 hybrid orbitals overlaps with another from an adjacent carbon atom to form a -bond.
6. Overlap of two orbitals between two carbon atoms results in an overlap along the line of the two atoms. 7. This is a -bond. 8. Perpendicular to this bond there is a p orbital on each carbon atom (unhybridised) 9. Overlap between these p orbitals occurs above and below the plane of the -bond, since the p orbitals have two lobes 10. This is called a -bond. 11. The p orbitals have less overlap than in the -bond and so the bond is not as strong. 12. Overall the combined bond is stronger and the nuclei are closer together. 13. The p orbital overlap can only occur when the structure is planar. 14. Overall the >C=C< is planar. 15. This double bond represents a region of electron density. 16. The electrons above and below the plane are open to attract from electrophiles (see later) 17. This means that alkenes are kinetically unstable. 18. The energy needed to break one -bond is more than compensated for in the formation of two new bonds with the addition molecule. 19. This makes alkenes energetically unstable with respect to their products.

20. Look on the e-learning platform for some presentations that show the bonding in alkenes

Alkene reactions
Addition 1. Two substances or molecules react to form one substance 2. Usually involves a double or triple bond Heterolytic fission 1. When a bond breaks both of the shared electrons go to one of the bonding atoms. 2. This then becomes a negatively charged anion 3. The remaining portion is a positively charged cation. 4. This type of fission can occur when the bonds are polar. 5. An ion with a positively charged carbon atom is called a carbocation. 6. An ion with a negatively charged carbon atom is called a carbanion 7. Both are unstable, highly reactive and short lived. Electrophile 1. This is a substance that attracts a region of high electron density. 2. Electrophiles may be cations e.g. NO+2 or the + of a polar molecule e.g. the hydrogen in hydrogen bromide.

Catalytic Hydrogenation 1. Alkenes will react with hydrogen in the presence of a finely divided catalyst at a temperature of about 140oC. 2. This process is also called hydrogenation and is a reduction process. 3. Palladium is a very good catalyst, however due to the cost nickel tends to be used in practice. 4. The process takes place on the catalyst surface. e.g. C2H4(g) + H2(g)
Ni

C2H6(g)

140oC

5. This process can be used as a measure of the degree of unsaturation in a compound by noting the number of moles of hydrogen used in the process. 6. Hydrogenation is used in industry in the manufacture of margarine. 7. Vegetable oils are the esters of long chained unsaturated carboxylic acids. 8. They are known as polyunsaturated due to the presence of a number of double bonds per molecule. 9. By hydrogenation the molecules become saturated and this increases their melting point making them solid at room temperature. 10. The degree of saturation will determine the hardness of the fat. 11. Some unsaturation is left since it is believed that unsaturated fats are healthier.

Bromine water 1. Alkenes can be identified by their reaction with bromine water. 2. Alkenes readily decolourise red/brown bromine water. 3. Alkanes would decolourise bromine water in the light however the reaction would take time. 4. The use of bromine water is safer than using bromine. e.g. CH2=CH2(g) + Br2(aq) + H2O(l) CH2BrCH2OH(aq)
2-bromoethanol (colourless)

brown

HBr(aq)

Bromine 1. Alkenes react readily with bromine decolourising it.

CH2=CH2(g) +

Br2(l)

CH2BrCH2Br(l)

1,2-dibromoethane

2. The mechanism for the reaction is one of electrophilic addition. Hydrogen bromide

1. Alkenes react readily with hydrogen bromide (and other hydrogen halides) to form the bromoalkane. e.g. CH2=CH2(g) + HBr(g) CH3CH2Br(g)
Bromoethane

Unsymmetrical alkenes

1. With unsymmetrical alkenes such as propene there are two possible products with hydrogen bromide CH3CHCH2 + HBr CH3CH2CH2Br
1-bromopropane

4%

or

CH3CHBrCH3

96%

2-bromopropane

2. The 2-bromopropane forms the major product with a small amount of 1bromopropane being produced. 3. The product formed can be determined using Markovnikovs Rule (Vladimir a Russian, spelling with ff also) When a compound HX adds to an unsaturated compound the hydrogen will become attached to the carbon atom that already has the most hydrogen atoms.

Potassium manganate (VII) 1. Alkaline potassium manganate (VII) is a weak oxidising agent 2. When mixed with an alkene e.g. bubble through ethene the purple colour of the potassium manganate (VII) is lost as ethene is oxidised to ethane-1,2-diol
H C H C H HO OH H

KMnO4, OH-

CH2

CH2

ethene

3. A diol is a compound with two hydroxyl groups

4. 5. 6. 7. 8.

This reaction is an example of addition and oxidation A brown suspension may be left of manganese (IV) oxide This reaction can be used as a test for alkenes Acidified potassium manganate (VII) will also react in the same way Ethane-1,2-diol is used as antifreeze in cars

Halogeno-compounds (Haloalkanes)
Terms: Elimination 1. The removal of a smaller molecule from a larger one. 2. Often results in the formation of a double bond. Nucleophile 1. These are species attracted to positive areas i.e. electron deficient. 2. They may be negative ions containing a lone pair of electrons or the - end of a molecule with alone pair of electrons.

Nucleophilic substitution 1. Haloalkanes are a homologous series with the functional group -C X where X is F, Cl, Br, or I. 2. The electronegativities of the halogens are F 4.0, Cl 3.0, Br 2.8 and I 2.5. 3. The electronegativity of carbon is 2.5 4. This makes the carbon halogen bond polar (except iodine) 5. The amount of polarity decreases down the group. 6. The polarity in the fluoro and chloro alkanes is high enough such that their boiling points are higher than those alkanes with equivalent masses. 7. However their polarity is not high enough to make them appreciably soluble in water. 8. The + charge on the carbon atom leaves it open to attack from nucleophiles such as CN-, OH- and NH3 with its lone pair of electrons. 9. The halide ion makes a stable leaving group. 10. Nucleophilic substitution involves heterolytic fission. 11. The rate or ease of reaction depends on two factors:

a. The strength of the C X bond b. The stability of the X- leaving group Bond strength 1. The following shows the strength of the C X bonds C F 485kJ mol-1 C Cl 338kJ mol-1 C Br 276kJ mol-1 C I 238kJ mol-1 2. Since the C I bond is weaker it breaks more easily and so the reaction is faster.

Stability of leaving group 1. In terms of stability F->Cl->Br->IThe above factors are in opposition. However bond strength is the determining factor and so reactivity increases from the fluoro alkanes to the iodo alkanes. In fact fluoro alkanes are considered as unreactive.

Cyanide ion 1. The haloalkane is heated under reflux with a solution of potassium cyanide in ethanol. 2. The product formed is a nitrile. e.g. CH3CH2Br + CN CH3CH2CN

Bromoethane

propanenitrile

3. This reaction is important since it brings about an increase in the carbon chain length. 4. The resulting nitrile can be hydrolysed by heating under reflux with either acid or alkali. 5. The product is a carboxylic acid. e.g.

H+

CH3CH2CN(l)

CH3CH2CONH2(aq)

H 2O

CH3CH2COOH(aq)

NH+

Or
NaOH H 2O

CH3CH2CN(l)

CH3CH2CONH2(aq)

CH3CH2COO-(aq)

NH3

Ammonia 1. Ammonia has a lone pair of electrons and so can act as a nucleophile. 2. Ammonia is heated with the haloalkane in a sealed container (bomb). e.g.

CH3CH2Br(l) +

NH3(g)

C2H5NH2

HBr

Ethylamine (Primary amine)

3. The nitrogen atom in ethylamine has a lone pair of electrons and so can act as a nucleophile. 4. Therefore with an excess of the haloalkane the reaction continues. e.g. CH3CH2Br + C2H5NH2 C2H5NHC2H5 + HBr

Diethylamine (Secondary amine)

5. The substitution reaction can continue e.g. CH3CH2Br + C2H5NHC2H5 (C2H5)3N + HBr

Triethylamine (Tertiary amine)

6. A final substitution is possible e.g.

CH3CH2Br

(C2H5)3N

(C2H5)4N+Br-

Tetraethylammonium bromide (Quaternary ammonium salt)

7. In practice a mixture of all four compounds is obtained. 8. The further substitution reactions can be minimised by the use of an excess of ammonia in the bomb.

Hydroxide 1. The process can be carried out by heating the haloalkane under reflux with aqueous sodium hydroxide solution. e.g. CH3CH2Br + OH C2H5OH + Br-

Elimination 1. The hydroxide ion is able to undergo substitution reactions with the haloalkane to form an alcohol. 2. The hydroxide ion can also act as a base by accepting a proton from the haloalkane. 3. The halide ion is then expelled and an alkene is formed.

e.g. CH3CH2Br + OH CH2 = CH2 + H 2O + Br-

4. This reaction is known as elimination 5. The two reactions of elimination and substitution are in competition with each other. 6. Elimination is favoured by a stronger base. 7. The reaction conditions can then be altered to provide the base in a nonaqueous solvent e.g. potassium hydroxide in ethanol, this favours elimination. 8. The temperature also affects the type of reaction. 9. The higher the temperature the more likely elimination is to occur. 10. A tertiary haloalkane is more likely to undergo elimination than a primary haloalkane. 11. A secondary haloalkane is likely to produce a mixture of products so the conditions are important. 12. By using a base in hot ethanol as opposed to warm aqueous we favour elimination.

Testing for halogeno-alkanes 1. You have learnt that the alkaline hydrolysis of a halogeno-alkanes will yield an alcohol and the halide ion 2. The halide ion can then be identified and so the original halogeno-alkane 3. First the halogeno-alkane is heated with aqueous sodium hydroxide solution 4. It is cooled and neutralised with hydrochloric acid 5. Silver nitrate solution is then added 6. A white precipitate would indicate a chloroalkane, a pale yellow precipitate would indicate a bromoalkane and a yellow precipitate would indicate an iodoalkane 7. If needs be ammonia solution could also be used on the precipitate Silver chloride is soluble in dilute and concentrated ammonia solution Silver bromide is insoluble in dilute ammonia (sparingly soluble) solution but soluble in concentrated ammonia solution Silver iodide is insoluble in dilute and concentrated ammonia solution e.g. RCl + OH ROH + Cl-

Ag+

Cl-

AgCl(s)

Alcohols
1. Aliphatic (straight chained) alcohols form a homologous series with the functional group OH 2. They have the general formula CnH2n+1OH 3. Alcohols can be classified as primary, secondary or tertiary depending on the number of alkyl groups attached to the carbon atom with the OH group. 4. A primary alcohol is RCH2OH e.g. butan-1-ol CH3CH2CH2CH2OH

A secondary alcohol is
R

CH

OH H3C

CH2 CH

CH3

e.g.
R OH butan-2-ol

5. A tertiary alcohol is

R CH3 R C OH H3C R C OH

e.g.
CH3 2-methylpropan-2-ol

Oxidation 1. Acidified potassium dichromate (VI) is an oxidising agent. 2. It is able to oxidise a primary alcohol to an aldehyde (carbonyl compound) 3. On warming further oxidation will take place and the aldehyde is oxidised to a carboxylic acid. 4. If the aldehyde only is wanted it can be distilled off. 5. If the carboxylic acid is wanted then the mixture should be heated under reflux. 6. Equations using these oxidising agents are quite complex and can be represented as [O]. 7. However the equation must still balance.

e.g. C2H5OH Then + [O] CH3CHO

Ethanal

H2

CH3CHO

[O]

CH3COOH

Ethanoic acid

8. Secondary alcohols are oxidised to ketones only. 9. Ketones are also carbonyl compounds

e.g. (CH3)2CHOH + [O] (CH3)2C=O + H 2O

10. Tertiary alcohols are not readily oxidised 11. However powerful oxidising agents would give a mixture of products. 12. During these oxidation reactions the potassium dichromate (VI) changes from orange to green as it is reduced to chromium (III) 13. This can be used to distinguish primary and secondary alcohols from tertiary alcohols. 14. Acidified potassium manganate (VII) is a strong oxidising agent and would change a primary alcohol straight to an acid.

Concentrated sulphuric acid 1. Heating an alcohol at 170oC with an excess of sulphuric acid results in the formation of an alkene. 2. This is of OH and a proton from an adjacent carbon atom (in effect water) e.g. C2H5OH
conc. H2SO4

170 C
o

C2H4 +

H 2O

3. This dehydrating reaction is an elimination reaction

Halogenation 1. Alcohols can be converted into halogeno-compounds using a number of different halogenating reagents Phosphorus (V) chloride (phosphorus pentachloride) 1. This will react in the cold with alcohols

e.g. C2H5OH(l)

PCl5(l)

C2H5Cl(l) + Chloroethane

POCl3(l) + phosphorus trichloride oxide

HCl(g)

2. This formation of hydrogen chloride (seen as steamy white fumes), which will turn damp blue litmus paper red, is used as a test for the presence of the hydroxyl group in a compound Sodium bromide and concentrated sulphuric acid 1. The sodium bromide and concentrated sulphuric acid act as a source of hydrogen bromide 2. The reaction mixture is distilled to produced the bromo-alkane e.g. C2H5OH(l)

HBr9g)

C2H5Br(l)

H2O(l)

Phosphorus and iodine 1. Red phosphorus and iodine act as a source of hydrogen iodide. 2. Concentrated sulphuric acid would oxidise the hydrogen iodide to iodine 3. The reaction mixture is distilled e.g. C2H5OH(l) + HI(g) C2H5I(l) + H2O(l)

Empirical and molecular formulae

Empirical Formula 1. This gives the relative number of the atoms of each element in a compound. 2. It is the simplest ratio of each type of atom in a compound.

3. 4. 5. 6.

It can be calculated from percentage composition and Ar of the elements Divide the percentage composition by the Ar Divide this answer by the smallest number. Multiply, if necessary, by a whole number to get the empirical formula.

Molecular Formula 1. 2. 3. 4. 5. 6. This shows the actual number of atoms of the elements in a compound. It is a multiple of the empirical formula. The Mr of the compound is needed. Find the Mr of the empirical formula. Divide the Mr of the compound by this value to give a whole number n Multiply the empirical formula by n.

Reacting masses 1. An equation gives us what is reacting and the amounts of the substances that are reacting. 2. We can use it to calculate the amount of product produced from the amount reacted and vice versa. 3. Amounts are converted in to moles.

Addition polymers
1. Due to the double bonds alkenes, under the right conditions, can be made to add to themselves. 2. The alkene molecules are the monomer which join to form the polymer. 3. Therefore it is known as addition polymerisation e.g. 2n CH2 = CH2 (-CH2 - CH2 - CH2 - CH2 -)n

Where n is a large number 4. Ethene was the first alkene to be polymerises by ICI in 1933, forming polythene.

5. Under high temperature, high pressure and a trace of oxygen low density polythene is formed. 6. This polythene has branching so the molecules dont pack close together. 7. It has a low melting point around 105oC. 8. It is used to make plastic bags and squeezy bottles. 9. Under a lower temperature and pressure and in the presence of a catalyst high density polythene is formed. 10. The molecules are branched and so are able to pack closer together. 11. It has a higher melting point and can be used to make buckets, bowls e.t.c. 12. The same principle can be applied to other alkenes e.g. propene forms polypropene. 13. The addition polymerisation occurs by a free radical mechanism 14. Propene also forms a polymer in the same way as polyethene 15. It finds use in plastic pipes and crates, it can also be made into fibres to make carpets and ropes

CH3

CH3

CH3 CH H CH CH H

HC

CH H

n n

HC

16. Chloroethene is ethene with a chlorine atom attached to it 17. With the double bond it can polymerise to form polychloroethane 18. This is used to make drainpipes and other pipe work and waterproofs

Cl H C C H HC Cl CH H HC CH H

2
Cl

n n

19. Tetrafluoroethene contains 4 fluorine atoms per ethene molecule

20. It can polymerise to form polytetrafluoroethane which is used as a nonstick coating on pans etc known as PTFE
F F F F

2
F

n
F

n
F F F F

Environmental
1. Herbicides often contain halogens such as chlorine e.g. DDT 2. The carbon halogen bond is a strong bond and as such it results in the long life of the product 3. Whilst this may be useful in terms of the pesticide remains around long enough to be able to do its job it also means that it can remain in the environment for a long time and become incorporated into the food chain 4. The same is true with some plastics that may also contain halogens but are stable in their nature since they are effectively alkanes 5. This means that they will persist in the environment for a long time