April 2001

Chem Factsheet
Reactions in organic chemistry

Number 16

Organic Chemistry II - Reactions I

To succeed with this topic you need to Be able to name and draw organic molecules (Factsheet 15) have revisited Factsheet 5 (Bonding) and Factsheet 06 (Structure of elements and compounds) so you understand the bonding and shapes of organic molecules. After working through this Factsheet you will Know the reactions of the families alkanes, alkenes and halogenoalkanes. Know the conditions and reagents for the reactions Understand how the bonding in the compounds influences their reactions Know some of the terms used in reaction mechanisms.
Exam Hint - Unfamiliar compounds are used in questions but the secret is to leam how the family of compounds reacts. You identify the family the unfamiliar compound belongs to, remember how the family reacts and then apply this to the compound. Again, being able to name organic compounds is essential.

Substitution When an atom or group in a molecule is replaced by another atom or group Addition When two molecules react to form a single product.

Reaction Mechanisms
When compounds or elements react then bonds are broken and bonds are formed in the chemical reaction. The reaction mechanism is the method used to show the bond making and breaking processes by explaining what happens to the electrons involved in bonding. N.B. A2 Units require a much more detailed use of reaction mechanisms. Elimination When a simple molecule e.g. HCl, HBr, H2O, is removed from a molecule and not replaced. Hydrolysis - When water reacts with a molecule and the molecule is split into two parts.

Alkanes
First let us revise what we covered in Factsheet number 15 about alkanes. Alkanes are hydrocarbons (made of carbon and hydrogen only). In an homologous series (differ from one another by only CH2). Alkanes have a general formula of CnH2n+2. Alkanes are saturated compounds (Contain only single carbon bonds i.e. CC). Reactions Alkanes are relatively unreactive because of the strength of the C C and C H bonds they contain. The two reactions all alkanes undergo are : 1. Burning in excess oxygen to form carbon dioxide and water e.g. Or C2H6 + 3O2 2CO2 + 3H2O 2C2H6 + 7O2 4CO2 + 6H2O)

Definition of Terms
Term Free Radical Definition A species with a single unpaired electron Example Cl2 Cl + Cl
. .

the . on the Cl represents the unpaired electron

_ +

Nucleophile (literally 'liking the nucleus/ positive charge') Electrophile (literally 'liking electrons/ negative charge')

A donator of a lone pair of electrons (which so forms a new covalent bond) An acceptor of a lone pair of electrons (so forming a new covalent bond) When a bond breaks and one electron goes to each atom (forming free radicals) When a bond breaks and both electrons go to one atom (forming ions)

HO : HO C
+

Reaction type : combustion 2. React with Cl2 or Br2 in the presence of UV light/sunlight to form a complex mix of halogenoalkanes and hydrocarbons. Cl2 + C2H6
UV Light

The C in the example above

C2H5Cl, C2H4Cl2, C2H3Cl3, etc + HCl

Homolytic Fission

x .

Reaction type: substitution Mechanism: free radical

Alkenes
Ax A Ax .
_

+ .B
x .

Unsaturated hydrocarbons (i.e. C=C) with a general formula of CnH2n. The C=C bond is
X

Heterolytic Fisson

B
+

. .

The double bond contains a -bond and a -bond. The bond is strong (the bond pair is in the plane between the two carbon nuclei) But the bond is weaker (the bond pair of electrons lies outside the plane of the nuclei). The -bond will break so other atoms / groups add on to the CC link.

Organic chemistry II - reactions I

Reactions 1. Burning in excess oxygen to form carbon dioxide and water. e.g. C2H4 + 3O2 2CO2 + 2H2O Reaction type: combustion H 2. Alkenes and hydrogen react when mixed over heated nickel catalyst H H C H alkene Reaction type: Condition: Mechanism: Addition Heat + Ni Electrophile H C H
Ni

Chem Factsheet
Markovnikov's Rule
When a hydrogen halide is added to a double bond, the hydrogen always goes to the C atom with the most H atoms on it already. H C H C H C H H + HBr

H H + H2
heat

H C

H C H H H C H Br H C C H H H C H H C Br C H

C H

H H alkane

H H correct

H H wrong

Exam Hint - This is very commonly tested in examinations

3. Alkenes react with bromine / chlorine (halogens) H H C H C H + Br2 H H C H C H

Halogenoalkanes (haloalkanes )
The general formula is CnH2n+1 X, where X = Cl, Br or I. This means the functional group is a halogen atom. All halogenoalkanes react in the same way with the same reagents, but the different halogens do affect the rates of reaction. The difference in the rate is explained by the bond energies shown below: CCl CBr CI 338 kJ mol 1 276 kJ mol 1 238 kJ mol 1

alkene Reaction type: Mechanism: Addition Electrophile

Br Br halogenalkane

A solution of bromine in hexane (or trichloromethene) without heating, decolourises when added to a compound containing a C=C or triple bonds. This is an important test used for dectecting unsaturation. NB. if bromine water (solution of bromine and water) is used, the solution is also decolourised, but a different product is formed. H H C H C H + Br2/H2O H H C H C H + HBr

Cl is a more electronegative atom that bromine which in turn is more electronegative than iodine, so creating dipoles, + C Cl
_

+ C

Br
_

+ C

Br OH 2-bromoethanol

The CCl bond is stronger than CBr, which means more energy is needed to break it so chloroalkanes will react slower than bromoalkanes, i.e. rates of reactions, CI > CBr > CCl

4. Alkenes add hydrogen halides (e.g. HCl, HBr, etc) H H C H alkene Reaction type: Mechanism: Addition Electrophile H C H C H C H H + HCl H H C H H C H C H C H

Reactions
In the following examples X is used for the halogen because Cl, Br and I will all react in the same way. 1. Reaction with aqueous sodium (or potassium) hydroxide to form an alcohol. CH3CH2X + NaOH CH3CH2OH + NaX haloalkane alcohol Reaction type: Conditions: Mechanism: Substitution Aqueous + boil under reflux Nucleophilic

H Cl H halogenoalkane

5. Oxidation by alkaline potassium manganate(VII) solution (KMnO4(aq)) H H H H H H H C H C C H + [O] + H2O H C C C H

2. Reaction with potassium cyanide to form a nitrile (or cyanide). CH3X + haloalkane Reaction type: Conditions: Mechanism: KCN CH3CN + KX cyanide (nitrile)

alkene Addition Alkaline Electrophile

H OH OH alcohol (diol)

Reaction type: Condition: Mechanism:

Substitution KCN in water/ethanol + boil under reflux Nucleophilic

The decolourisation of an alkaline potassium manganate(VII) solution is another test for C=C bonds/unsaturation.

Organic chemistry II - reactions I

3. Reaction with ammonia to form amines. X CH3 CH CH3 + 2NH3 NH 2 CH 3 CH amine Substitution N3 in ethanol + heat Nucleophilic CH3 + NH4X

Chem Factsheet
5. 2bromopropene will react with each of the following: (i) KCN (ii) KOH (aq) (iii) NH 3 For each reaction give the (a) balanced chemical equation (b) reagents and conditions 6. Give the name and structural formula of the organic product in each reaction. NaOH(aq) (a) CH3CHICH3 A (b) CH3 CH2 Br (c) CH 3 CH CH 2
H2 ethanolic KOH HBr

haloalkane Reaction type: Conditions: Mechanism:

4. Reaction with ethanolic potassium hydroxide to form alkenes. H H C H C H + KOH H H C H C H + KX + H2O

B C

H X Reaction type: Conditions:

Elimination KOH in ethanol + boil under reflux

(d) CH2

CH2

Tests for functional groups

Group/Family Alkene C=C Test Shake with bromine water, Br2(aq) Result Colour of bromine solution goes from brown to colourless

Answers
1. (a) UV Light / Sunlight (b) HBr, C3H7Br, C3H6Br2, C3H5Br3, etc (c) Substitution 2. (a) C3H6 + 4O2 3CO2 + 3H2O (or doubled) (b) C8H18 + 12O2 8CO2 + 9H2O (or doubled) (c) C4H10 + 6O2 4CO2 + 5H2O (or doubled) 3. (a) alkane (b) alkene (c) alkene (d) alkane

Chloroalkane C-Cl Bromoalkane C-Br Iodoalkane C-I

1. Warm with NaOH(aq) White precipitate soluble in dil.NH3(aq) 2. Add dilute HNO3 until just acidic 3. Add AgNO3(aq) Cream precipitate soluble in conc. NH3(aq) Yellow precipitate insoluble in conc. NH3(aq)

4. (i) CH3CH2CH=CH2 + HI CH3CH2CHCH3 Condition: goes at room teperature (ii) CH3CH2CH=CH2 + Br2 CH3CH2CHICH2 Condition: Br2 in hexane at room temperature (iii) CH3CH2CH=CH2 + [O] + H2O CH3CH2CHBr-CH2Br Condition: KMnO4 in alkaline soultion (iv) CH3CH2CH=CH2 + H2 CH3CH2CH2CH3 Condition: Heat + Nickel catalyst CN Br 5. (i) CH3-CH-CH3 + KCN CH3-CH-CH3 + KBr Condition: boil KCN dissolved in mixture of water and ethanol OH Br (ii) CH3-CH-CH3 + NaOH CH3-CH-CH3 + NaBr Condition: boil under reflux with NaOH(aq) Br NH 2 (iii) CH3-CH-CH3 + 2NH3 CH3-CH-CH3 + NH4Br Condition: heat concentrated solution of NH3 in ethanol 6. A = B = C = D = CH3CHOHCH3 CH 2=CH2 CH3CHBrCH3 CH 3CH3 Propan-2-ol Ethene 2-bromopropane Ethane

Exam Hint - Candidates will be expected to know the tests for functional /family groups.Thorough knowlege of the reactions outlined in this Factsheet may be expected.

Practice Questions
1. Propane will react with bromine under the correct conditions. (a) What are the conditions used? (b) Give the formula of four compounds likely to be formed by the reactions. (c) What type of reaction is this? 2. Write the balanced chemical equations for the reaction of the following compounds with oxygen. (a) Propane (b) Octane (c) Butane 3. Which family do the following hydrocarbons belong to? (a) C5H12, (b) C10H20 (c) C4H8 (d) C11 H24 4. But1ene reacts with each of the following: (i) HI (ii) Br2 (iii) KMnO4 For each reaction give the (a) Balanced chemical equation (b) reactions and conditions (iv) H2

Acknowledgements: This Factsheet was researched and written by Sam Goodman & Kieron Heath Curriculum Press, Unit 305B, The Big Peg, 120 Vyse Street, Birmingham, B18 6NF ChemistryFactsheets may be copied free of charge by teaching staff or students, provided that their school is a registered subscriber. No part of these Factsheets may be reproduced, stored in a retrieval system, or transmitted, in any other form or by any other means, without the prior permission of the publisher. ISSN 1351-5136