AN INTRODUCTION TO THE CHEMISTRY OF ALCOHOLS

AN INTRODUCTION TO THE CHEMISTRY OF ALCOHOLS KNOCKHARDY PUBLISHING

KNOCKHARDY PUBLISHING THE CHEMISTRY OF ALCOHOLS INTRODUCTION This Powerpoint show is one of several produced to help students understand selected topics at AS and A2 level Chemistry. It is based on the requirements of the AQA and OCR specifications but is suitable for other examination boards. Individual students may use the material at home for revision purposes or it may be used for classroom teaching if an interactive white board is available. Accompanying notes on this, and the full range of AS and A2 topics, are available from the KNOCKHARDY SCIENCE WEBSITE at... www.knockhardy.org.uk/sci.htm Navigation is achieved by... either clicking on the grey arrows at the foot of each page or using the left and right arrow keys on the keyboard

CLASSIFICATION OF ALCOHOLS Aliphatic• general formula CnH2n+1OH - provided there are no rings • the OH replaces an H in a basic hydrocarbon skeleton

CLASSIFICATION OF ALCOHOLS Aliphatic• general formula CnH2n+1OH - provided there are no rings • the OH replaces an H in a basic hydrocarbon skeleton Aromatic • in aromatic alcohols (or phenols) the OH is attached directly to the ring • an OH on a side chain of a ring behaves as a typical aliphatic alcohol The first two compounds are classified as aromatic alcohols (phenols) because the OH group is attached directly to the ring.

CLASSIFICATION OF ALCOHOLS Aliphatic• general formula CnH2n+1OH - provided there are no rings • the OH replaces an H in a basic hydrocarbon skeleton Aromatic • in or phenols, the OH is attached directly to the ring • an OH on a side chain of a ring behaves as a typical aliphatic alcohol The first two compounds are classified as phenols because the OH group is attached directly to the ring. Structural differences • alcohols are classified according to the environment of the OH group • chemical behaviour, eg oxidation, often depends on the structural type PRIMARY 1° SECONDARY 2° TERTIARY 3°

THE CHEMISTRY OF ALCOHOLS • CONTENTS • Structure of alcohols • Nomenclature • Isomerism • Physical properties • Chemical properties of alcohols • Identification using infra-red spectroscopy • Industrial preparation and uses of ethanol • Revision check list

SOLVENT PROPERTIES OF ALCOHOLS SolubilityLow molecular mass alcohols are miscible with water Due to hydrogen bonding between the two molecules Heavier alcohols are less miscible Solvent propertiesAlcohols are themselves very good solvents They dissolve a large number of organic molecules

BOILING POINTS OF ALCOHOLS Increases with molecular size due to increased van der Waals’ forces. Alcohols have higher boiling points than similar molecular mass alkanes This is due to the added presence of inter-molecular hydrogen bonding. More energy is required to separate the molecules. Mr bp / °C propane C3H8 44 -42 just van der Waals’ forces ethanol C2H5OH 46 +78 van der Waals’ forces+ hydrogen bonding

BOILING POINTS OF ALCOHOLS Increases with molecular size due to increased van der Waals’ forces. Alcohols have higher boiling points than similar molecular mass alkanes This is due to the added presence of inter-molecular hydrogen bonding. More energy is required to separate the molecules. Mr bp / °C propane C3H8 44 -42 just van der Waals’ forces ethanol C2H5OH 46 +78 van der Waals’ forces+ hydrogen bonding Boiling point is higher for “straight” chain isomers. bp / °C butan-1-ol CH3CH2CH2CH2OH 118 butan-2-ol CH3CH2CH(OH)CH3 100 2-methylpropan-2-ol (CH3)3COH 83 Greater branching = lower inter-molecular forces

INDUSTRIAL PREPARATION OF ALCOHOLS FERMENTATION Reagent(s) GLUCOSE - produced by the hydrolysis of starch Conditions yeast warm, but no higher than 37°C EquationC6H12O6 ——> 2 C2H5OH + 2 CO2 Advantages LOW ENERGY PROCESS USES RENEWABLE RESOURCES - PLANT MATERIAL SIMPLE EQUIPMENT Disadvantages SLOW PRODUCES IMPURE ETHANOL BATCH PROCESS

INDUSTRIAL PREPARATION OF ALCOHOLS HYDRATION OF ETHENE Reagent(s) ETHENE - from cracking of fractions from distilled crude oil Conditions catalyst - phosphoric acid high temperature and pressure EquationC2H4+ H2O ——> C2H5OH

INDUSTRIAL PREPARATION OF ALCOHOLS HYDRATION OF ETHENE Reagent(s) ETHENE - from cracking of fractions from distilled crude oil Conditions catalyst - phosphoric acid high temperature and pressure Equation C2H4 + H2O ——> C2H5OH Advantages FAST PURE ETHANOL PRODUCED CONTINUOUS PROCESS Disadvantages HIGH ENERGY PROCESS EXPENSIVE PLANT REQUIRED USES NON-RENEWABLE FOSSIL FUELS TO MAKE ETHENE Uses of ethanol ALCOHOLIC DRINKS SOLVENT - industrial alcohol / methylated spirits FUEL - petrol substitute in countries with limited oil reserves

USES OF ALCOHOLS ETHANOL DRINKS SOLVENT industrial alcohol / methylated spirits (methanol is added) FUEL used as a petrol substitute in countries with limited oil reserves METHANOL PETROL ADDITIVE improves combustion properties of unleaded petrol SOLVENT RAW MATERIAL used as a feedstock for important industrial processes FUEL Health warning Methanol is highly toxic

STRUCTURAL ISOMERISM IN ALCOHOLS Different structures are possible due to... A Different positions for the OH group and B Branching of the carbon chain butan-1-ol butan-2-ol 2-methylpropan-2-ol 2-methylpropan-1-ol

NAMING ALCOHOLS Alcohols are named according to standard IUPAC rules • select the longest chain of C atoms containing the O-H group; • remove the e and add ol after the basic name • number the chain starting from the end nearer the O-H group • the number is placed after the an and before the ol ... e.g butan-2-ol • as in alkanes, prefix with alkyl substituents • side chain positions are based on the number allocated to the O-H group e.g. CH3 - CH(CH3) - CH2 - CH2 - CH(OH) - CH3 is called 5-methylhexan-2-ol

THE CHEMISTRY OF ALCOHOLS • Before you start it would be helpful to… • BE AWAKE!!!!!!!

REACTIONS INVOLVING BREAKING THE O-H BOND 1. SODIUM . Conditionsroom temperature Product sodium alkoxide and hydrogen Equation2CH3CH2OH(l) + 2Na(s) ——> 2CH3CH2O¯ Na + + H2(g) sodium ethoxide Notes alcohols are organic chemistry’s equivalent of water water reacts with sodium to produce hydrogen and so do alcohols the reaction is slower with alcohols than with water. Alkoxides are white, ionic crystalline solids e.g. CH3CH2O¯ Na+

2. ESTERIFICATION OF ALCOHOLS Reagent(s) carboxylic acid + strong acid catalyst (e.g conc. H2SO4 ) Conditions reflux Product ester Equatione.g. CH3CH2OH(l) + CH3COOH(l) CH3COOC2H5(l) + H2O(l) ethanol ethanoic acid ethyl ethanoate NotesConcentratedH2SO4 is a dehydrating agent - it removes water causing the equilibrium to move to the right and increases the yield

ESTERIFICATION OF ALCOHOLS Reagent(s) carboxylic acid + strong acid catalyst (e.g conc. H2SO4 ) Conditions reflux Product ester Equation e.g. CH3CH2OH(l) + CH3COOH(l) CH3COOC2H5(l) + H2O(l) ethanol ethanoic acid ethyl ethanoate Notes Concentrated H2SO4 is a dehydrating agent - it removes water causing the equilibrium to move to the right and increases the yield Uses of esters Esters are fairly unreactive but that doesn’t make them useless Used as flavourings Naming esters Named from the alcohol and carboxylic acid which made them... CH3OH + CH3COOHCH3COOCH3+ H2O fromethanoic acidCH3COOCH3from methanol METHYLETHANOATE

3. BROMINATION OF ALCOHOLS Reagent(s)sodium (or potassium) bromide and concentrated sulphuric acid Conditions reflux Product haloalkane EquationC2H5OH(l) + conc. HBr(aq) ———> C2H5Br(l) + H2O(l) Mechanism The mechanism starts off similar to that involving dehydration (protonation of the alcohol and loss of water) but the carbocation (carbonium ion) is attacked by a nucleophilic bromide ion in step 3 Step 1 protonation of the alcohol using a lone pair on oxygen Step 2 loss of a water molecule to generate a carbocation (carbonium ion) Step 3 a bromide ion behaves as a nucleophile and attacks the carbocation

OXIDATION OF ALCOHOLS All alcohols can be oxidised depending on the conditions Oxidation is used to differentiate between primary, secondary and tertiary alcohols The usual reagent is acidified potassium dichromate(VI) PrimaryEasily oxidisedto aldehydes and then to carboxylic acids. SecondaryEasily oxidised to ketones TertiaryNot oxidised under normal conditions. They do break down with very vigorous oxidation PRIMARY 1° SECONDARY 2° TERTIARY 3°

OXIDATION OF PRIMARY ALCOHOLS Primary alcohols are easily oxidised to aldehydes e.g. CH3CH2OH(l) + [O] ——> CH3CHO(l) + H2O(l) ethanol ethanal it is essential to distil off the aldehyde before it gets oxidised to the acid CH3CHO(l) + [O] ——> CH3COOH(l) ethanal ethanoic acid

OXIDATION OF PRIMARY ALCOHOLS • Primary alcohols are easily oxidised to aldehydes • e.g. CH3CH2OH(l) + [O] ——> CH3CHO(l) + H2O(l) • ethanol ethanal • it is essential to distil off the aldehyde before it gets oxidised to the acid • CH3CHO(l) + [O] ——> CH3COOH(l) • ethanal ethanoic acid • Practical details • the acidified K2Cr2O7 is dripped into the warm alcohol • aldehydes have low boiling points - no hydrogen bonding - they distil off immediately • if it didn’t distil off it would be oxidised to the equivalent carboxylic acid • to oxidise an alcohol straight to the acid, reflux the mixture • compound formula intermolecular bonding boiling point • ETHANOL C2H5OH HYDROGEN BONDING 78°C • ETHANAL CH3CHO DIPOLE-DIPOLE 23°C • ETHANOIC ACID CH3COOH HYDROGEN BONDING 118°C

OXIDATION OF PRIMARY ALCOHOLS Controlling the products e.g. CH3CH2OH(l) + [O] ——> CH3CHO(l) + H2O(l) then CH3CHO(l) + [O] ——> CH3COOH(l) OXIDATION TO ALDEHYDES DISTILLATION OXIDATION TO CARBOXYLIC ACIDS REFLUX Aldehyde has a lower boiling point so distils off before being oxidised further Aldehyde condenses back into the mixture and gets oxidised to the acid

OXIDATION OF SECONDARY ALCOHOLS Secondary alcohols are easily oxidised to ketones e.g. CH3CHOHCH3(l) + [O] ——> CH3COCH3(l) + H2O(l) propan-2-ol propanone The alcohol is refluxed with acidified K2Cr2O7. However, on prolonged treatment with a powerful oxidising agent they can be further oxidised to a mixture of acids with fewer carbon atoms than the original alcohol.

OXIDATION OF SECONDARY ALCOHOLS Secondary alcohols are easily oxidised to ketones e.g. CH3CHOHCH3(l) + [O] ——> CH3COCH3(l) + H2O(l) propan-2-ol propanone The alcohol is refluxed with acidified K2Cr2O7. However, on prolonged treatment with a powerful oxidising agent they can be further oxidised to a mixture of acids with fewer carbon atoms than the original alcohol. OXIDATION OF TERTIARY ALCOHOLS Tertiary alcohols are resistant to normal oxidation

OXIDATION OF ALCOHOLS Why 1° and 2°alcohols are easily oxidised and 3° alcohols are not For oxidation to take place easily you must have two hydrogen atoms on adjacent C and O atoms.

H H R C O + [O]R C O + H2O H H OXIDATION OF ALCOHOLS Why 1° and 2°alcohols are easily oxidised and 3° alcohols are not For oxidation to take place easily you must have two hydrogen atoms on adjacent C and O atoms. 1°

H H R C O + [O]R C O + H2O H H H H R C O + [O]R C O + H2O RR OXIDATION OF ALCOHOLS Why 1° and 2°alcohols are easily oxidised and 3° alcohols are not For oxidation to take place easily you must have two hydrogen atoms on adjacent C and O atoms. 1° 2°

H H R C O + [O]R C O + H2O H H H H R C O + [O]R C O + H2O RR OXIDATION OF ALCOHOLS Why 1° and 2°alcohols are easily oxidised and 3° alcohols are not For oxidation to take place easily you must have two hydrogen atoms on adjacent C and O atoms. 1° 2° This is possible in 1° and 2° alcoholsbut not in 3° alcohols.

1° 2° H H R C O + [O]R C O + H2O H H H H R C O + [O]R C O + H2O RR R H R C O + [O] R 3° OXIDATION OF ALCOHOLS Why 1° and 2°alcohols are easily oxidised and 3° alcohols are not For oxidation to take place easily you must have two hydrogen atoms on adjacent C and O atoms. This is possible in 1° and 2°alcoholsbut not in 3° alcohols.

INFRA-RED SPECTROSCOPY Chemical bonds vibrate at different frequencies. When infra red (IR) radiation is passed through a liquid sample of an organic molecule, some frequencies are absorbed. These correspond to the frequencies of the vibrating bonds. Most spectra are very complex due to the large number of bonds present and each molecule produces a unique spectrum. However the presence of certain absorptions can be used to identify functional groups. BOND COMPOUND ABSORBANCE RANGE O-H alcohols broad 3200 cm-1 to 3600 cm-1 O-H carboxylic acids medium to broad 2500 cm-1 to 3500 cm-1 C=O ketones, aldehydes strong and sharp 1600 cm-1 to 1750 cm-1 esters and acids

INFRA-RED SPECTROSCOPY IDENTIFYING ALCOHOLS USING INFRA RED SPECTROSCOPY DifferentiationCompound O-H C=O ALCOHOLYESNO ALDEHYDE / KETONENOYES CARBOXYLIC ACIDYESYES ESTERNOYES ALCOHOL CARBOXYLIC ACID ESTER BUTAN-1-OL PROPANOIC ACID ETHYL ETHANOATE O-H absorption O-H + C=O absorption C=O absorption

LABORATORY PREPARATION OF ALCOHOLS from haloalkanes - reflux with aqueous sodium or potassium hydroxide from aldehydes - reduction with sodium tetrahydridoborate(III) - NaBH4 from alkenes - acid catalysed hydration using concentrated sulphuric acid Details of the reactions may be found in other sections.

AN INTRODUCTION TO THE CHEMISTRY OF ALCOHOLS