1. AN INTRODUCTION TO CARBOXYLIC ACIDS AND THEIR DERIVATIVES KNOCKHARDY PUBLISHING 2008 SPECIFICATIONS

2. 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 orusing the left and right arrow keys on the keyboard KNOCKHARDY PUBLISHING CARBOXYLIC ACIDS

3. CONTENTS Structure of carboxylic acids Nomenclature Physical properties of carboxylic acids Preparation of carboxylic acids Chemical properties of carboxylic acids Esters Triglycerides and fats Biofuels CARBOXYLIC ACIDS

4. Before you start it would be helpful to… Recall the definition of a covalent bond Recall the difference types of physical bonding Be able to balance simple equations Be able to write out structures for simple organic molecules Understand the IUPAC nomenclature rules for simple organic compounds Recall the chemical properties of alkanes and alkenes CARBOXYLIC ACIDS

5. STRUCTURE OF CARBOXYLIC ACIDS contain the carboxyl functional group COOH the bonds are in a planar arrangement

6. STRUCTURE OF CARBOXYLIC ACIDS contain the carboxyl functional group COOH the bonds are in a planar arrangement include a carbonyl (C=O) group and a hydroxyl (O-H) group

7. STRUCTURE OF CARBOXYLIC ACIDS contain the carboxyl functional group COOH the bonds are in a planar arrangement include a carbonyl (C=O) group and a hydroxyl (O-H) group are isomeric with esters :- RCOOR’

8. HOMOLOGOUS SERIES HCOOH CH 3 COOH C 2 H 5 COOH Carboxylic acids form a homologous series

9. HOMOLOGOUS SERIES HCOOH CH 3 COOH C 2 H 5 COOH With more carbon atoms, there can be structural isomers C 3 H 7 COOH (CH 3 ) 2 CHCOOH

10. INFRA-RED SPECTROSCOPY IDENTIFYING CARBOXYLIC ACIDS USING INFRA RED SPECTROSCOPY DifferentiationCompoundO-H C=O ALCOHOLYES NO CARBOXYLIC ACIDYES YES ESTER NO YES ALCOHOL CARBOXYLIC ACID ESTER O-H absorption O-H + C=O absorption C=O absorption

11. Acids are named according to standard IUPAC rules select the longest chain of C atoms containing the COOH group; remove the e and add oic acid after the basic name number the chain starting from the end nearer the COOH group as in alkanes, prefix with alkyl substituents side chain positions are based on the C in COOH being 1 e.g. CH 3 - CH(CH 3 ) - CH 2 - CH 2 - COOH is called 4-methylpentanoic acid NAMING CARBOXYLIC ACIDS

12. Acids are named according to standard IUPAC rules select the longest chain of C atoms containing the COOH group; remove the e and add oic acid after the basic name number the chain starting from the end nearer the COOH group as in alkanes, prefix with alkyl substituents side chain positions are based on the C in COOH being 1 NAMING CARBOXYLIC ACIDS METHANOIC ACIDETHANOIC ACID PROPANOIC ACID

13. Acids are named according to standard IUPAC rules select the longest chain of C atoms containing the COOH group; remove the e and add oic acid after the basic name number the chain starting from the end nearer the COOH group as in alkanes, prefix with alkyl substituents side chain positions are based on the C in COOH being 1 NAMING CARBOXYLIC ACIDS BUTANOIC ACID2-METHYLPROPANOIC ACID

14. NAMING CARBOXYLIC ACIDS Acids are named according to standard IUPAC rules Many carboxylic acids are still known under their trivial names, some having been called after characteristic properties or their origin. FormulaSystematic name (trivial name)origin of name HCOOH methanoic acid formic acidlatin for ant CH 3 COOH ethanoic acid acetic acidlatin for vinegar C 6 H 5 COOH benzenecarboxylic acidbenzoic acidfrom benzene

15. 101°C 118°C 141°C 164°C PHYSICAL PROPERTIES BOILING POINT Increases as size increases - due to increased van der Waals forces

16. Greater branching = lower inter-molecular forces = lower boiling point Boiling point is higher for “straight” chain isomers. 101°C 118°C 141°C 164°C 164°C 154°C PHYSICAL PROPERTIES BOILING POINT Increases as size increases - due to increased van der Waals forces

17. PHYSICAL PROPERTIES BOILING POINT Increases as size increases - due to increased van der Waals forces Carboxylic acids have high boiling points for their relative mass The effect of hydrogen bonding on the boiling point of compounds of similar mass CompoundFormulaM r b. pt. (°C)Comments ethanoic acidCH 3 COOH60 118 propan-1-olC 3 H 7 OH60 97 h-bonding propanalC 2 H 5 CHO58 49 dipole-dipole butaneC 4 H 10 58 - 0.5 basic V der W

18. PHYSICAL PROPERTIES BOILING POINT Increases as size increases - due to increased van der Waals forces Carboxylic acids have high boiling points for their relative mass arises from inter-molecular hydrogen bonding due to polar O—H bonds AN EXTREME CASE... DIMERISATION extra inter-molecular attraction = more energy to separate molecules HYDROGEN BONDING

19. PHYSICAL PROPERTIES SOLUBILITY carboxylic acids are soluble in organic solvents they are also soluble in water due to hydrogen bonding HYDROGEN BONDING

20. PHYSICAL PROPERTIES SOLUBILITY carboxylic acids are soluble in organic solvents they are also soluble in water due to hydrogen bonding small ones dissolve readily in cold water as mass increases, the solubility decreases benzoic acid is fairly insoluble in cold but soluble in hot water HYDROGEN BONDING

21. PREPARATION OF CARBOXYLIC ACIDS Oxidation of aldehydesRCHO + [O] ——> RCOOH Hydrolysis of estersRCOOR + H 2 O RCOOH + ROH Hydrolysis of acyl chloridesRCOCl + H 2 O ——> RCOOH + HCl Hydrolysis of nitrilesRCN + 2 H 2 O ——> RCOOH + NH 3 Hydrolysis of amidesRCONH 2 + H 2 O ——> RCOOH + NH 3

22. CHEMICAL PROPERTIES ACIDITY weak acidsRCOOH + H 2 O (l) RCOO¯ (aq) + H 3 O + (aq) form saltsRCOOH + NaOH (aq) ——> RCOO¯Na + (aq) + H 2 O (l) 2RCOOH + Mg (s) ——> (RCOO¯) 2 Mg 2+ (aq) + H 2 (g)

23. CHEMICAL PROPERTIES ACIDITY weak acidsRCOOH + H 2 O (l) RCOO¯ (aq) + H 3 O + (aq) form saltsRCOOH + NaOH (aq) ——> RCOO¯Na + (aq) + H 2 O (l) 2RCOOH + Mg (s) ——> (RCOO¯) 2 Mg 2+ (aq) + H 2 (g) The acid can be liberated from its salt by treatment with a stronger acid. e.g.RCOO¯ Na + (aq) + HCl (aq) ——> RCOOH + NaCl (aq) Conversion of an acid to its water soluble salt followed by acidification of the salt to restore the acid is often used to separate acids from a mixture.

24. CHEMICAL PROPERTIES ACIDITY weak acidsRCOOH + H 2 O (l) RCOO¯ (aq) + H 3 O + (aq) form saltsRCOOH + NaOH (aq) ——> RCOO¯Na + (aq) + H 2 O (l) 2RCOOH + Mg (s) ——> (RCOO¯) 2 Mg 2+ (aq) + H 2 (g) The acid can be liberated from its salt by treatment with a stronger acid. e.g.RCOO¯ Na + (aq) + HCl (aq) ——> RCOOH + NaCl (aq) Conversion of an acid to its water soluble salt followed by acidification of the salt to restore the acid is often used to separate acids from a mixture. QUALITATIVE ANALYSIS Carboxylic acids are strong enough acids to liberate CO 2 from carbonates Phenols are also acidic but not are not strong enough to liberate CO 2.

25. ESTERIFICATION Reagent(s)alcohol + strong acid catalyst (e.g. conc. H 2 SO 4 ) Conditionsreflux Productester Equation e.g.CH 3 CH 2 OH (l) + CH 3 COOH (l) CH 3 COOC 2 H 5 (l) + H 2 O (l) ethanol ethanoic acid ethyl ethanoate

26. ESTERIFICATION Reagent(s)alcohol + strong acid catalyst (e.g. conc. H 2 SO 4 ) Conditionsreflux Productester Equation e.g.CH 3 CH 2 OH (l) + CH 3 COOH (l) CH 3 COOC 2 H 5 (l) + H 2 O (l) ethanol ethanoic acid ethyl ethanoate NotesConc. H 2 SO 4 is a dehydrating agent - it removes water causing the equilibrium to move to the right and thus increases the yield of the ester

27. ESTERIFICATION Reagent(s)alcohol + strong acid catalyst (e.g conc. H 2 SO 4 ) Conditionsreflux Productester Equation e.g.CH 3 CH 2 OH (l) + CH 3 COOH (l) CH 3 COOC 2 H 5 (l) + H 2 O (l) ethanol ethanoic acid ethyl ethanoate NotesConc. H 2 SO 4 is a dehydrating agent - it removes water causing the equilibrium to move to the right and thus increases the yield of the ester Naming estersNamed from the original alcohol and carboxylic acid CH 3 OH + CH 3 COOH CH 3 COOCH 3 + H 2 O from ethanoic acid CH 3 COOCH 3 from methanol METHYL ETHANOATE

28. CHLORINATION OF CARBOXYLIC ACIDS Chlorinationinvolves replacing the OH with a Cl Productacyl chloride Reagentthionyl chloride SOCl 2 ConditionsDRY conditions EquationCH 3 COOH + SOCl 2 ——> CH 3 COCl + SO 2 + HCl Alternative methodCH 3 COOH + PCl 5 ——> CH 3 COCl + POCl 3 + HCl phosphorus(V) chloride

29. ESTERS StructureSubstitute an organic group for the H in carboxylic acids Nomenclaturefirst part from alcohol, second part from acid e.g. methyl ethanoate CH 3 COOCH 3 ETHYL METHANOATE METHYL ETHANOATE

30. ESTERS StructureSubstitute an organic group for the H in carboxylic acids Nomenclaturefirst part from alcohol, second part from acid e.g. methyl ethanoate CH 3 COOCH 3 PreparationFrom carboxylic acids, acyl chlorides and acid anhydrides ReactivityUnreactive compared with acids and acyl chlorides ETHYL METHANOATE METHYL ETHANOATE

31. ESTERS StructureSubstitute an organic group for the H in carboxylic acids Nomenclaturefirst part from alcohol, second part from acid e.g. methyl ethanoate CH 3 COOCH 3 PreparationFrom carboxylic acids, acyl chlorides and acid anhydrides ReactivityUnreactive compared with acids and acyl chlorides IsomerismEsters are structural isomers of carboxylic acids ETHYL METHANOATE METHYL ETHANOATE

32. Classification CARBOXYLIC ACID ESTER Functional Group R-COOH R-COOR Name PROPANOIC ACID METHYL ETHANOATE Physical propertiesO-H bond gives rise No hydrogen bonding to hydrogen bonding; insoluble in water get higher boiling point and solubility in water Chemical propertiesacidic fairly unreactive react with alcohols hydrolysed to acids STRUCTURAL ISOMERISM – FUNCTIONAL GROUP

33. PREPARATION OF ESTERS - 1 Reagent(s)alcohol + carboxylic acid Conditionsreflux with a strong acid catalyst (e.g. conc. H 2 SO 4 ) Equation e.g.CH 3 CH 2 OH (l) + CH 3 COOH (l) CH 3 COOC 2 H 5 (l) + H 2 O (l) ethanol ethanoic acid ethyl ethanoate NotesConc. H 2 SO 4 is a dehydrating agent - it removes water causing the equilibrium to move to the right and thus increases the yield of the ester For more details see under ‘Reactions of carboxylic acids’

34. PREPARATION OF ESTERS - 2 Reagent(s)alcohol + acyl chloride Conditionsreflux under dry conditons Equation e.g. CH 3 OH (l) + CH 3 COCl (l) ——> CH 3 COOCH 3 (l) + HCl (g) methanol ethanoyl methyl chloride ethanoate NotesAcyl chlorides are very reactive but must be kept dry as they react with water.

35. PREPARATION OF ESTERS - 3 Reagent(s)alcohol + acid anhydride Conditionsreflux under dry conditons Equation e.g. CH 3 OH (l) + (CH 3 CO) 2 O (l) ——> CH 3 COOCH 3 (l) + CH 3 COOH (l) methanol ethanoic methyl ethanoic anhydride ethanoate acid NotesAcid anhydrides are not as reactive as acyl chlorides so the the reaction is slower. The reaction is safer - it is less exothermic. Acid anhydrides are less toxic.

36. HYDROLYSIS OF ESTERS Hydrolysis is the opposite of esterification ESTER + WATER CARBOXYLIC ACID + ALCOHOL HCOOH + C 2 H 5 OH METHANOIC ETHANOL ACID ETHYL METHANOATE

37. HYDROLYSIS OF ESTERS Hydrolysis is the opposite of esterification ESTER + WATER CARBOXYLIC ACID + ALCOHOL HCOOH + C 2 H 5 OH METHANOIC ETHANOL ACID ETHYL METHANOATE METHYL ETHANOATE

38. HYDROLYSIS OF ESTERS Hydrolysis is the opposite of esterification ESTER + WATER CARBOXYLIC ACID + ALCOHOL HCOOH + C 2 H 5 OH METHANOIC ETHANOL ACID CH 3 COOH + CH 3 OH ETHANOIC METHANOL ACID ETHYL METHANOATE METHYL ETHANOATE

39. HYDROLYSIS OF ESTERS Hydrolysis is the opposite of esterification ESTER + WATER CARBOXYLIC ACID + ALCOHOL The products of hydrolysis depend on the conditions used... acidic CH 3 COOCH 3 + H 2 O CH 3 COOH + CH 3 OH alkaline CH 3 COOCH 3 + NaOH ——> CH 3 COO¯ Na + + CH 3 OH

40. HYDROLYSIS OF ESTERS Hydrolysis is the opposite of esterification ESTER + WATER CARBOXYLIC ACID + ALCOHOL The products of hydrolysis depend on the conditions used... acidic CH 3 COOCH 3 + H 2 O CH 3 COOH + CH 3 OH alkaline CH 3 COOCH 3 + NaOH ——> CH 3 COO¯ Na + + CH 3 OH If the hydrolysis takes place under alkaline conditions, the organic product is a water soluble ionic salt

41. HYDROLYSIS OF ESTERS Hydrolysis is the opposite of esterification ESTER + WATER CARBOXYLIC ACID + ALCOHOL The products of hydrolysis depend on the conditions used... acidic CH 3 COOCH 3 + H 2 O CH 3 COOH + CH 3 OH alkaline CH 3 COOCH 3 + NaOH ——> CH 3 COO¯ Na + + CH 3 OH If the hydrolysis takes place under alkaline conditions, the organic product is a water soluble ionic salt The carboxylic acid can be made by treating the salt with HCl CH 3 COO¯ Na + + HCl ——> CH 3 COOH + NaCl

42. USES OF ESTERS Despite being fairly chemically unreactive, esters are useful as... flavouringsapple2-methylbutanoate pear3-methylbutylethanoate banana1-methylbutylethanoate pineapplebutylbutanoate rum2-methylpropylpropanoate solventsnail varnish remover - ethyl ethanoate plasticisers

43. TRIGLYCERIDES AND FATS Triglycerides are the most common component of edible fats and oils are triesters of the alcohol glycerol, (propane-1,2,3-triol) and fatty acids glycerol a triglyceride

44. TRIGLYCERIDES AND FATS Triglycerides are the most common component of edible fats and oils are triesters of the alcohol glycerol, (propane-1,2,3-triol) and fatty acidsSaponification alkaline hydrolysis of triglycerol esters produces soaps a simple soap is the salt of a fatty acid as most oils contain a mixture of triglycerols, soaps are not compounds the quality of a soap depends on the oils from which it is made

45. FATTY ACIDS Carboxylic acids that are obtained from natural oils and fats; they can be… Saturated SaturatedCH 3 (CH 2 ) 16 COOH octadecanoic acid (stearic acid)

46. FATTY ACIDS Carboxylic acids that are obtained from natural oils and fats; they can be… Saturated SaturatedCH 3 (CH 2 ) 16 COOH octadecanoic acid (stearic acid) 9 Unsaturated UnsaturatedCH 3 (CH 2 ) 7 CH=CH(CH 2 ) 7 COOHoctadec-9-enoic acid (oleic acid) cis (Z) isomer trans (E) isomer

47. FATTY ACIDS Carboxylic acids that are obtained from natural oils and fats; they can be… Saturated SaturatedCH 3 (CH 2 ) 16 COOH octadecanoic acid (stearic acid) 9 Unsaturated UnsaturatedCH 3 (CH 2 ) 7 CH=CH(CH 2 ) 7 COOHoctadec-9-enoic acid (oleic acid) cis (Z) isomer trans (E) isomer 12 9 CH 3 (CH 2 ) 4 CH=CHCH 2 CH=CH(CH 2 ) 7 COOH octadec-9,12-dienoic acid (linoleic acid)

48. FATTY ACIDS AND HEALTH Saturated Saturated solids at room temperature found in meat and dairy products are bad for health increase cholesterol levels - can lead to heart problems

49. FATTY ACIDS AND HEALTH Saturated Saturated solids at room temperature found in meat and dairy products are bad for health increase cholesterol levels - can lead to heart problems Mono unsaturated unsaturated contain just one C=C thought to be neutral to our health found in olives, olive oil, groundnut oil, nuts, avocados

50. FATTY ACIDS AND HEALTH Saturated Saturated solids at room temperature found in meat and dairy products are bad for health increase cholesterol levels - can lead to heart problems Mono unsaturated unsaturated contain just one C=C thought to be neutral to our health found in olives, olive oil, groundnut oil, nuts, avocadosPoly unsaturated unsaturated are considered to be ‘good fats’ contain more than one C=C bond tend to be liquids at room temperature, eg olive oil. can be split into two main types... Omega 3 - fatty acids Omega 6 - fatty acids

51. FATTY ACIDS AND HEALTH Saturated Saturated solids at room temperature found in meat and dairy products are bad for health increase cholesterol levels - can lead to heart problems Mono unsaturated unsaturated contain just one C=C thought to be neutral to our health found in olives, olive oil, groundnut oil, nuts, avocadosPoly unsaturated unsaturated are considered to be ‘good fats’ contain more than one C=C bond tend to be liquids at room temperature, eg olive oil. can be split into two main types... Omega 3 - fatty acids Omega 6 - fatty acids

52. OMEGA 3 and 6 FATTY ACIDS Omega 3 - fatty acids Omega 3 - fatty acidslower the total amount of fat in the blood and can lower blood pressure and decrease the risk of cardiovascular disease 3  (omega) endCH 3 CH 2 CH=CHCH 2 CH 2 CH 2 CH 2 CH=CH(CH 2 ) 7 COOH The omega numbering system starts from the opposite end to the carboxylic acid group

53. OMEGA 3 and 6 FATTY ACIDS Omega 3 - fatty acids Omega 3 - fatty acidslower the total amount of fat in the blood and can lower blood pressure and decrease the risk of cardiovascular disease 3  (omega) endCH 3 CH 2 CH=CHCH 2 CH 2 CH 2 CH 2 CH=CH(CH 2 ) 7 COOH Omega 6 - fatty acids Omega 6 - fatty acidsreduce the risk of cardiovascular disease but can contribute to allergies and inflammation 6  (omega) endCH 3 CH 2 CH 2 CH 2 CH 2 CH=CHCH 2 CH=CH(CH 2 ) 7 COOH

54. CHOLESTEROL a fatty substance which is found in the blood it is mainly made in the body plays an essential role in how every cell in the body works eating too much saturated fat increases cholesterol levels too much cholesterol in the blood can increase the risk of heart problems

55. CHOLESTEROL a fatty substance which is found in the blood it is mainly made in the body plays an essential role in how every cell in the body works eating too much saturated fat increases cholesterol levels too much cholesterol in the blood can increase the risk of heart problems Ways to reduce cholesterol levels cut down on saturated fats and trans fats (trans fats are more stable and difficult to break down in the body) replace them with monounsaturated fats and polyunsaturated fats eat oily fish have a high fibre diet; porridge, beans, fruit and vegetables exercise regularly

56. BIOFUELS What are they? Liquid fuels made from plant material and recycled elements of the food chainBiodiesel An alternative fuel which can be made from waste vegetable oil or from oil produced from seeds. It can be used in any diesel engine, either neat or mixed with petroleum diesel. It is a green fuel, does not contribute to the carbon dioxide (CO 2 ) burden and produces drastically reduced engine emissions. It is non-toxic and biodegradable. vegetable oilglycerolbiodiesel

57. BIOFUELS Advantages Advantages renewable - derived from sugar beet, rape seed dramatically reduces emissions carbon neutral biodegradable non-toxic fuel & exhaust emissions are less unpleasant can be used directly in unmodified diesel engine high flashpoint - safer to store & transport simple to make used neat or blended in any ratio with petroleum diesel

58. BIOFUELS Advantages Advantages renewable - derived from sugar beet, rape seed dramatically reduces emissions carbon neutral biodegradable non-toxic fuel & exhaust emissions are less unpleasant can be used directly in unmodified diesel engine high flashpoint - safer to store & transport simple to make used neat or blended in any ratio with petroleum diesel Disadvantages Disadvantages poor availability - very few outlets & manufacturers more expensive to produce poorly made biodiesel can cause engine problems

59. BIOFUELS Advantages Advantages renewable - derived from sugar beet, rape seed dramatically reduces emissions carbon neutral biodegradable non-toxic fuel & exhaust emissions are less unpleasant can be used directly in unmodified diesel engine high flashpoint - safer to store & transport simple to make used neat or blended in any ratio with petroleum diesel Disadvantages Disadvantages poor availability - very few outlets & manufacturers more expensive to produce poorly made biodiesel can cause engine problemsFuture problems problems there isn’t enough food waste to produce large amounts crops grown for biodiesel use land for food crops a suitable climate is needed to grow most crops some countries have limited water resources

60. © 2009 JONATHAN HOPTON & KNOCKHARDY PUBLISHING THE END AN INTRODUCTION TO CARBOXYLIC ACIDS AND THEIR DERIVATIVES