Unit 2 Module 1 Carboxylic acids and their derivatives CARBOXYLIC ACIDS AND DERIVATIVES Structure of a typical carboxylic acid

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This group

is the functional group

This is an example of an aliphatic acid Aromatic carboxylic acids have a carboxyl group attached directly to an aromatic ring. Reactions of carboxylic acids 1. With highly reactive metals and inorganic bases/alkalis to form the salt and hydrogen gas for highly reactive metals and a salt and water formed from inorganic bases 2CH3COOH(aq) + Na(s) ethanoic sodium acid CH3COONa(aq) + sodium ethanoate H2(g) hydrogen gas

2CH3COOH(aq) + NaOH(aq) ethanoic sodium acid hydroxide 2. Amide formation

CH3COONa(aq) + H2O(l) sodium water ethanoate

With ammonia to form an ammonium salt, which then decomposes by heat (remember this reaction is done in reflux) to form an amide RCOOH + NH3 RCOO-NH4+ RCOO-NH4+ RCONH2 + H2O

Amides have the functional group below

Unit 2 Module 1 Carboxylic acids and their derivatives 3. Ester formation

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Reflux with alcohols in the presence of conc. sulphuric acid and 170 C to form an ester and water (Note esters are low molecular mass compounds, which have sweet smells and are insoluble in water) RCOOH + R1OH conc.H2SO4 4. Acid chloride formation With chlorinating agents e.g. dichlorosulphur (IV) oxide SOCl2 or phosphorous (V) chloride PCl5 to form an acid chloride RCOOH PCl5 or SOCl2 RCOCl + HCl
Acid chlorides have the following functional group

RCOOR1 + H2O

5. With carbonates and hydrogen carbonates to give a salt, carbon dioxide and water 2RCOOH + Na2CO3 2RCOO-Na+ + CO2 + H2O RCOOH + NaHCO3 RCOO-Na+ + CO2 + H2O 6. Reduction
With LiAlH4 or any other reducing agent to form the corresponding alcohol

RCOOH LiAlH4 (in ether) RCH2OH

7. Anhydride formation When 2 molecules of a carboxylic acid is reacted with a dehydrating agent such as phosphorous (V) oxide P 4O10, a molecule of water is eliminated and an acid anhydride is formed. 2RCOOH distilled in P4O10 (RCO)2O

Unit 2 Module 1 Carboxylic acids and their derivatives Checkpoint A

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Unit 2 Module 1 Carboxylic acids and their derivatives Reactions of acid derivatives

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1. Hydrolysis Acid chlorides are hydrolysed to give carboxylic acid and hydrogen chloride gas RCOCl + H2O RCOOH + HCl Esters are also hydrolysed to give the original alcohol and if the reagent is a strong mineral acid, then the carboxylic acid is formed RCOOR1 + H+ ROH + RCOOH If the reagent is a strong alkali, then the original alcohol is formed and the salt of the carboxylic acid RCOOR 1 + OH- ROH + RCOO2. Ester formation Acid and aroyl chlorides react readily with a) alcohols to form an ester and hydrogen chloride gas b) phenols in alkaline solutions to form an ester and hydrogen chloride gas

3. Amide formation Amides are formed by reaction of acid chlorides with ammonia and with primary and secondary amines RCOCl + NH3 RCONH2 + HCl RCOCl + R2NH RCONR2 + HCl
4.

Anhydride formation
When an acid chloride is heated with the sodium salt of a carboxylic acid, the acid anhydride is formed RCOCl + RCOO-Na+ (RCO)2O + NaCl NB acid anhydrides react in a similar way to acid chlorides; they form esters with alcohols and phenols and they form amides with ammonia and primary and secondary amines.

Unit 2 Module 1 Carboxylic acids and their derivatives Checkpoint B

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Saponification (alkaline hydrolysis of fats/oils) When fats/oils are hydrolysed by an alkali, soap is produced. How is a fat/oil molecule formed? By the reaction of glycerol and long chain fatty acids (carboxylic acids with hydrocarbon chains containing 12 or more carbon atoms) Glycerol is propane-1,2,3-triol Long chain fatty acids could be: C15H31COOH palmitic acid (saturated), C17H35COOH stearic acid (saturated) C17H33COOH oleic acid (unsaturated)

Unit 2 Module 1 Carboxylic acids and their derivatives

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When a fat/oil molecule is hydrolysis by an alkali, the glycerol is formed as well as the sodium salt of the long chain fatty acid. The sodium salt of the acid is the soap.

Transesterification biodiesel production Biodiesel production is the act of producing the biofuel, biodiesel, through either transesterification or alcoholysis. The process involves reacting vegetable oils or animal fats catalytically with a short-chain aliphatic alcohols (typically methanol or ethanol). The vegetable oil is reacted with alkali in the presence of ethanol or methanol as a catalyst under reflux, which produces the esters of the fatty acids and glycerol. The biodiesel is the collection of the esters produced. Checkpoint C What advantages would there be for the use of biodiesel or biofuel in general? .......

Unit 2 Module 1 Carboxylic acids and their derivatives page 7 of 8 Explanation of relative acidities of acids and chlorine substituted acids Carboxylic acids are only partially ionised in aqueous solution, making them weak acids.

The relative strength of acids is attributed to the stability of the acid anion. The more stable the acid anion, the stronger the acid. The longer the hydrocarbon acid, the WEAKER the acid. However, the more electronegative atoms present in the molecule e.g. Cl atoms present in the aliphatic chain the STRONGER the acid. In order of DECREASING ACID STRENGTH of aliphatic acids

(Cl)3CCOOH

CH(Cl)2COOH

CH2ClCOOH

CH3COOH

CH3CH2COOH

In aliphatic acids, the more electron withdrawing groups present, this represents a GREATER spreading of the charge on the oxygen atom (from the anion formed from dissociation in aqueous solution) which results in a more stable acid anion. Therefore trichloroethanoic acid is more acidic than dichloroethanoic acid etc. Propanoic acid is a weaker acid than ethanoic acid since the hydrocarbon chain is longer. NB The lower the pKa value, the stronger the acid. Note that aliphatic alcohols show the weakest acidic character, then phenols are stronger and finally carboxylic acids show the strongest acidic character.

The acid anion of carboxylic acids are therefore the most stable, then the acid anion from phenols and finally the acid anion from ethanol. Note that acid chlorides are MORE reactive than corresponding carboxylic acids.

Unit 2 Module 1 Carboxylic acids and their derivatives Checkpoint C

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