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    4.1.3 Carboxylic Acids & Esters

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    Fin Brickman
    Carboxylic acids contain the carboxyl functional group and are weak acids that are more acidic than alcohols and phenols. They can form hydrogen bonds, giving them higher melting and boiling points compared to similar organic molecules. Carboxylic acids undergo nucleophilic substitution reactions and can be converted to esters, acid chlorides, amides, anhydrides, and nitriles. Esters are volatile compounds derived from carboxylic acids and alcohols that have pleasant smells. Natural fats and oils are triglyceride esters of glycerol and fatty acids; hydrolysis of these esters produces soap, while transesterification produces biodiesel.

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    4.1.3 Carboxylic Acids & Esters

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    Fin Brickman
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    Carboxylic acids contain the carboxyl functional group and are weak acids that are more acidic than alcohols and phenols. They can form hydrogen bonds, giving them higher melting and boiling points compared to similar organic molecules. Carboxylic acids undergo nucleophilic substitution reactions and can be converted to esters, acid chlorides, amides, anhydrides, and nitriles. Esters are volatile compounds derived from carboxylic acids and alcohols that have pleasant smells. Natural fats and oils are triglyceride esters of glycerol and fatty acids; hydrolysis of these esters produces soap, while transesterification produces biodiesel.

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    Carboxylic acids contain the carboxyl functional group and are weak acids that are more acidic than alcohols and phenols. They can form hydrogen bonds, giving them higher melting and boiling points compared to similar organic molecules. Carboxylic acids undergo nucleophilic substitution reactions and can be converted to esters, acid chlorides, amides, anhydrides, and nitriles. Esters are volatile compounds derived from carboxylic acids and alcohols that have pleasant smells. Natural fats and oils are triglyceride esters of glycerol and fatty acids; hydrolysis of these esters produces soap, while transesterification produces biodiesel.

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    © All Rights Reserved
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    49 views5 pages

    4.1.3 Carboxylic Acids & Esters

    Uploaded by

    Fin Brickman
    Carboxylic acids contain the carboxyl functional group and are weak acids that are more acidic than alcohols and phenols. They can form hydrogen bonds, giving them higher melting and boiling points compared to similar organic molecules. Carboxylic acids undergo nucleophilic substitution reactions and can be converted to esters, acid chlorides, amides, anhydrides, and nitriles. Esters are volatile compounds derived from carboxylic acids and alcohols that have pleasant smells. Natural fats and oils are triglyceride esters of glycerol and fatty acids; hydrolysis of these esters produces soap, while transesterification produces biodiesel.

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    of 5

    CARBOXYLIC ACIDS & ESTERS

    Carboxylic Acids

    Carboxylic acids contain the carboxyl functional group:

    e.g. methanoic acid ethanoic acid benzoic acid

    ethanedioic acid benzene-1,2-dicarboxylic acid

    Physical Properties

    The ability of carboxylic acids to form hydrogen bonds means that they have fairly
    high melting and boiling points in comparison to most other organic molecules of
    similar size. They can exist as hydrogen bonded dimers in the liquid and solid states:

    The lower members of the series are pungent smelling, and very soluble in water,
    with solubility decreasing as the carbon chain length increases.

    Chemical Reactivity

     Carboxylic acids are weak acids

    Carboxylic acids show typical acidic properties, acting as proton donors and reacting
    with metals, bases and carbonates to form salts etc.

    e.g. sodium hydroxide + ethanoic acid  sodium ethanoate + water


    NaOH(aq) + CH3COOH(aq)  CH3COONa(aq) + H2O(l)

    When carboxylic acids ionise, carboxylate anions are formed:

    RCOOH ⇌ RCOO- + H+
    Carboxylic acids are more acidic than alcohols and phenols because the negative
    charge is delocalised over the carboxylate group, making the anion more stable:

     Carboxylic acids are susceptible to nucleophilic attack

    The carboxyl carbon is extremely electron deficient (+), making it a possible site for
    nucleophilic attack:

    This leads to the formation of several carboxylic acid derivatives in which the OH
    group of the acid has been replaced:

    acid (acyl) chlorides (acid) amides

    esters nitriles (acid) anhydrides

    Reactions of Carboxylic Acids

     Esterification

    carboxylic acid + alcohol ⇌ ester + water

    e.g.

    C6H5COOH + CH3OH ⇌ C6H5COOCH3 (methyl benzoate) + H2O

    Reagents: conc. H2SO4 (catalyst) Conditions: heat under reflux

    Esters can also be produced by reacting an alcohol with an acid anhydride. An acid
    anhydride can effectively be regarded as the condensation product of two carboxylic
    acids. Acid anhydrides are more reactive than the parent carboxylic acid and this
    synthetic route gives a better yield of the ester. No catalyst is required.
    acid anhydride + alcohol  ester + carboxylic acid

    e.g.

    Esters have no OH groups and therefore cannot form H-bonds. Thus they are fairly
    volatile in comparison to carboxylic acids and alcohols of similar relative molecular
    mass. Volatile esters have pleasant, fruity smells. (See below.)

     Reaction with phosphorous pentachloride

    The carboxylic acid OH group is replaced, giving an acid (acyl) chloride:

    e.g.

    CH3COOH + PCl5  CH3COCl + POCl3 + HCl(g)

    Conditions: room temperature, anhydrous

    This is a similar reaction to that of alcohols with PCl5; the white fumes of HCl given
    are a useful indication of the presence of the OH group.

     Reduction

    A stronger reducing agent is required to reduce carboxylic acids than to reduce


    aldehydes and ketones.

    Lithium aluminium hydride (LiAlH4) is a very powerful reducing agent, and must be
    used in a dry ether solvent as it reacts violently with water.

    e.g.

    C6H5COOH + 4[H]  C6H5CH2OH + H2O

    The reaction mixture is then carefully hydrolysed with dilute acid to liberate the
    product alcohol.
    Esters

    Esters are volatile, sweet smelling compounds derived from carboxylic acids by
    replacing the acidic hydrogen of the carboxylic acid with an alkyl or aryl group.

    Aliphatic esters are important flavouring and aroma components of many fruits;
    synthetic esters are used in perfumes, food and drink flavourings and as solvents.
    Many synthetic polymers contain ester linkages (polyesters).

    We have seen that one way esters can be synthesised is by the reaction of a
    carboxylic acid with an alcohol (see above). Esters are named after the alcohols and
    carboxylic acids that combine to make them. Here are a few examples:

    Alcohol Carboxylic Acid Ester Formed Structure


    ethanol ethanoic acid ethyl ethanoate CH3COOC2H5
    ethanol propanoic acid ethyl propanoate C2H5COOC2H5
    methanol ethanoic acid methyl ethanoate CH3COOCH3
    butanol ethanoic acid butyl ethanoate CH3COOC4H9
    propanol methanoic acid propyl methanoate HCOOC3H7

    Esters are not particularly reactive, but are readily hydrolysed. The esterification
    reaction is easily reversible, and ester hydrolysis can be achieved under acidic or
    alkaline conditions:

     Acid hydrolysis

    e.g. C6H5COOCH3 + H2O ⇌ C6H5COOH + CH3OH

    Reagents: dilute H2SO4(aq) conditions: heat under reflux

    This is an equilibrium, and some ester will always remain unhydrolysed.

     Alkaline hydrolysis (‘saponification’)

    e.g. C6H5COOCH3 + NaOH  C6H5COO-Na+ (sodium benzoate) + CH3OH

    reagents: (excess) NaOH(aq) conditions: heat under reflux

    If the ester is boiled with sufficient aqueous alkali, the carboxylic acid formed reacts
    with the alkali to form its carboxylate salt (as shown). This means that the hydrolysis
    goes to completion, so this is the more efficient process. The free carboxylic acid
    can be obtained by acidification:
    e.g. C6H5COO-Na+ + HCl(aq)  C6H5COOH + NaCl(aq)
    Fats and Oils - Triglyceride Esters

    Natural fats and oils are triglycerides, esters of the trihydric alcohol glycerol
    (propane-1,2,3-triol) and long chain carboxylic acids (‘fatty acids’).

    An example of a fatty acid is octadecanoic acid (stearic acid), CH 3(CH2)16COOH.

     Soaps

    Hydrolysis of triglyceride esters is the basis for the production of soaps. Soaps are
    the carboxylate salts of these long-chain fatty acids. Soaps were the first detergents,
    made by boiling animal and vegetable fats (or oils) with sodium or potassium
    hydroxide. The alkaline hydrolysis of such esters is known as ‘saponification’.

    e.g.

    a triglyceride ester a soap glycerol

    (R represents a long side chain of 12 to 20 carbons)

    An example of a soap is sodium octadecanoate (stearate), CH3(CH2)16COO-Na+.

     Biodiesel

    Methyl or ethyl esters of fatty acids are increasingly being produced for use as
    biodiesel. Biodiesel is produced by ‘transesterification’ of triglycerides from
    vegetable oils or animal fats. The trigycerides are reacted with methanol (or ethanol)
    in the presence of a sodium hydroxide catalyst. Glycerol is again a by-product:

    e.g.

    a triglyceride ester biodiesel glycerol

    (R represents a long side chain of 12 to 20 carbons)

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