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Carboxylic acids

Paper 1Paper 2Paper 3Paper 4

This section is examined in Paper 1, Paper 2, Paper 3 and Paper 4.

Structure of Carboxylic Acids
Carboxylic acids are organic compounds containing the carboxyl group (-COOH). This functional group consists of a carbonyl group (C=O) and a hydroxyl group (-OH) attached to the same carbon atom.

The general formula for the first members of this homologous series is C_nH_{2n+1}COOH. The naming convention replaces the '-e' ending of the corresponding alkane with '-oic acid'. For example, a 2-carbon chain (ethane) becomes ethanoic acid.

Building on the concept of functional groups, the carboxyl group is responsible for the acidic properties of these molecules. The hydrogen atom in the -OH part can dissociate in water to form H^+ ions, making the solution acidic.

Displayed Formula Requirements:
When asked to draw a displayed formula, you must show all atoms and all bonds. A common error is omitting the bond between the oxygen and hydrogen in the -OH group or drawing the structure as an ether (C-O-C) instead of a carboxylic acid.
Esterification
Esterification is the reaction between a carboxylic acid and an alcohol to form an ester and water. This reaction requires an acid catalyst (typically concentrated sulfuric acid) and heat.

The general equation is:
\text{Carboxylic Acid} + \text{Alcohol} \rightleftharpoons \text{Ester} + \text{Water}

Naming Esters:
The name of an ester has two parts:

  1. The first part comes from the alcohol (ending in '-yl').
  2. The second part comes from the carboxylic acid (ending in '-oate').

For example, ethanoic acid + ethanol \rightarrow ethyl ethanoate.

Reactions of Ethanoic Acid
Ethanoic acid (CH_3COOH) behaves as a weak acid. It reacts with metals, bases, and carbonates to form salts.
Salt Formula
CH_3COONa
CH_3COONa
CH_3COONa
CH_3COONa
Note on Salt Formulae:
The ethanoate ion is CH_3COO^-. When writing salt formulae, ensure the charges balance. For example, calcium forms Ca^{2+} ions, so it requires two ethanoate ions: calcium ethanoate (CH_3COO)_2Ca.
Formation of Ethanoic Acid (Oxidation)

Ethanoic acid can be formed by the oxidation of ethanol (C_2H_5OH). There are two main methods:

  1. Laboratory Method: Ethanol is warmed with acidified aqueous potassium manganate(VII) (KMnO_4) or acidified potassium dichromate(VI). The solution changes colour (e.g., purple to colourless for KMnO_4, or orange to green for dichromate).

  2. Industrial/Biological Method: During vinegar production, ethanol is oxidized by bacteria in the presence of oxygen from the air. This is a slower process occurring at room temperature.

Why Reflux?
In the laboratory oxidation of primary alcohols to carboxylic acids, the mixture is heated under reflux. Reflux is necessary because ethanol and the intermediate aldehyde (ethanal) are volatile. Heating under reflux ensures that these vapours condense and return to the flask, preventing them from escaping before they can be fully oxidized to ethanoic acid.
Esterification Example: Propanoic Acid + Butan-1-ol
Let's determine the products when propanoic acid reacts with butan-1-ol.

  1. Identify the components:

    • Carboxylic acid: Propanoic acid (3 carbons)
    • Alcohol: Butan-1-ol (4 carbons)
  2. Name the ester:

    • From alcohol 'butan' \rightarrow butyl
    • From acid 'propanoic' \rightarrow propanoate
    • Ester Name: Butyl propanoate
  3. Determine the Formula:

    • Propanoic acid part: CH_3CH_2COO-
    • Butan-1-ol part: -C_4H_9 (specifically -CH_2CH_2CH_2CH_3)
    • Combined Ester Formula: CH_3CH_2COOC_4H_9

Condensed Formula Convention:
We use CH_3CH_2COO- to represent the propanoate group derived from the acid, and -C_4H_9 for the butyl group derived from the alcohol. The oxygen atom in the ester linkage (-COO-) comes from the carboxylic acid.

⚠︎ Incorrect Salt Formulae and Ester Linkage
Mistake 1: Incorrect Salt Formulae
Students often write the salt name correctly but fail to provide the correct formula. For example, for calcium ethanoate, writing CH_3COOCa is incorrect because it does not balance the charges (Ca^{2+} vs CH_3COO^-). The correct formula is (CH_3COO)_2Ca.

Mistake 2: Swapping the Ester Oxygen
When drawing esters, students sometimes draw the linkage as R-O-C(=O)-R'. This is incorrect. The carbonyl carbon (C=O) must be directly attached to the oxygen from the acid, not the alcohol. The correct linkage is R-C(=O)-O-R'.

Mistake 3: Omitting Bonds in Displayed Formulae
When drawing ethanoic acid, students often omit the covalent bond between the oxygen and hydrogen in the -OH group. Always show all bonds explicitly.

Naming Esters and Identifying Reactants
Tip: Reverse Engineering Ester Names
When asked to identify the reactants that form a specific ester, split the name at the space. The first word (ending in '-yl') is the alcohol. The second word (ending in '-oate') is the carboxylic acid.

Example: If the ester is propyl ethanoate:

  • 'Propyl' \rightarrow Reactant is propan-1-ol.
  • 'Ethanoate' \rightarrow Reactant is ethanoic acid.

This phrasing is accepted because it directly addresses the nomenclature rules where the alkyl group from the alcohol precedes the alkanoate group from the acid.

Tip: Describing Oxidation Conditions
When describing the formation of ethanoic acid from ethanol, always mention acidified potassium manganate(VII) or dichromate(VI). Simply saying 'potassium manganate' is insufficient because the acid provides the H^+ ions necessary for the redox reaction. Examiners look for the term acidified to confirm understanding of the reaction conditions.
Practice Questions
Q:
Draw the displayed formula of ethanoic acid.
A:
Show a central carbon atom double-bonded to one oxygen atom (C=O) and single-bonded to an -OH group. The carbon is also bonded to a methyl group (CH_3). All bonds must be shown explicitly.
Q:
Name the salt formed when ethanoic acid reacts with calcium.
A:
Calcium ethanoate
Q:
What is the formula of the salt formed when ethanoic acid reacts with calcium?
A:
(CH_3COO)_2Ca
Q:
Name the ester formed from the reaction of propanoic acid and butan-1-ol.
A:
Butyl propanoate
Q:
Describe the formation of ethanoic acid from ethanol using potassium manganate(VII).
A:
Ethanol is warmed with acidified aqueous potassium manganate(VII). The purple solution turns colourless as the ethanol is oxidized to ethanoic acid.
Q:
What is the role of the acid catalyst in the reaction between a carboxylic acid and an alcohol?
A:
The acid catalyst (e.g., concentrated sulfuric acid) speeds up the reaction rate by providing H^+ ions, facilitating the formation of the ester.
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