Hydrolysis of Esters

Ester hydrolysis is breaking down an ester into its constituent carboxylic acid and alcohol this takes place in an acidic or basic medium. The mechanisms of acid-catalyzed ester hydrolysis differ, with base-catalyzed hydrolysis being irreversible.

In this article, we look into what ester is, the hydrolysis of ester, its reaction, mechanism, application, etc.

What is an Ester?

Ester is a chemical compound derived from an acid in which at least one hydroxyl group (–OH) is replaced by an alkyl (–O–) or alkoxy (–O–) group. Esters are common in organic chemistry and biological materials and often have a pleasant, fruity odor.

General formula for Ester is ROOR’

where,

• R and R’ can be any Alkyl or Aryl Group

[e.g. Methyl(-CH₃), Ethyl(-C₂H₅)] or Aryl [(e.g. Phenyl(-C₆H₅)] or Hydrogen Atom (-H)]

Some examples of Ester are:

• Methylformate (CH₃OOCH)
• Propylpropanoate(C₂H₅COOC₃H₇)
• Phenylacetate(C₆H₅COOCH₃) etc.

What is Hydrolysis?

The word hydrolysis is derived from the Greek words hydro, which means water, and lysis, which means to break apart. It is a chemical process in which water breaks down a compound into smaller molecules. Then, water molecules attach to two parts of a molecule, breaking a covalent bond in the compound by inserting a water molecule across it.

For example, An ester hydrolysis gives alcohol and carboxylic acid or carboxylate salt.

Ester Hydrolysis

Ester hydrolysis is a reaction that involves splitting an ester bond using water, catalyzed by either an acid or a base. There are two types of ester hydrolysis: acidic hydrolysis and basic hydrolysis, also known as (saponification). The choice between acidic and basic hydrolysis depends on the specific reaction conditions and the desired products.

Ester Hydrolysis with NaOH

Ester hydrolysis with NaOH, also known as base-catalyzed ester hydrolysis, is the reaction of an ester with water under a basic medium. In this process, an ester is heated under reflux with dilute NaOH to yield carboxylate salt and alcohol. This reaction is also known as saponification, as it is used to synthesize soap.

Example of Basic hydrolysis (Saponification):

C₆H₅COOCH₃ + NaOH → C₆H₅COONa + CH₃OH

Mechanism of Hydrolysis of Ester with NaOH

When an ester is hydrolyzed with sodium hydroxide (NaOH), the process involves a two-step mechanism known as nucleophilic acyl substitution. The steps involved in the mechanism of ester hydrolysis with NaOH are:

• Nucleophilic Attack: The hydroxide ion (OH^–) from NaOH acts as a nucleophile and attacks the electrophilic carbon of the ester’s carbonyl group, breaking the π bond and forming a tetrahedral intermediate.

• Elimination: The tetrahedral intermediate undergoes elimination, forming a carboxylate ion and an alcohol.

• Acid-Base Reaction: The carboxylate ion is then protonated by the NaOH, yielding the carboxylate salt.

This reaction is one-way rather than reversible, and the products are easier to separate than acid-catalyzed ester hydrolysis.

Ester Hydrolysis with H₂SO₄

The reaction of an ester with water, catalyzed by the hydroxonium ion (H₃O⁺) present in the acidic solution, involves breaking an ester bond using sulfuric acid. A large excess of water can be used, as the dilute acid provides both the acid catalyst and the water. The reaction is reversible, so an excess of water is necessary to shift the equilibrium towards the formation of carboxylic acid and alcohol.

Example of Acid Hydrolysis

C₆H₅COOCH₃ + H₂O + H₂SO₄ → C₆H₅COOH + CH₃OH

Mechanism of Hydrolysis of Esters with H₂SO₄

The mechanism of ester hydrolysis with H₂SO₄ is as follows:

• Protonation: H₂SO₄ protonates the carbonyl oxygen of the ester, forming an intermediate that is susceptible to nucleophilic attack by water.

• Nucleophilic Attack: Water attacks the carbonyl carbon, breaking the carbon-oxygen bond and forming a tetrahedral intermediate.

• Tetrahedral Intermediate Breakdown: The tetrahedral intermediate breaks down, reforming the carbonyl group and releasing an alcohol molecule.

• Proton Transfer: H₂SO₄ donates a proton to the leaving alcohol molecule, forming an alcohol molecule and regenerating the H₂SO₄ catalyst.

Overall reaction is:

RCOOR’ + H₂O + H₂SO₄ → RCOOH + R’-OH + H₂SO₄

This reaction is commonly used to synthesize certain types of ethers and dehydrate alcohols to alkenes.

Synthesis of Ester

Esterification is the process of combining an organic acid (RCOOH) with an alcohol (ROH) to form an ester (RCOOR) and by-product. The reaction is characterized by combining an acid and an alcohol (with an acid catalyst) to give an ester.

There are three main methods for esterification:

• Esterification of Carboxylic Acid and Alcohol
• Esterification of Anhydride
• Esterification of Acid Chloride

Let’s learn about them in detail.

Esterification of Carboxylic Acid and Alcohol

This method involves heating carboxylic acids with alcohols in the presence of an acid catalyst, such as sulfuric acid (H₂SO₄)

Carboxylic Acid + Alcohol → Ester + Water

Example:

C₆H₅COOH + C₂H₅OH → C₆H₅COOC₂H₅ + H₂O

Esterification of Anhydride

This method involves the reaction of an acid anhydride with an alcohol.

Anhydride + Alcohol → Ester + Carboxylic Acid

Example:

C₆H₅-CO-O-CO-C₆H₅ + C₂H₅-OH → C₆H₅-CO-O-C₂H₅ + C₆H₅-COOH

Esterification of Acid Chloride

This method involves the reaction of an acid chloride with an alcohol.

Acyl Chloride + Alcohol → Ester + Hydrogen Chloride

Example:

CH₃COCl + CH₃OH → CH₃COOCH₃ + HCl

This reaction is slow and reversible.

Reaction of Ester

Reaction of ester are as,

• Reaction with Anhydride
• Reaction with Acyl Halide

Reaction with Anhydride

The reaction for the same is added below,

Reaction with Acyl Halide

The reaction for the same is added below,

Hydrolyzing Ester to Make Soap

Process of hydrolyzing esters to make soap is called saponification. When esters are treated with a base such as sodium hydroxide, they are converted into carboxylate salts, which, upon neutralization, yield carboxylic acids. It is a reversible reaction, but excess water is used to complete the hydrolysis as thoroughly as possible.

The resulting carboxylate salts are the essential ingredients in soap, as they have both hydrophobic and hydrophilic properties, enabling them to act as surfactants and form micelles, which are essential for the cleaning ability of soap. The name “saponification” comes from the Latin word “sapo,” which means soap, as soap used to be made by the ester hydrolysis of fats.

During saponification, a base catalyzes the hydrolysis of the ester groups of oil to form soap molecules with a long hydrophobic carbon chain and a hydrophilic carboxylate ion, making them effective for cleaning.

Application of Ester

Esters have a very large of applications in various industries.

• They are pleasant-smelling organic compounds used in manufacturing soaps, perfumes, and polyesters.

• They are employed in producing synthetic flavors, fragrances, and cosmetics.

• Industrially, esters are used as lacquers, paints, and varnish solvents.

• They can be converted into essential polymers, such as polyesters, with diverse applications, including clothing and plastic manufacturing.

• They are found in natural waxes, fats, and oils and are also used as softening agents for resins and plastics.

Read More,

• Ethers
• Ester and Ether
• Reaction of Esters

Frequently Asked Questions on Ester Hydrolysis

What Happens in Hydrolysis of Esters?

Hydrolysis of an Ester gives a carboxylic acid and an alcohol.

What is Order of Hydrolysis of Ester?

Hydrolysis of Ester in acidic medium is a first order reaction.

What is Function of Acid and Base in Acid-Catalyzed/Base-Catalyzed Reaction?

In acid-catalyzed reactions, acids speed up the process, while bases play that role in base-catalyzed reactions. Imagine acids and bases as chemical helpers that make reactions happen faster.

Is Ester Hydrolysis Endothermic?

No, ester hydrolysis is generally exothermic, meaning it releases heat. When esters react with water in a hydrolysis reaction, they break apart into an alcohol and a carboxylic acid. This breaking of bonds releases energy, making the overall process exothermic.

What is Saponification?

Saponification is a process where fats or oils react with a strong base to create soap and glycerol. This chemical reaction turns ingredients like oils into soap, making it useful for cleaning and washing.

What are Uses of Ester?

Esters have everyday roles in our lives. They create pleasant scents in perfumes, flavor our fruits, and are the most important in making nail polish and many cosmetics. And also, some esters are used as solvents and contribute to the flavors of many foods we enjoy

How can you Synthesize Ester?

We combine Alcohol with Acid in the presence of a catalyst, to create Ester. This process, is known as esterification.