PRACTICAL 2: Methyl benzoate by Fischer esterification

Aim: To prepare methyl benzoate

Objectives
i.
ii.

To react benzoic acid with methanol

To collect the methyl benzoate produced

Overview

Methyl benzoate is an ester compound; an organic functional group that has an oxygen atom
connected to two carbons with one of these carbons is doubly-bonded to another oxygen atom.
The methyl benzoate can be synthesized by esterification of benzoic acid with methanol using
sulfuric acid as a catalyst. The experiment was performed to isolate the product methyl benzoate
and to separate out the unreacted benzoic acid, by the method of base extraction. Then, the
success of the reaction and the purity of the product were evaluated using FT-IR and GC. Finally,
the results obtained from the FT-IR and GC data revealed that the reaction did occur successfully
and the p
The ester is formed when a carboxylic acid reacts with excess alcohol. The reaction is
acid catalysed and heat is required. This type of reaction is commonly referred to as
Fischer esterification and is generally represented by the following equation:
RCOOH +RIOH H+/ heat
General mechanism

RCOORI + H2O

In this experiment, benzoic acid and excess methanol are refluxed in the presence of a
catalytic amount of sulphuric acid. Water and ether are added, the water layer
withdrawn and the ether layer washed with water, bicarbonate and saturated salt
solutions. After drying over calcium chloride, the ether is evaporated and finally the
product, methyl benzoate is distilled.
Reagents and Apparatus
Benzoic acid; methanol; concentrated sulphuric acid; practical grade ether; 5% sodium
bicarbonate; hydrochloric acid; saturated sodium chloride solution; anhydrous sodium
sulphate; reflux condenser; separating funnel; boiling beads; heat source; distillation
unit; round bottomed flask
Procedure
Safety Considerations
! Methanol is an extremely toxic compound which can cause blindness or death if drunk in small
quantities or absorbed in large quantities through the skin. If you spill small amounts on the
skin, rinse it off immediately with water. If you spill a larger quantity on your clothing or skin,
notify your instructor promptly.
The following chemicals 10.000g of benzoic acid and 25ml of methanol were placed in
a 250ml round bottomed flask, the mixture was cooled in ice, 3ml of concentrated
sulphuric acid was added to the mixture slowly and carefully down the walls of the flask,
and then swirling was perfomered to mix the components.
After attaching a reflux condenser with two boiling beads, the mixture was gently
refluxed for 1 hour.This was followed by cooling the solution, decanting into a separating
funnel containing 50ml of water and rinsing the flask with 35ml of practical grade ether.
The ether was added to the separating funnel, shaking thoroughly and draining off the

water layer which contains sulphuric acid and the bulk of methanol was perfomed in that
order.
The ether was washed with 25ml of water followed by 25ml of 5% sodium bicarbonate
to remove unreacted benzoic acid. Shaking was repeated, with frequent release of
pressure by inverting the separatory funnel and opening the stop cock until no further
reaction is apparent and the bicarbonate layer was then drain off into a beaker. The
ether layer in the separatory funnel was then washed with saturated sodium chloride
solution and dried the solution was dried over anhydrous sodium sulphate in a conical
flask. After 10 minutes the dry ether solution was decanted into a round bottomed flask,
the drying agent was washed with an additional 5ml of ether then decanted again into
the round bottomed flask.
Simple distillation was used to remove ether. To the residual oil , 2,5 g of anhydrous
sodium sulphate was added and heating of the mixture was done for 5 minutes.This
was followed by decanting the methyl benzoate into a 50ml round bottomed flask, a
still-head was attached and an air cooled condenser, and material boiling above 190 0C
was collected.
Weighing of benzoate
Beaker+benzoic
78,050
78,052
acid/g
Empty beaker/g
68,050
68,051
Mass of benzoic
10,000
10,001
acid/g
Mean mass of benzoic acid=10,000+10,001+9,9999/3

78,0501
68,0502
9,9999

=10,000g
Weighing mass of final product
Beaker+product/g
Empty beaker/g
Mass of product/g

74,913
68,050
6,863

74,913
68,051
6,862

74,915
68,0502
6,863

39,613

39,6113

39,6115

37,113
2,500

37,113
2,500

37,115
2,500

Mass of methylbenzoate=6,863g
Weighing the mass of sodium carbonate
Beaker+sodium
carbonate/g
Empty beaker/g
Mass of sodium

carbonate/g
Mass of sodium carbonate =2,500g
Results Analysis

Calculation of the Equilibrium Constant, Keq.

Calculation of a value for the equilibrium constant K eq was based upon the weight of
recovered benzoic acid. In addition, calculation of the percent yield of the synthesis was
based upon the amount of starting benzoic acid used, and another percent yield based
upon the amount of benzoic acid that actually reacted (as determined by the weight of
recovered benzoic acid).
Calculation of the Equilibrium Constant Keq:

Since the volume of the reaction mixture is the same for each component, we can use
moles instead of molarities as the units in our Keq expression. Let Bi = initial moles of
benzoic acid, let Mi = initial moles of methanol, and let X = final moles of methyl
benzoate produced at equilibrium.
Based upon the stoichiometry of equation 1, it was concluded about X, X = final moles
of water produced at equilibrium, X = moles of benzoic acid consumed when equilibrium
is established, and X = moles of methanol consumed when equilibrium is established.
Using our definitions, equation 2 becomes:

Since Bi and Mi are known. All we need to do before we can calculate K eq is to Put X in
terms of something known, like the amount of benzoic acid recovered. Let B f = final
moles of benzoic acid present at equilibrium. Thus B f = Bi - X, or X = Bi - Bf.
Substituting(Bi - Bf) for X in equation 3 gives:

Bi,moles of benzoic acid used=10gbenzoic acid/122g/mole benzoic acid=0,082moles

Bf,moles of benzoic acid recovered=Bi-moles of methylbenzoate produced
= 0,082-0,0504=0,032moles
Mi-mole of methanol=density of methanol x volume used/molecular molar mass of methanol.
=0,791g/mL x 25mL/32,04g/mole
=0,62moles

Keq =( 0,0504)2/0,032x(0,62-0,032)
= 2,54 x 10-3/ 1,882 x 10-2
=1,35 x 10-1

We can now calculate Keq by entering the appropriate values of the moles of benzoic
acid used (Bi), the moles of methanol used (Mi), and the moles of benzoic acid
recovered (Bf) into equation 5.
Calculation of the % Yield based upon initial amount of benzoic acid used:
Let E = moles of methyl benzoate ester obtained. Note that this calculation is valid only
if benzoic acid is the limiting reagent.

% yield

0,0504
0,082

x100

= 61,46%
Calculation of the % Yield based upon amount of benzoic acid that is consumed:

% yield

0,0504
0,0504

x100

= 100%

Discussion
The purpose of washing with saturated sodium chloride is to remove water from the ether later.
Because ether has a highly electronegative oxygen atom in the molecule, water can hydrogen
bond with it.
Consequently, water is slightly soluble in ether and vice versa. A saturated salt solution,

because it is so concentrated, will seek to dilute itself by extracting water from the wet
ether solution. For this reason, ether extracts are often washed with saturated salt
solutions as the last of several washings with aqueous solutions
Theoritical IR and NMR of benzoic acid and methanol:
African Journal of pure and Applied chemistry vol.3(7) pp.199-125 July 2009
Available online at http://www.academicjournals.org/AJPAC

IR and proton NMR of Benzoic Acid :

IR and proton NMR of Methyl Benzoate

The IR and NMR for the obtained methylbenzoate was not performed,so as to be
compared with the the spectroscopes above.This was due to the unavailability of
electricity during the time of doing the experiment.
The crude product was distilled ( crude methyl benzoate) (b.p. 199), collecting anything that
boils between 170C and 200C. Weigh the sample of methyl benzoate and determine the yield.
Weigh the sample of recovered benzoic acid.
The mechanism of the reaction between benzoic acid and methanol is as follows:

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