Exercise 13A report

Group No. 3

21/10/2021

Liudvikas Launikonis s194723@student.dtu.dk

Group No. 3 13A Organic Synthesis 21/10/2021

Abstract
The purpose of the exercise was to perform large-scale esterification of methyl formate. The reaction was
carried out in a semi-batch reactor which had its temperature regulated by a heating jacket. The reaction
kinetics appear to be governed by the temperature and formation of hydrogen bonds between the reactants
and byproduct water. The equilibrium constant at 40°C was determined to be 1.24. The product was
continuously isolated from the reactor vessel using a low boiling point. The synthesis concluded with a total
yield of 78.59%, furthermore 99.5% purity was achieved.

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Table of Contents
Abstract ......................................................................................................................................................... 2
List of symbols............................................................................................................................................... 4
Introduction .................................................................................................................................................. 5
Experimental ................................................................................................................................................. 7
Results and Analysis ...................................................................................................................................... 8
1. Graphs of TI2, TI4, WT2 and product concentration versus time. ........................................................ 8
2. The composition of the initial product, the distillate at ~40°C equilibrium, and the final product
composition in a T-xy diagram. ............................................................................................................... 10
3. Mass balance and process yield for the equilibrium situation at ~40°C............................................. 10
4. The reaction equilibrium constant at ~40°C, based on mass balance in question no. 3. ................... 11
5. Comparison of experimentally and theoretically determined equilibrium constants. ...................... 11
6. Total yield and product purity. ........................................................................................................... 12
7. Order of reaction and the size of the rate constant. .......................................................................... 12
8. Volume of reaction mixture. ............................................................................................................... 14
9. Carrying out the reaction as a continuous process............................................................................. 15
Discussions and conclusions ....................................................................................................................... 16
Calculation examples .................................................................................................................................. 17
References .................................................................................................................................................. 18

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List of symbols
Symbol Description Unit or Value
T Temperature [°𝐶]
P Pressure [bar]

V Volume [𝐿]
R Ideal gas constant [J/mol K]
t Time [ℎ]

m Mass [kg]

ρ Liquid Density [𝑘𝑔/𝐿]

M Molecular Weight [g/mol]

N Molar quantity [mol]

C Concentration [mol/ L]
Molar fraction of methyl
x -
formate in gas phase
Molar fraction of methyl
y -
formate in vapour phase
γ Molar fraction -
r Rate of reaction [𝑚𝑜𝑙/𝐿]

k Rate constant [ℎ−1 ]

ΔG𝑓° Gibbs standard free energy [𝐽/𝑚𝑜𝑙]

ΔH𝑓° Standard heat of formation [𝐽/𝑚𝑜𝑙]

K Equilibrium constant -

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Introduction
The unit operation performed in this lab exercise was organic synthesis. The task was to perform
esterification of methyl formate from formic acid and methanol with sulphuric acid acting as a catalyst. The
reactor used was a 20-liter spherical glass bowl that had attached an electrically heated jacket and a
pneumatically driven agitator. To separate and capture the gaseous product, a Raschig-ring filled rectifying
column with a water-cooled condenser was used. The process can be classified as semi-batch due to the
continuous removal of the product. The operational steps are:

• Inert the vessels T1 and T4 by adding N2.

• Allow the flow of cooling water to the condenser.

• Add methanol to T1 and transfer to T4.

• Add catalytic sulphuric acid to T1, turn on the stirrer and transfer to T4.

• Add formic acid to T1 and slowly transfer to T4.

• Proceed with monitoring the reaction. If it is desired to push the equilibrium towards the products,
the heating jacket surrounding the reactor vessel can be turned on.
The P&I of the system can be found below:

Figure 1. The relevant section of the P&I diagram for the organic synthesis
exercise.

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It is paramount for the training of chemical engineers to familiarize with this unit operation since it is one
of the most common operations in the industry. For instance, a large variety of organic compounds are
synthetized in petrochemical, pharmaceutical, and biochemical industries. By the same token, the primary
goal was to attain a deeper understanding of and to verify the theory behind the process.

Theory
The synthesis is an esterification between formic acid and methanol, catalyzed by sulphuric acid.

HCOOH + CH3 OH ↔ HCOOCH3 + H2 O

Reaction 1. Methyl formate synthesis reaction scheme.

Methanol is kept in slight excess to minimize residual formic acid. The equilibrium constant can be
expressed in terms of concentrations and activity coefficients:

{𝐶}{𝐷} 𝐶𝐶𝛾 ∙ 𝐶𝐷𝜀

𝐾= = (1)
{𝐴}{𝐵} 𝐶 𝛼 ∙ 𝐶 𝛽
𝐴 𝐷

Gibbs-Helmholtz equation permits to calculate an equilibrium constant at another temperature:

∆𝐻𝑅o 1 1 ∆𝐶𝑝 𝑇 𝑇0
ln(𝐾𝑇 ) = ln(𝐾𝑇0 ) − ∙( − )+ ∙ ln ( + − 1) (2)
𝑅 𝑇 𝑇0 𝑅 𝑇0 𝑇
Where 𝐾𝑇 is equilibrium constant at a chosen temperature 𝑇. 𝑇0 is the initial temperature. The rate of
reaction r is assumed to be expressed as:
𝑑 𝐶𝐶
−𝑟𝐴 = 𝑟𝐶 = = 𝑘 𝐶𝐶𝑛 (3)
𝑑𝑡
Where k is the rate constant and n is the order of reaction. 𝑟𝐶 is the rate of formation of methyl formate and
equal to the rate of disappearance of formic acid 𝑟𝐴 .
The Arrhenius equation defines the relationship between rate constant, activation energy, and temperature:
−𝐸𝐴
𝑘 = 𝐴 ∗ 𝑒 ( 𝑅∗𝑇 ) (4)
The mass balance for methyl formate in the esterification process can be written as:

Formic acid reacted = Product formed

= Product removed by evaporation + product accumulated in reactor
The concentration of formic acid/methanol at a particular timepoint can be expressed in terms of initial
molar quantity 𝑁𝐴𝑜 , the volume of reaction mixture 𝑉(𝑡) and the degree of reaction X:

𝑁𝐴 𝑁𝐴𝑜 (1 − 𝑋)
𝐶𝐴 = = (5)
𝑉(𝑡) 𝑉(𝑡)
assuming ∆𝑉𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 ~0:

𝑉(𝑡) = 𝑉(0) − volume of evaporated product

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Correlation between weight% of methyl formate and the density ρ at 25°C of the solution.

weight%methyl formate = 546.18 𝜌 − 430.57 (6)

Percent yield can be expressed as:

𝑚𝑎𝑐𝑡𝑢𝑎𝑙 𝑜𝑓 𝑝𝑟𝑜𝑑𝑢𝑐𝑡
%𝑦𝑖𝑒𝑙𝑑 = ∙ 100% (7)
𝑚𝑡ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑜𝑓 𝑝𝑟𝑜𝑑𝑢𝑐𝑡

Percent purity can similarly be said to be equal to:

𝑚𝑑𝑒𝑠𝑖𝑟𝑒𝑑 𝑝𝑟𝑜𝑑𝑢𝑐𝑡
%𝑝𝑢𝑟𝑖𝑡𝑦 = ∙ 100% (8)
𝑚𝑐𝑟𝑢𝑑𝑒 𝑝𝑟𝑜𝑑𝑢𝑐𝑡

The product volume can be calculated to be:

6.9 ∗ (𝑚𝑐𝑟𝑢𝑑𝑒 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 − 𝑚𝑚𝑒𝑡ℎ𝑦𝑙 𝑓𝑜𝑟𝑚𝑎𝑡𝑒 ) (9.42 ∙ 𝑚𝑚𝑒𝑡ℎ𝑦𝑙 𝑓𝑜𝑟𝑚𝑎𝑡𝑒 )

𝑉𝑐𝑟𝑢𝑑𝑒 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 = + (9)
5.46 9.15

Where 6.9 and 5.46 are numbers that define proportionality between mass and volume for methanol.
Similarly, 9.42 and 9.15 define the relationship for methyl formate.
The weight of methyl formate was calculated using a cumulative mathematical relationship:

𝑡𝑖𝑚𝑒𝑝𝑜𝑖𝑛𝑡 2 𝑡𝑖𝑚𝑒𝑝𝑜𝑖𝑛𝑡 1 𝑤𝑒𝑖𝑔ℎ𝑡%𝑚.𝑓𝑜𝑟𝑚. 𝑡𝑖𝑚𝑒𝑝𝑜𝑖𝑛𝑡 2 𝑡𝑖𝑚𝑒𝑝𝑜𝑖𝑛𝑡 1

𝑚𝑚.𝑓𝑜𝑟𝑚. = 𝑚𝑚.𝑓𝑜𝑟𝑚. + ∗ (𝑚𝑐𝑟𝑢𝑑𝑒 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 − 𝑚𝑐𝑟𝑢𝑑𝑒 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 ) (10)
100
The standard equation relating Gibbs free energy change and equilibrium constant:
∆𝐺 𝑜 = −𝑅𝑇𝑙𝑛(𝐾) (11)
Where R is the gas constant and T is the reference temperature (standard conditions) at which the Gibbs
free energy change values were conceived.

Experimental
Before adding reagents to begin the reaction, the system was inerted with N2. Firstly, methanol was added
to a holding tank from which it was poured into the reactor. Thereafter, first sulfuric acid and afterwards
formic acid were added slowly over ten minutes to prevent excessive heat. While adding the compounds,
the temperature of the mixture must not have exceeded 45°C. Furthermore, the cooling water system was
started to prevent a temperature surge. When all compounds had been added and the temperature had
dropped, the vessel was kept at 40°C until product distillation had considerably slowed down. When the
equilibrium at 40°C had settled, the temperature of the reactor was stepwise raised to 70°C over a period
of one and a half hour.

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Table 1. Quantities of reactants.

Formic acid Methanol Sulfuric acid, 96-98%

Mass 7.0 kg 5.46 kg 0.66 kg
Volume 5.75 L 6.9 L 0.36 L
Amount 152.3 mole 170.4 mole 6.7 mole

The density of the product was measured every 10 minutes during the synthesis. To get consistent
measurements, all sample tubes were cooled in a water bath prior to analysis. Once the reaction had finished,
the heating jacket was turned off and the residual reaction liquid inside the reactor was disposed of.

Results and Analysis 35

1. Graphs of TI2, TI4, WT2 and
product concentration versus time.
Temperature, [°C]

Throughout the experiment different 30

variables of interest were logged by the
help of a computer program.
The sensor TI4 measured the temperature 25
inside the reactor. The temperature was
controlled throughout the experiment. At
the beginning, the reactor was charged
slowly with formic acid to avoid an 20
exothermic meltdown. Throughout most 0.00 0.70 1.39 2.09 2.78 3.48 4.17 4.87
of the experiment, the temperature was Elapsed time, [h]
kept at 40°C until the equilibrium point
Figure 2. Product vapour temperature at the bottom of the cooling
(around timepoint 3.66 h). Subsequently,
column with respect to elapsed time.
the temperature was increased stepwise
up to 70°C. It can be observed that the
distillation of the product began at 75
approximately 0.5 h (see Figure 3). This 70
is because that was the point at which the 65
60
Temperature, [°C]

temperature became high enough for the

product to evaporate. Subsequently, the 55
product accumulated at a rate that 50
decreased as it was reaching the point of 45
equilibrium. At around 3.66 h the 40
distillation of the products was sped up by 35
ramping up the reactor temperature. 30
25
20
0.00 0.70 1.39 2.09 2.78 3.48 4.17 4.87
Elapsed time, [h]
Figure 3. Temperature inside the reactor with respect to elapsed time.

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It can be observed that the vapour

temperature at the bottom of the 8.000
cooling column did not change at all
for a substantial part of operating time.
Since it was stated in the manual that 6.000
the vapour temperature should be

Weight, [kg]
around 33°C, while the graph shows
that it suddenly jumped to reference 4.000
temperature over a very short period
(see Figure 2), it is assumed that there
was a measurement collection glitch. 2.000

As the product consists of only methyl

formate and methanol; by the same 0.000
token, we are given the weight percent 0.00 0.70 1.39 2.09 2.78 3.48 4.17 4.87
of methyl formate as a function of Elapsed time, [h]
density, it is possible to deduce the
concentration of each by knowing Figure 4. Product weight accumulation with respect to elapsed time.
their densities and by calculating the
volume occupied by these two 15.22
species. While the reactor was kept at 15.2
Product concentration, [mol/L]

40°C, the concentration slowly 15.18

increased to 15.2 mol/L. As soon as 15.16
the reactor temperature was raised, the
15.14
concentration started to decrease due
15.12
to the methanol enrichment of the
distillate. 15.1
15.08
15.06
15.04
15.02
15
0.66 1.15 1.65 2.15 2.64 3.14 3.66 4.39
Elapsed time, [h]

Figure 5. Concentration of methyl formate in product tank with respect to

elapsed time.

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2. The composition of the initial product, the distillate at ~40°C equilibrium, and the final
product composition in a T-xy diagram.

Figure 6. Vapor-liquid equilibrium diagram for the methanol – methyl formate mixture. Pressure equal to
1 bar.

From the T-xy diagram it can be inferred that all products—initial, equilibrium, and final—were formed in
the gas phase with a molar fraction close to 0.9. As the product passed through the rectifying column, it
cooled and reached the dewpoint line, subsequently split into two phases, shortly thereafter passed the
bubble point, and finally condensed into a liquid phase. Where the product was split into two phases, the
gas was primarily volatile methyl formate, while in the liquid phase methyl formate had a molar fraction
bigger than one half. These conditions allowed for the separation of the product because methanol
condensed and could not pass through the column. However, methyl formate in the liquid phase was
returned to the reaction mixture as well. This means that, to be successfully separated, some methyl formate
molecules had to come up to the column several times.

3. Mass balance and process yield for the equilibrium situation at ~40°C.
It was assumed that all methyl formate was in the product vessel. Sulfuric acid is not considered in the mass
balance because it is a catalyst.

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Table 2. Species mass balance.

HCOOH CH3OH HCOOCH3 H2O
m(initial) 7.0 kg 5.46 kg 0 kg 0 kg
m(equilibrium) 3.77 kg 3.2 kg 4.2 kg 1.28 kg
m(end) 1.5 kg 1.62 kg 7.19 kg 2.16 kg

It can be observed that a significant percentage of total mass is made up of water.

4. The reaction equilibrium constant at ~40°C, based on mass balance in question no. 3.
By utilizing the mass balance and given densities, volumes for each species were found. These volumes—
together with number of moles—were used to calculate concentrations at equilibrium. Finally, the
experimental equilibrium constant was determined by formula (1) :

𝐶𝑤𝑎𝑡𝑒𝑟 1
𝐾𝐶 = = 0.07145
𝐶𝑚𝑒𝑡ℎ𝑎𝑛𝑜𝑙 1 ∗ 𝐶𝑓𝑜𝑟𝑚𝑖𝑐 𝑎𝑐𝑖𝑑 1

As can be observed, at equilibrium the reaction had a primitive equilibrium constant less than one. This
would imply that the reaction had begun to favour the reactants, which can be rebuked by looking at
experimental data (see Figure 4). The error can be largely attributed to unknown activity coefficients.
Reaction activity determination is analysed further in the discussion section.

5. Comparison of experimentally and theoretically determined equilibrium constants.

First, the change in Gibbs free energy was found by adding up the Gibbs free energy change of formation
for the products and reactants, and then taking the difference between them. In the following table the
∆𝐺𝑓𝑜 (𝑙𝑖𝑞. ) of formic acid is 20 kJ/mol greater than the value stated in the manual. This was done because
the manual stated that the value of formic acid can vary by as much as 20 kJ/mol. What is more, a value
with an increase of only 10 kJ/mol was also included to see how that affects the equilibrium constant.
Finally, equilibrium constant was calculated by the equation (11). The results can be seen in the tables
below:
Table 3. Gibbs free energy and free energy change of formation.
Formic acid Methanol Methyl formate Water
∆𝐺𝑓𝑜 (𝑙𝑖𝑞. )𝑘𝐽/𝑚𝑜𝑙 -341.4 -166.6 -280 -237.1
𝑜
∆𝐺 𝑘𝐽/𝑚𝑜𝑙 -9.1

Table 4. Gibbs free energy and free energy change of formation.

Formic acid Methanol Methyl formate Water

∆𝐺𝑓𝑜 (𝑙𝑖𝑞. )𝑘𝐽/𝑚𝑜𝑙 -351.4 -166.6 -280 -237.1
∆𝐺 𝑜 𝑘𝐽/𝑚𝑜𝑙 -0.9

To account for the temperature deviation from standard conditions, integrated Gibbs-Helmholtz equation
(2) was utilized. The results can be seen in the following table:

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Table 5. Equilibrium constants at standard and operating conditions.

Formic acid ∆𝐺𝑓𝑜 increased by Formic acid ∆𝐺𝑓𝑜 increased by

20 kJ/mol 10 kJ/mol
𝐾298𝐾 39.36 1.44
𝐾313𝐾 33.99 1.24

When Gibbs free energy of formation for formic acid was adjusted by 10 kJ/mol, the resulting equilibrium
constant is equal to 1.24 at equilibrium operating conditions. This is very close to what was observed in
real life. The theoretical value is a much better approximator of the real equilibrium constant value than the
experimental one with missing activity coefficients. See the discussion section for a further discussion
regarding activity of reaction.

6. Total yield and product purity.

Table 6. Yields and purity.
Total yield Percent yield Product purity
7.19 kg 78.59% 94.5%

For the calculation of yield and purity, a cumulative mathematical relationship (10) was used. Since at
different time points the temperature can differ, the new crude product coming out of the condenser might
be split into different molar fractions than the product at a previous timepoint. Therefore, the fraction of
methyl formate in the product stream was multiplied only with the net increase in product mass since the
last time stamp. This was then added to the mass at a previous time stamp. Performing the calculations by
this method, instead of continuing to multiply the total mass by the dynamic weight percentage, gave a
yield that is about 5 percent higher. Furthermore, the purity improved by about 6 percent.

7. Order of reaction and the size of the rate constant.

First, two modes of operation must be defined:
1. From 0.66 hours to 3.66 hours the reactor was approaching equilibrium.
2. Thereafter, the temperature was 14
gradually increased by 5°C from 12
Concentration, [mol/L]

40°C to 70°C.
10
It can be noted from the concentration of
8
formic acid with respect to time graph
(see Figure 7) that the concentration was 6
decreasing at a constant rate during the 4
first mode of operation. As the
2
temperature creeped upward, the rate of
consumption of formic acid—and 0
likewise rate of production of methyl 0.66 0.98 1.31 1.65 1.98 2.31 2.64 2.98 3.31 3.66 4.22 4.59 4.91
formate—steeply increased and reached a Elapsed time, [h]
maximum at 4.22 hours, or 55°C.
Afterwards, the rate sharply decreased Figure 7. Formic acid concentration with respect to elapsed time.

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again. The decrease can be attributed to a low amount of reactants because pushing the equilibrium towards
the products was performed towards the end of the synthesis. Another possibility is that a backwards
reaction rate became more favourable and started to lessen the product output.
By examining the first mode of operation more closely, the ratios between initial/final concentrations and
reaction rates can be computed:
Table 7. Ratios of initial/final concentrations and reaction rates during the first mode of operation.

Initial/Final concentrations Initial/Final reaction rates

Ratio 0.876 0.701

As the ratios are so close to each other, it can be approximated that order of reaction is equal to 1. Since the
finite difference theorem was used to approximate the derivative of concentration with respect to time
(reaction rate), the deviations from the trendline are assumed to be approximation inaccuracies (see Figure
9).
Subsequently, the rate constant was then determined simply by dividing the rate of reaction at equilibrium
by the concentration of formic acid.
𝑘 ≅ 0.05 ℎ−1
The assumption is valid because sharp changes in reaction rate after an increase in temperature are due to
a changed rate constant k. From the Arrhenius equation it follows that rate constant k depends on
temperature via an exponential function (4). Moreover, linear changes in temperature reproduce exponential
behaviour as evidenced by the 2nd mode of operation in the reaction rate graph.

Figure 8. Reaction rate with respect to elapsed time.

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Figure 9. Concentration of formic acid versus reaction rate at various timestamps

during operational mode 1.

8. Volume of reaction mixture.

The volume for the reaction mixture was logically deduced to be:
𝑉(𝑡) = 𝑉𝑚𝑒𝑡ℎ𝑎𝑛𝑜𝑙𝑟𝑒𝑎𝑐𝑡𝑜𝑟 (𝑡) + 𝑉𝑓.𝑎𝑐𝑖𝑑 (𝑡) + 𝑉𝑤𝑎𝑡𝑒𝑟 (𝑡)

Where the volumes for each component follow the general formula:
𝑚𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 (𝑡) 𝑛𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 (𝑡) ∗ 𝑀𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡
𝑉𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 (𝑡) = =
𝜌𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 𝜌𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡

And the methanol inside the reactor is accounted for by:

𝑉𝑚𝑒𝑡ℎ𝑎𝑛𝑜𝑙𝑟𝑒𝑎𝑐𝑡𝑜𝑟 (𝑡) = 𝑉𝑚𝑒𝑡ℎ𝑎𝑛𝑜𝑙𝑡𝑜𝑡𝑎𝑙 (𝑡) − 𝑉𝑚𝑒𝑡ℎ𝑎𝑛𝑜𝑙𝑝𝑟𝑜𝑑𝑢𝑐𝑡 (𝑡)

It was assumed that the reaction mixture contains no methyl formate due to the difficulty of inferring such
variable. As we saw in question 2, it is likely that some methyl formate in the liquid phase got returned to
the reactor. Nevertheless, this amount is relatively insignificant in the big picture.
The difference between the sum of initial and final reaction and product volumes shows that the total
volume increased by 0.169L . This can be attributed to changing molar fractions of species with different
densities. Overall, however, it is reasonable to assume that the volume of the reaction is constant since the
reaction in reaction mixture occurs without a sizeable gas phase.

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13.044

11.044

9.044
Volume, [L]

7.044

5.044

3.044

1.044
0.66 1.16 1.66 2.16 2.66 3.16 3.66 4.16 4.66
Elapsed time, [h]
V of reaction mixture V of crude product

Figure 10. Calculated volumes of reaction mixture and crude product.

9. Carrying out the reaction as a continuous process.

The reaction could be continuously performed if the reactor type was Continuously Stirred Tank Reactor
(CSTR) or Plug Flow Reactor (PFR). Moreover, improving the final conversion is of interest. Therefore,
by utilizing the mole balances for CSTR and PFR, volumes of reactors with respect to recirculation ratio
can be derived. Recirculation dilutes the feed; consequently, it also reduces the reaction rate. Nevertheless,

Figure 11. Volumes with respect to recirculation ratio for PFR (left) and CSTR (right).

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reducing the reaction rate helps to control the reactor temperature. The desired final conversion was selected
to be 0.9, an increase from 0.786 achieved in this unit plant exercise.
As can be observed, a PFR yields a high conversion with a much smaller volume than what would be
required for a CSTR. Thus, the reactor of choice would be plug flow. The total feed concentration and rate
𝑚𝑜𝑙
constant were taken to be equal to the rate of molar consumption of formic acid doubled — 𝐹0 = 40 ℎ
— and rate constant during the first mode of operation of unit plant, 𝑘 = 0.05 ℎ−1. The molar consumption
is doubled because methanol is being consumed at the same rate as formic acid. To make the reactor
operation safer, the sulphuric acid should be premixed with the methanol feed line. Furthermore, as the
reaction takes place in the liquid phase and the stoichiometric coefficients are equal to one, the total
volumetric flow rate can be assumed to be constant and equal to volumes occupied by 20 moles of either
reactant added together. 20 moles were chosen for the calculation of volumetric flow rate because that is
𝐿
how many moles of each reactant is consumed per one hour. The volumetric flow rate is then = 1.563 .
ℎ

Discussions and conclusions

On a closer inspection, the component for methyl formate is missing from the equilibrium constant. This is
due to the semi-batch nature of the reactor, as the product was continuously being drawn out. Furthermore,
the activity coefficients are unknown. Since the reaction rate at equilibrium had become quite small, it can
be hypothesized that the equilibrium constant has a value close to and slightly above that of 1. To conserve
the balance, species concentrations must then take activity coefficients in their exponents. Activities of all
species must be logically interlinked due to hydrogen bond formation between water and hydroxyl groups
present on both methanol and formic acid. As the water fraction increases, hydrogen bond formation starts
competing with the acid-facilitated creation of nucleophile-electrophile systems. Moreover, reaction
direction depends exponentially on the favourability of a particular reaction direction activation barrier. It
can be hypothesized that the activities of methanol and formic acid are a function of concentration of water.
The higher the fraction of reactants hydrogen-bound to water, the higher prevention for forming methyl
formate. From Raoult’s law it is known that the activity coefficient for water in an ideal solution is equal
to the molar fraction of water (Osato Miyawaki, 1997). Our solution is surely not ideal due to temperature
changes, mixing, and a slight increase in total volume after operation. Nevertheless, for investigative
purposes this can be taken as a starting point for development of a mathematical relationship that would
approximately model the change in equilibrium constant as a function of time. After some numerical
experimentation, the following formula, where 𝛾𝑤𝑎𝑡𝑒𝑟 is the molar fraction of water, was found:

(𝑙𝑛(𝐶𝑤𝑎𝑡𝑒𝑟 )−𝑙𝑛(𝐶𝑓𝑜𝑟𝑚𝑖𝑐 𝑎𝑐𝑖𝑑 )+𝑙𝑛(𝐶𝑚𝑒𝑡ℎ𝑎𝑛𝑜𝑙 )) (𝑙𝑛(𝐶𝑤𝑎𝑡𝑒𝑟 )−𝑙𝑛(𝐶𝑚𝑒𝑡ℎ𝑎𝑛𝑜𝑙 )+𝑙𝑛(𝐶𝑓𝑜𝑟𝑚𝑖𝑐 𝑎𝑐𝑖𝑑 ))

(𝛾𝑤𝑎𝑡𝑒𝑟 ) (𝛾𝑤𝑎𝑡𝑒𝑟 )
𝑒 𝑒
𝐾≈ +
2 2
to yield a descriptive graph:

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Figure 12. Approximation of the equilibrium constant with the assumption that product formation is
chiefly impeded by the molar fraction of water in reaction mixture.
As can be observed, the reaction favours the products in the beginning of reaction and then drops to around
1.1. Thereafter, it remains at that level for the remainder of the equilibrium mode of operation. When the
temperature is increased, the reaction starts favouring the products again because additional temperature
increases molecular vibrations, thus helping reactants overcome hydrogen bonds and form methyl formate.
It must be noted, however, that the method is a pure hypothetical approximation and that the proof of it is
beyond the scope of this report. To conclude, the reaction kinetics seem to be governed by hydrogen bond
formation between product water and the reactants as well as temperature. From the general equation
connecting Gibbs free energy change and equilibrium constant, the reaction at 40°C was calculated to
proceed with an equilibrium constant of 1.24.
A particularly interesting observation is that operating at 55°C with maximum rate does not severely impact
the purity of the product. Knowing that the purity of the product reached its maximum at equilibrium, the
percent purity change between equilibrium and 55°C can be calculated to be only -0.148. This means that
the reactor could be operated at a higher temperature with insignificant detrimental effects.
Over the course of the synthesis, a total yield of 78.59% was achieved with an overall purity of 94.5%.

Calculation examples
𝛾
𝐶𝐶 ∙ 𝐶𝜀𝐷 8.8131
𝐾= 𝛽
= = 0.07145
𝐶𝛼𝐴 ∙ 𝐶𝐷 10.0424 ∗ 12.2832

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∆𝐻𝑅o 1 1 ∆𝐶𝑝 𝑇 𝑇0
ln(𝐾𝑇 ) = ln(𝐾𝑇0 ) − ∙( − )+ ∙ ln ( + − 1) =
𝑅 𝑇 𝑇0 𝑅 𝑇0 𝑇
((−386.1 − 285.8) − (−425.0 − 239.2)) ∗ 1000
= ln(1.437979001) −
𝑅
1 1 (75.3 + 120 − 99 − 81) 313 298
∙( − )+ ∙ ln ( + − 1) => 𝐾313 = 1.2417
313 298 8.314 298 313
𝑁𝐴𝑜 (1 − 𝑋) 152.3 ∗ (1 − 0.467) 𝑚𝑜𝑙
𝐶𝐴 = = = 10.05
𝑉(𝑡) 8.077 𝐿
weight%methyl formate = 546.18 ∗ 𝜌 − 430.57 = 546.18 ∗ 0.9605 − 430.57 = 94.035
𝑚𝑎𝑐𝑡𝑢𝑎𝑙 𝑜𝑓 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 4.275
%𝑦𝑖𝑒𝑙𝑑 = ∙ 100% = ∗ 100% = 46.72%
𝑚𝑡ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑜𝑓 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 9.15
𝑚𝑑𝑒𝑠𝑖𝑟𝑒𝑑 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 4.275
%𝑝𝑢𝑟𝑖𝑡𝑦 = ∙ 100% = ∗ 100% = 95.04%
𝑚𝑐𝑟𝑢𝑑𝑒 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 4.498

6.9 ∗ (𝑚𝑐𝑟𝑢𝑑𝑒 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 − 𝑚𝑚𝑒𝑡ℎ𝑦𝑙 𝑓𝑜𝑟𝑚𝑎𝑡𝑒 ) (9.42 ∙ 𝑚𝑚𝑒𝑡ℎ𝑦𝑙 𝑓𝑜𝑟𝑚𝑎𝑡𝑒 )

𝑉𝑐𝑟𝑢𝑑𝑒 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 = +
5.46 9.15
6.9 ∗ (4.498 − 4.275) 9.42 ∗ 4.275
= + = 4.6829 𝐿
5.46 9.15
𝑡𝑖𝑚𝑒𝑝𝑜𝑖𝑛𝑡 2 𝑡𝑖𝑚𝑒𝑝𝑜𝑖𝑛𝑡 1 𝑤𝑒𝑖𝑔ℎ𝑡%𝑚.𝑓𝑜𝑟𝑚. 𝑡𝑖𝑚𝑒𝑝𝑜𝑖𝑛𝑡 2 𝑡𝑖𝑚𝑒𝑝𝑜𝑖𝑛𝑡 1
𝑚𝑚.𝑓𝑜𝑟𝑚. = 𝑚𝑚.𝑓𝑜𝑟𝑚. + ∗ (𝑚𝑐𝑟𝑢𝑑𝑒 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 − 𝑚𝑐𝑟𝑢𝑑𝑒 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 )
100
= 4.199 + 0.94 ∗ (4.498 − 4.418) = 4.274 𝑘𝑔

References
IHUN. (2019, 05 29). ORGANIC SYNTHESIS. DTU.

Osato Miyawaki, A. S. (1997). Activity and Activity Coefficient of Water in Aqueous Solutions and Their
Relationships with Solution Structure Parameters. Bioscience, Biotechnology, and Biochemistry,
5. Retrieved from
https://www.tandfonline.com/doi/pdf/10.1271/bbb.61.466#:~:text=When%20the%20solution%
20is%20ideal,solution%20according%20to%20Raoult%27s%20law.&text=where%20Xs%20is%20
the%20molar%20fraction%20of%20solute.&text=v%2C%20number%20of%20ions%20after%20c
omplete%

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