CH 3522: Unit Operations Lab

Batch Absorption

Batch - R, Group - 05​

Date of Experiment: 22nd January, 2025
Date of Submission: 29th January, 2025 ​

Roll Numbers Group Members

CH22B019 N. Pranavi

CH22B020 Deepanjhan Das

CH22B021 Siddhartha R

CH22B022 P. Ganesh

1.​ Objective
●​ To study gas absorption of CO₂ in water and ethanol solvents.
●​ To calculate solubility and bulk mass transfer coefficient at room temperature for the absorption
of CO₂ gas in water and ethanol solvents.​

2.​ Introduction
​ Absorption is a mass transfer process where atoms, molecules, or ions from one phase (gas,
liquid, or solid) enter another phase. It can be classified as physical (no chemical reaction) or
chemical (involving chemical reactions). Gas absorption involves dissolving a gas into a liquid, with
mass transfer occurring from the gas phase to the liquid phase. The reverse process, gas desorption,
transfers mass from the liquid to the gas phase.

Gas-liquid absorption is a critical process in many chemical and environmental engineering

applications, such as carbon capture, beverage carbonation, and chemical synthesis. The batch
absorption of CO₂ in ethanol and water provides an opportunity to study solubility and mass transfer
phenomena. Understanding the solubility of CO₂ in solvents like ethanol and water is essential for
optimizing industrial processes. Factors such as temperature, pressure, and solvent composition
significantly influence the absorption efficiency. By analyzing the pressure drop of CO₂ in a closed
system containing these solvents, researchers can estimate parameters like Henry's Law constant and
absorption rate, which are crucial for designing efficient gas absorption systems. This knowledge
aids in developing effective methods for carbon capture and utilization, contributing to
environmental sustainability.
 CH 3522: Unit Operations Lab
3.​ Theory
In this experiment we use CO₂ and ethanol & water to perform the absorption process. For each of
them, we take the solvent in the reaction container (vessel) and insert CO₂ in the container through a
supply line. The gas starts to dissolve in the solvent and there is a pressure change due to this reason.
We note the pressure change and the time spent for experimental use.

Figure 1: Absorption process at gas-liquid interface

We use the Ideal gas law to fit the data. It is the equation of state of a hypothetical ideal gas.
It is a good approximation of the behavior of many gases under many conditions, although it may
have its limitations. It was first stated by Emile Clapeyron in 1834 as a combination of Boyle’s law,
Charles’s law and Avogadro’s law. It (used to calculate C from P data) is given as
​ ​ 𝑃𝑉 = 𝑛𝑅𝑇 => 𝐶 = 𝑛/𝑉 = 𝑃/𝑅𝑇 (1)
Where P is the pressure of the gas,
V is the volume of the gas,
n is the amount of gas (in moles),
R is the universal gas constant,
T is the absolute temperature of the gas.

We also used the Peng–Robinson equation of state to fit the data for our experiment by
calculating the C values. This equation of state is used for real gases and it is represented as follows:
𝑅𝑇 𝑎×α
𝑃 = 𝑉𝑚 − 𝑏
− 2 2 (2)
(𝑉𝑚 + 2𝑏𝑉𝑚 − 𝑏 )

Where 𝑉𝑚 is the molar volume of the gas and it is given by 𝑉𝑚 = 𝑉/𝑛, ​

P is the pressure,
T is the absolute temperature,
n is the number of moles,
R is the universal gas constant,
a, b and α are gas constants.
 CH 3522: Unit Operations Lab

We got the expressions for the constants from literature and they are provided below
2 2
0.45724 𝑅 𝑇𝑐
𝑎 = 𝑃𝑐
(3)

0.07780 𝑅 𝑇𝑐
𝑏 = 𝑃𝑐
(4)

0.5 2
α = (1 + κ(1 − 𝑇𝑟 )) (5)
2
κ = 0. 37464 + 1. 54226ω − 0. 26992ω , when ω <= 0. 49 (6)
3 4
κ = 0. 379642 + 1. 48503ω − 0. 164423ω + 0. 016666ω , when ω > 0. 49 (7)
𝑇
𝑇𝑟 = 𝑇𝑐
(8)

Where 𝑇𝑐 is the critical temperature of the gas,

𝑃𝑐 is the critical pressure of the gas and ω is acentric factor.

Also, we know the following relation for mass transfer process,

𝑑𝑐
𝑑𝑡
= 𝑘𝑎(C* - C) (9)
Where C is the concentration of the gas,
𝑠𝑎𝑡
C* (or 𝐶 ) is the solubility of the gas (concentration at saturation) in the liquid,
𝑘𝑎 is the volumetric mass transfer coefficient.

By integrating equation (8) we obtain the following equation,

𝑠𝑎𝑡 𝑖𝑛𝑖 𝑠𝑎𝑡
𝐶 = 𝐶 + (𝐶 − 𝐶 )𝑒𝑥𝑝(− 𝑘𝑎𝑡) (10)
And by multiplying with RT we get (this conversion is possible only for the ideal case)
𝑠𝑎𝑡 𝑖𝑛𝑖 𝑠𝑎𝑡
𝑃 = 𝑃 + (𝑃 − 𝑃 )𝑒𝑥𝑝(− 𝑘𝑎𝑡) (11)
Where 𝑃 is the pressure of the gas,
𝑠𝑎𝑡
𝑃 is the saturation pressure,
𝑖𝑛𝑖
𝑃 is the initial pressure & 𝑡 is the time.
We can use the equation (11) to find the volumetric mass transfer coefficient only for the ideal case
since in the real scenario the interconversion between C & P is not straightforward (coming from PR
equation, eq(2)). Hence rather than using P to fit a model, we will calculate the C from each of ideal
& real equations (eq 1 & 2) and then using equation 10, we will fit a non-linear model to obtain the
estimated C values. And these values will further be used to perform model adequacy checking.
 CH 3522: Unit Operations Lab

4.​ Apparatus Required

●​ Infinite source of CO₂ (supplied from cylinder; as the reaction container is small enough)
●​ Reaction container,
●​ Pressure Gauge attached to container,
●​ Heating plate, Magnetic stirrer,
●​ Measuring cylinder,
●​ Thermocouple, Stopwatch
●​ Distilled water, Ethanol, Gasket,
●​ Clamp & Stands, PVC tubing, Soap Solution

5.​ Schematic of Experimental Setup

Experimental setup includes the following components:

●​ Batch reactor (sealed container/vessel)

●​ Pressure gauge connected to the reactor
●​ Inlet valve for CO₂ gas
●​ Magnetic stirrer below the reactor
●​ Temperature control unit

​ ​
Figure 2: Line Diagram of Experimental Setup​
​
We also show the set-up used while performing the experiment in the laboratory. All the components
provided above can easily be found in the following figure (figure 3) too.
 CH 3522: Unit Operations Lab
​

​
Figure 3: Setup used in Laboratory

6.​ Procedure
Reactor volume measurement:
1.​ First, we measure the volume of the absorption vessel by filling it completely with water, and
measuring the volume of water.
2.​ Volume of the vessel is found to be 135 mL.

Solvent (H₂O/Ethanol) + Gas (CO₂):

1.​ Now fill the vessel with 67.5 mL (half the container) of solvent.
2.​ The vessel is kept at room temperature of around 26.7 ̊C while performing the absorption of
CO₂ in water and it was around 27 ̊C during the absorption experiment of CO₂ in ethanol.
3.​ We close the container and clamp the lid so that it does not move during the experiment after
placing a magnetic palette into the vessel for uniform mixing of the reactants.
4.​ We use a magnetic stirrer at 300-330 rpm for uniform mixing of reactants.
5.​ We also use a silicone gasket to seal the vessel and, using a bracket, close the vessel tightly to
prevent leakage.
6.​ We attach the source of gas to the valve on the lid of the container and open the gas cylinder and
let the CO₂ enter the container.
7.​ We operate at around 3 bar pressure and the pressure decreases with time.
8.​ After the gas enters the container, we detach the valve and observe the pressure readings.
9.​ We take the pressure readings and the time readings corresponding to it till pressure becomes
constant and note them down for calculations.
 CH 3522: Unit Operations Lab

7.​ Experimental Observations

In both cases the RPM was around 300-310 and the vessel volume was 135 mL. All the experimental
observations that were tabulated during the laboratory session are included in order at the end.

In the following two tables, the data for the pressure of CO₂ in the vessel (batch system) containing CO₂
& a solvent is provided with the corresponding time it was measured. In the case of CO₂ absorption in
ethanol the room temperature was set to be 27 ̊C.

CO₂ and EtOH CO₂ and EtOH

​ ​
Time (min) Pressure (Bar) Time (min) Pressure (Bar)
​
0 3.15 16 1.15
​
​ 1 2.30 17 1.15
​ 2 1.90 18 1.15
​
3 1.70 19 1.15

4 1.55 20 1.10

5 1.45 21 1.10

6 1.40 22 1.10

7 1.30 23 1.10

8 1.30 24 1.10

9 1.25 25 1.10

10 1.20 26 1.10

11 1.15 27 1.10

12 1.15 28 1.10

13 1.15 29 1.10

14 1.15 30 1.10

15 1.15 31 1.10

Table 1: Data for CO₂ absorption in Ethanol

 CH 3522: Unit Operations Lab

Now, in the case of CO₂ absorption in water, the room temperature was around 26.7 ̊C.
CO₂ and H₂O CO₂ and H₂O CO₂ and H₂O

Time (min) Pressure (Bar) Time (min) Pressure (Bar) Time (min) Pressure (Bar)

0 3.10 18 2.35 39 1.95

0.5 2.95 19 2.30 40 1.95

1 2.95 20 2.30 41 1.95

1.5 2.90 21 2.30 42 1.95

2 2.85 22 2.25 43 1.95

2.5 2.85 23 2.25 44 1.95

3 2.85 24 2.20 45 1.90

4 2.80 25 2.15 46 1.90

5 2.75 26 2.15 47 1.90

6 2.70 27 2.15 48 1.85

7 2.70 28 2.15 49 1.85

8 2.60 29 2.15 50 1.85

9 2.60 30 2.10 51 1.85

10 2.55 31 2.10 52 1.85

11 2.50 32 2.05 53 1.85

12 2.50 33 2.05 54 1.85

13 2.50 34 2.05 55 1.85

14 2.45 35 2.05 56 1.85

15 2.40 36 2.05 57 1.85

16 2.40 37 2.0 58 1.85

17 2.40 38 2.0

Table 2: Data for CO₂ absorption in Water

 CH 3522: Unit Operations Lab

8.​ Sample Calculations

Since the model estimation requires all the data points we have, it’s insignificant to show sample
calculation for a single tabulation. Rather we will demonstrate the flow of calculations done in
MATLAB to obtain each of the results described and presented in the “Results” section.

We obtain the values of several constants corresponding to CO₂ from literature & these are
𝑇𝑐 = 304. 25 𝐾; 𝑃𝑐 = 7. 39 𝑀𝑃𝑎; ω = 0. 228
Using these values the gas constants are calculated which are coming out to be
5 −2 −2 −5 3
𝑎 = 0. 395895 𝑘𝑔. 𝑚 . 𝑠 . 𝑚𝑜𝑙 ; 𝑏 = 2. 663028 × 10 𝑚
Since for CO2, the ω is less than 0.49, thus using equation 6, we get
κ = 0. 712243 and α is a function of T which we have to take differently for the two different
cases since the room temperature was set to two slightly different values.

3
Thereafter using the corresponding equations we calculated C (𝑚𝑜𝑙/𝑚 ) from the experimental P
values. For ideal state assumption, the equation is straightforward unlike the case of the real state
assumption, where we have used a numerical method fsolve to find the experimental values of C
corresponding to the P (pressure) data. Then we have used a concise form of equation (10) in order
to perform the regression on it, which is as follows:
𝑠𝑎𝑡 𝑖𝑛𝑖 𝑠𝑎𝑡
𝐶 = 𝐶 + (𝐶 − 𝐶 )𝑒𝑥𝑝(− 𝑘𝑎𝑡) => 𝑦 = 𝐴 + 𝐵 × 𝑒𝑥𝑝 (− 𝐷 × 𝑡) (12)
Since the above equation can not be expressed in linear form, a non-linear regression is performed
using MATLAB’s in-built optimization function lsqnonlin which requires some initial values for A,
B & D and therefore they are chosen randomly but keeping in mind of their respective orders for
better convergence of the objective function. Each model thus obtained, is presented in the latter
section along with proper case descriptions.
After this step, respective models are used to calculate the estimated concentration values and these
are further used to recalculate the pressure. And for each of C & P the time-dependent plots are
shown in the latter section too.
Since we know that 𝐶 = 𝑛 / 𝑉, an alternate representation of PR equation (eq 2) is used to
calculate the P using estimated C, which is as follows:
𝑅𝑇 𝑎×α
𝑃 = (1/𝐶) − 𝑏
− 2 2 (13)
(1/𝐶) + (2𝑏/𝐶) − 𝑏
2
And at the end the in order to perform “model adequacy checking”, the 𝑅 score of each model is
computed. The result section ends with providing the amount of moles of CO₂ that got absorbed in
the experiment, estimated from each of these models.​
 CH 3522: Unit Operations Lab
9.​ Results & Discussions
Absorption of CO₂ in Ethanol:
This sub-experiment is modelled using two different equations, one being ideal and the other is the
real equation of state, discussed in “Theory” section of this report. Each of them is discussed below.

Case 1: Ideal behaviour is assumed

The resulting plot we obtained is shown below:

Figure 4: CO₂ absorption in Ethanol estimated using Ideal Equation of State

In the legend the terms “Exp” implies that data to be obtained from experiment and “Ideal State est”
implies the estimation is performed using the ideal equation of state respectively. And further figures
will also have such explanatory legends. The following are the results of concern:

𝑚𝑜𝑑𝑒𝑙: 𝐶(𝑡) = 45. 3149 + (76. 8781)𝑒𝑥𝑝(− 0. 3962 × 𝑡)

𝑠𝑎𝑡 3 𝑖𝑛𝑖 𝑠𝑎𝑡 3
𝑝𝑎𝑟𝑎𝑚𝑒𝑡𝑒𝑟𝑠: 𝐶 = 45. 3149 𝑚𝑜𝑙/𝑚 ; (𝐶 − 𝐶 ) = 76. 8781 𝑚𝑜𝑙/𝑚
−1
𝑚𝑎𝑠𝑠 𝑡𝑟𝑎𝑛𝑠𝑓𝑒𝑟 𝑐𝑜𝑒𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑡: 𝑘𝑎 = 0. 3962 𝑠
𝑖𝑛𝑖 𝑠𝑎𝑡
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐶𝑂2 𝑏𝑒𝑖𝑛𝑔 𝑎𝑏𝑠𝑜𝑟𝑏𝑒𝑑: 𝑛𝑎𝑏𝑠𝑜𝑟𝑏𝑒𝑑 = (𝐶 − 𝐶 ) * 𝑉 = 0. 00518927 𝑚𝑜𝑙𝑒𝑠.
2
𝑚𝑜𝑑𝑒𝑙 𝑎𝑐𝑐𝑢𝑟𝑎𝑐𝑦: 𝑅 = 0. 986774
 CH 3522: Unit Operations Lab
Case 2: Real behaviour is assumed
The resulting plot we obtained is shown below:

Figure 5: CO₂ absorption in Ethanol estimated using Real (PR) Equation of State

In all the results obtained, the V that is used to compute the number of moles of CO₂ being absorbed is
half of the volume of the vessel used which is 67.5 mL. Now in this case, the results we obtained are:

𝑚𝑜𝑑𝑒𝑙: 𝐶(𝑡) = 45. 6903 + (80. 7423)𝑒𝑥𝑝(− 0. 4101 × 𝑡)

𝑠𝑎𝑡 3 𝑖𝑛𝑖 𝑠𝑎𝑡 3
𝑝𝑎𝑟𝑎𝑚𝑒𝑡𝑒𝑟𝑠: 𝐶 = 45. 6903 𝑚𝑜𝑙/𝑚 ; (𝐶 − 𝐶 ) = 80. 7423 𝑚𝑜𝑙/𝑚
−1
𝑚𝑎𝑠𝑠 𝑡𝑟𝑎𝑛𝑠𝑓𝑒𝑟 𝑐𝑜𝑒𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑡: 𝑘𝑎 = 0. 4101 𝑠
𝑖𝑛𝑖 𝑠𝑎𝑡
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐶𝑂2 𝑏𝑒𝑖𝑛𝑔 𝑎𝑏𝑠𝑜𝑟𝑏𝑒𝑑: 𝑛𝑎𝑏𝑠𝑜𝑟𝑏𝑒𝑑 = (𝐶 − 𝐶 ) * 𝑉 = 0. 00545011 𝑚𝑜𝑙𝑒𝑠.
2
𝑚𝑜𝑑𝑒𝑙 𝑎𝑐𝑐𝑢𝑟𝑎𝑐𝑦: 𝑅 = 0. 991497

We have also plotted the estimated pressure values obtained from each of the above 2 models along
with the experimental values of P and showed the result in the end of “Result” section in figure 8. All
these plots significantly justify the experimental values obtained.

Also it is to note that the real state model got better accuracy than the idealized assumptions implying
that the real equation of state (eq 2) captured the relationship between P & t better.
 CH 3522: Unit Operations Lab
Absorption of CO₂ in Water:
This sub-experiment similarly contains the following two cases. And here also the combined plot of
estimated P values from both the models are shown in the end (fig. 9) along with the experimental data.

Case 3: Ideal behaviour is assumed

The resulting plot we obtained is shown below:

Figure 6: CO₂ absorption in H₂O estimated using Ideal Equation of State

Here also, the notations are self-explanatory. So we provide the results we obtained from this case.

𝑚𝑜𝑑𝑒𝑙: 𝐶(𝑡) = 67. 7241 + (52. 1901)𝑒𝑥𝑝(− 0. 0387 × 𝑡)

𝑠𝑎𝑡 3 𝑖𝑛𝑖 𝑠𝑎𝑡 3
𝑝𝑎𝑟𝑎𝑚𝑒𝑡𝑒𝑟𝑠: 𝐶 = 67. 7241 𝑚𝑜𝑙/𝑚 ; (𝐶 − 𝐶 ) = 52. 1901 𝑚𝑜𝑙/𝑚
−1
𝑚𝑎𝑠𝑠 𝑡𝑟𝑎𝑛𝑠𝑓𝑒𝑟 𝑐𝑜𝑒𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑡: 𝑘𝑎 = 0. 0387 𝑠
𝑖𝑛𝑖 𝑠𝑎𝑡
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐶𝑂2 𝑏𝑒𝑖𝑛𝑔 𝑎𝑏𝑠𝑜𝑟𝑏𝑒𝑑: 𝑛𝑎𝑏𝑠𝑜𝑟𝑏𝑒𝑑 = (𝐶 − 𝐶 ) * 𝑉 = 0. 00352283 𝑚𝑜𝑙𝑒𝑠.
2
𝑚𝑜𝑑𝑒𝑙 𝑎𝑐𝑐𝑢𝑟𝑎𝑐𝑦: 𝑅 = 0. 995182

Case 4: Real behaviour is assumed

The resulting plot we obtained is shown below (figure 7):
 CH 3522: Unit Operations Lab

Figure 7: CO₂ absorption in H₂O estimated using Real (PR) Equation of State

𝑚𝑜𝑑𝑒𝑙: 𝐶(𝑡) = 68. 9004 + (54. 6065)𝑒𝑥𝑝(− 0. 0402 × 𝑡)

𝑠𝑎𝑡 3 𝑖𝑛𝑖 𝑠𝑎𝑡 3
𝑝𝑎𝑟𝑎𝑚𝑒𝑡𝑒𝑟𝑠: 𝐶 = 68. 9004 𝑚𝑜𝑙/𝑚 ; (𝐶 − 𝐶 ) = 54. 6065 𝑚𝑜𝑙/𝑚
−1
𝑚𝑎𝑠𝑠 𝑡𝑟𝑎𝑛𝑠𝑓𝑒𝑟 𝑐𝑜𝑒𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑡: 𝑘𝑎 = 0. 0402 𝑠
𝑖𝑛𝑖 𝑠𝑎𝑡
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐶𝑂2 𝑏𝑒𝑖𝑛𝑔 𝑎𝑏𝑠𝑜𝑟𝑏𝑒𝑑: 𝑛𝑎𝑏𝑠𝑜𝑟𝑏𝑒𝑑 = (𝐶 − 𝐶 ) * 𝑉 = 0. 00368594 𝑚𝑜𝑙𝑒𝑠.
2
𝑚𝑜𝑑𝑒𝑙 𝑎𝑐𝑐𝑢𝑟𝑎𝑐𝑦: 𝑅 = 0. 995824

Here also the results imply that the real-case assumption captured a better essence of the theory
behind this experiment compared to the idealised model.

The comparative analysis between the solvents used in the absorption of CO₂ is done in the
“Conclusions” section. This discussion is preceded by two more plots (figure 8 & 9) which include
each of these model scenarios for a single type of solvent and contain the pattern of estimated pressure
data. Though the apparent view of the two estimated models with each solvents from the following
plots show almost similar trend, one might misunderstand the essence captured by each of them and
that’s the reason why model adequacy checking gives us deeper understanding.
CH 3522: Unit Operations Lab

Figure 8: CO₂ absorption in Ethanol

Figure 9: CO₂ absorption in H₂O

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10.​ Conclusions
●​ The absorption for carbon dioxide is thus studied with two different solvents. And from the
values of mass transfer coefficient it’s vivid that CO₂ gets absorbed in ethanol with a greater
rate than that of in water.
●​ The number of models of CO₂ that got absorbed is also higher in ethanol.
●​ The above findings also follow the literature.
●​ With each of the solvents, the real-state models capture better essence than the idealised mod-​
2
els since the 𝑅 is closer to 1 in the real-state models than the other counterparts.
●​ These studies help researchers make better decisions in the context of choice of solvents which
further helps in design aspects in industrial level where processes like CO₂ capture are taken
care of.​

11.​ References
I.​ CH 3030 Applications of Mass Transfer Course Notes.
II.​ Treybal, Robert E. Mass-transfer Operations. New York: McGraw-Hill, 1980.
III.​ Source of literature data used for equations of state & to find values of the constants.
IV.​ Carbon Capture Science & Technology, to study application of CO₂ absorption.
V.​ The GitHub repository contains all the related data and coded scripts used for
calculations.
CH 3522: Unit Operations Lab
CH 3522: Unit Operations Lab