CH 3522: Unit Operations Lab
Adsorption Kinetics
Batch - R, Group - 05
Date of Experiment: 29th January, 2025
Date of Submission: 4th February, 2025
Roll Numbers Group Members
CH22B019 N. Pranavi
CH22B020 Deepanjhan Das
CH22B021 Siddhartha R
CH22B022 P. Ganesh
1. Objective
● To determine the mass transfer coefficient 𝐾𝑐 for batch adsorption of dye on activated charcoal.
● To compare the mass transfer coefficients with correlation-derived estimates for similar systems.
2. Introduction
Adsorption kinetics is a fundamental aspect of chemical engineering, playing a crucial role
in processes such as catalysis, water treatment, and separation technologies. Understanding the rate
at which adsorbates adhere to solid surfaces enables engineers to design and optimize systems for
efficient contaminant removal and resource recovery.
Figure 1: Adsorption Phenomenon
CH 3522: Unit Operations Lab
In this experiment, we investigate the adsorption kinetics of methylene blue dye onto activated
charcoal. By monitoring the concentration of the dye over time, we aim to determine key parameters
such as the rate constant and equilibrium adsorption capacity. These parameters are essential
for modeling adsorption processes and scaling them for industrial applications.
Through this study, we will apply kinetic models to experimental data, enhancing our understanding
of the mechanisms governing adsorption. This knowledge is vital for the development of effective
adsorption-based systems in various chemical engineering fields.
3. Theory
Few of the important theoretical aspects behind the current experiments are explained below.
Adsorption
Adsorption is a surface phenomenon where molecules or particles (adsorbates) adhere to the
surface of a solid or liquid material (adsorbent). This process is distinct from absorption, where
substances are taken up into the bulk of the material. The adhesion occurs due to intermolecular
forces between the adsorbate and the surface of the adsorbent.
Adsorption can be classified into two types based on the nature of the interaction between the
adsorbate and adsorbent:
● Physisorption (Physical Adsorption):
a. Involves weak van der Waals forces.
b. It is a reversible process that occurs at lower temperatures.
c. There is no significant electron transfer or chemical bonding involved.
d. Example: Adsorption of gases like oxygen or nitrogen on activated carbon.
● Chemisorption (Chemical Adsorption):
a. Involves strong chemical bonds, either covalent or ionic.
b. This process is irreversible and occurs at higher temperatures.
c. It is specific to certain adsorbent-adsorbate pairs.
d. Example: Adsorption of oxygen on metal surfaces during catalysis.
In a batch adsorption experiment, commonly used to study adsorption in liquids, a known
amount of dye is introduced into a liquid with an initial concentration. The system is then stirred or
agitated, and at intervals, samples are taken to measure the concentration of the dye as it decreases
due to adsorption until it reaches a constant value, signifying equilibrium.
UV-Vis Spectroscopy for Dye Concentration Measurement
UV-Vis spectroscopy is a powerful technique to analyze the concentration of substances,
particularly dyes, in a solution. A double-beam UV-Vis spectrophotometer is typically used, where
CH 3522: Unit Operations Lab
one beam passes through a reference solution and the other through the sample solution. The
intensity of light transmitted through the sample is measured and compared to the reference
solution. The absorbance (A) is calculated using the relation,
𝐼0
𝐴 = 𝑙𝑜𝑔10( 𝐼
) (1)
Where 𝐼0is the intensity of light passing through the reference solution which is assumed to
undergo minimal particle scattering, meaning that maximum light intensity passes through it. , and 𝐼
is the intensity of light transmitted through the sample.
And Beer-Lambert's law proposes that the concentration (C) of the dye in the sample is proportional
to the absorbance.
𝐶 ∝ 𝐴 (2)
Adsorption Kinetics
The adsorption kinetics model is more complex and requires the use of differential
equations. The pseudo-first-order model, in which 𝑘𝑙 is the rate constant and 𝑞𝑡 is the amount of dye
adsorbed at time t, is one that is frequently used
𝑑𝑞𝑡
𝑑𝑡
= 𝑘𝑙 (𝑞𝑒 − 𝑞𝑡) (3)
Assuming a linear model for equilibrium, i.e.
𝑞 = 𝑘𝐶𝑒 (4)
Mass balance gives
𝑉(𝐶0 − 𝐶) = 𝑚(𝑞 − 𝑞0) = 𝑚 × 𝑞 [ 𝑠𝑖𝑛𝑐𝑒, 𝑞0 = 0 ] (5)
where,
● 𝑞𝑡 is the amount of dye adsorbed at time t,
● 𝑞𝑒is the equilibrium amount of dye adsorbed,
● V is the volume of the system.
If 𝐾𝑐 is the mass transfer coefficient & 𝑎 is this is the area available for mass transfer per unit
volume, we can write
𝑑𝐶
𝑑𝑡
= 𝐾𝑐𝑎 (𝐶𝑒 − 𝐶) (6)
Making the assumptions of first order kinetics,
CH 3522: Unit Operations Lab
𝑑𝐶 𝑞
𝑑𝑡
= 𝐾𝑐𝑎 ( 𝑘 − 𝐶) (7)
𝑑𝐶 𝑉(𝐶0−𝐶)
=> 𝑑𝑡
= 𝐾𝑐𝑎 ( 𝑘
− 𝐶)
𝑑𝐶
=> 𝑉 𝑉 = − (𝐾𝑐𝑎) 𝑑𝑡
[(1+ 𝑚𝑘
)𝐶 − ( 𝑚𝑘 )𝐶0]
Integrating both the sides we get the final expression of the model we will be the our
experimentally obtained data against,
𝑉 𝐶 𝑉 𝑉
𝑙𝑛[(1 + 𝑚𝑘
) 𝐶0
− ( 𝑚𝑘 )] = (1 + 𝑚𝑘
) × (− 𝐾𝑐𝑎𝑡)
𝑉 𝑉 𝐶0𝑚𝑘
=> 𝐶 = [𝑒𝑥𝑝{(1 + 𝑚𝑘
) × (− 𝐾𝑐𝑎𝑡)} + 𝑚𝑘
] (𝑉+𝑚𝑘)
(8)
Figure 2: UV-Vis Spectrophotometer
CH 3522: Unit Operations Lab
4. Apparatus Required
● Methylene Blue Dye
● Pipettes, Microbalance
● Activated Charcoal, Distilled water
● UV-Vis Spectrophotometer (shown in figure 2)
● Heating plate, beakers and test tubes
● Magnetic stirrer (operated at low rpm, around 300)
5. Schematic of Experimental Setup
Experimental setup includes the following components:
● Adsorbent – Activated charcoal used for dye adsorption.
● Dye Solution – Prepared solution of the target dye for adsorption studies.
● Agitation System – Magnetic stirrer as orbital shaker ensuring uniform mixing of adsorbent
and dye solution.
● Spectrophotometer – Measures the absorbance of the supernatant to determine dye
concentration.
● Cuvettes and Pipettes – For sample handling and preparation before absorbance measurement.
Figure 3: Schematic representation of the experimental set-up
CH 3522: Unit Operations Lab
The schematic (figure 3) illustrates the adsorption experiment workflow, beginning with the
preparation of a dye solution and the introduction of an adsorbent. The mixture undergoes agitation
to facilitate adsorption. The supernatant is then collected and analyzed using a spectrophotometer to
measure absorbance, providing insights into the adsorption efficiency.
We also show the samples taken in test-tubes & the microbalance used while performing the
experiment in the laboratory in the following figures.
Figure 4: Samples in test-tubes & Microbalance for accurate weight measurements
6. Procedure
Dye solution preparation:
● Weigh 0.1g of methylene blue dye on a microbalance and transfer to the beaker.
● Make 1L of the dye solution using distilled water.
Dye sample preparation for calibration:
● 10 mL of the dye solution is pipetted out and transferred to sample vials and diluted with
appropriate amounts of distilled water.
● Samples of varying concentrations (1, 2, 3 , 4 and 5 ppm) made for preparing the calibration
data set of concentration-absorbance using a UV-Vis spectrophotometer.
Batch Adsorption:
● 4g of activated charcoal of known quality is added to the dye solution.
● The activated charcoal is kept suspended by mild stirring of the slurry using a magnetic
stirrer (keep a moderate stirring rate).
CH 3522: Unit Operations Lab
Sampling for UV-Vis Analysis:
● At periodic intervals of time, stop the stirring, wait for the suspension to settle down, and
draw 5 mL of particle free liquid sample for analysis of the concentration using the UV-Vis
spectrophotometer.
● Sufficient quantity of the sample is transferred to the cuvette for analysis.
Concentration analysis of sample:
● After turning on the spectrophotometer and the computer, run the spectrum analysis and
measurement software.
● Adjust the measurement parameters, including the wavelength range and scan rate.
● Prior to measuring the samples, make reference measurements with distilled water.
● Insert the sample into the allotted slot, making sure its transparent side is facing the laser
beam.
● Ensure that the sample slot is clean to prevent fingerprint marks interference. Store purified
water in the designated reference slot.
● Start the process of gathering data. After the data is collected, find the absorbance values and
peak position.
7. Experimental Observations
The RPM was set to 290-310 throughout. All the experimental observations that were tabulated
during the laboratory session are included in order at the end.
In the following two tables, we include the calibration data along with the experimental values of the
absorbance obtained from the specific solution samples of concern after specific time intervals. The
wavelength at which the calibration data was taken is 663 nm.
Concentration of Solution (ppm) Absorbance
0 0.0001
1 0.1582
2 0.3242
3 0.5281
4 0.7360
5 0.9034
Table 1: Calibration Table
CH 3522: Unit Operations Lab
Now the absorbance data obtained from each of the samples after certain amount of dilution is,
Sampling Time (min) Absorbance Dilution Level
5 0.1727 100 (times diluted)
10 0.1331 100
15 0.5568 20
20 0.5492 20
25 0.4509 20
35 0.2783 20
45 0.2439 20
55 0.2680 20
65 0.1412 20
75 0.1629 20
90 0.1200 20
Table 2: Experimentally obtained absorbance values for each sample
8. Sample Calculations
At the very first, we used the calibration data to come up with the calibration model given as
equation (14) in the “Results & Discussions” section. This model is used in the later step where we
have the absorbance values of several samples at different time-stamps in order to find their
concentrations. For example at time-step 10 minutes, the sample we obtained has an absorbance
value of 0.1331. Now using the model (eq 14) we get,
𝑐𝑜𝑛𝑐 (𝑝𝑝𝑚) = (5. 422739) * (0. 1331) + 0. 104957 = 0. 826724 𝑝𝑝𝑚
Then using the known dilution value from table 2 we get the original / corrected concentration of
the undiluted sample which contains the information of the amount of dye being adsorbed after 10
minutes the experiment commenced. So the actual concentration is 82.6724 ppm. The values of
the corrected concentrations estimated from this model are tabulated in table 3 in the “Results &
Discussions” section.
CH 3522: Unit Operations Lab
Then these concentration values are used to fit a non-linear model provided as equation 8 in the
“Theory” section. The equation 8 can simply simply be written as follows
𝐶 = 𝐴 𝑒𝑥𝑝(− 𝐵𝑡) + 𝐷 (9)
And the parameters A, B & D are estimated using a non-linear optimization in MATLAB using
in-built function lsqnonlin. The estimates are as follows
𝐴 = 97. 4965; 𝐵 = − 0. 000590; 𝐷 = 10. 8756
These values used to extract out the unknown quantities in the equation 8 which are 𝑘 & 𝐾𝑐𝑎 & the
results are discussed in the following section and a plot of the fitted model is also given in figure 6.
The known quantities are,
𝐶0 = 100 𝑝𝑝𝑚 (the initial concentration of the solution, the adsorption experiment started with),
the mass of the adsorbent (activated charcoal) is 4g or 4000 mg and the volume of the beaker is 1 L
which is nothing but the initial volume of the solution.
At the end, the experimentally found mass transfer coefficient is compared with the theoretical
correlation of finding mass transfer coefficient. Thus this “Sample Calculation” section not only
provides the individual computation of a result of a subpart of the whole flow but also provides the
complete flow of calculation methodology that is being followed to obtain the required results.
Calculation of Theoretical 𝐾𝑐 from correlations:
The adsorption in the setup can be related to single spherical particle adsorption to calculate the mass
transfer coefficient. The correlation for the same is
1/3 0.5
𝑆ℎ = 𝑆ℎ0 + 0. 74 × 𝑆𝑐 × 𝑅𝑒 (10)
Here 𝑆ℎ0 = 2. To calculate the Reynold’s number, velocity is averaged across the beaker.
Considering beaker diameter as 13 cm and from the expression of Reynold’s number we get
𝑅𝑒 = ν𝑑𝑝 / µ (11)
Similarly, the Schmidt number can be calculated as
𝑆𝑐 = ν/𝐷𝐿 (12)
7
which is coming out to be 1. 0503 × 10 , where 𝐷𝐿 is the molecular diffusion coefficient. Thus the
Sherwood number is coming out to be 8457.7165. Now using, the definition of Sherwood number,
𝑆ℎ = 𝐾𝑐𝑑𝑝 / 𝐷𝐿 (13)
Here, the characteristic length considered is the average length of adsorbent particles, we get the
−7
mass transfer coefficient as 𝐾𝑐 = 2. 6337 × 10 𝑚/𝑠.
CH 3522: Unit Operations Lab
9. Results & Discussions
At first we have used the calibration data to obtain a model and using TLS objective we have got the
Figure 5: Calibration curve
following model,
𝑐𝑜𝑛𝑐 (𝑝𝑝𝑚) = (5. 422739) * 𝑎𝑏𝑠𝑜𝑟𝑏𝑎𝑛𝑐𝑒 + 0. 104957 (14)
2
And the coefficient of determination (𝑅 ) value of this model comes out to be 0.997628, which is a
quite good model for calibration purposes since this gives the result of the following parts of the
flow of the calculation described in the “Sample Calculation” section. The plot of the fitted model
is given in the above figure (figure 5).
Now we provide the table containing the corrected concentrations of the samples taken in the
specified time-steps (table 2) which are further used in building the adsorption kinetics model.
The fitted model on the concentration data is given in the following figure (figure 6). The parameters
give the resulting mass transfer coefficient & equilibrium constant values which are coming out to be
−1
𝑘 = 0. 002049 𝐿/𝑚𝑔 = 0. 002049 𝑝𝑝𝑚 ;
−1 2
𝐾𝑐 × 𝑎 = 0. 0005259775 𝑠 and these are obtained from a model which has a 𝑅 value of 0.967.
CH 3522: Unit Operations Lab
Sampling Time (min) Absorbance Corrected Concentration (ppm)
5 0.1727 104.14641
10 0.1331 82.6724
15 0.5568 62.4868
20 0.5492 61.6625
25 0.4509 51.0014
35 0.2783 32.2821
45 0.2439 28.5513
55 0.2680 31.1650
65 0.1412 17.4129
75 0.1629 19.7664
90 0.1200 15.1137
Table 3: Corrected Concentrations of the Solution Samples
Considering the radius of the adsorbent particles to be 1mm, the value of the liquid mass transfer
coefficient is coming out to be,
−7
𝐾𝑐 = 0. 0005259775 / 𝑎 = 0. 0005259775 × 0. 001 × (1/3) = 1. 75326 × 10 𝑚/𝑠.
From the trend found in figure 6, we can represent the equation 8 as follows,
𝐶 = (𝐶0 − 𝐶∞) 𝑒𝑥𝑝(− 0. 0005259775 × 𝑡) + 𝐶∞ (15)
And using the estimates of the model parameters (A, B & D), we can extract the values of initial and
saturated concentration values, which are
𝐶∞ = 10. 8756 𝑝𝑝𝑚 and 𝐶0 = 108. 372144 𝑝𝑝𝑚 respectively.
10. Conclusions
● As expected, the absorbance vs concentration plot demonstrated conformity to the linear
model (used as calibration model here).
● The concentration vs time graph exhibited an anticipated exponential decay trend.
● Both the calibration data and the concentration data are fitted to the obtained models really
well, confirmed from the value of the coefficient of determination which implies that the
CH 3522: Unit Operations Lab
Figure 6: The change in concentration of dye due to adsorption on activated charcoal
raw data collection process has been done significantly well.
−7
● The experimental & theoretical liquid mass transfer coefficient values are 1. 75326 × 10
−7
m/s & 2. 6337 × 10 m/s, which are pretty close. Though one might use more complex
correlation of Sherwood number such as given in equation 16 to obtain even more accurate
results to correlate with the experimental result.
𝐾𝑐𝑑𝑝 0.62 0.36 0.17
𝑆ℎ = 𝐷𝐿
= 𝑆ℎ0 + (0. 47)(𝑅𝑒) (𝑆𝑐) (𝑑𝑖𝑚𝑝𝑒𝑙𝑙𝑒𝑟/𝑑𝑏𝑒𝑎𝑘𝑒𝑟) (16)
The above correlation is given by Levins & Glastonbury and was also used in the paper
“Liquid-to-Particle Mass-Transfer in a Stirred Batch Adsorption Tank with non-linear
Isotherm”.
● Though from the model (equation 9 & 15) the value of 𝐶0 is coming out to be 108. 372144
ppm, but according to the experiment conditions, the initial concentration of the solution was
100 ppm. This erroneous estimation has come because the raw data collected might have
issues with the values of dilution or absorbance.
● We might control some factors while taking the raw data to avoid further possibilities of
human and machine errors.
CH 3522: Unit Operations Lab
● Some experimental sources of error include inadequate amount of solution was sampled,
even during decantation, instrument errors cause erroneous amounts. Besides inaccuracies
in UV spectrometer measurements and errors brought on by sample weight loss during
solution preparation.
11. References
I. CH 2014 : Heat & Mass Transfer Course Notes.
II. Application note on Theory of Absorbance by Trilogy Laboratory.
III. Liquid-to-Particle Mass-Transfer in a Stirred Batch Adsorption Tank with non-linear
Isotherm, 1982 paper to obtain the theoretical correlation & kinetic model for adsorption.
IV. Liquid-Solid Mass Transfer in Adsorption systems - An Overlooked Resistance, 2020 paper to
obtain more inference on adsorption theory.
V. Determination of Mass Transfer Coefficients for Adsorption of Pb and Cd Onto Coir Pith
and Statistical Analysis, 2020 paper to get the derivation of the frequently used kinetic model
to capture the adsorption phenomenon.
◦
VI. The Engineering Toolbox to find the kinematic viscosity of water at 30 𝐶 used in the
computation of Sherwood number.
◦
VII. Valves Instruments Plus Ltd. provided list to obtain density of water at 30 𝐶.
VIII. Diffusion Coefficient article by Thermopedia.
IX. The GitHub repository contains all the related data and coded scripts used for
calculations.
CH 3522: Unit Operations Lab
CH 3522: Unit Operations Lab