ChE 35

Activity No. 2

Adsorption

Group 2

Writer: Arquillano, Christian Philippe (20140004089)

Co – worker: Lopez Fine Dale (20150007451)

Mendoza, Karryle Wenzel Ashley (20140003798)

Sialana, Shania Eve (20150007750)

Date Performed: July 12, 2019

Date Submitted: July 15, 2019

Instructor: Dr. Shierlyn S. Paclijan

Abstract

Adsorption is the process by which liquids or gas molecules or solutes travel and adheres to
a solid/liquid surface to form a thin film. In the experiment, different concentrations of methylene
blue diluted in water was to be adsorbed using ten milligrams of activated carbon with constant
mixing and at constant temperature. The concentrations were recorded every two-minutes for twenty
minutes using the UV-vis Spectrophotometer. The adsorption of methylene blue fitted the Langmuir
isotherm with an R2 of 0.830 compared to the R2 of the Freundlich isotherm which has a value of
0.0011.

Introduction

Adsorption is the surface phenomena of the building up of large quantities of molecular

species at the surface of liquid or solid phase. Adsorption occurs due to the imbalance or spaces that
are present in the solid or liquid surface. These open spaces tend to attract and store the molecular
species that come in contact with the surface.

Adsorption is very different from Absorption. Absorption is the process of uniform

distribution of a substance throughout the whole material while adsorption only happens at the
surface of the substance.

The process of adsorption has two main components: Adsorbent and Adsorbate. The
adsorbent is the substance on the surface where the adsorption occurs. Adsorbents usually are very
porous and have high thermal stability. Examples of common adsorbents are activated carbon, silica
gel and zeolites. On the other hand, Adsorbate is the substance which is being adsorbed by the
adsorbent. (Chemistry Learning 2009)

Adsorption is usually described through isotherms, which is the amount of adsorbate on the
adsorbent as a function of its pressure or concentration at constant temperature. Some common types
of isotherms are Linear isotherm, Langmuir isotherm and Freundlich Isotherm. The Linear isotherm
is the simplest since it represents the amount adsorbate adsorbed to be proportional to its partial
pressure of the adsorptive gas. Langmuir isotherm describes the adsorption process by assuming the
adsorbate behaves as an ideal gas at constant temperature. Lastly, Freundlich isotherm gives the
empirical relationship between the solute’s concentration on the adsorbent’s surface to the solute’s
concentration in the liquid for which the adsorbent is in contact with. (Chemistry Learning 2009)

The objectives of this experiment are to study the adsorption of methylene blue from an
aqueous solution by activated charcoal, examine the validity of Freundlich & Langmuir’s isotherm
and determine the maximum amount of adsorbate per gram of adsorbent, A max, and adsorption
constant, k.
Theoretical Background

The general adsorption procedure comprises of a progression of steps in arrangement. At the point
when the fluid is flowing past the adsorbent in a fixed bed, the solute initially diffuses from the bulk
fluid to the gross outside surface of the adsorbent. At that point the solute diffuses inside the pore to
the outside of the pore. Then, the solute is adsorbed superficially. Henceforth, the general adsorption
procedure is a progression of steps (Geankoplis 2014, 762).

The adsorption isotherm is the equilibrium relationship between the concentration in the
fluid phase and the concentration in the adsorbent particles at a given temperature. For gases, the
concentration is typically given in mole percent or as a partial pressure. For liquids, the
concentration is frequently communicated in mass units, for example, mg/L (ppm) or μg/L (ppb).
The concentration on the solid is given as mass adsorbed per unit mass of original adsorbent
(McCabe et al 2006, 840).

Fig. 2.1. Some common types of adsorption isotherms (from Geankoplis 2014,762).

Data that pursue a linear law can be communicated by a condition like Henry's law:

𝑞 = 𝐾𝑐 (2.1-1)
3
where K is a constant determined experimentally, m /kg adsorbent. This direct isotherm is not
normal, yet in dilute area it very well may be utilized to surmised information for many systems.

The Freundlich isotherm equation, which is experimental, frequently rough data for many
adsorption systems and is especially helpful for liquids:

𝑞 = 𝐾𝑐 (2.1-2)
where K and n are constants and must be determined experimentally. In the event that a log-log plot
is made for q versus c, the slope is the dimensionless exponent n. The dimensions of K rely upon the
estimation of n. This equation is sometimes used to connect information for hydrocarbon gases on
activated carbon.
 The Langmuir isotherm has a theoretical basis and is given by the following, where qo and K
are empirical constants:
𝑞 𝑐 (2.1-3)
𝑞=
𝐾+𝑐

where qo is kg adsorbate/kg solid and K is kg/m3. The equation was derived assuming that there are
only a fixed number of active sites available for adsorption, that only a monolayer is formed, and
that the adsorption is reversible and reaches an equilibrium condition. By plotting 1/q versus 1/c, the
slope is K/qo and the intercept is 1/qo (Geankoplis 2014, 763).

Procedure
 A calibration curve from 0 to 20 ppm of methylene blue solution relating absorbance to
concentration was prepared. This was done using a UV Vis spectrophotometer. The five adsorption
setups were prepared by adding 10.0 mg of activated charcoal first and then adding the 100 mL
distilled water, 5 ppm, 10 ppm, 15 ppm, and 20 ppm to each Erlenmeyer flask. The flasks were
stirred in the gyrotory shaker for 20 mins. Samples were taken for UV Vis analysis every after 2.0
minutes. The readings were then plotted and analyzed and then the appropriate adsorption isotherm
was determined.

Results

There are many isotherm models that are present. Isotherms are used to describe adsorption
which connects the amount of adsorbate on the adsorbent with its pressure (in gas) or concentration
(in liquid). Among of these adsorption isotherm models are the Freundlich isotherm, Langmuir
Isotherm, and BET isotherm. However, in this experiment, the aim is to determination on which
among the two common adsorption isotherm model (Langmuir and Freundlich) will be the data
most fitted. The following plot shows the evident adsorption isotherm model for the data obtained.

Table A1. Calibration Curve Data

Concentration Absorbance
0 0.038
5 1.273
10 1.545
15 3.031
20 3.257

Concentration vs. Absorbance

25
y = 5.7869x - 0.5832
20 R² = 0.9486
Concentration, ppm

15

10

0
0 1 2 3 4
-5 Absorbance

Figure 2.2. Calibration Curve

 Table A3. Calculated Concentration over Time
Initial Time (min)
Conc. 2 4 6 8 10 12 14 16 18 20
(ppm)
0 -
0.13748 0.25018 3.2242 -0.583 0.16339 0.209682 2.958032 0.007172 2.865456 -0.03333
5 3.01011 2.7382 5.5733 5.0584 5.42865 2.500938 5.613806 6.24448 3.38041 5.9146
10 7.5579 6.7247 7.1355 6.3428 9.75658 9.606146 6.990874 9.814442 6.892512 9.415208
15 13.292 6.6553 9.7045 8.8254 9.23006 12.37764 9.623504 11.66596 9.496212 12.60908
20 19.338 0.9792 16.566 18.783 16.31212 16.31212 16.2774 18.5108 18.5108 18.5108

.
Concentration vs. Time
25

20 0 ppm
Concentration, ppm

5 ppm
15
10 ppm
10
15 ppm
5 20 ppm
0
0 5 10 15 20
-5
Time, min

Figure 2.3. The concentration of each solution over time

Table A5. Tabulated Data for Isotherm fitting at 18 mins

Freundlich Langmuir
qe c lnCe (x) ln qe (y) 1/n ln(K) Ce (x) Ce/qe (y)
1/qm K/qm
(slope) (y-int.) (slope) (y-int.)
0.016196 2.865456 1.217997 -4.123 0.028 -3.733 3.38041 208.7201 73.47 -241.6
0.031075 3.38041 1.930436 -3.47136 6.892512 221.8033
0.055038 6.892512 2.250893 -2.89973 9.496212 172.5396
0.014892 9.496212 2.918354 -4.20693 18.5108 1243.003

.
 Langmuir Isotherm
1400
1200 y = 73.471x - 241.6
R² = 0.8301
1000
800
ce/qe

600
400
200
0
0 5 10 15 20
ce
Figure 2.4. Equilibrium Data fitted to Langmuir isotherm

Freundlich isotherm
0
0 0.5 1 1.5 2 2.5 3 3.5
-1

-2
y = 0.0282x - 3.7339
ln(qe)

-3 R² = 0.0011

-4

-5
ln(ce)

Figure 2.5. Equilibrium Data fitted to Freundlich isotherm.

Discussion of Results:

The results gathered from the experiment demonstrated that concentration of the solution is
directly proportional to its absorbance. Adsorption process is generally studied through adsorption
isotherms. Adsorption isotherms are the graphs which describe the interaction of adsorbates with
adsorbents. In this experiment, the adsorbate is the methyl blue while the adsorbent is the activated
carbon.
Adsorption isotherms provide more details about adsorption process. In Figures 3 and 4, it
shows the graphs of Langmuir isotherm and Freundlich isotherm, respectively. The adsorption
isotherm model that most fitted the data obtained was the Langmuir isotherm. In Figure 3, it clearly
illustrates the interaction and the validity of the data. It has a 𝑠𝑙𝑜𝑝𝑒 = 73.47 and 𝑏 = −241.6 an
and 𝑅 = 0.830. On the other hand, the Freundlich isotherm model with y = 0.028x - 3.733 as an
equation of the graph and 𝑅 = 0.001. The correlation coefficient for Langmuir isotherm are more
significantly higher and valid than that of the Freundlich isotherm. Thus, Langmuir isotherm model
is the model that most fitted the data. Moreover, Langmuir isotherm model conforms the behavior of
methyl blue on activated carbon.

Conclusion and Recommendation

The researchers concluded the following statements:

i.) The concentration of the solution is directly proportional to its absorbance
ii.) The concentration of the solution decreases through time.
iii.) The adsorption of methylene blue fitted the Langmuir isotherm better (𝑅 = 0.830) compared
to the Freundlich isotherm (𝑅 = 0.001).
iv.) The rate of the adsorption is the fastest just after the addition of activated carbon to the solution

The researchers’ recommendations for the radiation experiments thus include:

i.) When sampling, the pipet used to withdraw the samples from the solution should be
covered with a filter paper or cotton to prevent activated carbon from being withdrawn
with the solution. The withdrawal of the activate carbon would causes errors in the
analysis.
ii.) When sampling, each solution must have its own pipet so that when withdrawing the
samples, it will not contaminate the other concentration.
iii.) More time could be allocated for the experiment to allow the solution and the adsorbent
to reach equilibrium. This will result to more accurate fitting for the isotherms.
iv.) The equipment used must be calibrated properly first to avoid fluctuations in the data
v.) To give more data points for the fitting of the isotherm, more solutions of different
concentrations could be prepared. This will increase the overall certainty of the isotherm
fitting.

Literature Cited
 Geankoplis, Christie John. 2014. Transport Processes & Separation Processes Principles
(Includes Unit Operations). 4th edition. Pearson New International Edition.

 McCabe, Warren L., Smith, Julian C., and Peter Harriott. 2006. Unit Operations of Chemical
Engineering. 7th. McGraw-Hill Education (Asia).

 Chemistry Learning. 2009. Adsorption. March 5. Accessed July 14, 2019.

http://www.chemistrylearning.com/adsorption/.
 Nomenclature
Symbol Description Unit
Concentrate of solute in fluid c 𝑔
𝑚𝐿
Initial Concentration of co 𝑔
solute in fluid 𝑚𝐿
Isotherm constant K
Isotherm constant n
Concentration of solute in q 𝑚𝑔
adsorbent 𝐿
Initial concentration of qo 𝑚𝑔
solute in adsorbent 𝐿
Volume of solution V L

Appendix
A. Raw Data and Tabulated Data
V=0.1 Liter=100 mL
Mass of activated carbon= 0.01 g=10 mg
Table A1. Calibration Data
Concentration Absorbance
0 0.038
5 1.273
10 1.545
15 3.031
20 3.257

Table A2. Absorbance over Time

Initial Time (min)
Concentration 2 4 6 8 10 12 14 16 18 20
(ppm)
0 0.077 0.144 0.658 0.000 0.129 0.137 0.612 0.102 0.596 0.095
5 0.621 0.574 1.064 0.975 1.039 0.533 1.071 1.180 0.685 1.123
10 1.407 1.263 1.334 1.197 1.787 1.761 1.309 1.797 1.292 1.728
15 2.398 1.251 1.778 1.626 1.696 2.240 1.764 2.117 1.742 2.280
20 3.443 0.270 2.964 3.347 2.920 2.920 2.914 3.300 3.300 3.300

Table A3. Concentration, ce (ppm) over Time

Initial Time (min)
Conc. 2 4 6 8 10 12 14 16 18 20
(ppm)
0 -0.13748 0.250184 3.224188 -0.583 0.163394 0.209682 2.958032 0.007172 2.865456 -0.03333
5 3.010106 2.738164 5.573304 5.05835 5.428654 2.500938 5.613806 6.24448 3.38041 5.914678
10 7.557902 6.724718 7.135524 6.342842 9.756582 9.606146 6.990874 9.814442 6.892512 9.415208
15 13.29183 6.655286 9.704508 8.825036 9.230056 12.37764 9.623504 11.66596 9.496212 12.60908
20 19.3382 0.97922 16.5667 18.78274 16.31212 16.31212 16.2774 18.5108 18.5108 18.5108
 Table A4. Calculated qe for Isotherm Fitting
Initial Time (min)
Conc. 2 4 6 8 10 12 14 16 18 20
(ppm)
5 0.019899 0.022618 -0.00573 -0.00058 -0.00429 0.024991 -0.00614 -0.01244 0.016196 -0.00915
10 0.024421 0.032753 0.028645 0.036572 0.002434 0.003939 0.030091 0.001856 0.031075 0.005848
15 0.017082 0.083447 0.052955 0.06175 0.057699 0.026224 0.053765 0.03334 0.055038 0.023909
20 0.006618 0.016628 0.034333 0.012173 0.036879 0.036879 0.037226 0.014892 0.014892 0.014892

Table A5. Tabulated Data for Isotherm fitting at 18 mins

Freundlich Langmuir
qe ce lnCe (x) ln qe (y) Ce (x) Ce/qe (y)
0.016196 2.865456 1.217997 -4.123 3.38041 208.7201
0.031075 3.38041 1.930436 -3.47136 6.892512 221.8033
0.055038 6.892512 2.250893 -2.89973 9.496212 172.5396
0.014892 9.496212 2.918354 -4.20693 18.5108 1243.003

B. Sample Calculations

Sample: 5 ppm at 18 minutes, where its absorption (x)=0.685

To solve for the concentration, ce: Use the equation from calibration curve

𝑦 = 5.786𝑥 − 0.583
𝑦 = 5.786(0.685) − 0.583
𝑐 = 𝑦 = 3.38041
To calculate for qe:

(𝑐 − 𝑐 )𝑉
𝑞 =
𝑚 .

5𝑚𝑔 3.38041𝑚𝑔
− (0.1𝐿)
𝐿 𝐿
𝑞 =
10 𝑚𝑔
𝑞 = 0.016196

Langmuir equation:
𝑦 = 𝑚𝑥 + 𝑏

𝑐 1∗𝑐 𝐾
= +
𝑞 𝑞 𝑞

Freundlich equation:
1
ln 𝑞 = ∗ ln 𝑐 + ln 𝐾
𝑛