Adsorption of Acetic Acid by a Solid

By: Courtney Molvig

CHEM 307 - 54

Lab Partners: Matthew Morrow and John McAlpine

Abstract

In this experiment, the purpose is to study and compare two adsorption isotherms of
acetic acid on activated carbon. The two adsorption isotherms were comparing are the Langmuir
and Freundlich isotherm. When graphing the Freundlich equation, the two experimentally
determined constants, n and k, are equal to 1.008 and 0.065, respectively. When looking at the
Langmuir adsorption isotherm, you get that Ymax is equal to 0.03156 and k is equal to 7.378. If
you look at the undiluted solution of acetic acid, the concentration of the solution prior to the
activated charcoal being added to it was 0.6098 M and the concentration after the activated
charcoal sat in the solution for a weak is 0.56914 M. These two principals we focus on in this lab
help us explain what adsorption is and how accurate our data is. When looking at our data, you
can see that the Freundlich equation better represents our data. The Freundlich model is often
used, because it can represent a wide range of concentrations and it is a good representation of
nonlinear adsorption isotherms.

Introduction

“Adsorption is a process that occurs when a gas or liquid solute accumulates on the
surface of a solid or liquid (adsorbent), forming a molecular or atomic film (the adsorbate)”
[1].When using catalysts, chemical adsorption is extremely important. Not only do many
industries use catalysts regularly, but many scientist and researchers also use catalyst regularly.
Adsorption is also important in industries that either oxidize or reduce metals.

In this experiment, the two principles we are focusing on are the Langmuir and
Freundlich isotherm. “The Langmuir adsorption isotherm is based on theoretical considerations”
[2]. The assumptions made in the Langmuir adsorption include: “The adsorbed phase forms a
layer of molecules one molecule deep; the system is in a state of equilibrium such that the rate of
adsorption equals the rate of desorption; the rate of adsorption is proportional to the
concentration and the fraction of the surface that is vacant; the rate of desorption is proportional
to the fraction of the surface that is already covered” [2]. In order to figure out if a system
actually does follow the Langmuir equation, you need to plot the concentration divided by the
substance amount of acetic acid adsorbed per gram of the charcoal against the concentration.
This graph should give you a straight line, and the slope will equal 1/Ymax and the intercept
would equal 1/kYmax.

To explain the Langmuir adsorption isotherm a little better, we must look at the different
equations used for it. In the following equation, θ is the fraction of the surface that is covered, Y
is the moles adsorbate per gram adsorbent, c is the concentration, and k is an experimentally
determined constant.

𝑌 𝑘𝑐 Equation 1
𝜃= =
𝑌𝑚𝑎𝑥 1 + 𝑘𝑐

If you rearrange the above equation, you get:

𝑐 1 𝑐 Equation 2
= +
𝑌 𝑘𝑌𝑚𝑎𝑥 𝑌𝑚𝑎𝑥
 The equation needed to solve for the substance amount of acetic acid absorbed per gram
is:

(𝐶𝑏 − 𝐶𝑎 ) ∗ 𝑉 Equation 3
𝑚= ,
𝑔

where m is the substance amount of acetic acid absorbed per gram of the charcoal (mol/g), Cb is
the concentration of acetic acid before adsorption (mol/L), Ca is the concentration of acetic acid
after adsorption (mol/L), V is the volume of the liquid phase used for adsorption (L), and g is the
mass of the adsorbent (g). In this case, the adsorbent is the charcoal.

The other type of isotherm we are examining is the Freundlich isotherm. This isotherm
should show an increase of adsorption when the concentration increases. This isotherm only
applies when the system is at constant temperature. The Freundlich isotherm is an empirical
equation. The equation given in Sime is:
Equation 4
1/𝑛
𝑌 = 𝑘𝑐 ,

where Y is the moles adsorbate per gram adsorbent (mol/g), c is the concentration (mol/L), and k
and n are experimentally determined constants [2]. If you take the log of both sides on equation
4, you get the following equation:
Equation 5
1
𝑙𝑜𝑔𝑌 = 𝑙𝑜𝑔𝑘 + 𝑙𝑜𝑔𝑐
𝑛
When seeing if the Freundlich model is a good representation of your data, you will plot the log
Y against the log c. With this graph, you should get a straight line. The slope of the line will
equal 1/n and the intercept will equal log k.

The reason why activated charcoal was used in this experiment is due to the structure.
Graphitized charcoal is homogeneous and active charcoal have a highly heterogeneous structure
[3].The activated charcoal is also used as an adsorbent, because it has a large surface area.
Shown below is an image of our solutions, after the activated charcoal sat in the solution for a
week.
 Image1 shows activated charcoal sitting in different acetic acid solutions. This image was taken prior
to doing any analysis on the solutions, but after the charcoal sat in the solution for a weak.
After doing some research, I expect that the Freundlich equation would be a better model
when compared to the Langmuir adsorption isotherm. After doing some research and reading
about the two isotherms, it seems that the Freundlich equation is good at showing a wide range
of concentration and it is a good representation of nonlinear adsorption isotherms.

Methods/Experiments

To begin this experiment, we had to make a sodium hydroxide solution (NaOH) and an
acetic acid solution (HAc). In order to make the solutions, we first filled up two one-liter
polyethylene bottles with DI water. We made sure that there was enough DI water, so it reached
just beneath the shoulder of the bottle. We then added between twenty and thirty milliliters of
approximately 17 M to 18 M sodium hydroxide to one bottle and a similar amount of
approximately 17 M acetic acid to the other bottle. We then shook the bottles to ensure that the
solution was evenly mixed.

Once the solutions were made, we then had to find the exact concentrations of our
solutions. We began by finding the concentration of our sodium hydroxide solution. To find the
concentration, we have to do an acid-base titration. To start this, we weighed potassium
hydrogen phthalate (KHP) and dissolving it in DI water in an Erlenmeyer flask. To weigh the
KHP, we used the weighing by difference method in hope of getting more accurate results. Once
all of the KHP was dissolved, we added phenolphthalein indicator, put a magnetic stir bar in the
flask, and placed the flask on a magnetic stir plate. We then added the sodium hydroxide solution
to a buret and slowly added the sodium hydroxide solution to the flask. We added enough of the
solution until the solution in the flask turned a light pink. We had to make sure the solution was
only light pink, because if it was dark pink it would indicate that we over titrated. We recorded
the initial and final volume of the buret and used the total volume delivered to find the
concentration of the solution. We did this three times to get an average concentration. The
calculation to find the concentration is:
 𝑔
𝑚𝑎𝑠𝑠 𝑜𝑓 𝐾𝐻𝑃 (𝑔) / 𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑜𝑓 𝐾𝐻𝑃( ) Equation 6
𝑚𝑜𝑙
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑁𝑎𝑂𝐻 𝑎𝑑𝑑𝑒𝑑 (𝐿)

Once we knew the concentration of the sodium hydroxide solution, we then did another
acid-base titration to find the concentration of the acetic acid solution. To do this, we added
twenty milliliters of the acetic acid solution to an Erlenmeyer flask. We then added
phenolphthalein indicator and a magnetic stir bar to the flask and placed the flask on a magnetic
stir plate. We had the sodium hydroxide solution in the buret and added the solution into the
flask until the flask had a light pink tint. Knowing how much solution was added to the flask, we
were able to calculate the concentration of the acetic acid solution. We were able to calculate the
concentration since the sodium hydroxide and acetic acid solution have a one to one ratio. The
equation used to find the concentration of the acetic acid solution is:

𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑁𝑎𝑂𝐻 𝑎𝑑𝑑𝑒𝑑 (𝐿) Equation 7

𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑁𝑎𝑂𝐻(𝑀) ∗
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑎𝑐𝑒𝑡𝑖𝑐 𝑎𝑐𝑖𝑑 𝑢𝑠𝑒𝑑 (𝐿)

Once we knew the concentration of the acetic acid solution, we diluted the solution. The
dilutions we used were 5%, 10%, 25%, 50%, 75%, and 100%. We added one hundred milliliters
of the dilutions into a glass bottle and added a certain mass of charcoal into the glass bottle and
let them soak for a week. Once a week went by, we took twenty-five milliliters from the 5%
dilution, twenty-five milliliters from the 10% dilution, twenty milliliters from the 25% dilution,
ten milliliters from the 50% dilution, ten milliliters from the 75% dilution, and ten milliliters
from the 100% dilution and put them into an Erlenmeyer flask. We then titrated these solutions
to see the new concentration of the acetic acid. We repeated each of these trials three times. To
find the new concentration of the acetic acid after adsorption, the equation you need to use is:

𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑁𝑎𝑂𝐻 𝑎𝑑𝑑𝑒𝑑 (𝐿) Equation 8

𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑁𝑎𝑂𝐻 (𝑀) ∗
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑎𝑐𝑒𝑡𝑖𝑐 𝑎𝑐𝑖𝑑 𝑢𝑠𝑒𝑑 (𝐿)

When all of the experiments were done, we were able to do calculations and use the
Langmuir and Freundlich isotherm to see how much acetic acid was absorbed by the charcoal.
The procedure used for this experiment was given in Sime. The only part of the procedure that
was changed was the milliliters of aliquot for analysis. For the 25% dilution, we used 20 mL of
aliquot instead of 25 mL. For the 5% dilution, we used 25 mL instead of 50 mL. We also ran
each concentration three times, instead of just doing it twice.
Results

Table 1 shows the data obtained from standardizing our sodium hydroxide solution and
acetic acid solution. We used acid-base titration to determine the concentrations. We repeated the
experiment three times for each solution to get an average concentration. The exact procedure for
obtaining this data can be found above, in the methods and experiment section
Table 1.
Standardizing Solutions
Solution Concentration (M) Standard Deviation

NaOH 0.8482 ± 0.005

HAc 0.6098 ± 0.04

Table 2 shows the average concentration of the different dilutions of the acetic acid
dilutions after adsorption. The concentrations were found using acid-base titration technique.
There were three trials for each experiment
Table 2.
Concentration after adsorption
Dilution Concentration (M) Standard Deviation

5% 0.01877 ± 0.0009

10% 0.04512 ± 0.003

25% 0.1289 ± 0.0009

50% 0.2757 ± 0.003

75% 0.4204 ± 0.002

100% 0.5691 ± 0.002

 Table 3 shows the average substance amount of acetic acid adsorbed per gram of the
charcoal. To calculate this, we used the average concentration for the concentration of acetic acid
before adsorption and the average concentration for the concentration of acetic acid after
adsorption. These numbers give you the same values whether you use the actual concentration
and take the average of that data or you just use the averages.
Table 3.
Substance amount of acetic acid adsorbed per gram of charcoal
Dilution Substance amount of acetic acid adsorbed per gram of
charcoal (mol/g)

5% 0.0387

10% 0.0363

25% 0.0319

50% 0.0222

75% 0.0123

100% 0.00272

Figure 1:
Freundlich Representation
0
-1.6 -1.4 -1.2 -1 -0.8 -0.6 -0.4 -0.2 0
-0.5

-1
y = 0.9922x - 1.1869
log (Y)

R² = 0.9998 -1.5

-2

-2.5

-3
log (C)

Figure 1: Freundlich Representation is a graph of the Freundlich equation. When you add a
linear line of best fit, the slope is equal to 1/n and the intercept is equal to log (k). As mentioned
in the introduction, k and n are experimentally determined constants. From the equation of the
line, you get n is equal to 1.008 and k is equal to 0.065.
 Figure 2:
Langmuir Representation
25
y = 31.681x + 4.2944
20 R² = 0.9756

15
C/Y

10

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
C

Figure 2: Langmuir Representation is a graph of the Langmuir equation. When you add a linear
line of best fit, the slope is equal to 1/Ymax and the intercept is equal to 1 /kYmax. As mentioned in
the introduction, k is an experimentally determined constant. From the equation of the line, you
get Ymax is equal to 0.03156 and k is equal to 7.378

Table 4 shows information on error analysis. All of the glassware that is used in lab are grade A
glassware. There is a certain tolerance associated with using each glassware [4]. Below is a chart
that list the errors associated with the glassware used in this lab experiment.
Table 4:
Error Analysis of glassware used
Equipment Tolerance
50 mL Buret 0.05 mL
10 mL transfer pipet 0.03 mL
20 mL transfer pipet 0.03 mL
25 mL transfer pipet 0.03 mL

Discussion

Adsorption is when certain gas or liquid molecules that are in a solution stick to a solids
surface. In this particular experiment, acetic acid is the solution that adheres to the activated
charcoals surface. The reason that activated charcoal is used is because the surface area is larger.
Adsorption can be affected by a couple different factors, including the experimental conditions,
activation of adsorbent, and the surface area of the adsorbent.

Adsorption is often studied by looking at graphs of various adsorption isotherms. In this

experiment, we focused on two adsorption isotherms, Langmuir and Freundlich. For the
Langmuir adsorption isotherm, we graphed the concentration/moles adsorbate per gram
adsorbent (c / Y) against the concentration (c). When using the Langmuir adsorption isotherm,
there are some assumptions you need to make, including: the rate of desorption is proportional to
the fraction of the surface that is already covered and the adsorbed phase forms a layer of
molecules one molecule deep [2]. When you plot c/Y against c, you should get a straight line.
The slope of the linear best fitted line will equal 1/Ymax, while the y-intercept will equal 1/kYmax.
K is a constant that are found experimentally. If you look at Figure 2, you can see the Langmuir
model on the data obtained in the lab. The graph gives a positive slope, which is expected from
the model.

As with most models, the Langmuir adsorption equation does have some limitations. One
major limitation of this model is there is the assumption that the absorbed gases behave ideally
when they are in the vapor phase. In order for the gas in the vapor phase to behave ideally, the
pressure of the system must be low. Since the Langmuir model is assuming the gases behave
ideally, there is also the assumption that the gas molecules do not interact, which we know that
this is not true. We also know that a solid’s surface is heterogeneous and that adsorption is not
monolayer, which fails some of the assumptions made when modeling the data with the
Langmuir adsorption model.

The other adsorption isotherm that we focused on in this lab is the Freundlich adsorption
isotherm. For this model, we plotted log(Y) against the log(c). These specific values are plotted
so that the graph becomes linearized. This graph gives a positive slope, which equals 1/n. When
you plot the best fitted linear line, you can get an equation for the data. The y-intercept given in
this equation log(k). Here, n and k are both constants that are found experimentally. As you can
see from figure 1, our data follows the Freundlich adsorption model pretty well. In this isotherm,
as well as the Langmuir isotherm, the constant k describes the adsorption and desorption
equilibrium. Not only are these good models to look at in this particular lab, but they can also be
used to describe and model solutions with different pressures and/or different temperatures.

When looking at our data, it shows that more solution is absorbed with the higher
concentration. It is interesting when looking at this, because at higher concentrations, there is
less room for solutions to be in contact with the solid surface. So at high concentrations, there
may be a large amount of solution on the surface, but the molecules are less connected to the
solid. What this means is that even if there are more molecules on a surface, the molecules have
less contact with the surface. However, in lower concentrations there are more rooms for the
molecules. Therefore, molecules can contact the surface and have many contacted points.

Conclusion

After activated carbon soaked in our acetic acid solutions for a week, we were then able
to do an acid-base titration on the different acetic acid solutions that were created. The dilutions
of the acetic acid made were 75%, 50%, 25%, 10%, and 5%. Looking at Figure 1 and Figure 2,
you can see that the concentration of the acetic acid solution has decreased. This is due to the
adsorption process. The adsorption process is where a liquid or gas solution adheres to a solid.
The larger the surface area, the more liquid or gas can be adsorbed. Since surface area plays a
large role in adsorption, we used activated charcoal instead of graphitized charcoal. The solution
sat for a week so that equilibrium could be reached.
Once we found the new concentrations, we were able to solve for moles adsorbate per
gram adsorbent. We then could use the equations mentioned in the introduction and plot two
different graphs. One graph would represent the Freundlich adsorption isotherm and the other
graph would represent the Langmuir adsorption isotherm. Looking at our data and these two
graphs, the Freundlich adsorption isotherm seemed to fit our data better. It is important to look at
both of these models, because it helps give an insight of the adsorption and what your data
means. One reason why the Langmuir adsorption isotherm may not have been the best fit for our
data could have been because of the assumptions required to use this model. One of the major
assumptions used is that the gas in vapor phase behaves as an ideal gas. We know that this is
incorrect and in fact, the molecules also react with each other. Due to these limitations, we
believe that the Freundlich equation better represents our data, since it can represent a wide range
of concentrations and can represent nonlinear adsorption isotherms.
In the future, I would like to do this experiment again, but I would add more steps. I test
the same isotherms, but change more of the experiment. One of the main things I would like to
do is have more dilutions, so that I can see if any dilutions are an outlier. I would also like to
compare the isotherms when the temperature is changed, as well as when the pressure is
changed. I would also like to compare the concentrations based off of the length the activated
charcoal has soaked in them. I think it would be interesting to compare the concentrations every
couple of days and see if the week was enough time for the adsorption/desorption to reach
equilibrium.
References

[1] Uhríková, D. (N.P.) Adsorption. Retrieved October 9, 2017, from

http://www.uobabylon.edu.iq/eprints/publication_1_14313_250.pdf

[2] Sime, Rodney J. Physical Chemistry: Methods, Techniques, and Experiments. Saunders
College, 1990.

[3] Rodriguez-Reinoso, F., Martin-Martinez, J.M., Prado-Burguete, C. & Mcenaney, B. (1987).

A standard adsorption isotherm for the characterization of activated carbons. The Journal of
Physical Chemistry, 91(3), 515-516.

[4] Harris, D. C. (2007). Quantitative chemical analysis. New York, NY: W.H. Freeman and Co.

https://www.scribd.com/doc/307194915/Adsorption-Isotherm-Of-Acetic-Acid-Solutions-On-Activated-
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subory/KFCHL/ENG/lectures/Physical_Chemistry/Exercise_5__Determination_of_adsorption_isotherm_
of_acetic_acid_on_activated_charcoal.pdf

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http://physicalpharmacylabreportgroupb.blogspot.com/2013/05/practical-3-adsorption-from-
solution.html

http://mimoza.marmara.edu.tr/~zehra.can/ENVE401/3.%20Adsorption%20Equilibria.pdf