ADSORPTION

ABSTRACT Adsorption process is the phenomena being studied and performed in this experiment. Serial dilutions were done for the preparation of the different HOAc solutions, which serve as the adsorbate. The adsorbent used was an activated charcoal. HOAc solutions were then added to the charcoal and filtered after it equilibrates. The filtrate was titrated using the standard NaOH solution and the volume delivered was recorded. Following certain formulas and calculations, the mass of the HOAc adsorbed was calculated. At the end of the experiment, the experimenters were able to construct the Langmuir Isotherm that leads to the Langmuir equation, which corresponds to the given Langmuir relationship for monomolecular adsorption. The determined Langmuir equation is y=0.7447x + 2.9886 and the values of a and b are 0.249180 and 1.342822 respectively. INTRODUCTION This experiment, which observes the process of adsorption, aims to determine adsorption isotherm of acetic acid on activated charcoal. The adsorption is studied using the Langmuir's relationship for monomolecular adsorption. For that, the experiment's objective, as well, is to determine the constants a and b in Langmuir equation by constructing and adsorption isotherm adsorbed from a solution into a porous solid. Adsorption is the adhesion of atoms, ions, biomolecules or molecules of gas, liquid, or dissolved solids to a surface. This process creates a film of the adsorbate (the molecules or atoms being accumulated) on the surface of the adsorbent. Through adsorption, the solid has the capability to attract to their surfaces molecules of gases or solutions with which they are in contact. Usually, adsorption is monomolecular. That is, adsorption ceases when the surface is completely covered with a layer of one molecular thick. The amount of adsorption therefore varies with the concentration of the solution. Solids that are used to adsorb gases or dissolved substances are called adsorbents; the adsorbed molecules are usually referred to collectively as the adsorbate. An example of an excellent adsorbent is the charcoal used in gas masks to remove poisons or impurities from a stream of air. For this experiment, the adsorbent used is an activated charcoal. Activated carbon is a highly porous, amorphous solid consisting of microcrystallites with a graphite lattice, usually prepared in small pellets or a powder. It is used for adsorption of organic substances and nonpolar adsorbates and it is usually used for waste gas and wastewater treatment. It is the most

widely used adsorbent since most of its chemical and physical properties can be tuned according to what is needed. Its usefulness also derives from its large micropore and sometimes mesopore volume and the resulting high surface area. Adsorption is always confused with absorption. It is different from absorption in a sense that absorption refers to processes in which a substance penetrates into the actual interior of crystals, of blocks of amorphous solids, or of liquids. Sometimes the word sorption is used to indicate the process of the taking up of a gas or liquid by a solid without specifying whether the process is adsorption or absorption. Adsorption is usually described through isotherms, that is, functions which connect the amount of adsorbate on the adsorbent, with its pressure (if gas) or concentration (if liquid). One can find in literature several models describing process of adsorption, namely Freundlich isotherm, Langmuir isotherm, BET isotherm, etc. For this experiment, the Langmuir isotherm will be used. In 1916, Irving Langmuir published an isotherm for gases adsorbed on solids, which retained his name. It is an empirical isotherm derived from a proposed kinetic mechanism. It is based on four hypotheses: 1. The surface of the adsorbent is uniform, that is, all the adsorption sites are equal. 2. Adsorbed molecules do not interact. 3. All adsorption occurs through the same mechanism. 4. At the maximum adsorption, only a monolayer is formed: molecules of adsorbate do not deposit on other, already adsorbed, molecules of adsorbate, only on the free surface of the adsorbent. For liquids (adsorbate), which for this experiment is acetic acid, adsorbed on solids (adsorbent), the Langmuir isotherm can be expressed by

Where:

x/m = the weight of adsorbed material per gram of adsorbent C = the concentration of the solution at equilibrium a = constant proportional to the heat of adsorption b = the amount of adsorption when the surface is covered with a monomolecular

film.

MATERIALS AND METHODS The experiment has a certain procedure to be observed and followed. However, before the experiment was done, the materials were first prepared and cleaned. The materials used for this experiment were, analytical balance, 250-mL Erlenmeyer flasks, 100-, 250- and 500-mL volumetric flasks, volumetric pipets, 50-mL buret and filter papers. First step done is the standardization of the 0.1N NaOH. For this, 2g of NaOH pellets were weighed accurately. These are placed in a 500-mL volumetric flask and diluted up to mark with water. In addition, a known amount of KHP was diluted to up to 10mL with water. The KHP serves as the analyte and it was titrated with the prepared NaOH. The volume of NaOH delivered was recorded and was used for the calculation of the true concentration of NaOH. After that, 10 Erlenmeyer flasks are prepared and labeled. In each flask, an accurately weighed 1.4g-1.6g of activated charcoal is placed. Simultaneously, different concentrations (0.75, 0.60, 0.50, 0.40, 0.25, 0.15, 0.1, 0.01, 0.001 and 0 M) of Acetic acid solution were prepared through successive dilutions. First, 0.75M was prepared from the 17.4M Acetic acid. After that, the remaining solutions with different concentrations were prepared from the 0.75M HOAc. 100mL of each of these HOAc solutions were added to the flasks with charcoal, respectively. Each flask were closed with stopper and swirled at frequent intervals.

Meanwhile, three 10mL aliquot of the original HOAc solution, which is 0.75M, was titrated with the standardized NaOH solution to be able to get the acetic acid titer. From the standardized HOAc solution, the true concentrations of the other HOAc solution were calculated. The solutions are then left to equilibrate for at least 24 hours. After the systems equilibrate, these were filtered. For the more concentrated solutions (0.75, 0.60, 0.50, 0.40, 0.25, 0.15), 10mL aliquots of the filtrate were titrated with the standard NaOH. For the more diluted solutions (0.1, 0.01, 0.001 and 0 M), 25mLaliquots were titrated. In each of the concentration or specific solution, two runs were conducted. The volumes of NaOH delivered were recorded for the calculations.

RESULTS AND DISCUSSION After performing the necessary method for this experiment, all the data observed, gathered and calculated are presented in tables below. Table 1. Serial Dilutions Initial Concentration of HOAc (mol/L) 17.4 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 Final concentration of HOAc (mol/L) 0.75 0.60 0.50 0.40 0.25 0.15 0.1 0.01 0.001 0.00

Initial Volume (mL) 21.55 80.00 66.67 53.33 33.33 20.00 13.33 1.33 0.13 0.00

Final Volume (mL) 500 100 100 100 100 100 100 100 100 100

The first data presented in table 1, contains the initial concentration of HOAc, the initial volume to be diluted and the final concentration needed for the experiment proper. The final concentration, initial and final volume being known, the initial volume to be diluted can be calculated using the formula, M1 V1 = M2 V2.

Table 2. Standardization of NaOH a.) 1st 500mL of NaOH Standard Volume of aliquot (mL) Volume of NaOH (mL) concentration of NaOH (mol/L) 100 10 50.71 29.40 0.0985897 0.0998156 Average Concentration of NaOH (mol/L) 0.09920265

Concentration Run of KHP (mol/L) 1 2 0.049985 0.293458

b.) 2nd 500mL of NaOH Standard Volume of aliquot (mL) Volume of NaOH (mL) concentration of NaOH (mol/L) 10 10 29.65 29.55 0.0990896 0.0994250 Average Concentration of NaOH (mol/L) 0.099257

Concentration Run of KHP (mol/L) 1 2 0.293801 0.293801

Table 2, which contains the data for the standardization of NaOH, has two sets. First is the standardization of the 1st set of 500mL NaOH and the next is the data for the standardization of the 2nd set of 500mL NaOH. With the known concentration of KHP and the volume of NaOH delivered in the titrating the KHP (analyte), the standard concentration of NaOH can be calculated by following the formula, MNaOH = [(VKHPMKHP) (1mol NaOH/1mol KHP)] / VNaOH. The first 500mL of NaOH was used for the titration of the HOAc solution with concentration from 0.75M to 0.50M, and the second 500mL was used for 0.40, 0.25, 0.15, 0.1, 0.01, 0.001, 0.0M of HOAc.

Table 3. Standardization of Original Acetic Acid Concentration of Original Acetic Acid (mol/L) 1 0.75 2 3 Run Standard Average

Volume of Aliquot (mL) 10 10 10

Concentration of NaOH (mol/L)

Volume of NaOH (mL) 75.19

Concentration Concentration of Original HOAc (mol/L) 0.74590 0.76098 0.74898 0.751953 of the HOAc (mol/L)

0.09920265

76.71 75.50

The data recorded and calculated for the standardization of the original acetic acid, which is 0.75M for this experiment, is presented in table 3. The volume of the aliquot for the three runs is 10mL and these are titrated with the standardized NaOH. The volume of NaOH delivered was recorded and used for the calculation of the true concentration of HOAc following the formula, MHOAc= [(VNaOHMNaOH) (1mol HOAc/1mol NaOH)] / VHOAc. The average is then calculated

Table 4. Titration of HOAc Solution Initial Flask No. Concentration of HOAc (mol/L) 1 0.751953 1 2 1 2 1 2 1 2 1 2 1 2 1 2 1 2 1 2 1 2 10 10 10 10 10 10 10 10 10 10 10 10 25 25 25 25 25 25 25 25 Run Volume of Aliquot (mL) Final Concentration of HOAc (mol/L) 0.690351 0.69144 0.55157 0.55157 0.46750 0.46750 0.37122 0.37420 0.23415 0.24268 0.14174 0.14174 0.093302 0.093302 7.5435 x10-3 7.9406 x10
-3

Volume of NaOH (mL) 69.59 69.70 55.60 55.60 47.10 47.10 37.40 37.70 23.59 24.55 14.28 14.28 23.50 23.50 1.90 1.60 0.24 0.24 0.08 0.09

Average Final Conc. of HOAc (mol/L) 0.69090

0.601562

0.55157

0.501327

0.46750

0.401017

0.37271

0.250626

0.24049

0.150391

0.14177

0.100235

0.093302 7.742x10-3 9.529x10-4

0.010000

0.001000

9.5287 x10-4 9.5287 x10-4 0 0

10

The next data presented above, in table 4, are obtained through the titration of the HOAc solutions with the standard NaOH. The initial concentrations of HOAc presented are the standard concentrations of the HOAc solutions used. These are obtained using the acetic acid titer. The initial concentration of HOAc and the volume of NaOH delivered being known and recorded, the final concentration of HOAc, or its concentration in equilibrium, is calculated. It can be observed that as the concentration of HOAc increases, the volume of NaOH delivered

decreases ad the final HOAc concentration increases. The results therefore follow the characteristic of adsorption, which is the dependence on the concentration of the adsorbate. Table 5. Moles and Masses of the HOAc Mole of HOAc adsorbed (mol) 6.105 x10-3 4.999 x10
-3

Initial Flask No. Moles of HOAc (mol) 1 2 3 4 5 6 7 8 9 10 0.075195 0.060156 0.050133 0.040102 0.025063 0.015039 0.010024 0.001000 0.000100 0

Final Moles of HOAc (mol) 0.069090 0.055157 0.046750 0.037271 0.024049 0.014174 9.330 x10 7.742 x10
-3 -4

Weight of adsorbed HOAc (g) 0.3666 0.3002 0.2032 0.1700 0.0609 0.0519 0.0417 0.01356 2.522 x10-4 0

Mass of Charcoal (g) 1.4810 1.5138 1.5261 1.4835 1.4661 1.4500 1.4492 1.4660 1.4906 1.4500 0.247535 0.198309 0.133150 0.114594 0.041539 0.035793 0.0287745 9.250 x10-3 1.692 x10-4 0

3.383 x10-3 2.831 x10-3 1.014 x10-3 8.650 x10-4 6.940 x10 2.258 x10
-4 -4

9.530 x10-5 0

4.700 x10-6 0

Table 5 presents the final and initial moles of HOAc. Subtracting the initial mole to the final, the mole of HOAc adsorbed was therefore obtained. The moles calculated are then multiplied with the molar mass of HOAc to calculate the mass (g). The mass adsorbed is now the variable x in the Langmuir equation. X/m, where m is the mass of the charcoal, in each corresponding flask no. is also presented. It can also be observed that the x/m increases as the mass adsorbed increases.

Table 6. Data for the Construction of the Langmuir Isotherm C2 0.69090 0.55157 0.46750 0.37271 0.24049 0.14177 0.093302 7.742x10-3 9.529x10-4 0 0.247535 0.198309 0.133150 0.114594 0.041539 0.035793 0.0287745 9.250 x10-3 1.692 x10-4 0 C2 / (x/m) 2.79112 2.78137 3.51108 3.25244 5.78950 3.96083 3.24252 0.83697 5.63180 0

Table 6 is presented for the construction of the Langmuir Isotherm.

Graph 1. C2 vs x/m

Final HOAc concentration vs. x/m

0.8 HOAc concentration (mol/L) 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.05 0.1 x/m 0.15 0.2 0.25 0.3 Linear (Final HOAc concentration vs. x/m) y = 2.7961x + 0.0305 R = 0.9643

0 -0.05-0.1 0

The first graph presented above is the plot of the final HOAc concentration vs. the x/m values. Using the best-fit line, the equation of the line is obtained and found to y = 2.7961 +

0.0305. it can be observed through the plot that there is direct proportion between concentration of HOAc and x/m; as C2 increases, x/m increases. Graph 2. C2/(x/m) vs C2

C/(x/m) vs Final HOAc conc.

7 6 C/(x/m) 5 4 3 2 1 0 -0.2 0 0.2 0.4 0.6 0.8 C (mol/L) C/(x/m) vs Final HOAc conc. Linear (C/(x/m) vs Final HOAc conc.) y = 0.7447x + 2.9886 R = 0.0107

The graph two presents the Langmuir isotherm, plotting the C2/(x/m) vs. C2. The graph seemed not to follow the typical Langmuir isotherm. It can be inferred therefore that there is an error somewhat, in the preparation of the more diluted HOAc solution. Since the NaOH solution used in the titration of the more diluted solutions is different with that of the more concentrated, and during the standardization of HOAc, only the first set of NaOH was used, there are discrepancies in the resulting values of calculations. Using the best-fit line, the equation of the line which corresponds to the Langmuir equation is y=0.7447x + 2.9886. SAMPLE CALCULATIONS Serial Dilutions M1 V1 = M2 V2 17.4 x V1 = 0.75 x 0.500 V1 = 0.02155 Standardization of NaOH

Conc. of KHP = .60g (1mol/204.22g) 0.010L = 0.293801M KHP MNaOH = (VKHPMKHP) (1mol NaOH/1mol KHP) VNaOH Stand. conc. of NaOH = 0.010L KHP (0.288904M KHP) (1molNaOH/1mol KHP) 0.02965L NaOH = 0.0990896M NaOH Standardization of Original HOAc MHOAc = (VNaOHMNaOH)(1mol HOAc/1mol NaOH) VHOAc Stand. conc. of HOAc = 0.07519L NaOH (0.09920265M NaOH) (1mol KHP/1mol NaOH) 0.010L = 0.74590M HOAc True Concentration of the diluted HOAc M1 V1 = M2 V2 0.751953 x 0.08 = M2 x .100 M2 = 0.601562 Concentration of HOAc in Equilibrium conc. of HOAc = 0.06959LNaOH (0.09920265M NaOH) (1mol HOAc/1mol NaOH) 0.010L HOAc = 0.690351 M HOAc Initial Moles of HOAc moles of HOAc = 0.751953M HOAc (.100L HOAc) = 0.075195 mol HOAc Final Moles of HOAc moles of HOAc = 0.69090M HOAc (.100L HOAc) = 0.069090 mol HOAc

Moles of HOAc Adsorbed moles of HOAc = Final moles HOAc - Initial moles HOAc = 0.069090 mol - 0.075195 mol = 6.105 x10-3 mol HOAc Weight of HOAc Adsorbed mass = Moles adsorbed x Molar mass of HOAc = 6.105 x10-3 mol (60.052g HOAc/1mol) = 0.3666g HOAc

CONCLUSION After performing all the necessary methods for this experiment, the experimenters were able to construct the Langmuir Isotherm. Therefore, the Langmuir equation obtained in this experiment is y=0.7447x + 2.9886. The equation corresponds to the given Langmuir relationship for monomolecular adsorption. The slope (1/b) is found to be 0.7447 and the y-intercept (1/ab) is 2.9886. The value of the constant a and b therefore are, 0.249180 and 1.342822 respectively.

REFERENCES http://www.britannica.com/EBchecked/topic/6565/adsorption (accessed March 14, 2011) http://en.wikipedia.org/wiki/Adsorption (accessed March 14, 2011) http://en.wikipedia.org/wiki/Adsorption#Activated_carbon (accessed March 14, 2011) http://en.wikipedia.org/wiki/Adsorption#Langmuir (accessed March 14, 2011) http://www.rensselaer.org/dept/chem-eng/Biotech-Environ/Adsorb/adsorb.htm (accessed March 14, 2011)