Experiment 15 Adsorption of Acetic Acid by a Solid Since solids exist because of intermolecular forces between the repeati units that make up the lattice, those intermolecular forces are unsaturat or unsatisfied at the surface of the solid. In the interior of a solid, ea molecule (if it is a molecular solid) is surrounded on all sides by identical 7 molecules. At the surface of such a solid, however, each molecule is only partially surrounded by identical molecules; where it is not surrounded by identical molecules, any available molecule or ion is adsorbed to its surface. The solid phase is called the adsorbent. The molecules that adsorbed on the adsorbent are collectively called the adsorbed phase adsorbate. The adsorbate is either a gas (molecules) or a solute (molecul or ions) in solution. In this experiment, we will investigate the adsorp' of acetic acid in aqueous solution on activated charcoal. Adsorption by a solid is not a very important process unless th solid has a very large surface compared to its mass. Consequently, cha made from bone, blood, or coconut shells is especially effective because: it has a highly porous structure. Charcoal is activated by being heated to quite high temperatures in a vacuum or in a stream of dry air. ' treatment probably desorbs the hydrocarbons that are adsorbed when the charcoal is first produced. Charcoal, a covalently bonded solid, ig more effective at adsorbing molecules than ions. Silver chloride, on other hand, forms as a precipitate of nearly colloidal dimensions if p cipitated rapidly; in colloidal form it has a very high surface-to-mass rati and readily adsorbs ions from solutions, often to the dismay of analytical chemists. i The amount of adsorption, given the symbol Y, has units of moles adsorbate per mass adsorbent. If the adsorbate isa gas, Y may have units? of volume adsorbate per mass adsorbent. The amount of adsorption ¥ increases with the concentration c of the adsorbate. The increase is very rapid at first, when the surface of the adsorbent is relatively free. As t surface fills with the adsorbate, the rate of adsorption dY/dc decreas Eventually, the surface of the adsorbent becomes full, and further inc! in the concentration cause no further increase in the amount adsorbe as shown in Figure 15-1. The amount adsorbed when the surface is j us covered with a monomolecular layer of the adsorbate is called Yinax- 4 a given concentration the amount adsorbed decreases with in i temperature. a . Se a 0529 Low temperature —_r__ . moles/gram High temperature € Figure 15-1 Typical adsorption moles/liter isotherms. The Freundlich Equation One of the earliest attempts to describe mathematically the adsorption isotherms shown in Figure 15-1 was the Freundlich equation (Freundlich, 1909): Y= kel!" (15-1) In this purely empirical equation, the units of Y are moles adsorbate per gram adsorbent, c is the concentration (mol/L), and k and n are exper- imentally determined constants. Since Equation 15-1 is valid only for a given adsorbed phase and adsorbent at a constant temperature, it is sometimes called the Freundlich isotherm. To test the validity of the Freundlich isotherm, take the logarithms of both sides of Equa- tion 15-1: I logio Y = logio k + a logio ¢ (15-2) If logio Y is plotted against logy c, a straight line results with the slope equal to 1 /n and the intercept equal to logiy k. The Langmuir Adsorption Isotherm The Langmuir adsorption isotherm is based on theoretical considerations. The postulates of the theory are as follows: 1. The adsorbed phase forms a layer of molecules one molecule deep.: 2. The system is in a state of equilibrium such that the rate of ad- sorption equals the rate of desorption. 3. The rate of adsorption is proportional to the concentration and the fraction of the surface that is vacant.4. The rate of desorption is proportional to the fraction of the that is already covered. If ¢ is the fraction of the surface that is covered, then 1 — 6 is the frac of the surface that is vacant. Consequently, kyl — 0) = ke _ _ ke O= Ct he If k is defined to be k,/k2, Equation 15-4 becomes . ke Oo Tyke Since the fraction of the surface covered is also equal to Y/Yinaxs We write Y __ke Yinax 1+ ke With rearrangement, Equation 15-6 becomes e 1 ye Y kY¥ max Ynax This is the equation of the Langmuir adsorption isotherm. If a sy: follows the Langmuir equation, then a plot of c/ Y versus ¢ is a stra line with a slope equal to 1 / Yimax and an intercept equal to 1/ KY wnax Determination of the Specific Area of the Adsorbent ; If the adsorption of the adsorbate leads to a maximum of a single mo lecular layer when the adsorption is complete, it is possible to calcul ate the area of the adsorbent. When a monomolecular layer is adsorb it may be assumed that the area of the adsorbent equals the total al the adsorbed molecules. The determination of the area of an adsorb molecule is simple in the case of small adsorbed gas molecules su helium, hydrogen, and nitrogen. When the adsorbed molecule is boxylic acid, however, the structure is clearly more complex. Neverth studies of the adsorption of straight-chain aliphatic monocarboxylic indicate that the number of moles of acid adsorbed per gram adsorb is independent of chain length (Hansen and Craig, 1954). This sugs that the acid molecules are adsorbed vertically, with the aliphatic chi up and the carboxyl group down and attached to the adsorbent. cross-sectional area A, of a straight-chain acid may be taken to be abo! &531 21 X 10°? m2. The specific area of the adsorbent S'(m7?/g) is then given by S = AN ¥inax (15-8) where N, is Avogadro’s number. Apparatus This experiment requires about 20 g activated charcoal (from blood); 12 glass-stoppered 125-ml Erlenmeyer flasks; 5-, 10-, 25-, and 50-ml pi- pets; medium-fine filter paper; 600 ml 0.4 M acetic acid; 500 ml 0.1 M sodium hydroxide (standardized); a phenolphthalein indicator; and a 50-ml buret. SAFETY CONSIDERATIONS If it is necessary to prepare the 0.4 M acetic acid from glacial acetic acid, take care not to breathe the fumes, and carry out the dilution in a ventilated hood. EXPERIMENTAL PROCEDURE a Weigh about 1.5 g charcoal into each of the dry glass-stoppered Erlenmeyer flasks. Record the weight to +1 mg. Prepare a series of acetic acid solutions of various concentrations according to Table 15-1. Add 100 ml of each solution to each charcoal sample. Swirl the flasks vigorously and let them stand overnight. Filter the solutions and titrate a suitable size aliquot (Table 15-1) of each filtrate with standard 0.1 M sodium hydroxide. Use progressively larger aliquots for the more dilute solutions. Run each concentration in duplicate. TABLE 15-1 es Suggested Volumes of 0.4 M Acetic Acid to Dilute to 100.00 mi 0.4 M Acetic Acid Aliquot for Analysis Sample" (ml) (ml) 1 100 10 2 15 10 3 50 10 4 25 25 5 10 25 6 5 50 * Prepare samples in duplicate.es ¢ Experiment Results and Calculations From the titration data determine the concentrations of the original aceti: acid solution and of the acid solutions in equilibrium with the adsorbent From the volume of the solutions, their equilibrium concentrations, an the original acid concentrations, calculate Y, the number of moles o acid adsorbed per gram of adsorbent. Prepare suitable tables of the quantities needed to test the validit of the Freundlich and Langmuir isotherms for the aqueous acetic acid charcoal system. Plot the duplicate runs independently (do not averag before plotting). Calculate Freundlich and Langmuir parameters an discuss the observed results. REFERENCES 1. Brunauer, S., “Adsorption of Gases in Multimolecular Layers,” J. Am. Chen Soc. 60:309, 1938. 2. Brunauer, S., Physical Adsorption, Princeton University Press, Princeton, Ne Jersey, 1971. 3. Duff, D. G., S. M. C. Ross, and D. H. Vaughn, “Adsorption from Solution J. Chem. Educ. 65:815-816, 1988. 4. Dunicz, B. L., “Surface Area of Activated Charcoal by Langmuir Adsorptic Isotherm,” J. Chem. Educ. 38:357, 1961. 5. Freundlich, H. M. F., Kappilarchemie, Leipzig, 1909. 6. Hansen, R. S., and R. P. Craig, “The Adsorption of Aliphatic Alcohols fro Aqueous Solutions by Non-Porous Carbons,” J. Phys. Chem. 58:211, 1954. 7, Langmuir, I, “The Constitution and Fundamental Properties of Solids ar Liquids,” J. Am. Chem. Soc. 38:2221, 1916. 8. Popiel, W. J., “Adsorption by Solids from Binary Solutions,” J. Chem. Ed 43:415-418, 1966.