Practical 3 Title: Adsorption from solution Aim: To study the adsorption of iodine from solution and to determine the

surface area of activated charcoal sample using Langmuir equation. Introduction: Adsorption is the attachment of free moving molecules of gas, liquid or dissolved solids (adsorbate) onto a surface of a solid (adsorbent). The force between adsorbent and adsorbate can influence the strength of their bond. Generally, adsorption can be divided into physical adsorption and chemisorption. Physisorption, also called physical adsorption, is a process which involves weak van der Waals forces between adsorbent and adsorbate. The induced dipole moment of a non-polar adsorbate interacts with its own image charge in the polarizable solid. It is a reversible and non-specific process. It can produce multilayer adsorption. On the other hands, chemisorption is an adsorption involves chemical bonds which is a strong interaction force. It is characterized by high temperatures, strong covalent bond between adsorbate and solid surface, high enthalpy, monolayer, high activation energy, increase in electron density in the adsorbent-adsorbate interface and not readily reversible. Adsorption isotherm is study of the relationship between the degree of adsorption and the partial pressure or concentration. It can determine the characteristics of solid and the reaction involved when adsorption occurs. Basically, physical adsorption is far more common than chemisorption. The extent of adsorption is influenced by several factors such as solute concentration, temperature, pH and surface area of absorbent. Surface area can affect the rate of dissolution and bioavailability of drugs through the gastrointestinal tract. Adsorption measurement is used to determine the surface area of a solid. With rough surfaces and pores, the actual surface area can be large when compared to the geometric apparent surface area. Adsorption of gas was used to measure the surface area by using the method of B.E.T (Brunauer, Emmett and Teller).

Materials and apparatus: 12 conical flasks, 6 centrifuge tubes, measuring cylinders, analytical balance, Beckman J6M/E centrifuge, burettes, retort stand and clamps, Pasteur pipettes, iodine solutions (specified in Table 1), 1% w/v starch solution, 0.1 M sodium thiosulphate solution, distilled water and activated charcoal.

Experimental procedures: 12 conical flasks (labeled 1-12) are filled with 50ml mixtures of iodine solutions (A and B) as stated in the Table 1 by using burettes or measuring cylinders. Table 1: Solution A: Iodine (0.05 M) Solution B: Potassium iodide (0.1 M) Flask 1 and 7 2 and 8 3 and 9 4 and 10 5 and 11 6 and 12 Volume of solution A (ml) 10 15 20 25 30 50 Volume of solution B (ml) 40 35 30 25 20 0

Set 1: Actual concentration of iodine in solution A (X) For flasks 1-6: 1) 1-2 drops of starch solution are added as an indicator. 2) The solution is titrated using 0.1 M sodium thiosulfate solution until the colour of the solution changes from dark blue to colourless. 3) The volume of the sodium thiosulfate used is recorded.

Set 2: Concentration of iodine in solution A at equilibrium (C) For flasks 7-12: 1) 0.1g of activated charcoal is added.

2) The flasks are capped tightly. The flask is swirled or shook every 10 minutes for 2 hours. 3) After 2 hours, the solutions are transferred into centrifuge tubes and they are labelled accordingly. 4) The solutions are centrifuged at 3000rpm for 5 minutes and the resulting supernatant is transferred into new conical flasks. Each conical flask is labelled accordingly. 5) Steps 1, 2 and 3 are repeated as carried out for flasks 1-6 in Set 1.

Results: Flask 1 2 3 4 5 6 7 8 9 10 11 12 Initial Volume (ml) 31.0 0.0 11.5 23.1 8.8 1.8 0.0 2.8 10.8 14.0 17.4 21.9 Final Volume (ml) 37.2 9.5 24.2 40.3 29.5 35.3 1.1 4.5 13.1 17.2 21.3 28.7 Volume (ml) 6.2 9.5 12.7 17.2 20.7 33.5 1.1 1.7 2.3 3.2 3.9 6.8 Used

GENERAL NOTES: Titration equation: Given: 1 mole iodine = 2 x 126.9 g 1 ml 0.1 M = 0.01269 g I If the amount of activated charcoal used is Y gram, therefore the total mole of iodine adsorbed by 1 g of activated charcoal (N) is given by the following equation: ( ) 1) Calculate N for iodine in each flask. N = (X-C) x 50/1000 x 1/y For flask 1 and 7: For X value: Mass of iodine = 6.21 x 0.01269 g = 0.078678 g Number of moles of iodine = 0.078678(2x 126.9) x 1 = 3.1 x 10-4 mole Concentration of iodine = 2.8 x 10-4 50 x 1000 = 6.2 x 10-3 mol dm-3 Thus, X = 6.2 x 10-3 mol dm-3 For C value: Mass of iodine = 1.11 x 0.01269 g = 0.013959 g Number of moles of iodine = 0.013959 (2x 126.9) x 1 = 5.5 x 10-5 mole Concentration of iodine = 5.5 x 10-5 12 x 1000 = 4.583 x 10-3 mol dm-3 Thus, C = 4.583 x 10-3 mol dm-3 N = (6.2 x 10-3 -4.583 x 10-3)x 50/1000 x 1/0.1 = 8.0850 x 10-4 mole

For flask 2 and 8: For X value: Mass of iodine = 9.51 x 0.01269 g = 0.120555 g Number of moles of iodine = 0.120555 (2x 126.9) x 1 = 4.75 x 10-4 mole Concentration of iodine = 4.75 x 10-4 50 x 1000 = 9.5 x 10-3 mol dm-3 Thus, X =9.5 x 10-3 mol dm-3 For C value: Mass of iodine = 1.7 1 x 0.01269 g = 0.021573 g Number of moles of iodine = 0.021573 (2x 126.9) x 1 = 8.5 x 10-5 mole Concentration of iodine = 8.5 x 10-5 12 x 1000 = 7.083 x 10-3 mol dm-3 Thus, C = 7.083 x 10-3 mol dm-3 N = (9.5 x 10-3 -7.083 x 10-3)x 50/1000 x 1/0.1 = 1.2085x 10-3 mol

For flask 3 and 9: For X value: Mass of iodine = 12.7 1 x 0.01269 g = 0.1612 g Number of moles of iodine = 0.1612 (2x 126.9) x 1 = 6.35 x 10-4 mole Concentration of iodine = 6.35 x 10-4 50 x 1000 = 12.7x 10-3 mol dm-3 Thus, X = 12.7x 10-3 mol dm-3 For C value: Mass of iodine = 2.3 1 x 0.01269 g = 0.029187 g Number of moles of iodine = 0.029187(2x 126.9) x 1 = 1.15 x 10-4 mole

Concentration of iodine = 1.15 x 10-4 12 x 1000 = 9.583 x 10-3 mol dm-3 Thus, C = 9.583 x 10-3 mol dm-3 N = (12.7 x
- 9.583 x

)x 50/1000 x 1/0.1

= 15.585 x 10-4 mol

For flask 4 and 10: For X value: Mass of iodine = 17.2 1 x 0.01269 g = 0.218268 g Number of moles of iodine = 0.218268 (2x 126.9) x 1 = 8.6x 10-4 mole Concentration of iodine = 8.6 x 10-4 50 x 1000 = 17.2x10-3 mol dm-3 Thus, X = 17.2x10-3 mol dm-3 For C value: Mass of iodine = 3.2 1 x 0.01269 g = 0.040608 g Number of moles of iodine = 0.040608 (2x 126.9) x 1 = 1.6 x 10-4 mole Concentration of iodine = 1.6 x 10-4 12 x 1000 = 13.333 x 10-3 mol dm-3 Thus, C = 13.333 x 10-3 mol dm-3 N = (17.2 x 10-3 -13.333 x 10-3)x 50/1000 x 1/0.1 = 19.335 x 10-4 mol

For flask 5 and 11: For X value: Mass of iodine = 20.7 1 x 0.01269 g = 0.262683 g Number of moles of iodine = 0.262683 (2x 126.9) x 1 = 1.035 x 10-3 mole Concentration of iodine = 1.035 x 10-3 50 x 1000 = 20.7 x 10-3 mol dm-3

Thus, X = 20.7 x 10-3 mol dm-3 For C value: Mass of iodine = 3.9 1 x 0.01269 g = 0.049491 g Number of moles of iodine = 0.049491 (2x 126.9) x 1 = 1.95 x 10-4 mole Concentration of iodine = 1.95 x 10-4 12 x 1000 = 16.25 x 10-3 mol dm-3 Thus, C = 16.25 x 10-3 mol dm-3 N = (20.7 x 10-3 -16.25 x 10-3)x 50/1000 x 1/0.1 = 22.250 x 10-4 mol

For flask 6 and 12: For X value: Mass of iodine = 33.5 1 x 0.01269 g = 0.425115 g Number of moles of iodine = 0.425115 (2x 126.9) x 1 = 1.675 x 10-3 mole Concentration of iodine = 1.675 x 10-3 50 x 1000 = 33.5 x 10-3mol dm-3 Thus, X = 33.5 x 10-3mol dm-3 For C value: Mass of iodine = 6.8 1 x 0.01269 g = 0.086292 g Number of moles of iodine = 0.086292 (2x 126.9) x 1 = 3.4 x 10-4 mole Concentration of iodine = 3.4 x 10-4 12 x 1000 = 28.333 x 10-3 mol dm-3 Thus, C = 2.54 x 10-2 mol dm-3 N = (33.5 x 10-3-28.333 x 10-3)x 50/1000 x 1/0.1 = 25.835 x 10-4 mol

2) Plot amount of iodine adsorbed (N) versus balance concentration of solution (C) at equilibrium to obtain adsorption isotherm.

Graph of amount of iodine adsorbed (N) versus balance concentration of solution (C) at equilibrium
30

25

Amount of iodine adsorbed, N (x 10M/g)

20

15

10

0
0 5 10 15 20 25 30 Balance concentration of solution (C) at equilibrium ( x 10 M)

3) According to Langmuir theory, if there is no more than a monolayer of iodine adsorbed on the charcoal, C/N = C/Nm = 1/KNm Where C = concentration of solution at equilibrium Nm = number of mole per gram charcoal required K = constant to complete a monolayer

Plot C/N versus C, if Langmuir equation is followed, a straight line with slope of 1/Nm and intercept of 1/KNm is obtained. Obtain the value of Nm, and then calculate the number of iodine molecule adsorbed on the monomolecular layer. Assume that the area covered by one adsorbed molecule is of charcoal in C (x 10 ) 4.583 7.083 9.583 13.333 16.250 28.333 N (x 10) 8.0850 12.085 15.585 19.335 22.250 25.835 C/N 5.6685 5.8610 6.1489 6.8958 7.3034 10.9669 , Avogadro no.= , calculate the surface area

Graph of C/N versus C

12

11

10

C/N

4 0 5 10 15 C (x 10) 20 25 30

( ( )

Gradient = 1/Nm = Thus, No. of moles of charcoal = x 0.1 g

= 4.5 x 10 mol No. of charcoal molecules = 4.5 x 10 mol x ( = 2.7104 x molecules x (3.2 x ) ) molecules/mol

Area covered by charcoal molecules = 2.7104 x = 86.7328 Surface area of charcoal = 86.7328 = 867.328 / 0.1 g

4) Discuss the results of the experiment. How do you determine experimentally that equilibrium has been reached after shaking for two hours? Equilibrium has been reached when the solution becomes homogenous and has no more colour changes.

Discussion: Adsorption is a process a soluble substance is being removed from the water by using a solid. The soluble substance is accumulated at the interface. In this experiment, activated charcoal is the solid. It is because the activated charcoal has large internal surface which makes it an ideal carbon for adsorption. Adsorption activity will be decreased if a polar substance is used whereas a non-polar substance will have a good adsorption activity by using activated charcoal. Hence, non-polar iodine is used in this practical. Solute concentration is also the factor that affects adsorption. When the solute concentration increases, the amount of adsorption occurring at equilibrium also will increase until a limiting value is reached. The graph of amount iodine adsorbed against balance concentration of solution(C) at equilibrium shows Langmuir isotherm for the adsorption of the iodine molecules on activated charcoal which is hyperbolic shape. When the concentration of iodine in solution A at equilibrium (C) increases from flasks 7 to 12, the total mole of iodine adsorbed by 1 g of activated charcoal (N) also increases. The actual concentration of iodine in solution A (X) is always smaller than the concentration of iodine in solution A at equilibrium. It is because the iodine is being adsorbed by the activated charcoal. Hence, the amount of iodine left is decreased. Equilibrium is established when there are no further change in the concentration of supernatant is observed when titrated with sodium thiosulphate solution. According to Langmuir Isotherm Adsorption, the thickness layer of gas molecules being adsorbed is monolayer. From the graph C/N against C obtained, a straight line is obtained. Thus, the Langmuir theory is obeyed. Monolayer of iodine had been adsorbed on the surface of charcoal. From the graph, we can obtain the number of mole per gram charcoal required (Nm) by calculating its gradient. Nm is a measure of the adsorptive capacity of the activated charcoal for the iodine molecule. The surface area of charcoal can be calculated from the value of Nm. There are few precaution steps that need to be taken to ensure the accuracy of result. Firstly, we must avoid the parallax error. Next, we must be careful when transferring supernatant so that activated charcoal in not taken in together. The conical flask need to be swirled continuously when titrated with sodium thiosulphate solution to ensure complete reaction occur.

Conclusion: Iodine can be adsorbed by activated charcoal. The surface area of activated charcoal sample used in this experiment is 867.328 .

Reference: 1. A.T.Florence and D.Attwood. ; 2006; Physicochemical Principals of Pharmacy, 4th Edition. Pharmaceutical Press. 2. Martin,A.N.2006. Physical Pharmacy: Physical Chemistry Principles in Pharmaceutical Sciences. 5th Ed. Philadelphia: Lea & Febiger. 3. Alfonso R.Gennaro al. 1995; Remington: The Science & Practice of Pharmacy; 19th edition.; Mack Publishing Company Easton, Pennsylavania; page 246