Sunday, 25 May 2014

LAB 3: Adsorption from solution

Title

Practical 3: Adsorption from solution

Introduction


Adsorption is the adhesion of molecules, ions or atoms of gas or liquid to a surface of an adsorbent (solid or liquid). This will lead to accumulation of the gas or liquid on the surrounding of the adsorbent which later will form a molecular or atomic film. Adsorption is different from absorption, in which a substance diffuses into a medium. 


Adsorption is a consequence of surface energy. Atoms on the clean surface of the adsorbent experience a bond deficiency because they are not wholly surrounded by other atoms. Thus, bond is favourable to be created with anything available surrounding it. Adsorption can be categorized into two groups that is chemical adsorption or physical adsorption.

Chemical adsorption occurs when the adsorption involves only chemical bonds between adsorbent and adsorbate. This type of adsorption acquires activation energy and it is can be very strong and not readily reversible and it forms monolayer film around the adsorbent. Meanwhile, physical adsorption is the term that refers to adsorption that occurs due to van der Waals forces between the adsorbent and adsorbate. This type of adsorption is more reversible and non-specific. Physical adsorption can be monolayer or multi layers.

Langmuir isotherm theory was published in 1916. Following this theory, the Langmuir equation was introduced which depicts a relationship between the number of active sites of the surface undergoing adsorption pressure.
One of the most famous application of adsorption is the adsorption on activated charcoal. In this experiment, adsorption of Iodine from solution onto activated charcoal was studied and Langmuir equation was used to estimate the surface area if activated charcoal.

Material and Apparatus

12 conical flasks, 6 centrifuge tubes, measuring cylinders, analytical balance, burettes, retort stand and clamps, Pasteur pipettes, iodine solutions, 1% w/v starch solution, 0.1M sodium thiosulphate solution, distilled water, activated charcoal


Procedures

Using measuring cylinders, 12 conical flasks (labelled 1-12) were filled with 50ml mixtures of iodine solutions (A and B) as stated in Table 1.

Flask
Volume of solution A (ml)
Volume of solution B (ml)
1 and 7
10
40
2 and 8
15
35
3 and 9
20
30
4 and 10
25
25
5 and 11
30
20
6 and 12
50
0

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

Set 2 : Concentration of iodine in solution A at equilibrium (C)
For flasks 7-12:
1) 0.1g of activated charcoal was added.
2) The flasks were capped tightly. The flasks were swirled or shook for every 10 minutes for 2 hours.
3) After 2 hours, the solution was transferred into centrifuge tubes and labelled accordingly.
4) The solutions were centrifuged at 3000 rpm for 5 minutes and the resulting supernatant were transferred into new conical flasks. Each conical flasks were labelled accordingly.


5) Steps 1, 2 and 3 were repeated as carried out for flasks 1-6 in Set 1.


Result

Flask
Vol. Of sodium Thiosulphate needed
flask
Vol. Of sodium Thiosulphate needed
1
10.15mL
7
7.7mL
2
14.65 mL
8
11.7mL
3
18.7 mL
9
15.9mL
4
23.2 mL
10
19.8mL
5
27.6 mL
11
23.8mL
6
45.1 mL
12
40.5mL


Questions





1)      calculate N for iodine


Flask
Vol. Of sodium Thiosulphate needed
Initial concentration of iodine, X
flask
Vol. Of sodium Thiosulphate needed
Concentration of Iodine at equilibrium, C
1
10.15mL
No of mole of Iodine
= 10.15 x 0.01269g/ 2x126.9gmol-1
=5.075x10-4mol

 X= 5.075x10-4mol / 0.05L
    =0.01M
7
7.7mL
No of mole of Iodine
= 7.7 x 0.01269g/ 2x126.9gmol-1
=3.85x10-4mol

 C= 3.85x10-4mol / 0.05L
=0.0077M
2
14.65 mL
No of mole of Iodine
=14.65 x 0.01269g/ 2x126.9gmol-1
=7.325x10-4mol

 X= 7.325x10-4mol / 0.05L =0.015M
8
11.7mL
No of mole of Iodine
=11.7 x 0.01269g/ 2x126.9gmol-1
=5.85x10-4mol

 C= 5.85x10-4mol / 0.05L
=0.0117M
3
18.7 mL
No of mole of Iodine
= 18.7 x 0.01269g/ 2x126.9gmol-1
=9.35x10-4mol

 X= 9.35x10-4mol / 0.05L =0.019M
9
15.9mL
No of mole of Iodine
=15.9 x 0.01269g/ 2x126.9gmol-1
=7.95x10-4mol

 C= 7.95x10-4mol / 0.05L
=0.0159M
4
23.2 mL
No of mole of Iodine
= 23.2 x 0.01269g/ 2x126.9gmol-1
=1.16x10-3mol

 X= 1.16x10-3mol / 0.05L =0.0232M
10
19.8mL
No of mole of Iodine
=19.8 x 0.01269g/ 2x126.9gmol-1
=9.9x10-4mol

 C= 9.9x10-4mol / 0.05L
=0.0198M
5
27.6 mL
No of mole of Iodine
= 10.15 x 0.01269g/ 2x126.9gmol-1
=1.38x10-3mol

 X= 1.38x10-3mol / 0.05L =0.0276M
11
23.8mL
No of mole of Iodine
=23.8 x 0.01269g/ 2x126.9gmol-1
=1.19x10-3mol

 C= 1.19x10-3mol / 0.05L
=0.0238M
6
45.1 mL
No of mole of Iodine
= 10.15 x 0.01269g/ 2x126.9gmol-1
=2.255x10-3mol

 X= 2.255x10-3mol / 0.05L =0.0451M
12
40.5mL
No of mole of Iodine
=40.5 x 0.01269g/ 2x126.9gmol-1
=2.025x10-3mol

 C= 2.025x10-3mol / 0.05L
=0.0405M


N= (X-C) X 50/1000 x 1/0.1


Flasks
Initial concentration of charcoal, X (M)
Concentration of Iodine at equilibrium, C (M)
Total mole of Iodine adsorbed by 1g of activated charcoal, N
(mol)
1 and 7
0.01
0.0077
3.5x10-4 mol
2 and 8
0.015
0.0117
1.8x10-4 mol
3 and 9
0.019
0.0159
3.9x10-4 mol
4 and 10
0.0232
0.0198
1.5x10-4 mol
5 and 11
0.0276
0.0238
3.0x10-4 mol
6 and 12
0.0451
0.0405
2.3x10-4 mol



1)      plot amount of Iodine adsorbed (N) versus balance concentration of solution (C) at equilibrium to obtain adsorption isotherm

Flasks
Concentration of Iodine at equilibrium, C (M)
Total mole of Iodine adsorbed by 1g of activated charcoal, N
(mol)
1 and 7
0.0077
3.5x10-4 mol
2 and 8
0.0117
1.8x10-4 mol
3 and 9
0.0159
3.9x10-4 mol
4 and 10
0.0198
1.5x10-4 mol
5 and 11
0.0238
3.0x10-4 mol
6 and 12
0.0405
2.3x10-4 mol








1)      according to Langmuir theory, if there is  no more than a monolayer of iodine adsorbed on the charcoal,

C/N = C/Nm + 1/KN
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 3.2x10-19 m2, Avogadro no = 6.023x1023 molecule, calculate the surface area of charcoal in m2g-1

Flasks
Concentration of Iodine at equilibrium, C (M)
C/N
1 and 7
0.0077
6.696
2 and 8
0.0117
7.091
3 and 9
0.0159
10.258
4 and 10
0.0198
11.65
5 and 11
0.0238
12.526

6 and 12
0.0405
17.609



The value of Nm from graph,
Gradient 1/Nm =341.7 g mol-1
Nm        = 1/341.7 g mol-1
= 2.927 x 10-3 g mol-1
= 0.00297 g mol-1
No. of molecules of charcoal = Nm x Avogadro no.
 0.00297 mol g-1 x 6.023x1023 molecules per mole
= 1.788831 x 10 21 molecule g-1
Surface area of charcoal = 3.2 x 10-19 m2 x 1.788831 x 10 21 molecule g-1
= 572.42592 m2 g-1

Discussion


Adsorption is the binding of free moving molecules of a gaseous or solutes of a solution onto the surface of the solid. In general, one uses solid adsorbents of small size and often with surface imperfections such as cracks and holes which serve to increase the surface area per unit mass greatly over the apparent geometrical area. Such small, porous particles may have specific areas in the range from 10 to 1000 m2g-1. The adsorption bond can be strong or weak which depends on the nature of forces between the adsorbent and adsorbate. Adsorbent refers to the solid whereas adsorbate refers to the molecules that undergo adsorption such as gas or dissolved solutes. 
             Adsorption occurs when particles such as ion, atom, or molecules on the surface of solids are capable of attracting other molecules due to the instability of energies around the particles resulting to the adsorption phenomena. The type of interaction between the adsorbed molecule and the solid surface varies over a wide range from weak nonpolar van der Waals’ forces to strong chemical bonding. Examples of adsorption where ionic or covalent bonding occurs are the adsorption of chloride ions and silver chloride (ionic) or of oxygen gas on metals where oxygen-metal bonds are formed (covalent). In these cases, the process is called chemisorption, and it is generally characterized by high heats of adsorption (from 10 to 100 kcal mol-1 of gas adsorbed).
             When the reaction between adsorbent and adsorbate is caused by van der Waal’s forces of attraction, it is known as physical adsorption. Physical adsorption forces are similar to those which cause condensation of gases into liquid or solids.
             The nature of adsorbent and adsorbate, surface area of adsorbent and physical conditions such as temperature and pH determines the extent of adsorption from the solution.  Adsorption process is usually studied through graphs known as adsorption isotherm. That is the amount of adsorbate on the adsorbent as a function if its pressure or concentration at constant temperature. Example of isotherm is Langmuir equation and it is most common isotherm equation to use due to its simplicity and its ability to fit a variety of adsorption data.
             In this experiment, Langmuir equation is used to estimate the surface area of activated charcoal sample. This theory is restricted to cases where only one layer of molecules can be adsorbed at the surface. Monolayer adsorption is usually observed in the case of chemisorption from the gas phase or adsorption from solution. Monolayer adsorption is distinguished by the fact that the amount adsorbed reaches a maximum value at moderate concentrations and remains constant with further increase in concentration.
             Solid surfaces can adsorb dissolved substances from solution. When a solution of iodine is shaken with activated charcoal, some of the iodine will be removed by the charcoal and the concentration of the solution decreases. From the results obtained, it is found that K increases as the concentration of iodine is decreases with respect to time. Therefore, the degree to which a solid will adsorb material depends on a number of factors such as temperature, nature of molecule being adsorbed, degree of surface pore structure, and solute and solvent concentration.


             The number of molecules adsorbed per gram of solid, N (mol/g), depends on the specific surface area of the solid, S(m2/g), the final liquid phase concentration Cf (mol/L) or equilibrium gas phase pressure p (atm or kPa), and the specific molecules undergoing adsorption. A plot of N versus Cf or N versus p, where the temperature is held constant, is referred to as an adsorption isotherm. Graph amount of iodine adsorbed (N) versus balance concentration of solution (C) at equilibrium is a non-linear graph and shows that the number of iodine adsorbed gradually increases in the solution. This is because the greater the solubility, the stronger are the solute-solvent bonds and hence the smaller the extent of the adsorption of iodine onto the activated charcoal. The linear plot graph with slope of 1/Nm and intercept of 1/KNm was obtained from graph C/N versus C.

Conclusion


The adsorption of iodine solution in charcoal follows the Langmuir theory of adsorption isotherm. The adsorption rate increases with increasing concentration of iodine. From the result obtained, the surface area of charcoal is.

Reference
Alexander T Florence, D. A. (2006). In Physicochemical Principles of Pharmacy (4th ed., pp. 194-201). London: Pharmaceutical Press.
Patrick J. Sinko, L. W. (n.d.). In Martin’s Physical Pharmacy and Pharmaceutical Sciences (5th ed., pp. 39-40).

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