Outline • Adsorption • Absorption • Sorption • Types of adsorption • Langmuir Isotherm • Factors Affecting the Adsorption • Medical & Pharmaceutical Application of Adsorption Adsorption • Definition: • “Adsorption is accumulation of a substance at interface or boundary between two heterogeneous phases e.g. solid-gas, two immiscible liquids, gas-liquid or solid-liquid.” • It is a surface phenomenon. • Most common industrial adsorbent are activated carbon, silica gel and alumina • Adsorbate: • Material which is adsorbed. • Adsorbent: • Material on which adsorbate gets adsorbed i.e. activated charcoal. Adsorption A b s o r p ti o n : Absorption implies the penetration of one component throughout the body of the second. The distinction between the adsorption and absorption is not always clear. S o r p ti o n : “When there is not any distinction between adsorption and absorption then a noncommittal word “sorption” is used.” D e s o r p ti o n : reverse to adsorption i.e process of removing adsorbed substances from the surface of an adsorbent. Adsorption Adsorbate: The phase that is going to be adsorbed is called adsorbate. Adsorbing substance is called adsorbate. Adsorbent: The phase that adsorbs a substance is called as adsorbent. E.g. talc, alumina, Kaolin, magnesium trisilicate. Types of Adsorption P h y s i c a l A d s o r p ti o n : also called as physisorption. Adsorption occurs at surface through “week Vander wall” attractive forces. Process can be reversed by heating or decreasing the pressure of adsorbate (as in case of gases). C h e m i c a l A d s o r p ti o n : also called as chemisorption. Involves the strong valance forces. More potent and usually involves “ion exchange” process. Involves cation exchange with the basic group of toxins and physical adsorption of reminder of molecule. Difference between physisorption and chemisorption Examples of Adsorption: Solid/liquid; Strychnine hydrochloride onto activated charcoal. Solid/gas; activated charcoal used in respirator for civilians and forces. Factors Affecting the Adsorption 1. Solubility of the Adsorbate: Highly soluble substances have poor or less adsorption on adsorbent. Phobic substances adsorb more than phillic. Factors Affecting the Adsorption 2.pH: Ionization affects the solubility of drugs. In drug with single molecules, adsorption increases when ionization is suppressed. For amphoteric compounds (with positive and negative charges), adsorption is maximum at isoelectric point. As far as pH and solubility are concerned, solubility has more pronounced effect upon adsorption. Example: Hyoscine is completely unionized but less adsorbed than atropine which is 50% ionized. Because hyoscine is highly soluble (1:95 parts of water) than atropine (1:400 parts of water) at 90°C. Factors Affecting the Adsorption 3. Nature of Adsorbent: Finely divided particles have more adsorption capacity. Adsorbent can be converted into the activated form to increase the capacity of adsorption. Example: Activated charcoal; a. Special treatment to remove surface impurities. b. To convert into small particles. Factors Affecting the Adsorption 4. Temperature: Mostly, exothermic process. temperature may change the nature of adsorption process. at room temperature there is no physisorption of N2 at iron surface. At 83K N2 is physisorbed at iron surface. if temperature is increased to 773K N2 is chemisorbed at iron surface at nitrogen atom. Factors Affecting the Adsorption 5. Pressure: x/m = KPn X = quantity adsorbed M = mass of adsorbent P = Pressure of adsorbate K = constant for adsorbent-adsorbate pair at given temperature. N = constant for adsorbent-adsorbate pair at given temperature. 6. Surface Area: Greater the surface area greater would be the adsorption. Isotherm Models • Relation between pressure of a gas and amount adsorbed at a fix temperature and pressure.
unit weight of adsorbent. • P = equilibrium gas pressure • K and n = constants depending upon temperature, nature of adsorbent and adsorbate.
• 1/n is the slop of graph while log
K gives the intercept. Langmuir Adsorption Isotherm • Important assumptions of Langmuir adsorption isotherm are; • The layer of adsorbed molecules is only one molecule thick i.e. the adsorbed layer is monomolecular. • Gas molecules are adsorbed at fixed site on the surface. • Rate of evaporation from the surface depends upon the filled sites on the surface. • Rate of condensation is proportional to the unfilled sites on the surface. Langmuir Adsorption Isotherm
• θ = Fraction of surface covered with gas at a given instance.
• 1 – θ = Fraction of surface uncovered with molecules.
• P = Pressure Langmuir Adsorption Isotherm • Final form of Langmuir isotherm can be written as;
• X = No. of molecules adsorbed at surface
• Xm = No. of molecules necessary to fill the surface. • Langmuir equation can be written in linear form as follows;
• Figure 2(a) and figure 3(I) show that at low
pressure, the amount of gas adsorbed is proportional to the pressure. • Adsorption becomes progressively less as the pressure is increased. Bet Adsorption Isotherm • BET adsorption isotherm explains the formation of multilayer. • Such type of situation occurs at low temperature and pressure near to saturation pressure when an S-shaped isotherm is formed i.e. Figure 3(II). • Bet isotherm assumed that; • Molecules adsorbed at the fixed sites and there was no lateral interaction between the molecules. • Heat of adsorption of a molecule to any layer other than the first layer was equal to the heat of condensation.
• P = Saturation vapor pressure
• Xm = Monolayer capacity • C = Constant Bet Adsorption Isotherm • Type II isotherm is best representation of BET isotherm and is characteristic of non-porous solids of very fine particles. • Type IV is the adsorption of water vapor on gel-like material such as cellulose, starches where uptake of water vapors with increase in pressure gives an adsorption isotherm which differ from the curve obtained during desorption of the gel. Medical & Pharmaceutical Application of Adsorption 1. Chromatography: Basis of their separation is their smallest difference in their absorbability or difference in distribution/partition between two phases. 2. Adsorption of Toxins from Alimentary Canal: 3. Removal of Toxic Elements from Blood: “hemodialysis”. 4. Treatment of Severe Drug Overdose: Microencapsulation of activated charcoal by acrylic hydrogel, a biocompatible material preventing embolism and removal of overdosed drug. Medical & Pharmaceutical Application of Adsorption 5. Decolourization: Color is removed by adding activated charcoal. Decolorization of alkaloids is done by kieselguhr (weaker adsorbent). 6. Adsorption of Water Vapours: Alumina and silica gel remain in solid forms even after 40% adsorption of water. 7. Adsorption of Pyrogens: Low molecular weight drugs can be made pyrogen free like glucose, sodium citrate and calcium gluconate etc. High molecular weight drugs get adsorbed highly on adsorbents so cannot be made pyrogen free.