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Objective

:
1. To demonstrate the adsorption phenomena. 2. To show students how to determine the adsorption parameters.

Theory:
Adhesion of atoms, ions, bimolecules or molecules of gas, liquid or dissolved solids to a surface is called adsorption. In this process creates a film of the adsorbate –the molecules or atoms being accumulated, on the surface of the adsorbent.

Examples:
   
Activated charcoal adsorbs gases like CO2 , SO2, Cl2 etc. Pt or Ni metal kept in contact with a gas adsorbs the gas - Hydrogenation of oils. Animal charcoal, when added to acetic acid solution and shaken vigorously, adsorbs acetic acid. Molasses is decolourised by activated charcoal. The molecules of gases or liquids or the solutes in solutions get adhered to the surface of the solids. In adsorption process two substances are involved. One is the solid or the liquid on which adsorption occurs and it is called adsorbent. The second is the adsorbate, which is the gas or liquid or the solute from a solution which gets adsorbed on the surface. i.e. Adsorbent : The substance on whose surface the adsorption occurs is known as adsorbent. Adsorbate : The substance whose molecules get adsorbed on the surface of the adsorbent ( i.e. solid or liquid ) is known as adsorbate. Adsorption is different from absorption. In absorption, the molecules of a substance are uniformly distributed in the bulk of the other, whereas in adsorption molecules of one substance are present in higher concentration at the surface of the other substance.

Types of adsorption:
Depending upon the nature of forces existing between adsorbate molecules and adsorbent, the adsorption can be classified into two types: 1. Physical adsorption (physisorption): If the force of attraction existing between adsorbate and adsorbent are Vander Waal’s forces, the adsorption is called physical adsorption. It is also known as Vander Waal’s adsorption. In physical adsorption the force of attraction between the adsorbate and adsorbent are very weak, therefore this type of adsorption can be easily reversed by heating or by decreasing the pressure.

pressure. Adsorption is independent of pressure. 4. . that is there are limited numbers of vacancies on the surface of the adsorbent. At high pressure. 2. therefore adsorption cannot be easily reversed.g.. The surface area of adsorbent. Basic Adsorption Isotherm: From the above we can predict that after saturation pressure Ps. Chemical adsorption (chemisorption): If the force of attraction existing between adsorbate and adsorbent are almost same strength as chemical bonds. It is also known as Langmuir adsorption. Experimental conditions. Factors affecting adsorption: The extent of adsorption depends upon the following factors: 1. Adsorption Isotherm: Adsorption process is usually studied through graphs known as adsorption isotherm.2. That is the amount of adsorbate on the adsorbent as a function if its pressure or concentration at constant temperature . In chemisorption the force of attraction is very strong. Nature of adsorbate and adsorbent. 3.The quantity adsorbed is nearly always normalized by the mass of the adsorbent to allow comparison of different materials. E. etc. adsorption does not occur anymore. Activation of adsorbent. temperature. At high pressure a stage is reached when all the sites are occupied and further increase in pressure does not cause any difference in adsorption process. the adsorption is called chemical adsorption.

value of C has to be very large in comparison to 1. Examples of Type-I adsorption are Adsorption of Nitrogen (N2) or Hydrogen (H) on charcoal at temperature near to -1800°C. The intermediate flat region in the isotherm corresponds to monolayer formation. Type I Adsorption Isotherm: Type I Adsorption Isotherm     The above graph depicts Monolayer adsorption. Type II Adsorption Isotherm: Type II Adsorption Isotherm    Type II Adsorption Isotherm shows large deviation from Langmuir model of adsorption. In BET equation. . If BET equation.Type of Adsorption Isotherm: Five different types of adsorption isotherm and their characteristics are explained below. when P/P0<<1 and c>>1. This graph can be easily explained using Langmuir Adsorption Isotherm. then it leads to monolayer formation and Type I Adsorption Isotherm is obtained.

This isotherm explains the formation of multilayer. Type III Adsorption Isotherm: Type III Adsorption Isotherm      Type III Adsorption Isotherm also shows large deviation from Langmuir model. There is no flattish portion in the curve which indicates that monolayer formation is missing. Examples of Type III Adsorption Isotherm are Bromine (Br2) at 790°C on silica gel or Iodine (I2) at 790°C on silica gel. Examples of Type-II adsorption are Nitrogen (N2 (g)) adsorbed at -1950°C on Iron (Fe) catalyst and Nitrogen (N2 (g)) adsorbed at -1950°C on silica gel. This explains formation of monolayer followed by multilayer. . In BET equation value if C <<< 1 Type III Adsorption Isotherm obtained. Type IV Adsorption Isotherm: Type IV Adsorption Isotherm  At lower pressure region of graph is quite similar to Type II.

Examples of Type IV Adsorption Isotherm are of adsorption of Benzene on Iron Oxide (Fe 2O3) at 500°C and adsorption of Benzene on silica gel at 500°C. This curve is also called the freundlich isotherm curve.  The intermediate flat region in the isotherm corresponds to monolayer formation. Example of Type V Adsorption Isotherm is adsorption of Water (vapors) at 1000°C on charcoal. This equation is known as Freundlich Adsorption Isotherm or Freundlich Adsorption equation or simply Freundlich Isotherm. As see the following diagram. Though Freundlich Isotherm correctly established the relationship of adsorption with pressure at lower values. . x/m = adsorption per gram of adsorbent which is obtained be dividing the amount of adsorbate (x) by the weight of the adsorbent (m). Type IV and V shows phenomenon of capillary condensation of gas. it failed to predict value of adsorption at higher pressure. P is Pressure. k and n are constants whose values depend upon adsorbent and gas at particular temperature . This can be explained on the basis of a possibility of gases getting condensed in the tiny capillary pores of adsorbent at pressure below the saturation pressure (PS) of the gas. The value of x/m is increasing with increase in p but as n>1 it does not increase suddenly.  Type V Adsorption Isotherm: Type V Adsorption Isotherm    Explanation of Type V graph is similar to Type IV. The saturation level reaches at a pressure below the saturation vapor pressure. Freundlich Adsorption Isotherm: In 1909. This relation is called as the freundlich adsorption isotherm. Freundlich expressed an empirical equation for representing the isothermal variation of adsorption of a quantity of gas adsorbed by unit mass of solid adsorbent with pressure. Where .

which retained his name. it can be assured that the freundlich adsorption isotherm is satisfied for this system. From this the value of slope equal to 1/n and the value of intercept equal to log k can be obtained. it the graph of log x/m against log p comes out to be a straight line. Irving Langmuir published a new model isotherm for gases adsorbed to solids. It is a semi-empirical isotherm derived from a proposed kinetic mechanism. if a graph of log x/m is plotted against log p. It is based on four assumptions: . This isotherm was based on different assumptions one of which is that dynamic equilibrium exists between adsorbed gaseous molecules and the free gaseous molecules. Over and above. Langmuir Adsorption Isotherm: In 1916. Hence.Taking the logarithms of a first equation. it will be a straight line in the following diagram.

only on the free surface of the adsorbent. that factor (1+KP) in denominator can almost be ignored. A(g) = unadsorbed gaseous molecule B(s) = unoccupied metal surface AB = Adsorbed gaseous molecule. that is. At lower pressure. The surface of the adsorbent is uniform. that factor (1+KP) in denominator is nearly equal to KP. 4. Langmuir suggested that adsorption takes place through this mechanism: Where . θ= the number of sites of the surface which are covered with gaseous molecule. The direct and inverse rate constants are k and k-1 Based on his theory. molecules of adsorbate. KP is so small. So Langmuir equation reduces to At high pressure KP is so large. So Langmuir equation reduces to . This equation is called Langmuir Equation. Langmuir derived an equation which explained the relationship between the number of active sites of the surface undergoing adsorption and pressure. At the maximum adsorption.1. only a monolayer is formed: molecules of adsorbate do not deposit on other. Where. The basic limitation of Langmuir adsorption equation is that it is valid at low pressure only. 3. All adsorption occurs through the same mechanism. all the adsorption sites are equivalent. P= pressure K =is the equilibrium constant for distribution of adsorbate between the surface and the gas phase . 2. Adsorbed molecules do not interact. already adsorbed.

in chromatography to separate the constituents' of a mixture. 1. in gas masks where activated charcoal adsorbs poisonous gases. in creating vacuum by adsorbing gases on activated charcoal. 2. Five well cleaned. Procedure of adsorption: 500 ml of 0. in certain titrations to determinate the end point using an adsorbent as indicator (Example: Flouroscein).Mechanism of Adsorption Using Adsorbent: Applications of adsorption: The principle of adsorption is employed. to control humidity by the adsorption of moisture on silica gel.5N oxalic acid are added followed by 0. 7. 20 and 10 ml of 0. These bottles were shaken thoroughly nearly for an hour by means of a mechanical shaker and they are set aside in a trough containing water to reach equilibrium. dried. 5. 10. .5N oxalic acid solution is prepared. reaction bottles (250 ml) are taken and are labeled. 30 and 40 ml of distilled water so that the total volume (50 ml) remains constant in each bottle. 6. 30. in heterogeneous catalysis. 3. in the refining of petroleum and decolouring cane juice. 20. About 2 g of the activated animal charcoal are accurately weighed and transferred carefully into each of the bottles. 40. By means of a burette 50. 4.

From the titre values. . the concentration of oxalic acid remaining and hence the amount of oxalic acid adsorbed are calculated. In order to test the validity of Freundlich adsorption isotherm plot log (x/m) against log Ce. A linear plot obtained shoe the applicability of the isotherm. Calculate the constants "a" and "b" from the slope and intercept on the ordinate axis.The supernatant liquid of each of the bottles are filtered through a small dry filter paper and the filtrate is collected in properly labeled conical flasks. It is titrated against standardized KMnO4 solution until a pink colour appears. Validity of Langmuir adsorption equation can be tested by plotting Ce/(x/m) Vs Ce. The titration is repeated to get concordant values. The slopes and intercepts of the plot will give 1/n and log k respectively and hence n and K can be calculated.(The initial 5 ml or 10 ml of the filtrate is rejected) 10 ml of the filtrate is pipetted out into a clean conical flask.

Oxalic acid 4. 6. Click the start button. 7. 3. Water Procedure: 1. Burette Stand Reagents: 1. Select the titrant. 2. Note down the end point. Corresponding graphs of Langmuir and Freudlich adsorption isotherm are obtained. Magnetic Stirrer 4. 5. Burette 2. 4.Materials Required: 1. Select the titrate. KMnO4 2. Conical Flask 3. Enter the value in the excel sheet. . Choose the volume of water and oxalic acid. Charcoal 3.

......... Freundlich Adsorption isotherm is verified.......5 2 40 10 10 0..5 2 10 40 10 log log(X/m) Ce/(X/ Ce Results: 1..... The value of constant 4.5 2 30 20 10 0.....1 0..1 0.. 3.. =.. When you enter the lab.5 2 50 0 10 0...... Always wear lab coat and gloves when you are in the lab.. The value of constant =..... 4..... KMnO4. .. switch on the exhaust fan and make sure that all the chemicals and reagents required for the experiment are available... prepare the reagents using the components for reagent preparation......1 0. KMnO4...... Once the experiment completed recap the reagent bottles.Observations and Calculations: Normality Volume Ci X=CiCe X/m Titrate o... Discard the used gloves in a waste bin.. 2...... Switch off the light. The value of constant 5..... If it is not available.......5 2 20 30 10 0... Langmuir Adsorption isotherm is verified. Clean all glass wares with soap and distilled water...... The value of constant 6..... =. 2..... Charcoal. Make sure to calibrate the electronic weigh balance before taking the measurements.. Points to Remember while Performing Experiment in a Real Laboratory: the 1....1 0. Make sure to clean all your working apparatus with chromic acid and distilled water and ensure that all the apparatus are free from water droplets while performing the experiment. 3.V2 Ce=(V2*N2)/V1 H2C2O4 H2C2O4 Water V1 in N2 m in mL mL 0..... =..... 5........1 0.... and exhaust fan before leaving the lab.......