Engineering Chemistry

Unit III: Surface Chemistry

Lecture Notes : Summary

Role of Adsorption

1.

In heterogeneous catalysis ( Contact Theory)

Mechanism The reaction in which the catalyst is in a different physical phase from the reactants and products is termed heterogenous catalysis. The most important of such reactions are those in which the reactants/products are in gas phase, while the catalyst is in solid state. This process is called contact catalysis since the reaction occurs by contact of reactants on the solid catalyst surface and not in gaseous phase.
Ni

Eg: CH2 = CH2 + H2 Ethylene

CH3 CH3

Eg: Hydrogenation of ethylene in presence of Ni

The various steps involved are: 1. Diffusion of ethylene and hydrogen towards surface 2. Adsorption of ethylene and hydrogen at the active sites of nickel by vanderwaals force; The reactant molecules get crowded on the catalyst surface thereby increasing the concentration on the surface.( fig 2) 3. Formation of activated complex: a. Dissociation of physisorbed hydrogen molecule into H- atoms and forms chemisorbed surface bond with Nickel . The heat of adsorption evolved during chemisorption provide necessary activation energy for the adsorption reaction and forms intermediate activated complex with ethylene b. Linking of H - atoms to ethylene to form activated complex which then decomposes to form ethane. (fig 3a , 3b)

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Engineering Chemistry

Unit III: Surface Chemistry

4. Desorption of ethane from the surface-(fig 4) Physisorbed hydrogen

Ni

Ni

Ni

Ni Fig : 2

Chemisorbed hydrogen Ni Ni Ni Ni Fig : 3a

H H C C H

Fig : 3b: Activated complex formation

Ni

Ni

Ni

Ni

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Engineering Chemistry

Unit III: Surface Chemistry

H C H

H C H H

Fig : 4: Desorption of products(ethane) from catalyst surface Ni Ni Ni Ni

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Branch: CSE B & CIVIL

Engineering Chemistry

Unit III: Surface Chemistry

2.

In Column Chromatography Adsorption chromatography is based on the differences in the adsorption of substances on solid. Principle: It is found that closely related substances with almost similar and physical and chemical properties which cannot be separated from one another by ordinary means are adsorbed to different extents on the surface of adsorbent. This facilitates separation and purification. If a solution containing different solutes is poured down a column filled with finely divided adsorbent, the solute most readily adsorbed is retained on the top layer along with smaller amounts of other constituents. The less readily adsorbed constituents are held on lower portions of the column. A partial separation of the constituents of the mixture is thus easily achieved. The separation is further enhanced by repeating and modifying the process. This process is known as column chromatography first developed by a Polish botanist, M.S.Tswett, to separate plant pigments. Some common adsorbents used are : aluminium oxide, silica gel, MgO, MgCO3, CaCO3,Charcoal, cellulose, Fullers earth. Solvents used are: benzene, cyclohexane, chloroform, ethylalcohol, water , CCl4, pyridine etc.

Process: The various stages are 1. Separation of mixture into different components : When a mixture of components dissolved in a suitable solvent is passed slowly through the column packed with alumina (say), a number of horizontal bands of different colors are produced in the column. This gives only a partial separation of various constituents. 2. Development of chromatogram This initial separation of constituents can be improved by passing either the original or some other suitable solvent slowly through the column. The solvent used is called Eluent.

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Engineering Chemistry

Unit III: Surface Chemistry

The various colored zones now becomes more sharply defined. The process of improving the separation of a mixture by passing the original solvent or some other suitable solvent is known as development of the chromatogram. The process of separation of a mixture of two components X and Y is illustrated below (fig a e next page)

3.

Isolation & Estimation of components :

In order to separate or to estimate the various constituents, the chromatogram after development is pushed out of the glass tube and the various zones are cut with a knife at the boundaries. The colored components are dissolved separately in suitable solvents and estimated quantitatively. The process of recovery of various substances from the chromatogram is known as Elution. Colorless compounds are observed by either exposing UV light on the column or by spraying suitable chemical reagent in order to make them colored. Applications: a. Quantitative separation of two or more components of a mixture (separation of metal ions) b. Purification of substances from their contaminants c. Concentration of solutes from dilute solutions d. Identification of products.(eg : isomers of organic compounds

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Engineering Chemistry

Unit III: Surface Chemistry

Schematic Representation ogf separation of components in a Mixture Fig : ( a ) : Mixture of X &Y

Fig : ( b )

Sample X+Y Adsorbent

Eluent Sample X+Y Y

Adsorbent

Fig : ( c ) Eluent X Sample X+Y Y

Fig : ( d )

Eluent Adsorbent X Y Adsorbent

Adsorbent

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Engineering Chemistry

Unit III: Surface Chemistry

Fig : ( e ) : Distinct bands of X & Y

Adsorbent Eluent X Eluent Y Eluent

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Branch: CSE B & CIVIL