Surface Chemistry

Category : UPSC

 Surface Chemistry

 

1.           Adsorption and Absorption

 

  • In adsorption, the substance is concentrated only at the surface and does not penetrate through the surface to the bulk of the adsorbent, while in absorption, the substance is uniformly distributed throughout the bulk of the solid. For example, when a chalk stick is dipped in ink, the surface retains the colour of the ink due to adsorption of coloured molecules while the solvent of the ink goes deeper into the stick due to absorption. On breaking the chalk stick, it is found to be white from inside.
  • A distinction can be made between absorption and adsorption by taking an example of water vapour. Water vapours are absorbed by anhydrous calcium chloride but adsorbed by silica gel. In other words, in adsorption the concentration of the adsorbate increases only at the surface of the adsorbent, while in absorption the concentration is uniform throughout the bulk of the solid,

 

  • Applications of Adsorption: The phenomenon of adsorption finds a number of application. Important ones are listed here :
  • Production of high vacuum: The remaining traces of air can be adsorbed by charcoal from a vessel evacuated by a vacuum pump to give a very high vacuum.
  • Gas masks: Gas mask (a device which consists of activated charcoal or mixture of adsorbents) is usually used for breathing in coal mines to adsorb poisonous gases.
  • Control of humidity: Silica and aluminium gels are used as adsorbents for removing moisture and controlling humidity.
  • Removal of colouring matter from solutions: Animal charcoal removes colours of solutions by adsorbing coloured impurities.
  • Heterogeneous catalysis: Adsorption of reactants on the solid surface of the catalysts increases the rate of reaction. There are many gaseous reactions of industrial importance involving solid catalysts. Manufacture of ammonia using iron as a catalyst, manufacture of \[{{H}_{2}}S{{O}_{4}}\] by contact process and use of finely divided nickel in the hydrogenation of oils are excellent examples of heterogeneous catalysis.
  • Separation of inert gases: Due to the difference in degree of adsorption of gases by charcoal, a mixture of noble gases can be separated by adsorption on coconut charcoal at different temperatures.
  • In curing diseases: A number of drugs are used to kill germs by getting adsorbed on them.
  • Froth floatation process: A low grade sulphide ore is concentrated by separating it from silica and other earthy matter by this method using pine oil and frothing agent.
  • Adsorption indicators: Surfaces of certain precipitates such as silver halides have the property of adsorbing some dyes like eosin, fluorescein, etc. and thereby producing a characteristic colour at the end point.
  • Chromatographic analysis: Chromatographic analysis based on the phenomenon of adsorption finds a number of applications in analytical and industrial fields.

 

2.           Catalysis

 

  • Diffusion of reaction products away from the catalyst's surface. The surface of the catalyst unlike the inner part of the bulk, has free valencies which provide the seat for chemical forces of attraction. When a gas comes in contact with such a surface, its molecules are held up there due to loose chemical combination. If different molecules are adsorbed side by side, they may react with each other resulting in the formation of new molecules. Thus, formed molecules may evaporate leaving the surface for the fresh reactant molecules.
  • This theory explains why the catalyst remains unchanged in mass and chemical composition at the end of the reaction and is effective even in small quantities. It however, does not explain the action of catalytic promoters and catalytic poisons.
  • The action of a catalyst is highly selective in nature, i.e., a given substance can act as a catalyst only in a particular reaction and not for all the reactions.

 

3.           Enzyme Catalysis

 

  • Enzymes are complex nitrogenous organic compounds which are produced by living plants and animals. They are actually protein molecules of high molecular mass and form colloidal solutions in water. They are very effective catalysts; catalyse numerous reactions, especially those connected with natural processes.
  • Numerous reactions that occur in the bodies of animals and plants to maintain the life process are catalysed by enzymes. The enzymes are, thus, termed as biochemical catalysts and the phenomenon is known as biochemical catalysis.
  • Soifte of the examples of enzyme-catalysed reactions :
  • Inversion of cane sugar: The invertase enzyme converts cane sugar into glucose and fructose.
  • Conversion of glucose into ethyl alcohol: The zymase enzyme converts glucose into ethyl alcohol and carbon dioxide.
  • Conversion of starch into maltose: The diastase enzyme converts starch into maltose.
  • Conversion of maltose into glucose: The maltase enzyme converts maltose into glucose.
  • Decomposition of urea into ammonia and carbon dioxide: The enzyme urease catalyses this decomposition.
  • In stomach, the pepsin enzyme converts proteins into peptides while in intestine, the pancreatic trypsin converts proteins into amino acids by hydrolysis.
  • Conversion of milk into curd: It is an enzymatic reaction brought about by lacto bacilli enzyme present in curd.
  • There are a number of cavities present on the surface of colloidal particles of enzymes, These cavities are of characteristic shape and possess active groups such as -\[N{{H}_{2}},\,-COOH,\,\,-SH\,-OH,\] etc. These are actually the active centres on the surface of enzyme particles. The molecules of the reactant (substrate), which have complementary shape, fit into these cavities just like a key fits into a lock. On account of the presence of active groups, an activated complex is formed which then decomposes to yield the products.

 

4.           Characteristics of enzyme catalysis

 

  • One molecule of an enzyme may transform one million molecules of the reactant per minute.
  • Each enzyme is specific for a given reaction, i.e., one catalyst cannot catalyse more than one reaction. For example, the enzyme urease catalyses the hydrolysis of urea only. It does not catalyse hydrolysis of any other amide.
  • The rate of an enzyme reaction becomes maximum at a definite temperature, called the optimum temperature. On either side of the optimum temperature the enzyme activity decreases. The optimum temperature range for enzymatic activity is 298-310 K. Human body temperature being 310 K is suited for enzyme-catalysed reactions.
  • The rate of an enzyme-catalysed reaction is maximum at a particular pH called optimum PH, which is between pH values 5-7.
  • The enzymatic activity is increased in the presence of certain substances, known as co-enzymes. It has been observed that when a small non-protein (vitamin) is present along with an enzyme the catalytic activity is enhanced considerably. Activators are generally metal ions such as \[N{{a}^{+}},\,M{{n}^{2+}},\,C{{o}^{2+}},C{{u}^{2+}},\] etc. These metal ions, when weakly bonded to enzyme molecules, increase their catalytic activity. Amylase in presence of sodium chloride i.e., \[N{{a}^{+}}\] ions are catalytically very active.
  • Like ordinary catalysts, enzymes are also inhibited or poisoned by the presence of certain substances. The inhibitors or poisons interact with the active functional groups on the enzyme surface and often reduce or completely destroy the catalytic activity of the enzymes. The use of many drugs is related to their action as enzyme inhibitors in the body.

 

5.           Colloids

 

  • Solutions are homogeneous system. We also know that sand in water when stirred gives a suspension, which slowly settles down with time. Between the two extremes of suspensions and solutions we come across a large group of systems called colloidal dispersions or simply colloids.
  • A colloid is a heterogeneous system in which one substance is dispersed (dispersed phase) as very fine particles in another substance called dispersion medium.
  • The essential difference between a solution and a colloid is that of particle size. While in a solution, the constituent particles are ions or small molecules, in a colloid, the dispersed phase may consist of particles of a single macromolecule (such as protein or synthetic polymer) or an aggregate of many atoms, ions or molecules.

 

  • Colloidal particles are larger than simple molecules but small enough to remain suspended. Their range of diameters is between 1 and 1000 nm (\[{{10}^{-9}}\]to \[{{10}^{-6}}\] m). Colloidal particles have an enormous surface area per unit mass as a result of their small size.
  • Colloids are classified on the basis of the following criteria :
  • Physical state of dispersed phase and dispersion medium
  • Nature of interaction between dispersed phase and dispersion medium
  • Type of particles of the dispersed phase.
  • Depending upon whether the dispersed phase and the dispersion medium are solids, liquids or gases, eight types of colloidal systems are possible, A gas mixed with another gas forms a homogeneous mixture and hence is not a colloidal system.
  • Many familiar commercial products and natural objects are colloids. For example, whipped cream is a foam, which is a gas dispersed in a liquid. Firefighting foams, used at emergency airplane landings are also colloidal systems. Most biological fluids are aqueous sols (solids dispersed in water). Within a typical cell, proteins and nucleic acids are colloidal-sized particles dispersed in an aqueous solution of ions and small molecules.
  • Out of the various types of colloids the most common are sols (solids in liquids), gels (liquids in solids) and emulsions (liquids in liquids).
  • Depending upon the nature of interaction between the dispersed phase and the dispersion medium, colloidal sols are divided into two categories, namely, lyophilic (solvent attracting) and lyophobic (solvent repelling). If water is the dispersion medium, the terms used are hydrophilic and hydrophobic.
  • The word 'lyophilic’ means liquid-loving. Colloidal sols directly formed by mixing substances like gum, gelatine, starch, rubber, etc., with a suitable liquid (the dispersion medium) are called lyophilic sols.
  • An important characteristic of these sols is that if the dispersion medium is separated from the dispersed phase (say by evaporation), the sol can be reconstituted by simply remixing with the dispersion medium. That is why these sols are also called reversible sols. Furthermore, these sols are quite stable and cannot be easily coagulated.
  • The word 'lyophobic' means liquid-hating. Substances like metals, their sulphides, etc., when simply mixed with the dispersion medium do not form the colloidal sol. Their colloidal sols can be prepared only by special methods. Such sols are called lyophobic sols. These sols are readily precipitated (or coagulated) on the addition of small amounts of electrolytes, by heating or by shaking and hence, are not stable.

 

6.           Tyndall Effect

 

  • If a homogeneous solution placed in dark is observed in the direction of light, it appears clear and, if it is observed from a direction at right angless to the direction of light beam, it appears perfectly dark.
  • Colloidal solutions viewed in the same way may also appear reasonably clear or translucent by the transmitted light but they show a mild to strong opalescence, when viewed at right angles to the passage of light, i.e., the path of the beam is illuminated by a bluish light.
  • This effect was first observed by Faraday and later studied in detail by Tyndall and is termed as Tyndall effect. The bright cone of the light is called Tyndall cone. The Tyndall effect is due to the fact that colloidal particles scatter light in all directions in space. This scattering of light illuminates the path of beam in the colloidal dispersion.
  • Tyndall effect can be observed during the projection of picture in the cinema hall due to scattering of light by dust and smoke particles present there. Tyndall effect is observed only when the following two conditions are satisfied.
  • The diameter of the dispersed particles is not much smaller than the wavelength of the light used; and
  • The refractive indices of the dispersed phase and the dispersion medium differ greatly in magnitude.
  • Tyndall effect is used to distinguish between a colloidal and true solution.

 

7.           Colloids Around Us

 

  • Most of the substances, we come across in our daily life, are colloids. The meals we eat, the clothes we wear, the wooden furniture we use, the houses we live in, the newspapers we read, are largely composed of colloids. Following are the interesting and noteworthy examples of colloids :
  • Blue colour of the sky: Dust particles along with water suspended in air scatter blue light which reaches our eyes and the sky looks blue to us.
  • Fog, mist and rain: When a large mass of air containing dust particles, is cooled below its dewpoint, the moisture from the air condenses on the surfaces of these particles forming fine droplets. These droplets being colloidal in nature continue to float in air in the form of mist or fog. Clouds are aerosols having small droplets of water suspended in air. On account of condensation in the upper atmosphere, the colloidal droplets of water grow bigger and bigger in size, till they come down in the form of rain. Sometimes, the rainfall occurs when two oppositely charged clouds meet. It is possible to cause artificial rain by throwing electrified sand or spraying a sol carrying charge opposite to the one on clouds from an aeroplane.
  • Food articles: Milk, butter, halwa, ice creams, fruit juices, etc, are all colloids in one form or the other.
  • Blood: It is a colloidal solution of an albuminoid substance. The styptic action of alum and ferric chloride solution is due to coagulation of blood forming a clot which stops further bleeding.
  • Soils: Fertile soils are colloidal in nature in which humus acts as a protective colloid. On account of colloidal nature, soils adsorb moisture and nourishing materials.
  • Formation of delta: River water is a colloidal solution of clay. Sea water contains a number of electrolytes. When river water meets the sea water, the electrolytes present in sea water coagulate the colloidal solution of clay resulting in its deposition with the formation of delta.

 

8.           Applications of Colloids

 

  • Colloids are widely used in the industry. Following are some examples:
  • Electrical precipitation of smoke: Smoke is a colloidal solution of solid particles such as carbon, arsenic compounds, dust, etc., in air. The smoke, before it comes out from the chimney, is led through a chamber containing plates having a charge opposite to that carried by smoke particles. The particles on coming in contact with these plates lose their charge and get precipitated. The particles thus settle down on the floor of the chamber. The precipitator is called Cottrell precipitator.
  • Purification of drinking water: The water obtained from natural sources often contains suspended impurities. Alum is added to such water to coagulate the suspended impurities and make water fit for drinking purposes.
  • Medicines: Most of the medicines are collodial in nature. For example, argyrol is a silver sol used as an eye lotion. Colloidal anitomy is used in curing kalaazar. Colloidal gold is used for intramuscular injection. Milk of magnesia, an emulsion, is used for stomach disorders. Colloidal medicines are more effective because they have large surface area and are therefore easily assimilated.
  • Tanning: Animal hides are colloidal in nature. When a hide, which has positively charged particles, is soaked in tannin, which contains negatively charged colloidal particles, mutual coagulation takes place. This results in the hardening of leather. This process is termed as tanning. Chromium salts are also used in place of tannin.
  • Photographic plates and films: Photographic plates or films are prepared by coating an emulsion of the light sensitive silver bromide in gelatin over glass plates or celluloid films.
  • Rabber industry: Latex is a colloidal solution of rubber particles which are negatively charged. Rubber is obtained by coagulation of latex.
  • Industrial products: Paints, inks, synthetic plastics, rubber, graphite lubricants, cement, etc., are all colloidal solutions.

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