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Surface Chemistry
Surface chemistry is the branch of chemistry in which we study physical and chemical processes taking place on the surfaces of solids and liquids. The surface or interface is the layer or slash which separates out two bulk phases (like solids and gases) that are not completely miscible. Since the gases are completely miscible, there is no interface between the gases. The study of nature of different surfaces is very important because the properties of liquids and solids are found to be different from the bulk phases. Actually the molecules present at the surface experience the intermolecular forces on one side only, so they try to interact with any molecule present in the other immediate phase. This tendency of surface molecules to interact with other molecules increases their activity as compared to the molecules present in the bulk (interior) phase. The process of dyeing, action of drugs, catalysis, rusting of metals, water purification, dissolution and crystallization are some of the common processes which involve the solid interfaces. In these processes, the forces existing at the surface of solids enable the solid to absorb gas or a substance from solution. The subject of surface chemistry finds many applications in industry, analytical work and daily life situations. In this unit we will study about the events that take place on the solid surfaces like sorption (i.e., absorption and absorption), catalysis and colloids including emulsions and gels.

Adsorption
Adsorption is the process of accumulation of molecules at the surface rather than in the bulk of a solid or liquid which results into the higher concentration of molecules at the surface. The substance which is absorbed at the surface is called adsorbate and the substance on which it is adsorbed is called absorbent. By applying heat or by reducing pressure, the reverse process, i.e. removal of the adsorbed substance from the surface occurs, called desorption. The adsorption of gases on the surface of metals is called occlusion. Generally, we confuse between the two terms adsorption and absorption, so following are the point differences between the two terms: Adsorption Absorption 1. It is a surface phenomenon in which substance is con-centrated only at the surface of adsorbent. 2. Rate of adsorption is initially high and then decreases till the equilibrium is attained. 1. It is a bulk phenomenon where the substance is uniformly distributed through- out the bulk of the solid. 2. Rate of absorption is uniform throughout the process.

Most common example which explains the distinction between the adsorption and absorption process is the interaction of water vapor with silica gel and anhydrous as illustrated in the following figure:

It is found that solids, in finely divided state act as good absorbents because of large surface area. Some examples of good absorbents are charcoal, alumina gel, silica gel, finely divided metals, clay, colloids, etc. (I) Mechanism of Adsorption

From the above figure, it is clear that inside the adsorbent or bulk, all the forces acting between the particles are mutually balanced. But on the surface the particles experience only the residual attractive forces by the atoms or molecules from one side i.e., from bulk side. These forces of adsorbent are responsible for attracting the adsorbate particles on its surface. During adsorption the residual forces on the surface decreases. As a result surface energy decreases which appears as heat. Thus adsorption is an exothermic process (i.e., is always negative). When a gas is adsorbed, its entropy decreases due to restriction of freedom of movement of its molecules (i.e., is also negative). As per the thermodynamic requirement, at constant pressure and temperature, must be negative, so the value of must have sufficiently high negative for a process to be becomes less and less negative and ultimately becomes spontaneous. As the adsorption proceeds, equal to , so that

becomes zero and the equilibrium state is obtained.

(ii) Types of Adsorption On the basis of the nature of bond between the adsorbate and adsorbent, adsorption may be of two types physical adsorption or physisorption and chemical adsorption or chemisorption. Following table describes the comparison between the two types of adsorption. Physisorption Chemisorption 1. It involves weak van der Waals forces between the 1. If involves the chemical bond (covalent or

adsorbate and adsorbent. 2. In this case, enthalpy of adsorption is low

ionic) between adsorbate and the adsorbent. 2. In this case, enthalpy of adsorption is high

3. No appreciable activation energy is required. 4. Not specific in nature as the van der Waals forces are same for all types of adsorbate. 5. Reversible in nature, i.e.,

3. High activation energy is required, thus also called activated adsorption. 4. Highly specific in nature because it occurs only if there is possibility of chemical bond between the adsorbate and adsorbent. 5. Irreversible in nature.

6. It depends on the chemical nature of gas, 6. It depends on the physical nature of gas, i.e., the gases i.e., gases which can react with the adsorbent which are more liquefiable can be easily adsorbed. show chemisorptions. 7. It results into multi-molecular layers on adsorbent surface under high pressure. 7. It results into unimolecular layer on adsorbent.

(iii) Effect of Pressure and Temperature on Adsorption In both types of adsorption, i.e., physisorption and chemisorption, when the pressure is increased, more of gas is adsorbed because the volume of the gas decreases (Le-chatelier principle). As the adsorption is an exothermic process, it readily occurs at low temperature and decreases with the rise in temperature according to Le-chateliers principle. But the chemisorption process is very slow at low temperature because of high activation energy; therefore it increases with the rise in temperature like most chemical changes. It is observed that physisorption of a gas adsorbed at low temperature may change into chemisorption at high temperature. (iv) Adsorption Isotherm A curve which shows the expression of the variation in the amount of gas (x) adsorbed by a definite mass of adsorbent (m) with the pressure (p) at constant temperature, is known as adsorption isotherm. Freundlich Adsorption Isotherm Given by Freundlich in 1909, according to which:

Where, k, p and n are constants which depend on the nature of adsorbent and the gas at a particular temperature. Taking log of both sides,

Following curve is the representation of Freundlich adsorption isotherm which indicates that at a fixed pressure, there is a decrease in physical adsorption with increase is temperature.

Fig. Plot of against p (Adsorption isotherm)

Fig. Plot of against log p (Freundlich isotherm)

The equation corresponds to straight line equation So, the Freundlich isotherm is valid only when a straight line is obtained in the above plot otherwise not valid.

Practically the value of ranges between 0 to 1 (Probable range 0.1 to 0.5) Freundlich isotherm is not applicable at high pressure because it doesnt explain why the experimental isotherms always seem to approach saturation at high pressure. (v) Adsorption of Solution by a Solid : Solids can also adsorb solutes from solution like they adsorb gases. For example, the litmus solution becomes colourless when shaken with charcoal. In the presence of magneson reagent, the precipitate of acquires blue colour which is due to adsorption of magneson. Freundlichs equation describes the behaviour of adsorption from solution. In this case, instead of pressure, concentration of solution (C) is taken into account. The equation is:

C = equilibrium concentration i.e., when adsorption is complete.

When a plot of against log C is drawn, a straight line is obtained that proves the validity of Freundlichs isotherm. (vi) Some Applications of Adsorption : (a) Silica and aluminium gels are used as adsorbents to remove the moisture and control humidity. (b) Gas mask which consists of activated charcoals or mixture of adsorbents, is used for breathing in coal mines to adsorb poisonous gases. (c) Adsorbent removes the colouring matter from solutions. For example, animal charcoal removes colours from solutions by adsorbing coloured impurities. (d) Adsorption helps in creating high vacuum. Charcoal removes the traces of air by its adsorption from a vessel evacuated by a vacuum pump to give a very high vacuum. (e) A number of drugs are used to kill the germs by getting adsorbed on them. (f) Chromatography has a number of applications in analytical and industrial fields. All chromatographic processes are based on the phenomenon of adsorption. (g) A mixture of noble gases can be separated by adsorption of gases on coconut charcoal at different temperatures due to the difference in degree of adsorption of gases by charcoal.

Catalyst and Catalysis

Substances, that alter the rate of a chemical reaction and themselves remain chemically and quantitatively unchanged after the reaction, are known as catalysts, and the process is known as catalysis.

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In fact, the rates of a number of chemical reactions can be altered by the mere presence of a catalyst. For example, the decomposition of potassium chlorate occurs at slow rate in the range of temperature 653 873K.

But, when a little amount of manganese oxide is added, same reaction occurs in lower temperature range i.e., 473 633K, at a much faster rate. Here the mass and composition of manganese oxide remains unchanged. Promoters are the substances that increase the activity of a catalyst while poisons decrease its activity. For example, molybdenum (Mo) acts as a promoter for the catalyst iron (Fe) in manufacture of ammonia by Habers process. Positive catalysts are those substances which increase the rate of reaction. For example, NO or acts as a positive catalyst in the oxidation of Negative catalysts are those substances which decrease the rate of reaction. For example, phosphoric acid in decomposition of and alcohol in case of oxidation of chloroform act as negative catalyst. (I) Types of Catalysis : On the basis of phase similarity of catalyst with the reactants, catalysis may be catagorised into two types: A. Homogenous Catalysis : In homogenous catalysis the catalyst and the reactants are in the same phase. Examples:

Here, the reactants

and the catalyst (NO) are in the same gaseous phase.

Here, the reactants

and the catalyst

are in the liquid phase. In

this reaction, hydrolysis of methyl acetate is catalysed by ions furnished by HCl. B. Heterogenous Catalysis : The catalytic process in which the reactants and the catalyst are in different phases, is known as heterogenous catalysis. Examples: (a) Reaction between dinitrogen and dihydrogen to form ammonia is catalysed by finely divided iron (Habers process). Here, the reactants the solid state: are in gaseous phase while the catalyst (Fe) is in

(b) Similarly, in Ostwalds process, oxidation of ammonia into nitric oxide is catalysed by solid platinum gauze:

Here the reactants are in gaseous state while the catalyst (Pt) is in the solid state. In heterogenous catalysis, the catalyst used is generally solid and the reactants are mostly gases and sometimes liquids. Since the reaction starts at the surface of the catalyst, this type of catalysis is also called surface catalysis. (ii) Adsorption theory of Heterogenous Catalysis :

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Modern adsorption theory is the combination of both the old adsorption theory and the intermediate compound formation theory, hence it is able to explain the catalytic action along with the mechanism of heterogenous catalysis. This theory also explains why a catalyst is effective in even a small quantity and its mass and chemical composition remains unchanged at the end of reaction. However, it fails to explain the action of catalytic promoters and catalytic poisons. In accordance with this theory there are free valences on the surface of solid crystals (generally metals) and the mechanism of catalysis involves the following five steps: (a) Diffusion of reactants to the surface of catalyst. (b) Adsorption of reactant molecules on the surface of the catalyst. (c) Occurrence of chemical reaction on the catalysts surface through formation of an intermediate. (d) Desorption of reaction products from the surface due to lack of its affinity for the catalyst surface, and thereby, making the surface available for more reactions to occur. (e) Diffusion of reaction products away from the surface of the catalyst.

Adsorption of reacting molecules, formation of intermediate and desorption of products (iii) Some important features of solid catalysts: (a) Activity: The ability of a catalyst to increase the rate of reaction, is called its activity. For example, do not combine normally but, in the presence of platinum (Catalyst), the combination of forms water with explosive violence.

The activity depends on the extent of chemisorption but the adsorption should not be so strong that the adsorbed molecules become immobile and there is no space on the surface of catalyst available for other molecules to get adsorbed. (b) Selectivity: Selectivity of a catalyst is its ability to direct the reaction in order to form a particular product. For example, in presence of different catalysts, form different products as follows:

(c) Specificity: Action of a substance as a catalyst is defined for a particular reaction i.e., a particular catalyst is specific for a particular reaction. Thus, a substance acting as a catalyst in one reaction may fail to catalyse other reaction. (iv) Shape selective catalysis and zeolites: Those catalytic reactions that depend on the pore structure of the catalyst and the size of reactant and product molecules are called shape selective catalysis. Zeolites act as good shape selective catalysts because of their honeycomb like structures. They are microporous three-dimensional network silicates in which some silicon atoms are replaced by aluminium atoms giving AlSi frame work. The size of their pores generally varies between 260 740pm. Thus, only those molecules can be adsorbed in these pores whose size is small enough to enter and leave easily. Thus zeolites act as selective adsorbents. Different types of zeolites are found in nature as well as synthesized in laboratory. An important zeolite catalyst used in the petroleum industry is ZSM5 (Zeolite sieve of Molecular porosity 5) which converts alcohol directly into gasoline (petrol) by dehydrating them to give a mixture of hydrocarbons.

Similarly, Many other zeolites are being widely used as catalysts is petrochemical industries for cracking of hydrocarbons and their isomerization. Zeolites form an important class of oxide catalysis. (v) Some industrially important catalytic processes: Process Catalyst 1. Habers process for the manufacture of ammonia Finely divided iron, molybdenum as promoter; conditions : 200 bar pressure and 723-773K temperature.

2. Ostwalds process for the manufacture of nitric acid.

Platinised asbestos; Temperature 537K.

Platinised asbestos or vanadium pentoxide 3. Contact process for the manufacture of sulphuric acid. temperature 673-723K

(vi) Enzyme Catalysis: Enzymes are complex nitrogenous organic compounds which are produced in living cells of plants and animals. They are also called biochemical catalysts because of their importance in biochemical processes. Characteristics:
Enzymes form a colloidal solution in water and hence they are very active catalysts. Like inorganic catalysts they do not disturb the final state of equilibrium of a reversible reaction. They are highly specific in nature, i.e., one catalyst cannot catalyse more than one reaction. They are highly specific to temperature. The optimum temperature of their activity is They are deactivated at Their activity is increased in the presence of certain substances, known as co-enzymes. A small quantity of enzyme catalyst is sufficient for a large change. They are destroyed by U.V. rays. Their efficiency is decreased in presence of electrolytes. .

Examples :

(e) In stomach, pepsin enzyme converts proteins into peptides, whereas in intestines, pancreas trypsin converts proteins into amino acids by hydrolysis. These amino acids are absorbed by blood and are used in the building of tissues. (f) Ptyalin enzyme present in human saliva converts starch into glucose.

(vii) Mechanism of Enzyme Catalysed Reaction The enzyme catalysed reactions may be considered to proceed in two steps.

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(a) Binding of enzyme to substrate to form an activated complex.

(b) Decomposition of the activated complex to form the product.

Colloids and Colloidal Solutions

Colloid or Colloidal dispersion is a heterogenous system between the two extremes of suspensions and solutions in which one substance is dispersed (dispersed phase) as very fine particles in another substance called dispersion medium. Following are the point differences between true solutions, colloidal solutions and suspensions: S. Properties True Solutions Colloidal Solutions Suspensions No. 1. Particle size (diameter) Quickly Particles not visible Between 1nm to 1000nm

2. Diffusion 3. Visibility

Slowly Particles visible under ultramicroscope

Do not diffuse. Particles visible to naked eye or under microscope. Filteration not possible. Settle on standing. Opaque

4. Filteration

Particles pass through ordinary Particles pass through ordinary filter paper as well as through filter paper but not through animal membrane. animal membrane. Do not settle Translucent

5.

Settlement of Do not settle particles Transparent and clear

6. Appearance

Among the above points of difference, the main distinction among the true solutions, colloids and suspensions is of the particle size. The colloidal particles are bigger than the particles of solution (molecules or ions) but smaller than the particles of suspensions (i.e., visible grains). In case of colloidal dispersions, the substance in solution is termed as the dispersed phase while the medium in which the particles are dispersed is called the dispersion medium.

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(I) Types of colloids on the basis of physical state of dispersed phase and dispersion medium: S. Dispersed phase Dispersion medium Types of colloid Examples No. 1. Solid 2. Solid 3. Solid 4. Liquid 5. Liquid 6. Liquid 7. Gas 8. Gas Solid Liquid Gas Solid Liquid Gas Solid Liquid Solid Sol Sol Aerosol Gel Emulsion Aerosol Solid foam Foam Some coloured glasses, gemstones Some paints, cellular fluids Smoke, dust Cheese, butter, jellies Milk, hair cream Fog, mist, cloud, insecticides, sprays Pumice stone, Foam rubber Froth, Soap leather, Whipped cream

In the above table, maximum 8 types of colloidal systems are possible with the different combinations of dispersed phase and dispersion medium. Since the mixture of gases is completely miscible, they form homogenous mixture and hence it is not a colloidal system. Out of the various types of colloids, the most common are sols (Solids in liquids), gels (liquids in solids) and emulsions (liquids in liquids). (ii) Types of colloids based on nature of dispersed phase and dispersion medium (a) Lyophobic Sols : Here particles of dispersed phase have no affinity for dispersion medium, rather they hate dispersion medium. They are not easily prepared and need stabilizing agents for their preservation. They are irreversible. Example : sols of gold, silver, , etc. They are also called extrinsic colloids. (b) Lyophilic Sols : Here particles of dispersed phase have great affinity for the dispersion medium. They are self stabilised because of strong attractive forces operating between the suspended particles and the dispersion medium. They are reversible in nature. Examples : gums, gelatin, starch, albumin, etc. They are also known as intrinsic colloids. (iii) Classification Based on Types of Particles of the Dispersed Phase : (a) Multimolecular Colloids : A large number of atoms or smaller molecules of a substance on dissolution aggregate together to form species having size in the colloidal range. Such species are called multimolecular colloids. Example : A sulphur sol contains thousands of sulphur molecules, a platinum or gold sol may have particles of various sizes having many atoms. (b) Macromolecular Colloids : Substances such as proteins, DNA, etc. which have larger molecular masses are called macromolecule. After their dispersal in dispersion medium, the system may have a size of the colloidal range. This system is called macromolecular colloids. Example : Natural starch, cellulose, proteins, vitamins, hormones, nucleic acid, etc. Synthetic or man-made Polyethylene (PE), nylon, dacron, polystyrene, synthetic rubber, etc. (c) Associated Collides (Miscelles) : There are certain substances which at low concentrations behave like normal strong electrolytes but at higher concentration behave as colloidal solutions due to the formation of aggregated particles. Such colloids are associated colloids and aggregated particles as miscelles. Examples : soaps and detergents. Surface Active Agents Those substances which when tend to concentrate on the surface of solution and therefore, lower the surface tension are called surface active agents e.g., soaps and detergents. (iv) Preparation of Colloidal Solutions

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A Dispersion Method: Bigger suspension particles (greater than

cm) are broken down into smaller

particles of colloidal size ( cm). (a) Mechanical Dispersion: A colloidal mill is used. Useful in manufacturing dyestuffs, printing inks, paints, varnishes, ointments and dental creams. (b) Electrodispersion: An arc is produced between rods of metals immersed in water containing KOH, surrounded by ice cold water. KOH is added to stabilize the sol. Ag, Au, Pt, Cu sols are prepared in this manner. The method is known as Bredig Arcs Method. (c) Dispersion by Third Substance: The process of passing a precipitate into a colloidal solution by adding an electrolyte is called peptization. In this process, dispersion medium (liquid) breaks up the precipitate into a colloidal state. Cellulose nitrate is peptized by organic solvents such as ethyl alcohol. The commercial name of the product is collodion. Example : Fresh precipitate of gets easily

dispersed into the colloidal solution of by adding solution. B Condensation Methods: In this case we start with molecular-sized particles of the substance and then build them to particles of colloidal dimensions. The different methods are : (a) By Chemical Reaction: Double Decomposition: Sulphides of metal are usually prepared by this method.

Hydrolysis: A red sol of is obtained by adding some ferric chloride to a beaker of boiling water.

Reduction: Colloidal gold, known as purple of cassius is prepared by reducing auric chloride by stannous chloride.

Oxidation: Colloidal solutions of non-metals like sulphur, selenium and iodine may be obtained by oxidation.

(b) By exchange of solvent i.e., by lowering of solubility: A substance is dissolved in a solvent and the solution is poured into another solvent in which it is less soluble. For example, sulphur sol is formed by pouring its solution in into water. (c) By excessive cooling: A colloidal solution of ice in an organic solvent like chloroform or ether can be prepared by excessive cooling of water in these solvents. (d) By cathodic reduction: When lead salts are electrolysed a sol of lead is obtained at cathode. (v) Purification of Colloidal Solutions (a) Dialysis: In this process colloidal solution is purified by passing it through a parchment membrane which allows the passage of ions or molecules but not of colloidal particles. It is a slow process but the movement of the ions can be made rapid by applying electric field (electrodialysis).

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The process of separating a crystalloid from a colloid by filtration or diffusion through a membrane is called dialysis. (b) Ultrafiltration : This is done by passing it through filters of unglazed porcelain called ultrafilters. Too much purification of colloid is never done as it sometimes brings about precipitation of colloid. In fact, small amount of electrolyte is essential for stability of the colloidal solution. (vi) Properties of Colloids: (a) Brownian Movement : Colloidal particles travel in a zig-zag path, when it is examined by ultra microscope. This movement is called Brownian movement after the name of its discoverer, Robert Brown (1827).

The movement is independent of the nature of particles. It is more rapid when size of the particle is small and the solution is dilute or less viscous. Cause : It is believed to have arisen due to unequal bombardment of colloidal particles by molecules of dispersion medium. With increase in size of particle chances of unequal bombardment decreases and as a consequence in suspension, Brownian movement is completely absent. (b) Tyndall Effect : When a strong beam of light passes through a colloidal solution, the path of light becomes visible and when viewed through microscope placed at right angle to the path of light, the colloidal particles appear as pin points of light moving against a dark background.

This phenomenon is known as Tyndall effect and the illuminated path is called Tyndall cone. This phenomenon is not observed in pure solvents or true solutions. Cause : This effect is observed due to scattering of light by colloidal particles.

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Determination of size of colloidal particle : Zsigmondy has even been able to determine the size of the colloidal particles by ultramicroscope fitted with a micrometer. The radius of the colloidal particle be easily determined with the help of the following equation : can

Where

is Avogadros number,

are number of particles at depth

respectively, are the densities of colloidal particles and dispersion medium respectively. (c) Cataphoresis or Electrophoresis : The movement of colloidal particles towards oppositely charged electrode in an electric field is called electrophoresis. After reaching the electrode the particles get discharged and precipitate out. This movement under electric field is also called cataphoresis. This term implies movement towards cathode only, which is not actually the case, electrophoresis is a better and more appropriate term. This process finds application in determination of charge, determination of rate of migration, removal of carbon from smoke, removal of dirt from sewage water and in electrodeposition of rubber. (d) Coagulation : The colloidal particles bear similar electric charge and that is why they stay away from each other due to repulsion. If the charge is removed, they come together and are precipitated. The precipitation and settling down of the discharged particles is called coagulation or flocculation. Example : sol is coagulated by the addition of ions. solution. The negative charge of

particles is neutralised by

Similarly, sol bearing +ve charge will be coagulated by ions on addition of solution. The coagulation power of different ions is different. Hardy-Schulze Law (a) The greater the valency of the action ion of the electrolyte, the greater will be its precipitating action. for -vely charged sols for +vely charged sols (b) The coagulation of +vely charged sols may be brought about by -vely charged sols also. This is called mutual coagulation. (c) Lyophilic sols are coagulated with difficulty. A large excess of the electrolyte has to be added. (d) Coagulation of sol is facilitated by increasing the temperature and applying centrifugal field.

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Coagulation value or flocculation value : It is defined as minimum number of millimoles of electrolyte required to coagulate 1 litre of colloidal solution.

Protection : Gold Number : A lyophobic sols can be prevented from being coagulated by previous addition of a more stable lyophilic colloid. For example, if a little gelatin is added to a gold sol, it is no longer coagulated by the addition of NaCl solution. In this case gelatin is said to protect the gold sol. This phenomenon is called protection. The action of protective colloid (lyophilic) differs from one sol to another. This is measured in terms of gold number. (Zsigmondy, 1903). The sol that is protected from being coagulated is known as protected colloid (lyophobic). The number of milligrams of a protective colloid which must be added to 10 ml given gold sol so that it is just prevented from coagulation by addition of 1 ml of 10% NaCl solution is known as the gold number of protective colloid. The smaller the gold number of the lyophilic sol, higher will be its protecting power. Gelatin has lowest gold number i.e., 0005 to 001 mg and highest starch (20 to 25 mg).

Summary
Adsorption Adsorbent Adsorbate Physisorption Chemisorption Enthalpy of Adsorption Extent of Accumulation of a substance in higher concentration at the surface than the adjoining bulk phases. The substance on the surface of which adsorption takes place. The substance which is adsorbed at the surface of adsorbent. Adsorption in which adsorbate is held on the surface of adsorbent by weak van der Waals forces. The adsorption in which adsorbate is held on the surface of adsorbent by chemical bonds (covalent or ionic). Enthalpy change accompanying the adsorption of one mole of adsorbate on the adsorbent. Enthalpy of adsorption is always negative. Extent of Adsorption decreases with increase in temperature and increases with

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Adsorption Adsorption Isotherm Freundlich Adsorption Isotherm

increases in pressure. A graph of extent of adsorption vs. pressure at constant temperature.

Adsorption Isobar A graph of extent of adsoption vs. temperature at constant pressure. Saturation Pressure Colloidal State Sol Lyophilic Sol Lyophobic Sol Macromolecular Colloid Multimolecular Colloid The pressure beyond which extent of adsorption becomes independent of pressure. A state in which the particle size of the substance is in the range 11000nm. A colloidal solution containing solid as the disperse phase and liquid as the dispersion medium. A colloidal solution in which there is great affinity between the disperse phase and the dispersion medium. A colloidal solution in which there is little affinity between the disperse phase and the dispersion medium. Lyphobic sols are less stable. A colloid in which colloidal particles are macromolecules. A colloid in which colloidal particles are clusters or aggregates of smaller molecules.

Associated Colloid A colloid which is formed when concentration of the solute exceeds a limit. Peptization Coagulation Coagulation Value Preparation of a colloidal solution by shaking the substance with dispersion medium in the presence of some suitable electrolyte. Precipitation of a colloidal solution by induced aggregation of colloidal particles. Minimum concentration of the electrolyte in millimoles per litre needed to cause coagulation of the sol.

In case of electrolytes, the ion carrying charge opposite to that of colloidal particles Hardy-Shulze Rules is effective in causing coagulation. Greater the valency of the ion causing the coagulation greater is the coagulating power. Brownian Movement Tyndall Effect Electrophoresis Gold Number Catalysis Heterogenous Catalysis The zig-zag movement of colloidal particles. Scattering of light by colloidal particles. The movement of colloidal particles towards one of the electrodes on passage of electricity through colloidal solution. A parameter used for expressing protective power of a lyophilic colloid. Acceleration of rate of a reaction by using some additional substance. Surface catalysis. Acts through adsorption.

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Zeolites

Shape selective catalysts.

Questions
1. What is electrophoresis? 1 Mark The phenomenon in which there is movement of colloidal particles either towards the cathode or anode, under the influence of the electrical field is called electrophoresis. 2. Artificial rain is caused by spraying salts over clouds. Give the reason. 1 Mark

Artificial rain is caused by spraying salts or oppositively charged colloidal dust over the clouds by aeroplane. Water molecules of clouds get neutralized and coagulate to bigger water drops and cause artificial rain. 3. Define catalysis. What is the difference between a catalyst and promoter. The process in which rate of the reaction is altered with the help of a catalyst. [1 mark]

Catalyst is a substance which can change the rate of a reaction without taking part in the reaction. [ mark] Promoters are the substances which enhance the activity of catalyst. For example: [ mark]

Fe(s) is a catalyst while Mo(s) is a promoter.

4. Draw adsorption isobars for physical and chemical adsorption.

[1 mark]

[1 mark]
5. How will you apply Freundlich adsorption isotherm in case of solutions. Give its mathematical expression. The process of adsorption can take place even in solutions. Freundlich adsorption isotherm is found to be applicable

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even in the adsorption from solutions. We use concentrations in place of equilibrium pressures of the adsorbates in the solution. [1 mark]

Thus, if we plot a graph between is equal to 1/n. [2 marks]

and log C, a straight line will be obtained. The slope of the line

6.

5 Marks

(a) What do you understand by activation of adsorbent? How is it achieved? (b) Describe chemical method each for the preparation of sols of sulphur and gold in water.
(a) An adsorbent has very high tendency for adsorption due to exposure to moisture or air etc. These gases are adsorbed on the surface. The removal of these adsorbed gases from the surface of a solid is called activation of the adsorbent. The activation of an adsorbent is done generally by heating in vacuum.

(b) Sulphur sol can be prepared by oxidation method when sulphur sol is formed.

is bubbled through bromine water,

Gold sol can be prepared by reduction of

with HCHO.

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Higher Order Thinking Skills (HOTS)

1. Bleeding from a fresh cut stops on applying alum. Why? Blood is a colloidal solution. Potash alum contains 2. Why is Ferric hydroxide sol positively charged? sol is prepared by the hydrolysis of which has positive charge because it preferentially adsorbs and which coagulate the blood. 1 Mark

ions on its surface from the solution as given below:

3. A small amount of anhydrous and silica gel are kept separately in two corners of a conical flask containing water vapour. What phenomenon will occur? Anhydrous will absorb water while adsorption of water vapour will occur on silica gel.

4. What is the effect of dissolved impurities of crystalloids on a colloidal solution? Colloidal solution becomes unstable and coagulation of the sol soon occurs. 5. Two test tubes, one containing concentrated solution of KCl while another dilute solution of KCl, are shaken with blood charcoal. What phenomenon will occur in both the test tubes? In first tube positive adsorption takes place while in second negative adsorption occurs. 6. A AgI sol can be positively or negative charged. Explain why. Charge on a sol is due to preferential adsorption of common ions on the surface. AgI on shaking with KI adsorbs ions and gets negatively charged. However on shaking with becomes positively charged. 7. Why is activated charcoal better adsorbent than ordinary charcoal? Activated charcoal is obtained on heating in absence of air. It has greater exposed surface area than ordinary charcoal. 8. Why are catalysts more effective in finely ground state? On grinding the surface area of a catalyst increases thus more adsorption occurs. 9. Why lyophilic colloids are more stable than lyophobic sols? Because lyophilic sols contains highly hydrated colloidal entities. 10. Why cannot we prepare a colloidal solution of gas in gas type? Gases form a true solution since they are freely miscible without any limit. solution, ions are adsorbed hence

Reasoning Questions
1. Why is alum added to purify muddy water? Hint: (Hint: Clay particles are charged) Solution: The clay particles are negatively charged. Alum contains charge of clay particles and settle at the bottom due to coagulation. 2. The colour of and ions, which neutralize the

discharges slowly in the beginning during its reaction with oxalic acid but quickly after

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sometime, why? Hint: (Hint: Auto catalyst) Solution: It is a redox reaction in which ions are formed which act as auto catalyst.

3. 0.1 M

solution is more effective than 0.1 M NaCl solution in coagulating is less effective than 0.1 M in coagulating solution. Why?

solution while 0.1 M

Hint: (Hint: Hardy Schulze rule) Solution: is why sol is negatively charged therefore to coagulate this, cation should possess greater valancy, that is more effective. Similarly sol is positively charged and for its coagulation anion should is more effective.

possess greater valiancy according to Hardy-Schulze rule, that is why 4. On mixing yellow sol of Why? with red sol of

in equivalent amount give rise to colourless solution.

Hint: (Hint: Both sols have opposite charge) Solution: sol is negatively charged while occurs leaving behind colourless water 5. Mercury sol is prepared by ultra sonic dispersion. Why? Hint: (Hint: Ultrasonic waves have greater frequency than sound waves) Solution: Ultra sonic vibrations have frequency greater than sound waves. They are passed through a beaker containing Hg and water. Hg vapourizes and then condenses in water to form mercury sol. 6. Gelatin is added to ice creams. Why? Hint: (Hint: Emulsifier) Solution: Gelatin is added in the preparation of ice creams to act as emulsifier. It stabilizes the emulsion (ice creams). 7. When benzoyl chloride is reduced by hydrogen in the presence of Pd, the product is benzyl alcohol. If mixed with the catalyst before passing the gas, the product is benzaldehyds. Give reason. Solution: Hydrogen reduces benzoyl chloride to benzyl alcohol in the presence of Pd catalyst as given below: is sol is positively charge thus mutual coagulation

On adding hydrogenation occurs upto the aldehyde because which reduces the efficiency of Pd.

acts as negative catalyst

8. The layer of fat in the container used for preparing soap can be washed by adding hot washing soda solution. Give reason. Hint: (Hint: Saponification) Solution: Washing soda gets hydrolysed to form NaOH which reacts with fats to form soap by saponification reaction. Thus soap helps in cleaning the container.