Colloidal State ia 6 LEARNING OBJECTIVES © Differentiate between true solutions, colloidal solutions and suspensions ‘© Understand the terms dispersed phase and dispersion medium. ‘* Classify colloids on the basis of physical state of dispersed phase and dispersion medium, appearance and solvent affinity ‘* Understand dispersion colloids, multimolecular colloids and macromolecular colloids Follow the cleansing action of soaps on the basis of micelle formation. Know the methods of preparation of colloids by dispersion methods, condensation methods and chemical methods. Study the mechanical, optical and electrical proportion of colloids Understand Hardy-Schulze rule and flocculation value Know about protective colloids and gold number Study different kinds of emulsions, emulsifiers and demulsification Study different classes of gels Determine the size of colloidal particles by different methods Study applications of colloids. 6.1 INTRODUCTION _ oe ee eceee Colloidal state was first conceptualised by Thomas Graham in 1861. He observed that solutions of certain substances such as sugar, salt, acids and bases diffused readily through parchment membrane while those of glue, gelatin and silicic acid could not. The substances belonging to the former category were called crystalloids and those from the second category were given the name colloids. This is how a new branch, colloid chemistry, emerged. However, it was realised that distinction between crystalloids and colloids was not rigid because many crystalloids could be converted into colloids by suitable methods. Also, it came to be known that the same substance behaves as a crystalloid in one solvent and a colloid in another solvent. For example, soaps show colloidal behaviour in water while they show crystalloidal behaviour in alcohol in which they dissolve completely. A solution of a crystalloids in a solvent in which it dissolves completely giving a transparent solution is called true solution. When water-soluble substances like glucose, copper sulphate, potassium chloride, etc., are put into water they dissolve and a homogeneous mixture is obtained. The particles of the solute are not visible and their size is molecular. Such mixtures are called molecular solutions or true solutions. Take muddy river water or an insoluble substance like lead sulphate or calcium sulphate and put it into water. The particles of the solute are visible even with the naked eye because their sizeis large. On keeping for some time, the particles settle down. These mixtures are called suspensions. Between these two extremes, there are particles which are bigger than molecules but are too small to be seen even by a microscope. The colloidal state can thus be regarded as the intermediate stage between molecules and particles of a coarse suspension. A colloidal solution is also referred to as solution. These three states are illustrated in Fig. 6.1. coo 0000 a 0 Oe O60 pos 6 ae oo 00000 O O a6 6 6 6 ote aCe eC ey io 00600000 oe oe ee VY XX ib 6 o 6 6 Go 6090006 O © SO 6 oa 6 6, 05 080 000 100nm ‘True solution Collvidal solution Suspension Fig. 6.1 Representation of true solution, colloidal solution and suspenstion. Colloidal particles have an enormous surface area per unit mass. This can be explained in terms of their small size. Consider a cube with one edge equal to 1 cm. It has a total surface area of 6 cm?. If we divide this cube into 10? smaller cubes, each small cube will have the size of a large colloidal particle. The total surface area of the 10! smaller cubes would be 60,000 cm?. Such a large surface area of colloidal particle is of great importance as we shall study later. The distinguishing characters of the three types of solutions are given in Table 6.1. Table 6.1 Difference between a true solution, colloidal solution and suspension True Solution 1. The solute molecules in a true solution are not visible, even with a powerful microscope. 2. The solute molecules can pass through even fine filter papers. 3. A tue solution forms a homogenous mixture, 4. When a strong beam of light is thrown on a true solution, the path of light is not illuminated. Colloidal Solution The molecules of the dispersed phase cannot be seen with naked eyes. However, they can be made visible through a powerful microscope called ultramicroscopie. The colloidal particles can also pass through ordinary filter papers but cannot pass through filter papers called ultra filters. A colloidal solution is heterogeneous. The path of light is visible due to scattering of light, when a strong beam of light is passed through a colloidal solution (Tyndall effect). Suspension The particles are so big that they are visible even with naked eye. They sometimes settle at the bottom of the container, when the mixture is allowed to stand. The suspended particles are retained even by ordinary filter papers. Suspension is completely a heterogeneous mixture. No Tyndall effect is observed.5. No electrical properties such as Colloidal solutions exhibit these electro-osmosis, electrical properties toa great No such electrical properties are cataphoresis and °c! exhibited. coagulation are - observed. . ne panicle size iS The particle size is 1-100 nm in _The particle size is above 100 nm aan diameter. in diameter. 7. The particles of the solute in fue The particles of a colloidal The suspension particles are Splntion can Pass solution can pass through a retained by a parchment parchment t parchment membrane. membrane. membrane. 8. The osmotic pressure exerted Colloidal solutions exert a very by the solution is low osmotic pressure. relatively more. No osmotic pressure is observed. 9. The solutions do not possess the Co jJpidal solutions possess property of The phenomenon of adsorption is adsorption Ge eaaneeeey much less marked. surface . phenomenon). Various Phases in a Colloidal Solution A colloidal solution is a heterogeneous system consisting of two phases, viz. the dispersed phase and the dispersion medium. 1. Dispersed Phase It is comparable to the solute in a solution. It can be said that the component which is present in smaller proportion is the dispersed phase. For example, in a colloidal solution of starch in water, starch is the dispersed phase. 2. Dispersion Medium It is comparable to the solvent in a true solution. It is the component which is present in greater proportion. In the example of colloidal solution of starch in water, water is the dispersion medium. It may be remembered that particles of the dispersed phase (colloidal particles) are bigger than those of the dispersion medium (molecules or ions). 6.2 CLASSIFICATION OF COLLOIDS: Colloids can be classified on the basis of physical state of dispersed phase and dispersion medium on the basis of appearance and on the basis of solvent affinity. Each of these is discussed as under. 6.2.1 Classification of Colloids on the Basis of Physical State ofDispersed Phase and Dispersion Medium Dispersed phase or the dispersion medium can be a solid or liquid or gas; there are eight different combinations possible. Table 6.2 describes the various colloids in which the dispersed phase and dispersion medium may have the same or different physical states. A colloidal solution with both the components in the gaseous state is not possible as according to Graham’s law of diffusion, they form a homogeneous mixture. Table 6.2 Classification of colloids based on physical state of the phases 1. Solid Solid Solid sol Coloured glass, alloys, gems : Paints, inks, egg white, colloidal Au, 2. Solid Liquid Sol ‘Colloidal Pt 3. Solid Gas Aerosol Smoke, dust 4. Liquid Solid Gel Curds, cheese, jelly, pudding 5 Liquid Liquid Emulsion Milk butter, oil in water 6 Liquid Gas Aerosol Mist, fog, clouds 7. Gas Solid Solid Cake, bread. pumice stone foam BGs Liquid Foam Soap lather, aerated water Colloids may be divided into the following two main categories on the basis of appearance: 1, Sols When a colloidal solution appears as a fluid, it is termed sol. Sols are named after the dispersion medium. For example, when the dispersion medium is water, they are called hydrosols. If the dispersion medium is alcohol, they are called alcosols and if it is benzene, they are called benzosols. 2. Gels When a colloid has a solidlike rigid appearance, it is called gel. The ridigity of a gel varies from substance to substance. Some substances may occur both as sols as well as gels. This depends upon the relative concentration of the dispersed phase and dispersion medium. The colloidal system in which the dispersed phase is a liquid and the dispersion medium is solid is known as gel. A gel is formed by interlocking of the dispersed phase particles. Gelatin dissolves in warm water to form a colloidal solution which sets into a gel. 6.2.3 Classification of Colloidal Solutions on the Basis of Solvent GunED When the dispersion medium exerts an attraction on the dispersed phase then we get a lyophilic sol(solvent loving). When the attraction between the dispersion medium and the dispersed phase is very little then the sol is called lyophobic sol (solvent hating). 1. Examples of Lyophobic Sols (nonreversible) Metals, sulphur, sulphides, silver halides, egg albumen, silicic acid and ferric hydroxide give nonreversible colloidal systems with water. 2. Examples of Lyophilic (Reversible) Sols Protein, starch, glue gelatin and agar-agar give reversible colloidal systems with water. Rubber in benzene is also a reversible colloidal system. The main points of difference between the two are given in Table 6.3. Table 6. + + +, + ++ + ae tay Fig. 6.2 Colloidal clay particles suspended in solution (Hydrophobic sol) Lyophilic (solvent loving) or Hydrophilic Lyophobic (solvent hating) or S.No. Candis Grater Hydrophobic Colloids (water as solvent) 1 Lyophilile colloids pass into the colloidal form Epp Hole coiolds do no! form the readily when brought in contact. colloidal solutions e 2. Colloids of metals (Au, PO), Substances like starch, proteins, gums, soaps and sulphur, arsenius sulphide and metasilicic acid are common examples. silver iodide are common examples of this class. 3. They are called reversible sols because they Cantey are called irreversible sols be recovered from the colloidal solutions and can jaca ey cannot be recovered ere eee from their colloidal forms. 4. The particles may or may not migrate in an Particles migrate only in one electric field. The migration may be in any direction. direction in the presence of electric field.5. ‘The particles are not easily detected in the ultra The particles are easily detected by microscope. an ultramicroscope. 6. Small quantities of electrolytes do not affect precipitation, but only large quantities of electrolytes cause precipitation 6.2.4 Dispersion Colloids, Multimolecular or Association Colloids, Even small quantities of electrolytes can cause precipitation. 1. Dispersion Colloids In case of colloidal solutions in which the dispersed phase has little affinity for the dispersion medium (i.e. solid substance is insoluble in the dispersion medium), the size of the solid particles (dispersed phase) lies in the colloidal range. This system is called a dispersion colloid. For example, gold sol, hydrated ferric oxide sol, colloidal sulphur, a colloidal dispersion of As)03 in water, etc. Generally, this type belongs to lyophobic sols. 2. Multimolecular or Association Colloids In this case, an individual colloidal particle consists of an aggregate of a large number of small atoms or molecules. The size of such species lies in the colloidal range. The species thus formed are called associated colloids or multimolecular colloids, for example, soap solution, dyes, surface active agents, etc. Generally in this type, there is occurrence of lyophobic and lyophilic portions in the same molecules. Thus, the aggregates of ions or molecules with lyophilic as well as lyophobic parts are called micelles. Micelles are of colloidal dimension though the individual ions or molecules may not be of the colloidal dimensions. 3. Macromolecular or Molecular Colloids In such systems, each particle of the dispersed phase is of colloidal dimensions. Mostly this type consist of lyophilic sols. This resembles true solutions in some respects. Examples of this type include proteins, cellulose, the solutions of rubber and high polymers in organic solvents, etc. 6.3 MICELLES There are certain strong electrolytes which give a normal solution at low concentration but show colloidal nature at higher concentration. These are called micelles. These substance may also be referred to as associated colloids. Soap is an example of this class. It forms a micelle. These substances commonly act as surface active substances. They consist of lyophilic as well as lyophobic parts in the same molecule. A long hydrocarbon chain serves as lyophobic and an ionic group like carboxy or sulphuric serves as lyophilic. A micelle may contain as many as 100 molecules. Water is not a good medium for cleaning our body or clothes. This is because of the high surface tension of water. It does not spread evenly over the dirt, particularly grease, in clothes or on the body. The exceptionally high value of surface tension of water could be explained in terms of hydrogen bonding. Without complete wetting of grease by water, we cannot expect efficient cleaning. The function of soap or other synthetic detergents is to decrease the surface tension of water. This is made possible by micelle formation as shown in Fig. 6.3. Ordinary soap is sodium stearate, Cy7H3sCOONa. It gives C)7Hj5COO™ in solution. The hydrocarbon chain consisting of 17 carbon atoms is hydrophobic in nature. A number of such hydrocarbon chains are directed towards grease as shown in Fig. 6.3. The negative poles of thestearate ions then attract the positive ends of water (water is a polar molecule) forming a micelle. i cH, CH; IL, Gh ih Gin th on Je CIN NN Nee ch oh CL cn CH; «CH: CH; - (Cyl sCOO> a ‘The anion of a soap is represented as follows Electrically Hydrocarbon chain “tail” changed head Sodium ion e LD-) LBsionie PRROII Le Sona " 1b) Elydrocarbon end of soap anion ©) Grease micelle is formed (Hydrophobic) dissolves in grease «By (2) Soap anion Fig. 6.3 A. Representation of a soap molecule B. Formation of a micelle. The micelles are then washed away with more water. Thus, soap helps in the cleaning of clothes or body. The function of soap is to reduce grease or oil to colloidal particles; therefore, soaps are emulsifying agents. Grease particles are prevented from coming closer because of the covering by soap molecules. Any synthetic detergent like sodium lauryl sulphate Cy7H75SO™4 Na* would form a micelle by a similar mechanism. A number of methods are available for the preparation of colloidal solutions. These are described under the following heads: 1 persion methods for the preparation of colloidal solutions are described as under: {a) Mechanical Dispersion or Disintegration It involves the following steps: (i) First of all, the substance is powdered thoroughly. (ii) The finely ground substance is brought in the form of coarse suspension, by shaking with the dispersion medium. (ili) The suspension is then made to pass through a colloid mill (disc mill), which consists of two metallic discs almost touching each other and rotating with a terrific speed in opposite directions (Fig. 6.4). The suspension is then subjected to a powerful shearing force, resulting in the breaking of suspended particles to form particles of colloidal dimensions.Suspension S— — biting beh Hollow shaft Colloidal & solution Driving belt —————, Fig. 6.4 Colloid mill The colloid mills are nowadays used in many industrial processes, such as the manufacture of dyestuffs, printing inks, varnishes, lacquers, paints, ointments, dental creams, oil and water colours, etc. (b) Peptization (Dispersion of a Precipitate) It is the redispersion of the coagulated sol. Peptization is defined as the process by which a colloidal solution can be obtained by dispersing the coagulated mass in which the colloidal particles pre-exist. For example, ferric hydroxide is a coagulated sol and is a precipitate. On adding ferric chloride solution (peptizing agent) to it, a reddish brown solution containing ferric hydroxide sol is obtained (Fig. 6.5). Add FeCl; @: @ Changed sol Precipitated wicks of 4 09 © neutral FaOH) and stir eo 28 a nel particles © ® © Fig. 6.5 Preparation of ferric hydroxide sol by peptization The excess of ferric chloride if any, can be removed by dialysis. Similarly, a precipitate of silver iodide can be peptised by shaking with dilute solution of either KI or AgNO3. When very dilute HCI acid is added to the freshly precipitated aluminum hydroxide, Al(OH)3, a colloidal solution of aluminum hydroxide is obtained. The acid should be in small quantity. (c) Electro-dispersion or Bredig’s Arc Method This method is employed for getting colloidal solutions of metals like gold, silver, copper, platinum, etc. The metal rods (electrodes) are immersed in the dispersion medium, say water. An arc is struck between the two electrodes (Fig. 6.6). Asa result of powerful heat of arc, metal is converted into its vapours which get condensed at once (the vessel being placed in a ice-cold water bath), resulting in the formation of colloidal size particles (to stabilize the solid, a small quantity of NaOH or KyCO3 is added).rt ‘Qt Metal & Electrodes Solvent Ice Fig. 6.6 Bredig's arc method : 2(Gendensation or Aagrea tion Methods for Preparation of Golekal ‘Condensation methods for the preparation of colloidal solutions are discussed as under: (a) Exchange of Solvent There are certain substances which are more soluble in one solvent as compared to another. Colloidal solution of such substances can be obtained by pouring the solution of the substances in which it is more soluble to the other solvent, in which it is soluble to a smaller degree. For example, (i) Sulphur and phosphorus are more soluble in alcohol than water. If their alcoholic solution is added to small quantity of water, hydrosol results. (ii) Phenolphthalein is soluble in alcohol but not in water. If its alcoholic solution is added to water, a milky solution is obtained which is the sol of phenolphthalein. (b) Excessive Cooling This method is employed to get colloidal solution of ice in an organic solvent like ether and chloroform. This is done by freezing a solution of water in the given solvent. The molecules of water can no longer be held in solution. They collapse together to yield colloidal-size particles. Chemical methods for preparing colloidal solutions are given below: {a) Hydrolysis A colloidal solution of ferric hydroxide is obtained by adding 2 or 3 ml of 30% solution of ferric chloride to about 500 ml of hot boiling water. FeCl, + 3H.O = Fe(OH); + 3HCI (deep red) (b) Reduction A colloidal solution of gold (violet coloured) may be obtained by adding stannous chloride solution (reducing agent) to a solution of gold chloride 2AuCl,; + 2Sn Cl > 3SnCl, + 2Au Violet (c) Double Decomposition A colloidal solution of arsenious sulphide is obtained by adding water saturated with HS gas, to a solution of arsenious oxide (one gram in 500 ml of water).A8;03 + 3H2$ > As2S3 + 3H,0 (a) Oxidation A colloidal solution of sulphur is obtained by passing H2S gas through a solution containing some oxidising agent, say oil of HNO3, or by passing HS into a solution of sulphur dioxide in water. H,S + [0] > H,0+S SO, + 2H2S > 3S + 2H,0 A sol contains electrolyte during its preparation. A small amount of electrolyte is essential for stability of the sol, but excess of it can cause coagulation. Therefore, it is essential to remove excess of electrolyte. The purification of the sol can be achieved by the following processes. 1. Dialysis The process of removing the dissolved electrolytes from the sol by means of a membrane is called dialysis. A dialyser consists of a bag made of parchment or cellophane and suspended in running water in a trough. The mixture of the colloid and the crystalloid is taken in the bag and apparatus fitted as shown in Fig. 6.7 (a). After some time, whole of the crystalloid in solution passes out while the colloid remains in the bag. It is further observed that the above process of separation can be accelerated if an electric field is applied around the parchment bag. The process is then called electrodialysis. This is shown in Fig. 6.7 (b). Upper part 7 = of a bottle 5 > Impure : colloidal = al solution 4 ‘ a cae = +O Membrane : \ Water >A J (a) Dialysis (b) Electrodialysis Fig. 6.7 Dialysis and Electrodialysis Explanation Due to bigger size, colloidal particles are unable to pass through the parchment bag while ions of the crystalloid are carried away by the running water in the dialyser. Further, on applying the electric field, the movement of the ions is accelerated An important application of dialysis is in the purification of blood in the artificial kidney machine. The dialysis membrane permits small particles to pass through but colloidal haemoglobin does not pass through.2. Ultra Filtration Colloidal particles pass through an ordinary filter paper. This is because its pores are too big to retain colloidal particles. If the filter paper is impregnated with collodion, the pore size of the filter paper is much reduced. Such a modified filter paper is called ultra filter. Separation of colloidal particles from a solution by filtration through an ultrafilter is called ultra filtration. Different properties of colloidal solutions are discussed under the following headings: 1. Mechanical Properties (Brownian Movement) If we examine the colloidal solutions with an ultramicroscope, we find that suspended particles are in a constant rapid zig zag motion (Fig. 6.8). This zig-zag motion is called Brownian movement. Robert Brown first noticed this movement while examining pollen grains suspended in water under a microscope. The kinetic theory gives a nice explanation of the phenomenon. The motion is due to unequal bombardment by the molecules of dispersion medium. With increase in size of particles, the probability of unequal bombardment diminishes and so Brownian movement decreases with increase of particle size. This motion counteracts the force of gravity acting on the colloidal particles and is thus responsible to a certain extent for the stability of colloids. PP 7 I yy f ie \y = yee Ge ay = (a) True solution (b) Colloidal particles {c) Suspensoids Fig. 6.8 Brownian movement {a) Diffusion Since the rates of diffusion decrease very rapidly with increase in the mass of the particles (Graham’s law), colloidal solutions would diffuse much more slowly than ordinary molecular solutions. This property has been made use of in determining molecular weights of colloids. Since the equation to be used for the purpose also has a term for the Avogadro's number (the number of molecules in a gram molecule), the latter can also be determined from it using solutes of known molecular masses. (b) Sedimentation of Suspensoids Although colloidal solutions are found to be fairly stable over considerable periods of time, they do very slowly settle down under the influence of gravity even though some may take years to do so. The rates of setting [or sedimentation, as it is called] can be readily determined because the boundary line between the clear medium and the sol can be easily made out.2. Optical Properties (Tyndall Effect) A beam of light entering a dark room lights up the dust particles floating in air. Similarly, when a strong beam of light is concentrated on a colloidal solution, the path of the beam is illuminated by a bluish light (and becomes visible when observed from the side). This phenomenon is known as Tyndall effect (Fig. 6.9). The scattering of light by the colloidal particle is responsible for this phenomenon. The intensity of scattered light depends upon the difference between refractive indices of dispersed phase and dispersion medium. Since this difference is quite appreciable in case of lyophobic collides, they show well-defined Tyndall effect. This phenomenon has been employed by Zsigmondy as the basic principle for the construction of ultra microscope. A normal microscope cannot be used to locate colloidal particles. It is this effect which is made use of in the ’test box’ in testing the purity of SO for the manufacture of sulphuric acid by the Contact Process. 3. Electrical Properties (Cataphoresis or Electrophoresis) Collidal particles carry an electric charge and, therefore, move towards the oppositely charged electrode when the solution is placed under the influence of an electric field (Fig. 6.10). This migration of colloidal particles under the influence of an electric field is called cataphoresis. The type of charge on a sol particle can be determined by noting the direction of their motion. y— Bright Vessel tyndall cone containing solution Fig. 6.9 Tyndall effect The important applications of cataphoresis are: (a) Removal of dirt particles (b) Electro-deposition of rubber 4. Electro-osmosis A sol is electrically neutral. This reveals that the dispersion medium carries an equal but opposite charge to the dispersed particles. If the dispersed phase is kept stationary by suitable means, it is observed that the dispersion medium itself begins to move under the influence of an electric field. This motion of the dispersion medium under the influence of an electric field is called electro-osmosis. 5. Colour Colour of a sol depends on the wavelength of light scattered by the dispersed phase which, in tum, depends upon the size and nature of the particles. In the case of silver sol, the following data is available.Anode Cathode ‘Coagulated sol particles —f+ = Migrating ‘sol particle Fig. 6.10 Cataphoresis Table 6.4 Colour of silver sols Orange yellow 6x 107° Orange red 9x 1075 Purple 13 x 1075 Violet 15 x 10° Colloidal solutions are stable; this is due to the fact that they are electrically charged. Colloidal particles carry either positive or negative charge. Since all the colloidal particles bear identical charge, they repel each other and do not precipitate easily under the effect of gravity. The electrical charges carried by colloidal particles of various substances dispersed in water, as determined by electrophoresis experiments, are shown in Table 6. Table 6.5 Charge on the colloidal particles 1. Haemoglobin 1. Clay2. Colloidal particles of Fe (OH)3 2. Metallic particles like those of gold, silver and platinum 3. Basic dye stuffs 3. Sulphides of Cu, Pb, As, Sb and Cd 4, Silicic acid, stannic acid and vanadium pentoxide 5. Gum-Arabic and soluble starch 6. Acid dye stuffs 6.5.2 Origin of Charge on Colloidal Particles The electric charge is acquired by sol particles by one or more of the following means: 1. Selective Adsorptions The sol particles have a tendency to adsorb anions or cations from the solution. For example, the colloidal particles of As)S3 can adsorb either As** or S?~ ions. Since during the precipitation of this sol, only sulphide ions from HS are in excess, therefore, on a colloidal particle of AsyS3, the S~ ions get adsorbed and the particles become negatively changed. Similarly, the sol of Fe(OH)3 obtained by the hydrolysis of FeCl is positively charged. In the medium are present Fe(OH) particles, Fe>* and Cl” ions. Fe** ions get adsorbed on the surface of Fe(OH); and particles become positively charged. * h is more nearly related chemically to the colloi isp) tially adsorl y it. The AgCl particles can adsorb CI” ions from a chloride solution and Ag* ions from solution containing Ag* ions. The colloidal particle becomes negatively charged in the first case and positively charged in the second case. *Stannic oxide sol provides an interesting example. If a freshly formed precipitate of stannic oxide is peptized by a small amount of hydrochloric acid, the sol carries a positive charge but if peptized by a small amount of sodium hydroxide, the sol carries a negative charge. In the former case, a small amount of stannic chloride SnCly is formed and the sol is positively charged due to preferential adsorption of Sn** ion. In the latter case, a small amount of sodium stannate, NagSn03, is formed and the sol is negatively charged due to preferential adsorption of gn", The chloride and sodium ions, known as counter ions, are directed towards the liquid phase. 2 Soap molecules dissociate to give ions. The cations pass into solution whereas the anions (CyH2n+1 COO™) aggregate together to form negatively charged big particles called micelles. 3. Friction The charge on the sol particles appears as a result of rubbing of the particles of dispersed phase against those of the dispersion medium. a Protein molecules yield colloidal solutions. Since a protein molecule contains an acidic group - COOH and also a basic group -NHp, it will give a positive colloidal particle in acidic medium and a negative particle in alkaline medium. In Acid: H,N- X- COOH + HCI > H}N-X-COOH + Clr In Alkani:H)N — X— COOH + NaOH > H;N- X COO” + Na* + H;O 6.5.3 Theory of Electrical Double Layer _ The electrical properties of colloids can be explained satisfactorily by postulating the existence of an electrical double layer of opposite charges at the surface of separation between a solid and a liquid, i.e. ata solid-liquid interface, According to modern views, when a solid is in contact with a liquid, a double layer of ions appears at the surface of separation, as shown in Fig. 6.11. One part of the double layer is fixed on the surface of the solid. This is known as the fixed part of the double layer, It consists of either positive ions or negative ions. The second part consists of a diffused or a mobile layer of ions which extends into the liquid phase. This layer consists of ions of both the signs but its net charge is equal and opposite to that on the fixed part of the double layer. Such an arrangement of charges is shown in (Fig. 6.11). In case one, the fixed part of the double layer carries positive charge while in the second case (Fig. 6.11b), the fixed part carries negative charge. It will be seen that in each case, the net charge on the diffuse layer is equal and opposite to that on the fixed layer. For example, in Fig. 6.11a, there are 9 positive charges on the fixed layer and net 9 negative charges (9 positive and 18 negative) on the diffused layer. This theory applies to colloidal systems also. The ions which are preferentially adsorbed by the colloidal particles, are held in the fixed part of the double layer. These ions give the characteristic charge to the colloidal particles. The ions carrying the opposite charge, i.e., the counter ions, are present more in the diffused portion of the double layer giving a net opposite charge to this layer. Zeta potential Zeta potential + + = + = + + + - - + - - = = eo 4 - + + + + = + a = + + = + + = + + + = - on - —— Uu—— Diffuse Fixed Diffuse layer layer layer {b) Fig. 6.11 The electrical double layer. The existence of charges of opposite signs on the fixed and diffuse parts of the double layer leads to the appearance of a difference of potential between the two layers, as shown in Fig. 6.11. This difference of potential between the two layers is known as zeta potential or electrokinetic potential. Thus, this theory explains the charge and hence the stability of the collodial particles. The zeta potential Z is given by the relation C=4nn u ie,where 1) and &; are the viscosity and dielectric constant respectively of the dispersion medium and u is the mobility of the colloidal particles It is a process in which the charge over colloidal particles is neutralised resulting in the precipitation of the colloidal particles. The process is brought about spontaneously by the addition of an electrolyte. For example, when barium chloride solution is added to arsenious sulphide sol, it becomes turbid and after some time, a precipitate of arsenious sulphide separates out. The charge on the colloidal particles gets neutralised. We know that arsenious sulphide is a negative sol. The colloidal particles carry negative charge. The sol is stable because of the mutual repulsion between the various colloidal particles having similar charge. But when barium chloride solution is added, the negative charge on the colloidal particles is neutralised by the + ve charge on the barium ions. Thus, the colloidal particles accumulate to form particles of larger size and coagulation results (Fig. 6.12). If the coagulated substance floats then it is called flocculation. ee 0 O a Oo bs 0% & ©ee0°0 O o | —| & 206 009 & e200 oo 0 & ‘Asscnious sulphide ‘The charge on Coagulated sol. particles: the coloidal sol particles carrying negative particles is charge neutralised on addition of Ba”* Fig. 6.12 Coagulation of arrenious sulphide particles by addition of barium ions. A cloudburst is an extreme amount of precipitation and is associated with the phenomenon of coagulation. Rapid precipitation from clouds is possible due so called Langmuir precipitation process in which large droplets can grow rapidly by coagulating with smaller droplets which fall down slowly. It is not essential that cloudbursts occur only when a cloud clashes with a mountain or whatever. They can occur even when hot water vapour mingles into the cold cloud. Sudden condensation of water vapours takes place when it happens In June 2013, a cloudburst occurred in Kedarnath and Rambara region of uttarakhand in India which killed thousands of people. It left nearly 84000 persons stranded for several days. The resulting flash-floods caused massive loss of life and property.Oppositely charge ions from the electrolyte are used up to effect coagulation. The power of an ion to effect coagulation depends upon its valency. According to Hardy-Schulze rule, higher the valency of an active ion, greater will be its power to coagulate colloidal solution, e.g. for the coagulation of negatively charged arsenious sulphide sol, trivalent cations (Al°*) are much more effective than bivalent (Ba2*) or monovalent (Na*) cations. Similarly, for the coagulation of positively charged ferric hydroxide sols, trivalent anions (PO4%) are more effective than divalent (SO74) or monovalent (CI") anions. Order of the negatively charged ions will be as under: Trivalent anion > Divalent anion > Monovalent anion The minimum concentration of an electrolyte in millimoles that must be added to one litre of a colloidal solution so as to bring about complete coagulation or flocculation is called the flocculation value. Coagulation can also be brought about by mixing two oppositely charged colloidal solutions. For example, by mixing ferric hydroxide sol with arsenious sulphide sol, a mutual coagulation takes place. Example 4 Arrange the following in increasing order offlocculation value for a negative sol. Solution: For a negative sol, greater the charge on the cation, greater is the flocculation value. The charges on the cation in the given electrolytes are as follows: Mg Cly Mg?* 42 Al2 (S04)3 ABt +3 Naz PO, Na* +1 Hence, the flocculation value of the electrolytes will be in the order Alp(SO,4)3 > MgCly > NagPO4 1. Protective Colloids Lyophobic colloids are sensitive and they tend to coagulate in the presence of electrolytes. But they can be stabilised if a small amount of a lyophilic sol like soap, gum, gelatine, etc. is added to them; this is called protective action. Such colloids which prevent the coagulation of other colloids are called protective colloids. It is believed that increase in the stability of the lyophobic colloids is due to the coating of lyophilic colloids on the lyophobic colloids2. Gold Number The protective action of the colloids is measured in terms of gold number. Gold number is defined as the number of milligrams of the protective colloid which just prevents the coagulation of 10 ml of gold solution when 1 ml of a 10% solution of sodium chloride is added to it. Gold number of a few protective colloids are given below: Table 6.6. Gold numbers of some protective colloids Gelatin 0.005 Albumin 0.08 Starch 25 Example 2 Define gold number. The gold numbers of A, B, C, and D are 0.005, 0.05, 0.5 and 5 respectively. Which of these has the greatest protective action? Explain your answer. Solution: A has the greatest protective action as we require the minimum quantity of A to prevent the coagulation of the gold solution when sodium chloride solution is added to it. Example 3 The coagulation of 100 ml of a colloidal solution of gold is completely prevented by addition of 0.25 g of starch to it after adding 1 ml of 10% NaCl solution, Find out the gold number of starch. Solution: As per the definition of gold number, it is the number of milligrams of protective colloid (starch in this case), which prevents the coagulation of 10 ml of gold solution when 1 ml of 10% NaCl solution is added to it. In the present case, 100 ml of colloidal solution required to prevent coagulation = 0.25 g starch 10 ml of colloidal solution required to prevent coagulation = 25 mg starch Hence, gold number of starch = 25 ets ‘Smoke Precipitated & [solide Fig. 6.16 Cottrell smoke precipitator 2. Sewage Disposal The sewage disposal carries dirt particles suspended in water. Separation of these particles from water is normally a difficult process. This difficulty is overcome by making the disposal water come in contact with an electrode of opposite charge in a big tank. Dirt particles are precipitated and separated. They serve as manure. 3. Formation of Deltas A delta is formed at a place where the river enters the sea. Sea water is rich in minerals whereas river water contains colloidal particles of clay. At the point of junction of the two waters, clay is deposited. This clay is fertile and is known as delta (Fig. 6.17).Fig. 6.17 Formation of delta. 4. Chemical Warfare Smoke and mist screens are formed by the explosion of bombs. They are harmful to humans, gas masks which contain colloidal charcoal come to the rescue. They adsorb the toxic smoke, 5. Purification of Drinking Water Ordinary water contains suspended impurities of colloidal size which do not settle down due to their charged nature. On adding a little of potash alum, the positive charge on aluminium ions neutralises the charge on colloidal particles, they settle down and water is cleaned for drinking. 6. Blue Colour of Sky Colour of a substance is the colour of the light transmitted by it. Colloidal particles of dust, etc., scatter only the blue light and absorb the rest of the light. Hence blue light reaches us and the sky appears to be blue (Fig. 6.18). Fig. 6.18 Blue colour of sky (illustration) 7. Photography The photographic film contains a colloidal solution of silver bromide in gelatin. A photographic film can also be obtained on a glass plate by depositing a mixture of silver bromide and gelatin. 8. Arti Kidney Machines (Dialysers) Those machines which work on the principle of separation of colloidal particles from those of electrolytes have saved the lives of thousands ofpeople who suffer from kidney failure. The function of kidney is to separate blood (Colloidal solution) from urea and uric acid (true solution). When the normal kidney stops working, it leads to accumulation of poisonous matter into the blood which causes death. In an artificial kidney machine (dialyser), blood is made to pass through a series of cellophane tubes surrounded by a washing solution in water. The toxic chemicals diffuse into the washing solution. Purified blood is returned to the patient (Fig. 6.19). Artery Bloodte vein Cellophane tube ‘Washing solution Fig. 6.19 Artificial kidney machine (dialyser) 9. Medicines A large number of medicines are being produced in the form of sols these days. Such medicines are more effective as they have greater assimilation and adsorption qualities. It is found that ferric chloride solution checks excessive bleeding from a cut. It coagulates the blood due to its charged nature. Applying Chemisry to Life Chrome-tanning of leather is brought about by the penetration of positively charged hydrated chromic oxide into the leather. The rate of penetration can be increased by electrophoresis (a) Chrome-tanning of leather (c) Rubber plating (b) Smoke sereens Fig. 6.20 Applications of colloids ‘Smoke screens are usually employed to conceal the movement of infantry in areas of exposure to enemy fire. A typical white screen uses titanium dioxide which shows maximum scattering of light and is, therefore, best for obscuring troops and naval vessels. Some colouring agents may be added for producing colour screens. The negatively charged particles of rubber (latex) are made to deposit onto various objects for insulation or decoration by electrophoresis. The article to be rubber plated is made the anode. The rubber particles migrate in an electric field towards the anode and deposited on it.SOLVED PROBLEMS Example 4 Comment on the statement “colloid is not a substance but a state of the substance” Solution: The same substance may exist as a colloid under certain conditions and as a crystalloid under certain other conditions. For example, NaCl in water behaves as a crystalloid while in benzene, it behaves as a colloid. Similarly, dilute soap solution behaves as a crystalloid while concentrated solution behaves as a colloid. It is the size of the particles which decides whether it is a colloid or a crystalloid. Example 5 Why is ferric chloride preferred over potassium chloride in the case of a cut leading to bleeding? Solution: Blood is a positively charged colloid. One molecule of ferric chloride produces three negative chloride ions while one molecule of potassium chloride producers one negative chloride ion. The greater the negative charge, the faster is the coagulation of blood. Example 6 How does soap help in washing clothes? Solution: Soap forms micelles around grease and dust particles. The lyopholic hydrocarbon ends (R) of soap are oriented towards grease droplets while the lyophilic COO™ parts of RCOO™ are oriented towards water. Water washes away the micelles along with the grease and dirt. AgNO: KI «I AgNO 1A) e) Example 7 A colloidal solution of Ag I is prepared by two different methods as shown below: (i) What is the charge of Agl colloidal particles in the two test tubes (A) and (B)? (ii) Give the reason for the origin of charge. Solution: (@ When AgNO3 is added to KI solution, the precipitate 5 of Agl will adsorb I” from the dispersion medium, i.e. KI solution. Agl and KI have I” as the common ion, thus, the colloidal particle of Agl will acquire negative charge. When KI is added to Ag NO3 solution, the precipitate of Agl will adsorb the common ion Ag* from the AgNO3 solution; therefore, Agl will acquire a positive charge (ii) Origin of charge can be explained in terms of adsorption of ions form the dispersion medium and with the help of Helmholtz electrical double layer. Example 8 How will you distinguish between dispersed phase and dispersion medium in an emulsion? Solution: Emulsion can be diluted to any extent on adding the dispersion medium. The dispersedphase forms a separate layer if added in excess. Example 9 How does it become possible to cause artificial rain by spraying silver iodide on the clouds? Solution: Clouds are colloidal in nature and carry a charge. On spraying silver iodide which is an electrolyte, the charge on the colloidal particles is neutralised. Clouds coagulate to form rain. Example 10 A colloid is formed by adding FeCl3 in excess of hot water. What will happen if excess sodium chloride is added to this colloid? Solution: A positively charged colloidal solution of hydrated ferric oxide is formed. On adding sodium chloride, negatively charged chloride ions neutralise the positive charge of the colloidal solution. Coagulation of the sol takes place. Example 11 How does leather gets hardened after tanning? Solution: Animal skin is colloidal in nature and carries positive charge. Tannin is a negatively charged colloidal solution. When leather is soaked in tannin, coagulation of leather takes place and it gets hardened. Example 12 A sol may be prepared by a precipitation reaction. Give one such example. How can we find the nature of electric charge on the sol particles ? Solution: AsyS3 sol may be prepared by precipitation reaction as per the following reaction: As:0, + 3H)S — As) S + 3H,O We can find the nature of charge on the colloidal particles by electrophoresis. The colloidal particles move towards the oppositely charged electrode in an electric field. For example, the colloidal particles of As 03 are negatively charged and move towards the positively charged electrode. Example 13 What happens in the following activities and why? (i) An electrolyte is added to a hydrated ferric oxide sol in water. (ii) A beam of light is passed through a colloidal solution. (iii) An electric current is passed through a colloidal solution. Solution: (i On adding an electrolyte to hydrated ferric oxide sol, precipitation of ferric oxide takes place. This is because the charge on the colloidal particles is neutralised by the addition of the electrolyte. (ii) Scattering of light by the colloidal particles takes place and the path of light becomes visible. This is known as Tyndall effect. (iii) On passing electric current through a colloidal solution, the colloidal particles move towards the oppositely charged electrodes and are accumulated there. This phenomenon is called electrophoresis. Example 14 Explain the following observations: (i) A lyophilic colloid is more stable than lyophobic colloid.(ii) Coagulation takes place when sodium chloride solution is added to a colloidal solution of ferric hydroxide. (iii) The sky appears blue in colour Solution: (W The stability of the lyophobic colloid is only on account of the charge while the stability of the lyophilic colloid is on account of charge as well as solvation of colloidal particles. (ii) Fe (OH)3 is positively charged which is coagulated by negatively charged Cl” present in sodium chloride solution. (iii) Sky appears blue in colour due to scattering of light by colloidal particles like dust, mist, etc. Example 15 What is the dispersed phase and dispersion medium of the following colloidal systems: (Smoke (ii) Milk Solution: Colloidal system Dispersed phase Dispersion medium @ Smoke Solid (carbon) Gas (air) Gi) Milk Liquid (fat) Liquid water SUMMARY 1. Solutions in which the particle of the solute are not visible are called true solutions. Solutions in which the particles of the solute are visible even with the naked eye are called suspensions. Colloidal solutions lie between these two solutions. 2. A colloidal solution is a heterogeneous system consisting of two phases, viz. the dispersed phase and the dispersion medium. 3. Colloids may be classified into different types on the basis of physical state of the dispersed phase and dispersion medium, on the basis of appearance (sols, gels), on the basis of solvent affinity (hydrophilic, hydrophobic) or as dispersion colloid, multimolecular colloid or macromolecular colloid. 4, Micelles are strong electrolytes which give a normal solution at low concentration but show colloidal nature at higher concentration. Cleansing action of soaps can be explained on the basis of micelle formation. 5. Colloids can be prepared by dispersion (mechanical, Bredig’s arc, peptisation) methods condensation (excessive cooling, exchange of solvent methods) and chemical methods. 6. Purification of colloidal solutions is achieved by dialysis. 7. Colloidal solutions show colour, display Tyndall effect, Brownian movement, diffusion and sedimentation. Colloidal solutions also show electrophoresis. 8. Charge on the colloidal particles can be explained on the basis of one or more of the following: friction, selective adsoption, electron capture, dissociation of surface molecules and presence of acidic or basic groups. 9, Electrical double layer: The electrical properties of colloids can be explained satisfactorily by postulating the existence of an electrical double layer of opposite charges at the surface of separation between a solid and a liquid, i.e. at the solid-liquid interface. 10. The process in which the charge over colloidal particles is neutralised in the precipitation of the colloidal particles is called coagulation.11, According to Hardy-Schulze rule, higher the valency of an active ion, greater will be its power to coagulate colloidal solution. 12. The minimum concentration of an electrolyte in millimoles that must be added to one litre of a colloidal solution so as to bring about complete coagulation or flocculation is called the flocculation value. 13. Gold number is defined as the number of milligram of the protective colloid which just prevents the coagulation of 10 ml of gold solution when 1 ml of a 10% solution of sodium chloride is added to it. 14, Colloidal solutions is which the dispersed phase as well as the dispersion medium are liquids are called emulsions. 15. A gel is a colloidal system in which the liquid is the dispersed phase and solid is the dispersion medium. Gels are of two types: elastic gels and non-elastic gels. 16. Size of the colloidal particles can be determined by using ultrafilters, from Brownian movement and from scattering of light. 17. Colloids find applications in purification of drinking water, pollution control, medicines, sewage disposal, photography, formation of deltas, explaining the blue colour of sky, chemical warfare and dialysers. KEY EQUATIONS + Size of particles by Brownian movement RE iy 2 N, b= A? = thy mip-p? m 3 ny and ng are the number of particles at two depths hy and hp. p and p’ are the densities of the particle and liquid medium. r is the radius of the particle. + Size of particles by light scattering method V3 sens] nis the number of particles per unit volume. m/p is the volume of the colloidal phase (volume = mass/density) mip = Sa? xathy Ane 9") or-[ ad EXERCISES Based on Different University Papers Objective Questions (A) Fill in the Blanks 1. Coloured glass is an example of colloidal solution of in 2. A small quantity of an electrolyte can cause precipitation of colloid. ES action of soaps can be explained on the basis of micelle formation.4, The process of removing the dissolved electrolytes from the sol by means of a membrane is called . 5. Oil-in-water emulsions have oil in the phase and water in medium. 6. Particle size in a colloidal solution is 7. What is a colloial system called if the dispersion medium is benzene? 8. Electrolytes which give a normal solution at low concentration but show colloidal nature at higher concentration are called 9. Bredig’s arc method is used for the preparation of colloided solution of 10. The electrical properties of colloids can be explained satisfactorily by postulating the existence of electrical (B) Multiple Choice Questions 1. The sky looks blue due to (@) dispersion effect (b) reflection (©) transmission (@) scattering 2. Which method is used to destroy a sol? (a) Condensation (b) Dialysis (©) Diffusion (d) Addition of electrolyte 3. Which substance gives positive sol? (a) Gold (b) Starch (©) Ferric hydroxide (d) Asp Sy 4, Which of the following is least effective in causing flocculating of ferric hydroxide sol? (@) Kg Fe (CN)g (b) Kz CrO4 (©) KBr (@) KyS04 5, Bleeding is stopped by applying FeClg because: (a) blood starts flowing in opposite direction (b) FeCly seals the blood vessels (©) blood gets coagulated (d) blood vessel is sealed 6. Who gave the rule ’’Greater the valency, higher is the coagulating power”? (a) Hardy-Schulze(b) Grahm (©) Faraday (@) Lewis 7. Tyndall phenomenon is shown by (@) dilute solutions (b) colloidal solutions (©) suspension (@) true solution. 8. Migration of colloidal particles under the influence of electric field is called: (@) Browian movement (b) cataphoresis (©) dialysis 9. The potential difference between fixed charged layer and diffused layer with opposite charge is called (@) colloidal potential (b) electrode potential (©) zeta potential (@) none 10. An emulsifier is a substance which (a) helps dispersion of liquid in liquid (b) stabilises the emulsion (©) purifies the emulsion (@) coagulates the emulsion 11. Kinectic activity of colloidal particles in dispersion medium is called (@) electro-osmosis () Brownian movement (©) cataphoresis 12. Gold number is measure of (a) amount of gold present in colloidal solution (b) amount of gold required to break the colloid (© amount of gold required to protect the colloidal, (@) none 13. Which of the following is emulsifier? (@) Soaps (b) Detergents (©) Both (@ None 14, Agl is used for producing artificial rain because Agl (@) has crystal structure similar to ice(b) is easy to spray at high altitudes (©) is easy to synthesise (@) is soluble in water 15, Bredig’s method is used for preparing (2) metal sol (b) organic compound (©) eutectic mixture (@) none 16. Which one of the following is +ve sol? (@) Blood (b) Clay soil (©) Smoke (@) Gelatin in acidic solution 17. The emulsifying agent in milk is (@) lactic acid (b) fat (©) lactose (@) casein 18. The gold number of sols A, B, C and D are 0.04, 0.002, 10 and 25 respectively. The protective powers are in the order: (@A>B>C>D (b)B>A>C>D ()D>C>B>A (@)C>A>B>D 19. The minimum concentration of an electrolyte required to cause coagulation of a sol is called: @) flocculation (b) gold number (©) Coagulation number (@) none 20. Stability of lyophilic sol is due to (@) Brownian motion of only (b) electric charge only (©) both Brownian motion and charge (@) particle size Answers (A) Fill in the Blanks 1. Solid, solid2. lyophilic 3. cleansing 4. dialysis 5. dispersed, dispersion 6. 1-100 nm 7. benzosol 8. gels 9. metals 10. double layer (B) Multiple-Choice Question 1.@ 2.(a) 3.0 40 5.0 6.@ 7.(b) 8.(b) 9.0 10. (b) 11.) 12.(@ 13.(2) 14. (@) 15. (a) 16. (©) 17.@ 18. (b) 19. (a) 20.) GENERAL QUESTIONS 1. (a) What is meant by peptization? Give a suitable example. (b) Describe a method for purifying colloidal solutions. (©) Discuss the function of a protective colloid. 2. What are emulsions and gels? What distinguishes elastic from non-elastic gels? 3. (a) What are lyophillic colloids? Why are they called reversible colloids?(b) Why is MgCly a better coagulant than KCI for As)S3 sol? 4, What are colloids? How are they classified? How would you prepare the colloidal solution of (@) gold (b) arsenious sulphide and (©) sulphur? 5. Discuss the origin of charge on colloidal particles. What is meant by electrical double layers? What is meant by zeta potential? 6. What is electrophoresis? How does this phenomenon provide information about the sign of charge on particles. 7. State different methods of preparation of colloidal dispersions. Describe Bredig’s arc method in detail. 8. (a) What is a colloid? Discuss the essential difference between lyophillic and lyophobic colloids. (b) Write short notes on (i) Tyndall effect and Brownian movement (ii) Electrophoresis and its applications 9. Give three points of difference between lyophobic and lyophillic colloids. 10. (a) What is the size range of colloidal particles? Distinguish between a molecular solution and a colloidal dispersion. (b) Describe one method for the preparation of colloidal solutions. 11. What are emulsions? How are they classified? How are they prepared? 12. Explain why: (a) Alum is used in town water supply (b) Alum is used in shaving (©) Tyndall concentrated is formed when a beam of light is concentrated on a colloidal solution 13. (a) What are emulsions and what is emulsifying agent? (b) What are micelles? Give examples. 14, Write a short note on origin of charge on colloidal particles. 15. Define gold number. The gold numbers of A, B, C and D are 0.005, 0.05, 0.5 and 5 respectively. Which of these has the greatest protective action? Explain your answer. 16. (a) Explain the stability of colloids. (b) Write the difference between gels and emulsions. (© Explain the Hardy-Schulze rule for coagulation. 17. (a) What is a protective colloid? How does a hydrophilic colloid stablise a hydrophobic one? Give an account of gold number in this context. (b) What do you understand by the coagulation value of an electrolyte? (©) What are gels? Give examples.