COLLOIDS

Thomas Graham from investigations on diffusion of various substances in a liquid medium classified substances as: Crystalloids: Which diffuse readily in solution and whose solution can readily pass through membranes. Eg.: Sugar, salts, acids, bases and other substances. Colloids: Which diffuse very slowly in solution and whose solution cannot pass through membranes. Eg.: Starch, glue, albumin, gelatin etc.

In recent years Grahams view about classification of substances has undergone a great change. In fact it is now well known that one and the same substance may show colloidal behaviour at one time and crystalloidal behaviour at another time depending upon the prevailing conditions. For e.g., Soaps show colloidal character in water but crystalloidal character in alcohol. NaCl is a crystalloid in water and colloid in benzene Metals like Cu, Ag, Au and Pb can also be

Colloidal State:
Definition: A substance is said to be in the colloidal state, when it is dispersed in another medium in the form of very small particles (diameters lying within 10 2000 range)

Types of Colloidal Systems:

A colloidal system is thus a two-phase system consisting of a dispersion medium in which extremely minute particles, lying within the colloidal range of a substance termed as dispersed phase are suspended.

Disperse Dispersion Name of d phase medium the colloid Solid Solid Solid Liquid Liquid Liquid Gas Gas Solid Liquid Gas Solid Liquid Gas Solid Liquid Solid sol Sol Aerosol Gel

Examples Coloured glass, gems, alloys Paints, inks, white of eggs, mud Smoke, dust Curds, pudding, cheese, jellies

Emulsion Milk, cream, butter, oil in water Liquid aerosol Clouds, mist, fog

Solid foam Cake, bread, lava, pumice stone Foam Soap lather, froth on beer, whipped cream

When dispersion medium is a gas, the colloidal system is called Aerosol. The systems with solids as dispersed phase and a liquid as dispersion medium are known as Sols.

Classification Of Sols
Sols are frequently classified, on the basis of their solvent affinity, into two classes: Lyophilic: Those in which the dispersion medium possesses great affinity for the dispersed phase. Eg: Starch, gelatin, glue and agar sols in water. Lyophobic: Those in which there is no apparent affinity interaction between the dispersion medium and the dispersed phase. Eg.: Arsenic sulphide, ferric hydroxide.

Property
Preparation

Lyophobic Sols
Difficult to prepare. Special methods are used. Addition of stabilizers is essential for their stability Irreversible, once precipitated does not easily pass into colloidal state Follows the law of mixtures

Lyophilic Sols
Easy to prepare. Only contact with the dispersion medium is needed to stabilize them Reversible. Once precipitated easily pass back into colloidal state by contact with dispersion medium
Physical properties do not follow the law of mixtures

Nature

Density and refractive index Colligative properties

High osmotic pressure, Relatively high osmotic small depression in pressure, depression in freezing point, less freezing point, elevation in boiling point and less lowering of vapour pressure

Property

Lyophobic Sols
that of the medium.

Lyophilic Sols
that of the medium. Viscosity is much higher than that of the medium.

Surface Tension Is usually the same as Is generally lower than Viscosity Visibility
Viscosity is about the same as that of the medium

The particles though The particles cannot be invisible, can be readily readily detected even detected by ultra under ultra microscope. microscope The particles are not hydrated to any large extent. Particles are extensively hydrated.

Hydration Action Of Electrolytes.

Addition of small qty. of Much larger qty. are electrolytes can cause needed to cause precipitation. precipitation.

Preparation of Sols
The different methods used for the preparation of colloidal solutions are broadly classified under two types. Dispersion methods:In these methods larger particles are broken down to a colloidal size in the dispersing phase and the resulting solutions are stabilized by adding a suitable stabilizer.

By Bredigs Arc Method:This method is used for preparing colloidal solutions of metals like Au, Ag. etc. An arc is struck between two electrodes of a metal like Pt, Au, Ag or Cu in water containing traces of alkali. The metal passes into colloidal solution of reasonable concentration. It is believed that by the heat of the spark, the metal first changes into vapour which then condenses in water to give aggregates of colloidal range. The alkali acts as a stabilizer.

By Peptisation The peptisation is due to the preferential adsorption of one of the ions of the electrolyte by the particles of the materials. As a result of the preferential adsorption of the ion which is more closely related chemically to the precipitate, the particles acquire a positive or a negative charge depending upon the charge on the ion adsorbed. Because of the presence of the same type of charge, the particles of the precipitate are pushed apart. The precipitate thus gets dispersed resulting in the formation of a stable sol.

Condensation methods: These methods involve the aggregation of particles into colloidal range in a medium in which the particles are already present as small ions, atoms or molecules. The conditions are adjusted in such a way that colloids are formed and actual precipitation is avoided. These can be broadly classified as (i) Physical methods (ii) Chemical methods

Physical methods : (a) condensation of vapours under a liquid phase: sols of certain elements can be obtained by passing their vapours into a cooled dispersion medium. e.g., Hg or S sol is obtained by boiling Hg or S and passing the vapours into cold water containing a stabilizing agent. (b) exchange of solvent: when a substance in a solution is shaken with another solvent in which it is less soluble, it changes into colloidal form. e.g., phenolphthalein in alcohol on shaking with water gives a colloidal solution

(c) Excessive cooling: Colloidal ice is obtained by chilling a mixture of a water and the organic solvent as chloroform, pentane or ether. (d) Cathodic reduction: Certain sols have been prepared by the rapid electrolysis of their solutions. e.g., sol of Pb is obtained at the cathode by electrolyzing Pb salts. Similarly, Pt black for electrodes is prepared by electrolyzing Pt(IV) chloride on a gold or Pt electrode.

(e) Controlled condensation: Colloidal sols of certain insoluble substances are prepared by their precipitation in the presence of peptiser or protective colloids. A sol of prussian blue may be prepared by this method. Chemical methods: 1. Oxidation: Sols of some non-metals are obtained by oxidation. e.g., S is obtained in colloidal form by passing H2S gas through bromine water or dil. HNO3. H2S + Br2 HBr + S (colloidal)

(b) By Reduction Colloidal solution of a number of metals such as Ag, Au are obtained by reducing the dilute aq. Solutions of their salts by reducing such as HCHO, H2O2, tannic acid, phosphorus, hydrazine, etc. e.g., Gold sol may be obtained by boiling 3 - 4 ml of 0.2 N K2CO3 solution and 1 ml of 1% AuCl3 solution in about 150 - 200 ml of distilled water, followed by gradual addition of 1 - 3 ml 0f 0.3% HCHO solution with continued stirring.
2AuCl3+ 3HCHO + 3H2O 2Au + 3HCOOH + 6HCl

ex. Silver sol is obtained by reducing a solution of AgNO containing alkaline dextrin as stabilizer

(c) By Double Decomposition: sols of insoluble salts can be prepared by this method. If the solution containing the component ions of an insoluble substance are mixed, a precipitate will result. If the substance has low solubility, the precipitate will be colloidal. (i) A sol of arsenic sulphide is obtained by passing H2S through a cold solution of arsenous oxide in water. As2O3 + 3H2S As2S3 + 3H2O (ii) Silicic acid sol is obtained by mixing dilute solutions of sodium silicate with dil. HCl. Na2SiO3 + 2HCl H2SiO3 + 2NaCl

(d) Hydrolysis Colloidal sols of heavy metals are obtained by the hydrolysis of the solutions of their salts. When a small amount of ferric chloride is added to boiling water, a red-brown sol of ferric hydroxide is obtained FeCl3 + 3H2O Fe(OH)3 + 3HCl

Purification Of Sols
The presence of a small amount of an electrolyte is necessary for the stability of a sol. But the presence of large amounts of electrolytes causes the precipitation of the sols. It is therefore necessary to eliminate the excess amount of electrolytes. The purification of sols is generally done by the following methods.

Dialysis
Principle:- Porous membranes such ass parchment paper, cellophane paper are permeable to molecules of solvent and not to colloidal particles. Whenever such a membrane separates colloids from distilled water, it permits the passage of only electrolyte through it but not the colloidal particles. The method of purification of colloids by dialysis is based on this principle.

Procedure:- The sol to be purified is enclosed in a bag made of the material chosen for dialysis membrane. The bag is kept immersed in distilled water. On standing, the ions present in the solution slowly pass through the membrane into distilled water, leaving behind pure sol. The process is quite slow, requiring days and occasionally weeks for its completion. It can be made faster by applying an electric field (electro dialysis).

Electrodialysis
The sol is placed in the middle compartment between two dialyzing membranes, while pure water is circulated into the outer compartments of the dialyser. There are two electrodes fixed one in each outer compartments. On applying a suitable e. m.f, the ions of the electrolyte diffuse through the membrane and migrate towards the oppositely charged electrodes, leaving behind the colloidal particles in the middle compartment.

It is usually not carried out to a point, where all the electrolytes are removed, since a small amount of electrolytes are required for the stability of sols.

Ultra filtration
The pores in the ultra filters (treated filter papers - i.e., pores of ordinary filter paper made smaller by soaking in a solution of gelatin and subsequently hardening them by soaking in HCHO) will be large enough to permit the passage of ions or molecules in true solutions, but will be small enough to withhold the colloidal particles. Since ulrafiltration proceeds very slowly, pressure is applied to speed up the process.

Properties Of Colloidal Systems

Optical properties:- It was observed by Tyndall that when a beam of light passed through a true solution it cannot be seen unless the eye is placed directly in its path. However when the same beam of light is passed through a colloidal dispersion, it becomes visible as a bright streak. This phenomena is known as the Tyndall effect and the illuminated path is known as Tyndall Cone.

This phenomenon is due to the scattering of light from the surface of colloidal particles. In a true solution there are no particles of sufficiently large diameter to scatter light and hence the beam is invisible. The visibility of dust particles in a semi-darkened room when a sun beam enters, or when a light is thrown from a projector are familiar examples of Tyndall effect. The dust particles are large enough to scatter light and thus render the path of light visible.

The intensity of the scattered light depends on the difference between the R.I. of the dispersed phase and the dispersion medium. In lyophobic colloids this difference is appreciable and hence the Tyndall effect is quite well defined. But in lyophilic colloids, the particles are largely solvated and this lowers the differences in the R. I. of the two phases and hence the Tyndall effect is much weaker.

The Tyndall effect has been used in devising the ultra microscope.

A strong beam of light from an arc lamp or any other is condensed by a system of lenses and passed through the colloidal solution and the scattered beam is viewed through a microscope placed at right angles to the beam. In this way, the colloidal particles which are too small to be seen under an ordinary microscope can be detected as spots of light moving irregularly. It may be emphasized that we do not see the actual particles but only the light scattered by them. Our eye pictures various spots of light as round or spherical particles.

Brownian Movement:- Robert Brown observed that pollen grains in aqueous suspensions were in constant motion. Later on when ultra microscope was invented, it was found that particles of lyophobic sols were also in a state of ceaseless erratic and random motion similar to pollen grains. This KINETIC activity of particles suspended in a liquid is called Brownian movement.

This is due to the bombardment of colloidal particles by molecules of dispersion medium which are in constant motion like molecules in a gas. As a result, the colloidal particles acquire almost the same energy as possessed by the molecules of the dispersion medium. But, since the colloidal particles are considerably heavier than molecules of the dispersion medium their movement is considerably slower than that of the molecules of the medium.

The Brownian movement is not observed in ordinary suspensions because the mass of each particle in this case is so large that the bombardment by molecules of the dispersion medium produces little effect on them. Brownian movement offers a visible proof of the random kinetic motion of molecules in a liquid.

Electrical Properties
The most important property of colloidal dispersion is that the particles carry an electric charge. All the particles in a given colloidal system carry the same charge and the dispersion medium has an opposite and equal charge, the system as a whole being electrically neutral.

The 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. The theory was first proposed by Helmholtz and later on modified by Guoy, Stern & others.

When a solid is in contact with a liquid, a double layer of ions appear at the surface of separation, as shown in the fig.

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 diffuse 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 the fig.

The ions which are preferentially adsorbed by the colloidal particles, are held in the fixed part of the double layer which give the characteristic charge to the colloidal particles. The ions carrying the opposite charge are present more in the diffuse portion of the double layer, giving a net opposite charge to this 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. This difference of potential between the two layers is known as Zeta potential or Electro kinetic potential.

It is obvious that when an electric field is applied, the particles and the liquid will migrate in opposite directions. When expts. are so arranged that the medium can move but not the particles, we come across the phenomenon of electro-osmosis. If on the other hand the expts. are designed in such a way that the particles can move, but not the medium, we have the phenomenon of electrophoresis.

ELECTRO-OSMOSIS

The colloidal system is placed in the central compartment A which is separated from the compartments B and C filled with water, by the dialysing membranes M and M1. The water in the compartments B and C also extends to the side tubes T and T1. The membranes prevent the movement of the colloidal particles. Therefore when a p.d. is applied across the electrodes held close to the membranes in the compartments B and C, as shown, the water begins to move.

If the particles carry positive charge the water will carry negative charge therefore it would start moving towards the anode and hence the level of water in the side tube T would be seen to rise. If on the other hand, the particles carry negative charge, the water which now carries positive charge, will start moving towards the cathode and the level of water in the side tube T1 would start rising.

This apparatus consists of a U tube fitted with a stopcock for drainage and a funnel shaped filling tube with stopcock attached to the back of the U tube. A solution of some suitable electrolyte of lower density than the sol is first placed in the tube and the sol next introduced through the funnel so as to displace the electrolyte upward and produce sharp boundaries in the two arms. Electrodes are then inserted, and connected to a source of potential, such as a high voltage battery.

When the colloidal particles are negatively charged, it is observed that the level of the sol falls gradually on the negative side and rises simultaneously on the positive side. Reverse process will take place if colloidal particles are positively charged. By noting whether colloid particles migrate in an electric field and the direction of migration, it is readily possible to determine whether the particles in the given colloid are charged and what is the sign of the charge.

Coagulation Of Colloids
The stability of colloid state rests on the existence of electrical charge on the particles. This charge, on account of electrical repulsion, prevents the particles from approaching sufficiently close to one another and to coalesce. However, when the charge is neutralized or lowered to a certain critical value, the particles approach close enough to coalesce and form bigger aggregates which lie outside the colloidal range.

This phenomenon of change of colloidal state to suspended state is known as coagulation or flocculation of colloidal solutions. Coagulation of colloids is generally brought about by any one of the following treatments:(1) By the mutual action of sols:When two sols carrying opposite charges are mixed together in suitable proportions, mutual precipitation occurs.

(2) By persistent dialysis:Traces of electrolytes are invariably associated with colloidal systems and that this is essential for their stability. If the sols are subjected to prolonged dialysis, these traces of electrolytes also pass out through the dialyzer and the colloids become unstable. (3) By the action of electrolytes:The presence of larger amounts of electrolytes causes their coagulation. The reason is that colloidal particles take up ions carrying charge opposite to that present on themselves. This results in partial or complete neutralization of the charge on the particles leading to their coagulation or flocculation. The ion carrying the opposite charge is called the

Hardy Schulze Rule:The greater the valency of the flocculating ion added, the greater is its power to cause precipitation. Thus, in the coagulation of negatively charged Arsenic Sulphide sol the flocculating power decreases in the order Al3+ > Ba2+ > Na+ and in the coagulation of the positively charged ferric hydroxide sol, the flocculating power decreases in the order [Fe(CN)6]4- > [PO4]3- > [SO4]2- > Cl-. However the rule is only approximate.

The minimum concentration of an electrolyte required to cause coagulation or flocculation of a sol is called its flocculation value. This is usually expressed in terms of milli-moles per Litre. Polyvalent ions are more effective in causing coagulation since much smaller concentrations are needed for the purpose.

Arsenic Sulphide Sol Electrolyte Cation valenc y Flocc. Value (m. moles/Ltr.)

Ferric Hydroxide Sol Electrolyte Cation valenc y Flocc. Value (m. moles/Ltr.)

NaCl HCl MgSO4 CaCl2 AlCl3

1 1 2 2 3

52 30 0.72 0.69 0.093

HCl KBrO3 K2CrO4 K2SO4

K3[Fe(CN)6]

1 1 2 2 3

132 31 0.315 0.210 0.096

Protective Colloids
Lyophilic colloids are much more stable than lyophobic colloids. The reason is that they are extensively hydrated. It is believed that the colloidal particles are covered by a sheath of the liquid in which they are dispersed. This sheath acts as a barrier and prevents them from coming together and forming larger aggregates. Lyophilic colloids also posses the property of protecting lyophobic colloids from precipitation by the action of electrolytes.

When a lyophilic sol is added to a lyophobic sol, it is believed that lyophilic particles form envelopes around the lyophobic particles and thus protect the latter from the action of electrolytes. Lyophilic colloids used for such purposes are called Protective Colloids. Thus, if a little gelatin (lyophilic colloid) is added to a gold sol (lyophobic sol), the latter is protected and a much higher concentration of NaCl solution is required now to cause its coagulation.

The lyophilic colloids differ in their protective powers. Zsigmondy introduced the term gold number to measure the protective powers of different colloids. The smaller is the gold number of a lyophilic colloid, the greater is its protective power.

Gold Number
The weight in milligrams of a protective colloid which prevents the coagulation of 10 ml of a given gold sol on adding 1 ml of a 10 % solution of sodium chloride. Different lyophilic sols have different gold numbers. Smaller the gold number of the protective colloid, greater is the protective power of the lyophilic sol. The gold numbers of sols is listed below. Gelatin 0.01 Haemoglobin 0.03 to 0.07 Albumin 0.1 to 0.2 Starch 10 to 15 Dextrin 125 to 150

Applications of Colloids
1. In everyday life:Colloids play an important role in our daily life. Protoplasm and blood are all colloidal in character. The food (milk, butter, cheese etc.) that we eat, the clothes and shoes that we wear are based on colloids. In fact, there is hardly any product that we use in everyday life, which does not depend on colloids.

2. In Medicine:Because of their easy assimilation and adsorption,the colloidal medicines are found to be much more effective. Eg. (i) argyrol & protargrol are colloidal sols of Ag and used as eye lotions. (ii) Colloidal gold, calcium and iron are used as oral medicines as well as injectibles for raising the vitality of human systems.

3. In Industry:1. Electrophoresis has been utilized in the following. 2. Smoke precipitation:- In big industrial cities, smoke is a nuisance, as it pollutes the atmosphere as well as is injurious to health. Smoke is a negatively charged colloidal solution consisting of carbon particles dispersed in air. For the precipitation of carbon particles of the smoke, it is passed through a chamber, provided with a highly positively charged metallic knob. The negatively charged smoke particles, on coming in contact with the knob, lose their charge and settle down on the floor of the chamber; while hot gases pass out to the chimney. The precipitated carbon is used as a by-product for making paints, indian ink

(ii) Removal of dirt from sewage (iii) Purification of water (iv) Electroplating of rubber (v) In leather tanning.