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“The phenomenon of the precipitation of a colloidal solution by the addition of the excess of an electrolyte is called coagulation or flocculation.”          The coagulation of the lyophobic sols can be carried out by following methods. (1) By electrophoresis : In electrophoresis the colloidal particles move towards oppositely charged electrode. When these come in contact with the electrode for long these are discharged and precipitated. (2) By mixing two oppositely charged sols : When oppositely charged sols are mixed in almost equal proportions, their charges are neutralised. Both sols may be partially or completely precipitated as the mixing of ferric hydroxide (+ve sol) and arsenious sulphide (–ve sol) bring them in precipitated form. This type of coagulation is called mutual coagulation or meteral coagulation. (3) By boiling : When a sol is boiled, the adsorbed layer is disturbed due to increased collisions with the molecules of dispersion medium. This reduces the charge on the particles and ultimately they settle down to form a precipitate. (4) By persistent dialysis : On prolonged dialysis, the traces of the electrolyte present in the sol are removed almost completely and the colloids become unstable.            (5) By addition of electrolytes : The particles of the dispersed phase i.e., colloids bear some charge. When an electrolyte is added to sol, the colloidal particles take up ions carrying opposite charge from the electrolyte. As a result, their charge gets neutralised and this causes the uncharged, particles to come closer and to get coagulated or precipitated. For example, if \[BaC{{l}_{2}}\]solution is added to \[A{{s}_{2}}{{S}_{3}}\] sol the \[B{{a}^{2+}}\]ions are attracted by the  negatively charged sol particles and their charge gets neutralised. This lead to coagulation.                (6) Hardy schulze rule : The coagulation capacity of different electrolytes is different. It depends upon the valency of the active ion are called flocculating ion, which is the ion carrying charge opposite to the charge on the colloidal particles. “According to Hardy Schulze rule, greater the valency of the active ion or flocculating ion, greater will be its coagulating power” thus, Hardy Schulze law state:       (i) The ions carrying the charge opposite to that of sol particles are effective in causing coagulation of the sol. (ii) Coagulating power of an electrolyte is directly proportional to the valency of the active ions (ions causing coagulation). For example to coagulate negative sol of \[A{{s}_{2}}{{S}_{3}}\], the coagulation power of different cations has been found to decrease in the order as,  \[A{{l}^{3+}}>M{{g}^{2+}}>N{{a}^{+}}\] Similarly, to coagulate a positive sol such as \[Fe{{(OH)}_{3}}\], the coagulating power of different anions has been found to decrease in the order :   \[{{[Fe{{(CN)}_{6}}]}^{4-}}>PO_{4}^{3-}>SO_{4}^{2-}>C{{l}^{-}}\] (7) Coagulation or flocculation value “The minimum concentration of an electrolyte which is required to cause the coagulation or flocculation of a sol is known as flocculation value.” or “The number of millimoles of an electrolyte required to bring about the coagulation of one litre of a colloidal solution is called its flocculation value.” Coagulation value or flocculating value \[\propto \frac{1}{\text{Coagulating power}}\] (8) Coagulation of lyophilic sols (i) more...

Sols are thermodynamically unstable and the dispersed phase (colloidal particles) tend to separate out on long standing due to the Vander Waal's attractive forces. However sols tend to exhibit some stability due to (1) Stronger repulsive forces between the similarly charged particles (2) Particle-solvent interactions : Due to strong particle-solvent (dispersion medium) interactions, the colloidal particles get strongly solvated.

  The origin of the charge on the sol particles in most cases is due to the preferential adsorption of either positive or negative ions on their surface. The sol particles acquire electrical charge in any one or more of the following ways. (1) Due to the dissociation of the surface molecules : Some colloidal particles develope electrical charge due to the dissociation / ionisation of the surface molecules. The charge on the colloidal particles is balanced by the oppositely charged ions in the sol. For example,  an aqueous solution of soap (sodium palmitate) which dissociates into ions as, \[\underset{\text{Sodium palmitate}}{\mathop{{{C}_{15}}{{H}_{31}}COONa}}\,\]\[{{C}_{15}}{{H}_{31}}CO{{O}^{-}}+N{{a}^{+}}\] The cations (Na+) pass into the solution while the anions \[({{C}_{15}}{{H}_{31}}CO{{O}^{-}})\]have a tendency to form aggregates due to weak attractive forces present in the hydrocarbon chains. (2) Due to frictional electrification (i) It is believed that the frictional electrification due to the rubbing of the dispersed phase particles with that of dispersion medium results in some charge on the colloidal particles. (ii) The dispersion medium must also get some charge, because of the friction. Since it does not carry any charge, the theory does not seem to be correct. (3) Due to selective adsorption of ions (i) The particles constituting the dispersed phase adsorb only those ions preferentially which are common with their own lattice ions.     (ii) For example, when a small quantity of silver nitrate \[(AgN{{O}_{3}})\]solution is added to a large quantity of potassium iodide \[(KI)\]solution, the colloidal particles of silver iodide adsorb \[{{I}^{-}}\] from the solution to become negatively charged, (at this stage \[KI\]is in excess, and \[{{I}^{-}}\]being common to \[AgI\]) \[\underset{(Colloidal\,\,particle)}{\mathop{AgI}}\,+\underset{(In\,\,excess\,\,in\,\,the\,\,medium)}{\mathop{{{I}^{-}}}}\,\xrightarrow{{}}\underset{\begin{smallmatrix} (Colloidal\,\,particle \\ becomes\,\,positively \\ \,\,\,\,\,\,\,\,\,\,\,\,\,\,charged) \end{smallmatrix}}{\mathop{(AgI){{I}^{-}}}}\,\] But, when a small quantity of potassium iodide \[(KI)\] solution is added to a large quantity of silver nitrate solution \[(AgN{{O}_{3}})\]; the colloidal silver iodide particles adsorb \[A{{g}^{+}}\] from the solution to become positively charged, (at this stage \[AgN{{O}_{3}}\]is in excess and \[A{{g}^{+}}\]is common to \[AgI\]),       \[\underset{(Colloidal\,\,particle)}{\mathop{AgI}}\,+\underset{(In\,\,excess\,\,in\,\,the\,\,medium)}{\mathop{A{{g}^{+}}}}\,\xrightarrow{{}}\underset{\begin{smallmatrix} (Colloidal\,\,particle \\ becomes\,\,positively \\  \,\,\,\,\,\,\,\,\,\,\,\,\,\,charged) \end{smallmatrix}}{\mathop{(AgI)A{{g}^{+}}}}\,\]  (iii) Depending upon the nature of charge on the particles of the dispersed phase, the colloidal solutions are classified into positively charged and negatively charged colloids. Some typical examples are as follows
(a) Negatively charged      colloids (b) Positively charged          colloids
·  Metal sulphides :      \[A{{s}_{2}}{{S}_{3\,}},CdS\] · Metal dispersions : \[Ag,\,Au,\,Pt\] · Acid dyes : Eosin, congo red · Sols of starch, gums, gold,    gelatin etc. · Metal hydroxides :   \[Al{{(OH)}_{3}},\,\] \[Fe{{(OH)}_{3}}\] · Metal oxide : \[Ti{{O}_{2}}\] · Basic dyes : Methylene blue · Haemoglobin · Sulphur sol

The main characteristic properties of colloidal solutions are as follows. (1) Physical properties (i) Heterogeneous nature : Colloidal sols are heterogeneous in nature. They consists of two phases; the dispersed phase and the dispersion medium. (ii) Stable nature : The colloidal solutions are quite stable. Their particles are in a state of motion and do not settle down at the bottom of the container. (iii) Filterability : Colloidal particles are readily passed through the ordinary filter papers. However they can be retained by special filters known as ultrafilters (parchment paper).                          (2) Colligative properties (i) Due to formation of associated molecules, observed values of colligative properties like relative decrease in vapour pressure, elevation in boiling point, depression in freezing point, osmotic pressure are smaller than expected.     (ii) For a given colloidal sol the number of particles will be very small as compared to the true solution. (3) Mechanical properties (i) Brownian movement (a) Robert Brown, a botanist discovered in 1827 that the pollen grains suspended in water do not remain at rest but move about continuously and randomly in all directions. (b) Later on, it was observed that the colloidal particles are moving at random in a zig – zag motion. This type of motion is called Brownian movement. (c) The molecules of the dispersion medium are constantly colloiding with the particles of the dispersed phase. It was stated by Wiener in 1863 that the impacts of the dispersion medium particles are unequal, thus causing a zig-zag motion of the dispersed phase particles. (d) The Brownian movement explains the force of gravity acting on colloidal particles. This helps in providing stability to colloidal sols by not allowing them to settle down. (ii) Diffusion : The sol particles diffuse from higher concentration to lower concentration region. However, due to bigger size, they diffuse at a lesser speed. (iii) Sedimentation : The colloidal particles settle down under the influence of gravity at a very slow rate. This phenomenon is used for determining the molecular mass of the macromolecules. (4) Optical properties : Tyandall effect (i) When light passes through a sol, its path becomes visible because of scattering of light by particles. It is called Tyndall effect. This phenomenon was studied for the first time by Tyndall. The illuminated path of the beam is called Tyndall cone. (ii) The intensity of the scattered light depends on the difference between the refractive indices of the dispersed phase and the dispersion medium. (iii) In lyophobic colloids, the difference is appreciable and, therefore, the Tyndall effect is well - defined. But in lyophilic sols, the difference is very small and the Tyndall effect is very weak. (iv) The Tyndall effect confirms the heterogeneous nature of the colloidal solution. (v) The Tyndall effect has also been observed by an instrument called ultra – microscope. Some example of Tyndall effect are as follows (a) Tail of comets is seen as a Tyndall cone due to the scattering of light by the tiny solid particles left by the more...

The following methods are commonly used for the purification of colloidal solutions. (1) Dialysis (i) The process of separating the particles of colloid from those of crystalloid, by means of diffusion through a suitable membrane is called dialysis. (ii) It’s principle is based upon the fact that colloidal particles can not pass through a parchment or cellophane membrane while the ions of the electrolyte can pass through it. (iii) The impurities slowly diffused out of the bag leaving behind pure colloidal solution (iv) The distilled water is changed frequently to avoid accumulation of the crystalloids otherwise they may start diffusing back into the bag. (v) Dialysis can be used for removing \[HCl\] from the ferric hydroxide sol. (2) Electrodialysis (i) The ordinary process of dialysis is slow. (ii) To increase the process of purification, the dialysis is carried out by applying electric field. This process is called electrodialysis. (iii) The important application of electrodialysis process in the artificial kidney machine used for the purification of blood of the patients whose kidneys have failed to work. The artificial kidney machine works on the principle of dialysis. (3) Ultra – filtration   (i) Sol particles directly pass through ordinary filter paper because their pores are larger (more than \[1\mu \] or \[1000m\mu \]) than the size of sol particles (less than \[200m\mu \]). (ii) If the pores of the ordinary filter paper are made smaller by soaking the filter paper in a solution of gelatin of colloidion and subsequently hardened by soaking in formaldehyde, the treated filter paper may retain colloidal particles and allow the true solution particles to escape. Such filter paper is known as ultra - filter and the process of separating colloids by using ultra – filters is known as ultra – filtration. (4) Ultra – centrifugation (i) The sol particles are prevented from setting out under the action of gravity by kinetic impacts of the molecules of the medium.        (ii) The setting force can be enhanced by using high speed centrifugal machines having 15,000 or more revolutions per minute. Such machines are known as ultra–centrifuges.  

Lyophilic and lyophobic colloidal solutions (or sols) are generally prepared by different types of methods. Some of the common methods are as follows. (1) Preparation of Lyophilic colloids (i) The lyophilic colloids have strong affinity between particles of dispersed phase and dispersion medium. (ii) Simply mixing the dispersed phase and dispersion medium under ordinary conditions readily forms these colloidal solutions. (iii) For example, the substance like gelatin, gum, starch, egg, albumin etc. pass readily into water to give colloidal solution. (iv) They are reversible in nature become these can be precipitated and directly converted into colloidal state. (2) Preparation of Lyophobic colloids : Lyophobic colloids can be prepared by mainly two types of methods. (i) Condensation method : In these method, smaller particles of dispersed phase are condensed suitably to be of colloidal size. This is done by the following methods. (a) By oxidation : A colloidal solution of sulphur can be obtained by bubbling oxygen (or any other oxidising agent like \[HN{{O}_{3}},\,B{{r}_{2}}\] etc.)  through a solution of hydrogen sulphide in water. \[2{{H}_{2}}S+{{O}_{2}}\,(\text{or}\,\text{any}\,\text{other}\,\text{oxidising}\,\text{agent)}\xrightarrow{{}}2{{H}_{2}}O+2S\]      (b) By reduction : A number of metals such as silver, gold and platinum, have been obtained in colloidal state by treating the aqueous solution of their salts, with a suitable reducing agent such as formaldehyde, phenyl hydrazine, hydrogen peroxide, stannous chloride etc. \[2AuC{{l}_{3}}+3SnC{{l}_{2}}\xrightarrow{{}}3SnC{{l}_{4}}+\underset{\text{Gold sol}}{\mathop{2Au}}\,\] \[2AuC{{l}_{3}}+3HCHO+3{{H}_{2}}O\xrightarrow{{}}\underset{\text{Gold}\,\text{sol}}{\mathop{2Au}}\,+3HCOOH+6HCl\]              The gold sol, thus prepared, has a purple colour and is called purple of cassius. (c) By hydrolysis : Many salt solutions are rapidly hydrolysed by boiling dilute solutions of their salts. For example, ferric hydroxide and aluminium hydroxide sols are obtained by boiling solutions of the corresponding chlorides.  \[FeC{{l}_{3}}+3{{H}_{2}}O\xrightarrow{{}}\underset{\text{Colloidal}\,\text{sol}}{\mathop{Fe{{(OH)}_{3}}}}\,+3HCl\] Similarly silicic acid sol is obtained by the hydrolysis of sodium silicate. (d) By double decomposition : A sol of arsenic sulphide is obtained by passing hydrogen sulphide through a cold solution of arsenious oxide in water. \[A{{s}_{2}}{{O}_{3}}+3{{H}_{2}}S\xrightarrow{{}}A{{s}_{2}}{{S}_{3}}+3{{H}_{2}}O\] (e) By excessive cooling : A colloidal solution of ice in an organic solvent like ether or chloroform can be prepared by freezing a solution of water in the solvent. The molecules of water which can no longer be held in solution, separately combine to form particles of colloidal size. (f) By exchange of solvent : Colloidal solution of certain substances such as sulphur, phosphorus, which are soluble in alcohol but insoluble in water can be prepared by pouring their alcoholic solution in excess of water. For example, alcoholic solution of sulphur on pouring into water gives milky colloidal solution of sulphur. (g) By change of physical state : Sols of substances like mercury and sulphur are prepared by passing their vapour’s through a cold water containing a suitable stabilizer such as ammonium salt or citrate. (ii) Dispersion methods : In these methods, larger particles of a substance (suspensions) are broken into smaller particles. The following methods are employed. (a) Mechanical dispersion
  • In this method, the substance is first ground to coarse particles.
  • It is then mixed with the dispersion more...

  (1) Phases of colloids : We know that a colloidal solution is of heterogeneous nature. It consists of two phases which are as follows (i) Internal phase or Dispersed phase (Discontinuous phase) : It is the component present in small proportion and is just like a solute in a solution. For example in the colloidal solution of silver in water (silver acts as a dispersed phase) (ii) External phase or Dispersion medium (continuous phase) : It is generally component present in excess and is just like a solvent in a solution. For example, in the colloidal solution of silver in water. Water act as a dispersion medium.       (2) Classification of colloids : The colloids are classified on the basis of the following criteria (i) Classification based on the physical state of the dispersed phase and dispersion medium : Depending upon the physical state of dispersed phase and dispersion medium whether these are solids, liquids or gases, eight types of colloidal systems are possible. Different types of colloidal systems
Dispersed phase Dispersion Medium Colloidal System Examples
Liquid Gas Aerosol of liquids Fogs, clouds, mists, fine insecticide sprays
Solid Gas Aerosol of solids Smoke, volcanic dust, haze
Gas Liquid Foam or froth Soap lather. Lemonade froth, foam, whipped cream, soda water
Liquid Liquid Emulsions Milk, emulsified oils, medicines
Solid Liquid Sols Most paints, starch in water, proteins, gold sol, arsenic sulphide sol, ink
Gas Solid Solid foam Pumice stone, styrene rubber, foam rubber
Liquid Solid Gels Cheese, butter, boot polish, jelly, curd
Solid Solid Solid sols (coloured glass) Ruby glass, some gem stones more...
(1) The foundation of colloidal chemistry was laid down by an English scientist, Thomas Graham, in 1861. The credit for the various advances in this field goes to eminent scientists like Tyndall, Hardy, Zsigmondy, N.R. Dhar, S.S. Bhatnagar and others. (2) Thomas Graham classified the soluble substances into two categories depending upon the rate of diffusion through animal and vegetable membranes or parchment paper. (i) Crystalloids : They have higher rate of diffusion and diffused from parchment paper. Examples : All organic acids, bases and salts and organic compounds such as sugar, urea etc. (ii) Colloids (Greek word, kolla, meaning glue-like) : They have slower rate of diffusion and can not diffused from parchment paper. Examples : Starch, gelatin, gums, silicic acid and hdemoglobin etc. (3) The above classification was discarded i.e., the terms colloid does not apply to a particular class of substances but is a state of matter like solid, liquid and gas. Any substance can be brought into colloidal state. (4) The colloidal state depends on the particle size. If is regarded as intermediate state between true solution and suspension.
Property Suspension Colloid solution True solution
Nature Heterogeneous Heterogeneous Homogeneous
Particle size > 100 nm 1 nm – 100 nm < 1 nm
Separation by (i) Ordinary filtration (ii) Ultra- filtration     Possible Possible   Not possible Possible   Not possible Not possible
Settling of particles Settle under gravity Settle only on centrifugation Do not settle
Appearance Opaque Generally transparent Transparent
Tyndall effect Shows Shows Does not show
Diffusion of particles Does not diffuse Diffuses slowly Diffuses rapidly
Brownian movement May show more...
(1) Zeolite are alumino–silicates of the general formula, \[{{M}_{x/n}}{{[Al{{O}_{2}}]}_{x}}.{{(Si{{O}_{2}})}_{y}}.m{{H}_{2}}O\], where, M may be simple cation like \[N{{a}^{+}}\], \[{{K}^{+}}\]or \[C{{a}^{2+}}\], n is the charge on the simple cation, m is the number of molecules of water of crystallization. (2) Some well known zeolites are as follows, Erionite \[\to N{{a}_{2}}{{K}_{2}}CaMg{{(Al{{O}_{2}})}_{2}}{{(Si{{O}_{2}})}_{2}}.6{{H}_{2}}O\] Gemelinite \[\to N{{a}_{2}}Ca{{(Al{{O}_{2}})}_{2}}{{(Si{{O}_{2}})}_{4}}.6{{H}_{2}}O\] Faujasite (natural) \[\to N{{a}_{56}}{{(Al{{O}_{2}})}_{56}}{{(Si{{O}_{2}})}_{136}}.250{{H}_{2}}O\] ZSM-5 \[\to {{H}_{x}}[{{(Al{{O}_{2}})}_{x}}{{(Si{{O}_{2}})}_{96-x}}].16{{H}_{2}}O\] Linde-A (synthetic) \[\to {{[N{{a}_{12}}{{(Al{{O}_{2}})}_{12}}{{(Si{{O}_{2}})}_{12}}.27{{H}_{2}}O]}_{8}}\] (3) The characteristic feature of zeolites is the openness of the structure, which permits cavities of different sizes. (4) The open structure is provided by silica in which aluminium occupies x/(x+y) fraction of the telrahedral sites. (5) The negative charge of the aluminosilicate framework is neutralized by the replaceable cations. (6) The void space forms more than 50% of the total volume, which is occupied by water molecules. (7) The reaction- selectivity of zeolites depends upon the size of cavities (cages), pores (apertures) and the distribution of pores in the structure. The pore size in zeolites generally varies from 260 pm to 740 pm.  (8) Zeolite have high porosity due to the presence of one, two, or three dimensional networks of interconnected channels and cavities of molecular dimensions. (9) There is a new class of highly siliceous zeolites with an optimal pore diameter of 550pm. ZSM-5 is one such zeolite having the formula. \[[{{H}_{x}}{{(Al{{O}_{2}})}_{x}}.{{(Si{{O}_{2}})}_{96-x}}].16{{H}_{2}}O\] (10) The zeolite catalyst ZSM-5 converts alcohols to gasoline (petrol) by dehydrating the alcohol and producing a mixture of wide variety of hydrocarbons.

(1) Activity : Activity is the ability of catalysts to accelerate chemical reaction, the degree of acceleration can be as high as \[{{10}^{10}}\] times in certain reactions. For example reaction between \[{{H}_{2}}\]and \[{{O}_{2}}\] to form \[{{H}_{2}}O\]in presence of platinum as catalyst takes place with explosive violence. In absence of catalyst, \[{{H}_{2}}\]and \[{{O}_{2}}\]can be stored indefinitely without any reaction.     (2) Selectivity : Is the ability of catalysts to direct reaction to yield particular products (excluding other). Example :     (i) \[n-\text{heptane}\xrightarrow{Pt}\]                               (ii) \[C{{H}_{3}}CH=C{{H}_{2}}\xrightarrow{BiMo{{O}_{4}}}C{{H}_{2}}=\overset{\,\,\,O}{\mathop{\overset{\,\,\,\,||}{\mathop{\underset{\text{Acrolein}}{\mathop{CHCH}}\,}}\,}}\,\]  


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