Textbook of Engineering Chemistry

Index

Chapter 1

Colloids

1.1 Introduction

All the macroscopic and microscopic particulate matter may be grouped into two categories (i) pure substances (ii) Mixtures.

Colloids particles range from 1 nm, (10 Å ), to 1000 nm and they consist of neutral molecules and charged particles like ions. They are not single phase solutions like true solutions but generally contains two phases. This fact could be demonstrated by studying the optical properties of a true solutions, a suspension and a colloidal solutions. For this take the suspension of soil in water in a test tube say (a), the true solution of sodium chloride in water in test tube (b) and a colloidal starch solution in test tube (c). Just by looking at the test tubes with our naked eye, we can identify that test tube (a) is a suspension but test tubes ‘b’ and ‘c’ both look fully transparent.

Now pass an intense beam of light through these test tubes. We will be able to trace the path in test tubes (a) and (c) while we cannot locate any ray in the tube (b). This is due to scattering of the light by the suspension particles and colloidal particles. The scattering of light by the colloidal particles was first noticed by Tyndall and is known as Tyndall effect. The distinguishing features of colloids are given in (Table 1.1.), although a detailed account of properties of colloids will be given later in section 1.6.

Table 1.1 Comparative statement of properties of true solutions, colloids and suspensions.

1.2 Types of Colloidal Dispersion

We come across various colloids daily. The milk we drink, the blood flowing through our veins, the protein solutions, the butter, cheese, jelly etc., that we eat. the clouds, the fog, the smoke are all different forms of colloidal dispersions or colloidal suspensions.

The colloidal phase and colloidal medium which form the colloidal dispersions can take all the possible combinations of three states of matter viz. solid, liquid and gas. A gas mixes in another gas in all proportions, uniformly at molecular level, this combination only results in a solution. Various colloidal dispersions with suitable example are listed in (Table 1.2.)

Table 1.2 Types of Colloidal Dispersions.

1.3 Classification of Colloids

A colloidal suspension has two phases, the disperse phase and dispersion medium. Basing on the affinity between these two phases colloids are classified into lyophobic sol and lyophilic sol. When the dispersion medium is water these are said to be hydrophobic and hydrophilic sols respectively.

Lyophobic sols : These are also termed as irreversible sols or suspension. This term has its origin in greek and means solvent hating or solvent averting. In the lyophobic colloids the disperse phase has very little affinity towards the dispersion medium. This lack of affinity accounts the difficulties encountered in the preparation and their easy precipitation. As the colloids are readily precipitated giving larger visible particles, they are called suspensoids and this process of precipitation is known as coagulation, irreversibility of this process brought the name irreversible colloids. Colloidal dispersions of metals like gold, silver, iron etc., and sparingly soluble salts like As2S3, Fe(OH)3 etc., are the examples for this class. They coagulate readily by the addition of even a trace amount of electrolyte. Normally stabilizing agents are added to prevent coagulation.

Lyophilic sols : Lyophilic means solvent loving or solvent liking. These colloids are formed readily by employing simple techniques like heating, shaking a colloidal particle phase in a suitable dispersion medium and called emulsoids or reversible colloids. In the house we notice the preparation of starch solution, just by adding starch powder to the boiling water. Protein solution, glue (gum), etc., are some typical examples of lyophilic sols. These sols obtained are of reversible type. A coagulated disperse phase could be brought back to the colloidal state just by diluting and wanning it again. These sols are self stabilized and require no stabilizer and small amounts of electrolyte have no effect.

The characteristics of lyophobic and lyophilic sols are given in (Table 1.3.)

Table 1.3 Characteristics of Lyophobic and lyophilic sols.

1.4 Methods of Preparation of Colloidal Solutions

It is possible to prepare colloidal solutions of all substances by selecting suitable dispersion medium. The particle size of colloidal dispersion is intermediate to true solutions and suspension. So we can have two approaches in preparing these dispersions. One approach involves breaking of macroscopic suspension particles into particles of the size of colloidal phase (1 nm - 1000 nm) employing mechanical methods or electrical methods or by creating conditions for the reversal of coagulation. The methods employed are called dispersion methods. The second approach involved bringing the microscopic atoms or molecules of true solutions together and forming colloidal particles. These methods are called condensation methods. These two approaches can be represented by the following flow chart.

A. Dispersion Methods

1. Mechanical dispersion : Coarser particles of a substance are broken into colloidal size by grinding them between two steels discs having a narrow clearance. For this a suspension along with a suitable stabilizer is charged through a hollow shaft of a colloidal mill (Fig. 1.1), where the steel discs are rotating at a high speed in opposite direction, and the colloidal dispersion is collected.

Fig. 1.1 Colloidal mill.

This way indian ink is prepared by grinding lamp black in the colloid mill and stabilizing the dispersion with gum arabic.

2. Electro-dispersion - Bredig's arc method : The colloids dispersion of metals like gold, silver, copper etc., in water are prepared by this method. The metal rods are dipped in the solvent and an arc is set by passing current through the rods. This arc liberates metal particles of colloidal size which are readily absorbed by the medium giving a colloidal suspension (Fig. 1.2). To prevent evaporation of the medium due to heat liberated by the arc the vessel is surrounded by ice and kept cool.

This method is not useful when we take organic solvents as dispersion medium, as the heat generated at the arc chars the medium.

Fig. 1.2 Bredig's setup for electro dispersion

3. Peptization : Peptization is inverse of coagulation. As discussed earlier coagulation is the result of lack of affinity between dispersed phase and dispersing medium. An affinity is created by the addition of a stabilizing agent, known as peptizing agent, which prompts the coagulated particles back to give colloidal solution and the process is called peptization.

A freshly prepared precipitate of ferric hydroxide, Fe(OH)3, is peptized, giving a colloidal dispersion, by the addition of some ferric chloride, FeCl3, solution. This is due to masking of uncharged colloidal particles of Fe(OH)3 by the aquated ferric ions, Fe³+ aq, and creating a net positive charge on the colloidal particle and thus bridging the affinity gap between hydrophobic Fe(OH)3, particle and dispersion medium.

As these colloidal particles are positively charged, addition of a negatively changed PO4³- ion to the colloidal solution neutralizes the charge causing destabilization of colloid and precipitation of disperse phase.

We come across many such systems in our day to day life. Milk is a colloidal dispersion of oil in water. As oil is a hydrophobic substance, casein in milk serves the purpose of peptizing agent. Milk coagulates by the addition of common salt. In the formation of indian ink, lamp black is peptized by gum arabic.

B. Condensation Methods

Concentrated solutions yield only suspensions. The excess of hy drogen sulphide is removed by boiling the solution which may otherwise lead to precipitation. Similarly on adding few drops of ferric chloride to a dilute solution of potassium ferrocyanide in the presence of a peptizing agent we get a sol of ferri cyanide.

(ii)   Oxidation : H2S on oxidation gives a colloidal solution of elemental sulphur

A moderate oxidizing agent as bromine or nitric acid could also be used for this purpose.

(iii)   Reduction : The colloids of metals such as gold, silver, lead and platinum could be conveniently prepared by reducing the metal salts with reducing agents such as formaldehyde, tannic acid stannous chloride etc

Zigmondy prepared the bright red gold sol by reducing the gold chloride (HAuC14.3H2O), and phosphorous colloid by reducing a dilute etherial layer of phosphorus.

(iv)   Hydrolysis : Colloidal dispersions are obtained by the hydrolysis of metal hydroxides, viz., Fe (OH)3 or Al (OH3) and stabilizing the colloids by the addition of little excess of solutions of corresponding metal chlorides.

For achieving stability of the colloid it is essential to remove HC1 by dialysis.

1.5 Purification of Colloidal Dispersion

The general impurities present in a colloidal dispersion are mainly the suspended particles and the electrolytes. The suspended particles could be easily separated by a simple filtration. The following methods are employed for freeing a colloidal solution from electrolytes.

Fig. 1.3 Graham dialyzer.

Fig. 1.4 Electrodialysis.

Electrodialysis is obviously not meant for removing uncharged impurities such as sugar, urea etc.

1.6 Properties of Colloids

1.6.1 State

Colloidal solutions are heterogeneous mixtures and have two phases, the disperse phase and the dispersion medium.

1.6.2 Particle size

They have a particle size of 1-1000 nm and can be seen only under a ultra microscope, particles are invisible to naked ey e and to even for powerful microscopes.

1.6.3 Filtration

Colloidal particles pass through ordinary filter paper. As mentioned in the purification methods specially prepared ultra filter retain the colloidal particles. They also can not pass through animal membranes.

1.6.4 Color

The color of a colloidal dispersion depends on

(a) The size and charge the of the particle

(b) The characteristic absorption, the disperse phase and dispersion medium.

(c) Whether the observer is receiving the transmitted light or reflected light.

(d) The wave length of the light falling.

For example, with the increase in the particle size gold sol changes its color gradually from red to blue. When the particle are small (say 200 nm) the blue component of the white light is reflected and w hen we observe in the direction of incidence only red color is observed. Similarly with the increase in particle size the gold particles start reflecting even the other wave length thereby start looking blue.

Dilute milk appears blue when observed at right angle to the incident light (reflected rays) and red when observed in the direction of incident light (transmitted light).

A beautiful demonstration of the color properties of colloidal particles is the chemical sunset scene produced by the transmitted light by the addition of hydrochloric acid to sodium thiosulphate. Here a sulphur colloid is produced initially, which gradually coagulates to give suspension particles.

1.6.5 Colligative Properties

The colligative properties viz., osmotic pressure, relative lowering of boiling point depend on the number of solute particles in a given weight of solvent. For a given concentration true solutions have far larger number of solute particles than the colloidal particles. This is due to aggregation of solute particles (about 1000 nm) to give new bigger size colloidal particles. Of the above mentioned colligative properties only osmotic pressure has a measurable value and changes in other properties are insignificant. The change in osmotic pressure of a colloid is a highly useful data in determining the average particle mass of starch particle which was found to be about 32,000 atomic mass units.

1.6.6 Optical Property-Tyndall Effect

As discussed already, when light passing through a true solution is observed at right angles to the path of incident ray, it looks completely dark. The same experiment if we repeat with a colloidal solution, we notice a luminescent path of the ray passing through the solutions. The path of the ray is made visible by the scattering of light by the colloidal particles. The particles of true solution can not scatter light because the wave length of light is larger than the size of the particles (< 10 nm).

This effect was first noticed by Faraday but detailed studies were made by Tyndall giving it the name Tyndall effect (Fig. 1.5). The appearance of bright path of the projection lamp in a theatre is due to scattering of light by the dust particles.

Fig. 1.5 Tyndall effect.

The two conditions that must be satisfied to show Tyndall effect are :

(i) The wave length of light used must not be much larger than the diameter or size of the particle.

(ii) The dispersed phase and dispersed medium should differ greatly in the magnitude of refractive indices.

Condition (i) was already explained and condition (ii) could be understood if we consider the colloidal suspension of freshly prepared albumin. Here the disperse phase, albumin and the dispersion medium water, have a very small difference of refractive indices and the Tyndall effect is not observable. On standing the particle size increases, bringing a change in the refractive index thus showing Tyndall effect.

Tyndall effect is strong for hydrophobic sols due to large difference in the refractive indices of disperse phase and dispersion medium. In case of lyophilic sols the difference in refractive indices is small, resulting in a weak Tyndall effect.

Siedentopf and Zsigmondy made successful attempt to see the colloid particles with the help of a microscope known as ultra microscope. Here a bright light beam from an arc is converged with a convex lens and allowed to fall on the colloidal solutions. We find two self-luminous bluish colored cones, called Tyndall cones, meeting at the focus of the lens. When a microscope is placed at right angles to the incident light, presence of colloidal particles can be detected as bright moving spots. This is due to initial absorption of light by the colloidal particle before it is scattered.

1.6.7 Kinetic Property - Brownian Movement

The invention of ultra-microscope by Siedentopf and Zsigmondy led to another invention by Robert Brown in 1827. Just like the constant directionless movement of pollen grains in an aqueous suspension, he noticed under microscope that the colloidal particles also move continuously in a zig-zag path without any destiny and this type of motion is called Brownian movement.

Fig. 1.6 Brownian movement.

This Brownian movement arises due to constant collisions or striking of the molecules of dispersion medium and colloidal particles. Fig. 1.6. Owing to the smaller size of the colloidal particles, the striking are limited and the colloidal particles which always move in a resultant direction.

A large particle (e.g., a suspension particle) has a higher inertia (inability of a body to move) due to its heavy mass and in addition due to numerous collisions in all the directions and cancellation of opposing forces the resultant force becomes extremely weak to cause any significant impact. Hence the particles of a suspension show no Brownian movement and settle under gravity.

1.6.8 Electrical Charge

Colloids often carry a charge on their surface. For example, ferric hydroxide sol particles are positively charged while the arsenous sulphide sols are negatively changed. The electrical neutrality of the sol is maintained by the dispersion medium taking equal and opposite charge of the colloidal particle.

A colloidal particle can take both positive and negative charges depending on the conditions employed in the preparation of the colloidal dispersions. The following two examples demonstrate this fact.

Example 1.

If a freshly prepared stannic oxide precipitate is peptized by a few drops of KOH solution the sol assumes a negative charge.

This is due to the adsorption of stannate ions.SnO3²- formed by the reaction between SnO2 and KOH.

When the SnO2 precipitate is peptized with the addition of few drops of HC1. die sol takes a positive charge.

Sn⁴+ absorbed on the sol particle formed by the reaction between SnO2 and HC1

Example 2.

If a dilute solution of potassium iodide is added to a concentrated solution of AgNO3 a positively charged colloid is formed due to adsorption of free Ag+ ion on the Agl surface and is represented as [Ag I] Ag+*NCO-3. Similarly a negatively charged colloid is produced when dilute silver nitrate is added to a concentrated solution of KI and is represented as [Ag I] I-Κ+.

Inspite of co-existence of oppositely charged disperse phase and dispersion medium, the reason for no charge neutralization, and unexpected stability is explained by the electrical double layer theory.

1.6.9 Electrical Double Layer Theory

This theory was propounded by Helmholtz. Consider a positively charged fixed layer in contact with a mobile or movable or diffused, medium. The negatively charged ions of the movable medium try to approach the fixed layer to neutralize the charge. But the constant thermal agitation or kinetic motion of the ions of the mobile layer create a varying electrical environment for the positively charged fixed layer. This constantly shifting environment results in a charge difference between the fixed layer and the mobile layer known as Zeta potential or electro kinetic potential.

Fig· 1.7 The electrical double layer.

The combination of the fixed layer and mobile layer forms an electrical double layer system Fig. 1.7. The stability of a colloidal dispersion, according to electrical double layer theory, is due to formation of a zeta potential screen between the dispersed particles (fixed layer) and dispersion medium (mobile layer) that restricts the neutralization of electrical charge on the fixed layer. This screen of electrical double layer is broken down when we add multivalent ions carrying the charge of dispersion medium, leading to coagulation of the sol. Thus positively charged ferric hydroxide, Fe(OH)3, sol is coagulated by the addition of trivalently charged PO4³- ions as shown in Fig. 1.8.

Fig. 1.8 Electrical double layer of Fe (OH) sol.

The phosphate anion, wherever it gets in contact with the colloidal particles, the Zeta potential approaches zero resulting in the coagulation of the sol particle.

1.6.10 Passage of Current

Passage of current through a colloidal solution results in the movement of colloidal particles, as they are charged, towards oppositely charged electrodes. We can design experiments either to allow the movement of the colloidal particles or restrict their motion. The former process is known as electrophoresis or cataphoresis and the later process is called electro-osmosis.

A. Electrophoresis : The migration of colloidal particles under the influence of applied electric field is known as electrophoresis. This migration helps us in deciding the charge associated with the colloidal particles to demonstrate electrophoresis, the sol is filled in a U-tube. Two electrodes are fixed, just above the colloidal solutions, in both the open ends of U-tube (Fig. 1.9).. Now water is added to the open ends to dip the electrodes. A high electrode potential is applied across the electrodes. Now we mark a movement of sol-water boundary depending on the charge of colloidal particles. For example, arsenic sulphide colloidal particles, charged negatively, move towards the anode causing a raise of level in the anode limb.

As in the first observation migration of boundaries was made with ferric hydroxide colloid, which migrated towards cathode, the phenomena was given a misnomer as cataphoresis.

Fig. 1.9 Electrophoresis.

The sol particles move at different velocities depending on the charge, mass and size of the particle. The distance travelled by the colloidal particles in one second under an applied potential of one volt per centimeter is called electrophoretic mobility. Knowing the electrophoretic mobility enables one to calculate the zeta potential using the formula

Knowledge of electrophoretic mobility also helps in separating the sols from a colloidal mixture. Thus from a mixture of metal sol and metal sulphide sol. the lighter colloidal metal sulphide particles are recovered first, followed by the metal sol particles. Biochemists use this technique in fractionating proteins, polynucleic acids and polysaccharides from their colloidal mixtures.

Depending on the Charge carried by colloidal particles they are grouped into positively charged sols and negatively charged sols. Few common sols are listed below Table. 1.4.

Table 1.4

Applications of electrophoresis : Electrophoresis has many industrial applications :

B. Electro-osmosis : The movement of the dispersion medium, when the colloidal particles are restricted from their motion, under the influence of electric field is known as electroosmosis. This could be demonstrated by constructing a simple apparatus shown in Fig. 1.10.

Fig. 1.10 Electroosmosis apparatus (for positive charged particle).

The apparatus consists of three compartments A,B and C separated by two dialyzing membranes MA and MB. The central compartment ‘C’ is filled with the colloidal solution, and the side compartments ‘A’ and 'E’ are fitted with side tubes TA and TB respectively.

The side compartments are fitted with platinum electrodes EA and EB. An electrode potential (D. C current) is applied across EA and EB. The dispersion medium and disperse phase start moving towards oppositely charged electrodes. For example if we take arsenic sulphide sol, the negatively charged As2S3 particles start moving towards EA, the anode and the dispersion medium towards EA the cathode. But the sol particles are not allowed to get into the anodic compartment ‘A’ by the dialyzing membrane Ma. The dispersing medium passes into the cathodic compartment 'B’ without any hindrance by the membrane MB. This results in a rise in the level of TB with a corresponding fall in the level of TA. In case of positively charged sol particle the rise is in the anodic compartment.

1.6.11 Coagulation

Coagulation is a process of growing the colloidal particle size resulting in the formation of suspension and ultimately leading to the precipitation of the particles of the dispersed medium. It may be spontaneous or accomplished either by the addition or complete removal of electrolyte or by mixing two oppositely charged colloidal solutions.

Since it is the charge on the ions of added electrolyte which is responsible for the coagulation, it is rational to assume that the valency of the ions is the root cause of precipitation. Hardy and Schulze after rigorous experiments found that higher the valency of the active ion the greater is its precipitating action and is known as Hardv-Schulze law. The precipitating actions of cations Na+, Ba²+, A1³+ on As2S3 sol has been found to be

The minimum concentration of an electrolyte which can cause precipitation is called the flocculation value.

Table 1.5 Flocculation values of As2S3 sol(milli mole per litre to produce precipitation)

Similarly for the positively charged colloidal particles (e.g.. Fe(OH)3 sol) we have to take the anion as the active ion. There the precipitating action is of the order

Table 1.6 Flocculation value of Fe(OH)3 sol(millie mole per litre required to produce precipitation)

When we compare the relative stability of hydrophobic and hydrophilic sols, the hydrophobic sols readily coagulate by the addition of electrolytes. In case of hydrophilic sols even after stripping away the charge present on the colloidal particle by die added electrolyte, the sol is not coagulated. This is due to a shield of water molecules formed around the colloidal particle as a result of aquation. Addition of a few drops of dehydrating agent like alcohol or acetone break opens the shield and coagulation sets in. This is represented in Fig. 1.11

Fig. 1.11 Coagulation of hydrophobic and hydrophilic sols.

1.6.12 Protection

As mentioned above the lyophilic colloids achieve extraordinary stability due to solvation of colloidal particles. When lyophilic sols arc added to lyophobic sols depending on their sizes either lyophobic sol is adsorbed in the surface of lyophilic sol or lyophilic sol is adsorbed on the surface of lyophobic sol as represented in Fig. 1.12). In both the cases the hydrophobic sols achieve additional stability. The process of addition of lyophilic sols by which the lyophobic sols are protected from precipitation on adding an electrolyte is known as protection, and the lyophilic colloid added as the protective colloid.

Fig. 1.12 Protection of a colloid.

Thus hydrophilic colloids such as gelatin, starch etc., act as protective colloids for the gold sol and prevent their precipitation by the addition of limited amounts of NaCl.

For a comparative study Zsigmondy introduced a scale of protective action for different protective colloids in terms of gold number. The gold number is the weight in milligrams of a protective colloid which checks the coagulation of 10 ml of a given gold sol on adding 1 ml of 10% sodium chloride. Thus smaller the gold number, greater is the protective action. The gold numbers of few commonly used protective colloids is given in Table. 1.7.

Table 1.7 Gold numbers of some protective colloids.

The data in Table. 1.7 suggests that gelatin is a very effective protective colloid.

1.6.13 The Donnan Membrane Equilibrium

The Donnan membrane equilibrium is a special case where a true solution of an electrolyte is separated from a salt which has a non-diffusible ion by a membrane, and at equilibrium the concentration of diffusible electrolyte on both the sides of membrane was found to be different. In case of colloids the nondiffusible ion is the charged colloidal particle.

Thus when we take C1 moles of sodium chloride as one side of the membrane compartment ‘A’ and sodium salt of non-diffusible colloidal ion, R on the other side of the membrane (compartment B) after allowing the system to attain an equilibrium, one finds an increase in the concentration of diffusible electrolyte in the compartment 'B'. If x moles/lit of sodium chloride diffused into the compartment ’A' dropping the concentration of electrolyte in compartment ‘A’ from an initial value of C1 to C1 -X, then the equilibrium may be represented as

Compartment A’Sodium chloride           Compartment B’Sodium salt

Donnan (1911) gave explanation for the migration of diffusible ions from one compartment to another compartments separated by a membrane that restricts the movement of non diffusible ions. If no non-diffusible ion is present in the system the electrolyte is present equally in both the compartments. The driving force behind this diffusion is known as Chemical potential and for an ideal electrolyte it is equal to the product of concentration of the ions in the electroly te. At equilibrium the chemical potential in both the compartments is equal.

When non-diffusible electrolyte of concentration C2 is separated from diffusible electrolyte of concentration C1 as represented above the chemical potential of diffusible ions at equilibrium are equal

X/C1 is the fraction of sodium chloride (diffusible electrolyte) that has diffused through the membrane. Higher the concentration of non diffusible electrolyte present low is the fraction of electrolyte diffused. From the above expression it is also clear that in the absence of non-diffusible electrolyte, half of the NaCl migrates from Compartment ‘A’ to Compartment ‘B’.

Total concentration of ions at equilibrium in compartment "A ' is 2(C7-A) and in compartment ‘B’ it is 2(C2 + X). Hence the concentration difference across the membrane is

As this system is comparable to an osmometer, the osmotic pressure 'B' of the solution is given by

but

Therefore,

By rearranging we have

When C1>>C2 the above expression reduces to

π = RTC2

Thus a measurement of osmotic pressure allows us to calculate the concentration of a non-diffusible electroly te or a charged colloidal particle, there by its molecular weight.

1.7 Emulsion(l/l)

When liquids form both the disperse phase and dispersion medium of a colloid, then that colloid is said be an emulsions. Any two partially Either liquids can yield an emulsion. Either liquid can be dispersed in the other. Fig. 1.13.

Fig. 1.13 Emulsion of oil in water and water in oil.

Thus we can have an emulsion of oil in water by shaking vigorously few drops of oil in excess water. Similarly an emulsions of water in oil can be obtained by taking few drops of water in oil. These are illustrated in Fig. 1.13.

The emulsions formed entirely of oil and water are quite unstable, as the molecules of the dispersed phase collide with one another and separate out into two layers on standing. Stability of an emulsions is achieved by the addition of a third substance known as emulsifying agent or emulsifier. The commonly used emulsifiers arc gelatin, soaps and gum arabic. The role of emulsifier, according to Brancraft, is to surround the particles of dispersed phase and reduC1ng the surface tension on one side of the water oil interphase than the other. As the spherical surface has always a minimum area the emulsion particle forms a spherical envelope that inhibits the colloidal particles come closer. Fig. 1.14.

Fig. 1.14 Oil particle dispersed in water.

Certain finely divided solid particles can also act as emulsifiers. They are wetted by both the liquids. The liquid that wets more forms the dispersion medium and the liquid that wets less is protected by the solid particles,Fig. 1.15.

Fig. 1.15 Protective action of soot particles.

We get an emulsions of water in kerosene on shaking them along with some soot particles.

1. Preparation of emulsions : Vigorous shaking or stirring of few drops of the disperse phase with dispersion medium in the presence of a liquid emulsifier or finely divided solid particles is suffiC1ent to given an emulsion.

Emulsions can be obtained by adding a solution to an excess another solvent, which readily dissolves the solvent of the added solution but keeps liquid solute undissolved. Thus an emulsion of oil in water is obtained by adding a dilute solution of oil in alcohol to excess of water.

Passing a vapor of oil into water containing emulsifying agent also gives an emulsion.

2. Properties of emulsions : The properties of emulsions are same as that of colloids. To avoid repetition of electrical, optical, brownian movement etc., only few selective properties are discussed here.

A. The stability : The stability of an emulsion is determined by two factors (i) the strength of the protective layer of the emulsifying agent(ii) the charge on the emulsoid (dispersed particle).

B. Coagulation : Coagulation or demulsification takes place by adding a substance that uncovers the emulsifier film. This can be affected by :

(i)    By adding an electrolyte that neutralizes the charge on emulsoid.

(ii)    By excessive heating, cooling and centrifuging.

(iii)   By passing current.

(iv)   By adding dehydrating agent to an emulsion of water in oil.

C. Vision : When the liquids partiC1pating in the formation of emulsion have refractive indices of the same order, the emulsion looks transparent and when they are different the emulsion is opaque or turbid.

3. Uses of emulsions : Emulsions of a substance has more surface area than the pure substance. The large surface area codliver oil emulsions helps in better assimilated by the stomach than pure oil. Similarly phenyl and lysol act as better disinfectants when emulsified in water.

1.8 Gels

Colloidal systems of liquids dispersed in solids are called gels. They are obtained by coagulation of the colloidal solutions yielding a semisolid mass. Thus on heating agar-agar with water first we get a colloid and on further boiling this solution agar-agar molecules come closer trapping water in a honey combed like structure and giving a semisolid mass of agar-agar gel.Fig. 1.16.

Fig. 1.16 Fonnation of a gel.

Similarly on adding alcohol to a saturated solution of calcium carbonate in water initially produces a colloidal solutions which coagulate to give a semisolid mass of C’aCO, in which alcohol is trapped. This gel of alcohol in calcium carbonate, called solid alcohol, is used as solid fuel in picnic stoves, military camps etc.

1.Properties of gels : On standing gels loose the medium (e.g., water) and shrink. This shrinking of gel with simultaneous exudation (sweating) of the gel is called synergisis or weeping of the gel. Gels are classified into three categories.(i) Elastic gels (ii) Rigid gels (iii) Thixotropic gels.

(i)   Elastic gels :These gels are defused by the application of a force but retains its original shape on the removal of applied force, e.g., Starch, gelatin, fruit jam and jellies.

(ii)   Rigid gels :There is no deformation on applying force. The strong covalent bonds between molecules give the rigidity of shape, e.g., silicic acid or commonly known as silica gel.

(iii)   Thixotropic gels : These become semisolid when kept aside but become liquid when agitated. Kiesel gel forms a thin paste on standing but readily flows on shaking. Solution of high polymers exhibit these properties.

2. Uses of gel :Commercially many gels are available in the market. The commonly used boot polishes, polishing waxes, soaps, some brands of tooth pastes and various foodstuffs as petha are all examples of gels.

1.9 Application of Colloid Chemistry

Applications of a class of colloids namely emulsions and gels have already been discussed in subheads 1.7 and 1.8. Application of other forms is given below.

1.   Colloids in medicine : Medicines in the form of colloids are easily absorbed by the body tissues. Some of the essential metals like silver, gold which can not be absorbed in the metallic form are administered as colloids.

(i)   Argyrol and protargal are protected silver colloids used in the cure of granulations.

(ii)   Colloids of gold, calcium, manganese, etc., are administered as intramuscular injections to enhance the vitality and cure tuberculosis and rickets.

2.   Colloids as pesticides : Sulphur colloids are sprayed on plants to kill various germs.

3.   Smoke precipitation : Smoke in the industrial exhausts contain particulate carbon and dust in the colloidal form and these are removed by the application of 30,000 volts and then allowed to escape into the atmosphere through the chimney Fig. 1.17.

Fig. 1.17 Cotrel smoke precipitator.

4.   Dialysis : Kidney removes urea and other unwanted electrolytes from the impure blood by passing it through a dialyzing membrane which holds back the colloidal blood. A kidney failure sends these toxic wastes into the blood. Patients having kidney problem are dialyzed externally.

5.   Purification of water : The clay particles present in the muddy water are removed by the addition of alum (contains Al³+ ions) which coagulated them leaving a clear water.

6.   Sewage disposal : The dirt particles present in the sewage water are in the colloidal form. These are removed in the presence of a high voltage and the clear water free from sewage sludge is let out into the irrigation fields. The sludge is also used as a manure.

7.   Cleaning action of soap : A cloth gets dirty by the sticking of grease and oil particles which in turn adsorb the dust from the air. Soap is a sodium salt of fatty acid.

It has a polar end and a non polar fatty acid chain. Polar end is water soluble (hydrophilic) while non polar end is oil soluble (hydrophobic). When soap is applied to the cloth the oil soluble end of soap emulsifies with the grease along with the dirt particles sticking to it. Polar ends are present away from the cloth and are water soluble. Hence after the application ol soap to the cloth, washing with excess water removes the emulsified grease, dirt particles by solubilizing the polar end of the emulsified soap,Fig. 1.18.

Fig. 1.18

8.   Other Miscellaneous Uses:

(a)   Photographic plates : Silver bromide emulsions are coated on the photographic plates, films etc.,

(b)   Formation of deltas : Rivers carry silt and other mud particles with them which are negatively charged, when the river water meets sea, the electrolytes in the sea water coagulate the silt forming fertile delta lands.

(c)   Industrial products : Various industrial products as inks, boot polish, creams, paints, rubber lubricants are all colloidal particles.

(d)   Rubber industry : Latex is a negatively charged colloidal solution. Coagulation of latex yields rubber.

(e)   Dairy industry : Dairy products as creams, butter, cheese, milk are all colloidal solutions.

(f)   Leather Industry : Skins and hides have proteins in them in the colloidal state. Skins are first soaked and put in a colloidal solution of tannin, a negatively changed colloid. Tannin enters the skins and mutual coagulation of tannin and protein takes place giving hardness to the leather.

(g)   Stopping bleeding : Blood is a colloid. So shaving cuts and other bleedings are stopped using alum which coagulates the blood forming a clot.

9.   Explanation of some interesting observations

(a)   Blue color of sky : Sun light falling on the earth is partially reflected back by the earth's surface. On its way back this light hits the dust particles present in the atmosphere. The colloidal particles of dust are quite small and are capable of reflecting only blue radiation while the radiations of other colors escape through the sky. This given the sky a blue color.

(b)   Tail of comets : Comets are celestial bodies moving at tremendous speeds. During their motion they leave behind tiny solid particles suspended in air. The light falling on them is scattered leaving a Tyndall cone like structure which we call the tail of comet.

(c)   Artificial rains : Clouds are colloids of tiny water droplets suspended in air. Artificial rains are caused by spraying a sol or an electrolyte that coagulates these water droplets into rain and this process is called seedling of clouds.

Short and Essay Type Questions

Self Test Questions

Chapter 2

Environmental Chemistry

2.1 Introduction

Consequences of introduction of any substance that disturbs destroys the purity or ecological balance of the nature is the subject matter of environmental chemistry. Study of environmental chemistry covers the sources, transport, absorption, biological control and remedies of various chemical species pumped into air, water, soil etc., out of human activity. Universe was never free from pollution but was in a low profile till the advent of industrialization, started just 300 years ago. In these three centuries, especially in the last century, earth was dumped with several hazardous chemicals, radioactive waste, concrete jungles, smoking chimneys, vehicles, etc., and polluted to such an extent that billions of yesteryears could not do.

The mankind has now marched to a point of no return where problems connected with population explosion and materialistsic comforts of the modem civilization cannot be sacrificed and human race is left with the only option of using their means judiciously and change their life styles to cause minimum pollution. This awareness is the heart of environmental chemistry.

We notice four main reasons for the present difficulties;

2.2 Pollutant and Contaminant

We have a small difference between a pollutant and contaminant.

Pollutant : Pollutant is a naturally existing substance introduced in greater than natural abundance into environment as a result of human activity, and has a detrimental affect on the living world, e.g., Toxic metals, carbon monoxide, sulphur dioxide, carbon dioxide, dust, etc.

Contaminant : Contaminant is a substance of synthetic origin or not present in a described surroundings and is introduced into environment as a result of human activity. Example : Oil spills that often take place due to wreckage of ships or tankers and leakage of harmful gases like MIC (Methy l isocyanate) that claimed a number of lives in Bhopal tragedy are the cases of few harmful contaminants. Polyethylene textiles, plastic carry bags, disposable syringes that are made out of biologically nondegradable materials are a menace in the environment but not directly harmful contaminants. When a contaminant assumes a detrimental effect on the environment or human health then the contaminant is termed as a pollutant.

2.3 Types of Pollution

Depending upon the place of occurrence, pollutants are classified into (i) Air pollution, (ii) Water pollution, (iii) Soil pollution.

2.3.1 Air Pollution

In the high school chemistry itself we are clear that air is composed of 78.09% of N2, 20.94% of O2, 0.93% of Ar and the remaining trace volume fractions of gases like CO2, CH4, He, Ne, etc. Introduction of any new toxic gas or unbalancing the natural composition may be termed as air pollution. The most important and most frequently occurring air pollutants, arranged according to their physical state, are given in Table 2.1.

Table 2.1 Air pollutants and their physical states.

Out of the big list of pollutants given in Table 2.1, the five primary pollutants which contribute to 90% of the global air pollution are (i) CO, (ii) ΝΟχ, (iii) SOX, (iv) Hydrocarbon and (v) Particulates.

A detailed account of the nature of above pollutants, their sources, sinks and detrimental effects are discussed in the following sections.

Man made air pollution in urban areas in often referred to as smog. The major source of air pollutions conies from automobiles and contribute for approximately two third of CO, one half of the hydrocarbons and nitrogen oxides. In addition engineering industries, chemical industries and power plants are responsible one fourth of the total air pollution. The air pollutants mainly cause lung and throat irritation