Colloids

A colloid is a substance microscopically dispersed evenly throughout another substance. A colloidal system consists of two separate phases: a dispersed phase (or internal phase) and a continuous phase(or dispersion medium). A colloidal system may be solid, liquid, or gaseous. The dispersed-phase particles have a diameter of between approximately 5 and 200 nanometers.[2] Such particles are normally invisible in an optical microscope, though their presence can be confirmed with the use of an ultramicroscope or an electron microscope. Homogeneous mixtures with a dispersed phase in this size range may be called colloidal aerosols, colloidal emulsions, colloidal foams, colloidal dispersions, or hydrosols. The dispersed-phase particles or droplets are affected largely by the surface chemistry present in the colloid. Some colloids are translucent because of the Tyndall effect, which is the scattering of light by particles in the colloid. Other colloids may be opaque or have a slight color This field of study was introduced in 1861 by Scottish scientist Thomas Graham .

Characteristic features
>> Solute doesn t completely dissolve in solvent but not visible to the naked eye. >> Will Scatter light gives an opaque , turbid appearance >> Exhibits characteristics of a molecular solution (Brownian motion, capacity for diffusion) >> Size 1nm - 0.5nm

Classification of colloids
Colloids can be classified as follows: Dispersed phase Medium / Phases Gas Liquid Solid

Gas

NONE (All gases are mutually miscible)

Liquid aerosol Examples: fog, mist, hair sprays

Solid aerosol Examples: smoke, cloud, air particulates

Continuous medium Liquid

Foam Example: whipped cream, Shaving cream

Emulsion Examples: milk, mayonnaise, hand cream

Sol Examples: pigmented ink, blood

Solid

Solid foam Gel Examples: aerogel, styrofoam, pumice Examples: agar, gelatin, jelly, opal

Solid sol Example: cranberry glass

-> Colloids can also be classified on the basis of interaction between Dispersed phase (DP) & Dispersion medium (DM)

a) Lyophillic colloids / Hydrophilic colloids :
(i) Strong affinity is present between particles of DP & DM. (ii) It¶s reversible because DP & DM can be separated. (iii) It¶s stable & don¶t get easily precipitated. (iv)When DM is water , it¶s called Hydrophilic.

b) Lyophobic colloids / Hydrophobic colloids :
(i) No or very low affinity is present between particles of DP & DM. (ii) It s irreversible because DP & DM can t be separated. (iii) It s very less stable & has tendency to get precipitated out easily. (iv)When DM is water , it s called Hydrophobic.

-> Colloids can be classified on the basis of size of colloidal particle : Multimolecular colloids - Colloidal particle is aggregate of small atom or molecule in which particles are held by van der Waal s force. Macromolecular colloids - Colloidal particles is big molecule or atom like colloidal solution of polymers. This type of colloidal system is very stable. No need of aggregation or subtraction.

Hydrocolloids
A hydrocolloid is defined as a colloid system wherein the colloid particles are dispersed in water. A hydrocolloid has colloid particles spread throughout water, and depending on the quantity of water available that can take place in different states, e.g., gel or sol (liquid). Hydrocolloids can be either irreversible (single-state) or reversible. For example, agar, a reversible hydrocolloid of seaweed extract, can exist in a gel and sol state, and alternate between states with the addition or elimination of heat.

PROPERTIES
The main characteristic properties of colloidal solutions are as follows.

(1) PHYSICAL PROPERTIES

(i) HETEROGENEOUS NATURE: Colloidal sols are heterogeneousin 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 1827that 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 1863that 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: TYNDALL 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 COLLOIDAL SOLUTION. (v) The Tyndall effect has also been observed by an instrument called ULTRA-MICROSCOPE.

(5) ELECTRICAL PROPERTIES
(i) ELECTROPHORESIS (a) The phenomenon of movement of colloidal particles under an applied electric field is called ELECTROPHORESIS. (b) If the particles accumulate near the negative electrode, the charge on the particles is POSITIVE. (c) On the other hand, if the sol particles accumulate near the positive electrode, the charge on the particles is NEGATIVE. (d) The apparatus consists of a U-tube with two Pt-electrodes in each limb.

(e) When electrophoresis of a sol is carried out with out stirring, the bottom layer gradually becomes more concentrated while the top layer which contain pure and concentrated colloidal solution may be decanted. This is called electro decanation and is used for the purification as well as for concentrating the sol. (f) The reverse of electrophoresis is called SEDIMENTATION POTENTIAL or DORN EFFECT. The sedimentation potential is setup when a particle is forced to move in a resting liquid. This phenomenon was discovered by Dorn and is also called Dorn effect.

(ii) ELECTRICAL DOUBLE LAYER THEORY (a) The electrical properties of colloids can also be explained by electrical double layer theory. According to this theory A DOUBLE LAYER OF IONS APPEAR AT THE SURFACE OF THE SOLID. (b) The ion preferentially adsorbed is held in fixed part and imparts charge to colloidal particles. (c) The second part consists of a diffuse mobile layer of ions. This second layer consists of both the type of charges. The net charge on the second layer is exactly equal to that on the fixed part. (d) The existence of opposite sign on fixed and diffuse parts of double layer leads to appearance of a difference of potential, known as ZETA POTENTIAL or ELECTROKINETIC POTENTIAL. Now when electric field is employed the particles move (electrophoresis)

(iii) ELECTRO-OSMOSIS (a) In it the movement of the dispersed particles are prevented from moving by SEMIPERMEABLE MEMBRANE. (b) Electro-osmosis is a phenomenon in which dispersion medium is allowed to move under the influence of an electrical field, whereas colloidal particles are not allowed to move. (c) The existence of electro-osmosis has suggested that when liquid forced through a porous material or a capillary tube, a potential difference is setup between the two sides called as streaming potential. So the reverse of electro-osmosis is called STREAMING POTENTIAL.

STABILITY OF COLLOIDS
Stabilization serves to prevent colloids from aggregating. When a Colloid is stabilized, both phases (dispersed and continuous) repulse each other by electrical forces, this is a property that lays on Coulomb¶s Law. Steric stabilization and electrostatic stabilization are the two main mechanisms for colloid stabilization.

Electrostatic stabilization to remove the electrostatic barrier that prevents the flocking of particles, this is possible by
adding some substance that changes or neutralizes the surface charge of the particles in suspension or changing the ph of the suspension. Stearic stabilization is by flocculating the particles, this means particles interact with a substance that aggregates them, particles become heavier and after precipitation is visible. The behavior of the colloid can be measured by an electrical potential called Z-potential , this allows to know the stability of the colloid. A colloid can also be separated by other methods, this methods involve: -Equivalent diameter: this means we have to use statistical tools to find a standard measure of the particle¶s diameter, this can also be considered in monosized, polisized, and pausizised.

- Proyected Area Diameter: this method can be described as it follows. We can take various pictures to the colloid and find one neat picture of a particle and make some scale to the picture and measure the diameter. -Aerodynamic diameter: this is a physical unitary property which depend on density, used in irregular particles, using the terminal settling ( speed of settling) of particles. -Mechanic Diameter: this a very used method, because it allows to separate particles from the colloid by mechanical methods, collision or adherence, using special tissues.

PREPARATION OF COLLOIDS:
For the preparation of lyophilic and lyophobic sols different methods are used.

Preparation of Lyophilic Sols
Since lyophilic sols are quite stable, they can be easily prepared by shaking the lyophilic substance with the dispersion medium. Examples are: Colloidal sols of gum, starch, gelatine and egg albumin.

Preparation of Lyophobic Sols
Lyophobic sols are prepared by two methods. They are: 1) Condensation methods 2) Dispersion methods.

Condensation methods
In condensation methods particles of atomic or molecular size are induced to combine to form aggregates of colloidal dimensions. To achieve this, chemical as well as physical methods are employed.

a) Chemical methods
Colloidal sols can be prepared by chemical reactions, which involve double decomposition, oxidation, reduction and hydrolysis. Examples of sols made by these methods are given below:
i) Double decomposition

ii) Oxidation

iii) Reduction

iv) Hydrolysis

Sols of silver halides are prepared by mixing dilute solution of silver salts with alkali halides in equivalent amounts. Similarly, silica gel sol is prepared by mixing dilute solutions of sodium silicate and HCl.

b) Physical methods
i) Exchange of solvent
In this method, a true solution in mixed with an excess of another solvent in which the solute is insoluble but the solvent is miscible. For e.g., a solution of sulphur in alcohol mixed with excess of water results in a colloidal sol of sulphur.

ii) By excessive cooling
A colloidal sol of ice in an organic solvent such as CHCl3 or ether is obtained by freezing a solution of water in the solvent. The molecules of water, which can no longer be held in solution separately come together to form particles of colloidal size.

Dispersion methods
In dispersion methods, colloidal particles are obtained by breaking large particles of a substance in the presence of a dispersion medium. Since the sols formed are unstable, they are stabilized by adding stabilizing agents. Some of the dispersion methods are:
a) Mechanical dispersion

b) Electrical disintegration
c) Peptization.

a) Mechanical dispersion
In mechanical dispersion, the coarse suspension of the substance is ground in a colloid mill, a ball mill or an ultrasonic disintegrator. The colloid mill consists of two metal discs, close together and rotating at high speed (7000 revolutions per minute) in opposite directions. By the process of such grinding, the suspension particles are torn off to the colloidal sizes.

b) Electrical disintegration or Bredig's Arc Method
In this method, an electric arc is struck between electrodes of the metal immersed in the dispersion medium.

fig 7.12 - Bredig's arc method
The intense heat produced by the arc vaporizes the metal, which then condenses to form particles of colloidal size. By this method, sols of metals such as gold, silver and platinum can be prepared.

c) Peptization
The process of converting a precipitate into a colloidal sol by shaking it with the dispersion medium, in the presence of a small amount of electrolyte, is called peptization. The electrolyte used is called the peptizing agent. This method is used to convert a freshly prepared precipitate into a colloidal sol.
In the process of peptization, the precipitate adsorbs one of the ion of the electrolyte onto its surface. The ion adsorbed on the surface is generally common with those of the precipitate. Adsorption of ion results in the development of positive or negative charge on precipitates and which ultimately break up into colloidal size particles. For e.g., a precipitate of silver iodide already formed can be dispersed by the addition of potassium iodide. Here potassium iodide is the peptizing agent.

PURIFICATION OF COLLOIDS:
The colloidal solutions prepared by various methods usually contain electrolytes and other soluble substances as impurities. These impurities if not removed can destabilize the sols. Impurities are removed by the following methods: 1) Dialysis 2) Ultra-filtration 3) Ultra-Centrifugation.

1.Dialysis
Removal of soluble impurities from sols by the use of semipermeable membrane is known as dialysis. Solutes present in a true solution can pass through a semipermeable membrane such as parchment paper or cellophane. However, sol particles cannot pass through such membranes. When a bag made up of such a

membrane is filled with the colloidal sol and then placed in fresh water, the soluble particles such as electrolytes pass through the membrane and go into the water leaving behind the colloidal sol. The movement of the ions across the membrane can be enhanced by applying electric potential across two electrodes. This is known as electrodialysis.

fig 7.13 - An apparatus for electrodialysis

2.Ultra-Filtration
In this method, colloidal sols are filtered through graded filters called ultra-filtrers. These filters allow the electrolytes to pass through but not the colloidal particles. These ultra-filters are made from ordinary filter papers by impregnating them with colloidal particles. Filtration is usually carried out by either by applying pressure or by the use of suction.

3.Ultra-Centrifugation
Ultra Centrifugation is used to separate colloidal particles from the impurities by centrifuging the colloidal sol. Centrifugation is carried out in a centrifuging machine where the tube containing the colloidal sol is rotated at very high speeds. The colloidal particles settle down at the bottom of the tube and the impurities remain in the solution called centrifugate. The settled colloidal particles are then mixed with an appropriate dispersing medium to regenerate the sol.

Applications Of Colloids
(i) Cleansing action of soaps & detergents :
A micelle consists of hydrophobic hydrocarbon ± like central core. The cleansing action of soap is due to the fact that soap molecules form micelle around the oil droplet in such a way that hydrophobic part of the stearate ions is in the oil droplet & hyrophillic part projects out of the grease droplet. Since the polar groups can interact with water, the oil droplet surrounded by stearate ions is now pulled in water & removed from the dirty surface. Thus soap helps in emulsification & washing away of oils & fats. The negatively charged sheath around the globules prevents them from coming together & forming aggregates.

(ii) Purification of water :

The water obtained from natural sources often contains suspended impurities. Alum is added to such water to coagulate the suspended impurities & make water fit for dinking purposes.

(iii) Medicines :
Most of the medicines are colloidal in nature. For example argyrols is a silver sol used as an eye lotion, colloidal antimony is used in curing kaalazar etc. Colloidal medicines are more effective because they have large surface area & are therefore easily assimilated.

(iv) Photographic plates & films :
Photographic plates & films are prepared by coating an emulsion of the light sensitive bromide in gelatin over glass plates or celluloid films.

(v) Tanning :
Animal hides are colloidal in nature. When a hide, which has positively charged particles, is soaked in tannin, which contains negatively charged colloidal particles , mutual coagulation takes place. This results in hardening of leather. This process in termed as tanning.

(vi) Rubber Industry :
Latex is colloidal solution of rubber particles which are negatively charged. Rubber is obtained by coagulation of latex.

(vi) Industrial purposes :
Paints, inks, synthetic plastics, rubber, graphite lubricants, cement etc., are all colloidal solutions.

(vii) DIALYSIS
Sometimes, toxic substances build up in the blood because the kidneys are not working efficiently specially in the case of patients suffering from Uremia. In order to clean the blood, it is made to flow across a large cellophane in an artificial kidney or dialyzing machine. This process is known as dialysis. DIALYSIS is the process of separating the contaminated ions and other smaller molecules from the colloidal particles of the blood by letting the true solutes to pass through a semi-permeable membrane.

(viii)Hemodialysis
In HEMODIALYSIS, the bloodstream is diverted from its normal course in the body and pumped through a dialyzing tube with the semi-permeable membrane. An aqueous solution containing ions, such as Na+, K+, and Cl- are of the same concentration as that of the blood on the other side of the dialyzing membrane (isotonic). To prevent blood clotting, an anticlotting agent is added to the dialyzing solution. It is however important that the dialyzing solution is isotonic because that ensures that the solute particles pass in and out of the blood at equal rates, resulting in no net removal of essential components of the blood. In this regard, only the contaminated ions are removed faster than they are returned to the blood. Within a certain time, the procedure reduces the level of toxic substances in the blood..

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