Chemistry

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Colloid

Milk is an emulsified colloid of liquid butterfat globules dispersed within a water-based fluid.
 
A colloid is a type of chemical mixture in which one substance is dispersed evenly throughout another.[1] The particles of the dispersed substance are only suspended in the mixture, unlike in a solution, in which they are completely dissolved. This occurs because the particles in a colloid are larger than in a solution - small enough to be dispersed evenly and maintain a homogeneous appearance, but large enough to scatter light and not dissolve. Because of this dispersal, some colloids have the appearance of solutions. 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.
Many familiar substances are colloids, as shown in the chart below. As well as these naturally occurring colloids, modern chemical process industries utilise high shear mixing technology to create novel colloids.
The subsequent table compares particle(s) diameters of colloids, homogeneous and heterogeneous mixture:
Particle size
less than 10−9 m 10−9 – 10−6 m greater than 10−6 m
homogenous mixture
colloids
non-homogeneous mixtures
Thus, colloid suspensions are intermediate between homogeneous and heterogeneous mixtures. They are sometimes classified as either "homogeneous" or "heterogeneous" based upon their appearance.
The dispersed-phase particles have a diameter of between approximately 5 and 200 nanometers.[2] Such particles are normally invisible to 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.
Colloidal systems (also called colloidal solutions or colloidal suspensions) are the subject of interface and colloid science. This field of study was introduced in 1861 by Scottish scientist Thomas Graham.

Classification of colloids

Because the size of the dispersed phase may be difficult to measure, and because colloids have the appearance of solutions, colloids are sometimes identified and characterized by their physico-chemical and transport properties. For example, if a colloid consists of a solid phase dispersed in a liquid, the solid particles will not diffuse through a membrane, whereas with a solution the dissolved ions or molecules will diffuse through a membrane.
Colloids can be classified as follows:
Medium / Phases Dispersed Phase
Gas
Liquid
Solid
Continuous Medium Gas
NONE
(All gases are mutually miscible)
Liquid Aerosol
Examples: fog, mist, hair sprays
Solid Aerosol
Examples: smoke, cloud, air particulates
Liquid
Foam
Example: whipped cream
Emulsion
Examples: milk, mayonnaise, hand cream
Sol
Examples: pigmented ink, blood
Solid
Solid Foam
Examples: aerogel, styrofoam, pumice
Gel
Examples: agar, gelatin, jelly, silicagel, opal
Solid Sol
Example: cranberry glass
In some cases, a colloid can be considered as a homogeneous mixture. This is because the distinction between "dissolved" and "particulate" matter can be sometimes a matter of approach.

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.
Many hydrocolloids are derived from natural sources. For example, agar-agar and carrageenan are extracted from seaweed, gelatin is produced by hydrolysis of proteins of bovine and fish origins, and pectin is extracted from citrus peel and apple pomace.
Gelatin desserts like jelly or Jell-O are made from gelatin powder, another effective hydrocolloid. Hydrocolloids are employed in food mainly to influence texture or viscosity (e.g., a sauce).
Hydrocolloid-based medical dressings are used for skin and wound treatment.

Interaction between colloid particles

The following forces play an important role in the interaction of colloid particles:
  • Excluded volume repulsion: This refers to the impossibility of any overlap between hard particles.
  • Electrostatic interaction: Colloidal particles often carry an electrical charge and therefore attract or repel each other. The charge of both the continuous and the dispersed phase, as well as the mobility of the phases are factors affecting this interaction.
  • van der Waals forces: This is due to interaction between two dipoles that are either permanent or induced. Even if the particles do not have a permanent dipole, fluctuations of the electron density gives rise to a temporary dipole in a particle. This temporary dipole induces a dipole in particles nearby. The temporary dipole and the induced dipoles are then attracted to each other. This is known as van der Waals force, and is always present (unless the refractive indexes of the dispersed and continuous phases are matched), is short-range, and is attractive.
  • Entropic forces: According to the second law of thermodynamics, a system progresses to a state in which entropy is maximized. This can result in effective forces even between hard spheres.
  • Steric forces between polymer-covered surfaces or in solutions containing non-adsorbing polymer can modulate interparticle forces, producing an additional steric repulsive force (which is predominantly entropic in origin) or an attractive depletion force between them. Such an effect is specifically searched for with tailor-made superplasticizers developed to increase the workability of concrete and to reduce its water content.

Stabilization of a colloidal dispersion (peptization)

Stabilization serves to prevent colloids from aggregating. Steric stabilization and electrostatic stabilization are the two main mechanisms for colloid stabilization. Electrostatic stabilization is based on the mutual repulsion of like electrical charges. In general, different phases have different charge affinities, so that a electrical double layer forms at any interface. Small particle sizes lead to enormous surface areas, and this effect is greatly amplified in colloids. In a stable colloid, mass of a dispersed phase is so low that its buoyancy or kinetic energy is too weak to overcome the electrostatic repulsion between charged layers of the dispersing phase. The charge on the dispersed particles can be observed by applying an electric field: All particles migrate to the same electrode and therefore must all have the same sign charge.

Destabilizing a colloidal dispersion (flocculation)

Unstable colloidal dispersions form flocs as the particles aggregate due to interparticle attractions. In this way photonic glasses can be grown. This can be accomplished by a number of different methods:
  • Removal of the electrostatic barrier that prevents aggregation of the particles. This can be accomplished by the addition of salt to a suspension or changing the pH of a suspension to effectively neutralize or "screen" the surface charge of the particles in suspension. This removes the repulsive forces that keep colloidal particles separate and allows for coagulation due to van der Waals forces.
  • Addition of a charged polymer flocculant. Polymer flocculants can bridge individual colloidal particles by attractive electrostatic interactions. For example, negatively-charged colloidal silica or clay particles can be flocculated by the addition of a positively-charged polymer.
  • Addition of non-adsorbed polymers called depletants that cause aggregation due to entropic effects.
  • Physical deformation of the particle (e.g., stretching) may increase the van der Waals forces more than stabilization forces (such as electrostatic), resulting coagulation of colloids at certain orientations.
Unstable colloidal suspensions of low-volume fraction form clustered liquid suspensions, wherein individual clusters of particles fall to the bottom of the suspension (or float to the top if the particles are less dense than the suspending medium) once the clusters are of sufficient size for the Brownian forces that work to keep the particles in suspension to be overcome by gravitational forces. However, colloidal suspensions of higher-volume fraction form colloidal gels with viscoelastic properties. Viscoelastic colloidal gels, such as bentonite and toothpaste, flow like liquids under shear, but maintain their shape when shear is removed. It is for this reason that toothpaste can be squeezed from a toothpaste tube, but stays on the toothbrush after it is applied.

Technique monitoring colloidal stability

Multiple light scattering coupled with vertical scanning is the most widely used technique to monitor the dispersion state of a product, hence identifying and quantifying destabilisation phenomena[3][4][5][6]. It works on concentrated dispersions without dilution. When light is send through the sample, it is backscattered by the particles / droplets. The backscattering intensity is directly proportional to the size and volume fraction of the dispersed phase. Therefore, local changes in concentration (e.g.Creaming and Sedimentation) and global changes in size (e.g.flocculation, coalescence) are detected and monitored.
Measurement principle of multiple light scattering coupled with vertical scanning

Accelerating methods for shelf life prediction

The kinetic process of destabilisation can be rather long (up to several months or even years for some products) and it is often required for the formulator to use further accelerating methods in order to reach reasonable development time for new product design. Thermal methods are the most commonly used and consists in increasing temperature to accelerate destabilisation (below critical temperatures of phase inversion or chemical degradation). Temperature affects not only the viscosity, but also interfacial tension in the case of non-ionic surfactants or more generally interactions forces inside the system. Storing a dispersion at high temperatures enables to simulate real life conditions for a product (e.g. tube of sunscreen cream in a car in the summer), but also to accelerate destabilisation processes up to 200 times. Mechanical acceleration including vibration, centrifugation and agitation are sometimes used. They subject the product to different forces that pushes the particles / droplets against one another, hence helping in the film drainage. However, some emulsions would never coalesce in normal gravity, while they do under artificial gravity[7] . Moreover segregation of different populations of particles have been highlighted when using centrifugation and vibration[8].

Colloids as a model system for atoms

In physics, colloids are an interesting model system for atoms. Micrometre-scale colloidal particles are large enough to be observed by optical techniques such as confocal microscopy. Many of the forces that govern the structure and behavior of matter, such as excluded volume interactions or electrostatic forces, govern the structure and behavior of colloidal suspensions. For example, the same techniques used to model ideal gases can be applied to model the behavior of a hard sphere colloidal suspension. In addition, phase transitions in colloidal suspensions can be studied in real time using optical techniques, and are analogous to phase transitions in liquids.

Colloidal crystals

Electron micrograph of a colloidal solid composed of amorphous hydrated colloidal silica (particle diameter 600 nm)
 
A colloidal crystal is a highly ordered array of particles that can be formed over a very long range (typically on the order of a few millimeters to one centimeter) and that appear analogous to their atomic or molecular counterparts.[9] One of the finest natural examples of this ordering phenomenon can be found in precious opal, in which brilliant regions of pure spectral color result from close-packed domains of amorphous colloidal spheres of silicon dioxide (or silica, SiO2).[10][11] These spherical particles precipitate in highly siliceous pools in Australia and elsewhere, and form these highly ordered arrays after years of sedimentation and compression under hydrostatic and gravitational forces. The periodic arrays of submicrometre spherical particles provide similar arrays of interstitial voids, which act as a natural diffraction grating for visible light waves, particularly when the interstitial spacing is of the same order of magnitude as the incident lightwave.[12][13]
Thus, it has been known for many years that, due to repulsive Coulombic interactions, electrically charged macromolecules in an aqueous environment can exhibit long-range crystal-like correlations with interparticle separation distances, often being considerably greater than the individual particle diameter. In all of these cases in nature, the same brilliant iridescence (or play of colors) can be attributed to the diffraction and constructive interference of visible lightwaves that satisfy Bragg’s law, in a matter analogous to the scattering of X-rays in crystalline solids.
The large number of experiments exploring the physics and chemistry of these so-called “colloidal crystals” has emerged as a result of the relatively simple methods that have evolved in the last 20 years for preparing synthetic monodisperse colloids (both polymer and mineral) and, through various mechanisms, implementing and preserving their long-range order formation. One of the best examples is the Gilson Opal.[14].

Colloids in biology

In the early 20th century, before enzymology was well understood, colloids were thought to be the key to the operation of enzymes; i.e., the addition of small quantities of an enzyme to a quantity of water would, in some fashion yet to be specified, subtly alter the properties of the water so that it would break down the enzyme's specific substrate,[citation needed] such as a solution of ATPase breaking down ATP. Furthermore, life itself was explainable in terms of the aggregate properties of all the colloidal substances that make up an organism. As more detailed knowledge of biology and biochemistry developed, the colloidal theory was replaced by the macromolecular theory, which explains an enzyme as a collection of identical huge molecules that act as very tiny machines, freely moving about between the water molecules of the solution and individually operating on the substrate, no more mysterious than a factory full of machinery. The properties of the water in the solution are not altered, other than the simple osmotic changes that would be caused by the presence of any solute. In humans, both the thyroid gland and the intermediate lobe (pars intermedia) of the pituitary gland contain colloid follicles.

Colloids in the environment

Colloidal particles can also serve as transport vector [15] of diverse contaminants in the surface water (sea water, lakes, rivers, fresh water bodies) and in underground water circulating in fissured rocks [16] (limestone, sandstone, granite, ...). Radionuclides and heavy metals easily sorb onto colloids suspended in water. Various types of colloids are recognised: inorganic colloids (clay particles, silicates, iron oxy-hydroxides, ...), organic colloids (humic and fulvic substances). When heavy metals or radionuclides form their own pure colloids, the term "Eigencolloid" is used to designate pure phases, e.g., Tc(OH)4, U(OH)4, Am(OH)3. Colloids have been suspected for the long-range transport of plutonium on the Nevada Nuclear Test Site. They have been the subject of detailed studies for many years. However, the mobility of inorganic colloids is very low in compacted bentonites and in deep clay formations [17] because of the process of ultrafiltration occurring in dense clay membrane. [18] The question is less clear for small organic colloids often mixed in porewater with truly dissolved organic molecules. [19]

Tyndall Effect

Tyndall observed this phenomenon in 1869. He observed that when a beam of light is allowed to pass through a colloidal solution, the path of light gets illuminated. This phenomenon is known as Tyndall Effect. It occurs because light is scattered by particles present in colloidal solution. The intensity of the scattered light depends on the difference between the refractive indices of the dispersed phase and the dispersion medium. Greater is the difference, greater the intensity of light.
colloid
Figure shows Tyndall Effect in which light is scattered by a colloidal solution in first beaker. Second beaker contains only water (pure solution) and does not show Tyndall Effect. Tyndall Effect can be used to distinguish between Colloidal Solution and pure solution
In case of lyophilic solution, the colloidal particles are highly solvated, which results into lower difference in refractive index of two phases. In lyophilic solution, Tyndall effect is not pronounced. In case of lyophobic solution, the difference is quite large and it shows Tyndall effect.

Brownian Movement

There are continuous collisions between the colloidal particles and molecules of dispersion medium which are in constant motion and passes kinetic energy to colloidal particles by striking it from all sides. This results into zigzag movement of colloidal particles. This zigzag movement of colloidal particles is known as Brownian movement.
Brownian movement of Colloidal Particles
Brownian movement of Colloidal Particles

Colligative Property

Colligative properties depend upon the number of moles of solute present in given mass of solvent. It does not depend on nature of solute particles. Colloidal particles are not simple molecules, they are aggregations of molecules. Hence, all colloidal dispersions give low value of osmotic pressure, depression in freezing point and elevation in boiling point.

Electrophoresis

The movement of colloidal particles under the influence of electric field is called Electrophoresis. When an electric field is applied across the colloidal solution, the colloidal particles migrate to oppositely charged electrode where they get neutralized. This phenomenon is known as electrophoresis.

Electro Osmosis

When electrophoresis of dispersed particle in a colloidal system is prevented by some suitable means, it is observed that dispersion medium itself begins to move in an electric field. This phenomenon is known as electro osmosis.


Applications of Colloids
     --are unlimited. Colloids find its applications in everyday life phenomena. Some of important applications of colloids are discussed.


Purification of water

Water contains colloidal impurities .These impurities can be weeded out by using electrolyte like Alum. Alum is positively charged Al3+ ion which attracts negatively charged colloidal impurities. These neutralized particles settle down and pure water is decanted off.  Thus Alum is used to remove dirt and impurities present in the colloidal solution.

Food Items

Large numbers of food articles which we use in our daily life are colloidal in nature. For example, milk, butter and ice creams are colloidal in nature.

Medicine

Most of the medicines are colloidal in nature. Colloidal calcium and gold are administered by injections to raise the vitality of human system.

Smoke Precipitation using Cottrell precipitator

Colloidal particles of Smoke and dust are major source of pollution in big industrial cities. Smoke precipitation is technique of precipitating smoke particles present in air.
Smoke particles are the electrically charged colloidal particle suspended in air. To remove these particles from air, Cottrell precipitator is used. Cottrell precipitator uses principle of electrophoreses (movement of colloidal particles under influence of electric field) to weed out smoke particles. Air containing smoke and dust particles are allowed to pass through metal electrodes present inside Cottrell precipitator. These charged particles moves towards oppositely charged electrodes and get deposited there from which they are scrapped mechanically.

Sewage disposal

Dirt and mud particles are electrically charged. By applying electric field in sewage tank, dirt particles reach the oppositely charged electrode, get neutralized and are coagulated. These coagulated particles are suspended in solution and are easily removed.

Artificial rain

Colloids find another application in producing artificial rain. Cloud consists of charged particles of water dispersed in air. These particles are neutralized by spraying oppositely charged particles over a cloud. These neutralized particles of water combine to form large water drops. Thus, artificial rain is caused by the aggregation of minute particles of water to form large particles.

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