1.

INTRODUCTION
Adsorption is the adhesion of atoms, ions, or molecules from a gas, liquid, or dissolved solid to a surface. This process creates a film of the adsorbate on the surface of the adsorbent. This process differs from absorption, in which a fluid (theabsorbate) permeates or is dissolved by a liquid or solid (the absorbent). Note that adsorption is a surface-based process while absorption involves the whole volume of the material. The term sorption encompasses both processes, whiledesorption is the reverse of adsorption. It is a surface phenomenon.

Brunauer, Emmett and Teller's model of multilayer adsorption is a random distribution of molecules on the material surface
Similar to surface tension, adsorption is a consequence of surface energy. In a bulk material, all the bonding requirements of the constituent atoms of the material are filled by other atoms in the material. However, atoms on the surface of the adsorbent are not wholly surrounded by other adsorbent atoms and therefore can attract adsorbates. The exact nature of the bonding depends on the details of the species involved, but the adsorption process is generally classified as physisorption or chemisorption . It may also occur due to electrostatic attraction. Adsorption is present in many natural physical, biological, and chemical systems, and is widely used in industrial applications such as activated charcoal, capturing and using waste heat to provide cold water for air conditioning and other process requirements (adsorption chillers), synthetic resins, increase storage capacity of carbide-derived carbons for tunable nanoporous carbon, and water purification. Adsorption, ion exchange, and chromatography are sorption processes in which certain adsorbates are selectively transferred from the fluid phase to the surface of
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insoluble, rigid particles suspended in a vessel or packed in a column. Lesser known, are the pharmaceutical industry applications as a means to prolong neurological exposure to specific drugs or parts thereof.

2. ISOTHERMS
Adsorption is usually described through isotherms, that is, the amount of adsorbate on the adsorbent as a function of its pressure (if gas) or concentration (if liquid) at constant temperature. The quantity adsorbed is nearly always normalized by the mass of the adsorbent to allow comparison of different materials. 2.1 Freundlich The first mathematical fit to an isotherm was published by Freundlich and Kster (1894) and is a purely empirical formula for gaseous adsorbates,

where

is the quantity adsorbed, and

is the mass of the adsorbent,

is the pressure

of adsorbate and

are empirical constants for each adsorbent-adsorbate pair and change

at a given temperature. The function has an asymptotic maximum as pressure increases without bound. As the temperature increases, the constants higher pressures are required to saturate the surface. 2.2 Langmuir In 1916, Irving Langmuir published a new model isotherm for gases adsorbed to solids, which retained his name. It is a semi-empirical isotherm derived from a proposed kinetic mechanism. It is based on four assumptions: 1. The surface of the adsorbent is uniform, that is, all the adsorption sites are equivalent. 2. Adsorbed molecules do not interact. 3. All adsorption occurs through the same mechanism. to reflect the empirical observation that the quantity adsorbed rises more slowly and

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4. At the maximum adsorption, only a monolayer is formed: molecules of adsorbate do not deposit on other, already adsorbed, molecules of adsorbate, only on the free surface of the adsorbent. These four assumptions are seldom all true: there are always imperfections on the surface, adsorbed molecules are not necessarily inert, and the mechanism is clearly not the same for the very first molecules to adsorb to a surface as for the last. The fourth condition is the most troublesome, as frequently more molecules will adsorb to the monolayer; this problem is addressed by the BET isotherm for relatively flat (nonmicroporous) surfaces. The Langmuir isotherm is nonetheless the first choice for most models of adsorption, and has many applications in surface kinetics (usually called Langmuir-Hinshelwood kinetics) and thermodynamics. Langmuir suggested that adsorption takes place through this mechanism: , where A is a gas molecule and S is an adsorption site. The direct and inverse rate constants are k and k-1. If we define surface coverage, , as the fraction of the adsorption sites occupied, in the equilibrium we have:

or

where

is the partial pressure of the gas or the molar concentration of the solution. and for high pressures

For very low pressures

is difficult to measure experimentally; usually, the adsorbate is a gas and the quantity adsorbed is given in moles, grams, or gas volumes at standard temperature and pressure (STP) per gram of adsorbent. If we call vmon the STP volume of adsorbate required to form a monolayer on the adsorbent (per gram of adsorbent), and we obtain an expression for a straight line:
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Through its slope and y-intercept we can obtain vmon and K, which are constants for each adsorbent/adsorbate pair at a given temperature. vmon is related to the number of adsorption sites through the ideal gas law. If we assume that the number of sites is just the whole area of the solid divided into the cross section of the adsorbate molecules, we can easily calculate the surface area of the adsorbent. The surface area of an adsorbent depends on its structure; the more pores it has, the greater the area, which has a big influence on reactions on surfaces. If more than one gas adsorbs on the surface, we define sites and we have: as the fraction of empty

Also, we can define

as the fraction of the sites occupied by the j-th gas:

where i is each one of the gases that adsorb. 2.3 BET Often molecules do form multilayers, that is, some are adsorbed on already adsorbed molecules and the Langmuir isotherm is not valid. In 1938 Stephen Brunauer, Paul Emmett, and Edward Teller developed a model isotherm that takes that possibility into account. Their theory is called BET theory, after the initials in their last names. They modified Langmuir's mechanism as follows:
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A(g) + S AS A(g) + AS A2S A(g) + A2S A3S and so on

Langmuir isotherm (red) and BET isotherm (green)

The derivation of the formula is more complicated than Langmuir's (see links for complete derivation). We obtain:

x is the pressure divided by the vapor pressure for the adsorbate at that temperature
(usually denoted ), v is the STP volume of adsorbed adsorbate, vmon is the STP volume of the amount of adsorbate required to form a monolayer and c is the equilibrium constant K we used in Langmuir isotherm multiplied by the vapor pressure of the adsorbate. The key assumption used in deriving the BET equation that the successive heats of adsorption for all layers except the first are equal to the heat of condensation of the adsorbate. The Langmuir isotherm is usually better for chemisorption and the BET isotherm works better for physisorption for non-microporous surfaces. 2.4 Kisliuk

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Two adsorbate nitrogen molecules adsorbing onto a tungsten adsorbent from the precursor state around an island of previously adsorbed adsobate (left) and via random adsorption (right
In other instances, molecular interactions between gas molecules previously adsorbed on a solid surface form significant interactions with gas molecules in the gaseous phases. Hence, adsorption of gas molecules to the surface is more likely to occur around gas molecules that are already present on the solid surface, rendering the Langmuir adsorption isotherm ineffective for the purposes of modelling. This effect was studied in a system where nitrogen was the adsorbate and tungsten was the adsorbent by Paul Kisliuk (b. 1922-d. 2008) in 1957. To compensate for the increased probability of adsorption occurring around molecules present on the substrate surface, Kisliuk developed the precursor state theory, whereby molecules would enter a precursor state at the interface between the solid adsorbent and adsorbate in the gaseous phase. From here, adsorbate molecules would either adsorb to the adsorbent or desorb into the gaseous phase. The probability of adsorption occurring from the precursor state is dependent on the adsorbates proximity to other adsorbate molecules that have already been adsorbed. If the adsorbate molecule in the precursor state is in close proximity to an adsorbate molecule which has already formed on the surface, it has a sticking probability reflected by the size of the SEconstant and will either be adsorbed from the precursor state at a rate of kEC or will desorb into the gaseous phase at a rate of kES. If an adsorbate molecule enters the precursor state at a location that is remote from any other previously adsorbed adsorbate molecules, the sticking probability is reflected by the size of the SD constant. These factors were included as part of a single constant termed a "sticking coefficient," kE, described below:

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As SD is dictated by factors that are taken into account by the Langmuir model, SD can be assumed to be the adsorption rate constant. However, the rate constant for the Kisliuk model (R) is different to that of the Langmuir model, as R is used to represent the impact of diffusion on monolayer formation and is proportional to the square root of the systems diffusion coefficient. The Kisliuk adsorption isotherm is written as follows, where (t) is fractional coverage of the adsorbent with adsorbate, and t is immersion time:

Solving for (t) yields:

2.5 Henderson-Kisliuk

The Henderson-Kisliuk adsorption equation prediction of normalised impedance as a function of adsorption time, where the first peak corresponds to the formation of an adsorbent surface that is saturated with MPA in its "lying down" structure. The curve then tends to an impedance value that is representative of an adsorbent saturated with "standing up" structure
This adsorption isotherm was developed for use with the new field of Self Assembling Monolayer (SAM) adsorption. SAM molecules adsorb to the surface of an adsorbent until the surface becomes saturated with the SAM molecules' hydrocarbon chains lying flat against the adsorbate. This is termed "lying down" structure (1st structure). Further adsorption then occurs, causing the hydrocarbon chains to be displaced by
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thiol groups present on the newly adsorbed SAM molecules. When this adsorption step takes place, electrostatic forces between the newly adsorbed SAM molecules and the ones previously adsorbed, causes a new structure to form, where all of the SAM molecules are occupying a "standing up" orientation (2nd structure). As further adsorption takes place, the entire adsorbent becomes saturated with SAM in a standing up orientation, and no further adsorption takes place. The SAM adsorbate is usually present in a liquid phase and the adsorbent is normally a solid. Hence, intermolecular interactions are significant and the Kisliuk adsorption isotherm applies. The sequential evolution of "lying down" and "standing up" mercaptopropionic acid (MPA) SAM structures on a gold adsorbent, from a liquid MPA-ethanol adsorbate phase, was studied by Andrew P. Henderson (b. 1982) et al. in 2009. Henderson et al. used electrochemical impedance spectroscopy to quantify adsorption and witnessed that the 1st structure had different impedance properties to the 2nd structure and that both structures evolved sequentially. This allowed four rules to be expressed:

That the amount of adsorbate on the adsorbent surface was equal to the sum of the adsorbate occupying 1st structure and 2nd structure. The rate of 1st structure formation is dependent on the availability of potential adsorption sites and intermolecular interactions. The amount of 1st structure is depleted as 2nd structure is formed. The rate of second structure formation is dictated by the amount of adsorbate occupying 1st structure and intermolecular interactions at immersion time, t.

From these statements, Henderson et al. used separate terms to describe rate of fractional adsorption for 1st structure [1(t)] and 2nd structure [2(t)] as a function of immersion time (t). Both of these terms were dictated by the Kisliuk adsorption isotherm, where variables with a subscript of 1 relate to 1st structure formation and a subscript of 2 relates to 2nd structure formation.

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These terms were combined in the Henderson adsorption isotherm, which determines the total normalised impedance detection signal strength caused by the adsorbate monolayer (z(t)) as a function of 1(t), 2(t), 1 and 2. Values of are weighting constants, which are normalized signal values that would result from an adsorbent covered entirely with either 1st structure or 2nd structure. This isotherm equation is shown below: Although the Henderson-Kisliuk adsorption isotherm was originally applied to SAM adsorption, Henderson et al. hypothesised that this adsorption isotherm is potentially applicable to many other cases of adsorption and that 1(t) and 2(t) can be calculated using other adsorption isotherms, in place of the Kisliuk model (such as the Langmuir adsorption isotherm equation). 2.6 Adsorption enthalpy Adsorption constants are equilibrium constants, therefore they obey van 't Hoff's equation:

As can be seen in the formula, the variation of K must be isosteric, that is, at constant coverage. If we start from the BET isotherm and assume that the entropy change is the same for liquefaction and adsorption we obtain that is to say, adsorption is more exothermic than liquefaction. ,

3. ADSORBENTS
3.1 Characteristics and general requirements

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Activated carbon is used as an adsorbent Adsorbents are used usually in the form of spherical pellets, rods, moldings, or monoliths with hydrodynamic diameters between 0.5 and 10 mm. They must have high abrasion resistance, high thermal stability and small pore diameters, which results in higher exposed surface area and hence high surface capacity for adsorption. The adsorbents must also have a distinct pore structure which enables fast transport of the gaseous vapors. Most industrial adsorbents fall into one of three classes:

Oxygen-containing compounds Are typically hydrophilic and polar, including materials such as silica gel and zeolites. Carbon-based compounds Are typically hydrophobic and non-polar, including materials such as activated carbon and graphite. Polymer-based compounds - Are polar or non-polar functional groups in a porous polymer matrix.

3.2 Silica gel Silica gel is a chemically inert, nontoxic, polar and dimensionally stable (< 400 C or 750 F) amorphous form of SiO2. It is prepared by the reaction between sodium silicate and acetic acid, which is followed by a series of after-treatment processes such as aging, pickling, etc. These after treatment methods results in various pore size distributions. Silica is used for drying of process air (e.g. oxygen, natural gas) and adsorption of heavy (polar) hydrocarbons from natural gas. 3.3 Zeolites Zeolites are natural or synthetic crystalline aluminosilicates which have a repeating pore network and release water at high temperature. Zeolites are polar in nature. They are manufactured by hydrothermal synthesis of sodium aluminosilicate or another silica source in an autoclave followed by ion exchange with certain cations (Na+, Li+, Ca2+, K+, NH4+). The channel diameter of zeolite cages usually ranges from 2

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to 9 (200 to 900 pm). The ion exchange process is followed by drying of the crystals, which can be pelletized with a binder to form macroporous pellets. Zeolites are applied in drying of process air, CO2 removal from natural gas, CO removal from reforming gas, air separation, catalytic cracking, and catalytic synthesis and reforming. Non-polar (siliceous) zeolites are synthesized from aluminum-free silica sources or by dealumination of aluminum-containing zeolites. The dealumination process is done by treating the zeolite with steam at elevated temperatures, typically greater than500 C (930 F). This high temperature heat treatment breaks the aluminum-oxygen bonds and the aluminum atom is expelled from the zeolite framework. 3.4 Activated carbon Activated carbon is a highly porous, amorphous solid consisting of microcrystallites with a graphite lattice, usually prepared in small pellets or a powder. It is non-polar and cheap. One of its main drawbacks is that it is reacts with oxygen at moderate temperatures (over 300 C).

Activated carbon nitrogen isotherm showing a marked microporous type I behavior

Activated carbon can be manufactured from carbonaceous material, including coal (bituminous, subbituminous, and lignite), peat, wood, or nutshells (e.g., coconut). The manufacturing process consists of two phases, carbonization and activation. The carbonization process includes drying and then heating to separate by-products,
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including tars and other hydrocarbons from the raw material, as well as to drive off any gases generated. The process is completed by heating the material over 400 C (750 F) in an oxygen-free atmosphere that cannot support combustion. The carbonized particles are then "activated" by exposing them to an oxidizing agent, usually steam or carbon dioxide at high temperature. This agent burns off the pore blocking structures created during the carbonization phase and so, they develop a porous, three-dimensional graphite lattice structure. The size of the pores developed during activation is a function of the time that they spend in this stage. Longer exposure times result in larger pore sizes. The most popular aqueous phase carbons are bituminous based because of their hardness, abrasion resistance, pore size distribution, and low cost, but their effectiveness needs to be tested in each application to determine the optimal product. Activated carbon is used for adsorption of organic substances and non-polar adsorbates and it is also usually used for waste gas (and waste water) treatment. It is the most widely used adsorbent since most of its chemical (e.g. surface groups) and physical properties (e.g. pore size distribution and surface area) can be tuned according to what is needed. Its usefulness also derives from its large micropore (and sometimes mesopore) volume and the resulting high surface area.

4. HOW ADSORPTION OCCURS?

The process of adsorption arises due to presence of unbalanced or residual forces at the surface of liquid or solid phase. These unbalanced residual forces have tendency to attract and retain the molecular species with which it comes in contact with the surface. Adsorption is essentially a surface phenomenon. Adsorption is a term which is completely different from Absorption .While absorption means uniform distribution of the substance throughout the bulk, adsorption essentially happens at the surface of the substance. When both Adsorption and Absorption processes take place simultaneously, the process is called sorption.

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Adsorption process involves two components Adsorbent and Adsorbate. Adsorbent is the substance on the surface of which adsorption takes place.Adsorbate is the substance which is being adsorbed on the surface of adsorbent. Adsorbate gets adsorbed. Adsorbate + Adsorbent gives rise to Adsorption

Oxygen molecules (red) adsorb on a bimetallic surface of platinum (purple) and cobalt (green). From P. B. Balbuena, D. Altomare, L. Agapito, and J. M. Seminario, Theoretical analysis of oxygen adsorption on Pt-based clusters alloyed with Co, Ni, or Cr embedded in a Pt matrix, J. Phys. Chem. B (in press). Some modern techniques have been used to study surface. 1. Low energy electron diffraction (LEED). 2. Photo electron spectroscopy (PES). 3. Scanning Tunneling microscopy (STM). Adsorption in liquids Adsorption can be understood by considering a simple example. In case of liquid state, water molecule present on the surface is attracted inwards by the molecules of water present in the bulk. This gives rise to surface tension. While the molecule of water
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present within the bulk is equally attracted from all the sides and the net force experienced by the water molecule in bulk is zero. This clearly shows that particles at surface and particles at the bulk are in different environment.

Water molecule on surface experiencing unbalanced forces as compared to molecule inside which experiences forces from all direction.
Adsorption in solids In case of solid state these residual forces arises because a of unbalanced valence forces of atoms at the surface. The generation of these forces on solid surface can be explained diagrammatically as follows:

Cleavage of a big crystal into smaller unit

Due to cleavage of a big crystal into smaller unit, residual forces or vacancies gets generated on the surface of the solid. Occupancy of these vacancies by some other molecular species results into Adsorption.

4. FACTS ABOUT ADSORPTION PROCESS

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Adsorption is a spontaneous process

For reaction or process to be spontaneous, there must be decreases in free energy of the system i.e. G of the system must have negative value. Also we know, G = H TS And during this process of adsorption, randomness of the molecule decreases which S is negative. We can rewrite above equation as Therefore for a reaction to be spontaneous H has to be negative and

Adsorption is an exothermic process

Adsorption process takes place by adsorbate getting adsorbed on adsorbent .Forces of attraction exist between adsorbate and adsorbent and due to these forces of attraction, heat energy is released. So adsorption is an exothermic process.

5. TYPES OF ADSORPTION
Adsorption can be classified into two categories as described below, (1) Depending upon the concentration : In adsorption the concentration of one substance is different at the surface of the other substance as compared to adjoining bulk or interior phase. (i) Positive adsorption : If the concentration of adsorbate is more on the surface as compared to its concentration in the bulk phase then it is called positive adsorption. Example :When a concentrated solution of KCl is shaken with blood charcoal, it shows positive adsorption. (ii) Negative adsorption : If the concentration of the adsorbate is less than its concentration in the bulk then it is called negative adsorption. Example :When a dilute solution of KCl is shaken with blood charcoal, it shows negative adsorption. (2) Depending upon the nature of force existing between adsorbate molecule and adsorbent
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(i) Physical adsorption : If the forces of attraction existing between adsorbate and adsorbent are Vander Waals forces, the adsorption is called physical adsorption. This type of adsorption is also known as physisorption or Vander Waals adsorption. It can be easily reversed by heating or decreasing the pressure. (ii) Chemical adsorption :If the forces of attraction existing between adsorbate particles and adsorbent are almost of the same strength as chemical bonds, the adsorption is called chemical adsorption. This type of adsorption is also called as chemisorption or Langmuir adsorption. This type of adsorption cannot be easily reversed.

Comparison between physisorption and chemisorption Physisorption (Vander Waal's adsorption)

Low heat of adsorption usually in range of 20-40kJ/mol Force of attraction areVander Waal's forces. It is reversible It is usually takes place atlow temperature and decreases with increasing temperature.

Chemisorption (Langmuir adsorption)

High heat of adsorption in the range of 50-400 kJ/mol Forces of attraction arechemical bond forces. It is irreversible It takes place at high temperature.

It is related to the case of liquefication It is not related. of the gas. It forms multimolecular layers. It forms monomolecular layers. It does not require any activation It requires high activation energy. energy. High pressure is favourable. Decrease High pressure is favourable. Decrease of pressure causesdesorption of pressure does not cause desorption.

It is not very specific.

It is highly specific.

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6. FACTORS AFFECT THE ADSORPTION

Factors which affect the extent of adsorption : The following are the factors which affect the adsorption,
(1) Nature of the adsorbate (gas) and adsorbent (solid) (i) In general, easily liquefiable gases e.g., CO2, NH3, Cl2 and SO2 etc. are adsorbed to a greater extent than the elemental gases e.g. H2, O2, N2, He etc. (while chemisorption is specific in nature.) (ii) Porous and finely powdered solid e.g. charcoal, fullers earth, adsorb more as compared to the hard non-porous materials. Due to this property powdered charcoal is used in gas masks. (2) Surface area of the solid adsorbent (i) The extent of adsorption depends directly upon the surface area of the adsorbent, i.e. larger the surface area of the adsorbent, greater is the extent of adsorption. (ii) Surface area of a powdered solid adsorbent depends upon its particle size. Smaller the particle size, greater is its surface area. (3) Effect of pressure on the adsorbate gas (i) An increase in the pressure of the adsorbate gas increases the extent of adsorption. (ii) At low temperature, the extent of adsorption increases rapidly with pressure.

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(iii) Small range of pressure, the extent of adsorption is found to be directly proportional to the pressure. (iv) At high pressure (closer to the saturation vapour pressure of the gas), the adsorption tends to achieve a limiting value. (4) Effect of temperature (i) As adsorption is accompanied by evolution of heat, so according to the LeChateliers principle, the magnitude of adsorption should decrease with rise in temperature.

(ii)The relationship between the extent of adsorption and temperature at any constant pressure is called adsorption isobar. (iii) A physical adsorption isobar shows a decrease in x/m (where m is the mass of the adsorbent and x that of adsorbate) as the temperature rises. (iv) The isobar of chemisorption show an increase in the beginning and then decrease as the temperature rises

7. APPLICATIONS OF ADSORPTION
Adsorption finds extensive applications both in research laboratory and in industry. A few applications are discussed below: In preserving vacuum: In Dewar flasks activated charcoal is placed between the walls of the flask so that any gas which enters into the annular space either due to glass imperfection or diffusion though glass is adsorbed. In glass masks:
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All gas masks are devices containing suitable adsorbent so that the poisonous gases present in the atmosphere are preferentially adsorbed and the air for breathing is purified. In clarification of sugar: Sugar is decolorized by treating sugar solution with charcoal powder. The latter adsorbs the undesirable colors present. In paint industry: The paint should not contain dissolved gases as otherwise the paint does not adhere well to the surface to be painted and thus will have a poor covering power. The dissolved gases are therefore, removed by suitable adsorbents during manufacture. Further, all surfaces are covered with layers of gaseous, liquid or solid films. These have to be removed before the paint is applied. This is done by suitable liquids which adsorbs these films. Such liquids are called wetting agents. The use of spirit as wetting agent in furniture painting is well known. In chromatographic analysis: The selective adsorbent of certain substances from a solution by a particular solid adsorbent has helped to develop technique for the separation of the components of the mixture. This technique is called chromatographic analysis. For example: in column chromatography a long and wide vertical tube is filled with a suitable adsorbent and the solution of the mixture poured from the top and then collected one by one from the bottom. In catalysis: The action of certain solids as catalysts is best explained in terms of adsorption. The theory is called adsorption theory. According to this theory, the gaseous reactants are adsorbed on the surface of the solid catalyst. As a result, the concentration of the reactants increases on the surface and hence the rate of reaction increases. The theory is also able to explain the greater efficiency of the catalyst in the finely divided state, the action of catalyst promoters and poisons. In adsorption indicators:
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Various dyes which owe their use to adsorption have been introduced as indicators particularly in precipitation titrations. For example: KBr is easily titrated with AgNO3 using eosin as an indicator. In softening of hard water: The use of ion exchangers for softening of hard water is based upon the principle of competing adsorption just as in chromatography. In removing moisture from air in the storage of delicate instruments: Such instruments which may be harmed by contact with the moist air are kept out of contact with moisture using silica gel.

8. BIBLIOGRAPHY

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