Adsorption is the adhesion of atoms, ions, or molecules from a gas, liquid, or dissolved solid to a surface.

[1] This process creates a film of the adsorbate on the surface of the adsorbent. This process differs from absorption, in which a fluid (the absorbate) permeates or is dissolved by a liquid or solid (the absorbent).[2] Note that adsorption is a surface-based process while absorption involves the whole volume of the material. The term sorption encompasses both processes, while desorption is the reverse of adsorption. It is a surface phenomenon.

.[4] The word "adsorption" was coined in 1881 by German physicist Heinrich Kayser (18531940).[5]s

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.

Freundlich Main article: Freundlich equation

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, is the mass of the adsorbent, is the pressure of adsorbate and and are empirical constants for each adsorbent-adsorbate pair at a given temperature. The function is not adequate at very high pressure because in reality has an asymptotic maximum as pressure increases without bound. As the temperature increases, the constants and change to reflect the empirical observation that the quantity adsorbed rises more slowly and higher pressures are required to saturate the surface.
Langmuir : Langmuir equation

Irving Langmuir was the first to derive a scientifically based adsorption isotherm in 1918.[6] The model applies to gases adsorbed on solid surfaces. It is a semi-empirical isotherm with a kinetic basis and was derived based on statistical thermodynamics. It is the most common isotherm equation to use due to its simplicity and its ability to fit a variety of adsorption data. It is based on four assumptions:
1. 2. 3. 4. All of the adsorption sites are equivalent and each site can only accommodate one molecule. The surface is energetically homogeneous and adsorbed molecules do not interact. There are no phase transitions. At the maximum adsorption, only a monolayer is formed. Adsorption only occurs on localized sites on the surface, not with other adsorbates.

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 (non-microporous) surfaces. The Langmuir isotherm is nonetheless the first choice for most models of adsorption, and has many applications in surface kinetics (usually called LangmuirHinshelwood 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 k1. 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. For very low pressures and for high 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), for a straight line: and we obtain an expression

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 we have: as the fraction of empty sites and

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.

BET BET theory

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:
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.
Kisliuk

Two adsorbate nitrogen molecules adsorbing onto a tungsten adsorbent from the precursor state around an island of previously adsorbed adsorbate (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 (19222008) in 1957.[7] 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 that has already formed on the surface, it has a sticking probability reflected by the size of the SE constant 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:

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:

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.

Adsorbents
Characteristics and general requirements

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 that enables fast tr gaseous vapors. Most industrial adsorbents fall into one of three classes:

ansport of the

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.

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.

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 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 than 500 C (930 F). This high temperature heat treatment breaks the aluminum-oxygen bonds and the aluminum atom is expelled from the zeolite framework.
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, 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.

Protein adsorption of biomaterials

Protein adsorption is a process that has a fundamental role in the field of biomaterials. Indeed, biomaterial surfaces in contact with biological media, such as blood or serum, are immediately coated by proteins. Therefore, living cells do not interact directly with the biomaterial surface, but with the adsorbed proteins layer. This protein layer mediates the interaction between biomaterials and cells, translating biomaterial physical and chemical properties into a "biological language".[8] In fact, cell membrane receptors bind to protein layer bioactive sites and these receptor-protein binding events are transduced, through the cell membrane, in a manner that stimulates specific intracellular processes that then determine cell adhesion, shape, growth and differentiation. Protein adsorption is influenced by many surface properties such as surface wettability, surface chemical composition [9] and surface nanometre-scale morphology.[10]

Adsorption chillers
Combining an adsorbent with a refrigerant, adsorption chillers use heat to provide a cooling effect. This heat, in the form of hot water, may come from any number of industrial sources including waste heat from industrial processes, prime heat from solar thermal installations or from the exhaust or water jacket heat of a piston engine or turbine. Although there are similarities between absorption and adsorption refrigeration, the latter is based on the interaction between gases and solids. The adsorption chamber of the chiller is filled with a solid material (for example zeolite, silica gel, alumina, active carbon and certain types of metal salts), which in its neutral state has adsorbed the refrigerant. When heated, the solid desorbs (releases) refrigerant vapour, which subsequently is cooled and liquefied. This liquid refrigerant then provides its cooling effect at the evaporator, by absorbing external heat and turning back into a vapour. In the final stage the refrigerant vapour is (re)adsorbed into the solid.[11] As an adsorption chiller requires no moving parts, it is relatively quiet.

Portal site mediated adsorption

Portal site mediated adsorption is a model for site-selective activated gas adsorption in metallic catalytic systems that contain a variety of different adsorption sites. In such systems, low-coordination "edge and corner" defect-like sites can exhibit significantly lower

adsorption enthalpies than high-coordination (basal plane) sites. As a result, these sites can serve as "portals" for very rapid adsorption to the rest of the surface. The phenomenon relies on the common "spillover" effect (described below), where certain adsorbed species exhibit high mobility on some surfaces. The model explains seemingly inconsistent observations of gas adsorption thermodynamics and kinetics in catalytic systems where surfaces can exist in a range of coordination structures, and it has been successfully applied to bimetallic catalytic systems where synergistic activity is observed. In contrast to pure spillover, portal site adsorption refers to surface diffusion to adjacent adsorption sites, not to non-adsorptive support surfaces. The model appears to have been first proposed for carbon monoxide on silica-supported platinum by Brandt et al. (1993).[12] A similar, but independent model was developed by King and co-workers[13][14][15] to describe hydrogen adsorption on silica-supported alkali promoted ruthenium, silver-ruthenium and copper-ruthenium bimetallic catalysts. The same group applied the model to CO hydrogenation (FischerTropsch synthesis).[16] Zupanc et al. (2002) subsequently confirmed the same model for hydrogen adsorption on magnesiasupported caesium-ruthenium bimetallic catalysts.[17] Trens et al. (2009) have similarly described CO surface diffusion on carbon-supported Pt particles of varying morphology.[18]

Adsorption spillover
In the case catalytic or adsorbent systems where a metal species is dispersed upon a support (or carrier) material (often quasi-inert oxides, such as alumina or silica), it is possible for an adsorptive species to indirectly adsorb to the support surface under conditions where such adsorption is thermodynamically unfavorable. The presence of the metal serves as a lowerenergy pathway for gaseous species to first adsorb to the metal and then diffuse on the support surface. This is possible because the adsorbed species attains a lower energy state once it has adsorbed to the metal, thus lowering the activation barrier between the gas phase species and the support-adsorbed species. Hydrogen spillover is the most common example of an adsorptive spillover. In the case of hydrogen, adsorption is most often accompanied with dissociation of molecular hydrogen (H2) to atomic hydrogen (H), followed by spillover of the hydrogen atoms present. The spillover effect has been used to explain many observations in heterogeneous catalysis and adsorption.[19]

Polymer adsorption
Main article: polymer adsorption

Adsorption of molecules onto polymer surfaces is central to a number of applications, including development of non-stick coatings and in various biomedical devices. Polymers may also be adsorbed to surfaces through polyelectrolyte adsorption.

Absorption vs Adsorption

Absorption is the process in which a fluid is dissolved by a liquid or a solid (absorbent). Adsorption is the process in which atoms, ions or molecules from a substance (it could be gas, liquid or dissolved solid) adhere to a surface of the adsorbent. Adsorption is a surfacebased process where a film of adsorbate is created on the surface while absorption involves the entire volume of the absorbing substance.

Improve this chart

Absorption Assimilation of molecular species throughout the bulk of the solid or liquid is termed as absorption.

Adsorption Accumulation of the molecular species at the surface rather than in the bulk of the solid or liquid is termed as adsorption. It is a surface phenomena. Exothermic process It is favoured by low temperature It steadily increases and reach to equilibrium

Definition:

Phenomenon: It is a bulk phenomena Heat exchange: Endothermic process Temperature: It is not affected by temperature Rate of reaction: It occurs at a uniform rate.

Carbon Adsorption on wiseGEEK:

Since groundwater accounts for 95% of the freshwater resources in the United States, groundwater resources are monitored by the Environmental Protection Agency (EPA), which governs groundwater cleanup in the event of environmental contamination. Some different methods of groundwater cleanup include bioremediation, carbon adsorption, air stripping, and the physical removal of contaminated substances. Groundwater remediation is one of the environmental remediation services required to prevent further contamination of the world's underground water supply. The most common methods used are bioremediation, carbon adsorption, and air stripping. Bioremediation involves introducing organisms to the affected groundwater so they can eat the contaminants. Adsorption is the accumulation or concentration of liquid or gas molecules (adsorbate) over the surface of a solid or a liquid (adsorbent). It is a surface phenomenon. Adsorbate: The gas or liquid that is accumulated over the surface of a liquid or solid is known as adsorbate. Adsorbent: The solid or liquid on whose surface, molecules of other substance are adsorbed. Solids, particularly in finely divided state, have large surface area and therefore act as good adsorbents. E.g. activated charcoal, silica gel, alumina gel, clay, colloids, metals in finely divided state, etc.

Illustration: If a gas is taken in a closed vessel containing finely powdered charcoal, it is observed that the pressure of the gas in the enclosed vessel decreases. It is due to accumulation of gas molecules over the surface of charcoal. Note: The charcoal is acting as adsorbent and gas as adsorbate.

Desorption: The reverse of adsorption is called as desorption.

ENERGETICS OF ADSORPTION
The surface atoms or molecules of adsorbent are relatively unstable due to positive surface free energy. Unlike in the bulk, there are unbalanced residual forces at the surface as the molecules at the surface are not symmetrically surrounded by other molecules. Hence they have tendency to attract adsorbate molecules and retain them to minimize the surface energy. Adsorption is an exothermic process (i.e., H = -ve) i.e., heat is liberated since new bonds are formed. However entropy of the system is also decreased (i.e., Ssys = -ve) due to decrease in the number of microstates and decrease in the freedom of movement of molecules. Hence adsorption is thermodynamically more favourable at low temperatures. Note: The value of G becomes negative, only at low temperatures, when both H and Ssys are negative. Therefore, in general, at higher temperatures, the bonds between adsorbate and adsorbent are weakened and the reverse of adsorption i.e. desorption is favored.

ADSORPTION VS ABSORPTION
Adsorption is different from absorption. Absorption involves the diffusion of molecules of a substance into the bulk of liquid or solid to form a solution. E.g., Hydrogen gas is absorbed into the bulk of palladium metal, which is also known as occlusion.

Absorption is a bulk phenomenon, whereas adsorption is a surface phenomenon. Sorption: If both adsorption and absorption occurs simultaneously, the process is called as sorption. Sorption = Adsorption + Absorption

TYPES OF ADSORPTION
Depending on the type of attractions between adsorbate and adsorbent, the adsorption can be divided into two types.

1) Physical adsorption or Physisorption:

If the adsorbate molecules are attracted by weak van der Waals forces towards the adsorbent molecules, the adsorption is known as physical adsorption or physisorption. Characteristics of physisorption: * Energetics & kinetics: Physisorption is an exothermic process. However it is characterized by low enthalpy values (20 40 kJ mol-1), due to weak van der Waals forces of attraction. The activation energy for physisorption is also very low and hence it is practically a reversible process. * Effect of temperature: Since physical adsorption is an exothermic process, it occurs more readily at lower temperatures and decreases with increase in temperature (Le-Chatelier's Principle). * Effect of pressure: In case of physisorption of gases over solids, the extent of adsorption increases with increase in pressure as the volume of the gases decrease during adsorption (Le-Chatelier's Principle).
During adsorption, the volume of gases decreases along with the liberation of heat. Hence at high pressures and low temperatures, adsorption is favored. Whereas at low pressures and high temperatures, desorption is favored.

* Specificity: Since the van der Waals forces are universal, a given surface of an adsorbent does not show any preference for an adsorbate in physisorption i.e. it is not specific with respect to adsorbent. * Nature of adsorbate: However, the extent of adsorption depends on the nature of gas (adsorbate). In general, easily liquefiable gases with higher critical temperatures) are readily adsorbed as the van der Waals forces are stronger, especially, near the critical temperatures. E.g. Sulphur dioxide (critical temperature 630K) is adsorbed more than methane (critical temperature 190K) over activated charcoal under given set of conditions. * Surface area of adsorbent: The extent of adsorption increases with the increase of surface area of the adsorbent. Hence finely powdered metals and porous substances having large surface areas perform well as adsorbents.
2) Chemical adsorption or Chemisorption:

If the adsorbate molecules are bound to the surface of adsorbent by chemical bonds, the adsorption is known as chemical adsorption or chemisorption. Characteristics of chemisorption: * Energetics & kinetics: Chemisorption is also an exothermic process and the enthalpy values are higher (80-240 kJ mol-1) as it involves formation of chemical bonds. However, the activation energy for chemisorption is high and occurs slowly. Hence it is also called activated adsorption. It is practically irreversible. * Effect of temperature: Even though chemical adsorption is an exothermic process, it does not occurs slowly at lower temperature due to high kinetic energy barrier. Hence, like most chemical changes, the extent of chemisorption increases with increase in temperature up to certain limit and then after that it starts decreasing. It is also observed that, in some cases, physisorption of a gas adsorbed at low temperature may change into chemisorption at a high temperatures.

* Effect of pressure: The chemisorption is not appreciably affected by small changes in pressure. However, very high pressures are favourable for chemisorption. * High specificity: Chemisorption is highly specific and occurs only if there is some possibility of chemical bonding between adsorbent and adsorbate. E.g. Oxygen is adsorbed on metals due to formation of oxide. * Surface area: Like physisorption, chemisorption also increases with increase of surface area of the adsorbent.

Surface Chemistry - TOC What is Adsorption?

Catalysis >

Adsorption is the phenomenon of accumulation of large number of molecular species at the surface of liquid or solid phase in comparison to the bulk.
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. 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 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.
Facts about Adsorption Process 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.
Types of Adsorption

Forces of attraction exist between adsorbate and adsorbent. These forces of attraction can be due to Vanderwaal forces of attraction which are weak forces or due to chemical bond which are strong forces of attraction. On the basis of type of forces of attraction existing between adsorbate and adsorbent, adsorption can be classified into two types: Physical Adsorption or Chemical Adsorption.
Physical Adsorption or Physisorption

When the force of attraction existing between adsorbate and adsorbent are weak Vanderwaal forces of attraction, the process is called Physical Adsorption or Physisorption. Physical Adsorption takes place with formation of multilayer of adsorbate on adsorbent. It has low enthalpy of adsorption i.e. Hadsorption is 20-40KJ/mol. It takes place at low temperature below boiling point of adsorbate.As the temperature increases in, process of Physisorption decreases.

Physical Adsorption vs. Temperature graph

Chemical Adsorption or Chemisorption

When the force of attraction existing between adsorbate and adsorbent are chemical forces of attraction or chemical bond, the process is called Chemical Adsorption or Chemisorption. Chemisorption takes place with formation of unilayer of adsorbate on adsorbent. It has high enthalpy of adsorption i.e.

It can take place at all temperature. With the increases in temperature, Chemisorption first increases and then decreases.

Chemical Adsorption vs. Temperature Graph

Adsorption Isotherm

The process of Adsorption is usually studied through graphs called as adsorption isotherm. It is the graph between the amounts of adsorbate (x) adsorbed on the surface of adsorbent (m) and pressure at constant temperature.
Applications of Adsorption

1. Charcoal is used as a decoloriser as it adsorbs the coloring matter from the coloured solution of sugar.

Pic Credit : Link 2. Silica gel adsorbs moisture from the desiccators.

Pic Credit : Link 3. Silica and alumina gels are used as adsorbents for removing moisture and for controlling humidity of rooms. 4. Activated charcoal is used in gas masks as it adsorbs all the toxic gases and vapours and purifies the air for breathing.

Pic Credit : Link 5 .Adsorption processes are useful in carrying out heterogeneous catalysis.
Factors on which Adsorption Depends Temperature

Adsorption increases at low temperature conditions.

Adsorption process is exothermic in nature. According to Le Chatleir principle, low temperature conditions would favour the forward direction.
Pressure

As depicted by Adsorption Isotherm, with the increases in pressure, adsorption increases up to a certain extent till saturation level is achieved. After saturation level is achieved no more adsorption takes place no matter how high the pressure is applied.
Surface Area

Adsorption is a surface phenomenon therefore it increases with increase in surface area.

Activation of Adsorbent

Activation of adsorbent surface is done so as to provide more number of vacant sites on surface of adsorbent. This can be done by breaking solid crystal in small pieces, heating charcoal at high temperature, breaking lump of solid into powder or other methods suitable for particular adsorbent.

Surface Area of Adsorbent

As adsorption is a surface phenomenon, surface area offered by Adsorbent becomes important factor for consideration. Volume of an ideal gas at STP = 22.4 L= 22.4 dm Also the number of gaseous molecules present at STP = 6.023*10 molecules Vmono be the adsorbed volume of gas at high pressure conditions so as to cover the surface with a unilayer of gaseous molecules. Let the total number of molecules of gas adsorbed corresponding to volume Vmono be N whose value is given as

Now area of a molecule having density and occupying volume V is calculated as follows

Where Vm is the total volume of the surface Now Total volume Vm is equal to volume of each molecule (V) multiplied by total number of molecule (NA) adsorbed on the surface at volume, V.

Molecule being spherical in nature, Volume of the molecule V is also given as

The radius, r occupied by each gas molecule is

Area occupied by each gas molecule is

This is the area occupied by one molecule. If the value multiplied by the total number of molecules adsorbed on the surface of adsorbent we will get the total surface area of the adsorbent.

Or,

Link To Adsorption :

<a href='http://w w w .chemistrylearni

ADSORPTION OF GASES ON SOLIDS ADSORPTION OF GASES ON SOLIDS The magnitude of adsorption of gases by solids depends on the following factors. 1. Nature of the adsorbent 2. The surface area of the adsorbent 3. Nature of the gases 4. Pressure of the gas 5. Temperature of the gas 6. Reversible character of the adsorbed gases 7. Activation of the adsorbent 8. Enthalpy of adsorption Factors infleunce adsorption of gases on solids 1. Nature of the adsorbent The adsorption depends upon the type of adsorbent used. The excellent adsorbents are highly porous in nature. The larger the pores, the greater is the adsorption. Ex : porous substances are silica gel, aluminia and charcoal. The adsorption power of these substances can further be enhanced by a pores called activation. During activation, the adsorbent is heated in steam to about 1500c. Heating drives out all impurities and leads to a lager free surface for adsorption. Ex. Charcoal adsorbs 0.011 gms of CCl4 at 24C. Activated charcoal adsorbs 1.48 gm of at 24C. The surface area of adsorbent

The extent of adsorption depends on the surface area. 1. The greater the surface area, the greater is the adsorption. 2. Larger pores on the adsorbent, larger is the adsorption. Ex. Charcoal and silica gel ( excellent adsorbents). Nature of gases The amount of gas adsorbed by a solid depends on the nature of the gas. Easily liquefiable gases like Hl, NH3, Cl2, SO2 etc., are adsorbed more easily then the permanent gases like H2, N2, O2 etc., This is due to the following reasons : i. Critical temperature The ease of liquifications depends on its critical temperature (i.e, the maximum temperature above which a gas cannot be liquefied). Thus if the critical temperature of the gas is more, it will be liquefied and adsorbed more readily. Ex. Adsorption of various gases on 1g of activated charcoal. ii. Vander waals forces Easily liquefiable gases possess greater vander waals forces than permanent gases, so they are adsorbed more readily. Posted by lokina at 1:40 AM Labels: Adsorption of gases on solids, critical temperature, Factors infleunce adsorption of gases on solids, Vanderwaal's forces No comments: Post a Comment

Factors Affecting Adsorption of Gases by Solids: Almost all the solids adsorb gases to some extent. However, the exact amount of a gas adsorbed depends upon a number of factors, as briefly explained below: 1. Nature of surface area of the adsorbent: It is observed that the same gas is adsorbed to different extents by different solids at the same temperature. Further, as may be expected, the greater the surface area of the adsorbent, greater is the volume of the gas adsorbed. It is for this reason that substances like charcoal and silica gel are excellent adsorbents because they have highly porous structures and hence large surface area. The surface area per gram of the adsorbent is called specific area. 2. Nature of the gas being adsorbed: Different gases are adsorbed to different extents by the same adsorbent at the same temperature. Higher the critical temperature of a gas, greater is the amount of that gas adsorbed. In other words, a gas which is more easily liquefiable or is more soluble in water is more readily adsorbed.

3. Temperature: We know that adsorption decreases with increase of temperature and vice versa. For example, one gram of charcoal adsorbs about 10 cm3 of N2 at 273 K, 20 cm3 at 244 K and 45 cm3 at 195 K. the decrease of adsorption with increase of temperature is explained below: Like any other equilibrium, adsorption is a process involving a true equilibrium. The two opposing processes involved are condensation i.e. adsorption of the gas molecules on the surface of the solid and evaporation i.e. desorption of the gas molecules from the surface of the solid into the gaseous phase. The amount of heat evolved when one mole of the gas is adsorbed on the adsorbent is called the heat of adsorption. 4. Pressure: At constant temperature, the adsorption of a gas increases with increase of pressure. It is observed that at low temperature, the adsorption of a gas increases very rapidly as the pressure is increased from small values. 5. Activation of the solid adsorbent: It means increasing the adsorbing power of an adsorbent. This is usually done by increasing the surface are of the adsorbent which can be achieved by any of the following ways: a) By making the surface of the adsorbent rough: For example: by mechanical rubbing or by chemical action or by depositing finely dispersed metals on the surface of the adsorbent by electroplating. b) By substituting the adsorbent into smaller pieces or grains: No doubt this method increases the surface area but it has a limitation that is if the adsorbent is broken into too fine particles that it becomes almost powder, then the penetration of the gas becomes difficult and this will obstruct adsorption. c) By removing the gases already adsorbed: For example: charcoal is activated by heating in superheated steam or in vacuum at a temperature ranges from 623 K to 1273 K.
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Category: Surface Chemistry

hat is Adsorption Isotherm?

The process of Adsorption is usually studied through graphs know as adsorption isotherm. It is the graph between the amounts of adsorbate (x) adsorbed on the surface of adsorbent (m) and pressure at constant temperature. Different adsorption isotherms have been Freundlich, Langmuir and BET theory.
Basic Adsorption Isotherm

In the process of adsorption, adsorbate gets adsorbed on adsorbent.

According to Le-Chatelier principle, the direction of equilibrium would shift in that direction where the stress can be relieved. In case of application of excess of pressure to the equilibrium system, the equilibrium will shift in the direction where the number of molecules decreases. Since number of molecules decreases in forward direction, with the increases in pressure, forward direction of equilibrium will be favored.

Basic Adsorption Isotherm From the graph, we can predict that after saturation pressure Ps, adsorption does not occur anymore. This can be explained by the fact that there are limited numbers of vacancies on the surface of the adsorbent. At high pressure a stage is reached when all the sites are occupied and further increase in pressure does not cause any difference in adsorption process. At high pressure, Adsorption is independent of pressure.
Freundlich Adsorption Isotherm

In 1909, Freundlich gave an empirical expression representing the isothermal variation of adsorption of a quantity of gas adsorbed by unit mass of solid adsorbent with pressure. This

equation is known as Freundlich Adsorption Isotherm or Freundlich Adsorption equation or simply Freundlich Isotherm.

Where x is the mass of the gas adsorbed on mass m of the adsorbent at pressure p and k, n are constants whose values depend upon adsorbent and gas at particular temperature. Though Freundlich Isotherm correctly established the relationship of adsorption with pressure at lower values, it failed to predict value of adsorption at higher pressure.
Langmuir Adsorption Isotherm

In 1916 Langmuir proposed another Adsorption Isotherm known as Langmuir Adsorption isotherm. This isotherm was based on different assumptions one of which is that dynamic equilibrium exists between adsorbed gaseous molecules and the free gaseous molecules.

Where A(g) is unadsorbed gaseous molecule, B(s) is unoccupied metal surface and AB is Adsorbed gaseous molecule. Based on his theory, he derived Langmuir Equation which depicted a relationship between the number of active sites of the surface undergoing adsorption and pressure.

Where the number of sites of the surface which are covered with gaseous molecule, P represents pressure and K is the equilibrium constant for distribution of adsorbate between the surface and the gas phase .The basic limitation of Langmuir adsorption equation is that it is valid at low pressure only. At lower pressure, KP is so small, that factor (1+KP) in denominator can almost be ignored. So Langmuir equation reduces to = KP At high pressure KP is so large, that factor (1+KP) in denominator is nearly equal to KP. So Langmuir equation reduces to

BET adsorption Isotherm

BET Theory put forward by Brunauer, Emmett and Teller explained that multilayer formation is the true picture of physical Adsorption. One of the basic assumptions of Langmuir Adsorption Isotherm was that adsorption is monolayer in nature. Langmuir adsorption equation is applicable under the conditions of low pressure. Under these conditions, gaseous molecules would possess high thermal energy and high escape velocity. As a result of this less number of gaseous molecules would be available near the surface of adsorbent. Under the condition of high pressure and low temperature, thermal energy of gaseous molecules decreases and more and more gaseous molecules would be available per unit surface area. Due to this multilayer adsorption would occur. The multilayer formation was explained by BET Theory. The BET equation is given as

The another form of BET equation is

Where Vmono be the adsorbed volume of gas at high pressure conditions so as to cover the surface with a unilayer of gaseous molecules,

the ratio is designated C. K1 is the equilibrium constant when single molecule adsorbed per vacant site and KL is the equilibrium constant to the saturated vapor liquid equilibrium.
Type of Adsorption Isotherm

Five different types of adsorption isotherm and their characteristics are explained below.

Type I Adsorption Isotherm

Where Vmono be the adsorbed volume of gas at high pressure conditions so as to cover the surface with a unilayer of gaseous molecules,

the ratio is designated C. K1 is the equilibrium constant when single molecule adsorbed per vacant site and KL is the equilibrium constant to the saturated vapor liquid equilibrium.
Type of Adsorption Isotherm

Five different types of adsorption isotherm and their characteristics are explained below.
Type I Adsorption Isotherm

Type I Adsorption Isotherm

The above graph depicts Monolayer adsorption. This graph can be easily explained using Langmuir Adsorption Isotherm. If BET equation, when P/P0<<1 and c>>1, then it leads to monolayer formation and Type I Adsorption Isotherm is obtained. Examples of Type-I adsorption are Adsorption of Nitrogen (N2) or Hydrogen (H) on charcoal at temperature near to -1800C.

Type II Adsorption Isotherm

Type II Adsorption Isotherm

Type II Adsorption Isotherm shows large deviation from Langmuir model of adsorption. The intermediate flat region in the isotherm corresponds to monolayer formation. In BET equation, value of C has to be very large in comparison to 1. Examples of Type-II adsorption are Nitrogen (N2 (g)) adsorbed at -1950C on Iron (Fe) catalyst and Nitrogen (N2 (g)) adsorbed at -1950C on silica gel.

Type III Adsorption Isotherm

Type III Adsorption Isotherm

Type III Adsorption Isotherm also shows large deviation from Langmuir model. In BET equation value if C <<< 1 Type III Adsorption Isotherm obtained. This isotherm explains the formation of multilayer. There is no flattish portion in the curve which indicates that monolayer formation is missing. Examples of Type III Adsorption Isotherm are Bromine (Br2) at 790C on silica gel or Iodine (I2) at 790C on silica gel.

Type IV Adsorption Isotherm

Type IV Adsorption Isotherm

At lower pressure region of graph is quite similar to Type II. This explains formation of monolayer followed by multilayer. The saturation level reaches at a pressure below the saturation vapor pressure .This can be explained on the basis of a possibility of gases getting condensed in the tiny capillary pores of adsorbent at pressure below the saturation pressure (PS) of the gas. Examples of Type IV Adsorption Isotherm are of adsorption of Benzene on Iron Oxide (Fe2O3) at 500C and adsorption of Benzene on silica gel at 500C.

Type V Adsorption Isotherm

Type V Adsorption Isotherm

Explanation of Type V graph is similar to Type IV. Example of Type V Adsorption Isotherm is adsorption of Water (vapors) at 1000C on charcoal. Type IV and V shows phenomenon of capillary condensation of gas.

What are the 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: 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: 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.

Applications of Adsorption
Some of the applications of adsorption are as follows: a. Activates charcoal is used in gas masks to remove poisonous gases such as carbon monoxide, methane etc. Animal charcoal is used to remove colouring matter from sugarcane juice in the manufacture of sugar. b. Ion exchange resin is used to remove hardness of water. c. Several organic compounds are purified by chromatographic adsorption. d. Silica gel is used for removing and controlling humidity. e. The catalytic effect of a number of catalysts like spongy iron (in the manufacture of ammonia) and nickel, platinum or palladium (used in the reduction of unsaturated hydrocarbons is based on the principle of adsorption. f. Production of high vacuum. g. Gas masks-It is a device which consists of activated charcoal. This is used to adsorb poisonous gases. h. Humidity control-Silica gel and aluminium gel are used for this purpose. i. Removal of colouring matter from solutions-Animal charcoal is used for decolorising cane sugar. j. Heterogeneous catalysis k. Separation of inert gases by coconut charcoal l. Softening of hard water m. De-jionising of water n. Cleaning agents o. Froth floatation process p. Adsorption indicators q. Chromatographic analysis r. In curing diseases.