& testbook.com Adsorption: Its Definition, Types, Mechanisms and Applications 2021/09/16 Adsorption is a part of surface chemistry. Surface Chemistry is the study of the chemical phenomena that occur at the surfaces, which can be solid-liquid, solid-gas, solid-vacuum, liquid-gas, ete. In this article, we are going to study Adsorption, its definition, types, Physisorption and Chemisorption Adsorption, Factors affecting the rate of adsorption, Adsorption Isotherm, Freundlich Theory, Langmuir Theory, BET theory, Differences Between Absorption and Adsorption and Applications of Adsorption. Read more about Equilibrium, here. What is Adsorption? ‘The surface of a solid has the tendency to attract and retain the molecules of the phase with which it comes into contact with it. These molecules remain only at the surface and do not go deeper into the bulk. The accumulation of molecular species at the surface rather than in the bulk of a solid or liquid is termed adsorption. Adsorption can take place in many physical, natural, chemical and biological systems. It is used in various industrial applications like the production of synthetic resins, activated charcoal and confining or utilizing waste heat to generate cold water to be used in air conditioning. Examples of Adsorption Gases like Nz, Hz, ete, get adsorbed on the surface of activated charcoal. Condensing water molecules stick to a drinking glass. 2 3, Painting isa form of chemical Adsorption Adsorbate The molecular substance that accumulates at the surface is termed adsorbate. In the above examples, the gases No, H2, Water molecules, paint are Adsorbates. Adsorbent ‘The material on the surface of which the adsorption takes place is called adsorbent. In the above examples, activated charcoal, glass and wall are adsorbents. Read about Emulsions and Suspensions here.VIICTOHGS VCLWOSH AUSUIPEIVE GH AWOUIV UU Properties Absorption Adsorption Definition Assimilation of molecular species Accumulation of the molecular species at the Unroughout the bulk of the solid or surface rather than in the bulk of the solid or liquid is termed absorption. liquid is termed adsorption. Phenomenon | It isa bulk phenomenon Itis a surface phenomenon. Heat exchange | Endothermie process Exothermie process Temperature | Itis not affected by temperature Itis favoured by low temperature Rate of It occurs at a uniform rate. Itsteadily inereases and reaches equilibrium reaction Concentration | Itis the same throughout the material. | Concentration on the surface of the adsorbent is different from that in the bulk Desorption Desorption is the release of adsorbate or absorbed substances, either from the surface of the adsorbent or through the surface absorbent. Desorption can occur when an equilibrium situation is altered, Example: Imagine a tank of water in equilibrium with its surroundings. The amount of oxygen entering and leaving the water from the air will be the same — and the oxygen concentration in the water will be constant. If the water temperature increases, the equilibrium and solubility are changed, and the oxygen will desorb from the water — lowering the oxygen content. Also, check out the notes on Chemical Equation, here. Mechanism of Adsorption When the particle on the surface and the particle in the bulk of the adsorbent are not in the same environment, adsorption occurs. In other words, the net force acting on them is not the same. The particle on the surface or adsorbate has unbalanced forces acting on it which are also called residual attractive forces. During the process of adsorption, charge transfer occurs between the adsorbate and the adsorbent. This results in a dipole moment. Hence, there is the adhesion of ions, atoms and molecules from liquid, gas and dissolved solids to a particular surface. Asa result, an adsorbate film is formed on the adsorbent surface.During adsorption, there is always a decrease in the residual attractive forces of the surface. Itis an exothermic process which means that energy is liberated during this process. The energy of the surface decreases and this appears as heat. This is called the heat of adsorption At constant temperature and pressure, adsorption occurs spontaneously. Spontaneous Adsorption and Gibbs Free Energy ‘The freedom of movement of adsorbate molecules becomes restricted when they are adsorbed on the surface of the adsorbent. Hence, AS the entropy decreases, Gibbs free energy is given by, \Delta{G}=\Delta{H}—T\Delta{S}. For spontaneous adsorption, \Delta{G} must be negative. This ean happen if AH has a significantly high negative value as ~T\Delta{S}. is positive. As the process continues, AH becomes less negative until it becomes equal to TAS. At this point, Equilibrium is, attained. Check more about Surface Chemistry, here. Types of Adsorption There are mainly two types of Adsorption: Physisorption and Chemisorption. Physisorption If the accumulation of gas on the surface of a solid occurs on account of weak van der Waals’ forces, the adsorption is termed physical adsorption or physisorption, Characteristics of Physisorption Itis reversible in nature and is dependent on the pressure as well as temperature. Itis a multi-layered process. Tt ean take place all over the adsorbent. Activation energy is less in physisorption. Itis favourable at lesser temperatures. Physisorption depends on the surface area of the adsorbent. Examples of Physisorption Hz on finely divided nickel as it involves weak van der Waals’ forces. Learn more about Catalysis, here. ChemisorptionWhen the gas molecules or atoms are held to the solid surface by chemical bonds, the adsorption is termed chemical adsorption or chemisorption. It involves high energy of activation and is, therefore, often referred to as activated adsorption. It has a high enthalpy of adsorption of the order of 40 to 400 kJ/mol. Characteristics of Chemisorption It is accompanied by an increase in temperature. The adsorbate and adsorbent get attached by chemical bonds which are either covalent or ionic in nature. High activation energy is required. High temperature is also favourable. Chemisorption is an irreversible proves. Examples of Chemisorption 2. 3. Haber process Hydrogenation of vanaspati ghee Rust or corrosion on the surface of the metal. Check the Development of the Periodic Table here. Factors Affecting Extent and Rates of Adsorption Adsorption occurs on the surface of almost all solids. However, the extent and rates of adsorption of an adsorbate on the surface of an adsorbent vary according to the following factors : 5B Effect of Pressure. Effect of Temperature. The Nature of the Adsorbate. The Nature of the Adsorbent. The Surface Area of the Adsorbent. Let us now discuss these factors briefly. Effect of Pressure In the case of Physisorption, the extent of adsorption increases with an increase in pressure as the volume of the gases decreases during adsorption. In the case of Chemisorption, The chemisorption process occurs slowly at low temperatures and occurs at a higher rate with an increase in pressure. Also, check out notes on VSEPR Theory, here. Effect of TemperatureAt lower temperatures, Physisorption has a high rate as it does not require much energy to form the weak bonds using van der Waals’ forces. At higher temperatures, Chemisorption has a high rate as more energy from the covalent or ionic bonds by exchange of charges. For He on finely divided nickel, at lower temperatures, hydrogen molecules get adsorped by van der Waals’ forces. However, as the temperature increases, hydrogen molecules dissociate into hydrogen atoms which are held on the surface by chemisorption. The Nature of the Adsorbate The gases which are more easily liquefiable or are more soluble in water are more readily adsorbed than others because the intermolecular forces are stronger in more easily liquefiable gases. Hence, they are adsorbed readily. The Nature of the Adsorbent Different adsorbents would adsorb different amounts of the same adsorbates even under similar conditions. The substances that are porous in nature and have rough surfaces are better adsorbents. Hence, Substances like charcoal and silica gel are excellent adsorbents. Read more about Amines, here. The Surface Area of the Adsorbent The extent of adsorption also depends upon the surface area of the solid. The greater the surface area the more is the surface available for adsorption and the greater is the adsorption. Difference between Physisorption and Chemisorption Physisorption Chemisorption Itis also known as physical adsorption. Itis also known as chemical adsorption. Itarises because of van der Waals’ forces. Itis caused by chemical bond formation. Itis not speeific in nature, Itis highly specific in nature Itis reversible in nature. Itis irreversible in nature. It depends on the nature of the gas. More easily | It also depends on the nature of the gas. Gases that can liquefiable gases are adsorbed readily. react with the adsorbent show chemisorption Low temperature is favourable for adsorption. It | High temperature is favourable for adsorption. It decreases with an increase in temperature. increases with the inerease in temperature.Physisorption has a very low adsorption enthalpy | Chemisorption has higher adsorption enthalpy, nearly of nearly about 20 to 40 kJ/mol. about 80 to 240 kJ/mol, than that of physisorption, Physical adsorption has less activation energy. | Chemical adsorption has high activation energy. Know all about Solutions, its Components, Types, Properties here. Adsorption Isotherm An adsorption isotherm is a graph drawn at a constant temperature, It showeases the variation in the amount of adsorbate adsorbed on the surface of the adsorbent with the change in pressure. Adsorption isotherm is the relationship between the adsorbate in the system and the adsorbate adsorbed on the surface of the adsorbent at equilibrium ata constant temperature, & testbook Adsorption isotherm pP— P—— Saturation pressure In the case of solutions, it tells us how the adsorption of a particular adsorbate on a particular adsorbent will be affected by the concentration of the adsorbate. In the ease of adsorption of a gas on solids, there will be an equilibrium established between the molecules in the gas phase and the corresponding adsorbed species which are bound to the surface of the solid. This equilibrium will depend upon 1, The relative stabilities of the adsorbed and gas-phase molecules fo, The temperature of the system. 3g, The pressure of the gas above the surface Adsorption Isotherms are important for Climate and Pollution studies.Adsorption isotherms are essential for the description of how pollutants’ concentration will interact with adsorbent surfaces and are useful to optimize the use of adsorbents for the removal of pollutants from aqueous solutions. Also, check out the notes on Polymers, here. Freundlich Adsorption Isotherm: Freundlich proposed this relation to show a relation between the extent of adsorption and pressure. Freundlich Adsorption Isotherm obeyed when the adsorbate forms a monomolecular layer on the surface of the adsorbent. {x\over{m}}=k(p)*{1/n} logtx\over{m}}=logk-+(1/n)log(p) Where, x: the amount of adsorbate m: mass of adsorbent p: pressure C: concentration of adsorbate Kand n: constants, n>1 always ° log, P—> Limitations of Freundlich Adsorption Isotherm Freundlich Adsorption Isotherm fails at high pressure. It could not explain the multi-layered adsorption process. Langmuir Theory In 1916, Irving Langmuir presented his model for the adsorption of species onto simple surfaces. He hypothesized that a given adsorbent surface has a certain number of equivalent sites to whieh an adsorbate can get adsorbed, either by physisorption or chemisorption.These sites are called elementary sites. Langmuir Theory could only predict linear adsorption at low adsorption densities and at maximum surface coverage at higher solute metal concentrations. ‘The Langmuir adsorption isotherm has the form: {\theta=K_p\over{(1+K_p)}}[/theta] Where, 6: the fraction of the surface covered by the adsorbed molecule. K: an equilibrium constant that is known as adsorption coefficient. (K+ ka/kd = rate constant for adsorption/ rate constant for desorption) p: the pressure. Know more about the Different Atomic Models, here. Assumptions of Langmuir Adsorption Isotherm All surface sites have the same adsorption energy for the adsorbate. The adsorbate is usually argon, krypton or nitrogen gas. ‘The surface site is defined as the area on the sample where one molecule of the gas can adsorb onto. Adsorption of the solvent at one site occurs independently of adsorption at the neighbouring sites. BEEP The activity of adsorbate is directly proportional to its concentration. 5, Adsorbates form « monolayer. Hence, each aetive site ean be oceupied only by one particle, Limitations of Langmuir Adsorption Isotherm Langmuir Adsorption Isotherm is valid only when monolayer adsorption takes place on a homogeneous surface and when there is no interaction between adsorbed molecules. BET Adsorption Isotherm Proposed by Brunauer, Emmett and Teller in 1938, this theory works for both partial and multilayer adsorption. Itaims to explain the physical adsorption of gas molecules on a solid surface, Surface areas are commonly termed as BET surface areas are obtained by applying the theory of Brunauer, Emmett, and Teller2o to nitrogen adsorption isotherms measured at 77 K. ‘The solid a has uniform BET surface areas and adsorption at one area does not affect adsorption at neighbouring areas. ‘The BET theory extends the Langmuir theory to multilayer adsorption. Langmuir Surfaces Vs. BET SurfaceAdsorbate ou: @ A A A A A A A A A A Tle ear le Bae lara @) (b) In BET surface area analysis, nitrogen is usually used because it is readily available in a highly pure state and it has strong interaction abilities with most solids. The BET Equation given below uses the information from the isotherm to determine the surface area of the sample. {u\over{X{(P_o/P)-1]})=(a\over{X_mC}}+{C-1\over{X_mC})({P\over{P_o}}) Where, X is the weight of nitrogen adsorbed at a given relative pressure (P/Po) Xm is monolayer capacity which is the volume of gas adsorbed at standard temperature and pressure (STP). STP is defined as 273 K and 1 atm. Cis constant. Check more important topies of Chemistry here. Applications of Adsorption Adsorption has many uses. Some of them are listed below: 1 2 3. Creating High Vacuum Ahigh vacuum can be created using the adsorption strategy. Airis absorbed by using activated charcoal. Gas Masks: Adsorption is used in the preparation of gas masks. Activated charcoal to adsorb poisonous gases like CO, CH4 ete. in order to prevent people from inhaling them. To Extract Sulphide Ores ‘The Froth floatation method used for the concentration of sulphide ores is based on adsorption.Removal of Moisture 7 Silica Gel or TEG-like gels absorb moisture from the air. Thisis used to control humidity. 5, Dyeing of clothes Mordants are used to absorb dye from colour to achieve the required hue. _ Acommonly used adsorbent is an alum. 6 CIP Gold Extraction . Acommon technique for mining metals is leach mining, where ore is dissolved in a chemical from which the desired metal is extracted. Carbon in Pulp (CIP) isa method to isolate these compounds, which simply involves flowing the dissolved ore through many containers of activated charcoal. ‘The charcoal is then removed from the tanks, where the gold complexes are extracted using high temperatures, or chemicals such as ethanol. >, Metal Finishing ‘A.common metal finishing technique is electroplating, which can completely cover an object with a thin, uniform layer of metal works on the principle of adsorption. s,_ Impurity Removal __ Drinking-Water Filtration: Activated charcoal-based water filter systems can remove Chlorine, Benzene, Lead, Copper, Mercury, Cadmium, Zine, and a large number of other imputities from drinking water. Sewage Treatment: Activated charcoal is often used as a filter for treated sewage. Activated charcoal helps to remove any leftover toxins and impurities after most of the solid and particulate material is removed through various processes. __ Air Treatment: Industrial applications often require the removal of volatile organic compounds (VOCS). It includes various fumes from gasoline, paints, and dry-cleaning chemicals. Special types of chareoal ean be used to remove mereury from emissions. Residential applications include dehumidification and odour removal. Charcoal is also found in gas/filter masks, __ Liquor Purification: Flowing aleohol or vodka or whiskey through activated charcoal ean improve its taste, colour, and odour. 9. Remove Poisons: , Activated charcoal that is charcoal designed for consumption is itself not toxic. __ Soit can be ingested in the event of poisoning to adsorb the poisons and prevent them from being absorbed into the body. __ Thisis an extremely effective method and is a very common modem treatment for poisoning. to, Catalysts: __ Heterogeneous catalysis involves specific chemical interactions between the surface of a solid and the reacting gas. The reactant forms complex compounds on the surface of the catalysts and then react to form products, which are desorbed from the surface of the catalyst Examples: In the synthesis of ammonia by Haber’s process, finely divided iron is used as a catalyst. During the alkylation process, H2 on finely divided nickel acts as a catalyst.Also, read more about the ‘Trends in Periodic Table, here. So, this is all about the Adsorption. Get some practice of the same on our free Testbook App. Download Now! Adsorption FAQs Q.1 What is the difference between adsorption and absorption? Ans.1 Assimilation of molecular species throughout the bulk of the solid or liquid is termed absorption. Accumulation of the molecular species at the surface rather than in the bulk of the solid or liquid is termed adsorption. Q.2 How many types of adsorption are there? Ans.2 There are mainly two types of Adsorption: Physisorption and Chemisorption. Q.3 Why is adsorption a spontancous process? Ans.3 For spontaneous adsorption, Gibbs free energy must be negative. This can happen if enthalpy change has a significantly high negative value as the product of temperature and entropy change is positive. As the process continues, enthalpy change becomes less negative until it becomes equal to the product of temperature and entropy change. At this point, Equilibrium is attained. Q.4 What is n in Freundlich adsorption isotherm? Ans.4 K and n: constants, n>1 always. Freundlich proposed this relation to show a relation between the extent of adsorption and pressure. Q.5 What is isotherm adsorption? Ans.5 An adsorption isotherm isa graph drawn at a constant temperature. It showcases the variation in the amount of adsorbate adsorbed on the surface of the adsorbent with the change in pressure. Adsorption isotherm is the relationship between the adsorbate in the system and the adsorbate adsorbed on the surface of the adsorbent at equilibrium at a constant temperature. Msgs) ee oo dC) =| ire | =F Previous Year Papers r ea ey hinPs The Complete Exam Preparation Platform Brey foo