oF PeEmM-O aH SIA) sy ii) O49 Interface Chemistry 1, GENERAL The heterogeneous processes proceed through solid-gas, solid-liquid, solid-solid, liquid- liquid, or liquid-gas interfaces (i.e., surface of separation or contact between two immiscible phases). The state of substance at the interface between contacting phases, differs from that inside these phases, owing to the difference in the molecular forces in different phases. This difference causes special surface phenomena at the interface of the phases. When the phase interface is great, it is impossible to neglect the properties of a substance near the interface, and as this surface increases, it begins to play a determining role in a system. Thus interface chemistry deals with all those phenomena, which occur at the interfaces of contacting Phases 2. TERMS AND THEIR MEANING js Adsorption Inside the solid or liquid, the molecular forces are balanced. But the state of particles at the surface of a liquid or solid is different from that in the bulk and molecular forces are in a state of imbalance or unsaturation. As a result of this unsaturation, the solid and liquid surfaces tend to satisfy their residual forces by attracting and retaining particles (atoms, ions or molecules) of other substances, with which they come in contact. As a result, the concentration of the substances on the surface (or interface) of a solid (or liquid) becomes greater than in the bulk. This phenomenon is known as adsorption. Hence adsorption is defined as the concentration of a substance at the interface between two immiscible phases (solid-liquid, solid-gas. liquid-liquid or liquid-solid). Adsorption is a surface phenomenon, the larger the surface area, greater will be the adsorption. Il. Adsorbent and Adsorbate ‘The substance on whose surface adsorption occurs is called adsorbent and the substance adsorbed from the bulk phase is called adsorbate. For example, NHy is adsorbed by charcoal; in this case, charcoal is the adsorbent and NH is the adsorbate. The greater the surface of an adsorbent is developed, the greater is the amount it adsorbs from bulk phase. A few examples of adsorbents ate : (@ Metals. They are good adsorbents and are being used for contact catalysis. Examples art Pd, Pt, Ni, Cu, etc. Gi) Colloids. As colloids possess high surface area per unit mass due to their small size. they act as good adsorbents. (iii) Silica gel. It acts as a good adsorbent. The examples of adsorbates are : (Various gases. (He, Ne, 0. Nz, NH, etc.) nzImerface Chemisiry (ii) Substances in solutton (NaCl, KCI etc.) HI. Specific Surface Area The surface area per gram of adsorbent is called the specific surface area. The active adsorbents have a very high specific surface area. The specific surface area of different adsorbents. may; vary quite greatly, The examples of very high specific surface area are (i) Nonporous bodies with specific area from several square metres to hundreds of square metres per gram ase representatives of the pigment and filler groups, ¢.g,, titanium dioxide pigment, aerosil- a highly dispersed silica uscd as a filler in many plastics and surface finishes, carbon blacks used as pigments and fillers in rubber. (ii) A still greater increase in the surface is usually due to the presence of narrow pores in a solid; examples of such highly dispersed porous bodies with a specifik surface area upto several hundred and even a thousand square metres per gram, are active charcoal, silica gel, porous crystals of zeolites etc. : IV. Absorption It is the phenomenon in which the substance is not only retained on the surface but passes through the surface, to become distributed throughout the body of a solid or liquid. Thus absorption is a bulk phenomenon. Examples of Adsorption and Absorption. (i) Water vapours are adsorbed by silica gel while water vapours are absorbed by anhydrous CaCl. (ii) NHy is absorbed by water to form NH,OH, while it is adsorbed by charcoal. (iii) When charcoal is stirred into a dilute solution of methylene blue, the depth (intensity) of colour of the solution decreases appreciably because charcoal adsorbs the coloured material and thus decolorises the solution. Hence this is an example of adsorption. (iv) When finely divided solid (¢.g., charcoal) is added to a gas at low pressure, the gas pressure is found to decrease. This is another example of adsorption, where gas is adsorbed on solid surface. (v) When sponge is put info water, it takes up water. The water enters the whole body of sponge. Hence it is the case of absorption. (vi) When a hot crucible is allowed to cool in open, a film of moisture is formed at the surface. Hence this is a case of adsorption of water vapours on the surface of the crucible. V. Sorption Where doubt exists as to whether a process is true adsorption or absorption. the noncommittal term sorption is sometimes used to include both the processes (adsorption and absorption). Hence sorption is a process in which both adsorption and absorption take place simultaneously. The examples of sorption are : (i) When Ha gas is brought in contact of charcoal, it first concentrates on its surface. This is adsorption. After some time the H gas penetrates inside the body of charcoal. forming solid solution. Hence this is a absorption. Thus charcoal adsorbs as well as absorbs H, gas. Therefore. this is an example of sorption. (ii) The taking up of gas by zeolites is an example of sorption. (iii) Dying of cotton fibres is an example of sorption, where dyestuff is adsorbed. as well as absorbed by cotton fibres. Adsorption, absorption and sorption are illustrated in the Figs. 10.1-10 3Fig. 10.1. Concentration of adsorbate on the interface. Hence it is adsorption. o ry PT SP POSER ‘© Adsorbent O- ig oe ° or oe QBS 80 re OOe 08 0 0 Basco stein eg Fig. 10.2. Uniform penetration of adsorbate molecules in the body of adsorbent. Hence it is absorption. Concentration of adsorbate on the interface. Hence “adsorption’. Uniform penetration of =~ adsorbate insi Hence ‘absorption’ Be \dsorbent. Fig. 10.3. Adsorption and absorption take place simultaneously. Hence itis the case of sorption. Difference between Adsorption and Absorption Adsorption Absorption 1. The concentration of substance only takes place on the interface between two phases | and not in the body of an adsorbent. 2. This is a surface phenomenon. That is, the concentration of substance is always greater on the interface than in the bulk phase. 3. Attainment of equilibrium is instantaneous. The isotherm for adsorption is usually. as shown in Fig. 10.4. . 3ix—> The substance is distributed throughout the body of adsorbent to form a solution or a compound, This is a bulk phenomenon. That is. it involves bulk penetration of molecules of the adsorbate in the whole body of adsorbent. ‘The equilibrium is attained very slowly. The isotherm for absorption is generally of the type shown in Fig. 10.5. ‘eee renee ative Adsorption rae snd New of a substance (absorbate) is more at the interface, the adsorption is If the concen! is he ii sal ‘adsorption. If the concen! ration of the adsorbate is less at he interface, the called positive Uf th ve ion. adsorption is said to*be negative adsorption. ain I ane of adsorption. That is, removal of an adsorbed substance from the surface of tis the revet adsorbent is called desorption. IX. Occlusion The sorption of, 3. STUDY OF ADSORPTION OF GASES ON SOLIDS I. Factors on which Adsorption Depends ' “The magnitude of adsorption of gases by solids depends on the following factors : (@ Nature of Adsorbent and its State of Subdivision. The adsorption is a surface phenomenon. Hence the magnitude (or extent) of adsorption depends on the surface area of the adsorbent. The greater the surface area of the adsorbent, the greater is the amount of substance it absorbs from bulk phase. Active adsorbents have very high surface area per gram i.e.. specific surface area. Subdivision of the adsorbent increases the specific surface area and hence the magnitude of adsorption increases. That is why finely divided metals (nickel, platinum) and porous substances (e.g., charcoal, silica gel etc.) provide very high specific area and hence they are very good solid absorbents. (ii) Nature.of Adsorbate (gas). The amount of gas adsorbed by solid adsorbent also depends ‘on the nature of the gas. The gases which liquify more easily (i.e:, which have high critical temperature) are adsorbed more readily than those gases which do not liquify easily (i.e., which have very-very low critical temperature €.8., Hz, Ny Oy He etc.). The reason is that easily liquefiable gases have greater van der Waals forces (molecular forces) of attraction. It can be fomcliaed that higher the critical temperature of the gas (adsorbate), the greater is the extent of lsorption. . (iii) Effect of Temperature. Adsorption is an exothermic i Le-Chatelier's principle, the rate of adsorption (i.e., magnitude of ae et by & sty ita ia increase with decrease in temperature and this actually takes place. (iv) Effect of Pressure. For a given gas and a given adsort i depends on the partial pressure of the gas. ‘Adsorption of gas aa seer a according to Le-Chatelier's principle magnitude of adsorption will increa: DT pressure and vice versa. am with Tnesenhy Ye Il. Kinds of Adsorption The study of adsorption of various gases on solid surfaces ha eo . are not the same in all cases. There are two types of adsorptions : cee eannE ones 1. Physical (van der Waals) Adsorption or Ph ion. WI ! ysisorption. When t i ce attraction hold the gas molecules on the surface of the solid, the cme now eal adsorption. The forces responsible for physical adsorption are : Ae (a) Dispersion Forces. These forces are due to coordina i p . ted motion of el molecules. Owing to the motion of electrons. even molecules with a symmetrical distribution of electron density, have Nuctuating deviations of this density from the average value. fluctuating dipoles,.quadrupoles. etc.. When the molecules approach one another, the motions of fice fluctuating dipoles, quadrupoles, etc... of different molecules are no longer independent, and i aé. this that leads to attraction. nae gases by metals is known as occlusion.Advanced Physical Chemisiry All these forces are forces of attraction, and w | and when the molecules of the adsorb: those of adsorbent surface, th i ee pase ot ce, they are balanced by forces of repulsion that rapidly grow over short _, The molecules being adsorbed, interact not with one centre on the adsorbent surface, but with many neighbouring centres. The total interacti ion of an adsorbate molecule with adsorbent, - the entire due to dispersion forces, is always greater than its interaction with one centre of the adsorbent. But the total electrostatic interaction can be neither greater nor smaller than the electrostatic interaction with one centre of adsorbent. (c) Short Range Repulsive Forces. These forces originate from the interpenetration of electronic clouds of the atoms. (4) Polarization. If the adsorbate molecule is nonpolar, the magnitude of adsorption potential will depend on polarisability of the molecule. . The forces holding gas molecules on the surface of adsorbents are very weak. Hence the physical adsorption is characterised by low heat of adsorption. The examples of physisorption are : (@) adsorption of gases on charcoal . . (6) adsorption of Nz on mica, 2. Chemical (Activated) Adsorption or Chemisorption. A strong chemical bond may appear between a molecule of adsorbate and the surface of adsorbent, with the formation of a new surface chemical compound. This phenomenon is called chemisorption. Hence, chemical forces are responsible for chemical adsorption. In chemisorption the forces involved are very-very strong, hence it is characterised by a high rate of adsorption, taking place at elevated temperature and is often an activated process. Chemisorption may propagate from the surface into the bulk of adsorbent, turning into an ordinary heterogeneous reaction. It may be dissociative, non-dissociative or reactive in nature. The examples of Chemisorption are : (a) Adsorption of oxygen by the surfaces of metals. (b) Ethyl alcohol vapours condensed on the finely divided nickel. (c) Adsorption of hydrogen on nickel. LL. Characteristics of Physical and Chemtcal Adsorptions (or Differences between Chemisorption and Physisorption) The differences between (or characteristic of) physisorption and chemisorption are given below Characteristics I Physisorntion Chemisorption 1. Nature of forces It involves weak physical forces. It] It involves very. strong chemical is an exothermic process. forces. It is also. an exothermic process 2. Heat of adsorption Heat of adsorption is tow and| It is very high and is of the order of generally less than 40 kJ/mole. 40 to 400 KJ! mole, 3. Occur nce 1 at high temperatures. (Contd.)Interface Chemistry nT Characteristics Physisorption Chemisorption 4. Attachment of involves weak forces, hence leads | The fcices involved are very strong Molecules to surface | to weaker attachment of gas | and lead to much firmer antachment molecules to the surface of the| of the gas to the surface. adsorbent, So Reversibility and| It is instantancous. Hence, | It may be rapid or slow. depending {peed of adsorption | adsorption equilibrium is) on the nature of chemical reaction establishment rapidly. It is| involved. The —_ adsorption reversible in nature, equilibrium is established slowly. tt is irreversible in the sense if subsequently pressure is reduced. desorption may not occur. 6. It is ‘not very specific. That is, magnitude of adsorption mainly depends upon the chemical nature It is often very specific. That is. it depends on the chemical nature of the adsorbates as well as the ‘of adsorbate and on roughness and | adsorbents. polar character of the surface of the adsorbent 7. Effect of temperature | is more pronounced at} occurs. usually at high temperatures below boiling point of | temperatures. It can occur even + adscrbate. It is appreciable at low | above boiling temperatures. temperatures. 8 Effect of pressure The rate of increase in adsorption | Rate of increase in adsorption with with pressure is much higher at] pressure progressively decreases, a5, higher pressures. pressure increases. 9. Structure of adsorbed layer Muhilayers (many molecule thick) are formed as shown in Fig. 10.6. Fig. 10.6, Monolayers (one molecule thick) or unilayers are formed as shown in Fig. 10.7. CCOCOSO Fig. 10.7. 10. Activation energy ‘Activation energy need —_is | Significant activation energy is insignificant, needed. 11. Desorption The desorption by heating is) The desorption by heating is graphically represented as shown in phically shown in Fig. 10.9 l an Te - 1 - ca \ Temp. —> | Fig, 10.8. Fig. 10.9. —w)—— (Cond )Characteristics Physisorption In physical, adsorption, seven types Types of adsorption 1 Adganced Physical Chemistry Chemisorption A typical lsotherm for chemical isotherm of adsorption isotherms are found. | adsorption is shown in Fi Some of them have been explained Panes by BELT. equation I p> Fig. 10.10. Adsorption increases with pressure and ultimately reaches a limiting value. 13. Scope leis a general phenomenon and may | ft is not so general in nature, Tv le be found in all instances, although it may possibly be masked by stronger type, It is a function of coverage. of ‘Surface, That is, greater the surface area of adsorbent, the greater is the magnitude of adsorption. 14 Surface phenomenon IV. Types of Adsorption Curves The amount of gas adsorbed on the surface of ads temperature. In other words, the amount of only. Mathematically, it can be represented as : x/m = f(P,T) where x= Amount of gas absorbed on mass m of adsorbent at This mathematical equation is called adsorption curve. or graphical curve, which represents relation between amount found only where there Is tendency towards compound formation between a gas and adsorbent. It takes place at fixed sites on the surface of the adsorbent. These are known as active centres. sorbent depends on pressure and Bas adsorbed is a function of temperature and pressure Pressure P and temperature T. Hence a mathematical expression t of gas adsorbed by the adsorbent at equilibrium pressure and temperature, is called an adsorption curve. The graphical representation of equation (1) will give three curves under different conditions of P, Tand x/ m. These curves are as follows : () Adsorption Isotherm. If T is kept constant, then equation (1) becomes a/m = f(P); (T = Cor The equation (2) gives variation of x / m with pressure at instant) . constant temperature. Hence, when x/ mis plotted against P at constant temperature, the curve obtained is called adsorption isotherm. Hence, adsorption isotherm is a mathematical expression or a-graphical curve, which represents the variation of adsorption with pressure, at constant temperature. (i) Adsorption Isobar. If P is kept constant, then equation (1) becomes a/m = F(T); (P = Constant) GF Equation (3) is called adsorption isobar. Hence adsorption isobar is a mathematical equation or a graphical curve, which expresses the variation of adsorption (x/m) with temperature, at constant pressure. | (iii) Adsorption Isostere. If the amount of adsorbed gas (x/m) is kept constant, then i becomes equation (D P=f() ( /m = Constant) = A) The equation (4) is called adsorption isostere. Hence adsorption isostere is a mathematicalInterface Chemistry ; . rn temperature, when amount of snowing the variation of Pressure witit temp pp expression or a eurve, 5! ee Adsorption Isotherms Physical . nit V. Types of trees T results, seven types of Physical adsorption isotherms have been \ On the basis of How : ; ‘lids. They are shown bel : / Se eet G gical Langmut ‘cotherm when the adsorption is monolayeric. This Type. This curve (Fig. 10.11) shows that limiting (satura ion) state is reached, which means that after certain value oe there is no change in x / m with the increase in pressure- For example adsorption of N; Jue of P, ‘on charcoal at ~ 195°C. Limiting T= Constant p> Fig. 10.11, Type Il. It represents a cas¢ of multimokécular layer physical adsorption, on nonporous materials. In this isotherm, there is a transition point B 10.12) which represents the pressure at which the formation of monolayer (or monomolecular layer) is complete and that of multilayer (or multimolecular layer) is being started. For example, adsorption of N2 on silica gel at -195°C. T = Constant -— Fig. 10.12. Type III. It represents the case of physical adsorption on isotherm (Fig. 10.13) there is no transition point. This isotherm formation starts even before the formation of monomolecular adsorption of Br, (or I) vapours on silica gel at 79°C, Porous materials. In this type of shows that multimolecular layer layer is complete. For example, T= Constant Bh >— Fig. 10.13.Advanced Physical Chemisiry there is a tend i state to be reached in the multimolecular region lency for saturation Bix T= Constant > Fig. 10.14. Type V. It represents the case of physical adsorption on porous material. It indicates the formation of multimotecular layer in the beginning. For example adsorption of benzene on ferric oxide gel at SO°C, (Fig. 10.15). -—> Fig. 10.15. Type VI. This type of adsorption isotherm (Fi ig. 10.16) is expected for nonwetting stsorbate-adsorbent systems, T=Constant Po= Saturated Vapour Pressure —_ _ Fig. 10.16,Interface Chemisiry . . m Type VII. This type of adsorption isotherm (Fig. 10.17) is also expected for nonwetting adsorbate-adsorbent systems. Po is called saturated vapour pressure. T= Constant + Bx ae Fig, 10.17. VI. Various Equations of Adsorption Isotherms (Or Various Adsorption Isotherms) AK ‘The various equations of adsorption isotherms (or various isotherms) are : 1, Freundlich adsorption isotherm. 2. Langmuir adsorption isotherm. , 3." BET. isotherm, Freundlich Equation of Adsorption Isotherm. Freundlich proposed an empirical relation in the form of a mathematical equation °~ x oye —=kp " or log = logk + 7 logp i where x = Mass of gas adsorbed on a mass m of adsorbent at pressure p k,n = Constants, depending on the nature of adsorbent, and gas and on temperature This mathematical equation is known as Freundlich equation of adsorption isotherm or simply Freundlich adsorption isotherm. ‘The Freundlich adsorption isotherm is also used for the adsorption of solute from solution and has been found saisfacory. The pressure in the equation (I) is replaced by equittrim concentration (C) of solute, i, Boos” ~@ or (4) = logk + t log C (a) Testing of Freundlich Eq follows : Method |. We know that raf This is an equation of ion. The validity of Freundlich equation can be tested as \ log k + t logp. ht line, It has been experimentally shown that plot of log (3) + against log p comes out to be a straight line (Fig. 10.18), hence Freundlich equi is valid. =From the Fig. 10.18, ; Slope of straight line = tan @ = t Intercept of the line = log k 1! eg P — Fig. 10.18. Freundlich adsorption isotherm. Freundlich equation explains the behaviour of adsorption approximately. The values of 1/n lie between 0 and 1. (® When 1/ n= 0, then ar aoe or = = k = Constant Equation (3) shows that magnitude of adsorption is independent of p1 (i) When Vn = 1, then . Zp we Rl? kp or zap w= (4) ‘The equation (4) shows that magnitude of adsorption is directly Proportional to pressure. Both the above conditions are supported by experimental results. Method 2. This is also called saturation test. x Va Zak m

>— Fig. 10.19. Adsorption of Nz by charcoal.mB, Interface Chemisiry it is it is clear. that. they tend to approach a saturation or From these experimental isotherms, it , d : . limiting value at high pressure. ‘This shows that Freundlich equation (or Freundlich adsorption ils at high pressures. ; | a cal ees of Freuitdlich Adsorption Isotherm: (i) Freundlich equation is purely jrical. It has no theoretical basis. ew The constants k and n are not temperature independent. They vary with temperature. ii) This equation is valid over a certain range of pressure only. 2#°2. Langmuir Equation of Adsorption Isotherm. The adsorption of gases on solid surfaces is either zero order or fraction order reaction, and the failure of Freundlich isotherm at higher pressures, indicated that Freundlich concept of physical adsorption might not be entirely, correct. In 1916 Langmuir introduced a new concept involving chemical forces. He derived a mathematical equation for adsorption, based on kinetic theory of gases. This equation is called Langmuir adsorption isotherm, which ‘s most easily considered in its application to adsorption of gases. ‘2.2 Postulates of Langmuir’s Theory. The following are the postulates on which Langmuir théSry is based : (i) The atoms of the adsorbent on the surface have residual force due to. unshared electrons, With striking gas molecules, a sort of covalency linking is formed between the gas molecules and the surface atoms. (id) The molecules of a gas até adsorbed only on vacant sites of the adsorbent surface. Each site can hold only one molecular or atomic species of the absorbate. e (iif) The bond between gas aid adsorbent may be a chemical or physical one, but it should be sufficiently strong to prevent motion 6f gas molecules along the surface. (iv) Langmuir considered that adsorption is localized, instead of being mobile. That is, molecules of adsorbate cannot wander along the surface of adsorbent. Whereas in mobile adsorption, the molecules of gas adsorbed are free to move along the surface of adsorbent. (v) At low temperatures, physically absorbed molecules are mainly localized, and at high temperatures they are mobile. Chemically adsorbed molecules are localized. (Fig. 10.20). | Nonlocalized Adsorption : DMILY 2 ocalized Adsorption eee Distance along Surtace ——__» Fig. 10.20. Localized and non-localized adsorption. Gas molecules + Vacant sites on adsorbent surface == Localized adsorption complex (vi) Langmuir assumed that adsorbed gas is unimolecular in thickness (one molecule thick) That is, once the surface atoms are covered up by gas molecules, no further adherence of gas molecules would occur. It means the adsorption is chemical in nature, (vii) The molecular species adsorbed on different sites (of adsorbent surtice) do not interact with each othéP®* Advanced Physical Chemistry (viii) Since adsorption would involve electron sharing, considerable heat changes would occur. The heat of adsorption is the same'for all the sites and is independent of the fraction of the adsorbent surface covered. (ix) The surface of adsorbent is uniform energetically. That is, energy of adsorbed particle is same anywhere on the surface and is independent of pressure. (x) The adsorption is a dynamic process, consisting of two opposite actions ~ (@) condensation of molecules from the gas phase on the surface and (b) an evaporation (desorption) of adsorbed gas molecules from the surface back into the body of gas. Thus an adsorption equilibrium is reached when the rate of adsorption is equal to the rate of desorption. mDerivation of Langmuir Adsorption Isotherm. Suppose, the fraction of surface of adsdrbent covered by gas = © <. The fraction of surface uncovered If, -68 n= Number of gas molecules striking the surface = Fraction of molecules condensing Then, number of molecules which condense on the surface = & -. Rate of condensation ‘Number of molecules condensing on uncovered surface na(l - @) Rate of evaporation (desorption) « (Area of surface covered) where * At equilibrium, Rate of condensation = Rate of desorption « : sna (1-0) = ~B 0 or na-nad= B.8 na ptna Now, number of gas molecules striking the surface varies as the pressure of the gas 5 ary or n=kp (k = Constant) Now let us calculate the value of Btn B+na_ fy; comeains ey1-—1— kpa (ka/B)p Beno 1 4, 1+hP bal na kp kip na __kip Or ce Ptna t+hp From equations (1) and (2) e- HPL T+ kp Let, x= Mass of gas adsorbed on mass m of the adsorbent. ‘Then, x/ m= Mass of gas adsorbed per unit mass of adsorbent. That is, magnitude of adsorption.. 5 75 Interface Chemistry Now, mass of gas adsorbed ptr unit mass of adsorbent varies as the fraction of surface covered. s x/m = ® or x/m = k.8 wn (4) ons (3) 4 ‘ From equations ( ) and ( ) ate yma or Equation (5) is known as Langmuir adsorption: isotherm or Langmuir's equation of adsorption isotherm. In this equation k and k, are constants. Method of Testing. The Lanigmuir adsorption isotherm is Peer rere x/m hh This equation represents a straight line. Hence, if on plotting aml is obtained, then the equation is valid (Fig. 10.21). This has been experimentally proved. against p, a straight line ! — Intercept o> Fig. 10.21. Testing of Langmuir adsorption isotherm. 1 The slope = tang = > slope = tan = 7, Iotercept = Thus we can also calculate k, and kp Interpretation (Discussion) of Langmuir Isotherm, 1. Langmuir equation is however, too much of a simplification. It assumes that adsorption is monolayeric in nature and no more. But the adsorption, in most of the cases, is of multilayer type. This limits the appli ; Langmuir adsorption isotherm. 2 y of 1 Pp G/m) ~ hha” It is evident from this equation that there can be the following limiting cases : Case 1. When pressure is very low, then in the equation 4, kihp m" T+ kpx 76 ~ iced Physical Chemistry the term kyp-will be negligible in comparison of 1. Hence we have ’ ~ x = = kk o ‘ Thus, the amount of gas adsorbed per unit mass of adsorbent Is direcily proportional to the pressure of the gas. Case 2. When pressure is very high. Then k, p >> 1. Hence | is neglected in comparison of kip and we get kikp 1P x z =k x or 5 ay i i a Constant , Hence the amount of gas adsorbed per unit mass of adsorbent is constant and independent of pressure. Case 3. When pressure is moderate. At very low pressure : . = p or = = Constant x p Tn very high pressui =" = Constant” ~. At intermediate pressiite the Langmuir equatic a or X= kp" which is Freundlich equation, when |! n lies between O and \. Another Form of Langmuir Adsorption Isotherm. This is obtained as follows : If, V = Volume of gas adsorbed at given pressure p Vm = Volume required to form a complete monomolecular layer to saturate the surface of the adsorbent ® = Fraction of surface covered v Then, o=7 Since, Hence ‘This equation is another form of Langmuir adsorption Isotherm. : - Usefulness of Langmutr Adsorption Isotherm. 1. This equation explains mechanism of chemisorption.Inse gece Chemistry 2. Langimuir’s theory is more satisfactory than Freundlich theory while explaining physica adsorption of gases on solids. ‘Limitations of Langmulr’s Theory. The limitations are : AS 1 This theory could not explain all the five types of experimental adsorption isotherms (Type I to Type V). 2, Langmuir adsorption isotherm is an equation of localized adsorption on a homogeneous surface in the absence of forces of attraction between the adsorbate molecules. This may be true only at very low pressure. Thus Langmuit's equation is expected to hold good at low pressures only. 4. In the derivation of this equation, the forces of repulsion are taken into account by the assumption that one site can be occupied by only one molecule of the absorbate. It is, however. too much of a simplification. 4. Apparent saturation of a surface is observed even when only a small fraction of the area of adsorbent is covered. 5. According to Langmuir’s theory. the saturation value of adsorption is independent of temperature. But experiments show that saturated value decreases with rise of temperature. 6. This theory assumes that the surface is capable of adsorbing a layer one molecule thick and no more. But in actual practice much thicker layers have been reported. tk. Isotherm Equation for Multilayer Adsorption of Gas or Vapour : B.E.T. Equation. ‘The various types of experimental adsorption isotherms could not be explained by monomolecular layer adsorption theory of Langmuir. Brunauer, Emett and Teller developed a theory of multimolecular ‘layer adsorption: of gases and vapours. This theory is known as B.E.T. theory ‘These workers extended Langmuir's theory to multilayer adsorption and derived a mathematical equation called 8.E;T. equatioit or B.E.T. adsorption isotherm, which explained satisfactorily all the five types of experimental adsorption isotherms. Postulates of B.E.T. Theory. This theory is based onthe following assumptions : —. (@ Adsorption involves the formation of multimolecular layer, rather than mono mole- cular layer. This is represented as follows : Vapour + free surface Vapour + single complex Double complexes Vapour + double complex Triple complexes, etc. (ii) Langmuit’s idea of fixed (localized) adsorption sites was retained. (iii) ‘The interactions between the adsorbate molecules in the adsorption layer are neglected. (iv) For the formation of single complexes, the assumption made in Langmuir’s theory is adopted. . (v) There is dynamic equilibrium between the successive layers. The rate of evaporation (desorption) from first layer is equal to the rate of condensation on the preceding layer. (i) The forces that produce condensation are responsible for binding energy in successive multilayers (Vii) After the first layer, the heat of adsorption is equal to latent heat of condensation of vapour. Statement of B.E.T. Equation. On the basis of above postulates Brunauer, Emmett and Teller derived the following equation : Single complexes aa p --',(c=1)e2 V(po- P) Va € Vn C ) Po This equation is called B.E.T. equation. In this equationAdvanced Physical Chemisiry Vv = Volume, reduced to standard Condition, of the gas adsorbed at Pressure P sno temperature T ro = Saturated vapour pressure of adsorbate (gas or vapour) at temperature T Vn = Volume of gas, reduced to standard conditions (ie., at NTP), adsorbed to form a saturated monolayer per gram of the adsorbent C = Acconstant equal to e+ ~ £0747 , Here Ey Heat of adsorption of first layer E,= Heat of condensation(liquefaction) of the gas E,- E, = Net heat of adsorption X interpretation (Discussion) of B.E.T. Equation. 1. B.ET-equation suggests that plot of P . a . versus 2 should give a straight line. This has been found to be so experimentally (Fig. Vm ~ Pp) Po . 2 y 10.22) which confirms the correctness (validity) of B.E.T. equation. Slope = tang Imercept = ye @ From equations (1) and (2), the value of Vq (volume of gas to form monomolecular layer) Fan be calete ee 10 see that when only unimolecular film is formed on the surface. the B.E-T: tion would reduce to Langmuir equation. ; oa a ‘The scheme of multilayer adsorption followed in B.t-T. theory can be represented as shown in Fig. 10.23.Interface Chemistry 729 4, B.E.T. equation is better obeyed by processes involving high value of (Ey - E,) as under such conditions only the adsorbate-adsorbent interaction is predominent. $5. Explanation of various types of experimental adsorption isotherms on the basis of B.E.T theory (i) Type | isotherm is explained when the adsorption is monolayeric. (ii) To explain Types I and III isotherms, it has been suggested that : (a) Type Il isotherm will follow when E, > Ey (b) Type Il isotherm will follow when Ey < Ey (iii) To explain Type IV isotherms, it has been suggested that substances showing such behaviour undergo not only multilayer adsorption but also condensation of gas in the pores and capillaries of the adsorbent, The two types arise again from the relative magnitude of E, and Ey. Thus - (a) When Ey > E,, Type IV isotherm is obtained. (6) When Ey < E; Type V isotherm will follow. Limitations of B.E.T. Theory. 1. ‘The assumption that adsorbate has liquid properties is not correct. 2. When the net heat of adsorption ( E, ~ E,) is low, the constant C in B.E.T. equation is small. At C< 2, the B.E;T. equation gives a concave isotherm... 3. BELT. equation: holds good when.p / po values lie betwegn 0.05 to 0.35. This equation fails if p / po is below 0.05 and above 0.35. 4. Coordinatioi aimber of molecules i the higher layers als8 adds to the criticisms of the ~ BET. equation in another way. i 5. Low adsorbaté-adsorbent energies, however, the absorbatéiadsorbent interactions cannot be neglected. In these cases the isotherm (ie., curves) are more complicated in shape. Thus B.E.T. equation is approximate and needs modification. _-Modification of B.E.T. Equation. The B.E-T. equation was modified on the assumption that multilayer formation is limited to certain number of layers (say n-layers). It does not extend to infinity. It means that the number of adsorbed layers cannot exceed a finite number (n). Then we Me ee fe tee te nee Ye (1 - x) [14(C 1s - Ce This is the modified form of 8.E.T. equation. (a) When n= 1, this equation converts into Langmuir's equation. (6) When n =e, then this equation changes into B.E.T. equation. VIL. Determination of Surfaces Area of Solid Adsorbents Generally the solid adsorbents are used in a fine state of subdivision and are often porous, 50 as to increase the surface area of adsorbent. This enhances the magnitude of adsorption. ‘The porous solid adsorbent possess two types of surface areas ~ (a) external of outer surface area of porous particles and, (b) inner surface area, which is due to surface of inner walls of capillaries and cracks in the porous catalyst particles. The roughness factor of the catalyst is defined as : Total_surface area Outer surface area Hence, (() for smooth surface, roughness factor is about unity. and (if) for rough surface, it is very-very high. Roughness factor =Advanced Physical Chemistry Surface area Mass of adsorbent The following methods are employed to determine the surface area of solid adsorbents : (@ BET. Method. (ii) Point B Method. (iii) Radioactive Tracer Method. (iv) Electron Micrograph Method. - 2X B.E-T. Method. This method is extensively used for determining the surface area, The BET. equation is c ) 2 V(po = P) sae Po The plot of TT CRRETED versus = will be a straight line (See Fig. 10.24). The slope and imtercept of which will be : Specific surface area = Cc-1 Slope = tang = 5; el) Intercept = oi 2 (2) ‘Adding equations (1). and (2) Slope +. Intercept The'Values of slopé’and intercept (3), Vm is-calculated. Intercept (erp) —> Fig. 10.24, Graphical representation of B.E.T. equation, “22400 ml of gas at NTP contains N molecules. 3 N. Vn 2. Vm mi of gas will contain 5758 If, A= Area of cross-section of each adsorbed molecule, i.¢., the area of surface covered by each adsorbed molecule m= Mass of adsorbent molecules. é Vn NA oa) ‘Then, surface area of solid adsorbent = “F575 — ” ~—a . mI | Innerfact CramBry and Specific surface area = Surface area per gm of adsorbent - Via NA (5) 22400 x m Putting the value of Va frdm equation (3) in equations (4) and (5), the values of surface area and specific surface are obtained respectively. s z In BET. method, nitrogen gas is commonly used and value is 16.2 A” (16.2 x 10"'*cm’) at the liquid Ny temperature. This method is simple in practice, and the results obtained are quite satisfactory (ii) Point B Method. In this method the relative pressure (p/p) is plotted against volume i of gas adsorbed. The curve as shown in Fig. 10.25 is obtained. ‘ZEFig. 10.25. Plot of (pipo) versus V. The point B is the first inflexion point in the curve and it corresponds to the condition when unimolecular layer is formed. If Vp = Volume of gas corresponding to B, reduced to standard conditions (pp = 1 atm. To = 273°C) Then, (= Moles of gas adsorbed) + Number of molecules adsorbed = nV N Po RI If, A = Cross sectional area of each adsorbed molecule AN poVa RT AN poVa mRTo where m = Mass of the adsorbent. This method cannot be applied to all types of gas adsorbates and solids. In this method generally Nz gas is employed. The value of A for Nz molecule is calculated as follows : ws M (4) Then, total surface area Specific surface area =