Government Engineering College

,
Bharuch(014)

Subject : Chemical Reaction Engineering-II

Topic : Adsorption Isotherms & Rate of Adsorption

Group No. : 10

Student’s Name Enrollment No.
Khoradiya Ravi 130140105015
Panchal Priyansh 130140105021
Patel Dhaval 130140105027
Patel Smit 130140105035
Parsana Sanket 130140105046

which may be molecules in a gas stream or a dissolved or suspended substance in a liquid stream. molecules or atoms or ions in a gas or liquid diffuse to the surface of a solid. The adsorbed solute is called the adsorbate. and the solid material is the adsorbent. where they bond with the solid surface or are held there by weak intermolecular forces. on the surface of a solid. . • In an adsorption process. Adsorption Definition: Adsorption can be simply defined as the concentration of a solute.

It occurs with some chemically reactive gases. which is similar to chemical reactions. The amount of heat evolved in chemisorption is large (e. Types of Adsorption • Adsorption on solid surfaces may be divided into two categories. The forces that attract the fluid molecules to the solid surface are weak van der Waals forces. The physical adsorption is also known as van der Waals adsorption. physical and chemical adsorption. chemisorption does not take place on all solids.g.. Physical adsorption is non-specific and similar to condensation. The surface coverage is limited to a monolayer. • Chemical adsorption or chemisorption is specific. Chemisorption is used for finding the active centers of a catalyst. It involves forces which are much stronger than physical adsorption. The process is often irreversible. • Unlike physical adsorption. viz. Chemisorption usually occurs at high temperatures. 50–500 kJ/mol). .

. Adsorption Isotherm • A relationship between an amount of adsorbate adsorbed on the surface of a given amount of adsorbent and an equilibrium concentration of adsorbate in contact with the adsorbent is known as an adsorption isotherm.

General types of Adsorption Isotherms Adsorption Isotherms can be broadly classified into two classes: 1) Adsorption with monolayer formation 2) Adsorption with multilayer formation Monolayer Adsorption Multilayer Adsorption .

Monolayer Adsorption occurs due to chemisorption whereas Multilayer Adsorption occurs due to physisorption. • Sometimes. General types of Adsorption Isotherms • Not always but generally. Multilayer adsorption occurs due to chemisorption followed by physisorption .

adsorption of gas increases very rapidly as the pressure rises. However. x/m = kH’ p • At low temp. is high. Limitation: This Isotherm is applicable to lower conc. x/m is proportional to p(or Ca) which is shown in fig. when the temp. in slide no. Of adsorbate since at lower conc. 4 ..(Ca ). the increase in adsorption is relatively less. Different types of Adsorption Isotherms Henry’s Law: It is a simple adsorption isotherm which is used to describe the adsorption at a gas-solid interface which can be represented by the following equation.

Different types of Adsorption Isotherms Freundlich’s Isotherm: It has been found that the relationship between x/m & p is not linear but varies according to the following equation. ln(x/m) = ln kF + (1/nF) ln p • Freundlich’s Isotherm can also be expressed in the terms of conc. nF > 1 Freundlich Isotherm Curve By applying ln both sides of the equation we get. x/m = kF(p)1/nF . Log x/m versus log p . If p is replaced by equilibrium conc. Ca .

Assumptions: 1) At a given temp. of adsorption sites on adsorbent surface some fraction of these sites are occupied by adsorbate. 4) No interaction between molecule & different sites. Different types of Adsorption Isotherms Langmuir Adsorption Isotherm: In this Adsorption Isotherm it is considered that the adsorbent surface possess a number of active interaction sites for adsorption. & press. . 2) Each site can hold one adsorbate molecule 3) Heat of Adsorption is same for each site & is independent of “Ө”. let it be “Ө”.. from fixed no.

the Langmuir adsorption isotherm may be obtained as follows: • Rate of adsorption of molecules on the surface of the adsorbent = ka Ce (1-Ө) • Rate of desorption = kd Ө At equilibrium. KL = is adsorption co efficient. Ө = = where x and xm are the amount of the adsorbent adsorbed at equilibrium concentration Ce and maximum amount of adsorbate for the formation of monolayer. . Since. respectively.  Different types of Adsorption Isotherm Langmuir Adsorption Isotherm: Considering the processes of adsorption and desorption of the molecules on the surface. kd Ө = ka Ce (1-Ө) Ө = = where.

and Xm will be replaced by p. Ce . Langmuir’s equation works very well but fails for the cases where multilayer formation takes place. we will get a straight line. Ce.  Different types of Adsorption Isotherms Langmuir Adsorption Isotherm: Rearranging the last previous equation. . and Vm.V. In the case for the adsorption of gaseous substrate. If we plot vs. X. respectively. Slope of which will be and intercept as Therefore. from values of intercept and slope of the plot values of Xm and KL could be calculated. Limitation: For chemisorption too.

Different types of Adsorption Isotherms Langmuir Adsorption Isotherm: Langmuir adsorption isotherm for several non-dissociatively adsorbed species: If two species A and B are adsorbed on the surface. …Equation (1) . we have. Then applying Langmuir hypothesis for species A.

Different types of Adsorption Isotherms Langmuir Adsorption Isotherm: Similarly for species B. …Equation (2) Now putting the value of ӨB from Equation (2) into (1) we get. .

Different types of Adsorption Isotherms Langmuir Adsorption Isotherm: Similarly we can obtain. .

Where the sum runs over all species. Different types of Adsorption Isotherms Langmuir Adsorption Isotherm: In general. Langmuir adsorption isotherm for species A under conditions of several non-dissociatively adsorbed species could be derived as. .

Rate of Adsorption The rate of adsorption. and A the pre-exponential (frequency) factor. of a molecule onto a surface can be expressed in the same manner as any kinetic process. For example.kinetic order  k' . then we obtain a kinetic equation of the form: Rads = A exp (   -Ea / RT ).partial pressure If the rate constant is then expressed in an Arrhenius form. P x where Ea is the activation energy for adsorption. Rads.rate constant P . when it is expressed in terms of the partial pressure of the molecule in the gas phase above the surface:   Rads = k' P x where: x . .

to consider the factors controlling this process at the molecular level. and the sticking probability . we can express the rate of adsorption (per unit area of surface) as a product of the incident molecular flux.gas pressure [ N m-2 ] [ molecules m s ] -2 -1 (2πmkT)1/2 m .. Rate of Adsorption It is much more informative.mass of one molecule [ kg ] T . F .temperature [ K ] . 1.   Rads = S .. S . The rate of adsorption is governed by..e. however. F [molecules m-2 s-1 ] The flux of incident molecules is given by the Hertz-Knudsen equation Where Flux F = P / P .the rate of arrival of molecules at the surface 2.the proportion of incident molecules which undergo adsorption i.

function of the existing surface coverage of adsorbed species. Ea is the activation energy for adsorption and f(θ) is some. as yet undetermined.   S = f (θ) . once again. Combining the equations for S and F yields the following expression for the rate of adsorption : . Rate of Adsorption In general. exp ( -Ea / RT ) where.

You ha nk T .