Heterogeneous catalysis

LEC.8

• Individual Steps in Heterogeneous Catalysis

Heterogeneously catalyzed reactions are composed of purely chemical and purely physical reaction steps.

• For the catalytic process to take place, the starting materials must be transported to the catalyst. Thus, apart from the actual chemical reaction, diffusion, adsorption, and desorption processes are of importance for the progress of the overall reaction.

Heterogeneous Catalysis: Fundamentals

Steps in catalytic reactions

• We will now consider the simplest case of a catalytic gas reaction on a porous catalyst.

• In heterogeneous catalysis chemisorption of the reactants and products on the catalyst surface is of central importance, so that the actual chemical reaction step can not be considered independently from adsorption and desorption steps.

• The measured reaction rate, known as the effective reaction rate, is determined by the most strongly inhibited and therefore slowest step of the reaction sequence. This rate-determining step also determines the reaction order.

The Importance of Adsorption in Heterogeneous Catalysis 1. Gas-phase reactions catalyzed by solid surfaces. • For a catalytic reaction to occur, at least one and frequently all of

the reactants must become attached to the surface. This attachment is known as adsorption and takes place by two different processes:

physical adsorption (physisorption) OR chemical adsorption (chemisorption).

• Physisorption is the result of van der Waals forces, and the accompanying heat of adsorption is comparable in magnitude to the heat of evaporation of the adsorbate.

• chemisorption, chemical bonds are formed between the catalyst and the starting material. The resulting surface molecules are much more reactive than free adsorbate molecules, and the heats of adsorption are comparable in magnitude to heats of chemical reaction.

• both types of adsorption are exothermic.

Comparison between physisorption and chemisorption.

• Physisorption is fast, and equilibrium is rapidly reached, even at low temperature.

• Chemisorption generally requires high activation energies. The rate of adsorption is low at low temperatures, but the process can be rapid at higher temperatures.

• The rate of both types of adsorption is strongly dependent on pressure. Chemisorption leads only to a monolayer, whereas in physisorption multilayers can form.

Factors affect the extent of adsorption on the catalyst surfaces:

(1) Nature of the adsorbate (gas) and

adsorbent (solid)

(2) Surface area of the solid adsorbent

(3) Effect of pressure on the adsorbate gas

(4) Effect of temperature

Details are in the supplementary file

The important factors influencing the reaction kinetics(Reaction order)

1) Adsorption is a necessary step preceding the actual

chemical reaction on solid catalyst surfaces.

2) Heterogeneous catalysis involves Chemisorption,

which has the characteristics of a chemical reaction in

that the molecules of the starting material react with the

surface atoms of the catalyst.

3) Catalyst surfaces have heterogeneous structures, and

chemisorption takes place preferentially at active sites

on the surface.

Fundamental laws of adsorption

• Adsorption– Adsorption is a process in which molecules from gas (or

liquid) phase land on, interact with and attach to solid surfaces.

– The reverse process of adsorption, i.e. the process in which adsorbed molecules escape from solid surfaces, is called Desorption.

– Molecules can attach to surfaces in two different ways because of the different forces involved.

– These are Physisorption (Physical adsorption) & Chemisorption (Chemical adsorption)

•

• Adsorption processAdsorbent and adsorbate– Adsorbent (also called substrate) - The solid that provides surface for

adsorption• high surface area with proper pore structure and size distribution is essential• good mechanical strength and thermal stability are necessary

– Adsorbate - The gas or liquid substances which are to be adsorbed on solid

Surface coverage, q The solid surface may be completely or partially covered by adsorbed

molecules

Adsorption heat– Adsorption is usually exothermic (in special cases dissociated

adsorption can be endothermic)– The heat of chemisorption is in the same order of magnitude of reaction

heat; the heat of physisorption is in the same order of magnitude of condensation heat.

Adsorption Mechanism

Adsorption Isotherms

Data relating adsorbed concentration (g/g of bed weight) to equilibrium gas phase concentration (g/ml of stream) is given in terms of adsorption isotherms.

Wads = f (P,T)

Three common types of isotherms: Langmuir Freundlich BET

• Characterisation of adsorption system– Adsorption isotherm - most commonly used, especially to catalytic

reaction system, T=const.– The amount of adsorption as a function of pressure at set

temperature– Adsorption isobar - (usage related to industrial applications)– The amount of adsorption as a function of temperature at set

pressure– Adsorption Isostere - (usage related to industrial applications)– Adsorption pressure as a function of temperature at set

volume.

Pressure

Vol

. a

dsor

bed T1

T2 >T1

T3 >T2

T4 >T3

T5 >T4

Vol

. a

dsor

bed

Temperature

P1

P2>P1

P3>P2

P4>P3

Pre

ssur

e

Temperature

V2>V1

V1

V3>V2

V4>V3

Adsorption Isotherm Adsorption Isobar Adsorption Isostere

1-Langmuir Isotherm

The earliest model of gas adsorption suggested by Langmuir

(1916). The classical Langmuir model is limited to monolayer

adsorption. It is assumed that gas molecules striking the surface

have a given probability of adsorption. Molecules already adsorbed

similarly have a given probability of desorption. At equilibrium,

equal numbers of molecules desorb and adsorb at any time. The

probabilities are related to the strength of the interaction between

the adsorbent surface and the adsorbate gas.

Rate of adsorption,

Rate of desorption,

)1( Pkr aa

dd kr

At equilibrium,

da

a

kPk

Pk

Langmuir Isotherm (cont’d)

CP

CP

W

Wads

1max

where,Wads = the mass of gas adsorbed at pressure P;

Wmax = the mass of gas which covers the entire adsorbing

surface with a monolayer;P = the partial pressure of interest in the gas phase;

= coverage;

C = a constant for the gas/solid combination = ka/kd

ka = the adsorption rate coefficient;

kd = the desorption rate coefficient.

1-

air

adsorbate

Langmuir Isotherm (cont’d)

CP

CP

W

Wads

1max

maxmax

1

W

P

CWW

P

ads

Some physisorption and most chemisoption

processes follow this isotherm. It is the one

with the best theoretical basis, which

assumes that adsorption is limited to one

monolayer on the surface.

One can obtain the two

constants by linearization

of the isotherm: take the

reciprocal and rearrange

P0

1

C

P/Wads

P

J = 1/CWmax

S = 1/Wmax

then/C

Langmuir Isotherm (cont’d)

n

iii

iii

i

i

Pb

Pb

W

W

1max,

It is particularly suited to represent binary and ternary systems.

Assignment

• Define the Langmuir Isothermin case of liquid phase.

2-Freundlich Isotherm

The Fruendlich isotherm model is valid for heterogeneous surfaces, monolayer coverage. Common for most adsorption work since it fits almost all data. It is empirical in nature, although some theoretical foundations do exit.

Freundlich IsothermThe expression ： Wads = KF P 1/n

(KF and n are experimentally determined parameters)

Wads

P

n = 1

n < 1

n > 1 When n = 1, the reaction is linear and called

“partitioning”. When n > 1, the reaction is said to be

“favorable” as the incremental change in amount sorbed decreases with increasing concentrations.

While n < 1 is called “unfavorable” because the reverse is true.

Most natural adsorbents exhibit either linear or favorable adsorption.

The Langmuir and Fruendlich models for n < 1 are concave downwards, so both models can be calibrated to similar data..

Freundlich Isotherm (cont’d)

Wads = KF P 1/n

Wads

P

n = 1

n < 1

n > 1

ln Wads

ln P

1/n

ln KF

log

lnWads = lnKF + 1/n lnP

Available for a wide variety of organic vapors on various activated carbon types Wads = KF P 1/n

Freundlich Isotherm Parameters

3-Brunauer-Emmett-Teller (BET) Isotherm

Brunauer, Emmett and Teller (BET) developed several models for gas adsorption on solids which have become the effective standard for surface area measurements.

BET isotherm is valid for multiple layers on homogeneous surfaces.

Brunauer-Emmett-Teller (BET) IsothermThe assumptions underlying the simplest BET isotherm

are:

1. Gas adsorbs on a flat, uniform surface of the solid with a uniform heat of adsorption due to van der Waals forces between the gas and the solid.

2. There is no lateral interaction between the adsorbed molecules.

3. After the surface has become partially covered by adsorbed gas molecules, additional gas can adsorb either on the remaining free surface or on top of the already adsorbed layer. The adsorption of the second and subsequent layers occurs with a heat of adsorption equal to the heat of liquefaction of the gas.

multi-layers adsorption

Wads

P

00 11

PP

CPP

CPfor n

1

1

)1(1)1(

)1(1

n

nn

CxxCx

nxxnCx for finite n

Work for almost any type of data on the adsorption of gases on solids. It

describes every type of isotherm including the linear, and Langmuir isotherms.

For single component the equation is,

Note that n is the number of adsorbed monolayers, and x = P/P0. Where, P is the

actual partial pressure of gas in the stream and P0 is the vapor pressure of the pure

gas.

BET Isotherm (cont’d)

Note: The BET simplifies to the Langmuir when relative pressure x < 0.01 and C >100 (Valsaraj et al., 1992).

BET Isotherm (cont’d)

maxmax

1)1(

)(

1

CWP

P

CW

C

PP

P

W ooads

)(

1

PP

P

W oads

P/Po

S = (C-1)/CWmax

J = 1/CWmax

J

SC 1

JSW

1max

To obtain the parameters in the BET equation, one needs to linearize the equation:

Empirical Equations for Adsorption

(1). Correlation using a logarithmic series expansion such as:

2101010 logloglog eqeqads CcCbaW

Note that: a, b and c are constants specific to a typical compound.

The most common isotherm models [Dastgheib and Rockstraw, 2002]