Chemical Reaction Engineering- II (2170501)

Semester – VII (CHEM)

Chapter Name: Catalysis (Chapter 5)

Catalysts
Catalysis is the increase in rate of reaction by addition of substance called ‘Catalyst’. Catalysts are those substances
/material that on addition will alter the path of reaction by forming temporary intermediate and thus lowering the
rate of reaction. There are two types of catalysts (i) Homogeneous catalyst (ii) Heterogeneous catalyst
(i) Homogeneous catalyst: A homogeneous catalyst is one whose molecules are dispersed in the same phase
(usually gaseous or liquid) as the reactant molecules
(ii) Heterogeneous catalysts: A heterogeneous catalyst is one whose molecules are not in the same phase as
the reactants, which are typically gases or liquids that are adsorbed onto the surface of the solid catalyst.
For e.g. Use of Vanadium Pentoxide in Haber’s Process, Use of Copper in conversion of Ethanol to Acetaldehyde
(Oxidation Process)

Physical Properties of Catalyst

The surface area of sold has pronounced effect on the amount of gas adsorbed and on its activity as catalyst. For
Example, if a fresh sample of fresh Raney Nickel which is highly porous and large surface area is held in hand, heat
can be felt due to oxygen adsorption which is exothermic in nature. Thus, larger surface are gives higher
Adsorption rate. The dependence of rate of adsorption and catalytic reaction on surface makes it imperative to
develop reliable method for analysis of surface area. The physical properties like surface area, Pore volume,
distribution, void volume, Solid density are important in any catalytic reaction.
(A) Determination of Surface Area:
The standard method to measure area is to conduct physical adsorption of gas on solid surface. For that, the amount
amount of Nitrogen gas adsorbed at equilibrium at normal boiling point is measured over pressure range below 1
atm.
The amount adsorbed when one molecular layer is attained must be identified in order to determine the area. For
this, BET i.e., Brunauer-Emmet-Teller method is used. Determination of internal surface area is based on
adsorption and condensation of N2 at liquid N2 temperature, 77K. Initially, the sample is evaporated at 293-523
K (120-250°C) followed by cooling to 77 K by liquid N2. Then gradually the partial pressure of nitrogen above
the sample is increased. Some quantity of gas will be adsorbed by the sample and removed from the gas
phase. After stabilization the equilibrated pressure is recorded and amount of nitrogen adsorbed at each
equilibrated pressure is noted. The isotherm, volume adsorbed as function of relative pressure p/po, is plotted
from the data. The pressure over the sample is gradually increased until pressure reaches near saturation
pressure, by when the complete adsorption isotherm is developed. The desorption isotherm is measured by a
step-wise reduction in pressure until a low pressure over the sample is achieved. Although the volumes are
adsorbed at different conditions, the values are reported at STP conditions.
The BET equation describes the relationship between volume adsorbed at given partial pressure and the volume
Adsorbed at monolayer coverage. BET equation can be written as:
𝑃 1 𝑃(𝐶 − 1)
=( )+
𝑣(𝑃 − 𝑃0) 𝑉𝑚𝐶 𝑉𝑚𝐶𝑃0

Where,
P, Partial pressure of N2 P0, Saturation Pressure at experimental
temperature

Prepared By: NIDHI R MEHTA Page

 Chemical Reaction Engineering- II (2170501)
Semester – VII (CHEM)
Chapter Name: Catalysis (Chapter 5)

V, volume adsorbed Vm, Volume adsorbed at monolayer coverage

C, constant. The is plotted as a function of . The plot is linear in the range of relative

pressures = 0.05 - 0.3. At higher relative pressure p/po, the BET plot deviates from linearity as non-ideality
or pore condensation was not accounted for the derivation of BET equation. Slope and intercept of this linear
plot is used for determination of monolayer capacity Vm.
The intercept and slope from the plot is given as

Then the monolayer volume vm is given as,

The total number of N2 molecules adsorbed corresponding to monolayer volume vm can be calculated as

Now each adsorbed N2 molecule occupies an area of surface comparable to its cross section area 0.162 nm2.

(B) Void Volume and Solid Density:

A void volume or pore volume of catalyst can be determined by boiling a weighed sample immersed in
water. After the air in the pores is displaced, the sample is superficially dried and weighed. The increase
in weight divided by density will give pore volume. The method used is Helium-Mercury method. In this
method, the volume of helium displaced by sample of catalyst is measured, then helium is removed and
the volume of mercury displaced is measured. From this, and the weight of sample, density of the solid
phase ρs can be obtained. Then void fraction of void volume ε is measured using following equation:
𝜀 = 𝜌𝑉
where V is void volume per gram particle.
In this way, pore volume and solid density of catalyst can be measured.
(C) Pore Volume Distribution:
There are two methods used for pore volume distribution measurement
(i) Mercury Penetration method: As mercury do not wet the catalyst surface because of significant
surface tension. The pressure required to force mercury into the pores depends on the pore radius. The
pressure varies inversely with 100 psi required to fill the pores of 1000 nm to 10000 psi for 10 nm.

Prepared By: NIDHI R MEHTA Page

 Chemical Reaction Engineering- II (2170501)
Semester – VII (CHEM)
Chapter Name: Catalysis (Chapter 5)

In second method, nitrogen gas is adsorbed until the nitrogen pressure approaches saturation value and
All void volume is filled with nitrogen. Then desorption isotherm is established by lowering the pressure
In increments and measuring the amount evaporated from capillary depends on radius of capillary.
Since, the vapour pressure of capillary depends on the radius of capillary, the data can be plotted for
void desorbed Vs pore radius. This will give Pore distribution.
Classification and Preparation of catalyst
In 1984, Dowden and coworkers proposed that catalyst maybe classified on the basis of electron
mobility as conductors, semiconductors and insulators. The Conductor catalyst are metal catalysts.
The metals that have strong electronic interaction with the adsorbates are included in this category. The
metals are used in various catalytic reactions such as methanol synthesis, oxidation, hydrogenation and
dehydrogenation processes.Examples of metal catalysts:Cu for water gas shift reaction and methanol synthesis;
Ag for oxidation of ethylene to ethylene oxide, Au for oxidation of methanol to formaldehyde; Fe for ammonia
synthesis; Pd and Pt for hydrogenation of olefins, dienes, aniline or nitriles as well as dehydrogenation of
alkanes, alcohols, cyclohexanes, cyclohexanols etc.
Semiconductors: The oxides and sulfides of transition metals that have catalytic activity are included in this
category. Similar to conducting metals, they are also capable of electronic interaction with adsorbed species
catalyze the same type of reactions. Usually the lower valence band electrons participate in bonding. The upper
conduction band separated by band gap energy is empty unless electrons are promoted by heat or radiation.
Semiconductor characteristics may be intrinsic or induced by addition of foreign ion, creating cationic or
anionic vacancies. Common transition oxides and sulfides such as CuO, AgO, NiO CoO, Fe2O3, MnO, Cr2O3,
V2O5 show conductivity. These materials participate in catalytic reactions and reaction occurs through
acceptation or donation of electrons between the reactant material and catalysts. Few applications of
semiconductor catalysts are: CuO for oxidation of nitric oxides, NiO for dehydrogenation of alkanes, MnO2 for
oxidation of alcohols, and V2O5 for oxidation of hydrocarbons.
Insulators: Catalytic functions of insulators are different from that of conductor and semi conductor materials.
Insulators have large values of band gap energy and very low concentration of impurity levels. The electrons
remain localized in valence bonds and redox type reactions involving electronic interaction as observed for metal
or semiconductor catalysts does not occur. However, insulators have sites that generate protons, thereby,
promote carbonium ion based reactions such as cracking, isomerization or polymerization. Al 2O3, SiO2, SiO2-Al2O3,
zeolites, MgO, CaO, MgAl2O4, SiO-MgO are few examples of the insulators used as catalysts.

Catalyst Preparation:
A solid catalyst contain three components (i) Catalytic agent (ii) Support/Carrier (iii) Promoter(if any)
(i) Catalytic agent: These are the catalytically active component in the catalyst. These components generate the
active sites that participate in the chemical reaction. Activity of any catalyst is proportional to the concentration
of these active sites. Though concentration of the active sites depends on the amount of catalytically active
component, however, it is not always directly proportional. Availability of active sites depends mainly on the
dispersion of catalytic agent. The dispersion is defined as ratio of total number of exposed atoms/molecules of

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 Chemical Reaction Engineering- II (2170501)
Semester – VII (CHEM)
Chapter Name: Catalysis (Chapter 5)

catalytic agent available for reaction to total number of atoms/molecules of catalytic agent present in the
catalyst sample.
(ii) Support/Carrier: Support or carrier provides large surface area for dispersion of small amount of catalytically
active agent. This is particularly important when expensive metals, such as platinum, ruthenium, palladium or
silver are used as the active agent. Supports give the catalysts its physical form, texture, mechanical resistance
and certain activity particularly for bi-functional catalysts. Area of the support can range from 1 - 1000 m2/gm.
Common supports are alumina, silica, silica-alumina, molecular sieves etc. The surface area of α - alumina is in
the range 1-10 m2/gm whereas the surface area for γ or η - alumina can be in the range 100 – 300 m2/gm.
The catalyst preparation methods can broadly categorized as follows:
1. Bulk preparation process: Bulk catalysts and supports are prepared by this method. Bulk preparation is mainly
done by the following methods:
(a)Precipitation process, (b)Sol-gel process
Impregnation process:
Supports are first prepared by bulk preparation methods and then impregnated with the catalytically active
material. The active materials can be deposited on the supports by various methods. Most of the methods
involve aqueous solutions and liquid solid interface. In some cases, deposition is done from the gas phase and
involve s gas- solid interface.
(a) Precipitation Process:
Precipitation provides method for forming porous catalyst. It consists of adding a precipitating agent to the
aqueous solution of the desired components. Washing, drying, and sometimes activation are subsequent steps
in the process. For example, preparation of Magnesium oxide catalyst. It can be prepared by precipitating
the magnesium from the nitrate solution by adding sodium carbonate. The precipitates of MgCO3 are then
Washed, dried and calcined to obtain the oxide form catalyst. Such variables as concentration of aqueous
solution, temperature, time of drying, and calcining steps may influence the surface area and pore structure
of final product. In some instance a porous material can be obtained by mixing the components with water
And milling to desired grain size, drying and calcining. After this the catalyst is impregnated over support.
The steps in preparation of catalyst impregnated over support includes (1) evacuating the carrier
(2) contacting he carrier with impregnating solution (3) removing the excess solution (4) drying (5)activation
For example, a nickel hydrogenation catalyst can be prepared on alumina by soaking the evacuated alumina
Particles with nickel nitrate solution, draining to remove excess solution and heating in oven to decompose
the nitrate to nickel oxide. The final step is reduction of oxide to metallic nickel is best carried out with the
particles in place in the reactor by passing the hydrogen through the equipment. Activation in situ prevents
contamination with air and other gases which might poison the reactive nickel.
(b) Sol-Gel method:
In this process initially stable colloidal solution called sol is formed. The sol is liquid suspension of solid particles
ranging in size 1 nm to 1 micron. It can be obtained by hydrolysis and partial condensation of precursor such as
inorganic salts. The further condensation of sol produces gel material. The gel is diphasic material in which the solid
encapsulates the solvent. The encapsulated liquid is removed either by drying or with supercritical extraction.

Prepared By: NIDHI R MEHTA Page

 Chemical Reaction Engineering- II (2170501)
Semester – VII (CHEM)
Chapter Name: Catalysis (Chapter 5)

The resulting solid product is called aerogel. When gels are dried using drying it is called aerogel and when it is dried
using extraction, it is called xerogel. The aerogel retains high porosity and has high pore volume.
For example, preparation of zirconium catalyst Zirconia propoxide is used as precursor. The sol is prepared using
aqueous solution of nitric acid and n-propanol. It is stabilized for 2 hour at room temperature and dried using
supercritical CO2 at 343 K and 2.1*107 Pa. The sol is then converted to gel which is calcined in two steps. In first
step it is calcined under vacuum for 3 hour at 383 K and in second it is calcined at 773 K in flowing O2 for 2 hour.
The final product obtained is Xerogel Zirconia.
Catalyst Promoters:
Promoters are generally defined as substances added during preparation of catalysts that improve the activity or
selectivity or stabilize the catalytic agents. The promoter is present in a small amount and by itself has little or
no activity. Promoters are termed as physical or chemical promoter depending on the manner they improve the
catalyst performance. The additives that maintain physical integrity of the support and/or deposited catalytic
agents are termed as physical promoters. For example, addition of small quantities of alumina to an iron catalyst
employed in ammonia synthesis prevents sintering of the iron crystallites. Thus, for this catalyst, alumina is a
physical promoter. The addition of K2O to the same catalyst increases the intrinsic activity of the iron crystallites
and therefore acts as a chemical promoter. The promoter can be added during catalyst preparation or during
reaction.
Catalyst Inhibitors:
Inhibitors act opposite to promoters. When added in small amount it can reduce catalysts activity, selectivity or
stability. Inhibitor is particular useful to prevent or reduce the activity of a catalyst for undesirable side
reactions. In oxidation of ethylene, ethylene dichloride is added to inhibit CO2 formation thus acting as an
inhibitor.
Catalyst Poison:
It is referred to the partial or total deactivation of a catalyst caused by exposure to a range of chemical
compounds. Poisoning may be desirable when it results in improved selectivity (e.g. Lindlar's catalyst) but may
be undesirable when the catalyst is rendered ineffective (e.g. Lead in catalytic converters). Poisoning refers
specifically to chemical deactivation, rather than other mechanism of catalyst degradation such as thermal
decomposition or physical damage.
Accelerators:
The material added to reactant stream to improve the performance of catalyst are called accelerators.
For e.g. Steam added to butene feed of dehydrogenation reactor appear to reduce the amount of coke formed
and increase the yield of butadiene. The catalyst in this case is Iron.
Nature and Mechanism of Catalytic reaction
A catalyst is effective in increasing the rate of chemical reaction because it makes possible route for alternative
which has lower energy than previous reaction. Consider the reaction of hydrogen and oxygen in presence of
Spongy Platinum catalyst. According to proposed concept, hydrogen combines with spongy Pt. to form
Intermediate substance, which then reacts with oxygen to provide the final product and reproduce the catalyst.

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 Chemical Reaction Engineering- II (2170501)
Semester – VII (CHEM)
Chapter Name: Catalysis (Chapter 5)

The general characteristics of catalyst may be summarized by:

1. A catalyst accelerates reaction by providing alternate paths to products, the activation energy of each catalytic
steps being less than that for homogeneous reaction.
2. In the reaction cycle active centres of catalyst are combined with at least one of the reactant and then freed
With the appearance of product. The reactant then again combines to reactant and cycle goes on.
3. Comparatively small active centres required to produce large product.
4. Equlibrium conversion is not altered by catalysis. A catalyst which accelerates forward reaction in equilibrium
Is a catlyst for the reverse reaction.
5. The catalyst can radically alter selctivity.

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 Chemical Reaction Engineering- II (2170501)
Semester – VII (CHEM)
Chapter Name: Catalysis (Chapter 5)
Typical mechanism
Catalysts generally react with one or more reactants to form intermediates that subsequently give the final
reaction product, in the process regenerating the catalyst. The following is a typical reaction scheme,
where C represents the catalyst, X and Y are reactants, and Z is the product of the reaction of X and Y:
X + C → XC (1)
Y + XC → XYC (2)
XYC → CZ (3)

CZ → C + Z (4)

Although the catalyst is consumed by reaction 1, it is subsequently produced by reaction 4, so it does not occur
in the overall reaction equation:

X+Y→Z

As a catalyst is regenerated in a reaction, often only small amounts are needed to increase the rate of the
reaction. In practice, however, catalysts are sometimes consumed in secondary processes.

The catalyst does usually appear in the rate equation. For example, if the rate-determining step in the above
reaction scheme is the first step
X + C → XC, the catalyzed reaction will be second order with rate equation v = kcat[X][C], which is
proportional to the catalyst concentration [C]. However [C] remains constant during the reaction so that the
catalyzed reaction is pseudo-first order: v = kobs[X], where kobs = kcat[C].

As an example of a detailed mechanism at the microscopic level, in 2008 Danish researchers first revealed the
sequence of events when oxygen and hydrogen combine on the surface of titanium dioxide (TiO2, or titania) to
produce water. With a time-lapse series of scanning tunneling microscopy images, they determined the
molecules undergo adsorption, dissociation and diffusion before reacting. The intermediate reaction states were:
HO2, H2O2, then H3O2 and the final reaction product (water molecule dimers), after which the water
molecule desorbs from the catalyst surface

Prepared By: NIDHI R MEHTA Page

 Chemical Reaction Engineering- II (2170501)
Semester – VII (CHEM)
Chapter Name: Catalysis (Chapter 5)

Prepared By: NIDHI R MEHTA Page