Chemical Reaction Engineering II

HETEROGENEOUS PROCESS AND SOLID CATALYSIS

 Rate equations for heterogeneous reactions

 Nature of catalysis
 Adsorption isothermal and rates of adsorption,
desorption and surface reaction
 Analysis of rate equation and rate controlling steps
 Surface area and pore-volume distribution
 Catalyst preparation
What is a catalyst ??

• Alters the rate of reaction

• Highly selective
• Does it participate in the reaction ??
• How does it change the rate ?? – Offers an
alternate path with low E.
• Does it affect HR, GR, and Eq. constant ??
• Does it affect yield & selectivity ??
Catalyst

Substance that affects the rate of a reaction

but emerged from the process unchanged

Catalyst changes only the rate of a reaction; it

does not affect the equilibrium

Catalysis
Occurrence, study and use of catalysts and
catalytic processes.
Representation of the action of catalyst
 Heterogeneous Reactions

• The reactants, products and catalysts are in the different

phases
Reactants Catalyst
  Products

Types
1. Catalytic type heterogeneous reactions
2. Non-Catalytic type heterogeneous reactions
 1. Catalytic type heterogeneous reactions

1. Gas-Solid Reactions
Ex: (i). Ammonia synthesis
(ii). Oxidation of SO2 to SO3 using V2O5 catalyst
(manufacture of H2SO4)
(iii). Catalytic cracking of crude oil

2. Gas-Liquid-Solid Reactions
Ex: (i). Catalytic hydrogenation of acetone to propanol
(ii). Catalytic oxidation of ethanol using O2 to acetic acid
 2. Non-Catalytic heterogeneous reactions
1. Gas-Liquid/Solid reactions
Ex: Combustion of coal, roasting of sulphide ores,etc.,
2. Gas-Liquid reactions
Ex: (i). Purification of gas mixtures (Absorption)
(ii). Ammonia+ aq.HNO3 -> Ammonium nitrate
(Absorption)
(iii). Chlorination of liquid hydrocarbons
3. Liquid-Liquid reactions
Ex: (i). soap preparation (acids + alkalies)
(ii). Nitration of organic compounds
4. Liquid-Solid reactions
Ex: calcium carbide+H2O -> Acetelyene
Burning of carbon
 Mechanism of Heterogeneous Catalysis:
1. Bulk Diffusion of reacting molecules to the surface of
the catalyst
2. Pore Diffusion of reacting molecules into the interior
pores of the catalyst
3. Adsorption of reactants (chemisorption) on the surface
of the catalyst
4. Reaction on the surface of the catalyst between
adsorbed molecules
5. Desorption of products
6. Pore Diffusion of product molecules to the surface of
the catalyst
7. Bulk Diffusion of product molecules
Mechanism of Heterogeneous Catalysis:
Mechanism of Heterogeneous Catalysis
Catalyst types
 Porous catalyst
 Eg. Raney nickel used in hydrogenation of vegetable & animal
oils- eg. Zeolites –porous itself act as a catalyst .
 Supported catalyst
 Eg. V2O5 on silica used to SO2 to SO3; Pt on Alumina
Supports- activated carbon, silica
 Monolithic catalyst-non porous, non supported
 Eg. Pt gauze in Nitric acid manufacture from ammonia,
 Ethanol to acetaldehyde-silver gauze
 Unsupported catalyst
 Eg. Promoted iron for NH3 synthesis
 Catalyst Properties
1. Surface Area
2. Void volume
3. Density of the solid material in
the particle
4. Pore volume distribution –
distribution of void volume
according to void size
 Rate equations for heterogeneous reactions

• No. of chemical steps (Series or Parallel steps)

• If the reaction consists of parallel steps
n
roverall   ri
i 1
• At steady state condition, the reaction consists of series
steps

roverall  r1  r2  r3  ......  rn
 Rate controlling step or rate limiting step
Consider the reaction type
A (g) + B (s) → R (g)
Condition:
1. First order reaction w.r.to gaseous reactant A
2. No ash is formed on the solid surface
Steps involved:
1. Gas (A) is transported from the bulk of gas to the solid
surface (B)
2. Surface reactions b/w A and B
3. Product R is transported from the solid surface to the
bulk gas
• The rate of mass transfer of A through gas film by
diffusion per unit surface to surface of B
 1 dN A
 rA"1   k g (C Ag  C As )
S dt
• The rate of reaction based on unit surface area of B
 1 dN A
 rA" 2
  k "C As
S dt
• These steps are in series. So at steady state,
Flux of A to the surface = Surface reaction

 rA"1  rA" 2
k g (CAg  C As )  k "C As
k g C Ag  (k  k g )CAs
"

k g C Ag
C As 
(k"  k g )
 1 dN A
Substitute C As into  r  "
A2  k "C As
S dt
k "k g
The overall rate of reaction  r  r 
" "
C Ag
k  kg
A1 A2 "
• For steps in series r1 = r2 = roverall
1
 rA"  rA" 2  rA"  C Ag
 1 1 
  
k "
 g k 
• This is the expression for overall rate in terms of bulk
reactant concentrations
• The overall rate of a heterogeneous process is
determined by the slowest step and hence it is called as
the rate controlling step.
• If kg>>k ” then the overall rate reduces to
-rA” = k” CAg
• Which implies the chemical reaction is the rate limiting
step (diffusion is rapid and reaction is slow)
• If k ” >> kg then the overall rate reduces to
-rA” = kg CAg

• Mass transfer is the rate limiting step and rapid surface

reaction
• If the reaction is taking place in the region of
intermediate b/w chemically controlled region and mass
transfer controlled region, then the overall rate equation
is
k "k g
 rA"  rA" 2  C Ag
k  kg
"
 Solid Catalyzed Reactions

• A substance that enhances the rate of a chemical

reaction and is recovered at the end of the reaction
without change in its mass and chemical composition is
called a catalyst.
• A catalyst which has a large area resulting from pores is
called as a porous catalyst.
• Characteristics of solid catalyst:
1. Activity – it is a measure of the accelerating effect that a
catalyst has on the rate of a given reaction.
2. Specificity (selectivity) – A property of a catalyst to
speed up the main reaction (produce desired product) in
the presence of several side reactions.
 Examples of catalytic reactions

• Catalytic cracking
• Catalytic reforming
• Aromatization
• Isomerization
• Hydrogenation of vegetable oils
• Enzymatic reactions in food processing
• Conversion of SO2 to SO3 with the presence of V2O5
• NH3 synthesis
 Characteristics of catalytic reactions

• Catalyst remains unchanged at the end of the reaction

• Very small quantity required
• Decreases the activation energy
• Develops a new mechanism
• Does not alter the chemical equilibrium
• Ea, for catalyst << Ea, for non-catalyzed reaction
• Catalyst plays a specific role in chemical reactions
 Catalyst Preparation Methods
1. Precipitation
2. Gel formation Entire material
3. Simple mixing of components constitutes catalyst
4. Impregnation Active material
dispersed on support
Properties or carrier
• Activity
• Physical Properties
– Surface area,
– particle size,
– pore size and
– particle structure.
1. Precipitation method
2. Gel formation method

Example:
Silica & Alumina catalyst
3. Simple mixing of components
 4. Impregnation method

Carriers provide a large surface area with

small amount of active material

Expensive agents such as platinum,

palladium, ruthenium and silver
4. Impregnation method
 Turnover Frequency (TOF)

• To quantify the activity of catalyst.

• Number of molecules reacting per site per second at the

conditions of the experiment.

• Dispersion – of the catalyst is the fraction of the metal

ions deposited that are on the surface.
 Promoters and Inhibitors

• Components of a catalyst include: carrier, promoters and

inhibitors
• Silica gel and Alumina are widely used as supports
• Promoter is defined as a substance added during
preparation of a catalyst which improves activity or
selectivity or stabilizes the catalytic agent so as to
prolong its life
• Will be present in small quantity. Some promoters are
used to increase the number of active sites hence
making the catalyst more active
Examples

K2O, CaO, SiO2, and Al2O3 is used as a promoter for Iron catalyst
in ammonia synthesis
 Inhibitor
• Opposite of a promoter
• substance added during preparation of a catalyst, it
lessens activity, selectivity or stability.
• Useful for reducing the activity of a catalyst for and
undesirable side reaction.
• Example: Oxidation of ethylene to ethylene oxide using
silver supported on alumina catalyst. Byproducts CO2
and H2O formation is suppressed by adding halogen
compounds inhibits the complete oxidation.
 Catalyst Deactivation (Poisoning)
• Activity of a catalyst decreases with time
• Catalysts for cracking and some other hydrocarbon
reactions lose much of their activity in seconds due to
poisons.
• Poisons are defined as substances either in the reactant
stream or produced by the reaction, which lowers the
activity of a catalyst
• Continuous regeneration of cracking catalysts is
necessary because of the deposition of one of the
products carbon on the surface
• The slow decrease in activity is due to chemisorption of
reactants, products or impurities in the liquid stream
• Rapid deactivation is caused by physical deposition of a
substance that blocks the active sites of a catalyst
• Rapid deactivation is also called as fouling
• Deactivation can also be caused by a change in the
structure of the catalyst due to prolong exposure to
elevated temperature in the reacting atmosphere.
Eg: sintering
 Types of Poisons

Based on the way poisons operate they are classified as :

1. Deposited poisons
2. Chemisorbed poisons
3. Selectivity poisons
4. Stability poisons
5. Diffusion poisons
Deposited Poisons
• Carbon deposition on catalyst is an example of this
category
• The carbon covers the active sites of the catalyst and
may plug the pore entrances
• This type is partially reversible and regeneration can be
achieved by burning CO to CO2 with air or steam
• Regeneration process is a gas-solid non catalytic
heterogeneous reaction
Chemisorbed Poisons
Compounds of sulphur and other materials are
chemisorbed on Ni, Cu, and Pt catalysts
• The decline in activity stops when an equilibrium is
reached b/w the poison in the reactant stream and that
on the catalytic surface
• If the strength of the bond is weak the activity of the
catalyst can be regained otherwise it is a permanent
poisoning
Selectivity Poisons
Some materials in the reactants get adsorbed on the
surface and catalyze undesirable reactions thus lowering
the selectivity
Example
very small quantities of Ni, vanadium, iron etc. in
petroleum stocks act as poisons in this way. When such
stocks are cracked the metals deposit on the catalyst
and act as dehydrogenation catalysis. This results in
increased yields of hydrogen and coke and lower yields
of gasoline
Stability Poisons
• When water vapour is present in SO2 - air mixture
supplied to a Pt- alumina catalyst, a decrease in
oxidation activity occurs
• This type of poisoning is due to the effect of water on the
structure of the alumina carrier.
• Temperature has pronounced effect on stability of
poisoning.
• Sintering and localized melting may occur as the
temperature is increased and thus changes the catalyst
structure
Diffusion Poison
Example
carbon deposition on cracking catalyst
• Blocking the pore mouths prevents the reactants from
diffusing into the inner surface
• Entrained solids in the reactants or fluids which can react
with the catalyst to form a solid residue, can cause this
type of poisoning
Accelerators
materials that are added to the reactant stream to
improve the performance of a catalyst are called as
accelerators.
Example

Butene Iron
 Butadiene
Steam added to the butene feed of a dehydrogenation
reactor appeared to reduce the amount of coke formed
and increase the yield of butadiene. The catalyst used is
iron
 Poisons for various catalysts
Catalyst Reaction Types of poisoning Poisons

Silica, cracking Chemisorption Organic bases

alumina Deposition Carbon
Stability Water
selectivity Heavy metals

Ni, Pt, Cu Hydrogenation, chemisorption Cpds of S Se, Te,

dehydrogenation P, As, Zn, Hg, etc

Silver C2 H4 + O C2H4O selectivity Methane, ethane

Vanadium oxidation chemisorption As

oxide

69
 Difference b/w Physisorption and Chemisorption
Parameter Physisorption Chemisorption
Adsorbent All solids Some solids
Adsorbate All gases below critical Some chemically reactive
temperature gases

Temperature range Low temperature High temperature

Heat of adsorption Low High
Rate , Ea Very rapid, low Ea Non activated, low Ea
Activated, high Ea

Coverage Multilayer Monolayer

Reversibility High reversible Often irreversible
Importance Determination of surface Determination of active-
area and pore size center area and elucidation
of surface reactive kinetics
 Autocatalytic reactions

• Reactions in which the rate increases with product

concentration also occur. (i.e. one of the product will be
acting as a catalyst)
• Organic feed + Microbes  inert Products +More yeast
(sugars) (Yeast) (alcohol)
 Adsorption isotherms
Adsorption (surface phenomena)
1. Physical adsorption (Physisorption, weak van der waals
force)
- surface area and pore-size distribution in porous
catalysts can be calculated
2. Chemical adsorption (Chemisorption, covalent bond)
(i). Activated chemisorption (slow process)
The rate of adsorption varies with the temperature
according to a finite Ea in the Arrhenius equation.
(ii). Non-activated chemisorption (rapid process)
Chemisorption occurs very rapidly, suggesting an Ea
near zero.
 Langmuir isotherms
Assumptions
1. Monolayer coverage on the surface of adsorbent
2. No interactions between the adsorbate atoms or
molecules
3. Coverage-independent binding energy
4. Thermodynamic equilibrium of adsorption and
desorption rate being equal.
 Adsorption isotherms
q e  K F C1e/ n
• Freundlich isotherms

q m K L Ce
• Langmuir isotherms qe 
1  K L Ce

• Redlich-Peterson isotherms

• Toth isotherms

• Temkin isotherms
 Surface area of catalyst

• The area provided for the adsorption per gram of

adsorbent is called as the surface area (m2/g).
• Catalytic substance and support
• The catalyst substance is dispersed on the surface of the
support or carrier.
• Silica gel and Alumina are widely used as supports
 Problems

Spray drying and other procedures for

manufacturing small particles can produce particles
as small as 2 to 5 microns. Calculate the external
surface area of nonporous spherical particles of 2
microns diameter. What size particles would be
necessary if the external surface is to be 100 m2/g.
The density of the particles is 2.0 g/cm3.
 Solution
• The external surface area per unit volume of a spherical
particle of diameter , dp, is d p2 6

d 3p /6 dp
• if the particle density is , p the surface area, per gm of
particles would be,
• where 6
Sg 
p d p
dp  2 microns  2  10 cm 4  p  2.0g / cm 3

6
(i ). S g  4
 1.5  10 4
cm 2
/ g (1.5  10 m / kg )  1.5
3 2
m2 / g
2( 2  10 )
6 6
(ii ). d p    0.03  10  4 cm  0.03  10 6 m  0.03 microns
p S g 2(100  10 )
4
 Solid catalysts

• Heterogeneous catalysis involves the use of a catalyst

in a different phase from the reactants. Typical examples
involve a solid catalyst with the reactants as
either liquids or gases.
• Solid catalysts are normally porous in order to be
effective
• Surface area plays an important role in this type of
catalyst
Examples
• The simplest example of this is the reaction between
ethene and hydrogen in the presence of a nickel
catalyst.

• One important industrial use is in the hydrogenation of

vegetable oils to make margarine, which also involves
reacting a carbon-carbon double bond in the vegetable
oil with hydrogen in the presence of a nickel catalyst.
 Determination of surface area
• The standard method for measuring catalyst areas is
based on the physical adsorption of a gas on the solid
surface.
• Usually the amount of nitrogen adsorbed at equilibrium
at the normal boiling point (- 195.8 oC) is measured over
a range of nitrogen pressures below 1 atm.
• Under these conditions several layers of molecules may
be adsorbed on top of each other on surface.
• The amount adsorbed when one molecular layer is
attained must be identified in order to determine the
area.
• .
 All-Glass Apparatus
• The apparatus operates at a low pressure which can be varied from
near zero up to about 1 atm. The operating temperature is in the
range of the normal boiling point.
• The data obtained are gas volumes at a series of pressures in the
adsorption. The observed volumes are normally corrected to cubic
centimeters at 0 oC and 1 atm (standard temperature and pressure)
and plotted against the pressure in millimeters, or as the ratio of the
pressure to the vapor pressure at the operating temperature.
• Typical results from Brunauer and Emmett’s work are shown in
figure for the adsorption of several gases on a 0.606 g sample of
silica gel.
• To simplify the classical experimental procedure a flow method has
been developed in which a mixture of helium (or other non-adsorbed
gas) and the gas to be adsorbed is passed continuously over the
sample of solid.
• The operating total pressure is constant, and the partial pressure of
adsorbable gas is varied by changing the composition of the
mixture.
• The procedure is to pass a mixture of known composition over the
sample until equilibrium is reached, that is, until the solid has
adsorbed an amount of adsorbable component corresponding to
equilibrium at its partial pressure in the mixture.
• Then the gas is desorbed is measured with a thermal-conductivity
cell or other detector. This gives one point on an isotherm, such as
shown in figure. Then the process is repeated at successively
different compositions of the mixture until the whole isotherm is
obtained.
• The curves in figure are similar to the extent that at low pressures
they rise more or less steeply and then flatten out for a linear section
at intermediate pressures.
• After a careful analysis of much data it was concluded that the lower
part of the linear region corresponded to complete monomolecular
adsorption.
Adsorption isotherms for various gases on a 0.606 g sample
of silica gel
• If this point could be located with precision, the volume of one
monomolecular layer of gas, vm, could then be read from the curve
and the surface area evaluated. The Brunauer – Emmett – Teller
method locates this point from an equation obtained by extending
the Langmuir isotherm to apply to multilayer adsorption.
p 1 p
  (1)
 K m  m
• Brunauer, Emmett and Teller adapted this equation for multilayer
adsorption and arrived at the result

p 1 (c  1)p
  ( 2)
(p o  p ) m c cm p o
• Where po is the saturation or vapor pressure and c is a constant for
the particular temperature and gas-solid system. According to
equation (2), a plot of vs should give a straight line,
p p
as shown in figure (2).
(p o  p ) po
Brunauer – Emmett – Teller method for finding
Surface area of catalyst
• Of additional significance is the fact that such straight lines can be
accurately extrapolated to (p/po = 0).The intercept I obtained from
this extrapolation, along with the slope s of the straight line, gives
two equations from which v m can be obtained.
1 p
I at 0 (3)
m c po
c 1
s ( 4)
m c
• Solving these equations for the volume of adsorbed gas
corresponding to a monomolecular layer gives

1
m  ( 5)
Is
• The volume vm can be readily converted to the number of molecules
adsorbed. However, to determine the surface area it is necessary to
select a value for the area covered by one adsorbed molecule. If this
is α, total surface area is given by,
  m N o 
Sg     ( 6)
 V 
• Where No is Avogadro’s number, 6.02 x 1023 molecules / mol
• V is volume per mole of gas at conditions of vm, since vm is recorded
at standard temperature and pressure, V = 22,400 cm3 / g mol.
• Emmett and Brunauer proposed that is projected area of a molecule
on the surface when the molecules are arranged in close two-
dimensional packing. This value is slightly larger than that obtained
by assuming that the adsorbed molecules are spherical and their
projected area on the surface is circular. The proposed equation is
2/3
 M 
  1.09 
N o  
(7)

• Where M is molecular weight and is the density of the adsorbed
molecules. 
• For Nitrogen

 
Sg  4.35104 v m (8)
  m N o 
Sg     ( 6)
 V 
2/3
 M 
  1.09   (7)

 o 
N
p 1 (c  1)p
  ( 2)
(p o  p ) m c cm p o
 p 1 (c  1)p
  ( 2)
(p o  p ) m c cm p o

p p
Plot (p o  p ) vs po

1 p c 1
I at 0 (3) s ( 4)
m c po m c
1
m  ( 5)
Is
 Void volume and Solid density
Helium-Mercury method
• The volume of helium is displaced by a sample of catalyst is
measured; then the helium is removed, and the volume of mercury
that is displaced is measured.
• Since mercury will not fill the pores of most catalysts at atmospheric
pressure, the difference in volumes gives the pore volume of the
catalyst sample.
• The volume of helium displaced is a measure of the volume
occupied by the solid material.
• From this and the weight of the sample, the density of the solid
phase,ρs , can be obtained. Then the void fraction, or porosity, of the
particle, may be calculated from the equation

void (pore ) volume of particle m p Vg Vg s

p   
total volume of particle m p Vg  m p (1 / s ) Vg s  1
where, mp = mass of the particle
Vg= void volume per gram of particles
• If the sample of particles is weighed, the mass divided by
the mercury volume gives the density p of the porous
particles. Note that the porosity is also obtainable from
this density by the expression

void volume Vg
p    p Vg
total volume 1 / p

• From the helium – mercury measurements the pore

volume, the solid density, and the porosity of the catalyst
particle can be determined.
Micropores: Void space within the particles (Pore dia<2nm)
Macropores: Void region between particles (Pore dia>50nm)

Bidisperse pore system: Pellet containing two pore regions:

small void spaces within the individual particles and larger
spaces between particles.
 Problems
1. In an experiment to determine the pore volume and catalyst-
particle porosity the following data were obtained on a sample
of activated silica (granular, 4 to 12 mesh size):

Mass of catalyst sample placed in chamber =101.5 g

Volume of helium displaced by sample =45.1 cm3
Volume of mercury displaced by sample =82.7 cm3
Calculate the required properties.

82.7  45.1
Vg   0.371 cm 3 / g
101 .5

101 .5
s   2.25 g / cm 3
45.1
Vg s 0.371  2.25
p    0.455
Vg s  1 (0.371  2.25)  1
 Pore volume distribution
1. Mercury-Penetration Method
2. Nitrogen-Desorption Method
3. Combination of Mercury-Penetration & Nitrogen-
Desorption Method
 1. Mercury penetration method
• The mercury-penetration method depends on the fact
that mercury has a significant surface tension and does
not wet most catalytic surfaces. This means that the
pressure required to force mercury into the pores
depends on the pore radius.
• The pressure varies inversely with a; 100 lb/in.2.
(approximately) is required to fill pores for which a = 10,
000 oA, and 10, 000 lb/in.2 is needed for a = 100 oA.
• Simple techniques and equipment are satisfactory for
evaluating the pore-volume distribution down to 100 to
200 oA, but special high-pressure apparatus is
necessary to go below a = 100 oA, where much of the
surface resides.
• By equating the force due to surface tension (which
tends to keep mercury out of a pore) to the applied force,
Ritter and Drake obtained

a 2p  2a cos 

 2 cos 
a
p

• Where θ is the contact angle between the mercury and

pore wall (figure).
• Then the working equation for evaluating the radius
corresponding to a given pressure is
8.75  10 5
a( A ) 
o
p(lb / in. 2 )
 2. Nitrogen-desorption method
• As the low temperature nitrogen-adsorption experiment is
continued to high pressures multilayer adsorption occurs,
and ultimately the adsorbed film are thick enough to
bridge the pore. Then further uptake of nitrogen will result
in capillary condensation.
• Since the vapor pressure decreases as the capillary size
decreases, such condensation will occur first in the
smaller pores. Condensation will be complete, as , (p/po
= 1) when the entire void region is filled with condensed
nitrogen.
• Now, if the pressure is reduced by a small increment, a
small amount of nitrogen will evaporate from the
meniscus formed at the ends of the largest pores.
• Pores which are emptied of condensate in this way will
be those in which the vapor pressure of nitrogen is
greater than the chosen pressure.
• The Kelvin equation gives the relationship between
vapor pressure and radius of the concave surface of the
meniscus of the liquid.
• Since some of the nitrogen is adsorbed on the surface,
and therefore not present because of capillary
condensation, the Kelvin relationship must be corrected
for the thickness of the adsorbed layers.
• With this correction, the pore radius is related to the
saturation pressure ratio (vapor pressure ’p’ in the pore
divided by the normal vapor pressure po) by
  2V1 cos 
a
R g T ln( p / p o )

Where, V1= molal volume of the condensed liquid

 = surface tension
 = contact angle between surface and condensate
• Since nitrogen completely wets the surface covered with
adsorbed nitrogen, θ= 0 and cos θ = 1 . The thickness δ
depends on p/po . The exact relationship has been the
subject of considerable study, but Wheeler’s form
1 / n
 po 
( A )  9.52 log 
o

 p 
• For nitrogen at – 195.8 oC (normal boiling point), for a-δ
in angstroms, becomes
1
 po 
a    9.52 log 
 p 

• For a chosen value of p/po , the above equation give the

pore radius above which all pores will be empty of
capillary condensate.
• Hence, if the amount of desorption is measured for
various p/po, the pore volume corresponding to various
radii can be evaluated.
• Differentiation of the curve for cumulative pore volume
vs. radius gives the distribution of volume.
 3. Combination of Mercury-Penetration and Nitrogen-
desorption method

• By combining mercury-penetration and nitrogen-desorption

measurements, pore-volume information can be obtained
over the complete range of radii in a pelleted catalyst
containing both macro- and micropores.
• Figure shows the cumulative pore volume for two alumina
pellets, each prepared by compressing porous particles of
boehmite (Al2O3.H2O). The only difference in the two is the
pelleting pressure.
• Increasing this pressure causes drastic reductions in the
space between particles (macropore volume) but does not
greatly change the void volume within the particles or surface
area. The derivative of the volume curves in figure (1) gives
the pore volume distribution, and these results are shown in
figure (2).
 Summary
1. The rate equations for the heterogeneous reactions and
its basics
2. Nature of solid catalyzed reactions
3. Adsorption isothermal and rates of adsorption,
desorption and surface reaction
4. Analysis of rate equation and rate controlling steps
5. The different methods available for the surface area and
pore-volume distribution
6. Methods available for the catalyst preparation