Determination of Surface area

Pore volume
 Surface Area Measurement

• Standard method is based on physical

adsorption of a gas on a solid surface.

• Usually use nitrogen at the normal boiling

point (-195.8°C).

• Adsorption isotherm determined based on

development by Brunauer-Emmett-Teller.
 Gas Adsorption Technique
 To measure the specific surface area and pore size distribution of
powdered or solid materials.

 Dry sample is usually evacuated of all gases and cooled to a temperature

of 77K (-195.8°C), the normal boiling point temperature of nitrogen.

 At this temperature nitrogen gas physically adsorbs on the surface of the

sample.

 Nitrogen is used most often to measure BET surface, but if the surface
area is very low, argon or krypton may be used as both give a more
sensitive measurement, because of their lower saturation vapor pressures
at liquid nitrogen temperature.

 This adsorption process can be considered to be a reversible

condensation or layering of molecules on the sample surface during which
heat is evolved. Nitrogen gas is ideal for measuring surface area and pore
size distribution.
 Surface Area Measurement
• A sample contained in an evacuated sample tube is cooled
(typically) to cryogenic temperature, then is exposed to analysis
gas at a series of precisely controlled pressures.
• With each incremental pressure increase, the number of gas
molecules adsorbed on the surface increases. The pressure at
which adsorption equilibrium occurs is measured and the
universal gas law is applied to determine the quantity of gas
adsorbed.
• As adsorption proceeds, the thickness of the adsorbed film
increases. Any micropores in the surface are quickly filled, then
the free surface becomes completely covered, and finally larger
pores are filled. The process may continue to the point of bulk
condensation of the analysis gas.
• Then, the desorption process may begin in which pressure
systematically is reduced resulting in liberation of the adsorbed Micromeritics
molecules. As with the adsorption process, the changing
quantity of gas on the solid surface is quantified. These two sets
ASAP 2010
of data describe the adsorption and desorption isotherms.
Analysis of the isotherms yields information about the surface
characteristics of the material
 Gas Adsorption Technique - BET
One or more data points of the adsorption isotherm must be measured and the
BET (Brunauer, Emmett and Teller) equation is used to give specific surface
area from this data.

The BET equation is used to give the volume of gas needed to form a
monolayer on the surface of the sample. The actual surface area can be
calculated from knowledge of the size and number of the adsorbed gas
molecules.

Nitrogen is used most often to measure BET surface, but if the surface area is
very low, argon or krypton may be used as both give a more sensitive
measurement, because of their lower saturation vapor pressures at liquid
nitrogen temperature.
 Surface Area Determination

• Langmuir Isotherm p

1

p
 Km m

• Brunauer, Emmett, p 1 c  1p

 
and Teller Isotherm (BET) po  p  mc cm po

p
• Plot of vs. p is linear with
po  p  po

1 c 1
intercept  slope 
m c cm
 Surface Area Determination

• Solve these slope/intercept equations for

the monolayer adsorption volume (um):

1 𝑐 −1
𝐼𝑛𝑡𝑒𝑟𝑐𝑒𝑝𝑡 =𝐼 = 𝑆𝑙𝑜𝑝𝑒 =𝑆=
𝑣𝑚 𝑐 𝑣𝑚 𝑐

1
𝑣𝑚=
𝐼 +𝑆
 Surface Area Determination

• If a is the total surface area covered by

one adsorbed molecule, the total surface
per gram of solid (Sg) can be found as,
where No is Avogadro’s number and V is
the volume of gas at conditions of um.

 m N o 
Sg   
 V 
 Surface Area Determination

• Emmett and Brunauer proposed that a is

simply the projected area of a molecule
on the surface when the molecules are
arranged in close 2D packing.

2
 M  3
 1.09 
 N o 
 Void Volume and Solid Density

• The void (pore) volume of a catalyst

particle can be estimated by filling the
pores with a liquid of known density,
followed by weighing of the particle.

• The weight difference (before/after filling)

is due to liquid contained in the pores.

• Standard system is helium-mercury.

 Void Volume and Solid Density

• Finding the void fraction:

VHg displaced  VHe displaced
Vg 
m catalyst sample
pore volumeof particle
p 
total volumeof particle m catalyst sample
m p Vg s 
 VHe displaced
m p Vg  m p 1 s 
Vgs  p porosity

Vgs  1 m p mass of particle
Vgp Vg void volumeper gram particles
s density of solid phase
p density of porous particle
 Catalyst Pellets
Pellets of Alumina (Al2O3) are widely used in a packed
bed.

Preparation of pellets:
Alumina particles: 20-200 microns diameter
Micropores in the particle: 10-200 Å
Particles are prepared by spray drying.
Particles are lumped together and pressurized.
Microporosity and macropore diameter depends
on the pelleting pressure.
 Pellets

• Five pellets prepared at five different pressures.

• Increasing pressure decreases the pellet size and increases the
pellet density. Pellet density is approximately proportional to the
applied pressure.
• Pressure causes increase in pellet density; its effect is more on
macropore volume than on micropore volume. We don’t want porous
activity our catalyst to get destroyed by losing porous volume.
 Pellets

• External surface area of even very small particles are

small in comparison with internal surface of pores.
• Predominant surface is the surface in pores within the
particles, and external area of pellet is negligible.
• Micropore and macropore volumes and porosities for
bidisperse catalyst pellets are calculated by the same
methods as used for monodisperse pore systems.
Macropores and micropores
Pores in catalysts
Catalyst with Support
 Pores

• Micro- and macro-pores formed in pellets are of random shape and

sizes.

• It will be very difficult task to study kinetics of catalyst w/o

quantifying the descriptions of pore structures.

• If these pores can be modeled in some shape, we can quantify

catalyst properties.

• Model a pore as a cylinder of radius, a, where a is a variable.

• Distribution of pores (void volume) is defined as a function of pore

radius, a.
 Pore-Volume Distribution

• Higher pore volume with low radii pores is possible, but

may be of no use.

• Effectiveness of internal surface for catalytic reactions

depends not only on the volume of void spaces, but also
on radius of the void regions.

• Pore volume – pore size distribution: how much volume

contribution by a specified sized pore.

• Void spaces are non-uniform in size, shape, and length,

and are normally interconnected. These characteristics
are not same for all catalysts.
 Methods for determining distribution
Mercury penetration method
• Mercury has significant surface tension and does not wet the most
catalyst surface

Hg in a capillary
Hg on a surface

• Pressure is required to force mercury into the pores and that depends
inversely on the radius: higher pressure for Hg penetration in lower radii
pore.
• Example: 100 lb/in.2 for a = 10,000 Å and 10,000 lb/in.2 for a = 100 Å.
 Methods for determining distribution

Mercury penetration method

• Using simple pressure varying equipments, pore
distribution up to 100 to 200 Å can be evaluated.

• Most pores reside below 100 Å  requires special

high pressure apparatus.
 Methods for determining distribution
Nitrogen desorption method
• Nitrogen adsorption experiment, operating at nitrogen B.P. (-158.7 °C) is
continued until pressure approaches the saturation value, 1 atm.
• At saturated pressure, all void volume is filled with adsorbed and condensed
nitrogen.
• Lowering the pressure, desorption isotherm is established: amount of
nitrogen desorbed w/ decreasing pressure  resembles evaporation of liquid
from a capillary.
• Vapor pressure of evaporating liquid depends on the radius of the capillary:
plot data for volume desorbed vs. pressure (pore radius).
• Vapor pressure is not affected significantly by radii of curvature greater than
200 Å, so not applicable for larger pores.
 Methods for determining distribution
• Use of both methods to cover entire range of pore radii (10 to
10,000 Å) – bidisperse catalyst or support, such as alumina pellets.
• Monodispirse pore (< 200 Å) distribution in silica gel - use of
nitrogen adsorption.
• In bidisperse pore system, predominant part of catalytic reactions
occurs in pores < 200 Å, that is the micropore region, and bulk
surface exists in this region.
• But diffusion of reactants in 200 Å (or less) pore occurs through
bigger pores, complete distribution of pore volume is required to
establish the effectiveness of the interior surface, that is, the global
rate of reaction.
 Mercury Penetration method
• Equate the force due to surface
Fp
tension, Fσ, and applied force, Fp:

 a 2 p 2 a cos(   )  2 a cos  θ

 2 cos 
a Fσ Hg
p
a
θ is the contact angle between the mercury and pore wall. It varies with the
nature of the solid surface; 140° is a good average approximation.
8.75 105
a (angstrom) 
p (lb / in.2 )
Mercury Penetration method
Mercury
Pressure Penetration pore radius, a
lb/in.2 cm3 (Å)
1.77 494350 (~50 micron) Hg penetration data:
116 0.002 7543
310 0.006 2823
344 0.01 2544
0.624 g sample of UO2 pellet
364 0.014 2404
410 0.02 2134 UO2 particles are non-porous  All pores
456 0.026 1919
484 0.03 1808 in a plellet are macropores only.
540 0.038 1620
620 0.05 1411 Initial pressure = 1.77 lb/in.2 abs
710 0.064 1232
800 0.076 1094
830 0.08 1054
Initial mercury displaced = 0.190 cm3
900 0.088 972
1050
1300
0.11
0.112
833
673 1 psi = 14.7 atm
1540 0.118 568
1900 0.122 461
2320 0.124 377
What would be the porosity of pellet?
3500 0.125 250
Pore-Volume distribution using Hg-penetration
method: larger pores

Data for 1.0 g of

UO2 pellet

Data for 0.624 g

of UO2 pellet

Cumulative
pore volume
with pores of
radius < a
Pore-Volume distribution using Hg-penetration
method: larger pores
 Nitrogen Desorption method
• Continuing low-temperature N2-adsorption to higher pressures
thickens the layer in the pore, and fill the pore, via multilayer
adsorption.
• Further uptake of N2 results in capillary condensation.

In capillary condensation, vapor

condenses below saturation vapor
pressure, p0, resulting from an
increased van der
Waals interactions between vapor
phase molecules inside the
confined space of a capillary.
 Nitrogen Desorption method

• Kelvin’s equation
p 2 H  Vl
ln 
p0 RgT

• p = equilibrium vapor pressure in pore,

• p0 = saturation vapor pressure,
• H = mean curvature of meniscus = cos  , where θ is contact angle between surface and
condensate a

• Vl = molar volume of condensed liquid,

• σ = liquid/vapor surface tension,
• Rg = gas constant,
• T = temperature
 Nitrogen Desorption method
• Vapor pressure decreases with decreasing capillary size.
Condensation will occur first in smaller pores and will
complete, as p/p0 → 1, when entire void region is filled
with condensed N2.

• Reducing pressure in a small increment results in

evaporation from meniscus of the largest pores, because
vapor pressure of N2 in these pores is higher than the
operating pressure.
 Nitrogen Desorption method
• If δ is the thickness of already adsorbed layer leaving condensation radius = a- δ.

Corrected Kelvin’s equation

p 2 Vl cos 
ln 
p0 RgT a   
2 Vl cos 
a   
RgT ln  p p0 
• Since N2 completely wets surface that is already covered with adsorbed N 2, θ = 0°,
and cosθ = 1.
• δ depends on ln  p p0 
1 n
 p 
• Wheeler’s form is commonly used:  (angstrom) 9.52  log 0 
 p 1
 p0 
• For N2 at -195.8 °C (a- δ) can be written as (a   ) in angstrom 9.52  log  . Get δ
 p
from above equation.
• For a chosen value of p/p0, above equations give the pore radius above which all
pores will be empty of capillary condensate.
Pore-Volume distribution using N2-desorption
method: smaller pores
 Analysis of larger (macro) and smaller
(micro) pores

• Combine Hg-penetration and N2 –desorption

measurements to obtain pore volume distribution
over the complete range of radii in pelleted
catalyst containing both macro- and micropores.
Complete range of Pore-Volume distribution

Bidisperse pores

At low pressure, macropore volume

dominates.

Increasing pressure affect

macropore volume greatly, but
does not affect micropore volume
and surface area. This indicates
that most of pores are micropores.
 Complete range of Pore-Volume distribution

Common characteristics of bisperse pores in alumina is vivid.

Most of pores are of 20Å  micropores
At low pressure, pores of 8000 Å dominate.
At higher pressure, most of pores > 2000 Å get squeezed.
 Average pore size
• Assume pores are straight, cylindrical, not interconnected and having same
radius, , and length, .
• Sg = surface area/g-cat, Vg = Pore volume/g-cat, mp = mass of catalyst, n =
number of pores

or

Example

Integration method gives 45 Å

Similar exercise can be done for micro and

macropores, separately.
 Theories of catalytic activity
• Chemical factor – formation of chemical compound (Sabatier). Ex. Nickel hydride
• Geometric properties – spacing of atoms facilitating adsorption of reactant
molecules (Taylor, Balandin and Beeck). Ex. Metallic films
• Electronic properties – electron mobility in catalysts (Dowden and coworkers)
– Conductor catalysts: Metals. Ex. Ag, Pt, V, Fe etc. Chemical adsorption by electron transfer
– Semiconductor catalysts: Oxides. Ex. NiO, Cu2O and ZnO.. These materials have capability
of interchanging electrons from filled valence bands when sufficient energy (may be heating)
is provided. Upon electron transfer, semiconductor becomes conductor.
– Insulator catalysts: Silica gel, alumina and their combinations. They do not conduct
electrons even at higher temperatures. They are strong acid, and catalyse hydrocarbon
reactions through formation of carbonium ions.

• To understand the behavior of solid catalysts, the chemical structure of adsorbed molecules
must be known.
• Examination of surface and bulk properties of solids provide good understanding.
• Characterization techniques: X-ray scattering, NMR, Raman spectroscopy, HR-TEM,
Extended X-ray absorption, Fine structure spectroscopy, and Photo-acoustic spectroscopy.
 Common Characterization Techniques for
Heterogeneous Catalysts

Source: https://www.uprm.edu/
 Classification of catalysts

Source: https://www.uprm.edu/
 Details of catalysts and their functions
• Metals:
– Chemisorb O2 and H2, hence are effective for oxidation-reduction, and hydrogenation-dehydrogenation
reactions.
– Pt for oxidation of SO2: SO2 + O2  SO3
– Ni for hydrogenation of hydrocarbons

• Metals oxides (semiconductor):

– Similar to metals but catalyse at higher temperatures
– Same kind of reactions
– Metals for strong chemisorption bond with O2 and CO, hence these gases poison the metal catalysts during
hydrogenation process
– Metal oxides are less susceptible to such poisoning

• Others:
– Oxides of transition metals, MoO3 and CrO3, are good catalysts for polymerization of olefins.
– Al(C2H5)3+TiCl4 is an excellent catalyst for producing isotactic polymers from olefins.
– Al2O3 and SiO2 for alkylation, isomerization, polymerization and cracking of hydrocarbons. Mechanism is –
reaction through formation of carbonium ions at acidic sites of catalyst. Homogeneous catalysts such as HF and
H2SO4, are well known as alkylation and isomerization catalysts.
 Details of catalysts and their functions
• Fe is used in Fischer-Tropsch process: producing hydrocarbons
from synthesis gas
• Dual functional catalysts: isomerization and reforming
reactions. Two active sites in close proximity. Ni or Pt on SiO2-
Al2O3 in isomerization of n-hexane. Improving octane number.
 Mechanism of isomerization
Isomerization over bifunctional catalysts containing noble metal on acidic carrier
occurs through intermediate olefins. Metal: hydrogenation/dehydrogenation. Acidic
carrier: skeletal isomerization

Example: conversion of n-butane to isobutane

Paraffin dehydrogenation on metal sites. Equilibrium conversion.

Olefin-acid catalyst binding, carbocation formation.

Rearrangement to stabilize carbocation.

+

Cation releases proton to give branched olefin and

+ to regenerate acidic catalyst.

Hydrogenation of olefin on metal site generating branched olefin.

Required catalyst: bifunctional catalyst

42
 Classification of catalysts
Process Typical catalysts poisons

Alkylation of hydrocarbons H2SO4(l), HF(l), AlCl3+HCl, H3PO4/kieselguhr Substance which reduce acidity

Hydrocarbon cracking Crystalline synthetic, SiO2-Al2O3 (zeolites) Nitrogen compounds, metals (Ni, V,
Cu) coke deposition

Chlorination of hydrocarbons CuCl2/Al2O3

Dehydration γ-Al2O3, SiO2-Al2O3, WO3 Coke deposition

Dehydrogenation Cr2O3/Al2O3, Fe, Ni, Co, ZnO, Fe2O3 H2O

Desulfurization of petroleum Sulfided Co-Mo/Al2O3

fractions
Fischer-Tropsch process Ni/kieselguhr, Fe+Fe2C+Fe3O4

Hydrogen from naphtha, coal Ni/refractory Sufur, arsenic, coke deposition

Hydrogenation Ni/kieselguhr, NiO, Ni-Al (Raney Ni), Pt/Al2O3, Pd/Al2O3, Sulfur, chlorine compounds
Ru/Al2O3
Hydrocracking of coal, heavy oil NiS, Co2O3-MoO3/Al2O3, Ru/Al2O3, W2O3, ZnCl2

Isomerization AlCl3+HCl, Pt/Al2O3

Oxidation, inorganic Pt, V2O5, Rh, CuCl2(HCl or Cl2) Arsenic, chlorine compounds

Oxidation, organic (liquid phase) CuCl2(aq)+PdCl2, Pd/Al2O3, Co+Cu acetates

Oxidation, organic (gas phase) V2O5/Al2O3, Ag-AgO, CuO, bismuth molybdate

Polymerization Al(C2H5)3, P2O5/kieselgurh, MoO3,-CoO/Al2O3, CrO3/(SiO2- H2O, O2, sulfur compounds, CO, CO 2
Al2O3), TiCl3-Al(C2H5)3
 Preparation of catalysts
• Entire porous catalysts can be prepared, or
can be prepared on support or carrier of large
surface area.
• Porous catalysts can be prepared by
– Precipitation method
– Gel formation method
– Mixing of components followed by treatment
Precipitation method

Variables:
• Concentration of aq. solutions
• Temperature
• Time of drying
• Calcining steps
• Washing to remove impurities may
itself induce poisons.
 Gel formation method
• Similar to precipitation method
 Mixing of components
• Mixing of components in water
• Milling to desired grain size
• Drying
• Calcination
• Example: MgO+CaO catalyst can be prepared by this method
using their carbonates.
Preparation of catalysts on support
• Impregnation method
– Evacuating the carrier
– Contacting carrier with impregnating solution
– Removing the excess solution
– Drying
– Calcination and activation
– Example: Ni on Al2O3 using NiNO3 solution.
 Catalysts on support

Reduction of NiO to Ni is best carried

out with by passing hydrogen gas.
 Effect of support
• Nature of support can affect catalyst activity and selectivity: support can
influence the surface structure of atoms dispersed.
• Electronic structure of Pt/Al2O3 is different than that of Pt/SiO2.
• There is an optimal amount of catalyst that should be deposited on
support for its optimized dispersion.
• Higher than optimal deposition may lead to larger clusters of catalysts,
non-uniform dispersion.
• Example:
– Ni/Al2O3 prepared by using 5 wt% NiNO3 solution is less active than that prepared by
using 0.5 wt% solution.
– 5 wt% NiO catalyst prepared by 10 individual depositions of 0.5 wt% solution was 11
times more active than that prepared by 5 wt% NiNO3 solution added in single
treatment, even if same amount of NiNO3 is for two preparations.
 Promoters
• Promoters
– Added during catalyst preparation
– Improves activity or selectivity, or stabilizes the catalytic agent for its prolonged
life.
– Present in small amount, and it has less activity.

Example of promoters:

- Adding Al2O3 on Fe catalysts for ammonia synthesis prevents reduction of surface

area by sintering. This increases activity for longer period of time. Other
promoters for this reaction are CaO and K2O.
- Chlorides are added as promoters to isomerization and hydrogenation catalysts
- Sulfides improves hydro-desulfurization (Co-Mo) catalysts
- Some promoters may increase number of active sites  making existing catalysts
more active.
 Inhibitors
• They function opposite to promoters
• Added in small amount. It lessens activity, stability, or selectivity
• They are helpful in reducing activity of catalyst for undesirable side reactions
• Example:
– Ag supported on Al2O3 is very good for oxidation  industrial ethylene epoxidation. But
complete oxidation produces CO2 + H2O.
Desired

Undesired

Inhibitor: Adding halogen compounds to the catalysts inhibit complete oxidation and improve
selectivity.
Catalyst deactivation (Poison)

https://link.springer.com/article/10.1007/s41050-020-00023-5

https://www.n-u.co.jp/
 Catalyst deactivation (Poisoning)
• Catalyst-activity decreases with time – life of catalyst is a major economic
consideration.
• Regenerating and replacing catalysts – may require shutdown of plant 
production and financial loss
• Highly active catalysts may lose its activity fast, and regeneration may not be
practical or economic.
• Regeneration may be required in months or years for slow-deactivating catalysts.
Chemisorption of poisoning . Example: catalysts for ammonia synthesis.
• Catalysts for cracking lose activity in seconds – requires continuous
regeneration. Reason: deposition of carbon on catalysts.
• Reason for catalyst deactivation – by poisons.
• Poisoning substances may be present in reactants or products
 Catalyst deactivation (Poisoning)
Types Poisons Regeneration
Deposited poisons Carbon deposition of cracking Burning to CO and CO2
Chemisorbed S, and others chemisorbed on Ni, Cu and Pt Poisoning will reach
poisons catalysts equilibrium, may be
permanent
Selectivity poisons Impurities of V, Ni, Fe in crude may induce Remove the metal impurities
dehydrogenation during cracking – increasing before cracking
yield of H2 and coke, lowering yield of
gasoline
Stability poisons • Water vapor affects structure of alumina – Remove moisture
decreases activity of Pt/Al2O3 in SO2
oxidation.
• High temperature induces sintering and
localized melting thus changes catalyst-
structure.
Diffusion poisons Poisons block pore mouth, preventing Remove entrained solids
reactants to reach active sites. from feed.
Ex. Deposited carbon or entrained solids in
feed.
Poisons