Factors affecting surface area
Interaction of solid with surrounding
➢Solid-Solid: Autohesiveness (cohesiveness) e.g flow, compactibility etc.
➢Solid-Liquid: Wetting, non-wetting, adsorption capacity etc.
➢Solid gas: Adsorption, Catalysis, etc.
In this presentation we will discuss about the solid-gas
interaction.
Suitable methods of determination
➢Gas adsorption allows probing of entire surface including irregularities
and pore interiors.
➢The amount adsorbed is a function of temperature, pressure and the
strength of attraction or interaction potential.
➢ Physisorption is generally weak and reversible. The solid must be
cooled and a method used to estimate the monolayer coverage from
which surface area can be calculated.
Adsorption Process
Adsorptive
Adsorbate
adsorbent
Different types of sorption
Typical several eVs
Physisorption
1.Van der Waals bonding (dipole) Typical 10 – 100 meV
2.Weak (<0.4 eV)
3.always atomic/molecular
4.Reversible and fast
5.surface symmetry insensitive
6.may form multilayers
Chemisorption
1.Covalent/metallic/ionic
2.Strong (>0.4 eV)
3.May be dissociative
4.Often irreversible
5.surface symmetry specific Typical 3 – 10 Å
6.limited to monolayer
Typical 1 – 3 Å
BET Equation
With the further assumption that the multilayer has an infinite thickness at
p/p0 = 1, it was possible to arrive at the well-known BET equation, which is
usually expressed in the following linear form:
where nm is the monolayer capacity
and C is an empirical constant
The quantity (E1 − EL) was originally known as the ‘‘net heat of
adsorption’’.
If C > 2, the mathematical form of is similar to that of the Type
II isotherm in Fig. 1. This has been called the S-shaped, or
sigmoid, isotherm.
However, if C < 2, the shape is changed and the point of
inflection is lost.
We obtain the specific surface area, aBET, from nm by assuming a value for
the area, σ, occupied by each adsorbate molecule
(i.e. the effective molecular cross-sectional area) in the completed monolayer
However, since the nitrogen–surface interactions are dependent on
the adsorbent structure, some variation in σN is to be expected.
The sorption behaviour in mesopores is determined
➢ By the adsorption potential (i.e. the fluid–wall interactions
➢ By the attractive interactions between the fluid molecules
➢Pore condensation is the phenomenon whereby a gas condenses
to a liquid-like phase in a pore at a pressure p less than the
saturation pressure p0 of the bulk liquid.
➢ This leads to the appearance of a Type IV adsorption isotherm in
the IUPAC classification
Capillary Condensation
➢ This upward swing is now associated with the filling of the
mesopores by capillary condensation.
➢Its occurrence at a pressure (which depends on the pore size)
below the normal saturation pressure is due to the formation of a
curved meniscus in a group of pores of particular size and shape.
➢If one assumes complete wetting behaviour of the pore
condensate,
Kelvin Equation
➢The equation relates the curvature of the liquid meniscus in
a pore to the relative pressure at which condensation occurs
Rearrangement of earlier equation and replacement of 1/r1 + 1/r2
by 2/rk gives the more familiar form of the Kelvin equation
Clearly, rk would represent the radius of curvature of a
hemispherical meniscus (since r1 = r2 = rk). If the pores are in the
form of parallel-sided slits, r2 =∞ and the meniscus is cylindrical
➢Thus, for cylindrical pores, the pore radius rp is given by rp = rk +t
For parallel-sided slits, the width wp is given by wp = rk + 2t
The modified Kelvin equation based on a cylindrical pore model
serves as the basis for many methods applied for mesopore analysis,
including the Barrett–Joyner–Halenda (BJH) method which is still widely
used.
The Isotherm
The amount of gas adsorbed is a function of –
➢The strength of interaction between gas and solid (intrinsic)
➢Temperature (fixed)
➢Pressure (controlled variable)
Isotherms (IUPAC classifications)
Microporous (chemisorption)
Non-porous or macroporous
Not common;
N2 adsorption on
polyethylene
Mesoporous
Mesoporous
Uniform non-porous surface
➢ Microporous adsorbents such as
zeolites and many activated carbons.
➢ The limiting uptake at the plateau
is mainly dependent on the accessible
micropore volume rather than on the
internal surface area
➢ A steep uptake at very low p/p0 is
due to enhanced adsorbent–adsorbate
interactions in ultramicropores
(micropores of molecular dimensions)
resulting in micropore filling at very
low p/p0
Reversible Type II isotherms
➢ Physisorption of gases on most non-
porous or macroporous adsorbents.
➢The shape is the result of
unrestricted monolayer–multilayer
adsorption up to high p/p0. If the
knee is sharp, point B – the beginning
of the middle almost linear section –
usually corresponds to the completion
of monolayer coverage.
➢ Amore gradual curvature (i.e. a less
distinctive point B) is an indication of a
significant amount of overlap of
monolayer coverage and the onset
of multilayer adsorption.
Reversible Type III isotherm
➢ In the extreme case of a there is no
point B and therefore no identifiable
monolayer; the adsorbent–adsorbate
interactions are now relatively weak
and the adsorbed molecules are
clustered around the most
favourable sites.
Type IV isotherms
➢This is by mesoporous adsorbents
(e.g. many oxide gels). In this case, the
initial monolayer–multilayer adsorption
on the mesopore walls is followed by
capillary condensation
Type V isotherm
➢ In the low p/p0 range, the shape is
similar to that of Type III and can be
attributed to relatively weak
adsorbent–adsorbate interactions.
At higher p/p0, molecular clustering
is followed by nanopore filling
