CHE 407 TOPIC II

ADSORPTION–DESORPTION
PHENOMENA
2019/2020 SESSION
PREPARED BY
DR. E. F. ARANSIOLA
 ADSORPTION–DESORPTION PHENOMENA

• Adsorption is a surface process in which atoms, ions or molecules

from a gas, liquid or dissolved solid must become attached to the
surface for a catalytic reaction to occur.
• Adsorption can be defined further based on the strength of the
interaction between the adsorbent (the substrate onto which
chemicals or reactants attach) and the adsorbed molecules.
• Desorption is the release of one substance from another, either from
the surface or through the surface.
• Desorption can occur when an equilibrium situation is altered.
 ADSORPTION–DESORPTION PHENOMENA CONT’D

• Aggregated systems (solids, liquids, and gases) have two energy types:
 1. Kinetic energy, EC, or thermal energy–inducing particles (atoms or ions) with different
possibilities of motions such as translation, rotation, and vibration.
 2. Interaction energy between particles, Ei, such as van der Waals and electrostatic forces.
• The order of magnitude of these energies defines the system.
 (a) When EC ˃˃Ei, the molecules have maximum freedom, since the distance between molecules
varies. The volume of the system is a function of the temperature, pressure, and number of
molecules. It is classified as an ideal gas system.
 (b) When EC ≈Ei, the molecules or atoms have less degree of freedom. Molecules move but the
distance between them varies in a little way. The volume of the system is a function of the
temperature, number of molecules, and ions, independent of pressure. It represents the liquid
state.
 (c) When EC ˂˂ Ei, the volume depends only on the number of molecules. Molecules and atoms
have only vibration-free movement, and the kinetic energy is attributed to the vibration of
molecules around the same position. It represents the adsorption of molecules on solids.
 ADSORPTION–DESORPTION PHENOMENA CONT’D

• Systems (b) and (c) are called condensed matter state, since the
volumes are defined and less sensible to pressure variation.
• For condensed systems, the molecules on the surface or at the
interface of another system present different situations:
1. Particles located inside the system are susceptible to forces in all
directions and the resultant force is zero.
2. Particles at the surface have forces deriving only from inner
particles.
• Figure 1 shows the different systems
Figure 1: Interaction between particles in a condensed system (solid or liquid).
 ADSORPTION–DESORPTION PHENOMENA
CONT’D
• A catalytic reaction involves physical–chemical phenomena of adsorption and desorption
besides chemical reaction.
• As shown in Figure 2, the energy barrier or activation energy of a catalytic reaction is
lower than the activation energy of a non-catalytic reaction due to the adsorption and
desorption phenomena.
• Thermodynamically, the adsorption phenomenon of a fluid at the surface can be
explained from the Gibbs free energy. It should be spontaneous and, thus, ΔGads < 0.
However, the final entropy of the system diminishes too, since the disorder is lower
when molecules are adsorbed, or ΔS < 0.
• (1)
Adsorption:

• (2)

• Since ΔGads < 0 and ΔS < 0, then the enthalpy change of the system is less than zero, and
thus the adsorption is an exothermal phenomenon.
• Depending on involved nature of forces, there are two types of adsorptions.
Figure 2: Comparison of a catalytic and a noncatalytic reaction. Potential energy
changes during the reaction path.
 Physical adsorption or physisorption
• Its characteristic is low interaction between molecules and solid surfaces.
• The resulting forces are of the same order of the van der Waals forces.
• The enthalpy of adsorption is in the same range of the condensation enthalpy
or evaporation gases (−0.5 – 5 kcal/mol).
• In this kind of adsorption, several layers of molecules can be formed and the
adsorption force decreases with increasing layers.
• The physisorption occurs at low temperatures and is more intense if the
temperature is near the condensation.
• The physisorption attains quickly the equilibrium,
• It is reversible.
• The physisorption of gases on solids is frequently used for textural analyses of
catalysts and solids, such as surface area and pore distribution and sizes.
 Chemical adsorption or chemisorption
• The chemisorption characteristic is the strong interaction between molecules and
surfaces.
• The chemisorption enthalpy (−ΔHads) is of the order of 10 – 100 kcal/mol, thus, of the
same order of the reaction involved in chemical bindings.
• It is irreversible and occurs at higher temperatures than the condensation temperature.
• Since the interaction is specific between molecules and solids, the adsorbed molecules
form a monolayer.
• The chemisorption processes need longer times to attain the equilibrium condition, in
particular at low temperatures.
• There are two types of chemisorptions:
– Activated chemisorption: The adsorption rate varies with temperature and with self-
activation energy. It follows the Arrhenius equation.
– Nonactivated chemisorption: This occurs quickly and indicates very low energy of
activation or zero-activation energy.
 Comparing physical and chemical adsorptions

• The adsorption phenomena can be illustrated by the potential energy

curve, as shown in Figure 3.
• Table 1 presents some properties comparing the physical and
chemical adsorptions.

Figure 3: Potential energy curve for physisorption (F) and

chemisorption (Q).
 Table 1: Differences between Physical and Chemical Adsorption

Parameters Physical Adsorption Chemical Adsorption

Adsorbents All solids Some solids

Adsorbate All gases below critical temperature Some chemically reactive gases

Temperature range Low temperature Generally high temperature

Heat of adsorption Low High

Rate, activation energy Very rapid, low Ea Low Ea for non-activated, high E a for activated

Coverage Multilayer Monolayer

Reversibility Highly reversible Often irreversible

Importance For determination of surface area and pore For determination of active centre areas and
sizes elucidation of surface reaction kinetics
 ADSORPTION ISOTHERMS

• The amount of gas adsorption in a solid is proportional to the mass

and depends on the temperature, pressure, solid, and gas nature.
Thus, the number of moles of gas adsorption at the surface is:
• n=f (P, T, gas, solid) (3)
• For constant temperature, the equation is simplified as:
• n=f (P)T,gas,solid (4)
• which is called “adsorption isotherm’’ relating the amount of gas
adsorbed with the equilibrium pressure at constant temperature.
• The experimental results are classified into six different types of
adsorption isotherms and are shown in Figure 4.
The isotherm of type I indicates chemisorption, where
saturation occurs at relatively low pressures, with the formation
of a complete monolayer. These isotherms represent
microporous material. Isotherms II and III indicate infinite
adsorption as P/P0→1, corresponding to physical adsorption on
multilayers occurring on nonporous or macroporous materials.
Isotherms IV and V are equivalent to isotherms II and III but
with finite adsorption, which indicates pore fill of the macro- or
mesoporous materials.
The last isotherm type VI (in steps) occurs on nonporous
uniform surfaces and indicates the adsorption layer by layer,
where each step corresponds to the maximum adsorption
capacity of a monolayer.