ADSORPTION

Adsorption is a surface phenomenon while absorption is a bulk phenomenon.

Adsorption is the selective concentration or retention of one or more components of a mixture on a

solid surface. It is the process by which molecules of a substance, such as a gas or a liquid, collect on the
surface of another substance.

Adsorbent: the solid that adsorbs a component.

Adsorbate: the component adsorbed.

Applications

• Heterogeneous Catalysis: This is probably the most important application relevant to chemical
engineering. The reaction mechanism of how a reactant reacts on a catalyst surface revolves around
adsorption. Therefore designing catalyst, reactors and studying them requires knowledge of
adsorption

• Separation- Adsorption is used as a separation process in many chemical as well as bio chemical
industries to separate gaseous or liquid mixtures. Designing adsorption equipment like fixed bed
adsorbers, gas drying, pressure swing adsorption etc., chromatography requires knowledge of
adsorption.

• Many experiments in the lab use adsorption as a process to calculate various parameters like
surface concentration, porosity, change in surface energies, pore surface area etc.

• Gas mask: This apparatus is used to adsorb poisonous gases (e.g. oxide of sulphur etc.) and thus
purify the air for breathing.

• For desiccation or dehumidification: These substances can be used to reduce/remove water vapors
or moisture present in the air. Silica gel and alumina are used for dehumidification in electronic
equipment.
• Removal of coloring matter from solution: (i) Animal charcoal removes colors of solutions by
adsorbing colored impurities. (ii) Animal charcoal is used as decolorizer in the manufacture of cane
sugar.

• Separation of inert gases: Due to the difference in degree of adsorption of gases by charcoal, a
mixture of inert gases can be separated by adsorption on charcoal at different low temperatures.

How does Adsorption occur?

• Adsorption of a substance on a solid surface occurs because of an “affinity” of the surface for the
particular substance, i.e. the interaction between adsorbent and adsorbate.

• For example: activated alumina has a strong affinity for moisture, but not for hydrocarbons.

• Classification: based on how strong is the interaction between adsorbent and adsorbate.

– Physisorption

– Chemisorption

Physisorption

• The force of interaction is rather weak between the adsorbent and adsorbate.

• The molecules adhere to the surface of the solid adsorbent as a result of intermolecular attractive
forces (Van der Waals, electrostatic force) between them.

• The process is reversible (recovery of adsorbent material or adsorbed gas is possible) by increasing
the temperature or lowering the adsorbate concentration.

• The adsorption rate is generally quite rapid.

Chemisorption

• Results from a chemical interaction between the adsorbate and adsorbent. Therefore, the formed
bond is much stronger than that for physical adsorption.

• It is frequently irreversible. On desorption, the chemical nature of the original adsorbate will have
undergone a change.

• Chemisorption occurs as an essential step of a heterogeneous catalytic reaction.

Desorption

• The reverse of adsorption is called desorption.

• The ‘reversible’ nature of physical adsorption is the basis of its exploitation for separation of
mixtures.

• In some applications, the adsorbed species may have a material value and its separation is followed
by recovery.

• The spent or loaded adsorbent bed is regenerated by desorption of solute and is used again.

• Pressure (or concentration) and temperature are the two most important variables that determine
the amount of a solute adsorbed per unit mass of the adsorbent at equilibrium.

• Adsorption is favored at a higher pressure and a lower temperature.

• Conversely, a lower pressure or a higher temperature favors desorption.

Adsorption Mechanism

In commercial processes,

• the adsorbent is usually in the form of small particles in a fixed bed

• The fluid is passed through the bed and the solid particles adsorb components from the fluid.

• When the bed is almost saturated, the flow in this bed is stopped and the bed is regenerated
(thermally or by other means).

• The adsorbed material (adsorbate) is recovered and the solid adsorbent is ready for another
cycle of adsorption.
Dual bed adsorption-desorption system

• Regeneration may be done by:

– Heating the bed (by passing a hot carrier or purge or stripping gas like superheated steam
through it) – thermal regeneration or temperature swing or thermal swing adsorption
(TSA)

– Reducing the pressure in the bed – pressure swing adsorption (PSA)

Commercial adsorbents

• Activated carbon

• Zeolites or Molecular sieves

• Silica gel

• Activated alumina

Characteristics & properties of adsorbents

• The following three important attributes of an adsorbent make it suitable and effective for
separation of a mixture:

(i) selectivity

(ii) adsorption capacity

 (iii) reversibility of adsorption

• Selectivity: determined by affinity, intraparticle diffusion rate and size.

• Adsorption capacity: depends upon affinity of adsorption and the specific surface area (m2/g).

• Reversibility of adsorption: necessary if the selectively adsorbed component is to be recovered or

the adsorbent is to be regenerated and reused.

Adsorption Equilibria

• At a constant temperature, the amount adsorbed per unit mass of the adsorbent depends upon the
partial pressure of the adsorbent in the gas phase (or on the concentration (liquid phase)).

• The adsorption isotherm is the equilibrium relationship between the concentration in the fluid
phase and the concentration in the adsorbent particles at a given temperature.

• For gases, the concentration is usually given in mole percent or as a partial pressure.

• For liquids, the concentration is expressed in mass units, such as mg/L (ppm) or µg/L (ppb).

• The concentration of adsorbate on the solid is given as mass adsorbed per unit mass of original
adsorbent.

• Some typical isotherms are shown in the figure below:

• The linear isotherm goes through the origin, and the amount adsorbed is proportional to the
concentration in the fluid.

• Isotherms that are convex upward are called favorable, because a relatively high solid loading can
be obtained at low concentration in the fluid.
• The limiting case of a very favorable isotherm is irreversible adsorption, where the amount
adsorbed is independent of concentration down to very low values.

• The adsorbate can still be removed by raising the temperature even for the cases labeled
“irreversible”, however, a much higher desorption temperature is required than when the isotherms
are linear.

• An isotherm that is concave upward is called unfavorable because relatively low solid loadings are
obtained.