ADSORPTION

OBJECTIVE

Students understand the principles of using solid adsorbent (activated

carbon) to adsorb gases and toxic organic chemicals, pigments in wastewater.

THEORY
Adsorption is a process that occurs when a gas or liquid solute
accumulates on the surface of a solid or a liquid (adsorbent), forming a molecular
or atomic film (the adsorbate). It is different from absorption, in which a
substance diffuses into a liquid or solid to form a solution. The term sorption
encompasses both processes, while desorption is the reverse process.
Adsorption is operative in most natural physical, biological, and chemical
systems, and is widely used in industrial applications such as activated charcoal,
synthetic resins and water purification.
Similar to surface tension, adsorption is a consequence of surface energy.
In a bulk material, all the bonding requirements (be they ionic, covalent or
metallic) of the constituent atoms of the material are filled. But atoms on the
(clean) surface experience a bond deficiency, because they are not wholly
surrounded by other atoms. Thus it is energetically favourable for them to bond
with whatever happens to be available. The exact nature of the bonding depends
on the details of the species involved, but the adsorbed material is generally
classified as exhibiting physisorption or chemisorption.
Typical Characteristics of Adsorption Processes
Physisorption or physical adsorption is a type of adsorption in which the
adsorbate adheres to the surface only through Van der Waals (weak
intermolecular) interactions, which are also responsible for the non-ideal
behaviour of real gases.
Chemisorptionis a type of adsorption whereby a molecule adheresto a
surface through the formation of a chemical bond, as opposed to the Van der
Waals forces which cause physisorption.

Chemisorption Physisorption

The forces operating in

The forces operating these are weak Vander The forces operating in
Waal’s forces. these cases are similar
 to those of a chemical
bond.

Near or below the

Virtually unlimited
Temperature Range condensation point of the
(but a given molecule
(over which adsorption gas
may effectively adsorb
occurs) (e.g. Xe < 100 K, CO2 <
only over a small range)
200 K)

Related to factors like

Wide range (related to the
molecular mass and
chemical bond strength) -
Adsorption Enthalpy polarity but typically 5-
typically 40 - 800 kJ mol-
1 40 kJ mol-1 (i.e. ~ heat of
liquefaction)

Crystallographic
Specificity
Marked variation Virtually independent of
(variation between
between crystal planes surface atomic geometry
different surface planes of
the same crystal)

Often dissociative Non-dissociative

Nature of Adsorption
May be irreversible Reversible

Multilayer uptake
Saturation Uptake Limited to one monolayer
possible

Very variable - often an Fast - since it is a non-

Kinetics of Adsorption
activated process activated process

Adsorption and absorption

Absorption is the process in which a fluid is dissolved by a liquid or a
solid (absorbent). Adsorption is the process in which atoms, ions or
molecules from a substance (it could be gas, liquid or dissolved solid) adhere
to a surface of the adsorbent. Adsorption is a surface-based process where a
film of adsorbate is created on the surface while absorption involves the entire
volume of the absorbing substance.
Adsorption and absorption are both sorption processes.
Absorption occurs when atoms pass through or enter a bulky material. During
absorption, the molecules are entirely dissolved or diffused in the absorbent
to form a solution. Once dissolved, the molecules cannot be separated easily
from the absorbent.
Adsorption is generally classified into physisorption (weak van der Waal’s
forces) and chemisorption (covalent bonding). It may also occur due to
electrostatic attraction. The molecules are held loosely on the surface of the
adsorbent and can be easily removed.
Absorption: The common commercial uses of absorption cycle are
absorption chillers for space cooling applications, ice production, cold
storage, turbine inlet cooling. High efficiency operation, environmentally
friendly refrigerants, clean-burning fuels and few moving parts that require
maintenance make absorption a very good choice for consumers.
The process of gas absorption by a liquid is used in hydrogenation of oils and
carbonation of beverages.
Adsorption: Some of the industrial applications for adsorption are air-
conditioning, adsorption chillers, synthetic resin and water purification. An
adsorption chiller does not require moving parts and hence is quiet. In
pharmaceutical industry applications, adsorption is used as a means to
prolong neurological exposure to specific drugs or parts thereof. Adsorption
of molecules onto polymer surfaces is used in various applications such as in
the development of non-stick coatings and in various biomedical devices.

Absorption Adsorption
Assimilation of molecular Accumulation of the molecular
species throughout the bulk species at the surface rather than
Definition
of the solid or liquid is in the bulk of the solid or liquid
termed as absorption. is termed as adsorption.
Phenomenon It is a bulk phenomenon It is a surface phenomenon.
Heat exchange Endothermic process Exothermic process
It is not affected by It is favoured by low
Temperature
temperature temperature
Rate of It occurs at a uniform rate. It steadily increases and reach to
reaction equilibrium
 It is same throughout the Concentration on the surface of
Concentration material. adsorbent is different from that
in the bulk

Factors Affecting Adsorption

The most important factors affecting adsorption are:
  Surface area of adsorbent. Larger sizes imply a greater
adsorption capacity.
 Particle size of adsorbent. Smaller particle sizes reduce
internal diffusional and mass transfer limitation to the penetration of the
adsorbate inside the adsorbent (i.e., equilibrium is more easily achieved
and nearly full adsorption capability can be attained). However,
wastewater drop across columns packed with powdered material is too
high for use of this material in packed beds. Addition of powdered
adsorbent must be followed by their removal.
 Contact time or residence time. The longer the time the more
complete the adsorption will be. However, the equipment will be larger.
 Solubility of solute (adsorbate) in liquid (wastewater).
Substances slightly soluble in water will be more easily removed from
water (i.e., adsorbed) than substances with high solubility. Also, non-
polar substances will be more easily removed than polar substances
since the latter have a greater affinity for water.
 Size of the molecule with respect to size of the pores. Large
molecules may be too large to enter small pores. This may reduce
adsorption independently of other causes.
 Degree of ionization of the adsorbate molecule. More highly
ionized molecules are adsorbed to a smaller degree than neutral
molecules.
 pH. The degree of ionization of a species is affected by the pH
(e.g., a weak acid or a weak basis). This, in turn, affects adsorption.
 Adsorbent
The adsorbent (adsorbent material) is usually granular materials with a
particle size of 6-10 nm to 200 nm, have large porosity. Surface area provided by
the internal pores of the solid. The large available surface area is effective pore
diameter a few times larger than molecular diameter. Adsorbent must meet the
following requirements:
 Have high adsorption capacity
 Have wide range of applications
 Have a necessary mechanical strength
 Have a high ability desorption
 Low cost

Activated carbon
Activated carbon is by far the most common adsorbent used in wastewater
or gas treatment. Since, during adsorption, the pollutant is removed by
accumulation at the interface between the activated carbon (absorbent) and the
wastewater (liquid phase) or gas the adsorbing capacity of activated carbon is
always associated with very high surface area per unit volume. The high surface
area per unit volume characteristic of activated carbon is obtained with a two-step
process used in carbon manufacturing:
  Pyrolysis of raw material (typically a high carbon source such as coal,
wood, nut shells) to drive off (distill) the lighter fraction producing a
charred, highly carbonaceous solid residue;
 Activation of the charred residue via oxidation (typically with air or
steam) to form a network of pores and passages with high surface area.
Pore Structure in activated carbons typically range from 10 to 10,000 Å in
diameter. Pores having a diameter larger than 1000 Å are called macropores.
Pores having a diameter smaller than 1000 Å are called micropores. Micropores
are primarily responsible for the adsorption characteristics of activated carbon.
Typical surface areas in activated carbons range from 500 to 1500 m2/g of carbon.

Activated carbon is produced in particle sizes up to a few millimeters. The

total surface area available for adsorption is not significantly affected the by
particle size since the micropore structure responsible for adsorption does not
change appreciably with particle size. This implies that the total adsorption
capabilities of small and large particles are not too different although the time to
achieve equilibrium can vary significantly because of diffusional effects. Carbon
having larger particle sizes (of the order of 1 mm or more) is termed granular.
This material can be packed in columns through which a liquid can be passed,
and can be regenerated after use. Carbon having smaller particle sizes (of the
order of tens of mm) is termed powdered. This material can only be used by direct
addition to a liquid and must be removed after use (e.g., by filtration) and
disposed of. In general, the larger the particle size the more expensive is the
carbon.
EXPERIMENT

Equipment, chemical

No. Equipment Number Note

1. Glass bottle have lines divided, 1
which consists of one long tube
down the bottom of the tube
and 1 short
2. Glass tube contain adsorbent 1

3. Bracket 1

4. Gas pump 1

5. Condenser 1

6. Electric stove 1

7. Pressure cooker 7

8. Glass funnel 7 100 ml

9. Graduated cylinders 7 100 ml

10. Erlenmeyer flask 7 250 ml

11. Pipette 7

12. Ethanol meter 5 measuring range 0 –

50o
13. Lab wash bottle 5

14. electronic balance 1

15. Ethanol 100% 1l

16. Activated carbon 400 g

Experiment

Figure 1: Adsorption and desorption

Adsorption process
- Weight all tubes containing the adsorbent is a gram
- Take activated carbon adsorbent into tubes containing. Weigh the b g
- Installation of adsorption tubes in the rack
- Connect the device by fitting the same order as in Figure 1a
- Check the entire system to ensure tight
- Turn on the aeration start time adsorption properties. Conduct adsorption
process in the right time 10'
During adsorption process, preparation and installation of desorption equipment
including pressure cooker and condenser (figure 1b)
- Stop the adsorption process. Next remove the adsorbed system. Measured
volume of alcohol remaining by graduated cylinders.
Conduct desorption process include:
- Connect the bottom of the tube containing the adsorbent with cryogenic
equipment. Condenser cooling by water flows continuously.
- Effluent water contain in by 250 ml flasks
- Connect the pipe to the top of the tube 1 containing the adsorbent.
Desorption conducted in about 30 minutes

Experiment Report Sheet

Coagulation and Flocculation

Date Lab Sec. Name

Desk No.
Principle of method

Description experiments

Achievements
- Measured volume of alcohol remaining
- Measured the amount of alcohol to evaporate

- Calculated adsorption capacity

- Calculated recovery efficient (measured by volume alcohol solution and

desorption)
Comment