Sorption

Adsorption vs. Absorption

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.

Example:
O2 gas adsorbed on activated
carbon

Absorption is the process in which a fluid is dissolved

by a liquid or a solid (absorbent).
Example: water absorbed by tissue paper
 Sorption Process
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.
 Absorption Adsorption

Gas-liquid absorption (a) and liquid-solid adsorption (b) mechanism

Blue spheres are solute molecules
Difference between Absorption and Adsorption

Absorption Adsorption

Substance penetrates the surface Surface phenomenon

Rate increases initially than it
It occurs at uniform rate
decreases

It is unaffected by temperature It is affected by temperature

It is an endothermic process It is an exothermic process

Concentration on the surface of

It is same throughout the material adsorbent is different from that in
the bulk
Adsorption
 Mechanism of Adsorption
The amount of heat evolved when one mole of the
adsorbate is adsorbed on adsorbent is called
enthalpy of adsorption.

Adsorption is an exothermic process and enthalpy

change is always negative.

When adsorbate molecules are adsorbed on the

surface, freedom of movement of molecules become
restricted and this results in decrease in entropy.

Adsorption is a spontaneous process at constant

pressure and temperature, thus Gibbs free energy is
also decreased.
The adsorption of molecules on to a surface is a
necessary pre-requisite to any surface mediated
chemical process.
For example, in the case of a surface catalyzed
reaction it is possible to break down the whole
continuously-cycling process into the following
five (5) basic steps :
(i) Diffusion of reactants to the active surface
(ii) Adsorption of one or more reactants onto the
surface
(iii) Surface reaction
(iv) Desorption of products from the surface
(v) Diffusion of products away from the surface
Hydrogenation of ethene on a
solid surface
Substrate - frequently used to describe the solid
surface onto which adsorption can occur; the
substrate is also occasionally referred to as the
adsorbent.
Adsorbate - the general term for the atomic or
molecular species which are adsorbed (or are
capable of being adsorbed) onto the substrate.
Adsorption - the process in which a molecule
becomes adsorbed onto a surface of another
phase.
 Adsorption is when a molecule in the gas
phase or in solution binds to atoms on the
solid or liquid surface.

The molecule that is binding is called the

adsorbate, and the surface to which it binds
is the adsorbent.

The process of the adsorbate binding to the

adsorbent is called adsorption. The reverse
of this process (the adsorbate splitting from
adsorbent) is called desorption.
 Adsorbent
A component can be separated from a mixture if it
selectively adsorbs onto a solid surface. This is the
basis of the adsorption unit process.

Adsorbents are usually porous solids, and

adsorption occurs mainly on the pore walls "inside"
the particles. Examples of adsorbents include:
- activated carbon
- silica gel (adsorbs moisture)
- activated alumina (adsorbs moisture)
- zeolites and molecular sieves
- synthetic resins
 Activated carbon

Zeolites
Silica gel
 Adsorption
There are two principal modes of adsorption of
molecules on surfaces :
(i) Physical Adsorption (Physisorption)
- van der Waals forces
(ii) Chemical Adsorption (Chemisorption)
- bond to solid
Adsorption is a surface phenomenon, so the
rate and extent of adsorption depends on the
surface area of the solids (adsorbent) used.
It involves adsorption of When the gas molecules or
gases on solid surface via atoms are held to the solid
weak Van der Waals forces. surface via chemical bonds.
 Physical Adsorption
Due to the weak forces of attraction or van der
Waals forces between molecules
Adsorbed molecules is free to move about over
the surface
Adsorbed material may condense and form
several superimposed layers on the surface of
the adsorbent
Generally quite reversible, the material can be
desorbed to the same extent it was originally
adsorbed
There is no significant redistribution of electron
density in either the molecule or at the substrate
surface.
Brunauer's model of multilayer adsorption
is a random distribution of molecules on the
material surface.
 Chemical Adsorption
A chemical bond, involving substantial rearrangement of
electron density, is formed between the adsorbate and
substrate. The nature of this bond may lie anywhere
between the extremes of virtually complete ionic or /
complete covalent character.
The result of much stronger forces, comparable to those
leading to formation of chemical compounds
Adsorbed material normally forms a monomolecular
layer over the surface (1 molecule thick) the capacity
of adsorbent is exhausted when the surface is covered
Molecules adsorbed are not considered free to move from
one surface site to another
Seldom reversible , generally must be heated to remove
adsorbed materials
 Typical Characteristics of Adsorption Processes

Chemisorption Physisorption
Material Specificity
(variation between Substantial variation Slight dependence upon
substrates of different between materials substrate composition
chemical composition)
Crystallographic
Specificity Marked variation Virtually independent of
(variation between between crystal surface atomic geometry
different surface planes planes
of the same crystal)
Chemisorption is Low temperature
Temperature accompanied by promotes physical
(over which adsorption increase in adsorption and high
occurs) temperature. temperature decreases
the rate of adsorption.
 Chemisorption Physisorption
Wide range (related to the Related to factors like
Adsorption chemical bond strength) molecular mass and
-1
Enthalpy - typically 40 - 800 kJmol polarity
-1
- typically 5-40 kJmol

Reversibility Irreversible Reversible

Saturation Multilayer uptake

Uptake Limited to monolayer possible

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

Adsorption activated process . activated process .
Activation energy is No activation energy is
needed. needed.
 "Favorable" isotherms permit
higher solid loadings at lower
solution concentrations.
These tend to start out steep
and level out.

Isotherms which start out

flat are "unfavorable",
since they only work well
at high concentrations of
solute.

Adsorption equilibrium data is typically plotted in the form of

an adsorption isotherm (i.e. at constant temperature) with
the mass adsorbed on the y-axis and the mass in the fluid on
the x-axis. The shape of the curve is significant and factors
heavily into design.
Usually, as temperature increases the amount adsorbed
decreases (permitting thermal regeneration).
Adsorption of gases on charcoal in relation
to pressure at constant temperature.
(Higher pressure, higher adsorption)
Adsorption of solutes on charcoal; temperature
and pressure constant. (Adsorption depends
on the nature of material and its concentration,
as well as the temperature)
Adsorption isotherms (ambient temperature)
from aqueous phenol solutions of various pH.
 Adsorption Isotherms
A quantitative relationship describing the
equilibrium between the concentration of
adsorbate in solution and its adsorbed
concentration (mass adsorbate/mass adsorbent)

3 isotherms commonly used depending on a

variety of factors, such as concentration and
number of adsorbates, types of adsorbent, type
of fluid and etc:
- Langmuir
- Freundlich
- BET (Brunauer - Emmett - Teller)
The Langmuir Model for Adsorption
The equation was developed by Irving Langmuir in 1916.

Irving Langmuir derived a simple model involving

a thermodynamic equilibrium to predict the fraction
of solid surface covered by an adsorbate as a
function of its gas pressure. This was later
extended to liquid systems, where the equilibrium
involved concentrations in solution.

The Langmuir equation or Langmuir isotherm

relates the coverage or adsorption of molecules on
a solid surface to gas pressure or concentration of
a medium above the solid surface at a fixed
temperature.
In this model, adsorbate and solvent molecules
compete to adsorb on sites on the surface of the powder.
Each site must be occupied by either a solvent molecule
or an adsorbate molecule.

Figure 1 illustrates this model

-- B represents a binding site,
S represents a solvent
molecule, and a shaded
eclipse represents an
adsorbate molecule.
 Assumptions in the Langmuir Model
Langmuir had to make several assumptions in order to
derive an adsorption expression:
All surface sites have the same adsorption energy
for the adsorbate
Adsorption (of either solvent or adsorbate) at one site
doesnt affect the availability of (block) the next site
to adsorb solvent or adsorbate
Adsorption (of either solvent or adsorbate) at one site
doesnt affect the energy of adsorption of the
neighboring sites (as they adsorb either solvent or
adsorbate)
The activity of the adsorbate is directly proportional
to its concentration
In fact, these assumptions are not satisfied for
many real-life cases.

However, the simplified version gives insight into

the dependence of surface coverage on
concentration in solution.

The driving force for adsorption on the surface is

proportional to the concentration of the species in
solution.

The driving force for desorption from the surface

is proportional to the fractional surface coverage
of the species on the surface.
 Langmuir Isotherm
Assumes that a single adsorbate binds to a
single site on the adsorbent and that all surface
sites on the adsorbent have the same affinity for
the adsorbate
q = adsorbed concentration
q = qmKadsC (mass adsorbate/mass
1+KadsC adsorbent)
1/q = 1 1 + 1/qm qm = max capacity of
qmKads C adsorbent for adsorbate
(mass adsorbate/mass
adsorbent)
Kads = measure of affinity
of adsorbate for C = aqueous conc. of
adsorbent adsorbate (mass/vol.)
Straight-line form of the Langmuir
isotherm
Langmuir adsorption isotherms of
lead ions on steel slag
 Freundlich Isotherm
The Freundlich equation or Freundlich
adsorption isotherm is an adsorption isotherm,
which is a curve relating the concentration of a
solute on the surface of an adsorbent, to the
concentration of the solute in the liquid with
which it is in contact.

It can be derived from the Langmuir isotherm by

assuming that there exists a distribution of sites
on the adsorbent that have different affinities
for different adsorbates with each site behaving
according to the Langmuir isotherm.
 Freundlich Isotherm
q = KC1/n
log q = log K + 1/n log C
K adsorption capacity (mass adsorbate/mass adsorbent);
n is a measure of how affinity for the adsorbate changes
with changes in adsorption density.
q = weight adsorbed per unit wt of adsorbent
C = concentration in fluid

When n = 1, the Freundlich isotherm becomes a

linear isotherm and all sites have equal affinity for
adsorbate.
When n > 1 indicate that affinities decrease with
increasing adsorption density.
Adsorption isotherms of methylene blue on the vetiver
roots ACs (A), on the sugar cane bagasse ACs (B)
Logarithmic plot of adsorption data
 Adsorption of heavy metals by fly ash
Freundlich isotherm plot for Zn, Pb and Cd and Cu at pH 4.5
 At higher pH, the adsorption was intense
resulting in the depletion of high-energy sites
as the heavy metal concentration increased.
Freundlich isotherm plot for Zn, Pb and Cd and Cu at pH 8
 Comparison of Langmuir & Freundlich Isotherm
The Langmuir adsorption isotherm describes quantitatively
the build up of a layer of molecules on an adsorbent
surface as a function of the concentration of the adsorbed
material in the liquid in which it is in contact. In a modified
form it can also describe a bi-layer deposition.

The shape of the isotherm (assuming the (x) axis

represents the concentration of adsorbing material in the
contacting liquid) is a gradual positive curve that flattens
to a constant value.

The Freundlich isotherm curves in the opposite way and

is exponential in form. It often represents an initial surface
adsorption followed by a condensation effect resulting from
extremely strong solute-solute interaction.