ADSORPTION

Adsorption: definition, nature of adsorption and adsorbate; adsorption. Equilibria (isotherms)

1. LEARNING OBJECTIVES
The following are the learning objectives
 Students to understand the definition of adsorption and related terms
 Students to understand the nature of adsorption , use of adsorption and adsorborate
 Students to understand adsorption and Equilibria isotherms

2. INTRODUCTION

 Sorption - the process of absorption of one substance by another

 Sorbent - absorber
 Sorbtiv (sorbate) - absorbed substance
 Adsorption - absorption by sorbent surface
 Absorption - absorption by the entire volume of the sorbent

Adsorption is defined as the adhesion of a chemical species onto the surface of particles.
Adsorption is a different process from absorption, in which a substance diffuses into a
liquid or solid to form a solution.

In adsorption, the gas or liquid particles bind to the solid or liquid surface that is termed
the adsorbent. The particles form an atomic or molecular adsorbate film.

Isotherms are used to describe adsorption because temperature has a significant effect on
the process. The quantity of adsorbate bound to the adsorbent is expressed as a function
of pressure of concentration at constant temperature. Several isotherm models have been
developed to describe adsorption, including the linear, Freundlich, Langmuir, BET (after
Brunauer, Emmett, and Teller), and Kisliuk theories

Examples of adsorbents include:

 silica gel
 alumina
 activated carbon or charcoal
 zeolites
 adsorption chillers used with refrigerants

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  biomaterials that adsorb proteins
Adsorption is present in many natural, physical, biological, and chemical systems, and is
widely used in industrial applications such as
 activated charcoal,
 capturing and using waste heat to provide cold water for air conditioning and
other process requirements (adsorption chillers),
 synthetic resins,
 increase storage capacity of carbide-derived carbons, and
 water purification.
Adsorption, ion exchange, and chromatography are sorption processes in which certain
adsorbates are selectively transferred from the fluid phase to the surface of insoluble,
rigid particles suspended in a vessel or packed in a column. Pharmaceutical industry
applications, which use adsorption as a means to prolong neurological exposure to
specific drugs.

3. NATURE OF ADSORPTION

Adsorption vs Absorption
Adsorption is a surface phenomenon in which particles or molecules bind to the top layer of a
material. Absorption, on the other hand, goes deeper, involving the entire volume of the
absorbent. Absorption is the filling of pores or holes in a substance.

What is the primary difference between adsorption and absorption

S.no Absorption Adsorption

1. It is a bulk phenomenon It is a surface phenomenon
It comes under the category of the
2. It is an endothermic process
exothermic process
It reaches equilibrium while increasing
3. It has a uniform state of the process
gradually and steadily
Absorption is the assimilation of the
Surface accumulation of the molecular
4. molecular species at the solid or liquid
species instead of the bulk of liquid or solid
form

Adsorption is the process in which matter is extracted from one phase and concentrated at the
surface of a second phase. (Interface accumulation). This is a surface phenomenon as
opposed to absorption where matter changes solution phase, e.g. gas transfer. This is
demonstrated in the following schematic.

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NATURE OF ADSOPRTION AND ADSORBATE

ADSORPTION

EQUILIBRIA ISOTHERMS

If we have to remove soluble material from the solution phase, but the material is neither
volatile nor biodegradable, we often employ adsorption processes. Also adsorption has
application elsewhere, as we will discuss later.
adsorbate: material being adsorbed
adsorbent: material doing the adsorbing.
(examples are activated carbon or ion exchange resin).

Surface Energy

An explanation of why material accumulates at the interface is based on the excess energy
associated with particles at interfaces. For example, in the case of pure water and air, the
water molecules at the air-water interface have higher energy than water molecules in the
interior of the water phase. The reason that these surface molecules have higher energy is
that, unlike the interior molecules, they have an unbalanced force component (on the airside
of the molecule).

These surface molecules have additional energy to balance the forces. It takes energy to put
molecules on the surface, since at least one of the interior bonds must be broken to get the
molecule to the surface. This excess energy is called surface tension. Since it takes energy to
create interfacial surfaces, the system will try to minimize the total interfacial surface area.
Hence we see spherical droplet, meniscus etc.

Thermodynamics of surface adsorption

In solutions certain particles tend to concentrate at the surface. These particles are those that
have low affinity for the water (solvent). These are hydrophobic molecules. Because they
have low affinity for the solvent the can get to the surface easily since they have low bond
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energy in the bulk phase. The water system prefers to have these molecules at the surface
because the placement at the surface requires less energy than a water molecule --
hydrophobic molecules decrease surface energy (surface tension) relative to a pure water
system.

Surface excess can be defined as:

(Cinitial  Cafter adsorption)" Volume"


"surface area"

Where "Volume" is the volume of the solution from which the adsorption is occurring onto
the surface with total surface area = "surface area".

Surface excess is defined as the mass adsorbed per surface area. A more fundamental
definition is given by the Gibbs relationship.

d   i d i
i
where: µi = the molar free energy of solute i. Ci is the bulk concentration of this solute. The
Gibb‟s expression simply uses  as a proportionality constant to relate the change in solute
molar free energy to surface tension () during adsorption.

The underlying principle here is that for the adsorption process changes in the sum of all
solute free energy must be accounted for in changes in the surface tension during the
adsorption process.
For a single solute:

d  d( 0  RT ln C)
dC
d  RT
C
d R T
 4
dC C
therefore

d
0
dC
results in increase in ( surface concentration)
d
0
dC
results in decrease in 

4. TYPES OF ADSORPTION:

1)Lack of solvent-solute interactions (hydrophobicity –surfactants)

2)Specific solid-solute interaction

Exchange adsorption (ion exchange)– electrostatic due to charged sites on the surface.
Adsorption goes up as ionic charge goes up and as hydrated radius goes down.

Physical adsorption: Van der Waals attraction between adsorbate and adsorbent. The
attraction is not fixed to a specific site and the adsorbate is relatively free to move on the
surface. This is relatively weak, reversible, adsorption capable of multilayer adsorption.
In physical adsorption the following should be noted
• The gas molecules adhere to the surface of the solid adsorbent as a result of
intermolecular attractive forces (van der Waals forces) between them
• The process is exothermic: the heat liberated is in the order of the the enthalpy of
condensation of vapor (2-20 kJ/gmole)
• The process is reversible (recovery of adsorbent material or adsorbed gas is possible) by
increasing the temperature or lowering the adsorbate conc.
• Physical adsorption usually directly proportional to the amount of solid surface area
• Adsorbate can be adsorbed on a monolayer or a number of layers
• The adsorption rate is generally quite rapid

Chemical adsorption: Some degree of chemical bonding between adsorbate and adsorbent
characterized by strong attractiveness. Adsorbed molecules are not free to move on the
surface. There is a high degree of specificity and typically a monolayer is formed. The
process is seldom reversible.
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In chemical adsorption the following is should be noted
• Results from a chemical interaction between the adsorbate and adsorbent. Therefore
formed bond is much stronger than that for physical adsorption
• Heat liberated during chemisorption is in the range of 20-400 kj/g mole
• It is frequently irreversible. On desorption the chemical nature of the original adsorbate
will have undergone a change.
• Only a monomolecular layer of adsorbate appears on the adsorbing medium

Generally some combination of physical and chemical adsorption is responsible for activated
carbon adsorption in water and wastewater.

5. ADSORPTION MECHANISM

6. USES OF ADSORPTION

There are many applications of the adsorption process, including:

 Adsorption is used to cool water for air conditioning units.
 Activated charcoal is used for aquarium filtration and home water filtration.
 Silica gel is used to prevent moisture from damaging electronics and clothing.
 Adsorbents are used to increase the capacity of carbide-derived carbons.
 Adsorbents are used to produce non-stick coatings on surfaces.
 Adsorption may be used to extend the exposure time of specific drugs.
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  Zeolites are used to remove carbon dioxide from natural gas, remove carbon
monoxide from reforming gas, for catalytic cracking, and other processes.
The process is used in chemistry labs for ion-exchange and chromatography.

7. ADSORPTION EQUILIBRIA

If the adsorbent and adsorbate are contacted long enough an equilibrium will be
established between the amount of adsorbate adsorbed and the amount of adsorbate in
solution. The equilibrium relationship is described by adsorption isotherms.

An adsorption isotherm is a curve relating the equilibrium concentration of a solute on the

surface of an adsorbent, qe, to the concentration of the solute in the liquid, Ce, with which it
is in contact.

The adsorption isotherm is also an equation relating the amount of solute adsorbed onto the
solid and the equilibrium concentration of the solute in solution at a given temperature.

Where
qe = mass of material adsorbed (at equilibrium) per mass of adsorbent.
Ce = equilibrium concentration in solution when amount adsorbed equals qe.
qe/Ce relationships depend on the type of adsorption that occurs, multi-layer, chemical,
physical adsorption, etc.

The adsorption capacity of activated carbon may be determined by the use of an adsorption
isotherm which can take multiple forms. Isotherms are found by doing lab tests
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Adsorption Isotherms
Add same initial target chemical concentration, Cinit, in each

Control

Different activated carbon dosage, Csolid, in each

qe mg/g or g/g=Co -Ce (mg/L) or = Co -Ce .V = mass
Csolid (g/L) X mass

An adsorption „isotherm‟ is a qe vs. Ce relationship at equilibrium.

Where
qe = mass of material adsorbed (at equilibrium) per mass of adsorbent.
Ce = equilibrium concentration in solution when amount adsorbed equals qe.
qe/Ce relationships depend on the type of adsorption that occurs, multi-layer, chemical,
physical adsorption, etc.

Isotherm models:

There are several models for predicting the equilibrium distribution. There are four models
that are commonly used. The figures below show that there are four common models for
isotherms.

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The most commonly used isotherms for the application of activated carbon in water and
wastewater treatment are the Freundlich and Langmuir isotherms. Freundlich isotherm is an
empirical equation. Langmuir isotherm has a rational basis.

Linear Isotherm

qe = K. Ce

qe is the amount of solute absorbed per unit weight of solid at equilibrium. Unit is g/g or
mg/g

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Ce is the equilibrium concentration of solute remaining in solution when the amount adsorbed
equals qe

Langmuir Isotherm:
Irving Langmuir was the first to derive a scientifically based adsorption isotherm in 1918.
The model applies to gases adsorbed on solid surfaces. It is a semi-empirical isotherm with a
kinetic basis and was derived based on statistical thermodynamics. It is the most common
isotherm equation to use due to its simplicity and its ability to fit a variety of adsorption data.

This model assumes monolayer coverage and constant binding energy between surface and
adsorbate.

Langmuir isotherm is defined by the following equation

K  Q0a  Ce
qe 
1  K  Ce

Q0a - is the maximum adsorption capacity for forming monolayer coverage. (g solute/g
adsorbent).
Ce has units of mg/L. Ce is the equilibrium concentration of solute remaining in solution when
the amount adsorbed equals qe
K has units of L/mg

The Langmuir isotherm was developed based on the following assumptions:-

• A fixed number of accessible sites are available on the absorbent surface , all have the
same energy
• Adsorption is reversible and is a second order reaction
• Equilibrium is reached when rate of adsorption of the surface molecules onto the
surface is the same as the rate of desorption of molecules from the surface. The rate
at which adsorption proceeds is proportional to the driving force, which is the
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 difference between the amount adsorbed at a particular concentration and the amount
that can be absorbed at that concentration. At the equilibrium, concentration this is
zero
• At the maximum adsorption, only a monolayer is formed. Adsorption only occurs on
localized sites on the surface, not with other adsorbates

These four assumptions are seldom all true: there are always imperfections on the surface,
adsorbed molecules are not necessarily inert, and the mechanism is clearly not the same for
the very first molecules to adsorb to a surface as for the last. The fourth condition is the most
troublesome, as frequently more molecules will adsorb to the monolayer; this problem is
addressed by the BET isotherm for relatively flat (non-microporous) surfaces. The Langmuir
isotherm is nonetheless the first choice for most models of adsorption, and has many
applications in surface kinetics and thermodynamics.

BET (Brunauer, Emmett and Teller) isotherm:

This is a more general, multi-layer model. It assumes that a Langmuir isotherm applies to
each layer and that no transmigration occurs between layers. It also assumes that there is
equal energy of adsorption for each layer except for the first layer.

K B  Ce  Q0a
qe 
(CS  Ce ){1  (K B  1)(Ce / CS )}

CS =saturation (solubility limit) concentration of the solute. (mg/liter)

KB = a parameter related to the binding intensity for all layers.
Note: when Ce << CS and KB >> 1 and K = KB/Cs BET isotherm approaches Langmuir
isotherm.

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It is based on the following assumptions:
• adsorption takes place on the lattice and molecules stay put,
• first monolayer is adsorbed onto the solid surface and each layer can start before
another is finished,
• except for the first layer, a molecule can be adsorbed on a given site in a layer (n) if
the same site also exists in (n-1) layer,
• at saturation pressure (P0), the number of adsorbed layers is infinite (i.e.,
condensation),
• except for the first layer, the adsorption enthalpy (HL) is identical for each layer

Freundlich Isotherm:

It is empirical and very widely used. For the special case of heterogeneous surface energies
(particularly good for mixed wastes) in which the energy term, “KF”, varies as a function of
surface coverage we use the Freundlich model.
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q e  K F Ce n

KF is an indicator of adsorption capacity.

Higher the maximum capacity, higher the KF.

1/n is a measure of intensity of adsorption.

Higher the 1/n value, more favorable is the adsorption.

Generally, n < 1 1/n 1

n and KF are system specific constants.

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8. DETERMINATION OF APPROPRIATE MODEL

To determine which model to use to describe the adsorption for a particular

adsorbent/adsorbate isotherms experiments are usually run. Data from these isotherm
experiments are then analyzed using the following methods that are based on linearization of
the models.

For the Langmuir model linearization gives:

Ce 1 C
  e0
q e K  Qa Qa
0

A plot of Ce/qe versus Ce should give a straight line with intercept :

1
K  Q0a

and slope: 1
Q0a

1 1 1 1
Or  0 
q e Q a K  Q a Ce
0

Here a plot of 1/qe versus 1/Ce should give a straight line with intercept 1/Qao and slope
1
K  Q0a

For the Freundlich isotherm use the log-log version :

1
log q e  log K F  log C
n
A log-log plot should yield an intercept of log KF and a slope of 1/n.

For the BET isotherm we can arrange the isotherm equation to get:

Ce K 1 C 1
 B 0 e 
(CS  Ce )  q e K B  Qa CS K B  Q0a

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Intercept = 1
K B  Q 0a

KB  1
Slope=
K B  Qa  Cs
0

9. FACTORS WHICH AFFECT ADSORPTION EXTENT

The factors which affect adsorption extent (and therefore affect isotherm) are:

Adsorbate:
a) Solubility
In general, as solubility of solute increases the extent of adsorption decreases. This is
known as the “Lundelius’ Rule”. Solute-solid surface binding competes with solute-
solvent attraction as discussed earlier. Factors which affect solubility include molecular
size (high MW- low solubility), ionization (solubility is minimum when compounds are
uncharged), polarity (as polarity increases get higher solubility because water is a polar
solvent).

b) pH

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 pH often affects the surface charge on the adsorbent as well as the charge on the solute.
Generally, for organic material as pH goes down adsorption goes up.
c) Temperature
Adsorption reactions are typically exothermic i.e., D H rxn is generally negative. Here heat
is given off by the reaction therefore as T increases extent of adsorption decreases.

d) Presence of other solutes

In general, get competition for a limited number of sites therefore get reduced extent of
adsorption or a specific material.

Adsorbent:
Virtually every solid surface has the capacity to adsorb solutes. From the
wastewater/water treatment point of view activated carbon (AC) is the adsorbent of
choice. AC prepared from many sources:
• Wood
• Lignite
• Coal
• Nutshells
• Bone
• These raw materials are pyrolyzed at high temperature under low oxygen conditions
(so we don‟t get complete combustion). This forms a “char”. The char is then
activated by heating to 300 – 1000 oC in the presence of steam, oxygen or C02.
• Result: “Activated carbon” which is highly porous, micro-crystalline material which
resembles graphite plates with some specific functional groups (e.g. COOH, OH)

Surface area of the Activated Carbon (AC) is huge. Most of the surface area is interior in
micro- and macropores. Typical surface area is in the range of 300-1500 m2/gram.

Quality and hardness of the AC are a function of the starting material and the activation
process.

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