ADSORPTION

Adsorption is a surface process that leads to transfer of a molecule from a fluid bulk to solid surface. This
can occur because of physical forces or by chemical bonds. Usually it is reversible (the reverse process is
called desorption); then it is responsible not only for a removal of substances but also for release. In most
of the cases, this process is described at the equilibrium by means of some equations that quantify the
amount of substance attached on the surface given the concentration in the fluid. These equations are
called isotherms (the most famous are the Langmuir and the Freundlich isotherms) because of the
dependence of their parameters on the temperature, which is one of the most important environmental
factors affecting adsorption.

The Adsorption Process

In adsorption processes one or more components are removed for gas or liquid stream by contact with a
solid phase.
The adsorbent is usually in the form of small particles with a high surface area. The internal surface area
of a particle is usually significantly larger than its external surface area.
To obtain a very large surface area per unit volume of solids requires that the solid is very porous. The
pores must have small diameters and be interconnected. The adsorbed solute is referred to as the absorbate
while the solid is referred as the absorbent.
In an adsorption process the molecules diffuse into the pores of the solid where they bond with the solid
surface by physical or chemical forces. The latter process is referred to as chemisorption.
In commercial processes, the solid particles are charged to a fixed bed. The fluid, from which a component
must be removed, passes through the bed. When the bed is nearly saturated the process is stopped and
normally it is thermally regenerated. In the regeneration step desorption of the absorbate occurs. The
adsorbate is recovered and the adsorbent is then ready to recycle.
Liquid phase adsorption is used for the removal of organic compounds from water and organic solutions,
the removal of Sulphur compounds from organic solutions and the decolourisation of solutions.
Gas phase adsorption includes the removal of organic and Sulphur compounds from vent streams, solvents
and odours from air, CO2 from natural gas and NOx from N2.

Physical and Chemical Adsorption

Adsorption is the process by which molecules or particles adhere to a surface. There are two main types
of adsorptions: physical adsorption (also known as physisorption) and chemical adsorption (also known
as chemisorption).
Physical adsorption (Physisorption) occurs when the adsorbate (the substance being adsorbed) is held
to the surface of the adsorbent (the material doing the adsorbing) by weak intermolecular forces, such as
van der Waals forces or hydrogen bonding. Physical adsorption is a reversible process, meaning that the
adsorbate can be easily removed from the surface of the adsorbent by changing the conditions, such as
temperature or pressure.

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Chemical adsorption (Chemisorption), on the other hand, results from a chemical reaction between the
adsorbate and the adsorbent, forming a chemical bond between them. The bond can be covalent or ionic,
and is typically much stronger than the intermolecular forces involved in physical adsorption. Chemical
adsorption is often more specific and selective than physical adsorption, and is usually irreversible.
In summary, physical adsorption is a non-specific and weak interaction between the adsorbate and
adsorbent, while chemical adsorption is a strong and specific interaction that involves a chemical reaction
between the two.

Physical Properties of Adsorbents

Adsorbents are normally small beads, pellets or granules ranging in size from 2Ằ to 150Ằ. Some typical
adsorbents and their physical properties are given in the following table.
Table 5.1

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Adsorption Isotherm
An adsorption isotherm is a graphical representation of the equilibrium between the concentration of the
adsorbate (substance being adsorbed) in the gas or liquid phase and the concentration of the adsorbate on
the surface of the adsorbent (material doing the adsorbing) at a given temperature and pressure. It
describes the relationship between the amount of adsorbate adsorbed and the pressure or concentration of
the adsorbate in the gas or liquid phase, and is commonly used to characterize adsorption behavior. There
are several types of adsorption isotherms, including:
1. Langmuir isotherm: Assumes a monolayer of adsorbate molecules on the adsorbent surface, and that
all adsorption sites are identical and energetically equivalent.
Langmuir adsorption isotherm model is usually adopted for homogenous adsorption and it is used
successfully in monomolecular adsorption processes.
𝑞𝑚 𝑏𝐶𝑒
𝑞𝑒 =
1 + 𝑏𝐶𝑒
Linear form of Langmuir model is expressed as
𝐶𝑒 1 𝐶𝑒
= +
𝑞𝑒 𝑞𝑚 𝑏 𝑞𝑚
where,
Ce is equilibrium constant of adsorbate (mg/L),
qe is amount of adsorbate adsorbed at equilibrium (mg/g),
qm is Langmuir constant related to adsorption capacity (mg/g),
b is Langmuir constant related to energy of adsorption capacity (L/mg).
The linear plot of Ce/qe versus Ce can be plotted and the constants qm and b can be calculated from slope
and intercept of the plot. The shape of the Langmuir isotherm can be investigated by the dimensionless
constant separation term (RL) to determine high affinity adsorption.
RL indicates the type of isotherm to be irreversible (RL= 0), favorable (0 < RL< 1), linear (RL = 1) (or)
unfavorable (RL > 1).
RL was calculated as follows
1
𝑅𝐿 =
1 + 𝑏𝐶𝑜
Where, C0 is the initial sorbate concentration (mg/L).

2. BET (Brunauer-Emmett-Teller) isotherm: Assumes multilayer adsorption on the surface of the

adsorbent, and is often used to describe adsorption on porous materials.
3. Freundlich isotherm: Assumes that the adsorption process is not limited to a single layer of
adsorbate molecules, and that the adsorption sites have different energies.
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Freundlich isotherm model helps to estimate the adsorption intensity of the adsorbate on the adsorbent
surface.
1⁄
𝑛
𝑞 = 𝑘𝑓 𝐶𝑒

Linear form of Freundlich model is expressed by

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𝑙𝑜𝑔𝑞𝑒 = 𝑙𝑜𝑔𝑘𝑓 + 𝑛 𝑙𝑜𝑔𝐶𝑒

where,
qe is sorbate concentration in solid at equilibrium (mg/g),
Ce is sorbate concentration in solution at equilibrium (mg/L),
kf is the Freundlich isotherm constant related to adsorption capacity(L/mg) and
n is the Freundlich exponent of the Freundlich isotherm constant related to adsorption intensity.
The linear plot of log qe versus log Ce provide the values of n and kf calculated from the slope and
intercept.
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values specify whether isotherm is
𝑛

Irreversible (1/n = 0), favourable (0 < 1/n < 1), unfavorable (1/n > 1)

4. Temkin isotherm: Assumes that the interaction between the adsorbate and the adsorbent is weakened
as the surface coverage increases.
The choice of isotherm depends on the specific adsorption system and the information required from the
isotherm. The isotherm can be used to determine the adsorption capacity of the adsorbent, the strength of
the adsorption interaction, and the type of adsorption mechanism (e.g. physical or chemical).
Temkin isotherm model predicts a uniform distribution of binding energies over the population of
surface binding adsorption.

𝑞𝑒 = 𝛽 𝑙𝑛(𝛼 𝐶𝑒 )
Linear form of Temkin equation was expressed by

qe =  ln  +  ln Ce

where,

RT
=
b
T is the absolute temperature in Kelvin, R is the universal gas constant, 8.314 J/mol
K and b is the Temkin constant related to heat of sorption (J/mg).

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A plot of qe versus lnCe enables the determination of the isotherm constants α and b and the parameters
are given in table below.

Equilibrium Relations
The equilibrium relationship between the concentration of an adsorbate in the fluid and its concentration
on the adsorbent resembles the equilibrium solubility of a gas in a liquid. Some typical isothermal
relationships are shown below.

Example 1

In batch experiments solutions of phenol in water were contacted with granular activated carbon. The
results were obtained at room temperature.

Ce, kg phenol/m3 qe, kg phenol/kg

Solution carbon
0.322 0.15
0.117 0.122
0.039 0.094
0.0061 0.059
0.0011 0.045

Assume that the Freundlich isothermal can be used to model the system. Determine the constants.

A log – log plot shows that the data are on a straight line.

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 0.18
0.16

qe, kg phenol/kg carbon 0.14

0.12
0.1
0.08
0.06
0.04
0.02
0
0 0.05 0.1 0.15 0.2 0.25 0.3 0.35
Ce, kg phenol/m3 Solution

𝑙𝑜𝑔𝑞1 − 𝑙𝑜𝑔𝑞2 −0.8239−(−1.3468)

Slope = n = = = 0.204
𝑙𝑜𝑔𝐶1 −𝑙𝑜𝑔𝐶2 −0.4921−(−2.9586)

logk = logq1 – 0.212logc1 = -0.8239 – 0.212(-0.4921) = -0.7196

kf = 0.191

qe = 0.191C0.212

Example 2
A textile wastewater containing 100mg/l of methylene blue (ionic dye) was treated with activated carbon
in batch adsorption process using an orbital shaker to enhance contact between adsorbent and adsorbate
using various adsorbent dosage. The percentage dye removal is as shown in the table below.
Determine the Langmuir, Freundlich and Temkin constant. State the model that best describe the
adsorption pattern.

Percentage
Dosage Dye
qe Log qe Log Ce Ce/qe 1/LogCe
(g/100ml) Removal
(%) Ce
1 12.65 12.65 1.10209053 1.10209053 1 0.90736648
2 26.66 13.33 1.12483015 1.42586015 2 0.70133106
3 51.42 17.14 1.23401082 1.71113207 3 0.58440843
4 75.18 18.795 1.27404233 1.87610232 4 0.53301997
5 98.61 19.722 1.29495095 1.99392096 5 0.50152439

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 6

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y = 0.045x + 0.6183
Ce/qe 4

0
0 20 40 60 80 100 120
Ce

Langmuir adsorption isotherm plot

1.35

1.3

1.25 y = 0.2364x + 0.8227

Log qe

1.2

1.15

1.1

1.05
1 1.2 1.4 1.6 1.8 2 2.2
Log Ce

Freundlich adsorption isotherm plot

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20 y = 8.5868x + 2.4012
15
qe

10

0
1 1.2 1.4 1.6 1.8 2 2.2
Log Ce

Temkin adsorption isotherm plot

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Constants of Langmuir, Freundlich and Temkin models and correlation coefficients

Model Constant Value

Langmuir
qm, (mg/g) 22.222
kL, (mg/g) 0.07278

Freundlich
Kf,(mg/L) 6.648
n, (mg/L) 4.2301
Temkin
α (mg/L) 1.903
β (mg/L) 8.5868
b (J/mg) 293.374

DESIGN OF FIXED BED COLUMNS

Mass transfer resistances are important here and the process is not in steady state. The equilibrium
conditions are still important but the overall dynamics of the process determine its efficiency. The fluid to
be treated is usually passed down the bed of granules. The concentrations in the fluid and of the adsorbent
change with time. It is assumed that the adsorbent contains no adsorbate at the inlet when the process is
started. Most of the mass transfer and adsorption occurs as the fluid first contact the inlet of the bed.
The concentration in the fluid drops very rapidly with distance in the bed and reaches zero before the end
of the bed is reached. After a short time, the solid at the entrance to the bed becomes nearly saturated and
adsorption now occurs slightly further away from the entrance. As the process continues, the point where
the bulk of the adsorption occurs moves further and further away from the entrance.
The concentration profiles at various times as function of bed height are shown as part (a) on the next
sketch. C0 is the feed concentration and C the fluid concentration at a point in the bed. Consider the graph
at time t1. At the entrance the adsorbent is nearly saturated while at height H1 practically no adsorption
has occurred. The dashed line at t3 shows the concentration in the fluid that is in equilibrium with the solid.
The difference in concentration is the driving force for mass transfer.

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Figure 5.2

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The total shaded area represents the total capacity of the bed. It can be shown that:

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 Parameter Unit
Adsorbent stability time (tt) hr
Breakthrough point time, (tu) hr
Fraction of total capacity to breakthrough %
Height of used bed (𝑯𝑻 ) cm
Length of used bed (𝑯𝑩 ) cm
Unused bed (𝑯𝑼𝑵𝑩) cm
Influent flowrate (Q) mg/h
Sorbate adsorbed mg
Adsorbent saturation capacity (qe) mgmb/gzeolite

Example 3
A stream of alcohol vapour in air was adsorbed by activated carbon in a packed bed with a diameter of
4cm and length of 14cm. the bed contained 79.2g carbon. The inlet gas stream had a concentration, Co of
600ppm and a density of 0.00115g/cm3. The inlet gas entered at 754cm3/s. the data below give the
concentrations of the breakthrough curve. The break-point concentration, Cb is set at Co = 0.01.
(a) Determine the break point time, the fraction of total capacity used up to the break point, the length of
unused bed and the saturation loading capacity of the carbon.
(b) If the break point time required for a new column is 6 hours, determine the height of the required
column.

Breakthrough Concentration
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 Time, h C/Co
0 0
3 0
3.5 0.002
4 0.03
4.5 0.155
5 0.396
5.5 0.658
6.0 0.909
6.2 0.933
6.5 0.975
6.8 0.993

(a) The data are plotted in the graph below

A1 = 3.55,
A2 = 1.55,
tb = 3.6h
∞
𝐶
𝑡𝑡 = ∫ (1 − ) 𝑑𝑡 = 𝐴1 + 𝐴2 = 3.55 + 1.55 = 5.1ℎ
0 𝐶0
3.55
𝐶
𝑡𝑢 = ∫ (1 − ) 𝑑𝑡 = 𝐴1 = 3.55ℎ
0 𝐶𝑜

Fraction of total capacity to breakthrough,

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𝑡𝑢 3.55
= = 0.696
𝑡𝑡 5.1
The length of the used bed is
𝑡𝑢
𝐻𝐵 = 𝐻 = 0.696 × 14 = 9.74𝑐𝑚
𝑡𝑡 𝑇
The unused bed is given by
𝑡𝑢
𝐻𝑈𝑁𝐵 = (1 − ) 𝐻 = (1 − 0.696)14 = 4.256𝑐𝑚
𝑡𝑡 𝑇
The saturation capacity is determined as follows;
Air flowrate =754 x 3600 x 0.00115 = 3122g/h.
600
Total alcohol adsorbed = 𝐶𝑜 𝑥 𝑄 𝑥 𝑡𝑡 = (106 ) 3122 × 5.1 = 9.55𝑔

Saturation capacity = 9.55/79.2 = 0.12galcohol/gcarbon

(b) For new tb = 6.0h
6.0
HB = 3.55 × 9.74 = 16.5𝑐𝑚

But
HT = HB + HUNB = 16.5 + 4.26 = 20 3.76cm

Note
In the scale up from the laboratory to production scale, it may be necessary not only to change the height
but also the diameter of the column. The mass velocity per unit cross-section must be the same for both
columns and this results in an increased column diameter for the plant scale.
Bed heights of 0.3m to 1.5m are typically used with downflow of the gas while superficial velocities are
between 0.15 and 0.5m/s. the pressure drops across the beds are low and of the order of a few cm water.
The adsorption time varies between 0.5 and 8h.
For liquids, the superficial velocity of the liquid varies between 0.03 and 0.07 m/s.

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Example
Equilibrium isothermal data for the adsorption of glucose from an aqueous solution by activated alumina
are as follows:

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