Simultaneous Heat and Mass

Transfer (SHMT)
CHE-402
Date: 16/11/2020
Today’s Topic
Adsorption (Chap. 25 of Unit Operations)
Types of Adsorption
Principle of Adsorption Process
Adsorption Equilibrium
Breakthrough Curve
 Adsorption
Def:
Adsorption is the phenomenon of attraction and retaining the molecules of a substance on the surface of
the liquid or solid resulting into a higher concentration of that molecules on the surface. (Exothermic
process)

Adsorbate: The substance adsorbed onto the

surface is called adsorbate.
For Example ‘B’ is adsorbate.

Adsorbent: The substance onto which the

new molecules are attached are adorbent
For Example ‘A’ is adsorbent.

Interface: The surface where the process

takes place is known as interface.
How Adsorption differs from Absorption
Adsorption is the surface phenomenon.
While, Absorption concerns the whole
mass of the absorbent. (related with the
bulk).
In adsorption the concentration of adsorbed molecules are
greater at the immediate vicinity of the surface rather than in
free phase, whereas absorption involves bulk penetration
through diffusion process.
Adsorption is a rapid process and happens quickly whereas
in Absorption the equilibrium takes place slowly.
Reverse of Adsorption is Desorption.
Types of Adsorption
There are two principal modes of adsorption of molecules on surfaces :
Physical Adsorption ( Physisorption )
Chemical Adsorption ( Chemisorption )

The basis of distinction is the nature of the bonding between the molecule and the
surface. With ...

Physical Adsorption: the only bonding is by weak Van der Waals - type forces.
There is no significant redistribution of electron density in either the molecule or
at the substrate surface.

Chemisorption: 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.
Types of Adsorption
Principle (Types of adsorbents)
Four basic types of adsorbent
Silica Gel
Molecular Sieve (Zeolites)
Activated Carbon
Activated Alumina
Additional terms:
Coverage - a measure of the extent of adsorption of a species onto a
surface (unfortunately this is defined in more than one way ! ).
Usually denoted by the lower case Greek "theta", ‘q’
 Exposure - a measure of the amount of gas which a surface has
seen; more specifically, it is the product of the pressure and time of
exposure (normal unit is the Langmuir, where 1 L = 10-6 Torr s ).
Principle of Adsorption
 Adsorption is the process by which molecules of a liquid or gas contact
and adhere to a solid surface. In this course we focus exclusively on gas
adsorption. Adsorption is used for dehydration in addition to a variety
of air pollution control problems such as:
 Applications:
 removal of trace concentrations (<100 ppm) of malodorous gases
 •solvent recovery - semiconductor industry, chemical industry, etc.
 •meeting emissions requirements (typically, adsorption is effective for
any organic compound having molecular weight exceeding ~45).
 •removal of trace quantities of hazardous air pollutants (HAPs) such as
polycyclic organic compounds, dioxins, furans, pesticides, phenolics,
complex synthetic organics etc. •removal of mercury vapor.
Principle of Adsorption
The most common configuration for industrial
adsorbers involves the use of fixed bed adsorption
systems.
Disadvantages of Adsorption
The capacity of of the adsorbent is limited.

Difficult to manufacture adsorbents with identical

adsorptive properties from batch to batch.

Slow operation.

More suited to batch operations

Desirable features of Adsorbent
Molecular Sieve
Actual Phenomenon
Most commercial applications use small particles of
adsorbent in a fixed bed. Fluid passes down through
the bed (down instead of up to avoid fluidization) and
components adsorb onto the solid. The steps can be
summarized:
1. solute diffuses through the fluid to an area near the
solid particle surface
2. solute diffuses into the pores of the particle
3. solute diffuses to the pore wall
4. solute adsorbs to the pore wall surface
Actual Phenomenon
Pore size: plays a role in determining what
compounds can be retained by a given adsorbent:
molecules that are too large to fit into a given pore
opening cannot be effectively adsorbed.
Molecular sieves are examples of adsorbents that are
engineered to have well-defined pore sizes.
For example, molecular sieve 3A has 3 Å pores, and will
not admit molecules larger than this.
Molecular sieves are often used to dehydrate gas
streams since they can remove water vapor while not
removing organics that are too big to be adsorbed.
Adsorption Equilibrium
Dynamic Adsorption
Adsorption for the control of indoor air contaminants is
a dynamic process which depends on
1) the physical and chemical properties of the adsorbent,
including material composition, particle size, media
thickness, total surface area, and pore volume.
2) The concentration and physical and chemical
properties of the gases to be removed (adsorbates).
 3) The concentration of other adsorbable gases and
vapors, including water vapor.
4) Temperature of the ambient air.
5) The residence time of the adsorbate in the filter
Dynamic Adsorption
The gas filtration process of diffusion, mass transfer,
physical adsorption/desorption and chemical
reaction is complex, but we can use several
simplified models to predict dynamic and
equilibrium behavior.
Breakthrough Curves
Adsorption is a transient process.
The amount of material adsorbed within a bed depends
both on position and time.
Consider the time dependence. As fluid enters the bed, it
comes in contact with the first few layers of absorbent.
Solute adsorbs, filling up some of the available sites.
 Soon, the adsorbent near the entrance is saturated and the
fluid penetrates farther into the bed before all solute is
removed.
Thus the active region shifts down through the bed as time
goes on.
Break Point
The fluid emerging from the bed will have little or no
solute remaining -- at least until the bulk of the bed
becomes saturated.
“The break point occurs when the concentration of the fluid
leaving the bed spikes as un-adsorbed solute begins to
emerge.”
The bed has become ineffective.
Usually, a breakpoint composition is set to be the maximum
amount of solute that can be acceptably lost, typically
something between 1 and 5 percent.
Breakthrough Curve
Adsorption Zone
Breakthrough curve
As the concentration wave moves through the bed,
most of the mass transfer is occurring in a fairly small
region.
This mass transfer zone moves down the bed until it
"breaks through".
The shape of the mass transfer zone depends on the
adsorption isotherm (equilibrium expression), flow
rate, and the diffusion characteristics.
Usually, the shape must be determined
experimentally.
Adsorption Zone
Just downstream of the saturated zone, there is region partially
in equilibrium with the adsorbate.
This region contains a concentration gradient and is referred to
as the mass transfer zone or adsorption zone.
As time progresses the adsorption zone moves deeper into the
system, and eventually approaches the exit from the bed. When
the adsorption zone has moved through the filter, the
concentration of the outlet air will be the same as that at the
inlet.
This process is described by the breakthrough curve. The time-
dependent concentration of the pollutant at the outlet from the
bed is shown before.
 Breakthrough Time
The breakthrough time (tb) is the time elapsed from the
start of filtration until the effluent concentration has
reached a maximum permissible concentration Cs
which is value acceptable from a toxicological or other
user point of view.
The breakthrough time of a specific adsorbent/
adsorbate system indicates the useful life of a filter for
control of that contaminant.
The breakthrough capacity is the amount of gas or
vapor adsorbed by the filter, expressed per mass of
adsorbent, when the breakthrough time is reached.
 Breakthrough Time

where Q is the volumetric flow rate. The mb

adsorption capacity is the maximum mass of
adsorbed species per mass of adsorbent. It is
determined at 100% breakthrough.
Usually, breakthrough curves are measured directly
or predicted from equilibrium
values of the rate coefficient, kn, and adsorption
capacity, We, with the modified Wheeler equation:
Adsorption Zone
where tb = breakthrough time (min);
Ce = exit concentration (g/cm3); By plotting tb versus W, the values of the
Ci = inlet concentration (g/cm3); rate coefficient and the adsorption capacity
Q = volumetric flow rate (cm3/min); can be determined from the intercept and
W = weight of adsorbent (g); slope. This exercise requires significant
pB = bulk density of packed bed experimentation. :
(g/cm3);
kn = rate coefficient (min-1);
We = adsorption capacity (g/g).
Different Adsorbents (Applications)