Department of Chemical and Petroleum Engineering

CHME 3706-Physical Chemistry 2 lab

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Experiment # 4
Adsorption of Dye by Using Activated Carbon

Objectives: To investigate the adsorption properties of activated carbon by studying the
equilibrium isotherms, adsorption kinetics and operational characteristics of a lab-scale packed-
bed reactor.
Introduction
Adsorption is the collection of a substance onto the surface of the adsorbent solids, whereas
Absorption is the penetration of the collected substance into the solid. Since both of these
frequently occur simultaneously, some choose to call the phenomena sorption. Although both
adsorption and absorption occur in sorption by activated carbon and other solids, the unit
operation referred to as adsorption.

Adsorption consists of using the capacity of an adsorbent to remove certain substances from a
gas or solution. Activated Carbon is an adsorbent that is widely used in water treatment,
advanced wastewater treatment, and the treatment of certain organic industrial wastewater,
because it adsorbs a wide variety of organic compounds and its use is economically feasible.
In water treatment it is used to remove compounds that cause objectionable taste, odor, or
color. It is generally used in granular form in batch, column (both fixed bed and
countercurrent bed), or fluidized-bed operations, fixed bed column being the most common.

Adsorption may be classified as Physical or Chemical adsorption. Physical Adsorption is
primarily due to van der Waals forces and is a reversible occurrence. When the molecular
forces of attraction between the solute and the adsorbent are greater than the forces of
attraction between the solute and the solvent, the solute will be adsorbed by activated surface.
An example of physical adsorption is the adsorption by activated carbon. Activated carbon
has numerous capillaries within the carbon particles, and the surface available for adsorption
includes the surface of the pores in addition to the external surface of the particles. Actually,
the pore surface area greatly exceeds the surface area of the particles, and most of the
adsorption occurs on the pore surfaces. For activated carbon the ratio of the total surface area
to the mass is extremely large. In chemical adsorption, a chemical reaction occurs between
the solid and the adsorbed solute, and the reaction is usually irreversible.

Activated carbon is made from numerous materials such as wood, sawdust, fruit pits and
coconut shells, coal, lignite, and petroleum base residues. When activated carbon particles
are placed in a solution containing an organic solute and the slurry is agitated or mixed to
give adequate contact, the adsorption of the solute occurs. The solute concentration will
decrease from an initial concentration,(C
o
)to an equilibrium value, (C
e
), if the contact time is
sufficient during the slurry tests, it is usually possible to obtain a relationship between the
equilibrium concentration (C
e
) and the amount of organic substance adsorbed (X) per unit
mass of activated carbon (m).


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The Freundlich isotherm, which is an empirical formulation, frequently will represent the
adsorption equilibrium over a limited range in solute concentration. One form of the equation
is:

x/m = X= K C
e
1/n


Where
x: mass of solute adsorbed
m: mass of adsorbent
X: mass ratio of the solid phase that is, the mass of adsorbed solute per mass of
adsorbent
C
e
:

equilibrium concentration of solute, mass/volume
K, n: Experimental Constants

The Linear form of Freundlich isotherm can derive from the above equation:


log X = log K + 1/n log C
e


Plotting log X on Y- axis versus log C
e
on X- axis the slope of the obtained line represents
1/n and intercept represents log K

One of the most important aspects of the Freundlich isotherm in relation to the feasibility of
using carbon adsorption is the numerical value of n and the value of x/m when C
e
=C
o
the n
value is the same regardless of the units used for the equilibrium concentration. The constant,
K, however, does fluctuate with different units employed for the equilibrium concentrations.
The larger the n value and the x/m value (when C
e
=C
o
), the more economically feasible is
the use of carbon adsorption.

Another Isotherm, which frequently will represent adsorption equilibrium, is the Langmuir
isotherm, which is

x/m = X = a
L
K
L
C
e
/1+KC
e


where : a
L
: mass of adsorbed solute required to saturate completely a unit mass of adsorbent


ACTIVATED CARBON ADSORPTION
ISOTHERMS, KINETICS & CONTINUOUS-FLOW OPERATION
BACKGROUND
Adsorption is a unit operation in which surface active materials in true solution are removed
from the solvent by inter-phase transfer to the surfaces of an adsorbent particle. This process is
used in environmental engineering practice for removal of various pollutants such as soluble
organics, dyes, pesticides, lignins, etc., from wastewaters and for removal of colour and taste
and odour-producing substances from natural waters that are to be used as potable water
supplies.
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Adsorption consists of using the capacity of an adsorbent to remove certain substances from a
gas or solution. Activated Carbon is an adsorbent that is widely used in water treatment,
advanced wastewater treatment, and the treatment of certain organic industrial wastewater,
because it adsorbs a wide variety of organic compounds and its use is economically feasible.
It is generally used in granular form in batch, column (both fixed bed and countercurrent
bed), or fluidized-bed operations, fixed bed column being the most common.
APPARATUS
Volumetric flasks, laboratory shaker, balance, glass column, pump, spectrophotometer,
stopwatch, solution holding tank, assorted tubing and glassware.
MATERIALS
1. Granular activated carbon; sieved, washed of fines, and dried to constant weight at 105C.
2. Methylene blue.
COMMENTS ON EXPERIMENT DESIGN
Each of the adsorption experiments hereinafter described employ a synthetic aqueous solution of
methylene blue as the test solution. Any other surface active material or sorbate such as organic
dyes, phenol, substituted phenols, alkyl benzene sulfonates, or high molecular weight alcohols,
however, may be substituted as the adsorbate. Further, natural waters or wastewaters containing
dissolved organics may also be employed as test solutions for these experiments provided that
they are first filtered to remove particulates. However, if methylene blue is replaced by another
adsorbate, then, it will be necessary to define appropriate analytical techniques for whatever
adsorbate is utilized.
PROCEDURE
A.
1. Prepare 1 litre of methylene blue solutions in three beakers at the following
concentrations: I:30, II:30 and III:60 mg/l.
Adsorption Kinetics
2. Place the solutions over magnetic stirrers and start stirring.
3. At time zero add 100 mg of granular activated carbon to the first, 250 mg of granular
activated carbon to the second and 250 mg of granular activated carbon to the third
beaker.
4. Take samples at 15 minute time intervals, and continue sampling until the system
equilibrates. If disintegration of the activated carbon should occur, samples may require
centrifugation or filtration.
5. Determine the remaining methylene blue concentrations, by utilizing the calibration
curve prepared before.
6. Plot the normalized solution phase concentration (C/Co) vs. time for each beaker.
7. Calculate the quantity of methylene blue that was transferred to the surface of the
activated carbon (moles of methylene blue/gram of carbon) for each sample that was
collected. Plot these uptake values vs. time on the same graphs developed in step 6
above.
8. Check whether the order of the rate of adsorption is defined.
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9. Show that the initial rate of adsorption is proportional to methylene blue concentration
and the concentration of granular activated carbon (note that desorption can be neglected
for initial phases of the process).
10. Discuss your observations on the rate of adsorption.
B.
1. Prepare a set of eleven 250-ml flasks by placing 100 ml of 125 mg/l of
methylene blue solution and the following weights of the granular activated
carbon into the flasks: 0, 15, 20, 25, 30, 40, 50, 70, 100, 150, 200 mg.
Adsorption Equilibria
2. Cover the flasks with parafilm and agitate them vigorously on a laboratory
shaker until the system in each flask equilibrates. Then settle or filter the
suspension to remove the carbon.
3. Measure the remaining methylene blue concentrations for each flask.
4. Calculate the quantity of methylene blue that was transferred to the surface of
activated carbon for each flask.
5. Plot the data in a standard adsorption isotherm format.
6. Determine the Freundlich and Langmuir adsorption constants.
7. Discuss the correspondence between the experimental data and the Langmuir
and Freunlich isotherms.
C.
1. Place granular activated carbon into the column. Note the dimensions of the
column.
Continuous Flow Systems
2. Prepare approximately 1500 mg/l methylene blue solution.
3. Feed the column with stated methylene blue solution at an appropriate rate and
record the time as time zero. Note that the column does not fluidize or expand at
that flow rate if the column is fed upward.
4. Sample and determine the concentration of methylene blue in the column effluent
until complete breakthrough of the column is attained (C/C
o
=1).
5. Plot the breakthrough curve showing the concentration of methylene blue in the
column effluent.
6. Calculate the quantity of methylene blue adsorbed as a function of time by
graphically integrating the area above the curve.
7. What is the capacity of granular activated carbon according to the breakthrough
curve?
8. Compare the capacities predicted from the breakthrough and form the isotherm test.
9. Discuss the results of your experiment in detail.
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Methylene Blue Calibration Curve