Experiments in Chemical Engineering, 2nd Adsorption and Ion Exchange

by Servillano S.B. Olaño, Jr.

EXPERIMENT D7

ADSORPTION AND ION EXCHANGE

INTRODUCTION

This is a two part experiment where students will be able to study the characteristics of a
batch absorption process using color as the adsorbate and a commercial ion-exchange resin as
the adsorbent solution. By the use of a spectrophotometer or a colorimeter, adsorption isotherms
as suggested by Freundlich and Langmuir can be investigated. The other part of the experiment
is to operate a continuous ion-exchange apparatus where presence of cations and anions in water
are reduced by using two different kinds of ion-exchange resins. The removal of the ions are
measured by means of a conductivity meter. The students will then be able to determine the
effect of flow rate on the extent of removal of the ions which is of prime importance in the
purification of water.

PART I. ADSORPTION EXPERIMENTS

OBJECTIVES:

1. To determine the Absorption band of a colored solution by colorimetric method.

2. To determine the adsorption isotherm of dilute permanganate or suitable colored

solution using a commercial ion-exchange resin under batch conditions.

3. To determine the rate of adsorption as a function of temperature and solid to solution

ratio.

THEORY

Adsorption is a unit operation where specific components of a fluid phase (gas or

liquid) are removed by allowing the components to be attracted on the surface of an
insoluble solid. The component that adheres to the surface is called the adsorbate or the
adsorbed phase while the substance to which it is attracted is called the adsorbent. The
phenomenon of adsorption is due to the fact that molecular forces at the surface of the solid
are in the state of unbalance or unsaturation. These residual forces are satisfied by attracting
onto and adhering on their surfaces gases or dissolved substances, molecular or ionic, with
which they come in contact.

Common adsorbents used are activated carbon in solvent recovery; bone char in the
decolorization of sugar solutions; alumina on the drying of gases; Fuller’s earth in refining

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Experiments in Chemical Engineering, 2nd Adsorption and Ion Exchange
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of petroleum products; silica gel in the purification of hydrogen products; and industrial ion-
exchage resins to separated selected types of ions in solution. All the adsorbents are
characterized not only on the preferential ability to adsorbed the adsorbate but also by its
high mechanical strength and its large surface to volume ratio.

Adsorption should be distinguished carefully from absorption. However, there are

instances when it is very difficult to determine the exact mechanism. In this case a more
general term of sorption is used. Two types of adsorption may be considered depending on
the mechanism by which the adsorbate is attached or attracted to the surface of the solid. If
adsorption is due to intermolecular attraction or Van der Waal's forces, the mode is physical
adsorption. If the linking of the adsorbate is due to chemical interaction, the mechanism is
referred to as chemisorption. In this case the adsorbate undergoes irreversible chemical
reaction facilitated or catalyzed by the adsorbent.

In this experiment, the adsorbent used is a gel-type synthetic cation exchange resin
of the sulfonated polystyrene type (Amberlite IR-20 Plus). It is supplied in the hydrogen or
sodium form as clear, light yellow spherical particles. The adsorbate to be separated is a
permanganate ion in a dilute aqueous solution.

Equilibrium Isotherm

The amount of ion adsorbed by a given quantity of adsorbent increases with the
concentration of the ion in solution. In some cases, the layer of adsorbed ions is only one
molecule deep, and further adsorption ceases when the surface of the adsorbent is covered.
The equilibrium between the dissolved solute and the material adsorbed depends also on the
nature of the solvent and the temperature, the amount adsorbed increasing at lower
temperatures.

The relation between the amount adsorbed and concentration in a limited

concentration range may be represented by the adsorption isotherm of Freundlich,

Y = k Xn (1)

where Y is the units ( weight, moles, color, etc) of the material adsorbed per unit mass of
adsorbent, X is the units of material adsorbed per unit weight or volume of solution. The
constants k and n are determined from experimental data by plotting log Y versus log X. The
constant k varies considerably with the temperature and nature of the adsorbent.

The adsorption equation of Langmuir is based upon the theoretical consideration of

the process of adsorption. This equation may be written

αX
Y= (2)
1 + βX

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Experiments in Chemical Engineering, 2nd Adsorption and Ion Exchange
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where α and β are constants. For cases where this equation represents the data, X/Y may be
plotted as a linear function of X and the constants evaluated from the slope and the intercept.
Show that the Langmuir equation is actually one description of the law of mass action by
considering the reaction

R - Cl + MnO4- R - MnO4 + Cl-

Method of Analysis

The concentration of the MnO4 ion or a suitable colored ion in solution may be
determined indirectly by the use of a colorimeter or spectrophotometer. The laboratory
colorimeter used is Model 6061 with peak wavelength selection of 430, 470, 490, 520, 540,
580, 600 and 710 nm. The solution is placed in a 10 mm styrene cuvette. See the manual for
the operating details and precautions to be observed in the use of the instrument. The
concentration may be expressed in terms of the absorbance or % transmittance as indicated
by the colorimeter. Before measurements are made, it is important that the absorption band
for the ion under analysis be determined. One method is to measure the decrease in the
intensity of the original light after passage through an absorbing medium as a function of
wavelength. The fraction of original light transmitted is then plotted as a function of the
wavelength. The minimum point gives the position of the absorption band. All
measurements must be based on this wavelength where the maximum absorption is attained.

It is important that you calibrate the colorimeter, as indicated in the operating manual,
before starting with the measurements.

A. Materials and Reagents

- 10 mL graduated cylinders - Aqueous KMnO4 solution

- 2 liter beaker - Amberlite IR-20 plus resin
- 500 mL beakers
- Magnetic stirring rods
- Stopwatch
- Pipette
- Magnifying glass
- Heater

PROCEDURE

I. Determination of the Absorption Band

1. Prepare three samples each in 10-ml graduated cylinders composed of solutions

prepared by diluting the base solution to twice, five times and ten times its volume.

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Experiments in Chemical Engineering, 2nd Adsorption and Ion Exchange
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2. Measure the transmittance of each sample as a function of wavelength. Determine the

absorption band for each concentration. Is the absorption band appreciably affected by
concentration?

II. Determination of Rate of Adsorption and Adsorption Isotherm

1. In a 2-liter beaker prepare 1500-ml of KMnO4 aqueous solution by diluting the base
solution to twice its volume. Measure the transmittance of this solution using the
wavelength corresponding to the absorption band.

2. Get three 500 ml beakers and put 300 ml each of the prepared KMnO4 solution. Put the
beaker each on top of the two stirrers. Put the magnetic stirring rods. The other beaker
will be stirred manually. Measure the temperature of the solutions.

3. Weigh separately 1.0, 1.5 and 2.0 gram samples of the Amberlite IR-20 plus resin.

4. Put the resin samples each to the beakers. Start the timed run when the stirrers are
turned on. Use reasonable and uniform rate of stirring. The other beaker is stirred
manually. By means of a pipette, withdraw samples for colorimetric measurements at
regular intervals of time, say 2 or 3 minutes. Sampling at the same time may not be
possible. What is important is that you know the time the samples were obtained. Also,
be careful not to withdraw solids to the samples.

5. End the test when the color of the solutions is no longer changing. Examine the
condition of the resins under a magnifying glass.

III. Effect of Temperature on the Rate of Adsorption

1. Get two 500-ml beakers and put 300 ml of the prepared KMnO4 solution. Weigh
separately two one-gram samples of resin.

2. Place the beaker on each stirrer and turn on the stirrer and heater to heat the solution to
about 40oC and 50oC.

3. When stable temperature is attained, put the resin to each beaker and start the timed
run. Get samples at regular intervals of time and measure the transmittance. Monitor
the temperatures to get an average value during the entire run.

4. End the test when the color of the solutions is no longer changing. Examine the
condition of the resins under a magnifying glass. Give the spent resin to the technician
for proper disposal.

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Experiments in Chemical Engineering, 2nd Adsorption and Ion Exchange
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DATA SHEET

Determination of Adsorption Band

Determination of Adsorption Isotherm

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Experiments in Chemical Engineering, 2nd Adsorption and Ion Exchange
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ANALYSES AND CALCULATIONS

1. Prepare a calibration curve as % Transmittance versus concentration of KMnO4 expressed in

Molarity (g-moles/liter of solution)

2. In one graph, plot the % Transmittance as a function of wavelength for the three
concentrations under study. In another graph plot the absorbance as a function of
wavelength. Compare the two graphs and identify the absorption band. Is the absorption
band affected by concentration?

3. In one graph, plot the % Transmittance as a function of time for each of the samples at
various solid to solution ratio.

4. Calculate the rate of adsorption and plot this rate as a function of concentration for various
solid to solution ratios.

5. In one graph, plot the % Transmittance as a function of time for the three temperatures with
the same solid to solution ratio.

6. Plot also the rate of adsorption as a function of concentration at various temperatures.

7. Determine the constants in the Freundlich and Langmuir equations. Which adsorption
isotherm is more applicable for this system? Explain.

GUIDE QUESTIONS

1. What is Lambert’s Law? Beer’s Law?

2. Explain how to determine the extinction coefficients. Give the significance of these
coefficients?

3. How would you regenerate the spent resins? Explain also the mechanisms or reactions
involved?

4. Describe the condition of the resins for the trials used in the experiment

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Experiments in Chemical Engineering, 2nd Adsorption and Ion Exchange
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PART II. ION-EXCHANGE EXPERIMENT

OBJECTIVES

1. To calibrate the flow meter in the ion-exchange apparatus.

2. To determine the ion separation characteristics of tap water through the ion-exchange
apparatus under continuous operations.

THEORY

Ion exchange is a type of separation operation that involves the exchange of one ion for
another. A very popular application is the removal and replacement of Ca++ and Mg++ ions
with Na+ ion in the softening of water. This is usually done by allowing the hard water to flow
through a bed of surface active resins and zeolites.

Another common industrial ion exchange is dimeniralization (or deionization). In

deminiralization the cations are exchanged for H+ and anions are exchanged for OH-. The H+
and OH- react to form water. Thus, unlike water softening, this process removes ions from the
solution. The cation and anion exchange resins are separately regenerated with acid and base.
One application of deionization is in the sugar industry where sugar yields can be decreased by
first deionizing. A second application is polishing (final purification to remove traces of ions) of
condensate for high pressure boilers. Ion exchange is also extensively used for recovery of metal
ions. This is done both in mining operations and in industrial reprocessing such as plating
operations. Examples are recovery of uranium, copper, gold silver, rare earths and transuranic
elements. Ion exchange chromatography is a common separation method in biotechnology.
Amino acids, peptides and proteins all have charged groups and can be exchanged on cation or
anion exchange resins.

For monovalent ion-exchange, the ion-exchange reaction for cations (+ ions) is

A+ + R-B+ + X- → R-A+ + B+ + X-
where: R- represents the fixed negatively charged ionic sites in the resin
A+ and B+ are the counter ions which are exchanging
X- is the co-ion which do not appear to enter into the reaction but may affect the
exchange equilibrium.

The complete ion-exchange cycle consists of loading step where the A+ goes to the resin,
a regeneration step where the A+ is removed from the resin by adding concentrated B+X-
solution and the wash step where excess B+X- is removed from the column.

For the exchange of divalent cation with a monovalent cation

D++ + 2R-B+ → R2-D++ + 2B+ + 2X-

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The divalent ion takes up two fixed sites in the resin. An example is the removal of Ca from
water by exchanging it for Na+. Regeneration can be done with a concentrated NaCl solution.

EQUIPMENT

B. Actual Equipment

Figure 1: Actual Laboratory Ion Exchange Apparatus

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Experiments in Chemical Engineering, 2nd Adsorption and Ion Exchange
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C. Schematic Diagram of the Equipment

Figure 2: Ion Exchange Apparatus Flow Diagram

D. Description of the Equipment

As shown in Figure 2, the Ion-Exchange Apparatus is composed of two columns, the left
column contains sulfonated polystyrene type cation exchange resin, Amberlite IR-20 Plus,
while the right column contains an ammonium anion exchange resin, Amberlite IRA 400.
The set up may be operated using a single column or combination of two columns in series
by adjusting the correct combination of valves. The initial or inlet liquid from the supply
tank goes through the flow meter while the final solution is allowed to flow directly to the
conductivity sensor.

PROCEDURE
1. For more details, refer to the manufacturer’s manual for the flow diagram of the
apparatus and the operating procedure.

2. Calibrate the flow meter by using a stopwatch and a graduated cylinder. Use the main
and by-pass valves to adjust the flow rate.

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Experiments in Chemical Engineering, 2nd Adsorption and Ion Exchange
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3. Put sufficient tap water in the reservoir at the back of the apparatus.

4. Determine the initial conductivity of the tap water by pumping the water from the
reservoir directly to the conductivity meter. Record the conductivity as a function of
time. Wait until the reading has stabilized.

5. Allow water to flow, at a given flow rate, through the first column directing the ouput to
the conductivity meter. Monitor the conductivity of the solution as a function of time.

6. Increase the flow rate for another run. Do three flow rates to end the single column test.

7. Allow water to flow through the left column with the effluent directed to the second
column. The final treated stream is allowed to flow through the conductivity meter
where the reading is monitored against time. Do three trials with several water flow rates.

DATA SHEETS
Calibration of Flow meter
Flowmeter Reading volume
time (s)
(1000mL/min) (mL)

Single Column
volume time conductivity
flow rate (1000mL/min)
(mL) (s) (uS)

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Experiments in Chemical Engineering, 2nd Adsorption and Ion Exchange
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Two Columns
volume time conductivity
flow rate (1000mL/min)
(mL) (s) (uS)

ANALYSIS

1. Plot the flow meter reading versus flow rate. Generate a calibration equation for the
flowmeter.

2. In one graph plot the conductivity reading as a function of time for the various trials. What
do you observe with regards to the degree of removal of ions in the tap water for the various
schemes and flowrates?

QUESTIONS

1. With the aid of a diagram, describe the principle of a conductivity meter.

2. What is a breakthrough point in the operation of an ion-exchange column? Was this reached
in your experiment? Explain.

3. List at least five other commercial ion-exchange resins and the types of ions that each is
capable of separating. List the important specifications of ion-exchange resins.

4. List two websites that can be consulted to determine the type of exchange resins that can be
used to separate special types of impurities or contaminants such as heavy metals, poisons,
bacteria etc.

5. Describe the procedure for regenerating the ion-exchange resins used in the experiment.

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