UNIT 10 ADSORPTION

Structure
10.1 Introduction
Objectives
10.2 Adsorption on Solids
Physisorption
Chemisorption
10.3 Adsorption Isotherms
10.4 Experiment 10 : Adsorption of Oxalic Acid from Solution on Activated Charcoal
Principle
Requirements
Procedure
Observations
Calculations
Result
10.5 Summary

10. INTRODUCTION
~ d s o r ~ t i is
o nan important surface related phenomenon which has many practical applica-
tions. Use of activated charcoal in gas masks for removal of harmful gases from air, use of
activated charcoal or Fuller's earth in decolorisation of solutions before crystallation, use of
ion exchange resins in demineralisation of water, heterogeneous catalysis, concentration of
ores by froth flotation process, etc. are only some of the examples which depict the applica-
tions of adsorption. In this unit, we shall discuss an experiment which is based on adsorption
phenomenon.
Aft& studying this unit and having performed the experiment described in the unit, you
should be able to :

Objectives

cite applications of adsorption,

differentiate between adsorption andabsorption,
define physisorption and chemisorption,
describe adsorption isotherms, and
study adsorption isotherms for adsorption of oxalic acid on activated charcoal.

10.2 ADSORPTION ON SOLIDS

In Unit 4, you studied that the molecules on the surface of a liquid experience an inward
pull. The liquid surface is thus in a state of unsaturation. The surface of a solid also behaves
hi a similar manner. In a solid, the ions or the molecules at the surface of a solid danot have
all their valancies satisfied by union with other particles. Such forces also arise due to the
fact that when a new surface is created by breaking a solid, some interatomic bonds are
broken and some of the valancies of surface atoms are left unsatisfied. As a result of these
residual forces, the surface of the solid has a tendency to attract and retain available molecules
and particles towards itself; such a condition is helpful in decreasing the surface energy of a
solid. The molecules so attracted are retained on the surface of the solid and do not go deeper
into the bulk. Their concentration is more on the surface than in the bulk of the solid. This
phenomenon of accumulation (higher concentration) of a substance on the surface of another
substance is called adsorption. The substance that accumulates on the surface is the
~pp~cstloo
nrs adsorbate and the underlying solid is the adsorbent. For example, charcoal adsorbs acetic
Tbcrmadynamic~
acid when kept in contact with it; here, acetic acid is adsorbate and charcoal is adsorbent.

Adorption should be clearly differentiated from absorption. In absorption, the substance is

not only retained on the surface but passes through the surface and is distributed throughout
the bulk of the solid. Thus, anhydrons calcium chloride absorbs water to form a hydrate,
while charcoal adsorbs acetic acid from its solution. Sometimes the term 'sorption' is used
when there is a doubt whether a process is true adsorption or absorption.

103 PHYSISORPTION AND CHEMISORPTION

Depending on the type of interaction between the adsorbate and the adsorbent, adsorption
is of two types -physisorption (physical adsorption) and chemisorption (chemical adsorp-
tion).

10.3.1 Physisorption
If the adsorbate molecules are weakly bound to the adsorbent,it is classified as physisorption.
It is also known as van der waals adsorption since the forces involved are of van der wads
type. The forces are of the same magnitude as are involved in the liquefaction of gases. The
enthalpy decrease (- A H) associated with physisorption is much low (less than 40
W mol-') and is of the same order as the enthalpy of condensation of the adsorbate.
Increase of temperature is not favourable to physisorption. Adsorption of gasesby charcoal
is an example of physisorption. Physisorption is generally independent of the chemical nature
of the adsorbate. All gases exhibit physisorption.

1032 Chemisorption
Chemisorption is very specific and can occur only if the adsorbate is capable of forming
a chemical bond with an active centre on the surface. The enthalpy decrease associated with
chemisorption is much high (between 40 kJ mol-' and 400 kJ mol-') and is of the order
of bond enthalpies. Many chemisorption processes involve activation energy as in a chemical
reaction. In such cases, the rates of chemisorption and desorption increase with temperature
in contrast with the rate of physisorption . Adsorption of nitrogen on iron surface at 770 K
is an example of chemisorption. Chemisorption results in release of large amounts of energy
and chemisorbed nitrogen is present as nitrogen atoms but not as molecules.
At room temperature, iron does not adsort nitrogen at all. But as temperature is lowered
and brought near 80 K, the boiling point of liquid nitrogen, iron adsorbs nitrogen gas
physically as NZmolecules.

103 ADSORPTION ISOTHERMS

Adsorption on solids can be from gaseous phase as well as from liquid solution. Extent of
adsorption in,any case of adsorption is defined as the quantity of adsorbate held on a unit
mass of the adsorbent. The extent of adsorption at equilibrium depends on a number of
factors such as :

e temperature at equilibrium,
e thenchemicalnature and surface area of the adsorbent, and
e the chemical nature and the concentration (pressure in case of gases) of the adsorbate.

Of particular interest is the relationship between the extent of adsorption and the concentra-
tion (pressure) of the adsorbate at equilibrium. This relationship is studied at constant
temperature and so is called adsorption isotherm. In general, experimental isotherms take
a variety of forms. In Unit 21 of the CHE-04 course, you might have studied Freundlich and
Langmuir adsorption isotherms for adsorption on solid surfaces. Here,we shall discuss an
 Adsorption
experiment to show that the adsorption of acetic acid from solution on activated charcoal
follows Freundlich and Langmuir adsorption isotherm equations.

10.4 EXPERIMENT 10 :ADSORPTION OF OXALIC ACID

FROM SOLUTION ON ACTIVATED CHARCOAL
Activated charcoal is a very good adsorbent. When activated charcoal is added to an aqueous Activated charcoal can be
solution of oxalic acid, and the contents are allowed to attain equilibrium, oxalic acid is obtained by heating wood
adsorbed on charcoal. Objectives of this experiment are to show that charcoal between 625 K and 1275
K in vacuum, air, steam, chlorine
or carbon dioxide. During heating,
the extent of adsorption of oxalic acid from solution on activated charcoal increases as hydrocarbons and other impurities
equilibrium concentration of oxalic acid in solution increases, and are removed from charcoal leading
thereby to a large surface area for
the adsorption of oxalic acid from solution on activated charcoal follows Freundlich and adsorption. The resulting
Langmuir adsorption isotherms. substance is called activated
charcoal.

10.4.1 Principle
For adsorption of a substance from a solution by a solid adsorbent, Freundlich gave an
empirical equation, which is known as Freundlich adsorption isotherm. This equation, as
shown below, gives the relationship between the amount of the adsorbate (x) adsorbed by a
particular mass (m) of the adsorbent and the equilibrium concentrataion (c) of the adsorbate
at a particular temperature, i.e., Q

where K and n are constants.

Taking logarithm of both the sides, we get

X
log- = logK
m
+ -n1 loge
X
If the plot of log - against log c is a straight line, it means that the adsorption follows
m
Freundlich adsorption isotherm. The slope of this line will be equal to lln and the intercept
will be equal to log K. Sincexlni and c are fractions (i.e., less than I), logxlrn and log c will
be negative quantities.

Since it is easier to plot with positive quantities, we shall multiply both sides of the above
equation by (-1) and write,

Hence, make a plot of (- logxlm) against (-log c) to verify the observance of Freundlich
isotherm. The plot should be a straight line. The slope of this line will be equal to lln and
the intercept will be equal to log K.
Langmuir derived another relationship between the amount adsorbed and the equilibrium
concentration of the solute by making certain basic assumptions. This you might have studied
in Unit 21 of the CHE-04 course. This relationship can be written as:

1 +pc
Taking inverse, l/(x/ni ) =
ac
Applications of
Thermodynamics

where a and /I are constants.

This equation can be verified by plotting c l(x/m) against c, which should result in a straight
line. The slope of the line will give /I/a and the intercept will give Va. Hence, the values of
constants a andb can be evaluated experimentally.

In this experiment, a known mass (m) of activated charcoal is added to an aqueous solution
of oxalic acid of known initial concentration (ci). The contents are shaken for some time and
allowed to attain equilibrium. Some oxalic acid is adsorbed on activated charcoal. Solution
is filtered. The equilibrium concentration of oxalic acid (c) is determined by titrating the
filtrate against a standard solution of potassium permanganate. For this purpose, Eq. 1.15
of Unit 1 of this course can be used.

The value ofx (i.e., the amount of oxalic acid adsorbed) can be calculated from the change
in concentration due toadsorption (i.e., s - c) and the initial volume of the solution (i.e., 100
cm3) as follows.

You can recognise that the concentration of oxalic acid decreases due to adsorption on the
activated charcoal. Hence, whatever amount of oxalic acid is adsorbed on the charcoal will
be equal to the decrease in the amount of oxalic acid in the solution.

Decrease in the concentration of oxalic acid

= (Initial concentration of oxalic acid) - (equilibrium concentration of oxalic acid)

The amount of oxalic acid adsorbed (x)

= Decrease in the amount of oxalic acid in the solution

= Decrease in the concentration of oxalic acid x Volume of solution in dm3

(as per Eq. 1.12 of Unit 1 of this course)

We intend to verify the observance of Freundlich isotherm and Langmuir isotherm by

graphical method. For this, we need atleast five variations. So you have to perform the
experiment with five oxalic acid solutions having different initial concentrations and each
time determine4 c and m. You enter 'these values in Table 10.2. For the purpose of malung
the plot, the modified values are entered in Table 10.3. Finally, the following plots are made:

(i) -log xlm against -log c (to verify Freundlich isotherm)

(ii) c/(xlm) against c (to verify Langmuir isotherm)

You must get a straight line in both the cases verifying the observance of both the isotherms.
10.4.2 Requirements
Apparatus

Burette 50 cm3 2 Nos.

Pipettes 25,U) and 10 cm3 1 No. each
Stoppered bottles or conical flasks
with corks, capacity 250 cm3 12 Nos.
Funnel 6 Nos.
Watch glasses 6 Nos.
Large water trough 1 Nos.
Thermometer 100" 1No.
Glazed paper 5 cm x 5 cm. 7 Nos.

Chemicals

1. Activated charcoal 15 g

Stock Solutions Provided

1. 2.000 x 10-I M Oxalic acid 200 cm3
2. 2.000 x lo-' M Potassium permanganate 500 cm3
3. 2 M Sulphuric acid 200 cm3

10.4.3 Procedure
Standard solutions are provided to you to save your time which you shall need for this rather
long experiment. Strengths of oxalic acid solutions are estimated by titration against KMn04
solution using an excess of dilute sulphuric acid. Please carry out a blank titration of dilute
sulphuric acid solution to confirm that it does not need any KMn04 solution. If it does, a
correction must be made in all the titre values. The solution to be titrated will need to
warmed to 60°C before starting the titration. 60°C is a temperature which isvery uncomfort-
able to bear on the reverse side of the hand. Over heatingmust be avoided. Reheating during
the titration will not be necessary as the ~ n ions
" produced in the reaction catalyse the
reaction. The reaction equation for the titration is:

Set up two 50 cm3burettes, rinse one of them with 2.000 x lo-' M oxalic acid and the other
with distilled water.

Take six 250 cm3dry stoppered bottles or corked conical flasks. Label them as A, B, C, D,
E and F. With the help of burettes measure into these, in order from A to E,

(i) 50 cm3,40 cm3,30 cm3,20 cm3and 10 cm3of 2.000 x lo-' M oxalic acid, and then

(ii) 50 cm3,60 cm3,70 cm" 80 cm3and 90 cm3of distilled water, respectively,

so that the total volume in each case becomes 100 cm" Measure 100 cm3of distilled water
into bottle F.

Place all the six bottles in a thermostat or water trough and set them aside to acquire the
temperature of the bath. Measure the temperature of the bath.

Take seven glazed paper pieces which are of equal mass. Place one of these paper pieces on
the left pan. Place a 2 gram weight over it. Place the other glazed paper pieces one by one
on the right pan and each time weigh 2 gram of charcoal powder. Keep the weighed powder
aside under watch glasses or funnels to avoid loss by air currents or spilling. When all the six
powders have been thus made ready, our experiment begins. All the operationsto follow will
be carried out with the six bottles in the same sequence.

Carefully pour weighed charcoal powder into solutions of bottles A to F and close each of
them. Shake each of the bottles for two minutes and place it back in the water trough. Do
it repeatedly for about an hour and half. Long contact periods like keeping overnight should
Appllcatlons of not affect the results. If they do, presence of reactive impurities in the charcoal powder can
Thermodynamics bc suspected. Shorter intervals will not be enough for the adsorption equilibrium state to be
reached due to the heterogeneous porosity of the charcoal powder.

Label the remaining six dry bottles A', B', C', D', E', and F' to correspond to the bottles
A to F. Place one funnel on each bottle. In each funnel set one high quality small dry filter
paper. When all this is set, shake the bottles A to F for the last time and allow the charcoal
to seltle. Record the temperature of water in the trough used for thermostating. In turn,
take these bottles one by one in the order A to F and filter their contents into the correspond-
ing bottles A' to F'. Each funnel should be covered with a watch glass to prevent
evaporation of solution during filtration. In each case reject about half a test-tube full of
filtrate coming out initially (since initial filtrate will have a slightly reduced concentration of
the acid due to adsorption of the acid by the dry filter paper used). After filtration, remove
the funnelsalong with the watch glasses, filter papers and used charcoal. Stopper the bottles
A' to F'. Titrate the contents of each bottle (from A' to F') against the standardized KMn04
solution.

Keeping in view the varied concentrations of oxalic acid in bottles A' to F', the volumes of
oxalic acid to be taken in each case for titration are indicated'below:

(i) 10 cm3from A' and B'

(ii) 20 cm9rom C' and D'

(iii) 25 cm3from E' and

(iv) 40 cm3from F'.

The volume of oxalic acid is taken as above for carrying out the titrations conveniently.

For each titration add one test tube full of 2 M HzS04warmed to 60°C approximately to
the ilask and titrate against standard KMn04solution from the burette. End point will be
marked by the appearance of a tight pink colour. In order to facilitate concordant titre values,
you have been asked to do three titrations using solution from each bottle. The results of
titrations are to be recorded in Table 10.1.

Observations :
Temperature of water in trough (i) Initial = ...."C
(ii) Final = ...."C
Total volume of oxalic acid solution in each bottle = 100 cm3

Total mass of charcoal powder added to each bottle = 2 g

Molarity of stock solution of KMn04 = 2.000 x lo-' M (standardized)

S1, Soln. (Volume Initial Final (Volume of KMn04

No. No. taken)/cm3 burette burette consumed)/cm3
reading reading

1. A' 10

2. A' 10

3. A' 10

10

5. 10
If KMn04 solution required for the filtrate from bottle F' is more than a few drops (say 3
drops), corresponding correction must.be made in the titre values of the remaining bottles.

10.4.4 Calculations
Initial concentration (ci)

You can calculate the initial concentrations (c,) of solutions A to E as follows:

50
Solution A : - x 2.000 x lo-' M = 1.000 x lo-' M
100

Solution B : -
40 x 2.000 x
100
lo-' M = 8.000 x lo-' M

30
Solution C : -
100
x 2.000 x lo-' M = 6.000 x lo-' M

20 lo-'
Solution D : - x 2.000 x M = 4.000 x lo-' M
100

lo
Solution E : - x 2.000 x lo-' M = 2.000 x10-' M
100

The values are entered in Table 10.2.

Equilibrium concentration (c)

Calculate the equilibrium concentrations (c) of solutions A to E i.e., the molarities of
solutions A ' to E' by using Eq. 1.15 given in Section 10.4.1. Enter the values in Table 10.2.
1

Amount of oxalic acid adsorbed

Calculate the amount of oxalic acid adsorbed (x) by using Eq. 10.5. Enter the values in Table
10.2.
 Table 10.2: Data for Adsorption of Oxalic Acid on Charcoal

Determine the values of log c, -log c, log (xlnz), -log (xlm) and cl(x1m). Enter these values
in Table 10.3.

Table 103 : Data for Plotting Graphs

-
Soln. cIM log c/M -106 c/M log (x/rn.ghnoI) -log @/m.g/mol) ( c / w l ) ) x
No. (mo4g.M)

A
Note that M, mol and g are
units for concentration, amount
and mass, respectively. B

To verify that the adsorption of oxalic acid follows Freundlich and Langmuir adsorption
isotherm equations, plot the following graphs:

For Freundlich isotherm :-log (xlnt) versus -log c

For Langmuir isotherm : cl(xltn) versus c

The graphs obtained should be straight lines.

10.4.1 Result

i) It is evident from the values of c andxlnz that the extent of adsorption increases as the
equilibrium concentration of oxalic acid increases.

ii) Graph plotted between -log.(xlnz) and -log c comes out to be a ......................

ii) \ Graph plotted between cl(x1nl) and c comes out to be a ............................

10.5 SUMMARY
In this unit you studied adsorption, physisorption, chemisorption, absorption and sorption.
You were told how to study the adsorption of oxalic acid from aqueous solution on activated
charcoal.
 APPENDIX I -
Oxalic acid :2.000 x lo-' M : Dissolve 25.20 g of (COOH)2.2H20in deionised water and
make up the volume to 1dm?

Sulphuric acid :2 M :Take 900 cm3of deionised water in a 2 dm3beaker. Carefully add to
it, 112 cm3 of conc. HS04 drop by drop with constant stirring. Be careful, the reaction is
highly exothermic.

I Potassium permmgmate :2.000 x M :Dissolve 16 g of KMn04 in 5 dm3of distilled

water. Standardise this solution by titrating against 2.000 x lo-' M oxalic acid.
Fill up the burette with the KMn04solution and mount the burette on a stand. Take 5 cm3
of 2.000 x lo-' M oxalic acid solution into a conical flask and add to it one test tube full of
2 M HS04 warmed to W C approximately. Add KMn04 solution drop by drop and shake
the conical flask continuously. The end point will be marked by the appearance of a light
pink colour. Note down the volume of KMn04required for the titration. Repeat the titration
I
till you get two concordant readings. Calculate the exact molarity of the KMn04solution
using Eq.1.15given in Unit 1of this course (molarity of the solution would be around
0.02 M).

Use the exact molarity of solution in your calculations.

I
 UNIT 11 PHASE EQUILIBRIA - I

Structure
11.1 Introduction
Objectives
11.2 Definition of Terms
Phase Rule
Application of Phase Rule to Two Component Systems
11.3 Experiment 11:To Construct a Phase Diagram for Naphthalene-Benzoic Acid
System
Principle
Requirements
Procedure
Observations
Result
11.4 Summary
11.5 Terminal Questions
11.6 Answers

1 1 . INTRODUCTION
In Unit 13 of the CHE-04 course, you studied the phase rule and its applications to various
one component and two component systems in equilibrium. The phase rule helps us in
understandig the effect of various parameters such as pressure, temperature and composi-
tion on the phase equilibria of a system. It also helps us in understanding many metallurgical
processes (e.g. Pattinsonsprocess for t'he extraction of silver) of great practical value. In this
unit, we will describe an experiment for constructingthe phase diagram for a simple eutectic
system consisting of two components.
,
After studying this unit and having performed the experiment described in it, you should be
able to:
I define the terms phase, component and degrees of freedom,
calculate the number of phases, components and degrees of freedom in a system,
state the phase rule,
I apply the phase rule to the study of a two component system, and
construct the phase diagram for a simple eutectic system.

11.2 DEFINITION OF TERMS

:I1 Before we proceed further, let us define some of the terms involved in phase equilibria.

Phase

Phase (P) is defined as a physically distinct and homogeneous part of the system that is
mechanically separable from other parts of the system. The definition as suggested by Gibbs
is that a phase is a state of matter that is uniform throughout, not only in chemical composition
but also in physical state.

Let us discuss some examples for counting the number of phases in a system.
A gas or a gaseous mixture is a single phase since there c a ~ obe
t an interface between
one gas and aqother. Air, for example, is in one phase only although it is a mixture of
many gases.
A system of totally miscible liquids will exist in one phase only as far as the liquid is
concerned. But since each liquid has its vapour above, the total number of phases in a