ADSORPTION STUDIES

AIM: - To Verify the Freundlich Equation by an adsorbing acetic acid on activated carbon
from an acetic acid solution and estimation of the constants of the equation.

APPARATUS:-

Five stoppered bottles, conical flask, burette with stand, funnel, pipette, measuring
Jar.
CHEMICALS REQUIRED:-

Standard solution of Oxalic acid, Sodium hydroxide solution, acetic acid, activated
Charcoal and Phenolphthalein indicator.
THEORY:-

Adsorption is a process that occurs when a gas or liquid solute accumulates on the
surface of a solid or a liquid (adsorbent), forming a molecular or atomic film (adsorbate).
Adsorption is a consequence of surface energy. In a bulk material, all the bonding
requirements (be they ionic, covalent or metallic) of the constituent atoms of the material are
filled. The adsorbed material is generally classified as exhibiting physisorption or
chemisorption.

Physisorption or physical adsorption is a type of adsorption in which the adsorbate

adheres to the surface only through Van der Waals (weak intermolecular) interactions.

Chemisorption is a type of adsorption whereby a molecule adheres to a surface

through the formation of a chemical bond, as opposed to the Van der Waals forces which
cause physisorption.

Freundlich adsorption isotherm - It is an empirical relation between the concentration of

a solute on the surface of an adsorbent to the concentration of the solute in the liquid with
which it is in contact.

The Freundlich adsorption isotherm is mathematically expressed as

𝟏
𝒙
𝒎
= 𝑲𝒑𝒏
where

x = mass of adsorbate
m = mass of adsorbent
p = Equilibrium pressure of adsorbate
c = Equilibrium concentration of adsorbate in solution.
K and n are constants for a given adsorbate and adsorbent at a particular temperature.

At high pressure 1/n = 0, hence extent of adsorption becomes independent of pressure.

On linearizing the above equation

𝒙 𝟏
𝐥𝐨𝐠 𝒎 = 𝐥𝐨𝐠 𝑲 + 𝐥𝐨𝐠 𝒑
𝒏

𝑥
Plotting the graph between log 𝑚 and log 𝑝 , we will get a straight line with value of

slope equal to 1/n an log K as y-axis intercept.

Slope = 1/n

𝑥 Intercept = log K
log 𝑚

log 𝑝

In terms of concentration for dilute solution the Freundlich equations can be given as :-

At a given temperature, the mass of a solute adsorbed by a solid adsorbent at various

amounts are given by the following empirical relation.

C* = K [V (C0 – C*)] n

Where C0 = initial concentration of acetic acid solution

C* = equilibrium concentration after adsorption
V = Volume of given solution / mass of solid
K, n are constants at a given temperature for a given solute and adsorbent.
Langmuir Adsorption Isotherm - Langmuir proposed another Adsorption Isotherm which
explained the variation of Adsorption with pressure. Based on his theory, he derived
Langmuir Equation which depicted a relationship between the number of active sites of the
surface undergoing adsorption and pressure.

Assumptions of Langmuir Isotherm:-

1. Fixed number of vacant or adsorption sites are available on the surface of solid.

2. All the vacant sites are of equal size and shape on the surface of adsorbent.

3. Each site can hold maximum of one gaseous molecule and a constant amount of heat
energy is released during this process.

4. Dynamic equilibrium exists between adsorbed gaseous molecules and the free gaseous
molecules.

A(s) + 𝐵(𝑔) 𝐴𝐵

Where A (g) is unadsorbed gaseous molecule,

B(s) is unoccupied metal surface and

AB is Adsorbed gaseous molecule.

5. Adsorption is monolayer or unilayer.

Langmuir Adsorption Equation:

𝑲𝑷
𝜽 = 𝟏+𝑲𝑷

𝑲
K= 𝑲𝒂
𝒅

θ = be the number of sites of the surface which are covered with gaseous molecules

Ka and Kd are equilibrium constant for forward and backward direction.

P= pressure
PROCEDURE: -
1. Prepare exactly 0.1 N Oxalic acid solution.
 2. Take 5 reagent bottles and label them 1 to 5.
3. Weight separately and accurately 0.5, 1, 1.5, 2, 2.5 gm of activated carbon and
transfer it in to 5 reagent bottles in the same order.
4. Prepare solution of 0.1 N HCl and 0.1 N NaOH solutions.
5. Verify the Normality of NaOH by taking 10 ml of standard Oxalic solution and
titrating against it.
6. From this NaOH solution, find exactly the normality of HCl solution by titration.
7. Carefully measure and transfer 50 ml of acetic acid solution of known
concentration (0.1N) to each reagent bottle.
8. Close the lids and keep the bottles in a shaker. Switch on the shaker and operate it
for about 30 minutes.
9. At which time the equilibrium is expected to reach between the liquid and solid
phases.
10. Remove the bottles from the shaker, filter the contents of each bottle and collect
the clear solution in to 5 separate 250ml conical flasks also numbered 1 to 5.
11. From each of these solutions take 10 ml with pipette and titrate against the
previously standardized NaOH solution using phenolphthalein indicator.

STANDARDISATION OF 1N NaOH:

Standard solution of Oxalic acid (1N) was prepared by dissolving 6.3g of Oxalic acid in
100ml of water.

Wash 50ml burette and rinse with 1N NaOH. Pipette out 10ml of std. Oxalic acid into conical
flask and titrate it with NaOH in burette using phenolphthalein indicator. The end point has
been reached when the pale pink color of the phenolphthalein persists for 30 seconds. There
should be a one-drop difference between when the solution is colourless and when it is pink.
If too much NaOH is added (that is, if you "over-shoot" the endpoint), discard the solution
and repeat the titration. A white piece of paper placed under the flask will aid in the colour
detection.

STANDARDISATION OF 1N HCl:
Wash 50ml burette and rinse with 1N NaOH. Pipette out 10ml of HCl into conical flask and
titrate it with NaOH in burette using phenolphthalein indicator. The end point has been
reached when a very light pink color persists for at least 30 seconds.

Observation Table

Flask Wt.of activated Volume of acetic Volume of water(ml)

carbon(gm) acid(ml)
1. 1.00 5 25
2. 1.01 10 20
3. 1.00 15 15
4. 1.00 20 10
5. 1.00 25 5
6. 1.01 30 0

Strength of NaOH solution=0.1N

Strength of acetic acid solution=0.09N

Temperature of stirring=40C

Speed of stirring=200rpm

Weight of activated carbon taken in each flask=1.0gm

Titration after Adsorption

Flask Volume of sample taken after Volume of NaOH rundown(ml)

adsorption(ml)
1 5 0.2
2 5 0.6
3 5 1.3
4 5 2.8
5 5 3.2

CALCULATION
Sample Calculation for Flask 1

Weight of activated carbon=1.00gm

Initial strength of acetic acid solution

Ni=5*0.09/30

=0.015N

Final Strength of acetic acid solution after adsorption

Nf=(0.2*.1)/5

=0.004N

=C0o14*60=0.9Kg/m3

C*=0.004*60

=0.24Kg/m3

V=30ml/1gm

V=0.03m3/kg

logC*=-0.6198

log[V(Co-C*)]=-1.703

CALCULATION TABLE

SL.n Wt. of Vol of V(m3/kg Co(kg/m C*(kg/m logC* log[V(C

o. adsorbent(gm acetic acid ) 3) 3) o-C*)]
) solution(m
l)
1 1.00 30 0.03 0.9 .24 -0.62 -1.70
2 1.01 30 0.0297 1.8 0.72 -0.14 -1.50
3 1.00 30 0.03 2.7 1.56 -0.19 -1.46
4 1.00 30 0.03 4.5 3.36 0.53 -1.46
5 1.01 30 0.0297 5.4 3.96 0.60 -1.37
 0.8

0.6

0.4

0.2

0 Series1
-2 -1.5 -1 -0.5 0
-0.2
log[V(Co-C*)]
-0.4

-0.6

-0.8

logC*=logK+nlog[V(Co-C*)]

From graph between logC* and log[V(Co-C*)]

Slope=n=3.5

At log C*=0.25

log[V(Co-C*)]=-1.45

So,0.25=logK+3.5(-1.45)

K=2.11*10^5

K=211 g/ml

RESULT

The constants of Freudlich equations are

N=3.5 & K=211 g/ml