Experiment 3: Adsorption

Abstract:
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 from solution follows generally the principle laid down for
the adsorption of gases. Variation of extent of adsorption with concentration of
solute is represented by Langmuir or Freundlich Isotherm. The amount of acetic acid
adsorbed per gram of charcoal will depend on the surface area of charcoal, the
temperature of the solution and the adsorbate concentration in solution. The
adsorption is followed by titrating the acetic acid not adsorbed by the charcoal and
the amount adsorbed by difference is determined. This is an example of physical
adsorption where dipole and van der waal force are predominant sources of
attraction.

Aim:
To study the adsorption of acetic acid by solid adsorbent activated carbon and then
test the validity of certain adsorption isotherm.

Introduction:
Adsorption is the process that uses special solids to remove substances from either
gaseous or liquid mixtures. It is an industrially important process occurs with the
attachment of the gas particles on to the solid surface. The special solids that gas or
liquid particles attached are called adsorbent. The substances adsorbed are called
adsorbate. Adsorption is a phenomenon occcurs at the surface; the molecules are
taken up by the surface. It should not be confused with absorption. Adsorption and
absorption are the two different processes: the molecules are taken up by the
volume in absorption, not by surface i.e. the solute is dissolved in the bulk material in
absorption. Adsorption can be classified into two different groups depending on the
type interaction between the adsorbed molecule and the solid surface.

 Physisorption; Physisorption is caused mainly by intermolecular forces

( Vander Waals) and electrostatic forces between adsorbate molecule and the
atoms which compose adsorbent surface. It will occur when the
 intermolecular attractive forces between and adsorbent and adsorbate are
greater than those existing between molecules of the adsorbate itself.
 Chemisorption; Chemisorption is the result of chemical interaction between
adsorbate and adsorbent. The adsorbate sticks to the solid by the formation
of a chemical with the surface. This interaction is much stronger than
physisorption. Unlike in physisorption only monolayer adsorption is observed.

Activated carbon is basically amorphous carbon based material exhibiting a high

degree of porosity and interparticulate surface area. Large surface area of activated
carbon provides excellent adsorbent characteristics. The surface area per gram of
materail can range 500 to 2000 m 2. Because of its good adsorption properties they
are useful in many industrial process. Filtration, purification, deodorization,
decolorization and separations are the examples of processes.

Adsorption Equilibrium

A large majority of adsorption operate through equilibrium adsorption of mixture.

The amount of gas or liquid adsorbed, n a by mass, per gram of solid, m s, depends on
the specific surface area of the solid, the equilibrium solute concentration in the
solution on, Ceq (Pressure for gas phase adsorption), the temperature, and the nature
of the molecules involved. For the given system at constant temperature it is
possible to write adsorption isotherm equation as follows

qeq=na / ms = f(Ceq) (1)

where qeq is the amount of adsorbate per unit mass of adsorbent.

The most common way of getting information about a given system is to take
experimental measurements, at constant temperature, of the amount of adsorbate
on the surface as the function of the concentration (or pressure) and then draw a
plot of qeq ( the amount of adsorbate per unit mass of adsorbent) versus C eq ( the
equilibrium solute concentration in adsorption from solution). Such graph is called an
adsorption isotherm.

The Freundlich isotherm

It applies over a limited range of the concentrations and is somewhat better for
liquid-solid systems. It has the form of

qeq=na / ms K. (Ceq)a (2)

where, na amount of the adsorbate (grams) & ms = Amount of the adsorbant

In Eqn (2) K and a are constants.

The Langmuir Isotherm

The theory of Langmuir is restricted to cases where only one layer of molecule can be
adsorbed on the surface. As mentioned before, in the case of chemisorption
monolayer adsorption is usually observed. The monolayer adsorption is distinguished
by the fact that the amount adsorbed reaches a maximum value at moderate
concentrations (corresponding a complete coverage of the surface of the adsorbent
by a layer of adsorbed molecules which is one molecule thick only), and remains
constant with further increase in concentration. The equation of Langmuir as derived
for the chemisorption of gases is:

θ=K.(Ceq)/(1+K.Ceq) (3)
where
θ: Fraction of the solid surface covered by the adsorbed molecules
K: Adsorption equilibrium constant
Ceq: Equilibrium concentration
Langmuir isotherm equation can be written for the gas adsorption by replacing C by
P, also note that
Ф=qeq/ qmeq (4)
Where qmeq is the amount of adsorbate per unit mass of adsorbent equired to form a
monolayer.
Hence Eqn 3 takes form of

qeq/ qmeq =K.(Ceq)/(1+K.Ceq) (5)

Ceq/q= Ceq/ qmeq + 1/(K. qmeq) (6)

 Chemicals Required:
Activated carbon, Acetic acid, Sodium Hydroxide, Phenolphthalein, Hydrochloric acid,
Potassium Hydrogen phthalate.

Procedure:
1. Weigh out 0.3 g of activated into each of 5 clean, stoppered 125mL conical
flasks
2. Add 40 ml of 0.20M acetic acid (Stock Solution) to the first flask and shake.
Then add 40mL to each of the other flasks at concentration of 0.15M, 0.10M
and 0.05M,
3. Shake each loosely stoppered flask periodically over 30 minutes noting the
room temperature. Then filter each solution through a filter paper (to remove
charcoal particles completely). It is important that the equilibrium acetic acid
concentration be accurately determined.
4. Pipette two 10mL potion of each filtrate add a few drops of phenolphthalein
indicator and titrate with 0.1 N NaOH. Record the volume of NaOH used.

Observation:
 Normality of NaOH used: 0.1N
 Volume of sample taken for titration: 10 mL

t = 30 min Langmuir isotherm, t = 30 min

C x/m C/(x/m)
Conc. of Amount of 0.035 0.015 2.333
Conc. of Volume of acetic acid acetic acid 0.079 0.021 3.762
acetic acid NaOH used after adsorbed per 0.11 0.04 2.750
(C0) adsorption mL NaoH 0.169 0.031 5.452
(Ce) (C0 - Ce) Freundlich isotherm, t = 30 min
(mL)
x/m ln(x/m) C lnC
0.05 3.5 0.035 0.015 0.015 4.200 0.035 3.352
0.1 7.9 0.079 0.021 0.021 3.863 0.079 2.538
0.15 11 0.11 0.04 0.04 3.219 0.11 2.207
0.2 16.9 0.169 0.031 0.031 3.474 0.169 1.778
 t = 60 min Langmuir isotherm, t = 60 min
C x/m C/(x/m)
Conc. of Amount of 0.033 0.017 1.941
Conc. of Volume of acetic acid acetic acid 0.074 0.026 2.846
acetic acid NaOH used after adsorbed per 0.105 0.045 2.333
(C0) adsorption mL NaoH 0.162 0.038 4.263
(Ce) (C0 - Ce) Freundlich isotherm, t = 60 min
(mL) x/m ln(x/m) C lnC
0.05 3.3 0.033 0.017 0.017 4.075 0.033 3.411
0.1 7.4 0.074 0.026 0.026 3.650 0.074 2.604
0.15 10.5 0.105 0.045 0.045 3.101 0.105 2.254
0.2 16.2 0.162 0.038 0.038 3.270 0.162 1.820

Freundlich isotherm:

It is given by equation ln ( mx )=ln ( k ) + 1n ln ⁡(C)

For t = 30 min,
Slope of ln(x/m) vs ln(C) curve = 0.5521
Which implies, 1/n = 0.5521 & n = 1.811

Intercept of ln(x/m) vs ln(C) curve = 2.3258

Which implies, ln (k) = 2.3258 & k = 10.234

For t = 60 min,
Slope of ln(x/m) vs ln(C) curve = 0.5811
Which implies, 1/n = 0.5811 & n = 1.721

Intercept of ln(x/m) vs ln(C) curve = 2.0582

Which implies, ln (k) = 2.0582 & k = 7.832

Langumir isotherm:

C 1 C
It is given by equation x /m = k k + k
1 2 2

For t = 30 min,
 Slope of C/(x/m) vs C curve = 20.811
Which implies, 1/k2 = 20.811 & k2 = 0.048

Intercept of C/(x/m) vs C curve = 1.5295

Which implies, 1/k1k2 = 1.5295 & k1 = 13.621

For t = 60 min,
Slope of C/(x/m) vs C curve = 16.46
Which implies, 1/k2 = 16.46 & k2 = 0.061

Intercept of C/(x/m) vs C curve = 1.3069

Which implies, 1/k1k2 = 1.3069 & k1 = 12.54

Conclusion:
We notice here that there isn’t much difference in the adsorption at 30 mins and 60
mins and they have almost the same readings. This clearly indicates that the
adsorption equilibrium is achieved within 30 mins only.