ADAMSON UNIVERSITY

College of Engineering
Chemical Engineering Department
Manila

Experiment 6: Absoption

PHYSICAL CHEM FOR ENGRS 2 LAB (51009)

Date Performed: September 11, 2017
Date Submitted: September 18, 2017

Proponents:
Bote, Joanne G. (201412264)
Ramos, Rem Camille C. (201410321)
Rivera, Anna Roselle L. (201410699)

Instructor:
Engr. Robert E. Delfin
Abstract
In this experiment, we were to determine the saturation value for monomolecular
coverage for the adsorption of acetic acid by activated charcoal, to determine the values of the
constant k and n in the Freundlich equation and the values of the constant a and b., It was found
out that the saturation value for a 1M acetic acid was 266.28, while for a 0.5M acetic acid was
113.25 and for a 0.0625M acetic acid was 6.10. Solving for k and n using the Freundlich
equation, was 0.1663 and 466.96 respectively and where a is equal to 13.692, while b is 478.058
by using the Langmuir equation. Adsorption is an accumulation of large number of molecular
species at the surface of liquid or solid phase in comparison to the bulk. Adsorbent is the
substance on the surface of which adsorption takes place. Adsorbate is the substance which is
being adsorbed on the surface of adsorbent. Adsorbate gets adsorbed. The amount of adsorbate
for a given quantity of adsorbent increases with the concentration of the solution. Hence, the
amount of glacial acetic acid (adsorbate) adsorbed per gram of charcoal (adsorbent) will
depend on the surface of the charcoal, the temperature of the solution and the absorbate
concentration in the solution.

I. Introduction
Adsorption is the phenomenon of accumulation of large number of molecular species at the
surface of liquid or solid phase in comparison to the bulk. Adsorption is a surface phenomenon.

The process of adsorption happens due to presence of unbalanced or residual forces at the
surface of liquid or solid phase. These unbalanced residual forces have tendency to attract and
retain the molecular species with which it comes in contact with the surface. Adsorption is
different from Absorption .Absorption means uniform distribution of the substance throughout
the bulk, adsorption essentially happens at the surface of the substance. When both Adsorption
and Absorption processes take place simultaneously, the process is called sorption.

Adsorption process involves two components Adsorbent and Adsorbate. Adsorbent is the
substance on the surface of which adsorption takes place. Adsorbate is the substance which is
being adsorbed on the surface of adsorbent. Adsorbate gets adsorbed. In this experiment, the
adsorbate is the charcoal, and the adsorbent is the glacial acetic acid.

II. Theoretical Background

Adsorption is the adhesion of atoms, ions, molecules of gas, liquid, or dissolved solids to a
surface. This process creates a film of the adsorbate (the molecules or atoms being accumulated)
on the surface of the adsorbent. It differs from absorption, in which a fluidpermeates or is
dissolved by a liquid or solid. The term sorption encompasses both processes, while desorption is
the reverse of adsorption. It is a surface phenomenon.

Adsorption is described through isotherms, that is, the amount of adsorbate on the adsorbent
as a function of its pressure (if gas) or concentration (if liquid) at constant temperature. The
quantity adsorbed is nearly always normalized by the mass of the adsorbent to allow comparison
of different materials. There are basically two well established types of adsorption isotherm: the
Freundlich adsorption isotherm and the Langmuir adsorption isotherm.

Freundlich Isotherm:

The Freundlich equation or Freundlich adsorption isotherm is an adsorption isotherm, which

is a curve relating 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. In 1909, Freundlich gave an
empirical expression representing the isothermal variation of Adsorption of a quantity of gas
adsorbed by unit mass of solid adsorbent with pressure. This equation is known as Freundlich
Adsorption Isotherm or Freundlich Adsorption equation.

The Freundlich Adsorption Isotherm is mathematically expressed as

1
x
=K p n  
m
It is also written as

log ( mx )=log K +( 1n )logp

or

1
x
                   =K c n  
m
It is also written as

log ( mx )=log K +( 1n )logc

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 is independent of pressure but at high pressure it is
dependent on pressure.

There are some limitations of Freundlich adsorption isotherm. Experimentally it was

determined that extent of adsorption varies directly with pressure till saturation pressure Ps is
reached. Beyond that point rate of adsorption saturates even after applying higher pressure. Thus
Freundlich Adsorption Isotherm failed at higher pressure.

The Langmuir isotherm relates the coverage or adsorption of molecules on a solid surface to
gas pressure or concentration of a medium above the solid surface at a fixed temperature. The
equation was developed by Irving Langmuir in 1916. The equation is stated as:

4θ or theta is the fractional coverage of the surface, P is the gas pressure or concentration, α
alpha is a constant.
 The constant α is the Langmuir adsorption constant and increases with an increase in the
binding energy of adsorption and with a decrease in temperature

III. Procedure
This is a single method experiment designed determine the saturation value for
monomolecular coverage for the adsoprtion of acetic acid by activated charcoal, to determine the
values of the constant k and n in the Freundlich equation and to determine the values of the
constant a and b in Langmuir’s equation. The experiment was subdivided into nine steps
discussed below.

First, 100ml of glacial acetic acid with concentrations of 1M, 0.5M, and .0625M was
prepared. 50ml of the 1M solution was measured and was placed into a 125ml Erlenmeyer flask
and 1.0g of accurately weighed activated charcoal was added. The mixture was shook and was
allowed to equilibriate for one hour. The mixture was then agitated from time to time during the
equilibrium process.

While equilibriation was taking place, 5ml of the original solution was pipetted into a 250ml
Erlenmeyer flask and was titrated with 1M NaOH to the phenolphthalein endpoint. The original
concentration was then calculated from the titration data.

After the equilibriation, the activated charcoal was then filtered and was titrated with 0.1M
NaOH to the phenolphthalein endpoint.

The equilibrium concentration and the specific adsorption for each concentration was then
calculated using the formula:

( C 1−C 2 ) x MW HOAc x V soln

y=
W charcoal

Initial Conc (C1) Final Conc (C2) Wacetic acid mcharcoal y

1.0 0.52 419.18 1.05 266.28
0.5 0.27 376.28 1.00 113.25
 0.0625 0.033 264.79 0.90 6.10
IV. Results

k 0.1663
n 466.96
a 13.692
b 478.0587

GRAPHS
 Y vs C1

266.28

113.25

6.1
0.06 0.5 Series 1 1

logY VS C1
3

2.5

1.5

0.5

0
0.06 0.5 1

Series 1
 C1/Y versus C1
0.01

0.01

0.01

0.01

0
0.06 0.5 1

Series 1

V. Discussion of Results

Solids have the property of holding molecules at their surfaces, and this property is quite
marked in the case of porous and finely divided material. Adsorption is the attachment of
molecules to the surface of a solid, and it is frequently quite specific, so that one solute may be
adsorbed selectively from a mixture.

The adsorbate refers to the substance that is adsorbed whereas the underlying material or
substrate refers to the adsorbent. The amount of adsorbate for a given quantity of adsorbent
increases with the concentration of the solution. In some cases, the layer of adsorbed molecules
is only one molecule deep and further adsorption ceases when the surface of the crystal lattice is
covered. The adsorbed and free reactant are in dynamic equilibrium during the adsorption
process, and the surface coverage depends upon surface composition and structure of the
adsorbent, the nature and concentration of the solvent as well as temperature and pressure.

The amount or pressure of reactant adsorbed for a given temperature is described by

adsorption isotherms. The adsorption of dissolved substances in liquid solutions by solids may be
formulated (within certain concentration limits) by the equation for the adsorption isotherm
proposed by Freundlich:

x/m = kyn (1)

where, x/m represents the mass of material adsorbed per unit mass of adsorbent, y is the
concentration in the solution, at equilibrium, k and n are the constants under the given
conditions.

Definite masses of the adsorbent is brought into contact with a series of solutions of
varying initial concentrations of the reagent to be adsorbed, after equilibrium has been
established, liquids are filtered and analyzed to determine the degree of adsorption in each case.
The amount adsorbed in each case is equal to the difference of the initial and final concentration.
The equation for the adsorption isotherm may be written in the logarithmic form as follows:

log x/m = log k + n log y (2)

According to this equation, a plot of log x/m against log y yields a straight line. The constants k
and n are evaluated from the intercept and the slope of the line.

The term adsorption is used to describe the fact that there is a greater concentration of the
adsorbed molecules at the surface of the solid than in the bulk solution. In general, one uses solid
adsorbents of small size and often with surface imperfections such as cracks and holes which
serve to increase the surface area per unit mass greatly over the apparent geometrical area. Such
small, porous particles may have specific areas in the range from 10 to 1000 m2g-1. Some
examples of adsorbents commonly used in experiments of this kind are charcoal, silica gel,
alumina, zeolites, and molecular sieves. The adsorption from aqueous solutions of acetic acid on
charcoal will be investigated in the present experiment.

The type of interaction between the adsorbed molecule and the solid surface varies over a
wide range from weak nonpolar van der Waals’ forces to strong chemical bonding. Examples of
adsorption where ionic or covalent bonding occurs are the adsorption of chloride ions and silver
chloride (ionic) or of oxygen gas on metals where oxygen-metal bonds are formed (covalent). In
these cases, the process is called chemisorption, and it is generally characterized by high heats of
adsorption (from 10 to 100 kcal mol-1 of gas adsorbed). Chemisorption is highly specific in
nature and depends on the chemical properties of both the surface molecules and the adsorbed
molecules. Adsorption arising from the weaker van der Waals’ and dipole forces is not so
specific in character and can take place in any system at low or moderate temperatures. This type
of adsorption is called physical adsorption and is usually associated with low heats of adsorption
(less than about 10 kcal mol-1). Physical adsorption forces are similar to those which cause
condensation of gases into liquid or solids. When an adsorbing molecule approaches the surface
of the solid, there is an interaction between that molecule and the molecule in the surface which
tends to concentrate the adsorbing molecules on the surface in much the same way that a gas
molecule is condensed onto the surface of bulk liquid. Another respect in which physical
adsorption is similar to liquid condensation is the fact that molar heats are of adsorption are of
the same order of magnitude as molar heats of vaporization.

The amount adsorbed per gram of solid depends on the specific area of the solid, the
equilibrium solute concentration in the solution (or pressure in the case of adsorption from the
gas phase), the temperature, and the nature of the molecules involved. From measurements at
constant temperature, one can obtain a plot of N, the number of moles adsorbed per gram of
solid, versus c, the equilibrium solute concentration. This is called an adsorption isotherm.

Often it is possible to represent experimental results over a limited range by an empirical

isotherm suggested by Freundlich:

N = Kca (1)

Where K and a are constants which have no physical significance, but can be evaluated by a plot
of log N versus log c. However, Eq. (1) fails to predict the behavior usually observed at low and
at light concentrations. At low concentrations, N is often directly proportional to c; at high
concentrations N usually approaches a constant limiting value which is independent of c.

Much effort has been devoted to developing a theory of adsorption which would explain
the observed experimental facts. In some simple systems, a theory derived by Langmuir can be
applied. This theory is restricted to cases where only one layer of molecules can be adsorbed at
the surface. Monolayer adsorption is usually observed in the case of chemisorption from the gas
phase or adsorption from solution. Monolayer adsorption is distinguished by the fact that the
amount adsorbed reaches a maximum value at moderate concentrations (corresponding to
complete coverage of the surface of the adsorbent by a layer one molecule thick) and remains
constant with further increase in concentration. The Langmuir isotherm can be derived from
either kinetic or equilibrium arguments and is most commonly applied to the chemisorption of
gases. We shall give a form appropriate to adsorption from solution:

(2)

Where θ is the fraction of the solid surface covered by adsorbed molecules and k is a constant at
constant temperature. Now θ = N/Nm, where N is the number of moles adsorbed per gram of
solid at an equilibrium solute concentration c and Nm is the number of moles per gram required
to form a monolayer. Making this substitution and rearranging Eq. (2), we obtain

(3)

If the Langmuir isotherm is an adequate description process, then a plot of c/N versus c
will yield a straight line with slope 1/Nm. If the area σ occupied by an adsorbed molecule on the
surface is known, the specific area A (in square meters per gram) is given by:

A = NmN0σ×10-20 (4)

Where N0 is Avogadro’s number and σ is given in square angstroms.

Soild surfaces can absorb dissolved substances from solution. When a solution of acetic
acid in water is shaken with activated charcoal, part of the acid is removed by the carbon and the
concentration of the solutionis decreased. From the results gathered, it is clear that K increases as
the concentration of acetic acid is decreased with respect to time. Hence, the degree to which a
solid will adsorb the material depends on a number of factors including temperature, nature of
the molecule being adsorbed, degree of surface pore structure, and solute concentration and
solvent. Other factors are important factors dealing with the process of adsorption of solutes
from aqueous solution by highly porous solids.
 Adsorption involves a substance being taken into a bulk of a phase, while absorption
involves a substance being taken onto a surface. The adsorption process is represented by

A + surface site → A (adsorbed)

It is assumed that the surface contains a set of site at each of which a molecule of A can be
adsorbed, and that only a single layer of molecules of A (a monolayer) can be adsorbed on the
surface. The sites might include all of the atoms of the solid surface, or might be special
locations such as a “step” between two layers of atoms. It is assumed that the total number of
surface sites is fixed for a fixed amount of catalyst. The fraction of the surface sites occupied by
adsorbed. A molecule is denoted by θ.

The activity level of adsorption is based on the concentration of substance in the water,
the temperature and the polarity of the substance. A polar substance (a substance which is good
soluble in water) cannot or is badly removed by active carbon, a non-polar substance can be
removed totally by active carbon. Every kind of carbon has its own adsorption isotherm and in
the water treatment business this isotherm is definite by the function of Freundlich.

For this experiment, it is influenced by the concentration of the solution. The type of
adsorption involve is chemisorption. Concentration of solution will affect the adsorption. As the
concentration increase, the rate of adsorption will increase too.

At a certain time, the adsorption will stop and remain constant as the layers of charcoals are
already full with acetic acid molecules.

Activated carbon is used as an adsorbent. Adsorbents are used usually in the form of
spherical pellets, rods, moldingsm or monoliths with hydrodynamic diameters between 0.5 mm
and 10mm. They must have high abrasion resistance, high thermal stability and small pore
diameters, which results in higher exposed surface area and hence high surface capacity for
adsorption. The adsorbents must also have a distinct pore structure which enables fast transport
of the gaseous vapors.

VI. Conclusion and Recommendation

 In this experiment, adsorption from solution follows generally the principles laid
down for the adsorption of gases. The variation of extend of adsorption with
concentration of solute is represented by the Freundlich and Langmuir equatins.
Surfaces exhibits a unique property and is an example of physical adsorption. The
amount of glacial acetic acid (adsorbate) adsorbed per gram of charcoal (adsorbent)
will be dependent on the charcoal, the temperature of the solution and the absorbate
concentation in the solution. The adsorption is followed by titrating the glacial acetic
acid being filtered by the charcoal and then the amount absorbed by difference is
determined.
While doing the experiment, it is important shake the solution properly and
examine it the solution still have some charcoal left in the bottom. If none, then
proceed to filtering.
The experimenter recommend to include the disposal of used chemicals in the
procedure and also the required formula for the specified experiment. Furthermore,
the burette should not be leaking and is clean to have a good and accurate results in
the titration process.

Literature Cited
Adsorption. (n.d.). Retrieved September 17, 2017, from
http://www.chemistrylearning.com/adsorption/

iitkgp.vlab.co.in,. (2013). ADSORPTION. Retrieved 17 September 2017, from

iitkgp.vlab.co.in/?sub=35&brch=107&sim=1531&cnt=1

Nomenclature
Adsorption - is the adhesion of atoms, ions, or molecules from a gas, liquid, or dissolved
solid to a surface. This process creates a film of the adsorbate on the surface of the adsorbent.
 Chemisorption - is a kind of adsorption which involves a chemical reaction between the
surface and the adsorbate. New chemical bonds are generated at the adsorbant surface.

Freundlich equation - or Freundlich adsorption isotherm, an adsorption isotherm, 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.

Langmuir monolayer - or insoluble monolayer is a one-molecule thick layer of an

insoluble organic material spread onto an aqueous subphase. Traditional compounds used to
prepare Langmuir monolayers are amphiphilic materials that possess a hydrophilic headgroup
and a hydrophobic tail.

Monolayer - is a single, closely packed layer of atoms, molecules, or cells. In some cases
it is referred to as a self-assembled monolayer. Monolayers of layered crystals like graphene and
molybdenum disulfide are generally called 2D materials.

Physisorption - also called physical adsorption, is a process in which the electronic

structure of the atom or molecule is barely perturbed upon adsorption.

Appendices
A1. Raw Data
A2. Sample Calculations

( C 1−C 2 ) x MW HOAc x V soln

y=
W charcoal
g
( 1.0−0.52 ) x 60.05 x 9.7 L
mol
y 1.0 M = =266.28
1.05 g
 g
( 0.5−0.27 ) x 60.05 x 8.2 L
mol
y 0.5 M = =113.25
1.00 g
g
( 0.0625−0.033 ) x 60.05 x 3.1 L
mol
y 0.0625 M = =6.10
0.9 g
Using Freundlich equation,
418.84 = k(0.52)n n = 0.1663
375.59 = k(0.27)n k = 466.96

Using Langmuir equation,

ab (0.52)
419.18= a = 13.692
1+ a(0.52)
ab(0.27)
376.28= b = 478.0587
1+a (0.27)
 Experiment 7

CHEMICAL EQUILIBRIUM

OBJECTIVE:
To be able to determine the equilibrium constant for the system:
Fe3+ + CNS F eCNS2+
Yellow colorless blood-red
DISCUSSION:
The word equilibrium suggests balance or stability. The fact that a chemical reaction occurs
means that the system is not in equilibrium. The process will continue until the system reaches
equilibrium. At this point, there is no observable change in the concentrations of reactants and
products. While the reaction appears to stop, the reality is that reactants are being converted to
products at the same rate that products are being converted to reactants.

These principles can be illustrated with a generic reaction:

aA + bB → cC + dD

If only A and B are present, the reaction will proceed to the right; if only C and D are present,
the reaction will proceed to the left. In both cases, the reaction will apparently stop
when equilibrium is reached.This state is characterized by a specific value for the
equilibrium constant K, defined for this reaction by the following expression.

[C] c [D] d
K= a b
[ A ] [ B]
Here the brackets signify the equilibrium concentrations (in M) of the various species. Note that
the coefficients in the balanced equation appear as exponents in the equilibrium constant and that
the products always appear in the numerator and the reactants in the denominator.

The value of the equilibrium constant depends on the chemical reaction and on temperature.
However, the value of K will not depend on the initial concentrations of reactants and products.
Furthermore, the specific mathematical form of the equilibrium constant must correspond to the
correct chemical equation for the reaction. If the equation is not correct – for example, if the
formula of one or more of the species is wrong – the value of K, even if calculated using accurate
concentrations and making no numerical errors, will not be constant.

3+
In this experiment you will investigate the reaction of the Fe [iron(III), or “ferric”] ion with
–
the SCN (thiocyanate) ion. The product of this reaction is a complex ion that imparts a red
color to aqueous solution. You are asked to experimentally determine the formula for the
complex ion and a numerical value for the equilibrium constant for the reaction in which it is
formed.

PROCEDURE:
1. Label 5 clean and dry test tube of identical size and make.
2. Prepare solutions of Fe(NO3)3 by serial dilution as follows:
a.) Place 20 mL of 0.20 M Fe(NO3)3 in a 25-mL graduated cylinder.
b.) Transfer 8 mL of the solution into test tube 1.
c.) Add distilled water to the remaining solution in the graduated cylinder to bring the
volume to 20 mL.
d.) Transfer 8 mL of diluted solution into test tube 2.
e.) Repeat procedures c and d until 5 different concentrations of Fe(NO3)3 are obtained.

3. Add 8 mL of 0.002 M KCNS to each diluted solutions from step 2.

4. Wrap each test tube with white paper.

5. By looking down into the solutions in the test tube, compare the color intensities of the
solutions in test tubes 1 and 2. (The process may be aided by placing a mirror below the
test tubes).

6. Adjust the height of the solution in test tube 1 by removing or adding some solution until
the observed color intensities appear to be equal. Transfer the solution in test tube 1 to
clean container with the aid of dropper.

7. Measure the heights of the solutions in test tubes 1 and 2 by means of a ruler.

8. Repeat steps 5, 6 and 7 with the test tubes 3, 4 and 5.

9. Record all measured heights of solution.

10. By assuming that all the limiting reagent in test tubes 1 was converted to the complex,
calculate the concentration of the complex in test tubes 2 to 6 by using test tube 1 as
standard and by applying Beer-Lambert’s law:

CS x hs = CU x hu
Where: CS=concentration of the standard
 hs= height of the standard
CU=concentration of the unknown
hU=height of unknown

11. Calculate the equilibrium concentrations of the reactant.

[Reactants] equilibrium = [Reactants]initial – [Reactants]converted

12. Record all the data in the table.

Experiment No. 7

CHEMICAL EQUILIBRIUM

PRELAB EXERCISES:

NAME: __________________________________________ DATE: _________________

PROFFESOR: ______________________________________

1. Discuss Beer-Lambert’s Law, its application and limitations.

 Experiment 7

CHEMICAL EQUILIBRIUM

PRELIMINARY DATA SHEET

Date: _______________ Score: _______

Group No.: ___________

SIGNATURE

Leader: ____________________________________ __________________________

Members: ____________________________________ __________________________

____________________________________ __________________________

____________________________________ __________________________

THEORETICAL FRAMEWORK: (PREPARE A FLOWCHART OF THE PROCEDURE

OF THE EXPERIMENT)
EXPERIMENTAL RESULTS AND OBSERVATION:
Test Tube No. 1 2 3 4 5
Before [Fe3+]
________ ________ ________ ________ ________
Mixing [CNS-]
________ ________ ________ ________ ________
After [Fe3+]
________ ________ ________ ________ ________
Mixing [CNS-]
________ ________ ________ ________ ________
hs (height of standard)
xxx ________ ________ ________ ________
hu (height of unknown)
xxx ________ ________ ________ ________
3+
[Fe ]
 xxx ________ ________ ________ ________
-
[CNS ]
xxx ________ ________ ________ ________
2+
[FeCNS ]
________ ________ ________ ________ ________
keq
xxx ________ ________ ________ ________
Computation of Average Keq:

GUIDE QUESTIONS AND PROBLEMS:

1. How is the value of the equilibrium constant affected by the concentration of the
reactants used?

2. How do you explain the above observation?

3. What factors affect the value of the equilibrium constant?