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Introduction
Surface chemistry deals with the physical and chemical interfacial processes between different phases
and have numerous applications. Irving Langmuir was awarded with Nobel prize in 1932 for his research
on surface chemistry and Gerhard Ertl was awarded Nobel prize in 2007 for his seminal work in the area
of surface science. Surface science has applications from adsorption phenomena to electrochemistry,
heterogeneous catalysis, Interface and colloids, fuel cells and in energy storage materials like metal-
organic frameworks (MOFs), etc.
Sorption is defined as a physical and/or chemical process whereby one substance becomes attached to
another. Sorption can be classified as absorption or adsorption. In absorption, the atoms, ions, or
molecules are taken up by the bulk of the phase (gas, liquid, or solid). On the other hand, adsorption
involves the adhesion of atoms, ions, or molecules of a gas, liquid, or dissolved solids to a surface of a
material. This process creates a film of adsorbate on the surface of adsorbent. The figure below depicts
the difference between adsorption and absorption. Desorption is the reverse of adsorption.
Adsorption happens in most natural, physical, biological, and chemical systems due to surface energy (or
surface tension). In bulk materials, all the bonding requirements of the constituent atoms of the material
are satisfied but atoms on the surface experience a bond deficiency, because they are not totally
surrounded by other atoms. Thus, it is energetically favorable for them to bond with other species to
lower their energies. The exact nature of the bonding depends on the details of the species involved, but
the adsorbed material is generally classified as exhibiting physisorption or chemisorption. A general
comparison is given below.
Properties Physisorption Chemisorption
Bonding Weak, long range Van der Waals Strong, short range chemical bonding
interactions (e.g. London dispersion, involving orbital overlap and charge
dipole-dipole) transfer
Graduate Chemistry Lab- CHEM503
Adsorption Isotherms
Adsorption is usually described through isotherms, that is, functions which connect the amount of
adsorbate on the adsorbent, with its pressure (if gas) or concentration (if liquid) at a constant
temperature. One can find in literature several models describing the process of adsorption. The most
applicable models are Freundlich adsorption isotherm and Langmuir adsorption isotherm.
1. Langmuir isotherm
Langmuir’s isotherm describes gas adsorption on solids based on a kinetic mechanism and is purely a
theoretical model. The main assumptions are:
• The surface of the adsorbent is uniform, that is, all the adsorption sites are equal
• Adsorbed molecules do not interact
• Adsorption involves the attachment of only one layer of molecules to the surface i.e., monolayer.
Let an adsorbate A form a monolayer on the surface of absorbent S. The relation is,
𝐴 + 𝑆 ↔ 𝐴𝑆
where AS represent A molecule attached to S site. The equilibrium constant is
[𝐴𝑆]
𝐾𝑎𝑑𝑠 =
[𝐴][𝑆]
Where [A] is concentration of A, and [S] and [AS] are two-dimensional equivalents of concentration with
units such as mol/cm2. Defining as fraction of adsorption sites attached to A,
𝜃 𝜃
𝐾𝑎𝑑𝑠 = =
[𝐴](1 − 𝜃) 𝐶(1 − 𝜃)
where [A] is basically concentration C. Re-arranging,
𝐾𝑎𝑑𝑠 𝐶 1-1
𝜃=
1 + 𝐾𝑎𝑑𝑠 𝐶
which is the final form of Langmuir adsorption isotherm. A typical Langmuir isotherm is shown in the
Figure below.
Graduate Chemistry Lab- CHEM503
2. Freundlich isotherm
Freundlich isotherm is an empirical model. The Freundlich model doesn’t have the restriction of
monolayer adsorption. This isotherm relates the concentration of a solute on the surface of adsorbent to
the concentration of solute in the liquid in contact and is commonly used for heterogeneous surfaces. This
isotherm is mathematically expressed as
1 𝑛 ⁄
𝐶𝑎𝑑𝑠 = 𝐾𝐶𝑒𝑞
Or
1 1-3
𝑙𝑜𝑔𝐶𝑎𝑑𝑠 = 𝑙𝑜𝑔𝐾 + 𝑙𝑜𝑔𝐶𝑒𝑞
𝑛
Graduate Chemistry Lab- CHEM503
K and n are characteristics constants for a given adsorbate and adsorbent at a particular temperature.
Thus, a plot of logCads vs logCeq will be a straight line with slope = 1/n and y-intercept = logK
Activated carbon is a solid and porous form of carbon with an exceptionally high surface area of ~500 –
2000 m2/g (Figure:). It is suitable for a wide range of applications e.g. gas purification, water purification,
food industry, medicine, pharmacy, military, etc. Some examples are:
• In pharmacy the activated charcoal is considered to be the most effective single agent available
as an emergency decontaminant in the gastrointestinal tract. It is used after a person swallows or
absorbs a toxic drug or chemical.
• Activated carbon is used as an adsorbent for the adsorption of mainly organic compounds along
with some larger molecular weight inorganic compounds such as iodine and mercury.
• Gas masks contain activated carbon which preferentially adsorbs the poisonous gases.
• Sugar is decolorized by treating sugar solution with charcoal powder which adsorbs the
undesirable colors.
Experimental Procedure:
1. Prepare aqueous solutions of acetic acid into numbered volumetric flasks following the scheme given
in the Error! Reference source not found.. The total volume of each solution is 60 mL. Use flasks fitted
with stoppers.
2. Use carefully washed and dried flasks, beakers, pipettes, etc.
3. Standardize NaOH by 0.1M KHP solution using phenolphthalein as an indicator.
4. Determine the initial concentration of acetic acid in each flask before adsorption (Mbefore) by titration
in this way:
a. Take away defined volume (i.e. 10 mL) of the solution
b. Add 2-3 drops of phenolphthalein and titrate by NaOH (0.1 M).
c. Once the endpoint has been reached, read the burette. It gives the volume of the base (mL)
that was required to reach the endpoint.
𝑉𝑜𝑙. 𝑜𝑓 𝑏𝑎𝑠𝑒 (𝑚𝑙) 𝑀 𝑜𝑓 𝑏𝑎𝑠𝑒
d. Calculate concentration of acetic acid after adsorption (Mbefore) = 10 (ml)
for
each flask.
5. Using practical balance and glazed paper, weigh 7 portions of activated charcoal, each portion 1.5 g.
The accuracy of weighing must be 0.01g.
6. Put activated charcoal (1.5 g) into numbered flasks with stoppers containing 25 mL of acetic acid
solution (1 portion per flask). Plug up the flasks, and shake them. Wait for 90 minutes (1.5 hrs); the
process of adsorption is in progress. Mix the mixtures for several times by shaking the flasks within
this period. (Remark: It is important to put charcoal into flasks at the same time, to provide adsorption
for the same period in each flask).
7. Filter the mixtures into clean and dry flasks. To minimize the experimental error, due to adsorption
of acetic acid into filtering paper, remove away the first portion of filtrate (~ 5 mL).
8. Determine the equilibrium concentration of acetic acid (Mafter) (mol/L) using equation give above.
9. Determine the equilibrium concentration of acetic acid Ceq (mg/L) using equation give above.
10. Determine the amount of acetic acid adsorbed per gram of charcoal ‘Cads’ in the individual flask as per
equation given above.
Graduate Chemistry Lab- CHEM503
11. Determine the maximum adsorbed concentration of acetic acid Cmax and distribution coefficient kd
using Langmuir and Freundlich isotherms,
Write down the obtained values in the table. On the basis of these values fit the experimental points
with linear functions and calculate the slopes and intercepts of respective adsorption isotherms.
Table 2: Determination of equilibrium concentration (Mafter) of acetic acid in different flask after
adsorption
Flask No 𝑉𝑜𝑙 𝑜𝑓 𝑁𝑎𝑂𝐻 𝑀𝑜𝑙𝑎𝑟𝑖𝑡𝑦 𝑜𝑓 Vol. of acetic acid Molarity of acetic
𝑢𝑠𝑒𝑑 (mL) NaOH used (mol/L) taken (mL) acid (mol/L)
Table 3: Calculations to determine concentration of acetic acids before and after adsorption in mg/L
and amount of acetic acid adsorbed in mg per g of adsorbent.
Flask No 1 2 3 4 5 6 7
Amount of charcoal used (g) 1.5 1.5 1.5 1.5 1.5 1.5 1.5
Acetic acid (M) Prepared 0.16 0.12 0.08 0.06 0.04 0.02 water
Total volume of acid used (mL) 60 60 60 60 60 60 60
Graduate Chemistry Lab- CHEM503
Initial (Ci) concentration of acetic acid before adsorption in mg/L = Molarity of acid (Mi) 60 1000
Equilibrium (Ceq) conc of acetic acid after adsorption in mg/L = Molarity of acid (Meq) 60 1000
𝐦𝐠
(𝑪𝒊−𝑪𝒆𝒒) ( ) 𝟎.𝟎𝟔 (𝐋)
𝐋
Amount of acetic acid adsorbed (Cads) per g of adsorbent in mg/g =
1.5 g of charcoal used
Table 4: All the parameters required to plot the isotherms.
Isotherm Langmuir Freundlich
Flask No Ceq/Cads (g/L) Ceq (mg/L) log Cads (mg/g) log Ceq (mg/L)