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Introduction:

The process that occurs when gaseous or liquid solutes accumulate onto surfaces of other solids
and liquids forming a molecular or atomic film is known as adsorption.

Physisorption/Physical Adsorption occurs when the adsorbate adheres to surfaces only through
van der Waals interactions with a binding energy of approximately 20kJmol-1.

Chemisorption/Chemical adsorption occurs when a molecule adheres to a surface through the


formation of a chemical bond with a binding energy of approximately 200kJmol-1.

This solution adsorption isotherm also known as the Langmuir Adsorption Isotherm was
mathematically formulated for liquid adsorption onto a solid surface:

C/N=N/Nm + 1/KNm (1)

C-solution concentration; Nm- number of moles required to form monolayer; K-rate constant ;

N-number of moles adsorbed per gram of adsorbate.

Procedure:

The experiment was done as in the lab manual.


Results:

Table 1: Molarities, volumes and masses of Acetic acid , Water and Charcoal used
for Groups 1, 2 and 3

Group 1 Group 2 Group 3


Experiment 1 2 3 1 2 3 1 2 3

Molarity(M) 0.08 0.06 0.02 0.10 0.04 0.01 0.07 0.03 0.005

Aliquots 5 10 25 5 10 25 5 10 25
(mL)

Volume of 40 30 10 50 20 5 35 15 2.5
Acid(mL)

Volume of 10 20 40 - 30 45 15 35 47.5
Water(mL)

Total 50 50 50 50 50 50 50 50 50
Volume(mL)

Mass of 1.0046 1.0045 1.0046 1.0005 1.0006 1.0004 0.9405 1.0109 1.0152
charcoal(g)
Table 2: Titration of Acetic acid filtrate with (NaOH) for Groups 1, 2 and 3

Group 1 Group 2 Group 3


Experiment 1 2 3 1 2 3 1 2 3

Avg. Titre Value(mL) 15.85 12.45 8.2 19.15 12.9 6.9 13.7 10.2 3.0

Initial number of moles 4.0 3.0 1.0 5.0 2.0 0.5 3.5 1.5 0.25
(mol) ×10-3
Final number of moles 3.17 2.49 1.64 3.83 2.58 1.38 2.74 2.04 0.6
(mol) ×10-4
Number of moles HAc 3.68 2.75 0.84 4.61 1.74 0.36 3.22 1.30 0.19
adsorbed by charcoal (mol)
×10-3
Number of moles adsorbed 3.67 2.74 0.83 4.62 1.74 0.36 3.43 1.28 0.19
per gram of adsorbate, N.
(molg-1) ×10-3
Final concentration of HAc, 6.34 2.49 0.66 7.66 2.58 0.55 5.48 2.04 0.24
C (mol) ×10-2

C/N 17.29 9.09 7.88 16.60 14.82 15.25 15.98 15.91 12.82
Calculations:

Sample calculation for:

Volume of Acid used =C1V1×C2V2


V1= (C2V2) ÷ C1
= (0.08×50) ÷0.1
= 40mL

Initial number of moles = (Concentration × Volume used) ÷ 1000mL


= (0.08M Acetic acid × 50mL H2O) ÷ 1000
= 4.0×10-3 moles

Final number of moles = (Concentration of NaOH ×Titre Volume used) ÷ 1000mL


= (0.02M NaOH × 15.85mL) ÷ 1000
= 3.17×10-4 moles

Number of moles HAc = Initial number moles – Final number moles


adsorbed by charcoal = 4.0×10-3 – 3.17×10-4
= 3.68×10-3 moles

Number of moles = Number of moles of HAc adsorbed by charcoal ÷ Mass of charcoal


adsorbed per gram of = 3.683×10-3 mol ÷ 1.0046g
adsorbate, N. = 3.67×10-3 molg-1

Final concentration of = (Number of moles of Hac ÷ Volume of Aliquots used) × 1000mL


HAc, C Reaction equation: HAc + NaOH → NaAc + H2O
Molar Ratio 1:1
Number of moles NaOH used = Number of moles HAc present
= (3.17×10-4 moles ÷5mL) × 1000mL
= 6.34×10-2 moles

C/N = Final concentration of HAc ÷ Number of moles adsorbed per gram of adsorbate
= 6.34×10-2 moles ÷ 3.666 ×10-3 molg-1
=17.29

Graph:
Calculations from the Graph:

Gradient = 72.248
72.248 =1/Nm
Nm= 1.38 ×10-2

Intercept= 11.711
11.711 = 1/KNm
K= 6.188 Lmol-1

Density of Acetic Acid = 1.049gcm-3

Molecular weight of = 60.05gmol-1


Acetic Acid, Mw

Excluded volume =Mw/(DNA)


=60.05gcm-3/(1.049gcm-3 × 6.022 x1023mol-1)
= 9.506 ×10-23cm3

Volume Excluded by = 4√2.R3


spheres R3=9.506 ×10-23/4√2
=1.680 ×10-23cm
R= 2.5 ×10 -8cm

Area Excluded by a = 2√3. R2


monolayer (σ) = 2√3.(2.5 ×10-8)2
= 2.165 ×10-15cm2

Surface area per gram (A) = NmNAσ


= 1.38 ×10-2 × 6.022 ×1023mol-1× 2.165 ×10-15cm2
= 1.799 ×107cm2g-1
Questions

(Question within text)


Stoppering the flask that contained the acetic acid and charcoal with parafilm was done to
prevent the evaporation of the acetic acid molecules into the gas phase as the acetic acid is very
volatile. Had the flask not been stoppered as the molecules escaped into the gas phase, and
entering the atmosphere displacing equilibrium so permitting further vaporization. Nevertheless
since the flask was stoppered, the molecules that enter the gas phase remain within the system
and this kept the system at equilibrium keeping more molecules in the liquid phase.

1. Discarding the first 10ml of the filtrate helps to keep the filter flask clean of any
contaminants and to saturate with acid any adsorption sites which may be on the filter
paper.

2. A. The surface of the adsorbent is uniform, that is, all the adsorption sites are equal.
B. Adsorbed molecules do not interact
C. All adsorption occurs through the same mechanism
D. At the maximum adsortion ,only a monolayer is formed: molecules of adsorbate do
not deposit on other, already adsorbed molecules of adsorbate, only on the free surface of
the adsorbent. For a given adsorbed phase and adsorbent at a constant temperature the
Freundlich isotherm is used. A graph of log10 Y(moles adsorbate per gram adsorbent)
plotted against log10 c(concentration) will result in a straight line with a slope equal to 1/n
and the intercept equal to log10 k.
Discussion and Conclusion:

The Langmuir Adsorption Isotherm is an empirical isotherm derived from a proposed kinetic
mechanism. It is based on the amount of a liquid adsorbed onto a solid surface (for this
experiment). Adsorption by a solid only becomes of interest if the surface area is very large
compared to its mass. For charcoal 1g of activated carbon equals 500m2 surface area. Charcoal is
thus very suitable because of its highly porous structure. The activated charcoal is produced from
the desorption of the hydrocarbons that are adsorbed when the charcoal is firstly produced.
In the experiment it was seen that as the molarity of the acetic acid used decreased so did the
volume of sodium hydroxide required to neutralize the solution. The use of simple stoicrometry
showed that the molar ratio between acetic acid and sodium hydroxide was 1:1, which allowed
the final concentration value to be determined. From plotted values the rate constant, K, for
adsorption of charcoal was found to be 6.18 Lmol-1. Solid surfaces can adsorb dissolved
substances from solution. When a solution of acetic acid in water is shaken with activated
carbon, part of the acid is removed by the carbon and the concentration of the solution decreased.
From the results gathered, it is realized that K increased as the concentration of acetic acid
decreased. Hence, the degree to which a solid will adsorb material depends on a number of
things including temperature, nature of molecule being adsorbed, degree of surface pore
structure, and, solute concentration & solvent. Bearing these factors in mind, one must also note
the possible errors that could have hinder the results, they include sample contamination, i.e
solutions may contain impurities; use of dirty apparatus, thus affecting volume measurements;
reading of burette should be to 2 decimal places approximation for higher accuracy; not taking
readings at eye level to avoid parallax errors and incorrect volume measurements made by the
experimenter.
To conclude adsorption from solution follows the principles laid down for the adsorption
of gases. Dissimilarity of extend of adsorption with concentration of solute is usually
represented by the Freundlich isotherm and the Langmuir isotherm. A boundary that
separates two phases is known as a surface or an interface. Surfaces show special
properties that are different from those of the phases themselves. This is an example of
physical adsorption, where dipole and van der Waals forces are the predominant sources
of attraction. For example, the surface of a solid often shows a strong affinity for molecules that
come into contact with it and which are said to be adsorbed. The amount of acetic acid
(adsorbate) adsorbed per gram of charcoal (adsorbent) will depend on the surface area
of the charcoal, the temperature of the solution and the absorbate concentration in
solution. The adsorption is followed by titrating the acetic acid not absorbed by the charcoal and
then the amount absorbed by difference is determined.