Theory outline

This experiment was performed as an investigative measure for the adsorption of a carboxylic acid
from solution of different concentrations to fit the theory of Langmuir and determine the specific
surface for charcoal. The hypothesis was that the Langmuir theory is more accurate than the
Freundlich theory. It was based on the principle that when an acid (Acetic acid in this case) is
exposed to charcoal the are some molecules of charcoal that will be adsorbed to charcoal. These
moles will not be available to participate in other chemical reactions like titration of acetic acid.
Hence the number of moles of acetic present in the reaction will be less than those that participate
in titration. The difference between these are the moles adsorbed. The moles adsorbed are expected
to increase with the concentration of acetic acid.

Theory outline

Graphical and tabulated results

Sample C initial(M) C Initial No. Final No. of No. of a(mol/gram of C/a( Ln a Ln C
final(M) of moles moles moles charcoal)
adsorbed
0.05 0.0524 0.0430 0.001048 0.000860 0.000188 0.00137 31.39 -7.663 -3.147
0.10 0.1088 0.0750 0.002176 0.001500 0.000676 0.00169 44.38 -6.383 -2.590
0.15 0.1635 0.1170 0.003272 0.002340 0.000932 0.00233 50.21 -6.062 -2.146
0.20 0.2185 0.1700 0.004372 0.003400 0.000972 0.00243 69.96 -6.020 -1.772
0.25 0.2643 0.2063 0.005288 0.004128 0.001160 0.00290 71.14 -5.843 -1.578
Control 0.0524 0.0524 0.000262 0.000262 0.00 0.00 0.00 - -2.94

Sample Equations:

Mean Volume delivered = V(Run1 + Run 2)/2

Mean Volume delivered = (5.22ml + 5.26ml)/2

Mean Volume delivered = 5.24ml

n(NaOH)titr= C X V

n(NaOH)titr= 0.05mol/L x (10.88/1000)L

n(NaOH)titr = 0.000544mol

CH3COOH + NaOH → CH3COONa H2O

n(NaOH)titr = n(CH3COOH)reacted

n(CH3COOH)reacted = 0.000544mol

[CH3COOH] = n/V

[CH3COOH] = 0.000544mol/(5X10-3L)

[CH3COOH] = 0.1088M (in 5ml)

5ml : 0.000544mol

20ml : X

X = 0.000544mol (20ml/5ml)

X = 0.000544mol (4)

X = 0.002176mol

No. of moles adsorbed = Initial No. of moles – Final No. of moles

No. of moles adsorbed = 0.002176mol - 0.001500mol

No. of moles adsorbed = 0.000676mol

a = No. of moles adsorbed / gram of charcoal

a = 0.000676mol / 0.4g

a = 0.00169mol/g

C/a = (0.0750mol/L)/(0.00169mol/g)

C/a = 44.38g/L

Figure 1: The figure above displays the relationship of the number of moles of acid adsorbed per gram of charcoal(a) and
equilibrium concentration(C). The figure shows that an increase in the equilibrium concentration results in an increase in a.
Figure 2: The figure above shows the relationship between Ln a and Ln C. As Ln C increases, Ln a also increases. The
increase or decrease of Ln a is dependent in that of Ln C.

From: Ln a = Ln K + 1/n(Ln C)

Ln K = intercept

Ln K = -3.998

K = e-3.998

K = 0.01835

K = 1.835x10-2

1/n = gradient

1/n = 1.066

n = 1/1.066

n = 0.9381mol
Figure 3: This figure shows the relationship between C/a and C, where the C/a equilibrium concentration (C) is dependent
on equilibrium concentration (C). As C increases, the C/a also increases.

From: C/a = 1/amK + 1/am(C)

1/am = gradient

1/am = 249.9

am = 1/249.9 mol

am = 0.04002 mol

am = 4.002x10-3 mol

1/amK = 22.87

K = 1/22.87am

K = 1/22.87(4.002x10-3)

K = 1.093

A = amNA1

A = (4.002x10-3 mol) x (6.023x10-23mol-1) x (21Å2)

A = 5.062x10-24 Å2/0.4g

A = 1.2655x10-17Å2/g x 1x1020(m2/g)/(Å2/g)

A = 1265.5m2/g

The literature value of specific surface area is 950-2000m2/g (JK Aronson,2016)

Discussion

The 1st filtrate may contain some contamination which will affect the outcome or results. This will decrease the reliability of
the obtained results. So, discarding the solution means the filter can be in contact with the solution before any of it is used
for the experiment so that any contaminant substances are discarded with the first filtrate.

The Langmuir’s theory in general is a better approach for adsorption of charcoal as compared to Freundlich. This is because
the Freundlich theory cannot correctly predict the behavior of the number of moles per gram of solute. Since these moles
become independent of the concentration when it becomes high. The shortcoming of the Langmuir theory is predictions
for gases as many layers are formed at higher pressures hence the results reliability is compromised and cannot be ensured.
However, the experiment performed included liquids and solids not gases. This therefore increases the reliability of the
Langmuir theory. The experiment was performed in a range of concentrations which implies that the theory of Freundlich’s
reliability is questionable and compromised.

According to the data obtained the Langmuir approach was the better approach for the adsorption of charcoal as it
showed that the specific surface area determined from this experiment (1265.5m2/g) is within the range of the literature
value (950-2000m2/g). This shows that the Langmuir theory was able to detect reliably the adsorption of charcoal. The
Freundlich approach was however not as reliable as the values were further apart even at low concentration and far from
the line of best fit.

The shaker was not working at the beginning of the reaction hence some time had to be taken to fix it before the shaking
process. The shaking process was done for lower than the stipulated time which means that the reaction could have not
reached completion. The flasks were put in the flask for only 20 minutes instead of the stipulated 40 minutes. Another
source of error could have been due to the apparatus used (burettes and pipettes) with the 0.01 error rates and how the
expand and contract with different temperatures.

am was determined to be 4.002x10-3 mol ± 1.65x10-7, K was found to be 1.093 ± 1.311x10-5. The specific surface area was
found to be 1265.5m2/g ± 4.29x10-5.

ρ = m(g)/Vcm3

1/ρ = V(cm3)/m(g)

1/1.0491 = V(m2)/m(g) x10-3

0.9532 = A x 10-3

A = (0.953)/10-3

A = (1/1.0491)/10-3

A = 953.2 m2/g

This calculation shows a value of specific surface area at 25oC that is lower than the one determined in this experiment.

Conclusion

The hypothesis was that the Langmuir’s theory would be a better approach for adsorption of charcoal measurement. The
experiment was a success as the results agreed with the hypothesis. The specific surface area deduced was 1265.6m2/g
within the literature range of 950-2000m2/g. The experiment also showed that an increase in the concentration of acetic
acid led to an increase in the moles adsorbed. The experiment can be improved by shaking the flasks for the stipulated
time. They could also be allowed to stand in a water bath for the time indicated in the manual. The titrations could be done
in triplicate to improve reliability of results and the titrations could be done by 1 person for precision.

References

 J.K. Aronson, Activated charcoal, Meyler's Side Effects of Drugs (Sixteenth Edition), Elsevier, Page 65, 2016
 P. Atkins and J. de Paula. Atkins’ Physical chemistry, 8th edition.
 Santhanalakshmi, J., S. Balaji, and Thirumalaiswamy Raja. "Adsorption studies of acetic acid dimers on activated
charcoal from organic solvents." In Proceedings of the Indian Academy of Sciences-Chemical Sciences, vol. 106,
pp. 893-902. Springer India, 1994.
 Dunicz BL. Surface area of activated charcoal by Langmuir adsorption isotherm. Journal of Chemical Education.
1961 Jul;38(7):357.