B.

Determination of the Adsorption Isotherm

As stated from the procedure in Chapter IIIB, the density of the samples was obtained by
dividing the mass of the sample taken from the prepared solutions in Chapter IVA to its volume.
Once the density at a certain time is approximately equal to its subsequent density after 2 minutes,
the determination of density stops. The following results are shown in the tables below.

Table 1: Density at 0.2 % w/w dye solution

Time, min Mass of Sample (±0.0001 g) Volume of Sample (±0.5 mL) Density, g/mL
2 23.8011 24.5 0.97147
4 24.1042 25.0 0.96417
6 22.9829 24.0 0.95762
8 23.4442 24.5 0.95691
10 22.9516 24.0 0.95632

Table 2: Density at 0.4 % w/w dye solution

Time, min Mass of Sample (±0.0001 g) Volume of Sample (±0.5 mL) Density, g/mL
2 23.7699 24.5 0.97020
4 23.5209 24.5 0.96004
6 23.4521 24.5 0.95723
8 22.9204 24.0 0.95502
10 22.9314 24.0 0.95548

Table 3: Density at 0.6 % w/w dye solution

Time, min Mass of Sample (±0.0001 g) Volume of Sample (±0.5 mL) Density, g/mL
2 24.6025 25.1 0.92565
4 24.0780 24.9 0.91257
6 24.0808 25.0 0.90897
8 24.0840 25.0 0.90909

Table 4: Density at 0.8 % w/w dye solution

Time, min Mass of Sample (±0.0001 g) Volume of Sample (±0.5 mL) Density, g/mL
2 24.0017 24.8 0.96781
4 22.6296 23.9 0.94685
6 22.6042 24.0 0.94184
8 22.7964 24.2 0.94200

Table 5: Density at 1.0 % w/w dye solution

Time, min Mass of Sample (±0.0001 g) Volume of Sample (±0.5 mL) Density, g/mL
2 23.8011 24.5 0.97147
 4 24.1042 25.0 0.96417
6 22.9829 24.0 0.95762
8 23.4442 24.5 0.95691
10 22.9516 24.0 0.95632

To put things simply, the density of the dye solution change with time as adsorption proceeds.
As time passes by, it can be observed that the density in each concentration (0.2%, 0.4%, 0.6%,
0.8% and 1.0 %) is decreasing. The reason for this is that the dye that was dissolved in the water
is slowly being adsorbed in the activated carbon, causing its mass to gradually decrease. However,
certain factors can also be considered like the adsorption capacity of the filter paper used in the
separation of the sample from the solution and small losses of activated carbon granules during
this process. It was due to this that the densities obtained are assumed to be inaccurate.

Another observation is that at the initial times from 2 to 4 minutes, sudden changes in densities
at two significant figures are shown, while the next passing minutes has small changes, having
difference only at 3 significant figures. According to Geankoplis (1993), when the fluid is passed
through the bed, the solid particles adsorb components from the fluid. When the bed is almost
saturated, the concentration would remain almost constant and the flow in the bed is stopped. This
is of somewhat similar case with that of obtained densities in the experiment. At time 2 to 4
minutes, the activated carbon just continuously adsorbs dye solute in the solution, however at the
subsequent minutes; the adsorber slowly becomes saturated causing a decreasing change in the
densities. Once it is fully saturated, the density remains almost constant from its previous density,
hence stopping the whole process. In the 0.2%, 0.4% and 1.0% w/w dye solutions, the density
became constant at 10 minutes, while it was 8 minutes for both 0.6% and 0.8% w/w dye solutions.

A more in-depth explanation is expounded in the study of Chattopadhyaya & al (2017),

according to him the removal of dye is rapid in initial stages but when it approaches equilibrium,
it slows down gradually. This is due to the availability of vacant surface sites during the
preliminary stage of adsorption, and after a certain period of time the vacant sites are occupied by
dye molecules, which lead to create a repulsive force between the adsorbate on the adsorbent
surface and in bulk phase. In the experiment, the attainment of equilibrium takes place after
agitating the solutions containing the adsorbent up to 8-10 minutes and once equilibrium was
attained, the percentage of adsorption of dye did not show any appreciable change with time. This
suggests that after equilibrium is attained, further treatment does not provide more removal.

However, since the hydrometer is not used in determining the densities, certain errors can be
derived in its calculation, proving them inaccurate. To compensate for this, the propagation of
errors, as shown in Appendix ???, were calculated, acquiring the density error and its minimum
and maximum corrected value. With the help of this data, the final density is determined from the
corrected range of errors.

Table 6: Summary of the final densities at different concentration (w/w %) dye solution
Time (min) 0.20% 0.40% 0.60% 0.80% 1.00%
2 0.939400 0.940608000 0.943647209 0.946550684 0.944609
4 0.932412 0.930556738 0.930528274 0.925469882 0.937569
6 0.925475 0.927779522 0.926874691 0.928186241 0.930695
8 0.925007 0.925372729 0.927000976 0.928384297 0.930187
10 0.924187 0.925825906 ------- ------- 0.929404

Note that the final density is merely an approximate. This density is used to determine the final
concentration of the dye solution after the adsorption process using the equation correlating the
density and concentration in Chapter IVA. Ideally, in an adsorption process, the concentration
obtained must be less than the initial concentrations (0.2%, 0.4%, 0.6%, 0.8% and 1.0 %) of the
solution. Unfortunately, due to some experimental factors like not using same methods in
determining the densities, results show increasing trends, which can be considered a failure in the
experiment. Nevertheless, by approximately calculating the final density through the corrected
range of errors using Excel®, the final density that is less than its initial value can be obtained,
creating a decreasing trend in concentration. Another basis of this is also the percentage removal
of the adsorber. In the study of Chattopadhyaya & al (2017), it was stated that when the initial
concentration of dye solution increases, the percentage removal of the adsorption process
decreases. The same goes in the study of Sharma and Uma (2009), stating that for low
concentration ranges, the percentage removal of the dye is higher. That said, assuming that the
optimum percentage removal to be greater than 95%, the initial assumption from 0.2% is greater
than 95% followed by a decreasing trend up to 1.0%. Overall, by using this method, the final
concentrations obtained has approximately ±0.0017 error.
 Afterwards, the mass of dye per volume of solution, c, and the mass of dye adsorbed per mass
of activated carbon, w, were calculated. A plot of c versus w was done to determine whether it is
a Freundlich Isotherm. Alternatively, a plot of 1/c versus 1/w was also done for Langmuir Isotherm.
This was done on time 2, 4, 6, and 8 minutes. Since both 0.6% and 0.8%, w/w dye solutions became
constant at 8 minutes, the data from time t = 10 minutes are not considered.

Table 7: R2 values of the Freundlich and Langmuir Isotherm Plots at different time t
Time (minutes) Freundlich Isotherm Langmuir Isotherm
2 0.7444 0.6829
4 0.0044 0.1054
6 0.7729 0.8558
8 0.9604 0.8541

Optimum results were shown at t = 8 minutes, having high values of R2 for both Freundlich
and Langmuir Isotherm. Others, especially at t = 4 minutes, have points that are too far away from
each other to form a line, thus, only t = 8 minutes will be further discussed in this experiment.

Table 8: Freundlich Isotherm Raw Data at t = 8 minutes

Concentration of Dye c w
Solution, w/w % ( g dye/mL solution ) ( g dye adsorbed/g AC )
1 0.000532887 0.010134648
0.8 0.000389761 0.008164909
0.6 0.000280309 0.006146290
0.4 0.000151895 0.004145200
0.2 0.000123100 0.002018277
 Figure 1: Plot of Freundlich Isotherm at t = 8 minutes

Table 9: Langmuir Isotherm Raw Data at t = 8 minutes

Concentration of Dye Solution, 1/c 1/w
w/w % ( mL solution/g dye ) ( g AC / g dye adsorbed )
1 1876.571 98.67140835
0.8 2565.677 122.4753418
0.6 3567.489 162.6997654
0.4 6583.494 241.2428659
0.2 8123.466 495.4722064
 Figure 2: Plot of Langmuir Isotherm at t = 8 minutes

Comparing both plots, the isotherm with the highest R2 is the Freundlich Isotherm, having a
value equal to 0.9604, while Langmuir Isotherm has only 0.8541, thus, the Freundlich Isotherm
fitted better since it is more accurate. Taking this into consideration, the adsorption isotherm
involved in the process is hence the Freundlich Isotherm. This is considered reasonable since
Geankoplis (1993) stated that this isotherm is particularly useful for liquids. By further calculations
and simplifications, the Freundlich Isotherm equation is determined to be w  18.1472175c 0.9834117406
.

References
Chattopadhyaya, M., & al, e. (2017, May). Adsorption characteristics for the removal of a toxic
dye, tartrazine from aqueous solutions by a low cost agricultural by-product. Arabian Journal of
Chemistry, X.

Sharma, Y., & Uma. (2009). Optimization of parameters for adsorption of Methylene Blue on
low cost activated carbon. Journal of Chemical & Engineering Data, 55(1), 435-439.