Determination of ion exchange capacity for anion-selective membranes – Lab.

Report

Authors : Andreas & Mehrafarin Hosseinpanah

Date of the exercise : 19th of April 2024

1. Introduction
Anion Exchange Membrane (AEM) is a membrane whose chemical structure is composed
of positive ionic groups such as ammonium, phosphonium, sulfone ions, which can associate
with anions, for example, OH-. (Feng, et al., 2023). Generally, there are two (2) types of ion-
exchange membranes, which are homogeneous and heterogeneous. Each type of membrane
has its own advantages and disadvantages. Heterogeneous membranes have very good
mechanical strength but their electrochemical performances are not so good. On the other hand,
homogeneous membranes have worse mechanical strength but better electrochemical
performance (Vyas, et al., 2001). Heterogeneous membranes have better mechanical strength
because they are made of a polymer matrix as a support material and embedded with several
functional groups, while homogeneous membranes are made of one polymeric matrix that
already contains functional groups within it. Each type of membrane has different uses.
Heterogeneous anion-exchange membranes are widely used in the water treatment industry
(for desalination and purification) and the chlor-alkali industry (for the production of chlorine
and sodium hydroxide), while homogeneous membranes are commonly used in fuel cells and
electrolysis (for hydrogen production).

2. Methodology
This experiment consists of 3 steps which are the pre-treatment of the membranes, solution
preparation, and characterization of the membranes.
• Pre-treatment of membranes
The prepared membranes which have an area of 1 cm2 immersed in 100 ml of 1 mol/l
KNO3 solution.
• Solution preparation
- 2 liters of 0.1 mol/l NaCl solution is prepared
- 100 ml of 0.1 mol/l NaCl solution pipetted into 9 beakers with the exact amount
- All of the membranes are rinsed with deionized water and placed into the beakers
- 100 ml of 1 g NO3-/l is prepared for the calibration curve measurement
 - Dilution of KNO3 solution to 100 ml solution with several concentrations (0.0; 2.5;
5.0; 7.5; 10; 12.5; 15.0 mg NO3-/l) using NaCl solution for calibration curve
measurement
• Membrane characterization
- Measurement of the absorbances of KNO3- solutions with different concentrations for
the calibration curve using Cary 50 UV-Vis spectrophotometer at wavelength 220 nm
- Measurement of the absorbances of samples (membranes)
- Measurement of the dimensions of the membranes in the wet and dry state by drying
all of the membranes using the moisture analyzer

3. Results and discussion

1,6

1,4

1,2
Mean Absorbance

0,8

0,6 y = 0,0536x + 0,3702

R² = 0,9976
0,4

0,2

0
0 2 4 6 8 10 12 14 16 18 20
Concentration (mg/l)

Figure 1. Calibration curve

Based on the measurements IEC curves can be plotted using the formula below.

𝑚𝑁𝑂3−
𝐼𝐸𝐶 = ( )/𝑚𝑑𝑟𝑦 𝑚𝑒𝑚𝑏𝑟𝑎𝑛𝑒
𝑀𝑁𝑂3−

Where 𝑀𝑁𝑂3− is 62 g/mol and 𝑚𝑁𝑂3− is the mass concentration obtained from the experiment.
Results are shown in the table below (also available in the Ms. Excel file attached).
 Table 1. Ion Exchange Capacity (IEC) calculations
Concentration
Membrane W(dry) - g (mg/L) mNO3- IEC(mmol/g)
Dabco 1 0.0213 10.5 1.05 0.795
Dabco 2 0.0199 10 1 0.810
Dabco 3 0.0221 10.7 1.07 0.7811
W56 - 1 0.0283 31.2 3.12 1.778
W56 - 2 0.0301 26.1 2.61 1.399
W56 - 3 0.0307 33.1 3.31 1.739
W63 -1 0.0411 17.2 1.72 0.675
W63 -2 0.0397 7.8 0.78 0.3177
W63 -3 0.0401 33.8 3.38 1.360

IEC results are plotted in the figure below. As shown in Figure 2, Dabco membranes show
consistent IECs in all samples. However, IEC values for W63 membranes vary significantly.
Knowing that the samples were cut from a bigger membrane, it is possible to guess that the
main membrane was not homogenous in different spots which resulted in samples with
different IECs. It is also evident that W56 shows a much higher IEC compared to Dabco and
W63. Therefore, it has a greater capability for ion exchange. Dabco and W63 show close
average IEC values (0.80 and 0.78).

W63 -3

W63 -2

W63 -1

W56 - 3

W56 - 2

W56 - 1

Dabco 3

Dabco 2

Dabco 1

0,00 0,50 1,00 1,50 2,00

IEC

Figure 2. IEC comparison

Using membranes’ dry and wet weights and dimensions and IEC values, swelling and the
amount of water absorbed per functional group can be calculated. Swelling is calculated as the
percentage increase in membrane area and water absorbed per functional group is calculated
by dividing the total amount of water absorbed by IEC. In this case, the total amount of water
absorbed is easily calculated by calculating the difference between membrane dry and wet
weight.

Table 2. Swelling calculations

Membrane A, wet- (cm2) A, dry – (cm2) Swelling (%)
Dabco 1 1.07 0.95 12.6
Dabco 2 1.02 0.91 11.5
Dabco 3 1.17 1.02 14.5
W56 - 1 1.19 1.06 11.6
W56 - 2 1.30 1.16 12.1
W56 - 3 1.39 1.20 16.2
W63 -1 1.49 1.05 41.2
W63 -2 1.45 0.99 46.5
W63 -3 1.50 1.03 45.5

Table 3. Water absorption calculations

Water per
Water
Membrane W, wet(g) W, dry(g) functional
absorbed (ml)
IEC group
Dabco 1 0.0282 0.0213 0.80 0.069 0.087
Dabco 2 0.0264 0.0199 0.81 0.065 0.080
Dabco 3 0.0295 0.0221 0.78 0.074 0.095
W56 - 1 0.0408 0.0283 1.78 0.125 0.070
W56 - 2 0.0402 0.0301 1.40 0.101 0.072
W56 - 3 0.0576 0.0307 1.74 0.269 0.155
W63 -1 0.0739 0.0411 0.67 0.328 0.486
W63 -2 0.0746 0.0397 0.32 0.349 1.101
W63 -3 0.076 0.0401 1.36 0.359 0.264
 In contrast to IEC values, results for swelling are consistent. Therefore, looking at the
average values can also give a relatively accurate picture. The figure below shows the average
swelling and water absorbed per functional group for each group of membranes.

0 0,1 0,2 0,3 0,4 0,5 0,6 0,7

W63 (Water)

W63 (Swelling)

W56 (Water)

W56 (Swelling)

Dabco (Water)

Dabco (Swelling)
0 5 10 15 20 25 30 35 40 45 50

Swelling Water absorbed per functional group

Figure 3. Average swelling and water absorbed per functional group for each group of
membranes

As expected, these two parameters are highly correlated since as water absorbed per
functional group increases, swelling increases as well. In this case, Dabco and W56 show close
results; however, W63 absorbed a much higher amount of water per its functional group
compared to them and had a higher swelling percentage.

4. Conclusion
In this experiment, 9 membranes with different functional groups and structures were
analyzed to compare their characteristics. Membrane W56 showed the highest number of
functional groups per gram. For each membrane, swelling and water absorbed were calculated.
in this case, these two values were highly correlated and W63 showed the highest average
swelling and water absorbed per functional group. However, it showed some fluctuations in
both the amount of water absorbed per functional group and IEC values while these values for
the other two membranes were almost constant. Therefore, it is unlikely that these fluctuations
are due to some experimental or calculation mistake and they might be related to the fact that
the original W63 membrane was not completely homogenous or the samples were cut from
different original membranes which could result in differences in IEC values.
References

Feng, Z., Gupta, G. & Mamlouk, M., 2023. A review of anion exchange membranes prepared
via Friedel-Crafts reaction for fuel cell and water electrolysis. Journal of Hydrogen Energy,
pp. 25830-25858.

Vyas, P. V. et al., 2001. Characterization of heterogeneous anion-exchange membrane.

Journal of Membrane Science, pp. 39-46.