CHEN310 – Transport Phenomena Lab 1 Ion-Exchange and Water Hardness

Baha and Walid Bassatne Department of Chemical Engineering

CHEN310: Transport Phenomena Lab

Experiment 01: Ion Exchange and Water Hardness

Conducted on: September 20, 2023

Razan Tarabay | Karim Assaf | Nadim Salameh

[email protected] | [email protected] | [email protected]

Group 4 | Section 2
CHEN310 – Transport Phenomena Lab 1 Ion-Exchange and Water Hardness

Abstract
The experiment and process of ion exchange is very important and valuable in solving common
industrial problems such as scale buildup in pipes and exposure to hard water that lead to cost
burdens. Ion exchange is used in industrial processes to cleanse and eliminate ionic impurities
from a solution.
Water is said to be hard when it has a high mineral concentration often in the form of calcium or
magnesium. Our experiment's main goal is to soften water that is high in Calcium ions coming
from Calcium Acetate by the process of ion exchange. The fundamental goal of the experiment is
to understand the mechanism of such a process, as well as to determine the capacity for exchange
of a cationic resin and the hardness of water. The process is mainly summarized as softening
water by ion exchange, regeneration of the resin column after exhaustion, and titration of
samples.
By the logic of ion exchange, the Calcium ions in the hard water interact with the Hydrogen ions
of the cationic resin column. Hard water is first pumped into the cationic resin column at a
flowrate of approximately 7 L/h. The conductivity and pH of samples are then measured at three-
minute intervals. Additionally, titration is performed to determine the concentration of Calcium
ions by using EDTA as a titrant. Water hardness can be determined using this method as well
since it is nothing but the concentration of Calcium and other impurities in water.
The parameters we are interested in are mainly the conductivity, pH level, and water hardness
which are all functions of the treated water volume, thus exhibit similar trends that are shown in
the figures plotted in the results section of the report.
In our case, consider the conductivity which starts out at 3.76 mS/cm and drops to a low of 0.541
mS/cm before plateauing and rising to 0.00372 S/cm. Similar to that, the pH reading is initially
7.52. Before quickly falling to its ultimate value of 6.61, it momentarily rises to a value of 4.72.
When compared to its initial value of 20456.8 parts per million, water hardness has decreased to
a value of 2191.8 parts per million. As the volume of treated water increases, the hardness
eventually increases to 15488.72 ppm. Therefore, the termination of the plateaus for all three
measurements indicates the resin's exhaustion point. In other words, the exchange of calcium and
hydrogen ions has stopped.
The exchange capacity of the resin is found to be 6.514904459 mEq/mL. There were many
potential sources of error in the experiment, but the major contributor was the variance and
inaccuracy of determining the equilibrium point and volume in titration. This report concludes
with recommendations for enhancing the experiment, such as increasing the quantity of samples
and using machines for titration instead of doing it manually.
CHEN310 – Transport Phenomena Lab 1 Ion-Exchange and Water Hardness

Table of Contents

I. Discussion of Results ……………………………………………….. 4-7

i. Determining the Exchange Capacity ……………………………………...… 4
ii. pH vs Treated Water Volume …………………………………………….…. 5
iii. Conductivity vs Treated Water Volume …………………………………..… 6
iv. Water Hardness vs Treated Water Volume ……………………………….… 7

II. Error Analysis …………………………………………………...….. 8-9

i. Sources of Error …………………………………………………..…………. 8
a. Random Errors ………………………………………………………...… 8
b. Systematic Errors ………………………………………………..…….. 8-9
ii. Error Propagation …………………………………………………….……… 9

III. Conclusions ……………………………………………..………… 10-11

IV. References ……………………………………………………...…….. 12

V. Appendices and Sample Calculations ……………………..……. 13-17

i. Appendix A: Raw Data ……………………………………………….… 13-14
ii. Appendix B: Calculations …………………………………………..……… 15
a. Equations Used ………………………………………………………… 15
b. Exchange Capacity – Sample Calculation ……………………...……… 16
c. Treated Water Volume – Sample Calculation ………………….……… 16
d. Water Hardness – Sample Calculation ………………………………… 16
iii. Appendix C: Error Analysis ………………………………………...……… 17
CHEN310 – Transport Phenomena Lab 1 Ion-Exchange and Water Hardness

List of Tables
Table 1: Uncertainty of Water Hardness …………………………………………...……….… 10
Table 2: Raw Data of Conductivity …………………………………………………………… 13
Table 3: Raw Data of pH ……………………………………………………………………… 13
Table 4: Raw Data of Water Hardness ……………………………………………………...… 14
Table 5: Constant Parameters ……………………………………………………………….… 15
Table 6: Calculated Parameters ……………………………………………………………..… 16

List of Figures
Figure 1- Plot of Ph Against the Treated Water Volume ……………………………….……… 5
Figure 2- Plot of Conductivity Against the Treated Water Volume …………………………… 6
Figure 3-Plot of Water Hardness Against the Treated Water Volume ………………………… 7
CHEN310 – Transport Phenomena Lab 1 Ion-Exchange and Water Hardness

I. Discussion of Results
Ion exchange is the chemical process that happens when undesired ions are exchanged for ions
of an equivalent charge by passing them through a resin. [1] Depending on the polarity of the ions
involved, the ionic exchange might be either cationic or anionic. In this experiment, we are
interested in the exchange of positively charged ions to evaluate the exchange capacity of the
cationic resin that we are using to soften the hard, calcium-rich water according to the reaction
provided to us in the lab manual:

M-A+ (solid) + B+ (solution) M-B+ (solid) + A+ (solution) [2]

Following this logic, the resin’s functional group is negatively charged to facilitate the
interaction and exchange of Ca2+ with H+.

For experimental purposes, we recorded the conductivity and pH values of the samples taken
every 3 minutes over 21 minutes. Moreover, we proceeded with titrating the samples with
Ethylenediaminetetraacetic acid (EDTA) to determine the water hardness in ppm, which is also
tabulated below.

From the pattern in the recorded data, we notice that in the last sample taken the values are very
close to the initial conditions, so this is our exhaustion point. The exhaustion point can be seen
in the graphs below and explained in Appendices A and B.

It is important to note that all the calculations and graphs presented in this section are prone to
having errors

i. Determining the Exchange Capacity: To calculate the exchange capacity, we

should use equation 1 which prompts us to also calculate the mass of Ca2+ in
Calcium Acetate and the volume of wet resin. You may find sample calculations in
Appendix B.
From equation 2, we get a volume of 141.3 mL for the given diameter of 20mm and
height of 450mm. To calculate the mass of Ca2+, we use equations 3 and 4 and get a
mass of 920.556 mEq.
Thus, by substituting the values of these parameters into equation 1, we get an
exchange capacity of 6.514904459 mEq/mL.
CHEN310 – Transport Phenomena Lab 1 Ion-Exchange and Water Hardness

ii. pH vs Treated Water Volume: The sample’s pH is a very important parameter to be

measured because pH can alter the charge on the molecules and thus affect binding
since as pH increases, it becomes harder for an ion to leave.[3] In the span of our
experiment, we are interested in measuring the pH to determine acidity and
concentration of H+ ions. As the concentration of H+ ions increase, indicating a
successful exchange of ions, the pH of the sample decreases so it becomes more
acidic. This inverse relationship between concentration and pH is because H+ ions are
acidic, thus lowering the pH towards the acidic side [0-7].
Figure 1 shows the recorded pH of our 8 samples plotted against volume of treated
water.

pH vs Treated Water Volume

8
7.52 6.61
7 Exhaustion point 6.13
6
4.72
5
pH

4 3.01 2.99 3.08

3
2 2.97
1
0
0 0.5 1 1.5 2 2.5

Treated Water Volume (L)

Figure 1: Plot of Ph Against the Treated Water Volume

As observed in the figure, the pH of the initial water sample is 7.52 due to the high
concentration of Ca2+ ions in the initially hard water, making our sample slightly
basic.
As the water is pumped to the column of resin, ion exchange starts and Ca2+ ions are
substituted by H+ ions. At a time of 3 minutes, the sample’s acidity increases, thus its
pH decreases from 7.52 to 3.01. At a volume of 1.05 L, we notice that the pH starts
increasing beyond this point which indicates that we are now at the exhaustion point.
From here, the pH of the samples gradually increases to 6.61 which is close to the
initial value, 7.52, and level of basicity. This increase in pH is because the column
CHEN310 – Transport Phenomena Lab 1 Ion-Exchange and Water Hardness

has already reached its exhaustion point so water passing through the column and
resin won’t undergo an exchange and it will remain with a high concentration of Ca2+.
iii. Conductivity vs Treated Water Volume: Just like the pH values, conductivity was
measured and recorded for our 8 samples. The recorded results are plotted against the
volume of treated water and represented in Figure 2, shown below.

Conductivity vs Treated Water Volume

0.004
0.00379 0.00364
0.0035
Conductivity (S)

0.00372
0.003
0.0025 Exhaustion point
0.002 0.00208
0.0015 0.000647

0.001 0.000568
0.0005 0.00049
0 0.00057
0 0.5 1 1.5 2 2.5

Treated Water Volume (L)

Figure 2: Plot of Conductivity Against the Treated Water Volume

Unlike Figure 1, here we can divide the curve into 3 regions: decreasing conductivity,
relatively stable conductivity, and increasing conductivity.
In the first region, we can correlate the drop in conductivity from 0.00379 S to
0.000647 S to the ion exchange between the Ca2+ ions in water and the H+ ions in the
resin column. Once Ca2+ are replaced by H+, the sample has more H+ which makes
the majority of ions to be of nonmetallic properties, thus reducing water conductivity.
Secondly, the relatively stable conductivity region is when the column is in the
constant range of the exchange capacity where it exchanges Ca2+ and H+ ions
simultaneously with a conductivity ranging between 0.000568 and 0.00049 for
volumes of 0.7 L and 1.4 L respectively.
Beyond the exhaustion point, as shown in the figure, we observe an increase in the
measured conductivity which is justified by the termination of ion exchange due to
the exhaustion of all available H+ ions in the column. Towards the end of the
experiment, we notice that the conductivity of sample 8, 0.00372 S, is relatively close
to the initial conductivity, 0.00379 S.
CHEN310 – Transport Phenomena Lab 1 Ion-Exchange and Water Hardness

iv. Water Hardness vs Treated Water Volume: Water hardness is defined to be the
concentration of Calcium Acetate in a certain volume of water. Water hardness can be
calculated by using Equation 5, and we have plotted the calculated values vs treated
water volume in Figure 3 shown below.

Water Hardness vs Treated Water Volume

25000
Water Hardness (ppm)

20456.8
20000
15488.72
15000 Exhaustion point

7306 13735.28
10000
4383.6
5000 2191.8
6137.04

0 2922.4
0 0.5 1 1.5 2 2.5

Treated Water Volume (L)

Figure 3: Plot of Water Hardness Against the Treated Water Volume

Since we are exchanging Ca2+ by H+ ions, the concentration of Ca2+ ions which
contributes to water hardness decreases. So, following the same logic in Figures 1 and
2, water hardness decreases from 20456.8 ppm to 2191.8 ppm as volume increases
from 0 L to 0.7 L, thus signifying the start of the ion exchange process.
It is important to note that EDTA reacts with Ca2+ and captures it, so as the
concentration of Ca2+ increases, volume of EDTA needed also increases. To reduce
the volume of EDTA needed, we have opted to dilute our sample before titration with
a dilution factor of either 5 or 10, depending on the concentration of the sample as
shown in Table 4.
The lowest value of water hardness recorded should correspond to the exhaustion
point of the experiment, which isn’t the case in this plot due to systematic and random
errors of this experiment. Following the exhaustion point, H+ ions are depleted so the
concentration of Ca2+ increases again, thus raising the water hardness to a value close
to the initial value. Because of experimental errors, the final value of water hardness
is not exact.
CHEN310 – Transport Phenomena Lab 1 Ion-Exchange and Water Hardness

II. Error Analysis

i. Sources of Error: Like all experiments, several sources of error are present here
that affect the accuracy of the results used. These errors can be categorized as
random and systematic errors. Random errors are errors relating to the
parameters measured and human error of measuring, while systematic errors are
related to the design of the experiment and its steps.

a. Random Errors: First, we may have encountered errors while preparing the
EDTA solution from the mass of EDTA added (±1g) and the 20 minutes of
mixing (±1min). Second, while collecting samples at a fixed interval of 3
minutes, we were using a phone timer not synchronized with the start of the
experiment, thus making room for errors. Since titration was done manually,
the random volume of EDTA solution added to observe a change of color had
errors since we may have added excess volume thus contributing to an
uncertainty of ±1 in pH and conductivity. Moreover, we only measured the pH
and conductivity of each sample only once, so we are not sure of the accuracy.
As for the glassware, both the pipette and burette had an error of 0.05 mL
each with a varying meniscus, and the beaker had an error of 0.01 mL.

b. Systematic Errors: Here we encounter systematic errors in the 3 parts of the

experiment: Ion Exchange, Titration, and Regeneration.
1. Ion Exchange: Systematic errors in this stage can be summarized as: the
volumetric flowrate fluctuations since it varied between 6 and 8 L/hr, the
instability of the pump’s power supply, and the fluctuations of
measurements in both the pH and conductivity meters due to either
improper calibration or poor cleaning procedures in between uses.
Moreover, we may have had some buildup that disturbed the flow between
the pipes and valves leading from the pump to the resin column.
2. Titration: The glassware used in this stage of the experiment, namely
flasks, burettes, and pipettes, are not suitable to give accurate values for
small volumes [we took only 10mL of the sample to titrate]. Titration has
CHEN310 – Transport Phenomena Lab 1 Ion-Exchange and Water Hardness

also been affected by the indicator we used, Eriochrome Black T (EBT),

which is only suitable for a pH range of 9-10. To use it with our samples
that had pH values between 2 and 7, we added drops of NaOH that may
have affected the titration procedure. EDTA was also used to monitor the
change of Ca2+ concentrations with varying volumes in every sample
which was visible from the change in color.
3. Regeneration: Inaccuracies could rise in case of partial regeneration of
the resin in the columns, this could lead to mistakes throughout the
experiment since regeneration is essential to allow H+ ions of HCl to
replace the trapped Ca2+ ions in the resin column.

Among all these errors, we believe that the error with most significance and
contribution to the experiment’s overall uncertainty is due to the varying
volume of EDTA added during titration. We didn’t have a base of the ‘right’
blue color to stop at, so titration was stopped at visually different shades in
every trial.

ii. Error Propagation: Water hardness is calculated from equation 5 where we have
2 main contributors to uncertainty: concentration of EDTA solution and the ratio
of titrant volume to sample volume since all other terms in equation 6 are
constant. The uncertainty in water hardness can be calculated by equation 7:

Thus, the errors in water hardness can be tabulated as shown in the table below:
CHEN310 – Transport Phenomena Lab 1 Ion-Exchange and Water Hardness

Hardness
Sample Time(mins) VEDTA (mL) Hardness(ppm) Uncertainty(ppm)
1 0 7 20456.8 722.655
2 3 2.5 7306 291.956
3 6 1.5 2191.8 105.297
4 9 2 2922.4 124.738
5 12 3 4383.6 168.337
6 15 2.1 6137.04 257.740
7 18 5.3 15488.72 555.417
8 21 4.7 13735.28 497.148

Table 1: Uncertainty of Water Hardness

Detailed error propagation and calculations are found in Appendix C.

III. Conclusions and Recommendations

i. Conclusions: In conclusion, we can summarize the goal of this experiment by
observing changes in water hardness and calculating the exchange capacity that
governs the amount if calcium ions at a given time.
Initially, we start with a pH value of 7.52, conductivity of 0.00379 S, and water
hardness of 20456.8 ppm that are the highest throughout the experiment. As we
increase the volume, we are forcing more ions to be exchanged, thus we observe a
decrease in Ca2+ ion concentration, pH, conductivity, and water hardness.
When the volume of treated water increases to 0.35 L at 6 minutes, the pH,
conductivity, and water hardness decrease to 2.99, 0.000568 S, and 2191.8 ppm
respectively. This shows that the concentration of Ca2+ ions present in the sample
affects the pH, conductivity, and water hardness in an inverse matter.
This behavior stops at the exhaustion point, where the resin reaches its threshold,
causing Ca2+ ion concentration, pH, conductivity, and water hardness to increase.
To support this claim, notice that the pH, conductivity, and water hardness at time
CHEN310 – Transport Phenomena Lab 1 Ion-Exchange and Water Hardness

9 minutes are 2.97, 0.00057 S, and 2922.4 ppm respectively. Slight variations in
values are there because of errors in the experiment.
Overall, the exchange capacity in this experiment is calculated to be 6.514904459
meq/ml of wet resin.
ii. Recommendations: The process of ion exchange is especially useful in multiple
industries such as food, decontamination, water treatment, etc. If we were to stick
to the field of water treatment, such experiment is important in eliminating
potential problems that rise from exposure to hard water such as damaging pipes,
decreasing machine efficiency, and buildup of contaminants that pose serious
health, safety, and cost risks.
To further improve the efficiency of our experiment, we have several
recommendations to consider. When measuring pH and conductivity of our
samples, we noticed great variability, so it is recommended that we use a better
indicator with a range that caters better to our reaction. Moreover, to make this
experiment more efficient, we can use larger resin columns to extend the period
before regeneration is required. In addition, we can try to use digital machinery to
automate the flowrate and detect titration to eliminate any error that might arise.
Finally, such results should be considered on a wider scale with additional studies
in the domain due to the benefits of increasing water quality for personal and
machinery usage.
CHEN310 – Transport Phenomena Lab 1 Ion-Exchange and Water Hardness

IV. References
[1] Winfield, S. (2022). What is Ion Exchange & How Does it Work? Water Defense.
https://waterdefense.org/water-softener/guide/ion-exchange-process/
[2] Ion Exchange Lab manual – CHEN310 moodle page
lms.aub.edu.lb/pluginfile.php/2272348/mod_resource/content/1/Ion Exchange
Experiment-AT2015-1-20.pdf
[3] Cytiva. (n.d.). Troubleshooting protein loss during IEX chromatography - Cytiva.
https://www.cytivalifesciences.com/en/us/solutions/protein-research/knowledge-
center/protein-purification-methods/ion-exchange-chromatography/troubleshooting-
proteinlossduringiex#:~:text=Weak%20ion%20exchangers%20can%20take%20up%20or
%20lose,a%20different%20selectivity%20compared%20to%20strong%20ion%20exchan
gers.
CHEN310 – Transport Phenomena Lab 1 Ion-Exchange and Water Hardness

V. Appendices
i. Appendix A: Raw Data

Sample Time (min) Flowrate VTreated Water Conductivity

(L/h) (L) (S/cm)
1 0 7 0 0.00379
2 3 7 0.35 0.000647
3 6 7 0.7 0.000568
4 9 7 1.05 0.00057
5 12 7 1.4 0.00049
6 15 7 1.75 0.00208
7 18 7 2.1 0.00364
8 21 7 2.45 0.00372

Table 2: Raw Data of Conductivity

Sample Time (min) Flowrate VTreated Water pH

(L/h) (L)
1 0 7 0 7.52
2 3 7 0.35 3.01
3 6 7 0.7 2.99
4 9 7 1.05 2.97
5 12 7 1.4 3.08
6 15 7 1.75 4.72
7 18 7 2.1 6.13
8 21 7 2.45 6.61

Table 3: Raw Data of pH

CHEN310 – Transport Phenomena Lab 1 Ion-Exchange and Water Hardness

Sample Time Flowrate VTreated Dilution VEDTA Water

Hardness
(min) (L/h) Water (L) Factor (mL)
(ppm)
1 0 7 0 10 7 20456.8
2 3 7 0.35 10 2.5 7306
3 6 7 0.7 5 1.5 2191.8
4 9 7 1.05 5 2 2922.4
5 12 7 1.4 5 3 4383.6
6 15 7 1.75 10 2.1 6137.04
7 18 7 2.1 10 5.3 15488.72
8 21 7 2.45 10 4.7 13735.28

Table 4: Raw Data of Water Hardness

CHEN310 – Transport Phenomena Lab 1 Ion-Exchange and Water Hardness

ii. Appendix B: Calculations

(Equation 1)

(Equation 2)

(Equation 5)

(Equation 6)

(Equation 7)

Constant Parameters
Parameter Value Unit
Flow 7 L/hr
VSample 10 mL
MWCaCO3 176.18 g/mol
Column Diameter 20 mm
Column Height 450 Mm
MWCa 40 g/mol
eV EDTA 0.05 mL
eV Sample 0.05 mL

Table 5: Constant Parameters

CHEN310 – Transport Phenomena Lab 1 Ion-Exchange and Water Hardness

Sample Calculations:

Exchange Concentration:

V Wet Resin= (π x 202 x 450) / 4 = 1413 mm3 = 141.3 mL

VExhaustion = 7/60 x 9 = 1.05 L

MCa2+ in grams = (20456.8 - 2922.4) x 1.05 x 10-3 = 18.41112 g

MCa2+ in meq = 18.41112 x 2/40 x 1000 = 920.556

Exchange Capacity = 920.556 / 141.3 = 6.514904459 meq/ml

Treated Water Volume:

for time 3 minutes:

Treated Water Volume = (3*7)/60 = 0.35 L

Water Hardness:

for time 3 minutes:

Water Hardness = 2.5/10 x 0.01 x 292.24 x 1000 x 10 = 7306 ppm

Calculated Parameters
Parameter Value Unit
Volume of Wet Resin 141300 mm3
Volume of Wet Resin 141.3 mL
VExhaustion 1.05 L
VExhaustion 1050 mL
Mass of Ca2+ 18.41112 g
Mass of Ca2+ 920.556 mEq
Exchange Capacity 6.514904459 mEq/mL
Table 6: Calculated Parameters
CHEN310 – Transport Phenomena Lab 1 Ion-Exchange and Water Hardness

iii. Appendix C: Error Analysis

Hardness Error:

For Sample 3:

= (((0.05/10)2 + (0.05/1.5)2 )½ ) x 1.5/10 = 0.05056

= Error (Vt/Vs)

= EDTA Mass error = 0.1 g

= EDTA Volume error = 1 ml

= (((0.1/2.9224)2 + (1/1000)2 )½ ) x 2.9224/1000

= Concentration error = 0.000100043 g/ml

= ((0.05056/0.15)2 + (0.000100043/0.01)2 )½ ) x 2191.8

= Hardness error = 105.29 ppm