Research Question: How does temperature change affect the pH of pool water?

Introduction:
I am a very dedicated swimmer and going to the pool occasionally is a huge concern for me as I
have very sensitive skin and suffer from skin problems, which is an issue among some of my peers as well.
Inappropriate pool water regulations have affected the daily lives of many swimmers and prevented them,
including myself, from returning to the pool for a long period of time. I wanted to take this opportunity to
investigate exactly where these issues come from and how to prevent them. I believe that the pH level is
one of the most important factors that determine not only the swimmers’ health, but also the hygiene of
the swimming pool as acidic or basic pool water corrodes tiles, machinery in the water circulation and
purification system, and increases the difficulty to maintain the free-chlorine level in pools.
Pool water all have a pH of 7.2 to 7.8 and contain a variety of chemical compounds. The
temperature of the environment needs to be taken in account when determining the amount of chemical
compounds the pool needs. The pH of any solution is dependent on its temperature. Based on molecule
properties, the rise of temperature will increase molecular vibrations. Increased vibrations will cause the
aqueous compounds to dissociate greater which will release more Hᐩ ions and OH⁻ ions, which will
decrease the pH. It is important to note that neutral compounds such as pure water will always stay
neutral despite changes in pH. This is because neutral compounds will always have the same
concentration of Hᐩ ions and OH⁻ ions despite changes in pH. Solutions will only become acidic if [Hᐩ]
surpasses [OH⁻] and vice versa.

Buffer Systems in Pool Water and ​Le Chatelier’s Principle

Pool chemicals combined with water molecules often form buffer systems in swimming pools.
Common buffer systems in swimming pools include the hydrolysis of chlorine, self-ionization of water,
and hydrolysis of sodium carbonate.
If we were to look at the self-ionization of water molecules, it is an endothermic reaction.
2H 2 O(l) + energy ⇌ H₃O⁺(aq) + OH⁻(aq)
ΔH= +
This means that when we raise the temperature, the
equilibrium shifts to the right and more Hᐩ ions and OH⁻
ions are produced, thus increasing the pH. An increase in
products will cause K w to increase as well (figure 1).
According to ​Le Chatelier’s Principle,​ when the
temperature changes, the equilibrium shifts to minimize
the change. Almost all of the reactions that occur in pool
water are endothermic.
In endothermic reactions, increasing the temperature
meant shifting the reaction to the right in order to reduce
the excess amount of heat, therefore producing more
products. One of the common chemical reactions in pools
include the reaction of sodium carbonate with water, which is the reaction that I will be looking at to
analyze pool water properties:
Full reaction equation: N a₂CO₃(aq) + H₂O(l) + energy ⇌ 2N aOH (aq) + CO₂(g)
Net Ionic equation: CO32−(aq) + H₂O(l) + energy ⇌ 2OH −(aq) + CO₂(g)
Carbonic acid formation in swimming pools: CO₂(g) + H₂O(l) ⇌ H₂CO₃(aq)

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 Increasing the temperature will produce more OH⁻ ions and CO₂ gas as this is an endothermic
reaction. The increase of OH⁻ ions will raise the pH, yet it is important to know that more H⁺ ions will
also be dissociated, which reduced the pH. The pH value will also be reduced by the increased production
of CO₂ molecules. The reaction of gaseous CO₂ molecules with water molecules in the pool produces
carbonic acid, lowering the pH.
Another two aspects to consider for this experiment is pressure and reaction systems. According
to ​Le Chatelier’s Principle,​ when the partial pressure of any gaseous reactant or product increases, the
equilibrium shifts to decrease its partial pressure and vice versa. A key note is that the reaction must be in
a closed system for it to be an equilibrium reaction. In my titration experiment, it is very difficult to avoid
the loss of gaseous reactants and products. I have to ensure the least amount of reactants and products
lost and assume that the reaction is in a closed system.
Calculation Method​:
Once I determine the half-equivalence point of the titration of sodium carbonate with 1M HCl
acid, I can use the pOH value as the pK b value due to this equation: pOH= pK b . Then, I could solve for the
pH of the solution when 0 cm³ of 1M HCl is added:
1. Since pK b = -log K b , K b = 10−pK b
[products]
2. Using the K b value, it is substituted to the expression: K b = [reactants] , where [products]=
[OH⁻]²[CO₂] and [reactants]= [CO₃] according to the reaction:
CO32−(aq) + H₂O(l) + energy ⇌ 2OH −(aq) + CO₂(g)
3. Using the equilibrium constant expression and the values from the ICE table, determine the value
of x, which indicates the concentration of OH⁻ ions.
4. Substitute [OH⁻] in pOH= -log[OH⁻]
5. Since pH= 14 - pOH, substitute [pOH⁻] to calculate the pH.
Hypothesis​:
Based on Le Chatelier’s Principle and the behaviours of particles, I hypothesize that the pH
readings of pool water will decrease with an increase in temperature. This is because molecular vibrations
increases with temperature and more Hᐩ ions and OH⁻ ions will be dissociated. Since more Hᐩ ions
dissociate due to the rise of temperature, pH increases as it is the measurement of [Hᐩ]. Because pool
water contains endothermic reactions with pool chemicals, increasing the temperature will favour the
forward reaction, producing more CO₂ molecules, which will increase the pH as the more CO₂ molecules
present, the more acidic the water. This is due to the creation of carbonic acid.

Methodology:
Variables:
Independent variable: temperature (273K, 293K, 323K, 348K, and 373K)
Dependent variable: pH of sodium carbonate solution to simulate that of pool water
Controlled variables:
Temperature:​ As discussed in the ​Background​, the pH of a solution is dependent on the temperature.
This variable is controlled as much as possible by keeping the sodium carbonate solution in a water bath
with the desired temperature measured with a thermometer with ±0.1K uncertainty. Values: Around
273K, 293K, 323K, 348K, and 373K
Concentration of N a₂CO₃(aq) : ​The concentration of the sodium carbonate solution determines the
concentrations of Hᐩ and OH⁻ ions present, which will affect the pH of Na₂CO₃. The amount of solid
Na₂CO₃ is measured with an electric balance with a high precision that has an uncertainty of ±0.001g.
5.000 g of solid Na₂CO₃ is dissolved in a 500 cm³ volumetric flask with distilled water. Values: c= 0.09M
Volume of N a₂CO₃(aq) : ​The amount of N a₂CO₃(aq) used directly impacts where the equivalence and
half-equivalence points occur. The titrant, HCl acid, is measured in a highly precise burette with an
uncertainty of ±0.05 cm³. Aqueous Na₂CO₃ is measured using a graduated cylinder with an uncertainty

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 of ±0.5 cm³. Values: 50 cm³ of N a₂CO₃ (aq) is used for each increment and trial.
Pressure: ​Stated in the ​Background​, since CO₂ is the product and reactant, it is important to keep the
pressure at a constant as pressure will affect the number of moles of carbon dioxide, which will alter the
pH values. Data collected by The Weather Network has shown that atmospheric pressure in London,
Ontario, stays relatively constant at 102 kPa. In addition, every trial for each increment is performed
using the same methodology to insure little to no pressure differences. Values: Atmospheric pressure: 102
kPa.
Apparatus:
- Goggles and gloves - 5 erlenmeyer flasks (200 cm³ or - TREE electronic balance (Model:
- 2-4 800 cm³ beakers for water 250 cm³) HRB203)
baths - Burette - scoopula
- Two 400 cm³ beakers to hold - Burette clamp - Volumetric flask (500 cm³)
distilled water and chemical - Support stand - Vernier pH sensor and LabQuest
residue (do not mix them) - Funnel - Test tube holder
- One 250 cm³ beaker to hold 1M - 100 cm³ graduated cylinder - Wire gauze
HCl acid - 1-4 Corning hot plate
- Beaker clamp - Flinn Scientific Inc. thermometer

Materials:
- Methyl Orange - 1 M HCl - pH 10 buffer solution
- Powdered sodium carbonate - Distilled water bottle - Ice cube
- Tap water - pH 4 buffer solution

Safety and Precautions​:

Since handling corrosive and reactive materials is involved, latex gloves and goggles are needed at all
times.
Hot material and glassware handling​: Use a beaker clamp to remove water baths from the
hot plate. Use test tube holders to handle hot erlenmeyer flasks filled with N a₂CO₃(aq) while mixing with
HCl acid during the titration. Handle glassware with caution. If broken, sweep it up with a dustpan and
brush and notify the supervisor.
Corrosive material handling​: Powdered sodium carbonate and 1 M HCl acid will cause
serious eye and skin damages. The buffer solutions with pH of 4 and 10 may be harmful if swallowed and
may cause skin and eye irritation. It is important to wear goggles and avoid as much skin contact as
possible using latex gloves and keeping a distance from
the materials. Do not touch skin, eyes or mouth with
gloves.
Disposal and clean-up procedures:​ Once finished,
rinse burette with base and dilute any chemicals with
water before pouring them into the sink except for 1 M
HCl acid. Dispose corrosive solutions in the 400 cm³
residue beaker. Turn off the hot plate and let it sit for at
least 5 min to cool down, then store it properly. In
addition, check if the pH sensor is submerged in the pH
storage solution (KCl solution) once finished.
Procedure:
1. Prepare water baths with temperatures close to
373K, 323K and 348K. There are five water baths with
temperatures: 273K, 293K, 323K, 348K, and 373K

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 2. Prepare Na₂CO₃ solution with 5 g of powdered Na₂CO₃ and 500 cm³ of distilled water using a 500
cm³ volumetric flask and pour distilled water in with a funnel. Fill until the mark. Shake and dissolve
well.
3. Measure 50 cm³ of solution using a graduated cylinder and pour it in each erlenmeyer flask. Fill 5
erlenmeyer flasks with 50 cm³ of the solution.
4. Let each flask sit for 3-4 min to achieve room temperature.
5. During the waiting time, prepare a burette with 1M HCl as the titrant. Clean the burette with acid then
fill the acid to 0 cm³.
6. Place the erlenmeyer flask under the burette and add 3 drops of methyl orange indicator.
7. Measure the temperature of the solution, Record data.
8. Calibrate Vernier pH sensor and lab quest (steps indicated below) and then place pH sensor into the
solution. Record data.
9. Perform a titration all the way past the end point until there are no more sufficient changes in pH.
Record the data of pH and volume (of titrant) for every 0.1 cm³ - 2.5 cm³ of HCl used.
10. Perform 4 other trials with the other 4 erlenmeyer flasks. It is best to keep all the trials for each
increment at very similar temperatures.
11. Repeat 2-10 with other 4 temperatures. Remember to remove hot water bath beakers with a beaker
clamp. Keep erlenmeyer flasks in water baths during every titration to keep the temperature as
constant as possible. When preparing Na₂CO₃ solutions with high temperatures, make sure to cover
the top of the erlenmeyer flask using the wire gauze to prevent as much CO₂ loss as possible.
12. Clean the work area and rinse the burette with base. Specific instructions indicated in ​Safety and
Precautions​.
To calibrate pH sensor:
1. Wash the sensor with distilled water and soak it into the pH 4 buffer solution and wait for 2 mins.
2. Calibrate by entering the pH of the buffer when the live voltage stabilizes (use buffer 4 and 10)
3. Repeat 1-2 using the pH 10 buffer solution.
4. Before putting the probe into the erlenmeyer flask for titration, wash with distilled water.
Note: In my preliminary work, as I added a few drops of the titrant to the pool water, drastic changes
occured in the pH and it was hard to pinpoint the equivalence point as pool water is too close to neutral.
Since pool water is slightly basic, I have come to the conclusion to simulate pool water with a basic
compound and aqueous sodium carbonate is the safest and most reliable material that I can use.

Raw Data:
Qualitative Data:
Table 1: Qualitative Observations of Titrating Na₂CO₃ Solution with 1 M HCl Acid for Every Trial and Increment

Before Titration During After

Observations - HCl acid is clear, aqueous
and has a strong odor
- Powdered Na₂CO₃ is
white and solid
- Aqueous Na₂CO₃ is clear
and odorless
- Added methyl orange
turns the analyte
orange-red
- Temperature of the
analyte is constant
- Analyte turns yellow at the endpoint and the color - Titrated analyte has
becomes extremely dense as more titrant is added past the a very dense yellow
endpoint color
- for high temperatures (323K, 348K, 373K) various - There is an
amounts of CO₂ gas is produced as bubbles form when the acceptable difference
titrant is added; gas is also released from the erlenmeyer between the initial
flasks when preparing high temperature analytes temperature and the
- Analytes with high temperatures at the beginning of the final temperature of
titration have their temperature drop throughout the the analyte
experiment; analytes with cold temperatures (273K) warm
up throughout the experiment

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Quantitative Data: pH Curves
What is shown here are the pH
curve graphs that demonstrate
the raw data collected for each
trial of each increment. The
trials that are considered as
outliers are indicated in the
legend. Please note that the
legend is written in order: trial 1
to 5 from top to bottom.

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Quantitative Data: Half-Equivalence Points

For Table 2, the red values are the outliers. However, please keep in mind that due to
experimental errors, the outliers might be theoretically accurate. For instance, the amount of
titrant needed to neutralize the analyte should decrease with increase in temperature as the
analyte becomes more acidic when heated.

As of Table 3, I have used the data of the most precise trial according to the mean values.

Processed Data:
Using the calculation process stated in the ​Background​, below are the calculated results of Temperature
VS. pH.
Calculation for the ​Increment ~273K​ with Uncertainty Calculations
To find K b value of the equilibrium reaction:
pOH=pKb= 14- pH half −equivalence point
=14-8.70 ±0.01
= 14-8.70±0.114942528%
=5.30±0.114942528%

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 N a₂CO₃(aq) + 2HCl(aq) ⇌ 2NaCl(aq) + H ₂ O(l) + CO ₂ (g)
n=? c= 1 M
V
v= 0.05 dm3±0.0005dm3 end−point = 0.0087 dm³±0.00005 dm³
V end−point = 0.0087 dm3 ±0.574712643%
n= 1M (0.0087 dm3 ±0.574712643%)
n=0.0087 mol ±0.574712643%
N a₂CO₃(aq) 1 x
HCl(aq) = 2 = 0.0087 mol ±0.574712643%
2x= 0.0087 mol ±0.574712643%
x= 0.00435 mol ±0.574712643%
2− −
Table 4: ICE Table Calculation Involving the reaction of CO3 (aq) + H₂O(l) ⇌ 2OH (aq) + CO₂(g) (Before Titration) to
Find the pH of N a₂CO₃(aq) (Note that the volume is 0.05dm3±0.0001dm3)
−
CO2−
3 (aq) 2OH (aq) CO₂(g)

Initial/n 0.00435 mol ±0.574712643% 0 0

Change/n -x +2x +x

Equilibrium/n 0.00435 mol ±0.574712643% -x 2x x

Kb= 10−pKb
=5.011872336× 10−6 ±0.114942528%
5.011872336× 10−6 ±0.114942528%= 0.00435 mol ±0.574712643%
2x²
−x Kb is too small, -x is negligible
2.180164466 × 10−8 mol ±0.689655171% = 2x²
0.0001044070033 mol ±0.689655171% = x
−
Since the number of moles of OH (aq) ions is 2x:
n of OH⁻ = 0.0002088140065 mol ±0.689655171%
[OH⁻]= 0.0002088140065 mol ±0.689655171%
0.05dm3±1%
=0.00417628013 mol dm⁻³ ± 1.689655171%
pOH= -log[OH⁻]
=2.379210378 ± 1.689655171%
pH= 14 - ​2.379210378​ ± 1.689655171%
=11.62078962 ± 1.689655171%
≈12 ±0.2

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Calculation for the ​Increment ~348K
pOH=pKb= 14- pH half −equivalence point
= 7.10
N a₂CO₃(aq) + 2HCl(aq) ⇌ 2NaCl(aq) + H ₂ O(l) + CO ₂ (g)
n=? c= 1 M
v= 0.05 dm3 V end−point = 0.0088 dm3
n= 1M ( 0.0088 dm3)
n= 0.0088 mol
N a₂CO₃(aq) 1 x
HCl(aq)
= 2
= 0.0088 mol
x= 0.0044 mol
Using the same ICE table in Table 4:
Kb= 7.943282347 × 10−8
7.943282347 × 10−8 = 0.00442x²mol −x Kb is too small, -x is
negligible
x =1.321938772× 10−5 mol
−
Since the number of moles of OH (aq) ions is 2x:
n of OH⁻ =2.643877544× 10−5 mol
−5
2.643877544×10 mol
[OH⁻]= 0.05dm3
=5.287755087 × 10−4 mol dm⁻³
pOH= -log 5.287755087 × 10−4 mol dm⁻³
=3.276728668
pH= 10.72327133
≈ 11

Table 5: Temperature VS. pH of Sodium Carbonate Solution Including Uncertainties Calculated

⁓2​73.0K ⁓​293.0K ⁓323.0K ⁓348.0K ⁓373.0K

pH 11.62078962 11.51573946 10.66827922 10.72327133 11.42078962

(unrounded)

Absolute ±0.196351272 ±0.196444967 ±0.184396317 ±0.195650615 ±0.194175645

Uncertainty
(unrounded)

pH 12 12 11 11 11
(rounded)

Absolute ±0.2 ±0.2 ±0.2 ±0.2 ±0.2

Uncertainty
(rounded)

Note: The reason I included the unrounded values, especially the pH values, is because having
specific values gives a more obvious contrast between the results of each increment.

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Evaluation:
According to the graph, Temperature VS. pH of Basic Solution Sodium Carbonate in the
Processed Data​ section, my hypothesis is correct as increasing the temperature is proven to decrease the
pH of a solution. Due to systematic errors, most of the data collected from increments 323K and 348K are
not accurate. For accuracy, we should look at the results of increments 273K, 293K and 373K as the pH
does decrease with increasing temperature. Although I am not able to find specific literature values for
this experiment, the results of the 3 increments conclude that the outcomes are fairly accurate. The results
are correct as increasing the temperature raises the kinetic energy in the molecules, which causes more
molecular vibrations. These vibrations cause more H⁺ ions to dissociate, lowering the pH. In addition,
according to ​Le Chatelier’s Principle,​ raising the temperature of the reactants side will increase the
number of products in endothermic reactions. As more molecules of CO₂(g) are produced when
Na₂CO₃(aq) is heated, more carbonic acid is produced, which also raises the pH. The reason I chose to
simulate pool water using Na₂CO₃(aq) is because both pool water and Na₂CO₃(aq) have similar
properties as they are both basic (yet Na₂CO₃(aq) is more basic) and both solutions involve endothermic
reactions. Another reason is that Na₂CO₃(aq) is one of the most common chemicals found in swimming
pools as it is used to alter the acidity of the pool. Therefore, the results obtained from the experiment with
Na₂CO₃ solution conclude that the pH of actual pool water will decrease with increase in temperature.
Reversely, decreasing the temperature will raise the pH.

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Weaknesses, Improvements and Strengths
Weakness: One of the major sources of error is that the reaction is not a closed
system​. This is a major limitation as a titration must be performed with an opening of the system
(erlenmeyer flask). Large amounts of CO₂ is lost as bubbles during titrations with high temperatures. Low
temperatures such as 273K and 293K have less amounts of CO₂ gas produced, so there is a minimum loss
of CO₂. Similarly, when preparing solutions with high temperatures, a large amount of CO₂ gas escaped
from the opening of the flask. The loss of CO₂ altered the pH values of the increments with high
temperatures. Increments 323K and 348K is more acidic than 373K as I have firmly placed a wire gauze
on top of the opening, therefore retaining the CO₂ gas which increased the pH. For 373K, due to
methodology errors, a wire gauze was not placed over the opening which released CO₂ gas into the
environment and made the initial pH value lower than it should be. ​Improvement:​ Cover erlenmeyer
flasks with wire gauze when preparing solutions with high temperatures. Seal any containers with
solutions not in use with provided materials to prevent gas leakage to and entrance from the environment.
During the titration, use strong plastic fabrics to link and cover the burette with the opening of the
erlenmeyer flask to prevent as much loss of CO₂ gas as possible. ​Strengths related​: During and within
experiments, solutions that are not in use are always sealed tightly with provided materials to maintain a
closed system.
Weakness: Temperature cannot be kept constant during experiments.​ Due to the
environment I am working with and the initial temperature of the titrant, high temperature analytes tend
to lose heat fast and cold temperature analyte (ie. 273K solution) tends to gain heat during the
experiment. For instance, the 373K analyte had decreasing temperature during the titration which slightly
increased its pH value. Therefore the calculated pH of the analyte before the titrant is added is slightly
higher than it should be. ​Improvement​: Submerging solutions in water baths with corresponding
temperature is a method to maintain the temperature as constant as possible. A better way of doing so is
wrapping the erlenmeyer flask with styrofoam. If possible, it would be best to perform the experiment in
environments with desired temperatures (e.g. cold storeroom). ​Strengths​: By submerging the
erlenmeyer flasks in water baths with desired temperatures during experiments really helped to preserve
the temperature as much as possible.
Weakness​: ​The concentration of initial Na₂CO₃ Solutions are not kept constant.​ It is
extremely difficult to obtain precisely 5.000g of solid Na₂CO₃​ ​each time when preparing the analyte. This
is one of the major factors of where the experimental errors come from. By having a greater mass of solid
Na₂CO₃ dissolved, the initial pH of the analyte will be greater than it should be and vice versa.
Improvement​: Method wise, it is best to make the analyte by dissolving 12.5 g of solid Na₂CO₃ with
water to make 1.25 dm3 of solution. This way, all trials and increments will have the same concentration
of Na₂CO₃(aq). ​Strengths​: A precise electric balance is used to mass materials as it has an uncertainty of
±0.001g. Almost all trials have the exact amount of dissolved solid Na₂CO₃.
Weakness: pH sensor readings cannot be kept constant.​ It takes at least 1 min for the pH
sensor to obtain a constant value as it tests the solutions. Oftentimes I had to record the pH reading
before it stabilized due to the time limit. Another reason is that if I wait too long, there will be greater
changes in the temperature, which will either increase or decrease the calculated initial pH of the analyte.
Thus not all pH values recorded in the raw data are extremely accurate. ​Improvement​: Data will be
more accurate as the pH sensor sits longer in the solution. If possible, it would be best to perform two
titrations at the same time to preserve time and allow the pH readings to stabilize. ​Strengths​: In terms of
method, every time the titrant is added, the pH sensor is able to obtain a more accurate reading as it is
allowed to sit in the analyte for at least 40 sec. In addition, the pH sensor is calibrated frequently to
achieve high accuracy as a calibration is performed between each and every trial.

10
 Weakness: Graduated cylinder gives a very large uncertainty. ​To measure 50 cm3 of
analyte (aqueous sodium carbonate), I used a graduated cylinder with an uncertainty of ±0.5dm3.
Therefore, the measured volume is not as precise and it will affect the pH calculations as the analyte is the
limiting reactant. If the volume is greater than it should be, the calculated concentration of OH⁻ ions
present will decrease. This will result in a lower pH than it should be. ​Improvement​: Using a pipette
with a smaller uncertainty will generate less errors. Therefore the calculated pH would be as close as
possible to the actual yield.

Extension:
A possible extension to this experiment is to use various pool water samples as different
increments. Samples include: Stabilized chlorinated pool water, unstabilized chlorinated pool water, salt
pool water, unstabilized bromine pool water and stabilized bromine pool water. Here, I shall conduct the
experiment with 2 various temperature values to determine how temperature change affects the pH of
various types of pools. This knowledge will prove helpful for determining which type of pool swimmers
should avoid to reduce the risk or eye, skin and hair damages during hot seasons.

11
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