Heats of Ionic Reactions

By: Courtney Molvig

CHEM 307 - 54

Lab Partners: Matthew Morrow and John McAlpine

Abstract

When there is a chemical reaction, the heat released or absorbed by the system can vary
in many different ways, depending on a bunch of different factors, including the pressure,
temperature, volume, compounds taking place in the reaction, heat capacities, and many more.
For this specific lab, we focused on the difference in energies of ionization of a monoprotic and
diprotic acid. The monoprotic acid we used was hydrochloric acid and the diprotic acid we used
was malonic acid. The base that was used to react with both of these acids was sodium
hydroxide. The monoprotic acid releases one proton per molecule when reacting, while the
diprotic acid releases two protons per molecule when reacting. We can use a calorimeter (in this
case ice water) to find the heat capacity of the Dewar and the change in enthalpy of the two
acids. When all of the measurements were completed, we found that the average change in
enthalpy for the hydrochloric acid reacted with sodium hydroxide is 808 J. The average change
in enthalpy for the first proton of malonic acid was 380 J, while the average change in enthalpy
for the second proton of malonic acid was 333 J. As you can see, the second proton of malonic
acid has a lower change in enthalpy compared to the first proton. All of the enthalpies calculated
in this experiment were positive, indicating that the reaction is endothermic, meaning that heat is
absorbed by the system.

Introduction

In this lab, the end goal is determine the difference in the energies of ionizations of a
monoprotic and a diprotic acid. Before even starting this experiment, it is important to know
what a monoprotic and diprotic acid is. “Monoprotic acids are acids that can release only one
proton per molecule and have one equivalence point… Polyprotic acids are acids that can lose
several protons per molecule.”[1] That being said, a diprotic acid, di meaning two, is an acid that
can lose two protons per molecule. What cause these acids to release a proton in the first place
are chemical reactions. Chemical reactions occur all around us, even when we do not realize it.
When our body is metabolizing food, our saliva is digesting sugar, our bikes are getting rusty
from sitting in the rainwater, we are burning wood to stay warm, we are baking a cake, our
banana is rotting, or we are using a chemical battery, we are experiencing chemical reactions. [2]

When working with chemical reactions, it is important to understand heats of reactions.

Heat of reaction is the amount of heat that must be added or removed during a chemical reaction
in order to keep all of the substances present at the same temperature. [3] Knowing the heat that
will be released from the system or gained by the system allows us to adjust what is needed to
maximize/ minimize the work and energy done on the system or by the system. In order to better
understand what is mentioned above, it is worth reviewing the first law of thermodynamics,
because this is the basis and once we understand this law, we can begin investigating more about
heat capacities. The first law of thermodynamics follows the following equation:

𝐸2 − 𝐸1 = 𝑄 − 𝑊,

where E is the internal energy, Q is the heat transfer into the system, and W is the work done by
the system.[4]
 Once we understand the basis of thermodynamics, we can begin to calculations for this
experiment. Once we have all of the data obtained from the lab, we can begin calculating the
heat capacities of the compounds we are working with. “The heat capacity of a defined system is
the amount of heat (usually expressed in calories, kilocalories, or joules) needed to raise the
system’s temperature by one degree (usually expressed in Celsius of Kelvin).”[5] The following
equation shows how you can calculate the heat capacity.

𝑄
𝐶= ,
∆𝑇
where Q is the heat, ∆𝑇 is the change in temperature, and C is the heat capacity. The units for the
heat capacity shown above are Joules/K. We can then use the heat capacity to find the change in
enthalpy, which has units of Joules. The equation for the change in enthalpy is:

∆𝐻 = 𝐶∆𝑇,

where ∆H is the change in enthalpy, C is the heat capacity, and ∆T is the change in temperature.

In this specific lab, we are using a Dewar flask that is representing a perfect adiabatic
system, which is not exactly the case and therefore why we used ice water for a calibration. What
an adiabatic system is supposed to do is prevent any loss or gain of heat between the
surroundings and the system. Using the Dewar flask and the ice water calibration, we can
calculate the heat capacity and enthalpy change from the data obtained in lab. Below is an image
of how the setup looks when we started using the Dewar flask and computer to collect data.

What we expect to see in terms of graphs is a steady temperature when the monoprotic or
diprotic acid is just sitting in the Dewar flask. Once we add the specific amount of base that is
used to react completely, there will be a rapid increase in temperature and then the temperature
will begin stabilizing again. Since we are only adding the amount of base need to react
completely with the acid, the reaction should be neutralized. That being said, the neutralized
reaction should also have a neutral pH (around a pH of 7). A monoprotic acid will only show one
major increase in temperature, since only one proton is released per molecule, while a diprotic
acid will show two major increases in temperature (stabilized temperature, increase in
temperature, stabilized temperature, increase in temperature, and one final stabilized
temperature), since two protons are released per molecule. Looking at the graphs from the class
document, I expect there to be a larger change in temperature when the monoprotic acid is
reacting with the base. For the diprotic acid, I believe that the first proton will have a larger
change in temperature than the second one.

Methods/Experiments

To begin this lab, we began by preparing a malonic acid solution, a sodium hydroxide
(NaOH) solution, and a hydrochloric acid (HCl) solution. To prepare the sodium hydroxide and
hydrochloric acid solution, we got two one – liter polyethylene bottles and added DI water until
it reached the neck of the bottles. In one of the bottles we added a splash of the HCl stock
solution, which has a concentration of about 10 M. We did the same for the second bottle, but we
added a splash of the NaOH stock solution which has a concentration of about 17-18 M. To
prepare the malonic acid solution, we weighed out a certain amount of the solid malonic acid and
dissolved it in a certain amount of DI water that was added to the last polyethylene bottle.

Once all of the solutions were made, we then had to determine the concentration of each
solution. To determine the concentration of malonic acid, we converted the mass of malonic acid
used to the number of moles and then divided the amount of moles of malonic used by the
volume of DI water used (in L). To find the concentration of NaOH, we did an acid-base titration
with KHP. To do this, we first weighed out a certain amount of KHP and dissolved it in some DI
water. You can then add phenolphthalein indicator to the KHP solution and begin titrating with
NaOH. Once the color turns a faint purple, you have reached the end point and you look at the
buret to find the total amount of NaOH added to reach endpoint. You can then calculate the
concentration of the NaOH solution with the mass of KHP used and converted into moles and the
volume of NaOH added to the KHP. This reaction is a 1:1 stoichiometry, so you just divide the
number of moles by the volume of NaOH added (in L) to get the concentration of the NaOH
solution. Once we knew the concentration of the NaOH solution, we then used the NaOH
solution to titrate the HCl solution, using an acid-base titration. We add a certain amount of HCl
into an Erlenmeyer flask and add a couple drops of phenolphthalein indicator. We put a magnetic
stir bar in the flask and place it on a magnetic stir plate. We then can begin titrating the solution
and when it turns a faint pink color and the color stays, we record the number of NaOH that was
added to the flask. We can then calculate the concentration of the HCl solution by the following
calculation:

𝑚𝑜𝑙 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑁𝑎𝑂𝐻 𝑎𝑑𝑑𝑒𝑑 (𝐿)

𝑚𝑜𝑙𝑎𝑟𝑖𝑡𝑦 𝑜𝑓 𝐻𝐶𝑙 (𝑀) = 𝑚𝑜𝑙𝑎𝑟𝑖𝑡𝑦 𝑜𝑓 𝑁𝑎𝑂𝐻 ( )∗
𝐿 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝐻𝐶𝑙 𝑡𝑖𝑡𝑟𝑎𝑡𝑒𝑑 (𝐿)

Now that we know all of the concentrations of our solutions, we can then get the vacuum
Dewar flask out and begin the actual part of the experiment. We first begin the experiment by
performing a calorimetry by using a standard, which in this case we used ice water. Prior to
staring the experiment, we made sure the automatic data logger and digital thermometer were all
working properly. We than sat a large beaker of DI water into an ice bath to form an “ice water”
solution. Once the ice water temperature seemed to stabilize, we placed 150 mL of the ice water
into the Dewar flask using a graduated cylinder, put a magnetic stir bar in the flask, sat the flask
on a magnetic stirring plate, and then began recording the data. Once we were sure the
temperature of the ice water was constant, we then added fifty milliliters of room temperature DI
water into the Dewar flask. We quit recording the data when the temperature began to stabilize
after the addition of the room temperature DI water. The reason why we chose to add 150 mL of
the ice water was because that is the amount that needed so that the probe would reach the
solution and accurately record the data. We repeated this process three times.

Once we were satisfied with how the data and graphs looked, we moved on to the HCl
solution. We added 150 mL of the HCl solution to the Dewar flask, put a magnetic stir bar in the
flask, sat the flask on a magnetic stirring plate, and began recording data. Once the temperature
seemed to remain constant, we used the syringe to inject a little over 29mL of NaOH. We
calculated the volume of NaOH needed to react with HCl (29 mL) and then we added a little
extra so that the HCl would react completely. Again, we did this process three times. We did a
similar process with malonic acid, but we had to inject NaOH twice, since the diprotic acid
releases two protons per molecule. For this step we continued using 150 mL of the acid, but this
time in order to react completely we had to add a little over 13.76 mL of NaOH for both
injections. Once the malonic acid alone had a stable temperature, we added the first injection of
NaOH and then waited for that temperature to stabilize before adding the second injection of the
NaOH. Again, we did three trials for this solution. With all nine trials we did above, we exported
an excel sheet so that we could get the graphs.

The general idea of this experiment and the theory of this experiment was given by the
textbook written by Garland.[6] However, my lab group came up with how exactly we wanted to
begin this experiment and the approximately concentration of the malonic acid solution, NaOH
solution, and HCl solution. We also figured out how to calculate the amount of NaOH needed to
complete the reaction.

Results

Table 1 shows the concentrations of the different solutions that we used in the lab. The
concentrations of the sodium hydroxide and hydrochloric acid solutions were calculated using
acid-base titrations and the concentration of malonic acid was calculated using the mass of solid
malonic acid and the amount of DI water that malonic acid was dissolved in.
Table 1:
Concentrations of the Solution
NaOH Solution HCl Solution Malonic Acid Solution
0.8482 M 0.1655 M 0.0778 M

Table 2 shows the starting temperature of the room temperature DI water, the initial temperature
of the ice water, the final temperature after room temperature DI water was added, and the
difference between the final and initial temperatures. Below shows all three water trials and the
temperatures were recorded from the computer, using the digital thermometer probe that came
with the Dewar flask.
Table 2:
 Temperatures of Water Trials
Starting Initial Final Difference in
Temperature of Temperature in Temperature in Temperatures
DI water the Dewar Flask the Dewar Flask (Final – Initial)
(Ice water) (ice water + DI
water)
Water Trial 1 20.2 °C 14.6 °C 15.7 °C 1.1 °C
Water Trial 2 20.2 °C 12.2 °C 13.7 °C 1.5 °C
Water Trial 3 20.2 °C 10.5 °C 12.3 °C 1.8 °C

Figure 1:
Water Trial 1
17
16.5
Temperature (°C)

16
15.5
15
14.5
14
0 10 20 30 40 50 60
Time (seconds)

Figure 1 shows the graph of the first water trial. This graph is temperature (in degrees Celsius)
vs. time (in seconds). The graph was created in excel using the data that was exported from the
computer program used in lab. As a side note, the graph that was produced in lab was a lot
smoother, which could have been affected from changing the program that graphed the data.
 Figure 2:
Water Trial 2
14.5

14
Tempearture (°C)

13.5

13

12.5

12
0 10 20 30 40 50 60
Time (seconds)

Figure 2 shows the graph of the second water trial. This graph is temperature (in degrees
Celsius) vs. time (in seconds). The graph was created in excel using the data that was exported
from the computer program used in lab. As a side note, the graph that was produced in lab was a
lot smoother, which could have been affected from changing the program that graphed the data.

Figure 3:
Water Trial 3
16
14
Temperature (°C)

12
10
8
6
4
2
0
0 10 20 30 40 50 60 70 80
Time (seconds)

Figure 3 shows the graph of the third water trial. This graph is temperature (in degrees Celsius)
vs. time (in seconds). The graph was created in excel using the data that was exported from the
computer program used in lab. As a side note, the graph that was produced in lab was a lot
smoother, which could have been affected from changing the program that graphed the data.

Table 3 shows the initial temperature the HCl in the Dewar flask, the final temperature after the
NaOH solution was added, and the difference between the final and initial temperatures. Below
shows all three HCl trials and the temperatures were recorded from the computer, using the
digital thermometer probe that came with the Dewar flask.
 Table 3:
Temperatures of HCl Solution Trials
Initial Temperature in Final Temperature in the Difference in
the Dewar Flask (HCl) Dewar Flask (HCl + Temperatures (Final –
NaOH) Initial)
HCl Trial 1 20.2 °C 22.0 °C 1.8 °C
HCl Trial 2 20.9 °C 22.6 °C 1.7 °C
HCl Trial 3 21.3 °C 22.9 °C 1.6 °C

Figure 4:
HCl Trial 1
22.5

22
Temperature (°C)

21.5

21

20.5

20
0 10 20 30 40 50 60 70 80
Time (Seconds)

Figure 4 shows the graph of the first HCl trial. This graph is temperature (in degrees Celsius) vs.
time (in seconds). The graph was created in excel using the data that was exported from the
computer program used in lab. As a side note, the graph that was produced in lab was a lot
smoother, which could have been affected from changing the program that graphed the data. It is
important to note the steep slopes in the graph at around 26 seconds shows that a monoprotic
acid releases one proton per molecule.
 Figure 5:
HCl Trial 2
23
22.5
Temperature (°C)

22
21.5
21
20.5
20
0 10 20 30 40 50 60 70 80
Time (seconds)

Figure 5 shows the graph of the second HCl trial. This graph is temperature (in degrees Celsius)
vs. time (in seconds). The graph was created in excel using the data that was exported from the
computer program used in lab. As a side note, the graph that was produced in lab was a lot
smoother, which could have been affected from changing the program that graphed the data. It is
important to note the steep slopes in the graph at around 37 seconds shows that a monoprotic
acid releases one proton per molecule.

Figure 6:
HCl Trial 3
23
Temperature ( °C)

22.5

22

21.5

21
0 10 20 30 40 50 60 70
Temperature (seconds)

Figure 6 shows the graph of the third HCl trial. This graph is temperature (in degrees Celsius)
vs. time (in seconds). The graph was created in excel using the data that was exported from the
computer program used in lab. As a side note, the graph that was produced in lab was a lot
smoother, which could have been affected from changing the program that graphed the data. It is
important to note the steep slopes in the graph at around 37 seconds shows that a monoprotic
acid releases one proton per molecule.
Table 4 shows the initial temperature the malonic acid in the Dewar flask, the final temperature
after the NaOH solution was added, and the difference between the final and initial temperatures.
It also shows the second initial temperature (the steady temperature after the first amount of
NaOH solution was added), the second final temperature (the stabilized temperature after the
second amount of NaOH solution was added) and the differences between the second final
temperature and the second initial temperature. Below shows all three malonic acid trials and the
temperatures were recorded from the computer, using the digital thermometer probe that came
with the Dewar flask.
Table 4:
Temperatures of Malonic Acid Solution Trials
Initial1 Final1 Difference in Inital2 Final2 Difference
Temperature Temperature Temperatures Temperature Temperature (Final2-
in the Dewar in the Dewar (Final1 – in the Dewar in the Dewar Initial2)
Flask Flask Inital1) Flask Flask
(Malonic (Malonic Malonic (Malonic
Acid) Acid + Acid + Acid +
NaOH1) NaOH1) NaOH1 +
NaOH2)
Malonic 21.3 °C 22.1 °C 0.8 °C 22.1 °C 22.8 °C 0.7 °C
Acid
Trial 1
Malonic 21.4 °C 22.2 °C 0.8 °C 22.2 °C 22.9 °C 0.7 °C
Acid
Trial 2
Malonic 21.5 °C 22.3 °C 0.8 °C 22.3 °C 23.0 °C 0.7 °C
Acid
Trial 3

Figure 7:
Malonic Acid Trial 1
23
Temperature (°C)

22.5

22

21.5

21
0 20 40 60 80 100 120
Time (seconds)
Figure 7 shows the graph of the first malonic acid trial. This graph is temperature (in degrees
Celsius) vs. time (in seconds). The graph was created in excel using the data that was exported
from the computer program used in lab. As a side note, the graph that was produced in lab was a
lot smoother, which could have been affected from changing the program that graphed the data.
It is important to note the two steep slopes in the graph at around 43 seconds and 70 seconds
shows that a diprotic acid releases two protons per molecule.

Figure 8:
Malonic Acid Trial 2
23
Temperature (°C)

22.5

22

21.5

21
0 20 40 60 80 100 120
Time (seconds)

Figure 8 shows the graph of the second malonic acid trial. This graph is temperature (in degrees
Celsius) vs. time (in seconds). The graph was created in excel using the data that was exported
from the computer program used in lab. As a side note, the graph that was produced in lab was a
lot smoother, which could have been affected from changing the program that graphed the data.
It is important to note the two steep slopes in the graph at around 43 seconds and 78 seconds
shows that a diprotic acid releases two protons per molecule.

Figure 9:
Malonic Acid Trial 3
23.5

23
Temperature (°C)

22.5

22

21.5

21
0 20 40 60 80 100 120 140
Time (seconds)
Figure 9 shows the graph of the third malonic acid trial. This graph is temperature (in degrees
Celsius) vs. time (in seconds). The graph was created in excel using the data that was exported
from the computer program used in lab. As a side note, the graph that was produced in lab was a
lot smoother, which could have been affected from changing the program that graphed the data.
It is important to note the two steep slopes in the graph at around 57 seconds and 87 seconds
shows that a diprotic acid releases two protons per molecule.

Table 5 shows the heat capacity of the Dewar flask and the change in enthalpy. To find the
information below, we used the equations above. To fit our data a little better, we used the
following equation to find the heat capacity of the Dewar:
(Cpdewar+ρVH2O,ColdCp)(Tf-Tc)=(ρVH2O,AmbCp(Tamb-Tf)
Table 5:
Heat Capacity of the Dewar Flask and Change in Enthalpy
of a Monoprotic and Diprotic Acid
Heat Heat Change in Change in Change in Change in
Capacity Capacity Enthalpy Enthalpy Enthalpy Enthalpy
(J/K) Average (1st proton) Average (1st (2nd proton) Average
(J/K) proton) (2nd proton)
Water 437
Trial 1
Water 489
Trial 2
Water 499
Trial 3
Water 475
Average
HCl 855 J
Trial 1
HCl 808 J
Trial 2
HCl 760 J
Trial 3
HCl 808 J
Average
Malonic 380 J 333 J
Acid
Trial 1
Malonic 380 J 333 J
Acid
Trial 2
Malonic 380 J 333 J
Acid
Trial 3
Malonic 380 J 333 J
Acid
Average

Table 6 shows the error analysis of this experiment. The percent error was found by accounting
the equipment error and recording the total error in that section of the experiment in percent
error. For example, when calculating the concentration of NaOH, we have an error associated
with the buret and an error associated with weighing the KHP.
Table 6:
Error Analysis
% Error
Concentration of NaOH 1.2%
Concentration of HCl 1.5%
Concentration of Malonic Acid 0.8%
Temperature Recorded by the Dewar 2.1%
Calculated Heat Capacity 2.6%
Calculated Change in Enthalpy 3.2%

Discussion

When performing this experiment, it is important to recognize that you are dealing with a
chemical reaction and what variables can affect the chemical reaction. In order to better
understand this, it is a good idea to look at the basis, which is the first law of thermodynamics.
The first law of thermodynamics states that the change in internal energy is equal to the heat
transferred into the system minus the work done by the system. [4]

However, since the Dewar flask is acting as an adiabatic system, then there cannot be any
heat losses or gains between the system and the surroundings. That being said, it is important to
note that the change in temperature is proportional to the quantity of heat released. We can
convert the change in temperature to the change in heat if we know the heat capacity of the
calorimeter (found using ice water). The equation used to calculate the heat capacity is
mentioned in the introduction section as well as in the caption of Table 5. Once the heat capacity
was calculated, we can then use that value to calculate the change in enthalpies for the
monoprotic and diprotic acids.

Using the theories and equations mentioned in the introduction, once you know the
change in temperature before and after the reaction, you can basically plug and chug your results
into the equations to get the heat capacity and the change in enthalpies. However, we can take a
closer look at our change in enthalpies calculated and the graphs obtained from the reactions. As
you can see from the all of the graphs above, when the reaction took place there was a positive
spike/increase in temperature of the system. When the temperature increases, it means that the
reaction is endothermic. However, if the overall system temperature would decrease, then that
would mean that the reaction was endoscopic. Now, if you look at all of the calculated change in
enthalpies, they are all positive. As you can read in any physical chemistry book, a positive
enthalpy indicates an endothermic process.
Conclusion

This experiment shows how the change in enthalpy changes when comparing a
monoprotic acid with a diprotic acid. As you can see from the graphs obtained in lab, the trend of
the graphs follows the predicted trend. For a monoprotic acid, the graph should begin at a steady
temperature and when the calculated amount of base is added there should be an immediate spike
in the graph and then it should level out at a higher temperature. For the diprotic acid, the graph
begins the same with a levelled starting temperature, then when the first amount of base added,
the temperature will spike and then level out at a higher temperature. When the final amount of
base is added to the diprotic acid, there is one more spike in temperature and then it levels out
again. This trend is explained in Garland, but it is also explained in a lot of other book and online
resources. [6] Once we made all of our calculations, we found the heat capacity of the calorimeter
which has an average of 475 J/K. Once we knew the heat capacity of the calorimeter, we were
then able to calculate the change in enthalpy of the monoprotic acid and the diprotic acid. The
diprotic acid has two changes of enthalpies, one for the first proton that is released and the other
for the second proton that is released. The average change in enthalpy for the monoprotic acid is
808 J, the average change in enthalpy for the first proton of the diprotic acid is 380 J, and the
average change in enthalpy for the second proton of the diprotic acid is 333 J. When calculating
the change in enthalpy of the diprotic acid, we only had to calculate the results for one set of data
since all the trials gave the same change in temperature.

When looking at the data, is important to consider many concepts of thermodynamics to

get the full picture of what is going on. All of the enthalpies are positive, which indicates that
they are all endothermic reactions and heat is absorbed by the system. This concept matches with
our data, because there is an increase in temperature when the reaction takes places, which also
indicated that heat is absorbed by the system, therefore it is an endothermic reaction. It is
important to recognize that you a chemical reaction is happening when you react the monoprotic
and diprotic acid with the bases and the various factors that can change how the reaction takes
place.

For future work, I would like to try different monoprotic acids and diprotic acids to see
how they compare to each other. I would also like to try a triprotic acid to see how the change in
enthalpy after the third proton was released compares to the two prior ones. I assume that once
the third proton is released that enthalpy change would be smaller than the second one, but I
would like to see test the results personally. I am also curious on whether the total enthalpy
change would be larger or smaller for the triprotic acid when compared to the monoprotic and
diprotic acids. When using the ice water for the calorimeter, I would like to have the water sit for
a long time before beginning the experiments. Even though we waited for about ten minutes for
the ice water to reach equilibrium and have the temperature stabilize, each trial had a different
starting temperature.
References

[1] L. (2016, July 21). Polyprotic Acids & Bases. Retrieved November 3, 2017.

[2] Helmenstine, A. M., Ph.D. (2017, September 01). Examples of Chemical Change We Experience Every
Day. Retrieved November 10, 2017.

[3] The Editors of Encyclopaedia Britannica. (2016, April 04). Heat of Reaction. Retrieved November 10,
2017.

[4] Hall, N. (2015, May 5). First Law of Thermodynamics. Retrieved November 10, 2017, from
https://www.grc.nasa.gov/www/k-12/airplane/thermo1.html

[5] L. (2017, February 09). Heat Capacity. Retrieved November 12, 2017.

[6] Garland, C. W., Shoemaker, D. P., & Nibler, J. W. Experiments in Physical Chemistry. McGraw-Hill
Higher Education, 2009.