Final Sophomore Research Paper

The Effect of Different Molarities of
Hydrochloric Acid on the Erosion of Calcium Carbonate
Brendan Cairney, Tyler Doral, and Victoria Kovac
Macomb Mathematics Science Technology Center
Honors Chemistry 10
10B
Mrs. Hilliard/ Mr. Supal/ Mrs. Dewey
23 May 2018
Cairney - Doral - Kovac
Table of Contents
Introduction…………………………………………………………………....…………1
Review of Literature……………………………………....………...……….………….3
Problem Statement………………………………...………………..…..……………...8
Experimental Design…………………………………………………………………….9
Data and Observations………………………………………………………………...11
Data Analysis and Interpretation……………………………………………………...24
Conclusion………………………………………………………………………………35
Acknowledgements…………………………………………………………………….38
Appendix A: Sample Calculations…………………………………………………….39
Works Cited………………………………………....…………………………………..41
1
Introduction
Five billion dollars worth in damages occurs in the midwest and eastern United
States annually due to acid rain (New York Times 2). Ranging from buildings to
agriculture, acid deposition continues to affect modern society, even after hitting its
peak in the 1980’s. Through continual research, more information has been gained and
regulations have been put in place to help lower the acidity of rain. Given the
significance of acid deposition, the objective of this research was to determine the effect
of acid on limestone. The research focused on determining the relationship between
the molarity of hydrochloric acid, HCl, on the erosion of calcium carbonate, CaCO3.
In the experiment, chalk was used in replacement of limestone. Each piece of
chalk was massed and then put into a HCl acid solution with a molarity of three, or six,
for two minutes. These molarities represented the most extreme acidity found in rain
from the eastern and western regions of the United States. The chalk remained in an
incubator to dry for 24 hours and was massed on an analytical scale to calculate the
percent mass loss. Two separate matched pairs t- tests were used to analyze the data.
The objective was to observe a higher percent mass loss in chalk exposed to the acid
with the higher concentration compared to chalk exposed to water and a lower
concentration of acid.
Acid rain affects the industrial world in conjunction with nature. Acid deposition
damages buildings and structures by deteriorating the stone or metal that is exposed to
the elements. Metals, limestone, and marble are commonly used as building materials
2
that are exposed to rain. These materials contain calcium carbonate or calcium-based
compounds, which react and deteriorate upon contact with acid rain. Agriculture also
experience major repercussions due to acid deposition. Limestone, which naturally acts
as a pH buffer in the soil, reacts and ionizes with the acid rain. The reaction causes
limestone to erode and the soil no longer has compounds to neutralize the acidity.
Crops and plants cannot grow as well in acidic environments, causing financial stress
and crop shortages for farmers.
The purpose of this experiment observed hydrochloric acid reacting with calcium
carbonate, a main component of both chalk and limestone. Data collected from this
experiment can be used to help architects decide the material of the buildings that they
make. The research could also benefit farmers advocate for a cleaner atmosphere
because acid rain damages and prevents growth of crops. Finally, it would help the
scientific community by further validating claims on the various detrimental effects of
acid rain.
Acid rain continues to prove a threat to modern day America due to the
hazardous effects of acid rain, so progression in modern research continues to be
critical. New, valid data helps build a strong argument to keep emission regulations in
place and prevent a more acidic atmosphere.
3
Review of Literature
Acid rain was a major environmental phenomenon of the 1980s. Factories
released mass amounts of sulfur and nitric oxides, causing the rain to become acidic.
Acid deposition degrades limestone in soil, which affects the growth of agriculture. The
purpose of this research experiment was to find the effect of hydrochloric acid, HCl, on
calcium carbonate, CaCO3, in order to simulate the corrosion that occurs on limestone
from acid deposition. Past and current research can further validate the destructive
effects that carbon emissions have on the world.
Figure 1. pH Scale (“Britannica”)
The rate at which erosion of limestone occurs depends on the pH, the potential of
hydrogen. It is the measurement of whether a solution is acidic or basic determined by
the measure of the hydrogen ion concentration (“What Is PH”). Solutions are rated on a
scale from one to 14, one being the most acidic and 14 being the most basic. A pH
reading less than seven indicates an acidic solution, while a reading more than seven is
considered a basic solution--solutions with a pH reading of seven are neutral.
Acid rain is caused by a chemical reaction that occurs when sulfur dioxide and
nitrogen oxides are released into the air. These substances rise into the atmosphere,
4
where they react with water, oxygen, and other chemicals to form a more acidic
pollutant, known as acid rain. Sulfur dioxide and nitrogen oxides dissolve easily in water
and can be carried far by the wind. This results in the widespread problem of acid
deposition (Gordon).
Figure 2. Annual pH in 1994 and 2006 (“Britannica”)
Figure 2, above, displays the pH levels of acid rain in 1994 and 2006 in the
United States. The east has lower pH levels of around four, while the west is higher with
levels around five. The east, which is much more industrialized, has much lower pH
levels since power plants and transportation vehicles release the majority of sulfur
dioxides when they burn fossil fuels (“What Causes”). There is a visual increase of the
lighter color and green color as opposed to a orange and yellow color as time
progresses from 1994 to 2006. This indicates that the pH of rain has increased and
become more basic, which is due to the Acid Rain Program, who requires major
emission reductions of sulfur dioxide, SO2, the primary precursor of acid rain (“Acid Rain
Program”). The act helped reduce acidity in rain water by reducing man-made
emissions. Based on the above pH levels, three molar and six molar hydrochloric acid
5
were used. The 6 M HCl acid represents the 4 pH on the east coast and the 3 M HCl
acid represents the 5 pH on the west coast. Although these molarities do not directly
correlate with pH’s of 4 and 5, they represent extremities that could occur if the
atmosphere became more acidic.
Limestone is commonly found throughout nature. Limestone frequently acts as
a buffer in soil that neutralizes acid rain. When acid rain, however, becomes
increasingly acidic, limestone is eroded faster than it naturally would. Due to this, water
bodies with calcium carbonate deficient soil are highly susceptible to a change in pH
levels (“Britannica”). The accelerated process of the erosion of limestone also affects
agriculture, which cannot grow as well in acidic soil. The chemical reaction between
calcium carbonate and hydrochloric acid demonstrates how limestone erosion occurs.
CaCO3 (s) + HCl (aq) → CaCl2 (aq) + CO2 (g) + H 2 O (l)
As shown in the chemical equation above, calcium carbonate comes into contact
with hydrochloric acid and ionizes into calcium chloride, carbon dioxide, and water.
When the carbon dioxide gas, water, and the calcium chloride becomes a product of the
reaction, the mass of the chalk decreases. The hydrochloric acid ionizes 100 percent,
due to the fact that it is a strong acid, it has a high H⁺ content. When the H⁺ content is
high, the pH goes down, making the solution more acidic, much like acid rain itself.
Various experiments have been conducted to deepen the understanding of the
effects of acid rain on carbonate stone structures. An experiment conducted by
Ryszard Kryza used three different types of rocks (travertine, limestone, and marble) to
test how they withstand weather elements. The acid rain was represented with sulfuric
6
acid, H2SO4, hydrochloric acid, HCl, nitric acid, HNO3, acetic acid, CH3COOH, and a
mixture of all these acids. In this experiment, only hydrochloric acid, HCl, were used.
Figure 3. Travertine Erosion (Kryza)
Figure 3, above, displays a cube of travertine before (left) and after (right) the
acid treatment. The rocks, cut into 2 x 2 x 2 cm cubes were dipped and left in 80 mL of
the acidic mixtures and taken out after a given amount of time. Deterioration that
resulted from the hydrochloric acid is clearly visible on the corners.
Another experiment, conducted by Philip A. Baedecker, found similar results.
Although the experimental design differed from Kryza’s design, he concluded that an
increase in concentration of acid leads to a greater concentration of limestone particles
(Baedecker). A greater concentration of limestone particles indicates an increase of
products, which is an increase of mass loss.
Through the knowledge of all these experiments, this research utilized a few of
these methods. Chalk represented limestone in the experiment due to chalk’s main
component being calcium carbonate and limestone being a sedimentary rock
comprising of at least 80% calcium carbonate (“Limestones”). Although nitric acid,
HNO3, and sulfuric acids, H2SO4, are the main components of acid rain, this research
7
experiment used hydrochloric acid to replicate acid rain. Since both hydrochloric acid
and nitric acid are monoprotic acids, it is acceptable to use HCl in place of HNO3.
Differing molarity levels of three and six were be used. The length of time in which the
chalk was exposed to HCl acid was modeled after Baedecker’s experiment, which was
two minutes. The chalk was cut 2 cm in length to model the 2 x 2 x 2 cm blocks of
limestone in Kryza’s experiment. The mass of the chalk was measured before and after
being introduced to the hydrochloric acid solutions, and the percent mass lost was
calculated to represent the corrosion that occurs.

Δmass
%Δmassloss = massbef ore
× 100
To calculate the percent change in mass, the change in mass must be calculated
by subtracting the initial mass from the final mass in grams, which is then divided by the
mass of the chalk before. After this, it is multiplied by 100 to get the %𝛥massloss.
Overall, calcium carbonate is frequently found in the environment. It is the main
component of limestone and is commonly found in the soil. There are many negative
consequences of acid rain’s effect on calcium carbonate, and identifying what has the
greatest effects on it is of the utmost importance. Using previous research as a basis,
this experiment will find the effect of hydrochloric acid at different molarities on calcium
carbonate.
8
Problem Statement
Problem:
To determine the effect of three molar and six molar hydrochloric acid, HCl, on
the erosion of calcium carbonate, CaCO3.
Hypothesis:
The highest molarity of six of the hydrochloric acid, HCl, will produce the greatest
percent mass loss of the chalk, CaCO3.
Data Measured:
Each piece of chalk was massed in grams on an analytical scale before coming
in contact with the treatments. The mass, in grams, of the chalk was re-massed on the
same analytical scale after the treatment. The independent variable is hydrochloric acid,
HCl, at the molarities of three and six. These molarities represent the acidity from the
eastern and western regions of the United States at the most extremes. The dependant
variable is the percent mass loss. The volume, in liters, of the treatment remained
constant, as well as the time the chalk was exposed to the treatment (two minutes). Two
separate matched pairs t- tests will be used to analyze the data.
9
Experimental Design
Materials:
(134) 2 cm Chalk Sticks (1) 25 mL Graduated Cylinder
2 L of 3 M HCl Solution (1) Delta 15” Scroll Saw
2 L of 6 M HCl Solution (1) Funnels
(1) Analytical Scale 0.0001g Precision (1) 100 mL Beaker
() Weigh Boats (2) 12 Well Spot Plate
(1) 36℃ Incubator (1) Tongs
(1) TI‑Nspire CX handheld graphing
calculator
Procedure:
1. Measure a chalk stick into 2 cm in length and cut using an automatic saw.
2. Measure and record the initial mass of one stick of chalk to 0.0001 gram
precision using the analytical scale.
3. Take a picture of the chalk stick
4. Place piece of chalk in beaker.
5. Use the Ti-Nspire random integer generator function by typing Randint(1,2) to

randomize which acid will be used for the stick of chalk.
6. Measure 25 mL of hydrochloric acid solution with a molarity of 3 or 6, depending

on which one was chosen, using graduated cylinder and a funnel.
7. Pour the hydrochloric acid solution over the corresponding chalk stick.
8. Take out chalk piece using tongs after two minutes.
9. Place chalk stick on a 12 well spot plate with the corresponding trial number and
molarity. See Figure 2 for reference.
10. Place both 12 spot well trays in incubator set at 36 degrees celcius for 24
hours.
11. Remove the trays from the incubator.
12. Weigh and record the final mass of the chalk sticks in 0.0001 gram precision
using an analytical scale.
13. Take a picture of the chalk.
10
14. Repeat steps 1-13 until 67 trials of each molarity are complete.
Diagram:
Figure 4. Materials
Figure 4, above, shows the materials used for the experiment. Not pictured is the
15” scroll saw and analytical scale.
11
Data and Observations
This section includes the data produced in the experiment. It includes the mass
in grams of the chalk before and after being exposed to 3 M HCl acid and 6 M HCl acid.
The change in mass (in grams) was calculated by subtracting the mass after from the
mass before.
Data:
Table 1
Before and After Mass of Chalk in 3 Molarity HCl Acid
Before and After Mass of Chalk in 3 M
Mass Mass After
Trial # Before (g) (g) ∆Mass (g)
1 2.6247 1.6525 0.9722
2 2.4977 1.6066 0.8911
3 2.4714 1.4975 0.9739
4 2.6174 1.6915 0.9259
5 2.6790 1.6828 0.9962
6 2.9008 1.9646 0.9362
7 2.5932 1.4939 1.0993
8 2.6419 1.6313 1.0106
9 2.7991 1.9283 0.8708
10 2.8533 1.8642 0.9891
11 2.4939 1.3648 1.1291
12 2.6866 1.6621 1.0245
13 2.5930 1.7103 0.8827
14 2.4844 1.3449 1.1395
15 2.5462 1.3978 1.1484
16 2.6040 1.7857 0.8183
17 2.5496 1.7830 0.7666
18 2.6779 1.4452 1.2327
19 2.3746 1.1824 1.1922
20 2.7321 1.6807 1.0514
12

Mass Mass After
21 2.6291 1.5805 1.0486
22 2.4145 1.3118 1.1027
23 2.5557 1.4901 1.0656
24 2.6841 1.7169 0.9672
25 2.6413 0.8261 1.8152
26 2.3710 1.7915 0.5795
27 2.3729 1.3408 1.0321
28 2.5885 1.7675 0.8210
29 2.6180 1.5185 1.0995
30 2.6287 1.7566 0.8721
31 2.6582 1.4918 1.1664
32 2.7074 1.7502 0.9572
33 2.7820 1.8625 0.9195
34 2.5518 1.7110 0.8408
35 2.2493 1.4755 0.7738
36 2.5326 1.7038 0.8288
37 2.5845 1.6846 0.8999
38 2.6091 1.7142 0.8949
39 2.5058 1.3498 1.1560
40 2.3190 1.2312 1.0878
41 2.5704 1.3394 1.2310
42 2.4350 1.3344 1.1006
43 2.7833 1.8311 0.9522
44 2.4694 1.5495 0.9199
45 2.6854 1.4325 1.2529
46 2.4242 1.1517 1.2725
47 2.8740 1.8679 1.0061
48 2.5652 1.1860 1.3792
49 2.9318 2.0096 0.9222
50 2.5701 1.6907 0.8794
13

Mass Mass After
51 2.4074 1.6216 0.7858
52 2.5354 1.7296 0.8058
53 2.5767 1.6592 0.9175
54 2.4918 1.7035 0.7883
55 2.8103 1.9568 0.8535
56 2.3925 1.6584 0.7341
57 2.6808 1.8711 0.8097
58 2.5773 1.6752 0.9021
59 2.6207 1.8245 0.7962
60 2.7968 1.8476 0.9492
61 2.5998 1.8398 0.7600
62 2.4611 1.6517 0.8094
63 2.3561 1.6362 0.7199
64 2.6045 1.5796 1.0249
65 2.7183 1.642 1.0763
66 2.6475 1.4836 1.1639
67 2.6168 1.7467 0.8701
Average: 2.5946 1.6114 0.9800
Table 1, above, shows all of the chalk that was tested during the trials using the 3
M HCl solution. It shows the trial number, the initial weight, the final weight and the
mass lost.
Table 2
Before and After Mass for 6 M HCl Acid
Mass Mass After
1 2.6925 2.0776 0.6149
2 2.6330 1.1532 1.4798
3 2.4638 2.2045 0.2593
14

Mass Mass After
4 2.7976 1.6456 1.1520
5 2.5343 1.4673 1.0670
6 2.7289 1.7217 1.0072
7 2.7724 1.6603 1.1121
8 2.6414 1.4928 1.1486
9 2.7451 1.7350 1.0101
10 2.4464 1.2262 1.2202
11 2.6700 1.8166 0.8534
12 2.5592 1.3197 1.2395
13 2.5883 1.4570 1.1313
14 2.6277 1.3202 1.3075
15 2.4147 1.0916 1.3231
16 2.6944 1.7954 0.8990
17 2.7166 2.3427 0.3739
18 2.5265 1.8279 0.6986
19 2.6421 1.5191 1.1230
20 2.6048 1.8989 0.7059
21 2.4611 1.3810 1.0801
22 2.5515 1.6678 0.8837
23 2.4695 1.2712 1.1983
24 2.4495 1.5511 0.8984
25 2.5409 2.2101 0.3308
26 2.6245 1.4376 1.1869
27 2.6022 1.5549 1.0473
28 2.7409 1.9035 0.8374
29 2.7460 1.9347 0.8113
30 2.6785 1.4890 1.1895
31 2.7233 1.6050 1.1183
32 2.4777 1.4176 1.0601
33 2.4605 2.2707 0.1898
15

Mass Mass After
34 2.5126 2.4002 0.1124
35 2.5141 1.2328 1.2813
36 2.4595 1.6399 0.8196
37 2.6267 1.4599 1.1668
38 2.3956 1.1099 1.2857
39 2.5655 1.0028 1.5627
40 2.5473 1.1622 1.3851
41 2.7174 1.2658 1.4516
42 2.7017 1.2624 1.4393
43 2.5592 1.4153 1.1439
44 2.8389 0.9637 1.8752
45 2.7064 1.1237 1.5827
46 2.4215 1.8627 0.5588
47 2.7993 1.5384 1.2609
48 2.4147 1.9124 0.5023
49 2.4192 2.3405 0.0787
50 2.4676 2.2432 0.2244
51 2.6320 2.5292 0.1028
52 2.7632 2.5623 0.2009
53 2.7201 2.4320 0.2881
54 2.6651 2.0287 0.6364
55 2.4619 1.6552 0.8067
56 2.7779 1.7563 1.0216
57 2.6011 1.7156 0.8855
58 2.8342 1.9282 0.9060
59 2.4463 1.5390 0.9073
60 2.8797 1.8870 0.9927
61 2.9821 2.3360 0.6461
62 2.3690 1.3912 0.9778
63 2.5373 1.9876 0.5497
16

Mass Mass After
64 2.4735 2.3739 0.0996
65 2.5337 1.3377 1.1960
66 2.6053 1.3433 1.2620
67 2.3988 1.3779 1.0209
Average: 2.5976 1.6595 0.9381
Table 2 shows all of the chalk that was tested during the trials using the 6 M HCl
solution. It shows the trial number, the initial weight in grams, the final weight, and the
mass lost.
Table 3
Chalk in Water Trial Before and After Mass
Before and After Mass of Chalk in
Water
Mass Before Mass After
Trial # (g) (g) ∆Mass (g)
1 2.5482 2.5349 0.0133
2 2.9620 2.9449 0.0171
3 2.5334 2.5230 0.0104
4 2.5872 2.5417 0.0455
5 2.6845 2.6712 0.0133
6 2.3536 2.3481 0.0055
7 2.8373 2.8252 0.0121
8 2.9106 2.9044 0.0062
9 2.4617 2.4511 0.0106
10 3.0184 3.0130 0.0054
11 2.4684 2.4441 0.0243
12 2.5408 2.5181 0.0227
Average: 2.6588 2.6433 0.0155
17
Table 3, above, shows all of the chalk that was tested during the trials using the
water control. It shows the trial number, the initial weight in grams, the final weight, and
the mass loss, which is the change in mass.
Observations:
This section includes observations made during the 3 M and 6 M trials. The
researchers that conducted each trial were recorded along with notable changes in
each trial.
Table 4
Chalk in 3 M HCl Acid Trial Observations
Trial Date Observation
New 3 M HCl acid solution was made. Researcher #2 conducted the
1 4/24/18 trial.
2 Researcher #1 conducted the trial.
5 Researcher #1 conducted trial.
6 Trial conducted by researcher #3.
9 Same researchers as trial 8.
11 4/25/18 Researcher #2 conducted the trial.
Left in room temperature for 24 hours, before being placed in
14 incubator for 24 hours. Researcher #1.
Left in room temperature for 24 hours,before being placed in
15 incubator for 24 hours. Same researcher setup.

18

20 Research #1 conducted trial.
The timer was set to the wrong time--ended 20 seconds early. Same
22 researcher setup.
23 Conducted by researcher #1.

Trial conducted by researcher #2. Left in for about 35 seconds
25 longer than intended.
31 4/26/18 Trial conducted by researcher #3.
33 4/30/18 Trial conducted by researcher #3.
35 Old solution was used by researcher #2.
36 Old solution was used. Same researcher setup as trial 35.
37 New 3 M HCl acid solution used (made by researcher #3).
Chalk was dropped onto the table by researcher #2 after being
38 exposed to 3 M solution.
45 30mL of HCl acid solution was poured by researcher #3.
19

47 Same researcher set up trial 46.
49 5/1/18 Left in incubator dried for 24 hours. Researcher #3.
50 Left in incubator dried for 24 hours. Researcher #1.
Left in incubator dried for 24 hours. Same researcher setup as trial
51 #50.
55 Left in incubator dried for 24 hours. Research setup from trial 53.
57 Research #1 did 3 M HCl acid trial.
58 Researcher #3.
61 Researcher #1.
65 Researcher #3.
67 Researcher #2.
Table 4, above, shows all of the observations throughout the duration of the
experiment of the chalk being exposed to the 3 M HCl acid.
Table 5
Chalk in 6 M HCl Acid Trial Observations
New 6 M HCl acid solution was made. Researcher #1 conducted the
1 4/24/18 trial.
2 Researcher #2 did the trial.
3 6 M chalk appeared discolored. Research #3 did the trial.
20

4 Researcher #1 conducted trial.
7 Researcher #3.
10 Research #3 did trial.
11 4/25/18 Research #1 conducted trial.
Left in room temperature for 24 hours, before being placed in
14 incubator for 24 hours. Researcher #1.
Left in room temperature for 24 hours,before being placed in
15 incubator for 24 hours. Same researcher setup.
16 Researcher #3.
19 Researcher #2 did trial.
20 Research #1 conducted the trial.
21 4/26/18 Research #1 conducted the trial.
The timer was set to the wrong time and ended 20 seconds early.
22 Same researcher setup.
26 Researcher #1.
31 4/26/18 Researcher #3.
33 4/30/18 6 M (researcher #3) barely bubbled.
21

34 6 M (researcher #2) barely bubbled.
35 Old solution was used. Researcher #1.
36 Old solution was used. Same researcher setup as trial 35.
37 New 6 M HCl acid solution used (made by researcher #3).
38 Researcher #1.
44 6 M solution was left in 30 seconds longer. Research #1.
30mL of each solution were poured. Trial conducted by researcher
45 #2.
46 6 M did not react (bubble). Researcher #1.
49 5/1/18 3 M and 6 M left in incubator dried for 24 hours. Researcher #3.
3 M and 6 M left in incubator dried for 24 hours. Researcher #2
50 conducted trial.
3 M and 6 M left in incubator dried for 24 hours. Did not bubble. Same
51 researcher setup as trial #50.
3 M and 6 M left in incubator dried for 24 hours. 6 M HCl acid did not
52 bubble.
3 M and 6 M left in incubator dried for 24 hours. Researcher #2 did 6
53 M.
54 3 M and 6 M left in incubator dried for 24 hours. Researcher #3.
3 M and 6 M left in incubator dried for 24 hours. Research setup from
55 trial 53.
56 3 M and 6 M left in incubator dried for 24 hours. Researcher #1.
58 Researcher #3.
59 Research #3.
60 Research #1 conducted the trial.
22

63 5/2/18 6 M (researcher #1) showed no signs of reaction.
64 6 M (researcher #2) showed little signs of reaction.
Table 5, above, shows all of the observations throughout the duration of the
experiment. Notable trials include trials 33, 34, 46, 40 through 52, 63, and 64 because
the 6 M solution did not visibly react with the chalk.
Figure 5. Before and After Pictures for Chalk Exposed to 3 Molar HCl Acid
Figure 5, above, shows a picture of chalk before being submerged in any of the 3
M HCl acid solution and after being set in a 36 degree celsius incubator for 24 hours.
23
Figure 6. Before and After Pictures for Chalk Affected by 6 Molar HCl Acid
Figure 6, above, shows a picture of chalk before being submerged in any of the 6
M HCl acid solution and after being set in a 36 degree celsius incubator for 24 hours.
24
Data Analysis and Interpretation
The data collected is reliable and valid because it meets all the requirements of
control, randomization, and replication. A control of water was used to eliminate the
possibility of water solely affecting the percent mass loss, which helps reduce
confounding. The experiment was randomized in several ways to reduce bias and
create similar trials. The chalk was randomly assigned to a trial number and the
molarity of acid was randomly chosen. To eliminate the possibility of human error,
different researchers were randomly selected to do each trial. The experiment was
conducted 67 times for both the 3 M and 6 M acids to ensure accurate data. According
to the Law of Large Numbers, as the number of trials increases, the sample mean, x ,
approaches the population mean, μ . By repeating the trials, variability was reduced and
the sample mean approached the true population mean.
The analysis performed on this experiment was a matched pairs t- test. This is
appropriate because the weight of the chalk was recorded before and after being
exposed to the hydrochloric acid, HCl. A matched pairs t test was then performed on
the average of the percent mass loss of each trial, which is calculated using before and
after data. All three conditions for a matched pairs t- test were met. A simple random
sample was conducted by randomly selecting chalk sticks. The number of trials was
greater than 30, so the sampling distribution of the data is assumed to be normal. The
population of all chalk sticks is greater than ten times the sample of 67 chalk sticks.
Table 6
Chalk in 3 and 6 Molarity HCl Acid Percent Mass Loss
Trial # 6 M Chalk 3 M Chalk
25
Percent Mass Loss

1 22.84% 37.04%
2 56.20% 35.68%
3 10.52% 39.41%
4 41.18% 35.37%
5 42.10% 37.19%
6 36.91% 32.27%
7 40.11% 42.39%
8 43.48% 38.25%
9 36.80% 31.11%
10 49.88% 34.67%
11 31.96% 45.27%
12 48.43% 38.13%
13 43.71% 34.04%5
14 49.76% 45.87%
15 54.79% 45.10%
16 33.37% 31.42%
17 13.76% 30.07%
18 27.65% 46.03%
19 42.50% 50.21%
20 27.10% 38.48%
21 43.89% 39.88%
22 34.63% 45.67%
23 48.52% 41.70%
24 36.68% 36.03%
25 13.02% 68.72%
26 45.22% 24.44%
27 40.25% 43.50%
28 30.55% 31.72%
29 29.54% 42.00%
6 M Chalk 3 M Chalk
Trial # Percent Mass Loss
26
30 44.41% 33.18%
31 41.06% 43.88%
32 42.79% 35.35%
33 7.71% 33.05%
34 4.47% 32.95%
35 50.96% 34.40%
36 33.32% 32.73%
37 44.42% 34.82%
38 53.67% 34.30%
39 60.91% 46.13%
40 54.38% 46.91%
41 53.42% 47.89%
42 53.27% 45.20%
43 44.70% 34.21%
44 66.05% 37.25%
45 58.48% 46.66%
46 23.08% 52.49%
47 45.04% 35.01%
48 20.80% 53.77%
49 3.25% 31.46%
50 9.09% 34.22%
51 3.91% 32.64%
52 7.27% 31.78%
53 10.59% 35.61%
54 23.88% 31.64%
55 32.77% 30.37%
56 36.78% 30.68%
57 34.04% 30.20%
58 31.97% 35.00%
59 37.09% 30.38%
6 M Chalk 3 M Chalk
Trial # Percent Mass Loss
27
61 21.67% 29.23%
62 41.27% 32.89%
63 21.66% 30.55%
64 4.03% 39.35%
65 47.20% 39.59%
66 48.44% 43.96%
67 42.56% 33.25%
Average: 35.38% 37.89%
Table 6 displays the percent mass loss for the chalk in 3 M HCl acid and in 6 M
HCl acid. The chalk exposed to 6 M HCl acid in trials 3, 17, 25, 33-34, 49-52, and 64
have a significantly lower percent mass loss compared to the average percent mass
loss. The chalk exposed to 3 M HCl acid in trial 25 also has a significantly higher
percent mass loss compared to the average percent mass loss. The calculations for
percent mass loss are demonstrated in Figure 16 in Appendix A.
28
Figure 7. Before and After Mass of Chalk in 3 M HCl Acid
Figure 7, above, shows the masses of the chalk before and after being
submerged in three molar hydrochloric acid. It can be seen that for the 3 M HCl chalk,
there is no overlap between the mass before and the mass after, which validates how
chalk loses mass after being exposed to acid. There is also a bigger spread of data,
which means that there is more variation of the data for the mass after as opposed to
the mass before. Finally, there is an outlier of 0.8261 grams for the mass after,
resulting in an increase of the standard deviation from 0.2035 to 0.2242.
Figure 8. Before and After Mass of Chalk in 6 M HCl Acid
Figure 8, above, shows the masses of the chalk before and after being
submerged in six molar hydrochloric acid. It can be seen that for the 6 M HCl chalk,
29
there is some overlap between the mass before and the mass after. There is also a
bigger variation of the data for the mass after as opposed to the mass before. Overlap
between the two box plots occurs, which could be caused by one of the heavier chalk
pieces not being eroded by the hydrochloric acid as much as one of the lighter chalk
pieces. There are no outliers for these two data sets.
Figure 9. Mass of Chalk in Water Control
Figure 9, above, displays the box plot for the percent mass loss of water. The
data is compact, with the standard deviation being 0.0042, and has little variability due
to water having a small effect on the change in mass. There appears to be one outlier
of 0.0176; however, it is still relatively small and does not appear to affect overall validity
of the water control. The outlier, however, pulls the mean toward the right, making the
boxplot right-skewed. This boxplot has a different scale than Figure 10 because the
standard deviation and spread of the water control data is significantly smaller than the
30
data from the 3 and 6 M HCl acid. When the boxplot is on the same scale, as
demonstrated in Figure 10, it is difficult to see and analyze.
Figure 10. Comparing 3 M, 6 M, and Water Percent Mass Loss
Figure 10, above, shows the percent mass loss of chalk when submerged in the
three molar HCl, 6 M HCl, and water. The water, which acted as the control, had almost
no variance, and all of its data was lower than the 3 M and 6 M data. This verifies the
data because it demonstrates how the water had little effect on the overall corrosion of
calcium carbonate. Figure 9 displays the water control numbers in detail. The six molar
and three molar data have a 100% overlap due to the large spread of the 6 M data. The
six molar data has a lower mean compared to the three molar data; however, the six
molar data has a higher median. This means that 50% of the the chalk in 6 M HCl acid
had a higher percent mass loss than the chalk in 3 M HCl acid. This is due to variability
that occured in the mass of the chalk after being exposed to 6 M HCl acid. The three
31
molar boxplot appears to be right-skewed, while the six molar boxplot is slightly
left-skewed. The three molar data is right-skewed because the mean is pulled to the
right due to the outlier.
Ho : μ = 0
Ha : μ > 0
Figure 11. Null and Alternative Hypothesis
Figure 11, above, shows the null and alternative hypotheses for the experiment.
The null hypothesis, H o , states that the population mean is equal to zero. This means
that there is no percent change in mass. The alternative hypothesis, H a , is that mu, μ ,
is greater than zero. This hypothesizes that the true population mean is greater than
zero, indicating that a percent change in mass will occur.
Figure 12. Chalk in 3 M HCl Acid t Test Results
Figure 12, above, is a visual representation showing the t- value of 41.9946 for
the 3 M chalk percent mass loss. The greater the magnitude of t, either positive or
negative, the greater the evidence against the null hypothesis, which states no
32
significant difference between the mass before and after. Because the t-value is large,
there is significant evidence against the null hypothesis. The p-value is also included in
this graph, but because of how small it is, it cannot be seen. This figure also displays
the calculations for a one-sample t test using the 3 M data. The n represents the
number of trials and x represents the mean of the sample data. Degrees of freedom,
df, is the sample size minus one.The number of standard deviations away from the null
hypothesis mean, zero, is represented by the letter t. The sx represents the relatively
small standard deviation of the data, resulting in increased significance of the test. The
null hypothesis is rejected because the p-value of 1.2157⨉ 10−49 is less than the alpha
level of 0.05. There is evidence that hydrochloric acid accelerates the erosion of
calcium carbonate solids. There is almost no chance of getting a sample mean of
0.3789 if the null hypothesis is true by chance alone. Evidence shows the chalk did not
erode by chance alone.
est Results
Figure 13. Chalk in 6 M HCl acid t T
33
Figure 13, above, is a visual representation of the t-value for the 6 M chalk
percent mass lost. Although the t-value of 18.4471 is smaller than the t- value of
41.9946 for the 3 M chalk mass loss, there appears to be significant evidence against
the null hypothesis due to its large distance from zero. The p- value is also included in
this graph, but because of how small it is, it cannot be seen. This figure also shows the
t-value, sample mean, number of trials, and degrees of freedom for the six molar chalk
data. All symbols are denoted in Figure 12. The standard deviation of 0.1570 is greater
than the standard deviation of 0.0739 from the 3 M results, which means that their is
greater variability for the 6 M t test. This results in a higher p-value. The null
hypothesis is rejected because the p-value of 4.7850⨉10-28 is less than the alpha level
of 0.05. There is evidence that hydrochloric acid accelerates the erosion of calcium
carbonate solids. There is almost no chance of getting a sample mean of 0.3538 if the
null hypothesis is true by chance alone. This means that there is significant evidence
that hydrochloric acid plays a role in the erosion of calcium carbonate.
34
Conclusion
The purpose of this experiment was to determine the effect of the molarity of
hydrochloric acid, HCl, on the erosion of chalk, which is mainly composed of calcium
carbonate (CaCO3). The hydrochloric acid was intended to simulate the effect of acid
rain on limestone (also mainly composed of calcium carbonate). It was hypothesized
that six molar hydrochloric acid, HCl, would produce a greater percent mass loss of the
chalk, CaCO3 compared to 3 M hydrochloric acid.
The hypothesis was rejected because the average percent loss of CaCO3 in

grams for chalk in 6 M HCl acid, 35.38%, was lower than the average percent loss in
grams of chalk exposed to 3 M HCl acid, 37.89%. This is due to the inconsistency and
range of the mass of the chalk after being exposed to the 6 M HCl acid. This acid did
not visually react with the chalk in trials 33, 34, 49, 50-52, and 64. Although the cause
of this is unknown, the average percent mass loss in grams was lowered.
The null hypothesis stated that the percent mass loss would be zero, suggesting
that the chalk would not lose mass after being exposed to hydrochloric acid. The null
hypothesis was rejected, however, due to a p-value of 1.2157⨉10-49 for chalk exposed
to 3 M HCl acid and 4.7850⨉10-28 for chalk exposed to 6 M HCl acid. This is lower than
the alpha level of 0.05 which means there is almost no chance that the chalk lost mass
by chance alone--there is significant evidence suggesting that HCl acid accelerates the
erosion of CaCO3.
The reaction between hydrochloric acid and calcium carbonate results in calcium
chloride, water, and carbon dioxide being formed. The calcium carbonate ionizes into
35
gas, liquids, and salts, which separate from the carbonate stone and dissolve into
solution. Due to this, the limestone rock becomes smaller as the hydrochloric acid
continues to react and ionize. An experiment conducted by Ryszard Kryza also
concluded that a higher concentration of acid resulted in a higher final mass loss of the
carbonate rock (Kyrza 8). It was also found an “increase in calcium ion particles when
the hydrogen ion concentration increased” (Baedecker 3). Both authors concluded that
increased acidity leads to increased mass loss in limestone. Results from this
experiment do not agree with current research because 3 M HCl acid eroded the chalk
more than the 6 M HCl acid due to lurking variables.
Although the experiment created valid data, several errors occurred. A major
error included the chalk absorbing the acid. The chalk was indirectly exposed to the
hydrochloric acid for a longer time since it was not possible to remove the acid
absorbed by the chalk after the timed two minutes. This led to an overall higher percent
mass loss for the chalk. The chalk should be sprayed with water after being taken out
of the solution to eliminate excess acid. The precaution would make sure the chalk is
only exposed for the intended two minute interval in future research. The duration of
time that the chalk was in the incubator was also a major flaw. Although all chalk was
supposed to be in the incubator for 24 hours, the chalk was left in the incubator for
22-24 hours. This led to some of the chalk not being fully dried, which contributed to a
higher mass.
The experimental design allowed every researcher to carry out the experiment in
the same manner. Following it limited the variability by eliminating lurking variables.
36
Conversely, the experimental design was not helpful because hydrochloric acid was
used as a substitute for nitric acid--a main component of acid rain. Since both
hydrochloric acid and nitric acid, however, are monoprotic acids, it is acceptable to use
them in place of each other.
This research could be expanded upon in several ways. An increase in trials
would help normalize the results and would most likely show that the 6 M HCl acid has
a greater effect on calcium carbonate compared to 3 M HCl acid. Cutting limestone into
symmetrical blocks would also be more beneficial since it would directly simulate
naturally occuring limestone. In addition, nitric and sulfuric acid could be used to help
directly relate acid rain and calcium carbonate erosion. The use of these acids would
be more practical since they are the two main components of acid rain, producing a
more accurate imitation of acid rain erosion on the limestone blocks. Since average pH
levels of rain in the eastern United States are 4, and 5 in the west, these pH levels
should be used in future experiments.
The data in this experiment simulated a more extreme effect of a highly acidic
solution on limestone. With an increase in global emissions, the rain could become
increasingly acidic, reacting and eroding all limestone in soil. Acidic soil would prevent
the growth of plants and agriculture. The conclusion from the experiment could be
helpful to scientists advocating for the curb of gas emissions because the data suggests
that the rain becoming more acidic from pollution is damaging to the agricultural
business by eroding the limestone. Overall, the research gives greater insight to the
hazardous effects of acid rain on limestone and the environment.
37
Acknowledgements
We would like to acknowledge the following people for their contributions to this
research paper:
● Mrs. Hilliard - For helping us with creating the experiment and understanding
everything chemistry related.
● Mrs. Dewey - For helping us understand what all the data meant.
● Mr. Supal - For helping us format everything correctly.
● Mrs. Cybulski - For helping us with the statistics of the research.
38
Appendix A: Sample Calculations
To analyze the data, a matched pairs t test was used, and was determined using
the formula below. The sample mean is represented by x , calculated by taking the
average percent mass loss of all trials. μ is the population mean which is always set to
zero in a matched pairs t test since it indicates no change. The standard deviation of the
data is represented by s, and n is the number of trials. The value t represents the
number of standard deviations above or below x in a t distribution.
x−μ
t= s/√n
The t-value had to be found for the three and six molar HCl acid using this
formula. The work is shown in figures 14 and 15 below.

x−μ
t= s/√n
0.3789−0
t= .0739/√67
t = 41.9944
Figure 14. Three Molar t Value
Figure 14, above, displays the t value for the 3 M matched pairs t test, calculated
to be 41.9944.
x−μ
t= s/√n
0.3538−0
t= .1570/√67
t = 18.4457
Figure 15. Six Molar t Value
39
Figure 15, above, displays the t value for the 6 M matched pairs t test, calculated
to be 18.4457.
To calculate the percent change in mass, take the change in mass (final mass
minus initial mass) and divide it by the initial mass. Then, multiply this number by 100
and that will give the percent mass loss.

Δmass
%Δmass = massbef ore
× 100
The percent mass loss had to be found for each chalk stick that was submerged
in HCl acid. The work is shown in figure 16 below.

Δmass
%Δmass = massbef ore
× 100
0.9722
%Δmass = 2.6247
× 100
%Δmass = 37.04%
Figure 16. Percent Mass Loss Sample Calculation
Figure 16, above, is a sample calculation of percent mass loss using the data
from trial one of the 3 M reaction.
40
Works Cited
“Acid Rain Program.” EPA, Environmental Protection Agency, 16 May 2017,
www.epa.gov/airmarkets/acid-rain-program.
Baedecker, Philip A., and Michael M. Reddy. “The Erosion of Carbonate Stone by Acid
Rain: Laboratory and Field Investigations.” ACS Publications, Feb. 1993,
pubs.acs.org/doi/pdf/10.1021/ed070p104.
Britannica, The Editors of Encyclopaedia. “Limestone.” Encyclopædia Britannica,
Encyclopædia Britannica, Inc., 9 Feb. 2018,
www.britannica.com/science/limestone.
“Carbonate Chemistry.” Science Learning Hub, 10 Oct. 2012,
www.sciencelearn.org.nz/resources/469-carbonate-chemistry.
Gordon, Glen E. “A Decade of Acid Rain Research.” ACS Symposium Series The
Chemistry of Acid Rain, 1987, pp. 2–9., doi:10.1021/bk-1987-0349.ch001.
Kryza, Ryszard, et al. “Acidic Weathering of Carbonate Building Stones.” Acidic
Weathering of Carbonate Building Stones: Experimental Assessment
(Preliminary Results), 2009, pp. 33–36.,
scholarcommons.usf.edu/cgi/viewcontent.cgi?article=1043&context=geologia.
“Limestones.” Limestone, people.ku.edu/~stalder/KS-limestone.html.
“Limestone Uses.” Science Learning Hub, Science Learning Hub, 25 Sept. 2012,
www.sciencelearn.org.nz/resources/472-limestone-uses.
Ophardt, Charles E. “Acid Rain Effects on Buildings.” Acid Rain Effects - Buildings,
Elmhurst College, 2003, chemistry.elmhurst.edu/vchembook/196buildings.html.
41
Philip Shabecoff and Special To the New York Times. “DRAFT STUDY PUTS ACID
RAIN DAMAGE AT $5 BILLION FOR 17 STATES.” The New York Times, The
New York Times, 18 July 1985,
www.nytimes.com/1985/07/18/us/draft-study-puts-acid-rain-damage-at-5-billion-f
or-17-states.html.
“Precipitation PH Over the United States 1994.” Slideplayer,
slideplayer.com/slide/6917590/.
“Precipitation PH Over the United States 2006.” IV. Acid Rain and PH - Tolland Public
Schools,
www.tolland.k12.ct.us/DistrictOffices/curriculum_and_instruction/tyl__carolyn/wor
kshops__training_materials/web_quests/web_quest_about_acids_and_bases/iv_
__acid_rain_and_ph/.
Ricci, Francis. “The Effects of Acid Rain on the Visible Light Absorption of Stained
Glass.” NHSJS, The National High School Journal of Science, 17 June 2012,
nhsjs.com/2012/the-effects-of-acid-rain-on-the-visible-light-absorption-of-stained-
glass/.
Shapley, Patricia. “Limestone and Acid Rain.” Limestone and Acid Rain, 2011,
butane.chem.uiuc.edu/pshapley/GenChem1/L26/3.html.
“Technical Documents.” Home, 30 Nov. 2017,
www.gsa.gov/real-estate/historic-preservation/historic-preservation-policy-tools/p
reservation-tools-resources/technical-documents?Form_Load=8834
“What Is PH.” What Is PH,
42
academic.brooklyn.cuny.edu/biology/bio4fv/page/ph_def.htm.
“What Causes Acid Rain?” EPA, Environmental Protection Agency,
www3.epa.gov/acidrain/education/site_students/whatcauses.html.
43

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Final Sophomore Research Paper

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The Effect of Different Molarities of

Hydrochloric Acid on the Erosion of Calcium Carbonate

Brendan Cairney, Tyler Doral, and Victoria Kovac

Macomb Mathematics Science Technology Center

Mrs. Hilliard/ Mr. Supal/ Mrs. Dewey

Data and Observations………………………………………………………………...11

Data Analysis and Interpretation……………………………………………………...24

Appendix A: Sample Calculations…………………………………………………….39

of acid on limestone. The research focused on determining the relationship between

In the experiment, chalk was used in replacement of limestone. Each piece of

and crop shortages for farmers.

scientific community by further validating claims on the various detrimental effects of

hazardous effects of acid rain, so progression in modern research continues to be

place and prevent a more acidic atmosphere.

Acid rain was a major environmental phenomenon of the 1980s. Factories

effects that carbon emissions have on the world.

Figure 1. pH Scale (“Britannica”)

hydrogen. It is the measurement of whether a solution is acidic or basic determined by

considered a basic solution--solutions with a pH reading of seven are neutral.

Figure 2. Annual pH in 1994 and 2006 (“Britannica”)

atmosphere became more acidic.

Limestone is commonly found throughout nature. Limestone frequently acts as

CaCO3 (s) + HCl (aq) → CaCl2 (aq) + CO2 (g) + H 2 O (l)

Various experiments have been conducted to deepen the understanding of the

effects of acid rain on carbonate stone structures. An experiment conducted by

Figure 3. Travertine Erosion (​Kryza​)

resulted from the hydrochloric acid is clearly visible on the corners.

Another experiment, conducted by Philip A. Baedecker, found similar results.

increase in concentration of acid leads to a greater concentration of limestone particles

(Baedecker). A greater concentration of limestone particles indicates an increase of

products, which is an increase of mass loss.

component being calcium carbonate ​and limestone being a sedimentary rock

comprising of at least 80% calcium carbonate ​(“Limestones”). Although nitric acid,

calculated to represent the corrosion that occurs.

Overall, calcium carbonate is frequently found in the environment. It is the main

greatest effects on it is of the utmost importance. Using previous research as a basis,

the erosion of calcium carbonate, CaCO​3​.

percent mass loss of the chalk, CaCO​3​.

3. Take a picture of the chalk stick

4. Place piece of chalk in beaker.

5. Use the Ti-Nspire random integer generator function by typing Randint(1,2) to

6. Measure 25 mL of hydrochloric acid solution with a molarity of 3 or 6, depending

8. Take out chalk piece using tongs after two minutes.

11. Remove the trays from the incubator.

13. Take a picture of the chalk.

15” scroll saw and analytical scale.

Data and Observations

Before and After Mass of Chalk in 3 M

Before and After Mass of Chalk in 3 M

Before and After Mass of Chalk in 6 M

Before and After Mass of Chalk in 6 M

Before and After Mass of Chalk in 6 M

the mass loss, which is the change in mass.

16 Researcher #1 conducted the trial.

Trial Date Observation

23 Conducted by researcher #1.

Trial Date Observation

experiment of the chalk being exposed to the 3 M HCl acid.

Trial Date Observation

Trial Date Observation

Trial Date Observation

the 6 M solution did not visibly react with the chalk.

Data Analysis and Interpretation

Figure 3. Travertine Erosion (Kryza)

component being calcium carbonate and limestone being a sedimentary rock

comprising of at least 80% calcium carbonate (“Limestones”). Although nitric acid,

the erosion of calcium carbonate, CaCO3.

percent mass loss of the chalk, CaCO3.

Figure 12. Chalk in 3 M HCl Acid t Test Results

chalk, CaCO3 compared to 3 M hydrochloric acid.

number of standard deviations above or below x in a t distribution.

Figure 14. Three Molar t Value

Figure 15. Six Molar t Value