Wednesday 1:00

Group 2

Matt Trivitayakhun - Manager

J. Cameron Crosby Recorder
Matthew Holloway Technician I
Michael Melvin Technician II

Acid Rain
Introduction:
As defined by the EPA, the term acid rain, refers to an air borne mixture of materials that
contains above average amounts of nitric and sulfuric acids present (1). Acid Rain can become
deposited into the environment through precipitation or by incorporating with dust or smoke and then
falling to the ground (1) These acids can be introduced into the environment through natural
occurrences, volcanic eruptions and vegetation decaying, and manmade sources, machinery that
consumes fossil fuels, which produce sulfur dioxide (SO2) and nitrogen oxides (NOx) gases (1). The
presences of these acids in the rain and the environment can cause a variety of effects. These effects
can range from acidification of both soils and surface water, which can cause significant damage to
plants not accustom to the acidic environment; acid erosion of statues, buildings, and landscapes; and
increased levels of these chemicals within the atmosphere can lead to health problems (2).
Within the environment, there are naturally occurring chemicals that have the ability to lessen
the effects of acid rain. These chemicals range from basic cations like Ca2+ and Mg2+ found in water to
ionic compounds like sodium carbonate (Na2CO3) which is found in limestone and wood ash. These
chemicals act as buffers, which means that it can resists pH change to a certain point. A buffer is made
up from the mixture of a weak acid and its conjugate base. For a chemical species to considered an
acid, when it reacts with water it donates a proton. For example, when hydrochloric acid (HCl) reacts
with water, it forms hydronium ion (H3O+) and chlorine ion (Cl-). Hydrochloric acid does this by
releasing a hydrogen ion (H+) which then reacts with the water to form the hydronium leaving a
chlorine ion. The pH is a measurement that is based on the concentration of the hydronium ion within a
solution. Mathematically pH is the log of either the concentration of hydrogen ion or hydronium ions

present within a solution. When calculating pH concentration is needed. To calculate the concentration
the equilibrium constant of the acid, Ka, is need in order to find the equilibrium concentration of the
hydrogen ions. To experimentally determine the pH and the Ka,a titration of an acidic solution into a
basic solution has to be performed and a titration curve created. A titration curve consists of the pH of a
solution graphed on the y axis compared to the volume of the titrant on the x axis. An example of this
was produced during this experiment. Within the curve there are values pKa1 and pKa2. These are the
mid points between consecutive equivalence point where the solution is acting like a buffer and the pH
is equal to the pKa. To find the Ka from these v alues you would raise 10 to the pKa value.

1 4 .0 0

1 M N a C O w ith 1 M H SO

1 2 .0 0

- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - p K a =p H =1 0 .7
1 0 .0 0

H
p

8 .0 0

6 .0 0

4 .0 0

2 .0 0

e q p o in t: H SO = H C O

- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -- - - - - - - - - -- - - - - - - - - -- - - - - - - - - -- - - - - - - -- - -- - - - - - - - - -- - - - - - - - - -- - p K a = p H = 6 .8
-

e q p o in t: H SO = H C O

0 .0 0
0 .0 0 0

5 .0 0 0

1 0 .0 0 0

1 5 .0 0 0

2 0 .0 0 0

2 5 .0 0 0

V o lu m e I n m L o f 1 M H SO A d d e d

3 0 .0 0 0

3 5 .0 0 0

4 0 .0 0 0

4 5 .0 0 0

Experimental Details.
For Acid Lab Day 1, we designed and tested a procedure to determine the pKas of carbonic
acid. First, we made a 1M sodium carbonate solution in two beakers via titration. Then, we prepared a
1M batch of sodium carbonate solution using around 5.32 grams of the solid form of sodium carbonate
and a 50 mL flask, which we diluted to the mark. After that, we transferred 40 mL of the 1M sodium
carbonate solution into an Erlenmeyer flask using a graduated cylinder. We then filled a buret with 1M
of sulfuric acid, and it took 40mL to neutralize the sodium carbonate solution. We then calibrated the
drop counter, gathered all the points and data we needed , made several graphs with the data, and then
exported them into a cvs file so we could store it in Excel.
For Acid Lab Day 2, we developed and tested a procedure to test if all areas in nature were
affected by acid rain. To do this, we first made 1M solutions of calcium carbonate, magnesium
carbonate, and titanium oxide. We made 5.0 grams of calcium carbonate in a 50 mL volumetric flask,
4.2 grams of magnesium carbonate, and 4.0 grams of titanium oxide, all in separate 50 mL volumetric
flasks. Then, we diluted the solutions and buffer to the mark, and then, we set and tested three separate
titrations using the calcium carbonate, magnesium carbonate, and titanium oxide. We then calibrated
the drop counter for that experiment, and we also began the titrating the sulfuric acid into the solutions.
During the titrations, we reran titrations rinsing the pH probes between tests for calcium carbonate,
magnesium carbonate, and titanium oxide.

Materials used during lab day 1:

Sodium carbonate
1M nitric acid

1M sulfuric acid
Vernier handhelds with pH electrodes and drop counters
Burets, pipets, and volumetric flasks

Materials used during lab day 2:

1M sulfuric acid
1M nitric acid
Calcium carbonate, magnesium carbonate, titanium oxide, and other chemical compounds in

minerals.
Vernier handhelds with pH electrodes and drop counters
Burets, pipets, and volumetric flasks

Data and Results of Calculations:

The two main goals of this experiment was to determine the pKa of Carbonic Acid, and to see
what chemical species that we were given would make the best buffer.
pKa can be determined from the following equation:
1

pH=pKa+log[conjugate base]/[acid], pKa can also be determined by a titration curve.

Half way to the equivalence point, the pH=pKa. This is because half way to the equivalence point, the
amount of acid added=amount of conjugate base formed. This gives us the equation:
pH=pKa+log[1]/[1]

pH=pKa

For the experiment above, 4.8=pKa1+log[HCO3-]/[H2SO4] and 6.8=pKa2+log[H2CO32-]/[H2SO4]

To determine whether TiO2 or CaCO3 was the better buffer, the titration curves can be of use.
The titration of Sulfuric acid with Calcium carbonate resisted changes in pH much better than TiO2. To
quantify the buffering capacity of CaCO3, the following equation can be used:
1

Buffer Capacity= Maximum # of moles of acid added before capacity is exceeded

Mass of solid used

For the experiment above,

the buffer capacity of CaCO3= 7.48*10-2 moles H2SO4/ 2.50g CaCO3
Buffer Capacity = 2.99*10-2 moles of acid/g CaCO3
Discussion of Results
The sodium carbonate titration curve that was generated during the lab has two distinct
equivalence points. At each equivalence point, an acid dissociation occurs. See Sodium Carbonate
Sulfuric Acid Titration curve.
The number of equivalence points in a titration curve can be described mathematically as the

number of times that hydrogen ions disassociate and form bonds with the base. See the equation below
(knockhardy.org).
Step 1:
Step 2:
Overall:

+ HCL NaH
NaH

+ HCL NaCl +

+ NaCl
+

+ 2HCL 2NaCl +

In the equation above, we see that the overall reaction takes place in two steps. In step one; we see that
the sodium carbonate reacts with the hydrochloric acid forming sodium bicarbonate (baking soda) and
common table salt. During this reaction, a sodium atom and a hydrogen atom swap places forming
the products described above. This first hydrogen atom swap is seen graphically as the first
equivalence point. The second equivalence point results in another similar atom swap, except this
time three products are produced: salt, water, and carbon dioxide (creative-chemistry).
The Henderson-Hasselbalch equation, which follows, can be used in the determination of pKa
for weak acids by performing a titration of that acid.
pH = pKa +

When the [weak acid] = [conjugate base], the equation is as follows:

pH = pKa + log(1)
pH = pKa + 0
pH = pKa
The [weak acid] = [conjugate base] when half the volume needed to reach the equivalence point has
been sufficiently added. At this volume, the pH and the pKa values are equal.
Both calcium and sodium carbonate acted like buffers when titrated. Evidence of this can be
seen by the fact that there is approximately a 1.00 change in the overall pH level of calcium carbonate

over a volume of approximately 4.75 mL. Sodium carbonate, on the other hand, had a much larger
range in which it acted as a buffer; however, it took a larger volume to reach this buffer solution.
Evidence of this can be seen by the fact that there is less than a 1.60 change in the pH level over a
volume of approximately 12.00 mL.
Conclusion:
There were two pKa values obtained for carbonic acid. pKa1 equaled 4.8, and pKa2 equaled 6.8.
TiO2 did not act like a buffer at all; its buffer capacity was 5.00*10-4 moles of acid/g TiO2. CaCO3 did
act like a buffer; its buffer capacity was 2.99*10-2 moles of acid/g CaCO3, much higher than that of
TiO2. This suggests that areas where there are high concentrations of CaCO3 will resist damage from
acid rain better than those areas that do not contain any.

Extension Questions:
Many different types of pollution cause the formation of acid rain. 1The combustion of fossil
fuels account for 86.6% of the conversion of SO2 to H2SO4, volcanoes account for 9.9%, and wild fires
account for 3.4%. The SO2 is converted to sulfuric acid by the following chemical equation:
SO2+OH-HOSO2-+O2HO2-+SO3(g)+H2O(l)H2SO4(l).
Since sulfur dioxide producing agents are now regulated, 1the emissions of nitrogen oxides, which
oxidize to form nitric acid are becoming of increasing concern. 1 Coal factories are the most
polluting. Gasses that make it into the atmosphere can be half way around the world before they fall as
acidic rain that has adverse effects.
Acid rain has been known to cause death in marine environments, damaging metals, and
destroying forests. In marine environments, the water of the lake or stream would become increasingly
acidic with the more acid rain that falls in the area. Biological systems are definitely affected by the
decrease in pH that would occur in the lakes and streams. For example, the chemical bonds that give
proteins their form and therefore their structure are affected by pH. The amino acids that comprise the
proteins act like buffers to keep the pH of the human body slightly acidic. If more and more acid is
added and the buffer capacity of the amino acids is reached, then the pH will begin to drop and the
bonds holding the proteins together will fall apart. This process is called protein denaturalization. If the
proteins of the organisms in the marine environment denaturalize, they will die and can cause
tremendous harm to huge ecosystems. 1Acids also steal the cations out of the soil and cause the
nutrients to be kept from the vegetation. This is also very bad for ecosystems, and alternative
technologies are needed to reduce the harmful effects of acid rain.
2
National Geographic say that the best way we can fight acid rain at this moment is to reduce
our consumption of fossil fuels. To do this though, a new energy source would be needed and it would
have to be relatively cheap. This way everyone would have access to it, and a dent could really be made
in the reduction of our fossil fuel consumption. Some of the promising replacement energy sources are

solar and wind power. If the manufacturing of solar cells were cheap enough so that they could be
massed produced on an enormous scale, then the problem could possibly be solved. Wind energy is
perhaps the cleanest energy. There are already wind turbine generators in the plains of America and
other countries. 2However, a wind turbine generator only transfers 1/3 of the kinetic energy of the air in
motion, mainly due to the mass of the blades and the friction that is created when they rotate.
3
On Library Indexes website, they say that the normal acidity of the lakes and streams in the
United States ranges from a pH of 6-8. Here is a table of what effects a low pH caused by acid rain can
have on the marine life.
4

Generalized short-term effects of acidity on fish

pH
Effect
range
6.59
No effect
6.06.4 Unlikely to be harmful except when carbon dioxide levels are very high (1000 mg I 1)
Not especially harmful except when carbon dioxide levels are high (20 mg I 1) or ferric ions
5.05.9
are present
Harmful to the eggs of salmon and trout species (salmonids) and to adult fish when levels of
4.54.9
Ca2+, Na+ and Cl- are low
4.04.4 Harmful to adult fish of many types which have not been progressively acclimated to low pH
3.53.9 Lethal to salmonids, although acclimated roach can survive for longer
3.03.4 Most fish are killed within hours at these levels

There are a few ways we can treat the acidity of lakes and streams though. Buffers like calcium
carbonate can be used to regulate the pH of lakes and streams. 5Louis A. Halfrich, a researcher at
Virginia Tech, says that limestone, which is primarily CaCO3, can also be applied to lakes, ponds, and
their surrounding watersheds to protect them from acidification, to add calcium, and to restore their
important ecological, economic, and recreational values. Adding limestone to maintain a near-neutral
pH (pH 7) keeps lake and pond water safe for aquatic life. This technique, known as 5liming, has
many advantages too. It is cheap, and this makes it easy to distribute to widely affected areas. It is nontoxic, so it can actually be administered when needed, and some lakes already have these calcium
carbonate lakebeds so they already resist pH changes on their own.