35

Acids in the Environment I:

Preparation and Properties of Gases
Introduction

Chem Connections
Burning fossil fuels generates many gases that are eventually released into the air. Once in the
atmosphere they are able to travel, react, and interact with our environment. In order to understand the
impact that an air pollutant has on the environment, it is important to consider all of the reactions it can
undergo while in the environment. During the next few weeks, we will be considering how certain
pollutants react in the environment to cause acid rain, as well as how acid rain can cause dramatic
changes in aquatic ecosystems.

First, we need to consider the interaction of gases with water. All gases can dissolve in water to a certain
extent, and some of these gas molecules can react with water to produce acids. The details of this
process are explained briefly below.
New Science
As mentioned above, many gases are able to dissolve in water. For example, the very important
atmospheric gas carbon dioxide dissolves in water. You have experienced this phenomenon many times
in drinking soda or other carbonated beverages. The chemical equation for this reaction is:
CO
2
(g) CO
2
(aq)
It turns out that carbon dioxide can dissolve rather effectively in water (i.e. we end up with a large amount
of products in the above reaction). We use something called a Henrys law constant (K
H
) to describe just
how much gas dissolves in water. A large K
H
implies that a large amount of gas has dissolved, or become
aqueous. One reason this can occur is that a secondary reaction takes place between the now aqueous
gas and water:
CO
2
(aq) + H
2
O (l) H
2
CO
3
(aq)
When the aqueous carbon dioxide is reacted with water, more carbon dioxide from the atmosphere can
dissolve. This is why some gases, like carbon dioxide, are so soluble in water.
The product of the above equation, carbonic acid (H
2
CO
3
), is exactly what its name implies: an acid.
Chemically, this means that carbonic acid produces the H
+
ion in water:
H
2
CO
3
(aq) HCO
3

(aq) + H
+
(aq)
HCO
3

(aq) CO
3
2
(aq) + H
+
(aq)
Experiment
3
36

The more H
+
ions that form, the more acidic a solution becomes. Working backwards, this means that the
more gas that dissolves in solution, the more H
+
is formed, and the more acidic the resulting solution is.
Acid rain is attributed to a similar set of reactions involving sulfur oxides and nitrogen oxides, collectively
referred to as SO
x
and NO
x
. Just like we discussed above, the K
H
values of the gases can tell us how
much they will dissolve in water, which in turn can help us determine how acidic the solutions will
become. We can measure the acidity of a solution by determining its pH. pH = -log[H
+
], where brackets
indicate molarity. Therefore, a high concentration of H
+
(i.e. an acidic solution) leads to a low pH.
Sulfur Oxides:
SO
2
(g) SO
2
(aq)
SO
2
(aq) + H
2
O (l) H
2
SO
3
(aq)
2 NO (g) + O
2
(g) 2 NO
2
(g)
NO
2
(g) NO
2
(aq)
NO
2
(g) + H
2
O(l) HNO
3
(aq) + HNO
2
(aq)
While an acid is a chemical that dissolves in water to form H
+
ions, a base is a chemical that produces
OH
-
ions in water. When you put them together, the following generic reaction occurs:
H
+
(aq) + OH
-
(aq) H
2
O (l)
Thus, the result of an acid-base reaction is neutral water, of pH 7. An excess of acid will result in a pH
slightly lower than 7, while an excess of base will give a pH slightly higher than 7.
In this experiment you will prepare carbon dioxide gas and observe its effects on water and a basic
solution (i.e. low H
+
concentration, or high pH) to model what happens when SO
2
and NO
x
dissolve to
form acid rain. You will use universal indicator to help to visualize the changes in solution. The indicator
changes color with changes in pH.
Color Changes of a Universal Indicator
pH
Universal
Indicator Color
Concentration of H
+

(M)
Concentration of OH

(M)
Description of
Solution
4.0 Red 10
4
10
10
acidic
5.0 Orange-Red 10
5
10
9
acidic
6.0 Yellow-Orange 10
6
10
8
acidic
7.0 Dark Green 10
7
10
7
neutral
8.0 Light Green 10
8
10
6
basic
9.0 Blue 10
9
10
5
basic
10.0 Reddish-Violet 10
10
10
4
basic
11.0 Violet 10
11
10
3
basic
12.0 Violet 10
12
10
2
basic
13.0 Violet 10
13
10
1
basic

37

Prelab Questions
Write the answers to the questions below in your laboratory notebook and be prepared to
participate in an in class discussion of your findings. Visit the popular topics listed on the
Environmental Protection Agency website (epa.gov) and read some of the information about
acid rain.
1) According to the EPA what are the primary sources of SO
x
and NO
x
in the United
States?
2) What are the natural causes of SO
x
and NO
x
in the atmosphere?
3) Using your preferred internet search engine, determine the current atmospheric
concentration of carbon dioxide in ppm?

Complete the table below using your own reasoning, your textbook or other resources.
Gas
Lewis Structure
(obeying octet rule)
Lewis Structure
(minimizing formal charge)
Henrys Law
Constant, K
H

(molesL
-1
atm
-1
)
Carbon dioxide, CO
2
2.310
-2

Oxygen, O
2

Nitrogen, N
2

Sulfur dioxide, SO
2
1.2
Sulfur trioxide, SO
3
infinite
Nitrogen oxide, NO 1.910
3
Nitrogen dioxide, NO
2
4.010
2


4) Of the molecules you have drawn, which have different structures depending on the
model of bonding used? (obeying the octet rule vs. minimizing formal charge)
5) What experimental data would you need to determine which model of bonding most
closely matches the true structure of the molecule?
6) Which of the gases above is the most soluble in water?
7) Which of the gases above react with water to produce acid rain? Use the epa.gov site to
help you in answering.
8) Is carbon dioxide considered a source of acid rain?


38

Experimental

The Problem
Characterize the effect that CO
2
gas has on solutions which contain base and an indicator.
The Approach
Work with one other person.

Equipment Needed:

1 well plate
Disposable pipet
Plastic ziplock bag (quart size)
Stopwatch/timer
60 mL plastic syringe
Syringe cap
Vial cap

Chemicals Needed:
0.1 M NaOH Stock Solution
Deionized water
Universal indicator
Sodium bicarbonate, NaHCO
3
, baking soda
Acetic Acid, CH
3
COOH, 1M


Making CO
2
gas:
1. Generate a syringe full of CO
2
gas using the instructions listed on the pages that follow.
You will make dilutions to obtain different concentrations of NaOH in your well plates.
2. Use a plastic pipet to transfer ~2 mL deionized water to each well. You do not need to
measure using the markings on the pipet. Fill up the pipet with the maximum amount of
water to obtain approximately 2 mL.
3. Using a plastic pipet, add 1 drop 0.1M NaOH to the first well. Add 2 drops 0.1 M NaOH
to the second well. Add 5 drops 0.1 M NaOH to the third well. The fourth well will
contain deionized water only.
4. Add 2 drops Universal Indicator to each well. Note the color of each well. Use the table
in the introduction to estimate the pH.
39

5. You should now have a well plate with four different solutions. Place the well plate in the
plastic bag and press down on the bag to push air out to minimize the amount of air in
the bag.
6. Open the bag slightly so that you can place the syringe in the bag and add the CO
2
.
Close the bag and start a timer.
7. Gently swirl the well plate. Record observations for 6 minutes, recording the color every
30 seconds. Continue to swirl the plate occasionally. If one of your well plates does not
turn green after 6 minutes, continue to monitor it and note the time it turns green.
8. Estimate the final pH of the solutions in the well plates using the table in the introduction.
Table 1: Observations

1 drop
of NaOH
2 drops
of NaOH
5 drops
of NaOH
water
Initial Color
Initial pH (estimate
based on table)

Color of Solutions
(minutes:seconds)

0:30
1:00
1:30
2:00
2:30
3:00
3:30
4:00
4:30
5:00
5:30
6:00
Final pH of
solutions (use table
to estimate)


40

The following procedure was adapted with permission from Microscale Gas Chemistry, Educational
Innovations, copyright Bruce Mattson, 2003
Order this book (Item #BK-590) from Educational Innovations, http://www.teachersource.com/

THE IN-SYRINGE METHOD FOR PREPARING GAS SAMPLES
PREPARATION OF CARBON DIOXIDE

General Safety Precautions
Always wear safety glasses. Gases in syringes may be under pressure and could spray liquid
chemicals. Follow the instructions and only use the quantities suggested.

Toxicity
Carbon dioxide is a relatively non-toxic gas. Like all gases other than oxygen, it is a simple
asphyxiant if inhaled in very large quantities. We will not be generating very large quantities of carbon
dioxide.

GETTING STARTED
Before we start making gases, we need to know a bit more about the equipment that we will use.
Many of the important pieces that we will use are pictured below. Lets start with the most dramatic, the
large syringe which may invoke pangs of fear and memories of visits to the doctors office. There are no
needles, however. You will notice that after working with these syringes a few times, you will no longer
think of them for their medical applications. (Incidentally, these 60 mL syringes are used by veterinarians
to treat large farm animals and are not normally used by medical doctors.)


41

The syringe is composed for two major parts the barrel (outside part) and the plunger (inside
part). Plungers and barrels are interchangeable. On one end of the plunger you will notice an air-tight
black rubber seal.


MAKING CARBON DIOXIDE
You are now about to prepare your first gas sample using the syringe equipment. The general
strategy of the method is to react two substances in a large syringe. The limiting reagent is always used
in solid form and is placed in a small vial cap. The second reagent is prepared as an aqueous solution.
For example, you will generate CO
2
(g) from acetic acid, used in excess, and solid baking soda or sodium
bicarbonate, NaHCO
3
.

1. Wear your safety glasses!

2. Lubricate the seal
If your syringe plunger does not move freely,
lubricate the black rubber seal of the plunger with
silicone oil.

3. Measure out the solid reagent
(Use ~0.2 g NaHCO
3
to make CO
2
. The
exact amount is not important
Place the vial cap on the balance and are (zero) the
vial cap and measure the solid directly into the vial
cap. This prevents losses from transferring small
amounts of solids.


4. Fill the syringe barrel with water
Fill the barrel with water. Place your finger over the
hole to form a seal. Fill completely to the top.

5. Float the vial cap
Float the vial cap containing the solid reagent on the
water surface. This is easiest if the syringe barrel is
filled completely to the top with water.

42

6. Lower the cap by flotation

Release the seal made by finger to lower the cap into the syringe
barrel without spilling its contents. Allow the syringe to drain into a
beaker. When successfully completed, the cap should rest upright
on the bottom of the syringe with all reagent still in the cap.


7. Install the plunger
Install the plunger while maintaining the syringe in a vertical
position. The plunger should fit snugly against the rim of the vial
cap. Push it all the way down. We dont want more residual air
space.


8. Draw aqueous reagent into syringe
(Use ~5 mL acetic acid to make CO
2
)
The aqueous reagent, measured into a small weighing
dish, is drawn into the syringe while maintaining the
vertical position of the syringe. The vial cap with the solid
reagent should float on the solution. DO NOT suck in
extra air, this will decrease the partial pressure of CO2
after the reaction is complete.


9. Install syringe cap
Put the syringe cap on by twisting the cap into the
threads of the syringe.


43

10. Generate the gas

Shake the syringe in order to mix the reagents. As
the liquid reagent splashes into the vial cap, gas
generation will commence and the syringe plunger
should move outward. It is sometimes necessary to
gently help the plunger move up the barrel.


11. Remove cap to stop gas collection
After the plunger has reached approximately 50 mL, tip the syringe
so that it is positioned with plunger downward and syringe cap
upward. Carefully remove the syringe cap assuming that the
syringe may be under positive pressure. (Burp that baby with its
head up!)


12. Discharge reagents
Turn the syringe 180
o
and discharge the liquid reagent into the
plastic cup. Caution: Never remove the syringe cap with the
cap end of the syringe directed downward: Reagents will
spray out of the syringe. Immediately cap the syringe with the
syringe cap to prevent loss of gas by effusion.


44

13. Wash away contaminants

The gas-filled syringe may be "washed" in order to remove traces of unwanted chemicals from the inside
surfaces of the syringe before the gas is used in experiments. To wash a gas:
1. Remove the
syringe cap,

2. draw 5 mL water
into the syringe,

3. cap the syringe,

4. shake syringe to
wash inside
surfaces,

5. remove cap,

6. discharge water
only, and finally

7. recap the syringe.

8. Rinse once more
with deionized
water.

OTHER USEFUL GAS SYRINGE TECHNIQUES

There are a several other techniques that come in handy when working with gases in syringes.
Here are the most important ones. Try to use these techniques as much as possible.

A. Controlled discharge of gas from a syringe
Plungers do not always move smoothly in their syringe barrels. As a result, gases may be
discharged in large unintended portions (such as 40 mL all at once) if the method shown in the left
diagram below is used. Instead, grasp the syringe by its plunger (right figure) and pull the barrel towards
your hand. This simple technique will give you excellent control of gas delivery.


INCORRECT WAY

CORRECT WAY

45

Clean-up and storage
At the end of the experiments, clean the syringe parts, caps and tubing with soap and water. Use
plenty of soap to remove oil from the rubber seal. This extends the life of the plunger. It may be
necessary to use a 3 cm diameter brush to clean the inside of the barrel. Rinse all parts with distilled
water. Be careful with the small parts because they can easily be lost down the drain. Important: Store
plunger out of barrel unless both are completely dry.


Collection and Treatment of Excess Chemicals
Unwanted CO
2
(g) samples can be safely discharged into the room. Place any used chemical in
the appropriate BSC containers located in our near the fume hood.


46

47

Experiment 3-Acids in the Environment I
Report Sheet
Name________________________________

Lab Partners__________________________

GSI:____________________ _____________________________________


Answer these questions with your lab mates and turn them in to your GSI at the end of the next lab
session. Answering these questions will serve as a good review of concepts for the exam.

1) The lab experiment instructs you to react 0.2g of NaHCO
3
with excess CH
3
COOH. How much CO
2

(g) in mL would this reaction generate if all the sodium bicarbonate reacts fully? (Recall 1 mole of gas
occupies ~24.5 L at room temperature and pressure.)






2) Order the solutions in terms of which one changed color first. Does this ranking make sense based
on how much NaOH was added?






Though this experiment was qualitative rather than quantitative, you can still estimate the concentration of
base in each of the well plates. The formula below is useful for calculating concentration changes
resulting from dilutions.
M
concentrated
V
concnetrated
=M
dilute
V
dilute


3) Assuming that 30 drops from the pipette totals 1 mL and that each well in a well plate has a volume of
2 mL calculate the concentration (M) of the NaOH in each of the basic solutions in the wells. Show an
example calculation below for 1 drop of NaOH in a well plate. Write the results of your calculations in a
table in your notebook like the one shown below.











48

4) In lecture you have observed a demonstration using a light bulb to detect the presence of ions in
solution. What would you predict for the light bulb experiment for each of the wells?

1 drop
of NaOH
2 drops
of NaOH
5 drops
of NaOH
water
Estimated concentration of NaOH (M)
Predicted Light Bulb Brightness
(none, dim, bright)



5) Predict what would happen if you changed the following parameters:
a. Inject half the amount of CO
2
.

b. Inject the same amount of CO
2
and an equal volume of air.


c. Inject twice the amount of CO
2
.

If there is time, feel free to test out your predictions.


6) Calcium carbonate is a very insoluble salt. If you added a few drops of 0.1M CaCl
2
(aq) to the wells,
what would you expect to see? How would the observations differ between the wells?





7) Explain why the different concentrations of NaOH in each of the wells take different times to react
with the CO
2
.





8) Draw the Lewis structures of CO
2
, H
2
CO
3
, HCO
3

and CO
3
2
. Rank these in order of increasing
attraction to water molecules. Explain your choice. What evidence do you have that supports your
predictions?