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In the Laboratory

Exploring the Ideal Gas Law through a Quantitative


Gasometric Analysis of Nitrogen Produced by the
Reaction of Sodium Nitrite with Sulfamic Acid
Anne Yu
Department of Chemistry, Pomona College, Claremont, California 91711, United States
anne.yu@pomona.edu

The gasometric analysis of nitrogen produced in a reaction


between sodium nitrite, NaNO2, and sulfamic acid, H(NH2)-
SO3, provides an alternative to more common general chemistry
experiments used to study the ideal gas law, such as the experi-
ment in which magnesium is reacted with hydrochloric acid and
others in which Boyle's law and Charles' law are investigated (1).
This experiment, in which the percent sodium nitrite of a sample
is determined with the use of equipment commonly found in a
general chemistry laboratory, was first published in 1946 (2),
and data culled over the last several years show that modifica-
tions to the original procedure have improved results in this
classic laboratory exercise while also reducing student anxiety
related to difficulties in the original procedure. In addition to
the ideal gas law, this experiment provides students with an
opportunity to analyze data using principles and concepts that
constitute core topics often presented in the first semester
of general chemistry, such as stoichiometry, redox equations,
Dalton's law of partial pressures, the vapor pressure of water,
and barometric pressure. Figure 1. The assembled apparatus.
The fundamental reaction in this analysis is
to provide a constant-temperature bath for the Erlenmeyer
NO2 - ðaqÞ þ Hþ ðaqÞ þ NH2 SO3 - ðaqÞ f N2 ðgÞ flask being used as a reaction vessel. The apparatus is shown in
þ HSO4 - ðaqÞ þ H2 OðlÞ ð1Þ Figure 1, and additional details are provided in the supporting
information.
A 0.25 M sulfamic acid solution is added in excess to samples of Before the reaction initiates and after it is completed, one
an unknown mixture containing sodium nitrite and sodium must ensure that the water in the buret is at the same level as the
chloride. The 55-85% sodium nitrite mixtures need to be dried water in the leveling bulb. This allows the student to employ the
at 110 !C for 1 h prior to the lab period and stored in desiccators barometric pressure as the total pressure of the system. Because
as the samples are hygroscopic. For each run, 20 mL of the the nitrogen is collected over water, its pressure can be calculated
sulfamic acid solution is required to completely react approxi- after determining the vapor pressure of water at the experimental
mately 0.15 g of unknown mixture. Once the apparatus is temperature as the total pressure is the sum of the two. The
assembled and tested for the leaks, the entire reaction proceeds apparatus must be assembled and checked to ensure that leakage
in 20-30 min so that three to five runs may be executed within a is minimized. The nitrogen gas produced displaces the water in
3- to 4-h lab period. the buret such that the volume can be easily determined using the
final and initial volumes.
Procedure According to eq 1, approximately 0.20-0.25 g of pure
sodium nitrite is needed to react completely with 20 mL of
The reaction takes place in a 50 mL Erlenmeyer flask sealed 0.25 M sulfamic acid. Approximately 0.14 g of unknown mixture
with a no. 2 one-hole rubber stopper with a 24 in. length of 6 mm is used for each run; thus, sulfamic acid is present in excess. An
glass tubing. A 15 in. length of 3/16 in. rubber tubing is attached easily acquired and inexpensive replacement for the glass vials
to the 6 mm glass tubing on one end and the other end of the used in the original experiment (2), which must be cleaned with
rubber tubing is attached to a 3 in. length of 5 mm glass inserted water, acetone, and briefly oven-dried in between runs, are
into a no. 00 one-hole rubber stopper placed at the top opening gelatin capsules. Between the time the capsule is introduced to
of a buret. An additional 20-30 in. of 1/4 in. rubber tubing, the the acid solution in the reaction vessel and the beginning of the
type commonly used for Bunsen burners, is used to connect the reaction, the student can adjust the leveling bulb to ensure that
tip of the buret to a leveling bulb. A funnel can also be used as a the level of the volume of the water in the bulb and the buret have
leveling bulb. An 800 mL beaker filled with water is required equalized. This adjustment often takes several minutes as does

r 2010 American Chemical Society and Division of Chemical Education, Inc. pubs.acs.org/jchemeduc Vol. 87 No. 12 December 2010 Journal of Chemical Education 1369
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10.1021/ed100353b Published on Web 10/06/2010
_
In the Laboratory

Table 1. Comparison of Results Using the Glass Vials and Gelatin Capsules
Results with Glass Vial Results with Gelatin Capsule

Sodium Nitrite in the Number of Standard Number of Standard


Unknown Mixture (%) Students Average (%) Deviation Students Average (%) Deviation

85.0 22 79 4.7 51 80. 4.3


75.0 21 70. 7.4 55 71 2.4
70.0 27 66 7.7 53 67 5.5
60.0 21 56 2.2 46 58 5.2
55.0 44 54 4.1 39 55 4.7

the time required for the acid to dissolve through the capsule. of 40 mL. The reaction of empty gelatin capsules with the acid
Consequently, the delay in the reaction that is inherent in using solution showed no contribution to the volume of gas pro-
gelatin capsules allows for the experiment setup to be executed duced.
more precisely. The error increases as the percent composition of sodium
nitrite increases in the unknown sample. This is likely due to the
Hazards and Disposal increase in reaction time. As more time is required to allow
complete evolution of gas, there is also an increase likelihood of
Students should wear eye protection and lab coats. leakage. This would decrease the volume change and thus the
Sulfamic acid should be handled carefully to avoid spilling amount of sodium nitrite calculated. Additional results similar to
and contact with the skin. Spills can be neutralized with those reported in Table 1 from previous years of using glass vials
sodium bicarbonate, which should be readily available in the can be provided upon request. The results indicate that there is
lab. Sodium nitrite is not combustible, but is a strong oxidizer an overall improvement in the average percent composition
and, similar to sulfamic acid, is harmful if swallowed and can using gelatin capsules with an overall smaller range of standard
be irritating to the skin, eyes, and respiratory tract. Contact deviations. For optimal precision and accuracy, unknown sam-
with the skin and eyes should be followed with flushing with ples that contain approximately 55-70% sodium nitrite work
water. If fresh air does not improve breathing after inhalation, best. The data in Table 1 are helpful in making peer comparisons
then seek medical attention. The instructor should caution should an instructor distribute a range of samples among the
students that when cleaning up after each run to dispose of the students.
gelatin capsule remainders into the trash, rather than down In the original experiment, an open glass vial was used, and
the sink. upon contact with the sulfamic acid, the reaction proceeded
immediately. It was common for the reaction to start inadver-
Data Analysis tently before students had time to equalize the water levels due
to accidental tipping over of the open sample vial in the beaker
The data collected are the barometric pressure, temperature, containing sulfamic acid. This would have led to misleading
volume change, and initial mass of the sodium nitrite unknown. volumes and greater deviations in the averages if runs had
The pressure of the gas is experimentally made equivalent to the initiated too early and on an inconsistent basis before water
barometric pressure and can be calculated employing Dalton's levels had been properly adjusted. The inadvertent tipping over
law of partial pressures after determining the vapor pressure of of the open glass vials was an enormous source of frustration,
water at the experiment temperature. The student is then able to and replacement of the glass vials with gelatin capsule has
employ the ideal gas law removed the anxiety associated with the experiment, increased
PV ¼ nRT ð2Þ efficiency during the lab period, and reduced the waste of
chemicals.
to determine the amount of nitrogen gas evolved. From this the
percent composition of sodium nitrite in the initial sample can Summary
be determined from the stoichiometric relationship given in
eq 1. The gasometric analysis of nitrogen produced in the
reaction of sodium nitrite with sulfamic acid is rich in
Results chemistry and can be executed largely with items commonly
found in a general chemistry laboratory. The experiment
Three years of student lab results are shown in Table 1. allows students to employ a variety of concepts presented in
Each student reported the average of at least three trials. The the lecture portion of the curriculum as they analyze data. The
table lists the averages and standard deviations of all student quantitative nature of the experiment is increasingly more
results for each of the unknown mixtures. The original article precise and accurate with replacement of the glass vials with
claims that an accuracy of 0.1 to 0.2% may be expected (2), but gel capsules as it provides more time to allow equalization of
the student data show otherwise. There is an expected error pressure. Though there are inherent and unavoidable errors,
ranging from 1-5% as a result of several inherent experimental the 50-70% sodium nitrite samples have resulted in better
errors. For example, a 1 !C rise in room and bath temperature accuracy, requiring less time to completely react than the
would result in a 0.5% error. The solubility of nitrogen gas may higher sodium nitrite content. Once the apparatus is set up,
cause another 0.15% error for a sample that generated a volume students are able to perform multiple runs in a 3- or 4-h lab

1370 Journal of Chemical Education Vol. 87 No. 12 December 2010 pubs.acs.org/jchemeduc r 2010 American Chemical Society and Division of Chemical Education, Inc.

_ _ _
In the Laboratory

period, which should yield ample data for a quantitative Literature Cited
analysis of the results.
1. Wilbraham, A.; Staley, D.; Simpson, C.; Matta, M. Chemistry
Acknowledgment Laboratory Manual, 2nd ed.; Addison-Wesley: New York, 1990;
pp 135-142.
The author thanks the members of the Pomona College 2. Brasted, R. J. Chem. Educ. 1946, 23, 320–321.
Chemistry Department who were initially involved in imple-
menting this experiment, especially Chuck Taylor for sugges-
Supporting Information Available
tions and discussion, Elena Branford (class of 2010), who tested
the modification, and the general chemistry students whose Instructions for the students; notes for the instructor. This
results are included here. material is available via the Internet at http://pubs.acs.org.

r 2010 American Chemical Society and Division of Chemical Education, Inc. pubs.acs.org/jchemeduc Vol. 87 No. 12 December 2010 Journal of Chemical Education 1371
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Last printed 4/5/2010 1:09:00 PM

LAB DOCUMENTATION for the student experiment

GAS ANALYSIS OF NITRITE

The objective of this experiment is to determine the percent of NaN02 in a


sample by measuring the volume of N2 gas liberated by the action of an
excess of sulfamic acid, H(NH2)SO3, and to gain an understanding of the
applications of the gas laws.

PRINCIPLES

The fundamental reaction in this analysis is

+ H+(aq)+ NH2SO3-(aq)! N2 (g) + HSO4-(aq) + H2O (l)


-
NO2 (aq) (1)
-
Although the reaction is specific for NO2 , the methods employed are very general and
could be applied to the analysis of any relatively rapid reaction in which a gas is evolved
as the result of mixing a liquid reagent with another solid or liquid. The method cannot
be applied (a) if the gas produced is very soluble in the liquid solution, (b) if the reaction
does not go to completion, or (c) if two or more gases are formed simultaneously and in
variable relative amounts.

This experiment also illustrates several different applications of the gas laws as well as
some aspects of the mechanical behavior of confined gases which are not always apparent
to the novice. The fundamental principles are discussed in your text, with the "ideal gas
law"

PV = nRT (2)

being basic to the entire discussion. In brief outline, chemical Eq. (l) shows that for every
-
mole of N2 (g) produced, one mole of NO2 must have been present in the original
unknown sample. Eq. (2) shows that the number of moles of N2(g) produced can be
obtained by measuring the volume of N2(g) at the measured conditions of temperature and
pressure. In this experiment, the total pressure (equal to barometric pressure, PB) is
measured. Because the N2 is evolved from an aqueous solution it is saturated with water
Gas Analysis of Nitrite 1
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vapor, and the total pressure is the sum of the pressure of the N2 gas that is produced and
the vapor pressure of water with which it is saturated. As a consequence, you must apply
Dalton's Law of partial pressures in order to obtain the true pressure of the N2 alone in the
measured volume; i.e.,

P B = P N2 + P H2 O or P N2 = P B - P H2 O

Since the measuring system is closed, the N2 is saturated with water vapor and PH2O will
be equal to the vapor pressure of the liquid water at the temperature of the experiment.
The barometric pressure, PB, can be read directly from the laboratory barometer.

Since small changes in temperature during the course of a given run can have a serious
effect, every effort must be made to keep the temperature constant. For example, if there
were 60 ml of trapped air in the closed system, a 1°C rise in room and bath temperature of
27°C would cause a change of (1/300) (60) = 0.2 ml in the water level of the buret, even
though no N2 had been generated. If 40 ml of N2 gas were actually generated, this error
would correspond to a percentage error of 0.5%. The other major error, but one over
which you have no control, is the solubility of the nitrogen (and therefore the loss of the
N2) in the reaction mixture. This solubility, over and above that already dissolved from
the air, which is 79% N2, is approximately 0.06 ml, an amount corresponding to about
0.15% error for a N2 volume of 40 ml. These and other small inherent errors combine to
make gas analysis, as illustrated by the simple apparatus of this experiment, appreciably
less precise than many of the other methods studied in this course. It is reasonable to
expect an overall relative error of the order of one percent.

EXPERIMENTAL PROCEDURE

1. Special Equipment Required

You will each need the following equipment:

(a) 1 leveling bulb

(b) 1 No. 00 one-hole rubber stopper with a 3-in. length of 5-mm glass tubing

(c) 1 No. 2 one-hole rubber stopper with a 24-in. length of 6-mm glass tubing
Gas Analysis of Nitrite 2
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(d) 1 15-in. length of 3/16-in. rubber tubing


2. Apparatus Assembly

(a) Assemble the gas analysis apparatus according to the following figure. The two
rubber stoppers should be slightly moistened so as to insure a gas-tight seal. Attach a
clamp to a ring stand for the purpose of holding the leveling bulb. Fill your 800-ml
beaker about three-fourths full with tap water so that it can be set aside and come
to room temperature while you are preparing for the experiment.

(b) Remove the stopper from the top of the buret and slowly pour de-ionized
water into the buret so that when the water level in the buret is just below the
Ourzero mark, theset-up
experimental other iswater level
similar to stands at the lowerInstead
a gas manometer. end ofofthe leveling bulb.
measuring a
height difference in the two arms, however, we adjust the height of the
Make certain that no air bubbles are trapped in the connecting tubing byleveling
bulb so that h = 0, and Pint = Patm. For this reason, all volume measurements
running the water back and forth between the bulb and the buret. Replace the
must be made when the water levels are equal.
Gas Analysis of Nitrite 3
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stopper at the top of the buret while the bulb is clamped level with the top of
the buret.

(c) Test for leaks by lowering the leveling bulb and observing whether, after the
initial drop in the water level in the buret, the level stays in a fixed position or
drops over a period of time due to a leak. If necessary, find and eliminate the
leak.

(d) Remove the 50-ml Erlenmeyer flask while the leveling bulb is level with the
top of the buret.

3. Weighing the Sample. Obtain an unknown sample from the desiccator at the side
shelf and transfer it immediately to your own desiccator. Record the sample number.
Calculate in advance the approximate weight of sample needed, assuming that the sample
contains about 70% NaNO2, you would like to collect about 35 ml of nitrogen gas, the
pressure is 710 torr, and the temperature is 22˚C. Tare a gelatin capsule on the balance.
To prevent picking up any residue from the balance, place the capsule on a clean watch
glass. Then quickly, but carefully transfer the pre-calculated amount of sample of the
unknown from your desiccator to creased weighing paper tared on the balance. Use the
crease in your weighing paper to quickly make a transfer of the unknown into the capsule.
Reweigh the enclosed unknown sample in the capsule to accurately determine the mass
that will be reacted. The samples are quite hygroscopic so keep your supply of unknown
in the desiccator when not needed for weighing. It will not affect your results if your
weighed sample picks up moisture after it has been weighed.

4. Preparing the Reaction Flask


(a) Use your 10-ml pipet to add approximately 20 ml of 0.25 M sulfamic acid
solution to the flask.

(b) Add your capsule with unknown into the flask. You will have about five
minutes before the capsule begins to dissolve to complete steps 4(c) – 5(b).

(c) Moisten the rubber stopper and carefully re-connect the Erlenmeyer flask. Bring
the 800-ml beaker of water up around the flask and support it with the tripod.
Place the leveling bulb near the buret and adjust the bulb up or down so
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that the water levels in the bulb and buret are at the same height. Wait a
few minutes to make certain temperature equilibrium is reached so that the
levels do not change.

5. Carrying out the Reaction


(a) Record the temperature of the water in the beaker and the air temperature in the
room, estimating it to the nearest 0.1°C. Record the water level in the buret,
estimating it to the nearest 0.01 ml.

(b) Lower the leveling bulb. Unclamp the glass tube holding the Erlenmeyer flask in
the water, remove the flask from the beaker, and then shake it gently. Replace the
flask in the beaker and again clamp the glass tube.

(c) Adjust the bulb so as to keep the two water levels at roughly the same height;
periodic readjustment will be needed for perhaps 15 minutes or more until the
capsule has dissolved enough to allow for all of its contents to react. It is
important to shake the reaction flask vigorously several times during this time to
make sure that the reaction has gone to completion. During this waiting period
you could also weigh out another sample of unknown in another vial, following
the precaution noted in 3.

(d) Continue to monitor the level of the water in the bulb and the buret after the
reaction has gone to completion. Adjust the level of the bulb so that the water
remains at the same height as it is in the buret. This may take a few minutes.
When the water levels remain unchanged for a few minutes, record the new water
level in the buret to the nearest 0.01 ml. Record also the temperature of the air
surrounding the buret to the nearest 0.1°C. When no further change in levels is
apparent, make sure that the temperature of the water in the beaker is identical to
that observed in 5(a). If the water temperature has changed in the beaker, stir the
water and cool (with ice) or heat (with burner) as needed. Do this with care, for it
is very easy to overdo it.

6. Repeating the Determination


(a) Remove beaker, disconnect the Erlenmeyer flask, and remove solution and vial.
Rinse the flask and dry the neck to prevent drops from contaminating your next
sample during its insertion into the flask.

Gas Analysis of Nitrite 5


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(b) Repeat the experiment as many times as desired (three minimum), following the
procedures 3-5. You may wish to adjust the sample size in succeeding runs to
give you a conveniently larger or smaller volume of gas.

(c) Determine the barometric pressure (PB) from your reading of the laboratory
barometer. If you are collecting data over more than one lab period, make sure to
read the pressure each day.

PRE-LAB

1) Calculate how many grams of unknown nitrite sample to use in each trial.
Assume your sample is 70.0 % NaNO2 and that the reaction produces a
volume of 35.00 mL at 730 torr and 22.0 °C? Remember to account for the
vapor pressure at this temperature.

2) Suppose your unknown sample were 60.0% nitrite. Would the volume
produced be higher or lower compared to the volume produced under the
same conditions given in question #1? Would you need more or less grams
of unknown to obtain a 35 mL volume change?

CALCULATIONS
1. Calculate the weight percent of NaNO2 in the original sample. Make sure
to take into account the vapor pressures of water, which can be looked up in a
reference manual, such as the CRC.
2. Calculate the mean value of your results, the standard deviation, and the
relative 95% confidence interval of the mean.
3. Hand in the report sheet summarizing your results.
4. Be sure to show your sample calculations and to answer the question on
the report sheet.

Gas Analysis of Nitrite 6


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Name _________________________________ Lab Section __________________

Date Report Submitted ________________ Sample No. __________________

GAS ANALYSIS OF NITRITE

1. Percentage NaNO2 in Sample


First Lab Day Second Lab Day

Observed barometric pressure, PB, mm __________ __________

Run Sample Gas Gas Water Moles %


PN2
Number Weight Volume Temp. Temp. N2 NaNO2

1 _______ _______ _______ _______ _______ _______ _______

2 _______ _______ _______ _______ _______ _______ _______

3 _______ _______ _______ _______ _______ _______ _______

4 _______ _______ _______ _______ _______ _______ _______

5 _______ _______ _______ _______ _______ _______ _______

Average _____________

Standard deviation _____________

Relative 95% confidence interval of the mean, % _____________

Indicate which runs are used to calculate the average by circling their
numbers.

2. Show sample calculations on the reverse side.


3. Solve the following problem. Show the calculations on the reverse
side.
For your first sample reported above how many moles of water vapor were
contained in your reported gas volume?

Moles of water vapor ____________

Gas Analysis of Nitrite 7


LAB DOCUMENTATION - the instructor’s notes

GAS ANALYSIS OF NITRITE-Instructor’s Notes

Before the demonstration have students fill their 800 ml beakers with tap water and allow to
equilibrate to room temperature. This is the constant temperature bath for the reaction.

Answers to pre- lab questions:

1. n (N2) = PV/RT = [(730-19.8) /760 ]atm x 0.0035L = 0.9344 x .035 =.000135


0.08206 Latm/mol K x (273+22) K 24.2077

0.00135 mol of N2 = 0.00135 mol of sodium nitrite !


0.00135 moles of sodium nitrite x 69 g/mol ! 0.09315 g of sodium nitrite

0.09315 g of sodium nitrite = .70 x (Y g of unknown) ! Y = 0.1331 g of unknown

2. The volume would be lower, requiring more grams of unknown.

Notes on experiment:
1. Discuss briefly the chemistry of this experiment and how the experiment illustrates the ideal gas law
and Dalton’s Law of Partial Pressures.

NO2-(aq) + H+ (aq) + NH2SO3- (aq) ! N2(g) + HSO4- (aq) + H2O(l)

PB = PN2 + PH2O

PH2O determined from reference source, such as CRC; note that students should interpolate
between tabulated values to get value at measured T.

2. Sample vials of unknown are obtained from a stock desiccator and immediately put into a transport
desiccator. NaNO2 samples are very hygroscopic. The sample should be weighed quickly and the
rest of sample in the sample vial returned to the transport desiccator immediately. Weigh only 1
sample at a time. At the end of the day, sample vials must be returned to the stock desiccators. A
sample vial cannot be stored in a transport desiccator from one period to the next period.

3. For estimating the size of sample to use, assume 70% NaNO2, 730 torr, 22.0 degrees C and a volume
of 35 ml. This was one of their pre-lab questions. After lst run adjust sample size to get 30-40 ml
volume change, if necessary.

4. Demonstrate and discuss the operation of the set-up.

1
a. Mention need to moisten stoppers and "twist," not push all connections. Be careful not to
break buret etc.

b. Fill buret with de-ionized water. Make sure there are no bubbles or leaks.

c. Show how easily to get and keep air bubbles out of leveling bulb tubes. Fill leveling bulb
with de-ionized water while pinching off the end of the rubber tubing. Then, while holding it
over the sink, suddenly let out a big slug of water. Finally, while it is still pinched off,
connect the tubing to the tip of the buret. The buret should already be full of de-ionized
water, but level below zero mark. Massage the rubber tubing to get rid of air bubbles,
especially where the tubing covers the tip of the buret.

d. Students should use LATEX tubing not pressure tubing with the leveling bulb.

e. Show how to test for leaks by attaching empty Erlenmeyer to close the system and then
lowering leveling bulb and reading buret. Don't forget to open stopcock! The stopper can
pop off if the gas buildups while the stopcock is shut. Wait 5 minutes and read again—level
should not change. This part is important because all of your results will be affected if there
is a leak. If necessary, find and eliminate leak. Be sure to remoisten Erlenmeyer stopper
each time you re-connect.

f. Demonstrate the various ways to adapt system to individual tripods: tall stands over buret
stand base; short ones to the side of the base.

g. Show how to fix leveling bulb ring stand for greatest flexibility and easiest matching of
water levels. You need to use footstands to substitute for the hoods in the lab.

h. 20 mL acid delivered via Mohr pipet (Discuss use of Mohr pipet including how to read
markings) in previous years, but the modified lab no longer requires the use of a Mohr pipet.
Pour approximate amount of sulfamic acid into beaker and pipet from there to avoid
contamination of stock solution.

I think the best way to go about a transfer into a capsule is to weigh an empty capsule on a
watchglass or weighing paper so it does not pick up any residue from the balance. Add a sample
to the weighing paper and transfer carefully to the capsule. Then reweigh the capsule, making
sure that no residue of the nitrite is on the outside of the capsule. It can wiped off with a
Kimwipe.

i. Before connecting the Erlenmeyer with the sample, raise leveling bulb until levels equalize
with the buret reading near 0 mL and only 2-3 cm of water showing in the leveling bulb.
Connect the Erlenmeyer carefully but firmly. Adjust buret and bulb water levels until they
are the same. Read buret volume. Measure the temperature of the bath and the temperature
of air near the top of the buret (for PV = nRT). Make sure thermometer is dry for the air
measurement. Lower leveling bulb before starting reaction.

2
j. Show how to hold flask while vigorously shaking it for complete evolution of gas; care with
connections, etc.; repeat shaking several times during course of reaction to ensure
completeness. Reaction takes 20-25 minutes. (During this time, students can measure out
another sample and/or prepare additional tables in their notebooks for the next run, etc.)

k. Re-measure the air and bath temperatures at the end of the reaction. The temperature of the
bath should be within ± 0.1 degree C of the initial temperature. Ice will be available in the
lab to adjust the beaker temperature when necessary.

l. Read buret volume at end of reaction with buret and bulb levels the same.

5. Show the students how to use the electronic barometer and where it will be in lab.

6. For estimating precision and for making the decision about whether additional runs should be made,
compare the ratios of observed volume of N2 to weight of sample, assuming that the pressure and
temperature for the runs being compared are the same. For best results, three successive runs within
l% relative range should be accomplished. (Should have time to do 2 or 3 runs the first day, and as
many as 4 or 5 the second day if necessary.)

Preparation:
Mixtures of NaCl and NaNO2 can be mixed in different percentages by mass. 50-75% works
better than higher percents. Mixtures are milled for 2hours to ensure homogeneity. Oven dry
unknowns at 110 oC for 1 hour. Keep stored in a dessicator. Each student will need about 0.20
grams of unknown for each run required.

0.25 M sulfamic acid (H2NSO3H) can be made by dissolve 24.5 grams anhydrous sulfamic acid
in 1 liter of water. Keep in colored glass bottles. Each student will need 20 mL of acid for each
run required.

CAS Registry Numbers:

NaCl 7647-14-5

NaNO2 7632-00-0

H2NSO3H 5329-14-6

Other Material(s):
Gel Capsules – size 00 ordered from SPI Supplies (#02302-SS)

3
In the Laboratory

Gasometric Determination of CO2 Released from


Carbonate Materials
Johan Fagerlund* and Ron Zevenhoven
Thermal and Flow Engineering Laboratory, Åbo Akademi University, Turku, Finland
*johan.fagerlund@abo.fi

Stig-Go
€ ran Hulde
" n and Berndt So € dergård
Combustion and Materials Chemistry, Åbo Akademi Process Chemistry Centre, Turku, Finland

As part of the ongoing mineral carbonation research, an pressure; however, we measure the pressure directly. Despite
inexpensive and simple method for determining the carbona- the simple design and reported high accuracy of the LANL
tion content of various carbonated materials (mainly carbo- system, we were unable to accurately repeat the tests on
nated brucite, the mineral form of magnesium hydroxide) was materials that may be low in carbonate and high in magnesium
required. Mineral carbonation is part of a larger carbon dioxide hydroxide and decided to use (similarly to refs 4-6)) the
capture and storage (CCS) portfolio and has received com- method described here.
paratively little attention despite its inherent potential
(natural process, abundant resources, and permanent CO2 Design and Construction of Apparatus
storage). For more information about this area, see, for
example, the latest literature reviews (1, 2). The equipment used to determine the CO2 release of a
The method described here is of value to mineral carbona- material is simple and available in most teaching laboratories, the
tion research owing to its simplicity, low cost, and accuracy, but it most important component being a pressure gauge. Any pressure
could also serve another purpose; that is, to expose undergraduate measurement device capable of determining the pressure to a
students to a hands-on implementation of the ideal gas law and precision of about 100 Pa could be used. In principle, a manometer
some basic inorganic chemistry. In addition, we consider aspects could suffice, although we used a PASPORT Absolute Pressure/
that could easily be overlooked in a theoretical approach, such as Temperature Sensor, PS-2146. Together with PASCO's software
the influence of the heat generated during the reaction between a called DataStudio, the pressure (and temperature) can be logged
solid carbonate and hydrochloric acid. In a classroom, these and displayed simultaneously as the experiment proceeds. This
aspects could be considered beforehand, for example, in groups, equipment is especially developed for educational purposes. In
but it could also be useful to allow the students to find these addition to a pressure gauge, a container for the sample, a smaller
parameters by simple trial and error. For instance, one student container for the acid, an airtight plug, and some flexible tubes to
might take the sample container into his or her hand without attach to the pressure gauge are needed. The container for the
realizing how much it affects the temperature inside the container sample needs to be durable and transparent, such as a sturdy glass jar
as the pressure builds up inside.
before he or she compares the obtained result with that of
An illustration of the experimental setup is shown in Figure 1.
others.
A magnetic stirrer is not shown as it is not necessary; however, it
The method presented here is based on the reaction
is preferable for more consistent results. The system should not
between a carbonated material and an aqueous solution of
be changed after it has been assembled as any change requires the
HCl, which generates CO2. This method is not new and
system to be recalibrated (see the calibration section). The
literature dating back to the late 1940s has described this
temperature sensor should be located inside the glass jar. It is
method (3). The reaction system is sealed and the pressure
also possible to assume constant temperature, but this gives less
increase is used as a measure of the carbonation degree of the
accurate results.
sample, as has also been noted by others more recently (4-6).
Choi and Wong used a similar method to determine the reaction Experimental Procedure
kinetics and carbonate content of eggshells, but did not assess the
accuracy of the method (4). Roser and McCluskey demonstrated The carbonated sample (0.1-0.5 g) is accurately weighed
the use of pressure measurement and data logging to determine ((0.1 mg) using a precision scale. About 2 mL of 5 M HCl
the stoichiometry of reactions between various carbonates and (overstoichiometric) is placed in a small cup that fits inside the
HCl (5). Horvath et al. was able to accurately determine the glass jar. The carbonate sample and the HCl container are carefully
carbonate content of soils measuring the pressure increase inside inserted into the glass jar together with a magnetic stir bar. The
a sealed vessel (6). The method described here takes a slightly glass jar is sealed with a rubber cap containing the temperature
different approach, combining several aspects not described in sensor and a tube that is connected to a pressure gauge. The data
any single literature source cited above. logger (if available) is started and the system is stabilized (humidity
Pile et al. from the Los Alamos National Laboratory builds up) for a short period of time. The magnetic stirring device
(LANL) developed a method for determining the carbonate is started, which spills the HCl solution, and the reaction is left to
content of mineral carbonates (7). They measure the carbonate go to completion, that is, until no more pressure increase is
content indirectly through volume change and hydrostatic observed.

1372 Journal of Chemical Education Vol. 87 No. 12 December 2010 pubs.acs.org/jchemeduc r 2010 American Chemical Society and Division of Chemical Education, Inc.

_ _ _
10.1021/ed1001653 Published on Web 10/08/2010
In the Laboratory

Figure 1. Experimental setup.

The experiment takes less than 10 min, but it is important


that the system is allowed sufficient time to reach thermody-
namic and chemical equilibrium before and after the stirring,
ensuring that all carbonates have dissolved. The steady state of
the system can be determined using the pressure gauge. If the
pressure is stable, so is the system. It is helpful for the students to
see the progress of the reaction on a computer screen (examples Figure 2. Relative humidity as a function of time inside the glass jar for
in Figure 4). two different experiments. Note the different time scales of the two
images.
Hazards
increase the system pressure to a small degree owing to the
Hydrochloric acid is corrosive and causes burns to all body inevitable vaporization of some of the water (HCl vaporization
tissue. contributes only a very small fraction of the water partial pressure
and is therefore neglected, see the supporting information and
Calculations ref 8). The vapor content increases can be seen as a small, yet steady,
increase in the pressure after the glass jar has been sealed. And it can
Using the ideal gas law with a constant volume system, one of be shown (Figure 2) that most of the water evaporating from the
remaining three variables can be determined knowing the other HCl solution takes place before the reaction (typically around 500 s)
two variables. In this experiment, the temperature and the pressure starts. Allowing the system to stabilize before the reaction elim-
are measured so the only unknown variable is the amount of the inates the small equilibrium increase in pressure from H2O.
substance. Assuming that the created atmosphere consists mostly of However, depending on the composition of the sample (e.g.,
CO2 and a small quantity of water, the mass of CO2 released from MgO, Mg(OH)2, or MgCO3) the system will behave differently.
the sample can be calculated. It is also worth mentioning that the The dissolution of MgO and Mg(OH)2 is more exothermic (9.3$
dissolution of CO2 into the solution is negligible owing to the high and 6.7$, respectively) than that of MgCO3; thus, more heat is
acidity of the solution and the magnetic stirring. The reaction released when either MgO or Mg(OH)2 is in the sample. This
taking place inside the reaction vessel is effect can clearly be seen from the data in Figure 2. In the case of the
sample containing only MgCO3, the relative humidity increase due
MgCO3 ðsÞ þ 2HClðaqÞ f Mg 2þ ðaqÞ
to the dissolution reaction is barely visible (around 1000 s), whereas
þ 2Cl - ðaqÞ þ H2 OðaqÞ þ CO2 ðgÞ ð1Þ in the case of a mixture of MgCO3 and Mg(OH)2, the increase in
both temperature and relative humidity is obvious (around 1600 s).
Similarly, knowing that most of the samples also contain magne- In other words, water vapor plays a less significant role in samples
sium hydroxide or magnesium oxide, the reaction equations for with a high carbonation degree, whereas samples with a lower
these with HCl are carbonation degree can easily be overestimated. The relative
humidity was measured by inserting a measuring (temperature,
MgOðsÞ þ 2HClðaqÞ f Mg2þ ðaqÞ þ 2Cl - ðaqÞ þ H2 OðaqÞ
humidity) probe into a glass jar, similar to an actual experiment run.
ð2Þ The carbonation degree is determined by comparing the
amount of CO2 released from the sample to the calculated release
MgðOHÞ2 ðsÞ þ 2HClðaqÞ f Mg 2þ ðaqÞ þ 2Cl - ðaqÞ from a 100% pure carbonate of the same species and mass. The
amount of CO2 in a 100% pure carbonate sample is calculated
þ 2H2 OðaqÞ ð3Þ knowing the molar mass of the carbonate
As can be seen from the equations, only the carbonates produce msample
CO2 giving rise to a pressure increase. However, the water that nCO2 , pure ¼ ð4Þ
forms and the water that is present in the HCl solution will also Mpure

r 2010 American Chemical Society and Division of Chemical Education, Inc. pubs.acs.org/jchemeduc Vol. 87 No. 12 December 2010 Journal of Chemical Education 1373
_ _ _
In the Laboratory

after the experiment, but in practice, this would require long


stabilization times.
In our experiments, we noticed that the temperature inside
the glass jar increases owing to the exothermic nature of the
reactions and it takes a long time before the temperature returns
to the initial value. Therefore, to speed up the process, the
temperature reading can be taken before the system has reached
steady state with its surroundings if a temperature sensor is
placed inside the glass jar.
Before any reaction has taken place in the reaction vessel, the
initial amount of gas (air) can be calculated using the ideal gas
law. Similarly, the final amount can be calculated knowing the
Figure 3. Calibration experiment results using CaCO3 of known purity final pressure and temperature
(99.9%). The figure shows the scattering of the test results as a function of pinit Vsystem
sample size. ninit ¼ ð6Þ
RTinit
where msample is the mass of the sample to be analyzed and Mpure
is the molar mass of the carbonate in question (e.g., MMgCO3 = pfinal Vsystem
nfinal ¼ ð7Þ
84.32 g/mol). Note that in some cases the dissolution of the RTfinal
sample generates more than 1 mol of CO2 per mole of dissolved
carbonate species. In such cases, this has to be accounted where pinit and pfinal are the pressure before and after the reaction,
for in the equation above with a stoichiometric constant. For respectively; Vsystem is the total volume of the system; R is the
example, in the case of pure dolomite, CaMg(CO3)2, 2 mol of universal gas constant; and Tinit and Tfinal are the temperatures
CO2 are released for every 1 mol of dolomite dissolved and the before and after the reaction, respectively. Vsystem is a term that
right side of the equation above should be multiplied by a factor could be measured or approximated knowing the dimensions of
of 2. the parts making up the experimental setup, but it is easier to
The mass and carbonate content of the sample to be simply obtain this value using a sample of known carbonate
analyzed determines the setup requirements. A larger sample content (e.g., 99.9% pure CaCO3). The calibration of the system
will generate more CO2 and require more HCl for a complete is only required the first time or when the setup has been altered.
reaction. Therefore, it is important to establish an upper
boundary for the sample size; it can be calculated based on the Calibration Experiment
stoichiometric reaction ratio between MgCO3 and HCl. For System Volume
every mole of MgCO3, 2 mol of HCl are required in accordance
with eq 1. Therefore, 2 mL of 5 M HCl could dissolve 0.42 g of To determine the system volume (including the glass jar and
MgCO3 or 0.50 g of CaCO3. It is also important to know how tubes and excluding measurement instruments), a calibration
much CO2 could possibly be generated for reasons of pressure experiment is necessary. A calibration experiment is done using a
increase and laboratory safety. Dissolving 0.42 g of MgCO3 calcium carbonate sample of a known carbonation degree.
would result in a significant pressure increase for a small (<200 mL) Measuring the temperatures and pressures before and after the
system volume. Assuming atmospheric pressure in the beginning and reaction allows the determination of Vsystem using
!
constant temperature throughout the reaction, the final pressure msample
would become 167.6 kPa for a 150 mL system and 199.3 kPa for a Rη
Mpure
100 mL system. Taking into account a relatively large temperature Vsystem ¼ ! " ! " ð8Þ
increase, for example, from 21 to 24 !C, the final pressure would not pfinal pinit
change much, increasing only 1.7 kPa for the 150 mL system and -
Tfinal Tinit
2.0 for the 100 mL system.
Knowing the sample and the maximum amount of CO2 Equation 8 was derived by combining eqs 4, 6, and 7 and solving
that a sample could generate allows for calculation of the for Vsystem (for details see the supporting information). Note that
carbonation degree. The carbonation degree is defined according CO2 is not an ideal gas, but under the pressure and temperature
to the following formula: range investigated, this is a valid assumption.
nCO2 , gen nfinal - ninit
η ¼ ¼ ð5Þ System Error
nCO2 , pure nCO2 , pure
Using the average calculated volume, the data were re-
where nCO2,gen is the amount of CO2 released or generated worked to obtain the carbonation degree of the known CaCO3
during an experiment and is the difference between the moles of sample. The results using 99.9% pure CaCO3 are displayed in
gas (air þ generated CO2) at the end, nfinal, and at the start (only Figure 3. The average of 38 samples is 99.97% and the standard
air), ninit. Thus, the carbonation degree is determined knowing (and relative standard) deviation is 0.9%. Two of the 38
only the initial and final conditions inside the sample holder (or measurements were excluded as outliers based on Peirce's criter-
glass jar). The most important aspect of this method is therefore ion (9). In an ideal case, all points would lie on the same
to accurately measure the pressure before any reactions inside the horizontal line, which would mark the 99.9% carbonation
glass jar take place and after, when all the reactions have stopped. degree. However, in practice, there are always errors, seen as
In an ideal case, the temperature should be the same before and the random scattering of points around the 99.9% line in

1374 Journal of Chemical Education Vol. 87 No. 12 December 2010 pubs.acs.org/jchemeduc r 2010 American Chemical Society and Division of Chemical Education, Inc.

_ _ _
In the Laboratory

Figure 3. More information and details about the calibration


calculation procedure can be found in the supporting information.

Experiment Data
For the calculations, we only need two data samplings during
an experiment, one at the start and one at the end. However, it is
also important to observe the temperature and pressure trends
obtained by continuous sampling, especially to assess stabiliza-
tion. A number of points for the temperature and pressure during
three typical carbonate analysis experiments are shown in Figure 4.
Notice that the ambient pressure can be obtained at time zero and
that shortly after this the rubber cap is inserted into the glass jar
(point A) resulting in a small pressure peak. In addition, the
temperature rises a little owing to compression of the gas inside the
glass jar, and because of the aqueous HCl solution, the humidity
inside the glass jar will also increase (see the supporting
information). This can be seen as a slight increase in pressure after
point A. The pressure stabilizes quickly, but usually the temperature
takes a little longer to stabilize. At this point, the magnetic stirrer
can be turned on (or the flask can simply be shaken by hand)
starting the reaction. The reaction is very fast as can be seen from
the steep increase in pressure at point B (the temperature follows
with a small delay). This increase in pressure is the result of CO2
formation in the system and can be used to determine the
carbonation degree of the sample.
The graphs of three experiments using different samples are
shown in Figure 4. The top graph was obtained using a mixture
of 0.0963 g of MgCO3 and 0.0982 g of Mg(OH)2, the middle
graph was obtained using 0.1555 g of Mg(OH)2, and the bottom
graph is the result of an experiment without a sample, just the
HCl solution. The values required for the calculations of the
carbonate content in Figure 4 are taken just before the stirring
(point B) and sometime after the peak pressure has been reached
(point C). The exact position of point C is not critical as long as
the temperature is recorded at the same time. However, it is
preferable to allow the temperature to stabilize for a while to obtain
a representative temperature value for the entire system. The large
drop in both temperature and pressure (point D) is due to the
removal of the rubber cap sealing the glass jar. Note the small increase
in pressure for the “no solid sample” experiment; this is caused by the Figure 4. Temperature and pressure profiles of carbonate analysis
increase in vapor pressure initialized by the stirring. The increase in experiments: (top) a mixture of 0.0963 g of MgCO3 and 0.0982 g of
pressure for the Mg(OH)2 experiment is caused by the small quantity Mg(OH)2; (middle) 0.1555 g of Mg(OH)2; and (bottom) no sample, only
of impurities (3.8%-wt CO3) in the sample. HCl. The letters denote steps in the experiment: A, container sealed; B,
sample and HCl mixed; C, maximum pressure; and D, container opened.
Verifying the Method The results of the five tests are given in Figure 5 showing the
For the purposes of determining the carbonation degree of a carbonation degree based on the certified laboratory results on
sample quickly and without expensive equipment, the method the y axis versus the measured carbonate content on the x axis. In
proposed here performs very well. The data in Figure 3 show that the best case, the dotted line in Figure 5 should pass perfectly
most of the experiments lie within a margin of (1% from the through all of the points and y would equal x. This is nearly the
target line. However, this is for calcium carbonate and we are case and the error is small (R2 = 0.995) showing that the method
more interested in magnesium carbonate/hydroxide mixtures. can be used to accurately find out carbonate contents of solid
Therefore, the method was also tested on a different set of materials. However, it should be noted that not all materials can
samples. The testing on samples consisted of a mix of SiO2 be used. Some materials could react to form other gaseous
(sand), commercial brucite (Dead Sea Periclase Ltd.), and components besides CO2 and H2O, causing the carbonate
magnesium carbonate (Fluka). The materials also contained content of the sample to be overestimated.
some impurities, so the carbonate content of the brucite and Sources of Error
magnesium carbonate was tested in a certified laboratory for
reference purposes. The commercial brucite contained 38 g Knowing how to solve a problem in theory is a completely
CO3/kg and the magnesium carbonate had 461 g CO3/kg. different than solving it in practice. Although the experiment

r 2010 American Chemical Society and Division of Chemical Education, Inc. pubs.acs.org/jchemeduc Vol. 87 No. 12 December 2010 Journal of Chemical Education 1375
_ _ _
In the Laboratory

content of a sample without any specific instructions or just a few


clues. For example, the students could be given the reaction in eq 1
and left to work toward this method in their own way.
If the laboratory does not own a computer logger for
monitoring the pressure and temperature in real time, the
method described by Pile et al. (7) could be used for determining
the carbonation content, although we found their method less
accurate with materials of low carbonate degree. A benefit of
logging the pressure and temperature data and plotting the data
simultaneously to the experiment is that it helps in detecting
possible errors immediately and predicting when the system has
reached a steady state. The method could be further improved by
investing in a hygrometer that would fit together with the
pressure and temperature sensor inside the glass jar. However,
the method works well without this additional data also. The
accuracy of the method is sufficiently high for determining the
Figure 5. Known carbonation degree (from certified laboratory) versus
measured results for five experiments.
carbonate content of mixed samples (e.g., MgCO3, Mg(OH)2,
MgO) with a standard deviation of 1.1%.
described here is fairly simple, students have to recognize various This method functions as a good demonstration technique
factors that could influence its accuracy. This is useful as it for students, providing insight into how the ideal gas law can be
provides a deeper understanding of the problem than that used and what assumptions are necessary when applying a theory
obtained from just calculations. There are several factors that to practice in an educational environment.
are difficult to account for when performing the experiment.
However, some of these “sources of error” can be avoided with a
little effort. First of all, atmospheric humidity has a small yet Literature Cited
noticeable effect on the results as it increases the pressure inside 1. Sipila, J.; Teir, S.; Zevenhoven, R. Carbon Dioxide Sequestration
the glass jar. This source of error can largely be avoided by by Mineral Carbonation: Literature Review Update 2005-2007;
allowing for a long enough settling time before the stirring is Report VT 2008-1; 2008; http://users.abo.fi/rzevenho/Mineral-
started (Figure 2). Accounting for errors is also possible by CarbonationLiteratureReview05-07.pdf (accessed Sept 2010).
running a few experiments without any carbonates and subtract- 2. Huijgen, W. J. J.; Comans, R. N. J. Carbon Dioxide Sequestration by
ing this result from all subsequent experiments. We have done Mineral Carbonation: Literature Review Update 2003-2004,
this and introduced a correction term called xcor (see the Report ECN-C--05-022; 2005; pp 1-52; http://www.ecn.nl/
supporting information). Another (small) source of error comes docs/library/report/2005/c05022.pdf (accessed Sept 2010).
from pushing the rubber cap into the glass jar. Depending on the 3. Williams, D. E. A Rapid Manometer Method for the Determination
way it is inserted into the glass jar, the volume of the system of Carbonate in Soils. Soil. Sci. Soc. Am. Proc. 1948, 13, 127–129.
changes (note that the problem can be altogether avoided if one 4. Choi, M.; Wong, P. Using a Datalogger To Determine First-Order
uses, for instance, a screw cap). However, the error is small and Kinetics and Calcium Carbonate in Eggshells. J. Chem. Educ. 2004,
not considered here in any more detail. 81, 859–861.
5. Roser, C.; McCluskey, C. Pressure and Stoichiometry. J. Chem. Educ.
Discussion and Conclusions 1999, 76, 638–639.
6. Horvath, B.; Opara-Nadi, O.; Beese, F. A Simple Method for
Although there are various ways of determining the carbo- Measuring Carbonate Content of Soils. Soil Sci. Soc. Am. J. 2005,
nation degree of a material, the method described here has the 69 (4), 1066–1068.
benefit of being affordable and easy to use. In addition, it
7. Pile, D.; Benjamin, A. S.; Lackner, K. S.; Wendt, C. H.; Butt, D. P. A
provides a hands-on feel for the application of thermodynamic Precise Method for Determining the CO2 Content of Carbonate
and chemical know-how to anyone who applies it. The fact that Materials. J. Chem. Educ. 1998, 75 (12), 1610–1614.
the method can be used for something of practical use works as a
8. Elm, N.; Zipprian, J.; Schaber, K. Vapor-Liquid Equilibria of Binary
motivator in the otherwise often theoretical studies of chemical and Ternary Aqueous Systems with HCl, HBr, and CaCl2 at Highly
engineers. Diluted Vapor Phases. Fluid Phase Equilib. 2001, 189 (1-2), 163–178.
On the basis of our experience, students with basic knowledge
9. Ross, S. Peirce's Criterion for the Elimination of Suspect Experi-
in inorganic chemistry and some laboratory experience have no mental Data. J. Eng. Technol. 2003, Fall, 1–12.
problems adapting the methodology described here. The number
of instruments and computer loggers restricts the number of
students performing the experiment simultaneously, but perform- Supporting Information Available
ing this experiment as a simple demonstration in front of the Details of calculating the carbonate content; how to correct for
classroom is also helpful. Still, perhaps the best results are achieved if evaporating water. This material is available via the Internet at http://
a group of students are given a task to determine the carbonate pubs.acs.org.

1376 Journal of Chemical Education Vol. 87 No. 12 December 2010 pubs.acs.org/jchemeduc r 2010 American Chemical Society and Division of Chemical Education, Inc.

_ _ _
Supporting Information for Gasometric Determination of
CO2 Released from Carbonate Materials
Johan Fagerlund* and Ron Zevenhoven
5 Thermal and Flow Engineering Laboratory, Åbo Akademi University, Turku, Finland
*johan.fagerlund@abo.fi

Stig-Göran Huldén and Berndt Södergård


Combustion and Materials Chemistry, Åbo Akademi Process Chemistry Centre, Turku,
Finland

10 This section shows the details of calculating the carbonate content according to the
method presented above. Also details regarding the calibration are presented.
A1. Calculations procedure for a calibration experiment
Input data required:
! !"#$%&'#"((')*+,'!("#$%&'
15 ! -./0/"%'$1&((21&')34"+,'"/./0'
! -./0/"%'0&#$&1"021&')5+,'#/./0'
! 6/."%'$1&((21&')34"+,'"7/."%'
! 6/."%'0&#$&1"021&')5+,'#7/."%'

Constants:
20 ! 8./9&1("%'*"(':;.(0".0,'$'<'=>?@A'BC)#;%D5+'
! E"1F;."0&'#;%"1'#"((')*C#;%+'

Example:
! !("#$%&'<'G>GHIA'*';7'E"EJ?')K1L,'II>I'M'$21&+'
! %E"EJ?'<'@GG>G=NI'*C#;%'

25 Obtain the required input data (see above):


! "/./0'<'@GA>A'34"'
! #/./0'<'OIN>@'5')OO>IPE+'
! "7/."%'<'@@I>@'34"'
! #7/."%'<'OIN>Q'5')O?>?PE+'

30 Calculate nfinal from Equation 7 and insert it together with Equations 6 and 4 into
Equation 5:
" pfinalVsystem % " pinit Vsystem %
$$ '' ! $ ''
$
n final ! n init #$ R Tfinal ''& #$ RTinit ''&
!= = (A1)
n CO 2, pure " msample %
$$ '
'
$$# M pure ''&

Solving the equation for Vsystem results in:


" msample %
R!$ '
# Mpure &
Vsystem = (A2)
" pfinal % " pinit %
$ ' ($ '
# Tfinal & # Tinit &

Journal of Chemical Education 9/23/10 1 of 3


JCE Ms #2010-001653.R1 Section–In the Laboratory

35 Inserting the example values into the equation gives:


J ! 0.0794 g $
8.314 0.999 # &
mol K "100.0869 g/mol %
Vsystem = '
( 119.1'10 3 Pa + ( 104.4 '10 3 Pa +
* -.* - (A3)
) (23.3 + 273.15) K , ) (22.9 + 273.15) K ,
ml
10 6 = 134.2 ml
m3
The obtained vale for Vsystem can then be used to evaluate samples of unknown
carbonation degree.
A1. Calculations procedure for a calibration experiment
40 Now that the volume of the system has been determined, samples of unknown
carbonate content can be analysed. The calculation procedure for this is very similar to that
given above and can easily be separated into three different steps:
First, calculate the initial amount of gas (air) in the system using Equation 6. Second,
calculate the final amount of gas using Equation 7 and finally insert the obtained values for
45 ninit and nfinal into Equation 5.
The accuracy of the method described in this paper is largely dependent on the
calibration experiment and performing several calibration experiments for the same system
reveals the methods precision. Below, a table of four calibration experiments is given, with
calcium carbonate (dry, 99.9% pure), the first one being the one in the above example.

50 Table 1. The results of four consecutive calibration experiments using CaCO3 (dry, 99.9% pure).
!" #!"#$%&'()*' $+,+-'(./"*' %+,+-'(0*'
@' G>GHIA' @GA>A' OIN>@'
O' G>GA?I' @GO>O' OIA>I'
?' G>GH?O' @GO>@' OIQ>O'
A' G>G=HQ' @G@>=' OIN>H'
" $1+,"%'(./"*' %1+,"%'(0*' &!2!-&#'(#%*'
@' @@I>@' OIN>Q' @?A>@'
O' @@G>O' OIQ>G' @??>I'
?' @@Q>O' OIQ>@' @?H>@'
A' @@H>Q' OIN>H' @?N>='

Notice how the system volume varies in Table 1, although the setup was not changed
between the experiments. This fluctuation is nothing more than small errors (weighing,
uneven temperature distribution, small variations in glass jar volume, humidity, ideal gas
55 assumption) contributing to the final result. Therefore, a good guess for the system volume is
the average value of however many calibration experiments have been performed. From
Table 1 the average system volume becomes 135.5 ml.
A2. Correcting for evaporating water
A good way to take into account the pressure increase due to H2O evaporation is
60 allowing for the system to stabilize before starting the reaction. The more saturated the jar is
with water vapor before the reaction is started, the more accurate the final result will be.
JCE Ms #2010-001653.R1 Section–In the Laboratory

However, not knowing what the composition of the material to be tested is, the final amount
of water vapor is hard to predict. Assuming that the gas inside the jar would be H2O
saturated after the reaction is also not accurate as shown by Figure 2.
65 Running experiments with inert materials, i.e. materials that do not form gaseous
reactants when exposed to HCl can give some insight to how much water evaporates due to
simple dissolution and stirring. The only source of pressure increase for such an experiment
is the increase in H2O vapor pressure and temperature. The pressure increase due to
evaporating HCl vapor is very low at the temperatures and HCl concentrations considered
70 (e.g. pHCl/pH2O = 0.15% for 5M HCl at 298K, equation 3 in (9)) and thus neglected. Then, by
measuring the temperature, the pressure increase can be fully attributed to the evaporating
water. Below, a table of four such experiments is given.

Table 2. The results of four consecutive empty experiments for H2O evaporation evaluation (Vsystem = 135.5 ml).
'" #!"#$%("()*" $+,+-"(./"*" %+,+)"(0*"
@' R' @G?>Q' OIA>N'
O' R' @G?>Q' OIQ>='
?' R' @G?>@' OIQ>A'
A' R' @G?>@' OIN>N'
" $1+,"%"(./"*" %1+,"%"(0*" *345'(#6%*"
@' @G?>=' OIA>I' @>@@D@GRQ'
O' @G?>=' OIN>A' A>IQD@GRN'
?' @G?>O' OIQ>N' @>NND@GRN'
A' @G?>O' OIN>I' RO>?ND@GRH'

75 The amount of water vapor that is released during a typical experiment run is small
compared to the released CO2 amount which is why the error is typically less than 1%. For
instance the water vapor (average nH2O value from Table 2) would stand for only 0.8% for
the smallest CaCO3 sample size (0.0439 g) in Table 1. Also notice that in one of the
experiments the change in the molar amount of water becomes negative. Therefore, lacking
80 an appropriate humidity sensor, an average value, xcor, is again chosen and applied to each
experiment. In other words, the calculated molar amount of CO2 at the end of each
experiment is lowered by the average value obtained from the no carbonate experiments.