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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
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In the Laboratory
Table 1. Comparison of Results Using the Glass Vials and Gelatin Capsules
Results with Glass Vial Results with Gelatin Capsule
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.
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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
PRINCIPLES
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
(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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(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.
(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
Gas Analysis of Nitrite 4
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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.
(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.
(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.
Average _____________
Indicate which runs are used to calculate the average by circling their
numbers.
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.
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.
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.
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.
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
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
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
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
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
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
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#;%'
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 ''&
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.