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In the Laboratory

Infrared Examination of the Transformation of Barium Sulfate


into Barium Carbonate
An Inorganic Infrared Qualitative and Quantitative Experiment

Gene E. Kalbus* and Van T. Lieu


Department of Chemistry and Biochemistry, California State University, Long Beach, CA 90840; *gekalbus@aol.com
Lee H. Kalbus
Department of Chemistry, California State University, San Bernardino, CA 92407

Student experiments and lectures on infrared spectroscopy are generally concerned with the investigation of organic materials. Experiments on the application of infrared
in the inorganic area are limited (15) and, consequently, students do not realize that infrared spectroscopy can have value
in such investigations. A number of publications on inorganic infrared spectroscopy are available, but generally consist of vibrational theory, spectrastructure correlations, and
compilations of inorganic spectra (613).
This experiment provides an interesting pedagogical exercise that not only introduces the students to the value that
infrared spectroscopy can have in studying inorganic systems,
but also illustrates a procedure used in classical wet chemical
qualitative analysis for sample preparation. In classical qualitative analysis, a water or acid insoluble sample, such as barium
sulfate, if boiled in a solution of sodium carbonate, can be
transformed into species that can be detected (1417).
BaSO4 + CO32

BaCO3 + SO42

(1)

The sulfate ion, now in solution, can be qualitatively detected,


and the barium ion detected after acid dissolution of the
barium carbonate. The extent of the transformation depends
on the time and temperature of the reaction, the initial reactant concentrations, and the relative solubility products of
barium sulfate and barium carbonate.
Since both barium sulfate and barium carbonate possess infrared active polyatomic anions that exhibit a number
of characteristic non-interfering absorption bands, infrared
spectroscopy is an ideal and convenient method of following
the reaction. Infrared spectroscopic examination of the residue qualitatively demonstrates that the reaction has occurred
and measurements of relative absorbances of selected barium
sulfate and barium carbonate bands permit quantitative calculations as to the extent of the transformation reaction. The
equilibrium constant for the reaction can be determined and
the influence of time and temperature on the reaction can
be studied.
Since the experiment involves the partial transformation
of one substance into another, the extent of the reaction can
be determined from the concentration ratio, (moles
BaCO3)(moles BaSO4), when the reaction is terminated. A
measurement of the experimentally determined absorbance
ratio of BaCO3BaSO4 can be converted to the mole ratio
through Beers law if the corresponding absorptivity ratio is
known. The absorptivity ratio is obtained by measuring the
absorbance ratio of a standard containing an equal number
of moles of barium carbonate and barium sulfate.

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A ratio method is used since it simplifies the procedure


and eliminates or reduces errors associated with an absolute
method based on the mass of a sample. The ratio method
has the following advantages: (i) the sample does not have to
be homogeneously dispersed in the potassium bromide matrix; (ii) the sample in the pellet does not have to be weighed
with the inherent error associated with weighing small quantities of sample; (iii) the samplepotassium bromide mixture
does not have to be quantitatively transferred from the grinding and die apparatus into the pellet form; (iv) grinding the
sample with potassium bromide for a sufficient time to reach
optimum dispersion, which is required for maximum constant absorbance, is not as critical (18, 19), and (v) the error
due to nonlinearity of Beers law plot in infrared spectroscopy may be reduced or minimized (20).
The reaction can be followed by measuring the absorbance ratio of any barium carbonate to any barium sulfate
band. However, the two bands selected must simultaneously
fall within the optimum region (20) for making absorbance
measurements (0.060.96). With the concentrations of the
two reactants used in this experiment, measurements on the
absorbances of the 1449 cm1 band of barium carbonate and
the 1197 cm1 band of barium sulfate are found to be suitable choices to satisfy this criterion.
Determination of the Absorptivity Ratio
of Barium Carbonate/Barium Sulfate
A standard sample of a 1:1 mole ratio of barium
carbonatebarium sulfate is prepared. The infrared spectrum
between 2000400 cm1 of an approximately 0.5% (wtwt)
sample in potassium bromide is illustrated in Figure 1, with
the barium carbonate and barium sulfate bands identified.
The ratio of the absorbance of barium carbonate at 1449 cm1
to the absorbance of the barium sulfate at 1197 cm1 is measured, using the base line technique (2022).
The student average for this absorbance ratio was found
to be approximately 2.0. This is also the ratio of the corresponding absorptivities since the standard contains an equal
mole ratio of the two constituents and the thickness term is
constant.
The Transformation Reaction
From a boiling mixture of 7.50 mmol of sodium carbonate and 2.00 mmol of barium sulfate in 100-mL distilled water, 5-mL samples are withdrawn through a tubing inserted
down a reflux condenser at time intervals of 0.5, 2, 5, 10, 15,

Vol. 83 No. 6 June 2006

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In the Laboratory

culated to be approximately 0.12. This would also be the ratio of the solubility product of barium sulfate to the solubility product of barium carbonate (17).
Effect of Temperature on the Reaction
Examination of the infrared spectrum by repeating the
experiment at room temperature for one hour shows that essentially no reaction occurs, demonstrating the importance
of temperature on the reaction.
Hazards
Barium carbonate is toxic by ingestion and should be
handled with care. Potassium bromide is moderately toxic
by ingestion and inhalation. Sodium carbonate is basic and
is an irritant. [Editors Note: CLIPs are available in J. Chem.
Educ. for BaSO4 (2006, 83, 33); Na2CO3 (2002, 79, 1315).]
Figure 1. Infrared spectrum of a 0.5% standard sample of a 1:1
mole ratio of barium carbonate/barium sulfate in potassium bromide.

Figure 2. Plot of percent transformation of barium sulfate to barium


carbonate as a function of time at boiling temperature.

and 20 min. After filtering, washing, and drying, infrared spectra are run and the ratio of the absorbance of barium carbonate (1449 cm1) to barium sulfate (1197 cm1) is measured
for each of the six samples. Using these absorbance ratios and
the student average of 2.0 for the absorptivity ratio, the mole
ratio of barium carbonatebarium sulfate is calculated. From
the initial concentrations of the reactants, the balanced equation (eq 1), and the mole ratio, the percent transformation of
the samples at each of the six time intervals is calculated (see
Student Handout of the Supplemental MaterialW for detailed
calculations). The plot of percent transformation versus time
of reaction (Figure 2) shows that equilibrium is established
after approximately 15 min with a transformation of approximately 40% (a smooth line has been drawn between the points
on the plot). Using the percent transformation, the equilibrium constant, K, which is the ratio of SO42CO32, is cal-

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Conclusion
Our students have performed this experiment and variations of it in our instrumental analysis laboratory for the past
15 years. The experiment is suitable for a variety of upperdivision laboratory courses in instrumental methods of analysis, physical, and inorganic chemistry. It works well, without
complication, and is well received by students. They find it
interesting and challenging while providing them with a valuable learning experience in various areas of chemistry. This
experiment demonstrates that infrared spectroscopy can be
of value in the study of inorganic systems. It visually illustrates the effectiveness of a procedure used in classical wet
chemical qualitative analysis for sample preparation. This
transformation of barium sulfate to barium carbonate would
be difficult to demonstrate by other means. Infrared examination of the residue qualitatively demonstrates that the reaction has occurred. Measurements of relative absorbances
of selected barium sulfate and barium carbonate bands can
be used to quantitatively calculate the percent transformation and the equilibrium constant for the reaction. The influence of time, temperature, and reactant concentrations on
the extent of the reactions can also be studied.
The student can easily complete the experiment in two,
three-hour laboratory periods. If the section on evaluating
the percent transformation over a series of time intervals is
omitted, one laboratory period would be sufficient to (i) prepare the standard 1:1 mole ratio of barium carbonatebarium
sulfate mixture, (ii) carry out the transformation reaction at
100 degrees for 15 minutes to equilibrium, (iii) simultaneously carry out the reaction at room temperature for 1 hour,
and (iv) obtain the infrared spectra of the three samples. Pellets can be saved and run at a later date.
This experiment can be varied by using different reactant concentrations or by performing the reverse reaction, that
is, the transformation of barium carbonate to barium sulfate.
The application of infrared spectroscopy to the study of inorganic systems can be extended to numerous other systems,
provided the species contain polyatomic infrared-active
groups such as chromate, oxalate, carbonate, thiocyanate, and
phosphate.

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In the Laboratory
W

Supplemental Material

Instructions for the students and notes for the instructor are available in this issue of JCE Online.
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Journal of Chemical Education

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