In the Laboratory

Preparation and Analysis of Multiple Hydrates of Simple Salts

Richard W. Schaeffer,* Benny C. Chan, Shireen R. Marshall, Brian Blasiole, Neetha Khan,
Kendra L. Yoder, Melissa E. Trainer, and Claude H. Yoder
Department of Chemistry, Franklin and Marshall College, Lancaster, PA 17604; *R_Schaeffer@fandm.edu

Many salts form more than one hydrate: MnC12ⴢ4H2O The preparation of ionic hydrates can be accomplished
crystallizes from water at room temperature, whereas by four methods:
MnCl2ⴢ2H2O can be obtained by crystallization at 65 °C; 1. slow evaporation of the solvent from a near saturated
CoCl2ⴢ6H2O crystallizes at room temperature, but above solution of the starting hydrate at a temperature within
52 °C, CoCl2ⴢ2H2O forms and above 90 °C, CoCl2ⴢH2O is the stability range of the desired hydrate
stable; CaCl2ⴢ2H2O is available commercially as a desiccant,
2. crystallization within the temperature range of the tar-
but CaCl2ⴢ6H2O is readily formed at room temperature (1).
get hydrate from a saturated solution prepared at
We have developed a laboratory project in which the student
higher temperature (assuming an endothermic heat of
prepares a series of hydrates of simple salts and then deter-
solution)
mines the extent of hydration of the product(s). In conjunction
with previously published articles in this Journal, we believe 3. crystallization within the temperature stability range
this project provides a good introduction to the concepts of from mixed solvents (“knocking the compound out of
solubility, saturation, recrystallization, relative compound solution” by adding a solvent such as 2-propanol to a
stability (e.g., a dihydrate vs tetrahydrate at elevated tempera- nearly saturated aqueous solution)
ture), and simple gravimetric analysis (2, 3). Moreover, the 4. heating a higher hydrate to the temperature range of
project lends itself to many variations. For example, a student the desired lower hydrate
could be given a “starting” hydrated salt and asked to prepare
We have found that the hydrates given in Table 1 are easily
another hydrate within the specified temperature range. Or
prepared by the method indicated. Determination of the
students could be given the formulas of several hydrates stable
water of hydration by heating gently in the Bunsen flame
over different temperature ranges and be asked to “discover”
produced values generally within 1–5% of the theoretical,
a method of preparation. If it is desired to extend the project,
clearly sufficient to determine an integral number of waters
the cation could be determined quantitatively by gravimetric
of hydration. Probably the greatest experimental problem
precipitation of the oxalate, for example, and the anion,
resides in filtration and removal of excess water and simulta-
chloride or sulfate, could be determined by precipitation with
neously protecting the lower hydrates from adsorption of
silver or barium ion, respectively, or by a variety of common
atmospheric water.
volumetric and colorimetric methods (4 ).
Hazards
C AUTION : Some of the compounds used in this exper-
Table 1. Summary of Student Data for Hydrated Salts iment are considered “moderately toxic” (e.g., cobalt chlo-
Hydration (%)
ride LD50, rat, oral = 766 mg/kg) and should be handled
Stability Starting Species Synth
Target Hydrate
Range/°C (CAS No.) Method
with care to avoid ingestion or inhalation of vapors or dust.
Exptl Theor
2-Propanol (CAS 67-63-0) is volatile (0.05 atm at 20 °C)
ZnSO4ⴢ6H2O 39-60 ZnSO4ⴢ7H2O EM 39.0 40.1
and flammable, and should not be ingested (LD50, rat, oral =
(7446-20-0)
5840 mg/kg). We recommend that all reagents be handled
ZnSO4ⴢH2O 6–l00 ZnSO4ⴢ7H2O EM 9.68 10.0
in an appropriate hood. We recommend the use of gloves
(7446-20-0)
and approved safety goggles.
CaCl2ⴢ6H2O 55–29 CaCl2ⴢ2H2O TDM 47.6 49.3
(10035-04-8)
Synthesis of Hydrates
CoCl2ⴢ2H2O 49–137 CoCl2ⴢ6H2O DH 21.9 21.7
(7791-13-1) Evaporation Method (EM)
CoCl2ⴢ2H2O 49–137 CoCl2ⴢ6H2O EM 24.3 21.7 A nearly saturated solution of approximately 2 g of the
(7791-13-1)
commercially available ionic hydrates from Table 1 was pre-
MnCl2ⴢ2H2O 5–135 MnCl2ⴢ4H2O EM 22.8 22.3 pared in an 8-in. test tube or 50-mL beaker by adding small
(13446-34-9) amounts of water (usually about 3–5 mL) until the solid dis-
MnCl2ⴢ2H2O 5–135 MnCl2ⴢ4H2O DH 23.2 22.3 solved. A 0.5-mL portion of 2-propanol was added to the
(13446-34-9) solution and the test tube was placed in a water bath or sand
FeCl2ⴢ2H2O 11–155 FeCl2ⴢ4H2O DH 21.3 22.1 bath maintained at a fairly constant temperature (an ordi-
(13478-10-9) nary hot-plate provided sufficient temperature control) within
FeCl2ⴢ2H2O 11–155 FeCl2ⴢ4H2O SAM 22.4 22.1 the stability range of the desired hydrate (see Table 1). The
(13478-10-9) solution was allowed to evaporate until crystals formed. In

JChemEd.chem.wisc.edu • Vol. 77 No. 4 April 2000 • Journal of Chemical Education 509

 In the Laboratory

no case was the solution allowed to evaporate to dryness. The Information for the Instructor
rate of evaporation was slowed in some cases by covering the
In this project, a series of inorganic ionic hydrates are
test tube or beaker with Parafilm tape into which several holes
prepared and analyzed for water content. The concepts of
were punched. The crystals were isolated by suction filtration,
hydration, solubility, saturation, crystallization, compound
washed with 2-propanol, and placed in a desiccator overnight.
stability, and simple gravimetric analysis are illustrated and
Temperature Difference Method (TDM) reinforced in a straightforward experiment. We believe the
experiment is probably most suited for the general chemistry
A nearly saturated solution of the commercially available
laboratory, and that the variations possible in the hydrates
hydrate was prepared by placing about 2 g of the starting
prepared and analytical methods employed within the frame-
metal hydrate in an 8-in. test tube or 50-mL beaker, which
work of the procedure described make this a versatile project.
was placed in a water bath or sand bath maintained at a
A glance at Table 1 reveals that not every synthetic method
temperature above the maximum limit for the target hydrate.
was used for each target hydrate. This paper is not meant to be
Distilled water was added dropwise to the test tube until all
an exhaustive report on the preparation of specific hydrates,
the solid was dissolved. One or two additional drops of dis-
but rather a report of an undergraduate-level experiment
tilled water were added and the test tube was again placed
suited to illustrate the topics mentioned. Each of the synthetic
into a water or sand bath maintained at a lower temperature
methods will work with a variety of common hydrates with
within the temperature range for stability of the target hydrate.
the exception of the thermal difference method (TDM),
The target hydrate typically crystallized within 30 min. The
which may not generate product if the target hydrate has a
crystals were isolated by suction filtration, washed with 2-pro-
higher solubility at a lower temperature or has nucleation
panol, and placed in the desiccator overnight.
problems. In one application the instructor could assign a
Solvent Addition Method (SAM) student or small group of students the synthesis and analysis
of a hydrate from Table 1 using all four techniques. Alterna-
A working solution of an ionic hydrate from Table 1 was
tively, multiple hydrates could be assigned using one or more
formed as described in the EM procedure. The test tube or bea-
synthetic approaches. The student would then “discover”
ker containing the working solution was placed into a water or
which approaches seem to work best for each hydrate.
sand bath maintained at a temperature within the stability range
Each of the synthetic methods described was tested by
of the target hydrate. After the temperatures equilibrated, 2-pro-
undergraduate students and the results are summarized in
panol was added dropwise until a precipitate formed. (Other
Table 1. Students were very successful in isolating the various
weakly complexing solvents that are miscible with water but less
hydrates by each of the techniques. Moreover, the analysis of
effective than water at solubilizing ionic materials could also be
the water of hydration was successful on the basis of a com-
used to precipitate the hydrate. 2-propanol is a good choice be-
parison of the expected mass percent of water from the “ideal”
cause it is readily available, reasonably safe, and inexpensive.)
formula with the experimental mass percent (see columns 5
The crystals were isolated by suction filtration, washed with 2-
and 6 in Table 1.). The average percent error for the com-
propanol, and placed in the desiccator overnight.
parisons reported was 3.4% (2.3% if one value with an espe-
Direct Heating (DH) cially large error, cobalt(II) chloride via the evaporation
method, is neglected).
Approximately 2 g of the starting hydrate was heated in
The instructor will probably want to include a discussion
an oven for 24 h at a temperature within the stability range
of the nature of hydrated salts (i.e., how is the water incor-
for the hydrate desired. The product hydrate was stored in a
porated into the structure) and the effect of temperature on the
desiccator until analyzed.
extent of hydration. We recommend the excellent discussion
Determination of Water of Hydration by Kauffman and Baxter (5) as a guide.
A 0.5–1.0 g (± l mg) hydrate sample was weighed into a
Literature Cited
porcelain crucible and heated gently with a low Bunsen
burner flame. After approximately 20 min the heat was 1. CRC Handbook of Chemistry and Physics, 75th ed.; Lide, D.
increased until there was no further evidence of the release R., Ed.; CRC: Boca Raton, FL, 1994.
of water. The sample should not be heated so strongly that 2. Silber, H. B. J. Chem. Educ. 1972, 49, 586–589.
decomposition occurs (as evidenced, for example, by an extreme 3. Kielland, J. J. Chem. Educ. 1937, 14, 412–414.
change in color—from blue or green to black in the case of 4. Procedures can be readily found in many laboratory manuals.
iron and copper salts). After cooling in a desiccator the sample See, for example: Day, R. A.; Underwood, A. L. Quantitative
was reweighed and the percent water of hydration was cal- Analysis, 5th ed.; Prentice-Hall: Englewood Cliffs, NJ, 1986.
culated from the difference in weight. 5. Kauffman, G. B.; Baxter, J. F. J. Chem. Educ. 1981, 58, 349–353.

510 Journal of Chemical Education • Vol. 77 No. 4 April 2000 • JChemEd.chem.wisc.edu