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Synthesis and Thermal Analysis of the Group 2 (IIA) Metal Oxalate Hydrates

Elizabeth Harrison

CHEM 2319 3A Group #7

6 May 2019
Purpose

For this lab, MC2O4 were prepared. M stands for the following group 2 metals: Mg2+, Ca2+,

Sr2+, and Ba2+. The percent yield and thermogravimetric analysis (TGA) spectra for these complexes

were obtained and used in the characterization of them. The purpose of this experiment was to

characterize these complexes in the form of metal oxalates and for the determining of the stability of

these compounds through TGA.

Theory

Oxalate ligand is considered a bidentate ligand: a molecule that can bind to an atom via two

coordinate covalent bonds at a time, in this case to the group 2 metals. A form of the oxalate ligand

is shown:

Oxalate ligand belonging in the D2h point group

The group 2 alkaline earth metals all have a 2+ charge, making them relatively reactive and

wanting to bond with other elements/ligands. The Group 2 metal ions forms insoluble oxalates

from neutral or weakly acidic solution. These oxalates precipitate as white crystalline hydrated

compounds or specific composition.

These complexes can be found as early as in the year of 1853 after being found on a column

in the Parthenon. Now they are seen in myriad substrates, including easel and wall paintings,

polychrome stone and wood, stone monuments and architecture, and even metal, glass, rock art and

paper. The presence of metal oxalates is overwhelming and are continuing to grow every day.
Experimental Process

For this lab, my partner and I had to synthesize four metal oxalates and so she and I split it

up where she did two and I did two. The four metals used in this experiment were Mg2+, Ca2+, Sr2+,

and Ba2+. I oversaw Ca2+ and Ba2+ while she synthesized the other two.

26 mg of calcium carbonate, 39 mg of strontium carbonate, 37 mg of barium carbonate, and 40 mg

of MgO were weighed into four separate 25-mL beaker. To each beaker, 2 mL of deionized water

and a magnetic stirring bar was also added. The beaker was then covered with a watch glass and set

on top of a hot plate. While it was being gently stirred and warmed up on the plate, 6M HCl was

added to the solution in the beaker until all the solid had dissolved.

The solution was then diluted to 10 mL with deionized water and one/two drops of 1%

methyl red indicator was added. The solution turned acidic and developed a light red color. 1.5 mL

of saturated ammonium oxalate solution and 1.5 g of solid urea was also added to the light red

solution. In the case of the magnesium, my partner added 4.5 g of urea.

Although the solution should have changed color from red to yellow as it was gently boiled

after all the above additions, it did not. There were no color change and no colorless crystals of

metal oxalates formed. For all four of the solutions, we had to add a few drops of 6M ammonia to

neutralize the excess acid. After adding those few drops, all precipitates formed except for MgC2O4.

Because there was no product using the MgO, my partner and I decided to repeat the steps a second

time still getting nothing at the end.

The solutions were cooled to room temperature and using a Hirsch funnel and water trap,

the three product crystals were collected using suction filtration. They were washed twice with cold

water and then the crystals were set in desiccator for a whole week.
The second week we were able to weigh the tree metal oxalates to be 22 mg of CaC2O4, 38

mg SrC2O4 and 38 mg BaC2O4. These yields were used to determine the percent yields and also the

TGA was run by the TA the second week as well.

Experimental Results

The adjusted percent yields after taking out the account for water for each are as follows:

58.18% for CaC2O4, 81.08% for SrC2O4, and 87.24% for BaC2O4.

The TGA spectra for CaC2O4 is shown below:

We are able to see three distinctive temperature ranges: 111.29-173.11˚C, 173.11-363.44˚C, and

437.07-514.17˚C. Since the decomposition of metal oxalate hydrates decompose in three steps:

(1) MC2O4·nH2O = MC2O4 + nH2O

(2) MC2O4 = MCO3 + CO

(3) MCO3 = MO + CO2


we can assume the first temperature range corresponds to the decomposition of (1), second range

corresponds to (2), and the third range corresponding to (3). The range from 514.17˚C and beyond

stabilized the weight at 64.34%.

The TGA spectra for SrC2O4 is shown below:

We can see two distinctive temperature ranges: 150-275˚C, 275-350˚C, and 350˚C beyond. This

spectrum was not as clear as the one for Ca oxalate. However, from it, we are still able to see the

decomposition of the water and at least one of the other decompositions. In the second range, there

is a little bump which could indicate the decomposition from (2) to the starting decomposition of

(3). It is very hard to see where the change occurs in that small range and it could mean that there

was not enough of the actual SrC2O4 product to begin with for the TGA analysis.
The third TGA spectrum for BaC2O4 is shown below:

Of all three TGA spectra we obtained, the BaC2O4 was the hardest to determine where the major

ranges lied. We can clearly see a range from 90-120˚C, 120-450˚C, 450-525˚C, and 525˚C beyond.

We can assume the initial small decline is from the decomposition of (1), however there was a big

flat range from 120-450˚C where there was really no change in the % weight. That could mean either

(2) or (3) didn’t happen for that period until it was hot enough for the decomposition of those steps.

Conclusion

The percent yields for SrC2O4 and BaC2O4 were both extremely well. Coming in at over 80%,

we were able to recover most of our product. However, for CaC2O4, the percent yield was

significantly less than the other two products. That could be due to a few possible errors. One major

error could have been that some of the crystals leaked through the filter paper as we were isolating

it. I think overall, the percent yields were a success and we were able to get products for three of the

four beginning metals.


The TGA literature values for CaC2O4 were close to our values. Below is a literature TGA

spectrum obtained for CaC2O4:

The three ranges were close to our experimental ranges and so the TGA was a success. I was not

able to find any literature values for BaC2O4 and SrC2O4, however, from looking at our TGA

spectra, it is clear to see those two did not turn out well as the calcium oxalate. In that area, I think

more purification was needed for a more precise TGA.

One major possible error we were not able to obtain any product using MgO was because

we accidentally did a part of the procedure wrong. For all the other three, we were to dilute the

solution using distilled water to 10 mL, but that was not the case for MgO. Instead of not diluting it,

both my partner and I diluted the solution to 10 mL using distilled water as we tried to synthesize

the magnesium oxalate. Because of the intense dilution that we should not have done, it most likely

caused our product not to form. Another possible error could be some of the product slipped

through the filter paper as we were filtering it and that caused our percent yields to be less. One final

error was not letting our products dry completely before taking the final weight and TGA. A reason
why our percent yield was so high could be due to the fact that there was still a lot of water left in

our product and possible filter paper which caused a discrepancy in our calculations. It would have

been better if we were able to dry it perhaps using a hair dryer to completely dry our product.

Overall, this experiment was successful because we were able to obtain 3 out of the four metal

oxalates and able to obtain TGA values for them.


References

Froberg, Linda. “Thermal Analysis: TGA/DTA.” Process Chemistry Centre, Abo Akademi University.

Miessler, Gary L, et al. Inorganic Chemistry, 5th edition., Pearson, 2014.

Szafran, Zvi, et al., “Experiment 2.” Microscale Inorganic Chemistry: A Comprehensive Laboratory

Experience, Wiley, 1991.

Lawson-Wood, K.; Robertson, I. Study of the Decomposition of Calcium Oxalate Monohydrate using a

Hyphenated Thermogravimetric Analyser - FT-IR System (TG-IR); PerkinElmer: Waltham, 2016.

Dollimore, D.; Heal, G.; Passalis, N. “The Thermal Analysis of Strontium Oxalate.” Thermochimica

Acta 1985, 92, 543-546.

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