CMY 285 Practical Experiment 3

Synthesis of Cobalt(III) Complexes

Suné Martins

u20518073

Wednesday Group

19 October 2022
 Contents
Introduction 1
Results 2
Discussion 8
References 9

i
Introduction
This experiment will focus on the importance of synthetic chemistry in regard to the
discoveries of properties of the Cobalt(III) complexes. Cobalt complexes are important as they
have applications in the metallurgical industry for steel production, in the chemical industry as
a catalyst, and in the ceramics industry.1 The main objective for this experiment is to
successfully synthesize five Cobalt(III) complexes and confirm Alfred Werner’s theory of the
structures and geometries of complex ions, determine the ligands bonded to the metal as well
as determine the number of ions in each product.

To accomplish this study Tetraamminecarbonatocobalt(III) Nitrate and Hexaminecobalt(III)

Chloride will be synthesized then Pentaaminechlorocobalt(III) Chloride,
Dinitritotetraamminecobalt(III) Nitrate and Dichlorotetraamminecobalt(III) Nitrate will be
synthesized using the Tetraamminecarbonatocobalt(III) Nitrate. The structures of these
products will be confirmed using IR Spectroscopy and by determining the conductivity of the
product the number of ions can be established.
Alfred Werner proposed the theory of transitional-metal complexes having more of a spherical
structure than a chain structure. Werner introduced the concept of ‘primary’ and ‘secondary’
valence, ‘primary valence’ being the oxidation state of the metal ion and ‘secondary valence’
being the coordination number.2 The coordination numbers establish structures such as
octahedral complexes, these complexes can form isomers. These new proposed structures
meant that covalent bonds would form giving rise to ions and counter ions. Due to these ions
the conductivity of the solutions can be measured.

The number of ions in the complex can be known by comparing the value of the molar
conductive power of the complex solution with the standard molar conductivity, the greater
value of conductivity the more ions present in the solution.3 The conductivity of a product can
also indicate the purity of the product. For example, if the proposed structure of a product
indicates that there should two ions in solution, but the value of conductivity is higher than
that of a standard solution with two ions there is most likely an impurity in the product.

An additional way to see the purity of a product is through IR Spectroscopy. Infrared

spectroscopy to determine the molecular composition of polymers by analyzing
the characteristic vibrations of functional groups.4 In IR the sample is irradiated with a broad
band of infrared frequencies, and the intensity of the reflected or transmitted infrared
radiation is measured as a function of frequency.5 By analyzing the peaks of the IR spectra the
purity of the compound can be determined due to the presence of certain peaks. If one product
is synthesized from another product, such as the case in this study, the IR spectra of the two
products can be compared to see if there are residues of the reactant in the product.

1
 Results
Structures and yields and crystals of products
Five Cobalt(III) complexes were synthesized, the structure of Tetraamminecarbonatocobalt(III)
Nitrate can be seen in Figure 1, Hexaminecobalt(III) Chloride can be seen in Figure 2,
Pentaaminechlorocobalt(III) Chloride can be seen in Figure 3, Dinitritotetraamminecobalt(III)
Nitrate can be seen in Figure 4 and Dichlorotetraamminecobalt(III) Nitrate can be seen in
Figure 5.

Figure 1 Proposed structure of

Figure 2 Proposed structure of Figure 3 Proposed structure of
[Co(NH3)4CO3]NO3
[Cu(NH3)]Cl3 [Co(NH3)5Cl]Cl2

Figure 4 Proposed structure of Figure 5 Proposed structure of

[Co(NH3)4(NO3)2]NO3 [Co(NH3)4Cl2]NO3

The following yield and theoretical yield were obtained for the synthesis of
Tetraamminecarbonatocobalt(III) Nitrate:

The equation of synthesis is as follows:

𝐻2 𝑂
2(𝑁𝐻4 )2 𝐶𝑂3 + 2[𝐶𝑜(𝐻2 𝑂)6 ](𝑁𝑂3 )2 + 6𝑁𝐻3 + 𝐻2 𝑂2 → 2[𝐶𝑜(𝑁𝐻3 )4 𝐶𝑂3 ]𝑁𝑂3 + 14𝐻2 𝑂 + 2𝑁𝐻4 𝑁𝑂3
The limiting reagent is [𝐶𝑜(𝐻2 𝑂)6 ](𝑁𝑂3 )2 thus the theoretical yield can be calculated as follows:
𝑚[𝐶𝑜(𝑁𝐻3)4𝐶𝑂3]𝑁𝑂3 = 𝑛[𝐶𝑜(𝐻2 𝑂)6](𝑁𝑂3)2 × 𝑀[𝐶𝑜(𝑁𝐻3)4𝐶𝑂3]𝑁𝑂3

= 0.05158 𝑚𝑜𝑙 × 249.069 g. 𝑚𝑜𝑙 −1

= 12.85𝑔
The actual yield was 9.45g making the percentage yield 74.24%

The following yield and theoretical yield were obtained for the synthesis of
Pentaaminechlorocobalt(III) Chloride:
2
The equation of synthesis is as follows:
𝐻2 𝑂
[𝐶𝑜(𝑁𝐻3 )4 𝐶𝑂3 ]𝑁𝑂3 + 2𝑁𝐻3 + 3𝐻𝐶𝑙 → [𝐶𝑜(𝑁𝐻3 )5 𝐶𝑙]𝐶𝑙2 + 𝐻2 𝑂 + 𝐶𝑂2 + 𝑁𝐻4 𝑁𝑂3

The theoretical yield is 5.03g and the actual yield was 1.59g making the percentage yield
31.61%

The following yield and theoretical yield were obtained for the synthesis of
Hexaminecobalt(III) Chloride:

The equation of synthesis is as follows:

𝐻2 𝑂
2𝐶𝑜𝐶𝑙2 ∙ 6𝐻2 𝑂 + 11𝑁𝐻3 + 𝐻𝐶𝑙 + 𝐻2 𝑂2 + 𝑁𝐻4 𝐶𝑙 → 2[𝐶𝑜(𝑁𝐻3 )6 ]𝐶𝑙3 + 14𝐻2 𝑂
The theoretical yield is 10.13g and the actual yield was 0.23g making the percentage yield
2.27%

The following yield and theoretical yield were obtained for the synthesis of
Dinitritotetraamminecobalt(III) Nitrate:

The equation of synthesis is as follows:

𝐻2 𝑂
[𝐶𝑜(𝑁𝐻3 )4 𝐶𝑂3 ]𝑁𝑂3 + 2𝐻𝑁𝑂3 + 2𝑁𝑎𝑁𝑂2 → [𝐶𝑜(𝑁𝐻3 )4 (𝑁𝑂2 )2 ]𝑁𝑂3 + 𝐻2 𝑂 + 𝐶𝑂2 + 2𝑁𝑎𝑁𝑂3

The theoretical yield is 1.16g and the actual yield was 0.41g making the percentage yield
35.34%

The following yield and theoretical yield were obtained for the synthesis of
Dichlorotetraamminecobalt(III) Nitrate:

The equation of synthesis is as follows:

𝐻2 𝑂
[𝐶𝑜(𝑁𝐻3 )4 𝐶𝑂3 ]𝑁𝑂3 + 2𝐻𝐶𝑙 → [𝐶𝑜(𝑁𝐻3 )5 𝐶𝑙2 ]𝑁𝑂3 + 𝐻2 𝑂 + 𝐶𝑂2

The theoretical yield is 1.05g and the actual yield was 0.10g making the percentage yield 9.52%
The data above has been summarized in Table 1 below:
Table 1 Yield and percentage yield of the five synthesized complexes

Product Theoretical Actual yield Percentage

yield (g) (g) yield (%)
Tetraamminecarbonatocobalt(III) Nitrate 12.85 9.54 74.24
Pentaaminechlorocobalt(III) Chloride 5.03 1.59 31.61
Hexaminecobalt(III) Chloride 10.13 0.23 2.27
Dinitritotetraamminecobalt(III) Nitrate 1.16 0.41 35.34
Dichlorotetraamminecobalt(III) Nitrate 1.05 0.10 9.52

3
 Figure 6 to Figure 10 show the final product after each synthesis

Figure 6 [Co(NH3)4CO3]NO3 crystals Figure 8 [Co(NH3)5Cl]Cl2 crystals Figure 7 [Co(NH3)4(NO3)2]NO3 crystals

Figure 9 [Cu(NH3)]Cl3 crystals Figure 10 [Co(NH3)4Cl2]NO3 crystals

4
Conductivity and ions
For the purposes of this study the following conductivity measured in Siemens (S) standards
will be used as seen in Table 2.
Table 2 Conductivity values and number of ions of known standards

Standard Number of ions Conductivity (S)

𝐾𝐶𝑙 2 519
𝐵𝑎𝐶𝑙2 ∙ 𝐻2 𝑂 3 595
𝐾3 [𝐹𝑒(𝐶𝑁)6 ] 4 895

The conductivity and number of ions of each synthesized product has been summarized in
Table 3.
Table 1 Conductivity and number of ions of synthesized products

Product Conductivity Expected Determined

(S) number of number of ions2
ions1
Tetraamminecarbonatocobalt(III) 464 2 2
Nitrate
Pentaaminechlorocobalt(III) Chloride 602 3 3
Hexaminecobalt(III) Chloride 891 4 4
Dinitritotetraamminecobalt(III) 756 2 4
Nitrate
Dichlorotetraamminecobalt(III) 655 2 3
Nitrate

1
Based off proposed structures
2
Number of ions determined based on conductivity values of known standards and their correlated number of
ions.
5
IR Spectroscopy
The characteristic peaks visible in the IR spectra of the synthesized products have been
summarized in Table 4.6–8
Table 2 Characteristic peaks in IR Spectra of ligands

Ligand Bond motion Wavenumber (cm-1) Appearance

NH3 N-H stretching 3000 – 2800 Strong and broad
NH3 N-H bending 1650 – 1580 Medium
CO32- C=O stretching 1790 – 1760 Medium
NO3- N=O stretching 1690 – 1525 Medium

Each product synthesized was analyzed using IR Spectroscopy. The IR spectra of each product
can be seen in Figure 11 to Figure 15.

Figure 11 IR spectra of synthesized Tetraamminecarbonatocobalt(III) Nitrate

Figure 12 IR spectra of synthesized Pentaaminechlorocobalt(III) Chloride

6
Figure 13 IR spectra of synthesized Hexaminecobalt(III) Chloride

Figure 14 IR spectra of synthesized Dinitritotetraamminecobalt(III) Nitrate

Figure 15 IR spectra of synthesized Dichlorotetraamminecobalt(III) Nitrate

7
Discussion
In Table 1 the overall percentage yields of the products are very low, except that of
Tetraamminecarbonatocobalt(III) Nitrate which has a high yield of 74.24% which is higher
than the 70%9 yield obtained in a similar experiment using a different method of synthesis. A
possible reason for the increase in yield could be that there are impurities or moisture present
in the product. Compared to the appearance of the crystals in Figure 6 our product appeared to
be a purple, denser which is due to the moisture retained in the fine crystals. The alternative
method was more time consuming but resulted in pure crystals which are described as violet-
red to carmine-red prisms9 and based off this literature the assumption can be made that there
are impurities in the product, but this will need to be confirmed using other techniques such as
X-ray Crystallography.

The yield of Hexaamminecobalt(III) Chloride is 42 times lower than the 80% yield10 obtained
by the alternate method.

In Inorganic Syntheses, Volume 9 the synthesis of Pentaaminechlorocobalt(III) Chloride is

described. The crystals are red-violet and rhomb-shaped, the percentage yield of the method
described is 91-95%.11 The crystals produced in this experiment were a fine violet powder with
an overall yield of 31.61%. The low yield of product could be due to impurities in the
Tetraamminecarbonatocobalt(III) Nitrate reactant.

Bonus Feedback
The practicals for this module were engaging in the way that we were required to develop our
understanding of the theory of the syntheses preformed through the trial of the experiments.
When the reasoning of the method was unclear we were able to increase our overall general
knowledge of the synthesis process by engaging with the demis. A more in depth background of
the connections between the practical components and theory components of this module
would have been beneficial. However we all developed as chemists through this experience.

8
References
1 A. R. Sotiles, F. Massarotti, J. C. de O. Pires, M. E. Facchin Ciceri and C. R. Budziak Parabocz, Orbital: The Electronic
Journal of Chemistry, , DOI:10.17807/orbital.v11i6.1242.

2 C. E. Housecroft and A. G. Sharpe, d-Block metal chemistry: the first row metals, Pearson, Harlow, England, 5th
edn., 2018.

3 M. K. Widowati, S. B. Rahardjo, S. Hastuti and B. F. Ariyani, IOP Conf Ser Mater Sci Eng, 2019, 578, 012007.

4 S. L. Hsu, IR Spectroscopy, Elsevier, 1989.

5 M. J. Kristo, Nuclear Forensics, Elsevier, 2012.

6 IR Spectrum Table, https://www.sigmaaldrich.com/ZA/en/technical-documents/technical-article/analytical-

chemistry/photometry-and-reflectometry/ir-spectrum-table, (accessed 29 October 2022).

7 B. C. Smith, Spectroscopy, 2018, 24–28.

8 C. Housecroft and A. Sharpe, Experimental techniques, Pearson, Harlow, England, 2018.

9 G. Schlessinger, J. W. Simmons, G. Jabs and M. M. Chamberlain, Carbonatotetramminecobalt(III) Nitrate, John

Wiley & Sons, Inc, 1960, vol. 6.

10 J. Bjerrum, J. P. McReynolds, A. L. Oppegard and R. W. Parry, in Inorganic Syntheses, ed. W. C. Fernelius, John
Wiley & Sons, Inc., 1946, vol. 2, pp. 217–2182.

11 G. G. Schlessinger, D. Britton and T. Rhodes, Chloropentaamminecobalt(III) Chloride, John Wiley & Sons, Inc.,
1967, vol. 9.