2.

Experimental

2.1 Synthesis of [Co(NH3)4CO3]NO3

Prior to weighing Ammonium carbonate, (NH4)2CO3, on a top loading balance, ammonium

carbonate was crushed using a glass mortar and pestle in order to facilitate the solubility. Afterward,

20.00 g of ammonium carbonate weighed on a top loading balance. Also, 15.00 g of cobalt nitrate

hexahydrate, [Co(OH2)6](NO3)2, was measured on a top loading balance. Ammonium carbonate was

transferred in a 150 mL glass beaker and dissolved in 60 mL of deionized water. In a 500 mL glass

beaker, 15.00 g of cobalt nitrate hexahydrate was dissolved in 30 mL of deionized water. The

ammonium carbonate solute was poured into the cobalt nitrate hexahydrate solution while stirring.

In the solution, 5 mL of 50% hydrogen peroxide was slowly added. The solution was

concentrated to about 90 mL using a hot plate. During the evaporation process, the temperature did

not exceed 85 °C and 5g of ammonium carbonate was in small portions. In order to accelerate

evaporation, air was blow to the surface of the solution. The concentrated solution was cooled in an

ice water bath until a bright red-violet precipitate formed. The red-violet crystalline was isolated by

suction filtration using a Buchner funnel with a side-arm Erlenmeyer flask. The product was washed

once with small amount of ice-cold water and twice with small amount of ice-cold 95% ethanol. The

washed product was dried in 100 °C oven for 5 minutes. The dried product weighed in an analytical

balance and the weight was 6.9250 g.

2.2 Synthesis of [Co(NH3)5Cl]Cl2

After synthesizing [Co(NH3)4CO3]NO3, 5.01 g of [Co(NH3)4CO3]NO3 was measured on a

top loading balance and dissolved in 50 mL of deionized water in a 500 mL glass beaker.

Concentrated hydrochloric acid, HCl, was added drop wise until there was no more evolution of

carbon dioxide gas. Total of 10 mL of concentrate hydrochloric acid was added. The acidic solution

was neutralized with concentrated ammonium hydroxide, NH3. The pH of the solution was checked

with pH paper. After the neutralization, an additional 5 mL of concentrated ammonium hydroxide was

added. The basic solution was heated for 20 minutes. While heating, the temperature of the solution
did not exceed 85 °C to avoid boiling. The solution was slightly cooled, and 75 mL of concentrated

hydrochloric acid was added to the solution slowly. The addition of concentrated hydrochloric acid

changed the color of the solution into more reddish color. After adding concentrated hydrochloric acid,

the solution was reheated for 20 minutes. As a solid purple precipitate formed, the aqueous layer

became more clear.

The solution was cooled to room temperature, and the purple precipitate was further formed.

The purple precipitate was separated from the aqueous layer by decantation. The final product was

washed twice with small amounts of ice-cold deionized water by decantation. After washing, the

crystalline product was isolated by suction filtration using a Buchner funnel with a side-arm

Erlenmeyer flask. The purple crystalline was finally washed with ice-cold 95 % ethanol. The washed

product was dried in 100 °C oven for 5 minutes. The dried product weighed in an analytical balance

and the weight was 3.3439 g.

2.3 Characterization of two crystals : [Co(NH3)4CO3]NO3 and [Co(NH3)5Cl]Cl2

Using a Perkin Elmer Spectrum One Infrared Spectrometer, the infrared spectra of the

crystals were obtained. The spectrum was collected in percent transmittance, and prominent peaks

were labelled. The IR spectra of crystals were compared with IR spectra of substrates. Using an

analytical balance, 0.0312 g of [Co(NH3)4CO3]NO3 and 0.0331 g of [Co(NH3)5Cl]Cl2 was measured..

Each crystal was transferred into a 25 mL volumetric flask individually and dissolved in 25 mL of

deionized water. Therefore, each solution had a concentration of 0.005 M. Using plastic cuvettes and a

Perkin Elmer Lambda 35 UV-visible spectrophotometer, the absorbance of the solutions were

collected from 300 nm to 800 nm. The UV-Vis absorbance was used to analyzed the colors of crystals

and relate the color with the energy and spectrochemical series. The conductivities of the solutions

were also measured using a Hanna Instruments HI9093 conductivity meter. The conductivity

measurements were compared with the conductivity of three different salts which contains different

number of ions.

3.Results and Discussion

3.1 Chemical Reactions and Theoretical Yields

The synthesis of [Co(NH3)4CO3]NO3 used following reaction:

Using the above reaction, the water ligands were exchanged with ammonia and carbonate ligands. The

starting material was cobalt nitrate hexahydrate, which is a cobalt(II) complex. Ligand exchange was

taken placed in an excess of ammonia and ammonium carbonate. However, the synthesis of

[Co(NH3)4CO3]NO3 required oxidation of the +2 cobalt metal to the +3 cobalt metal. Therefore,

hydrogen peroxide, an oxidizing agent, was used to oxidize the cobalt(II) to cobalt(III). After

oxidation, the cobalt(III) underwent ligand exchange and formed [Co(NH3)4CO3]NO3. The limiting

reagent was cobalt nitrate hexahydrate. The theoretical yield should be 12.84g, but the actual yield

was 6.9250 g. Therefore, the percent yield was 53.94 %. The percent yield was not 100 %, because

water was not evaporated all, and the product was still dissolved in water.[lab manual, text book, education]

The goal of the second synthesis was producing [Co(NH3)5Cl]Cl2. The second synthesis

process followed series of reactions:

[Co(NH3)4CO3]NO3 + 2HCl → [Co(NH3)4(OH2)2]3+ + CO2(g) + 2Cl- + NO3- + H2O

[Co(NH3)4(OH2)2]3+ + NH3 → [Co(NH3)5(OH2)]3+ + H2O

[Co(NH3)5(OH2)]3+ + HCl → [Co(NH3)5Cl]Cl2(s) + H3O+.

Concentrated HCl was added to remove the carbonate ion. The removal of carbonate ion could be

observed by the evolution of carbon dioxide. The excess acid was neutralized with NH3, and an excess

of NH3 was further added to remove water ligand and from [Co(NH3)5(OH2)]3+. Finally, a large

amount of HCl was added to for chloride salts, which precipitated in water. The limiting reagent was

[Co(NH3)4CO3]NO3. The theoretical yield should be 5.04 g, but the actual yield was 3.3439 g. The

percent yield was 66.38 %. The percent yield was not 100 %, because it was not possible to

precipitate all [Co(NH3)5Cl]2+ from the water. Additional evaporation process might be able increase

percent yield.
3.2 UV-Vis Spectra and Spectrochemical Series

The UV-Vis spectra of each cobalt complexes were measured from 300 nm to 800 nm using

[ ]. All three complexes, including cobalt nitrate hexahydrate, had reddish purple colors in

solutions. The reddish purple color of the solutions were consistent with the absorbance near 500 nm

which is green light. The absorbance measurements provide more information about the cobalt

complexes. Crystal filed theory predicts the splitting of the d orbitals in a metal complex, and the

splitting pattern to be dependent on the crystal field and types of ligands. Three cobalt complexes are

expected to be octahedral. In the octahedral crystal filed, the d orbitals are split into eg symmetry and

t2g symmetry. The energy separation between the two is Δoct. The absorption results from the

excitation of electron configuration. Therefore, the measurement of wavelength can be related to the

Δoct by

𝑐
∆𝑜𝑐𝑡 = ℎ
𝜆

where h is Planck's constant, c is the speed of light, and λ is the wavelength. Table 1 summarizes the

wavelength and absorbance at the peak and energy related to the wavelength. The spectrochemical

series ranks ligands and metals by field strength. The stronger the field is the greater energy

separation increases. The cobalt complex with weak field ligands, such as the chloride in

[Co(NH3)5Cl]Cl2, have smaller Δoct. The Δoct of [Co(NH3)5Cl]Cl2 smaller than the [Co(NH3)4CO3]NO3,

because CO3 and is a stronger ligand. The ligands of Co(NO3)2·6H2O complex have weaker field s

thane the CO3, but of Co(NO3)2·6H2O still had higher Δoct because the field strength of Co(II) is

stronger than the Co(III).

Table

3.3 Conductivity Measurements

Conductivity of tap water, deionized water, three different salts, and two synthesized cobalt
complex was measured using Hanna Instruments Conductivity Meter. The probe of an instrument has

two electrodes. The instrument applies potential between the two electrodes and current is generated,

and the amount of current generated depends on both the concentration and number of ions. Since a

voltage and a current are known, a resistivity of the solution can be calculated using Ohm’s law. Also,

the cell geometry correction facto is known, so the specific resistance of the solution can be calculated.

The reciprocal of the specific resistance is the specific conductance. Using the specific conductance,

the molar conductance, Ʌm can be calculated. The molar conductance is the conductivity of one

mole of solute in 1cm3 cube solution, and it can be calculated using following equation:

1000 L
Ʌm = in S cm2 /mol
M

where L is the conductivity, and M is molarity. The conductivity L can be calculated using following

equation:

l
L= in S/cm
A∗R

where A is the cell area, and R is resistance.

The three different salts and two synthesized cobalt complexes were prepared as 0.005 M

solution. Table 2 summarizes number of ions, conductivity measurements, and calculated molar

conductivity of each solution. Tap water had some conductivity of its own, so the solution was prepare

in deionized water, which had zero conductivity. The molar conductivity of [Co(NH3)4CO3]NO3 was

close to the KCl solution, and the molar conductivity of [Co(NH3)5Cl]Cl2 was close as MgCl2. This

measurement suggested that the [Co(NH3)4CO3]NO3 produces two ions, and [Co(NH3)5Cl]Cl2

produces three ions in a solution.

3.4 IR spectra of three cobalt complexes and relevant compounds