Yi Cheng Zeng, SID: 450201077

Procedure 3

Synthesis and determination of an amminecobalt(III) bromide

complex.

Abstract

The product of an amminecobalt bromide complex synthesis was prepared and

analysed. CoCl2.6H2O was dissolved in a solution of concentrated ammonium hydroxide and

ammonium chloride, followed by 30 % hydrogen peroxide and concentrated HCl. The

solution was heated, followed by filtration of the solid, where it was heated again in

ammonium hydroxide solution. Concentrated HBr was added in excess until the solution was

acidic, followed by further heating and finally filtration and recrystallisation of the product.

Spectrophotometry, cation column chromatography, UV-vis spectrophotometry and

qualitative anion tests were used to determine the identity of the compound. The final product

is speculated to be pentaamminebromidocobalt (III) bromide dihydrate

([Co(NH3)5Br]Br2.2H2O), however, further analysis is required to confirm this.

1
 Experimental

Refer to 'Procedure 3'. Heating was carried out at 50-60oC, unless otherwise stated.

Data

Figure 1. Final product of the cobalt complex synthesis

After addition of HCl in the procedure, the solution (and its resulting precipitates)

formed a bright red-pink colour, which shifted slightly in hue throughout the reaction process

until the addition of 2 M ammonium hydroxide, in which the solution and its precipitates

remained mostly a dark purple. The final compound prepared was a dark-purple powder-like

solid (Fig.1).

Apart from the presence of ammine ligands and the possibility of aqua ligands or the

complex being in its hydrate form, qualitative tests showed only the presence of bromide

species in the complex, either as ligand(s) coordinated to the Co (III) centre or as counterions,

when a solution of the solid reacted in a boiling water bath for 1 min with an equal amount of

15 M HNO3, forming an orange discolouration of the cyclohexane layer added after cooling.

Solubility data is summarised in Table 1. The solution of the complex was a similar

purple-lavender colour.

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 Table 1. Measurements in solubility test

Amount of complex (mg) Volume of water required for complete dissolution (mL)
33.7 30.0

The measurement of the cobalt content in the sample was achieved by conversion of

the cobalt (III) in the complex to [Co(NCS)4]2-, a complex that strongly absorbs light at 621

nm. During the preparation, at the step of the second heating of the reacting solution with the

reagents caused the solution to turn deep green as expected, with white solid precipitate

suspended in the test tube. After cooling, the solution began to fade into a yellow-brown

colour. Upon dissolution of the solution and the white precipitate, the solution was a deep

yellow colour, before a further 1 in 10 dilution and mixing with reagent grade acetone and

ammonium thiocynate. The measurements of the prepared solutions and standards are given

in Tables 2 and 3:

Table 2. Absorbance at 621 nm of the

standard [Co(NCS)4]2- solutions.

Concentration (M) Absorbance

2.000 X10-4 0.361

3.000 X10-4 0.504

5.000 X10-4 0.821

Table 3. Absorbance at 621 nm of the prepared

solutions with given starting weight of samples.

Starting amount (mg) Absorbance

109 0.446

103 0.418

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 The anion (counterion) content determination was conducted using cation column

chromatography (acidic cation exchange resin Dowex 50W) followed by titration of the

eluent against the 0.1 M NaOH standard solution. After all of the solution of the complex was

added to the column and followed by the addition of water until pH 5, there was

approximately half a centimetre of a dark violet solid deposit above the resin, which had also

partly turned purple. The measured data is summarised in Table 4:

Table 4. Measurements in the determination of anion content

Amount of complex (mg) Volume of NaOH (0.1 M) titrated (mL)

157.9 9.70

UV-visible spectrophotometry of a fully saturated solution of the compound produced

the following spectrum (Fig.2) in the range of 400 - 700 nm, with peak wavelength (λmax) at

548 nm with an absorbance of 0.4216.

Figure 2. Spectrum of cobalt complex solution as displayed on the spectrophotometer.

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 Results

Solubility

The solubility of the complex in g L-1 is calculated from the experimental data (Table

1). Given 33.7 mg of the solid required 30.0 mL of water to dissolve, the solubility is thus

given by:

Solubility = 33.7 mg / 30.0 mL = 1.12 mg ml-1

= 1.12 g L-1

Determination of cobalt content and molecular weight

To determine the amount of cobalt present in our sample, the extinction coefficient (ε)

of [Co(NCS)4]2- was first found from the absorbances (A) and known concentrations (c) of

the standard solutions using Beer-Lambert's Law:

A = εcℓ

where ℓ is the length of the path of light, which was 1 cm for all spectrophotometers

used in this experiment, and so does not contribute to the following calculations. Rearranging,

we get:

ε = A/cℓ

and hence we get the extinction coefficient as the absorbance divided by the

concentration. The average extinction coefficient of the 3 standard solutions was calculated,

along with the standard deviation of the extinctions. The percentage error was calculated as

the standard deviation divided by the average extinction coefficient. These calculations are

5
summarised in Table 5:

Table 5. Summary of calculations of ε from measurements of standard solutions

Concentration Absorbance ε (M-1 cm-1) Average ε Standard % Error

(M) (at 621 nm) (M-1 cm-1) Deviation of
ε
2.000 X10-4 0.361 1810 1710 88.9 5.20

3.000 X10-4 0.504 1680

5.000 X10-4 0.821 1640

Given ε for the [Co(NCS)4]2- solution, we can find the concentration from the

absorbance by rearranging the Beer-Lambert law:

c = A/εℓ

The concentration of [Co(NCS)4]2- in the sample solutions is equal to the

concentration of cobalt in the solutions, and hence we can back-calculate to find the content

of cobalt in the complex.

As an example, say the absorbance of the solution (with a starting amount of 100 mg

of the original complex) of unknown concentration is 0.500. Then the concentration of the

spectrophotometrically analysed sample is:

c = 0.500 / (1710 M-1 cm-1 * 1 cm) = 2.92 X10-4 M

This is the solution that has had a 1 in 10 dilution (10 mL of the original solution

diluted to 100 mL), and so reversing we multiply by 10 to get the concentration of

[Co(NCS)4]2- and consequently the concentration of cobalt to be 2.92 X10-3 M. Since molar

concentration is moles per litre, the volume of the solution pre-dilution was 100 mL or 0.1 L,

and so we calculate the number of moles of Co to be:

moles (Co) = concentration of cobalt in solution * volume of solution

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 = 2.92 X10-3 mol L-1 * 0.1 L = 2.92 X10-4 mol.

Now, given the atomic weight or molar mass of cobalt is 58.933 g mol-1, the mass of

cobalt in the sample is given by:

mass (Co) = molar mass (Co) * moles (Co) = 2.92 X10-4 mol * 58.933 g mol-1

= 1.72 X10-2 g = 17.2 mg

The percentage of cobalt (%Co) present in our sample (w/w) is given by:

%Co = (mass (Co) / mass (sample) ) * 100 %

And so the percentage of cobalt in this example is

%Co = (17.2 mg / 100 mg) * 100 % = 17.2 %

The results obtained from the experiment are summarised in Table 6:

Table 6. Summary of data for determining the cobalt content.

Mass of Absorbance Concentration Amount of Co %Co Average Standard

sample (at 621 nm) (in dilute in sample (mg) (w/w) %Co deviation
(mg) solution) (M) (w/w) of %Co
(w/w)
109 0.446 2.60 X10-4 15.3 14.1 14.1 0.0707
103 0.418 2.45 X10-4 14.4 14.0

To find the molecular weight of the complex, we know that one mole of the complex

contains one mole of Co, and so the molar mass of Co is 14.1 % of the total mass for one

mole of the complex.

Total mass = 100% (w/w) of sample = (molar mass (Co) / %Co ) * 100

This yields the molecular weight to be 418 g mol-1.

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 Determination of anion content

The moles of anions is calculated after titration of the eluent (containing 157.9 mg of

the sample complex) with 0.1 M NaOH standard. To find the moles of NaOH titrated, and

conesequently the moles of anions:

Volume titrated * concentration NaOH standard = moles of OH- = moles of H+

displaced by complex = moles of "positive charges" on the complex = moles of anions in the

complex

9.70 mL of 0.1 M NaOH was required to reach the endpoint (phenolphthalein

indicator) of the collected eluent. Hence:

Moles of anions = 9.70 X10-3 L * 0.1 mol L-1 = 9.70 X10-4 mol

Given that Br- (molar mass 79.904 g mol-1) was the only detected anion in the sample,

the percentage (w/w) of bromide as the counterion(s) in the sample is thus:

%Br as counterions = (molar mass (Br) * moles of anions / mass of sample) * 100%

= (79.904 g mol-1 * 9.70 X10-4 mol / 0.1579 g) * 100%

= 49.1 %

The moles of bromide counterion(s) in one mole of the complex is given by:

(%Br as counterions * Molecular weight of complex * 1 mol) / Molar mass (Br)

= (49.1 % * 418 g) / 79.904 g mol-1

= 2.57 moles

The ratio of (complex) : (Br_ counterions) is hence 1 : 2.57

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 UV-Visible spectrum

The peak wavelength (λmax) of a completely dissolve solution of the compound was

determined to be 548 nm, with an absorbance (A) of 0.4216. The concentration (c) of the

solution was calculated by:

c = Solubility of complex / Molecular weight of complex

= 1.12 g L-1 / 418 g mol-1

= 2.68 X10-3 mol L-1

The molar absorptivity (extinction coefficient ε) at λmax is thus calculated from

rearranging the Beer-Lambert law (where ℓ is 1 cm), giving:

ε = A/cℓ

= 0.4216 / (2.68 X10-3 M * 1 cm)

= 157 M-1 cm-1

Calculation and summary of the composition of the complex

Since bromine is the only anion detected, there must be 3 Br- ions per Co3+ in order to

balance the charge, and so that gives its percentage composition (w/w) as:

(3 * Molar mass(Br) / Molecular weight of complex) * 100 %

= (3 * 79.904 g mol-1 / 418 g mol-1) *100 %

= 57.3 %

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 The percentage composition of ammonia and water in the complex is the remaining

portion of the complex unaccounted for. Hence, the overall composition of the complex is

shown in Table 7.

Table 7. Species in complex and counterions and their percentage composition

Species Percentage composition (% w/w) Mass per one mole of the complex
(g)
Co3+ /Co (III) 14.1 58.9
Br- 57.3 239.7
NH3 and/or H2O 28.6 119.4
Total 100 418

Discussion

Overall, the synthesis of the cobalt complex occurred without many disruptions to the

experimental or unexpected observations. Some of the intermediate product was lost due to

perforations of the filter paper during the first vacuum filtration, however this did not

drastically affect the reaction and purification processes nor the final yield.

Some errors were made during the analytical phase of the experiment. During the

spectrophotometric determination of the cobalt content, there were initially 3 sample

solutions being prepared, however, one had to be discarded due to overfilling of the mark on

the volumetric flask, thus its concentration could not be accurately determined. However the

two samples that were measured were fairly similar in the final calculation of the cobalt

content, with a standard deviation of 0.0707 from the average %Co (see Table 6).

The dissolution of the complex in water for UV-visible spectrophotometry was

initially conducted by attempting to dissolve 74.4 mg of the complex in 25 mL of water at

room temperature. Not all of the complex could be dissolved, so after mixing and settling of

10
the solid, care was taken to only remove the dissolved aqueous layer, followed by absorption

analysis of the saturated solution. The analysis in the future would be completed again

avoiding incomplete dissolution to obtain a more accurate reading void of any presence of

solid particles suspended in the solution.

As described in the Data section, the column of the ion exchange resin had a small

deposit of either undissolved complex or the bound complex with resin. Further down, there

was definite evidence of a colour change of the resin likely to be a result of the complex

binding to the sulfonic acid groups. This colour (dark red-violet) appeared continuous with

the deposit, but the deposit was slightly lighter and more like that of the original solid (see

Fig. 1). Thus, it may be that not all the complex was bound to the resin, affecting the

measurement in the titration and consequently limiting the confidence of the calculated moles

of anions. The data of the anion content suggests that the complex has a +2 or +3 charge, as

the calculation results in a counterion content around halfway between both.

The identification of the synthesised cobalt complex is limited by the lack of some

analysis in determining more information about elemental content and properties such as

charge of the complex. Hydrogen, nitrogen and oxygen content was unavailable, and this

leads to several possible combinations of the remaining species that could make up the

complex, given only the deducted percentage of composition. Similarly, infrared

spectroscopy may also reveal specific vibrational energies that correspond to the relative

presence or absence of ligands hypothesised. The combinations of possible ammonia and

water species based on only the composition data are given in Table 8. Due to the

unavailability of the conductivity meter, the molar conductivity of the complex in solution

could not be determined, which would have aided the determination of the charge of the

compound.

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 Table 8. Combinations of NH3 and H2O that would give a molecular weight ~120 g mol-1 and their
corresponding empirical formulae of the cobalt bromide compound. The experimental molecular mass
of the complex is 418 g mol-1.

# (NH3)x(H2O)y Molecular Corresponding empirical Molecular weight of

weight* (g mol- formula complex (g mol-1)
1
)
1 (NH3)7 119.217 Co(NH3)7Br3 417.862
2 (NH3)6(H2O) 120.201 Co(NH3)6(H2O)Br3 418.846
3 (NH3)5(H2O)2 121.185 Co(NH3)5(H2O)2Br3 419.83
4 (NH3)4(H2O)3 122.169 Co(NH3)4(H2O)3Br3 420.814
5 (NH3)3(H2O)4 123.153 Co(NH3)3(H2O)4Br3 421.798
6 (NH3)2(H2O)5 124.137 Co(NH3)2(H2O)5Br3 422.782
7 (NH3)(H2O)6 125.121 Co(NH3)(H2O)6Br3 423.766
8 (H2O)7 126.105 Co(H2O)7Br3 424.750
*Given the molar mass of the following elements: H, 1.008 g mol -1; N, 14.007 g mol-1; O, 15.999 g mol-1

Table 9. Possible molecular formulas that have a charge of 2+ or 3+ on the complex and where all the
ammonia are coordinated as ammine ligands

Empirical formula # Molecular formula

(from Table 8)
2 [Co(NH3)6]Br3.H2O
3 [Co(NH3)5Br]Br2.2H2O ; [Co(NH3)5H2O]Br3.H2O
4 [Co(NH3)4 (H2O)Br]Br2.2H2O ; [Co(NH3)4 (H2O)2]Br3.H2O
5 [Co(NH3)3 (H2O)2Br]Br2.2H2O; [Co(NH3)3 (H2O)3]Br3.H2O
6 [Co(NH3)2 (H2O)3Br]Br2.2H2O ; [Co(NH3)2 (H2O)4]Br3.H2O
7 [Co(NH3) (H2O)4Br]Br2.2H2O ; [Co(NH3) (H2O)3]Br3.H2O

Despite these limitations, we draw upon what data is available in order to narrow

down what possible or expected formulae we have for the compound. For instance, we can

rule out the formulae for #1 of Table 8, as the complex has a coordination number of 6, and

we assume that ammonia only acts as ligands in these aqueous environments. Formulae #2 is

closest in contention, as it is the closest in molecular weight to that determined

experimentally. Furthermore, the reaction conditions containing initially concentrated

amounts of ammonium, which form ammonia under basic conditions such as that provided by

ammonium hydroxide, suggest that they would be contenders as ammine ligands over aqua

ligands of the complex. Under similar conditions to those in this experiment, Hynes,

Yanowski and Shiller(1) synthesised purple pentaaminechloridocobalt (III) chloride

([Co(NH3)5Cl]Cl2) using HCl instead of HBr, which suggests that the ammonium ions from

the solutions of ammonium hydroxide and ammonium chloride coordinate around cobalt

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under these reaction conditions. Diehl, Clark and Willard(2) noted that after addition of

ammonium and ammonia (in excess) and oxidation by 30 % hydrogen peroxide, the addition

of HBr at which the solution is just neutralised formed pentaamineaquacobalt (III) bromide

([Co(NH3)5H2O]Br3), while excess HBr resulted in the displacement of the aqua ligand by

bromide to form pentaaminebromidocobalt (III) bromide ([Co(NH3)5Br]Br2). The addition of

excess HBr was also executed in this procedure, leading to the hypothesis that aqua ligands

may not have formed in this complex, but water may have been present as hydrates, even

though theoretically the process of desiccation should have removed all water molecules.

There are not many past studies that have examined the compounds of empirical

formula (and their consequent molecular formulas) #5-8 (see Tables 8 and 9). Historically

however, many amminecobalt(III) complexes used to be named by their colour(3).

Hexaamminecobalt (III) derivatives for exapmple (i.e. [Co(NH3)6]Br3.H2O in Table 9) were

called "luteosalts" (yellow orange), and have generally reported physical colours of the

yellow to red spectrum (such as [Co(NH3)6]Br2(BF4) prepared and characterised by Bala et

al.(4)). Pentaaminehalidocobalt (III) derivatives were often described as being purple in colour
(1)(3)
, and also specifically pentaamminebromidocobalt (III) bromide ([Co(NH3)5Br]Br2) (5).

However, colour of a compound is not always a useful justification of the identity of the

compound, as many complexes form similar hues of colours (i.e. [Co(NH3)4 (H2O)Br]Br2 is

also a reddish-violet crystal(6)), or reported to have different colours, such as

[Co(NH3)5Br]Br2 forming dark red crystals in Diehl et al.'s study(2).

However, we could lean towards pentaamminebromidocobalt (III) bromide

([Co(NH3)5Br]Br2) as the complex that has been formed on the basis of similarly recorded

λmax. Loehlin, Kahl and Darlington(7) reported the λmax of their preparations of

[Co(NH3)5Br]2+ to be 552 nm, close to the value of 548 nm observed in the current

experiment. The difference in these values may be due to instrumental differences, but it is

13
equally likely that forming this conclusion about the identity of our complex based only on a

few non-unique physical properties is a stretch.

Ultimately, without important pieces of information such as the H, N and O content of

the compound, there cannot be a confident conclusion as to the identity of the complex. From

the gathered experimental data, we can say that the complex formed is either an

ammineaquacobalt (III) or amminecobalt (III) complex, with one or no bromido ligands, 2 or

3 bromide counterions and probably existing in a hydrate form. Speculation by comparing the

current results against observations in previous studies suggest that the complex salt that was

formed in this experiment is potentially pentaamminebromidocobalt (III) bromide dihydrate

([Co(NH3)5Br]Br2.2H2O), the structure of which is shown in Fig 2.

Figure 2. Structure of pentaamminebromidocobalt (III) bromide dihydrate ([Co(NH3)5Br]Br2.2H2O)

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 References

(1)
W.A. Hynes, L.K. Yanowski, M. Shiller. J. Am. Chem. Soc., 60 (1938) 3053

(2)
H. Diehl, H. Clark, H. H. Willard, J. C. Bailar, Bromopentamminocobalti Bromide,

in "Inorganic Syntheses", Volume 1 (ed H. S. Booth), John Wiley & Sons, Inc., Hoboken, NJ,

USA (1939)

(3)
M. Eagleson "Concise Encyclopedia Chemistry", Walter de Gruyter and Co., Berlin

(1994)

(4)
R. Bala, R. J. Sharma, U. Sharma, A. D. Burrows, K. Cassar, J. Mol. Struct., 832,

(2007), 156

(5)
K. A. Hofmann "Lehrbuch der anorganischen Chemie", Braunschweig, F. Vieweg

& Sohn (1919)

(6)
A. Werner, A. Wolberg, Ber. Dtsch. Chem. Ges., 38, (1905) 2009

(7)
J. H. Loehlin, S. B. Kahl, J. A. Darlington, J. Chem. Edu., 59 (1982) 1048

15