Adrián Alonso Canales 29-Nov.

-24

Percentage compound determination of pentaammineaquacobalt (III)

trichloride and pentaamminecobalt (III) trichloride

Abstract:

In this semester-long project, a number of experiments have been performed with the

main goal of obtaining the percentage of each compound present in two cobalt

compounds, and the equivalent weights in order to determine their structural formula,

charge, nomenclature and molecular weights. The first compound, named as red cobalt

compound, had a composition of 6.424% H2O, 41.77% Cl, 32.635% NH3 and 25.20%

Co, and the second one, the purple cobalt compound, had the same values with the

absent of H2O. The structural formulas of the compounds respectively are: [Co(III)

(NH3)5(H2O)]3+(Cl3)3 and [Co(III)(NH3)5]2+(Cl3)2. Its IUPAC nomenclatures:

pentaammineaquacobalt (III) trichloride and pentaamminecobalt (III) trichloride.

Finally, their respective molecular weights were determined in: 268.4g/mol and

250.4g/mol.

Introduction:

The Analytical Chemistry laboratory is a second integrant part of the class, in which by

performing experiments students will be able to put in practice the knowledge obtained

during the lesson. The laboratory focuses on obtaining precise and accurate data,

minimizing error for obtaining the most reliable values possible. Because of this, the

main focus of the class is a semester-long project, in which students will follow the

procedures in their lab manuals in order to synthesize and analyze two cobalt (III)

compounds, named as red and purple. To obtain the data various wet/classical methods

such as gravimetric determination by drying or precipitation of a compound, and

volumetric determination by titration will be performed. As well as that modern

Adrián Alonso Canales 29-Nov.-24

spectroscopic methods will be used, such as chromatography or spectrophotometric

determination. As a way of maximize accuracy and precision of the techniques, prior to

the analysis of the cobalt (III) compounds, several Quality Control compounds

unknown to students but known to the instructor will also be analyzed, using the same

technique, and cobalt (III) compound analysis will not be performed until obtaining

precise enough data in the QC compound. After all the experiments have been

completed, the percentage compositions of each different molecules in red and purple

cobalt compounds will be obtained, meaning that their empirical formulas can be

deduced, which is the main goal of the project.

Experimental:

Gravimetric determination of % water

To determine the H2O percent content in the formula of the Red Co(III) coordination

compound, a gravimetric analytical method could be used, in this case a heating-

cooling-weighing cycle until the product reaches constant mass after losing all the

water.

100-110ºC

[Co(NH3)x(Cl)y(H2O)z] (red) [Co(NH3)x(Cl)y] (purple)) + H2O (vapor)

For this procedure, three trials will be performed, by weighing 0.3-0.4g of the red

Co(III) inside three pre-weighed weighing bottles. Before adding the compound, it is

necessary to be sure that the weighing bottles does not contain any H2O present. They

are placed inside a watch glass covered beaker heated in the oven at 100-110ºC for 4

hours, and then cooled down for 1 hour in a desiccator before proceeding to get a

weight of the bottles. In order to get a constant weight, the heating-cooling-weighing

process should be repeated with 1 hour of heating and 30 minutes of cooling as many
Adrián Alonso Canales 29-Nov.-24

times as possible. Once a constant mass is obtained we will proceed to add the weighed

red Co(III) to each pre-weighed and labeled bottles and perform the same cycle until

obtaining constant mass.

Gravimetric determination of % Chloride

Chloride can be determined gravimetrically by a dissolution of the sample in water and

precipitating the chloride as silver chloride. The amount of chloride present can be

calculated from the amount of silver chloride collected.

Cl- (aq) + Ag+ (aq)  AgCl (s)

For the experiment it is necessary to prepare the crucibles which are going to be used to

filter the solution. In first place, each crucible is scrubbed with detergent and then

placed in a suction flask-rubber for been cleaned with previously made nitric acid, in

cases they still seem dirty a 6M ammonia solution will be used. After the cleaning, they

should be brought to constant weight by putting them in a big beaker, covered with a

watch glass, and then placed in the oven at 100-110ºC and then letting cool down in a

desiccator. The cycle should be repeated until they are at constant weight.

Three sets of purple Co(III) will be measured and mixed with distilled water and 6M

HNO3, pre-made AgNO3 will be added until creation of precipitate and 5mL excess, and

then heated until boiling. For the collection of precipitate, the filtering crucibles will be

used by decanting the supernatant through them with a solution of 6M HNO3 and helped

with distilled water. The solids collected will be later dried in the oven until obtaining

constant mass.
Adrián Alonso Canales 29-Nov.-24

Standardization of 0.1 M NaOH:

Solid NaOH cannot be used as primary standard reagent as it absorbs CO2 from the

atmosphere, in order to obtain the exact concentration of NaOH it is necessary a

standardization by a titration with a primary standard as KHP. This is a 1:1 ratio reaction

and as K+ dissociates in water, it will be an acid-base titration with Phenolphthalein as

the perfect indicator (PH 8.0-9.6).

HP- + OH-  P2- + H2O

In first place the preparation of 0.1 M NaOH is done by boiling the water that is going

to be used for the solution to remove CO2, and add to it the necessary amount of 50%

NaOH to create the concentration. Also, the buret for the titration should be prepared,

first rinsed with distilled water and later with the 0.1 M NaOH, before being filled with

the titrant (NaOH) and proceed to the titration. Three samples of KHP are weighed and

dissolved in pre-boiled H2O, then the titration is started, adding NaOH until the end

point, a faint pink color of the solution. Total volume of NaOH needed is recorded and

from here the exact molar concentration of NaOH.

Determination of equivalent weight:

The determination of the equivalent weights of both red and purple Cobalt compounds

is based on the acid-base titration of H+ produced after passing the sample through a

cation exchange column, which are exchanged for the cations in the sample. The

number n+ charge ions carried by the cobalt compound will be exchanged by the same

number of H+ ions from the column. The equivalent weight is the mass of one

equivalent material or the portion of material which can replace one mole of H +. The

hydrogen ions exchanged are collected and acid-base titrated with a standard solution of
Adrián Alonso Canales 29-Nov.-24

NaOH, so the equivalent weight is calculated from the mass of the sample and moles of

H+ determined in the titration.

H+ + OH-  H2O

A preparation of cation exchange columns is needed, for this we will pour Dowex HCR-

W2, 16-40 mesh, hydrogen form resin washed with distilled water into a buret and

make sure to eliminate all unbound H+ with distilled water. After that, the buret will be

filled with our Co compounds, separately and in duplicate. The ion-exchange

chromatography is performed by adding distilled water in portions, the resin will be

eluted and the eluent should be collected for later titration with NaOH solution and

phenolphthalein as the indicator.

Determination of % ammonia in red cobalt compound

The NH3 percentage in the red cobalt compound will be determined by Kjeldahl

method, which is a very useful method for the determination of nitrogen in a variety of

organic samples. In this experiment we will perform a variation of the typical Kjeldahl

method as the reduction and digestion steps are eliminated as the sample is already

present in ammonia. The process will start with the distillation step, followed by

collection and titration. Sample is dissolved in H2SO4 in order to convert NH3 into NH4+,

then transferred to Kjeldahl distillation apparatus, the ammonia is released by a

concentrated base, distilled and collected in acidic solution, in this case H3BO3-, and

then titrated with HCL in an indirect titration as moles of titrant indirectly gives the

moles of NH3. The indicator used will be bromocresol green (PH range 3.8-5.4) as the

equivalence point is acidic.

H3BO3 + NH3  NH4+ + H2BO3-

H2BO3- + HCl  H3BO3 +Cl-

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A 0.1 M solution of HCl should be standardized against the standard solution of NaOH

prepared previously, this will be performed by a titration using phenolphthalein

indicator in order to get the exact concentration. This 0.1 M HCl should be later

converted to 0.01 M HCl in since the analysis is a micro-analysis being a smaller

concentration more accurate, this is done by dilution factor. The sample is prepared by

measuring dissolving the purple cobalt compound with a 1M H2SO4 solution in a

100mL flask. After the final preparation of the Kjeldahl distillation apparatus we can

proceed to distillation of the samples, in this case we skipped the distillation of method

blank.

Boric acid will be pipetted and added to a flask with indicator to place under the outlet

of condenser, distillation is initiated with the addition of the sample into the chamber,

followed by a number of washings with distilled water and 50% solution of NaOH.

Distillate is collected and titrated with the standardized 0.01 m HCl; two samples are

prepared for increasing precision.

Standardization of Co (II):

In order to complete the determination of percent cobalt is the compound it is necessary

to use a standardized solution of cobalt (II). By dissolving CoSO4 7H2O in water and

EDTA complexometric titration the cobalt solution is standardized. EDTA is a

hexadentate ligand which forms a chelate complex with most metals in 1:1 ratio, with

drying it can be used as a primary standard.

Co(II) + H2Y2-  [Co-Y]2- + 2H+

For EDTA is necessary to use metal ion indicators, these release metal to EDTA at the

end point since it binds weaker to the metal than EDTA, in this experiment it will be

murexide, which color depends on solution PH.

Adrián Alonso Canales 29-Nov.-24

Co(II) + In (red, pH 4)  [Co-In] (yellow)

[Co-In] (yellow) + H2Y2-  [Co-Y]2- (colorless) + In (purple, pH 11)

Both the Co(II) stock solution and EDTA solution should be prepared previously. A 0.1

M CoSO4 7H2O solution is prepared dissolving the solid using 0.5 M H2SO4. Finally, a

0.020M EDTA solution is prepared dissolving the solid with distilled water, with the

EDTA solution we will fill up a buret for the acid-base titration. An aliquot of the 0.1 M

Co(II) solution is mixed with 0.5 M sodium acetate and the indicator, this solution´s pH

should be adjusted, so under a hood, ammonia is added until obtaining a golden-yellow

color. With the solution ready, the titration can start by adding the EDTA until reaching

the end point with a deep purple color change. During the titration H+ could be

neutralized by extra ammonia and color could turn orange-red, if this happen a few

ammonia drops should be added until reaching lemon-yellow color again.

Determination of % Co in Cobalt compound:

Cobalt, as a transition metal with d orbitals absorbs visible light via electronic

transition, and their solution are colorful. Its 7 d orbitals split into lower and higher

energy sets; the absorption of light provides a way to obtain it´s concentration by

spectrophotometric determination by Beer´s law: A= εbC. Since ε is characteristic of

the material and b (light path) is constant, the measurement of absorbance gives the

concentration, this is done by plotting a calibration curve of A vs C in which ε could be

obtained as the slope of the line. Absorbance can be measured by a spectrophotometer;

it measures the incident light intensity and the transmitted light intensity of a beam of

light passing through a cell containing the sample solution. With this two parameters

transmittance is measured as the division of the second to the first, and getting the -log

of transmittance we obtain absorption.

Adrián Alonso Canales 29-Nov.-24

Four solutions using the 0.1 M Co(II) standardized stock solutions, will be created

ranging in concentration between 0.010 M to 0.100 M by dilution with 0.5 M H2SO4. All

four solutions and the stock solution will be taken to the spectrophotometer and from

most diluted to least will get a UV-Visible spectrum in order to obtain absorbance at

maximum absorption wavelength. Using an excel sheet absorbance vs concentration is

plotted and fitted with linear fitting. From the slope of the line ε is determined, which is

going to be used in further calculations.

For the analysis of the purple compound, a thermal decomposition through high heat

should be done in order to convert purple cobalt compound into Co(II).

Co(NH3)x(Cl)y (purple)  CoCl2 (l) + NH3 (g) + N2 (g) + NH4Cl (s)

Three samples of purple cobalt compound are heated strongly until turning into deep

blue liquid. 3M H2SO4 is added to dissolve the liquid and diluted with distilled water

before measuring absorbance of all three solutions at max wavelength. With this

absorbance concentration can be calculated from the calibration curve and with atomic

mass, mass of Co can be determined to get % Co in purple cobalt compound.

Results:

Table 1: The percent composition oh H2O in red cobalt compound.

Trial # 1 2 3

H2O% 7.36% 6.61% 5.30%

Average H2O% 6.424%±0.8513

Table 2: The percent composition of Cl, NH3 and Co in purple cobalt compound.

Trial # 1 2 3
Adrián Alonso Canales 29-Nov.-24

Cl% 41.68% 41.91% 41.71%

Average Cl% 41.77%±0.1250

NH3% 33.35% 31.92%

Average NH3% 32.635%±0.715

Co% 25.29% 26.81% 23.49%

Average Co% 25.20 ±1.357

Table 3: The equivalent weights for the red and purple cobalt compounds.

Trial # 1 2

EW purple compound 124.5 g/eq 123.8 g/eq

Average EW purple Co 124.15±0.35

EW red compound 100.81 g/eq 88.52 g/eq

Average EW red Co 94.665±6.145

Table 4: Beer´s law graph of Co(II) (Absorbance vs Molarity)

Solution # Molarity (M) Absorbance

1 0.008128 0.0410

2 0.01626 0.0828

3 0.03251 0.1470

4 0.04877 0.2461

Stock 0.1016 0.4990

Adrián Alonso Canales 29-Nov.-24

Figure1: Beer´s law graph of Co(II) (Absorbance vs Molarity) with the slope of line

(molar extinction coefficient).

Discussion:

Assuming 100g of a sample of purple cobalt compound, and based on the percentage of

each of its components: %Cl, 32.635% NH3 and 25.20% Co; by finding the moles of

each component and dividing each by the smallest mole, the molar ratio of each

component is found.

41.77% Cl  41.77gCl x 1.000molCl/35.453gCl = 1.178molCl

1.178molCl/0.4276molCo = 2.75  3

32.635% NH3  32.635gNH3 x 1.000molNH3/17.031gNH3 = 1.916molNH3

1.916molNH3/0.4276molCo = 4.48  5

25.20% Co  25.20gCo x 1.000molCo/58.93gCo = 0.4276molCo

0.4276molCo/0.4276molCo = 1
Adrián Alonso Canales 29-Nov.-24

Using these molar ratios the formula for the purple cobalt compound would be:

Co(NH3)5Cl3 MM(Co)(NH3)(Cl)= 250.4 g/mol

Red cobalt compound´s formula differs from purple cobalt compound in the presence of

H2O in the first one. The molar ratio of H2O can be calculated from the %H2O using the

atomic mass of H2O and molar mass of the purple cobalt compound.

6.424% = m x 18.02/(m x 18.02 + 250.4) x 100

m=0.9542 1

Using these molar ratios, the formula of the red cobalt compound would be:

Co(NH3)4(H2O)Cl3 MM(Co)(NH3)(H2O)(Cl)= 268.4 g/mol

Both cobalt compounds are complex salts made of complex cations and counter ions

which balance the charges of the complex ion. With the molar mass of both compounds

and their respective equivalent weights, the charge of the compound is calculated.

Chargepurple Co = 250.4g/mol/124.15g/eq = 2.017  2

Chargered Co = 268.4g/mol/94.665g/eq = 2.835  3

Including the charge in the formula and taking in account that Cl- serves as counterion,

as it forms negatively charged ions that balance the positive charge of the cations in

both compounds, the complete formulas for both purple and red cobalt compounds is:

Purple Co compound: [Co(III)(NH3)5]2+(Cl3)2

Red Co compound: [Co(III)(NH3)5(H2O)]3+(Cl3)3

Following IUPAC nomenclature rules, the names for each compound are:

Red Co compound: pentaammineaquacobalt(III) trichloride

Adrián Alonso Canales 29-Nov.-24

Purple Co compound: pentaamminecobalt(III) trichloride

A movement of electrons is always associated with a change color, the same occur in

both red and purple cobalt compounds during different steps of the experiment. Co(III)

has a valence of six, meaning that is always surrounded by six ligands, when there is a

change on any of these ligands, a color change occurs in the compound as the structure

of the ion complex changes.

The first color change observed, occurs during the dehydration of the red cobalt

compound, giving as a result the purple cobalt compound, with the only difference of

the absence of H2O in the formula. The ligand(s) between Co(III) and H2O disappear

meaning that the compound will have orbitals available for electrons, and as a result, it

will be able to absorb a different wavelength than previously, in this case a less

energetic wavelength because of this. As a red cobalt compound, the wavelength

absorbed was of 470-500nm, meaning that it absorbed blue-green wavelengths showing

its red color. With the loss of H2O, it starts absorbing a wavelength of 500-520nm,

absorbing the green color and appearing as a purple-red compound.

The second color change observed takes place in the determination of %Cl in the purple

cobalt compound, after the complete precipitation of the chloride as AgCl, turning back

into a red compound. In this process, the purple cobalt compound which was

surrounded by its six ligands, loses the ones connected to the chlorides, and as happened

in the dehydration of the red cobalt compound it will have orbitals available for

electrons, but in this case the wavelength absorbed will be less and so a more energetic

light will be absorbed. As a purple compound the wavelength absorbed was of 500-

520nm, absorbing green color, with the precipitation of chloride, the compound turns

red again, absorbing a wavelength of 470-500nm which are blue-green colors.

Adrián Alonso Canales 29-Nov.-24

Ammonia NH3 Chloride Cl Cobalt Co Water H2O

Theorical % 34.00% 42.47% 23.53% 6.711%

Experimental % 32.635% 41.77% 25.20% 6.424%

Absolute error 1.365 0.700 1.670 0.2870

Percent error 4.015% 1.648% 7.097% 4.277%

In terms of accuracy, percent chloride has the highest with just 1.648% error, meaning

that the experiment has been performed with success and that the values extracted from

it are completely reliable in terms of obtaining the percent chloride of a compound.

Talking about the precision of Cl%, the standard deviation is very low of just 0.1250,

the lowest of all percent compounds, meaning that precision is very high between all

three samples. Although, the precision could always be higher and some random and

systematic errors could have occurred during the experiment. There exists always a

random error in the measurements of weight from the scale, as well as a systematic error

in case the scale or glassware are not calibrated, or in the contamination of samples.

Random errors could be variations in precipitate filtration, incomplete washing of the

precipitate, or a badly performed drying process, while systematic errors could have

happened with the solubility of the silver chloride precipitate or the precipitation of

other ions,

The accuracy of H2O percentage is substantially high. A value of percent error just over

4 percent, means that the experiment has been performed with success and that it gives

accurate percent values. Talking about the precision of the H2O% analysis, the standard

deviation of the three samples was of 0.8513, meaning that there exists a fluctuation of

less than 1% of percent compound between samples, what is not high, but it could
Adrián Alonso Canales 29-Nov.-24

probably be substantially lower if some errors would not have happened. There exists

always a random error in the measurements of weight from the scale, as well as a

systematic error in case the scale or glassware are not calibrated, or in the contamination

of samples. Some systematic errors could have been done in case the compounds would

not have been left in the oven or desiccator for enough time or proper temperature,

affecting clearly the accuracy or the reaction.

For percent ammonia, the accuracy is high, a value of percent error of right on 4%

shows a good job in terms of obtaining a fairly similar percent value as the expected,

meaning that the experiment has been performed in the proper way. NH3% precision

was ruled by a standard deviation of 0.715, which again, is not a high one, by there is

still a deviation in the first decimal, what is not optimal. As always, there exists a

random error in the measurements of weights from the scale, as well as a systematic

error in case the scale or the glassware are not calibrated, and contamination of samples.

Potential random errors include variations in the volume of solution transferred during

pipetting or the endpoint the student determines during titration. Added to those errors’

incomplete digestion of the sample, or sample losses during distillation are two

systematic errors that may have occur.

Accuracy for percent cobalt was the lowest of all compounds, but with a percent error of

right over 7%, it is still a pretty high accuracy and it can be determined that the

experiment have been performed with success. The standard deviation obtained in the

%Co was of 1.357, which is the highest of all percentage determinations. The value is

not very high, but a variation higher than 1% between trials is far from being perfect,

meaning that some random or systematic error might have occur. Added to the random

and systematic errors from measurements of the scale and the possibility of the use of

non-calibrated scale or glass material, and the contamination of solutions; some random
Adrián Alonso Canales 29-Nov.-24

and systematic errors could have happened. In first case, by standardizing the Co(III)

error should be eliminated, but in case there was some error in that calculation have

been carried to the Co% determination. In this case, random error could have been in

unpraised readings of the buret meniscus, improper mixing of solutions, non-perfect

endpoint color change perception, and the presence or air bubbles in the buret during

titration. During the spectrophotometric determination, random errors could go from

fluctuations in sample temperature, the variation of cuvettes used and how they were

positioned and inconsistencies in sample mixing. Following these, some systematic

errors could go from the loss of material remaining in the beaker in the conversion of

Co(III) to Co(II), this was observed in my A and C samples, as well as the use of dirty

cuvettes for the measurements and variation in light interference during the

measurements.

Bibliography:

Brennan, J. (2022, March 24). Why do hydrates change color when heated? Sciencing.

[Link]

%20the%20hydrate%20loses%20the,light%20than%20it%20did%20before.

Fan, J. (2024). CHEMISTRY 302 ANALYTICAL CHEMISTRY LABORATORY

MANUAL. The Department of Chemistry and Biochemistry Manhattan College.