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EXERCISE 9:

METAL-COMPLEX EQUILIBRIA

I. Introduction

Compounds of the transition metals naturally exhibit different colors because these metals
can absorb visible light of specific wavelengths—they make up a significant group of colored
substances. Many of these were isolated and studied by a lot of chemists even before the periodic
table was introduced for they showed some properties which was contradicting to the bonding
theories at the time. These colors vary depending upon the involved metal center and ligands in
a metal complex. The Swiss chemist Alfred Werner further explained that the arrangement of
ligands can also cause the variation of colors in complexes (Brown, LeMay, Bursten, Murphy,
Woodward, 2009).

Species which are formed from the assembly of a central metal ion bonded to a group of
surrounding molecules or ions known as ligands (from the Latin word ligare, meaning “to bind”)
are called metal complexes. They are also called complex ions when the complexes carry a net
charge. The metal ion and its ligands comprise the coordination sphere of the complex. An
example of this is [Ag(NH3)2]+ which has two NH3 ligands bonded to Ag+. Each of this ligand acts
as a Lewis base that donates atom to the metal to form a bond. This means that every ligand has
at least one unshared pair of valence electrons. Compounds that contain metal complexes are
known as coordination compounds (Brown, et al., 2009). The formation reaction of a metal
complex can be written as:

M + L ⇔ ML equation 9.1

Where:

M = central metal ion

L = ligand attached to the central metal ion

ML = metal complex formed

The stability constant, also called the formation constant Kf, gives the measure of the tendency
of a metal ion to form a complex (Chang, 2008). The stability of a complex ion in aqueous solution
can be obtained by the size or amount of the equilibrium constant for its formation from the
hydrated metal ion (Brown, et al., 2012). This can be computed by simply substituting the
equilibrium concentrations of the involved species and can be written as:

Kf = [ ML ] equation 9.2
[M] [L]

Where:

M at equilibrium = concentration of metal at equilibria

L at equilibrium = concentration of ligand at equilibria

ML at equilibrium = concentration of product at equilibria (complex formed)


The list below, which is an abbreviated list of common ligands arranged in order of increasing
interaction strength with metal ions, is known as the spectrochemical series. Weak-field ligands
lie on the low end of the spectrochemical series while the strong-field ligands lie on the high end
(Brown, et al., 2009). Strong-field ligands cause a large splitting of the d orbital energy levels and
absorb light of shorter wavelength, while the weak-field ligands cause the d orbitals to split to a
lesser extent and absorb radiation of longer wavelength. In other words, ligands are arranged in
increasing order of their abilities to split the d orbital energy levels in this series. The order does
not change no matter which metal atom is present and the magnitude of the splitting of the d-
orbitals in a transition metal complex mainly depends on the nature of the ligands, oxidation state
of the metal, and the geometry of the metal complex. (Chang, 2008).

I- < Br- < Cl- < OH- < F- < H2O < NH3 < en < NO2- (N-Bonded) < CN- < CO

The objectives of this exercise are to successfully prepare various cobalt (III) complexes
with the use of different ligands, and to write complexation reactions and formation constant
expressions. Constructing spectrochemical series based on the colors of the solutions formed is
also an expected outcome in this exercise.

II. Materials
A. Reagents
 1 mL of 0.05 M cobalt chloride solution
 Few drops of 6 M ammonia
 1.0 mL of 6% hydrogen peroxide solution
 Few drops of 0.05 M sodium nitrite solution
 1.5 mL glacial acetic acid
 1.0 mL of saturated sodium bicarbonate
 1.0 mL of concentrated 6 M nitric acid

B. Apparatus and Equipment


 Four test tubes labeled as A, B, C, and D
 Pasteur pipette
 100 mL pipette
 Aspirator

III. Procedure
A. Preparation of different Cobalt (III) metal complexes
1 mL of 0.05 M cobalt chloride solution was placed in three clean, dry test tubes.
The pink Co(H2O)62+ complex with water as ligand caused the color of this solution.
These test tubes were labeled as A, B and C, then a few drops of 6 M ammonia were
added to test tube A before mixing it thoroughly. After this, 1.0 mL of 6% hydrogen
peroxide solution was added.
For test tube B, a few drops of 0.05 M sodium nitrite solution were added, followed
by 1.5 mL of glacial acetic acid. Finally, 1.0 mL of saturated sodium bicarbonate and
1.0 mL 6% hydrogen peroxide solution were added to test tube C.
1.0 mL of the solution from test tube C was transferred to a clean, dry test tube,
then it was labeled as D. Slowly, 1.0 mL of concentrated 6 M nitric acid was added to
produce [Co(H2O)6]3+. Color changes, precipitate formation and evolution of gas was
observed and noted down on Table 9.2.

B. Predicting the arrangement of the ligands in the spectrochemical series

The complexes were arranged based on the amount of light absorbed using Table
9.1. Then the ligands were also arranged based on field strength.

C. Waste Management

All mixtures were thrown away in the waste bottle designated for Cobalt containing
wastes.

IV. Data/Observation

The observations noted upon the addition of the given ligands to the cobalt chloride solutions
were recorded in Table 9.2. Upon the addition of a few drops of 6 M ammonia, the cobalt chloride
solution’s color changed to bluish green, then it altered to color orange-brown when 1.0 mL of 6%
hydrogen peroxide solution was added. Formation of precipitation was also observed. No
changes were noted upon adding a few drops of 0.05 M sodium nitrite solution, but the addition
of 1.5 mL of glacial acetic acid transformed the color of the solution to light pink. When 1.0 mL of
saturated sodium bicarbonate was added to test tube C, the color of the solution turned violet.
Upon adding 1.0 mL of 6% hydrogen peroxide, the solution exhibited the color dark green
accompanied by the formation of bubbles. Lastly, adding 1.0 mL of concentrated 6 M nitric acid
to the 1.0 mL solution transferred from test tube C to test tube B turned the solution to yellow.

The theoretical colors for the test tubes A, B, C, and D are brown, yellow, green, and blue
respectively. The complex formed upon the addition of the ammonia ligand is [Co(NH3)6]3+,
[Co3(NO2)6]3- was formed when the nitrite ligand was added, carbonate ligand resulted to the
formation of [Co(CO3)6]3-, and the complex [Co(OH2)6]3+ was formed upon adding the water ligand.
These data, as well as the colors observed in each test tube, were recorded in Table 9.3, while
the perception of color based on the wavelength of light absorbed is indicated in Table 9.1.

V. Discussion

The binding of cobalt metal ion from the cobalt chloride solution to the different ligands are
examples of metal complexes. Colors exhibited in each formation reaction depend on the
ligands attached to the metal ion. When 6 M ammonia was added to the solution, the color
bluish green was observed which means it absorbed red and wavelength of 605-750 nm. Upon
the addition of 6% hydrogen peroxide solution, the color turned orange-brown, indicating that
the absorbed color and wavelength were greenish blue and 480-490 nm respectively. No
changes occurred in adding 0.05 M sodium nitrite solution to test tube B, but the addition of 6%
hydrogen peroxide solution resulted to the color light pink. However, the expected final color for
this set-up was yellow, absorbing color blue and wavelength ranging from 435-480 nm. For test
tube C, color violet was exhibited upon adding saturated sodium bicarbonate. It denotes that
560-580 nm of wavelength and yellowish green was absorbed in this. The addition of 6%
hydrogen peroxide turned the color of the solution to dark green, which means it absorbed
orange and wavelength ranging from 595-605 nm. Lastly, adding 6 M nitric acid to test tube D
turned the solution yellow. However, the expected color for this set-up was blue, absorbing color
yellow and wavelength of 580-595 nm.

For test tubes B and D, the experimental colors (light pink and yellow) were different from
the theoretical colors (yellow and blue). The sources of error could involve the presence of
impurities, temperature, and validity of substance.

Following the formula given in equation 9.1, each ligand will have the resulting formation
reactions:

Ammonia: Co3+ + 6NH3 ⇔ [Co(NH3)6]3+


Nitrite: Co3+ + 6NO2- ⇔ [Co(NO2)6]3-
Carbonate: Co3+ + 6CO32- ⇔ [Co(CO3)3]3-
Water: Co3+ + 6H2O ⇔ [Co(OH2)6]3+

Attaching these ligands to the central metal ion resulted to different colors because they
absorb varying wavelengths as stated above. Based from the gathered data and observations,
carbonate was found to absorb the longest wavelength, followed by water, ammonia, and then
nitrite. Since weak-field ligands absorb radiation of longer wavelength compared to the strong-
field ones, this means that carbonate lies on the low end of the spectrochemical series. The four
ligands arranged in terms of increasing field strength is shown below.

CO32- < H2O < NH3 < NO2-

Addition of different ligands to the cobalt chloride solution resulted to the transformation of
variety of colors, and formation of bubbles and precipitation.

Cobalt chloride solution exhibit the color pink because of the presence of the water as its ligand.

The unknown solvent and unknown solution were observed gradually turning transparent
before completely melting at 90°C and 85°C respectively. The samples started to solidify again at
75°C and 72°C respectively and they slowly turned back to their original color. This is because in
solid form, the crystallites in the samples scattered light which resulted to higher opacity, but when
they were exposed to high temperature, these crystallites melted leaving the liquid with clear
appearance. At 70°C and 68.8°C respectively, the samples completely turned opaque and solid.

Figure 4.1 shows a gradual decreasing trend which means that as the samples cooled down,
the temperature decreases. The curved graph shows the declining of the difference between the
temperature of the substance and the environment. It also displays the state of the substance—
whether they’re undergoing phase change or not. Based on the data recorded, the temperature
of the unknown samples in the test tube kept decreasing until it reached a certain value where it
remained constant for a few seconds before it continued to fall again. This point shows that the
temperature wasn’t changing because the kinetic energy wasn’t changing as well (according to
Charles’ Law), unlike the potential energy which was altering during this point. The figure also
showed the freezing points of the unknown solvent and solution which were 77°C and 72°C
respectively. Their temperature remained constant for more than one 15-second interval as it was
undergoing phase change (liquid to solid).

The freezing point depression can be obtained by multiplying the molality of the solution and
the freezing point depression constant of the solvent. The freezing point depression of the solution
is lower than that of a pure solvent because it is a colligative property of the solution. This means
that it is dependent on the number of the dissolved particles in it and they are directly proportional
to each other. Its application can be seen when people put salt on ice roads to prevent the melting
ice from freezing back. Salt can also be used to make the ice colder when the two of them are
put together in a container. Another practical use of this is the mixture of ethylene glycol and water
which makes up the radiator fluid of an automobile. This helps in keeping the radiators from
freezing during winter. The introduction of solute to the solvent also makes the freezing point of
the mixture lower than the freezing point of a pure substance because the solute concentration
increases as the solvent freezes.

The cooling curves show the freezing point of the solvent and solution which are 77°C and
72°C respectively. By comparing the freezing point of the unknown solvent to the given freezing
points of other substances, it was found out that the experimental freezing point of the unknown
solvent was closest to that of Napthalene’s which is 80°C as shown in Table 4.4, hence, it is
identified as Napthalene. Its cooling curve is shown in Figure 4.1.

The equation for the freezing point depression will be used in order to identify the unknown
solute:

ΔTf = Tf (solvent)−Tf (solution)= kfm

Where:

ΔTf = freezing point depression

Tf = freezing point

kf = freezing point depression constant of the solvent

m = molality of the solution

Deriving the formula for the molality of the solution from this and plugging in the values will
give us the equation and answer:
(𝚫𝐓𝐟 )
𝒎=
𝐤𝐟
|(𝟖𝟎−𝟕𝟐)| 𝒎𝒐𝒍
𝒎= 𝟔.𝟗
𝒎 = 𝟏. 𝟏𝟔 𝒌𝒈

The theoretical freezing point of the solvent was used in the equation above which is 80°C
while the freezing point depression (kf) was given in Table 4.4. The molecular mass of the solute
can now be computed using this value of molality with the given data from Table 4.3.
𝒎𝒐𝒍 (𝒎𝒐𝒍𝒔𝒐𝒍𝒖𝒕𝒆 )
𝟏. 𝟏𝟔 =
𝒌𝒈 𝒌𝒈𝒔𝒐𝒍𝒗𝒆𝒏𝒕
𝒎𝒐𝒍 (𝒎𝒐𝒍𝒔𝒐𝒍𝒖𝒕𝒆 )
𝟏. 𝟏𝟔 =
𝒌𝒈 𝟐. 𝟎𝟐𝒙𝟏𝟎^ − 𝟑 𝒌𝒈

molsolute = (1.16 mol/kg) (𝟐. 𝟎𝟐𝒙𝟏𝟎^ − 𝟑 kg) = 2.34x10^-3 mol

MM = g/mol = 0.35 g / 2.34x10^-3 mol = 149.37g/mol

Now that the molecuar mass of the unknown solute is computed, it can be compared to the
list of probable identity of the solute shown in Table 4.5 to find out what it is. The closest molecular
mass to this is the molecular mass of Benzoic acid which is 122.12 g/mol. The unknown solvent
can now be identified as Benzoic acid whose cooling curve is shown in Figure 4.2.

To compute for the value of the freezing point depression of this experiment, the obtained
values from the previous calculation are substituted into the equation:

ΔTf = kfm

Hence, the answer will be:

8.004°C = (6.9)(1.16 mol/kg)

For the computation for the % error of the freezing point and molecular mass the equation
below will be used:

% error = |accepted – experimental| x 100


accepted

Plugging in the obtained values will result to the % error of the freezing point:

3.75% = |80 – 77| x 100


80

While substituting the obtained values for computing the % error of molecular mass will give
the answer:

22.31% = |122.12 – 149.37| x 100


122.12

Table 4.4 shows that the experimental freezing point of Napthalene which is 77°C is different
from its expected freezing point which is 80.2°C. One of the reasons for this difference could be
the inconsistent stirring of the water bath which was supposed to distribute the heat evenly
throughout the bottom of the beaker. This could have caused the temperature to decrease more
slowly. The recorded 15-second interval time recorded from the stopwatch could have also
affected the results of the experiment as well as the air-conditioned room where this experiment
took place. If the temperature was also recorded more often rather than by 15-second interval
only, the data obtained would’ve been more precise. Another possible source of error is the
inaccurate reading of the thermometer during the heating of the samples.
As stated above, reading the temperature of the sample more often can help in obtaining more
precise values and decreasing the percent error of the experiment. Making sure that the stirring
bath is continuously stirred during the heating process will also give better results.

VI. Conclusion

From the conducted experiment, the following conclusions were made:

 The plotted cooling curves showed a decreasing trend which means that the
temperature (°C) of the samples is inversely proportional to the time (sec). The observed
states in the cooling curves were liquid, semi-solid, and solid states.
 It was also found out that the solution has lower experimental freezing point than the
solvent—72°C and 77°C respectively. The difference between the freezing point in 5°C.
This proves that the properties of a solution indeed differ from its components which are
the solute and solvent.
 From the obtained data, we have proved that the presence of the particles of a solute
decreases its freezing point and changes its molecular order.
 Freezing point depression was observed in the difference between the freezing point of
the pure solvent which is greater than the freezing point of the solution. The computed
freezing point depression is 8.004°C.
 The unknown solvent was identified as Napthalene with a freezing point of 80°C and the
unknown solute was identified as Benzoic Acid with a molecular mass of 149.45 g/mol,
while the computed molality of the solution is 1.16 mol/kg.
VII. Literature Cited/Bibliography

Brown, T., LeMay, H., Bursten, B., Murphy, C., & Woodward, P. (2009). Chemistry: The

Central Science (11th ed.). Singapore: Pearson Education South Asia.

Chang, R. (2008). General Chemistry: The Essential Concepts (5th ed.). New York:

McGraw-Hill.

Wysession, M., Frank, D., & Yancopoulos, S. (2004). Physical Science: Concepts in Action

with Earth and Space Science. New Jersey: Pearson Prentice Hall.

Zumdahl, S. S., & Zumdahl, S. A. (2007). Chemistry (7th ed.). U.S.A.: Houghton Mifflin

Company.
Appendices

Table 9.1. Perception of color based on the wavelength of light absorbed.

Wavelength absorbed (nm) Color absorbed Color observed


400-435 Violet Greenish yellow
435-480 Blue Yellow
480-490 Greenish blue Orange
490-500 Bluish green Red
500-560 Green Reddish violet
560-580 Yellowish green Violet
580-595 Yellow Blue
595-605 Orange Greenish blue
605-750 Red Bluish green

Table 9.2. Observations on the upon addition of different ligands to the cobalt chloride solution.

Test Tube Ligand Added Observations


The color changed to bluish green, then
upon the addition of hydrogen peroxide,
A Ammonia
the color changed to orange-brown and
precipitation was formed
There were no observations noted, but
B Nitrite upon the addition of glacial acetic acid, the
color turned to light pink
The color changed to violet, and upon
adding hydrogen peroxide, the color
C Carbonate
turned dark green and bubbles were
formed
D Water The solution turned yellow

Table 9.3. Complex formed, theoretical and experimental colors observed upon adding different
ligands to the cobalt chloride solution.

Test Tube Theoretical Color Color Observed Complex Formed

A Brown Orange-brown [Co(NH3)6]3+

B Yellow Light Pink [Co3(NO2)6]3-

C Green Dark Green [Co(CO3)6]3-

D Blue Yellow [Co(OH2)6]3+


Table 4.3. Data obtained on the determination of the molecular mass of the unknown solute.

Parameter Value
Unknown Solvent Solvent 1 Solvent 2
Mass of container + sample, g 188.36 g 159.72 g
Mass of container, g 186.30 g 157.70 g
Mass of sample, g 2.06 g 2.02 g
Freezing point, °C 77°C 77°C
Freezing point depression constant, °C/m 6.9°C/m
Unknown Solute
Mass of container + sample, g 158.05 g
Mass of container, g 157.70 g
Mass of sample, g 0.35 g
Freezing point of solution, °C 72 °C
Molality of solution, mol/kg 0.7246 mol/kg
Molecular mass of unknown solute, g/mol 239.1g/mol

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