Khylla Mheryl Y. Caballes Y.

Caballes October 20, 2018

17L October 28, 2018
2

METAL COMPLEX EQUILIBRIA

I. Introduction
Coordination compounds play many important roles in animals and plants. They
are essential in the storage and transport of oxygen, as electron transfer agents, as
catalysts, and in photosynthesis (Chang, 2010). Coordination compounds are made
up of a complex and a counter ion(s). The Lewis acid-base interaction paved way to
the formation of metal complex. Complex ion forms from metal ion and a ligand. The
positively charged metal ion acts as a Lewis acid, and the ligand, with one or more
lone pairs of electrons, acts as a Lewis base. Small, highly charged metal ions, such
as Cu2+ or Ru3+, have the greatest tendency to act as Lewis acids, and consequently,
they have the greatest tendency to form complex ions (Equilibrium of Metal
Complexes, 2016).

M + L ⇆ ML
When equilibrium is attained from the reactions of metal complexes the
formation constant or the stability constant can be written and determined by
substituting the concentrations of the species involved.
[ML]
𝐾𝑓 =
[𝑀][𝐿]
The value KF can be used to determine the stability and probability of existence
of the complex such that the higher the value the more stable and the higher the
probability of existence (Arche, et al., 2018).
The spectrochemical series is the list of ligands arranged in order of the strength
of metal-ligand interaction in the complex. The stability of the metal complex
depends on the strength of the metal-ligand interaction (Arche, et al., 2018).
According to Arche, et al. (2018) metal complexes usually formed colored
solutions. The wavelength complementary to the color perceived (the wavelength of
the color absorbed) is important in determining the field strength of the ligands. The
 field strength of the ligands depends on its crystal field splitting (∆) which is given
by the equation:
ℎ𝑐
∆= 𝐸 = ℎ𝑣 =
𝜆
A higher the crystal field splitting results to a higher the field strength of a ligand
(Chang, 2010).
This experiment aimed to delve on the metal complexes, and its equilibrium.
Specifically it aimed to; let the students prepare different cobalt (III) complexes
using different ligands and based from it write the complexation reactions and the
formation of the constant expression of the complexes, and construct a
spectrochemical series based on the color of the solutions formed.

II. Materials
A. Reagents
The reagents used in the experiment were 3 1mL of 0.05 cobalt chloride
solution, [Co(H2O)6], few drops of 6M ammonia, NH3, 2 1mL of 1mL and few drops
of 6% hydrogen peroxide, H2O2, few drops of 0.05M sodium nitrite, NaNO2, 1.5 mL
of glacial acetic acid, CH3COOH, 1 mL sodium bicarbonate solution, NaHCO3, and 6M
nitric acid HNO3.
B. Apparatus and Equipment
The apparatus and equipment used were 4 test tubes, 2 droppers, 5 pipets and
respirators

III. Procedures
A. Preparation of Different Cobalt (III)
The materials used were prepared, glass wares were cleaned and all liquids
were ready. Four (4) test tubes were labeled A, B, C, and D indicating the set
ups. 1 mL of 0.5 M cobalt chloride solution was placed in set-ups labeled A, B,
and C. In each test tube different liquids were added and mixed. A few drops of
6M of ammonia followed by 1 mL 6% hydrogen peroxide were placed in set-up.
In set up B, a few drops of 0.05 sodium nitrite solution followed by 1.5 mL of
glacial acetic acid were put. While in set-up C a few drops of 1.0 mL of saturated
sodium bicarbonate followed by 1.0 mL of 6% hydrogen peroxide solution were
 added. Then, 1 mL of the solution in test tube C was transferred in test tube D,
then 1.0 mL of 6M nitric acid were slowly added to it to produce [Co(H20)6]3+.
B. Predicting the arrangement of ligands in the spectrochemical series
The color wheel was used to determine the light absorbed by the solution
based on the color perceived in the experiment. The Table about the perception
of color based on the wavelength of light absorbed was utilized in determining
the arrangement of ligands in the spectrochemical series (Table 9.1) (Arche, et
al., 2018).

C. Waste Management
Wastes were managed by disposing all materials the bottle assigned for
Cobalt containing waste.

IV. Data and Observations

The data obtained was recorded and analyzed

A. Color observed in the solution and the predicted complexation formed

SET-UPS COLOR OBSERVED Complexation formed

Original complex Pink [Co(OH2)6]2+
hexaamminocobalt(III)

A Red Orange [Co(NH3)6]2+

hexaamminocobalt(III)

B Yellow [Co(NO2)6]3-
hexanitritocobalt(III)

C Green [Co(CO3)3]3-
tricarbonatocobalt(II)

D Blue [Co(OH2)6]2+
hexaaquacobalt(III)

The test tubes of different set-ups showed significant color changes from the
original pink solution of cobalt chloride to different colors such as red orange,
yellow, green and blue. This was due to the complexation of cobalt (III) with
other ligands.
B. Net ionic equation of the complexation formed and Kf expressions
Metal complexes Net Ionic Equation Kf expressions
Original complex [Co(OH2)6]2+ + Cl- ⇆ [CoCl4]2- +
6H2O
[Co(NH3)6]2+ Co3+ + 6NH3⇆[Co(NH3)6]2+ 𝐾𝑓 =
[Co(𝑁𝐻3 )6 ]2+
[𝐶𝑜3+ ][𝑁𝐻3 ]6

[Co(NO2)6]3- Co3+ + 6NO2- ⇆[Co(NO2)6]3- 𝐾𝑓 =

[Co(𝑁𝑂2 )6 ]3−
[𝐶𝑜3+ ][𝑁𝑂2 )− ]6

[Co(CO3)3]3- Co3+ + 3CO32- ⇆[Co(CO3)3]3- 𝐾𝑓 =

[Co(𝐶𝑂3 )3 ]3−
[𝐶𝑜3+ ][𝐶𝑂3 )2− ]3

[Co(OH2)6]2+ Co3+ + 6NO2- ⇆[Co(OH2)6]2+ 𝐾𝑓 =

[Co(O𝐻2 )6 ]2+
[𝐶𝑜3+ ][𝐻2 𝑂]6

Analysis of the data yields the net ionic equation involved in the complexation
of the Cobalt (III) and the species formation constant, Kf. The principle of
equilibrium was used to evaluate these equations.

C. Analysis of the color of the solution to predict the arrangement of ligands in the
spectrochemical series

COMPLEXATION COLOR REFLECTED COLOR ABSORBED WAVELENGTH (nm)

[Co(NH3)6]2+ Red Orange Bluish Green 490-500
[Co(NO2)6]3- Yellow Violet 400-435
[Co(CO3)3]3- Green Red 500-560
[Co(OH2)6]2+ Blue Orange 595-605
 The data was further examined through the color wheel which generated the
colored absorbed by the cobalt (III) complexes.
The concept of reflected light wherein the color of the light seen by the eye
is complementary to the color absorbed by the medium (solution) and its
wavelength, was actualized in the analysis of data. The difference in colors of the
complexes acquired different wavelengths thus yielding different energies.
D. Field strength
COMPLEXATION LIGANDS WAVELENGTH (nm) ENERGY ∆ (kJ/mol)

[Co(NH3)6]2+ NH3 495 241.76

[Co(NO2)6]3- NO2- 417.5 286.97
[Co(CO3)3]3- CO32- 530 225.80
[Co(OH2)6]2+ OH2 600 199.44
Spectrochemical series
OH2 < CO32- < NH3 < NO2-

The data was further inspected by comparing the field strength of the
ligands. The higher absorbed wavelength the weaker the field strength and the
lower the absorbed wavelength the stronger the field strength. OH2 ligand was
the weakest and the NO2- was the strongest in terms of field strength.

V. Discussion

A. Metal Complex Equilibrium

Complex ions undergo ligand exchange (or substitution) reactions in solution. In
studying this ligand exchange reactions, it is useful to differentiate between the
stability of the complex ions and its kinetic lability (the tendency to react). Stability in
this concept is a thermodynamic property, which is measured in terms of the
species’ formation constant Kf (Chang, 2010). The Kf is used in determining the
stability of the complex such that a high value means the complex is stable and the
higher the probablity that the complex will exist (Arche, et al., 2018).
 There are two classification of complexes in accordance to their kinetic lability,
the labile complexes and inert complexes.. Labile complexes are complexes which
undergoes rapid ligand exchange reactions. While inert complexes are complexes
which undergoes very slow exchange reactions (on the order of hours or even days)
(Schaller, 2017). Inert complexes of of were utilized in the experiment. Most
complex ions containing Co3+, Cr3+, and Pt2+ are kinetically inert. Due to their ability
to exchange ligands very slowly, they are easy to study in solution. This is the
reason why the chemical knowledge of the bonding, structure, and isomerism of
coordination compounds has come largely from studies of these compounds (Chang,
2010).

B. Crystal field splitting

The color that was perceived in the experiment and the magnetic properties of

complexes can be explained by the crystal field splitting (∆) theory. When the
metal-ligand interaction and electrostatic repulsion causes the five d orbital in an
octahedral complex to split into two sets of energy levels. The crystal field splitting

(∆) is the energy difference between two sets of d orbitals in a metal atom when

ligands are present. The magnitude of ∆ depends on the metal and the nature of
the ligands; it has a direct effect on the color and magnetic properties of complex
ions (Chang, 2010). Ligands with a high d orbital splitting has a higher field strength
(low spin) than that of the ligands with lower d orbital spliting (high spin) . Usually
tetrahedral field has intrinsically lower crystal field splitting than that of the
octahedral field. For most purposes purposes the relationship relationship may be

represented represented as ∆t = 4/9 ∆o (Crystal Field Splitting in an Octahedral

Field). Quantitative value of the crystal field splitting can be obtained through
spectroscopy or the the technique of splitting light (or more precisely
electromagnetic radiation) into its constituent wavelengths (Jay, 2018). In the
experiment the wavelength was determined by the concept of reflected and
absorbed light.
This wavelength can be used in determining the crystal field splitting by the
formula:
 ℎ𝑐
∆= 𝐸 = ℎ𝑣 =
𝜆
Where
h = Planck’s constant
v = frequency
c = speed of light
𝜆 = wavelength
The amount calculated is the energy needed to excite a complex ion. Aided by
spectroscopic data for a number of complexes, all having the same metal ion but
different ligands, chemists calculated the crystal splitting for each ligand and
established a spectrochemical series, which is a list of ligands arranged in increasing
order of their abilities to split the d orbital energy levels (Chang, 2010)
I- < Br- < Cl- < OH- < F- < H2O < NH3 < en < CN- < CO

These ligands are arranged in the order of increasing value of ∆. Co and CN- are
called strong-field ligands, because they cause a large splitting of the d orbital
energy levels. The halide ions and hydroxide ion are weak-field ligands, because
they split the d orbitals to a lesser extent (Chang, 2010).

VI. Conclusion
Metal complexes are formed from the interaction of the metal ion and ligands
and the stability of the metal complex formed depends on the metal-ligand
interactions. The stability can also be quantitatively calculated using the species
formation constant such that the higher the Kf the higher the stability. The formation
of the same metal center but different ligands produces the different in colors of the
solution which is due to the concept of the reflected and absorbed light wherin the
color perceived is complementary to the wavelength to the wavelenth of lights
absorbed by the complex. The wavelength of the light absorbed is used to calculate

the crystal field splitting energy (∆). The crystal field splitting or the splitting of the
d orbitals into two sets and energy level. This crystal splitting value was utilized to
form the spectrochemical series which determines the weakness and strength of the
field of the ligands or its ability to interact closely with the metal center. This study
therefore proven that the longer the absorb wavelength which means the lower the
 crystal field spliting energy, the weaker the field of strength of the ligands and the
smaller the absorb wavelength which means the higher the crystal field spliting
energy, the stronger the field of strength of the ligands.

VII. Literature Cited

Equilibrium of Metal Complexes. (2016, July 20). Retrieved October 26, 2018, from Chemistry
Libretexts:
https://chem.libretexts.org/LibreTexts/Heartland_Community_College/HCC%3A_Chem_1
62/24%3A_Chemistry_of_Coordination_Compounds/24.3%3A_Equilibrium_of_Metal_Co
mplexes

Arche, P. A., Clavecilla , D. F., Gabog, K. C., Delmo, N., Molino, V. E., de Quina, P., et al.
(2018). CHEM 18.1 University Chemistry Laboratory. Los Banos: University of the
Philippines Los Banos.

Chang, R. (2010). Chemistry 10th Edition. Avenue of the Americas Ney, York City: McGraw-Hill,
a business unit of The McGraw-Hill Companies, Inc.,.

Crystal Field Splitting in an Octahedral Field. (n.d.). Retrieved October 25, 2018, from CHEM
102: http://home.iitk.ac.in/~madhavr/CHM102/Lec3.pdf

Jay. (2018). Introduction to infrared spectroscopy. Retrieved October 25, 2018, from Khan
Academy: https://www.khanacademy.org/science/organic-chemistry/spectroscopy-
jay/infrared-spectroscopy-theory/v/introduction-to-infrared-spectroscopy

Schaller, C. (2017, March 31). CC10. Ligand Field and Lability. Retrieved October 26, 2018,
from Libretexts:
https://chem.libretexts.org/Textbook_Maps/Inorganic_Chemistry/Supplemental_Modules
_(Inorganic_Chemistry)/Organometallic_Chemistry/Ligand_Binding_in_Coordination_Co
mplexes/CC10._Ligand_Field_and_Lability