Name of Student: Jalotjot, Christine Joy F.

Date Performed: October 17, 2018

Section: 56 L Date Submitted: October 26, 2018
Group: 3

METAL-COMPLEX EQUILIBRIA
I. Introduction

When a metal ion reacts with a Lewis base in solution a complex ion is formed. This
reaction can be described in terms of chemical equilibria. A complex ion is comprised of two
important parts: the central atom and its surrounding ligands. The central atom can be any
metallic ion (usually a transition metal). The ligands are any combination of anions that can
donate an electron pair, effectively meaning they are all Lewis bases. When combined they
form coordinate covalent bonds.
Chemical equilibrium is the state of a reversible reaction where the rate of the
forward reaction equals the rate of the reverse reaction. While a reaction is in equilibrium the
concentration of the reactants and products are constant. The equilibrium constant, K,
expresses the relationship between products and reactants of a reaction at equilibrium with
respect to a specific unit.
Complex ion equilibria are no exception to this and have their own unique equilibrium
constant. This formation constant, 𝐾𝑓 , describes the formation of a complex ion from its
central ion and attached ligands. This constant may be called a stability constant or
association constant; the units depend on the specific reaction it is describing. The formation
reaction is shown below:
M+L ML
At its most basic level, 𝐾𝑓 can be explained as:
[𝑀𝑥 𝐿𝑦 ]
𝐾𝑓 =
[𝑀]𝑥 [𝐿]𝑦
where M is a metal ion, L is a ligand, and x and y are coefficients.
𝐾𝑓 values tend to be very large in magnitude because complex ion formation
reactions heavily favor the product.
II. Materials
A. Reagents
 0.05 M cobalt chloride solution
 6 M ammonia
 6% hydrogen peroxide solution
 0.05 M sodium nitrite solution
 glacial acetic acid
 saturated sodium bicarbonate solution
 6 M nitric acid
B. Apparatus and Equipment
 Test tubes
 Test tube rack
 Graduated cylinder

III. Procedure

A. Preparation of different Cobalt (III) metal complexes

In three clean, dry test tubes, place 1 mL of 0.05 M cobalt chloride solution. The color
of this solution is due to the pink Co(H2 O)6 2+ complex with water as ligand. The formation
reaction can be written as:

[Co(H2 O)6 ]2+ (aq) + 4Cl− [CoCl4 ]2− (aq) + 6 H2 O

Label them as A, B, and C. Add a few drops of 6 M ammonia to test tube A and mix
well. Then, add 1.0 mL of 6% hydrogen peroxide solution. If color change is observed, this is
due to the complexation of Cobalt (III) with ammonia.

To test tube B, add few drops of 0.05 M sodium nitrite solution, followed by .5 mL of
glacial acetic acid. Then, add 1.0 mL of saturated sodium bicarbonate solution to test tube C,
followed by 1.0 mL of 6% hydrogen peroxide solution.

Transfer 1.0 mL of the solution in test tube C to a clean test tube labeled D, and then
slowly adds 1.0 mL of concentrated 6 M nitric acid to produce [Co(H2 O)6 ]3+. Observe for
color changes, precipitate formation and evolution of gas. Record the results on Table 9.2.

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

Using Table 9.1, arrange the complexes in terms of the amount of light absorbed,
and then arrange the ligands in terms of field strength.
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 – 705 Red Bluish green

Waste Management

Dispose all mixtures in the waste bottle designated for Cobalt containing waste.

IV. Data/Observations

Table 9.2. Observations on the upon addition of different ligands to the Cobalt Chloride
solution

Test Tube Ligand Observation Theoretical Complex Formed

- Chloride, Cl− Blue Blue
- Water, H2 O (Co2+ ) Pink Pink
A Ammonia, NH3 Brown Red-Orange / Orange Brown [Co(NH3 )6 ]3+
B Nitrite, NO2 − Light Pink Yellow [Co(NO2)6]3−
C Carbonate, CO32− Green Green [Co(CO3 )3 ]3−
D Water, H2 O (Co3+ ) Yellow Blue [Co(OH2 )6 ]3+

V. Discussion

Crystal Field Theory (CFT) is a model that describes the breaking of degeneracies of
electron orbital states, usually d or f orbitals, due to a static electric field produced by a
surrounding charge distribution (anion neighbors). This theory has been used to describe
various spectroscopies of transition metal coordination complexes, in particular optical
spectra (colors). CFT successfully accounts for some magnetic properties, colors, hydration
enthalpies, and spinel structures of transition metal complexes, but it does not attempt to
describe bonding. CFT was developed by physicists Hans Bethe and John Hasbrouck van
Vleck in the 1930s. CFT was subsequently combined with molecular orbital theory to form
the more realistic and complex ligand field theory (LFT), which delivers insight into the
process of chemical bonding.

Electrons in the d orbital split into high energy and low energy orbitals when ligands
are attached to a transition metal (to form a coordination complex). The difference in energy
of the two levels is denoted as ∆, and it is a property of both metal and ligands.

If the energy difference is large, and much energy is required to promote electrons
into the high energy orbitals, the electrons will instead pair in the lower energy orbitals,
resulting in a "low spin" complex and associated with a “strong field” ligand; however, if the
energy difference is small, and it takes little energy to occupy the higher orbitals, the
electrons will do so, and remain unpaired (until there are more than five electrons), resulting
in a “high spin” complex and associated with a “weak field” ligand.

A photon equal to the energy difference, ∆o, can be absorbed, promoting an electron
to the higher energy level. As certain wavelengths are absorbed in this process, subtractive
color mixing occurs and the coordination complex solution becomes colored.

In general, a larger energy difference indicates that higher energy photons are
absorbed, and the solution appears further to the right on the electromagnetic spectrum.
This relationship is described in the equation ∆=hc/λ, where h and c are constants, and λ is
the wavelength of light absorbed.

Using a color wheel can be useful for determining what color a solution will appear
based on what wavelengths it absorbs. If a complex absorbs a particular color, it will have
the appearance of whatever color is directly opposite it on the wheel.

Figure 1. Color wheel with corresponding wavelength in nanometers.

 The theoretical result is arranged from weakest to strongest ligand field as shown in
Figure 2.

Weak Carbonate
Water

Strong Ammonia
Nitrite

Figure 2. Theoretical spectrochemical series of ligands

Upon doing the experiment, the following are the net ionic equations involved in the
formation of cobalt (III) complexes and its corresponding K f expressions.

 Test Tube A

Net Ionic Equation:

3+ 3+
[Co(H2 O)6 ] (aq) + 6NH3 (aq) [Co(NH3 )6 ] (aq) + 6H2 O(l)

K f expression for the equilibrium reaction:

3+
[Co(NH3 )6 ]
Kf = 3+
[Co(H2 O)6 ][NH3 ]6

 Test Tube B

Net Ionic Equation:

[Co(H2 O)6 ]3+ + 6NO2 − (aq) [Co(NO2 )6 ]3− + 6H2 O(l)

(aq) (aq)

K f expression for the equilibrium reaction:

3−
[Co(NO2 )6 ]
Kf = 3+
[Co(H2 O)6 ][NO2 − ]6

 Test Tube C

Net Ionic Equation:

3+ 3−
[Co(H2 O)6 ] (aq) + 3CO3 2− (aq) [Co(CO3 )3 ] (aq) + 6H2 O(l)
K f expression for the equilibrium reaction:
3−
[Co(CO3 )3 ]
Kf = 3+ 3
[Co(H2 O)6 ][CO3 2− ]

 Test Tube D

Net Ionic Equation:

[Co(CO3 )3 ]3− + 6H2 O(l) [Co(H2 O)6 ]3+ + 3CO3 2− (aq)

(aq) (aq)

K f expression for the equilibrium reaction:

3+ 3
[Co(H2 O)6 ][CO3 2− ]
Kf = 3−
[Co(CO3 )3 ]

VI. Conclusion

VII. Literature Cited/Bibliography

Chemical Equilibrium. (2018). Retrieved from https://www.siyavula.com/read/science/grade-

12/chemical-equilibrium/08-chemical-equilibrium-01

The Equilibrium Constant. (2018). Retrieved from https://chem.libretexts.org/

Textbook_Maps/Physical_and_Theoretical_Chemistry_Textbook_Maps/Supplemental_Modu
les_(Physical_and_Theoretical_Chemistry)/Equilibria/Chemical_Equilibria/The_Equilibrium_
Constant

Complex-Ion Equilibria (2018). Retrieved from https://chem.libretexts.org/

Textbook_Maps/Inorganic_Chemistry/Supplemental_Modules_(Inorganic_Chemistry)/Coordi
nation_Chemistry/Complex_Ion_Equilibria/Complex-Ion_Equilibria

Crystal Field Theory. (2018, October 9). Retrieved from https://en.wikipedia.org/

wiki/Crystal_field_theory

Colors of Coordination Complexes. (2018). Retrieved from https://chem.libretexts.org/

Textbook_Maps/Inorganic_Chemistry/Supplemental_Modules_(Inorganic_Chemistry)/Crysta
l_Field_Theory/Colors_of_Coordination_Complexes