The Effect of Ligand Field Strength On The Absorption Spectra of Copper (II) Complexes

SURNAME & INITIALS:
STUDENT NUMBER: 201…
GROUP MEMEBERS:
DAY OF EXPERIMENT: WEDNESDAY
DATE OF EXPERIMENT: 20/04/2022
DATE OF SUBMISSION: 18/05/2022
COURSE CODE: C374
EXPERIMENT 6: THE EFFECT OF LIGAND FIELD STRENGTH ON THE ABSORPTION SPECTRA OF

COPPER (II) COMPLEXES
ABSTRACT
By preparing the solution of copper complexes at differing amounts of ammonium hydroxide

and copper nitrate, the effect of the ligand field strength was determined and It was found that
high coordination number of ammonium ligands resulted in high field strength on the
absorption Spectra of Cupper (II) ammine aqua compounds. Increasing ammonium ligand
results in increased Crystal field stabilization energy since ammonia is regarded as a strong field
ligand. The wavenumbers reflected Crystal field stabilization energy exerted by the complex
cations and showed the consistent increase. However, Jahn Teller distortions are observed
where ammonia has a coordination number 5. The color intensity increased with the increase
in the coordination number of ammonia therefore it was concluded that the ligand field
strength really has an effect on the absorption spectra of copper (II) complexes. The overall aim
of the experiment was achieved which was to study the effect of ligand field strength on the
copper (II) complexes.
INTRODUCTION
Ligand field theory describes the bonding, orbital arrangement, and other characteristics of
coordination complexes. It represents an application of molecular orbital theory to transition
metal complexes. The Cu (II) ion takes on the ground state configuration t2g6eg3 in a strictly
octahedral structure. The configuration is however strongly conditioned to the Jahn-Teller
effect, so the structure of a Cu (II) complex tends to diverge from the octahedron, undertaking
a tetragonally elongated structure most often. The shape of the transition metal complex is
determined by the tendency of electron pairs to occupy positions as far away from each other
as possible (1) and the d orbital being either symmetrically or asymmetrically filled affects the
shapes of transition metal complexes. Repulsion by six ligands in an octahedral complex splits
the d orbitals on the central metal into t2g and eg and this causes the energy level diagram to
split.
Copper (II) ion forms an octahedral complex (the most common type of complex) upon its
reaction with water and ammonia solution. This complex formed is obtained from the formula
((NH3)n (H₂O) 6-n 2+ The water and ammonia molecules are the ligands in this case. In the case of
the octahedral complex, six ligands (H2O and NH3 in this case) form an octahedron around the
metal ion.
The absorption spectra of the series of complexes [(Cu (NH3)6-n (H₂O)n ]2+ (n=1 to 6) were
studied in this experiment. Coordinated water molecules were replaced by ammonia as
ammonia was added to the solution containing [Cu (H₂O)6]2+ since ammonia is a stronger-field
ligand than water, successive substitution of ammonia for resulted in a shift of ℷmax to a shorter
wavelength. Different complexes were produced by substitution method.
PROCEDURE
As outlined in the lab manual.
RESULTS
Table 1: 2.5 Spectra of copper complexes and their wavenumbers
Complex Number of Ammonia Ligands Maximum absorbance

wavenumber (cm3)
[Cu(H2O)6] 2+ 0 12.531
[Cu(NH3)(H2O)5] 2+ 1 13.661
[Cu(NH3)2(H2O)4] 2+ 2 13.966
[Cu(NH3)3(H2O)3] 2+ 3 14.577
[Cu(NH3)4(H2O)2] 2+ 4 17.094
[Cu(NH3)5(H2O)]2+ 5 14.456
CALCULATIONS
1m = 100cm
1m= 1 x 109nm
Vmax =798nm
798𝑛𝑚 + 100𝑐𝑚
Vmax = 100 000 000
= 7.98 x 10-5 cm
1
Reciprocal wavelength= Vmax
= 1/7.98 x 10-5cm
=12531.33cm-1
=12531 cm-1
DISCUSSION
Strong field ligands like ammonia theoretically, cause huge spilt in the electromagnetic spectra
exerted by the ligands in a complex compound. It is therefore an expectation that the copper
(II) compounds with high ammonium coordination number establish greater splits and this is
shown on the energy level diagrams attached.
When the coordination number contributed by ammonia ligands rises, the complex results in a
larger wave number (2). This is due to the fact that ammonia is a strong field ligand and hence
causes greater splits in the field. Successive substitution of ammonia for water resulted into a
shift to a shorter wavelength as water is a weak field ligand and establishes longer wavelengths.
The trend of the first four additions of ammonia shows that the maximum wavelength is
decreasing on by the addition of ammonia molecules, resulting into the corresponding increase
in wavenumber as indicated by the curve in the graph attached. This shows that as the splitting
energy decreases, the wavelength increases and this is defined by the equation; E = hv = hc/ℷ.
The trend changed on the fifth ammonia molecule, (shown by the downward bend on the
curve) addition due to the Jahn-Teller effect, which distorted the octahedral complex and made
the fifth band weak therefore giving a longer wavelength
CONCLUSION
It can be concluded that the crystal splitting energy of some copper complexes does increase
with increasing concentration and number NH3 ligands present in the complex. Due to the fact
that different ligands generate crystal fields of different strengths, different colors can be seen.
For a given metal ion, weaker field ligands create a complex with a smaller Δ, which will absorb
light of longer wavelengths and thus lower frequencies. Conversely, stronger field ligands
create a larger Δ, absorb light of shorter wavelengths, and thus higher frequencies.
REFERENCES
1. Lee. J.D, 1996 concise Inorganic Chemistry, 5th Edition, Blackwell Science Ltd Malaysia
2. NJ. Tro, TD. Fridgen & LE.Shaw, Chemical kinetics in Chemistry A Molecular Approach,
United States,2011, 3rded

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SURNAME & INITIALS:

STUDENT NUMBER: 201…

DAY OF EXPERIMENT: WEDNESDAY

DATE OF EXPERIMENT: 20/04/2022

DATE OF SUBMISSION: 18/05/2022

COURSE CODE: C374

EXPERIMENT 6: THE EFFECT OF LIGAND FIELD STRENGTH ON THE ABSORPTION SPECTRA OF

By preparing the solution of copper complexes at differing amounts of ammonium hydroxide

As outlined in the lab manual.

Table 1: 2.5 Spectra of copper complexes and their wavenumbers

Complex Number of Ammonia Ligands Maximum absorbance

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