The Electronic Spectrum of Copper (II) in compounds:

Introduction*
The most immediately obvious characteristic of transition metal compounds is their colour. The
colour is a result of absorptions in the visible region of the electromagnetic spectrum and these
absorptions are usually a result of the redistribution of electrons within the incomplete set of d-
orbitals. Some transition metal compounds and many non-transition metal compounds are coloured
as a result of redistribution of electrons between the metal and ligand. This is known as charge
transfer.

Crystal field theory suggests that in, for example, octahedral complexes, the d-orbitals lose their
degeneracy and are split energetically into two groups: eg containing the d(x2−y2) and dx2
high energy and t2g containing [dxy, dyz, dxz ] low energy :

When copper (II) sulphate is dissolved in water, a solution containing [Cu(H20)6]2+ and sulphate ions is
produced. The Cu(II) atom in [Cu(H20)6]2+ has the electron configuration [Ar]3d9 and in the ground
state the d electron configuration is t62g e3g
orbitals. An electron is promoted from the t2g to the eg orbitals by visible radiation. The actual
spectrum apparently consists of one broad band with a maximum at about 800 nm. This value of
800 nrn, expressed in appropriate energy units, is the value of o, the crystal field splitting energy,
for the system Cu (II) surrounded octahedrally by six water molecules.
 
Metal ions in aqueous solution are often hydrated resulting in hexaaqua complexes [M(H2O)6]z+. The
addition of stronger ligands results in a stepwise displacement of H 2O.

[M(H2O)6]z+(aq)+L(aq)⟶[M(H2O)5L]z+(aq)+H2O

The equilibrium constant Ki is characteristic for each step. 

Ki=[M(H2O)5L]z+[M(H2O)6]z+(aq)×[L]

The overall reaction with six ligands leads to the following:

[M(H2O)6]z+aq + 6L(aq) [ML6]z+aq + 6H2O
  [M(H2O)6]z+(aq)+6L(aq)⟶[ML6]z+(aq)+6H2O

The more ligands are complexed instead of water, the smaller the equilibrium constant gets.
*Additional Introduction [Thanks to Lukas Stulik DT212/3C, 2007-08

Crystal field theory

Overview of Crystal Field Theory from Chemistry Libre
The crystal field theory is an electrostatic model using ligand electrons to create an electric field
around the metal centre that gives insight into structures, magnetic properties and electronic
properties. Ligands are considered as point charges resulting in the fact that there are no metal-
ligand covalent interactions. In octahedral complexes, each ligand is treated as negative point charge
resulting in electrostatic attraction between the metal ion and the ligands. There are also repulsive
interactions between electrons in d-orbitals and the pint charges. The dZ2 and dx2 - y2 orbitals pint
directly at the ligands while the dxy, dyz and dxz pint between them. The dZ2 and dx2 - y2 orbitals are
destabilized to greater extent than the other three. In a special field the dZ2 and dx2 - y2 atomic orbitals
are destabilized while the other three are stabilized. Resulting in the definition that the dZ2 and dx2 -
y have eg symmetry and the others possess t2g symmetry where Δoct is the energy gap between the
2

eg and the t2g set. The overall stabilization of the t2g equals the overall destabilization of the eg set.

The stabilization and the destabilization of the eg and t2g sets are given in terms of Δoct (magnitude
determined by strength of crystal field) which can be determined from spectroscopic data at λ max.
 
Where NA = Avogado’s Number, h = Planck’s constant, c = speed of light, and λmax in meters:
 

Δo= [hc/λmax×10−9]×NA (J mol−1)

 
The complexation of different ligands results in different ligand field strengths resulting in the
possibility of differentiating between species by spectroscopic data: for example in the following
cobalt compounds:
[Co(H2O)6]3+ : Δoct = 18200cm-1
[Co(NH3)6]3+ : Δoct = 22900cm-1

Electronic spectra
Information about structure and bonding are obtainable from spectroscopic data. Different
vibrational and rotational states of the compound combined in an electronic spectrum.
A characteristic feature of d-block metal complexes is their colours due to absorption of light in the
visible region. There are two different ways that absorption due to transitions between electronic
energy levels can occur. The first is based on metal-centred orbitals possessing d-character (d-d
transitions) and the second one is metal-centred and ligand-entered molecular orbitals with a charge
transfer from metal to ligand or from ligand to metal. Charge transfer has more intensive
absorptions than d-d transitions and takes place at higher energy than d-d transitions.

Lambert-Beer’s Law relates the absorbance to the extinction coefficient as follows:

Lambert-Beer’s Law is A = 𝜀cl
The value for ε can be calculated from the known values for Amax (at λmax), c (concentration) and t
(thickness of the cell i.e. path length). Typical values for ε associated with d-d-transitions are 1-1000.
Pre-Laboratory Questions
1. Write a scientific Introduction citing appropriate references.
2. Write out the electronic configuration for (i) elemental copper and (ii) Cu2+ ion
3. Sketch the [Cu(H2O)6] complex (it is an octahedral transition metal coordinate compound)
4. Sketch a diagram to show the effect of the ligands on the d orbital and electrons of the central
metal in this complex.

Chemical Risk Assessment and Safety

Safety data sheets for this practical are available. A safety manual is available. Please consult
supervisor if you have any queries.
Hazard identification and risk assessment
Chemical Hazard Classification Hazard Statements H
and Risks
Copper Sulfate Acute toxicity (Cat 4) Causes serious eye irritation. H319
Eye irritation (Cat 2) Causes skin irritation. H315
Skin irritation (Cat2) Harmful if swallowed. H302
WARNING Acute aquatic toxicity (Cat 1) Very toxic to aquatic life with long H410
Chronic aquatic toxicity (Cat 1) lasting effects.
Ammonia Skin corrosion (Category 1B) Causes severe skin burns and eye H314
Solution 5M Specific target organ toxicity - single damage. H335
exposure (Category 3) May cause respiratory irritation. H400
Acute aquatic toxicity (Category 1) Very toxic to aquatic life.

DANGER
Ammonium Classified as non-hazardous    
Sulfate
Precautions
• Read about the hazards and risks in the table above
• Acids and bases in a concentrated form are corrosive and can cause burns. More dilute forms
can cause irritation. Wash all splashes with water immediately.
• Check all glassware is intact before use
• Wash all glassware clean of chemicals before leaving the lab.
Wash hands with soap and water after the practical.
The Electronic Spectrum of Copper (II) complexes
Procedure: (to study the effect of successive displacement of one ligand by another)
A solution of copper (II) sulphate (0.01 mol dm-3) in aqueous ammonium sulphate (2 mol
dm-3) is prepared and its visible spectrum recorded, (may be provided).
Use the stock solutions as outlined below.
A further series of solutions are now prepared in which 1, 2, 3, 4, 5 and 6 equivalents of
ammonia are added.
The spectrum of each solution is recorded. Ensure the copper (II) ion concentration remains
constant.  

The following stock solutions are prepared:

• 100 cm3 of 2M (NH4)2SO4 [supplied}

• 100 cm3 of 0.02M CuSO4 from solid or from a solution of known molarity provided
(when preparing add approx. 50cm3 of aqueous ammonium sulphate (2 mol dm-3)
before making up to the 100 cm3 mark.
• 50 cm3 of 0.12M NH3 (from conc NH3 or from a solution of known molarity provided)

o Using calibrated pipettes dispense accurately the solutions as outlined in the table
below.
o Using a 1cm cell record the spectrum (350-850 nm) for each of the 7 solutions
(starting at the most concentrated in NH3,). Superimpose the spectra. (Use overlay
function on the spectrometer).
o Note the maximum Absorbance and corresponding wavelength (λmax) for each.

0.02M CuSO4 cm3 0.12M NH3 cm3 2M (NH4)2SO4 Record λmax in nm Max. Absorbance

6 0 6
6 1 5
6 2 4
n6 3 3
6 4 2
6 5 1
6 6 0
 RESULTS (note the resultant molarity of Cu2+ is 0.01M in all )
Molar Molar λmax Max. Calculated values
Ratio Ratio
nm Absorbance
Cu2+ NH3 cm3

𝜀 Please Δo Δo
include the -1
in cm in
units you get Joules/mole
1 0
1 1
1 2
1 3
1 4
1 5
1 6

Post lab questions:

Complete the table above: Remember for q1-3 to elaborate on all equations and show the units
1. Calculate the value of Δo, the crystal field splitting energy for Cu(II) in cm-1
Because E= Δo = [1/ λmax (cm)] as E~1/ remember to convert λmax from nm to cm so as to find a value
in cm-1 (see information above)
2. Calculate the value of Δo, the crystal field splitting energy for Cu(II) in Joules per mole
(remember to convert λmax from nm to meters, see information above)
Δo= [hc/λmax×10−9]×NA (J mol−1)where NA =Avocados Number, h=Planck’s constant and c= speed
of light (remember to elaborate on these equations)
3. Calculate the value of the extinction coefficients in SI units, 𝜀 for each spectrum,
4. Comment on the values of 𝜀 calculated.
5. Explain why each of the absorption spectra consist of a band rather than a line? (A band may be
thought of as a number of closely spaced lines).
6. Compare the spectra recoded upon addition of the different molar equivalents Cu(II)-
NH3 and comment fully on the shifts due to addition of extra ligand molecules. Comment
on the difference between the values of Δo as calculated.

Useful References
• Nicholls, D., 2017.  Complexes and first-row transition elements. Macmillan International
Higher Education.
• Housecroft, C.E. and Sharpe, A.G., 2018. Inorganic Chemistry. Harlow, England.
• Contreras, J.S., 1999. Inorganic spectroscopic methods/AK Brisdon. Oxford: Oxford
University Press, 1998. 91 p. Revista de Química, 13(2), pp.105-106.
• Dunne, T.G., 1967. Spectra of Cr (III) complexes. An inorganic chemistry
experiment. Journal of Chemical Education, 44(2), p.101.
• Cotton, F.A. and Wilkinson, G., Inorganic chemistry. John Wiley.
• http://www.chemguide.co.uk/inorganic/complexions/colour.html#top