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THE SPECTROCHEMICAL SERIES

Report due: Two weeks after completion of experiment.

Requirements of report: Hand in completed laboratory report.

Attach overlaid spectra.

Resources and references: Given at the end of these notes.

For immediate feedback: See exit checklist at the end of these

notes.

Introduction

When a metal ion forms a complex in a ligand field of octahedral symmetry, the d orbitals
(shown below) are no longer degenerate. For an octahedral complex, the donor atoms (the
atom of the ligand that is directly bound to the metal) can be considered to lie on the Cartesian
axes:

L
L
L
M
L
L
L

z
The dz2 and dx2-y2 orbitals (the eg orbitals) also
z lie along the axes
z so there will be significant
electronic repulsions between the ypair of electrons ofy the donor atom yand electrons in the eg
orbitals. This will increase
x the energy of electrons
x in these orbitals,
x relative to those in the dxy,
dxz, dyz orbitals (the t2g orbitals):
dxz dyz dxy

z z

y y
x x
dx2-y2 dz2

The Spectrochemical Series, page 1

The t2g orbitals lie between the Cartesian axes. Interelectronic repulsions between the ligand
electrons and electrons in the t2g orbitals are less than for the eg orbitals:

z
z z
y y y
x x x

dxz dyz dxy

z z
This means that the d orbitals are split into two energy levels separated by an energy Δo (o for
y y
octahedral not 0 (zero)):
x x
dx2-y2 dz2 dx2-y2, dz2
eg
o

t2g dxy,, dxz, dyz

Free ion Spherical field Octahedral ligand field

For a particular metal ion, the magnitude of Δo depends on the nature of the ligand. From many
spectral studies, it has been found that it is possible to rank the order of field strength for
ligands (which is found to be independent of the metal ion). This ranking list is known as the
“spectrochemical series” and an excerpt is given below (donor atoms in polyatomic ions or
molecules are shown in bold):

I < Br < Cl < NO3 < F < diethyldithiocarbamate (S) < OH < C2O42 < H2O < SCN
< NH3 ≈ pyridine (N) < ethylenediamine (N) < NO2 ≈ 2,2'-bipyridine (N) << CN

There is some correlation of donor atom with position on the spectrochemical series. An
example is that N-donors consistently rank above O-donors. The fact that N-donor ligands
usually produce stronger ligand fields than O-donor ligands is reinforced by the following table,
where values of Δo for various Ni(II) complexes are given:

TABLE Δo Values for Ni(II) Complexes

Ligand (number) Donor Set Δo (cm1)

2,2'-bipyridine (3) N6 12 650

ethylenediamine (3) N6 11 700
pyridine (6) N6 10 150
imidazole (6) N6 10 150
NH3 (6) N6 10 750
H2O (6) O6 8 500

The Spectrochemical Series, page 2

 methanol (6) O6 8 430
pyridine N-oxide (6) O6 8 400
dimethylsulfoxide (6) O6 7 730

This information suggests that, for a series of complexes of a particular metal ion, the value of
Δo should increase from an O6 donor set to N2O4 to N4O2 to N6, if it were possible to prepare a
series of complexes with ligands chosen to provide the appropriate donor sets. In this
experiment, solutions of Cu(II) complexes of the first three donor sets (O6, N2O4 and N4O2) are
prepared and the value of Δo is measured from the visible spectra. Unfortunately, it is extremely
difficult to prepare Cu(II) complexes with an N6 donor set.

Copper(II) complexes have been chosen because Cu2+ is a d9 ion (equivalent to d1 in spectral
terms, taking account of positive-hole formalism (i.e. only one possible electronic excitation)) so
is spectrally simple with one broad absorption band observed. Note that spectra which arise
from d-d electronic transitions are very weak (low molar absorptivities) because the transitions
are forbidden by the Laporte selection rule.

Part A: Calculation of molar masses and structure of complex ions

In this experiment you will prepare three solutions of differing Cu(II) complex ions. Each of the
complexes contains different ligands with different donor sets of atoms. You will then collect
the visible spectrum of each solution, thus identifying λmax for each complex and the
corresponding absorbance of the solution at that wavelength. The absorbance value can be
used to calculate ε (molar absorptivity at λmax) for each complex, while λmax can be converted to
wavenumber (𝜈). Wavenumber is a parameter that is directly proportional to energy of the
electronic transition (see appendix). Thus the three ligands can be ranked in order of their ligand
field splitting parameter (∆o).

Caution: Make sure that you calculate you molar masses carefully. Incorrect values for some
of these compounds exist on the internet.

Solution 1: Copper(II) sulfate pentahydrate is dissolved in water. The complex cation that is
produced in solution is the hexaaquacopper(II) ion (O6 donor set).

Report the molar mass of copper(II) sulfate pentahydrate here (units: g mol1):

The Spectrochemical Series, page 3

Draw the structure of the hexaaquacopper(II) ion in the box below:

Solution 2: Excess EDTA (as the disodium salt) is added to copper(II) acetate monohydrate. The
complex anion that is produced in solution is the ethylenediaminetetraacetatocuprate(II) ion
(N2O4 donor set).

Report the molar mass of copper(II) acetate monohydrate here (units: g mol1):

Draw the structure of the ethylenediaminetetraacetatocuprate(II) ion in the box below (use the
common representation of a curved wedge for the polydentate ligand, but be sure to show all
donor atoms in your structure):

The Spectrochemical Series, page 4

Solution 3: Diaquabis(ethylenediamine)copper(II) iodide is dissolved in water. The complex
cation that is produced in solution is the diaquabis(ethylenediamine)copper(II) ion (N4O2 donor
set).

Report the molar mass of diaquabis(ethylenediamine)copper(II) iodide here (units: g mol1):

Draw the structure of the diaquabis(ethylenediamine)copper(II) ion in the box below (use the
common representation of a curved wedge for the polydentate ligand, but be sure to show all
donor atoms in your structure):

The Spectrochemical Series, page 5

Finally, draw the fully labelled crystal field splitting diagram for an octahedral copper(II)
complex ion. Include the d electrons in your diagram:

Before proceeding to part B, check your answers to part A with your demonstrator.

The Spectrochemical Series, page 6

Part B: Preparation of solutions

Safety and handling instructions

When carrying out this experiment wear appropriate

personal protective equipment consisting of lab coat,
General
enclosed footwear, safety glasses and nitrile gloves when
handling organic chemicals.

Aquatic poison – dispose of in aqueous heavy metal waste

Copper
Irritating to eyes, skin and respiratory system – wear gloves
complexes
and use in well ventilated areas. Do not breathe dust.

Solution 1:
Weigh, accurately (analytical balance, record mass!), approximately 0.5 g of copper(II) sulfate
pentahydrate into a weighing boat. Quantitatively transfer the solid to a 50 mL volumetric
flask, then dissolve the solid in about 30 mL of deionised water and then add more water to
make up to volume.

Record your mass of copper(II) sulfate pentahydrate weighed here:

Solution 2:
Weigh, accurately (analytical balance, record mass!), approximately 0.075 g (0.000375 mol) of
copper(II) acetate monohydrate into a weighing boat. Quantitatively transfer the solid to a
50 mL volumetric flask. Add solid Na2H2EDTA.2H2O (0.2 g, 0.0005mol). This amount should
ensure complete formation of the [Cu(EDTA)]2 species. Dissolve the solids in about 30 mL of
deionised water and then add more water to make up to volume.

Record your mass of copper(II) acetate monohydrate weighed here:

The Spectrochemical Series, page 7

Solution 3:
Weigh, accurately (analytical balance, record mass!), approximately 0.25 g of
diaquabis(ethylenediamine)copper(II) iodide into a weighing boat. Quantitatively transfer the
solid to a 50 mL volumetric flask. Dissolve the solid in about 30 mL of deionised water and
then add more water to make up to volume.

Record your mass of diaquabis(ethylenediamine)copper(II) iodide weighed here:

Part C: Visible spectroscopy of the complexes and determination of ε and 

 Record the uv-vis spectrum of each solution over the range λ = 900 to 400 nm in
absorbance mode and overlay the spectra on one chart (for direct comparison of the
position of the absorbance peak).

 Determine the wavelength of maximum absorbance (λmax, units: nm) for each solution.

 Convert the wavelength (λmax, units: nm) to wavenumber ( , units: cm1) using the
following formula:

10 7
 max  cm1
max

 Calculate the molar absorptivities, ε, at λmax for each of the copper species. The molar
absorptivity can be calculated by rearranging Beer's Law:

A = εcl

In this expression A is the absorbance (dimensionless), l is the path length of the cell (in cm (l = 1
cm)) and c is the concentration of the species in mol L1. Note that the units of ε are L mol1
cm1.

The Spectrochemical Series, page 8

Solution 1 (hexaaquacopper(II), O6 donor set):

Calculate the molar absorptivity and then convert wavelength (λ / nm) to wavenumber (𝜈 /
cm1):
𝐴 107
𝜀= 𝜈=
𝑐𝑙 𝜆𝑚𝑎𝑥

Solution 2 (ethylenediaminetetraacetatocuprate(II) ion, N2O4 donor set):

Calculate the molar absorptivity and then convert wavelength (λ / nm) to wavenumber (𝜈 /
cm1):
𝐴 107
𝜀= 𝜈=
𝑐𝑙 𝜆𝑚𝑎𝑥

The Spectrochemical Series, page 9

Solution 3 (diaquabis(ethylenediamine)copper(II) ion, N4O2 donor set):

Calculate the molar absorptivity and then convert wavelength (λ / nm) to wavenumber (𝜈 /
cm1):
𝐴 107
𝜀= 𝜈=
𝑐𝑙 𝜆𝑚𝑎𝑥

Summary of results (consider significant figures!):

solution 1 solution 2 solution 3

O6 N2O4 N4O2
molar absorptivity, ε
(L mol1 cm1)
wavelength, 𝜆𝑚𝑎𝑥
(nm)
wavenumber, 𝜈𝑚𝑎𝑥
(cm1)

The Spectrochemical Series, page 10

Do your results support the hypothesis that N donor atom ligands rank above O donor
atom ligands in the spectrochemical series? Explain.

The complex ion in solution 3 has two geometric isomers (cis- and trans- forms). However
only one of these geometric isomers has an optical isomer. Which one is it? Explain.

The Spectrochemical Series, page 11

 Do your values of ε reflect the symmetry of each complex ion? Explain.

Appendix

Wavenumber is often used in preference to wavelength in discussing positions of spectral bands

(particularly in IR spectra) because it can be considered as frequency related to a distance
dimension rather than a time dimension. Like frequency, wavenumber is directly proportional to
energy, so values of wavenumber can be directly compared when discussing the magnitude of
∆o in transition metal complex spectra.

Consider the following relationship between frequency ( ) and wavelength (λ):

c
=


where c is the speed of light (for electromagnetic radiation). As c is a constant, it follows that:

1



Wavenumber,  , is the inverse of  measured in cm1:

1
 


The Spectrochemical Series, page 12

Therefore wavenumber is directly proportional to frequency. For electromagnetic radiation, the
energy, E, of a particular frequency is given by:

E = h

where h is Planck's constant, and, as:

 

it follows that:

E

Frequency and wavenumber are used practically interchangeably so the symbol for frequency
( ) is also used for wavenumber ( ).

Exit checklist
For immediate feedback, see your demonstrator before leaving. He/ she will
check the following:
 Part A has been completed correctly.
 Overlaid spectra have been recorded showing correct peak positions
and intensities.

Resources:
 Module 3 and 4 lectures
 M.J. Winter ‘d-Block Chemistry’, Oxford Chemistry Primers, Oxford Science Publications
OUP (2015), chapters 5 and 7.

The Spectrochemical Series, page 13