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Introduction

Metal ions, especially transition metal ions, possess the ability to form complexes with
ions, organic and inorganic molecules or ions called ligands. Transition metal ions in aqueous
solutions generally exist as complex ions in which water molecules, acting as Lewis bases,
coordinate or bond with the small cation (which acts as a Lewis acid). The water molecules in
these structures are known as ligands. Historically this kind of attachment has been called either
a coordinate covalent bond or a dative bond. The distinguishing characteristic of such bonds is
that the shared electron pairs which constitute the bonds come from only one of the bonded
species. In normal covalent bonding the assumption is that each atom donates one electron to the
shared pair that is the bond. The number of ligand attachments to the metal ion is called the
coordination number. Common coordination numbers are 2, 3, 4, 5, and 6. Ligands which can
make only one bond with an ion are called monodentate ligands (one tooth). Bidentate ligands
are generally larger structures which can attach twice to an ion (e.g. ethylene diammine and 1,10phenanthroline).
1,10-phenanthroline (C12H8N2, ortho-phenanthroline or o-Phen) is a tricyclic nitrogen
heterocyclic compound that reacts with metals such as iron, nickel, ruthenium, and silver to form
strongly colored complexes. This property provides an excellent and sensitive method for
determining these metal ions in aqueous solution. For example, o-Phenanthroline reacts with
ferrous ion to produce a deeply colored red complex:
Fe2+ + 3 o-Phen Fe(o-Phen)3 2+

The molar absorptivity () of the ferrous complex, [(C12H8N2)3Fe]2+, is 11,100 L/molcm at the wavelength of maximum absorbance intensity, max = 508 nm. This large value
indicates the complex absorbs very strongly. The intensity of the color is independent of pH in
the range 2 to 9. The complex is very stable and the color intensity does not change appreciably
long periods of time. Beers law is obeyed, over about 1.5-2 orders of magnitude of iron
concentration.
Beers Law is a very simple relationship: A = bc
where A is the absorbance of a substance at a specified wavelength ; b is the length of the light
path through the sample; is the molar absorptivity of the absorbing species at .

The formula of a metal ion/ligand complex in the solid state can be determined by direct
analysis of the stoichiometric amounts of each element that make up the complex. Once in
solution however, determination of the complex formula is not quite as direct. Using a method of
continuous variation, a technique first developed by Job, allows us to find the formula for the
complex in solution. In this method, several solutions are prepared in which the concentrations of
the metal ion and the ligand are varied but the sum of the concentrations is kept constant. Using
these solutions, the light absorption or the conductivity of the solutions is measured and plotted
versus the mole fraction of the ligand. Mole fraction is the ratio of the number of moles of one
component in a mixture to the total number of moles of all substances in that mixture. The
symbol for mole fraction is . For example, in a mixture of metal, M, and ligand, L, the mole
fraction of component L (L) would be calculated according to the following formula: L =
moles L moles M + moles L. The objective of this experiment is to determine the mole ratio of
Iron: 1,10- phenanthroline in the complex.
Conclusion and Recommendations
There are two methods used employing spectrophotometry that can be used to determine
the stoichiometry of a complex or the ratio of metal to ligand in the complex. These are
Continuous Variation and Mole-Ratio. Based on the two methods used, the complex formed by
Iron (II) and 1,10-phenanthroline has stoichiometry of 1:3. This means that every molecule of
iron in the solution can accommodate 3 phenanthroline ligands. The Mole-Ratio Method is better
to use for complexes having large ligand to metal ratio, because the results are distinctly shown
in the plot while the Continuous Variation Method is not ideal if the reactants form more than
one complex. It is not also very useful for complexes with many ligands. It is recommended that
the volumes of the reagents be measured accurately because it directly affects the results.