Chem 1B Dr.
White Saddleback College
Experiment 23: Determination of the Formula of a Complex Ion
Objectives
 To explore complex ions and coordination
numbers.
 To use absorption spectroscopy and Job’s
method to determine the formula of a complex
ion.
Introduction
Technique: Absorbance Spectroscopy
Concept Under Investigation: Complex Ions
Metal ions, especially transition metal ions, possess the
ability to form complexes (as shown below) with ions,
organic and inorganic molecules or ions called ligands.
Mn+
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 1,10-phenanthroline). A few
ligands are polydentate (such as EDTA).
The existence of metal ion-water complexes is mainly
due to the attraction of the lone pairs of the water
molecules for the high, concentrated, positive charge on
the metal cations. Silver ion, for example, is typically
coordinated with two water molecules. Although it is
1
+
usual to write aqueous silver ions as Ag , a more
+
accurate representation would be [Ag(H2O)2]
(diaquasilver ion). Similarly, aqueous copper(II) ions are
generally coordinated with four water molecules
2+
resulting in the species [Cu(H2O)4]
(tetraaquacopper(II) ion). Although these examples
include only water molecules as ligands, other neutral
molecules, anions, and even some cations are also
possible.
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 χ. For example, in a mixture of metal, M, and
ligand, L, the mole fraction of component L (χL) would
be calculated according to the following formula:
moles L
χL =
moles M + moles L
From our hypothetical metal ion/ligand complex shown
above, a plot of absorbance versus mole fraction of
€
ligand would have a graph as shown here
Maximum
absorbance
at χ = 0.80
 Chem 1B Dr. White Saddleback College 2

From the graph, note the maximum absorbance for the Procedure
absorbing species occurs at 0.80 mole fraction of
ligand, indicating 4 out of 5 reactants (4/5 = 0.80) 1. Obtain thirteen, clean, dry small test tubes and a test
making up the complex are ligands and the formula is tube holder. Label the twelve tubes with 1-12 and label
M1(ligand)4. Since the ligand is monodentate, the the last tube “blank”.
coordination number is 4. Alternatively, since there is
only 1 mole of metal cation in each complex ion, you 2. To measure out the desired quantities of reagents,
could solve for the number of ligands by setting up the use a clean 5-mL graduated pipet. When pipeting any
following equation: reagents, do NOT pipet directly from the container with
the reagent. To avoid contamination, pour the desired
x moles L amount into a clean, dry beaker, and pipet from there
χL = the necessary amount. Be sure to rinse the pipet at
1 mole M + x moles L least once with the solution you will be pipeting to
x replace any water or other solution that may be in the
0.80 =
1 + x pipet with the desired solution before actually
x=4 measuring your samples.
-4
3. Using the stock solutions of 3.00 x 10 M iron(II) and
In today’s experiment, you will find the find the formula -4
3.0 x 10 M 1,10-phenanthroline, prepare the following
for an iron (II)-phenanthroline complex (meaning diluted solutions in your test tubes:
€ determining the number of phenanthroline ligands
2+
attached to an Fe ion) and the coordination number Tube
2+
Vol. of Fe stock Vol. of 1,10-
(meaning the number of ligand attachments). Both the solution (mL) phenanthroline
iron(II) ion and the free phenanthroline molecules are solution (mL)
colorless in solution; however, an iron ion with at least 1 4.50 0.50
one phenanthroline molecule attached will be a reddish- 2 4.00 1.00
orange color in solution.
3 3.50 1.50
4 3.00 2.00
Fe2+ + y phen → Fe(phen)y2+ 5 2.50 2.50
Colorless Red-Orange 6 2.00 3.00
7 1.50 3.50
where phen = 1,10-phenanthroline = C12H8N2 = 8 1.00 4.00
9 0.80 4.20
10 0.60 4.40
11 0.40 4.60
12 0.20 4.80
Blank 0.00 5.00

4. Mix each solution well by covering the tube with

Parafilm and inverting it many times.

5. Calibrate the spectrometer by filling a clean, dry

cuvette ¾ full with the solution in the tube labeled
“blank”. Use a grease pencil to make a small mark on
the cuvette so that you can place it in the same
orientation throughout the experiment. Wipe the
cuvette with a KimWipe and place it in the
spectrometer. Select Calibrate ► Spectrometer from
the Experiment menu. The calibration dialog box will
display the message: “Waiting . . . seconds for lamp to
warm up.” The minimum warmup time is one minute.
Follow the instructions in the dialog box to complete the
calibration. Click .
Chem 1B Dr. White
6. Empty the blank cuvette and rinse it twice with small
amounts of the solution in test tube 5. Fill the cuvette ¾
full with the test tube 5 solution and place it in the
spectrometer. Click . A full spectrum
graph of the solution will be displayed. Note that one
area of the graph contains a peak absorbance. Click
to complete the analysis. Record the
absorbance at the wavelength of maximum absorbance
(λmax). (Note: The λmax should be between 460 and
560 nm).
7. Return solution 5 to its test tube. Starting with the
least colored sample, pour a small amount into the
cuvette. With this small amount, careful to coat the
inside of the cuvette. Discard this rinse. Pour the
remaining solution into the cuvette and then Click
(a dialog box will pop up; select “clear
latest run”) and then . Record the
absorbance of this tube at the same wavelength of
maximum absorbance determined earlier.
8. Return the solution back to its original tube in case
you need to re-measure the sample. Continue with the
next most colored sample. Be sure to rinse the sample
cuvette with a small portion of the solution each time
before you fill it with the appropriate solution. Measure
the absorbance of each of the standard solutions using
this method. Record all of the absorbance readings in
your notebook.
Saddleback College 3
the equation of the line.
d. To add the second line (descending
absorbance values to the same plot), be sure
that your chart, with its line, is selected. Now go
to the Design tab under Chart Tools and hit
select data at the top. A dialogue box should
appear labeled Select Data Source, select the
Add button to add a new series. Another
dialogue box should appear labeled Edit
Series. Highlight or select the box labeled x
values. With your mouse, drag over the new
column of data to be used as x-values (mole
fraction of phenanthroline where the
absorbance decreases – column 3). Now do the
same with the y values box, using the new data
from the (descending ) Absorbance column
(column 4). Click OK.
e. You can now independently fit these data by
clicking on them and inserting a Trendline as
before.
f. To make the lines intersect, right click one of
the lines and select format trendline. In the
dialogue box under forecast, change the
values from 0 to 0.1 for both forward and
backward until the lines intersect. If they still do
not intersect, adjust this value until they do.

8. Using Microsoft Excel (you may need to reference

the instructions used in the graphing activity), generate
a graph of absorbance as a function of mole fraction of
phenanthroline. You will want to graph your data as two
sets (ascending and descending values). Plot both sets
of data on the same set of axes (as described below).
2
Add equations and R values to both sets of data. Using
the equations of both lines, solve for the intersection
point of the two lines.

Excel Instructions for plotting 2 data sets:

a. Input your data into 4 separate columns. The

first set of ascending absorbance will go into
the first 2 columns (mole fraction and
absorbance) and the second set of descending
absorbance values (mole fraction and
absorbance) will go into the next two columns.

b. Plot the first data set as a scatter plot (see

graphing activity for detailed instructions).

c. Fit the first data set using linear regression as

you did in the graphing activity. You will need
Chem 1B Dr. White Saddleback College 4
Experiment 23: Complex Ion Pre-Lab Assignment

Determine the mole fraction for the following 12 solutions. Both stock solutions have a
concentration of 3.00 x 10-4 M. Show at least one sample calculation below the table.

Tube Vol. of Fe2+ stock Vol. of 1,10- Mole Fraction of

solution (mL) phenanthroline Phenanthroline
(C12H8N2)
solution (mL)
1 4.50 0.50
2 4.00 1.00
3 3.50 1.50
4 3.00 2.00
5 2.50 2.50
6 2.00 3.00
7 1.50 3.50
8 1.00 4.00
9 0.80 4.20
10 0.60 4.40
11 0.40 4.60
12 0.20 4.80
Chem 1B Dr. White Saddleback College 5

Name: ___________________________ Lab Day/Time: ______________

Experiment 23: Complex Ion Data and Results

Absorbance Data

In the table below, record the results of your calculations for each of the standard solutions you
made.
Tube No. Volume Fe2+ Volume Mole Fraction Absorbance
(mL) Phenanthroline Phenanthroline
(mL)
1 4.50 0.50
2 4.00 1.00
3 3.50 1.50
4 3.00 2.00
5 2.50 2.50
6 2.00 3.00
7 1.50 3.50
8 1.00 4.00
9 0.80 4.20
10 0.60 4.40
11 0.40 4.60
12 0.20 4.80

In the space below, show your calculation for the mole fraction of 1,10-phenanthroline for tube
#5. Be sure to include units where appropriate.

• Attach a copy of your Excel graph you generated showing the absorbance of the iron (II)-
phenanthroline complex at different mole fractions of phenanthroline.
Chem 1B Dr. White Saddleback College 6
Equation of the line generated by the
ascending values:
Rewrite the equation of the line for the
ascending values replacing x and y with
the actual variables.
Equation of the line generated by the
descending values:
Rewrite the equation of the line for the
descending values replacing x and y with
the actual variables.
What is the value of the point (x,y) if you
extrapolate both lines until they intersect?
(just eyeball the point)
What is the value of the point (x,y) if you
use the two equations to solve for the
point of intersection?
In the space below, show your calculation for the determination of the point of
intersection using the two equations.

The ratio of Fe2+ to phenanthroline is: 1 Fe2+ to __________ phenanthrolines

The formula for the Fe(II) phenanthroline

complex is:
The coordination number is:

In the space below, show your calculation for the determination of the ratio of Fe2+ to
phenanthroline ligands.
Chem 1B Dr. White Saddleback College 7

Questions

1. Why is the absorbance lower when the mole fraction of ligand to metal is lower?

2. For the complex ion Ag(NH3)2+, what mole fraction of ligand to metal ion would produce a
solution with the greatest absorbance? Please briefly explain your answer.

2+ 2+
3. A certain metal ion, M , forms a complex ion with ammonia molecules to form M(NH3)x . plot of absorbance
versus mole fraction of ligand was obtained. Determine the formula for the complex ion.

Complex ion Formula: _____________

Coordination Number: __________