Ecaldre, Alvek I.

Chemistry 27.1- FEG

Catalig, Antonio Mari P.
Experiment 7

Spectrophotometric Determination of the

Stoichiometry of a Complex
I. Abstract
The experiment aims to demonstrate, compare and contrast three of the most
common spectrophotometric methods used in determining the stoichiometry of a complex,
namely: (1) Continuous Variations Method (CVM), (2) Mole-Ratio Method (MRM) and (3)
Slope-Ratio Method (SRM). These methods involve a play in the concentration of the
reagents in the reactionvarying them from a sample to anotherall of which subjected to
analysis under a UV-Vis spectrophotometer. The recorded absorbance were plotted against
the mole fraction, mole ratio, and concentrations of the reagents for CVM, MRM and SRM,
respectively. After much consideration, a final stoichiometry could not be concluded from
the data gathered from CVM, MRM and SRM for they were 50%, 25% and 50% erroneous,
respectively (comparing their 1:4, 1:6 and 1:2 metal to ligand correspondence to the 1:3
theoretical).
Keywords: spectrophotometry, stoichiometry, absorbance, continuous-variations, mole-ratio, slope-ratio
II. Introduction
Spectrophotometry, a process
involving the interaction between
molecules and light, is a useful technique
in understanding the behaviour/nature of
complex ions in solution; from its
stoichiometry to even its formation
constant. In this technique, reagents are
allowed to react, forming the complex.
Absorbance values are gathered, by
analysing these solutions under a
spectrophotometer. These values, when
analysed, can give valuable information
about the analyte.
There are three most commonly
used methods for complex ion analyses,
these are: (1) the method of continuous
variation, (2) the mole-ratio method and
(3) the slope-ratio method.
The continuous variations method
(CVM) deals with solution samples with
constant total volume and constant total
molar concentration, only varying the mole
ratio of the reactants (usually with one
increasing and the other, decreasing). The
absorbance values are plotted against the
mole fraction
III. Methodology
The first major step of this
experiment was the removal of inhibitor
from commercial styrene. In a small

separatory funnel, 10-ml commercial

styrene, 4-ml of 3M NaOH, and 15-ml
water were mixed thoroughly. Layers were
allowed to separate to withdraw the
aqueous layer. The organic layers was
sequentially washed with two 8ml
portions of water to separate the organic
layer thoroughly from the aqueous layer.
The styrene was dried in a small
Erlenmeyer flask containing a little
anhydrous Calcium Chloride. The flask
was swirled, and the mixture was allowed
to stand for 5-10 minutes. Decantation
was performed to separate the liquid from
the drying agent.
The second major step of this
experiment is the polymerization of pure
styrene. In a small soft-glass test tube, 23ml of dry styrene and 2-3 drops of tertbutylperoxybenzoate were mixed. The test
tube was clamped in a vertical position
over wire gauze, and a thermometer was
inserted so that its bulb is in the liquid.
The mixture was heated with a small
burner flame.
The flame was temporarily removed
when the temperature reached 140
.
Heating was resumed to maintain gentle

boiling. The temperature rose to 180-190

after
the
onset
of
polymerization,
increasing the viscosity of the mixture. The
thermometer was removed and the
styrene was poured in a watch glass when
the temperature started to decrease.
IV. Results and Discussions
Continuous Variations Method
This
method
involves
an
absorbance versus mole fraction plot
evaluated by first, taking the intersection
of the lines extrapolated from the
increasing and decreasing portions of the
curve
and
then
identifying
its
corresponding ratio. Notice in Figure 1 that
the intersection lies at the maximum,
implying that the complex has higher
absorbance at the given wavelength as
compared to those of the reagents.
To
obtain
the
complexs
stoichiometry,
the
intersections
xcoordinate was calculated from the given
trend lines equations as in Solution 1.
These calculations gave a 1:4, metal to
ligand correspondence (with the metal
having a mole franction of 0.2).
Mole-Ratio Method
This method, like the previous one,
also involves taking the intersection of two
extrapolated lines (one from the increasing
and the other from the decreasing
portion). Unlike the CVM, however, this
method uses an absorbance versus moleratio plot; directly giving the stoichiometry
of the complex.
Solution 2 shows the calculation for
the intersections x-coordinate giving a
value approaching 6; meaning, there is a
1:6 correspondence between the metal
and the ligand, respectively.
Slope-Ratio Method
This last method is unlike the
previous twographically, at least. Instead
of extracting the intersection of trend

lines, SRM shows the stoichiometry of the

complex by comparing the slopes two
curves: one, for when the volume of the Fe
solution is held constant (i.e. Figure 3) and
the other for when it Is the ligands volume
that is maintained (i.e. Figure 4).
With the equations of the curves
displayed in the plots, the ratio was easily
calculated (as in Solution 3) giving a 1:2,
metal to ligand correspondence.

.
VI. Conclusion
Free radical polymerization is a
process wherein a polymer forms by the
consecutive addition of free radicals. Free
radicals are formed usually by splitting of
the radical inhibitor. Free radicals initiate
the process of addition, thereby causing
the polymer chain to grow longer.
While in the process, several
factors must be observed, such as the
boiling point of the reactant and viscosity
of the product.
Free-radical polymerization is one of
the easiest way and is also very important
in synthesizing various polymer products
that are widely used in the world.

VII. References
[1] Figure 1. Mechanism of free radical
polymerization. Image retrieved
from google.com.
Bruice, P. (2006). The essentials of organic
chemistry. Pearson Education, inc.
Chanda, Manas. Introduction to Polymer
Science and Chemistry. Boca
Raton:
Taylor and Francis Group LLC, 2006

Chiu, H.H. & Villarante, N.R. Laboratory

manual in Organic Chemistry II.
Klein, D. (2012). Organic Chemistry. John
Wiley & Sons, inc.
Matyjaszewski, K. & Davis, T. Handbook of
radical
polymerization.
John Wiley & Sons. Inc.

Savin,

D.
A.
(2008).
Free-radical
polymerization. University of
Southern Mississippi.

Wnsch, J.
R.
Polystyrene:
Synthesis, production
applications. iSmithers
Publishing. Copyright.

and
Rapra