Experiment 3 2
Experiment 3 2
Experiment 3 2
Issue No.1
Determination of Iron (Fe3+) and Salicylic acid (C7H6O3) complex composition using Jobs Method of
Continuous Variation, Mole-Ratio Method, and Slope-Ratio Method
Maquiling, Kenth Roger A.*a, Paredes, Trisha Aerielle B.*a, Dr. Kathlia De Castro-Cruz*b
Mapa Institute of Technology, Muralla Street, Intramuros, Manila 1002, Philippines
ABSTRACT
Article Information
Article History:
Performed 04 August 2016
Submitted 18 August 2016
Keywords:
Potentiometry
Ion-selective electrode
Calibration Curve
Standard Addition
Fluoride
Potentiometry measures the potential of an electrochemical cell under static conditions and
relate it as a function of phenomena occurring at the interface of an electrode and the
solution. Hence, the species concentration which remains unchanged in the course of
analysis can be determined. Potentiometers are composed of reference (SHE, SCE,
Ag/AgCl) and indicator electrodes. Membrane electrodes including glass and crystalline solidstate ion-selective electrode are the ones usually used in pH meters and other
potentiometers, respectively. Calibration curve and standard addition methods were then
employed in the quantitative analysis of the data obtained in fluoride measurements. Results
showed that all shampoo samples were acidic with pH ranging from 4 to 6, as intently
manufactured containing acidic ingredients that regulates the natural environment of scalp
and hair. T-test on the concentrated and diluted samples revealed a significant difference
between the two. Moreover, calibration curve and standard addition method posed limitations
in their usage that led to the inconsistencies of the results obtained in the two methods. In
conclusion, the present experiment thoroughly demonstrated the principles and application of
potentiometry as a method of analysis.
1. INTRODUCTION
Various analytical techniques such as electrochemical
oxidation reduction, molecular absorption, chromatography,
and atomic emission or absorption spectroscopy are well
established methods for qualitative, quantitative and
characterization applications. UV/Vis spectrophotometry in
particular, a molecular absorption spectroscopy, has been
widely used in different characterization studies, including
those that aim to determine the stoichiometry of metalligand complexes and determining equilibrium constants
(Harvey, 2000).
Complexation reactions otherwise known as Lewis acidbase reactions, involve the chemical joining of separate
groups of atoms, molecules or ions yielding a single ion
called a complex ion, which features a notably brighter
shade of color. In here, a single ion, usually metal, which
serves as the central component of the complex contains
a
M + yL M L y
Eq. 1
Three methods employed in this undertaking are Jobs
method of continuous variations, mole-ratio method and
slope-ratio method, all involving UV/vis spectrophotometry.
Of these three, Jobs method is considered the most
popular wherein a series of solutions is prepared such that
the total moles of metal and ligand, in each solution is the
same. The concentration of the metal-ligand complex is
Figure 1. Mole-ratio plots used to determine the stoichiometry of a metal-ligand complexation reaction.
then determined by the limiting reagent, with the greatest
concentration occurring at the point where the metal and
ligand are mixed stoichiometrically. Monitoring the
complexation reaction at certain wavelength where solely
the complex absorbs, a plot of absorbance versus the mole
fraction of ligand would generate two linear branches: (1)
when the ligand acts as the limiting reagent; and (2) when
the metal is the limiting reagent. The intersection of these
linear lines denotes the point where a stoichiometric mixing
of metal and ligand is reached (Harvey, 2013). Projecting
this intersection to the mole fraction of ligand determines
the value of y for the complex, MLy.
y=
XL
1X L
Eq. 2
3
aqueous solution of salicylic acid, tables 1, 2, and 3 were
referred to following the specific volumes of the metal and
ligand to be added in every solution.
2.4.1 Jobs Method
Table 1. Jobs Method of Continuous Variation
2. EXPERIMENTAL SECTION
2.1 Chemical Reagents
The present study required the use of the following
chemical reagents: concentrated sulfuric acid, ferric nitrate,
salicylic acid and distilled water. The concentrated sulfuric
acid serves as the chemical reagent used for standard
preparation, specifically in the preparation of 0.0025M Fe 3+
standard, acting as the metal component. The 0.0025M
salicylic acid solution on the other hand served as the
ligand component of the complex.
2.2 Equipment and Apparatuses
The glassware used in this study were 100 ml volumetric
flasks, volumetric pipettes, graduated cylinders, beakers,
stirring rod and watch glasses. The equipment employed
on the other hand were electronic balance and UV/vis
spectrometer.
2.3 Samples
The samples used in the experiment are the 0.0025M Fe 3+
and 0.0025M salicylic acid solutions, which are the metal
and the ligand respectively in the complexation reaction.
2.4 Methodology
The experiment focused on the three methods used in the
determination of the stoichiometry of metal-ligand complex.
After preparation of 0.0025M Fe3+ standard solution and
Soln
Vol. Fe3+
(ml)
Vol. Salicylic
acid (ml)
Total Volume
(mL)
1
2
3
4
5
6
7
8
9
10
11
0
1
2
3
4
5
6
7
8
9
10
10
9
8
7
6
5
4
3
2
1
0
25
25
25
25
25
25
25
25
25
25
25
Soln
Vol. Fe3+
(ml)
Vol. Salicylic
acid (ml)
Total Volume
(mL)
1
2
3
4
5
6
2
2
2
2
2
2
1
2
3
4
5
6
10
10
10
10
10
10
4
Table 3. Slope-Ratio Method
Soln
Vol. Fe3+
(ml)
Vol. Salicylic
acid (ml)
Total Volume
(mL)
1
2
3
4
5
6
7
8
9
10
11
12
10
10
10
10
10
10
1
2
3
4
5
6
1
2
3
4
5
6
10
10
10
10
10
10
20
20
20
20
20
20
20
20
20
20
20
20
Soln
1
2
3
4
5
6
7
8
9
10
11
Absorbance
4.112
4.162
4.236
4.306
4.355
4.609
4.306
4.240
4.111
4.021
3.736
3+
Fe(C 7 H 6 O3)
However, it is crucial to take note that the Jobs Method on
its own has limitations, which includes: (1) a single metalligand complex should be formed; (2) it should obey Beers
Law; (3) the metal-ligand complexs formation constant
should be large enough to avoid significant curvature of the
plot of absorbance versus XL; and (4) pH of the solutions
must be held constant (McCarthy et. al., 1986).
With these limits taken, mole-ratio and slope-ratio method
were undertaken which addressed the limitations of Jobs
method and to further investigate on the stoichiometry of
the iron-salicylic acid complex. Since the Jobs method
suggested a 1:1 ratio of ligand-metal, it is imperative to
prove that no other stoichiometric ratio exists for the said
complex.
Results in mole-ratio method as shown in table 5 and figure
5 gave two ratios for the complex formation of Fe 3+ and
salicylic acid, which were 1:1 and 2:1, denoted by the two
inflection points in the plot when projected to the x-axis.
Unlike Jobs method, the mole-ratio method is used for
complexation reactions that occur in a stepwise-fashion,
assuming that the molar absorptivities of the metal-ligand
complexes differ and the formation constants are
significantly different (Skoog, 2014). Through this, it can be
asserted that the iron(III)-salicylic acid complex does not
solely exist in a 1:1 ratio and that its complexation reaction
based on the results, occurs in a stepwise fashion resulting
into a 2:1 ratio.
3+
3++(C7 H 6 O3) Fe(C 7 H 6 O3 )2
Fe(C 7 H 6 O3 )
Table 5. Data on Mole-Ratio Method plot.
Soln
1
2
3
4
5
6
Absorbance
4.418
4.556
4.601
4.656
4.665
4.674
5
6
7
8
9
10
11
12
0.000625
0.00075
0.000125
0.00025
0.000375
0.0005
0.000625
0.00075
5.407
5.841
4.326
4.556
4.601
4.756
4.865
5.174
To further prove this observation, the third method, sloperatio was performed. This method specifically addresses
the limitations of the previous two in which it does not rely
on an extrapolation of absorbance data under conditions in
which a linear relationship exists between absorbance and
the relative amounts of metal and the ligand. This is
particularly advantageous on metal-ligand complexes that
are very weak.
Table 6 and figure 6 depict the result for this method, and
by calculating the ratio of the slopes, the gathered data all
pointed to a ratio of 2:1 for the ligand-metal complex. An
important assumption to this method is that the
complexation reaction continues to completion in the
presence of a sufficiently large excess of metal or ligand
(Skoog, Holler and Crouch, 2007).
Table 6. Data on Slope-Ratio Method plot.
Soln
1
2
3
4
Absorbance
4.285
4.519
4.794
5.126
4. CONCLUSION
Aside from the quantitative applications of UV/vis
spectroscopy, its use also spans qualitative or
characterization applications. In the current experiment,
this characterization prowess of UV/vis spectroscopy has
been evaluated through the determination of the complex
composition of iron (III)-salicylic acid via Jobs, mole-ratio,
and slope-ratio methods. The use of these three methods
address each methods limitations coming up with a
wholesome analysis with increased accuracy of the data
gathered. In conclusion, as with the results of the
experiment, the stoichiometric ratios of the iron(III)-salicylic
acid complex are 1:1 and 2:1 (salicylic acid: iron). The
6
results further elucidated the crucial decision to undertake
the three aforementioned methods.
For future experiments on the same objectives, it is
recommended that the standard solutions (metal and
ligand) be prepared with accuracy for this can be a critical
source of errors. Furthermore, it must always be taken into
consideration that the methods obey Beers law and with
such, the pH, ionic strength and the total concentration
must be closely monitored.
5. REFERENCES
SUPPORTING INFORMATION