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Volume No.

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

vacant electronic orbitals allowing formation of bonds with


the other atoms, ions or molecules called ligand.
Furthermore, a phenomenon called ligand exchange
According to Huang (1982), the final charge of the complex
is the summation of the charges of individual components,
hence it may have a positive, negative or neutral.
Furthermore, one or more ligands may be replaced by
another in a phenomenon called ligand exchange and a
redox reaction may as well occur leading to a change in the
oxidation state of the metal atom.
An inquisitive dilemma in complex formations is that the
metal and ligand do not always react in a 1:1 ratio. Thus a
variety of research works, which includes the present study
focuses on the determination of the stoichiometry of a
metal-ligand complex which follows a general form:

Student, CHM115L/B30, School of ChE-Chm, Mapa Institute of Technology, kramaquiling@mymail.edu.ph


Professor, School of ChE-Chm, Mapa Institute of Technology

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

On the other hand, in mole-ratio method, the amount in


moles of one reactant, the metal usually, is held constant,
while that of the ligand is varied. A plot of absorbance as a
function of the ligand-to-metal mole ratio as shown in figure
1 is then made generating two seemingly linear branches
with inflection points which corresponds to the mole ratio
and hence the complexs formula. Lastly, in slope-ratio
method two sets of solutions are prepared. First set is
made such that there is a constant amount of metal and a
variable amount of ligand, with the total concentration of
metal, is much greater than the total concentration of

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

ligand. Under this condition it is assumed that all the ligand


is complexed. The second set is prepared having fixed
ligand concentration and is much greater than the variable
concentration of metal. The ratio of the two slopes
determines the mole ratio of the ligand-to-metal in the
complex.
A study by Xiaoxia and colleagues (2010) on the
determination of stoichiometry of iron-atrazine further
proves the effectiveness of the methods and that it is still
used at present. In this experiment, Iron-salicylic acid
complex, exhibiting purple colored solution, is investigated
to determine its composition and to what ratio(s) it exists
using UV/vis spectroscopy viathe three aforementioned
methods.

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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

Figure 1. Iron-salicylic acid complex possible composition.

Figure 2. Iron ion and salicylic complexes exhibiting a purple


colored solution.

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

After obtaining the absorbance of each solution, a plot of


absorbance versus mmole ligand/mmole total was
generated. Two linear branches were observed and their
intersection was projected to the x-axis to know the mole
fraction of ligand. From this, the formula of the complex
was calculated.
2.4.2Mole-Ratio Method
Table 2. Mole-Ratio Method

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

A plot of absorbance against mmole ligand/mmole metal


was generated and the inflection points of the lines were
projected to the x-axis, obtaining the combining ratio of the
ligand over metal.
2.4.3Slope-Ratio Method

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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

The absorbance readings for the two sets of solutions were


plotted against the concentration of ligand for the first set
and against the metals concentration for the second set of
solutions. The slope of the second set linear line is then
divided by that of the first set, which gave the ratio of the
complex formed.

3. RESULTS AND DISCUSSION


For all three methods, the absorbance was read at 216.1
nm wavelength, to which the complex is assumed to be the
only absorbing component. Table 4 providesthe data in the
Jobs Method plot seen on figure 4, the mole fraction of the
ligand and the measured absorbance for each solution.
Moreover, it is important to note that the overall
concentration of the solution was maintained at 0.0025 M.
Table 4. Data on Jobs Method plot.

Soln
1
2
3
4
5
6
7
8
9
10
11

mmol Ligand /mmol Total


1.0
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0.0

Absorbance
4.112
4.162
4.236
4.306
4.355
4.609
4.306
4.240
4.111
4.021
3.736

Figure 3. Jobs Method of Continuous Variation plot.

As depicted on figure 4, Jobs Method plot suggests that


the iron (III)-salicylic acid complex combination ratio is 1:1,
given by the ligand mole fraction value of 0.5 when the
intersection of the two linear branch is projected to the xaxis. With this in mind, the proposed complex formula is
therefore:

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

mmol Ligand /mmol Metal


0.5
1.0
1.5
2.0
2.5
3.0

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

Figure 5. Slope-Ratio Method plot.

Figure 4. Mole-Ratio Method plot.

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

[Salicylic acid] or [Iron(III)]


0.000125
0.00025
0.000375
0.0005

Absorbance
4.285
4.519
4.794
5.126

The results of the present study agree to that of previous


studies conducted on iron(III)-salicylic acid complex.
Ogawa and Tobe (1966) found that three complex species
Fe(Sa)+, Fe(Sa)2-, and Fe(Sa)33- are formed in acid
solutions and that an increasing complex formation
constants is observed. Furthermore, the same proponents
ascertained that salicylic acid can be used as a reagent for
determining iron (III) in the presence of iron (II) if the
spectroscopic measurements are made in the pH range
from 2 to 3. Another study (Koch, Reid, and Meyerhoff,
2008) concluded that 1:3 iron:salicylate complex is typical
result in the determination of iron (III)-salicylic acid complex
stoichiometry, but may represent just a minor complex, and
1:1 iron:salicylate complex is the predominant
stoichiometry of the reaction.

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

6]Skoog, D.A., Holler, F.J., & Crouch, S.R. (2007).


Principles of instrumental analysis. Thomson Brooks/Cole.
Belmont, California.
9]Skoog, D.A. (2014). Fundamentals of analytical
chemistry. Brooks/Cole Cengange Learning. Belmont,
California.
10]Xiaoxia, O., Wang, C., Zhang, F., Quan, X., Ma, Y., &
Liu,, H. (2010). Complexation of iron by salicylic acid and
its effect in atrazine photodegradation in aqueous solution.
Front. Environ. Sci. Engin. China, 4, 157-163.

1]Harvey, D. (2000). Modern analytical chemistry. McGraw


Hill Companies.
2]Huang, C. (1982). Determination of Binding
Stoichiometry by the Continuous Variation Method: The Job
Plot. Methods in Enzymology, 87, 509-525.

SUPPORTING INFORMATION

3]MacCarthy, P. and Hill, Z. (1986). Novel Approach to


Job's Method. Journal of Chemical Education, 63, 162
167.
4]Mitchel-Koch, J., Reid, K., & Meyerhoff, M. (2008).
Salicylate detection by complexation with iron (III) and
optical absorbance spectroscopy. Journal of Chemical
Education. 85(12), 1658-1659.
5]Ogawa, K., & Tobe, N. (1966). A spectrophotometric
study of the complex formation between iron (III) and
salicylic acid. Bulletin of the Chemical Society of Japan, 39,
227-232.

Figure 6 Perkin-Elmer 35 UV-Vis Spetrophotometer.