NCHE 312: EXPERIMENT 1

Spectrophotometric
Determination of the
coordination Number of
a complex
Charmaine Moyo
32306938
Abstract
Spectrometry is frequently used to track the status of reactions and the equilibrium
point. Given that pertinent restrictions (such as the regions over which Beer's law is
valid) are acknowledged, spectrophotometric measurements are frequently simple
to perform and the method is sensitive and precise. There are numerous different
methods that can be used to determine the formulae of inorganic complexes, and
spectroscopic techniques are helpful for doing so. Using Job's technique, we
investigate the complex formed by salicylic acid and ferric ions in this experiment,
and we also use two separate methods to calculate the stability constant.
Introduction
Theory
Job's method of continuous variation [1] is
a simple method for finding the formula of a complex [2, 3]. It is most effective when
only a single complex is formed.
The success of a Job’s method experiment depends upon the extent to which Beer’s
law is followed. Beer’s law is one of the most widely-applied relationships in
chemistry, and is usually cast in terms of the absorbance A of a solution, defined by
(1)
A=log10 I0/I
in which Io is the intensity of light incident up on a sample and I the intensity of the
transmitted light. The absorbance is related to concentration of the solution, c,
through Beer’s law, which is (2)
A=εcl
In this equation
ε is the molar extinction coefficient for a species and l is the optical path length

The compositions of many different coordination complexes have been identified,

even some that are nonisolable in the solid state. The fact that a coordination
complex has not been isolated does not necessarily imply that the metal-ligand
interactions are weak. In many instances, complex equilibria make it difficult to
selectively crystallize each of the species separately from solution.
The identity of the other species must be established and verified by other
techniques. The formulae of highly coloured complex ions may be determined in
solution using spectrophotometric techniques. Consider the general reaction
between a metal ion Mz+ and a ligand L that form the coordination complex [MLn] z+
(eq. 1): Mz+ + n L º [MLn] z+

The procedure used in this experiment is known as the Job’s Method of Continuous
Variations. The method will be applied to the reaction of Fe3+ with SCN- in water (eq.
3), and must determine the empirical formula of the complex ion that is produced
under the specified conditions. A series of solutions of various concentrations of
ligand (SCN- ) and metal ion (Fe3+) are prepared and examined
spectrophotometrically to determine the concentration ratio that generates the
highest concentration of complex ion. By plotting the absorbance of each solution
against the mole fraction of ligand, the ligand concentration that corresponds to the
maximum concentration of complex ion may be determined.
[Fe(H2O)6] 3+ + n SCN- →[Fe(H2O)6-n(SCN)n] 3-n + n H2O
Method/Procedure

Solutions were prepared in two 250ml Volumetric flasks

X: 0.002mol/l Fe(NO3)3 in 0.02mol/L HNO3

Y: 0.002mol/L KSCN in 0.03mol/L HCl
Each with a total ionic strength I: 0.032mol/L. Solutions were transferred into two
burettes and mixtures where already mixed together.
So with the mixtures,two of them were mixed, which was 5ml of each of them.
Then 5 absorbance was measure with different wavelengths: 451, 453, 455, 457 and
459.
With the wavelengths given, a maximum absorbance needed to be found and which
wavelength could give that.

Results/ Calculations
Wavelength Absorbance
451 0.914
453 0.915
455 0.916
457 0.917
459 0.915
Table 1: Results retrived from finding the highest absorbance

To find the Mole faction for X for the table below

The mole fraction of a component i is given by:

 =  , where   is the number of moles of the ith component and   is the
total number of moles of all the components in the solution.
Here, the concentration of KSCN and Fe(NO3)3 solution are the same,i.e, 0.002 M,
thus moles of each component is directly proporitonal to it's volume. Hence, for the
first solution, where volume of SCN- = 9.5 mL and volume of Fe+3 = 0.5 mL, the mole
fraction is given by:
 0.5
Xi= =0.05. Others were calculated in a similar manner. Now the four
0.5+ 9.5
column table is shown below:

Mole Fraction of Fe3+ Mole Fraction of SCN-

0.05 0.95
0.1 0.9
0.15 0.85
0.2 0.8
0.25 0.75
0.3 0.7
0.35 0.65
0.4 0.6
0.45 0.55
0.5 0.5
0.55 0.45
0.6 0.4
0.65 0.35
0.7 0.3
0.75 0.25
0.8 0.2
0.85 0.15
0.9 0.1
0.95 0.05

Absorbance vs Mole Fraction

1
0.9
0.8
0.7
0.6
Absorbance

0.5
0.4
0.3
0.2
0.1
0
0 5 10 15 20 25

Mole fraction

Series2
Number 5 on the question below

In the case of the solution X: ¿

¿

C¿¿
3−
+¿(aq)+ NO (aq)¿
HNO3 (aq ) → H
C¿¿
1
Thus : I = ¿
2
0.02 M (−1)2 ¿=0.0320 M

In the case of the solution Y:  [KSCN]= 0.002 M and [HCl]=0.02 M.

−

KSC N (aq ) → K +¿(aq)+ SC N (aq )¿

C¿
−
+¿(aq)+Cl (aq)¿
HCl (aq) → H
C¿
1
Thus : I = ¿
2
0.03 M (−1)2 ¿=0.0320 M
The equation is given as:
E1 /2 −¿
Its more like a straight line y=mx+c
Y= E1 /2 −¿
0.0591
C= − logK
2
0.0592
m= − n
2
x= log [N H 3 ]

−1
[NH 3 ]/mol . L 0 3.14 3.68 4.75 7.20 8.86
E1 /2 /V -0.752 -0.840 -0.856 -0.872 -0.904 -0.920

log [N H 3 ] 0.4969 0.5866 0.6767 0.8573 0.9574

E1 /2 −¿/V -0.088 -0.104 -0.12 -0.152 -0.168

Basically E1 /2 /V is -0.752 because [NH 3 ]/mol . L−1 on the first column is 0.

So for [NH 3 ]= 3.14
E1 /2 −¿/V= -0.840-(-0.752) = -0.088
This was done with the other columns also, the calculations are the same.
log [N H 3 ] was calculated like just punching log(3.14)=0.4969 on the calculator
similar to other values.

The log [N H 3 ] vs the difference in half wave potential was plotted in the graph
below:

log[NH3]
vs E1/2-(E1/2)s

0
0.4 0.5 0.6 0.7 0.8 0.9 1
-0.02
-0.04
-0.06
E1/2-(E1/2)s

-0.08
-0.1 f(x) = − 0.174519962580566 x − 0.00162171715414691
R² = 0.999710210067251
-0.12
-0.14
-0.16
-0.18
log[NH3]
The slope line is = -0.1745
0.0592
Which means − n =− 0.1745
2
n 0.0592=2× 0.1745
0.349
n= =5.895
0.0592
Rounded off its n= 6

The compound=[cd(NH3)6]2+
Discussion
Numerous metal coordination compounds exhibit color as a result of energy
absorption in the electromagnetic spectrum's visible region. This property can be
used in the scientific technique known as spectrophotometry. The correlation
between the quantity and absorbance of an absorbing species is provided by Beer's
Law:
Absorbance (A) = ε l c
where ε = is the molar absorptivity, cm is the route length, and c is the solution's
concentration (in M). By measuring the light absorption at a given wavelength for a
blank solution (solvent alone) and for a solution of the, the absorbance is calculated
complex. The absorbance for the complex alone accounts for the variation in
absorbance between these two solutions. Because l is fixed for a sample cell it is
possible to calculate the concentration of a given solution if ε is known for a specific
complex.
In order to determine ε for your complex, you will prepare a standard curve. A
standard solution of compounds X and Y will be provided to you, from which you will
create a number of solutions with known concentrations. You will measure the
solutions' absorbance and create a diagram of the relationship between absorbance
and concentration. You can calculate the slope of the solid line from this image,
which is just ε. The standard curve should not be applied in this area because the
absorbance measurements start to flatten out at higher concentrations.
Spectrophotometric analysis is essential for determining biomolecule concentration
of a solution and is employed ubiquitously in biochemistry and molecular biology.
The application of the Beer-Lambert-Bouguer Lawis routinely used to determine the
concentration of DNA, RNA or protein.
The 5 solutions were measured and absorptions were taken after that. The highest
absorption’s wavelength that was used was 457nm and that was the wavelength that
was used to determine the absorptions of all 19 samples. Mole fraction was
determined and Ionic strength was discovered that it is constant.

Conclusion. The future of spectrophotometry lies especially in the improvement of

pathological diagnostics, disease detection and general clinical research as “uv-vis
spectroscopy enables safer, non-invasive analysis of soft tissue, and can enhance
accuracy and speed in clinical diagnostics and medical research.”
References
 R.J. Angelici Synthesis, 1977, Technique in Inorganic Chemistry, 2nd ed.,
Philadelphia : Saunders.
 B.Z. Shakhashiri, G. E.Dirreen, 1982,Manual for Laboratory Investigations in
General Chemistry.
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etal_Ion_with_Organic_Reagent
 https://www.researchgate.net/publication/
336809680_Spectrophotometric_Determination_of_The_Complexation_of_Heavy_M
etal_Ion_with_Organic_Reagent
Mindmap: A Kinetic Study of the
"Breathalyzer" Reaction
Charmaine Moyo 32306938

To determine whether Two students will be

Objective: To study assigned to work
the reaction is zero, first
the kinetics of the or second order with together to prepare
reaction of ethanol respect to dichromate. one reaction
and acidic To determine the rate solution.
potassium .constant of the
dichromate. reaction.

Each pair will be Compounds that contain

assigned to a specific chromium (VI) are toxic
computer and Mindmap: and suspected
SpectroVis Plus, which carcinogens. Wear
Experiment 5
they must gloves. Wash your hands
use to acquire all their thoroughly with soap
measurements and water after
throughout the course handling solutions that
of the experiment. contain Cr(VI).

Do not pour any 2. Is the reaction zero, 4. Thermal

solution containing first or second order with decomposition of
chromium down the respect to dichromate? nitrogen dioxide to nitric
sink!Calculations What is the value of the oxide and Oxygen occurs
1. Hand in the three rate constant? What are according to the
plots (zero, first and the units? Use the value following reaction:
second order) and the 3.58 x 102 M-1 for εl 2 NO2→2 NO + O2
Excel worksheet of your , if necessary.
data and results.