CHM 423: Physical Chemistry Laboratory
Experiment 8: Spectrometric Characterization of Chemical Formula and Stability Constant of a
Coordination Complex
Gourav Das, 18095
Aim: To determine the stoichiometry and stability constant for the coordination complex formed
between ferric ions and thiocyanate ligand at room temperature using the Job’s method.
Materials Required:
• • UV-Visible Spectrophotometer
• • Bath sonicator
• • Test tubes (20 mL ten units)
• • Test tube stand (one unit)
• • Graduated pipette (10 mL volume two units)
• • Volumetric flasks (100 mL two units, 250 mL one unit)
• • Beakers (100 mL volume two units)
• • Glass rod (one unit)
• • Dropper (one unit)
• • Hydrochloric Acid (10 mM, as provided)
• • Nitric Acid (15 mM, as provided)
• • Potassium thiocyanate (stock solution, 4 mM)
• • Ferric Nitrate (stock solution, 4 mM)
Theory - Coordination complexes are defined as class of chemicals that are characterized
by a central metal ion surrounded by electron donating groups (ligands) that are covalently
bonded to the metal ion. They are omnipresent and play numerous crucial roles in our day-
to-day life. For instance, the prosthetic group “heme” of the oxygen transport protein
haemoglobin and green pigment chlorophyll in plants that help in light absorption are all
coordination complexes. Characterizing the chemical formula of such complexes is a
fundamental task that is encountered by a scientist to understand the properties (colour, light
absorption, binding ability, etc.) that arise from them. In 1928, Paul Job devised a
methodology to characterize formation and stability of such coordination complexes in
solution that is popularly known as Job’s method, also referred to as method of continuous
variation. Consider a reaction between a metal ion Mn+ and ligand L that results in the
formation of the complex [MLx]y+ (where ‘x’ is the number of ligands surrounding the metal
ion in the complex and ‘y+’ is the net charge following complexation depending upon the
charge of L).
Job’s method is based on the following idea where a series of solutions are prepared each
of which consisting of the same total number of moles of Mn+ and L with each solution in the
series with varying mole ratio of Mn+ to L, define as ‘R’. The maximum product is formed
when the mole ratio matches exactly with the stoichiometry of the coordination complex, i.e.
when M:L is in the ratio 1:x as shown in equation 1. R is systematically varied low
concentration of L to high concentration of Mn+, keeping the total number of moles constant.
The complex formation is monitored by analytical techniques, with spectrophotometric
measurements being common and convenient as coordination complexes are commonly
observed to possess vibrant colours. The plot of the physical variable measured as a
function of R would result in a curve where a maximum is observed as R approaches ‘x’,
thus providing the stoichiometry of the complex. Subsequently, the equilibrium constant can
also be measured by determining the absolute concentration of the coordination complex.
Spectrophotometric measurements are not only qualitative but are also quantitative as
explained by the Beer-Lamberts law. The law states that the rate of decrease of intensity of
radiation with thickness of absorbing solution (“l”) is proportional to the intensity of the
radiation and to the molar concentration (“c”) of the solute in solution.
Integrating the above equation within limits of I = Io (intensity of incident radiation) to I = I
(intensity of transmitted radiation) across the length of the sample 𝑙 = 0 to 𝑙 = 𝑙 (where l is the
length of the sample encountered by the radiation, generally pathlength of cuvette), we
arrive at the Beer-Lambert’s law, with ε is molar absorption/extinction coefficient (a.k.a molar
absorptivity).
This depends on the nature of the absorbing species, wavelength of light, temperature and
the choice of units (concentration/length). Generally, concentration is expressed in molar
(mol•L-1), length defined in cm (generally 1 cm cuvettes are used), ε is expressed in L•mol-
1•cm-1.
Absorbance is defined as log(Io/I) and is a dimensionless number. Molar absorptivity is
measured from the slope of the linear fit obtained from A as a function of known ‘c’.
Experimental procedure:
1. Room temperature was measured using the thermometer. As this is an equilibrium
experiment, temperature must be clearly mentioned.
2. 1 mM ferric nitrate solution in the provided 10 mM nitric acid solution was
prepared In two separate 100 mL volumetric flasks (solution A) and (solution B) 1
mM potassium thiocyanate solution in the provided 15 mM hydrochloric acid.
3. The following series of solution was prepared as recommended in the Job’s method by
keeping the total number of moles (1 mM) and the total volume (10 mL) constant using the
two solutions (A & B) prepared in step 2.
4. UV visible spectrum was recorded in the spectrophotometer between the wavelength 300-
800 nm with 1 nm bandwidth. Observations was recorded of absorbance at the maximum
absorbance (𝝺max) as shown in table 1.
5. Job’s plot: absorbance at 𝝺max as a function of mole fraction of thiocyanate ligand (table
1) was plotted . Determine the empirical formula of the complex.
Equation to consider
Sr. No. Fe(NO3)3 in mLKCNS in mL Con.Fe+3 in mM Conc. CNS- mMMole Fraction CNS-
1 1 9 0.1 0.9 0.9
2 2 8 0.2 0.8 0.8
3 3 7 0.3 0.7 0.7
4 4 6 0.4 0.6 0.6
5 5 5 0.5 0.5 0.5
6 6 4 0.6 0.4 0.4
7 7 3 0.7 0.3 0.3
8 8 2 0.8 0.2 0.2
9 9 1 0.9 0.1 0.1
0.35
0.3
0.25
0.2
0.15
Absorbance (A)
0.1
0.05
0
0 0.5 1
X/A vs A Graph y = -0.3911x + 1.0115
R² = 0.674
1
0.98
0.96
0.94
0.92
0.9
0.88
0.86
0.84
0 0.05 0.1 0.15 0.2 0.25 0.3 0.35
Absorbance (A)xy/A
0.092 0.97826087
0.167 0.958083832
0.219 0.95890411
0.26 0.923076923
0.289 0.865051903
0.265 0.905660377
0.226 0.92920354
0.172 0.930232558
0.094 0.957446809
Calculation
From the Graph Between XY/A vs A we can get the slope value of -0.391 and intercept is
1.0115
From the Equation
We get that (𝜀𝑙)−2 = 0.391 and = =1.0115 so by putting the values of x, y we
get 𝜀𝑙 = 5.057 and k= 0.24
So from
ΔGº = - RTln(K)
We will get
ΔGº = - RTln(0.243) =-8.314 x 298 x -0 = + 3504.96J ( By taking 25oc as room temperature)
And the complex forms by this experiment is K3[Fe(SCN)6]
