5.

DETERMINATION OF STOICHIOMETRY OF METAL COMPLEXES USING

SPECTROPHOTOMETRY (JOB’S METHOD)

Aim:

To determine the composition of the complex formed between Iron (III) and salicylic acid and to

determine its stability constant spectrophotometrically by Job's method of continued variation.

Principle:

Many phenolic compound give strongly coloured products with solutions of ferric salts. They are

weak complexes of iron in equilibrium with reactants. The intensities of colour at different proportion

are a measure of their stoichiometry. Job‟s theory states that when equimolar solutions of the two

reactants are mixed in various proportions, the maximum amount of equilibrium product is formed,

when the proportion of the reactants employed corresponds to the empirical formula of the product.

aA + bB = Aa Bb

the maximum amount of complex Aa Bb will be formed when a‟ part of x molar solution of A is

mixed with „b‟ parts of y molar solution of B.

If a/b = 1, then the complex will be AB.

The stability constant can be measured by doing experiments at two different concentrations and

considering that the complex concentration is the same when the optical density is equal for the two

different sets.

Apparatus & Chemicals Required:

Sl. No Apparatus Chemicals

1 Spectrophotometer and 0.002M Salicylic acid
accessories
2 Stoppered test tubes 0.002M Ferric ammonium sulphate
3 pH meter/ pH paper 0.002M Hydrochloric acid
Procedure:

Take 10 stoppered test tubes and mix 0.002MFe3+ and 0.002M salicylic acid solution in different

proportions as shown in the Table I. Since the complex formed between the two reactants is stable at

pH 2.6 to 2.8, 0.002MHCl is used.

Switch on the spectrophotometer and allow it to stabilize for 10 minutes. Use 0.002MHCl as blank

solution to eliminate the background absorption if any. Using the most coloured solution, scan the

wave length range for obtaining λ max. Now measure absorbance of each one of the solutions at the

selected λ max. Now, measure the absorbance of each one of the solutions at the selected λmax and

note down the absorbance under set I.

Dilute the stock Fe3+ and salicylic acid solutions to 0.001M. Repeat the procedure employed for set I

and note down their absorbance under set II.

Identify the solutions that give the same absorbance.

Draw a plot of Absorbance Vs. the volume of salicylic acid used.

Volume of HCl in each tube = 5mL

Solution number Volume of Fe+3 Volume of Absorbance at

salicylic acid (mL) 1×10-3 M 5×10-4 M
1 1 9
2 2 8
3 3 7
4 4 6
5 5 5
6 6 4
7 7 3
8 8 2
9 9 1
10 9.5 0.5
Blank

Calculations:

Composition of the complex:

Identify the ratio of Fe3+ and salicylic acid that gives the maximum absorbance. Note this as the

composition of the complex.

Stability constant of the complex:

The two sets of mixtures give the same absorbance value when the concentration of the complex

formed is the same.

Select the samples in set I and set II that give the same absorbance value.

Calculate the concentrations of Fe3+ and salicylic acid in each.

If A1 and B1 are the respective concentrations of iron and salicylic acid for set 1 and A2 and B2 are

their respective concentrations for set 2 that gives the same absorbance value and if the complex

concentrations is x, then the stability constant K is given as

The value of K can be calculated from X

Result:

1. Wavelength at maximum absorbance λ max =

2. Stability constant of the complex from the graph K =

Calculation:

Conc of Fe+3 son (A1): N1V1 =N2V2 = (vol of Fe+3 x 0.002M)/total volume

Conc of SA (B1) = (From graph (V1) x 0.001M)/total volume

Conc of Fe+3 son (A2) = (vol of Fe+3 son x 0.001M)/total volume

Conc of SA (B2) = (From graph (V2) x 0.001M)/total volume

X = (A1B1-A2B2)/[(A1+B1)-(A2+B2)]

K = X/(A1-X)(B1-X) = X/(A2-X)(B2-X)