COMPLEXOMETRY

Determination of Cr (III) and Iron (III) in a Mixture Kinetic Masking

PRINCIPLE INVOLVED
Reaction: Complexation
reaction
Titration:
Residual
Titration
Indicator: Xylenol Orange
Excess Titrant: 0.01M
EDTA
Back
Titrant:
0.01M
Pb(NO3)2
Endpoint: lemon yellow
red-violet
Titration Conditions:
Fe - cold and acidic (excess
EDTA)
Cr - boiled and acidic (excess
EDTA)
Pb - slightly acidic (back)

PROCEDURE

Reasons for Important Steps

Place 10 mL of the solution containing

the two metals (concentration of
neither exceeds 0.01 M) in a 600 mL
beaker.

->This titration serves as a 2-in-1 titration

for 2 ions

Dilute to 100 mL with deionized

water

3+

3+

2+

Kinetic Masking
- a case in which a metal

ion does
not effectively enter into the
complexation reaction because of
its kinetic inertness
- difference in rates of reaction with
EDTA of metal cations are utilized
**For this case, the slow reaction of
chromium (III) with EDTA makes it
possible to titrate the other metal
ion which is Fe (III) without
interference from Cr (III).

->EDTA forms a complex with Fe3+, but not

with Cr3+ due to differences in the rate of
formation of their respective complexes
with EDTA. The Fe (III)-EDTA complex
forms rapidly in cold solutions.
->Hexamine serves as a buffer.

Add a few drops of the indicator

solution and titrate the excess
EDTA with the standard lead
nitrate solution to the formation
of a red-violet color.
To the resulting solution, add a 20
mL portion of standard EDTA
solution. Add nitric acid (1 M) to
adjust pH to 1-2 and boil the
solution for 15 minutes.
Cool, dilute to 400 mL using
deionized water, and add
hexamine to pH 5-6. Add more of
the indicator solution and titrate
excess EDTA with the standard
lead nitrate solution.
**Each milliliter of 1N H2SO4 is
equivalent to 29.16 mg of Mg(OH)2.

Fe3+
+
Cr3+
+

->Deionized water is used to prevent

interference from other metal ions.

Add 20 mL of standard EDTA

solution

Add hexamine to adjust the pH to

5-6.

CHEMICAL EQUATIONS,
COMPUTATIONS INVOLVED

Pb2+
+
Fe (III) content (VEDTA and VPbNO3 are
from 1st addition):

%Fe 3+

->Xylenol orange is used as the indicator

since it is stable in an acidic medium. It is
also used since it is specific for Fe 3+ and
Cr3+ at the specified pH and temperature.
PbNO3 is used as the back-titrant since the
Pb-EDTA complex has a lower stability
constant (18.04) compared to the Fe (III)EDTA complex (25.10).

->This portion of EDTA reacts with Cr3+.

Boiling is done to increase the rate of
formation of the Cr (III)-EDTA complex.

Cr

[ ( MEDTA x VEDTA )( MPbNO

Vsolution

Cr (III) content (VEDTA and VPbNO3 are

from 2nd addition):

[ ( MEDTA x VEDTA ) ( MPbNO

%Cr
3+

*For Cr (III) in computations, the volume to plug-in

Vsolution
are the second volumes, not the total volume. The
2nd volume added in the titration has taken into
account the fact that the Fe will not interfere with
the complexation thus only Cr will react to EDTA.

REFERENCES:

->The Pb-EDTA has a lower stability

constant compared to Cr (III)-EDTA (23.4).

Christian, G.D. (2004) Analytical Chemistry (6th ed) USA: John

Wiley and Sons,
Inc.
Harvey, D. (2000) Modern Analytical Chemistry (1st ed) Usa:
McGraw-Hill
Companies, Inc.
Jeffery, G. H., Bassett, J., Mendham, J. and Denney, R. C.
(1989).
Vogel's Textbook of Quantitative Chemical Analysis. (5th
ed.).
England: Longman Scientific & Technical. p. 335
McPherson, P.A.C. (2015). Practical Volumetric Analysis.
Cambridge:

DEMATA, ESTEVES, FELIPE, FELIZARTE