PRINCIPLE
-
In this reaction carbon is oxidized by the dichromate ion.
Excess dichromate ion is then back titrated with ferrous ion.
- Dichromate ion reacts with carbon as follows:
Cr2O72 3Co+ 16H+ 4Cr3+ + 3CO2 + 8H2O
- Ferrous ion reacts with dichromate as follows:
6Fe2+ + Cr2O72 + 14H+ 2Cr3+ + 6Fe3+ + 7H2O
- Dichromate ion reacts with carbon as follows:
REAGENTS
- Potassium Dichromate: K2Cr2O7
- Ferrous Ammonium Sulfate: Fe(NH4)2(SO4)26H2O
- Sulfuric Acid: H2SO4
- Phosphoric Acid: H3PO4
- Sodium Fluoride: NaF
- Diphenylamine: C6H5NHC6H5
SOLUTIONS
- 1 N Potassium Dichromate:
- Weigh 49.04 g potassium dichromate (previously dried for 2 hours at 100 °C) into a 1 liter volumetric flask. Dissolve and dilute to volume with deionized water and mix well.
- 0.5 N Ferrous Ammonium Sulfate
- Slowly add 20 mL sulfuric acid to a 1 liter volumetric flask containing 800 mL deionized water.
- Add 196.1 g ferrous ammonium sulfate. Dissolve, dilute to volume with deionized water, and mix well.
- Prepare daily.
- Diphenylamine Indicator:
- Dissolve 0.500 g diphenylamine in 20 mL deionized water.
- Slowly add 100 mL sulfuric acid. Carefully mix with a glass stirring rod. CAUTION: this solution is corrosive and can cause sever burns. Proper precautions are given on the MSDS sheet for sulfuric acid.
PROCEDURE
- Weigh 1.00 g soil into a 500 mL erlenmeyer flask.
- Add 10 mL of 1 N potassium dichromate solution.
- Add 20 mL sulfuric acid and mix by gentle rotation for 1 minute, taking care to avoid throwing soil up onto the sides of the flask. Let stand for 30 minutes.
- Dilute to 200 mL with deionized water.
- Add 10 mL phosphoric acid, 0.2 g ammonium fluoride, and 10 drops diphenylamine indicator.
- Titrate with 0.5 N ferrous ammonium sulfate solution until the color changes from dull green to a turbid blue. Add the titrating solution drop by drop until the end point is reached when the color shifts to a brilliant green.
- Prepare and titrate a blank in the same manner.
- Prepare one duplicate sample and one quality control sample with each set of samples analyzed.
CALCULATION
% Organic Matter = 10 [ 1 (S ÷ B) ] × 0.67
S = sample titration
B = blank titration
QUALITY CONTROL
- Values on the duplicate samples must agree within 20% of the average of the two values.
- Values on the quality control sample must lie within the limits established for this sample.
NOTE
This procedure requires the routine use of sulfuric acid. Sulfuric acid is a corrosive, strong oxidant and should be handled with caution. Refer to the MSDS sheet for proper handling.
REFERENCES
- Jackson, M. L. 1958. Soil Chemical Analysis. 214-221.
- Walkley, A. 1947. A Critical Examination of a Rapid Method for Determination of Organic Carbon in Soils - Effect of Variations in Digestion Conditions and of Inorganic Soil Constituents. Soil Sci. 63:251-257.
- Walkley, A. and I. A. Black. 1934. An Examination of Degtjareff Method for Determining Soil Organic Matter and a Proposed Modification of the Chromic Acid Titration Method. Soil Sci. 37:29-37.
- Schollenberger, C. J. 1927. A Rapid Approximate Method for Determining Soil Organic Matter. Soil Sci. 24:65-68.