CHEM 302- EXPERIMENT 4

DETERMINATION OF SOIL ORGANIC MATTER USING THE WALKLEY BLACK

LEAMANG SEGOMELO

16000419

PURE AND APPLIED CHEMISTRY

1. AIM

To determine the soil organic matter using the Walkley-Black method.

2. INTRODUCTION

Soil organic matter (SOM) is the organic matter component of soil, consisting of plant and
animal residues at various stages of decomposition, cells and tissues of soil organisms, and
substances synthesized by soil organisms. The presence of SOM is regarded as being critical
for soil function and soil quality. SOM is important to fertility, since it performs several
functions such as cycling, water and nutrient retention and soil aggregation, in addition to
being an energy requirement for biological activity. In soils and sediments, a wide variety of
organic carbon forms are present and range from freshly deposited litter (e.g., leaves, twigs,
branches) to highly decomposed forms such as humus. Natural occurring organic carbon
forms are derived from the decomposition of plants and animals. Determination of total
organic carbon is a measure of the chemical components of organic matter present in a soil or
sediment sample. Soils and sediments contain a large variety of organic materials ranging
from simple sugars and carbohydrates to the more complex proteins, fats, waxes, and organic
acids. The spills or releases of contaminants into the environment increase the total carbon
content present in the soil or sediment. The amount and type of organic matter influences soil
moisture holding capacity, the storage and supply of exchangeable cations and other plant
nutrients such as nitrogen and phosphorus and the maintenance of stable soil structure and
aeration.

The organic matter fractions very heterogeneous and includes plant, animal and microbial
residues as well as stabilized products of decomposition generally termed humus (Skjemstad,
J. and Taylor, J. 1999). This study proposes new trends to the Embrapa, Walkley-Black, and
Mebius methods that allowed the determination of SOM by spectrophotometry, increasing
functionality (Kelting, R. and Rice, E. 1952)). The determination of soil organic carbon is
based on the Walkley-Black (WB) titration method, which is one of the classical methods for
rapid analysis of organic carbon (OC) in soils and sediments. The method is based on the
oxidation of organic matter by potassium dichromate (K2Cr2O7)-sulfuric acid mixture
followed by back titration of the excessive dichromate by ferrous ammonium sulfate
(Fe(NH4)2(SO4)2*6H2O) which gives a volume of ferrous sulfate in ml. The OM will then
be calculated using the difference between the total volumes of dichromate added and the
volume titrated after reaction. Although the method is widely used for organic matter analysis
in soils and sediments, the problems with this procedure include organic matter in the soil and
difficult end point determination also WB results in production of chromate which is
hazardous chemical.
3. PROCEDURE

1.00 g of mineral soil was weighed into a 250 ml wide mouth graduated Erlenmeyer flask and
10 ml of potassium dichromate was pipetted into each of the flask containing the unknown
soil and thereafter mixing by carefully rotating the flask to wet all the soil. Under the fume
hood 20ml of concentrated sulfuric acid was added and the flasks were allowed to stand for
five minutes under the fume hood, pure water was added to each flask to make the final
volume to be approximately 125 ml and the reaction mixture was mixed gently by swirling.
The samples were allowed to cool and return to room temperature and the volume was
rechecked after 30 minutes. 5-6 drops of phenanthroline complex were added and
immediately after it was titrated using ferrous sulfate solution until the solution reached the
end point which was noticed by a reddish-brown color and each.

4. RESULTS

BLANK 1 BLANK 2
Final burette reading (mL) 10.22 20.53
Initial burette reading (mL) 0.01 10.22
Volume used (mL) 10.20 10.31
Average volume ferrous sulphate used (mL) 10.3
Table 1: Volume of Ferrous Sulphate used in Blank titration

1 2 3

Final burette reading (mL) 9.91 19.91 29.80

Volume used (mL) 9.81 10.00 9.99

Table 2: Volume of Ferrous Sulphate used in titration of soil sample

Calculation of % easily oxidizable organic C

( B−S ) × Mof Fe ×12 ×100

Where
B = ml of Fe2+ solution used to titrate blank
S= ml of Fe2+ solution used to titrate sample
12/4000 = mill equivalent weight of C in g

( 10.30−10.0 ) ml × 1 M ×12 ×100

= 0.09%

%total C = 0.09/0.77

= 0.12%

% total C ×1.72
% organic matter=
0.58

= 0.35%

5. DISCUSSION

The percentage of the organic matter in the mineral soil sample under investigation was
found to have a 2.23% which is relatively low. The concentration of SOM in soils generally
ranges from 1% to 6% of the total topsoil mass for most upland soils. More than 6% organic
matter are hard to titrate because of rapid color change during the titration. Soils whose upper
horizons consist of less than 1% organic matter are mostly limited to desert areas, while the
SOM content of soils in low-lying, wet areas can be as high as 90% (Foth, H. 2010). The
volume of the ferrous sulphate used in the blank titration is more than the ferrous used in
titration of the sample, this is due to the oxidation of the OM which increased the color
change time and it was also difficult to determine the end point as the colors were just dark
to differentiate the colors. Under very extreme conditions, where drainage and soil aeration
may be unsatisfactory, the soil may contain more organic matter than mineral matter, in
which case it is classified as a muck (Allison et al, 1965). There are some of the factors which
could have led to deviation from the true value of the organic matter in the soil, the usual
titration errors which include, Titrating at wrong temperature since some indicators are
sensitive to temperature changes therefore fluctuations of the temperatures in the lab can have
an effect in the way the indicators reacted, and some reactions need correct temperature range
to keep stoichiometry. solution could be contaminated leading to false results, too vigorous
swirling can end up in the contents of the flask splashing out of the titration flask before the
end point had been reached and lastly leaking of the burette where sometimes burettes leak
slowly enough to allow titration, but will lose several tenths of milliliter if left for several
minutes after titrant level has been set to zero and all of these can lead to deviation from
precision. The latter were minimized in the best possible ways by careful swirling and also by
making sure the burette was tightly closed when not in use.
6. CONCLUSION

The amount of organic matter was found to be 0.35% in the mineral soil that was under study
using the Walkley-Black method.

7. REFERENCES

Foth, H. (2010). Fundamentals of Soil Science. Canada: John Wiley & Sons, Inc.

Kelting, R. and Rice, E. (1952). A Simplified Apparatus for Organic Carbon Determination by
the Walkley and Black Method. Ecology, 33(4), pp.578-579.
Rhodes, E., Kamara, P. and Sutton, P. (1981). Walkley-Black Digestion Efficiency and
Relationship to Loss on Ignition for Selected Sierra Leone Soils1. Soil Science Society of
America Journal, 45(6), p.1132.
Skjemstad, J. and Taylor, J. (1999). Does the walkley‐black method determine soil
charcoal? Communications in Soil Science and Plant Analysis, 30(15-16), pp.2299-2310.
Allison, LE in Black, CA et al. 1965, Methods of Soil Analysis.

Bartlett, GN, Craze, B, Stone, MJ & Crouch, R (ed) 1994, Guidelines for Analytical
Laboratory Safety. Department of Conservation & Land Management, Sydney