The direct determination of SOC may be accomplished by the wet digestion of a soil sample in a

K2Cr2O7-H2SO4 solution. This technique, known as the Walkley-Black method, was once the
standard for SOC determinations; however, it is labor intensive, requires a great deal of analytical
skill, employs strong oxidants and acids that must be heated, and generates a hazardous waste
(and has been replaced by the dry combustion methods described above). In this method, a mass
of soil is placed in a glass digestion tube, to which is added a standardized K2Cr2O7 solution and
concentrated H2SO4. The tube is then placed in a digestion block and heated to 150C for 30
minutes. During this period, the following oxidation-reduction reaction occurs:

where CH2O(s) represents an average chemical formula for SOC. In this reaction, the carbon in
SOC, assumed to have an average oxidation state of zero (C0), is oxidized to CO2(g) (CIV) by the
(aq) (CrVI) in an excess of acid (provided by H2SO4). Following digestion, the soil suspension
is cooled and titrated to the N-phenylanthranilic acid end point with a solution containing standard
Fe(NH4)2(SO4)2. During the titration, the (aq) that was not consumed by SOC is reduced by
Fe2according to the reaction:

The determination of total organic carbon by oxidation with potassium dichromate in

a strong acid open medium, was proposed first by Schollenberger (1927) then by
Walkley and Black (1934) from which it takes its name. After a stage of
oxidation/mineralization at the temperature of reaction for a given length of time, the
non-reduced dichromate in excess is back titrated by ferrous iron.
Many authors have studied the factors that affect C mineralization: acid
concentration (H2SO4, H3PO4), potassium dichromate concentration, oxidation
temperature (from the temperature of reaction to +210°C), the time of contact, the
need to condense the vapour to avoid too high concentration of the medium, and to
limit destruction of the oxidant by avoiding overheating of the walls. The choice of the
temperature resulted in two different types of methods:
– At the temperature of reaction  120°C (Walkley and Black 1934).
– At standardized boiling  150°C (Anne 1945; Mebius 1960).
Different procedures were proposed for back titration of dichromate excess such as
soil/solution separation by centrifugation and filtration, but direct volumetric titration in
the soil suspension was the most widely adopted. Redox indicators (diphenylamine,
barium diphenylamine sulphonate, N-phenyl anthranilic acid, ferrous O-phenanthroline)
can be absorbed on clays. Additives (e.g. NaF, H3PO4) allow better reading by
sequestering the coloured products that are formed or dissolved (e.g. Fe3+) and
which can mask the reaction.

Principle
Mineralization
Organic forms of C are oxidized in the presence of excess dichromate. The reaction in a
concentrated acid medium is exothermic (120°C). Itdevelops at a fast kinetics under the
following conditions:
The amount of reduced dichromate is considered to be quantitatively linked to the organic
C content of the sample. The likelihood of reduction is assumed to be identical for different
forms of organic C and the reducing power is assumed to be constant during
mineralization. In practice, at the temperature of reaction without heating, a factor of
correction will be required because only the most active forms are oxidized, i.e. 60%–80%
of organic matter. This factor was fixed at 1.30 (100/76) to take the variable reactivity of
the organic forms into account, but can vary between 1.10 and 1.45 depending on the soils
and on the types of vegetation. The inorganic forms (carbonates, bicarbonates) are
destroyed and do not play any role except in the consumption of acid and the production of
foam. The precipitation of calcium sulphate can be problematic during final titration if a
spectro-colorimetric method is used.
CaCO3 + H2SO4 CaSO4+ H2O + CO2


Soil organic carbon (SOC) content is measured using dry or wet combustion techniques. Dry combustion utilizes either
medium-temperature resistance or high-temperature induction furnaces that provide the heat necessary for the combustion
of organic C to CO2. The CO2 liberated is then quantified using gravimetric, titrimetric, volumetric, infrared, or thermal
conductimetric methods. Resistance furnaces heat samples by radiation, conduction, and convection in a sample holder
surrounded by high-resistance materials. Accelerators such as CuO are often mixed with a soil sample to promote the
combustion of SOC. Induction furnaces use high frequency electromagnetic radiation as the heat source. Since soils
cannot be heated by induction, it is necessary to add susceptors (Fe or Sn) that indirectly heat the sample by radiation,
conduction, and convection. Wet combustion usually involves digesting a sample with a 60: 40 H2SO4 : H3PO4 mixture
containing K2Cr2O7 and boiling the sample at 210 "C. The SOC content is determined from the CO2 evolved, which is
adsorbed by a suitable adsorbent and weighed, or it is absorbed by a standard base and titrated. Since dry and wet
combustion techniques are a measure of total soil C content (organic plus inorganic C), it is necessary to correct
for the inorganic C contribution. This is accomplished by predigesting the sample to remove inorganic C present as
carbonates, or measuring inorganic C and subtracting it from the total C content. Alternately, soil organic matter content is
frequently determined using the Walkley-Black method, described in detail by Allison (1965). This method, which
involves oxidation of soil organic C by Cr2O7 2–, can be described by the following reaction:

where organic C is assumed to have an average valence of zero. The excess dichromate is then titrimetrically measured
with a standard FeSO4 solution and the amount of organic C oxidized is calculated from the amount of dichromate
reduced. A colorimetric determination of the amount of Cr3þ produced can also be used to quantify organic C.