Chemical Oxygen Demand
(COD Vials)
LR COD: 0 - 150 mg/L
HR COD: 0 - 1500 mg/L
HR+ COD: 0 - 15,000 mg/L
SAFETY INFORMATION
COD reagent vials contain sulfuric acid, which causes severe
burns. Read the SDS before using. Wear appropriate personal
protective equipment. Perform this test procedure under a
hood.
TEST METHOD
Chemical oxygen demand is a measure of the oxidizable
organic matter content of a wastewater sample. The sample
is reacted with an acidic solution of potassium dichromate in
the presence of a catalyst (silver) and digested for 2 hours at a
temperature of 150°C. Oxidizable organic compounds reduce
the dichromate ion (Cr2O7²-) to the chromic ion (Cr3+). In the
LR COD kits, the decrease in dichromate ion is measured
colorimetrically. In the HR and HR+ COD kits, the amount
of chromic ion produced is measured. The test results are
expressed as the number of milligrams of oxygen consumed
per liter of sample (mg/Liter COD).
OPTIONS FOR OBTAINING TEST RESULTS
• Use preprogrammed CHEMetrics instrumentation for direct
readout. Follow the Set-up and Measurement procedures
in the instrument’s operator’s manual.
• Use the supplied calibration equation (Step 12 of Test
Procedure) for other brand spectrophotometers.
• Generate a standard curve specific to the instrument being
used by preparing a series of five standard solutions (one
of which is a blank) which covers the expected range of
the test.
NOTE: COD standard solutions are used to check the accuracy of
the test or to generate an instrument specific calibration
curve.
SAMPLE COLLECTION
Collect samples in glass bottles. When it is necessary
to preserve samples for storage, acidify to pH < 2 with
concentrated sulfuric acid. Store preserved samples at
4°C for no longer than 28 days after collection.
TEST PROCEDURE
1. Homogenize 500 mL of sample for 2 minutes in a
blender.
Note: Blending ensures an even distribution of any solids
that may be present in the sample, thus improving the
accuracy and reproducibility of the test.
2. Preheat the digester block to 150°C.
3. Remove the cap from a COD vial.
4. Pipet 2.00 mL (0.20 mL for HR+ COD) of sample into
the vial. The contents of the vial will become hot.
5. Secure the cap onto the COD vial. Do not overtighten
as this may compromise the closure integrity.
6. Immediately invert the vial 10 times to mix well.
Caution: When mixing, hold the vial by the cap only.
The contents of the vial will become very hot.
7. Wipe the vial with a damp towel and place it in the
preheated digester block.
8. Prepare the reagent blank by repeating Steps 3
through 7, using deionized water rather than sample
in Step 4.
Note: At least one reagent blank must be run with each set of
samples and with each new lot number of COD vials.
Use a blank vial from the same lot as the test COD
vials.
9. Allow the vials to heat in the digester block at 150°C
for 2 hours.
10. Turn the digester block off and allow the vials to
remain in the unit to cool for 15 to 20 minutes.
11. Use caution, the glass vials are still very hot.
Carefully remove each vial from the digester. Make
certain that the cap is secured tightly, then invert
each vial several times. Place the vial in a rack to
cool. Store the vials in the dark and allow at least
30 minutes for them to cool to room temperature. If
COD vials are not cooled to room temperature, the
accuracy of the test results may be compromised.
CAUTION: Hot vials may shatter if dropped or cooled
rapidly.
12. For instrument setup when using preprogrammed
CHEMetrics instrumentation, refer to the
instrument’s operator’s manual. For other brand
spectrophotometers, use the following information:
Range Wavelength Calibration Equation
LR COD 420 ppm (mg/L) = (-331)(abs) - 0.6
HR COD 620 ppm (mg/L) = (2301)(abs) - 3
HR+ COD 620 ppm (mg/L) = (23010)(abs) - 3
13. Wipe the exterior of the reagent blank vial until it
is clean and dry. Place the reagent blank vial into
the instrument sample compartment to zero or set
reagent blank.
14. Wipe the exterior of a test COD vial until it is clean
and dry. Place the vial into the instrument sample
compartment to obtain test results.
Note: When using the HR+ COD Vials with the V-2000
Photometer or the A-7325 HR COD SAM, multiply
the photometer output by 10 to obtain the actual test
result. This is necessary for any direct read photometer
that uses the same program for HR and HR+ COD
vials.
15. If applicable, use the range specific calibration
quation in Step 12 to convert absorbance values to
test results in mg/L COD.
SOURCES OF ERROR
Mercury containing LR COD and HR COD reagents are
formulated to withstand interferences from up to 2000
ppm chloride. Mercury containing HR+ COD reagent
can be used on samples containing up to 20,000 ppm
chloride without interference. Samples with higher
chloride concentrations require dilution. Also, samples
that contain high levels of chloride (>1000 ppm) and
low levels of COD (<30% of the product range) will give
false positive test results. In this case, sample dilution is
recommended.
Mercury free LR COD and HR COD reagents are
available for samples containing less than 100 ppm
chloride (less than 1000 ppm for the mercury free HR+
COD kit).
Choosing the correct range COD Kit is important. If the
COD concentration in the sample is significantly above
the range of the test kit being used, false low test results
may be obtained.
The COD reagent is light sensitive. Store vials in the
dark and at room temperature when not in use.
Good technique and elimination of contamination are
necessary for accurate results. Wash all glassware with
20% Sulfuric Acid.
For COD testing, LED based photometers do not
produce accuracy, precision and sensitivity equivalent
to that attainable with spectrophotometers. For NPDES
reporting purposes for COD, a spectrophotometer is the
preferred method of measurement.
REFERENCES
APHA Standard Methods, 22nd ed., method 5220 D - 1997.
ASTM D 1252-06, Chemical Oxygen Demand (Dichromate Oxygen Demand) of Water, Test
Method B.
EPA Methods for Analysis of Waters and Wastes, method 410.4 (1983).
A. M. Jirka and M. J. Carter, “Micro Semi-Automated Analysis of Surface and Wastewaters for
Chemical Oxygen Demand,” Analytical Chemistry, Vol. 47, p. 1397 (1975).
J. A. Winter, “Method Research Study 3, Demand Analysis, An Evaluation of Analytical Methods for
Water and Wastewater,” USEPA, (1971).
June 24, Rev. 39