Dqo 5220
Dqo 5220
Dqo 5220
5220 A. Introduction
Chemical oxygen demand (COD) is defined as the amount of a
specified oxidant that reacts with the sample under controlled
* Approved by Standard Methods Committee, 1997.
conditions. The quantity of oxidant consumed is expressed in Joint Task Group: 20th EditionClarence G. Johnson (chair), Donald G. Miller,
terms of its oxygen equivalence. Because of its unique chemical John T. Pivinski.
properties, the dichromate ion (Cr2O72) is the specified oxidant in The most common interferent is the chloride ion. Chloride
Methods 5220B, C, and D; it is reduced to the chromic ion (Cr 3) reacts with silver ion to precipitate silver chloride, and thus
in these tests. Both organic and inorganic components of a sample inhibits the catalytic activity of silver. Bromide, iodide, and any
are subject to oxidation, but in most cases the organic component other reagent that inactivates the silver ion can interfere similarly.
predominates and is of the greater interest. If it is desired to Such interferences are negative in that they tend to restrict the
measure either organic or inorganic COD alone, additional steps oxidizing action of the dichromate ion itself. However, under the
not described here must be taken to distinguish one from the rigorous digestion procedures for COD analyses, chloride,
other. COD is a defined test; the extent of sample oxidation can bromide, or iodide can react with dichromate to produce the
be affected by digestion time, reagent strength, and sample COD elemental form of the halogen and the chromic ion. Results then
concentration. are in error on the high side. The difficulties caused by the
COD often is used as a measurement of pollutants in presence of the chloride can be overcome largely, though not
wastewater and natural waters. Other related analytical values are completely, by complexing with mercuric sulfate (HgSO4) before
biochemical oxygen demand (BOD), total organic carbon (TOC), the refluxing procedure. Although 1 g HgSO4 is specified for 50
and total oxygen demand (TOD). In many cases it is possible to mL sample, a lesser amount may be used where sample chloride
correlate two or more of these values for a given sample. BOD is concentration is known to be less than 2000 mg/L, as long as a
a measure of oxygen consumed by microorganisms under specific 10:1 weight ratio of HgSO4:Cl is maintained. Do not use the test
conditions; TOC is a measure of organic carbon in a sample; TOD for samples containing more than 2000 mg Cl/L. Techniques
is a measure of the amount of oxygen consumed by all elements designed to measure COD in saline waters are
in a sample when complete (total) oxidation is achieved. available.1,2
In a COD analysis, hazardous wastes of mercury, hexavalent Halide interferences may be removed by precipitation with
chromium, sulfuric acid, silver, and acids are generated. Methods silver ion and filtration before digestion. This approach may
5220C and D reduce these waste problems but may be less introduce substantial errors due to the occlusion and carrydown
accurate and less representative. (See 2 below.) of COD matter from heterogenous samples.
Ammonia and its derivatives, in the waste or generated from
1. Selection of Method
nitrogen-containing organic matter, are not oxidized. However,
The open reflux method (B) is suitable for a wide range of elemental chlorine reacts with these compounds. Hence,
wastes where a large sample size is preferred. The closed reflux corrections for chloride interferences are difficult.
methods (C and D) are more economical in the use of metallic salt Nitrite (NO2) exerts a COD of 1.1 mg O2/mg NO2-N. Because
reagents and generate smaller quantities of hazardous waste, but concentrations of NO2 in waters rarely exceed 1 or 2 mg NO2-
require homogenization of samples containing suspended solids N/L, the interference is considered insignificant and usually is
to obtain reproducible results. Ampules and culture tubes with ignored. To eliminate a significant interference due to NO 2, add
premeasured reagents are available commercially. Measurements 10 mg sulfamic acid for each mg NO2-N present in the sample
of sample volumes as well as reagent volumes and concentrations volume used; add the same amount of sulfamic acid to the reflux
are critical. Consequently, obtain specifications as to limits of vessel containing the distilled water blank.
error for premixed reagents from manufacturer before use. Reduced inorganic species such as ferrous iron, sulfide,
Determine COD values of 50 mg O2/L by using procedures manganous manganese, etc., are oxidized quantitatively under the
5220B.4a, C.4, or D.4. Use procedure 5220B.4b to determine, test conditions. For samples containing significant levels of these
with lesser accuracy, COD values from 5 to 50 mg O2/L. species, stoichiometric oxidation can be assumed from known
initial concentration of the interfering species and corrections can
2. Interferences and Limitations be made to the COD value obtained.
The silver, hexavalent chromium, and mercury salts used in the
Oxidation of most organic compounds is 95 to 100% of the COD determinations create hazardous wastes. The greatest
theoretical value. Pyridine and related compounds resist problem is in the use of mercury. If the chloride contribution to
oxidation and volatile organic compounds will react in proportion COD is negligible, HgSO4 can be omitted. Smaller sample sizes
to their contact with the oxidant. Straight-chain aliphatic (see 5220C and D) reduce the waste. Recovery of the waste
compounds are oxidized more effectively in the presence of a material may be feasible if allowed by regulatory authority. 3
silver sulfate catalyst.
3. Sampling and Storage dilutions for wastes containing a high COD to reduce the error
inherent in measuring small sample volumes.
Preferably collect samples in glass bottles. Test unstable
4. References
samples without delay. If delay before analysis is unavoidable, 2. BAUMANN, F.I. 1974. Dichromate reflux chemical oxygen demand: A
preserve sample by acidification to pH 2 using conc H2SO4. proposed method for chloride correction in highly saline waters. Anal.
Blend (homogenize) all samples containing suspended solids Chem. 46:1336.
before analysis. If COD is to be related to BOD, TOC, etc., ensure 3. HOLM, T.R. 1996. Treatment of Spent Chemical Oxygen Demand
CHEMICAL OXYGEN DEMAND (COD) (5220)/Open Reflux Method
1. BURNS, E.R. & C. MARSHALL. 1965. Correction for chloride
interference in the chemical oxygen demand test. J. Water Pollut.
Control Fed. 37:1716.
a. Treatment of samples with COD of 50 mg O 2/L: Blend remaining sulfuric acid reagent (70 mL) through open end of
sample if necessary and pipet 50.00 mL into a 500-mL refluxing condenser. Continue swirling and mixing while adding sulfuric
flask. For samples with a COD of 900 mg O2/L, use a smaller acid reagent. CAUTION: Mix reflux mixture thoroughly before
portion diluted to 50.00 mL. Add 1 g HgSO4, several glass beads, applying heat to prevent local heating of flask bottom and a
and very slowly add 5.0 mL sulfuric acid reagent, with mixing to possible blowout of flask contents.
dissolve HgSO4. Cool while mixing to avoid possible loss of Cover open end of condenser with a small beaker to prevent
volatile materials. Add 25.00 mL 0.04167M K2Cr2O7 solution and
mix. Attach flask to condenser and turn on cooling water. Add
* GFS Chemicals, Inc., Columbus, OH, or equivalent.
4. Procedure
2. Apparatus
Wash culture tubes and caps with 20% H2SO4 before first use
a. Digestion vessels: Preferably use borosilicate culture tubes, to prevent contamination. Refer to Table 5220:I for proper sample
16- 100-mm, 20- 150-mm, or 25- 150-mm, with and reagent volumes. Make volumetric measurements as accurate
TFElined screw caps. Alternatively, use borosilicate ampules, 10- as practical; use Class A volumetric ware. The most critical
mL capacity, 19- to 20-mm diam. volumes are of the sample and digestion solution. Use a
Digestion vessels with premixed reagents and other accessories microburet for titrations. Measure H2SO4 to 0.1 mL. The use of
are available from commercial suppliers. Contact supplier for hand-held pipettors with non-wetting (polyethylene) pipet tips is
specifications.* practical and adequate. Place sample in culture tube or ampule
b. Block heater or similar device to operate at 150 2C, with and add digestion solution. Carefully run sulfuric acid reagent
holes to accommodate digestion vessels. Use of culture tubes down inside of vessel so an acid layer is formed under the sample-
probably requires the caps to be outside the vessel to protect caps digestion solution layer. Tightly cap tubes or seal ampules, and
from heat. CAUTION: Do not use an oven because of invert each several times to mix completely. C AUTION: Wear face
shield and protect hands from heat produced when contents of
vessels are mixed. Mix thoroughly before applying heat to prevent
* Hach Co., Bioscience, Inc., or equivalent. local heating of vessel bottom and possible explosive reaction.
CHEMICAL OXYGEN DEMAND (COD) (5220)/Closed Reflux, Titrimetric Method
the possibility of leaking samples generating a corrosive and Place tubes or ampules in block digester preheated to 150C
possibly explosive atmosphere. Also, culture tube caps may not and reflux for 2 h behind a protective shield. C AUTION: These
withstand the 150C temperature in an oven. sealed vessels may be under pressure from gases generated
c. Microburet. during digestion. Wear face and hand protection when handling.
d. Ampule sealer: Use only a mechanical sealer to insure If sulfuric acid is omitted or reduced in concentration, very high
strong, consistent seals. TABLE 5220:I. SAMPLE AND REAGENT QUANTITIES FOR VARIOUS DIGESTION
VESSELS
3. Reagents Sulfuric Total
Acid Final
Digestion
Reagent Volume
a. Standard potassium dichromate digestion solution, Sample Solution
mL mL
0.01667M: Add to about 500 mL distilled water 4.903 g Digestion Vessel mL mL
K2Cr2O7, primary standard grade, previously dried at 150C for
Culture tubes:
2 h, 167 mL conc H2SO4, and 33.3 g HgSO4. Dissolve, cool to 16100 mm 2.50 1.50 3.5 7.5
room temperature, and dilute to 1000 mL.
20150 mm 5.00 3.00 7.0 15.0
b. Sulfuric acid reagent: See Section 5220B.3b.
25150 mm 10.00 6.00 14.0 30.0
c. Ferroin indicator solution: See Section 5220B.3c.
Dilute Standard 10-mL
ampules 2.50 1.50 3.5 7.5
this reagent by a factor of 5 (1 4).
d. Standard ferrous ammonium sulfate titrant (FAS), and dangerous pressures will be generated at 150C. Cool to
approximately 0.10M: Dissolve 39.2 g Fe(NH4)2(SO4)2 6H2O room temperature and place vessels in test tube rack. Some
in distilled water. Add 20 mL conc H2SO4, cool, and dilute to mercuric sulfate may precipitate out but this will not affect the
1000 mL. Standardize solution daily against standard K2Cr2O7 analysis. Remove culture tube caps and add small TFE-covered
digestion solution as follows: magnetic stirring bar. If ampules are used, transfer contents to a
Pipet 5.00 mL digestion solution into a small beaker. Add 10 larger container for titrating. Add 0.05 to 0.10 mL (1 to 2 drops)
ferroin indicator and stir rapidly on magnetic stirrer while titrating
mL reagent water to substitute for sample. Cool to room
temperature. Add 1 to 2 drops diluted ferroin indicator and titrate with standardized 0.10M FAS. The end point is a sharp color
change from blue-green to reddish brown, although the bluegreen
with FAS titrant.
may reappear within minutes. In the same manner reflux and
AGGREGATE ORGANIC CONSTITUENTS (5000)
titrate a blank containing the reagents and a volume of distilled For this procedure to be applicable, all visible light-absorbing
water equal to that of the sample. interferents must be absent or be compensated for. This includes
insoluble suspended matter as well as colored components. If
either type of interference occurs, the test is not necessarily lost
5. Calculation because COD can be determined titrimetrically as in 5220C.
2. Apparatus
(AB) M 8000
COD as mg O2/L mL a. See Section 5220C.2. Ensure that reaction vessels are
sample
ofoptical quality. Other types of absorption cells with varying
path lengths may be used. Use the extinction coefficients of the
where: ions of interest for this approach.
A mL FAS used for blank, b. Spectrophotometer, for use at 600 nm and/or 420 nm
B mL FAS used for sample, with access opening adapter for ampule or 16-, 20-, or 25-mm
M molarity of FAS, and tubes. Verify that the instrument operates in the region of 420 nm
8000 milliequivalent weight of oxygen1000 mL/L. and 600 nm. Values slightly different from these may be found,
depending on the spectral bandpass of the instrument.
Preferably analyze samples in duplicate because of small
sample size. Samples that are inhomogeneous may require 3. Reagents
multiple determinations for accurate analysis. Results should
agree within 5% of their average unless the condition of the a. Digestion solution, high range: Add to about 500 mL
sample dictates otherwise. distilled water 10.216 g K2Cr2O7, primary standard grade,
previously dried at 150C for 2 h, 167 mL conc H 2SO4, and 33.3
g HgSO4. Dissolve, cool to room temperature, and dilute to 1000
6. Precision and Bias
mL.
b. Digestion solution, low range: Prepare as in 3a, but use
Sixty synthetic samples containing potassium hydrogen only 1.022 g potassium dichromate.
phthalate and NaCl were tested by six laboratories. At an average
c. Sulfuric acid reagent: See Section 5220B.3b.
COD of 195 mg O2/L in the absence of chloride, the standard
d. Sulfamic acid: See Section 5220B.3f.
deviation was 11 mg O2/L (coefficient of variation, 5.6%). At an
e. Potassium hydrogen phthalate standard: See Section
average COD of 208 mg O2/L and 100 mg Cl/L, the standard
5220B.3g.
deviation was 10 mg O2/L (coefficient of variation, 4.8%).
5220 D. Closed Reflux, Colorimetric Method
1. General Discussion 4. Procedure
a. Principle: See Section 5220B.1a. When a sample is a. Treatment of samples: Measure suitable volume of
digested, the dichromate ion oxidizes COD material in the sample and reagents into tube or ampule as indicated in Table
sample. This results in the change of chromium from the 5220:I.
hexavalent (VI) state to the trivalent (III) state. Both of these Prepare, digest, and cool samples, blank, and one or more
chromium species are colored and absorb in the visible region of standards as directed in Section 5220C.4. Note the safety
the spectrum. The dichromate ion (Cr2O72) absorbs strongly in precautions. It is critical that the volume of each component be
the 400-nm region, where the chromic ion (Cr3) absorption is known and that the total volume be the same for each reaction
much less. The chromic ion absorbs strongly in the 600-nm vessel. If volumetric control is difficult, transfer digested sample,
region, where the dichromate has nearly zero absorption. In 9M dilute to a known volume, and read. Premixed reagents in
sulfuric acid solution, the approximate molar extinction digestion tubes are available commercially.
coefficients for these chromium species are as follows: Cr3 50 b. Measurement of dichromate reduction: Cool sample to
L/mole cm at 604 nm; Cr2O72 380 L/mole cm at 444 nm; Cr3 25 room temperature slowly to avoid precipitate formation. Once
L/mole cm at 426 nm. The Cr3 ion has a minimum in the region samples are cooled, vent, if necessary, to relieve any pressure
of 400 nm. Thus a working absorption maximum is at 420 nm. generated during digestion. Mix contents of reaction vessels to
For COD values between 100 and 900 mg/L, increase in Cr 3 in combine condensed water and dislodge insoluble matter. Let
the 600-nm region is determined. Higher values can be obtained suspended matter settle and ensure that optical path is clear.
by sample dilution. COD values of 90 mg/L or less can be Measure absorption of each sample blank and standard at selected
determined by following the decrease in Cr2O72 at 420 nm. The wavelength (420 nm or 600 nm). At 600 nm, use an undigested
corresponding generation of Cr3 gives a small absorption increase blank as reference solution. Analyze a digested blank to confirm
at 420 nm, but this is compensated for in the calibration good analytical reagents and to determine the blank COD;
procedure. subtract blank COD from sample COD. Alternately, use digested
b. Interferences and limitations: See Section 5220C.1b. blank as the reference solution once it is established that the blank
has a low COD.
At 420 nm, use reagent water as a reference solution. Measure of water. D1252-95, ASTM Annual Book of Standards. American
all samples, blanks, and standards against this solution. The Soc. Testing & Materials, Philadelphia, Pa.
absorption measurement of an undigested blank containing
dichromate, with reagent water replacing sample, will give initial 8. Bibliography
dichromate absorption. Any digested sample, blank, or standard
JIRKA, A.M. & M.J. CARTER. 1975. Micro semi-automated analysis of
that has a COD value will give lower absorbance because of the
surface and wastewaters for chemical oxygen demand. Anal. Chem.
decrease in dichromate ion. Analyze a digested blank with
47:1397.
reagent water replacing sample to ensure reagent quality and to
HIMEBAUGH, R.R. & M.J. SMITH. 1979. Semi-micro tube method for
determine the reagents contribution to the decrease in chemical oxygen demand. Anal. Chem. 51:1085.
absorbance during a given digestion. The difference between
absorbances of a given digested sample and the digested blank is
a measure of the sample COD. When standards are run, plot
differences of digested blank absorbance and digested standard
absorbance versus COD values for each standard.
c. Preparation of calibration curve: Prepare at least five
standards from potassium hydrogen phthalate solution with COD
equivalents to cover each concentration range. Make up to
volume with reagent water; use same reagent volumes, tube, or
ampule size, and digestion procedure as for samples. Prepare
calibration curve for each new lot of tubes or ampules or when
standards prepared in 4a differ by 5% from calibration curve.
Curves should be linear. However, some nonlinearity may occur,
depending on instrument used and overall accuracy needed.
5. Calculation
mg O2 in final volume
1000 COD as mg O2/L
mL sample