You are on page 1of 55

CHEMICAL OXYGEN DEMAND

Training-Workshop in Wastewater Analysis RLC Laboratory, Robinsons Place Manila, Ermita , Manila September 17 21, 2012

by Diana C. Galicia

Chemical Oxygen Demand


The Chemical Oxygen Demand (COD) test is used to measure the oxygen equivalent of the amount of organic matter content of both wastewater and natural waters oxidizable by a strong chemical oxidizing agent in an acidic medium.

RLC LAB "Training-Workshop in Wastewater Analysis 2012"

Lets review

Oxidation Reduction Process


RLC LAB "Training-Workshop in Wastewater Analysis 2012" 3

RLC LAB "Training-Workshop in Wastewater Analysis 2012"

The Oxidation-Reduction Process


An oxidation-reduction (or redox) reaction is said to occur if the reactants undergo a change in oxidation.

Oxidation describes an increase in oxidation


number, a process resulting from a loss of electrons.

Reduction describes a decrease gain in oxidation


number, a process resulting from a gain of electrons

RLC LAB "Training-Workshop in Wastewater Analysis 2012"

The Oxidation-Reduction Process


Oxidizing Agent or Oxidant the substance causing the oxidation.
Reducing Agent or Reductant the substance causing the reduction

RLC LAB "Training-Workshop in Wastewater Analysis 2012"

The Oxidation-Reduction Process


To cause an oxidation, the oxidizing agent must take one or more electrons from the substance being oxidized. As a result, the oxidizing agent is reduced. Conversely, a reducing agent is oxidized in a chemical reaction.

RLC LAB "Training-Workshop in Wastewater Analysis 2012"

The Oxidation-Reduction Process


2Fe3+
Oxidizing agent

Sn2+ Sn4+
Reducing agent

2Fe2+

Half Reaction: Reduction : Fe3+ + e Fe2+ Oxidation : Sn2+ Sn4+ + 2e


RLC LAB "Training-Workshop in Wastewater Analysis 2012" 8

Oxidant
Because of its unique chemical properties, Potassium dichromate (K2Cr2O7) is the specified oxidizing agent in the Standard Methods for the Examination of Water and Wastewater.

RLC LAB "Training-Workshop in Wastewater Analysis 2012"

Advantages of Using Potassium Dichromate as Oxidant


Stability Acidic solutions of potassium
dichromate are exceptionally stable. Even boiling for a long periods of time does not measurably alter their concentrations (assuming the evaporated water is replaced). Preparation and Storage Potassium dichromate is available in primary- standardgrade purity and dissolve readily in water and dilute acid. No special precautions need to be observed in storing solutions of this oxidant
RLC LAB "Training-Workshop in Wastewater Analysis 2012" 10

Advantages of Using Potassium Dichromate as Oxidant


Preparation and Storage Potassium dichromate is available in primary- standardgrade purity and dissolve readily in water and dilute acid.
No special precautions need to be observed in storing solutions of this oxidant

RLC LAB "Training-Workshop in Wastewater Analysis 2012"

11

Selection of Method

Open-Reflux Method
This method is suitable for wastes where large sample size is preferred.

A sample is reflux in strongly acidic solution for with a known excess of K2Cr2O7 for 2 hours after which the remaining unreduced K2Cr2O7 is titrated with ferrous ammonium sulfate
RLC LAB "Training-Workshop in Wastewater Analysis 2012" 12

Selection of Method

Closed Reflux Method


More economical in the use of metallic salt reagents and generate smaller quantities of hazardous waste, but require homogenization of samples containing suspended solids to obtain reproducible results.
Volatile organic compounds are more completely oxidized in the closed system because of longer contact with the oxidant.
RLC LAB "Training-Workshop in Wastewater Analysis 2012" 13

Selection of Method

Closed Reflux Method 1. Titrimetric Method This procedure is applicable to COD values between 40 and 400 mg/L. The sample is place in a tube or ampules and digested in a block heater with holes at 150+ 2C. After digestion, the sample is transferred to a beaker for titration
RLC LAB "Training-Workshop in Wastewater Analysis 2012" 14

Selection of Method

Closed Reflux Method 2. Colorimetric Method During digestion, the chromium changes from the hexavalent (VI) state to the trivalent (III) state. Both of these species are colored and absorb in the visible region of the spectrum.
RLC LAB "Training-Workshop in Wastewater Analysis 2012"

15

Selection of Method
2. Colorimetric Method

Dichromate ion (Cr2O72-) absorbs strongly in the 400-nm region Chromic ion (Cr3+) absorbs strongly in the 600-nm region

RLC LAB "Training-Workshop in Wastewater Analysis 2012"

16

Selection of Method
2. Colorimetric Method

COD values of 90 mg/L or less is determined by following the decrease in Cr2O72- at the maximum working absorption of 420 nm. COD values between 100 and 900 mg/L, increase in Cr3+ in the 600-nm region is determined.
RLC LAB "Training-Workshop in Wastewater Analysis 2012" 17

Selection of Method
2.Colorimetric Method The dichromate ion (Cr2O72-) absorbs strongly in the 400-nm region, whereas the chromic ion (Cr3+) absorption is much less. The chromic ion (Cr3+) absorbs strongly in the 600-nm region , whereas the dichromate has nearly zero absorption.

RLC LAB "Training-Workshop in Wastewater Analysis 2012"

18

Interferences and Limitations


The most common interferent is the chloride ion. Chloride reacts with silver ion to precipitate silver chloride, and thus inhibits the catalytic activity of silver. Bromide, iodide and any other reagent that inactivates the silver ion can interfere similarly as chloride ion.

RLC LAB "Training-Workshop in Wastewater Analysis 2012"

19

Interferences and Limitations


Reduced inorganic species such as ferrous iron, sulfide, manganous manganese, etc. are oxidized quantitatively under the test conditions.

For samples containing significant levels of these species, stoichiometric oxidation can be assumed from a known initial concentration of the interfering species and correction can be made to the COD value obtained.
RLC LAB "Training-Workshop in Wastewater Analysis 2012" 20

Interferences and Limitations


Ammonia and its derivatives, in the waste or generated from nitrogen-containing organic matter, are not oxidized. However, elemental chlorine reacts with these compound. Hence, corrections for chloride interferences are difficult.

RLC LAB "Training-Workshop in Wastewater Analysis 2012"

21

Interferences and Limitations


Nitrite (NO2) exerts COD of 1.1 mg O2/mg NO2-N. Because concentrations of NO2 in water rarely exceed 1 or 2 mg NO2-N/L, the interference is considered insignificant and usually ignored. To eliminate significant interference due to NO2, 10 mg of sulfamic acid is added for each mg NO2-N present in the sample volume used.
RLC LAB "Training-Workshop in Wastewater Analysis 2012" 22

Sampling and Storage


Preferably, samples are collected in glass bottles. Unstable samples should be analyzed without delay. If delay is unavoidable, sample is preserved by acidification to pH< 2 using concentrated H2SO4. Blend (homogenize) all samples containing suspended solids before analysis.
RLC LAB "Training-Workshop in Wastewater Analysis 2012" 23

Open Reflux Method


Apparatus
1.

Reflux apparatus Consisting of 250-ml erlenmeyer flask with ground-glass 24/40 neck and 300mm jacket Liebig West condensers with 24/40 ground-glass joint, and a hot plate.

RLC LAB "Training-Workshop in Wastewater Analysis 2012"

24

Reflux Apparatus
Iron stand Condenser Clamp Rubber Tubing

Ground joint Erlenmeyer flask

Hot Plate

RLC LAB "Training-Workshop in Wastewater Analysis 2012"

25

Open Reflux Method


2.
3. 4. 5. 6.

Apparatus Blender Pipets, Class A, wide-bore Digital burette Analytical balance Acid Dispenser

RLC LAB "Training-Workshop in Wastewater Analysis 2012"

26

Reagents
Standard Potassium dichromate solution, 0.04167M This reagent undergoes a six-electron reduction reaction, thus the equivalent concentration is 6 x 0.04167M = 0.2500N
RLC LAB "Training-Workshop in Wastewater Analysis 2012" 27

Reagents
Sulfuric acid reagent A mixture of reagent grade Ag2SO4 and concentrated H2SO4 at the rate of 5.5g Ag2SO4 /kg H2SO4. Silver sulfate acts as a catalyst. Straightchain aliphatic compounds are oxidized effectively in the presence of silver sulfate.
RLC LAB "Training-Workshop in Wastewater Analysis 2012" 28

Reagents
Ferroin indicator solution Tris(1,10-phenanthroline)iron(II) This complex is an iron (II) chelate. Three bidentate 1-10, phenanthroline ligands coordinate to a ferrous ion, giving the formula:
RLC LAB "Training-Workshop in Wastewater Analysis 2012" 29

Ferroin indicator solution


Tris(1,10-phenanthroline)iron(II)
N Fe N

or Fe(phen)3 2+

RLC LAB "Training-Workshop in Wastewater Analysis 2012"

30

Ferroin Indicator Solution


This complex ion undergoes a reversible redox reaction represented by Fe(phen)33+ + e Fe(phen)32+ E=1.06V
ferriin(pale blue) ferroin(red)

RLC LAB "Training-Workshop in Wastewater Analysis 2012"

31

Ferroin Indicator Solution


Because the color of the iron (III) complex is quite pale, only about 10% of the indicator needs to be in the iron (II) form for the solution to appear completely red. As a result, an end point based on the formation of a red color occurs at a potential of about 1.11V in 1M H2SO4.

RLC LAB "Training-Workshop in Wastewater Analysis 2012"

32

Ferroin Indicator Solution


Advantages of using Ferroin The most nearly ideal nonspecific redox indicator. Color change is very sharp and noticeable. Its solutions is easy to prepare and very stable. The indicator reaction is usually fast and reversible.
RLC LAB "Training-Workshop in Wastewater Analysis 2012" 33

Standard ferrous ammonium sulfate (FAS) titrant Fe(NH4)2(SO4)26H2O Also known as Mohrs salt.
In titrations, FAS undergoes a simple one electron oxidation to ferric ion.

Reagents

Fe3+ + e Fe2+

E=0.77V

The fairly large E means that Fe2+ is a weak reducing agent


RLC LAB "Training-Workshop in Wastewater Analysis 2012" 34

Stability The atmospheric oxidation of ferrous ion is quite rapid in neutral solution but slow considerably as the acidity is increased. Preparation and Storage Reagents are available in primary standard-grade purity, and dissolves readily in acidic solution to yield Fe2+ . FAS should not be oven dried as it decomposes on heating.
RLC LAB "Training-Workshop in Wastewater Analysis 2012" 35

FAS

Standardization FAS titrant is standardized against standard K2Cr2O7 solution.


1. 2. 3.

FAS

Dilute 10 ml K2Cr2O7 to 100 ml. Add 30 ml concentrated sulfuric acid and cool. Titrate with FAS using 0.10 to 0.15 ml (2 to 3 drops) ferroin indicator.

RLC LAB "Training-Workshop in Wastewater Analysis 2012"

36

Reagents
Mercuric sulfate, HgSO4, crystals or powder Mercuric sulfate is added to the sample before digestion for complexing the chloride ion that interferes with the test. Mercury salts used in the COD determination creates hazardous waste and should be contained and treated correctly.
RLC LAB "Training-Workshop in Wastewater Analysis 2012" 37

Reagents
Sulfamic acid required only if the interference of nitrite is to be eliminated. Potassium hydrogen phthalate (KHP) standard HOOCC6H4COOK

KHP has a theoretical COD of 1.176 mg O2/mg. This solution is stable when refrigerated, but only for approximately one week. Check for visible biological growth before use.
RLC LAB "Training-Workshop in Wastewater Analysis 2012" 38

Treatment of Samples
COD of >50 mg O2/L: Blend samples if total suspended solids is present and pipette 20 ml into 250-ml refluxing flask. COD of >900mg O2/L: Use smaller sample volume diluted to 20 ml.

RLC LAB "Training-Workshop in Wastewater Analysis 2012"

39

Procedure
1.

2.

Weigh approximately 0.4 g HgSO4 and transfer to Erlenmeyer flask. Add appropriate sample volume to the flasks. Run blank and QC standard together with the sample.
RLC LAB "Training-Workshop in Wastewater Analysis 2012" 40

Procedure
3.

4.

Add several glass beads, and very slowly add 5.0 ml of sulfuric acid reagent, with mixing to dissolve HgSO4. Add 10 ml of 0.25N K2Cr2O7 solution and mix.

RLC LAB "Training-Workshop in Wastewater Analysis 2012"

41

Procedure
4.

5.

Attach flask to condenser and turn on cooling water. Add remaining sulfuric acid reagent (30ml) through the open end of the condenser. Continue mixing and swirling while adding sulfuric acid reagent.

RLC LAB "Training-Workshop in Wastewater Analysis 2012"

42

CAUTION!!!
Mix reflux mixture thoroughly before applying heat to prevent local heating of flask bottom and a possible blowout of flask contents.

RLC LAB "Training-Workshop in Wastewater Analysis 2012"

43

Procedure
7.

Cover end of condenser with a small beaker to prevent foreign material from entering the refluxing mixture and reflux for 2 hours.
RLC LAB "Training-Workshop in Wastewater Analysis 2012" 44

Procedure
8.

Cool and wash down condenser with 40 ml DDW.

RLC LAB "Training-Workshop in Wastewater Analysis 2012"

45

Procedure
9.

Disconnect reflux condenser

RLC LAB "Training-Workshop in Wastewater Analysis 2012"

46

Procedure
10.

Dilute mixture with 50 ml DDW.

RLC LAB "Training-Workshop in Wastewater Analysis 2012"

47

Procedure
11.

Cool to room temperature and titrate excess K2Cr2O7 with FAS using 3 drops of ferroin indicator to the first sharp color change from blue-green to reddish brown as the endpoint.

RLC LAB "Training-Workshop in Wastewater Analysis 2012"

48

During the titration, the Fe2+ in the titrant reacts with the chromic ions: 3Fe2+ + Cr6+ 3Fe3+
yellow

Cr3+
green

Ferroin indicator reacts with Fe2+ but no color with Fe3+. Thus, when reduction of Cr6+ to Cr3+ is complete, Fe2+ reacts to form the ferroin complex.
RLC LAB "Training-Workshop in Wastewater Analysis 2012" 49

Procedure
For low COD sample: Use standard 0.004167M or 0.0025N K2Cr2O7. Titrate with standardized 0.025M FAS. Exercise extreme care with this procedure because even a trace or organic matter on the glassware or from the atmosphere may cause gross errors.
RLC LAB "Training-Workshop in Wastewater Analysis 2012" 50

Procedure
For low COD sample:

RLC LAB "Training-Workshop in Wastewater Analysis 2012"

51

Chemical Reactions
When oxygen is used as the primary standard oxidant in the oxidation of potassium acid pthalate, the equation below describes the reaction, KC8H5O4 + 7.5O2 8CO2 + 2H2O + KOH

RLC LAB "Training-Workshop in Wastewater Analysis 2012"

52

Seven and one-half molecules of oxygen (O2) consume one molecule of KHP. On weight basis, the theoretical oxygen demand for KHP is 1.175 mg O2 per mg KHP

RLC LAB "Training-Workshop in Wastewater Analysis 2012"

53

References

SMEWW 21st Edition. 2005. APHA, AWWA. WEF Analytical Chemistry Principles and Techniques. Hargis

RLC LAB "Training-Workshop in Wastewater Analysis 2012"

54

END
Thank you.