College of Natural and Computational

Science
Center for Environmental Science
Seminar III

Advances in the Determination of Chemical Oxygen Demand (COD)

Dawit Firemichael

November, 2019
Addis Ababa, Ethiopia
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 Outline

 Introduction

 Classical way of determination of COD

 Contemporary approach of COD determination
 Modified standard methods

 New technology or method

 Conclusion and future perspective

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 Introduction
• Water is the source of life. The survival and production of people
cannot go on without continuous water supply.

However, approximately 80% of wastewater

worldwide remains uncollected and
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 Con’t…
• The most relevant pollution impact of wastewater is organic
matter.

• The pollution level of organic matter in water bodies is

roughly predicted by analyzing chemical oxygen demand
(COD) or biological oxygen demand (BOD)
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 Con’t…
• COD is defined as a measure of the oxygen equivalent of the organic matter
content of a sample susceptible to oxidation by strong chemical oxidants.

• Conventionally, COD indexes have two types, namely CODCr and CODMn.

• Determining COD using K2Cr2O7 and KMnO4 is called CODCr and CODMn

respectively.

• CODCr is mainly used for assessing the water quality in moderately or

heavily contaminated water bodies (e.g., sewage and wastewater), and

• CODMn is preferred in relatively clean water bodies (e.g., surface water and

river water) with low-level COD values.

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 Con’t…
• The standard methods for COD determination are widely

adopted by numerous industries, such as environmental

monitoring and wastewater treatment, etc., conventionally.

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 Conventional methods for COD determination

The reaction of KHP by K2Cr2O7 is as follows:

2KC8H5O4+ 10K2Cr2O7+ 41H2SO4 16CO2 + 46H2O +10Cr2(SO4)3 + 11K2SO4

when K2Cr2O7 is substituted by O2, the equation becomes:

2KC8H5O4 + 15O2+ H2SO4 16CO2 + 6H2O + K2SO4

After digestion, the remaining unreduced dichromate is determined by

potentiometric titration using a Fe2+ solution according to the following equation:

Cr2O72- + 6Fe2+ +14H+ 2Cr3+ + 6Fe3+ + 7H2O

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 Con’t…
• The two types of standard methods :
Standard Application Sample time Used reagents Range Cl Conc.
no. scope amount (h) (mg L-1) range
(mL) (mg L-1)
ISO 6060- Water 10.0 2 0.040 mol/L K2Cr2O7 30-700 ˂1000
1989 15 mL AgSO4-H2SO4
0.4 g HgSO4
ISO Domestic 2.0 2 0.10 mol/L K2Cr2O7 6–1,000 ˂1000
15705- sewage & 0.0385 mol/L AgSO4
2002 Industrial
wastewater 15-1,000
1.8 mol/L,4 mol/LH2SO4
1.35 mol/L HgSO4

However, both methods show some limitations, including a long reflux time, high
cost of chemical reagents, similar concentration range of chloride ion (Cl -)
interference, and usage of toxic reagents. Moreover, the two approaches
demonstrate inappropriateness for the online monitoring.

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 Modified standard methods
• There are modified standard methods are propased based on
reflux digestion and K2Cr2O7 titration or sealed digestion and
spectrometry.
 Improved digestion methods,

 Alternative methods of digestion reagents,

 Optimized spectrophotometric methods, and
 Optimized detection methods prevailing over chloride
interference

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 Con’t…
• C.E. Domini et al. 2006, “ Comparison of three optimized digestion
methods for rapid determination of chemical oxygen demand: Closed
microwaves, open microwaves and ultrasound irradiation ”
• Mean COD recoveries obtained with the optimized digestion methods
applied to the RMs

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• Comparison between the COD values and their relative standard deviations
for several organic compounds using the assisted digestion methods and the
reference method.

• The recovery values are in the range of 95–100, 68–101, 71–99 and 77–
100% for classical, closed microwaves, open microwaves and ultrasound-
assisted digestion methods, respectively.
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 • Mean COD recoveries obtained with the optimized digestion methods
applied to real samples

• CMWD: 90 psi pressure, 475 W power and 4 min irradiation time

• OMWD: 150 0C temperature and 4 min irradiation time
• USD: 90% of power (180 W), 0.9-s pulses /second and 1 min irradiation time
• The most striking conclusion of this work is the experimental proof of usefulness of
ultrasound radiation for fast and efficient sample preparation for COD determination.

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 Con’t…

• DG. Miller et al., 2001 “Chemical Oxygen Demand Analysis of

Wastewater Using Trivalent Manganese Oxidant with Chloride
Removal by Sodium Bismuthate Pretreatment”.

2KMnO4 + 8MnSO4 + 8H2SO4 5Mn2(SO4)3 + K2SO4 + 8H2O

2Mn3+ Mn2+ + Mn4+

The oxidation potential of the half-reactions:
– manganese(III)–manganese(II) is 1.541 E°/V,

– permanganate (VII)–permanganate (II) is 1.507 E°/V

– Chromium (VI)– Chromium (III) is 1.350 E°/V

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 Con’t…
• After testing multiple oxidants, solid
sodium bismuthate in dilute sulfuric
acid was found to oxidize chloride to
chlorine rapidly and at room
temperature, without significantly
affecting most organic compounds.

2Cl- + Bi5+ Cl2 + Bi3+

• Manganese(III) has a broad absorbance peak

with a single maximum at 510 nm that lends
itself readily to photometric analysis.
• The permanganate scan shows multiple peaks
and shoulders between approximately 480
and 580 nm.

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 Con’t…
• This method is rapid, simple, and economical.
Chloride removal is effective at and above the
levels found in most COD samples.
• Test results correlate well with those of current
dichromate COD tests and can be used to predict
COD values for defined wastewater streams.

Table 1: Manganese(III) and dichromate COD results with selected organic compounds. a

Paired t-test (@ 95% CI)

Tcrtical = 1.79
Ttable = 2.26
The null hypothesis was
accepted.

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 New technologies or methods

• Recently, several techniques have also been employed for

COD measurement in water bodies
 CL methods
 FIA methods

 Ozone oxidation technique

 Combination of several techniques

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 Con’t…
• X. Yu et al. 2016 , “Determination of Chemical Oxygen
Demand Using UV/O3”

• Basic principle :

O3 + H2O hv H202 + O2
H2O2 hv 2OH.
O3 + H2O2 HO2. + OH. + O2

Fig. 1: Schematics of the UV/O3 COD measurement system

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 Con’t…
• The COD value (ppm) depends on O3 consumption as the
following function:

Calibration curve of UV
absorption of indigo solution
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 Con’t…
• the complete digestion time of organic matter can since be determined by

analyzing the evolution of CO2 during the process.

(R2= 0.991)

Evolution of CO2 concentration

Calibration curve for COD calculation

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 Con’t…
Comparison of methods published for COD determination

In summary,
• This method uses UV/O3 treatment instead of toxic chemicals for organic

species digestion and amount of consumed O3 is used for determining COD

value.
• In addition, the complete digestion time of organic matter can be monitored
by measuring generated CO2concentration.
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 Con’t…
• H. Yao et al., 2009 “A high throughput chemiluminescence
method for determination of chemical oxygen demand in
waters”

16MnO4−+5C5H8O2+48H+→ 5Mn(II)∗+25CO2+24H2O

Mn(II)∗→ Mn(II) +hv ( λ= 640 nm) ∆I = Ia− Ib

CL kinetic curve of
KMnO4–glutaraldehyde

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 Con’t…
• Correlation between the ∆I and the theoretical COD.
1. D-glucose
2. Citric acid
3. Na2C2O
4. Malonic acid
5. Succinic acid
6. Glutaric acid
7. Glycine
8. Mixture of compounds 1–8 with equal COD concentration of each;
9. The linear fit for all data from 1–8 (error bands calculated for a
confidential level of 95%).
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 Con’t…
• Correlation between the CL COD and the standard permanganate COD methods
for the real sample measurements

• The presented CL method agreed very

well with the standard titrimetric
method.
• Therefore, CL method is suitable to the
COD determination of water sample.

• Recoveries in COD values with spike test (mean ± SD, n = 3)

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 Con’t…
• H. Hue et al., 2017 “3-step Chemiluminescence Method for
Chemical Oxygen Demand Measurement”
• Due to the complexity of organic pollutants present in water
body , there are no standard for the 1-step CL COD method.
• Many organic compounds also give no signal in 1-step CL
COD methods.
• Generally, the difference in the oxidation yield of the CODMn
method for different organic compounds is b/c of the
difference in the chemical structure

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 Con’t…
• The main difference b/n the CODMn method and the 1-step CL COD
method is the reaction time (30 min versus approx. 4 s).

♦ : Pyrogallol
■ : Itaconic
▲ : Gallic
X : Salicylate
+ : Fumaric acid
◊ : Phenol
* : Oxic acid

Correlation b/n CL COD method and CODMn method

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 Con’t…
• Principle of 3- step CL COD method is based on flow injection analysis
and the process that resembles the back titration process.
1-step : organic mater in the sample is oxidized by excess amount of permanganate
reagent under heating
2- step : the remaining permanganate is neutralized by pyrogallol which used as
standard reagent
3- step : the remaining pyrogallol is detected by permanganate CL reaction using photodiode
detector
S : Sample
D.I : deionized water
RC1, RC2 & RC3 : reaction coils
R1, R2 : permanganate solution
T : T-shaped connector
P1, P2 : peristaltic pump
I : flow injection set
DG : degasser
CD : CL detector
W : waste solution
Pyro : pyrogallol

Schematic diagram of the instrument manifold for 3-step CL COD method

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 Con’t…
• CL detector

(a) spiral cell of CL detector

(b) mixing point of CL detector
T : T-shaped connector
I1, I2: in let ports
O : out let port
C : reaction cell
G: transparent pyrex glass
(c) CL detector
1 & 6 : upper & lower
holder
2 : photodiode detector
3 : O-ring rubber
4 : transparent Pyrex glass
5 reaction cell (Teflon)

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 Con’t…

• Optimization of different
variable

Conclusion:
• The 3-step CL COD method is applicable
for the measurement of real sample and
successful in obtaining signal from some
sample detected by 1-step CL method.
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 Summery and future perspective
• This review has identified the main technological strategies of COD measurement,
which is used as an indicator of the degradability of organic matter in water bodies.

• In an attempt to increase the oxidation efficiency, reduce the analytical time, and
avoid environmental pollution, different alternative methods have been investigated
and reviewed.

• These methods mainly include the following: modified standard methods and new
technologies or methods.

• To overcome the shortcomings of the traditional methods, the improved and

optimized methods extending their detection limit, significantly shorten their
detection time, and decrease their detection cost.

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 Con’t…
• However, the environmental pollution caused by chemical reagents could
not be avoided, and the oxidation ability to the refractory organics was
insufficient.
• FIA, CL, or a combination of several techniques have also been employed
to determine COD in water bodies. Low detection limit could be achieved,
detection time could be shortened again, and environmental pollution
caused by the reagents could be dramatically reduced.
• Nevertheless, the reliability, cost and stability of these new technologies
still depend on the advance of new theories and techniques. A substantial
amount of effort should be devoted to improving the development space of
high COD concentration determination in wastewater samples.

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 Con’t…
Our hypothesis

a. injection zone
b. reaction zone 1
c. Reaction zone 2
d. waste zone

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 Thank you for your attention !!

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