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Oxygen Demand
• Objective
– To know the different expressions of Oxygen Demand
and their chemical basis,
– their use in Environmental Engineering,
– and the methods of laboratory determination.
• Reference
• Sawyer C.N. et al Chemistry for
Environmental Engineers
Oxygen Demand
 Concept derives from 19th Century
 pollution of rivers with faeces, household
wastes
 ie organic wastes
 Stinking rivers, incapable of supporting fish
 Rivers devoid of oxygen
 Polluting potential expressed in terms of
– oxygen demand
Oxygen Demand is a measure of
organic carbon
 Organic pollutants complex carbon molecule
 Enormous range of organics
 Impossible to identify and quantify organics
 Oxygen consumed as bacteria consume organics
Eg Aerobic Metabolism
 Quantity of oxygen consumed is a measure of the
concentration of organics in water
Options for measuring OD
 Biochemical Oxygen Demand
 BOD
 Chemical Oxygen Demand
 COD
 Total Organic Carbon
 TOC
0
5
10
15
20
25
30
35
40
45
0 5 10 15 20 25
Time (days)
Oxygen
Demand
(mg/l)
Carbonaceous oxygen demand
Biochemical Oxygen Demand
 "Amount of oxygen required by bacteria to break down
decomposable organic matter under aerobic conditions"
Ultimate oxygen demand
BODu = L
5 Day oxygen demand
BOD5
BOD
 Bioassay
 Amount of oxygen used up under defined
conditions
 Temp 20 C
 Virtually all degradable matter oxidised in 20
days - BODu or ultimate BOD
 5 day BOD used
– BOD5 is 70-80% of the BODu
 BOD wastewater (mg/l)
– <200 weak
– 300 typical
– 1000 strong
Complications of BOD
 Conditions critical
– rigorous attention to and control of conditions
 nutrients and seed must be present
 toxins must be absent
 Theoretical BOD > BOD ultimate
– 1. not all biodegradable carbon oxidised
 E.g. BODu glucose = 85% of theoretical BOD
C6H12O6 + 6O2 6CO2 + 6H2O
– 2. not all carbon biodegradable under conditions
 sometimes called humus
 eg lignin
 Ammonia also exerts an oxygen demand
– Nitrification
 Nitrification controlled for by
– 5 day test (nitrifiers grow slowly)
– inhibitors eg Alkylthiourea (ATU), TCMP
Oxygen
Demand
25
higher oxygen demand
exerted due to nitrification
0
5
10
15
20
25
30
35
40
45
0 5 10 15 20
Time (days)
(mg/l)
Carbonaceous oxygen demand
5 Day oxygen demand
BOD5
Measuring dissolved oxygen
 Winklers Method (titration)
– Mn2+ oxidised to MnO2
Mn2+ + 2OH
-
+ 1/2 O2 MnO2 + H2O
– At low pH MnO2 oxidises Iodide
MnO2 + 2I
-
+ 4H+ Mn2+
+ I2 + 2H2O
– Care required with sampling and interference
 DO probe
– Quick simple, reliable
– Must calibrate carefully (temp sensitive)
– Probe is an electrode system covered by a PTFE coat
 Organic matter oxidised chemically (2-3 hours)
 Virtually all organic matter oxidised,
– non-biodegradable material degraded, COD > BODu
– COD correlated BOD
– E.g. raw wastewater
 Many oxidizing agents
– Potassium dichromate (K2Cr2O7) used at a high temp and v.
acidic conditions
– Silver catalyst required
– Mercuric ion required to control Cl
-
effects
– Aromatics and pyridine not oxidised
 Samples oxidised with in presence of excess Cr2O7
2-
– quantity of Cr2O7
2-
remaining determined by titration with
ferrous ammonium sulphate
COD > BODu > BOD5
Chemical Oxygen Demand
TOC
 Sample heated in
– oxygen
– gold catalyst
 All carbon converted to CO2
 CO2 measured by infrared spectroscopy
 Quick, but kit expensive, increasingly reliable
Oxygen Demand
• Summary
– The differences between COD and BOD
– How they are measured
– What they are used for in Environmental Engineering.

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BODCOD.ppt

  • 1. Oxygen Demand • Objective – To know the different expressions of Oxygen Demand and their chemical basis, – their use in Environmental Engineering, – and the methods of laboratory determination. • Reference • Sawyer C.N. et al Chemistry for Environmental Engineers
  • 2. Oxygen Demand  Concept derives from 19th Century  pollution of rivers with faeces, household wastes  ie organic wastes  Stinking rivers, incapable of supporting fish  Rivers devoid of oxygen  Polluting potential expressed in terms of – oxygen demand
  • 3. Oxygen Demand is a measure of organic carbon  Organic pollutants complex carbon molecule  Enormous range of organics  Impossible to identify and quantify organics  Oxygen consumed as bacteria consume organics Eg Aerobic Metabolism  Quantity of oxygen consumed is a measure of the concentration of organics in water
  • 4. Options for measuring OD  Biochemical Oxygen Demand  BOD  Chemical Oxygen Demand  COD  Total Organic Carbon  TOC
  • 5. 0 5 10 15 20 25 30 35 40 45 0 5 10 15 20 25 Time (days) Oxygen Demand (mg/l) Carbonaceous oxygen demand Biochemical Oxygen Demand  "Amount of oxygen required by bacteria to break down decomposable organic matter under aerobic conditions" Ultimate oxygen demand BODu = L 5 Day oxygen demand BOD5
  • 6. BOD  Bioassay  Amount of oxygen used up under defined conditions  Temp 20 C  Virtually all degradable matter oxidised in 20 days - BODu or ultimate BOD  5 day BOD used – BOD5 is 70-80% of the BODu  BOD wastewater (mg/l) – <200 weak – 300 typical – 1000 strong
  • 7. Complications of BOD  Conditions critical – rigorous attention to and control of conditions  nutrients and seed must be present  toxins must be absent  Theoretical BOD > BOD ultimate – 1. not all biodegradable carbon oxidised  E.g. BODu glucose = 85% of theoretical BOD C6H12O6 + 6O2 6CO2 + 6H2O – 2. not all carbon biodegradable under conditions  sometimes called humus  eg lignin  Ammonia also exerts an oxygen demand – Nitrification
  • 8.  Nitrification controlled for by – 5 day test (nitrifiers grow slowly) – inhibitors eg Alkylthiourea (ATU), TCMP Oxygen Demand 25 higher oxygen demand exerted due to nitrification 0 5 10 15 20 25 30 35 40 45 0 5 10 15 20 Time (days) (mg/l) Carbonaceous oxygen demand 5 Day oxygen demand BOD5
  • 9. Measuring dissolved oxygen  Winklers Method (titration) – Mn2+ oxidised to MnO2 Mn2+ + 2OH - + 1/2 O2 MnO2 + H2O – At low pH MnO2 oxidises Iodide MnO2 + 2I - + 4H+ Mn2+ + I2 + 2H2O – Care required with sampling and interference  DO probe – Quick simple, reliable – Must calibrate carefully (temp sensitive) – Probe is an electrode system covered by a PTFE coat
  • 10.  Organic matter oxidised chemically (2-3 hours)  Virtually all organic matter oxidised, – non-biodegradable material degraded, COD > BODu – COD correlated BOD – E.g. raw wastewater  Many oxidizing agents – Potassium dichromate (K2Cr2O7) used at a high temp and v. acidic conditions – Silver catalyst required – Mercuric ion required to control Cl - effects – Aromatics and pyridine not oxidised  Samples oxidised with in presence of excess Cr2O7 2- – quantity of Cr2O7 2- remaining determined by titration with ferrous ammonium sulphate COD > BODu > BOD5 Chemical Oxygen Demand
  • 11. TOC  Sample heated in – oxygen – gold catalyst  All carbon converted to CO2  CO2 measured by infrared spectroscopy  Quick, but kit expensive, increasingly reliable
  • 12. Oxygen Demand • Summary – The differences between COD and BOD – How they are measured – What they are used for in Environmental Engineering.