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Chemical Characteristics

• Chemical Characteristics: In sanitary sewage about 75 %


of suspended solids and 40% of filterable solids are organic. These
solids are derived from both animals and plant along with human.
Organic compounds are usually consists of C; H; O; N along with S; P
and Iron. The organic substances found in sewage are Protein (40-
60%); Carbohydrates (25-50%) and 10% as fats and oils. Along with
these organic compounds small amount of synthetic organic
compounds like VOCs, Pesticides, insecticides, Organic Priority
Pollutants are also presents in sewage. Sewage also contain inorganic
substances. All the test representing these organic and inorganic
constituents come under the heading of chemical characteristics. Test
like BOD, COD, Nitrogen, phosphorus, alkalinity etc give the chemical
characteristics of sewage.
Chemical Characteristics
• BOD (Biochemical Oxygen Demand): When biodegradable Organic
Matters is released into a water body, microorganisms feed on the wastes,
breaking them into simpler organic and inorganic substances. When this
decomposition occurs in aerobic environment the process produces non-
objectionable, stable end products like CO2, SO4, PO4 and NO3. A simplified
form of Aerobic decomposition is
• O.M + O2 +Microorganisms CO2 + H2O + C5 H7 NO2 (New
Cells )+ stable Products like NO3; PO4; NO3….)

When insufficient O2 is available Anaerobic decomposition occurs by


different microorganisms. They produce end products that can be highly
objectionable, including H2S; NH3 and CH4 .
The reaction is O.M +Microorganisms CO2 + H2O + C5 H7
NO2 (New Cells)+ Unstable Products (NH3; H2S; CH4….). CH4 is a stable
gas, while other products are usually unstable.
Bacteria placed in contact with organic matter will utilize it as food source.
Biochemical Oxygen Demand (BOD)
In the utilization of the organic material it will eventually be oxidized to
stable end products such as CO2 and H2O etc.

The amount of oxygen required by the bacteria to oxidize the organic


matter present in sewage to stable end products is known as
biochemical oxygen demand.
Significance: -
Used in design of waste water treatment plants.
Used to measure efficiently of waste water treatment plant.
DERIVATION OF BOD EQUATION

Biological oxidation of organic matter by bacteria is considered to be a first


order reaction for all practical purposes. In a first order reaction, the rate of
reaction is proportional to the concentration of the reactant present. So, we
can say that in case of biological oxidation of organic matter by bacteria,
the rate of oxidation is proportional to the organic matter REMAINING.
BOD EQUATION
Let Lt = the amount of BOD remaining or the organic matter
remaining at any time t

L0 = the initial concentration of Organic matter or BOD remaining at


time =0 also known as ultimate BOD
• Mathematically dL/dt α -L (the negative sign show that L is
decreasing) or dL/dt = -kL where K is reaction rate constant. It
depends on a number of factors like nature of waste, ability of
microbes to decompose waste and temperature. Its value is
0.23/day at 20 0C
Or dL /L = -Kt

Taking integration, the equation is


𝐿𝑡 𝑡
‫𝐿׬‬0 𝑑𝐿/𝐿 = −𝑘 ‫׬‬−0 𝑡 =ln Lt – ln Lo= -Kt or ln Lt/Lo = -Kt

L t/Lo = e –Kt or Lt = Lo e –Kt


BOD EQUATION
Let ‘y’ be the concentration of organic matter (BOD) consumed up to time ‘t’

y = Lo – Lt

y = Lo – Lo e –Kt => y = Lo ( 1 - e –Kt)

i.e BOD consumed = ultimate BOD (1 – e –Kt) in ‘t’ days

Typical value of K = 0.23 per day for domestic sewage at 20oC. Value of ‘K’
is temperature dependent. KT = K20 (θ) T-20 where θ = 1.047

KT = K20 (1.047) T-20

KT = Value of K at temperature T in 0C

Limitation in BOD test: The limitation of the BOD test are as

i. A high concentration of active microorganisms required

ii. Pre-treatment is required if toxic materials are present in wastewater

iii. Only biodegradable organics are measured

iv. Long time is required to calculate BOD


BOD Sketch

TBOD
L0 NBOD

BOD CBOD
mg/l
Lo

y
Lt

0 1 2 3 4 5 6 7 8 9 ----
--days
Example
Calculate the ultimate BOD for a sewage whose 5 day BOD at 20oC is 250 mg/l. Assume K = 0.23 per
day what will be BOD after 2 days.

Solution: y = Lo (1 – e Kt)

250 = Lo (1 – 5 x 0.23)

Lo = 365.83 mg/l

y2 = 365.83 (1 – e –0.23 x 2)

y2 = 134.89 mg/l = 135 mg/l Answer

Example: The BOD5 of waste water is determined to be 150 mg/L at 200C. The k Value is
known to be 0.23 per day. What would be the BOD8 if test were run at 150C.

Solution: Yt = L0 (1- e –kt) => Y5 = L0( 1-e -0.23* 5)

150 = L0 (1-e -1.15) => 150/0.683 = 219.50 mg/L

Now KT = K 20Θ(T-20) = K15 = K 20(1.047)-5 = 0.23 * 1.047 -5 = 0.183

Now Y8 = L0 (1-e-kT) = 219.5 (1-e -0.183*8) = 168.73 mg/L Answer


Example
The BOD remaining in a sewage sample after 4 and 8 days was 160 and 60 mg/l respectively at 20oC
calculate the 5 day BOD of the sewage at 25oC.

SOLUTION:
BOD exerted / consumed = y
BOD remaining = L
L = Lo e-Kt
160 = Lo e-K x 4
60 = Lo e-K x 8
Lo = 160 / e –4K
60 = [160 / e –4K ] e–K8
60 = 160 e –8K +4K
0.375 = e –4K
ln (0.375) = -4k
K = 0.245 per day

Lo = 160/e –4 x 0.245 =426.3 mg/l

At 25oC
K25 = K20 (1.047) T-20
K25 = 0.245 (1.047) 25-20
K25 = 0.308 per day
Y5 = Lo (1 - e –Kt)
Y5 = 426.3 (1 – e –0.308 x 5)
Y5 = 335 mg/l
DERIVATION OF BOD EQUATION for Nitrogenous O.M
• As Carbonaceous BOD is easily decomposed into various compounds, the
Nitrogen which is a critical element for protein synthesis is bound up in
complex organic molecules is released as ammonia nitrogen. Similarly the
living organisms when died, nitrogen is converted into ammonia. The
oxidation of ammonia required oxygen. Also it is an important nutrient for
algal growth.
• Increased nitrogen control utilizes aerobic bacteria to convert ammonia(NH3 )
to Nitrite
(NO2 -). This type of bacteria is known as Nitrosomonas. The Nitrate bacteria
(Nitrobactor) convert
convert nitrite to Nitrate ((NO3 -). This process is termed as nitrification. The
Nitrogenous Oxygen demand consists of two steps.
NH3 + 3 O2 Nitrosomonas → 2 NO2 -+ 2H + + 2H2O
• 2 NO2 - + O2 → Nitrobactor 2 NO3-
• The overall reaction is NH3 +2O2 → NO3 - + H+ +H2O
DERIVATION OF BOD EQUATION for Nitrogenous O.M
As Oxygen is consumed in this reaction. This type of oxygen demand is
termed as Nitrogenous Oxygen Demand.
The total concentration of Organic and ammonia nitrogen in sewage is
known as Kjeldahl Nitrogen (TKN).
Theoretical NBOD = grams of Oxygen used / Grams of Nitrogen Oxidized
=(4*16)/ 14 = 4.57 gram of O2/ gram of Nitrogen.
For Untreated waste water Ultimate CBOD = 250-350 mg/L; Ultimate
NBOD = 70-230 mg/L
Also Ultimate NBOD = 4.57 * TKN
Example of NBOD
• A domestic sewage has 30 mg/L of nitrogen in the form of ammonia.
Calculate (a) the ultimate nitrogenous oxygen demand and (b) the ratio
of the ultimate NBOD to the concentration of nitrogen in the waste.

• Solution: the overall nitrification reaction is

• NH3 +2O2 → NO3 - + H+ +H2O

• The molecular weight of ammonia is 17, while of oxygen is 32. It means


one gram mole of ammonia required two gram mole of
oxygen(2*32=64). Since ammonia contains 14 gram of Nitrogen, and
the concentration of nitrogen is 30 grams

• So NBOD = 30mg/L* (17g NH3 /14 gram of N)*(64 gram O2/17


gramNH3)=137.142 grams.

• The oxygen demand to nitrogen is (137.142 mg O2 /L)/(30 mg N/L) =


4.57 mg of O2 / mg of N
Chemical Oxygen demand (COD)
• In addition to CBOD and NBOD measured, there are two other indicators
to describe the oxygen demands of wastewater. They are Chemical
oxygen demand and theoretical oxygen demand.
• Chemical Oxygen Demand (COD): The biodegradable organic matters
are degraded completely by microorganisms either of CBOD or NBOD.
There are some organic matters like cellulose, phenols, benzene and
tannic acid which are resists to biodegradation. Similarly other organic
matters like pesticides, insecticides and various industrial chemicals are
non biodegradable and they are toxic to microorganisms. The COD is a
measured quantity that does not depend on microorganisms. To
calculate the concentration of oxygen for non biodegradable materials a
strong oxidizing agent known as potassium dichromate will be used. The
reaction is Organic matter (CaHbOc) +Cr2O7 -2+ H2O -Cr +3 + CO2 +
H2O
COD and TheoD
• The COD test is much quicker than BOD test, but it does not distinguish
between the biodegradable and non biodegradable organic matter. The
measured COD is usually more than BOD if there is non biodegradable
impurity present. If all are the biodegradable organic matter then COD
remains the same as that of BOD. Roughly the BOD/COD is 0.4 to 0.8.
• Theoretical Oxygen Demand (TheoD): Organic matter of animal or
vegetable origin in wastewater is generally a combination of carbon,
hydrogen, oxygen, nitrogen and other elements. If the chemical
composition of an organic matter is known then the amount of oxygen
required to oxidize it to carbon dioxide and water can be calculated
using stoichiometry. This amount of oxygen is known as Theoretical
Oxygen Demand. If that oxidation is carried out by bacteria then it is
BOD, if by chemical process then it is COD. If a combination of both
then it is TheoD
TheoD Example
• The following data have been obtained from a waste water characterization. BOD5 =
400 mg/L; k = 0.29 d-1; NH3 = 80 mg/L. Estimate the total quantity of oxygen in mg/L
that must be furnished to completely stabilize this waste water. What is the COD and
TheoD for this waste.
• Solution: The Carbonaceous BOD is
• BOD5 = Y5 = Lo (1-e(-5k) ) => 500 = Lo (1-e (-5*0.29) => Lo = 500 / (1- e (-5*0.29 ) )= 523.23
mg/L.
• The Nitrogenous BOD is NH3 +2O2 → HNO3 +H2O.
• (80 mg/L of NH3 / 17 g/mol of NH3)* (2 molO2 /mol NH3)*32 g/ molO2 )= 301.17 mg/L.
• Total amount of Oxygen = 523.23 + 301.17 =824.40 mg/L.
• The BOD/COD varies from 0.4 to 0.8. let it may be 0.6 then COD = 400/0.6 = 666.67
mg/L
• The theoretical oxygen demand is
• TheoD = COD +NBOD = 666.67 + 301.17 = 967.84 mg /L
• as COD already having CBOD.
Biological/Micro bacteriological Characteristics of sewage

• In sewage a lot of Suspended, colloidal or dissolved degradable organic


material, present in certain quantities and ratios which depends on the
nature of the wastewater. Most biological waste and wastewater
treatment processes employ bacteria as primary microorganisms; certain
other microorganisms may also play an important role. Bacteria is a single
cell organisms. Their mode of reproduction is usually binary fission. The
three categories of bacteria are spherical (0.5 to 1.0 μm in dia.), cylindrical
(0.5 to 1.0 μm in width by 1.5 to 3.0 μm in length) or helical (0.5 to 5.0 μm
in width by 6.0 to 15.0 μm in length). Bacteria are usually consists of 80%
water and 20% dry material, of which 90% is organic and 10% in organics.
An approximate formula for organics fraction is C5 H7 O2 N, when
phosphorus is considered then the formula is C60 H 87 O23 N12 P.

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Biological/Micro bacteriological Characteristics of sewage

• The inorganic portion is P2O5, SO3, Na2O, CaO, Mg O, K2O and Fe2 O3 .As
all of these elements and compounds are derived from environment, a
shortage of any of these substances would limit and in some cases,
change the growth. Population dynamics of bacteria in biological
treatment depends on environmental factors which include: pH;
temperature; type and concentration of the substrate; essential nutrient
concentration and its availability; (nitrogen, phosphorous, sulfur, etc.);
essential minerals; media toxicity; byproducts; and degree of mixing.

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