cmutsvangwa:, Wastewater Engineering, Dept. of Civil and Water Eng.
, NUST9/26/2006 3-1
Chapter 3
BOD KINETICS
The kinetics of the BOD reactions are formulated in accordance with the first-order
reaction kinetics. The first-order rate model is assumed because actual BOD curve
is difficult to model. First order rates of reaction are proportional to the
concentration of the reactant (one reactant), and Second order reactions depend
on the concentrations of two reactants.
⎧Rate of change of BOD removal ⎫ ⎧Amount of BOD present ⎫
⎨ ⎬α ⎨ ⎬
⎩i.e. rate of oxidation of organic matter ⎭ ⎩ or remaining BOD unoxidosed ⎭
dLt
αLt
dt
dLt
⇒ = −kLt (Phelp’s law
dt
Where:
Lo =total ultimate BOD (usually taken to be equal to the COD in the
absence of a measurement of the ultimate BOD (Fig. 3.1)
Lt =amount of the first stage BOD remaining in wastewater at time t
k =reaction constant, 1
days
t =time in days
dLt
Lt t
Integrating: ∫L0 L
t
= −k ∫ dt
0
Lt
⇒ ln Lt − ln Lo = −kt ⇒ ln = −kt
Lo
Lt L
Or = e − kt (k to base e) or 10 − kt = t (k to base 10)
Lo Lo
⎛ ⎞
k ⎜ base e ⎟
k (base10 ) = ⎝ ⎠
2.303
1
Chapter 3: BOD Kinetics
cmutsvangwa:, Wastewater Engineering, Dept. of Civil and Water Eng., NUST9/26/2006 3-2
Hence Lt = Lo e − kt or Lt = LO 10 − kt
⎧Organic matter oxidised i.e.⎫ ⎧organic matter to be oxidised⎫
⎪ ⎪ ⎪ ⎪
⎨amount of BOD that has ⎬ + ⎨i.e. amount of BOD that has ⎬ = {Ultimate BOD}
⎪ been exerted at any time t ⎪ ⎪ been exerted at any time t ⎪
⎩ ⎭ ⎩ ⎭
⇒ Yt + Lt = Lo
⇒ Yt = Lo − Lt
Substituting Lt in the above equation:
(
Yt = Lo 1 − e − kt )
e.g. 5-day BOD (
Y5 = Lo 1 − e − k ×5 )
BOD Original BOD (Lo)
Yt BOD exerted from 0 to t
Actual BOD removal curve
Lo
Idealised BOD removal curve
Lt=organic matter to be oxidised
time, t
Fig. 3.1 Schematic illustration of BOD curves
Chapter 3: BOD Kinetics
cmutsvangwa:, Wastewater Engineering, Dept. of Civil and Water Eng., NUST9/26/2006 3-3
Determination of BOD k-rate
• k can be computed from BOD values measured at various times
• values of the cube root of time in days over BOD in mg/l are calculated from
the laboratory data and plotted
• the best fit line is drawn through these points
• the gradient of the line gives k to base 10
B
• k = 2.61 where: B= slope and A=intercept
A
For polluted wastewaters, typical values of k to base e at 20oC range from 0.05 -
0.3d-1 (Hammer, 1986). Typical values of K20 values (base e) for domestic
wastewater are in the range of 0.2 to 0.3 d-1 (Tchobanoglous and Schroeder, 1985).
Reaction constant kT at any other temperature is given by Arrhenius equation:
k T = k 20θ (T − 20 )
Where: kT =k at temperature T
k20 =k at temperature of 20oC
θ =Arrhenius coefficient and θ varies from 0.056 to1.135
The commonly used value of θ is 1.047 or for 4<T<20oC, θ =1.135, and for
T>20oC, θ =1.056 (Tchobanoglous and Schroeder, 1985).
Method of least squares to determine k
The least squares method approximates the actual BOD curve for the first order
kinetics. The equations for to perform a least-square fit of experimental data is
given as:
na + b∑ y − ∑ y / = 0
a ∑ y + b∑ y 2 − ∑ y / y = 0
Where; y =BODt value, g/m3
n =number of data points used
b =-k, d-1 (to base e)
a =-bBODu, g/m3.d
⎛ y − y n −1 ⎞
y/ = ⎜ n +1 ⎟
⎝ 2∆t ⎠
BOD data in Table 3.1 was used to analyse a sample of wastewater to determine
the 5 day BOD and k-rate constant in a BOD bottle of 300ml.
Chapter 3: BOD Kinetics
cmutsvangwa:, Wastewater Engineering, Dept. of Civil and Water Eng., NUST9/26/2006 3-4
Fig. 2
Chapter 3: BOD Kinetics
cmutsvangwa:, Wastewater Engineering, Dept. of Civil and Water Eng., NUST9/26/2006 3-5
Fig. 3
Example (Tchobanoglous, 1985)
For the data below, determine the values of k and BODu.
Time, d 1 2 3 4 5 6
3
BOD, g/m 15.8 26.7 37.4 45.9 50.1 56.1
Note the number of data points used is n-1 because of the definition of y/.
t y y2 y/ yy/
(d) g/m3 (g/m3)2 (g/m3.d) (g/m3)2d-1
0 0 - - -
1 15.8 249.6 13.4 211.7
2 26.7 712.9 10.8 288.4
3 37.4 1398.6 9.6 359
4 45.9 2106.8 6.4 293.8
5 50.1 2510 5.1 255.5
6 56.1 3147.2 - -
∑ 175.9* 6978.2 45.3 1408.4
*Sum based on t=1 to 5 d
Determine the values of k and BODu
5a + 175.9b − 45.3 = 0
Chapter 3: BOD Kinetics
cmutsvangwa:, Wastewater Engineering, Dept. of Civil and Water Eng., NUST9/26/2006 3-6
175.9a + 6978.2b − 1408.4 = 0
Solving for a and b yields:
a = 17.3
b = −0.23
and therefore:
⎛ ⎞
k = −b = 0.23d −1 ⎜ base e ⎟
⎝ ⎠
a
BODu = − = 73.8 g / m 3
b
Fig. 3.4: BOD data and least square fitted curve(BOD, g/m3 and t in days)
Fujimoto approach
An arithmetic plot is prepared of BODt+1 versus BODt. using data in previous
example (Fig. 5). The value at the intersection of the plot with a line of slope 1
corresponds to the ultimate BOD (BODu=74g/m3). The rate constant, k is
determined from previous equations using the BODu and one of the BOD values,
and the corresponding time.
Chapter 3: BOD Kinetics
cmutsvangwa:, Wastewater Engineering, Dept. of Civil and Water Eng., NUST9/26/2006 3-7
Fig.3.5: Graphical solution of Fujimoto ((BOD, g/m3)
References
1. Hammer M. J., (1986), Water and wastewater technology, Prentice Hall, USA
2. Mara D, D, Sewage treatment in hot climates
3. Metcalf and Eddy, (1995), Wastewater engineering, treatment, disposal and
reuse, McGraw Hill, New York, USA
4. Tchobanoglous G., and Schroeder E., (1988), Water Quality, Addison-Wesley,
USA.
Chapter 3: BOD Kinetics
