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Experimental Methods in Environmental Engineering CE213 Lab Report

Date: 1st February 2012 Biochemical Oxygen Demand Kinetics Study

Submitted by Name: Apoorva R Shastry S. R No. : 07-05-02-10-41-11-1-08364 Course: M.E. Department: Civil Engineering


Objective To determine the rate constant of reaction (k) and the ultimate BOD (Lo) of the influent of the waste water treatment plant. Significance The BOD reactions are first order in character, that is, the rate of the reaction is directly proportional to the amount of biodegradable organic matter remaining at anytime as modified by the population of active organisms. Once the population of organisms has reached a level at which only minor variations occur, he reaction rate is controlled by the amount of food available to the organisms and may be expressed as follow: = where C represents the concentration of biodegradable organic matter at time t, k is the rate constant of the reaction. This means that the rate of the reaction gradually decreases as the concentration C of biodegradable organic matter or the food for the bacteria decreases. The major concern with the biodegradation of organic matter in natural waters is the resulting oxygen consumption, and the impact it has on the oxygen content of water. CnHaObNc + (n+4 2
3 4

)O2 nCO2 +

2 H2O + cNH3

Thus it became customary to describe the biodegradable organic matter in terms of its equivalent oxygen consumption potential. Towards this end for BOD consideration it is customary to use Lt in place of C where Lt represents the ultimate BOD or oxygen equivalent of the biodegradable organic matter remaining at anytime t.

Theory If Lo is the concentration of BOD at time t= 0, Lt is the concentration at time t. the above equation can be written as = Upon integration the expression obtained is, = The amount of BOD exerted is determined by determining the amount of oxygen in a given time interval. The BOD exerted is represented by y, where y = Lo - Lt y = Lo (1- e-kt ) In the BOD test, y is measured rather than Lt. This value, the oxygen uptake through the bio oxidation of the degradable organic matter, is measured through oxygen concentration decrease in a sample in a closed bottle with time. If t is long enough e-kt approaches zero, y = Lo. Thus measurements of y are used to estimate Lo. Apparatus a. Aspirator bottle 10L capacity b. Air pump to aerate the dilution water c. BOD incubator adjusted at 20 1C. d. BOD bottles 300mL capacity

a. Dilution water i. ii. iii. iv. Phosphate buffer solution Ferric Chloride Magnesium sulphate Calcium Chloride

b. Starch indicator

c. Concentrated sulphuric acid, H2 SO4 d. Manganese sulphate solution, MgSO4 Alkali azide Sodium thiosulphate solution, Na2S2O3

Procedure 1. Preparation of dilution water 5L of DDW is taken in aspirator bottle and 10mL each of reagent phosphate buffer, MgSO4, CaCl2 and FeCl2 is added. The aspirator bottle is filled up to 10L with DDW. The dilution water is continuously aerated with the help of an aeration pump. The dilution water must be saturated with O2 and maintained at 20 1C. 2. Sample dilution Diluted sample: The samples with suspected high BOD having no or very little DO level need to be diluted, 50 to 100 times with dilution water to obtain the sufficient level of DO in the sample. Hence, a clear depletion of DO during five days, incubation can be achieved to obtain an appropriate value of BOD in the samples. The influent with high BOD is diluted 60 times 3. DO measurement Modified Winker Method a. A 300mL BOD bottle is rinsed with sample. The sample is poured into the BOD bottle in such a way that it is allowed to overflow to avoid any entrapment of air bubbles. The bottle is closed with stopper carefully. b. The stopper is removed and 2mL MnSO4 reagent followed by 2mL alkaline iodide-azide agent is added. The stopper is replaced so that no air is entrapped in the bottle. Any excess water is poured off the bottle rim and the bottle is inverted several times to mix. A brownish-orange flocculent precipitate will form, if sample contains DO. In absence of DO, a white precipitate will appear. c. The sample is allowed to stand until the floc has settled and left the top half of the solution clear. Again the bottle is inverted several times and let stand until the upper half of the solution is clear. This is to ensure the complete reaction of chemicals with available DO. d. The stopper is removed and 2mL concentrated H2 SO4 is immediately added. The stopper is carefully replaced to avoid trapping air bubbles. It is inverted several

times to mix. The floc will dissolve and leave a yellowish-orange iodine colour if DO is present. e. 204mL of sample is measured, which corresponds to 200mL of the original sample into a 250mL Erlenmeyer flask f. This solution is titrated with 0.025N Na2S2O3 titrant to a faint yellow colour. 12mL of starch indicator is added and swirled to mix. A dark blue colour will develop. g. The titration is continued until the solution changes from blue to colourless. 1.0mL of 0.025N Na2S2O3 200g DO So the total number of mL Na2S2O3 solution used is equal to the mg/L DO available in the sample.

4. Measurement of BOD a. 5mL of influent sample is measured with the help of pipettes and added in 5 BOD bottles. b. The bottles are filled with enough dilution water c. 5 bottles are filled with blank solution. d. The bottle is stoppered carefully without entrapment of any air bubbles. e. Initial DO is measured using Winker method. f. The samples are incubated at 20C. g. The DO is measured at regular intervals for 12 days, k and Lo is determined as follows.

Observations and Calculations Observations Day

Initial Reading

Final Reading Dissolved Oxygen Initial Reading

Initial Reading Dissolved Oxygen

0 3 7 9 12 Calculations


15.2 30.4 40.2 47.6 53.6

7.8 6.4 5 4.8 4.6

15.2 30.4 40.2 45.7 51

22.8 35.2 42.6 47.8 52.8

7.6 4.8 2.4 2.1 1.8

24 35.2 42.8 49


D.O of Blank

D.O. of Sample

BOD of Sample




















Sample Calculation for day 9 (row 4) BOD exerted by blank = (D.O. of day 0-D.O. of day 9) x D.F. = (7.8 -4.8) x 60 = 180 mg/l

BOD exerted by blank and sample

= (D.O of day 0-D.O. of day 9) x D.F = (7.6 -2.1) x 60 = 330 mg/l

BOD exerted by sample

= BOD exerted by blank and sample - BOD exerted by blank = 330-180 mg/l = 150 mg/l

0.45 0.4 0.35 0.3 0.25 0.2 0.15 0.1 0.05 0 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 y = 0.0314x + 0.2992 (t/BOD)^(1/3)

BOD Linear (BOD)

time in days

Plot of (t/BOD) 1/3 vs. time

Using Thomson Graphical Method, (t/BOD) 1/3 = (1/kLo)1/3 + ( k2/3/ 6Lo 1/3) t From the above plot, (1/kLo)1/3 = 0.299 ( k2/3/ 6Lo 1/3) =0.031 By the solution of two equations it is obtained that, k = 0.117 day-1, Lo = 319.658 mg/l Result
Reaction rate constant, k = 0.117 day-1 Ultimate BOD, Lo = 319.658 mg/l

Conclusion For the given sample, an ultimate BOD of 319.658 mg/l is obtained with a decay rate constant of 0.117/day. Under these conditions it will take more than 50 days to exert the entire BOD in the sample at a temperature of 20 C.