ProblemsAndSolutions

Problems
And Solutions
On
DO BOD COD ThOD TOC
DO,BOD,COD,ThOD,TOC

Solubility of Oxygen
SolubilityofOxygen
Whatisthesolubilityofoxygeninwaterin
p
contactwithairwhentheatmospheric
pressureis0.88atm,thetemperatureis16C,
and the chloride concentration is 1000 mg/L?
andthechlorideconcentrationis1000

Henry Constants for Various Gases

HenryConstantsforVariousGases

Temperature dependence of Henry constant

TemperaturedependenceofHenryconstant
LiqGas :
GasLiq :

kH :Henry'sconstant foragiventemperature,
T :anygiventemperature,inK,
: any given temperature in K
T o :standardtemperature(298K)
Valuesof C (inK).
Gas
C

O2
1700

H2
500

CO2
2400

N2
1300

He
230

Ne
490

Ar
1300

CO
1300

Solubility of O2 againstTempandSalinity
SolubilityofO
against Temp and Salinity

 FFrom the
th Table:
T bl
at25C DO:8.4mg/L
at 16C DO:10.0mg/L
at16C
DO : 10 0 mg/L
This Table does involve the temp dependence ofKH
Use asimple direct proportion rule and find DOat16Cfor
,
0.88atm,i.e.:At16C:
For 1atm
DO:10.0mg/L
For 0.88atm DO:?

Then,use again simple proportion to find DOfor 1000mg/L

salinity (intrapolation between 05000mg/Lsalinity).i.e.,
For 0mg/Lsalinity
0 mg/L salinity
DO:10.0mg/L
DO : 10 0 mg/L
For 5000mg/Lsalinity DO:9.5mg/L

Solubility of Oxygen
SolubilityofOxygen
Calculatethepercentsaturationofdissolved
yg
p
temperature
p
oxygeninawatersamplewitha
of22Candadissolvedoxygenconcentration
of 5 3 mg/L when the atmosphericpressureis
of5.3mg/Lwhenthe
atmospheric pressure is
1atm.Assumethesamplesalinityislessthan
100 mgIL
100mgIL.

 FromtheTable
At22C DO:8.8m/Lwhichisthesaturationconcn.
/

Then,
%Saturation=(8.8
(
5.3)/8.8=66%
)/
Theeffectofsalinitymaybeassumedtobe
negligeblesinceitisclosetozero
li bl i
it i l
t

Theoretical COD
TheoreticalCOD
WhatisthetheoreticalCODofsamples
g
g
containing300mg/Lof
(a)ethanol (C2H5OH),
(b) phenol(C
h
l (C6H5OH),and
OH) d
((c)leucine(C
)
( 6H13NO2))?

Theoretical COD
TheoreticalCOD
Asanexample,lets
l l workk onphenol,
h
l
The theoretical oxidation rxn isasfollow:
C6H5OH+7O2 6CO2 +3H2O
94 gr
94gr224gr
224 gr
300mg/L715mg/L:Theoretical COD

C6H13NO2 +.O2 6CO2 +.H2O+NO3
Complete the stoichiometry and dothe restof
the calculations.
calculations

Theoretical CODand
COD and estimation ofL
of L0
((a)EstimatetheCODofasolutioncontaining500
) E ti t th COD f
l ti
t i i 500
mgIL ofbutanol(C4H9OH)
(b)Ifthecompoundwerereadilydegradable
(b) If the compound were readily degradable
biologically,aboutwhatwouldyou expectthe5
day BOD to be?
dayBODtobe?
Solution:
Solution:
(a)You know how to calculate ThCOD
C4H9OH+O
OH + O2 4CO
4 CO2 +H
+ H2O

(b)
(b)Use
Use the Table 23.2inthe
23 2 in the text to estimate the
percentage ofBOD5 asfollows

Theoretical CODand
COD and estimation ofL
of L0
Chooseakvalueforthehighestbiodegradabilityand
estimate5dayBOD

Notations about BOD

NotationsaboutBOD
Ultimate
Ulti t BOD:L
BOD L0 or BODu
BODatany time:yt or BODt
5day BOD:y5 or BOD5
k20 :rateconstant attemp 20C
kT :rateconstant attemp T

BOD and Biodergadability

BODandBiodergadability
Whatcouldbeinferredfromthefollowing
y
g
ease
analyticalresultsconcerningtherelative
ofbiodegradabilityofeachwaste?

5 day BOD test

5dayBODtest

D0 D5
__________
BOD(mg/l)=
P

Pisdecimalvolumetricfraction
P
is decimal volumetric fraction
ofwastewaterusedintest
Disdissolvedoxygen
concentrationatTime=0
and Time 5 days
andTime=5days

BOD and Pollution Flowrate

BODandPollutionFlowrate
AwastewaterstreamhasaBODof4000mg/L.
h
f
/
Calculatetheflowrate ofBOD(inkg/hr)ifthe
wastewaterhasaflowrate of5000m3/hr.
/
Assume,ifnecessary,thedensityofwastewater
as1,05gr/cm3

Solution:
BOD Flowrate inkg/hr
BODFlowrate
in kg/hr =
(5000 m3/hr)x(4000mg/L)x
(1 k /106mg)x(10
(1kg/10
) (1033 L/1m
L/1 3)=200kg/hr
) 200 k /h

Time dependent BOD values

TimedependentBODvalues
Asample
l ofwastewater
f
h
hasanultimate
li
BODof
O f
280mg/Land a5day BODof240mg/L.Calculate
20 d BODofthis
20day
BOD f thi sample.
l
Solution:
y20 =L0 ((1ek*20)):
First calculate k using given data
y5 =L0 ((1ek*5)) 240=280(1e
( k*5)) k=0.39d1
Then 20day BOD:
y20 =L0 (1ek*20)=280(1e0.39*20)=279.9mg/L

Time dependent BOD values

TimedependentBODvalues
y1 =L0 (1ek*t1)
(1eek*t2)
y2 =LL0 (1
y1/y2 =(1ek*t1)/(1ek*t2)
If2differentdaysofBODsareknown,k value
canbecalculated.ThenL0 canbecalculated.

Sample Calculation forBOD

SampleCalculation
for BOD
Determinethe5dayBODfora15mlsamplethatisdiluted
y
p
withdilutionwatertoatotalvolumeof300mlwhentheinitial
DOconcentrationis8mg/landafter5days,hasbeenreduced
to2mg/l.
2
/l
D0=8
=8
D5 =2
P=15ml/300ml=0.05
BOD(mg/l)

8 2
=_______=120
0 05
0.05

Sample Calculation forBOD

SampleCalculation
for BOD

Sample Calculation forBOD

SampleCalculation
for BOD

Sample Calculation forBOD

SampleCalculation
for BOD

Sample Calculation forBOD

SampleCalculation
for BOD
b)Correctthekvaluefor15C
kT =kk20 T20

k15 =0.23(1.047
= 0 23 (1 0471520)=0.18d
) = 0 18 d1

c)Calculatey
)C l l t 8
y8 =220(1 e0.18x8)=168mg/L

Sample Calculation forBOD

SampleCalculation
for BOD

Thomas Method
ThomasMethod
Variouswaysexisttodeterminek andBODu.
ThemethodwewilluseistheThomas
methodWater SewageandWorks,Vol.97pg.
123 1950
123,1950.
Thomasrecognizedthesimilarityoftheseries
kt
kt andkt[1+(kt/6)]
expansions for1e
f
k [ (k / )]33 andthe
h
BODequationanddevelopedtheapproximate
formula:

Thomas Method
ThomasMethod

Thomas Method
ThomasMethod
linearizinggives(howtolinearize?)

Plotting
Plotting(t/BOD)
(t/BOD)1/3 vst
vs t givesastraightline,
gives a straight line
where

Thomas Method
ThomasMethod

Example on Thomas Method

ExampleonThomasMethod

Example on Thomas Method

ExampleonThomasMethod
Solution
1. Plot Measured BOD vs Time as shown on
1.PlotMeasuredBODvsTimeasshownon
Figure1;Columns(3)vs(1)

Example on Thomas Method

ExampleonThomasMethod
2.IflagtimeexistsinFigure1,subtract itfrom
(
)
CorrectedTime
Time(Column1)toobtain
(Column2).

Example on Thomas Method

ExampleonThomasMethod
3.CalculateColumn(4)usingCorrected Time
andMeasuredBOD
4.PlotColumn(4)vsColumn(2)as shownin
Figure 2
Figure2

Example on Thomas Method

ExampleonThomasMethod
5.From Figure
i
2:
intercept =0.22
slope
p =0.0108

6
6.ManipulateSlope
Manipulate Slope and Intercept eqns to
to
solve simultaneouslyforkandBODu gives:
k=0.2951/d
/
BODu =319mg/L
g/

Example on Thomas Method

ExampleonThomasMethod
7.Usingtheabovecoefficientsgivesthe
g
governingBODtequation,
g
q

Effect ofTemperature on
k(BODrxn rateconstant)
Temperaturestronglyinfluencesreactionrate;
g
p g
y
higherthetemp,greaterthedecay
Temperaturechangesareaccountedforusing
the van'ttHoffArrheniusrelationship.
thevan
Hoff Arrhenius relationship

Problem 23 9:
Problem23.9:
A
Awastewaterhasanestimated5dayBODof160mg/L.
t
t h
ti t d 5 d BOD f 160
/L
Assumingyouweregoing touseathreebottledilution
seriesand310 mL bottleswereused,howmanymL of the
wastewaterwouldyouputineachbottle?
Answer:
Estimated BODvalue falls in2% dilution range (see Table
23.11))
For threebottle experiment,use one lower and one upper
dilution ranges,i.e.1% and 5% together with 2%.
Dothe
D th restofthe
t f th solution
l ti for
f calculating
l l ti the
th absolute
b l t
sample amounts ofthe respective dilutions in310ml
volume

Problem 23 10:
Problem23.10:
Awastewaterhasanestimated5dayBODof300mg/L.
/
Assumingyouweregoing touseathreebottledilutionseries,
what percent mixture of sample would you prepareforadding
whatpercentmixtureofsamplewouldyou
prepare for adding
toeachbottle?
Answer:
Similarwayofsolutionasinproblem23.9
Similar way of solution as in problem 23 9

Problem23.18:
Thefollowingdatawereobtainedintheanalysisofanindustrial
waste:After5days ofincubationat20C,theresidualdissolved
oxygeninblankswas7.80mg/L,andin
yg
g/ ,
a0.1percentdilutionofthe
p
wastewas2.80mg/L.
(a)Whatisthe5dayBODofthewaste?
(b)Howmanypoundsof5
(b) How many pounds of 5day
dayBODarecontainedin10,000gallonsof
BOD are contained in 10 000 gallons of
thewaste?
Answer.
A
(a)Use simplified Eqn (23.14)inthe text to calculate the BOD5value.
Please read the explanation for the simplified eqn
Result is
is(7.82.8)/(0.1/100)=5000mg/LBOD
(7 8 2 8)/(0 1/100)=5000 mg/L BOD5
(b)1gallon=3.785L10000gal=37850L
1Lwaste
1L
t contains
t i 5gofBOD
5 f BOD5.So,37850Lwaste
S 37850 L
t contains
t i
(5gr/L*37850L)=189250g=417poundofBOD5for 10000gal of
waste.

Problem 23 19:
Problem23.19:
D
Determinethe10daycarbonaceousBODofariver
t
i th 10 d
b
BOD f i
samplefromthefollowingdata (assume nodilution
)
used).

Theformulaweightforeachnitrogenspeciesistaken
as14heresincethevaluesare reportedasnitrogen,
not as the respective ammonia nitrite or nitrate
notastherespectiveammonia,nitrite,ornitrate

 Answer 23.19:
Before studying the answer,you need to understand the solutions of
Examples 23.1and 23.3.Then study the following solution
Total10day BODis(8.31.4)=6.9mg/L.
This totalBODcontains Carbonaceous and Nitrogeneous oxygen
demand.
demand
Nitrogeneous oxygen demand should becalculated separately and
subtracted from the totalabove.
Lets examine the datagiven inthe Table:

Totaloxidized NH3Nis2.10.8=1.3mg/L,
Oxidation to NO2Nis0.1mg/L
O id ti to
Oxidation
t NO3Nis2.10.5=1.6mg/L
Ni 21 05 16
/L
Ammonia nitrogen (NH3N)which was formed during BODtestis
1.6+0.11.3=0.4mg/L

Totalnitrogeneousoxygendemandisthesumof
g
yg
theoxidationtonitrite(Eqn.23.7)and
theoxidationtonitrate(Eqn.23.8):

Oxidationtonitrite:

3*32 g Oxygen
3*32gOxygen

2*46gNO2

Fortheformationof92gNO2,96goxygenisneeded;
For0.33mg/LNO2(0.1mg/LNO2N),0.34mg/Loxygen(BOD)is
needed
d d

 Oxidationtonitrate:
Oxidation to nitrate:
32gOxygen

2*62gNO3

For
Fortheformationof124gNO
the formation of 124 g NO3,32goxygenisneeded;
32 g oxygen is needed;
For7.1mg/LNO3(1.6mg/LNO3N),1.83mg/Loxygen(BOD)
is needed.
isneeded.
Then,

TotalNitrogeneousBOD=0.34+1.83=2.17mg/L
CarbonaceousBOD=TotalBOD NitrogeneousBOD

=6.9 2.17=4.73mg/L
/

Problem 23 20:
Problem23.20:

Determinethe12daycarbonaceousBODofariversamplefromthe
h
d
b
f
l f
h
followingdata inwhichthedilutedsamplemixturecontained10percent
ofsample.

Theformulaweightforeachnitrogenspeciesistakenas14heresincethe
valuesare reportedasnitrogen,notastherespectiveammonia,nitrite,or
nitrate.
i
Answer:
Reexamine
Re
examinethesolutionsof23.18and23.19forthesolutionofthis
the solutions of 23 18 and 23 19 for the solution of this
problem

Problem 23 21:
Problem23.21:
InProbs.23.19and23.20,thesummationoftheinorganic
nitrogenspeciesshownat theendofincubationarehigher
than at day 0 Explain why this might occur
thanatday0.Explainwhythismightoccur.
Answer:
TheanswerisinthesolutionofProblem23.18.Reexamine
the steps of that solution
thestepsofthatsolution

TOC
TOC
TOCisthe
i th TotalOrganic
T t lO
i Carbon,
C b
i th Carbon
i.e.,the
C b content
t t
oforganic materials.
AnExample:

C6H5OH+7O2 6CO2
2 +3H2O
94gr224gr
94mg/L224mg/LThOD
300mg/L715mg/LTheoretical CODor ThOD

TOCisthe
TOC
i th amountt ofCarbon
f C b only.i.e.
l i
TOC:6*12=72mg/Lfor 94mg/Lphenol
For 300mg/Lphenol
300 mg/L phenol ThOD =Th
Th COD=715mg/L
COD 715 mg/L
For 300mg/Lphenol TOC=300*(72/94)=229.8mg/L