WATER

CHEMISTRY
M.Eng (Civil Engineering)
(Examination Solutions)
Olayinka Okeola
Course Lecturer
Department of Civil Engineerig
Faculty Of Engineering & Technology
University Of Ilorin
Nigeria
Water Chemistry (CVE 731) examination solutions. 2012/2013 session
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University Of Ilorin, Ilorin
Department Of Civil Engineering
M.Eng Degree in Water Resources and Environmental Engineering
First Semester Examination 2012/2013 Session
Time Allowed: 2 Hours
CVE 731 (Water Chemistry)
Instruction: Attempt Questions 1, 2, and any other two Questions.
QUESTION ONE (30 Marks)
1.1 Why is Water Chemistry very important in M.Eng (Water Resources and Environmental
Engineering) programme?
1.2 What is the essence of BOD and COD in wastewater treatment?
1.3 In a precipitation water softening, lime is used to remove calcium hardness by the reaction
CaO + Ca (HCO
3
)
2
----- 2CaCO
3
+ H
2
O
What dosage of lime with a purity of 78% CaO is required to combine with 70 mg/l of Ca?
1.4 What dosage of sodium hydroxide is required to neutralize an industrial wastewater with an
acidity of equivalent to 6 mg/l of Sulphuric acid?
1.5 In the determination of BOD of a slaughter house, the following information was obtained:
1 in 50 dilution 1 in 100 dilution
Initial Do 9.1 9. 1
Final Do 0.4 4.0
Initial DO of dilution water =9.1mg/l
Final DO of dilution water = 8.6 mg/l
Determine the probable BOD of the waste. The COD value for this waste was 3500mg/l.
Comment on the significance of the BOD and COD values.
QUESTION TWO (30 Marks)
2.1 Explain why dissolved oxygen is of great importance in water quality studies and discuss the
principles used to established the mathematical expression for oxygen deficit
,
t k
a
t k t k
a
t
D
K K
L K
D
2 2 1
10 10 10
1 2
1

+

=
Where the symbols have their usual meaning.
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2.2 Identify three routes in which highly toxic compound such chlorinated aromatic compound (DDT)
get into water body.
2.3 What is the name of non pathogenic organisms commonly used in bacteriological examination of
water? Explain the suitability for this purpose.
2.4 A stream with a BOD of 2mg/L and saturated with DO has a mean flow of 2.26 m
3
/s. A sewage
effluent discharge of 0.755 m
3
/s with BOD of 30mg/l and DO of 5mg/l is discharged to the stream.
Assuming that the temperature is constant at 20
0
c, determine the DO deficits over the next 5 days
and plot the sag curve. Calculate the maximum deficit and the time at which it occurs.
K
1
, for stream/ effluent mixture -0.17/d
K
2
, for stream -0.4/d
Saturation concentration of DO at 20
0
c =9.1mg/L
QUESTION THREE (20 Marks)
3.1 Outline the importance, principles and techniques in the determination of the following
parameters in water or waste water sample:
(i) Turbidity (ii) Chemical Oxygen Demand (iii) Dissolved Oxygen and (iv) Grease.
3.2 With the aid of a clear and well labeled diagram, described the response of an initially clean
stream to
effluent discharge within a very short distance downstream. How does the population of fish,
protozoa, bacteria and the DO parameter vary with travel distance?
3.3 A manometric BOD apparatus is used to conduct BOD test on a treatment plant effluent with daily
readings as follows;
Time (days) 0 1 2 3 4 5 6 7 8 9
BOD (mg/l) 0 1 12 18 20 22 24 30 36 40
Plot the BOD-Time curve. Identify the lag and nitrification portions.
What is the best estimated 5-day BOD value?
Why is it necessary to recognize time lag in oxygen uptake for industrial wastes?
QUESTIONS FOUR (20 Marks)
4.1 Describe the origin and importance of the following in water quality and wastewater studies.
(i) Hydrocarbons (ii) Alcohols (iii) Proteins and (iv) Fats.
4.2 Discuss the principles involved in the removal of pollutants in water/ wastewater by
Coagulation and flocculation.
4.3 In what forms does detergents and pesticide appear in water or wastewater?
How can these and odour be controlled satisfactorily?
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4.4 A milk products industry discharges a wastewater to a stream. Characteristics of the wastewater
and the stream are shown below:
Parameter Wastewater Stream
Flow 1000 m
3
/d 19,000 m
3
/d
BOD5 @ 20
o
C 1250 mg/l 2.0 mg/l
DO 0 mg/l 10.0 mg/l
Temperature,
o
C 50 10
K
1
@ 20
o
C, d
-1
0.35d
-1
-
K
2
@ 20
o
C, d
-1
- 0.55d
-1
(a) If no treatment at all is given to the wastewater, what will be the lowest oxygen level in the
stream as a result of the discharge?
(b) If the stream is a trout fishery and the stream standards require a minimum DO of 5.0 mg/l,
what is the maximum BOD
5
(20
o
C) that can be discharged?
QUESTION FIVE (20 Marks)
5.1 There are a number of analytical procedures for measuring selected parameters in water and
wastewater without discussing the methods in detail, enumerate the advantages and flaws of the:
Gravimetric, Volumetric, Colorimetric, and Electrode techniques.
5.2 Distinguish clearly between Acid Base, oxidation/Reduction and Precipitation reactions as
frequently used in water /wastewater analysis.
5.3 A municipal wastewater treatment plant discharge 18,925 m
3
/d of treated wastewater to
a stream. The wastewater has a BOD
5
of 30 mg/l with a k
1
of 0.23d
-1
. The temperature of
the wastewater is 27
o
C and the DO is 2.0 mg/l.
The stream just above the point of wastewater discharge flows at 0.65 m
3
/s, has a BOD
5
of 5.0 mg/l and is 90% saturated with oxygen. The temperature of the stream is 23
o
C.
After mixing, the stream and wastewater flow at velocity of 0.5 m/s and re-aeration
constant is 0.45 d
-1
.
(a) What is the oxygen level of the stream after 2 d?
(b) What is the critical oxygen level in the stream and how far downstream will it occurs?
SOLUTIONS BEGIN NEXT PAGE
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QUESTION ONE
1.1 1. Chemistry of H
2
O actually governs the behavior of pollutants in aqueous system
2. Chemistry of H
2
O including dissolved or particulate matters is the backbone of aquatic systems
and biogeochemical cycles
3. Understanding of water chemistry is a prerequisite for the appropriate use of technical
processes for water treatment and purification.
1.2 1. Physical processes : i. Sedimentation ii. Filtration iii. Gas transfer
2. Chemical processes : i. Chemical addition for precipitation ii. Chemical coagulation
iii. Chemical adjustment of pH
3. Biological process : It is used extensively in wastewater treatment: convert biodegradable
organics etc to manageable form.
1.3 1 mole of
2 3
) (HCO Ca contains 40.1g of Ca
70mg/L of Ca is = 70/40.1 X 162 or 283mg/L of
2 3
) (HCO Ca
56.1g of CaO reacts with 162g of
2 3
) (HCO Ca
283mg/L of
2 3
) (HCO Ca react with
CaO of L mg / 98 283
163
1 . 56
=
For a purity of 78% the dosage of Lime required is L mg / 126
78 . 0
98
=
1.4
4 2 2 4 2
2 2 SO Na O H NaOH SO H + = +
2 moles of NaOH neutralizes 1 mole of
4 2
SO H
or 80g (2 X 40) of NaOH react with 98.1mg of
4 2
SO H
NaOH required = NaOH of L mg / 9 . 4
1 . 98
6 80
=

1.5 , , 5 . 410
2
100
100
2 100
6 . 8 1 . 9 4 . 0 1 . 9 =

= BOD
, , 5 . 460
1
100
100
99
6 . 8 1 . 9 4 . 0 1 . 9 =

= BOD
Probable BOD of waste
= , 2 5 . 460 5 . 410 +
= L mg / 435
But COD = L mg / 3500
Comment
The BOD value is much lower than the COD value because:
1. Waste may contain complex hydrocarbon chain which may not have been metabolized at
the end of 5-day period.
2. Waste may also contain inhibiting substances for biological degradation processes.
3. Nitrification oxygen demand may be high and have not been accounted for in the BOD test.
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QUESTION TWO
2.1 (a) Life sustenance (fish + aquatic animal species required O
2
)
BOD satisfaction
DO rate of usage functions of:
1. Organic quantity
2. Biodegradable ease
3. Stream dilution capacity
(b) Principle
Based on the model develop by Streeter and Phelps in 1925 which predict changes in the
deficit as a function of BOD exertion and stream reaeration.
2.2 1. Direct application (pesticides et c.)
2 Percolation and runoff
3. Industrial waste discharge
2.3 Esherichia coli
Fecal streptococci
Presence of coliform bacterial is an indication of contamination from feacal sources:
Man; Farm animal and Soil erosion
2.4
Stream
K
1
= 0.17/d
Q =3.035m
3
/s
BOD = 30mg/L
DO = 5mg/L
Q
2
= 0.775m
3
/s
Effluent
Stream + effluent
K
2
=0.4/d
BOD =2mg/L
DO =9.1mg/L
Q
1
= 2.26m
3
/s
To calculate DO (initial) use mass balance
2.26 x 9.1 + 0.775 x 5 = (2.26 + 0.775) DO
DO = 8.05 mg/L
DO
i
= SC - DO
i
= 9.1- 8.05 = D
a
= 1.05mg/L
BOD ultimate L
a
= ?
Apply BOD mass balance
, L 775 . 0 26 . 2 30 775 . 0 2 26 . 2 + = +
L
a
= 9.012 mg/L
L mg
L
L L L
t K
a
t K
u
/ 49 . 10
10 1
012 . 9
10 1
10 1
5 17 . 0
1
1
=

= =
|

'

,
|
|

'

=
1
1 2
1
2
1 2
1 log
1
k L
k k D
k
k
k k
t
a
a
c
= 1.34day
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Deficit
(mg/L)
L mg L
k
k
D
c
t k
a c
/ 64 . 2 10
1
2
1
= =

t t 4 . 0 17 . 0
10 704 . 6 10 754 . 7

=
Hence, D = F (t)
t (days) D
t
0 1.05
1 2.57
2 2.48
3 1.97
4 1.45
5 1.03
Plot D
t
Vs t
1 2 3
4
t k
a
t k t k
a
t
D
k k
L k
D
2 2 1
10 10 10
1 2
1

+ |

'

=
5
6
1
2
3
D
c
(max Deficit)
DO Sag Curve
t
c
QUESTION 3
3.1 1.*Caused by clay, silt and other colloidal impurities
*Imparts a brown or other colour to water bodies
*Provides adsorption sites for chemicals which may be harmful or cause undesirable taste and odour.
*Simply defined as the interference of light passage through water
*Measured by the Jackson candle turbidimeter
2. COD
*Assessment of the organic strength of wastewater and pollution of natural water
*Measure of O
2
amount required to chemically oxidize organic matter
*COD =
, j ,
Sample ml
Normality SO NH Fe tirant Sample ml black ml 800
4
2
4

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3. DO
*Principal Measurement in pollution survey
*Biochemical decomposition of organic matter uses DO
*Low DO level can stifle aquatic life
*Aerobic treatment processes highly dependent on constant availability of oxygen
*DO determination with electrodes
4 Grease
*Fats, oils, waxes, high molecular mass fatty acid.
*Low solubility
*Reduces biological treatability of waste
*Grease determination: soxhlet extraction method
3.2 - Diagram
- Description
3.3 - Plot the Graph
- From graph 5-day value = 24 mg/l
- Lag period used by bacteria to acclimatized. Inhibiting substances such as grease, oil, heavy
metals, kill bacteria. Biochemical activities will not start if there is insufficient food for bacteria.
QUESTION FOUR
4.1 1. Hydrocarbon
-Organic compound with only C & H
-Source : chemical in gasoline & petroleum product
-Vegetable oil contains a large number of unsaturated bonds
2. Alcohol
-Derived from hydrocarbons by replacement of one or more hydrogen atom by hydroxyl group
(OH
-
)
3. Proteins are long strings of amino acids containing C, H, N and P.
-Fats are biochemical substances with the property of being soluble in organic solvent but
sparingly soluble in H
2
O.
4.2 Most of organics and inorganics matter in a turbid natural water are of hydrophobic colloidal
nature. Chemical coagulation aims at destabilizing suspended contaminants. The particles
contact, agglomerate and form flocs which later flush out by sedimentation.
Flocculation is slow mixing process. Coagulation is the term used to describe the entire mixing and
flocculation.
4.3 As DDT (chlorinated aromatic compound), Endrin and alkyl benzene sulfonate
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Wastewater
4.4 (a)
NB:
s m Q
stream
/ 22 . 0
3600 24
19000
3
=

=
s m Q
waste
/ 012 . 0
3600 24
1000
3
=

=
Mass balance for BOD
, , , ) ( 012 . 0 22 . 0 1250 012 . 0 0 . 2 22 . 0
5
mixed BOD + = +
L mg mixed BOD / 6 . 66
232 . 0
44 . 15
) (
5
= =
Convert BOD5 to BODu
,
kt
u
e BOD mix BOD

= 1 ) (
5
,
L mg
e
BOD
u
/ 2 . 80
1
6 . 66
75 . 1
=

=

Mass balance for DO
, , , ) ( 012 . 0 22 . 0 0 012 . 0 10 22 . 0 mix DO + = +
L mg mix DO / 5 . 9
232 . 0
2 . 2
) ( = =
Mass balance for Temperature
, , , ) ( 012 . 0 22 . 0 50 012 . 0 10 22 . 0 mix T + = +
C mix T
o
1 . 12
232 . 0
8 . 2
) ( = =
At T = C
o
1 . 12 , the equilibrium concentration of oxygen in freshwater is 10.8 (Ref: Table 19.8 Water
Resources Engineering by Linsley et al.,)
:. DO = 10.8 9.5 = L mg / 3 . 1
Stream
K
1
= 0.35/d
Q = 0.232m
3
/s
Stream + effluent
K
2
= 0.55d
-1
BOD
5
= 2.0mg/L
DO = 10.0mg/L
Q
1
= 0.22m
3
/s
T
1
=10
o
C
K
1
= 0.35d
-1
BOD
5
= 1250mg/L
DO = 0.0mg/L
Q
2
= 0.012m
3
/s
T
2
= 50
o
C
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For BOD reaction rate
,
20
20 1 . 12
047 . 1

=
T
K K
,
20 1 . 12
1 . 12
047 . 1 35 . 0

= K
,
20 1 . 12
1 . 12
047 . 1 35 . 0

= K
,
9 . 7
1 . 12
047 . 1 35 . 0

= K
1
1 . 12
24 . 0

= d K
For stream Reaction rate (K2)
,
20
20 1 . 12
016 . 1

=
T
K K
,
9 . 7
1 . 12
016 . 1 55 . 0

= K
1
1 . 12
48 . 0

= d K
Hence
,

]

|
|

'

=
o
c
L K
K K
DO
K
K
K K
t
1
1 2
1
2
1 2
1 ln
1
,

'

=
2 . 80 24 . 0
24 . 0 48 . 0
3 . 1 1
24 . 0
48 . 0
ln
24 . 0 48 . 0
1
c
t
, 96 . 1 ln 20 . 4 =
c
t
days t
c
8 . 2 67 . 0 2 . 4 = =
c
t K
c
e
K
K
D Therefore
1
ln :
1
2
=
8 . 2 24 . 0
2 . 80
24 . 0
48 . 0

= e
67 . 0
2 . 80 2

= e
512 . 0 4 . 160 =
L mg / 12 . 82 =
The lowest oxygen level in the stream due to the discharge = 10.8mg/L 82.12mg/L
= -71.32mg/L l mg / 0
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(b)
Mass Balance for DO when DOmin = 5.0 mg/L
, , , DO 012 . 0 22 . 0 012 . 0 0 0 . 5 22 . 0 + = +
232 . 0
1 . 1
= DO
L mg DO / 74 . 4 =
At temp T= 20
o
C, the DO of freshwater = L mg / 1 . 9
L mg D
t
/ 1 . 4 0 . 5 1 . 9 = =
j
t K
o
t K t K a
t
e D e e
K K
L K
D
2 2 1
1 2
1
+

=
L mg D
o
/ 3 . 4 8 . 4 1 . 9 = =
, ,
j
5 35 . 0 5 55 . 0 5 35 . 0
3 . 4
35 . 0 55 . 0
35 . 0
1 . 4

+

= e e e
L
a
j 0639 . 0 3 . 4 0639 . 0 1738 . 0
2 . 0
35 . 0
1 . 4 + =
a
L
2750 . 0 75 . 1 1 . 4 + =
a
L
L mg L
a
/ 9 . 19 =
,
t K
u
e BOD BOD
1
1 (max)
5

=
,
5 35 . 0
1 9 . 19

= e
8262 . 0 9 . 19 =
L mg / 4 . 16 =
L mg C BOD Maximum
o
/ 4 . 16 20 @
5
=
QUESTION FIVE
5.1 Grav - good balance required (Highly sensitive)
Vol - required indicators for end points determination
Col - A tedious methods (frequent standards)
- Subject to serious error because of individual judgement on colour
Elec - Fast
- No need for solution preparation
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Wastewater
5.2 Acid base - Neutralization
Oxidation/Reduction - Removal of ions (Fe
2+
), odour and taste
Precipitation - Removal of undesirable ions
5.3 (a)
90% saturated DO @ 23
o
C
0.9 X 8.6 = 7.7mg/L
Mass balance for BOD5
, , , , mixed BOD
5
65 . 0 22 . 0 0 . 5 65 . 0 30 22 . 0 + = +
L mg mixed BOD / 3 . 11
87 . 0
85 . 9
) (
5
= =
Stream
v
1
= 0.5/s
Q = 0.87m
3
/s
Stream + effluent
K
2
= 0.45d
-1
BOD
5
= 5.0mg/L
DO = 7.7mg/L
Q
1
= 0.65m
3
/s
T = 23
0
C
K
1
= 0.23d
-1
BOD
5
= 30mg/L
DO = 2.0mg/L
Q
2
= 0.22m
3
/s
T = 27
0
C
From Table 19.8
At 22
o
C DO = 8.7mg/L
At 24
o
C DO = 8.4mg/L
22 24
22 23
7 . 8 4 . 8
7 . 8
23

DO
L mg DO / 6 . 8
23
=
s m Q
waste
/ 22 . 0
3600 24
925 , 18
3
=

=
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2
Mass balance for DO
, , , ) ( 65 . 0 22 . 0 20 22 . 0 7 . 7 65 . 0 mix DO + = +
L mg mix DO / 3 . 6
87 . 0
45 . 5
) ( = =
Mass balance for Temperature
, , , ) ( 65 . 0 22 . 0 27 22 . 0 23 65 . 0 mix T + = +
C mix T
o
24
87 . 0
89 . 20
) ( = =
For BOD reaction rate
,
,
20
20 24 1
047 . 1

=
T
K K
,
,
20 24
24 1
047 . 1 23 . 0

= K
,
,
4
24 1
047 . 1 23 . 0 = K
,
1
24 1
28 . 0

= d K
For stream Reaction rate (K2)
,
,
20
20 24 2
06 . 1

=
T
K K
,
,
4
24 2
06 . 1 55 . 0 = K
,
1
24 2
48 . 0

= d K
FromStreeter Phelps Equation
j
t K
o
t K t K a
t
e D e e
K K
L K
D
2 2 1
1 2
1
+

=
At t=24
o
C the equilibrium concentration of Oxygen in freshwater is 8.4mg/L
L mg DO / 1 . 2 3 . 6 4 . 8 = =
Calculate ultimate BOD
u
= L
u
, day t e L mix BOD
t K
u
5 : 1 ) (
1
5
= =

,
5 23 . 0
1 3 . 11

= e l
u
, 3166 . 0 1 3 . 11 =
u
l
L mg L
u
/ 6 . 16
68 . 0
3 . 11
= =
When t = 2 days,
, ,
j
2 48 . 0 2 48 . 0 2 28 . 0
1 . 2
28 . 0 48 . 0
6 . 16 28 . 0

+

= e e e D
t
, ,
j
96 . 0 96 . 0 56 . 0
1 . 2
2 . 0
65 . 4

+ = e e e D
t
j 3829 . 0 1 . 2 3827 . 0 5712 . 0 3 . 23 + =
t
D
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1
3
j 80 . 0 1883 . 0 3 . 23 + =
t
D
L mg D
t
/ 2 . 5 =
L mg is days after stream the of level O dissolve the / 2 . 3 2 . 5 4 . 8 2
2
=
(b)
,

]

|
|

'

=
o
c
L K
K K
DO
K
K
K K
t
1
1 2
1
2
1 2
1 ln
1
,

'

=
6 . 16 28 . 0
28 . 0 48 . 0 1 . 2
1
28 . 0
48 . 0
ln
28 . 0 48 . 0
1
c
t
, j 09 . 0 1 71 . 1 ln
2 . 0
1
=
c
t
, 56 . 1 ln 5 =
c
t
days t
c
2 . 2 =
c
t K
o c
e L
K
K
D Therefore
1
2
1
:

=
2 . 2 28 . 0
48 . 0
28 . 0

= e l D
o c
L mg D
c
/ 2 . 5 =
The critical oxygen level in the stream is 8.4-5.2 = 3.2mg/L
This will occur at a distance "x downstream
c
t Vel x =
km x 95 95040 2 . 2 3600 24 5 . 0 ~ = =
the critical
2
O level of the stream is 5.2mg/L occurs at a distance 95kmdownstream after the
discharge point.