Ch4 Solutions

4-1
4
CHAPTER 4
SOLUTIONS
4-1 Show that 1 g/m = 1000 kg/m
Given: Conversion factors inside back cover
Solution:
g kg mL L kg
1 0.001 1000 1000 3 = 1000 3
mL g L m m
4-2 Show that 4.50% = 45.0 kg/m
Given: % by weight in water
Solution:
a. Assume density of water = 1000 kg/m
b. Calculate % by weight
0.045 x 1000 kg/m = 45.0 kg/m3
4-3 Concentration of NH3 in mg/L
Given: Household ammonia at 3.00% by weight, H2O = 1000 kg/m3
Solution:
a. Calculate the mass of NH3
(0.0300)(1000 kg/m3) = 30 kg/m3
b. Convert kg/m3 to mg/L
(30 kg/m3)(106 mg/kg)(10-3 m3/L) = 30,000 mg/L
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4-2
4-4 Concentration of Cl2 in mg/L
Given: Household bleach at 5.25% by weight, H2O = 1000 kg/m3
Solution:
a. Calculate the mass of Cl2
(0.0525)(1000 kg/m3)(106 mg/kg)(10-3 m3/L) = 52,000 mg/L
4-5 Show that 1 mg/L = 1 g/m3
Given: Conversion factors inside back cover
Solution:
mg g L g
1 0.001 1000 3 = 1 3
L mg m m
4-6 Arsenic standard in mg/L
Given: Standard is 10 ppb
Solution:
a. Convert ppb to ppm
10 3 ppm
10ppb = 10 10 3 ppm or 0.010 ppm
ppb
b. from Eqn. 4-5, 1ppm = 1 mg/L
therefore 10 ppb = 0.010 mg/L
4-7 Convert m3/s to MGD
Given: Flows of 0.0438; 0.05; 0.438; 0.5; 4.38; 5; all in m3/s
Solution: Use conversion factor from inside back cover
a. 0.0438 (3 significant figures)
(0.0438 m3/s)(22.8245) = 0.99971 or 1.00 MGD
4-3
b. 0.05 (1 significant figure)
(0.05)(22.8245) = 1.14123 or 1. MGD
c. 0.438
(0.438)(22.8245) = 9.99713 or 10.0 MGD
d. 0.5
(0.5)(22.8245): = 11.41 or 10 MGD
e. 4.38
(4.38)(22.8245) = 99.9713 or 100. MGD
f. 5
(5)(22.8245) = 114.1225 or 100 MGD
4-8 Molarity and Normality
Given: Concentrations in mg/L
Solution: Molecular Weights are on inside of front cover. In each case:
mg L of species
Molarity =
(1000 mg g )(molecular weight )
Normality = (molarity)(n)
a. HCN
200.0
Molarity = = 0.005485M
(1000)(36.4609)
Normality = (0.005485)(1) = 0.005485 N
b. H2SO4
150.0
(1000)(98.07)
Normality = (0.001529)(2) = 0.003059 N
4-4
c. Ca(HCO3)2
100.0
Molarity = = 0.0006168M
(1000)(162.1122)
Normality = (0.0006169)(2) = 0.001234 N
d. H3PO4
70.0
(1000)(97.9951)
Normality = (0.000714)(3) = 0.00214 N
4-9 Molarity and Normality
Given: concentrations in g/L
Solution:
a. HNO3
Converting micrograms to milligrams

(80 g L ) 1
= 0.08 mg L
1000 g mg
0.08
Molarity = = 1.3 10 6 M
(1000)(63.015)
Normality = (1.3 x 10-6 M)(1) = 1.3 x 10-6 N
b. CaCO3

(135 g L ) 1
= 0.135 mg L
1000 g mg
0.135
Molarity = = 1.3 10 6 M
(1000)(100.09)
Normality = (1.3 x 10-6 M)(2) = 2.7 x 10-6 N
4-5
c. Cr(OH)3

(10 g L ) 1
= 0.01 mg L
1000 g mg
0.01
Molarity = = 1.0 10 7 M
(1000)(103.02)
Normality = (1.0 x 10-7 M)(3) = 3 x 10-7 N
d. Ca(OH)2

(1000 g L ) 1
= 1.0 mg L
1000 g mg
1.0
Molarity = = 1.35 10 5 M
(1000)(74.096)
Normality = (1.35 x 10-5 M)(2) = 2.7 x 10-5 N
4-10 Calculate molarity and normality
Given: 0.05 mg/L As; 0.005 mg/L Cd; 0.002 mg/L Hg; 0.10 mg/L Ni
Solution:
mg L of species
Molarity =
(1000 mg g )(molecular weight )
Normality = (molarity)(n)
a. As3+
0.05
Molarity = = 6.67 10 7 M
(1000)(74.92)
Normality = (6.67 x 10-7 M)(3) = 2.00 x 10-6 N
b. Cd2+
4-6
0.005
Molarity = = 4.45 10 8 M
(1000)(112.4)
Normality = (4.45 x 10-8 M)(2) = 8.90 x 10-8 N
c. Hg2+
0.002
Molarity = = 9.97 10 9 M
(1000)(200.6)
Normality = (9.97 x 10-9 M)(2) = 1.99 x 10-8 N
d. Ni2+
0.10
Molarity = = 1.70 10 6 M
(1000)(58.69)
Normality = (1.7 x 10-6 M)(2) = 3.41 x 10-6 N
4-11 Converting to mg/L
Given: Molarity and normality
Solution:
a. Ca2+ (n = 2 since charge is +2)
(0.01000 N ) 40.08 g
eq (1000 mg g ) = 200.4 mg L
2
b. HCO3- (n = 1 since charge is 1)
(1.000 M)(61.016 g/mole)(1000 mg/g) = 61.020 mg/L
c. H2SO4 (n = 2)
(0.02000 N ) 98.07 g
eq (1000 mg g ) = 980.7 mg L
2
d. SO42-
(0.02000 M)(96.054 g/mole)(1000 mg/g) = 1,921 mg/L
4-7
4-12 Converting to g/L
Given: Molarity and normality
Solution:
a. H2CO3 (n = 2)
(0.05 N)(62.01 g/eq)(1/2)(1,000,000 g/g) = 1.6 x 106 g/L
b. CHCl3
(0.0010 M)(119.37 g/mole)(1,000,000 g/g) = 1.2 x 105 g/L
c. Ca(OH)2 (n = 2)
(0.03 N)(74.096 g/eq)(1/2)(1,000,000 g/g) = 1.1 x 106 g/L
d. CO32-
(0.0080 M)(60.011 g/mole)(1,000,000 g/g) = 4.8 x 105 g/L
4-13 Convert to mg/L
Given: 0.250 M NaOH; 0.0704 M Na2SO4; 0.0340 M K2Cr2O7; 0.1342 M KCl
Solution:
mg/L of species = (molarity)(10000 mg/g)(GMW)
a. NaOH
mg/L = (0.250)(1000)(40.00) = 10,000 mg/L
b. Na2SO4
mg/L = (0.0704)(1000)(142.05) = 10,000 mg/L
c. K2Cr2O7
mg/L = (0.0340)(1000)(294.20) = 10,003 or 10,000 mg/L
d. KCl
4-8
mg/L = (0.1342)(1000)(74.55) = 10,005 or 10,000 mg/L
4-14 Solubility of Mg in mg/L
Given: Solution 0.001000 M in OH
Solution:
From Table 4-2 pKSP = 11.25 for Mg(OH)2
KSP = 10-11.25 = 5.62 x 10-12
KSP = [Mg2+][OH-]2
[Mg ] = 5.62 10
12
2+
= 5.62 10 6 mole L
(0.001) 2
Mg2+ = (5.62 x 10-6 mole/L)(24.305 x 103 mg/mole)

Mg2+ = 0.1367 mg/L
4-15 pH to precipitate iron
Given: Groundwater has 1.800 mg/L Fe and desired concentration is 0.30 mg/L
Solution: From Table 4-2 pKSP = 38.57 for Fe(OH)3
KSP = 10-38.57 = 2.69 x 10-39
[Fe] = 0.30 mg L
= 5.37 10 6 mole L
(55.85 g mole)(1000 mg g )
KSP = [Fe][OH]3
13
[OH ] 2.69 10 39
= 6

(
= 5.01 10 33 )
13
= 7.94 10 12 mole L
5.37 10
pOH = -log (7.94 x 10-12)
pOH = 11.10 and pH = 14.00 - 11.10 = 2.90
4-9
4-16 pH to precipitate Cu
Given: Starting concentration = 2.00 mg/L; ending concentration = 0.200 mg/L
Solution:
a. Notes:
(1) The starting concentration is not relevant to the solution of this problem
(2) From Appendix A
Cu (OH )2 Cu 2+ + 2OH
KSP = 2.0 x 10-19
b. Molar concentration of Cu required
[Cu ] = (63.55 g0.mole

2+ 200 mg L
)(1000 mg g )
= 3.15 10 6
mole L
c. Solve KSP equation for [OH-]
KSP = [Cu2+] [OH-]2
12
[OH ] 2.0 10 19
= 6

(
= 6.36 10 14 )
12
= 2.52 10 7 mole L
3.15 10
d. Calculate pOH
pOH = -log(2.52 x 10-7) = 6.60
e. Calculate pH
pH = 14.00 6.60 = 7.40
4-17 Calcium remaining in solution
Given: Saturated solution of CaCO3 and addition of 3.16 x 10-4 moles/L of Na2CO3
Solution: This solution requires the solution of a quadratic equation.
a. Begin with the equilibrium reaction (Eqn 4-9 or Table 4-2.)
4-10
2
CaCO 3 Ca 2+ + CO 3
b. Write the equilibrium expression using KSP from Table 4-2
KSP = [Ca2+][CO32-] = 10-8.305 = 4.95 x 10-9
c. Calculate the molar concentration of Ca2+ and CO32- at equilibrium (before the addition
of Na2CO3).
[Ca2+] = [CO32-] = (4.95 x 10-9)1/2 = 7.04 x 10-5
d. Set up quadratic equation where x = amount of Ca that will be removed from solution.
[Ca ] = (7.04 10 ) x
2+ 5
[CO ] = (7.04 10 ) + (3.16 10 ) x

3
2 5 4
( )( )
K SP = 7.04 10 5 x 3.86 10 4 x = 4.95 10 9
x 2 (4.57 10 4 )(x ) + (2.23 10 8 ) = 0
e. Solving the quadratic we get roots of
x = 4.01 10 4 and x = 5.56 10 5
Since 4.01 10 4 is greater than what we started with, we select the root x = 5.56 10 5
f. The amount of Ca2+ remaining is then
[Ca ] = (7.04 10 ) (5.56 10 ) = 1.48 10

2+ 5 5 5
mole L
NOTE: Because the carbonate buffer system is affected, the pH and solubility of CaCO3
also change.
4-18 Fluoride solubility
Given: Solubility product of CaF2 = 3.45 x 10-11, F- = 1.0 mg/L and Ca2+ = 200 mg/L
Solution:
4-11
a. Convert Ca and F to moles/L
[Ca ] = (40.08 g 200

2+ mg L
mole)(1000 mg g )
= 4.99 10 3
mole L
[F ] = (19.00 g 1mole
.0 mg L
)(1000 mg g )
= 5.26 10 6
mole L
b. Calculate solubility of F with 200 mg/L of Ca in solution.
KSP = [Ca2+][F-]2
KSP = [4.99 x 10-3][F-]2 = 3.45 x 10-11
12
[ ]
3.45 10 11
F = 3
= 8.31 10 5 mole L
4.99 10
c. Since 8.31 x 10-5 is greater than 5.26 x 10-5, the 1.0 mg/L of F will be soluble.
4-19 Concentrations of Ca and SO4
Given: CaSO4 solution, addition of 5.00 x 10-3 M Na2SO4, pKSP = 4.31
Solution:
a. From Appendix A
2
CaSO 4 Ca 2+ + SO 4
KSP = 10-4.31 = 4.898 x 10-5
b. Calculate the molar concentrations of Ca2+ and SO42- at equilibrium
[Ca2+] = [SO42-] = (4.898 x 10-5)1/2 = 6.998 x 10-3
c. Set up quadratic equation where
[Ca ] = (6.998 10 ) x
2+ 3
[SO ] = (6.998 10 ) + (5.00 10 ) x = (1.200 10 ) x

4
2 3 3 2
4-12
( )( )
K SP = 6.998 10 3 x 1.200 10 2 x = 4.898 10 5
(8.398 10 ) (1.899 10 )x + x
5 2 2
= 4.898 10 5
x 2 (1.899 10 2 )x + (8.398 10 5 ) = 4.898 10 5
x 2 (1.899 10 2 )x + (3.500 10 5 ) = 0
d. Solve the quadratic equation for roots
x=
[(
1.899 10 2 1.899 10 2 )
2
(
4 3.500 10 5 )]
12
x=
[
1.899 10 2 1.485 10 2 ]
2
x = 3.384 10 2 and x = 4.137 10 3
e. Because 3.384 x 10-2 > 6.998 x 10-3, or more than we started with, select x = 4.137 x
10-3
f. The amount of Ca2+ remaining is
[Ca2+] = 6.998 x 10-3 4.137 x 10-3 = 2.86 x 10-3 mole/L
g. The amount of sulfate remaining is
[SO42-] = 6.998 x 10-3 + 5.00 x 10-3 4.137 x 10-3 = 7.861 x 10-3 mole/L
4-20 Amount of base to neutralize acid
Given: Acid concentrations in Example 4-6
Solution:
a. The reaction is
H 2 SO 4 + 2 NaOH Na 2SO 4 + 2H 2 O
Therefore two moles of NaOH are required to neutralize each mole of H2SO4.
Assuming one liter:

4-13
100.00mg x
=
98.07 mg mole 2(39.996 mg mole)
x = (1.0197)(2)(39.997)
x = 81.5683 or 81.6 mg
4-21 Neutralize finished softened water
Given: pH is 10.74; normality of H2SO4 is 0.02000
Solution:
a. Assume only OH is present. Then
pOH = 14.00 - 10.74 = 3.26
[OH-] = 10-3.26 = 5.50 x 10-4 mole/L
b. Since n = 1 for OH- the normality = molarity. Then since
N x mL = N x mL
We can say
(5.50 x 10-4)(1000 mL) = (0.02000)(mL acid)
c. Solving for (mL acid)

mL acid = 27.477 or 27.5 mL
4-22 Neutralize finished water with HCl
Given: Problem 4-21
Solution: Since the normality is exactly the same as in Problem 4-21 the form of the acid
is irrelevant and the answer is the same as in Problem 4-21, i.e. 27.5 mL
4-23 Titration curve
Given: 50 mL solution of 0.0200 N NaOH; titrate with 0.0200 N HCl
Solution:
4-14
a. This is a strong base strong acid titration. The reaction is
NaOH + HCl NaCl + H 2 O
b. For this reaction n = 1 for both reactants and the molarity is equal to the normality.
c. The initial pH of the NaOH then is the pH of 0.0200 M OH-
pOH = -log(0.0200) = 1.699
pH = 14.00 1.699 = 12.30
d. After reaction with 1.0 mL of 0.0200 N HCl the molar concentration of NaOH is
(50.0mL )(0.0200 N ) (1.00mL)(0.0200 N ) = 0.0192 mole L

51.0mL
e. The pH is then
pOH = -log(0.0192) = 1.716
pH = 14.00 1.716 = 12.28
f. See spreadsheet below for remaining tabular calculations and plot.
Titrant
HCl 0.0200 N
Analyte
NaOH 0.0200 N
50.00 mL
Milliequivalents and moles of NaOH

meq = 1.0000
moles = 0.0010
Note that in each case the number of moles per liter = the number of equivalents per liter
Initial pOH = 3.00

Initial pH = 11.00
4-15
Moles of HCl Moles of NaOH

Milliters of acid pOH pH
Added Remaining
5 0.0001 0.0009 3.045757 10.95424
10 0.0002 0.0008 3.09691 10.90309
15 0.0003 0.0007 3.154902 10.8451
20 0.0004 0.0006 3.221849 10.77815
25 0.0005 0.0005 3.30103 10.69897
30 0.0006 0.0004 3.39794 10.60206
35 0.0007 0.0003 3.522879 10.47712
40 0.0008 0.0002 3.69897 10.30103
45 0.0009 0.0001 4 10
46 0.00092 0.0001 4.09691 9.90309
47 0.00094 0.0001 4.221849 9.778151
48 0.00096 0.0000 4.39794 9.60206
49 0.00098 0.0000 4.69897 9.30103
49.2 0.000984 0.0000 4.79588 9.20412
49.4 0.000988 0.0000 4.920819 9.079181
49.6 0.000992 0.0000 5.09691 8.90309
49.8 0.000996 0.0000 5.39794 8.60206
50 0.001 0.0000 7 7
At the equivalence point the pOH = 7.00
From the equivalence point on, pH is calculated directly.
Moles of HCl Moles of HCl

Milliters of acid pH pOH
Added Excess
55 0.0011 0.0001 4 10
60 0.0012 0.0002 3.69897 10.30103
70 0.0014 0.0004 3.39794 10.60206
80 0.0016 0.0006 3.221849 10.77815
90 0.0018 0.0008 3.09691 10.90309
100 0.002 0.0010 3 11
110 0.0022 0.0012 2.920819 11.07918
115 0.0023 0.0013 2.886057 11.11394
120 0.0024 0.0014 2.853872 11.14613
4-16
Problem 4-23 Titration Curve
12
10
8
pH
0
0 10 20 30 40 50 60
Milliters of HCl
Figure S-4-23: Titration curve
4-24 pH of water containing carbonic acid
Given: 0.6580 mg/L H2CO3; assume [H+] = [HCO3-]
Solution:
a. From Table 4-4, pKa = 6.35 for H2CO3
b. Convert mg/L to moles/L
0.6580mg
= 1.061 10 5 mole L
(62.026 g mole)(1000 mg g )
c. Write equilibrium expression
4-17
Ka =
[H ][HCO ] = 10
+
3

6.35
= 4.467 10 7
[H 2 CO 3 ]
d. Substitute carbonic acid concentration
=
[H ][HCO ] = 4.467 10
+
7
[1.061 10 ]
3
Ka 5
e. Assuming [H+] = [HCO3-]
[H+]2 = 4.739 x 10-12
[H+] = 2.177 x 10-6
pH = -log (2.177x10-6) = 5.66
4-25 HCO3- concentration at a pH of 4.50
Given: Problem 4-24
Solution:
a. From Table 4-4 pKa = 6.35 for H2CO3
b. The molar concentration of H2CO3 is
[H 2 CO 3 ] = 0.6580 mg L
= 1.061 10 5 mole L
(62.026 g mole)(1000 mg g )
c. Calculate [H+]
[H+] = 10-4.50 = 3.16 x 10-5
d. Solve the equilibrium expression for [HCO3-]
K a [H 2 CO 3 ] (10 6.35 )(1.061 10 5 mole L )

[HCO ] 3

=
[ ]
H+
=
3.16 10 5 mole L
= 1.498 x 10-7 or 1.50 x 10-7 mole/L
4-18
4-26 pH of water containing hypochlorous acid
Given: 0.5000 mg/L HOCl; assume equilibrium
Solution:
a. From Table 4-4, pKa = 7.54 for HOCl.
b. Convert mg/L to mole/L
0.5000mg
= 9.53 10 6 mole L
(52.45 g mole)(1000 mg g )
Ka =
[H ][OCl ] = 10
+
7.54
= 2.884 10 8
[HOCl]
d. Substitute hypochlorous acid concentration
Ka =
[H ][OCl ] = 2.884 10
+
8
[9.53 10 ]
6
e. Assuming [H+] = [OCl-]
[H+]2 = 2.748 x 10-13
[H+] = 5.24 x 10-7
pH = -log (5.24 x 10-7 ) = 6.28
4-27 OCl- concentration
Given: Data in Problem 4-26 and pH = 7.00
Solution:
a. From Table 4-4, pKa = 7.54 for HOCl.
b. Convert mg/L to mole/L
0.5000mg
= 1.371 10 5 mole L
(36.46 g mole)(1000 mg g )
4-19
Ka =
[H ][OCl ] = 10
+
7.54
= 2.884 10 8
[HOCl]
d. With [H+] = 10-7 and hypochlorous acid concentration
Ka =
[10 ][OCl ] = 2.884 10
7
8
[1.371 10 ] 5
e. Solve for [OCl-]
[OCl-] = 3.954 x 10-6 mole/L
f. Convert to mg/L
(3.954 x 10 6 mole/L)(51.452 g/mole)(1000 mg/g) = 0.2034 mg/L
4-28 Converting from mg/L to mg/L as CaCO3
Given: Concentrations in mg/L as ion.
Solution: E.W. of CaCO3 = 50.04
a. Ca2+ (n = 2 because valence = 2)
40.08
E.W. = = 20.04
2
50.04
mg/L as CaCO3 = 83.00 mg L = 207.3
20.04
b. Mg2+ (n = 2 because valence = 2)
24.305
E.W. = = 12.1525
2
50.04
mg/L as CaCO3 = 27.00 mg L = 111.2
12.1525
c. CO2 (n = 2 because H2CO3 has 2 hydrogens)

4-20
44.01
E.W. = = 22.00
2
50.04
mg/L as CaCO3 = 48.00 mg L = 109.2
22.00
d. HCO3- (n = 1 because valence = 1)
61.02
E.W. = = 61.02
1
50.04
mg/L as CaCO3 = 220.00 mg L = 180.4
61.02
e. CO32- (n = 2 because valence = 2)
60.01
E.W. = = 30.00
2
50.04
mg/L as CaCO3 = 15.00 mg L = 25.02
30.00
4-29 Converting from mg/L to mg/L as CaCO3
Given: Concentrations in mg/L as ion
Solution: E.W. of CaCO3 = 50.04
a. HCl (n = 1 because 1 replaceable H)
36.461
E.W. = = 36.461
1
50.04
mg/L as CaCO3 = 200.00 mg L = 274.5
36.461
b. CaO (n = 2 since Ca must be replaced by 2 H+)
56.08
E.W. = = 28.04
2
4-21
50.04
mg/L as CaCO3 = 280.00 mg L = 499.7
28.04
c. Na2CO3 (n = 2 because Na must be replaced by 2 H+)
105.99
E.W. = = 53.00
2
50.04
mg/L as CaCO3 = 123.45 mg L = 116.6
53.00
d. Ca(HCO3)2 (n = 2 as in b.)
162.12
E.W. = = 81.06
2
50.04
mg/L as CaCO3 = 85.05 mg L = 52.5
81.06
e. Na+ (n = 1 because valence = 1)
22.9898
E.W. = = 22.9898
1
50.04
mg/L as CaCO3 = 19.90 mg L = 9.143
22.9898
4-30 Converting from mg/L as CaCO3 to mg/L
Given: Concentrations in mg/L as CaCO3
Solution:
a. SO42- (n = 2 because valence = 2)
96.06
E.W. = = 48.03
2
48.03
mg/L = 100.00 mg/L as CaCO3 = 95.98
50.04
4-22
b. HCO3- (n = 1 because valence = 1)
61.016
E.W. = = 61.016
1
61.016
mg/L = 30.00 mg/L as CaCO3 = 36.58
50.04
c. Ca2+ (n = 2 because valence = 2)
40.08
E.W. = = 20.04
2
20.04
mg/L = 150.00 mg/L as CaCO3 = 60.07
50.04
d. H2CO3 (n = 2 because 2 H)
62.03
E.W. = = 31.02
2
31.02
mg/L = 10.00 mg/L as CaCO3 = 6.198
50.04
e. Na+ (n = 1 because valence = 1)
22.9898
E.W. = = 22.9898
1
22.9898
mg/L = 150.00 mg/L as CaCO3 = 68.91
50.04
4-31 Converting from mg/L as CaCO3 to mg/L
Given: Concentrations in mg/L as CaCO3
Solution:
a. CO2 (n = 2 because H2CO3 has 2 H+ replaceable)
4-23
44.01
E.W. = = 22.00
2
22.00
mg/L = 10.00 mg/L as CaCO3 = 4.397
50.04
b. Ca(OH)2 (n = 2 because Ca requires 2 H+ for replacement)
74.09
E.W. = = 37.045
2
37.045
mg/L = 13.50 mg/L as CaCO3 = 9.994
50.04
c. H3PO4 (n = 3 because of 3 H)
97.9951
E.W. = = 32.6650
3
32.6650
mg/L = 481.00 mg/L as CaCO3 = 314.0
50.04
d. H2PO4 (n = 2 because of 2 H)
96.9872
E.W. = = 48.4936
2
48.4936
mg/L = 81.00 mg/L as CaCO3 = 78.50
50.04
e. Cl- (n = 1 because valence = 1)
35.453
E.W. = = 35.453
1
35.453
mg/L = 40.00 mg/L as CaCO3 = 28.34
50.04
4-24
4-32 Convert N to mg/L as CaCO3
Given: 0.0100 N Ca2+
Solution:
a. Convert N to molarity (Eqn. 4-8)
N=M*n
M = (0.0100 N) / 2 = 0.0050 M
b. Convert M to mg/L
mg/L of species = (molarity)(GMW)(1000 mg/g)
= (0.0050)(40.08)(1000) = 200.40 mg/L as Ca2+
c. Calculate equivalent weights (n = 2 for each)
40.08 + 12.01 + 3(16.00 ) 100.09

E.W. CaCO3 = = = 50.045
2 2
40.08
E.W. Ca = = 20.04
2
d. Convert mg/L to mg/L as CaCO3 using Eqn. 4-40
50.04
mg/L as CaCO3 = 200.40 mg L = 500.4 or 500 mg/L as CaCO3
20.04
4-33 Exact alkalinity
Given: HCO3- = 0.6580 mg/L; pH = 5.66; CO32- = 0.00
Solution:
a. Convert HCO3- to mg/L as CaCO3
50.04
0.6580 = 0.53963 mg/L as CaCO3
61.016
b. Convert pH to [H+]
4-25
[H+] = 10-5.66 = 2.188 x 10-6 moles/L
c. In mg/L
mg/L = (2.1886 x 10-6 mole/L)(1.0079 x 103 mg/mole) = 2.205 x 10-3
d. In mg/L as CaCO3
(2.205 10 ) 150.0079
3 .04
= 0.10948

e. Convert pH to OH
pOH = 14.00 - 5.66 = 8.34
[OH] = 10-8.34 = 4.571 x 10-9 mole/L
f. In mg/L
mg/L = (4.571 x 10-9)(17.007 x 103 mg/mole) = 7.774 x 10-5
g. In mg/L as CaCO3
(7.774 10 ) 1750.007
5 .04
= 2.287 10
4
h. Exact alkalinity (all in mg/L as CaCO3)
ALK = HCO3- + CO32- + OH- - H+
ALK = 0.53963 + 0 + 2.287 x 10-4 - 0.10948
ALK = 0.4302 or 0.43 mg/L as CaCO3
4-34 Calculate approximate alkalinity
Given: HCO3- = 120 mg/L; CO32- = 15.00 mg/L
Solution:
a. Convert to mg/L as CaCO3
HCO3- (120 mg/L)(50.04/61.02) = 98.41

4-26
CO32- (15.00 mg/L)(50.04/30.00) = 25.02
b. Calculate approximate alkalinity
ALK = 98.41 + 25.02 = 123.43 or 123. mg/L as CaCO3
4-35 Exact alkalinity
Given: Problem 4-34; HCO3- = 120 mg/L; pH = 9.43; CO32- = 15.00 mg/L
Solution:
a. Convert HCO3- to mg/L as CaCO3
50.04
120.0 = 98.41 mg/L as CaCO3
61.016
b. Convert CO32- to mg/L as CaCO3
50.04
15.0 = 25.02 mg/L as CaCO3
30.004
c. Convert pH to H
[H+] = 10-9.43 = 3.715 x 10-10 mole/L
d. In mg/L
mg/L = (3.715 x 10-10 mole/L)(1.0079 x 103 mg/mole) = 3.745 x 10-7
e. In mg/L as CaCO3
(3.745 10 ) 150.0079
7 .04
= 1.86 10
5
f. Convert pH to [OH-]
pOH = 14.00 - 9.43 = 4.57
[OH-] = 10-4.57 = 2.692 x 10-5 mole/L
g. In mg/L
4-27
mg/L = (2.692 x 10-5)(17.007 x 103 mg/mole) = 0.4578
h. In mg/L as CaCO3
50.04
0.4578 = 1.347
17.007
i. Exact alkalinity (all in mg/L as CaCO3)
ALK = HCO3- + CO32- + OH- - H+
ALK = 98.41 + 25.02 + 1.347 - (1.86 x 10 5)
ALK = 124.78 mg/L as CaCO3
4-36 Approximate alkalinity
Given: 15.00 mg/L HCO3-, 120.0 mg/L CO32-
Solution:
HCO3- (15.00 mg L ) 50.04 = 12.30

61.02
CO32- (120.0 mg L ) 50.04 = 200.16

30.00
b. Approximate alkalinity
ALK = 12.30 + 200.16 = 212.46 or 212.5 mg/L as CaCO3
4-37 Derivations
Given: Equations 4-28, 4-36, 4-38, 4-39
Solution:
a. Starting with
Eqn. 4-28 Kw = [OH-][H+]

4-28
Eqn. 4-36 Alk = [HCO3-] + 2[CO32-] + [OH-] - [H+]
Eqn. 4-38 H2CO3 = H+ + HCO3- pKa1 = 6.35
Eqn. 4-39 HCO3- = H+ + CO32- pKa2 = 10.33
b. From equilibrium reactions (Eqns. 4-38, 4-39)
K1 =
[H ][HCO ]
+
3

[H 2 CO 3 ]
=
[H ][CO ]+ 2
[HCO ]
3
K2
3
c. From definition of alkalinity where A = Alkalinity
[HCO3-] = A - 2[CO32-] - [OH-] + [H+]
d. Substituting from Eqn. 4-28
[HCO ] = A 2[CO ] [KH ] + [H ]

3

3
2 w
+
+
e. Substituting the K2 equilibrium expression for CO32-
[HCO ] = A 2 K [[HCO ] K + [H ]
+
H ] [H ]
2 3 w
3 + +

f. Collecting terms
[HCO ] [
K 2 HCO 3 ] = A K
[H ] [ ]

+ 2 + H+
[ ]
w
3
H+ +

g. Factor out [HCO3-]
[HCO ]1 + 2[HK ] = A [KH ] + [H ]

3

+
2 w
+
+
h. Solve for HCO3-

4-29
[ ] [ ]
Kw
A + H+
[HCO ]
+
H
3 =
2K 2
1 + +
H [ ]
i. Since we need bicarbonate alkalinity in mg/L as CaCO3, a factor of 5 x 104 is used to
convert [HCO3-] to mg/L as CaCO3 (5x104 = 50 x 1000 = E.W. of CaCO3 x mL/L)
(
A 5 10 4 ) [KH ] + (5 10 )[H ]
w
+
4 +

HCO 3 =
2K 2
1 + +
H [ ]
(5 10 ) 5 A10 [KH ] + [H ]
4
4
w
+
+
HCO 3

=
2K 2
1 + +
H [ ]
j. An equation for CO32- can be derived by putting the HCO3- expression into the K2
equilibrium expression:
[ ] [ ]
Kw
A + H+
[CO ] [ ]
+
2 2K H
3 = +2
H 2K
1 + +2
[ ]
H
k. In terms of mg/L CaCO3 alkalinity
(5 10 ) 5 A10 [KH ] + [H ]
4 w
+
+
2 2K
4

= +2
CO 3
[ ]
H 2K
1 + +2

[ ]
H
[ ][ ]
2 2K
CO 3 = +2 HCO 3
H
4-30
4-38 Calculating bicarbonate and carbonate alkalinity
Given: Total alkalinity = 233.00 mg/L as CaCO3; pH = 10.47; Eqns. from Prob. 4-37.
Solution:
233.00 10.47 10 14
5 10
4
+ 10 10.47
5 10 4 10
=
( )
HCO 3
2 4.68 10 11
1 + 10.47

10
HCO 3 =
(
5 10 4 4.66 10 3 + 3.388 10 11 2.951 10 4 )
1 + 2.762
2.182 10 2
HCO 3 = = 58.01 mg/L as CaCO3
3.762
CO 3
2
= 58.01
(
2 4.68 10 11 )
10 10.47

= (58.01)(2.762 ) = 160.22 mg/L as CaCO3

2
CO 3
The total (58.01 + 160.22 = 210.23) does not equal total alkalinity (233.0) because the
OH-alkalinity is significant at a pH of 10.47.
With pOH = 14.00 10.47 = 3.53
[OH-] = 10-3.53
and the OH- alkalinity in mg/L as CaCO3 is
(10-3.53)(17.01)(1000 mg/g)(50.04/17.01) = 14.77 mg/L as CaCO3
Thus the total alkalinity = 58.01 + 160.22 + 14.77 = 233.0
4-39 Calculate bicarbonate and carbonate alkalinity
Given: Solution to Problem 4-37 and water specified in 4-43. Total alkalinity = 284.0
mg/L as CaCO3, pH = 7.6
Solution:
4-31
a. Bicarbonate
284.0 10 14
5 10 4 + 10 7.6 7.6

= 50000 10
( )
HCO 3 11
2 4.68 10
1 +
10 7.6
HCO 3 =
(
5 10 4 5.68 10 3 + 2.512 10 8 3.981 10 7 )
1 + 3.726 10 3
HCO3- = 2.829 x 102 mg/L as CaCO3
b. Carbonate
CO 3
2
= 2.892 10 2
(
2 4.68 10 11 ) = 1.08 mg/L as CaCO3
10 7.6

Check total alkalinity
Total ALK = 282.9 + 1.08 = 283.99 or 284.0 mg/L as CaCO3
4-40 Bicarbonate alkalinity as ion
Given: CO32- = 120.00 mg/L as ion; pH = 10.30
Solution:
a. Convert CO32- to mg/L as CaCO3
50.04
120.00 = 200.16 or 200.2 mg/L as CaCO3
30.00
b. From Problem 4-37
200.16 =
(
2 4.68 10 11 )(
HCO 3

)
10.30
10
c. Solve for HCO3-
4-32
200.16
HCO 3 = = 107.177 mg/L as CaCO3
1.868
d. Convert to ion
61.016
HCO 3 = 107.177 = 130.686 or 130.7 mg/L
50.04
4-41 Determining pH from carbonate and bicarbonate
Given: HCO3- = 120.00 and CO32- = 15.00 mg/L as ion
Solution:
HCO3- = 120.00 (50.04/61.016) = 100.053
CO32- = 15.00 (50.04/30.00) = 25.020
b. Use solution to Problem 4-37 and solve for [H+]
(
2 4.68 10 11
25.020 =
) (100.053)
[ ]
H+

[H ] = 9.365
9
+ 10
= 3.743 10 10
25.020
pH = -log(3.743 x 10-10) = 9.427 or 9.43
4-42 Calculating alkalinity by two methods
Given: Data in Problem 4-40 and equations from Problem 4-37
Solution:
a. Calculate CO32- and HCO3 concentrations in mg/L as CaCO3 in the same fashion as in
Problem 4-40.
CO32- = 200.16 mg/L as CaCO3
HCO3- = 107.177 mg/L as CaCO3

4-33
b. Setup equation from Problem 4-37 and solve for "A"
A 10.30 10 14
5 10 4 + 10
5 10 4 10 10.30
107.177 =
(
2 4.68 10 11
1 +
)

10.30
10
A = 317.07 mg/L as CaCO3
c. By the exact method we need [H+] and [OH-] in units of mg/L as CaCO3
d. Convert pH to [H+]
[H+] = 10-10.30 = 5.012 x 10-11 mole/L
e. In mg/L
mg/L = (5.012 x 10-11 mole/L)(1.0079 x 103 mg/mole)
= 5.051 x 10-8
f. In mg/L as CaCO3
(5.051 10 ) 150.0079
8 .04
= 2.508 10
6
g. Convert pH to [OH-]
pOH = 14.00 - 10.30 = 3.70
[OH-] = 10-3.70 = 1.995 x 10-4 mole/L
h. In mg/L
mg/L = (1.995 x 10-4)(17.007 x 103 mg/mole) = 3.393
i. In mg/L as CaCO3
50.04
3.393 = 9.984 mg/L as CaCO3
17.007
4-34
j. Exact alkalinity (all in mg/L as CaCO3)
ALK = HCO3- + CO32- + OH- - H+
ALK = 107.177 + 200.16 + 9.984 - (2.508 x 10-6)
ALK = 317.32 mg/L as CaCO3
4-43 Total carbonate and noncarbonate hardness
Given: Concentrations as ion, see table below
Solution:
a. Begin by converting to mg/L as CaCO3
Compound mg/L as ion EW/EW mg/L as CaCO3

Ca2+ 67.2 2.50 168.0
2+
Mg 40.0 4.12 164.8
HCO3- -- -- 284.0
b. Calculate TH, CH and NCH
TH = 168.0 + 164.8 = 332.8 mg/L as CaCO3
CH = HCO3- = 284.0 mg/L as CaCO3
NCH = TH - CH = 332.8 - 284.0 = 48.8 mg/L as CaCO3
4-44 Compute exact TH, CH and NCH
Given: Data from Problem 4-43
Solution:
a. Begin by converting to mg/L as CaCO3. Note valences may be found in appendix.

Ca2+ 67.20 2.50 168.00
Mg2+ 40.00 4.12 164.80
HCO3- -- -- 284.00
Fe3+ 0.20 2.69 0.54
Ba 0.50 0.73 0.36
B 0.10 13.89 1.39
4-35
TH = 168.0 + 164.8 + 0.54 + 0.36 + 1.39 = 335.1 mg/L as CaCO3
CH = HCO3- = 284.0 mg/L as CaCO3
c. Calculate percent error.
335.1 332.8
Error in TH = 100 = 0.69%
335.1
Error in CH = 0.00%
51.1 48.8
Error in NCH = 100 = 4.5%
51.1
4-45 Total, Carbonate, Non Carbonate Hardness
Given: Concentrations as shown below
Solution:

Ca2+ 78.0 2.50 195.0
Mg2+ 32.0 4.12 131.8
HCO3- -- -- 494.0
TH = 195.0 + 131.8 = 326.8 mg/L as CaCO3
CH = 326.8 mg/L as CaCO3 (all hardness is carbonate)
NCH = 0.0 mg/L as CaCO3
4-46 Total, Carbonate, Non Carbonate Hardness
Given: Concentrations as shown below
Solution:
4-36

Ca2+ 96.8 2.50 242.0
Mg2+ 30.4 4.12 125.3
HCO3- 318.0 0.82 260.9
TH = 242.0 + 125.3 = 367.3 mg/L as CaCO3
CH = 260.9 mg/L as CaCO3
4-47 Total, Carbonate, and Non-carbonate hardness
Given: Kool Artesian Water analysis
Solution:
a. Using solution from Problem 4-32 to find bicarbonate concentration
285.0 10 14
5 10 4 + 10 7.6 7.6

= 50000 10
( )
HCO 3
2 4.68 10 11
1 +
10 7.6

=
(
5 10 4 5.70 10 3 + 2.512 10 8 3.981 10 7 )
HCO 3
(
1 + 3.762 10 3 )
HCO3- = 285.0 mg/L as CaCO3
b. Convert Ca2+ and Mg2+ concentrations to mg/L as CaCO3
50.04
Ca 2+ = (37.0 mg L ) = 92.39 mg/L as CaCO3
20.04
50.04
Mg 2+ = (18.1 mg L ) = 74.51 mg/L as CaCO3
12.16
4-37
c. TH, CH, and NCH
TH = 92.39 + 74.51 = 166.90 mg/L as CaCO3
NCH = 0.0 mg/L as CaCO3
4-48 Reaction order and rate constant
Given: Data table
Solution:
a. The data plot as a straight line on semi log paper. Thus, the reaction order is first order
based on the linearized forms shown in Table 4-6.
Problem 4-48 Rate Constant
10.00
Concentration, mmoles/L
1.00
-0.1401x
y = 2.8002e
0.10
0 5 10 15 20 25
Time, min
Figure S-4-48: Rate constant plot
4-38
b. The rate constant may be determined by selecting values of A0, A, and the
corresponding time increment.
A
ln = Kt
A0
At t = 5 min
1.39
ln = K (5)
2.80
-0.7003 = -K(5)
K = 0.1401 min-1
4-49 Reaction order and rate constant
Given: Data table
Solution:
a. The data plot as a straight line on arithmetic paper if the concentration is plotted as
1/[A0]. Thus, the reaction order is second order based on the linearized forms shown
in Table 4-6.
4-39
Problem 4-49 Rate Constant
1.6
1.4
1.2
1
1/[A]
0.8
y = 0.1399x + 0.0208
0.6
0.4
0.2
0
0 5 10 15
Time, min
Figure S-4-49: Rate constant plot
b. The rate constant may be determined by selecting values of A0, A, and the
corresponding time increment.
1 1
+ = Kt
A A0
At t = 5 min
= K (5)
1 1
+
1.39 48.0
0.72 + 0.021 = K(5)
K = 0.1482 min-1
(Slightly different K will result for other time intervals.)
4-40
4-50 Alkalinity remaining after alum dose
Given: Total alkalinity = 130.0 mg/L as CaCO3; pH = 7.4; alum dose = 60.00 mg/L
Solution:
a. Since pH is 7.4 all alkalinity may be assumed to be bicarbonate
b. Convert alum to CaCO3 equivalent. From the equivalent weight equation and the
discussion that follows the Eqn., n=6
594.346
E.W. = = 99.058
6
50.04
60.00 = 30.31 mg/L as CaCO3
99.058
c. This is equal to the amount of alkalinity that will be destroyed. Thus, the alkalinity
remaining is
HCO3- remaining = 130.0 - 30.31 = 99.69 or 100 mg/L as CaCO3
4-51 Alkalinity remaining after ferric chloride dose
Given: Total alkalinity = 136.0 mg/L as CaCO3; pH = 7.6; ferric chloride dose = 30.00
mg/L
Solution:
a. With pH = 7.6 assume all alkalinity is HCO3-
b. Convert ferric chloride to CaCO3 equivalent. From Eqn 4-53, note that each mole of
ferric chloride destroys 3 moles of alkalinity and n = 3.
162.206
E.W. = = 54.069
3
50.04
30.00 = 27.76 mg/L as CaCO3
54.069
HCO3- remaining = 136.0 - 27.8 = 108.2 mg/L as CaCO3

4-41
4-52 Alkalinity remaining after alum dose
Given: Total alkalinity = 29.5 mg/L as CaCO3; pH = 7.2; alum dose = 40.00 mg/L
Solution:
a. Since pH is 7.2 all alkalinity may be assumed to be bicarbonate
b. Convert alum to CaCO3 equivalent. From the equivalent weight equation and the
discussion that follows the Eqn., n = 6
594.346
E.W. = = 99.058
6
50.04
40.00 = 20.21 mg/L as CaCO3
99.058
c. This is equal to the amount of alkalinity that will be destroyed. Thus, the alkalinity
remaining is
HCO3- remaining = 29.5 - 20.21 = 9.29 mg/L as CaCO3
4-53 Bar chart of Problem 4-43
Given: Data in Problem 4-43
Solution:
a. E.W. CaCO3
4-42
Ion mg/L as ion EW ion mg/L as CaCO3

Fe3+ 0.20 2.69 0.54
Mn 0.00 1.82 0.00
NH3 0.50 2.78 1.39
Na 4.70 2.18 10.25
K 0.90 1.28 1.15
Ca 67.20 2.50 168.00
Mg 40.00 4.12 164.80
Ba 0.50 0.73 0.36
SiO2 20.00 0.83 16.60
F 0.35 2.63 0.92
B 0.10 13.89 1.39
NO3 0.00 0.81 0.00
Cl 4.50 1.41 6.35
SO4 29.00 1.04 30.16
HCO3 -- -- 284.00
pH = 7.6
b. CO2 calculation
With pH < 8.3 assume all alkalinity is HCO3-
K a1 =
[H ][HCO ]
+
3

[H 2 CO 3 ]
pKa = 6.35 from Table 4-4
Assume 1 mole H2CO3 = 1 mole CO2
CO 2 + H 2 O H 2 CO 3
Convert HCO3- mg/L as CaCO3 to mole/L
[HCO ]

61E.W.HCO 3
= (284 mg L )
1 1

3 50E.W.CaCO
61 g mole 1000 mg g 3
[HCO3-] = 5.68 x 10-3 mole/L
Convert pH to mole/L
4-43
[H+] = 10-7.6 = 2.51 x 10-8 mole/L
Convert pKa1 to Ka
Ka1 = 10-6.35 = 4.47 x 10-7
Solve for H2CO3
[H 2 CO 3 ] = (2.51 10 )(5.687 10 )
8 3
(4.47 10 )
[H2CO3] = 3.19 x 10-4 mole/L
Since CO2 = H2CO3
[CO2] = 3.19 x 10-4 mole/L
Convert mole/L to mg/L as CaCO3
(3.19 10 ) 50.04
mole L (44 g mole)(1000 mg g )
4

22.00
CO2 = 31.9 mg/L as CaCO3
Solution:
a. E.W. CaCO3
4-44

Fe3+ 0.42 2.69 1.13
Mn 0.04 1.82 0.07
NH3 11.00 2.78 30.58
Na 78.00 2.18 170.04
K 2.60 1.28 3.33
Ca 78.00 2.50 195.00
Mg 32.00 4.12 131.84
Ba 0.50 0.73 0.37
Cu 0.01 1.57 0.02
Zn 0.01 1.53 0.02
SiO2 20.00 0.83 16.60
F 0.30 2.63 0.79
B 0.30 13.89 4.17
NO3 0.00 0.81 0.00
Cl 9.00 1.41 12.69
SO4 0.00 1.04 0.00
HCO3 -- -- 494.00
pH = 7.7
b. Calculate CO2
Ka =
[H ][HCO ]
+
3

[H 2 CO 3 ]
CO 2 + H 2 O H 2 CO 3
[HCO ]

61E.W.HCO 3
= (494 mg L )
1 1
3
1000 mg g 50E.W.CaCO
61 g mole 3
[HCO3-] = 9.88 x 10-3 mole/L
4-45
[H+] = 10-7.7 = 2.00 x 10-8 mole/L
Convert pKa1 to Ka
Ka1 = 10-6.35 = 4.47 x 10-7
Solve for [H2CO3]
[H 2 CO 3 ] = (2.00 10 )(9.887 10 )
8 3
(4.47 10 )
[H2CO3] = 4.42 x 10-4 mole/L
Since CO2 = H2CO3
[CO2] = 4.42 x 10-4 mole/L
( ) 50.04
CO 2 = 4.42 10 4 mole L (44 g mole)(1000 mg g )
22.00
Solution:
a. E.W. as CaCO3 (continued on following page)
4-46

F 1.10 2.63 2.89
Cl 4.00 1.41 5.64
NO3 0.00 0.81 0.00
Na 14.00 2.18 30.52
K 1.60 1.28 2.05
Ca 96.80 2.50 242.00
Mg 30.40 4.12 125.25
SiO2 13.40 0.83 11.12
HCO3 318.00 0.82 260.76
SO4 52.00 1.04 54.08
Fe 0.50 2.69 1.35
Mn 0.07 1.82 0.13
Zn 0.27 1.53 0.41
Ba 0.20 0.73 0.15
b. Because the pH is not given the CO2 concentration cannot be calculated.
4-56 Bar chart of Lake Michigan water
Given: Lake Michigan data
Solution:
a. Convert constituents to mg/L as CaCO3
Constituent mg/L as ion EW ion mg/L as CaCO3

Ca 38.4 2.5 96
Mg 11.4 4.12 46.968
Fe 0.1 2.69 0.269
Na 5.8 2.18 12.644
Cl 14 1.41 19.74
SO4 26 1.04 27.04
SiO2 1.2 0.83 0.996
-
HCO3 -- -- 115
b. Calculate CO2 (ignoring carbonate alkalinity)
K a1 =
[H ][HCO ]
+
3

[H 2 CO 3 ]
pKa1 = 6.35 From Table 4-4

4-47
CO 2 + H 2 O H 2 CO 3
[HCO ]

61E.W.HCO 3
= (115 mg L )
1 1
3
61 g mole 3
[HCO3-] = 2.30 x 10-3 mole/L
[H+] = 10-8.4 = 3.98 x 10-9
Convert pKa1 to Ka1
Ka1 = 10-6.35 = 4.47 x 10-7
Solve equilibrium expression for [H2CO3]
[H 2 CO 3 ] = (3.98 10 )(2.307 10 ) = 2.05 10 5 mole L

9 3
(4.47 10 )
Since CO2 = H2CO3
[CO2] = 2.05 x 10-5 mole/L
( ) 50.04
CO 2 = 2.05 10 5 mole L (44 g mole)(1000 mg g )
22.00
4-57 Water softening; Mg < 40 mg/L as CaCO3
Given: Ca = 120.0; Mg = 30.0; HCO3- = 70.0; CO2 = 10.0; all mg/L as CaCO3.
Solution:
a. Compute TH, CH and NCH
4-48
TH = 120.0 + 30.0 = 150.0 mg/L as CaCO3
NCHi = 150.0 - 70.0 = 80.0 mg/L as CaCO3
b. Compute Lime Additions (all as mg/L as CaCO3)
Lime = CO2 = 10.0
Lime = HCO3- = 70.0
Since Mg2+ is < 40 add lime = 20.0
Total Lime = 10.0 + 70.0 + 20.0 = 100.0 mg/L as CaCO3
c. Compute Soda (all as mg/L as CaCO3)
NCHf = 80.00 - 40.0 = 40.0
NCHR = NCHi - NCHf = 80.00 - 40.00 = 40.00
Add soda = 40.0 mg/L as CaCO3
Given: CO2 = 4.6, Ca = 257.9, Mg =22.2, HCO3- = 248.0, SO42+ = 32.1; all mg/L as
CaCO3
Solution:
a. Calculate TH, CH, and NCHi
TH = 257.9 + 22.2 = 280.10 mg/L as CaCO3
NCHi = 280.10 248.0 = 32.10 mg/L as CaCO3
b. Computer lime additions (all mg/L as CaCO3)
Lime = CO2 = 4.60
Lime = HCO3- = 248.0
4-49
Since Mg2+ < 40 add an excess of lime = 20.0
Total lime = 4.6 + 248.0 + 20.0 = 272.6 mg/L as CaCO3
c. Compute Soda ash additions (all mg/L as CaCO3)
NCHf = 80.0 40.0 = 40.0
NCHR = 32.10 40.0 = -7.90
Negative number, therefore no soda ash required.
Given: Ca = 210.0; Mg = 23.0; HCO3- = 165.0; CO2 = 5.0; all mg/L as CaCO3. Lime is
90% pure and soda ash is 97% pure.
Solution:
TH = 210.0 + 23.0 = 233.0 mg/L as CaCO3
NCHi = 233.0 - 165.0 = 68.0 mg/L as CaCO3
b. Compute Lime Additions (all as mg/L as CaCO3)
Lime = CO2 = 5.0
Lime = HCO3- = 165.0
Since Mg2+ is < 40 add lime = 20.0
c. Compute Soda (all as mg/L as CaCO3)
NCHf = 80.00 - 40.0 = 40.0
NCHR = NCHi - NCHf = 68.0 - 40.0 = 28.0
Soda = 28.0 mg/L as CaCO3
4-50
d. Convert lime to CaO and correct for purity

(Note E.W. of CaO = 28 and E.W. of CaCO3 = 50)
28 1
(190.0 mg/L as CaCO3) = 118.22 or 118 mg/L CaO
50 0.9
e. Convert soda to Na2CO3 and correct for purity

(Note: E.W. of Na2CO3 = 53)
53 1
(28.0 mg/L as CaCO3) = 30.59 or 31 mg/L Na2CO3
50 0.97
4-60 Soften water
Given: Ca = 220.0; Mg = 75.0; HCO3- = 265.0; CO2 = 17.0 all mg/L as CaCO3
Solution:
TH = 220.0 + 75.0 = 295.0 mg/L as CaCO3
NCH = 295.0 - 265.0 = 30.0 mg/L as CaCO3
b. Compute Lime Additions (all as CaCO3)
Lime = CO2 = 17.0
Lime = HCO3- = 265.0
Since Mg is > 40 add lime = 75.0 - 40.0 = 35.0

and Delta = 35.0
Is Delta > 40? No
Is Delta < 20? No
Add lime = Delta = 35.0
Total Lime = 17.0 + 265.0 + 35.0 + 35.0 = 352.0 mg/L as CaCO3
c. Compute Soda
4-51
NCHf = 70.0 - 40 = 30
NCHR = NCHi - NCHf = 30.0 - 30.0 = 0
Add no soda ash
4-61 Water softening; (Mg 40) is >20 and < 40
Given: CO2 = 39.8, Ca = 167.7, Mg = 76.3, HCO3- = 257.9; all in mg/L as CaCO3
Solution:
a. Calculate TH, CH, and NCH
TH = 167.7 + 76.3 = 244.0 mg/L as CaCO3
Because HCO3- > TH, all the hardness is CH.
CH = 244.0
NCHi = 0.0
b. Calculate lime additions (all mg/L as CaCO3)
Lime = CO2 = 39.8
Lime = HCO3- = 257.9
Lime = Mg 40 = 76.3 40 = 36.3
Because (Mg 40) is > 20 and < 40 add excess lime = Mg 40 = 36.3
Total Lime = 39.8 +257.9 +36.3 + 36.3 = 370.3 mg/L as CaCO3
4-62 Soften water
Given: Ca = 137.0; Mg = 56.0; HCO3- = 128.0; CO2 = 7.0 all mg/L as CaCO3. Lime is
93% pure and soda ash is 95% pure.
Solution:
TH = 137.0 + 56.0 = 193.0 mg/L as CaCO3

4-52
NCH = 193.0 - 128.0 = 65.0 mg/L as CaCO3
b. Compute Lime Additions (all as CaCO3)
Lime = CO2 = 7.0
Lime = HCO3- = 128.0

and Delta = 16.0
Is Delta > 40? No
Is Delta < 20? Yes
Add lime = 20.0
Total Lime = 7.0 + 128.0 + 16.0 + 20.0 = 171.0 mg/L as CaCO3
c. Compute Soda
NCHf = 80.0 - 40 = 40
NCHR = NCHi - NCHf = 65.0 - 40.0 = 15.0
d. Convert lime to CaO and correct for purity

(Note E.W. of CaO = 28 and E.W. of CaCO3 = 50)
28 1
(171.0 mg/L as CaCO3) = 102.97 or 103 mg/L CaO
50 0.93
e. Convert soda to Na2CO3 and correct for purity

(Note: E.W. of Na2CO3 = 53)
53 1
(15.0 mg/L as CaCO3) = 16.74 or 17 mg/L Na2CO3
50 0.95
4-53
4-63 Water softening; Mg > 40 mg/L as CaCO3
Given: CO2 = 44.2, Ca = 87.4, Mg = 96.3, HCO3- = 204.6; all mg/L as CaCO3
Solution:
a. Calculate TH, CH, and NCH (all mg/L as CaCO3)
TH = 87.4 + 96.3 = 183.7
Because HCO3- > TH, all the hardness is CH.
CH = 183.7
NCHi = 0.0
b. Lime addition (all mg/L as CaCO3)
Lime = CO2 = 44.2
Lime = HCO3- = 204.6
Lime = Mg 40 = 96.3 40 = 56.3
Because (Mg 40) is > 40, add excess lime = 40.0
Total Lime = 44.2 + 204.6 +56.3 + 40.0 = 345.1 mg/L as CaCO3
c. Compute soda ash additions
Because there is no NCH, add no soda ash.
4-64 Soften water
Given: Water described in Prob. 4-43

Ca = 67.2 mg/L as ion
Mg = 40.0 mg/L as ion
Alkalinity = 284. mg/L as CaCO3
pH = 7.6
Required: Soften water to 100.0 mg/L as CaCO3
Solution:
a. Calculate CO2 content

4-54
Since pH < 8.3 assume all alkalinity is HCO3-
Ka =
[H ][HCO ]
+
3

[H 2 CO 3 ]
CO 2 + H 2 O H 2 CO 3
[HCO ]

61E.W.HCO 3
= (284 mg L )
1 1

3 50E.W.CaCO
61 g mole 1000 mg g 3
[HCO3-] = 5.68 x 10-3 mole/L
[H+] = 10-7.6 = 2.51 x 10-8 mole/L
Convert pKa1 to Ka
Ka1 = 10-6.35 = 4.47 x 10-7
Solve for H2CO3
[H 2 CO 3 ] = (2.51 10 )(5.687 10 )
8 3
(4.47 10 )
[H2CO3] = 3.19 x 10-4 mole/L
Since CO2 = H2CO3

[CO2] = 3.19 x 10-4 mole/L
(3.19 10 4
) 50.04
mole L (44 g mole)(1000 mg g ) = 44.2 mg/L as CaCO3
22.0
b. Calculate concentration of Ca and Mg as mg/L as CaCO3

4-55
Ca = (67.2 mg/L) (2.50 EW CaCO3/EW ion) = 168 mg/L as CaCO3
Mg = (40.0 mg/L) (4.12 EW CaCO3/EW ion) = 164.8 mg/L as CaCO3
c. Calculate TH, CH and NCH
TH = 168.0 + 164.8 = 332.8 mg/L as CaCO3
CH = lesser of TH or alkalinity = 284.mg/L as CaCO3
NCH = 332.8 - 284.0 = 48.8 mg/L as CaCO3
d. Soften the water (All additions are mg/L as CaCO3)
Lime = CO2 = 31.90
Lime = HCO3- = 284.
Lime = Mg - 40. = 164.8 - 40. = 124.8 and Delta = 124.8
Since Delta is > 40, excess lime = 40.
Total Lime = 31.90 + 284. + 124.8 + 40 = 480.7 or 481 mg/L as CaCO3
NCH = 100.0 - 40.0 = 60.0 mg/L as CaCO3
NCH = 48.8 - 60.0 = 11.20 mg/L as CaCO3
No soda ash is required
4-65 Soften water
Given: Water described in Prob. 4-50
TH = 260 mg/L as CaCO3

Ca = 235 mg/L as CaCO3
Mg = 25 mg/L as CaCO3
Alkalinity = 130mg/L as CaCO3
pH = 7.4
Required: Soften water to 90 mg/L as CaCO3
Solution:
4-56
Ka =
[H ][HCO ]
+
3

[H 2 CO 3 ]
CO 2 + H 2 O H 2 CO 3
[HCO ] = (130 mg L) 61g 1mole 10001mg g 50

61E.W.HCO
3
3
E.W.CaCO 3
[HCO3-] = 2.60 x 10-3 mole/L
[H+] = 10-7.4 = 3.98 x 10-8 mole/L
Convert pKa1 to Ka
Ka1 = 10-6.35 = 4.47 x 10-7

Solve for H2CO3
[H 2 CO 3 ] = (3.98 10 )(2.607 10 )
8 3
(4.47 10 )
[H2CO3] = 2.31 x 10-4 mole/L
Since CO2 = H2CO3
[CO2] = 2.31 x 10-4 mole/L
(2.31 10 4
) 50.04
22.0
4-57
b. Calculate CH and NCH
CH = lesser of TH or alkalinity = 130. mg/L as CaCO3
NCH = TH - CH = 260. - 130. = 130. mg/L as CaCO3
c. Lime additions (All additions mg/L as CaCO3)
Lime = CO2 = 21.15
Lime = HCO3- = 130.00
Since Mg < 40, lime = Mg to be removed = 0.0
Excess lime = 20.0
Total lime = 21.15 + 130.0 + 20.
= 171.15 or 171. mg/L as CaCO3
d. Soda
NCHf = 90.0 - 40.0 = 50.0 mg/L as CaCO3
NCHR = 130.0 - 50.0 = 80.0 mg/L as CaCO3
Add Soda = 80. mg/L as CaCO3
4-66 Water softening for Village of Galena
Given: Water analysis, HCO3- = 276.6 mg/L as CaCO3, pH = 7.2, Ca = 177.8 mg/L as
ion, Mg = 16.2 mg/L as ion, Pb = 0.020 mg/L as ion
Solution:
a. Compute CO2 in mg/L as CaCO3
K a1 =
[H ][HCO ]
+
3

[H 2 CO 3 ]
pKa1 = 6.35 from Table 4-4
Assume 1 mole H2CO3 = 1 mole CO2 from

4-58
CO 2 + H 2 O H 2 CO 3
Convert HCO3- in mg/L as CaCO3 to mole/L
[HCO ]

61E.W.HCO 3
= (276.6 mg L )
1 1
3
61 g mole 3
[HCO3-] = 5.53 x 10-3 mole/L
[H+] = 10-7.2 = 6.31 x 10-8 mole/L
Convert pKa1 to Ka1
Ka1 = 10-6.35 = 4.47 x 10-7 mole/L
Solve for [H2CO3]
[H 2 CO 3 ] = (6.31 10 )(5.537 10 )
8 3
(4.47 10 )
[H2CO3] = 7.81 x 10-4 mole/L
b. Calculate soda ash (mg/L as CaCO3)
NCHf = 80 40 = 40.0
NCHR = 234.06 40 = 194.06 or 194.1
Add soda ash = 194.1 mg/L as CaCO3
c. Lime as CaO (93% pure)
1 28.04E.W.CaO
(408.1) = 245.9 or 246 mg/L as CaO
0.93 50.04E.W.CaCO 3
d. Soda ash as Na2CO3 (95% pure)
4-59
1 52.99E.W.Na 2 CO 3
(194.1) = 216.3 or 216 mg/L as Na2CO3
0.95 50.04E.W.CaCO 3
e. Lead removal
The concentration of Pb is 0.020 mg/L. This is
(0.020) 50.04E.W.CaCO 3 = 0.0097 mg/L as CaCO3

103.6E.W.Pb
This amount will be removed by the excess lime if the solubility is low enough. From
table of solubility products in Appendix A, the solubility of PbCO3 is less than CaCO3. It
will be removed.
4-67 Soften water
Given: Ca = 200; Mg = 100; HCO3- = 150; CO2 = 22; all mg/L as CaCO3; lime =
$100/megagram (Mg); soda = $200/megagram (Mg); flow = 0.5 m3/s.
Solution:
TH = 200.0 + 100.0 = 300.0 mg/L as CaCO3
NCHi = 300.0 - 150.0 = 150.0 mg/L as CaCO3
b. Compute Lime Additions (all mg/L as CaCO3)
Lime = CO2 = 22.0
Lime = HCO3- = 150.0
Delta = 60.0
Since Delta is > 40 add lime = 40.0
Total lime = 22.0 + 150.0 + 60.0 + 40.0 = 272.0 mg/L as CaCO3
4-60
c. Compute Soda
NCHf = 80.0 - 40.0 = 40.0
NCHR = 150.0 - 40.0 = 110.0 mg/L as CaCO3
d. Lime as CaO
28.04E.W.CaO
(272.00) = 152.41 mg L
50.04E.W.CaCO 3
e. Soda as Na2CO3
105.99
E.W. = = 52.99
2

(110.00) 52.99E.W.Na 2 CO 3 = 116.49 mg L
50.04E.W.CaCO 3
f. Annual cost
(0.50 m s )(86400 s d )(365 d y) = 15,768,000 = 1.58 10

3 7
m3
(1000 L/m3)(1.58 x 107 m3) = 1.58 x 1010 L
CaO
(152.41 mg/L)(1.58 x 1010 L) = 2.40 x 1012 mg
(2.40 x 1012 mg)(10-9 Mg/mg) = 2.40 x 103 Mg
(2.40 x 103 Mg)($100.00/Mg) = $240,326.45
Na2CO3
(116.49 mg/L)(1.58x1010 L)(10-9 Mg/mg) = 1.84 x 103 Mg
(1.84 x 103 Mg)($200.00/Mg) = $367,376.80
Total Cost
240,326.45 + 367,376.80 = 607,703.25 or $608,000

4-61
4-68 Soften water
$61.70/megagram (Mg); soda = $172.5/megagram (Mg); flow = 1.35 m3/s. Lime
is 87% pure and soda is 97% pure.
Solution:
TH = 293.0 + 55.0 = 348.0 mg/L as CaCO3
NCHi = 348.0 - 301.0 = 47.0 mg/L as CaCO3
Lime = CO2 = 3.0
Lime = HCO3- = 301.0
Since Mg is > 40 add lime = 55.0 40.0 = 15.0
Delta = 15.0
Since Delta is < 40 add lime = 20.0
Total lime = 3.0 + 301.0 + 15.0 + 20.0 = 339.0 mg/L as CaCO3
c. Compute Soda
NCHf = 120.0 - 40.0 = 80.0
NCHR = 80.0 - 47.0 = 33.0 mg/L as CaCO3
d. Lime as CaO (87% pure)
1 28.04E.W.CaO
(339.0) = 218.34 mg L
0.87 50.04 E.W.CaCO 3
4-62
e. Soda as Na2CO3 (97% pure)
105.99
E.W. = = 52.99
2
1 52.99E.W.Na 2 CO 3
(33.0 ) = 36.02 mg L
0.97 50.04E.W.CaCO 3
f. Annual cost
(1.35 m3/s)(86400 s/d)(365 d/y) = 42,573,600 = 4.26 x 107 m3
(1000 L/m3)(4.26 x 107 m3) = 4.26 x 1010 L

CaO
(218.34 mg/L)(4.26 x 1010 L) = 9.30 x 1012 mg
(9.30 x 1012 mg)(10-9 Mg/mg) = 9.30 x 103 Mg
(9.30 x 103 Mg)($61.70/Mg) = $573,810
Na2CO3
(36.02 mg/L)(4.26 x 1010 L)(10-9 Mg/mg) = 1.53 x 103 Mg
(1.53 x 103 Mg)($172.50/Mg) = $264,698
Total Cost
$573,810 + $264,698 = $838,508
4-69 Soften water
Given: Hardin, IL water
Ca = 102.0 mg/L as ion

Mg = 45.2 mg/L as ion
Alkalinity = 344. mg/L as CaCO3
pH = 7.2
Q = 0.150 m3/s
Required: (1) Soften water to 95.0 mg/L as CaCO3
4-63
(2) Determine annual chemical cost using prices from Prob. 4-67. CaO
price is $100.000/Mg; Na2CO3 price is $200.00/Mg
Solution:
K a1 =
[H ][HCO ]
+
3

[H 2 CO 3 ]
pKa1 = 6.35 from Table 4-4
CO 2 + H 2 O H 2 CO 3
[HCO ] = (344 mg L) 61g 1mole 10001mg g 50

61E.W.HCO
3
3
E.W.CaCO 3
[HCO3-] = 6.88 x 10-3 mole/L
[H+] = 10-7.2 = 6.31 x 10-8 mole/L
Convert pKa1 to Ka1
Ka1 = 10-6.35 = 4.47 x 10-7
Solve for H2CO3
] = (6.31 10 )(6.88 10 )
8 3
[H 2 CO 3
(4.47 10 ) 7
[H2CO3] = 9.71 x 10-4 mole/L
Since CO2 = H2CO3
[CO2] = 9.71 x 10-4 mole/L

4-64
(9.71 10 4
) 50.04
22.00
b. Convert Ca and Mg to CaCO3
Ca = (102.0)(2.50) = 255.0 mg/L as CaCO3
Mg = (45.2)(4.12) = 186.2 mg/L as CaCO3
c. Calculate CH and NCH
TH = 255.0 + 186.2 = 441.2 mg/L as CaCO3
CH = lesser of TH or alkalinity = 344. mg/L as CaCO3
NCH = 441.2 - 344. = 97.2 mg/L as CaCO3
d. Lime additions (all mg/L as CaCO3)
Lime = CO2 = 97.10
Lime = HCO3- = 344.
Lime = Mg - 40. = 186.2 - 40 = 146.2
Delta = 146.2
Since Delta > 40, excess lime = 40.
Total Lime = 97.10 + 344. + 146.2 + 40. = 627.3 or 627. mg/L as CaCO3
e. Soda calculations
NCH = 95.0 - 40.0 = 55.0 mg/L as CaCO3
NCH = 97.2 - 55.0 = 42.2 mg/L as CaCO3
Soda ash = 42.2 mg/L as CaCO3
f. Calculate cost
4-65
Convert lime and soda from mg/L as CaCO3 to mg/L as compound.

E.W. CaO = 28.04; E.W. Na2CO3 = 52.994
CaO (87% pure)
(627.3) 28.04 1
= 415.63 or 416 mg/L
50.04 0.87
Na2CO3 (97% pure)
1
(42.2) 52.994 = 46.08 or 46 mg/L
50.04 0.97
Estimate annual use. (Note that 1 mg/L = 1 g/m3)
Lime = (415.63 g/m3)(0.150 m3/s)(86,400 s/d)(365 d/y)
= 1.97 x 109 g/y or 1966 Mg/y
Soda = (46.08 g/m3)(0.150 m3/s)(86,400 s/d)(365 d/y)
= 2.18 x 108 g/y or 218 Mg/y
Estimate annual cost
Lime = ($100.00/Mg)(1966 Mg/y) = $196,610./y
Soda = ($200.00/Mg)(218 Mg/y) = $43,598./y
Total Cost = $196,610./y + $43,598./y = $240,208/y or $240,000
4-70 Soften water
$61.70/megagram (Mg); soda = $172.5/megagram (Mg); flow = 0.05 m3/s. Lime
is 90% pure and soda is 97% pure.
Solution:
TH = 137.0 + 40.0 = 177.0 mg/L as CaCO3

4-66
NOTE: CH = alkalinity (HCO3-) or TH whichever is less. In this case TH < CH
NCHi = 177.0 - 177.0 = 0.0 mg/L as CaCO3
Lime = CO2 = 9.0
Lime = HCO3- = 197.0
NOTE: must still add lime = HCO3- to raise pH to achieve precipitation
Since Mg is < 40 add lime = 20.0
Total lime = 9.0 + 197.0 + 20.0 = 226.0 mg/L as CaCO3
c. Compute Soda
NCHf = 90.0 - 40.0 = 50.0
NCHR = 0.0 - 50.0 = 50.0 mg/L as CaCO3
Therefore, ADD NO SODA
d. Lime as CaO (90% pure)
(226.0) 28.04 1
= 140.71 mg L
50.04 0.90
e. Soda as Na2CO3 = 0.0 mg/L
f. Annual cost
(0.05 m3/s)(86,400 s/d)(365 d/y) = 1,576,800 = 1.58 x 106 m3
(1000 L/m3)(1.58 x 106 m3) = 1.58 x 109 L
CaO
(140.71 mg/L)(1.58 x 109 L) = 2.22 x 1011 mg
(2.22 x 1011 mg)(10-9 Mg/mg) = 2.22 x 102 Mg
4-67
(2.22 x 102 Mg)($61.70/Mg) = $13,717.31
Na2CO3 = $0.00
Total Cost = $13,717.31 or $13,700
4-71 Design a split treatment system
Given: CO2 = 42.7, Ca = 102.0, Mg = 45.2 all in mg/L as ion, HCO3- = 344.0 mg/L as
CaCO3
Solution:
a. Convert all relevant compounds to mg/L as CaCO3
E.W.CaCO 3
CO 2 = (42.7 mg L ) 2.28 = 97.36 mg/L as CaCO3
E.W.ion
E.W.CaCO 3
Ca = (102.0 mg L ) 2.50 = 255.0 mg/L as CaCO3
E.W.ion
E.W.CaCO 3
Mg = (45.2 mg L ) 4.12 = 186.22 mg/L as CaCO3
E.W.ion
b. Because Mg is greater than 40 mg/L as CaCO3, design for a split treatment system
where in the first stage, the water is softened to practical solubility limits.
c. Chemical additions
Lime Soda
(meq/L) (meq/L)
CO2 0.40
HCO3- 2.72
Mg 1.12
Ca + Mg - HCO3- -- 0.56
Excess (Mg - 40 > 40) 0.40
Totals 4.64 0.56
d. Calculate the split
4-68
40 10
X= = 0.17
186.22 10
The fraction passing through the first stage is 1 - 0.17 = 0.83 or 83%.
e. Check to see if hardness is less than normally accepted level
(0.17)(255 + 186.22) + (0.83)(40) = 108.2 mg/L as CaCO3
This is below the limit of 120 mg/L as CaCO3. No further softening is required.
4-72 Design a split treatment system
Given: CO2 = 0.40, Ca = 2.16, Mg = 1.12, HCO3- = 2.72, all as meq/L
Solution:
a. Because Mg is greater than 40 mg/L as CaCO3 (1.12 meq/L x 50 mg CaCO3/meq),

design for a split treatment system where in the first stage, the water is softened to
practical solubility limits.
b. Chemical additions
Lime Soda
(meq/L) (meq/L)
CO2 0.40
HCO3- 2.72
Mg 1.12
Ca + Mg - HCO3- -- 0.56
Excess (Mg - 40 > 40) 0.40
Totals 4.64 0.56
d. Calculate the split
40 10
X= = 0.65
{(1.12 meq L )(50mg CaCO 3 meq )} 10
The fraction passing through the first stage is then 1 - 0.65 = .35 or 35%
e. Check to see if hardness is less than normally accepted level
(0.65)(2.72 + 1.12) + (0.35)(0.60 + 0.20) = 2.78 meq/L
4-69
(2.78 meq/L)(50 mg CaCO3/meq) = 139 mg/L as CaCO3
This is above the design limit of 120 mg/L as CaCO3. Therefore second stage softening is
required.
f. Chemical additions (NOTE: no further reduction in Mg is required)
Lime
(meq/L)
CO2 0.40
HCO3- 2.72
Total 3.12
g. The chemical additions in proportion to the flows
Lime = (0.35)(4.64) + (0.65)(3.12) = 3.65 meq/L
Soda = (0.35(0.56) + (0.65) (0.0) = 0.20 meq/L
h. In terms of CaO and Na2CO3
Lime as CaO = 3.65(28 mg/meq) = 102.2 or 102 mg/L
Soda as Na2CO3 = (0.20)(53 mg/meq) = 10.6 or 11 mg/L
4-73 Design a split treatment system for What Cheer
Given: Water analysis in mg/L as CaCO3
Solution:
a. Calculate TH, CH, and NCH (all mg/L as CaCO3)
TH = 167.7 +76.3 = 244.0
Because HCO3- is > TH, all the hardness is CH.
CH = 244.0
NCH = 0.0
b. Split calculation
4-70
40 10
X= = 0.4525
76.3 10
c. First stage softening chemical additions
Lime (mg/L
as CaCO3)
CO2 39.80
-
HCO3 257.90
Mg 76.30
Excess (Mg - 40 > 40) 36.30
Total 410.30
d. TH of mixed water
(0.4525)(244.0) + (1 0.4525)(40) = 132.3 mg/L as CaCO3
Because 132.3 mg/L is > 120 mg/L desired, need second stage softening.
e. Second stage softening to remove Ca only
Lime = CO2 = 39.8
Lime = HCO3- = 257.9
Excess Lime = 36.3
f. Final hardness
Ca = solubility limit = 30 mg/L as CaCO3
Mg = design = 40 mg/L as CaCO3
Total = 30 + 40 = 70 mg/L as CaCO3
g. Split scheme
4-71
First Stage Second Stage
Soften Settle Soften Settle Recarbonate
(X)(Q)
4-74 Volume of rapid mix tank
Given: Flow = 0.05 m3/s; detention time = 10 s (NOTE: in the first printing of the third
edition the detention time was given as 60 s.)
Solution:
V = Qt0
V = (0.05 m3/s)(10 s) = 0.5 m3
4-75 Volume of flocculators
Given: Flow = 0.150 m3/s; detention time = 20 minutes; two parallel tanks
Solution:
V = Qt0 = (0.150 m3/s)(20 min)(60 s) = 180 m3
180
Volume for each tank = = 90m 3
2
4-76 Detention time
Given: 2 sedimentation tanks in parallel, combined Q = 0.1000 m3/s, volume of each tank
= 720 m3
Solution:
a. Sketch of system
4-72
Q/2 = 0.0500 m3/s

Q = 0.1000 m3/s
Q/2 = 0.0500 m3/s
b. Convert flow rate to m3/h
Q = (0.0500 m3/s)(3600 s/h) = 180 m3/h
c. Detention time
V 720m 3
= = = 4.00h
Q 180 m 3 h
4-77 Power input for rapid mix
Given: Data from Problem 4-74; G = 700 s-1; temp = 20oC
Solution:
a. Find viscosity from Appendix A and convert to proper units
= 1.002 x 10-3 Pa-s
b. Solve Eqn 4-74 for P using volume of 0.5 m3 from Prob. 4-74
P = G2()(V) = (700)2(1.002 x 10-3)(0.5)
P = 245.49 or 250 W or 0.25 kW
4-78 Power input for flocculator
Solution:
= 1.081 x 10-3 Pa-s
P = G2()(V) = (36)2(1.081 x 10-3)(90.0)
P = 126.09 or 126 W or 0.126 kW

4-73
4-79 Power input for rapid mix at lower water temp
Solution:
= 1.307 x 10-3 Pa-s
P = G2()(V) = (700)2(1.307 x 10-3)(0.5)
P = 320.21 or 320 W or 0.32 kW
4-80 Power input for flocculator at lower water temp
Solution:
= 1.307 x 10-3 Pa-s
P = G2()(V) = (36)2(1.307 x 10-3)(90.0)
P = 152.44 or 152 W or 0.15 kW
4-81 Rotational speed of impeller
Given: Example 4-20
Solution:
a. For 2nd compartment
P = 152 W from example
NP = 0.31
4-74
D = 1.4 m
13
152
13
= (0.0912)
152W
n= =
13
( 5
(0.31) 1000 kg m (1.4)
3
) 1667.25
n = 0.45 rps or 27 rpm
b. For 3rd compartment
P = 54.7 W
13
54.7
13
= (0.0328)
54.7 W
n= =
13
(
(0.31) 1000 kg m (1.4)
3 5
) 1667.25
n = 0.32 rps or 19 rpm
4-82 Rapid mix tank for Eau Gaullie
Given: Q = 0.1065 m3/s, Temperature = 29oC, 1 tank, circular with depth = 2x diameter,
detention time = 10 s, velocity gradient = 800 s-1, Impeller = turbine, 6 flat blades,
NP = 5.7
Solution:
a. Calculate tank dimensions
( )
V = Q = (10s ) 0.1065 m 3 s = 1.065m 3
with H = 2T
T 2 T 3
V = (2T ) =
4 2
T 3
1.065m 3 =
2
(1.065)(2 )
13
T= = (0.678) = 0.8785m or 0.88 m diameter

13
and H = 2(0.88) = 1.76 m depth
b. Calculate the power input

4-75
With a water temperature of 19oC, use Appendix A to find = 1.027 x 10-3 Pa-s
P = (800)2(1.027 x 10-3)(1.065) = 700 W or 0.7 kW
c. Evaluate the available impeller diameters. Assume B = 1/3 of depth
T= 0.88 m
H= 1.76 m
B= 0.586661 m
Radial Turbine Impeller

Geometric Allowable Impeller Diameters, m
Ratio Range
0.45 0.6 1.2
D/T 0.14 - 0.5 0.51 0.68 1.36
H/D 2.0 - 4.0 3.91 2.93 1.47
H/T 0.28 - 2.0 2.00 2.00 2.00
B/D 0.7 - 1.6 1.30 0.98 0.49
Best available diameter = 0.45 m
d. Calculate rotational speed
13
700W 700
13
n= = = 6.66rps or 400 rpm

( )
(5.7 ) 1000 kg m (0.45m )
3 5
105.18
4-83 Rapid Mix Tank for Laramie
Given: Q = 0.168 m3/s, Temperature = 5oC, square tank with depth = width, detention
time = 5 s, velocity gradient = 700 s-1, impeller = turbine, 6 flat blades, NP = 5.7
Solution:
( )
V = Q = (5s ) 0.168 m 3 s = 0.84m 3
with H = T and square tank
T3 = 0.84m3
T = (0.84)1/3 = 0.94 m
H = T = 0.94 m
4-76
Equivalent T
(4)(0.94)2
12
Te = = (1.125) = 1.06m
12

b. Calculate power input
With a water temperature of 5oC, use Appendix A to find = 1.519 x 10-3 Pa-s
P = (700)2(1.519 x 10-3)(0.84) = 625 W or 0.625 kW
c. Evaluate the available impeller diameter. Assume B = 1/3 of depth.
T= 1.06 m
H= 0.94 m
B= 0.31333 m

Ratio Range
0.45 0.6 1.2
D/T 0.14 - 0.5 0.42 0.57 1.13
H/D 2.0 - 4.0 2.09 1.57 0.78
H/T 0.28 - 2.0 0.89 0.89 0.89
B/D 0.7 - 1.6 0.70 0.52 0.26
13
625W 625
13
n= = = 1.81rps or 110 rpm

( )
5
(5.7 ) 1000 kg m (0.45m )
3
105.18
4-84 Rapid Mix Tank for Waffle
Given: Q = 0.050 m3/s, Temperature = 8oC, circular tank with depth = 1.0 m, detention
time = 5 s, velocity gradient = 750 s-1, impeller = turbine, 6 flat blades, NP = 3.6
Solution:
( )
V = Q = (5s ) 0.050 m 3 s = 0.25m 3
4-77
with H = 1.0 m
T 2
0.25m 3 = (1.0)
4
(4)(0.25)
12 12
1.0
T= = = 0.5642 or 0.56 m
(1.0)
b. Calculate power input
With water temperature of 8oC, use Appendix A to find .
5oC = 1.519 x 10-3 Pa-s
10oC = 1.307 x 10-3 Pa-s
85 x 1.519
=
10 5 1.307 1.519
3 x 1.519
=
5 0.212
x 1.519 = -0.1272
x = 1.392
Therefore, = 1.392 x 10-3 Pa-s
P = (750)2(1.392 x 10-3)(0.25) = 195.75 or 196 W
c. Evaluate available impeller diameter. Assume B = 1/3 of depth
4-78
T= 0.56 m
H= 1 m
B= 0.33333 m

Ratio Range
0.25 0.5 1
D/T 0.14 - 0.5 0.45 0.89 1.79
H/D 2.0 - 4.0 4.00 2.00 1.00
H/T 0.28 - 2.0 1.79 1.79 1.79
B/D 0.7 - 1.6 1.33 0.67 0.33
13
196W 196
13
n= = = 3.82rps or 230 rpm

( ) 5
(3.6) 1000 kg m (0.25m )
3
3.52
4-85 Flocculation Tank for Eau Gaullie
Given: Problem 4-82; 2 tanks; 3 compartments with G = 90 s-1, 60 s-1, and 30 s-1; G =
120,000; length = width = depth; axial flow impeller; impeller diameter available
= 1.0 m, 1.5 m, and 2.0 m; NP = 0.31
Solution:
a. Based on G value and average G for the 3 compartments, calculate the detention time
90 + 60 + 30
G avg = = 60s 1
3
G 120000
= = = 2000s
G avg 60
b. Calculate the volume of each flocculation basin
( )
V = Q = 0.1065 m 3 s (2000s ) = 213m 3
Since the flow will be divided into 2 tanks
Volume for each tank = 213/2 = 106.5 m3
4-79
c. Since each basin will be divided into 3 compartments, the volume of each compartment
will be
Volume for each compartment = 106.5/3 = 35.5 m3
d. Compartment dimensions with compartment length = depth = width (w)
(w)3 = 35.5 m3
w = (35.5)1/3 = 3.29 or 3.3 m
So the compartment dimensions are 3.3 m by 3.3 m by 3.3 m
e. Power input with temperature = 19oC
1. For first compartment with G = 90 s-1
P = G2()(V) = (90)2(1.027 x 10-3)(35.5) = 295 W or 0.295 kW
2. For second compartment with G = 60 s-1
P = G2()(V) = (60)2(1.027 x 10-3)(35.5) = 131 W or 0.131 kW
f. Calculate equivalent tank diameter
Area = 3.3 x 3.3 x 3.3 = 10.89 m3
(4)(10.89)2
12
Te = = (13.86) = 3.72m
12

g. Evaluate available impeller diameter. Assume B = 1/3 of depth
4-80
T= 3.72 m
H= 3.3 m
B= 1.099989 m

Ratio Range
1 1.5 2
D/T 0.14 - 0.5 0.27 0.40 0.54
H/D 2.0 - 4.0 3.30 2.20 1.65
H/T 0.28 - 2.0 0.89 0.89 0.89
B/D 0.7 - 1.6 1.10 0.73 0.55
Based on trial calculation, 1.0 m diameter yields a tip speed of 3.1 m/s.
This is > allowable tip speed of 2.7 m/s.
Therefore, best available diameter = 1.5 m
h. Calculate rotational speed of impeller
1st compartment
13
295W 295
13
n= = = 0.50rps or 30 rpm
( )
5
(0.31) 1000 kg m (1.5m )
3
2354
2nd compartment
13
130W 130
13
n= = = 0.38rps or 23 rpm
( )5
(0.31) 1000 kg m (1.5m )
3
2354
i. Check tip speed of 1st compartment impeller
Tip Speed = (0.50 rps)()(1.5) = 2.4 m/s
This is less than 2.7 m/s so okay.
4-86 Flocculation Tank for Laramie
Given: Problem 4-83; 2 tanks; 3 compartments with G = 90 s-1, 60 s-1, 30 s-1; G =

120,000; length = width = depth; axial flow impeller; impeller diameters available
= 1.0 m, 1.8m, 2.4m, NP = 0.40
Solution:
a. Based on G value and average G for the 3 compartments, calculate the detention time.
4-81
90 + 60 + 30
G avg = = 60s 1
3
G 120000
= = = 2000s
G avg 60
b. Calculate the volume of each flocculation basin
( )
V = Q = 0.168 m 3 s (2000s ) = 336m 3
Since the flow will be divided into 2 tanks
Volume for each tank = 336/2 = 168 m3
c. Since each basin will be divided into 3 compartments, the volume of each compartment
will be
Volume for each compartment = 168/3 = 56 m3
d. Compartment dimensions with compartment length = depth = width (w)
(w)3 = 56 m3
w = (56)1/3 = 3.83 or 3.8 m
So the compartment dimensions are 3.8 m by 3.8 m by 3.8 m
e. Power input with temperature = 5 oC
P = G2()(V) = (90)2(1.519 x 10-3)(56) = 690 W or 0.69 kW
P = G2()(V) = (60)2(1.519 x 10-3)(56) = 310 W or 0.31 kW
f. Calculate equivalent tank diameter
Area = 3.8 x 3.8 x 3.8 = 14.44 m2
4-82
(4)(14.44)2
12
Te = = (18.39) = 4.29m
12

g. Evaluate available impeller diameter. Assume B = 1/3 of depth
T= 4.29 m
H= 3.8 m
B= 1.266654 m

Ratio Range
1 1.8 2.4
D/T 0.14 - 0.5 0.23 0.42 0.56
H/D 2.0 - 4.0 3.80 2.11 1.58
H/T 0.28 - 2.0 0.89 0.89 0.89
B/D 0.7 - 1.6 1.27 0.70 0.53
Based on trial calculation, 1.0 m diameter yields a tip speed of 3.8 m/s.
This is > allowable tip speed of 2.7 m/s.
Therefore, best available diameter = 1.8 m
h. Calculate rotational speed of impeller
1st compartment
13
690 W 690
13
n= = = 0.45rps or 27 rpm
( 5
(0.40) 1000 kg m (1.8m )
3
) 7558
2nd compartment
13
310W 310
13
n= = = 0.34rps or 21 rpm
( 5
(0.40) 1000 kg m (1.8m )
3
) 7558
i. Check tip speed of 1st compartment impeller
Tip Speed = (0.45 rps)()(1.8) = 2.5 m/s
This is less than the allowable tip speed of 2.7 m/s so okay.
4-83
4-87 Flocculation tank for Waffle
Given: Problem 4-84; 1 tank; 3 compartments with G = 60 s-1, 50 s-1, 20 s-1; detention
time = 30 min; width = 3.5 m; axial flow impellers; available impeller diameter =
1.0 m, 1.5 m, 2.0 m; NP = 0.43
Solution:
a. Calculate the volume of the flocculation tank
V = Q = (0.050 m3/s)(30 min)(60 s/min) = 90 m3
b. With 3 compartments,
Volume for each compartment = 90/3 = 30 m3
c. Compartment dimensions with depth = 3.5 m
30m 3
Area = = 8.57 m 2
3.5m
With length = width
L = w = (8.57)1/2 = 2.93 m
d. Calculate equivalent tank diameter
(4)(8.57 )2
12
Te = = (10.91) = 3.3m
12

e. Evaluate available impeller diameters. Assume B = 1/3 of depth
4-84
T= 3.3 m
H= 3.8 m
B= 1.266654 m

Ratio Range
1 1.5 2
D/T 0.14 - 0.5 0.30 0.45 0.61
H/D 2.0 - 4.0 3.80 2.53 1.90
H/T 0.28 - 2.0 1.15 1.15 1.15
B/D 0.7 - 1.6 1.27 0.84 0.63
Both the 1 m and the 1.5 m impeller are acceptable.

I chose the 1.0 m impeller.
f. Calculate power input
From Problem 4-84, the temperature is 8oC and = 1.392 x 10-3 Pa-s
P = G2()(V) = (60)2(1.392 x 10-3)(30) = 150 W or 0.15 kW
P = G2()(V) = (50)2(1.392 x 10-3)(30) = 104 W or 0.10 kW
g. Calculate rotational speed of impeller
1st compartment
13
150W 150
13
n= = = 0.70rps or 42 rpm
( )
5
(0.43) 1000 kg m (1.0m )
3
430
2nd compartment
13
104W 104
13
n= = = 0.62rps or 37 rpm
( )
5
(0.43) 1000 kg m (1.0m )
3
430
h. Calculate tip speed for 1st compartment
Tip speed = (0.70 rps)()(1.0 m) = 2.2 m/s
This is less than the maximum allowable tip speed of 2.7 m/s.
4-85
4-88 Percent removal of particles; horizontal clarifier
Given: v0 = 0.80 cm/s; vp = 0.70 cm/s
Solution:
0.70
% Re moval = 100% = 87.50 or 88%
0.80
4-89 Percent removal of particles; upflow clarifier
Given: vS = 2.80 mm/s; v0 = 0.560 cm/s
Solution:
2.80 mm s
vS = = 0.280 cm s
10 mm cm
Since vS << v0 no particles will be removed (retained)
% Retained = 0.0%
4-90 Percent removal; horizontal clarifier
Given: vS = 0.30 cm/s, v0 = 0.25 cm/s
Solution:
0.30 cm s
% Re moval = 100% = 120%
0.25 cm s
The settling tank cannot remove more than 100%. Thus, the answer is 100%.
4-91 Repeat 4-88 with increased flow rate
Given: Data in Problem 4-88, increase in flow rate from 0.150 m3/s to 0.200 m3/s
Solution:
a. Since the surface area of the tank remains constant and overflow rate is directly
proportional to flow rate, the new overflow rate is
v0 0.200
=
0.80 0.150
4-86
v0 = 1.07 cm/s
b. New % Removal
0.70
% Re moval = 100% = 65%
1.07
4-92 Repeat Problem 4-89 with increased flow rate
Given: Data in Problem 4-89, doubling of flow rate
Solution:
Since no particles were removed at the lower flow rate, the increase in flow rate would
only decrease the efficiency. The answer remains the same: 0.00% removal.
4-93 Percent removal; horizontal clarifier
Given: Problem 4-90, double flow rate
Solution:
a. Calculate new overflow rate
The surface area of the tank remains constant and the overflow rate is
proportional to flow rate. The new overflow rate is
v0 2Q
=
0.25 Q
v0 = (2)(0.25) = 0.50 cm/s
b. % Removal
0.30 cm s
% Re moval = 100% = 60%
0.50 cm s
4-94 Surface area of sedimentation tank
Given: Q = 1.0 m3/s, 10 sedimentation basins, v0 = 15 m3/d-m2
Solution:
4-87
a. Convert flow rate to same units
Q = (1.0 m3/s)(86400 s/d) = 86400 m3/d
86400 m 3 d
= 8640 m 3 day tan k
10 tan ks
8640 m 3 d
As = = 576.0m 2
15 m d m
3 2
4-95 Surface area for two tanks for lime floc
Given: Two tanks to handle 0.05162 m3/s of lime softening floc
Solution:
a. From Table 4-18 select 57 m3/d-m2 as conservative overflow rate, i.e. one that will
yield the larger and, hence, more conservative surface area.
b. Since two tanks (assume in parallel):
0.05162 m 3 s
Q= = 0.02581 m 3 s
2
c. And surface area of each tank
As =
(0.02581 m s )(86400 s d ) = 39.123 or 39 m2
3
57 m 3 d m 2
4-96 Surface area for two tanks for iron/alum floc
Given: Two tanks to handle 0.05162 m3/s of lime softening floc
Solution:
a. From Table 4-18 select 20 m3/d-m2 as conservative overflow rate, i.e. one that will
yield the larger and, hence, more conservative surface area.
b. Since two tanks (assume in parallel):
0.05162 m 3 s
Q= = 0.02581 m 3 s
2
4-88
c. And surface area of each tank
As =
(0.02581 m s )(86400 s d ) = 111.49 or 111 m2
3
20 m 3 d m 2
4-97 Detention time and surface area
Given: Two sedimentation tanks operate in parallel, total Q = 0.1000 m3/s, depth = 2.00
m, = 4.00 h
Solution:
a. Sketch of flow scheme
Q/2 = 0.0500 m3/s
Q = 0.1000 m3/s
Q/2 = 0.0500 m3/s
b. Convert Q to m3/h for each tank
Q = (0.0500 m3/s)(3600 s/h) = 180 m3/h
c. Solve Eqn. 2-27 for V
V
=
Q
V = Q = (4.00h )(180 m 3 h ) = 720m 3
d. Surface area
V = (H )(A s )
V 720m 3
As = = = 360m 2
H 2.00m
e. Overflow rate
4-89
Q 180 m 3 h
v0 = = 2
= 0.50 m 3 h m 2 or 12.0 m3/d-m2
As 360m
4-98 Detention time and overflow rate
Given: Settling column test data; reduction in suspended solids concentration from 33.0
mg/L to 15.0 mg/L.
Solution:
a. Plot isoconcentration lines as in Figure 4-40
20% 30% 40% 50% 60% 70% 80%

Time [min] Depth [m] Depth [m] Depth [m] Depth [m] Depth [m] Depth [m] Depth [m]
0 0 0 0 0 0 0 0
10 2.5 1.7 1 0.5 0.3 0.3 0.1
20 3.5 2 1.1 0.75 0.7 0.22
30 3.1 1.7 1.2 1 0.45
40 4.5 2.3 1.7 1.35 0.7
50 3.1 2.3 1.7 0.95
60 3.8 2.75 2.1 1.2
70 3.4 2.45 1.58
80 4.05 2.8 1.9
90 3.2 2.28
4-90
Problem 4-98 Solution

Batch Settling Curves
0 % Removal
0.5 100 % 20%

1 30%
1.5
Depth, m
80% 40%
2
50%
2.5
3 60%
20%
3.5 70%
60%
4 80%
4.5
Extrapolate
0 25 minutes
50 100 150
40.5 minutes
Time, min
Figure S-4-98a: Batch Settling Curves
b. Required removal is
33.0 mg L 15.0 mg L
% Re moval = 100% = 54.54%
33.0 mg L
c. Calculate overflow rate, % removal and detention time for 40% removal line.
1. Overflow rate (Note: time is where 40% line intersects bottom of settling
column, i.e. 4.5 m)
v0 =
4 .5 m
(1440 min d ) = 160.0 m d
40.5 min
2. % removal (from vertical line at 40.5 min)

%R T 40 = 40 +
3 .4
(50 40) + 2.0 (60 50) + 1.5 (70 60) + 1.0 (80 70) + 0.35 (100 80)
4 .5 4 .5 4 .5 4 .5 4 .5
4-91
%RT40 = 40 + 7.56 + 4.56 + 3.33 + 2.22 + 1.56
%RT40 = 59.11%
(Note: this exceeds the 54.54% required, so calculate next lower %R and
interpolate)
3. Detention time = = 40.5 min
d. At 30% removal line
column, i.e. 4.5 m)
v0 =
4 .5 m
(1440 min d ) = 259.2 m d
25 min
2. % removal (from vertical line at 25 min)
%R T 30 = 30 +
3.5
(40 30) + 1.9 (50 40) + 1.2 (60 50) + 0.95 (70 60) + 0.6 (80 70) + 0.18 (100 80)
4.5 4.5 4.5 4.5 4.5 4.5
%RT30 = 30 + 7.78 + 4.22 + 2.67 + 2.11 + 1.33 + 0.80
%RT30 = 48.91%
3. Detention time = = 25 min
e. Plot % Removal versus detention time and % Removal versus overflow rate. Assume
linear between points and use 54.54% removal to find:
= 33 min
v0 = 204 m/d
4-92
Detention Time
61
59
57
% Removal
55
53
51
49
47
45
20 25 30 35 40 45
Detention time [min]
Figure S-4-98b: Detention time
Overflow Rate
61
59
57
% Removal
55
53
51
49
47
45
160 180 200 220 240 260 280
Overflow rate [m/d]
Figure S-4-98c: Overflow rate
f. Apply scale up factors
= (33 min)(1.75) = 57.75 or 60 min
v0 = (204 m/d)(0.65) = 132.6 or 130 m/d
Given: Settling column test data; reduction in suspended solids concentration of 60%
Solution:
4-93
a. Convert suspended solids concentrations to percent removal by:
C
% Re moval = 1 i 100%
C0
where Ci = measured concentration at time and depth

C0 = original concentration
Tabular results are as follows:
Depth [m] Time [min]

10 20 35 50 70 85
0.5 30 50 65 69 75 80
1.0 25 35 47 59 65 70
1.5 23 29 40 50 61 65
2.0 20 27 37 45 55 60
2.5 15 25 35 43 50 56
b. Plot isoconcentration lines as in Figure 4-40
20% 30% 40% 50% 60% 65% 70%

0 0 0 0 0 0 0 0
10 2 0.5 0.35 0.23 0.18 0.12 0.05
20 1.4 0.75 0.5 0.35 0.25 0.15
30 1.22 0.75 0.55 0.42 0.23
40 1.8 1.1 0.75 0.57 0.34
50 1.5 1 0.72 0.46
60 1.95 1.25 0.85 0.6
70 2.5 1.55 1.03 0.75
80 1.85 1.33 0.9
4-94

0 % Removal
100 % 20%
0.5
30%
70%
Depth, m
1 40%
50%
1.5 60%
60%
20%
65%
2
Extrapolate 70%
2.5
0 46 minutes 50 100
70 minutes
Time, min
c. Calculate overflow rate, % removal and detention time for 50% removal line.
column, i.e. 2.5 m)
v0 =
2 .5 m
(1440 min d ) = 51.43 m d
70 min
%R T 50 = 50 +
2 .0
(60 50) + 1.3 (65 60) + 0.9 (70 65) + 0.38 (100 70)
2 .5 2 .5 2 .5 2 .5
%RT50 = 50 + 8.0 + 2.6 + 1.8 + 4.56
%RT50 = 66.96 %
4-95
(Note: this exceeds the 60% required, so calculate next lower %R and interpolate)
d. At 40% removal line
column, i.e. 2.5 m)
v0 =
2 .5 m
(1440 min d ) = 78.26 m d
46 min
%R T 40 = 40 +
1 .9
(50 40) + 1.1 (60 50) + 0.75 (65 60) + 0.55 (70 65) + 0.2 (100 70)
2 .5 2 .5 2 .5 2 .5 2 .5
%RT40 = 40 + 7.60 + 4.40 + 1.50 + 1.10 + 2.40
%RT40 = 57.0 %
e. Plot % Removal versus detention time and % Removal versus overflow rate. Assume
linear between points and use 60% removal to find:
= 53.5 min
v0 = 70 m/d
Detention Time
69
67
65
% Removal
63
61
59
57
55
40 45 50 55 60 65 70 75

4-96
Overflow Rate
69
67
65
% Removal
63
61
59
57
55
40 45 50 55 60 65 70 75 80 85
Overflow rate [m/d]
= (53.5 min)(1.75) = 93.63 or 94 min
v0 = (70 m/d)(0.65) = 45.5 or 46 m/d
Given: Settling column test data, 33 NTU initial turbidity, 88% removal required
Solution:
a. Convert NTU to percent removal by
C
% Re moval = 1 i 100%
C0
where Ci = measured NTU at time and depth

C0 = original NTU
Tabular results are as follows (all in % removed)
4-97
Depth [m] Time [min]

30 60 90 120
1.0 83 94
2.0 66 82 92
3.5 56 70 80 90
b. Plot isoconcentration lines
55% 60% 65% 70% 75% 80% 90%

0 0 0 0 0 0 0 0
10 0.5 0.3 0.1
20 1 0.6 0.25
30 1.5 0.9 0.4
40 2.05 1.2 0.6
50 2.65 1.5 0.75
60 3.5 1.85 1
70 2.25 1.25
80 2.7 1.5
90 3.5 1.8
100 2.3
110 2.8
120 3.5
4-98

0 % Removal
0.5 100 % 55%

1 60%
Depth, m
1.5 65%
2 70%
70%
2.5 90%
75%
3 80%
3.5 90%
Extrapolate
4
96 minutes
0 50 65 minutes
100 150
Time, min
c. Calculate overflow rate, % removal, and detention time for 70% removal line
1. Overflow rate
v0 =
4 .0 m
(1440 min d ) = 88.62 m d
65 min
2. % removal from vertical line at 65 min
%R T 70 = 70 +
3 .0
(80 70 ) + 1.6 (90 80) + 0.6 (100 90 )
4 .0 4 .0 4 .0
%RT70 = 70 + 7.5 + 4.0 + 1.5
%RT70 = 83.0%
(Note: this is less than 88% desired so calculate next higher %R and interpolate)
4-99
d. Calculate overflow rate, % removal, and detention time for 80% removal line
1. Overflow rate
v0 =
4 .0 m
(1440 min d ) = 60.00 m d
96 min
2. % removal from vertical line at 96 min
%R T 80 = 80 +
3 .1
(90 10) + 1.1 (100 90)
4 .0 4 .0
%RT80 = 80 + 7.75 + 2.75
%RT80 = 90.5%
e. Plot % removal vs detention time and % removal vs overflow rate. Assume linear
between points and use 88% removal to find
= 85 min
v0 = 69 m/d
Detention Time
95
90
% Removal
85
80
75
70
50 55 60 65 70 75 80 85 90 95 100

4-100
Overflow Rate
95
90
% Removal
85
80
75
70
50 55 60 65 70 75 80 85 90 95
Overflow rate [m/d]
= (85 min)(1.75) = 148.8 or 150 min
v0 = (69 m/d)(0.65) = 44.85 or 45 m/d
4-101 How many filters at standard loading?
Given: Q = 0.8 m3/s; each filter 10 m x 20 m; loading rate = 110. m3/d-m2
Solution:
a. Determine Q in m3/d
Q = (0.8 m3/s)(86,400 s/d) = 69,120 m3/d
b. Determine total area required
69120 m 3 d
As = = 628.36m 2
110 m d m
3 22
c. Number of filters (must round to next highest integer)
628.36m 2
No. = = 3.14 or 4 filters
(10m )(20m )
4-101
4-102 How many filters at high loading?
Given: Q = 0.8 m3/s; each filter 10 m x 20 m; loading rate = 300. m3/d-m2
Solution:
a. Determine Q in m3/d
Q = (0.8 m3/s)(86,400 s/d) = 69,120 m3/d
b. Determine total area required
69120 m 3 d
As = = 230.4m 2
300 m d m
3 22
c. Number of filters (must round to next highest integer)
230.4m 2
No. = = 1.152 or 2 filters
(10m )(20m )
4-103 Flow rate through filters
Given: Four filters (each 5.00 m x 10.00 m) loaded at 280 m/d.
Solution:
a. Note that 280 m/d = 280 m3/d-m2
b. Compute flow in m3/d
Q = (280 m3/d-m2)(4)(5.00 m)(10.00 m)
Q = 56,000 m3/d
c. Convert to m3/s
56000 m 3 d
Q= = 0.648 m 3 s
86400 s d
4-102
4-104 Plant expansion filter beds
Given: Example 4-25, mono-media filter loading of 600 m3/d-m2, filter box limit of 50m2
Solution:
a. Surface area required (Note: Q = 0.5 m3/s from Example 4-25)
As =
(0.5 m s )(86400 s d ) = 72m
3
2
600 m d m
3 2
b. If the maximum surface area is 50 m2, then the number required is
72m 2
= 1.44 filter boxes
50m 2
Therefore use 2 filter boxes.
c. Check with one filter box out of service
va =
(0.5 m s )(86400 s d ) = 864 m d
3
(1filters)(50 m filter )
2
This is greater than the design loading rate.
d. A number of alternatives are available. One example is to provide 4 filter boxes at 25

m2 each. With one out of service
va =
(0.5 m s )(86400 s d ) = 576 m d
3
(3filters)(25 m filter )
2
This is less than the design loading rate.
4-105 Grain size analysis for Eau Gaullie
Given: U.S. sieve number and mass % retained
Solution:
a. Convert sieve number to size using Table 4-19 and compute cumulative mass %.
Tabulation is shown below:
4-103
Cumul. Mass Grain size [mm] U.S. Sieve Number

0 0.149 100
0.1 0.21 70
3.8 0.297 50
24 0.42 40
68 0.59 30
93.9 0.84 20
99.6 1.19 16
99.99 1.68 12
b. Plot (following page)
10
Grain size [mm]
0.1
0 20 40 60 80 100
Cumulative mass % <
Figure S-4-105
c. From the graph find:
E = P10 = 0.35 mm
P60 0.56mm
U= = = 1.60
P10 0.35mm
4-104
d. The effective size just fits the lower end of the acceptable range of 0.35 to 0.55 mm.
The uniformity coefficient falls within the acceptable range of 1.3 to 1.7. Therefore,
the sand meets the specifications.
4-106 Grain size analysis for Laramie
Given: U.S. sieve number, mass retained and sample size of 500.00 g
Solution:
a. Convert sieve number to size using Table 4-19 and compute cumulative mass %.
Tabulation is shown below:

0.015 0.297 50
1.8 0.42 40
32 0.59 30
86.5 0.84 20
99.6 1.19 16
b. Plot
10
Grain size, mm
0.1
1 10 100
Cumulative mass % <
Figure S-4-106
4-105
E = P10 = 0.495 mm
P60 0.68mm
U= = = 1.37
P10 0.495mm
d. The effective size fits the acceptable range of 0.35 to 0.55 mm. The uniformity
coefficient meets the acceptable range of 1.3 to 1.7. Therefore, the sand meets the
specifications.
4-107 Rework Example 4-26
Given: Data in Example 4-26 with 70, 100 and 140 sieve fractions removed.
Solution:
a. Recompute cumulative % passing assuming that 4.0% of the sand (i.e. % passing the
No. 70 sieve) is removed. For computational purposes assume 100 g was in original
sample and 4.0 grams of lower sized fractions were removed. The tabulations are
shown below. The computations for the 3rd, 4th and5th columns are explained below
the table.

6.21 0.297 50
18.74 0.42 40
37.27 0.59 30
58.74 0.84 20
74.11 1.19 16
92.11 1.68 12
b. Plot (following page)
4-106
10
Grain size, mm
0.1
0 20 40 60 80 100
Cumulative mass % <
Figure S-4-107
E = P10 = 0.34 mm
P60 0.84mm
U= = = 2.47
P10 0.34mm
d. The effective size does not quite fit the acceptable range of 0.35 to 0.55 mm. The
uniformity coefficient exceeds the acceptable range of 1.3 to 1.7. Therefore, the sand
does not meet specifications but is improved from the example effective size of 0.30
mm and uniformity coefficient of 2.8.
4-108 Head loss for clean filter bed - Eau Gaullie
Given: Filter and sand data for Eau Gaullie
Solution:
4-107
a. The following tabulation for computing the solution was obtained from a spreadsheet
program.
-4
Sieve No. % Retained d [m x 10 ] Re CD ((CD)(f)/d) x 104
8-12 0.01 20 2.7 11.056 0.00005528
12-16 0.39 14.2 1.917 15.029 0.004127683
16-20 5.7 10 1.35 20.703 0.1180071
20-30 25.9 7.14 0.964 28.299 1.026532353
30-40 44 5.05 0.682 39.184 3.414051485
40-50 20.2 3.57 0.482 54.469 3.08199944
50-70 3.7 2.52 0.34 70.56 1.036
70-100 0.1 1.78 0.24 99.894 0.056120225
SUM (CD)(f)/d = 8.7369 x 104
b. Compute the approach velocity (va) in m/s
120 m 3 d m 2
= 0.0013889 m s
86400 s d
c. The total head loss is then
1.067(0.0013889 m s ) (0.60m )
(8.7369 10 )
2
hL = 4
(1.00 )(9.80 )(0.42) 4
hL = 0.3538 or 0.35 m
4-109 Height of expanded bed - Eau Gaullie
Given: Data from Problem 4-108 and backwash rate of 1,000 m/d
Solution:
program.
NOTE: The sieve ranges and fractions (f) are not shown due to space limitations. They
are the same as in Problem 4-108. Also note that the backwash velocity (vb) of
1,000 m/d is the same as 0.01157 m/s used to calculate e using Eqn. 4-107.
4-108
Estimated v s [m/s] Re CD Calculated v s [m/s] e f/(1 - e)

0.3 583 0.505 0.2785 0.4967 0.0002
0.2 276 0.608 0.214 0.5263 0.00823
0.15 145.8 0.753 0.1613 0.5601 0.12957
0.1 69.4 1.046 0.1157 0.6026 0.65174
0.07 34.4 1.55 0.0799 0.6537 1.2706
0.05 17.3 2.444 0.0535 0.714 0.70623
0.03 7.35 4.713 0.0323 0.7974 0.18267
0.02 3.46 8.89 0.0198 0.8884 0.00896
SUM f/(1 - e) = 2.9582
b. Using Eqn. 4-106 the expanded bed depth is
De = (1 - 0.42)(0.60)(2.9582) = 1.0294 or 1.03 m
4-110 Head loss for clean filter bed Laramie
Given: Filter and sand data for Laramie
Solution:
a.
-4
Sieve No. % Retained d [m x 10 ] Re CD ((CD)(f)/d) x 104
12-16 0.4 14.2 2.265 12.932 0.003642817
16-20 13.1 10 1.595 17.765 0.2327215
20-30 54.5 7.14 1.139 24.229 1.849412465
30-40 30.2 5.05 0.805 33.483 2.002349703
40-50 1.785 3.57 0.569 46.471 0.232355
50-70 0.015 2.52 0.402 59.719 0.003554702
SUM (CD)(f)/d = 4.324 x 104
b. Compute the approach velocity (va) in m/s
230 m 3 d m 2
= 0.0026620 m s
86400 s d
c. The total head loss is then
1.067(0.0026620 m s ) (0.75m )
(4.324 10 )
2
hL = 4
(0.91)(9.80 )(0.50) 4
hL = 0.44 m
4-109
4-111 Backwash rate and height of backwash troughs - Laramie
Given: Data from Problem 4-110
Solution:
a. The maximum backwash rate is determined by estimating the settling velocity of the
smallest sand grain size that makes up the filter bed. From Figure 4-46, this is
estimated to be 3.0 cm/s for the particle size 0.0252 cm. Using this velocity to
estimate the Reynolds number yielded a calculated settling velocity of 2.9 cm/s. A
backwash velocity of 2.9 cm/s cannot be used because it yields a negative expanded
depth. A 2.8 cm/s backwash velocity was used to estimate the depth of the expanded
bed and the height of the backwash troughs.
program.
NOTE: The sieve ranges and fractions (f) are not shown due to space limitations. They
are the same as in Problem 4-110. Also note that the backwash velocity (vb) of 0.028
m/s was used to calculate e using Eqn. 4-107.
Estimated v s [m/s] Re CD Calculated v s [m/s] e f/(1 - e)

0.2 170.1 0.711 0.2167 0.6375 0.01103
0.15 89.9 0.924 0.1596 0.6819 0.41182
0.1 42.8 1.36 0.1111 0.7384 2.0834
0.07 21.2 2.125 0.0748 0.8057 1.5543
0.05 10.7 3.502 0.0489 0.8843 0.15427
0.03 4.52 7.049 0.029 0.9923 0.01957
SUM f/(1 - e) = 4.2343
b. Using Eqn. 4-106 the expanded bed depth is

De = (1 - 0.50)(0.75)(4.2343) = 1.59 m
c. The height of the backwash troughs should be

(1.59 m - 0.75 m) + 0.15 m = 0.99 or 1 m above top of sand surface
Given: Example 4-27 with 100 - 140 sieve fraction removed
Solution:
4-110
a. The problem is not explicitly clear that the % retained fractions should be recalculated.
This is further confused by the fact that the example calculation ignores that fraction
of the sand that is greater than the No. 8 sieve, so calculating the new fractional
percentages is not straight forward. The solution yields a new head loss of 0.72 m.
b. The simple approach to solving this problem (and the one I would expect most students
to take) is simply to insert 0.0% in the 100 -140 row and recompute. This yields a new
head loss of 0.69 m.
Given: Example 4-28 with 100 - 140 sieve fraction removed.
Solution:
a. See discussion for Prob. 4-112. With new sieve percentages, the depth of the expanded
bed is 0.79 m.
b. With the simple approach of removing the 100 -140 fraction, the depth of the expanded
bed is 0.76 m.
4-114 Percent reduction
Given: 2.5 log inactivation
Solution:
a.
100
y = 100
10 x
100
y = 100 = 100 0.32 = 99.68%
10 2.5
4-115 Log inactivation
Given: 99.96 percent inactivation
Solution:
a. Solve for x
4-111
100
y = 100
10 x
100
y 100 =
10 x
100
10 x =
y 100
100
( )
log 10 x = log
y 100
100
x = log
y 100
b. Substitute value of y = 99.96%
100
x = log = log(2500) = 3.3979 or 3.4
99.96 100
Therefore there is a 3.4 log inactivation of Giardia lambia
4-112
DISCUSSION QUESTIONS
4-1 pH of carbonated beverage
Given: carbonated beverage
Solution:
The pH will be below 7. This is an application of the carbonate buffer system. Since the
beverage container is closed the addition of CO2 forces the carbonate buffer system
reaction to the right. Carbonic acid is formed. The dissociation results in an increase in
hydrogen ion concentration and a lowering of the pH. See Equation 4-35 and Figure 4-5.
4-2 Explain turbidity
Given: mayor of community
Solution:
Turbidity is finely suspended particulate matter that refracts light. Materials that may
cause turbidity include clay, silt, finely divided organic matter and algae.
4-3 Chemicals to make water palatable
Given: surface water
Solution:
Surface water may be unpalatable because of turbidity, color, taste, or odor. The
chemicals used to treat the water to remove these contaminants are listed below:
turbidity and color - alum or ferric chloride
taste and odor - activated carbon (GAC or PAC)
4-4 Microorganisms and formation of hardness
Given: statement that microorganisms play a role in formation of hardness
Solution:
The answer is true.

The release of CO2 by microorganisms causes the formation of carbonic acid which aids
in the dissolution of calcium carbonate and magnesium carbonate. See Figure 4-14.
4-5 Chemicals required to soften water
Given: well water with no bicarbonate

4-113
Solution:
If there is no bicarbonate, then the water has only noncarbonate hardness and the
chemicals required are lime and sodium carbonate (soda ash).
4-6 Partial removal in settling tank
Given: Horizontal flow clarifier, settling velocity of particles is 1/4 that of the overflow
rate.
Solution:
See Figure 4-37.
4-7 Why chlorine residual?
Given: U.S. chlorine is preferred as disinfectant.
Solution:
The presence of a residual is important because it provides some protection in case of

contamination of the water distribution system. It also provides a means to check for
contamination because contaminants deplete the chlorine residual. The absence of a
chlorine residual during routine examination is an indicator of contamination.
4-8 Sludge dewatering
Given: softening sludge to be disposed of in Lubbock, TX
Solution:
Cheap, available land favors lagoons and sand drying beds. The sand drying beds would
provide more drying capacity in less space but at a higher capital cost. If the sludge is to
be spread on the land for agricultural use, then the lagoons would probably be selected.
If the sludge was to be buried, then sand drying beds would probably be selected.

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4-1

4-1 Show that 1 g/m = 1000 kg/m

Given: Conversion factors inside back cover

4-2 Show that 4.50% = 45.0 kg/m

Given: % by weight in water

a. Assume density of water = 1000 kg/m

0.045 x 1000 kg/m = 45.0 kg/m3

4-3 Concentration of NH3 in mg/L

Given: Household ammonia at 3.00% by weight, H2O = 1000 kg/m3

a. Calculate the mass of NH3

(0.0300)(1000 kg/m3) = 30 kg/m3

b. Convert kg/m3 to mg/L

(30 kg/m3)(106 mg/kg)(10-3 m3/L) = 30,000 mg/L

4-4 Concentration of Cl2 in mg/L

Given: Household bleach at 5.25% by weight, H2O = 1000 kg/m3

a. Calculate the mass of Cl2

(0.0525)(1000 kg/m3)(106 mg/kg)(10-3 m3/L) = 52,000 mg/L

4-5 Show that 1 mg/L = 1 g/m3

Given: Conversion factors inside back cover

4-6 Arsenic standard in mg/L

Given: Standard is 10 ppb

a. Convert ppb to ppm

b. from Eqn. 4-5, 1ppm = 1 mg/L

therefore 10 ppb = 0.010 mg/L

4-7 Convert m3/s to MGD

Given: Flows of 0.0438; 0.05; 0.438; 0.5; 4.38; 5; all in m3/s

Solution: Use conversion factor from inside back cover

a. 0.0438 (3 significant figures)

(0.0438 m3/s)(22.8245) = 0.99971 or 1.00 MGD

b. 0.05 (1 significant figure)

(0.05)(22.8245) = 1.14123 or 1. MGD

(0.438)(22.8245) = 9.99713 or 10.0 MGD

(4.38)(22.8245) = 99.9713 or 100. MGD

(5)(22.8245) = 114.1225 or 100 MGD

4-8 Molarity and Normality

Given: Concentrations in mg/L

Solution: Molecular Weights are on inside of front cover. In each case:

4-9 Molarity and Normality

Given: concentrations in g/L

Converting micrograms to milligrams

4-10 Calculate molarity and normality

4-11 Converting to mg/L

Given: Molarity and normality

a. Ca2+ (n = 2 since charge is +2)

b. HCO3- (n = 1 since charge is 1)

(1.000 M)(61.016 g/mole)(1000 mg/g) = 61.020 mg/L

(0.02000 M)(96.054 g/mole)(1000 mg/g) = 1,921 mg/L

4-12 Converting to g/L

Given: Molarity and normality

(0.05 N)(62.01 g/eq)(1/2)(1,000,000 g/g) = 1.6 x 106 g/L

(0.0010 M)(119.37 g/mole)(1,000,000 g/g) = 1.2 x 105 g/L

(0.03 N)(74.096 g/eq)(1/2)(1,000,000 g/g) = 1.1 x 106 g/L

(0.0080 M)(60.011 g/mole)(1,000,000 g/g) = 4.8 x 105 g/L

4-13 Convert to mg/L

Given: 0.250 M NaOH; 0.0704 M Na2SO4; 0.0340 M K2Cr2O7; 0.1342 M KCl

mg/L of species = (molarity)(10000 mg/g)(GMW)

mg/L = (0.250)(1000)(40.00) = 10,000 mg/L

mg/L = (0.0704)(1000)(142.05) = 10,000 mg/L

mg/L = (0.0340)(1000)(294.20) = 10,003 or 10,000 mg/L