5-1

Introduction to Environmental
Engineering 5th Edition Davis
Solutions Manual
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CHAPTER 5
SOLUTIONS

5-1 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

5-2 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

5-3 Concentration of NH3 in mg/L

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

Solution:

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 5-2
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

5-4 Concentration of Cl2 in mg/L

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 5-3

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

5-5 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

5-6 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. 5-5, 1ppm = 1 mg/L

therefore 10 ppb = 0.010 mg/L

5-7 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

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 5-4

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

5-8 Molarity and Normality

Given: Concentrations in mg/L

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

mg L of sp ecies

M olarity =
(1000 mg g )(molecular  weight )

Normality = (molarity)(n)
a. HCN

200.0
Molarity = =
(1000)(36.4609) 0.005485M

Normality = (0.005485)(1) = 0.005485 N

b. H2SO4

150.0
Molarity = = 0.001529M
(1000)(98.07 )

Normality = (0.001529)(2) = 0.003059 N

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 5-5

c. Ca(HCO3)2

100.0
Molarity = = 0.0006168M
(1000)(162.1122)

Normality = (0.0006169)(2) = 0.001234 N

d. H3PO4

70.0
Molarity = = 0.000714M
(1000)(97.9951)

Normality = (0.000714)(3) = 0.00214 N

5-9 Molarity and Normality

Given: concentrations in µg/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 

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 5-6
0.135
Molarity = = 1.3 10 −6 M
(1000)(100.09)

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 5-7

Normality = (1.3 x 10-6 M)(2) = 2.7 x 10-6 N

c. Cr(OH)3

 
(10 g L) 1
 = 0.01mg 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

5-10 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 sp ecies

M olarity =
(1000 mg g )(molecular  weight )

Normality = (molarity)(n)

a. As3+
0.05 ( 000)(74.92)
Molarity = = 1
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 5-8
6.67 10
−7
M

Normality = (6.67 x 10-7 M)(3) = 2.00 x 10-6 N

b. Cd2+

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 5-9

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

5-11 Converting to mg/L

Given: Molarity and normality

Solution:

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

(0.01000N ) 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)

(0.02000N ) 98.07 g 

eq (1000 mg g ) = 980.7 mg L
2 


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 5-10

d. SO42-

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 5-11

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

5-12 Converting to µg/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 µg/L

b. CHCl3

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

d. CO32-

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

5-13 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

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 5-12

d. KCl

mg/L = (0.1342)(1000)(74.55) = 10,005 or 10,000 mg/L

5-14 Solubility of Mg in mg/L

Given: Solution 0.001000 M in OH

Solution:

From Table 5-1 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

5-15 pH to precipitate iron

Given: Groundwater has 1.800 mg/L Fe and desired concentration is 0.30 mg/L

Solution: From Table 5-1 pKSP = 38.57 for Fe(OH)3

KSP = 10-38.57 = 2.69 x 10-39

Fe = 0.30 mg L
=  −6
(55.85g mole )(1000 mg g ) 5.37 10 mole L

KSP = [Fe][OH]3
13
 2.69 10−39 
OH −
=  = (5.0110 −33 )
13
= 7.94 10 −12 mole L
 5.37 10 −6 
 

pOH = -log (7.94 x 10-12)

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 5-13
pOH = 11.10 and pH = 14.00 - 11.10 = 2.90

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 5-14

5-16 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 2+ =  0.200 mg L
=  −6
(63.55g mole )(1000 mg g ) 3.15 10 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

5-17 Calcium remaining in solution

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 5-15

Given: Saturated solution of CaCO3 and addition of 3.16 x 10-4 moles/L of Na2CO3

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 5-16

Solution: This solution requires the solution of a quadratic equation.

a. Begin with the equilibrium reaction (Eqn 5-9 or Table 5-1.)

CaCO 3  Ca 2+ + CO 3 2−

b. Write the equilibrium expression using KSP from Table 5-1

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
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 5-17
also change.

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 5-18

5-18 Fluoride solubility

Given: Solubility product of CaF2 = 3.45 x 10-11, F- = 1.0 mg/L and Ca2+ = 200 mg/L

Solution:

a. Convert Ca and F to moles/L


Ca 2+ =  200 mg L
=  −3
(40.08g mole )(1000 mg g ) 4.99 10 mole L

F  = (19.00 g 1.0
− mg L
mole )(1000 mg g )
=  −6

5.26 10 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.

5-19 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
CaSO 4  Ca 2+ + SO 42−

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

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 5-19

c. Set up quadratic equation where

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 5-20

Ca  = (6.99810 ) − x
2+ −3

SO  = (6.99810 ) + (5.00 10 ) − x = (1.200 10 ) − x

4
2− −3 −3 −2

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
x = 4.137 10 −3
and

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

5-20 Amount of base to neutralize acid

Given: Acid concentrations in Example 5-7

Solution:
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 5-21

a. The reaction is

H 2SO 4 + 2NaOH  Na 2SO 4 + 2H 2 O

Therefore two moles of NaOH are required to neutralize each mole of H2SO4.

Assuming one liter:

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

5-21 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

5-22 Neutralize finished water with HCl

Given: Problem 5-21

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 5-22

Solution: Since the normality is exactly the same as in Problem 5-21 the form of the acid
is irrelevant and the answer is the same as in Problem 5-21, i.e. 27.5 mL

5-23 Titration curve

Given: 50 mL solution of 0.0200 N NaOH; titrate with 0.0200 N HCl

Solution:

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 )(0.0200N ) − (1.00mL)(0.0200N )= 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.

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 5-23

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

Moles of HCl Moles of NaOH Milliters of

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

At the equivalence point the pOH = 7.00

From the equivalence point on, pH is calculated directly.

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 5-24

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

Problem 5-23 Titration Curve

12

10

pH
6

0
0 10 20 30 40 50 60
Milliters of HCl

Figure S-5-23: Titration curve

5-24 pH of water containing carbonic acid

Given: 0.6580 mg/L H2CO3; assume [H+] = [HCO3-]

Solution:
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 5-25

a. From Table 5-3, pKa = 6.35 for H2CO3

b. Convert mg/L to moles/L

0.6580mg
= 1.061  10 mole L
−5

(62.026 g mole )(1000 mg g )

c. Write equilibrium expression

H HCO 
+
3
−
−6.35 −7
Ka = = 10 = 4.467 10
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

5-25 HCO3- concentration at a pH of 4.50

Given: Problem 5-24

Solution:

a. From Table 5-3 pKa = 6.35 for H2CO3

b. The molar concentration of H2CO3 is

0.6580 mg L
H 2 CO 3  = =  −5
(62.026 g mole )(1000 mg g ) 1.061 10 mole L

c. Calculate [H+]
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 5-26

[H+] = 10-4.50 = 3.16 x 10-5

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 5-27

d. Solve the equilibrium expression for [HCO3-]

HCO  = K H CO  = (10 )(1.06110

− a 2 3 −6.35 −5 mole L)
3
H  +
3.16 10 −5 mole L

= 1.498 x 10-7 or 1.50 x 10-7 mole/L

5-26 pH of water containing hypochlorous acid

Given: 0.5000 mg/L HOCl; assume equilibrium

Solution:

a. From Table 5-3, pKa = 7.54 for HOCl.

b. Convert mg/L to mole/L

0.5000mg
= 9.53  10 mole L
−6

(52.45g mole )(1000 mg g )

c. Write equilibrium expression

H OCl  −7.54 −8
Ka = + −
= 10 = 2.884 10
HOCl

d. Substitute hypochlorous acid concentration

 
+ −

K a = H OCl−6 = 2.884  10 −8

9.5310 

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

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 5-28

5-27 OCl- concentration

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 5-29

Given: Data in Problem 5-26 and pH = 7.00

Solution:

a. From Table 5-3, pKa = 7.54 for HOCl.

b. Convert mg/L to mole/L

0.5000mg
= 1.371  10 mole L
−5

(36.46 g mole )(1000 mg g )

c. Write equilibrium expression

H OCl  −7.54 −8
Ka = + −
= 10 = 2.884 10
HOCl

d. With [H+] = 10-7 and hypochlorous acid concentration

K =
10 OCl  = 2.884 10
−7 −
−8

a
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

5-28 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

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 5-30

mg/L as CaCO3 = 83.00 mg L 

50.04 
 = 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)

44.01
E.W. = = 22.00
2

mg/L as CaCO3 = 48.00 mg L 

50.04 
 = 109.2
 22.00 

d. HCO3- (n = 1 because valence = 1)

61.02
E.W. = = 61.02
1

mg/L as CaCO3 = 220.00 mg L 

50.04 
 = 180.4
 61.02 

e. CO32- (n = 2 because valence = 2)

60.01
E.W. = = 30.00
2

mg/L as CaCO3 = 15.00 mg L 

50.04 
 = 25.02
 30.00 

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 5-31
5-29 Converting from mg/L to mg/L as CaCO3

Given: Concentrations in mg/L as ion

Solution: E.W. of CaCO3 = 50.04

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 5-32

a. HCl (n = 1 because 1 replaceable H)

36.461
E.W. = = 36.461
1

mg/L as CaCO3 = 200.00 mg L 

50.04 
 = 274.5
 36.461 

b. CaO (n = 2 since Ca must be replaced by 2 H+)

56.08
E.W. = = 28.04
2

 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

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 5-33
 50.04 
mg/L as CaCO3 = 19.90 mg L   = 9.143
 22.9898 

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 5-34

5-30 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

mg/L = 100.00 mg/L as CaCO3 

48.03 
 = 95.98
 50.04 

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

mg/L = 150.00 mg/L as CaCO3 

20.04 
 = 60.07
 50.04 

d. H2CO3 (n = 2 because 2 H)

62.03
E.W. = = 31.02
2

mg/L = 10.00 mg/L as CaCO3 

31.02 
 = 6.198

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 5-35
+
e. Na (n = 1 because valence = 1)  50.04 

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 5-36

22.9898
E.W. = = 22.9898
1

 22.9898 
mg/L = 150.00 mg/L as CaCO3   = 68.91
 50.04 

5-31 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)

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

mg/L = 13.50 mg/L as CaCO3 

37.045 
 = 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
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 5-37
2

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 5-38

 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

mg/L = 40.00 mg/L as CaCO3 

35.453 
 = 28.34
 50.04 

5-32 Convert N to mg/L as CaCO3

Given: 0.0100 N Ca2+

Solution:

a. Convert N to molarity (Eqn. 5-8)

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. 5-40

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 5-39

mg/L as CaCO3 = 200.40 mg L 

50.04 
 = 500.4 or 500 mg/L as CaCO3
 20.04 

5-33 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+]

[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 ) 1.0079

−3 50.04 
 = 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 ) 17.007

−5 50.04 
 = 2.287 10
−4

 

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 5-40

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

5-34 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

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

5-35 Exact alkalinity

Given: Problem 5-34; 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 CaCO 3
 61.016 

b. Convert CO32- to mg/L as CaCO3

 50.04 
15.0  = 25.02 mg/L as CaCO 3
 30.004 

c. Convert pH to H

[H+] = 10-9.43 = 3.715 x 10-10 mole/L

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 5-41

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 ) 1.0079

−7 50.04 
 = 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

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

5-36 Approximate alkalinity

Given: 15.00 mg/L HCO3-, 120.0 mg/L CO32-

Solution:

a. Convert to mg/L as CaCO3

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 5-42

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

5-37 Derivations

Given: Equations 5-28, 5-36, 5-38, 5-39

Solution:

a. Starting with

Eqn. 5-28 Kw = [OH-][H+]

Eqn. 5-36 Alk = [HCO3-] + 2[CO32-] + [OH-] - [H+]

Eqn. 5-38 H2CO3 = H+ + HCO3- pKa1 = 6.35

Eqn. 5-39 HCO3- = H+ + CO32- pKa2 = 10.33

b. From equilibrium reactions (Eqns. 5-38, 5-39)

K1 =
H HCO 
+
3
−

H 2 CO 3 

H CO 
+ 2−

K2 =
HCO 
3
−
3

c. From definition of alkalinity where A = Alkalinity

[HCO3-] = A - 2[CO32-] - [OH-] + [H+]

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 5-43
d. Substituting from Eqn. 5-28

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 5-44

HCO  = A − 2CO − K  + H 
− 2− w +

H+
3 3

e. Substituting the K2 equilibrium expression for CO32-

 =  
H   
K HCO Kw
−   +
+ H+
HCO 3 −
 
−
A 2 −
H 
2 3
 +

f. Collecting terms

HCO  
 K 2 HCO3 −  = A − K
+ 2
H  + H 
− +
 
w
3
H+  +
 

g. Factor out [HCO3-]


HCO − 1 +  
  2K 2  K
 = A − w + H +
     
3  +  H+
  H 

h. Solve for HCO3-

=   
Kw
A− +H +

HCO  =
3
− H+

  2K2 
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 ) KH  +(5 10 )H 
+
w 4 +

−
HCO 3 =
  2K 
1 + + 
 
2

  H 
4  A Kw + 
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 5-45
(5 10 ) − 
+H
  
4 +

HCO 3 =
− 5 10 H 
  2K2 
1 + + 
 
  H 

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 5-46

j. An equation for CO32- can be derived by putting the HCO3- expression into the K2
equilibrium expression:
K
A − w + H+  

CO −
=   
+
 
H
2  2K 2  H
3  +  2K 2 
 
1+  + 
 
 H 

k. In terms of mg/L CaCO3 alkalinity

 A + 

Kw
5(  10 4 ) − + +H
  
4

 2K   5 10 H 
=  +2 
 
2−
CO 3
H  2K 
1 +  +2 
 
 H 
 
−  K 
 −

 
2 2 2
CO 3 =  +  HCO3
 H 

5-38 Calculating bicarbonate and carbonate alkalinity

Given: Total alkalinity = 233.00 mg/L as CaCO3; pH = 10.47; Eqns. from Prob. 5-37.

Solution:
4  233.00 10 −14 
−10.47

5 10  + 10 − −10.47 
5 10 4 10
−
=  
( )
HCO3
 2 4.68 10 −11 
1+  
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 5-47

10 −10.47 

− 5 10 4 (4.66 10 −3 +3.388 10 −11 −2.95110 −4 )

HCO3 =
1+ 2.762

− 2.182 10 2
HCO 3 = = 58.01 mg/L as CaCO3
3.762

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 5-48

(
 2 4.68 10 −11 
CO 3 2− = 58.01 
)
 10 −10.47 

= (58.01)(2.762) = 160.22 mg/L as CaCO 3

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

5-39 Calculate bicarbonate and carbonate alkalinity

Given: Solution to Problem 5-37 and given water specifications. Total alkalinity = 284.0
mg/L as CaCO3, pH = 7.6

Solution:

a. Bicarbonate
 284.0 10 −14 
5 10 4  + 10 −7.6 − 
−7.6

HCO3 =
− 50000 10 
(
 2 4.68 10 −11 )
1+  
 10 −7.6 

− 5 10 4 (5.68 10 −3 +2.512 10 −8 −3.98110 −7 )

HCO3 =
1+ 3.726 10 −3

HCO3- = 2.829 x 102 mg/L as CaCO3

b. Carbonate

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 5-49

−
CO 3 2 = 2.892 10 2 
(
 2 4.68 10 −11  )
 = 1.08 mg/L as CaCO3
−7.6
 10 

Check total alkalinity

Total ALK = 282.9 + 1.08 = 283.99 or 284.0 mg/L as CaCO3

5-40 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 5-37

2(4.68 10 −11 )

200.16 =
10 −10.30
( HCO3− )
c. Solve for HCO3-

200.16
HCO =  = 107.177 mg/L as CaCO
−  
3 3
 1.868 

d. Convert to ion
61.016
HCO = 107.177  = 130.686 or 130.7 mg/L
−  
3
 50.04 

5-41 Determining pH from carbonate and bicarbonate

Given: HCO3- = 120.00 and CO32- = 15.00 mg/L as ion

Solution:
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 5-50
a. Convert to mg/L as CaCO3

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 5-51

HCO3- = 120.00 (50.04/61.016) = 100.053

CO32- = 15.00 (50.04/30.00) = 25.020

b. Use solution to Problem 5-37 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

5-42 Calculating alkalinity by two methods

Given: Data in Problem 5-40 and equations from Problem 5-37

Solution:

a. Calculate CO32- and HCO3 concentrations in mg/L as CaCO3 in the same fashion as in
Problem 5-40.

CO32- = 200.16 mg/L as CaCO3

HCO3- = 107.177 mg/L as CaCO3

b. Setup equation from Problem 5-37 and solve for "A"

4 A −10.30 10 −14 
5 10  + 10 − −10.30 
5 10 4 10
 
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

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 5-52
+
d. Convert pH to [H ]

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 5-53

[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 ) 1.0079

−8 50.04 
 = 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 CaCO
 
 17.007 
3

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

5-43 Reaction order and rate constant

Given: Data table

Solution:

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 5-54

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 5-5.

Problem 5-43 Rate Constant

10.00

oncentration
, mmoles/L
1.00

y = 2.8002e-0.1401x

0.10
0 5 10 15 20 25
Time, min

Figure S-5-43: Rate constant plot

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
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 5-55

5-44 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 5-5.

Problem 5-44 Rate Constant

1.6
1.4
1.2
1/[A] 1
0.8
y = 0.1399x + 0.0208
0.6
0.4
0.2
0
0 5 10 15
Time, min

Figure S-5-44: 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

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 5-56

1 1
+ = K (5)
1.39 48.0

0.72 + 0.021 = K(5)

K = 0.1482 min-1

(Slightly different K will result for other time intervals.)

DISCUSSION QUESTIONS

5-1 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.

5-2 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.

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