Chapter 2.

Environmental Chemistry

Chapter 2. Environmental Chemistry

1. Introduction

most of pollution problems have a chemical basis

chemical principles and the techniques of chemical engineering

design an emission control system or a waste treatment plant

In this brief chapter, the topics have been selected with the goal of providing
only the essential chemical principles required to understand the nature of the
pollution problems that we face and the engineering approaches to their
solutions.

2. Stoichiometry

EXAMPLE 1 Combustion of Butane

<Question>

Butane(C4H10)
100 g

CO2
? g

<Solution>

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Chapter 2. Environmental Chemistry

moles of solute
1 L of solution

Molarity =

mg/L =

Molarity

(mol)
(L)

MW

103

(g)
(mol)

(mg)
(g)

EXAMPLE 2 Theoretical Oxygen Demand

Glucose(C6H12O6)
1.6710-3 M

<Question>

O2
?

CO2 + H2O

<Solution>
Equation :
mass :
Concentration
of glucose

C6H12O6
180

6O2
192

6CO2
264

6H2O
108

1.6710-3 (mol) 180 (g) 103 (mg)

=

= 301 mg/L
(L)
301

O2 requirement

(mol)

mg glucose

=
L

192

(g)
g O2

180 g glucose

- 2 -

= 321 mg/L O2

Chapter 2. Environmental Chemistry

Standard Temperature and Pressure(STP) : 0 and 1 atm

1 mole of an ideal gas=22.4 L=0.0224 m3=6.021023 molecules

EXAMPLE 3 Carbon Emissions from Natural Gas

<Given Data>
- Worldwide methane consumption : about 10.91016 kJ/yr
- Energy of methane : 39103 kJ/m3(at STP) = 39103 kJ/Nm3
<Question> ? CO2/yr and ?MT C/yr
<Solution>
10.91016

Nm3

kJ

moles of CH4 =

yr

39103

mol
22.410-3

kJ

Nm3

= 12.51013
mol/yr

From stoichiometry of methane burning(balance equation),

CH4 + 2O2 CO2 + 2H2O : 1 mol of CH4 1 mol of CO2
12.51013
mass of CO2

Carbon
Emission

mol

44

=
yr

mol

5.51015 g CO2 12
yr

MT = 1.5109

g C

44 g CO2

- 3 -

= 5.51015 g CO2/yr

1106

MT C/yr

Chapter 2. Environmental Chemistry

3. Enthalpy in Chemical System

U1 + Q = U2 + W

(4)

where
U1 = internal energy of the chemical system at the beginning
U2 = internal energy at the end
Q = heat absorbed during the reaction
W = work dobe by the system during the reaction
W = F d = (P A) d = P(V2 - V1)

(5)

Eq(5)Wq(4) : (U2 + PV2) - (U1 + PV1) = Q

(6)

By definition of Enthalpy(H), H = U + PV

(7)

H2 H1 = H = Q

(8)

H > 0 endothermic(heat absorb)

H < 0 exothermic(heat liberate)
H0298(kJ/mol) = standard enthalpy at 1 atm and 298 K(25)
H0298 of pure elements at stable state = 0

TABLE 1 Standard Enthalpies for Selected Species (kJ/mol)

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Chapter 2. Environmental Chemistry

EXAMPLE 4 Gross Heat of Combustion for Methane

<Question> Heat of burning reaction of CH4 = ?
<Solution>
CH4(g)
(-74.9)

2O2(g)
2 (0)

CO2(g)
(-393.5)

2H2O(L)
2 (-285.8)

Heat of Rx = Products Enthalpy Reactants Enthalpy

= [2 (-285.8) + (-393.5)] -[(-74.9) + 2 (0)]
= -890.2 kJ/mol of CH4 negative Exothermic
Higher Heating Value(HHV) : Gross Heat of Combustion
includes the heat released when water condenses to liquid form
Lower Heating Value(LHV) : Net Heat of Combustion
the heat of reaction when water is assumed to remain in the vapor state

EXAMPLE 5 The Net Heat of Combustion

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Chapter 2. Environmental Chemistry

<Question> Net heat of combustion of CH4 burning?

<Solution>
CH4(g)
(-74.9)

2O2(g)
2 (0)

CO2(g)
(-393.5)

2H2O(g)
2 (-241.8)

Heat of Rx = Products Enthalpy Reactants Enthalpy

= [2 (-241.8) + (-393.5)] -[(-74.9) + 2 (0)]
= -802.2 kJ/mol of CH4

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Chapter 2. Environmental Chemistry

4. Chemical Equilibria

aA + bB cC + dD

(13)

where
a, b, c, d = coefficients corresponding to the number of molecules or
ions of the respective substances.
A, B, C, D = chemical species
[C]c [d]d
[A]a [B]b

At equilibrium,

= K, equilibrium constant

(14)

where [ ] = molarity of the substances

When Eq(14) is applied to Dissociation of molecules,
K = dissociation constant or ionization constant
When solid dissolves in solution, K = Ksp = solubility product
When gas dissolves in water, K = KH = Henrys constant
X = 10pX or pX = log X

(16)

<Acid-Base Reaction>
H2O H

+ OH

At equilibrium,

[H +][OH ]
[H2O]

= K

(18)

[H2O] = 55.56 mol/L = constant, since water dissociates only slightly, the
molar concentration after ionization is not changed enough to be of significance.

[H +][OH ] = Kw = 11014 at 25

(19)

where Kw = dissociation constant for water

pH = log [H+] or [H+] = 10pH

(21)

pH of unpolluted rainfall = 5.6

pH of actual acid rain by industrial pollutants < 2.0

EXAMPLE 7 pH of Tomato Juice

- 7 -

Chapter 2. Environmental Chemistry

<Question> [H+] = ?, [OH] = ? in tomato juice having a pH of 4.1.
<Solution>
Eq(21) [H+] = 10pH = 104.1 = 7.94105 mol/L
Eq(19) [OH] = 1014/[H+] = 1014/7.94105 = 1.261010 mol/L

Acetic acid in water

CH3COOH + H2O CH3COO + H+ + H20
CH3COOH CH3COO + H+

(22)

H2O appears as both side usually dropped from equation.

Dissociation Constant, Ka =

Ka
[H+]

Ka
10pH

[CH3COO][H+]
[CH3COOH]
[CH3COO]
[CH3COOH]

For acid, pH Degree of Dissociation

When [H+] = Ka(pH = pKa)

= 104.76
Degree of
Dissociation

[CH COOH] = [CH COO ]

FIGURE 3 diagram for acetic acid in water

TABLE 2 Dissociation Constants and Chemical Formulas for Some Acids of

- 8 -

(23)

(24)

Chapter 2. Environmental Chemistry

Environmental Importance

EXAMPLE 8 Drinking Water Disinfection Using Chlorine

<Question> pH ? to 1 =

[HOCl]
[OCl ] + [HOCl]

> 95%

<Solution> HOCl OCl + H+

(25)
[OCl][H+]
[HOCl]

Table 2 Dissociation Constant, Ka1 =

Eq(26) [H+] =

Ka1[HOCl]
[OCl]

107.6 95
5

= 107.6

= 4.77107

(26)

= 106.32

pH < 6.32 to minimum 95% of Cl will be in HOCl form.

<Solubility Product(Ksp)>
Solid aA + bB
Eq(14)

Equilibrium constant =

(27)
[A]a[B]b
[Solid]

= K

If solid is present at equilibrium, [A]a[B]b = Ksp (Solubility Constant)

TABLE 3 Selected Solubility Product Constants at 25

- 9 -

(28)

Chapter 2. Environmental Chemistry

EXAMPLE 9 Fluoride Solubility

Ca

2+

<Question> CaF2

+ 2F in pure water

[F] at equilibrium in units of mol/L and mg/L?

<Solution> Table 3

sp

= 3 1011 = [Ca2+][F]2

Let [Ca2+] = s, [F] = 2s by stoichiometry.

Eq(30)

310

11

= [Ca2+][F]2 = s (2s)2 = 4s3

[F] = 2s = 410

(30)

s = 210

mol/L

= 4104 mol/L 19 g/mol 103 mg/g = 7.6 mg/L

Recommended F ion concentration in drinking water : 1.8 mg/L

<Solubility of Gases in Water>

Henrys Law : [gas] = K P

(31)

H g

where
[gas] = concentration of dissolved gas(mol/L)

KH = Henrys law constant(mol/(L atm))

Pg = partial pressure of the gas in air(atm)

1 atm = 101,325 pascals(Pa) = 101,325 N/m

P change according to altitude, P = P 1.1510
2

where
P = atmospheric pressure at altitude H(atm)
H = altitude(m)
P0 = atmospheric pressure at sea level(atm)

- 10 -

H (32)

Chapter 2. Environmental Chemistry

atm))

TABLE 4 Henrys Law Coefficients, (mol/(L

EXAMPLE 10 Solubility of Oxygen in Water

<Given Data>

Concentration of O in air is about 21 %(v/v)

KH = 0.001263 mol/(Latm)
2

<Question>

Equilibrium [O ] in water at 25C and 1 atm?

Same at an altitude of 1,525 m?
2

<Solution>

Equilibrium [O ] in water at 25C and 1 atm?

Eq(31) [O ] = K P = 0.001263 0.21 = 2.6510
2

[O2] =

H g

2.65104 mol
L

32 g
mol

103 mg
= 8.5
g

mol/L

mg
L

Same at an altitude of 1,525 m

Eq(32)P=P 1.1510 H=0.211.1510 1525=0.825 atm
4

Pg = 0.825 atm 0.21 = 0.173 atm

Eq(31)
[O2] =

[O ] = K P
2

H g

= 0.001263 0.173 = 2.19104 mol/L

2.19104 mol
L

32 g
mol

103 mg
= 7.0
g

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mg
L

Chapter 2. Environmental Chemistry

Gas(NH , H S, VOC) Striping

3

Henry constant of NH3 = 57 mol/(L atm) at 25

NH (g)+ H
By adding the base(OH, hydroxide ion) or pH
NH + OH NH (g) + H O
By driving the acid/base equilibrium, NH4+

(33)

(34)

EXAMPLE 11 Ammonia Stripping

<Given Data>

In wastewater, [NH ] + [NH (g)] = 7.110 M

Henry constant of NH = 57 mol/(Latm) at 25
4

<Question>

[N] and [NH (g)] = f(pH) ?

[TN] at equilibrium when pH=10 and [NH ] in air=510
3

10

atm?

<Solution>

[N] and [NH (g)] = f(pH)

Eq(33) and Table 2 K =
3

[NH3][H+]
[NH4+]

[NH3]
[NH3] + [NH4+]

Fraction of NH3 =

Eq(37)Eq(36) :
Eq(35)

[H+]
Ka

Fraction of NH3 =
=

[NH4+]
[NH3]

= 109.26

(35)

1
1 + [NH4+]/[NH3]

= [H+] 109.26

1
1 + [H ] 109.26
1
1 + 10(9.26pH)
+

- 12 -

(36)

(37)

1 +

10pH

109.26
(38)

Chapter 2. Environmental Chemistry

FIGURE 4 Dependence of the ammonia fraction, a1, on pH.

[TN] at equilibrium when pH=10 and [NH ] in air=510 atm

57 mol 510 atm
Eq(31)[NH ]=K P =
=2.8510 mol/L
Latm
Eq(38) Fraction of NH at pH 10 = 0.846
TN = 2.8510 mol/L / 0.846 = 3.36910 mol/L
3.36910 M
% removal of TN = 1
= 0.99995 = 99.995%
7.110 M
10

10

H g

8
4

<The Carbon System>

Chemical species including carbon system

Aqueous carbon dioxide

CO2(aq)

Carbonic acid

H2CO3

Bicarbonate ion

HCO3

Carbonate ion

CO32

Henrys Law [CO ] = K P

P = 360 ppmv or 36010 atm in atmosphere
2 aq

CO2

H g
6

- 13 -

(39)

Chapter 2. Environmental Chemistry

Carbonic acid(H CO ) : Diprotic acid

Chemical Reactions
CO (aq) + H O H CO H
HCO H + CO
CaCO (s) Ca + CO
2

+ HCO3

(40)

(41)

2+

2
3

(42)

At 25

Eq(40) & Table 2

[H+][HCO3]
[CO2(aq)]

= K1 = 4.47107 mol/L

][CO ]
[H[HCO
= K = 4.6810 mol/L
]
Eq(42) & Table 3 [Ca ][CO ] = K = 4.5710 mol /L
+

Eq(41) & Table 2

11

2+

(43)

sp

(44)
(45)

Four possible conditions

with CaCO3

Open to atmosphere

without CaCO3

Close to atmosphere

Rainfall : open system not in contact with a carbonate solid

[CO ]
K
K
Eq(44)[H ]
=
=
= 4.6810

[HCO ]
[H ]
10
2

2
+

- 14 -

2
pH

(pH 11)

(47)

Chapter 2. Environmental Chemistry

FIGURE 5 diagram for the carbonate system.

0 = fraction of the total carbonate in the system that is in the carbonic

acid form(H2CO3)

1 = fraction in the bicarbonate anion form(HCO3)

2 = fraction in the carbonate anion form(CO32).

At high pH, [CO32] : dominant

At middle pH, [HCO3] : dominant

At low pH, [H2CO3] : dominant

EXAMPLE 12 The pH of Natural Rainwater

and 1 atm

<Given Data> [CO2] = 390 ppmv at 25

<Assumption> only substance affecting it is the absorption of CO2 from the

atmosphere
<Question> pH of natural rainwater ?
<Solution>
Neutrality

[H ] = [HCO ] + 2[CO
+

At acidic condition, [CO32] = negligible

+ [OH]

- 15 -

(48)

Chapter 2. Environmental Chemistry

So, Eq(48)

[H ] = [HCO ] + [OH]
+

(49)

[H ][OH] = K = 10
Eq(19) Eq(49) : [H ] = [HCO ] + 10 / [H ]
K [CO (aq)]
Eq(43) [HCO ] =
Eq(50)
[H ]
+

Eq(19)

14

14

14

(aq)]
10
[H ] = K [CO
+
=
[H ]
[H ]
Rearrange to [H ] [H ] = K [CO (aq)] + 10
1

(50)

2
+

Eq(50)

(19)

2
+

+ 2

K1[CO2(aq)] + 1014
[H+]

14

(52)

To find saturation [CO2], from Eq(39)

[CO2]aq = KHPg
0.033363 mol 390106 atm
= 1.3105
L atm

[CO2]aq = KHPg =
Eq(52)

[H ]

+ 2

= 4.47107 1.3105 + 1014

= 5.8111012 + 1014
= 5.8211012

[H ] = 2.4110
+

or pH =

log [H ] = 5.62
+

- 16 -

mol
L