ENVIRONMENTAL CHEMISTRY

I. Physical Chemistry
1. Stoichiometry

2. Chemical Equilibrium
It is achieved when rates of the forward and reverse reactions are equal and concentrations of the reactants and products remain
constant.
It can be used to analyze a variety of different aqueous reactions of interest to an environmental engineer or environmental
engineering student.
It can be used in determining the amount of base to add to an acid spill, amount of acid to neutralize a basic process wastewater,
solubility of metal in a chemical waste stream, estimated amount of phosphorus removed in a wastewater treated with lime,
and solubility of mercury complexed in seawater.

Given a reaction,

aA + bB cC + dD
where: a, b, c, d = stoichiometric coefficients
A, B, C, D = substances with concentration in mol/L

Equilibrium Constant (Kc)

Formulated by Cato Guldbery and Peter Waage in 1864
Mathematical expression of Law of Mass Action which states that for a reversible reaction at equilibrium and constant
temperature, a certain ratio of reactant and product concentration has a constant value, K c
Tells whether an equilibrium reaction favors the reactants or products
Include only substances in the gas or aqueous phase; solid and liquid concentrations do not change during a chemical
reaction
C c Dd concentration of products raised to its respective stoichiometric coefficient
KC = a b =
A B concentration of reactants raised to its respective stoichiometric coefficient

Examples:
1. CH3COOH(aq) + H2O(l) CH3COO-(aq) + H3O+(aq)

2. HF(aq) + H2O(l) H3O+(aq) + F-(aq)

3. NO(g) + O2(g) NO2(g)

Predicting the Direction of a Reaction

For reactions that have not reached equilibrium, we get the reaction quotient (Qc) by substituting the initial concentrations into the
equilibrium constant expression.
Qc > K c the system proceeds from right to left (consuming products, forming reactants) to reach equilibrium
Qc = K c initial concentrations are equilibrium concentrations, system is at equilibrium
Qc < K c the system proceeds from left to right (consuming reactants, forming products) to reach equilibrium;
to reach equilibrium, reactants must be converted to products

Q c Kc Q c Kc Qc Kc
reactant product equilibrium reactant product

Example:
At the start of a reaction, there are 0.249 mol N2, 3.21 x 10-2 mol H2, and 6.42 x 10-4 mol NH3 in a 3.50 liter reaction vessel at 375oC.
If the equilibrium constant, Kc, for the reaction is 1.2 at this temperature, decide whether the system is at equilibrium. If it is not,
predict which way the net reaction will proceed.
N2(g) + H2(g) NH3(g)

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Calculating Equilibrium Concentrations
Use Initial Change Equilibrium (ICE) method

Examples:
1. A mixture of 0.5 mol H2 and 0.5 mol I2 was placed in a 1 liter stainless steel flask at 430oC. The equilibrium constant, Kc, for
the reaction
H2(g) + I2(g) HI(g)
is 54.3 at this temperature. Calculate the concentrations of H2, I2, and HI at equilibrium.

2. For the same reaction and temperature as above, suppose that the initial concentrations of H 2, I2, and HI are 0.00623 M,
0.00414 M, and 0.0224 M respectively. Calculate the concentrations of these species at equilibrium.

Autoionization of Water
Water is a weak electrolyte and is a poor conductor of electricity but it undergoes ionization to a small extent which is called
autoionization of water.
H2O(l) H+(aq) + OH-(aq)

Therefore, the equilibrium constant equation for water is,

[H + ][OH ]
Kc =
[H2 O]

K w = [H + ][OH ]

In pure water at 25oC, the concentrations of H+ and OH- ions are equal and found to be 1.0 x 10-7 M. Thus,
K w = (1.0 x 107 )(1.0 x 107 ) = 1.0 x 1014
pK w = pH + pOH = 14
pH = log [H + ]
pOH = log [OH ]

Acid Ionization Constant (Ka)

Equilibrium constant for the ionization of a weak acid since weak acids only ionize to a limited extent in water
Strong acids undergo neutralization
Always has H+ product

Examples:
1. Calculate the pH of 0.5 M HF solution at 25oC. (Ka = 7.1 x 10-4)

a. Method of Successive Approximation

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 To check:
x
x 100 5%
x0

b. Quadratic Equation

2. Calculate the pH of a 0.036 M nitrous acid (HNO2) solution. (Ka = 4.5 x 10-4)

Percent Ionization
ionized acid concentration at equilibrium
% ionization = x 100
initial concentration of acid

[H + ]
% ionization = x 100
[HA]0

Base Ionization Constant (Kb)

Equilibrium constant for the ionization of a weak base since weak bases only ionize to a limited extent in water
Strong bases undergo neutralization
Always has OH- product

Example:
What is the pH of a 0.4 M ammonia (NH3) solution? (Kb = 1.8 x 10-5)

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Environmental Engineering
Solubility Product Constant (Ksp)
Indicates solubility of ionic compound
Product of the molar concentrations of the constituent ions, each raised to the power of its stoichiometric coefficient in the
equilibrium equation
High Ksp indicates that the ionic compound is more soluble while a low K sp indicates that the ionic compound is less soluble
in water

Examples:
1. MgF2:

2. Ag2CO3:

3. Ca3(PO4)2:

Molar solubility number of moles of solute in 1 liter of a saturated solution (mol/L)

Solubility number of grams of solute in 1 liter of a saturated solution (g/L)

Examples:
1. The solubility of calcium sulfate is found experimentally to be 0.67 g/L. Calculate the value of K sp for calcium sulfate. (Ca =
40.1 g/mol, S = 32 g/mol)

2. Calculate the solubility of copper (II) hydroxide, Cu(OH) 2, in g/L. (Ksp = 2.2 x 10-20; Cu = 63.55 g/mol)

3. What pH is required to reduce a high concentration of dissolved Mg+2 to 43 mg/L? (Ksp = 10-11.16; Mg = 24.3 g/mol)
Mg(OH)2 Mg+2 + OH-

4. Calculate the pH necessary to lower the concentration of dissolved Fe+2 to 0.0030 M? (Ksp = 1.6 x 10-14)
Fe(OH)2 Fe+2 + OH-

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Environmental Engineering