CIVI 361

Introduction to Environmental
Engineering
Lecture Notes:
DR. RIHAM A.MOHSEN Chapter 3
Environmental
Chemistry

Adapted from
James R. Mihelcic, Julie B. Zimmerman “Environmental Engineering:
Fundamentals, Sustainability, Design”, 2nd Edition.
 CHAPTER 3
ENVIRONMENTAL CHEMISTRY

Outline

❑Chemical Equilibrium

❑Precipitation-Dissolution

❑Sorption, Adsorption, Absorption

❑Chemical Kinetics
❑ Approaches in Environmental Chemistry

Two major approaches …

• Kinetics ➔ deal with the rates of reactions
• Equilibrium ➔ deal with the final result or stopping place of reactions
Ex: acid-base reactions, and some phase-transfer reactions such as volatilization
❑ Activity and concentration

Concentration- “Actual concentration” ( )

Activity- “ effective concentration” that participate in a chemical reaction. ( )
❑ Reaction Stoichiometry

• Law of conservation of mass ➔ in a closed system, the mass of material present remains constant; the material
may change form, but the total mass remains the same.
• Stoichiometry ➔ calculation of reactants and products in chemical reactions
Reaction Stoichiometry

Stoichion + Metry : element + measure

Determine the amount of substance that is consumed or produced by a reaction
Reaction stoichiometry: based on conservation law
- Number of atoms of each element must be the same on both sides of the reaction
equation.
-Sum of charges on each side of a reaction equation must be equal.
-Balance between the number of protons and electrons also must remain constant in a
closed system

Balance in mass and charge

Stoichiometry to convert units of concentration and to calculate inputs and outputs.
❑ Volatilization
❑ Air-Water Equilibrium
Oxygen in air and water
• Henry's Law
The weight of any gas that will dissolve in a given volume of a
liquid, at a constant temperature, is directly proportional to the
pressure the gas exerts above the liquid. Equilibrium can be expressed as

Cs = KH×Pg
where
• Cs → the concentration of gas dissolved in the liquid at
equilibrium
• KH → Henry’s law constant for the gas at the given
temperature
• Pg → partial pressure of the gas above the liquid Partial pressure
of O2 in air

Example:

What is the equilibrium concentration of O2 in water at 20 °C ✓ Engineering application→ The addition of

and in the pressure of 1 atm of air? Henry’s law constant for oxygen by aeration to maintain aerobic
conditions
O2 in water at 20 °C = 43.8 mg/L•atm.

Solution: ✓ Henry’s law for equilibrium → show how

Air contains 20.9% by volume of oxygen far a gas-liquid system is from equilibrium.
Partial pressure of O2 = 0.209 atm
The equilibrium concentration of O2 in water at 20 °C and in
the pressure of 1 atm of air ➔ 43.8 × 0.209 = 9.15 mg/L
❑ Acid-Base Chemistry
✓ Ionization of water
• pH [H+][OH-] = Kw = 10-14
H2 O H+ + OH- Pure water dissociates
Ionization constant
for pure water
1
pH = -log10 [H+] = log 10 Acid: [H+] = 10-3 mol/L ➔ pH = 3
[H+]
Base: [OH-] = 10-3 mol/L ➔ pH = 11
[H+] = [OH-] = 10-7 mol/L ➔ pH = 7
pH?
Coffee → pH 5
Vinegar → pH 3

Lemon juice → pH 2
In stomach → pH 1.5-3.5
Baking soda → pH 9.5
Bleach → pH 13
 HA H + + A-

pKa = -log(Ka)
• Strong acid ➔ strong tendency to dissociate
➔ high K a, low pK a, pK a < 2
• Weak acid ➔ less tendency to dissociate
➔ low Ka, high pKa
 1 for solid

Solubility ➔ the maximum quantity of a

substrate (the solute) that can dissolve in a unit
volume of solvent under specified conditions.
Example: precipitation-dissolution equilibrium

What pH is required to reduce a high

concentration of dissolved Mg2+ to 43 mg/L? Ksp for
the following reaction is 10-11.16.

Solution:
Unit conversion to mole/L

[OH-] = 6.2 × 10-5 M

[H+] = 10-9.79 M

pH = 9.79
 Sorption includes
adsorption and absorption ...
❑Adsorption ➔ accumulation on surfaces of solids
Example: NH3 is adsorbed by charcoal.
❑Absorption ➔ interpenetration or intermingling
with solids
Example: NH3 is absorbed in water forming NH4OH.

❑ Sorbate ➔ substance that is adsorbed

❑ Sorbent ➔ the solid

Sorbate
Adsorption Absorption
(“partitioning”)

Liquid Liquid Sorbent

Solid Solid

liquid
CIVI 361 INTRODUCTION TO ENVIRONMENTAL ENGINEERING
The Jargon of Sorption
Sorption Isotherms
Sorbate (pollutant)

- The amount of material sorbed is

determined as a function of the
concentration at constant temperature, and
C (mg/L in solution) the resulting function is called sorption
isotherms.
Sorbent

Sorption Isotherms
Q (mg/g on sorbent )
Liquid
Dose • Describe equilibrium partitioning between
(g/L) amount sorbed and in liquid phase.

Define the following:

Qe = mass of material sorbed per mass of sorbent
at equilibrium (x/m=X)

Ce = equilibrium concentration in solution when

amount sorbed equals Q e.
Example: how to get Ce and Qe

Time: 0 h Time: 24 h
Adsorbent:
Pesticide in
Activated Carbon
water
➔1g
➔10 mg/L
Liquid: water
➔ 100 mL
Ce, Q e ➔ ?
Pesticide in water
➔100 mg/L

Assumption: 24 h → enough for reaching equilibrium

No degradation
3

Ce = 10 mg/L

(C0 – Ce)×V
Qe = • Adsorption ‘isotherm’ is a Q e -- C e relationship
madsorbent at equilibrium.
• Relationships depend on the type of adsorption
(100 mg/L – 10 mg/L) × 100 mL
that occurs.
=
1g • Adsorption isotherms can have many shapes.

= 9 mg/g
Linear ➔ all sites have
equal energy
Favorable ➔ added
adsorbates are bound with
weaker and weaker
energies
Unfavorable ➔ more
adsorbate presence
enhances the free energies
of further adsorption
Three most popular adsorption
isotherm models Linear Isotherm Model

1) Linear Qe = K d Ce
2) Langmuir
Kd = Partition coefficient
3) Freundlich
Adsorption ➔ linearly related to
aqueous concentration

For low concentration (i.e., when most sorption sites are

unoccupied), the linear isotherm is a good description.

Freundlich Isotherm Model

Langmuir Isotherm Model
Qe = K f Cen
K LC e
Qe = Qmax
1+ K LCe
Kf = Freundlich adsorption coefficient
Qmax = maximum adsorbed amount of adsorbent (mg/g) n = empirical coefficient
KL = Langmuir constant (L/mg)

Interpretation ➔ multiple types of adsorption

This model assumes constant binding energy between sites, exhibiting a diversity of free energies
surface and adsorbate.
Example
Adsorption of benzene onto activated carbon has been
reported to obey the following Freundlich isotherm
equation, where C is in mg/L and Q is in mg/g:

Q = 50.1 C 0.533
e e
A solution at 25 oC containing 0.50 mg/L benzene is
to be treated in a batch process to reduce the
concentration to less than 0.01 mg/L. Compute the
required activated carbon dose.

Cini = 0.50 mg/L, Ce = 0.01 mg/L

The adsorption density of benzene in equilibrium can be
determined from the isotherm model:

Q = 50.1 C0.533 = 4.30 mg/g

e e
A mass balance on the contaminant can then be written
and solved for the activated carbon dose:
Cini V = Ce V + Qe  M AC
M 
Cini = Ce + Qe   AC 
 V 
0.50 mg/L = 0.010 mg/L + (4.30 mg/g ) DoseAC

DoseAC = 0.114 g/L

• Koc ➔ soil –water partition coefficient normalized to organic carbon.

• Kow ➔ octanol –water partition coefficient

The higher Kow ➔ the greater the tendency of the compound to partition from the water into organic phase
 A B
❑ Chemical Kinetics
Kinetics – how fast does a reaction proceed?
Reaction rate is the change in the concentration of a
reactant or a product with time (M/s).
time
A B

[A] [A] = change in concentration of A over [A]

rate = - rate = -
t time period t t
Because [A] decreases with time, [A] is negative.
[B]
rate =
[B] [B] = change in concentration of B over t
rate =
t time period t
• Reaction Orders ✓ Zero-order rate equation:

rate = - [A] = k [A]0 [A]t - [A]0 = - kt

A reaction has an individual order “with respect to” or “in” t
each reactant. ✓ First-order rate equation:
[A]t
For the simple reaction A → products: rate = - [A] = k [A] ln = - kt
t [A]0
✓ If the rate keeps as a constant → zero order
✓ If the rate doubles when [A] doubles, the rate depends ✓ Second-order rate equation:
on [A]1 and the reaction is first order with respect to A. rate = - [A] = k [A]2 1 1
- = kt
✓ If the rate quadruples when [A] doubles, the rate depends t [A]t [A]0
on [A]2 and the reaction is second order with respect to
[A]. [A]t is the concentration of A at any time t
[A]0 is the concentration of A at time t=0

Reaction orders must be determined from

experimental data and cannot be deduced
from the balanced equation.
Plots of reactant concentration, [A], vs. time Plots of rate vs. reactant concentration, [A],
for first-, second-, and zero-order reactions. for first-, second-, and zero-order reactions.
Example
How long will it take the carbon monoxide (CO) concentration in a room to decrease 99% after the source of CO is removed
and the windows are opened? Assume the first-order rate constant for CO removal (due to dilution by incoming clean air) is
1.2/h. No chemical reaction is occurring.

0.01= e-kt t = 3.8 h