Basic Chemistry for Water and Wastewater Operators

W ater and wastewater operators

must have an understanding of
basic chemistry in order to properly
implement the chemical phases of
treatment, including coagulation,
sedimentation, softening, and disin-
fection. Basic Chemistry provides
easy-to-understand explanations of
chemical
concepts that operators will use in
their daily work activities and
includes sample
problems to encourage
further reading.
Darshan Singh Sarai

1P-1M-20494-4/02-UG
BasicChemistry.book Page i Monday, February 18, 2002 5:03 PM

Basic Chemistry
for Water and
Wastewater Operators
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001Chemistry.fm Page iii Thursday, February 28, 2002 11:27 AM

Basic Chemistry
for Water and
Wastewater Operators

Darshan Singh Sarai

BasicChemistry.book Page iv Monday, February 18, 2002 5:03 PM

Copyright © 2002 American Water Works Association

All rights reserved. No part of this publication may be repro-

duced or transmitted in any form or by any means, electronic
or mechanical, including photocopy, recording, or any infor-
mation or retrieval system, except in the form of brief excerpts
or quotations for review purposes, without the written permis-
sion of the publisher.

Library of Congress Cataloging-in-Publication Data has

been applied for.

Printed in the United States of America

American Water Works Association
6666 West Quincy Avenue
Denver, CO 80235

ISBN 1-58321-148-9 Printed on recycled paper

BasicChemistry.book Page v Monday, February 18, 2002 5:03 PM

Table of Contents

Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xi

Chapter 1 Introduction . . . . . . . . . . . . . . . . . . . . 1
Matter and Energy . . . . . . . . . . . . . . . . 1
Matter . . . . . . . . . . . . . . . . . . . . . . . . 1
Energy . . . . . . . . . . . . . . . . . . . . . . . . 4
Properties . . . . . . . . . . . . . . . . . . . . . 4
Questions . . . . . . . . . . . . . . . . . . . . . . . 5

Chapter 2 Measurements in Chemistry . . . . . . 7

The Metric System . . . . . . . . . . . . . . . . 7
Metric Units . . . . . . . . . . . . . . . . . . . 7
Exponential or Scientific
Notation . . . . . . . . . . . . . . . . . . . 10
Questions . . . . . . . . . . . . . . . . . . . . . . 11

Chapter 3 Elements . . . . . . . . . . . . . . . . . . . . . . 13
Chemical Symbols . . . . . . . . . . . . . . . 14
Atomic Structure . . . . . . . . . . . . . . . . 15
Atomic Weight . . . . . . . . . . . . . . . . . . 16
Avogadro Number and Mole . . . . . . . 16
Periodic Table. . . . . . . . . . . . . . . . . . . 17
Periodic Law . . . . . . . . . . . . . . . . . . . . 22
Questions . . . . . . . . . . . . . . . . . . . . . . 23

Chapter 4 Compounds. . . . . . . . . . . . . . . . . . . . 25
Ionic Compounds . . . . . . . . . . . . . . . 26
Covalent Compounds . . . . . . . . . . . . 28
Chemical Formulae . . . . . . . . . . . . . . 30
Naming Compounds . . . . . . . . . . . . . 33
Questions . . . . . . . . . . . . . . . . . . . . . . 35

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Chapter 5 Chemical Equations . . . . . . . . . . . . . 37

Law of Conservation of Masses . . . . . 37
Steps in Writing a Balanced
Equation . . . . . . . . . . . . . . . . . . . 38
Quantitative Calculations or
Stoichiometry in Chemical
Reactions. . . . . . . . . . . . . . . . . . . . . 39
Various Types of Chemical
Reactions. . . . . . . . . . . . . . . . . . . . . 41
How to Balance a Redox Equation. . . 44
Questions . . . . . . . . . . . . . . . . . . . . . . 45

Chapter 6 Acids, Bases, and Salts . . . . . . . . . . 47

Acids . . . . . . . . . . . . . . . . . . . . . . . . . . 47
Properties of Acids . . . . . . . . . . . . . 48
Naming Acids . . . . . . . . . . . . . . . . . 49
Bases . . . . . . . . . . . . . . . . . . . . . . . . . . 49
Properties of Bases . . . . . . . . . . . . . 50
Amphiprotic Compounds . . . . . . . 50
Anhydrides . . . . . . . . . . . . . . . . . . . 51
pH Values . . . . . . . . . . . . . . . . . . . . 51
pH Scale . . . . . . . . . . . . . . . . . . . . . 52
Methods of pH Measurement. . . . . 53
Alkalinity and Acidity in Natural
Water. . . . . . . . . . . . . . . . . . . . . . 53
Salts . . . . . . . . . . . . . . . . . . . . . . . . . . 54
Questions . . . . . . . . . . . . . . . . . . . . . . 54

Chapter 7 Solutions . . . . . . . . . . . . . . . . . . . . . . 55
Concentration of a Solution . . . . . . . 56
Saturated Solution . . . . . . . . . . . . . . . 60
Unsaturated Solutions . . . . . . . . . . 60
Supersaturated Solutions . . . . . . . . 61
Dilute and Concentrated
Solutions . . . . . . . . . . . . . . . . . . . 61
Standard Solutions . . . . . . . . . . . . . 61
Factors That Affect Solubility. . . . . . . 63
Questions . . . . . . . . . . . . . . . . . . . . . . 63

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Chapter 8 Colloids and Coagulation . . . . . . . . 65

Methods of Colloid Formation . . . . . 65
Types of Colloids . . . . . . . . . . . . . . . . 66
General Properties . . . . . . . . . . . . . . . 68
Methods of Precipitating Colloids . . . 70
Questions . . . . . . . . . . . . . . . . . . . . . . 71

Chapter 9 Water. . . . . . . . . . . . . . . . . . . . . . . . . 73
Physical Properties of Water . . . . . . . 73
Structure and Properties of Water
Molecules . . . . . . . . . . . . . . . . . . . . 74
Water as a Standard . . . . . . . . . . . . . . 74
Chemical Behavior. . . . . . . . . . . . . . . 75
Questions . . . . . . . . . . . . . . . . . . . . . . 76

Chapter 10 Ionization Theory . . . . . . . . . . . . . . 79

Assumptions of Modern Theory . . . . 80
Dissociation of Ionic
Compounds. . . . . . . . . . . . . . . . . 80
Ionization of Polar Covalent
Compounds (Acids) . . . . . . . . . . 83
Ionization of Water . . . . . . . . . . . . 84
Electrolysis and Ionization. . . . . . . . . 85
Questions . . . . . . . . . . . . . . . . . . . . . . 86

Chapter 11 The Gas Laws . . . . . . . . . . . . . . . . . . 87

Kinetic Theory . . . . . . . . . . . . . . . . . . 87
Properties of Gases . . . . . . . . . . . . . . . 88
Henry’s Law . . . . . . . . . . . . . . . . . . 89
Graham’s Law of Diffusion . . . . . . 89
Dalton’s Law of Partial Pressure . . . 90
Boyle’s Law . . . . . . . . . . . . . . . . . . . 90
Charles’s Law . . . . . . . . . . . . . . . . . 91
Gay-Lussac’s Law of Combining
Volumes of Gases . . . . . . . . . . . . 92
Avogadro’s Hypothesis . . . . . . . . . . 92
Questions . . . . . . . . . . . . . . . . . . . . . . 93

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Chapter 12 Organic Chemistry. . . . . . . . . . . . . . 95

Carbon Atoms and Bonding . . . . . . . 96
Classification of Organic
Compounds . . . . . . . . . . . . . . . . . . 97
Hydrocarbons . . . . . . . . . . . . . . . . . 97
Carbohydrates . . . . . . . . . . . . . . . 105
Lipids . . . . . . . . . . . . . . . . . . . . . . 109
Proteins . . . . . . . . . . . . . . . . . . . . . 111
Questions . . . . . . . . . . . . . . . . . . . . . 112

Chapter 13 Hardness . . . . . . . . . . . . . . . . . . . . . 115

Lather Formation and Hardness . . . 116
Types of Hardness. . . . . . . . . . . . . 116
Problems Due to Hardness . . . . . . 116
Softening Methods . . . . . . . . . . . . 117
Iron and Manganese in Water . . . . . 119
Problems Caused by Iron and
Manganese . . . . . . . . . . . . . . . . 119
Removal . . . . . . . . . . . . . . . . . . . . 120
Aeration . . . . . . . . . . . . . . . . . . . . 120
Questions . . . . . . . . . . . . . . . . . . . . . 122

Chapter 14 Corrosion and Its Control. . . . . . . 123

Types of Corrosion. . . . . . . . . . . . . . 124
Various Factors Affecting
Corrosion . . . . . . . . . . . . . . . . . 126
Corrosion Control . . . . . . . . . . . . 126
Various Indices . . . . . . . . . . . . . . . 128
Phosphate Treatment . . . . . . . . . . 129
Questions . . . . . . . . . . . . . . . . . . . . . 132

Chapter 15 Disinfection . . . . . . . . . . . . . . . . . . 133

Chlorine as a Water Disinfectant. . . 134
Chlorine Properties. . . . . . . . . . . . 134
Various Forms of Chlorine Used
in Disinfection . . . . . . . . . . . . . 135
Breakpoint Chlorination . . . . . . . 136

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Chlorine Demand. . . . . . . . . . . . . 139

Factors Affecting Chlorination. . . 139
Types of Chlorination . . . . . . . . . 141
Chlorine and Health. . . . . . . . . . . 142
Chlorine and Safety . . . . . . . . . . . 143
Chloramines as Water
Disinfectants . . . . . . . . . . . . . . . . . 143
Bromine as a Water Disinfectant . . . 144
Iodine as a Water Disinfectant. . . . . 145
Chlorine Dioxide as a Water
Disinfectant . . . . . . . . . . . . . . . . . 145
Ozone as a Water Disinfectant . . . . 147
Ultraviolet Light. . . . . . . . . . . . . . . . 149
Silver Ions. . . . . . . . . . . . . . . . . . . . . 150
Questions . . . . . . . . . . . . . . . . . . . . . 150
Appendix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153
Glossary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 159
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 169
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 171

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Preface

This book is the result of 30 years of teaching and

practical experience in the water and wastewater fields. A
strong educational background—I have a masters with
honors degree in biology from Punjab University, India,
and a doctorate degree from the University of Alberta,
Canada, in environmental entomology and I am a board-
certified entomologist and a registered sanitarian—was
very helpful in completing this work. I spent nine years
teaching water and wastewater chemistry at Water and
Wastewater Technical School, in Neosho, Missouri,
without the help of a good textbook. I felt a serious need
for a basic chemistry book tailored just for water and
wastewater operating staff who generally have little or
no knowledge of chemistry. A large part of this work was
initiated at that time.
After teaching, I had the opportunity to work at
Water District #1 of Johnson County, Kansas, for more
than 20 years. This provided a unique chance to apply
my teaching knowledge in the treatment of water
because I was in charge of the water treatment and qual-
ity control laboratory and responsible for training oper-
ating staff. During this time, I also taught part-time at a
community college and for the Department of Natural
Resources of the State of Missouri. I was compiling mate-
rial while working both in the field and classroom.
After retiring, I was encouraged by my family, stu-
dents, and friends to publish a book. While preparing
the manuscript, I received a very timely letter from
Colin Murcray, Manager of Business and Acquisitions
for the American Water Works Association, that asked

xi
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the question, Are you a walking encyclopedia? The let-

ter was sent to water personnel asking them to publish
based on their experience in the water industry.
Most concepts covered in this book are in a basic
form. For further details, the reader can refer to the refer-
ences at the end of the book. A set of simple self-test
questions are given at the end of each chapter to encour-
age the reader to further study the subject matter.
I hope this publication will serve its intended pur-
pose of helping operating staff by giving them pertinent
chemistry information, which will help them comply
with US Environmental Protection Agency regulations. I
sincerely acknowledge the help of all those who made
this work possible.

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1 Introduction

C hemistry is a science that deals with the

structure, the composition, and changes in composition
of matter as well as the laws that govern these changes.
Knowledge of basic chemistry concepts is essential for a
person in the water and wastewater field to understand
chemical phases of treatment such as coagulation, sedi-
mentation, softening, disinfection, and chemical removal
of the various undesirable substances.

Matter and Energy

Matter
Matter is anything that occupies space and has
mass. All materials consist of matter, and mass of a body
is its quantity of matter. Mass is responsible for the
weight of the body—the larger the mass, the heavier the
body. Weight is the measurement of earth’s attraction
to the body. It changes with the distance of the body
from the center of the earth—the greater the distance,
the less the body weighs, and vice versa. The mass of the
body is constant, but weight changes with altitude. An
astronaut in space is weightless, although he has the
same mass as on earth. For practical purposes, mass and
weight are used interchangeably.

Three States of Matter

All matter exists in one or more of three states: solid,
liquid, and/or gas. In the solid state, matter has a definite

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Basic Chemistry for Water and Wastewater Operators

volume and a definite shape (e.g., a block of wood). In

the liquid state, there is only definite volume (e.g., water
in a glass). In the gas state, there is neither a definite vol-
ume nor a definite shape (e.g., air). Some substances can
exist in nature in all three states. Water, for example, can
be a solid (ice), a liquid (water), and a gas (vapor).
In many instances, the physical state of a substance
transforms with a change in temperature: iron into liq-
uid at 3,000°C, ice into water at 0°C, and water into
steam at 100°C. At very high temperatures, gases change
to a fourth rather rare state of matter called plasma.

Changes in Matter
There are two types of changes in matter—physical
and chemical. A physical change is a change in the phys-
ical state, such as from solid to liquid and liquid to gas,
or ice into water and water into steam. A chemical
change is a change in the chemical composition of a sub-
stance and, therefore, in its properties, such as the burn-
ing of wood to form carbon dioxide, water, and ashes.

Density and Specific Gravity

Density of a substance is the mass per unit volume. A
unit of mass in chemistry is a gram and a unit of volume
is a cubic centimetre. For gases, it is grams per litre at
standard temperature (0°C) and standard pressure
(760 mm mercury). The formula for calculating density is

M
D = -----
V

where:
D = density
M = mass in grams
V = volume as cubic centimetres or litres

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Chapter 1 Introduction

Sample Problems
1. 10 cm3 of iron weighs 78.6 g. What is the density of
iron?

78.6 g
Density of iron = -------------------3-
10 cm
3
= 7.86 g/cm

2. 100 L of oxygen at STP (standard temperature and

pressure) measures 143 g. Calculate the density of
oxygen.

143 g
Density of oxygen = ---------------
100 L
= 1.43 g/L

Specific gravity is the ratio of the density of a sub-

stance to that of a standard. The standard for solids
and liquids is water with the density of 1 g/cm3. For
gases, the standard is air with the density of 1.29 g/L.
For solids and liquids,

density of the substance

specific gravity = -------------------------------------------------------------------
density of water

For gases,

density of the gas

specific gravity = -------------------------------------------------
density of air

3. Calculate the specific gravity of gold with the density

19.3 g/cm3.
3
19.3 g/cm
Specific gravity of gold = ------------------------------
3
1 g/cm
= 19.3

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Basic Chemistry for Water and Wastewater Operators

4. Calculate the specific gravity of oxygen gas with the

density 1.43 g/L.

1.43 g/L
Specific gravity of oxygen = -----------------------
1.29 g/L
= 1.11

Energy
Energy is the capacity to do work. Common forms of
energy include heat, light, and electricity, as well as
chemical and mechanical energy. Two types of mechan-
ical energy are kinetic and potential. Energy due to
motion is known as kinetic energy, e.g., the energy from
wind or water turning the wheel of a mill. Energy due to
position is known as potential energy, e.g., falling water
in a dam creates energy to turn a turbine.

Law of Conservation of Energy

Energy can be transformed from one form to
another; it is neither created nor destroyed. The total
amount of energy in the universe is constant.
Einstein has proved through his famous equation,
E = mc2, where “E” stands for energy, “m” for mass, and
“c” for a constant (speed of light), that energy can be
converted into mass and mass into energy. Therefore,
the above given law can be written as the total amount of
energy or matter in the universe is constant.

Properties
Properties of a substance can be classified into three
categories:
1. Physical properties: The chemical composition of a
substance in these properties is unchanged and
includes color, taste, odor, solubility, density,
hardness, and melting and boiling points.

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Chapter 1 Introduction

2. Chemical properties: These properties are determined

by changing the chemical composition (e.g.,
through interaction with other substances, burning,
and reaction to heat and light).
3. Specific properties: These properties are used for the
identification of a substance.

Questions
1. Why is chemistry important in water treatment?
2. What is matter?
3. Distinguish between (a) mass and weight, and
(b) density and specific gravity.
4. Calculate the density of zinc when 20 cm3 of it
weighs 142.8 g.
5. What is the density of hydrogen if 100 L weighs
about 9 g?
6. Define chemical and physical properties.
7. Define a chemical change and give examples of a
chemical change and a physical change.
8. Define energy and state the law of conservation of
energy.

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2 Measurements in
Chemistry

The Metric System

T
he English system of measurements has the
disadvantage of lacking a simple numerical relationship
between the units and their parts. To overcome this dis-
advantage, the metric system was developed in France
near the end of the eighteenth century. Fractional and
multiple parts of the metric basic unit have a simple
numerical relationship based on the number 10.
This system is commonly used all over the world in
scientific works.

Metric Units
A gram is the basic unit of mass. Originally, a gram
was defined as the mass of 1 cm3 of water at 4°C. Now, it
is 1/1,000 of the mass of a standard kilogram weight kept
at the International Bureau of Weights and Measures
near Paris, France. One gram is equal to 0.0022 lb.
A metre, the basic unit of length, was originally
defined as 1/10,000,000 of the distance from the North
Pole to the equator along the Paris Meridian. Today, it is
the distance between two parallel lines engraved on a
platinum-iridium bar kept at the International Bureau of
Weights and Measures. One metre is equal to 39.37 in.

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Basic Chemistry for Water and Wastewater Operators

A litre is the unit of volume. It is the volume of 1 kg

of water at 4°C. Thus, 1 g of water equals 1 mL or 1 cm3.
One litre is equal to 0.264 gal.
Prefixes are used with these units to complete the
system. Multiple or ascending values use Greek prefixes:

Deka-, D = 10 basic units

Hecto-, H = 100 basic units
Kilo-, K = 1,000 basic units
Mega-, M = 1,000,000 basic units
Giga-, G = 1,000,000,000 basic units
Tera-, T = 1,000,000,000,000 basic units

Fractional or descending values are identified by Latin

prefixes:

Deci-, d = 1/10 of basic unit

Centi-, c = 1/100 of basic unit
Milli-, m = 1/1,000 of basic unit
Micro-, µ = 1/1,000,000 of basic unit
Nano-, n = 1/1,000,000,000 of basic unit
Pico-, p = 1/1,000,000,000,000 of basic unit
Femto-, f = 1/1,000,000,000,000,000 of basic unit
Atto-, a = 1/1,000,000,000,000,000,000 of basic unit

By using a metre as an example, these prefixes are

used as follows:

Kilometre = 1,000 metres

= 100 dekametres
= 10 hectometres

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Chapter 2 Measurements in Chemistry

Hectometre = 100 metres

Dekametre = 10 metres
Metre
Decimetre = 1/10 metre
Centimetre = 1/100 metre
Millimetre = 1/1,000 metre
= 1/100 decimetre
= 1/10 centimetre

Temperature in the metric system is measured on the

centigrade (Celsius) scale, which has two fixed points:
0°C, the freezing point of water, and 100°C, the boiling
point of water at standard atmospheric pressure. The
scale between these two points is divided into 100 equal
intervals, the centigrade degrees.
The Fahrenheit scale was devised for practical use in
everyday life. The freezing point of water is 32°F, and the
boiling point is 212°F; thus, there are 180 units (212 – 32)
between these fixed points. Therefore, 1 unit on the cen-
tigrade scale is equal to 9⁄ 5 unit on the Fahrenheit scale,
and 1 Fahrenheit unit is equal to 5⁄ 9 of a centigrade unit.

Centigrade Fahrenheit Absolute

(°C) (°F) (°A)

Boiling point of water 100 212 373

75 167 348

50 122 323

25 77 298

Freezing point of water 0 32 273

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Basic Chemistry for Water and Wastewater Operators

Conversion formulae:
°F = (°C × 9⁄ 5) + 32
°C = (°F – 32) × 5⁄ 9
The absolute (Kelvin) scale is used for the relation-
ship of the volume of a gas and its temperature. The
interval between the freezing and boiling points as on
the centigrade scale is 100. The freezing point on the
absolute scale is 273°A and the boiling point is 373°A.
°A = °C + 273 or °C = °A – 273

Sample Problems
1. Convert 35°C to degrees Fahrenheit.
Degrees F = (35 × 9⁄ 5) + 32
= 95
1. Convert 68°F to degrees centigrade.
Degrees C = (68 – 32) × 5⁄ 9
= 20
2. Convert 290°A to degrees centigrade.
Degrees C = 290 – 273
= 17

Exponential or Scientific Notation

Scientific notation is a shorthand method for writing
very large or very small numbers, such as the distance of
the earth from the sun (93,000,000 mi), or the weight
of a proton (0.000,000,000,000,000,000,000,001,673 g).
Exponential notation is expressed as
M × 10n
where:
M = a number 1 to 9.99
n = exponent or the power of the base 10 (n is pos-
itive for numbers higher than 10 and negative
for numbers less than 1)

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Chapter 2 Measurements in Chemistry

The power of 10 is the number of places the deci-

mal point is moved to have only one digit to the left.
If the decimal point is moved to the left, the power is
positive and if moved to the right, it is negative. Expo-
nential notation for 93,000,000 mi is 9.3 × 107 mi and
for 0.000,000,000,000,000,000,000,001,673 g it is 1.673 ×
10–24 g.

Questions
1. Define gram, litre, metre, and 0°C.
2. Give the basic number of the metric system.
3. How many millimetres are in 10 km?
4. Convert the following temperatures to centigrade:
a. 113°F
b. 50°F
c. –40°F
5. Convert the following temperatures to Fahrenheit:
a. 30°C
b. –40°C
c. 50°C
6. Make the following conversions into absolute degrees:
a. 95°F
b. 30°C
c. 104°F
7. Write the following numbers in exponential nota-
tion form:
a. 30,000,000,000 cm/sec, the speed of light
b. 0.000,000,000,5 cm
c. 602,200,000,000,000,000,000,000.0 particles, the
Avogadro number

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3 Elements

E
lements are basic substances, such as carbon,
oxygen, nitrogen, and chlorine, that singly or in combi-
nation constitute all matter. At present, there are 112
known elements; 92 are naturally occurring and the
remaining are synthesized.
An element is defined as a chemical substance that
cannot be decomposed into simpler substances by ordi-
nary chemical changes. The smallest particle of an ele-
ment that can exist and retain the chemical properties of
that element is known as an atom.
Atoms are ordinarily unbreakable, but they can be
split by using special techniques from the atomic energy
field. After splitting, an atom does not have the original
properties of its element. It becomes an atom of a lighter
element. This process is known as fission.
Elements are generally divided into two general
classes: metals and nonmetals. Metals are mostly solids,
such as gold, silver, copper, and iron. Mercury, a liquid
metal, is an exception. They have luster, are good con-
ductors of electricity and heat, and are mostly malleable
(can be hammered into sheets) and ductile (can be
drawn into wires). Nonmetals are solids or gases. Car-
bon, sulfur, and phosphorus are solids; whereas, oxygen,
fluorine, and chlorine are gases. Bromine is an example
of a liquid nonmetal. Solid nonmetals are brittle and dull
and are poor conductors of heat and electricity.
Hydrogen is the lightest element, and oxygen is the
most abundant element in the earth’s crust.

13
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Basic Chemistry for Water and Wastewater Operators

Chemical Symbols
Each element is assigned a symbol to avoid the writ-
ing of its name. Symbols are written in English letters.
The symbol is either the first letter of the name of the ele-
ment or the first letter and a second well-pronounced
letter from the name. The second letter is used when
more than one element starts with the same letter. The
first letter of a symbol is capitalized, and the second let-
ter, when present, is lowercased. In several cases, the
symbols come from foreign languages, such as Latin,
Greek, and German. See Table 3-1 for a partial list of ele-
ments and their symbols.

Element Symbol
Aluminum Al
Arsenic As
Bromine Br
Calcium Ca
Carbon C
Chlorine Cl
Chromium Cr
Cobalt Co
Copper Cu
Fluorine F
Gold Au (from Latin name Aurum)
Hydrogen H
Iron Fe (from Latin name Ferrum)
Magnesium Mg
Manganese Mn
Nitrogen N
Oxygen O
Table 3-1 Symbols for Some Common Elements

14
BasicChemistry.book Page 15 Monday, February 18, 2002 5:03 PM

Chapter 3 Elements

Atomic Structure
Atoms are very small particles that cannot be seen
even with an ordinary microscope. Atomic diameter
ranges from 1–5 angstroms (Å) (an angstrom is 1/
100,000,000 of a centimetre, 10–8 cm). An atom consists
of two main parts: a positively charged central part, the
nucleus, and a negatively charged outer part, the shells, or
energy levels. The nucleus is about 1/100,000 of an ang-
strom and it contains two kinds of particles, positively
charged protons and uncharged neutrons. A proton has
a mass of 1.673 × 10–24 g, which is approximately the
mass of a hydrogen atom. A neutron weighs almost the
same as a proton (1.675 × 10–24 g); thus, a proton or a
neutron weigh about as much as a hydrogen atom. Shells
are the orbits of electrons, which are very small particles
revolving around the nucleus. An electron carries a neg-
ative charge. The mass of an electron is 9.110 × 10–28 g.
It is an insignificant mass as compared to a proton or a
neutron. The number of protons in an uncombined
atom is equal to the number of electrons. An atom is,
therefore, electrically neutral. The atomic number of an
element is the number of protons in its atom. Some ele-
ments may have atoms with different numbers of neu-
trons; these atoms are known as isotopes. Most elements
exist as a number of isotopes. Hydrogen, for example,
has three isotopes: protium, deuterium, and tritium,
with 0, 1, and 2 neutrons, respectively.

1e 1e 1e

1p+ 1p+ 1p+

1n 2n

Protium Deuterium Tritium

Isotopes of Hydrogen

15
BasicChemistry.book Page 16 Monday, February 18, 2002 5:03 PM

Basic Chemistry for Water and Wastewater Operators

The mass number of an isotope is the sum of its pro-

tons and neutrons. It is termed “mass number” because
protons and neutrons contribute atomic mass. It is writ-
ten after the name of the element, e.g., hydrogen-1,
hydrogen-2, oxygen-16, and carbon-14. In symbolic
form, the oxygen-16 isotope is 8O16, where 16 is the
mass number and 8 is the atomic number. In some
books, it is shown simply as O16.

Atomic Weight
Atoms are too small to be weighed individually;
therefore, a system of relative masses was developed in
which C12 (carbon isotope with mass number 12) is
assigned a mass of 12 atomic mass units (AMU) and is
used as a standard for atomic weights of all other ele-
ments. The atomic weight of an element is, therefore,
defined as the average mass of its isotopes as compared
to a C12 atom, which equals 12 AMU. The atomic mass
unit is a very small mass.

1 g = 6.022169 × 1023 AMU

Avogadro Number and Mole

The Avogadro number is a constant in chemistry. It
is 6.022169 × 1023 particles of a substance. (See its use in
above equation.) The amount of a substance (an element
or a compound) in grams containing an Avogadro num-
ber of its particles is known as a mole. Whenever grams
replace atomic mass units of the mass of a particle, the
number of particles changes from 1 to 6.02 × 1023 parti-
cles. Thus, the atomic weight of an element with mass
units in grams is a mole of that element and is also
known as gram atomic weight.
1 hydrogen atom = 1.008 AMU

6.02 × 1023 hydrogen atoms = 1.008 g

16
BasicChemistry.book Page 17 Monday, February 18, 2002 5:03 PM

Chapter 3 Elements

Therefore, 1.008 g is a mole or a gram atomic weight

of hydrogen. Similarly, 12.0111 g is a mole of carbon,
and 15.9994 g is a mole of oxygen.

Periodic Table
The periodic table (see Tables 3-2 and 3-3) is a chart
of the elements arranged according to their atomic num-
bers. Each element is assigned a block. A horizontal row
of blocks on the table is called a period or series. Periods
are indicated by Arabic numerals (1,2,3—or 7). A vertical
column, called a group or family, is indicated by a Roman
numeral (I, II—or VIII), which represents the electrons in
the outermost shell.

Period

Group

The number of periods indicates the number of shells

in its elements. There are seven shells and, thus, seven
periods. Elements of the first period (hydrogen and
helium) have one shell; elements of the second period
(lithium through neon), two shells; and, thus, elements
of the seventh period, seven shells. The seven shells are
known as K through Q, or one through seven from inside
outward. Each shell can hold only a certain number of
electrons. K shell can hold a maximum of 2 electrons;
L shell, 8; and M shell, 18. Most of the shells are further
divided into sublevels identified by the letters s, p, d, and
f in order of ascending energy. The s sublevel can hold a
maximum of one pair; p, three pairs; d, five pairs; and f,
seven pairs of electrons. The path of a pair of electrons is
known as an orbital. Thus, s sublevel has one orbital; p,
three; d, five; and f, seven orbitals. Table 3-4 shows the
electronic shells (levels) and sublevels and the maximum
number of electrons in each shell.

17
 Inert
IA IIA IIIB IVB VB VIB VIIB VIII IB IIB IIIA IVA VA VIA VIIA Gases
1 1 2
H H He
1.00797 1.00797 4.0026
3 4 5 6 7 8 9 10

18
Li Be B C N O F Ne
6.939 9.0122 10.811 12.0112 14.0067 15.9994 18.9984 20.183
11 12 13 14 15 16 17 18
Na Mg Al Si P S Cl Ar
22.9898 24.312 26.9815 28.086 30.9738 32.064 35.453 39.948
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
39.102 40.08 44.956 47.90 50.942 51.996 54.9380 55.847 58.9332 58.71 63.54 65.37 69.72 72.59 74.9216 78.96 79.909 83.80
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
85.47 87.62 88.905 91.22 92.906 95.94 (99) 101.07 102.905 106.4 107.870 112.40 114.82 118.69 121.75 127.60 126.904 131.30
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
BasicChemistry.book Page 18 Monday, February 18, 2002 5:03 PM

*
Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
132.905 137.34 138.91 178.49 180.948 183.85 186.2 190.2 192.2 195.09 196.967 200.59 204.37 207.19 208.980 (210) (210) (222)
87 88 ‡ 89 104 105 106 107 108 109 110 111 112
Fr Ra Ac Rf Db Sg Bh Hs Mt ? ? ?
(223) (226) (227) (261) (262) (266) (262) (265) (266) (271) (272) (277)
Basic Chemistry for Water and Wastewater Operators

* Lanthanide Series
Numbers in parenthesis are mass
numbers of most stable or most 58 59 60 61 62 63 64 65 66 67 68 69 70 71
common isotope.
Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
Atomic weights corrected to 140.12 140.907 144.24 (147) 150.35 151.96 157.25 158.924 162.50 164.930 167.26 168.934 173.04 174.97
conform to the 1963 values of the ‡ Actinide Series
Commission on Atomic Weights.
90 91 92 93 94 95 96 97 98 99 100 101 102 103
The group designations used here
are the former Chemical Abstract
Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
Service numbers. 232.038 (231) 238.03 (237) (242) (243) (247) (247) (249) (254) (253) (256) (256) (257)

Table 3-2 Periodic Table

BasicChemistry.book Page 19 Monday, February 18, 2002 5:03 PM

Chapter 3 Elements

Atomic Atomic
Name Symbol Number Weight
Actinium Ac 89 227*
Aluminum Al 13 26.98
Americium Am 95 243*
Antimony Sb 51 121.75
Argon Ar 18 39.95
Arsenic As 33 74.92
Astatine At 85 210*
Barium Ba 56 137.34
Berkelium Bk 97 247*
Beryllium Be 4 9.01
Bismuth Bi 83 208.98
Bohrium Bh 107 262
Boron B 5 10.81
Bromine Br 35 79.90
Cadmium Cd 48 112.40
Calcium Ca 20 40.08
Californium Cf 98 249*
Carbon C 6 12.01
Cerium Ce 58 140.12
Cesium Cs 55 132.91
Chlorine Cl 17 35.45
Chromium Cr 24 52.00
Cobalt Co 27 58.93
Copper Cu 29 63.55
Curium Cm 96 247*
Dubnium Db 105 262
Dysprosium Dy 66 162.50
Einsteinium Es 99 254*
Erbium Er 68 167.26
Europium Eu 63 151.96
Fermium Fm 100 253*
Fluorine F 9 19.00
Francium Fr 87 223*
Gadolinium Gd 64 157.25
Gallium Ga 31 69.72
Germanium Ge 32 72.59
Gold Au 79 196.97
Hafnium Hf 72 178.49
Hassium Hs 108 265
Helium He 2 4.00
Holmium Ho 67 164.93
Hydrogen H 1 1.01
Indium In 49 114.82
Iodine I 53 126.90
Iridium Ir 77 192.22
Iron Fe 26 55.85
Krypton Kr 36 83.80
Lanthanum La 57 138.91
Lawrencium Lr 103 257*
Lead Pb 82 207.2
Lithium Li 3 6.94
Lutetium Lu 71 174.97
Magnesium Mg 12 24.31
Manganese Mn 25 54.94
Meitnerium Mt 109 265
Mendelevium Md 101 256*

* Mass number of most stable or best-known isotope.

† Mass of most commonly available, long-lived isotope.

Table 3-3 List of Elements

Table continues next page

19
BasicChemistry.book Page 20 Monday, February 18, 2002 5:03 PM

Basic Chemistry for Water and Wastewater Operators

Atomic Atomic
Name Symbol Number Weight
Mercury Hg 80 200.59
Molybdenum Mo 42 95.94
Neodymium Nd 60 144.24
Neon Ne 10 20.18
Neptunium Np 93 237.05†
Nickel Ni 28 58.71
Niobium Nb 41 92.91
Nitrogen N 7 14.01
Nobelium No 102 254*
Osmium Os 76 190.2
Oxygen O 8 16.00
Palladium Pd 46 106.4
Phosphorus P 15 30.97
Platinum Pt 78 195.09
Plutonium Pu 94 242*
Polonium Po 84 210*
Potassium K 19 39.10
Praseodymium Pr 59 140.91
Promethium Pm 61 147*
Protactinium Pa 91 231.04*
Radium Ra 88 226.03†
Radon Rn 86 222*
Rhenium Re 75 186.2
Rhodium Rh 45 102.91
Rubidium Rb 37 85.47
Ruthenium Ru 44 101.07
Rutherfordium Rf 104 261
Samarium Sm 62 150.4
Scandium Sc 21 44.969
Seaborgium Sg 106 263
Selenium Se 34 78.96
Silicon Si 14 28.09
Silver Ag 47 107.87
Sodium Na 11 22.99
Strontium Sr 38 87.62
Sulfur S 16 32.06
Tantalum Ta 73 180.95
Technetium Tc 43 98.91†
Tellurium Te 52 127.60
Terbium Tb 65 158.93
Thallium Tl 81 204.37
Thorium Th 90 232.04†
Thulium Tm 69 168.93
Tin Sn 50 118.69
Titanium Ti 22 47.90
Tungsten W 74 183.85
Uranium U 92 238.03
Vanadium V 23 50.94
Xenon Xe 54 131.30
Ytterbium Yb 70 173.04
Yttrium Y 39 88.91
Zinc Zn 30 65.38
Zirconium Zr 40 91.22

* Mass number of most stable or best-known isotope.

† Mass of most commonly available, long-lived isotope.

Table 3-3 List of Elements (continued)

20
BasicChemistry.book Page 21 Monday, February 18, 2002 5:03 PM

Chapter 3 Elements

Maximum Number of
Shell Sublevels Electrons in Shell
s p d f
K 2 2
L 2 6 8
M 2 6 10 18
N 2 6 10 14 32
O 2 6 10 14 32
P 2 6 10* 8 or 18
Q 2 6* 2 or 8
* Only sometimes present.
Table 3-4 Shells, Their Sublevels, and Maximum Number of
Electrons

Shell

Q 5f
7s 5f
6p 7s
5d 6p
P 4f 6s
5d 4f
5p 6s
4d 5p
O 5s
4d
4p 5s
Increasing energy

3d4s 4p
N
4s 3d
3p
M 3s 3p
3s

2p
L 2p
2s
2s

K 1s
1s

Figure 3-1 Electronic Configuration Based on Energy Level

(from Modern Chemistry by Metcalf, Williams, and Castka
1966. Publisher: Holt Rinehart & Winston, Inc.)

21
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Basic Chemistry for Water and Wastewater Operators

The electronic arrangement of an atom depends on the

energy level of various electrons. They are mostly arranged
in such a way that the electrons with minimum energy are
closest to the nucleus (in K shell) and with maximum, far-
thest away. Energy increases from K shell to Q and from s
sublevel to f; thus, both the shells and the sublevels are to
be considered in determining the place of an electron
around the nucleus. Figure 3-1 shows the relative energy
levels of electrons in various shells and sublevels.
The electronic structure of an element can be deter-
mined by arranging electrons from the base up the elec-
tronic energy scale. For example, hydrogen, atomic
number 1, has only one electron, which will be in the K
shell and s sublevel. It is represented as 1s1 where coeffi-
cient 1 indicates the shell number and superscript 1 indi-
cates the number of electrons in that sublevel. Helium’s
electronic structure is 1s2, lithium is ls22s1, and sodium
is 1s22s22p63sl. The sum of the superscripts is, therefore,
the atomic number of the element. Each period starts
with an element with one electron in its outermost shell
and ends with the element at a stable state. There are two
stable states in the atoms: two electrons in the K shell,
when it is the only shell as in the case of the elements in
period 1, and eight electrons in the outermost shell,
when more than one shell is present. The outermost
shell when it is not stable is known as a valence shell and
its electrons known as valence electrons.

Periodic Law
The chemical properties of elements repeat periodically
as the atomic numbers increase. Chemical properties are
determined by the electrons in the outermost shell. Ele-
ments in the same group have similar properties. As the
atomic number increases, after every certain number of
elements, there are the same number of electrons in the

22
BasicChemistry.book Page 23 Monday, February 18, 2002 5:03 PM

Chapter 3 Elements

outermost shell. For example, after atomic number 3,

which is lithium, sodium with atomic number 11 and
potassium with atomic number 19 have one electron in
their outermost shells, and they all belong to the same
group IA and have similar chemical properties.
The group number indicates the number of electrons
in the outermost shell. Group IA has one electron, IIA
two electrons, IIIA three electrons . . . and VIIIA eight
electrons in their outermost shells. Helium, in group
VIIIA, is the only element with two electrons, as it has
only a K shell, which is in the stable state with two elec-
trons. In the middle of the table, there are 30 elements,
known as transition elements. They have electrons in the
d sublevels of the third, fourth, and fifth shells. The
lower two rows of 14 elements each, known as rare earth
elements, have electrons in the f sublevels of the fourth
and fifth shells. Transition and rare earth elements have
one or two electrons in their valence shells.
Atoms of different elements combine to achieve the
stable state (two or eight electrons in the outermost
shell). Commonly, elements with one to three electrons
in their valence shell (e.g., metals) lose electrons to those
elements with valence electrons from five to seven as
nonmetals to form compounds. Thus, elements in groups
IA to IIIA, transition and rare earth elements, lose elec-
trons and are known as metals, and those in groups VA to
VIIA gain electrons and are known as nonmetals. A
heavy, staircase-like line on the periodic table separates
metals from nonmetals. Elements of group VIIIA are in
the stable state and ordinarily do not react with other ele-
ments and are, therefore, known as inert or noble gases.

Questions
1. Define element, atom, proton, neutron, and electron.
2. What is the difference between a group and a period?

23
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Basic Chemistry for Water and Wastewater Operators

3. Write symbols for:

a. Iron
b. Manganese
c. Carbon
d. Mercury
e. Copper
f. Silver
4. What is the difference between atomic number and
atomic weight?
5. Fill in the blanks:

Atomic Mass
Element Protons Number Number Electrons Neutrons

Carbon ____ 6 ____ ____ 6

Oxygen ____ 8 17 ____ ____

Chlorine 17 ____ 35 ____ ____

6. a. How many carbon atoms are in exactly 12 g of

carbon-12?
b. What is the name for this number?
c. What is the term for the amount of a substance
containing this number of particles?
7. a. How many shells are in elements in period 6?
b. How many electrons are in the outermost shell of
elements in group VA?
8. What is the name for atoms with the same atomic
number, but different mass number?
9. Define valence shell and valence electrons.

24
BasicChemistry.book Page 25 Monday, February 18, 2002 5:03 PM

4 Compounds

Every substance in the world is either an ele-

ment, a compound, or a mixture of various compounds
and elements. A compound is formed of two or more ele-
ments, which are always present in the same definite pro-
portion. For example, water is formed of 88.89 percent
oxygen and 11.11 percent hydrogen by weight.
Law of definite composition: The composition of a
chemical compound always contains the same propor-
tions, or a chemical compound has a definite composi-
tion by weight. Why do different elements combine to
form compounds? They do so to have their outermost
shell in the stable state. Electrons are either transferred
from the valence shell of one atom to that of another or
shared between the valence shells of two atoms to
accomplish atomic stability.
Some substances can be mixed together without
combining them, such as sugar and salt. The following
table shows differences between a compound and a
mixture:

Compound Mixture

1. Has a definite composi- 1. Components may be

tion by weight. present in any
proportion.

2. Usually, there is evi- 2. No such evidence.

dence of chemical
change in a compound
formation in the form
of heat or light.

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Basic Chemistry for Water and Wastewater Operators

Compound Mixture
3. Components lose 3. Components retain
their identities and their identities and can
cannot be separated be separated by
mechanically. mechanical means.

Examples of compounds Example of a mixture is

are water, carbon dioxide, air, formed mainly of
etc. nitrogen and oxygen.

Oxidation number (valence): This number, assigned to

each element, indicates the number of electrons lost,
gained, or shared by its atom in the compound forma-
tion. This number is either positive (+) or negative (–). An
atom that loses electrons gains a positive charge and its
oxidation number is positive because in an uncombined
atom, the number of protons is equal to the number of
electrons. The number of electrons lost leaves the atom
with the same number of positive charges. Similarly, an
atom that gains electrons, gains negative charges equal to
the number of electrons gained.
As in the formation of different compounds, the same
element may have a different number of electrons
involved, so it may have more than one oxidation number.
Metals lose electrons and thus have positive oxidation
numbers, and nonmetals gain electrons and have negative
oxidation numbers. Metals in group IA–IIIA have +1, +2,
and +3 oxidation numbers because they lose one, two, and
three electrons, respectively. Nonmetals in group VA–VIIA
have –3, –2, and –l oxidation numbers because they gain
three, two, and one electrons, respectively. The rules for
determining oxidation numbers are listed in Table 4-1.

Ionic Compounds
Ionic compounds are formed when a transfer of elec-
trons occurs, which produces ionic or electrovalence

26
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Chapter 4 Compounds

1. For simple ions, the oxidation number is the charge on the

ion; i.e.,
Na+ = +1, Cl– = –1, A1+3 = +3

2. The oxidation number for a free element is zero; i.e.,

H2 = 0, O2 = 0, N2 = 0, Fe = 0, O3 = 0

3. The normal oxidation number of hydrogen is +1 and of

oxygen is –2.

4. The algebraic sum of the oxidation numbers within a radical

is equal to its charge.

5. The total charge on a chemical compound is zero.

Table 4-1 Rules for Determining Oxidation Numbers

bonding. Ionic bonds are formed when metals combine

with nonmetals. The formation of sodium chloride by
transferring one electron from a sodium atom to a chlo-
rine atom is an example of ionic bonding (Figure 4-1).
Sodium and chlorine atoms are no longer neutral—
the sodium atom has gained a positive charge and the
chlorine atom a negative charge. A charged particle is
known as an ion. A positively charged ion is termed cat-
ion and a negatively charged ion is anion. In ionic com-
pounds, positive and negative ions are held together by
electrical forces due to their opposite charge. These
forces form an ionic bond. Because only valence shells
are involved in the compound formation, they are
shown with electrons as dots in a compound formation
diagram. For example, sodium chloride and calcium
chloride are shown as

Na Cl Cl Ca Cl

Sodium Chloride = NaCl Calcium Chloride = CaCl2

27
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Basic Chemistry for Water and Wastewater Operators

8e 8e

2e 2e

Na Cl
11p+ 17p+

Na Cl
+ –
Na Cl = NaCl

Ionic Bond

Figure 4-1 Ionic Bonding Between Sodium and Chlorine Atoms

Oxidation is any chemical change in which electrons

are lost. In the above examples, it is the oxidation of
sodium and calcium atoms. A substance that is oxidized
is known as a reducing agent.
Reduction is the reverse of oxidation. Reduction is a
chemical change in which electrons are gained. In the
case of sodium chloride, the chlorine atom has under-
gone the reduction. A substance that is reduced is known
as an oxidizing agent, such as chlorine in sodium chlo-
ride. Metals are reducing agents and nonmetals are oxi-
dizing agents.

Covalent Compounds
Covalent compounds are formed by sharing of electrons.
Sharing of electrons occurs when a nonmetal combines
with a nonmetal, or when atoms of the same element com-
bine to form molecules. A molecule is the smallest and most
stable and neutral particle of a substance. The following are
some examples of covalent bonding:

28
BasicChemistry.book Page 29 Monday, February 18, 2002 5:03 PM

Chapter 4 Compounds

Hydrogen molecule = H2 = H H = H–H

covalent bond

Two hydrogen atoms share a pair of their electrons

to form a covalent bond of its molecule.

Water = H2O = H O H = H–O–H

covalent bonds

In water formation, two hydrogen atoms share two

electrons with an oxygen atom, as shown in the above
diagram, and all three atoms are at the stable state. The
measure of attraction of an atom for the shared electrons
between it and another atom is called electronegativity.
Maximum electronegativity, which is 4, is assigned to
the element fluorine. More electronegativity means
more attraction, and vice versa. If the electronegativity
difference between two combining atoms is more than
1.6, there is ionic bonding; if less than 1.6, then covalent
bonding. When this difference is 0.6–1.6, there is
unequal sharing of electrons, which means the atom
with more electronegativity shares more than the other.
The atom that shares more is assigned a negative oxida-
tion number, and the other a positive number. These
compounds are known as polar covalent compounds
because they carry positive and negative poles on their
molecules. (See Table 4-2 for examples of the electroneg-
ativity difference and bonding.)
Radicals are charged groups of covalently bonded
atoms. They are ions and part of a compound. Most radi-
cals have oxygen bonded with a nonmetal, such as sulfate
(SO4–2), nitrate (NO3–), carbonate (CO3–2), and phosphate
(PO4–3). There are some that contain metals, such as per-
manganate (MnO4–) and dichromate (Cr2O7–2). Table 4-3
lists some common ions and their charges (oxidation

29
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Basic Chemistry for Water and Wastewater Operators

Electronegativity
Difference Bonding Examples
0 H2 = H – H
2.1 – 2.1 = 0
O2 = O – O
3.5 – 3.5 = 0
CH4
Covalent 2.5 – 2.1 = 0.4
0.6
HCl
Polar Covalent 2.1 – 3.0 = 0.9
H2O
1.6 2.1 – 3.5 = 1.4

NaCl

Ionic 0.9 – 3.0 = 2.1

Calcium oxide = CaO
1.0 – 3.5 = 2.5
3.2

Table 4-2 Electronegativity Difference (Absolute) and

Chemical Bonding

numbers). The oxidation number of a radical is the

algebraic sum of the oxidation number of the atoms in
its formula.

Chemical Formulae
A chemical formula is a shorthand notation using
chemical symbols and numerical subscripts to represent
the chemical composition of a compound. The subscript
indicates the number of combined atoms of its respec-
tive element. There are three kinds of chemical formulae:

30
BasicChemistry.book Page 31 Monday, February 18, 2002 5:03 PM

Chapter 4 Compounds

Cations
Oxidation Number
+1 +2 +3
Ammonium NH4+ Barium Ba++ Aluminum Al+++
Lithium Li+ Calcium Ca++ Iron (III), Fe+++
ferric
Sodium Na+ Copper (II), Cu++
cupric
Potassium K+ Iron (II), Fe++
ferrous
Silver Ag+ Lead Pb++
Copper (I), Cu+ Magnesium Mg++
cuprous
Nickel (II) Ni++
Zinc Zn++

Anions
Oxidation Number
–1 –2 –3
Acetate C2H3O2 – Carbonate CO3 = Phosphate PO4≡
Azide N3– Chromate CrO4=
Chloride Cl– Dichromate Cr2O7=
Bromide Br – Oxide O=
Iodide I– Peroxide O2=
Hydroxide OH– Sulfate SO4=
Hydrogen HCO3 – Sulfide S=
Carbonate
(Bicarbonate)
Hydrogen HSO4– Sulfite SO3=
Sulfate
(Bisulfate)
Nitrate NO3– Thiosulfate S2O3=
Nitrite NO2–
Chlorate ClO3–
Hypochlorite ClO– or OCl–

Table 4-3 Some Common Ions and Their Oxidation Numbers

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Basic Chemistry for Water and Wastewater Operators

Empirical Molecular Structural

Compound Formula Formula Formula
Water H2O H2O H–O–H

Ammonia NH3 NH3 H–N–H

H

Hydrogen peroxide HO H2O2 H–O–O–H

Methane CH4 CH4 H

H–C–H
H

Table 4-4 Examples of Formulae

empirical, molecular, and structural. An empirical for-

mula shows relative numbers of atoms, a molecular for-
mula shows the actual number of combined atoms in a
molecule, and a structural formula shows the bonding of
the atoms. Examples of these formulae are shown in
Table 4-4.
In the case of most inorganic compounds (com-
pounds of elements other than carbon), the empirical
formula is the same as the molecular formula.
A chemical formula is neutral and formed of two
parts: the first part has a positive oxidation number (less
electronegativity) and the second part has a negative oxi-
dation number (more electronegativity). When writing
the formula of a compound, write the positive part first
and the negative part second with their respective oxida-
tion numbers and balance the plus charge with the minus
by assigning appropriate subscripts, if required. If both
parts of the formula have the same oxidation number
(e.g., in sodium chloride, sodium is +1 and chlorine –1),
the charge is already balanced, and, therefore, no sub-
scripts are required. When the oxidation numbers of two
parts are different, then the charge is commonly balanced
by exchanging the oxidation number of the first part for

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Chapter 4 Compounds

the subscript of the second part, and vice versa. For exam-
ple, the formula for sodium sulfate, Na+1 SO4–2, is Na2SO4;
two sodium atoms have a +2 charge, and one sulfate rad-
ical has a –2 charge. When a radical has a subscript higher
than 1, use parentheses and write the subscript outside
the parentheses. Study the following examples:

Compound Oxidation Numbers Formula

Water H+1O–2 H2O

Calcium oxide Ca+2O–2 CaO

Calcium hydroxide Ca+2OH– Ca(OH)2

Aluminum sulfate Al+3SO4–2 Al2(SO4)3

Ammonium sulfate NH4+SO4–2 (NH4)2SO4

Naming Compounds
In most instances, the name of a compound is
formed from the name of the first part of the formula fol-
lowed by the name of the second part. CaSO4 is calcium
sulfate. The name of a binary compound (a compound
formed of only two elements), however, is formed from
the full name of the first element and the root of the
name of the second element ending with -ide.

Binary Compound Name

NaCl Sodium chloride
NaI Sodium iodide
FeS Iron sulfide
H2S Hydrogen sulfide
CaO Calcium oxide

When the same two elements form more than one

compound, use appropriate prefixes. Carbon and oxy-
gen form CO and CO2, which are known as carbon

33
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Basic Chemistry for Water and Wastewater Operators

monoxide and carbon dioxide, respectively. PBr5 is

known as phosphorus pentabromide, and PBr3 is phos-
phorus tribromide.
Formula weight is the sum of weights of all the atoms
in a formula. The following table has formula weights of
some compounds:

Compound Formula Weight

Water, H2O (1 × 2) + 16 = 18

Methane, CH4 12 + (1 × 4) = 16

Calcium hydroxide, Ca(OH)2 40 + (16 × 2) + (1 × 2) = 74

The gram formula weight of a compound is its mole

because it contains an Avogadro number of its formulae.
1 H2O molecule = 18 AMU

6.02 × 1023 H2O molecules = 18 g = 1 mol of water

The percentage composition of a compound is the per-

centage by mass of various constituent elements in a
compound. Percentage is parts per 100 parts. It is a quan-
titative or stoichiometric relationship of various ele-
ments in a compound.

Percentage of an element in a compound =

total atomic weight of the element
× 100
formula weight

Sample Problems
1. Calculate percentage composition of water.
Formula weight of H2O = 18
% of hydrogen = (2⁄ 18) × 100 = 11.11
% of oxygen = (16⁄ 18) × 100 = 88.89

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Chapter 4 Compounds

2. Calculate percentage composition of sodium carbon-

ate, Na2CO3.
Formula weight of Na2CO3 = 106
% of Na = (2 × 23)/106 × 100 = 43.4
% of C = (1 × 12)/106 × 100 = 11.3
% of O = (3 × 16)/106 × 100 = 45.3
3. Calculate percentage composition of aluminum sul-
fate, Al2(SO4)3.
Formula weight of Al2(SO4)3 = 342
% of Al = (2 × 27)/342 × 100 = 15.8
% of S = (3 × 32)/342 × 100 = 28.1
% of O = (12 × 16)/342 × 100 = 56.1

Questions
1. Define compound, ion, radical, and molecule.
2. Name the two types of bonds in compounds. How
are they formed?
3. Write the formulae for the following compounds:
a. Carbon dioxide
b. Ammonia
c. Calcium sulfate
d. Sodium carbonate
4. Name these compounds:
a. Na2O
b. H2S
c. Ca(OH)2
d. Fe2O3
5. Calculate percentage composition of calcium carbon-
ate (CaCO3).

35
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BasicChemistry.book Page 37 Monday, February 18, 2002 5:03 PM

5 Chemical Equations

A chemical equation is a concise symbolized

picture of a chemical reaction. It has both qualitative
and quantitative significance. It tells us which sub-
stances are reacting and in what amounts to produce
which and how much of new substances.
Hydrogen + Oxygen → Water
2H2 + O2 → 2H2O

Mass Ratio 2 × 2 : 2 × 16 : 2 × 18
This equation shows that 4 mass units of hydrogen
react with 32 mass units of oxygen to produce 36 mass
units of water. Reacting substances are known as reac-
tants, which are written on the left side of the equation.
Substances produced are termed products, which are writ-
ten on the right side. An arrow separates reactants from
products and indicates the direction of the reaction.
Arrows facing both ways indicate a reaction reversing
under ordinary experimental conditions.

Reactants Products
An arrow facing down (CaCO3↓) indicates precipita-
tion of a product, and an arrow facing up (CO2↑) means
a product is a gas.

Law of Conservation of Masses

The law of conservation of masses states that in
ordinary chemical reactions, the total mass of reactants
is equal to the total mass of products. Only atoms of
reactants are rearranged to form products in a chemical

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Basic Chemistry for Water and Wastewater Operators

reaction. Therefore, if there is the same number of

atoms of each element on each side of the equation, the
law is satisfied and the equation is balanced.

Steps in Writing a Balanced Equation

1. Write the equation in words for the reaction.
2. Give the correct formulae or symbols for all reactants
and products.
3. Balance the equation by assigning appropriate coef-
ficients to reactants and products.
4. Make sure that coefficients are in the smallest whole
number ratio.
Here is the reaction of water formation from hydro-
gen and oxygen, written step-by-step to balance the
equation.
1. Hydrogen + Oxygen → Water
2. H2 + O2 → H2O
To get two oxygen atoms on the right side, we need
two water molecules, which makes four hydrogen
atoms on the right side. So we need two hydrogen
molecules on the left to balance the equation.
3. 2H2 + O2 →2H2O
4. 2 : 1 :2
Coefficients are in the smallest whole number ratio.
The elements hydrogen, nitrogen, oxygen, fluorine,
chlorine, bromine, and iodine occur in a diatomic
(two-atom) molecular state, and all others occur as
single atoms. They are written as H2, N2, O2, F2, Cl2,
Br2, and I2 in chemical reactions.
Once these four steps are understood, they can be
written in two steps to balance the equation. These two
steps are word equation and balanced formula equation.

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Chapter 5 Chemical Equations

Examples:
1. Mercury (II)/mercuric oxide → Mercury + Oxygen
2HgO → 2Hg + O2↑
2. Calcium hydroxide + Calcium bicarbonate →
Calcium carbonate + Water
Ca(OH)2 + Ca(HCO3)2 → 2CaCO3↓ + 2H2O
3. Aluminum sulfate + Calcium hydroxide →
Aluminum hydroxide + Calcium sulfate
Al2(SO4)3 + 3Ca(OH)2 → 2Al(OH)3↓ + 3CaSO4
If the same radical is present on both sides of the
equation, it is easier to balance it as a single unit. Because
3SO4–2 is on the left, make 3SO4–2 on the right by using
coefficient 3 for CaSO4.

Quantitative Calculations or
Stoichiometry in Chemical Reactions
Equations also have quantitative significance. The
quantitative relationship of reactants and their products
is known as stoichiometry. We can calculate amounts of
reactants required to produce any desired amount of a
product by using the mass ratio of these substances from
their formula weights. Let us return to the equation in
the previous example where calcium hydroxide reacts
with calcium bicarbonate to produce calcium carbonate
and water. The balanced equation shows that 1 formula
weight of Ca(OH)2 reacts with 1 formula weight of
Ca(HCO3)2 to produce 2 formula weights of CaCO3 and
2 formula weights of H2O.
Mass ratio 74 : 162 : 200 : 36
Ca(OH)2 + Ca(HCO3)2 → 2CaCO3↓ + 2H2O

This also means that 1 mol (gram formula weight) of

Ca(OH)2 and 1 mol of Ca(HCO3)2 are needed to produce

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Basic Chemistry for Water and Wastewater Operators

2 mol of CaCO3 and 2 mol of H2O. By converting moles

into grams, we learn that 74 g of Ca(OH)2 react with
162 g of Ca(HCO3)2 to produce 200 g of CaCO3 and 36 g
of H2O.
Using this information, we can calculate the amount
of any substance corresponding to the given mass of any
other substance in the reaction. Let us calculate the
amount of Ca(OH)2 required to produce 100 g of CaCO3.
The equation shows that 200 g of CaCO3 will be pro-
duced from 74 g of Ca(OH)2. Thus, 100 g of CaCO3
would require 37 g (one half of 74) of Ca(OH)2. There-
fore, the mass ratio of Ca(OH)2 to CaCO3 stays the same
in both cases.
This calculation can be done systematically in three
steps:
1. Balance the equation.
2. Establish the mass ratio of the two substances.
3. From the mass ratio, calculate the mass of one sub-
stance corresponding to the given mass of the other
as follows:
(3) X 100 g
(2) 74 g 200 g
(1) Ca(OH)2 + Ca(HCO3)2 → 2CaCO3↓ + 2H2O
X 100 g
------------ = ---------------
74 g 200 g
100
X = ---------- × 74 g
200
= 37 g

How many milligrams per litre of calcium oxide are

required to react with 5 mg/L of carbon dioxide in water?
(3) X 5 mg
(2) 56 mg 44 mg
(1) CaO + CO2 → CaCO3↓

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Chapter 5 Chemical Equations

X 5 mg
----------------- = -----------------
56 mg 44 mg
5
X = ------ × 56 mg
44
= 6.36 mg/L

Various Types of Chemical Reactions

Chemical reactions can be classified into composi-
tion, decomposition, replacement, ionic, and redox
reactions.
Composition reactions: In these reactions, two or more
substances combine to form a new compound. For
example, iron and sulfur combine to form iron sulfide:
Fe + S → FeS
Hydrogen and oxygen react to form water:
2H2 + O2 → 2H2O

Sodium and chlorine combine to form sodium

chloride:
2Na + Cl2 → 2NaCl

Decomposition reactions: They are the reverse of the

composition reactions. A complex substance breaks
down into simpler substances. For example, electrolysis
(decomposition by means of electricity) of water pro-
duces hydrogen and oxygen:
2H2O → 2H2↑ + O2↑

Quicklime (CaO) is formed by heating limestone

(CaCO3):
 CaO + CO ↑
CaCO3 → 2
 stands for heat

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Basic Chemistry for Water and Wastewater Operators

Replacement reactions: In these reactions, an element

is replaced in a compound by another element. The
stronger element replaces the weaker element. For exam-
ple, iron replaces copper from a solution of copper sulfate
(CuSO4), forming iron sulfate and copper. It happens
because iron is a stronger reducing agent than copper.
Fe + CuSO4 → FeSO4 + Cu↓

Table 5-1 shows the increasing strength of oxidizing

and reducing agents. This table helps to determine
which element can replace other elements.
Ionic reactions or double replacement: In these reac-
tions, a part of an ionic compound is exchanged with a
part of another when their solutions are mixed together.
One set of ions forms an insoluble compound that pre-
cipitates out. Following are some examples of ionic reac-
tions from water and wastewater treatment.
In the removal of turbidity, alum (Al2(SO4)3) and
lime (Ca(OH)2) are mixed with water to form Al(OH)3,
the floc:
Al2 (SO4)3 + 3Ca(OH)2 → 2Al(OH)3↓ + 3CaSO4

In the removal of permanent hardness caused by sul-

fate, chloride, or nitrate of calcium, soda ash (Na2CO3) is
used and calcium carbonate (CaCO3) is formed and pre-
cipitates out:
CaSO4+ Na2CO3 → CaCO3↓ + Na2SO4

Magnesium hardness is removed by using lime

(Ca(OH)2):
MgSO4 + Ca(OH)2 → Mg(OH)2↓ + CaSO4

Redox reactions: The term redox comes from reduction

and oxidation. In these reactions, two elements have dif-
ferent oxidation numbers on two sides of the equation.
Any equation with a free element in it is a redox reaction.

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Chapter 5 Chemical Equations

Oxidation Potential,
Reduced State Oxidized State volts
Cs Cs+ + e– 3.02
Li Li+ + e– 3.02
K K+ + e– 2.99
Ba Ba++ + 2e– 2.90
Ca Ca++ + 2e– 2.87
Na Na+ + e– 2.71
Mg Mg++ + 2e– 2.34
Al Al+3 + 3e– 1.67
Mn Mn++ + 2e– 1.05

Increasing Strength of Oxidizing Agent

Increasing Strength of Reducing Agent

Zn Zn++ + 2e– 0.76

Cr Cr+3 + 3e– 0.71
Fe Fe++ + 2e– 0.44
Co Co++ + 2e– 0.28
Ni Ni++ + 2e– 0.25
Sn Sn++ + 2e– 0.14
Pb Pb++ + 2e– 0.13
H2 2H+ + 2e– 0.00
Sn++ Sn+4 + 2e– –0.15
Cu Cu++ + 2e– –0.34
2I– I2 + 2e– –0.53
Fe++ Fe3 + e– –0.75
Hg Hg+ + e– –0.80
Ag Ag+ + e– –0.80
Hg Hg++ + 2e– –0.85
Hg+ Hg++ + e– –0.91
2Br – Br2 + 2e– –1.06
2Cl– Cl2 + 2e– –1.36
2F– F2 + 2e– –3.03

Table 5-1 Electromotive Series

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Basic Chemistry for Water and Wastewater Operators

All replacement reactions, therefore, are redox reactions.

For example, formation of a salt and hydrogen gas when
an acid reacts with a metal is shown as
Zn + 2HCl → ZnCl2 + H2↑

The rusting of iron is shown as

4Fe + 3O2 → 2Fe2O3↓

The formation of iodine from sodium iodide (NaI) by

chlorine is shown as
2NaI + Cl2 → 2NaCl + I2

How to Balance a Redox Equation

Suppose the reaction is
Hydrogen sulfide + Oxygen → Sulfur Dioxide + Water
Step 1: Write the skeleton equation for the reaction.
H2S + O2 → SO2 + H2O

Step 2: Assign oxidation numbers to all elements and

determine which one is oxidized and which one is
reduced.
+1–2 0 +4–2 +1–2
H2S + O2 → SO2 + H2O

Sulfur, in this case, is oxidized from –2 to +4 and oxy-

gen is reduced from 0 to –2.
Step 3: Write the electronic equations for the oxida-
tion process and reduction process.

S–2 – 6e– → S+4

O02 + 4e– → 2O–2

Step 4: Adjust the coefficients in both electronic

equations so that the number of electrons lost equals
electrons gained. The smallest number common to both
equations is 12.

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Chapter 5 Chemical Equations

2S–2 – 12e– → 2S+4

3O02 + 12e– → 6O–2

Step 5: Use the above coefficients in the skeleton

equation and balance the rest of the equation by trial-
and-error method.
2H2S + 3O2 → 2SO2 + H2O

Balanced equation:
2H2S + 3O2 → 2SO2 + 2H2O

Questions
1. What is a chemical equation?
2. Write an equation for formation of water by burning
hydrogen in oxygen.
3. What is the practical use of chemical equations?
4. State the law of conservation of masses.
5. Balance the following equations:
a. Oxygen Ozone
O2 O3
b. Ca(OH)2 + CO2 → CaCO3↓ + H2O
c. Ca(OH)2 + Mg(HCO3)2 → CaCO3↓ + MgCO3 + H2O
d. CaCO3 + H2SO4 → CaSO4 + H2CO3
Sulfuric acid

e. Ca(OCl)2 + H2O → Ca(OH)2 + HOCl

Calcium hypochlorite Hypochlorous acid

f. NH3 + HOCl → NHCl2 + H2O

6. Balance the following equation and calculate the
amount of oxygen required to react with 5 g of
hydrogen sulfide.
H2S + O2 → H2SO4

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BasicChemistry.book Page 47 Monday, February 18, 2002 5:03 PM

6 Acids, Bases, and Salts

C ompounds whose water solutions contain

ions are acids, bases, or salts.

Acids
An acid is a substance that gives hydrogen ions (pro-
tons) in its water solution. According to the more general
modern concept, an acid is a substance that donates pro-
tons to another substance.
A hydrogen ion (H+) is known as a proton because
there is a single proton in the hydrogen nucleus that
gives a positive charge after the loss of the electron. A
hydrogen ion in a water solution exists only in associa-
tion with a water molecule as hydronium ion (H3O+).

H+ + H2O = H3O+

HCl + H2O → H3O+ + Cl–

Sometimes, this equation is simplified as

HCl → H+ + Cl–
A hydronium ion is responsible for the properties of
the acids, such as sour taste and the ability to turn blue
litmus paper red.
All acids are polar covalent compounds; hydrogen,
the common element in all acids, is commonly the first
part of their formula. In general, they are water solutions.
Hydrochloric acid (HCl), nitric acid (HNO3), and sul-
furic acid (H2SO4) are known as mineral acids. They are
some of the strong acids. Acetic acid (HC2H3O2), carbonic

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Basic Chemistry for Water and Wastewater Operators

acid (H2CO3), and hydrosulfuric acid (H2S), which is

hydrogen sulfide gas dissolved in water, are some of the
weak acids. The strength of an acid depends on the
degree of its ionization (ion formation). More ionization
means more hydronium ions in the solution and there-
fore stronger acid.

HCl + H2O → H3O+ + Cl–

Hydrochloric acid is a strong acid because there is

about 99 percent ionization into H3O+ and Cl– ions. Nor-
mally, the more hydrogen atoms in the formula, the
weaker the acid.

Properties of Acids
1. Acid solutions are sour.
2. Acids form hydronium ions in their water solution.
3. Acids neutralize hydroxides.
H2SO4 + Ca(OH)2 → CaSO4 + 2H2O
4. Acids react with metals and produce hydrogen gas
(H2).
Zn + 2HCl → ZnCl2 + H2↑
5. Acids react with oxides of metals to form a salt and
water.
CuO + H2SO4 → CuSO4 + H2O
6. Acids react with carbonates to liberate carbon diox-
ide (CO2).
CaCO3 + 2HCl → CaCl2 + H2O + CO2↑
7. Acids change the color of certain indicators.

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Chapter 6 Acids, Bases, and Salts

Naming Acids
Binary acids (acids formed of only two elements) start
with hydro- and end with -ic. After hydro, comes the root
of the name of the second element.
HCl = hydrochloric acid
HBr = hydrobromic acid
H2S = hydrosulfuric acid
Ternary acids (acids formed of three elements: hydro-
gen, middle element, and oxygen) commonly have the
root of the name of the middle element with the ending
-ic or -ous.
H2SO4 = sulfuric acid
HNO3 = nitric acid
H2CO3 = carbonic acid
H3PO4 = phosphoric acid
If the same three elements form more than one acid,
use the following system:
HClO4 = per chloric (one oxygen atom more than
chloric acid)
HClO3 = chloric acid
HClO2 = chlorous (one oxygen atom less than
chloric acid)
HOCl or HClO = hypochlorous (two oxygen atoms
less than chloric acid)

Bases
A base is a substance that accepts the protons. A com-
mon base is the hydroxide ion (OH–). Because hydrox-
ides such as Ca(OH)2 and NaOH furnish OH– ions to
their solutions, they are commonly known as bases.

Ca(OH)2 → Ca+2 + 2OH–

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Basic Chemistry for Water and Wastewater Operators

OH– + H3O+ → 2H2O

Some common hydroxides are:

Lye, sodium hydroxide = NaOH
Milk of Magnesia, magnesium hydroxide = Mg(OH)2
Lime, calcium hydroxide = Ca(OH)2
Ammonia aqua, ammonium hydroxide = NH4OH
The strength of a base, like an acid, depends on its
degree of dissociation (ion formation). NaOH dissociates
strongly and is a strong base; whereas, Ca(OH)2 dissoci-
ates poorly and is a weak base.

Properties of Bases
1. Hydroxides are ionic compounds. Their solutions are
bitter and slippery.
2. Base solutions change the color of certain indicators.
3. Bases neutralize acids.
4. Bases react with oxides of nonmetals to produce salts
and water.
CO2 + Ca(OH)2 → CaCO3↓ + H2O

Amphiprotic Compounds
Amphiprotic compounds behave as proton donors
with some substances and proton acceptors with other
substances. They accept protons from strong acids and
donate protons to strong bases. They are weak bases.
Base Acid
Zn(OH)2 + 2HCl → ZnCl2 + 2H2O

Acid Base
Zn(OH)2 + 2NaOH → Na2ZnO2 + 2H2O
Sodium zincate

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Chapter 6 Acids, Bases, and Salts

Acid Base
HCl + H2O → H3O+ + Cl–

Base Acid
NH3 + H2O → NH4+ + OH–

Zinc hydroxide and water are amphiprotic compounds.

Anhydrides
Anhydrides are oxides that react with water to pro-
duce acids or hydroxides. Acid anhydrides are oxides of
nonmetals that form acids in water, and basic anhydrides
are oxides of metals that form hydroxides in water.
CO2 + H2O → H2CO3
Acid anhydride Carbonic acid

CaO + H2O → Ca(OH)2

Basic anhydride Calcium hydroxide

Thus, oxides of nonmetals, such as CO2, cause acid-

ity in water, and soluble oxides of metals, like CaO, cause
alkalinity in water.

pH Values
pH or the hydronium ion index scale measures
hydronium ion concentration in solutions. Numerically,
pH is the common log of the number of litres of a solu-
tion containing 1 mol of hydronium ions (19 g) or
hydrogen ions (1 g). The number of litres having 1 mol
of H3O+ ions is the reciprocal of the number of moles of
H3O+ ions per litre. Therefore, pH is the log of the recip-
rocal of the H3O+ ion concentration expressed as moles
per litre (mol/L). Suppose 1 L of a solution contains
0.001 mol of H3O+ ions. Then, 1,000 L would contain
1 mol of H3O+ ions. And the pH of the solution would be
3 (the common log of 1,000).

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Basic Chemistry for Water and Wastewater Operators

H3O+ ion concentration = 0.001 mol or 1/1,000 mol/L

Reciprocal of 1/1,000 = 1,000/1
= 103
or log of 1,000 = 3
pH = 3

pH may also be defined as minus log of hydronium

ion concentration expressed as moles per litre.
Mathematically, pH = –log [H3O+]. (The use of brack-
ets [ ] means concentration as moles per litre.)

pH = –log [H3O+] (In the above example.)

pH = –log 1/1,000
pH = –(–3) = 3

pH Scale
Water at a temperature of 25°C, due to self-ionization,
contains 10–7 (0.0000001) mol of hydronium ions per litre.

H2O + H2O H3O+ + OH–

Therefore, its pH is 7. Hydroxide ion (OH–) concen-

tration is also 10–7 mol/L at the same time. Thus, pH 7
indicates a neutral solution. Water and most of the
diluted solutions in a laboratory at 25°C have [H3O+] ×
[OH–] = 10–14 mol2/L2. It is derived by substituting 10–7
mol/L for each of the H3O+ and OH– ions. 10–7mol/L ×
10–7mol/L = 10–14 mol2/L2, which is known as Kw, the
water constant.

[OH –] 10–14 10–13 10–12 10–11 10–10 10–9 10–8 10–7 10–6 10–5 10–4 10–3 10–2 10–1 10–0
[H 3O+] 100 10–1 10–2 10–3 10–4 10–5 10–6 10–7 10–8 10–9 10–10 10–11 10–12 10–13 10–14
pH 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14

Increasing strength of an acid Neutral Increasing strength of a base

Figure 6-1 pH Scale

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Chapter 6 Acids, Bases, and Salts

The pH scale (Figure 6-1) ranges from 0 to 14, based

on the water constant. It measures 1 mol/L of H3O+ ion
concentration as the maximum at 0 and 1 mol/L of OH–
ion concentration at 14. Therefore, using the previous
equation, when H3O+ ion concentration is 1 mol/L, OH–
ion is 10–14 mol/L, and vice versa.

Methods of pH Measurement
Colorimetric: An indicator such as phenol red or
bromthymol blue is added to the solution. It produces a
certain intensity of color that is then matched with the
permanent standard. pH is estimated to the nearest
0.1 pH unit.
Potentiometer or pH meter: This is the most convenient
and accurate method of pH measurement. The meter
measures the voltage difference developed between the
electrodes due to hydronium ions in the solution. This
difference is then read on the scale in pH units.
Hydrion paper: Dip a piece of this paper in the solu-
tion and match the color developed with the permanent
standard.

Alkalinity and Acidity in Natural Water

Acidity in water is usually due to CO2 (acid anhy-
dride), mineral acids, or hydrolysis of some heavy metal
salts such as aluminum sulfate (Al2(SO4)3). Hydrolysis is
decomposition of a substance by reacting with water.
Al2(SO4)3 + 6H2O → 2Al(OH)3↓ + 3H2SO4

Alkalinity may be defined as the capacity to neutral-

ize acidity. It is caused in surface waters by hydroxides,
carbonates, and bicarbonates.
Ca(OH)2 + H2SO4 → CaSO4 + 2H2O

CaCO3 + H2SO4 → CaSO4 + Ca(HCO3)2

Ca(HCO3)2 + H2SO4 → CaSO4 + 2CO2↑ + 2H2O

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Basic Chemistry for Water and Wastewater Operators

Salts
A salt is an ionic compound containing anions
formed from an acid after the donation of protons. For
example, in the case of sodium chloride (NaCl), a salt,
Cl– comes from HCl. In the case of Na2SO4, sulfate (SO4=)
comes from H2SO4. Some common examples of salts are
chlorides, bromides, iodides, nitrates, sulfates, carbon-
ates, and phosphates. A salt is produced when an acid
reacts with a base.
HCl + NaOH → NaCl + H2O
Salt

Questions
1. Which element is common in all acids?
2. Define acid, base, salt, and pH.
3. A set of solutions has pH values of 3, 4, 7, and 10.
Which solution is the most acidic, which one is the
most basic, and which one is neutral?
4. What would be the pH of a solution containing
0.001 mol of H3O+ ion concentration per litre?
5. Name various methods of measuring the pH of a
solution.
6. What is the water constant?
7. Differentiate an acid from a base.
8. Which ion causes acidity?
9. When an acid reacts with a base, what products get
produced?
10. Is sodium hydroxide an acid or a base?

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7 Solutions

A solution is a homogeneous mixture of two or

more substances, with its composition varying within
certain limits. A solution, therefore, has uniform compo-
sition. Examples are sugar and table salt in water. The
dissolving medium is the solvent and the dissolved sub-
stance, the solute. Water in the above-mentioned solu-
tions is the solvent, and sugar and salt are the solutes.
A heterogeneous mixture of two or more substances
is called a suspension, e.g., clay in water. In this case, sus-
pended particles of the dispersed substance, clay, are
distributed nonuniformly in the medium. The bottom
part of the mixture has more particles than the upper.
When suspended particles are too small to settle by the
force of gravity and too large to dissolve to form a solu-
tion, the suspension is known as a colloid. Particle size in
a colloidal suspension is 1–100 nm. A nanometre is
equal to 1/1,000,000 mm or 10–6 mm. These particles
show peculiar dancing movements known as Brownian
motions due to their continuous collisions with water
molecules. Suspended particles of a colloid cause turbid-
ity. Colloids are discussed in detail in chapter 8.
Solutions of ionic compounds and acids in water
conduct electricity because they produce ions. These
substances are known as electrolytes. Most of the covalent
compounds stay as molecules in their solutions and do
not conduct electricity. Such substances are known as
nonelectrolytes. Sodium chloride and hydrochloric acid
are electrolytes, and sugar is an example of a
nonelectrolyte.

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Basic Chemistry for Water and Wastewater Operators

Solutions can be classified as solids, liquids, and

gases, depending on their physical states, which depend
on the solvent. Metals mix with metals and form alloys,
which are solid solutions; some solids and liquids mix in
liquids to form liquid solutions; and gases mix with gases
to form gas solutions. Copper in nickel, alcohol in water,
and oxygen in nitrogen (air) are examples of solid, liq-
uid, and gas solutions, respectively.

Concentration of a Solution
Percent concentration is parts of the solute in 100 parts
of the solution by mass.
Percentage concentration can be expressed as

Mass of solute
% Concentration = --------------------------------------------- × 100
Mass of solution

Therefore, 10 g of sugar in 90 g of water is a 10 per-

cent sugar solution.
Molarity (M) is the number of moles (gram formula
weights of compounds) of the solute per litre of its solu-
tion. A molar (M) solution contains 1 mol of the solute
per litre, and a 2 molar (2M) solution contains 2 mol of
the solute per litre. A molar solution of HCl, for example,
contains about 36.5 g of HCl per litre of solution and is
labeled as M HCl. A solution with 73 g of HCl per litre is
2M HCl and one with 18.25 g of HCl per litre is 0.5M
HCl. Molarity is also known as formality.
M H2SO4 contains 98 g of H2SO4 per litre of the
solution.
0.25M H2SO4 contains 98 × 0.25 or 24.5 g of H2SO4
per litre of the solution.
M NaOH contains 40 g/L of the solution.
0.10M NaOH contains 40 × 0.1 or 4 g/L of the
solution.

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Chapter 7 Solutions

Molality (m) is the number of moles of the solute per

kilogram of the solvent. It expresses the quantity of sol-
ute in quantity of the solvent. One mol of a solute dis-
solved in 1 kg of the solvent forms a “molal” solution.
Normality (N) is the number of gram equivalent
weights of a solute per litre of the solution. Gram equiv-
alent weight of a substance may be defined as the mass
of a substance in grams that contains, replaces, or reacts
with the Avogadro number of hydrogen atoms (a mole
or 1 g of hydrogen atoms). A mole of hydrogen atoms
offers an Avogadro number of electrons in a reaction
because a hydrogen atom has only one electron to offer.
Therefore, gram equivalent weight may be defined as the
mass of a substance in grams that has an Avogadro num-
ber of electrons to participate in a chemical reaction.
Gram equivalent weights of various substances are calcu-
lated by the following formulae:
Gram equivalent weight of an element =
mole or gram atomic weight
-------------------------------------------------------------------------------
oxidation number

Examples:
1g
Gram equivalent weight of hydrogen = -------- = 1 g
1

Gram equivalent weight of chlorine = 35.5 g

----------------- = 35.5 g
1

16 g
Gram equivalent weight of oxygen = ------------ = 8 g
2

Gram equivalent weight of a compound =

mole or gram formula weight
------------------------------------------------------------------------------------
positive charge in the formula

Examples:
36.5 g
Gram equivalent weight of HCl = ----------------- = 36.5 g
1

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Basic Chemistry for Water and Wastewater Operators

98 g
Gram equivalent weight of H2SO4 = ------------ = 49 g
2
Gram equivalent weight of H3PO4 (phosphoric acid) =
98 g
------------ = 32.66 g
3
74 g
Gram equivalent weight of Ca(OH)2 = ------------ = 37 g
2
342 g
Gram equivalent weight of Al2(SO4)3 = --------------- = 57 g
6
100 g
Gram equivalent weight of CaCO3 = --------------- = 50 g
2
In case of acids and hydroxides, gram equivalent
weight may be determined by dividing the mole by
the replaceable hydrogen atoms and hydroxide ions,
respectively.
In case of redox reactions, the gram equivalent
weight of a reactant is calculated by dividing its mole
by the total change in its oxidation number in its
one formula unit. The total change in oxidation
number is determined by determining oxidation
numbers of all the elements in the formula on the
reactant and product sides of the equation. Study the
following examples.

Examples:
Determine gram equivalent weights of potassium
permanganate (KMnO4), potassium dichromate
(K2Cr2O7), and sodium thiosulfate (Na2S2O3) in the
following redox reactions:

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Chapter 7 Solutions

a.
+1 +7–2 +1 +2 –2
2K MnO4 + 5H2C2O4 + 3H2SO4 → K2SO4 + 2MnSO4 + 10CO2 + 8H2O

Total oxidation numbers (+1 +7 –8) (+1 +2 –8)

K Mn O4 → K, Mn, 4O
Difference = +5
mole
Gram equivalent weight of KMnO4 in this reaction = --------------
5
158
= ---------- g
5
= 31.6 g
b.
+1 +6 –2 +1 +3 –2
K2Cr2O7 + 6KI+7H2SO4 → 4K2SO4 + Cr2(SO4)3 + 7H2O + 3I2

Total oxidation numbers (+2 +12 –14) (+2 +6 –14)

K2Cr2O7 → 2K,2Cr,7O
Difference = +6
mole
Gram equivalent weight of K2Cr2O7 = --------------
6
294
= ---------- g
6
= 49 g
c.
+1 +2 –2 +1 +2.5–2
2 Na2 S2O3 + I2 → Na2S4O6 + 2NaI
Total oxidation numbers (+2 +4 –6) (+2 +5 –6)
Na2S2O3 → 2Na, 2S, 3O
Difference = –1
mole
Gram equivalent weight of Na2S2O3 = --------------
1
158
= ---------- g
1
= 158 g

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Basic Chemistry for Water and Wastewater Operators

The last two chemicals are used in chemical oxygen

demand and dissolved oxygen determinations and
their gram equivalent weights used are 49 g and
158 g, respectively.
A normal solution contains one gram equivalent
weight of a solute per litre, and a 0.5N solution contains
0.5 g equivalent weight per litre of the solution.

N HCl contains 36.5 g of HCl per litre of the solution.

0.5N HCl contains 18.25 g of HCl per litre of the
solution.
N H2SO4 contains 49 g of H2SO4 per litre of the
solution.
0.02N H2SO4 contains 0.98 g of H2SO4 per litre of
the solution.

Saturated Solution
A saturated solution contains maximum dissolved
solute under specified conditions. Dissolved particles of
the solute are in equilibrium with the undissolved parti-
cles. The rate of dissolving is equal to the rate of
crystallizing.
Dissolving
NaNO3(s) Na + (aq) + NO3–(aq)
Crystallizing
where:
s = solid
aq = dissolved

Unsaturated Solutions
A solution with any amount of dissolved solute less
than the amount required to make a saturated solution
is considered to be unsaturated.

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Chapter 7 Solutions

Supersaturated Solutions
A supersaturated solution contains more dissolved
solute than required for preparing a saturated solution
and can be prepared by heating a saturated solution,
adding more solute, and then cooling it gently. Excess
dissolved solute crystallizes by seeding supersaturated
solution with a few crystals of the solute.

Dilute and Concentrated Solutions

These terms are vague as they lack quantitative pre-
ciseness. A dilute solution contains less solute and a con-
centrated solution, more.

Standard Solutions
A standard solution is an accurately prepared solution
used to determine the concentration of other solutions,
which are then known as standardized solutions. In the
laboratory, we can use a standard acid solution to stan-
dardize a base solution, and vice versa. The volumetric
technique of matching a standard solution and a solu-
tion of unknown concentration is known as titration.
This process of comparison is known as standardization.
To indicate the completion of a reaction, another sub-
stance called an indicator is used. An indicator has a dif-
ferent color in the standard and the standardized
solutions. For example, let’s standardize a solution of
sodium hydroxide (NaOH) with a standard sulfuric acid
(H2SO4) solution. Add a few drops of phenolphthalein,
the indicator, to a known volume of NaOH solution and
the solution will turn pink. Then slowly add a standard
H2SO4 solution to it until the pink color disappears. Phe-
nolphthalein is colorless in acid solutions.
Determine concentration (normality) of NaOH solu-
tion by using the equation

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Basic Chemistry for Water and Wastewater Operators

NV = N1V1

where:
N = normality of standard
V = volume (mL) of standard
N1 = normality of the standardized
V1 = volume of the standardized
Suppose in the above titration we took 100 mL of
NaOH solution and used 50 mL of 0.1N H2SO4 to reach
the end of the reaction or equivalence point (end point).
Normality of NaOH can be calculated as

H 2 SO 4 NaOH
-----------------
- = -----------------
NV N1 V1

0.1 × 50 = N1 × 100

0.1 × 50
N1 = --------------------- = 0.05
100

Sodium hydroxide is 0.05N NaOH solution. This

equation can also be used for making dilute solutions
from stock solutions.
Suppose we prepare 1,000 mL of 0.02N H2SO4 from
1N H2SO4 stock solution. It requires only 20 mL of 1N
H2SO4 to be diluted in 1 L according to the equation.

Stock Dilute
--------------- = -----------------
NV N1 V1

1 × V = 0.02 × 1,000 mL
V = 20 mL
This equation is based on the fact that the volume of
a solution is inversely proportional to the concentration
and also that equal volumes of solutions with the same
normality are chemically equivalent.

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Chapter 7 Solutions

Factors That Affect Solubility

Temperature: A rise in temperature usually increases
solubility of a solid in a liquid except for a few substances
such as slaked lime (Ca(OH)2) and sodium sulfate
(Na2SO4). In the case of gases, however, the lower the
temperature, the higher the solubility, and vice versa.
For example, dissolved oxygen in surface waters is 14.62
and 9.17 mg/L at 0° and 20°C, respectively.
Pressure: Pressure has an insignificant effect on the
solubility of a solid or liquid in a solid or liquid. Solubil-
ity of a gas in a liquid or a solid increases with the rise in
pressure, and vice versa. Henry’s law states that the mass
of a dissolved gas in a liquid is directly proportional to
the pressure of the gas in contact with the liquid, at a
constant temperature.
Carbonated beverages in a capped bottle have 5–10
atmospheres pressure. Without the cap, there is efferves-
cence (rapid evolution of a gas from a solution) due to
lower solubility at a lower pressure.
Nature of the solute and the solvent: Like substances
dissolve in like solvents. Inorganic substances dissolve in
inorganic solvents and organic substances, in organic
solvents. Solubility of a substance depends on two types
of forces: attractive forces among the solute particles and
attractive forces between solute and solvent particles.
The former cause lower solubility and the latter, more.

Questions
1. Define the following:
a. Solution
b. Solute
c. Solvent
d. Colloidal suspension
e. Gram equivalent weight

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Basic Chemistry for Water and Wastewater Operators

f. Saturated solution
g. Unsaturated solution
h. Standard solution
2. Calculate gram equivalent weights of the following:
a. HCl
b. H2SO4
c. NaOH
d. Na2CO3
e. Fe2(SO4)3
3. How many grams of NaOH are required to prepare
500 mL of 0.1N NaOH solution?
4. Calculate the normality of a HCl solution in a titra-
tion when 100 mL of it used 75 mL of 0.25N NaOH.
What will be its molarity?
5. a. State Henry’s law.
b. Will there be more or less dissolved oxygen at
(1) higher oxygen pressure and (2) at higher
temperature?
6. Differentiate a solution from a suspension.
7. How many different states are in solutions?
8. What is meant by molarity of a solution?
9. Differentiate between a normal and a molar solution.

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8 Colloids and Coagulation

The term colloid means glue in Greek and it

was coined by Thomas Graham in 1861. A colloid is
formed of dispersed particles and dispersing medium.
The dispersed particles range from 1–100 nm in diame-
ter as compared to particles of true solutions, which are
0.1–1 nm (see Table 8-1).
Colloidal particles may be aggregates of atoms or
molecules that are big enough to be filtered out and
small enough to stay suspended against the force of grav-
ity. These particles are visible with a light-powered
microscope. Some common examples of colloids are fog,
smoke, foam, cream, cheese, paints, and glue.

Suspension
Coarse Fine Colloid Solution
1,000 100–1,000 1–100 0.1–1
Table 8-1 Particle Size of Suspensions and Solutions (nm)

Methods of Colloid Formation

Any insoluble material in the dispersion medium
can produce a colloid. Colloidal particles can be pro-
duced by the following:
1. Colloid mills . . . coarse grinders.
2. Ionic reactions . . . formation of insoluble products.
3. Mixing of some insoluble organic compounds in
water, such as soap, starch, gelatin, agar, gum arabic,
and albumin. In these cases, water can disperse the
particles only into colloidal suspension.

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Basic Chemistry for Water and Wastewater Operators

Types of Colloids
Classification of colloids is based on the state of the
dispersed phase and the dispersion medium. There are
only eight classes because a gas does not form suspen-
sion in a gas.

Colloidal Dispersion Examples

Solid in solid Ruby glass

Solid in liquid Glue, India ink

Solid in gas Smoke

Liquid in solid Jelly

Liquid in liquid Cream, emulsions

Liquid in gas Fog

Gas in solid Floating soap

Gas in liquid Foam, whipped cream

Colloids may be classified into sols or gels based on

their liquid or jelly-like state, respectively. Or, colloids
may be classified into lyophilic or lyophobic colloids,
depending on the affinity of the dispersed phase with
the dispersion medium.
1. Lyophilic (medium-loving) colloids: If a small amount
of powdered gelatin is mixed in water and dispersion
is allowed to stand, it sets to form a gel or jelly. The
dispersed particles of gelatin have great affinity for
the dispersing medium and become thoroughly
hydrated. This traps the water in such a way that vis-
cosity of dispersion increases, which is known as
emulsoid. Other examples are soap, soluble starch,
soluble protein, blood serum, and gum arabic.

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Chapter 8 Colloids and Coagulation

2. Lyophobic (medium-hating) colloids: Dispersed parti-

cles have a poor affinity for the dispersing medium
and, thus, there is no significant change in the vis-
cosity of the medium. They are, therefore, as fluid as
the medium and are highly susceptible to coagula-
tion, which is the separation of colloidal particles
from the medium by adding electrolytes, e.g., coagu-
lants like alum and ferric sulfate in water treatment.
These colloids are known as suspensoids. The terms
hydrophilic and hydrophobic are used when the disper-
sion medium is water.
Colloids can also be classified as positive and nega-
tive (see Figure 8-1). All colloids are electrically charged,
but the charge varies considerably in magnitude with
the nature of the colloidal material. A colloidal charge
may change with a change in external conditions. For
this reason, both Al(OH)3 and Fe(OH)3 flocs may be pos-
itive or negative. The charge is gained by the selective
adsorption of ions from the surrounding medium or due
to ionization of surface components of the colloid par-
ticles. Most colloids in water that cause turbidity and
color are negative.

Negative Colloidal Positive Colloidal

Particles Particles

Figure 8-1 Negative and Positive Colloidal Particles

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Basic Chemistry for Water and Wastewater Operators

General Properties
Colloidal particles are very small, but their surface
area in relation to mass is very great. If a 1-cm3 cube is
divided into a 1-nm3 cubes, the surface area increases
from 6 cm2 to 600 m2. Due to this fact, surface phenom-
ena predominate and control the behavior of colloids.
The mass of colloidal particles is so small that gravita-
tional effects are unimportant.

Adsorption
Adsorption is the acquiring of a gas, liquid, or solid
on the surface of a liquid or solid with which it is in con-
tact. Adsorbing material is known as adsorbent and
adsorbed as adsorbate. For example, powdered activated
carbon is used in water treatment as adsorbent for pesti-
cides, and chemicals causing tastes and odors are the
adsorbates. Because of the large surface area of dispersed
particles of a colloid, a remarkable amount of adsorption
may occur. Adsorption is generally preferential in nature,
with some ions preferred and others excluded. This selec-
tive action yields a charge on colloidal particles and is
important in the stability of many colloidal dispersions.

Effect on Freezing and Boiling Points

Colloidal dispersions have less effect on the freezing
and boiling points of liquids than the solutes due to the
fact that dispersions are very diluted with only a few dis-
persed particles. Each particle may be formed of hun-
dreds or thousands of molecules.

Dialysis
The separation of colloids from crystalloids by diffu-
sion through a semipermeable membrane is dialysis. Due

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Chapter 8 Colloids and Coagulation

to their large particle size, colloids do not pass through a

semipermeable membrane, whereas solute particles do.

Electrical Properties
Colloidal particles are charged, as mentioned before,
due to the adsorption of ions or ionization on the surface
of the colloidal particle. Many colloidal dispersions are
dependent on the electrical charge for their stability.
Like charges repel; therefore, similarly charged particles
of colloid do not form aggregates or floc, thus making
the system stable. The magnitude of the charge at the
boundary between the volume held (total volume of col-
loidal particles, adsorbed ions, and water associated with
the aggregate) and the surrounding medium is known as
zeta potential. The magnitude of zeta potential may be
estimated from electrophoretic measurements of particle
movements.
Zeta potential or repulsion between colloidal parti-
cles is counteracted by van der Waals forces, Brownian
motions, and gravitational forces to destabilize or coag-
ulate the system. The van der Waals forces are intermolec-
ular attractive forces. Brownian motions are random
movements of colloidal particles caused by bombard-
ment of molecules of the dispersion medium. Brownian
motions, when vigorous due to high temperature, cause
effective collisions among colloidal particles. The objec-
tive of chemical coagulation is to reduce the zeta poten-
tial to almost zero for effective turbidity removal.

Tyndall Effect
Because colloidal particles have dimensions greater
than the average wavelength of white light, they reflect
light. Therefore, a beam of light, passing through a col-
loidal suspension, is visible to an observer at the right
angle of the beam.

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Basic Chemistry for Water and Wastewater Operators

Methods of Precipitating Colloids

Electrophoresis
This is the coagulation of a colloid in an electrical
field. Colloid particles will accumulate at the pole of
opposite charge.

Addition of a Colloid of Opposite Charge

When colloids of opposite charge are mixed, there is
mutual precipitation. This method is used less frequently
in sanitary engineering because large volumes of a sec-
ond colloid will be required.

Addition of Electrolytes
Electrolytes contribute ions of opposite charge than
that of a colloid. In case of water and wastewater treatment,
the more the charge on the cation, the better and more
effective the coagulation. This phenomenon was worked
out by Schultze and Hardy. The Schultze–Hardy rule states
that the precipitation of a colloid is affected by that ion of
an added electrolyte, which has a charge opposite in sign to
that of the colloidal particles, and the effect of such ion
increases markedly with the number of charges it carries.
The precipitation effect of a bivalent ion is 50–60 times as
great as a monovalent ion, and that of a trivalent ion is
600–700 times as great as a monovalent ion. This is the rea-
son that aluminum and iron compounds are used as com-
mon coagulants in water and sewage treatment.
Cations or ions of opposite charge force their way
into the colloidal particles and, thus, decrease the zeta
potential and form the floc.
Trivalent salts in coagulation of water act in three
capacities: (a) Salts ionize to yield trivalent cations, some
of which reach targets and neutralize colloidal particles.
(b) Others combine with hydroxide ions and form colloid

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Chapter 8 Colloids and Coagulation

metallic hydroxides. (c) These hydroxides precipitate out,

being insoluble and in excess of the amount needed to
neutralize colloids causing color and turbidity. Sulfates
neutralize the positive colloidal metallic hydroxides
more effectively than chlorides. That is why they are pre-
ferred in water and sewage treatment.
Coagulation occurs in three steps. First, by rapid
mixing of Al+3 or Fe+3 ions, a considerable portion of the
colloids is neutralized. Second, due to aggregation, they
form microfloc, which is still invisible. Microfloc, due to
its positive charge, still attracts negative ions. At the
third stage, microfloc particles agglomerate with the for-
mation of large floc particles that can settle.

Boiling
Boiling of a hydrophobic colloidal dispersion often
results in coagulation. This is due to the modification in
the degree of hydration and higher Brownian motions,
which bring about agglomeration.

Freezing
During the freezing process, crystals of pure water
form, thus, the concentration of colloids and crystalloids
increases and coagulation occurs.

Questions
1. Define the following:
a. Colloid
b. Lyophilic
c. Zeta potential
2. Give three general properties of colloids.
3. Give common methods of precipitating colloids.
4. Explain the Schultze–Hardy rule.
5. Name various coagulants used in water and waste-
water treatment.

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BasicChemistry.book Page 73 Monday, February 18, 2002 5:03 PM

9 Water

W ater is the most abundant and most

useful liquid in nature. Surface water covers about
three-fourths of the earth’s surface. Furthermore,
there is subterranean water known as groundwater.
Water is formed of 11.11 percent hydrogen and 88.89
percent oxygen. Sixty-five percent of our body weight
is water.

Physical Properties of Water

Pure water is a colorless, odorless, and tasteless liq-
uid. The blue or bluish green tint of water is due to its
depth. Various dissolved substances, such as minerals
and gases like sulfur dioxide and chlorine, may cause
tastes and odors. Water’s freezing point is 0°C and its
boiling point is 100°C. When frozen, it expands by one-
ninth of its original volume. Therefore, the density of ice
is 0.9 g/cm3. This expansion causes bursting of some
pipes during winter. Water has a maximum density of
1g/cm3 at 4°C and, therefore, is lighter above and below
4°C. This variation of density at different temperatures
causes the stratification of lakes.
The boiling point of water depends upon the pres-
sure on its surface. The higher the pressure, the higher
the boiling point. At 15 psi pressure, water boils at
121°C. This principle is used by a pressure cooker for
quick cooking and sterilization. By lowering the pres-
sure, the boiling point is lowered for quick evaporation
of water. This principle is used for condensing milk, etc.
One litre of water forms 1,700 L of steam at normal
atmospheric pressure.

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Basic Chemistry for Water and Wastewater Operators

Structure and Properties of Water Molecules

A water molecule is formed of two atoms of hydro-
gen and one atom of oxygen bonded by polar covalent
bonds. The angle between the two bonds is 105°. Since
oxygen is more strongly electronegative than hydrogen,
there is a slight negative charge at the oxygen part and a
slight positive charge at the hydrogen parts. This polar-
ity causes water molecules to join together to form
groups of 4–8 molecules depending upon the tempera-
ture, where the hydrogen part of one molecule is weakly
bonded with the oxygen part of the other molecule, and
vice versa. This weak bonding is known as hydrogen bond-
ing. This association of water molecules results in the
higher boiling point of water as compared to other cova-
lent compounds of similar molecular weight. It also
causes an open hexagonal grouping in the ice, which
makes the water expand when frozen. At 4°C, there is
collapsing of the hexagonal pattern and the maximum
crowding of water molecules, which results in its maxi-
mum density. Above 4°C, the higher kinetic energy
pushes water molecules further apart and the density
decreases. At the boiling point, all hydrogen bonds are
broken and water molecules are free to vaporize.

Water as a Standard
Due to water’s unique physical properties and its
availability in a pure state, water is used as a standard for
several parameters.
1. Gram: Gram is mass of 1 cm3 of water at 4°C.
2. Temperature scale: Under the standard atmospheric
pressure, the freezing point of water is 0°C and the
boiling point is 100°C.
3. Calorie: It is the unit of heat. Calorie is the amount
of heat required to raise the temperature of 1 g of
water by 1°C.

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Chapter 9 Water

4. Specific gravity: Density of water is used to determine

the specific gravity of solids and liquids.

Chemical Behavior
Water is a universal solvent and it reacts with and
dissolves a large number of substances, including the
following:
1. Metals: A number of metals react with water to form
hydroxides and hydrogen gas.
2Na + 2H2O → 2NaOH + H2↑

Ca + 2H2O → Ca(OH)2 + H2↑

2. Metallic oxides: Water reacts with the soluble oxides

of metals, such as sodium, potassium, calcium, and
aluminum, to form hydroxides.
CaO + H2O → Ca(OH)2

Al2O3 + 3H2O → 2Al(OH)3 ↓

These oxides of metals are known as basic

anhydrides.
3. Oxides of nonmetals: Oxides of nonmetals react with
water to form acids.
CO2 + H2O → H2CO3

These oxides are known as acid anhydrides. Other

examples of acid anhydrides are sulfur oxides, nitro-
gen oxides, and phosphorus oxides.
4. Water of crystallization: When water is evaporated
from a solution of certain crystalline compounds, a
specific number of water molecules stays associated
with cations and anions to maintain the crystalline
state. This specific number of water molecules is
known as water of crystallization or hydration. These
crystalline compounds are called hydrates. Water of

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Basic Chemistry for Water and Wastewater Operators

crystallization is written after the formula with a

raised dot indicating the loose attachment.
For example:
Alum = Al2(SO4)3·14H2O

Copper sulfate = CuSO4·5H2O

Ferrous sulfate = FeSO4·7H2O

When a hydrate is heated above 100°C, the water is

evaporated, the crystals crumble, and the compound
becomes a dry powder known as anhydrous.
Some hydrates have a higher vapor pressure and lose
water of crystallization when exposed to the atmo-
sphere. This phenomenon is known as efflorescence. For
example, Na2CO3·10H2O (sodium carbonate dekahy-
drate) becomes Na2CO3·1H2O (monohydrate).
The opposite of efflorescence is deliquescence. Certain
hydrates, due to their lower water vapor pressure than
that of the atmosphere, will gain water when exposed to
air, e.g., calcium chloride (CaCl2) and magnesium chlo-
ride (MgCl2), which is a very deliquescent compound.
These substances are used in desiccators. Any substance
that gains moisture is known as hygroscopic.

Questions
1. Give four important properties of water.
2. Why is ice lighter than water?
3. At what temperature does water have maximum
density and why?
4. Define the following terms:
a. Water of crystallization
b. Deliquescence
c. Efflorescence

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Chapter 9 Water

5. Why does water have a higher boiling point than

other covalent compounds with about the same
molecular weight?
6. Complete and balance the following equations:
a. SO2 + H2O →
b. Na + H2O →
c. CaO + H2O →

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BasicChemistry.book Page 79 Monday, February 18, 2002 5:03 PM

10 Ionization Theory

I
onization theory deals with
ion formation by electrolytes and the behavior of their
solutions. Ionic compounds and acids conduct electric-
ity in their water solutions and are known as electrolytes;
whereas, covalent compounds (other than acids) do not
conduct electricity in their water solutions and are called
nonelectrolytes. Because electrolytes exist as ions (their
cations move toward the negative pole and anions,
toward the positive pole), electricity is conducted. Non-
electrolytes do not form ions in their solutions and they
do not conduct electricity.
Some common examples of electrolytes are sodium
chloride (NaCl) and sulfuric acid (H2SO4), while non-
electrolytes include sugars and various other organic
compounds.
Michael Faraday (1791–1867), an English chemist,
first observed that conducting solutions have charged
particles. He named these charged particles ions (wan-
derer) and thought they were produced by electrodes. He
also coined the terms electrolytes and nonelectrolytes.
The Swedish scientist Svante Arrhenius published a
report, in 1887, on the theory of ionization. He consid-
ered ions to be electrically charged and formed by ioniza-
tion of molecules.
In modern theory, the solvent has an important role
in the solution process. The polar covalent nature of
water molecules is very important in understanding ion
formation.

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Assumptions of Modern Theory

1. An electrolyte in solution forms ions.
2. An ion is an atom or a radical that carries a charge.
3. A water solution of an electrolyte carries an equal
number of positive and negative charges.

Dissociation of Ionic Compounds

In forming ions, atoms become electrically charged
to gain chemical stability. Ionic compounds exist as crys-
tals made up in an orderly manner, with every anion
close to a cation.
When some crystals of sodium chloride (NaCl) are
dropped into a beaker of water, water dipoles exert an
attractive force on the ions of the surface layer of the
crystal. The negative oxygen poles of a number of water
molecules associate with the sodium cations (Na+). Sim-
ilarly, the positive hydrogen part of water molecules is
attracted by the chloride (Cl–) anions. The association of
water molecules with the ions is known as hydration of
ions. These ions are then separated from the crystals and
diffuse throughout the solution, loosely bonded to the
water molecules.
Sodium chloride is said to be dissociated when it is
dissolved in water (see Figure 10-1). The symbol for solid
is “s”; for liquid, “l”; and for gas, “g.” We can represent
dissociation of sodium chloride (NaCl) as

NaCl (s) → Na+ (aq) + Cl– (aq)

The number of water molecules needed for dissociation
of an ion depends upon the size and charge of the ion.
The more the charge and the heavier the ion, the greater
the number of water molecules needed for its dissocia-
tion. Water molecules are interchanged from ion to ion
and from ion to solvent. In certain cases, water mole-
cules are not involved in reforming the crystal structure

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Chapter 10 Ionization Theory

+ –
Na Cl

+
–
+ –
+
+ –
+
+ + +
–
+ –
+
+

+ –

+
–
+

+
–

++

–
–

+
+

+
–
–

+
+
+

+
+ + +
– –

Hydrated Sodium Ion Hydrated Chloride Ion

Figure 10-1 Dissociation of Sodium Chloride

after the evaporation of solvent (e.g., sodium chloride

(NaCl)). However, in case of hydrates, a specific number
of water molecules is retained by the ions in forming the
crystal, which is known as water of crystallization (dis-
cussed in chapter 9). Extensive hydration of the solute
ions ties up a large number of water molecules. This
reduces the number of free water molecules in the spaces
separating hydrated ions of opposite charge. The attrac-
tion between ions of opposite charge becomes stronger
and crystals begin to form again. The saturation point is
reached as the rate of dissolving equals the rate of
crystallizing.
Some ionic compounds are only slightly soluble
because a large number of water molecules is required to
separate their ions, e.g., silver chloride (AgCl), calcium
carbonate (CaCO3), magnesium hydroxide (Mg(OH)2),

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Basic Chemistry for Water and Wastewater Operators

and aluminum hydroxide (Al(OH)3). These are known as

insoluble compounds.
Both silver nitrate (AgNO3) and sodium chloride
(NaCl) are soluble in water, whereas silver chloride
(AgCl) is only slightly soluble. Ag+ (aq) + Cl– (aq) ions
will be present only in a very small number in a saturated
solution of AgCl.
If concentrated solutions of NaCl and AgNO3 are
mixed, there will be four types of ions in a single solu-
tion environment: Na+, Cl–, Ag+, and NO3–.

NaCl (s) Na+ (aq) + Cl – (aq)

= precipitate
AgNO3 (s) Ag+ (aq) + NO3– (aq)

The concentration of Ag+ (aq) and Cl– (aq) will

greatly exceed the solubility of AgCl. All Ag+ and Cl– in
excess of a saturated solution will separate from the solu-
tion as a precipitate of a solid, AgCl. The separation of a
solid from a solution is called precipitation. As Na+ + NO3–
did not take any part in the reaction, they are known as
spectator ions. This reaction can be shown as a simplified
equation:
NaCl + AgNO3 → AgCl↓ + NaNO3

This is the basis of ionic or double-replacement reac-

tions. This principle is used in the flocculation and soft-
ening of water.
Al2(SO4)3 + 3Ca(OH)2 → 2Al(OH)3↓ + 3CaSO4

CaSO4 + Na2CO3 → CaCO3↓ + Na2SO4

MgSO4 + Ca(OH)2 → Mg(OH)2↓ + CaSO4

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Chapter 10 Ionization Theory

+ + H Cl –

–
+

–1
+ +1
Cl
+

H3O+ Cl –

Figure 10-2 Ionization of Hydrochloric Acid

Ionization of Polar Covalent Compounds (Acids)

Acids are polar covalent compounds having the
hydrogen part of the molecule with a positive pole and
the other part with a negative pole.
The covalent bond is generally a strong bond. How-
ever, when acid molecules are in water, the association
of water molecules weakens the bond enough to pull the
molecule apart. The hydrogen part separates as hydro-
gen ion (H+), which associates with a water molecule to
form a hydronium ion (H3O+), while the rest of the acid
molecule forms an anion.
The ions did not exist in the undissolved acid but
were formed by the action of water. This process of ion
formation from the polar covalent solutes by the action
of water molecules is known as ionization (see
Figure 10-2).
Acids that ionize completely in water are known as
strong acids and those that ionize poorly are called weak
acids.
Acetic acid:
99% 1%
–
H C2H3O2 + H2O H3 O+ + C2H3O2 weak

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Basic Chemistry for Water and Wastewater Operators

Hydrochloric acid:
1% 99%
HCl + H2O H3O+ + Cl– strong

Strong and weak refer to the degree of ionization,

and dilute and concentrated refer to the amount of acid
dissolved in the solvent.

Ionization of Water
Water, being a polar covalent compound, ionizes
very poorly to form hydronium (H3O+) and hydroxide
(OH–) ions. This low concentration of ions, however, is
insignificant when compared with electrolytes such as
NaCl and H2SO4. Therefore, for all practical purposes,
pure water is considered a nonelectrolyte.

H2O + H2O H3O+ + OH–

Nonelectrolyte covalent compounds that do not

ionize have very little (0 to 0.4) electronegativity differ-
ence between combined atoms and, thus, they are not
affected by water molecules to form ions.

Effects of Electrolytes on the Freezing and Boiling Points of

the Solvent
The freezing and boiling points depend on the num-
ber of particles in the solution. The higher the number
of particles, the lower the freezing point and the higher
the boiling point. An electrolyte ionizes and contributes
two, three, or more times the number of particles than a
nonelectrolyte. Electrolytes, therefore, are correspond-
ingly more effective than nonelectrolytes in lowering
the freezing point and raising the boiling point of the
solvent. One Avogadro number of solute particles per
kilogram of water raises the boiling point by about
0.52°C and lowers the freezing point by 1.86°C.

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Chapter 10 Ionization Theory

Electrolysis and Ionization

Electrolysis is the decomposition of a substance with
electricity. Because water ionizes only slightly in the
decomposition of water, additional ions must be pro-
vided for an adequate conduction of electricity between
the electrodes. Sulfuric acid (H2SO4) is used for this pur-
pose. Any substance that forms ions can undergo elec-
trolysis, e.g., water and ionic compounds.
In the electrolysis of water when electrodes are con-
nected to a source of direct current, OH– and SO4= ions
start going to the anode (positive pole) and H3O+ to the
cathode (negative pole).
H3O+ gains an electron and combines with another
H3O+ ion to form H2O and H2; 4OH– ions lose an elec-
tron each and form two molecules of H2O and O2.

2H3+O + 2e– → 2H2O + H2↑ at cathode

4OH– – 4e– → 2H2O + O2↑ at anode

O2 is liberated at the anode in preference to other non-

metallic ions and H2 in preference to metallic ions at the
cathode.
Electrolysis of sodium chloride (NaCl) yields sodium
at the cathode and chlorine at the anode (Figure 10-3).

Cathode Anode

– +
Na Cl2
Na+ Cl – –
Cl
Na+ Na+ Na+
–
Cl –
Na
+ Cl
–
+ – Cl
Na Cl

Figure 10-3 Electrolysis of Sodium Chloride

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Basic Chemistry for Water and Wastewater Operators

Questions
1. Define the following:
a. Electrolyte
b. Nonelectrolyte
c. Ionization
d. Dissociation
e. Precipitation
2. What is the effect of the dissolved electrolytes and
nonelectrolytes on the boiling point and the freezing
point of water?
3. Give three assumptions of the ionization theory.

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11 The Gas Laws

G
as is the lightest, thinnest,
and most fluid form of matter. Gases pass through each
other more easily than do other forms of matter.

Kinetic Theory
The particles composing all matter are atoms, mole-
cules, or ions. Kinetic theory helps explain the properties
of gases, liquids, and solids in terms of the forces
between the particles of matter and the energy they
possess.
There are three basic assumptions of the kinetic
theory:
1. Matter is composed of very tiny particles. The chem-
ical properties of these particles depend on their
composition. Their physical properties depend on
the forces they exert on each other and the distance
separating them.
2. These particles of matter are in constant motion.
Their average energy of motion depends on temper-
ature. The higher the temperature, the greater the
energy.
3. The particles of matter do not lose energy in colli-
sions. Collisions with each other or with walls of a
container are perfectly elastic.
We can explain the behavior or properties of gases
using the kinetic theory.

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Properties of Gases
1. Expansion: Gases do not have a definite volume or a
definite shape. All gases are made of millions of tiny
particles that move freely at random. As these parti-
cles are widely separated, they travel in random
directions at a high speed of about 103 m/sec. They
undergo about 5.0 × 109 collisions per second. Mat-
ter in a gaseous state occupies about 1,000 times
more volume than in a solid or liquid state. One mL
of gas contains about 3.0 × 1019 molecules. An ordi-
nary molecule is about 4 Å in diameter. They are
about 40 Å apart.
2. Pressure: Gases exert pressure. Pressure is due to the
bombardment of molecules with the walls of the
container. If we put more gas molecules in the same
space, there will be more bombardment and, thus, a
higher pressure. If the temperature is raised, more
kinetic energy causes higher pressure.
3. Low density: The density of a gas is very low. It is
about 10–3 times the density of the same substance
in a liquid or solid state.
4. Diffusion: The spontaneous scattering of the gas mol-
ecules to fill a space uniformly is diffusion. Gases,
therefore, do not have a definite volume or shape. If
the stopper of an ammonia bottle is removed, its irri-
tating smell is evident throughout the room rather
quickly. This is due to the diffusion of ammonia
molecules, which are spaced well apart and are inde-
pendently moving in all directions.
5. Plasma: A gas at a very high temperature or by pass-
ing an electric current becomes ionized into elec-
trons and protons and is known as plasma, the
fourth state of matter.

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Chapter 11 The Gas Laws

Henry’s Law
The mass of a dissolved gas in a liquid is directly pro-
portional to the pressure of the gas in contact with the
liquid at a constant temperature. Due to lower atmo-
spheric pressure at an elevation of 9,642 ft, solubility of
oxygen at 20°C in the surface water is 6 mg/L. At sea level
at the same temperature, it is 9.17 mg/L.
Mathematically,

S 1 P = SP 1 or

S S
-----1- = ---
P1 P

where:
S = solubility at pressure P
S1 = solubility at pressure P1

Suppose the solubility of a gas at 1 atmospheric pres-

sure is 5 mg/L, its solubility at 3 atmospheric pressure
will be 15 mg/L at a constant temperature.

Graham’s Law of Diffusion

The rate of diffusion of a gas is inversely propor-
tional to the square root of its molecular weight. There-
fore, the lower the molecular weight of a gas, the faster
it will diffuse.
Mathematically,

V1 m
------ = -------2-
V2 m1

where:
V1 = rate of diffusion of a gas, with molecular weight m1
V2 = rate of diffusion of a gas, with molecular weight m2

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Basic Chemistry for Water and Wastewater Operators

Assume hydrogen diffuses at a rate of 1,000 m/sec.

What will be the rate of diffusion of oxygen? Substitut-
ing these values in the formula, the rate of diffusion of
oxygen would be 250 m/sec if V1 and m1 are of hydrogen
and V2 and m2 of oxygen.

1,000 32
--------------- = ------ or
V2 2

1,000
--------------- = 4 or
V2

1,000
V2 = --------------- m/sec = 250 m/sec
4

Dalton’s Law of Partial Pressure

The total pressure of a mixture of gases is the sum of
their partial pressures. Gases are generally collected by
displacing water in a tube closed at the upper end. This
tube is known as an eudiometer. Pressure exerted by a gas
is a pressure due to gas and water vapor at that tempera-
ture. To determine the pressure of the dry gas, the vapor
pressure of water is subtracted from the total pressure.
Suppose a gas collected over water exerts 750 mm of mer-
cury pressure at 20°C; the pressure due to gas alone or
dry gas would be 750 minus 17.5 mm Hg (the water
vapor pressure at 20°C) or 732.5 mm of Hg.

Boyle’s Law
The volume of a dry gas is inversely proportional to
the pressure at a constant temperature. It means the
higher the pressure, the lower the volume.
Mathematically,

V P
------1 = ------ or
V P1

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Chapter 11 The Gas Laws

P
V 1 = ------ × V
P1

where:
V1 = volume corresponding to pressure P1
V = volume corresponding to pressure P

Suppose 200 mL of a dry gas exerts 740 mm Hg pres-

sure. What will be the volume if pressure changes to
750 mm Hg?
Substituting these values in the equation:

740
V 1 = ---------- × 200 mL = 197.33 mL
750

Charles’s Law
The volume of a dry gas is directly proportional to
the absolute temperature at a constant pressure.
Mathematically,

V1 T
------ = -----1- or
V T

T1
V 1 = ------ × V
T

where:
V1 = new volume
T1 = new temperature
V = original volume
T = original temperature

Example: If a gas measures 500 mL at 20°C, what will

be its volume at 0°C?

273 + 0
V 1 = ----------------------- × 500 = 466 mL
273 + 20

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Boyle’s and Charles’s laws combined can be

expressed mathematically as

V1 P T1
------ = ------ × ------
V P1 T

Now we can determine any one of the six values by

knowing the other five.

Gay-Lussac’s Law of Combining Volumes of Gases

Under similar conditions of temperature and pres-
sure, the volumes of reacting gases and of their gaseous
products are expressed in a ratio of small whole num-
bers. This ratio is the same as that of the molecules in the
balanced equations.

2H2 + O2 → 2H2O

2 vol : l vol : 2 vol

HCl + NH3 → NH4Cl

1 vol : l vol : 1 vol

Avogadro’s Hypothesis
Equal volumes of gases under similar conditions of
temperature and pressure contain the same number of
molecules. Note that 22.4 L of most of the gases contain
an Avogadro number of their molecules (1 mol) at the
standard temperature (0°C) and standard pressure
(760 mm Hg). Therefore, 22.4 L is known as molar or
gram molecular volume. Density of a gas is the mass in
grams per litre at standard temperature and pressure
(STP); therefore, it is the mole of a gas divided by 22.4 L.

32 g
Density of O2 = ----------------- = 1.43 g/L
22.4 L

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Chapter 11 The Gas Laws

Using this principle, the molecular weights of gases

may be determined if the mass of some volume of a gas
and conditions are specified.
Example: A sample of a certain gas measured at 20°C
and 757.5 mm Hg pressure weighs 2 g and its volume is
300 mL. What is its molecular weight? Water vapor pres-
sure at 20°C is 17.5 mm Hg.
Using equation

V1 P T1
------ = ------ × ------
V P1 T

where:
V = 300 mL
P = 757.5 – 17.5 mm Hg
P1 = 760 mm Hg
T = 273 + 20°A
T1 = 273°A

740 273
Volume at STP = ---------- × ---------- × 300 = 272 mL
760 293
2.0 g
Gram molecular mass = ------------- × 22.4 × 1,000 = 164 g
272
Molecular weight = 164

Questions
1. Give properties of gases.
2. Which one of the following gases will diffuse the
fastest?
a. Chlorine (Cl2)
b. Carbon dioxide (CO2)
c. Hydrogen sulfide (H2S)
3. A sample of a gas measures 500 mL at standard con-
ditions. What is its volume at 20°C and 750 mm Hg
pressure?

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Basic Chemistry for Water and Wastewater Operators

4. Calculate the density of methane (CH4).

5. Calculate the molecular weight of a gas weighing 3 g
and measuring 700 mL at 10°C and 700 mm mercury.

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12 Organic Chemistry

T
his branch of chemistry
deals with the compounds of carbon, both natural and
synthetic, and their derivatives. Originally, it was limited
to substances found in and produced by plants and ani-
mals. In 1828, Friedrick Wohler obtained urea, an
organic compound, by heating potassium cyanate
(KCNO) with ammonium sulfate ((NH4)2SO4).

O
2KCNO + (NH4)2SO4 → K2SO4 + 2H2N–C–NH2
urea

Since then, synthesis of various kinds of organic

compounds started. Organic chemistry is important in
water and wastewater treatment because organics are
decomposed in wastewater treatment and removed in
water treatment.
As compared to inorganic substances, organics have
the following characteristics:
1. They are generally combustible.
2. They have a lower melting point and boiling point.
3. They are less soluble in water.
4. They have isomerism, meaning the existence of a
number of compounds with the same molecular for-
mula but different structural formulae.
5. They are mostly covalent compounds.
6. They have high molecular weight, often over 1,000.
7. Most serve as a source of food for bacteria.

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Basic Chemistry for Water and Wastewater Operators

Carbon Atoms and Bonding

A carbon atom does not give or take electrons in the
compound formation. It shares electrons and forms
covalent bonds. It has the tendency to share electrons
with other carbon atoms to form chains. That is why
organic compounds are covalent with high molecular
weight. Each carbon atom has four valence electrons and
shares four from other atoms; thus, there are four cova-
lent bonds with each carbon atom in the organic com-
pounds. The angle between every two bonds is 109.28°,
and all four bonds are equally strong.
In a chain of carbon atoms, there can be single, dou-
ble, or triple covalent bonds.

H H
H–C–C–H, C2H6 = ethane has single bonds
H H

H H
H–C=C–H, C2H4 = ethene has a double bond

H–C≡C–H, C2H2 = ethyne or acetylene has a triple bond

Due to isomerism, in organic chemistry, structural

formulae rather than molecular formulae are used. As
most of the organic compounds are formed of carbon,
nitrogen, oxygen, and hydrogen, these elements have
four, three, two, and one covalent bonds, respectively.

–C– –N– –O– –H

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Chapter 12 Organic Chemistry

For example, in urea:

H O H
N–C–N
H H

Classification of Organic Compounds

For our purpose, organic compounds can be divided
into four main classes: hydrocarbons, carbohydrates, lip-
ids, and proteins. The last three groups are known as nat-
ural organic compounds.

Hydrocarbons
Hydrocarbons are compounds formed of hydrogen
and carbon only. They are straight chain, branched
chain, or ringed in their molecular structure. Open-
chain hydrocarbons are classified into different series, as
shown in Table 12-1.

Alkane Alkene
(Paraffin) (Olefin) Alkyne
Alkyl Group Series Series Series Alkadiene

Methyl, CH3– Methane, CH4

Ethyl, C2H5 – Ethane, C2H6 Ethene, C2H4 Ethyne, C2H2

Propyl, C3H7– Propane, C3H8 Propene, C3H6 Propyne, C3H4

Butyl, C4H9– Butane, C4H10 Butene, C4H8 Butyne, C4H6 Butadiene, C4H6

Pentyl, C5H11– Pentane, C5H12 Pentene, C5H10 Pentyne, C5H8 Pentadiene, C5H8

Hexyl, C6H13– Hexane, C6H14 Hexene, C6H12 Hexyne, C6H10 Hexadiene, C6H10

Table 12-1 Hydrocarbon Series

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Alkane Series
The alkane series are straight- or branched-chain
hydrocarbons with single covalent bonds in between
carbon atoms. The general formula for them is CnH2n+2
where n = number of C atoms in the chain.

H H H H
n. Butane, H–C–C–C–C–H, C4H10
H H H H

Because the most common bonding of carbon atoms is

with hydrogen atoms, sometimes hydrogen is not writ-
ten in the formula; e.g., methane,

H
H–C–H
H

may be written as

–C–

An unbranched chain is indicated by “n.” in front of

the name of the hydrocarbon, e.g., n. butane.

Alkene Series
The alkene series are straight- or branched-chain
hydrocarbons in which there is a double bond in the
molecule. For example:

H H
Ethene (C2H4) is H–C=C–H

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Chapter 12 Organic Chemistry

H H H H H H
Hexene (C6H12) is H–C–C–C=C–C–C–H
H H H H

A double bond will reduce the number of hydrogen

atoms by two; therefore, the general formula for the alk-
ene series is CnH2n.

Alkyne Series
The alkyne series are straight- or branched-chain
hydrocarbons with a triple bond in between carbon
atoms in the chain. Because a triple covalent bond
reduces the number of hydrogen atoms by 4, the general
formula is CnH2n–2.
Ethyne or acetylene, H–C≡C–H, C2H2

Alkadiene Series
The alkadiene series differ from the other series by
having two double bonds in the chain. For example,
butadiene is

H H H H
C=C–C=C, C4H6
H H

Its general formula, like alkyne, is CnH2n–2.

Benzene Series or Aromatic Series

These hydrocarbons have a benzene ring(s). A ben-
zene ring is a hexagonal ring, with each corner repre-
sented by a carbon atom with alternating double bonds.

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H
C
H C C H
Benzene (C6H6), or simply
H C C H
C
H

Benzene is prepared commercially by the distillation of

coal tar. Because benzene has a pleasant aromatic odor,
its compounds are known as aromatic hydrocarbons
(e.g., naphthalene and anthracene).

H H
—

—
C — —C—
H—C —
— C C—H
—

—
—

or simply
H—C—
— C— C—H
C— C—
—
—
—

H H
Naphthalene, C10H8

H H H
—

C—
— C—
— C—
—
H—C — C— C — C—H
—

H—C — C C C—H
— — — — —
C C C
—
—

H H H
Anthracene, C14H10

When other groups replace hydrogen atoms in benzene

molecules, the compounds are named as ortho, meta, and
para, for bonding with consecutive carbon atoms, alter-
nate carbon atoms, and opposite carbon atoms, respec-
tively. For example, two methyl groups (CH3–) with the
benzene ring form a xylene that is an ortho, meta, and
para type depending on the position of the bonds.

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Chapter 12 Organic Chemistry

CH3 CH3

CH3
CH3 CH3
CH3
Ortho-xylene Meta-xylene Para-xylene
The molecule of a hydrocarbon with one hydrogen
replaced is known as an alkyl group in an alkane series
and a phenyl group in a benzene series. They are repre-
sented in the general formula by “R.”

H
H
H H
H
Phenyl (C6H5–)

Derivatives of Hydrocarbons
These compounds are produced by the substitution
of hydrogen in the hydrocarbon compounds by other
groups known as functional groups (shown in Table 12-2).

Alcohols
They are hydrocarbons with one or more hydrogens
replaced by a hydroxyl (–OH) group. Their names end
with -nol.

H
Methanol, H–C–OH , CH3OH
H

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Derivative General Formula Name (Trivial, IUPAC*)

Alcohol R–OH Ethyl alcohol, Ethanol

Ether R–O–R Diethyl ether, Ethoxyethane

Aldehyde O Acetyldehyde, Ethanal

Formaldehyde, Methanal
R–C–H

Ketone O Acetone, Propanone

R–C–R

Acid† O Formic acid, Methanoic acid

Butyric acid, Butanoic acid
R–C–O–H
Valeric acid, Pentanoic

Ester† O Ethyl acetate

Glyceryl trinitrate
R–C–O–R

Amines† R–NH2 Propylamine

Methyl ethyl amine
Methyl ethyl n. propylamine

Amides† OH Acetamide
R–C–N–R

Chloroorganics† R–Cl(s) Trichloromethane

Chlorobenzene

* International Union of Pure and Applied Chemistry.

† Have trivial names, generally.

Table 12-2 Derivatives of Hydrocarbons

H H
Ethanol, H–C–C–OH , C2H5OH
H H

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Chapter 12 Organic Chemistry

Ethers
They are organic oxides. They are derivatives of
water in which both hydrogen atoms are replaced by
alkyl groups.

H H H H
H–C–C–O–C–C–H , C2H5OC2H5
H H H H

Diethyl ether or ethoxyethane

Aldehydes
They have a hydrogen of the hydrocarbon replaced
by the formyl groups,

O
–C–H

O
Methanal or formaldehyde H–C–H , CH2O

Their technical names end with -al, e.g., methanal and

ethanal.

Ketones
These compounds have hydrocarbon hydrogen,
replaced by a carbonyl group

O
–C–

Their names end with -one. For example, propanone or

acetone is

O
H3C–C–CH3

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Acids
All organic acids have a carboxylic group (–COOH)
substituting hydrogen atom(s). Their names end with
-noic. For example:

O
Methanoic (formic) acid, H–C–OH

O
Butanoic acid, H7C3–C–OH

Esters
They are produced when acids react with alcohols. A
water molecule is produced when an acid group reacts
with an alcohol group. Bonding between an acid and
alcohol molecule is known as esterification. Ethyl acetate
is the product of ethyl alcohol and acetic acid.

C2H5 – OH + CH3COOH CH3COOC2H5 + H2O

O H H H
–

–
–
=

CH3COO C2H5 = H–C–C–O–C–C–H

–

–
–

H H H

Esterification

Amines
They are derivatives of ammonia in which one, two,
or all three hydrogen atoms of the ammonia molecule are
replaced by alkyl groups. For example, propylamine is

H
C2H5–N , C2H5NH2
H

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Chapter 12 Organic Chemistry

Amides
They are formed when an amine is bonded with a
carboxylic group (–COOH) of an acid. For example, in
proteins where –COOH of one amino acid is bonded
with the amine (NH2–) group of another. The bond
formed is known as an amide bond:

H H CH3
O

–
–
=
H2N – C – C – N – C – COOH

–
–
H H
Amide bond
Glycine Alanine

Chloroorganics
A large number of chloroorganic compounds are
formed when chlorine reacts with hydrocarbons and
replaces hydrogen. They have health effects and are con-
taminants of drinking water (see Figure 12-1). Some
important chloroorganic classes are volatile organics and
chlorine disinfection by-products.

Carbohydrates
Carbohydrates contain the elements carbon, hydro-
gen, and oxygen. Hydrogen and oxygen atoms in all car-
bohydrates are in a 2:1 ratio as in water; therefore, the
name is carbohydrates. Sugars, starches, celluloses, and
substances closely related to them are all naturally occur-
ring carbohydrates. Most common carbohydrates have
proved to be condensation polymers (formed of several
molecules of a simple compound) of simpler molecular
sugar units, known as monosaccharides, or simple sug-
ars. Glucose, galactose, and fructose are simple sugars.
They are isomers with a molecular formula of C6H12O6.
Formulas are simplified by omitting C and H, except in
glucose, for clarification.

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Cl O

—
—
—
Cl C — C — CH3
H
—

—
—
C—
— — Cl H
Cl Cl
Chloroform, Dichloropropanone
Trichloromethane
NO2

—
Cl Cl Cl — C — Cl

—
—

C—
—C
Cl
—

Cl H Chloropicrin,
Trichloroethylene
Trichloronitromethane

Cl — C —
—N
Cyanogenchloride
H H
—

C
—

Cl Cl
Methylenechloride,
Cl —
Dichloromethane

Monochlorobenzene
N
—
—
—

C Cl
—

Cl — C — Cl
—

Cl —
Cl

Trichloroacetonitrile Orthodichlorobenzene

Figure 12-1 Some Chloroorganic Contaminants of Drinking

Water

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Chapter 12 Organic Chemistry

CH2OH

—
C O

—
H H
H

—
C C

—
OH H

—
HO OH

—
—
C C

—
H OH
Glucose

CH2OH
——

O
OH
— —

——

OH
OH
——
——

OH
Galactose

O
HOCH2
—

—
—

HO HO CH2OH
——
——

OH

Fructose

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Disaccharides
Two monosaccharides combine to form a disaccha-
ride and a water molecule. Examples of disaccharides are
sucrose, maltose, and lactose. Glucose and fructose form
sucrose, glucose and glucose form maltose, and glucose
and galactose form lactose.

CH2OH
O
HOCH2 O

HO
HO OH
CH2OH

OH O OH
Sucrose

CH2OH CH2OH
O O
OH

HO OH OH
O
OH OH
Maltose

OH CH2OH
O
OH
OH
OH
OH
O O
CH2OH OH
Lactose

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Chapter 12 Organic Chemistry

Polysaccharides
Polysaccharides are formed when several monosac-
charides combine together. Three common polysaccha-
rides are starch, cellulose, and glycogen. They are
polymers of glucose.

CH2OH CH2OH CH2OH

O O O

OH OH OH
O O O O
OH OH OH
Starch: A Polymer of “α” Glucose

CH2OH OH CH2OH
O
O O O
OH
OH OH
O O O
OH CH2OH OH
Cellulose: A Polymer of “β” Glucose

Disaccharides yield two simple sugars by taking one

molecule of water. Polysaccharides react with water to
produce many monosaccharides. This decomposition
with water is known as hydrolysis.

Lipids
Lipids are mainly fats and oils that contain the same
elements (C, H, O) as carbohydrates but have compara-
tively less oxygen. Upon hydrolysis, fats yield fatty acids
and glycerol. They are esters of glycerol and long-chain
fatty acids, usually with an even number of C atoms,
from 12–20. Lipids are found in animal and plant tissue.
They are insoluble in water and soluble in solvents, such
as ether, chloroform, or benzene.

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O O

=
H2C–O–C–C17H35 H2C–O–C–C17H33
O O

–
=

=
HC–O–C–C17H35 HC–O–C–C17H33

–
H2C–O–C–C17H35 H2C–O–C–C17H33

=
O O
Stearin, a fat Olein, an oil
Glycerol + Stearic Acid Glycerol + Oleic Acid
melting point = 71oC melting point = –4oC

The molecular structure in fats and oils is the same.

Oils are liquid at room temperature due to the presence
of some double bonds (unsaturated) in the carbon chain
of their fatty acids that lowers the melting point. Fats
have single bonds (saturated) and are solid at room
temperature.

Saponification
Saponification is the hydrolysis of a lipid by using a
solution of a strong hydroxide to form soaps.

H2C–COO–R

HC–COO–R1 + 3NaOH → RCOONa + R1COONa + R2COONa + C3H5(OH)3

soap
H2C–COO–R2

Soaps are generally made by hydrolyzing fats and

oils with superheated water at about 250°C under a pres-
sure of about 50 atmospheres. The long-chain carboxylic
acids formed are neutralized with sodium hydroxide to
yield a mixture of sodium salts, which constitutes soap.

Hydrogenation
Hydrogenation is the conversion of an oil into a fat.
This is achieved by adding hydrogen to the unsaturated
fatty acid and making it saturated. The hydrogenation is

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Chapter 12 Organic Chemistry

controlled so that the resulting product is not com-

pletely saturated.

… –C–C=C–C– … … –C–C–C–C– …

C17H33 COOH + H2 → C17H35 COOH

Oleic acid Stearic acid

Proteins
Proteins contain carbon, hydrogen, oxygen, and
nitrogen. Some proteins also contain sulfur (S) and
phosphorus (P) as additional elements. They are known
as nitrogenous organics. They are formed of chains of
amino acids linked by amide bonds. Hydrolysis of pro-
teins yields amino acids. An amino acid contains both
–NH2 and –COOH groups.
The general formula of an amino acid and a protein is

R
|
H2N–C–COOH
|
H
Amino acid

R O R O R O
H2N–C–C–N–C–C–N–C–C– …
H H H H H
Amide bond
Protein
Proteins form two-thirds of the dry weight of all liv-
ing cells. While fats and carbohydrates are used mainly
as sources of energy, proteins are involved in a variety of
living activities of the cell. Some examples of proteins
are the white of an egg, enzymes, hormones, and anti-
bodies. They are the main component of nails, hair, and
muscles. Proteins have a key position in the architecture

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and functioning of living matter. Protein means preemi-

nent or first in Greek.

Classification of Proteins
Proteins can be classified into three groups:
Simple proteins: They yield only amino acids on
hydrolysis, e.g., egg albumin.
Conjugated proteins: They are combined with a char-
acteristic nonamino acid substance, e.g., glycoproteins,
lipoproteins, nucleoproteins, and phosphoproteins.
Derived proteins: They are the products derived from
either the simple or conjugated proteins. Proteins, when
digested, form peptides, amino acids, and ammonia.
Polypeptides → Dipeptides → Amino acids → Ammonia
The amount of heat produced by the oxidation of
fats, carbohydrates, and proteins is approximately 9.3,
4.1, 4.1Kcal/g, respectively. Lipids and carbohydrates are
oxidized completely to H2O and CO2, while proteins
undergo incomplete oxidation and some end products
still contain C and H and, thus, some energy. End prod-
ucts of proteins are ammonia and hydrogen sulfide,
which are finally oxidized to nitrates and sulfates.

Questions
1. Give the differences between organic and inorganic
compounds.
2. Define:
a. Isomerism
b. Ether
c. Esterification
d. Saponification

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Chapter 12 Organic Chemistry

3. Give the general formulae of the following:

a. Alcohol
b. Carboxylic acid
c. Aldehyde
d. Ketone
e. Amino acid
4. Differentiate:
a. Carbohydrate from a hydrocarbon
b. Fat from oil
c. Monosaccharides from disaccharides
d. Simple protein from a conjugated protein

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BasicChemistry.book Page 115 Monday, February 18, 2002 5:03 PM

13 Hardness

H
ardness is caused by the
presence of dissolved calcium and magnesium com-
pounds. In natural waters, it varies considerably depend-
ing on the source. Areas with limestone (CaCO3) and
dolomite (CaCO3 and MgCO3) deposits have more hard-
ness than others. Hardness results in an increased con-
sumption of soap. The harder the water, the higher the
consumption of soap, and vice versa. Commonly, hard-
ness is caused by the bicarbonates (HCO3–), sulfates
(SO4=), nitrates (NO3–), and chlorides (Cl–) of calcium
and magnesium.
Rainwater usually contains carbon dioxide, CO2, in
solution as carbonic acid, H2CO3. As this water percolates
through deposits of limestone and dolomite, some of
these carbonates are converted into soluble bicarbonates.
CaCO3 + H2CO3 → Ca(HCO3)2

Rainwater also dissolves sulfates and chlorides of cal-

cium and magnesium. The presence of other metals such
as iron (Fe) and manganese (Mn) may also cause hard-
ness. Waters are classified into various types depending
on the degree of hardness.

Hardness Water
15–50 mg/L as CaCO3* Soft
50–100 mg/L as CaCO3 Medium hard
100–200 mg/L as CaCO3 Very hard
*Units mg/L (ppm, parts per million) are expressed as CaCO3,
meaning equivalent to CaCO3.

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Lather Formation and Hardness

Common washing soap is a water-soluble salt of
sodium and a fatty acid, e.g., sodium stearate
(NaC18H35O2).
When soap is added to hard water, it reacts with the
calcium and magnesium compounds to form insoluble
compounds, the scum or curd, that deposit on clothes.
CaSO4 + 2NaC18H35O2 → Ca(C18H35O2)2↓ + Na2SO4
scum
This reaction continues until all the calcium and
magnesium ions are precipitated. Soft water does not
contain these ions and, therefore, lathers easily when
soap is added.

Types of Hardness
1. Carbonate or temporary hardness is commonly due
to bicarbonates (HCO3–) of calcium and magnesium
and sometimes due to their carbonates. It is common
in areas with limestone and dolomite deposits. It is
considered “temporary” because it can be removed
by boiling the water.
2. Noncarbonate or permanent hardness is caused by
soluble compounds such as sulfates (SO4=), nitrates
(NO3–), and chlorides (Cl–) of calcium and magne-
sium. These compounds are more stable in their
solutions than bicarbonates. They cannot be
removed by boiling the water.

Problems Due to Hardness

1. It is a nuisance in laundering, due to the wasting of
soap and the collecting of precipitate on fibers.
2. It is a nuisance in bathing.

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Chapter 13 Hardness

3. It causes the formation of a scale inside steam boil-

ers. The scale is formed by the carbonate hardness. It
may act as a heat insulator, preventing proper trans-
fer of heat.

Softening Methods

Boiling
Boiling removes carbonate hardness. Bicarbonates
are converted into insoluble carbonates.
Ca(HCO3)2 → CaCO3↓ + H2O + CO2↑

Precipitation
Precipitation is the addition of basic solutions such
as Ca(OH)2 or NH4OH to form CO3= and H2O from
bicarbonates. Magnesium carbonate (MgCO3) is further
reacted with Ca(OH)2 to precipitate magnesium hydrox-
ide (Mg(OH)2).
Ca(HCO3)2 + Ca(OH)2 → 2CaCO3↓ + 2H2O

Mg(HCO3)2 + Ca(OH)2 → MgCO3 + CaCO3↓ + 2H2O

MgCO3 + Ca(OH)2 → Mg(OH)2↓ + CaCO3↓

The removal of magnesium carbonate hardness

requires double the amount of lime and pH above 10.6;
whereas, calcium is removed above pH 9.4.
Lime (Ca(OH)2) and sodium carbonate (Na2CO3) or
soda ash are added to remove noncarbonate hardness.
Calcium and magnesium precipitate out as insoluble car-
bonate and hydroxide, respectively.
CaSO4 + Na2CO3 → CaCO3↓ + Na2SO4
MgSO4 + Ca(OH)2 → Mg(OH)2↓ + CaSO4

This method is known as lime–soda ash softening

and is commonly used in water treatment. Because soda

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ash is a relatively expensive chemical and waters with

less than 50 mg/L of residual hardness can seldom be
produced, it is normal to leave about two-thirds of the
residual hardness in the permanent form using the lime–
soda ash process. Therefore, the soda ash requirement
may be calculated as follows:
Noncarbonate hardness – 2⁄ 3 expected residual hardness
106
× ---------- = Na2CO3 dose required as mg/L.
100
Na2CO3 dose as mg/L is 1⁄ 3 permanent hardness × 1.06.

It is impossible to produce waters with less than

25 mg/L hardness by the lime–soda ash method because
Mg(OH)2 has a solubility of 9 mg/L and CaCO3, 17 mg/L.
Proper detention time is not practical; therefore, in waters
softened by this method, there is normally 50–80 ppm
(mg/L) hardness.

Ion Exchange
Certain natural minerals, known as zeolites (boiling
stone), have a porous, three-dimensional network of
alumino–silicate groups that act as large, fixed ions car-
rying a negative charge. They occur in cavities and
cracks of rocks, such as granite and basalt. Metallic ions
such as Na+ are attached to these ions to form large mol-
ecules. If hard water is allowed to stand in sodium zeo-
lite, Ca++ and Mg++ ions replace Na+ ions.
CaSO4 + Na2Z → CaZ + Na2SO4

where:
Z = zeolite
An exhausted zeolite is regenerated by immersing it in a
strong solution of sodium chloride, NaCl. Presently, syn-
thetic zeolites are replacing natural zeolites. Also, ion
exchange resins are used for the same purpose. Resins act
similar to zeolites. The reactions are

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Chapter 13 Hardness

Ca(HCO3)2 + H2R → CaR + 2H2O + 2CO2↑

CaSO4 + H2R → CaR + H2SO4

where:
R = resin
These resins are regenerated with acids. Natural
water treated by a combination of cation and anion
exchange resins is called deionized or demineralized
water, which is required sometimes for industrial use
and in laboratories.

Iron and Manganese in Water

Iron and manganese are commonly present in water
with low pH and a lack of molecular oxygen. Many water
supplies contain quantities of iron and manganese that
cause them to be unsatisfactory for domestic or indus-
trial use without treatment. Both iron and manganese
can be present in all groundwaters. Waters containing
more than 0.3 ppm of iron and 0.05 ppm of manganese
are objectionable.

Problems Caused by Iron and Manganese

1. Iron and manganese in water will stain clothes yel-
low and enamel black.
2. Their oxides are undesirable for bottling, laundries,
paper mills, tanning, and ice manufacturing.
3. They cause taste and color problems. Iron in water
spoils the taste and color of vegetables.
4. Iron deposits as oxides in distribution systems and in
water meters, causing the latter to give inaccurate
readings.
Mostly, these metals are present as bicarbonates due
to the action of carbonic acid, H2CO3.
Fe + 2H2CO3 → Fe(HCO3)2 + H2↑

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Mn + 2H2CO3 → Mn(HCO3)2 + H2↑

Sometimes their sulfates are also present due to the bac-

terial action on sulfides forming H2S, which gets con-
verted into H2SO4.

Removal
These metals can be removed by several methods
depending upon the nature of the water.

Aeration
Aeration is the mixing of air in water to dissolve oxy-
gen and to remove carbon dioxide. It is done before soft-
ening for effective precipitation of these metals.
The removal of carbon dioxide (CO2) raises the pH
because CO2 in water is carbonic acid (H2CO3). For effec-
tive iron removal, pH should be raised to 7.5.

Aeration Process
Fe(HCO3)2 → FeO + 2CO2↑ + H2O
4FeO + O2 → 2Fe2O3↓
Rust
Mn(HCO3)2 → MnO + 2CO2↑ + H2O
6MnO + O2 → 2Mn3O4
an unstable compound
4Mn3O4 + O2 → 6Mn2O3↓
Manganese oxidizes slower than iron, and higher pH
is required for its removal. Manganous oxide will rapidly
oxidize to Mn3O4, which slowly converts into a precipi-
tate of Mn2O3. Both Fe2O3 and Mn2O3 have 3H2O as
water of hydration and, therefore, are also written as
Fe(OH)3 and Mn(OH)3.
Fe2O3·3H2O or 2Fe(OH)3

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Chapter 13 Hardness

Chemical Precipitation
Iron is commonly present in well water as ferrous
iron, which can be removed by increasing pH to 9.4 with
lime.
4Fe(HCO3)2 + 8Ca(OH)2 + O2 → 2Fe2O3↓ + 8CaCO3↓ + 12H2O
Manganese will also be removed to some extent by
Ca(OH)2. It requires a higher pH.
2Mn(HCO3)2 + 4Ca(OH)2 + O2 → 2MnO2↓ + 4CaCO3↓ + 6H2O
Manganese dioxide (MnO2) is comparatively less
soluble.

Chlorination
Chlorine also helps in the removal of iron and man-
ganese, especially if the water contains microbes.
3MnO + HOCl → Mn3O4 + HCl
2Mn3O4 + HOCl → 3Mn2O3↓ + HCl
2FeO + HOCl → Fe2O3↓ + HCl

With Zeolites
Removal of iron and manganese by the cation
exchange method is similar to and simultaneous with the
removal of calcium and magnesium. In order to avoid the
accumulation of ferric hydroxide in the zeolite bed, it is
important that all iron in water be in the ferrous (Fe+2)
form. Therefore, there should not be any aeration of
water, and iron contents should not be very high.
For iron and manganese removal, zeolites are pre-
treated with manganous sulfate (MnSO4) and potassium
permanganate (KMnO4), respectively.

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Basic Chemistry for Water and Wastewater Operators

Questions
1. Name the elements that cause hardness in water.
2. Differentiate carbonate hardness from noncarbonate
hardness.
3. Give various methods for removing hardness.
4. Give various problems caused by hardness in water.
5. Why is removal of magnesium hardness more
expensive than that of calcium?
6. Give acceptable limits of the amounts of Fe and Mn
in drinking water.

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14 Corrosion and Its Control

C
orrosion is the deterioration
of a substance due to its reaction with the environment.
In water systems, it is the dissolving of metals, such as
iron, lead, or copper. It is a natural process that returns
processed metals back to their natural state as minerals.
Corrosion is essentially an electrochemical reaction
formed of three parts: the anode, the cathode, and an
electrolyte. The anode, the positive electrode, is the site
where the metal is dissolving by losing electrons. The
cathode, the negative electrode, is where an oxidizing
agent accepts the electrons. The electrolyte is the con-
ducting medium, which is water. The loss of electrons is
the oxidation and the increase in electrons is the reduc-
tion; therefore, corrosion is a redox reaction. A reaction
will not take place unless all three of its parts are
present. Reducing agents are mostly metals, such as
iron, lead, and copper, which are anodic. Oxidizing
agents are oxygen, hydrogen ions, and other metals,
which become cathodic. Here is an example of the cor-
rosion of iron in water.
Anode (positive electrode)
Fe → Fe+2 + 2e–
Cathode (negative electrode)
In the presence of O2
1⁄ 2 O2 + H2O + 2e– → 2(OH–)

Overall reaction is
Fe+2 + 2(OH–) → Fe(OH)2

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All of these reactions can be summarized as

2Fe + O2 + 2H2O → 2Fe(OH)2

Under acidic conditions

2H+ + 2e– → H2↑

Ferrous hydroxide (Fe(OH)2) is soluble. But in the pres-

ence of oxygen, it is further oxidized into ferric hydrox-
ide (Fe(OH)3), which is rusty in color and insoluble.
4Fe(OH)2 + O2 + 2H2O → 4Fe(OH)3↓
Rusty slurry
At the dead ends, the oxygen is depleted by these
reactions forming the rusty slurry. Some of this rusty
“slurry” is swept from the anode site by higher water
velocities, causing rusty water complaints. As corrosion
proceeds, a pit may form at the anodic site with blackish
gray Fe(OH)2 inside and an insoluble, rusty (Fe(OH)3)
layer on the outside. This outside growth is known as a
tubercle. High velocity or diffusion of water into the
tubercle can rupture it and release Fe(OH)2, which is
readily oxidized to rust (Fe(OH)3).

Types of Corrosion
There are many ways to classify corrosion, but
mostly it is based on its forms and causes.
1. Physical corrosion: It is erosion due to high-velocity
(i.e., over 5 ft/sec), particulate matter, or when dis-
persed gas bubbles erode the surface of a pipe.
2. Stray current corrosion: It occurs as a localized attack
caused by the potential differential from an outside
source, such as grounding appliances, through pipes.
Corrosion occurs where the current leaves the pipe.
3. Uniform corrosion: It takes place at an equal rate all
over the surface of the metal due to the uniform

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Chapter 14 Corrosion and Its Control

presence of many electrochemical cells through-

out the surface. Mostly this is associated with low
pH of the water. Any one site on the metal surface
may be anodic one instant and cathodic the next.
The loss in weight is directly proportional to the
time of exposure.
4. Localized or pitting corrosion: It occurs where there is
an exposed area of an otherwise coated metal surface
due to stress. This localized area becomes anodic and
is surrounded by a large cathodic area. The pit
remains anodic and becomes larger and larger as cor-
rosion progresses. Often, the pit is covered with a
tubercle.
5. Concentration cell corrosion: It is a function of the dif-
ference in concentration of various dissolved sub-
stances, such as metal and hydrogen ions or oxygen
molecules, on the adjacent portions of the metal sur-
face. The corrosion process will tend to equalize the
metal ion concentration by dissolving the areas with
less concentration, which become anodic. Similarly,
the part with less oxygen acts anodic, the one with
more oxygen acts cathodic.
6. Galvanic corrosion: This occurs when two dissimilar
metals are connected together in the water lines.
One metal becomes anodic and the other cathodic.
A metal on top (more active) in an electromotive
series becomes an anode and the one below, the
cathode. For example lead-solder and copper pipe
will have lead as the anode and copper as the cath-
ode, causing the corrosion of lead.
7. Bacterial corrosion: At dead ends of pipes where anaer-
obic conditions exist (lack of oxygen), sulfates are
converted into hydrogen sulfide, H2S, by anaerobic
bacteria. Because H2S is an acid, it increases H+ con-
centration and dissolves iron, which causes very
unpleasant tastes and odors.

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Basic Chemistry for Water and Wastewater Operators

Various Factors Affecting Corrosion

Dissolved Solids
Different types of ions and their concentrations have
different effects on corrosion. Carbonates, polyphos-
phates, and silicates normally reduce corrosion by form-
ing a protective film on the metal surface; whereas,
chlorides may increase corrosion by creating acidic con-
ditions that interfere with the protective film.

Dissolved Gases
Carbon dioxide and oxygen are the most common
dissolved gases. Carbon dioxide forms carbonic acid
(H2CO3) in water. It is an amphiprotic compound with
an important buffering effect in water. Oxygen, as previ-
ously discussed, acts cathodic and as a depolarizer as it
combines with hydrogen to form water. A higher con-
centration of oxygen causes more corrosion, and vice
versa. Other gases of interest are chlorine, ammonia, and
hydrogen sulfide. Chlorine as hypochlorous acid causes
acidic conditions and thus more corrosion. Hydrogen
sulfide is also an acid and thus causes corrosion. Ammo-
nia forms chloramines with chlorine, which are known
to inhibit corrosion.

Temperature
As a rule, the higher the temperature, the higher the
rate of corrosion. There is less corrosion during winter
than summer. Soft waters (with alkalinity less than
50 mg/L) are very corrosive during summer.

Corrosion Control
As previously discussed, the corrosion process has
three basic parts and all are important for a reaction to

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Chapter 14 Corrosion and Its Control

take place. By preventing any one of these three parts,

corrosion can be prevented. The slowest part determines
the rate of corrosion. The cathodic reaction is generally
the slowest due to uncertain availability of oxygen or
hydrogen ions. If the cathode surface is covered with
OH– ions and H2 molecules, it creates a barrier for further
reaction, and corrosion is controlled. This physical bar-
rier is known as polarization. The disruption or removal
of this barrier is called depolarization, which causes the
resumption of corrosion. Depolarization can be caused
by increasing acidity, which neutralizes OH– ions; by
increasing oxygen concentration, which combines with
hydrogen to form water; or by increasing the water
velocity, which sweeps away OH– ions and hydrogen
gas. Nitrates and chlorine are also depolarizers.
In fact, almost any metal in contact with water will
corrode. In many cases, the electron acceptor is the H+
ion produced by water itself due to self-ionization.

H2O H+ + OH–

Therefore, for full protection, the metal should not

be allowed to come in direct contact with water. This can
be achieved either by providing a mechanically applied
coating, such as a cement lining, with the tar coating,
paint, plastic, rubber, etc., or by providing a water that
coats the surface of the pipe. Coatings formed by contact
with flowing water include calcium carbonate (CaCO3),
a phosphate, or a silicate coating.
CaCO3 coating size and rate depend mainly upon
the pH of the water and its calcium carbonate contents.
At a high pH and a high calcium carbonate concentra-
tion, there can be too much CaCO3 deposition (scale for-
mation) in the filter media and the lines. At a low pH and
a low calcium carbonate concentration, there can be lit-
tle or no deposition. For this reason, water is treated to
be slightly depositing. There are two general methods of

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Basic Chemistry for Water and Wastewater Operators

stabilizing hard waters softened by the lime and soda ash

method. First is the use of a small amount of polyphos-
phates, such as sodium hexametaphosphate 6(NaPO3),
to prevent too much precipitation of CaCO3 by seques-
tering. The second method is recarbonation, which is
the passing of carbon dioxide (CO2) through the water
to lower its pH and thus convert insoluble CaCO3 into
soluble bicarbonate (HCO3–).
Various indices have been developed to determine
the stability of water based on various factors affecting
the CaCO3 deposition characteristics of water.

Various Indices
1. Marble test: This test is based on the alkalinity of the
water. The water to be tested is saturated with CaCO3
by adding CaCO3 powder to it, shaking it, and keep-
ing it overnight. Alkalinity of the sample is deter-
mined before and after saturation. If the initial
alkalinity is equal to the final alkalinity, the water is
stable. If the initial alkalinity is higher, then water is
depositing; if it is less, then it is corrosive. This is a
simple, easy, and good way for an operator to control
corrosion.
2. Baylis curve: This shows the solubility of CaCO3 with
regard to alkalinity and pH (see Figure 14-1). If the
point of intersection of pH and alkalinity of the
water is above the equilibrium curve, the water is
depositing; if it is below, the water is corrosive; and
if it is equal, the water is stable.
3. Langelier saturation index (LSI): This is a commonly
used index in the water utility industry (see
Figure 14-2). It determines the CaCO3 deposition
property of the water by calculating saturation pH
(pHs). pHs is calculated from total dissolved solids,
temperature, alkalinity, and calcium contents of the
water. If the pH of the water is equal to the pHs, the

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Chapter 14 Corrosion and Its Control

10.0
Curve of values necessary to
produce a coating of CaCO3
Curve of CaCO3 equilibrium
9.0 Curve of values necessary to
Intermediate
Zones of Possible prevent iron stains
Corrosion
pH Values

8.0 Zone of No
Corrosion

7.0
Zone of Serious Corrosion

6.0
0 50 100 150 200 250 300 350
Alkalinity, ppm

Figure 14-1 Stability Curve Showing Relationship Between

pH Values and Alkalinity

water is stable; if it is higher, the water is depositing;

and if it is less, the water is corrosive.
LSI = pH – pHs

4. Ryzner index (RI) or stability index: This index is two

times pHs minus pH of the water.
RI = 2pHs – pH

An RI value less than 6 indicates a depositing water,

and more than 6 indicates corrosion. The higher the
RI, the more corrosive is the water in the lines.

Phosphate Treatment
There are three types of corrosion-inhibiting phos-
phates: orthophosphates, polyphosphates, and zinc-
containing phosphates. Orthophosphates are simple
phosphate compounds: phosphoric acid (H3PO4), sodium
phosphate (Na3PO4), sodium monohydrogen phosphate
(Na2HPO4), and sodium dihydrogen phosphate

129
 Column 1 Column 2 Column 3 Column 4 Column 3
Pivot Line Ca pHs Alk.
7.5 1 1
2.9 12.5
2.8

130
11.5 2
2.7 7.0 2

1
2.6 11.0 3
3
2.5 6.5

1
0o C 4 10.5 4
2.4 5 5
6 10.0 6
10oC 2.3 7
6.0 7 8
2.2 8 9
9 9.5 10
2.1 10
20oC 5.5 9.0 15
25oC 2.0 15
o
1.9 20
30 C 20 8.5
25
1.8 5.0 30
30 8.0
40oC 1.7 40
40 50
1.6 4.5 7.5
o 50 60
50 C 1.5 70
60 80
70 7.0
o 90
BasicChemistry.book Page 130 Monday, February 18, 2002 5:03 PM

60 C 1.4 80
4.0 100
1.3 90 6.5
o 100

Temperature – Total Solids Constant (pK 2 – pK 3)

70 C 150
1.2
o
150 6.0 200
80 C 1.1 3.5
200 250
o 1.0 5.5
300
90 C
3.0 300 400
0 100 200 300 400 500 600 700 800 5.0
400 500
Total Dissolved Solids in Parts Per Million
Basic Chemistry for Water and Wastewater Operators

600
500 4.5 700
800
900
1,000
Graph and nomogram for determination of pH saturation by Instructions for using chart.
Langelier's formula (applicable within pH range 7.0–9.5) (a) Knowing temperature and total dissolved solids, find temperature and total solids constant on column 1.
Data required for determing pH saturation. (b) Align this constant with given value of calcium on column 3 of chart, then locate point on column 2 of chart (pivot line).
(a) Total alkalinity, as parts per million of CaCO3. (c) Align this point on pivot line with given alkakinity on column 5; read pH saturation on column 4.
(b) Calcium in parts per million. Saturation index is pH actual minus pH saturation, e.g., pH actual. pH saturation. Saturation index.
(c) Total dissolved solids, in parts per million. 7.6–8.1 = –0.5 (corrosive)
(d) Temperature, in degrees centigrade, at which pH saturation is desired. 8.4–7.8 = +0.6 (scale forming)

Figure 14-2 Riehl’s Graph and Nomogram for Determination of pH Saturation by Langelier’s Formula
BasicChemistry.book Page 131 Monday, February 18, 2002 5:03 PM

Chapter 14 Corrosion and Its Control

(NaH2PO4). Polyphosphates are long-chain phosphates

formed by reacting phosphoric acid with sodium or potas-
sium compounds. A common example of polyphosphate
is sodium hexametaphosphate, 6(NaPO3), which is com-
monly known as Calgon. Polyphosphates have been
reported to be effective in reducing red water complaints.
Their function differs under different conditions of water
and their dose. At a low pH such as 5, they form a protec-
tive coating on the cathodic site in the presence of cal-
cium and iron ions. At high pH and a low dose, they
dissolve iron and calcium by a sequestering mechanism,
thus preventing excessive scale formation.
Polyphosphates are more effective for corrosion
control at high velocities of water and at high doses.
They remove corrosion products from the anode by
forming positively charged colloidal particles of ferric
oxide and calcium compounds and metaphosphates,
which are then deposited on the cathode area. Increas-
ing polarization of the cathode reduces corrosion. If
little or no calcium is present in the water, sodium
hexametaphosphate will attack iron and cause corro-
sion. The calcium/polyphosphate ratio should be
between 0.2 and 0.5.
Rusty water is not always an indication of corrosion,
as iron may be naturally present in water and red scales
may be a deposition of calcium together with oxidized
natural iron.
Zinc-containing phosphates contain zinc in various
concentrations (10–30 percent) with orthophosphates or
polyphosphates. The protective film is formed of zinc
phosphate and carbonates. The higher zinc concentra-
tion acts faster by rapid film formation. The higher the
pH, the lower the zinc required for adequate control.

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Basic Chemistry for Water and Wastewater Operators

Questions
1. Corrosion is an electrochemical reaction. True or
False.
2. Give the three parts of the corrosion process.
3. A corroding metal becomes anodic or cathodic.
4. Which are the common electron acceptors?
a. Lead and copper
b. Calcium ions
c. Oxygen and hydrogen ions
5. In galvanic corrosion, a metal at the top in the elec-
tromotive series will serve as (a/an)
a. Cathode
b. Anode
6. Define polarization and depolarization.
7. What is a tubercle formed of?
8. What is a sequestering agent? Give an example.
9. What is the function of Calgon when used in very
low doses?
10. Give the difference between Langelier and Ryzner
indices. If the LSI is 0, is water stable, corrosive, or
depositing?
11. Briefly give the use of the following in corrosion control:
a. Sodium hexametaphosphate
b. Zinc orthophosphate
12. In case of a depositing water, what gets deposited?
a. Calcium carbonate
b. Sodium carbonate

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15 Disinfection

D
isinfection of water or sew-
age means destruction or inactivation of waterborne
pathogens (disease-causing microorganisms). Pathogens
are present in our gastrointestinal tract and are dis-
charged with fecal matter into the sewage system, which
enters the sources of our water supply, especially surface
waters. Therefore, water becomes their carrier.
At present, the well-established waterborne diseases
are cholera, typhoid, paratyphoid, Legionnaire’s disease,
bacillary dysentery, amoebic dysentery, giardiasis,
cryptosporidiosis, and infectious hepatitis. Out of these
waterborne pathogens, Giardia lamblia, causing giardia-
sis, and Cryptosporidium parvum, causing cryptosporidio-
sis, are the hardest to kill. Waterborne pathogens exist in
small numbers and are difficult to identify; therefore,
coliform bacteria that are commonly and abundantly
present in human excreta are used as indicator organ-
isms of fecal contamination and thus a possible presence
of waterborne pathogens. The destruction of the
coliform group is a good criterion to determine adequate
disinfection. Coliform bacteria are represented by fecal
(mainly Escherichia coli) and nonfecal lactose ferment-
ing, nonsporulating, gram negative (red stained), aero-
bic, and facultative bacilli (rod shaped).
The first large-scale disinfection of a public water sup-
ply in the United States was undertaken in 1908 at Jersey
City, N.Y., by using chlorine. Chlorine has been a popular
disinfectant in North America; it is effective, economical,
and commonly available. The free residual chlorine, how-
ever, reacts with naturally occurring organics as humic

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Basic Chemistry for Water and Wastewater Operators

acids and bromides to produce carcinogenic trihalo-

methanes (THMs). After this discovery in 1974, alterna-
tive disinfectants—such as chloramines, chlorine dioxide,
ozone, potassium permanganate, hydrogen peroxide,
silver, high pH, and ultraviolet radiation, alone or in
combination—have been explored. The goal is the proper
balance between adequate disinfection and acceptable levels
of disinfection by-products. Of these disinfectants, chloram-
ines, chlorine dioxide, and ozone are the most consid-
ered and well-studied practical alternatives.

Chlorine as a Water Disinfectant

Chlorination is the act of applying chlorine to water.
It is the most common method of disinfection. Before
1974, more than 95 percent of municipalities used chlo-
rine for disinfection. Besides disinfection, chlorine
removes tastes, odors, iron, and manganese and controls
slime-producing bacteria. It also helps in coagulation
and destruction of cyanides and phenols.

Chlorine Properties
Discoverer Carl Wilhelm Scheele first isolated chlo-
rine in 1774. At room temperature, chlorine is a greenish
yellow gas. Its boiling point is –34.6°C and its melting
point is –101°C. It can, therefore, be compressed easily
into a liquid state. One mL of liquid forms 450 mL of gas.
The density of chlorine is 3.21 g/L at standard tempera-
ture and pressure, while air is only 1.29 g/L. Thus, chlo-
rine is about 2.5 times heavier than air. It is a very strong
oxidizing agent. It reacts with various types of organic
substances, metals, and ammonia. Chlorine has a strong,
unpleasant smell and is corrosive to metals and flesh
when wet.

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Chapter 15 Disinfection

Chlorine reacts with water to produce hydrochloric

acid and hypochlorous acid. Hypochlorous acid (HOCl)
is a strong disinfectant.
H2O + Cl2 → HCl + HOCl

Hypochlorous acid is a weak acid. It ionizes into

hypochlorite ion (OCl–) and hydrogen ion (H+) in water;
the latter forms hydronium ion (H3O+).

HOCl + H2O → H3O+ + OCl–

According to the old theory, hypochlorous acid

decomposes into hydrochloric acid (HCl) and nascent
oxygen (O by itself); the latter combines with the oxidiz-
able cell structures in the microorganisms and kills
them. Recent theory states that chlorine unites with the
enzymes of microorganisms (possibly at the nitrogen
site) and inactivates them. Enzymes are proteins, which
are formed of four essential elements: nitrogen, carbon,
hydrogen, and oxygen.
Sometimes, chlorination causes the disappearance of
the bacterial bodies, probably by converting them into
soluble compounds. Whatever the mechanism, chlorine
inactivates the pathogens and renders the water potable
or safe for drinking.

Various Forms of Chlorine Used in Disinfection

Pure Chlorine
Pure chlorine is available in a gas or liquid state in
100-, 150-, or 2,000-lb containers. It is also available in
tank car lots of 15–90 tons. It is applied to the water by
means of a special apparatus for dosage control known as
a chlorinator.

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Basic Chemistry for Water and Wastewater Operators

Hypochlorites
Hypochlorites of sodium and calcium are solid forms
of chlorine. They produce hypochlorous acid when dis-
solved in water. High-test hypochlorite, commonly
known as HTH, is calcium hypochlorite (Ca(ClO)2),
which contains about 70 percent available chlorine.
Sodium hypochlorite (NaClO) is only 15 percent avail-
able chlorine and is common household bleach.
Ca(ClO)2 + 2H2O → Ca(OH)2 + 2HOCl

Hypochlorites are used as solutions in water disinfec-

tion. The apparatus used to dispense them into the water
is known as a hypochlorinator.

Chloride of Lime
Chloride of lime is also known as bleaching powder.
Its chemical formula is CaClOCl. It is produced by pass-
ing chlorine gas over slaked lime (Ca(OH)2).
Ca(OH)2 + Cl2 → CaClOCl + H2O

Chloride of lime contains 33–35 percent available

chlorine. It is also applied as solution. Like hypochlo-
rites, it produces hypochlorous acid in water.
2CaClOCl + 2H2O → CaCl2 + Ca(OH)2 + 2HOCl

Breakpoint Chlorination
Breakpoint chlorination is a technique used in chlori-
nation of waters containing organic matter and ammonia
to ensure proper disinfection by producing free residual
chlorine. Increasing doses of chlorine are added to a series
of samples.
At first, residual chlorine increases to a point, known
as a “hump,” after which a further increase in the dose
results in a decrease of residual chlorine, which reaches
the lowest point, the “breakpoint” or “dip.” After the

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Chapter 15 Disinfection

1 2 3 4

Chlorine Residual

Breakpoint

Free
Available
Residual

Chlorine Added

NOTE: Numbers indicate points within treatment where chlorine is added.

Figure 15-1 Breakpoint Chlorination Curve

breakpoint, an increase in dose results in a correspond-

ing increase in residual chlorine. This residual chlorine is
known as free residual chlorine or breakpoint residual,
which is hypochlorous acid under normal pH (below
7.5) conditions. The breakpoint indicates the comple-
tion of reactions of chlorine with bacteria and all other
substances such as iron (Fe), manganese (Mn), hydrogen
sulfide (H2S), and ammonia (NH3). Breakpoint chlorina-
tion affords, in many cases, better control of bacteria,
tastes, odors, and red and black waters. Figure 15-1 illus-
trates the breakpoint chlorination curve.

Chemistry of Breakpoint Chlorination

The sequence in which chlorine reacts with various
substances in the water is as follows:
1. Reducing agents: These agents include iron, manga-
nese, hydrogen sulfide, nitrites, and thiosulfates,
which neutralize chlorine and result in the formation

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Basic Chemistry for Water and Wastewater Operators

of chlorides. Thus, iron, manganese, and hydrogen

sulfide are removed. They cause red water, black
water, and tastes and odors, respectively. Due to neu-
tralization of chlorine into chlorides, there is no
residual chlorine at this stage. Chlorides do not have
any disinfecting properties.
H2S + 4Cl2 + 4H2O → H2SO4 + 8HCl at high pH
H2S + Cl2 → 2HCl + S at low pH
2. Organic matter: Organic substances, including micro-
organisms and phenols, react with chlorine after
reducing agents to produce chloroorganic com-
pounds. This area in the curve also presents taste-
and-odor problems.
3. Ammonia: Chlorine forms chloramines (NH2Cl) with
ammonia until a hump is reached.
The following reactions occur:
NH3 + HOCl → NH2Cl + H2O
Hypochlorous acid is the form of chlorine produced
after reacting with water; therefore, instead of Cl2,
HOCl is used in the equations. Both chloroorganic
compounds and chloramines are known as combined
residual chlorine. If chlorination comes after sedimenta-
tion and filtration, the combined residual chlorine is
commonly represented by chloramines due to the pres-
ence of ammonia and the absence of organic matter.
4. Destruction of combined residual chlorine: Chlorine
reacts with chloroorganic compounds and chlora-
mines and thus gets neutralized, resulting in a drop of
residual chlorine. The end products of these reactions
are nitrogen gas (N2), nitrous oxide (N2O), hydrochlo-
ric acid, and nitrogen trichloride (NCl3). Nitrogen
trichloride is also known as trichloramine. These reac-
tions occur between the hump and the breakpoint.
After the breakpoint (dip), chlorine in the water is free
residual chlorine mostly as hypochlorous acid.

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Chapter 15 Disinfection

The object of breakpoint chlorination is to produce

and maintain free residual chlorine because free residual
chlorine can exist in the water only after the breakpoint
or complete oxidation of substances, which react with
chlorine.

Chlorine Demand
Chlorine demand is the amount of chlorine con-
sumed in the water during a certain contact period,
commonly 30 min. It is calculated by subtracting resid-
ual chlorine from the chlorine dose. Suppose we used a
5-mg/L chlorine dose in a sample. After 30 min (normal
contact time period), there is 2 mg/L residual. The chlo-
rine demand of water is 3 mg/L.

Factors Affecting Chlorination

The effectiveness of chlorine is affected by pH, tem-
perature, contact time period, concentration, and resid-
ual chlorine type. The amount of hypochlorous acid
depends on the pH of the water. The following table
shows the predominant form of free residual chlorine at
various pH values:

pH Predominant Free Residual Chlorine

6–7.5 HOCl, chlorine as hypochlorous acid

7.5–9 OCl–, chlorine as hypochlorite ion

Hypochlorous acid is ionized more than 50 percent

into H+ and OCl+ ions above pH 7.5. Since hypochlorous
acid and not the hypochlorite ion (OCl–) is the principal
disinfectant, effectiveness of chlorine starts declining
above pH 7.5. The following table suggests the minimum
free residual chlorine required at different pH values for
disinfection:

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Basic Chemistry for Water and Wastewater Operators

pH Free Residual Chlorine, ppm

6–8 0.2
8–9 0.4
9–10 0.8

These amounts at normal water temperature (about

20°C) will disinfect water adequately in about 10 min
contact time.
Effectiveness of chlorine varies directly with temper-
ature. The higher the temperature, the quicker the kill of
microorganisms; thus, less contact time is required.
Chlorine requires a certain amount of time to react with
microorganism cells. The longer the contact time, the
more effective is the disinfection. That is why the CT
concept is adopted for proper disinfection. C stands for
concentration of disinfectant as milligrams per litre and T
stands for contact time in minutes. CT is a constant for
each disinfectant. The contact period normally recom-
mended for chlorine is 15–40 min. Thirty minutes are
allowed for proper disinfection.
Concentration of free residual chlorine under differ-
ent pH and temperature conditions is an important fac-
tor. Minimum effective amounts of free residual chlorine
at different pH values are already discussed. Normally,
0.5–1 mg/L free residual chlorine will effectively disin-
fect the water; remove iron, manganese, tastes, odors,
and colors; and control slime and algae.
Combined residual chlorine (chloramines) is less
effective than free residual chlorine (HOCl). Normally,
chloramines require a higher dose and longer contact
time than free residual chlorine for the same degree of
disinfection.

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Chapter 15 Disinfection

Types of Chlorination
Prechlorination may be defined as the application of
chlorine to raw water, which means before any water
treatment. It helps in the coagulation and removal of
tastes and odors. It kills a large number of bacteria, algae,
and other microorganisms, which settle out in the clari-
fiers. Prechlorination is especially useful for surface water
treatment and ensures disinfection while water flows
through pipes and the treatment plant. The chlorine
residual should be 0.2–0.5 mg/L in the settled water
reaching the filters; a higher amount can cause formation
of THM and other harmful disinfection by-products. The
chemical nature of these chemicals is discussed in
chapter 12.
Superchlorination is the application of a very high
concentration of chlorine, primarily for sterilizing pipes
and controlling tastes and odors caused by microorgan-
isms. Normally, dechlorination is required after super-
chlorination.
Postchlorination is the chlorination of completely
treated water. It is used for proper disinfection and to
maintain the desired amount of residual chlorine in the
reservoir and distribution system as a way to prevent any
accidental contamination and slime-forming bacterial
growth. The presence of residual chlorine in the system
indicates that an adequate amount of chlorine has been
used for disinfection. The amount of residual chlorine is
a quicker method than bacteriological tests to determine
potability of water.
Dechlorination is the destruction of chlorine by
using activated carbon or reducing agents, such as sul-
fur dioxide (SO2), sodium sulfite (Na2SO3), sodium
bisulfite (NaHSO3), or sodium thiosulfate (Na2S2O3).
Dechlorination is required to maintain the desired level
of residual chlorine in the water. It is mainly done after

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Basic Chemistry for Water and Wastewater Operators

superchlorination or in water supplies for some indus-

trial uses. Chlorine is not desirable for some ion
exchange resins, which are used in water softeners.
Hypochlorination is the use of hypochlorites for chlo-
rination. Hypochlorites of sodium and calcium are com-
mon compounds used for this purpose. They are
available in powder or tablet form; thus, they have the
advantage of easy storage and application. They are espe-
cially useful for disinfecting lines and discontinuous
treatment of small-scale operations. Hypochlorites react
with water and produce hypochlorous acid and hydrox-
ides. Hydroxides tend to raise the pH, which may cause
the precipitation of calcium carbonate (CaCO3). A com-
plex of phosphate, sodium hexametaphosphate, is
added to overcome this problem.
Hypochlorites are used as solutions by means of
hypochlorinators. All hypochlorites are corrosive to
some degree; therefore, store them in wood, glass, plas-
tic, or rubber containers.

Chlorine and Health

Chlorine is a highly toxic chemical even in small
concentrations in air. The following table shows the
physiological effects of various concentrations of chlo-
rine by volume in air:

Effects Chlorine, ppm in air

Least detectable by odor Below 3.5

Produces throat irritation 15

Produces coughing 30

Dangerous after 30-min exposure 40–60

Rapidly fatal 1,000

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Chapter 15 Disinfection

Twenty to 50 mg/L of chlorine in water for a few

days did not show any bad physiological effects.

Chlorine and Safety

When using chlorine, observe the following
precautions:
1. Use a mask when entering a chlorine-containing
atmosphere.
2. Apparatus, lines, and cylinder valves should be
checked regularly for leaks. Use ammonia fumes to
test leaks. Ammonia and chlorine produce white
fumes of ammonium chloride, which indicate leaks.
3. Because it is heavier than air, always store chlorine
on the lowest floor; it will collect at the lower level.
For the same reason, never stoop down when a chlo-
rine smell is noticed.
Handle chlorine carefully and respectfully, as she is
the “green goddess of water.”

Chloramines as Water Disinfectants

Chloramines are produced by reacting ammonia
with chlorine. Despite their weaker disinfecting proper-
ties and slower disinfection rate, they have been used
successfully by a large number of utilities in the United
States. Ammonia is used ahead of chlorine to prevent
formation of THMs. Reaction rate and type of chlora-
mine, such as mono-, di-, or trichloramine formation,
depend on the pH and chlorine-to-ammonia ratio. At
pH 8 and a ratio of chlorine to ammonia between 4 and
5, monochloramine is the predominant chloramine
species, which is preferred because it is less odorous. At
a pH of 5–8, both mono- and dichloramines are present;
at pH 4.4–5, dichloramine predominates; and below pH
4.4, trichloramine predominates. As the chlorine-to-
ammonia ratio progresses, monochloramine (NH2Cl)

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Basic Chemistry for Water and Wastewater Operators

changes to dichloramine (NHCl2), then to trichlora-

mine (NCl3), and finally to nitrogen and chlorides until
free residual chlorine is formed.
NH3 + HOCl → NH2Cl + H2O

NH2Cl + HOCl → NHCl2 + H2O

NHCl2 + HOCl → NCl3 + H2O

2NH2Cl + HOCl → 3HCl + H2O + N2↑

Chloramines are more effective at a higher pH

(above 8) and require about 70 times more contact time
and much higher concentration than hypochlorous
acid. Chloramines, however, are comparable to
hypochlorite ion, which is free residual chlorine above
pH 7.5.
Some other disadvantages of chloramines are that
they induce hemolytic anemia and thus cause problems
with the use of dialysis machines. They are harmful for
tropical fish. Due to these disadvantages, they are not
accepted as good disinfectants by many utilities.

Bromine as a Water Disinfectant

Bromine is a halogen with disinfection properties
like chlorine. It is a dark red liquid about three times
heavier than water. It readily evaporates, and its vapor is
very irritating to the eyes and throat. It forms in water
hypobromous acid and hydrobromic acid. Hypobro-
mous acid is a strong disinfectant.
H2O + Br2 → HBr + HOBr

The major difference between hypobromous acid

and hypochlorous acid is that its effectiveness starts
declining at pH 8.5. Bromine produces bromoamines
with ammonia, which are as effective as hypobromous
acid. Bromine has been used for disinfection of swim-
ming pools and waters with high ammonia content.

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Chapter 15 Disinfection

Because bromine is scarce, it is more expensive than

chlorine. It also is physiologically more active to
humans; thus, its use as a disinfectant is limited.

Iodine as a Water Disinfectant

Iodine (I2), a bluish black solid, is another halogen
with disinfecting properties. Iodine forms hypoiodous
(HOI) acid in water, which is an effective disinfectant.
I2 + H2O → HI + HOI

Iodine’s great advantage is that it does not react with

ammonia. Its effectiveness is not affected by pH. By
appropriate control of the dose, it provides a broad spec-
trum of germicidal capability. Iodine is quite expensive,
scarce, and physiologically active, which results in lim-
ited use. It is useful in a small-scale, noncontinuous
application, such as swimming pool disinfection and as
tablets for individual water supply disinfection in the
armed forces.

Chlorine Dioxide as a Water Disinfectant

Sir Humphry Davi first discovered chlorine dioxide,
a yellow to red gas, in 1811, by reacting potassium chlo-
rate with hydrochloric acid.
4KClO3 + 4HCl → 4KCl + 4ClO2↑ + 2H2O + O2↑

It was first used by a water utility in Niagara Falls in

1944 for taste and odor control. By 1997, about 400
water utilities in North America used it for predisinfec-
tion. Commercially, it is produced by reacting sodium
chlorite with chlorine and/or an acid.

2NaClO2 + Cl2 2NaCl + 2ClO2↑

5NaClO2 + 4HCl 5NaCl + 4ClO2↑ + 2H2O

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Basic Chemistry for Water and Wastewater Operators

Both processes use a similar generator formed of a

cylindrical reactor of polyvinyl chloride or Pyrex glass.
The Rio-Linda in Sacramento, Calif., generator uses chlo-
rine gas rather than chlorine solution and the yield is
improved to 96–98 percent compared to 95 percent or
less in other generators where pH is regulated to 3–4 by
adjusting chlorine feed for a better efficiency.
Electrolysis of NaClO2 is another method, which is
quite promising, as it provides 100 percent chlorine
dioxide solution. There is oxidation of ClO–2 to ClO2 at
the anode and reduction of Na+ to Na at the cathode.
NaClO2 → Na + ClO2↑
Cathode Anode
Chlorine dioxide is a strong disinfectant and, unlike
chlorine, its effectiveness is not affected by ammonia
and pH; furthermore, it does not produce THMs. Its
effectiveness against Giardia and Cryptosporidium is quite
good. It is very promising when chlorine dioxide treat-
ment is followed by chlorine or chloramines. This sequen-
tial disinfection has a synergistic effect. A 1.5-mg/L
chlorine dioxide dose gave more than 90 percent inacti-
vation; whereas, this dose followed by 1.6 mg/L chlorine
or 2.8 mg/L chloramines gave about 99 percent inactiva-
tion of these pathogens. Chloramine and chlorine alone,
however, had insignificant effects. Chlorine dioxide
apparently weakens the organisms to be effectively
destroyed by chlorine or chloramines.
There are disadvantages of using chlorine dioxide. It
is relatively expensive to generate and is explosive at a
concentration above 10 percent in the air. Chlorine
dioxide is unstable and reverts to chlorite, which can
cause anemia in some individuals. Therefore, it is gener-
ated at the site and applied immediately. Also, sodium
chlorite is hazardous to handle. Chlorine dioxide use is
further limited due to the potential health effects of
chlorite and chlorate, the by-products. Thus, the use of

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Chapter 15 Disinfection

chlorine dioxide in the water industry is somewhat lim-

ited mainly due to chlorite formation and its dose
restriction.
Various chemicals such as activated carbon, sulfur
dioxide, sulfite, and ferrous compounds have been stud-
ied to control chlorite. It is well documented that chlorite
can be effectively controlled by using ferrous ions (Fe+2)
in water treatment. About 3 mg/L ferrous ion reduces
chlorite by 1 mg/L, which is a stoichiometric ratio.

Ozone as a Water Disinfectant

Ozone, a colorless gas with a peculiar pungent odor,
is a triatomic form of oxygen (O3). It was discovered by
M. van Marum in 1785 and was named ozone by
C.F. Schönbein in 1840 after the Greek word ozein, mean-
ing to smell. It is generated by passing air or oxygen
through a high-voltage arc between two electrodes, or
ultraviolet radiation. Commercially, it is generated by a
silent electric discharge or corona discharge by using a
high-voltage (over 15,000 volts). A small percentage of
oxygen is converted (1–3 percent from air and 2–6 per-
cent from oxygen feed) into ozone in this process. It is 20
times more soluble in water than oxygen, which helps in
its dispersion in water.

3O2 2O3
Oxygen Ozone
Ozone is a very unstable gas; its molecule readily
decomposes into an oxygen molecule and nascent oxy-
gen. Its half-life at room temperature is only 15–20 min.
Nascent oxygen apparently causes disinfection.
O3 → O2 + O

Immediately after generation, the ozone is dis-

persed through the water. Microorganisms are killed
immediately upon contact with the ozone. Their cells

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Basic Chemistry for Water and Wastewater Operators

are ruptured (lysis), resulting in death. Ozone is the

strongest disinfectant used in water treatment. Ozone
has very strong germicidal properties with very rapid
effects. Its effectiveness is not impaired by ammonia
and pH. It leaves dissolved oxygen after its decomposi-
tion. Ozone’s disadvantages are that it must be gener-
ated at the site of application, does not have a residual
effect, and is quite expensive to generate. Due to these
shortcomings, ozonation is not as common as chlorina-
tion. It is more accepted in France, Switzerland, and
Germany (over 1,000 installations). They believe in
treating the water to pure, unpolluted groundwater
form without any chemical odor. The first major ozone
installation was in 1905 in Nice, France, followed by
Paris in 1906. Canada has about 20 major installations,
including a 60-mgd plant in Quebec. In the United
States, the first major installation was at Whiting, Ind.,
in 1939, followed by Philadelphia in 1949.
The ozonation treatment of water can be divided
into three parts: preparation of feed gas, production, and
contaction. Preparation of feed gas is mainly filtration of
air to remove dust and then drying, as moisture produces
nitric acid from air feed by combining oxygen and nitro-
gen. Oxygen feed is a more efficient system for better
conversion rate and less corrosion problems due to lack
of nitrogen. Production is simply passing the feed at low
pressure between two electrodes separated by a dielectric
and a gap across which an alternating potential of about
15,000 volts is maintained for ozone production. A large
amount of heat is released in the process, which needs a
cooling system, primarily using water. Contaction is the
passing of the ozone oxygen/air mixture through the
water by dispersing it mostly by diffusers at the bottom
of a contact chamber to have the maximum transfer of
ozone into the water.
Ozone, besides being an excellent disinfectant, con-
trols tastes and odors, color, algae, slime growth, THM

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Chapter 15 Disinfection

formation and other organics, cyanides, sulfides, sulfites,

iron, manganese, and turbidity. There are some disad-
vantages, such as the high cost of production; there is
almost no residual effect; and it is difficult to adjust to
the variations in treatment, load, or demand. It is also
selective in oxidation of some organics such as ethanol,
which does not readily react with it and sometimes
causes fragmentation of large molecules that encourages
bacterial growth in the distribution system. Ozonation is
followed by chlorination or chloramination for the
residual effect. Furthermore, its by-products are still not
properly understood.
Due to high capital cost and lack of residual effect,
various combinations of ozone and other disinfectants
have been studied.
Peroxone is the use of hydrogen peroxide and ozone
together. It is demonstrated that this combination accel-
erated the oxidation of some organics 2–6 times. Perox-
one is known as an advanced oxidation process, which
produces hydroxyl (OH–) radical, a very active interme-
diate that generally has far greater oxidizing power than
ozone by itself. Hydrogen peroxide and ozone in a ratio
of 2:4 mg/L are very effective. Peroxone is almost one
half as expensive as ozone alone. Peroxone (2:4 mg/L)
followed by 1.5 mg/L of chloramines has been an effec-
tive disinfection treatment for some utilities.
Soozone, a combination of ultrasonic waves and
ozone, has been used in Indian Town, Fla., to treat sew-
age. Ultrasonic waves break organic particles and ozone
oxidizes them.

Ultraviolet Light
Ultraviolet light rays cause death of microorganisms
by oxidation of their enzymes. The most effective wave-
length is 2,650 angstrom (1 Å = 10–8cm). Thus, rays with
a wavelength less than 3,100 Å are effective. The mercury

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Basic Chemistry for Water and Wastewater Operators

vapor lamp is an economical method of producing

ultraviolet light of 2,537 Å. For disinfection with ultra-
violet light, water should be clear, colorless, and shallow
(3–5 in. deep) to allow effective penetration of rays.
These requirements as well as no residual effect and cost
of application limit the use of this method to very small
water supplies.

Silver Ions
Silver ions in very low concentration (0.01 ppm) are
sometimes used for water disinfection. Disinfection is
obtained by passing water between electrically charged
silver plates, which disperse silver ions into the water.
The effectiveness of silver ions is decreased by the pres-
ence of organic substances in water. Silver is not a prac-
tical disinfectant for water supplies. It is too expensive
and has a very limited use.

Questions
1. What is the main purpose of disinfection of water?
2. Why is chlorine used commonly for water
disinfection?
3. Are there any other uses of chlorination besides
disinfection?
4. Disease-producing bacteria are called:
a. Aerobic
b. Facultative
c. Pathogenic
5. Chlorine is a highly toxic gas. True or False.
6. Chlorine is lighter than air. True or False.
7. Free residual chlorine is a better disinfectant than
combined residual chlorine. True or False.

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Chapter 15 Disinfection

8. Should chlorine be stored on the upper or lower floor

of the building?
9. Postchlorination is the chlorination of water before
any treatment. True or False.
10. How would you detect a chlorine leak?
a. By feeling a leak.
b. By looking for a greenish gas coming out.
c. By using carbon dioxide vapor.
d. By using ammonia vapor.
11. Name six waterborne diseases.
(1) ____________________________
(2) ____________________________
(3) ____________________________
(4) ____________________________
(5) ____________________________
(6) ____________________________
12. What are the characteristics of coliform bacteria?
13. How does chlorine kill microorganisms?
14. Define prechlorination, postchlorination, and hypo-
chlorination.
15. Differentiate between free residual and combined
residual chlorine.
16. What is the purpose of breakpoint chlorination?
17. Draw a breakpoint curve and explain its various parts.
18. Which of these is a preferred chloramine species and
why?
a. Monochloramine
b. Dichloramine
c. Trichloramine
19. What is the ratio of chlorine to ammonia for proper
chloramination?

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Basic Chemistry for Water and Wastewater Operators

20. Chlorine dioxide is one of the preferred predisinfec-

tants. Why?
21. What is the end product of chlorine dioxide and
how is it controlled?
22. Give advantages and disadvantages of ozonation.
23. Ozone is a form of oxygen. True or False.
24. Chlorine or chloramines are more effective when
used after ozone or chlorine dioxide treatment. True
or False.
25. CT value is the product of milligrams pre litre of the
disinfectant and its contact time in minutes. True or
False.

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Appendix

153
 Chemical Name Common Name Chemical Formula Used for

Aluminum sulfate Alum Al2(SO4)3·14H2O Coagulation

154
Ammonia Ammonia gas NH3 (ammonia gas)

Ammonia aqua NH4OH (ammonia solution) Chloramination

Calcium bicarbonate Ca(HCO3)2 Alkalinity

Calcium carbonate Limestone CaCO3

Calcium hydroxide Hydrated lime or slaked lime Ca(OH)2 Softening

Calcium hypochlorite HTH Ca(ClO)2 Chlorination

BasicChemistry.book Page 154 Monday, February 18, 2002 5:03 PM

Calcium oxide Unslaked lime or quick lime CaO Softening

Carbon Activated carbon C Taste, odors, and pesticide

removal
Basic Chemistry for Water and Wastewater Operators

Chlorine Cl2 Disinfection

Chlorine dioxide ClO2 Disinfection

Copper sulfate Blue vitriol CuSO4·5H2O Algae control

Some Chemicals Used in Water and Wastewater Treatment

Table continues next page
 Chemical Name Common Name Chemical Formula Used for

Ferric chloride FeCl3·6H2O Coagulation

Ferric sulfate Fe2(SO4)3 Coagulation

Ferrous chloride FeCl2 Chlorite control

Fluosilicic acid Fluoride H2SiF6 Fluoridation

(hydrofluosilicic acid)

Hydrochloric acid Muriatic acid HCl

Ozone O3 Disinfection
BasicChemistry.book Page 155 Monday, February 18, 2002 5:03 PM

Potassium dichromate K2Cr2O7

Potassium permanganate KMnO4 Taste and odor control

Sodium aluminate NaAlO2 Coagulation

Sodium bicarbonate Baking soda NaHCO3 Alkalinity

Sodium carbonate Soda ash Na2CO3 Softening

Sodium chloride Salt NaCl

Some Chemicals Used in Water and Wastewater Treatment (continued)

155
Appendix

Table continues next page

156
Chemical Name Common Name Chemical Formula Used for

Sodium chlorite NaClO2 Chlorine dioxide formation

Sodium fluoride NaF Fluoridation

Sodium fluosilicate Na2SiF6 Fluoridation

Sodium hexametaphosphate Calgon Na6(PO3)6 or 6(NaPO3) Sequestering

Sodium hydroxide Lye NaOH Alkalinity

BasicChemistry.book Page 156 Monday, February 18, 2002 5:03 PM

Sodium hypochlorite Bleach NaClO Chlorination

Sodium phosphate Na3PO4·12H2O

Sodium thiosulfate Na2S2O3

Basic Chemistry for Water and Wastewater Operators

Sulfuric acid Oil of vitriol H2SO4

Zinc orthophosphate Zn3(PO4)2 Corrosion control

Some Chemicals Used in Water and Wastewater Treatment (continued)

BasicChemistry.book Page 157 Monday, February 18, 2002 5:03 PM

Appendix

Some Equations Common in Water and

Wastewater Chemistry

Softening

Ca(OH)2 + Ca(HCO3)2 → 2CaCO3↓ + 2H2O

Ca(OH)2 + Mg(HCO3)2 → CaCO3↓ + MgCO3 + 2H2O
Ca(OH)2 + MgCO3 → CaCO3↓ + Mg(OH)2↓
CaSO4 + Na2CO3 → CaCO3↓ + Na2SO4
Ca(OH)2 + MgSO4 → CaSO4 + Mg(OH)2↓

Coagulation

Al2(SO4)3 + 3Ca(OH)2 → 2Al(OH)3↓ + 3CaSO4

Fe2(SO4)3 + 3Ca(OH)2 → 2Fe(OH)3↓ + 3CaSO4

Disinfection

Cl2 + H2O → HCl + HOCl

Ca(OCl)2 + 2H2O → Ca(OH)2 + 2HOCl
NH3 + HOCl → NH2Cl + H2O
NH3 + 2HOCl → NHCl2 + 2H2O

Neutralization

CO2 + Ca(OH)2 → CaCO3↓ + H2O

CaCO3 + H2SO4 → CaSO4 + H2O + CO2↑
Ca(HCO3)2 + H2SO4 → CaSO4 + 2H2O + 2CO2↑

Compounds Causing Acidity and Alkalinity in Water

CO2 + H2O → H2CO3

Al2(SO4)3 + 3H2O → 2Al(OH)3↓ + 3H2SO4
CaO + H2O → Ca(OH)2

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BasicChemistry.book Page 159 Monday, February 18, 2002 5:03 PM

Glossary

Acid A compound that forms hydronium ions in water

solution. It is a proton donor.
Acid anhydride A nonmetallic oxide that reacts with water
to form an acid.
Adsorption The acquisition of a gas, liquid, or solid on the
surface of a solid particle.
Alcohol An organic compound containing a hydrocarbon
group and one or more –OH groups.
Allotropy The existence of an element in two or more forms
in the same physical state.
Amphiprotic Capable of acting either as an acid or as a base.
Angstrom A unit of linear measure; 10–8 cm.
Anhydrous Without water of crystallization.
Anion A negative ion.
Anode Electrode that attracts anions. A positively charged
pole. The electrode where oxidation takes place.
Atom The smallest particle or unit of an element that is
capable of entering into combinations with other elements.
Atomic number The number of protons in the nucleus of an
atom.
Atomic weight The relative average atomic mass of an
element compared to 1⁄ 12 the mass of carbon-12 isotope.
Avogadro number The number of carbon-12 atoms in
exactly 12 g of this isotope: 6.022169 × 1023.
Base A substance that accepts protons from another
substance.

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Basic Chemistry for Water and Wastewater Operators

Base, conjugate The part of an acid molecule that is left after

it has donated protons.
Basic anhydride A metallic oxide that combines with water
to form a hydroxide.
Binary compounds Compounds that are formed of two
elements.
Blue vitriol Hydrate copper (II) sulfate, CuSO4·5H2O.
Boiling point The temperature at which equilibrium vapor
pressure is equal to the prevailing atmospheric pressure.
Brownian motions The peculiar dancing movements of
colloid particles as a result of collisions with the molecules
of water.
Buffer A substance that resists any change in pH.
Calorie The quantity of heat required to raise the
temperature of 1 g of water by 1°C.
Catalyst A substance that alters the rate of a chemical
reaction but remains unchanged itself at the end of the
reaction.
Cathode A negatively charged electrode. It attracts cations.
The electrode where reduction occurs.
Cation A positively charged ion.
Chemical bond The bondage between atoms produced by
transfer or sharing of electrons.
Chemical change A change in which new chemicals with
new properties are formed.
Colloidal suspension Suspended particles (1–100 nm in
diameter) in a dispersing medium.
Compound A substance composed of two or more elements
combined in a definite proportion.
Concentrated Containing a large amount of solute.
Covalence Covalent bonding.
Covalent bond Bond formed by a pair of shared electrons.
Dehydration The removal of water from a substance.

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Glossary

Deliquescence Taking up water by a substance from the air

to form a solution.
Density The mass per unit volume of a substance.
Diatomic Particle consisting of two atoms.
Diffusion The process of spreading out of particles to
uniformly fill a space.
Dilute Containing a small amount of dissolved solute.
Dipole A polar molecule with one region positive and the
other negative.
Diprotic An acid that can donate two protons per molecule.
Dissociation The separation of ions of an ionic solute during
the solution formation.
Ductile Capable of being drawn into a wire.
Effervescence The rapid release of a dissolved gas from a
liquid.
Electrochemical Pertaining to spontaneous oxidation
reduction reactions used as a source of electric energy.
Electrolysis Decomposition of a substance by electricity.
Electrolyte A substance whose water solution conducts
electricity.
Electron A negatively charged particle revolving around the
nucleus of an atom.
Electronegativity The force by which shared electrons are
attracted by a combining atom.
Electrovalence Ionic bonding.
Element A substance that cannot be decomposed by
ordinary chemical means.
Emulsoid or emulsion Dispersion of a liquid in a liquid.
End point or equivalence point Point in a titration at
which quantities of the standard and standardized
chemicals are chemically equivalent.
Endothermic A reaction in which heat is absorbed.

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Basic Chemistry for Water and Wastewater Operators

Energy level A region around the nucleus of an atom in

which electrons revolve.
Enzyme A catalyst produced by living cells.
Equilibrium A dynamic state in which two opposing
processes proceed at the same rate at the same time.
Equilibrium vapor pressure The pressure of a vapor in
equilibrium with its liquid.
Ester An organic oxide.
Evaporation The escape of molecules from the surface of
liquids and solids.
Exothermic reaction A chemical reaction that liberates
heat.
Fat An organic oxide formed of glycerol and long carbon
chain acids.
Formality See molarity.
Formula A shorthand representation of the composition of a
chemical using chemical symbols and numerical subscripts.
Freezing point The temperature at which a liquid becomes a
solid.
Functional group A group of atoms occurring in many
molecules that possesses a characteristic reactivity.
Gas A state of matter in which a substance does not possess
a definite shape or volume.
Gram A metric unit of mass equal to the mass of 1 mL of
water at 4°C.
Gram atomic weight The mass in grams of one mole of
naturally occurring atoms of an element. It is the atomic
weight of an element expressed in grams.
Heat A form of energy.
Heterogeneous Having different properties in different
parts.
HTH, high-test hypochlorite Calcium hypochlorite, a solid
form of chlorine.

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Glossary

Homogeneous Having uniform properties throughout.

Hydrate A crystallized substance with water of
crystallization.
Hydration Association of water molecules to particles of the
solute.
Hydrocarbon A compound composed of hydrogen and
carbon.
Hydrogen bond A weak chemical linkage between a
hydrogen atom in one polar molecule and the more
electronegative atom in a second polar molecule of the
same substance.
Hydrolysis A chemical reaction in which water is involved
for decomposition.
Hydronium ion A hydrated proton (hydrogen ion); H3O+
ion.
Hygroscopic substance A substance that absorbs and retains
moisture from the atmosphere.
Indicator A substance that changes in color from a standard
reagent to the standardized.
Insoluble substance A sparingly soluble substance with the
solubility less than 0.1 g per 100 g of water.
Ion An atom or group of atoms with an electric charge.
Ionic bonding Chemical bonding in which electrons are
transferred from one atom to another.
Ionization The formation of ions from polar solute
molecules by the action of polar molecules of the solvent.
Isomers Compounds having the same molecular formula
but different molecular structure.
Kelvin (absolute scale) temperature Temperature on Kelvin
scale where 273 = 0°C.
Kinetic energy Energy of motion.
Lime Calcium oxide, CaO, also known as quicklime, and
Ca(OH)2, slaked lime.

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Basic Chemistry for Water and Wastewater Operators

Lipids Organic compounds composed of carbon, hydrogen,

and oxygen; fats; and oils.
Liquid A state of matter that has a definite volume but no
definite shape.
Litre Volume occupied by 1 kg of water at 4°C.
Lye A commercial grade of sodium hydroxide or potassium
hydroxide.
Malleable Capable of being hammered into different shapes.
Mass Quantity of matter of a body.
Mass number The total number of protons and neutrons in
an atom.
Matter Anything that occupies space and has mass.
Melting point The temperature at which a solid changes
into a liquid.
Metre A metric unit of length equal to 39.37 in. (1/
10,000,000 of the north polar quadrant of the Paris
Meridian).
Mixture A material composed of two or more substances,
each retaining its own properties.
Molality An expression of the number of moles of a solute
per kilogram of solvent.
Molar volume The volume of 1 mol of any gas in litres at 0°C
and 760 mm Hg pressure. It is 22.4 L.
Molarity An expression of the moles of solute per litre of
solution. It is also called formality.
Mole Amount of a substance in grams that contains an
Avogadro number of its particles. Practically, it is gram
atomic weight for an element and gram formula weight of
a compound.
Molecular formula A chemical formula representing the
composition of a molecule of a substance.
Molecular weight The formula weight of a molecular
substance.

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Glossary

Molecule The smallest stable and neutral unit of a

substance.
Monoprotic An acid capable of donating one proton per
molecule.
Neutralization The reaction between a base and an acid to
produce a salt and water.
Neutron A neutral particle in the atomic nucleus with
almost the same mass as that of a proton.
Nonelectrolyte A substance that does not conduct electricity
in its water solution.
Normal solution A solution containing 1 g equivalent
weight of a solute per litre of solution.
Normality An expression of the number of gram equivalent
weights of a solute per litre of solution.
Nucleus The positively charged and centrally located part of
an atom.
Octet Outer shell of an atom having eight electrons.
Organic Regarding carbon compounds and their
derivatives.
Oxidation A chemical reaction in which electrons are lost.
Oxidation number Number of electrons of an element
participating in compound formation. It is equal to the
electrons in a neutral atom minus the electrons in a
combined atom.
Oxidation-reduction reaction Any chemical reaction in
which electrons are transferred.
Oxidizing agent A substance that gains electrons in a
chemical reaction.
Period A horizontal row of elements in the periodic table.
Permanent hardness (noncarbonate hardness) Hardness
in water due to the presence of sulfates, nitrates, and
chlorides of calcium and magnesium.
Peroxone A combination of hydrogen peroxide and ozone
for disinfection.

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pH Minus logarithm of the hydronium ion concentration

expressed as moles per litre.
Physical change A change in which the chemical
composition of a substance remains unchanged.
Physical properties Properties that can be determined
without changing chemical composition of a substance.
Plasma An ionized gas. The fourth state of matter.
Polar covalent bond A covalent bond in which there is an
unequal sharing of electrons and thus an unequal
distribution of a charge.
Polar molecules Molecules formed by polar covalent
bonding.
Polarization Accumulation of hydrogen gas and hydroxide
ions on the cathode in a corrosion process.
Potential energy Energy of position.
Precipitation The separation of an insoluble compound
from a solution.
Protein An organic compound formed essentially of carbon,
hydrogen, oxygen, and nitrogen.
Proton A positively charged particle in the nucleus.
Radical A group of covalently bonded atoms carrying a
charge.
Redox Regarding reduction-oxidation reactions.
Reducing agent A substance that loses electrons in a
chemical reaction.
Reduction Any reaction in which electrons are gained.
Reversible reaction A chemical reaction in which the
products reform the reactants.
Salt An ionic compound formed of cations and conjugate
base anions.
Saturated (1) A solution in which the rate of dissolving is
equal to the rate of crystallization. (2) An organic com-
pound with single covalent bonds in the carbon chain.

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Glossary

Shell A part of an atom around the nucleus of an atom in

which electrons revolve.
Slaked lime Calcium hydroxide, Ca(OH)2.
Soft water Water with low calcium and magnesium
contents.
Solute The dissolved substance in a solution.
Solution The homogeneous mixture of two or more
substances.
Solution equilibrium The physical state in a solution at
which the rate of crystallization is equal to the rate of
dissolving.
Solvent A dissolving medium in a solution.
Soozone A combination of ultrasonic waves and ozone for
disinfection.
Specific gravity The ratio of the density of a substance to the
density of a standard. The standard for solids and liquids is
water with the density of 1 g/cm3; for gases, the standard is
air with the density of 1.29 g/L at standard temperature and
pressure.
Spectator ion An ion in a reaction system that does not
participate in the reaction.
Standard solution A solution with the precise concentration
of the solute.
Stoichiometry Quantitative relationship between reactants
and products in a chemical reaction.
STP The abbreviation for standard temperature (0°C) and
pressure (760 mm Hg).
Structural formula A formula that shows the bonding in a
molecule.
Supersaturated A solution that contains more dissolved
solute than a saturated solution would contain under
similar conditions.
Temporary hardness (carbonate hardness) Hardness
caused by bicarbonates of calcium and magnesium.

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Titration The technique where the concentration of a

reagent is determined by reacting it with a reagent of
known concentration.
Triprotic An acid capable of donating three protons per
molecule.
Tyndall effect The dispersion of light by colloidal particles.
Valence electrons Electrons in the outermost shell.
van der Waals forces Forces of attraction between the
nonpolar covalent molecules.
Vapor Gaseous state of substances that normally exist as
solids or liquids.
Vapor pressure Pressure due to vapor of a confined liquid or
solid.
Volatile Easily vaporized.
Zeta potential The magnitude of the charge at the boundary
between the colloidal particle and the solution.

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References

American Water Works Association. 1982. Treatment Tech-

niques for Controlling Trihalomethanes in Drinking Water.
Denver, Colo.: AWWA.
American Water Works Association Research Foundation.
1996. Internal Corrosion of Water Distribution Systems.
Denver, Colo.: AWWA and AwwaRF.
Baylis, J.R. 1930. How to Avoid Loss by Pipe Corrosion by
Water. Water Works Engrg., 83.
Glage, W.H. and K.W. Kang. 1988. Advanced Oxidation Pro-
cesses for Treating Groundwater Contaminated with
TCE and PCE: Lab Studies. Jour. AWWA, 80:5:57.
Griffin, A.E. and R.J. Baker. 1959. The Break-point Process for
Free Residual Chlorination. Jour. NEWWA.
Hurst, G.H. and W.R. Knocke. 1997. Evaluating Ferrous Iron
for Chlorite Ion Removal. Jour. AWWA, 89:8:98.
Langelier, W.F. 1936. The Analytical Control of Anti Corro-
sion, Water Treatment. Jour. AWWA, 28.
McGuire, M.J. and M.K. Davis. 1989. Treating Water With Per-
oxone: A Revolution in the Making. Water Engrg. and
Mngmt., 135:5:42.
Metcalf, H.C., J.E. Williams, and J.F. Catska. 1966. Modern
Chemistry. New York, London, Toronto, Sydney: Holt,
Rinehart, and Winston.
Quick, F.J. 1965. Introduction to Chemistry. New York: McMillan
Company.
Ryzner, J.W. 1944. A New Index for Determining Amount of
Calcium Carbonate Formed by Water. Jour. AWWA,
36:4:474.

169
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Basic Chemistry for Water and Wastewater Operators

US Environmental Protection Agency. 1977. Water Supply

Research, Office of Research and Development. Ozone,
Chlorine Dioxide and Chloramines as Alternatives to Chlo-
rine for Disinfection of Drinking Water. State of the Art. Cin-
cinnati, Ohio: USEPA.

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Index

Note: f. indicates figure; t. indicates table

A Anions, 27
Absolute scale, 10 Anodes, 123
Acid anhydrides, 75 Aromatic series. See Benzene
Acidity in water, 53 series
equations, 157 Atomic number, 15, 22
Acids, 47–48, 104. See also Polar Atomic weight, 16
covalent compounds Atoms, 13
binary, 49 structure, 15–16
defined, 47 Avogadro number, 16, 57
and electrolytes, 55 Avogadro’s hypothesis, 92–93
mineral, 47
naming, 49 B
properties, 48 Bases, 49–50
strong, 47, 83–84 properties, 50
ternary, 49 Baylis curve, 128, 129f.
weak, 47–48, 83–84 Benzene series, 99–101
Adsorption, 68 Binary acids, 49
Aeration, 120 Boyle’s law, 90–91
Alcohols, 101–102 Bromine, 144–145
Aldehydes, 103 Brownian motions, 55, 69
Alkadiene series, 99
Alkalinity, 53 C
equations, 157 Calcium, 115
Alkane series, 98 Calcium carbonate, 127–128
Alkene series, 98–99 Calories, 74
Alkyne series, 99 Carbohydrates, 105
Amides, 105 disaccharides, 108
Amines, 104 polysaccharides, 109
Amphiprotic compounds, 50–51 Carbon, 95
Anhydrides, 51, 75 bonding of atoms, 96–97
Anhydrous substances, 76 Cathodes, 123

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Cations, 27 and organic matter, 138

Celsius scale. See Centigrade properties, 134–135
scale pure, 135
Centigrade scale, 9 and reducing agents, 137–138
conversion to Fahrenheit, residual, 136–137, 137f., 139
9–10 and trihalomethanes, 134
Charles’s law, 91–92 Chlorine dioxide, 134, 145–147
Chemical formulae, 30–33 Chloroorganics, 105, 106f.–107f.
types of, 30–32, 32t. Coagulation, 70, 71
Chemical properties, 5 equations, 157
Chemical reactions, 41–44 Coliform bacteria, 133
Chemicals used in water and Colloids, 55, 65
wastewater treatment, adsorption, 68
154–156 Brownian motions, 69
Chemistry, defined, 1 dialysis, 68–69
Chloramines, 134, 143–144 effect on freezing and boiling
Chlorination, 134. See also points, 69
Chlorine eight basic classes of, 66
breakpoint, 136–139, 137f. electrical properties, 69
dechlorination, 141–142 electrophoresis, 70
factors affecting, 139–140 general properties, 68–69
hypochlorination, 142 lyophilic, 66
in iron and manganese lyophobic, 66, 67
removal, 121 methods of formation, 65
postchlorination,141 mutual precipitation by
prechlorination, 141 addition of colloids of
superchlorination, 141 opposite charge, 70
Chlorine, 133. See also particle size, 65, 65t.
Chlorination positive or negative, 67, 67f.
and ammonia, 138 precipitation by addition of
chloride of lime, 136 electrolytes, 70–71
combined residual, 138, 140 precipitation by boiling, 71
contact time, 140 precipitation by freezing, 71
CT concept, 140 Schultze–Hardy rule, 70
demand, 139 sols or gels, 66
free residual, 133–134, 136, Tyndall effect, 69
137, 137f., 138–140 types of, 66–67
health and safety concerns, van der Waals forces, 69
142–143 zeta potential, 69
hypochlorites, 136, 139, 142 Colorimetric method, 53
hypochlorous acid, 135, 139 Composition reactions, 41

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Index

Compounds, 25. See also Acids, D

Bases, Salts Dalton’s law of partial pressure, 90
amphiprotic, 50–51 Decomposition reactions, 41–42
distinguished from mixtures, Deliquescence, 76
25–26 Density, 2–3
ionic, 26–28 Depolarization, 127
naming, 33–34 Dialysis, 68–69
percentage composition of, Disaccharides, 108
34 Disinfection, 133–134. See also
Corrosion, 123–124 Bromine, Chloramines,
bacterial, 125 Chlorination, Chlorine,
Baylis curve, 128, 129f. Chlorine dioxide, Hydrogen
concentration cell, 125 peroxide, Iodine, Ozone,
control, 126–128 Peroxone, Silver ions,
depolarization, 127 Soozone, Ultraviolet light
and dissolved solids or gases, equations, 157
126 Disinfection by-products, 134
galvanic, 125 Double replacement, 42
Langelier saturation index,
128–129, 130f. E
localized (pitting), 125 Efflorescence, 76
marble test, 128 Electrolysis, 85, 85f., 146
physical, 124 Electrolytes, 55, 79
polarization, 127 in corrosion, 123
Ryzner index, 129 effects on freezing and boiling
stability indices, 128–129 points of solvents, 84
stray current, 124 in precipitation of colloids,
and temperature, 126 70–71
treatment with Electromotive series, 43t.
orthophosphates, 129 Electronegativity, 29, 30t.
treatment with Electrons, 15, 22
polyphosphates, 131 arrangement and relative
treatment with zinc energy levels, 21f., 22
phosphates, 131 maximum number of in each
uniform, 124–125 shell, 17, 21f.
Covalent bonding, 28–29, 30t. Electrophoresis, 70
in water molecules, 74 Elements, 13
Covalent compounds, 28 classes, 13
as nonelectrolytes, 79 defined, 13
Cryptosporidium parvum, list of, 19t.–20t.
133, 146 and periodic law, 22–23
CT, 140 symbols, 14, 14t.

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Empirical formulae, 32, 32t. Dalton’s law of partial

Energy, 4 pressure, 90
Equations, 37 diffusion, 88
coagulation, 157 expansion, 88
composition reactions, 41 Gay-Lussac’s law of
compounds causing acidity combining volumes of
and alkalinity, 157 gases, 92
decomposition reactions, Graham’s law of diffusion,
41 89–90
disinfection, 157 Henry’s law, 89
ionic reactions, 42 inert, 23
and law of conservation of low density, 88
masses, 37–38 and plasma, 88
neutralization, 157 pressure, 88
and products, 37 Gay-Lussac’s law of combining
and reactants, 37 volumes of gases, 92
redox reactions, 42–45 Giardia lamblia, 133, 146
replacement reactions, 42 Graham’s law of diffusion,
softening, 157 89–90
steps in writing, 38–39 Gram atomic weight, 16–17
stoichiometry (quantitative Gram equivalent weight, 57–60
calculations), 39–41 Grams, 7, 74
Escherichia coli, 133 Groups, 17
Esters, 104
Ethers, 103 H
Eudiometers, 90 Hardness, 115. See also Softening
Exponential notation, 10–11 carbonate (temporary), 116
classification scheme, 115
F and lather formation, 116
Fahrenheit scale, 9 noncarbonate (permanent),
conversion to centigrade, 9 116
Families. See Groups problems due to, 116–117
Fission, 13 Henry’s law, 89
Formality. See Molarity Hydrates, 75–76
Formula weight, 34 Hydration, 75–76
Functional groups, 101 of ions, 80
Hydrion paper, 53
G Hydrocarbons, 97, 97t.
Gases, 2, 13, 87 acids, 104
Avogadro’s hypothesis, 92–93 alcohols, 101–102
Boyle’s law, 90–91 aldehydes, 103
Charles’s law, 91–92 alkadiene series, 99

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Index

alkane series, 98 of polar covalent compounds,

alkene series, 98–99 83–84
alkyne series, 99 of water, 84
amides, 105 Ions, 27, 79
amines, 104 oxidation numbers, 31t.
benzene (aromatic) series, spectator, 82
99–101 Iron and manganese, 119
chloroorganics, 105 problems caused by, 119–120
derivatives, 101–105, 102t. removal methods, 120–121
esters, 104 Isomerism, 95, 96
ethers, 103 Isotopes, 15–16, 15f.
and functional groups, 101
ketones, 103 K
Hydrochloric acid, 135 Kelvin scale. See Absolute scale
ionization of, 83f. Ketones, 103
Hydrogen bonding, 74 Kinetic energy, 4
Hydrogen peroxide, 134, 149 Kinetic theory, 87
Hydrogenation, 110–111
Hydronium ions, 47 L
Hygroscopic substances, 76 Langelier saturation index,
Hypochlorites and 128–129, 130f.
hypochlorination, 136, Law of conservation of
139, 142 energy, 4
Hypochlorous acid, 135, 139 Law of conservation of masses,
37–38
I Law of definite composition,
Indicators, 61 25
Insoluble compounds, 81–82 Lipids, 109–110
Iodine, 145 hydrogenation, 110–111
Ion exchange, 118–119 saponification, 110
Ionic bonding, 26–27, 28f., 30t. Liquids, 2
Ionic compounds, 26–28 Litres, 8
dissociation of, 80–82, 81f. LSI. See Langelier saturation
as electrolytes, 55, 79 index
Ionic reactions, 42
and colloid formation, 65 M
Ionization, 83 Magnesium, 115
and electrolysis, 85 Manganese. See Iron and
history of theory, 79 manganese
of hydrochloric acid, 83f. Marble test, 128
modern theory, 79–84 Mass number, 16

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Matter P
chemical changes, 2 Pathogens, 133
defined, 1 Percent concentration, 56
physical changes, 2 Percentage composition of a
three states of, 1–2 compound, 34
Metals, 13, 23 Periodic law, 22–23
Metres, 7 Periodic table, 17–22, 18t.
Metric system, 7 Periods, 17
prefixes, 8–9 Peroxone, 149
units, 7–8 pH, 51–52
Molality, 57 high levels for disinfection,
Molarity, 56 134
Molecular formulae, 32, 32t. measurement methods, 53
Molecules, 28 scale, 52–53, 52f.
Moles, 16–17, 51 Physical properties, 4
Moles per litre, 51 Plasma, 88
Polar covalent compounds, 29
N ionization of, 83–84
Nanometres, 55 Polarization, 127
Neutralization equations, 157 Polyphosphates, 128
Neutrons, 15 Polysaccharides, 109
Nonelectrolytes, 55, 79 Potassium permanganate, 134
Nonmetals, 13, 23 Potential energy, 4
Normality, 57, 60 Potentiometers, 53
Nucleus, 15 Precipitation, 82
of colloids, 70–71
O in removal of iron and
Orbitals, 17 manganese, 121
Organic chemistry, 95 in softening, 117–118
Organic compounds, 95. See also Products, 37
Carbohydrates, Properties, 4–5
Hydrocarbons, Lipids, Proteins, 111–112
Proteins classifications, 112
classification of, 97 Protons, 15, 47
Oxidation, 28
Oxidation numbers, 26, 27t. R
of radicals, 30 Radicals, 29–30
of some common ions, 31t. and subscripts, 33
Oxidizing agents, 28, 42, 43t. Reactants, 37
Ozone, 134, 147–149 Recarbonation, 128

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Index

Redox reactions, 44–45 percent concentration, 56

corrosion as, 123 and pressure, 63
Reducing agents, 28, 42, 43t. saturated, 60
Reduction, 28 standard, 61–62
Replacement reactions, 42 standardized, 61–62
RI. See Ryzner index supersaturated, 61
Ryzner index, 129 and temperature, 63
titration, 61
S unsaturated, 60
Salts, 54 Solvents, 55
Saponification, 110 Soozone, 149
Schultze–Hardy rule, 70 Specific gravity, 3–4, 75
Scientific notation. See Specific properties, 5
Exponential notation Spectator ions, 82
Series. See Periods Stability index. See Ryzner
Shells, 15, 17, 22. See also index
Valence shells Stable states, 22, 23, 25
sublevels, 17, 21t. Stoichiometry, 39–41
Silver ions, 134, 150 Structural formulae, 32, 32t.
Softening in organic chemistry, 96
boiling, 117 Suspensions, 55
equations, 157 particle size, 65, 65t.
ion exchange, 118–119
precipitation, 117–118 T
Solids, 1–2, 13 Temperature scales, 9–10
Solutes, 55 conversion between
Solutions, 55–56 Fahrenheit and centigrade,
concentrated, 61 9–10
concentration of, 56–60 water as standard for, 74
defined, 55 Ternary acids, 49
dilute, 61 Titration, 61
factors affecting solubility, 63 Transition elements, 23
gram equivalent weight, Trihalomethanes, 134
57–60 Tubercles, 124
indicators, 61 Turbidity, 55
and like substances, 63 Tyndall effect, 69
molality, 57
molarity, 56 U
normality, 57, 60 Ultrasonic waves, 149
particle size, 65, 65t. Ultraviolet light, 134, 149–150

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V and oxides of nonmetals, 75

Valence. See Oxidation numbers physical properties, 73
Valence electrons, 22 as a standard, 74–75
Valence shells, 22, 23, 25 as universal solvent, 75
and compound formation, 27 Water of crystallization, 75–76,
van der Waals forces, 69 81
Water softening. See Softening
W Waterborne diseases, 133
Water, 73
Z
and hydrogen bonding, 74
and metallic oxides, 75 Zeolites, 121
and metals, 75 Zeta potential, 69
molecular structure and
properties, 74

178