SCI 401 General Chemistry Module PDF

SCI 401
General Chemistry
Lectures and Laboratory

Angelica A. Macalalad
Dr. Norrie E. Gayeta
Jennifer A. Basilan

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Copyright:
This module handbook © 2020
All rights reserved. No part of this module may be reproduced, stored in a retrieval system or
transmitted in any form or by any means, electronic, mechanical, photocopying, recording or
otherwise, without the prior written consent of the authors.
SCI 401 –GENERAL CHEMISTRY

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Foreword
As COVID-19 spreads rapidly across the globe, life is drastically different. Everyone is
adapting to the new norm of social distancing, closed facilities, and virtual learning. This
module was prepared in hopes to be used for an online platform to minimize the binge of
COVID -19.
The aim of this module is to introduce the General Chemistry to engineering students and
develop the groundwork needed for their profession. This includes the energy, the chemistry
of engineering materials and chemistry of the environment. It also includes chemical safety,
which is an important aspect in the laboratory.
Angelica A. Macalalad
Norrie E. Gayeta
Jennifer A. Basilan
MACALALAD – GAYETA - BASILAN | BATSTATEU

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Table of Contents

Overview 7

PART I
Unit 1: Introduction, Laboratory Safety and Waste Management
Laboratory Safety, Policies, Safety Data Sheet and Waste Management 10
Common Laboratory Glassware and Materials 16
Measurements
Basic Types of Quantities 19
Significant Figures 20
Precision and Accuracy 23
Dimensional Analysis 24
Temperature 28
Assessment Task 29

Unit 2: Matter and Energy
Characteristics of Matter and Calculations in Chemistry
Classification, Physical and Chemical Properties of Matter 30
Changes of Matter 33
Assessment Task 41
Energy Changes in Chemical Reactions
Heat Capacity and Calorimetry 42
Enthalpy 49
Spontaneity 53
Laws of Thermodynamics 57
Assessment Task 59
Electrochemical Energy
Oxidation-Reduction Reactions 61
Galvanic and Electrochemical Cells 62
Cell Potentials and Spontaneity 64
Assessment Task 69
Nuclear Chemistry and Energy
Nuclear Stability 71
Transmutation, Nuclear Fission and Fusion 75
Assessment Task 79
Fuels
Introduction to Fuels and Combustion 80
Characteristics and Classification of a Good Fuel 82
Calorific Values 85
Assessment Task 86

Unit 3: The Chemistry of Engineering Materials
Basic Concepts of Crystal Structures
Crystal Structure 88

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Unit Cells 89
Density Computations 96
X-ray Diffraction by Crystals 98
Types of Crystals 99
Amorphous Solids 102
Assessment Task 105
Metals
Occurrence of Metals 106
Metallurgical Processes 107
Purification of Metals 111
Band Theory of Electrical Conductivity 113
Periodic Trends in Metallic Properties 115
Assessment Task 124
Polymers
Properties and Characterization of Polymers 125
The Chemistry of Polymers 126
Molecular Structure of Polymers 128
Common Polymeric Materials 130
Molecular Weight and Degree of Polymerization 131
Thermoplastics and Thermosetting Polymers 134
Copolymers 134
Polymer Crystallinity 135
Assessment Task 137
Engineered Nanomaterials
Introduction to Nanotechnology and Nanomaterials 138
Nanotechnology and Conventional Technology 138
Formation of Nanomaterials 141
Properties and Applications of Nanomaterials 145
Assessment Task 148

Unit 4: The Chemistry of the Environment
The Chemistry of the Atmosphere
Earth’s Atmospheric Cycle 149
Air Pollutants and Treatment 152
Assessment Task 156
The Chemistry of Water
Properties and Characteristics of Water 157
Classification of Water by Source 157
Reactions of Acids and Bases in Water (pH measurement) 159
Pollutants in Water 164
Water Treatment 167
Assessment Task 171
The Soil Chemistry
Nature and Composition of Soil 172
The Inorganic and Organic Matter in Soil 174
Adjustment of Soil Acidity 177

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Macro- and Micronutrients in Soil 179

Soil Pollutants 183
Soil Preservation and Restoration 189
Assessment Task 192

Final Requirement: Research Paper
Special Topics Specific to the Different Fields of Engineering 193

PART II
LABORATORY EXPERIMENTS
Experiment No. 1: Common Chemistry Laboratory Equipment 196
Experiment No. 2: Phase Changes of Matter 198
Experiment No. 3: Enthalpy Determination 200
Experiment No. 4: Daniell Cell 203
Experiment No. 5: Half-life of a Radioisotope 206
Experiment No. 6: The Energy Content of Fuels 208
Experiment No. 7: Determination of pH 210

Appendix
Periodic Table 213


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Overview
SCI 401 – General Chemistry
General Chemistry for engineering students covers basic concepts and applications of
the principles of chemistry that are important in the engineering profession. The topics
include energy, the chemistry of engineering materials and chemistry of the environment. It
also includes chemical safety, which is an important aspect in the laboratory. In addition,
students are expected to do research on special topics related to their specific field of
expertise.
INTENDED LEARNING OUTCOMES

Upon completion of this course the students should be able to:
• Discuss the application of Chemistry in relation to generation of energy

• Explain the chemical principles and concepts of structures and bonding of common
materials, and chemical processes that takes place in the natural environment and its
relationship with human activities
• Apply key chemistry concepts in designing strategies, technologies, and methods
through research related to specific field of engineering for sustainable management
and restoration of environments
STUDY SKILLS
Broad academic, technical and study skills which the students will need to successfully
complete the course. The academic section includes resources for subject areas of writing
composition, grammar, math and chemistry. The technical section links to sites that provides
instruction for students in basic web skills including e-mail and file uploads, how to navigate
and search on the web, and it also features a list of resources for student support specific to
learning management (LMS) platforms. The study skills provide a list of resources geared to
learners studying online; skill development for time management, study planning and
prioritizing.

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ASSESSMENT
There are online assessment tasks to assess students’ comprehension for each unit. The
assessment task will use an online platform specifically google classroom. All assessments
tasks and other requirements must be submitted in order to pass the course.
MATERIAL
The following Tools and Online Resources are important materials that will be necessary to
learn this module:
• Internet-based as a references of the learners

• Computer-based assessment (CBA)
• Multimedia delivery (including video conferencing)
• e-Library and data base utilization
• Interactive discussions/chat sessions thru G-suite for Education Core Services
• Recommended textbooks and reference (including web pages) materials

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Part I: Lectures

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Unit 1 – INTRODUCTION, LAB SAFETY, AND

WASTE MANAGEMENT
Laboratory Safety Policies, safety data

sheet and Waste Management
LEARNING OBJECTIVES
• The students are expected to follow proper laboratory safety

protocol, proper waste disposal procedures and integrate current
good laboratory practices in performing each laboratory experiment
Laboratory Safety Rules and Guidelines
1. Dress appropriately in the laboratory. Wear a

laboratory gown or coat to protect your clothing and
minimize skin exposure. Shoes should completely cover
the feet area (sandals are not allowed and as much as
possible heeled shoes should not be used). Long hair
should be tied back.

2. Wear protective goggles or glasses at all times in the
laboratory. Goggles are eye-protection so that when
there are liquid that splashes it will not come into the
eyes. Contact lenses increase the risk of problems with
eye safety even when protective goggles are worn.

Inform your instructor if you are wearing contact
lenses.

3. Keep your working areas organized and clean as
you work. Put your personal belonging like bags and
books away from the work areas. Chairs and other
obstacles should be set aside. After each laboratory
experiments and activities, clean your work areas and
make sure that gas valves and water faucets are closed.
Clean and dry glassware and equipment before
returning to the stock room.

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4. Keep all chemical reagents (solids and liquids) in

the assigned dispensing area. Do not bring the
containers of any chemical reagents in your work
area. Use test tubes, beakers, weigh boats and other
applicable containers to obtain chemicals from the
dispensing areas.

5. Keep the balance and weighing area clean. Do not
place chemicals directly on the balance pans instead
use weighing papers or boats or any applicable
containers for your samples. Never weigh hot
objects.

6. Check the name on the chemical reagent bottles
before using them. Label every beaker, test tubes
and containers where chemicals are transferred.

7. Avoid contaminating chemical reagents.
a. Never return unused chemicals to the reagent
bottles. This is a possible source of possible
contamination on the entire content of the bottle.
Do not insert medicine droppers or pipets into
reagent bottles; instead pour a little into a smaller
container.
b. Use a clean, dry spatula in getting solids out of the
reagent bottle. A dirty spatula will contaminate
both the portion taken and that which is left in the
reagent bottle.
c. To put solids in a test tube, a folded piece of paper

about 2 inches long and slightly wider than the
diameter of the test tube is used. Hold the test tube
in a horizontal position and slide the folded paper
with a solid at one end. Incline the test tube and
gently tap the paper until all the solids are at the
bottom of the tube. In this way, the side of the tube
is kept clean.
d. The covers of the reagents bottle should not be
interchanged.


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e. To weigh solid reagents, a clean, dry watch glass

can be used as container. Weigh the container first,
then place the solid and get the total mass. To
determine the weight of the solid reagent, subtract
the mass of the container from the total mass.

8. Dispose waste properly. Do not put anything into
the trash or sink without thinking.

a. Broken glasses should be pick and return to the
stock area for proper disposal.
b. Organic solvents should not be poured into the
sink since they are immiscible with water. Return
the waste to the stock area to be put on the
“organic solvent wastes”. Solutions with heavy
metals should be put on containers for “heavy
metal waste”.
c. Solutions poured in the sink should be washed
with plenty of water.
d. Ask your instructor if you are not sure how to
properly dispose your wastes.
e. In order to minimize damage to the environment,
chemical wastes must be separated into categories
and carefully labelled as to their contents. Please
read and follow the labels on the waste bottles to
ensure that your chemical wastes are treated
safely and appropriately. You will find containers
for:
i. General Organic Waste (flammable)
ii. Halogenated Hydrocarbons (non-
flammable)
iii. Chromic Acid Solutions (these have been
phased out)
iv. Lead
v. Silver

vi. Other Heavy Metals
vii. Waste from specific experiments in some
cases
viii. Acids


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ix. Bases
In some experiments, acids and bases will be neutralized to a pH of 6 -
10 (State law) as part of the experiment and flushed down the drain with
lots of water. Your instructor will give you instructions in particular
cases. Indicator solution or paper will be available in the lab.
x. Broken thermometers. It create the special problem of spilled mercury (a
toxic heavy metal). Report such accidents immediately to your
instructor; usually any mercury which cannot be collected is reacted
with sulfur or absorbed with a special kit before disposal as heavy metal
waste.
xi. Broken glass. Broken glass or porcelain is swept up into a dust pan and
disposed of in a special container for broken glass. Please don't use your
fingers.

9. Avoid all direct contact with chemicals.
a. Wash your hands immediately anytime
you get chemicals on them and after every
laboratory activities.
b. Clean immediately all spillage before it
dries up or goes into your skin and things.
c. Never use your mouth when using a pipet.
d. Never eat or drink in the laboratory.
e. Do not look directly into the open end of a

test tube while a reaction is being
conducted. Do not point the open end of a
test tube at someone while heating or
mixing.
f. Inhale odors and chemicals with great
caution. To determine the odor of any
chemicals, do not inhale the fumes directly.
Waft vapors with your hand toward your
nose. Use the fume hood for all irritating and
toxic vapors.


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10. Handle glasses with precautions.

a. Do not heat graduated cylinders, burets,
pipets or bottles with a Bunsen burner
flame.
b. Do not hold a test tube in your hands during
a chemical reaction.
c. In heating a small amount of solid or liquid
I a test tube, hold the test tube with a test
tube holder then incline it at an angle of 450
while moving it back and forth over the
flame on the Bunsen burner. Avoid looking
at the test tube directly while it is being
heated. Never point the mouth of the test
tube towards anyone while heating
d. Do not touch glass that has been near a

flame. Use proper holder to handle them.
Do not put directly on the laboratory table
any heated containers.
e. Always fire-polish the ends of freshly cut
glass tubing. NEVER attempt to force glass
tubing through the hole of a stopper.
Instead, make sure that both tubing and
hole are wet with soapy water. Protect
hands with several layers of towel when
inserting glass into a stopper and insert the
tubing with a screw-like motion.
f. Never use a thermometer as a stirrer!
Always support a thermometer in a beaker
or flask with a clamp. If a mercury
thermometer breaks, immediately contact
the laboratory instructor and restrict

access to the area of contamination until
cleanup can be arranged.


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10. Learn the location and proper use of safety

equipment (fire extinguisher, eye wash, safety
shower and first aid kits).
a. Fire extinguisher can be used on small or minor fire

or for smothering fires. To use the fire extinguisher:
Pull the pin.

Aim the nozzle at the base of the fire

Squeeze the handle.
Sweep the fire.

b. Eye Wash Fountain for rinsing chemicals from the
eyes.

c. Safety Shower for rinsing chemicals off the body.

11. Be aware of Material Safety Data Sheet (MSDS). It
is a document that provides workers with
procedures for safely handling or working with a
particular substance. It includes technical
information like boiling points, toxicities,
reactivities, and various numbers. It also includes
instructions regarding necessary protective
equipment, how to handle spills, first aid
suggestions, storage and disposal, and the general
health effects. Its main purpose is to safeguard
occupational health.

12. Never work alone in the laboratory area.
13. Report all accidents to your instructor no
matter how small it may seem.
14. Do not perform unauthorized experiments.
15. Do not enter the laboratory room without your
instructor.


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Common Laboratory Glassware and

Materials
Glassware used in all chemistry courses:
Glassware commonly used for conducting reactions and purifications:

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Tools used in all chemistry courses:
Various equipment in the organic chemistry laboratory:
Clamps for securing apparatuses

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Burners and tubing:
Glassware used in microscale work

LEARNING ENRICHMENT ACTIVITIES
Watch the video on the Chemical Laboratory by Rebelen Cabello

https://www.youtube.com/watch?v=9Ni5UOGp0hk&feature=youtu.be

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Measurements
Making observations is fundamental to all science. These observations can be
qualitative or quantitative. A quantitative observation is called a measurement, which
always has two parts: a number and a scale (called a unit). Both parts must be present for a
measurement to be meaningful. It is the process of getting the actual measure of an object’s
dimension or property in comparison with the standard unit of acquiring the value. A
qualitative observation does not involve a number.
Scientists recognized long ago that standard systems of units had to be adopted if
measurements were to be useful. Different standards were adopted in different parts of the
world. The two major systems are the English system used in the United States and the metric
system used by most of the rest of the industrialized world.
Most scientists in all countries have used the metric system for many years. In 1960,
an international agreement set up a system of units called the International System (le
Systè me International in French), or the SI system. This system is based on the metric system
and units derived from the metric system. The fundamental SI units are listed in the Table 1.
Table 1. Fundamental SI Units
Physical Quantity Name of Unit Abbreviation
Mass kilogram kg
Length meter m
Time second s
Temperature kelvin K
Electric Current ampere A
Amount of Substance mole mol
Luminous Intensity candela Cd

Because the fundamental units are not always convenient, prefixes are used to change
the size of the unit. These are listed in Table 2.


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Table 2. Prefixes Used in the SI System

Prefix Symbol Meaning Exponential Notation
exa E 1 000 000 000 000 000 000 1018
peta P 1 000 000 000 000 000 1015
tera T 1 000 000 000 000 1012
giga G 1 000 000 000 109
mega M 1 000 000 106
kilo k 1 000 103
hecto h 100 102
deka da 10 101
- - 1 100
deci d 0.1 10-1
centi c 0.01 10-2
milli m 0.001 10-3
micro μ 0.000001 10-6
nano n 0.000000001 10-9
pico p 0.000000000001 10-12
femto f 0.000000000000001 10-15
atto a 0.000000000000000001 10-18

One physical quantity that is very important in chemistry is volume, which is not a
fundamental SI unit but is derived from length.
The most common conversion factors for volume is shown below.
1 L = 1 (dm)3 = (10 cm)3 = 1000 cm3
1cm3 = 1 mL
1L = 100 cm3 = 100 Ml

1.0 Basic Types of Quantity:
a. Fundamental Quantities. It is referred to as the basic quantities. Quantities which
are measured by the direct method. The units assigned to the fundamental quantities
are called fundamental units.
The fundamental units meter, kilogram and second (MKS) are the standard units
for length, mass, and time, respectively. However for smaller quantities, centimeter,
gram, and second are used as fundamental units (CGS). It is important to consider these
units, particularly in solving problems.

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b. Derived Quantities. Quantities that emanate or a result of the combination of

fundamental quantities after a set of operations. Area, volume, and density are some
examples of derived quantities.

2.0 Significant Figures
It is very important to realize that a measurement always has some degree of
uncertainty. The uncertainty of a measurement depends on the precision of the measuring
device. Consider the measurement of the volume of a liquid using a buret.

Table shows that the first three numbers (20.1) remain the same regardless of who
makes the measurement; these are called certain digits. However, the digit to the right of the
1 must be estimated and therefore varies; it is called an uncertain digit. We customarily
report a measurement by recording all digits that are known with certainty plus the first
uncertain digit. This is done by always recording the certain digits and the first uncertain
digit (the estimated number). These numbers are called the significant figures of a
measurement.

Rules for Counting Significant Figures
1. Non-zero integers. Non-zero integers always count as significant figures. The number
1458 has four (4) non-zero digits, all of which count as significant figures.
2. Zeros. There are three classes of zeros:
a. Leading zeros are zeros that precede all the non-zero digits. These do not count
as significant figures. The number 0.0025, the three zeros simply indicate the
position of the decimal point. This number has only two (2) significant figures.
b. Captive zeros are zeros between non-zero digits. These always count as significant
figures. The number 1.008 has four (4) significant figures.

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c. Trailing zeros are zeros at the right end of the number. They are significant only
if the number contains a decimal point. The number 100 has only one significant
figure, whereas the number 1.00 x 102 has three (3) significant figures. The
number one hundred written as 100. Also has three (3) significant figures.

3. Exact numbers. Many times calculations involve numbers that were not obtained
using measuring devices but were determined by counting: 10 experiments, 3 apples,
8 molecules. Such numbers are called exact numbers. They can be assumed to have
an infinite number of significant figures. Other examples of exact numbers are the 2
in 2πr (the circumference of a circle) and the 4 and the 3 in 4/3πr3 (the volume of a
sphere). Exact numbers also can arise from definitions. For example, 1 inch is defined
as exactly 2.54 centimeters. Thus, in the statement 1 in 5 2.54 cm, neither the 2.54
nor the 1 limits the number of significant figures when used in a calculation.

Note that the number 1.00 x 102 is written in exponential notation. This type of
notation has at least two advantages: the number of significant figures can be easily
indicated, and fewer zeros are needed to write a very large or very small number. For
example, the number 0.000060 is much more conveniently represented as 6.0 x 10-5. (The
number has two significant figures.) It is often necessary to set the decimal point using the
power-of-10 notation to avoid introducing the appearance of unwanted significant figures.
Scientific notation is a form of shorthand used to write an extremely large and

exceedingly small numbers. A number in scientific notation has two parts. The first part is a
number between 1 and 10 (N). The second part is a power of 10 (10n) as shown below
N x 10n
The exponent n can be a positive or negative integer. To write numbers in scientific
notation, move the decimal point such that you have a number between 1 and 10. Determine
the correct exponent by counting the number of times the decimal point is moved. When the
decimal point is moved to the right, the exponent is written as a negative number. When the
decimal point is moved to the left, the exponent is written as a positive number.


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Example:
a. 0.00567 5.67 x 10-3 b. 456000 4.56 x 105

Rules for Significant Figures in Mathematical Operations

a. For multiplication or division, the number of significant figures in the result is the same
as the number in the least precise measurement used in the calculation. For example,
consider the calculation
4.56 x 1.4 = 6.38 Final answer = 6.4

Limiting term has two Two significant
significant figures figures

The product should have only two significant figures, since 1.4 has only two significant
figures.

b. For addition or subtraction, the result has the same number of decimal places as the
least precise measurement used in the calculation. For example, consider the sum
22.13
17.0 Limiting term has one
2.024 decimal place
_____________
41.154 Final answer 41.2

One decimal place

The correct result is 31.1, since 18.0 has only one decimal place.

3.0 Precision and Accuracy
Two terms often used to describe the reliability of measurements are precision and
accuracy. Accuracy refers to the agreement of a particular value with the true value. Precision
refers to the degree of agreement among several measurements of the same quantity.
Precision reflects the reproducibility of a given type of measurement. The difference between
these terms is illustrated by the results of three different dart throws shown below

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a b c

Poor precision Good precision Good precision
Poor accuracy Poor accuracy Good accuracy

Two different types of errors are illustrated in Figure above. A random error (also
called an indeterminate error) means that a measurement has an equal probability of being
high or low. This type of error occurs in estimating the value of the last digit of a
measurement. The second type of error is called systematic error (or determinate error).
This type of error occurs in the same direction each time; it is either always high or always
low. Fig. (a) indicates large random errors (poor technique). Fig. (b) indicates small random
errors but a large systematic error, and Fig. (c) indicates small random errors and no
systematic error.

4.0 Dimensional Analysis
It is often necessary to convert a given result from one system of units to another. The
best way to do this is by a method called the unit factor method or, more commonly,
dimensional analysis. The pattern to illustrate the use of this method is shown below.

Desired unit

Given unit x ___________________ = Desired unit
Given unit

Some equivalents in the English and metric systems are given below.

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Example 1

A pencil is 7.00 in long. What is its length in centimeters?

Solution
Since we want to convert from inches to centimeters, we need the equivalence
!.#$ &'
statement 2.54 cm = 1 in. The correct unit factor in this case is
( )*

!.#$ &'
7.00 𝑖𝑛 𝑥 ( )*
= 7.00 (2.54)𝑐𝑚 = 17.8 𝑐𝑚

Here the inch units cancel, leaving centimeters, as requested.


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Example 2
A student has entered a 10.0 km run. How long is the run in miles?

Solution

This conversion can be accomplished in several different ways. Since we

have the equivalence statement 1 m = 1.094 yd, we will proceed by a path
that uses this fact. Before we start any
calculations, let us consider our
strategy. We have kilometres, which we want to change to miles. We can do

this by the following route:

kilometers meters yards miles

Sample Problem 3
To proceed in this way, we need the following equivalence statements.

1 km = 1 000 m

1 m = 1.094 yd
1760 yd = 1 mi
1000 𝑚 1.094 𝑦𝑑 1 𝑚𝑖
10.0 𝑘𝑚 𝑥 𝑥 𝑥 = 6.216 𝑚𝑖
1 𝑘𝑚 1 𝑚 1 760 𝑦𝑑

Note in this case that 1 mi equals exactly 1760 yd by designation.
Thus 1760 is an exact number.

Since the distance was originally given as 10.0 km, the result can
have only three significant figures and should be rounded to 6.22 mi. Thus,

10.0 km =6.22 mi


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Example 3
The speed limit on many highways in the United States is 55 mi/h. What
number would be posted in kilometres per hour?
Solution
We use the following unit factors to make the required conversion:

55 𝑚𝑖 1760 𝑦𝑑 1 𝑚𝑖 1 𝑘𝑚
𝑥 𝑥 𝑥 = 88 𝑘𝑚/ℎ
ℎ 1 𝑚𝑖 1 .094 𝑦𝑑 1 000 𝑚
Result obtained by
rounding only at the
end of the calculation

Note that all units cancel except the desired kilometres per hour

Example 4

A Japanese car is advertised as having a gas mileage of 15 km/L. Covert this
rating to miles per gallon.
Solution

15 𝑘𝑚 1000 𝑚 1.094 𝑦𝑑 1 𝑚𝑖 1 𝐿 4 𝑞𝑡
𝑥 𝑥 𝑥 𝑥 𝑥 = 35 𝑚𝑖/𝑔𝑎𝑙
𝐿 1 𝑘𝑚 1 𝑚 1 760 𝑦𝑑 1.06 𝑞𝑡 1 𝑔𝑎𝑙

Result obtained by
rounding only at the
end of the calculation

Example 5
The latest model Corvette has an engine with a displacement of 6.20 L. What
is the displacement in units of cubic inches?
Solution
1 𝑓𝑡 + (12 𝑖𝑛)+
6.20 𝐿 𝑥 𝑥 = 378 𝑖𝑛+
28.32 𝐿 (1 𝑓𝑡)+

Note that the unit factor for conversion of feet to inches must be cubed to

accommodate the conversion of ft3 to in3


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7.0 Temperature
Although many of the SI units have found their way gradually into everyday use, the
units for temperature may be the least familiar. Temperature scales arise from the choice of
two standard reference points that can be used to calibrate temperature with the use of a
thermometer. The familiar Fahrenheit scale originally chose body temperature as one
reference and set it at 100°F. The second reference point was the coldest temperature that
could be achieved by adding salt to ice water, a practice that lowers the melting point of ice.
This established 0°F, and the temperature range between the two points was divided into
100 equal units. The scale is now defined by setting the freezing point of water at 32°F and
the boiling point of water at 212°F. The Celsius scale was developed in a similar way, but
with the freezing point of pure water set at 0°C and the boiling point of water at 100°C.
Conversions between the two scales are given by the following expressions:
°F = (1.8 × °C) + 32 (1.1)
°C = (°F − 32) /1.8
Conversions between Celsius degrees and kelvins are common in science and are also
more straightforward.
K = °C + 273.15
°C = K − 273.15

References:
Brown, L., Brown, L. S., & Holme, T. (2011). Chemistry for engineering students. Nelson
Education.

Macalalada A. A. & Magoling B. A. (2015). Laboratory Manual in Organic Chemistry for Allied
Health Sciences.

Skoog, D., West, D., Holler, J., Crouch, S., Chen, S. (2011). Introduction to Analytical Chemistry.
(Philippine Edition), Cengage Learning,

Zumdahl S. S. & Zumdahl S. A. (2014). Chemistry (9th edition), Cengage Learning.

https://study.com/academy/lesson/material-safety-data-sheet-msds-definition-
purpose.html

https://chem.libretexts.org/

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ASSESSMENT TASK

I. Give the number of significant figures for each of the following data.
a. 0.0105 g ________
b. 8.050 x 10-3 s ________
c. 0.0035 cm ________
d. 55.0 cm3 ________
e. 0.8900 kg ________
f. 26.030 m3 ________
II. Write the following number in scientific notation:
a. 0.000 543
b. 0. 000 000 870
c. 50.7 x 105
d. 63.8 x 10-3
e. 0. 0000234
f. 560 000 000 000.0
III. Perform these calculations and express the result with the proper number of
significant figures.
a. (4.850 g – 2.34 g)/1.3 mL
b. (4.66 ´ 10–3) ´ 4.666
c. 0.003400/65.2
IV. Solve the following problems correctly:
1. How far in centimeters is a distance of one femtometer?
2. The density of gold is 19.32 grams per cubic centimeter. How many kilograms per
cubic meter is this?
3. In many ideal gas problems, room temperature is considered to be at 300 K to make
calculations easier. What is this temperature in Celsius?
4. Dry ice, or frozen carbon dioxide sublimes (phase change between solid to gas) at -
78.5 °C under normal atmospheric pressures. What is this temperature in
Fahrenheit?

30
Unit 2 - Matter and Energy

Characteristics of Matter and Calculations
in Chemistry

LEARNING OBJECTIVES

• Classify matter and distinguish between physical and chemical
properties/changes.

1.0 Classification, Physical and Chemical Properties of Matter
Classifications of Matter
Chemistry is the he study of matter and the changes it undergoes. Matter is anything
that occupies space and has mass. Chemists distinguish among several subcategories of
matter based on composition and properties. The classifications of matter include
substances, mixtures, elements, and compounds.
A substance is a form of matter that has a definite (constant) composition and distinct
properties. Examples are water, ammonia, table sugar (sucrose), gold, and oxygen. While,
mixture is a combination of two or more substances in which the substances retain their
distinct identities. Some familiar examples are air, soft drinks, milk, and cement. Mixtures do
not have constant composition.
Mixtures are either homogeneous or heterogeneous. When a spoonful of sugar
dissolves in water homogeneous mixture is obtain in which the composition of the mixture
is the same throughout. If sand is mixed with iron filings, however, the sand grains and the
iron filings remain separate. This type of mixture is called a heterogeneous mixture because
the composition is not uniform. Any mixture, whether homogeneous or heterogeneous, can
be created and then separated by physical means into pure components without changing
the identities of the components. After separation, the components of the mixture will have
the same composition and properties as they did to start with.


31
Elements and Compounds

Substances can be either elements or compounds. An element is a substance that
cannot be separated into simpler substances by chemical means. For convenience, chemists
use symbols of one or two letters to represent the elements. Atoms of most elements can
interact with one another to form compounds. Compound is composed of atoms of two or
more elements chemically united in fixed proportions. Unlike mixtures, compounds can be
separated only by chemical means into their pure components.
The relationships among elements, compounds, and other categories of matter are
summarized in the figure below.

Substances can exist in three states: solid, liquid, and gas. Distances between
molecules distinguish them from one another. Solid, molecules are held close together in
an orderly fashion with little freedom of motion. Molecules in a liquid are close together
but are not held so rigidly in position and can move past one another. In a gas, the
molecules are separated by distances that are large compared with the size of the
molecules.
The diagram below shows the molecular arrangement of the three states of matter.

32
Refer to this simulation link to explore more understanding on the three

states of matter
https://phet.colorado.edu/sims/html/states-of-matter/latest/states-of-matter_en.html

Physical and Chemical Properties of Matter
Substances are identified by their properties as well as by their composition. A
physical property can be measured and observed without changing the composition or
identity of a substance. Color, melting point, and boiling point are physical properties.
On the other hand, chemical property is the characteristic of a substance that is
observed during a reaction in which the chemical composition or identity of the substance is
changed. After such change, the original chemical substance vanished, and all that will be left
is a different chemical substance
All measurable properties of matter fall into one of two additional categories:
extensive properties and intensive properties. The measured value of an extensive property
depends on how much matter is being considered. The value of an extensive quantity
depends on the amount of matter. Mass, length, and volume are examples of extensive
properties. On the other hand, intensive property does not depend on how much matter is
being considered. Color, odor, taste, density, and temperature such as boiling point and
melting point are examples of intensive properties.


33
2.0 Changes of Matter

Chemical reaction is a process in which a substance (or substances) is changed into
one or more new substances. To represent chemical reaction chemical equation is used. A
chemical equation uses chemical symbols to show what happens during a chemical reaction.
A chemical equation is a shorthand method of representing chemical reaction using chemical
symbols and formulas to indicate the reactants and the products. Reactants are the starting
materials in a chemical reaction and product is the substance formed as a result of a chemical
reaction. In a chemical equation, the reactants are conventionally written on the left and the
products on the right of the arrow. To provide additional information, chemists often
indicate the physical states of the reactants and products by using the letters g for gas, l for
liquid, s for solid, and aq for aqueous.
Knowing the states of the reactants and products is especially useful in the laboratory.
For example, when potassium bromide (KBr) and silver nitrate (AgNO3) react in an aqueous
environment, a solid, silver bromide (AgBr), is formed. This reaction can be represented by
the equation:

KBr(aq) + AgNO3(aq) KNO3(aq) + AgBr(s)

If the physical states of reactants and products are not given, an uninformed person
might try to bring about the reaction by mixing solid KBr with solid AgNO3. These solids
would react very slowly or not at all.
The important principles to remember about chemical equations is that every
compound has a formula which cannot be altered and a chemical reaction must account for
every atom that is used. This is an application of the Law of Conservation of Mass which
states that in chemical reaction atoms are neither created nor destroyed.

Completing and Balancing Chemical Equations
In order to be able to predict the products in a reaction we shall consider the simple
types of reaction such as combination, decomposition, replacement (displacement),
metathesis (double displacement) and the neutralization reaction.
When writing equations we follow these steps:

34
a. Write the correct formulas of the reactants, if necessary.

b. Decide what type of reaction it is and thus what the products are.
c. Write the correct formula (s) for the product (s)
d. Balance the equation

Types of Chemical Reactions
1. Combination Reactions – two or more substances combine to form one product.
General Form: A + B AB
Patterns for Combination Reactions:
a. Metal + Nonmetal Binary compound
Example: 4AI(s) + 3O2(g) 2AI2O3(s)

Note: For metals with variable oxidation number, the final product depends
on the reaction condition.

b. Nonmetal + oxygen Nonmetal oxide
Example: 2C(s) + O2 (limited) 2CO(g)
C(s) + O2 (unlimited) CO2(g)
c. Metal oxide + water metal hydroxide (base)
Note: Metal oxide is sometimes called basic oxide or basic anhydride
Example: CaO(s) + H2O(I) Ca(OH)2(aq)

d. Nonmetal oxide + H2O oxyacid (acid)
Note: Nonmetal oxide is sometimes called acid oxide or acid anhydride
Example: SO2(g) + H2O(I) H2SO3(aq)
SO3(g) + H2O(I) H2SO4(aq)

e. Metal oxide + Nonmetal oxide salt
Example: CaO(s) + SO2(g) CaSO3(s)

2. Decomposition Reaction– a compound decomposed to form two or more substances

35

General Form: AB Δ A + B
Patterns for Decomposition Reactions:
a. Hydrates Δ salt + water
Example: CuSO4.5H2O Δ CuSO4(s) + 5H2O(g)
b. IA bicarbonates Δ Carbonates + H2O + CO2
Example: 2 KHCO3 Δ Cu2CO3(s) + H2O(g) + CO2(g)
c. IIA bicarbonates Δ Metal oxide + H2O + CO2
Example: Mg(HCO3)2(s) Δ Mg0(s) + H2O + CO2
d. Carbonates Δ Metal oxide + CO2
Example: Na2CO3(s) Δ Na2O (s) + CO2(g)
e. Chlorates Δ Chloride + Oxygen
Example: 2KCIO3(s) Δ 2KCI(I) +302(g)
f. Metal oxide Δ Metal + oxygen
Example: CaO(s) Δ Ca(s) + O2(g)
g. H2O(I) Δ H2 (g) + O2 (g)

3. Displacement Reaction– more active metal can displace a less active metal, while a
less active one can’t displace the more active.
General Form: AY + B BY + A
Where: A & B are metals (refer to activity series)
Example: Fe(s) + CuSO4(aq) FeSO4(aq) + Cu(s)
Zn(s) + MgSO4(aq) no reaction
Below is a list of metals arranged in the order of decreasing activity, called
electromotive or activity series.

36

• Metals above hydrogen displace hydrogen gas from an acid.
Example: 2AI(s) + 6HCI(aq) 2AICI3(aq) + 3H2(g)
• There are also replacement reactions involving non-metals. For example,
for the halogens, the series would be fluorine, chlorine, bromine and iodine.
Example: Cl2(g) + 2NaBr(aq) 2NaCl(aq) + Br2(aq)
I2(g) + 2NaBr(aq) no reaction

4. Metathesis (Double Displacement Reaction) – the positive ions exchange
partners with the negative ions to form two new compounds.
General Form: AX + BY AY + BX
• All neutralization reaction involving acids and bases are actually
metathesis reaction.
Example: AgNO3(aq) + HCI(aq) AgCl(aq) +HNO3(aq)
Na2SO4(aq) + Pb(NO3)2(aq 2 NaNO39aq) + PbSO4(aq)
• Any carbonate, either in the solid state or aqueous solution, react with acid
to form water, carbon dioxide gas, and salt.

Example: CaCo3(s) + 2HCl(aq) CaCl2(aq) + CO2(g)


37
5. Neutralization Reaction
Types of neutralization reaction:
a. Acid + base salt + water
Example: HCl(aq) + NaOH(aq) NaCl(aq) + H2O(I)

b. Metal oxide + acid salt + water
Example: CaO(s) + 2HCl(aq) CaCl2(aq) + H2O(I)

c. Nonmetal oxide + base salt +water
Example: SO2(g) + 2NaOH Na2SO3 + H2O

d. Ammonia + Acid ammonium salt
Example: NH3 + HCl NH4Cl

6. Combustion Reaction – reaction of elements and compounds with oxygen.
Example: C(s) + O2 (limited) CO
C(s) + O2 (excess) CO2
C2H4 + O2 (limited) CO + H2O
C2H4 + O2 (excess) CO2 + H2O
Stoichiometric Calculations
Stoichiometry is a term used to describe quantitative relationships in chemistry. It is
the quantitative study of reactants and products in a chemical reaction. Whether the units
given for reactants (or products) are moles, grams, liters (for gases), or some other units,
moles is used to calculate the amount of product formed in a reaction. This approach is called
the mole method, which means simply that the stoichiometric coefficients in a chemical
equation can be interpreted as the number of moles of each substance.
To perform the calculations involved in stoichiometry, it is necessary to understand
the mole and how to calculate the number of moles from the mass of a substance and its
molar mass. The molar mass of a substance is the mass in grams of one mole of the substance.

38
Molar masses are calculated by summing the atomic masses of all the elements appearing in
a chemical formula
To understand this clearly, first consider the significance of a chemical equation. For
example, the balances equation in a combination reaction of aluminum oxide and water is
Al2O3 + 3H2O 2Al(OH)3
Quantitatively, this means that 1 mole of aluminum oxide reacts with 3 moles of
water yield 2 moles of aluminum hydroxide. Also from the coefficients in the balanced
equation you can derive the following relationships:
1 mole Al2O3 = 2 moles Al(OH)3
1 mole Al203 = 3 moles H2O
Then you are going to consider the mole concept to find the mass of a mole of each
of the substances involve.
The following are the general approach for solving stoichiometry problems:
1. Write a balanced equation for the reaction.
2. Convert the given amount of the reactant (in grams or other units) to number of moles.
3. Use the mole ratio from the balanced equation to calculate the number of moles of
product formed.
5. Convert the moles of product to grams (or other units) of product.


39

Example 1
What mass of AgNO3 (169.9 g/mol) is needed to convert 2.33 g of Na2CO3
Stoichiometry parang test
(106.0 g/mol) to Ag2CO3? What mass of Ag2CO3 (275.7 g/mol) will be
http://web.mst.edu/~gbert/Aj2.HTML?JAVA/stoic1a.HTM
formed?
Na CO (aq) + 2AgNO (aq) Ag2CO3(s) + 2NaNO3(aq)
2 3 3

Solution
To solve for the mass of AgNO
3:

1 𝑚𝑜𝑙 𝑁𝑎! 𝐶𝑂+ 2 𝑚𝑜𝑙 𝐴𝑔𝑁𝑂+ 170𝑔 𝐴𝑔𝑁𝑂+
2.33 𝑔 𝑁𝑎! 𝐶𝑂+ 𝑥 106 𝑔 𝑁𝑎! 𝐶𝑂+ 𝑥 1 𝑚𝑜𝑙 𝑁𝑎! 𝐶𝑂+ 𝑥 1 𝑚𝑜𝑙 𝐴𝑔𝑁𝑂+
= 7.47 𝑔 𝐴𝑔𝑁𝑂+

To solve for the mass of Ag 2CO3 formed:
1 𝑚𝑜𝑙 𝑁𝑎! 𝐶𝑂+ 1 𝑚𝑜𝑙 𝐴𝑔! 𝐶𝑂+ 275.7 𝑔 𝐴𝑔! 𝐶𝑂+

2.33 𝑔 𝑁𝑎! 𝐶𝑂+ 𝑥 𝑥 𝑥
106 𝑔 𝑁𝑎! 𝐶𝑂+ 1 𝑚𝑜𝑙 𝑁𝑎! 𝐶𝑂+ 1 𝑚𝑜𝑙 𝐴𝑔! 𝐶𝑂+
= 6.06 𝑔 𝐴𝑔! 𝐶𝑂+

Example 2
Calculate the number of grams of aluminum sulfate that could be obtained by

the action of 12.5 grams of aluminum on an excess of sulfuric acid.

2 Al + 3H2SO4 Al2(SO4)3 + 3H2

Solution
To solve for the mass of aluminum sulfate, we need to get first the molar mass
of aluminum sulfate which is 342 g.

1 𝑚𝑜𝑙 𝐴𝑙 1 𝑚𝑜𝑙 𝐴𝑙! (𝑆𝑂$ )+ 342𝑔 𝐴𝑙! (𝑆𝑂$ )+
12.5 𝑔 𝐴𝑙 𝑥 𝑥 𝑥
27 𝑔 𝐴𝑙 1 𝑚𝑜𝑙 𝐴𝑙 1 𝑚𝑜𝑙 𝐴𝑙! (𝑆𝑂$ )+
= 79.2 𝑔 𝐴𝑙! (𝑆𝑂$ )+

40

Example 3
Given the equation:

3 Cu + 8HNO3 3Cu(NO3)2 + 2NO + 4H2O
Calculate the number of grams of copper (II) nitrate that could be produced

from 5.25 moles of copper.

Solution
To solve for the mass of copper (II) nitrate we need to get first the molar mass
of copper (II) nitrate which is 188 g.

3 𝑚𝑜𝑙 𝐶𝑢(𝑁𝑂+ )! 188𝑔 𝐶𝑢(𝑁𝑂+ )!
5.25 𝑚𝑜𝑙 𝐶𝑢 𝑥 𝑥 = 987 𝑔 𝐶𝑢(𝑁𝑂+ )!
3 𝑚𝑜𝑙 𝐶𝑢 1 𝑚𝑜𝑙 𝐶𝑢(𝑁𝑂+ )!


Practice your knowledge in solving stoichiometric problem using the following
link:
http://web.mst.edu/~gbert/Aj2.HTML?JAVA/stoic1a.HTM
https://teachchemistry.org/classroom-resources/chemical-reactions-stoichiometry-simulation

References:
Chang, R. and Goldsby, K. A. (2017). Chemistry, (12th International Edition), New York:
McGraw-Hill.

Education.

Silberberg, M. (2012). Principles of general chemistry. McGraw-Hill Education.


41

ASSESSMENT TASK

I. Given the reactants below, complete, balance and give the type of chemical reaction.

1. Calcium carbonate + heat

2. Ethane + Oxygen

3. Silver nitrate + Hydrogen sulfide

4. Manganese oxide + Hydrochloric acid

5. Sodium bicarbonate + heat

II. Solve the following problems analytically.

1. In the reaction 2Cu2S + 3O2 2 Cu2O + 2SO2

How many grams of sulfur dioxide are formed when 10.0 mol of copper (I) sulfide is

roasted? (Atomic mass: S-32, O-16)

2. How many moles of oxygen can be obtained by the decomposition of 7.5 mol of

reactant in the reaction given below?
2 H2O2 → 2 H2O + O2

3. If sodium sulfate reacts with aluminum nitrate, calculate

a. Number of moles of sodium sulfate that would react with 15 grams of aluminum

nitrate.
b. Number of moles of aluminum nitrate that could be formed from 2.75 moles of
sodium sulfate.
c. Number of grams of sodium sulfate that would be required to produce 120

grams of aluminum sulfate.


42
Energy Changes in Chemical Reactions

LEARNING OBJECTIVES

• Become acquainted with a new term for energy, called enthalpy.

• Learn ways to measure the heats of reaction or calorimetry, specific

heat and heat capacity.

• Know the standard enthalpies of formation of reactants and products.

1.0 Heat Capacity and Calorimetry

All chemical reactions exhibits the two fundamental laws: the law of conservation of
mass and the law of conservation of energy.
Energy become a word of mouth of everyone especially now we are experiencing
pandemic. To some the feeling of exhaustion, means lack of energy and seeing their special
someone makes them fully charge.
Energy, is defined as the capacity to do work. Energy, unlike matter, cannot be seen,
touched, smelled, or weighed but all of its form are capable of doing work. Chemists define
work as directed energy change resulting from a process. There are different forms of energy
namely: kinetic energy, thermal energy, chemical energy and potential energy. All forms of
energy can be transformed from one form to another. Every time we take our zumba, the
chemical energy stored within our bodies are converted to kinetic energy. Although energy
can be transformed, scientist do believed that it can neither be created nor destroyed. This
phenomenon is summarized by the law of conservation of energy: the total quantity of
energy in the universe is assumed constant.

43
Most of the chemical reactions absorb or produce energy in the form of heat. Heat is
the transfer of thermal energy between two bodies that are at different temperatures. When
describing the energy changes that occur during a process, we normally say “heat absorbed”
or “heat released”. Thermochemistry is the study of heat change in chemical reactions.
To study energy changes, we must first define the system, or the specific part of the
universe that is of interest to us. The surroundings are the rest of the universe outside the
system. There are three types of system: open, closed and isolated system. An open system
can exchange mass and energy, usually in the form of heat with its surroundings while a
closed system allows the transfer of energy (heat) but not mass. An isolated system does
not allow the transfer of either mass or energy.
The combustion of hydrogen gas in oxygen is a chemical reactions that releases
considerable amount of energy.
2H2(g) + O2(g) à 2H2O(l) + energy
The reacting mixture (hydrogen, oxygen and water molecules) are the system and the
rest of the universe is the surroundings. Since the energy is cannot be created or destroyed,
any energy lost from the system is gained by the surroundings. The heat released from the
combustion process is transferred from the system to its surroundings. The combustion
reactions is an exothermic process, which is any process that gives off heat.
Let us consider another reaction, the decomposition of mercury (II) oxide (HgO) at
high temperatures:
energy + 2HgO(s) à 2Hg(l) + O2(g)
This is an example of endothermic process, in which heat has to be supplied to the
system by the surroundings.

In the laboratory, heat changes in physical and chemical processes are determined
using a calorimeter which is a closed container designed specifically to measure heat changes.
Calorimetry is the measurement of heat changes. The specific heat (s) of a substance is the
amount of heat required to raise the temperature of one gram of the substance by one degree

44
Celsius. It has the units J/g·°C. The heat capacity (C) of a substance is the amount of heat
required to raise the temperature of a given quantity of the substance by one degree Celsius.
Its units are J/°C. Specific heat is an intensive property whereas heat capacity is an extensive
property.
The relationship between the heat capacity and specific heat of a substance is
C = ms
where m is the mass of the substance in grams.

If we know the specific heat and the amount of a substance, then the change in the
sample’s temperature (Δt ) will tell us the amount of heat (q) that has been absorbed or
released in a particular process. Heat (q) is a path function, which values are dependent on
the path taken. The equations for calculating the heat change are given by
q = msΔt
q = CΔt
where Δt is the temperature change:
Δt = tfinal - tinitial
The sign convention for q; positive for endothermic process and negative for
exothermic process.


45

Example 1
A 466-g sample of water is heated from 8.50°C to 74.60°C. Calculate
the amount of heat absorbed (in kilojoules) by the water.
Strategy We know the quantity of water and the specifi c heat of water.
With this information and the temperature rise, we can
calculate the amount of heat absorbed (q).
Solution
𝑞 = 𝑚𝑠∆𝑡
,
= (466𝑔)(4.184 - ∙ .𝐶 )(74.60 .𝐶 − 8.50 .𝐶 )

(/,
= 1.29 𝑥 10# 𝐽 𝑥 (000,

= 129 𝑘𝐽

Practice Exercise 1

An iron bar of mass 869 g cools from 94°C to 5°C. Calculate the heat
released (in kilojoules) by the metal.

Heat of combustion is usually measured by placing a known mass of a compound in a

steel container called a constant-volume bomb calorimeter, which is filled with oxygen at
about 30 atm of pressure. The closed bomb is immersed in a known amount of water and the
sample is ignited electrically, and the heat produced by the combustion reaction can be
calculated accurately by recording the rise in temperature of the water. The heat given off by
the sample is absorbed by the water and the bomb. The special design of the calorimeter
enables us to assume that no heat (or mass) is lost to the surroundings during the time it
takes to make measurements. Therefore, we can call the bomb and the water in which it is
submerged an isolated system. Because no heat enters or leaves the system throughout the
process, the heat change of the system (qsystem) must be zero and we can write
qsystem = qcal + qrxn
qsystem = 0
where qcal and qrxn are the heat changes for the calorimeter and the reaction,
respectively. Thus,
qrxn = -qcal
To determine qcal, we need to know the heat capacity of the calorimeter (Ccal) and the
temperature rise

46
qcal = CΔt
The quantity of Ccal is calibrated by burning a substance with an accurately known
heat of combustion.


47

Example 2

A quantity of 1.435 g of naphthalene (C10H8), a pungent-smelling
substance used in moth repellents, was burned in a constant-volume
bomb calorimeter. Consequently, the temperature of the water rose
from 20.28°C to 25.95°C. If the heat capacity of the bomb plus water
was 10.17 kJ/°C, calculate the heat of combustion of naphthalene on a
molar basis; that is, find the molar heat of combustion.
Strategy Knowing the heat capacity and the temperature rise, how
do we calculate the heat absorbed by the calorimeter? What
is the heat generated by the combustion of 1.435 g of
naphthalene? What is the conversion factor between grams
and moles of naphthalene?
Solution
𝑞&12 = 𝐶&12 ∆𝑡
= (10.17 𝑘𝐽/°𝐶)(25.95°𝐶 2 20.28°𝐶)

= 57.66 𝑘𝐽

Solution Because qsys = qcal + qrxn. The heat change of the reaction is

257.66 kJ. This is the heat released by the combustion of

1.435 g of C 10 H 8; therefore, we can write the conversion

factor as

3#4.55 /,
(.$+# - 6!" 7#

The molar mass of naphthalene is 128.2 g, so the heat of
combustion of 1 mole of naphthalene is

−57.66𝑘𝐽 128.2 𝑔 𝐶(0 𝐻8
𝑚𝑜𝑙𝑎𝑟 ℎ𝑒𝑎𝑡 𝑜𝑓 𝑐𝑜𝑚𝑏𝑢𝑠𝑡𝑖𝑜𝑛 = 𝑥
1.435 𝑔 𝐶(0 𝐻8 1 𝑚𝑜𝑙 𝐶(0 𝐻8

= −5.151 𝑥 10+ 𝑘𝐽/𝑚𝑜𝑙

Practice Exercise 2

A quantity of 1.922 g of methanol (CH 3 OH) was burned in a constant-
volume bomb calorimeter. Consequently, the temperature of the water rose

by 4.20°C. If the heat capacity of the bomb plus water was 10.4 kJ/°C,
calculate the molar heat of combustion of methanol.

48
There is a simpler device that the constant-volume calorimeter and that is constant-
pressure calorimeter, which is used to determine the heat changes for noncombustion
reactions. In the laboratory, students can measure heat changes using an improvised
constant-volume calorimeter from two Styrofoam coffee cups. In this improvised
calorimeter, we neglect the small heat capacity of the coffee cups in our calculations. They
used it in measuring the heat effects of a variety of reactions such as acid-base neutralization.
Heat of solution and dilution. The heat changes for the process (qrxn) is equal to the enthalpy
change (ΔH).

Watch the video on the Heat of Neutralization by Ali Hayek

https://youtu.be/eEdqC6hkhRs

49
2.0 Enthalpy
Most reactions are prepared under constant pressure (usually atmospheric pressure)
since constant-volume conditions are difficult and impossible to achieve. The reaction is
considered as expansion when there is a net increase in the number of moles of a gas after
the reaction and conversely, it is compression if more gas molecules are consumed than are
produced. The work is done one the surroundings for an expansion process and it is done on
the system for a compression process. There is no work done if there is no net change in the
number of moles of gases from the reactants to products.
In general, for a constant-pressure process we write

*where the subscript “p” means constant-pressure condition.
Enthalphy (H) is defined by the equation
H =E + PV
where E is the internal energy of the system and P and V are the pressure and volume
of the system, respectively. Enthalpy, pressure, energy and volume are all state functions,
that is, the changes depend only on the initial state and final state.

For any process, the change in enthalpy according is given by
ΔH =ΔE + Δ(PV)
If the pressure is held constant, then
ΔH =ΔE + PΔV
The two quantities, ΔE and ΔH, are can be associated with a reaction. If the reaction
occurs under constant-volume conditions, then the heat change, qv , is equal to ΔE. On the
other hand, when the reaction is carried out at constant pressure, the heat change, qp is equal
to ΔH.

50
Since most of the reactions are at constant pressure condition, we can use enthalpy
to quantify the heat flow into or out of a system in the process. we can equate the heat change
in these cases to the change in enthalpy. For any reaction of the type
reactants à products
From the reaction, we can compute for the enthalpy of reaction, ΔH, as the difference
between the enthalpies of the products and the enthalpies of the reactants. The enthalpy of
reaction can be positive or negative, depending on the process. For an endothermic process
(heat absorbed by the system from the surroundings), ΔH is positive (that is, ΔH > 0). For an
exothermic process (heat released by the system to the surroundings), ΔH is negative (that
is, ΔH < 0).

At 0°C and a pressure of 1 atm, ice melts to form liquid water. Measurements show
that for every mole of ice converted to liquid water under these conditions, 6.01 kilojoules
(kJ) of heat energy are absorbed by the system (ice). Because the pressure is constant, the
heat change is equal to the enthalpy change, ΔH. Furthermore, this is an endothermic
process, as expected for the energy-absorbing change of melting ice. Therefore, ΔH is a
positive quantity. The equation for this physical change is
H2O(s) à H2O(l) ΔH = 6.01 kJ/mol
The “per mole” in the unit for ΔH means that this is the enthalpy change per mole of
the reaction (or process) as it is written; that is, when 1 mole of ice is converted to 1 mole of
liquid water.

51
As another example, consider the combustion of methane (CH4), the principal

component of natural gas:

The natural gas, methane, when burned releases heat to the surroundings exhibiting
an exothermic process. The enthalpy change must have a negative sign since the process
releases heat. The per mole of reaction unit for ΔH means that when 1 mole of CH4 reacts
with 2 moles of O2 to produce 1 mole of CO2 and 2 moles of liquid H2O, 890.4 kJ of heat
energy are released to the surroundings. It is important to remember that the ΔH value does
not refer to a particular reactant or product. It simply means that the quoted ΔH value refers
to all the reacting species in molar quantities. Thus, the following conversion factors can be
created:

Expressing ΔH in units of kJ/mol (rather than just kJ) conforms to the standard
convention; its merit will become apparent when we continue our study of thermodynamics.
Thermochemical equations shows the enthalpy change as well as the mass
relationships. It is essential to specify a balanced equation when quoting the enthalpy change
of a reaction. The following guidelines are helpful in writing and interpreting
thermochemical equations.

52

Example 3

Given the thermochemical equation

2SO2(g) + O2(g) à 2SO3(g) ΔH = -198.2 kJ/mol

calculate the heat evolved when 87.9 g of SO2 (molar mass 5 64.07

g/mol) is converted to SO3 .

Strategy The thermochemical equation shows that for every 2 moles

of SO2 reacted, 198.2 kJ of heat are given off (note the negative

sign). Therefore, the conversion factor is

−198.2 𝑘𝐽

2 𝑚𝑜𝑙 𝑆𝑂!

How many moles of SO2 are in 87.9 g of SO2? What is the

conversion factor between grams and moles?

Solution We need to first calculate the number of moles of SO2 in

87.9 g of the compound and then find the number of kilojoules

produced from the exothermic reaction. The sequence of

conversions is as follows:

grams of SO2 à moles of SO2 à kJ of heat generated

1 𝑚𝑜𝑙 𝑆𝑂! −198.2 𝑘𝐽
𝛥𝐻 = 87.9 𝑔 𝑆𝑂! 𝑥 𝑥
64.07 𝑔 𝑆𝑂! 2 𝑚𝑜𝑙 𝑆𝑂!

= −136 𝑘𝐽

∴ the heat released to the surroundings is 136 kJ.

Practice Exercise 3

Calculate the heat evolved when 266 g of white phosphorus (P4)
burns in air according to the equation
P4(s) + 5O2(g) à P4O10(s) ΔH = - 3013 kJ/mol


53
3.0 Spontaneity
Thermodynamics deals with the interconversion of heat and other forms of energy.
This enables us to use information gained from experiments on a system to draw conclusions
about other aspects of the same system without further experimentation. Studying
thermodynamics will enable us to determine whether or not a reaction will occur when
reactants are brought together under a specific conditions example temperature, pressure
and concentration. This is important for most of the researchers and chemist doing their
synthesis of a particular compounds in the laboratory. A reaction that does occur under the
given set of conditions is called spontaneous reaction. If a reaction does not occur under
specified conditions, it is said to be nonspontaneous.

These examples show that processes that occur spontaneously in one direction
cannot, under the same conditions, also take place spontaneously in the opposite direction.

54
Experience tells us that ice melts spontaneously above 0°C even though the process is
endothermic. In this case, the assumption that spontaneous processes always decrease a
system’s energy fails. Exothermicity favors the spontaneity of a reaction but does not
guarantee it. Just as it is possible for an endothermic reaction to be spontaneous, it is possible
for an exothermic reaction to be nonspontaneous. In other words, we cannot decide whether
or not a chemical reaction will occur spontaneously solely on the basis of energy changes in
the system. To make this kind of prediction we need another thermodynamic quantity, which
turns out to be entropy.
Entropy
We have to introduce a new thermodynamic quantity called entropy to determine the
spontaneity of the reaction. Entropy (S) is described as a measure of how spread out or
dispersed the energy of a system is among the different possible ways that system can contain
energy. The greater the randomness, the greater the entropy. Most processes are
accompanied by a change in entropy. A cup of hot water has a certain amount of entropy due
to the dispersal of energy among the various energy states of the water molecules (for
example, energy states associated with the translational, rotational, and vibrational motions
of the water molecules). If left standing on a table, the water loses heat to the cooler
surroundings. Consequently, the entropy of the system increases because closely spaced
energy levels leads to a greater dispersal among the energy levels.
In 1868 Boltzmann showed that the entropy of a system is related to the natural log
of the number of microstates (W):
S = klnW
where k is called the Boltzmann constant (1.38 x 10-23 J/K). Thus, the larger the W,
the greater is the entropy of the system. Entropy is a state function and the change can be
measured as:
ΔS = Sf – Si
where Si and Sf are the entropies of the system in the initial and final states,
respectively.
ΔS = klnWf – klnWi
9
= kln 9$
%
where Wi and Wf are the corresponding numbers of microstates in the initial and final
state. Thus, if Wf . Wi, ΔS > 0 and the entropy of the system increases.

55

Standard entropy is the absolute entropy of a substance at 1 atm and 25°C. (Recall
that the standard state refers only to 1 atm. The reason for specifying 25°C is that many
processes are carried out at room temperature.) The units of entropy are J/K or J/K·mol for
1 mole of the substance. We use joules rather than kilojoules because entropy values are
typically quite small. Entropies of elements and compounds are all positive (that is, S° . 0).
For different substances in the same phase, molecular complexity determines which ones
have higher entropies. Both diamond and graphite are solids, but diamond has a more
ordered structure and hence a smaller number of microstates. Therefore, diamond has a
smaller standard entropy than graphite. Consider the natural gases methane and ethane.

56
Ethane has a more complex structure and hence more ways to execute molecular motions,
which also increase its microstates. Therefore, ethane has a greater standard entropy than
methane. Both helium and neon are monatomic gases, which cannot execute rotational or
vibrational motions, but neon has a greater standard entropy than helium because its molar
mass is greater. Heavier atoms have more closely spaced energy levels so there is a greater
distribution of the atoms’ energy among the levels. Consequently, there are more microstates
associated with these atoms.

Example 4

Predict whether the entropy change is greater or less than zero for each of
the following processes: (a) freezing ethanol, (b) evaporating a beaker of
liquid bromine at room temperature, (c) dissolving glucose in water, (d)
cooling nitrogen gas from 80°C to 20°C.

Strategy To determine the entropy change in each case, we examine
whether the number of microstates of the system increases or
decreases. The sign of ΔS will be positive if there is an increase in
the number of microstates and negative if the number of
microstates decreases.
Solution (a) Upon freezing, the ethanol molecules are held rigid in position.
This phase transition reduces the number of microstates and
therefore the entropy decreases; that is, ΔS < 0.
(b) Evaporating bromine increases the number of microstates
because the Br2 molecules can occupy many more positions in
nearly empty space. Therefore, ΔS > 0.
(c) Glucose is a nonelectrolyte. The solution process leads to a
greater dispersal of matter due to the mixing of glucose and
water molecules so we expect ΔS > 0.
(d) The cooling process decreases various molecular motions.
This leads to a decrease in microstates and so ΔS < 0.
Practice Exercise 4

How does the entropy of a system change for each of the following

processes? (a) condensing water vapor, (b) forming sucrose crystals from a

supersaturated solution, (c) heating hydrogen gas from 60°C to 80°C, and (d)

subliming dry ice.


57
4.0 Laws of Thermodynamics

The First Law of Thermodynamics states that energy can be converted from one
form to another, but it cannot be created or destroyed. One measure of these changes is the
amount of heat given off or absorbed by a system during a constant-pressure process, which
chemists define as a change in enthalpy (ΔH).
The Second Law of Thermodynamics is defined as the entropy of the universe
increases in a spontaneous process and remains unchanged in an equilibrium process.

The second law of thermodynamics tells us that a spontaneous reaction increases the
entropy of the universe; that is, ΔSuniv > 0. In order to determine the sign of ΔSuniv for a
reaction, however, we would need to calculate both ΔSsys and ΔSsurr. In general, we are usually
concerned only with what happens in a particular system. Therefore, we need another
thermodynamic function to help us determine whether a reaction will occur spontaneously
if we consider only the system itself.
We know that for a spontaneous process, we have

Now we have a criterion for a spontaneous reaction that is expressed only in terms of
the properties of the system (ΔHsys and ΔSsys) and we can ignore the surroundings.

This equation says that for a process carried out at constant pressure and
temperature T, if the changes in enthalpy and entropy of the system are such that ΔHsys -
TΔSsys is less than zero, the process must be spontaneous.
In order to express the spontaneity of a reaction more directly, we introduce another
thermodynamic function called Gibbs† free energy (G), or simply free energy:
G = H – TS
All quantities pertain to the system, and T is the temperature of the system. You can
see that G has units of energy (both H and TS are in energy units). Like H and S, G is a state
function.
The change in free energy (ΔG) of a system for a constant-temperature process is
ΔG = ΔH – TΔS

58

The standard free-energy of reaction (ΔGo ) is the free-energy change for a reaction
when it occurs under standard-state conditions.

The Third Law of thermodynamics states that entropy of a perfect crystalline
substance is zero at the absolute zero of temperature.

Example 5
Calculate the standard free-energy changes for the following reactions at
25°C.
(a) CH4(g) + 2O2(g) à CO2(g) + 2H2O(l)
(b) 2MgO(s) à 2Mg(s) + O2(g)
Strategy To calculate the standard free-energy change of a reaction, we
look up the standard free energies of formation of reactants and
products. Note that all the stoichiometric coefficients have no units
so ΔG°rxn is expressed in units of kJ/mol, and ΔG°f for O2 is zero
because it is the stable allotropic element at 1 atm and 25°C.
Solution
(a) ΔG°rxn = [ΔG°f(CO2) + 2ΔG°f(H2O)] - [ΔG°f(CH4) + 2ΔG°f(O2)]
=[(-394.4 kJ/mol) + (2)(-237.2 kJ/mol)] - [(-50.8 kJ/mol) + (2)(0
kJ/mol)]
=-818.0 kJ/mol
(b) ΔG°rxn = [2ΔG°f(Mg) + ΔG°f(O2)] - [2ΔG°f(MgO)]
=[(2kJ/mol) + (0 kJ/mol)] - [ (2)(-569.6kJ/mol)]
=1139 kJ/mol

Practice Exercise 5
Calculate the standard free-energy changes for the following reactions at
25°C:

(a) H2(g) + Br2(l) à 2HBr(g)
(b) 2C2H6(g) + 7O2(g) à 4CO2(g) + 6H2O(l)

59

ASSESSMENT TASK

1. Define the following terms:

a) Thermodynamics
b) Isolated system
c) Spontaneous
d) Enthalpy
e) Entropy

2. On what law is the first law of thermodynamics based? Explain the sign
conventions in the equation ΔE = q + w.

3. Explain what is meant by a state function. Give two examples of quantities that
are state functions and two that are not.

4. What is the difference between specifi c heat and heat capacity? What are the

units for these two quantities? Which is the intensive property and which is the
extensive property?

5. A sheet of gold weighing 10.0 g and at a temperature of 18.0°C is placed flat on a

sheet of iron weighing 20.0 g and at a temperature of 55.6°C. What is the final
temperature of the combined metals? Assume that no heat is lost to the
surroundings. (Hint: The heat gained by the gold must be equal to the heat lost
by the iron.)

6. State whether the sign of the entropy change expected for each of the following
processes will be positive or negative, and explain your predictions.

a) PCl3(l) + Cl2(g) à PCl5(s)

b) 2HgO(s) à 2Hg(l) + O2(g)
c) H2(g) à 2H(g)
d) U(s) + 3F2(g) à UF6(s)


60
References:
McGraw-Hill.

Education.

Fahlman, B. D., Purvis-Roberts, K. L., Kirk, J. S., Bentley, A. K., Daubenmire, P. L., Ellis, J. P., &
Mury, M. T. (2018). Chemistry in Context: Applying Chemistry to Society (No. 540
C517cc). McGraw-Hill.


61
Electrochemical Energy

LEARNING OBJECTIVES

• Determine the standard reduction potentials and use them to
calculate the emf of a cell and hence the spontaneity of a cell
reaction.

1.0 Oxidation-Reduction Reaction

From the different forms of energy, electrical energy has remarkable practical
importance. A day without electricity from either the power company or batteries is
unimaginable in our technological society. The area of chemistry that deals with the
interconversion of electrical energy and chemical energy is electrochemistry.
Electrochemical processes are redox (oxidation-reduction) reactions in which the
energy released by a spontaneous reaction is converted to electricity or in which electricity
is used to drive a nonspontaneous chemical reaction.
In redox reactions, electrons are transferred from one substance to another. The
reaction between magnesium metal and hydrochloric acid is an example of a redox reaction:

Recall that the numbers above the elements are the oxidation numbers of the
elements. The loss of electrons by an element during oxidation is marked by an increase in
the element’s oxidation number. In reduction, there is a decrease in oxidation number
resulting from a gain of electrons by an element. In the preceding reaction, Mg metal is
oxidized and H+ ions are reduced; the Cl- ions are spectator ions.


62

Watch the following videos for review on redox reactions:

• https://www.physicsandmathstutor.com/chemistry-revision/a-level-ocr-
a/module-2/redox-videos/
• https://www.youtube.com/watch?v=YWl4KHsUxuw
2.0 Galvanic and Electrochemical Cells

When a piece of zinc metal is placed in a CuSO4 solution, Zn is oxidized to Zn2+ ions
while Cu2+ ions are reduced to metallic copper.
Zn(s) + Cu2+(aq) à Zn2+(aq) + Cu(s)
The electrons are transferred directly from the reducing agent (Zn) to the oxidizing
agent (Cu2+) in solution. Though, if we physically isolated the oxidizing agent from the
reducing agent, the transfer of electrons can take place via an external conducting medium
(a metal wire). As the reaction progresses, it sets up a constant flow of electrons and hence
generates electricity. The apparatus for producing electricity through the use of a
spontaneous reaction is called a galvanic cell or voltaic cell, after the Italian scientists Luigi
Galvani and Alessandro Volta, who constructed early versions of the device. A zinc bar is
immersed in a ZnSO4 solution, and a copper bar is immersed in a CuSO4 solution. The cell
operates on the principle that the oxidation of Zn to Zn2+ and the reduction of Cu2+ to Cu can
be made to take place simultaneously in separate locations with the transfer of electrons
between them occurring through an external wire. The zinc and copper bars are called
electrodes. This particular arrangement of electrodes (Zn and Cu) and solutions (ZnSO4 and
CuSO4) is called the Daniell cell. By definition, the anode in a galvanic cell is the electrode at
which oxidation occurs and the cathode is the electrode at which reduction occurs.
For the Daniell cell, the half-cell reactions, that is, the oxidation and reduction
reactions at the electrodes, are

To complete the electrical circuit, the solutions must be connected by a conducting
medium through which the cations and anions can move from one electrode compartment
to the other. This requirement is satisfied by a salt bridge, which, in its simplest form, is an
inverted U tube containing an inert electrolyte solution, such as KCl or NH4NO3, whose ions
will not react with other ions in solution or with the electrodes. During the course of the
overall redox reaction, electrons fl ow externally from the anode (Zn electrode) through the
wire to the cathode (Cu electrode). In the solution, the cations (Zn2+, Cu2+, and K+) move

63
toward the cathode, while the anions (SO4 -2 and Cl-) move toward the anode. Without the
salt bridge connecting the two solutions, the buildup of positive charge in the anode
compartment (due to the formation of Zn2+ ions) and negative charge in the cathode
compartment (created when some of the Cu2+ ions are reduced to Cu) would quickly prevent
the cell from operating. An electric current flows from the anode to the cathode because
there is a difference in electrical potential energy between the electrodes. This flow of
electric current is analogous to that of water down a waterfall, which occurs because there
is a difference in gravitational potential energy, or the flow of gas from a high-pressure
region to a low-pressure region. Experimentally, the difference in electrical potential
between the anode and the cathode is measured by a voltmeter.

64
The voltage across the electrodes of a galvanic cell is called the cell voltage, or cell
potential. Another common term for cell voltage is the electromotive force or emf (E),
which, despite its name, is a measure of voltage, not force. We will see that the voltage of a
cell depends not only on the nature of the electrodes and the ions, but also on the
concentrations of the ions and the temperature at which the cell is operated. The
conventional notation for representing galvanic cells is the cell diagram. The single vertical
line represents a phase boundary.
2+ 2+
Zn (s) | Zn (1 M) || Cu (1 M) | Cu (s)

3.0 Cell Potentials and Spontaneity
When the concentrations of the Cu21 and Zn21 ions are both 1.0 M, we find that the
voltage or emf of the Daniell cell is 1.10 V at 25°C. The overall cell reaction can be thought of
as the sum of two half-cell reactions, the measured emf of the cell can be treated as the sum
of the electrical potentials at the Zn and Cu electrodes. Knowing one of these electrode
potentials, we could obtain the other by subtraction (from 1.10 V). It is impossible to
measure the potential of just a single electrode, but if we arbitrarily set the potential value
of a particular electrode at zero, we can use it to determine the relative potentials of other
electrodes. The hydrogen electrode serves as the reference for this purpose.
The superscript “°” denotes standard-state conditions, and E° is the standard
reduction potential, or the voltage associated with a reduction reaction at an electrode when
all solutes are 1 M and all gases are at 1 atm. Thus, the standard reduction potential of the
hydrogen electrode is defined as zero. The hydrogen electrode is called the standard
hydrogen electrode (SHE).

The cell diagram is

65
The Pt electrode provides the surface on which the reduction takes place. When all
the reactants are in their standard states (that is, H2 at 1 atm, H+ and Zn2+ ions at 1 M), the
emf of the cell is 0.76 V at 25°C, We can write the half-cell reactions as follows:

By convention, the standard emf of the cell, E°cell, which is composed of a
contribution from the anode and a contribution from the cathode, is given by

66

67
It is important to know the following points about the table in calculations:
• The E° values apply to the half-cell reactions as read in the forward (left to
right) direction.
• The more positive E° is, the greater the tendency for the substance to be
reduced.
• The half-cell reactions are reversible. Depending on the conditions, any
electrode can act either as an anode or as a cathode.
• Under standard-state conditions, any species on the left of a given half-cell
reaction will react spontaneously with a species that appears on the right of
any half-cell reaction located below it.
• Changing the stoichiometric coefficients of a half-cell reaction does not affect
the value of E° because electrode potentials are intensive properties. This
means that the value of E° is unaffected by the size of the electrodes or the
amount of solutions present.
• Like ΔH, ΔG, and ΔS, the sign of E° changes but its magnitude remains the
same when we reverse a reaction.

Example 1
Predict what will happen if molecular bromine (Br2) is added to a solution
containing NaCl and NaI at 25°C. Assume all species are in their standard states.
Strategy To predict what redox reaction(s) will take place, we need to
compare the standard reduction potentials of Cl2, Br2, and I2 and
apply the diagonal rule.
Solution we write the standard reduction potentials as follows:
Cl2(1 atm) + 2e- à 2Cl2(1 M) E° = 1.36V
Br2(l) + 2e à 2Br2(1 M)
- E° = 1.07 V
I2(s) + 2e à 2I (1 M)
- - E° = 0.53 V
Applying the diagonal rule we see that Br2 will oxidize I2 but will not
oxidize Cl2. Therefore, the only redox reaction that will occur
appreciably under standard-state conditions is
Oxidation: 2I-(1 M) à I2(s) + 2e-
Reduction: Br2(l) + 2e- à 2Br2(1 M)
Overall: 2I-(1 M) + Br2(l) à I2(s) + 2Br-(1 M)

Practice Exercise 1

Can Sn reduce Zn2+(aq) under standard-state conditions?


68
The measured emf (Ecell) is the maximum voltage the cell can achieve. The negative
sign indicates that the electrical work is done by the system (galvanic cell) on the
surroundings. we defined free energy as the energy available to do work. Specifically, the
change in free energy (ΔG) represents the maximum amount of useful work that can be
obtained in a reaction. For a spontaneous reaction, ΔG is negative.

Study the following links on electrochemistry:
• https://chem.libretexts.org/Bookshelves/General_Chemistry/Map%3A_Gener
al_Chemistry_(Petrucci_et_al.)/20%3A_Electrochemistry/20.3%3A_Ecell%2C_
%CE%94G%2C_and_K
• https://chem.libretexts.org/Bookshelves/General_Chemistry/Map%3A_Chemi
stry_(Zumdahl_and_Decoste)/11%3A_Electrochemistry

69

ASSESSMENT TASK


a) Anode
b) Cathode
c) Cell Voltage
d) Electromotive Force
e) Standard Reduction Potential

2. Describe the basic features of a galvanic cell. Why are the two components of the
cell separated from each other?

3. What is the function of a salt bridge? What kind of electrolyte should be used in
a salt bridge?

4. What is a cell diagram? Write the cell diagram for a galvanic cell consisting of an

Al electrode placed in a 1 M Al(NO3)3 solution and a Ag electrode placed in a 1 M
AgNO3 solution.

5. After operating a Daniell cell for a few minutes, a student notices that the cell emf

begins to drop. Why?

6. Discuss the spontaneity of an electrochemical reaction in terms of its standard
emf (E° cell).

References:
McGraw-Hill.

Education.


70


71
Nuclear Chemistry and Energy

LEARNING OBJECTIVES

• Discuss the theories of nuclear stability.

• Determine the difference between nuclear fission and fusion.

1.0 Nuclear Stability

Nuclear Chemistry is the study of reactions involving changes in atomic nuclei. It all
started with the discovery of natural radioactivity by Antoine Becquerel and grows with the
works of Pierre and Marie Curie and many others.
All nuclei contain two kinds of fundamental particles, proton and neutron, except ((𝐻.
Some nuclei are unstable; they emit particles and/or electromagnetic radiation
spontaneously this is known as radioactivity. All elements having an atomic number greater
than 83 are radioactive.
To understand the nuclear reactions, we need to learn how to write and balance
equations. Writing a nuclear equation differs somewhat from writing equations for chemical
reactions. In addition to writing the symbols for various chemical elements, we must also
explicitly indicate protons, neutrons, and electrons. In fact, we must show the numbers of
protons and neutrons present in every species in such an equation.
The symbols for elementary particles are as follows:

72

The symbol 3(0𝑒 represents an electron in or from an atomic orbital. The symbol 3(0𝛽
represents an electron that, although physically identical to any other electron, comes from
a nucleus (in a decay process in which a neutron is converted to a proton and an electron)
and not from an atomic orbital. The positron has the same mass as the electron, but bears a
+1 charge. The α particle has two protons and two neutrons, so its atomic number is 2 and
its mass number is 4.
• The total number of protons plus neutrons in the products and in the reactants
must be the same (conservation of mass number).
• The total number of nuclear charges in the products and in the reactants must
be the same (conservation of atomic number).
If we know the atomic numbers and mass numbers of all the species but one in a
nuclear equation, we can identify the unknown species by applying these rules.

Example 1
Balance this nuclear equations (that is, identify the product X):
!(! !08
8$𝑃𝑜 → 8!𝑃𝑏 + 𝑋
Strategy In balancing nuclear equations, note that the sum of atomic
numbers and that of mass numbers must match on both sides
of the equation.
Solution
a) The mass number and atomic number are 212 and 84, respectively,
on the left-hand side and 208 and 82, respectively, on the right-hand
side. Thus, X must have a mass number of 4 and an atomic number
of 2, which means that it is an a particle. The balanced equation is
!(! !08 $
8$𝑃𝑜 → 8!𝑃𝑏 + !𝛼
Practice Exercise 1
(+4 (+4
##𝐶𝑠 → #5𝐵𝑎 + 𝑋


73
The nucleus occupies a very small portion of the total volume of an atom, but it
contains most of the atom’s mass because both the protons and the neutrons reside there. In
studying the stability of the atomic nucleus, it is helpful to know something about its density,
because it tells us how tightly the particles are packed together.
The enormously high density of the nucleus prompts us to wonder what holds the
particles together so tightly. From Coulomb’s law we know that like charges repel and unlike
charges attract one another. We would thus expect the protons to repel one another strongly,
particularly when we consider how close they must be to each other. This indeed is so.
However, in addition to the repulsion, there are also short-range attractions between proton
and proton, proton and neutron, and neutron and neutron. The stability of any nucleus is
determined by the difference between coulombic repulsion and the short-range attraction.
If repulsion outweighs attraction, the nucleus disintegrates, emitting particles and/or
radiation. If attractive forces prevail, the nucleus is stable. The principal factor that
determines whether a nucleus is stable is the neutron-to proton ratio (n/p). For stable atoms
of elements having low atomic number, the n/p value is close to 1. As the atomic number
increases, the neutron-to-proton ratios of the stable nuclei become greater than 1. This
deviation at higher atomic numbers arises because a larger number of neutrons is needed to
counteract the strong repulsion among the protons and stabilize the nucleus. The following
rules are useful in predicting nuclear stability:
• Nuclei that contain 2, 8, 20, 50, 82, or 126 protons or neutrons are generally
more stable than nuclei that do not possess these numbers. For example, there
are 10 stable isotopes of tin (Sn) with the atomic number 50 and only 2 stable
isotopes of antimony (Sb) with the atomic number 51. The numbers 2, 8, 20,
50, 82, and 126 are called magic numbers. The significance of these numbers
for nuclear stability is similar to the numbers of electrons associated with the
very stable noble gases (that is, 2, 10, 18, 36, 54, and 86 electrons).
• Nuclei with even numbers of both protons and neutrons are generally more
stable than those with odd numbers of these particles
• All isotopes of the elements with atomic numbers higher than 83 are
radioactive. All isotopes of technetium (Tc, Z 5 43) and promethium (Pm, Z 5
61) are radioactive.


74

75

Review the Nuclear Stability using the following sites:
https://chem.libretexts.org/Bookshelves/General_Chemistry/Map%3A_Chemistry_(Zu
mdahl_and_Decoste)/20%3A_The_Nucleus_A_Chemists_View/20.1%3A_Nuclear_Stab
ility_and_Radioactive_Decay
https://www.youtube.com/watch?v=gqrh8wbPXVE
https://www.youtube.com/watch?v=mzLOT6uOfO4
https://teachchemistry.org/classroom-resources/half-life-investigation-simulation

2.0 Transmutation, Nuclear Fission and Fusion
Nuclear transmutation is the result from the bombardment of nuclei by neutrons,
protons, or other nuclei. An example of a nuclear transmutation is the conversion of
atmospheric ($4𝑁 𝑡𝑜 ($5𝐶 𝑎𝑛𝑑 ((𝐻, which results when the nitrogen isotope captures a neutron
(from the sun). In some cases, heavier elements are synthesized from lighter elements. This
type of transmutation occurs naturally in outer space, but it can also be achieved artificially.
Nuclear transmutation differs from radioactive decay in that the former is brought about by
the collision of two particles.

76
Particle accelerators made it possible to synthesize the so-called transuranium

elements, elements with atomic numbers greater than 92. Neptunium (Z 5 93) was fi rst
prepared in 1940. Since then, 23 other transuranium elements have been synthesized. All
isotopes of these elements are radioactive. A particle accelerator uses electric and magnetic
fi elds to increase the kinetic energy of charged species so that a reaction will occur.

Nuclear fission is the process in which a heavy nucleus (mass number. 200) divides
to form smaller nuclei of intermediate mass and one or more neutrons. Because the heavy
nucleus is less stable than its products, this process releases a large amount of energy. The
first nuclear fission reaction to be studied was that of uranium-235 bombarded with slow
neutrons, whose speed is comparable to that of air molecules at room temperature.


77

Although many heavy nuclei can be made to undergo fission, only the fission of
naturally occurring uranium-235 and of the artificial isotope plutonium-239 has any
practical importance.
The significant feature of uranium-235 fission is not just the enormous amount of
energy released, but the fact that more neutrons are produced than are originally captured
in the process. This property makes possible a nuclear chain reaction, which is a self-
sustaining sequence of nuclear fission reactions. The neutrons generated during the initial
stages of fission can induce fission in other uranium-235 nuclei, which in turn produce more
neutrons, and so on. In less than a second, the reaction can become uncontrollable, liberating
a tremendous amount of heat to the surroundings. For a chain reaction to occur, enough
uranium-235 must be present in the sample to capture the neutrons. Otherwise, many of the
neutrons will escape from the sample and the chain reaction will not occur. In this situation
the mass of the sample is said to be subcritical.
In contrast to the nuclear fission process, nuclear fusion, the combining of small
nuclei into larger ones, is largely exempt from the waste disposal problem.
For the lightest elements, nuclear stability increases with increasing mass number.
This behavior suggests that if two light nuclei combine or fuse together to form a larger, more
stable nucleus, an appreciable amount of energy will be released in the process. This is the
basis for ongoing research into the harnessing of nuclear fusion for the production of energy.
Nuclear fusion occurs constantly in the sun. The sun is made up mostly of hydrogen and
helium. Because fusion reactions take place only at very high temperatures, they are often
called thermonuclear reactions. A major concern in choosing the proper nuclear fusion
process for energy production is the temperature necessary to carry out the process. These

78
reactions take place at extremely high temperatures, on the order of 100 million degrees
Celsius, to overcome the repulsive forces between the nuclei. In contrast to the fission
process, nuclear fusion looks like a very promising energy source, at least “on paper.”
Although thermal pollution would be a problem, fusion has the following advantages: (1)
The fuels are cheap and almost inexhaustible and (2) the process produces little radioactive
waste. If a fusion machine were turned off, it would shut down completely and instantly,
without any danger of a meltdown.

79

ASSESSMENT TASK


a) Nuclear Stability
b) Transmutation
c) Fusion
d) Fission
e) Chain Reaction

2. How do nuclear reactions differ from ordinary chemical reactions?.

3. What are the steps in balancing nuclear equations?

4. What is the difference between an electron and a positron?

5. Complete the following nuclear equations and identify X in each case:

a)

b)

c)

References:
McGraw-Hill.

Education.



80
Fuels

LEARNING OBJECTIVES

• Students are expected to determine good fuels based on its
characteristics and calorific values.

1.0 Introduction to Fuels and Combustion
Since the beginning of recorded history, fire has been central to our society as a
source of heat, light, and security. Our modern fuels, the substances we burn or combust, are
available in many different forms. We use coal in power plants to generate electricity. We
use gasoline to run our cars. We use natural gas or heating oil to warm our homes. We use
propane, charcoal, or wood to cook our food at a summer barbecue. We might even use wax
to provide light for a romantic candlelit dinner. In each of these cases, using fuels means
burning them. This process of combustion causes a difference in energy between the
reactants and products of combustion, and that energy is released as light and heat—a flame!
A fuel is any solid, liquid, or gaseous substance that may be combusted (burned) to
produce heat or work. Sources of fuel date back to prehistoric times, where solids such as
grass and straw were burned for heat. The use of coal as a fuel actually dates back to ancient
civilizations, where it was used to isolate copper from ore in northeastern China as early as
1000 BC. However, the Industrial Revolution in the late 18th century sparked the large-scale
use of coal for steam engines and steelmaking. The development of drilling technology for
oil wells in the mid-19th century in the U.S. gave rise to the petroleum industry and mass
consumption of petroleum products for transportation, electricity, heating, and even plastics
fabrication. Currently, the world’s energy needs are provided by burning fossil fuels, coal,
and/or oil.
A fuel is considered valuable if it ignites easily at a low temperature and produces a
large quantity of heat during its combustion. In addition, fuels should be inexpensively
isolated and have properties that allow for their safe and efficient storage or transport.
Lastly, a desirable fuel should leave little residue behind after being burned, and produce by-
products that are not harmful to human health or the environment. Unfortunately, no fuel
satisfies all of these conditions. Humans currently use coal, petroleum products (e.g.,

81
gasoline, diesel, propane, etc.), and natural gas as our primary sources of fuel. Contrary to
popular belief, these so-called fossil fuels are not the prehistoric remains of dinosaurs. In
fact, most of the fossil fuels we use today were formed from decaying plant life that
flourished millions of years before the first dinosaurs appeared.
Considering how long it takes to convert plant life to fossil fuels, the rate at which we
are burning coal, petroleum, and natural gas is not sustainable, at least in terms of having
enough of it available to meet current and future energy needs.
Burning fossil fuels for energy fails to meet the criteria of sustainability in two ways.
First, the fuels themselves are nonrenewable. Once gone, they cannot be replaced—at least
within a useful timescale. Second, the waste products of combustion have adverse effects on
our environment, both today and in the future.
There are three necessary requirements to generate a fire—a source of heat, a fuel,
and an oxidizer. When these components are combined, a chemical reaction takes place that
releases a variety of by-products and a significant amount of heat. Once a fire is generated,
the heat or ignition source is no longer needed. The fire will continue to burn until either the
oxygen or fuel source is removed. For instance, fire blankets are used to extinguish a fire by
preventing available oxygen from reacting with the fuel source. Regardless of the specific
source of fuel or oxidizing agent, the general chemical reaction is the same.
∆
Fuel + Oxidizer → Products
The identity of the products will differ, depending on the fuel and oxidizer used for
combustion. However, the chemical makeup of these products is rarely straightforward. The
great majority of fuels are hydrocarbons, compounds made up only of the elements hydrogen
and carbon.

Watch the video on the Fuel by Dr N S Gramopadhye.

https://www.youtube.com/watch?v=4O3nC9l_lF0

82
2.0 Characteristics and Classifications of a Good Fuel

A good fuel should satisfy the following requirements:
• It should have a high calorific value i.e., it should evolve a large amount of
heat when it is burnt.
• Its moisture content should be low so that its heating value should be high.
• An ideal fuel should have moderate ignition temperature.
• It should not produce harmful products like CO2, SO2, H2S and other
poisonous gases on burning since they pollute the atmosphere.
• A fuel should have low content of non-combustible matter in the form of ash
or clinker. Since the presence of on-combustible matter will enhance the cost
of storage, handling and disposal of waste.
• The combustion of fuel should be controllable so that it can be started or
stopped.
• It should not give any offensive odor
• It should have moderate velocity of combustion.

Fuels may broadly be classified in two ways, i.e
• according to the physical state in which they exist in nature – solid, liquid and
gaseous, and
• according to the mode of their procurement – natural and manufactured.

None of these classifications, however, gives an idea of the qualitative or intensive
value of the fuels, i.e. their power of developing the thermal intensity or calorimetric
temperature under the normal condition of use, i.e. combustion of fuels in mixture with
atmospheric air in stoichiometric proportion.
We shall now proceed with the further description of the fuels. A brief description of
natural and manufactured fuels is given below:

Natural and Manufactured Fuels
Natural Fuel Manufactured Fuel
Solid Fuels
Wood Tanbark, Bagasse, Straw
Coal Charcoal
Oil Shale Coke
Briquettes
Liquid Fuels
Petroleum Oils from distillation of petroleum
Coal tar
Shale-oil
Alcohols, etc.

83
Gaseous Fuels
Natural Gas Coal gas
Producer gas
Water gas
Hydrogen
Acetylene
Blast furnace gas
Oil gas

Solid fuels are mainly classified into two categories, i.e. natural fuels, such as wood,
coal, etc. and manufactured fuels, such as charcoal, coke, briquettes. The various advantages
and disadvantages of solid fuels are given below:

Advantages Disadvantages
They are easy to transport. Their ash content is high.
They are convenient to store without any Their large proportion of heat is wasted.
risk of spontaneous explosion.
Their cost of production is low. They burn with clinker formation
They possess moderate ignition Their combustion operation cannot be
temperature. controlled easily.
Their cost of handling is high.

The liquid fuels can be classified as Natural or crude oil, and Artificial or
manufactured oils.

They possess higher calorific value per The cost of liquid fuel is relatively much
unit mass than solid fuels. higher as compared to solid fuel.
They burn without dust, ash, clinkers, Costly special storage tanks are required
etc. for storing liquid fuels.
Their firing is easier and also fire can be There is a greater risk of five hazards,
extinguished easily by stopping liquid particularly, in case of highly
fuel supply. inflammable and volatile liquid fuels.
They are easy to transport through pipes. They give bad odor.
They can be stored indefinitely without For efficient burning of liquid fuels,
any loss. specially constructed burners and
spraying apparatus are required.
They are clean in use and economic to
handle.
Loss of heat in chimney is very low due
to greater cleanliness.
They require less excess air for complete
combustion.

84
They require less furnace space for

combustion.

Petroleum is a basic natural fuel. It is a dark greenish brown, viscous mineral oil,
found deep in earth’s crust. It is mainly composed of various hydrocarbons (like straight
chain paraffins, cycloparaffins or napthenes, olefins, and aromatics) together with small
amount of organic compounds containing oxygen nitrogen and sulfur. The average
composition of crude petroleum is : C = 79.5 to 87.1%; H = 11.5 to 14.8%; S = 0.1 to 3.5%, N
and O = 0.1 to 0.5%.
Petroleums are graded according to the following physicochemical properties :
a) Specific gravity
b) Calorific value
c) Fish point or ignition point
d) Viscosity
e) Sulphur contents
f) Moisture and sediment content, and
g) Specific heat and coefficient of expansion
Gaseous fuels occur in nature, besides being manufactured from solid and liquid fuels.
The advantages and disadvantages of gaseous fuels are given below :

They can be conveyed easily through The cost of liquid fuel is relatively much
pipelines to the actual place of need, higher as compared to solid fuel.
thereby eliminating manual labor in
transportation.
They can be lighted at ease. Costly special storage tanks are required
for storing liquid fuels.
They have high heat contents and hence There is a greater risk of five hazards,
help us in having higher temperatures. particularly, in case of highly
inflammable and volatile liquid fuels.
They can be pre-heated by the heat of hot They give bad odor.
waste gases, thereby affecting economy
in heat.
Their combustion can readily by For efficient burning of liquid fuels,
controlled for change in demand like specially constructed burners and
oxidizing or reducing atmosphere, length spraying apparatus are required.
flame, temperature, etc.
They are clean in use. Very large storage tanks are needed.
They do not require any special burner. They are highly inflammable, so chances
of fire hazards in their use is high.
They burn without any shoot, or smoke
and ashes.

85
They are free from impurities found in

solid and liquid fuels.

Natural gas is generally associated with petroleum deposits and is obtained from
wells dug in the oil-bearing regions. The approximate composition of natural gas is :
CH4 = 70.9%, C2H6 = 5.10%, H2 = 3%, CO + CO= = 22%
The calorific value varies from 12,000 to 14,000 kcal/m3. It is an excellent domestic
fuel and is conveyed in pipelines over very large distances. In America, it is available to a
great extent, and so, is quite popular as a domestic fuel. It is now used in manufacture of
chemicals by synthetic process. It is a colorless gas and is non-poisonous. Its specific gravity
is usually between 0.57 to 0.7.

3.0 Calorific Values
Energy content or calorific value is the same as the heat of combustion, and can be
calculated from thermodynamical values, or measured in a suitable apparatus. Calorific
value refers to the amount of heat produced by unit volume of a substance by complete
combustion.
The efficiency of fuel mainly depends on the calorific value. If the value is high, its
efficiency will also be high. If the value is low, its efficiency would also decrease. Calorific
value is directly proportional to its efficiency.
It is very important to have a knowledge of the calorific value of fuel to carry out our
day-to-day activities. This knowledge helps us to determine the amount of energy we
transport. The gas shippers and suppliers require dis information to bill gas consumers. It
also helps to determine transportation charges of gas shippers and suppliers.
The calorific value is measured either as gross calorific value or net calorific value.
The difference being the latent heat of condensation of the water vapor produced during the
combustion process. Gross calorific value (GCV) assumes all vapor produced during the
combustion process is fully condensed. Net calorific value (NCV) assumes the water leaves
with the combustion products without fully being condensed. Fuels should be compared
based on the net calorific value.
The calorific value of coal varies considerably depending on the ash, moisture content
and the type of coal while calorific value of fuel oils are much more consistent.

86

ASSESSMENT TASK

1. Name two liquid fuels, solid fuels and gaseous fuels used in boilers.

2. What is the difference between natural and manufactured fuels?

3. Explain the difference between gross calorific value and net calorific value.

4. Identify the chemical characteristics of a fuel and describe how they make a fuel

useful

5. All of these terms fit under the heading of fuels: renewable fuel, nonrenewable
fuel, coal, petroleum, biodiesel, natural gas, and ethanol. Use a diagram to show
the relationship among them. Also find a way to show where the terms fossil
fuel and biofuel fit.


87
References:
Education.



88
Unit 3 – The Chemistry of Engineering

Materials
Basic Concepts of Crystal Structures

LEARNING OBJECTIVES

• Describe the basic structural unit or building block of the crystal
structure.
• Determine to compute the density of a solid given its unit cell.

• Classify the four types of crystals.

• Describe the characteristics of amorphous solids.

1.0 Crystal Structures
Crystalline and amorphous are the two categories of solids. For example, ice which is
a crystalline solid possesses the following characteristics: has rigid and long-range order
and its atoms, molecules, or ions occupy specific positions. In a crystalline solid, the
arrangement of particles is such that the net attractive intermolecular forces are at their
maximum. The molecular forces responsible for the stability of a crystal can be ionic forces,
covalent bonds, van der Waals forces, hydrogen bonds, or a combination of these forces. For
amorphous solids such as glass, absence of a well-defined arrangement and long-range
molecular order can be observed.
Atoms or ions (described as crystalline structures) are thought of as being solid
spheres having well-defined diameters. This is known as the atomic hard-sphere model in
which spheres representing nearest-neighbor atoms touch one another. Figure 2c showed
an example of the hard-sphere model for the atomic arrangement found in some of the
common element metals. In this specific case all the atoms are identical. Sometimes the word
lattice is used in the context of crystal structures; in this sense lattice means a three-
dimensional array of points coinciding with atom positions or sphere centers.


89
2.0 UNIT CELLS

A unit cell is the basic structural (repeating) unit of a crystalline solid. Figure 1 shows
a unit cell and its extension in three dimensions. For each sphere, it denotes an atom, ion, or
molecule and it is called a lattice point. In many crystals, the lattice point does not actually
contain such a particle. Rather, there may be several atoms, ions, or molecules identically
arranged about each lattice point. To be simple, we can assume that each lattice point is
occupied by an atom where cases are mostly metals. Table 1 shows the seven types of unit
cells where every crystalline solid can be expressed.

a) b)

Figure 1. (a) unit cell and (b) an extension of unit cell in three dimensions. The black spheres
denote either atoms or molecules (Chang & Goldsby, 2017).
Table 1. The seven types of unit cells. Angle α is defined by edges b and c, angle β by edges a
and c, and angle γ by edges a and b (Chang & Goldsby, 2017).
Unit cells Figure Dimensions and angle

Simple cubic 𝑎 = 𝑏 = 𝑐
𝛼 = 𝛽 = 𝛾 = 90°

Tetragonal 𝑎 = 𝑏 ≠ 𝑐
𝛼 = 𝛽 = 𝛾 = 90°

Orthorhombic 𝑎 ≠ 𝑏 ≠ 𝑐
𝛼 = 𝛽 = 𝛾 = 90°


90

Rhombohedral 𝑎 = 𝑏 = 𝑐
𝛼 = 𝛽 = 𝛾 ≠ 90°

Monoclinic 𝑎 ≠ 𝑏 ≠ 𝑐
𝛾 ≠ 𝛼 = 𝛽 = 90°

Tricilinic 𝑎 ≠ 𝑏 ≠ 𝑐
𝛼 ≠ 𝛽 ≠ 𝛾 ≠ 90°

Hexagonal 𝑎 = 𝑏 ≠ 𝑐
𝛼 ≠ 𝛽 = 90°, 𝛾 = 120°

The Face-Centered Cubic Crystal Structure

A unit cell of cubic geometry is considered to be the crystal structure found for many
metals. The face-centered cubic (FCC) is a crystal structure with atoms located at each of
the corners and the center of all the cube faces. Some familiar metals having this crystal
structure are copper, aluminum, silver, and gold (See Table 2). Figure 2a shows a hard-
sphere model for the FCC unit cell, whereas in Figure 2b the atom centers are represented
by small circles to provide a better perspective on atom positions. The aggregate of atoms in
Figure 2c represents a section of crystal consisting of many FCC unit cells. These spheres or
ion cores touch one another across a face diagonal; the cube edge length a and the atomic
radius R are related through

𝑎 = 2𝑅√2 Equation 1

Table 3 shows the relationship between the edge length (a) and radius (r) of atoms in the
SCC, BCC and FCC cell.


91

Example 1. Calculate the volume of an FCC unit cell in terms of the atomic

radius R.

Solution:

V = 𝑎+ 𝑏𝑢𝑡 𝑎 =? 𝑡ℎ𝑒𝑛 𝑠𝑜𝑙𝑣𝑒 𝑓𝑜𝑟 𝑎.

From the figure, solve for a: 𝑎! + 𝑎! = (4𝑅)!

Therefore, 𝑎 = 2𝑅√2

The FCC unit cell volume 𝑉& may be computed from

𝑉& = 𝑎+ = (2𝑅√2)+ = 𝟏𝟔𝑹𝟑 √𝟐

Table 2. Atomic Radii and Crystal Structures for 16 Metals (Callister & Rethwisch, 2014).

Metal Crystal Atomic Metal Crystal Atomic
Structure* Radius** Structure* Radius**
(nm) (nm)
Aluminum FCC 0.1431 Molybdenum BCC 0.1363
Cadmium HCP 0.1490 Nickel FCC 0.1246
Chromium BCC 0.1249 Platinum FCC 0.1387
Cobalt HCP 0.1253 Silver FCC 0.1445
Copper FCC 0.1278 Tantalum BCC 0.1430
Gold FCC 0.1442 Titanium (𝛼) HCP 0.1445
Iron (𝛼) BCC 0.1241 Tungsten BCC 0.1371
Lead FCC 0.1750 Zinc HCP 0.1332
*FCC = face-centered cubic; HCP = hexagonal close-packed; BCC=body-centered cubic.
**A nanometer (nm) equals 10-9m; to convert nanometers to angstrom units (Å), multiply the
nanometer value by 10.

92
a) b) c)
Figure 2. For the face-centered cubic crystal structure, (a) a hard-sphere unit cell
representation, (b) a reduced- sphere unit cell, and (c) an aggregate of many atoms (Callister
& Rethwisch, 2014).
In determining the number of atoms associated with each unit cell that depends on
an atom’s location, shared with adjacent unit cells may be considered. That is, some fraction
of the atom is assigned to a specific cell. For example, for cubic unit cells, an atom completely
within the interior “belongs” to that unit cell, one at a cell face is shared with one other cell,
and an atom residing at a corner is shared among eight. The number of atoms per unit cell,
N, can be computed using the following formula:
<$ <&
𝑁 = 𝑁) + !
+ 8
Equation 2
Where Ni = the number of interior atoms; Nf = number of face atoms and Nc = number
of corner atoms
For the FCC crystal structure, there are eight corner atoms, six face atoms and no interior
atoms. Therefore, from Equation 2.
6 8
𝑁 = 0 + + = 4
2 8
A total of four whole atoms may be assigned to a given unit cell.
There are two important characteristics of a crystal structure: (a) the coordination
number (for metals) wherein each atom has the same number of nearest-neighbor or
touching atoms; and (b) atomic packing factor (APF) which is the sum of the sphere
volumes of all atoms within a unit cell (assuming the atomic hard-sphere model) divided by
the unit cell volume. For FCCs, the coordination number is 12 as can be seen in Figure 2a.
Front face atoms has four nearest neighboring atoms around it, four face atoms that are link
from behind, and four other equivalent face atoms positioned in the next unit cell to the front
which is not shown.
From the definition of APF, the formula is:

=.2>'? .@ AB? 1A.'C )* 1 >*)A &?22
𝐴𝑃𝐹 = D.A12 >*)A .@ &?22 =.2>'?
Equation 3

93
Example 2. Show that the atomic packing factor for the FCC crystal structure
is 0.74.

Solution:

=.2>'? .@ AB? 1A.'C )* 1 >*)A &?22 =
𝐴𝑃𝐹 = D.A12 >*)A .@ &?22 =.2>'?
= ='
&
Volume of a sphere (𝑉C ) in terms of the atomic radius R is equal to

$
+
𝜋𝑅+ , and the number of atoms per FCC unit cell if four. Therefore, the total

FCC atom or sphere volume is
$ (5
𝑉C = (4) + 𝜋𝑅+ = +
𝜋𝑅+

From Example 1, the total unit cell volume is

𝑉& = 16𝑅+ √2

Therefore, the atomic packing factor is

!(
= GE )
𝐴𝑃𝐹 = =' = (5E
)
)
= 𝟎. 𝟕𝟒
& √!

The Body-Centered Cubic Crystal Structure

A body-centered cubic (BCC) is another common metallic crystal structure that also
has a cubic unit cell with atoms located at all eight corners and a single atom at the center of
the cube. Figures 3a and 3b showed the diagrams of BCC unit cells with the atoms
represented by hard-sphere and reduced-sphere models while Figure 3c displayed a
collection of spheres depicting this crystal structure. Corner atoms and center touch one
another along with the diagonal of the cube, and unit cell length a and atomic radius R are
related by the way of
$E
𝑎 = Equation 4
√+
From Equation 2, the number of atoms per BCC is

<$ <& 8
𝑁 = 𝑁) + !
+ 8
= 1 + 0 + 8 = 2

94
The BCC crystal structure has 8 coordination number. The atomic packing factor for
BCC 0.68 which is lower than for FCC, since BCC has lesser coordination number.
a) b) c)
Figure 3. Body-centered cubic crystal structure, (a) a hard-sphere unit cell representation,
(b) a reduced-sphere unit cell, and (c) an aggregate of many atoms (Callister & Rethwisch,
2014).
The possibility of a unit cell that consists of atoms placed only at the corners of a cube
do exist and it is called the simple cubic (SC) crystal structure. The illustration is shown in
Figure 4a and 4b. Polonium, a metalloid or a semi-metal is the only simple-cubic element that
has a relatively low atomic packing factor.
a) b)
Figure 4. Simple cubic crystal structure, (a) hard-sphere unit cell, and (b) a reduced-sphere
unit cell (Callister & Rethwisch, 2014).

Table 3. The Relationship Between the edge length (a) and radius (r) of atoms in the SCC,
BCC and FCC cell (Chang & Goldsby, 2017).

Unit cells Figure Relationship

Simple Cubic a= 2r


95
Body-centered cubic

b2 = a2 + a2
c2 = a2 + b2 = 3a2
c = √3a = 4r
a = 4r
√3

Face-centered cubic
b = 4r
b2 = a2 + a2
16r2 = 2a2
a = √8r

The Hexagonal Close-Packed Crystal Structure
The final common metallic crystal structure to be discussed is the hexagonal close-
packed (HCP). The top and bottom faces of the unit cell is consist of six atoms that form
regular hexagons and surround a single atom in the center. Between the top and bottom
planes, there is another plane that provides three additional atoms to the unit cell. The atoms
in this midplane have as nearest neighbors atoms in both of the adjacent two planes. Figure
5a shows a reduced-sphere unit cell for HCP structure and Figure 5b presents an assemblage
of several HCP unit cells.
To compute the number of atoms per unit cell for HCP crystal structure, the formula
is shown below:
<$ <&
𝑁 = 𝑁) + !
+ 5
Equation 5

One-sixth of each corner atom is designated to a unit cell instead of 8 as with the cubic
structure. This is because, HCP has 6 corner atoms in each of the top and bottom faces for a
total of 12 corner atoms, 2 face center atoms (one from each of the top and bottom faces),
and 3 midplane interior atoms. Using Equation 5, the value of N for HCP can be found.

! (!
𝑁 = 3 + (! + 5 = 6 (there are 6 atoms assigned to each unit cell)

96

a) b)

Figure 5. The hexagonal close-packed crystal structure, (a) a reduced-sphere unit cell (a
and c represent the short and long edge lengths, respectively), and (b) an aggregate of
many atoms (Callister & Rethwisch, 2014).

3.0 DENSITY COMPUTATIONS
A theoretical density (𝜌) can be computed with a knowledge of the crystal structure
of a metallic solid through the relationship

!"
𝜌 = # $ Equation 6
! "

Where n = number of atoms associated with each unit cell
A = atomic weight
VC = volume of the unit cell
NA = Avogadro’s number (6.022 x 1023 atoms/mol)

Example 3. Copper (A=63.5 g/mol) has an atomic radius of 0.128 nm, an FCC
crystal structure, and an atomic weigh of 63.5 g/mol. Compute its theoretical
density, and compare the answer with its measured density.

Solution:
!"#$ !"#$
𝜌=# =
# $" (&'(% )*)$"

(, ./012/(4!5/ 6788))('9.; </108)
=
&')*(&.*= > &?&' 61)% /4!5/ 6788] ('.?**>&?(% ./012/10876487)

𝒈
= 𝟖. 𝟖𝟗 𝒄𝒎𝟑


97

Example 4. Gold (Au) crystallizes in a cubic close-packed structure (the
face-centered cubic unit cell) and has a density of 19.3 g/cm3. Calculate the
atomic radius of gold in picometers.

Solution:

The sequence of steps is summarized as follows:

Density of unit cellàvolume of unit cellàedge length of unit cellàradius
of Au atom

𝑚𝑎𝑠𝑠
𝜌 = ; 𝑠𝑜𝑙𝑣𝑒 𝑓𝑜𝑟 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑎 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙
𝑣𝑜𝑙𝑢𝑚𝑒

$ 1A.'C ( '.2 (I4.0 - J>
𝑚 = ( >*)A &?22 𝑥 5.0!!H(0*) 1A.'C 𝑥 ( '.2 J> =
-K1'
1.31 𝑥 103!( >*)A &?22

Solve for volume
' (.+(H(0+*! -
𝑉 = L = , = 6.79𝑥103!+ 𝑐𝑚+
(I.+
&-)

Solve for the edge a
)
𝑉 = 𝑎+ ; 𝑇ℎ𝑒𝑟𝑒𝑓𝑜𝑟𝑒, 𝑎 = √𝑉 =
)
√6.79𝑥1𝑜 3!+ 𝑐𝑚+ = 4.08𝑥1038 𝑐𝑚

From Table 2 we see the radius of an Au sphere (r) is related to the edge
length by
𝑎 = √8 𝑟

Therefore,
1 $.08H(0+# &' (H(0+* ' (M'
𝑟 = = = 1.44𝑥1038 𝑐𝑚 𝑥 ( &'
𝑥 (H(0+!* '
√8 √8

𝒓 = 𝟏𝟒𝟒 𝒑𝒎


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4.0 X-Ray Diffraction by Crystals

X-ray diffraction refers to the scattering of X-rays by the units of a crystalline solid. The
patterns produced by scattering, or diffraction are used to deduce the particle arrangement
in the solid lattice.
Figure 5 shows the interference phenomenon associated with waves. Since X-rays are
one form of electromagnetic radiation, therefore, we would expect that waves exhibit such
behavior under relevant conditions. In 1912, Max von Laue, a German physicist
recommended that since the wavelength of X-rays is comparable in magnitude to the
distances between lattice points in a crystal, then the lattice should be able to diffract X-rays.
Interference in the waves associated with X-rays produced an X-ray diffraction pattern.

Figure 6. Constructive interference (a) and destructive interference
(b) of two waves of the same wavelength and amplitude (Chang &
Goldsby, 2017).

a) b)

Figure 7 shows a typical X-ray diffraction setup. A beam of X rays is directed at a

mounted crystal. Atoms in the crystal absorb some of the incoming radiation and then reemit
it; the process is called the scattering of X rays

Figure 7. (a) An arrangement for obtaining the X-ray diffraction pattern of a crystal. The
shield prevents the strong undiffracted X rays from damaging the photographic plate. (b) X-
ray diffraction pattern of crystalline lysozyme, a protein. The white "L" is a shadow of the
sample holder and shield (Chang & Goldsby, 2017).

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The X-ray diffraction technique gives the most accurate method for determining bond
lengths and bond angles in molecules in the solid state. Chemists can construct an electron-
density contour map from the diffraction patterns because X-rays are scattered by electrons
but it is with the use of a complex mathematical procedure. An electron-density contour map
basically tells us the relative electron densities at various locations in a molecule. The
densities reach a maximum near the center of each atom and in this manner we can
determine the positions of the nuclei and thus the molecular geometric parameters.

5.0 TYPES OF CRYSTALS
In determining the structures and properties of crystals, such as melting point,
density, and hardness it is important to consider the kinds of forces that hold the particles
together. The classification of any crystal has four types: ionic, covalent, molecular, or
metallic.

Ionic Crystals
There are two important characteristics of ionic crystals and they are as follows: (1)
They are composed of charged species and (2) anions and cations are generally quite
different in size. The radii of the ions must be known because it is helpful in understanding
the structure and stability of these compounds. It is hard to measure the radius of an
individual ion but sometimes it is possible to come up with an estimation. For example, if we
know the radius of 𝐼 3 𝑖𝑛 𝐾𝐼 is about 216 pm, we can determine the radius of 𝐾 N 𝑖𝑜𝑛 𝑖𝑛 𝐾𝐼,
and from that, the radius of 𝐶𝑙 3 𝑖𝑛 𝐾𝐶𝑙, and so on. For example, the 𝑁𝑎𝐶𝑙 crystal which has
a face-centered cubic lattice (see Figure 8) shows that the edge length of the unit cell of 𝑁𝑎𝐶𝑙
is twice the sum of the ionic radii of 𝑁𝑎N 𝑎𝑛𝑑 𝐶𝑙 3 . Getting the values of ionic radius given in
some references the we calculate the length of the edge to 2(95 + 181) 𝑝𝑚, 𝑜𝑟 552 𝑝𝑚. In
Figure 8, the edge length shown was determined by X-ray diffraction which has a value of
564 𝑝𝑚. The difference between these two values tells us that the radius of an ion actually
varies slightly from one compound to another. Figure 9 shows the portions of the Na+ and
Cl- ions within a unit cell.

Figure 8. Relation between the radii of Na+ and Cl- ions and the unit cell dimensions. Here
the cell edge length is equal to twice the sum of the two ionic radii (Chang & Goldsby, 2017).

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Figure 9. Portions of 𝑁𝑎N 𝑎𝑛𝑑 𝐶𝑙 3 Na+ ions within a face-centered cubic unit cell (Chang &
Goldsby, 2017).
Figure 10 shows the crystal structures of three ionic compounds:

𝐶𝑠𝐶𝑙, 𝑍𝑛𝑆, 𝑎𝑛𝑑 𝐶𝑎𝐹! . 𝐶𝑠𝐶𝑙 has the simple cubic lattice because 𝐶𝑠 N is considerably larger
than 𝑁𝑎N . 𝑍𝑛𝑆 has the zincblende structure, which is based on the face-centered cubic lattice.
If the 𝑆 !3 ions occupy the lattice points, the 𝑍𝑛!N ions are located one-fourth of the distance
along each body diagonal. Other ionic compounds that have the zincblende structure include
𝐶𝑢𝐶𝑙, 𝐵𝑒𝑆, 𝐶𝑑𝑆, 𝑎𝑛𝑑 𝐻𝑔𝑆. 𝐶𝑎𝐹! has the fluorite structure. The 𝐶𝑎!N ions occupy the lattice
points, and each 𝐹 3 ion is tetrahedrally surrounded by four 𝐶𝑎!N ions. The compounds
𝑆𝑟𝐹! , 𝐵𝑎𝐹! , 𝐵𝑎𝐶𝑙! , 𝑎𝑛𝑑 𝑃𝑏𝐹! also have the fluorite structure.

a) b) c)

Figure 10. Crystal structures of (a) 𝐶𝑠𝐶𝑙, (b) 𝑍𝑛𝑆, and (c) 𝐶𝑎𝐹! . In each case, the cation is the
smaller sphere (Chang & Goldsby, 2017).

Most ionic crystals have high melting points which is an indication of the strong
cohesive forces holding the ions together. A measure of the stability of ionic crystals is the
lattice energy; the higher the lattice energy, the more stable the compound. Since the ions
are fixed in position, therefore these solids do not conduct electricity. The ions are free to
move when in the molten state (melted) or dissolved in water, thereby the resulting liquid
is conducting electricity.

Covalent Crystals
Covalent crystals exists when atoms are held together in an extensive three-
dimensional network altogether by covalent bonds. Examples are the two allotropes of
carbon: diamond and graphite. Each carbon atom of diamond is 𝑠𝑝+ ℎ𝑦𝑏𝑟𝑖𝑑𝑖𝑧𝑒𝑑 where it is
bonded to four other atoms (Figure 11). The unusual hardness and very high melting point

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(3550°𝐶) of diamond are attributed with the strong covalent bonds that exist in three
dimensions while for graphite, carbon atoms are arranged in six-membered rings. The atoms
are all sp2-hybridized and each atom is covalently bonded to three other atoms. There is a
remaining unhybridized 2𝑝 orbital that is used in 𝑝𝑖 bonding.

a) b)

Figure 11. (a) The structure of diamond. Each carbon is tetrahedrally bonded to four other
carbon atoms. (b) The structure of graphite. The distance between successive layers is 335
pm (Chang & Goldsby, 2017).
Graphite is considered as a good conductor of electricity in directions along the planes

of carbon atoms, this is because electrons are free to move around in this extensively
delocalized molecular orbital. The hardness of graphite is caused by the covalent bonds that
exist in its layers which are held together by weak van der Waals forces. Furthermore, the
layers of graphite can slide one another, that’s why it is slippery to the touch and is effective
as lubricant. It is also used in pencils and ribbons made for computer printers and
typewriters.
Another example of covalent crystal is quartz (𝑆𝑖𝑂! ). The silicon atoms in quartz has
a similar arrangement to that of carbon in diamond, but in quartz there is a presence of
oxygen atom between each pair of 𝑆𝑖 atoms. A polarity exist in 𝑆𝑖 − 𝑂 bond because 𝑆𝑖 and
𝑂 have different electronegativities. Still, 𝑆𝑖𝑂! is similar to diamond in many aspects because
of its hardness and high melting point of 1610 °𝐶 .

Molecular Crystals
The lattice points in a molecular crystal are occupied by molecules which has a van
der Waals forces and/or hydrogen bonding. Solid sulfur dioxide (𝑆𝑂! ) is an example in which
the predominant attractive force is a dipole-dipole interaction. The intermolecular hydrogen
bonding is mainly responsible for maintaining the three-dimensional lattice of ice.
𝐼! , 𝑃$ 𝑎𝑛𝑑 𝑆8 are other examples of molecular crystals.
The molecules in a molecular crystals (except for ice) are packed together as closely
as their size and shape allow. Since van der Waals and hydrogen bonding are generally quite
weak as compared with ionic and covalent bonds, molecular crystals are more easily broken
apart than ionic and covalent crystals. Additionally, most molecular crystals melt at
temperature below 100 °𝐶.

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Metallic Crystals
Metallic crystals has the simplest structure because every lattice points in the crystal
are occupied by an atom of the same metal. Metallic crystals are usually body-centered cubic,
face-centered cubic or hexagonal close-packed, therefore metallic elements are usually very
dense.
The bonding electrons in a metal are delocalized over the entire crystals which is
actually different from other types of crystals. The metal atoms in a crystal can be imagined
as an array of positive ions immersed in a sea of delocalized valence electrons and these
delocalized electron makes metals a good conductor of heat and electricity. And also, metal’s
strength is caused by the great cohesive forces resulting from delocalization.
Table 4 summarizes the properties of the four different types of crystals.
Table 4. Types of Crystals and General Properties (Chang & Goldsby, 2017).
Type of Crystal Force(s) Holding General Properties Examples
the Units Together
Ionic Electrostatic Hard, brittle, high NaCl, LiF, MgO,
attraction melting point, poor CaCO3
conductor of heat
and electricity
Covalent Covalent bond Hard, high melting C (diamond)**, SiO2
point, poor (quartz)
conductor of heat
and electricity
Molecular* Dispersion forces, Soft, low melting Ar, CO2, I2, H2O,
dipole-dipole forces, point, poor C12H22O11 (sucrose)
hydrogen bonds conductor of heat
and electricity
Metallic Metallic bond Soft to hard, low to All metallic
high melting point, elements; for
good conductor of example, Na, Mg, Fe,
heat and electricity Cu
*Included in this category are crystals made up of individual atoms.
**Diamond is a good thermal conductor.

6.0 AMORPHOUS SOLIDS
We all know that crystalline form of solids are most stable, but if it solidify rapidly
then its atoms or molecules do not have time to align themselves and may become locked in
positions other than those of regular crystals. This resulting solid is said to be amorphous.
Amorphous solids lack a regular three-dimensional arrangement of atoms.

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Glass is an example of an amorphous solid. Glass commonly refers to an optically

transparent fusion product of inorganic materials that has cooled to a rigid state without
crystallizing. By product of a fusion, we mean that the glass is formed by mixing molten
silicon dioxide (𝑆𝑖𝑂! ), with compounds such as sodium oxide (𝑁𝑎! 𝑂), boron oxide (𝐵! 𝑂+ ),
and certain transition metal oxides for color and other properties. Silicon dioxide is the chief
component of glass. In some aspect glass acts more like a liquid than a solid. Glass lacks a
long-range periodic order as results shown in X-ray diffraction studies.
X-ray diffraction studies show that

Figure 12 shows two-dimensional schematic representations of crystalline quartz
and amorphous quartz glass.
a) b)

Figure 12. Two-dimensional representation of (a) crystalline quartz and (b) noncrystalline
quartz glass. The small spheres represent silicon. In reality, the structure of quartz is three-
dimensional. Each Si atom is tetrahedrally bonded to four O atoms (Chang & Goldsby, 2017).

There are about 800 different types of glass in common use today. Figure 12 shows
two-dimensional schematic representations of crystalline quartz and amorphous quartz
glass.

Table 5. Composition and Properties of Three Types of Glass (Chang & Goldsby, 2017)
Name Composition Properties and Uses
Pure quartz glass 100% SiO2 Low thermal expansion, transparent to
wide range of wavelengths. Used in
optical research.
Pyrex glass SiO2, 60-80% Low thermal expansion; transparent to
B2O3, 10-25% visible and infrared, but not to UV
Al2O3, small amount radiation. Used mainly in laboratory
and household cooking glassware.
Soda-lime glass SiO2, 75% Easily attacked by chemicals and
Na2O, 15% sensitive to thermal shocks. Transmits
CaO, 10% visible light, but absorbs UV radiation.
Used mainly in windows and bottles.


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The color of the glass is because of the presence of metal ion (as oxides). For example,
green glass contains iron(III) oxide, 𝐹𝑒! 𝑂+ , or copper(II) oxide, 𝐶𝑢𝑂; yellow glass contains
uranium(IV) oxide, 𝑈𝑂! ; blue glass contains cobalt(II) and copper(II) oxides, 𝐶𝑜𝑂 𝑎𝑛𝑑 𝐶𝑢𝑂;
and red glass which contains small particles of gold and copper. Most of the ions mentioned
are derived from the transition metals.

Watch the videos to learn more about the topic

https://www.youtube.com/watch?v=qAeaHYSX0hs

https://www.youtube.com/watch?v=RyIARZ8jG1c

Refer to the link below to explore more understanding about the topic
https://chem.libretexts.org/Bookshelves/General_Chemistry/Map%3A_General_Chemistry_(Petrucc
i_et_al.)/12%3A_Intermolecular_Forces%3A_Liquids_And_Solids/12.6%3A_Crystal_Structures

105
ASSESSMENT TASK

a. crystalline solid
b. lattice point
c. unit cell
d. coordination number
e. atomic packing factor
f. simple cubic
g. body-centered cubic
h. face-centered cubic
i. hexagonal close-packed

2. Calculate the density of metallic iron which has a body-centered cubic unit cell

with an edge length of 286.6 pm.

3. Describe and give examples of the following types of crystals:

a) ionic crystals
b) covalent crystals
c) molecular crystals
d) metallic crystals

4. What is an amorphous solid? How does it differ from crystalline solid?

5. Define glass. What is the chief component of glass? Name three types of glass.

References:

Callister, W. D. (2014). Materials Science and Engineering: An Introduction. John Wiley & Sons,

New York

Chang, Raymond and Kenneth A. Goldsby, (2017) Chemistry, (12th International Edition), New

York: McGraw-Hill]

- BASILAN | BATSTATEU
MACALALAD – GAYETA

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Materials
Metals

LEARNING OBJECTIVES

• Describe the occurrence and abundance of metals in the Earth’s crust.

• Explain the processes involve
in the metallurgy of iron and steel
making.

• Explain the concept of the Band Theory of Electrical Conductivity

• Discuss the periodic trends of some metals and their reactivity.
1.0 OCCURRENCE OF METALS

A mineral where most metals come from, is a naturally occurring substance with a
range of chemical composition. A mineral deposit concentrated enough to allow economical
recovery of a desired metal is known as ore. Thus, an ore is a deposit in Earth’s crust of one
or more valuable minerals. Table 1 has the lists of principal types of minerals.
Aluminum, iron, calcium, magnesium, sodium, potassium, titanium and manganese
are the most abundant metals which exists as minerals in the Earth’s crust. Seawater is a rich
source of some metal ions, such as 𝑁𝑎N , 𝑀𝑔!N , 𝑎𝑛𝑑 𝐶𝑎!N . Moreover, vast areas of the ocean
floor are covered with manganese nodules which are made up mostly of manganese, along
with iron, nickel, copper, and cobalt in a chemically combine state. Manganese nodules are
combinations of rock on the sea bottom which is composed of concentric layers of iron and
manganese hydroxides around a core.

Table 1. Principal Types of Minerals (Chang & Goldsby, 2017)
Type Minerals
Uncombined 𝐴𝑔, 𝐴𝑢, 𝐵𝑖, 𝐶𝑢, 𝑃𝑑, 𝑃𝑡
metals
Carbonates 𝐵𝑎𝐶𝑂+ (witherite), 𝐶𝑎𝐶𝑂+ (calcite, limestone), 𝑀𝑔𝐶𝑂3

107
(magnesite), 𝐶𝑎𝐶𝑂+ ∙ 𝑀𝑔𝐶𝑂+ (dolomite), 𝑃𝑏𝐶𝑂+ (cerussite), 𝑍𝑛𝐶𝑂+

(smithsonite)
Halides 𝐶𝑎𝐹! (fluorite), 𝑁𝑎𝐶𝑙 (halite), 𝐾𝐶𝑙 (sylvite), 𝑁𝑎+ 𝐴𝑙𝐹5 (cryolite)
Oxides 𝐴𝑙! 𝑂+ ∙ 2𝐻! 𝑂 (bauxite), 𝐴𝑙! 𝑂+ (corundum), 𝐹𝑒! 𝑂+ (hematite),
𝐹𝑒+ 𝑂$ (magnetite), 𝐶𝑢! 𝑂 (cuprite),
𝑀𝑛𝑂! (pyrolusite), 𝑆𝑛𝑂! (cassiterite), 𝑇𝑖𝑂! (rutile), 𝑍𝑛𝑂 (zincite)
Phosphates 𝐶𝑎+ (𝑃𝑂$ )! (phosphate rock), 𝐶𝑎# (𝑃𝑂$ )+ 𝑂𝐻 (hydroxyapatite)
Silicates 𝐵𝑒+ 𝐴𝑙! 𝑆𝑖5 𝑂(8 (beryl), 𝑍𝑟𝑆𝑖𝑂$ (zircon), 𝑁𝑎𝐴𝑙𝑆𝑖+ 𝑂8 (albite),
𝑀𝑔+ (𝑆𝑖$ 𝑂(0 )(𝑂𝐻)! (talc)
Sulfides 𝐴𝑔! 𝑆 (argentite), 𝐶𝑑𝑆 (greenockite), 𝐶𝑢! 𝑆 (chalcocite), 𝐹𝑒𝑆! (pyrite),
𝐻𝑔𝑆 (cinnabar), 𝑃𝑏𝑆 (galena), 𝑍𝑛𝑆 (sphalerite)
Sulfates 𝐵𝑎𝑆𝑂$ (barite), 𝐶𝑎𝑆𝑂$ (anhydrite), 𝑃𝑏𝑆𝑂$ (anglesite),
𝑆𝑟𝑆𝑂$ (celestite), 𝑀𝑔𝑆𝑂$ ∙ 7𝐻! 𝑂 (epsomite)

2.0 METALLURGICAL PROCESSES
The science and technology of separating metals from their ores and of compounding
alloys is called metallurgical process. An alloy is a solid solution either of two or more
metals, or of a metal or metals with one or more nonmetals. The three principal steps in the
recovery of a metal from its ore are (1) preparation of the ore, (2) production of the metal,
and (3) purification of the metal.

Preparation of the Ore
In ore prior treatment, the desired mineral is separated from waste materials that is
usually clay and silicate minerals which are collectively called the gangue. Flotation is a very
useful process for carrying out this separation. In this process, the ore is finely ground and
added to water containing oil and detergent. The liquid mixture is then beaten or blown to
form a froth. The oil preferentially wets the mineral particles, which are then carried to the
top in the froth, while the gangue settles to the bottom. The froth is skimmed off, allowed to
collapse, and dried to recover the mineral particles.
Another physical separation process makes use of the magnetic properties of certain
minerals. Ferromagnetic metals are strongly attracted to magnets. The mineral magnetite
(𝐹𝑒3𝑂4), in particular, can be separated from the gangue by using a strong electromagnet.
Cobalt is another ferromagnetic metal.
Mercury forms amalgams with a number of metals. An amalgam is an alloy of
mercury with another metal or metals. Mercury can therefore be used to extract metal from
ore. Mercury dissolves the silver and gold in an ore to form a liquid amalgam, which is easily
separated from the remaining ore. The gold or silver is recovered by distilling off mercury.


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Production of Metals
Because metals in their combined forms always have positive oxidation numbers, the
production of a free metal is a reduction process. Preliminary operations may be necessary
to convert the ore to a chemical state more suitable for reduction. For example, an ore may
be roasted to drive off volatile impurities and at the same time to convert the carbonates and
sulfides to the corresponding oxides, which can be reduced more conveniently to yield the
pure metals:
𝐶𝑎𝐶𝑂+ (𝑠) → 𝐶𝑎𝑂(𝑠) + 𝐶𝑂! (𝑔)
2𝑃𝑏𝑆(𝑠) + 3𝑂! (𝑔) → 2𝑃𝑏𝑂(𝑠) + 2𝑆𝑂! (𝑔)

This last equation points out the fact that the conversion of sulfides to oxides is a
major source of sulfur dioxide, a notorious air pollutant. Most major metallurgical processes
now in use involve pyrometallurgy, procedures carried out at high temperatures.

Chemical Reduction
We can use a more electropositive metal as a reducing agent to separate a less
electropositive metal from its compound at high temperatures:
𝑉! 𝑂# (𝑠) + 5𝐶𝑎(𝑙) → 2𝑉(𝑙) + 5𝐶𝑎𝑂(𝑠)
𝑇𝑖𝐶𝑙$ (𝑔) + 2𝑀𝑔(𝑙) → 𝑇𝑖(𝑠) + 2𝑀𝑔𝐶𝑙! (𝑙)
𝐶𝑟2𝑂3(𝑠) + 2𝐴𝑙(𝑠) → 2𝐶𝑟(𝑙) + 𝐴𝑙2𝑂3(𝑠)
3𝑀𝑛+ 𝑂$ (𝑠) + 8𝐴𝑙(𝑠) → 9𝑀𝑛(𝑙) + 4𝐴𝑙2𝑂3(𝑠)

In some cases, even molecular hydrogen can be used as a reducing agent, as in the
preparation of tungsten (used as filaments in lightbulbs) from tungsten(VI) oxide:
𝑊𝑂3(𝑠) + 3𝐻2(𝑔) → 𝑊(𝑠) + 3𝐻2𝑂(𝑔)

Electrolytic Reduction
Electrolytic reduction is suitable for very electropositive metals, such as sodium,
magnesium, and aluminum. The process is usually carried out on the anhydrous molten
oxide or halide of the metal:
2𝑀𝑂(𝑙) → 2𝑀 (𝑎𝑡 𝑐𝑎𝑡ℎ𝑜𝑑𝑒) + 𝑂2 (𝑎𝑡 𝑎𝑛𝑜𝑑𝑒)
2𝑀𝐶𝑙(𝑙) → 2𝑀 (𝑎𝑡 𝑐𝑎𝑡ℎ𝑜𝑑𝑒) + 𝐶𝑙2 (𝑎𝑡 𝑎𝑛𝑜𝑑𝑒)

The Metallurgy of Iron
Iron exists in Earth’s crust in many different minerals, such as iron pyrite (𝐹𝑒𝑆2),
siderite (𝐹𝑒𝐶𝑂3), hematite (𝐹𝑒2𝑂3), and magnetite (𝐹𝑒3𝑂4, often represented as 𝐹𝑒𝑂 ∙
𝐹𝑒2𝑂3). Hematite and magnetite are predominantly suitable for the extraction of iron. The
metallurgical processing of iron involves the chemical reduction of the minerals by carbon
(in the form of coke) in a blast furnace (Figure 1). The concentrated iron ore, limestone
(𝐶𝑎𝐶𝑂3), and coke are feed into the furnace from the top. A blast of hot air is forced up the

109
furnace from the bottom, that’s why it is called a blast furnace. The oxygen gas reacts with
the carbon in the coke to form mostly carbon monoxide and some carbon dioxide. These
reactions are highly exothermic, and as the hot 𝐶𝑂 𝑎𝑛𝑑 𝐶𝑂2 gases rise, they react with the
iron oxides in different temperature zones, as shown in Figure 1. The key steps in the
extraction of iron are:
3𝐹𝑒2𝑂3(𝑠) + 𝐶𝑂(𝑔) → 2𝐹𝑒3𝑂4(𝑠) + 𝐶𝑂2(𝑔)
𝐹𝑒3𝑂4(𝑠) + 𝐶𝑂(𝑔) → 3𝐹𝑒𝑂(𝑠) + 𝐶𝑂2(𝑔)
𝐹𝑒𝑂(𝑠) + 𝐶𝑂(𝑔) → 𝐹𝑒(𝑙) + 𝐶𝑂2(𝑔)

The decomposition of limestone in the furnace is shown the equation below:
𝐶𝑎𝐶𝑂3(𝑠) → 𝐶𝑎𝑂(𝑠) + 𝐶𝑂2(𝑔)

The calcium oxide then reacts with the impurities in the iron, which are mostly sand
(𝑆𝑖𝑂2) and aluminum oxide (𝐴𝑙2𝑂3):
𝐶𝑎𝑂(𝑠) + 𝑆𝑖𝑂2(𝑠) → 𝐶𝑎𝑆𝑖𝑂3(𝑙)
𝐶𝑎𝑂(𝑠) + 𝐴𝑙2𝑂3(𝑠) → 𝐶𝑎(𝐴𝑙𝑂2)2(𝑙)

A mixture of calcium silicate and calcium aluminate that remains molten at the
furnace temperature is known as slag.
By the time the ore works its way down to the bottom of the furnace, most of it has
already been reduced to iron.

Figure 1. A blast furnace. Iron ore, limestone,
and coke are introduced at the top of the
furnace. Iron is obtained from the ore by
reduction with carbon (Chang & Goldsby,
2017).

Iron extracted in this way contains many impurities and is called pig iron; it may
contain up to 5 percent carbon and some silicon, phosphorus, manganese, and sulfur. Some

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of the impurities stem from the silicate and phosphate minerals, while carbon and sulfur
come from coke. Pig iron is granular and brittle. It has a relatively low melting point (about
1180°𝐶), so it can be cast in various forms; for this reason it is also called cast iron.
Steelmaking
Steel is an iron alloy that contains from 0.03 to 1.4 percent carbon plus various
amounts of other elements. The wide range of useful mechanical properties associated with
steel is primarily a function of chemical composition and heat treatment of a particular type
of steel.
The conversion of iron to steel is essentially an oxidation process in which the
unwanted impurities are removed from the iron by reaction with oxygen gas. One of several
methods used in steelmaking is the basic oxygen process.
Figure 2 shows the basic oxygen process. Molten iron from the blast furnace is poured
into an upright cylindrical vessel. Pressurized oxygen gas is introduced via a water-cooled
tube above the molten metal. Under these conditions, manganese, phosphorus, and silicon,
as well as excess carbon, react with oxygen to form oxides. These oxides are then reacted
with the appropriate fluxes (for example, CaO or SiO2) to form slag. If the main impurities
are silicon and phosphorus, a basic flux such as CaO is added to the iron:
𝑆𝑖𝑂2(𝑠) + 𝐶𝑎𝑂(𝑠) → 𝐶𝑎𝑆𝑖𝑂3(𝑙)
𝑃4𝑂10(𝑙) + 6𝐶𝑎𝑂(𝑠) → 2𝐶𝑎3(𝑃𝑂4)2(𝑙)

Figure 2. The basic oxygen process of

steelmaking. The capacity of a typical
vessel is 100 tons of cast iron (Chang
& Goldsby, 2017).

On the other hand, if manganese is the main impurity, then an acidic flux such as
𝑆𝑖𝑂2 is needed to form the slag:
𝑀𝑛𝑂(𝑠) + 𝑆𝑖𝑂2(𝑠) → 𝑀𝑛𝑆𝑖𝑂3(𝑙)


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The properties of steel depend not only on its chemical composition but also on the
heat treatment. At high temperatures, iron and carbon in steel combine to form iron carbide,
𝐹𝑒3𝐶, called cementite:
3𝐹𝑒(𝑠) + 𝐶(𝑠) ⟺ 𝐹𝑒3𝐶(𝑠)

The forward reaction is endothermic, so that the formation of cementite is favored at
high temperatures. When steel containing cementite is cooled slowly, the preceding
equilibrium shifts to the left, and the carbon separates as small particles of graphite, which
give the steel a gray color. (Very slow decomposition of cementite also takes place at room
temperature). If the steel is cooled rapidly, equilibrium is not attained and the carbon
remains largely in the form of cementite, 𝐹𝑒3𝐶. Steel containing cementite is light in color,
and it is harder and more brittle than that containing graphite.
Heating the steel to some appropriate temperature for a short time and then cooling
it rapidly in order to give it the desired mechanical properties is known as “tempering.” In
this way, the ratio of carbon present as graphite and as cementite can be varied within rather
wide limits. Table 2 shows the properties, composition and uses of various types of steels

Table 2. The properties and uses of various types of steel.

Composition (Percent by Mass)
Type C Mn P S Si Ni Cr Others Uses
Plain 1.35 1.65 0.04 0.05 0.06 - - Cu(0.2- Sheet products,
0.6) tools
High- 0.25 1.65 0.04 0.05 0.15- 0.4- 0.3- Cu(0.01- Construction, steam
strength 0.9 1.0 1.3 0.08 turbines
Stainless 0.03- 1.0- 0.04- 0.03 1-3 1- 4.0- - Kitchen utensils,
1.2 10 0.06 22 27 razor blades

3.0 Purification of Metals
Metals prepared by reduction usually need further treatment to remove impurities.
The extent of purification, of course, depends on how the metal will be used. Three common
purification procedures are distillation, electrolysis, and zone refining.

Distillation
Metals that have low boiling points, such as mercury, magnesium, and zinc, can be
separated from other metals by fractional distillation. One well-known method of fractional
distillation is the Mond process (named after Ludwig Mond, a British chemist of German
origin) for the purification of nickel. Carbon monoxide gas is passed over the impure nickel

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metal at about 70°𝐶 to form the volatile tetracarbonylnickel (𝑏. 𝑝. 43°𝐶), a highly toxic
substance, which is separated from the less volatile impurities by distillation:
𝑁𝑖(𝑠) + 4𝐶𝑂(𝑔) → 𝑁𝑖(𝐶𝑂)$ (𝑔)

Pure metallic nickel is recovered from 𝑁𝑖(𝐶𝑂)$ by heating the gas at 200°𝐶:
𝑁𝑖(𝐶𝑂)$ (𝑔) →→ 𝑁𝑖(𝑠) + 4𝐶𝑂(𝑔)
The carbon monoxide that is released is recycled back into the process.
Electrolysis
Another important purification technique is electrolysis. The copper metal obtained
by roasting copper sulfide usually contains impurities such as zinc, iron, silver, and gold. The
more electropositive metals are removed by an electrolysis process in which the impure
copper acts as the anode and pure copper acts as the cathode in a sulfuric acid solution
containing 𝐶𝑢!N ions (Figure 3). The reactions are:
𝐴𝑛𝑜𝑑𝑒(𝑜𝑥𝑖𝑑𝑎𝑡𝑖𝑜𝑛): 𝐶𝑢(𝑠) → 𝐶𝑢!N (𝑎𝑞) + 2𝑒 3
𝐶𝑎𝑡ℎ𝑜𝑑𝑒 (𝑟𝑒𝑑𝑢𝑐𝑡𝑖𝑜𝑛): 𝐶𝑢!N (𝑎𝑞) + 2𝑒 3 → 𝐶𝑢(𝑠)

Reactive metals in the copper anode, such as iron and zinc, are also oxidized at the
anode and enter the solution as 𝐹𝑒 !N and 𝑍𝑛!N ions. They are not reduced at the cathode,
however. The less electropositive metals, such as gold and silver, are not oxidized at the
anode. Eventually, as the copper anode dissolves, these metals fall to the bottom of the cell.
Thus, the net result of this electrolysis process is the transfer of copper from the anode to
the cathode.

Figure 3. Electrolytic purification of copper (Chang &
Goldsby, 2017).

Zone Refining
In this process, a metal rod containing a few impurities is drawn through an electrical
heating coil that melts the metal (Figure 4). Most impurities dissolve in the molten metal. As
the metal rod emerges from the heating coil, it cools and the pure metal crystallizes, leaving

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the impurities in the molten metal portion that is still in the heating coil. (This is analogous
to the freezing of seawater, in which the solid that separates is mostly pure solvent—water.
In zone refining, the liquid metal acts as the solvent and the impurities as the solutes.) When
the molten zone carrying the impurities, now at increased concentration, reaches the end of
the rod, it is allowed to cool and is then cut off.

Figure 4. Zone-refining technique for purifying metals. Top to bottom: An impure metal rod
is moved slowly through a heating coil. As the metal rod moves forward, the impurities
dissolve in the molten portion of the metal while pure metal crystallizes out in front of the
molten zone (Chang & Goldsby, 2017).
4.0 BAND THEORY OF ELECTRICAL CONDUCTIVITY

Band theory (a model use to study metallic bonding) states that delocalized electrons
move freely through “bands” formed by overlapping molecular orbitals. This theory can also
be applied to certain elements that are semiconductors.

Conductors
Metals are characterized by high electrical conductivity. For example, magnesium has
an electron configuration of [𝑁𝑒]3𝑠2, so each atom has two valence electrons in the 3s
orbital. In a metallic crystal, the atoms are packed closely together, so the energy levels of
each magnesium atom are affected by the immediate neighbors of the atom as a result of
orbital overlaps. The interaction between two atomic orbitals leads to the formation of a
bonding and an antibonding molecular orbital. Because the number of atoms in even a small
piece of magnesium is enormously large (on the order of 1020 atoms), the number of
molecular orbitals they form is also very large. These molecular orbitals are so closely spaced
on the energy scale that they are more appropriately described as a “band” (Figure 5). The
closely spaced filled energy levels make up the valence band. The upper half of the energy
levels corresponds to the empty, delocalized molecular orbitals formed by the overlap of the
3p orbitals. This set of closely spaced empty levels is called the conduction band.

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Figure 5. Formation of conduction bands in magnesium (Chang & Goldsby, 2017).

The electrons in the 1s, 2s, and 2p orbitals are localized on each Mg atom. However,
the 3s and 3p orbitals overlap to form delocalized molecular orbitals. Electrons in these
orbitals can travel throughout the metal, and this accounts for the electrical conductivity of
the metal.
The great cohesive force resulting from the delocalization is partly responsible for the
strength noted in most metals. Because the valence band and the conduction band are
adjacent to each other, the amount of energy needed to promote a valence electron to the
conduction band is negligible. There, the electron can travel freely through the metal,
because the conduction band is void of electrons. This freedom of movement accounts for
the fact that metals are good conductors, that is, they are capable of conducting electric
current.

Why don’t substances like wood and glass conduct electricity as metals do?
Basically, the electrical conductivity of a solid depends on the spacing and the state of
occupancy of the energy bands. In wood and glass, there is a gap between the valence band
and the conduction band is considerably greater than that in a metal. Consequently, much
more energy is needed to excite an electron into the conduction band. Lacking this energy,
electrons cannot move freely. Therefore, glass and wood are insulators, ineffective
conductors of electricity.

Semiconductors
Semiconductors normally are not conductors, but will conduct electricity at elevated
temperatures or when combined with a small amount of certain other elements (examples
are silicon and germanium from Group 4A elements). The use of semiconductors has
changed the electronic industry in recent decades, leading to increased miniaturization of
electric component. Transistors and solar cells are two examples of semiconductor’s
applications.

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If the energy needed to excite electrons from the valence band into the conduction
band is provided, the solid becomes a conductor. Note that this behavior is opposite that of
the metals. A metal’s ability to conduct electricity decreases with increasing temperature
because the enhanced vibration of atoms at higher temperatures tends to disrupt the flow of
electrons.
Enhancement of semiconductor’s ability to conduct electricity can be done, this is by
means of adding small amount of certain impurities to the element, this process is called
doping. Impurities of this type are known as donor impurities, because they provide
conduction electrons. Solids containing donor impurities are called n-type semiconductors,
where n stands for negative (the charge of the “extra” electron).

5.0 PERIODIC TRENDS IN METALLIC PROPERTIES
Figure 6 shows the positions of the representative metals and the Group 2B metals in
the periodic table. There is an increase of electronegativity of these metals from left to right
across a period and from bottom to top in a group. The metallic character of metals increases
in just the opposite directions, that is, from right to left across a period and from top to
bottom in a group. Low electronegativities of metals results to the formation of cations and
almost have positive oxidation numbers in their compounds. However, beryllium and
magnesium in Group 2A and metals in Group 3A and beyond also form covalent compounds.

Figure 6. Representative metals and Group 2B metals according to their positions in the
periodic table (Chang & Goldsby, 2017).

The Alkali Metals
The most electropositive or the least electronegative elements known are the alkali
metals (the Group 1A elements). These metals have a body-centered crystal structure with
low packing efficiency. They are also known because of their low melting point and soft
enough to be sliced with a knife. The lightest known metal is lithium and has great chemical
reactivity. Lithium never occur naturally in elemental form and they are found with halide,
sulfate, carbonate, and silicate ions. Other properties of alkali metals are shown in Table 3.

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This module will discuss the chemistry of the two most important element in this group;
sodium and potassium.

Table 3. Properties of Alkali Metals (Chang & Goldsby, 2017)
Li Na K Rb Cs
( ( ( (
Valence electron 2𝑠 3𝑠 4𝑠 5𝑠 6𝑠(
configuration
Density (g/cm3) 0.534 0.97 0.86 1.53 1.87
Melting point 179 97.6 63 39 28
(°𝐶)
Boiling point 1317 892 770 688 678
(°𝐶)
Atomic radius 152 186 227 248 265
(pm)
Ionic radius (M+) 78 98 133 148 165
(pm)
Ionization 520 496 419 403 375
energy (kJ/mol)
Electronegativity 1.0 0.9 0.8 0.8 0.7

Sodium and Potassium
Electrolysis is the process where metallic sodium is ideally obtained from molten
sodium chloride. This compound (𝑁𝑎𝐶𝑙) has a high melting point (801°𝐶) where much
energy is needed to keep large amounts of the substance molten. Addition of 𝐶𝑎𝐶𝑙! , can
lower the melting point to about 600°𝐶 which is an ideal temperature for the electrolysis
process.
Metallic potassium is soluble to molten 𝐾𝐶𝑙, that’s why it cannot be prepared easily
by the electrolysis process. Moreover, it vaporizes readily at the operating temperatures,
creating hazardous conditions. Instead, it is usually obtained by the distillation of molten 𝐾𝐶𝑙
in the presence of sodium vapor at 892°𝐶. The reaction that takes place at this temperature
is
𝑁𝑎(𝑔) + 𝐾𝐶𝑙(𝑙) ⇔ 𝑁𝑎𝐶𝑙(𝑙) + 𝐾(𝑔)

Sodium and potassium are about equally abundant in nature. They occur in silicate
minerals such as albite (NaAlSi3O8) and orthoclase (KAlSi3O8). These elements are also both
extremely reactive, but potassium is the more reactive of the two. Both react with water to
form the corresponding hydroxides. In a limited supply of oxygen, sodium burns to form
sodium oxide (𝑁𝑎2𝑂). However, in the presence of excess oxygen, sodium forms the pale-
yellow peroxide:

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2𝑁𝑎(𝑠) + 𝑂2(𝑔) → 𝑁𝑎2𝑂2(𝑠)

Sodium peroxide reacts with water to give an alkaline solution and hydrogen
peroxide:
𝑁𝑎2𝑂2(𝑠) + 2𝐻2𝑂(𝑙) → 2𝑁𝑎𝑂𝐻(𝑎𝑞) + 𝐻2𝑂2(𝑎𝑞)

Like sodium, potassium forms the peroxide. In addition, potassium also forms the
superoxide when it burns in air:
𝐾(𝑠) + 𝑂2(𝑔) → 𝐾𝑂2(𝑠)
2𝐾𝑂2(𝑠) + 2𝐻2𝑂(𝑙) → 2𝐾𝑂𝐻(𝑎𝑞) + 𝑂2(𝑔) + 𝐻2𝑂2(𝑎𝑞)

This reaction is applied in breathing equipment. Exhaled air contains both moisture
and carbon dioxide. The moisture reacts with 𝐾𝑂2 in the apparatus to generate oxygen gas
as shown in the preceding equation. Furthermore, 𝐾𝑂2 also reacts with exhaled 𝐶𝑂2, which
produces more oxygen gas:
4𝐾𝑂2(𝑠) + 2𝐶𝑂2(𝑔) → 2𝐾2𝐶𝑂3(𝑠) + 3𝑂2(𝑔)

Sodium and potassium are essential elements of living matter. Sodium ions and
potassium ions are present in intracellular and extracellular fluids, and they are essential for
osmotic balance and enzyme functions.

Sodium Chloride
Sodium chloride (table salt) is a typical ionic compound, a brittle solid with a high
melting point (801°𝐶) that conducts electricity in the molten state and in aqueous solution.
Rock salt is one source of sodium chloride which can be found in subterranean deposits
where often hundreds of meters thick. It is also obtained from seawater or brine (a
concentrated NaCl solution) by solar evaporation. Sodium chloride also occurs in nature as
the mineral halite.

Sodium Carbonate
Sodium carbonate (called soda ash) is used in all kinds of industrial processes,
including water treatment and the manufacture of soaps, detergents, medicines, and food
additives. For many years 𝑁𝑎! 𝐶𝑂+ was produced by the Solvay process (named after Ernest
Solvay, a Belgian chemist), in which ammonia is first dissolved in a saturated solution of
sodium chloride. Bubbling carbon dioxide into the solution results in the precipitation of
sodium bicarbonate as follows:
𝑁𝐻+ (𝑎𝑞) + 𝑁𝑎𝐶𝑙(𝑎𝑞) + 𝐻! 𝐶𝑂+ (𝑎𝑞) → 𝑁𝑎𝐻𝐶𝑂+ (𝑠) + 𝑁𝐻$ 𝐶𝑙(𝑎𝑞)

Sodium bicarbonate is then separated from the solution and heated to give sodium
carbonate:

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2𝑁𝑎𝐻𝐶𝑂+ (𝑠) → 𝑁𝑎! 𝐶𝑂+ (𝑠) + 𝐶𝑂! (𝑔) + 𝐻! 𝑂(𝑔)

Sodium Hydroxide and Potassium Hydroxide
Sodium hydroxide and potassium hydroxide (has similar properties) are prepared by
the electrolysis of aqueous 𝑁𝑎𝐶𝑙 𝑎𝑛𝑑 𝐾𝐶𝑙 solutions; both hydroxides are strong bases and
very soluble in water. Sodium hydroxide is used in the manufacture of soap and many
organic and inorganic compounds. Potassium hydroxide is used as an electrolyte in some
storage batteries, and aqueous potassium hydroxide is used to remove carbon dioxide and
sulfur dioxide from air.
Sodium chloride (molten state), an ionic compound, can be electrolyzed to form
sodium metal and chlorine. The electrolytic cell contains a pair of electrodes connected to
the battery. The battery serves as an “electron pump,” driving electrons to the cathode,
where reduction occurs, and withdrawing electrons from the anode, where oxidation occurs.
The reactions at the electrodes are:
𝐴𝑛𝑜𝑑𝑒 (𝑜𝑥𝑖𝑑𝑎𝑡𝑖𝑜𝑛): 2𝐶𝑙 3 (𝑙) → 𝐶𝑙! (𝑔) + 2𝑒 3
𝐶𝑎𝑡ℎ𝑜𝑑𝑒(𝑟𝑒𝑑𝑢𝑐𝑡𝑖𝑜𝑛): 2𝑁𝑎N (𝑙) + 2𝑒 3 → 2𝑁𝑎(𝑙)

𝑂𝑣𝑒𝑟𝑎𝑙𝑙: 2𝑁𝑎N (𝑙) + 2𝐶𝑙 3 (𝑙) → 2𝑁𝑎(𝑙) + 𝐶𝑙! (𝑔)

This process is a major source of pure sodium metal and chlorine gas.

Sodium Nitrate and Potassium Nitrate
Sodium nitrate decomposes with the evolution of oxygen at about 500°𝐶:
2𝑁𝑎𝑁𝑂+ (𝑠) → 𝑁𝑎𝑁𝑂! (𝑠) + 𝑂! (𝑔)

Potassium nitrate is prepared beginning with the “reaction”
𝐾𝐶𝑙(𝑎𝑞) + 𝑁𝑎𝑁𝑂+ (𝑎𝑞) → 𝑁𝑎𝑁𝑂+ (𝑎𝑞) + 𝑁𝑎𝐶𝑙(𝑎𝑞)

Because 𝐾𝑁𝑂+ is the least soluble salt at room temperature, it is separated from the solution
by fractional crystallization. Like 𝑁𝑎𝑁𝑂3, 𝐾𝑁𝑂3 decomposes when heated ( a temperature
below 100°𝐶).
Gunpowder consists of potassium nitrate, wood charcoal, and sulfur in the
approximate proportions of 6:1:1 by mass. When gunpowder is heated, the reaction is
2𝐾𝑁𝑂+ (𝑠) + 𝑆(𝑙) + 3𝐶(𝑠) → 𝐾! 𝑆(𝑠) + 𝑁! (𝑔) + 3𝐶𝑂! (𝑔)

The sudden formation of hot expanding gases causes an explosion.

The Alkaline Earth Metals
The alkaline earth metals are considerably less electropositive and less reactive than
the alkali metals. Except for beryllium which resembles aluminum. The oxidation number of

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alkaline earth metals in the combined form is almost always +2. Table 4. lists some common
properties of these metals. Radium is not included in the list because all of its isotopes are
radioactive and the study of its chemistry is expensive as well.

Table 4. Properties of Alkaline Earth Metals
Be Mg Ca Sr Ba
! ! ! !
Valence electron 2𝑠 3𝑠 4𝑠 5𝑠 6𝑠 !
configuration
Density (g/cm3) 1.86 1.74 1.55 2.6 3.5
Melting point 1280 650 838 770 714
(°𝐶)
Boiling point 2770 1107 1484 1380 1640
(°𝐶)
Atomic radius 112 160 197 215 222
(pm)
Ionic radius 34 78 106 127 143
(M2+) (pm)
First ionization 899 738 590 548 502
energy (kJ/mol)
Second 1757 1450 1145 1058 958
ionization
energy
Electronegativity 1.5 1.2 1.0 1.0 0.9

Magnesium
Magnesium is the sixth most plentiful element in Earth’s crust (about 2.5 percent by
mass). Among the principal magnesium ores are brucite, Mg(OH)2; dolomite, 𝐶𝑎𝐶𝑂3 ∙
𝑀𝑔𝐶𝑂3; and epsomite, 𝑀𝑔𝑆𝑂4 ∙ 7𝐻2𝑂. Seawater is a good source of magnesium and there
are about 1.3 g of magnesium in each kilogram of seawater. Metallic magnesium is obtained
by electrolysis from molten chloride, 𝑀𝑔𝐶𝑙2.
The chemistry of magnesium is intermediate between that of beryllium and the
heavier Group 2A elements. Magnesium does not react with cold water but does react slowly
with steam:
Mg(s) + H2O(g) → MgO(s) + H2(g)

It burns in air to produce magnesium oxide and magnesium nitride:
2Mg(s) + O2(g) → 2MgO(s)
3Mg(s) + N2(g) → Mg3N2(s)


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This property makes magnesium (in the form of thin ribbons or fibers) useful in flash
photography and flares.
Magnesium oxide reacts very slowly with water to form magnesium hydroxide, a
white solid suspension called milk of magnesia, which is used to treat acid indigestion:
MgO(s) + H2O(l) → Mg(OH)2(s)

Calcium
Calcium is about 3.4% by mas in the Earth’s crust. Calcium can be found in limestone,
calcite, chalk, and marble as 𝐶𝑎𝐶𝑂3; in dolomite as 𝐶𝑎𝐶𝑂3 ∙ 𝑀𝑔𝐶𝑂3; in gypsum as 𝐶𝑎𝑆𝑂4 ∙
2𝐻2𝑂; and in fluorite as 𝐶𝑎𝐹2. Metallic calcium is best prepared by the electrolysis of molten
calcium chloride (𝐶𝑎𝐶𝑙2).
Calcium (like strontium and barium) reacts with cold water to produce the
corresponding hydroxide, although the rate of reaction is much slower than those involving
the alkali metals:
𝐶𝑎(𝑠) + 2𝐻2𝑂(𝑙) → 𝐶𝑎(𝑂𝐻)2(𝑎𝑞) + 𝐻2(𝑔)

Calcium hydroxide [𝐶𝑎(𝑂𝐻)2] is commonly known as slaked lime or hydrated lime. Lime
(CaO), which is also referred to as quicklime, is one of the oldest materials known to
mankind. Quicklime is produced by the thermal decomposition of calcium carbonate:
𝐶𝑎𝐶𝑂3(𝑠) → 𝐶𝑎𝑂(𝑠) + 𝐶𝑂2(𝑔)

while slaked lime is produced by the reaction between quicklime and water:
𝐶𝑎𝑂(𝑠) + 𝐻2𝑂(𝑙) → 𝐶𝑎(𝑂𝐻)2(𝑎𝑞)

Aluminum
Aluminum is the most abundant metal and the third most plentiful element in Earth’s
crust which is 7.5 percent by mass. The elemental form cannot be found in nature; its
principal ore is bauxite (𝐴𝑙2𝑂3 ∙ 2𝐻2𝑂). Other minerals containing aluminum are orthoclase
(𝐾𝐴𝑙𝑆𝑖3𝑂8), beryl (𝐵𝑒3𝐴𝑙2𝑆𝑖6𝑂18), cryolite (𝑁𝑎3𝐴𝑙𝐹6), and corundum (𝐴𝑙2𝑂3).
Aluminum is usually prepared from bauxite with silica (𝑆𝑖𝑂2), iron oxides, and
titanium(IV) oxide. The ore is first heated in sodium (𝑁𝑎𝑂𝐻) solution to convert the silica
into soluble silicates:
𝑆𝑖𝑂! (𝑠) + 2𝑂𝐻3 (𝑎𝑞) → 𝑆𝑖𝑂+!3 (𝑎𝑞) + 𝐻! 𝑂(𝑙)

Aluminum oxide is also converted to the aluminate ion (𝐴𝑙𝑂!3 ):
𝐴𝑙2𝑂3(𝑠) + 2𝑂𝐻3 (𝑎𝑞) → 2𝐴𝑙𝑂!3 (𝑎𝑞) + 𝐻2𝑂(𝑙)

Unaffected iron oxide and titanium oxide by this treatment are filtered off.
To precipitate the insoluble aluminum hydroxide, the solution is treated with acid.
𝐴𝑙𝑂!3 (𝑎𝑞) + 𝐻+ 𝑂N (𝑎𝑞) → 𝐴𝑙(𝑂𝐻)+ (𝑠)

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After filtration, the aluminum hydroxide is heated to obtain aluminum oxide:

2𝐴𝑙(𝑂𝐻)3(𝑠) → 𝐴𝑙2𝑂3(𝑠) + 3𝐻2𝑂(𝑔)

Anhydrous aluminum oxide, or corundum, is reduced to aluminum by the Hall process
(named after Charles Martin Hall, an American inventor). The cathode is also made of carbon
and constitutes the lining inside the cell. The key to the Hall process is the use of cryolite, or
𝑁𝑎+ 𝐴𝑙𝐹5 (melting point is 1000 °C), as the solvent for aluminum oxide (melting point is 2045
°C). The mixture is electrolyzed to produce aluminum and oxygen gas:
𝐴𝑛𝑜𝑑𝑒 (𝑜𝑥𝑖𝑑𝑎𝑡𝑖𝑜𝑛): 3[2𝑂!3 → 𝑂! (𝑔) + 4𝑒 3 ]
𝐶𝑎𝑡ℎ𝑜𝑑𝑒 (𝑟𝑒𝑑𝑢𝑐𝑡𝑖𝑜𝑛): 4[𝐴𝑙 +N + 3𝑒 3 → 𝐴𝑙(𝑙)]

𝑂𝑣𝑒𝑟𝑎𝑙𝑙: 2𝐴𝑙! 𝑂+ → 4𝐴𝑙(𝑙) + 3𝑂! (𝑔)

Oxygen gas reacts with the carbon anodes (at elevated temperatures) to form carbon
monoxide, which escapes as a gas. The liquid aluminum metal (melting point is 660.2 °C)
sinks to the bottom of the vessel, from which it can be drained from time to time during the
procedure.

Transition Metals
Transition metals typically have incompletely filled d subshells or readily give rise to
ions with incompletely filled d subshells. (The Group 2B metals—Zn, Cd, and Hg—do not
have this characteristic electron configuration and so, although they are sometimes called
transition metals, they really do not belong in this category.) This attribute is responsible for
several notable properties, including distinctive coloring, formation of paramagnetic
compounds, catalytic activity, and especially a great tendency to form complex ions. In this
section we focus on the first-row elements from scandium to copper, the most common
transition metals.
As we read across any period from left to right, atomic numbers increase, electrons
are added to the outer shell, and the nuclear charge increases by the addition of protons. In
the third-period elements—sodium to argon—the outer electrons weakly shield one another
from the extra nuclear charge. Consequently, atomic radii decrease rapidly from sodium to
argon, and the electronegativities and ionization energies increase steadily.
For the transition metals, the trends are different. Looking at Table 5 we see that the
nuclear charge, of course, increases from scandium to copper, but electrons are being added
to the inner 3d subshell. These 3d electrons shield the 4s electrons from the increasing
nuclear charge somewhat more effectively than outer-shell electrons can shield one another,
so the atomic radii decrease less rapidly. For the same reason, electronegativities and
ionization energies increase only slightly from scandium across to copper compared with
the increases from sodium to argon.

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Although the transition metals are less electropositive (or more electronegative) than
the alkali and alkaline earth metals, the standard reduction potentials of the first-row
transition metals suggest that all of them except copper should react with strong acids such
as hydrochloric acid to produce hydrogen gas. However, most transition metals are inert
toward acids or react slowly with them because of a protective layer of oxide.

Table 5. Electron Configurations and Other Properties of the First Row Transition Metals
Sc Ti V Cr Mn Fe Co Ni Cu
Electron
Configuration
(M) 4𝑠 . 3𝑑/ 4𝑠 . 3𝑑. 4𝑠 . 3𝑑0 4𝑠/ 3𝑑1 4𝑠 . 3𝑑1 4𝑠 . 3𝑑2 4𝑠 . 3𝑑3 4𝑠 . 3𝑑4 4𝑠/ 3𝑑/5
(M2+) --- 3𝑑. 3𝑑0 3𝑑6 3𝑑1 3𝑑2 3𝑑3 3𝑑4 3𝑑7
(M3+) [Ar] 3𝑑/ 3𝑑. 3𝑑0 3𝑑6 3𝑑1 3𝑑2 3𝑑3 3𝑑4
Electronegativity 1.3 1.5 1.6 1.6 1.5 1.8 1.9 1.9 1.9
Ionization
energy (kJ/mol)
First 631 658 650 652 717 759 760 736 745
Second 1235 1309 1413 1591 1509 1561 1645 1751 1958
Third 2389 2650 2828 2986 3250 2956 3231 3393 3578
Radius (pm)
(M) 162 147 134 130 135 126 125 124 128
(M2+) --- 90 88 85 91 82 82 78 72
(M )
3+ 83 68 74 64 66 67 64 --- ---

General Physical Properties
Most of the transition metals have a close-packed structure in which each atom has a
coordination number of 12. Furthermore, these elements have relatively small atomic radii.
The combined effect of closest packing and small atomic size results in strong metallic bonds.
Therefore, transition metals have higher densities, higher melting points and boiling points,
and higher heats of fusion and vaporization than the Group 1A, 2A, and 2B metals.

Chemistry of Iron
After aluminum, iron is the most abundant metal in Earth’s crust (6.2 percent by
mass). It is found in many ores; some of the important ones are hematite, Fe2O3; siderite,
FeCO3; and magnetite, Fe3O4.
Pure iron is a gray metal and is not particularly hard. It is an essential element in living
systems.
Iron reacts with hydrochloric acid to give hydrogen gas:
Fe(s) + 2H1(aq) → Fe2+(aq) + H2(g)
Concentrated sulfuric acid oxidizes the metal to Fe3+, but concentrated nitric acid
renders the metal “passive” by forming a thin layer of Fe3O4 over the surface. One of the best-
known reactions of iron is rust formation. The two oxidation states of iron are +2 and +3.

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Iron(II) compounds include FeO (black), FeSO4 ∙ 7H2O (green), FeCl2 (yellow), and FeS
(black). In the presence of oxygen, Fe2+ ions in solution are readily oxidized to Fe3+ ions.
Iron(III) oxide is reddish brown, and iron(III) chloride is brownish black.

Chemistry of Copper
Copper, a rare element (6.8𝑥103+ percent of Earth’s crust by mass), is found in nature
in the uncombined state as well as in ores such as chalcopyrite, CuFeS2. The reddish-brown
metal is obtained by roasting the ore to give Cu2S and then metallic copper:
2CuFeS2(s) + 4O2(g) → Cu2S(s) + 2FeO(s) + 3SO2(g)
Cu2S(s) + O2(g) → 2Cu(l) + SO2(g)
Impure copper can be purified by electrolysis. After silver, which is too expensive for
large-scale use, copper has the highest electrical conductivity. It is also a good thermal
conductor. Copper is used in alloys, electrical cables, plumbing (pipes), and coins.
Copper reacts only with hot concentrated sulfuric acid and nitric acid. Its two
important oxidation states are +1 and +2. The +1 state is less stable and disproportionates
in solution:
2Cu+(aq) → Cu(s) + Cu2+(aq)
All compounds of Cu(I) are diamagnetic and colorless except for Cu2O, which is red.
The Cu(II) compounds are all paramagnetic and colored. The hydrated Cu2+ ion is blue. Some
important Cu(II) compounds are CuO (black), CuSO4 ∙ 5H2O (blue), and CuS (black).


Watch the videos to learn more about the topic
https://www.youtube.com/watch?v=7uIIq_Ofzgw

https://www.youtube.com/watch?v=mvDHeYI-a00


https://chem.libretexts.org/Bookshelves/General_Chemistry/Map%3A_General_Chemistry_(Petrucc
i_et_al.)/12%3A_Intermolecular_Forces%3A_Liquids_And_Solids/12.6%3A_Crystal_Structures


124

ASSESSMENT TASK

a) mineral
b) ore
c) metallurgy

2. List three metals that are usually found in an uncombined state in nature and
three metals that are always found in combined state in nature.

3. Write the chemical formulas for the following minerals:
a) calcite f) magnetite
b) dolomite g) beryl
c) fluorite h) galena
d) halite i) epsomite
e) corundum j) anhydrite

4. Describe the main step involved in the preparation of an ore.

5. Briefly discuss the steelmaking process.

6. Briefly discuss the nature of bonding in metals, insulators, and semiconducting
elements.

7. Briefly discuss the properties and characteristics of the following:
a) alkali metals
b) alkaline earth metals
c) aluminum

Reference:


York: McGraw-Hill]


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Materials
Polymers

LEARNING OBJECTIVES

• Describe the properties and
structure of polymers and know the
common polymeric materials.
•
Determine the average molecular weights of polymers and degree of

polymerization.

• Cite the differences in behavior and molecular structure of

thermoplastic and thermosetting polymers.

• Describe the sequencing arrangements along polymer chains and

crystalline state in polymeric materials.

1.0 PROPERTIES AND CHARACTERIZATION OF POLYMERS
A polymer is a molecular compound that can be distinguished by a high molar mass,
ranging into thousands and even millions of mass and they are made up of many repeating
units. Synthetic (man-made) polymers were first developed in the early 20th century, and
these polymers remarkably transformed our world as different materials can be created
with properties that are ideal for different applications. Natural polymers have been around
since life itself began. Cellulose, starch, and other complex carbohydrates are examples of
natural polymers. Natural rubber is a polymer obtained from rubber trees and even the code
for life itself, DNA, is a natural polymer.
Because of the size polymers, we might expect that molecules containing thousands
of carbon and hydrogen atoms can form a massive number of structural and geometric
isomers (if 𝐶 = 𝐶 𝑏𝑜𝑛𝑑𝑠 𝑎𝑟𝑒 𝑝𝑟𝑒𝑠𝑒𝑛𝑡). Nevertheless, these molecules are made up of
monomers, simple repeating units, and this type of composition markedly restricts the
number of possible isomers. Monomers (mono meaning “one”; meros meaning “unit”) are
the small molecules that are used for synthesizing polymers and each monomer is analogous
to a link in a chain. Polymers (poly means “many”) can be created from one monomer, of from
a combination of two or more different monomers. If a polymer is made up of only type of
monomer (e.g. polyethylene), then it is known as homopolymer. Other homopolymer that

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are synthesized by the radical mechanism are TeflonTM, polytetrafuoroethylene and

poly(vinyl chloride) (PVC).
Synthetic polymers can be made from many different starting materials which usually
come from crude oil (raw material). Presently, crude oil is the starting material for many
plastics, pharmaceuticals, fabrics, and other carbon-based products.

Polymer Molecules
The molecules in polymers are gigantic and because of their size they are often
referred to as macromolecules. The backbone of each of a carbon-chain polymer is a string
of carbon atoms and within each molecule, the atoms are bound together by covalent
interatomic bonds. Many times each carbon atom singly bonds to two adjacent carbon atoms
on either side which is represented as follows:

| | | | | | |
−𝐶 − 𝐶 − 𝐶 − 𝐶 − 𝐶 − 𝐶 − 𝐶 −
| | | | | | |

Each of the two remaining valence electrons for every carbon atom may be involved
in side bonding with atoms or radicals that are positioned adjacent to the chain. Of course,
both chain and side double bonds are also possible.

2.0 THE CHEMISTRY OF POLYMER MOLECULES
The hydrocarbon ethylene (C2H4) is a gas at ambient temperature and pressure which
has the following molecular structure:

Under appropriate conditions, ethylene gas reacted and it will transform to
polyethylene (PE) which is a solid polymeric material. This process begins when an active
center is formed by the reaction between an initiator or catalyst species (R·) and the ethylene
monomer, as follows:


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Next, the polymer chain forms by the sequential addition of monomer units to this
actively growing chain molecule which is represented schematically as follows:

After the addition of
many ethylene monomer units, the final result is the polyethylene molecule (Figure 1).
Representation of polyethylene chain structure is shown below:

or alternatively as

Here, the repeat units are enclosed in parentheses, and the subscript n indicates the
number of times it repeats.

a) b)
Figure 1. For polyethylene, (a) a schematic representation of repeat unit and chain
structures, and (b) a perspective of the molecule, indicating the zigzag backbone structure
(Callister & Rethwisch, 2014).

Other chemistry of polymer structure such as tetrafluoroethylene monomer to form
polytetrafluoroethylene (PTFE) is shown below:

Polytetrafluoroethylene (having the trade name Teflon) belongs to a family of
polymers called the fluorocarbons.
The vinyl chloride monomer (CH2=CHCl) is a slight variant of that for ethylene, in
which one of the four H atoms is replaced with a Cl atom. Its polymerization is represented
as


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and leads to poly(vinyl chloride) (PVC), another common polymer.
Some polymers may be represented using the following generalized form:

where the R represents either an atom [i.e., H or Cl, for polyethylene or poly(vinyl chloride),
respectively] or an organic group such as CH3, C2H5, and C6H5 (methyl, ethyl, and phenyl)
(Figure 2).

a)

b)

c)

Figure 2. Repeat unit and chain structures for (a) polytetrafluoroethylene, (b) poly(vinyl
chloride), and (c) polypropylene (Callister & Rethwisch, 2014).

3.0 MOLECULAR STRUCTURE OF POLYMERS

Molecular weight and shape of a polymer is not the only basis of its physical
characteristics, the difference in the structure of the molecular chains must also be
considered.


129
Table 1. Description and schematic representations of linear, branched, crosslinked, and

network (three-dimensional) molecular structures. Circles designate individual repeat units
(Callister & Rethwisch, 2014).

Polymer Description Figure
Structure
Linear -Linear polymers are those in which the repeat
units are joined together end to end in single
chains.
-These long chains are flexible where each circle
represents a unit.
-There may be extensive van der Waals and
hydrogen bonding between the chains.
-Some of the common polymers that form with
linear structures are polyethylene, poly(vinyl
chloride), polystyrene, poly(methyl methacrylate),
nylon, and the fluorocarbons.
Branched -The chain packing efficiency is reduced with the
formation of side branches, which results in a
lowering of the polymer density.
-For example, high-density polyethylene (HDPE) is
primarily a linear polymer, whereas low-density
polyethylene (LDPE) contains short-chain
branches.
Crosslinked -Adjacent linear chains are joined one to another
at various positions by covalent bonds.
-The process of crosslinking is achieved either
during synthesis or by a nonreversible chemical
reaction.
-Often, this crosslinking is accomplished by
additive atoms or molecules that are covalently
bonded to the chains.
-Many of the rubber elastic materials are
crosslinked.


130
Network -These are multifunctional monomers forming

three or more active covalent bonds make three-
dimensional networks.
-A polymer that is highly crosslinked may also be
classified as a network polymer.
-These materials have distinctive mechanical and
thermal properties; the epoxies, polyurethanes,
and phenol-formaldehyde belong to this group.

Note that polymers may have more than one distinctive structural type, for example,
a linear polymer may have limited branching and crosslinking.

4.0 COMMON POLYMERIC MATERIALS
Presently, there are more than 60,000 synthetic polymers known, with this, six types
of polymers (Table 2) account for roughly 75% of those used in both Europe and the United
States.

Table 2. Six Common Polymers (Symbols retrieved from:
https://www.acmeplastics.com/content/your-guide-to-plastic-recycling-symbols/)
Polymer Recycle Monomer Properties of Uses of Polymer
Symbol Polymer
Polyethylene Ethylene -Translucent if not Bags, films, sheets,
pigmented. bubble wrap, toys,
-Soft and flexible. wire insulation.
-Unreactive to acids
LDPE and bases.
-Strong and tough.

Polyethylene Ethylene -Similar to LDPE Opaque milk, juice,
-More rigid, tougher, detergents, and
slightly more dense. shampoo bottles.
Buckets, crates, and
HDPE fencing
Polyvinyl chloride Vinyl chloride -Variable. Rigid if Rigid: Plumbing
not softened with a pipe, house siding,
plasticizer. Clear charge cards, hotel
and shiny, but often room keys.
pigmented. Softened: Garden

PVC or V Resistant to most hoses, waterproof


131
chemicals, including boots, shower

oils, acids, and curtains, IV tubing.
bases.
Polystyrene -Variable. “Crystal” “Crystal” form: Food
form transparent, wrap, CD cases,
sparkling, transparent cups.
somewhat brittle. “Expandable” form:
-“Expandable” form Foam cups,
PS Styrene lightweight foam. insulated
-Both forms rigid containers, food
and degraded in packaging trays, egg
many organic cartons, packaging
solvents. peanuts.
Polypropylene Propylene -Opaque, very Bottle caps. Yogurt,
tough, good cream, and
weatherability. High margarine
melting point. containers.
PP -Resistant to oils. Carpeting, casual

furniture, luggage.
Polyethylene Ethylene glycol -Transparent, Soft-drink bottles,
terephthalate 𝐻𝑂 − 𝐶𝐻! 𝐶𝐻! − 𝑂𝐻 strong, shatter- clear food
resistant. - containers,
Terephthalic acid Impervious to acids beverage glasses,
and atmospheric fleece fabrics, carpet
gases. yarns, fiber-fill
PETE or PET -Most costly of the insulation.

six.

5.0 MOLECULAR WEIGHT AND DEGREE OF POLYMERIZATION
Polymers with very long chains has extremely large molecular weights but during
polymerization process, not all polymer chains will grow to the same length and this results
in a distribution of chain lengths or molecular weights. Usually, an average molecular weight
is specified, which can be determined by the measurement of various physical properties
such as viscosity and osmotic pressure.
There are several ways of defining average molecular weight. The number-average
molecular weight Mn is obtained by dividing the chains into a series of size ranges and then
determining the number fraction of chains within each size range (Figure 3). The number-
average molecular weight is expressed as

132
‡‡‡‡
𝑀* = ˆ 𝑋) 𝑀) 𝐸𝑞𝑢𝑎𝑡𝑖𝑜𝑛 1
where Mi represents the mean (middle) molecular weight of size range i, and Xi is the fraction
of the total number of chains within the corresponding size range.
A weight-average molecular weight Mw is based on the weight fraction of molecules

within the various size ranges. It is calculated according to
‡‡‡‡‡
𝑀 O = ˆ 𝑊) 𝑀) 𝐸𝑞𝑢𝑎𝑡𝑖𝑜𝑛 2
where, again, Mi is the mean molecular weight within a size range, whereas Wi denotes the
weight fraction of molecules within the same size interval.
Degree of Polymerization (DP) is an alternative way of expressing average chain
size of a polymer. DP represents the average number of repeat units in a chain and it is
related to the number-average molecular weight Mn by the equation
‡‡‡‡
𝑀*
𝐷𝑃 = 𝐸𝑞𝑢𝑎𝑡𝑖𝑜𝑛 3
𝑚
where m is the repeat unit molecular weight.
a) b)

Figure 3. Hypothetical polymer molecule size distributions on the basis of (a) number and
(b) weight fractions of molecules (Callister & Rethwisch, 2014).
The length of polymer chains has affected many polymer properties. For example, as
molecular weight (about 100,000 g/mol) of a polymer increases, its melting or softening
temperature also increases. But for polymers with very short chains or having a molecular
weights on the order of 100 g/mol, will usually exist as liquids at room temperature. Those
with molecular weights of approximately 1000 g/mol exists as waxy solids (e.g. paraffin
wax) and soft resins. For polymers with molecular weights ranging between 10,000 and
several million g/mol exist as solid, they are sometimes termed as high polymers. Therefore,
the same polymer material can acquire various properties if it is produced with different
molecular weight.

133

Example 1. Assume that the molecular weight distributions shown in
Figure 3 are for poly(vinyl chloride). For this material, compute (a) the
number-average molecular weight, (b) the degree of polymerization, and
(c) the weight-average molecular weight.
Data to be used for Number/Weight-Average Molecular Weight

Computations in Example 1.
𝒈
Molecular Weight Mean 𝑴𝒊 𝒎𝒐𝒍 𝑿𝒊 𝑾𝒊
𝒈
Range !𝒎𝒐𝒍"
5,000 - 10,000 7,500 0.05 0.02

10,000 – 15,000 12,500 0.16 0.10
15,000 – 20,000 17,500 0.22 0.18
20,000 – 25,000 22,5000 0.27 0.29
25,000 – 30,000 27,500 0.20 0.26
30,000 – 35,000 32,5000 0.08 0.13
35,000 – 40,000 37,500 0.02 0.02

Solution:
a) Use Equation 1 for solving the number-average molecular weight
‡‡‡‡
𝑀* = ∑ 𝑋) 𝑀)
‡‡‡‡
𝑀* = 7,500(0.05) + 12,500(0.16) + 17,500(0.22) +
22,500(0.27) + 27,500(0.20) + 32,500(0.08) + 37,500(0.02)
𝑴𝒏 = 𝟐𝟏𝟏𝟓𝟎 𝒎𝒐𝒍
𝒈

b) Use equation 3 for solving degree of polymerization
22222
1
𝐷𝑃 3
&
; 𝑠𝑜𝑙𝑣𝑒 𝑓𝑜𝑟 𝑚 𝑤ℎ𝑖𝑐ℎ 𝑖𝑠 𝑡ℎ𝑒 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑟𝑒𝑝𝑒𝑎𝑡 𝑢𝑛𝑖𝑡

𝐹𝑜𝑟 𝑃𝑉𝐶 𝑡ℎ𝑒 𝑟𝑒𝑝𝑒𝑎𝑡 𝑢𝑛𝑖𝑡 𝑖𝑠 𝐶𝐻! 𝐶𝐻𝐶𝑙
- - - -
𝑚 = 2 Ž12.01 '.2• + 3 Ž1.01 '.2• + 35.45 '.2 = 62.50 '.2

!((#0 -/'.2 𝒈
𝐷𝑃 = 5!.#0 -/'.2 = 𝟑𝟑𝟖. 𝟒 𝒎𝒐𝒍

c) Use Equation 2 for solving weight-average molecular weight

‡‡‡‡‡
𝑀 O = ∑ 𝑊) 𝑀)
‡‡‡‡‡
𝑀O = 7,500(0.02) + 12,500(0.10) + 17,500(0.18) +
22,500(0.29) + 27,500(0.26) + 32,500(0.13) +
37,500(0.02)
𝒈
𝑴𝑾 = 𝟐𝟑𝟐𝟎𝟎 𝒎𝒐𝒍


134
6.0 THERMOPLASTIC AND THERMOSETTING POLYMERS

Molecular structure has a great effect on how polymers react to mechanical forces at
elevated temperatures. Indeed, one classification for these materials is according to behavior
with rising temperature. Thermoplastics (or thermoplastic polymers) and thermosets (or
thermosetting polymers) are the two subdivisions.
Thermoplastics soften upon heating and later liquefy, then it hardens when cooled.
This process is reversible and can be repeated. As the temperature is increased, secondary
bonding forces of the molecules are decreased (through increased molecular motion) so that
the relative movement of adjacent chains is facilitated when a stress is applied. Exposure of
a molten thermoplastic polymer to a very high temperature results to an irreversible
degradation. Examples of common thermoplastic polymers are polyethylene, polystyrene,
poly(ethylene terephthalate), and poly(vinyl chloride).
For thermosetting polymers which are network polymers, they do not soften upon
heating and they become permanently hard during their formation. Network polymers have
covalent crosslinks between adjacent molecular chains. During heat treatment, the bonds
fasten the chains together to resist the vibrational and rotational chain motions at high
temperatures. Therefore, the materials do not soften when heated. Excessive heating
temperatures will cause severance of these crosslink bonds and polymer degradation. As
compared to thermoplastics, these thermoset polymers are generally harder and stronger
and have better dimensional stability. Examples of these thermosets (crosslinked and
network polymers) are vulcanized rubbers, epoxies, phenolics, and some polyester resins.

7.0 COPOLYMERS
A copolymer is composed of two repeat units as represented in Table 3. It is possible
that there are different sequencing arrangements along the polymer chains which depends
on the polymerization process and the relative fractions of these repeat unit types. Synthetic
rubbers are usually copolymers.

Table 3. Schematic representations of random, alternating, block, and graft copolymers. The
two different repeat unit types are designated by blue and red circles (Callister & Rethwisch,
2014).

Copolymer Description Figure
Random two different units are randomly
dispersed along the chain
Alternating two repeat units alternate chain positions


135
Block identical repeat units are clustered in

blocks along the chain

Graft homopolymer side branches of one type
may be grafted to homopolymer main
chains that are composed of a different

repeat unit

8.0 POLYMER CRYSTALLINITY
In crystalline state, the atomic arrangement in polymer materials are more complex
as compared to metals and ceramics because in polymers it involves molecules instead of
just atoms or ions. Polymer crystallinity is the packing of molecular chains to produce an
ordered atomic array. Crystal structures may be specified in terms of unit cells, which are
often quite complex. Figure 4 shows the example of a unit cell for polyethylene and its
relationship to the molecular chain structure (unit has orthorhombic geometry). Obviously,
the chain molecules also extend beyond the unit cell as shown in Figure 4.
Molecular substances having small molecules (e.g. water and methane) are normally
either totally crystalline (as solids) or totally amorphous (as liquids). As an effect of their size
and usual complexity, polymer molecules are often partially crystalline (or semicrystalline),
having crystalline regions dispersed within the remaining amorphous material. An
amorphous region is the result of any chain disorder or misalignment, a case that is quite
common, because twisting, kinking, and coiling of the chains hinder the strict ordering of
every segment of every chain. The extent of crystallinity may range from completely
amorphous to almost entirely (up to about 95%) crystalline. If compared to metal specimens
(almost always entirely crystalline) and many ceramics (either totally crystalline or totally
noncrystalline) polymeric materials behave differently.

Figure 4. Arrangement of molecular chains in a unit cell for polyethylene (Callister &
Rethwisch, 2014).

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Watch the video to learn more about the topic

https://www.youtube.com/watch?v=rHxxLYzJ8Sw


https://chem.libretexts.org/Courses/Sacramento_City_College/SCC%3A_Chem_400_-

_General_Chemistry_I/Text/12%3A_Solids_and_Modern_Materials/12.9%3A_Polymers_and_Plastics
References:

New York
York: McGraw-Hill.

Mury, M. T. (2018). Chemistry in context: applying chemistry to society (No. 540 C517cc).
McGraw-Hill,.

137
ASSESSMENT TASK

a) monomer
b) polymer
c) homopolymer
d) copolymer

2. Which of the six common polymers most likely would be used for these
applications?
a) clear soda bottles
b) opaque laundry detergent bottles
c) clear, shiny shower curtains
d) tough indoor-outdoor carpet
e) plastic baggies for food
f) packaging peanuts
g) containers of milk

3. The number-average molecular weight of a polypropylene is 1,000,000 g/mol.
Compute the degree of polymerization.

4. a) Compute the repeat unit molecular weight of polystyrene.
b) Compute the number-average molecular weight for a polystyrene for which the
degree of polymerization is 25,000.

5. Compare thermoplastic and thermosetting polymers (a) on the basis of
mechanical characteristics upon heating and (b) according to possible molecular
structures.
6. Differentiate the following terms by description and illustration: (a) random, (b)
alternating, (c) block, and (d) graft copolymers.
7. Explain briefly why the tendency of a polymer to crystallize decreases with

increasing molecular weight.

138

Materials
Engineered Nanomaterials

LEARNING OBJECTIVES

•
Determine the basic concepts in nanotechnology and learn the formation

of nanomaterials.
• Describe the properties and application of nanomaterials in different
fields.

1.0 Introduction to Nanotechnology and Nanomaterials
Nanomaterials has attractive properties and amazing technological possibilities,
which can be any one of the four basic types - metals, ceramics, polymers or composites. But
difficulties with nanomaterials arise from the fact that, in contrast to conventional materials,
a profound knowledge of materials science is not sufficient. Nanomaterials lie at the
intersection of materials science, physics, chemistry, and for many of the most interesting
applications – also of biology and medicine.
The first – and broadest – definition of nanomaterials states that, these are materials
where the sizes of the individual building blocks are less than 100 nm (a very small scale), at
least in one dimension (nm; equivalent to the diameter of approximately 500 atoms). Usually
nanomaterials are developed to show innovative characteristics compared to the same
material without the nanoscale features which includes, increased strength, chemical
reactivity or conductivity.

2.0 NANOTECHNOLOGY AND CONVENTIONAL TECHNOLOGY
The main difference between nanotechnology and conventional technologies is that
the “bottom-up” approach is favored in nanotechnology, whereas conventional technologies
generally use the “top-down” approach. On examining these technologies more closely, the
expression “top-down” means starting from large pieces of material and producing the
expected structure by mechanical or chemical methods This situation is shown schematically
in Figure 1. As long as the structures are within a range of sizes that are accessible by either

139
mechanical tools or photolithographic processes, then top-down processes have an

unmatched flexibility in their application.

block or sheet of metal structured part

Figure 1. Conventional goods are produced via top-down processes, starting from bulk
materials. The intended product is obtained by the application of mechanical and/or
chemical processes (Vollath, 2013).

The condition is different in “bottom-up” processes where atoms or molecules are
used as the building blocks to produce nanoparticles, nanotubes, or nanorods, or thin films
or layered structures. Given their dimensionality, these features are also referred to as zero-
, one-, or two-dimensional nanostructures (see Figure 2). Figure 2 also reveals the building
of particles, layers, nanotubes, or nanorods from atoms (ions) or molecules. Although such
processes provide exceptional freedom among the resultant products, the number of
possible structures to be obtained is comparatively small. In order to obtain ordered
structures, bottom-up processes must be supplemented by the self-organization of
individual particles.

product dimensiona
lity
particles zero

atoms

nanotubes one
or rods

molecules
layers two


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Figure 2. The bottom-up process starting with atoms and molecules as the building blocks
that produced particles, nanotubes or nanorods and these products are also characterized
by their dimensionality (Vollath, 2013) .

Nanotubes and nanorods are usually referred to as one-dimensional nanoparticles,
nanoparticles and fullerenes, in contrast, are generally denominated as zero-dimensional
structures. Consequently, nanoplates, in particular graphenes, could be considered as two-
dimensional nanoparticles. A typical example of nanorods (in this case ZnO) is shown in
Figure 3. These rods are over 5 mm long (most are about 15 mm long), with diameters
ranging from 120 to 140 nm, and are clearly separated. For nanoplates, an example (in this
case gold nanoplates) is shown in Figure 4a. The size of these platelets is approximately 400
nm in the plane and their thickness ranges from 25 to 60 nm. As can be seen from the
hexagonal shape of the platelets, the nanoplates have a single orientation with the direction
perpendicular to the plane.

(Reproduced by permission of Springer.)
Figure 3. Secondary electron micrograph of ZnO nanorods. These nanorods have lengths of
about 15 mm and diameters ranging from 120 to 140 nm. (Vollath, 2013).

(Reproduced with permission by The American Institute of Physics.)


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Figure 4. (a) Electron micrograph of the gold platelets; these are about 400 nm wide, with
thickness ranging from 25 to 60 nm. (b) Electron diffraction pattern of a gold platelet as
shown in (a) (Vollath, 2013).
The hexagonal symmetry of the diffraction pattern indicates that the direction of the
platelets was perpendicular to the faces of the platelet; in other words, the electron beam
was exactly parallel to the direction.

3.0 FORMATION OF NANOMATERIALS
Formation of Rods and Plates
In the formation of nanorods and nanoplates, the influence of surface energy is to be
considered. For nonspherical nanostructures, this is especially important in the case of
anisotropic (noncubic) structures. But for surface-active molecules it is possible to grow rods
or plates even from isotropic materials. In this context, it should be noted that even from
gold, the existence of cubic material, nanorods, and nanoplates is well known (see Figure 4).
The second possibility of obtaining nanorods and nanotubes is related to layered
structures, where the crystal structure is built from layers held together with van der Waals
forces rather than by electrostatic attraction. The general arrangement of a particle
crystallized in such a layered structure is shown schematically in Figure 5a, where the layers
are independent. At the circumference of each layer, the bonds are not saturated (these
“dangling bonds” are indicated in Figure 5b). Based on this explanation, it is clear that all
compounds that crystallize in layered structures show a tendency to form nanotubes. Typical
examples are boron nitride (BN), WS2, MoS2, WSe2, MoSe2, and, most importantly, carbon.

Figure 5. Layout of a particle that crystallizes in a layered structure. (a) Particle set-up.
(b) One layer of a particle as depicted in (a). The bindings at the circumference of the layer
are not saturated (Vollath, 2013).
The dangling bonds (short lines) need additional energy; thus, there is a strong
tendency to saturate these dangling bonds.
The use of compounds that crystallize in only one dimension is the third possibility
of obtaining nanotubes. In concept, this is the most promising way to obtain long fibers, but

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unfortunately the importance of this route is negligible as the numbers of compounds

coming into question is small.
Imogolite is the most important compound in this context with an ideal composition
of Al2SiO3(OH)4. The ratio of silicon over aluminum is fairly flexible and can be used to adjust
the tube diameter. Imogolite tubes with the ideal composition are very narrow, with internal
diameters of 1 nm and external diameters of 2 nm. The structure of imogolite (see Figure 6)
is characterized by aluminum, silicon, oxygen, and OH- ions arranged in rings. This structure
allows the addition of organic molecules (to “functionalize”) at the surface.

Figure 6. Arrangement of ions in imogolite (Vollath, 2013).
Attachment of organic compounds at the outer layer consisting of oxygen ions is a

possibility where tube diameter can be adjusted by altering the aluminum/silicon ratio.
Formation of Carbon Nanotubes

Discussions about graphite and fullerenes as special modification of carbon is
essential in order to understand carbon nanotubes. The modifications of a substance differ
in the ways in which the atoms are arranged and bond with each other, and so different
modifications will have different physical and chemical properties. For example, graphite
crystallizes in a layered hexagonal structure (Figure 7) in which each carbon atom is bound
covalently to its three neighbors.

Figure 7. Structure of graphite. Each layer consists of interconnected hexagons with one
carbon atom at each vertex (Vollath, 2013).

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Consequently, only three of the four valences of the carbon atom are saturated. The
fourth electron of the atoms remains unbound and becomes delocalized across the
hexagonal atomic sheets of carbon. Electrons in graphite are mobile which shows electrical
conductivity within the layers; perpendicularly to the layers, graphite is an insulator. Within
the layers are strong covalent bonds, whereas in between the layers are weak van der Waals
bonds and, accordingly, it is possible to cleave pieces of monocrystalline graphite. These
single layers of graphite are known as graphene, and because of its structure and bonding
graphene is often denominated as an infinitely extended, two-dimensional aromatic
compound.
The bonding is shown in Figure 8a, representing one elementary hexagon and its first
row of neighbors clearly shows the interplay between single and double bonds.
In boron nitride (BN), one observes single bonds only, as nitrogen as well as boron
are both in their three valency state. Hence, there are no free electrons, with the consequence
that bulk BN is an isolator. (BN nanotubes, however, are wide-band semiconductors.) In
correlation to Figure 8a, Figure 8b displays the elementary hexagon of BN and its first
neighbors.

a) b)

Figure 8. (a) Structure elements of graphene and (b) boron nitride (BN). In contrast to
graphene, BN has only single bonds (Vollath, 2013).

In the sense that graphene is a two-dimensional aromatic compound, fullerenes,
which also exist in the case of BN, are three-dimensional aromatics. Fullerenes consist of a
combination of hexagons and pentagons; Figure 9 illustrates one pentagon surrounded by
five hexagons. The arrangement leaves gaps between the hexagons, the closure of these (as
indicated by an arrow in Figure 9) leads to the formation of a three-dimensional structure.
This is the basic structural element of fullerenes. Spherical shapes are formed by combining
a larger number of these structures.
The most common fullerene, and the first to be identified consists of 60 carbon atoms
(this is written as C60), with the molecular structure comprising 12 pentagons and 20
hexagons. The fullerene with the least number of carbon which is identified
(experimentally) is C20 while the smallest stable fullerene is C36. These fullerenes are most
stable, where each pentagon is surrounded by hexagons only. In addition to C60, the most
important other fullerenes are C70, C76, C78, and C84. The appearances of C60 and C70 are shown

144
in Figure 10a and b. It is possible to attach metal atoms or other molecules at the surface of
fullerene even if it is quite stable, this reaction is of major importance in view of the
applications of fullerenes. Fullerenes also appear quite often in many layers; these
aggregates are known as “nested fullerenes” or “onion molecules.”

Figure 9. Five hexagons surrounding a pentagon. Closing the gaps between the hexagons
leads to a three-dimensional structure – the basic element of fullerenes (Vollath, 2013).
a) b)
Figure 10. Two different fullerenes. The hexagons and pentagons – the constitutive
elements of fullerenes – can be seen easily in both models. (a) C60 fullerene. (b) C70 fullerene
(Vollath, 2013).
It may be easily conceived that single graphite layers (graphene) reduce the energy
stored in the dangling bonds by forming tubes. There are, however, alternative possibilities
for these planes to form coils and this determines the properties of the carbon nanotubes.
Nanotubes are formed by wrapping graphene layers of limited size to form a tube.
After rolling the graphene sheet to form a tube, a nanotube with a diameter of 1.35 nm has
the appearance (armchair type) illustrated in Figure 11.

Figure 11. Armchair-type carbon nanotube. The diameter is calculated as 1.35 nm (Vollath,
2013)

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The formation of nanotubes is not limited to single graphene layers and, as for
fullerenes, both “multiwall” and “single-wall” nanotubes may be observed. The multiwall
nanotubes consist of a series of coiled graphene layers and can be described perfectly using
electron microscopy (see Figure 12).

Figure 12. Example of a multiwall carbon nanotube. The outer diameter of this multiwall
nanotube is 1.25 nm (Vollath, 2013).

4.0 PROPERTIES AND APPLICATIONS OF NANOMATERIALS

Nanocarbons
Nanocarbons which are a class of recently discovered materials have innovative and
exceptional properties and are currently being used in some cutting-edge technologies and
will certainly play an important role in future high-tech applications. Three nanocarbons that
belong to this class are fullerenes, carbon nanotubes, and graphene.

Fullerenes
The material composed of C60 molecules is known as buckminsterfullerene, (or
buckyball for short) (Figure 10), named in honor of R. Buckminster Fuller, who invented the
geodesic dome; each C60 is simply a molecular replica of such a dome. The term fullerene is
used to denote the class of materials that are composed of this type of molecule.
In the solid state, the C60 units form a crystalline structure and pack together in a face-
centered cubic array. This material is called fullerite, and Table 1 lists some of its properties.
A few fullerene compounds have been developed which have uncommon chemical,
physical and biological characteristics and does have the potential to be used in a of new
applications. Some of these compounds involve atoms or groups of atoms that are enclosed
within the cage of carbon atoms (and are termed endohedral fullerenes). For other
compounds, atoms, ions, or clusters of atoms are attached to the outside of the fullerene shell
(exohedral fullerenes). Uses and potential applications of fullerenes include antioxidants in
personal care products, biopharmaceuticals, catalysts, organic solar cells, long-life batteries,
high- temperature superconductors, and molecular magnets.


146
Table 1. Properties of Carbon Nanomaterials (Callister & Rethwisch, 2014).
Material
Property C60 (Fullerite) Carbon Graphene
Nanotubes (In-Plane)
(Singled
Walled)
-
Density (&') ) 1.69 1.33-1.40 -
Modulus of elasticity (GPa) - 1000 1000
Strength (MPa) - 13,000 - 53,000 130,000
9
Thermal Conductivity Ž' ∙ 𝐾• 0.4 ~2000 3000 - 5000
Coefficient, Thermal Expansion - - ~-6

(1035 𝐾 3( )
Electrical Resistivity (Ω ∙ 𝑚) 1014 10-6 10-8

Carbon Nanotubes
Carbon nanotubes are another molecular form of carbon which has recently been
discovered that has some unique and technologically promising properties. Its structure
consists of a single sheet of graphite (i.e., graphene) that is rolled into a tube; the term single-
walled carbon nanotube (abbreviated SWCNT) is used to denote this structure. Each
nanotube is a single molecule composed of millions of atoms; the length of this molecule is
much greater (on the order of thousands of times greater) than its diameter. Multiple-walled
carbon nanotubes (MWCNTs) consisting of concentric cylinders also exist (see Figure 12).
Nanotubes are extremely strong and stiff and relatively ductile. Additionally,
nanotubes have relatively low densities. Table 1 shows several properties of single-walled
nanotubes. On the basis of their exceedingly high strengths, carbon nanotubes have the
potential to be used in structural applications. On the other hand, most current applications
are limited to the use of bulk nanotubes—collections of unorganized tube segments. Thus,
bulk nanotube materials will most likely never achieve strengths comparable to individual
tubes. Bulk nanotubes are currently being used as reinforcements in polymer-matrix
nanocomposites to improve not only mechanical strength, but also thermal and electrical
properties.
Carbon nanotubes also have unique and structure-sensitive electrical characteristics.
Depending on the orientation of the hexagonal units in the graphene plane (i.e., tube wall)
with the tube axis, the nanotube may behave electrically as either a metal or a
semiconductor. As a metal, they have the potential for use as wiring for small-scale circuits.
In the semiconducting state they may be used for transistors and diodes. Furthermore,
nanotubes are excellent electric field emitters. As such, they can be used for flat-screen
displays (e.g., television screens and computer monitors).

147
Other potential applications are varied and numerous, and include the following:
• More efficient solar cells
• Better capacitors to replace batteries
• Heat removal applications
• Cancer treatments (target and destroy cancer cells)
• Biomaterial applications (e.g., artificial skin, monitor and evaluate engineered
tissues)
• Body armor
• Municipal water-treatment plants (more efficient removal of pollutants and
contaminants)

Graphene
Graphene as the newest member of the nanocarbons, is a single-atomic-layer of
graphite, composed of hexagonally sp2 bonded carbon atoms (see graphite in Figure 7).
These bonds are extremely strong, yet flexible, which allows the sheets to bend. The first
graphene material was produced by peeling apart a piece of graphite, layer by layer using
plastic adhesive tape until only a single layer of carbon remained (micromechanical
exfoliation, or the adhesive-tape method). Although pristine graphene is still produced using
this technique (which is very expensive), other processes have been developed that yield
high-quality graphene at much lower costs.
Two characteristics of graphene make it an exceptional material. First is the perfect
order found in its sheets where no atomic defects such as vacancies exist; also these sheets
are extremely pure and only carbon atoms are present. The second characteristic relates to
the nature of the unbonded electrons: at room temperature, they move much faster than
conducting electrons in ordinary metals and semiconducting materials.
In terms of its properties (some are listed in Table 1), graphene could be labeled the
ultimate material. Furthermore, it is transparent, chemically inert, and has a modulus of
elasticity comparable to the other nanocarbons (~1 TPa).
Given this set of properties, the technological potential for graphene is enormous, and
it is expected to modernize many industries to include electronics, energy, transportation,
medicine/biotechnology, and aeronautics. However, before this revolution can begin to be
realized, economical and reliable methods for the mass production of graphene must be
developed.
The following is a short list of some of the potential applications for graphene: touch-
screens, conductive ink for electronic printing, transparent conductors, transistors, heat
sinks (electronics); polymer solar cells, catalysts in fuel cells, battery electrodes,
supercapacitors (energy); artificial muscle, enzyme and DNA biosensors, photoimaging
(medicine/biotechnology); chemical sensors (for explosives); and nanocomposites for
aircraft structural components (aeronautics).


148


Watch the video to learn more about the topic
https://www.youtube.com/watch?v=IGjCOJqINPA


https://chem.libretexts.org/Bookshelves/Inorganic_Chemistry/Book%3A_Introduction_to_Inorganic_

Chemistry/11%3A_Basic_Science_of_Nanomaterials

ASSESSMENT TASK

1. What is the first and broadest definition of nanomaterials?

2. What is the difference between nanotechnology and conventional technology.

3. Briefly discus the formation of nanorods, nanoplates and carbon nanotubes.

4. Illustrate two of the most important fullerene (C60 and C70).

5. Briefly discuss the properties and applications of nanomaterials (fullerenes,
carbon nanotubes, and graphene.

References:

New York

Vollath, D. (2013). Nanomaterials an introduction to synthesis, properties and application.
Wiley-VCH Verlag GmbH & Co. KGaA

149
Unit 4 – The Chemistry of the Environment
The Chemistry of the Atmosphere

LEARNING OBJECTIVES

• Determine the structure and composition of the atmosphere
and understand the Earth's Atmospheric Cycle.
• Identify the sources and effects of air pollutants and discuss
the existing treatment technologies.

1.0 The Earth's Atmospheric Cycle
Earth is unique among the planets of our solar system in having an atmosphere that
is chemically active and rich in oxygen.
The atmosphere is a protective blanket which nurtures life on the Earth and protects
it from the hostile environment of outer space. It is generally believed that three billion or
four billion years ago, Earth’s atmosphere consisted mainly of ammonia, methane, and water.
There was little, if any, free oxygen present. Ultraviolet (UV) radiation from the sun probably
penetrated the atmosphere, rendering the surface of Earth sterile. However, the same UV
radiation may have triggered the chemical reactions (perhaps beneath the surface) that
eventually led to life on Earth. Primitive organisms used energy from the sun to break down
carbon dioxide (produced by volcanic activity) to obtain carbon, which they incorporated in
their own cells. The major by-product of this process, called photosynthesis, is oxygen.
Another important source of oxygen is the photodecomposition of water vapor by UV light.
Over time, the more reactive gases such as ammonia and methane have largely disappeared,
and today our atmosphere consists mainly of oxygen and nitrogen gases. Biological
processes determine to a great extent the atmospheric concentrations of these gases, one of
which is reactive (oxygen) and the other unreactive (nitrogen).
Molecular nitrogen, with its triple bond, is a very stable molecule. However, through
biological and industrial nitrogen fixation, the conversion of molecular nitrogen into
nitrogen compounds, atmospheric nitrogen gas is converted into nitrates and other

150
compounds suitable for assimilation by algae and plants. Another important mechanism for
producing nitrates from nitrogen gas is lightning.

The steps are:

About 30 million tons of HNO3 are produced this way annually. Nitric acid is
converted to nitrate salts in the soil. These nutrients are taken up by plants, which in turn
are ingested by animals. Animals use the nutrients from plants to make proteins and other
essential biomolecules. Denitrification reverses nitrogen fixation to complete the cycle. For

151
example, certain anaerobic organisms decompose animal wastes as well as dead plants and
animals to produce free molecular nitrogen from nitrates.
The main processes of the global oxygen cycle is complicated by the fact that oxygen
takes so many different chemical forms. Atmospheric oxygen is removed through respiration
and various industrial processes (mostly combustion), which produce carbon dioxide.
Photosynthesis is the major mechanism by which molecular oxygen is regenerated from
carbon dioxide and water.

Scientists divide the atmosphere into several different layers according to
temperature variation and composition. As far as visible events are concerned, the most
active region is the troposphere, the layer of the atmosphere that contains about 80 percent
of the total mass of air and practically all of the atmosphere’s water vapor. The troposphere is
the thinnest layer of the atmosphere (10 km), but it is where all the dramatic events of
weather—rain, lightning, hurricanes—occur. Temperature decreases almost linearly with
increasing altitude in this region.
Above the troposphere is the stratosphere, which consists of nitrogen, oxygen, and
ozone. In the stratosphere, the air temperature rises with altitude. This warming effect is the
result of exothermic reactions triggered by UV radiation from the. One of the products of this
reaction sequence is ozone (O3), which, as we will see shortly, serves to prevent harmful UV
rays from reaching Earth’s surface. In the mesosphere, which is above the stratosphere, the
concentration of ozone and other gases is low, and the temperature decreases with

152
increasing altitude. The thermosphere, or ionosphere, is the uppermost layer of the

atmosphere. The rise in temperature in this region is the result of the bombardment of
molecular oxygen and nitrogen and atomic species by energetic particles, such as electrons
and protons, from the sun.

2.0 AIR POLLUTANTS AND TREATMENT
The demands of increasing population coupled with the desire of most people for a
higher material standard of living are resulting in worldwide pollution on a massive scale.
Environmental pollution can be divided among the categories of water, air, and land
pollution. All three of these areas are linked. For example, some gases emitted to the
atmosphere can be converted to strong acids by atmospheric chemical processes, fall to the
earth as acid rain, and pollute water with acidity. Improperly discarded hazardous wastes
can leach into groundwater that is eventually released as polluted water into streams. In
some cases pollution is a clear-cut phenomenon, whereas in others it lies largely in the eyes
of the beholder.
A reasonable definition of a pollutant is a substance present in greater than natural
concentration as a result of human activity that has a net detrimental effect upon its
environment or upon something of value in that environment. Contaminants, which are not
classified as pollutants unless they have some detrimental effect, cause deviations from the

153
normal composition of an environment. Every pollutant originates from a source. The source
is particularly important because it is generally the logical place to eliminate pollution. After
a pollutant is released from a source, it may act upon a receptor. The receptor is anything
that is affected by the pollutant. Humans whose eyes smart from oxidants in the atmosphere
are receptors. Eventually, if the pollutant is long-lived, it may be deposited in a sink, a long-
time repository of the pollutant. Here it will remain for a long time, though not necessarily
permanently.
Some air pollutants, particularly those that may result in irreversible global warming
or destruction of the protective stratospheric ozone layer, are of such a magnitude that they
have the potential to threaten life on earth.
Modern technology has provided the means for massive alteration of the
environment and pollution of the environment specifically the atmosphere. However,
technology intelligently applied with a strong environmental awareness also provides the
means for dealing with problems of environmental pollution and degradation.
Oxides of carbon, sulfur, and nitrogen are important constituents of the atmosphere
and are pollutants at higher levels. Of these, carbon dioxide, CO2, is the most abundant. It is
a natural atmospheric constituent, and it is required for plant growth. However, the level of
carbon dioxide in the atmosphere, now at about 360 parts per million (ppm) by volume, is
increasing by about 1 ppm per year. This increase in atmospheric CO2 may well cause general
atmospheric warming—the “greenhouse effect,” with potentially very serious consequences
for the global atmosphere and for life on earth. Though not a global threat, carbon monoxide,
CO, can be a serious health threat because it prevents blood from transporting oxygen to
body tissues. The two most serious nitrogen oxide air pollutants are nitric oxide, NO, and
nitrogen dioxide, NO2, collectively denoted as “NOx.” These tend to enter the atmosphere as
NO, and photochemical processes in the atmosphere can convert NO to NO2. Further
reactions can result in the formation of corrosive nitrate salts or nitric acid, HNO3. Nitrogen
dioxide is particularly significant in atmospheric chemistry because of its photochemical
dissociation by light with a wavelength less than 430 nm to produce highly reactive O atoms.
This is the first step in the formation of photochemical smog. Sulfur dioxide, SO2, is a reaction
product of the combustion of sulfur-containing fuels such as high-sulfur coal. Part of this
sulfur dioxide is converted in the atmosphere to sulfuric acid, H2SO4, normally the
predominant contributor to acid precipitation.
The most abundant hydrocarbon in the atmosphere is methane, CH4, released from
underground sources as natural gas and produced by the fermentation of organic matter.
Methane is one of the least reactive atmospheric hydrocarbons and is produced by diffuse
sources, so that its participation in the formation of pollutant photochemical reaction
products is minimal. The most significant atmospheric pollutant hydrocarbons are the
reactive ones produced as automobile exhaust emissions. In the presence of NO, under
conditions of temperature inversion low humidity, and sunlight, these hydrocarbons
produce undesirable photochemical smog manifested by the presence of visibility-

154
obscuring particulate matter, oxidants such as ozone, and noxious organic species such as
aldehydes.
Particles ranging from aggregates of a few molecules to pieces of dust readily visible
to the naked eye are commonly found in the atmosphere. Some atmospheric particles, such
as sea salt formed by the evaporation of water from droplets of sea spray, are natural and
even beneficial atmospheric constituents. Very small particles called condensation nuclei
serve as bodies for atmospheric water vapor to condense upon and are essential for the
formation of rain drops. Colloidal-sized particles in the atmosphere are called aerosols.
Those formed by grinding up bulk matter are known as dispersion aerosols, whereas
particles formed from chemical reactions of gases are condensation aerosols; the latter tend
to be smaller. Smaller particles are in general the most harmful because they have a greater
tendency to scatter light and are the most respirable (tendency to be inhaled into the lungs).
Much of the mineral particulate matter in a polluted atmosphere is in the form of oxides and
other compounds produced during the combustion of high-ash fossil fuel. Smaller particles
of fly ash enter furnace flues and are efficiently collected in a properly equipped stack
system. However, some fly ash escapes through the stack and enters the atmosphere.
Unfortunately, the fly ash thus released tends to consist of smaller particles that do the most
damage to human health, plants, and visibility.
The removal of particulate matter from gas streams is the most widely practiced
means of air pollution control. A number of devices have been developed for this purpose
which differ widely in effectiveness, complexity, and cost. The selection of a particle removal
system for a gaseous waste stream depends upon the particle loading, nature of particles
(size distribution), and type of gas-scrubbing system used.

Particle Removal by Sedimentation and Inertia
The simplest means of particulate matter removal is sedimentation, a phenomenon
that occurs continuously in nature. Gravitational settling chambers may be employed for the
removal of particles from gas streams by simply settling under the influence of gravity. These
chambers take up large amounts of space and have low collection efficiencies, particularly
for small particles.
Gravitational settling of particles is enhanced by increased particle size, which occurs
spontaneously by coagulation. Thus, over time, the sizes of particles increase and the number
of particles decreases in a mass of air that contains particles. Brownian motion of particles
less than about 0.1 µm in size is primarily responsible for their contact, enabling coagulation
to occur. Particles greater than about 0.3 µm in radius do not diffuse appreciably and serve
primarily as receptors of smaller particles. Inertial mechanisms are effective for particle
removal. These depend upon the fact that the radius of the path of a particle in a rapidly
moving, curving air stream is larger than the path of the stream as a whole. Therefore, when
a gas stream is spun by vanes, a fan, or a tangential gas inlet, the particulate matter may be

155
collected on a separator wall because the particles are forced outward by centrifugal force.
Devices utilizing this mode of operation are called dry centrifugal collectors (cyclones).

Particle filtration
Fabric filters, as their name implies, consist of fabrics that allow the passage of gas
but retain particulate matter. These are used to collect dust in bags contained in structures
called baghouses. Periodically, the fabric composing the filter is shaken to remove the
particles and to reduce back-pressure to acceptable levels. Typically, the bag is in a tubular
configuration. Numerous other configurations are possible. Collected particulate matter is
removed from bags by mechanical agitation, blowing air on the fabric, or rapid expansion
and contraction of the bags.

Although simple, baghouses are generally effective in removing particles from
exhaust gas. Particles as small as 0.01 µm in diameter are removed, and removal efficiency
is relatively high for particles down to 0.5 µm in diameter. Aided by the development of
mechanically strong, heat-resistant fabrics from which the bags are fabricated, baghouse
installations have increased significantly in the effort to control particulate emissions.

Scrubbers
A venturi scrubber passes gas through a device which leads the gas stream through a
converging section, throat, and diverging section. Injection of the scrubbing liquid at right
angles to incoming gas breaks the liquid into very small droplets, which are ideal for
scavenging particles from the gas stream. In the reduced-pressure (expanding and,
therefore, cooling) region of the venturi, some condensation can occur of vapor from liquid
initially evaporated in the generally hot waste gas, adding to the scrubbing efficiency. In
addition to removing particles, venturis may serve as quenchers to cool exhaust gas, and as
scrubbers for pollutant gases. Ionizing wet scrubbers place an electrical charge on particles

156
upstream from a wet scrubber. Larger particles and some gaseous contaminants are
removed by scrubbing action. Smaller particles tend to induce opposite charges in water
droplets in the scrubber and in its packing material and are removed by attraction of the
opposite charges.

ASSESSMENT TASK

1. Which size range encompasses most of the particulate matter mass in the
atmosphere?

2. Why are aerosols in the 0.1–1 µm size range especially effective in scattering
light?

3. Make a brief discussion about air pollutants and treatment technologies

References:
Chang, Raymond and Kenneth A. Goldsby, (2017) Chemistry, (12th International Edition),
New York: McGraw-Hill.

Manahan, S. E. (2010). Environmental Chemistry. CRC press.

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Unit 4 – Chemistry of the Environment
THE CHEMISTRY OF WATER

LEARNING OBJECTIVES

• Describe the properties , sources and unique characteristics of water

• Explain the dissociation process of acids and bases in water and

interpret the importance of monitoring pH in our bodies of water.
• Identify different water contaminants and learn various water
treatment techniques.of water. Understand the movement and conservation of
water through hlogical

1.0 PROPERTIES AND CHARACTERISTICS OF WATER
Water has various distinctive properties that are fundamental to life. These
astonishing properties are acquired from its molecular structure (see Figure 1) and the
interaction among individual molecules. There are few special characteristics of water which
includes: the tendency to form hydrogen bonds, its polar character, and capability to hydrate
metal ions. These properties are listed in Table 1.
H2O is the chemical formula of water, its bond is covalent in nature with a bent
molecular geometry (Figure 1). The water molecule is made up of two hydrogen atoms
bonded to an oxygen atom.

a) b)

Figure 1. (a) Lewis structures and structural formula; (b) space-filling model. (Fahlman,
2018)

Capability to hydrogen bond formation is another characteristic of the water molecule.
Hydrogen bonds are a special type of bond that can form between the hydrogen in one water
molecule and the oxygen in another water molecule. This bonding takes place because the
oxygen has a partial negative charge and the hydrogen a partial positive charge. This is an
example of an intermolecular force; that is, a force that occurs between molecules.

158
Hydrogen bond is also described as an electrostatic attraction between a hydrogen

atom, which is bonded to a highly electronegative atom (oxygen, nitrogen or fluorine), and a
neighboring oxygen, nitrogen or fluorine atom—either in another molecule, or in a different
part of the same molecule. Do not be baffled with hydrogen bond and a covalent bond
because covalent has a much stronger bonds which connects atoms within molecules.
Furthermore, the atoms involved in hydrogen bonding are farther apart than they are in
covalent bond (Figure 2).

Figure 2. Hydrogen and covalent bonding in water molecules (Fahlman, 2018)

The three atoms in water molecule (H-O-H) are not in a straight line (Figure 3);
instead, they form an angle of 104.5°. The bent structure of water molecule is due to fact that
there is a stronger attraction between oxygen and the negative electron than with the
hydrogen atoms and also the water molecule acts like a dipole having opposite electrical
charges at either end. The water dipole may be attracted to either positively or negatively
charged ions.
For example, when sodium chloride (NaCl) dissolves in water as positive sodium ions
(Na+) and negative chloride ions(Cl-), the positive Na+ are surrounded by water molecules
with their negative ends pointed at the ions, and the Cl- are surrounded by water molecules
with their positive ends pointing at the negative ions (Figure 3). This kind of attraction for
ions is the reason why water dissolves many ionic compounds and salts that do not dissolve
in other liquids.

N 3
𝑁𝑎𝐶𝑙(C) → 𝑁𝑎(1Y) + 𝐶𝑙(1Y)

Figure 3. Sodium Chloride dissolving in water. (Fahlman et al., 2018)

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At standard temperature and pressure (STP), water is a liquid with a temperature of

25 °C and pressure of 1 atm. Water has a high boiling point of 100 °C (212 °F) but this
property vary with liquids that has same molecular structures such as hydrogen sulfide (H2S)
that has much lower boiling points. Additionally, when water freezes, it expands while most
liquids contract when they solidify.
Table 1. Important Properties of Water (adapted from Manahan, 2010)

Property Effects and Significance
Excellent solvent Transport of nutrients and waste products, making
biological processes possible in an aqueous
medium
Highest dielectric constant of any common liquid High solubility of ionic substances and their
ionization in solution
Higher surface tension than any other liquid Controlling factor in physiology; governs drop
and surface phenomena
Transparent to visible and longer-wavelength Colorless, allowing light required for
fraction of ultraviolet light photosynthesis to reach considerable depths in
bodies of water
Maximum density as a liquid at 4 ̊C Ice floats; vertical circulation restricted in
stratified bodies of water
Higher heat of evaporation than any other material Determines transfer of heat and water molecules
between the atmosphere and bodies of water
Higher latent heat of fusion than any other liquid Temperature stabilized at the freezing point of
except ammonia water
Higher heat capacity than any other liquid except Stabilization of temperatures of organisms and
ammonia geographical regions

2.0 CLASSIFICATION OF WATER BY SOURCE
Potable water. A potable water is safe for drinking, cooking, bathing and washing
dishes. In contrast, non-potable water is contaminated with pollutants that include
particulates from dirt, toxic metals (e.g. arsenic), or bacteria that cause cholera. Although it
is not drinkable, non-potable water has its uses like washing sidewalks, reducing roadway
dust or for irrigation.
Surface water. Surface water is the most convenient source for human activities. It
can be found in lakes, rivers, and streams.
Groundwater. Groundwater is less convenient to access. It is the fresh water found
in underground reservoirs also known as aquifers. People worldwide pump groundwater
from wells drilled deep into these underground reservoirs. Fresh water is also found in our
atmosphere in the form of mists, fogs, and humidity. The characteristics of surface and
groundwater is shown in Table 2.


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Table 2. General Characteristics of Groundwater and Surface Water (adapted from Masten
& Davis, 2014)
Ground Surface
Composition is constant Composition is varying
Mineral content is high Mineral content is low
Turbidity is Low Turbidity is high
Has low or no color Has color
May be bacteriologically safe Presence of microorganisms
Absence of dissolved oxygen Presence of dissolved oxygen
Has high hardness Has low hardness
Presence of H2S, Fe, Mn Has taste and odor
Chemical toxicity is possible Chemical toxicity is possible

THE HYDROLOGICAL CYCLE
The hydrological cycle shown in Figure 4 is a cycle that includes all of the water
present on and in the earth which includes salt and fresh water, surface and groundwater,
water present in the clouds and trapped water in rocks far below the earth’s surface.
Hydrological cycle mainly describes the movement and conservation of water on Earth.
Two distinct processes for the transfer of water to the earth’s atmosphere:
a) Evaporation. Evaporation is the conversion of liquid water from lakes, streams,
and other bodies of water to water vapor.
b) Transpiration. Transpiration is the process by which water is emitted from plants
through the stomata, small opening on the underside of leaves that are connected to the
vascular tissue. Predominantly, it occurs at the leaves while the stomata are open for the
passage of carbon dioxide (CO2) and oxygen (O2) during photosynthesis.
It is sometimes difficult to identify which process that has took place between true
evaporation and transpiration, this is the reason why hydrologists used the term
evapotranspiration to describe the combined losses of water due to transpiration and
evaporation.
Precipitation is the primary mechanism by which water is released from the
atmosphere. Precipitation takes several forms, the most common of which in temperate
climates is rain. Additionally, water can fall as hail, snow, sleet, and freezing rain.
As water falls to the earth’s surface, the droplets either run over the ground into
streams and rivers (referred to as surface runoff, overland flow, or direct runoff), move
laterally just below the ground surface (interflow), or move vertically through the soils to
form groundwater (infiltration or percolation).


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Figure 4. The hydrological cycle. The percentages represent the volume in each of the
different compartments (Masten & Davis, 2014).

THE CHARACTERISTICS OF BODIES OF WATER
The chemical and biological processes that occur in water was strongly influenced by
the physical condition of a body of water.
Surface water. Surface water occurs primarily in streams, lakes, and reservoirs.
Wetlands. Wetlands are flooded areas (permanently or seasonally) in which the
water is shallow enough to enable growth of bottom-rooted plants.
Estuaries. Estuaries are arms of the ocean into which streams flow. Estuaries has
unique chemical and biological properties because of the mixing of fresh and salt water. The
preservation of estuaries is very important because it is the breeding ground of much marine
life.
Water which has a unique temperature-density relationship produces the formation
of distinct layers within nonflowing bodies of water (Figure 5).
During the summer a surface layer (epilimnion) is heated by solar radiation and,
because of its lower density, floats upon the bottom layer, or hypolimnion. This
phenomenon is called thermal stratification. When an appreciable temperature difference
exists between the two layers, they do not mix but behave independently and have very
different chemical and biological properties. The shear-plane, or layer between epilimnion
and hypolimnion, is called the metalimnion or thermocline.


162

Figure 5. Stratification of a Lake (Manahan, 2010)

Concentration Units in Aqueous Solutions
Solvent. A substance often a liquid that is capable of dissolving one or more pure
substances.
Solute. A solid, liquid or gas that dissolves in a solvent.
Solution. A homogeneous (of uniform composition) mixture of a solvent and one or
more solutes.
Aqueous solution. A solution in which water is the solvent.
Concentration. It is the ratio of the amount of solute to the amount of solution. Solute
concentrations in aqueous solutions are expressed with different units—percent (%), parts
per million (ppm), parts per billion (ppb), and molarity (M).
Weight percent, P. It is frequently used to express approximate concentrations of
commercial chemicals or of solid concentrations of sludges. The term specifies the grams of
substance per 100 g of solution or suspension and is mathematically expressed as

𝑊
𝑃 = 𝑥 100%
𝑊 + 𝑊0

Where P = percent of substance by weight
W = mass of substance (grams)
𝑊0 = mass of solute (grams)

In case of many substances dissolved in drinking water that has a very low
concentration, parts per million (ppm) is more commonly used.
For example, water that contains 1 ppm of magnesium ions contains the equivalent
of 1 gram of magnesium (in the form of the magnesium ion) dissolved in 1 million grams of
water. The water we drink contains substances naturally present in the parts per million

163
range. For example, the acceptable limit for nitrate ions, 𝑁𝑂+3 , found in well water in some
agricultural areas, is 10 ppm; the limit for fluoride ions, 𝐹 3 , is 4 ppm.
Although parts per million is a useful concentration unit, measuring 1 million grams
of water is not very convenient. We can do things more easily by switching to the unit of a
liter. One ppm of any substance in water is equivalent to 1 mg of that substance dissolved in
a liter of solution (1 𝑝𝑝𝑚 = 1 𝑚𝑔/𝐿).
In environmental science and engineering it is often assumed that the substance does
not change the density of the water. This is generally true in dilute solutes at constant
temperature, but it is not valid for concentrated solutions, in air, or in cases of large
temperature fluctuations.

1 𝑔 𝑠𝑜𝑙𝑢𝑡𝑒 1000 𝑚𝑔 𝑠𝑜𝑙𝑢𝑡𝑒 1000 𝑔 𝑤𝑎𝑡𝑒𝑟 1 𝑚𝑔 𝑠𝑜𝑙𝑢𝑡𝑒
1 𝑝𝑝𝑚 = 5
𝑥 𝑥 =
1𝑥10 𝑔 𝑤𝑎𝑡𝑒𝑟 1 𝑔 𝑠𝑜𝑙𝑢𝑡𝑒 1 𝐿 𝑤𝑎𝑡𝑒𝑟 1 𝐿 𝑤𝑎𝑡𝑒𝑟

Some contaminants are of concern at concentrations much lower than parts per million, and
are reported as parts per billion (ppb). In aqueous solutions, 1 ppb = 1 μg/L.
One contaminant found in the range of parts per billion is mercury. One part per
billion of mercury (Hg) in water is equivalent to 1 gram of Hg dissolved in 1 billion grams of
water. In more convenient terms, this means 1 microgram (1 μg or 1 × 10–6 g) of Hg dissolved
in 1 liter of water. The acceptable limit for mercury in drinking water is 2 ppb:

2 𝑔 𝐻𝑔 1𝑥105 𝜇𝑔 𝐻𝑔 1000𝑔 𝐻! 𝑂 2𝜇𝑔 𝐻𝑔
2 𝑝𝑝𝑏 𝐻𝑔 = 𝑥 𝑥 =
1𝑥10I 𝑔 𝐻! 𝑂 1𝑔 𝐻𝑔 1𝐿 𝐻! 𝑂 1𝐿 𝐻! 𝑂

Molarity (M). It is defined as a concentration unit expressed by the number of moles
of solute present in 1 liter of solution.

𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒
𝑀𝑜𝑙𝑎𝑟𝑖𝑡𝑦 (𝑀) =
𝑙𝑖𝑡𝑒𝑟 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛

A great advantage of molarity is that solutions of the same molarity contain exactly
the same number of moles of solute, and hence the same number of molecules (ions or
atoms) of solute. The mass of a solute varies depending on its identity. As an example,
consider a solution of NaCl in water. The molar mass of NaCl is 58.5 g/mol; therefore, 1 mol
of NaCl has a mass of 58.5 g. By dissolving 58.5 g of NaCl in some water and then adding
enough water to make exactly 1.00 L of solution, we would have a 1.00 M NaCl aqueous
solution.


164

Example 1. A water sample has 150 ppm of dissolved mercury, Hg

2+. What is
this concentration expressed in molarity?

!N !N
150 𝑝𝑝𝑚 𝐻𝑔!N = 150 𝑚𝑔 𝐻𝑔 𝑥 1 𝑔 𝐻𝑔 1 𝑚𝑜𝑙 𝐻𝑔!N
𝑥
1 𝐿 𝐻! 𝑂 1000 𝑚𝑔 𝐻𝑔!N 200.6 𝑔 𝐻𝑔!N
3$ !N
7.5𝑥10 𝑚𝑜𝑙 𝐻𝑔
=
1 𝐿 𝐻! 𝑂

Thus, a sample of water containing 150 ppm of mercury also can be expressed

3𝟒 𝟐N
as 𝟕.
𝟓𝒙𝟏𝟎 𝑴 𝑯𝒈 .

3.0 REACTION OF ACIDS AND BASES IN WATER (pH Measurement)
Acid (at a molecular level) is a compound that releases hydrogen ions (𝐻N ), in aqueous
solution. A hydrogen atom is electrically neutral and consists of one electron and one proton.
If the electron is lost, the atom becomes a positively charged ion, H N . Because only a proton
remains, sometimes 𝐻N is referred to as a proton.
For example, consider hydrogen chloride (HCl), a compound that is a gas at room
temperature. Hydrogen chloride is composed of HCl molecules that dissolve readily in water
to produce a hydrochloric acid solution. As the polar HCl molecules dissolve, they become
surrounded by polar water molecules. Once dissolved, these molecules break apart into two
ions producing aqueous hydrogen ion, H+(aq) and aqueous chloride ion, Cl–(aq). This
equation represents the two steps of the reaction:

7* Z
𝐻𝐶𝑙(𝑔) –⎯˜ 𝐻𝐶𝑙 (𝑎𝑞) → 𝐻N (𝑎𝑞) + 𝐶𝑙 3 (𝑎𝑞)

HCl dissociates into H+ and Cl+. No HCl molecules remain in solution because they
dissociate completely in water, which is referred to as a strong acid.
When dissolved in water, each HCl molecule donates a proton (H+) to an H2O
molecule, forming a hydronium ion (H3O+). Here is a representation of the overall reaction:

N 3
𝐻𝐶𝑙(1Y) + 𝐻! 𝑂(2) → 𝐻+ 𝑂(1Y) + 𝐶𝑙(1Y)

A chemical reaction with the presence of H3O+ has the characteristic property of an
acid but chemists often simply write H+ when referring to acids and it is understood that this
means H3O+ in aqueous solutions.
Hydrogen chloride is but one of several gases that dissolves in water to produce an
acidic solution. Sulfur dioxide and nitrogen dioxide are two others. These two gases are

165
emitted during the combustion of certain fuels (particularly coal) to produce heat and
electricity. SO2 and NO2 both dissolve in rain and mist which produce acids that in turn fall
back to Earth’s surface in rain or snow.
As compared to more polar compound such as SO2 and NO2, carbon dioxide is far
soluble in water. Even so, it dissolves to produce a weakly acidic solution.

𝐶𝑂! (𝑎𝑞) + 𝐻! 𝑂(𝑙) → 𝐻! 𝐶𝑂+ (𝑎𝑞)
The carbonic acid (𝐻! 𝐶𝑂! ) dissolves to produce H+ and the hydrogen carbonate ion,
also known as the bicarbonate ion 𝐻𝐶𝑂+3 :

𝐻! 𝐶𝑂+ (𝑎𝑞) ⟺ 𝐻N (𝑎𝑞) + 𝐻𝐶𝑂+3 (𝑎𝑞)

The double-arrow symbol indicates that this reaction occurs only to a limited extent,
producing small amounts of 𝐻N and 𝐻𝐶𝑂+3 . Thus, a carbonic acid is considered to be a weak
acid; that is, an acid that dissociates only to a small extent in aqueous solution.
For base, it is a compound that releases hydroxide ions (OH–) in aqueous solution.
Aqueous solutions of bases have their own characteristic properties attributable to the
presence of OH–(aq). Common examples of bases include household ammonia (an aqueous
solution of NH3) and NaOH (sometimes called lye). Many common bases are compounds
containing the hydroxide ion. For example, sodium hydroxide (NaOH), a water-soluble ionic
compound, dissolves in water to produce sodium ions (Na+) and hydroxide ions (OH–):

7* Z
𝑁𝑎𝑂𝐻(C) –⎯˜ 𝑁𝑎N (𝑎𝑞) + 𝑂𝐻3 (𝑎𝑞)

Although sodium hydroxide is very soluble in water, most compounds containing the
hydroxide ion are not, according to the solubility rules of ionic compounds. Bases that
dissociate completely in water, such as NaOH, are called strong bases.
For the reaction of molecules of aqueous ammonia in water, the water molecule
transfers H+ to the NH3 molecule. An ammonium ion, NH4+(aq), and a hydroxide ion, OH–(aq),
are formed. But the reaction only occurs to a small extent and that small amount of OH-(aq)
is produced.
𝑁𝐻+ (𝑎𝑞) + 𝐻! 𝑂(𝑙) ⟺ 𝑁𝐻$N (𝑎𝑞) + 𝑂𝐻3 (𝑎𝑞)
weak base acid conjugate acid conjugate base

In the reaction above, an acid will donate a proton, H+, to a base. In this case, water
acts as the acid, which donates a proton to NH3. The double-arrow of this reaction indicates
that this is an equilibrium reaction, one that proceeds in both directions to continually form
both products and reactants. In the reverse (right–left) direction, the 𝑁𝐻$N ion donates a
proton to 𝑂𝐻3 . Hence, 𝑁𝐻$N is referred to as a conjugate acid of the base NH3, and OH– is
the conjugate base of the acid H2O.

166
The Use of pH Scale in Quantifying Acidity/Basicity:

a) The notation pH is always written with a small p and a capital H that stands for
“power of hydrogen”.
b) pH is usually between 0 and 14 that indicates the acidity (or basicity) of a solution.
c) pH 7 separates acidic from basic solutions, this is at the midpoint on the scale.
d) Solutions with a pH less that 7 are acidic, those with a pH greater than 7 are basic
(alkaline).
e) Solutions of pH 7 (e.g. pure water) have equal concentrations of H+ and OH- and are
said to be neutral.
f) pH is related to the concentration of hydrogen ion concentration thru this equation:
𝑝𝐻 = −log [𝐻N ]

pH and the Environment
The balance in our oceans and other sources of water can be affected by a change in
pH. It is known that ocean water have small amounts of carbonate ion, bicarbonate ion and
carbonic acid that arise from dissolved carbon dioxide which play a role in maintaining the
pH of ocean at approximately 8.2. These three species (Figure 6) also help maintain the pH
of our blood at about 7.4.

carbonate ion bicarbonate ion carbonic acid
3! 3
𝐶𝑂+ 𝐻𝐶𝑂+ 𝐻! 𝐶𝑂+

Figure 6. Lewis structures for the carbonate and bicarbonate ion and carbonic acid.

Many organisms, such as mollusks, sea urchins, and coral have relation to the
chemistry of our oceans because they build their shells out of calcium carbonate, CaCO3.
Changing the amount of one chemical species in the ocean (such as carbonic acid) can affect
the concentration of the others, in turn affecting marine life. In the past years, the amount of
carbon dioxide released into the atmosphere has increased. As a consequence, the pH of
seawater has dropped that corresponds to a 26% increase in the amount of H+ in seawater.
The lowering of pH in our ocean due to the increased atmospheric carbon dioxide is called
ocean acidification. Figure 7 shows the chemistry of carbon dioxide in the ocean and the
interaction of carbonate ion, bicarbonate ion and carbonic acid.


167

Figure 7. Chemistry of Carbon dioxide in the ocean (Fahlman et al., 2018).

In surface waters, organisms experience a difference in environment when acid rain
(also called acidic precipitation) fills lakes and streams. Healthy lakes have a pH of 6.5 or
slightly above. If the pH is lowered below 6.0, fish and other aquatic life are affected (see
Figure 8). Only a few hardy species can survive below pH 5.0. At pH 4.0, lakes become
essentially dead ecosystems. Numerous studies have reported the progressive acidification
of lakes and rivers in certain geographic regions, along with reductions in fish populations.
Monitoring pH in our bodies of water is important, humans are not the only creatures
bearing the costs of acidification.

Figure 8. Aquatic life and pH (Fahlman et al., 2018)

When acid rain falls on or runs off into a lake, the pH of the lake drops (becomes more
acidic) unless the acid is neutralized, or somehow used by the surrounding vegetation. In
some regions, the surrounding soils may contain bases that can neutralize the acid. The
capacity of a lake or other body of water to resist a decrease in pH is called its acid-
neutralizing capacity.
For example, If a lake has a geology of much is limestone, CaCO3, then it has a high
acid-neutralizing capacity because limestone slowly reacts with acid rain. Perhaps most

168
importantly, the lakes and streams also have a relatively high concentration of calcium and
bicarbonate ions. This occurs as a result of the reaction of limestone with carbon dioxide and
water:
𝐶𝑎𝐶𝑂+ (𝑠) + 𝐶𝑂! (𝑔) + 𝐻! 𝑂(𝑙) → 𝐶𝑎!N (𝑎𝑞) + 2 𝐻𝐶𝑂+3 (𝑎𝑞)

Because acid is consumed by the carbonate and bicarbonate ions, the pH of the lake
remains more or less constant.

Example 2. The pH of rainwater collected in a certain region of the northeastern

United States on a particular day was 4.82. Calculate the 𝐻N ion concentration of

the rainwater.

Solution: pH is defined as 𝑝𝐻 = −log [𝐻N ] then we can solve for [𝐻N ] by

taking the antilog of the pH; that is, [𝐻N ] = 103M7

Therefore,

𝑝𝐻 = −log [𝐻N ] = 4.82

𝑙𝑜𝑔 𝐻N = −4.82

𝐻4 = 1056.89 = 𝟏. 𝟓 𝒙 𝟏𝟎5𝟓 𝑴

AQUATIC LIFE
The living organisms (biota) in an aquatic ecosystem may be classified as either
autotrophic or heterotrophic.
Autotrophic. These are organisms that use solar or chemical energy to fix elements
from simple, nonliving inorganic material into complex life molecules that compose living
organisms. Algae are the most important autotrophic aquatic organisms because they are
producers that utilize solar energy to generate biomass from CO2 and other simple inorganic
species.
Heterotrophic. These are organisms that use the organic substances produced by
autotrophic organisms as energy sources and as the raw materials for the synthesis of their
own biomass.
Decomposers (or reducers). These are a subclass of the heterotrophic organisms
and consist of chiefly bacteria and fungi, which ultimately break down material of biological
origin to the simple compounds originally fixed by the autotrophic organisms.
The ability of a body of water to produce living material is known as its productivity.
Productivity results from a combination of physical and chemical factors. High productivity
requires an adequate supply of carbon (CO2), nitrogen (nitrate), phosphorus

169
(orthophosphate), and trace elements such as iron. Excessive productivity results in decay
of the biomass produced, consumption of dissolved oxygen, and odor production, a condition
called eutrophication .
Dissolved oxygen (DO) (pronounced “dee oh”). It is frequently considered as the key
substance in determining the extent and kind of life in a body of water. Deficiency in oxygen
is fatal to many aquatic animals such as fish but in contrast, the presence of oxygen can be
equally fatal to many kinds of anaerobic bacteria.
Biochemical oxygen demand (BOD). It refers to the amount of oxygen utilized when
the organic matter in a given volume of water is degraded biologically.
Carbon dioxide (CO2) . It is produced by respiratory processes in water and
sediments and can also enter water from the atmosphere. Carbon dioxide is required for the
photosynthetic production of biomass by algae and in some cases is a limiting factor. High
levels of carbon dioxide produced by the degradation of organic matter in water can cause
excessive algal growth and productivity.

SOURCES OF POLLUTANTS IN WATER
Point Sources. These are domestic and industrial wastes that are usually collected by a
network of pipes or channels and transmitted to a single point of discharge into the receiving
water. Domestic sewage along with any industrial wastes that are permitted to be discharged
into the sanitary sewers are termed as municipal sewage.

Nonpoint Sources. These are urban and agricultural runoff which are characterized by
multiple discharge points. The polluted water usually flows over the surface of the land or
along common drainage channel to the nearest body of water. Storm water run off from
different sources can transport pollutants such as nitrogen from fertilizers, herbicides
applied to lawns and golf courses, oil, greases, ethylene glycol and other organic debris.

4.0 WATER POLLUTANTS
Oxygen-Demanding Material. These are anything that can be oxidized in the receiving
water resulting in the consumption of dissolved molecular oxygen. This material is usually
biodegradable organic matter but also includes certain inorganic compounds. The
consumption of dissolved oxygen (DO) poses a threat to fish and other higher forms of
aquatic life that must have oxygen to live. The critical level of DO varies greatly among
species. For example brook trout may require about 7.5 mg · L-1 of DO, whereas carp can
survive at 3 mg · L-1. As a rule, the most desirable commercial and game fish require high
levels of dissolved oxygen.

Nutrients. Two nutrients (i.e. nitrogen and phosphorus) of primary concern, are considered
pollutants when they become too much of a good thing. These nutrients are required for the
growth of all living things. But excessive nutrient level can be a problem when some

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organisms multiply or propagate at the expense of others. For example, too much nutrients
can cause large growths of algae, which in turn become oxygen-demanding material when
they die and settle to the bottom. Phosphorus-based detergents, fertilizers, food-processing
wastes, as well as animal and human excrement are some of the majors sources of nutrients.

Pathogenic Organisms. Pathogenic microorganisms found in wastewater include bacteria,
viruses, and protozoa excreted by diseased persons or animals. When discharged into
surface waters, they make the water unfit for drinking (i.e., nonpotable). If the concentration
of pathogens is sufficiently high, the water may also be unsafe for swimming and fishing.
Certain shellfish can be toxic because they concentrate pathogenic organisms in their tissues,
making the toxicity levels in the shellfish much greater than the levels in the surrounding
water.

Suspended Solids (SS). These are organic and inorganic particles that are carried by
wastewater into a receiving water. When the speed of the water is reduced by flow into a
pool or a lake, many of these particles settle to the bottom as sediment. In common usage,
the word sediment also includes eroded soil particles that are being carried by water even if
they have not yet settled. Colloidal particles, which do not settle readily, cause the turbidity
found in many surface waters. As excessive sediment loads are deposited into lakes and
reservoirs, the turbidity increases, light penetration decreases, the bacterial population
often increases, and the solids deposit on the bottom of the water body, destroying the
habitat for many benthic organisms.

Pesticides. These are chemicals used by farmers, households, or industry to regulate and
control various types of pests or weeds. The major types of pesticides are herbicides,
insecticides, and fungicides. Herbicides are used to kill unwanted plants (i.e., weeds).
Insecticides are used to kill insects that would otherwise destroy crops, gardens, or
structures. Fungicides are employed to control the growth of fungi, many of which cause
plant diseases.

Pharmaceuticals and Personal Care Products (PPCPs). These are a class of compounds
that are applied externally or ingested by humans, pets, and other domesticated animals.
They are released to the environment through the disposal of expired, unwanted, or excess
medications to the sewage system by individuals, pharmacies, or physicians. Another source
of PPCPs in the environment is through metabolic excretion—the excretion of the chemically
unaltered parent compound and metabolized by-products in urine and feces. PPCPs, such as
deodorants and sunscreens, can be washed into our waterways during bathing, washing, and
swimming. Some PPCPs are also used as pest-control agents.


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Endocrine-Disrupting Chemicals (EDCs). These are class of chemicals known as endocrine

disrupters. EDCs include the polychlorinated biphenyls, commonly used pesticides such as
atrazine and other triazine chemicals, and the phthalates. EDCs can mimic estrogens,
androgens, or thyroid hormones, or their antagonists, although the structures of many EDCs
bear little resemblance to that of natural hormones with which they interfere. The chemicals
can also alter the normal physiological function of the endocrine system and can affect the
synthesis of hormones in the body. EDCs can also target tissues where the hormones exert
their effects.

Other Organic Chemicals. There are numerous other organic chemicals whose release into
the environment can be problematic. These chemicals include hydrocarbons from
combustion processes and oil and gasoline spills, and solvents used in dry cleaning and metal
washing. The hydrocarbons formed during combustion include chemicals such as methane,
benzene, and a class of compounds called polycyclic aromatic hydrocarbons. The polycyclic
aromatic hydrocarbons (PAHs) contain two or more fused benzene rings. Several of the PAHs
are known human carcinogens.

Toxic Metals. These are heavy metals that enter aquatic environments through the
discharge of industrial waste and waste-water treatment plants, storm-water runoff, mining
operations, smokestack emissions, and other diffuse sources (such as from vehicles). The
most commonly occurring heavy metals are arsenic, cadmium, chromium, copper, nickel,
lead, and mercury. As heavy metals persist in the environment, they tend to accumulate in
soils, sediments, and biota. Heavy metals can also bioaccumulate and biomagnify.

Nanoparticles. Defined as those particles that have a dimension less than 100 nm. Included
in this group of chemicals are naturally occurring humic material (derived from plant and
animal matter); titania particles used in painkilling creams; fullerene nanotube composites
used in the manufacture of tires, tennis rackets, and video screens; fullerene cages used in
cosmetics; and protein-based nanomaterials used in the production of soaps, shampoos, and
detergents. As a result of their small size and large specific surface area, nanoparticles can
sorb and transport toxic pollutants, which when inhaled can cause a number of pulmonary
diseases in mammals.

5.0 WATER TREATMENT
In the development of a water supply system, it is necessary to examine carefully all
the factors that might adversely affect the intended use of a water supply source.
The following four categories are used to describe the quality of a drinking water:
1. Physical: Physical quality correlate to the characteristic of water for domestic use and
are usually associated with the appearance of water, color or turbidity, temperature,
and, in particular, taste and odor.

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2. Chemical: The chemical classification of drinking water includes the identification of

its components and their concentrations.
3. Microbiological: Microbiological agents are important to public health and may also
be significant in modifying the physical and chemical characteristics of water.
4. Radiological: Radiological factors must be considered in areas where the water may
have come in contact with radioactive substances. The radioactivity of the water is
of public health concern.
In a typical water treatment plant (Figure 9), the first step is to pass the water through
a screen that physically removes large impurities. The next step is to add aluminum sulfate
(Al2(SO4)3) and calcium hydroxide (Ca(OH)2).
Aluminum sulfate and calcium hydroxide are flocculating agents; that is, they react
in water to form a sticky floc (gel) of aluminum hydroxide, Al(OH)3. This gel collects
suspended clay and dirt particles on its surface. As the Al(OH)3 gel slowly settles, it carries
particles with it that were suspended in the water. Any remaining particles are removed as
the water is filtered through charcoal or gravel and then sand.
𝐴𝑙! (𝑆𝑂$ )+ (𝑎𝑞) + 3 𝐶𝑎(𝑂𝐻)! (𝑠) → 2 𝐴𝑙(𝑂𝐻)+ (𝑠) + 3 𝐶𝑎𝑆𝑂$ (𝑎𝑞)

Figure 9. A typical municipal water treatment facility. (Fahlman et al., 2018).

The crucial step comes next—disinfecting the water to kill disease-causing microbes.
In the United States, this is most commonly done with chlorine-containing compounds.
Chlorination is accomplished by adding chlorine gas (Cl2), sodium hypochlorite (NaClO), or
calcium hypochlorite (Ca(ClO)2). All of these compounds generate the antibacterial agent
hypochlorous acid, HClO. A very low concentration of HClO, 0.075 to 0.600 ppm, remains to

173
protect the water against further bacterial contamination as it passes through pipes to the
user. Residual chlorine refers to the chlorine-containing chemicals that remain in the water
after the chlorination step. These include hypochlorous acid (HClO), hypochlorite ions
(ClO−), and dissolved elemental chlorine (Cl2). When used properly, chlorine is effective, and
practical. It has several advantages over other disinfectants. It is long-lasting and, therefore,
provides a residual in the distribution system. The major disadvantages of chlorine are the
formation of chlorinated by-products due to the reaction of chlorine with naturally occurring
organic matter and the lack of effectiveness of chlorine in inactivating Cryptosporidium
oocysts.
Fluoridation, the addition of fluoride to strengthen teeth enamel and reduce the
number of cavities, especially in children, can also be a part of the treatment process
Many European and a few U.S. cities use ozone to disinfect their water supplies. One
advantage is that a lower concentration of ozone relative to chlorine is required to kill
bacteria. Furthermore, ozone is more effective than chlorine against water-borne viruses.
But ozonation also comes with disadvantages. One is cost. Ozonation only becomes
economical for large water-treatment plants. Another is that ozone decomposes quickly, and
hence does not protect water from possible contamination as it is piped through the
municipal distribution system. Consequently, a low dose of chlorine must be added to
ozonated water as it leaves the treatment plant.
Disinfecting water using ultraviolet (UV) light is gaining in popularity. By UV, we
mean UVC, the high-energy UV radiation that can break down DNA in microorganisms,
including bacteria. Disinfection with UVC is fast, leaves no residual by-products, and is
economical for small installations, including rural homes with unsafe well water. Like ozone,
however, UVC does not protect the water after it leaves the treatment site. Again, a low dose
of chlorine must be added.


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Click the link below and watch the videos for more understanding about the topic.

https://www.youtube.com/watch?v=A88ih2PQDNs

https://www.youtube.com/watch?v=MgdlAt4CR-4

https://www.youtube.com/watch?v=al-do-HGuIk&t=100s

https://www.youtube.com/watch?v=yEci6iDkXYw

https://www.youtube.com/watch?v=9z14l51ISwg

References:

Mury, M. T. (2018). Chemistry in Context: Applying Chemistry to Society (No. 540 C517cc).
McGraw-Hill,.

Manahan, S. E. (2010). Environmental Chemistry. CRC press.

Masten, S. J., & Davis, M. L. (2014). Principles of Environmental Engineering and Science.
McGraw-Hill Education.


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ASSESSMENT TASK


a) potable water f) ocean acidification

b) surface water g) acid rain

c) wetlands h) dissolved oxygen (DO)

d) estuaries i) biochemical oxygen demand (BOD)

e) thermal stratification j) autotrophic

2. (a) Explain what the dashed lines between water molecules in Figure 2

represent.

(b) In the same figure, label the atoms on two adjacent water molecules with

𝛿 N 𝑜𝑟 𝛿 3 . How do these partial charges help explain the orientation of the

molecules?

3. What makes water unique from other compound in terms of its properties
and characteristics?

4. Briefly discuss the hydrological cycle.

5. Briefly discuss the dissociation process of acids and bases in water.

6. What are the importance of pH monitoring in our bodies of water?

7. Make a brief discussion about different water pollutants (choose only five).

8. Describe the step by step process about how a typical municipal water
treatment plant facility undergo its water treatment operation.


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Unit 4 – Chemistry of the Environment
The Soil Chemistry

LEARNING OBJECTIVES

• Describe the nature and composition of soil.
• Discuss the effects of different compounds in soil.
• Explore different pollutants in soil and remediation techniques for
the conservation of soil.

1.0 NATURE AND COMPOSITION OF SOIL
It is known that soil has its importance in different aspects. For example, in the
production of food; maintaining the balance of carbon, nitrogen, and phosphorus; and for the
construction of building materials.
The chemical nature of soil is that, it is a mixture of weathered rocks and minerals;
decayed plants and animal material (humus and detritus); and small living organisms which
includes plants, animals and bacteria. Soil is also consists of water and air. A typical
productive soil has a solid fraction of almost five (5) percent organic matter and ninety five
(95) percent inorganic matter. There are other soils which has as at least one (1) percent
organic matter but some soil such as peat soils may contain as much as ninety five (95)
percent organic matter.

Distinctive Layers of a Typical Soil
A layer of a typical soil which is called horizon, is the product of complex interactions
between processes that develop during weathering. The rainwater that percolates through
the soil bring dissolved and colloidal solids to lower horizons where they are deposited.
Bacterial decay of residual plant biomass (biological process) produce slightly acidic
carbon dioxide (CO2), organic acids, and complexing compounds that are carried by
rainwater to lower horizons where they combine with clays and other minerals resulting to
the change in the properties of minerals.
The A horizon or topsoil which is the top layer of soil is several inches in thickness.
Maximum biological activity in the soil happens in this layer. This layer also contains most of

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the soil organic matter and is important in the productivity of plant. Figure 1 describes
numerous soils that may have a variety of horizons.
In determining the composition of soils, the parent rocks where soils are formed
definitely play an important role. There are other characteristics of soil which includes:
strength, workability, soil particle size, permeability and extent of maturity.

Vegetation (O) horizon from decayed and decaying plant biomass

(A) horizon, topsoil, rich in partially decayed organic
Regolith matter (humus), plant roots, high biological activity

(E) horizon, layer of elution of clay and aluminum and
iron oxides, generally weathered, leached

(B) horizon, subsoil, accumulation of organic matter,
salts, and clays eluted from upper layers

(C) horizon, weathered parent rock

Bedrock

Figure 1. Profile of soil showing horizons (Manahan, 2010).

Water and Air in Soil
For the production of most plant materials, large quantities of water is basically
important because large quantities of water are needed for the production of most plant
materials. Water is part of the three-phase, solid−liquid−gas system making up soil. It is the
basic transport medium for carrying essential plant nutrients from solid soil particles into
plant roots and to the farthest reaches of the plant’s leaf structure (Figure 2). The water in a
plant evaporates into the atmosphere from the plant’s leaves, a process called transpiration.

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Figure 2. Plants transport water from the soil to the
atmosphere by transpiration (Manahan, 2010).

Soil carries the nutrients to the plant extremities by this process wherein plants
remove carbon dioxide from the atmosphere and add oxygen by photosynthesis. The reverse
of this process occurs during plant respiration.
The water phase is not totally independent of soil and matter because of the presence
of small capillaries and pores in the soil and generally because of its small size particles.
Water present in larger spaces of soil is relatively more available to plants and readily drains
away. Water held in smaller pores or between the unit layers of clay particles is held much
more strongly. Soils containing high organic matter may hold more water than other soils,
but it is somewhat less available to plants because of physical and chemical sorption of the
water by the organic matter.
A much strong interaction between clays and water in soil do exist, clay particles
absorbed water on its surface. Much amount of water may be bound in this manner because
of the high surface/volume ratio of colloidal clay particles. But as soils becomes saturated
with water, there will be a dire change in its physical, chemical, and biological properties.
Oxygen in such soil is immediately consumed by the respiration of microorganisms that
causes degradation of organic matter in soil. The bonds holding soil colloidal particles
together are broken, which causes disruption of soil structure. It is known that the excess
water in such soils is detrimental to plant growth, and the soil does not contain the air
required by most plant roots. Most important crops (exception of rice) cannot grow on soil
soaked with water.

2.0 THE INORGANIC AND ORGANIC MATTER IN SOIL
The Inorganic Components Of Soil
The formation of inorganic colloids from the inorganic soil components are produced
from the weathering of parent rocks and minerals. These colloids are repositories of water
and plant nutrients which can be made available to plants as needed. Inorganic soil colloids
plays a role in the detoxification of substances that could harm plants because these colloids

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often absorb toxic substances in soils. In determining soil productivity, the abundance and
nature of inorganic colloidal material in soil are certainly an important aspect.
The uptake of plant nutrients by roots often involves complex interactions with the
water and inorganic phases. For example, a nutrient held by inorganic colloidal material has
to traverse the mineral/water interface and then the water/root interface. This process is
often strongly influenced by the ionic structure of soil inorganic matter.
The most common elements on the earth’s crust are oxygen, silicon, aluminum, iron,
calcium, sodium, potassium, and magnesium. Therefore, minerals composed of these
elements—particularly silicon and oxygen—constitute most of the mineral fraction of the
soil. Common soil mineral constituents are finely divided quartz (𝑆𝑖𝑂!) , orthoclase
(𝐾𝐴𝑙𝑆𝑖+ 𝑂8 ), albite (𝑁𝑎𝐴𝑙𝑆𝑖+ 𝑂8 ), epidote {𝐶𝑎! }{𝐴𝑙! 𝐹𝑒 +N }(𝑆𝑖! 𝑂4 )(𝑆𝑖𝑂$ )𝑂(𝑂𝐻), goethite
¡𝐹𝑒𝑂(𝑂𝐻)¢, magnetite (𝐹𝑒+ 𝑂$ ), calcium and magnesium carbonates (𝐶𝑎𝐶𝑂+ , 𝑀𝑔𝐶𝑂+ ), and
oxides of manganese and titanium.

Organic Matter In Soil
Organic matter mostly determines soil productivity even though it typically
constitutes only less than five percent of a productive soil. Importance of organic matter in
soil are: (a) source of food for microorganisms, undergoes ion exchange chemical reaction,
contribute to the weathering of mineral matter (process by which soil is formed). An
example for this process is when oxalate ion (C2O42-) produced as a soil fungi metabolite
which occurs in soil as the calcium salts whewellite and weddellite. Oxalate in soil dissolves
minerals, therefore speeding the weathering process and increasing the availability of
nutrient ion species. Oxalate complexation of iron or aluminum in minerals which is involve
in the weathering process is expressed by the reaction:

3𝐻N + 𝑀(𝑂𝐻)+ (𝑠) + 2𝐶𝑎𝐶! 𝑂$ (𝑠) → 𝑀(𝐶! 𝑂$ )3 !N
! (𝑎𝑞) + 2𝐶𝑎 (𝑎𝑞) + 3𝐻! 𝑂

in which M is Al or Fe. Some soil fungi produce citric acid and other chelating organic acids
that react with silicate minerals and release potassium and other nutrient metal ions held by
these minerals.
The build-up of organic matter in soil is greatly influenced by temperature and by the
availability of oxygen. Since the rate of biodegradation decreases with decreasing
temperature, organic matter does not degrade rapidly in colder climates and tends to build
up in soil. In water and in waterlogged soils, decaying vegetation does not have easy access
to oxygen, and organic matter accumulates. The organic content may reach 90% in areas
where plants grow and decay in soil saturated with water. The organic compounds in soil
are summarized in Table 1.


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Table 1. Major Classes of Organic Compounds in Soil (Manahan, 2010)
Compound Type Composition Significance
Humus* Degradation-resistant Most abundant organic component,
residue from plant decay, improves soil physical properties,
largely C, H, and O exchanges nutrients, reservoir of
fixed N
Fats, resins, and Lipids extractable by organic Generally, only several percent of
waxes solvents soil organic matter, may adversely
affect soil physical properties by
repelling water, perhaps phytotoxic
Saccharides Cellulose, starches, hemi Major food source for soil
cellulose, gums microorganisms, help stabilize soil
aggregates
N-containing Nitrogen bound to humus, Provide nitrogen for soil fertility
organics amino acids, amino sugars,
other compounds
Phosphorus Phosphate esters, inositol Sources of plant phosphate
compounds phosphates (phytic acid),
phospholipids
*Humus - a water-insoluble material that biodegrades very slowly, makes up the bulk of soil organic matter.

Soil Humus
Humus is composed of a base-soluble fraction called humic and fulvic acids (an
organic material that remains in the acidified solution), and an insoluble fraction called
humin (is the residue left when bacteria and fungi biodegrade plant material). Humic
substances has an influence in properties of soil even though it has a small percentage in soil
composition. They have an acid-base character which serve as buffers in soil and they
significantly increase the water-holding capacity of soil. Humic substances also strongly bind
metals and serve to hold micronutrient metal ions in soil. The aggregates of soil particles can
also be stabilize by these substances and additionally, can increase the sorption of organic
compounds by soil.

The Soil Solution
The soil solution is the aqueous portion of soil that contains dissolved matter from
the chemical and biochemical processes in soil and from the exchange with the hydrosphere
and biosphere. This medium transports chemical species to and from soil particles and
provides contact between the solutes and the soil particles. It is also an important pathway
for the exchange of plant nutrients between roots and solid soil aside from water which is
vital for plant growth. Most of the solutes present in soil as salts are composed of:
𝐻N , 𝐶𝑎!N , 𝑀𝑔!N , 𝐾 N 𝑎𝑛𝑑 𝑁𝑎N cations (with lower levels of 𝐹𝑒 !N , 𝑀𝑛!N , 𝑎𝑛𝑑 𝐴𝑙 +N ) and

181
𝐻𝐶𝑂+3 , 𝐶𝑂+3 , 𝐻𝑆𝑂$3 , 𝑆𝑂$!3 , 𝐶𝑙 3 , 𝑎𝑛𝑑 𝐹 3 anions. The 𝐹𝑒 !N , 𝑀𝑛!N , 𝑎𝑛𝑑 𝐴𝑙 +N cations are generally
present in hydrolyzed forms or bound with humic substances. Some anions become bound
with 𝐻N (e.g. 𝐻𝐶𝑂+3 - formed from 𝐶𝑂+3 ). Multicharged ions tend to form ion pairs in solution
such as 𝐶𝑎𝑆𝑂$ (𝑎𝑞).

Acid–Base And Ion-Exchange Reactions In Soils
The mineral and organic portions of soils both exchange cations. Clay minerals
undergo this process because of the presence of negatively charged sites on the minerals
resulting from the substitution of an atom of lower oxidation number for one of higher
number (e.g. magnesium for aluminum).
Cation exchange in soil is the mechanism by which potassium, calcium, magnesium,
and essential trace-level metals are made available to plants. When nutrient metal ions are
taken up by plant roots, hydrogen ion is exchanged for the metal ions. This process, plus the
leaching of calcium, magnesium, and other metal ions from the soil by water containing
carbonic acid, tends to make the soil acidic:

{𝑆𝑜𝑖𝑙 }𝐶𝑎!N + 2𝐶𝑂! + 2𝐻! 𝑂 → {𝑆𝑜𝑖𝑙}(𝐻N )! + 𝐶𝑎!N (𝑟𝑜𝑜𝑡) + 2𝐻𝐶𝑂+3

The buffering capacity of soil depends upon its type wherein the soil acts as a buffer
and resists changes in pH.

3.0 ADJUSTMENT OF SOIL ACIDITY
Most common plants grow best in soil with a pH near neutrality. If the soil becomes
too acidic for optimum plant growth, it may be restored to productivity by liming through
the addition of calcium carbonate:

{𝑆𝑜𝑖𝑙 }(𝐻N )! + 𝐶𝑎𝐶𝑂+ → {𝑆𝑜𝑖𝑙 }𝐶𝑎!N + 𝐶𝑂! + 𝐻! 𝑂

In areas of low rainfall, soils may become too basic (alkaline) due to the presence of
basic salts such as 𝑁𝑎! 𝐶𝑂+ . Alkaline soils may be treated with aluminum or iron sulfate,
which release acid during hydrolysis:

2𝐹𝑒 +N + 3𝑆𝑂$!3 + 6𝐻! 𝑂 → 2𝐹𝑒(𝑂𝐻)+ (𝑠) + 6𝐻N + 3𝑆𝑂!!3

Sulfur added to soils is oxidized by bacterially mediated reactions to sulfuric acid:

3
𝑆 + 𝑂! + 𝐻! 𝑂 → 2𝐻N + 𝑆𝑂$!3
2


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and sulfur is used, therefore, to acidify alkaline soils. The huge quantities of sulfur now being
removed from fossil fuels to prevent air pollution by sulfur dioxide may make the treatment
of alkaline soils by sulfur much more attractive economically.
The concentrations of chemicals in soil are given in mass units: parts per million
(ppm), milligrams per kilogram (mg/kg), or micrograms per kilogram (𝜇g/kg). The units
vary somewhat based on the magnitude of the mass of chemical present per unit mass
(usually kilograms) of soil. For example, when dealing with carbon, the concentration is
usually given in percent because carbon generally accounts for about 1 to 25% of soil
material. On the contrary, when working with nutrient concentrations (e.g., nitrogen,
phosphorus, etc.) units of milligrams per kilogram are used. When working with many
hazardous wastes, whose concentrations are usually small, we use units of parts per billion
or micrograms per kilogram.
The movement of ionic nutrients such as nitrate, ammonia, and phosphate is
governed by ion-exchange reactions. For example, sodium ions may be attached to the soil
surface by electrostatic interactions. If water containing calcium is passed through the soil,
the calcium will be preferentially exchanged for the sodium according to this reaction.

2 (𝑁𝑎N − 𝑆𝑜𝑖𝑙) + 𝐶𝑎!N = 𝐶𝑎!N − (𝑆𝑜𝑖𝑙)! + 2 𝑁𝑎N

By this reaction, two sodium ions are released for every ion of calcium exchanged;
thus maintaining the charge balance. Thus, an important characteristic of soil is its exchange
capacity. Exchange capacity is, essentially, the extent to which a unit mass of soil can
exchange a mass of a certain ion of interest. Exchange capacity (reported in units of
equivalents of ions per mass of soil) is an important characteristic of soil in terms of its ability
to leach ions such as magnesium, calcium, nitrate, and phosphate.
Another important process that occurs in soils is sorption. Sorption is essentially the
attachment of a chemical to either the mineral or organic portions of soil particles and
includes both adsorption and absorption.
With low concentrations of pollutants, sorption can be described mathematically by
a linear expression.
𝐶C (𝑚𝑜𝑙 ∙ 𝑘𝑔3( )
𝐾] =
𝐶O (𝑚𝑜𝑙 ∙ 𝐿3( )

Where 𝐶O = the equilibrium concentration of the chemical in the water (mass per
volume of water)
𝐾] = a partition coefficient describing sorption equilibrium of chemical-
distribution ratio = (mass per mass of soil)(mass per volume of water)-1
𝐶C = the equilibrium concentration of the chemical on the soil (mass per mass
of soil)


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The partition coefficients of various organic pollutants can vary over at least eight
orders of magnitude, depending predominately on the chemical characteristics of the
pollutant, but also on the nature of the soil itself.
With most neutral organic chemicals, sorption occurs predominately on the organic
fraction of the soil itself (as long as the fraction of organic material on the soil is “significant”).
In these cases,
𝐶C ≈ 𝐶.' 𝑓.'

Where 𝐶.' = concentration of organic chemical in the organic matter of the soil
𝑓.' = fraction of organic matter in the soil.
68- @8-
Therefore, 𝐾] = 69

Example 1. A soil sample is collected and the soil water is analyzed for the

chemical compound 1,2-dichloroethane (DCA). The concentration in the

water is found to be 12.5 𝜇𝑔 ∙ 𝐿3( . The organic matter content of the soil is

1.0%. Determine the concentration of DCA that would sorbed to the soil and

that associated with the organic matter. DCA has a 𝐾] of 0.724 (𝜇𝑔 ∙

𝑘𝑔3( )(𝜇𝑔 ∙ 𝐿3( )3( .

Solution:

Using the equation:
𝐶C
𝐾] =
𝐶O

Solve for 𝐶C :

𝐶C = 𝐾] 𝐶O = [0.724 (𝜇𝑔 ∙ 𝑘𝑔3( )(𝜇𝑔 ∙ 𝐿3( )3( ](12.5𝜇𝑔 ∙ 𝐿3( )

= 9.05 𝜇𝑔 ∙ 𝑘𝑔3(

Lastly, solve for 𝐶.' :

𝐶C (9.05 𝜇𝑔 ∙ 𝑘𝑔3( )
𝐶.' = = = 𝟗. 𝟎𝟓 𝝁𝒈 ∙ 𝒌𝒈3𝟏
𝑓.' 0.01


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4.0 MACRO- AND MICRONUTRIENTS IN SOIL

Macronutrients In Soil
Elements that occur in substantial levels in plant biomass and fluids are called
macronutrients. The elements that are usually recognized as essential macronutrients
includes: carbon, hydrogen, oxygen, nitrogen, phosphorus, potassium, calcium, magnesium,
and sulfur. These macronutrients can be absorbed from the atmosphere (carbon, hydrogen
and hydrogen) while others which are also essential macronutrients can be obtained from
soil. But nitrogen, phosphorus and potassium are commonly added to soil as fertilizers.
Calcium-deficient soils are relatively uncommon. Application of lime, a process used
to treat acid soils provides a more than adequate calcium supply for plants. However, calcium
uptake by plants and leaching by carbonic acid (𝐻! 𝐶𝑂+ ) may produce a calcium deficiency in
soil. Acid soils may still contain an appreciable level of calcium which, because of competition
by hydrogen ion, is not available to plants. Treatment of acid soil to restore the pH to near
neutrality generally remedies the calcium deficiency. In alkaline soils, the presence of high
levels of sodium, magnesium, and potassium sometimes produces calcium deficiency
because these ions compete with calcium for availability to plants.

Sulfur is assimilated by plants as the sulfate ion, 𝑆𝑂$3! . Lack of sulfur in soil do not
support plant growth well, largely because sulfur is a component of some essential amino
acids and of thiamin and biotin. Sulfate ion is generally present in the soil as immobilized
insoluble sulfate minerals or as soluble salts that are readily leached from the soil and lost
as soil water runoff. Unlike the case of nutrient cations such as potassium ion (K+), little
sulfate is adsorbed to the soil (i.e., bound by ion-exchange binding), where it is resistant to
leaching while still available for assimilation by plant roots.
Organic nitrogen content in soil is over ninety percent (90%) which is usually the
product of the biodegradation of dead plants and animals (see Figure 3). It is eventually
hydrolyzed to ammonium ion (𝑁𝐻$N ), which can be oxidized to nitrate ion (𝑁𝑂+3 ) by means
of bacterial activities in the soil. Nitrogen is an important component of proteins and other
constituents of living matter and its attachment to soil humus (serves as a reservoir of
nitrogen required by plants) is essential in maintaining soil fertility. Whereas, nitrogen is not
a significant product of mineral weathering, unlike potassium or phosphate.
Inorganic nitrogen from fertilizers and rainwater which is often largely lost by
leaching has the additional advantage that its rate of decay then can release nitrogen to
plants, roughly parallels plant growth. This is of great help since nitrogen-fixing organisms
generally cannot supply sufficient nitrogen to meet peak demand.
Nitrogen is an essential component of proteins and other constituents of living
matter. Plants and cereals grown on nitrogen-rich soils not only provide higher yields, but
are often substantially richer in protein and, therefore, more nutritious. Nitrogen is most
generally available to plants as nitrate ion.


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Figure 3. Nitrogen sinks and pathways in soil (Manahan, 2010).

Phosphorus, like nitrogen must be present in a simple inorganic form before it can be
taken up by plants. Although it has a low percentage in plant material but still it is an
important component of plants. In the pH range that is present in most soils, dihydrogen
phosphate ion (𝐻! 𝑃𝑂$_ ) and hydrogen phosphate ion (𝐻𝑃𝑂$!3 ) are the predominant
orthophosphate species. Orthophosphate is most available to plants at pH values near
neutrality. It is believed that in relatively acidic soils, orthophosphate ions are precipitated
or sorbed by species of Al(III) and Fe(III). In alkaline soils, orthophosphate may react with
calcium carbonate to form relatively insoluble hydroxyapatite:

3 𝐻𝑃𝑂$!3 + 5 𝐶𝑎𝐶𝑂+ (𝑠) + 2 𝐻! 𝑂 → 𝐶𝑎# (𝑃𝑂$ )+ (𝑂𝐻)(𝑠) + 5𝐻𝐶𝑂+3 + 𝑂𝐻3

In general, because of these reactions, little phosphorus applied as fertilizer leaches
from the soil. This is important from the standpoint of both water pollution and utilization
of phosphate fertilizers.
For potassium, its high levels are utilized by growing plants. Potassium activates
some enzymes and it is also essential for some carbohydrate transformations. Lack of
potassium in soil can generally reduce crop yields. Due to this, the higher the productivity of
the crop, the more potassium will be removed from the soil. When nitrogen fertilizers are
added to soils to increase productivity, removal of potassium is enhanced. Therefore,
potassium may become a limiting nutrient in soils heavily fertilized with other nutrients.


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Micronutrients In Soil
Essential plant micronutrients includes: boron, chlorine, copper, iron, manganese,
molybdenum (for nitrogen fixation), and zinc. Low levels of these elements are needed by
plants but usually higher levels of these micronutrients are toxic to plants.
Most of these elements function as components of essential enzymes. Manganese,
iron, chlorine, and zinc may be involved in photosynthesis. It is possible that sodium, silicon,
nickel, and cobalt may also be an essential nutrients for some plants.
Iron and manganese occur in a number of soil minerals. Sodium and chlorine (as
chloride) occur naturally in soil and are transported as atmospheric particulate matter from
marine sprays. Some of the other micronutrients and trace elements are found in primary
(unweathered) minerals that occur in soil.
Boron is substituted isomorphically for Si in some micas and is present in tourmaline,
a mineral with the formula 𝐴𝑙5 𝐵+ 𝐹𝑒+ 𝐻(0 𝑁𝑎𝑂+( 𝑆𝑖5 .
Copper is isomorphically substituted for other elements in feldspars, amphiboles,

olivines, pyroxenes, and micas; it also occurs as trace levels of copper sulfides in silicate
minerals.
Molybdenum occurs as molybdenite (𝑀𝑜𝑆! ).
Vanadium is isomorphically substituted for Fe or Al in oxides, pyroxenes,
amphiboles, and micas.
Zinc is present as the result of isomorphic substitution for Mg, Fe, and Mn in oxides,
amphiboles, olivines, and pyroxenes and as trace zinc sulfide in silicates.
Other trace elements that occur as specific minerals, sulfide inclusions, or by
isomorphic substitution for other elements in minerals are chromium, cobalt, arsenic,
selenium, nickel, lead, and cadmium.

Fertilizers
Major components of crop fertilizers are nitrogen, phosphorus and potassium but
magnesium, sulfate and micronutrients may also be added. Fertilizers are designated by
number, such as six (6) for nitrogen (equivalent to 6%) expressed as N, twelve (12) for
phosphorus (equivalent to 12%) expressed as 𝑃! 𝑂# , and eight (8) for potassium (equivalent
to 8%) expressed as 𝐾! 𝑂. Farm manure corresponds to an approximately 0.5-0.24-0.5
fertilizer. The organic fertilizers such as manure must undergo biodegradation to release the
simple inorganic species (𝑁𝑂+3 , 𝐻H 𝑃𝑂$H3+ , 𝐾 N ) absorbed by plants.

𝑁! + 3𝐻! → 2𝑁𝐻+

The anhydrous ammonia product has a very high nitrogen content of 82%. It may be
added directly to the soil, for which it has a strong affinity because of its water solubility and
formation of ammonium ion:

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𝑁𝐻+ (𝑔)(𝑤𝑎𝑡𝑒𝑟) → 𝑁𝐻+ (𝑎𝑞),

𝑁𝐻+ (𝑎𝑞) + 𝐻! 𝑂 → 𝑁𝐻$N + 𝑂𝐻3

A special equipment is needed because of the toxicity of ammonia gas, that’s why the
use of aqua ammonia which is a thirty percent (30%) solution of 𝑁𝐻+ in water must observe
greater safety. It is sometimes added directly to irrigation water. It should be noted that
ammonia vapor is toxic and 𝑁𝐻+ is reactive in some substances and it is considered as a
hazardous waste.
Ammonium nitrate, 𝑁𝐻$ 𝑁𝑂+, is a common solid nitrogen fertilizer which has 33.5%
nitrogen. It is made by oxidizing ammonia over a platinum catalyst, converting the nitric
oxide product to nitric acid and reacting the nitric acid with ammonia. Although convenient
for its application to soil, it requires considerable care during manufacture and storage
because it is explosive.
One of the common problem that can be produced from the use of fertilizer is water
pollution from agricultural runoff which is enriched in nitrogen, phosphorus, and potassium
from fertilizers. A process known as eutrophication can occur. It is the excessive growth of
algae in water body which is caused by the nutrients in fertilizers. Due to this, there would
be algal biomass decay that will consume oxygen, and bodies of water are seriously damaged
because of oxygen depletion. As a non-point source of pollution, fertilizer runoff presents a
challenging environmental problem.

5.0 SOIL POLLUTANTS
Pollutants from Livestock Production
Livestock production generates significant amounts of environmental pollutants.
Livestock manure has a very high BOD and can rapidly deplete oxygen when it gets into
waterways. Decomposition of animal waste products produces inorganic nitrogen that can
contaminate water with potentially toxic nitrate. Inorganic nitrogen and phosphorus
released to water from the decomposition of livestock wastes can cause eutrophication of
water. Nitrous oxide (𝑁! 𝑂) released to the atmosphere from livestock waste degradation can
be an air pollutant. Methane generated in the anaerobic degradation of livestock wastes is a
potent greenhouse gas.

Pesticides and their Residues In Soil
The following are four major concerns regarding pesticides in soil that need to be
considered with respect to their licensing and regulation:
a) carryover of pesticides and biologically active degradation products to crops
grown in later seasons
b) biological effects on organisms in terrestrial and aquatic ecosystems including
bioaccumulation and transfer through food chains

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c) groundwater contamination
d) effects on soil fertility

Herbicides are considered as the most common chemicals that affect soil and
organisms that it supports because the effectivity of herbicides come into direct contact with
soil. It is well studied that these pesticides and other foreign compounds that remain in soil
for a long period of time have its effects. Some are listed below:
a) the substances become increasingly resistant to extraction and desorption process
b) they become significantly less bioavailable to organisms
c) overall toxicity is decreased

The bioavailability and extractability effects are usually associated to interaction of
the pollutant (a compound) with the organic matter in soil and are more pronounced for
soils that has high organic matter content. Micropores of the organic matter trapped these
molecules and become less environmentally reactive. The probable increase in binding time
may be due to the slow migration of molecules into smaller micropores and perhaps there is
a formation of covalent bonds to the organic matter.

Wastes in Soil
It is given that large quantities of waste products are received by soil. Sulfur dioxide
emitted in the burning of sulfur-containing fuels ends up as sulfate in soil. Nitrogen oxides
from the atmosphere that are converted to nitrates are eventually deposited in soil.
Particulate lead from the exhaust of an automobile is found at high concentration in soil
along heavily traveled highways. And also, elevated levels of heavy metals from mines and
smelters are found on soil near such facilities.
Soil is the receptor of many hazardous wastes from landfill leachate, lagoons, and
other sources. In some cases, land farming of degradable hazardous organic wastes is
practiced as a means of disposal and degradation. The degradable material is worked into
the soil, and soil microbial processes bring about its degradation.
The various constituents of soil have different affinities for organic contaminants.
Natural organic matter, primarily humic substances, have a relatively high affinity for
organic contaminants and heavy metal ions. Many soils contain elemental carbon, black
carbon, material in the ash left over from the burning of crop residues, including sugarcane
trash, wheat straw, and rice straw. This material is probably an important repository of
organic contaminants in soil.
Volatile organic compounds (VOCs) such as benzene (𝐶5 𝐻5 ), toluene (𝐶4 𝐻8 ), xylenes
(𝐶8 𝐻(0 ), dichloromethane (𝐶𝐻! 𝐶𝑙! ), trichloroethane (𝐶𝐻+ 𝐶𝐶𝑙+ ), and trichloroethylene
(𝐶! 𝐻𝐶𝑙+ ), may contaminate soil in industrialized and commercialized areas, particularly in
countries in which enforcement of regulations is not very stringent. Some of the sources of

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these VOCs are: leaking underground storage tanks, landfills built before current stringent
regulations were enforced and improperly discarded solvents.
Soil receives enormous quantities of pesticides as an inevitable result of their
application to crops. The degradation and eventual fate of these pesticides on soil largely
determines their ultimate environmental effects. Among the factors to be considered are the
sorption of the pesticide by soil; leaching of the pesticide into water, as related to its potential
for water pollution; effects of the pesticide on microorganisms and animal life in the soil; and
possible production of relatively more toxic degradation products.

Soil Loss and Degradation
Soil is a fragile resource that can be lost by erosion or become so degraded that it is
no longer useful to support crops.
The physical properties of soil and, hence, its susceptibility to erosion, are strongly
affected by the cultivation practices to which the soil is subjected. Desertification refers to
the process associated with drought and loss of fertility by which soil becomes unable to
grow significant amounts of plant life. Desertification involves a number of interrelated
factors, including erosion, climate variations, water availability, loss of fertility, loss of soil
humus, and deterioration of soil chemical properties.
A related problem is deforestation, loss of forests. The problem is particularly acute
in tropical regions, where the forests contain most of the existing plant and animal species.
In addition to extinction of these species, deforestation can cause devastating deterioration
of soil through erosion and loss of nutrients.
Soil erosion is the loss of soil by the action of both water and wind; water is the
primary source of erosion.

6.0 SOIL PRESERVATION AND RESTORATION
Soil Preservation
Food as the most basic need of humans is an important aspect in order to have the
sustainability of means to produce food as a top priority. The preservation of soil and its
ability to support plant life is the most basic part of food sustainability and soil erosion is
considered as one of the problem that could affect our precious soil. The preservation of soil
from erosion is commonly termed soil conservation. There are numerous traditional
solutions to the soil problem which is a well-known agricultural practices such as terracing,
contour plowing, and periodically planting fields with cover crops. For some crops
conservation tillage (no-till agriculture) surely decreases erosion. This practice consists of
planting a crop among the residue of the previous year’s crop without plowing. In the newly
planted crop row, weeds are killed by application of a herbicide prior to planting. The surface
residue of plant material left on top of the soil prevents soil erosion.


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Agroforestry
Trees are a known perennial plants which are very effective in stopping soil erosion.
In the past, trees were often allowed to grow naturally with native varieties without the
benefit of any special agricultural practices such as fertilization. The productivity of biomass
from trees can be greatly increased with improved varieties including those that are
genetically engineered and with the improved cultivation and fertilization.
Agroforestry is a promising alternative in sustainable agriculture in which crops are
grown in strips between rows of trees (see Figure 4). The trees help to preserve or balance
the soil particularly on sloping terrain. For example, choosing trees with the capability to fix
nitrogen then the system can be efficient in this essential nutrient.

FIGURE 4. Alley cropping of crops between rows of trees running across sloping land can be
an effective means of practicing agroforestry sustainably.

Soil Restoration
Soil can be impaired by loss of fertility, erosion, buildup of salinity, contamination by
phytotoxins, such as zinc from sewage sludge, and other insults. Soil has a degree of
resilience and can largely recover whenever the conditions leading to its degradation are
removed. However, in many cases, more active measures called soil restoration are required
to restore soil productivity, through the application of restoration ecology. Measures taken
in soil restoration may include physical alteration of the soil to provide terraces and
relatively flat areas not subject to erosion. Organic matter can be restored by planting crops
the residues of which are cultivated into the soil for partially decayed biomass. Nutrients
may be added and contaminants neutralized.

Green Chemistry and Sustainable Agriculture
The practice of green chemistry may significantly enhance agricultural productivity
and sustainability.
The application of green chemistry to agriculture holds promise for preventing or
alleviating problems such as the following:
a) Pesticides, herbicides, and fertilizers and their products have accumulated on
agricultural lands and waters leading to adverse effects on wildlife, the environment, and
potentially humans as well.

191
b) Nontarget organisms have suffered and insect and weed pests have built up
resistance to agents used in their eradication.
c) Poorly trained and inadequately protected personnel in less developed countries
have suffered adverse effects from modern agricultural products.
d) Disposal problems have arisen with respect to obsolete pesticides.

Agriculture is a science of living organisms applied to human needs for food and fiber
production. So in attempting to find more sustainable and environment-friendly approaches
to agriculture, it is reasonable to look to natural ecosystems that have evolved over the years
that enable various species of plants and animals to thrive. Such an approach is based upon
biomimetics in which humans attempt to mimic natural life systems.
Pesticides that come from natural sources such as plants or bacteria are called
biopesticides. These substances are usually more environmentally friendly than synthetic
pesticides, although the blanket assumption that anything from a natural source is
automatically safer than synthetic materials should not be made.
Biopesticides has its advantages which include a generally lower toxicity than
conventional pesticides, has high specificity for target pests, effective even in very small
quantities and rapid decomposition. Biopesticides are commonly most effective when used
in integrated pest management program.

Click the link below and watch the videos for more understanding about the topic.
https://www.youtube.com/watch?v=moexid5puSI
https://www.youtube.com/watch?v=nEShY_S_KGc


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ASSESSMENT TASK

1: What are the composition of soil?

2. Briefly discuss and illustrate the distinctive layers of a typical soil.

3. What are the effects of inorganic components in soil?

4. How does temperature affect the organic matter in soil?

5. What are the major classes of organic compounds in soil? Briefly discuss

their significance.

6. What are the macro- and micronutrients found in soil that are important
to plants?

7. What are the sources of pollution in soil?

8. Briefly discuss the remediation techniques for the preservation and
conservation of soil.

References:

Manahan, S. E. (2011). Fundamentals of Environmental Chemistry. CRC press.

Masten, S. J., & Davis, M. L. (2014). Principles of Environmental Engineering and Science.

McGraw-Hill Education.


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Special Topics Specific to the Different Fields of Engineering

Final Requirement
Research Paper

Learning Outcome:
Write and present a research paper on the applications of chemistry in specific field
of specialization.
Learning Tasks:
1. All students are required to submit a research paper specific to the different fields of
Engineering by groups consisting of 3 to 5 members.
2. Each group must present through google meet the research proposal consisting of
research title and specific objectives on the 3rd and 4th week of the semester. It will
be subjected for critiquing of the chemistry teacher for approval.
3. From your approved research title and specific objectives, prepare your research
paper.
4. Consult and provide updates to your chemistry instructor on the progress of your
paper every week. There will be 30 minute consultation period allotted per week.
5. Your research should consist of the following parts:
INTRODUCTION – this part should highlights the overview, problem,
importance, literature, objectives and time and place of
study.
MATERIALS AND METHODS - this part should highlight the following

(whichever is applicable to your study): Statistical/research
design, number and distribution of respondents/samples
used, analysis used/evaluation criteria, replications, time of
year when research was conducted, plot or basic
experimental unit, condition of the experiment, and data
collection procedures.
RESULTS AND DISCUSSIONS - this part should present the data gathered using
tables or graphs. Presentation, analysis and interpretation of
significant results must be highlighted in this part.
SUMMARY AND CONCLUSIONS – this should state the concise form of the
findings based on the analysis and interpretation of data
gathered out of the instruments used and presented
according to the specific questions.

194
REFERENCES – this should present the list of source materials used.
QUESTIONNAIRE (or any gathering instruments applicable to your study)
6. Be ready to present the full paper at the 16th and 17th week of the semester through
google meet for final critiquing. Your paper will be graded depending upon the
punctuality, completeness, and correctness of the paper.

7. Submit the soft copy of your research paper in the google classroom on or before the
last week of the semester.

Suggested Readings:

https://www.scientificamerican.com/chemistry/

https://www.popularmechanics.com

https://www.nature.com/nchem/

https://www.sciencemag.org/category/chemistry?page=1

https://www.sciencedaily.com/news/matter_energy/engineering/

https://cen.acs.org/index.html


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Part II:
Laboratory
Experiments

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Name: ________________________________________ Date Submitted: ________________

Course/Year/Section: ______________________ Instructor: ______________________

Experiment No. 1
Common Chemistry Laboratory Equipment
I. Introduction:
Effective learning and teaching of chemistry concepts involves handling, seeing and
manipulating real materials and objects. These science processes can only be done through
laboratory experiments that will provide greater opportunities for learning and help
encourage a deeper understanding of concepts. These offer students the opportunity of
learning science through hands on experiences.
Proper knowledge on how to use the chemical and laboratory equipment, and
procedures properly are necessary before engaging in any laboratory experiments. Without
having the accurate information or knowledge, it can be too tough as well as risky to go with
the experiments. Use of lab equipment can have dangerous side effects if not handled
properly.
II. Objectives:
1. To identify the names and uses of common laboratory equipment used in
chemistry laboratory
2. To explain some important guidelines and procedures in performing
laboratory activities inside the chemistry laboratory

III. Procedure:
Explore the laboratory equipment, its uses, and some policies and guidelines in
chemistry laboratory by viewing the video by Rebelen Cabello using this link:
https://www.youtube.com/watch?v=9Ni5UOGp0hk&feature=youtu.be
After viewing, answer the following guide questions:

1. Why should the spatula used for spooning solid chemicals from a reagent
bottle be clean and dry?

2. Why must flat-topped stoppers be laid with their flat sides on the table?


197
3. What is the use of the glass rod in transferring liquid reagents?

4. In heating liquids in a test tube, why should the tube not be pointed to
anyone while it is being heated?

5. When heating liquids in a test tube, why is the test tube moved back and
forth across the flame?

6. What precaution should be followed in preparing dilute acid solution?

7. Give at least five of the following:
a. Common laboratory equipment used in chemistry lab and its uses
b. Safety rules or precautions inside the chemistry laboratory

8. Explain the importance of knowing laboratory safety rules, guidelines, and
waste management.


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Experiment No. 2
Phase Changes of Matter
I. Introduction:
All matter can move from one state to another. Phase transition is when a
substance changes from a solid, liquid, or gas state to a different state. Every
substance can change from one phase to another at a specific combination of
temperature or pressure. Every substance is in one of these three phases at certain
temperatures. Phase changes happen when it reaches certain special points. It may
require energy for such change to take place. Heat is probably the easiest energy that
can be used to change its physical state. The temperature at which the substance will
change is very dependent on the intermolecular forces that are acting on the
molecules and atoms of the substance.

II. Objectives:
1. Compare the properties of the three states of matter
2. Determine the effect of temperature in phase changes
III. Procedure:
1. Open the simulation link: https://teachchemistry.org/classroom-
resources/heating-curve-of-water-simulation
2. Click on blue line once, then click the reset button.
3. Repeat the procedure in different portions of the blue line.
4. Take note of the molecular arrangement and phase shown in the lower portion
of T1 while repeating this procedure several times in another portion of the
blue line.

a. At what temperature range the phase is in solid, liquid, and gas?
b. What generalization can you make from your observation?


199
5. Try clicking any portion of the blue line where you noticed a solid phase, then
click a second point where you noticed a liquid phase.
6. Calculate the energy required by clicking the calculate button.
7. Take note of the calculated energy required that appear.
8. Perform several trials to counter check your observation by clicking the reset
button.
9. Repeat this procedure in other points such as from the liquid portion to gas
portion of the blue line or from the solid portion to gas portion of the blue line.

c. What pattern did you noticed on the calculated energy required as you move
the points from one phase to another?
d. What generalization can you make from your observation?

IV. Observation:

V. Conclusion:


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Experiment No. 3
Enthalpy Determination
I. Introduction:
When a process occurs at constant pressure, the heat evolved (either released
or absorbed) is equal to the change in enthalpy. Enthalpy (H) is the sum of the internal
energy (U) and the product of pressure and volume ( PV ) given by the equation:
H = U + PV
When a process occurs at constant pressure, the heat evolved (either released
or absorbed) is equal to the change in enthalpy. Enthalpy is a state function which
depends entirely on the state functions T , P and U . Enthalpy is usually expressed
as the change in enthalpy ( ΔH ) for a process between initial and final states:
ΔH = ΔU + P ΔV
Also at constant pressure the heat flow (q) for the process is equal to the
change in enthalpy defined by the equation:
ΔH = q

II. Objectives:
• Determine the enthalpy change of neutralization
• Improvise a constant-pressure calorimeter
III. Procedure:
1. Measure 25 cm3 hydrochloric acid using a measuring cylinder and add it to a
polystyrene cup.
2. Place the cup in a 250 cm3 glass beaker.
3. Construct a suitable table to record the temperature of the acid at minute
intervals for up to 10 minutes
4. Measure 25 cm3 of sodium hydroxide into a measuring cylinder.
5. Start the timer and record the initial temperature of the hydrochloric acid in
the cup.

201
6. Continue to record the temperature each minute for three minutes.

7. At the fourth minute, add the sodium hydroxide to the cup. Do not record the
temperature.
Note: Sodium hydroxide - can cause severe eye damage and skin burns.
8. At the fifth minute, continue recording the temperature up until 10 minutes.
Stir the solution in the cup each time the temperature is recorded.

IV. Observation:
Calculations
• Plot a graph of temperature (y axis) against time (x axis).
• Draw a line of best fit through the points before the addition of the sodium
hydroxide then draw a second line of best fit through the points after the
addition of sodium hydroxide. Extrapolate both of these lines to 4 minutes.
• Use the graph to determine the temperature change at the fourth minute.
• Calculate the energy absorbed by the solution using the equation q = msΔT
• Calculate the amount of HCl used.
• Calculate the enthalpy change of neutralization.


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V. Conclusion:


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Experiment No. 4
The Daniell Cell
I. Introduction:
Many of the things we deal with in life are related either directly or indirectly
to electrochemical reactions. The Daniell cell is an electrochemical cell named after
John Frederic Daniell, the British chemist who invented it in 1836.
A galvanic or voltaic cell is a redox reaction that produces electricity.
In the Daniell cell, a piece of zinc metal is placed in a solution of zinc sulfate in
one container, and a piece of copper metal is placed in a solution of copper(II) sulfate
in another container. These strips of metal are called the cell’s electrodes.

The electrodes act as a terminal, or a holding place, for electrons. A wire
connects the electrodes, but nothing happens until you put a salt bridge between the
two containers. The salt bridge, normally a U-shaped hollow tube filled with a
concentrated salt solution, provides a way for ions to move from one container to the
other to keep the solutions electrically neutral. With the salt bridge in place, electrons
can start to flow. Zinc is being oxidized, releasing electrons that flow through the wire
to the copper electrode, where they’re available for the ions to use in forming copper

204
metal. Copper ions from the copper(II) sulfate solution are being plated out on the
copper electrode, while the zinc electrode is being consumed.
The cations in the salt bridge migrate to the container containing the copper
electrode to replace the copper ions being consumed, while the anions in the salt
bridge migrate toward the zinc side, where they keep the solution containing the
newly formed cations electrically neutral.
The zinc electrode is called the anode, the electrode at which oxidation takes
place, and is labeled with a “–” sign. The copper electrode is called the cathode, the
electrode at which reduction takes place, and is labeled with a “+” sign.

II. Objective:
• Prepare and observe Daniell Cell

III. Procedure:
Prepare a concentrated solution of copper sulfate in distilled water and
another solution of similar concentration of zinc sulfate in distilled water. For
both of these solutions, use about 10-30 grams of dry chemical per 100cc of
distilled water. Construct a setup as shown in figures 4 and 5. Pour the CuSO4
solution in wif the copper electrode and the ZnSO4 solution in with the zinc
electrode. When you measure the voltage across these electrodes, you should find
it to be about 1.1 volts. You would need electrodes with much greater surface area
and more concentrated electrolyte to be able to power a very small light bulb wif
dis device. Try instead a LED.

IV. Observation:


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V. Conclusion:


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Experiment No. 5
Half-life of a Radioisotope
I. Introduction:
The half-life of a radioisotope is the amount of time it takes for one-half of a
sample to decay. Each radioisotope has a characteristic half-life that depends on the
stability of the nucleus.
Half-lives can be calculated from measurements on the change in mass of a
nuclide and the time it takes to occur. The only thing we know is that in the time of
that substance's half-life, half of the original nuclei will disintegrate. Although
chemical changes were sped up or slowed down by changing factors such as
temperature, concentration, etc., these factors have no effect on half-life. Each
radioactive isotope will have its own unique half-life that is independent of any of
these factors.

II. Objective:
• Exhibit modelling half-lives

III. Procedure:
1. Get a piece of graph paper and a licorice stick.
2. Draw a vertical and horizontal axis on the paper
a. Label the vertical axis as radioactive atoms
b. Label the horizontal axis as minutes
3. Place the licorice stick against the vertical axis and mark its full height at 0
minutes
4. At the end of 1 minute tear the stick in half and record the new height
5. Repeat after 1 minute intervals (tearing the stick in half) until you cannot
divide the licorice stick any further
6. Connect the points

VI. Observation:
1. How long is the half-life of the “radioactive” licorice?


207
2. Suppose you ate 20.0 grams of “radioactive” licorice.

3. How many grams of How many grams of “radioactive radioactive” licorice
remain after 3 minutes?

V. Conclusion:


208

Experiment No. 6
The Energy Content of Fuels
I. Introduction:
Fuels are substances that burn to give off a relatively large amount of heat. In
an overall sense, such burning is simply a combustion reaction between the fuel and
oxygen. How much heat is generated depends on what kind of fuel is used and how
much of it is burned.
Many fuels are hydrocarbons such as methane (CH4) and propane (C3H8), i.e.
compounds containing only hydrogen and carbon. Other fuels such as ethanol
(C2H5OH) contain oxygen in addition to carbon and hydrogen. These “oxygenated”
fuels are currently mandated in many urban areas because they are believed to lead
to less pollution. In this experiment, the amount of heat given off by known amounts
of several fuels will be measured – butane (C4H10), methanol (CH3OH), ethanol
(C2H5OH), kerosene, lamp oil, and candle wax. Kerosene, lamp oil, and candle wax are
each mixtures of hydrocarbons, but we will approximate their compositions as
C10H22, C12H26, and C40H82 respectively.
The experimental procedure is to use the fuels to heat water and then measure
the amount of energy absorbed by the water. It takes 1 “calories” (cal) of energy to
raise the temperature of 1 gram of liquid water 1°C.

II. Objective:
• Calculate the amount of heat per gram of fuel burned.

III. Procedure:
IMPORTANT NOTE ABOUT WEIGHING: since many students are using the
balances, it is important to re-check the zero and leveling bubble before each
weighing.
1. Obtain a dry soda can with two holes punched in opposite sides near the top.
2. Weigh the empty soda can to the nearest 0.1 gram.

209
3. Add approximately 100 mL of water to the can.

4. Weigh the can + water to the nearest 0.1 gram, and calculate the mass of the
water in the can.
5. Thread a glass rod through the holes in the can and suspend it from the ring
attached to a ring stand.
6. Put a thermometer in the can and measure the temperature of the water,
estimating it to the nearest 0.1 degree.
7. Place a fuel burner under the can. Adjust the ring so that the bottom of the can
is about 2 cm from the top of the wick of the burner.
8. Weigh the fuel burner and determine its mass to the nearest 0.001 gram
9. Place the fuel burner under the soda can and light the burner. (Do this fairly
quickly after weighing.)
10. If necessary, cautiously adjust the height of the can so that the top of the flame
is just below the bottom of the can.
11. Heat the water until the temperature has increased about 20 oC, then
extinguish the flame.
12. Stir the water gently until the temperature stops rising and then carefully read
the temperature, estimating it to the nearest 0.1 degree.
13. As quickly as possible, determine the mass of the fuel used by reweighing the
fuel burner (to the nearest 0.001 g), then subtract that mass from the original
mass of the burner

IV. Observation:
To determine the amount of heat absorbed by the water from the burning fuel
(q), you must obtain the following information for each experiment: the mass
of the water that was heated, the change in temperature of the water, and the
mass of the fuel burned.

V. Conclusion:


210
Name: _________________________________ Date Submitted:________________

Course/Year/Section: _____________________ Instructor: ______________________

Experiment No. 7
Determination of pH

I. Introduction:
pH is a measure of how acidic/basic water is. The range goes from 0 to 14 and
It is a common knowledge that neutral water has a pH of 7, acids have a pH less than
7 and bases have a pH greater than 7. pH measure the relative amount of free
hydrogen and hydroxyl ions in the water. Since pH can be affected by chemicals in
the water, pH is an important indicator of water that is changing chemically. pH is
reported in "logarithmic units". Each number represents a 10-fold change in the
acidity/basicness of the water. Water with a pH of five is ten times more acidic than
water having a pH of six.
The pH scale describes the hydronium ion concentration in aqueous systems
pH = -log[H3O+]
[H3O+] = 10-pH = 1/10pH
II. Objective:
To develop an understanding of logarithms scales by developing a pH scale.

III. Procedure:
1. Open the simulation link: http://chemcollective.org/vlab/100
Note: Please use Firefox or Chrome web browser to access this page, errors have
been reported when using Internet Explorer.

2. Click on the “Introductory Video and Support Information” for tutorial on
how to use the virtual lab.

3. With the virtual lab, fill 5 flasks with a constant amount of water (less than
half the volume of the flask). For simplicity, use 20 mL, but any amount will do.

Virtual lab tip. You can right click on each flask and label it using the Rename menu
item.

4. Now add the same amount of stock 1M HCl to the first flask (20 mL), and
note that the concentration has been diluted in half, [H3O+] = 0.500M or 1/2 (1/21) the
original molarity.


211
5. From this flask transfer 20 mL to the second flask and note the it has been
diluted in half again,[H3O+]= 0.250M or is one fourth (1/22)the concentration of the
original stock solution.

6. Repeating this procedure with the remaining 3 flasks gives:
3rd dilution: [H3O+] = 0.12500 or 1/8 (1/23) the original stock molarity
4th dilution: [H3O+] = 0.06250 or 1/16 (1/24) the original stock molarity
5th dilution: [H3O+] = 0.03125 or 1/32 (1/25) the original stock solution.
Let’s look at this in more detail:
[H3O+] = 2-n = 1/2n

Where n is the number of successive dilutions and by using a dilution factor of one to
two, you have come up with a log base 2 scale.

Question: Would changing the volume of the original stock solution and the incremental
dilution volumes to a new constant value effect the successive concentrations. Say by starting
with 10 mL and transferring 10 mL increments? If you say yes, repeat the above with 10 mL
increments and explain.

IV. Observation:

V. Conclusion:

212
Appendix

213

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SCI 401

SCI 401 –GENERAL CHEMISTRY

MACALALAD – GAYETA - BASILAN | BATSTATEU

SCI 401 –GENERAL CHEMISTRY

MACALALAD – GAYETA - BASILAN | BATSTATEU

Macro- and Micronutrients in Soil 179

SCI 401 –GENERAL CHEMISTRY

INTENDED LEARNING OUTCOMES

• Discuss the application of Chemistry in relation to generation of energy

MACALALAD – GAYETA - BASILAN | BATSTATEU

• Internet-based as a references of the learners

SCI 401 –GENERAL CHEMISTRY

MACALALAD – GAYETA - BASILAN | BATSTATEU

Unit 1 – INTRODUCTION, LAB SAFETY, AND

Laboratory Safety Policies, safety data

• The students are expected to follow proper laboratory safety

Laboratory Safety Rules and Guidelines

1. Dress appropriately in the laboratory. Wear a

SCI 401 –GENERAL CHEMISTRY

4. Keep all chemical reagents (solids and liquids) in

MACALALAD – GAYETA - BASILAN | BATSTATEU

e. To weigh solid reagents, a clean, dry watch glass

SCI 401 –GENERAL CHEMISTRY

MACALALAD – GAYETA - BASILAN | BATSTATEU

10. Handle glasses with precautions.

SCI 401 –GENERAL CHEMISTRY

10. Learn the location and proper use of safety

a. Fire extinguisher can be used on small or minor fire

Pull the pin.

MACALALAD – GAYETA - BASILAN | BATSTATEU

Common Laboratory Glassware and

Glassware used in all chemistry courses:

Glassware commonly used for conducting reactions and purifications:

SCI 401 –GENERAL CHEMISTRY

Tools used in all chemistry courses:

Various equipment in the organic chemistry laboratory:

Clamps for securing apparatuses

MACALALAD – GAYETA - BASILAN | BATSTATEU

Burners and tubing:

Glassware used in microscale work

Watch the video on the Chemical Laboratory by Rebelen Cabello

SCI 401 –GENERAL CHEMISTRY

MACALALAD – GAYETA - BASILAN | BATSTATEU

Table 2. Prefixes Used in the SI System

SCI 401 –GENERAL CHEMISTRY

b. Derived Quantities. Quantities that emanate or a result of the combination of

MACALALAD – GAYETA - BASILAN | BATSTATEU

Scientific notation is a form of shorthand used to write an extremely large and

SCI 401 –GENERAL CHEMISTRY

Rules for Significant Figures in Mathematical Operations

41.154 Final answer 41.2

MACALALAD – GAYETA - BASILAN | BATSTATEU

SCI 401 –GENERAL CHEMISTRY

MACALALAD – GAYETA - BASILAN | BATSTATEU

SCI 401 –GENERAL CHEMISTRY

MACALALAD – GAYETA - BASILAN | BATSTATEU

SCI 401 –GENERAL CHEMISTRY

MACALALAD – GAYETA - BASILAN | BATSTATEU

Unit 2 - Matter and Energy