General chemistry for engineers

Gaffney
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GENERAL CHEMISTRY
FOR ENGINEERS
 GENERAL
CHEMISTRY
FOR ENGINEERS
JEFFREY S. GAFFNEY
NANCY A. MARLEY
Elsevier
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 Preface
In 2000, the Accreditation Board for Engi-
neering and Technology, Inc (ABET) released
its “Engineering Criteria 2000,” which be-
came the standard for accreditation of all
ABET accredited Engineering Programs pri-
marily in the United States, but also in 30
other countries. The focus of the new criteria
was to be on outcomes, or what the student
has learned. This was a departure from the
previous focus on inputs, or what was being
taught. The important learning outcomes are
listed as a set of 11 skills or abilities that an
engineering student must possess after grad-
uation in order to assure that they are ade-
quately prepared to enter the profession
and perform well under the challenges of
the modern world. These are:
(1) apply the knowledge of mathematics,
science, and engineering
(2) design and conduct experiments, as
well as to analyze and interpret the data
obtained from experiment
(3) design a system, component, or process
to meet desired needs
(4) function on multidisciplinary teams
(5) identify, formulate, and solve
engineering problems
(6) demonstrate an understanding of
professional and ethical responsibility
(7) communicate effectively
(8) obtain the broad education necessary to
understand the impact of engineering
solutions in a global and societal context
(9) recognize the need for and an ability to
engage in life-long learning
(10) acquire a knowledge of contemporary
issues
ix
(11) use the techniques, skills, and modern
engineering tools necessary for
engineering practice.
The curriculum requirements listed in the
Engineering Criteria 2000 were given as
general subject areas only. Details of specific
required courses were not given. The curric-
ulum requirements included:
(1) one year of a combination of college level
mathematics and basic sciences,
with some experimental experience
(2) one and one-half years of engineering
topics, consisting of engineering sciences
and engineering design
(3) a general education component that
complements the technical content of the
curriculum
The “Criteria for Accrediting Engineering
Programs” released by ABET for 2012–13 is a
bit more specific as to the required curricula
for each of its 28 Engineering Areas, listing a
broad or thorough knowledge of chemistry
as a requirement for 11 of the Programs.
An additional 10 programs are listed as re-
quiring a solid knowledge of materials prop-
erties and/or environmental interactions
with materials as well as environmental im-
pacts and sustainability. With the new ABET
focus on ethics, communication skills, team
building, and global awareness, many pro-
grams are turning to additional courses
and/or including study abroad programs
to address the newly added learning
outcomes. This additional curriculum re-
quirement has led many schools to reduce
the two semesters of general chemistry
x PREFACE
requirement to only one semester. This has
led to a problem. The first semester of any
two semester general chemistry course
designed for chemistry students will not ful-
fill the needs of an engineering student. This
is because many topics important to engi-
neering studies such as kinetics, thermody-
namics, etc. are taught during the second
semester and not covered in the first semes-
ter. To remedy this problem, some schools
have adopted a separate one semester accel-
erated course for all areas of engineering re-
quiring a knowledge of chemistry with the
exception being chemical engineering pro-
grams which require more semesters of
chemistry education.
Since this trend is likely to continue, a one
semester course in chemistry should be spe-
cially designed to adequately address the
needs of engineering students, that is, with
a major focus on materials, sustainable en-
ergy, safety, and the environment. To meet
these goals, General Chemistry for Engineers
takes an approach that first establishes a
solid foundation in chemical principles for
the engineering student and then focuses
on how these principles can be applied to
lead to the understanding of the chemistry
and properties of materials by using exam-
ples that reinforce the learning process
throughout the book. By understanding
materials on a molecular level, a more
thorough understanding of their formation
and bulk properties can be achieved and
predicted. The study of the reactions of
materials with each other and the environ-
ment leads to the understanding of their
durability and mechanisms of possible
failure as well as the production of environ-
mental hazards. Additionally, an under-
standing of the formation of materials that
includes the energy required to produce
them is key to developing sustainable en-
ergy and safe methods for their production
and usage.
Special attention is also given to the learn-
ing outcomes added by ABET in 2000 and
specifically identified in 2012–13. Profes-
sional and ethical responsibility in the global
community is addressed by the introduction
of the concepts of green engineering and sus-
tainability. Care has been given to stress the
advantages of interdisciplinary teams work-
ing together and is demonstrated by
presenting chemists (as well as other scien-
tists) and engineers as partners in solving
the problems of society. The engineers of
the future working with chemists and other
scientific disciplines will be instrumental in
the development of solutions to problems
facing the world today and tomorrow. These
include new, safe, and more efficient energy
sources, as well as new designs and pro-
cesses to adapt to the consequences of cli-
mate change. The answers to these
problems will only be achieved through in-
terdisciplinary teams working together and
chemistry and engineering will be at the fore-
front of this effort.
Recognizing the need for a focused and
logically organized textbook for the chemi-
cal education of our future engineers, we
have attempted to combine the ABET goals
and learning outcomes with the fundamen-
tal chemical understanding of thermody-
namics, kinetics, materials, and their
applications with specific examples. Gen-
eral Chemistry for Engineers is organized
to start the engineering student out with
the fundamentals of chemistry and each
chapter builds upon the previous chapter
in order for the development of a thorough
understanding of the basics. Each chapter
contains case studies that show how chem-
istry is applied to a process or measure-
ment and how it is used to solve
problems related to materials and engineer-
ing. Example problems show the student
how to perform critical thinking skills in
setting up chemistry problems and
 PREFACE
determining the correct answer stressing
the correct use of units. After each chapter,
a list of important terms, study questions,
and problems are given to assist the stu-
dent in mastering the material.
The book begins with covering why chem-
istry is important for engineers and going
over basic units of measurements and the
physical states of matter. This textbook takes
an atom’s first approach by presenting the
simple shell model of the atom, covering
the atomic electronic configurations and
showing how these relate to the periodic ta-
ble of the elements along with periodic
trends of the elements in Chapter 2. Once
the student has an understanding of atom
basics, Chapter 3 addresses the types of
chemical bonding of atoms to form mole-
cules after first discussing the difference be-
tween atoms and ions. Ionic, covalent, and
mixed covalent/ionic bonding are covered
along with molecular orbitals, geometry, po-
larity, and describe intermolecular forces
that result from the molecular structures.
The first three chapters give the students a
fundamental basis of the reasons for chemi-
cal reactions that are then introduced in
Chapter 4. This chapter covers the basic con-
cepts of the mole, stoichiometry, and
balancing chemical equations. The concepts
of limiting reagents and percent yield are
addressed, along with aqueous solubility of
ionic compounds, precipitation reactions,
and concentrations in aqueous solutions.
Chapter 5 defines acids and bases in aque-
ous solutions and covers their reactions
along with developing the concept of pH
and other p functions used in chemistry.
Buffers are explained and the method of
chemical titration is introduced to the stu-
dent. A historical perspective of the develop-
ment of the gas laws is given in Chapter 6,
leading to the Ideal Gas Law. Nonideal gas
behavior, the determination and use of par-
tial gas pressures, and gas phase chemical
xi
reactions are also covered in this chapter. Re-
versible reactions resulting in an equilibrium
process and how to determine the reversible
reaction equilibrium constants are detailed
in Chapter 7. Le Chatelier’s principle and
the use of a reaction quotient to determine
concentrations after an equilibrium is dis-
turbed is examined as well. Given the foun-
dation set in the first seven chapters, the
textbook then covers the basics in thermody-
namics in Chapter 8 and chemical kinetics in
Chapter 9.
Chapter 10 introduces the students to
oxidation-reduction chemical reactions and
balancing them. The use of standard cell po-
tentials and the Nernst equation are
presented and their use in chemical electrol-
ysis and the development and use of batte-
ries and fuel cells that are important
engineering are stressed. The properties
and types of solids are reviewed in
Chapter 11 keeping with the materials focus.
Solution chemistry and the effects of temper-
ature and pressure on solutions, the process
of dissolution, ionic solids solubility,
complexing agents, and surfactants are
reviewed in Chapter 12. The chemistry of
carbon is briefly covered in Chapter 13. This
material is usually not covered in this detail
in a normal general chemistry course, but is
needed for the engineering student to have a
basic understanding of how organic reac-
tions can lead to the formation of organic
polymers so often used as materials in engi-
neering today. This chapter stresses the im-
portance of orbital hybridization in the
chemistry of carbon, and goes over the bond-
ing and geometry of sp, sp2, and sp3 carbon
atoms interactions with the common reac-
tants, i.e., H, N, O, and halogens. This allows
the student to then understand free radical
and condensation reaction mechanisms in-
volved in basic organic polymer formations.
Also, it allows for the students to under-
stand their chemical reactivity based on
xii
their chemical structure and their physical
properties.
Nuclear and radiochemistry including ra-
dioactive decay processes, nuclear fission,
and nuclear fusion are addressed in
Chapter 14. This chapter gives the students
an important knowledge base concerning
the use of nuclear energy, along with radia-
tion safety and the application of radioiso-
topes. Basic types of separation and
instrumentation that are commonly used in
the laboratory and in undergraduate teach-
ing laboratories are described
Chapter 15. Considering that a typical se-
mester is 15 weeks in length and involves
3 h of lecture accompanied by 3 h of labora-
tory, this book was written and organized
in this manner to allow the instructor some
flexibility in the material covered during
the course. For example, it would be reason-
able for the instructor to make use of
Chapter 15 as background material for many
of the engineering chemistry laboratory as-
signments. To that end, we have also added
three appendices. The first is working with
units, the second is Using Excel, and the third
is a list of Standard Half-cell Potentials. All of
which should be useful in connection with
the student working with problems in the
classroom as well as the laboratory.
PREFACE
Having worked together with numerous
engineers during our professional careers,
we have recognized and agreed with ABET
that it is extremely important for all engi-
neering disciplines to have a basic under-
standing of chemistry and the common
methods used in chemical analysis. This ba-
sic chemical knowledge is needed for engi-
neers to be able to communicate and work
effectively with chemists in solving current
and future problems involving materials
and sustainable energy. Working together,
in chemists and engineers must also attempt
to make sure that those solutions are envi-
ronmentally safe and sound. We hope that
General Chemistry for Engineers will serve as
the foundation for a one semester chemistry
course for engineering students in the United
States and other countries. We believe that
this chemistry textbook will not only assist
in the training of future engineers as per
ABET accreditation, but will also be a very
useful reference for trained engineers
throughout their careers when a chemistry
basics refresher is needed.
Jeffrey S. Gaffney
Nancy A. Marley
 Acknowledgments
General Chemistry for Engineers evolved
from a one semester course developed and
taught by Dr. Gaffney while he was the Chair
and Professor of Chemistry at the University
of Arkansas at Little Rock. During the devel-
opment of this course, it became clear that
there was not a suitable textbook available
for the engineering students in chemical ba-
sics that they needed as most of the students
had minimal exposure to chemistry before
taking the course. During the course of writ-
ing this book, many questions arose
concerning the best ways to present the
chemistry and how it would best connect
with engineering. We wish to acknowledge
all of the faculty members of Department
xiii
of Chemistry in the College of Arts, Letters,
and Science at the University of Arkansas
at Little Rock for numerous helpful conver-
sations and their constant encouragement
in completing this book. We also want to
acknowledge the assistance of College of
Engineering at the University of Arkansas
at Little Rock faculty for their encourage-
ment. Finally, we want to thank the students
in CHEM 1406 who used the first three chap-
ters of this book in their class and gave us
very useful and positive feedback that
helped us to know we were on the right track
in writing and publishing this book for the
chemical training of future engineers.
 C H A P T E R

1
Introduction
O U T L I N E

1.1 The Role of Chemistry in Engineering 1 1.6 Separation of Mixtures 26

1.2 Green Engineering 4 Important Terms 34
1.3 Measurement and Calculations 5 Study Questions 35
1.4 The Physical States of Matter 14 Problems 37
1.5 Classification of Matter 21

1.1 THE ROLE OF CHEMISTRY IN ENGINEERING

Engineering has been called an applied science. The various disciplines of engineering fo-
cus on the design and construction of structures, machines, apparatus, or processes to solve
problems. This requires an in-depth knowledge of the properties of materials and a broad
knowledge of science and mathematics. Although engineers use scientific principles in their
designs, they must also consider economics and safety issues as well as efficiency, reliability,
and ease of construction. In many cases, the best choice of materials for a design may not be
economically feasible and compromises must be made.
The Accreditation Board for Engineering and Technology (ABET) lists 28 different areas of en-
gineering in their 2012–13 “Criteria for Accrediting Engineering Programs.” These range from
Chemical, Biochemical, Biomolecular Engineering, which use chemical principles on a daily
basis, to Systems Engineering, which is typically not directly involved with chemical princi-
ples. In between these two extremes are disciplines that require a basic knowledge of chem-
istry, materials science, and/or environmental science to fully understand the problems they
are to solve. Even those areas of engineering that do not use chemical principles directly are
involved with them indirectly because chemical principles dictate the properties and behav-
ior of materials, electrical systems, and electronic devices, as well as energy production and
environmental impacts.

General Chemistry for Engineers 1 # 2018 Elsevier Inc. All rights reserved.
https://doi.org/10.1016/B978-0-12-810425-5.00001-1
2 1. INTRODUCTION

An engineer uses the macroscopic properties of materials such as the hardness, strength,
malleability, or conductivity to determine the appropriate choice of materials for a specific
project. Many times, these macroscopic properties are experimentally measured. Chemistry
is the study of the properties and behavior of matter on the microscopic or the atomic/mo-
lecular scale. This description of matter on the microscopic scale lays the foundation for the
underlying reasons for the properties and behavior of materials observed on the macroscopic
scale. By understanding the atomic and molecular forces that lead to the basic properties of
materials, their macroscopic properties and their reactions to external stresses can be better
understood and predicted.

CASE STUDY: SCRATCH HARDNESS

The scratch hardness of a material is the measure of its resistance to being scratched or abraded
by a sharp object. This is a prime consideration in choosing materials for construction of mechanical
tools or machines where friction is an issue. One of the oldest measures of hardness is the Mohs
scale, created in 1812 by the German geologist Friedrick Mohs. This scale was originally designed
to describe the hardness of minerals with diamond as the hardest known mineral at a value of 10 and
talc as the softest known mineral with a value of 1. Other minerals were given intermediate values
based on the ability of one mineral to scratch another mineral.
Table 1.1 lists the scratch hardness of some common materials. The minerals specified by Mohs
are listed in the Table along with some other materials which were determined later to fall between
the levels designated by Mohs. As we shall see in later Chapters, this trend in scratch hardness can
be explained by an understanding of the types of bonding between atoms in the materials on the
microscopic scale. Although diamonds and graphite are both composed of carbon atoms, the hard-
ness of the two materials differs by almost a factor of 10 on the Mohs scale. However, the Mohs scale
is a relative designation and is not a linear scale. The difference between the hardness of graphite
and diamond is much larger on the linear scale of Absolute Hardness. Absolute hardness is a mod-
ern scale of scratch hardness measured by a sclerometer, an instrument that determines the width of
a scratch produced by a moving diamond stylus under a constant force. The scratch hardness num-
ber on the Absolute Hardness scale is the applied force divided by the scratch width multiplied by a
geometrical constant determined for the instrument.
The key to understanding this large difference in the scratch hardness of different forms of car-
bon lies in the structure and bonding between the carbon atoms at the microscopic level, which can
only be explained using chemical principles. These differences in microscopic structure also give the
different forms of carbon large differences in other useful properties as will be explained in
Chapter 11. Because of their extreme hardness, diamonds are used in cutting tools for the manufac-
ture of high precision auto parts, stone building materials, and for cutting cores in well drilling ap-
plications. Graphite is used in pencils and drawing materials due to its softness and ease of removal
from the parent crystal. The same microscopic properties that produce its softness also make it a
good lubricant. Another form of carbon, carbon nanotubes have become more and more important
in engineering due to their excellent mechanical properties, chemical stability, and electrical and
thermal conductivities. The scratch hardness of carbon nanotubes cannot be measured on the mac-
roscopic level with a sclerometer due to their small size. However, the scratch hardness can be es-
timated on the relative scale by understanding the nature of the carbon bonds as well as the crystal
structure of the nanotubes. This has led to the estimation of the scratch hardness of nanocrystalline
diamond as greater than 10 on the Mohs scale.
 1.1 THE ROLE OF CHEMISTRY IN ENGINEERING 3
TABLE 1.1 The Mohs Scale of Hardness Compared to Absolute Hardness as Measured by a Sclerometer. The
original minerals used by Mohs to define the scale are shown in bold
Material Mohs Hardness Absolute Hardness
Cesium, rubidium 0.2–0.3
Lithium, sodium, potassium 0.5–0.6

Talc 1 1
Graphite, tin, lead 1.5 2
Gypsum, calcium, cadmium 2 3
Calcite, copper, arsenic 3 9
Fluorite, iron, nickel 4 21
Steel, platinum 4.5 25

Apatite, cobalt, palladium 5 48

Beryllium, molybdenum 5.5 50
Feldspar, manganese, uranium 6 72
Glass, silicon, opal 6.5 85
Quartz, porcelain, osmium 7 100
Emerald, hardened steel, tungsten 7.3 150

Topaz, cubic zirconia 8 200

Chromium, silicon nitride 8.5 300
Corundum, silicon carbide 9 400
Boron, boron nitride 9.5 1 000
Diamond 10 1 600
Nanocrystalline diamond >10 Not available

An important property of a material, which may limit its usefulness, is its ability to react
with other materials or the environment. A metal that is easily corroded in air may not be
the best choice for an outdoor structure. The ability of metals to react with oxygen in the
air can also be determined by their molecular or atomic properties. In Chapter 10, corro-
sion is explained as a transfer of electrons from the metal to oxygen in the air, resulting in
degradation of the metal and formation of the metal oxide. The same chemical principles
are also responsible for the sometimes unexpected corrosion of metals in contact with each
other as with electroplated materials. This reaction can be explained by understanding the
atomic structure of the metals and the chemical principles that drive the reaction. Armed
with this knowledge, the probability of corrosion occurring under different conditions can
be determined and used in selecting materials for different applications in different
environments.
4 1. INTRODUCTION

1.2 GREEN ENGINEERING

There is an increasing awareness among scientists and engineers that the Earth’s re-
sources are limited and the ever-growing world population and rapid technological de-
velopment places increasing stress on the available global resources. The rapid
advancement of technology without regard to the negative impacts on human health
and the environment will eventually have disastrous consequences. This realization
has led scientists and engineers to promote the “Green Chemistry” and “Green Engineer-
ing” initiatives. Green Chemistry focuses primarily on the elimination or reduction of the
use and generation of substances that are hazardous to human health and the environ-
ment. Green Engineering has a somewhat broader view. It focuses on the design,
development and use of products, processes, and systems that are economically feasible,
while minimizing the risks to human health and the environment. Basically, green engi-
neering seeks to conduct its professional activities in a manner that lessens the negative
impacts on the planet and its ability to sustain life and focuses on how to achieve eco-
nomic, social, and environmental sustainability through the application of green science
and technology.
These goals go beyond the impacts of the products or processes themselves and must
include the entire life cycle of the materials and forms of energy used in the design. Life
cycle design begins with the impacts of the acquisition of the necessary raw materials.
These could include the environmental effects of the mining, drilling, or harvesting tech-
niques used to obtain the raw materials. The life cycle assessment continues through the
manufacturing, distribution, use, and eventual disposal or recycle of a product. Many
times, products are presented as green because the product itself has no negative impacts
on the environment. However, a thorough life cycle analysis can sometimes reveal toxic
effects in its manufacture or disposal. Green Engineering seeks to assure that all materials
and energy sources involved in a process as well as final products are as nonhazardous as
possible, while minimizing energy consumption and material use and preventing waste
generation. Materials and energy sources should be renewable rather than depleting and
final products, processes, and systems should be designed from production to disposal or
recycle with this concept in mind.
The principles of Green Engineering have been outlined by the American Chemical Society
and the Environmental Protection Agency. These principles are intended to be used as guide-
lines to achieve the optimization of sustainability in the design of products, processes, and
systems. The major points in both these lists of green principles are:
• The use of materials and energy sources that are inherently nonhazardous.
• To prevent waste rather than rely on after treatment.
• To minimize consumption of energy and materials.
• The use of renewable materials and energy.
• To minimize the number of material types used in a process.
• To make use of local sources of materials and energy.
• To design for recycle.
• To maximize efficiency.
 1.3 MEASUREMENT AND CALCULATIONS 5
• To choose simplicity over complexity.
• To maximize durability without environmental immortality.
• To meet needs while minimizing excess.
These principles of Green Engineering are built on the idea that it is easier, more efficient,
and less costly to incorporate the prevention of negative environmental impacts at the begin-
ning of a design rather than relying on clean up after they occur. The laws of thermodynamics,
outlined in Chapter 8, tell us that there is no process totally without waste and no energy
source that is totally without environmental impacts. Choices must be made to minimize
these impacts as much as possible while still meeting the needs of society. Engineers make
decisions daily that have potentially significant impacts on the environment. These decisions
can either contribute to our environmental problems and the depletion of our natural re-
sources or they can reduce the negative effects of technology on the environment and help
us achieve environmental, social, and economic sustainability.
The National Academy of Engineering lists mitigation and adaptation to climate change and
the development of clean energy sources at the top of the “Grand Challenges for Engineering”
in the next millennium. These global problems are listed as threatening the future itself.
Slowing the effects of climate change will require new methods for capturing carbon pro-
duced during the combustion of fuels and sequestering it in an environmentally benign form.
At the same time, the emissions of carbon and other greenhouse gases need to be reduced as
much as possible. Adapting to the impacts of climate change will require designing infra-
structure and agricultural processes that can withstand more severe storms, heat waves,
floods, and drought. Although use of carbon-free energy sources such as solar or nuclear
are attractive, their wide use will require the development of more efficient, economical,
and less hazardous manufacturing and operating processes. These challenges bridge across
the fields of engineering and chemistry and meeting them will require a broad knowledge of
both disciplines. The development of sustainable solutions to meet these challenges will re-
quire engineers and chemists working together in interdisciplinary teams on a global scale.

1.3 MEASUREMENT AND CALCULATIONS

The disciplines of chemistry and engineering are both quantitative in nature. That is, they
deal primarily with numerical measurements of the amount of a material or its properties.
Chemists then search for relationships between the physical and chemical properties of a ma-
terial to determine the molecular basis for the observed results. Recording the measurements
of any physical property requires both a number and a unit. This involves working with a
variety of different units and a wide range of numerical values. In order to more easily per-
form calculations involving very large or very small numbers, scientists, mathematicians, and
engineers use a compact standard format called scientific notation, which expresses the
numbers as powers of 10. This format simplifies the calculations, makes it easier to estimate
the magnitude of the result, and decreases the chance of errors in transcribing very large or
very small decimal numbers. It is also more specific than other numerical formats as to the
number of significant figures in a measurement value. Any number written in scientific
6 1. INTRODUCTION

notation is expressed as a number from 1 to less than 10 multiplied by a power of 10. To write
any number in scientific notation:
1. shift the decimal point so that there is only one nonzero digit to the left of the decimal point,
2. multiply the number by a power of 10 that is equal to the number of places the decimal
point has been moved,
3. use a positive power of 10 if the decimal point is moved to the left and a negative power of
ten if the decimal point is moved to the right.
For example, the number 1246 is expressed as 1.246
103 and the number 0.00046 is expressed
as 4.6
10–4 in scientific notation.
Engineering notation is a variant of scientific notation where the powers of ten are re-
stricted to be multiples of three. Therefore, in engineering notation, the restriction of having
only one nonzero digit to the left of the decimal point is dropped in order to maintain the
exponent as a multiple of three. In engineering notation, 1246 will still be expressed as
1.246
103 since it is a multiple of 3. However, 0.00046 would be expressed as 460
10–6.
The advantage of engineering notation is that it is in line with the commonly used units of
measure, which have different names for every 103 increase in value. So, in this format, num-
bers are always stated in terms of thousands, millions, billions, etc. The main disadvantage of
using engineering notation is that the number of significant figures in a measurement is not as
easily determined as it is with scientific notation. For this reason, all measurements and cal-
culations in this text will use scientific notation.
Measurements of physical and chemical properties are not exact. They are subject to un-
certainties, which are caused by errors inherent to the methods of measurements used. These
measurement uncertainties are described by the accuracy and precision of the measurement
method. The accuracy of a measurement is the degree of closeness of the measurements to the
actual or true value. Large deviations from the true value are described as a low degree of
measurement accuracy. This is caused by systematic errors in the measurement method. Sys-
tematic errors are constant and always of the same sign. They result in a constant offset, either
positive or negative, from the true value. Examples of a systematic error would be mass mea-
surements made with a balance that does not read zero with nothing on it or time measure-
ments made with a clock that has not been set properly. The measurement accuracy is
determined by calibration of the measurement method through comparison of the measured
result obtained on a known standard to its certified true value. Calibration of a balance would
involve recording the measurement of a sample of known mass, such as a calibrated weight.
Once this comparison is made, the systematic error can be corrected and the accuracy of the
results improved by either electronically or manually subtracting or adding the offset value
from the measurement.
The precision of a measurement is the degree to which repeated measurements give the
same value whether or not that value is true. Precision is often called reproducibility and is an
indicator of the scatter in a series of measured values made on the same sample. The accuracy
of a measurement can never be any greater than its precision. Large differences in the values
of repeated measurements are described as a low degree of measurement precision. This is
caused by random errors in the measurement method. A random error is one that produces
both positive and negative variations from an average value. They are caused by
unpredictable fluctuations in the measurement apparatus, in the environmental conditions,
or in the operator’s interpretation of the instrumental reading. Examples of some causes of
 1.3 MEASUREMENT AND CALCULATIONS 7
random errors are: the electronic noise in an electrical instrument, the effect of temperature
changes, vibrations and air movement on balances, and using volumetric glassware with
poor resolution to measure volumes. The measurement precision can be determined by re-
peating the measurement several times on the same sample and recording the variation in
the values. Since random errors produce both positive and negative variations in the mea-
surement, the measurement precision can be improved by reporting the average of a series
of measurements made on the same sample.
When the result of a measurement is recorded, the precision of the measurement is indi-
cated in the number of significant figures used in the numerical value. The number of sig-
nificant figures given in a reported measurement is simply the number of digits in the value
that are known with some degree of reliability. The last significant digit reported in the mea-
sured value is the one that is uncertain. All other reported digits are known with a high level
of certainty. For example, the length of a steel bar is reported to be 25.34 cm. This result has
four significant figures, which implies a value of 25.3 to be known with certainty and the last
digit 25.34 to be uncertain.

EXAMPLE 1.1: DETERMINING SIGNIFICANT FIGURES

Determine the number of significant figures in the following measurements of length: (a) 1000 m,
(b) 124.50 km, (c) 200.4 m, (d) 3450 mm, (e) 0.5 m.
1. Convert all measurements to scientific notation:
(a) 1000 m ¼ 1
103 m
(b) 124.50 km ¼ 1.2450
102 km
(c) 200.4 m ¼ 2.004
102 m
(d) 3450 mm ¼ 3.45
103 mm
(e) 0.5 m ¼ 5
10–1 m
2. Determine the number of significant figures by counting the number of digits used in the
scientific notation.
(a) 1
103 ¼ 1 significant figure
(b) 1.2450
102 ¼ 5 significant figures
(c) 2.004
102 ¼ 4 significant figures
(d) 3.45
103 ¼ 3 significant figures
(e) 5
10–1 ¼ 1 significant figure
Remember that trailing zeros are only kept in scientific notation if a decimal point is present in decimal
notation. If a decimal point is not used, the trailing zeros are assumed not to be significant.

The margin of error in last significant digit is determined by repeating the measurement
several times on the same sample and recording the variation in the measured values. The
result is then reported as the average of the series of measurements with a plus or minus
() value written after the measurement. The result of 25.34  0.02 cm for the steel bar means
that all the values obtained were between 25.32 and 25.36 cm. If the measurement method has
been adequately calibrated, it is also implied that the true value lies within this same range.
The number of significant figures in a recorded measurement is equal to the number of digits
used when the value is expressed in scientific notation format.
8 1. INTRODUCTION

EXAMPLE 1.2: SIGNIFICANT FIGURES AND MEASUREMENT

ERRORS
Determine the number of significant figures in the following measurements of length:
(a) 1000  10 m, (b) 124.50  0.05 km, (c) 200.4  0.02 m, (d) 3450  1 mm, (e) 0.5  0.1 m.

1. Convert all measurements to scientific notation based on the uncertainties given.

(a) 1000  10 m ¼ 1.00
103 m
(b) 124.50  0.05 km ¼ 1.2450
102 km
(c) 200.4  0.02 m ¼ 2.004
102 m
(d) 3450  1 mm ¼ 3.450
103 mm
(e) 0.5  0.1 m ¼ 5
10–1 m
2. Determine the significant figures by counting the digits used in scientific notation.
(a) 1.00
103 ¼ 3 significant figures
(b) 1.2450
102 ¼ 5 significant figures
(c) 2.004
102 ¼ 4 significant figures
(d) 3.450
103 ¼ 4 significant figures
(e) 5
10–1 ¼ 1 significant figure
The addition of absolute measurement errors to the measurements removes the ambiguity associated with
trailing zeros.

The results of a calculation based on measurements are only as certain as the least certain
measurement used in the calculation. When adding and subtracting measurements, the un-
certainty of the result is determined by the uncertainty of the least precise measurement. The
least precise measurement is the one with the least significant decimal place. For example,
addition of the measurements: 0.132 + 1.25 + 1.0 gives a result of 2.4 (rounded up from
2.38). The least precise measurement is 1.0, with a least significant decimal place of tenths.
So the result also contains one decimal place (rounded to the tenths place). Addition of the
measurements: 240 + 100 + 1.10 gives a result of 400 (rounded up from 350.1). In this case,
the least precise measurement is 100, with a least significant decimal place of hundreds.
So the result is rounded to the hundreds place. If the measurements were given as:
(249  1) + (100  10) + (1.10  0.02), the result would be 350 since the measurement error indi-
cates that the uncertainty is in the tens place.

EXAMPLE 1.3: DETERMINING SIGNIFICANT FIGURES IN

ADDITION AND SUBTRACTION OF MEASUREMENTS
Give the result of each of the following calculations to the appropriate number of significant fig-
ures: (a) 100 + 2.5 + 20.55, (b) 15 – 12.82, (c) 125.173 + 129.2 + 52.25, (d) 5.671
102 + 6.3
10–3,
(e) 1.4
103–5.5
10–1.
Continued
 1.3 MEASUREMENT AND CALCULATIONS 9

1. Determine the result of each calculation.

Scientific notation is not required for this determination.
(a) 100 + 2.5 + 20.55 ¼ 123.05
(b) 15 – 12.82 ¼ 2.18
(c) 125.173 + 129.2 + 52.25 ¼ 133.45
(d) 5.671
102 + 6.3
10–3 ¼ 567.1063
(e) 1.4
103 – 5.5
10–1 ¼ 1399.45
2. Determine the least significant decimal place in each calculation.
Least significant digit is highlighted in red:
(a) 100 + 2.5 + 20.55
(b) 15 – 12.82
(c) 125.173 + 129.2 + 52.25
(d) 5.671
102 + 6.3
10–3
(e) 1.4
103 – 5.5
10–1
3. Determine the number of significant figures from the least significant decimal place.
Least significant digit is highlighted in red:
(a) 100 + 2.5 + 20.55 ¼ 1 significant figure
(b) 15 – 12.82 ¼ 1 significant figure
(c) 125.173 + 129.2 + 52.25 ¼ 4 significant figures
(d) 5.671
102 + 6.3
10–3 ¼ 4 significant figures
(e) 1.4
103 – 5.5
10–1 ¼ 2 significant figures
4. Round the result to the appropriate number of significant figures.
(a) 100 (rounded from 123.05)
(b) 2 (rounded from 2.18)
(c) 133.5 (rounded from 133.45)
(d) 567.1 (rounded from 567.1063)
(e) 1400 (rounded from 1399.45)

When multiplying and dividing measurements, the result must contain the same num-
ber of significant figures as the measurement with the least number of significant figures.
Thus, (1.3
10–3)
(1.25
102) ¼ 1.7
10–1 (rounded from 1.625
10–1). Since 1.3
10–3 has
two significant figures and 1.25
102 has three significant figures, the result should have
two significant figures. Since significant figures are used to express experimental uncer-
tainty, only experimentally measured numbers or results of calculations that use experi-
mentally measured numbers use significant figures. Numbers that are defined to be a
specific value, such as conversion factors, or the result of a count are exact numbers. Since
they do not have measurement uncertainties associated with them, they are considered to
have an infinite number of significant figures. When used in calculations with numbers
generated from measurements, they do not affect the number of significant figures in
the result.
10 1. INTRODUCTION

EXAMPLE 1.4: DETERMINING SIGNIFICANT FIGURES IN

MULTIPLICATION AND DIVISION OF MEASUREMENTS
Determine the number of significant figures in each of the following calculations: (a) 2000/115,
(b) (136.50)
(0.0014), (c) 200.6/0.25, (d) 3450
2.0, (e) 0.5/2.
1. Convert all values to scientific notation to determine the measurement with the smallest number
of significant figures.
(a) 2000/115 ¼ (2
103)/(1.15
102)
(b) (136.50)
(0.0014) ¼ (1.3650
102)
(1.4
10–3)
(c) 200.6/0.25 ¼ (2.006
102)/(2.5
10–1)
(d) 3450
2.0 ¼ (3.45
103)
2.0
(e) 0.5/2 ¼ (5
10–1)/(2)
2. Determine the result of each calculation in scientific notation.
(a) (2
103)/(1.15
102) ¼ 2
105
(b) (1.3650
102)
(1.4
10–3) ¼ 1.9
10–2
(c) (2.006
102)/(2.5
10–1) ¼ 8.0
102
(d) (3.45
103)
2.0 ¼ 6.9
103
(e) (5
10–1)/(2) ¼ 3
10–1
3. Determine the number of significant figures from the scientific notation.
(a) 2
105 ¼ 1 significant figure
(b) 1.9
10–2 ¼ 2 significant figures
(c) 8.0
102 ¼ 2 significant figures
(d) 6.9
103 ¼ 2 significant figures
(e) 3
101 ¼ 1 significant figure

The global standard and most widely used system of measurement units in both science
and engineering is the International System of Units, abbreviated SI from the French “Le
Système International d’Unit
es.” These SI units are based on seven “base units,” which are
defined in an absolute way without referring to any other units. All other SI units, called SI
“derived units,” can be defined algebraically in terms of the fundamental base units,
although their definitions based on other derived units are more commonly used. For ex-
ample, the SI unit of pressure is the pascal (Pa). It is commonly defined to be a force per
unit area equal to one newton per square meter (N/m2) using the SI derived unit for
force (newton). However, the technical definition in terms of the SI base units is one
kilogram per meter per second squared (kg • m1• s2). Currently, there are 22 accepted
SI derived units for a total of 29 base and derived units. The base units and the most com-
mon derived SI units are listed in Table 1.2. Other SI derived units not included in
Table 1.2 are simple mathematical combinations of the base units that do not have special
names attached to them. For example, the SI unit of area is m2, arising directly from the
algebraic formula for area; length (m)
width (m) ¼ area (m
m ¼ m2). In a similar
manner, the unit for volume is m3, the unit for velocity is m/s, and the unit for density
is kg/m3.
 1.3 MEASUREMENT AND CALCULATIONS 11
TABLE 1.2 The SI System of Units; Base Units Are Listed in Bold
Unit Symbol Measured Property Base Equivalent Derived Equivalent
kilogram kg Mass –

mole mol Amount of substance –

meter m Distance –
radian rad Plane angle m/m ¼ dimensionless
steradian sr Solid angle m2/m2 ¼ dimensionless
second s, sec Time –
kelvin K Temperature –

degree Celsius o
C Temperature K – 273.15
ampere A, amp Electric current –
coulomb C Electric charge A•s
farad F Electric capacitance kg1 • m2 • s4 • A2 C/V
3 2
Ohm Ω Electric resistance kg • m • s 2
•A V/A
1 2 3 2
seimens S Electrical conductance kg •m •s •A A/V
2 3 1
Volt V Electric potential kg • m • s •A W/A
2
newton N Force kg • m • s
pascal Pa Pressure kg • m1 • s2 N/m2
joule J Energy, work kg • m2 • s2 N•m
2 3
watt W Power kg • m • s J/s
2 2 1
webber Wb Magnetic flux kg • m • s •A V•s
2 1
tesla T Magnetic field strength kg • s •A Wb/m2
henry H Inductance kg • m2 • s2 • A2 Wb/A
candela cd Intensity of light –
lumen lm Flux of light cd • sr
Lux lx Flux per unit area cd • m2 lm/m2

hertz Hz Frequency s–1

becquerel Bq Radioactive decay rate s1
gray Gy Radiation dose m2 • s2 J/kg
2 2
sievert Sv Equivalent dose m •s J/kg
1
katal kat Catalytic activity s • mol
12 1. INTRODUCTION

The SI units use a set of prefixes that precede the basic unit of measure which act as
decimal-based multipliers of the unit. These prefixes are listed in Table 1.3. Each prefix name
has an associated symbol which can be used in combination with the symbols for the units of
measure. For example, the prefix “milli” is used to indicate that the unit of measurement is
multiplied by a factor of 10–3. Thus, 1 mm is equal to 1
10–3 m ¼ 0.001 m. Since the symbol for
meter is “m” and the symbol for the prefix “milli” is “m,” the symbol for millimeter is “mm”
(0.001 m ¼ 1 mm). Only one prefix can be used at a time with a unit of measure. This also
applies to units of mass. The SI base unit for mass is the kilogram (not the gram!) and
this unit already uses a designated prefix. So, the prefixes are used with the derived unit
of mass the “gram,” which is defined as the base unit kilogram divided by 1000
(1 g ¼ 1 kg/1000 ¼ 0.001 kg). So, 0.000001 kg (1
10–6 kg) is equal to 0.001 g, which is called
the milligram (mg) not the microkilogram (μkg).

TABLE 1.3 SI Unit Prefixes Used to Define Powers of Ten

Prefix Symbol Multiplier Decimal Equivalent English
24
yotta Y 10 1,000,000,000,000,000,000,000,000 Septillion
21
zetta Z 10 1,000,000,000,000,000,000,000 Sextillion
18
exa E 10 1,000,000,000,000,000,000 Quintillion
15
peta P 10 1,000,000,000,000,000 Quadrillion
12
tera T 10 1,000,000,000,000 Trillion
9
giga G 10 1,000,000,000 Billion
6
mega M 10 1,000,000 Million
3
kilo k 10 1000 Thousand
2
hecto h 10 100 Hundred
1
deka da 10 10 Ten
0
10 1 One
–1
deci d 10 0.1 Tenth
–2
centi c 10 0.01 Hundredth
–3
milli m 10 0.001 Thousandth
–6
micro μ 10 0.000001 Millionth
–9
nano n 10 0.000000001 Billionth
–12
pico p 10 0.000000000001 Trillionth
–15
femto f 10 0.000000000000001 Quadrillionth
–18
atto a 10 0.000000000000000001 Quintillionth
–21
zepto z 10 0.000000000000000000001 Sextillionth
–24
yocto y 10 0.000000000000000000000001 Septillionth
 1.3 MEASUREMENT AND CALCULATIONS 13

EXAMPLE 1.5: CONVERTING BETWEEN UNIT PREFIXES

The distance between carbon atoms in a diamond is 0.154 nm. What is this distance in meters? In
picometers?

1. Convert from nanometers to meters.

The conversion factor from nanometers to meters is: 1 nm ¼ 1
10–9 m
0.154 nm
(1
10–9 m/nm) ¼ 1.54
10–10 m
2. Convert from meters to picometers.
The conversion from meters to picometers is: 1 m ¼ 1
1012 pm
1.54
10–10 m
(1
1012 pm/m) ¼ 1.54
102 pm ¼ 154 pm
Remember that conversion factors are exact numbers and do not affect the number of significant figures in
the result.

EXAMPLE 1.6: CONVERTING BETWEEN POWERS OF TEN

The mass of the earth is 5.97219
1022 kg. What is this mass in teragrams?
1. Convert from kilograms to grams.
1 kg ¼ 1
103 g
(5.97219
1022 kg) (1
103 g/kg) ¼ 5.97219
1025 g
2. Convert from grams to teragrams.
1 g ¼ 1
10–12 Tg
5.97219
1025 g
(1
10–12 g/Tg) ¼ 5.97219
1013 Tg
Remember that ratios of units are cancelled in the same manner as numbers.
This same calculation can be done in one step.
(5.97219
1022 kg)
(1
103 g/kg)
(1
10–12 Tg/g) ¼ 5.97219
1013 Tg
Be sure that all units cancel except for Tg.
For further help with working with units and powers of 10 see Appendix I.

Although the SI system of units can be used to make any physical measurement, some
non-SI units are still widely used in science and engineering. These units have been used for
so long that they most likely will be continued to be used for the foreseeable future. A lim-
ited number of these other units have been defined in terms of the SI units in a similar
manner as the SI derived units in order to assure that their continued use will be consistent
across the globe. These commonly used non-SI units are listed in Table 1.4 with their SI
definitions.
14 1. INTRODUCTION

TABLE 1.4 Commonly Used Units Not Included in the SI System of Units
Unit Symbol Measured Property Base Equivalent Derived Equivalent
minute min Time 60 • s

hour h Time 3600 • s 60 • min

day d Time 86,400 • s 24 • h
degrees Fahrenheit °F Temperature (1.8 • (K – 273.15)) + 32 (1.8•°C) + 32
degree ° Plane angle π/180 • rad
minute ’ Plane angle π/10,800 • rad 1/60•°
00
second Plane angle π/64,800 • rad 1/60•’
3
liter L Volume 0.001 • m
metric ton t Mass 1000 • kg
electronvolt eV Energy 1.602
10–19 • J
atomic mass unit u Mass 1.660
10–27 • kg
ångstr€
om Å Distance 1
10–10 • m

bar bar Pressure 1
105 • Pa

curie Ci Radioactive decay rate 3.7
1010 • Bq
rad rad Radiation dose 1
10–2 • Gy
rem rem Equivalent dose 1
10–2 • Sv

1.4 THE PHYSICAL STATES OF MATTER

Matter is traditionally defined as anything that has mass (m) and volume (V). A material is
defined as anything that is made of matter. Although the term “matter” is most often used by
chemists and physicists in a general sense and the term “material” is most often used by en-
gineers in a more specific sense, in many ways they are the same. The ratio of the mass to the
volume (m/V) of a material is the density, which is most commonly symbolized with the
Greek letter ρ.
ρ ¼ m=V (1)
The SI units for density are given in terms of mass/volume, such as kilograms/cubic meter
(kg/m3) or grams/cubic centimeter (g/cm3). The commonly used non-SI unit of density is
grams/milliliter (g/mL). Since a liter is defined as equal to 0.001 m3, 1 mL is equal to 1 cm3.
The density of a material varies with temperature and pressure. Increasing the pressure on
a compressible material decreases the volume, and since the mass remains constant, its den-
sity is increased according to Eq. (1). Increasing the temperature of a material generally in-
creases its volume and therefore decreases its density. The density of a material may
change abruptly as the temperature rises as shown in Fig. 1.1. Each of these rapid decreases
 1.4 THE PHYSICAL STATES OF MATTER 15
Vapor FIG. 1.1 The changes in the volume and density of a pure
substance as the temperature increases.

Liquid
Volume
Density

Crystalline

Temperature

in density with increasing temperature corresponds to a rapid increase in volume as the ma-
terial undergoes a change in phase or state.

CASE STUDY: NUCLEAR FUEL RODS

A nuclear power plant is powered by a fissionable fuel material, usually uranium dioxide (UO2),
contained in a nuclear reactor. The nuclear reaction produces heat which is then used to produce
energy by more conventional means such as operation of multisteam turbines. Early commercial
nuclear power plant designs incorporated Generation II reactors. Generation II reactors used ura-
nium fuel that is formed into rods and canned inside of zirconium alloy tubes. These tubes are
grouped together into clusters of 20–40 evenly spaced rods. As the nuclear reaction takes place,
the high energies produced by the reaction cause the temperature of the fuel material to increase.
A circulating water cooling system is used to prevent overheating and to maintain a stable operating
temperature inside the fuel rods.
In this design, if the cooling system should fail, the temperature inside the fuel rods would rap-
idly increase and cause the solid uranium fuel to expand. Due to the fixed volume of the fuel tubes,
the rising temperatures would cause pressures inside the tubes to increase. This rising pressure
would eventually lead to rupture of the containment vessel and rapid vaporization of the remaining
water coolant. These early plant designs relied exclusively on active safety features involving elec-
trical or mechanical operations, initiated automatically or by plant operators, to attempt to shut
down the reactor and stop the nuclear reaction and the runaway temperature rise during coolant
failures. In the case of complete electrical failure, such as during the Fukushima tsunami event
of 2011, the rapidly rising temperatures within the fuel could eventually reach melting temperatures
of the solid fuel.
Today’s more advanced nuclear power plant designs include passive safety features which do
not require actions of an operator or electrical mechanisms to shut down the reactor in case of cool-
ant failure. Instead, they rely on the inherent expansion properties of the fuel and cladding under
rising temperatures to act as an automatic feedback mechanism. If the coolant system should fail and
the temperature of the fuel begins to increase, the fuel and cladding are designed to allow the solid
fuel to expand as the temperature rises. As shown in Fig. 1.2, when the fuel expands, the volume of
the solid fuel increases and the density of the fuel decreases. Under normal operating conditions, the
density of the uranium fuel is sufficient to maintain the nuclear chain reaction. Any decrease in
16 1. INTRODUCTION

FIG. 1.2 Density change in uranium 10

dioxide nuclear fuel with increasing Solid
temperature. Data from W.D. Downing,
CONF-810696-1. 9.5

Density (g/cm3)
9
Liquid
8.5

8
2750 2800 2850 2900 2950 3000 3050
Temperature (°C)

density of the fuel interferes with the fission process as will be discussed in Chapter 14. Therefore,
the decrease in fuel density with the expansion of the fuel as temperature rises automatically slows
down the nuclear reaction which allows the temperature of the fuel to decrease spontaneously. This
shuts down the nuclear reaction automatically and keeps the fuel from reaching melting
temperatures.
This passive failsafe design was tested in 1986 by nuclear engineers at Argonne National Labo-
ratory. A coolant failure was simulated by shutting off the coolant pumps with the reactor at full
power. The reactor power dropped to near zero within about 300 s of coolant shut down and no
damage to the fuel or the reactor was observed. This test demonstrated that even with a loss of
all electrical power and no capability to shut down the reactor using the normal systems, this reactor
design will shut down automatically without danger or damage to the system.

There are some important exceptions to this trend of decreasing density with increasing
temperature, the most notable being water. The density of water increases as the temperature
is increased from below 0oC up to 100oC, implying a decrease in volume as the temperature
rises. This behavior seems opposite to that which would be expected from the observation of
the macroscopic properties of water alone and can only be explained with a thorough under-
standing of the forces and properties that control the behavior of water on a molecular level.
This anomalous behavior of water arises from some very important properties that set it apart
from other materials, which will be discussed in detail in Chapter 3.
The most readily observable macroscopic property of matter is its physical state. The five
physical states of matter are: superfluids, solids, liquids, gases, and plasmas. There are four
states of matter observable in everyday life. These are, in the order of increasing temperature
and decreasing densities: solid, liquid, gas, and plasma. A fifth state of matter has most re-
cently been identified that is important to engineers because of its close relationship to super-
conductivity. This state, which exists only at very low temperatures, is called a superfluid.
The three classical states of matter important to chemistry are solid, liquid, and gas. These
classical states of matter were first defined by the differences in their observed macroscopic
properties and the changes in these properties as the temperature was increased (Table 1.5).
A solid has a fixed shape and volume, is noncompressible, and maintains a constant density
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 TABLE

PROLOGUE 7
I. — DEUX HOMMES, DEUX CHIMÈRES 23
II. — LES CAVALIERS… 34
III. — … ET LEUR MONTURE 55
IV. — PROPOS ENTRE CIEL ET TERRE 64
V. — LE JOUR VIOLET 77
VI. — SUR LA PIERRE BRUNE 91
VII. — CEINTRAS ÉGARE SON OMBRE ET SA RAISON 101
VIII. — LA FACE AURÉOLÉE D’ÉTOILES 118
IX. — HEURES D’ATTENTE 130
X. — L’ÊTRE SE MONTRE 143
XI. — EXCURSIONS SOUTERRAINES 163
XII. — FAUX DÉPART 189
XIII. — L’AGONIE DE LA LUMIÈRE 206
XIV. — ÉCRIT SOUS LA DICTÉE DE LA MORT 226
ÉPILOGUE 233
 ACHEVÉ D’IMPRIMER
Le vingt-sept mai mil neuf cent sept
PAR

ARRAULT ET Cie
A TOURS
pour le
MERCVRE
DE
FRANCE
*** END OF THE PROJECT GUTENBERG EBOOK LE PEUPLE DU
PÔLE ***

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