AN IN TRODUCTION T0

CHEMISTRY

SCIENCE
Resource Guide
2022–2023
 Table of Contents

INTRODUCTION . . . . . . . . . . . . . . . . . . . . . 5
SECTION I: THE STRUCTURE OF
MATTER . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
THE “SCIENTIFIC REVOLUTION” . . . . . . 6
Section I Introduction . . . . . . . . . . . . . . . 7
Atomic Theory and Atomic Structure . . 7
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
The Determination of Atomic Masses . . . . . . . . 7
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
Binding Forces . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
Intramolecular Forces . . . . . . . . . . . . . . . . . . . . . . . 16
Polarity of Bonds . . . . . . . . . . . . . . . . . . . . . . . . . . 17
Intermolecular Forces . . . . . . . . . . . . . . . . . . . . . . . 18
The Importance of Hydrogen Bonding in
Living Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
HENRY CAVENDISH AND THE
DISCOVERY OF HYDROGEN . . . . . . . . . 20

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The Effect of Bond Types on the Structures
JOHN DALTON’S LAW OF PARTIAL
of Solid Compounds . . . . . . . . . . . . . . . . . . . . . . . 20
PRESSURES AND ATOMIC THEORY . . . 8 Ionic Lattice . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
Covalent Network or Molecular Solid . . . . . . . . . 20
Atomic Number, Mass Number, and
Isotopes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10 How Intermolecular Forces Determine
The Use of Symbols for Isotopes . . . . . . . . . . . . . .10 States of Matter (Solid, Liquid, Gas) at Room
Standard for Atomic Mass 126C = 12.00000 . . . . . . . 10 Temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
Properties and Importance of Commonly
Recognized Isotopes—2H, 14C, 60Co . . . . . . . . . . . . .10 Molecular Models . . . . . . . . . . . . . . . . . 22
Calculating Weighted Averages . . . . . . . . . . . . . . . . 11 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
Lewis Structures for Atoms and Covalent
Electron Energy Levels and Emission and
and Ionic Compounds . . . . . . . . . . . . . . . . . . . . . 22
Absorption Atomic Spectra . . . . . . . . . . . . . . . . 11
Valence Bond Concept . . . . . . . . . . . . . . . . . . . . . 23
The Wave and Particle Nature of the
Hybridization of Atomic Orbitals as an
Electron and Photon . . . . . . . . . . . . . . . . . . . . . . 12
Explanation for Molecular Shapes . . . . . . . . . 23
Electron Orbitals . . . . . . . . . . . . . . . . . . . . . . . . . 13
The Formation of Molecular Orbitals . . . . . . 23
Periodic Relationships—Definitions,
Oxidation States . . . . . . . . . . . . . . . . . . . . . . . . . . 25
General Trends, and Causes . . . . . . . . . . . . . . . 13
The VSEPR Model . . . . . . . . . . . . . . . . . . . . . . . . . 26
Trends Across a Period of the Periodic
The Resonance Concept Model . . . . . . . . . . . . 26
Table . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
The Geometry of Molecules and Ions . . . . . . . 27
Trends Down a Group of the Periodic
Dipole Moments of Molecules . . . . . . . . . . . . . . 27
Table . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
The Relationship between Molecular
Electronegativity . . . . . . . . . . . . . . . . . . . . . . . . . 15
Properties and Molecular Structure . . . . . . . 27
Chemical Bonding and Intermolecular
Nuclear Chemistry . . . . . . . . . . . . . . . . 28
Forces . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15

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 Nuclear Equations, Half-lives, and
Radioactivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
Nomenclature for Isotopes (Nuclides) . . . . . . . . 28
Decay Equations and Predicting the Products
of Decays . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
Alpha Bombardment Reactions . . . . . . . . . . . . . . . 29
Fission and Fusion Reactions . . . . . . . . . . . . . . 29
Section I Summary . . . . . . . . . . . . . . . . 29
SECTION II: STATES OF MATTER . . . . . 32
Section II Introduction . . . . . . . . . . . . . . 32
Gases . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
Laws of Ideal Gases . . . . . . . . . . . . . . . . . . . . . . . . 32
JACQUES CHARLES AND CHARLES’S
LAW . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
Partial Pressures and the Correction of Gas
Volumes Collected over Water . . . . . . . . . . . . . 35
Kinetic-Molecular Theory (KMT) . . . . . . . . . . 35
The Relation of Particle Speed to Mass,
Collision Frequency, Volume, and Pressure . . 36
Avogadro’s Law . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
AMEDEO AVOGADRO AND AVOGADRO’S
LAW . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
Volume and Mass of One Mole of Ideal Gas at
Standard Temperature and Pressure (STP) . . 37
The Dependence of Kinetic Energy of
Molecules on Temperature . . . . . . . . . . . . . . . . 38
The Ideal Gas Equation . . . . . . . . . . . . . . . . . . . 38
CARL WILHELM SCHEELE, JOSEPH
PRIESTLEY, ANTOINE LAVOISIER, AND
THE DISCOVERY OF OXYGEN . . . . . . . .38
The Behavior of Gases under Extreme
Conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
The Dependence of Relative Rates of Diffusion
and Effusion on Molecular Mass and
Temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
Liquids . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
Solids . . . . . . . . . . . . . . . . . . . . . . . . . . . .42
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Phase Diagrams of One-Component
Systems . . . . . . . . . . . . . . . . . . . . . . . . . . 43
Water and Its Phases and Phase
Transitions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
Carbon Dioxide . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
JOSEPH BLACK AND THE DISCOVERY
OF CARBON DIOXIDE . . . . . . . . . . . . . . .46
Solutions . . . . . . . . . . . . . . . . . . . . . . . . . 46
Types of Solutions and Factors Affecting
Solubility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
Aqueous Solutions . . . . . . . . . . . . . . . . . . . . . . . . . 47
Organic (Nonpolar) Solvents . . . . . . . . . . . . . . 48
Methods of Expressing Concentration . . . . . 48
Percent Composition . . . . . . . . . . . . . . . . . . . . . . . . 48
Molarity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
Molality . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
Raoult’s Law and Colligative Properties . . . 49
Section II Summary . . . . . . . . . . . . . . . . 51
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SECTION III: REACTIONS . . . . . . . . . . . 53
Section III Introduction . . . . . . . . . . . . . 53
Types of Reactions . . . . . . . . . . . . . . . . .53
ANTOINE LAVOISIER, THE
CONSERVATION OF MASS, AND THE
BIRTH OF MODERN CHEMISTRY . . . . . 56
Acid-Base Reactions . . . . . . . . . . . . . . . 57
Arrhenius Acids and Bases . . . . . . . . . . . . . . . . 57
Brønsted-Lowry Acids and Bases . . . . . . . . . . 57
The Acidity Scale: pH . . . . . . . . . . . . . . . . . . . . . 57
Titrations—Mixing Acidic and Basic
Solutions to Measure the Concentration
of an Unknown . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
Acid-Base Reactions and Salts . . . . . . . . . . . . . 59
Precipitation Reactions . . . . . . . . . . . . . 59
Precipitates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
Oxidation-Reduction Reactions . . . . . . 62
Oxidation Numbers . . . . . . . . . . . . . . . . . . . . . . . 62
The Role of the Electron in Oxidation-
Reduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
Electrochemistry . . . . . . . . . . . . . . . . . . 64
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
Cell Potentials . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
LUIGI BRUGNATELLI AND THE
DEVELOPMENT OF
ELECTROPLATING . . . . . . . . . . . . . . . . . . 66
The Nernst Equation . . . . . . . . . . . . . . . . . . . . . . 68
Stoichiometry . . . . . . . . . . . . . . . . . . . . . 69
Ionic and Molecular Species Present in
Chemical Systems: Net Ionic Equations . . . . 69
Balancing Redox Equations . . . . . . . . . . . . . . . 69
Mass and Volume Relations . . . . . . . . . . . . . . . 69
JOSEPH-LOUIS PROUST AND THE LAW
OF DEFINITE PROPORTIONS . . . . . . . . 70
Equilibrium . . . . . . . . . . . . . . . . . . . . . . . . 71
Chemical Equilibrium . . . . . . . . . . . . . . . . . . . . . 71
Equilibrium Constants . . . . . . . . . . . . . . . . . . . . 71
Quantitative Treatment of Equilibrium . . . . 71
Activity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
Equilibrium Constants for Gaseous Reactions:
Kp, Kc . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
Equilibrium Constants for Reactions in
Solution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
Constants for Acids and Bases: pK ; pH . . . . . . . . 72
Solubility Product Constants and their
Application to Precipitation and the
Dissolution of Slightly Soluble Compounds . . . 72
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Kinetics . . . . . . . . . . . . . . . . . . . . . . . . . . 73
The Concept of Rate of Reaction . . . . . . . . . . . 73
The Effect of Temperature, Concentration, and
Surface Area Changes on Reaction Rates . . . . 73
Reaction Potential Energy Diagrams, Energy
of Activation, and the Role of Catalysts . . . . . 74
Thermodynamics . . . . . . . . . . . . . . . . . . 74
JOSEPH BLACK AND LATENT HEAT . . . 75
State Functions . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
The First Law of Thermodynamics . . . . . . . . . 76
Hess’s Law . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
The Second Law of Thermodynamics . . . . . . . 76
Relationship of Change in Free Energy
to Equilibrium Constants and Electrode
Potentials . . . . . . . . . . . . . . . . . . . . . . . . 77
Section III Summary . . . . . . . . . . . . . . . 78
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CONCLUSION . . . . . . . . . . . . . . . . . . . . . 81
GLOSSARY . . . . . . . . . . . . . . . . . . . . . . . .82
APPENDIX: PERIODIC TABLE OF THE
ELEMENTS . . . . . . . . . . . . . . . . . . . . . . . . 91
NOTES . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
BIBLIOGRAPHY . . . . . . . . . . . . . . . . . . . .93
 Introduction
This Science Resource Guide provides an overview of
important concepts in the discipline of chemistry. In
Section I of the resource guide, you will learn about
chemists’ theories for the way matter is arranged and
held together by the forces of nature. Only a relatively
few simple particle types are needed to build the
enormous variety of substances found in nature and
manufactured by chemists.
Section II of the resource guide explores how
substances exist in different phases as gases, liquids,
or solids depending on variables such as temperature
and pressure. You will also learn about the laws and
theories that govern how substances change from one
phase to another. In addition, you will learn that the
basis for our understanding of chemistry is a model
that has small particles moving, vibrating, or rotating.
Furthermore, you will learn about simple ways that
substances can mix together in solutions.
Chemistry is a science of change. Section III deals
with how chemicals interact with one another to make
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new structures and substances. Section III will review
the laws and principles that govern chemical reactions,
and you will learn how to use these laws and principles
to predict what will happen in certain reactions and
how fast these reactions will occur.
Given that the theme of this year’s Academic
Decathlon is the Age of Transformation, we will also
consider American historical developments in chem-
istry that were roughly contemporaneous with the colo-
nial period and the Revolutionary War. This period was
an incredibly rich and exciting time in the history of
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chemistry, and you will learn about some truly revolu-
tionary advancements made by chemists in the eigh-
teenth and early nineteenth centuries.
NOTE TO STUDENTS: Throughout the resource guide
you will notice that some terms have been boldfaced. These
boldfaced terms can be found in the glossary at the end of the
guide.
 Sect ion 1
The Structure of Matter

THE “SCIENTIFIC REVOLUTION”

Your overarching topic of study in this year’s Academic
Decathlon is the American Revolution, and while
that revolution was largely a political one, the term
“revolution” is often used more broadly to describe
any sort of largescale change or transition. In fact, the
period of the American Revolution was one that not only
witnessed many other significant political revolutions,
but also saw momentous changes in other realms,
including science. The eighteenth century brought

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numerous inventions, such as the steam engine, power
looms, and gas lighting, all of which played a role in the
Industrial Revolution. But, even prior to the eighteenth
century, there was a revolution afoot in human
understanding of scientific phenomena that is often An illuminated page from a book on alchemical processes and
referred to as the Scientific Revolution. receipts, c. fifteenth century.
Source: Wellcome Collection
Traditionally, historians have used the term “Scientific
Revolution” to refer to developments in science that
occurred in the sixteenth and seventeenth centuries, though the dates given may vary somewhat depending on
the source. It is important to note, however, that much current scholarship questions the concept of a Scientific
Revolution:
Many historians are now no longer satisfied that there was any singular and discrete event, localized
in time and space, that can be pointed to as “the” Scientific Revolution. … And many historians do not
now accept that the changes wrought on scientific beliefs and practices during the seventeenth century
were as “revolutionary” as has widely been portrayed.1
Thus, many historians do not view the period commonly referred to as the “Scientific Revolution” as a time
profoundly different from the period preceding it or the period that followed it. Rather, scholars now see
advancements in science during the sixteenth and seventeenth centuries as part of a continuum of human
exploration and experimentation, which flowed from the development of natural philosophy in medieval times
and expanded into eighteenth- and nineteenth-century advancements in fields such as chemistry and biology.2
Whether it is fair to term it a revolution or not, there was undoubtedly significant progress made in the field of
chemistry beginning in the seventeenth century. In the earlier part of the century, most scientists still ascribed to
the Aristotelian view that there were four elements: earth, air, fire, and water. At this time, chemistry overlapped
to a significant degree with the field of alchemy, which often involved mystical or supernatural explanations for
natural phenomena. However, the seventeenth century saw a transition toward empiricism—more and more

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scientists came to develop scientific conclusions based on evidence gleaned from scientific experiments.
The seventeenth century also saw the founding of numerous scientific societies, which offered a venue in which
to critique old ways of thinking and propose new ones. Whereas in the past scientific discoveries were often
carefully guarded and even written in secretive, coded language, the formation of scientific societies encouraged
the sharing of knowledge and the publication of scientific papers, which in turn led to careful examination
and review of new theories and conclusions. Experiments could be replicated by others, which often exposed
mistakes and refined scientific understanding. It was not simply what was being discovered but how it was
being discovered that was rather revolutionary, as the scientific method, grounded in experimentation, careful
observation, and empirical reasoning, became the dominant approach to understanding the natural world.

SECTION I INTRODUCTION FIGURE 1

In this section of the resource guide, we will review
how matter is structured and holds together. All
matter is made up of a few fundamental particles, and
tremendous variety occurs in nature because of the
many ways in which these particles can be arranged.
After we discuss these fundamental particles and learn
about how their properties differ, we will examine
the forces that can hold them together in different
ways and will explore how just a few basic bonding

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principles can explain how almost every kind of matter
is held together. Understanding these principles can
enable us to predict both structures and properties of
materials. We will also see how chemists have learned
Usually atoms have a neutral charge; however, atoms can
to organize enormous amounts of information into lose or gain one or more electrons to form, respectively,
tables that summarize properties by emphasizing positive or negative ions.
trends rather than specific information. Source: Sciencenotes.org

ATOMIC THEORY AND ATOMIC
STRUCTURE
Introduction
Atoms are the smallest distinct particles that make up
matter. Each of over one hundred chemical elements is
made up of atoms that have a distinctive structure and
mass. The internal structure of the atom determines
the element’s chemical behavior. This internal atomic
structure is made up of positive, negative, and neutral
particles. Atoms of identical structure all behave in the
same manner. Usually atoms have a neutral charge;
however, atoms can lose or gain one or more electrons
to form, respectively, positive or negative ions.
The Determination of Atomic Masses
Generally, a single atom cannot be weighed. However,
by measuring a large number of identical atoms
simultaneously, chemists can calculate the mass of
one atom. Chemists performed these calculations by
carefully measuring the relative masses of atoms that
combine to form compounds. For example, the mass
of hydrogen that combines with a mass of fluorine to
form the compound HF was found to be in the ratio
1:19 (or 1 gram of hydrogen always combines with 19
grams of fluorine). By measuring many ratios, chemists
established a table of relative atomic masses. Then, by
fixing a standard mass, they were able to construct a
complete mass table for all the chemical elements.
In modern laboratories, chemists can use instruments
called mass spectrometers to determine the relative
masses of single atoms quite accurately. Mass
spectrometers can also measure the masses of atoms
bonded in compounds. Mass spectrometers are even
used at airports to check that passengers are not
carrying compounds that are typical explosives. A
mass spectrometer is able to separate and measure
atoms and compounds because moving charged
species (ions) of different mass (and energy) are

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affected differently by magnetic or electric
fields. A mass spectrometer has three basic FIGURE 2
components:
1. An ion source where compounds or
atoms are converted into (usually
positive) ions;
2. A mass analyzer where the ions are
accelerated in magnetic fields and
take different pathways;
3. A detector that measures the number
of ions of each mass that are present.
In one type of mass spectrometer, the
ions are sent into a curved path by using
a curved magnet. Another type of mass
spectrometer that is commonly used at
airports for security purposes features
a straight pathway used with a cycling
magnetic field. The substances must first be
made into a gas and then introduced into a

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vacuum. The scanning of different masses is
accomplished by varying the magnetic field Diagram of a simple mass spectrometer with a sector-type mass
and/or the detector position. analyzer.

JOHN DALTON’S LAW OF PARTIAL PRESSURES AND ATOMIC THEORY

John Dalton (1766−1844) was an English chemist,
meteorologist, and physicist who made significant
contributions to the field of chemistry, and to this
day, Dalton’s atomic theory remains a landmark
contribution to science. The notion that matter is
comprised of extremely small, indivisible particles
was not originated by Dalton—it was an idea that had
existed for several centuries prior. In the fifth century,
the Greek philosopher Leucippus proposed a concept of
atomism, suggesting that all substances are comprised
of very small indivisible particles. Leucippus’s student
Democritus expanded on this idea by proposing that
there are many different types of particles and that a
substance’s properties are determined by the properties
of the particles of which it is comprised. While the
contributions of ancient scholars are worth noting, it
was Dalton who truly advanced our understanding of
atoms’ behavior and put forth the first modern atomic
theory in the early nineteenth century.
Dalton had a keen interest in meteorology and
maintained daily records of the weather for fifty-seven Portrait of John Dalton, c. 1834, by Charles Turner.

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years, from 1787 until his death in 1844. This interest in
weather led Dalton to become especially focused on the
behavior of gases. Beginning in 1800, he presented a series
of papers to the Manchester Literary and Philosophical
Society describing his experiments with gases and the
conclusions he made concerning their behavior. Dalton
found that the variation of vapor pressure for all liquids
was the same, if given the same variation in temperature
and constant pressure. Dalton also observed that at
constant pressure, different liquids expanded the same
amount if they were subjected to the same increase in
temperature. These observations led Dalton to formulate
what eventually became known as Dalton’s law of partial
pressures, which stated that the total pressure of a mixture
of gases is equal to the sum of the pressures of each
individual gas: PTotal = PA + PB.
As he studied the behavior of gases, Dalton found that some
gases could only combine in specific proportions. Dalton’s
research drew upon the work of two major contributors
to the field of chemistry—the French chemists Antoine
Lavoisier and Joseph Louis Proust. In 1789, Lavoisier had
proposed the law of conservation of mass, which stated that

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during a chemical reaction, matter is neither created nor
destroyed, and thus the mass of the reactants is equal to the
mass of the products. Proust’s law of definite proportions,
put forth in 1799, stated that a substance is always composed
of the same proportion of each element.
Building upon these concepts, Dalton proposed the law
of multiple proportions, postulating that if two elements Various atoms and molecules as depicted in Dalton’s A
combine to form more than one compound, the ratios of New System of Chemical Philosophy (1808).
their masses are whole numbers that are determined by
the atomic weights of the elements involved. This finding led Dalton to propose his atomic theory, which is
considered the first modern atomic theory. In 1808, Dalton published A New System of Chemical Philosophy,
which presented his major conclusions on atomic behavior:

 All matter is composed of very small, indivisible particles called atoms.

 Atoms of the same element have the same properties (size, mass, etc.) while atoms of different elements
will have different properties (e.g., hydrogen has different properties than lead).
 Atoms cannot be divided any further and cannot be created or destroyed.
 Atoms of different elements can combine in whole-number ratios to form compounds.
 Chemical reactions can cause atoms to combine, separate, and rearrange.
Dalton’s theory was incredibly significant. Prior to his work, atomism had largely been described in general
philosophical terms from antiquity, but Dalton put forth a detailed description of atoms that was rooted in
scientific experimentation. We now know that not all aspects of Dalton’s atomic theory hold true. We know, for
example, that atoms can be broken down into subatomic particles (i.e., electrons, neutrons, and protons). We also
know, thanks to mass spectrometry, that different isotopes of the same atom can have different atomic masses.
Yet despite these and other flaws, Dalton’s atomic theory stands as a major achievement that greatly advanced
our understanding of matter.

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 FIGURE 3
Atoms consist of a positively charged central nucleus and
surrounding negative electrons.
Atomic Number, Mass Number, and
Isotopes
It is important for chemists to be able to identify and
communicate the exact composition of an atom. Since
each chemical element has different but unique types
of atoms, standardized identification symbols are
useful. Atoms consist of a positively charged central
nucleus and surrounding negative electrons, symbol
e –. The nucleus always contains at least one positive
proton, symbol p+, and, except for hydrogen, one or
more neutrons, symbol n0.
The Use of Symbols for Isotopes
A
The symbol format used by chemists is Z X , where
X is the element symbol, Z is the atomic number or
number of protons in the nucleus of the atom, and A
is the mass number, which is equal to the number of
neutrons plus the number of protons. Although the
proton number for an atom of a given element can’t
change, atoms can have different numbers of neutrons
in their nucleus. The same type of atom with a different
mass number is called an isotope of the element. Any
arrangement of protons and/or neutrons forming a
nucleus is called a nuclide. The mass number minus
the number of protons will indicate the number of
neutrons. For example, carbon has three isotopes that
are found in nature: 12
C, which has six (12 – 6 = 6)
6 spectrometer, deuterium can be used as a “tracer” to
neutrons in its nucleus, 136 C, which has seven (13 – 6
= 7) neutrons, and 146 C, which has eight (14 – 6 = 8)
neutrons. 146 C atoms are unstable and decay over time
and are therefore classified as radioactive atoms.
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FIGURE 4
Natural isotopes of carbon.
12
Standard for Atomic Mass 6 C = 12.00000
Originally, hydrogen was established as having a mass
of 1, but then it was found more convenient to establish
the mass of a carbon atom as equal to 12 mass units
(named atomic mass units, or amu). This only made a
slight change to the relative scale, but solid carbon was
easier to use for comparison purposes than hydrogen
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gas. Hydrogen, with a mass of 1, is 1/12 the mass of a
carbon. Helium, with a mass of 4, is 1/3 the mass of
carbon.
Properties and Importance of Commonly
Recognized Isotopes—2H, 14C, 60Co
Isotopes are important in chemistry, life sciences, and
earth sciences. An isotope is a form of an element
whose nucleus contains a different number of neutrons
than an atom of that element but has the same number
of protons. Thus, an isotope has the same chemical
properties as other atoms of that element because
the number of protons (and electrons) determines the
chemical properties of the atom.
Many isotopes exist in nature. For example, all forms
of compounds containing hydrogen, such as water,
contain small amounts of deuterium, the isotope of
hydrogen that contains a neutron in its nucleus and so
is written as symbol 21 H to distinguish it from regular
hydrogen, symbol 11 H. The actual amount is one atom
of deuterium for every 6,500 atoms of hydrogen. Since
deuterium can be separated and measured using a mass
find out how chemical reactions of hydrogen occur.
This is done by enhancing the amount of deuterium
(above the normal 1/6,500 ratio) in a reactant and
then following to see where deuterium shows up in

FIGURE 5
Isotopes of hydrogen.
the product(s). Deuterium is the nuclide that is most
commonly used in fusion reactors as it combines in
a fusion reaction with another isotope of hydrogen,
tritium, to release large amounts of energy.
14
6C is an isotope of carbon that is found together
with most forms of carbon. It is formed in the upper
atmosphere as a result of cosmic rays hitting nitrogen
atoms. It mixes with atmospheric carbon dioxide and
then becomes part of the biosphere, entering the bodies
of all living systems. However, this isotope is not
permanently stable and is therefore radioactive, with a
half-life of about 5,730 years.3
14
The most well-known use for 6C
is the dating of
materials containing carbon, such as wood or bones.
When a living system dies, it ceases to maintain
14
equilibrium with the 6 C being produced by cosmic
rays, and so the amount of the isotope decreases at the
half-life rate. This means there will be one-half of the
original amount in 5,730 years. Thus, by measuring the
14
amount of 6C left, archeologists can determine when
the material ceased to be alive.
Even though it is present in very small amounts,
14
because of its radioactivity 6 C can also be a tracer
for what happens to carbon atoms in chemical and
14
biochemical reactions. 6 C was used to work out the
detailed chemistry of photosynthesis and respiration
reactions in plants and animals. It is also being used to
study global climate change effects, as climatologists
look at how rapidly carbon from carbon dioxide cycles
through various reservoirs in the biogeochemical cycle
of carbon.
60
The isotope of cobalt, 27 Co, does not occur in nature,
but can be made in nuclear reactors from cobalt metal.
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It is highly radioactive and has a half-life of 5.3 years.
The radiation emitted as it decays is very penetrating
to the human body and will kill living cells. It has
thus been used to kill cancerous tumor cells. The
radiation will also kill harmful bacteria, so the isotope
is used to sterilize foods for longer storage and
medical equipment prior to use in surgery. In steel, the
60
penetrating power of the radiation from 27 Co is greater
than that from X-rays, and so its radiation is used
to examine steel components and welds for possible
flaws. Since radioactive cobalt darkens photographic
film in the same way as X-rays, photographs of the
welds or other objects can be made.4
Calculating Weighted Averages
When the mass of atoms found in nature is determined
by measuring the masses of elements combined in
chemical compounds, enormous numbers of atoms
have to be used to make the measurement. As a result,
when several isotopes of an element exist, the mass
determined is a weighted average of the masses of the
isotopes. To calculate the weighted average atomic
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mass for an element, you need to know the mass and
the abundance of each isotope.
For an element with two isotopes, such as natural
35
chlorine, which has 75 percent 17 Cl atoms and 25
percent
37
17 Clatoms, we can use the following formula
to determine the weighted average mass of a chlorine
atom:
weighted average mass of a chlorine atom
35 37
= (0.75 x mass 17 Cl atom) + (0.25 x mass 17 Cl atom)
Since the majority, 75 percent, of the chlorine atoms
have a mass of 35, we know that the average mass
will be closer to 35 than to a mass of 37. The accepted
value of the weighted average atomic mass for chlorine
found in nature is 35.453 amu.
Electron Energy Levels and Emission
and Absorption Atomic Spectra
Electrons surround the nucleus of every atom. The
total number of electrons equals the number of protons
(atomic number, Z), but electrons must occupy specific
energy levels in the atom. To determine these energy
levels, chemists excite electrons. When atoms are
heated strongly, electrons can be excited, or raised to
a higher energy level, by the absorption of a quantum
of light energy (photon). When the atom returns to a
 FIGURE 6
The Bohr model of the atom.
lower energy state from the excited state, a photon can
be emitted. When the absorbed or emitted photons are
examined for their energy, the result is known as an
absorption spectrum or emission spectrum.
By measuring the exact energies of the photons, the
differences between the energy levels of the electrons
can be determined. In this way, the Danish physicist
Niels Bohr (1885−1962) and others established a
detailed model of the electronic structure of atoms that
matched the observed spectra. This model is known
as the “Bohr model of the atom.” In the Bohr atom,
the negatively charged electrons occupy stationary
(meaning apparently unchanging) orbits around the
central positively charged nucleus. Each orbit is at
a certain distance from the center of the atom and
provides the electron-nucleus charged pair with a
certain potential energy. No more than two electrons
can occupy the same exact orbit, and even these two
would have slightly different properties. If an electron
can occupy an orbit closer to the nucleus, the emission
of light will occur at an energy corresponding to the
potential energy difference in the atom. The absorption
of light results in the electron moving further from the
nucleus to a higher energy condition.
Scientists also came to recognize that all matter
appeared to have wave properties as well as mass
properties. This was especially noticeable for
extremely light particles such as the electron. This
idea eventually led to a model of the atom in which
electrons exhibited these wave properties. In this
model, the electrons are not at exact distances or fixed
locations and do not rotate in orbits. This model of the
atom is called the “quantum mechanical model.”
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FIGURE 7
The Bohr model versus the quantum mechanical model of
the atom. In the quantum mechanical model, the electrons
are not at exact distances or fixed locations and do not
rotate in orbits.
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The Wave and Particle Nature of the
Electron and Photon
All matter is now known to exhibit both particle
and wave properties—a phenomenon known as the
“wave-particle duality” of matter. The mysterious
properties of light first alerted scientists to the notion
that wavelike properties and particle properties could
be exhibited simultaneously in experiments. Today
we believe all matter can be represented by wave
equations but recognize that matter also exhibits
properties typical of a particle. The field of quantum
physics deals with such issues.
Particles are sometimes thought of as “wave packets”
that can essentially arrive instantaneously to give
the effect of a particle arriving. Light as a particle
was demonstrated most clearly in the photoelectric
effect, where a light “photon” transfers its energy to an
electron, which then is emitted from a metal surface.
Nowadays, this phenomenon is very common in
photocells in digital cameras. The wave properties of
electrons were shown in the classic Davisson-Germer
experiment where electrons scattered at preferred
angles from a nickel crystal.
 FIGURE 8
The photoelectric effect occurs when a light “photon”
transfers its energy to an electron, which then is emitted
from a metal surface.
By Ponor - Own work, CC BY-SA 4.0, https://commons.wikimedia.org/w/
index.php?curid=92684859
Electron Orbitals
Each electron located as a wave in an atom creates an
electron “cloud” that fits exactly at a specific distance
and energy around the nucleus. This location is called
an orbital. Figure 9 shows two atomic electron orbitals,
which are called s and p to differentiate their shapes.
The number and shapes of electron orbitals in a
specific atom determine the kind of chemical bonding
that the atom can undergo. When the atom combines
with other atoms to form a chemical compound, the
structures and shapes of the molecules that are formed
depend on the electron orbitals present. The limitations
imposed by how the electron waves fit underlie the fact
that as protons and electrons are added to build larger
atoms, certain patterns of relationships recur. When all
known stable atoms are placed in a chart according to
their electronic orbital structures, this is found to agree
precisely with a pattern originally based on physical
and chemical properties. This chart is known as the
periodic table.
In the modern periodic table, the elements are arranged
in order of increasing atomic number. Within the table,
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FIGURE 9
Atomic orbitals, s and p.
horizontal rows are called periods, and vertical columns
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are called groups. The group numbering can be done
in two ways—consecutive numbering from 1 to 18 or
using letters “A” or “B” next to a number. There are
eight “A” groups and ten “B” groups in the periodic
table. The “A” groups are called the main groups.
Elements within those groups have greater similarities
in their properties because they have the same amount
of valence electrons. The number of valence electrons
for the elements in the main groups is equal to the group
number. Overall, the position of an element on the
periodic table allows one to predict its properties.
Periodic Relationships—Definitions,
General Trends, and Causes
The position of elements in the periodic table depends
on variations in their orbital structure. As each
element is added to the table, one proton is added to
the nucleus, increasing the atomic number by one.
This also increases the number of electrons by one for
each consecutive element. When the type of orbital
is repeated, the properties appear to repeat, so a new
period is formed, and the next element is placed in
the new row under the position furthest to the left.
Filling the period then continues. In the first period,
only one orbital exists, and it can hold two electrons.
Thus, the next period begins at element three. At the
next distance, two orbitals exist, which between them
 FIGURE 10
A carbon atom has six protons and six electrons.
can hold eight electrons, and so the third period begins
at element eleven. The trends in properties across the
periods and down the groups of the periodic table are
readily explained as a result of the changing trends in
the electronic orbital structures of the atoms and the
attractive forces between the nucleus and the electrons
with the greatest effect on the outer part of the atom.
Trends Across a Period of the Periodic
Table
Atomic radius (a measure of atomic size) decreases
from left to right across a period in the periodic table.
As one proton and one electron are added to an atom,
there is one more proton to attract the electrons. If the
added electrons are approximately the same distance
away from the nucleus, then the increased attraction
will shrink the radius or size of the atom. For example,
a carbon atom has six protons and six electrons. The
next atom in the period, nitrogen, has seven protons
and seven electrons. There is room for the seventh
electron in nitrogen to be about the same distance from
the nucleus as the outer four electrons already there, so
nitrogen atoms are smaller than carbon atoms due to
the increased nuclear charge pulling them in closer.
The ionization energy is the energy required to
entirely remove an outer electron from an atom. Thus,
the ionization energy measures the force of attraction
holding the electron to the nucleus. Ionization energy
increases from left to right across a period in the
periodic table. As the number of protons increases,
so too does the average force pulling on the atoms’
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FIGURE 11
A nitrogen atom has seven protons and seven electrons.
electrons. Thus, it will take more energy to remove an
electron from a nitrogen atom than from a carbon atom.
Nitrogen has a higher ionization energy than carbon.
Electron affinity is a term applied to an atom as a
measure of the fact that most neutral atoms still exhibit
a small attraction for an electron. If the electron is
permanently attracted, then a negative ion results;
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for example, F + e – → F–. This property follows the
same trend as those described above for ionization
energy, generally increasing from left to right across a
period of the periodic table as a result of the increased
effective positive charge. So, fluorine will have a
higher electron affinity than oxygen. Unfortunately,
there are some exceptions (such as N) that may occur
due to details of the atoms’ electronic orbital structure.
Trends Down a Group of the Periodic
Table
Once a period across the table has been completed, there
is no more room for electron orbitals at about the same
distance. The next orbital allowed is at a significantly
greater distance from the nucleus. This increase is
often referred to as starting a new “shell.” Once a shell
begins to fill, it can continue until all the orbitals at that
distance from the nucleus are filled. The elements in a
vertical column of the periodic table have such similar
properties that they are referred to as a group or family.
Atomic radius increases down a group of the periodic
table. This is a result of the increase in the distance of
the outer electrons from the nucleus due to the added
electron shell. Since the outer electrons are farther away,
they are shielded from the attractive pull of the nucleus.
 be an ionic compound, or Na+ – F–. On the other hand,
FIGURE 12 atoms with electronegativity differences between 0.5
and 1.8 form a polar covalent bond. For example, C–O,
H with a difference of 3.5 – 2.5 = 1.0, would be expected
to be an electron sharing or covalent compound,
2.1
but with some dipole moment. A dipole moment
is a measurement of the separation of two opposite
Li Be B C N O F electrical charges. Dipole moments occur in molecules
1.0 1.5 2.0 2.5 3.0 3.5 4.0 that have a positive end and a negative end and provide
a measure of the molecule’s polarity. If EN values are
Na Mg Al Si P S Cl identical, or very similar (less than 0.5), as in H2 or
F2, then a truly equal electron sharing gives rise to a
0.2 1.2 1.5 1.8 2.1 2.5 3.0
nonpolar, covalent compound.
A portion of the periodic table showing Pauling
electronegativities. CHEMICAL BONDING AND
Ionization energy decreases down a group of the INTERMOLECULAR FORCES
periodic table. This is a result of the extra distance Introduction
from the outer electrons to the nucleus, and thus there Atoms of elements cluster together in arrangements that
is a reduced attractive force. only break apart if energy is applied. Such a “cluster”
is a chemical compound, and the specific arrangement
Electron affinity decreases down a group in the periodic
of forces between two atoms is called a chemical bond.
table. This is a result of the extra distance from the

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A group of atoms held together in a constant ratio by
electrons to the nucleus, and thus there is a reduced
strong covalent bonds is often called a molecule.
residual attractive force.
For example, carbon dioxide, with the formula CO2, is
Electronegativity a molecule. Some strongly bonded compounds exist
Electronegativity is a measure of one atom’s
attraction of electrons from an adjacent atom to which
it is chemically bonded.5 Linus Pauling (1901–94) FIGURE 13
devised a method of arriving at a single numerical
Examples of Molecules
value for relative electronegativity, and this value
is referred to as a Pauling electronegativity. A few
such values are exhibited for the small portion of the
periodic table shown in Figure 12.
The higher the value of the Pauling electronegativity,
the greater the attraction for neighboring electrons.
Notice that the trend in values is to increase from left
to right and to decrease from top to bottom. This is
a measure of how much the positive charge on the
nucleus penetrates to the outside of the atom, enabling
the attraction of nearby negative electrons.
You can think of electronegativity, or EN, as a way
to measure the winner in a “tug of war” for bonding
electrons. If the EN values of the two atoms forming
a bond are widely different (greater than 1.8), then the
one with the higher value will pull the electrons away
from the other, forming an ionic bond. So, Na–F, with Molecules can be comprised of atoms of the same element
a difference of 4.0 – 0.2 = 3.8, would be predicted to or atoms of different elements.

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FIGURE 14
a)
= Silicon atom
Si O2
= Oxygen atom
b)
Cl-
Na
Some strongly bonded compounds exist in the form of a
network that extends over a very large number of atoms,
for example silica (image a), which is similar to sand and
has the formula SiO2 , or a large number of ions, like in
table salt, with the formula NaCl (image b).
in the form of a network that extends over a very large
number of atoms—as, for example, with silica (similar
to sand), with the formula SiO2—or a very large number
of ions—as in table salt, with the formula NaCl. The
chemical formula for such compounds represents the
ratio of atoms (or ions) that exist in the large lattice, not
the total number of atoms in the lattice.
There are forces of attraction between most molecules
and neighboring molecules. These forces are called
intermolecular forces. Intermolecular forces are
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responsible for the physical properties of substances.
For instance, strong intermolecular forces between
water molecules (H2O) are the reason that water has a
relatively high boiling point (100 ℃) whereas relatively
weak intermolecular forces between methane (CH4)
molecules result in a very low boiling point for liquid
methane (–162 ℃).
Binding Forces
Five types of attractive forces are associated with
atoms and molecules. All these forces originate in just
one type of fundamental force of attraction—the force
of attraction between positive and negative charges,
which is known as the electrostatic force. Whereas
intermolecular forces exist between molecules,
intramolecular forces bond atoms together within a
molecule.
Intramolecular Forces
Chemists further distinguish intramolecular forces as
those that occur mostly between two atoms in such close
association that a chemical bond is formed. These bonds
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are classified as ionic, covalent, or metallic bonds.
Chemical bonds need substantial energy to break apart
and generally are only broken in chemical reactions.
 Ionic bonds result when one or more electrons
+ transfer from one atom to another, forming
a positive and a negative ion. These ions are
strongly attracted to one another and form an
ionic bond. A common example is sodium
chloride, which forms the ions Na+ and Cl–.
 Covalent bonds are formed when two atoms
share a pair of electrons. The pair of electrons
attracts the nuclei of both atoms, creating the
force that holds the nuclei together and forms
the covalent bond.
 Metallic bonds exist when atoms, generally of
the same element, are bonded in such a way as
to allow many electrons to move more freely
among the atoms. This is called an electron
“sea.” These moving electrons make up
electricity; hence, metals have good electrical
conductivity. Examples of metals are sodium
(Na) and gold (Au). When more than one
element is present, the metal is called an alloy.
Brass (made from copper and zinc) is a metal
alloy and is a good conductor of electricity.
 FIGURE 15

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A summary of intramolecular forces.

Intramolecular forces are summarized in Figure 15,

which also shows typical energies and examples of FIGURE 16
substances containing each type of force.

Polarity of Bonds
The individual covalent bonds in molecules have an
electron pair holding the two nuclei together. If the two
atoms are identical, such as in H–H, or H2, molecules,
then the electrons are symmetrically distributed
between the two nuclei. Because of the symmetry,
there is no net charge separation, so the bond is
nonpolar. However, in most molecules, the bond is not
between two identical atoms. In this case, the electrons
are not symmetrically distributed, but rather are
more attracted toward the atom that has the greatest
electronegativity value.
Water is polar because oxygen and hydrogen have different
Since the electrons come from atoms that were electronegativity values. The oxygen side has a partial
originally neutral in charge, one atom is now getting negative charge, and the hydrogen side has a partial
positive charge.
“more than its fair share” of the electronic charge and
so will be somewhat negatively charged, leaving the
other atom with an equal but positive charge. Such

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 FIGURE 17
A summary of intermolecular forces.
a situation creates a polar bond. Partial charges are
indicated by adding a δ sign (δ+ or δ–). Molecules with
such bonds will have permanent van der Waals forces
when they come close to other similar or identical
molecules. An example of this is water.
Intermolecular Forces
Intermolecular forces are weaker forces of attraction
than intramolecular forces. Intermolecular forces are
responsible for causing a clustering effect in liquids
and solids. Intermolecular forces are readily broken
apart and/or formed when substances undergo physical
changes, such as when substances interchange from
gases to liquids or to solids.
Van der Waals force is the name given to

an intermolecular force first recognized by
the Dutch scientist Johannes van der Waals
(1837–1923). This force results from the
partial charges existing either temporarily or
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permanently on molecules as a result of a lack
of complete symmetry in the distribution of
positive and negative charges. Molecules are
said to be polar molecules if a permanent
distance can be measured between the center
of positive charge and the center of negative
charge. Such a molecule is also said to have
a dipole moment, meaning that a rotational
force will exist if the molecule is placed in an
electric field. Molecules can develop induced
dipoles as a result of the motion of the electron
orbitals on atoms in a molecule. Even though
these are temporary dipoles, they are still a
source of attractive intermolecular forces. Such
forces were delineated by the German physicist
Fritz London (1900–54) and are known as
London dispersion forces. These are the
only type of intermolecular forces between
nonpolar molecules.
 FIGURE 18 FIGURE 19

Two sample base-pairings from a DNA molecule.

Image Credit: John W. Kimball. Copyright ©2008 John W. Kimball.
All rights reserved.

 Hydrogen bonds are formed when a strongly

electronegative atom (e.g., O, N, or F) is bonded

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with hydrogen that is covalently bonded to
a strongly electronegative atom in another
molecule. This is an example of a strong dipole-
dipole interaction. In Figure 16, partial charges
are indicated by adding a δ sign (δ+ or δ–).
The most common example is water, H2O. In
liquid and solid water, the H atom on one water
molecule forms a weak bond to the strongly
electronegative oxygen atom on the next water
molecule. Because these hydrogen bonds must
break for water molecules to move around,
they are the reason that water must be strongly
heated to melt or boil. The rigidity conferred
by these bonds is also responsible for the rather
open structure found in solid water, commonly
known as ice. This open structure is responsible
for giving ice a lower density than liquid water
(at a temperature just above its melting point),
and so ice floats on water.
Intermolecular forces are summarized in Figure 17,
which also shows typical energies and examples of
substances containing each type of force.
The Importance of Hydrogen Bonding
in Living Systems
Hydrogen bonds are especially strong dipole-dipole
interactions between hydrogen atoms and strongly
The structure of part of a DNA double helix.
electronegative atoms, such as oxygen or nitrogen.
Hydrogen bonds play important roles in the structure
and function of many biological molecules like
proteins and deoxyribonucleic acid (DNA). These
molecules contain the necessary ingredients for
hydrogen bonding, namely: H atoms, O atoms, and
N atoms. Examples of such “pairings” via hydrogen
bonds in DNA are shown in Figure 18.
In the 1950s, James Watson and Francis Crick
established a model of DNA based on X-ray studies
of DNA by Rosalind Franklin and Maurice Wilkins,
which suggested that the hydrogen bonds between
specific parts of the molecules caused DNA to form a
double helix structure as is shown in Figure 19.
Subsequent studies confirmed this and established
mechanisms by which the genetic code contained in
the sequence of the monomer nucleic components of
the original long DNA strand could be passed on.

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 HENRY CAVENDISH AND THE DISCOVERY OF HYDROGEN
In the early sixteenth century, the renowned alchemist
Paracelsus (c.1493−1541) experimented with dissolving
metals in acids and unwittingly produced hydrogen—
the most abundant element in our universe and the
simplest, having just one proton and one electron.
However, Paracelsus did not know that the flammable
gas being released in his experiments was different
from other flammable gases. In 1671, the Anglo-Irish
chemist Robert Boyle (1627−91) likewise took note that
a flammable gas was produced when iron was dissolved
in acid. Boyle also observed that this gas was lighter
(i.e., less dense) than air.
It was nearly a century later, in 1766, when the British
chemist Henry Cavendish (1731−1810) identified
hydrogen as an element distinct from other gases and
described its properties in great detail. It had previously
been thought that water and oxygen were the only basic
elements. Cavendish questioned this premise, and the

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results of his experiments bore out his suspicions as

Sketch of the British chemist Henry Cavendish.

he saw that the reaction of a metal with acid released

a substance distinct from other gases. At the time,
this substance was referred to as “flammable air” or
phlogiston. The renowned French chemist Antoine
Lavoisier would later name this gas hydrogène. In 1781,
Cavendish confirmed that the burning of hydrogen
produced water. Cavendish made numerous other
contributions to science, and his work with gases laid
the foundation for further advancements in chemistry
A sketch of the apparatus that Cavendish used in his
experiments with hydrogen.
made by Lavoisier and others.

The Effect of Bond Types on the
Structures of Solid Compounds
Ionic Lattice
The electrostatic forces created by the positive and
negative charges in an ionic bond extend in all
directions, so multiple neighboring ions of opposite
charge are attracted. Therefore, compounds with ionic
bonds exist as lattice networks extending in three
dimensions. The most common example is sodium
chloride, which consists of a lattice of alternating Na+
and Cl– ions repeated over and over again until the
edge of a crystal of salt is reached.
Covalent Network or Molecular Solid
The force creating a covalent bond is focused on
just the two atoms involved. However, depending on
their electronic structure, many atoms can repeat the

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 FIGURE 20 FIGURE 21

In a methane (CH4) molecule, carbon forms four covalent

Compounds with ionic bonds exist as lattice networks bonds with hydrogen atoms.

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extending in three dimensions. Sodium chloride consists of
a lattice of alternating Na+ and Cl– ions.
FIGURE 22
sharing process several times, bonding to multiple
atoms. For instance, while hydrogen only forms a
single covalent bond in the compound, carbon can
form four covalent bonds with other atoms, as in
methane (CH4) shown in Figure 21. Covalently bonded
molecules can exist as small discrete units, such as
methane (CH4) and water (H2O), or as a covalent
network, as with a diamond, which consists of carbon
atoms, each bonded covalently to four other carbon
atoms in a lattice of such bonds, forming one of the
strongest known substances (Figure 22).
Diamond is a covalent network of carbon atoms and is one
Metals with metallic bonds are highly ordered solids of the strongest known substances.
with atoms packed quite closely together. As a result,
metals are strong, but they can be bent, hammered into translational motion occurs, but the molecules stay in
thin sheets, or pulled into wires, as layers of the atoms close contact. In a gas, the molecules are free to move
can slide over one another relatively easily. throughout the container in which the gas is placed.
When substances change from solid to liquid or from
How Intermolecular Forces Determine liquid to gas, energy must be added to overcome any
States of Matter (Solid, Liquid, Gas) at intermolecular forces that are preventing the molecules
Room Temperature from moving around more freely.
In a solid, molecules are not moving over long distances,
The temperature of a substance is a direct measure of
a type of motion called translational motion, to
molecular motion. So, at any given temperature, the
distinguish it from vibrational motion and rotational
state of matter (solid, liquid, or gas) is determined by
motion, which do occur in solids. In a liquid, limited

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 FIGURE 23 FIGURE 24
subliming
boiling,
liquefying, vaporising,
melting evaporating

freezing,
solidifying
Cl- condensing,
liquefying

SOLID LIQUID GAS

molecules held in molecules packed close molecules widely
fixed pattern but together in a random separated, move at
vibrating fashion, free to move great speed

Three states of matter: solid, liquid, and gas.

Some compounds, such as liquid water, have both polar

the strength of the intermolecular forces that can inhibit dipole and covalent bonds.
molecular motion. As a result, we can predict the state
that a substance will have at room temperature if we
know the types of intermolecular forces it contains. FIGURE 25
Solids are formed if strong forces exist in all three-
dimensions among the molecules and/or atoms.
Thus, ionically bonded substances, such as sodium
chloride (NaCl), and those forming covalent networks,

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such as silica (SiO2) or diamond (C), will be solids.
Compounds with intermediate strength forces, like
hydrogen bonds, are liquids, such as water (H2O).
Very few naturally occurring compounds are liquids at
room temperature. Compounds such as methane (CH4)
and carbon dioxide (CO2) have weak intermolecular
forces that are called dispersion forces since there are
no permanent dipoles in these molecules. Since these
molecules are easy to separate from each other, they
are gases at room temperature.
It is important to be clear about the difference between
intramolecular (covalent) bonds and intermolecular
(hydrogen) bonds. In liquid water, each individual
molecule has two strong covalent H−O bonds
(intramolecular bonds) and then forms up to four
hydrogen bonds (intermolecular bonds) that “join” it to
adjacent water molecules.
MOLECULAR MODELS
Introduction
Chemists build real and mathematical models to help
them understand the properties of matter and how atoms
and compounds react to form new compounds. These
models also help chemists predict future reactions and
the properties of new materials. Chemists perform
laboratory experiments to test their predictions and
Representative Lewis structures.
continually seek to develop new models or refine
old ones to make predictions that better agree with
experiments. However, even models that are known to
incorrectly represent the real situation are kept if they
assist in making useful predictions.
Lewis Structures for Atoms and
Covalent and Ionic Compounds
Gilbert N. Lewis (1875–1946), a physical chemist at
the University of California, developed an idea that
helps account for where electrons are in atoms and
compounds by using a dot to represent each electron.
While the modern view of electrons in atoms does not
visualize them as dots, Lewis’s model helps account
for all the electrons and the common bonding observed
for each atom. The number of electrons involved in
bonding (which is usually less than the total number of
electrons in the atom) is known as the valence for that
atom. The electrons used in forming bonds are outer
electrons that are called valence electrons.

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 FIGURE 26
A Lewis structure depicting the formation of an ionic bond
between sodium and chlorine.
Lewis structures can be drawn for individual atoms,
ions, and atoms in compounds. Complete Lewis
structures sometimes show all the electrons, though
usually only valence electrons are shown. Lewis also
decided that covalent bonds should each have a pair
of electrons. The structures shown in Figure 25 are
representative Lewis structures.
Notice that the structures for F2, H2O, and NH3 have
electron pairs in bonds, but also electron pairs that are
not involved in bonding. These are known as non-
bonding electron pairs, or simply “lone pairs.” The
total number of electrons in each neutral structure
must add up to the total number of protons in the
nuclei of the atoms. In ions, this number can differ by
the amount of the value of the ion’s charge.
Figure 26 shows how a complete Lewis structure can
be used to show the change as a sodium atom gives up
its one outer valence electron to the nearly full valence
shell of the chlorine atom to form ions of opposite
charge that then attract one another in an ionic bond.
Valence Bond Concept
As chemists developed the idea that electrons in atoms
were in orbitals, they needed to fit the successful Lewis
electron pair bond that explained compound formation
and formulas into this picture. This was done by
supposing that an electron in an orbital on atom A
interacted with an electron in an orbital on atom B
with which it formed a bond.
Figure 27 illustrates the idea that the electron orbital
shapes, which represent the map of electron density,
overlap between the atoms to provide the attractive
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FIGURE 27
A depiction of a single covalent bond.
Image courtesy of Dr. Gary Trammell, University of Illinois at
Springfield.
FIGURE 28
A depiction of double and triple covalent bonds.
force in the bond. Such a bond is called a “single”
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covalent bond.
In some cases, atoms can overlap more than one orbital
at the same time to form “double” or even “triple”
bonds as shown in Figure 28. Carbon and oxygen share
two pairs of electrons in forming two double bonds in
carbon dioxide, while nitrogen atoms share three pairs
of electrons in forming a triple bond in nitrogen gas.
Hybridization of Atomic Orbitals as
an Explanation for Molecular Shapes
Sometimes the interaction of the two atomic orbitals
doesn’t seem to predict the correct shapes of the
molecules. In response to this concern, chemists
developed the idea that two (or more) electron orbitals in
an atom could combine to form new orbitals that had a
different shape. This process is known as hybridization
and can be used to rationalize the symmetric shapes of
many molecules. Figure 29 shows how one s and three p
type orbitals can hybridize to form four sp3 orbitals.
The Formation of Molecular Orbitals
When two or more atoms combine to form a chemical
molecule, the bonding electrons take up new physical
arrangements between the atoms, pulling the
atoms together and forming the bond. Theoretical
(mathematical) models can trace out the “electron
waves” that constitute these electron positions and
 FIGURE 29

Hybridize

s orbital p orbital

Two sp hybrid sp hybrid orbitals

orbitals shown together
(large lobes only)
A sample diagram of the hybridization of atomic orbitals.

shapes, which are called “molecular orbitals,” or MOs
for short. The simplest model suggests that the original
atomic orbitals combine or overlap to form the new
MOs. Two kinds of overlap are predicted: those in
which the new MO is concentrated along an imaginary
line connecting the atoms, which is called a sigma
MO or sigma bond, and those where the electron wave
shape is concentrated between the atoms, but away
The diagrams in Figure 30 show how these orbitals
and bonds are envisioned, with the atomic orbitals on
the left and the MOs that are formed on the right.
Note that the types of MO that form depend on the
atomic orbital (AO) in which the electrons exist prior to
bonding. In the examples shown, 1s AOs can overlap
to form a sigma MO, whereas p AOs can overlap to

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from the center line. This second type of overlap is form a pi MO since they have the correct orientation.
called a pi MO or pi bond. The 2px AOs (aligned in the x-coordinate direction) can

FIGURE 30

Two types of molecular orbitals: a sigma bond and a pi bond.

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FIGURE 31
An illustration showing that sigma and pi bonds can form
simultaneously between atoms that have sufficient electrons
in the appropriate atomic orbitals.
form a pi bond as shown.
Sigma and pi bonds often form simultaneously
between atoms that have sufficient amounts of
electrons in the appropriate atomic orbitals. Thus F2,
with 14 valence electrons, needs to share only one pair
of electrons to satisfy a valence octet on each atom
and therefore forms one sigma bond. O2, with only 12
valence electrons, needs to share two pairs to complete
its atomic octets and thus forms one sigma and one pi
bond. N2, with only 10 valence electrons, shares three
pairs of electrons in one sigma and two pi bonds as is
illustrated in Figure 31.
FIGURE 32
A depiction of the sharing of electrons in the CO2 molecule.
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With CO2, there are a total of 4 + (2 x 6) = 16 valence
electrons, so to satisfy the octets on C and on each of the
two O atoms, there will be one sigma and one pi bond
(two pairs of shared electrons) between the carbon and
each oxygen atom. The way the electrons are shared
(without the orbital shapes) is shown in Figure 32. In the
final step, each line represents a pair of electrons.
The full theory concerning molecular orbitals is much
more complex and detailed than is presented here and
includes the idea that orbitals can be non-bonding or
anti-bonding as well as “bonding.”
Oxidation States
Oxidation states are numbers that can be assigned to
an atom to represent how the atom has lost or gained
electrons to form an ion or bond(s) to other atoms.
Oxidation states are computed by starting with the
number of valence electrons the atom had before
bonding or ionizing and then determining whether
the atom has lost or gained one or more electrons as it
bonded or ionized.
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For example, in Li+, the lithium atom had three electrons
and has lost one, so its oxidation state is +1. In H2O,
the hydrogen atom has effectively given up its electron
to form the bond, so it has an oxidation state of +1.
The oxygen has gained two electrons (one from each
hydrogen atom) in forming the bonds and so has an
oxidation state of –2. Note that the total oxidation state
for all atoms in a neutral molecule must sum up to zero.
For a charged species such as NH4+, the total sum of the
oxidation numbers will be equal to the charge, namely
+1. So, in NH4+, if each H is +1, N must be –3.
 FIGURE 33
Molecules shown in two-dimensions via Lewis structures
(left) and three-dimensions via VSEPR models (right).
The VSEPR Model
Lewis structures only tell part of the story about
chemical molecules because they are two dimensional,
whereas all real molecules are three dimensional.
Therefore, additional models are needed to understand
and predict the geometric shapes of molecules. One of
the most successful such models is the Valence Shell
Electron Pair Repulsion model, abbreviated VSEPR.
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FIGURE 34
These Lewis structures are equivalent except for the
placement of the electrons (i.e., the location of the double
bond).
Diagram courtesy of Dr. Michael Blaber.
FIGURE 35
This indicates that the ozone molecule is described by an
average of the two Lewis structures (i.e., the resonance
forms).
Diagram courtesy of Dr. Michael Blaber.
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FIGURE 36
Bonding in an O3 molecule, with partial charges shown.
This model takes the electron pair bond one step
further by proposing that electrons form pairs, but then
the pairs, being all negatively charged, will mutually
repel one another in three dimensions.
The Resonance Concept Model
Resonance applies in some instances to bonding in
molecules with more than two atoms. It was introduced
to explain the experimental finding that bond properties
(length and strength of bonds) were equal, even when
insufficient valence electrons were available to form
bonds and satisfy each atom’s octet requirement. This is
most readily explained with an example such as ozone,
O3.6 This molecule has eighteen valence electrons.
However, experiments show only one type of “bond”
exists between the oxygens. So, is the bonding double to
the right or the left? (See Figure 34.) This is resolved in
the resonance model by assuming that both exist, as is
shown in Figure 35.
 FIGURE 37 FIGURE 38

Bonding in the molecule SO3.

The original idea was that somehow the molecule

oscillated between the two, hence the terminology of
“resonance.” However, now we know that the bonding A VSEPR model (right) for a methane molecule.
is truly equivalent and can best be thought of as 1.5
bonds on each side.19 This concept is represented in
Figure 36, which has partial bonds and charges added. FIGURE 39
The molecule SO3 can be treated similarly since
all three bonds in this molecule are experimentally
identical. The result can be represented as is shown in
Figure 37. The dashed bonds represent 1/3 of a bond, so
each resulting bond total for the link between the two
atoms is 11/3 bonds.
With detailed molecular orbital treatments that
allow for sigma and pi bond formation and include
“delocalized” orbitals that can bond more than two
atoms together with a pair of electrons, a very modern
theory—molecular orbital theory, or MO theory—
has come to replace the resonance model. Depiction of a linear molecular structure.

The Geometry of Molecules and Ions
VSEPR makes predictions about the geometry of
simple molecules by focusing on the central atom; for
example, if there are four electron pairs forming bonds
around a central atom, these will point toward the
corners of a tetrahedron, as is shown Figure 38, which
shows a model for a methane molecule.
Dipole Moments of Molecules
Earlier, we described dipoles and polar bonds. One
of the clues to the geometry of a molecule that has
polar bonds is whether the entire molecule has a dipole
moment. If it does not, then symmetry must have
allowed for the sum of dipoles pointing one way to
cancel the sum of dipoles pointing the other way. (If you
have learned about vectors in math, this means that the
addition of vectors equals zero.) If the molecule does
have a significant dipole moment, then there must be a
geometry in which the bond dipoles do not cancel.
For example, in CO2 (carbon dioxide) the C=O bonds
are polar (i.e., they have dipoles, or charge separation),
but the molecule has zero dipole moment. So, we
conclude that one C=O bond must exactly oppose the
other. Thus, the structure of the molecule is linear as is
shown in the model pictured in Figure 39.
The Relationship between Molecular
Properties and Molecular Structure
The polarity and shapes of molecules affect the way
in which intermolecular forces are distributed. Highly
polar molecules will exhibit strong van der Waals
forces, making the molecules more difficult to separate.
Such molecules therefore have higher melting points
and boiling points than molecules with lower polarity.
Molecules that are nonpolar have the lowest melting and
boiling points.

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 FIGURE 40 FIGURE 41

β = beta particle, ν = neutrino

Types of decay. (Note: A neutrino is a subatomic particle
that is very similar to an electron, but it has no electrical
charge and a very small mass.7) The alpha decay of plutonium.

NUCLEAR CHEMISTRY
FIGURE 42
Nuclear Equations, Half-lives, and
Radioactivity
Nomenclature for Isotopes (Nuclides)
Recall from our discussion earlier that the nuclear

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structure of an atom is defined by the symbol AZ X ,
where X is the chemical symbol, Z is the atomic number
or number of protons, and A is the mass number, which
is equal to the number of neutrons (N) plus the number
of protons. So, A = Z + N.
While many stable nuclei exist, varying the ratio of
neutrons to protons (N/Z) can lead to unstable nuclei,
making the atom radioactive. Radioactive atoms can
regain stability via a number of pathways. Alpha
decay involves the loss of a helium nucleus. With beta
decay, a neutron transforms into a proton with the
emission of a beta minus particle (electron), or a proton
transforms into a neutron in beta plus (positron) decay.
These three pathways are shown in the nuclear decay
equations in Figure 40.
Decay Equations and Predicting the Products
of Decays
Unstable nuclei result in radioactive decay. Alpha
decay results in the loss of two neutrons and two
protons from the parent nucleus. Nuclei generally
break up by alpha decay if they are very large. The
very stable alpha particle can form within the nucleus
and tunnel its way out. Nuclei larger than bismuth (Z
= 83) frequently break down by alpha decay. Figure 41
shows an example of the alpha decay of plutonium.
Sample equations for beta-minus and beta-plus
(positron) decay.
Image Credit: Jefferson Lab - Office of Science Education –
http://education.jlab.org/.
Beta minus decay results in the loss of one neutron
and the gain of one proton from the parent nucleus.
The antineutrino shares energy with the emitted
electron. Positron (or beta plus) decay results in the
gain of one neutron and the loss of one proton from
the parent nucleus. The neutrino shares energy with
the positron. Figure 42 shows sample equations for
beta-minus and beta-plus (positron) decay. The high-
energy, high-speed electrons (beta-minus decay) and
positrons (beta-plus decay) emitted during beta decay
are referred to as beta particles.
Predictions of beta decay are based on the
understanding that a nucleus is unstable because of an
imbalance between the number of neutrons and the

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 FIGURE 43
An equation for uranium fission.
number of protons. Generally, if there are too many
neutrons, beta minus decay (as was shown above for 14C,
which has six protons and eight neutrons) with electron
emission occurs. In this way, the nucleus converts a
neutron to a proton, which results in a closer to 1:1 ratio
of protons to neutrons, such as in 14N, which has a 7:7
ratio of protons to neutrons. If too few neutrons are
present, positron (positively charged electron) emission
occurs. This was shown above for 10C, which has six
protons and only four neutrons. The product is 10B,
which has a more stable 5:5 ratio of neutrons to protons.
Alpha Bombardment Reactions
In 1919, the physicist Ernest Rutherford announced
that he had shown that the bombardment of nitrogen
atoms with alpha particles created oxygen atoms. The
balanced equation for that reaction looks like this:
4 14 17 1 must have enough energy to overcome the repulsion
2He + 7N → 8O + 1H. Note that the sum of the
upper numbers (mass numbers) on one side of the
equation is equal to the sum of the upper numbers
(mass numbers) on the other side of the equation. The
same is true for the lower atomic numbers. This is
done to conserve neutrons and protons, which do not
convert in alpha decay. (Be aware, however, that they
do convert one to another in beta decay.)
Fission and Fusion Reactions
Uranium fission and the fusion reaction of deuterium
(2H) with tritium (3H) are both possible sources of
energy for human use. During uranium fission in a
nuclear reactor, the uranium is hit by a free neutron,
whose binding energy provides the energy for the
breakup of the uranium. Each reaction can yield
different products, but generally one product has a
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FIGURE 44
The equations for deuterium-deuterium fusion and
deuterium-tritium fusion.
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mass of about 130 amu, and the other has a mass of
about 100 amu. In addition, two or three neutrons
are released. All these products fly apart with a large
amount of kinetic energy. This is heat that can be
used to raise the temperature of water, make steam,
and drive the turbine of an electric power generator.
One possible balanced equation for uranium fission is
shown in Figure 43.
For the two nuclei of hydrogen isotopes to fuse, they
force of the two positive charges. This is a great deal
of energy, which is why it has not yet been possible for
this process to be carried out on a large enough scale to
produce electric power. The equations for deuterium-
deuterium fusion and deuterium-tritium fusion are
shown in Figure 44.
SECTION I SUMMARY
 Matter consists of atoms, neutral particles made
of protons (+1 charge), neutrons (0 charge), and
electrons (–1 charge).
 An element has one type of atom distinguished
by its number of protons. Isotopes of an element
can have a different number of neutrons.
 Mass is a characteristic that defines an atom and
 may be used for its identification. Masses are
compared to a carbon isotope defined as having
a mass of exactly twelve atomic mass units.
 Mass spectrometers can separate and measure
atoms and compounds.
 John Dalton formulated Dalton’s law of partial
pressures, which states that the total pressure
of a mixture of gases is equal to the sum of
the pressures of each individual gas: PTotal =
PA + PB. Dalton also proposed the first modern
atomic theory.
 A definitive symbol system has been agreed
upon for atoms. This system shows the number
of protons, the chemical symbol, and the mass
number.
Atomic masses of elements are weighted

averages of their isotopic masses.
Each electron in an atom has a discrete energy

and “cloud” wave shape called an orbital. The
early Bohr model of the atom had the electrons
in circular orbits around the atomic nucleus.
 All matter exhibits both particle and wave
properties.
 Elements placed in order of atomic number
show periodically varying properties and can
be arranged in a periodic table.
 Properties of elements placed correctly in the
periodic table exhibit trends across and down
the table that can be explained by the electronic
orbital structure of the atoms of an element.
 These properties include atomic radius,
ionization energy, electron affinity, and
electronegativity.
 Electronegativity is a measure of an atom’s
attraction of electrons from an adjacent atom to
which it is chemically bonded.
 The value of an atom’s relative electronegativity
is referred to as a Pauling electronegativity. The
higher the Pauling electronegativity, the greater
the attraction for neighboring electrons.
 Five types of forces of attraction have been
identified that hold atoms together in clusters
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called molecules or that attract one molecule
to another. These forces include ionic bonds,
covalent bonds, metallic bonds, van der Waals
forces, and hydrogen bonds.
 Intramolecular forces, which hold atoms tightly
together in molecules or networks, are those
found in chemical bonds. Ionic, covalent, or
metallic bonds are the three types of bonds that
explain all molecular and network structures.
 In most molecules, bonds are not between
two identical atoms, and thus electrons are
not evenly distributed but rather are more
attracted toward the atom that has the greatest
electronegativity value. This causes the atom
that attracts more electrons to have a partial
negative charge and leaves the other atom with
an equal but positive charge. Such a situation
creates a polar bond.
 Intermolecular forces are weaker than
intramolecular forces. Intermolecular forces
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account for the differences in physical properties
of substances, including whether a substance is
a solid, a liquid, or a gas at room temperature.
 Hydrogen bonds are especially strong dipole-
dipole interactions between hydrogen atoms
and strongly electronegative atoms (e.g.,
oxygen or nitrogen) and play important roles in
the structure and function of many biological
molecules like proteins and deoxyribonucleic
acid (DNA).
 Henry Cavendish identified hydrogen as
an element distinct from other gases and
described its properties.
 Lewis dot structures show electron distributions
in atoms and molecules. Lewis structures are
useful for illustrating the formation of covalent
or ionic bonds according to Lewis’s idea
that two electrons are used in covalent bond
formation.
When two or more atoms combine, the bonding

electrons take up new physical arrangements.
These electron positions and shapes are called
molecular orbitals (MO) and can take the form
of a sigma bond or a pi bond.
 Oxidation states are numbers that represent
how an atom has lost or gained electrons to
form an ion or bond to other atoms.
 The Valence Shell Electron Pair Repulsion
Model (VSEPR) is used to explain the three-
dimensional shapes of simple molecules. When
multiple covalent bonds are formed by one
atom, hybrid atomic orbitals are sometimes
needed in order to explain the shape that is
found by experiment.
 The resonance concept model was introduced
to explain the experimental finding that bond
properties (length and strength of bonds) were
equal even when insufficient valence electrons
were available to form bonds and satisfy each
atom’s octet requirement.
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 Knowing the shape of a molecule enables a
chemist to predict its polarity. In turn, polarity
is useful for predicting physical properties. For
example, polar molecules have higher boiling
points than nonpolar molecules.
 Changes in the nucleus of an atom follow
patterns similar to electronic changes.
Radioactivity involves changes in nuclear
structure to gain stability.
 Balanced equations can be written for alpha
and beta decay pathways for all radioactive
atoms and for nuclear fusion and fission
transformations.
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 Sect ion 2
States of Matter
SECTION II INTRODUCTION
Humans live their lives amidst a sea of chemical
substances that are in different physical states, either
gas, liquid, or solid. Most are not single substances but
rather are mixtures of substances. If a mixture looks as
if it is a single substance, it is called a solution. There
are several different kinds of solutions, although most
people think of solutions as liquids dissolved in liquids,
or solids dissolved in liquids. Examples of these types
of solutions include lemon juice in water and sugar in
water, which make a solution called lemonade. Chemists
also recognize gas in gas solutions and solid in solid
solutions. For example, you breathe the gases that are
found in the gas solution called air; you drink solutions
in which gas, liquid, or solid is dissolved in liquid water
when you enjoy beverages such as soda-pop, lemonade,
tea, or coffee; and you may ride a bicycle made of high-
strength solid solutions called steels. Only gas in gas
solutions and solid in liquid solutions will be reviewed
in this section of the resource guide.
This section of the guide will explore the properties
of each state of matter and how they vary with
composition, temperature, and pressure. We will begin
our discussion with pure gases and then proceed to pure
liquids. You will learn that chemists discovered that
all substances (except at absolute zero temperature)
can be considered as an ensemble of rapidly moving
particles. The dynamic motion and energy of these
particles form the basis of the kinetic-molecular theory
of matter. This particulate model can be used with
appropriate mathematics to explain the laws that govern
the behavior of gases, which were discovered much
earlier by experiment.
You will also learn about the major differences between
gases, liquids, and solids and about “phase diagrams,”
which show how all three states for a pure substance
can exist under different conditions and how they
can interchange in a process of molecular dynamic
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equilibrium. Then we will examine the properties of
solutions in water and in organic solvents. You will
learn that these properties can be predicted if the
molecular properties and the relative concentrations of
the components of the solutions are known.
GASES
Laws of Ideal Gases
In the seventeenth and eighteenth centuries, scientists
were fascinated by the behavior of gases, which they
had learned to isolate from one another or from air.
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These scientists observed that gases exhibited a high
degree of regularity of behavior. If a certain mass
of gas was trapped in a flexible container, such as
a balloon, and then extra pressure (P) was applied,
the volume (V) of the balloon always decreased
in a direct proportion to the applied pressure. This
behavior pattern became known as Boyle’s law, which
can be stated in a simple algebraic equation: P x V =
a constant, or PV = C. Pressure is usually measured
in atmosphere units and volume in liters, so C is
measured in units of liter-atmospheres (L-atm).
Similarly, Charles’s law states that if you heat the
trapped gas, the volume increases in direct proportion
to the temperature change, so that V/T = a constant,
or V/T = D. With volume in liters and temperature in
degree units, the constant is measured in units of liters
per degree.
In experimenting with gases, scientists made an
interesting discovery. They found that when a gas was
trapped in a cylinder with a movable piston and the
weight of the piston applied a constant pressure to the
gas, as the temperature was lowered from about 70 ℃ to
–100 ℃, the volume of the trapped gas decreased from
60 mL to 30 mL. Other measurements would show that
a straight line could be drawn through all the observed
volumes. However, this straight line extrapolates to
 Celsius), you simply add 273. So, on this scale, 70 ℃
FIGURE 45 is 70 + 273 = 343 K. Notice that since the Kelvin unit
is defined as “degrees Kelvin” no degree (°) sign is
placed in front of the K. Since the Kelvin temperature
scale is linear and starts from 0, it is this unit that must
be used in all equations relating to Charles’s law.
Combining Boyle’s law and Charles’s law algebraically
is quite simple. If P x V = C, and V/T = D, then PV/T
= CD, a new constant. In using this relationship,
we usually consider a set of pressure, volume, and
temperature conditions (1) changing to a new set of
P1V1 P2V2
conditions (2), so we can then write = .
T1 T2
This relationship can be applied both qualitatively and
quantitatively to predict new conditions.
For example, consider the following problems:

A graphical depiction of determining absolute zero

1. A sample of gas is in a cylinder with a movable
temperature. piston (See Figure 45). If the pressure is
increased while the temperature is unchanged,

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zero volume at a very low temperature. Scientists were will the volume increase, decrease, or remain
surprised to find that this plot worked for every gas the same?
they tried, and that the “zero volume” temperature was
always the same, namely –273 ℃. See Figure 45 for a Answer: The volume will decrease to balance
graphical depiction of this phenomenon. the pressure increase.

Since it seemed that no temperature can ever go lower
than –273 ℃ (and this has been found to be the rule),
this temperature was called “absolute zero.” Since
that time, it has been agreed that this temperature
is a fundamental starting point for temperature
measurements, so a scale called the Kelvin scale (unit
K) is used that starts at –273 ℃, which is defined as
0 K. To convert from the more familiar ℃ (degrees
2. A sample of gas in a rigid container of volume
1.0 liter has a pressure of 2.0 atmospheres
at a temperature of 200 K. What will be the
pressure at 400 K?
Answer: The volume and amount of gas is
constant, so P/T must stay constant. And, if T
doubles from T1 to T2, then P must also double,
so the new pressure, P2, is 4.0 atmospheres.

JACQUES CHARLES AND CHARLES’S LAW

While many early chemists were motivated by an interest in alchemy, wishing to transmute lead into gold, or
by an interest in developing medical treatments, the French scientist Jacques Charles (1746−1823) was largely
motivated by his interest in hot air balloons. Charles studied the conclusions of the Anglo-Irish chemist Robert
Boyle (1627−91) that had been published about a century earlier in the mid-seventeenth century. Boyle had been
the first to suggest the relationship between the pressure and volume of a gas, namely that the pressure of a fixed
amount of an ideal gas at a constant temperature is inversely proportional to the volume of the gas. As he studied
the properties of gases, Charles came up with the idea that hydrogen could be used to fuel balloon flight.
Charles developed a design for such a craft and worked with engineers and brothers Anne-Jean Robert

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 (1758−1820) and Nicolas-Louis Robert (1760−1820)
to make his design a reality. To the great wonder of
a crowd of spectators (which incidentally included
Benjamin Franklin) Charles and the Roberts launched
the first hydrogen-powered balloon on August 27,
1783. The flight was a success, lasting about forty-
five minutes, though it came to a rather violent end as
startled peasants at the landing site attacked the strange
balloon with their pitchforks.
A couple months later, on December 1, 1783, Charles
and the Roberts again worked together to launch a
hydrogen-fueled balloon, but this time the balloon had
passengers, namely Charles and Nicolas-Louis Robert.
The flight was again a success, this time lasting just
over two hours. It was only the second manned balloon
flight ever, and the first had occurred only about a week
and a half prior. This time, thankfully, the balloon
was not destroyed by frightened peasants, and Charles
decided to try to ascend once again. He suffered ear
pain due to the rapid ascent and thus decided to land
a short while later. This was Charles’s last balloon

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flight though the Roberts brothers continued to be avid
Portrait of Jacques Charles by Adélaïde Labille-Guiard, balloonists. The hydrogen balloon came to be referred
c. 1798. to as a Charlière in Charles’s honor.
Though he never flew in a hot air balloon again,
Charles did remain fascinated with the potential power in heating hydrogen and other gases, and it was his
work with gases, more so than his fascination with balloons, that became his greatest legacy. In c. 1787, Charles
conducted an experiment in which he filled five balloons with the same volume of five different gases. Charles
observed that when he increased the temperature, the volume of each of the five balloons increased the same
amount. This led Charles to conclude that under
conditions of constant pressure, a heated gas will
expand in volume. Charles never published his findings,
but when Joseph-Louis Gay-Lussac (1778−1850)
published a paper on the relationship between the
volume and temperature of a gas in 1802, he credited
Charles. To this day, we utilize Charles’s law, which
states that at constant pressure, the volume of a gas
is directly proportional to its absolute temperature
(i.e., the measurement of temperature beginning at
absolute zero on the Kelvin scale), meaning that as the
temperature increases, the volume increases, and as the
temperature decreases, the volume decreases. Charles’s
A drawing of villagers attempting to destroy the balloon built
V1 V2
law is expressed by the following formula: T = T . by Jacques Charles and the Roberts brothers.
1 2

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Partial Pressures and the Correction FIGURE 46
of Gas Volumes Collected over Water
The effect of changing pressure, volume, and
temperature for mixtures of ideally behaving gases
is more difficult to predict than when making such
changes to a single gas. However, as discussed in
Section I, Daltons’ law of partial pressures enables us
to consider each gas separately.
In gases, the gas particles move rapidly and far apart.
The pressure these particles exert is due to their
collisions with the walls of the container. Assuming
the particles behave ideally and do not stick together
or react with one another, adding other gas particles
simply increases the collision rate in proportion to
the number of gas molecules added. So, each gas
exerts its “own” pressure on the walls, and the total In a closed system, such as a jar of gas over water, the
water contributes some pressure as a result of its vapor
pressure is proportional to the number of particles of
pressure.
each gas (usually expressed as the number of moles
of gas present in the container). We can then express is only 760.0 – 17.5 or 742.5 mm Hg. This is useful
the amount of each gas as its “mole fraction”—the because if the volume, V, is known, then the number
moles of gas A, for example, divided by the sum of the

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moles of all the gases present. This could be written in
equation form as follows:
nA
mole fraction (A) = . Kinetic-Molecular Theory (KMT)
n A + n B + nC + ...
As a consequence of the ideal gas law, PV = nRT,
pressure, P, is directly proportional to numbers of
moles, n. So, we can also write mole fraction
pA
(A) = . This expression is Daltons’
p A + p B + pC + ...
law.
In a closed system, such as a jar of gas over water, the
water contributes some pressure as a result of its vapor
pressure. There is equilibrium between liquid water
and its vapor above the water, and the value of the
water vapor pressure only depends on the temperature
of the liquid. Therefore, the water vapor pressure can
be looked up in a standard table.
For example, if a gas such as nitrogen is being
collected in the apparatus shown in Figure 46, and the
gas pressure is measured to be 760.0 mm Hg pressure,
and the temperature is 20 ℃, we can simply refer to a
table that tells us the water vapor pressure at 20 ℃ is
17.5 mm Hg. Thus, the actual pressure of the nitrogen
of moles of nitrogen can be calculated using PV = nRT
(remembering to use T in Kelvin, not Celsius, and the
appropriate units for R).
In our previous discussion of the ideal gas laws, we
assumed that gas molecules behave in a very ideal way.
A scientific model called the kinetic-molecular theory
(KMT) of gases uses this approach. Specifically, KMT
makes four assumptions about ideal gases and their
molecules:
1. A pure gas consists of identical molecules that
are very small, so the actual volume of the
molecules is negligible.
2. The molecules are moving very rapidly in all
directions, but not all at the same speed.
3. No forces of attraction or repulsion exist
between one molecule and another.
4. Gas pressure is a result of collisions of the
molecules with the walls of the container.
While the molecules change direction as they
bounce off the walls, they lose no energy
during these collisions.

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The Relation of Particle Speed to
Mass, Collision Frequency, Volume,
and Pressure
Using these assumptions, it is possible to derive
mathematical expressions for the pressure of a gas.
We start by defining the average speed of a molecule,
u. This can be used to determine the frequency
of collisions with the walls, given the size of a
container—a cubic box with sides of length . Next, we
consider the momentum transferred to the walls of the
container as a result of the gas molecule collisions.
The force on a container wall is a direct result of the
momentum change of a molecule as it bounces off the
wall. For a molecule that travels a distance  between
collisions, the physics of mechanics tells us this is
mu2
Force = , where m is the mass of the molecule, and
ℓ
u is its average speed in meters/second directed toward
the wall.
In a three-dimensional box, if the area of one side is
will see later how Charles’s law and the temperature of
a gas can also be rationalized using this model.
Avogadro’s Law
It is important to note that in our discussion of gases
thus far, we have been referring to a fixed amount
of trapped gas. What happens if the amount of gas
changes? The scientists studying gases found that
the pressure and volume of a gas did change in a
predictable way as the amount of the gas was varied.
However, mass wasn’t the only factor; what mattered
was the ratio of the total mass of gas to the mass of the
individual molecules of the gas.
For example, four grams of helium gas have the same
volume as two grams of hydrogen gas at the same
temperature and pressure. Sixteen grams of methane
(chemical formula CH4) are needed to reach the same
volume, temperature, and pressure conditions.
This behavior provides the basis for establishing the
molecular theory of matter. The molecular theory of
matter states that many pure substances, especially

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A, then the volume is A. If N molecules are in the gases, exist as small discrete units called molecules,
box, 1/3 of them will be traveling in each of the three and it is the number of these molecules that are
dimensions. So, the pressure, P, or force/unit area (P = present that determines the properties, not the mass.
Force/A) on the walls of the container because of gas An extension of this concept was made by Amedeo
collisions totals: Avogadro, an Italian scientist who suggested that no
matter the nature of the gas, at a given temperature,
1 Nmu2 1 pressure, and volume, there would be the same number
P= or PV = Nmu2.
3 V 3 of molecules. This concept is known as Avogadro’s
In qualitative terms, this is the relationship that hypothesis. Since it turned out to be correct (except for
explains Boyle’s law. It also states that the product minor perturbations under unusual conditions), it is
of P x V will depend directly on the mass of the gas also known as Avogadro’s law.
molecules and the square of their average speed. We

AMEDEO AVOGADRO AND AVOGADRO’S LAW

The Italian scientist Amedeo Avogadro (1776−1856) is most notable for his development of what is now known
as Avogadro’s law, which states that at constant temperature and pressure, the volume of a gas is directly
proportional to the number of moles of the gas. A mole is the standard international base unit used to measure
the amount of a substance and is based on the number of carbon atoms in 12.000 grams of carbon-12. Students
of chemistry also likely associate Avogadro with Avogadro’s number, which gives us the number of atoms in
12 grams of carbon-12, which is 6.022 x 1023 atoms (or molecules). If we have one mole of a substance, it means
that we have 6.022 x 1023 atoms (or molecules) of it. However, while this number is named in Avogadro’s honor
in recognition of his contributions, Avogadro did not actually determine this number. It was the French physicist
Jean Baptiste Perrin (1870−1942), who first used the term “Avogadro’s number” when he gave an estimate of
Avogadro’s number in 1909.

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Avogadro was very interested in John Dalton’s work
on atomic theory and in Joseph-Louis Gay-Lussac’s
discovery in 1805 that when gases react with one
another, the volumes of the reactants and the products are
always in whole number ratios to each other. Gay-Lussac
showed, for example, that two volumes of hydrogen and
one volume of oxygen were needed to produce water.
Experiments by Gay-Lussac and others made it clear that
when hydrogen and oxygen were burned at a constant
pressure and temperature, the resulting water vapor was
twice the volume of the original amount of oxygen.
It was Avogadro who proposed an explanation for this
in 1811, as he came to understand that many gases are
actually comprised of two identical molecules bonded
together, such as H2, O2, N2, and so on. Avogadro
proposed that the volume (V) of a gas at constant
temperature and pressure is directly proportional to the
number of moles (n) of the gas. So, for example, if the
number of moles of a gas is doubled, then the volume of
the gas will double, so long as temperature and pressure
remain the same. Avogadro’s law can be written as

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V1 V2
follows: n1 = n2, given constant temperature and pressure.
Portrait of Amedeo Avogadro, who is best known for
Avogadro’s hypothesis, sadly, was not readily accepted developing Avogadro’s law.
by the scientific community of his day and would be
largely ignored for another fifty years or so.

Volume and Mass of One Mole of Ideal
Gas at Standard Temperature and
Pressure (STP)
Quantitatively, chemists define a specific number of
molecules (or atoms, particles, or ions) as a unit called
the mole. For historical reasons, the mole was defined
as the number of molecules in a volume of 22.4 liters
at 1 atmosphere of pressure, and a temperature of
273 K. A more recent agreed-upon definition of one
mole is the number of atoms in exactly 12 grams of
the carbon isotope 12C. Considerable effort has gone
into measuring this number with greater and greater
precision, but it may never be known exactly. Some
scientists have suggested that it should be redefined as
an exact number, but history and generations of college
chemistry majors who have learned the number are
probably against such a redefinition.
The number was found to be 6.022 x 10 molecules.
23
This number is known as Avogadro’s number in honor
of Avogadro, though he did not actually determine
it. So, there will be 6.022 x 1023 atoms of helium in a
22.4-liter container of helium gas if the pressure is 1
atmosphere and the temperature 273 K. This helium
will have a mass of 4 grams. This number is known as
the molar mass of helium, which is 4 g/mol. Similarly,
there will be 6.022 x 1023 molecules of methane (CH4)
in a 22.4-liter container at 1 atmosphere pressure at
273 K. The methane will have a mass of 16 grams. The
molar mass of methane is 16 g/mol.
You can calculate the molar mass of any substance
by multiplying the atomic masses of the atoms by the
number of atoms of that element in the molecule and
then adding them up. So, for example, to determine the
molar mass of methane, we have 1 C and 4 H’s = 12
(atomic mass C) + 4 x 1 (atomic mass H) = 16.
The concept of moles as the unit of substance has been
widely adopted in chemistry for all substances, not just
for gases. So, for example, we can have 1 mole of salt

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(sodium chloride, NaCl), which will have a mass of (1
x 23.0) + (1 x 35.5) or 58.5 grams. The molar mass of
NaCl is 58.5 g/mol.
The Dependence of Kinetic Energy of
Molecules on Temperature
The speed of a single, isolated, moving molecule
determines its energy. Physics provides us with
moving. If we apply this equation to helium atoms (such
as might be in your birthday helium balloon on a warm
day), put in a molar mass, M, of 4, and a temperature,
T, of 298 K (25℃ or 77℉), and get all the units correct,
we find a root mean square speed of 1,360 meters per
second. That’s almost a mile per second!
The calculation looks like this:

the equation: energy = 1/2 mv2 for a moving
particle of mass, m, and velocity, v. Physicists also
determined that energy of motion is directly related
to temperature, if temperature is determined on the
Kelvin scale. So, the energy of a molecule = 3/2 kT,
where T is the temperature of the gas (in K), and
k is a universal constant known as the Boltzmann
constant.
Since both expressions represent the same molecule’s
energy, we can put them together and do some algebra
to give us an equation for an average molecule’s speed,
u:
√
3 × 8.31 kg × m2 × s−2 × mol−1 × K−1 × 298K
u=
4 × 10−3 kg × mol−1
It is clear that the helium atoms inside the balloon are
zipping backward and forward, making many thousands
of trips across the balloon every second, bouncing off
the walls, and creating the pressure inside the balloon.
The Ideal Gas Equation
If we now substitute the expression for u into the
equation we worked out previously, namely
PV = 1/3 Mu2 (since Nm = M), we find:
PV = 1/3 M x 3RT/M = RT

√
3kT
u= m .
Since this is derived by taking a square root, it is
known as the “root mean square” speed. If we now
consider N molecules, instead of just one, where N
is Avogadro’s Number, we have 1 mole of gas, and
the mass becomes the mass of 1 mole of molecules,
the molar mass, M. The Boltzmann constant can be
recomputed for 1 mole of gas and given the symbol R,
which is known as the “universal molar gas constant.”
The equation for root mean square speed of molecules
√
3RT
in a mole of gas is u = M .
It is interesting to question how fast gas molecules are
This equation is known as the universal gas equation,
or the “ideal gas equation.” We should keep in mind
that here we have assumed 1 mole of gas. However,
we can modify the equation easily for any number of
moles of gas by including n moles, so PV = nRT.
Note that this has exactly the same form as the
combined Boyles and Charles law equations for a
fixed amount of gas, since R and n will be constant:
P1V1 P2V2
= . It was very satisfying to early physicists
T1 T2
and chemists that they could model the behavior of
gases by making the assumptions of kinetic-molecular
theory and using equations for the motion of a particle.

CARL WILHELM SCHEELE, JOSEPH PRIESTLEY, ANTOINE LAVOISIER,

AND THE DISCOVERY OF OXYGEN
Like many scientific discoveries, the discovery of oxygen was accomplished by multiple scientists working
mostly independent of one another. Carl Wilhelm Scheele (1742−1786), a German Swedish chemist, is one of
three scientists who is often credited with discovering oxygen. The timeline for Scheele’s discovery is a bit
murky since the results of his experiments were not published until 1777 even though he had been conducting
his work in the early 1770s. Sometime around 1772 (perhaps as early as 1770), Scheele became the first scientist
to produce O2, which he referred to as “fire-air,” by heating various oxides. Scheele observed that oxygen was
odorless and tasteless and that it supported respiration and combustion better than air.8

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38
 A sketch of the equipment used by Antoine Lavoisier in his
phlogiston experiment.
Engraving from the title page of Scheele’s Chemical Treatise
on Air and Fire (1777).
The English chemist Joseph Priestley, one of the most
accomplished scientists of the eighteenth century,
like Scheele became interested in learning about the
properties of gases as he examined “airs” that were
released when certain substances were heated. In 1774,
Priestley heated a sample of mercuric oxide, HgO, and

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observed that as the sample began to decompose, it
released a substance that made flames burn brighter and
hotter and that was pleasant to inhale. Like many of his
contemporaries, Priestley was an adherent of phlogiston
theory—the idea that as materials burned, they
released phlogiston, an undetectable substance. Thus,
Priestley referred to the gas that was released during his
experiments as “dephlogisticated air” since he believed it
was air with its phlogiston removed.9 Priestley published
his findings in 1775, and thus he, more often than Scheele,
Sketch of the equipment used by Joseph Priestley in his is credited with the discovery of oxygen. (Oxygen was
experiments with gases. just one of eight gases that Priestley is credited with
isolating.) While Priestley and Scheele both were able to
produce oxygen by heating oxides, neither of these scientists correctly ascertained how combustion occurred as both
adhered to the popular view that a substance called phlogiston was released when oxides were heated.
The French chemist Antoine Lavoisier claimed that he discovered oxygen independent of Priestley and Scheele’s
experiments. However, some historians question how much Lavoisier may have benefited from work done by
Scheele and Priestley. In fact, Scheele wrote a letter to Lavoisier in 1774 in which he discussed his experiments
with oxygen, writing “ . . . I hope that you will see how much air is formed during this reduction, and whether
a lighted candle can keep burning and animals live in this air.”10 Priestley, too, shared his findings concerning
oxygen with Lavoisier on a visit to Paris in 1774.
While it may not be possible to know exactly how much Lavoisier benefited from the work done by Scheele and
Priestley, it is clear, that of the three scientists, it was Lavoisier who truly came to understand how combustion
worked through quantitative experiments. Lavoisier debunked the theory of phlogiston and established the
principle of conservation of mass, which to this day remains a foundational tenet of modern chemistry.
Moreover, it was Lavoisier who named the gas released during the heating of oxides “oxygène.”

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FIGURE 47
Plotting the experimentally determined value of (PV/RT)
for exactly one mole of various real gases as a function of
pressure, P, shows a deviation from the value that would be
expected from an ideal gas.
The Behavior of Gases under Extreme
Conditions
Under extreme conditions of temperature and pressure,
most gases exhibit behavior that doesn’t agree with the
ideal gas equation. The three key assumptions made in
kinetic-molecular theory (KMT) are as follows:
1. Gas molecules have no volume;
2. There are no intermolecular forces between the
molecules;
3. Collisions are truly elastic—only kinetic
energy is transferred.
If gas pressures are low, the volume is large, and
molecules are moving very rapidly (i.e., the temperature
is high), then the KMT conditions are satisfied for most
common gases. However, in the opposite conditions of
high pressure, low volume, and low temperature, most
gases do not behave ideally as is shown in the plot in
Figure 47, which compares the ideal value of 1.0 for
PV/RT for 1 mole of the gas as the pressure is increased.
Generally, this behavior is measured by how well the
gas pressure agrees with the rearranged formula
P = nRT/V. The Dutch physicist Johannes van der
Waals (1837–1923) developed a useful equation to
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monitor the behavior of non-ideal gases, which is now
known by his name and corrects for the two main
effects as is shown below:
Van der Waals introduced two parameters, a and
b, that can be measured and used in his equation to
calculate the “true” pressure. The values for a and b
for many gases can be found in tables in textbooks
and on the internet; the smaller the values, the more
ideal the gas behavior is. The value for a is a correction
value for the attraction that gas molecules may have
for each other during collisions while b is a correction
value for the volume of the gas molecules. The table
below shows just a few such values.
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Substance a (L2 atm/mol2) b (L/mol)
He 0.0341 0.0237
O2 1.36 0.0318
CH4 2.25 0.0428
CO2 3.59 0.0427
NH3 4.23 0.0371
A refrigerator works by compressing a gas to make it
into a liquid. The liquid is then allowed to evaporate
through a small hole and, in doing so, cools itself and
its immediate surroundings. Conservation of energy is
maintained since compressing the gas causes heating
that balances the cooling. In a refrigerator, this heat is
dissipated into the surrounding room. Obviously, if the
gas does not easily liquefy, then it is a poor choice for
a refrigerator liquid. Therefore, gases with large van
der Waals constants make good choices for refrigerator
liquids. For many years, chlorofluorocarbons (CFCs)
were chosen as having excellent properties for
refrigeration; however, these caused environmental
damage by destroying Earth’s ozone layer and so are
no longer used. Ammonia (NH3) and carbon dioxide
(CO2) are good substitutes.
The Dependence of Relative Rates of
Diffusion and Effusion on Molecular
Mass and Temperature
One obvious consequence of accepting that a gas
consists of large numbers of small particles moving at
high speed is that we can predict that gases will rapidly
travel great distances if released from a container. The
atoms in the helium example discussed previously were
moving at a mile a second. We become very familiar
with this idea as we experience, almost instantaneously,
the smell from a perfume bottle opened across the room
or the odor from a skunk killed on the road.
Two concepts are at play in these examples. The one
that is demonstrated by the perfume molecules is
called diffusion. The other, which involves how fast a
gas will leave a container through a small leak such as
a pinhole, is a process called effusion.
The simplest calculation used for the helium assumes
that molecules can travel uninterrupted in a straight line.
This works in a vacuum, but it doesn’t work in practice
because outside of a vacuum the molecule makes many
collisions with other molecules that divert it from a
straight-line path. So, we can easily calculate a relative
diffusion or effusion rate, but probably would need an
elaborate computer model to compute the absolute rate
at which the average molecule in a gas will diffuse
across a room or effuse from a pinhole leak.
Applying algebra to the root mean square speed
equation, we can see that for two gases, (1) and (2), at
the same temperature:
√
3RT
√
3RT
u1 = and u2 =
M1 M2 .
Since the only variable on the right-hand side is M, if
we take a ratio, we can write:
√
u1 M2
u2 = M1
Stated in words, the relative speeds of gas molecules
(u) are inversely proportional to the square root of the
mass of the gas molecules (M).
As an example, consider this problem: If helium atoms
(M = 4) are traveling at 1 mile per second, how fast
are hydrogen molecules (M = 2) traveling at the same
temperature?
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41
√
4
Answer: We have uH2 = × uHe = √2 x 1 mile/sec =
2
1.4 miles per second.
Qualitatively, we can easily see that the heavier the gas
molecules are, the slower they will move (at a given
temperature), and so we can predict that diffusion and
effusion will be slower. Thus, in the above problem we
could immediately state that H2 molecules (M = 2) will
travel faster than He atoms (M = 4) if they are at the
same temperature.
For another example, consider the following problem:
A scientist at a lab bench opens a bottle of ammonia
(NH3) and a bottle of acetone (C3H6O) at the same
time. Both have a distinctive odor. Which substance
will someone on the other side of the room detect first
by its smell?
Answer: The molar mass of ammonia = 14 + 3 = 17,
while the molar mass of acetone = 36 + 6 + 16 = 58.
So, clearly the ammonia molecules have the smaller
mass and therefore will be sensed first. Since they are
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in the same room, the temperature will be the same for
both substances.
LIQUIDS
In the previous section focusing on gases, we considered
ideal gases, where the molecules (or atoms in the gas
of noble gases) of gas are independent and have no
intermolecular forces causing them to stick together.
In a solid substance, the individual particles can be
molecules or atoms or ions. These are held firmly by
attractive forces in a network or lattice structure that
allows almost no movement from one place to another
(translational motion). This is not to say that the particles
are still. In fact, there are rapid vibrations and rotations
occurring in every solid at all temperatures above
absolute zero. However, these vibrations and rotations
generally do not change the average position of a
particle in relation to its nearest neighbors. The structure
of a solid remains much the same, with only slight
expansion due to increased vibrations as the temperature
is raised, until it changes phase, either melting to a
liquid or subliming to a gas. One way to describe a gas
in comparison to a solid is that a solid has a high degree
of order at short distances (called short-range order)
whereas a gas has no ordered structure at all.
A liquid is somewhere in between a gas and a solid.
Individual particles or “clusters” of particles weakly
 FIGURE 48
Water can take form as a solid, liquid or gas.
“stuck” together by intermolecular forces may move
readily (and may vibrate and rotate) throughout the
liquid. Experiments show that over a long distance a
liquid has a form of ordering, but over short distances
the molecules appear randomly distributed. A liquid
may thus be said to exhibit long-range order. The
degree of ordering depends very much on the nature of
the liquid and the temperature. A liquid such as water,
which has strong intermolecular forces due to the
hydrogen bonds between the water molecules, has a
much higher degree of ordering than does a liquid such
as octane (a component of gasoline), which has very
weak forces between the octane molecules.
The differences between gases, liquids, and solids are
illustrated in Figure 48. The molecular views show that
the molecules in the gas are much further apart than
those in the liquid or solid. The molecules in the liquid
do not have the orderly arrangement seen in the solid.
Notice, also, that a usual distinction is that the density
(mass per volume) and the packing of particles in a
solid is the greatest, and in a gas is the least, with the
liquid state being in between.
SOLIDS
Solids have a distinctive structure in the sense that
they are highly ordered. While vibrations do occur, we
can take an instantaneous snapshot of a solid showing
its components (atoms, molecules, or ions) in specific,
essentially fixed, positions relative to one another.
The component particles are held firmly by the ionic,
covalent, or van der Waal’s forces described in Section
I of this Resource Guide. In Section I, we also identified
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42
FIGURE 49
a b c
d e f
g h
Allotropes of carbon: a) Diamond; b) Graphite; c)
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Lonsdaleite; d) C60 (Buckminsterfullerene); e) C540 (see
Fullerene); f) C70 (see Fullerene); g) Amorphous carbon; h)
Single-walled carbon nanotube.
Images created by Michael Ströck.
four types of solids: ionic lattice solids, covalent
network solids, molecular solids, and metallic solids.
Some chemical compounds and elements can exist in
several different solid forms. When an element shows
this property, the different forms are called allotropes
of the element. One excellent example is the element
carbon, which has been identified as existing in several
different forms, each with its own distinct properties.
Figure 49 shows eight forms (allotropes) in which pure
carbon has been found.
Properties can differ a lot among these allotropes. For
example, graphite conducts electricity, but diamond
is an insulator. Some of these forms (for example,
nanotubes) have been identified only recently and may
have incredible applications, such as in forming parts
of circuits that can control nano-robots.
Because of the many different bonding arrangements
carbon atoms can have that form stable structures,
carbon is found in many forms. Each structure does
differ slightly in its energy content. The most stable
form of carbon, defined in terms of energy at room
temperature, is the graphite structure. However, the
other forms of carbon do not convert at any appreciable
rate into graphite when at room temperature. Natural
diamond (that found on Earth) is formed from graphite
at high temperatures and pressures underground.
Scientists have now learned how to simulate such
conditions and thus can manufacture artificial diamonds
from graphite.
In addition to bonding ability, another factor that affects
how solids are arranged is the size of the particles in
the solid. This is especially true for ionic lattice solids
and for metallic solids. The forces that hold particles
together, and hence the energy, can be maximized when
the particles are packed as tightly as possible.
Among the most closely packed structures are pure
metals, which have atoms of one single element present.
Metals have a regular crystalline structure.11 You can
see crystals of zinc on the surface of a galvanized
object, such as a bucket or garden watering can. The
atoms of a metal are organized in successive layers and
can be organized in three simple forms. These forms
are determined by how many “nearest neighbors” (i.e.,
similar particles at the nearest identical distance) an
atom has.
In a pure metal, the nearest neighbors are always
identical atoms. The three simplest structures seen are
body-centered cubic, which has eight nearest neighbors
(iron is an example); face-centered cubic, which has
twelve nearest neighbors (silver is an example); and
close-packed hexagonal, which also has twelve nearest
neighbors (zinc is an example).12 Generally, the closer
the packing, the “softer” the metal will be, as its layers
can more easily slide over one another. The preferred
structure of the metal is determined by the size of the
atoms.
The very tight structure of metals causes them to have
the following properties:
 Metals have a lustrous appearance (shiny)
because of the reflection of light from the
regular arrangement of atoms.
 They are good conductors of heat because of
this structure. Sound waves can travel through
the lattice, and so metals are sonorous (they
ring when struck).
 They are good conductors of electricity because
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FIGURE 50
The three simplest crystalline structures of metal are
close-packed hexagonal, face-centered cubic,
and body-centered cubic.
the closeness of the structure helps atoms give
up some of their outer electrons to move freely
in the solid as a whole.
 They are very malleable—they can be beaten
into different shapes; and they are ductile—
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they can be pulled into a wire. The evenly
spaced layers of atoms can slip over each other
without losing their attractive forces.
The reason that impurities are added to metals—or
that two or more metals are mixed to form an alloy—is
because this disrupts the smooth layers, decreasing the
sliding of layers, and thereby increasing the strength
of the metal for structural purposes. Steel is much
stronger than pure iron for this reason.
PHASE DIAGRAMS OF ONE-
COMPONENT SYSTEMS
A pure substance can exist as a gas, a liquid, or a
solid, depending on the temperature. The relationships
between the three phases and the transitions between
them can be summarized in a phase diagram. It is
important to understand how a phase diagram is
constructed in order to understand what happens as one
phase changes into another. There are several important
concepts involved:
1. Most phase diagrams are constructed as if
there is a single substance present in a sealed
container. Not even air is present.
2. Molecules (or particles) are constantly moving
from one phase to another in what is known as
dynamic transfer.
 FIGURE 51
A typical phase diagram.
Image courtesy of ThinkQuest, Oracle Education Foundation.
3. Equilibrium conditions can be measured
such that the rate at which particles leave a
phase is the same as the rate at which they
enter the phase. This is a condition of dynamic
equilibrium.
4. At any temperature, any phase of a substance
will have a small amount of its gas present.
When the substance is not wholly a gas, the
gas present is known as a vapor. In a sealed
container, this gas will have a gas pressure
associated with it. This pressure will also be
“transmitted” to any liquid or solid present, so
all are at the same pressure.
A typical phase diagram for almost any substance is
shown in Figure 51.
 With regard to the phase diagram shown in
Figure 51, the pressure in the container is plotted
on the vertical axis, and the temperature of
the container of the substance is plotted on the
horizontal axis.
 Each phase is represented by a region of
pressure-temperature values.
The curved lines dividing the phase regions

represent the values of pressure and temperature
when dynamic equilibrium exists between two
phases.
A single point, called the triple point,

represents the only value of pressure and
temperature at which solid, liquid, and gas can
exist in equilibrium.
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FIGURE 52
The phase diagram for water.
Image courtesy of ThinkQuest, Oracle Education Foundation.
 Horizontal lines represent familiar transitions
from one phase to another as a result of
changes in temperature with pressure
remaining constant.
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 Vertical lines represent familiar transitions
from one phase to another as the temperature
remains fixed, but the pressure is allowed to
change as a result of changing the container
size (e.g., by moving a piston).
A critical point is shown at the temperature

and pressure at which the distinction between a
gas and a liquid is no longer apparent, and the
two phases exhibit the same properties.
Water and Its Phases and Phase
Transitions
The phase diagram for water, one of the world’s most
common substances, is shown in Figure 52.
Notice that normal melting point, Tm (0 ℃), and
boiling point, Tb (100 ℃), can be defined as the
temperature at which the two-phase equilibrium in
question has a pressure equal to atmospheric pressure,
which is defined as 1.0 atmosphere. The critical point
for water is at a very high temperature (374 ℃) and
pressure (218 atmospheres).
The unusual feature of the phase diagram for water is
that as pressure increases, the melting point is reduced
below 0 ℃. The backward sloping line for the solid-
liquid equilibrium rising from the triple point on the
 FIGURE 53

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A comparison of the phase diagrams of water (left) and carbon dioxide (right).
Image Credit: Chemistry, The Central Science, 11th edition, by Theodore Brown, Eugene LeMay, and Bruce Bursten, Prentice Hall, 2009. Copyright ©
Pearson Prentice Hall, Inc.

diagram in Figure 52 shows this. This effect is easily
demonstrated by squeezing two ice cubes firmly
together. The ice cubes start to melt where they touch,
but if you relax the pressure, then the liquid that was
formed re-freezes and welds the two cubes together.
This phenomenon also explains why sharp skates glide
easily over an ice rink surface.
The effect is a consequence of the strong hydrogen
bonds between water molecules that create a rigid open
structure for ice. Solid water (ice) has a slightly lower
density than liquid water just above the melting point.
As a result, ice floats on cold water, which is a very
important physical property that has allowed for life
to survive on Earth during glacial periods of Earth’s
history as well as in the present day. Just imagine
if lakes froze from the bottom up! Almost no other
substance shows this effect of an increase in pressure
lowering the melting point of its solid phase.
Carbon Dioxide
Carbon dioxide has a more typical phase diagram than
water. The diagrams in Figure 53 show a comparison
of the phase diagrams of water and carbon dioxide.
Note that there is a difference in the scales used and
that the scales are not linear. For CO2, the triple point
is at 5.11 atmospheres and –56.4 ℃. This means that
liquid CO2 cannot be observed unless the pressure is
at least 5.11 times the normal atmospheric pressure on
Earth and unless the temperature is well below normal
temperatures seen on Earth.
Chemists and industrialists have been seeking
substances that can be good solvents for applications
such as making new medications and removing grease
stains from clothes. Carbon dioxide in its liquid state
is a good solvent for many such applications. However,
carbon dioxide must be maintained at high pressures
to remain a liquid. Above the critical point, found at
point C on the diagram above, for CO2 at 73 atm and
31.1 ℃, CO2 becomes supercritical. This means that
its behavior has qualities of both a gas and a liquid. It
retains the density of a liquid but becomes as mobile as
a gas, both of which are ideal properties for a solvent.
In recent years, engineers have designed apparatus that

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can maintain the necessary pressure and temperature value, so the CO2 just boils away. In most designs, the
for the use of supercritical CO2 in many industries. The CO2 is captured and recycled, so it doesn’t add to the
main advantage is that the solvent is easily removed CO2 burden in the atmosphere.
by reducing the pressure to slightly below the critical

JOSEPH BLACK AND THE DISCOVERY OF CARBON DIOXIDE

The Scottish chemist Joseph Black (1728−99) is

credited with the discovery of carbon dioxide, which
he called “fixed air.” Black was interested in alkaline
substances such as lime water since they were thought
to be effective in treating kidney stones, so in 1754 he
conducted experiments in which he heated calcium
carbonate (limestone). Black observed that heating
produced a gas that was heavier than air and could be
poured like a liquid. He also noted that this “fixed air”
could extinguish flames and kill animals that were
surrounded by it. Furthermore, Black determined that
this gas was present in the air we exhale. He presented
his findings in 1755 in a paper titled “Experiments upon
Magnesia Alba, Quicklime, and Some Other Alcaline

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Substances.” Soon after Black’s discovery of carbon
dioxide, gases like hydrogen, nitrogen, and oxygen
were also isolated for the first time—the latter half of
the eighteenth century was truly a remarkable time of
advancement in our understanding of respiratory gases.

Engraved portrait of Joseph Black.

SOLUTIONS in which the solvent is a nonpolar substance such as

Solutions are mixtures of substances that are
homogenous, meaning that no change in properties
can be detected throughout a sample, no matter how
you measure it. In our discussion here, we will only
consider solutions consisting of just two substances
mixed together. Obviously, many solutions can contain
more than two substances. For example, lemonade has
water, lemon juice, and sugar.
For any solution, it is standard to define the substance
that is present in the largest amount as the solvent and
the other substance as the solute. We will consider two
types of solutions in this section: aqueous solutions,
in which the solvent is water, and organic solutions,
octane. Most of the solutions considered will feature a
solid solute dissolved in a solvent liquid.
Important parameters for all solutions include the
following:
 Solubility – the amount of solute that will
dissolve in a certain amount of solvent
 Concentration – the relative amounts of
solute and solvent present; you will learn that
there are several different ways to express the
concentration of a solution.
 Changes in physical properties that occur as a
consequence of forming a solution.

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FIGURE 54
A salt crystal surrounded by water is disrupted by
interaction with water molecules until the salt ions are
completely separated, and each ion is surrounded by water
of hydration.
Types of Solutions and Factors
Affecting Solubility
Chemists generally distinguish between two types of
solvents: those that have polar molecules that interact
strongly with electrically charged or polar solutes
and those that are nonpolar and interact better with
nonpolar solutes. A very general rule of solubility is
“like dissolves like.”
Water is the most important solvent of the polar type,
as the O-H bond is strongly polar. Ionic compounds,
such as salts, and non-ionic substances that are also
polar, such as sugar, dissolve well in water. A nonpolar
solvent such as octane dissolves other nonpolar
compounds such as vegetable oil.
When salts such as sodium chloride dissolve in water,
the actions between the water molecules and the ions
in the crystal lattice are so strong that that the lattice
is disrupted, and the positive and negative ions are
separated, with each ending up with a sheath of water
molecules around it. Chemists call this interaction with
water strong hydration. This process is illustrated in
Figure 54.
Most ionic salts are soluble. A few ionic salts are
insoluble since the forces of hydration are insufficient
compared to the lattice forces of such salts. Following
is a common set of solubility rules that has been
constructed for many substances:
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(a) All common compounds of Group I and
ammonium ions are soluble.
(b) All nitrates, acetates, and chlorates are soluble.
(c) All binary compounds of the halogens (other
than F) with metals are soluble, except those of
silver, mercury (I), and lead. Lead halides are
soluble in hot water.
(d) All sulfates are soluble, except those of
barium, strontium, calcium, lead, silver, and
mercury (I).
(e) Except for rule (a), carbonates, hydroxides,
oxides, silicates, and phosphates are insoluble.
(f) Most sulfides are insoluble except for calcium,
barium, strontium, and magnesium.
Note that these solubility rules will be important when
we begin to predict the results of possible precipitation
reactions in Section III of this resource guide.
Aqueous Solutions
In aqueous solutions, each solute, whether classified as
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soluble or insoluble, reaches a maximum amount that
can be dissolved depending upon the temperature. A
solution containing exactly the maximum amount of
a solute is called a saturated solution. If additional
compound is added to a saturated solution, it does not
dissolve. Since solubility for most substances increases
with increasing temperature, if a hot saturated solution
is cooled, less solute can stay in solution, so the excess
will form a solid. If the solute is a crystalline substance,
solid crystals will form. If this is done slowly, large,
attractively shaped crystals may be produced. This
practice is the basis for crystal growing procedures.
Aqueous solutions are often encountered where
more than one salt ion is added. If the ions present in
solution happen to form an insoluble substance when
combined, then a precipitate will form, assuming that
the saturation point is exceeded. This is the basis for
many tests for the presence of certain ions in water.
For example, if water is to be tested for the presence of
chloride ions (Cl–), adding some silver ions (Ag+) will
create the insoluble compound silver chloride (AgCl),
which will form as a precipitate on the bottom of the
container.
A similar concept is involved in the formation of
stalactites and stalagmites in caves. Water dripping
into caves contains dissolved calcium (Ca2+) ions.

As calcium carbonate precipitates slowly on the roof or floor
of a cave, stalactites and stalagmites form.
Carbon dioxide in the air in the cave dissolves in
the water, producing carbonate ions (CO32–). The
compound calcium carbonate (CaCO3) is insoluble and
precipitates slowly on the roof or the floor of the cave
to form stalactites and stalagmites. We will learn more
about the mixing of solutions that form precipitates in
Section III of this resource guide.
Compounds such as glucose (a relative of sugar )
dissolve in water because they, too, contain O−H
bonds. These substances are able to engage in hydrogen
bonding with the water molecules, and so polar
compounds such as sugars and alcohols are soluble
in water. The structure of glucose is shown in Figure
55. Notice the five O−H groups, which make glucose
similar to water (H−O−H) with five hydrogen bonding
sites. Hence, glucose is very soluble in water.
Organic (Nonpolar) Solvents
Nonpolar solvents are generally compounds that contain
only carbon and hydrogen. Carbon and hydrogen have
similar values for electronegativity, so their bonds
have very little polar nature. The intermolecular forces
in nonpolar solvents are rather weak. As a result,
interactions with nonpolar solute molecules are weak,
and the substances dissolve easily since they can
disperse throughout the solvent without forming strong
clusters that would create separate liquid layers. A
few other solvents fall into this category because their
molecules are so symmetric that the dipoles in the bonds
geometrically cancel, yielding a nonpolar molecule.
These nonpolar solvents are important for cleaning
purposes, as many oils and greases are essentially
nonpolar and dissolve only in nonpolar solvents. The
dry-cleaning industry has depended on nonpolar
solvents for many years to remove grease and oil stains
from clothes. A problem with the use of nonpolar
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FIGURE 55
The chemical structure of glucose.
solvents is ultimately their disposal, as they are quite
toxic to humans, and the only way to remove them
from the environment is by burning them to form
carbon dioxide and water.
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Chemists have worked hard over many years to invent
chemicals that will convert oils and greases to water-
soluble compounds so that water may be used as a
solvent for cleaning purposes. Soaps and detergents
are the result of these efforts. Soaps and detergents
are comprised of molecules that have one end that is
relatively polar attached to another end that is relatively
nonpolar. The nonpolar end interacts well with grease or
oil molecules, while the polar end allows the molecules,
dragging their greasy add-on with them, to dissolve
more readily in the polar water. Super critical fluids
have been developed for use as “super” solvents.
Methods of Expressing Concentration
Scientists need to be able to communicate about
solutions in a quantitative way so that properties can
be accurately compared. There are several methods of
expressing the relative proportions of solute and solvent.
Percent Composition
The simplest method to express the proportions of solute
and solvent is by mass. The composition of a solution
can be expressed as x grams of solute in y grams of
solvent. Most often this is a percentage: x grams of
solute in 100 grams of solution. For example, a bleach
solution may be labeled as containing 5 percent bleach.
This means that there are 5 grams of bleach molecule
(NaOCl) in every 100 grams of bleach solution.
For the sake of clarity, in some applications this may
be written as “% w/w,” where w stands for “weight,”
a substitute for mass. For example, a toothpaste tube
may be labeled “0.5% sodium fluoride %w/w.”
Molarity
In scientific applications, chemists are not interested
in the grams present but rather in the moles present.
Remember, the number of moles represents the
number of molecules, not their mass. Since the solute
molecules are the most important, it is the solute moles
that are calculated (by dividing the mass of solute, in
grams, by the molar mass of the solute, in grams per
mole). The easily measured unit for a liquid solution is
the volume of that solution in liters, and so molarity
is expressed as moles of solute in 1 liter (exactly) of
solution. For example, a solution containing 5.85 grams
of sodium chloride (molar mass = 58.5 g/mol) in 1 liter
(exactly) of a salt solution has a concentration of 0.100
M. The M stands for the unit of molarity (moles/liter).
Molality
Some of the physical properties of solutions, such
as boiling point or freezing point, are dependent on
the relative numbers of moles of solute and solvent.
These properties are called colligative properties. A
unit known as mole fraction expresses this exactly.
However, chemists decided they needed a simpler
way to communicate how properties change with
concentration. For a specific solvent, the mass present
is a direct measure of the number of moles, and so the
molality unit was developed by using a fixed mass of
solvent. Concentration in molality units is the number
of moles of solute dissolved in 1 kilogram (exactly)
of solvent. Molality tracks physical properties in a
linear manner. As an example, consider that if a 0.100
molal solution of sugar in water freezes at −0.186 ℃, a
solution that is 0.200 molal will freeze at 2 x (−0.186) =
−0.376 ℃.
Raoult’s Law and Colligative
Properties
Colligative properties of solutions are properties
that depend on the amounts of substances present,
i.e., the concentrations of solutions. These properties
include boiling point (temperature), freezing point, and
osmotic pressure. The French chemist François Raoult
(1830–1901) formulated specific rules to explain this
behavior, and these rules became known as Raoult’s
law. Raoult established that the key factor determining
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Reverse osmosis was selected as the desalinization method for
the desalinization plant in Carlsbad, California.
the physical properties of a solution was the relative
number of moles of solute in the solution.
For example, if you dissolve 1.80 grams (0.010 mol)
of glucose (C6H12O6, molar mass = 180 g/mol) in 1
kilogram of water, you will change the freezing point
of the water from 0.0000 ℃ to –0.0186 ℃, and if you
add ten times that amount (18.0 grams or 0.10 mol), you
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will change the freezing point by ten times as much,
or to –0.186 ℃. If you use any other kind of sugar, you
will get the same effect from 0.01 mol or 0.10 mol; the
chemical doesn’t matter, only the moles do. The same
impact is seen on the boiling point, except that the
temperature at which the solution boils is raised, rather
than lowered, by a fixed (but different) amount.
The explanation for this change in melting or boiling
point lies in the effect that any solute has on the vapor
pressure of a solvent as is shown in the phase diagram
in Figure 56.
The solute particles interfere with the ability of solvent
molecules to enter the vapor phase, thus shifting the
temperatures at which the phase changes will be
observed. The diagram shows the shifts in the freezing
point, ΔTf , and boiling point, ΔTb, of a solution
compared to the pure solvent.
However, an intriguing effect is observed when salts
are dissolved in water. In such cases, larger than
expected changes occur, given the number of moles
added. For example, 1 mole of sodium chloride, NaCl,
added to water causes a change in boiling point twice
the amount that would otherwise be expected. This
increase is readily explained since NaCl completely
ionizes in water, forming Na+ and Cl– ions. Thus,

FIGURE 56
This phase diagram depicts the effect of a solute on the
vapor pressure of the solvent, showing the shifts in the
freezing point, ∆Tf , and boiling point, ∆Tb, of a solution
compared to the pure solvent.
Image Credit: Chemistry, The Central Science, 11th edition, by Theodore
Brown, Eugene LeMay, and Bruce Bursten, Prentice Hall, 2009.
Copyright © Pearson Prentice Hall, Inc.
there are two moles of ions present for every mole of
the moles of original salt. Calcium chloride, CaCl2,
produces three moles of ions per mole of calcium
chloride in solution. Indeed, this is found to have three
times the effect on freezing and boiling points than
would be expected from just one mole.
The idea of adding salts to water or ice on roads to
lower the freezing temperature and prevent or reduce
ice formation has been around for a long time. Mostly
sodium chloride has been used since it is available
inexpensively. However, the subsequent salt solution
run-off has been found to be harmful to roadside plants
and animals and increases concrete damage.20 Calcium
magnesium acetate has been proposed as a much less
damaging alternative along with some other options,
but these are more expensive.
It is important to note that in all the solutions discussed
above, the solute doesn’t contribute anything to the
vapor above the solution. The vapor above the solution
is pure solvent! So, if it can somehow be captured and
removed, samples of pure solvent would be obtained,
and the solution would gradually become more

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salt added. Therefore, the colligative property effects concentrated in solute. This is exactly the principle
depend on the number of particle species present, not behind distillation as a means to purify solvents such

FIGURE 57

A typical laboratory still for obtaining pure water.

Image Credit: Chemistry, The Central Science, 11th edition, by Theodore Brown, Eugene LeMay, and Bruce Bursten, Prentice Hall, 2009.
Copyright © Pearson Prentice Hall, Inc.

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as water. Impure or contaminated water cannot be used
for a number of applications. A decreasing supply of
pure water is becoming a major issue for the expanding
human population and the agriculture on which
humans depend for food. A typical laboratory still for
obtaining pure water is shown in Figure 57.
A commercial unit involves a large scaling up of such
a device. The most viable alternative to distillation is
to use a process called reverse osmosis, which relies
on a different colligative property of solutions. In
reverse osmosis, water is pumped at high pressure
through a semi-permeable membrane that allows
water molecules to pass through but restricts impure
molecules, including salts, from passage. Pure water
is then collected on the inside of the membrane tubes.
Reverse osmosis was selected as the method of choice
for the desalination operation in Carlsbad, California.
Methods of water purification/desalination must be
compared for a given amount of pure water produced
on the basis of several general as well as local factors,
including:
Energy used

Pretreatment needed

Waste to be discharged

 Product purity
 Maintenance frequency and costs
Advantages of distillation over reverse osmosis include
the fact that with distillation it is easier to scale up
to large sizes; there is less need for shut-downs or
membrane cleaning; there is less pretreatment needed;
and there is less waste to dispose of. Advantages of
reverse osmosis over distillation include the fact that
reverse osmosis has lower energy needs (pumping water
uses less energy than heating water); reverse osmosis
has a lower discharge water temperature (which is less
damaging to the ecosystem); reverse osmosis also has
purer water output (no volatile contaminants) and does
not require as large a plant as does distillation.
SECTION II SUMMARY
 All matter exists in three common states: gas,
liquid, or solid.
 These three states of matter each have
distinctive properties.
 The properties of gases were found to follow
simple rules, or laws. These gas laws are
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associated with the names of the scientists who
worked them out.
 Boyle’s law states that the volume of a gas is
inversely proportional to its pressure.
Charles’s law states that the volume of a gas is

directly proportional to its temperature.
An examination of Charles’s law leads to the

notion of an absolute zero temperature at which
gas volume would theoretically be zero.
 The temperature scale derived from this idea is
known as the Kelvin scale.
 Dalton’s law sets rules for dealing with mixtures
of gases.
 Kinetic-molecular theory provides a theoretical
basis for explaining all the gas laws. It relies
on the idea that a gas consists of very small
rapidly moving particles.
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 Amedeo Avogadro proposed that under given
conditions of temperature and pressure, every
gas contains the same specific number of small
particles.
 Chemists use the unit of a mole to express an
Avogadro’s number of particles.
 There are 6.022 x 1023 particles in 1 mole of
any substance.
 The average speed of molecules in a gas
depends only on the temperature of the gas and
the mass of the gas particles.
 Oxygen was discovered by multiple scientists—
Carl Wilhelm Scheele, Joseph Priestley,
and Antoine Lavoisier—working mostly
independent of one another in the 1770s.
 The Van der Waals equation adjusts the ideal
gas law to account for the behavior of non-ideal
gases.
 Relative effusion and diffusion rates can be
calculated if the mass of the gas particles is
known.
 Liquids and solids differ from gases with
regard to the freedom of motion of the particles
 of which they are comprised.
 Intermolecular forces between the particles
in liquids and solids create an ordering that
doesn’t exist in gases.
 Solids have a very specific ordering of the
particles (ions, molecules, or atoms) of which
they are comprised.
 Some substances, such as carbon, can exist in
a variety of solid structural forms, each with
very distinctive properties.
 Metals have highly ordered structures that give
rise to their unique physical properties, such
as luster, malleability, and good conduction of
heat and electricity.
 Transitions between the various states, or
phases, of a sample of a pure substance can
be summarized in a phase diagram that shows
how the individual phases are in equilibrium as
they transition from one to another.
 The processes of melting, freezing, condensing,
vaporization, sublimation, and deposition can be
explained using a phase diagram.
 Water has unique physical properties that
can be explained by its phase diagram and its
hydrogen-bond-type intermolecular forces.
 Carbon dioxide has a more typical phase
diagram than water. Liquid carbon dioxide
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is a useful solvent for industrial and medical
applications.
 Joseph Black is credited with the discovery of
carbon dioxide.
 Solutions are formed when a solute dissolves in
a solvent.
 Solubility depends on the structure of the
solute and the solvent in terms of the polarity
of their molecules. A general rule is “like
dissolves like.”
 Solubility “rules” exist for ionic compounds
in water because certain combinations of ions
may interact to form precipitates, reducing
solubility.
 Solutions have important applications in our
society; for example, they have many uses as
cleaning products.
 How much solute dissolves in a solvent can be
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expressed in several different ways: including
percent composition, molarity, or molality.
 Physical properties of solutions, called
colligative properties, can be examined
qualitatively. The physical properties of
solutions also can be made quantitative by
using Raoult’s law.
 The processes of distillation and reverse osmosis
can be used to purify solvents such as water.
 Sect ion 3
Reactions
SECTION III INTRODUCTION FIGURE 58
Chemistry is all about reactions. Reactions occur when
atoms in chemical substances rearrange under certain
conditions to form new substances that have different
physical and chemical properties. In this section of the
resource guide, you will learn how chemists classify
different reaction types and how they keep track of the
atoms involved in the changes. You will also learn about
the conditions that determine whether reactions allow
for the complete reorganization of atoms, or only partly
so. In addition, you will learn how certain conditions
determine how fast reactions will take place and how

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chemists track energy changes. Lastly, you will learn
about energy changes since they enable chemists to
predict which reactions will occur and which will not.
TYPES OF REACTIONS
There are five basic types of reactions that we will
study here:
1. Synthesis
2. Decomposition
3. Double replacement
4. Single replacement
5. Combustion
These different types of reactions are distinguished
by the pattern of atom rearrangement that takes place.
Learning about these patterns will be helpful when you
need to predict the products in a reaction. Within these
patterns, reactions may be further classified according
to the properties of the substances that are reacting or
the products that are formed.
The reaction of potassium with chlorine.
Image from Chemistry: The Molecular Nature of Matter and Change,
4th edition, by Martin Silberberg, published by McGraw-Hill, © 2006.
of an arrow. The arrow means “yields” or “to make.”
The products of the reaction are found on the right-
hand side of the arrow.
You might expect an equation to have an equal sign,
and in fact, reaction equations used to have equal
signs, but chemists decided that it was better to use
an arrow to indicate the direction of the reaction.
However, these reactions are still referred to as
equations because the number and type of atoms on
the left side must equal the number and type of atoms
on the right side. For example, the equation A + B → C
+ D indicates that A and B are reactants and C and D
are products, or what is made in the reaction.

Before we look at the patterns of atom rearrangement
that can occur in reactions, we need to understand
chemical equations. Chemical equations track the
atoms in chemicals and the manner in which they are
rearranged during a reaction. In chemical equations,
reacting substances are indicated on the left-hand side
Synthesis, or combination reactions, involve combining
two or more reactants and making one product. The
equation for a synthesis reaction will have the form A +
B → C. An example of this type of reaction is 2Na + Cl2
→ 2NaCl. A different example is shown in Figure 58,
which depicts the reaction of potassium with chlorine.

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 FIGURE 59
A decomposition reaction in which mercury oxide is broken
down into mercury and oxygen.
Image from Chemistry: The Molecular Nature of Matter and Change,
4th edition, by Martin Silberberg, published by McGraw-Hill, © 2006.
In decomposition reactions, one reactant breaks into
several products, taking the general format A → B +
C. One example of this type of reaction is 2H2O2 →
2H2O +O2. Figure 59 depicts another decomposition
reaction that several chemists used to make oxygen gas
when it was first identified in 1774.
Double replacement reactions involve two ionic
compounds in solution trading ions. Double replacement
reactions have the general formula of AB + CD → AD
+ CB. Pb(NO3)2(aq) + 2KI(aq) → PbI2(s) + 2KNO3(aq)
is an example of a double replacement reaction, and this
reaction is shown in Figure 60.
Single replacement reactions have one atom moving
into a compound and another atom moving out of the
compound. Single replacement reactions have two
different formats, depending on whether the atom is
from a metallic element or a nonmetallic element. If
the incoming atom is a metal, M, the format is M + BC
→ MC + B. If the starting element is a nonmetal, N,
the format is N + BC → BN + C.
An example of a metal single replacement reaction is
Cu(s) + 2AgNO3(aq) → Cu(NO3)2(aq) + 2Ag(s). An
example of a nonmetal single replacement reaction
is Cl2 + 2KBr → 2KCl + Br2. Metal replacement
reactions are quite common. A metal replacement
reaction with copper wire being added to silver nitrate
is pictured in Figure 61.
Figure 62 shows the addition of lithium metal to water.
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FIGURE 60
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A double replacement reaction.
Image from Chemistry: The Molecular Nature of Matter and Change,
4th edition, by Martin Silberberg, published by McGraw-Hill, © 2006.
In this case, the lithium displaces H+ in the water, and
elemental hydrogen gas results.
So how does one predict whether a single replacement
reaction will take place? Familiarity with the activity
series of the metals is needed. The activity series
shown in Figure 63 indicates which reactions will take
place. In the reactions shown previously, copper was
able to take the place of silver ion. The activity series
shows that copper is above silver, which indicates that
it is more reactive. If silver metal were to be put in a
copper solution, no reaction would occur. The series
also indicates which metals can displace H+ from water
and form hydrogen gas. This means that any atom
above hydrogen can displace hydrogen from its source.
Combustion reactions are reactions of a reactant
substance with oxygen gas (O2). If the reactant is an
organic hydrocarbon, then the complete combustion
products will be water and carbon dioxide, as is shown
here in the combustion of methane (natural gas):
CH4 + 2O2 → 2H2O + CO2.
FIGURE 61 FIGURE 62

A metal replacement reaction with copper wire being A reaction involving the addition of lithium metal to water.
added to silver nitrate. Image from Chemistry: The Molecular Nature of Matter and Change,
Image from Chemistry: The Molecular Nature of Matter and Change, 4th edition, by Martin Silberberg, published by McGraw-Hill, © 2006.
4th edition, by Martin Silberberg, published by McGraw-Hill, © 2006.

FIGURE 63

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The activity series for metals.

Image from Chemistry: The Molecular Nature of Matter and Change, 4th edition, by Martin Silberberg, published by McGraw-Hill, © 2006.

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To understand all chemical reactions, we must look substances and how they react by examining three
at the properties of the substances that are reacting. types of reactions: acid-base reactions, precipitation
While there are many possible chemicals that react, reactions, and oxidation-reduction reactions.
here we will learn about three common types of

ANTOINE LAVOISIER, THE CONSERVATION OF MASS, AND THE BIRTH

OF MODERN CHEMISTRY
Chemistry’s origins are rooted in humankind’s interest
in nature and natural materials, and for many centuries,
this interest fueled the field of alchemy. Alchemists were
intent on transforming less valued substances into more
valuable ones, attempting, for example, to change lead
into gold, in a process known as transmutation. While
such pursuits did not meet with success, alchemists
nevertheless played a significant role in the development
of chemistry. Alchemists’ efforts focused on using
observation and experimentation—essential aspects of
modern science—and alchemists pioneered the chemical
processes of distillation, percolation, and extraction.13
A depiction of Antoine Lavoisier conducting an experiment on

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The importance of chemistry’s applications to the respiration in the 1770s.
science of medicine also provided a major impetus
for the development of modern chemistry. Johann Baptista van Helmont (1579–1644) was a Belgian physician
who had a noted interest in medical chemistry and believed that if he could better understand chemistry, he
would better understand the causes of disease. Van Helmont made numerous advancements—he introduced the
term “gas,” developed an effective balance, anticipated the law of conservation of mass (which would later be
conclusively demonstrated by Antoine Lavoisier’s experiments), and provided several refutations of the notion
of alchemy and element transmutation.14,15 Van Helmont’s ideas were at first challenged by leading physicians
but were supported and followed closely by an expanding group of non-medical scientists working in France and
Britain, notably Robert Boyle (1627–91), Joseph Black (1728–99), Henry Cavendish (1731–1810), Joseph Priestley
(1733–1804), and Antoine Lavoisier (1743–94).
These scientists, and many others, began the modern practice of operating research laboratories, producing
more frequent publications, and encouraging the exchange of scientific ideas. Several even visited one another
to observe each other’s laboratory experiments. Much of their practice and discussion focused on reactions in
air, as they tried to explain the results of reactions of metals and carbon compounds heated in air—reactions
that are now known as “oxidation.” In the late seventeenth century, scientists had tried to determine what caused
matter to change form, but such investigations were hampered by the dominance of phlogiston theory. This
faulty theory proposed that as materials burned, they released a substance—termed phlogiston—that could
not be detected. Highly combustible materials were thought to contain much phlogiston while less combustible
materials were thought to contain very little. While this theory was widely held, as scientists experimented, they
made observations that raised questions to which phlogiston theory had no answers, notably the question of why
air is required for combustion.
It was Antoine Lavoisier who developed a scientific explanation for combustion that refuted phlogiston theory.
In his experiments, Lavoisier heated mercury calx, causing it to decompose into mercury and a gas. Lavoisier
noted that the combined masses of the mercury and the gas were the same as the original mass of the calx prior
to burning. Lavoisier conducted a reverse experiment in which he heated the mercury and the gas and found that
it yielded mercury calx of the same mass. It was significant that the total mass remained constant because that

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conclusion countered the notion that the substance was releasing phlogiston.
Lavoisier believed that when metals formed a calx, they combined with a gas that was in the surrounding air. He
explored this idea via an experiment in which he heated mercury in a specific volume of air to create mercury
calx and observed that this decreased the volume of the air. Lavoisier then put a lit candle into the container of
air and saw that the candle’s flame was extinguished. This indicated to him that the gas that had been mixed with
the mercury was required for combustion. Lavoisier called this gas oxygen (oxygène in French) and referred to
metal calxes as metal oxides.
Lavoisier’s experiments not only led to the naming of oxygen and a better understanding of the process of
combustion, but also led to the principle of conservation of mass. Lavoisier established that mass is neither
created nor destroyed during a chemical reaction, as was made clear by the fact that the mass of the reactants
was equal to the mass of the products in his experiments with mercury calc. This finding was incredibly
significant to the development of modern chemistry and science as a whole.
Lavoisier, who is often called the “father of modern chemistry,” created a more coherent picture of what the
“rules” of chemistry are and made numerous influential findings that have held true over the course of time. He
discovered that air is composed primarily of oxygen and nitrogen; that water cannot be converted into Earth; and
that matter is conserved in chemical and physical interactions. Lavoisier also began (with others) to systematize
the naming of chemical compounds, and his system of chemical nomenclature continues to be used by scientists
in the present day.16

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ACID-BASE REACTIONS
This section introduces acids and bases and the
concept of pH. There are several theories of acids and
bases, but here we will only discuss those introduced
by Svante Arrhenius (1859−1927) and Johannes
Brønsted (1879−1947) and Thomas Lowry (1843−1909)
(the Brønsted-Lowry acid-base theory).
Arrhenius Acids and Bases
The first theory concerning acids and bases was
developed by the Swedish scientist Svante Arrhenius,
who stated that acids break apart in water to yield
H+(hydrogen ion) and that bases break apart in water
to yield OH– (hydroxide ion). However, this theory was
incomplete, as it could not explain why, for example,
tests would show that NH3(ammonia) solution was basic
despite the fact that ammonia does not contain OH–.
Brønsted-Lowry Acids and Bases
Danish chemist Johannes Brønsted and British chemist
Thomas Martin Lowry took a different approach from
Arrhenius and looked at how a substance reacted.
According to their theory, an acid is defined as any
reactant that donates an H+ in a reaction, and a base is
defined as any H+ acceptor in the reaction.
This could explain the behavior of NH3 in water. In
the reaction NH3 + H2O → NH4+ + OH–, the water
donates an H+ to the ammonia, making water an acid
and ammonia a base. Ammonia becomes a positive
ammonium ion, and the other product is OH–. The
solution has an excess of OH– ions and thus is basic. The
Brønsted-Lowry model also explains all Arrhenius acids
and bases.
In other situations, water can behave as a base by
accepting an H+ and forming H3O+(hydronium ion).
For example, when acetic acid (HC2H3O2) is added
to water to make vinegar, the reaction that occurs is:
HC2H3O2 + H2O → H3O+ + C2H3O2– . The acetic acid
has transferred an H+ to water and is acting as an acid
in solution. The water has acted as a base by accepting
the H+ and forming a negative acetate ion. The excess
of H3O+ ions makes the solution acidic.
The reactions just described indicate that water can
be either an acid or a base depending on the situation.
Because water demonstrates this behavior, we say that
water is amphoteric.
The Acidity Scale: pH
pH is a measure of the acidity or basicity of an aqueous
solution. A logarithmic scale called the pH scale
relates the acid concentration, which is defined as
the concentration of H3O+ in units of moles per liter.

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The equation is pH = – log[H3O+], where the square
brackets indicate concentration in the units of molarity. FIGURE 64
Chemists usually abbreviate [H3O+] to simply [H+].
The pH scale generally ranges from 0 to 14, where
any substance with pH below seven is acidic, which
indicates that [H+] is greater than 1.0 x 10 –7 M. A pH of
seven is neutral, [H+] = 1.0 x 10 –7 M. Substances with a
pH above seven are basic, so [H+] is smaller than 1.0 x
10 –7 M. This means that a solution with a low pH (acidic)
has a lot of H+ compared to pure water. Conversely, a
high pH (basic) solution has very little H+.
Note that acid and base solutions always contain both
acid and base. In acidic solutions, there is more acid A depiction of a titration.
than base, and in basic solutions, there is more base Image from Chemistry: The Molecular Nature of Matter and Change,
than acid. Neutral solutions (pH exactly = 7.00) have 4th edition, by Martin Silberberg, published by McGraw-Hill, © 2006.
an equal amount of acid and base. This is because in
a sample of pure water some of the water molecules called a titration. In this method, pictured in Figure
transfer a few H+ ions, making OH–, but there are equal 64, a given amount of acid with an unknown molarity
concentrations of H+ ions and OH–, both at 1.0 x 10 –7 is placed into a flask, and a solution of a base of known
M, and thus pure water has a neutral pH = 7.0. molarity is added by using a buret. The long tube
being used in Figure 64 is a buret, which has a device

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Titrations—Mixing Acidic and
Basic Solutions to Measure the
Concentration of an Unknown
Acid-base reactions are a type of double replacement
reaction where an acid + a base yields a salt + water.
A salt is the compound formed when the H+ of an acid
is replaced by a metal ion or its equivalent. In the salt
NaCl, the H+ in HCl has been replaced by the metal
ion Na+. Many acids can be recognized as substances
whose formulas start with atoms of hydrogen, such as
HCl, HBr, H2SO4, HC2H3O2, and HNO3.
In water solutions, the hydrogen atom is transferred to
water as a positive ion, H+. Strong acids are those that
will transfer all their H+ to water. Weak acids are those
that will transfer only a few molecules of H+ to water. A
base is any substance that accepts H+ ions. Many bases
have an OH– ion, and so H+ + OH– → H2O. Water is
formed as a product in such an acid-base reaction.
The salts that are formed when acids and bases react
can be acidic, basic, or neutral. The salts that are neutral
are those made from a strong acid and strong base. For
example, NaCl is made by reacting HCl and NaOH. KBr
is a salt from the reaction of HBr and KOH.
When acids and bases are mixed together and the pH
is measured as different amounts react, the process is
called a stopcock that opens and closes, allowing for
the solution to be added by drops into the Erlenmeyer
flask. Usually, the acid is in the flask, and the base is in
the buret, but it can be done the opposite way with the
base in the flask and the acid in the buret.
The buret allows for accurately measured volumes of a
liquid to be introduced. When the moles of acid in the
flask are exactly equal to the moles of added base, the
reaction has reached the equivalence point or endpoint
of the titration. To help identify this point, chemists use
a pH indicator, a compound that has different color at
different pH. As the reaction reaches the endpoint, the
indicator, which is sensitive to a certain pH, changes
color. Titrations, as well as the pH state of any solution,
can also be performed by using an instrument called a
“pH meter.”
Since the moles of acid and base are equal at the
equivalence point, we can write the equation MaVa =
MbVb, where a represents total acid, and b represents
total base. M is the molarity of each substance, and V
is the volume of each substance. The reason this has to
be written for total acid content or H+ is that sometimes
acid substances are diprotic, such as H2SO4, or
triprotic, such as H3PO4. A diprotic acid can provide
2 H+ ions to the reaction for every mole of acid added,
and a triprotic acid can provide up to 3 H+ ions for

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every mole of acid added. These differences have to be
accounted for in the equation.
Let’s look at an example. If 50.0 mL of HCl of unknown
molarity were titrated with 25.0 mL of 1.50 M NaOH,
the equation would have Va = 50.0 mL = 0.0500 L; Mb =
1.50 M; and Vb = 25.0 mL = 0.0250 L. So, Ma x 0.0500
L = 1.50 M x 0.0250 L. The unknown quantity is Ma,
which means the acid concentration must be 0.750 M.
Acid-Base Reactions and Salts
A salt is an ionic compound that is a product of the
reaction between an acid and a base. When the salt
dissolves in water, its ions can interact with water
molecules in a reaction called hydrolysis. If hydrolysis
results in the anion of the salt reacting with water
to produce the conjugate acid of the anion and the
hydroxide ion, then the solution will be basic. If,
instead, the cation reacts significantly with water to
form the conjugate base and H+, then the solution will
be acidic. If neither ion reacts significantly, or if both
react equally, then the solution will be neutral. An
example of each scenario is given below.
(a) Basic Salt: dissolving solid sodium acetate in
water; sodium and acetate ions are formed. The acetate
ion (an anion) accepts a proton from water, forming
excess hydroxide ion:
CH3COO – (aq) + H2O(l) ↔ CH3COOH(aq) + OH– (aq)
The conjugate acid produced, acetic acid, is a weak acid
that does not ionize to a great extent. Since the acetate
ion has accepted a proton, it has behaved as a base. The
solution will have a pH > 7 as a result of the hydroxide
ions produced. The sodium ions are “spectators.” In
general, anions of weak acids will form basic salts.
(b) Acidic Salt: dissolving solid ammonium chloride
in water; ammonium and chloride ions are formed.
The ammonium ion donates a proton to water, forming
the hydronium ion:
NH4+(aq) + H2O(l) ↔ NH3(aq) + H3O+(aq)
The conjugate base produced, ammonia, is a weak
base that does not ionize to any great extent. Since the
ammonium ion has donated a proton to water, it has
behaved as an acid. The solution will have a pH < 7 as
a result of the hydronium ions produced. The chloride
ions are spectators. In general, cations of weak bases
will form acidic salts.
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(c) Neutral Salt: dissolving sodium chloride in water;
sodium and chloride ions are produced. Neither reacts
appreciably with water in an acid-base hydrolysis
reaction, so the pH = 7, and hence it is a neutral solution:
Na+(aq) + Cl– (aq) + H2O(l) → no reaction
Neutral salts are formed from the cation of a strong
base and the anion of a strong acid.
The following table shows some typical cations and
anions and the salts they will form:
Cation Anion
pH
Examples Examples
Cl–, Br–, I–,
Na+, K+, Rb+,
= 7, neutral ClO4 –, BrO4 –,
Cs+, Mg2+, Ca2+
NO3–
NH4+, CH3NH3+,
< 7, acidic
Cu2+
F–, HCO3–,
> 7, basic
SO42–, CH3COO –
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Thus, to predict whether a salt will dissolve to form an
acidic, basic, or neutral solution, one has to know if the
ions composing the salt will undergo hydrolysis.
PRECIPITATION REACTIONS
Precipitation reactions are a specialized type of double
replacement reaction. In precipitation reactions, two
solutions, each containing ions in water, are mixed,
and one of the products will be a solid precipitate
that forms in the solution, often appearing as a cloud.
The precipitate may settle slowly to the bottom of the
container. Occasionally, two products may both be
precipitates. The ions that do not form precipitates and
remain in the solution are known as spectator ions
because no change occurs to them during the reaction—
hence they are simply watching what is going on like
spectators.
Let’s look at an example of a precipitation reaction. If
silver nitrate solution is mixed with sodium chloride
solution, a balanced equation can be written to
represent the reaction:
AgNO3(aq) + NaCl(aq) → AgCl(s) + NaNO3(aq)
However, if the ions in the solution are separately
represented, we can write the following:
 FIGURE 65
Different types of chemical equations.
Image from Chemistry: The Molecular Nature of Matter and Change,
4th edition, by Martin Silberberg, published by McGraw-Hill, © 2006.
Ag+(aq) + NO3– (aq) + Na+(aq) + Cl– (aq) → AgCl(s) +
NO3– (aq) + Na+(aq)
Then, we notice that the NO3– (aq) and the Na+(aq) are
the same on both sides of the equation, so these ions
are the spectators while the AgCl is the precipitate.
The net reaction omits spectators and thus is written:
Ag (aq) + Cl (aq) → AgCl(s)
+ –
Figure 65 provides another example, showing different
equations and the spectator ions.
To predict which ions form precipitates and which will
be spectators, chemists use the solubility rules that we
discussed in Section II of this resource guide. Here are
the solubility rules briefly listed again:
1. Group I nitrates, acetates, and chlorates and
ammonium ions are soluble, except for those
listed previously. Carbonates, hydroxides,
oxides, silicates, and phosphates are insoluble.
2. Only Ag, Hg(I), and Pb(II) form precipitates
with chloride, bromide, and iodide.
3. All sulfates are soluble, except those of barium,
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FIGURE 66
Precipitation Region
Log molal concentration
MOH
+
M
Soluble
-
MO
Soluble
pH
Diagram showing the precipitation region for typical metal
hydroxides.
Image Credit: Geoenvironmental Engineering: Contaminated Soils,
Pollutant Fate, and Mitigation, by Raymond N. Yong, CRC Press, © 2001.
strontium, calcium, lead (II), silver, and
mercury (I). Most sulfides are insoluble except
for calcium, barium, strontium, magnesium,
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sodium, potassium, and ammonium.
Let’s look at a couple of examples that will demonstrate
how these rules can be applied to two different
reactions. If chloride ions are mixed with sodium ions,
rule 2 suggests that no precipitate will form, and the
sodium and chloride ions will remain as spectators:
Na+(aq) + Cl– (aq) → no reaction
However, if lead ions are mixed with chloride ions,
rule 2 says that a precipitate of lead chloride (PbCl2)
will form:
Pb2+(aq) + 2Cl– (aq) → Pb(Cl)2(s)
Precipitates
The phenomenon of precipitation has been described
as an equilibrium process. For many chemical
substances, the range of conditions under which
substances dissolve in water or precipitate is
limited, as is shown in the diagram for typical metal
hydroxides shown in Figure 66. The precipitation of
metal hydroxide depends on the concentration of OH–.
At low pH, OH– concentration is low and increases as
the pH increases. As OH– increases further, it reacts
with the metal hydroxide to form a soluble oxide ion.
Precipitation often has significant environmental
 FIGURE 67

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The aquatic mercury cycle.

ramifications. For example, the control of soil pH is
important for plant growth. Unless nutrients dissolve,
they are unavailable to plants, and so farmers must
add acidic or basic substances to their soils to optimize
the dissolution of nutrients. In some regions, acid
rain is responsible for lowering soil pH. This must
be balanced by the addition of basic chemicals to
neutralize the effects of the acid rain. Efforts to
adjust soil pH may inhibit efforts to remove toxic
contaminants that have been added to the environment
by increasing their solubility.
emitted into the atmosphere from fossil fuel power
plants and enters lakes and soils as waste from the
use of mercury in electrolytic cells for the production
of chemicals, such as chlorine. Improved practices
have been able to reduce the release of mercury from
electrolytic cells to quite low levels.
Mercury from the atmosphere enters the aquatic
environment, precipitating in various forms, which
then cycle back into the water and the biosphere in
complex ways, as is shown in Figure 67.

Perhaps the most well-known contaminant is mercury, Many other precipitates cause problems in the
which enters the environment as metallic mercury environment, including those being transported in mine

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run-off and toxic materials absorbed on iron hydroxide
precipitate. Another source of harmful precipitates
is in the atmosphere. Atmospheric particles, called
particulate matter, enter the lungs where they may stick
or exchange harmful components that damage lung
tissue. Unfortunately, seemingly harmless particles,
such as sea salt, can absorb other chemicals on their
surfaces and transport them into the lungs.
Toxic substances are easier to bury or handle than
solutions. So, using precipitation to remove dissolved
toxic substances from large amounts of contaminated
water is a common process. Care must then be taken
to see that the precipitates are themselves carefully
disposed of and cannot reenter the environment as
particulates or by re-dissolving.
One example of this approach is the recovery of silver
metal from used photographic chemicals. Before
digital cell phone cameras became so widely used,
an enormous number of photographs were processed.
Almost all of these involved the use of silver halide salts.
After the exposure and development of the image, which
consisted of silver metal on paper or plastic, excess
silver had to be removed in a process called fixing.
Large amounts of silver in the waste solutions were then
complexed with the chemical sodium thiosulfate. The
silver could be precipitated as metallic silver by adding
iron (in the form of steel wool) or as silver chloride by
adding chloride ion. Subsequently, the silver could be
melted into ingots, or the chloride could be dissolved in
nitric acid, and the silver could be electrolytically plated.
OXIDATION-REDUCTION
REACTIONS
Oxidation-reduction, or “redox,” reactions involve
a transfer of electrons from one molecule to another.
How and why do the electrons transfer? Every neutral
atom has a number of electrons equal to its proton
number. For instance, sodium has eleven electrons of
which one is a valence, or outermost, electron. When
the sodium atom changes to a sodium ion with a +1
charge and with only ten electrons, it has freed up one
electron and has undergone oxidation. The oxidation
part of a reaction frees up electrons from one reactant
that are then used in the reduction of the other reactant.
For example, the freed electron from the sodium
can then be used to reduce a silver ion with forty-six
electrons and a +1 charge to the charge-neutral silver
atom with forty-seven electrons. An electron transfers
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from the sodium to the silver ion:
Na + Ag+ → Na+ + Ag
Oxidation-reduction reactions are the types of reactions
that run batteries. To be able to determine what is
occurring in these reactions, it helps to first identify
oxidation numbers. These numbers help determine the
number of electrons transferring in a reaction.
Oxidation Numbers
Oxidation numbers provide us with an accounting
process for atomic electrons. The oxidation number
for an element in a compound is equal to the number
of electrons that must be added or subtracted from
the atom in its combined state to get to the number of
electrons of its free, neutral atom. Oxidation numbers
can be positive, negative, or equal to zero.
Let’s look at some examples. In AgCl Ag is +1 and Cl
is –1, whereas in Al2O3, Al is +3 while O is –2. In the
metal sodium, Na has an oxidation number of 0.
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Some standard rules help us to determine the oxidation
numbers for different elements. Following are two
simple rules that are true for nearly all compounds that
they form:
(1) H and group 1 elements have oxidation
numbers of +1.
(2) The oxidation number of O is –2.
(There are exceptions: H has an oxidation number
of –1 in metal hydrides, such as AlH3, and O has an
oxidation number of –1 in peroxides, such as H2O2.)
The table shown in Figure 68 indicates possible
oxidation numbers for the elements.
We can state four other rules concerning oxidation
numbers:
(3) The oxidation number of all monatomic ions is
the charge on the ion.
(4) All neutral atoms have an oxidation number of
0.
(5) Oxidation numbers of atoms in neutral
compounds must add up to 0.
(6) The sum of the oxidation numbers of atoms in
polyatomic ions must be equal to the charge on
the ion.
In most cases, it helps to set up a mathematical
 FIGURE 68
1 18
1A 8A
1 2
H He
+1
–1
2 13 14 15 16 17
2A 3A 4A 5A 6A 7A
3 4 5 6 7 8 9 10
Li Be B C N O F Ne
+1 +2 +3 +4 +5 +2 –1
+2 +4 –½
–4 +3 –1
+2 –2
+1
–3
11 12 13 14 15 16 17 18
Na Mg Al Si P S Cl Ar
+1 +2 +3 +4 +5 +6 +7
–4 +3 +4 +6
+5
3 4 5 6 7 8 9 10 11 12 –3 +2 +4
–2 +3
3B 4B 5B 6B 7B 8B 1B 2B +1
–1

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19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
K Ca Se Ti V Cr Ma Fe Co Ni Cu Zn Ga Ge As Se Br Kr
+1 +2 +3 +4 +5 +6 +7 +3 +3 +2 +2 +2 +3 +4 +5 +6 +5 +4
+3 +4 +5 +6 +2 +2 +1 –4 +3 +4 +3 +2
+2 +3 +4 +4 –3 –2 +1
+2 +3 +3 –1
+2 +2
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
+1 +2 +3 +4 +5 +6 +7 +8 +4 +4 +1 +2 +3 +4 +5 +6 +7 +6
+4 +4 +6 +6 +3 +2 +2 +3 +4 +5 +4
+3 +4 +4 +2 –3 –2 +1 +2
+3 –1

55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
+1 +2 +3 +4 +5 +6 +7 +8 +4 +4 +3 +2 +3 +4 +5 +2 –1
+4 +6 +4 +3 +2 +1 +1 +1 +2 +3
+4

Possible oxidation numbers for the elements.

Image from Chemistry, 7th edition, by Raymond Chang, published by McGraw-Hill, © 2002.

relationship applying rules (5) and (6). For example,
in the neutral compound potassium permanganate,
KMnO4, using rules (1) and (2), K is +1 and O is –2.
So, to determine the oxidation number of the Mn, we
can let Mn be x, and we can set up the equation: 1 +
x + (4 –2) = 0. Therefore, x = +7.
Once oxidation numbers are determined, it is then
possible to determine how many electrons are involved
in changing from one form of an atom to another.
For instance, if during a reaction Ag+ (Ag = +1) is
changing to Ag (Ag = 0), a one-electron change is
observed as one electron must be added to reduce the
positive silver ion (cation) to its neutral atom.

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 FIGURE 69

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Selected Standard Electrode Potentials.
Image from Chemistry: The Molecular Nature of Matter and Change, 4th edition, by Martin Silberberg, published by McGraw-Hill, © 2006.

The Role of the Electron in Oxidation-
Reduction
In an oxidation reaction, the electron is freed and then is
used in the reduction reaction. To balance equations for
these types of reactions, it is important to note that the
number of electrons freed during oxidation must equal
the number of electrons added during the reduction
process. Electrons are conserved in nature. Even in a
battery, which is a source of electrons, a complete circuit
must deliver the electrons back after they have done any
outside work or else the battery cannot operate.
To help construct oxidation-reduction reaction
equations, half-reactions are written to identify what
is happening separately in the oxidation and reduction
parts of the reaction and to determine how many
electrons are being used. Then, you use a multiplying
factor (if needed) to balance out the number of electrons
added in one half-reaction with the number removed in
the other half-reaction, and the half-reactions are added
together to make the reaction equation complete.
Let’s look at an example where copper reacts with silver
ion: Cu + Ag+ → Cu2+ + Ag. The two half reactions are
as follows:
1. Cu → Cu2+ +2e –
2. Ag+ + 1e – → Ag
The second reaction must be multiplied by 2 to have a
two-electron change, as that is how many electrons the
first reaction is yielding, so we have the following:
3. 2Ag+ + 2e – → 2Ag
Summing equations 1 and 3 gives us the following
balanced equation:
4. Cu + 2Ag+ → Cu2+ + 2Ag
ELECTROCHEMISTRY
Introduction
Electrochemistry involves the use of the oxidation-
reduction reactions we have just introduced. In

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 FIGURE 70

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Components of a typical galvanic electrochemical cell.
Image from Chemistry: The Molecular Nature of Matter and Change, 4th edition, by Martin Silberberg, published by McGraw-Hill, © 2006.

electrochemistry, we wish to understand what governs Cell Potentials

which reactions will occur and how this can be used—
as, for example, in the process of electroplating.
Perhaps the most common example of electroplating is
chrome plating, which is used to create shiny parts on
appliances and automobiles.
The tendency of an electron to leave an atom or to join
an atom is measured as electrical energy in units of
volts. Since this energy can be measured even when an
actual transfer has barely taken place, it is called a cell
potential. It represents the potential energy that could
do some work. This concept is the basis for a battery.

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Until the battery is used, it retains its potential or
voltage. When all the reaction has been completed and
the system reaches chemical equilibrium, the battery
has run down (is dead).
Each half-reaction described in the previous section can
be assigned a potential. Such a potential can be found
in a table of reduction potentials, where the direction of
the reaction is assumed to be electron gain, also known
as reduction. These are relative voltages that have been
measured under the standard conditions of a 1 molar
solution of the appropriate ion and at 1 atmosphere of
pressure. All standard half-cell potentials are measured
relative to the reaction 2H+ + 2e– → H2 (gas).
A brief table showing standard reduction potentials
is shown in Figure 69. Since all the reactions are
reductions, the reaction that is oxidation is just the
reverse of these, and the potential of the cell is the
same, but the sign is changed. For example, if the
oxidation reaction is Cu → Cu2+ + 2e –, then the E°
(standard oxidation potential) of the half-cell is –0.34
Cu → Cu2+ +2e – E0 = –0.34 V
Ag+ + 1e – → Ag E0 =+0.80 V
The sign of the Cu half-reaction voltage was
changed since it was the oxidizing half-reaction. (Or,
alternatively, you can think of it as subtracting the
reduction potential of the oxidation reaction from the
reduction potential of the reduction reaction.) Now, the
two half-reactions are added together (–0.34 + 0.80)
for a complete cell voltage of + 0.46 V. Since this is a
positive number, this is a naturally occurring reaction
or, as chemists say, spontaneously occurring.
An example of a nonspontaneous reaction is Li+ + Fe3+
→ Li + Fe2+. The two half-reactions are as follows:
Li+ + e – → Li E° = –3.05 V
Fe2+ → Fe3+ + e – E° = –0.77 V
The combination of the two half-reactions –3.05 V
+ (–0.77 V) gives us a cell voltage of –3.82 V. This
reaction will occur naturally only in the reverse
direction, or Li + Fe3+ → Li+ + Fe2+ when the cell

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V. voltage is +3.82 V.

Half-cell potentials are combined to provide
information on a complete reaction. The potential
value is not affected by the balancing of the reaction
equation. The possible voltage is the difference
between the reduction potential of the reduction
reaction and the reduction potential of the oxidation
reaction (i.e., Eored – Eoox). If the total voltage is a
positive value, then the reaction will proceed in the
forward direction (from left to right as written). If the
voltage is negative, then the reaction will proceed in
the reverse direction, or from product to reactant.
Let’s look at some examples that illustrate this. For the
reaction Cu + 2Ag+ → Cu2+ + 2Ag described earlier,
the voltage of the reaction is determined by first
identifying the potential of each half reaction:
Figure 70 illustrates the components of a typical
galvanic electrochemical cell and shows how its
voltage could be measured. In a galvanic cell, the
electrodes at which the two half reactions are occurring
are identified by the terms anode and cathode. The
anode is the electrode where oxidation occurs, and the
cathode is the electrode where reduction occurs.
This oxidation half-cell has a potential of +0.76
V which combined with the reduction half-cell of
+0.34 V gives the overall cell potential of +1.10 V.
This is a positive value, so this reaction will happen
spontaneously under standard conditions. This cell
was invented by the English scientist J. F. Daniell in
1836 and was the earliest reliable battery. Spontaneous
reactions are clearly quite useful in providing us with
batteries to power our electrical devices.

LUIGI BRUGNATELLI AND THE DEVELOPMENT OF ELECTROPLATING

The idea of coating an object in metal to protect it or keep it from tarnishing is a concept that has been
experimented with since ancient times. Yet it is the Italian chemist Luigi Brugnatelli (1761−1818) who is most
frequently given credit for developing the modern process of electroplating. Electricity was a burgeoning field of
research and fascination in the late eighteenth and early nineteenth centuries. In the 1780s, the Italian physician and
scientist Luigi Galvani (1737−98) found that when he dissected frogs hung on metal hooks, the frogs would twitch if
touched with another piece of metal. Galvani believed this resulted from electricity that originated within the body

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of the animal, which he termed “animal electricity.”
However, the Italian physicist and chemist Alessandro
Volta (1745−1827), who became a preeminent pioneer
in the field of electricity, disagreed with Galvani’s
conclusion. Volta believed the electricity was not coming
from within the frogs, but rather was being generated by
the metals.17
In 1799, Volta conducted experiments that proved
his theory to be correct as he built a voltaic pile that
was the world’s first battery to provide a continuous
electrical current. Volta published his findings in 1800,
and his friend and fellow scientist Luigi Brugnatelli
took note. In 1805, Brugnatelli discovered that if he
wired items made of metal to the negative end of a
battery and then immersed them in a solution of gold
salts, the objects would be coated in a thin film of
gold. This was due to the fact that when the positively
charged gold ions came in contact with the electrons
at the battery’s negative terminal, they were reduced
to elemental gold, in an electrochemical reduction
reaction. This occurs because the positively charged

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metal ions are attracted to the negative electrode, which
in turn gives electrons to the metal, turning it into a
neutral metal species that is no longer soluble, and thus
it forms a coating on the electrode’s surface.18
Though the process of electroplating was discovered Engraved portrait of Luigi Brugnatelli.
at the turn of the nineteenth century, it was not until
the 1840s that it became widely used in industry.
Electroplating is a commercially valuable technique because the metal coating generated in the process of
passing an electrical current through a solution containing a cation like Cu2+ and reducing it to Cu adds corrosion
protection and aesthetic qualities to a surface. For instance, in the auto and aerospace industries, plating with
chromium provides hardness, corrosion and wear
resistance, and enhances the appearance of a car. Tests
show that chromium-plated parts can last ten times
longer than parts that are not plated.
The aerospace industry also uses gold plating on
certain components used in rocket and space shuttle
designs. This gold coating protects the parts from
reacting with any other chemical substances on Earth
or in outer space. Since gold is highly reflective to
solar radiation, it also helps the components stay
cooler. Almost 41 kilograms of gold was used in the
construction of the space shuttle Columbia.

The James Webb Space Telescope’s hexagonal component Platinum, palladium, nickel, copper, silver, and rhodium
mirrors are coated with gold to optimize them for the are metals that are often used in plating. The metal
reflection of infrared light. chosen depends on the qualities desired. Over many
Photo Credit: NASA years, uses and fashions have changed. Many parts that

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used to be plated are now made from stainless steel. Silver was often used on iron cutlery, but it required frequent
polishing or cleaning. Platinum gives a silver-gray finish that resists corrosion and so is often used on sterling silver
as well as on surgical instruments. Palladium finishes are often mistakenly called “white gold” and are used in
expensive watches. Rhodium can be used to plate silver items to prevent tarnishing. Rhodium has a white color
with high reflection, and it also resists body oils that can dull non-gold jewelry.
The amount of energy used in electroplating is dependent on the amount of material to be electroplated and the
number of electrons that will be needed to reduce a metal ion to its element. Michael Faraday (1791–1867), an
English chemist, determined that it took one mole of electrons to convert one mole of silver ion, Ag+, to silver metal.
The electric charge on one mole of electrons was named the Faraday in his honor. To convert one mole of Cu2+
to copper metal, would take 2 Faradays of electrical change. Since the chromium ion is Cr3+, it takes 3 Faradays
to plate one mole, or 52 grams of chromium. The Faraday has 96,500 coulombs of charge, so 3 Faradays would
have 96,500 x 3 = 289,500 coulombs of charge. If a voltage of about 2 volts is used for the plating, then the energy
needed to create 52 grams of chromium plate is coulombs x volts = 579,000 joules, or 579 kilojoules.

E = E° – RT ln Q / nF
FIGURE 71
E is the cell potential in volts, E° is its value under
standard state conditions (at 298 K ), T is the
temperature in Kelvin, R is the universal gas constant,
n is the number of electrons transferred per unit

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The Nernst equation connects cell potentials to free energy
changes for chemical reactions.
Image Credit: Chemistry, The Central Science, 11th edition, by Theodore
Brown, Eugene LeMay, and Bruce Bursten, Prentice Hall, 2009. Copyright
© Pearson Prentice Hall, Inc.
The Nernst Equation
The German chemist Walther Nernst (1864–1941)
developed a way to make predictions about oxidation-
reduction reactions, and an equation known as the
Nernst equation resulted from his work. The Nernst
equation connects cell potentials to free energy
changes for chemical reactions. The equation can be
used for any set of concentrations of reactants and
products at any temperature. In its most fundamental
form, it is written as follows:
reaction (moles per mole), and Q is the ratio of product
concentrations to reactant concentrations.
Most often the equation is shown in a logarithm to the
base 10 version, where the Faraday constant value, F, is
included, the temperature is assumed to be 298 K (25
o
C), and the value of R has been included in appropriate
units. So, the most useful version of the equation is
written as follows:
E = E° – (0.0592 log Q) / n
E is the cell potential in volts, E0 is its value under
standard state conditions (at 298K ), n is the number
of electrons transferred per unit reaction (moles per
mole), and Q is the ratio of product concentrations to
reactant concentrations.
Let’s consider an example in which this equation
can be used. For the reaction Zn(s) + Cu2+(aq) →
Zn2+(aq) + Cu(s), the E° of the cell shown in Figure
71 is + 1.10 volts; the moles of electrons transferred,
n, per mole of zinc is 2 and in the usual equilibrium
constant formulation; and solids are not included in the
concentrations ratios.
The Nernst expression is therefore:
E = +1.10 V– 0.0592 V/2 log [Zn2+]/[Cu2+].
So, if concentrations of solutions in the cell are known,

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the cell voltage can be calculated. For instance, if [Zn2+]
= 0.50 M, and [Cu2+] = 0.10 M, then the cell voltage is
predicted to be +1.10 – 0.0296 x log 5 = +1.10 – 0.02 =
+1.08 volts. Notice that any time the concentrations of
reactants and products are equal, the cell voltage is the
standard cell voltage. One other conclusion that can be
drawn is that even if a cell has the same chemical in
each compartment, if the concentrations are not equal,
then there will be a cell voltage, even though E° is = 0.
Such a cell is called a concentration cell.
STOICHIOMETRY
In the kitchen, when a cook doubles a recipe to
make twice as many cookies, they are practicing
stoichiometry. We have already been using
stoichiometric principles in the earlier sections of this
resource guide, as we tracked the numbers of atoms
taking part in chemical and physical processes. This
is the same thing that an accountant at a bank does in
keeping track of dollars going into or out of a bank
account. In this section, we will review the principles
of stoichiometry and illustrate how important they are
in helping us to determine the amounts of substances
formed in chemical reactions. Stoichiometry uses a
balanced equation to keep track of chemical substances
changing from one compound to another compound.
A balanced equation is just a recipe that keeps track
of what is put together as ingredients (reactants) and
what is made in the end (products). The units used are
moles. In an earlier section, you learned that chemists
invented mole units to keep track of numbers of atoms
or molecules. When hydrogen burns in air to form
water, the balanced equation is:
2H2 + O2 → 2H2O
This “translates” to 2 moles of hydrogen combine with
1 mole of oxygen to make 2 moles of water. If you only
had 1 mole of hydrogen, then only ½ mole of oxygen
is needed to react, and only 1 mole of water would
be formed. This is an example of how stoichiometry
can be used. Now, we will review a few specific
applications of stoichiometric principles.
Ionic and Molecular Species Present in
Chemical Systems: Net Ionic Equations
If a chemical substance is an ion in solution, it is
shown as an ion and not a compound. For instance,
in solution, NaCl is Na+(aq) and Cl– (aq). However,
the numbers (moles) of positive and negative charges
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in any solution must be equal, so MgCl2 in solution
is Mg2+ and 2Cl–. Net ionic equations are written
to eliminate any spectator ions. (You will recall our
earlier discussion of spectator ions in precipitation
reactions.) For molecular and ionic species, the number
(of moles) of atoms of each element in reactants (left
side of the equation) must be equal to the numbers
of the same atoms in the products (right-hand side).
Atoms are always conserved in chemical reactions.
Let’s look at an example showing equations for the
reaction that occurs when solutions of silver nitrate and
sodium sulfide are mixed to yield a solution of sodium
nitrate and a precipitate of silver sulfide:
2AgNO3(aq) + Na2S(aq) → 2NaNO3(aq) + Ag2S(s)
The ionic equation is the following:
2Ag+(aq) + 2NO3– (aq) + 2Na+(aq) + S2– (aq) →
2Na+(aq) + 2NO3– (aq) + Ag2S(s)
Canceling spectator ions leaves the following balanced
ionic equation:
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2Ag+(aq) + S2– (aq) → Ag2S(s)
Balancing Redox Equations
When redox (i.e., oxidation-reduction) equations
are balanced by using the half-reaction method, the
electron change of the two half-reactions must be
balanced as well. This was explained previously in our
discussion of single replacement reactions.
Mass and Volume Relations
Compounds can be represented by either molecular
or empirical formulas. Empirical formulas provide
the lowest mole ratio of atoms to each other in a
formula. For example, acetylene, C2H2, could be CH.
However, chemists know that CH doesn’t exist as a
stable molecule, whereas C2H2 does, even though the
mathematical relationship is the same. Determining
this from experimental data is a common experiment
in chemistry.
Chemical equations and stoichiometry are used to
determine yields in more measurable units by using
molar masses. For instance, using the example given
previously, 2H2 + O2 → 2H2O, we can state that “4
grams of hydrogen react with 32 grams of oxygen to
make 36 grams of water.” Note that this restatement
uses the established facts that the molar mass of H =
1 g/mol, and the molar mass of O = 16 g/mol. Simple
math can then be used to establish that 2H2 has the
mass of 4 moles of H, that O2 has the mass of 2 moles
of O, and that molar masses are additive in calculating
that water has a molar mass of 18 g/mol.
A very common problem in chemistry is determining
a “limiting reactant” where exact stoichiometric
amounts are not present. This is also easy to relate to
cooking. If a recipe calls for four cups of flour, and you
only have two cups, it will limit the amount of product,
for example cake, that you can make. A chemist uses
a balanced equation to determine how much of each
ingredient (i.e., reactant) will be needed for a reaction
and how much product can be made.
Let’s consider the same sample reaction we just
discussed: 2H2 + O2 → 2H2O. If there are initially 12 g
of H2 and 32 g of O2, which reactant is limiting? And
how much water product can be made?
Answer: Since balanced equations are in moles, 12
g of H2 must be changed to moles by dividing by its
molar mass of 2 g/mol. This gives us 6 moles of H2.
Doing the same for the O2, we have 32 divided by the
molar mass of oxygen, which is 32 g/mol. This gives
us 1 mole of O2. With 6 moles of H2, the balanced
equation indicates that 3 moles of O2 would be needed
for a complete reaction since the ratio of H2 to O2 is 2:1.
Since we only have 1 mole of O2, there is not enough
O2 to react with all the H2. This means that 4 moles of
H2 will be left over since only 2 moles of H2 can react
with the 1 mole of O2. Therefore, the H2 is said to be in
excess, and the O2 is said to be the “limiting reagent.”
The total amount of product that can be made, called
the reaction yield, will be 2 moles of water, or 2 mol x
18 g/mol = 36 grams.

JOSEPH-LOUIS PROUST AND THE LAW OF DEFINITE PROPORTIONS

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Students of chemistry may take it as a given that chemical
compounds are comprised of constant and defined ratios of
elements. We know, for example, that carbon dioxide, CO2,
contains one carbon atom and two oxygen atoms, and thus
the mass of carbon dioxide adheres to the fixed ratio of 12:32
(which can be simplified to 3:8) since the atomic mass of carbon
is twelve and the atomic mass of oxygen is sixteen (thus, the
two oxygen atoms yield a mass of thirty-two).19 However, this
knowledge was not always accepted as a given. In fact, through
the late eighteenth century, many leading scientists believed that
elements did not necessarily mix together in fixed ratios.
The French chemist Joseph-Louis Proust (1754−1826) is
credited with establishing the fact that elements do combine in
defined ratios to form compounds, and thus the law of definite
proportions is sometimes referred to as Proust’s law. In the
1790s and into the early 1800s, Proust conducted experiments in
which he carefully studied the composition of water and copper
carbonate. Based on his observations, Proust concluded that
elements combine to form compounds in constant and defined
ratios that are determined by their mass. When he published his
Engraved portrait of Joseph-Louis Proust.
findings, Proust’s idea was rejected by some leading scientists,
Source: Wellcome Collection
most notably the French chemist Claude Louis Berthollet
(1748−1822). However, others, such as the noted English scientist John Dalton, supported Proust’s conclusions.
Dalton’s atomic theory—which proposed that each element is comprised of a particular type of atom and that
atoms combine in fixed proportions to form compounds—both supported and was supported by Proust’s law of
definite proportions. Proust’s law is an essential basis for stoichiometry.

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EQUILIBRIUM
Chemical Equilibrium
Many reactions do not go to completion but instead
start to reverse as product is made. So, while reactant
turns into product, some of the product turns back into
reactant. Obviously, this is important, as the amount
of product you get when the reaction has apparently
stopped might not be the same amount that we
calculated in the previous section.
For our example reaction A + B → C + D, this means
that soon after the reaction starts in the forward
direction as written above, some products may start to
react together in the reverse process, C + D → A + B.
Chemists often combine these two reactions together
into one equation by using a double-headed arrow to
indicate the two directions in which the reactions can
proceed: A + B↔C + D.
It is crucial to recognize that chemical reactions do not
happen instantaneously. In the next section, you will
learn about what controls how fast reactions take place.
The speed, in terms of how much material reacts in
each time unit (e.g., one minute) is known as a reaction
rate. Most reactions will eventually reach a point when
the rate of the forward reaction is the same as the rate
of the reverse reaction. When this point occurs, the
reaction is said to be at equilibrium. Even though both
reactions are still occurring, the system appears not
to change. This does not mean that the amount of any
remaining reactant equals the amount of any product
formed, but rather that the amounts of each component
of the reaction remain the same.
Equilibrium Constants
At equilibrium, chemists found that if they multiplied
the equilibrium concentrations of products together
and divided this number by the mathematical product
of the concentrations of the reactants, as long as
certain conditions were unchanged, this ratio had
a constant value. This number is known as the
equilibrium constant, and the relation from which it
can be calculated is known as the equilibrium constant
expression.
For our typical reaction A + B ↔ C + D, the
equilibrium constant expression is as follows:
[C][D]
K=
[A][B]
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Here K is the equilibrium constant, and the symbols
[A], [B], [C], and [D] represent the concentrations of the
individual reactants and products at their equilibrium
values. Each reactant or product molecule involved
in reacting or being produced must be included in the
expression.
So, for example, for the reaction A + B → 2C, the K
expression is:
2
[C][C] , which simplifies to [C]
K= K=
[A][B] [A][B]
For the completely general reaction aA + bB → cC +
dD, the equilibrium expression is:
[C]c [D]d
K=
[A]a [B]b
The constant, K, has a different numerical value for
different reactions. Chemists give special names and
expressions to these equilibrium constants, depending
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on the type of reaction involved. If the reaction
involves acids, then the equilibrium constant is called
Ka. If the reaction involves a base, then it is called
Kb. If the reaction involves forming a precipitate, then
the constant is called Ksp. If it is a reaction involving
pressures of gases, then the equilibrium constant is
called Kp. If it involves solutions and concentrations,
then the equilibrium constant is called Kc, although
this is often just written as K.
The value of the constant is an indicator of how far the
reaction will proceed, moving forward or backward. If
the K value is greater than 1, then the reaction favors
products; the value of the mathematical product of the
concentrations of products is greater than the value of
the mathematical product of the concentrations of the
reactants. In simple language, this means that when
equilibrium has been reached, there is more product
than reactant. If the value of K is less than one, then
there is more reactant than product, and so the reverse
reaction is favored. This is true regardless of the type
of equilibrium reaction.
Quantitative Treatment of Equilibrium
To solve equilibrium problems, a general understanding
of an equilibrium expression is needed. As a reminder,
the [A] indicates the concentration of substance A
in moles per liter (molarity, M). Any substance that
is a pure solid or pure liquid is dropped from the
equilibrium expression. This is because its concentration
in itself does not change or is said to have an activity of
1, and therefore including it doesn’t change the value of
the equilibrium constant. Thus, it is extremely important
that phases be known and shown in balanced equations.
Activity
Technically the concentration value used in equilibrium
expressions is the activity of the substance, defined
as the ratio of its concentration to a standard state
concentration. For aqueous solutions, the standard state
is defined as a 1 M solution, so a 0.25 M solution has
an activity of 0.25 M/1 M = 0.25 (with no unit). Hence
K values do not have units. But for gases, the standard
state is sometimes taken at 1 atm pressure, and a gas
at 0.33 atm pressure has an activity of 0.33 atm/1 atm
= 0.33 (with no unit). For a pure solid or liquid, its
standard state is taken as the pure substance, so its
activity is 1, and therefore it is usually not included in
the equilibrium expression.
Equilibrium Constants for Gaseous
Reactions: Kp, Kc
As mentioned previously, Kp is a unique equilibrium
expression for gas pressures, p, and is written slightly
differently. For the same general equation aA + bB ↔
cC + dD,
p C c p Dd
Kp =
p Aa p B b
There is an equation that allows us to convert from
a Kc to a Kp value. This equation is Kp = Kc(RT)∆n,
where ∆n represents the change in moles of gas in
the balanced equation of (total products) – (total
reactants), or (c + d) – (a + b). When the change in
moles of gas is 0, then Kp = Kc.
Equilibrium Constants for Reactions
in Solution
Equilibrium reactions in solution use Kc expressions.
Constants for Acids and Bases: pK ; pH
Because acid and base reactions involve H+ and
OH–, calculations of the pH or acid content can be
performed, and Ka, the equilibrium constant for acids,
or Kb, the equilibrium constant for bases, can also
be evaluated. The constant itself lets us know the
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characteristic of the acid or base just by the value of
the number—the smaller the number, the weaker the
acid or base. Remember that when weak acids are in
water, not all of the H dissociates from the acid to form
H+. The fewer H+ there are, the smaller the Ka will be.
For example, when acetic acid is in water (in vinegar),
the balanced reaction is HC2H3O2 ↔ H+ + C2H3O2– for
[H +][C2 H3O −2]
which the Ka expression is: [HC2 H3O2] , and the Ka value
is found to be 1.8 x 10 –5. This means that the amount of
H+ is very small compared to the concentration of the
unreacted acid (in the denominator), and so acetic acid
is classified as a weak acid. The less the acid reacts, the
smaller the Ka value. This means that the weaker the
acid, the smaller the Ka value will be.
For a base reaction such as NH3 +H2O ↔ NH4+ + OH–,
[NH4 +][OH −]
the equilibrium expression is: [NH3]
Here, too, the amount of the NH3 (ammonia) that
reacts is an indication of the strength of the base. If it
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does not react very much, the Kb value will be small.
For ammonia, the Kb value is only 1.8 x 10 –5—it is a
weak base. The weaker the base, the smaller the Kb
value will be. This is another way we can compare the
strengths of acids and bases.
Solubility Product Constants and
their Application to Precipitation and
the Dissolution of Slightly Soluble
Compounds
Ksp equilibrium constant values indicate how much a
solid will ionize in solution. For an insoluble substance
this also indicates its solubility. For example, for
the reaction AgCl(s) ↔ Ag+(aq) + Cl– (aq), the Ksp
expression is Ksp = [Ag+][Cl–]. Since the value is only
1 x 10 –10, silver chloride is an insoluble substance,
though the Ksp indicates a very small amount does
indeed dissolve. The smaller the Ksp value, the more
insoluble the compound is.
As mentioned in the earlier discussion of precipitation
reactions, if ions of silver and chloride become mixed
in the same solution, the small value for Ksp indicates
that a precipitate will form. Ksp values can be used to
predict exactly how much precipitate will form in a
precipitation reaction.
 FIGURE 72 FIGURE 73

A graph showing instantaneous rates of reaction.

Image from Chemistry, 7th edition, by Raymond Chang, published by
McGraw-Hill, © 2002. The “essential” energy of collision is called the activation
energy, Ea .
KINETICS
Kinetics is the study of how fast reactions occur and
what affects the rate at which the reaction proceeds. An
FIGURE 74
algebraic equation called a rate law can be determined
from studying experimental evidence about a reaction.

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A rate law shows how changing the concentration of
a reactant affects how fast the reaction occurs. There
is no set rate law for all reactions; the rate law is
different for different reactions.

The Concept of Rate of Reaction

As a reaction takes place, there is a loss of reactant
and a gain of product. The rate of the reaction can be
determined by tracking the change in concentrations
over time. In a car, the rate or speed is the distance
traveled over a period of time. If this changes, one
can use an average speed. The same can be done for
a reaction, but instead of measuring miles traveled,
with reactions we measure the change in concentration
over a unit of time. This will give us the average rate
of change. To determine an instantaneous rate, or the
rate at one moment in time, a chemist can construct
a graph as is shown in Figure 72. By making a line
tangent to the curve at a point and finding the slope of
the line, you obtain the instantaneous rate.
The Effect of Temperature,
Concentration, and Surface Area
Changes on Reaction Rates
The best model for chemical reactions, called the
collision model, is similar to the Kinetic Theory
described earlier in this guide. Molecules must collide
A catalyst provides a lower energy pathway for the reaction.
Image © Sinauer Associates, Inc.
in order to react. Thus, if we examine how changing
conditions affect the rate of collisions, we will be
able to predict how the reaction rate will change. For
example, every day we put foods in the freezer to keep
them longer (i.e., slow down the rate of decomposition
or decay), or we heat food to increase the rate of
chemical change by cooking it. Increasing temperature
generally increases reaction rates.
As another example, consider that an antacid tablet
such as Alka-Seltzer® clearly dissolves much more
quickly in hot water than it does in cold water. The
tablet also reacts much more quickly if it is broken into

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small pieces. An increase in surface area increases the
number of possible collisions per second with the water
molecules.
Concentration affects rates of collision and therefore
the reaction rate because if fewer molecules are present
in a given volume, then it is less likely that they will
collide and react.
Reaction Potential Energy Diagrams,
Energy of Activation, and the Role of
Catalysts
For a successful reaction to occur, not only must
reacting molecules collide, but the collision must
also happen with a certain amount of energy. Each
collection of chemically reacting molecules has a
specific energy before and after reaction. These
energies are commonly shown on a potential energy
diagram. As the reaction progresses, the energy
changes are shown from left to right on the diagram.
The “essential” energy of collision is called the
activation energy, Ea, and is shown in Figure 73.
The rate of reaction depends on the size of the
activation energy. The higher the activation energy is,
the slower the reaction will progress.
Some substances, called catalysts, can be added to
reactions to lower the required activation energy and
thus speed up the reactions. A catalyst provides a lower
energy pathway for the reaction. Imagine you need to
get to a certain destination, and there is a mountain in
front of you. Instead of climbing to the top to get to the
other side, you might find a route through a lower pass
between the mountains to the other side. This approach
would take much less energy and would be faster. The
diagram in Figure 74 shows that two reactions may
begin in the same place and end at the same place as
before, but the catalyzed reaction requires less energy.
There are many types of catalysts. Most chemical
reactions in the human body use catalysts called
enzymes to increase reaction rates at body temperature.
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FIGURE 75
Diagrams of an exothermic reaction (a) and an
endothermic reaction (b).
Image from Chemistry, 7th edition, by Raymond Chang, published
by McGraw-Hill, © 2002. Image reproduced with permission from
McGraw-Hill.
THERMODYNAMICS
Measuring energy changes in chemical reactions is
called thermochemistry. Thermodynamics is based
on the ideas of energy and temperature related to the
particle motion in the kinetic-molecular theory model
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and ultimately explains whether or not a reaction will
happen. Because movement is so important, scientists
must define very carefully what they are studying. A
part of the universe such as the number of moles of
a chemical in a beaker is called the system. All the
rest of the universe is called the surroundings. To a
thermodynamics expert: System + Surroundings =
Universe. The movement of matter and/or energy
between a system and its surroundings must be
understood in order for the laws of thermodynamics to
make sense.
Thermochemistry allows us to determine the amount
of heat released or taken in by a chemical reaction.
Endothermic processes are reactions that have a net
absorption of heat, whereas exothermic reactions have
a net release of heat. Energy diagrams for reaction
progress show this change. Reaction (a) in the diagram
shown in Figure 75 is exothermic. Reaction (b) is
endothermic. Note that a catalyzed reaction, which
we discussed earlier, has the same overall loss or gain
in thermal energy (heat released or taken in), which
is determined by the difference in the energies of
products and reactants.
 JOSEPH BLACK AND LATENT HEAT
The Scottish chemist Joseph Black, whom we discussed
earlier with regard to his discovery of carbon dioxide,
also made foundational contributions to the field of
thermochemistry, the branch of chemistry that focuses
on the quantities of heat evolved or absorbed during
chemical reactions. As early as the 1750s, Black began
to focus his research on the topic of heat. Like anyone
who has observed melting snow, Black understood
that even after the air temperature has risen above the
freezing point, a quantity of snow will not immediately
melt but rather will melt quite slowly.
To investigate why this is so, Black conducted an
experiment in which he observed one container filled
with five ounces of water at 33 °F in a room whose
temperature was 47 °F and a second container with five
ounces of ice at 32 °F. Black observed that in thirty
minutes time, the water had warmed to a temperature
of 40 °F. The ice, meanwhile, took ten and a half hours

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to warm to a temperature of 40 °F. In other words, the
ice took twenty-one times the amount of time to arrive
at the same temperature as the water. Therefore, Black
concluded that the ice absorbed 147 units of heat
(40 − 33) x 21 = 147. The water, by comparison, had
absorbed 8 units of heat. Black thus proposed that 139
units of heat (147−8) had been absorbed by the melting
ice and were in the water that had melted from the ice.20
Black conducted additional experiments in which he
came to better understand the concept of latent heat.
Although he never formally published his findings,
Black lectured on his discoveries, and he is credited
with being the first to describe latent heat—the heat The world’s first ice-calorimeter, which was used in 1782–83
that is added or lost when a substance changes its state, by Antoine Lavoisier and Pierre-Simon Laplace to determine
such as when water freezes and becomes solid ice or the heat evolved in various chemical changes. Their
evaporates and becomes steam. The latent heat involved calculations were based on Joseph Black’s prior discovery of
latent heat.
in the melting of a solid or the freezing of a liquid
is referred to as the heat of fusion. The latent heat
involved in vaporizing a liquid or solid or condensing a gas is called the heat of vaporization. Black’s findings
not only revolutionized our understanding of thermochemistry, but they also led to major changes in the world at
large. James Watt, the Scottish inventor of the steam engine—the advancement that drove much of the Industrial
Revolution—was a student and friend of Black’s who utilized the concept of latent heat to develop his invention.

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State Functions
State functions are properties of a system that are only
determined by where the system is, not how it arrived
there. Examples of state functions are volume, V, energy
content, E, and pressure, P. When a state function
quantity changes, chemists use the ∆ symbol to indicate
the amount of change. It is also true that for ∆V, ∆E, and
∆P, the pathway is not important; only the initial state
and the final state are important. It is usually easy to
measure a change of state function values, but it is not
easy to establish the absolute magnitude of some state
function parameters for a system.
The First Law of Thermodynamics
Systems have an energy content that can be tracked by
measuring the heat given off or taken in by a chemical
reaction. This energy content, called enthalpy, can be
assigned to individual chemical substances. Enthalpy is
a state function and is given the symbol H. Changes in
enthalpy are thus denoted ∆H. The enthalpy is directly
proportional to the amount (in moles) of chemical
present. If heat given off by a reaction is measured, the
total enthalpy change per mole can be assigned energy
units, usually kilojoules.
For example, if 1 mole of carbon (e.g., as coal) is
converted to 1 mole of carbon dioxide, then 393.5
kilojoules of energy are given off as heat. This is
known as a “heat of reaction.” Each compound can be
assigned an enthalpy change of formation or heat of
formation, (∆Hformation) if 1 mole of the compound is
made from its elements under standardized conditions.
The process by which these enthalpy changes are
measured is called calorimetry. For example, to
measure the heat of a reaction between an acid and a
base, the change in temperature of the reacting mixture
(ΔT) is measured. This change is compared to the
change in temperature of a sample of the same mass
of pure water as heat is added from a burner. Chemists
have established that it takes 4.18 joules of heat to raise
the temperature of 1.00 gram of water by 1.00 degree
Celsius, so they do not have to re-measure this each
time.
Hess’s Law
The Swiss-Russian chemist Germain Hess (1802–50)
formulated a principle known as Hess’s Law, which
states that the heat evolved or absorbed in a chemical
process is the same whether the process takes place in
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one or in several steps. This is essentially a restatement
of the law of conservation of energy (that everything
energy-wise must “add up”), and it is sometimes
referred to as the law of constant heat summation.
Hess’s law is especially useful for computing heat
(enthalpy) changes for chemical processes that have
not been measured directly. It can do this by using
tabulations of data from related reactions.
For example, it may be difficult to measure the
enthalpy of formation of carbon monoxide, CO. The
reaction equation for this process is as follows: C(s) +
½ O2(g) → CO(g), and ∆Hf (CO) is desired.
However, enthalpy for the formation of CO2 can easily
be measured as can the enthalpy of oxidation of CO
to CO2. The application of Hess’s Law, with all values
under standard conditions, enables us to make this
calculation.
If C(s) + O2(g) → CO2(g), ∆Hf = –393 kJ/mol, and CO
+ ½ O2 → CO2, ∆H = –283 kJ/mol, then subtracting
the second equation from the first gives us: C + ½ O2
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→ CO ∆Hf = –393 – (–283) = –110 kJ/mol.
The equation shows the enthalpy of formation of
CO to be –110 kJ/mol. Remember the negative sign
indicates that this reaction is exothermic (i.e., heat is
given to the surroundings). Many other examples of the
use of Hess’s law are provided in standard chemistry
textbooks and online.
The Second Law of Thermodynamics
The second law of thermodynamics involves the
idea of entropy or chaos. Chemists found that the
measurement of heat changes (enthalpy) alone was
insufficient to account for everything that happened
during chemical and physical changes of matter. So,
chemists associated an energy content with the actual
ordering process within and among the particles of
matter. A new state symbol, S, was defined for entropy,
which indicates the energy associated with disorder.
The smaller the entropy value is, the greater the order.
All natural processes result in an increase in entropy
for the universe, but not necessarily for the system.
Remember: System + Surroundings = Universe.
So, a decrease in entropy can occur in a system if a
matching increase occurs in the surroundings. Solids
are the most ordered state of matter; liquids are the
next most ordered, then solutions, and lastly gases are
 FIGURE 76
Factors affecting the sign of ∆G in the relationship ∆G = ∆H – T∆S.
Image from Chemistry, 7th edition, by Raymond Chang, published by McGraw-Hill, © 2002.
the most disordered.
The final decision as to whether or not a chemical
reaction will occur must be based on a consideration
of changes in both enthalpy (∆H) and entropy (ΔS).
Changes in these state functions can be positive or
negative, so signs are very important. J. W. Gibbs
(1839−1903), an early American chemist, determined
a simple relationship of enthalpy and entropy, and the
resultant state function is named in his honor. This
state function is Gibbs Free Energy, which has the
symbol G. We can now determine whether or not a
chemical reaction will occur by using the equation
connecting changes in G, H, and S, or: ∆G = ∆H –
TΔS, where T is the temperature (in Kelvin units).
The sign of ∆G determines if a reaction (as written left
to right) will be spontaneous or not. Because the signs
of the other terms can be known, and temperature is
always positive (+), we can establish the conditions
needed for a reaction to be spontaneous, as is shown
in the table in Figure 76. If ∆H is negative and ∆S is
positive, then the reaction occurs spontaneously. If
∆H is positive and ∆S is negative, then the reaction
is nonspontaneous. When both ∆H and ∆S have the
same sign, whether or not the reaction is spontaneous
depends upon the temperature.
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RELATIONSHIP OF CHANGE IN
FREE ENERGY TO EQUILIBRIUM
CONSTANTS AND ELECTRODE
POTENTIALS
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Free energy has a direct relationship to equilibrium
constants and electrode potentials. If a reaction has
a negative ∆G, then this indicates that the reaction
is spontaneous in the forward direction. A positive
galvanic cell voltage, E, also indicates that a reaction
is spontaneous in the forward direction. As a reaction
approaches equilibrium, its ∆G and E will approach
zero. At equilibrium, ∆G and E will be equal to zero.
For prediction purposes and to compare different
reactions, it is useful to consider values of ∆G and E
when reactants and products are all in their defined
“standard states.” Then, it is possible to say whether
a reaction from that condition will have a large (>1)
or small (<1) value for its equilibrium constant, and
we can determine the sign of its cell potential. These
results are summarized in the table shown in Figure 77.
The equation that allows us to change from free energy
to equilibrium constants at standard states is ∆G° =
–RTlnK. And, the equation to change to standard cell
potential is ∆G° = –nFE°cell. The negative signs allow
for a change from the negative value of free energy to
the corresponding positive values of K and E.
 FIGURE 77
Relationships among ∆G°, K, and E°cell .
Image from Chemistry, 7th edition, by Raymond Chang, published by McGraw-Hill, © 2002.
SECTION III SUMMARY
The starting substances in reactions are called

reactants, and the ending substances are called
products.
 Synthesis reactions combine substances
to make one product while decomposition
reactions start with one reactant and break it
apart.
 Double replacement reactions have two
reactants that trade anions to make new
products.
 Single replacements reactions have an atom
and a compound as reactants and then trade
to have a different atom and compound as
products.
 Metal atoms can replace metal ions based on
the activity series of the metals.
 Combustion reactions involve substances
reacting with oxygen. If the reaction is with an
organic molecule, the products will be carbon
dioxide and water.
 Antoine Lavoisier’s experiments led to the
naming of oxygen and a better understanding
of the process of combustion as well as the
principle of conservation of mass.
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 The pH scale is a measure used to define the
acidity of a water solution. Acidic solutions
have a pH that is lower than seven, and basic
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solutions have a pH that is greater than seven.
The Arrhenius and Brønsted-Lowry theories
can explain why some substances are acids and
others are bases.
 The equation for determining the pH is pH =
– log[H3O+], where H3O+ is called hydronium
or simply hydrogen ion concentration in pH =
–log[H+].
 An amphoteric substance can behave as either
an acid or a base. Water is an example of an
amphoteric substance.
 A titration is a method used when acids and
bases are mixed, and the pH is monitored as
different amounts react. A titration uses a piece
of equipment called a buret to measure the
volume of solution added.
 In a titration, when the amount of acid equals
the amount of base, the equivalence point
or endpoint has been reached. This can be
indicated by graphing, by using a pH indicator
that changes color at the appropriate pH, or by
using a pH meter.
 Salts are products of acid-base reactions. Salts
can be acidic, basic, or neutral depending upon
 the strength of the acid or base that was used
to make them. When a salt dissolves in water,
its ions interact with the water molecules—a
reaction called hydrolysis.
 Precipitation reactions involve two ionic
solutions being combined and an insoluble
product forming. The reactant ions that do
not change form (remain as ions) are called
spectator ions. There are solubility rules that
help predict whether a precipitate will form.
 Oxidation-reduction reactions, or redox
reactions, involve the transfer of electrons.
To determine which substance is freeing up
electrons (being oxidized) for another reacting
substance (being reduced) to use, the oxidation
numbers must be determined.
 Electrochemistry uses redox reactions to
perform many common types of useful
reactions, including those used in batteries and
electroplating.
 Cell potentials are the potential energy a
reaction has to do work. Cell potentials are
measured in volts. If the total voltage of a
reaction is positive, then the reaction will be
spontaneous.
 Oxidation occurs at the anode, and reduction
occurs at the cathode in an electrolytic cell.
 When a cell will not run because of a negative
potential, energy can be applied to make it run.
This process is called electrolysis.
 Luigi Brugnatelli is credited with developing
the modern process of electroplating, a process
in which an electrical current is passed
through a salt solution containing a metal ion,
depositing a thin coat of the metal onto the
surface of an object.
 The Nernst equation connects cell potentials
to free energy changes for chemical reactions
and can be used for any set of concentrations of
reactants and products at any temperature. The
most useful version of the equation is: E = E° –
(0.0592 log Q) / n.
 Using a balanced equation, stoichiometry is a
method of relating moles of one substance in
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the equation to moles of another substance in
the equation. Conversions can then be made
from moles to obtain masses in grams.
 Stoichiometry is used both to predict the yield
of reactions and to determine limiting reagents.
A limiting reagent is a substance that, because
of its starting amount, will limit the amount of
product that can be made.
 Joseph-Louis Proust established the law of
definite proportions, which states that elements
combine in defined ratios to form compounds.
 Some reactions do not go to completion
and instead run in both forward and reverse
directions. When the rate of the forward
reaction is equal to the rate of the reverse
reaction, the reaction is said to have reached
equilibrium.
 Reactions at equilibrium have a special number
that can be calculated, called an equilibrium
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constant, K. The formula for the equilibrium
constant for the general reaction aA + bB →
[C]c [D]d
cC + dD is: K =
[A]a [B]b
 Concentration values used in equilibrium
expressions are technically activities,
defined as a ratio of the concentration to the
concentration of a standard state, usually 1 M
for aqueous solutions or 1 atm for gases.
 The type of reaction determines if the value
is called a Ka (acid), Kb (base), Kp (gas),
Kc (concentration), or Ksp (precipitate). The
size of the number indicates which reaction
(forward or reverse) is more favored to occur. If
the constant is larger than 1, then the forward
reaction is favored. If the constant is less than
1, then the reverse reaction is favored. If the
constant is equal to 1, then they are equally
favorable.
 Reactions occur at different rates. Reaction
rates are studied in the field of kinetics. All
reactions have different factors that affect
their rate. By studying reactions, scientists
can determine rate laws that show how
concentrations affect the rates of reactions.
 Kinetics is understood using the collision
model. Collision theory states that molecules
need to collide with each other with the right
orientation and sufficient energy for a reaction
to occur. Some substances, called catalysts, can
speed up reactions by lowering the activation
energy needed for the reaction.
 Thermochemistry measures overall energy
changes in reactions. Reactions that absorb
energy are called endothermic, and reactions
that release energy are called exothermic.
 Calorimetry is a method of measuring the heat
of a reaction.
 Joseph Black revolutionized thermochemistry
with his experiments involving the concept of
latent heat, the heat released or absorbed by a
substance when it changes its phase or physical
state without changing its temperature.
 State functions are properties of systems where
the pathway is not important, but the beginning
and ending state are. Examples include
temperature, volume, pressure, enthalpy,
entropy, and free energy of systems.
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 Hess’s law states that the heat evolved or
absorbed in a chemical process is the same
whether the process takes place in one or in
several steps.
 The energy content of a system is called
enthalpy, and the disorder of a system is called
entropy.
 For enthalpy, entropy, and Gibbs Free Energy,
one is generally only interested in a change in
the value of these state functions (e.g., ΔH, ΔS,
and ΔG) rather than absolute values, which are
harder to obtain.
 Calculations of Gibbs Free Energy change
can be used to determine if a reaction will
be spontaneous. If the Gibbs Free Energy
change is negative, then the reaction will
occur. If it is equal to zero, then the reaction is
at equilibrium. And, if it is positive, then the
reaction will not occur. Different relationships
are used depending on the data that is
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available. If cell potential is known, then the
equation is ∆G° = –nFE°cell . If the equilibrium
constant is known, then the equation is ∆G°
= –RTlnK. And, if entropy and enthalpy are
known, then the equation is ∆G = ∆H – TΔS.
 Conclusion
Chemistry is the science of matter, involving the study
of how matter is structured and how those structures
can experience chemical and physical changes.
Chemistry has been both an art and a science. For
thousands of years, creative people experimented with
substances that occurred naturally on Earth and found
that these substances could be changed to improve
their appearance and to better function to benefit
human lives in both aesthetic and practical ways.
Individuals, especially Greek philosophers, created
theories to explain what was observed and came up
with ideas about the inner structure of matter.
It wasn’t until the seventeenth century that these early
theories about the nature and structure of matter
were further extended, as more precise methods
of measuring became available. As a result, many
“rules” by which nature operated became clear. In
the eighteenth century, Antoine Lavoisier and others,
working mostly in France and England, brought order
to the rapidly expanding field of experiments and
theories by proposing, among many other things, a
nomenclature system for chemical compounds and a
better explanation for combustion reactions.
Modern chemistry has since developed many methods
of exploring the properties of natural materials and
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many ways to manufacture new ones that are of
considerable benefit to human existence. Modern
chemists have refined the “rules” (physical laws) of
science, using theoretical models to enable reliable
predictions about the properties and behaviors
of materials. These successful models rely on a
consideration of how minute particles of matter interact
with each other through the application of only a few
types of force and using fundamental properties of
both waves and particles. Mathematics, with the aid of
fast computers, can turn these particulate models into
realistic representations of matter and its behaviors on
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the large scale at which people observe them.
In this resource guide, you have studied how such
models can explain or predict the way that matter
is shaped and held together by bonding and/or
intermolecular forces. You have learned how to
apply the models to rationalize the varied ways in
which matter can undergo both spontaneous and
nonspontaneous change, and you have learned what
determines the rates at which such changes happens.
You have also learned how different forms of energy,
including enthalpy and entropy, are involved in
determining the structures of matter and should now
better understand the laws governing changes among
those structures.
 Glossary

Absolute zero temperature – the theoretical as either an acid or base

temperature at which the volume of an ideal gas is
Anion– any negatively charged ion
zero and all molecular motion stops
Anode – the positive electrode of an electrolytic cell
Absorption spectrum– the spectrum produced when
and the site of oxidation
atoms absorb specific wavelengths of incoming
light and become excited from lower to higher Aqueous solution – a solution made by dissolving a
energy levels; this pattern of absorption can be substance in the solvent water
used in identifying an element.
Arrhenius, Svante – Swedish Nobel Laureate
Acids– a class of compounds that produce an excess chemist known for his theory on acids and bases
of hydrogen ions (H ) when in water solutions;
+
Atom – the smallest whole unit of an element that

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such solutions will test below 7 on the pH scale
contains a nucleus and electrons around the
Activation energy – in a collision of reactants, the nucleus and is neutrally charged
amount of energy required for a reaction to form
Atomic mass – the average mass of an atom of an
transition states and proceed to products
element; it is the weighted average of the isotopes
Activity series– an arrangement of metals sequenced based on the proportion of each isotope in a given
in decreasing order of their ability to act as a element sample.
reducing agent in aqueous solutions
Atomic mass unit– Abbreviated amu and also called
Alchemy − a practice that was particularly popular a Dalton, it is the mass equal to 1/12 the mass of a
during the Middle Ages that focused on trying to carbon-12 atom.
change other metals into gold or silver
Atomic number – the number of protons in the
Allotrope – one of several possible forms of an nucleus of an atom; this identifies the type of
element; for instance, carbon can be graphite, atom; for example, all atoms with seven protons
diamond, or buckminsterfullerene (commonly are nitrogen.
called “buckyballs”).
Atomic radius – half the distance between two
Alloy – a solid or liquid mixture of two or more adjacent atoms in an element’s crystal
metals; some common alloys include steel, brass,
Avogadro’s law − a gas law that states that equal
and bronze.
volumes of an ideal gas contain equal numbers of
Alpha decay – a type of radioactive decay where particles at constant temperature and pressure and
the nucleus emits two neutrons and two protons, thus the volume of a gas is directly proportional to
4
which is the equivalent of a helium nucleus, 2He 2+ the number of moles of the gas
Alpha particle – the helium nucleus, 42He2+, emitted Avogadro’s number − a number representing the
in an alpha decay number of atoms in 12.0 g of C-12; the number is
6.022 x 1023
Amphoteric– describes a substance that can behave

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82
Base– any substance that produces an excess of OH– Calx − the powdery substance that remains after a
ions in aqueous solution metal or mineral is burnt; now known as an oxide
Beta decay – radioactive atom decay that emits a Catalyst – a substance that increases the rate of a
charged particle; if this particle is negative, then chemical reaction by lowering the activation
it is an electron; if it is positive, then it is called a energy needed for the reaction by altering the
positron. reaction pathway
Beta particle – a negatively charged or positively Cathode – the negative electrode of an electrolytic
charged particle with the mass of an electron that cell and the site of reduction
is emitted in beta decay
Cation – any positively charged ion
Binary– describes a substance made of two elements
Cell potential – electromotive force (emf) or cell
Body-centered cubic– a unit cell of a crystal where voltage; the electrical potential difference between
there is a particle at each corner of a cube and one the two electrodes in an electrolytic cell
in the center
Charles’s law− a gas law that states that at constant
Bohr model of the atom– a model of the atom where pressure, the volume of a fixed amount of gas is
electrons orbit the nucleus like planets around the proportional to its absolute temperature
sun, but at predetermined distances; electrons can
Chemical bond – an attractive force that exists
transition from one orbit to a different empty one.
between two atoms such that the combination
Boiling point – the temperature at which the of atoms behaves as a unit that requires force

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vapor pressure of a liquid substance equals the (energy) to break apart
atmospheric pressure; normal boiling points are
Chemical formula – a written expression using
defined at 1 atmosphere of pressure.
symbols and subscripts to indicate the number
Boltzmann constant – defines the relation between and type of each atom in a chemical unit
absolute temperature and the kinetic energy
Chrome plating – the technique of electroplating a
contained in each molecule of an ideal gas; it is
thin layer of chrome onto an object
equal to 1.380649×10−23 J∙K−1.
Close-packed hexagonal – a crystal structure based
Boyle’s law – a gas law stating that the volume of a
on a hexagonal unit cell layering
gas is inversely proportional to its pressure when
the number of gas molecules and the temperature Colligative properties – physical properties of
remain constant; P1V1 = P2V2 solutions that depend on the ratio of the amount of
solute to the solvent
Brass – an alloy of primarily copper and zinc with
varying proportions of each metal Collision model – a model used to explain reaction
rates using the number of molecules colliding per
Brønsted-Lowry acid-base theory – an acid-base
second with a certain required minimum energy
theory based on the transfer of a proton; according
to this theory, an acid is a proton donor, and a base Combustion – a reaction involving oxygen as a
is a proton acceptor. reactant
Buret – a liquid measuring device used in titrations; Compound – a molecule that contains at least two
the liquid is dispensed through the bottom of the different elements that are chemically combined
device via a stopcock that opens and closes to in a fixed ratio
control the flow of liquid.
Concentration– the measurement of how much solute
Calorimetry– the measurement of heat evolution or is in a given amount of solution; depending on the
absorption in chemical reactions type of problem, different types of concentration

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 units can be used, such as molarity and molality. state decreases, and thus it is reduced.
Covalent bond– the sharing of a pair of electrons by Electrochemistry – the division of chemistry that
two atoms in a chemical bond studies the relationship between reactions and
electrical parameters such as voltage and current
Covalent network – an extended lattice formed of
covalent bonds, such as in SiO2 or diamond Electrolysis – the nonspontaneous splitting of a
substance by adding electrical energy; an example
Critical point – the endpoint of the liquid-gas curve
is the splitting of water into hydrogen and oxygen
on a phase diagram; it is the point at which a vapor
by applying a voltage and current.
and liquid become indistinguishable.
Electron – a fundamental particle of matter that has
Crystalline– a solid with a well-defined lattice shape
a negative charge; discovered by J. J. Thompson
due to an orderly arrangement of its particles
in 1896
within the solid
Electron affinity – the energy change, in kJ, when
Decomposition – a type of chemical reaction where
one mole of atoms of an element adds a mole of
a substance breaks down into simpler substances;
electrons (one per atom)
such reactions have one reactant and two or more
products. Electron “cloud” – the representation of the areas
occupied by electrons in the atom; the types of
Diffusion – the movement of one fluid through
electron clouds include ones with different shapes
another from an area of high concentration to an
called “orbitals.”
area of lower concentration

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Electronegativity – the ability of an atom to attract
Dipole – a polar molecule in which the centers of
shared electrons in relative units
positive and negative charge are separated
Electroplating – the deposition of a thin coat of a
Dipole moment– the product of one of the equal but
metal onto the surface of an object by passing
opposite charges on two atoms in a molecule and
an electrical current through a salt solution
the distance separating them
containing the metal ion to be deposited
Diprotic– describes an acid capable of donating two
Electrostatic force– a force created by the attraction
H+ ions per molecule; for example, sulfuric acid,
of oppositely charged ions or charged particles
H2SO4
Elements – the simplest type of substance with
Dispersion force – the intermolecular attraction
unique physical and chemical properties
between any two particles resulting from the
polarization of the electrons in the electron clouds; Emission spectrum – the line spectrum produced
also called London dispersion forces when excited atoms return to lower energy levels
and emit photons characteristic of the element;
Double replacement – the reaction of two ionic
the pattern of emission can be used in identifying
compounds to form two new ionic compounds
an element.
Ductile – the property of a metal that describes how
Empirical formula– a chemical formula reduced to
easily the metal can be pulled into a wire without
lowest terms; for example, C2H2 reduced to CH
breaking
Empiricism − the process of relying on experiments
Effusion – the process by which a gas escapes from
and observations in the natural sciences
its container through a tiny hole
Endothermic – describes a chemical reaction that
Electrochemical reduction – the transformation of
absorbs heat from the surroundings
metallic cations to metals by electron transfer;
when a substance gains an electron, its oxidation Endpoint – the point in an acid-base titration when

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 the pH indicator changes color system to a cooler system resulting in changes in
molecular motion; measured in kilojoules
Enthalpy – a thermodynamic quantity (H) that
measures the heat content under constant pressure Heat of formation– the enthalpy change that occurs
when a unit of mass of a compound is produced
Entropy – a thermodynamic quantity (S) that is a
from its elements
measure of the state of order in a substance
Heat of fusion − the enthalpy change that occurs
Equilibrium – the condition of a chemical reaction
when a unit of mass of a solid substance melts
when the forward rate and the reverse rate are
equal, so there is no apparent change Heat of vaporization − the enthalpy change that
occurs when 1 gram of a liquid substance
Equilibrium constant – the number obtained if
vaporizes
concentrations and/or pressures of the products
are divided by those of the reactants when the Homogenous – describes a solution that features a
reaction is at equilibrium. uniform dispersion of its components
Equivalence point– the point in a titration when the Hybridization – the process when electron orbitals
moles of the two reactants are equal; in an acid- like s and p mix together to form new orbitals such
base titration, the moles of H transferred equals
+
as sp; the total number of orbitals is conserved, so
the moles of OH . –
1s + 1p electron orbitals yields 2sp hybrids.
Exothermic – describes a reaction that releases heat Hydration – the process of being surrounded by
to the surroundings water solvent molecules; this process can also

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form solid crystals called hydrates.
Face-centered cubic – describes a crystal structure
that has atoms at each corner of the cube and six Hydrogen bond – a type of dipole-dipole force
atoms at each face of the cube between molecules involving the attraction of
a hydrogen, which is bound to one strongly
Force – mass x acceleration or time derivative of
electronegative atom, either a nitrogen, oxygen, or
momentum; force creates change in a physical
fluorine atom in another molecule; for example,
system.
the bond that occurs when the hydrogen in a water
Galvanic electrochemical cell – a spontaneous molecule is attracted to the nitrogen atom in an
reaction used to generate electrical potential ammonia molecule.
(voltage) and deliver energy
Hydronium ion – a hydrogen ion (H+) bonded to a
Gas – a state of matter characterized by molecules water molecule in hydration to form H3O+
being spread out from each other and therefore
Ideal gas equation – an equation that relates
highly compressible; takes the shape of any
temperature, pressure, volume, and moles of gas
container it is in, creating uniform pressure in all
together (PV=nRT)
directions
Induced dipole – a weak attraction that results from
Gibbs Free Energy– a thermodynamic quantity that
a polar molecule inducing a dipole in an atom
indicates whether a reaction will be spontaneous
or in a nonpolar molecule by disturbing electron
and how much work it can do; a spontaneous
arrangement of the nonpolar species
reaction has a release of free energy (∆G) found
from the equation ∆G = ∆H–T∆S, where ∆H is the Insoluble – describes a substance that does not
enthalpy change, and ∆S is the entropy change. dissolve in a solvent such as water
Group– a column on the periodic table; for example, Instantaneous rate– the rate of a reaction at any one
alkali metals (group 1) or noble gases (group 18) point in time
Heat – an amount of energy transferred from a hot Insulator – any substance with a low thermal

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 conductivity and/or low electrical conductivity
Intermolecular force– the type of force that attracts
one molecule to another molecule
Intramolecular force– the force in a bond that holds
the atoms within a molecule together
Ion– a charged particle formed when an atom either
gives up one or more electrons or gains one or
more electrons
Ionic bonds – bonds that occur between two
oppositely charged ions
Ionic lattice – an arrangement formed of alternating
cations and anions in an ionic crystal
Ionization energy– the amount of energy needed to
remove a mole of electrons from a mole of atoms
(one electron per atom) in the gaseous state; Limiting reactant (limiting reagent) – the reactant
measured in kilojoules per mole
Isotope – an alternate form of the same element that
has a different mass number due to its having a London dispersion force– see dispersion force
that a compound is always composed of the same
elements in the same ratio according to mass
Law of multiple proportions − a mass law that
states if two elements react to form more than
one compound, the masses of one element will
combine with the other element in a whole number
ratio
Law of partial pressures− a law stating that the total
pressure of a mixture of gases is the sum of the
pressures of the individual gases in the mixture
Lewis structures– a structural formula representation
used to depict the arrangement of atoms, electrons,
and bonds in a molecule using dots to represent
electrons and a line to represent the sharing of an
electron pair
in a reaction that determines the maximum
amount of product that can be made

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different number of neutrons
Lustrous – refers to the appearance of a substance’s
Kelvin– a scale that is the SI (international system of surface in reflected light; metals have luster.
units) unit of temperature; the lowest temperature
Malleable – describes the property of a substance
is zero K; water boils at 373K
indicating it can easily be flattened into thin sheets
Kinetic energy – the energy of any particle of matter
Mass number – the total number of protons and
due to its motion
neutrons in the nucleus of an atom
Kinetic-molecular theory– a model of gas behavior
Mass spectrometer– an instrument used to measure
that explains how the random motion of particles
the relative masses of ions
gives gas volume and pressure; it also explains
rates of diffusion and effusion of gases. Melting point– the temperature at which a substance
transitions from a solid to a liquid; usually
Kinetics– a branch of chemistry that studies the rates
measured at 1 atmosphere of pressure
of reactions
Metallic bond – a type of bond that forms between
Latent heat − the heat released or absorbed by a
metal atoms in a solid metal, where the atoms act
substance when it changes its phase or physical
as if positive ions form and electrons are mobile
state (e.g., from a solid to a liquid) without
in a “sea” and so can conduct an electric charge
changing its temperature
Mixture – two or more substances that are
Law of conservation of mass − In any chemical
intermingled with each other but not chemically
reaction, the total amount of matter of the
bonded together
reactants is equal to the total amount of matter of
the products, and thus no mass is lost or gained as Molar mass– the mass of one mole of entities (atoms,
substances change in a reaction. molecules, or formula units) of a substance; given
in units of g/mol
Law of definite proportions − the law that states

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Molality – a measure of concentration in moles of
solute per kilogram of solvent
Molarity – a measure of concentration in moles of
solute per liter of solution
Mole– the amount of a substance containing 6.022 x
1023 particles of the substance
Mole fraction– a measure of concentration based on
the number of moles of one substance compared
to the total number of moles of all substances
present
Molecular orbital theory – a model that describes
a molecule as a collection of nuclei and electrons
in which the electrons occupy orbitals that extend
over the entire molecule
Molecular solid – a solid held together by weak
intermolecular forces between the molecules;
typical molecular solids have relatively low
melting points and boiling points.
fully surrounded by hydrogen atoms; the chemical
formula for octane is C8H18.
Orbital – in an atom, the area in space around the
nucleus where an electron is found; each orbital
holds only one or two electrons.
Organic – describes compounds in which carbon is
bonded, often to itself, in chains or rings; organic
compounds usually contain many hydrogen
atoms.
Oxidation number – the number of electrons that
must be added to or subtracted from an atom
of an element in a compound to convert it to its
elemental state of zero charge
Oxidation-reduction– a type of reaction where one
reactant loses one or more electrons while another
reactant gains those electrons; often abbreviated
“redox”
Oxidation state– essentially equivalent to oxidation
number (see above); the number that indicates the

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Molecule – a compound consisting of two or more
oxidation state is equal to the effective charge on
atoms held together by a chemical bond
an atom.
Net ionic equation – a type of chemical equation
Period – a row on the periodic table; period 1 has
where spectator ions have been eliminated to
only H and He
highlight the actual chemical reaction taking place
Periodic table – a table showing all the elements,
Neutron – a fundamental particle of matter found
symbols, and masses arranged into seven rows and
in the nucleus that has a mass of 1.009 amu but
eighteen columns according to increasing proton
no electric charge; first identified by Sir James
number and similar electron configurations
Chadwick in 1932
pH – a number scale that indicates whether a solution
Nonpolar molecules – a molecule without a net
is acidic or basic; in aqueous solutions, a pH below
permanent dipole
seven indicates an acid while a pH above seven
Nonspontaneous– describes a reaction that does not indicates a base
naturally occur in the direction indicated (from
pH indicator – a species that has a different color
left to right)
at different pH values, typically one color in acid
Nucleus – the very dense positively charged center and a different color in base; this color change can
part of the atom that contains the protons and indicate the endpoint of a reaction.
neutrons and, consequently, most of the mass of
pH meter – an instrument used to indicate the pH of
the atom
a solution
Nuclide– a nuclear species of an atom characterized
Phase – a state of matter such as a solid, liquid, or gas
by mass (protons + neutrons), charge (protons),
and energy content Phase diagram – a diagram that shows the temperature
and pressure conditions of a pure substance as it
Octane – a hydrocarbon with eight carbons in its
changes from one state of matter to another
chain, all of which are single bonded together and

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Phlogiston theory − an incorrect theory of Radioactive atom– an atom whose nucleus will break
combustion that posited that when a substance up to form a more stable arrangement of the nuclear
is burned, it releases an undetectable substance particles; natural or artificial transmutation was
called phlogiston first discovered by Antoine Henri Becquerel in
1896; radioactivity is not affected by the chemical
Photoelectric effect – the emission of an electron
state of the atom, and thus processes like burning
from a metal’s surface as a result of the absorption
do not destroy an atom’s radioactivity.
of a photon (electromagnetic radiation); this
phenomenon was first explained by Albert Radioactive decay – the process through which an
Einstein; the amount of energy varies depending atomic species transmutates into a new species;
on the metal and the wavelength of the photon. for instance, U-238 decays initially to thorium-234
and then through a series of steps into Pb-206.
Photon– a discrete unit or quantum of electromagnetic
radiation; forms include microwaves, light waves, Rate law – an equation that shows the factors that
X rays, and gamma rays; photons are emitted affect the rate of the reaction and how they affect it
when electrons move from one energy state to
Reactants – the starting substances in a chemical
another in an atom, for example, when an excited
reaction
electron drops from the sixth energy level to the
second energy level; the energy released to make Redox– see oxidation-reduction
the change is the energy of the emitted photon.
Rotational motion – the movement of a molecule
Polar molecule– a molecule with an unequal overall circling around its central atom or the movement
distribution of permanent positive and negative of an individual group within a molecule rotating

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charge; such a molecule has a net dipole moment
that is not equal to zero.
Potential energy diagram – a diagram that shows
the energy of the reactants, the activation energy,
and the energy of the products in relationship
to one other; this type of diagram can show if a
reaction is endothermic or exothermic and how
fast the reaction will occur.
Precipitate – the insoluble product of a precipitation
reaction
Precipitation reaction – a reaction of two soluble
ionic solutions that when combined form an
insoluble product called a precipitate
Products – the substances that are formed in a
chemical reaction
Proton – a subatomic particle found in the nucleus
that has a positive charge and a mass of 1.008 amu
Quantum– the smallest possible unit of energy; this
unit can apply to any form of energy.
Quantum Mechanical Model – a model of the
atom that explains the presence of electrons as
“stationary” waves in orbitals
about a bond
Salt– an ionic compound resulting from the reaction
between an acid and base; sodium chloride and
lithium fluoride are both salts; sodium chloride is
often referred to as “common salt” or just “salt.”
Saturated solution – a solution containing the
maximum amount of solute that can be dissolved
at a given temperature
Scientific Revolution− a term often used to describe
the emergence of modern science during the
sixteenth and seventeenth centuries; much current
scholarship questions the concept of a Scientific
Revolution.
Single replacement – a type of reaction where an
element combines with a compound, and the
element displaces a species in the compound that
then becomes an element.
Solubility– the maximum amount of a solute that can
dissolve in a solvent at a particular temperature;
often expressed in grams per liter
Soluble – describes the ability of a solute to dissolve
in a solvent at a particular temperature

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Solute– the substance being dissolved in a solvent to measure of the thermal (motion) energy content
form a solution of a system
Solution – a homogeneous (uniformly dispersed) Temporary dipoles – a momentary induced dipole
mixture created when a polar molecule distorts the electron
cloud of a nonpolar molecule
Solvent – the substance doing the dissolving in a
solution; the solvent generally constitutes the Thermochemistry – a branch of chemistry focusing
main component of a solution on the heat transferred during chemical reactions
Sonorous– producing sound Thermodynamics – the study of the mathematical
relationships among work, temperature, and
Spectator ions – ions that are not involved in a
different forms of energy in chemical systems,
reaction but are in the solution
especially chemical reactions
Spontaneous– a reaction that occurs naturally
Titration– a method used in chemistry to determine
Stalactites – formations in a cave that descend from an unknown concentration of a substance by
the ceiling and are made of calcium carbonate and comparing it with another substance; typically
other minerals used with acid and base solutions
Stalagmites – formations in a cave that grow upward Toxic – describes substances that can cause damage
from the floor due to dripping minerals, including to living tissue, especially upon ingestion or
calcium carbonate inhalation

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State function – a property of a system that is Translational motion – the net movement of an
determined by its current state and not how it got object through space (in a solid, liquid, or gas),
there; volume, V, is an example of a state function; excluding vibration or rotation
since chemistry mostly involves studying change,
Transmutation – the natural or artificial process
it often focuses on change in a state function;
of changing an atom from one type of atom to
this also does not depend on the pathway; for
another as the result of a nuclear reaction; in
instance, only Vinitial and the Vfinal are important for
alchemy, the act of changing a substance from
determining ∆V.
one form or state to another; alchemists believed
Steel – a metal alloy made with primarily iron that base metals could be changed into precious
and carbon whose composition varies; other metals such as silver and gold.
components can include nickel, chromium, cobalt,
Triple point – the one temperature and pressure at
molybdenum, or zirconium.
which all three phases of a substance (solid, liquid,
Stoichiometry – the establishment and use of mass- and gas) exist at the same time in equilibrium with
mole relationships in balanced chemical equations each other
STP – standard temperature and pressure for a gas Triprotic – describes an acid that has the ability to
which is at 0 °C (273K) and 1 atm donate three protons (H+ ions); for example, H3PO4
Supercritical fluid – a dense gas that is above its Valence electrons – the outermost electrons in an
critical temperature and pressure and behaves as atom that are used in bonding
a viscous fluid
Valence Shell Electron Pair Repulsion (VSEPR)
Synthesis – a type of reaction where two or more model – a model that is used to explain or
reactants make a new product predict the shape of many molecules and ions by
minimizing electron pair repulsions around the
Temperature – a measure of how hot or cold a
central atom
substance is relative to another substance; a

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Van der Waals force – weak forces of attraction energy difference between two electrodes when
between atoms or molecules that result from no current is flowing
permanent or temporary electrostatic forces
Volts– the SI unit of electrical potential
Vibrational motion – the motion of two atoms in
Volume – the space occupied completely by a sample
a molecule that results from the stretching or
of matter
bending of a bond in the molecule
Yield– the amount of product made in a reaction
Voltage – (or cell voltage) the electrical potential

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APPENDIX: PERIODIC TABLE OF THE ELEMENTS

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 Notes
1 Steven Shapin, The Scientific Revolution, 2nd Edition (Chicago: The
University of Chicago Press, 2018) 3−4.
2 Ibid. 4.
3 Argonne National Laboratory, EVS, “Carbon-14,” Human Health Fact
Sheet (August 2005) 7 December 2021 https://remm.hhs.gov/ANL_
ContaminantFactSheets_All_070418.pdf.
4 “Fact Sheet #26: Cobalt-60,” Washington State Department of Health:
Division of Environmental Health Office of Radiation Protection (July
2002) 7 December 2021 https://www.doh.wa.gov/portals/1/Documents/
Pubs/320-078_co60_fs.pdf.
5 Jim Clark, “Electronegativity,” Chemguide (2000) 7 December 2021
http://www.chemguide.co.uk/atoms/bonding/electroneg.html.
6 Michael Blaber, “Resonance Structures,” Basic Concepts of Chemical
Bonding (1996) 7 December 2021 http://www.mikeblaber.org/oldwine/
chm1045/notes/Bonding/Resonan/Bond07.htm.
7 Askel L. Hallin, “What is a neutrino,” Scientific American 7 September
1999, Accessed 7 December 2021 https://www.scientificamerican.com/
article/what-is-a-neutrino/.
8 John B. West, “Carl Wilhelm Scheele, the discoverer of oxygen, and a
very productive chemist,” American Journal of Physiology 1 December
2014.
9 Ian C. Stewart and Justin P. Lomont, The Handy Chemistry Answer
Book (Caton, MI: Visible Ink Press, 2014) 9.
10 J ohn B. West, “Carl Wilhelm Scheele, the discoverer of oxygen, and a
very productive chemist,” American Journal of Physiology 1 December
2014.
11 “Metal Structures,” Dr.Chung Chieh’s Applied Chemistry Course
Website, University of Waterloo, 13 October 2008.
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12 “3-D Crystal Lattice Images,” Building a Physics Education Network by
Using the World Wide Web, 13 October 2008.
13 Martin S. Silberberg, Chemistry: The Molecular Nature of Matter and
Change, 4th Edition (New York: McGraw Hill, 2006) 8.
14 O rtus medicinae, published 1648, English translation, Oriatrike or
Physick Refined, published 1662. Quoted in Partington, James R. A
Short History of Chemistry (Mineola: Dover, 1989).
15 “The Leuven Local Heroes in Thermal Sciences and Engineering,”
Katholieke Universiteit Leuven (1999) 13 October 2008 http://people.
mech.kuleuven.be/~erik/local_heroes.html; and “Inspired by the Art
of Fire,” Chemistry Chronicles, American Chemistry Society, (Aug.
2004) 1 October 2021 http://pubs.acs.org/subscribe/journals/tcaw/13/i08/
pdf/804chronicles.pdf?sessid=1314#search=%22Jan%20Baptista%20
Van%20Helmont%20%22.
16 Derek B. Lowe, The Chemistry Book: From Gunpower to Graphene,
250 Milestones in the History of Chemistry (New York: Sterling
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Publishing, 2016) 86.
17 “Alessandro Volta, Electric Battery,” Lemelson-MIT, 30 January 2022,
https://lemelson.mit.edu/resources/ alessandro-volta.
18 Ian Stewart and Justin P. Lomont, The Handy Chemistry Answer Book
(Canton, MI: Visible Ink Press, 2014) 107.
19 Students should be aware that while Proust’s law is very widely
applicable, it is not true for every case—there are nonstoichiometric
compounds that are comprised of elements in varying ratios.
20 h ttps://journals.physiology.org/doi/full/10.1152/ajplung.00020.2014#B13
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