2022/3/8 16:42 chemistry -- Britannica Online Encyclopedia

chemistry
chemistry, the science that deals with
TABLE OF CONTENTS
the properties, composition, and
structure of substances (defined as Introduction
elements and compounds), the
The scope of chemistry
transformations they undergo, and the
The methodology of chemistry
energy that is released or absorbed
Chemistry and society
during these processes. Every substance,
The history of chemistry
whether naturally occurring or artificially
produced, consists of one or more of the
hundred-odd species of atoms that have been identified as elements.
Although these atoms, in turn, are composed of more elementary particles,
they are the basic building blocks of chemical substances; there is no
quantity of oxygen, mercury, or gold, for example, smaller than an atom of
that substance. Chemistry, therefore, is concerned not with the subatomic
domain but with the properties of atoms and the laws governing their
combinations and how the knowledge of these properties can be used to
achieve specific purposes.

The great challenge in chemistry is the development of a coherent

explanation of the complex behaviour of materials, why they appear as they
do, what gives them their enduring properties, and how interactions among
different substances can bring about the formation of new substances and
the destruction of old ones. From the earliest attempts to understand the
material world in rational terms, chemists have struggled to develop
theories of matter that satisfactorily explain both permanence and change.
The ordered assembly of indestructible atoms into small and large
molecules, or extended networks of intermingled atoms, is generally
accepted as the basis of permanence, while the reorganization of atoms or
molecules into different arrangements lies behind theories of change. Thus
chemistry involves the study of the atomic composition and structural
architecture of substances, as well as the varied interactions among
substances that can lead to sudden, often violent reactions.

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Chemistry also is concerned with the utilization of natural substances and

the creation of artificial ones. Cooking, fermentation, glass making, and
metallurgy are all chemical processes that date from the beginnings of
civilization. Today, vinyl, Teflon, liquid crystals, semiconductors, and
superconductors represent the fruits of chemical technology. The 20th
century saw dramatic advances in the comprehension of the marvelous and
complex chemistry of living organisms, and a molecular interpretation of
health and disease holds great promise. Modern chemistry, aided by
increasingly sophisticated instruments, studies materials as small as single
atoms and as large and complex as DNA (deoxyribonucleic acid), which
contains millions of atoms. New substances can even be designed to bear
desired characteristics and then synthesized. The rate at which chemical
knowledge continues to accumulate is remarkable. Over time more than
8,000,000 different chemical substances, both natural and artificial, have
been characterized and produced. The number was less than 500,000 as
recently as 1965.

Intimately interconnected with the intellectual challenges of chemistry are

those associated with industry. In the mid-19th century the German chemist
Justus von Liebig commented that the wealth of a nation could be gauged
by the amount of sulfuric acid it produced. This acid, essential to many
manufacturing processes, remains today the leading chemical product of
industrialized countries. As Liebig recognized, a country that produces large
amounts of sulfuric acid is one with a strong chemical industry and a strong
economy as a whole. The production, distribution, and utilization of a wide
range of chemical products is common to all highly developed nations. In
fact, one can say that the “iron age” of civilization is being replaced by a
“polymer age,” for in some countries the total volume of polymers now
produced exceeds that of iron.

The scope of chemistry

The days are long past when one person could hope to have a detailed
knowledge of all areas of chemistry. Those pursuing their interests into
specific areas of chemistry communicate with others who share the same
interests. Over time a group of chemists with specialized research interests
become the founding members of an area of specialization. The areas of

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specialization that emerged early in the history of chemistry, such as

organic, inorganic, physical, analytical, and industrial chemistry, along with
biochemistry, remain of greatest general interest. There has been, however,
much growth in the areas of polymer, environmental, and medicinal
chemistry during the 20th century. Moreover, new specialities continue to
appear, as, for example, pesticide, forensic, and computer chemistry.

Analytical chemistry
Most of the materials that occur on Earth, such as wood, coal, minerals, or
air, are mixtures of many different and distinct chemical substances. Each
pure chemical substance (e.g., oxygen, iron, or water) has a characteristic set
of properties that gives it its chemical identity. Iron, for example, is a
common silver-white metal that melts at 1,535° C, is very malleable, and
readily combines with oxygen to form the common substances hematite and
magnetite. The detection of iron in a mixture of metals, or in a compound
such as magnetite, is a branch of analytical chemistry called qualitative
analysis. Measurement of the actual amount of a certain substance in a
compound or mixture is termed quantitative analysis. Quantitative analytic
measurement has determined, for instance, that iron makes up 72.3 percent,
by mass, of magnetite, the mineral commonly seen as black sand along
beaches and stream banks. Over the years, chemists have discovered
chemical reactions that indicate the presence of such elemental substances
by the production of easily visible and identifiable products. Iron can be
detected by chemical means if it is present in a sample to an amount of 1
part per million or greater. Some very simple qualitative tests reveal the
presence of specific chemical elements in even smaller amounts. The yellow
colour imparted to a flame by sodium is visible if the sample being ignited
has as little as one-billionth of a gram of sodium. Such analytic tests have
allowed chemists to identify the types and amounts of impurities in various
substances and to determine the properties of very pure materials.
Substances used in common laboratory experiments generally have impurity
levels of less than 0.1 percent. For special applications, one can purchase
chemicals that have impurities totaling less than 0.001 percent. The
identification of pure substances and the analysis of chemical mixtures
enable all other chemical disciplines to flourish.

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The importance of analytical chemistry has never been greater than it is

today. The demand in modern societies for a variety of safe foods,
affordable consumer goods, abundant energy, and labour-saving
technologies places a great burden on the environment. All chemical
manufacturing produces waste products in addition to the desired
substances, and waste disposal has not always been carried out carefully.
Disruption of the environment has occurred since the dawn of civilization,
and pollution problems have increased with the growth of global
population. The techniques of analytical chemistry are relied on heavily to
maintain a benign environment. The undesirable substances in water, air,
soil, and food must be identified, their point of origin fixed, and safe,
economical methods for their removal or neutralization developed. Once the
amount of a pollutant deemed to be hazardous has been assessed, it
becomes important to detect harmful substances at concentrations well
below the danger level. Analytical chemists seek to develop increasingly
accurate and sensitive techniques and instruments.

Sophisticated analytic instruments, often coupled with computers, have

improved the accuracy with which chemists can identify substances and
have lowered detection limits. An analytic technique in general use is gas
chromatography, which separates the different components of a gaseous
mixture by passing the mixture through a long, narrow column of absorbent
but porous material. The different gases interact differently with this
absorbent material and pass through the column at different rates. As the
separate gases flow out of the column, they can be passed into another
analytic instrument called a mass spectrometer, which separates substances
according to the mass of their constituent ions. A combined gas
chromatograph–mass spectrometer can rapidly identify the individual
components of a chemical mixture whose concentrations may be no greater
than a few parts per billion. Similar or even greater sensitivities can be
obtained under favourable conditions using techniques such as atomic
absorption, polarography, and neutron activation. The rate of instrumental
innovation is such that analytic instruments often become obsolete within
10 years of their introduction. Newer instruments are more accurate and
faster and are employed widely in the areas of environmental and medicinal
chemistry.

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Inorganic chemistry
Modern chemistry, which dates more or less from the acceptance of the law
of conservation of mass in the late 18th century, focused initially on those
substances that were not associated with living organisms. Study of such
substances, which normally have little or no carbon, constitutes the
discipline of inorganic chemistry. Early work sought to identify the simple
substances—namely, the elements—that are the constituents of all more
complex substances. Some elements, such as gold and carbon, have been
known since antiquity, and many others were discovered and studied
throughout the 19th and early 20th centuries. Today, more than 100 are
known. The study of such simple inorganic compounds as sodium chloride
(common salt) has led to some of the fundamental concepts of modern
chemistry, the law of definite proportions providing one notable example.
This law states that for most pure chemical substances the constituent
elements are always present in fixed proportions by mass (e.g., every 100
grams of salt contains 39.3 grams of sodium and 60.7 grams of chlorine).
The crystalline form of salt, known as halite, consists of intermingled sodium
and chlorine atoms, one sodium atom for each one of chlorine. Such a
compound, formed solely by the combination of two elements, is known as
a binary compound. Binary compounds are very common in inorganic
chemistry, and they exhibit little structural variety. For this reason, the
number of inorganic compounds is limited in spite of the large number of
elements that may react with each other. If three or more elements are
combined in a substance, the structural possibilities become greater.

After a period of quiescence in the early part of the 20th century, inorganic
chemistry has again become an exciting area of research. Compounds of
boron and hydrogen, known as boranes, have unique structural features that
forced a change in thinking about the architecture of inorganic molecules.
Some inorganic substances have structural features long believed to occur
only in carbon compounds, and a few inorganic polymers have even been
produced. Ceramics are materials composed of inorganic elements
combined with oxygen. For centuries ceramic objects have been made by
strongly heating a vessel formed from a paste of powdered minerals.
Although ceramics are quite hard and stable at very high temperatures, they
are usually brittle. Currently, new ceramics strong enough to be used as
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turbine blades in jet engines are being manufactured. There is hope that
ceramics will one day replace steel in components of internal-combustion
engines. In 1987 a ceramic containing yttrium, barium, copper, and oxygen,
with the approximate formula YBa Cu O , was found to be a
2 3 7
superconductor at a temperature of about 100 K. A superconductor offers
no resistance to the passage of an electrical current, and this new type of
ceramic could very well find wide use in electrical and magnetic applications.
A superconducting ceramic is so simple to make that it can be prepared in a
high school laboratory. Its discovery illustrates the unpredictability of
chemistry, for fundamental discoveries can still be made with simple
equipment and inexpensive materials.

Many of the most interesting developments in inorganic chemistry bridge

the gap with other disciplines. Organometallic chemistry investigates
compounds that contain inorganic elements combined with carbon-rich
units. Many organometallic compounds play an important role in industrial
chemistry as catalysts, which are substances that are able to accelerate the
rate of a reaction even when present in only very small amounts. Some
success has been achieved in the use of such catalysts for converting natural
gas to related but more useful chemical substances. Chemists also have
created large inorganic molecules that contain a core of metal atoms, such
as platinum, surrounded by a shell of different chemical units. Some of these
compounds, referred to as metal clusters, have characteristics of metals,
while others react in ways similar to biologic systems. Trace amounts of
metals in biologic systems are essential for processes such as respiration,
nerve function, and cell metabolism. Processes of this kind form the object
of study of bioinorganic chemistry. Although organic molecules were once
thought to be the distinguishing chemical feature of living creatures, it is
now known that inorganic chemistry plays a vital role as well.

Organic chemistry
Organic compounds are based on the chemistry of carbon. Carbon is unique
in the variety and extent of structures that can result from the three-
dimensional connections of its atoms. The process of photosynthesis
converts carbon dioxide and water to oxygen and compounds known as
carbohydrates. Both cellulose, the substance that gives structural rigidity to
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plants, and starch, the energy storage product of plants, are polymeric
carbohydrates. Simple carbohydrates produced by photosynthesis form the
raw material for the myriad organic compounds found in the plant and
animal kingdoms. When combined with variable amounts of hydrogen,
oxygen, nitrogen, sulfur, phosphorus, and other elements, the structural
possibilities of carbon compounds become limitless, and their number far
exceeds the total of all nonorganic compounds. A major focus of organic
chemistry is the isolation, purification, and structural study of these naturally
occurring substances. Many natural products are simple molecules.
Examples include formic acid (HCO H) in ants, ethyl alcohol (C H OH) in
2 2 5
fermenting fruit, and oxalic acid (C H O ) in rhubarb leaves. Other natural
2 2 4
products, such as penicillin, vitamin B , proteins, and nucleic acids, are
12
exceedingly complex. The isolation of pure natural products from their host
organism is made difficult by the low concentrations in which they may be
present. Once they are isolated in pure form, however, modern instrumental
techniques can reveal structural details for amounts weighing as little as
one-millionth of a gram. The correlation of the physical and chemical
properties of compounds with their structural features is the domain of
physical organic chemistry. Once the properties endowed upon a substance
by specific structural units termed functional groups are known, it becomes
possible to design novel molecules that may exhibit desired properties. The
preparation, under controlled laboratory conditions, of specific compounds
is known as synthetic chemistry. Some products are easier to synthesize than
to collect and purify from their natural sources. Tons of vitamin C, for
example, are synthesized annually. Many synthetic substances have novel
properties that make them especially useful. Plastics are a prime example, as
are many drugs and agricultural chemicals. A continuing challenge for
synthetic chemists is the structural complexity of most organic substances.
To synthesize a desired substance, the atoms must be pieced together in the
correct order and with the proper three-dimensional relationships. Just as a
given pile of lumber and bricks can be assembled in many ways to build
houses of several different designs, so too can a fixed number of atoms be
connected together in various ways to give different molecules. Only one
structural arrangement out of the many possibilities will be identical with a
naturally occurring molecule. The antibiotic erythromycin, for example,
contains 37 carbon, 67 hydrogen, and 13 oxygen atoms, along with one
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nitrogen atom. Even when joined together in the proper order, these 118
atoms can give rise to 262,144 different structures, only one of which has
the characteristics of natural erythromycin. The great abundance of organic
compounds, their fundamental role in the chemistry of life, and their
structural diversity have made their study especially challenging and
exciting. Organic chemistry is the largest area of specialization among the
various fields of chemistry.

Biochemistry
As understanding of inanimate chemistry grew during the 19th century,
attempts to interpret the physiological processes of living organisms in
terms of molecular structure and reactivity gave rise to the discipline of
biochemistry. Biochemists employ the techniques and theories of chemistry
to probe the molecular basis of life. An organism is investigated on the
premise that its physiological processes are the consequence of many
thousands of chemical reactions occurring in a highly integrated manner.
Biochemists have established, among other things, the principles that
underlie energy transfer in cells, the chemical structure of cell membranes,
the coding and transmission of hereditary information, muscular and nerve
function, and biosynthetic pathways. In fact, related biomolecules have been
found to fulfill similar roles in organisms as different as bacteria and human
beings. The study of biomolecules, however, presents many difficulties. Such
molecules are often very large and exhibit great structural complexity;
moreover, the chemical reactions they undergo are usually exceedingly fast.
The separation of the two strands of DNA, for instance, occurs in one-
millionth of a second. Such rapid rates of reaction are possible only through
the intermediary action of biomolecules called enzymes. Enzymes are
proteins that owe their remarkable rate-accelerating abilities to their three-
dimensional chemical structure. Not surprisingly, biochemical discoveries
have had a great impact on the understanding and treatment of disease.
Many ailments due to inborn errors of metabolism have been traced to
specific genetic defects. Other diseases result from disruptions in normal
biochemical pathways.

Frequently, symptoms can be alleviated by drugs, and the discovery, mode

of action, and degradation of therapeutic agents is another of the major

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areas of study in biochemistry. Bacterial infections can be treated with

sulfonamides, penicillins, and tetracyclines, and research into viral infections
has revealed the effectiveness of acyclovir against the herpes virus. There is
much current interest in the details of carcinogenesis and cancer
chemotherapy. It is known, for example, that cancer can result when cancer-
causing molecules, or carcinogens as they are called, react with nucleic acids
and proteins and interfere with their normal modes of action. Researchers
have developed tests that can identify molecules likelyto be carcinogenic.
The hope, of course, is that progress in the prevention and treatment of
cancer will accelerate once the biochemical basis of the disease is more fully
understood.

The molecular basis of biologic processes is an essential feature of the fast-

growing disciplines of molecular biology and biotechnology. Chemistry has
developed methods for rapidly and accurately determining the structure of
proteins and DNA. In addition, efficient laboratory methods for the synthesis
of genes are being devised. Ultimately, the correction of genetic diseases by
replacement of defective genes with normal ones may become possible.

Polymer chemistry
The simple substance ethylene is a gas composed of molecules with the
formula CH CH . Under certain conditions, many ethylene molecules will
2 2
join together to form a long chain called polyethylene, with the formula
(CH CH ) , where n is a variable but large number. Polyethylene is a tough,
2 2n
durable solid material quite different from ethylene. It is an example of a
polymer, which is a large molecule made up of many smaller molecules
(monomers), usually joined together in a linear fashion. Many naturally
occurring substances, including cellulose, starch, cotton, wool, rubber,
leather, proteins, and DNA, are polymers. Polyethylene, nylon, and acrylics
are examples of synthetic polymers. The study of such materials lies within
the domain of polymer chemistry, a specialty that has flourished in the 20th
century. The investigation of natural polymers overlaps considerably with
biochemistry, but the synthesis of new polymers, the investigation of
polymerization processes, and the characterization of the structure and
properties of polymeric materials all pose unique problems for polymer
chemists.
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Polymer chemists have designed and synthesized polymers that vary in

hardness, flexibility, softening temperature, solubility in water, and
biodegradability. They have produced polymeric materials that are as strong
as steel yet lighter and more resistant to corrosion. Oil, natural gas, and
water pipelines are now routinely constructed of plastic pipe. In recent years,
automakers have increased their use of plastic components to build lighter
vehicles that consume less fuel. Other industries such as those involved in
the manufacture of textiles, rubber, paper, and packaging materials are built
upon polymer chemistry.

Besides producing new kinds of polymeric materials, researchers are

concerned with developing special catalysts that are required by the large-
scale industrial synthesis of commercial polymers. Without such catalysts,
the polymerization process would be very slow in certain cases.

Physical chemistry
Many chemical disciplines, such as those already discussed, focus on certain
classes of materials that share common structural and chemical features.
Other specialties may be centred not on a class of substances but rather on
their interactions and transformations. The oldest of these fields is physical
chemistry, which seeks to measure, correlate, and explain the quantitative
aspects of chemical processes. The Anglo-Irish chemist Robert Boyle, for
example, discovered in the 17th century that at room temperature the
volume of a fixed quantity of gas decreases proportionally as the pressure
on it increases. Thus, for a gas at constant temperature, the product of its
volume V and pressure P equals a constant number—i.e., PV = constant.
Such a simple arithmetic relationship is valid for nearly all gases at room
temperature and at pressures equal to or less than one atmosphere.
Subsequent work has shown that the relationship loses its validity at higher
pressures, but more complicated expressions that more accurately match
experimental results can be derived. The discovery and investigation of such
chemical regularities, often called laws of nature, lie within the realm of
physical chemistry. For much of the 18th century the source of mathematical
regularity in chemical systems was assumed to be the continuum of forces
and fields that surround the atoms making up chemical elements and
compounds. Developments in the 20th century, however, have shown that

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chemical behaviour is best interpreted by a quantum mechanical model of

atomic and molecular structure. The branch of physical chemistry that is
largely devoted to this subject is theoretical chemistry. Theoretical chemists
make extensive use of computers to help them solve complicated
mathematical equations. Other branches of physical chemistry include
chemical thermodynamics, which deals with the relationship between heat
and other forms of chemical energy, and chemical kinetics, which seeks to
measure and understand the rates of chemical reactions. Electrochemistry
investigates the interrelationship of electric current and chemical change.
The passage of an electric current through a chemical solution causes
changes in the constituent substances that are often reversible—i.e., under
different conditions the altered substances themselves will yield an electric
current. Common batteries contain chemical substances that, when placed
in contact with each other by closing an electrical circuit, will deliver current
at a constant voltage until the substances are consumed. At present there is
much interest in devices that can use the energy in sunlight to drive
chemical reactions whose products are capable of storing the energy. The
discovery of such devices would make possible the widespread utilization of
solar energy.

There are many other disciplines within physical chemistry that are
concerned more with the general properties of substances and the
interactions among substances than with the substances themselves.
Photochemistry is a specialty that investigates the interaction of light with
matter. Chemical reactions initiated by the absorption of light can be very
different from those that occur by other means. Vitamin D, for example, is
formed in the human body when the steroid ergosterol absorbs solar
radiation; ergosterol does not change to vitamin D in the dark.

A rapidly developing subdiscipline of physical chemistry is surface chemistry.

It examines the properties of chemical surfaces, relying heavily on
instruments that can provide a chemical profile of such surfaces. Whenever a
solid is exposed to a liquid or a gas, a reaction occurs initially on the surface
of the solid, and its properties can change dramatically as a result.
Aluminum is a case in point: it is resistant to corrosion precisely because the
surface of the pure metal reacts with oxygen to form a layer of aluminum
oxide, which serves to protect the interior of the metal from further
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oxidation. Numerous reaction catalysts perform their function by providing

a reactive surface on which substances can react.

Industrial chemistry
The manufacture, sale, and distribution of chemical products is one of the
cornerstones of a developed country. Chemists play an important role in the
manufacture, inspection, and safe handling of chemical products, as well as
in product development and general management. The manufacture of
basic chemicals such as oxygen, chlorine, ammonia, and sulfuric acid
provides the raw materials for industries producing textiles, agricultural
products, metals, paints, and pulp and paper. Specialty chemicals are
produced in smaller amounts for industries involved with such products as
pharmaceuticals, foodstuffs, packaging, detergents, flavours, and fragrances.
To a large extent, the chemical industry takes the products and reactions
common to “bench-top” chemical processes and scales them up to
industrial quantities.

The monitoring and control of bulk chemical processes, especially with

regard to heat transfer, pose problems usually tackled by chemists and
chemical engineers. The disposal of by-products also is a major problem for
bulk chemical producers. These and other challenges of industrial chemistry
set it apart from the more purely intellectual disciplines of chemistry
discussed above. Yet, within the chemical industry, there is a considerable
amount of fundamental research undertaken within traditional specialties.
Most large chemical companies have research-and-development capability.
Pharmaceutical firms, for example, operate large research laboratories in
which chemists test molecules for pharmacological activity. The new
products and processes that are discovered in such laboratories are often
patented and become a source of profit for the company funding the
research. A great deal of the research conducted in the chemical industry
can be termed applied research because its goals are closely tied to the
products and processes of the company concerned. New technologies often
require much chemical expertise. The fabrication of, say, electronic
microcircuits involves close to 100 separate chemical steps from start to
finish. Thus, the chemical industry evolves with the technological advances

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of the modern world and at the same time often contributes to the rate of
progress.

The methodology of chemistry

Chemistry is to a large extent a cumulative science. Over time the number
and extent of observations and phenomena studied increase. Not all
hypotheses and discoveries endure unchallenged, however. Some of them
are discarded as new observations or more satisfying explanations appear.
Nonetheless, chemistry has a broad spectrum of explanatory models for
chemical phenomena that have endured and been extended over time.
These now have the status of theories, interconnected sets of explanatory
devices that correlate well with observed phenomena. As new discoveries
are made, they are incorporated into existing theory whenever possible.
However, as the discovery of high-temperature superconductors in 1986
illustrates, accepted theory is never sufficient to predict the course of future
discovery. Serendipity, or chance discovery, will continue to play as much a
role in the future as will theoretical sophistication.

Studies of molecular structure

The chemical properties of a substance are a
function of its structure, and the techniques
of X-ray crystallography now enable
chemists to determine the precise atomic
molecular structure
A ball-and-stick model of arrangement of complex molecules. A
molecular structure, showing atoms
molecule is an ordered assembly of atoms.
bonded together.
© asiseeit/iStock.com Each atom in a molecule is connected to one
or more neighbouring atoms by a chemical
bond. The length of bonds and the angles between adjacent bonds are all
important in describing molecular structure, and a comprehensive theory of
chemical bonding is one of the major achievements of modern chemistry.
Fundamental to bonding theory is the atomic–molecular concept.

Atoms and elements

As far as general chemistry is concerned, atoms are composed of the three
fundamental particles: the proton, the neutron, and the electron. Although

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the proton and the neutron are themselves composed of smaller units, their
substructure has little impact on chemical transformation. As was explained
in an earlier section, the proton carries a charge of +1, and the number of
protons in an atomic nucleus distinguishes one type of chemical atom from
another. The simplest atom of all, hydrogen, has a nucleus composed of a
single proton. The neutron has very nearly the same mass as the proton, but
it has no charge. Neutrons are contained with protons in the nucleus of all
atoms other than hydrogen. The atom with one proton and one neutron in
its nucleus is called deuterium. Because it has only one proton, deuterium
exhibits the same chemical properties as hydrogen but has a different mass.
Hydrogen and deuterium are examples of related atoms called isotopes. The
third atomic particle, the electron, has a charge of -1, but its mass is 1,836
times smaller than that of a proton. The electron occupies a region of space
outside the nucleus termed an orbital. Some orbitals are spherical with the
nucleus at the centre. Because electrons have so little mass and move about
at speeds close to half that of light, they exhibit the same wave–particle
duality as photons of light. This means that some of the properties of an
electron are best described by considering the electron to be a particle,
while other properties are consistent with the behaviour of a standing wave.
The energy of a standing wave, such as a vibrating string, is distributed over
the region of space defined by the two fixed ends and the up-and-down
extremes of vibration. Such a wave does not exist in a fixed region of space
as does a particle. Early models of atomic structure envisioned the electron
as a particle orbiting the nucleus, but electron orbitals are now interpreted
as the regions of space occupied by standing waves called wave functions.
These wave functions represent the regions of space around the nucleus in
which the probability of finding an electron is high. They play an important
role in bonding theory, as will be discussed later.

Each proton in an atomic nucleus requires an electron for electrical

neutrality. Thus, as the number of protons in a nucleus increases, so too
does the number of electrons. The electrons, alone or in pairs, occupy
orbitals increasingly distant from the nucleus. Electrons farther from the
nucleus are attracted less strongly by the protons in the nucleus, and they
can be removed more easily from the atom. The energy required to move an
electron from one orbital to another, or from one orbital to free space, gives

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a measure of the energy level of the orbitals. These energies have been
found to have distinct, fixed values; they are said to be quantized. The
energy differences between orbitals give rise to the characteristic patterns of
light absorption or emission that are unique to each chemical atom.

A new chemical atom—that is, an element—results each time another

proton is added to an atomic nucleus. Consecutive addition of protons
generates the whole range of elements known to exist in the universe.
Compounds are formed when two or more different elements combine
through atomic bonding. Such bond formation is a consequence of electron
pairing and constitutes the foundation of all structural chemistry.

Ionic and covalent bonding

When two different atoms approach each other, the electrons in their outer
orbitals can respond in two distinct ways. An electron in the outermost
atomic orbital of atom A may move completely to an outer but stabler
orbital of atom B. The charged atoms that result, A+ and B-, are called ions,
and the electrostatic force of attraction between them gives rise to what is
termed an ionic bond. Most elements can form ionic bonds, and the
substances that result commonly exist as three-dimensional arrays of
positive and negative ions. Ionic compounds are frequently crystalline solids
that have high melting points (e.g., table salt).

The second way in which the two outer electrons of atoms A and B can
respond to the approach of A and B is to pair up to form a covalent bond. In
the simple view known as the valence-bond model, in which electrons are
treated strictly as particles, the two paired electrons are assumed to lie
between the two nuclei and are shared equally by atoms A and B, resulting
in a covalent bond. Atoms joined together by one or more covalent bonds
constitute molecules. Hydrogen gas is composed of hydrogen molecules,
which consist in turn of two hydrogen atoms linked by a covalent bond. The
notation H for hydrogen gas is referred to as a molecular formula.
2
Molecular formulas indicate the number and type of atoms that make up a
molecule. The molecule H is responsible for the properties generally
2
associated with hydrogen gas. Most substances on Earth have covalently
bonded molecules as their fundamental chemical unit, and their molecular

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properties are completely different from those of the constituent elements.

The physical and chemical properties of carbon dioxide, for example, are
quite distinct from those of pure carbon and pure oxygen.

The interpretation of a covalent bond as a localized electron pair is an

oversimplification of the bonding situation. A more comprehensive
description of bonding that considers the wave properties of electrons is the
molecular-orbital theory. According to this theory, electrons in a molecule,
rather than being localized between atoms, are distributed over all the
atoms in the molecule in a spatial distribution described by a molecular
orbital. Such orbitals result when the atomic orbitals of bonded atoms
combine with each other. The total number of molecular orbitals present in a
molecule is equal to the sum of all atomic orbitals in the constituent atoms
prior to bonding. Thus, for the simple combination of atoms A and B to form
the molecule AB, two atomic orbitals combine to generate two molecular
orbitals. One of these, the so-called bonding molecular orbital, represents a
region of space enveloping both the A and B atoms, while the other, the
anti-bonding molecular orbital, has two lobes, neither of which occupies the
space between the two atoms. The bonding molecular orbital is at a lower
energy level than are the two atomic orbitals, while the anti-bonding orbital
is at a higher energy level. The two paired electrons that constitute the
covalent bond between A and B occupy the bonding molecular orbital. For
this reason, there is a high probability of finding the electrons between A
and B, but they can be found elsewhere in the orbital as well. Because only
two electrons are involved in bond formation and both can be
accommodated in the lower energy orbital, the anti-bonding orbital remains
unpopulated. This theory of bonding predicts that bonding between A and
B will occur because the energy of the paired electrons after bonding is less
than that of the two electrons in their atomic orbitals prior to bonding. The
formation of a covalent bond is thus energetically favoured. The system
goes from a state of higher energy to one of lower energy.

Another feature of this bonding picture is that it is able to predict the energy
required to move an electron from the bonding molecular orbital to the
anti-bonding one. The energy required for such an electronic excitation can
be provided by visible light, for example, and the wavelength of the light
absorbed determines the colour displayed by the absorbing molecule (e.g.,
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violets are blue because the pigments in the flower absorb the red rays of
natural light and reflect more of the blue). As the number of atoms in a
molecule increases, so too does the number of molecular orbitals.
Calculation of molecular orbitals for large molecules is mathematically
difficult, but computers have made it possible to determine the wave
equations for several large molecules. Molecular properties predicted by
such calculations correlate well with experimental results.

Isomerism
Many elements can form two or more covalent bonds, but only a few are
able to form extended chains of covalent bonds. The outstanding example is
carbon, which can form as many as four covalent bonds and can bond to
itself indefinitely. Carbon has six electrons in total, two of which are paired in
an atomic orbital closest to the nucleus. The remaining four are farther from
the nucleus and are available for covalent bonding. When there is sufficient
hydrogen present, carbon will react to form methane, CH . When all four
4
electron pairs occupy the four molecular orbitals of lowest energy, the
molecule assumes the shape of a tetrahedron, with carbon at the centre and
the four hydrogen atoms at the apexes. The C–H bond length is 110
picometres (1 picometre = 10-12 metre), and the angle between adjacent C–
H bonds is close to 110°. Such tetrahedral symmetry is common to many
carbon compounds and results in interesting structural possibilities. If two
carbon atoms are joined together, with three hydrogen atoms bonded to
each carbon atom, the molecule ethane is obtained. When four carbon
atoms are joined together, two different structures are possible: a linear
structure designated n-butane and a branched structure called iso-butane.
These two structures have the same molecular formula, C H , but a
4 10
different order of attachment of their constituent atoms. The two molecules
are termed structural isomers. Each of them has unique chemical and
physical properties, and they are different compounds. The number of
possible isomers increases rapidly as the number of carbon atoms increases.
There are five isomers for C H , 75 for C H , and 6.2 × 1013 for C H .
6 14 10 22 40 82
When carbon forms bonds to atoms other than hydrogen, such as oxygen,
nitrogen, and sulfur, the structural possibilities become even greater. It is this

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great potential for structural diversity that makes carbon compounds

essential to living organisms.

Even when the bonding sequence of carbon compounds is fixed, further

structural variation is still possible. When two carbon atoms are joined
together by two bonding pairs of electrons, a double bond is formed. A
double bond forces the two carbon atoms and attached groups into a rigid,
planar structure. As a result, a molecule such as CHCl=CHCl can exist in two
nonidentical forms called geometric isomers. Structural rigidity also occurs
in ring structures, and attached groups can be on the same side of a ring or
on different sides. Yet another opportunity for isomerism arises when a
carbon atom is bonded to four different groups. These can be attached in
two different ways, one of which is the mirror image of the other. This type
of isomerism is called optical isomerism, because the two isomers affect
plane-polarized light differently. Two optical isomers are possible for every
carbon atom that is bonded to four different groups. For a molecule bearing
10 such carbon atoms, the total number of possible isomers will be 210 =
1,024. Large biomolecules often have 10 or more carbon atoms for which
such optical isomers are possible. Only one of all the possible isomers will
be identical to the natural molecule. For this reason, the laboratory synthesis
of large organic molecules is exceedingly difficult. Only in the last few
decades of the 20th century have chemists succeeded in developing
reagents and processes that yield specific optical isomers. They expect that
new synthetic methods will make possible the synthesis of ever more
complex natural products.

Investigations of chemical transformations

Basic factors
The structure of ionic substances and covalently bonded molecules largely
determines their function. As noted above, the properties of a substance
depend on the number and type of atoms it contains and on the bonding
patterns present. Its bulk properties also depend, however, on the
interactions among individual atoms, ions, or molecules. The force of
attraction between the fundamental units of a substance dictate whether, at
a given temperature and pressure, that substance will exist in the solid,

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liquid, or gas phase. At room temperature and pressure, for example, the
strong forces of attraction between the positive ions of sodium (Na+) and
the negative ions of chlorine (Cl−) draw them into a compact solid structure.
The weaker forces of attraction among neighbouring water molecules allow
the looser packing characteristic of a liquid. Finally, the very weak attractive
forces acting among adjacent oxygen molecules are exceeded by the
dispersive forces of heat; oxygen, consequently, is a gas. Interparticle forces
thus affect the chemical and physical behaviour of substances, but they also
determine to a large extent how a particle will respond to the approach of a
different particle. If the two particles react with each other to form new
particles, a chemical reaction has occurred. Notwithstanding the unlimited
structural diversity allowed by molecular bonding, the world would be
devoid of life if substances were incapable of change. The study of chemical
transformation, which complements the study of molecular structure, is built
on the concepts of energy and entropy.

Energy and the first law of thermodynamics

The concept of energy is a fundamental and familiar one in all the sciences.
In simple terms, the energy of a body represents its ability to do work, and
work itself is a force acting over a distance.

Chemical systems can have both kinetic energy (energy of motion) and
potential energy (stored energy). The kinetic energy possessed by any
collection of molecules in a solid, liquid, or gas is known as its thermal
energy. Since liquids expand when they have more thermal energy, a liquid
column of mercury, for example, will rise higher in an evacuated tube as it
becomes warmer. In this way a thermometer can be used to measure the
thermal energy, or temperature, of a system. The temperature at which all
molecular motion comes to a halt is known as absolute zero.

Energy also may be stored in atoms or molecules as potential energy. When

protons and neutrons combine to form the nucleus of a certain element, the
reduction in potential energy is matched by the production of a huge
quantity of kinetic energy. Consider, for instance, the formation of the
deuterium nucleus from one proton and one neutron. The fundamental
mass unit of the chemist is the mole, which represents the mass, in grams, of

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6.02 × 1023 individual particles, whether they be atoms or molecules. One

mole of protons has a mass of 1.007825 grams and one mole of neutrons
has a mass of 1.008665 grams. By simple addition the mass of one mole of
deuterium atoms (ignoring the negligible mass of one mole of electrons)
should be 2.016490 grams. The measured mass is 0.00239 gram less than
this. The missing mass is known as the binding energy of the nucleus and
represents the mass equivalent of the energy released by nucleus formation.
By using Einstein’s formula for the conversion of mass to energy (E = mc2),
one can calculate the energy equivalent of 0.00239 gram as 2.15 × 108
kilojoules. This is approximately 240,000 times greater than the energy
released by the combustion of one mole of methane. Such studies of the
energetics of atom formation and interconversion are part of a specialty
known as nuclear chemistry.

The energy released by the combustion of methane is about 900 kilojoules

per mole. Although much less than the energy released by nuclear reactions,
the energy given off by a chemical process such as combustion is great
enough to be perceived as heat and light. Energy is released in so-called
exothermic reactions because the chemical bonds in the product molecules,
carbon dioxide and water, are stronger and stabler than those in the
reactant molecules, methane and oxygen. The chemical potential energy of
the system has decreased, and most of the released energy appears as heat,
while some appears as radiant energy, or light. The heat produced by such a
combustion reaction will raise the temperature of the surrounding air and, at
constant pressure, increase its volume. This expansion of air results in work
being done. In the cylinder of an internal-combustion engine, for example,
the combustion of gasoline results in hot gases that expand against a
moving piston. The motion of the piston turns a crankshaft, which then
propels the vehicle. In this case, chemical potential energy has been
converted to thermal energy, some of which produces useful work. This
process illustrates a statement of the conservation of energy known as the
first law of thermodynamics. This law states that, for an exothermic reaction,
the energy released by the chemical system is equal to the heat gained by
the surroundings plus the work performed. By measuring the heat and work
quantities that accompany chemical reactions, it is possible to ascertain the
energy differences between the reactants and the products of various
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reactions. In this manner, the potential energy stored in a variety of

molecules can be determined, and the energy changes that accompany
chemical reactions can be calculated.

Entropy and the second law of thermodynamics

Some chemical processes occur even though there is no net energy change.
Consider a vessel containing a gas, connected to an evacuated vessel via a
channel wherein a barrier obstructs passage of the gas. If the barrier is
removed, the gas will expand into the evacuated vessel. This expansion is
consistent with the observation that a gas always expands to fill the volume
available. When the temperature of both vessels is the same, the energy of
the gas before and after the expansion is the same. The reverse reaction
does not occur, however. The spontaneous reaction is the one that yields a
state of greater disorder. In the expanded volume, the individual gas
molecules have greater freedom of movement and thus are more
disordered. The measure of the disorder of a system is a quantity termed
entropy. At a temperature of absolute zero, all movement of atoms and
molecules ceases, and the disorder—and entropy—of such perfectly
compacted substances is zero. (Zero entropy at zero temperature is in
accord with the third law of thermodynamics.) All substances above absolute
zero will have a positive entropy value that increases with temperature.
When a hot body cools down, the thermal energy it loses passes to the
surrounding air, which is at a lower temperature. As the entropy of the
cooling body decreases, the entropy of the surrounding air increases. In fact,
the increase in entropy of the air is greater than the decrease in entropy of
the cooling body. This is consistent with the second law, which states that
the total entropy of a system and its surroundings always increases in a
spontaneous reaction. Thus the first and second laws of thermodynamics
indicate that, for all processes of chemical change throughout the universe,
energy is conserved but entropy increases.

Application of the laws of thermodynamics to chemical systems allows

chemists to predict the behaviour of chemical reactions. When energy and
entropy considerations favour the formation of product molecules, reagent
molecules will act to form products until an equilibrium is established
between products and reagents. The ratio of products to reagents is

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specified by a quantity known as an equilibrium constant, which is a

function of the energy and entropy differences between the two. What
thermodynamics cannot predict, however, is the rate at which chemical
reactions occur. For fast reactions an equilibrium mixture of products and
reagents can be established in one millisecond or less; for slow reactions the
time required could be hundreds of years.

Rates of reaction
When the specific rates of chemical reactions are measured experimentally,
they are found to be dependent on the concentrations of reacting species,
temperature, and a quantity called activation energy. Chemists explain this
phenomenon by recourse to the collision theory of reaction rates. This
theory builds on the premise that a reaction between two or more chemicals
requires, at the molecular level, a collision between two rapidly moving
molecules. If the two molecules collide in the right way and with enough
kinetic energy, one of the molecules may acquire enough energy to initiate
the bond-breaking process. As this occurs, new bonds may begin to form,
and ultimately reagent molecules are converted into product molecules. The
point of highest energy during bond breaking and bond formation is called
the transition state of the molecular process. The difference between the
energy of the transition state and that of the reacting molecules is the
activation energy that must be exceeded for a reaction to occur. Reaction
rates increase with temperature because the colliding molecules have
greater energies, and more of them will have energies that exceed the
activation energy of reaction. The modern study of the molecular basis of
chemical change has been greatly aided by lasers and computers. It is now
possible to study short-lived collision products and to better determine the
molecular mechanisms that fix the rate of chemical reactions. This
knowledge is useful in designing new catalysts that can accelerate the rate
of reaction by lowering the activation energy. Catalysts are important for
many biochemical and industrial processes because they speed up reactions
that ordinarily occur too slowly to be useful. Moreover, they often do so with
increased control over the structural features of the product molecules. A
rhodium phosphine catalyst, for example, has enabled chemists to obtain 96
percent of the correct optical isomer in a key step in the synthesis of L-dopa,
a drug used for treating Parkinson’s disease.
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Chemistry and society

For the first two-thirds of the 20th century, chemistry was seen by many as
the science of the future. The potential of chemical products for enriching
society appeared to be unlimited. Increasingly, however, and especially in
the public mind, the negative aspects of chemistry have come to the fore.
Disposal of chemical by-products at waste-disposal sites of limited capacity
has resulted in environmental and health problems of enormous concern.
The legitimate use of drugs for the medically supervised treatment of
diseases has been tainted by the growing misuse of mood-altering drugs.
The very word chemicals has come to be used all too frequently in a
pejorative sense. There is, as a result, a danger that the pursuit and
application of chemical knowledge may be seen as bearing risks that
outweigh the benefits.

It is easy to underestimate the central role of chemistry in modern society,

but chemical products are essential if the world’s population is to be
clothed, housed, and fed. The world’s reserves of fossil fuels (e.g., oil,
natural gas, and coal) will eventually be exhausted, some as soon as the 21st
century, and new chemical processes and materials will provide a crucial
alternative energy source. The conversion of solar energy to more
concentrated, useful forms, for example, will rely heavily on discoveries in
chemistry. Long-term, environmentally acceptable solutions to pollution
problems are not attainable without chemical knowledge. There is much
truth in the aphorism that “chemical problems require chemical solutions.”
Chemical inquiry will lead to a better understanding of the behaviour of
both natural and synthetic materials and to the discovery of new substances
that will help future generations better supply their needs and deal with
their problems.

Progress in chemistry can no longer be measured only in terms of

economics and utility. The discovery and manufacture of new chemical
goods must continue to be economically feasible but must be
environmentally acceptable as well. The impact of new substances on the
environment can now be assessed before large-scale production begins, and
environmental compatibility has become a valued property of new materials.
For example, compounds consisting of carbon fully bonded to chlorine and

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fluorine, called chlorofluorocarbons (or Freons), were believed to be ideal for

their intended use when they were first discovered. They are nontoxic,
nonflammable gases and volatile liquids that are very stable. These
properties led to their widespread use as solvents, refrigerants, and
propellants in aerosol containers. Time has shown, however, that these
compounds decompose in the upper regions of the atmosphere and that
the decomposition products act to destroy stratospheric ozone. Limits have
now been placed on the use of chlorofluorocarbons, but it is impossible to
recover the amounts already dispersed into the atmosphere.

The chlorofluorocarbon problem illustrates how difficult it is to anticipate

the overall impact that new materials can have on the environment.
Chemists are working to develop methods of assessment, and prevailing
chemical theory provides the working tools. Once a substance has been
identified as hazardous to the existing ecological balance, it is the
responsibility of chemists to locate that substance and neutralize it, limiting
the damage it can do or removing it from the environment entirely. The last
years of the 20th century will see many new, exciting discoveries in the
processes and products of chemistry. Inevitably, the harmful effects of some
substances will outweigh their benefits, and their use will have to be limited.
Yet, the positive impact of chemistry on society as a whole seems beyond
doubt.

Melvyn C. Usselman
The history of chemistry
Chemistry has justly been called the central science. Chemists study the
various substances in the world, with a particular focus on the processes by
which one substance is transformed into another. Today, chemistry is
defined as the study of the composition and properties of elements and
compounds, the structure of their molecules, and the chemical reactions
that they undergo. Rather than starting with such modern concepts, though,
a fuller appreciation of the subject requires an examination of the historical
processes that led to these concepts.

Philosophy of matter in antiquity

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Indeed, the philosophers of antiquity could have had no notion that all
matter consists of the combinations of a few dozen elements as they are
understood today. The earliest critical thinking on the nature of substances,
as far as the historical record indicates, was by certain Greek philosophers
beginning about 600 BCE. Thales of Miletus, Anaximander, Empedocles, and
others propounded theories that the world consisted of varieties of earth,
water, air, fire, or indeterminate “seeds” or “unbounded” matter.
Leucippus and Democritus propounded a materialistic theory of invisibly
tiny irreducible atoms from which the world was made. In the 4th century
BCE, Plato (influenced by Pythagoreanism) taught that the world of the
senses was but the shadow of a mathematical world of “forms” beyond
human perception.

In contrast, Plato’s student Aristotle took

the world of the senses seriously. Adopting
Empedocles’s view that the terrestrial
region consisted of earth, water, air, and fire,
Aristotle taught that each of these materials
Thales of Miletus was a combination of qualities such as hot,
Thales of Miletus (6th century
cold, moist, and dry. For Aristotle, these
BCE
), philosopher, astronomer, and
“elements” were not building blocks of
geometer, who was renowned as matter as they are thought of now; rather,
one of the Seven Wise Men of
they resulted from the qualities imposed on
antiquity. He identified water as the
original substance and basis of the otherwise featureless prime matter.
universe. Consequently, there were many different
Courtesy of the Rijksmuseum,
Amsterdam kinds of earth, for instance, and nothing
precluded one element from being
transformed into another by appropriate adjustment of its qualities. Thus,
Aristotle rejected the speculations of the ancient atomists and their
irreducible fundamental particles. His views were highly regarded in late
antiquity and remained influential throughout the Middle Ages.

For thousands of years before Aristotle, metalsmiths, assayers, ceramists,

and dyers had worked to perfect their crafts using empirically derived
knowledge of chemical processes. By Hellenistic and Roman times, their
skills were well advanced, and sophisticated ceramics, glasses, dyes, drugs,
steels, bronze, brass, alloys of gold and silver, foodstuffs, and many other
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chemical products were traded. Hellenistic Alexandria in Egypt was a centre

for these arts, and it was apparently there that a group of ideas emerged
that later became known as alchemy.

Alchemy
Three different sets of ideas and skills fed into the origin of alchemy. First
was the empirical sophistication of jewelers, gold- and silversmiths, and
other artisans who had learned how to fashion precious and semiprecious
materials. Among their skills were smelting, assaying, alloying, gilding,
amalgamating, distilling, sublimating, painting, and lacquering. The second
component was the early Greek theory of matter, especially Aristotelian
philosophy, which suggested the possibility of unlimited transformability of
one kind of matter into another. The third of alchemy’s roots consisted of a
complex combination of ideas derived from Asian philosophies and
religions, Hellenistic mystery religions, and what became known as the
Hermetic writings (a body of pseudonymous Greek writings on magic,
astrology, and alchemy ascribed to the Egyptian god Thoth or his Greek
counterpart Hermes Trismegistos). It is important to note, however, that
Hellenistic Egypt is only one of several candidates for the homeland of
alchemy; at about the same time, similar ideas were developing in Persia,
China, and elsewhere.

In general, alchemists sought to manipulate the properties of matter in

order to prepare more valuable substances. Their most familiar quest was to
find the philosopher’s stone, a magical substance that would transmute
ordinary metals such as copper, tin, iron, or lead into silver or gold.
Important materials in this craft included sulfur, mercury, and electrum (a
gold-silver alloy). However, many other alchemists spurned alchemical
transmutation (aurifaction), devoting their efforts instead to a
pharmaceutical preparation known as the “elixir of life” that would cure
any disease, including the ultimate disease, death. The philosopher’s stone
and the elixir of life could be considered parallel quests, for each would
“cure” metallic or human bodies, respectively, yielding immortal
perfection. There was a parallel religious dimension to all this as well. Finally,
some alchemists spurned material manipulations entirely, devoting

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themselves to meditation with the goal of achieving spiritual purity and

ultimate redemption.

After the rise of Islam, Arabic-speaking scholars of the 9th century

translated Greek scientific and philosophical works into their own language.
Thereafter, philosophers in the Islamic world pursued chemical and
alchemical ideas with enthusiasm and success. The sizable number of
modern chemical words derived from Arabic—alcohol, alkali, alchemy,
zircon, elixir, natron, and others—suggests the importance of this period for
the history of chemistry. One of the leading ideas of medieval Arabic
alchemy was the theory that all metals were formed of sulfur and mercury in
various proportions and that altering those proportions could transform the
metal under study—even to produce silver or gold from lead or iron. Not
every alchemist, however, believed in the possibility of such transmutations.

Later, scholars in Christian western Europe learned of ancient Greek and

early medieval Arabic philosophy by translating these books into Latin. Thus,
the alchemical tradition, along with the rest of the Greco-Arabic
philosophical and scientific corpus, passed to the West in the course of the
12th century. Well-known Scholastic philosophers of the 13th century, such
as Roger Bacon in England and Albertus Magnus in Germany and France,
wrote on alchemy. Alongside this learned literature, the empirical chemical
arts continued to flourish and comprised a largely separate realm of
expertise among artisans, engineers, and mechanics.

An important Western alchemist of the late 13th century was the

pseudonymous Latin writer who called himself Geber in homage to the 8th-
century Arab alchemist Jābir ibn Ḥayyān. Geber was the first to record
methods for the preparation and use of sulfuric acid, nitric acid, and
hydrochloric acid; the earliest clear evidence for widespread familiarity with
distilled alcohol also does not much predate his day. These substances could
only have been produced by novel stills that were more robust and efficient
than their predecessors, and the appearance of these remarkable new
materials produced dramatic changes in the repertoire of chemists.

The Renaissance saw even stronger interest in the science. The German-
Swiss physician Paracelsus practiced alchemy, Kabbala, astrology, and magic,

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and in the first half of the 16th century he championed the role of mineral
rather than herbal remedies. His emphasis on chemicals in pharmacy and
medicine was influential on later figures, and lively controversies over the
Paracelsian approach raged around the turn of the 17th century. Gradually
the Hermetic influence declined in Europe, however, as certain celebrated
feats of putative aurifaction were revealed as frauds.

It would be a mistake to think that open-minded empirical investigation that

is well integrated with theory (which is how one might define science) was
absent from the history of alchemy. Alchemy had many quite scientific
practitioners through the centuries, notably including Britain’s Robert
Boyle and Isaac Newton—heroes of the scientific revolution of the 17th
century—who applied systematic and quantitative method to their (mostly
secret) alchemical studies. Indeed, as late as the end of the 17th century
there was little to distinguish alchemy from chemistry, either substantively
or semantically, since both words were applied to the same set of ideas. It
was only in the early 18th century that chemists conferred different
definitions on the two words, banishing alchemy to the ashbin of discredited
occult pseudosciences.

Phlogiston theory
This shift was partly simple self-promotion by chemists in the new
environment of the Enlightenment, whose vanguard glorified rationalism,
experiment, and progress while demonizing the mystical. However, it was
also becoming ever clearer that certain central ideas of alchemy (especially
metallic transmutation) had never been demonstrated. One of the leaders in
this regard was the German physician and chemist Georg Ernst Stahl, who
vigorously attacked alchemy (after dabbling in it himself) and proposed an
expansive new chemical theory. Stahl noted parallels between the burning of
combustible materials and the calcination of metals—the conversion of a
metal into its calx, or oxide. He suggested that both processes consisted of
the loss of a material fluid, contained within all combustibles, called
phlogiston.

Phlogiston became the centrepiece of a broad-ranging theory that

dominated 18th-century chemical thought. Phlogiston, in short, was

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thought to be a material substance that defined combustibility. When

metallic iron becomes red rust, it loses its phlogiston, just as a burning log
does. The ashes of the log and the red rust “ashes” (calx) of iron can no
longer burn because they no longer contain the principle of combustibility,
or phlogiston. But iron calx can be converted back to the metal if it is
strongly heated in the presence of a phlogiston-rich substance such as
charcoal. The charcoal donates its phlogiston (becoming ashes itself), while
the calx turns into molten metallic iron. Thus, smelting (reduction) of
metallic ores could also be understood in phlogistic terms. Later
phlogistonists added respiration to the number of phenomena that the
theory could elucidate. An animal breathes air, emitting phlogiston in an
analogy to a slow fire, fueled by the phlogiston-rich food it consumes.
Earth’s atmosphere avoids excess accumulation of phlogiston because
plants incorporate it into combustible plant tissues that can then be used as
animal food. Combustion, calcination, or respiration eventually cease in an
enclosed space because air has a limited capacity to absorb the phlogiston
emitted from the burning, calcining, or respiring entity.

The phlogiston theory became popular both because of its great success in
explaining phenomena and guiding further investigation and because of a
certain Enlightenment predilection for materialistic physical theories (the
putative fluid of heat became known as caloric, and there were other
suggested fluids of electricity, light, and so on). This materialist-mechanist
trend can also be seen in the diffuse but powerful influence of Newton and
René Descartes on chemists of the 18th century. Enlightenment chemists
established distinctive scientific communities and a well-defined discipline
(closely allied, to be sure, with medical and artisanal studies) in the major
countries of Europe. The chemist’s workplace or laboratory (the word itself
had been coined in the Renaissance to apply to the chemical arts) was now
closely associated with the field, and a standardized repertoire of operations
was taught there.

Still unsettled were some fundamental issues relating to chemical

composition. To a phlogistonist, a metallic calx was elemental, and the
associated metal was a compound of calx plus phlogiston. This puzzled
some, though, since the metal gained rather than lost weight when it
supposedly lost phlogiston to become a calx. The issues were sharpened in
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the 1770s, when the virtuoso English chemist (and Unitarian minister)
Joseph Priestley produced a new gas by heating certain minerals. A candle
burned in this gas with extraordinary vigour, and in an enclosed space a
mouse breathing it survived far longer than one could in ordinary air.
Priestley’s explanation was that the new gas had been radically
dephlogisticated and, hence, had much greater capacity than air for
absorbing phlogiston.

Actually, gases (then usually known as airs) were a relatively novel object of
chemical attention. In Scotland in 1756, Joseph Black studied the gas given
off in respiration and combustion, characterizing it chemically and following
its participation in certain chemical reactions. (Black, a physician, taught
chemistry as a branch of medicine, as did most academic chemists of this
era.) He called the new gas “fixed air,” since it was also found “fixed” in
certain minerals such as limestone. His discovery that this gas was a normal
component of common air (at a fraction of a percent, to be sure) was the
first clear indication that atmospheric air was a mixture rather than a
homogeneous element. In the following quarter century, many new gases
were discovered and studied, by such workers as Priestley, the English
physicist and chemist Henry Cavendish, and the Swedish pharmacist Carl
Scheele.

The chemical revolution

The new research on “airs” attracted the attention of the young French
aristocrat Antoine-Laurent Lavoisier. Lavoisier commanded both the wealth
and the scientific brilliance to enable him to construct elaborate apparatuses
to carry out his numerous ingenious experiments. In the course of just a few
years in the 1770s, Lavoisier developed a radical new system of chemistry,
based on Black’s methods and Priestley’s dephlogisticated air.

Lavoisier first determined that certain metals and nonmetals absorb a

gaseous substance from the air in undergoing calcination or combustion
and, in the process, increase in weight. Initially, he thought that this gas
must be Black’s fixed air, for he knew of no other chemical species present
in ordinary air; moreover, fixed air was known to be produced in smelting, so
it seemed reasonable to think that it was present in the calx that was

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smelted. At this point (October 1774), Priestley communicated to Lavoisier

his discovery of dephlogisticated air. Further experiments led Lavoisier to
continuously modify his ideas, until it finally became clear to him that it was
this new gas, and not fixed air, that was the active entity in combustion,
calcination, and respiration. Moreover, he determined (or so he thought, at
least) that this gas was contained in all acids. He renamed it oxygen, Greek
for “acid producer.”

Lavoisier’s oxygen was in some respects the inverse of phlogiston. Rather

than releasing anything, the combustible or metal absorbed (more precisely,
chemically combined with) oxygen in the process that Lavoisier now called
oxidation. He showed that atmospheric air was a mixture of two principal
components, oxygen and a physiologically inert gas (known to Priestley)
that he called azote or nitrogen. He also showed that water is a chemical
compound of two substances, oxygen and what Cavendish had called
“inflammable air.” The latter gas was now renamed hydrogen (“water
producer”). Black’s fixed air proved to be a gaseous form of oxidized
carbon, or carbon dioxide. The various parts of Lavoisier’s new system were
beginning to fit together beautifully.

The keys to Lavoisier’s success were twofold. First, he carefully accounted

for all the substances, including gases, entering into and emerging from the
chemical reactions he studied by tracking their weights with the greatest
possible precision. He knew to do this partly from Black’s example, but he
proceeded with a mastery that the science had never before seen. Second,
he established a simple operational definition of a chemical element—
namely, a substance that could not be reduced in weight as the result of any
chemical reaction that it undergoes. Oxygen, carbon, iron, and sulfur were
now regarded as elements, along with close to 30 other substances.
Lavoisier wrote a textbook to promote the new oxygenist chemistry, Traité
élémentaire de chimie (1789), which appeared in the same year the French
Revolution began. He and his associates also developed a new
nomenclature—essentially the one used today for inorganic compounds—
along with a new journal. As an aristocrat of the ancien régime and an
investor in a tax-collection agency, Lavoisier was executed in the Reign of
Terror, but by that time (1794) the chemical revolution that he had started
had largely succeeded in replacing phlogistonist chemistry.
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Atomic and molecular theory

Lavoisier’s set of chemical elements, and the new way of understanding
chemical composition, proved to be invaluable for analytic and inorganic
chemistry, but in a real sense the chemical revolution had only just begun.
Around the turn of the century, the English Quaker schoolteacher John
Dalton began to wonder about the invisibly small ultimate particles of which
each of these elemental substances might be composed. He thought that if
the atoms of each of the elements were distinct, they must be characterized
by a distinct weight that is unique to each element. Although these atoms
were far too small to weigh individually, he realized that he could deduce
their weights relative to each other—the ratio of the weight of an atom of
oxygen to one of hydrogen, for instance—by examining reacting weights of
macroscopic quantities of these elements. In fact, the laws of stoichiometry
(combining weights of elements) were just then being developed, and
Dalton used these regularities to justify his inferences. His first discussion of
these issues dates to 1803, and he presented his atomic theory in the
multivolume New System of Chemical Philosophy (1808–27).

Dalton’s atomic theory was a landmark event in the history of chemistry,

but it had a crucial flaw. His procedure required that one know the formulas
of the simple compounds resulting from the combination of the elements.
For example, analytical data of that day indicated that water resulted from
the combination of seven parts by weight of oxygen with one part of
hydrogen. If the resulting water molecule was HO (one atom of each
element combining to form a molecule of water), then the weight ratio of
the atoms of these elements must be the same, seven to one. However, if
the formula were H O, then the weight of an oxygen atom would have to be
2
14 times the weight of a hydrogen atom. There was simply no way to
determine molecular formulas at that time, so Dalton made assumptions
based on the simplicity of nature. He chose HO as his water formula and,
therefore, seven as the relative atomic weight of oxygen.

In the following years, several leading chemists adopted essential elements

of Dalton’s theory, but many objected to the hypothetical elements just
described; some also doubted the very possibility of investigating the world
of the invisibly small. In 1808 the French chemist Joseph-Louis Gay-Lussac
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discovered that when gases combine chemically, they do so in small integral

multiples by volume. Three years later the Italian physicist Amedeo
Avogadro argued that this fact suggested that equal volumes of gases
contain equal numbers of constituent particles (Avogadro’s law), physical
conditions being the same. This idea provided a physical method of
determining certain molecular formulas. For instance, Gay-Lussac had
pointed out that exactly two volumes of hydrogen combine with precisely
one of oxygen to form water. If Avogadro was right, the formula for water
had to be H O. But this line of reasoning also led to the uncomfortable
2
notion that elementary gases had polyatomic molecules (O , H , and so on),
2 2
and therefore many chemists rejected Avogadro’s hypotheses.

By far the greatest of the early atomists was the Swede Jöns Jacob Berzelius,
who accepted parts of Avogadro’s ideas and developed an elaborate
version of chemical atomism by 1826. It was Berzelius who in 1813 had
proposed the alphabetic system for denoting elements, atoms, and
molecular formulas, and the use of formulas as an aid for studying chemical
composition and reactions began to blossom about 1830. However, different
chemists were still making different assumptions regarding the formulas of
simple compounds such as water, and so, for decades, various inconsistent
systems of atomic weights and formulas were in use in the various European
countries.

Berzelius also developed a theory of chemical combination based on the

electrochemical studies that the invention of the battery (1800) had
spawned. He became convinced that all molecules were held together by
the Coulomb force, the electrostatic attraction between oppositely charged
objects. (Berzelius assumed that a molecule’s constituent atoms or groups
of atoms were not neutral, and he called these charged components
radicals.) This theory of electrochemical dualism worked well with inorganic
compounds, but organic substances seemed anomalous. Particularly in the
1830s, when chemists learned how to replace the hydrogen of organic
compounds with chlorine atoms, Berzelius’s theory appeared to be
threatened—after all, hydrogen and chlorine had opposite electrochemical
characteristics, yet the substitution seemed to make little difference in the
properties of the compounds. In the 1840s and ’50s, extensive debates

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over rival systems of chemical atomism and over electrochemical dualism

enlivened the journal literature.

Organic radicals and the theory of chemical structure

Both problems were finally resolved through the further development of
organic chemistry. The leading organic chemists of the day were the German
Justus von Liebig and the Frenchman Jean-Baptiste-André Dumas. In 1830
Liebig invented a device that made organic analysis rapid, convenient, and
accurate, and his laboratory institute at the tiny University of Giessen in
Hesse became the most famous chemical school in the world. Liebig taught
an enormous number of chemists, and his students assisted in his research
program. He was the leading figure in the rise of the research university and
in the idea of a research group. As a professor at Giessen, and later at the
University of Munich, he laid much emphasis on practical applications of
chemistry, especially for physiology, agriculture, and consumer products.
Dumas exerted a similar influence in France, training students and pursuing
research at a private laboratory in Paris.

Both Liebig and Dumas initially accepted the Berzelian scheme and sought
to understand organic molecules as composed of identifiable radicals held
together electrochemically. The younger French chemists Auguste Laurent
and Charles Gerhardt pursued chlorine substitution reactions and cast doubt
on this simple model; sometime after 1840 Liebig and Dumas both retreated
into positivism. In 1852 Liebig’s English former postdoctoral assistant
Edward Frankland noticed a regularity in the combining capacity of the
atoms of certain metals and semimetals. At about the same time, two
former students of both Liebig and Dumas, Alexander Williamson in London
and Charles-Adolphe Wurtz in Paris, were independently approaching the
same idea from a different direction. Using a system of atomic weights and
formulas developed by Gerhardt and Laurent—a modified version of
Berzelius’s system that incorporated Avogadro’s ideas more consistently
—they proposed that oxygen atoms could combine with two other simple
atoms, such as hydrogen, or with two organic radicals and that nitrogen
atoms could combine with three. This was the beginning of the concept of
atomic valence.

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In 1858 the young German theorist August Kekule then expanded this
concept to carbon, not only proposing that carbon atoms were tetravalent
but adding the idea that they could bond to each other to form chains,
comprising a molecular “skeleton” to which other atoms could cling.
Kekule’s theory of chemical structure clarified the compositions of
hundreds of organic compounds and served as a guide to the synthesis of
thousands more. (The self-chaining of carbon atoms was independently
developed by the Scottish chemist Archibald Scott Couper.) This theory
experienced dramatic expansion when Kekule successfully applied it to
aromatic compounds (after 1865) and after Jacobus Henricus van ’t Hoff of
the Netherlands and Joseph LeBel of France independently began to
investigate molecular structures in three dimensions—later called
stereochemistry.

Mendeleev’s periodic law

Kekule’s innovations were closely connected with a reform movement that
gathered steam in the 1850s, seeking to replace the multiplicity of atomic
weight systems with Gerhardt’s and Laurent’s proposal. Indeed, Kekule
could not have succeeded with structure theory if he had not started with
the reformed atomic weights. Kekule, Wurtz, and German chemist Carl
Weltzien were organizers of the first international chemical conference, held
at Karlsruhe in southwestern Germany in September 1860, which was
intended to gain unity and understanding across the European chemical
community. The Italian chemist Stanislao Cannizzaro played perhaps the
most critical role at the conference. The reformers’ success was incomplete,
but the Karlsruhe Congress can stand as an appropriate symbol of the era
when chemistry attained a recognizably modern appearance.

The widespread adoption of a single

reformed set of atomic weights for the 60-
odd known elements appears to have
prompted renewed speculation on the
relationships of the elements to each other,
Dmitri Mendeleev and various proposals for systems of
Russian chemist Dmitri Mendeleev
arranged the 63 known elements
classification were developed in the 1860s.
into a periodic table based on By far the most successful of these systems

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atomic mass, which he published in was that of the Russian chemist Dmitry
Principles of Chemistry (1869).
© Photos.com/Thinkstock Mendeleev. In 1869 he announced that when
the elements were arranged horizontally
according to increasing atomic weight, and a new horizontal row was begun
below the first whenever similar properties in the elements reappear, then
the resulting semi-rectangular table revealed consistent periodicities. The
vertical columns of similar elements were called groups or families, and the
entire array was called the periodic table of the elements. Mendeleev
demonstrated that this manner of looking at the elements was more than
mere chance when he was able to use his periodic law to predict the
existence of three new elements, later named gallium, scandium, and
germanium, which were discovered in the 1870s and ’80s.

To be sure, there were still many anomalies. For example, 15 chemically

similar rare earth elements had been discovered by the end of the century.
These elements were resistant to any periodic system; eventually they were
grouped together in a separate category, the lanthanides (later called the
lanthanoids; see transition element). Then in the 1890s British scientists
William Ramsay and Lord Rayleigh discovered the inert, or rare, gases argon,
helium, neon, krypton, and xenon. These were all clearly members of a
single chemical family, but there were no vacant spaces in the table for
them. Soon after the turn of the 20th century, chemists decided simply to
create an extra group for them.

Structuralist ideas from organic chemistry, as

well as the development of the periodic
table, gave new impetus to the study of
inorganic compounds in the late 19th
century. The leading chemical field in the
periodic table second half of the century, however, was
Modern version of the periodic
table of the elements.
clearly organic chemistry, and the leading
Encyclopædia Britannica, Inc. country was Germany. It was the Germans
who exploited the structure theory most
aggressively, and their success was measured by the explosive growth of
university institutes as well as by practical applications developed in
commercial enterprises. Organic chemists such as August Wilhelm von
Hofmann and Emil Fischer at the University of Berlin and Adolf von Baeyer at
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the University of Munich developed large research groups that turned out
novel compounds, research publications, and doctoral dissertations by the
score. By the late 19th century, German chemistry, both academic and
industrial, dominated Europe and the world.

The rise of physical chemistry

This is not to say that other approaches to chemistry were neglected, nor
that other countries failed to participate in the excitement. Physical studies
of chemical compounds and reactions began early in the century, and the
field of physical chemistry had achieved maturity by the 1880s. Michael
Faraday in England, Hermann Kopp and Robert Bunsen in Germany, and
Henri-Victor Regnault in France carried out investigations on the physical
characteristics of substances in the period 1830–60. Studies of heat, work,
and force led to the rise of thermodynamics around 1850; originally oriented
almost entirely to the science of physics, figures such as the American Josiah
Willard Gibbs, the Frenchmen Marcellin Berthelot and Pierre Duhem, and the
Germans Hermann von Helmholtz and Wilhelm Ostwald then applied
energy and entropy concepts to chemistry in the 1870s and ’80s.
Electrochemistry, invented by the independent efforts of Berzelius and
Humphry Davy in England at the beginning of the century, was pursued
fruitfully by Faraday and others. Bunsen and Gustav Kirchhoff of Germany
developed chemical spectroscopy in the late 1850s. Studies on the kinetics
of chemical reactions began in the 1860s.

All this work culminated in the “official” establishment of the field of

physical chemistry, traditionally considered to be when the Zeitschrift für
Physikalische Chemie (“Journal of Physical Chemistry”) began publication
in 1887. The editors were Ostwald and van ’t Hoff, with Svante Arrhenius of
Sweden, a future Nobelist, an especially important member of its editorial
board. Controversies over the reality of ionic dissociation and other issues
connected with electrochemistry, the theory of solutions, and
thermodynamics enlivened early issues of the journal.

Physical chemists were in increasing demand as universities turned to them

for instruction in basic courses on general and theoretical chemistry. This
was nowhere more true than in the United States, with its vigorously

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expanding educational structure, including both private and state (land-

grant) universities and emerging German-influenced doctoral programs.
Soon after the turn of the century, two chemists at the Massachusetts
Institute of Technology (MIT) who had studied with Ostwald, Arthur Noyes
and Gilbert Lewis, formed the nucleus of a rising American chemical
community. Noyes continued his career at Throop Polytechnic in Pasadena
(later renamed the California Institute of Technology, commonly known as
Caltech), and Lewis went on to the University of California at Berkeley.

Physical chemistry was profoundly altered by what some have called the
second scientific revolution—namely, the discoveries of the electron, X-rays,
radioactivity, and new radioactive elements, the understanding of
radioactive emissions and nuclear decay processes, and early versions of the
theories of quantum mechanics and relativity. All of this happened in just 10
years, from 1895 to 1905, and the scientific bombshells continued in the
following years. In 1911 the British physicist Ernest Rutherford proposed a
nuclear model of the atom, but his orbiting electrons seemed to violate
classical electromagnetic theory, and the model was not immediately
embraced. However, two years later the Danish physicist Niels Bohr resolved
some of these anomalies by applying spectroscopic data and the quantum
theory of the German physicists Max Planck and Albert Einstein to
Rutherford’s model (see figure). Bohr went on to head an international
theoretical research group in Copenhagen that led in developing quantum
mechanics during the 1920s. In the meantime, Rutherford revealed the
existence of the proton and Einstein advanced his theory of general
relativity.

Electronic theories of valence

So much for the physicists; but the chemists
were not sitting on their hands through all of
this. Since its discovery a half century earlier,
one of the greatest puzzles in chemistry had
Rutherford atomic model
Physicist Ernest Rutherford been the central phenomenon of valence. It
envisioned the atom as a miniature was as inexplicable as it was incontrovertibly
solar system, with electrons
orbiting around a massive nucleus, true that oxygen atoms had exactly two
and as mostly empty space, with valence “hooks” with which to form bonds
the nucleus occupying only a very
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small part of the atom. The neutron and carbon normally had four (that is to say,
had not been discovered when
Rutherford proposed his model, oxygen is divalent, carbon tetravalent).
which had a nucleus consisting Moreover, these bonds were not radially
only of protons.
Encyclopædia Britannica, Inc.
symmetrical like electrostatic charges or
gravitation but seemed to be directed at
distinct spatial angles around the atom. And
the existence of highly stable elementary
molecules such as H was downright
2
embarrassing—for what could be the basis
for the strong attraction of two identical
Bohr model of the atom
In the Bohr model of the atom, atoms for each other? Some scientists, such
electrons travel in defined circular as the great Swiss chemist Alfred Werner,
orbits around the nucleus. The
orbits are labeled by an integer, the used combinations of structural-organic and
quantum number n. Electrons can ionic theories to develop a scheme that
jump from one orbit to another by
brilliantly explained the structures of
emitting or absorbing energy. The
inset shows an electron jumping complex inorganic substances known as
from orbit n=3 to orbit n=2,
coordination compounds.
emitting a photon of red light with
an energy of 1.89 eV.
Encyclopædia Britannica, Inc. Others would take their cue from the
discovery of the electron. As early as 1902,
taking into account the work of the English physicist J.J. Thomson, Werner,
and Ramsay and Rayleigh on the rare gases, Lewis privately drew casual
sketches—depicting cubic atoms with outer electrons—that constituted the
first step toward an electronic theory of chemical bonding. However, it was
not until after Rutherford and Bohr had provided the early development of
the nuclear theory of the atom that Lewis’s ideas gelled. (Simultaneously
and independently, the German physicist Walther Kossel published a similar
theory.) Lewis suggested that a chemical bond consisted of a pair of
electrons that was shared between the combining atoms. By equal sharing
of electrons (forming what the American physical chemist Irving Langmuir
was soon to call a covalent bond), each atom could complete its outer
electron shell and thus achieve stability. The normally complete outer shell,
Lewis thought, contained eight electrons—the configuration of the notably
stable (that is, inert) rare gases. This was the octet rule, and it helped to
explain why Mendeleev’s periodicities often came in multiples of eight.

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The Lewis-Kossel-Langmuir electronic theory

of valence (1916–23) was very incomplete,
but was also extraordinarily fruitful for
further developments, and essential
elements of it survived for decades. In 1922
polar covalent bond Bohr proposed electron configurations in the
In polar covalent bonds, such as
that between hydrogen and oxygen
so-called K, L, M, and N shells. The theory
atoms, the electrons are not was soon thereafter modified by breaking
transferred from one atom to the
developments in quantum mechanics
other as they are in an ionic bond.
Instead, some outer electrons achieved by Bohr, German physicist Werner
merely spend more time in the Heisenberg, Austrian physicist Erwin
vicinity of the other atom. The
effect of this orbital distortion is to Schrödinger, and others. In 1927 two
induce regional net charges that German researchers working with
hold the atoms together, such as in
water molecules. Schrödinger in Zürich, Fritz London and
Encyclopædia Britannica, Inc. Walter Heitler, produced the first-ever
quantum mechanical treatment of a chemical
system, the hydrogen molecule.

The American physical chemist Linus Pauling (along with another American,
John Slater) independently developed this approach into what he called the
valence bond method of understanding chemical combination. The orbitals
in the various electron shells (classified by the letters s, p, d, and f) could be
mathematically “hybridized,” resulting in the directed bonds actually
observed in chemical compounds. Pauling also made extensive use of the
quantum mechanical resonance effect, especially for understanding
aromatic compounds. All of this was summarized in his classic work The
Nature of the Chemical Bond (1939). An alternative quantum mechanical
method of understanding chemical bonding, called the molecular orbital
method, was developed by the American chemist Robert Mulliken and the
German physicist Friedrich Hund. Although mathematically more complex,
this approach has largely replaced Pauling’s. In any case, ever since Lewis
and Bohr, it has been understood that all chemical reactions and all chemical
bonding involves the outer electron shells—the valence electrons—of
participating atoms.

Organic chemists also incorporated electronic ideas into their theories. In

the 1920s the Englishmen Robert Robinson and Christopher Ingold—bitter
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rivals then and later—led in the development of electronic theories of

organic reaction mechanisms by focusing on rearranging electron pairs over
the course of chemical reactions. Not only did this allow chemists to
understand the intimate details of reactions in a way that had not previously
been possible, but it also allowed them to successfully predict the
reactivities of organic compounds in different chemical environments. Other
studies of quantum mechanics applied to organic substances, combined
with the kinetics of reactions, the nature of acids and bases, and
instrumental methods of understanding compounds, led to a well-
developed specialty field of physical organic chemistry.

Biochemistry, polymers, and technology

Organic chemistry, of course, looks not only in the direction of physics and
physical chemistry but also, and even more essentially, in the direction of
biology. Biochemistry began with studies of substances derived from plants
and animals. By about 1800 many such substances were known, and
chemistry had begun to assist physiology in understanding biological
function. The nature of the principal chemical categories of foods—proteins,
lipids, and carbohydrates—began to be studied in the first half of the
century. By the end of the century, the role of enzymes as organic catalysts
was clarified, and amino acids were perceived as constituents of proteins.
The brilliant German chemist Emil Fischer determined the nature and
structure of many carbohydrates and proteins. The announcement of the
discovery (1912) of vitamins, independently by the Polish-born American
biochemist Casimir Funk and the British biochemist Frederick Hopkins,
precipitated a revolution in both biochemistry and human nutrition.
Gradually, the details of intermediary metabolism—the way the body uses
nutrient substances for energy, growth, and tissue repair—were unraveled.
Perhaps the most representative example of this kind of work was the
German-born British biochemist Hans Krebs’s establishment of the
tricarboxylic acid cycle, or Krebs cycle, in the 1930s.

But the most dramatic discovery in the history of 20th-century biochemistry

was surely the structure of DNA (deoxyribonucleic acid), revealed by
American geneticist James Watson and British biophysicist Francis Crick in
1953—the famous double helix. The new understanding of the molecule

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that incorporates the genetic code provided an essential link between

chemistry and biology, a bridge over which much traffic continues to flow.
The individual “letters” that make the code—four nucleotides named
adenine, guanine, cytosine, and thymine—were discovered a century ago,
but only at the close of the 20th century could the sequence of these letters
in the genes that make up DNA be determined en masse. In June 2000,
representatives from the publicly funded U.S. Human Genome Project and
from Celera Genomics, a private company in Rockville, Md., simultaneously
announced the independent and nearly complete sequencing of the more
than three billion nucleotides in the human genome. However, both groups
emphasized that this monumental accomplishment was, in a broader
perspective, only the end of a race to the starting line.

DNA is, of course, a macromolecule, and an understanding of this centrally

important category of chemical compounds was a precondition for the
events just described. Starch, cellulose, proteins, and rubber are other
examples of natural macromolecules, or very large polymers. The word
polymer (meaning “multiple parts”) was coined by Berzelius about 1830,
but in the 19th century it was only applied to special cases such as ethylene
(C H ) versus butylene (C H ). Only in the 1920s did the German chemist
2 4 4 8
Hermann Staudinger definitely assert that complex carbohydrates and
rubber had huge molecules. He coined the word macromolecule, viewing
polymers as consisting of similar units joined head to tail by the hundreds
and connected by ordinary chemical bonds.

Empirical work on polymers had long predated Staudinger’s contributions,

though. Nitrocellulose was used in the production of smokeless gunpowder,
and mixtures of nitrocellulose with other organic compounds led to the first
commercial polymers: collodion, xylonite, and celluloid. The last of these was
the earliest plastic. The first totally synthetic plastic was patented by Leo
Baekeland in 1909 and named Bakelite. Many new plastics were introduced
in the 1920s, ’30s, and ’40s, including polymerized versions of acrylic acid
(a variety of carboxylic acid), vinyl chloride, styrene, ethylene, and many
others. Wallace Carothers’s nylon excited extraordinary attention during
the World War II years. Great effort was also devoted to develop artificial
substitutes for rubber—a natural resource in especially short supply during

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wartime. Already by World War I, German chemists had substitute materials,

though many were less than satisfactory. The first highly successful rubber
substitutes were produced in the early 1930s and were of great importance
in World War II.

During the interwar period, the leading role for chemistry shifted away from
Germany. This was largely the result of the 1914–18 war, which alerted the
Allied countries to the extent to which they had become dependent on the
German chemical industries. Dyes, drugs, fertilizers, explosives,
photochemicals, food chemicals (such as chemicals for food additives, food
colouring, and food preservation), heavy chemicals, and strategic materiel of
many kinds had been supplied internationally before the war largely by
German chemical companies, and, when supplies of these vital materials
were cut off in 1914, the Allies had to scramble to replace them. One
particularly striking example is the introduction of chlorine gas and other
poisons, starting in 1915, as chemical warfare agents. In any case, after the
war ended, chemistry was enthusiastically promoted in Britain, France, and
the United States, and the interwar years saw the United States rise to the
status of a world power in science, including chemistry.

All this makes clear why World War I is sometimes referred to as “the
chemists’ war,” in the same way that World War II can be called “the
physicists’ war” because of radar and nuclear weapons. But chemistry was
an essential partner to physics in the development of nuclear science and
technology. Indeed, the synthesis of transuranium elements (atomic
numbers greater than 92) was a direct consequence of the research leading
to (and during) the Manhattan Project in World War II. This is all part of the
legacy of the dean of nuclear chemists, American Glenn Seaborg, discoverer
or codiscoverer of 10 of the transuranium elements. In 1997, element 106
was named seaborgium in his honour.

The instrumental revolution

As far as the daily practice of chemical
research is concerned, probably the most
dramatic change during the 20th century
was the revolution in methods of analysis. In

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Nobel Prize: chemical elements 1930 chemists still used “wet-chemical,” or

discovered by winners
Chemical elements discovered by test-tube, methods that had changed little in
Nobel Prize recipients. the previous hundred years: reagent tests,
Encyclopædia Britannica, Inc.
titrations, determination of boiling and
melting points, elemental combustion
analysis, synthetic and analytic structural arguments, and so on. Starting
with commercial labs that provided an out-source for routine analyses and
with pH meters that displaced chemical indicators, chemists increasingly
began to rely on physical instrumentation and specialists rather than
personally administered wet-chemical methods. Physical instrumentation
provides the sharp “eyes” that can see to the atomic-molecular level.

In the 1910s J.J. Thomson and his assistant Francis Aston had developed the
mass spectrograph to measure atomic and molecular weights with high
accuracy. It was gradually improved, so that by the 1940s the mass
spectrograph had been transformed into the mass spectrometer—no longer
a machine for atomic weight research but rather an analytical instrument for
the routine identification of complex unknown compounds (see mass
spectrometry). Similarly, colorimetry had a long history, dating back well
into the previous century. In the 1940s colorimetric principles were applied
to sophisticated instrumentation to create a range of usable
spectrophotometers, including visible, infrared, ultraviolet, and Raman
spectroscopy. The later addition of laser and computer technology to
analytical spectrometers provided further sophistication and also offered
important tools for studies of the kinetics and mechanisms of reactions.

Chromatography, used for generations to separate mixtures and identify the

presence of a target substance, was ever more impressively automated, and
gas chromatography (GC) in particular experienced vigorous development.
Nuclear magnetic resonance (NMR), which uses radio waves interacting with
a magnetic field to reveal the chemical environments of hydrogen atoms in
a compound, was also developed after World War II. Early NMR machines
were available in the 1950s; by the 1960s they were workhorses of organic
chemical analysis. Also by this time, GC-NMR combinations were introduced,
providing chemists unexcelled ability to separate and analyze minute
amounts of sample. In the 1980s NMR became well known to the general
public, when the technique was applied to medicine—though the name of
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the application was altered to magnetic resonance imaging (MRI) to avoid

the loaded word nuclear.

Many other instrumental methods have seen vigorous development, such as

electron paramagnetic resonance and X-ray diffraction. In sum, between
1930 and 1970 the analytical revolution in chemistry utterly transformed the
practice of the science and enormously accelerated its progress. Nor did the
pace of innovation in analytical chemistry diminish during the final third of
the century.

Organic chemistry in the 20th century

No specialty was more affected by these changes than organic chemistry.
The case of the American chemist Robert B. Woodward may be taken as
illustrative. Woodward was the finest master of classical organic chemistry,
but he was also a leader in aggressively exploiting new instrumentation,
especially infrared, ultraviolet, and NMR spectrometry. His stock in trade was
“total synthesis,” the creation of a (usually natural) organic substance in
the laboratory, beginning with the simplest possible starting materials.
Among the compounds that he and his collaborators synthesized were
alkaloids such as quinine and strychnine, antibiotics such as tetracycline, and
the extremely complex molecule chlorophyll. Woodward’s highest
accomplishment in this field actually came six years after his receipt of the
Nobel Prize for Chemistry in 1965: the synthesis of vitamin B , a notable
12
landmark in complexity. Progress continued apace after Woodward’s
death. By 1994 a group at Harvard University had succeeded in synthesizing
an extraordinarily challenging natural product, called palytoxin, that had
more than 60 stereocentres.

These total syntheses have had both practical and scientific spin-offs. Before
the “instrumental revolution,” syntheses were often or even usually done
to prove molecular structures. Today they are a central element of the search
for new drugs. They can also illuminate theory. Together with a young
Polish-born American chemical theoretician named Roald Hoffmann,
Woodward followed up hints from the B synthesis that resulted in the
12
formulation of orbital symmetry rules. These rules seemed to apply to all
thermal or photochemical organic reactions that occur in a single step. The

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simplicity and accuracy of the predictions generated by the new rules,

including highly specific stereochemical details of the product of the
reaction, provided an invaluable tool for synthetic organic chemists.

Stereochemistry, born toward the end of the 19th century, received steadily
increasing attention throughout the 20th century. The three-dimensional
details of molecular structure proved to be not only critical to chemical (and
biochemical) function but also extraordinarily difficult to analyze and
synthesize. Several Nobel Prizes in the second half of the century—those
awarded to Derek Barton of Britain, John Cornforth of Australia, Vladimir
Prelog of the Soviet Union, and others—were given partially or entirely to
honour stereochemical advances. Also important in this regard was the
American Elias J. Corey, awarded the Nobel Prize for Chemistry in 1990, who
developed what he called retrosynthetic analysis, assisted increasingly by
special interactive computer software. This approach transformed synthetic
organic chemistry. Another important innovation was combinatorial
chemistry, in which scores of compounds are simultaneously prepared—all
permutations on a basic type—and then screened for physiological activity.

Chemistry in the 21st century

Two more innovations of the late 20th century deserve at least brief
mention, especially as they are special focuses of the chemical industry in
the 21st century. The phenomenon of superconductivity (the ability to
conduct electricity with no resistance) was discovered in 1911 at
temperatures very close to absolute zero (0 K, −273.15 °C, or −459.67 °F). In
1986 two Swiss chemists discovered that lanthanum copper oxide doped
with barium became superconducting at the “high” temperature of 35 K
(−238 °C, or −397 °F). Since then, new superconducting materials have been
discovered that operate well above the temperature of liquid nitrogen—77 K
(−196 °C, or −321 °F). In addition to its purely scientific interest, much
research focuses on practical applications of superconductivity.

In 1985 Richard Smalley and Robert Curl at Rice University in Houston, Tex.,
collaborating with Harold Kroto of the University of Sussex in Brighton, Eng.,
discovered a fundamental new form of carbon, possessing molecules
consisting solely of 60 carbon atoms. They named it buckminsterfullerene

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(later nicknamed “buckyball”), after Buckminster Fuller, the inventor of the

geodesic dome. Research on fullerenes has accelerated since 1990, when a
method was announced for producing buckyballs in large quantities and
practical applications appeared likely. In 1991 Science magazine named
buckminsterfullerene their “molecule of the year.”

Two centuries ago, Lavoisier’s chemical revolution could still be questioned

by the English émigré Joseph Priestley. A century ago, the physical reality of
the atom was still doubted by some. Today, chemists can maneuver atoms
one by one with a scanning tunneling microscope, and other techniques of
what has become known as nanotechnology are in rapid development. The
history of chemistry is an extraordinary story.

Alan J. Rocke

Citation Information
Article Title: chemistry
Website Name: Encyclopaedia Britannica
Publisher: Encyclopaedia Britannica, Inc.
Date Published: 20 December 2021
URL: https://www.britannica.com/science/chemistry
Access Date: March 08, 2022

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