History of chemistry

From Wikipedia, the free encyclopedia

The 1871 periodic table constructed by Dmitri Mendeleev. The periodic table is one of the
most potent icons in science, lying at the core of chemistry and embodying the most
fundamental principles of the field.

The history of chemistry represents a time span from ancient history to the present. By 1000
BC, civilizations used technologies that would eventually form the basis of the various
branches of chemistry. Examples include extracting metals from ores, making pottery and
glazes, fermenting beer and wine, extracting chemicals from plants for medicine and
perfume, rendering fat into soap, making glass, and making alloys like bronze.

The protoscience of chemistry, alchemy, was unsuccessful in explaining the nature of matter
and its transformations. However, by performing experiments and recording the results,
alchemists set the stage for modern chemistry. The distinction began to emerge when a clear
differentiation was made between chemistry and alchemy by Robert Boyle in his work The
Sceptical Chymist (1661). While both alchemy and chemistry are concerned with matter and
its transformations, chemists are seen as applying scientific method to their work.

Chemistry is considered to have become an established science with the work of Antoine
Lavoisier, who developed a law of conservation of mass that demanded careful measurement
and quantitative observations of chemical phenomena. The history of chemistry is intertwined
with the history of thermodynamics, especially through the work of Willard Gibbs.[1]

Contents
 1 Ancient history
o 1.1 Early metallurgy
o 1.2 Bronze Age
o 1.3 Iron Age
o 1.4 Classical antiquity and atomism
 1.4.1 Ancient world
 2 Medieval alchemy
o 2.1 The philosopher's stone
o 2.2 Problems encountered with alchemy
o 2.3 Alchemy in the Islamic world
 3 17th and 18th centuries: Early chemistry
 o 3.1 Robert Boyle
o 3.2 Development and dismantling of phlogiston
o 3.3 Volta and the Voltaic pile
o 3.4 Antoine-Laurent de Lavoisier
 4 19th century
o 4.1 John Dalton
o 4.2 Jöns Jacob Berzelius
o 4.3 New elements and gas laws
o 4.4 Wöhler and the vitalism debate
o 4.5 Mid-1800s
o 4.6 Perkin, Crookes, and Nobel
o 4.7 Mendeleev's periodic table
o 4.8 Josiah Willard Gibbs
o 4.9 Late 19th century
 4.9.1 Ramsay's discovery of the noble gases
 4.9.2 Marie and Pierre Curie
 4.9.3 Ernest Rutherford
 5 20th century
o 5.1 Niels Bohr
o 5.2 Gilbert N. Lewis
o 5.3 Quantum mechanics
o 5.4 Quantum chemistry
o 5.5 Molecular biology and biochemistry
o 5.6 Late 20th century
 6 Mathematics and chemistry
 7 Scope of chemistry
o 7.1 Chemical industry
 8 See also
o 8.1 Histories and timelines
o 8.2 Notable chemists
 9 Notes
 10 References
 11 Further reading
 12 External links

Ancient history
Early metallurgy

Main articles: History of ferrous metallurgy and History of metallurgy in the Indian
subcontinent

The earliest recorded metal employed by humans seems to be gold which can be found free
or "native". Small amounts of natural gold have been found in Spanish caves used during the
late Paleolithic period, c. 40,000 BC.[2]

Silver, copper, tin and meteoric iron can also be found native, allowing a limited amount of
metalworking in ancient cultures.[3] Egyptian weapons made from meteoric iron in about
3000 BC were highly prized as "Daggers from Heaven".[4]
Arguably the first chemical reaction used in a controlled manner was fire. However, for
millennia fire was seen simply as a mystical force that could transform one substance into
another (burning wood, or boiling water) while producing heat and light. Fire affected many
aspects of early societies. These ranged from the simplest facets of everyday life, such as
cooking and habitat lighting, to more advanced technologies, such as pottery, bricks, and
melting of metals to make tools.

It was fire that led to the discovery of glass and the purification of metals which in turn gave
way to the rise of metallurgy.[citation needed] During the early stages of metallurgy, methods of
purification of metals were sought, and gold, known in ancient Egypt as early as 2900 BC,
became a precious metal.

Bronze Age

Main article: Bronze Age

Certain metals can be recovered from their ores by simply heating the rocks in a fire: notably
tin, lead and (at a higher temperature) copper, a process known as smelting. The first
evidence of this extractive metallurgy dates from the 5th and 6th millennium BC, and was
found in the archaeological sites of Majdanpek, Yarmovac and Plocnik, all three in Serbia.
To date, the earliest copper smelting is found at the Belovode site,[5] these examples include a
copper axe from 5500 BC belonging to the Vinča culture.[6] Other signs of early metals are
found from the third millennium BC in places like Palmela (Portugal), Los Millares (Spain),
and Stonehenge (United Kingdom). However, as often happens with the study of prehistoric
times, the ultimate beginnings cannot be clearly defined and new discoveries are ongoing.

Mining areas of the ancient Middle East. Boxes colors: arsenic is in brown, copper in red, tin
in grey, iron in reddish brown, gold in yellow, silver in white and lead in black. Yellow area
stands for arsenic bronze, while grey area stands for tin bronze.

These first metals were single ones or as found. By combining copper and tin, a superior
metal could be made, an alloy called bronze, a major technological shift which began the
Bronze Age about 3500 BC. The Bronze Age was period in human cultural development
when the most advanced metalworking (at least in systematic and widespread use) included
techniques for smelting copper and tin from naturally occurring outcroppings of copper ores,
and then smelting those ores to cast bronze. These naturally occurring ores typically included
arsenic as a common impurity. Copper/tin ores are rare, as reflected in the fact that there were
no tin bronzes in western Asia before 3000 BC.

After the Bronze Age, the history of metallurgy was marked by armies seeking better
weaponry. Countries in Eurasia prospered when they made the superior alloys, which, in turn,
made better armor and better weapons.[citation needed] This often determined the outcomes of
battles.[citation needed] Significant progress in metallurgy and alchemy was made in ancient
India.[7]

Iron Age

Main article: Iron Age

The extraction of iron from its ore into a workable metal is much more difficult than copper
or tin. It appears to have been invented by the Hittites in about 1200 BC, beginning the Iron
Age. The secret of extracting and working iron was a key factor in the success of the
Philistines.[4][8]

In other words, the Iron Age refers to the advent of ferrous metallurgy. Historical
developments in ferrous metallurgy can be found in a wide variety of past cultures and
civilizations. This includes the ancient and medieval kingdoms and empires of the Middle
East and Near East, ancient Iran, ancient Egypt, ancient Nubia, and Anatolia (Turkey),
Ancient Nok, Carthage, the Greeks and Romans of ancient Europe, medieval Europe, ancient
and medieval China, ancient and medieval India, ancient and medieval Japan, amongst
others. Many applications, practices, and devices associated or involved in metallurgy were
established in ancient China, such as the innovation of the blast furnace, cast iron, hydraulic-
powered trip hammers, and double acting piston bellows.[9][10]

Classical antiquity and atomism

Main article: Atomism

Democritus, Greek philosopher of atomistic school.

Philosophical attempts to rationalize why different substances have different properties

(color, density, smell), exist in different states (gaseous, liquid, and solid), and react in a
different manner when exposed to environments, for example to water or fire or temperature
changes, led ancient philosophers to postulate the first theories on nature and chemistry. The
history of such philosophical theories that relate to chemistry can probably be traced back to
every single ancient civilization. The common aspect in all these theories was the attempt to
identify a small number of primary classical element that make up all the various substances
in nature. Substances like air, water, and soil/earth, energy forms, such as fire and light, and
more abstract concepts such as ideas, aether, and heaven, were common in ancient
civilizations even in absence of any cross-fertilization; for example in Greek, Indian, Mayan,
and ancient Chinese philosophies all considered air, water, earth and fire as primary
elements.[citation needed]

Ancient world

Around 420 BC, Empedocles stated that all matter is made up of four elemental substances—
earth, fire, air and water. The early theory of atomism can be traced back to ancient Greece
and ancient India.[11] Greek atomism dates back to the Greek philosopher Democritus, who
declared that matter is composed of indivisible and indestructible atoms around 380 BC.
Leucippus also declared that atoms were the most indivisible part of matter. This coincided
with a similar declaration by Indian philosopher Kanada in his Vaisheshika sutras around the
same time period.[11] In much the same fashion he discussed the existence of gases. What
Kanada declared by sutra, Democritus declared by philosophical musing. Both suffered from
a lack of empirical data. Without scientific proof, the existence of atoms was easy to deny.
Aristotle opposed the existence of atoms in 330 BC. Earlier, in 380 BC, a Greek text
attributed to Polybus argues that the human body is composed of four humours. Around 300
BC, Epicurus postulated a universe of indestructible atoms in which man himself is
responsible for achieving a balanced life.

With the goal of explaining Epicurean philosophy to a Roman audience, the Roman poet and
philosopher Lucretius[12] wrote De Rerum Natura (The Nature of Things)[13] in 50 BC. In the
work, Lucretius presents the principles of atomism; the nature of the mind and soul;
explanations of sensation and thought; the development of the world and its phenomena; and
explains a variety of celestial and terrestrial phenomena.

Much of the early development of purification methods is described by Pliny the Elder in his
Naturalis Historia. He made attempts to explain those methods, as well as making acute
observations of the state of many minerals.

Medieval alchemy
See also: Minima naturalia, a medieval Aristotelian concept analogous to atomism

Seventeenth century alchemical emblem showing the four Classical elements in the corners
of the image, alongside the tria prima on the central triangle.
The elemental system used in Medieval alchemy was developed primarily by the Persian
alchemist Jābir ibn Hayyān and rooted in the classical elements of Greek tradition.[14] His
system consisted of the four Aristotelian elements of air, earth, fire, and water in addition to
two philosophical elements: sulphur, characterizing the principle of combustibility; "the stone
which burns", and mercury, characterizing the principle of metallic properties. They were
seen by early alchemists as idealized expressions of irreducibile components of the
universe[15] and are of larger consideration within philosophical alchemy.

The three metallic principles: sulphur to flammability or combustion, mercury to volatility

and stability, and salt to solidity. became the tria prima of the Swiss alchemist Paracelsus. He
reasoned that Aristotle's four-element theory appeared in bodies as three principles.
Paracelsus saw these principles as fundamental and justified them by recourse to the
description of how wood burns in fire. Mercury included the cohesive principle, so that when
it left in smoke the wood fell apart. Smoke described the volatility (the mercurial principle),
the heat-giving flames described flammability (sulphur), and the remnant ash described
solidity (salt).[16]

The philosopher's stone

Main article: Alchemy

"The Alchemist", by Sir William Douglas, 1855

Alchemy is defined by the Hermetic quest for the philosopher's stone, the study of which is
steeped in symbolic mysticism, and differs greatly from modern science. Alchemists toiled to
make transformations on an esoteric (spiritual) and/or exoteric (practical) level.[17] It was the
protoscientific, exoteric aspects of alchemy that contributed heavily to the evolution of
chemistry in Greco-Roman Egypt, the Islamic Golden Age, and then in Europe. Alchemy and
chemistry share an interest in the composition and properties of matter, and prior to the
eighteenth century were not separated into distinct disciplines. The term chymistry has been
used to describe the blend of alchemy and chemistry that existed before this time.[18]

The earliest Western alchemists, who lived in the first centuries of the common era, invented
chemical apparatus. The bain-marie, or water bath is named for Mary the Jewess. Her work
also gives the first descriptions of the tribikos and kerotakis.[19] Cleopatra the Alchemist
described furnaces and has been credited with the invention of the alembic.[20] Later, the
experimental framework established by Jabir ibn Hayyan influenced alchemists as the
discipline migrated through the Islamic world, then to Europe in the twelfth century.

During the Renaissance, exoteric alchemy remained popular in the form of Paracelsian
iatrochemistry, while spiritual alchemy flourished, realigned to its Platonic, Hermetic, and
Gnostic roots. Consequently, the symbolic quest for the philosopher's stone was not
superseded by scientific advances, and was still the domain of respected scientists and
doctors until the early eighteenth century. Early modern alchemists who are renowned for
their scientific contributions include Jan Baptist van Helmont, Robert Boyle, and Isaac
Newton.

Problems encountered with alchemy

There were several problems with alchemy, as seen from today's standpoint. There was no
systematic naming scheme for new compounds, and the language was esoteric and vague to
the point that the terminologies meant different things to different people. In fact, according
to The Fontana History of Chemistry (Brock, 1992):

The language of alchemy soon developed an arcane and secretive technical

vocabulary designed to conceal information from the uninitiated. To a large degree,
this language is incomprehensible to us today, though it is apparent that readers of
Geoffery Chaucer's Canon's Yeoman's Tale or audiences of Ben Jonson's The
Alchemist were able to construe it sufficiently to laugh at it.[21]

Chaucer's tale exposed the more fraudulent side of alchemy, especially the manufacture of
counterfeit gold from cheap substances. Less than a century earlier, Dante Alighieri also
demonstrated an awareness of this fraudulence, causing him to consign all alchemists to the
Inferno in his writings. Soon after, in 1317, the Avignon Pope John XXII ordered all
alchemists to leave France for making counterfeit money. A law was passed in England in
1403 which made the "multiplication of metals" punishable by death. Despite these and other
apparently extreme measures, alchemy did not die. Royalty and privileged classes still sought
to discover the philosopher's stone and the elixir of life for themselves.[22]

There was also no agreed-upon scientific method for making experiments reproducible.
Indeed, many alchemists included in their methods irrelevant information such as the timing
of the tides or the phases of the moon. The esoteric nature and codified vocabulary of
alchemy appeared to be more useful in concealing the fact that they could not be sure of very
much at all. As early as the 14th century, cracks seemed to grow in the facade of alchemy;
and people became sceptical.[citation needed] Clearly, there needed to be a scientific method
where experiments can be repeated by other people, and results needed to be reported in a
clear language that laid out both what is known and unknown.

Alchemy in the Islamic world

Jābir ibn Hayyān (Geber), a Persian alchemist whose experimental research laid the
foundations of chemistry.
Main article: Alchemy and chemistry in medieval Islam

In the Islamic World, the Muslims were translating the works of the ancient Greeks and
Egyptians into Arabic and were experimenting with scientific ideas.[23] The development of
the modern scientific method was slow and arduous, but an early scientific method for
chemistry began emerging among early Muslim chemists, beginning with the 9th century
chemist Jābir ibn Hayyān (known as "Geber" in Europe), who is considered as "the father of
chemistry".[24][25][26][27] He introduced a systematic and experimental approach to scientific
research based in the laboratory, in contrast to the ancient Greek and Egyptian alchemists
whose works were largely allegorical and often unintelligble.[28] He also invented and named
the alembic (al-anbiq), chemically analyzed many chemical substances, composed lapidaries,
distinguished between alkalis and acids, and manufactured hundreds of drugs.[29] He also
refined the theory of five classical elements into the theory of seven alchemical elements after
identifying mercury and sulfur as chemical elements.[30][verification needed]

Among other influential Muslim chemists, Abū al-Rayhān al-Bīrūnī,[31] Avicenna[32] and Al-
Kindi refuted the theories of alchemy, particularly the theory of the transmutation of metals;
and al-Tusi described a version of the conservation of mass, noting that a body of matter is
able to change but is not able to disappear.[33] Rhazes refuted Aristotle's theory of four
classical elements for the first time and set up the firm foundations of modern chemistry,
using the laboratory in the modern sense, designing and describing more than twenty
instruments, many parts of which are still in use today, such as a crucible, cucurbit or retort
for distillation, and the head of a still with a delivery tube (ambiq, Latin alembic), and various
types of furnace or stove.[citation needed]

For practitioners in Europe, alchemy became an intellectual pursuit after early Arabic
alchemy became available through Latin translation, and over time, they improved.
Paracelsus (1493–1541), for example, rejected the 4-elemental theory and with only a vague
understanding of his chemicals and medicines, formed a hybrid of alchemy and science in
what was to be called iatrochemistry. Paracelsus was not perfect in making his experiments
truly scientific. For example, as an extension of his theory that new compounds could be
made by combining mercury with sulfur, he once made what he thought was "oil of sulfur".
This was actually dimethyl ether, which had neither mercury nor sulfur.[citation needed]
17th and 18th centuries: Early chemistry

Agricola, author of De re metallica

Workroom, from De re metallica, 1556, Chemical Heritage Foundation

See also: Timeline of chemistry and Corpuscularianism

Practical attempts to improve the refining of ores and their extraction to smelt metals was an
important source of information for early chemists in the 16th century, among them Georg
Agricola (1494–1555), who published his great work De re metallica in 1556. His work
describes the highly developed and complex processes of mining metal ores, metal extraction
and metallurgy of the time. His approach removed the mysticism associated with the subject,
creating the practical base upon which others could build. The work describes the many kinds
of furnace used to smelt ore, and stimulated interest in minerals and their composition. It is
no coincidence that he gives numerous references to the earlier author, Pliny the Elder and his
Naturalis Historia. Agricola has been described as the "father of metallurgy".[34]

In 1605, Sir Francis Bacon published The Proficience and Advancement of Learning, which
contains a description of what would later be known as the scientific method.[35] In 1605,
Michal Sedziwój publishes the alchemical treatise A New Light of Alchemy which proposed
the existence of the "food of life" within air, much later recognized as oxygen. In 1615 Jean
Beguin published the Tyrocinium Chymicum, an early chemistry textbook, and in it draws the
first-ever chemical equation.[36] In 1637 René Descartes publishes Discours de la méthode,
which contains an outline of the scientific method.

The Dutch chemist Jan Baptist van Helmont's work Ortus medicinae was published
posthumously in 1648; the book is cited by some as a major transitional work between
alchemy and chemistry, and as an important influence on Robert Boyle. The book contains
the results of numerous experiments and establishes an early version of the law of
conservation of mass. Working during the time just after Paracelsus and iatrochemistry, Jan
Baptist van Helmont suggested that there are insubstantial substances other than air and
coined a name for them - "gas", from the Greek word chaos. In addition to introducing the
word "gas" into the vocabulary of scientists, van Helmont conducted several experiments
involving gases. Jan Baptist van Helmont is also remembered today largely for his ideas on
spontaneous generation and his 5-year tree experiment, as well as being considered the
founder of pneumatic chemistry.

Robert Boyle

Robert Boyle, one of the co-founders of modern chemistry through his use of proper
experimentation, which further separated chemistry from alchemy

Title page from The sceptical chymist, 1661, Chemical Heritage Foundation

Anglo-Irish chemist Robert Boyle (1627–1691) is considered to have refined the modern
scientific method for alchemy and to have separated chemistry further from alchemy.[37]
Although his research clearly has its roots in the alchemical tradition, Boyle is largely
regarded today as the first modern chemist, and therefore one of the founders of modern
chemistry, and one of the pioneers of modern experimental scientific method. Although
Boyle was not the original discoverer, he is best known for Boyle's law, which he presented
in 1662:[38] the law describes the inversely proportional relationship between the absolute
pressure and volume of a gas, if the temperature is kept constant within a closed system.[39][40]

Boyle is also credited for his landmark publication The Sceptical Chymist in 1661, which is
seen as a cornerstone book in the field of chemistry. In the work, Boyle presents his
hypothesis that every phenomenon was the result of collisions of particles in motion. Boyle
appealed to chemists to experiment and asserted that experiments denied the limiting of
chemical elements to only the classic four: earth, fire, air, and water. He also pleaded that
chemistry should cease to be subservient to medicine or to alchemy, and rise to the status of a
science. Importantly, he advocated a rigorous approach to scientific experiment: he believed
all theories must be proved experimentally before being regarded as true. The work contains
some of the earliest modern ideas of atoms, molecules, and chemical reaction, and marks the
beginning of the history of modern chemistry.

Boyle also tried to purify chemicals to obtain reproducible reactions. He was a vocal
proponent of the mechanical philosophy proposed by René Descartes to explain and quantify
the physical properties and interactions of material substances. Boyle was an atomist, but
favoured the word corpuscle over atoms. He commented that the finest division of matter
where the properties are retained is at the level of corpuscles. He also performed numerous
investigations with an air pump, and noted that the mercury fell as air was pumped out. He
also observed that pumping the air out of a container would extinguish a flame and kill small
animals placed inside. Boyle helped to lay the foundations for the Chemical Revolution with
his mechanical corpuscular philosophy.[41] Boyle repeated the tree experiment of van
Helmont, and was the first to use indicators which changed colors with acidity.

Development and dismantling of phlogiston

Joseph Priestley, co-discoverer of the element oxygen, which he called "dephlogisticated air"

In 1702, German chemist Georg Stahl coined the name "phlogiston" for the substance
believed to be released in the process of burning. Around 1735, Swedish chemist Georg
Brandt analyzed a dark blue pigment found in copper ore. Brandt demonstrated that the
pigment contained a new element, later named cobalt. In 1751, a Swedish chemist and pupil
of Stahl's named Axel Fredrik Cronstedt, identified an impurity in copper ore as a separate
metallic element, which he named nickel. Cronstedt is one of the founders of modern
mineralogy.[42] Cronstedt also discovered the mineral scheelite in 1751, which he named
tungsten, meaning "heavy stone" in Swedish.

In 1754, Scottish chemist Joseph Black isolated carbon dioxide, which he called "fixed
air".[43] In 1757, Louis Claude Cadet de Gassicourt, while investigating arsenic compounds,
creates Cadet's fuming liquid, later discovered to be cacodyl oxide, considered to be the first
synthetic organometallic compound.[44] In 1758, Joseph Black formulated the concept of
latent heat to explain the thermochemistry of phase changes.[45] In 1766, English chemist
Henry Cavendish isolated hydrogen, which he called "inflammable air". Cavendish
discovered hydrogen as a colorless, odourless gas that burns and can form an explosive
mixture with air, and published a paper on the production of water by burning inflammable
air (that is, hydrogen) in dephlogisticated air (now known to be oxygen), the latter a
constituent of atmospheric air (phlogiston theory).

In 1773, Swedish chemist Carl Wilhelm Scheele discovered oxygen, which he called "fire
air", but did not immediately publish his achievement.[46] In 1774, English chemist Joseph
Priestley independently isolated oxygen in its gaseous state, calling it "dephlogisticated air",
and published his work before Scheele.[47][48] During his lifetime, Priestley's considerable
scientific reputation rested on his invention of soda water, his writings on electricity, and his
discovery of several "airs" (gases), the most famous being what Priestley dubbed
"dephlogisticated air" (oxygen). However, Priestley's determination to defend phlogiston
theory and to reject what would become the chemical revolution eventually left him isolated
within the scientific community.

In 1781, Carl Wilhelm Scheele discovered that a new acid, tungstic acid, could be made from
Cronstedt's scheelite (at the time named tungsten). Scheele and Torbern Bergman suggested
that it might be possible to obtain a new metal by reducing this acid.[49] In 1783, José and
Fausto Elhuyar found an acid made from wolframite that was identical to tungstic acid. Later
that year, in Spain, the brothers succeeded in isolating the metal now known as tungsten by
reduction of this acid with charcoal, and they are credited with the discovery of the
element.[50][51]

Volta and the Voltaic pile

A voltaic pile on display in the Tempio Voltiano (the Volta Temple) near Volta's home in
Como.

Italian physicist Alessandro Volta constructed a device for accumulating a large charge by a
series of inductions and groundings. He investigated the 1780s discovery "animal electricity"
by Luigi Galvani, and found that the electric current was generated from the contact of
dissimilar metals, and that the frog leg was only acting as a detector. Volta demonstrated in
1794 that when two metals and brine-soaked cloth or cardboard are arranged in a circuit they
produce an electric current.

In 1800, Volta stacked several pairs of alternating copper (or silver) and zinc discs
(electrodes) separated by cloth or cardboard soaked in brine (electrolyte) to increase the
electrolyte conductivity.[52] When the top and bottom contacts were connected by a wire, an
electric current flowed through the voltaic pile and the connecting wire. Thus, Volta is
credited with constructing the first electrical battery to produce electricity. Volta's method of
stacking round plates of copper and zinc separated by disks of cardboard moistened with salt
solution was termed a voltaic pile.

Thus, Volta is considered to be the founder of the discipline of electrochemistry.[53] A

Galvanic cell (or voltaic cell) is an electrochemical cell that derives electrical energy from
spontaneous redox reaction taking place within the cell. It generally consists of two different
metals connected by a salt bridge, or individual half-cells separated by a porous membrane.

Antoine-Laurent de Lavoisier

Portrait of Monsieur Lavoisier and his wife, by Jacques-Louis David

Main articles: Antoine Lavoisier and Chemical Revolution

Although the archives of chemical research draw upon work from ancient Babylonia, Egypt,
and especially the Arabs and Persians after Islam, modern chemistry flourished from the time
of Antoine-Laurent de Lavoisier, a French chemist who is celebrated as the "father of modern
chemistry". Lavoisier demonstrated with careful measurements that transmutation of water to
earth was not possible, but that the sediment observed from boiling water came from the
container. He burnt phosphorus and sulfur in air, and proved that the products weighed more
than the original. Nevertheless, the weight gained was lost from the air. Thus, in 1789, he
established the Law of Conservation of Mass, which is also called "Lavoisier's Law."[54]

The world's first ice-calorimeter, used in the winter of 1782-83, by Antoine Lavoisier and
Pierre-Simon Laplace, to determine the heat involved in various chemical changes;
calculations which were based on Joseph Black's prior discovery of latent heat. These
experiments mark the foundation of thermochemistry.

Repeating the experiments of Priestley, he demonstrated that air is composed of two parts,
one of which combines with metals to form calxes. In Considérations Générales sur la
Nature des Acides (1778), he demonstrated that the "air" responsible for combustion was also
the source of acidity. The next year, he named this portion oxygen (Greek for acid-former),
and the other azote (Greek for no life). Lavoisier thus has a claim to the discovery of oxygen
along with Priestley and Scheele. He also discovered that the "inflammable air" discovered
by Cavendish - which he termed hydrogen (Greek for water-former) - combined with oxygen
to produce a dew, as Priestley had reported, which appeared to be water. In Reflexions sur le
Phlogistique (1783), Lavoisier showed the phlogiston theory of combustion to be
inconsistent. Mikhail Lomonosov independently established a tradition of chemistry in
Russia in the 18th century. Lomonosov also rejected the phlogiston theory, and anticipated
the kinetic theory of gases. Lomonosov regarded heat as a form of motion, and stated the idea
of conservation of matter.

Lavoisier worked with Claude Louis Berthollet and others to devise a system of chemical
nomenclature which serves as the basis of the modern system of naming chemical
compounds. In his Methods of Chemical Nomenclature (1787), Lavoisier invented the system
of naming and classification still largely in use today, including names such as sulfuric acid,
sulfates, and sulfites. In 1785, Berthollet was the first to introduce the use of chlorine gas as a
commercial bleach. In the same year he first determined the elemental composition of the gas
ammonia. Berthollet first produced a modern bleaching liquid in 1789 by passing chlorine
gas through a solution of sodium carbonate - the result was a weak solution of sodium
hypochlorite. Another strong chlorine oxidant and bleach which he investigated and was the
first to produce, potassium chlorate (KClO3), is known as Berthollet's Salt. Berthollet is also
known for his scientific contributions to theory of chemical equilibria via the mechanism of
reverse chemical reactions.
Traité élémentaire de chimie

Lavoisier's Traité Élémentaire de Chimie (Elementary Treatise of Chemistry, 1789) was the
first modern chemical textbook, and presented a unified view of new theories of chemistry,
contained a clear statement of the Law of Conservation of Mass, and denied the existence of
phlogiston. In addition, it contained a list of elements, or substances that could not be broken
down further, which included oxygen, nitrogen, hydrogen, phosphorus, mercury, zinc, and
sulfur. His list, however, also included light, and caloric, which he believed to be material
substances. In the work, Lavoisier underscored the observational basis of his chemistry,
stating "I have tried...to arrive at the truth by linking up facts; to suppress as much as possible
the use of reasoning, which is often an unreliable instrument which deceives us, in order to
follow as much as possible the torch of observation and of experiment." Nevertheless, he
believed that the real existence of atoms was philosophically impossible. Lavoisier
demonstrated that organisms disassemble and reconstitute atmospheric air in the same
manner as a burning body.

With Pierre-Simon Laplace, Lavoisier used a calorimeter to estimate the heat evolved per unit
of carbon dioxide produced. They found the same ratio for a flame and animals, indicating
that animals produced energy by a type of combustion. Lavoisier believed in the radical
theory, believing that radicals, which function as a single group in a chemical reaction, would
combine with oxygen in reactions. He believed all acids contained oxygen. He also
discovered that diamond is a crystalline form of carbon.

While many of Lavoisier's partners were influential for the advancement of chemistry as a
scientific discipline, his wife Marie-Anne Lavoisier was arguably the most influential of them
all. Upon their marriage, Mme. Lavoisier began to study chemistry, English, and drawing in
order to help her husband in his work either by translating papers into English, a language
which Lavoisier did not know, or by keeping records and drawing the various apparatuses
that Lavoisier used in his labs.[55] Through her ability to read and translate articles from
Britain for her husband, Lavoisier had access knowledge from many of the chemical
advances happening outside of his lab.[55] Furthermore, Mme. Lavoisier kept records of
Lavoisier's work and ensured that his works were published.[55] The first sign of Marie-
Anne's true potential as a chemist in Lavoisier's lab came when she was translating a book by
the scientist Richard Kirwan. While translating, she stumbled upon and corrected multiple
errors. When she presented her translation, along with her notes to Lavoisier [55] Her edits and
contributions led to Lavoisier's refutation of the theory of phlogiston.

Lavoisier made many fundamental contributions to the science of chemistry. Following

Lavoisier's work, chemistry acquired a strict quantitative nature, allowing reliable predictions
to be made. The revolution in chemistry which he brought about was a result of a conscious
effort to fit all experiments into the framework of a single theory. He established the
consistent use of chemical balance, used oxygen to overthrow the phlogiston theory, and
developed a new system of chemical nomenclature. Lavoisier was beheaded during the
French Revolution.

19th century
In 1802, French American chemist and industrialist Éleuthère Irénée du Pont, who learned
manufacture of gunpowder and explosives under Antoine Lavoisier, founded a gunpowder
manufacturer in Delaware known as E. I. du Pont de Nemours and Company. The French
Revolution forced his family to move to the United States where du Pont started a gunpowder
mill on the Brandywine River in Delaware. Wanting to make the best powder possible, du
Pont was vigilant about the quality of the materials he used. For 32 years, du Pont served as
president of E. I. du Pont de Nemours and Company, which eventually grew into one of the
largest and most successful companies in America.

Throughout the 19th century, chemistry was divided between those who followed the atomic
theory of John Dalton and those who did not, such as Wilhelm Ostwald and Ernst Mach.[56]
Although such proponents of the atomic theory as Amedeo Avogadro and Ludwig Boltzmann
made great advances in explaining the behavior of gases, this dispute was not finally settled
until Jean Perrin's experimental investigation of Einstein's atomic explanation of Brownian
motion in the first decade of the 20th century.[56]

Well before the dispute had been settled, many had already applied the concept of atomism to
chemistry. A major example was the ion theory of Svante Arrhenius which anticipated ideas
about atomic substructure that did not fully develop until the 20th century. Michael Faraday
was another early worker, whose major contribution to chemistry was electrochemistry, in
which (among other things) a certain quantity of electricity during electrolysis or
electrodeposition of metals was shown to be associated with certain quantities of chemical
elements, and fixed quantities of the elements therefore with each other, in specific
ratios.[citation needed] These findings, like those of Dalton's combining ratios, were early clues to
the atomic nature of matter.

John Dalton
John Dalton is remembered for his work on partial pressures in gases, color blindness, and
atomic theory
Main articles: John Dalton and Atomic theory

In 1803, English meteorologist and chemist John Dalton proposed Dalton's law, which
describes the relationship between the components in a mixture of gases and the relative
pressure each contributes to that of the overall mixture.[57] Discovered in 1801, this concept is
also known as Dalton's law of partial pressures.

Dalton also proposed a modern atomic theory in 1803 which stated that all matter was
composed of small indivisible particles termed atoms, atoms of a given element possess
unique characteristics and weight, and three types of atoms exist: simple (elements),
compound (simple molecules), and complex (complex molecules). In 1808, Dalton first
published New System of Chemical Philosophy (1808-1827), in which he outlined the first
modern scientific description of the atomic theory. This work identified chemical elements as
a specific type of atom, therefore rejecting Newton's theory of chemical affinities.

Instead, Dalton inferred proportions of elements in compounds by taking ratios of the weights
of reactants, setting the atomic weight of hydrogen to be identically one. Following Jeremias
Benjamin Richter (known for introducing the term stoichiometry), he proposed that chemical
elements combine in integral ratios. This is known as the law of multiple proportions or
Dalton's law, and Dalton included a clear description of the law in his New System of
Chemical Philosophy. The law of multiple proportions is one of the basic laws of
stoichiometry used to establish the atomic theory. Despite the importance of the work as the
first view of atoms as physically real entities and introduction of a system of chemical
symbols, New System of Chemical Philosophy devoted almost as much space to the caloric
theory as to atomism.

French chemist Joseph Proust proposed the law of definite proportions, which states that
elements always combine in small, whole number ratios to form compounds, based on
several experiments conducted between 1797 and 1804[58] Along with the law of multiple
proportions, the law of definite proportions forms the basis of stoichiometry. The law of
definite proportions and constant composition do not prove that atoms exist, but they are
difficult to explain without assuming that chemical compounds are formed when atoms
combine in constant proportions.
Jöns Jacob Berzelius

Jöns Jacob Berzelius, the chemist who worked out the modern technique of chemical formula
notation and is considered one of the fathers of modern chemistry
Main article: Jöns Jacob Berzelius

A Swedish chemist and disciple of Dalton, Jöns Jacob Berzelius embarked on a systematic
program to try to make accurate and precise quantitative measurements and insure the purity
of chemicals. Along with Lavoisier, Boyle, and Dalton, Berzelius is known as the father of
modern chemistry. In 1828 he compiled a table of relative atomic weights, where oxygen was
set to 100, and which included all of the elements known at the time. This work provided
evidence in favor of Dalton's atomic theory: that inorganic chemical compounds are
composed of atoms combined in whole number amounts. He determined the exact elementary
constituents of large numbers of compounds. The results strongly confirmed Proust's Law of
Definite Proportions. In his weights, he used oxygen as a standard, setting its weight equal to
exactly 100. He also measured the weights of 43 elements. In discovering that atomic weights
are not integer multiples of the weight of hydrogen, Berzelius also disproved Prout's
hypothesis that elements are built up from atoms of hydrogen.

Motivated by his extensive atomic weight determinations and in a desire to aid his
experiments, he introduced the classical system of chemical symbols and notation with his
1808 publishing of Lärbok i Kemien, in which elements are abbreviated by one or two letters
to make a distinct abbreviation from their Latin name. This system of chemical notation—in
which the elements were given simple written labels, such as O for oxygen, or Fe for iron,
with proportions noted by numbers—is the same basic system used today. The only
difference is that instead of the subscript number used today (e.g., H2O), Berzelius used a
superscript (H2O). Berzelius is credited with identifying the chemical elements silicon,
selenium, thorium, and cerium. Students working in Berzelius's laboratory also discovered
lithium and vanadium.

Berzelius developed the radical theory of chemical combination, which holds that reactions
occur as stable groups of atoms called radicals are exchanged between molecules. He
believed that salts are compounds of an acid and bases, and discovered that the anions in
acids would be attracted to a positive electrode (the anode), whereas the cations in a base
would be attracted to a negative electrode (the cathode). Berzelius did not believe in the
Vitalism Theory, but instead in a regulative force which produced organization of tissues in
an organism. Berzelius is also credited with originating the chemical terms "catalysis",
"polymer", "isomer", and "allotrope", although his original definitions differ dramatically
from modern usage. For example, he coined the term "polymer" in 1833 to describe organic
compounds which shared identical empirical formulas but which differed in overall
molecular weight, the larger of the compounds being described as "polymers" of the smallest.
By this long superseded, pre-structural definition, glucose (C6H12O6) was viewed as a
polymer of formaldehyde (CH2O).

New elements and gas laws

Humphry Davy, the discover of several alkali and alkaline earth metals, as well as
contributions to the discoveries of the elemental nature of chlorine and iodine.
Main article: Humphry Davy

English chemist Humphry Davy was a pioneer in the field of electrolysis, using Alessandro
Volta's voltaic pile to split up common compounds and thus isolate a series of new elements.
He went on to electrolyse molten salts and discovered several new metals, especially sodium
and potassium, highly reactive elements known as the alkali metals. Potassium, the first metal
that was isolated by electrolysis, was discovered in 1807 by Davy, who derived it from
caustic potash (KOH). Before the 19th century, no distinction was made between potassium
and sodium. Sodium was first isolated by Davy in the same year by passing an electric
current through molten sodium hydroxide (NaOH). When Davy heard that Berzelius and
Pontin prepared calcium amalgam by electrolyzing lime in mercury, he tried it himself. Davy
was successful, and discovered calcium in 1808 by electrolyzing a mixture of lime and
mercuric oxide.[59][60] He worked with electrolysis throughout his life and, in 1808, he
isolated magnesium, strontium[61] and barium.[62]

Davy also experimented with gases by inhaling them. This experimental procedure nearly
proved fatal on several occasions, but led to the discovery of the unusual effects of nitrous
oxide, which came to be known as laughing gas. Chlorine was discovered in 1774 by
Swedish chemist Carl Wilhelm Scheele, who called it "dephlogisticated marine acid" (see
phlogiston theory) and mistakenly thought it contained oxygen. Scheele observed several
properties of chlorine gas, such as its bleaching effect on litmus, its deadly effect on insects,
its yellow-green colour, and the similarity of its smell to that of aqua regia. However, Scheele
was unable to publish his findings at the time. In 1810, chlorine was given its current name
by Humphry Davy (derived from the Greek word for green), who insisted that chlorine was in
fact an element.[63] He also showed that oxygen could not be obtained from the substance
known as oxymuriatic acid (HCl solution). This discovery overturned Lavoisier's definition
of acids as compounds of oxygen. Davy was a popular lecturer and able experimenter.

Joseph Louis Gay-Lussac, who stated that the ratio between the volumes of the reactant gases
and the products can be expressed in simple whole numbers.
Main articles: Joseph Louis Gay-Lussac and Gay-Lussac's law

French chemist Joseph Louis Gay-Lussac shared the interest of Lavoisier and others in the
quantitative study of the properties of gases. From his first major program of research in
1801–1802, he concluded that equal volumes of all gases expand equally with the same
increase in temperature: this conclusion is usually called "Charles's law", as Gay-Lussac gave
credit to Jacques Charles, who had arrived at nearly the same conclusion in the 1780s but had
not published it.[64] The law was independently discovered by British natural philosopher
John Dalton by 1801, although Dalton's description was less thorough than Gay-
Lussac's.[65][66] In 1804 Gay-Lussac made several daring ascents of over 7,000 meters above
sea level in hydrogen-filled balloons—a feat not equaled for another 50 years—that allowed
him to investigate other aspects of gases. Not only did he gather magnetic measurements at
various altitudes, but he also took pressure, temperature, and humidity measurements and
samples of air, which he later analyzed chemically.

In 1808 Gay-Lussac announced what was probably his single greatest achievement: from his
own and others' experiments he deduced that gases at constant temperature and pressure
combine in simple numerical proportions by volume, and the resulting product or products—
if gases—also bear a simple proportion by volume to the volumes of the reactants. In other
words, gases under equal conditions of temperature and pressure react with one another in
volume ratios of small whole numbers. This conclusion subsequently became known as
"Gay-Lussac's law" or the "Law of Combining Volumes". With his fellow professor at the
École Polytechnique, Louis Jacques Thénard, Gay-Lussac also participated in early
electrochemical research, investigating the elements discovered by its means. Among other
achievements, they decomposed boric acid by using fused potassium, thus discovering the
element boron. The two also took part in contemporary debates that modified Lavoisier's
definition of acids and furthered his program of analyzing organic compounds for their
oxygen and hydrogen content.
The element iodine was discovered by French chemist Bernard Courtois in 1811.[67][68]
Courtois gave samples to his friends, Charles Bernard Desormes (1777–1862) and Nicolas
Clément (1779–1841), to continue research. He also gave some of the substance to Gay-
Lussac and to physicist André-Marie Ampère. On December 6, 1813, Gay-Lussac announced
that the new substance was either an element or a compound of oxygen.[69][70][71] It was Gay-
Lussac who suggested the name "iode", from the Greek word ιώδες (iodes) for violet
(because of the color of iodine vapor).[67][69] Ampère had given some of his sample to
Humphry Davy. Davy did some experiments on the substance and noted its similarity to
chlorine.[72] Davy sent a letter dated December 10 to the Royal Society of London stating that
he had identified a new element.[73] Arguments erupted between Davy and Gay-Lussac over
who identified iodine first, but both scientists acknowledged Courtois as the first to isolate
the element.

In 1815, Humphry Davy invented the Davy lamp, which allowed miners within coal mines to
work safely in the presence of flammable gases. There had been many mining explosions
caused by firedamp or methane often ignited by open flames of the lamps then used by
miners. Davy conceived of using an iron gauze to enclose a lamp's flame, and so prevent the
methane burning inside the lamp from passing out to the general atmosphere. Although the
idea of the safety lamp had already been demonstrated by William Reid Clanny and by the
then unknown (but later very famous) engineer George Stephenson, Davy's use of wire gauze
to prevent the spread of flame was used by many other inventors in their later designs. There
was some discussion as to whether Davy had discovered the principles behind his lamp
without the help of the work of Smithson Tennant, but it was generally agreed that the work
of both men had been independent. Davy refused to patent the lamp, and its invention led to
him being awarded the Rumford medal in 1816.[74]

Amedeo Avogadro, who postulated that, under controlled conditions of temperature and
pressure, equal volumes of gases contain an equal number of molecules. This is known as
Avogadro's law.
Main articles: Amedeo Avogadro and Avogadro's law

After Dalton published his atomic theory in 1808, certain of his central ideas were soon
adopted by most chemists. However, uncertainty persisted for half a century about how
atomic theory was to be configured and applied to concrete situations; chemists in different
countries developed several different incompatible atomistic systems. A paper that suggested
a way out of this difficult situation was published as early as 1811 by the Italian physicist
Amedeo Avogadro (1776-1856), who hypothesized that equal volumes of gases at the same
temperature and pressure contain equal numbers of molecules, from which it followed that
relative molecular weights of any two gases are the same as the ratio of the densities of the
two gases under the same conditions of temperature and pressure. Avogadro also reasoned
that simple gases were not formed of solitary atoms but were instead compound molecules of
two or more atoms. Thus Avogadro was able to overcome the difficulty that Dalton and
others had encountered when Gay-Lussac reported that above 100 °C the volume of water
vapor was twice the volume of the oxygen used to form it. According to Avogadro, the
molecule of oxygen had split into two atoms in the course of forming water vapor.

Avogadro's hypothesis was neglected for half a century after it was first published. Many
reasons for this neglect have been cited, including some theoretical problems, such as Jöns
Jacob Berzelius's "dualism", which asserted that compounds are held together by the
attraction of positive and negative electrical charges, making it inconceivable that a molecule
composed of two electrically similar atoms—as in oxygen—could exist. An additional barrier
to acceptance was the fact that many chemists were reluctant to adopt physical methods (such
as vapour-density determinations) to solve their problems. By mid-century, however, some
leading figures had begun to view the chaotic multiplicity of competing systems of atomic
weights and molecular formulas as intolerable. Moreover, purely chemical evidence began to
mount that suggested Avogadro's approach might be right after all. During the 1850s,
younger chemists, such as Alexander Williamson in England, Charles Gerhardt and Charles-
Adolphe Wurtz in France, and August Kekulé in Germany, began to advocate reforming
theoretical chemistry to make it consistent with Avogadrian theory.

Wöhler and the vitalism debate

Structural formula of urea

Main articles: Vitalism, Friedrich Wöhler, and Wöhler synthesis

In 1825, Friedrich Wöhler and Justus von Liebig performed the first confirmed discovery and
explanation of isomers, earlier named by Berzelius. Working with cyanic acid and fulminic
acid, they correctly deduced that isomerism was caused by differing arrangements of atoms
within a molecular structure. In 1827, William Prout classified biomolecules into their
modern groupings: carbohydrates, proteins and lipids. After the nature of combustion was
settled, a dispute about vitalism and the essential distinction between organic and inorganic
substances began. The vitalism question was revolutionized in 1828 when Friedrich Wöhler
synthesized urea, thereby establishing that organic compounds could be produced from
inorganic starting materials and disproving the theory of vitalism.

This opened a new research field in chemistry, and by the end of the 19th century, scientists
were able to synthesize hundreds of organic compounds. The most important among them are
mauve, magenta, and other synthetic dyes, as well as the widely used drug aspirin. The
discovery of the artificial synthesis of urea contributed greatly to the theory of isomerism, as
the empirical chemical formulas for urea and ammonium cyanate are identical (see Wöhler
synthesis). In 1832, Friedrich Wöhler and Justus von Liebig discovered and explained
functional groups and radicals in relation to organic chemistry, as well as first synthesizing
benzaldehyde. Liebig, a German chemist, made major contributions to agricultural and
biological chemistry, and worked on the organization of organic chemistry. Liebig is
considered the "father of the fertilizer industry" for his discovery of nitrogen as an essential
plant nutrient, and his formulation of the Law of the Minimum which described the effect of
individual nutrients on crops.

Mid-1800s

In 1840, Germain Hess proposed Hess's law, an early statement of the law of conservation of
energy, which establishes that energy changes in a chemical process depend only on the
states of the starting and product materials and not on the specific pathway taken between the
two states. In 1847, Hermann Kolbe obtained acetic acid from completely inorganic sources,
further disproving vitalism. In 1848, William Thomson, 1st Baron Kelvin (commonly known
as Lord Kelvin) established the concept of absolute zero, the temperature at which all
molecular motion ceases. In 1849, Louis Pasteur discovered that the racemic form of tartaric
acid is a mixture of the levorotatory and dextrotatory forms, thus clarifying the nature of
optical rotation and advancing the field of stereochemistry.[75] In 1852, August Beer proposed
Beer's law, which explains the relationship between the composition of a mixture and the
amount of light it will absorb. Based partly on earlier work by Pierre Bouguer and Johann
Heinrich Lambert, it established the analytical technique known as spectrophotometry.[76] In
1855, Benjamin Silliman, Jr. pioneered methods of petroleum cracking, which made the
entire modern petrochemical industry possible.[77]

Formulas of acetic acid given by August Kekulé in 1861.

Main articles: Stanislao Cannizzaro and Karlsruhe Congress

Avogadro's hypothesis began to gain broad appeal among chemists only after his compatriot
and fellow scientist Stanislao Cannizzaro demonstrated its value in 1858, two years after
Avogadro's death. Cannizzaro's chemical interests had originally centered on natural products
and on reactions of aromatic compounds; in 1853 he discovered that when benzaldehyde is
treated with concentrated base, both benzoic acid and benzyl alcohol are produced—a
phenomenon known today as the Cannizzaro reaction. In his 1858 pamphlet, Cannizzaro
showed that a complete return to the ideas of Avogadro could be used to construct a
consistent and robust theoretical structure that fit nearly all of the available empirical
evidence. For instance, he pointed to evidence that suggested that not all elementary gases
consist of two atoms per molecule—some were monatomic, most were diatomic, and a few
were even more complex.

Another point of contention had been the formulas for compounds of the alkali metals (such
as sodium) and the alkaline earth metals (such as calcium), which, in view of their striking
chemical analogies, most chemists had wanted to assign to the same formula type.
Cannizzaro argued that placing these metals in different categories had the beneficial result of
eliminating certain anomalies when using their physical properties to deduce atomic weights.
Unfortunately, Cannizzaro's pamphlet was published initially only in Italian and had little
immediate impact. The real breakthrough came with an international chemical congress held
in the German town of Karlsruhe in September 1860, at which most of the leading European
chemists were present. The Karlsruhe Congress had been arranged by Kekulé, Wurtz, and a
few others who shared Cannizzaro's sense of the direction chemistry should go. Speaking in
French (as everyone there did), Cannizzaro's eloquence and logic made an indelible
impression on the assembled body. Moreover, his friend Angelo Pavesi distributed
Cannizzaro's pamphlet to attendees at the end of the meeting; more than one chemist later
wrote of the decisive impression the reading of this document provided. For instance, Lothar
Meyer later wrote that on reading Cannizzaro's paper, "The scales seemed to fall from my
eyes."[78] Cannizzaro thus played a crucial role in winning the battle for reform. The system
advocated by him, and soon thereafter adopted by most leading chemists, is substantially
identical to what is still used today.

Perkin, Crookes, and Nobel

In 1856, Sir William Henry Perkin, age 18, given a challenge by his professor, August
Wilhelm von Hofmann, sought to synthesize quinine, the anti-malaria drug, from coal tar. In
one attempt, Perkin oxidized aniline using potassium dichromate, whose toluidine impurities
reacted with the aniline and yielded a black solid—suggesting a "failed" organic synthesis.
Cleaning the flask with alcohol, Perkin noticed purple portions of the solution: a byproduct of
the attempt was the first synthetic dye, known as mauveine or Perkin's mauve. Perkin's
discovery is the foundation of the dye synthesis industry, one of the earliest successful
chemical industries.

German chemist August Kekulé von Stradonitz's most important single contribution was his
structural theory of organic composition, outlined in two articles published in 1857 and 1858
and treated in great detail in the pages of his extraordinarily popular Lehrbuch der
organischen Chemie ("Textbook of Organic Chemistry"), the first installment of which
appeared in 1859 and gradually extended to four volumes. Kekulé argued that tetravalent
carbon atoms - that is, carbon forming exactly four chemical bonds - could link together to
form what he called a "carbon chain" or a "carbon skeleton," to which other atoms with other
valences (such as hydrogen, oxygen, nitrogen, and chlorine) could join. He was convinced
that it was possible for the chemist to specify this detailed molecular architecture for at least
the simpler organic compounds known in his day. Kekulé was not the only chemist to make
such claims in this era. The Scottish chemist Archibald Scott Couper published a
substantially similar theory nearly simultaneously, and the Russian chemist Aleksandr
Butlerov did much to clarify and expand structure theory. However, it was predominantly
Kekulé's ideas that prevailed in the chemical community.
A Crookes tube (2 views): light and dark. Electrons travel in straight lines from the cathode
(left), as evidenced by the shadow cast from the Maltese cross on the fluorescence of the
righthand end. The anode is at the bottom wire.

British chemist and physicist William Crookes is noted for his cathode ray studies,
fundamental in the development of atomic physics. His researches on electrical discharges
through a rarefied gas led him to observe the dark space around the cathode, now called the
Crookes dark space. He demonstrated that cathode rays travel in straight lines and produce
phosphorescence and heat when they strike certain materials. A pioneer of vacuum tubes,
Crookes invented the Crookes tube - an early experimental discharge tube, with partial
vacuum with which he studied the behavior of cathode rays. With the introduction of
spectrum analysis by Robert Bunsen and Gustav Kirchhoff (1859-1860), Crookes applied the
new technique to the study of selenium compounds. Bunsen and Kirchhoff had previously
used spectroscopy as a means of chemical analysis to discover caesium and rubidium. In
1861, Crookes used this process to discover thallium in some seleniferous deposits. He
continued work on that new element, isolated it, studied its properties, and in 1873
determined its atomic weight. During his studies of thallium, Crookes discovered the
principle of the Crookes radiometer, a device that converts light radiation into rotary motion.
The principle of this radiometer has found numerous applications in the development of
sensitive measuring instruments.

In 1862, Alexander Parkes exhibited Parkesine, one of the earliest synthetic polymers, at the
International Exhibition in London. This discovery formed the foundation of the modern
plastics industry. In 1864, Cato Maximilian Guldberg and Peter Waage, building on Claude
Louis Berthollet's ideas, proposed the law of mass action. In 1865, Johann Josef Loschmidt
determined the exact number of molecules in a mole, later named Avogadro's number.

In 1865, August Kekulé, based partially on the work of Loschmidt and others, established the
structure of benzene as a six carbon ring with alternating single and double bonds. Kekulé's
novel proposal for benzene's cyclic structure was much contested but was never replaced by a
superior theory. This theory provided the scientific basis for the dramatic expansion of the
German chemical industry in the last third of the 19th century. Today, the large majority of
known organic compounds are aromatic, and all of them contain at least one hexagonal
benzene ring of the sort that Kekulé advocated. Kekulé is also famous for having clarified the
nature of aromatic compounds, which are compounds based on the benzene molecule. In
1865, Adolf von Baeyer began work on indigo dye, a milestone in modern industrial organic
chemistry which revolutionized the dye industry.

Swedish chemist and inventor Alfred Nobel found that when nitroglycerin was incorporated
in an absorbent inert substance like kieselguhr (diatomaceous earth) it became safer and more
convenient to handle, and this mixture he patented in 1867 as dynamite. Nobel later on
combined nitroglycerin with various nitrocellulose compounds, similar to collodion, but
settled on a more efficient recipe combining another nitrate explosive, and obtained a
transparent, jelly-like substance, which was a more powerful explosive than dynamite.
Gelignite, or blasting gelatin, as it was named, was patented in 1876; and was followed by a
host of similar combinations, modified by the addition of potassium nitrate and various other
substances.

Mendeleev's periodic table

Main articles: Dmitri Mendeleev, Periodic table, and History of the periodic table

Dmitri Mendeleev, responsible for organizing the known chemical elements in a periodic
table.

An important breakthrough in making sense of the list of known chemical elements (as well
as in understanding the internal structure of atoms) was Dmitri Mendeleev's development of
the first modern periodic table, or the periodic classification of the elements. Mendeleev, a
Russian chemist, felt that there was some type of order to the elements and he spent more
than thirteen years of his life collecting data and assembling the concept, initially with the
idea of resolving some of the disorder in the field for his students. Mendeleev found that,
when all the known chemical elements were arranged in order of increasing atomic weight,
the resulting table displayed a recurring pattern, or periodicity, of properties within groups of
elements. Mendeleev's law allowed him to build up a systematic periodic table of all the 66
elements then known based on atomic mass, which he published in Principles of Chemistry in
1869. His first Periodic Table was compiled on the basis of arranging the elements in
ascending order of atomic weight and grouping them by similarity of properties.

Mendeleev had such faith in the validity of the periodic law that he proposed changes to the
generally accepted values for the atomic weight of a few elements and, in his version of the
periodic table of 1871, predicted the locations within the table of unknown elements together
with their properties. He even predicted the likely properties of three yet-to-be-discovered
elements, which he called ekaboron (Eb), ekaaluminium (Ea), and ekasilicon (Es), which
proved to be good predictors of the properties of scandium, gallium, and germanium,
respectively, which each fill the spot in the periodic table assigned by Mendeleev.

At first the periodic system did not raise interest among chemists. However, with the
discovery of the predicted elements, notably gallium in 1875, scandium in 1879, and
germanium in 1886, it began to win wide acceptance. The subsequent proof of many of his
predictions within his lifetime brought fame to Mendeleev as the founder of the periodic law.
This organization surpassed earlier attempts at classification by Alexandre-Émile Béguyer de
Chancourtois, who published the telluric helix, an early, three-dimensional version of the
periodic table of the elements in 1862, John Newlands, who proposed the law of octaves (a
precursor to the periodic law) in 1864, and Lothar Meyer, who developed an early version of
the periodic table with 28 elements organized by valence in 1864. Mendeleev's table did not
include any of the noble gases, however, which had not yet been discovered. Gradually the
periodic law and table became the framework for a great part of chemical theory. By the time
Mendeleev died in 1907, he enjoyed international recognition and had received distinctions
and awards from many countries.

In 1873, Jacobus Henricus van 't Hoff and Joseph Achille Le Bel, working independently,
developed a model of chemical bonding that explained the chirality experiments of Pasteur
and provided a physical cause for optical activity in chiral compounds.[79] van 't Hoff's
publication, called Voorstel tot Uitbreiding der Tegenwoordige in de Scheikunde gebruikte
Structuurformules in de Ruimte, etc. (Proposal for the development of 3-dimensional
chemical structural formulae) and consisting of twelve pages text and one page diagrams,
gave the impetus to the development of stereochemistry. The concept of the "asymmetrical
carbon atom", dealt with in this publication, supplied an explanation of the occurrence of
numerous isomers, inexplicable by means of the then current structural formulae. At the same
time he pointed out the existence of relationship between optical activity and the presence of
an asymmetrical carbon atom.

Josiah Willard Gibbs

Main articles: Josiah Willard Gibbs and Statistical mechanics

J. Willard Gibbs formulated a concept of thermodynamic equilibrium of a system in terms of
energy and entropy. He also did extensive work on chemical equilibrium, and equilibria
between phases.

American mathematical physicist J. Willard Gibbs's work on the applications of

thermodynamics was instrumental in transforming physical chemistry into a rigorous
deductive science. During the years from 1876 to 1878, Gibbs worked on the principles of
thermodynamics, applying them to the complex processes involved in chemical reactions. He
discovered the concept of chemical potential, or the "fuel" that makes chemical reactions
work. In 1876 he published his most famous contribution, "On the Equilibrium of
Heterogeneous Substances", a compilation of his work on thermodynamics and physical
chemistry which laid out the concept of free energy to explain the physical basis of chemical
equilibria.[80] In these essays were the beginnings of Gibbs’ theories of phases of matter: he
considered each state of matter a phase, and each substance a component. Gibbs took all of
the variables involved in a chemical reaction - temperature, pressure, energy, volume, and
entropy - and included them in one simple equation known as Gibbs' phase rule.

Within this paper was perhaps his most outstanding contribution, the introduction of the
concept free energy, now universally called Gibbs free energy in his honor. The Gibbs free
energy relates the tendency of a physical or chemical system to simultaneously lower its
energy and increase its disorder, or entropy, in a spontaneous natural process. Gibbs's
approach allows a researcher to calculate the change in free energy in the process, such as in
a chemical reaction, and how fast it will happen. Since virtually all chemical processes and
many physical ones involve such changes, his work has significantly impacted both the
theoretical and experiential aspects of these sciences. In 1877, Ludwig Boltzmann established
statistical derivations of many important physical and chemical concepts, including entropy,
and distributions of molecular velocities in the gas phase.[81] Together with Boltzmann and
James Clerk Maxwell, Gibbs created a new branch of theoretical physics called statistical
mechanics (a term that he coined), explaining the laws of thermodynamics as consequences
of the statistical properties of large ensembles of particles. Gibbs also worked on the
application of Maxwell's equations to problems in physical optics. Gibbs's derivation of the
phenomenological laws of thermodynamics from the statistical properties of systems with
many particles was presented in his highly influential textbook Elementary Principles in
Statistical Mechanics, published in 1902, a year before his death. In that work, Gibbs
reviewed the relationship between the laws of thermodynamics and statistical theory of
molecular motions. The overshooting of the original function by partial sums of Fourier
series at points of discontinuity is known as the Gibbs phenomenon.

Late 19th century

German engineer Carl von Linde's invention of a continuous process of liquefying gases in
large quantities formed a basis for the modern technology of refrigeration and provided both
impetus and means for conducting scientific research at low temperatures and very high
vacuums. He developed a methyl ether refrigerator (1874) and an ammonia refrigerator
(1876). Though other refrigeration units had been developed earlier, Linde's were the first to
be designed with the aim of precise calculations of efficiency. In 1895 he set up a large-scale
plant for the production of liquid air. Six years later he developed a method for separating
pure liquid oxygen from liquid air that resulted in widespread industrial conversion to
processes utilizing oxygen (e.g., in steel manufacture).

In 1883, Svante Arrhenius developed an ion theory to explain conductivity in electrolytes.[82]

In 1884, Jacobus Henricus van 't Hoff published Études de Dynamique chimique (Studies in
Dynamic Chemistry), a seminal study on chemical kinetics.[83] In this work, van 't Hoff
entered for the first time the field of physical chemistry. Of great importance was his
development of the general thermodynamic relationship between the heat of conversion and
the displacement of the equilibrium as a result of temperature variation. At constant volume,
the equilibrium in a system will tend to shift in such a direction as to oppose the temperature
change which is imposed upon the system. Thus, lowering the temperature results in heat
development while increasing the temperature results in heat absorption. This principle of
mobile equilibrium was subsequently (1885) put in a general form by Henry Louis Le
Chatelier, who extended the principle to include compensation, by change of volume, for
imposed pressure changes. The van 't Hoff-Le Chatelier principle, or simply Le Chatelier's
principle, explains the response of dynamic chemical equilibria to external stresses.[84]

In 1884, Hermann Emil Fischer proposed the structure of purine, a key structure in many
biomolecules, which he later synthesized in 1898. He also began work on the chemistry of
glucose and related sugars.[85] In 1885, Eugene Goldstein named the cathode ray, later
discovered to be composed of electrons, and the canal ray, later discovered to be positive
hydrogen ions that had been stripped of their electrons in a cathode ray tube; these would
later be named protons.[86] The year 1885 also saw the publishing of J. H. van 't Hoff's
L'Équilibre chimique dans les Systèmes gazeux ou dissous à I'État dilué (Chemical equilibria
in gaseous systems or strongly diluted solutions), which dealt with this theory of dilute
solutions. Here he demonstrated that the "osmotic pressure" in solutions which are
sufficiently dilute is proportionate to the concentration and the absolute temperature so that
this pressure can be represented by a formula which only deviates from the formula for gas
pressure by a coefficient i. He also determined the value of i by various methods, for example
by means of the vapor pressure and François-Marie Raoult's results on the lowering of the
freezing point. Thus van 't Hoff was able to prove that thermodynamic laws are not only valid
for gases, but also for dilute solutions. His pressure laws, given general validity by the
electrolytic dissociation theory of Arrhenius (1884-1887) - the first foreigner who came to
work with him in Amsterdam (1888) - are considered the most comprehensive and important
in the realm of natural sciences. In 1893, Alfred Werner discovered the octahedral structure
of cobalt complexes, thus establishing the field of coordination chemistry.[87]

Ramsay's discovery of the noble gases

Main articles: William Ramsay and Noble gas

The most celebrated discoveries of Scottish chemist William Ramsay were made in inorganic
chemistry. Ramsay was intrigued by the British physicist John Strutt, 3rd Baron Rayleigh's
1892 discovery that the atomic weight of nitrogen found in chemical compounds was lower
than that of nitrogen found in the atmosphere. He ascribed this discrepancy to a light gas
included in chemical compounds of nitrogen, while Ramsay suspected a hitherto
undiscovered heavy gas in atmospheric nitrogen. Using two different methods to remove all
known gases from air, Ramsay and Lord Rayleigh were able to announce in 1894 that they
had found a monatomic, chemically inert gaseous element that constituted nearly 1 percent of
the atmosphere; they named it argon.

J.J. Thomson

The following year, Ramsay liberated another inert gas from a mineral called cleveite; this
proved to be helium, previously known only in the solar spectrum. In his book The Gases of
the Atmosphere (1896), Ramsay showed that the positions of helium and argon in the
periodic table of elements indicated that at least three more noble gases might exist. In 1898
Ramsay and the British chemist Morris W. Travers isolated these elements—called neon,
krypton, and xenon—from air brought to a liquid state at low temperature and high pressure.
Sir William Ramsay worked with Frederick Soddy to demonstrate, in 1903, that alpha
particles (helium nuclei) were continually produced during the radioactive decay of a sample
of radium. Ramsay was awarded the 1904 Nobel Prize for Chemistry in recognition of
"services in the discovery of the inert gaseous elements in air, and his determination of their
place in the periodic system."

In 1897, J. J. Thomson discovered the electron using the cathode ray tube. In 1898, Wilhelm
Wien demonstrated that canal rays (streams of positive ions) can be deflected by magnetic
fields, and that the amount of deflection is proportional to the mass-to-charge ratio. This
discovery would lead to the analytical technique known as mass spectrometry in 1912.[88]
Marie and Pierre Curie

Marie Curie, a pioneer in the field of radioactivity and the first twice-honored Nobel laureate
(and still the only one in two different sciences)
Main articles: Marie Curie, Pierre Curie, and Henri Becquerel

Marie Skłodowska-Curie was a Polish-born French physicist and chemist who is famous for
her pioneering research on radioactivity. She and her husband are considered to have laid the
cornerstone of the nuclear age with their research on radioactivity. Marie was fascinated with
the work of Henri Becquerel, a French physicist who discovered in 1896 that uranium casts
off rays similar to the X-rays discovered by Wilhelm Röntgen. Marie Curie began studying
uranium in late 1897 and theorized, according to a 1904 article she wrote for Century
magazine, "that the emission of rays by the compounds of uranium is a property of the metal
itself—that it is an atomic property of the element uranium independent of its chemical or
physical state." Curie took Becquerel's work a few steps further, conducting her own
experiments on uranium rays. She discovered that the rays remained constant, no matter the
condition or form of the uranium. The rays, she theorized, came from the element's atomic
structure. This revolutionary idea created the field of atomic physics and the Curies coined
the word radioactivity to describe the phenomena.

Pierre Curie, known for his work on radioactivity as well as on ferromagnetism,

paramagnetism, and diamagnetism; notably Curie's law and Curie point.
Pierre and Marie further explored radioactivity by working to separate the substances in
uranium ores and then using the electrometer to make radiation measurements to ‘trace’ the
minute amount of unknown radioactive element among the fractions that resulted. Working
with the mineral pitchblende, the pair discovered a new radioactive element in 1898. They
named the element polonium, after Marie's native country of Poland. On December 21, 1898,
the Curies detected the presence of another radioactive material in the pitchblende. They
presented this finding to the French Academy of Sciences on December 26, proposing that
the new element be called radium. The Curies then went to work isolating polonium and
radium from naturally occurring compounds to prove that they were new elements. In 1902,
the Curies announced that they had produced a decigram of pure radium, demonstrating its
existence as a unique chemical element. While it took three years for them to isolate radium,
they were never able to isolate polonium. Along with the discovery of two new elements and
finding techniques for isolating radioactive isotopes, Curie oversaw the world's first studies
into the treatment of neoplasms, using radioactive isotopes. With Henri Becquerel and her
husband, Pierre Curie, she was awarded the 1903 Nobel Prize for Physics. She was the sole
winner of the 1911 Nobel Prize for Chemistry. She was the first woman to win a Nobel Prize,
and she is the only woman to win the award in two different fields.

While working with Marie to extract pure substances from ores, an undertaking that really
required industrial resources but that they achieved in relatively primitive conditions, Pierre
himself concentrated on the physical study (including luminous and chemical effects) of the
new radiations. Through the action of magnetic fields on the rays given out by the radium, he
proved the existence of particles electrically positive, negative, and neutral; these Ernest
Rutherford was afterward to call alpha, beta, and gamma rays. Pierre then studied these
radiations by calorimetry and also observed the physiological effects of radium, thus opening
the way to radium therapy. Among Pierre Curie's discoveries were that ferromagnetic
substances exhibited a critical temperature transition, above which the substances lost their
ferromagnetic behavior - this is known as the "Curie point." He was elected to the Academy
of Sciences (1905), having in 1903 jointly with Marie received the Royal Society's
prestigious Davy Medal and jointly with her and Becquerel the Nobel Prize for Physics. He
was run over by a carriage in the rue Dauphine in Paris in 1906 and died instantly. His
complete works were published in 1908.

Ernest Rutherford

Ernest Rutherford, discoverer of the nucleus and considered the father of nuclear physics
New Zealand-born chemist and physicist Ernest Rutherford is considered to be "the father of
nuclear physics." Rutherford is best known for devising the names alpha, beta, and gamma to
classify various forms of radioactive "rays" which were poorly understood at his time (alpha
and beta rays are particle beams, while gamma rays are a form of high-energy
electromagnetic radiation). Rutherford deflected alpha rays with both electric and magnetic
fields in 1903. Working with Frederick Soddy, Rutherford explained that radioactivity is due
to the transmutation of elements, now known to involve nuclear reactions.

Top: Predicted results based on the then-accepted plum pudding model of the atom. Bottom:
Observed results. Rutherford disproved the plum pudding model and concluded that the
positive charge of the atom must be concentrated in a small, central nucleus.

He also observed that the intensity of radioactivity of a radioactive element decreases over a
unique and regular amount of time until a point of stability, and he named the halving time
the "half-life." In 1901 and 1902 he worked with Frederick Soddy to prove that atoms of one
radioactive element would spontaneously turn into another, by expelling a piece of the atom
at high velocity. In 1906 at the University of Manchester, Rutherford oversaw an experiment
conducted by his students Hans Geiger (known for the Geiger counter) and Ernest Marsden.
In the Geiger–Marsden experiment, a beam of alpha particles, generated by the radioactive
decay of radon, was directed normally onto a sheet of very thin gold foil in an evacuated
chamber. Under the prevailing plum pudding model, the alpha particles should all have
passed through the foil and hit the detector screen, or have been deflected by, at most, a few
degrees.

However, the actual results surprised Rutherford. Although many of the alpha particles did
pass through as expected, many others were deflected at small angles while others were
reflected back to the alpha source. They observed that a very small percentage of particles
were deflected through angles much larger than 90 degrees. The gold foil experiment showed
large deflections for a small fraction of incident particles. Rutherford realized that, because
some of the alpha particles were deflected or reflected, the atom had a concentrated centre of
positive charge and of relatively large mass - Rutherford later termed this positive center the
"atomic nucleus". The alpha particles had either hit the positive centre directly or passed by it
close enough to be affected by its positive charge. Since many other particles passed through
the gold foil, the positive centre would have to be a relatively small size compared to the rest
of the atom - meaning that the atom is mostly open space. From his results, Rutherford
developed a model of the atom that was similar to the solar system, known as Rutherford
model. Like planets, electrons orbited a central, sun-like nucleus. For his work with radiation
and the atomic nucleus, Rutherford received the 1908 Nobel Prize in Chemistry.
20th century

The first Solvay Conference was held in Brussels in 1911 and was considered a turning point
in the world of physics and chemistry.

In 1903, Mikhail Tsvet invented chromatography, an important analytic technique. In 1904,

Hantaro Nagaoka proposed an early nuclear model of the atom, where electrons orbit a dense
massive nucleus. In 1905, Fritz Haber and Carl Bosch developed the Haber process for
making ammonia, a milestone in industrial chemistry with deep consequences in agriculture.
The Haber process, or Haber-Bosch process, combined nitrogen and hydrogen to form
ammonia in industrial quantities for production of fertilizer and munitions. The food
production for half the world's current population depends on this method for producing
fertilizer. Haber, along with Max Born, proposed the Born–Haber cycle as a method for
evaluating the lattice energy of an ionic solid. Haber has also been described as the "father of
chemical warfare" for his work developing and deploying chlorine and other poisonous gases
during World War I.

Robert A. Millikan, who is best known for measuring the charge on the electron, won the
Nobel Prize in Physics in 1923.

In 1905, Albert Einstein explained Brownian motion in a way that definitively proved atomic
theory. Leo Baekeland invented bakelite, one of the first commercially successful plastics. In
1909, American physicist Robert Andrews Millikan - who had studied in Europe under
Walther Nernst and Max Planck - measured the charge of individual electrons with
unprecedented accuracy through the oil drop experiment, in which he measured the electric
charges on tiny falling water (and later oil) droplets. His study established that any particular
droplet's electrical charge is a multiple of a definite, fundamental value — the electron's
charge — and thus a confirmation that all electrons have the same charge and mass.
Beginning in 1912, he spent several years investigating and finally proving Albert Einstein's
proposed linear relationship between energy and frequency, and providing the first direct
photoelectric support for Planck's constant. In 1923 Millikan was awarded the Nobel Prize
for Physics.

In 1909, S. P. L. Sørensen invented the pH concept and develops methods for measuring
acidity. In 1911, Antonius Van den Broek proposed the idea that the elements on the periodic
table are more properly organized by positive nuclear charge rather than atomic weight. In
1911, the first Solvay Conference was held in Brussels, bringing together most of the most
prominent scientists of the day. In 1912, William Henry Bragg and William Lawrence Bragg
proposed Bragg's law and established the field of X-ray crystallography, an important tool for
elucidating the crystal structure of substances. In 1912, Peter Debye develops the concept of
molecular dipole to describe asymmetric charge distribution in some molecules.

Niels Bohr

Niels Bohr, the developer of the Bohr model of the atom, and a leading founder of quantum
mechanics
Main articles: Niels Bohr and Bohr model

In 1913, Niels Bohr, a Danish physicist, introduced the concepts of quantum mechanics to
atomic structure by proposing what is now known as the Bohr model of the atom, where
electrons exist only in strictly defined circular orbits around the nucleus similar to rungs on a
ladder. The Bohr Model is a planetary model in which the negatively charged electrons orbit
a small, positively charged nucleus similar to the planets orbiting the Sun (except that the
orbits are not planar) - the gravitational force of the solar system is mathematically akin to the
attractive Coulomb (electrical) force between the positively charged nucleus and the
negatively charged electrons.

In the Bohr model, however, electrons orbit the nucleus in orbits that have a set size and
energy - the energy levels are said to be quantized, which means that only certain orbits with
certain radii are allowed; orbits in between simply don't exist. The energy of the orbit is
related to its size - that is, the lowest energy is found in the smallest orbit. Bohr also
postulated that electromagnetic radiation is absorbed or emitted when an electron moves from
one orbit to another. Because only certain electron orbits are permitted, the emission of light
accompanying a jump of an electron from an excited energy state to ground state produces a
unique emission spectrum for each element.

Niels Bohr also worked on the principle of complementarity, which states that an electron can
be interpreted in two mutually exclusive and valid ways. Electrons can be interpreted as wave
or particle models. His hypothesis was that an incoming particle would strike the nucleus and
create an excited compound nucleus. This formed the basis of his liquid drop model and later
provided a theory base for the explanation of nuclear fission.

Moseley's Staircase

In 1913, Henry Moseley, working from Van den Broek's earlier idea, introduces concept of
atomic number to fix inadequacies of Mendeleev's periodic table, which had been based on
atomic weight. The peak of Frederick Soddy's career in radiochemistry was in 1913 with his
formulation of the concept of isotopes, which stated that certain elements exist in two or more
forms which have different atomic weights but which are indistinguishable chemically. He is
remembered for proving the existence of isotopes of certain radioactive elements, and is also
credited, along with others, with the discovery of the element protactinium in 1917. In 1913,
J. J. Thomson expanded on the work of Wien by showing that charged subatomic particles
can be separated by their mass-to-charge ratio, a technique known as mass spectrometry.

Gilbert N. Lewis

Main article: Gilbert N. Lewis

American physical chemist Gilbert N. Lewis laid the foundation of valence bond theory; he
was instrumental in developing a bonding theory based on the number of electrons in the
outermost "valence" shell of the atom. In 1902, while Lewis was trying to explain valence to
his students, he depicted atoms as constructed of a concentric series of cubes with electrons at
each corner. This "cubic atom" explained the eight groups in the periodic table and
represented his idea that chemical bonds are formed by electron transference to give each
atom a complete set of eight outer electrons (an "octet").
Lewis's theory of chemical bonding continued to evolve and, in 1916, he published his
seminal article "The Atom of the Molecule", which suggested that a chemical bond is a pair
of electrons shared by two atoms. Lewis's model equated the classical chemical bond with the
sharing of a pair of electrons between the two bonded atoms. Lewis introduced the "electron
dot diagrams" in this paper to symbolize the electronic structures of atoms and molecules.
Now known as Lewis structures, they are discussed in virtually every introductory chemistry
book.

Shortly after publication of his 1916 paper, Lewis became involved with military research.
He did not return to the subject of chemical bonding until 1923, when he masterfully
summarized his model in a short monograph entitled Valence and the Structure of Atoms and
Molecules. His renewal of interest in this subject was largely stimulated by the activities of
the American chemist and General Electric researcher Irving Langmuir, who between 1919
and 1921 popularized and elaborated Lewis's model. Langmuir subsequently introduced the
term covalent bond. In 1921, Otto Stern and Walther Gerlach establish concept of quantum
mechanical spin in subatomic particles.

For cases where no sharing was involved, Lewis in 1923 developed the electron pair theory
of acids and base: Lewis redefined an acid as any atom or molecule with an incomplete octet
that was thus capable of accepting electrons from another atom; bases were, of course,
electron donors. His theory is known as the concept of Lewis acids and bases. In 1923, G. N.
Lewis and Merle Randall published Thermodynamics and the Free Energy of Chemical
Substances, first modern treatise on chemical thermodynamics.

The 1920s saw a rapid adoption and application of Lewis's model of the electron-pair bond in
the fields of organic and coordination chemistry. In organic chemistry, this was primarily due
to the efforts of the British chemists Arthur Lapworth, Robert Robinson, Thomas Lowry, and
Christopher Ingold; while in coordination chemistry, Lewis's bonding model was promoted
through the efforts of the American chemist Maurice Huggins and the British chemist Nevil
Sidgwick.

Quantum mechanics

Quantum mechanics in the 1920s

From left to right, top row: Louis de Broglie (1892–
1987) and Wolfgang Pauli (1900–58); second row:
Erwin Schrödinger (1887–1961) and Werner
Heisenberg (1901–76)
Main articles: Louis de Broglie, Wolfgang Pauli, Erwin Schrödinger, and Werner Heisenberg

In 1924, French quantum physicist Louis de Broglie published his thesis, in which he
introduced a revolutionary theory of electron waves based on wave–particle duality in his
thesis. In his time, the wave and particle interpretations of light and matter were seen as being
at odds with one another, but de Broglie suggested that these seemingly different
characteristics were instead the same behavior observed from different perspectives — that
particles can behave like waves, and waves (radiation) can behave like particles. Broglie's
proposal offered an explanation of the restriction motion of electrons within the atom. The
first publications of Broglie's idea of "matter waves" had drawn little attention from other
physicists, but a copy of his doctoral thesis chanced to reach Einstein, whose response was
enthusiastic. Einstein stressed the importance of Broglie's work both explicitly and by
building further on it.

In 1925, Austrian-born physicist Wolfgang Pauli developed the Pauli exclusion principle,
which states that no two electrons around a single nucleus in an atom can occupy the same
quantum state simultaneously, as described by four quantum numbers. Pauli made major
contributions to quantum mechanics and quantum field theory - he was awarded the 1945
Nobel Prize for Physics for his discovery of the Pauli exclusion principle - as well as solid-
state physics, and he successfully hypothesized the existence of the neutrino. In addition to
his original work, he wrote masterful syntheses of several areas of physical theory that are
considered classics of scientific literature.

The Schrödinger equation

In 1926 at the age of 39, Austrian theoretical physicist Erwin Schrödinger produced the
papers that gave the foundations of quantum wave mechanics. In those papers he described
his partial differential equation that is the basic equation of quantum mechanics and bears the
same relation to the mechanics of the atom as Newton's equations of motion bear to planetary
astronomy. Adopting a proposal made by Louis de Broglie in 1924 that particles of matter
have a dual nature and in some situations act like waves, Schrödinger introduced a theory
describing the behaviour of such a system by a wave equation that is now known as the
Schrödinger equation. The solutions to Schrödinger's equation, unlike the solutions to
Newton's equations, are wave functions that can only be related to the probable occurrence of
physical events. The readily visualized sequence of events of the planetary orbits of Newton
is, in quantum mechanics, replaced by the more abstract notion of probability. (This aspect of
the quantum theory made Schrödinger and several other physicists profoundly unhappy, and
he devoted much of his later life to formulating philosophical objections to the generally
accepted interpretation of the theory that he had done so much to create.)

German theoretical physicist Werner Heisenberg was one of the key creators of quantum
mechanics. In 1925, Heisenberg discovered a way to formulate quantum mechanics in terms
of matrices. For that discovery, he was awarded the Nobel Prize for Physics for 1932. In 1927
he published his uncertainty principle, upon which he built his philosophy and for which he is
best known. Heisenberg was able to demonstrate that if you were studying an electron in an
atom you could say where it was (the electron's location) or where it was going (the electron's
velocity), but it was impossible to express both at the same time. He also made important
contributions to the theories of the hydrodynamics of turbulent flows, the atomic nucleus,
ferromagnetism, cosmic rays, and subatomic particles, and he was instrumental in planning
the first West German nuclear reactor at Karlsruhe, together with a research reactor in
Munich, in 1957. Considerable controversy surrounds his work on atomic research during
World War II.

Quantum chemistry

Main article: Quantum chemistry

Some view the birth of quantum chemistry in the discovery of the Schrödinger equation and
its application to the hydrogen atom in 1926.[citation needed] However, the 1927 article of Walter
Heitler and Fritz London[89] is often recognised as the first milestone in the history of
quantum chemistry. This is the first application of quantum mechanics to the diatomic
hydrogen molecule, and thus to the phenomenon of the chemical bond. In the following years
much progress was accomplished by Edward Teller, Robert S. Mulliken, Max Born, J. Robert
Oppenheimer, Linus Pauling, Erich Hückel, Douglas Hartree, Vladimir Aleksandrovich Fock,
to cite a few.[citation needed]

Still, skepticism remained as to the general power of quantum mechanics applied to complex
chemical systems.[citation needed] The situation around 1930 is described by Paul Dirac:[90]

The underlying physical laws necessary for the mathematical theory of a large part of
physics and the whole of chemistry are thus completely known, and the difficulty is
only that the exact application of these laws leads to equations much too complicated
to be soluble. It therefore becomes desirable that approximate practical methods of
applying quantum mechanics should be developed, which can lead to an explanation
of the main features of complex atomic systems without too much computation.

Hence the quantum mechanical methods developed in the 1930s and 1940s are often referred
to as theoretical molecular or atomic physics to underline the fact that they were more the
application of quantum mechanics to chemistry and spectroscopy than answers to chemically
relevant questions. In 1951, a milestone article in quantum chemistry is the seminal paper of
Clemens C. J. Roothaan on Roothaan equations.[91] It opened the avenue to the solution of the
self-consistent field equations for small molecules like hydrogen or nitrogen. Those
computations were performed with the help of tables of integrals which were computed on
the most advanced computers of the time.[citation needed]
In the 1940s many physicists turned from molecular or atomic physics to nuclear physics
(like J. Robert Oppenheimer or Edward Teller). Glenn T. Seaborg was an American nuclear
chemist best known for his work on isolating and identifying transuranium elements (those
heavier than uranium). He shared the 1951 Nobel Prize for Chemistry with Edwin Mattison
McMillan for their independent discoveries of transuranium elements. Seaborgium was
named in his honour, making him the only person, along Albert Einstein and Yuri
Oganessian, for whom a chemical element was named during his lifetime.

Molecular biology and biochemistry

Main articles: History of molecular biology and History of biochemistry

By the mid 20th century, in principle, the integration of physics and chemistry was extensive,
with chemical properties explained as the result of the electronic structure of the atom; Linus
Pauling's book on The Nature of the Chemical Bond used the principles of quantum
mechanics to deduce bond angles in ever-more complicated molecules. However, though
some principles deduced from quantum mechanics were able to predict qualitatively some
chemical features for biologically relevant molecules, they were, till the end of the 20th
century, more a collection of rules, observations, and recipes than rigorous ab initio
quantitative methods.[citation needed]

Diagrammatic representation of some key structural features of DNA

This heuristic approach triumphed in 1953 when James Watson and Francis Crick deduced
the double helical structure of DNA by constructing models constrained by and informed by
the knowledge of the chemistry of the constituent parts and the X-ray diffraction patterns
obtained by Rosalind Franklin.[92] This discovery lead to an explosion of research into the
biochemistry of life.

In the same year, the Miller–Urey experiment demonstrated that basic constituents of protein,
simple amino acids, could themselves be built up from simpler molecules in a simulation of
primordial processes on Earth. Though many questions remain about the true nature of the
origin of life, this was the first attempt by chemists to study hypothetical processes in the
laboratory under controlled conditions.[citation needed]

In 1983 Kary Mullis devised a method for the in-vitro amplification of DNA, known as the
polymerase chain reaction (PCR), which revolutionized the chemical processes used in the
laboratory to manipulate it. PCR could be used to synthesize specific pieces of DNA and
made possible the sequencing of DNA of organisms, which culminated in the huge human
genome project.

An important piece in the double helix puzzle was solved by one of Pauling's students
Matthew Meselson and Frank Stahl, the result of their collaboration (Meselson–Stahl
experiment) has been called as "the most beautiful experiment in biology".

They used a centrifugation technique that sorted molecules according to differences in

weight. Because nitrogen atoms are a component of DNA, they were labelled and therefore
tracked in replication in bacteria.

Late 20th century

Buckminsterfullerene, C60

In 1970, John Pople developed the Gaussian program greatly easing computational chemistry
calculations.[93] In 1971, Yves Chauvin offered an explanation of the reaction mechanism of
olefin metathesis reactions.[94] In 1975, Karl Barry Sharpless and his group discovered a
stereoselective oxidation reactions including Sharpless epoxidation,[95][96] Sharpless
asymmetric dihydroxylation,[97][98][99] and Sharpless oxyamination.[100][101][102] In 1985, Harold
Kroto, Robert Curl and Richard Smalley discovered fullerenes, a class of large carbon
molecules superficially resembling the geodesic dome designed by architect R. Buckminster
Fuller.[103] In 1991, Sumio Iijima used electron microscopy to discover a type of cylindrical
fullerene known as a carbon nanotube, though earlier work had been done in the field as early
as 1951. This material is an important component in the field of nanotechnology.[104] In 1994,
Robert A. Holton and his group achieved the first total synthesis of Taxol.[105][106][107] In 1995,
Eric Cornell and Carl Wieman produced the first Bose–Einstein condensate, a substance that
displays quantum mechanical properties on the macroscopic scale.[108]

Mathematics and chemistry

Classically, before the 20th century, chemistry was defined as the science of the nature of
matter and its transformations. It was therefore clearly distinct from physics which was not
concerned with such dramatic transformation of matter. Moreover, in contrast to physics,
chemistry was not using much of mathematics. Even some were particularly reluctant to use
mathematics within chemistry. For example, Auguste Comte wrote in 1830:

Every attempt to employ mathematical methods in the study of chemical questions

must be considered profoundly irrational and contrary to the spirit of chemistry.... if
 mathematical analysis should ever hold a prominent place in chemistry -- an
aberration which is happily almost impossible -- it would occasion a rapid and
widespread degeneration of that science.

However, in the second part of the 19th century, the situation changed and August Kekulé
wrote in 1867:

I rather expect that we shall someday find a mathematico-mechanical explanation for

what we now call atoms which will render an account of their properties.

Scope of chemistry
As understanding of the nature of matter has evolved, so too has the self-understanding of the
science of chemistry by its practitioners. This continuing historical process of evaluation
includes the categories, terms, aims and scope of chemistry. Additionally, the development of
the social institutions and networks which support chemical enquiry are highly significant
factors that enable the production, dissemination and application of chemical knowledge.
(See Philosophy of chemistry)

Chemical industry

Main article: Chemical industry

The later part of the nineteenth century saw a huge increase in the exploitation of petroleum
extracted from the earth for the production of a host of chemicals and largely replaced the use
of whale oil, coal tar and naval stores used previously. Large-scale production and refinement
of petroleum provided feedstocks for liquid fuels such as gasoline and diesel, solvents,
lubricants, asphalt, waxes, and for the production of many of the common materials of the
modern world, such as synthetic fibers, plastics, paints, detergents, pharmaceuticals,
adhesives and ammonia as fertilizer and for other uses. Many of these required new catalysts
and the utilization of chemical engineering for their cost-effective production.

In the mid-twentieth century, control of the electronic structure of semiconductor materials

was made precise by the creation of large ingots of extremely pure single crystals of silicon
and germanium. Accurate control of their chemical composition by doping with other
elements made the production of the solid state transistor in 1951 and made possible the
production of tiny integrated circuits for use in electronic devices, especially computers.

See also
Histories and timelines

 Atomic theory
 Cupellation
 History of chromatography
 History of electrochemistry
 History of the molecule
 History of molecular biology
 History of physics
  History of science and technology
 History of the periodic table
 History of thermodynamics
 History of energy
 History of molecular theory
 History of materials science
 List of years in science
 Nobel Prize in chemistry
 Timeline of atomic and subatomic physics
 Timeline of chemical elements discoveries
 Timeline of chemistry
 Timeline of materials technology
 Timeline of thermodynamics, statistical mechanics, and random processes
 The Chemical History of a Candle
 The Mystery of Matter: Search for the Elements (PBS film)

Notable chemists

listed chronologically:

 List of chemists
 Robert Boyle, 1627–1691
 Joseph Black, 1728–1799
 Joseph Priestley, 1733–1804
 Carl Wilhelm Scheele, 1742–1786
 Antoine Lavoisier, 1743–1794
 Alessandro Volta, 1745–1827
 Jacques Charles, 1746–1823
 Claude Louis Berthollet, 1748–1822
 Amedeo Avogadro, 1776-1856
 Joseph-Louis Gay-Lussac, 1778–1850
 Humphry Davy, 1778–1829
 Jöns Jakob Berzelius, inventor of modern chemical notation, 1779–1848
 Justus von Liebig, 1803–1873
 Louis Pasteur, 1822–1895
 Stanislao Cannizzaro, 1826–1910
 Friedrich August Kekulé von Stradonitz, 1829–1896
 Dmitri Mendeleev, 1834–1907
 Josiah Willard Gibbs, 1839–1903
 J. H. van 't Hoff, 1852–1911
 William Ramsay, 1852–1916
 Svante Arrhenius, 1859–1927
 Walther Nernst, 1864–1941
 Marie Curie, 1867–1934
 Gilbert N. Lewis, 1875–1946
 Otto Hahn, 1879–1968
 Irving Langmuir, 1881–1957
 Linus Pauling, 1901–1994
 Glenn T. Seaborg, 1912–1999
 Robert Burns Woodward, 1917-1979
  Frederick Sanger, 1918-2013
 Geoffrey Wilkinson, 1921-1996
 Rudolph A. Marcus, 1923-
 George Andrew Olah, 1926-2017
 Elias James Corey, 1928-
 Akira Suzuki, 1930-
 Richard F. Heck, 1931-2015
 Harold Kroto, 1939-2016
 Jean-Marie Lehn, 1939-
 Peter Atkins, 1940-
 Barry Sharpless, 1941-
 Richard Smalley, 1943–2005
 Jean-Pierre Sauvage, 1944-

Notes
1. Selected Classic Papers from the History of Chemistry
2. "History of Gold". Gold Digest. Retrieved 2007-02-04.
3. Photos, E., 'The Question of Meteorictic versus Smelted Nickel-Rich Iron:
Archaeological Evidence and Experimental Results' World Archaeology Vol. 20, No.
3, Archaeometallurgy (February 1989), pp. 403–421. Online version accessed on
2010-02-08.
4. W. Keller (1963) The Bible as History, p. 156 ISBN 0-340-00312-X
5. Radivojević, Miljana; Rehren, Thilo; Pernicka, Ernst; Šljivar, Dušan; Brauns,
Michael; Borić, Dušan (2010). "On the origins of extractive metallurgy: New
evidence from Europe". Journal of Archaeological Science. 37 (11): 2775.
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6. Neolithic Vinca was a metallurgical culture Stonepages from news sources November
2007
7. Will Durant wrote in The Story of Civilization I: Our Oriental Heritage:

"Something has been said about the chemical excellence of cast iron in ancient India,
and about the high industrial development of the Gupta times, when India was looked
to, even by Imperial Rome, as the most skilled of the nations in such chemical
industries as dyeing, tanning, soap-making, glass and cement... By the sixth century
the Hindus were far ahead of Europe in industrial chemistry; they were masters of
calcinations, distillation, sublimation, steaming, fixation, the production of light
without heat, the mixing of anesthetic and soporific powders, and the preparation of
metallic salts, compounds and alloys. The tempering of steel was brought in ancient
India to a perfection unknown in Europe till our own times; King Porus is said to have
selected, as a specially valuable gift from Alexander, not gold or silver, but thirty
pounds of steel. The Moslems took much of this Hindu chemical science and industry
to the Near East and Europe; the secret of manufacturing "Damascus" blades, for
example, was taken by the Arabs from the Persians, and by the Persians from India."

8. B. W. Anderson (1975) The Living World of the Old Testament, p. 154, ISBN 0-582-
48598-3
9. R. F. Tylecote (1992) A History of Metallurgy ISBN 0-901462-88-8
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Discovery, and Invention (3rd edition). London: André Deutsch. pp. 44–56.
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11. Will Durant (1935), Our Oriental Heritage:

"Two systems of Hindu thought propound physical theories suggestively similar to

those of Greece. Kanada, founder of the Vaisheshika philosophy, held that the world
was composed of atoms as many in kind as the various elements. The Jains more
nearly approximated to Democritus by teaching that all atoms were of the same kind,
producing different effects by diverse modes of combinations. Kanada believed light
and heat to be varieties of the same substance; Udayana taught that all heat comes
from the sun; and Vachaspati, like Newton, interpreted light as composed of minute
particles emitted by substances and striking the eye."

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18. William Royall Newman. Atoms and Alchemy: Chymistry and the experimental
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20. Stanton J. Linden. The alchemy reader: from Hermes Trismegistus to Isaac Newton
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1943). Repr. By Fuat Sezgin, (Natural Sciences in Islam. 67-68), Frankfurt. 2002:

"To form an idea of the historical place of Jabir's alchemy and to tackle the problem
of its sources, it is advisable to compare it with what remains to us of the alchemical
literature in the Greek language. One knows in which miserable state this literature
 reached us. Collected by Byzantine scientists from the tenth century, the corpus of the
Greek alchemists is a cluster of incoherent fragments, going back to all the times
since the third century until the end of the Middle Ages."

"The efforts of Berthelot and Ruelle to put a little order in this mass of literature led
only to poor results, and the later researchers, among them in particular Mrs.
Hammer-Jensen, Tannery, Lagercrantz, von Lippmann, Reitzenstein, Ruska, Bidez,
Festugiere and others, could make clear only few points of detail…

The study of the Greek alchemists is not very encouraging. An even surface
examination of the Greek texts shows that a very small part only was organized
according to true experiments of laboratory: even the supposedly technical writings,
in the state where we find them today, are unintelligible nonsense which refuses any
interpretation.

It is different with Jabir's alchemy. The relatively clear description of the processes
and the alchemical apparatuses, the methodical classification of the substances, mark
an experimental spirit which is extremely far away from the weird and odd
esotericism of the Greek texts. The theory on which Jabir supports his operations is
one of clearness and of an impressive unity. More than with the other Arab authors,
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